Nitrogen-metal coordination fertilizers and methods of manufacture

Abstract

Efficient, controlled release crystalline fertilizers may be produced by reacting urea and a metal salt. The crystalline fertilizers include at least one component in the classes of crystalline coordination polymer fertilizer; crystalline coordination complex fertilizer; and crystalline ionic compound fertilizer may be developed as controlled release, efficient fertilizers. The method of producing such crystalline fertilizers produces at least one composition having a nitrogen-metal polymer or a nitrogen metal complex that may be used as a fertilizer.

Description

[0001] TITLE Nitrogen-Metal CoordinaƟon FerƟlizers and Methods of Manufacture FIELD OF THE INVENTION 5 Crystalline composiƟons comprising at least one component in the classes of crystalline coordinaƟon polymer ferƟlizer; crystalline coordinaƟon complex ferƟlizer; and crystalline ionic compound ferƟlizer may be controlled release, efficient ferƟlizers. The method of producing such crystalline ferƟlizers includes reacƟng a metal salt and a urea to form a nitrogen-metal polymer ferƟlizer and / or a nitrogen-metal complex ferƟlizer. 10 BACKGROUND Global populaƟon projecƟons indicate a substanƟal increase to approximately 9.5 billion by 2050, necessitaƟng a corresponding increase in world food producƟon to meet growing demand. A criƟcal component of supporƟng this expanded agricultural output is the effecƟve 15 provision of essenƟal plant nutrients. Nutrients are fundamental for plant growth, development, and overall crop yield. The agricultural sector, along with nurseries, landscapers, and homeowners, widely uƟlizes nutrient- based products to support plant vitality. These substances contribute vital elements to soils and plants, sƟmulaƟng growth while also playing a role in regulaƟng soil pH and ferƟlity. 20 Plant nutriƟon systems typically involve both macronutrients and micronutrients. Macronutrients are required in relaƟvely large quanƟƟes for robust plant development, with nitrogen (N), phosphorus (P), and potassium (K) being primary examples. Nitrogen, in parƟcular, is oŌen required in the largest quanƟƟes, with urea represenƟng a significant source due to its high nitrogen content and versaƟlity. Secondary macronutrients, such as calcium (Ca), 25 magnesium (Mg), sulfur (S), and chlorine (Cl), are also vital. Micronutrients, including boron (B), cobalt (Co), nickel (Ni), chromium (Cr), manganese (Mn), iron (Fe), zinc (Zn), copper (Cu), molybdenum (Mo), silicon (Si), and selenium (Se), are equally criƟcal for healthy plant growth, though needed in smaller amounts. 1

[0002] Many of these essenƟal macro- and micronutrients are supplied in the form of metal salts, which are inorganic compounds. These metals can include, but are not limited to, calcium, potassium, magnesium, zinc, copper, manganese, sodium, iron, molybdenum, boron, cobalt, nickel, silicon, selenium, and chromium. The salts can comprise various anions such as sulfates 5 (SO4), nitrates (NO3), chlorides (Cl), oxides (O), hydroxides (OH), carbonates (CO3), phosphates (PO4), and acetates (OAc). A significant challenge in plant nutrient delivery is the inherent interacƟon of nutrients with the soil environment. Nutrients, parƟcularly nitrogen from sources like urea, are suscepƟble to rapid chemical transformaƟons and physical losses. For instance, urea readily 10 undergoes enzymaƟc hydrolysis by ubiquitous soil microorganisms, converƟng it into gaseous ammonia and carbon dioxide (CH4N2O+H2O→2NH3+CO2). This ammonia can then volaƟlize into the atmosphere, a process influenced by factors such as wind speed, temperature, soil pH, and water content. Despite its value as a nutrient source, this suscepƟbility to degradaƟon results in substanƟal nutrient loss. 15 Furthermore, many metal salts, including those providing essenƟal micronutrients like iron, manganese, zinc, and copper, are prone to oxidaƟon, precipitaƟon, orfixaƟon within the complex soil matrix. These reacƟons can render the nutrients chemically bound to soil parƟcles, significantly reducing their availability for plant uptake. Without inherent protecƟon, the efficacy of these nutrient sources is diminished, oŌen necessitaƟng higher applicaƟon rates to 20 meet plant requirements. These challenges highlight a pervasive need across all macronutrient and micronutrient categories for advanced nutrient delivery systems that inherently provide improved efficiency and enhanced environmental safety. Such systems are sought to miƟgate nutrient losses arising from natural soil reacƟons like complex formaƟon,fixaƟon, precipitaƟon, and leaching. 25 The pursuit of more efficient and sustainable nutrient management strategies has been a conƟnuous focus within agricultural science. Fundamental chemistry principles, including coordinaƟon chemistry, soluƟon chemistry, and crystallizaƟon principles, are indispensable in understanding and designing systems that address these inherent nutrient management challenges. 2

[0003] CoordinaƟon chemistry, a disƟnct subdiscipline of inorganic chemistry, invesƟgates and describes molecules or ions where a central metal atom or ion is bonded to surrounding molecules or ions (ligands) via coordinate covalent bonds. The unique structures, bonding, reacƟvity, and properƟes of these coordinaƟon compounds are governed by coordinaƟon 5 chemistry principles. Both molecular-level coordinaƟon complexes and their solid-state crystalline forms are fundamentally described by thisfield. While crystallography offers insights into long-range order and bulk properƟes, the core idenƟty, bonding, and funcƟonality of these systems derive from coordinaƟon chemistry. This dual understanding is crucial for ensuring that nutrient delivery systems effecƟvely transiƟon from molecular design to pracƟcal crystalline 10 forms, bridging fundamental chemistry with real-world agricultural technologies. By leveraging coordinaƟon chemistry principles, it is possible to design sophisƟcated metal-ligand systems that inherently enhance nutrient delivery and miƟgate environmental impact. In a chemical context, a coordinaƟon complex is a species with a central metal atom or ion bonded to ligands. A crystalline composiƟon refers to such a coordinaƟon structure exisƟng 15 in an ordered, three-dimensional solid state. The properƟes of a crystalline structure are influenced by both the nature of the coordinaƟon structure itself and its arrangement within the crystal laƫce. These inherent properƟes are key to transforming raw materials into forms suitable for advanced nutrient delivery. SoluƟon chemistry and thermodynamics, involving dissoluƟon, solvaƟon, chemical equilibrium, and reacƟon kineƟcs, are also fundamental to 20 understanding the behavior and formaƟon of such systems. Urea, chemically an organic amide with two ammine (NH2) groups joined by a carbonyl funcƟonal group, is widely used due to its high nitrogen content and ease of transport. However, it is suscepƟble to rapid decomposiƟon by ubiquitous soil microorganisms, leading to transient availability for plants. This inherent suscepƟbility to conversion into gaseous ammonia 25 and carbon dioxide underscores a primary challenge in nitrogen management. The broader objecƟve within nutrient management is to develop approaches that inherently improve nutrient uptake and reduce nutrient loss by regulaƟng the rate of release or changing the interacƟons between soil and nutrient sources. There is a conƟnuous search for 3

[0004] efficacious, economical, and environmentally sustainable soluƟons to the inherent challenges of nutrient producƟon and applicaƟon in agriculture. SUMMARY 5 FerƟlizers are any natural or arƟficial substances that if applied to soil or directly to the plant supply plant nutrients. FerƟlizers may be used to increase the ferƟlity of the soil and improve plant growth and producƟvity. Plants need water and specific nutrients to grow and thrive. FerƟlizers nitrogen (N), phosphorus (P), and potassium (K), which are needed in large quanƟƟes by plants, may be added to the soil to enhance soil ferƟlity. FerƟlizers may replenish 10 nutrients that have been used by crops or are otherwise deficient in the soil. By providing essenƟal nutrients, ferƟlizers help plants grow faster and larger, potenƟally resulƟng in increased yields offlowers, fruits, and vegetables. FerƟlizers include inorganic ferƟlizers. Inorganic ferƟlizers are man-made using chemical processes. Inorganic ferƟlizers may be fast-acƟng, controlled release (slower acƟng), and 15 contain precise nutrient raƟos for the specific or class of plants or crops to be grown. As described above, ferƟlizers may comprise nitrogen (N) which is crucial for leafy green growth, phosphorus (P) which aids root development,flowering, and fruiƟng and potassium (K) which supports strong stem growth and overall plant health. However, over-applicaƟon of ferƟlizers can damage or kill plants and negaƟvely impact the environment through nutrient runoff. 20 Urea, also known as carbamide, is a widely used syntheƟc nitrogen ferƟlizer. Urea is a common source of nitrogen for plants because it contains the highest nitrogen content (46%) compared to other common solid nitrogen ferƟlizers. Urea also has other beneficial properƟes including different applicaƟons methods, lower handling, storage, and transportaƟon costs compared to ferƟlizers with lower nitrogen content and provides readily available nitrogen for 25 rapid uptake and uƟlizaƟon. However, urea may be difficult to properly apply since urea may break down to ammonia and volaƟze, thereby losing nitrogen to the atmosphere. Further, urea comprises biuret which can be toxic to some plants, parƟcularly at high concentraƟons or when placed near seeds. There is a tendency to over apply urea due to the potenƟal of loss through volaƟlity. Over- 4

[0005] applicaƟon of urea can result in increased costs, ferƟlizer burn, and excessive nitrogen use can contribute to environmental problems like nitrogen leaching and greenhouse gas emissions. Embodiments of the ferƟlizer described herein provide a low volaƟlity urea based ferƟlizer and metals. The ferƟlizers comprise crystalline ferƟlizer composiƟons. An embodiment 5 of the method of producing a crystalline ferƟlizer composiƟon may comprise reacƟng a metal salt with urea. At least one metal salt may be mixed with a nitrogen source comprising urea. The metals salt or metal salts may be mixed with the urea in a solvent. In certain embodiments, the solvent may comprise water to form a reacƟon mixture. The method may comprise heaƟng the reacƟon mixture to a temperature sufficient to 10 form the crystalline ferƟlizer composiƟon in a resultant mixture. The temperature, Ɵme at temperature, molar raƟo of reactants, molar raƟo of metal salt to urea, specific metal salt, cooling rate, composiƟon of the solvent, and other factors produce different crystalline structures. Thus, the composiƟon of thefinal product may be engineered by controlling these and other parameters of the method. 15 The basic reactants include at least one metal salt and urea. From these basic reactants, the products produced from these reactants may generally be classified as crystalline ferƟlizer composiƟons in the following groups. A) crystalline coordinaƟon polymer ferƟlizers; B) crystalline coordinaƟon complex ferƟlizers; and 20 C) crystalline ionic compound ferƟlizers. Each of these crystalline ferƟlizers may include the following composiƟons: The crystalline coordinaƟon polymer ferƟlizer may include one or more of the following: 1) crystalline coordinaƟon nitrogen-metal polymer ferƟlizers; and 2) crystalline coordinaƟon non-nitrogen-metal polymer ferƟlizers; 25 The crystalline coordinaƟon complex ferƟlizers may may include one or more of the following: 1) crystalline coordinaƟon nitrogen-metal complex ferƟlizers; and 2) crystalline coordinaƟon non-nitrogen-metal complex ferƟlizers, The crystalline ionic compound ferƟlizer may include one or more of the following: 1) crystalline nitrogen-ionic compound ferƟlizers; and 5

[0006] 2) crystalline non-nitrogen-ionic compound ferƟlizers. In one embodiment, the crystalline ferƟlizers comprise a crystalline coordinaƟon nitrogen-metal polymer ferƟlizer, and a crystalline coordinaƟon nitrogen-metal complex ferƟlizer. 5 The crystalline coordinaƟon nitrogen-metal polymer ferƟlizers may comprise a unit cell comprising at least one of an ammonium-metal polymer, a urea-metal polymer, and an ammine-metal polymer. It is theorized that the urea and metal salt react to form these coordinaƟon polymers directly or from the unit cells precursors. The crystalline coordinaƟon nitrogen-metal complex ferƟlizer comprising at least one of 10 an ammonium-metal complex, a urea-metal complex, and an ammine-metal complex. The raƟo of these components depends on the reacƟon parameters as discussed above. Further components may also be present also based upon the engineered reacƟon parameters. The crystalline ferƟlizers describe herein provide a low volaƟle, efficient ferƟlizer that may be more accurately, and cost effecƟvely applied. The crystalline coordinaƟon non-nitrogen-metal 15 polymer ferƟlizer may comprise unit cells comprising a metal salt. The metal salt may be a sulfate. In further embodiments, the crystalline ferƟlizers may comprise crystalline ionic compounds including at least one of a crystalline nitrogen-ionic compound ferƟlizer and crystalline non-nitrogen-ionic compound. 20 Embodiments of the method comprise producing these crystalline ferƟlizer composiƟons by mixing at least one metal salt, a nitrogen source comprising urea, and a solvent comprising water, to form a reacƟon mixture. The reacƟon mixture may be sƟrred to solubilize the metal salt and the urea and / or be heated to a temperature sufficient to form the crystalline ferƟlizer composiƟon in a resultant mixture. The temperature may be controlled to control the 25 equilibrium of the reacƟon. In specific embodiments, the reacƟon mixture may be heated to a temperature that causes the reacƟon to iniƟate and proceed, for example, the temperature may be a temperature greater than 70°C, a temperature greater than 50°C and less than 135°C, or to a temperature of approximately 100°C. Temperature control is one method of engineering the 6

[0007] desired crystalline ferƟlizer composiƟon. The resultant mixture is a crystalline ferƟlizer composiƟon that comprises the engineered solid-state structures. Embodiments of the method may further comprise mixing at least one metal salt, a nitrogen source comprising urea, and a solvent comprising water, to form a reacƟon mixture, 5 wherein the molar raƟo of metal salt to urea is in the range from 1:25 to 25:1. In other embodiments, the molar raƟo of metal salt to urea is in the range from 1:6 to 6:1; in sƟll other embodiments, the molar raƟo of metal salt to urea is in the range from 1:1 to 1:12; and in a specific embodiment, the molar raƟo of metal salt to urea is between 1: 1.5 to 1:8.5. The engineered solid-state structures may comprise a crystalline coordinaƟon polymer 10 ferƟlizer, a crystalline coordinaƟon complex ferƟlizer, and combinaƟons thereof. For some reactants and methods, cooling the resultant mixture may facilitate formaƟon of the crystalline ferƟlizer composiƟon. Further, the resultant mixture may comprise more water than desired and the method may include drying the crystalline ferƟlizer composiƟon to form a recovered crystalline ferƟlizer composiƟon. 15 The metal may be any metal that coordinates with urea to form polymer and complex ferƟlizers. For example, a metal of the at least one metal salt may comprise at least one of zinc, copper, manganese, boron, calcium, potassium, sodium, iron, magnesium, molybdenum, boron, cobalt, selenium, nickel, silicon, and chromium. The metal salt of these metals may be a sulfate, nitrate, chloride, oxide, hydroxide, carbonate, phosphate, and acetate, for example. Preferably, 20 the crystalline coordinaƟon nitrogen-metal polymer ferƟlizer and the crystalline coordinaƟon nitrogen-metal complex ferƟlizer comprise a metal coordinaƟon by at least one ligand having a donor atom selected from oxygen, nitrogen, sulfur, or chlorine. The reactants may be solubilized in a solvent. Typically, the solvent will comprise water or another liquid that can sufficiently solubilize the reactants. In some embodiments, the 25 solvent may comprise at least one carboxylic acid. The carboxylic acids may include citric acid, aceƟc acid, oxalic acid, malic acid, lacƟc acid, tartaric acid, and derivaƟves or combinaƟons thereof. Examples of products in different resultant mixtures from methods starƟng with different metal salt reactants include, but are not limited to, a crystalline coordinaƟon urea- 7

[0008] metal polymer ferƟlizer produced by the method may have a crystalline structure of (CH4N2O)4Ca(SO4) or tetrakis(urea) calcium sulfate; a crystalline coordinaƟon ammonium-metal complex ferƟlizer produced by the method may have a crystalline structure of (NH4)2Mg(SO4)2(H2O)6; a crystalline coordinaƟon ammonium-metal complex ferƟlizer produced 5 by the method may have a crystalline structure of (NH4)2Zn(OH2)6(SO4)2; a crystalline coordinaƟon ammine-metal polymer ferƟlizer produced by the method may have a crystalline structure of [(H3N)2Zn(SO4)2]2-×2(H4N+), a crystalline coordinaƟon ammonium-metal complex ferƟlizer produced by the method may have a crystalline structure of (NH4)2Fe(SO4)2(H2O)6; a crystalline coordinaƟon urea-metal polymer ferƟlizer having a crystalline structure of 10 Mn2(SO4)2(CH4N2O)6; and a crystalline coordinaƟon ammine-metal complex ferƟlizer produced by the method may have a crystalline structure of Cu(SO4)(NH3)4(H2O), for example. BRIEF DESCRIPTION OF THE DRAWINGS FIG 1. depicts a process flow diagram illustrating a plant layout for Crystalline Coordination 15 Nitrogen-Metal Polymer and Complex Fertilizer production process, including granulation and coating of nitrogen-metal complex fertilizers; FIG 2. depicts a process flow diagram illustrating a plant layout for nitrogen-metal polymer and complex fertilizers with coating process; FIG 3. depicts the core composition of (CH4N2O)4Ca(SO4): Crystalline coordination nitrogen- 20 metal polymer fertilizer, urea-metal sulfate composition; FIG 4. depicts the unit cell of (CH4N2O)4Ca(SO4): Crystalline coordination nitrogen-metal polymer fertilizer – urea-metal composition; FIG 5. depicts the core composition of [(H3N)2Zn(SO4)2]2-×2(H4N+): Crystalline coordination nitrogen-metal polymer fertilizer – ammine-metal composition; 25 FIG 6. depicts the unit cell of [(H3N)2Zn(SO4)2]2-×2(H4N+): Crystalline coordination nitrogen-metal polymer fertilizer – ammine-metal composition; FIG 7. depicts the core composition of (NH4)2Mn2(SO4)3: Crystalline coordination nitrogen-metal polymer fertilizer – ammonium-metal composition; 8

[0009] FIG 8. depicts the unit cell of (NH4)2Mn2(SO4)3: Crystalline coordination nitrogen-metal polymer fertilizer – ammonium-metal composition; FIG 9. depicts the core composition of Zn₂K(SO₄)₂(OH)(H₂O): Crystalline coordination non- nitrogen-metal polymer fertilizer composition; 5 FIG 10. depicts the unit cell of Zn₂K(SO₄)₂(OH)(H₂O): Crystalline coordination non-nitrogen- metal polymer fertilizer composition; FIG 11. depicts the core composition of Cu3(SO4)(OH)4: Crystalline coordination non-nitrogen- metal polymer fertilizer composition; FIG 12. depicts the unit cell of Cu3(SO4)(OH)4: Crystalline coordination non-nitrogen-metal 10 polymer fertilizer composition; FIG 13. depicts the core composition of Fe(CH4N2O)6(SO4)(H2O): Crystalline coordination nitrogen-metal complex fertilizer – urea-metal composition; FIG 14. depicts the unit cell of Fe(CH4N2O)6(SO4)(H2O):Crystalline coordination nitrogen-metal complex fertilizer – urea-metal composition; 15 FIG 15. depicts the core composition of (NH4)2Mg(SO4)2(H2O)6: Crystalline coordination nitrogen-metal complex fertilizer – ammonium-metal composition; FIG 16.depicts the unit cell of (NH4)2Mg(SO4)2(H2O)6: Crystalline coordination nitrogen-metal complex fertilizer – ammonium-metal composition; FIG 17. depicts the core composition of Cu(SO4)(NH3)4(H2O): Crystalline coordination nitrogen- 20 metal complex fertilizer – ammine-metal composition; FIG 18. depicts the unit cell of Cu(SO4)(NH3)4(H2O): Crystalline coordination nitrogen-metal complex fertilizer – ammine-metal composition; FIG 19. depicts the core composition of (NH₄)₂SO₄:Crystalline nitrogen-ionic compound fertilizer – ammonium-ionic composition; 25 FIG 20. depicts the unit cell of (NH₄)₂SO₄:Crystalline nitrogen-ionic compound fertilizer – ammonium-ionic composition; FIG 21. depicts the core composition of K₂(SO₄): Crystalline non-nitrogen-ionic compound fertilizer composition; and 9

[0010] FIG 22. depicts the unit cell of K₂(SO₄): Crystalline non-nitrogen-ionic compound fertilizer composition. DETAILED DESCRIPTION 5 The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the scope of the claimed invention, its application, or uses, thus the embodiments are claimed to be preferred non-limiting embodiments. The preferred non-limiting embodiments are illustrated in the Brief Description of the Drawings according to principles of patent assembly and the present invention is intended to be 10 read in connection with the accompanying powder and single crystal x-ray diffraction crystallography findings. More efficient fertilizers are needed to meet the growing food production demands and to simultaneously reduce the environmental impact of fertilizing crops. Conventional fertilizers must be applied at greater rates than are used by plants to compensate for soil complexing, 15 run-off, leaching, emissions, and other nutrient losses and inefficiencies. Embodiments of the fertilizers described herein and the fertilizers produced by the methods herein protect and stabilize nutrients for more efficient delivery of nutrients for plant uptake while reducing negative environmental effects. Coordination, thermodynamics / kinetics, and crystallization are core chemistry principles 20 behind this invention, they are indispensable in the development of the fertilizers described herein and determining its properties and benefits as a fertilizer. Using these principles allows optimization of the crystalline coordination structure, functionality, and sustainability of fertilizers. By leveraging urea- and metal-ligand interactions, these fertilizers can achieve targeted nutrient delivery, reduce environmental impact, and enhance crop productivity. 25 Fertilizers are natural or artificial substances containing chemical elements that improve growth and productivity of plants. Fertilizers enhance the natural fertility of the soil or replace chemical elements taken from the soil by previous crops. Crystallography is a branch of science that deals with discerning the arrangement and bonding of atoms in crystalline coordination solids and with the geometric structure 10

[0011] of crystal lattices. Classically, the optical properties of crystals were of value in mineralogy and chemistry for the identification of substances. Modern crystallography is largely based on the analysis of the diffraction of X-rays by crystals acting as optical gratings. Using X-ray crystallography, scientists can determine the internal structures and bonding 5 arrangements of minerals and molecules. Crystalline coordination polymers and complexes comprise ions, molecules, or atoms that are organized in a coordinated dimensional way and are held together by a substantially ordered, cohesive force. Furthermore, the crystalline coordination complexes form regular, repeating arrangement of atoms or molecules. Crystalline coordination polymers and 10 complexes can be described based on the type of atoms, ions or molecules that are made of, how they are bonded together, the dimensional shape that the bonding creates, and the properties of the crystalline coordination structure. Materials that feature a crystal structure can be defined as crystalline. Crystalline polymers and complexes may comprise ordered and symmetrical chemical bonds that affect the overall shape and properties of the material, such 15 as nutrient concentration, bonding, density, stability, and strength. It’s these properties that promote a tightly bound and stable coordination polymer and complex fertilizer derived from urea and metal salts for improved delivery to soil and plants. Catalytic action provided by metal salts is a chemical reaction between the catalyst and a reactant, typically forming chemical intermediates that can react more readily with each 20 other or with another reactant, to form the desired resultant composition. Crystalline coordination polymers and complexes are inorganic or organometallic structures containing metal ion centers linked by ligands, often in a crystalline composition. More formally a coordination polymer and complex are coordination structures with repeating coordination entities extending in 1, 2, or 3 dimensions. 25 Biological activity and plant uptake mechanisms refer to the act of acquisition or interaction between soils, soil microbes, and plant anatomy and physiology in which nutrients are acquired or sequestered from the composition and taken into cells. In the preferred non-limiting embodiments, the present invention is directed to a urea and metal salt solvated reaction process. As described further herein, the urea and metal salt 11

[0012] solvated process may be suitable for making and using the resultant composition as a fertilizer, whereby the fertilizer exhibits improved biological and environmental stability as a crystalline coordination polymer and crystalline coordination complex fertilizer and / or crystalline ionic compound fertilizer. 5 In the preferred non-limiting embodiments, a crystalline fertilizer composition of the present invention may be formed by reacting, in a solvated process, urea and metal salts and mixtures thereof. The metal of the metal salts may be selected from the group comprising of zinc, copper, manganese, boron, calcium, potassium, sodium, iron, magnesium, molybdenum, boron, cobalt, selenium, nickel, silicon and chromium, and mixtures thereof, for example, and 10 metal salt may be selected from the group comprising sulfates, nitrates, chlorides, oxides, hydroxides, carbonates, phosphates, acetates, and mixtures thereof, for example. Non-limiting examples of solvents may include water and at least one carboxylic acid and mixtures thereof. In the preferred non-limiting embodiments, urea, metal salts and water, and / or mixtures thereof, were introduced into a reaction vessel and heated to a reaction temperature 15 sufficient to initiate the reaction between the metal salt and urea, for example, 100^C. With water in the reaction vessel, the urea and metal salts solubilized. Once the urea is dissolved into the solution, the chemical conversion was complete resulting in a crystalline coordination structure and mixture thereof. The crystalline coordination structure comprises a crystalline fertilizer composition. 20 As used herein, the term ”crystalline fertilizer composition” refers to a single chemical compound structure that is formed from at least two distinct starting materials, whereby the starting materials of the present invention correspond to the urea and the metal salts. The crystalline fertilizer composition has some efficacy as a fertilizer. Thus, reactants are converted into distinct crystalline coordination polymer fertilizers and crystalline coordination complex 25 fertilizers and, in some cases, ionic compound fertilizers. The metal salts and the urea may be added directly into the reaction mixture or precursors of the urea and the metal salts may be added to the reaction mixture to subsequently form the reactants. Further, derivatives of urea that react with the metal salts may also be in the reaction mixture. 12

[0013] In the preferred non-limiƟng embodiments, urea, the source of nitrogen, was transformed through the solvated urea and metal salts process into various forms of crystalline coordinaƟon nitrogen-metal polymer and complex ferƟlizer and nitrogen-ionic compound ferƟlizer and mixtures thereof. The crystalline coordinaƟon nitrogen-metal polymer and 5 complex ferƟlizer and nitrogen-ionic compound ferƟlizer and mixtures thereof may include, but may not be limited to, 1) ammonium-metal ferƟlizer and / or 2) urea-metal -ferƟlizer and / or 3) ammine-metal ferƟlizer forms. The inventors have found that the transiƟon of urea and metal salts into ammonium-metal, urea-metal and / or ammine-metal ferƟlizers and mixtures thereof is an innovaƟve approach to transform urea nitrogen into efficient ferƟlizers under the herein10 solvated process. Transforming urea and metal salts into a crystalline coordinaƟon nitrogen- metal polymer and complex ferƟlizer and nitrogen-ionic compound ferƟlizer provides a method of manufacturing that provides enhanced efficiency ferƟlizers. In the preferred non-limiting embodiments, crystalline coordination polymer and complex fertilizer comprised of covalent bonds that stabilize and protect the fertilizer and limit 15 the rate and amount of decomposition of nutrients for more efficient delivery to plants and reduced environmental impact. In the preferred non-limiting embodiments, the present disclosure provides compositions comprising crystalline fertilizers compositions that originate from urea. In the preferred non-limiting embodiments, the present disclosure compositions 20 comprise crystalline fertilizer compositions comprising metal salts in the form of macronutrients and / or micronutrients and mixtures thereof that are protected, stable and more efficient for soil application, plant production and reduced environmental impacts compared with conventional macronutrients and micronutrients. In the preferred non-limiting embodiments, the present disclosure describes crystalline 25 fertilizer compositions providing enhanced efficiency fertilizer properties to support improved environmental conservation through reduction in soil and emissions loss of nutrients by volatilization, leaching, fixation, precipitation, complexing, and run-off. In the preferred non- limiting embodiments, the present disclosure describes crystalline fertilizer compositions that are economical in method of manufacturing for use in large agricultural systems. 13

[0014] In the preferred non-limiting embodiments, the present disclosure describes crystalline fertilizer compositions that contain less than 1 wt% biuret, a toxic component to plant life. Biuret is not produced in significant concentrations by the reaction process comprising urea and metal salts. 5 In the preferred non-limited embodiments, the present disclosure describes crystalline fertilizer compositions that are completely biodegradable supporting best practices in green fertilizer properties, and soil, crop, and environmental agriculture conservation. In the preferred non-limited embodiments, the present disclosure describes crystalline fertilizer compositions wherein the fertilizer is a coating agent for a second fertilizer. 10 In the preferred non-limited embodiments, the present disclosure describes crystalline fertilizer compositions wherein the fertilizer is a coating agent for a second fertilizer, with other coating agents, such as sulfur, wax, polymers, and others that can be added to improve coating properties. In the preferred non-limiting embodiments, the present disclosure describes crystalline 15 fertilizer compositions produced by the process comprising reacting urea and metal salts in water at a reaction temperature, for example, a set-point of 100°C, as water was released into the reaction vessel, urea solubilized (under endothermic conditions). As the urea solubilized, it lowered the temperature of the reaction mix to 90°C until urea was substantially dissolved. The temperature then rose to over 100°C when the reaction is completed. 20 In the preferred non-limiting embodiments, the present describes crystalline fertilizer compositions that can use a broad range of molar ratios of urea to metal salts to provide for selected crystalline fertilizer compositions and their properties, profiles, and concentrations. In the preferred non-limiting embodiments, the present disclosure describes crystalline fertilizer compositions with a mixture of metal salts and urea to best provide for the desired 25 crystalline fertilizer composition and their properties, profiles, and concentrations. In the preferred non-limiting embodiments, crystalline fertilizer compositions, comprising engineered solid-state structures formed by reacting at least one metal salt and a nitrogen source selected from urea, and derivatives thereof, in a solvent comprising water, wherein said engineered solid-state structures are selected from the group consisting of: A) a 14

[0015] crystalline coordination polymer fertilizer; B) a crystalline coordination complex fertilizer; C) a crystalline ionic compound fertilizer; and combinations thereof. “Engineered solid-state structures" refers to crystalline fertilizer compositions that have been synthesized to achieve properties, particularly related to nutrient delivery and release in 5 agricultural applications. It highlights the deliberate design aspect of crystalline fertilizer compositions, differentiating them from simple mixtures or conventional bulk fertilizers. Engineered solid-state structures, are selected from the group consisting of: A) crystalline coordination polymer fertilizer: These are compounds comprising metal ions linked by organic ligands (like urea) into extended, repeating 1D, 2D, or 3D frameworks. The 10 nature of these bonds (coordinate covalent bonds) and the extended network contribute to their specific properties. B) crystalline coordination complex fertilizer: These are discrete molecular units comprising a central metal ion bonded to a specific number of ligands (like urea). While discrete, they form ordered crystalline lattices in the solid state, contributing to stability and controlled release. 15 C) crystalline ionic compound fertilizer: These are compounds formed by electrostatic attraction between positively charged ions (cations, e.g., metal ions or ammonium) and negatively charged ions (anions, e.g., chloride, sulfate, phosphate). While fundamentally different in bonding from coordination structures, they still form ordered crystalline lattices. The term "engineered solid-state structures" is the chosen broad umbrella term to cover 20 the distinct types of crystalline fertilizer compositions invented and synthesized. By explicitly stating that these "engineered solid-state structures comprise" at least one of coordination polymers, coordination complexes, and ionic compounds. Ionic compound fertilizers differ chemically from coordination polymer and complex fertilizers, they are still "solid-state structures" that are "engineered" (i.e., intentionally 25 produced via a specific reaction and crystallization process) to serve as fertilizers. The "engineered" aspect comes from the method of synthesis (reacting urea and metal salts in a specific way to form these crystalline fertilizer compositions as described herein), rather than just mixing pre-existing solid fertilizer components. 15

[0016] Compared to designed coordination polymer or complex fertilizers, traditional or simple ionic compound fertilizers generally have less inherent controlled-release capability. Ionic compound fertilizer (like ammonium nitrate, potassium chloride, simple sulfates): Primarily rely on dissolution in soil water. Their release rate is largely dictated by their intrinsic solubility, 5 crystal size, and the amount of water present. They tend to dissolve relatively quickly, leading to rapid nutrient release and higher losses through leaching, volatilization, and runoff. Coordination Polymer and Complex fertilizers: The very nature of the coordination bonds and the extended framework (in polymers) or the stable complex (in discrete complexes forming a crystal) provides a mechanism for slower, more controlled degradation and release. 10 The nutrient is often "bound" within a more robust structure, which needs to degrade or otherwise break down (e.g., through hydrolysis, microbial action, or ion exchange) before the nutrient becomes fully available. This intrinsic stability and degradation mechanism is the core of the "engineered" controlled-release property. Considerations: 151) Crystal Size and Morphology: Even for ionic compounds, a larger crystal size can lead to slower dissolution. So, an "engineered" ionic compound with specific crystal morphology could exhibit some degree of slower release compared to a fine powder of the same material. 2) Solubility Differences: Some ionic compounds are less soluble than others. So, an "engineered" insoluble or slightly soluble ionic compound would inherently have a slower release rate. 203) The "Engineered" Aspect: Even if some of the ionic compounds might not exhibit the same degree or mechanism of controlled release as coordination polymers and complexes, they are still compositions of the specific engineered synthesis route from the method. 4) Coating vs. Intrinsic Structure: Many commercial controlled-release fertilizers achieve their effect by coating conventional ionic fertilizers (like urea) with polymers or sulfur. This invention, 25 by contrast, focuses on intrinsic structural engineering to achieve controlled release, which is a key differentiator. Though does not preclude coating and may be a coating for other fertilizers. The emphasis on "controlled release" is most directly and intrinsically supported by the dominant properties of the coordination polymer and complex fertilizers. The method may produce crystalline ionic compounds and their "controlled release" properties (if any) would 16

[0017] likely stem from factors related to their inherent solubility or engineered crystal size / form, rather than the unique chemical stability provided by coordination bonds as in the other categories of fertilizers produced by the reaction. In the preferred non-limiting embodiments, crystalline fertilizer compositions 5 comprising; three (3) overarching definitive structural classifications (A, B and C) and six (6) definitive structural sub-classifications (1-6) of the invention; comprising, A) crystalline coordination polymer fertilizer; 1) crystalline coordination nitrogen-metal polymer fertilizer; and 2) crystalline coordination non-nitrogen-metal polymer fertilizer; B) crystalline coordination complex fertilizer; 3) crystalline coordination nitrogen-metal complex fertilizer; and 4) 10 crystalline coordination non-nitrogen-metal complex fertilizer, and, C) crystalline ionic compound fertilizer; 5) crystalline nitrogen-ionic compound fertilizer; and 6) crystalline non- nitrogen-ionic compound fertilizer. In the preferred non-limiting embodiments, crystalline fertilizer compositions comprising three (3) overarching definitive structural classifications and six (6) definitive 15 structural sub-classifications encompass the features and distinctions of the invention, comprising, a) Crystalline Fertilizer; comprising a solid material where the constituent particles (atoms, ions, or molecules) are arranged in a highly ordered, repeating one, two or three-dimensional pattern that extends throughout the entire material. This orderly arrangement is called a crystal 20 lattice. key Features and Distinctions of Crystalline Structure Fertilizer: ^ Ordered Arrangement: The most defining feature is the precise and predictable arrangement of particles. Unlike amorphous solids (like glass or rubber) where particles are randomly arranged, in crystalline solids, there's a long-range order. 25 ^ Repeating Pattern (Unit Cell): This ordered arrangement is built from a fundamental, smallest repeating unit called a unit cell. Imagine bricks in a wall – each brick is a unit cell and stacking them perfectly in three dimensions builds the entire crystalline structure. The unit cell completely reflects the symmetry and structure of the entire crystal. 17

[0018] ^ Long-Range Order: The repeating pattern extends uniformly over long distances within the solid, from the microscopic to the macroscopic level. ^ Well-Defined Geometry: Due to this internal order, crystals often exhibit distinct external geometric shapes with flat faces and sharp edges. Even if a macroscopic crystal isn't 5 perfectly shaped, its internal atomic arrangement is still ordered. ^ Anisotropy: Many physical properties of crystalline solids (like electrical conductivity, thermal conductivity, refractive index, and mechanical strength) can vary depending on the direction in which they are measured. This is because the arrangement of particles and the strength of bonds might be different along different axes. 10 ^ Sharp Melting Point: Crystalline solids have a distinct and sharp melting point. This is because all the particles are held in place by uniform intermolecular forces, and a specific amount of energy is required to break these forces simultaneously, leading to an abrupt transition from solid to liquid. ^ Clean Cleavage: When a crystalline solid is broken, it tends to cleave (break) along 15 specific, well-defined planes. This is a direct consequence of the regular arrangement of particles and the planes of weaker bonds within the crystal lattice. b) Crystalline Coordination Fertilizer; comprising a solid material where metal ions (or metal clusters) are arranged in a highly ordered, repeating three-dimensional pattern throughout the material, linked together by ligands via coordinate covalent bonds. This means the atoms, ions, 20 or molecules are not randomly arranged but form a precise, repeating, long-range order in a crystal lattice. This internal order often leads to well-defined external crystal shapes. This refers to the arrangement of ligands around a central metal atom or ion, forming a coordination complex, where the bonding between the metal and the ligands is primarily coordinate covalent (i.e., one atom donates both electrons to form the bond). 25 Key Features and distinctions of Crystalline Coordination Structure Fertilizer: ^ Metal Centers and Ligands: The fundamental building blocks are metal ions (or metal clusters) and organic or inorganic molecules / ions called ligands. ^ Coordinate Covalent Bonding: The ligands attach to the metal centers through coordinate covalent bonds, where the ligand donates a lone pair of electrons to the metal. 18

[0019] ^ Repeating Units (Unit Cell): Like all crystalline materials, they are built from a repeating unit cell that defines the entire 3D structure. ^ Long-Range Order: The specific arrangement of metal centers and ligands repeats consistently throughout the solid material. 5 ^ Dimensionality: Crystalline coordination structures can exist in various dimensionalities: o 0D (Discrete Molecular Complexes): These are individual, isolated molecules where ligands surround a single metal center, and these discrete molecules then pack into a crystal lattice complex, ions arrange themselves in a crystal. o 1D (Chains): Metal centers are linked by bridging ligands to form continuous 10 chains. o 2D (Layers / Sheets): Chains are linked together, or metal centers are linked by bridging ligands, to form extended two-dimensional sheets. o 3D (Frameworks / Coordination Polymers / MOFs): Metal centers are linked in all three dimensions by bridging ligands to form extended, porous or non-porous frameworks. 15 Metal-Organic Frameworks (MOFs) are a prominent subclass of 3D coordination polymers, characterized by their porosity. ^ Tunability: The properties of crystalline coordination structures (e.g., porosity, stability, magnetism, optical properties, and crucially, nutrient release rates in fertilizers) can be precisely tuned by changing the metal ion, the type of ligand, and the synthesis conditions, 20 which dictates the resulting crystalline structure and dimensionality. c) Crystalline Coordination Polymer Fertilizer; comprising a specific type of crystalline solid characterized by its extended, repeating network where metal ions (or metal clusters) are linked together by organic or inorganic bridging ligands through coordinate covalent bonds, forming a polymer that extends in one, two or three dimensions, and critically, possesses long- 25 range order. This is the core concept. It's a compound formed by linking metal ions or metal clusters with organic or inorganic ligands through coordination bonds. The "polymer" aspect means these linkages repeat, forming an extended structure, unlike discrete molecular complexes. The ligands are typically "bridging ligands" (also called "linkers" or "struts") meaning 19

[0020] they are capable of coordinating to two or more metal centers, thus connecting them into an extended network. Key Features of Crystalline Coordination Polymer Fertilizer: ^ Extended Dimensionality: This is a defining feature. CPs extend in at least one 5 dimension: o 1D: Forming infinite chains. o 2D: Forming extended layers or sheets. o 3D: Forming complex, interconnected frameworks that span all three dimensions. ^ Metal-Organic Hybrid Materials: Many coordination polymers, especially those with 10 organic ligands, are considered "organic-inorganic hybrid materials," combining the properties of both components. ^ Metal-Organic Frameworks (MOFs): MOFs are a highly studied subclass of 3D crystalline coordination polymers that are specifically characterized by their porosity (having intrinsic pores or voids). While all MOFs are crystalline coordination polymers, not all crystalline 15 coordination polymers are MOFs (some may be dense or non-porous). ^ Self-Assembly: Crystalline coordination polymers are often formed through self- assembly processes, where metal salts and ligands spontaneously come together under specific conditions (e.g., solvothermal synthesis) to form the ordered polymeric structure. ^ Tunability: The precise structure and properties (like pore size, stability, gas adsorption, 20 catalytic activity, and nutrient release for fertilizers) can be highly tuned by selecting different metal ions, ligands, and synthesis conditions. d) Crystalline Coordination Complex Fertilizer; comprising a solid material where discrete, individual coordination complex molecules or ions are arranged in a highly ordered, repeating three-dimensional pattern throughout the entire material. This is a discrete molecular entity (or 25 a discrete ion) consisting of a central metal atom or ion bonded to a set number of surrounding molecules or ions called ligands via coordinate covalent bonds. Key Features and Distinctions of Crystalline Coordination Complex Fertilizer: ^ 0-Dimensional (0D) Coordination Entity: From a coordination chemistry perspective, each individual coordination complex itself is a 0D entity (it doesn't extend infinitely by 20

[0021] coordination bonds). When these 0D entities crystallize, they form a 3D crystal lattice through weaker intermolecular forces (like ionic interactions, hydrogen bonding, Van der Waals forces) between the discrete complexes. ^ Discrete Units: The fundamental building block that repeats in the crystal is the entire 5 coordination complex molecule or ion, rather than repeating metal-linker-metal connections that form an extended network. ^ Bonding: o Intra-complex: Strong coordinate covalent bonds hold the metal and ligands together within each discrete complex. 10 o Inter-complex: Weaker intermolecular forces (hydrogen bonds, ionic attractions if counterions are present, van der Waals forces) or ionic bonds (if the complex is an ion and forms a salt with counterions) hold the discrete complexes together in the crystal lattice. ^ Solubility and Release: Many crystalline coordination complexes tend to be more readily soluble and exhibit faster dissolution / release rates compared to extended coordination 15 polymers, as their release typically involves the dissolution of the entire discrete complex rather than the breakdown of a network. e) Crystalline Ionic Compound Fertilizer; comprising an ionic compound, meaning they consist of positively charged ions (cations) and negatively charged ions (anions) held together by strong electrostatic forces called ionic bonds. Ionic compounds are one of the most classic and 20 straightforward examples of materials that form crystalline structures. Key Features and Distinctions of Crystalline Ionic Compound Fertilizer: ^ Constituent Particles: For ionic compounds, the particles are ions (cations and anions). ^ Ordered Arrangement: These oppositely charged ions arrange themselves in a way that maximizes attractive forces and minimizes repulsive forces, leading to a highly ordered, 25 repeating pattern. ^ Crystal Lattice: This ordered arrangement forms an ionic crystal lattice. For example, in sodium chloride (NaCl), each Na+ ion is surrounded by six Cl− ions, and each Cl− ion is surrounded by six Na+ ions, creating a cubic lattice that repeats throughout the entire crystal. ^ Long-Range Order: This order extends throughout the entire macroscopic crystal. 21

[0022] ^ Well-Defined Geometry: This is why table salt often forms cubic crystals. ^ Constituent Particles: For ionic compounds, the particles are ions (positively charged cations and negatively charged anions). ^ Ordered Arrangement: These oppositely charged ions arrange themselves in a way that 5 maximizes attractive forces and minimizes repulsive forces. This leads to a highly ordered, repeating pattern in three dimensions. For example, in table salt (sodium chloride, NaCl), each Na+ ion is surrounded by six Cl− ions, and each Cl− ion is surrounded by six Na+ ions, forming a cubic lattice that repeats throughout the entire crystal. ^ Crystal Lattice: This specific ordered arrangement of ions forms what is called an ionic 10 crystal lattice. ^ Long-Range Order: This precise order extends uniformly over vast distances within the solid, giving the macroscopic crystal its distinct properties. ^ Well-Defined Geometry: This internal order is why many ionic compounds naturally form macroscopic crystals with distinct geometric shapes (e.g., cubic salt crystals). 15 f) Crystalline Coordination Nitrogen-Metal Polymer and Complex Fertilizer; comprising a nitrogen fertilizer covalently bonded to metal salts in the form that encompass a) urea-metal and b) ammine-metal, in which these nitrogen-metal structures provide ligands to a central metal, and in which it encompasses a nitrogen-metal structure in the form of c) ammonium- metal, participating in a nitrogen-metal structure as a counterion. 20 g) Crystalline Coordination Non-Nitrogen-Metal Polymer and Complex Fertilizer; comprising a structure devoid of nitrogen fertilizer in the form of urea, ammine, and ammonium fertilizer. It comprises a crystalline coordination metal salt polymer and complex fertilizer with no structural attachment to urea, ammine, and ammonium fertilizer. The features and distinctions of this fertilizer encompasses the features and distinctions of crystalline coordination polymer and 25 complex fertilizer. h) Crystalline Nitrogen-Ionic Compound Fertilizer: comprising a urea-ionic compound and ammonium-ionic compound but can contain any nitrogen fertilizer that is part of an ionic compound fertilizer. The features and distinctions of this fertilizer encompass the features and distinctions of crystalline ionic compound fertilizer. 22

[0023] i) Crystalline Non-Nitrogen-Ionic Compound Fertilizer; comprising an ionic compound that is devoid of a nitrogen source, such as urea, ammonium, or any other fertilizer nitrogen. The features and distinctions of this fertilizer encompass the features and distinctions of crystalline ionic compound fertilizer. 5 In the preferred non-limiting embodiments, crystalline fertilizer compositions comprising coordination polymer and complex fertilizers have features and distinctions specifically emphasizing their impact on stability, protection, efficiency, and controlled release for plant uptake. 1. Dimensionality & Connectivity: 10 ^ Definition: Describes the extent (0D, 1D, 2D, or 3D) to which metal centers and ligands form an extended, chemically bonded network within the crystal. Connectivity details the precise linking pattern. ^ Value for Fertilizers: o Stability & Protection: Higher dimensionality (1D, 2D, 3D polymers) generally 15 confers greater chemical and thermal stability, acting as a physical barrier to premature degradation and nutrient loss from leaching or fixation in soil. o Controlled Release & Efficiency: Controls the rate at which the fertilizer dissolves and releases nutrients.0D complexes may be rapid-release, while 1D, 2D, or 3D polymeric networks can be engineered for slow-release or controlled-release profiles by limiting water 20 access and bond cleavage, thereby optimizing nutrient availability to plants over time. 2. Bridging Ligand & Mode: ^ Definition: A ligand that coordinates to two or more metal atoms, forming a structural link (e.g., μ2, μ3). The mode specifies how it binds. Value for Fertilizers: 25 o Stability & Protection: Essential for constructing robust, high-dimensional coordination polymers. The strength and number of bridging bonds directly contribute to the overall physical and chemical stability of the fertilizer particle. o Controlled Release & Efficiency: The chemical nature (e.g., lability, degradability) of the bridging ligand dictates the mechanism and rate of framework breakdown. Ligands that 23

[0024] break down in response to specific soil conditions (pH, microbial activity, root exudates) can enable a triggered or controlled release of nutrients, ensuring efficient delivery synchronized with plant demand. 3. Metal Coordination Sphere: 5 ^ Definition: The central metal atom / ion and all ligands directly bonded to it, including the coordination number, geometry, and bond lengths. ^ Value for Fertilizers: o Stability & Protection: Dictates the immediate environment of the metal nutrient. Stable coordination bonds prevent the metal from undergoing rapid precipitation or 10 fixation reactions in the soil, thus protecting its plant-available form. o Controlled Release & Efficiency: Influences the solubility and bioavailability of the metal nutrient. Ligands and their binding strength can be tuned to maintain the metal in a soluble form for extended periods, facilitating root uptake and contributing to controlled release. This is particularly critical for micronutrients prone to fixation. 15 4. Crystallographic Proof: ^ Definition: Experimental determination of the material's precise 3D atomic arrangement (e.g., via Single-Crystal X-ray Diffraction). It provides definitive data on atomic positions, bond lengths / angles, and overall packing. ^ Value for Fertilizers: 20 o Stability & Protection: Provides fundamental understanding of the exact bonding and network architecture, which is crucial for predicting and enhancing the stability and physical integrity of the fertilizer. It confirms the formation of the desired polymer or complex structure. o Controlled Release & Efficiency: Indispensable for establishing structure- 25 property relationships. It allows for the rational design of structures with specific porosity, bond lability, or surface features that directly govern the controlled release mechanism and optimize nutrient efficiency. It validates if the intended "slow-release" features are actually present. 5. Functional Link: 24

[0025] ^ Definition: The specific, engineered relationship between the crystalline structure's atomic / molecular features and its intended performance as a fertilizer, particularly regarding nutrient release. ^ Value for Fertilizers: 5 o Stability & Protection: Explains how the structure specifically protects nutrients (e.g., encapsulating them, forming insoluble barriers, or preventing premature chemical reactions). o Controlled Release & Efficiency: Directly describes the mechanism by which the fertilizer achieves controlled release (e.g., diffusion through pores, dissolution triggered by 10 specific pH, enzymatic degradation of ligands). This clarity is vital for designing fertilizers that provide the right nutrients at the right time for maximum plant efficiency. 6. Hydrogen Bonding: ^ Definition: A strong non-covalent interaction between an electronegative atom and a hydrogen atom bound to another electronegative atom. It contributes to the overall crystal 15 packing. ^ Value for Fertilizers: o Stability & Protection: Extensive hydrogen bonding networks can provide significant additional cohesive forces within the crystal, enhancing the overall physical and chemical stability of the fertilizer particle and contributing to its mechanical strength. 20 o Controlled Release & Efficiency: Influences surface properties, wettability, and the rate of water penetration into the crystal. This can play a role in modulating the dissolution kinetics and thus the controlled release profile, influencing how quickly nutrients become available to the plant. 7. Void Volume: 25 ^ Definition: The empty space or pores within the crystalline structure, expressed as a percentage of the total crystal volume or by pore dimensions. ^ Value for Fertilizers: 25

[0026] o Stability & Protection: For most granular fertilizers, minimizing large, interconnected void volumes typically contributes to greater physical density and mechanical stability, reducing friability and nutrient exposure. o Controlled Release & Efficiency: In specialized designs (e.g., certain MOFs or 5 porous coordination polymers), precisely engineered void volume can serve as a reservoir for additional nutrients or active agents, facilitating controlled release through diffusion out of the pores. It can also influence the rate of water infiltration and subsequent dissolution. In the preferred non-limiting embodiments, crystalline fertilizer compositions comprising three (3) overarching definitive structural classifications (A, B and C) and six (6) 10 definitive structural sub-classifications (1-6) of the invention; comprising, A) crystalline coordination polymer fertilizer; 1) crystalline coordination nitrogen-metal polymer fertilizer; and 2) crystalline coordination non-nitrogen-metal polymer fertilizer, these account for the entirety of coordination polymer fertilizer; comprising, B) crystalline coordination complex fertilizer; 3) crystalline coordination nitrogen-metal complex fertilizer; and 4) crystalline 15 coordination non-nitrogen-metal complex fertilizer, these account for the entirety of coordination complex fertilizer; and comprising, C) crystalline ionic compound fertilizer; 5) crystalline nitrogen-ionic compound fertilizer; and 6) crystalline non-nitrogen-ionic compound fertilizer, these account for the entirety of ionic compound fertilizer. In the preferred non-limiting embodiments, the present disclosure comprises crystalline 20 fertilizer compositions that support crystalline coordination fertilizers as the dominant engineered solid-state structures synthesized by the method of manufacture compared with all structures made, which reflect a minor number of ionic compound fertilizer synthesized. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions that support crystalline coordination polymer fertilizer as the dominant 25 engineered solid-state structures synthesized by the method of manufacture, compared with crystalline coordination complex fertilizer synthesized. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions that support crystalline coordination nitrogen-metal polymer and complex fertilizer as the dominant engineered solid-state structures synthesized by the method 26

[0027] of manufacture, compared with crystalline coordination non-nitrogen-metal polymer and complex fertilizer synthesized. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions that support crystalline coordination nitrogen-metal and non-nitrogen- 5 metal polymer fertilizer as the dominant engineered solid-state structures synthesized by the method of manufacture, compared with crystalline coordination nitrogen-metal and non- nitrogen-metal complex fertilizer synthesized. In the preferred non-limiting embodiments, the present invention relates to crystalline fertilizer compositions and methods for their engineered synthesis. A rigorous and 10 comprehensive crystallographic characterization program, utilizing both Single-Crystal X-ray Diffraction (SCXRD) and Powder X-ray Diffraction (PXRD), was meticulously performed on all forty-five (45) distinct crystalline compositions obtained from the inventive urea:metal salt reactions. This thorough analysis has fully elucidated the precise atomic-level structure of each composition, providing unprecedented insight into their structural diversity and the capabilities 15 of the disclosed synthetic methodology. Overall Compositional Breakdown: The detailed crystallographic analysis revealed a remarkable distribution among the 45 compositions: ^ Coordination Chemistry Dominance: A substantial 84% of all compositions were 20 identified as coordination compounds, signifying that the inventive urea:metal salt reaction system primarily facilitates the formation of complex structures where the metal center is directly bonded to various ligands. The remaining 16% of compositions were identified as ionic compounds, often comprising well-known and industrially significant fertilizer species such as ammonium sulfate, potassium sulfate, and ammonium phosphate, among others. 25 ^ Prevalence of Polymeric Frameworks: Within the identified coordination compounds, a significant and advantageous distribution was observed: 68% were characterized as coordination polymer compositions, demonstrating a strong tendency or engineered preference of the inventive method to form extended, network-like structures. The remaining 32% were discrete coordination complex compositions. 27

[0028] ^ Tunable Metal-Ligand Bonding: Further structural insight into the coordination compounds revealed a clear distinction in metal-ligand bonding: 63% were identified as nitrogen-metal compositions, where nitrogen in the form of urea and / or ammine are directly coordinated to the metal center, and / or ammonium acts as a counterion. The remaining 37% 5 were non-nitrogen-metal compositions, primarily exhibiting coordination from metal salts, with no nitrogen in the form of urea, ammine or ammonium, involvement in the coordination. This distribution highlights the inventive method's precise control over the metal's coordination environment. This comprehensive analysis reveals that the inventive urea:metal salt reactions provide 10 a versatile platform capable of producing a broad spectrum of crystalline fertilizer compositions. Importantly, the method is not limited to coordination compounds but also robustly yields significant proportions of crystalline ionic compounds, often co-existing or selectively forming under specific conditions, demonstrating the breadth and utility of the disclosed synthetic approach. 15 Discovery of Reproducibility of Valuable Forms: The comprehensive structural characterization of the synthesized materials confirmed the ability of the inventive methods to produce a diverse range of valuable crystalline forms: Value and Significance of Structural Findings: The aforementioned detailed structural findings and the underlying controlled synthesis 20 methodologies yield profound value for the development of advanced fertilizer compositions: ^ Precise Engineering of Nutrient Release: The ability to selectively yield predominantly coordination compositions (84%), and particularly coordination polymers (68% of coordination compositions), allows for the precise engineering of intrinsic physicochemical properties that govern nutrient release. The extended, chemically bonded frameworks of these polymers 25 inherently enable controlled and sustained nutrient liberation into the soil, minimizing losses and maximizing plant uptake efficiency, a significant improvement over conventional fertilizer. Furthermore, it’s another approach to deliver enhanced efficiency fertilizers. 28

[0029] ^ Tailorable Stability and Degradation Profiles: The demonstrated control over metal- ligand bonding (nitrogen-metal vs. non-nitrogen-metal coordination) provides a crucial handle for fine-tuning the stability, degradation, and protection characteristics of the compositions. ^ Robust and Scalable Discovery Platform: Crystalline fertilizer compositions, particularly 5 novel coordination polymers, positions this inventive method as a highly robust and scalable platform for generating new intellectual property in fertilizer chemistry. These novel compounds, fully defined by their unique crystallographic fingerprints, represent new solutions for complex agricultural challenges. ^ Industrial Applicability and Versatility: The method's demonstrated capacity to reliably 10 produce a wide spectrum of desirable crystalline fertilizer composition forms—from novel structures to established synthetic compositions and environmentally relevant minerals— underscores its practical utility and industrial applicability. This versatility allows for the target production of diverse fertilizer products with specific dissolution rates, nutrient content, and long-term stability. 15 ^ Multi-Nutrient Integration: The coordination chemistry inherent to the majority of these compositions enables the stable integration of multiple essential plant nutrients (e.g., metal and non-metal macronutrients and micronutrients) within a single crystalline matrix, offering comprehensive and synchronized nutrient delivery. ^ Efficient Synthesis of Conventional and Hybrid Fertilizers: The inventive method's 20 capability to consistently produce well-known ionic fertilizer compositions (such as ammonium sulfate, potassium sulfate, and ammonium phosphate) as 16% of the total output, often alongside or interchangeably with coordination compounds, represents a significant advancement. This provides a new, potentially more efficient, cost-effective, or environmentally benign synthetic route for these established fertilizers. Furthermore, it enables 25 the creation of unique, multi-component crystalline materials where both coordination compounds and ionic compounds are formed in a single process, potentially leading to novel hybrid fertilizer compositions with combined beneficial properties and tailored release characteristics. 29

[0030] These findings collectively confirm that the present invention provides not merely new fertilizer compositions, but a fundamental advancement in the engineered synthesis of crystalline fertilizer compositions with controlled intrinsic solid-state topologies and highly desirable agricultural properties. 5 Structure No.1: A) Crystalline Coordination Polymer Fertilizer, 1) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination urea-metal polymer fertilizer, designed to deliver nitrogen, calcium, sulfate sulfur, and carbon to plants in a protected, stable, and efficient form, with a polymer ((CH4N2O)4Ca(SO4)) identified in crystallography as a "known synthetic structure.” 10 IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer tetrakis(urea)calcium sulfate. Tetrakis(urea)calcium sulfate is a recognized method of slow- release nitrogen fertilizer. The solvated method used herein allows for an improved method of urea and calcium sulfate transformation to tetrakis(urea)calcium sulfate. As such, it is below 1 wt% in biuret, a toxic component to plants. Under the preferred non-limiting embodiment, 15 tetrakis(urea)calcium sulfate is manufactured by reacting urea and metal salts and mixtures thereof. In one example, urea reacts with two metal salts, calcium hydroxide and copper sulfate, resulting in urea-metal complex fertilizer providing tetrakis(urea)calcium sulfate. Structural Description: ^ Dimensionality & Connectivity: 1D chains via μ₂-SO₄ bridges (Ca–O–S–O–Ca) 20 ^ Bridging Ligand & Mode: μ₂-SO₄²⁻ κO:κO' ^ Metal Coordination Sphere: Ca²⁺ 7-coordinate; 4× urea-O (2.45 Å) + 2× SO₄-O (2.40 Å) ^ Crystallographic Proof: CCDC 1278455; 2θ: 9.2°, 12.7° ^ Functional Link: Gradual N-release via urea-O cleavage ^ Hydrogen Bonding: N–H⋯O^^₄: 2.85 Å (urea–SO₄) 25 ^ Void Volume: Helical channels (4.2 Å) along

[0001] Structure No.2: A) Crystalline Coordination Polymer Fertilizer, 1) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination ammonium-metal polymer fertilizer, designed to deliver nitrogen, copper, sulfate sulfur to plants in a protected, stable and efficient form, with a 30

[0031] polymer ((NH₄)₂Cu(SO₄)₂(H₂O)₂) identified in crystallography as a "known synthetic structure.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature is named polymer ammonium copper(II) sulfate dihydrate. Structural Description: 5 ^ Dimensionality & Connectivity: 2D sheets via Cu–O–S–O–Cu chains ^ Bridging Ligand & Mode: μ₂-SO₄²⁻ κO:κO' ^ Metal Coordination Sphere: Cu²⁺ octahedral; 4× SO₄-O (1.95 Å) + 2× H₂O (2.35 Å) ^ Crystallographic Proof: PDF 00-025-1486; d-spacings: 7.8 Å, 3.9 Å ^ Functional Link: Rapid NH₄⁺ release; slow Cu²⁺ dissoluƟon 10 ^ Hydrogen Bonding: N–H⋯O: 2.78 Å (NH₄⁺–SO₄) ^ Void Volume: Interlayer spacing (7.8 Å) for ion diffusion. Structure No.3: A) Crystalline Coordination Polymer Fertilizer, 1) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination urea-metal polymer fertilizer, designed to deliver nitrogen, 15 copper, sulfate sulfur to plants in a protected, stable and efficient form, with a polymer (Cu(SO₄)₂(H₂O)₂-Cu(CH4N2O)₂(H₂O)₂) identified as “novel” as “of a new kind”, unknown and unreported in crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer diaquabis(urea)copper(II) (Cu(urea)2(H2O)2). Structural Description – as an unpublished SCXRD, a detailed description is provided: 20 ^ Dimensionality & Connectivity: 2D sheets formed by Cu–L–Cu linkages (L = sulfate / urea ligands); contains discrete Cu(SO₄)₂ and Cu(urea)₂ units. ^ Bridging Ligand & Mode: Sulfate (SO42−) acts as a primary bridging ligand. Urea (CO(NH2)2) also coordinates to copper. ^ Metal Coordination Sphere: Cu²⁺ centers coordinated by oxygen atoms from sulfate, 25 urea, and water ligands. (Exact coordination geometry / bond lengths determined from full structure analysis). ^ Crystallographic Proof: Triclinic system (Space Group P-1). Unique unit cell parameters: a=5.253 Å, b=7.387 Å, c=10.161 Å; α=72.33∘, β=83.66∘, γ=69.90∘; V=352.79 Å3; Z=1. Confirms novel crystalline structure. 31

[0032] ^ Functional Link: Structure supports controlled nutrient release (Cu, N, S) and enhanced stability. ^ Hydrogen Bonding: Extensive H-bonding inferred from water and urea moieties, contributing to overall structural stability. 5 ^ Void Volume: Specific void volume inferred from packing efficiency; potential for ion diffusion / retention. Structure No.4: A. Crystalline Coordination Polymer Fertilizer, 1) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination urea-metal polymer fertilizer, designed to deliver nitrogen, 10 potassium, zinc, chloride, and carbon to plants in a protected, stable, and efficient form, with a polymer (KZnCl₃(urea)) identified in crystallography as a "known synthetic structure.” This structure, with Zn as a central metal and O- and Cl-donor ligands is documented to be an effective urease inhibitor, which disrupts the nickel-active site of urease (Casali L., et.al, Chem. Commun. (Cambridge) 2018, 54, 7637-7640). 15 IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer potassium trichlorido(urea)zincate(II). Structural Description: ^ Dimensionality & Connectivity: 1D chains via Zn–Cl–Zn linkages ^ Bridging Ligand & Mode: μ2-Cl (chloride) 20 ^ Metal Coordination Sphere: Zn2+ tetrahedral; typically, 3× Cl + 1× urea-O ^ Crystallographic Proof: PDF Card – 04-025-1366 ^ Functional Link: Gradual Zn2+ / N-release ^ Hydrogen Bonding: N–H⋯Cl (from urea to chloride); N–H⋯O (from urea to urea / other O in crystal lattice) 25 ^ Void Volume: Negligible (densely packed, no significant channels) Structure No.5: A) Crystalline Coordination Polymer Fertilizer, 1) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination urea-metal polymer fertilizer, designed to deliver nitrogen, magnesium, sulfate sulfur, and carbon to plants in a protected, stable and efficient form, with a 32

[0033] polymer (Mg(CH4N2O)₄(H₂O)(SO₄)) identified as “novel” as “of a new kind”, yet unknown and unreported in crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer tetrakis(urea)aquamagnesium(II) sulfate. Structural Description – as an unpublished SCXRD, a detailed description is provided: 5 ^ Dimensionality & Connectivity: Forms 1D chains via Mg–O–S–O–Mg linkages. ^ Bridging Ligand & Mode: Sulfate (SO42−) is the primary bridging ligand, exhibiting a μ₂- SO₄²⁻ κO:κO' coordination mode. Urea (CO(NH2)2) and water (H2O) are also coordinated to magnesium. ^ Metal Coordination Sphere: Mg²⁺ centers are coordinated by oxygen atoms from urea, 10 water, and bridging sulfate anions. (Likely octahedral geometry for Mg(II) in this environment). ^ Crystallographic Proof: Monoclinic system (Space Group (7)). Unique unit cell parameters: a=19.024 Å, b=22.272 Å, c=10.503 Å; α=90∘, β=90.478∘, γ=90∘; V=4449.9 Å3; Z=12. Confirms a novel / new crystalline structure. ^ Functional Link: The 1D polymeric structure supports controlled and sustained nutrient 15 release (Mg, N, S). This arrangement provides enhanced stability for both the magnesium and the urea components. ^ Hydrogen Bonding: Extensive H-bonding is inferred from the presence of urea and water moieties, which significantly contributes to the crystal packing and overall structural stability. ^ Void Volume: Specific void volume is inferred from the crystal packing efficiency 20 (density / unit cell) and the 1D chain arrangement; this has potential implications for influencing solubility, dissolution rates, and nutrient accessibility within the fertilizer matrix. Structure No.6: A) Crystalline Coordination Polymer Fertilizer, 1) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination ammine-metal polymer fertilizer, designed to deliver nitrogen, zinc, and 25 sulfate sulfur to plants in a protected, stable and efficient form, with a polymer ([(H3N)2Zn(SO4)2]2-×2(H4N+)) identified as “novel” as “of a new kind”, yet unknown and unreported in crystallography. N- and O-donor ligands are well-documented as effective urease inhibitors, particularly when complexed with transition metals. N- and O-donor ligands form stable complexes with transition metals (e.g., Zn, Cu), which disrupt the nickel-active site of 33

[0034] urease (M. Kulig-Adamiak et al., RSC Advances, 2017; R. D. Al-Sultani et al., RSC Advances, 2021; and R. Shah et al., ACS Omega, 2020, 5, 17, 10174–10183). IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer diammonium diamminedisulfatozincate(II). 5 Structural Description – as an unpublished SCXRD, a detailed description is provided: ^ Dimensionality & Connectivity: Forms a 1D coordination polymer with two Zn centers connected via repeating linkages. The structure is built from [(H₃N)₂Zn(SO₄)₂]²⁻ units. ^ Bridging Ligand & Mode: Sulfate (SO42−) acts as a primary bridging ligand between zinc centers, exhibiting a μ₂-SO₄²⁻ κO:κO' coordination mode. Ammine (NH3) molecules are also coordinated 10 to zinc. ^ Metal Coordination Sphere: Zn²⁺ centers are tetrahedrally coordinated by nitrogen atoms from two ammine (NH3) molecules and oxygen atoms from two bridging sulfate (SO42−) anions. ^ Crystallographic Proof: Monoclinic system (Space Group (12)). Unique unit cell parameters: a=12.167 Å, b=6.431 Å, c=7.375 Å; α=90∘, β=112.94∘, γ=90∘; V=531.37 Å3; Z=2. Confirms a 15 novel crystalline structure. ^ Functional Link: The 1D polymeric structure supports controlled and sustained nutrient release (Zn, N, S) and provides enhanced stability to the incorporated nutrients. ^ Hydrogen Bonding: Extensive H-bonding is inferred from the presence of ammine and ammonium moieties, playing a crucial role in the crystal packing and overall structural integrity. 20 ^ Void Volume: Specific void volume derived from crystal packing efficiency (density / unit cell) and the 1D polymeric arrangement; potentially influencing dissolution rates and nutrient accessibility within the fertilizer matrix. Structure No.7: A) Crystalline Coordination Polymer Fertilizer, 1) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise 25 crystalline coordination urea-metal polymer fertilizer, designed to deliver nitrogen, manganese, sulfate sulfur, and carbon to plants in a protected, stable and efficient form, with a polymer ((Mn2(SO4)2(CH4N2O)6) identified as “novel” as “of a new kind”, yet unknown and unreported in crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer di-μ-sulfato-hexakis(urea)dimanganese(II). 34

[0035] Structural Description – as an unpublished SCXRD, a detailed description is provided: ^ Dimensionality & Connectivity: Forms a coordination polymer via Mn–Sulfate–Mn linkages. (Specific dimensionality, e.g., 1D, 2D, or 3D, determined from full structure analysis). ^ Bridging Ligand & Mode: Sulfate (SO42−) acts as a primary bridging ligand between manganese 5 centers. Urea (CH4N2O) molecules are also coordinated to manganese. ^ Metal Coordination Sphere: Mn²⁺ centers are coordinated by oxygen atoms from urea and bridging sulfate anions. (Likely octahedral geometry for Mn(II)). ^ Crystallographic Proof: Orthorhombic system (Space Group (19)). Unique unit cell parameters: a=7.941 Å, b=14.512 Å, c=20.291 Å; α=β=γ=90∘; V=2338.4 Å3; Z=4. Confirms a novel crystalline 10 structure. ^ Functional Link: The polymeric structure supports controlled nutrient release (Mn, N, S) and provides enhanced stability to the fertilizer components. ^ Hydrogen Bonding: Extensive H-bonding is inferred from the numerous urea moieties, contributing to crystal packing and overall structural integrity. 15 ^ Void Volume: Specific void volume derived from crystal packing efficiency (density / unit cell); potentially influencing dissolution rates and nutrient accessibility within the fertilizer matrix. Structure No.8: A) Crystalline Coordination Polymer Fertilizer, 1) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination ammonium-metal polymer fertilizer, designed to deliver nitrogen, 20 manganese, and sulfate sulfur to plants in a protected, stable and efficient form, with a polymer ((NH4)2Mn2(SO4)3) identified as “novel” as “of a new kind”, unknown and unreported in crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer diammonium trisulfatodimanganate(II). Structural Description – as an unpublished SCXRD, a detailed description is provided: 25 ^ Dimensionality & Connectivity: Forms a coordination polymer with a complex Mn–Sulfate–Mn and Mn–Hydroxide–Mn bridging network. The structure incorporates ammonium cations (NH4+) and water molecules (H2O). ^ Bridging Ligand & Mode: Sulfate (SO42−) and hydroxide (OH−) anions act as primary bridging ligands between manganese centers. 35

[0036] ^ Metal Coordination Sphere: Mn²⁺ centers are coordinated by oxygen atoms from sulfate, hydroxide, and water molecules. (Likely octahedral or distorted octahedral geometry for Mn(II) in this complex environment). ^ Crystallographic Proof: Orthorhombic system (Space Group (36)). Unique unit cell parameters: 5 a=18.553 Å, b=7.757 Å, c=9.963 Å; α=β=γ=90∘; V=1433.83 Å3; Z=4. Confirms a novel crystalline structure. ^ Functional Link: The polymeric framework and incorporation of multiple nutrients (Mn, N, S) suggest controlled and sustained nutrient release, along with enhanced stability for the fertilizer components. 10 ^ Hydrogen Bonding: Extensive H-bonding is inferred from the presence of ammonium cations and water molecules, significantly contributing to the overall crystal packing and structural integrity. ^ Void Volume: Specific void volume derived from crystal packing efficiency (density / unit cell); potentially influencing dissolution rates and nutrient accessibility within the fertilizer matrix. 15 Structure No.9: A) Crystalline Coordination Polymer Fertilizer, 1) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination ammonium-metal polymer fertilizer, designed to deliver nitrogen, manganese, and sulfate sulfur to plants in a protected, stable and efficient form, with a polymer ((NH4)2Mn3(SO4)3(OH)2(H2O)2) identified as “novel” as “of a new kind”, unknown and 20 unreported in crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer diammonium di-μ-hydroxo-tris(sulfato)diaquatrimanganate(II). Structural Description – as an unpublished SCXRD, a detailed description is provided: ^ Dimensionality & Connectivity: Forms a coordination polymer with a complex Mn–Sulfate–Mn and Mn–Hydroxide–Mn bridging network. The structure incorporates ammonium cations (NH4+25 ) and water molecules (H2O). ^ Bridging Ligand & Mode: Sulfate (SO42−) and hydroxide (OH−) anions act as primary bridging ligands between manganese centers. 36

[0037] ^ Metal Coordination Sphere: Mn²⁺ centers are coordinated by oxygen atoms from sulfate, hydroxide, and water molecules. (Likely octahedral or distorted octahedral geometry for Mn(II) in this complex environment). ^ Crystallographic Proof: Orthorhombic system (Space Group (36)). Unique unit cell parameters: 5 a=18.553 Å, b=7.757 Å, c=9.963 Å; α=β=γ=90∘; V=1433.83 Å3; Z=4. Confirms a novel crystalline structure. ^ Functional Link: The polymeric framework and incorporation of multiple nutrients (Mn, N, S) suggest controlled and sustained nutrient release, along with enhanced stability for the fertilizer components. 10 ^ Hydrogen Bonding: Extensive H-bonding is inferred from the presence of ammonium cations and water molecules, significantly contributing to the overall crystal packing and structural integrity. ^ Void Volume: Relatively low void volume, with any interstitial spaces potentially filled or stabilized by extensive hydrogen bonding. 15 Structure No.10: A) Crystalline Coordination Polymer Fertilizer, 1) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination urea-metal polymer fertilizer, designed to deliver nitrogen, iron, sulfate sulfur, and carbon to plants in a protected, stable and efficient form, with a polymer (Fe(SO4)(CH4N2O)(OH2)2) identified as “novel” as “of a new kind”, unknown and unreported in 20 crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer diaquasulfato(urea)iron(II). Structural Description – as an unpublished SCXRD, a detailed description is provided: ^ Dimensionality & Connectivity: It forms a 1D coordination polymer. Iron(II) centers are bridged by sulfate (SO42−) anions, creating extended chains. Urea molecules and water molecules 25 coordinate to the iron centers as terminal ligands. ^ Metal Coordination Sphere: Each Fe(II) center adopts an octahedral coordination environment, bonded to oxygen atoms from the urea molecule, water molecules, and the bridging sulfate anions. 37

[0038] ^ Crystallographic Proof: The compound crystallizes in the triclinic crystal system, most likely Space Group P-1 (No.2). Its unique unit cell parameters (a=5.295Å, b=7.623Å, c=10.277Å, α=69.5°, β=85.9°, γ=70.5°) define a distinct crystalline structure (Volume = 365.97 ų), with two formula units per cell (Z=2). The calculated density is 2.251 gcm⁻³. 5 ^ Functional Link: The polymeric framework, which incorporates essential nutrients (Iron, Sulfur, Nitrogen from urea), inherently supports controlled and sustained nutrient release. This extended, chemically bound structure suggests a slower dissolution profile, contributing to prolonged nutrient availability. ^ Hydrogen Bonding: Extensive hydrogen bonding from urea and water molecules significantly 10 contributes to the crystal's overall stability and dense packing. ^ Void Volume: The calculated high density and compact triclinic crystal system suggest a low void volume. This dense packing can restrict solvent access, influencing dissolution rates. Structure No.11: A) Crystalline Coordination Polymer Fertilizer, 1) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise 15 crystalline coordination ammonium-metal polymer metal fertilizer, designed to deliver nitrogen, magnesium, and sulfate sulfur to plants in a protected, stable, and efficient form, with a polymer ((NH4)2Mg3(SO4)3(OH)2(H2O)2) identified in crystallography as a "known synthetic structure.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer diammonium di-μ-hydroxo-tris(sulfato)diaquatrimagnesate(II). 20 Structural Description: ^ Dimensionality & Connectivity: 2D layers via Mg–O–S–O–Mg and Mg–OH–Mg ^ Bridging Ligand & Mode: μ₂-SO₄²⁻ κO:κO' + μ₃-OH ^ Metal Coordination Sphere: Mg²⁺ octahedral; 4× O (2.05 Å avg.) ^ Crystallographic Proof: PDF 04-025-4931; d-spacings: 8.2 Å, 4.1 Å 25 ^ Functional Link: Slow Mg²⁺ / N-release ^ Hydrogen Bonding: N–H⋯O: 2.75 Å (NH₄⁺–OH) ^ Void Volume: Interlayer galleries (6.5 Å) Structure No.12: A) Crystalline Coordination Polymer Fertilizer, 1) Nitrogen-Metal: 38

[0039] In the preferred non-limited embodiments, the present disclosure compositions comprise crystalline coordination ammonium-metal polymer fertilizer, designed to deliver nitrogen, phosphorus, and zinc to plants in a protected, stable and efficient form, it can also act as a coating agent for a second fertilizer due to its low solubility, with a polymer ((NH₄)Zn(PO₄)) 5 identified in crystallography as ebnerite (hexagonal) and epiebnerite (monoclinic), a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer ammonium zinc phosphate. The water solubility of (NH₄)Zn(PO₄), also known as ammonium zinc phosphate, is generally considered low to sparingly soluble. Phosphate Salts: Many metal phosphates, including zinc phosphate (Zn₃(PO₄)₂), are known to 10 have low solubility in water. The phosphate ion (PO₄³⁻) tends to form insoluble salts with many divalent and trivalent metal cations. The solubility product constant (Ksp) for zinc phosphate (Zn₃(PO₄)₂) is very low, around 9.1 x 10⁻³³. This indicates a very limited extent of dissolution in water. Structural Description: 15 ^ Dimensionality & Connectivity: 1D chains via Zn–O–P–O–Zn ^ Bridging Ligand & Mode: μ₂-PO₄³⁻ κO:κO' ^ Metal Coordination Sphere: Zn²⁺ tetrahedral; 4× PO₄-O (1.92 Å) ^ Crystallographic Proof: PDF 04-016-1290; 2θ: 11.2°, 22.4° ^ Functional Link: Slow Zn²⁺ / P-release 20 ^ Hydrogen Bonding: N–H⋯O: 2.73 Å (NH₄⁺–PO₄) ^ Void Volume: Tunnels (5.2 Å) Structure No.13: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver calcium and 25 sulfate sulfur to plants in a protected, stable, and efficient form, with a polymer (Ca(SO₄)(H₂O)₂) identified in crystallography as Gypsum, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer calcium sulfate dihydrate. Structural descripƟon: 39

[0040] ^ Dimensionality & ConnecƟvity: 2D layers via Ca–O–S–O–Ca bridges ^ Bridging Ligand & Mode: μ₂-SO₄²⁻ κO:κO' ^ Metal CoordinaƟon Sphere: Ca²⁺ 8-coordinate; 4× SO₄-O (2.40 Å) + 4× H₂O (2.38 Å) ^ Crystallographic Proof: PDF 04-015-8262; d-spacings: 7.6 Å, 4.3 Å 5 ^ FuncƟonal Link: Slow Ca²⁺ / SO₄²⁻ release via layered erosion ^ Hydrogen Bonding: O–H⋯O: 2.70 Å (H₂O–SO₄) ^ Void Volume: Interlayer voids (10.1 Å) store H₂O Structure No.14: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise 10 crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver calcium and sulfate sulfur to plants in a protected, stable, and efficient form, with a polymer (Ca₂(SO₄)₂(H₂O)) identified in crystallography as Bassanite, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature is named polymer calcium sulfate hemihydrate. 15 Structural descripƟon: ^ Dimensionality & Connectivity: 1D chains via Ca–O–S–O–Ca bridges ^ Bridging Ligand & Mode: μ₂-SO₄²⁻ κO:κO' ^ Metal Coordination Sphere: Ca²⁺ 7-coordinate; 3× SO₄-O (2.39 Å) + 3× H₂O (2.41 Å) ^ Crystallographic Proof: PDF 04-011-1765; d-spacings: 6.0 Å, 3.5 Å 20 ^ Functional Link: Moderate Ca²⁺ release via chain dissolution ^ Hydrogen Bonding: O–H⋯O: 2.68 Å (H₂O–SO₄) ^ Void Volume: Axial channels (3.8 Å) for H₂O diffusion Structure No.15: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise 25 crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver iron and sulfate sulfur to plants in a protected, stable and efficient form, with a polymer (Fe(SO₄)₂(H₃O)(H₂O)₃) identified in crystallography as Rhomboclase, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer hydronium triaquairon(III) disulfate. 40

[0041] Structural Description: ^ Dimensionality & Connectivity: 1D chains via Fe–O–S–O–Fe ^ Bridging Ligand & Mode: μ₂-SO₄²⁻ κO:κO' ^ Metal Coordination Sphere: Fe³⁺ octahedral; 6× O-ligands 5 ^ Crystallographic Proof: PDF 04-013-2664; 2θ: 9.1°, 18.3° ^ Functional Link: Acid-triggered Fe³⁺ release ^ Hydrogen Bonding: O–H⋯O: 2.60 Å (H₃O⁺–SO₄) ^ Void Volume: Proton-conducting channels (3.2 Å) Structure No.16: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: 10 In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver manganese and carbonate to plants in a protected, stable, and efficient form, with a polymer (MnCO₃) identified in crystallography as Rhodochrosite, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer 15 manganese(II) carbonate. Structural Description: ^ Dimensionality & Connectivity: 3D framework via Mn–O–C–O–Mn ^ Bridging Ligand & Mode: μ₂-CO₃²⁻ κO:κO' ^ Metal Coordination Sphere: Mn²⁺ octahedral; 6× CO₃-O (2.18 Å) 20 ^ Crystallographic Proof: PDF-Card 04-001-7250; 2θ: 10.8°, 31.6° ^ Functional Link: Slow Mn²⁺ release ^ Hydrogen Bonding: None ^ Void Volume: Minimal (dense) Structure No.17: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: 25 In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver potassium, zinc and sulfate sulfur to plants in a protected, stable and efficient form, with a polymer (Zn₂K(SO₄)₂(OH)(H₂O)) identified as “novel” as “of a new kind”, unknown and unreported in 41

[0042] crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer potassium dizinc disulfate hydroxide monohydrate. Structural Description – as an unpublished SCXRD, a detailed description is provided: ^ Dimensionality & Connectivity: Forms a coordination polymer with a complex Zn–Sulfate–Zn 5 and Zn–Hydroxide–Zn bridging network. Potassium cations (K+) and water molecules (H2O) are integrated into the structure. ^ Bridging Ligand & Mode: Sulfate (SO42−) and hydroxide (OH−) anions act as primary bridging ligands between zinc centers. ^ Metal Coordination Sphere: Zn²⁺ centers are coordinated by oxygen atoms from sulfate, 10 hydroxide, and water molecules. The specific coordination geometry for Zn(II) would be determined from a full structural analysis. ^ Crystallographic Proof: Monoclinic system (Space Group (12)). Unique unit cell parameters: a=8.871 Å, b=6.328 Å, c=7.478 Å; α=90∘, β=114.08∘, γ=90∘; V=383.20 Å3; Z=2. This confirms a novel / new crystalline structure. 15 ^ Functional Link: The polymeric framework, incorporating multiple nutrients (Zn, K, S) and hydroxide, suggests controlled and sustained nutrient release, along with enhanced stability for the fertilizer components. ^ Hydrogen Bonding: Extensive H-bonding is inferred from the presence of hydroxide and water molecules, significantly contributing to the overall crystal packing and structural integrity. 20 ^ Void Volume: Specific void volume derived from crystal packing efficiency (density / unit cell); potentially influencing dissolution rates and nutrient accessibility within the fertilizer matrix. Structure No.18: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver nitrogen, 25 potassium, zinc, sulfate sulfur, and chloride to plants in a protected, stable, and efficient form, with a polymer (KZn(SO4)Cl) identified in crystallography as Belousovite, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer potassium chlorosulfatozincate(II). Structural descripƟon: 42

[0043] ^ Dimensionality & ConnecƟvity: 3D framework via Zn–O–S–O–Zn and Zn–O–K–Cl–K ^ Bridging Ligand & Mode: μ₂-SO₄²⁻ κO:κO' ^ Metal CoordinaƟon Sphere: Zn²⁺ tetrahedral; 4× O (1.95 Å avg.) ^ Crystallographic Proof: PDF 04-025-4218; d-spacings: 4.8 Å, 3.2 Å 5 ^ FuncƟonal Link: Controlled Zn²⁺ / K⁺ / Cl⁻ release ^ Hydrogen Bonding: None ^ Void Volume: Minimal (dense) Structure No.19: A) Crystalline CoordinaƟon Polymer FerƟlizer, 2) Non-Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise 10 crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver iron and sulfate sulfur to plants in a protected, stable and efficient form, with a polymer (Fe₃(O)(OH)(SO₄)₃(H₂O)₄) ) identified in crystallography as a "known synthetic structure.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer μ-oxo-μ- hydroxo-tris(sulfato)tetraaqua-triiron(III). 15 Structural description: ^ Dimensionality & Connectivity: 3D framework via Fe–O–Fe, Fe–OH–Fe, Fe–O–S–O–Fe ^ Bridging Ligand & Mode: μ₂-SO₄²⁻ κO:κO' + μ₃-O + μ₂-OH ^ Metal Coordination Sphere: Fe³⁺ octahedral; mixed O / OH / SO₄ ^ Crystallographic Proof: ICSD_CollCode136272 20 ^ Functional Link: Sustained Fe³⁺ release ^ Hydrogen Bonding: O–H⋯O: 2.63 Å (H₂O–SO₄) ^ Void Volume: Micropores (3.0 Å) Structure No.20: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise 25 crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver copper and sulfate sulfur to plants in a protected, stable and efficient form and provides a coating agent for a second fertilizer, with a polymer (Cu3(SO4)(OH)4) identified in crystallography as Antlerite, a “known mineral found in nature.” Antlerite (Cu3(SO4)(OH)4) is described as not readily soluble or insoluble in water in mineralogical literature and safety data sheets. Some sources indicate it 43

[0044] might dissolve slightly in acidic solutions but have very limited solubility in neutral water. The solubility product constant (Ksp) for Antlerite is reported to have a Ksp value of approximately 2.53×10−48. IUPAC (InternaƟonal Union of Pure and Applied Chemistry) nomenclature names polymer tetrakis(μ-hydroxo)sulfatotripper(II). 5 Structural description: ^ Dimensionality & Connectivity: 2D sheets via Cu–O–S–O–Cu and Cu–OH–Cu ^ Bridging Ligand & Mode: μ₂-SO₄²⁻ κO:κO' + μ₃-OH ^ Metal Coordination Sphere: Cu²⁺ 5-coordinate; 3× OH (1.98 Å) + 2× SO₄-O (2.30 Å) ^ Crystallographic Proof: PDF 04-012-1884; d-spacings: 5.3 Å, 2.7 Å 10 ^ Functional Link: Ultra-slow Cu²⁺ release ^ Hydrogen Bonding: None significant ^ Void Volume: Minimal (dense packing) Structure No.21: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise 15 crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver copper and sulfate sulfur to plants in a protected, stable and efficient form, with a polymer (Cu₃(SO₄)(OH)₂(H₂O)₄) identified as “novel” as “of a new kind”, unknown and unreported in crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature is named polymer tricopper sulfate dihydroxide tetrahydrate. 20 Structural Description – as an unpublished SCXRD, a detailed description is provided: ^ Dimensionality & Connectivity: Forms a coordination polymer with a complex Cu–Sulfate–Cu and Cu–Hydroxide–Cu bridging network. Water molecules (H2O) are integrated into the structure. ^ Bridging Ligand & Mode: Sulfate (SO42−) and hydroxide (OH−) anions act as primary bridging 25 ligands between copper centers. ^ Metal Coordination Sphere: Cu²⁺ centers are coordinated by oxygen atoms from sulfate, hydroxide, and water molecules. The precise coordination geometry for Cu(II) would be determined from a full structural analysis. 44

[0045] ^ Crystallographic Proof: Triclinic system (Space Group (2)). Unique unit cell parameters: a=5.503 Å, b=7.061 Å, c=7.579 Å; α=103.236∘, β=98.833∘, γ=105.147∘; V=269.517 Å3; Z=1. This confirms a novel crystalline structure. ^ Functional Link: The polymeric framework, incorporating copper (a key micronutrient), suggests 5 controlled and sustained nutrient release, along with enhanced stability for the fertilizer components. ^ Hydrogen Bonding: Extensive H-bonding is inferred from the presence of hydroxide and water molecules, significantly contributing to the overall crystal packing and structural integrity. ^ Void Volume: Specific void volume derived from crystal packing efficiency (density / unit cell); 10 potentially influencing dissolution rates and nutrient accessibility within the fertilizer matrix. Structure No.22: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver potassium, zinc and sulfate sulfur to plants in a protected, stable and efficient form, with a polymer 15 (Zn3K2(SO4)3(OH)2(H2O)2) identified as “novel” as “of a new kind”, yet unknown and unreported in crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer dipotassium di-μ-hydroxo-tris(sulfato)trizincate(II) dihydrate. Structural Description – as an unpublished SCXRD, a detailed description is provided: 20 ^ Dimensionality & Connectivity: Forms a coordination polymer with a complex Zn–Sulfate–Zn and Zn–Hydroxide–Zn bridging network. Potassium cations (K+) and water molecules (H2O) are integral to the structure. ^ Bridging Ligand & Mode: Sulfate (SO42−) and hydroxide (OH−) anions act as primary bridging ligands between zinc centers. 25 ^ Metal Coordination Sphere: Zn²⁺ centers are coordinated by oxygen atoms from sulfate, hydroxide, and water molecules. The specific coordination geometry for Zn(II) would be determined from a full structural analysis. 45

[0046] ^ Crystallographic Proof: Orthorhombic system (Space Group (36)). Unique unit cell parameters: a=18.051 Å, b=7.529 Å, c=9.776 Å; α=β=γ=90∘; V=1328.57 Å3; Z=2. This confirms a novel crystalline structure. ^ Functional Link: The polymeric framework, incorporating multiple nutrients (Zn, K, S) and 5 hydroxide, suggests controlled and sustained nutrient release, along with enhanced stability for the fertilizer components. ^ Hydrogen Bonding: Extensive H-bonding is inferred from the presence of hydroxide and water molecules, significantly contributing to the overall crystal packing and structural integrity. ^ Void Volume: Specific void volume derived from crystal packing efficiency (density / unit cell); 10 potentially influencing dissolution rates and nutrient accessibility within the fertilizer matrix. Structure No.23: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination non-nitrogen-metal polymer metal fertilizer, designed to deliver iron to plants in a protected, stable and efficient form and provide for a slow-release biodegradable 15 coating agent for a second fertilizer, with a polymer (FeO(OH)) identified in crystallography as Goethite, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer iron(III) oxide-hydroxide. A method of reacting urea with two metal salts, the metal hydroxide is calcium hydroxide, and the metal sulfate is iron sulfate, and the resultant polymer comprises FeO(OH). FeO(OH) is generally considered to be 20 very low to nearly insoluble at neutral pH (around pH 7). Insoluble in Neutral Water: Most sources indicate that FeO(OH) does not readily dissolve in pure water at a neutral pH. The solubility product constant (Ksp) for iron(III) hydroxide [Fe(OH)₃], which is related to FeO(OH) in aqueous solutions, is very low (around 2.79 × 10⁻³⁹). This low Ksp value indicates poor solubility. Soluble in Acidic Solutions: FeO(OH) will dissolve in acidic solutions because the hydroxide and 25 oxide ions react with H⁺ ions, shiŌing the equilibrium and leading to the formaƟon of soluble Fe³⁺ ions and water. Structural description: ^ Dimensionality & Connectivity: 1D double chains via Fe–O–Fe and Fe–OH–Fe ^ Bridging Ligand & Mode: μ₂-O + μ₂-OH 46

[0047] ^ Metal Coordination Sphere: Fe³⁺ octahedral; 3× O (1.94 Å) + 3× OH (2.09 Å) ^ Crystallographic Proof: PDF 01-084-8280; d-spacings: 4.2 Å, 2.4 Å ^ Functional Link: Ultra-slow Fe³⁺ release ^ Hydrogen Bonding: O–H⋯O: 2.63 Å (inter-chain) 5 ^ Void Volume: Nanotunnels (2.8 Å) Structure No.24: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver calcium and phosphate phosphorus to plants in a protected, stable, and efficient form, with a polymer 10 (Ca(HPO)) identified in crystallography as Monetite, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer dibasic calcium phosphate. Structural Description: ^ Dimensionality & Connectivity: 2D layers via Ca–O–P–O–Ca 15 ^ Bridging Ligand & Mode: μ₂-HPO₄²⁻ κO:κO' ^ Metal Coordination Sphere: Ca²⁺ 7-coordinate; mixed O-ligands ^ Crystallographic Proof: PDF 04-009-3755; d-spacings: 7.2 Å, 3.6 Å ^ Functional Link: Slow Ca²⁺ / P-release ^ Hydrogen Bonding: O–H⋯O: 2.59 Å (HPO₄–HPO₄) 20 ^ Void Volume: Interlayer gaps (8.5 Å) Structure No.25: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver calcium and sulfate sulfur to plants in a protected, stable, and efficient form, with a polymer (β-CaSO₄) 25 identified in crystallography as Anhydrite, a “known mineral found in nature. “ IUPAC (International Union of Pure and Applied Chemistry) nomenclature named polymer beta- calcium sulfate hemihydrate. Structural Description: ^ Dimensionality & Connectivity: 3D framework via Ca–O–S–O–Ca and Ca–O–Ca 47

[0048] ^ Bridging Ligand & Mode: μ₂-SO₄²⁻ κO:κO' + μ₂-O ^ Metal Coordination Sphere: Ca²⁺ 8-coordinate; 8× O (2.35–2.50 Å) ^ Crystallographic Proof: PDF 01-086-2270; d-spacings: 3.50 Å, 2.85 Å ^ Functional Link: Ultra-slow Ca²⁺ release 5 ^ Hydrogen Bonding: None ^ Void Volume: Micropores (3.5 Å) resist hydration Structure No.26: A) Crystalline Coordination Polymer Fertilizer, 2) Non-Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination non-nitrogen-metal polymer fertilizer, designed to deliver potassium, 10 magnesium, and sulfate sulfur to plants in a protected, stable, and efficient form, with a polymer (K₂Mg₂(SO₄)₃) identified in crystallography as Langbeinite, a “known mineral found in nature. “ IUPAC (International Union of Pure and Applied Chemistry) nomenclature names polymer dipotassium dimagnesium trisulfate. Structural Description: 15 ^ Dimensionality & Connectivity: 3D framework via Mg–O–S–O–Mg and K–O–S–O ^ Bridging Ligand & Mode: μ₂-SO₄²⁻ κO:κO' ^ Metal Coordination Sphere: Mg²⁺ octahedral; 6× O (2.05 Å); K⁺ 12-coordinate ^ Crystallographic Proof: ICDD 04-008-2-79; d-spacings: 4.2 Å, 3.0 Å ^ Functional Link: Sustained Mg²⁺ / K⁺ release 20 ^ Hydrogen Bonding: None ^ Void Volume: Minimal (dense) Structure No.27: B. Crystalline Coordination Complex Fertilizer, 3) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination urea-metal complex fertilizer, designed to deliver nitrogen, iron, sulfate 25 sulfur, and carbon to plants in a protected, stable and efficient form, with a complex (Fe(CH4N2O)6(SO4)(H2O)) identified as “new” as in “unknown”, but not “novel” as it reflects a similar crystalline coordination structure (referred to as an isomorphous compound) to other identified compounds in crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature names complex aquahexakis(urea)sulfatoiron(II). In another example, 48

[0049] urea reacts with two metal salts, the metal hydroxide is calcium hydroxide, and the metal sulfate is iron sulfate, and the resultant nitrogen-metal complex comprises urea iron sulfate including Fe(CH4N2O)6(SO4)(H2O). Structural Description, a “new” as in “unknown, but not “novel,” based on a Co analogue: 5 ^ Dimensionality & Connectivity: 0D discrete [Fe(urea)₆]²⁺ complex ^ Bridging Ligand & Mode: None ^ Metal Coordination Sphere: Fe²⁺ octahedral; 6× urea-O (2.12 Å) ^ Crystallographic Proof: PDF 00-042-0674, CCDC 1278464, CSD URCOSM ^ Functional Link: Gradual Fe²⁺ / N-release 10 ^ Hydrogen Bonding: N–H⋯O: 2.85 Å (urea–SO₄) ^ Void Volume: Packing voids (68 ų) Structure No.28: B. Crystalline Coordination Complex Fertilizer, 3) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination ammonium-metal complex fertilizer, designed to deliver nitrogen, 15 magnesium, and sulfate sulfur to plants in a protected, stable, and efficient form, with a complex ((NH4)2Mg(SO4)2(H2O)6) identified in crystallography as Boussingaultite, a “known mineral found in nature. “ IUPAC (International Union of Pure and Applied Chemistry) nomenclature names complex diammonium magnesium disulfate hexahydrate. Structural Description: 20 ^ Dimensionality & Connectivity: 0D discrete [Mg(H₂O)₆]²⁺ complexes ^ Bridging Ligand & Mode: None ^ Metal Coordination Sphere: Mg²⁺ octahedral; 6× H₂O (2.10 Å) ^ Crystallographic Proof: PDF 04-009-3829 ^ Functional Link: Rapid NH₄⁺ / Mg²⁺ release 25 ^ Hydrogen Bonding: N–H⋯O: 2.75 Å (NH₄⁺–SO₄) ^ Void Volume: Ionic lattice voids (72 ų) Structure No.29: B. Crystalline Coordination Complex Fertilizer, 3) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination ammonium-metal complex fertilizer, designed to deliver nitrogen, zinc, 49

[0050] and sulfate sulfur to plants in a protected, stable, and efficient form, with a complex ((NH4)2Zn(OH2)6(SO4)2) identified in crystallography as Katerinopoulosite, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names complex diammonium hexaaquazinc(II) disulfate. 5 Structural Description: ^ Dimensionality & Connectivity: 0D discrete [Zn(H₂O)₆]²⁺ complexes ^ Bridging Ligand & Mode: None ^ Metal Coordination Sphere: Zn²⁺ octahedral; 6× H₂O (2.08 Å) ^ Crystallographic Proof: PDF 04-007-5463; 2θ: 9.5°, 19.0° 10 ^ Functional Link: Immediate NH₄⁺ / Zn²⁺ release ^ Hydrogen Bonding: O–H⋯O: 2.67 Å (H₂O–SO₄) ^ Void Volume: Lattice voids (75 ų) Structure No.30: B. Crystalline Coordination Complex Fertilizer, 3) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise 15 crystalline coordination urea-metal complex fertilizer, designed to deliver nitrogen, magnesium, chloride, and carbon to plants in a protected, stable, and efficient form, with a complex ((CH4N2O)₆MgCl₂·(CH4N2O)₄) identified in crystallography as a "known synthetic structure.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names complex hexakis(urea)magnesium dichloride tetra(urea). 20 Structural Description: ^ Dimensionality & Connectivity: 0D discrete [Mg(urea)6]2+complexes; Cl−anions and neutral lattice urea molecules ^ Bridging Ligand & Mode: None ^ Metal Coordination Sphere: Mg2+ octahedral; 6× urea-O 25 ^ Crystallographic Proof: CAD NUXTROS ^ Functional Link: Rapid Mg2+ / N-release ^ Hydrogen Bonding: Extensive N–H⋯Cl, N–H⋯O ^ Void Volume: Interstitial spaces Structure No.31: B. Crystalline Coordination Complex Fertilizer, 3) Nitrogen-Metal: 50

[0051] In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination ammonium-metal complex fertilizer, designed to deliver nitrogen, magnesium, and chloride to plants in a protected, stable, and efficient form, with a complex (MgCl2(NH4)2Cl(H2O)6) identified in crystallography as the rare mineral Novograblenovite, a 5 “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names complex ammonium hexaaquamagnesium(II) trichloride. Structural Description: ^ Dimensionality & Connectivity: Ionic lattice with discrete [Mg(H₂O)₆]²⁺ complexes ^ Bridging Ligand & Mode: None 10 ^ Metal Coordination Sphere: Mg²⁺ octahedral; 6× H₂O (2.10 Å) ^ Crystallographic Proof: ICSD 183507 ^ Functional Link: Rapid Mg²⁺ / NH₄⁺ / Cl⁻ release ^ Hydrogen Bonding: O–H⋯Cl: 3.15 Å (H₂O–Cl⁻) + N–H⋯Cl: 3.10 Å (NH₄⁺–Cl⁻) ^ Void Volume: Ionic lattice voids (70 ų) 15 Structure No.32: B. Crystalline Coordination Complex Fertilizer, 3) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination urea-metal complex fertilizer, designed to deliver nitrogen, magnesium, chloride, and carbon to plants in a protected, stable, and efficient form, with a complex (MgCl2(H2O)2(CH4N2O)4) identified in crystallography as a "known synthetic structure.” IUPAC 20 (International Union of Pure and Applied Chemistry) nomenclature names complex diaquatetrakis(urea)magnesium(II) chloride. Structural Description: ^ Dimensionality & Connectivity: 0D discrete [Mg(urea)₄(H₂O)₂]²⁺ complexes ^ Bridging Ligand & Mode: None 25 ^ Metal Coordination Sphere: Mg²⁺ octahedral; 4× urea-O (2.07 Å) + 2× H₂O (2.05 Å) ^ Crystallographic Proof: CSD Refcode NUTVOQ ^ Functional Link: Gradual Mg²⁺ / N-release ^ Hydrogen Bonding: N–H⋯Cl: 3.10 Å (urea–Cl⁻) ^ Void Volume: Molecular packing voids (65 ų) 51

[0052] Structure No.33: B. Crystalline Coordination Complex Fertilizer, 3) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination urea-metal complex fertilizer, designed to deliver nitrogen, magnesium, chloride, and carbon to plants in a protected, stable and efficient form, with a complex 5 ([Mg(CH4N2O)6]Cl2) identified as “novel” as “of a new kind”, unknown and unreported in crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature names complex hexakis(urea)magnesium(II) chloride. Structural Description - as an unpublished SCXRD, a detailed description is provided: ^ Dimensionality & Connectivity: This structure forms a 0D (zero-dimensional) discrete 10 coordination complex. It consists of positively charged [(urea)₆Mg]²⁺ complex caƟons that are charge-balanced by chloride anions (Cl−) within the crystal lattice. ^ Bridging Ligand & Mode: There are no bridging ligands that create an extended network. All urea molecules are terminally coordinated to the magnesium center. Chloride anions act as counterions. 15 ^ Metal Coordination Sphere: Mg²⁺ centers are coordinated by oxygen atoms from six urea molecules. (This strongly suggests an octahedral coordination geometry for Mg(II)). ^ Crystallographic Proof: Monoclinic system (Space Group (15)). Unique unit cell parameters: a=16.665 Å, b=15.750 Å, c=8.276 Å; α=90∘, β=109.084∘, γ=90∘; V=2053.1 Å3; Z=4. This confirms a novel / new crystalline structure. 20 ^ Functional Link: The discrete complex nature of this structure supports controlled nutrient release (Mg, N) and provides enhanced stability to the incorporated urea. ^ Hydrogen Bonding: Extensive H-bonding is expected from the numerous urea molecules, significantly contributing to the overall crystal packing and structural integrity. ^ Void Volume: The specific void volume derived from the crystal packing efficiency (density / unit 25 cell) could influence properties like solubility and the rate at which nutrients are released from the fertilizer. Structure No.34: B. Crystalline Coordination Complex Fertilizer, 3) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination urea-metal complex fertilizer, designed to deliver nitrogen, magnesium, 52

[0053] sulfate sulfur, and carbon to plants in a protected, stable and efficient form, with a complex (Mg(CH4N2O)₆(SO₄)(H₂O)₀.₅) identified as “novel” as “of a new kind”, unknown and unreported in crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature names complex magnesium hexakis(urea) sulfate hemihydrate. 5 Structural Description - as an unpublished SCXRD, a detailed description is provided: ^ Dimensionality & Connectivity: This structure forms a 0D (zero-dimensional) discrete coordination complex. It consists of positively charged [Mg(urea)6(H₂O)]²⁺ complex caƟons that are charge-balanced by sulfate anions (SO42−) within the crystal lattice. ^ Bridging Ligand & Mode: There are no bridging ligands that create an extended network. Urea 10 and water molecules are terminally coordinated to the magnesium center. Sulfate anions act as outer-sphere counterions, not direct ligands. ^ Metal Coordination Sphere: Mg²⁺ centers are coordinated by oxygen atoms from four urea molecules and one water molecule. This likely results in an octahedral coordination geometry for Mg(II). 15 ^ Crystallographic Proof: Monoclinic system (Space Group (7)). Unique unit cell parameters: a=19.024 Å, b=22.272 Å, c=10.503 Å; α=90∘, β=90.478∘, γ=90∘; V=4449.9 Å3; Z=12. This confirms a novel crystalline structure. ^ Functional Link: The discrete complex nature of this structure supports controlled nutrient release (Mg, N, S) and provides enhanced stability to the incorporated magnesium and urea. 20 ^ Hydrogen Bonding: Extensive H-bonding is inferred from the presence of urea and water moieties, which significantly contributes to the crystal packing and overall structural stability, especially between the complex cations and sulfate anions. ^ Void Volume: Specific void volume is inferred from the crystal packing efficiency (density / unit cell); this has potential implications for influencing solubility, dissolution rates, and nutrient 25 accessibility within the fertilizer matrix. Structure No.35: B. Crystalline Coordination Complex Fertilizer, 3) Nitrogen-Metal: In the preferred non-limiting embodiments, the present disclosure compositions comprise crystalline coordination urea-metal complex fertilizer, designed to deliver nitrogen, magnesium, sulfate sulfur, and carbon to plants in a protected, stable and efficient form, with a complex 53

[0054] (Mg(CH4N2O)4(H₂O)(SO₄)) identified as “novel” as “of a new kind”, unknown and unreported in crystallography. IUPAC (International Union of Pure and Applied Chemistry) nomenclature names complex aqua tetrakis(urea)magnesium(II) sulfate. Structural Description - as an unpublished SCXRD, a detailed description is provided: 5 ^ Dimensionality & Connectivity: This structure forms a 0D (zero-dimensional) discrete coordination complex. It consists of positively charged [Mg(urea)₄(H₂O)]²⁺ complex caƟons that are charge-balanced by sulfate anions (SO42−) within the crystal lattice. ^ Bridging Ligand & Mode: There are no bridging ligands that create an extended network. Urea and water molecules are terminally coordinated to the magnesium center. Sulfate anions act as 10 outer-sphere counterions, not direct ligands. ^ Metal Coordination Sphere: Mg²⁺ centers are coordinated by oxygen atoms from four urea molecules and one water molecule. This likely results in an octahedral coordination geometry for Mg(II). ^ Crystallographic Proof: Monoclinic system (Space Group (7)). It has unique unit cell parameters: 15 a=19.024 Å, b=22.272 Å, c=10.503 Å; α=90∘, β=90.478∘, γ=90∘; V=4449.9 Å3; Z=12. This confirms a novel crystalline structure. ^ Functional Link: The discrete complex nature of this structure supports controlled nutrient release (Mg, N, S) and provides enhanced stability to the incorporated magnesium and urea. ^ Hydrogen Bonding: Extensive H-bonding is inferred from the presence of urea and water 20 moieties, which significantly contributes to the crystal packing and overall structural stability, especially between the complex cations and sulfate anions. ^ Void Volume: Specific void volume is inferred from the crystal packing efficiency (density / unit cell); this has potential implications for influencing solubility, dissolution rates, and nutrient accessibility within the fertilizer matrix. 25 Structure No.36: B. Crystalline Coordination Complex Fertilizer, 3) Nitrogen-Metal: In the preferred non-limited embodiments, the present disclosure compositions comprise crystalline coordination ammonium-metal complex fertilizer, designed to deliver nitrogen, iron, and sulfate sulfur to plants in a protected, stable, and efficient form, with a complex ((NH4)2Fe(SO4)2(H2O)6) identified in crystallography as Mohrite, a “known mineral found in 54

[0055] nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names complex diammonium hexaaquairon(II) disulfate. In another example, urea reacts with two metal salts, the metal hydroxide is calcium hydroxide, and the metal sulfate is iron sulfate, the resultant nitrogen-metal complex comprises ammonium iron sulfate including 5 (NH4)2Fe(SO4)2(H2O)6.Structural Description: ^ Dimensionality & Connectivity: 0D discrete [Fe(H₂O)₆]²⁺ complexes ^ Bridging Ligand & Mode: None (terminal SO₄) ^ Metal Coordination Sphere: Fe²⁺ octahedral; 6× H₂O (2.12 Å) 10 ^ Crystallographic Proof: PDF 04-025-0291; 2θ: 10.4°, 20.9° ^ Functional Link: Immediate NH₄⁺ release; slow Fe²⁺ hydrolysis ^ Hydrogen Bonding: O–H⋯O: 2.70 Å (H₂O–SO₄) ^ Void Volume: Isolated cavities (68 ų) for NH₄⁺ Structure No.37: B. Crystalline Coordination Complex Fertilizer, 3) Nitrogen-Metal: 15 In the preferred non-limited embodiments, the present disclosure compositions comprise crystalline coordination ammine-metal complex fertilizer, designed to deliver nitrogen, copper, and sulfate sulfur to plants in a protected, stable, and efficient form, with a complex (Cu(SO4)(NH3)4(H2O)) identified in crystallography as a "known synthetic structure.” N- and O- donor ligands are well-documented as effective urease inhibitors, particularly when complexed 20 with transition metals. N- and O-donor ligands form stable complexes with transition metals (e.g., Zn, Cu), which disrupt the nickel-active site of urease (M. Kulig-Adamiak et al., RSC Advances, 2017; R. D. Al-Sultani et al., RSC Advances, 2021; and R. Shah et al., ACS Omega, 2020, 5, 17, 10174–10183). IUPAC (International Union of Pure and Applied Chemistry) nomenclature names complex tetraammineaquasulfatocopper(II). 25 Structural Description: ^ Dimensionality & Connectivity: 0D discrete [Cu(NH₃)₄(H₂O)(SO₄)] complexes ^ Bridging Ligand & Mode: None ^ Metal Coordination Sphere: Cu²⁺ octahedral; 4× NH₃ (2.05 Å) + 1× H₂O + 1× SO₄-O ^ Crystallographic Proof: PDF 04-011-0483; d-spacings: 6.2 Å, 3.1 Å 55

[0056] ^ Functional Link: Rapid Cu²⁺ / N-release ^ Hydrogen Bonding: N–H⋯O: 2.72 Å (NH₃–SO₄) ^ Void Volume: Isolated sites (50 ų) Structure No.38: B. Crystalline Coordination Complex Fertilizer, 3) Nitrogen-Metal: 5 In the preferred non-limited embodiments, the present disclosure compositions comprise crystalline coordination ammine-metal complex fertilizer, designed to deliver nitrogen, zinc, and chloride to plants in a protected, stable, and efficient form, with a complex (Zn(NH₃)₂Cl₂) identified in crystallography as a "known synthetic structure.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names complex diamminedichloridozinc(II). 10 Structural Description: ^ Dimensionality & Connectivity: 0D discrete Zn(NH₃)₂Cl₂ complexes ^ Bridging Ligand & Mode: None ^ Metal Coordination Sphere: Zn²⁺ tetrahedral; 2× NH₃ (2.02 Å) + 2× Cl⁻ (2.20 Å) ^ Crystallographic Proof: PDF 00-024-1435; 2θ: 12.0°, 24.1° 15 ^ Functional Link: Fast Zn²⁺ / N-release ^ Hydrogen Bonding: N–H⋯Cl: 3.05 Å (NH₃–Cl⁻) ^ Void Volume: Molecular cavities (45 ų) Structure No.39: C. Crystalline Ionic Compound Fertilizer, 5) Nitrogen-Ionic: In the preferred non-limiting embodiments, the present disclosure compositions comprise a 20 nitrogen-ionic compound (ammonium sulfate) fertilizer, designed to deliver nitrogen and sulfate sulfur fertilizer, with an ionic compound ((NH₄)₂SO₄) identified in crystallography as Mascagnite, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names complex diammonium sulfate. A process for producing an ammonium sulfate containing fertilizer, comprising reacting urea with metal salts, 25 a copper sulfate, or iron sulfate or manganese sulfate and having the crystalline structure (NH4)2SO4. The metals, copper (Cu), iron (Fe), and manganese (Mn) are transition metals. They belong to the d-block of the periodic table and exhibit characteristic properties of transition elements. The formation of both nitrogen-metal compositions and ammonium sulfate in 56

[0057] reactions involving urea with copper, iron, or manganese sulfates arises from two competing pathways, influenced by reaction conditions: Structural Description: ^ Dimensionality & Connectivity: Ionic lattice (no coordination bonds) 5 ^ Bridging Ligand & Mode: None ^ Metal Coordination Sphere: None (no metals) ^ Crystallographic Proof: PDF 04-005-8533; 2θ: 10.0°, 20.2° ^ Functional Link: Rapid N-release ^ Hydrogen Bonding: N–H⋯O: 2.70 Å (NH₄⁺–SO₄) 10 ^ Void Volume: Lattice channels (4.0 Å) Structure No.40: C. Crystalline Ionic Compound Fertilizer, 5) Nitrogen-Ionic: In the preferred non-limiting embodiments, the present disclosure compositions comprise a nitrogen-ionic compound (ammonium chloride) fertilizer, designed to deliver nitrogen and chloride fertilizer, with an ionic compound (NH₄Cl) identified in crystallography as Salammoniac, 15 a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names ionic compound ammonium chloride. Structural Description: ^ Dimensionality & Connectivity: Ionic lattice ^ Bridging Ligand & Mode: None 20 ^ Metal Coordination Sphere: None ^ Crystallographic Proof: ICDD 04-016-0227; d-spacings: 3.1 Å, 1.9 Å ^ Functional Link: Immediate N-release ^ Hydrogen Bonding: N–H⋯Cl: 3.15 Å (NH₄⁺–Cl⁻) ^ Void Volume: Minimal (cubic close packing) 25 Structure No.41: C. Crystalline Ionic Compound Fertilizer, 5) Nitrogen-Ionic: In the preferred non-limiting embodiments, the present disclosure compositions comprise a nitrogen-ionic compound (urea-ammonium chloride) fertilizer, designed to deliver nitrogen and chloride fertilizer, with an ionic compound (Urea(NH₄Cl)) identified in crystallography as a 57

[0058] "known synthetic structure.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names ionic compound urea—ammonium chloride. Structural Description: ^ Dimensionality & Connectivity: Co-crystal ionic lattice 5 ^ Bridging Ligand & Mode: None ^ Metal Coordination Sphere: None ^ Crystallographic Proof: CSD URAMCL01 ^ Functional Link: Rapid N-release ^ Hydrogen Bonding: N–H⋯Cl: 3.08 Å (urea–Cl⁻) + N–H⋯O: 2.95 Å (NH₄⁺–urea) 10 ^ Void Volume: Molecular planes (5.5 Å) Structure No.42: C. Crystalline Ionic Compound Fertilizer, 5) Nitrogen-Ionic: In the preferred non-limiting embodiments, the present disclosure compositions comprise a nitrogen-ionic compound (ammonium phosphate) fertilizer, designed to deliver nitrogen and phosphate phosphorus fertilizer, with an ionic compound ((NH₄)(H₂PO₄)) identified in 15 crystallography as Biphosphammite, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names ionic compound ammonium phosphate. Structural Description: ^ Dimensionality & Connectivity: Ionic lattice 20 ^ Bridging Ligand & Mode: None ^ Metal Coordination Sphere: None ^ Crystallographic Proof: PDF 04-007-7071; d-spacings: 4.4 Å, 3.7 Å ^ Functional Link: Rapid N / P-release ^ Hydrogen Bonding: N–H⋯O: 2.65 Å (NH₄⁺–H₂PO₄) 25 ^ Void Volume: Hydrogen-bonded layers Structure No.43: C. Crystalline Ionic Compound Fertilizer, 5) Nitrogen-Ionic: In the preferred non-limiting embodiments, the present disclosure compositions comprise a nitrogen-ionic compound (diammonium phosphate) fertilizer, designed to deliver nitrogen and phosphate phosphorus fertilizer, with an ionic compound ((NH₄)₂(HPO₄)) identified in 58

[0059] crystallography as Phosphammite, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature names ionic compound diammonium phosphate. Structural Description: 5 ^ Dimensionality & Connectivity: Ionic lattice ^ Bridging Ligand & Mode: None ^ Metal Coordination Sphere: None ^ Crystallographic Proof: PDF 04-009-3766; 2θ: 10.3°, 20.6° ^ Functional Link: Immediate N / P-release 10 ^ Hydrogen Bonding: N–H⋯O: 2.68 Å (NH₄⁺–HPO₄) ^ Void Volume: Isolated cavities (62 ų) Structure No.44: C. Crystalline Ionic Compound Fertilizer, 6) Non-Nitrogen-Ionic: In the preferred non-limiting embodiments, the present disclosure compositions comprise a non- nitrogen-ionic compound (potassium chloride) fertilizer, designed to deliver potassium and 15 chloride fertilizer, with an ionic compound (KCl)) identified in crystallography as Sylvite, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature is named ionic compound potassium chloride. Structural Description: ^ Dimensionality & Connectivity: Ionic lattice 20 ^ Bridging Ligand & Mode: None ^ Metal Coordination Sphere: None ^ Crystallographic Proof: ICDD 00-041-1471; d-spacings: 3.1 Å, 2.2 Å ^ Functional Link: Fast K⁺ / Cl⁻ release ^ Hydrogen Bonding: None 25 ^ Void Volume: None (dense) Structure No.45: C. Crystalline Ionic Compound Fertilizer, 6) Non-Nitrogen-Ionic: In the preferred non-limiting embodiments, the present disclosure compositions comprise a non- nitrogen-ionic compound (potassium sulfate) fertilizer, designed to deliver potassium and sulfate sulfur fertilizer, with an ionic compound (K₂(SO₄)) identified in crystallography as 59

[0060] Arcanite, a “known mineral found in nature.” IUPAC (International Union of Pure and Applied Chemistry) nomenclature named ionic compound potassium sulfate. Structural Description: ^ Dimensionality & Connectivity: Ionic lattice 5 ^ Bridging Ligand & Mode: None ^ Metal Coordination Sphere: None ^ Crystallographic Proof: PDF 00-002-2164; 2θ: 11.5°, 23.0° ^ Functional Link: Fast K⁺ release ^ Hydrogen Bonding: None 10 ^ Void Volume: Minimal In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions wherein structural engineering enables the formation of a protected, stable, and highly efficient framework for nutrient delivery. The invention is fundamentally characterized by its ability to achieve controlled and sustained release of essential nutrients 15 into the plant root zone, precisely matching plant uptake requirements over extended periods. These crystalline fertilizer compositions offer numerous significant advantages. They facilitate nitrogen stabilization and delivery by transforming urea and metal salts into diverse, stable nitrogen-metal fertilizer forms, including urea-metal, ammonium-metal, and ammine-metal structures, thereby substantially reducing environmentally detrimental nitrogen loss. 20 Furthermore, these engineered solid-state structures enable multi-nutrient and simultaneous delivery, integrating various essential macro- and micronutrients within a single particle for balanced and synchronized release. This leads to enhanced fertilizer efficiency, maximizing nutrient utilization and resulting in maximized crop yields and quality. The improved nutrient protection and stability, inherent to the coordination polymer and complex framework, reduce 25 premature degradation and immobilization. This also contributes to superior environmental protection by minimizing runoff and emissions and enables reduced application frequency and costs. Additionally, the controlled release profile helps in mitigating salt burn in plants. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which: Principles of Crystalline Fertilizer Formation: Various aspects of 60

[0061] the present disclosure support the process of reacting urea and metal salts in an aqueous solution with heat added to form crystalline fertilizer compositions involves several fundamental chemistry principles: I. Coordination Chemistry Fundamentals 51. Lewis Acid-Base Theory: o Metal Ions as Lewis Acids: Metal ions, especially transition metal ions, act as Lewis acids because they have empty valence orbitals and can accept electron pairs. o Urea as a Lewis Base (Ligand): Urea, with its lone pairs of electrons on the carbonyl oxygen and to a lesser extent, the nitrogen atoms, acts as a Lewis base (ligand). It donates these electron 10 pairs to the metal ion. o Coordinate Covalent Bonds: The bond formed between the metal ion and the urea ligand is a coordinate covalent bond (or dative bond), where both electrons in the shared pair come from the ligand. 2. Coordination Number and Geometry: 15o Metal ions tend to achieve a specific coordination number (the number of donor atoms directly bonded to the metal) and geometry (e.g., octahedral, tetrahedral, square planar) that minimizes steric repulsion and maximizes orbital overlap. Urea can coordinate in various ways, often as a monodentate ligand through its oxygen. o The specific metal ion and its electron configuration will influence the preferred coordination 20 number and geometry. 3. Ligand Exchange / Substitution: o In aqueous solution, metal ions are typically "aquated," meaning they are already coordinated to water molecules (e.g., [M(H2O)6]n+). o The reaction with urea involves a ligand exchange or substitution reaction, where urea 25 molecules replace water molecules in the metal's coordination sphere. This process is driven by the relative stability of the metal-urea bond compared to the metal-water bond, and by entropy changes (releasing water molecules from the coordination sphere can increase overall disorder). 4. Charge Balance: 61

[0062] o The overall charge of the resulting coordination complex must be balanced by counter-ions from the original metal salt. If the metal salt is MCl2, and a neutral urea ligand coordinates, the resulting complex will likely have a positive charge balanced by chloride ions outside the coordination sphere (e.g., [M(urea)x]Cl). 5 II. Solution Chemistry and Thermodynamics 1. Dissolution and Solvation: o Metal Salts: Metal salts must first dissolve in water. This involves the dissociation of the ionic lattice into solvated metal cations and anions. The solubility depends on the lattice energy of the salt and the solvation energy of its ions. 10o Urea: Urea's high water solubility allows it to readily dissolve and become available for coordination. o Solvent (Water) Effects: Water acts as the solvent, facilitating the movement and interaction of ions and molecules. It also participates in the initial solvation of metal ions and can be displaced during complex formation. 152. Chemical Equilibrium: o The formation of the complex is an equilibrium process: Mn+(aq)+xUrea(aq)⇌[M(Urea)x]n+(aq) o Gibbs Free Energy (Delta G): The spontaneity and extent of complex formation are determined by the change in Gibbs free energy (Delta G= Delta H−T Delta S). For the reaction to be favorable, Delta G should be negative. 20 Enthalpy (Delta H): Heat is often added, suggesting that the formation of the complex might be endothermic (requires heat, Delta H greater than 0) or that heating simply speeds up the reaction. However, strong metal-ligand bonds generally lead to exothermic complex formation (Delta H less than 0). The overall Delta H also includes the energy released from breaking metal- water bonds and forming new metal-urea bonds. 25 Entropy (Delta S): The displacement of several organized water molecules by fewer urea molecules can lead to an increase in disorder (positive Delta S), which favors complex formation, especially at higher temperatures. 62

[0063] o Le Chatelier's Principle: Heat addition can shift the equilibrium. If the complexation is endothermic, increasing temperature will favor product formation. If it's exothermic, heating might initially speed it up but ultimately reduce yield at equilibrium. 3. Kinetics: 5o Reaction Rate: Heat addition increases the kinetic energy of the reacting species, leading to more frequent and energetic collisions between metal ions and urea molecules. This generally increases the rate of reaction, allowing the complex to form more quickly. o Activation Energy: Heat helps overcome the activation energy barrier for the ligand exchange process. 10 III. Crystallization Principles 1. Supersaturation: o For crystals to form, the solution must become supersaturated with respect to the coordination complex. This means the concentration of the composition in solution exceeds its solubility limit at that temperature. 15o Supersaturation can be achieved by: Cooling: As the solution cools after heating, the solubility of most solids (including coordination complexes) decreases, causing the complex to come out of solution. Solvent Evaporation: Removing some of the water solvent (e.g., by prolonged heating or leaving the solution open to air) increases the concentration of the complex, leading to 20 supersaturation. 2. Nucleation: o This is the initial formation of tiny, stable crystal nuclei from the supersaturated solution. It can occur spontaneously (homogeneous nucleation) or be initiated by impurities, rough surfaces, or adding "seed" crystals (heterogeneous nucleation). 253. Crystal Growth: o Once nuclei are formed, more molecules of the complex from the supersaturated solution deposit onto the surfaces of these nuclei, causing them to grow into macroscopic crystals. o Controlled Cooling / Evaporation: Slow cooling or controlled evaporation generally leads to larger, more well-formed crystals because it allows molecules to deposit in an ordered fashion 63

[0064] onto existing crystal faces rather than forming many small, disordered crystals (which happens with rapid cooling / evaporation). 4. Lattice Energy and Crystal Structure: o The formation of a stable crystalline solid is driven by the minimization of energy. The 5 coordination molecules or ions arrange themselves into a repeating, ordered one, two or three- dimensional crystal lattice. o Intermolecular Forces: Hydrogen bonding (between urea ligands, and with co-crystallized water), ionic interactions (between complex ions and counter-ions), and van der Waals forces play roles in stabilizing the crystal lattice. 10o The specific crystal structure (e.g., monoclinic, orthorhombic) depends on the size and shape of the complex, the counter-ions, and the solvent molecules (if co-crystallized). The entire process is an interplay of how metal ions and ligands interact in solution (coordination chemistry), how these interactions are influenced by energy and entropy (thermodynamics / kinetics), and how the product can then be isolated in a pure, solid form 15 (crystallization). In the preferred non-limiting embodiments, the present disclosure supports crystalline fertilizer composition, it represents an innovative approach to nutrient delivery in agriculture. By combining the benefits of coordination chemistry and crystalline structures, they offer the potential for more efficient and environmentally sustainable fertilization practices. 20 In the preferred non-limiting embodiments, the present disclosure supports a fertilizer approach that aims to deliver nitrogen and other nutrients to plants in a more controlled and efficient manner compared to traditional fertilizers. In the preferred non-limiting embodiments, the present disclosure supports a type of fertilizer that combines advanced coordination chemistry with agronomic needs, offering a 25 sustainable solution to enhance crop productivity while mitigating environmental impacts. In the preferred non-limiting embodiments, the present disclosure supports enhanced efficiency fertilizers that provide significant long-term economic benefits through reduced input costs, higher yields, and avoided environmental penalties. Advancements in sustainable materials and government support are driving adoption. Farmers transitioning to enhanced 64

[0065] efficiency fertilizers are reported to achieve 20–30% cost savings over conventional fertilizers while supporting ecological resilience. In the preferred non-limiting embodiments, the present disclosure provides a crystalline fertilizer compositions, a specialized type of fertilizer designed to provide nitrogen (N) and 5 essential macronutrients and micronutrients to plants through a structured coordination fertilizer. In the preferred non-limiting embodiments, the present disclosure provides crystalline fertilizer composition structure: these coordination fertilizers are arranged in a highly ordered, repeating one, two or three-dimensional structure, forming crystals. 10 In the preferred non-limiting embodiments, the present disclosure supports the crystalline nature in this invention for fertilizer application, such as controlled dissolution, the rate at which the fertilizer dissolves in the soil and releases nutrients can be influenced by the crystal structure and size. This can lead to a more sustained release of nutrients, reducing losses due to leaching or rapid conversion; improved handling, crystalline solids are generally easier to 15 handle, store, and apply; enhanced stability and protection, the ordered arrangement in a crystal lattice can enhance the chemical stability and protection of the coordination compositions. In the preferred non-limiting embodiments, the present disclosure provides two distinct features; crystalline fertilizer compositions arranged in a substantially regular, repeating lattice 20 structure, enhancing stability and ease of handling; and coordination compositions, having a central metal ion bonded to ligands, ligands donate electron pairs to the metal, forming stable coordination bonds. In the preferred non-limiting embodiments, the present disclosure supports specific metal ion and the type and number of ligands that determine the complex's structure, stability, and 25 properties. In the preferred non-limiting embodiments, the present disclosure supports a multiple nutrient supply; nitrogen and metal salts that provide numerous combinations of macronutrient and micronutrients. 65

[0066] In the preferred non-limiting embodiments, the present disclosure supports controlled release mechanism, degradation depends on soil moisture, pH, microbial activity, or root exudates, ensuring sustained nutrient availability. In the preferred non-limiting embodiments, the present disclosure provides advantages, 5 such as environmental benefits, minimizing nitrogen and macronutrient and micronutrient soil losses and environmental contamination by nutrients; efficiency, attempts to match nutrient release with plant uptake, reducing application frequency; and multi-nutrient, supplies several required nutrients. In the preferred non-limiting embodiments, the present disclosure supports precision 10 agriculture and environmentally sensitive areas. In the preferred non-limiting embodiments, the present disclosure supports enhanced nitrogen delivery, a primary purpose of this fertilizer invention is to supply nitrogen in a more efficient form, an essential macronutrient for plant growth. In the preferred non-limiting embodiments, the present disclosure provides coordinating 15 nitrogen-rich molecules from urea with metal salts, that are transformed into a form of nitrogen-metal compositions potentially offering benefits; reducing volatilization as ammonia gas, improving nitrogen use efficiency and enhanced uptake, and metal salts provide coordination metal ion center that positively influences the plant's ability to absorb the nutrients. 20 In the preferred non-limiting embodiments, the present disclosure supports enhanced crop yield and quality; by providing nutrients in a more optimized way, these fertilizers could potentially lead to improved plant growth and productivity. In the preferred non-limiting embodiments, the present disclosure supports that urea and metal salts, combined, have a synergy to readily transform into crystalline fertilizer 25 compositions. In the preferred non-limiting embodiments, the present disclosure supports a crystalline fertilizer composition between urea and metal salts that promote enhanced efficiency fertilizers. 66

[0067] In the preferred non-limiting embodiments, the present disclosure supports that urea can act as a structure-directing agent, influencing the architecture of crystalline fertilizer compositions and framework. In the preferred non-limiting embodiments, the present disclosure supports that urea and 5 metal salts, combined, demonstrate that they are highly effective at generating crystalline fertilizer compositions with coordination framework. In the preferred non-limiting embodiments, the present disclosure support that urea and metal salts readily donate lone pairs of electrons to central metal ions to form coordination covalent bonds. 10 In the preferred non-limiting embodiments, the present disclosure support that urea and metal salts provide three critical components in the formation of a crystalline fertilizer compositions coordination framework : 1) central metal atom (sourced from metal salts); 2) urea atoms that act as donor ligands that surround the central metal atom or act as counterions; and 3) non-metal (salt) atoms that act as donor ligands that surround the central 15 metal atom. In the preferred non-limiting embodiments, the present disclosure support urea and metal salts that donate the following ligands that surround the metal center to form a coordination composition: 1) urea can donate a oxygen atom from its carbonyl (C=O) group and two nitrogen atoms from its amide (NH2)2group (making it a tridentate (3) ligand in coordination chemistry); 20 and 2) non-metal salts can donate oxygen atoms from oxide, hydroxide, carbonate, sulfate, phosphate, nitrate, and acetate; and a chlorine atom from chloride. In the preferred non-limiting embodiments, the present disclosure provides that oxygen, nitrogen, and sulfate are the most common coordination atoms (ligands), and chloride is also a coordination atom (ligand), used in coordination framework. 25 In the preferred non-limiting embodiments, the present disclosure support coordination framework synergy between urea and metal salts, is the quality of the complexes synthesized and the degree of coordination – many of the complexes have a high-degree of coordination, meaning they have a high coordination number (6 to 8). 67

[0068] In the preferred non-limiting embodiments, the present disclosure supports that coordination frameworks provide stable, protected, efficient and available nutrients to the plant. In the preferred non-limiting embodiments, the present disclosure supports improved 5 nutrient use efficiency, sustainable agriculture, and reduction in environmental impact, as such it qualifies as an enhanced efficiency fertilizer. In the preferred non-limiting embodiments, the present disclosure supports large-scale manufacturing, with a simplified and cost-effective approach to making crystalline fertilizer compositions. 10 In the preferred non-limiting embodiments, the present disclosure provides for a crystalline fertilizer composition, referring to a class of substances with chemical structures in which a central metal atom is surrounded by non-metal atoms or groups of atoms, called ligands, joined to it by chemical bonds. In the preferred non-limiting embodiments, the present disclosure support that urea has a 15 multifunctional role as a ligand, combined with metal salts, makes them a valuable component in synthesizing crystalline fertilizer compositions with tailored properties for fertilizer application. In the preferred non-limiting embodiments, the present disclosure provides crystalline fertilizer compositions that protect a structure by forming strong, stable bonds with specific 20 sites on a molecule, essentially acting to encapsulate, which helps maintain the molecule's shape and prevent it from undergoing structural changes or degradation, thus safeguarding its structural integrity. In the preferred non-limiting embodiments, the present disclosure provides for coordination covalent bonds that are formed by two atoms sharing a pair of electrons, it plays a 25 significant role in maintaining a crystalline structure, particularly in coordination framework where a central metal ion forms multiple coordinate bonds with surrounding ligands, creating a stable, repeating lattice arrangement that defines the crystalline structure. In the preferred non-limiting embodiments, the present disclosure support crystalline fertilizer composition mechanisms, urea and metal salts, combined, produce an effect greater 68

[0069] than the sum of their individual effects, essentially meaning that together they are a much more effective and beneficial as a fertilizer than if used individually: 1) formation of crystalline fertilizer compositions ; and 2) urea conversion to a more efficient form of nitrogen for plant uptake, such as coordination ammonium-metal , coordination urea-metal and coordination 5 ammine-metal frameworks. In the preferred non-limiting embodiments, the present disclosure supports improved nutrient use efficiency, sustainable agriculture, and reduction in environmental impact. In the preferred non-limiting embodiments, the present disclosure provides for crystalline fertilizer compositions that are nitrogen-metal framework, meaning it contains nitrogen in the 10 framework and non-nitrogen-metal framework, meaning it contains no nitrogen in the framework. Various aspects of the present disclosure provide for crystalline fertilizer compositions with nitrogen-ionic compound fertilizer, meaning it contains nitrogen in the crystalline fertilizer composition and non-nitrogen-ionic compound fertilizer, meaning it contains no nitrogen in the 15 crystalline fertilizer composition. In the preferred non-limiting embodiments, the present disclosure provides for urea and metal salt crystalline fertilizer compositions that protect and resist soil interaction for more efficient delivery to the plant. In the preferred non-limiting embodiments, the present disclosure provides for urea as the 20 primary nitrogen source, compared with other nitrogen sources it is highly compatible with metal salts, has a lower cost and is widely available, making it well suited as a key component in crystalline fertilizer compositions. In the preferred non-limiting embodiments, the present disclosure provides for urea and metal salts in a crystalline fertilizer composition that is non-toxic, biodegradable, 25 environmentally safe, and aligned with green chemistry principles. In the preferred non-limiting embodiments, the present disclosure supports urea's ability to form hydrogen bonds that can enhance crystalline fertilizer composition stability and influence physical properties like crystallinity or melting points. 69

[0070] In the preferred non-limiting embodiments, the present disclosure supports urea's natural occurrence in biological systems making it safe for crystalline fertilizer compositions. In the preferred non-limiting embodiments, the present disclosure provides for reactions involving urea and metal salts that typically require mild conditions (e.g., moderate 5 temperatures, aqueous media), making it safe and simplifying synthesis and reducing energy consumption. In the preferred non-limiting embodiments, the present disclosure provides an invention that controls the nutrient profile and nutrient concentration of the crystalline fertilizer compositions. 10 In the preferred non-limiting embodiments, the present disclosure provides for crystalline fertilizer compositions that can be in the form of a liquid, powder, granule, pellet, extruded fertilizer and applied as a foliar or spreadable fertilizer. In the preferred non-limiting embodiments, the present disclosure provides crystalline fertilizer compositions that have different solubility, density, and pH sensitivity properties. 15 In the preferred non-limiting embodiments, the present disclosure provides methods of biodegradable synthesis of fertilizer in the form of crystalline fertilizer compositions using urea and metal salts and mixtures thereof. In the preferred non-limiting embodiments, the present disclosure provides methods and compositions for crystalline fertilizer that have enhanced efficiency fertilizer properties and 20 provide another method of urea enhanced efficiency fertilizer application. In the preferred non-limiting embodiments, the present disclosure provides methods and compositions for crystalline fertilizer compositions that promotes a new category for urea enhanced efficiency fertilizers, unlike the prior established technologies applying chemical agents / coatings and / or urease inhibitors to urea to slow of control ammonia volatility in soils. 25 In the preferred non-limiting embodiments, the present disclosure provides methods and compositions for crystalline fertilizer compositions that bind metal salts to nitrogen for higher nutrient use efficiency of nitrogen and metals. 70

[0071] In the preferred non-limiting embodiments, the present disclosure provides compositions comprising crystalline fertilizer compositions that are either one-, two- and / or three- dimensional coordination frameworks and mixtures thereof. In the preferred non-limiting embodiments, the present disclosure provides compositions 5 comprising crystalline fertilizer compositions that are one or two-dimensional anionic or neutral coordination networks or coordination complexes with nitrogen source between chains or layers and mixtures thereof. The layers or chains may be neutral or anionic, with no isolated metal or metal framework cations or anions. In the preferred non-limiting embodiments, the present disclosure provides compositions 10 comprising crystalline fertilizer compositions with a neutral metal complex in which metal atoms are coordinated via a variable number of oxygen atoms to the same metal atom and a nitrogen source is also bound via an oxygen or other donor atom and mixtures thereof. In the preferred non-limiting embodiments, the present disclosure provides compositions comprising crystalline fertilizer compositions that have metals coordinated to anions and / or to 15 water molecules, depending on the exact structure and mixtures thereof. In the preferred non-limiting embodiments, the present disclosure provides compositions comprising crystalline fertilizer compositions that have a nitrogen source that exhibit charge assisted strong hydrogen bonds and anions and cations bound by hydrogen bonding and metal salts bound by ionic bonding and mixtures thereof. 20 In the preferred non-limiting embodiments, the present disclosure supports crystalline fertilizer compositions with coordination framework that comprises polymer fertilizer and complex fertilizer framework. In the preferred non-limiting embodiments, the present disclosure supports crystalline fertilizer compositions comprising coordination framework for controlled release, reduced 25 environmental impact, and enhanced nutrient efficiency. This is directly aligned with the Association of American Plant Food Control Officials (AAPFCO) definition of enhanced efficiency fertilizer’s (EEF’s). In the preferred non-limiting embodiments, the present disclosure provides crystalline fertilizer compositions that can be assigned to at least one of three crystallography categories. 71

[0072] CCDC (Cambridge Crystallographic Data Centre, Boston, MA 02108, USA) categorizes crystallographic entries into three distinct groups based on structural and compositional properties. Here's a concise breakdown of each category: 1) “known minerals found in nature”, these are minerals with well-documented crystal structures that occur naturally.; 2) “novel” 5 structures, a structure is classified as "novel" (of a new kind) if it represents a previously unreported crystalline arrangement. This could involve a unique topology, coordination geometry, or lattice configuration not seen in any prior crystallographic studies.; and 3) “new” (isomorphous) structures, these are distinct structures that share the same crystal structure as a known material (isomorphous). For example, a compound where a metal ion in a known 10 structure is replaced that would be "new" but not novel. The structural motif is already recognized, even though the chemical composition differs. However, if we determine that a crystalline fertilizer composition is previously identified as a synthetic crystalline structure and listed in a crystallography database, it is identified as a "known synthetic structure.” In the preferred non-limiting embodiments, the present disclosure provides crystalline 15 fertilizer compositions that have only limited or no solubility in water and / or are soluble in water and a mixture thereof. In the preferred non-limiting embodiments, the present disclosure provides crystalline fertilizer compositions with solubilities that are pH dependent by demonstrating various solubilities in pH from 3 to 8 and a mixture thereof. 20 In the preferred non-limiting embodiments, the present disclosure provides crystalline fertilizer compositions that provide for solid and liquid forms of fertilizers. In the preferred non-limiting embodiments, the present disclosure provides crystalline fertilizer compositions suitable for coating a second fertilizer and / or for coating plant seeds. As a coating agent other components can be added to it, such as sulfur, wax, polymers, and other 25 agents to improve coating properties. In the preferred non-limiting embodiments, the present disclosure provides crystalline fertilizer compositions comprising multi-nutrient simultaneous delivery system, wherein nitrogen in the form of ammonium, urea and ammine and mixtures thereof and other 72

[0073] macronutrients and / or micronutrients (metal salts) and mixtures thereof are integrated into a common crystalline coordination framework for simultaneous delivery. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which crystalline coordination nitrogen-metal polymer and complex 5 Fertilizer, comprising a nitrogen fertilizer covalently bonded to metal salts in the form that encompass a) urea-metal and b) ammine-metal, in which these nitrogen-metal structures provide ligands to a central metal, and in which it encompasses a nitrogen-metal structure in the form of c) ammonium-metal, participating in a nitrogen-metal structure as a counterion. In the preferred non-limiting embodiments, the present disclosure comprises crystalline 10 fertilizer compositions in which crystalline coordination non-nitrogen-metal polymer and complex fertilizer, comprising a structure devoid of nitrogen fertilizer in the form of urea, ammine and ammonium or any other form of nitrogen fertilizer. It is comprising a crystalline coordination metal salt polymer and complex fertilizer with no structural attachment to any form of nitrogen fertilizer. The features and distinctions of this fertilizer encompasses the 15 features and distinctions of crystalline coordination polymer and complex fertilizer. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which crystalline nitrogen-ionic compound fertilizer, comprising a urea-ionic compound and ammonium-ionic compound but can contain any nitrogen fertilizer that is part of an ionic compound fertilizer. The features and distinctions of this fertilizer 20 encompass the features and distinctions of crystalline ionic compound fertilizer. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which crystalline non-nitrogen-ionic compound fertilizer, comprising an ionic compound that is devoid of a nitrogen source, such as urea, ammonium, or any other fertilizer nitrogen. The features and distinctions of this fertilizer encompass the features and 25 distinctions of crystalline ionic compound fertilizer. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which coordination polymers and complexes forming a regular, repeating arrangement of atoms or molecules, called a lattice. Every ion, molecule, or atom is 73

[0074] organized in a coordinated dimensional way and is held together by a highly ordered, cohesive force. Symmetrical chemical bonds affect the overall shape and properties of the material. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which coordination polymers and complexes form nitrogen-metal 5 fertilizer compositions and mixtures thereof. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which coordination polymers and complexes form non-nitrogen-metal fertilizer compositions and mixtures thereof. In the preferred non-limiting embodiments, the present disclosure comprises crystalline 10 fertilizer compositions in which coordination polymers and complexes form nitrogen-metal and non-nitrogen-metal fertilizer compositions and mixtures thereof. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which form nitrogen-ionic compound fertilizer and non-nitrogen-ionic compound fertilizer and mixtures thereof. 15 In the preferred non-limiting embodiments, the present disclosure comprise crystalline fertilizer compositions in which potassium, rarely forming traditional coordination polymers and / or complexes, in coordination chemistry it’s considered difficult to make a coordinated polymers and / or complexes with potassium (K) because potassium ions are large and have a low charge (+1), making them weak Lewis Acids with a low tendency to form stable coordinate 20 covalent bonds with ligands; essentially, they don't readily attract electron pairs from other molecules to form polymers and / or complexes. In principle, all two valent transition metals (Zn, Fe, Cu, Mn) should be able to assist in the participation of K into crystalline coordination polymers and / or complexes. Examples were provided in embodiments using the transition metal zinc (Zn), crystalline coordination compositions (KZn(SO4)Cl), (KZnCl3(urea)), 25 (Zn3K2(SO4)3(OH)2(H2O)2), and (Zn2K(SO4)2(OH)(H2O)) demonstrated that Zn incorporated K into polymer and / or complexes. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which transition metals play a crucial role in forming crystalline coordination compositions with other metals due to a unique combination of: 74

[0075] Electronic and structural properties: 1. Variable oxidation states: o Transition metals can exhibit multiple oxidation states (charges). This allows them to interact and bond with a variety of other metal ions and ligands in different ways, leading to 5 the formation of complex structures with diverse stoichiometries. o This variability is due to the relatively small energy difference between their (n-1)d and ns orbitals, allowing for the loss of different numbers of electrons. 2. Partially filled d orbitals: o The presence of partially filled d orbitals is fundamental to the formation and properties of 10 coordination complexes. o These d orbitals can accept electron pairs from ligands (Lewis bases), forming coordinate covalent bonds. o The specific arrangement and energy levels of these d orbitals influence the geometry, stability, color, and magnetic properties of the resulting complexes. 15 3. Ability to form coordinate bonds: o Transition metal ions act as Lewis acids, readily accepting electron pairs donated by ligands (which are Lewis bases). o These ligands can be other metal ions (though less common in simple complexes), or more frequently, anions or neutral molecules with lone pairs of electrons (e.g., water, ammonia, 20 halides, organic molecules). o This ability to form coordinate bonds is the very definition of a coordination complex. 4. Variety of coordination numbers and geometries: o Transition metals can accommodate a wide range of coordination numbers (the number of ligands directly bonded to the central metal ion), typically from 2 to 12, although 4 and 6 25 are most common. o This leads to a rich diversity of geometric arrangements of the ligands around the metal center, such as linear, tetrahedral, square planar, trigonal bipyramidal, and octahedral. o The specific geometry adopted depends on factors like the metal ion's size and electronic configuration, and the size and electronic properties of the ligands. 75

[0076] 5. Formation of stable complexes: o Transition metal complexes often exhibit significant stability due to factors like: o Chelate effect: When polydentate ligands (ligands that bind to the metal ion through more than one donor atom) are involved, they form ring-like structures (chelates) that enhance 5 the stability of the complex. o Crystal Field Stabilization Energy (CFSE): In complexes with certain d-electron configurations and geometries, the splitting of the d orbitals in the ligand field leads to a net stabilization energy, making the complex more stable and thus more likely to form crystalline solids. o While most coordination complexes feature a transition metal as the central atom and non- 10 metal ligands, it's possible for a transition metal ion to act as a ligand towards another metal ion, forming polymetallic complexes. In such cases, the properties mentioned above are still crucial. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which transition metals play a crucial role in forming crystalline 15 coordination compositions comprise zinc (Zn) as a dominant transition metal for fertilizer as many soils are deficient in this metal. While other transition metals like iron (Fe), manganese (Mn), copper (Cu), molybdenum (Mo), and nickel (Ni) are also essential micronutrients and used in fertilizers when deficiencies occur, zinc stands out due to the frequency of its deficiency and its widespread application as a micronutrient fertilizer. As such, it is a common metal added to 20 fertilizers. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which coordination polymers and / or complexes comprise oxygen (O), nitrogen (N), and sulfate (S) as the most common atoms (ligands), phosphate (PO4) and chloride (Cl) are also atoms (ligands) demonstrated in the embodiments. Well-studied N- and O-donor 25 ligand systems with transition metals support diverse biological activities, such as catalysis, bioactivity, and material science, including urease inhibition. This embodiment is reflected in coordination polymer identified as [(H3N)2Zn(SO4)2]2-×2(H4N+) and coordination complex identified as Cu(SO4)(NH3)4(H2O). These coordination compositions, in particular, are crystalline coordination ammine-metal (nitrogen-metal) fertilizers. In coordination chemistry, N- and Cl- 76

[0077] donor and O- and Cl-donor ligand combinations exhibit distinct properties due to donor atom electronegativity, bonding strength, and metal-ligand interactions. This embodiment is reflected in coordination compositions identified as Zn(NH₃)₂Cl₂, KZn(SO4)Cl and KZnCl3(urea). In the preferred non-limiting embodiments, the present disclosure comprises crystalline 5 fertilizer compositions and mixtures thereof, mixing at least one metal salt and urea or another nitrogen source that binds to the metal salt and in a solvent comprising water to form a reaction mixture, wherein the molar ratio of urea to metal salt is in a ratio from 1 to 25 to 25 to 1. In the preferred non-limiting embodiments, the present disclosure comprises crystalline 10 fertilizer compositions and mixtures thereof and includes a mixture of nutrients, fillers, carriers, binders, humate (humic acid), urease inhibitors, nitrification inhibitors, chemical additives, herbicides, pesticides, and fungicides that are most suitable for best practices in soil, crop, and environmental agricultural applications. In the preferred non-limiting embodiments, the present disclosure comprises crystalline 15 fertilizer compositions and mixtures thereof for coating plant and / or turf and / or grain seed to promote germination and are most suitable for best practices in soil, crop, and environmental agricultural applications. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which fertilizer formulations allow for flexible concentrations of urea 20 and metal salts and mixtures thereof and are most suitable for best practices in soil, crops, and environmental agricultural applications. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions with an approach to transform urea into a form of nitrogen that is protected and stable for more efficient plant uptake, averting urea fixation, nitrogen run-off 25 and leaching and ammonia volatility and other related emissions. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer composition in which macronutrients and micronutrients are protected and stable for efficient plant uptake and minimal loss in soils. 77

[0078] In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in a biologically available form that can be efficiently used for plant uptake. In the preferred non-limiting embodiments, the present disclosure comprises crystalline 5 fertilizer compositions that are non-toxic to soils and plants, as all compositions contain safe, biodegradable, and essential nutrients for efficient plant uptake. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which a method of producing fertilizer comprises mixing at least one metal salt with a urea in a solvent to form a reaction mixture and providing conditions for 10 reaction between the metal salt and the urea to form a fertilizer. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which the conditions for reaction may include adjusting the temperature of the reaction mixture, adding more or less solvent, adding catalysts to the reaction mixture, adding further processing agents, adding pH modifiers, pressurizing the 15 reaction vessel, adding further reactants, or providing other reaction conditions. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which the reaction mixture comprises the metal salt and the urea comprising water to form a reaction mixture. In the preferred non-limiting embodiments, the present disclosure comprises crystalline 20 fertilizer compositions in which some embodiments, the molar ratio of water to metal salt is between a ratio from 1 to 12 to 12 to 1. In other embodiments, the molar ratio is between a ratio from 1 to 8 to 8 to 1 or between 1 to 1 to 1 to 7. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which the process may comprise heating the reaction mixture to a 25 temperature high enough to form a crystalline coordination nitrogen-metal complex fertilizer solution from a reaction between the metal salt and the urea. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which some embodiments, the heating will cause the solid reactants to dissolve into the solvent. The reaction may occur in either the solid forms of the reactants or the dissolved forms or both. 78

[0079] In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which the reaction mixture may be driven to complete conversion based upon the stoichiometric ratio of components or to partial conversion. In the preferred non-limiting embodiments, the present disclosure comprises crystalline 5 fertilizer compositions in which some embodiments, the reactants may also be fertilizers, minerals, or other components beneficial to the growth of plants. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which the process may comprise post processing of the reaction mixture to complete conversion or to produce the desired form of the fertilizer. The post 10 processing steps may include, but are not limited to, drying the crystalline fertilizer composition solution to form a crystalline fertilizer composition, cooling the crystalline fertilizer composition solution to form a crystalline fertilizer composition, and solubilizing the crystalline fertilizer composition solution to form a crystalline fertilizer composition, for example. In the preferred non-limiting embodiments, the present disclosure comprises crystalline 15 fertilizer compositions in which the metal salt may be any metal salt that can react with the urea. The metal salt may comprise at least one of zinc, copper, manganese, boron, calcium, potassium, sodium, iron, magnesium, molybdenum, boron, cobalt, selenium, nickel, silicon, and chromium, for example. In the preferred non-limiting embodiments, the present disclosure comprises crystalline 20 fertilizer compositions in which some embodiments, the metal salt is at least one of a sulfate, nitrate, chloride, oxide, hydroxide, carbonate, phosphate, and acetate, for example. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which the solvent may be any solvent. Preferably, the solvent is a liquid that does not provide detrimental properties to the resultant fertilizer. In embodiments, 25 the solvent comprises water. The solvent may comprise additional components that may or may not be reactive with the primary components, the metal salt and urea. The additional components may be fertilizers, nutrients, acids, carboxylic acids, catalyst, and processing components, for example. 79

[0080] In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which the carboxylic acid is selected from the group consisting of citric acid, acetic acid, oxalic acid, malic acid, lactic acid, tartaric acid, and combinations thereof. In the preferred non-limiting embodiments, the present disclosure comprises crystalline 5 fertilizer compositions in which the reaction mixture may be heated to a reaction temperature to initiate or increase the rate of reaction, to solubilize the reactants, or for other purposes. For example, the reaction mixture may be heated to a reaction temperature of greater than 70°C or to a reaction temperature of approximately 100°C. The reaction mixture may be kept below a temperature that results in the formation of byproducts including adverse byproducts. In some 10 embodiments, adverse byproducts such as biuret may be produced at a reaction temperature of approximately 135°C or above. In some embodiments, the heating of the reaction mixture may be to a temperature greater than 50°C and less than 135°C. The amount of undesired byproducts such as biuret may be controlled by controlling the processing conditions. The processing conditions, in some embodiments, may be controlled such that the resultant 15 fertilizer does not comprise a significant amount of biuret. For example, the fertilizer may comprise biuret in a concentration less than 1 wt. percent. In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which some embodiments, the method comprises cooling the reaction mixture after the urea has solubilized. 20 In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which after the reaction, the crystalline fertilizer composition solution may comprise at least one of at least one ammonium-metal polymer and / or complex fertilizer, at least one ammine-metal polymer and / or complex fertilizer; and at least one urea-metal polymer and / or complex fertilizer. The at least one of at least one ammonium-metal polymer 25 and / or complex fertilizer, at least one ammine-metal polymer and / or complex fertilizer; and at least one urea-metal polymer and / or complex fertilizer may be in various composition ratios and various compositions based upon the reactants, the reaction time, the reaction temperature, the solvent, the additional components in the solvent, the reaction pressure, or other reaction conditions. 80

[0081] In the preferred non-limiting embodiments, the present disclosure comprises crystalline fertilizer compositions in which embodiments of a method may produce a metal tetrakis(urea) sulfate, such as a calcium tetrakis(urea) sulfate. Such a method may comprise mixing a urea, a metal hydroxide, and a metal sulfate in a solvent comprising water to form a reaction mixture, 5 wherein the molar ratio of urea to metal salt is between a ratio from 1 to 8 to 8 to 1. The reaction mixture may be heated to a temperature greater than 50°C to form a nitrogen-metal polymer fertilizer solution. In one example, the metal hydroxide is calcium hydroxide, and the metal sulfate is copper sulfate. In this example, the resultant nitrogen-metal polymer fertilizer solution comprises a 10 calcium tetrakis(urea) sulfate. The calcium tetrakis(urea) sulfate may be a crystalline structure of (CH4N2O)4(Ca)(SO4). In another example, the metal hydroxide is calcium hydroxide, the metal sulfate is iron sulfate, and the resultant nitrogen-metal polymer fertilizer solution comprises iron urea sulfate including Fe(urea)6(SO4)(H2O). The nitrogen-metal polymer fertilizer solution may further 15 comprise iron urea sulfate including (NH4)2Fe(SO4)2(H2O). In the preferred non-limiting embodiments, the present disclosure of the fertilizer comprise at least one ammonium-metal polymer and / or complex fertilizer; at least one ammine-metal polymer and / or complex fertilizer; and at least one urea-metal polymer and / or complex fertilizer. 20 In the preferred non-limiting embodiments, the present disclosure provides the resultant crystalline fertilizer compositions from any of the above methods may comprise a crystalline coordination nitrogen-metal polymer and / or complex fertilizer and a crystalline coordination non-nitrogen-metal polymer and / or complex fertilizer, or mixtures thereof. The crystalline coordination nitrogen-metal and non-nitrogen-metal polymer and / or complex fertilizers, and 25 mixtures thereof, may be one- or two- or three-dimensional coordination networks. The crystalline coordination nitrogen-metal and non-nitrogen-metal polymer and / or complex fertilizers are one- or two- or three-dimensional coordination networks are anionic or neutral crystalline coordination nitrogen-metal and non-nitrogen-metal polymer and / or complex fertilizers are one- or two- or three-dimensional coordination networks. 81

[0082] In the preferred non-limiting embodiments, the present disclosure some embodiments, the fertilizer will not comprise a significant amount of isolated metal or metal cations or anions. In most cases, the reaction will be controlled or allowed to proceed sufficiently to react all the isolated metal, metal cations, or metal anions with the urea or another source of nitrogen or 5 other reactant such as, but not limited to, another cation or anion. At least a portion of metal atoms may be coordinated with a plurality of oxygen atoms and the nitrogen of the ammine, ammonium, or urea is bound to one of the oxygen atoms, for example. These metal complexes may further be coordinated with water molecules. In the preferred non-limiting embodiments, the present disclosure that the process may 10 comprise adding a nitrogen source to bind, coordinate, or establish a framework with the metal of the metal salt to form the fertilizer or blend of fertilizers. The nitrogen source may be, but is not limited to, ammonium, ammine, and urea. Preferably, and in some embodiments, the nitrogen sources may have strong hydrogen bonding capability and are or form anions or cations bound by hydrogen bonding. The nitrogen sources or portions of the nitrogen sources 15 may be bound by ionic bonding to the metals from the metal salts. Fertilizers made from this process may be further processed as known in the art to produce solid or liquid fertilizers to be applied to residential or commercial land, hydroponic systems, aquatic systems, or other agriculture areas that would benefit from fertilization. The fertilizer may be used as a coating agent on to a second fertilizer or coated with another 20 component, such as sulfur, wax, polymer, or other material on to a second fertilizer, for example. The coating may be substantially insoluble in water. In the preferred non-limiting embodiments, the present disclosure embodiments, the resultant crystalline fertilizer composition solution may comprise at least one of at least one ammonium- metal polymer and / or complex fertilizer, at least one ammine-metal polymer and / or complex 25 fertilizer, at least one urea-metal complex fertilizer. In certain embodiments, the at least one ammonium-metal polymer and / or complex fertilizer is in a concentration of 0 to 95 wt%; the at least one ammine-metal sulfate polymer and / or complex fertilizer is in a concentration of 0 to 50 wt%; the urea is in a concentration of 0 to 80 wt%; at least one urea-metal sulfate polymer and / or complex fertilizer is a tetrakis calcium sulfate urea complex in a concentration of 20 to 82

[0083] 90 wt%; and the metal sulfate is in a concentration of 0 to 70 wt%. The metal of these polymer and / or complex fertilizer may be one or more of calcium, potassium, phosphorus, zinc, manganese, iron, magnesium, and copper, for example. The fertilizer may comprise additional components including but not limited to, at least one of 5 nutrients, fillers, carriers, binders, humate (humic acid), urease inhibitors, nitrification inhibitors, chemical additives, conventional fertilizers, herbicides, pesticides, and fungicides to the fertilizer. The fertilizers have many uses including, but not limited to, the fertilizer being a coating for seed to promote germination. The seed may be any seed including, but not limited to, a plant, turf, or grain seed. 10 EXAMPLES Selected examples are illustrative of advantages that may be obtained compared to alternative methods, and these advantages are accordingly illustrative of preferred non-limiting embodiments and not necessarily indicative of the characteristics of all aspects of the invention. The following methodology was used in the examples below. Granular Urea (Alpha 15 Chemicals), finely ground metal salt(s) (Alpha Chemicals) and tap water were added to a glass beaker at ambient temperature. The mixture was stirred with a glass rod to evenly distribute the beaker’s contents. The glass rod was removed, and a magnetic stir bar was added to the beaker. The beaker was placed on a hot-plate that was pre-heated to a set-point of 255 degrees Celsius. The stir-bar speed was set to 240 RPM’s. As the mixture heated, the Urea cools the 20 mixture as it goes into solution while the metal salt(s) start to form an aquo complex. The simultaneous cooling and heating of the reaction mix controls the reaction and allows for an exchange of ions that would not occur under different conditions as demonstrated by the new compounds formed by this methodology. The reaction time for the examples listed below is 15 minutes to 1 hour. The reaction is finished when the temperature in the beaker reaches 100 25 degrees Celsius. Examples run at mol ratios of 1:1 (urea:metal salts) begin to solidify / crystallize once the mix reaches 100 degrees Celsius. Examples run at mol ratios 1:2 (urea:metal salts) and above are liquid at 100 degrees Celsius and solidify / crystallize upon cooling. After crystallization, samples can be trim-dried, or air cooled to improve handling. When drying, the product temperature was kept below 100 degrees Celsius. 83

[0084] Example no.1, Sample No. Ca_AM_AP328011B_1to1 Ingredient Mol Wt. Mols Addition 5 Calcium Sulfate Dihydrate 172.164 1 172.164 Urea 60.056 1 60.056 Water, added, 6 mols 108.090 1 108.090 ------------------------------------------------------------------------------------------------------------------- Total Weight 340.310 10 The crystallization reaction contained a total of 8 waters, 2 bound waters and 6 added waters required for the formation of the Aquo complex (6 waters) plus 2 for urea solubility. Lab Scale Weights Ingredient Grams 15 Calcium Sulfate Dihydrate 50.59 Water, added 31.76 Urea 17.65 --------------------------------------------------------- Total 100.00 20 Ingredient % Calcium Sulfate Dihydrate 50.59 Water, added 31.76 Urea 17.65 --------------------------------------------------------- 25 Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Two phases were identified: 84

[0085] Ca(SO4)(H2O)2(PDF Card – 04-015-8262, Mineral name Gypsum) (CH4N2O)4Ca(SO4) (CCDC 1278455, Refcode URCASU) The ratio of components (weight %) refined to 56.9 to 43.1%, respectively. 5 Example no.2, Sample no. CRU_AM_SP320201A_1to4 Ingredient Mol Wt. Mols Addition Calcium Sulfate Dihydrate 172.164 1 172.164 Urea 60.056 4 240.224 Water, added, 6 mols 108.090 1 108.090 10 ------------------------------------------------------------------------------------------------------------------- Total Weight 502.478 The crystallization reaction contained a total of 8 waters, 2 bound waters and 6 added waters required for the formation of the Aquo complex (6 waters) plus 2 for Urea solubility. Lab Scale Weights 15 Ingredient Grams Calcium Sulfate Dihydrate 33.08 Water, added 20.77 Urea 46.15 --------------------------------------------------------- 20 Total 100.00 Ingredient % Calcium Sulfate Dihydrate 33.08 Water, added 20.77 Urea 46.15 25 --------------------------------------------------------- Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were 85

[0086] identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Three phases were identified: (CH4N2O)4Ca(SO4) (CCDC 1278455, Refcode URCASU) Ca2(SO4)2(H2O) (PDF Card - 04-011-1765, Mineral name Bassanite) 5 Urea (PDF Card - 04-009-3709) The ratio of components (weight %) refined to 85.0 to 5.9 to 9.1%, respectively. Example no.3, Sample no. Cu_AM_SP422001A Ingredient Mol Wt. Mols Addition 10 Copper Sulfate Pentahydrate 249.677 4 998.708 Urea 60.056 1 60.056 Water 18.015 3 54.045 ------------------------------------------------------------------------------------------------------------ Total 1,274.994 15 The crystallization reaction contained a total of 32 waters, 5 bound waters and 3 added waters per mol of Copper Sulfate Pentahydrate required for the formation of the Aquo complex (6 waters) plus 2 for Urea solubility, multiplied by 4 for 4 mols of Copper Sulfate Pentahydrate total. Lab Scale Weights 20 Ingredient Grams Copper Sulfate Pentahydrate 78.33 Urea 4.71 Water 16.96 ----------------------------------------------------------- 25 Total 100.00 Ingredient % Copper Sulfate Pentahydrate 78.33 Urea 4.71 Water 16.96 86

[0087] ----------------------------------------------------------- Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were 5 identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Three phases were identified: (NH4)2Cu(SO4)2(H2O)2(PDF Card – 00-025-1486) Cu(SO4)2(H2O)2-Cu(urea)2(H2O)2(Unpublished Single Crystal Data) Cu3(SO4)(OH)2(H2O)4(Unpublished Single Crystal Data) 10 The ratio of components (weight %) refined to 24.3 to 33.0 to 42.5%, respectively. Example no.4, Sample no. Cu_AM_SP326011A Ingredient Mol Wt. Mols Addition Copper Sulfate Pentahydrate 249.677 1 249.677 15 Urea 60.056 1 60.056 Water 18.015 3 54.045 ------------------------------------------------------------------------------------------------------------ Total 363.778 The crystallization reaction contained a total of 8 waters, 5 bound waters and 3 added waters 20 required for the formation of the Aquo complex (6 waters) plus 2 for Urea solubility. Lab Scale Weights Ingredient Grams Copper Sulfate Pentahydrate 68.63 Urea 16.51 25 Water 14.86 ----------------------------------------------------------- Total 100.00 Ingredient % Copper Sulfate Pentahydrate 68.63 87

[0088] Urea 16.51 Water 14.86 ----------------------------------------------------------- Total 100.00 5 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Three phases were identified: Cu3(SO4)(OH)4(PDF Card - 04-012-1884, Mineral name Antlerite) 10 (NH4)2SO4(PDF Card - 04-005-8533, Mineral name Mascagnite) Cu(SO4)(NH3)4(H2O) (PDF Card - 04-011-0483) The ratio of components (weight %) refined to 49.0 to 43.2 to 7.8%, respectively. Example no.5, Sample no. Cu_AM_SP422001A 1 to 4 15 Ingredient Mol Wt. Mols Addition Copper Sulfate Pentahydrate 249.677 1 249.677 Urea 60.056 4 240.224 Water 18.015 2 36.030 ------------------------------------------------------------------------------------------------------------ 20 Total 543.946 The crystallization reaction contained a total of 8 waters, 5 bound waters and 3 added waters required for the formation of the Aquo complex (6 waters) plus 2 for Urea solubility. Lab Scale Weights Ingredient Grams 25 Copper Sulfate Pentahydrate 45.90 Urea 44.16 Water 9.94 ----------------------------------------------------------- Total 100.00 88

[0089] Ingredient % Copper Sulfate Pentahydrate 45.90 Urea 44.16 Water 9.94 5 ----------------------------------------------------------- Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD 10 databases. Five phases were identified: Urea (PDF Card - 04-009-3709) (NH4)2SO4(PDF Card - 04-005-8533, Mineral name Mascagnite) Cu(SO4)(NH3)4(H2O) (PDF Card - 04-011-0483) Cu3(SO4)(OH)4(PDF Card - 01-082-2873) 15 (NH4)2Cu(SO4)2(H2O)2(PDF Card – 00-025-1486) The ratio of components (weight %) refined to 51.4 to 19.1 to 9.8 to 17.1 to 2.6%, respectively. Example no.6, Sample no. Cu_AM_SP324111B_1to1_pHadjusted Ingredient Mol Wt. Mols Addition 20 Copper Sulfate Pentahydrate 249.677 1 249.677 Urea 60.056 1 60.056 Calcium Hydroxide 76.108 0.656 49.930 Water 18.015 2 36.030 ------------------------------------------------------------------------------------------------------------ 25 Total 395.693 The crystallization reaction contained a total of 8 waters, 5 bound waters and 3 added water required for the formation of the Aquo complex (6 waters) plus 2 for Urea solubility. Note – An additional water was required on this run due to the low solubility of Ca(OH)2per the example listed below. 89

[0090] Lab Scale Weights Ingredient Grams Copper Sulfate Pentahydrate 72.21 Urea 17.37 5 Calcium Hydroxide 14.44 Water 18.25 Additional water (Ca(OH2) solubility) 12.17 ------------------------------------------------------------------ Total 134.44 10 Ingredient % Copper Sulfate Pentahydrate 53.71 Urea 12.92 Calcium Hydroxide 10.74 Water 22.63 15 ------------------------------------------------------------------ Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD 20 databases. Four phases were identified: Cu3(SO4)(OH)4(PDF Card - 04-012-1884, Mineral name Antlerite) Ca(SO4)(H2O)2(PDF Card - 04-015-8262, Mineral name Gypsum) (CH4N2O)4Ca(SO4) (CCDC 1278455, Refcode URCASU) Urea (PDF Card - 04-009-3709) 25 The ratio of components (weight %) refined to 41.6 to 28.9 to 27.0 to 2.5%, respectively. Example no.7, Sample no. Fe_AM_SP323111B_1to1 Ingredient Mol Wt. Mols Addition Iron Sulfate Heptahydrate 278.006 1 278.006 90

[0091] Urea 60.056 1 60.056 Water 18.015 1 18.015 ------------------------------------------------------------------------------------------------------------ Total 356.077 5 The crystallization reaction contained a total of 8 waters, 7 bound waters and 1 added water required for the formation of the Aquo complex (6 waters) plus 2 for Urea solubility. Lab Scale Weights Ingredient Grams Iron Sulfate Heptahydrate 78.07 10 Urea 16.87 Water 5.06 ----------------------------------------------------------- Total 100.00 Ingredient % 15 Iron Sulfate Heptahydrate 78.07 Urea 16.87 Water 5.06 ----------------------------------------------------------- Total 100.00 20 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Four phases were identified: Fe(SO4)(urea)(OH2)2(Unpublished Single Crystal Data) 25 (NH4)2Fe(SO4)2(H2O)6(PDF Card - 04-025-0291, Mineral Name Mohrite) Fe(SO4)2(H3O)(H2O)3(PDF Card - 04-013-2664, Mineral Name Rhomboclase) Fe3(O)(OH)(SO4)3(H2O)4(ICSD_CollCode136272) The ratio of components (weight %) refined to 71.3 to 23.3 to 2.6 to 2.8%, respectively. 91

[0092] Example no.8, Sample no. Fe_AM_SP323111A_1to4 Ingredient Mol Wt. Mols Addition Iron Sulfate Heptahydrate 278.006 1 278.006 Urea 60.056 4 240.224 5 Water 18.015 1 18.015 ------------------------------------------------------------------------------------------------------------ Total 536.245 The crystallization reaction contained a total of 8 waters, 7 bound waters and 1 added water required for the formation of the Aquo complex (6 waters) plus 2 for Urea solubility. 10 Lab Scale Weights Ingredient Grams Iron Sulfate Heptahydrate 51.84 Urea 44.80 Water 3.36 15 ----------------------------------------------------------- Total 100.00 Ingredient % Iron Sulfate Heptahydrate 51.84 Urea 44.80 20 Water 3.36 ----------------------------------------------------------- Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were 25 identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Six phases were identified: Fe(urea)6(SO4)(H2O) (Co analogue, PDF Card 00-042-0674, CCD C1278464, CSD URCOSM) (NH4)2SO4(PDF Card - 04-005-8533, Mineral Name Mascagnite) Urea (PDF Card - 04-009-3709) 92

[0093] (NH4)2Fe(SO4)2(H2O)6(PDF Card - 04-025-0291, Mineral Name Mohrite) Fe(SO4)2(H3O)(H2O)3(PDF Card - 04-013-2664, Mineral Name Rhomboclase) Fe3(O)(OH)(SO4)3(H2O)4(ICSD_CollCode136272) The ratio of components (weight %) refined to 36.8 to 5.2 to 32.1 to 8.8 to 2.2 to 14.9%, 5 respectively. Example no.9, Sample no. Fe_AM_SP324111A_pH-adjusted_1to1 Ingredient Mol Wt. Mols Addition Iron Sulfate Heptahydrate 278.006 1 278.006 10 Urea 60.056 1 60.056 Calcium Hydroxide 76.108 0.73 55.560 Water 18.015 1 18.015 ------------------------------------------------------------------------------------------------------------ Total 411.636 15 The crystallization reaction contained a total of 8 waters, 7 bound waters and 1 added water required for the formation of the Aquo complex (6 waters) plus 2 for Urea solubility. Note – Additional water was required on this run due to the low solubility of Ca(OH)2per the example listed below. Lab Scale Weights 20 Ingredient Grams Iron Sulfate Heptahydrate 78.08 Urea 16.87 Calcium Hydroxide 15.61 Water 5.06 25 Additional Water (dissolve Ca(OH)2) 20.00 ------------------------------------------------------------------ Total 135.62 Ingredient % Iron Sulfate Heptahydrate 57.57 93

[0094] Urea 12.44 Calcium Hydroxide 11.51 Water 3.37 Additional Water (dissolve Ca(OH)2) 14.75 5 ----------------------------------------------------------------- Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD 10 databases. Four phases were identified: Fe(urea)6(SO4)(H2O) (Co analogue, PDF Card 00-042-0674, CCD C1278464, CSD URCOSM) (NH4)2Fe(SO4)2(H2O)6(PDF Card - 04-025-0291, Mineral Name Mohrite) FeO(OH) (PDF Card 01-084-8280, Mineral Name Goethite) Ca(SO4)(H2O)2(PDF Card 04-015-8262, Mineral Name Gypsum) 15 The ratio of components (weight %) refined to 5.0 to 7.2 to 21.7 to 66.1%, respectively. Example no.10, Sample no. MgClN_AM_SP426080A Ingredient Mol Wt. Mols Addition Magnesium Chloride Hexahydrate 179.451 1 203.301 20 Urea 60.056 1 60.056 Water 18.015 2 36.030 ------------------------------------------------------------------------------------------------------------ Total 299.387 The crystallization reaction contained a total of 8 waters, 6 bound water and 2 added waters.6 25 waters for the Metal Aquo Solution complex plus 2 extra for Urea solubility. Lab Scale Weights Ingredient Grams Magnesium Chloride Hexahydrate 67.91 Urea 20.06 94

[0095] Water 12.03 -------------------------------------------------------------------- Total 100.00 Ingredient % 5 Magnesium Chloride Hexahydrate 67.91 Urea 20.06 Water 12.03 -------------------------------------------------------------------- Total 100.00 10 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Three phases were identified: MgCl2(NH4)2Cl(H2O)6(ICSD 183507)) 15 NH4Cl (ICDD 04-016-0227, Mineral name Salammoniac) MgCl2(H2O)2(urea)4(CSD Refcode NUTVOQ) The ratio of components (weight %) refined to 51.6 to 10.9 to 37.5 %, respectively. Example no.11, Sample no. Mg-AM-SP320101A 20 Ingredient Mol Wt. Mols Addition Magnesium Sulfate Heptahydrate 246.466 1 246.466 Urea 60.056 1 60.056 Water 18.015 1 18.015 ------------------------------------------------------------------------------------------------------------------- 25 Total 324.537 The crystallization reaction contained a total of 8 waters, 7 bound waters and 1 added water required for the formation of the Aquo complex (6 waters) plus 2 for urea solubility. Lab Scale Weights Ingredient Grams 95

[0096] Magnesium Sulfate Heptahydrate 78.00 Urea 19.00 Water 5.70 ----------------------------------------------------------------- 5 Total 102.70 Ingredient % Magnesium Sulfate Heptahydrate 75.94 Urea 18.51 Water 5.55 10 ----------------------------------------------------------------- Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD 15 databases. Two phases were identified: (NH4)2Mg(SO4)2(H2O)6(PDF Card - 04-009-3829, Mineral name Boussingaultite) (NH4)2Mg3(SO4)3(OH)2(H2O)2(PDF Card - 04-025-4931) The ratio of components (weight %) refined to 22.2 to 78.8%, respectively. 20 Example no.12, Sample no. Mg-AM-SP420390B 1 to 4 Ingredient Mol Wt. Mols Addition Magnesium Sulfate Heptahydrate 246.466 1 246.466 Urea 60.056 4 240.224 Water 18.015 1 18.015 25 ------------------------------------------------------------------------------------------------------------------- Total 504.705 The crystallization reaction contained a total of 8 waters, 7 bound waters and 1 added water required for the formation of the Aquo complex (6 waters) plus 2 for urea solubility. Lab Scale Weights 96

[0097] Ingredient Grams Magnesium Sulfate Heptahydrate 48.83 Urea 47.60 Water 3.57 5 ----------------------------------------------------------------- Total 100.00 Ingredient % Magnesium Sulfate Heptahydrate 48.83 Urea 47.60 10 Water 3.57 ----------------------------------------------------------------- Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were 15 identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Four phases were identified: Urea (PDF Card - 04-009-3709) (NH4)2Mg(SO4)2(H2O)6(PDF Card 00-035-0771, Mineral name Boussingaulite) Mg(urea)6(SO4)(H2O)0.5(CSD entry code SAVQAH) 20 Mg(urea)4(H2O)(SO4) (Unpublished Single Crystal Data) The ratio of components (weight %) refined to 21.0 to 14.9 to 15.3 to 48.8%, respectively. Example no.13, Sample No. Manganese_AM_SP326101B 1:1 Ingredient Mol Wt. Mols Addition 25 Manganese Sulfate Monohydrate 169.009 1 169.009 Urea 60.056 1 60.056 Water 18.015 7 126.105 ------------------------------------------------------------------------------------------------------------------- Total 355.170 97

[0098] The crystallization reaction contained a total of 8 waters, 1 bound waters and 7 added waters required for the formation of the Aquo complex (6 waters) plus 2 for Urea solubility. Lab Scale Weights Ingredient Grams 5 Manganese Sulfate Monohydrate 47.59 Urea 16.91 Water 35.50 ------------------------------------------------------------------ Total 100.00 10 Ingredient % Manganese Sulfate Monohydrate 47.59 Urea 16.91 Water 35.50 ------------------------------------------------------------------- 15 Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Three phases were identified: 20 (NH4)2Mn2(SO4)3(PDF Card - 04-011-9560) (NH4)2Mn3(SO4)3(OH)2(H2O)2) (Unpublished Single Crystal Data) Mn2(SO4)2(CH4N2O)6(Unpublished Single Crystal Data) The ratio of components (weight %) refined to 46.7 to 19.9 to 33.5%, respectively. 25 Example no.14, Sample No. Mn_AM_SP326021A_1to4 Ingredient Mol Wt. Mols Addition Manganese Sulfate Monohydrate 169.009 1 169.009 Urea 60.056 4 240.224 Water 18.015 7 126.105 98

[0099] ------------------------------------------------------------------------------------------------------------------ Total 535.338 The crystallization reaction contained a total of 8 waters, 1 bound waters and 7 added waters required for the formation of the Aquo complex (6 waters) plus 2 for Urea solubility. 5 Lab Scale Weights Ingredient Grams Manganese Sulfate Monohydrate 31.57 Urea 44.87 Water 23.56 10 ------------------------------------------------------------------ Total 100.00 Ingredient % Manganese Sulfate Monohydrate 31.57 Urea 44.87 15 Water 23.56 ------------------------------------------------------------------- Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were 20 identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Five phases were identified: (NH4)2Mn2(SO4)3(PDF Card - 04-011-9560) Mn2(SO4)2(CH4N2O)6(Unpublished Single Crystal Data) Urea (PDF Card - 04-009-3709) 25 MnCO3(PDF-Card 04-001-7250, Mineral name Rhodochrosite) (NH4)2SO4(PDF Card - 04-005-8533, Mineral name Mascagnite) The ratio of components (weight %) refined to 10.2 to 14.4 to 62.5 to 7.8 to 5.1%, respectively. Example no.15, Sample no. KMgSO4_Urea_ AM_SP422090C 99

[0100] Ingredient Mol Wt. Mols Addition Potassium Magnesium Sulfate 414.975 1 414.972 Urea 60.056 8 480.448 Water 18.015 16 288.240 5 ------------------------------------------------------------------------------------------------------------ Total 1183.663 The crystallization reaction contained a total of 16 waters.6 waters for the Metal Aquo Solution complex plus 2 waters for Urea solubility and 8 additional waters for Potassium Magnesium Sulfate solubility. 10 Lab Scale Weights Ingredient Grams Potassium Magnesium Sulfate 35.06 Urea 40.59 Water 24.35 15 ------------------------------------------------------------------- Total 100.00 Ingredient % Potassium Magnesium Sulfate 35.06 Urea 40.59 20 Water 24.35 ------------------------------------------------------------------- Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were 25 identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Five phases were identified: KCl (ICDD 00-041-1471, Mineral name Sylvite) K2Mg2(SO4)3(ICDD 04-008-2-79, Mineral name Langbeinite) (urea)4Mg(SO4)(H2O) (CSD NILSEG) 100

[0101] (urea)6MgCl2-(urea)4(Unpublished Single Crystal Data) Urea(NH4Cl) (CSD URAMCL01) The ratio of components (weight %) refined to 19.1 to 43.9 to 16.2 to 17.5 to 3.4%, respectively. 5 Example no.16, Sample No. K2SO4_ZnSO4_Urea_1_1_1_SP423211A Ingredient Mol Wt. Mols Addition Potassium Sulfate 174.253 1 174.253 Zinc Sulfate Monohydrate 179.451 1 179.451 Urea 60.056 1 60.056 10 Water 18.015 7 126.105 ------------------------------------------------------------------------------------------------------------ Total 539.865 The crystallization reaction contained a total of 8 waters, 1 bound water and 7 added waters.6 waters for the Metal Aquo Solution complex plus 2 extra for Urea solubility. 15 Lab Scale Weights Ingredient Grams Potassium Sulfate 32.28 Zinc Sulfate Monohydrate 33.24 Urea 11.12 20 Water 23.36 ----------------------------------------------------------- Total 100.00 Ingredient % Potassium Sulfate 32.28 25 Zinc Sulfate Monohydrate 33.24 Urea 11.12 Water 23.36 ----------------------------------------------------------- Total 100.00 101

[0102] Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Three phases were identified: 5 K2(SO4) (PDF Card - 00-002-2164, Mineral name Arcanite) Zn2K(SO4)2(OH)(H2O) (Unpublished Single Crystal Data) Zn3K2(SO4)3(OH)2(H2O)2(the isomorphous Co compound) (Unpublished Single Crystal Data) The ratio of components (weight %) refined to 50.3 to 13.5 to 36.2%, respectively. 10 Example no.17, Sample no. KCl_ZnSO4_Urea_1_1_1_SP425211A Ingredient Mol Wt. Mols Addition Potassium Chloride 113.647 1 113.647 Zinc Sulfate Monohydrate 179.451 1 179.451 Urea 60.056 1 60.056 15 Water 18.015 7 126.105 ------------------------------------------------------------------------------------------------------------ Total 479.259 The crystallization reaction contained a total of 8 waters, 1 bound water and 7 added waters.6 waters for the Metal Aquo Solution complex plus 2 extra for Urea solubility. 20 Lab Scale Weights Ingredient Grams Potassium Chloride 23.71 Zinc Sulfate Monohydrate 37.45 Urea 12.53 25 Water 26.31 ----------------------------------------------------------- Total 100.00 Ingredient % Potassium Chloride 23.71 102

[0103] Zinc Sulfate Monohydrate 37.45 Urea 12.53 Water 26.31 ----------------------------------------------------------- 5 Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Five phases were identified: 10 K2(SO4) (PDF Card - 00-002-2164, Mineral name Arcanite) Zn(NH3)2Cl2(PDF Card - 00-024-1435) KZnCl3(urea) (PDF Card - 04-025-1366) KZn(SO4)Cl (PDF Card - 04-025-4218, Mineral name Belousovite) Zn3K2(SO4)3(OH)2(H2O)2(Unpublished Single Crystal Data) 15 The ratio of components (weight %) refined to 38.1 to 28.1 to 63.7 to 22.6 to 4.5%, respectively. Example no.18, MCP_Urea Sample No.SP524010A 1to4 Ingredient Mol Wt. Mols Addition Monocalcium Phosphate 234.042 1 234.042 20 Urea 60.056 4 240.224 Water 18.015 8 144.120 ------------------------------------------------------------------------------------------------------------ Total 618.386 The crystallization reaction contained a total of 8 waters, 0 bound waters and 8 added waters.6 25 waters for the Metal Aquo Solution complex plus 2 extra for Urea solubility. Lab Scale Weights Ingredient Grams Monocalcium Phosphate 37.85 Urea 38.85 103

[0104] Water 23.30 ----------------------------------------------------------- Total 100.00 Ingredient % 5 Monocalcium Phosphate 37.85 Urea 38.85 Water 23.30 ----------------------------------------------------------- Total 100.00 10 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Four phases were identified: (NH4)(H2PO4) (PDF Card - 04-007-7071, Mineral name Biphosphammite) 15 (NH4)2(HPO4) (PDF Card - 04-009-3766, Mineral name Phosphammite) Urea (PDF Card - 04-009-3709) Ca(HPO4) (PDF Card - 04-009-3755, Mineral name Monetite) The ratio of components (weight %) refined to 6.1 to 15.2 to 61.7 to 16.7%, respectively. 20 Example no.19, Sample no. MCP_ZnSO4_Urea_1to1to1_SP520110A Ingredient Mol Wt. Mols Addition Monocalcium Phosphate 234.042 1 234.042 Zinc Sulfate Monohydrate 179.451 1 179.451 Urea 60.056 2 120.110 25 Water 18.015 7 126.105 ------------------------------------------------------------------------------------------------------------ Total 659.708 The crystallization reaction contained a total of 8 waters, 1 bound water and 7 added waters.6 waters for the Zinc Metal Aquo Solution complex plus 2 extra for Urea solubility. 104

[0105] Lab Scale Weights Ingredient Grams Monocalcium Phosphate 35.47 Zinc Sulfate Monohydrate 27.20 5 Urea 18.21 Water 19.12 ----------------------------------------------------------- Total 100.00 Ingredient % 10 Monocalcium Phosphate 35.47 Zinc Sulfate Monohydrate 27.20 Urea 18.21 Water 19.12 ----------------------------------------------------------- 15 Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Four phases were identified: 20 beta-CaSO4– Anhydrite (PDF Card - 01-086-2270) (NH4)2SO4(PDF Card - 04-005-8533, Mineral name Mascagnite) Urea (PDF Card - 04-009-3709) (NH4)Zn(PO4) (PDF Card - 04-016-1290) The ratio of components (weight %) refined to 34.1 to 16.2 to 4.1 to 45.6%, respectively. 25 Example no.20, Sample no. Zinc-AM-SP321101A Ingredient Mol Wt. Mols Addition Zinc Sulfate Monohydrate 179.451 1 179.451 Urea 60.056 1 60.056 105

[0106] Water 18.015 7 126.105 ------------------------------------------------------------------------------------------------------------ Total 365.612 The crystallization reaction contained a total of 8 waters, 1 bound water and 7 added waters.6 5 waters for the Zinc Metal Aquo Solution complex plus 2 extra for Urea solubility. Lab Scale Weights Ingredient Grams Zinc Sulfate Monohydrate 49.10 Urea 16.42 10 Water 34.48 ----------------------------------------------------------- Total 100.00 Ingredient % Zinc Sulfate Monohydrate 49.10 15 Urea 16.42 Water 34.48 ----------------------------------------------------------- Total 100.00 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were 20 analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Two phases were identified: (NH4)2Zn(OH2)6(SO4)2(PDF Card - 04-007-5463, Mineral name Katerinapoulosite) Urea (PDF Card - 04-009-3709) 25 The ratio of the identified components (weight %) refined to 83.8 to 16.3 %, respectively. Example no.21, Sample no. CRU_Zn_AM_SP523240B_1to4 Ingredient Mol Wt. Mols Addition Zinc Sulfate Monohydrate 179.451 1 179.451 106

[0107] Urea 60.056 4 240.224 Water 18.015 7 126.105 ------------------------------------------------------------------------------------------------------------ Total 545.780 5 The crystallization reaction contained a total of 8 waters, 1 bound water and 7 added waters.6 waters for the Metal Aquo Solution complex plus 2 extra for Urea solubility. Lab Scale Weights Ingredient Grams Zinc Sulfate Monohydrate 32.88 10 Urea 44.01 Water 23.11 ----------------------------------------------------------- Total 100.00 Ingredient % 15 Zinc Sulfate Monohydrate 32.88 Urea 44.01 Water 23.11 ----------------------------------------------------------- Total 100.00 20 Using Powder and Single Crystal (if unable to identify structure) XRD Data Analysis, data were analyzed using the HighScore software of Panalytical. The phases present in the sample were identified via Search-Match against the ICDD database and verified against the CCDC and ICSD databases. Two phases were identified: [(H3N)2Zn(SO4)2]2-^2(H4N+) (Unpublished Single Crystal Data) 25 Urea (PDF Card - 04-009-3709) The ratio of components (weight %) refined to 48.8 to 51.2%, respectively. 107

Claims

1. CLAIMS 1. A method of producing a crystalline fertilizer composition, comprising: a. mixing at least one metal salt, a nitrogen source comprising urea, and a solvent comprising water, to form a reaction mixture; and 5 b. heating the reaction mixture to a temperature sufficient to form the crystalline fertilizer composition in a resultant mixture, wherein the crystalline fertilizer composition comprises engineered solid-state structures.

2. The method of claim 1, wherein the engineered solid-state structures comprise a crystalline coordination polymer fertilizer, a crystalline coordination complex fertilizer, and 10 combinations thereof.

3. The method of claim 2, wherein the crystalline coordination polymer fertilizer comprises a crystalline coordination nitrogen-metal polymer fertilizer.

4. The method of claim 3, wherein the crystalline coordination nitrogen-metal polymer fertilizer comprises at least one of an ammonium-metal polymer, a urea-metal polymer, and an 15 ammine-metal polymer.

5. The method of claim 2, wherein the crystalline coordination polymer fertilizer comprises at least one crystalline coordination non-nitrogen-metal polymer fertilizer.

6. The method of claim 2, wherein the crystalline coordination complex fertilizer comprises a crystalline coordination nitrogen-metal complex fertilizer. 20 7. The method of claim 3, wherein the crystalline coordination nitrogen-metal complex fertilizer comprises at least one of an ammonium-metal complex, a urea-metal complex, and an ammine-metal complex.

8. The method of claim 2, wherein the crystalline coordination complex fertilizer comprising a crystalline coordination non-nitrogen-metal complex fertilizer, wherein the 25 crystalline coordination non-nitrogen-metal complex fertilizer comprises unit cells comprising a metal salt.

9. The method of claim 7, wherein the metal salt is a sulfate.

10. The method of claim of 2, wherein the engineered solid-state structures comprise a crystalline ionic compound. 10811. The method of claim 10, wherein the crystalline ionic compound comprises at least one of a crystalline nitrogen-ionic compound fertilizer and crystalline non-nitrogen-ionic compound.

12. The method of claim 11, wherein the crystalline nitrogen-ionic compound fertilizer comprises at least one of ammonium-ionic compound. 5 13. The method of claim 1, comprising mixing the at least one metal salt and the urea to form a blend of reactants prior to adding the blend of reactants to the solvent.

14. The method of claim 1, comprising solubilizing the at least one metal salt and the urea in the solvent to form the reaction mixture.

15. The method of claim 1, comprising cooling the resultant mixture to facilitate formation 10 of the crystalline fertilizer composition.

16. The method of claim 1, comprising drying the crystalline fertilizer composition to form a recovered crystalline fertilizer composition.

17. The method of claim 1, wherein heating the reaction mixture comprises heating the reaction mixture to a temperature greater than 70°C. 15 18. The method of claim 1, wherein heating the reaction mixture comprises heating the reaction mixture to a temperature of approximately 100°C.

19. The method of claim 1, wherein the heating the reaction mixture to a temperature greater than 50°C and less than 135°C.

20. The method of claim 1, wherein a metal of the at least one metal salt comprises at least 20 one of zinc, copper, manganese, boron, calcium, potassium, sodium, iron, magnesium, molybdenum, boron, cobalt, selenium, nickel, silicon, and chromium.

21. The method of claim 20, wherein the metal salt is at least one of a sulfate, nitrate, chloride, oxide, hydroxide, carbonate, phosphate, and acetate.

22. The method of claim 1, wherein the at least one metal salt comprises calcium sulfate. 25 23. The method of claim 22, wherein the at least one metal salt is phosphogypsum and wherein the phosphogypsum comprises the calcium sulfate.

24. The method of claim 1, wherein the solvent comprises at least one carboxylic acid. 10925. The method of claim 24, wherein the carboxylic acid is selected from the group consisting of citric acid, acetic acid, oxalic acid, malic acid, lactic acid, tartaric acid, and combinations thereof.

26. A method of producing a fertilizer, comprising: 5 a. mixing at least one metal hydroxide, at least one metal sulfate, and urea in a solvent comprising water to form a reaction mixture; and b. heating the reaction mixture to greater than 50°C to form a reaction mixture comprising a crystalline fertilizer composition.

27. The method of claim 26, wherein the metal hydroxide is calcium hydroxide, and the 10 metal sulfate is copper sulfate, and wherein the crystalline fertilizer composition comprises crystalline coordination nitrogen-metal polymer fertilizer of the formula (CH4N2O)4Ca(SO4), a urea-calcium polymer fertilizer.

28. The method of claim 26, wherein the metal hydroxide is calcium hydroxide, and the metal sulfate is iron sulfate, and wherein the crystalline fertilizer composition comprises 15 crystalline coordination nitrogen-metal complex fertilizer of the formula Fe(CH4N2O)6(SO4)(H2O), a urea-iron complex fertilizer.

29. The method of claim 26, wherein a metal of the metal sulfate and the metal hydroxide is selected from the group comprising of zinc, copper, manganese, boron, calcium, potassium, sodium, iron, magnesium, molybdenum, cobalt, selenium, nickel, silicon, and chromium. 20 30. A crystalline fertilizer, comprising: a crystalline coordination polymer fertilizer, and a crystalline coordination complex fertilizer, and combinations thereof.

31. The crystalline fertilizer of claim 30, wherein the crystalline coordination polymer fertilizer comprises a crystalline coordination nitrogen-metal polymer fertilizer. 25 32. The crystalline fertilizer of claim 31, wherein the crystalline coordination nitrogen-metal polymer fertilizer comprises at least one of an ammonium-metal polymer, a urea metal polymer, and an ammine-metal polymer.

33. The crystalline fertilizer of claim 31, wherein the crystalline coordination polymer fertilizer comprises at least one crystalline coordination non-nitrogen-metal polymer fertilizer. 11034. The crystalline fertilizer of claim 30, wherein the crystalline coordination complex fertilizer comprises a crystalline coordination nitrogen-metal complex fertilizer.

35. The crystalline fertilizer of claim 31, wherein the crystalline coordination nitrogen-metal complex fertilizer comprises at least one of an ammonium-metal complex, a urea metal 5 complex, and an ammine-metal complex.

36. The crystalline fertilizer of claim 30, wherein the crystalline coordination complex fertilizer comprising a crystalline coordination non-nitrogen-metal complex fertilizer, wherein the crystalline coordination non-nitrogen-metal complex fertilizer comprises unit cells comprising a metal salt. 10 37. The crystalline fertilizer of claim 36, wherein the metal salt is a sulfate. C crystalline ionic compound 38. The crystalline fertilizer of claim of 30, wherein the engineered solid-state structures comprise a crystalline ionic compound.

39. The crystalline fertilizer of claim of claim 38, wherein the crystalline ionic compound15 comprises at least one of a crystalline nitrogen-ionic compound fertilizer and crystalline non- nitrogen-ionic compound.

40. The crystalline fertilizer of claim of claim 39, wherein the crystalline nitrogen-ionic compound fertilizer comprises at least one of ammonium-ion, a urea-ion, and an ammine ion.

41. The crystalline fertilizer composition of claim 39, wherein crystalline non-nitrogen-ionic 20 compound comprises a macronutrient metal.

42. The crystalline fertilizer composition of claim of 39, wherein crystalline non-nitrogen- ionic compound comprises a micronutrient metal.

43. The crystalline fertilizer composition of claim 30, wherein the crystalline coordination nitrogen-metal polymer fertilizer and the crystalline coordination complex fertilizer comprise a 25 metal coordinated by at least one ligand having a donor atom selected from oxygen, nitrogen, sulfur, or chlorine.

44. The crystalline fertilizer composition of claim 30, comprising biuret in a concentration less than 1 wt. percent. 11145. The crystalline fertilizer composition of claim 30, wherein a metal of the at least one metal salt is selected from the group consisting of zinc, copper, manganese, boron, calcium, potassium, sodium, iron, magnesium, molybdenum, cobalt, selenium, nickel, silicon, and chromium. 5 46. The crystalline fertilizer composition of claim 45, wherein the at least one metal salt further comprises an anion selected from the group consisting of sulfate, nitrate, chloride, oxide, hydroxide, carbonate, phosphate, and acetate.

47. The crystalline fertilizer composition of claim 30, wherein the crystalline coordination nitrogen-metal polymer fertilizer and the crystalline coordination nitrogen-metal complex 10 fertilizer comprise a metal center and wherein the metal center is coordinated by at least one ligand having a donor atom selected from the group consisting of oxygen (O), nitrogen (N), sulfur (S), and chlorine (Cl).

48. The crystalline fertilizer composition of claim 47, wherein the metal centers comprises at least one metal selected from the group consisting of zinc, copper, manganese, boron, 15 calcium, potassium, sodium, iron, magnesium, molybdenum, cobalt, selenium, nickel, silicon, and chromium, and wherein the crystalline coordination nitrogen-metal polymer fertilizer and the crystalline coordination nitrogen-metal complex fertilizer are coordinated by at least one nitrogen-containing ligand.

49. A coated fertilizer composition, comprising: 20 a core fertilizer; and a coating crystalline fertilizer applied to the core fertilizer, the coating crystalline fertilizer comprising: the crystalline fertilizer composition comprising at least one selected from the group consisting of Cu₃(SO₄)(OH)₄, FeO(OH), and (NH₄)Zn(PO₄). 25 50. The coated fertilizer composition of claim 49, wherein the coating crystalline fertilizer comprising at least one additional coating agent selected from the group consisting of sulfur, wax, and a polymer.

51. The coated fertilizer composition of claim 49, wherein the coating crystalline fertilizer, comprises a crystalline coordination nitrogen-metal polymer or crystalline coordination 112complex fertilizer comprising at least one nitrogen-containing moiety selected from the group consisting of a urea-metal coordination fertilizer, an ammine-metal coordination fertilizer, and an ammonium-metal coordination fertilizer. 5 52. The crystalline fertilizer composition of claim 30, comprising at least one crystalline coordination urea-metal polymer fertilizer having a crystalline structure of (CH4N2O)4Ca(SO4) or tetrakis(urea) calcium sulfate.

53. The crystalline fertilizer composition of claim 30, comprising at least one crystalline 10 coordination ammonium-metal complex fertilizer having a crystalline structure of (NH4)2Mg(SO4)2(H2O)6.

54. The crystalline fertilizer composition of claim 30, comprising at least one crystalline coordination ammonium-metal complex fertilizer having a crystalline structure of (NH4)2Zn(OH2)6(SO4)2. 15 55. The crystalline fertilizer composition of claim 30, comprising at least one crystalline coordination ammine-metal polymer fertilizer having a crystalline structure of [(H3N)2Zn(SO4)2]2-×2(H4N+).

56. The crystalline fertilizer composition of claim 30, comprising at least one crystalline coordination ammonium-metal complex fertilizer having a crystalline structure of 20 (NH4)2Fe(SO4)2(H2O)6.

57. The crystalline fertilizer composition of claim 30, comprising at least one crystalline coordination urea-metal polymer fertilizer having a crystalline structure of Mn2(SO4)2(CH4N2O)6.

58. The crystalline fertilizer composition of claim 30, comprising at least one crystalline coordination ammine-metal complex fertilizer having a crystalline structure of 25 Cu(SO4)(NH3)4(H2O).

59. A process for producing a nitrogen-ionic compound fertilizer comprising ammonium sulfate fertilizer, comprising: reacting urea with at least one metal sulfate to form an ammonium sulfate, wherein the ammonium sulfate has a crystalline nitrogen-ionic compound fertilizer (NH4)2(SO4). 11360. The process of claim 59, wherein the metal sulfate comprises copper sulfate.

61. The process of claim 59, wherein the metal sulfate comprises iron sulfate.

62. The crystalline fertilizer composition of claim 30, comprising at least one of nutrients, fillers, carriers, binders, humate (humic acid), chemical additives, urease inhibitors, nitrification 5 inhibitors, herbicides, pesticides, and fungicides to the fertilizer.

63. The method of claim 12, wherein the ammonium ionic compound is at least one of ammonium sulfate and ammonium phosphate.

64. The method of claim 12, wherein the ammonium ionic compound is at potassium phosphate. 10 65. The method of claim 40, wherein the ammonium ionic compound is at least one of ammonium sulfate and ammonium phosphate.

66. The method of claim 40, wherein the ammonium ionic compound is at potassium phosphate. 114115

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