A Cheap and Efficient Methodology for the Solvent‐Free,One‐pot and Multi‐component Synthesis of 3,4‐Dihydropyrimidin‐2(1H)‐ones Catalyzed by Mesoporous NH4H2PO4/MCM‐48 and Comparison of Its Catalytic Efficacy with NH4H2PO4/MCM‐41

The catalytic efficiency of ammonium dihydrogenphosphate was evaluated in the two heterogeneous forms of NH₄H₂PO₄/MCM‐48 and NH₄H₂PO₄/MCM‐41, as mesoporous catalysts, in the solvent free synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones through one‐pot three‐component condensation of ethyl acetoacetate, an aryl aldehyde and urea. Different reaction parameters including catalytic efficacy, solvent effect, and urea concentration are considered.     

Crystal Growth,Single‐Crystal Structure Refinement and Unusual Ligand‐Field Splittings of Lazulite‐Type Oxidephosphates MTi2O2(PO4)2 (M = FeII,CoII, NiII)

Single crystals of oxidephosphates MTi₂O₂(PO₄)₂ [M: Fe (dark red), Co (pinkish red), Ni (green)] with edge‐lengths up to 0.4 mm were grown by chemical vapour transport. FeTi₂O₂(PO₄)₂ and CoTi₂O₂(PO₄)₂ are isotypic to NiTi₂O₂(PO₄)₂. The crystal structure of the latter was previously solved from powder data [FeTi₂O₂(PO₄)₂ (data for CoTi₂O₂(PO₄)₂ and NiTi₂O₂(PO₄)₂ in brackets): monoclinic, P2₁/c, Z = 2, a = 7.394(3) (7.381(6), 7.388(4)) Å, b = 7.396(2) (7.371(5), 7.334(10)) Å, c = 7.401(3) (7.366(6), 7.340(3)) Å, β = 120.20(3) (120.26(6), 120.12(4))°, R₁ = 0.0393 (0.0309, 0.0539) wR₂ = 0.1154 (0.0740, 0.1389), 2160 (1059, 1564) independent reflections, 75 (76, 77) variables]. The single‐crystal study allowed improved refinement using anisotropic displacement parameters, yielded lower standard deviations for the structural parameters and revealed a small amount of cation disordering. Twinning and cation disordering within the structures are rationalized by a detailed crystallographic classification of the MTi₂O₂(PO₄)₂ structure type in terms of group‐subgroup relations. The structure is characterized by a three‐dimensional network of [PO₄] tetrahedra and [M^IITi₂O₁₂] groups formed by face‐sharing of [M^IIO₆] and [TiO₆] octahedra. Electronic absorption spectra of MTi₂O₂(PO₄)₂ in the UV/VIS/NIR region show rather large ligand‐field splittings for the strongly trigonally distorted chromophors [M^IIO₆] (M = Fe, Co, Ni) with interelectronic repulsion parameters beeing slightly smaller than in other phosphates. Interpretation of the spectra within the framework of the angular overlap model reveals a significant second‐sphere ligand field effect of Ti^IV ions on the electronic levels of the Ni^II and Co^II.     

Syntheses and Crystal Structures of Three Organically Templated Gallium Phosphates

Three open‐framework gallium phosphates [C₆H₁₆N₂][Ga(HPO₄)(PO₄)] ( 1 ), {H[C₆H₁₆N₂]₂[Ga₇(OH)₂(PO₄)₈]} ( 2 ), and {H[C₄H₁₂N₂]₂[Ga₇(OH)₂(PO₄)₈] · 2H₂O} ( 3 ) were solvothermally synthesized in the presence of 2,6‐dimethylpyrazine, N‐ethylpiperazine, and piperazine as templates, respectively. Compound 1 possesses an infinite one‐dimensional chain structure connected by hydrogen‐bond interactions to generate a 3D supramolecular framework. Compounds 2 and 3 show similar inorganic framework structures, which may be viewed as the assembly of a secondary building unit (SBU), Ga₆P₈ containing two GaO₄, two GaO₅, two GaO₆ as well as eight PO₄ groups. The SBUs are linked with each other by vertex‐sharing oxygen atoms to form 2D sheets, which are further connected by GaO₄ tetrahedra to result in the final 3D open‐framework with left‐ and right‐handed helical chains. In these materials, the well‐ordered organic species reside in the voids of structures and interact with the framework by way of hydrogen bonds.     

Ferric Phosphate Hydroxide Microcrystals for Highly Efficient Visible‐Light‐Driven Photocatalysts

Fe₄(OH)₃(PO₄)₃ microcrystals are successfully synthesized by a simple hydrothermal method. Due to a possible self‐etching mechanism, different morphologies of Fe₄(OH)₃(PO₄)₃ microcrystals are obtained. Several reactions with different temperatures and times are performed to confirm the supposed self‐etching mechanism. Moreover, as a result of their different micro/nanostructures, these microcrystals present different photocatalytic activities for visible‐light‐driven photodegragadation of methylene blue.     

Assembly of Na3V2(PO4)3 Nanoparticles Confined in a One‐Dimensional Carbon Sheath for Enhanced Sodium‐Ion Cathode Properties

Structural and morphological control is an effective approach for improvement of electrochemical properties in rechargeable batteries. One‐dimensionally assembled structure composed of NASICON‐type Na₃V₂(PO₄)₃ nanoparticles were fabricated through an electrospinning method to meet the requirements for the development of efficient electrode materials in Na‐ion batteries. High‐temperature treatment of electrospun precursor fibers under an argon flow provides a nonwoven fabric of nanowires comprising crystallographically oriented nanoparticles of NASICON‐type Na₃V₂(PO₄)₃ within a carbon sheath. The mesostructure comprising NASICON‐type Na₃V₂(PO₄)₃ and carbon give a short sodium‐ion transport pass and an efficient electron conduction pass. Electrochemical properties of NASICON‐type Na₃V₂(PO₄)₃ are improved on the basis of one‐dimensional nanostructures designed in the present study.     

Werner transition‐metal complex (WTMC)‐mediated mild and efficient chemo‐selective acylation of phenols and anilines under solvent‐free condition

Werner‐type transition‐metal complexes (WTMC) such as [Co(NH₃)₅Cl]Cl₂, Cu[(NH₃)₄]SO₄, Mn(acac)₃, Ni[(NH₃)₆]Cl₂, Ni[(en)₃]S₂O₃, and Hg[Co(SCN)₄] efficiently promote the chemoselective acetylation of phenols and anilines under solvent‐free condition. The results of this study clearly shows that the optimal condition for the acetylation of anilines/phenols (1 mmol) ( 2a–r ) with acetic anhydride (1.2 mmol) in the presence of WTMC (1 mmol) and two drops of H₃PO₄ on heating for 10 min under solvent‐free condition gives the corresponding acetanilides/phenyl acetate ( 3a–r ) in good to excellent yield. Furthermore, the method is simple, efficient, chemoselective, and eco‐friendly under solvent‐free condition for the acetylation of anilines and phenols promoted by WTMC by using acetic anhydrate as the acetylating agent. The simple preparation of the catalyst, easy procedure of the acetylation reaction, and simple work‐up indicate the importance of WTMC for such reactions.     

Immobilization of cerium (IV) and erbium (III) in mesoporous MCM‐41: Two novel and highly active heterogeneous catalysts for the synthesis of 5‐substituted tetrazoles,and chemo‐ and homoselective oxidation of sulfides

Two well‐ordered 2D ‐ hexagonal cerium (IV) and erbium (III) embedded functionalized mesoporous MCM ‐ 41(MCM‐41@Serine/Ce and MCM ‐ 41@Serine/Er) have been developed via functionalization of mesoporous MCM ‐ 41. The surface modification method has been used in the preparation of serine‐grafted MCM ‐ 41 and led to the development of MCM‐41@Serine. The reaction of MCM‐41@Serine with Ce (NH₄)₂(NO₃)₆·2H₂O or ErCl₃·6H₂O in ethanol under reflux led to the organization of MCM‐41@Serine/Ce and MCM‐41@Serine/Er catalysts. The structures of these catalysts were determined using scanning electron microscopy, mapping, energy‐dispersive X‐ray spectroscopy, Fourier transform‐infrared, thermogravimetric analysis, X‐ray diffraction, inductively coupled plasma, and Brunauer–Emmett–Teller analysis. These MCM‐41@Serine/Ce and MCM‐41@Serine/Er catalysts show outstanding catalytic performance in sulfides oxidation and synthesis of 5‐substituted tetrazoles. These catalysts can be recycled for seven repeated reaction runs without showing a considerable decrease in catalytic performance.     

Corrosion‐Mediated Self‐Assembly (CMSA): Direct Writing Towards Sculpturing of 3D Tunable Functional Nanostructures

Inexpensive and readily available metal foils have been extracted and sculptured into nanocomposites without the expense of applied energy. The unwanted corrosion phenomenon has been contrarily utilized to realize desirable 3D nanostructures through a corrosion‐mediated self‐assembly (CMSA) method, which is unattainable by conventional 2D patterning routes. By virtue of electrochemical dissolution/re‐deposition initiated by brass corrosion, ionic derivatives (Zn²⁺ and Cu²⁺) are continuously supplied and seized by etchant ions (PO₄^3?) to self‐assemble into well‐defined nanocomposites. Beyond 3D geometry patterning, CMSA enables arbitrarily tailoring of structures and chemical compositions with in situ multiphase amalgamation of hybrid materials, which improves homogeneity and thus mitigates phase separation issues. Importantly, the CMSA technique is demonstrated on transition metals for functional photocatalytic applications.     

A Yolk–Shell‐Structured FePO4 Cathode for High‐Rate and Long‐Cycling Sodium‐Ion Batteries

Amorphous iron phosphate (FePO₄) has attracted enormous attention as a promising cathode material for sodium‐ion batteries (SIBs) because of its high theoretical specific capacity and superior electrochemical reversibility. Nevertheless, the low rate performance and rapid capacity decline seriously hamper its implementation in SIBs. Herein, we demonstrate a sagacious multi‐step templating approach to skillfully craft amorphous FePO₄ yolk–shell nanospheres with mesoporous nanoyolks supported inside the robust porous outer nanoshells. Their unique architecture and large surface area enable these amorphous FePO₄ yolk–shell nanospheres to manifest remarkable sodium storage properties with high reversible capacity, outstanding rate performance, and ultralong cycle life.     

A novel route for FePO4 olivine synthesis from sarcopside oxidation

Heterosite FePO₄ is synthesized for the first time by direct thermal oxidation of sarcopside Fe₃(PO₄)₂. Both FePO₄ and Fe₃(PO₄)₂ have a pseudo olivine structure. Complete isostructural conversion of sarcopside into FePO₄ is achieved at a temperature of 450 °C within 3 days according to the reaction Fe₃(PO₄)₂ + ¾ O₂ → 2 FePO₄ + ½ Fe₂O₃ which leads to the extraction of iron from the sarcopside structure. Appropriate heating ramp must be applied in order to avoid the crystallization of Fe₇(PO₄)₆. Electrochemical performances of the oxidation product are consistent with those of olivine FePO₄.     

Characterization of Two Zincophosphates (UH‐6 and UH‐10) Synthesized using the Cobalt(III) Sarcophagine Complex as Structure‐directing Agent

The novel zincophosphates UH‐6 (sum formula |[Co(diAMHsar)]| [Zn₂(HPO₄)₃(PO₄)] · H₂O) and UH‐10 (sum formula |([Co(diAMHsar)])₂| [{Zn₂(HPO₄)₃(PO₄)}₂] · H₂O) were synthesized in hydrothermal syntheses employing the chiral sarcophagine complex [Co(diAMHsar)]⁵⁺ as the structure‐directing agent. The inorganic part of UH‐6 consists of pearl‐like chains of alternating [ZnO₄] and [PO₄] tetrahedra, which are connected to the incorporated cobalt complex via numerous hydrogen bonds. UH‐10 was synthesized under similar conditions, but at higher reaction temperatures. In consequence, the crystal structures of UH‐6 and UH‐10 are closely related, although systematic disorder in UH‐10 and the lower symmetry result in a unit cell twice as large as the corresponding unit cell of UH‐6. Interestingly, in both zincophosphates only one enantiomer of the cobalt complex is present, despite the fact that a racemic mixture of the complex salt is used for synthesis. Thermogravimetric analysis and powder X‐ray diffraction of a thermally treated sample of UH‐6 reveals a phase transformation at ca. 300 °C.     

Green Template‐Free Synthesis of Hierarchical Shuttle‐Shaped Mesoporous ZnFe2O4 Microrods with Enhanced Lithium Storage for Advanced Li‐Ion Batteries

In the work, a facile and green two‐step synthetic strategy was purposefully developed to efficiently fabricate hierarchical shuttle‐shaped mesoporous ZnFe₂O₄ microrods (MRs) with a high tap density of ～0.85 g cm³, which were assembled by 1D nanofiber (NF) subunits, and further utilized as a long‐life anode for advanced Li‐ion batteries. The significant role of the mixed solvent of glycerin and water in the formation of such hierarchical mesoporous MRs was systematically investigated. After 488 cycles at a large current rate of 1000 mA g^?1, the resulting ZnFe₂O₄ MRs with high loading of ～1.4 mg per electrode still preserved a reversible capacity as large as ～542 mAh g^?1. Furthermore, an initial charge capacity of ～1150 mAh g^?1 is delivered by the ZnFe₂O₄ anode at 100 mA g^?1, resulting in a high Coulombic efficiency of ～76 % for the first cycle. The superior Li‐storage properties of the as‐obtained ZnFe₂O₄ were rationally associated with its mesoprous micro‐/nanostructures and 1D nanoscaled building blocks, which accelerated the electron transportation, facilitated Li⁺ transfer rate, buffered the large volume variations during repeated discharge/charge processes, and provided rich electrode–electrolyte sur‐/interfaces for efficient lithium storage, particularly at high rates.     

Synthesis of Mesoporous Transition‐Metal Phosphates by Polymeric Micelle Assembly

Mesoporous iron phosphate (FePO₄) was synthesized through assembly of polymeric micelles made of asymmetric triblock co‐polymer (polystyrene‐b‐poly‐2‐vinylpyridine‐b‐ethylene oxide; PS‐PVP‐PEO). The phosphoric acid solution stimulates the formation of micelles with core–shell‐corona architecture. The negatively charged PO₄^3? ions dissolved in the solution strongly interact with the positively charged PVP⁺ units through an electrostatic attraction. Also, the presence of PO₄^3? ions realizes a bridge between the micelle surface and the metal ions. The removal of polymeric template forms the robust framework of iron phosphate with 30 nm pore diameter and 15 nm wall thickness. Our method is applicable to other mesoporous metal phosphates by changing metal sources. The obtained materials were fully characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), N₂ adsorption–desorption, Raman spectroscope, and other techniques.     

2,11-二硫代[3.3]二聚对二甲苯与线性氟代二羧酸银之配位聚合物的合成

本文主要描述了由配体2,11-二硫代[3.3]二聚对二甲苯与线性氟代二羧酸银反应制得的三个银配合物的结构。这些配合物的结构因氟代二羧酸银的不同,差别也很大。配体2,11-二硫代[3.3]二聚对二甲苯与氟代丁二酸银反应得到的配合物1是一维链状结构;将银盐换成氟代戊二酸银则获得了三维立体结构的配合物2;若使用氟代己二酸银,则得到了二维多孔的配合物3。在多孔配合物3中,每个孔中容纳了两个客体三甲苯分子,在150℃时这些客体分子可被完全脱除。     

Struktur und 1D‐magnetische Eigenschaften von (pipzH2)[MnF4(H2PO4)]

Structure and 1D‐magnetic properties of (pipzH₂)[MnF₄(H₂PO₄)] From hydrofluoric and phosphoric acid solution of Manganese(III), using piperazinium(2+) counter cations (pipzH₂²⁺) the chain‐anion [MnF₄(H₂PO₄)]^2— can be stabilized providing an interesting model system for studying the magnetic exchange interaction via phosphate bridges. Depending on the HF/H₃PO₄ excess (pipzH₂)[MnF₄(H₂PO₄)] crystallizes in two polymorphs I und II , differing mainly in the orientation of the cations. Form I is monoclinic, space group P2₁/c, Z = 4, a = 6.749(1), b = 12.039(1), c = 12.501(1) Å, β = 94.420(4)°, R = 0.023, Form II crystallizes in the same space group type P2₁/c, Z = 4, a = 6.651(1), b = 12.799(1), c = 12.825(1) Å, β = 110.312(5)°, R = 0.037. The Mn³⁺ ions are octahedrally surrounded by four terminal fluoride ligands and axially by bidentate bridging dihydrogenphosphate groups. The shape of the chain anions is very close in both modifications and characteristic for ferrodistortive Jahn‐Teller ordering.The Mn—O‐bonds along the chain direction are strongly elongated (distances 2.16 to 2.21 Å) whereas all Mn—F bond (1.81—1.88Å) are ruther short. On a large single crystal of form I 1D‐antiferromagnetic properties were found. By fitting an appropriate model based on the temperature dependence of the correlation lengths using an anisotropy constant D/k = —2.9 K a remarkably high exchange energy of J/k = —1.6(1) K along the chains could be determined.     

Exploring the Symmetry,Structure, and Self‐Assembly Mechanism of a Gigantic Seven‐Fold Symmetric {Pd84} Wheel

The symmetry, structure and formation mechanism of the structurally self‐complementary { Pd₈₄ } = [Pd₈₄O₄₂(PO₄)₄₂(CH₃CO₂)₂₈]^70? wheel is explored. Not only does the symmetry give rise to a non‐closest packed structure, the mechanism of the wheel formation is proposed to depend on the delicate balance between reaction conditions. We achieve the resolution of gigantic polyoxopalladate species through electrophoresis and size‐exclusion chromatography, the latter has been used in conjunction with electrospray mass spectrometry to probe the formation of the ring, which was found to proceed by the stepwise aggregation of {Pd₆}^? = [Pd₆O₄(CH₃CO₂)₂(PO₄)₃Na_6?nH_n]^? building blocks. Furthermore, the higher‐order assembly of these clusters into hollow blackberry structures of around 50 nm has been observed using dynamic and static light scattering.     

Beiträge zum thermischen Verhalten und zur Kristallchemie von wasserfreien Phosphaten XXXII [1] Neue Orthophosphate des zweiwertigen Chroms — Mg3Cr3(PO4)4, Mg3, 75Cr2, 25(PO4)4, Ca3Cr3(PO4)4 und Ca2, 00Cr4, 00(PO4)4

Contributions on Crystal Chemistry and Thermal Behaviour of Anhydrous Phosphates. XXXII. New Orthophosphates of Divalent Chromium — Mg₃Cr₃(PO₄)₄, Mg_{3, 75}Cr_{2, 25}(PO₄)₄, Ca₃Cr₃(PO₄)₄ and Ca_{2, 00}Cr_{4, 00}(PO₄)₄ Solid state reactions via the gas phase led in the systems A₃(PO₄)₂ / Cr₃(PO₄)₂ (A = Mg, Ca) to the four new compounds Mg₃Cr₃(PO₄)₄ ( A ), Mg_3.75Cr_2.25(PO₄)₄ ( B ), Ca₃Cr₃(PO₄)₄ ( C ), and Ca_2.00Cr_4.00(PO₄)₄ ( D ). These were characterized by single crystal structure investigations [( A ): P2₁/n, Z = 1, a = 4.863(2) Å, b = 9.507(4) Å, c = 6.439(2) Å, β = 91.13(6)°, 1855 independend reflections, 63 parameters, R1 = 0.035, wR2 = 0.083; ( B ): P2₁/a, Z = 2, a = 6.427(2) Å, b = 9.363(2) Å, c = 10.051(3) Å, β = 106.16(3)°, 1687 indep. refl., 121 param., R1 = 0.032, wR2 = 0.085; ( C ): P‐1, Z = 2, a = 8.961(1) Å, b = 8.994(1) Å, c = 9.881(1) Å, α = 104.96(2)°, β = 106.03(2)°, γ = 110.19(2)°, 2908 indep. refl., 235 param., R1 = 0.036, wR2 = 0.111; ( D ): C2/c, Z = 4, a = 17.511(2) Å, b = 4.9933(6) Å, c = 16.825(2) Å, β = 117.95(1)°, 1506 indep. refl., 121 param., R1 = 0.034, wR2 = 0.098]. The crystal structures contain divalent chromium on various crystallographic sites, each showing a (4+n)‐coordination (n = 1, 2, 3). For the magnesium compounds and Ca_2.00Cr_4.00(PO₄)₄ a disorder of the divalent cations Mg²⁺/Cr²⁺ or Ca²⁺/Cr²⁺ is observed. Mg_3.75Cr_2.25(PO₄)₄ adopts a new structure type, while Mg₃Cr₃(PO₄)₄ is isotypic to Mg₃(PO₄)₂. Ca₃Cr₃(PO₄)₄ and Ca_2.00Cr_4.00(PO₄) ₄ are structurally very closely related and belong to the Ca₃Cu₃(PO₄)₄‐structure family. The orthophosphate Ca₉Cr(PO₄)₇, containing trivalent chromium, has been obtained besides C and D .     

Investigation of Chromophoric Behavior of Water‐Soluble LaIII‐CuII Polynuclear Metallamacrocyclic 15‐MC‐5 Complex

The visible absorption spectrum of the water soluble polynuclear metallamacrocyclic La^III‐Cu^II complex La(H₂O)₃[15‐MC_{Cu(II)Phalaha}‐5](Cl)₃ ( 1 ) based on α‐phenylalaninehydroxamic acid appears to be solvent‐ and ion‐sensitive. The copper(II) d–d transitions of the complex 1 dissolved in methanol, ethanol, water, dimethylformamide, dimethylsulfoxide, pyridine, and N‐methylpyrrolidone were studied. The chromophoric behavior of complex 1 was investigated in the presence of the Cl^–, Br^–, I^–, HSO₄^–, CO₃^2–, HCO₃^–, H₂PO₄^–, CN^–, SCN^–, and N₃^– anions. A considerable change of the d–d transition of the central copper(II) atom was observed for the strongly coordinating cyanide and azide anions. In the presence of HSO₄^–, the d–d intensity of copper(II) also decreased significantly. The molecular structure of La₂(H₂O)₇[15‐MC_{Cu(II)Phalaha}‐5]₂(SO₄)₄ ( 2 ), obtained as result of the substitution of the coordinated water molecules in 1 by the SO₄^2– anions, was investigated by X‐ray crystallography.     

Neue Zirconiumphosphatfluoride mit 3D‐Gerüststruktur

New Zirconium Phosphate Fluorides with 3D‐Framework From aqueous solutions of ZrOCl₂, H₃PO₄, HF, and various amines, two new compounds of the general formula [amH₂]_1/2[Zr₂(HPO₄)(PO₄)₂F] · nH₂O ( I : am = N,N‐dimethylethylenediamine, n = 0,5; II : am = N,N‐dimethyl‐1,3‐diaminopropane, n = 0) adopting the ZrPOF‐1 structure type have been synthesized under hydrothermal conditions. In contrast to the monoclinic ZrPOF‐1, both compounds crystallize in the space group P 1 with a = 6.611(3), b = 9.109(4), c = 11.560(5) Å, α = 85.62(4), β = 89.60(4), γ = 70.57(4)° in I , and a = 6.616(2), b = 9.045(3), c = 11.565(4) Å, α = 85.26(4), β = 88.86(4), γ = 71.46(4)° in II . Compound III (am = ethylenediamine, n = 0) has been obtained by dehydration of ZrPOF‐1 and occurs in the space group P1 with a = 6.605(2), b = 8.787(3), c = 11.499(5) Å, α = 93.07(4), β = 90.42(4) and γ = 104.66(4)°. The structural motifs of the frameworks of the three compounds have much in common. The template and the PO₃OH tetrahedra in I and II are disordered. Differences in the water content in both compounds are due to differences in the chain lengths of the amines. The absence of crystal water in compound III breaks the template disordering which is present in ZrPOF‐1. The rotation of the PO₃OH tetrahedra in II and III compared with I and ZrPOF‐1 is discussed in regard with the absence of stabilizing H‐bridges in the former compounds.     

Structures and Properties of Three Solvent‐Dependent Chiral Compounds Based on N‐Benzoyl‐L‐glutamic Acid

Three solvent‐dependent chiral copper(II) compounds, {[Cu₂(bzgluO)₂(H₂O)₂]·4H₂O}_n ( 1 ), {[Cu₂(bzgluO)₂(DMSO)₂]·H₂O}_n ( 2 ) and [Cu₂(bzgluO)₂(DMF)₂]_n ( 3 ) (H₂bzgluO=N‐benzoyl‐L‐glutamic acid) have been synthesized under ambient temperature conditions and characterized by elemental analysis, IR spectra, UV spectra, thermogravimetric analysis, powder X‐ray diffraction (PXRD) and single‐crystal X‐ray diffraction. Compounds 1 and 2 both crystallize in the orthorhombic space group P2₁2₁2₁. Compound 3 crystallizes in the tetragonal space group P4₃. Compound 1 exhibits a ladder‐like 1D chain structure, which is extended by hydrogen‐bonding interactions to form a 3D supramolecular network. Compounds 2 and 3 both give a diamond‐like 3D structure. Besides, there are hydrogen‐bonding interactions in 2 . The structural difference indicates that the solvent system plays a crucial role in modulating structures of coordination compounds. Circular dichroism (CD) and the magnetic properties of the compounds have also been investigated.