Solvothermal Synthesis,Crystal Structures,and Magnetic Properties of Two Organically Templated Iron Sulfates with Chain Structures

Two new one‐dimensional (1D) organically templated iron(III) sulfates [C₂NH₈]₃ [Fe₃(μ₃‐O)₂(SO₄)₄] ( 1 ) and [C₂N₂H₁₀][C₂NH₇]_0.5[FeF(SO₄)₂] ( 2 ) were synthesized under solvothermal conditions and characterized by single‐crystal X‐ray diffraction, powder X‐ray diffraction (XRD), FT‐IR spectroscopy, elemental analyses, ICP analyses, and thermogravimetric analyses. Single‐crystal structure analysis reveals that both compounds show linear‐chain structures, involving FeO₆ (FeF₂O₄) octahedra and SO₄ tetrahedra. The magnetic properties of the two compounds have also been investigated.     

Synthesis,Crystal Structure,Bonding, and Properties of (Ba6O)(OsN3)2

The new barium nitridoosmate oxide (Ba₆O)(OsN₃)₂ was prepared by reacting elemental barium and osmium (3:1) in nitrogen at 815–830 °C. The crystal structure of (Ba₆O)(OsN₃)₂ as determined by laboratory powder X‐ray diffraction ( , No 148: a=b=8.112(1) Å, c=17.390(1) Å, V=991.0(1) ų, Z=3), consists of sheets of trigonal OsN₃ units and trigonal‐antiprismatic Ba₆O groups, and is structurally related to the “313 nitrides” AE₃MN₃ (AE=Ca, Sr, Ba, M=V–Co, Ga). Density functional calculations, using a hybrid functional, likewise indicate the existence of oxygen in the Ba₆ polyhedra. The oxidation state 4+ of osmium is confirmed, both by the calculations and by XPS measurements. The bonding properties of the OsN₃^5? units are analyzed and compared to the Raman spectrum. The compound is paramagnetic from room temperature down to T=10 K. Between room temperature and 100 K it obeys the Curie–Weiss law (μ=1.68 μ_B). (Ba₆O)(OsN₃)₂ is semiconducting with a good electronic conductivity at room temperature (8.74×10^?2 Ω^?1 cm^?1). Below 142 K the temperature dependence of the conductivity resembles that of a variable‐range hopping mechanism.     

Oxamido‐bridged N4 Macrocyclic Complexes CuII/MII/CuII (M = Mn,Co): Synthesis,Crystal Structures and Magnetic Properties

Two new oxamido‐bridged N₄ macrocyclic complexes [(CuL)₂Mn(C₂H₅OH)₂](ClO₄)₂ · 2C₂H₅OH ( 1 ) and [(CuL)₂Co‐(C₂H₅OH)₂](ClO₄)₂ · 2C₂H₅OH ( 2 ) (H₂L = 2,3‐dioxo‐5,6:14,15‐di‐benzo‐7,13‐diphenyl‐1,4,8,12‐tetraazacyclo‐pentadeca‐7,13‐diene) have been synthesized and structurally characterized by X‐ray crystallographic investigations. In the two complexes, all copper(II) ions adopt a slightly distorted square‐planar configuration and the central manganese(II) and cobalt(II) ions are set in a distorted octahedral coordination sphere, connected to the other CuL fragments through exo‐cis oxamido bridges. The analyses of the magnetic properties were carried out by means of the theoretical expression of the magnetic susceptibility deduced from the spin Hamiltonian ? = –2J?₁?₂, leading to J = –14.58 cm^–1 for complex 1 and J = –26.95 cm^–1 for complex 2 , respectively.     

Heterotrimetallic Coordination Polymers: {CuIILnIIIFeIII} Chains and {NiIILnIIIFeIII} Layers: Synthesis,Crystal Structures,and Magnetic Properties

The use of the [Fe^III(AA)(CN)₄]^? complex anion as metalloligand towards the preformed [Cu^II(valpn)Ln^III]³⁺ or [Ni^II(valpn)Ln^III]³⁺ heterometallic complex cations (AA=2,2′‐bipyridine (bipy) and 1,10‐phenathroline (phen); H₂valpn=1,3‐propanediyl‐bis(2‐iminomethylene‐6‐methoxyphenol)) allowed the preparation of two families of heterotrimetallic complexes: three isostructural 1D coordination polymers of general formula {[Cu^II(valpn)Ln^III(H₂O)₃(μ‐NC)₂Fe^III(phen)(CN)₂ {(μ‐NC)Fe^III(phen)(CN)₃}]NO₃ ? 7 H₂O}_n (Ln=Gd ( 1 ), Tb ( 2 ), and Dy ( 3 )) and the trinuclear complex [Cu^II(valpn)La^III(OH₂)₃(O₂NO)(μ‐NC)Fe^III(phen)(CN)₃] ? NO₃ ? H₂O ? CH₃CN ( 4 ) were obtained with the [Cu^II(valpn)Ln^III]³⁺ assembling unit, whereas three isostructural heterotrimetallic 2D networks, {[Ni^II(valpn)Ln^III(ONO₂)₂(H₂O)(μ‐NC)₃Fe^III(bipy)(CN)] ? 2 H₂O ? 2 CH₃CN}_n (Ln=Gd ( 5 ), Tb ( 6 ), and Dy ( 7 )) resulted with the related [Ni^II(valpn)Ln^III]³⁺ precursor. The crystal structure of compound 4 consists of discrete heterotrimetallic complex cations, [Cu^II(valpn)La^III(OH₂)₃(O₂NO)(μ‐NC)Fe^III(phen)(CN)₃]⁺, nitrate counterions, and non‐coordinate water and acetonitrile molecules. The heteroleptic {Fe^III(bipy)(CN)₄} moiety in 5 – 7 acts as a tris‐monodentate ligand towards three {Ni^II(valpn)Ln^III} binuclear nodes leading to heterotrimetallic 2D networks. The ferromagnetic interaction through the diphenoxo bridge in the Cu^II?Ln^III ( 1 – 3 ) and Ni^II?Ln^III ( 5 – 7 ) units, as well as through the single cyanide bridge between the Fe^III and either Ni^II ( 5 – 7 ) or Cu^II ( 4 ) account for the overall ferromagnetic behavior observed in 1 – 7 . DFT‐type calculations were performed to substantiate the magnetic interactions in 1 , 4 , and 5 . Interestingly, compound 6 exhibits slow relaxation of the magnetization with maxima of the out‐of‐phase ac signals below 4.0 K in the lack of a dc field, the values of the pre‐exponential factor (τ_o) and energy barrier (E_a) through the Arrhenius equation being 2.0×10^?12 s and 29.1 cm^?1, respectively. In the case of 7 , the ferromagnetic interactions through the double phenoxo (Ni^II–Dy^III) and single cyanide (Fe^III–Ni^II) pathways are masked by the depopulation of the Stark levels of the Dy^III ion, this feature most likely accounting for the continuous decrease of χ_M T upon cooling observed for this last compound.     

Synthesis,Crystal Structure,and Properties of the Sodium Molybdate Fluoride Na3MoO4F

The compound Na₃MoO₄F was synthesized by high temperature solution methods. Single‐crystal X‐ray diffraction analysis reveals that Na₃MoO₄F crystallizes in the orthorhombic space group Pnma (No. 62) with lattice constants a = 5.588(2) Å, b = 7.515(3) Å, c = 12.876(5) Å, and Z = 4. The crystal structure consists of isolated MoO₄ groups and [FNa₃]_∞ chains, which are connected by Na–O bonds to form a three‐dimensional framework. A detailed structure comparison between Na₃MoO₄F and NaMoO₃F was carried out. IR spectroscopy and bond valence sum analysis of Na₃MoO₄F indicate that the structure is reasonable. In addition, the electronic structure was investigated by the first‐principles method.     

Synthesis,Crystal Structures,and Optical Properties of AM2(OH)(SeO3)2 (A = Na,Rb; M = Mg,Zn)

Sodium magnesium selenite NaMg₂(OH)(SeO₃)₂ and rubidium zinc selenite RbZn₂(OH)(SeO₃)₂ were prepared by hydrothermal reactions. The crystal structures of the title compounds were determined by single‐crystal X‐ray diffraction. NaMg₂(OH)(SeO₃)₂ crystallizes in the orthorhombic space group Pnma (no. 62) with lattice parameters a = 13.1919(10), b = 6.0415(4), c = 8.2182(6) Å, and Z = 4 and RbZn₂(OH)(SeO₃)₂ crystallizes in the triclinic space group P$\bar{1}$ (no. 2) with lattice parameters a = 4.8698(5), b = 7.3446(8), c = 11.7796(12) Å, α = 82.554(3), β = 78.456(2), γ = 71.603(3)°,and Z = 2. The structure of NaMg₂(OH)(SeO₃)₂ is a three‐dimensional framework consisting of edge‐sharing MgO₆ octahedra and trigonal pyramidal SeO₃^2– groups, whereas the structure of RbZn₂(OH)(SeO₃)₂ is a two‐dimensional layers structure consisting of corner‐sharing [Zn₂O₇] dimers linked by trigonal pyramidal SeO₃^2– groups. The compounds were characterized by the solid state UV/Vis/NIR diffuse reflectance, and FT‐IR spectroscopy.     

Synthesis,Crystal Structures,and Photoluminescence of Lanthanide Coordination Polymers with 4‐Acetamidobenzoate

The reactions of Ln(NO₃)₃ · 6H₂O and 4‐acetamidobenzoic acid (Haba) with 4,4′‐bipyridine (4,4′‐bpy) in ethanol solution resulted in three new lanthanide coordination polymers, namely {[Ln(aba)₃(H₂O)₂] · 0.5(4,4′‐bpy) · 2H₂O}_∞ [Ln = Sm ( 1 ), Gd ( 2 ), and Er ( 3 ), aba = 4‐acetamidobenzoate]. Compounds 1 – 3 are isomorphous and have one‐dimensional chains bridged by four aba anions. 4,4′‐Bipyridine molecules don’t take part in the coordination with Ln^III ions and occur in the lattice as guest molecules. Moreover, the adjacent 1D chains in the complex are further linked through numerous N–H ··· O and O–H ··· O hydrogen bonds to form a 3D supramolecular network. In addition, complex 1 in the solid state shows characteristic emission in the visible region at room temperature.     

Synthesis,Crystal Structure and Selected Properties of Mono(dithiocarbamato)‐gold(I), AuS2CNH2

The title compound AuS₂CNH₂ was prepared from an aqueous solution by reaction of dicyanidoaurate [Au(CN)₂]^– with excess of ammoniumdithiocarbamate NH₄S₂CN H ₂ at pH ≈ 2. The compound crystallizes in the orthorhombic space group Cmma with a = 6.4597(2), b = 12.6556(3), and c = 5.3235(1) Å. The crystal structure comprises linear S–Au–S dumbbells forming unbranched zigzag chains in combination with the dithiocarbamate ligands. The three‐dimensional arrangement of the molecules is realized by aurophilic Au^I–Au^I and hydrogen bonding interactions, respectively. AuS₂CNH₂ presents orange luminescence due to a broad emission band between 12000 cm^–1 and 23000 cm^–1 (ν = 26316 cm^–1).     

Synthesis and Crystal Structures of Novel Copper(I) Clusters with Bridging Silyl Amide Ligands

Treatment of copper(I) chloride with R₂Si(NLiPh)₂ (R = Me, Ph) in thf led to the formation of the octanuclear cluster compounds [Cu₈{(R₂Si(NPh)₂}₄] [R = Me ( 1 ), Ph ( 2 ).] Compound 1 crystallizes in the tetragonal space group P4/n, with a = 1505.41(5) and c = 1911.32(7) pm. The X‐ray crystal structure determination revealed a cube shaped Cu₈ cluster core with μ₄ bridging Me₂Si(NPh)₂^2– ligands. The copper atoms display an almost linear coordination with Cu–N distances in the range of 191.1(3)–191.4(3) pm. The Cu–Cu distances are 265.7(1)–267.3(1) pm. Compound 2 forms monoclinic crystals, space group P2₁/n, with a = 1461.87(4), b = 2483.77(6), c = 2725.49(8) pm, β = 100.77(1)°. The cluster core of compound 2 consists formally of two mutually perpendicular arranged trigonal prisms, which share a common square face. Like in the case of compound 1 the square faces of the cluster core are capped by μ₄ bridging Ph₂Si(NPh)₂^2– ligands. The copper atoms adopt a nearly linear N–Cu–N coordination with Cu–N distances of 190.0(4)–195.1(4) pm. The Cu–Cu distances are 252.3(1)–305.6(1) pm.     

Crystal Structures and Emitting Properties of Trifluoromethylaminoquinoline Derivatives: Thermal Single‐Crystal‐to‐Single‐Crystal Transformation of Polymorphic Crystals That Emit Different Colors

2,4‐Trifluoromethylquinoline (TFMAQ) derivatives that have amine ( 1 ), methylamine ( 2 ), phenylamine ( 3 ), and dimethylamine ( 4 ) substituents at the 7‐position of the quinoline ring were prepared and crystallized. Six crystals including the crystal polymorphs of 2 (crystal GB and YG) and 3 (crystal B and G) were obtained and characterized by X‐ray crystallography. In solution, TFMAQ derivatives emitted relatively strong fluorescence (${\lambda {{{\rm f}\hfill \atop {\rm max}\hfill}}}$ =418–469 nm and Φ_f(s)=0.23–0.60) depending on the solvent polarity. From Lippert–Mataga plots, Δμ values in the range of 7.8–14 D were obtained. In the crystalline state, TFMAQ derivatives emitted at longer wavelengths (${\lambda {{{\rm f}\hfill \atop {\rm max}\hfill}}}$ =464–530 nm) with lower intensity (Φ_f(c)=0.01–0.28) than those in n‐hexane solution. The polymorphous crystals of 2 and 3 emitted different colors: 2 , ${\lambda {{{\rm f}\hfill \atop {\rm max}\hfill}}}$ =470 and 530 nm with Φ_f(c)=0.04 and approximately 0.01 for crystal GB and YG, respectively; and 3 , ${\lambda {{{\rm f}\hfill \atop {\rm max}\hfill}}}$ =464 and 506 nm with Φ_f(c)=0.28 and approximately 0.28 for crystal B and G, respectively. In both crystal polymorphs of 2 and 3 , crystals GB and G showed emission color changes by heating/melting/cooling cycles that were representative. By following the color changes in heating at the temperature below the melting point with X‐ray diffraction measurements and X‐ray crystallography, the single‐crystal‐to‐single‐crystal transformations from crystal GB to YG for 2 and from crystal B to G for 3 were revealed.     

Lead‐Free Halide Perovskite Nanocrystals: Crystal Structures,Synthesis, Stabilities,and Optical Properties

In recent years, there have been rapid advances in the synthesis of lead halide perovskite nanocrystals (NCs) for use in solar cells, light emitting diodes, lasers, and photodetectors. These compounds have a set of intriguing optical, excitonic, and charge transport properties, including outstanding photoluminescence quantum yield (PLQY) and tunable optical band gap. However, the necessary inclusion of lead, a toxic element, raises a critical concern for future commercial development. To address the toxicity issue, intense recent research effort has been devoted to developing lead‐free halide perovskite (LFHP) NCs. In this Review, we present a comprehensive overview of currently explored LFHP NCs with an emphasis on their crystal structures, synthesis, optical properties, and environmental stabilities (e.g., UV, heat, and moisture resistance). In addition, strategies for enhancing optical properties and stabilities of LFHP NCs as well as the state‐of‐the‐art applications are discussed. With the perspective of their properties and current challenges, we provide an outlook for future directions in this rapidly evolving field to achieve high‐quality LFHP NCs for a broader range of fundamental research and practical applications.     

Synthesis,Crystal Structure,Theoretical Calculation,Specific Heat Capacity,and Thermodynamic Properties of 4,4'-Bis(3-N-methoxyformyl thioureido)-diphenyloxide

4,4′‐Bis(3‐N‐methoxyformyl thioureido)‐diphenyloxide was prepared via reaction of 4,4′‐diaminodiphenyl alter with potassium sulfocyanate and ethyl chloroacetate in ethyl acetate. The single crystal of the title compound was cultured by slow evaporation method at room temperature. The crystal structure was determined with X‐ray diffractometer. It is a monoclinic crystal, space group C2/c with a=0.95911(19) nm, b=0.75922(15) nm, c=2.7161(5) nm, α=90°, β=97.675 (3) °, γ=90°, V=1.9601(7) nm³, Z=4, D_c=1.472 g·cm⁻³, F(000) =904, µ=0.311 cm⁻¹, R₁=0.0367, wR₂=0.1408. The specific heat capacity of the title compound was determined with continuous C_p mode of mircocalorimeter. The thermal behavior of the title compound was studied under a non‐isothermal condition by DSC method.     

Cadmium(II) Complexes with a Bulky Anthracene‐based Carboxylate Ligand: Syntheses,Crystal Structures,and Luminescent Properties

To explore the coordination possibilities of anthracene‐based ligands, three cadmium(ιι) complexes with anthracene‐9‐carboxylate ( L ) and relevant auxiliary chelating or bridging ligands were synthesized and characterized: Cd₂( L )₄(2bpy)₂(μ‐H₂O) ( 1 ), Cd₂( L )₄(phen)₂(μ‐H₂O) ( 2 ), and {[Cd₃( L )₆(4bpy)]}_∞ ( 3 ) (2bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, and 4bpy = 4,4′‐bipyridine). Structural analyses show that complexes 1 and 2 both take dinuclear structures by incorporating the chelating 2bpy or phen ligand, which are further interlinked by intermolecular hydrogen‐bonding, π ··· π stacking, and/or C–H ··· π supramolecular interactions to generate higher‐dimensional supramolecular frameworks. Complex 3 has a one‐dimensional (1D) ribbon‐like structure, which is further assembled into a two‐dimensional (2D) layer, and a three‐dimensional (3D) framework by the co‐effects of interchain C–H ··· O hydrogen‐bonding and C–H ··· π supramolecular interactions. Moreover, the luminescent properties of these complexes were further investigated in detail.     

Metal Ion Induced Assembly of Two Coordination Polymers with Different Topological Nets: Syntheses,Crystal Structures,and Luminescent Properties

The coordination polymers [Zn₂(NDA)(HNDA)₂(IPT)₂]_n ( 1 ) and [Mn(NDA)(IPT)]_n ( 2 ) [H₂NDA = naphthalene‐1,4‐dicarboxylic acid and IPT = 4′‐(4‐(1H‐imidazol‐1‐yl)phenyl)‐4,2′:6′,4′′‐terpyridine] were synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction. Complex 1 features a one‐dimensional ladder‐like chain, whereas complex 2 shows a three‐dimensional CdS topology. The different coordination modes for organic ligands and topological nets for complexes 1 and 2 are mainly related with the metal ions.     

Synthesis,Structure, and Photoluminescence Properties of an Organically‐Templated Uranyl Selenite

The organically‐templated uranyl selenite, (H₂en)[(UO₂)(SeO₃)(HSeO₃)](NO₃) · 0.5H₂O ( 1 ) (en = 1,2‐ethylenediamine) was synthesized and characterized by elemental analyses, IR spectroscopy, TG, and single‐crystal X‐ray diffraction. Compound 1 crystallizes in the orthorhombic system, space group Pbca, with a = 13.170(3) Å, b = 11.055(2) Å, c = 18.009(4) Å, V = 2621.8(9) ų, M = 1316.19, Z = 4, D_cal = 3.334 g · cm^–3, μ(Mo‐K_α) = 17.998 mm^–1, GOF = 1.059, R₁ = 0.0263, wR₂ = 0.0532 [I>2σ(I)]. The X‐ray diffraction analysis reveals that compound 1 has a three‐dimensional (3D) supramolecular structure. It contains negatively charged [UO₂(HSeO₃)(SeO₃)]^– inorganic anion layers and is balanced by [H₂en]²⁺ cations and NO₃^– anions located in the interlayers. Furthermore, the photoluminescence properties of 1 were investigated.     

(Ba6O)(ReN3)2: Synthesis,Crystal Structure and Physical Properties

The reaction of a mixture of barium and rhenium (3:1) at 850 °C under flowing nitrogen yielded the nitride‐oxide (Ba₆O)(ReN₃)₂ (R (No. 148); a = 8.1178(2) Å, c = 17.5651(4) Å; V = 1002.43(5) Å³; Z = 6). According to a structure refinement on X‐ray powder diffraction data, this compound is isostructural to a recently described nitride‐oxide of osmium of analogous composition. The structure consists of sheets of trigonal ReN₃ units and trigonal antiprismatic Ba₆O groups. The Ba–O distance of 2.73 Å is close to the sum of the respective ionic radii. The trigonal ReN₃^5– nitride anion displays a Re–N bond length of 1.94 Å, and is planar within the limits of experimental error. The constitution of the anion was confirmed by IR and Raman spectroscopy. The nitride‐oxide is stable up to 1000 °C, semiconducting (σ = 4.57 × 10^–3 Ω^–1 · cm^–1 at RT), and paramagnetic down to 25 K. A Curie–Weiss analysis resulted in a magnetic moment of μ = 0.68 μ_B per rhenium atom.     

Dimorphic Modification of the Trinuclear Nickel(II) Complex [Ni3(NCS)6(pdz)6]: Synthesis,Crystal Structure,Thermal, Magnetic and Spectroscopic Properties

Reaction of nickel(II) thiocyanate and pyridazine (pdz) as organic spacer ligand leads to the formation of the ligand‐rich 1:2 (1:2 = metal to ligand ratio) trinuclear nickel(II) complex of composition [Ni₃(NCS)₆(pdz)₆]. Depending on the reaction solvent, different polymorphic modifications are obtained: Reaction in acetonitrile leads to the formation of the new modification 1I and reaction in ethanol leads to the formation of modification 1II reported recently. In their crystal structures discrete [Ni₃(NCS)₆(pdz)₆] units are found, in which each of the Ni²⁺ cations exhibits a NiN₆ distorted octahedral arrangement. The central Ni²⁺ cation is coordinated by four bridging pdz ligands and two thiocyanato anions in trans positions. Both thiocyanato anions exhibit the end‐on bridging mode. The peripheral Ni²⁺ cations are bridged by one thiocyanato anion and by two pdz ligands with the central Ni²⁺ cation. Further they are coordinated by two terminal N‐bonded thiocyanato anions and one terminal N‐bonded pdz ligand. The structure of 1I was determined by X‐ray single crystal structure investigation and emphasized by infrared spectroscopy. Magnetic measurements revealed a quasi Curie behavior with net ferromagnetic interactions for 1I and net antiferromagnetic interactions for 1II . Solvent‐mediated conversion experiments clearly show that modification 1I represents the thermodynamic most stable form at room temperature and that modification 1II is metastable. On thermal decomposition, both modification transform quantitatively in a new ligand‐deficient intermediate. Elemental analysis revealed a 3:4 compound of composition [Ni₃(NCS)₆(pdz)₄]. A structure model supported by IR spectroscopic investigations was assumed, in which three coordination modes of the thiocyanato anion exist, resulting in a 2D polymeric network.     

The Synthesis and Crystal Structure of NpSe3

Neptunium triselenide, NpSe₃, was synthesized in high yield by the reaction of the elements in a Sb₂Se₃ flux at 1223 K. Its structure has been determined by single‐crystal X‐ray diffraction methods. Thecompound crystallizes with two formula units in space group C$\rm^{2}_{2h}$ –P2₁/mof the monoclinic system in the TiS₃ structure type with cell constants at 100 K of a = 5.592(3) Å, b = 4.002(2) Å, c = 9.422(5) Å,β = 97.40(1) °. The asymmetric unit comprises one neptunium and three selenium atoms, each with site symmetry m. Np–Se interatomic distances range from 2.859(2) to 2.927(3) Å; the Se–Se bond length of 2.340(3) Å is typical of a single bond. The compound may thus be charge‐balanced and formulated as Np⁴⁺Se^2–Se₂^2–.     

Two Supramolecular Nickel(II) Complexes: Syntheses,Crystal Structures and Solvent Effects

Two nickel(II) complexes, namely {[NiL(MeOH)(μ‐OAc)]₂Ni} · 2CH₂Cl₂ · 2MeOH ( 1 ) and {[NiL(EtOH)(μ‐OAc)]₂Ni} · 2EtOH ( 2 ) {H₂L = 5, 5′‐dimethoxy‐2, 2′‐[(ethylene)dioxybis(nitrilomethylidyne)]diphenol}, were synthesized and structurally characterized. Two trinuclear Ni^II complexes are both hexacoordinate around the central Ni^II atoms, showing octahedral coordination arrangements, and each complex comprises three divalent Ni^II atoms, two deprotonated L^2– ligands, in which four μ‐phenoxo oxygen atoms forming two [NiL(X)] (X = MeOH or EtOH) units, and coordinated and non‐coordinated solvent molecules. Complex 1 exhibits a 2D supramolecular network through intermolecular O–H ··· O, C–H ··· O and C–H ··· π interactions, whereas complex 2 forms an infinite 1D chain by intermolecular C–H ··· O hydrogen bonding interactions.