Molecular and Low‐dimensional Coordination Compounds of Copper(II) and 3, 5‐Dimethylpyrazole — Synthesis,Crystal Structure,and Properties

Three 3, 5‐dimethylpyrazole (pz*) copper(II) complexes, [Cu(pz*)₄(H₂O)](ClO₄)₂ ( 1 ), [Cu(pz*)₂(NCS)₂]·H₂O ( 2 ), and [Cu(pz*)₂(OOCCH=CHCOO)(H₂O)]·1.5H₂O ( 3 ), have been synthesized and characterized with single crystal X‐ray structure analysis. 1 crystallizes in the tetragonal space group, 14/m, with a = 14.027 (3) Å, c = 16.301 (5) Å, and Z = 4. 2 crystallizes in the monoclinic space group, P2₁/c, with a = 8.008 (3) Å, b = 27.139 (9) Å, c = 8.934 (3) Å, β = 106.345 (6)°, and Z = 4. 3 crystallizes in the triclinic space group, P1¯, with a = 7.291 (9) Å, b = 10.891 (13) Å, c = 11.822 (14) Å, α = 80.90 (2)°, β = 79.73(2)°, γ = 70.60(2)°, and Z = 2. In 1 , one water molecule and four pz* ligands are coordinated to Cu^II. Two [Cu(pz*)₄(H₂O)]²⁺ units are connected to ClO₄^— via hydrogen bonds. One lattice water molecule is found in the unit cell of 2 , which forms an one‐dimensional chain via intermolecular hydrogen bonds with the N‐H atom of pz*. In 3 , the oxygen atom of the coordinated water molecule is connected with two C=O groups of two neighbouring maleic acid molecules to form a linear parallelogram structure. Another C=O group of maleic acid forms a hydrogen bond with the N‐H atom of pz* to create a two‐dimensional structure. The spectroscopic and bond properties are also discussed.     

Synthesis,Structure, and Properties of a New Calcium(II) Complex of 1,10‐Phenanthroline, 1,2,4,5‐Benzenetetracarboxylic Acid,and a New Precursor to Produce Pure Phase Micro‐crystalline Calcite Particles

The self‐assembly of 1, 0‐phenanthroline (phen) and 1,2,4,5‐benzenetetracarboxylic acid(H₄btc) with Ca(NO₃)₂ gives rise to a two‐dimensional network structure coordination polymer, [Ca(phen)(btc)_0.5(H₂O)] ( 1 ), which was characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. This compound is monoclinic, space group C2/c, with Z = 8 in a unit cell with dimensions a = 21.744(3) Å, b = 10.0151(12) Å, c = 14.7122(17) Å, β = 110.2850(10)°. The structure contains one crystallographic unique Ca^II atom, one phen coordinated molecule and a half of btc^4– anion. The phen molecule acts as a didentate ligand chelating with a Ca^II atom, whereas the btc^4– anion acts as a μ₆‐bridge linking six different Ca^II atoms to form a two‐dimensional network with (4, 4) topological structure. The three dimensional stacking structures are formed by C–H ··· O hydrogen bonding and π–π interaction. The thermal stability and fluorescent properties of 1 were investigated. Calcite particles are produced by calcination of compound 1 at 580 °C. The obtained calcite was characterized by XRD and SEM analyses.     

Inorganic−Organic Hybrid Polymers via Hydrothermal Syntheses: Tetraaquahexakis(pyrazine‐2‐carboxylato)pentacopper(4+) Hexacosaoxooctamolybdate(4−) Polymer ({[Cu5(pzca)6(H2O)4][Mo8O26]}n; pzca=Pyrazine‐2‐carboxylate) and Dicopperdecaoxo(pyrazine)trimolybdenum Polymer ([Mo3Cu2O10(pz)]n; pz=pyrazine)

Hydrothermal reactions of MoO₃, CuO, and pyrazine‐2‐carboxylic acid (Hpzca) resulted in two polymeric complexes, {[Cu₅(pzca)₆(H₂O)₄][Mo₈O₂₆]}_n ( 1 ; pzca=pyrazine‐2‐carboxylate) and [Mo₃Cu₂O₁₀(pz)]_n ( 2 ; pz=pyrazine). The former crystallized in the monoclinic space group P2₁/c with a=10.805(3) Å, b=13.061(5) Å, c=13.337(10) Å, β=90.20(4)°, V=2729(2) ų, and Z=2. The later crystallized in the orthorhombic space group Pnma with a=12.385(2) Å, b=7.6044(9) Å, c=12.7880(14) Å, V=1204.4(2) ų, and Z=4. X‐Ray diffraction analysis revealed that 1 possesses a two‐dimensional wave‐like structure, formed from a zigzag one‐dimensional chain, and 2 is a three‐dimensional network structure formed from a one‐dimensional chain and a pz bridging ligand. The temperature‐dependent magnetic behavior of 1 was studied.     

Supramolecular Assemblies of Mononuclear and Polymeric Nickel(II) Glutarato Complexes via π‐π Stacking Interactions and Hydrogen Bonds: [Ni(H2O)3(phen)(C5H6O4)] · H2O and [Ni(H2O)2(phen)(C5H6O4)]

Syntheses of the sky blue complex compounds [Ni(H₂O)₃(phen)(C₅H₆O₄)] · H₂O ( 1 ) and [Ni(H₂O)₂(phen)(C₅H₆O₄)] ( 2 ) were carried out by the reactions of 1,10‐phenanthroline monohydrate, glutaric acid, NiSO₄ · 6 H₂O and Na₂CO₃ in CH₃OH/H₂O at pH = 6.9 and 7.5, respectively. The crystal structure of 1 (P 1 (no. 2), a = 14.289 Å, b = 15.182 Å, c = 15.913 Å, α = 67.108°, β = 87.27°, γ = 68.216°, V = 2934.2 ų, Z = 2) consists of hydrogen bonded [Ni(H₂O)₃‐ (phen)(C₅H₆O₄)]₂ dimers and H₂O molecules. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, three water O atoms and one carboxyl O atom from one monodentate glutarato ligand (d(Ni–N) = 2.086, 2.090 Å; d(Ni–O) = 2.064–2.079 Å). Through the π‐π stacking interactions and intermolecular hydrogen bonds, the dimers are assembled to form 2 D layers parallel to (0 1 1). The crystal structure of 2 (P2₁/n (no. 14), a = 7.574 Å, b = 11.938 Å, c = 18.817 Å, β = 98.48°, V = 1682.8 ų, Z = 4) contains [Ni(H₂O)₂(phen)(C₅H₆O₄)_2/2] supramolecular chains extending along [010]. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, two water O atoms and two carboxyl O atoms from different bis‐monodentate glutarato ligands with d(Ni–N) = 2.082, 2.105 Å and d(Ni–O) = 2.059–2.087 Å. The supramolecular chains are assembled into a 3 D network by π‐π stacking interactions and interchain hydrogen bonds. A TG/DTA of 2 shows two endothermic effects at 132 °C and 390 °C corresponding to the complete dehydration and the lost of phen.     

catena‐Poly[[[pentaaquathulium(III)]‐μ‐5‐sulfonatobenzene‐1,3‐dicarboxylato] 4,4′‐bipyridyl 1.5‐solvate hemihydrate]

The crystal structure of the title compound, {[Tm(C₈H₃O₇S)(H₂O)₅]·1.5C₁₀H₈N₂·0.5H₂O}_n, is built up from two [Tm(SIP)(H₂O)₅] molecules (SIP³⁻ is 5‐sulfonatobenzene‐1,3‐dicarboxylate), three 4,4′‐bipyridyl (bpy) molecules and one solvent water molecule. One of the bpy molecules and the solvent water molecule are located on an inversion centre and a twofold rotation axis, respectively. The Tm^III ion coordination is composed of four carboxylate O atoms from two trianionic SIP³⁻ ligands and five coordinated water molecules. The Tm³⁺ ions are linked by the SIP³⁻ ligands to form a one‐dimensional zigzag chain propagating along the c axis. The chains are linked by interchain O—H...O hydrogen bonds to generate a two‐dimensional layered structure. The bpy molecules are not involved in coordination but are linked by O—H...N hydrogen bonds to form two‐dimensional layers. The two‐dimensional layers are further bridged by the bpy molecules as pillars and the solvent water molecules through hydrogen bonds, giving a three‐dimensional supramolecular structure. π–π stacking interactions between the parallel aromatic rings, arranged in an offset fashion with a face‐to‐face distance of 3.566 (1) Å, are observed in the crystal packing.     

Synthesis and Structure of a New Vanadium(IV)‐Cadmium(II) Compound with the Nitrilotriacetate Ligand: {(NH4)2[(VIVO)2(μ2‐O)(nta)2Cd(H2O)2]·H2O}n

A polymeric V^IV‐Cd compound, {(NH₄)₂[(V^IVO)₂(μ₂‐O)(nta)₂Cd(H₂O)₂]·H₂O}_n (H₃nta = nitrilotriacetic acid), has been prepared and characterized by single‐crystal X‐ray diffraction. The compound crystallizes in the monoclinic space group C2/c with a = 17.3760(2) Å, b = 8.0488(1) Å, c = 17.3380(2) Å, β = 107.9690(10)°, V = 2306.55(5) ų, Z = 4, and R₁ = 0.0303 for 1958 observed reflections. The structure exhibits a heterometallic three‐dimensional network formed by polymeric [(V^IVO)₂(μ₂‐O)(nta)₂Cd(H₂O)₂]^2? anions.     

Crystal Structure and Thermal Behaviour of the Mixed‐Valent Basic Mercury Nitrate HgI2(OH)(NO3)·HgIIO

Single crystals of the hitherto unknown compound Hg₂(OH)(NO₃)·HgO were obtained unintentionally during hydrothermal phase formation experiments in the system Ag—Hg— As—O. Hg₂(OH)(NO₃)·HgO (orthorhombic, Pbca, Z = 8, a = 6.4352(8), b = 11.3609(14), c = 15.958(2) Å, 1693 structure factors, 83 parameters, R1[F² > 2σ(F²)] = 0.0431) adopts a new structure type and is composed of two types of mercury‐oxygen zig‐zag‐chains running perpendicular to each other and of intermediate nitrate groups. One type of chains runs parallel [010] and consists of (Hg—Hg—OH) units with a typical Hg—Hg distance of 2.5143(10) Å for the mercury dumbbell, whereas the other type of chains runs parallel [100] and is made up of (O—Hg—O) units with short Hg—O distances of about 2.02Å. Both types of chains are concatenated by a common O atom with a slightly longer Hg—O distance of 2.25Å. The three‐dimensional assembly is completed by nitrate groups whose O atoms show Hg—O distances > 2.80Å. Weak hydrogen bonding between the OH group and one oxygen atom belonging to the nitrate group stabilizes this arrangement. Hg₂(OH)(NO₃)·HgO decomposes above 200 °C to HgO.     

一个新颖的由Zn配合物修饰的Keggin型钴钨酸盐：[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O

通过水热合成技术,一个新颖的基于Zn配合物修饰的Keggin型钴钨酸的有机-无机杂化化合物：[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O已经被合成,化合物通过红外光谱、热重分析和单晶X-射线衍射进行了表征。单晶X-射线衍射的结果显示标题化合物是由一个单支撑的{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2}6-多阴离子,三个[Zn(2,2’-bipy)3]2+阳离子和一个水分子构成。有趣的是[Zn(1)(2,2’-bipy)3]2+阳离子通过氢键连接在一起形成螺旋链。另外标题化合物在空气中是稳定的,并且在室温下显示了强的荧光。     

A Two-coordinate Copper(I) Complex Constructed from Cyanuric acid and 4,4′-bipyridyl: Synthesis, Structure and Photoluminescence

A two-coordinate copper（Ⅰ） complex, Cu2（bipy）（H2L）2 （1） （H3L=cyanuric acid, bipy=4,4＇-bipyridyl）, which exhibits strong photoluminescence, has been synthesized under hydrothermal conditions and structurally characterized by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P21/n, with cell parameters： Mr= 539.42, a= 13.4806（5）A↑°, b=4.5234（2） A↑°, c= 15.4952（8）A↑°,β = 105.526（3）°, V=910.39（7）A↑°^3, Z=2 and μ=3.52 mm^ -1. In the structure the two Cu（Ⅰ） ions are bridged by bipy to form a two-coordinate copper（Ⅰ） dimer. The adjacent dimer units are connected by hydrogen bonding interactions, resulting in 1D zigzag chains along the c axis. 1 emits intense yellow light when excited with UV light.     

Synthesis,Spectrothermal Behaviour and Molecular Structure of Aquaorotatotriethanolaminenickel(II) Monohydrate

The aquaorotatotriethanolaminenickel(II) monohydrate, [Ni(HOr)(H₂O)(tea)]·H₂O ( 1 ), was synthesized and characterized by means of elementel analysis, IR and UV‐Vis, spectroscopy, magnetic susceptibility, thermal analysis and X‐ray diffraction techniques. The nickel ion in [Ni(C₅H₂N₂O₄)(H₂O)(N(C₂H₄OH)₃)] is chelated to the deprotonated N3 pyrimidine atom and to the carboxylate oxygen atom of the bidentate orotate dianion, and to the one nitrogen and two oxygen atoms of the tridentate triethanolamine molecule and its octahedral geometry is completed by an aqua ligand. It crystallizes in the monoclinic system, space group P2₁/c with lattice parameters a = 7.1528(5) Å, b = 19.4903(14) Å, c = 11.8085(8) Å, β = 106.237(5)°, V = 1580.55(19) ų, Z = 4. An extensive three dimensional network of O_w‐H…O, N‐H…O and O‐H…O hydrogen bonds, π‐π and π‐ring interactions are responsible for crystal stabilization. The decomposition reaction take places in the temperature range 20‐1000 °C in the static air atmosphere. Thermal decomposition of 1 proceeds in three stages.     

catena‐Poly­[[(di‐2‐pyridyl­amine)­silver(I)]‐μ‐nicotinato] and catena‐poly­[[(di‐2‐pyridyl­amine)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato]

In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐nico­tinato‐κ²N:O], [Ag(C₆H₄NO₂)(C₁₀H₉N₃)]_n, the Ag^I atom is tetracoordinated by two N atoms from the di‐2‐pyridyl­amine (BPA) ligand [Ag—N = 2.3785 (18) and 2.3298 (18) Å] and by one N atom and one carboxyl­ate O atom from nicotinate ligands [Ag—N = 2.2827 (15) Å and Ag—O = 2.3636 (14) Å]. Bridging by nicotinate N and O atoms generates a polymeric chain structure, which extends along [100]. The carboxyl O atom not bonded to the Ag atom takes part in an intrachain C—H⋯O hydrogen bond, further stabilizing the chain. Pairs of chains are linked by N—H⋯O hydrogen bonds to generate ribbons. There are no π–π interactions in this complex. In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato‐κ²O¹:O²], [Ag(C₇H₅O₄)(C₁₀H₉N₃)]_n, the Ag^I atom has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand [Ag—N = 2.286 (5) and 2.320 (5) Å] and to one carboxyl­ate O atom from the 2,6‐di­hydroxy­benzoate ligand [Ag—O = 2.222 (4) Å]; the fourth, weaker, Ag‐atom coordination is to one of the phenol O atoms [Ag⋯O = 2.703 (4) Å] of an adjacent moiety, and this interaction generates a polymeric chain along [100]. Pairs of chains are linked about inversion centers by N—H⋯O hydrogen bonds to form ribbons, within which there are π–π interactions. The ribbons are linked about inversion centers by pairs of C—H⋯O hydrogen bonds and additional π–π interactions between inversion‐related pairs of 2,6‐di­hydroxy­benzoate ligands to generate a three‐dimensional network.     

Synthesis and Crystal Structure of [(1‐(Phenyltriazenido)‐2‐(phenyltriazeno)benzene)(nitrato)mercury(II)], {Hg[PhN3C6H4N3(H)Ph](NO3)}, a Complex with Weak Metal‐Arene π‐Interactions

The reaction of PhN₃(H)C₆H₄N₃(H)Ph with Hg(NO₃)₂ in THF in the presence of triethylamine yields {Hg[PhN₃C₆H₄N₃(H)Ph](NO₃)} as a yellow powder that can be recrystallized from THF/acetone. The crystals belong to the monoclinic system, space group P2₁ with the cell dimensions a = 9.639(2), b = 5.412(1), c = 19.675(4) Å, β= 97.47(3)°, V = 1017.7 (4) ų, Z = 2. The crystal structure determination (2668 unique reflections with [I>2σ(I)], 262 parameters, R₁ = 0.0393) shows that the structure consists of mononuclear complexes. Hg atoms are linearly coordinated by one N_α atom of the triazenide unit of the planar ligand [Hg‐N(1) = 2.101(8) Å] and an O atom of the NO₃^— ion [Hg‐O(1) = 2.11(1) Å]. Additional weak Hg‐N contacts [Hg‐N(4) = 2.662(9) and Hg‐N(3) = 2.851(9) Å] and an intramolecular hydrogen bond between the triazenide hydrogen and an O atom of the nitrate group are observed [N(6)‐H(6)···O(2) = 2.92(2) Å]. The complexes are stacked to infinite chains by metal‐arene π‐interactions. Each Hg atom is coordinated by the terminal phenyl rings of two neighboring complexes [Hg‐C from 3.40(1) to 4.10(1) Å] in a η² fashion.     

Synthesis,Crystal Structure,and Magnetic Properties of {[Cu(phen)]2(C4H2O4)2} · 4.5H2O with C4H4O4 = Maleic Acid

Reaction of CuCl₂ · 2H₂O, phenanthroline, maleic acid and NaOH in CH₃OH/H₂O (1:1 v/v) at pH = 7.0 yielded blue {[Cu(phen)]₂(C₄H₂O₄)₂} · 4.5H₂O, which crystallizes in the monoclinic space group C2/c (no. 15) with cell dimensions: a = 18.127(2)Å, b = 12.482(2)Å, c = 14.602(2)Å, β = 103.43(1)°, U = 3213.5(8)ų, Z = 4. The crystal structure consists of the centrosymmetric dinuclear {[Cu(phen)]₂(C₄H₂O₄)₂} complex molecules and hydrogen bonded H₂O molecules. The Cu atoms are each square‐pyramidally coordinated by two N atoms of one phen ligand and three carboxyl O atoms of two maleato ligands with one carboxyl O atom at the apical position (d(Cu‐N) = 2.008, 2.012Å, equatorial d(Cu‐O) = 1.933, 1.969Å, axial d(Cu‐O) = 2.306Å). Two square‐pyramids are condensed via two apical carboxyl O atoms with a relatively larger Cu···Cu separation of 3.346(1)Å. The dinuclear complex molecules are assembled via the intermolecular π—π stacking interactions into 1D ribbons. Crossover of the resulting ribbons via interribbon π—π stacking interactions forms a 3D network with the tunnels occupied by H₂O molecules. The title complex behaves paramagnetically between 5—300 K, following the Curie‐Weiss law _χm(T—θ) = 0.435 cm³ · mol^—1 · K with θ = 1.59 K.     

Synthesis,Crystal Structures and Electrochemical Properties of Complexes [M(ImH)4(tfbdc)(H2O)] (M=Co,Ni)

The title complexes [M(ImH)₄(tfbdc)(H₂O)] ( 1 : M=Co; 2 : M=Ni) (ImH=imidazole, tfbdc=2,3,5,6‐tetrafluoroterephthalate) were synthesized by the reaction of M(OAc)₂·4H₂O, H₂tfbdc and ImH in water solution. The complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, cyclic voltammetry and X‐ray single crystal structure analysis. Structural analysis reveals that 1 and 2 possess isostructure: monoclinic, P2₁/c, Z=4. M(II) ion in complexes 1 and 2 has a distorted octahedral geometry coordinated by one oxygen atom from water, one oxygen atom from tfbdc^2? and four nitrogen atoms from ImHs. They are discrete zero‐dimensional molecular complexes. And the adjacent monomeric components are connected by hydrogen bonds to form a supramolecule. Electrochemical properties of the complexes 1 and 2 show that electron transfer of M(II) between M(III) in electrolysis is a quasi‐reversible process.     

Synthesis,crystal structure and magnetic properties of Co(NIT4Py)(H2PDA)(H2O)3

A Co(II)-pyridyl substituted nitronyl nitroxide complex Co(NIT4Py)(H₂PDA)(H₂O)₃ has been synthesized and structurally characterized (NIT4Py: 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and H₂PDA: 2,5-pyridine dicarboxylic acid). The compound is in the monoclinic space group P2(1)/c, a = 16.892(5) Å, b = 7.371(2) Å, c = 18.856(5) Å, β = 108.770(5)°, V = 2223.0(11) ų, Z = 4 and F(000) = 1064. The cobalt is in a distorted octahedral environment with one nitrogen from NIT4Py, one oxygen atom from H₂PDA, two oxygens from two water molecules in the basal plane and one nitrogen from H₂PDA and one water in the axial positions. The molecules are connected as a layered structure by intermolecular hydrogen bond interactions. Variable temperature magnetic susceptibility measurements reveal the occurrence of weak antiferromagnetic interactions in the compound.     

Two Glutarato Bridged Coordination Polymers: ${_{\infty}^1}${[Mn(phen)]2L4/2} and ${_{\infty}^1}${[Zn(phen)(H2O)]L2/2}·H2O with H2L = Glutaric Acid

Two new glutarato bridged coordination polymers {[Mn(phen)]₂(C₅H₆O₄)_4/2} ( 1 ) and {[Zn(phen)(H₂O)](C₅H₆O₄)_2/2}· H₂O ( 2 ) were structurally characterized on the basis of single crystal X‐ray diffraction data. Crystal data: ( 1 ) P2/c (no. 13), a = 10.340(2)Å, b = 10.525(2)Å, c = 13.891(2)Å, β = 98.31(1)°, U = 1495.9(5)ų, Z = 2; ( 2 ) P2₁/n (no. 14), a = 6.738(1)Å, b = 25.636(3)Å, c = 10.374(1)Å, β = 106.13(1)°, U = 1721.4(4)ų, Z = 4. Complex 1 consists of 1D ribbon‐like {[Mn(phen)]₂(C₅H₆O₄)_4/2} chains, in which the [Mn(phen)] units were interlinked by glutarato ligands to generate 8‐ and 16‐membered rings. The Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms of three glutarato ligands with d(Mn‐N) = 2.270, 2.276Å, d(Mn‐O) = 2.114—2.283Å. Through the interchain π‐π stacking interactions, the 1D chains are assembled into 2D puckered layers, which are further held together by interlayer π‐π stacking interactions into a 3D network. Complex 2 is built up by 1D {[Zn(phen)(H₂O)](C₅H₆O₄)_2/2} linear chains and hydrogen bonded H₂O molecules. The Zn atoms are coordinated by two N atoms of one phen ligand and three O atoms of one H₂O molecule and two glutarato ligands to form slightly elongated trigonal bipyramids with the water O atom and one phen N atom at the apical positions (d(Zn‐N) = 2.101, 2.168Å, d(Zn‐O) = 1.991—2.170Å). The 1D linear chains result from [Zn(phen)(H₂O)] units bridged by bis‐monodentate glutarato ligands. The resulting 1D chains are assembled by π‐π stacking interactions into 2D layers, between which the hydrogen bonded H₂O molecules are situated.     

Z and E isomers of butenedioic acid with 2‐amino‐1,3‐thiazole: 2‐amino‐1,3‐thiazolium hydrogen maleate and 2‐amino‐1,3‐thiazolium hydrogen fumarate

Maleic acid and fumaric acid, the Z and E isomers of butenedioic acid, form 1:1 adducts with 2‐amino‐1,3‐thiazole, namely 2‐amino‐1,3‐thiazolium hydrogen maleate (2ATHM), C₃H₅N₂S⁺·C₄H₃O₄⁻, and 2‐amino‐1,3‐thiazolium hydrogen fumarate (2ATHF), C₃H₅N₂S⁺·C₄H₃O₄⁻, respectively. In both compounds, protonation of the ring N atom of the 2‐amino‐1,3‐thiazole and deprotonation of one of the carboxyl groups are observed. The asymmetric unit of 2ATHF contains three independent ion pairs. The hydrogen maleate ion of 2ATHM shows a short intramolecular O—H...O hydrogen bond with an O...O distance of 2.4663 (19) Å. An extensive hydrogen‐bonded network is observed in both compounds, involving N—H...O and O—H...O hydrogen bonds. 2ATHM forms two‐dimensional sheets parallel to the ab plane, extending as independent parallel sheets along the c axis, whereas 2ATHF forms two‐dimensional zigzag layers parallel to the bc plane, extending as independent parallel layers along the a axis.     

Adipato‐Bridged Mixed Ligand catena Complexes: ${_{\infty}^1}${[M(phen)(H2O)]L2/2} with M = NiII,CuII, ZnII; H2L = Adipic Acid

Three adipato bridged mixed ligand catena complexes {[M(phen)(H₂O)]‐(C₆H₈O₄)_2/2} with M = Ni^II ( 1 ), Cu^II ( 2 ), Zn^II ( 3 ) were synthesized. Structure determination based on X‐ray diffraction shows that they crystallize isostructurally in the monoclinic space group C2/c (no. 15) with cell dimensions of: 1 a = 22.451(4)Å, b = 9.041(1)Å, c = 17.440(2)Å, β = 103.41(1)°, U = 3443.4(9)ų, Z = 8; 2 a = 22.479(2)Å, b = 9.067(1)Å, c = 17.494(3)Å, β = 103.67(1)°, U = 3464.6(8)ų, Z = 8; 3 a = 22.635(3)Å, b = 9.052(1)Å, c = 17.571(3)Å, β = 103.24(1)°, U = 3504.5(9)ų, Z = 8. The crystal structure consists of 1D {[M(phen)(H₂O)]‐(C₆H₈O₄)_2/2} zigzag chains, in which the metal atoms are all octahedrally coordinated by two N atoms of one phen ligands and four O atoms of one H₂O molecule and two adipato ligands. The zigzag chains are held together by interchain π‐π stacking interactions and interchain hydrogen bonds.     

Neodymium(III) triaquatrihydroxo(1,3-diamino-2-propanoltetraacetato)germanium(IV) hydrate [Ge(OH)(μ-HHpdta)(μ-OH)Nd(OH)(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>] · H<Subscript>2</Subscript>O: Synthesis and crystal and molecular structure

The heteronuclear germanium(IV) and neodymium(III) complex with 1,3-diamino-2-propanoltetraacetic acid (H₅Hpdta) [Ge(OH)(μ-HHpdta)(μ-OH)Nd(OH)(H₂O)₃] · H₂O has been synthesized for the first time and characterized by physicochemical methods (elemental analysis, X-ray powder diffraction, thermogravimetry, IR spectroscopy, X-ray crystallography). The crystals are monoclinic: a = 9.331(3) Å, b= 10.279(4) Å, c = 21.474(7) Å, β = 94.59(3)°, V = 2053.0(12) ų, Z = 4, space group P2₁/n, R1 = 0.0245 for 4060 reflections with I > 2σ(I). The compound is built of complex binuclear molecules [Ge(OH)(μ-HHpdta)(μ-OH)Nd(OH)(H₂O)₃] and water molecules of crystallization. The germanium and neodymium atoms are bridged by the oxygen atom of the hydroxo group (Ge-O, 1.798(2) Å; Nd-O, 2.539(2) Å) and the deprotonated oxygen atom of the isopropanol group of the HHpdta^4? ligand (Fe-O, 1.858(2)Å; Nd-O, 2.420(2) Å) to form a dimeric molecule. Each coordination sphere (of the Ge atom and of the Nd atom) contains one nitrogen atom (Ge-N, 2.096(3) Å; Nd-N, 2.807(2) Å) and two carboxylic oxygen atoms from four acetate branches of the octadentate HHpdta^4? ligand (av. Ge-O, 1.928(2) Å; Nd-O, 2.391(2) Å). The coordination polyhedron of the Ge atom is completed to a distorted octahedron by the oxygen atom of the terminal hydroxo group (Ge-O 1.811(2) Å), and the polyhedron of the Nd atom is completed to a nine-vertex polyhedron by the oxygen atoms of the terminal hydroxo group (Nd-O 2.494(3) Å) and three water molecules (Nd-O, 2.512(3), 2.520(3), and 2.723(3) Å). In the crystal structure, the complex molecules and the water molecules of crystallization are joined by a hydrogen bond system.     

Syntheses,Crystal Structures,and Thermal Behavior of Co(phen)(HL)2 and [Co2(phen)2(H2O)4L2]·H2O with H2L = Pimelic Acid

Two Co^II complexes, Co(phen)(HL)₂ ( 1 ) and [Co₂(phen)₂(H₂O)₄L₂]·H₂O ( 2 ) (H₂L = HOOC‐(CH₂)₅‐COOH), were synthesized and structurally characterized on the basis of single crystal X‐ray diffraction data. In complex 1 the Co atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different hydrogenpimelato ligands. Through π—π stacking interactions between carboxyl group and phen ligand, the complex molecules are assembled into 1D columnar chains, which are connected by intermolecular hydrogen bonds. Complex 2 consists of the centrosymmetric dinuclear [Co₂(phen)₂(H₂O)₄L₂] molecules and hydrogen bonded H₂O molecules. The Co atoms are each octahedrally surrounded by two N atoms of one phen ligand and four O atoms from two bis‐monodentate pimelato ligands and two H₂O molecules at the trans positions. The results about thermal analyses, which were performed in flowing N₂ atmosphere, on both complexes were discussed. Crystal data: ( 1 ) C2/c (no. 15), a = 13.491(1)Å, b = 9.828(1)Å, c = 19.392(2)Å, β = 100.648(1)°, U = 2526.9(4)ų, Z = 4; ( 2 ) P1 (no. 2), a = 11.558(1)Å, b = 11.947(3)Å, c = 15.211(1)Å, α = 86.17(1)°, β = 75.55(1)°, γ = 69.95(1)°, U = 1910.3(3)ų, Z = 2.