吡啶配位的夹心型杂多阴离子{[Na(H2O)2]3[Ni(C5H5N)]3(AsW9O33)2}9-的结构及磁学性质

The pyridine coordinated sandwich-type heteropolytungstate Na7[Ni（H2O）6] { [Na（H2O）2]3[Ni（C5H5N）]3（AsW9O33）2}·28H2O was obtained by the reaction of Na2WO4·2H2O, NaAsO2 and pyridine with NiCl2·6H2O at pH =7.0 and characterized by elemental analysis, IR, UV-Vis,^1H NMR spectra and magnetic measurement. The structure of this heteropolytungstate was determined by X-ray diffraction analysis, which crystallized in triclinic system, space group P1 with a= 1.3153（9） nm, b= 1.7228（12） nm, c=2.6866（19） nm, a=74.130（11）°,β=78.032（12）°, γ = 73.179（12）° and Z= 2, R1 = 0.0604, wR2 = 0.0915 [I〉 2σ（I）]. Polyanion {[Na（H2O）2]3[Ni（C5H5N）]3（AsW9O33）2}^9- has approximately C3 symmetry, and three pyridine coordinated Ni（C5H5N）^2＋ and three Na（H2O）2^＋ are encapsulated between two AsW9O33^9- . Magnetic measurements show that central Ni3 unit in the polyanion exhibits ferromagnetic Ni-Ni exchange interactions （J=6.17 cm^-1）.     

Synthesis,Crystal Structure and Magnetic Property of Sanwich‐Type Heteropolyoxometalate Na9[(Na(H2O),}3{Cu(H20)}3(BiW9O33)2] 42H2O

The heteropolytungstate Na₉[{Na(H₂O)₂}₃{Cu(H₂O)}₃(BiW₉O₃₃) 42H₂O is obtained by the reaction of Na₂WO₄·2H₂O, Bi(NO₃)₃ · 5H₂O with CuCl₂ · 2H₂O at pH≠6. The structure and chemical composition are determined by X‐ray diffraction analysis and elemental analysis. The crystal data and main structure refinement are: a = 1.410(3) nm, b=2.338(5) nm, c=3.173(6) nm, β=98.06(4)°. V= 10.354(35) nm³. monoclinic crystal system, space group: C2/c, Z = 4, R₁= 0.0471. wR₂ = 0.0642 I>2σ(I)]. R₁= 0.1371, wR₂ = 0.0868 (all data). [(Na(H₂O)₂}₃{Cu(H₂O)}₃W₉O₃₃)₂]^9– has D₃₄ symmetry. IR, UV‐vis spectra, TG curve and magnetic property of the complex were also discussed. The compound exhibits an antiferromagnetic coupling with J= ‐8.08 cm^?1 and g =2.21.     

Two Heteroleptic Zinc(II) Complexes: [Zn(phen)(C9H15O6)2] and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O

Reactions of a freshly prepared Zn(OH)_2‐2x(CO₃)x · yH₂O precipitate, phenanthroline with azelaic and sebacic acid in CH₃OH/H₂O afforded [Zn(phen)(C₉H₁₅O₄)₂] ( 1 ) and [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] · 3H₂O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C₉H₁₅O₄)₂] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C₉H₁₅O₄)₂] complexes. Compound 2 is built up from crystal H₂O molecules and the centrosymmetric binuclear [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] complex, in which two [Zn(phen)(H₂O)]²⁺ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H₂O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)ų, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)ų, Z = 1.     

[M(en)3] (ndt)•H2O的水热合成、晶体结构和光学性能 ( M=NiⅡ, CoⅡ, MnⅡ and ndt=1,5-naphthalenedithiolate )

水热条件下，合成了三个新的配合物[Ni(en)₃] (ndt) ·H₂O 1, [Co(en)₃] (ndt) ·H₂O 2 和[Mn(en)₃] (ndt) ·H₂O 3。晶体结构通过X-射线单晶衍射进行了表征。三个配合物均属于单斜晶系，Cc空间群。[M(en)₃]²⁺阳离子、ndt阴离子和结晶水分子通过氢键自组装出相同结构的三维网。通过紫外-可见-近红外漫反射光谱对这三个配合物的光吸收性能和能带进行了测定。     

Koordinationspolymere 1, 2‐Dithiooxalato‐ und 1, 2‐Dithioquadratato‐Komplexe. Synthese und Strukturen von [BaCr2(bipy)2(1, 2‐dtox)4(H2O)2], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)2(H2O)2]·2H2O und [H3O][H5O2][Cu(cyclam)]3[Cu2(1, 2‐dtsq)3]2

Coordination Polymeric 1, 2‐Dithiooxalato and 1, 2‐Dithiosquarato Complexes. Syntheses and Structures of [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H2₂, and [H₃O][H₅O₂][Cu(cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ 1, 2‐Dithioxalate and 1, 2‐dithiosquarate ions have a pair of soft and hard donor centers and thus are suited for the formation of coordination polymeric complexes containing soft and hard metal ions. The structures of four compounds with building blocks containing these ligands are reported: In [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂] Barium ions and pairs of Cr(bipy)(1, 2‐dtox)₂ complexes form linear chains by the bisbidentate coordination of the dithiooxalate ligands towards Ba²⁺ and Cr³⁺. In [Ni(cyclam)(1, 2‐dtsq)]·2DMF short NÖH···O hydrogen bonds link the NiS₂N₄‐octahedra with C_2v‐symmetry to an infinite chain. In [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H₂O the 1, 2‐dithiosquarato ligand shows a rare example of S‐coordination towards manganese(II). The sulfur atoms of cis‐MnO₂S₄‐polyedra are weakly coordinated towards the axial sites of square‐planar NiN₄‐centers, thus forming a zig‐zag‐chain of Mn···Ni···Mn···Ni polyhedra. [H₃O][H₅O₂][Cu (cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ contains square planar [Cu^II(cyclam)]²⁺ ions and dinuclear [Cu^I₂(1, 2‐dtsq)₃]^4— ions. Here each copper atom is trigonally planar coordinated by S‐donor atoms of the ligands. The Cu…Cu distance is 2.861(4)Å.     

Kristallstruktur von Natrium‐Dihydrogencyamelurat‐Tetrahydrat Na[H2(C6N7)O3] · 4 H2O

Crystal Structure of Sodium Dihydrogencyamelurate Tetrahydrate Na[H₂(C₆N₇)O₃] · 4 H₂O Sodium dihydrogencyamelurate‐tetrahydrate Na[H₂(C₆N₇)O₃]·4 H₂O was obtained by neutralisation of an aqueous solution, previously prepared by hydrolysis of the polymer melon with sodium hydroxide. The crystal structure was solved by single‐crystal X‐ray diffraction ( a = 6.6345(13), b = 8.7107(17), c = 11.632(2) Å, α = 68.96(3), β = 87.57(3), γ = 68.24(3)°, V = 579.5(2) ų, Z = 2, R1 = 0.0535, 2095 observed reflections, 230 parameters). Both hydrogen atoms of the dihydrogencyamelurate anion are directly bound to nitrogen atoms of the cyameluric nucleus, thus proving the preference of the keto‐tautomere in salts of cyameluric acid in the solid‐state. The compound forms a layer‐like structure with an extensive hydrogen bonding network.     

mer‐Di­aqua­bis(1H‐imidazole‐κN3)(orotato‐κ2N3,O4)­nickel(II)

The title mononuclear complex, [Ni(C₅H₂N₂O₄)(C₃H₄N₂)₂(H₂O)₂] or [Ni(HOr)(im)₂(H₂O)₂] (im is imidazole and H₃Or is orotic acid, or 2,6‐dioxo‐1,2,3,6‐tetra­hydro­pyrimidine‐4‐carboxylic acid), has been synthesized and the crystal structure determination is reported. The Ni^II ion in the complex has a distorted octahedral coordination geometry comprised of one deprotonated pyrimidine N atom and the adjacent carboxyl­ate O atom of the orotate ligand, two tertiary imidazole N atoms and two aqua ligands. An extensive three‐dimensional network of OW—H⋯O and N—H⋯O hydrogen bonds, and π–π and π–ring interactions are responsible for crystal stabilization.     

Neue Heteropolyanionen des M2X2W20‐Typs mit Antimon(III) als Heteroatom

New Heteropolyanions of the M₂X₂W₂₀ Structure Type with Antimony(III) as a Heteroatom The syntheses of two new heteropolyanions of the M₂X₂W₂₀ structure type are presented. They are characterized by X‐ray structure analysis and vibrational spectra. Na₆(NH₄)₄[Zn₂(H₂O)₆(WO₂)₂(SbW₉O₃₃)₂]·36H₂O (1) is monoclinic (P2₁/n) with a = 12.873(3)Å, b = 25.303(4)Å, c = 15.975(4)Å and β = 91.99(3)°. Na₁₀[Mn₂(H₂O)₆(WO₂)₂(SbW₉O₃₃)₂]·40H₂O (2) also crystallizes in the space group P2₁/n with a = 12.892(3)Å, b = 25.219(5)Å, c = 16.166(3)Å and β = 94.41(3)°. Both polyanions are isostructural to anions of this structure type containing other heteroatoms. They are built up by two β‐B‐SbW₉ fragments, which are derived from defect structures of the Keggin anion. These subÍunits are connected by two formal WO₂ groups with further stabilization by addition of two M(H₂O)₃ groups (M = Zn^II, Mn^II, Fe^III, Co^II) leading to the M₂X₂W₂₀‐type heteropolytungstates.     

(Acetato‐κO)aqua(1H‐imidazole‐κN3)(picolinato‐κ2N,O)copper(II) 0.87‐hydrate: a Z′> 1 structure

The crystal structure of the title compound, [Cu(C₆H₄NO₂)(C₂H₃O₂)(C₃H₄N₂)(H₂O)]·0.87H₂O, has a square‐pyramidal‐coordinated Cu^II centre (the imidazole is trans to the picolinate N atom, the acetate is trans to the picolinate –CO₂ group and the aqua ligand is in a Jahn–Teller‐elongated apical position) and has two symmetry‐independent molecules in the unit cell (Z′ = 2), which are connected through complementary imidazole–picolinate N—H...O hydrogen bonding. The two partially occupied solvent water molecules are each disordered over two positions. The disordered solvent water molecules, together with pseudosymmetry elements, support the notion that a crystal structure with multiple identical chemical formula units in the structural asymmetric unit (Z′ > 1) can represent a crystal `on the way', that is, a kinetic intermediate form which has not yet reached its thermodynamic minimum. Neighbouring molecules form π–π stacks between their imidazole and picolinate N‐heterocycles, with centroid–centroid distances in the range 3.582 (2)–3.764 (2) Å.     

catena‐Poly[[nickel(II)‐μ2‐[1,3‐bis(imidazol‐1‐ylmethyl)benzene‐κ2N3:N3′]‐μ2‐(5‐carboxybenzene‐1,3‐dicarboxylato‐κ4O1,O1′:O3,O3′)] 0.41‐hydrate]

The title compound, {[Ni(C₉H₄O₆)(C₁₄H₁₄N₄)]·0.41H₂O}_n, exhibits a three‐dimensional hydrogen‐bonded supramolecular framework. The Ni^II cation is six‐coordinated in a distorted triangular prism defined by two N atoms from two 1,3‐bis(imidazol‐l‐ylmethyl)benzene (bix) ligands and four O atoms from two 5‐carboxybenzene‐1,3‐dicarboxylate (HBTC) dianions. The bix molecules and HBTC dianions both act as bidentate ligands, linking the Ni^II cations to form a one‐dimensional coordination polymer. A two‐dimensional wave‐like net is constructed by O—H...O hydrogen bonds linking adjacent chains. Partially occupied solvent water molecules fill the cavities and link these layers to form a three‐dimensional supramolecular structure via O—H...O hydrogen bonds. The title compound was also characterized by powder X‐ray diffraction and thermogravimetric analysis.     

An unusual P312 framework for the Ni(4,4′‐bipyridine)(H2O)4 chain

catena‐Poly[[[tetra­aqua­nickel(II)]‐μ‐4,4′‐bipyridine‐κ²N:N′] thio­sulfate dihydrate], {[Ni(C₁₀H₈N₂)(H₂O)₄]S₂O₃·2H₂O}_n, (I), and catena‐poly[[[tetra­aqua­nickel(II)]‐μ‐4,4′‐bipyridine‐κ²N:N′] sulfate methanol solvate monohydrate], {[Ni(C₁₀H₈N₂)(H₂O)₄]SO₄·CH₄O·H₂O}_n, (II), are built up of {[Ni(4,4′‐bipy)(H₂O)₄]²⁺}_n chains (4,4′‐bipy is 4,4′‐bipyridine) inter­woven in an unusual P3₁ fashion. Voids are filled by the corresponding counter‐anions and solvate mol­ecules, defining a complex three‐dimensional network surrounding them. In both structures, the cationic chains evolve around a set of twofold axes passing through the Ni^II ions and bis­ecting the aromatic amines through their N (and their opposite C) atoms.     

Three oxo complexes with a tetra­nuclear [Cu4(μ2‐Cl)6(μ4‐O)] unit

The three title compounds, namely 4‐phenyl‐1H‐imidazolium hexa‐μ₂‐chloro‐chloro‐μ₄‐oxo‐tris­(4‐phenyl‐1H‐imidazole‐κN¹)­tetra­copper(II) monohydrate, (C₉H₉N₂)[Cu₄Cl₇O(C₉H₈N₂)₃]·H₂O, hexa‐μ₂‐chloro‐μ₄‐oxo‐tetra­kis­(pyridine N‐oxide‐κO)tetra­copper(II), [Cu₄Cl₆O(C₅H₅NO)₄], and hexa‐μ₂‐chloro‐tetra­kis(2‐methyl‐1H‐imidazole‐κN¹)‐μ₄‐oxo‐tetra­copper(II) methanol trisolvate, [Cu₄Cl₆O(C₄H₆N₂)₄]·3CH₄O, exhibit the same Cu₄OCl₆ framework, where the O atom at the centre of an almost regular tetra­hedron bridges four copper cations at the corners. This group is in turn surrounded by a Cl₆ octa­hedron, leading to a rather globular species. This special arrangement of the Cu^II cations results in a diversity of magnetic behaviours.     

Bimetallic assemblies, [Ni(en)2]3[M(CN)6]2·3H2O (en = H2NCH2CH2NH2; M = Fe,Co)

The reaction between tris(ethyl­enedi­amine)­nickel(II) cations and hexa­cyanometallate(III) anions (M = Fe, Co) yields ordered bimetallic assemblies, catena‐poly­[[tris­(ethyl­enedi­amine)­nickel‐bis(μ‐hexa­cyano­iron‐N,N′)] trihydrate] and catena‐poly­[[tris­(ethyl­enedi­amine)­nickel‐bis(μ‐hexa­cyano­cobalt‐N,N′)] trihydrate], [{Ni(C₂H₈N₂)₂}₃{M(CN)₆}₂]·3H₂O, in which both cis and trans [Ni(en)₂] and [M(CN)₆] moieties are linked to give S‐shaped Ni–NC–M–CN–Ni–NC–M–CN–Ni units which are cross­linked to give ribbons parallel to the b axis. The two compounds are isomorphous with mean metal–ligand distances Fe—C = 1.940 (3), Co—C = 1.844 (3) and Ni—N = 2.102 (2) Å for the iron, and 2.105 (3) Å for the cobalt compound. These compounds appear to be identical with those formulated as [Ni(en)₂]₃[M(CN)₆]₂·2H₂O [Ohba, Maruona, Okawa, Enoki & Latour (1994). J. Am. Chem. Soc. 116 , 11566–11567; Ohba, Fukita & Okawa (1997). J. Chem. Soc. Dalton Trans. pp. 1733–1737] which were indexed on a smaller unit cell and described as disordered.     

[Be3(μ3‐O)3(MeCN)6{Be(MeCN)3}3](I)6 – ein Berylliumkomplex mit Cyclo‐(Be3O3)‐Kern und sein Hydrolyseprodukt [Be(H2O)4](I)2·2MeCN

Single crystals of [Be₃(μ₃‐O)₃(MeCN)₆{Be(MeCN)₃}₃](I)₆·4CH₃CN ( 1 ·4CH₃CN) were obtained in low yield by the reaction of beryllium powder with iodine in acetonitrile suspension, which probably result from traces of beryllium oxide containing the applied beryllium metal. The compound 1 ·4CH₃CN forms moisture sensitive, colourless crystal needles, which were characterized by IR spectroscopy and X‐ray diffraction (Space group Pnma, Z = 4, lattice dimensions at 100(2) K: a = 2317.4(1), b = 2491.4(1), c = 1190.6(1) pm, R₁ = 0.0315). The hexaiodide complex cation 1 ⁶⁺consists of a cyclo‐Be₃O₃ core with slightly distorted chair conformation, stabilized by coordination of two acetonitrile ligands at each of the beryllium atoms and by a {Be(CH₃CN)₃}²⁺ cation at each of the oxygen atoms. This unique coordination behaviour results in coplanar OBe₃ units with short Be–O distances of 155.0 pm and 153.6 pm on average of bond lengths within the cyclo‐Be₃O₃ unit and of the peripheric BeO bonds, respectively. Exposure of compound 1 ·4CH₃CN to moist air leads to small orange crystal plates of [Be(H₂O)₄]I₂·2CH₃CN ( 3 ·2CH₃CN). According to the crystal structure determination (Space group C2/c, Z = 4, lattice dimensions at 100(2) K: a = 1220.7(1), b = 735.0(1), c = 1608.5(1) pm, β = 97.97(1)°, R₁ = 0.0394), all hydrogen atoms of the dication [Be(H₂O)₄]²⁺ are involved to form O–H ··· N and O–H ··· I hydrogen bonds with the acetonitrile molecules and the iodide ions, respectively. Quantum chemical calculations (B3LYP/6‐311+G**) at the model [Be₃(μ₃‐O)₃(HCN)₆{Be(HCN)₃}₃]⁶⁺ show that chair and boat conformation are stable and that the distorted chair conformation is stabilized by packing effects.     

Synthese,Kristallstruktur und Eigenschaften von Tetranatrium‐bis(trimetaphosphimato)cuprat(II)‐Decahydrat,Na4{Cu[(PO2NH)3]2} · 10 H2O

Synthesis, Crystal Structure, and Properties of Tetrasodium Bis(trimetaphosphimato)cuprate(II) Decahydrate, Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O Tetrasodium bis(trimetaphosphimato)cuprate(II) decahydrate, Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O, was obtained by the reaction of an aqueous solution of Na₃(PO₂NH)₃ · 4 H₂O with Cu(NO₃)₂ · 3 H₂O (molar ratio 2 : 1). The structure of Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O ( 1 ) was solved by single‐crystal X‐ray methods (P 1, a = 912.51(6), b = 932.14(6), c = 966.10(6) pm, α = 94.840(5), β = 108.652(6), γ = 118.588(6)°, Z = 1). The P₃N₃ rings of the trimetaphosphimate ions exhibit a slightly distorted sofa conformation. The conformation of the anions have been analysed using torsion angles, displacement asymmetry parameters, and puckering parameters. The trimetaphosphimate ions act as bidentate ligands of Cu²⁺. With additionally coordinated water molecules, anionic complexes {Cu[(PO₂NH)₃]₂ · 2 H₂O}^4– are formed. In the crystal these complexes are interconnected by N–H…O und O–H…O hydrogen bonds and they coordinate the Na⁺. Thus, a three‐dimensional network is formed.     

Syntheses,structures and characterization of isomorphous CoII and NiII coordination polymers based on 2‐[(1H‐imidazol‐1‐yl)methyl]‐6‐methyl‐1H‐benzimidazole and benzene‐1,4‐dicarboxylate

Careful choice of the organic ligands is one of the most important parameters in the rational design and synthesis of coordination polymers. Aromatic polycarboxylates have been widely used in the preparation of metal–organic polymers since they can utilize various coordination modes to form diverse structures and can act as hydrogen‐bond acceptors and donors in the assembly of supramolecular structures. Nitrogen‐heterocyclic organic compounds have also been used extensively as ligands for the construction of polymers with interesting structures. In the polymers catena‐poly[[[diaquabis{2‐[(1H‐imidazol‐1‐yl)methyl]‐6‐methyl‐1H‐benzimidazole‐κN ³}cobalt(II)]‐μ₂‐benzene‐1,4‐dicarboxylato‐κ²O ¹:O ⁴] dihydrate], {[Co(C₈H₄O₄)(C₁₂H₁₁N₄)₂(H₂O)₂]·2H₂O}_n , (I), and catena‐poly[[[diaquabis{2‐[(1H‐imidazol‐1‐yl)methyl]‐6‐methyl‐1H‐benzimidazole‐κN ³}nickel(II)]‐μ₂‐benzene‐1,4‐dicarboxylato‐κ²O ¹:O ⁴] dihydrate], {[Ni(C₈H₄O₄)(C₁₂H₁₁N₄)₂(H₂O)₂]·2H₂O}_n , (II), the Co^II or Ni^II ion lies on an inversion centre and exhibits a slightly distorted octahedral coordination geometry, coordinated by two N atoms from two imidazole rings and four O atoms from two monodentate carboxylate groups and two water molecules. The dicarboxylate ligands bridge metal ions forming a polymeric chain. The 2‐[(1H‐imidazol‐1‐yl)methyl]‐6‐methyl‐1H‐benzimidazole ligands coordinate to the Co^II or Ni^II centres in monodentate modes through an imidazole N atom and are pendant on opposite sides of the main chain. The two structures are isomorphous. In the crystal, the one‐dimensional chains are further connected through O—H…O, O—H…N and N—H…O hydrogen bonds, leading to a three‐dimensional supramolecular architecture. In addition, the IR spectroscopic properties, PXRD patterns, thermogravimetric behaviours and fluorescence properties of both polymers have been investigated.     

Das Lanthan‐Dodekahydro‐closo‐Dodekaborat‐Hydrat [La(H2O)9]2[B12H12]3·15 H2O und sein Oxonium‐Chlorid‐Derivat [La(H2O)9](H3O)Cl2[B12H12]·H2O

The Lanthanum Dodecahydro‐closo‐Dodecaborate Hydrate [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O and its Oxonium‐Chloride Derivative [La(H₂O)₉](H₃O)Cl₂[B₁₂H₁₂]·H₂O By neutralization of an aqueous solution of the free acid (H₃O)₂[B₁₂H₁₂] with basic La₂O₃ and after isothermic evaporation colourless, face‐rich single crystals of a water‐rich lanthanum(III) dodecahydro‐closo‐dodecaborate hydrate [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O are isolated. The compound crystallizes in the trigonal system with the centrosymmetric space group (a = 1189.95(2), c = 7313.27(9) pm, c/a = 6.146; Z = 6; measuring temperature: 100 K). The crystal structure of [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O can be characterized by two of each other independent, one into another posed motives of lattice components. The [B₁₂H₁₂]²⁻ anions (d(B–B) = 177–179 pm; d(B–H) = 105–116 pm) are arranged according to the samarium structure, while the La³⁺ cations are arranged according to the copper structure. The lanthanum cations are coordinated in first sphere by nine oxygen atoms from water molecules in form of a threecapped trigonal prism (d(La–O) = 251–262 pm). A coordinative influence of the [B₁₂H₁₂]²⁻ anions on La³⁺ has not been determined. Since “zeolitic” water of hydratation is also present, obviously the classical H–O^δ–···^+δH–O‐hydrogen bonds play a significant role in the stabilization of the crystal structure. During the conversion of an aqueous solution of (H₃O)₂[B₁₂H₁₂] with lanthanum trichloride an anion‐mixed salt with the composition [La(H₂O)₉](H₃O)Cl₂[B₁₂H₁₂]·H₂O is obtained. The compound crystallizes in the hexagonal system with the non‐centrosymmetric space group (a = 808.84(3), c = 2064.51(8) pm, c/a = 2.552; Z = 2; measuring temperature: 293 K). The crystal structure can be characterized as a layer‐like structure, in which [B₁₂H₁₂]²⁻ anions and H₃O⁺ cations alternate with layers of [La(H₂O)₉]³⁺ cations (d(La–O) = 252–260 pm) and Cl⁻ anions along [001]. The [B₁₂H₁₂]²⁻ (d(B–B) = 176–179 pm; d(B–H) = 104–113 pm) and Cl⁻ anions exhibit no coordinative influence on La³⁺. Hydrogen bonds are formed between the H₃O⁺ cations and [B₁₂H₁₂]²⁻ anions, also between the water molecules of [La(H₂O)₉]³⁺ and Cl⁻ anions, which contribute to the stabilization of the crystal structure.     

Stabilization of Substituted Triazenide Oxides: Synthesis and X‐ray Structural Features of Polymeric Potassium 3‐(4‐carboxylatophenyl)‐1‐methyltriazene N‐oxide‐hydrate, {K[O2C‐C6H4‐N(H)NN(CH3)O]·4H2O}n

3‐(4‐carboxyphenyl)‐1‐methyltriazene N‐oxide reacts with KOH in methanol/pyridine to give {K[O₂C‐C₆H₄‐N(H)NN(CH₃)O]·4H₂O}_n, Potassium‐3‐(4‐carboxylatophenyl)‐1‐methyltriazene N‐oxide). The terminal carboxylato group of the anion does not interact with the cation. In the crystal lattice of {K(C₈H₈N₃O₃)·4H₂O}_n each three of the four water molecules interact with two potassium cations, every K⁺ ion being the centre of six bridging K···O interactions. Potassium cations interact further with the terminal N‐oxigen atom of single [C₈H₈N₃O₃]^? anions achieving two parallel {C₈H₈N₃O₃^?K⁺}_n chains, which are linked through water molecules. The resulting polymeric, one‐dimensional chain, is operated by a screw axis 2₁ parallel to the crystallographic direction [010], along and equidistant to the K⁺ centres. The coordination of the K⁺ centres involves a distortion of the boat conformation of elementary sulfur (S₈) with the ideal C_2v symmetry.     

Tris[2‐(1,3‐thiazol‐2‐yl‐κN)‐1H‐benzimidazole‐κN3]zinc(II) dinitrate ethanol hemisolvate monohydrate at 100 K

The Zn^II center in the dicationic complex of the title compound, [Zn(C₁₀H₇N₃S)₃](NO₃)₂·0.5C₂H₅OH·H₂O, is in a distorted octahedral environment with imperfect noncrystallographic C₃ symmetry. Each 2‐(1,3‐thiazol‐2‐yl)‐1H‐benzimidazole ligand coordinates in a bidentate manner, with the Zn—N(imidazole) bond lengths approximately 0.14 Å shorter than the Zn—N(thiazole) bond lengths. Charge‐assisted hydrogen bonds connect cations, anions and water molecules. A lattice void is occupied by an ethanol solvent molecule disordered about a crystallographic inversion center and π‐stacking is observed between one type of symmetry‐related benzene rings.     

A Pentanuclear Cobalt Complex with two [CoII(CH3O)3]– Units Wrapping a Triangular [CoIII3O]7+ Core: Synthesis,Structure, and Magnetic Properties

The reaction of Hppko (Hppko = phenyl 2‐pyridyl ketone oxime) and CoCl₂ · 6H₂O in the CH₃OH solvent with the presence of triethylamine (NEt₃) at room temperature and the exposure to air resulted in the formation of a new pentanuclear, mixed‐valence cobalt complex with the molecular formula [{Co^II(CH₃O)₃}₂{Co^III₃(μ₃‐O)(ppko)₃}Cl₂]. X‐ray single crystal analysis displays a trigonal bipyramid configuration with the terminal two Co^II ions wrapping an triangle [Co^III₃O]⁷⁺ core. The intermolecular C–H ··· O and C–H ··· Cl interactions form a 2D network framework. The analysis of magnetic susceptibility revealed the dominant antiferromagnetic interactions and strong orbital contribution of Co^II ions.