Crystal Structures and Thermal Properties of Two Transition-Metal Compounds {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O and Pb(DNI)2(H2O)4 (DNI?=?2,4-Dinitroimidazolate)

Abstract  

Two transition-metal compounds derived from 2,4-dinitroimidazole, {[Ni(DNI)₂(H₂O)₃][Ni(DNI)₂(H₂O)₄]}·6H₂O, 1, and Pb(DNI)₂(H₂O)₄, 2, were characterized by elemental analysis, FT-IR, TG-DSC and X-ray single-crystal diffraction analysis. Crystal data for 1: monoclinic, space group C2/c, a = 26.826(3), b = 7.7199(10), c = 18.579(2) ?, β = 111.241(2)° and Z = 4; 2: monoclinic, space group C2/c, a = 6.5347(6), b = 17.1727(17), c = 14.1011(14) ?, β = 97.7248(10) and Z = 4. Compound 1 contains two isolated nickel centers in its structure, one being six-coordinate and another five-coordinate. The structure of 2 contains a lead (II) center surrounded by two chelating DNI ligands and four water molecules in distorted square-antiprism geometry. The abundant hydrogen bonds in two compounds link the molecules into three-dimensional network and stabilize the molecules. The TG-DSC analysis reveals that the first step is the loss of water molecules and the final residue is the corresponding metal oxides and carbon.     

Crystal Structures of Two Aromatic Zinc(II) Carboxylates: [Zn(4-Chlorosalicylato)2(H2O)4]·2theophylline·(H2O)2 and Unique [Zn(5-Chlorosalicylato)2(isonicotinamide)2(H2O)]

Abstract  

The crystal structures of two zinc(II) 4-chloro- and 5-chlorosalicylate complexes, [Zn(4-ClC₆H₃-2-(OH)COO)₂(H₂O)₄]·2tph·(H₂O)₂ (I) and [Zn(5-ClC₆H₃-2-(OH)COO)₂(ina)₂(H₂O)] (II), where tph is theophylline and ina is isonicotinamide, have been determined using X-ray diffraction methods. Crystals of both (I) and (II) are triclinic, space group P-1, with Z = 1 in a cell with a = 7.2220(3), b = 8.59700(10), c = 16.0210(5) ?, α = 75.990(2), β = 83.959(2), γ = 68.455(2)°, V = 897.54(5) ?³ (I) and with Z = 2 in a cell with a = 11.4148(11), b = 11.5327(10), c = 12.0685(13) ?, α = 63.458(6), β = 87.547(8), γ = 89.387(7)°, V = 1419.9(2) ?³ (II). The coordination environment of the zinc(II) atom of compound (I) consists of two unidentate carboxylate oxygen atoms and four oxygen atoms of aqua ligands, forming a distorted octahedral configuration. Two theophylline molecules and the remaining water molecules are bound only by hydrogen bonds. The Zn atom of compound (II) is pentacoordinated with two unidentate carboxylate oxygen atoms, two pyridine nitrogen atoms of isonicotinamide ligands, and the oxygen atom of the aqua ligand, forming a distorted configuration between square pyramid and trigonal bipyramid. In both complexes intramolecular O–H···O hydrogen-bonding interactions are present. In the crystal structures, molecules are linked by intermolecular O–H···O and N–H···O hydrogen bonds. The structures are analyzed and compared to the similar Zn(II) complexes, with the chromophores ZnO₆ and ZnO₃N₂.     

Synthesis and structure of K2[(UO2)4(O)2(OH)2(C2O4)(CH3COO)2(H2O)2]·2H2O

Single crystals of the compound K₂[(UO₂)₄(O)₂(OH)₂(C₂O₄)(CH₃COO)₂(H₂O)₂]·2H₂O (I) are synthesized, and their structure is investigated using X-ray diffraction. Crystals of compound I belong to the triclinic system with the unit cell parameters a = 7.6777(6) ?, b = 7.9149(7) ?, c = 10.8729(9) ?, α = 72.379(2)°, β = 86.430(3)°, γ = 87.635(2)°, V = 628.33(9) ?³, space group P , Z = 1, and R ₁ = 0.0323. The main structural units of the crystals are [(UO₂)₄(O)₂(OH)₂(C₂O₄)(CH₃COO)₂(H₂O)₂]²⁻ chains, which belong to the crystal-chemical group A ₄ M ₂³ M ₂² K ⁰² B ₂⁰¹ M ₂¹ (A = UO₂²⁺, M ³ = O²⁻, M ² = OH⁻, K ⁰² = C₂O₄²⁻, B ⁰¹ = CH₃COO⁻, M ¹ = H₂O) of the uranyl complexes. The chains are formed by linking the centrosymmetric tetramers of the composition (UO₂)₄(O)₂(OH)₂(CH₃COO)₂(H₂O)₂ via tetradentate bridging oxalate ions. The uranium-containing groups are joined into a three-dimensional framework through the electrostatic interaction with potassium cations and a system of hydrogen bonds, which are formed with the participation of atoms involved in the composition of the water molecules, hydroxide ions, and uranyl ions. Original Russian Text ? L.B. Serezhkina, A.V. Vologzhanina, N.A. Neklyudova, V.N. Serezhkin, 2009, published in Kristallografiya, 2009, Vol. 54, No. 3, pp. 483–487.     

Synthesis and X-ray structural investigation of (C3N6H7)4(CN3H6)2[UO2(CrO4)4] · 4H2O and (H3O)6[UO2(CrO4)4]

Single crystals of the compounds (C₃N₆ H₇)₄(CN₃H₆)₂[UO₂(CrO₄)₄] · 4H₂O (I) and (H₃O)₆[UO₂(CrO₄)₄] (II) are synthesized, and their structures are investigated using X-ray diffraction. Compound I crystallizes in the triclinic system with the unit cell parameters a = 6.3951(8) ?, b = 10.8187(16) ?, c = 16.9709(18) ?, α = 93.674(4)°, β = 97.127(4)°, γ = 92.020(4)°, space group, P Z = 1, V = 1161.6(3) ?³, and R = 0.0470. Crystals of compound II belong to the monoclinic system with the unit cell parameters a = 14.3158(4) ?, b = 11.7477(3) ?, c = 13.1351(4) ?, β= 105.836(1)°, space group C2/c, Z = 4, V = 2125.2(1) ?³, and R = 0.0213. The uranium-containing structural units of crystals I and II are mononuclear anionic complexes of the composition [UO₂(CrO₄)₄]⁶⁻ with an island structure, which belong to the crystal-chemical group Am ₁⁴ (A = UO₂₊², M ¹ = CrO₂₋⁴) of the uranyl complexes. The [UO₂(CrO₄)₄]⁶⁻ anionic complexes are joined into a three-dimensional framework through the electrostatic interactions with outer-sphere cations and a system of hydrogen bonds. Original Russian Text ? L.B. Serezhkina, E.V. Peresypkina, A.V. Virovets, A.G. Verevkin, D.V. Pushkin, 2009, published in Kristallografiya, 2009, Vol. 54, No. 2, pp. 284–290.     

Structure, thermal, and infrared analyses of [NH3(CH2)3NH3]2[Ni(HP2O7)2(H2O)2] ? 4H2O

[NH₃(CH₂)₃NH₃]₂[Ni(HP₂O₇)₂(H₂O)₂] 4H₂O (NiDAP) is a new diphosphate of transition metallic and organic cations obtained from a mixture of H₄P₂O₇, 2NiCO₃ Ni(OH)₂ 4H₂O and NH₂(CH₂)₃NH₂ in a 1:1/6:1 molar ratio. This mixed organo-mineral compound crystallizes in the triclinic system, P¯, with the unit cell dimensions: a = 7.3678(3)~Å, b = 7.8018(5)Å, c = 11.1958(7)Å, = 76.914(4), = 81.052(4), = 85.46(1), V = 618.57(6)ų and Z = 1. The crystal structure of NiDAP consists of a complex anion, [Ni(HP₂O₇)₂(H₂O)₂]^4– and a diammoniumpropane cation. The complex anion is built up from two neutral water molecules (OW1) and two diphosphosphoric anions coordinated to Ni(II) in a bidentate chelating manner. (OW1) molecules link anionic complexes, [Ni(HP₂O₇)₂(H₂O)₂]^4– to create a thick bidimensional layers parallel to the (a, b) plane. These layers are interconnected in three dimensions through hydrogen bonds established between organic cations, the remaining water molecules OW2, OW3, and some external oxygen atoms of the anionic complex arrays. NiDAP was also characterized by IR spectroscopy, TG-DTA, and DSC analyses.     

A study of the mechanisms of defect formation in K2Ni(SO4)2 · 6H2O/K2Co(SO4)2 · 6H2O bicrystals grown from aqueous solutions

The K₂Co(SO₄)₂ · 6H₂O-K₂Ni(SO₄)₂ · 6H₂O system has been studied, and a series of K₂Ni(SO₄)₂ · 6H₂O/K₂Co(SO₄)₂ · 6H₂O bicrystals have been grown. The processes of defect formation at the substrate/layer interface K₂Co(SO₄)₂ · 6H₂O/K₂Ni(SO₄)₂ · 6H₂O are studied by probe microanalysis, X-ray topography, and optical microscopy. It is found that inclusions and threading dislocations are formed at the interface, due to which elastic stresses relax in the crystal. Nickel is nonuniformly distributed in the layer; its concentration decreases with an increase in the layer thickness, which is indicative of substrate dissolution in the initial stage of interaction. A way for the elastic mismatch stresses to relax in heterostructures of brittle crystals obtained from solutions at low temperatures is proposed which implies the formation of inclusions at the substrate/layer interface. Original Russian Text ? M.S. Grigor’eva, A.é. Voloshin, E.B. Rudneva, V.L. Manomenova, S.N. Khakhanov, V.Ya. Shklover, 2009, published in Kristallografiya, 2009, Vol. 54, No. 4, pp. 679–687.     

Synthesis and Structure of a Novel Polyoxomolybdate Lanthanide Complex: [Er2(H2O)14Cr(OH)6Mo6O18][Cr(OH)6Mo6O18]?·?14H2O

Abstract  A novel polyoxometalate compound consisting of Anderson-type anions and trivalent lanthanide cations, [Er₂(H₂O)₁₄Cr(OH)₆Mo₆O₁₈][Cr(OH)₆Mo₆O₁₈]·14H₂O (1), has been synthesized in aqueous solution and characterized by single crystal X-ray diffraction, elemental analyses, IR spectrum and TG analyses. Single crystal X-ray diffraction reveals that compound 1 crystallizes in the triclinic space group P-1 with a = 11.046 (5) ?, b = 11.653 (5) ?, c = 13.935 (5) ?, α = 75.006 (5)°, β = 84.497(5)°, γ = 89.515(5)°. The bulk ions of compound 1 in the cell unit exhibit orthorhombic C-centered packing mode, the eight [Cr(2)(OH)₆Mo₆O₁₈]³⁻ anions occupy the eight corners and the two [Er₂(H₂O)₁₄Cr(OH)₆Mo₆O₁₈]³⁺ cations occupy the centres of two opposite faces, whereas anions and cations are linked together via hydrogen bonding interactions tightly forming a three-dimensional supramolecular architecture, which contains one-dimensional channels occupied by free water molecules. Index Abstract  The bulk ions of compound 1 in the cell unit exhibit orthorhombic C-centered packing mode, the eight [Cr(2)(OH)₆Mo₆O₁₈]³⁻ anions occupy the eight corners and the two [Er₂(H₂O)₁₄Cr(OH)₆Mo₆O₁₈]³⁺ cations occupy the centres of two opposite faces, whereas anions and cations are linked together via hydrogen bonding interactions tightly forming a three-dimensional supramolecular architecture, which contains one-dimensional channels occupied by free water molecules. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal and molecular structure of Sr2( Edta ) · 5H2O, Sr2(H2 Edta )(HCO3)2 · 4H2O, and Sr2(H2 Edta )Cl2 · 5H2O strontium ethylenediaminetetraacetates

Three Sr²⁺ compounds with the Edta ⁴⁻ and H₂ Edta ²⁻ ligands—Sr₂(Edta) · 5H₂O (I), Sr₂(H₂ Edta)(HCO₃)₂ · 4H₂O (II), and Sr₂(H₂ Edta)Cl₂ · 5H₂O (III)—are synthesized, and their crystal structures are studied. In I, the Sr(1) atom is coordinated by the hexadentate Edta ⁴⁻ ligand following the 2N + 4O pattern and by two O atoms of the neighboring ligands, which affords the formation of zigzag chains. The Sr(2) atom forms bonds with O atoms of five water molecules and attaches itself to a chain via bonds with three O atoms of the Edta ⁴⁻ ligands. The Sr(1)-O and Sr(2)-O bond lengths fall in the ranges 2.520(2)–2.656(3) and 2.527(3)–2.683(2) ?, respectively. The Sr(1)-N bonds are 2.702(3) and 2.743(3) ? long. In II and III, the H₂ Edta ²⁻ anions have a centrosymmetric structure with the trans configuration of the planar ethylenediamine fragment. The N atoms are blocked by acid protons. In II, the environment of the Sr atom is formed by six O atoms of three H₂ Edta ligands, two O atoms of water molecules, and an O atom of the bicarbonate ion, which is disordered over two positions. In III, the environment of the Sr atom includes six O atoms of four H₂ Edta ²⁻ ligands and three O atoms of water molecules. The coordination number of the Sr atoms is equal to 8 + 1. In II and III, the main bonds fall in the ranges 2.534(3)–2.732(2) and 2.482(2)–2.746(3) ?, whereas the ninth bond is elongated to 2.937(3) and 3.055(3) ?, respectively. In II, all the structural elements are linked into wavy layers. The O-H…O interactions contribute to the stabilization of the layer and link neighboring layers. In III, hydrated Sr²⁺ cations and H₂ Edta ^– anions form a three-dimensional [Sr₂(H₂ Edta)(H₂O)₃] _n ²ⁿ⁺ framework. The Cl⁻ anions are fixed in channels of the framework by hydrogen bonds with four water molecules. In II and III, the N-H groups form four-center N-H…O₃ hydrogen bonds, which include one intermolecular and two intramolecular components. PACS numbers: 61.66.Hq Original Russian Text ? I.N. Polyakova, A.L. Poznyak, V.S. Sergienko, 2009, published in Kristallografiya, 2009, Vol. 54, No. 2, pp. 262–267.     

Synthesis and X-ray structural investigation of K8[(UO2)2(C2O4)2(SeO4)4] · 2H2O

Single crystals of the compound K₈[(UO₂)₂(C₂O₄)₂(SeO₄)4] · 2H₂O (I) are synthesized, and their structure is investigated using X-ray diffraction. Compound I crystallizes in the monoclinic system with the unit cell parameters a = 14.9290(4) ?, b = 7.2800(2) ?, c = 15.3165(4) ?, β = 109.188(1)°, V = 1572.17(7) ?³, space group P2₁/n, Z = 2, and R = 0.0297. The uranium-containing structural units of crystals I are dimers of the composition [(UO ₂)₂(C₂O₄)₂(SeO₄)₄]⁸⁻, which belong to the crystal-chemical group AB ⁰¹ B ² M ¹ (A = UO₂²⁺, B ⁰¹ = C₂O₄²⁻, B ² = SeO₄²⁻, M ¹ = SeO₄²⁻) of the uranyl complexes. The [(UO₂)₂(C₂O₄)₂(SeO₄)₄]⁸⁻ dimers are joined into a three-dimensional framework through electrostatic interactions with the outer-sphere potassium cations. Original Russian Text ? L.B. Serezhkina, E.V. Peresypkina, A.V. Virovets, A.G. Verevkin, D.V. Pushkin, 2009, published in Kristallografiya, 2009, Vol. 54, No. 1, pp. 68–71.     

Syntheses, Characterization and Structural Determination of Nine Coordinated N2H5[Ce(edta)(H2O)3]·4H2O and N2H5[Eu(edta)(H2O)3]·4H2O

Abstract  

Hydrazinium complexes of Ce(III) and Eu(III) ethylenediaminetetra-acetate hydrates have been synthesized in aqueous solution and characterized by hydrazine and metal analyses, elemental analysis, infrared spectra, X-ray power diffraction and single crystal X-ray diffraction techniques. The Ce^IIIN₂O₇ parts in the complex anion has a pseudomono-capped square antiprismatic nine-coordinate structure, in which the six coordinated atoms (two N and four O) from the ethylenediaminetetraacetate ion and three water molecules are coordinated to the central rare earth metal ion directly. The Eu^IIIN₂O₇ part in the complex anion has the same structure as Ce^IIIN₂O₇ part. The crystal of the cerium complex belongs to the orthorhombic crystal system and Fdd2 space group. The crystal data are the follows: a = 19.7281(7) ?, b = 35.7790(11) ?, c = 12.3244(4) ?, α = β =γ = 90^°, V = 8699.2(5) ?³. The final R and Rw are 0.020 and 0.0589 for with I > 2σ (I) and 3,842 reflections, respectively. The crystal of the europium complex is isostructural with the cerium complex. The crystal data of europium complex are: a = 19.7281(7) ?, b = 35.7790(11) ?, c = 12.3244(4) ?, α = β =γ = 90^°, V = 8699.2(5) ?³. The final R and Rw are 0.0252 and 0.687 for with I > 2σ (I) and 3,842 reflections, respectively. The X-ray powder diffraction patterns and infrared spectra of the complex are super imposable indicating their structural similarity.     

Synthesis, Crystal Structure and Magnetic Behaviour of {[Yb(1,4-BDC)1.5(H2O)4]·H2O}n (1,4-BDC?=?1,4-benzenedicarboxylate)

Abstract  

The title complex {[Yb(1,4-BDC)_1.5(H₂O)₄]·H₂O}_n (1) (1,4-BDC = 1,4-benzenedicarboxylate) has been hydrothermally synthesized and structurally characterized by the single crystal X-ray diffraction. Crystals of compound 1 belongs to the triclinic crystal system, space group P-1; a = 7.549(3) ?, b = 10.072(4) ?, c = 10.470(4) ?, α = 87.810(4)°, β = 82.531(4)°, γ = 86.306(4)°, V = 787.3(5) ?³, Z = 2. The Yb(III) atoms are linked by the deprotonated 1,4-BDC ligands in two kinds of bridging modes. Four Yb(III) atoms at each corner (nodes) and four 1,4-BDC ligands at each edge (spacers) form a edge–sharing 36-membered rings. The rhombohedral Yb₄(1,4-BDC)₄ arranged in an alternating fashion to construct a 1D ladder-like chain along the c axis. Two neighboring chains are linked to each other in a parallel fashion to construct 3D supramolecular structure by O–H···O hydrogen bonds and π–π stacking interactions. In addition, the properties of thermogravimetric analysis and magnetic behaviors of the complex have been also discussed.     

Synthesis and structure of {NH2(C2H5)2}2[(UO2)2(C2O4)(CH3COO)4] · 2H2O

Single crystals of the compound {NH₂(C₂H₅)₂}₂[(UO₂)₂C₂O₄(CH₃COO)₄] · 2H₂O (I) are synthesized, and their structure is investigated using X-ray diffraction. Compound I crystallizes in the monoclinic system with the unit cell parameters a = 9.210(2) ?, b = 14.321(3) ?, c = 12.659(3) ?, β = 105.465(13)°, V = 1609.2(6) ?³, space group P2₁/c, Z = 2, and R = 0.0198. The structural units of crystals I are binuclear groups of the composition [(UO₂)₂C₂O₄(CH₃COO)₄]²⁻ with an island structure, which belong to the crystal-chemical group A ₂ K ⁰² B ₄⁰¹ (A = UO₂²⁺, K ⁰² = C₂O₄²⁻, B ⁰¹ = CH₃COO⁻) of the uranyl complexes, diethylammonium cations, and water molecules. The uranium-containing groups are joined into a three-dimensional framework through electrostatic interactions with diethylammonium cations and a system of hydrogen bonds, which are formed with the participation of the atoms involved in the composition of the water molecules, oxalate ions, acetate ions, and diethylammonium cations. Original Russian Text ? L.B. Serezhkina, A.V. Vologzhanina, N.A. Neklyudova, V.N. Serezhkin, 2009, published in Kristallografiya, 2009, Vol. 54, No. 1, pp. 65–67.     

A Novel Keggin-Type Aluminotungstate Dimeric Compound: H3.5[Ni(2,2′-bipy)3]3{[AlW 10VI W 2V O40Ni(2,2′-bipy)2(H2O)]2Na0.5}

Abstract  A novel dimeric compound H_3.5[Ni(2,2′-bipy)₃]₃{[AlW₁₂O₄₀Ni(2,2′-bipy)₂(H₂O)]₂Na_0.5} prepared by the hydrothermal method consists of a {[AlW₁₂O₄₀Ni(2,2′-bipy)₂(H₂O)]₂Na_0.5}^9.5− heteropolyanion, and in the anion, two reduced Keggin heteropolyanions [AlW^VI ₁₀W₂^VO₄₀]⁷⁻ are bridged via Na coordination ion by means of an O–Na1–O linkage (O atoms from the surface bridging oxygen atoms of [AlW^VI ₁₀W₂^VO₄₀]⁷⁻) and two Ni coordination ions are linked to the Na1 square planar moiety by making use of Ni–Ow–Na1–Ow–Ni bridges. The crystal belongs to the monoclinic-space group C2/c, a = 46.592(9), b = 14.306(3), c = 25.967(5) ?, β = 90.14(3)°, V = 17308(6) ?³, Z = 4, D _c  = 3.116 Mg/m³. Index Abstract  A novel dimeric compound H_3.5[Ni(2,2′-bipy)₃]₃{[AlW₁₂O₄₀Ni(2,2′-bipy)₂(H₂O)]₂Na_0.5} prepared by the hydrothermal method consists of a {[AlW₁₂O₄₀Ni(2,2′-bipy)₂(H₂O)]₂Na_0.5}^9.5− heteropolyanion, and in the anion, two reduced Keggin heterpolyanions [AlW^VI ₁₀W^V ₂O₄₀]⁷⁻ are bridged via Na coordination ion by means of an O–Na1–O linkage (O atoms from the surface bridging oxygen atoms of [AlW^VI ₁₀W^V ₂O₄₀]⁷⁻) and two Ni coordination ions are linked to the Na1 square planar moiety by making use of Ni7–Ow7–Na17–Ow7–Ni bridges.      

Preparation, Crystal Structure and Spectroscopic Properties of Dimeric [Zn(2-bromobenzoato)2(phenazone)]2 and Monomeric [Zn(2-bromobenzoato)2(thiourea)2]·2H2O

Abstract  

The binuclear zinc complex bis(2-bromobenzoato-O)-bis(μ ₂ -2-bromobenzoato-O,O′)-bis(phenazone-O)-dizinc(II) (I) and the mononuclear dihydrate bis(2-bromobenzoato-O)-bis(thiourea-S)-zinc(II) (II) have been synthesized and characterized by means of elemental analysis and spectroscopic methods (IR, ¹H and ¹³C NMR, EDS). The solid state structures of both compounds were determined by single-crystal X-ray diffractometry. Compound [Zn(2-BrC₆H₄COO)₂(phen)]₂ (phen—phenazone) (I) crystallized as a dimeric compound with a triclinic lattice (space group P − 1), where both zinc atoms, interconnected by two carboxylate groups, possess a distorted tetrahedral coordination environment. The crystallographic data of complex I: a = 9.9410(3) ?, b = 10.7309(3) ?, c = 12.9237(4) ?, α = 93.6004(17)°, β = 92.5898(11)°, γ = 116.2192(16)°, V = 1230.26(6) ?³, Z = 1. Complex [Zn(2-BrC₆H₄COO)₂(tu)₂]·2H₂O (tu—thiourea) (II) crystallized with an orthorhombic lattice (space group Aba2) as a monomeric compound, where the coordination environment of the central zinc atom is a distorted tetrahedron. The crystallographic data of complex II are: a = 9.8595(3) ?, b = 19.7052(5) ?, c = 12.5908(3) ?, V = 2446.18(11) ?³, Z = 4. The modes of the carboxylate binding were assigned from the IR spectra using the magnitude of the separation between the carboxylate stretches (Δ), which correlated well with the crystal structures. The computed theoretical IR spectrum agreed well with the experimental data.     

Structures and Characterization of [Zn(n-chlorosalicylato)2(N-methylnicotinamide)2(H2O)2] (n?=?4 or 5) Ligand Isomers

Abstract  

Two ligand isomers [Zn{4-ClC₆H₃-2-(OH)COO}₂(Menia)₂(H₂O)₂] (I) and [Zn{5-ClC₆H₃-2-(OH)COO}₂(Menia)₂(H₂O)₂] (II) (Menia = N-methylnicotinamide) were prepared and characterized by elemental analysis, IR spectroscopy and thermal analysis. The X-ray crystal structures of complexes (I) and (II) were determined. Compound (I) crystallizes in the triclinic space group P[`1] P\bar{1} with a = 8.105(1) ?, b = 10.036(2) ?, c = 10.545(2) ?, α = 109.088(9)°, β = 91.416(8)°, γ = 102.757(9)°, V = 786.2(2) ?<sup>3</sup>, Z = 1. Compound (II) crystallizes in the triclinic space group P[`1] P\bar{1} . Its cell parameters are: a = 8.133(1) ?, b = 10.119(2) ?, c = 10.428(1) ?, α = 66.44(1)°, β = 74.32(1)°, γ = 80.16(1)°, V = 755.5(2) ?³, Z = 1. The molecular structure of both isomers is monomeric. Each Zn(II) atom is hexacoordinated by three pairs of unidentate ligands in trans-positions (ZnO₄N₂). The 5-Clsal complex is somewhat less distorted than 4-Clsal complex (Cl-sal = chlorosalicylate). The structural data are compared with those found in similar [Zn(RCOO)₂(NL)₂(H₂O)₂].     

配位聚合物{[Mn（H2BCPBA）2（H2O）4]}n的合成和表征

采用3,5-bi(4-carboxy-phenoxy)-benzoic acid(H3BCPBA)为配体,以Mn为中心离子采用自组装的方法合成了配位聚合物{[Mn(H2BCPBA)2(H2O)4]}n,采用单晶衍射仪,红外光谱,热重,固体紫外和元素分析对其进行了晶体结构的解析和表征。它属于三斜晶系,P1空间群,晶胞参数分别为a=0.58423(13)nm,b=1.3644(3)nm,c=1.3910(3)nm,α=109.173(2)°,β=98.927(3)°,γ=99.123(3)°,V=1.0082(4)nm,Mr=913.63,Z=1,Dc=1.505 g/cm3,μ=0.414 mm-1,F(000)=471.0。热重分析表明,该配合物在410℃下稳定,UV固体光谱表明,该配合物有很弱的吸收。     

Sandwich-Type Manganese-Substituted Polyoxometalate, [(α-B-ZnW9O34)2W2Mn2(H2O)2]8?

Abstract  

The novel dimeric manganese-substituted polyoxotungstate Na₁₀[(α-B-ZnW₉O₃₄)₂W₂Mn₂(H₂O)₂](OH)₂·34H₂O (1) has been designed and synthesized from the hydrothermal reaction of Na₂WO₄·2H₂O, MnCl₂·4H₂O, and ZnCl₂ in a Teflon-lined stainless steel autoclave at 140°. X-ray diffraction analysis results reveal that compound (1) crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.0901(3) ?, b = 17.8242(4) ?, c = 21.2401(5) ?, β = 93.6380(10)°, Z = 1, V = 4945.8(2) ?³, F(000) = 5244, Dc = 3.974 g/cm⁻³, μ(Mo-Kα) = 2.4037 cm⁻¹, λ(Mo-Kα) = 0.71073 ?. The structure was refined to R = 0.0631 and wR = 0.1532. The polyoxoanion of [(α-B-ZnW₉O₃₄)₂W₂Mn₂(H₂O)₂]⁸⁻ consist of two Keggin lacunary α-B-ZnW₉O₃₄ ¹²⁻ moieties linked via a rhomblike W₂Mn₂O₁₆ group leading to a sandwich-type structure.     

The X-Ray Structure and Spectroscopic Characterization of [Zn(H2O)6][{Zn(H2O)}2(ttha)]·4H2O (ttha?=?Triethylenetetraamine-N,N,N′,N″,N?,N?-hexaacetate)

Abstract  

[Zn(H₂O)₆][{Zn(H₂O)}₂(ttha)]·4H₂O (ttha = triethylenetetraamine-N,N,N′,N″,N‴,N‴-hexaacetate) has been structurally characterized (triclinic, P-1, a = 7.4014(4) ?, b = 8.5521(4) ?, c = 15.0309(7) ?, α = 73.582(1)°, β = 85.173(1)°, γ = 69.935(1)°; V = 857.15(7) ?³; Z = 1). The two Zn²⁺ ions bound by the [ttha]⁻⁶ ligand are in distorted octahedral environments. While there exists a center of symmetry in the [{Zn(H₂O)}₂(ttha)]²⁻ anion in the crystalline state, ¹³C{¹H} NMR spectroscopy demonstrates the absence of a center of symmetry in aqueous solution. Furthermore, electronic absorption spectroscopy reveals that [Zn(H₂O)₆][{Zn(H₂O)}₂(ttha)]·4H₂O reacts with vanadyl(IV) acetate in aqueous solution at room temperature to yield [(VO)₂(ttha)]²⁻. This reaction implies that Zn²⁺ can dissociate from [{Zn(H₂O)}₂(ttha)]²⁻ in aqueous solution.     

Synthesis and Structural Studies of [Na(C7H6O4)(H2O)3](C7H5O4)?·?2H2O

Abstract  The mononuclear complex [Na(C₇H₆O₄)(H₂O)₃](C₇H₅O₄) · 2H₂O has been synthesized and characterized by IR, single crystal X-ray and thermal analysis. The compound crystallizes in the monoclinic space group P2₁ with a = 3.623(2) ?, b = 15.872(6) ?, c = 15.650(5) ?, β = 93.13(4)°, V = 896.6(7) ?³ and Z = 2. The central sodium ion is six coordinated with distorted octahedral geometry by two oxygen atoms from two bridging 3,5-dihydroxybenzoate ligands and four ones from different water molecules. The notable feature of the title complex is the formation of a three-dimensional network, through the combination of coordination bonds, hydrogen bonds and π···π interactions. There are one-dimensional channels in the structure, filled in by water molecules. The compound dehydrates in the temperature range of 70–125 °C and then is stable up to 230 °C. Index Abstract  The mononuclear complex [Na(C₇H₆O₄)(H₂O)₃](C₇H₅O₄) · 2H₂O has been synthesized and characterized by IR, single crystal X-ray and thermal analysis.      

Syntheses, Spectroscopic Data, and X-ray Diffraction Structures of the Heterometallic RuRe Face-shared Bioctahedral (η6-cymene)Ru(μ-Cl)3Re(CO)3 and MnRu2 Edge-shared Trioctahedral [fac-ClRu(CO)3]2(μ-Cl)4Mn(H2O)2 Complexes

Abstract  Thermolysis of the diruthenium compound [(η⁶-cymene)RuCl₂]₂ (1) with ClRe(CO)₅ (2) leads to the formation of the new confacial bioctahedral compound (η⁶-cymene)Ru(μ-Cl)₃Re(CO)₃ (3) in good yields; the same product has also been isolated when a mixture of 1 and 2 is irradiated with near UV–vis light for an extended period of time. Heating 1 and ClMn(CO)₅ (4) does not furnish the corresponding manganese analogue of 3 but rather the trioctahedral halide-bridged product [fac-ClRu(CO)₃]₂(μ-Cl)₄Mn(H₂O)₂ (5). 3 and 5 have been fully characterized in solution and their molecular structures established by X-ray crystallography. Graphical Abstract  Thermolysis of [(η⁶-cymene)RuCl₂]₂ (1) with the respective pentacarbonyl ClM(CO)₅ [where M = Re (2); Mn(4)] affords the halide-bridged compounds (η⁶-cymene)Ru(μ-Cl)₃Re(CO)₃ (3) and [fac-ClRu(CO)₃]₂(μ-Cl)₄Mn(H₂O)₂ (5). 3 and 5 have been isolated and characterized spectroscopically in solution and their molecular structures established by X-ray crystallography.