Crystal structure of [Co(NH3)5Cl]2(W10O32)·4H2O

By single crystal X-ray diffraction the crystal structure of the complex salt [Co(NH₃)₅Cl]₂(W₁₀O₃₂)·4H₂O is determined and the IR spectrum is interpreted. The crystal chemical analysis of the structure of complex cations and decatungstate anions and their packing in the structure is performed.     

Synthesis and crystal structure of the salt of the protonated thiamine cation with the palladium(II) tetrachloride anion [HTA]2[PdCl4]Cl2 · 2H2O

The reaction of thiamine chloride hydrochloride with a solution of palladium chloride in hydrochloric acid gave a protonated thiamine salt [HTA]₂[PdCl₄]Cl₂ · 2H₂O (I) (TA is 4-methyl-3-[(2??-methyl-4??-amino-3??,4??-dihydropyrimidinyl-5??)methyl]-5-(2-hydroxyethyl)thiazolium cation, C₁₂H₁₆N₃O₂S). The crystal structure of I was determined by X-ray diffraction. The crystals are triclinic: a = 11.459(8) ?, b = 12.239(8) ?, c = 6.910(1) ?, ?? = 103.24(3)°, ?? = 76.95(3)°, ?? = 106.04(3)°, Z = 2, space group P $\bar 1$ . The structural units of I are doubly charged [HTA]²⁺ cations, [PdCl₄]^2? and Cl^? anions, and crystallization water molecules combined by hydrogen bonds and electrostatic interactions. The planar thiazolium and pyrimidine rings are in the F conformation, ??_t = 1.0°, ??_p = ?86.6°, and the dihedral angle between the planes is 85.5°. The torsion angles of the hydroxyethyl group are as follows: C(9)C(10)C(11)O(1), 175.6°; S(1)C(9)C(10)C(11), 33.2°; it is involved in the hydrogen bond with the free Cl^? anion. The sulfur atom forms a short (3.052 ?) intermolecular S-Cl contact with the chlorine atom of the [PdCl₄]^2? anion, which forms supramolecular chains.     

Magneto-structural studies of two new cobalt(II)-N,N-diisobutylisonicotinamide compounds: [CoLCl2]n and [Co(L)2(H2O)4][CoLBr3]2·2H2O

Two similar synthetic pathways using the ligand N,N-diisobutylisonicotinamide (L) with anhydrous CoX(2) salts (being X = Cl(-), Br(-)) led to different species: a one-dimensional system, [CoLCl(2)](n), 1, and an ionic product [Co(L)(2)(H(2)O)(4)][CoLBr(3)](2)·2H(2)O, 2, respectively. Compound 1 is a polymer in which ligand L coordinates to tetrahedral Co(II) ions in a bidentate bridging fashion using the pyridine nitrogen and carbonyl oxygen atoms. Compound 2 consists of one octahedral cationic [Co(L)(2)(H(2)O)(4)](2+) entity and two tetrahedral anionic [CoLBr(3)](-) units. In this system, the ligand molecules coordinate only through the pyridine nitrogen atoms. The magnetic properties of 1 and 2 were investigated in the temperature range of 2.0 to 300.0 K and correlations between both (due to the existence of similar features) examined. The study of the magnetic properties of 1 was carried out by considering each Co(II) ion as a perfectly isolated system, hence, J = 0, but taking into account a significant zero-field splitting contribution due to distortions on the tetrahedral environment of the cobalt atoms. The fit of the magnetic susceptibility data together with reduced magnetization vs H/T measurements provided similar parameters (|D| = 10.8 cm(-1), g(⊥) = 1.92, g(‖) = 2.92 for the former and |D| = 11.04 cm(-1)and g = 2.05 for the latter, respectively). On the other hand, the magnetic response of compound 2 has been analyzed using a model which considers the presence of two tetrahedral and one octahedral Co(ii) ions (Co(Td) and Co(Oh)). The study was carried out in two separated blocks, above and below 80 K, where only the most significant effects at each interval of temperature were considered. As a result, the analysis of the magnetic data shows weak antiferromagnetic interactions between the Co(Oh)and the two Co(Td) ions (J = -0.41 cm(-1)) in 2. The best fit parameters were g(Co(Td)) = 2.89, g(Co(Oh)) = 3.50, |D(Co(Td))| = 10.62 cm(-1), |E(Co(Td))| = 2.95 cm(-1), Δ = 240.9 cm(-1) and J(L-S) = -107.1 cm(-1), from where λ was calculated with a final value of -144.8 cm(-1) (J(L-S) = Aκλ). The approximations performed to obtain these values provide reasonable results in agreement with compound 1 and also to other systems in the literature.     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

Synthesis, crystal structure and properties of a new organic-inorganic hybrid Dawson-like polyoxotungstate [Co(2,2''''-bpy)3]2[Co(2,2''''-bpy)2Cl][Co(2,2''''-bpy)2]H2-[SbW18O60]·4H2O

A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9-, formulated [Co(2,2'-bpy)3]2[Co(2,2'-bpy)2Cl][Co(2,2'-bpy)2]H2[SbW18O60]·4H2O (2,2'-bpy= 2,2(-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2'-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9- encapsulating a pyramidal {SbO3} group within the {W18} cluster cage. EPR spectra show that the high-spin octahedral CoⅡ and low-spin CoⅡ ions coexist in the title compound. Magnetic properties indicate that the compound is antiferromagnetic.     

Thermal dehydration and decomposition of cobalt chloride hydrate (CoCl2·xH2O)

Dehydration and decomposition of an undried and a partly dried sample of hydrated CoCl₂ have been investigated by using both isothermal and non-isothermal weight loss methods. The intermediate products of dehydration and decomposition at different temperatures have been characterized by chemical analysis, X-ray diffraction, microscopy, infrared and diffuse reflectance spectroscopy. Though XRD failed to identify clearly the formation of basic salt, infrared spectra reveal the occurrence of hydrogen bonded OH groups in the samples heated at even 500°–600°C. This is further supported from the diffuse reflectance spectra of dehydrated samples which indicate tetragonally distorted co-ordination structures due to the presence of H₂O. Thermodynamic functions for different steps of dehydration have been calculated and discussed in the light of structural changes taking place in the dehydrated salts.The authors wish to express their sincere thanks to Mr. D. N. Ney, head of Pyrometallurgy Division for his keen interest and support during the course of investigation. Thanks are also due to Director R. R. L. Bhubaneswar for his kind permission to publish the paper. One of the authors is thankful the CISR, New Delhi for awarding a Junior Research Fellowship.     

Synthesis and structure of [Zn8(HPO4)8(H2PO4)8]•[(C2H8N)8]•4H2O

A chain-like zincophosphate [Zn₈(HPO₄)₈(H₂PO₄)₈]•[(C₂H₈N)₈]•4H₂O was obtained at room temperature from a ZnO/P₂O₅/dimethylamine/H₂O mixture. The crystal structure was determined by single crystal X-ray diffraction. The symmetry is monoclinic a=1.26450(7)nm, b=1.08477(5)nm, c=1.46311(4)nm, β=98.793(5)°, space group Cc. The structure consists of chains of zinc-corner-sharing Zn₂P₂O₄ four rings. The negative charge of the chains is compensated by the protonated dimethylamine. The characterization by ³¹P solid state nmr spectroscopy is also reported.     

[Bi2Cl10(H2-Norf)4(H2O)8](H-Norf是诺氟沙星)

CommentDuringinvestigationsonvariousmetalcomplexeswithH鄄Norf[1,2],complexationwithBiwasinvestigated.Fig.1showsthestructureofthefirstBi髥complexcontainingtheantibacterialdrugNorfloxacin○,[Bi2Cl10(H2鄄Norf)4(H2O)8].Thisisanioniccompoundcompris鄄ingfour[H2     

Synthesis and structure of the organoantimony peroxide solvates [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·1.5C4H8O2 and [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·6C4H8O2

The organoantimony peroxide (Ar₂SbO)₄(O₂)₂ (Ar = C₆H₃OMe-2, Br-5) was synthesized by the oxidation of Ar3Sb with hydrogen peroxide in the presence or acetoxime or acetophenone oxime in dioxane. The product crystallizes with various content of the solvent molecules in the crystal unit cell [1.5 (I) and 6 (II), respectively]. An X-ray diffraction analysis of the solvates was performed. Four antimony atoms in the peroxide are in the octahedral coordination, and are linked through bridging oxygen atoms and two peroxide groups. The distances Sb-C, Sb-O_bridge, Sb-O_peroxide, O-O and Sb...Sb are 2.117–2.122, 1.960–1.972, 2.193–2.235, 1.461, 1.465 and 3.223–3.237 Å in I, and 2.112, 2.119, 1.957, 1,966, 2.204, 2,246, 1,467, and 3.2439 Å in II.     

Four chromophores in one building block: synthesis,structure and characterization of trans-[Ru(MQ)4Cl2]4+ and trans-[Ru(4,4’-bpy)4Cl2] (MQ+ = N-methyl-4,4’-bipyridinium,bpy = bipyridine)

We report the synthesis, crystal structure, electrochemical and spectroscopic properties of trans-[Ru(MQ)₄Cl₂]⁴⁺ (1⁴⁺), where MQ⁺ = N-methyl-4,4′-bipyridinium. The crystal structure of 1⁴⁺ shows the pyridinic rings bound in a trans fashion to the Ru ion. In 1⁴⁺ and in its analog trans-[Ru(4,4′-bpy)₄Cl₂] (2, bpy = bipyridine), the electrochemical reduction waves of the four iminic ligands occur at very closely spaced potentials. In comparison with previously reported analogues, 1⁴⁺ and 2 present high molar extinction coefficients (ε = 20,000–50,000 M^–1cm^–1), and red-shifted absorptions (up to 800 nm for 1⁴⁺ and up to 600 nm for 2) in acetonitrile. Upon protonation of the four exposed nitrogens of 2 and electrochemical reduction of the ligands in 1⁴⁺ and 2, spectral changes occur with retention of isosbestic points, revealing the presence of four independent chromophores. These results suggest poor electronic communication between the aromatic ligands within each compound, in contrast to related complexes such as cis-[Ru(2,2′-bpy)₂Cl₂] (3).     

Electronic properties and crystal structure of aqua (mepirizole-oxalato)copper(II)monohydrate: [Cu(C11H14N4O2)C2O4·H2O]H2O

A Cu(ll) complex with mepirizole: 4-methoxy-2-(5-methoxy-3-methyl-pyrazoll-yl)-6-methylpyrimidine (L) and oxalate as ligands with the formula [CuL(C₂O₄)(H₂O)]·H₂O has been synthesized. The crystal structure has been determined by X-ray diffraction analysis: monoclinic, space group P2₁/n, Z = 4, a = 7.707(1), b = 14.951(3), c = 14.986(2) Å,β = 92.40(2)°, V = 1725.2(8) ų, D_m = 1.61(1) g cm⁻³, D_c = 1.62 g cm⁻³, R = 0.032 and R_w = 0.035 for 2016 observed reflections. The CuN₂O₂O′chromophore can be described as square pyramidal strongly distorted towards trigonal bipyramidal. The basal coordination positions are occupied by the two oxygen atoms of the bidentate oxalate group, the coordinated water molecule and one nitrogen atom of the bidentate mepirizole group; the other coordinated nitrogen atom occupies the apical position. Magnetic moment, IR, electronic reflectance and ESR spectra are interpreted in accordance with the proposed stereochemistry.     

Synthesis and structure of Mu-4, the new layered aluminophosphate [(C2H5)2NH2]4[Al8P10O40H2]·[H2O]2.5

The title compound (named Mu-4) is a new layered aluminophosphate with a unusual A1/P ratio for this kind of materials. Mu-4 was obtained from a quasi non-aqueous mixture involving mainly diethylformamide (DEF) as solvent, in addition to limited amounts of water. DEF is decomposed during the synthesis and the resulting protonated diethylamine is occluded in the as-synthesized material. The crystal structure was determined by single crystal X-ray diffraction. The symmetry is triclinic, a=8.632(4) Å, b=9.267(7) Å, c= 17.461(10) Å, α=86.66(5)°, β=82.20(4)° and γ=89.28(5)°, space group P-1. The structure consists of anionic double sheets essentially built from double 4-ring (D4R) units. The inorganic layers are in strong interaction with water and the protonated amine which is located in the interlayer spacing. Another type of diethylamine protrudes into the 8-membered rings (8-MR) present in the layers. The characterization of this new aluminophosphate by ¹³C, ²⁷Al and ³¹P solid state NMR spectroscopy is also reported.     

[Co(NH3)6]2[Cd8(C2O4)11(H2O)4]·8H2O：A 5-connected sqp topological metal-organic framework co-templated by Co(NH3)63+ cation and (H2O)4 cluster

In our efforts to construct new metal-organic frameworks (MOFs) by template-directing method, a new cadmium oxalate, [Co(NH3)6]2[Cd8(C2O4)11(H2O)4]·8H2O (denoted HNU-1), has been synthesized under hydrothermal condition in the presence of Co(NH3)6Cl3. The crystal structure of HNU-1 was determined by single-crystal X-ray diffraction (monoclinic, C2/c), a = 11.126(2)Å, b = 17.361(4)Å, c = 16.119(3)Å, β = 102.40(3)°, V = 3040.8(10)Å3 and Z = 8. The open framework of HNU-1 contains 12-ring channels and exhibits a 5-connected sqp topological network with dinuclear Cd(Ⅱ) clusters acting as nodes. The Co(NH3)63+ cations and unusual hydrogen-bonded (H2O)4 clusters are found in the 12-ring channels with an alternative arrangement. It is believed that the (H2O)4 clusters play a co-templating role in the crystallization of HNU-1.     

Synthesis and crystal structure of a neutral open framework cobalt(II) phosphate Co6(PO4)4·7H2O with a channel structure

Using tri-ethyl phosphate as a phosphate source, the hydrothermal reaction of cobalt(II) oxalate di-hydrate, zinc oxide and 1,8 di-amino octane at 200°C gave purple crystals of Co₆(PO₄)₄?·?7H₂O (1), along with a mixture of open-framework zinc–cobalt phosphates Co–Zn–HPO₄, and Co₃(HPO₄)₂(2OH). Compound 1, has been characterized by thermal analysis, FTIR and single crystal X-ray diffraction. The single crystal structure of Co₆(PO₄)₄?·?7H₂O reveals cobalt in four, five and six-fold coordination with linkages through the bridging water molecules and the oxygen atoms of the phosphate in the subunits. Four subunits are connected together through the oxygen atoms (PO₄), to form the three dimensional open framework structure, with a 20-member ring channel that hosts two uncoordinated water molecules. Thermal removal of the water molecules occurs between 400–600°C, with the collapse of the structure above 600°C.     

Complexes [Cu(H2L)](NO3)2 and [Cu(H2L)Cl]2[CuCl2]Cl · 0.5H2O (H2L is chiral bis(menthane) propylenediaminodioxime): Synthesis and structure

The synthesis of the [Cu(H₂L)](NO₃)₂ complex (I) and of a mixed-valent complex [Cu(H₂L)Cl]₂[CuCl₂]Cl·0.5H₂O (II), where L is chiral bis(menthane) propylenediaminodioxime. According to the data of single-crystal X-ray diffraction analysis, compounds I and II have ionic structures. In complex cations, the Cu²⁺ ion coordinates four N atoms of tetradentate chelate ligand, namely, the H₂L molecule. The coordination surrounding of the Cu atom in I is a distorted square CuN₄, while in II, it is a distorted square pyramid CuN₄Cl. The complex anion [CuCl₂]^? in II has linear structure. The mutual arrangement of oxime groups in H₂L corresponds to amphi-configuration of a ligand and therefore, intramolecular hydrogen bond O...H-O are formed in H₂L. The complex cations in compound II are joined in dimers through hydrogen bonds Cl...H-O. The values μ_eff for I and II are equal to 1.82 and 2.82 μ_B, respectively.     

Synthesis and structure of [C3N2H5][Cu(H2PO4)2Cl]·H2O with a chain structure: the first example of an organically templated copper (II) phosphate

A new one-dimensional copper (II) phosphate, [C₃N₂H₅][Cu(H₂PO₄)₂Cl]·H₂O, I, with pseudo-10-membered channels along the b-axis formed by the hydrogen bonded chains, containing imidazolium ions has been synthesized and characterized by single-crystal X-ray diffraction. The compound being the first example of an organically templated copper (II) phosphate, crystallizes in the monoclinic space group P2₁/n (No. 14) with a=8.9998(14) Å, b=7.0189(11) Å, c=18.986(3) Å; β=102.964(3)°; V=1168.8(3) ų; Z=4. The copper chlorophosphate chains in I are topologically similar to those observed in fornacite and vauquelinite.     

Synthesis and crystal structure of Cs7[BW12O40][Rh2(CH3COO)4Cl]2 · 8H2O

The binary salt Cs₇[BW₁₂O₄₀][Rh₂(CH₃COO)₄Cl]₂ · 8H₂O was obtained by heating of K₈[HBW₁₁O₃₉] · 13H₂O with [Rh₂(CH₃COO)₄(H₂O)₂] in water followed by crystallization in the presence of CsCl. The crystal structure of the salt was determined by X-ray diffraction. Its ionic structure consists of the Cs⁺ cations, the Keggin-type heteropoly anions [BW₁₂O₄₀]^5?, and the polymeric chain anions catena-[Rh₂(CH₃COO)₄Cl] _n ^n? .     

Synthesis and spectroscopic characterization of trans-[Co(en)2(NO2)2]X (X = dodecyl sulfate,picrate, diclofenac or saccharinate) and the single-crystal X-ray structure of the saccharinate salt,trans-[Co(en)2(NO2)2](C7H4NSO3)·H2O

trans-[Co(en)₂(NO₂)₂]X complexes, where X?=?C₁₂H₂₅SO₄ (1), C₆H₂N₃O₇ (2), C₁₄H₁₀Cl₂NO₂ (3) and C₇H₄NSO₃ (4), have been synthesized by slowly mixing aqueous solutions of trans-dinitrobis(ethylenediamine)cobalt(III) nitrate and sodium dodecyl sulfate, picrate, diclofenac and saccharinate, respectively, at a 1?:?1 mol ratio. Good crystals of trans-dinitrobis (ethylenediamine)cobalt(III) saccharinate monohydrate, [Co(en)₂(NO₂)₂](C₇H₄NSO₃)·H₂O, were obtained. The salt is orthorhombic, space group P2₁2₁2, with a?=?21.553(2), b?=?8.503(1), c?=?10.238(1)?Å, Z?=?4, V?=?1876.3(3)?ų, R ₁?=?0.0286 and wR ₂?=?0.0727. A structure determination revealed an ionic structure consisting of discrete [Co(en)₂(NO₂)₂]⁺ cations and [C₇H₄SO₃N]^– anions.