Synthesis, structure and supramolecular assembly in the crystalline state of a bifunctionalized arylimido derivative of hexamolybdate [n-Bu4N]2[Mo6O17(o,p-(MeO)2C6H3N)2]

A novel bifunctionalized arylimido derivative of hexamolybdate [n-Bu₄N]₂[Mo₆O₁₇(o,p-(MeO)₂C₆H₃N)₂] (1) was synthesized by self-assembled metathesis of α-type octamolybdate ion and 2,4-dimethoxyaniline and structurally characterized by crystal X-ray diffraction. Crystallographic data for1: monoclinic system, space group:C2/c,a = 17.319(4),b = 18.087(4),c = 21.357(5) ?, β = 106.486(4),V = 6415(2) ?³, andZ = 4,D_c = 1.693 g/cm³,R₁ = 0.0439. The complex has a short Mo–N bond length of 1.735(5) ? and an imido (Mo–N–C) bond angle of 177.8(4)^∘. The complex has also been characterized by¹H NMR, IR, and UV–vis spectroscopy.     

Synthesis, Spectroscopic Characterization and Crystal Structure of a New Acetyl phosphorylamidate P(O)[NHC(O)C6H4(4-NO2)][N(CH(CH3)2)(CH2C6H5)]2

Abstract  

A new acetyl phosphorylamidate P(O)[NHC(O)C₆H₄(4-NO₂)][N(CH(CH₃)₂)(CH₂C₆H₅)]₂ has been synthesized and characterized by elemental analysis, ¹H, ¹³C and ³¹P NMR, IR and single crystal X-ray diffraction. Single crystal X-ray analysis shows that it belongs to triclinic system, space group P[`1] P\bar{1} , with a = 10.5868(16) Å, b = 11.8058(18) Å, c = 12.4364(19) Å, α = 65.410(3)°, β = 67.492(4)°, γ = 85.879(3)°, V = 1,298.6(3) Å³, and Z = 2. The intermolecular PO···HN hydrogen bond makes H-bonded dimer of molecule with Ci symmetry. In the crystal network, the dimers are aggregated in the chain arrays through π-stacking between p-NO₂–C₆H₄–C(O)–NH– moieties. Moreover, weak C–H···O and C–H···π interactions exist in the crystal network.     

Synthesis and crystal structure of Cu3(Bipy)2(L1)2(L2)2? 4H2O(Bipy = 2,2′-bipyridine, L1 =1-((2-sulfonateethylimino)methyl)-2-naphthol), L2 = 2-hydroxy-1-naphthaldehyde)

The title compound, Cu₃(Bipy)₂(L¹)₂(L²)₂⋅4H₂O, was synthesized in the methanol solution of Bipy and Cu(II) in the presence of 1-((2-sulfonate-ethylimino)-methyl)-2-naphthol (L¹), which was condensation compound of taurine and 2-hydroxy-1-naphthaldehyde. This complex crystallized in the space group P-1 with a = 9.825(2) ?, b = 12.626(2) ?, c = 14.342(3) ?, α = 90.29(1)^∘, β = 100.67(1)^∘, γ = 101.67(2)^∘, and Z = 2. In the trinuclear Cu(II) complex, there are two type Cu atoms which have square and square pyramid geometries, respectively. The Cu–N distances vary from 1.965(3) to 2.000(4) ?, while the Cu–O distances are between 1.896(3) and 2.337(4) ?.     

Reactions of triosmium clusters with indole: X-ray structures of [Os3(CO)10(μ-OH)(μ-OMeCO)] and [Os3(μ-H)(CO)10(μ-1, 2-η2-NC8H6)]

Treatment of [Os₃(CO)₁₂] with indole in presence of a methanolic solution of Me₃NO⋅2H₂O at 60^∘C afforded the previously reported compounds [(μ-H)Os₃(CO)₁₀(μ-OMe)] 2, [(μ-H)Os₃(CO)₁₀(μ-OH)] 3 and [Os₃(CO)₁₀(μ-OH)(μ-OMeCO)] 4 in 10, 5 and 20% yields, respectively. The reaction of [Os₃(CO)₁₀(MeCN)₂] with indole at room temperature gave [(μ-H)Os₃(CO)₁₀(μ-1,2-η²-NC₈H₆)] 5 in 40% yield. Compounds 4 and 5 have been characterized by single crystal X-ray diffraction studies. Compound 4 crystallizes in the monoclinic space group P2(1)/c with a = 23.1239(3), b = 9.8087(4), c = 16.9017(6) ?, β = 92.6998(14)^∘, Z = 8 and V = 3829.3(2) ?³ and 5 crystallizes in the monoclinic space group P2(1)/c with a = 9.009(3), b = 9.764(4), c = 24.906(6) ?, β = 93.452(14)^∘, Z = 4 and V = 2186.9(13) ?³. Compound 4 consists of an open cluster of three osmium atoms with the hydroxy and methoxycarbonyl ligands bridging the open Os–Os edge. Compound 5 consists of an isosceles triangle of osmium atoms with one elongated Os–Os edge which is bridged by the hydride and the indolyl ligands.     

Structure of diaqua(itaconato) cadmium(II), [Cd(C5H4O4)(OH2)2]

[Cd(C₅H₄O₄)(OH₂)₂] (1), crystallizes in the monoclinic system, space groupP2₁/n, with lattice parametersa=7.323(2),b=16.028(6),c=7.202(2) Å, β=113.11(1)°, andZ=4. The Cd atom coordinates to seven oxygens in a monocapped trigonal antiprism fashion. The antiprisms share one vertex to form chains which run approximately parallel to thec axis. The itaconate ligands link the chains to form layers which stack along theb axis.     

Crystal and Molecular Structures of C6H5CH2SOCH2CONHCH2C6H5 and C6H5SOCH2CON(iC3H7)2

Abstract  The crystal structures for two of the ligands C₆H₅CH₂SOCH₂CONHCH₂C₆H₅ (1) and C₆H₅SOCH₂CON(ⁱC₃H₇)₂ (2) have been determined by X-ray diffraction. These compounds crystallize in orthorhombic system with space groups and cell parameters, Pca21(no. 29), a = 8.4600(5) ?, b = 5.3534(5) ?, c = 32.136(2) ?, V = 1455.42(15) ?³ and Pna21(no. 33) a = 17.5563(11) ?, b = 5.7902(4) ?, c = 14.2866(9) ?, V = 1452.30(16) ?³, respectively. These molecules are stabilized in solid state by various intra and intermolecular hydrogen bonding interactions to give polymeric structures. The reported IR spectra of these compounds in solid state could be explained on the basis of the observed intermolecular hydrogen bonding interactions. Index Abstract  The title compounds C₆H₅CH₂SOCH₂CONHCH₂C₆H₅ (1) and C₆H₅SOCH₂CON(ⁱC₃H₇)₂ (2) were prepared by the oxidation of corresponding sulfides with H₂O₂/SeO₂ in methanol and their structures were determined. The structures show that the SO and CO groups are having “anti” configuration in 1 and “syn” configuration in 2. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal structure of a new basic nitrate of neodymium(III), [Nd6O(OH)8(H2O)14(NO3)6](NO3)2 · 2H2O

A new basic Nd³⁺ nitrate, [Nd₆O(OH)₈(H₂O)₁₄(NO₃)₆](NO₃)₂ · 2H₂O (I), is isolated in the crystal form and studied. Compound I differs from the basic Ln nitrates containing [Ln ₆O(OH)₈] clusters in that it involves a larger number of water molecules. The incorporation of additional water molecules is accompanied by changes in the coordination environment of one of the three crystallographically independent Nd³⁺ cations. Two cations have coordination polyhedra in the form of a monocapped tetragonal antiprism with a coordination number of 9, and the third cation has a polyhedron in the form of a bicapped tetragonal antiprism with a coordination number of 10. Original Russian Text ? I.A. Charushnikova, C. Den Auwer, 2007, published in Kristallografiya, 2007, Vol. 52, No. 2, pp. 248–251.     

Structural determination by X-Ray diffraction and 183W NMR spectroscopy of mono substituted hexatungstates [(n-C4H9)4N]3MW5O19 (M = Nb, V)

The tetrabutylammonium salt of mononiobotungstate [(n-C₄H₉)₄N]₃NbW₅O₁₉ (1) and the tetrabutylammonium salt of monovanadotungstate [(n-C₄H₉)₄N]₃VW₅O₁₉ (2) are isotypes; both crystallize in the monoclinic system, space group C2/c (N° 15) with Z=8. The cell parameters for 1 are a=30.4038(8) ?, b=18.5948(8) ?, c=27.3330(3) ?, β=112.4555(6)°, V=14281.1(7) ?³ and the final reliability factors are R=0.043 and R _w=0.047 for 5801 reflections. The cell parameters for 2 are a=30.096(8) ?, b=18.373(3) ?, c= 27.201(6) ?, β=112.402(14)°, V=13906(5) ?³ and the final reliability factors are R=0.048 and R _w=0.054 for 6122 reflections. Both anions, [NbW₅O_19] ³⁻ and [VW₅O_19] ³⁻ exhibit the Lindqvist structure of the parent hexatungstate anion. The six metal positions are disordered and for each metal site the occupation factor is close to 1/6 M (M=Nb, V) and 5/6 W. Furthermore the two compounds were characterized by IR in the solid state, and ¹⁸³W solution NMR. The ¹⁸³W spectrum of [NbW₅O_19] ³⁻ presents two resonances with relative intensities 4:1 in agreement with the C_4v symmetry of the anion.     

A novel representative {[Rb1.94(H2O,OH)3.84](H2O)0.1}{Al4(OH)4[PO4]3} in the pharmacosiderite structure type

The crystal structure of a new synthetic aluminophosphate {[Rb_1.94(H₂O,OH)_3.84](H₂O)_0.1}{Al₄(OH)₄[PO₄]₃} synthesized under mild hydrothermal conditions (T = 280°C, P = 100 atm) in the Rb₂O-Al₂O₃-P₂O₅-H₂O system is determined using X-ray diffraction (Stoe IPDS diffractometer, λMoK _α, graphite monochromator, 2θ_max = 64.33°, R = 0.032 for 312 reflections). The main crystal data are as follows: a = 7.4931(6) ?, space group P 3m, Z = 1, and ρ_calcd = 2.76 g/cm³. It is shown that the synthesized compound belongs to the pharmacosiderite structure type with a characteristic mixed open microporous framework composed of octahedra and tetrahedra. A comparative crystal chemical analysis of related phases is performed, and the chemical compositions of promising absorbents, i.e., hypothetical compounds potentially possible in the structure type under consideration, are proposed. It is established that pharmacosiderite and rhodizite are homeotypic to each other. Original Russian Text ? O.V. Yakubovich, W. Massa, O.V. Dimitrova, 2008, published in Kristallografiya, 2008, Vol. 53, No. 3, pp. 442–449.     

Crystal structure of the Lanthanum(III) complex [La(DMSO)6(H2O)PW12O40] · C2H5OH (DMSO is dimethyl sulfoxide)

The crystal structure of the [La(DMSO)₆(H₂O)PW₁₂O₄₀] · C₂H₅OH complex (I) (where DMSO is dimethyl sulfoxide) is determined by X-ray diffraction analysis. The coordination polyhedron of the La atom is a distorted tricapped trigonal prism in which two cap sites are occupied by oxygen atoms of the heteropolyanions. For these atoms, the La-O distances [2.760(9) and 2.801(9) Å] are considerably longer than the other distances [ranging from 2.441(10) to 2.569(10) Å] in the environment of the La atom. __________ Translated from Kristallografiya, Vol. 47, No. 6, 2002, pp. 1039–1041. Original Russian Text Copyright ? 2002 by Grigoriev, Shirokova, Fedoseev, Den Auwer.     

Solvothermal Syntheses and Crystal Structures of Neodymium Thiostannates [Nd(dien)3]2[(Sn2S6)Cl2] and [Nd(dien)3]2[(Sn2S6)(SH)2]

Abstract  

Two neodymium thiostannates [Nd(dien)₃]₂[(Sn₂S₆)Cl₂] (1) and [Nd(dien)₃]₂[(Sn₂S₆)(SH)₂] (2) (dien = diethylenetriamine) were synthesized by the reaction of tin and sulfur in the presence of NdCl₃ and Nd₂O₃, respectively under solvothermal conditions. Compounds 1 and 2 crystallize in monoclinic space group P2₁/n. Crystallographic data for 1: a = 11.6722(16), b = 15.119(2), c = 14.1566(19) ?, β = 96.213(3)°, V = 2483.6(6) ?³, Z = 4. For 2: a = 11.7190(14), b = 15.2168(19), c = 14.2209(18) ?, β = 95.775(4)°, V = 2523.1(5) ?³, Z = 4. The nine-coordinate [Nd(trien)₃]³⁺ complex cation formed in situ acts as the counter ion to the [Sn₂S₆]⁴⁻ anion. The [Nd(dien)₃]³⁺, [Sn₂S₆]⁴⁻ and Cl^– (or SH^–) ions form a 3-dimensional network structure through the N–H···S and N–H···Cl hydrogen bonds.     

Crystal structure of M4[(UO2)2C2O4(SO4)2(NCS)2] ( M = K+, Rh+) and K4[(UO2)2C2O4(SeO4)2(NCS)2]

Three heteroacidoligand uranyl complexes M ₄[(UO₂)₂C₂O₄(SO₄)₂(NCS)₂] (M = K⁺ (I), Rb⁺ (II)) and K₄[(UO₂)₂C₂O₄(SeO₄)₂(NCS)₂] (III) have been synthesized and their crystal structure has been determined by X-ray diffraction analysis. The compounds I–III are isostructural and crystallized in the monoclinic system, sp. gr. P2₁/c, Z = 2, a = 11.5548(3) ?, b = 7.0847(1) ?, c = 13.5172(3) ?, β = 93.130(1)°, V = 1104.90(4), R = 0.015 (I); a = 11.5854(9) ?, b = 7.3841(6) ?, c = 13.9072(9) ?, β = 95.754(3)°, V = 1183.74(15), R = 0.0235 (II); a = 11.6715(3) ?, b = 7.1418(2) ?, c = 13.8546(1) ?, β = 93.539(1)°, V = 1152.66(5), R = 0.0126 (III). Basic structural units of these crystals are [(UO₂)₂C₂O₄(XO₄)₂(NCS)₂]⁴⁻ chains, which belong to the crystallochemical group A ₂ K ⁰² B ₂² M ₂¹ (A = UO₂²⁺, K ⁰² = C₂O₂₋⁴, B ² = SO₄²⁻ or SeO₄²⁻, M ¹ = NCS⁻) of uranyl complexes. Uranium-containing chains are connected into a 3D framework via a system of electrostatic interactions with potassium or rubidium cations from outer spheres. Original Russian Text ? I.V. Medrish, E.V. Peresypkina, A.V. Virovets, L.B. Serezhkina, 2008, published in Kristallografiya, 2008, Vol. 53, No. 3, pp. 495–498.     

Synthesis and structure of (NH4)4[(DMF)2Mo8O26]· 2CH3CH2OH·2H2O (DMF= N , N -dimethylformamide)

A new organic-inorganic hybrid γ-octamolybdate complex, (NH₄)₄[(C₃H₇NO)₂Mo₈O₂₆]·2CH₃CH₂OH·2H₂O was synthesized from the mixture of ethanol, DMF, 4-aminobenzoic acid, (NH₄)₆Mo₇O₂₄·4H₂O, HCl and H₂O. The structure was determined by X-ray crystallography. It crystallizes in monoclinic P2₁/n space group with the crystal cell parameters of a = 8.8825(4), b = 21.1608(10), c = 11.1343(6) ?, β = 104.7720(10)°, V = 2023.64(17) ?³ and Z = 2. The crystal X-ray analysis shows that two DMF molecules are bound to γ-octamolybdate anion. The molecular structure is stabilized by the complex hydrogen bonding.     

A Novel 1:1 Co-Crystal of Bis(1,10-Phenanthroline)(1,10-Phenanthroline-5,6-Dione)Nickel(II) Hexafluorophosphate and Tris(1,10-Phenanthroline)Nickel(II) Hexafluorophosphate Complexes, [Ni(phen)2(phen-dione)] [Ni(phen)3] (PF6)4

Abstract  

The purpose of this study was to investigate whether co-crystals form by simply mixing pure solutions of [Ni(phen)₃](PF₆)₂ and [Ni(phen)₂(phen-dione)](PF₆)₂ where phen is 1,10-phenanthroline and phen-dione is 1,10-phenanthroline-5,6-dione. The 1:1 cocrystal, [Ni(phen)₂(phen-dione)][Ni(phen)₃](PF₆)₄·CH₃CN has been characterized by elemental analysis, IR, paramagnetic NMR, and UV–vis spectroscopies, cyclic voltammetry, and single crystal X-ray structure analysis. The title complex crystallized in triclinic crystal system (z = 2) with space group of Pī, a = 13.201(2) ?, b = 14.782(3) ?, c = 22.294(4) ?, α = 81.575(15)^o, β = 88.756(15)^o, γ = 88.032(15)^o and V = 4300.1(14) ?³. A careful inspection of the packing pattern in the lattice reveals that non-covalent interactions of three different types, viz. C–H···F, C=O···H−C and C−H···π interactions, are active in the lattice. The coordination around the Ni(II) centers is a distorted octahedral, with bite angles of 78.3−79.8^o for the chelating phen and phen-dione ligands. Cyclic voltammetry of this co-crystal shows that the Ni(III/II) couple is quasi-reversible. The effective magnetic moment (μ_eff) of the co-crystal was measured to be 2.87 BM per Ni(II) ion by Evans method. The magnitude of μ_eff is consistent with magnetic moment for octahedral Ni(II) complexes.     

Solubility phase diagrams of Me 2SO4-NiSO4-H2O systems and the growth of Me 2Ni(SO4)2 · n H2O crystals [ Me = Na, Rb, Cs; n = 4, 6]

On the basis of the physicochemical analysis of the solubility phase diagrams for the Me ₂SO₄-NiSO₄-H₂O ternary systems (Me = Na, Rb, or Cs), the optimum concentration and temperature conditions for the crystallization of the Me ₂Ni(SO₄)₂ · nH₂O solid phases were found. Techniques for growth of single crystals of these binary salts have been developed. Such techniques allow application of mother liquors containing hydrates or anhydrous sulfates of Na, Rb, Cs, and Ni as raw materials. Na₂Ni(SO₄)₂ · 4H₂O, Rb₂Ni(SO₄)₂ · 6H₂O, and Cs₂Ni(SO₄)₂ · 6H₂O single crystals (28–34) × (8–13) × (5–10) mm³ in size have been grown from aqueous solutions in the dynamic regime. Original Russian Text ? L.V. Soboleva, 2007, published in Kristallografiya, 2007, Vol. 52, No. 6, pp. 1141–1144.     

A new dabco templated metal sulfate, (C6H14N2)[Mn (H2O)6](SO4)2. Chemical preparation, hydrogen-bonded structure and thermal decomposition

The crystal structure of manganese sulfate templated by 1,4-diaza-bicyclo[2.2.2]octane (abbreviated dabco), (C₆H₁₄N₂)[Mn(H₂O)₆](SO₄)₂, was investigated using single crystal X-ray diffraction data. It crystallises in the monoclinic system (space group P2₁/c) with the following unit-cell parameters: a = 12.1392(2) ?, b = 12.3117(2) ?, c = 12.2765(2) ?, β = 104.607(1)°, V = 1775.47(5) ?³ and Z = 4. The structure has been solved using direct methods and refined by least-squares analysis [R ₁ = 0.0381, wR ₂ = 0.1082]. The crystal structure of the title compound is built from isolated [Mn(H₂O)₆]²⁺ octahedral cations, 1,4-diaza-bicyclo[2.2.2]octandiium cations (C₆H₁₄N₂)²⁺ and sulfate anions (SO₄)²⁻ connected by a three-dimensional hydrogen-bond network. The thermal decomposition of the precursor, studied by thermogravimetry and temperature-dependent X-ray powder diffraction, proceeds through four stages giving rise to the mixture of Mn₂O₃and Mn₃O₄. Supplementary Material CCDC 620298 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.     

The triethyl ammonium salt of O,O′-bis(o-tolyl) dithiophosphate [Et3NH]+[(2-MeC6H4O)2PS2]?

The X-ray structure of the triethyl ammonium salt of O,O′-bis(o-tolyl)dithiophosphate, [Et₃NH]⁺[(2-MeC₆H₄O)₂PS₂]⁻, has been determined. Crystal data: Monoclinic, P2₁/c, a = 15.4342(6) Å, b = 10.1913(4) Å, c = 14.0729(6) Å, β = 100.855(1)^∘, V = 2174.0(2) Å⁻³, Z = 4. The immediate environment around phosphorous is distorted tetrahedral with two sulfur and two oxygen atoms in the coordination sphere, with N–H–S bonding involving only one of the sulfur atoms.     

Crystal structure of PbUO2(CH3COO)4(H2O)3

Single crystals of PbUO₂(CH₃COO)₄(H₂O)₃ have been investigated by X-ray diffraction (R = 0.029 for 3175 reflections). The structure of this compound is formed by [Pb(CH₃COO)(H₂O)₃]⁺ chains, which are oriented along the [100] axis and limited by one-core complexes [UO2(CH₃COO)₃]⁻. The coordination numbers of the Pb(II) and U(VI) atoms are 8, and the coordination polyhedron of uranium is a hexagonal bipyramid whose vertices contain oxygen atoms of three bidentate cyclic acetate groups and the uranyl group. Taking into account the different crystallographic roles of acetate ions, the crystal-chemical formula of [PbUO₂(CH₃COO)₄(H₂O)₃] chains can be written as AA′B ²¹ B ¹¹(B ⁰¹)₂ M ₃¹, where A = Pb; A′ = UO₂²⁺; M ¹ = H₂O; and B ²¹, B ¹¹, and B ⁰¹ are CH₃COO⁻ groups.     

A Novel Three Dimensional Organic–Inorganic Hybrid Based Porous Phase: Synthesis and Characterization of Reduced Oxovanadium pyromellitate, [VIV2O2(H2O)2(C6H2(COO)4)]

The hydrothermal reaction of a mixture of VOSO₄ · xH₂O, 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid) and 0.1 M H₂SO₄ for 72 h at 160 °C gives blue needle like crystals of [V^IV ₂O₂(H₂O)₂(C₆H₂(COO)₄)] in 30% yield. The compound has a porous 3-D extended network structure having a rigid architecture which is held together by the multidentate functionalities of 1,2,4,5-benzenetetracarboxylate ligand. Crystal data for the compound: monoclinic space group C 2/c (No:15), a = 11.756(5) ?, b = 9.645(3) ?, c = 11.822(7) ?, β = 107.10(4)°, Z = 8. The compound constitutes the first example of a fully reduced oxovanadium based solid incorporating the organic ligand. This article consists of synthesis, crystal structure and characterization of [V^IV ₂O₂(H₂O)₂(C₆H₂(COO)₄)].     

Synthesis and crystal structure of (NH4)3[UO2(CH3COO)3]2[UO2(CH3COO)(NCS)2(H2O)]

Single crystals of the compound (NH₄)₃[UO₂(CH₃COO)₃]₂[UO₂(CH₃COO)(NCS)₂(H₂O)] (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 = 18.3414(6) ?, b = 16.3858(7) ?, c = 12.4183(5) ?, β = 92.992(1)°, space group C2/c, Z = 4, V = 3727.1(3) ?³, and R = 0.0253. The uranium-containing structural units of crystals I are mononuclear complexes of two types with an island structure, i.e., the [UO₂(CH₃COO)₃]⁻ anionic complexes belonging to the crystal-chemical group (AB ₃⁰¹ = UO₂²⁺, B ⁰¹ = CH₃COO⁻) of the uranyl complexes and the [UO₂(CH₃COO)(NCS)₂(H₂O)]⁻ anionic complexes belonging to the crystal-chemical group AB ⁰¹M₃¹ (A = UO₂²⁺, B ⁰¹ = CH₃COO⁻, M ¹ = NCS⁻ or H₂O).