Hydrothermal synthesis of a mixed-valence hexamolybdate cluster: crystal structure of [HN(CH2CH2)3N]2[HMoVMoVI5O19]·[N(CH2CH2)3N]

The hydrothermal reaction of MoO₃, V, Na₂WO₄· 2H₂O, [N(CH₂CH₂)₃N](1,4-diazabicyclo[2.2.2] octane), and H₂O at 160°C for 90h gave dark-brown crystals of [HN(CH₂CH₂)₃N]₂[HMo^VMo^VI ₅O¹⁹]·[N(CH₂CH₂)₃N], (1), in 40% yield. Complex (1) is the first one-electron reduced mixed-valence hexamolybdate to be crystallized and structurally characterized. The crystal structure of (1) consists of discrete [HMo^VMo^VI ₅O₁₉]^2– anions, [HN-(CH₂CH₂)₃N]⁺ cations, and neutral [N(CH₂CH₂)₃N] molecules of crystallization.     

Hydrothermal syntheses and crystal structures of two organic–inorganic hybrid molybdovanadates based on [V2Mo6(OH)2O24]4− and [VMo12O40]3− polyoxoanions

Two new organic–inorganic hybrid cobalt-molybdovanadates [Co(phen)₃]H₂[H₂V₂Mo₆O₂₆] · 7H₂O (1) and [Co(2,2′-bipy)₃][Na(H₂O)₇][VMo₁₂O₄₀] (2) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR, UV, XPS spectroscopy, thermogravimetric (TG) analyses, and X-ray single crystal diffraction. The molecular structure of 1 consists of a [V₂Mo₆(OH)₂O₂₄]^4? polyoxoanion, a [Co(phen)₃]²⁺, two H⁺ and seven lattice water molecules. The structure of [V₂Mo₆(OH)₂O₂₄]^4? consists of six MoO₆ octahedra and two VO₄ tetrahedra; six MoO₆ octahedra are linked by edge-sharing oxygens forming a {Mo₆} ring, and two VO₄ tetrahedra cap opposite sides of the {Mo₆} ring. The molecular structural unit of 2 is constructed from a typical Keggin-type [VMo₁₂O₄₀]^3? polyoxoanion and a [Co(2,2′-bipy)₃]²⁺ cation and a Na⁺ countercation; Co²⁺ is coordinated by six nitrogens from three 2,2′-bipyridines forming a distorted octahedron.     

Hydrothermal synthesis and crystal structure of a heteropolyoxotungstate formed by sandwich-type heteropolyanion [Gd(PW11O39)2]11− and reduced [Cu(en)2] + cations

A heteropolyoxotungstate, [Cu(en)₂]₂H₈[Gd(PW₁₁O₃₉)₂] ·?(H₂en)_0.5 ·?3H₂O (1), has been hydrothermally synthesized and characterized by IR, XPS, TGA and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P 1, with a =?12.651(2) ų, b =?20.559(3) ų, c =?21.729(3) ų, α =?71.379(2), β =?82.829(2), γ =?75.532(2)°, V =?5179.5(14) ų, Z =?2, R ₁ =?0.0702 and ωR ₂ =?0.1479. The heteropolyanion is composed of two monovacant [α-PW₁₁O₃₉]^7? Keggin moieties linked via a Gd atom leading to a sandwich-type structure. The Gd center is in a distorted square antiprismatic coordination environment with eight oxygen atoms, four from each of the two [α-PW₁₁O₃₉]^7?moieties.     

Hydrothermal synthesis and crystal structure of a 1-D compound constructed from molybdovanadate clusters [V2Mo6O26]6− and copper complexes

A 1-D organic–inorganic hybrid compound, {Cu(en)₂}[V₂Mo₆O₂₆{Cu(en)₂}₂] · 4H₂O [en = ethylenediamine] (1), was hydrothermally synthesized and characterized by IR, UV spectroscopy, TG/DTA analyses, and single crystal X-ray diffraction. The X-ray crystallography analysis reveals an infinitely extended 1-D chain constructed from a molybdovanadate cluster [V₂Mo₆O₂₆]^6? as a building unit, two copper(II) complex fragments, {Cu(en)₂}²⁺, as attached groups and a copper(II) fragment, {Cu(en)₂}²⁺, as a bridging group. Each chain links to adjacent chains through weaker secondary Cu–O interactions forming an interesting 3-D supramolecular architecture.     

The crystal structure of tetraphenylphosphonium pentacyanonitridorhenate(V), (PPh4)3[ReN(CN)5]·7H2O

Summary The crystal structure of (PPh₄)₃[ReN(CN)₅]·7H₂O has been determined from three dimensional X-ray diffraction data. The orange crystals are triclinic, space group , with cell dimensions a=12.514(3), b=15.8514), c=19.030(3) Å, =77.62(2), =84.61(1) and =74.03(2)^o, z=2, D_obsd=1.40(1) g cm^–3 and D_calc=1.37(1) g cm^–3. The anisotropic refinement of 5861 observed reflections converged to R=0.049.The [ReN(CN)₅]^3– ion has a distorted octahedral geometry. Bond distances: ReN=1.68(1), Re–C_av (planar)=2.12(1), Re–C (axial)=2.39(1) Å. The Re atom is displaced by 0.31 Å out of the plane formed by the four carbon atoms towards the nitrido ligand.     

Unexpected preparation and X-ray crystal structure of the dinuclear complex Mo2(μ-P(O)(OCH3)2)2(CO)4(P(OCH3)3)2(CF3COO)2

Prolonged reaction of CF₃COOH with Mo(CO)₃(P(OCH₃)₃)₃ in CH₂Cl₂ yields the dimer [Mo(CO)₂(μ(O)P(OCH₃)₂)P(OCH₃)₃CF₃COO]₂ in low yield. The complex has been characterized by the usual spectroscopic methods and by an X-ray crystal structure determination. The molybdenum atoms are linked by two OP bridges, the six-membered dimetallacycle adopting a twisted-boat conformation. Each molybdenum is seven-coordinated and has a capped trigonal prism geometry, the capping position being occupied by an oxygen atom of the bridging OP(OCH₃)₂ group. A mechanism similar to the well-known Michaelis-Arbuzov rearrangement is proposed and substantiated by the concomitant apparition of CF₃COOCH₃ during the reaction.     

Comparative study of crystal structures of [M(NH3)5NO2]XY and [M(NH3)5ONO]XY. Crystal structure of [Co(NH3)5NO2](NO3)2·0.25H2O

The crystal structure of [Co(NH₃)₅NO₂](NO₃)₂·0.25H₂O has been determined. Co₁N₈O_8.25H_15.5, a=7.582(3), c=10.331(3) Å, V=593.9(5) ų, d_calc=1.782 g/cm³ for Z=2, space group I 4mm (C _4v ⁹ , No. 107). The structure is of the island type. Complex (distorted octahedral) cations are bonded to the NO ₃ ^? anions by electrostatic forces. Crystallization water is located in the vicinity of the labile NO₂ group.     

Synthesis and crystal structure of [NEt4]2[HFe3Rh(CO)12], the first tetranuclear FeRh hydridocarbonyl cluster

The anion [HFe₃Rh(CO)₁₂]²⁻ was obtained by reaction of [HFe(CO)₄]⁻ with Rh₂(CO)₄Cl₂ in refluxing THF. Its solid state structure consists of a tetrahedron of metal atoms with three edge-bridging and nine terminal carbonyl groups. The hydridic ligand bridges a face containing the rhodium atom. [NEt₄]₂[HFe₃Rh(CO)₁₂] crystallizes in the orthorhombic space group Pnnma, with a 19.983(5) Å, b 15.168(4) Å. c 11.915(2) Å, V 3611(2) ų, Z = 4, R = 0.043, R_w = 0.054 for 1680 unique reflections with I > 3σ(I).     

Platinum-silver clusters: synthesis and crystal structure of [Pt3Ag(μ-CO)3(PPh3)5]ClO4 · 2H2O

Reaction of [NBu₄]₂[Pt₁₂(CO)₂₄] with [Ag(PPh₃)₄]ClO₄ and PPh₃ leads to two isolable platinum-silver clusters; the title complex was characterised by single crystal X-ray diffraction. the Pt₃Ag core is tetrahedral; one Pt atom is seven-coordinated, the other two are six-coordinate.     

Synthesis and crystal structure of Cs2[(UO2)2(C2O4)3] and Cs2[UO2(C3H2O4)2] · H2O

Cs₂[(UO₂)₂(C₂O₄)₃] (I) and Cs₂[UO₂(C₃H₂O₄)₂] · H₂O (II) have been synthesized and studied by X-ray diffraction. The crystals of complexes I and II are monoclinic: a = 8.1453(2) Å, b = 8.9831(2) Å, c = 11.3897(4) Å, β = 104.0950(10)°, V = 808.29(4) ų, space group P2₁/n, Z = 2, and R ₁ = 0.0255 for I and a = 9.6998(2) Å, b = 17.8686(3) Å, c = 8.2074(2) Å, β = 97.5780(10)°, V = 1410.10(5) ų, space group P2₁/c, Z = 4, and R ₁ = 0.0287 for II. The uranium-containing structural units of complexes I and II are [(UO₂)₂(C₂O₄)₃]^2? chains and [UO₂(C₃H₂O₄)₂] ₂ ^4? dimers, which belong to the AK _0.5 ⁰² T¹¹ and AT¹¹B⁰¹ crystallochemical groups (A = UO ₂ ²⁺ , K⁰² and T¹¹ = C₂O ₄ ^2? , T¹¹ and B⁰¹ = C₃H₂O ₄ ^2? ) of uranyl complexes.     

Synthesis and structure of bismuth-containing complexes [Ph3PMe] 2 + [BiI5]2− and [Ph3PMe] 2 + [BiI5 · C5H5N]2− · C5H5N

The complexes [Ph₃PMe] ₂ ⁺ [BiI₅]^2? (I) and [Ph₃PMe] ₂ ⁺ [BiI₅ · C ₅H₅N]^2? · C ₅H₅N (II) were synthesized by the reaction of bismuth triiodide with triphenylmethylphosphonium iodide, and their structures were determined by X-ray diffraction analysis. The P atom in cation I has slightly distorted tetragonal coordination polyhedron (the CPC angles 109.42(4)° and 109.52(4)°, the bond lengths P-C_Ph 1.779(2), P-C_Me 1.793(1) Å. The Bi atom in the anion of complex I has an ideal trigonal-bipyramidal coordination polyhedron (Bi-I_eq 3.0031(4), Bi-I_eq 3.0485(5) Å). The crystal of complex II consists of the anions [BiI₅ · C ₅H₅N]^2?, solvated pyridine molecules, and two types of crystallographically independent tetrahedral triphenylmethylphosphonium cations (the angles CPC 106.9(1)°–111.7(1)°, the distances P-C_Ph 1.785(3)–1.792(3), P-C_Me 1.793(3), 1.786(3) Å). The Bi atoms in the anion of complex II have a distorted octahedral coordination polyhedron (Bi-I 3.0878(4)–3.1240(3), Bi-N(1) 2.628(3) Å).     

The synthesis and crystal structure of a copper-sulfur cluster [Cu4(S5)2(C5H5N)4]·S8

The cluster [Cu₄(S₅)₂(C₅H₅N)₄]·S₈ with cage structure has been obtained by reaction of copper powder with sulfur and K₂S _x in pyridine, and its structure was determined by X-ray crystallography. The crystal data for the title compound: triclinic, P (No. 2),Z = 2,a = 11.818(4) Å,b = 13.155(3) Å,c = 14.177(4) Å, = 93.79(2)°, = 96.68(2)°, = 115.76(2)°,V = 1954.52(1) ų. The structure was refined toR = 0.038R _w = 0.053) for 6444 data withI > 3.0(I).Dedicated to Professor Jiaxi Lu on the occasion of his 80th birthday.     

Crystal and molecular structure and ion selective and complexing properties of 1,5-bis[2-(dioxyphosphoryl-4-methoxy)phenoxy]-3-oxapentane dihydrate [(OH)2(O)P(C6H3OCH3)(OCH2CH2)2 O(C6H4OCH3)P(O)(OH)2] · 2H2O

Ion selective and complexing properties of 1,5-bis[2-(dioxyphosphoryl-4-methoxy)phenoxy]-3-oxapentane dihydrate H₄M² · 2H₂O (I) were described. X-ray diffraction analysis for compound I was performed. The crystals are orthorhombic, a = 7.9818(16) ?, b = 30.553(6) ?, c = 9.0559(17) ?, V = 2208.5(8) ?³, Z = 4, space group Pnma, R = 0.0500 over 1372 reflections with I > 2??(I). In I, the H₄M² molecules are combined by hydrogen bonds (HB) with two crystallographically independent H₂O(7) and H₂O(8) molecules to give neutral H₄M² · 2H₂O aggregates. The HB between the phosphoryl and hydroxyl oxygen atoms of the aggregates and the donor O(7)-H??O(8) HB give rise to a layered structure. Conclusions about the Cu(H₂M²) compound structure were drawn based on the X-ray diffraction, DTA, and vibrational spectroscopy data.     

The vibrational spectra of [Nb(O2)F5]2−

The Raman and i.r. spectra of solid K₂[Nb(O₂)F₅] · H₂O and the Raman spectrum of its aqueous solution are reported, and assignments for the vibrations of the anion proposed.     

Synthesis and Crystal Structure of[Co3(CO)9(μ3-C)C(O)OCH2]2

The title compound [Co3(CO)9(μ3-C)C(O)OCH2]2 was synthesized by the reaction of [Cl3CC(O)OCH2]2 with Co2(CO)8 at 40～50 ℃. Crystal data: C24H4O22Co6, Mr=997.88, monoclinic, space group P21/n(#14), a=9.330(2), b=15.197(4), c=11.783(4), β=91.16(2)°, V=1670.4(7) 3, Z=2, Dc=1.984 g/cm3, μ(MoKα)=30.01 cm-1, F(000)=972.00, T=293K, final R=0.045, Rw=0.051 for 1936 observed reflections with I＞2σ(I). The structure contains two centrosymmetric dimeric molecules in a unit cell, each of which has two tetrahedral skeletons (CCo3) connected through a C(O)OCH3CH2OC(O) bridge.     

Synthesis and structure of the polymeric cluster compound [Mn(H2O)4]3[W4S4(CN)12]·nH2O containing very large cavities

The compound [Mn(H₂O)₄]₃[W₄S₄(CN)₁₂]·nH₂O (1) was prepared by the reaction of an aqueous solution of MnSO₄ with a glycerol solution of KCs₅[W₄S₄(CN)₁₂]·4H₂O. Complex 1 was characterized by X-ray diffraction analysis and IR spectroscopy. According to the X-ray diffraction data, the three-dimensional polymeric framework of 1 comprises only 24.2% of the unit-cell volume. The volume of the cavities per formula unit is 1664 ³. The cavities are occupied by highly disordered water molecules.