Reactivity of triangular oxalate cluster complexes [M<Subscript>3</Subscript>Q<Subscript>7</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript>]<Superscript>2−</Superscript> (M = Mo or W; Q = S or Se)

The reactions of the oxalate complexes [M₃Q₇(C₂O₄)₃]²⁻ (M = Mo or W; Q = S or Se) with Mn^II, Co^II, Ni^II, and Cu^II aqua and ethylenediamine complexes in aqueous and aqueous ethanolic solutions were studied. The previously unknown heterometallic complexes [Mo₃Se₇(C₂O₄)₃Ni(H₂O)₅]·3.5H₂O (1) and K₃{[Cu(en)₂H₂O]([Mo₃S₇(ox)₃]₂Br)}·5.5H₂O (2) were synthesized. In these complexes, the oxalate clusters serve as monodentate ligands. The K(H₂en)₂[W₃S₇(C₂O₄)₃]₂Br·4H₂O salt (3) was isolated from solutions containing Co^II, Ni^II, or Cu^II aqua complexes and ethylenediamine. The reaction of [Mo₃Se₇(C₂O₄)₃]²⁻ with HBr produced the bromide complex [Mo₃Se₇Br₆]²⁻, which was isolated as (Bu₄N)₂[Mo₃Se₇Br₆] (4). Complexes 1–3 were characterized by X-ray diffraction, IR spectra, and elemental analysis. The formation of 4 was detected by electrospray mass spectrometry. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1645–1649, September, 2007.     

Synthesis of Molybdovanadates Coordinated by Oxalato Ligands. The Crystal Structure of K6[Mo6V2O24(C2O4)2]·6H2O

The oxalato complex of a polyoxomolybdovanadate, K₆[Mo₆V₂O₂₄(C₂O₄)₂]·6H₂O has been obtained by reaction of potassium molybdate, ammonium vanadate and tartaric or ascorbic acid. Such conversion of dicarboxylate into oxalate ions indicates the catalytic role of molybdenum. Complexes of analogous composition also were obtained in the reactions of MoO₃, V₂O₅ and potassium oxalate, or M ₂CO₃ (M = Rb, Cs) and oxalic acid. The centrosymmetrical molybdovanadate anion [Mo₆V₂O₂₄(C₂O₄)₂]^6- consists of six MoO₆ and two VO₆ edge-sharing octahedra to give the n -[Mo₆O₂₆]^4- structure. All complexes were characterized by powder and single crystal X-ray analyses, ESR and IR spectra and TG and DSC measurements.     

Heteropoly Complexes Na0.5Cs2 ? x[H0.5 ? xM

Crystals of novel heterepoly complexes (HPC) Na_0.5Cs_{2 − x} [H_{0.5 − x} M _x ^II X^III(OH)₆Mo₆O₁₈] · 7−8H₂O (M^II = Fe, Mn; X^III = Cr, Al) are synthesized. Crystal structures of the complexes Na_0.5Cs_{2 − x} [H_{0.5 − x} Fe_xCr(OH)₆Mo₆O₁₈] · 7H₂O (I) (x = 0.19) and Na_0.5Cs_{2 − x} [H_{0.5 − x} Mn_xAl(OH)₆Mo₆O₁₈] · 8H₂O (II) (x = 0.22) are determined (space group Pbcn, Z = 8, a = 23.023(4) Å, b = 22.064(4) Å, c = 11.606(3) Å, V = 5895.66 ų for I and a = 22.972(9) Å, b = 22.002(8) Å, c = 11.543(5) Å, V = 5834.18 ų for II, respectively). The [X^III(OH)₆Mo₆O₁₈]³⁻ ligands were found to be coordinated in monodentate fashion to M atoms due to the participation of a terminal O atom of the cis-MoO₂ group in coordination with the Fe and Mn atoms, which was confirmed by IR data. __________ Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 9, 2005, pp. 663–676. Original Russian Text Copyright ? 2005 by Gavrilova, Molchanov.     

A new hybrid material constructed from octamolybdate anion and neutral dinuclear copper units

A new organic–inorganic hybrid material constructed from octamolybdate anion and neutral dinuclear copper(I) units, H₄{[Cu₂(ophen)₂]₂[Mo₈O₂₆]}[Cu₂(ophen)₂] · H₂O (1) (Hophen =2-hydroxy-1,10-phenanthroline), has been prepared under hydrothermal condition and characterized by elemental analysis, IR, XPS, TGA and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P 1, with a = 9.9091(8), b = 13.3981(8), c = 14.8266(10) Å, α = 84.6310(10), β = 83.0620(10)°, γ = 77.7800(10), V = 1905.0(2) ų, Z = 1. Compound 1 contains a centrosymmetric polyoxoanion {[Cu₂(ophen)₂]₂[Mo₈O₂₆]}^4?, in which the β-[Mo₈O₂₆]^4? is bisupported by two copper(I) coordination groups through the terminal oxygen atoms. The discrete molecules of 1 are extended into a 3-D supramolecular array through C–H ··· O hydrogen bonds and strong aromatic π–π stacking contacts.     

Hydrothermal Synthesis and Structure of Two New Mo(V)-Oxide Phosphates

Two new members of Mo(V) phosphates were synthesized by hydrothermal methods. (enH₂)(enH)[NaMo₁₂O₂₄(OH)₆(HPO₄)₂(H₂PO₄)₆]·(en)₄·20H₂O(1)(en=H₂ NCH₂CH₂NH₂)[HAD-H₂]₂[HAD-H]₂[Zn₃Mo₁₂O₂₄(OH)₆(PO₄)₂(HPO₄)₆]·6H₂O (2) (HAD=H₂N(CH₂)₆NH₂). Compound 1 crystallized in the space group P2(1)/n, a=15.93120(10) Å, b=15.8946(2) Å, c=17.0665(2) Å, V=4316.02(8), =92.9060(10)°, Z=2. Compound 2 crystallized in the space group P(–1) with a=12.3726(3) Å, b=14.1948(3) Å, c=14.2310(4) Å, =72.7100(10), =65.0230(10), =69.5600(10)°, Z=2089.70(9) ų, and Z=1. The structure of 1 consists of sandwich-shaped cluster anion [Na{Mo^V ₆O₁₂(OH)₃(HPO₄)(H₂PO₄)₃}₂]^3– ({Na(Mo ^V ₆ ) ₂ }) held together via intermolecular hydrogen-bonding contacts. For the compound 2, the sandwich-shaped clusters Zn[Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃]₂ ({Zn(Mo ^V ₆ ) ₂} are linked by tetrahedrally-coordinated zinc into layers. Organic cations ([H₃N(CH₂)₆NH₃]²⁺ and [H₃N(CH₂)₆NH₂]⁺) are filled in the spaces between lamellas. The layers are held together by a hydrogen-bonded network, which involves the terminal phosphate P-OH groups, as well as organic cations and several waters of solvation.     

(Se4)2[Mo2O2Cl8][MCl6](M = Zr,Hf) — Tetraselenium(2+)Halometalates with two Different Anions

The reaction of Se₄[Mo₂O₂Cl₈] with Se₄[MCl₆] (M = Zr, Hf) or of Se, SeCl₄, MoOCl₄, and MCl₄ (M = Zr, Hf) at 120 °C in sealed evacuated glass ampoules gives (Se₄)₂[Mo₂O₂Cl₈][MCl₆] (M = Zr, Hf) in the form of dark‐green, air sensitive crystals in quantitative yield. The crystal structure analyses of both isotypic compounds (monoclinic, P2₁/c, Z = 2, a = 1336(2), b = 716(1), c = 1518(4) pm, β = 106.0(2)° for M = Zr; a = 1334.1(8), b = 715.03(9), c = 1518.2(3) pm, β = 106.00(2)° for M = Hf) show the presence of square‐planar Se₄²⁺, of dinuclear [Mo₂O₂Cl₈]^2—, and of almost regular octahedral [MCl₆]^2— ions. X‐ray crystallographic investigations on (Se₄)₂[Mo₂O₂Cl₈][ZrCl₆] give no hint for solid state phase transitions between —160 and 200 °C. This is in contrast to the related compounds Se₄[Mo₂O₂Cl₈] and Se₄[ZrCl₆] which both undergo phase transitions accompanied by reorientation of the cations and anions. (Se₄)₂[Mo₂O₂Cl₈][ZrCl₆] is paramagnetic and obeys the Curie‐Weiss law with a Weiss constant of —4(7) K indicating only weak interaction between the paramagnetic centres. The magnetic moment of 1.7(1) μ_B is consistent with the presence of Mo^V (d¹ configuration) and supports the ionic formula.     

Syntheses and structures of two new lithium-heptamolybdates

The synthesis, crystal structures, IR, UV–vis, ⁷Li NMR spectra, electrochemical investigations, and conductivity studies of two new lithium-heptamolybdates, (NH₄)₄[Li₂(H₂O)₇][Mo₇O₂₄]·H₂O (1) and (NH₄)₃[Li₃(H₂O)₄(μ₆-Mo₇O₂₄)]·2H₂O (2), are reported. In 1 the (NH₄)⁺ and [Li₂(H₂O)₇]²⁺, cations are charge balanced by the heptamolybdate anion. In 2, the [Mo₇O₂₄]^6? anion is coordinated to three unique Li⁺ ions via a μ₆-hexadentate-binding mode resulting in the formation of a two-dimensional (2-D) [Li₃(H₂O)₄(μ₆-Mo₇O₂₄)]^3? anionic complex, charge neutralized by three (NH₄)⁺ ions. The cations, anions, and the lattice water molecules in 1 and 2 are linked by weak H-bonding interactions.     

Synthesis and characterization of oxomolybdate clusters containing coordinatively bound organo-diazenido units: the crystal and molecular structure of the hexanuclear diazenido-oxomolybdate, (NBun4)3[Mo6O18(N2C6H5)]

(NBuⁿ₄)₃[Mo₆O₁₈(N₂C₆H₅)] has been obtained by treating (NBuⁿ₄)₂[Mo₆O₁₉] with an equivalent amount of phenylhdyrazine in benzene. X-ray crsytallography reveals the identity of the deep red crystalline material as a polymolybdate species incorporating a coordinatively bound organo-diazenido unit. The anion [Mo₆O₁₈(N₂C₆H₅)]³⁻ is structurally similar to the precursor [Mo₆O₁₉]²⁻, with the terminally bound phenyldiazenido group replacing a terminal oxo unit of the hexamolybdate moiety. (NBuⁿ₄)₃[Mo₆O₁₈(N₂C₆H₅)] crystallizes in the orthorhombic space group Pmcn with a = 17.162(3) Å, b = 17.577(3) Å, c = 23.860(4) Å, V = 7197.7(8) ų, Z = 4, and D_c = 1.56 g cm⁻³ [μ = 10.60 cm⁻¹, Mo-K_α (λ = 0.71069 Å)]. Solution and refinement based on 2118 reflections with I_o ⩾ 3σ(I_o gave a final reisdual of 0.080.     

Hydrothermal syntheses and characterizations of two new hydrogen bond-supported supramolecular compounds based on polyoxometalates

Two new polyoxometalates [HN(C₂H₅)₃]₃[PMo₁₂O₄₀] (1) and [NH₂(C₂H₄NH₃)₂]₂[Mo₅P₂O₂₃] (2) have been hydrothermally synthesized and characterized by IR, UV-Vis, XPS spectra, TG analyses, and single crystal X-ray diffraction. Crystal data for 1: monoclinic, space group C2/c, a = 24.651(5) Å, b = 10.822(2) Å, c = 22.413(5) Å, β = 120.37(3)°, and V = 5158.7(18) ų; for 2: triclinic, space group P-1, a = 9.821(2) Å, b = 9.948(2) Å, c = 14.687(3) Å, α = 95.490(3)°, β = 98.870(3)°, γ = 95.710(3)°, and V = 1401.7(5) ų. The crystal structure analyses reveal complex hydrogen bonds in both 1 and 2 in 3-D supramolecular arrays constructed from different polyoxoanions and organic ligands.     

Cuboidal oxalate cluster complexes with the Mo<Subscript>3</Subscript>CuQ<Subscript>4</Subscript><Superscript>5+</Superscript> cluster core (Q = S or Se): synthesis,structure, and electrochemical properties

The reactions of the [Mo₃(μ₃-Q)(μ₂-Q)₃(H₂O)₃(C₂O₄)₃]²⁻ complex (Q = S or Se) with CuX salts (X = Cl, Br, I, or SCN) in water produce the cuboidal heterometallic clusters [Mo₃(CuX)(μ₃-Q)₄(H₂O)₃(C₂O₄)₃]²⁻, which were isolated as the potassium and tetraphenylphosphonium salts. Two new compounds, K₂[Mo₃(CuI)(μ₃-S)₄(H₂O)₃(C₂O₄)₃]·6H₂O and (PPh₄)₂[Mo₃(CuBr)(μ₃-S)₄(H₂O)₃(C₂O₄)₃]·7H₂O, were structurally characterized. All compounds were characterized by elemental analysis and IR spectroscopy. The K₂[Mo₃(CuI)(μ₃-Se)₄(H₂O)₃(C₂O₄)₃] compound was characterized by the ⁷⁷Se NMR spectrum; the (PPh₄)₂[Mo₃(CuI)(μ₃-S)₄(H₂O)₃(C₂O₄)₃], (PPh₄)₂[Mo₃(CuI)(μ₃-Se)₄(H₂O)₃(C₂O₄)₃] and K₂[Mo₃(CuSCN)(μ₃-S)₄(H₂O)₃(C₂O₄)₃]·7H₂O compounds, by electrospray mass spectra. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1639–1644, September, 2007.     

Hydrothermal synthesis and structural characterization of three reduced phosphomolybdates

Three reduced molybdenum(V) phosphates, Na₂[H₂DaHex]_4.5[H₃O]{Mn[Mo₆O₁₂(OH)₃(HPO₄)₂(PO₄)₂]₂}·2H₂O (1), [H₂DaHex]₄[Zn(H₂O)]₂{Zn[Mo₆O₁₂(OH)₃(HPO₄)₂(PO₄)₂]₂}·6H₂O (2), and [H₂DaHex]_3.5[Cd(H₂O)₂]_1.5[Cd(H₂O)]{Cd[Mo₆O₁₂(OH)₃(HPO₄)₂(PO₄)₂]₂}·3.5H₂O (3) (DaHex?=?1,6-diaminylhexane), were hydrothermally synthesized by using the same organic template (DaHex) and characterized by elemental analysis, IR, TGA, powder XRD, and single-crystal X-ray diffraction. Crystallographic analysis reveals that the compounds contain M[P₄Mo₆]₂ (M?=?Mn for 1, Zn for 2, Cd for 3) polyanions, which are further connected by various metal ions to form different topological structures. In 1, the cluster anion Mn[P₄Mo₆]₂ is discrete. For 2 and 3, M[P₄Mo₆]₂ (Zn for 2, Cd for 3) clusters are linked by transition metal ions to form different infinite chains. Then, all the 1-D chains are further packed into 3-D supramolecular structures via hydrogen-bonding interactions. The formations of 1, 2, and 3 demonstrate that not only organic templates, but transition metal ions also play very important roles in the M-P₄Mo₆ system.     

A series of new hybrid compounds constructed from Dawson-type phosphomolybdates and metal–organic coordination complexes

In this study, a series of compounds based on Dawson-type phosphomolybdates, H₃(C₆NO₂H₆)₂[K(H₂O)₃(C₆NO₂H₅)₃][P₂Mo₁₈O₆₂] ? 5.5H₂O (1), (C₆NO₂H₆)₆[Ln(H₂O)₇(C₆NO₂H₅)₂]₂[P₂Mo₁₈O₆₂]₂·13.5H₂O (Ln = Ce (2), La (3)) have been synthesized and characterized by elemental analysis, IR and UV-Vis spectroscopy methods, TG analysis, and single-crystal X-ray diffraction. Compound 1 consists of [P₂Mo₁₈O₆₂]^6? building units joined by potassium-pyridine-3-carboxylic acid complexes, resulting in a wavelike polyoxometalate (POM) chain, which further interacts with each other via intermolecular interactions to form a 3-D supramolecular channel framework containing guest water molecules. Compounds 2 and 3 possess a 3-D supramolecular framework with 1-D tunnel constructed from [P₂Mo₁₈O₆₂]^6? and mononuclear lanthanide coordination complex fragments. To the best of our knowledge, 1 not only represents the first example of 1-D hybrid assembly based on Dawson-type phosphomolybdate, but also the first hybrid compound constructed from Dawson-type POMs and alkali–metal coordination complex fragments.     

Hydrothermal synthesis and structural characterization of two new reduced phosphomolybdates based on an organoamine template and copper ion

Two new compounds, (H₂en)₃(H₂enMe)₄(H₃O){Cu^I[Mo^V ₆O₁₂(OH)₃(HPO₄)(PO₄)₃]₂}?·?6H₂O (1) and (H₂enMe)₄{Cu^ICu^II[Mo^V ₆O₁₂(OH)₃(PO₄)(HPO₄)₂(H₂PO₄)]₂}?·?3H₂O (2), were hydrothermally synthesized and characterized by elemental analysis, IR, TGA, and single-crystal X-ray diffraction analysis. Crystallographic analysis reveals that 1 is constructed from cluster anions {Cu^I[Mo^V ₆O₁₂(OH)₃(HPO₄)(PO₄)₃]₂}^15?, protonated organic amines, and water molecules. Each cluster is bridged through hydrogen bonds to form a 3-D supermolecular structure. For 2, {Cu^I[Mo^V ₆O₁₂(OH)₃(PO₄)(HPO₄)₂(H₂PO₄)]₂}^11? are connected by Cu^II cations to form an infinite chain. The formation of 1 and 2 reveals that organoamines influence the structures of the crystals.     

Über Thallium(I)-chlorooxomolybdate: Synthese und Kristallstrukturen von Tl[MoOCl4(NCCH3)], Tl[Mo2O2Cl7] und Tl2[Mo4O4Cl14] und die Struktur von Tl2[MoCl6]

On Thallium(I)-oxochloromolybdates: Synthesis and Crystal Structures of Tl[MoOCl₄(NCCH₃)], Tl[Mo₂O₂Cl₇], and Tl₂[Mo₄O₄Cl₁₄] and the Structure of Tl₂[MoCl₆] Black crystals of Tl₂[MoCl₆] are formed in the reaction of TlCl with MoOCl₃ in a sealed evacuated glass ampoule at 350 °C. The crystal structure analysis shows that Tl₂[MoCl₆] (cubic, Fm 3¯m, a = 986.35(7) pm) adopts the K₂[PtCl₆] structure with a Mo–Cl bond length of 236.6 pm. Tl[MoOCl₄(NCCH₃)] was obtained by the reaction of TlCl with MoOCl₃ in acetonitrile in form of yellow, moisture sensitive crystals. The structure (orthorhombic, Cmcm, a = 746.0(1), b = 1463.8(3), c = 857.3(2) pm) is built of Tl⁺ cations and octahedral [MoOCl₄(NCCH₃)]^– anions in which the acetonitrile ligand is bound in trans position to the oxygen. The reaction of TlCl and MoOCl₃ in dichloromethane yields Tl[Mo₂O₂Cl₇] and Tl₂[Mo₄O₄Cl₁₄] as green moisture sensitive crystals. The structure of Tl[Mo₂O₂Cl₇] (orthorhombic, Pmmn, a = 694.3(1), b = 951.9(2), c = 904.7(1) pm) consists of Tl⁺ cations and dinuclear [Mo₂O₂Cl₇]^– anions, with two equidistant chlorine bridges of 248.2 and one longer chlorine bridge of 265.7 pm. The oxygen atoms are located in the trans positions of the longer chloro bridge. The structure of Tl₂[Mo₄O₄Cl₁₄] (triclinic, P1¯, a = 692.8(1), b = 919.6(1), c = 998.9(1) pm, α = 104.94(1)°, β = 90.31(1)°, γ = 108.14(1)°) is build of Tl⁺ cations and [Mo₄O₄Cl₁₄]^2– anions which form tetramers of distorted octahedral, edgesharing (MoOCl₅) units with chlorine atoms in the bridging positions. The oxygen atoms are located in the trans positions of the longest chlorine bridges.     

Synthesis and Crystal Structure of Two New Molydenum(V) Pyrophosphate Complexes

Two new reduced molybdenum pyrophosphates, Na₂₈[Na₂{(Mo₂O₄)₁₀(P₂O₇)₁₀(HCOO)₁₀}]·108H₂O ( 1 ) and Na₂₂(H₃O)₂[Na₄{(Mo₂O₄)₁₀(P₂O₇)₁₀(CH₃COO)₈(H₂O)₄}]·91H₂O ( 2 ) have been synthesized and characterized by single‐crystal X‐ray diffraction. Red crystals of 1 are triclinic, space group , with a = 17.946(4) Å, b = 18.118(4) Å, c = 21.579(4) Å, α = 114.47(3)°, β = 93.54(3)°, γ = 114.39(3)° and V = 5581.8(19) ų, and orange crystals of 2 are monoclinic, space group P2₁/n, with a = 21.467(4) Å, b = 23.146(5) Å, c = 24.069(5) Å, β = 101.76(3)° and V = 11708(4) ų. They are both constructed by Mo^V dimers ({Mo₂O₄(O_P)₄(HCOO)} in 1 , {Mo₂O₄(O_P)₄(CH₃COO)} and {Mo₂O₄(O_P)₄(H₂O)₂} in 2 ) and pyrophosphoric groups. Their structures can be described as two interconnected nonequivalent wheels which are approximately perpendicular, delimiting a large cavity. The larger wheel contains six Mo^V dimers, while the smaller one has four dimers.     

Molybdänhalogenidcluster mit sechs terminalen Alkoholatliganden: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH und (C18H36N2O6Na2)2[Mo6Cl8(OC6H5)6]

Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6CH₃OH and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] . The reaction of Na₂[Mo₆Cl₈(OCH₃)₆] and 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6 CH₃OH ( 1 ), which is converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo₆Cl₈ⁱ(OR^a)₆]^2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo₆Cl₈(OC₆H₅)₆]^2? is investigated by means of UV/VIS spectroscopy and EHMO calculations.     

两个新颖的铜-二氮杂菲和钼(磷,硒)杂多酸组成的有机-无机杂合化合物:合成和晶体结构

水热法合成了两个新颖的有机-无机杂合化合物{[Cu(o-phen)(H₂O)]₃[Mo₅P₂O₂₃]}•4.5H₂O (1) 和{[Cu(o-phen)- (H₂O)]₂[Mo₅Se₂O₂₁]} (2) (o-phen＝1,10-phenanthroline). 通过红外光谱和单晶X射线衍射分析确定了它们的结构. 结构分析表明两个分子结构中的相邻[Mo₅P₂O₂₃]^6－或[Mo₅Se₂O₂₁]^4－阴离子均由两个桥式的[Cu(o-phen)(H₂O)]单元连接成分别为风车状和双侧桥联状一维聚合链, 化合物1的双金属链又通过若干链间氢键形成层状堆积结构. 讨论了钼杂多酸阴离子和第二种金属-配体亚单元阳离子之间的相互匹配关系.     

The rigid isomeric 5-(x-pyridyl)-1H-tetrazole ligands-directed various isopolymolybdate-based compounds: assembly,structures, and properties

Two new isopolymolybdate-based metal–organic complexes, [Cu₂(2-ptz)₂(Mo₄O₁₄)_0.5] (1) and [Cu₃(OH)₂(3-ptz)₄(γ-H₄Mo₈O₂₆)(H₂O)₄]·10H₂O (2) (2-ptzH = 5-(2-pyridyl)-1H-tetrazole, 3-ptzH = 5-(3-pyridyl)-1H-tetrazole), constructed from isomeric ligands with different N-donor sites were synthesized under hydrothermal conditions. In 1, each [Mo₄O₁₄]^4? cluster connected with six neighboring [Mo₄O₁₄]^4? clusters through six binuclear [Cu₂(2-ptz)₂]²⁺ subunits to yield a 2-D layer. In 2, bidentate inorganic [Mo₈O₂₆]^4? anions link the trinuclear [Cu₃(OH)₂(3-ptz)₄] clusters to construct a 1-D chain. Adjacent chains connect through Mo–N bonds between the [Mo₈O₂₆]^4? anions and pyridyl groups from the trinuclear clusters to form a 2-D layer. The effect of the N-donor sites of the rigid isomeric ligands on the structures of 1 and 2 was discussed. The electrochemical properties and photocatalytic activities of 1 and 2 have also been studied.     

Crystal structure of K2[Mo3(PdPPh3)S4(C2O4)3(H2O)3]·0.5H2O

By the reaction of [Mo₃S₄(C₂O₄)₃(H₂O)₃]²⁻ with PdCl₂ and NH₄H₂PO₂ as a reducing agent, followed by the addition of PPh₃, a new oxalate cuboidal cluster complex [Mo₃(PdPPh₃)S₄(C₂O₄)₃(H₂O)₃]²⁻ is obtained. It was isolated and structurally characterized as K₂[Mo₃(PdPPh₃)S₄(C₂O₄)₃(H₂O)₃]·0.5H₂O. Original Russian Text Copyright ? 2008 by A. L. Gushchin, M. N. Sokolov, D. Yu. Naumov, and V. P. Fedin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 775–778, May–June, 2008.