Bridged Coordination Polymers Research Articles

Meso–meso directly linked dipyrrolyl ligand dimer that shows the formation of metal-coordination polymers

A novel dipyrrolyl metal-coordination ligand dimer directly connected at the meso positions showed the formation of a ZnII -bridged coordination polymer and the spontaneous transformation to a meso–meso- and singly β–β-fused tetrapyrrolyl molecule in solution by C–C bond formation and concomitant proton migration.

Novel semiconducting metal-organic framework: Synthesis, structural characterisation and electrical conductivity studies of manganese based two dimensional coordination polymer

New Manganese(II) dichloro and pyrazine bridged coordination polymer containing rectangular framework [Mn(μ-pz)(μ-Cl)2]n was synthesised and structurally characterised. Single crystal X-ray structure of the coordination polymer [Mn(μ-pz)(μ-Cl)2]n displayed 2D rectangular framework with infinite sheet structure. Thermogravimetric analysis showed that the [Mn(μ-pz)(μ-Cl)2]n coordination polymer is stable and robust up to 310 °C. Electrical conductivity measurements of [Mn(μ-pz)(μ-Cl)2]n were carried out as a function of frequency at various temperatures and the coordination polymer exhibited semiconducting property with activation energy Ea = 0.70 (± 0.03) eV.

A new luminous end-to-end thiocyanato bridged heptacoordinated coordination polymer of lead(II) containing a tetradentate Schiff base

A new end-to-end thiocyanato bridged coordination polymer [Pb(enbzpy)(μ 1,3 -NCS)(NCS)] n ( 1 ) has been synthesized using a one-pot reaction of Pb(OAc) 2 .3H 2 O, tetradentate Schiff base N,N΄ -(bis(pyridine-2-yl)benzylidene)ethane-1,2-diamine (enbzpy) and NH 4 NCS in MeOH solution at room temperature. Single crystal X-ray diffraction measurement reveals that each lead(II) adopts a pentagonal bipyramidal geometry with a PbN 6 S chromophore coordinated through four N atoms of enbzpy, two μ 1,3 -bridged N and S atoms and one terminal N atom of thiocyanates. In crystalline state, 1 forms a 2D honeycomb like (6 3 ) topology through S∙∙∙S interaction and the layers stack through face-to-face π∙∙∙π interaction giving rise to a 3D network. At room temperature DMF solution of 1 displays a high-energy intraligand 1 (π-π*) fluorescence. Synthesis, structure and luminescence property of an 1D coordination polymer [Pb(enbzpy)(μ 1,3 -NCS)(NCS)] n ( 1 ) is described in which 2D honeycomb like (6 3 ) topology through S∙∙∙S interaction is formed, and the layers stack through π∙∙∙π interaction giving rise to a 3D network. ► One μ 1,3 -thiocyanato bridged 1D coordination polymer of lead(II) is isolated. ► X-ray study reveals interesting 2D honeycomb like (6 3 ) topology through S∙∙∙S interaction. ► The compound with the tetradentate Schiff base is example of luminous material. ► Thermogravimetric analyses show their thermal stability and decomposition pattern.

Syntheses, structures and magnetic properties of μ 1,5 dicyanamide bridged coordination polymers of copper(II) and nickel(II) containing a tetradentate N-donor Schiff base

One neutral [Cu 2(enbzpy)(dca) 4] n ( 1) and one polycationic [Ni(enbzpy)(dca)] n (ClO 4) n ( 2) [enbzpy = N,N′-(bis-(pyridin-2-yl)benzylidene)ethane-1,2-diamine; dca = dicyanamide] 1D coordination polymers are synthesized and characterized. X-ray structural analyses reveal each copper(II) center in 1 to adopt a distorted square pyramidal geometry with a CuN 5 chromophore coordinated through two N atoms of the Schiff base behaving as a binucleting bis(bidentate) ligand and three nitrile N atoms of one terminal and two single μ 1,5 dca units leading to a 1D ladder structure. In 2, each nickel(II) center has a distorted octahedral coordination environment with an NiN 6 chromophore bound by four N atoms of enbzpy through tetradentate chelation and two nitrile N atoms of two different single bridged μ 1,5 dca units; the latter connects other neighboring metal centers in a non-ending fashion affording a 1D chain. Variable-temperature magnetic susceptibility measurements of 1 and 2 show weak antiferromagnetic interactions among the metal centers through μ 1,5 dca bridges.

Varying structural motifs in oxyanions (NO3−, CO32−) and phenoxyacetate (PhOAc−) bridged coordination polymers derived from alkoxo-bridged dicopper building blocks with {Cu2O2} core

The oxyanions (NO3−, CO32−) and phenoxyacetate (PhOAc−) bridged three 1D-coordination polymeric chains, {[Cu2(μ-hep)2(μ-NO3)]2}n (1), {[Cu2(μ-hep)2(H2O)2]·2H2O(μ-CO3)}n (3) and {[Cu2(μ-hep)2(μ-PhOAc−)]2}n (2) (hep-H = 2-(2-hydroxyethyl)pyridine) have been synthesized. In 1–3 the alkoxide bridged dicopper building units, [Cu(μ-hep)]2 with Cu2O2 core, are linked via the respective anions. Detailed structural analysis reveals that in 1 or 2, two units of NO3− (1) or PhOAc− (2), respectively, bind with the four copper ions in two adjacent alkoxide bridged dimeric units in head-to-head and tail-to-tail fashion and the same binding mode continues along the polymeric chain. This in effect yields a 12-membered metallacyclic ring in between two dimeric core units. However, in 3 only one CO32−group bridges the two copper centres associated with the two neighbouring alkoxide bridged dimeric units in head-to-tail mode which in turn forms a zig-zag polymeric chain. Two coordinated and two lattice water molecules from two adjacent polymeric layers in the structure of 3 form water tetramers. Furthermore, the interaction of water tetramer with the uncoordinated –CO group of the bridging CO32− develops an additional zig-zag chain which is being trapped between the two outer zig-zag coordination polymeric chains in 3. The polymeric chains in 1–3 further develop a 2D-network pattern via an extensive non-covalent hydrogen bonding as well as C–H⋯π and π⋯π interactions.

Structural and Magnetic Properties of One-Dimensional Squarate Bridged Coordination Polymers Containing 2-Aminomethylpyridine Ligand

Three novel one-dimensional (1D) coordination polymers with general formula {[M(μ-sq)2(amp)2]·H2O}n [M=Cu(II) (1), Zn(II) (2)] and [Cd(μ-sq)2(amp)2]n (3) [sq: Squarate; amp:2-aminomethylpyridine] have been prepared and spectroscopically studied. Each metal (II) ion in 1–3 is octahedrally coordinated by two sq and two amp ligands. The amp ligands are N,N′ coordinated, while the sq ligands bridge the metal centers forming 1D linear chain structure. The individual chains are linked by O–H···O hydrogen bonds involving the hydrogens of water molecules (1–2), amino hydrogens and squarate O atoms (1–3). The hydrogen bonded layers are further assembled into three-dimensional supramolecular networks by weak aromatic π–π interactions. EPR results indicate that the ground state of the paramagnetic electron in 1 and Cu2+ doped complexes 2–3 is \( d_{{x^{2} - y^{2} }} \). Magnetic measurements reveal that complex 1 shows paramagnetic behavior.

Copper–thioarylazoimidazole complexes: Structures, photochromism and redox interconversion between Cu(II) ↔ Cu(I) and correlation with DFT calculation

Reaction of Cu(ClO 4) 2·6H 2O, SRaaiNR′ (1-alkyl-2-[( o-thioalkyl)phenylazo]imidazole) and NH 4SCN (1:1:2 mol ratio) affords distorted square pyramidal, [Cu II(SRaaiNR′)(SCN) 2] ( 3) compound while identical reaction with [Cu(MeCN) 4](ClO 4) yields –SCN– bridged coordination polymer, [Cu I(SRaaiNR′)(SCN)] n ( 4). These two redox states [Cu II and Cu I] are interconvertible; reduction of [Cu II(SRaaiNR′)(SCN) 2] by ascorbic acid yields [Cu I(SRaaiNR′)(SCN)] n while the oxidation of [Cu I(SRaaiNR′)(SCN)] n by H 2O 2 in presence of excess NH 4SCN affords [Cu II(SRaaiNR′)(SCN) 2]. They are structurally confirmed by single crystal X-ray diffraction study. Cyclic voltammogram of the complexes show Cu(II)/Cu(I) redox couple at ∼0.4 V and azo reductions at negative to SCE. UV light irradiation in MeCN solution of [Cu I(SRaaiNR′)(SCN)] n ( 4) show trans-to- cis isomerisation of coordinated azoimidazole. The reverse transformation, cis-to- trans, is very slow with visible light irradiation while the process is thermally accessible. Quantum yields ( ϕ t→c) of trans-to- cis isomerisation are calculated and free ligands show higher ϕ than their Cu(I) complexes. The activation energy ( E a) of cis-to- trans isomerisation is calculated by controlled temperature experiment. Copper(II) complexes, 3, do not show photochromism. DFT and TDDFT calculation of representative complexes have been used to determine the composition and energy of molecular levels and results have been used to explain the solution spectra, photochromism and redox properties of the complexes.

Three NEW butane-1,2,3,4-tetracarboxylato-bridged coordination polymers: Syntheses, crystal structures and charaterization

Three new butane-1,2,3,4-tetracarboxylato bridged coordination polymers [Zn2(H2O)4(BTC)]·3H2O 1, [Cd2(H2O)4(BTC)]·2H2O 2 and [Y2(H2O)6(H2BTC)(BTC)]·5H2O 3 (H4BTC = butane-1,2,3,4-tetracarboxylic acid) were synthesized and characterized by IR spectroscopy, TG–DTA analyses, elemental analyses and single-crystal X-ray diffraction, and their fluorescence properties were also investigated. In 1, the trigonal pyramidally coordinated Zn atoms are brigded by both μ6η6 and μ6η8 centrosymmetric BTC4− anions into 2D layers, which are connected by the octahedrally coordinated Zn atoms to build up 3D (44·610·8)(44·62)2(44·68·82·10) topological framework with the lattice water molecules in cavities. In 2, the CdO7 pentagonal bipyramids and the CdO8 4,4′-bicapped triagonal antiprisms are edge-shared to generate the Cd2O13 bipolyhedra, which are further corner-shared into 1D metal-oxide chains. The resulting chains are interconnected by the μ6η8 BTC4− anion to form 2D (43)2(46·66·83) networks, which are assembled via interlayer hydrogen bonds into a 3D (411·611·86)(43)(49·6) topological supramolecular architecture with the lattice H2O molecules located in holes. The distorted 4,4′-bicapped triagonal antiprismatically coordinated Y atoms in 3 are interconnected μ4η4 H2BTC2− and μ4η6 BTC4− anions to from 2D (44·62) topological networks, which are held together via strong interlayer hydrogen bonds into a 3D fsc topological supramolecular architecture with the lattice water molecules residing in cavities.

The structures of tellurium(iv) halides in the gas phase and as solvated molecules

The structures of molecular tellurium tetrafluoride and tellurium tetrachloride were determined by a combination of gas-phase electron diffraction, mass spectrometry and quantum chemical calculations. The combined GED/MS experiments showed no evidence of decomposition of TeF(4) and TeCl(4). No ions of oligomeric (dimeric, trimeric, etc.) or any other composition were found in the mass spectra. The monomeric molecules possess a pseudo trigonal bipyramidal structure (C(2v) symmetry) with the equatorial Te-X distances being shorter than the axial ones. The fluorine atoms are bent away from the lone pair resulting in X(eq)-Te-X(eq) and X(eq)-Te-X(ax) bond angles smaller than 120 and 90 degrees, respectively. The structure of solvates TeF(4) (THF)(2), TeF(4) (dioxane) TeF(4) (DME)(2), TeF(4)(Et(2)O) TeF(4)(toluene), TeCl(4)(CH(3)CN)(2), TeCl(4)(DME)(2) and TeCl(4)(dioxane) were determined by X-ray diffraction. The structures of tellurium tetrafluoride solvates are strongly influenced by the choice of the solvent molecules. Monomeric TeF(4) units were obtained with THF, DME and dioxane whereas fluoride bridged coordination polymers were formed using diethyl ether or toluene. All tellurium tetrachloride solvates studied contain monomeric TeCl(4) units with coordinated solvent molecules. Coordination numbers range from four in the gas phase to eight in the TeF(4) dimethoxyethane solvate. Geometric parameters of the TeX(4) molecules in the crystal, solvates and gas phase were compared. DFT, MP2, CCSD, CCSD(T) methods were applied for calculation of geometric and vibrational characteristics of free TeX(4) molecules (X = F, Cl). The pseudorotation barriers were estimated and an NBO analysis was performed. It was shown that both, GED and theoretical, quantitative results are in agreement with the qualitative results of the VSEPR model.

Syntheses, crystal structures and properties of two thiocyanato bridged coordination polymers

Two thiocyanato bridged coordination polymers {[Cd(μ-SCN) 2(htm)(H 2O)]·H 2O} n ( 1) and [Cu(μ-SCN) 2(Him) 2] n ( 2) (htm = hexamethylenetetramine, Him = imidazole) have been synthesized and characterized by single-crystal X-ray analyses. For these two compounds, the adjacent metal centers are bridged by a pair of μ 1,3-SCN − to form 1-D array, which are further linked to 2-D supramolecular network by hydrogen bonds. And, the interactions between metal center and sulfur atom of thiocyanato ligand obey the HSAB rule. Compound 1 exhibits good fluorescent emissions. Compound 2 exhibits intra-chain Cu(II)–Cu(II) ferromagnetic coupling with J = 1.58 cm −1.

Second-sphere hydrogen-bonding in heteroditopic mercaptopyridinium copper(I) frameworks

A series of Cu(I) complexes of 4-mercaptopyridine (LH) are reported that form three-dimensional hydrogen-bonded frameworks in the solid-state. The 4-mercaptopyridine ligands co-ordinate to the Cu(I) cations via thiolate donors, leaving a pyridinium hydrogen-bond donor available for interaction with the relevant counter-anions. Four new Cu(I) complexes, [Cu2(LH)6]·2Cl 1, [Cu2(LH)6]·SiF6·2MeOH 2, [Cu4(LH)10]·4NO3·MeOH·H2O 3 and {[Cu6(LH)13]·2BF4·2SiF6·7.5MeOH}∞4 are reported and have been structurally characterised by single crystal X-ray diffraction. In each case hydrogen-bonded arrays are formed via N–H⋯anion hydrogen-bonds or by including hydrogen-bonding to guest solvent molecules. Whereas compound 1 adopts a rutile-like structure with [Cu2(LH)6]2+ and Cl− nodes adopting six- and three-connected arrangements, respectively, compounds 2 and 3 adopt six-connected nets of α-Po (41263) topology. Compound 4 forms a thiolate bridged co-ordination polymer constructed from repeating units of six Cu(I) centres connected by ten bridging and three terminal thiolate-bound LH donors, with complex hydrogen-bonding observed between the polymer cation and counter-anions.

Molecular and Crystal Structures of Mononuclear trans‐[Fe(CN)2(tOcNC)4] and trans‐[Mn(CN)(CO)(tOcNC)4] as well as of Cyanide Bridged Coordination Polymers Derived from trans‐[M(CN)2(tOcNC)4] (M = Fe, Ru)

AbstractThe octahedral complexes trans‐[Fe(CN)2(tOcNC)4] and trans‐[Mn(CN)(CO)(tOcNC)4] are produced by the reaction of 2‐isocyano‐2,4,4‐trimethyl‐pentane (tert. octyl‐isocyanide) with the corresponding transition metal carbonyls Fe2(CO)9 and Mn2(CO)10. In contrast to isostructural compounds with less bulky tert.‐butylisocyanide ligands the cyanide groups in trans‐[Fe(CN)2(tOcNC)4] and trans‐[Mn(CN)(CO)(tOcNC)4] do not act as hydrogen bond acceptors towards solvent molecules in the crystal structures. In addition, the corresponding cis‐isomers are configurationally unstable. The reaction of trans‐[Fe(CN)2(tOcNC)4] and trans‐[Ru(CN)2(tOcNC)4] with MnCl2, NiCl2 and Co(NO3)2 ends up in the formation of cyanide bridged coordination polymers. X‐ray structure determinations of the cobalt compounds reveal different molecular structures. Whereas the former produces highly distorted infinite polymeric chains with the nitrate anions still coordinated to the cobalt centers, the latter forms polymers with the cobalt atoms being coordinated by four ethanol molecules to which the anions are bound via hydrogen bond interactions. The coordination geometries around ruthenium and cobalt in this coordination polymer are therefore nearly perfectly octahedral and tetrahedral, respectively. Measurements of the magnetic susceptibility of the coordination polymers at different temperatures are indicative of weak antiferromagnetic coupling of the paramagnetic centers along the polymeric chains.

Bridged Coordination Polymer Multilayers with Tunable Properties

Coordination multilayers consisting of Pd(II) pincer-type complexes and poly(vinyl pyridine) were synthesized and characterized. Film properties were found to be dependent on and could be tuned by varying bath deposition concentrations, polymer molecular weight, and solution additives that compete with binding. Generally, smoother, thinner films were obtained with lower poly(vinyl pyridine) deposition bath concentrations. Likewise, film thickness and roughness could be reduced by employing a higher-molecular-weight poly(vinyl pyridine). Film properties could also be influenced by using acetonitrile as a solution additive, effectively driving the binding equilibrium slightly toward the free species.

Spin transition in three-dimensional bridged coordination polymers of iron(II)–urea-triazoles

Three-dimensional spin-crossover (SCO) networks of [Fe 2( n-Rdubtrz) 3](X) 4 · nH 2O ( n-R = (CH 2) y , y = 4, 6, 8, 12; du = diurea; btrz = bis-triazole; X = BF 4 - , ClO 4 - , triflate, tosylate) coordination polymers are prepared by reaction of bridging aliphatic bis-urea triazoles ( n-Rdubtrz) with the iron-salts (FeX 2). Investigations of the properties are supported by studies of one-dimensional compounds of [Fe(Rtrzu) 3](X) 2 (R = n-propyl, t-butyl; trzu = urea triazole). Characterization of the complexes is carried out with IR-spectroscopy, elemental analysis, TGA and atomic absorption spectroscopy. SCO-behaviour of all complexes is inspected by magnetic susceptibility measurements and 57Fe Mössbauer. While the SCO in the polymeric networks shows strong dependency on the counter ions, in the complexes no pronounced change is observed for different methylene bridging lengths. For [Fe(Rtrzu) 3](X) 2 compounds hysteresis effects are ascertained.

Synthesis, structure and magnetic properties of a geminal μ 2-tetracyanoethylene radical anion bridged coordination polymer

A tetracyanoethylene (TCNE) bridged coordination polymer, [Mn(cyclen)(μ 2-TCNE)] · TCNE ( 1), (cyclen = 1,4,7,10-tetraazacyclododecane, TCNE = tetracyanoethylene), has been synthesized by combining [Mn II(cyclen)] 2+ and the potassium salt of TCNE radical anion, K[TCNE]. The compound crystallizes in two polymorphs. Both structures feature formal TCNE radical anion ligands in an unusual geminal (or 1,1−) bridging geometry between two high spin Mn(II) centers. The N TCNE–Mn–N TCNE bond angles of two bridging TCNE /− ligands are 88.07(9)° 1a and 85.44(14)° 1b, respectively. Each bridging TCNE /− is π stacked with an uncoordinated TCNE /− to form what can be construed as a diamagnetic dianion, TCNE 2 2 - , containing a 4-center 2-electron (4c/2e −) bond. The results of variable-temperature magnetic susceptibility measurements indicate behavior consistent with weak antiferromagnetic coupling between two Mn(II) centers with no significant contribution of spin from the organic radicals.

Zinc complexes of the biomimetic N,N,O ligand family of substituted 3,3-bis(1-alkylimidazol-2-yl)propionates: the formation of oxalate from pyruvate.

The coordination chemistry of the 2-His-1-carboxylate facial triad mimics 3,3-bis(1-methylimidazol-2-yl)propionate (MIm2Pr) and 3,3-bis(1-ethyl-4-isopropylimidazol-2-yl) propionate (iPrEtIm2Pr) towards ZnCl2 was studied both in solution and in the solid state. Different coordination modes were found depending both on the stoichiometry and on the ligand that was employed. In the 2:1 ligand-to-metal complex [Zn(MIm2Pr)2], the ligand coordinates in a tridentate, tripodal N,N,O fashion similar to the 2-His-1-carboxylate facial triad. However, the 1:1 ligand-to-metal complexes [Zn(MIm2Pr)Cl(H2O)] and [Zn(iPrEtIm2Pr)Cl] were crystallographically characterized and found to be polymeric in nature. A new, bridging coordination mode of the ligands was observed in both structures comprising N,N-bidentate coordination of the ligand to one zinc atom and O-monodentate coordination to a zinc second atom. A rather unique transformation of pyruvate into oxalate was found with [Zn(MIm2Pr)Cl], which resulted in the isolation of the new, oxalato bridged zinc coordination polymer [Zn2(MIm2Pr)2(ox)]·6H2O, the structure of which was established by X-ray crystal structure determination.

Dipyridyl bridged coordination polymers of Cu(II): Synthesis, crystal structure and magnetic study

Two coordination polymers, [Cu(bpp)(H 2O) 2(ClO 4) 2] n ( 1) and {[Cu(bpds) 2(ClO 4) 2] · 1.5(H 2O)} n ( 2) [bpp, 1,3-bis(4-pyridyl)propane and bpds, 4,4′-bipyridyl disulfide] have been synthesized and characterized by X-ray single crystal diffraction study and magnetic measurement. Both the coordination polymers display 1D chains with perchlorate anions acting as pendant ligands. In 1 undulated polymers are built by Cu(H 2O) 2(ClO 4) 2 units connected by single bpp and in complex 2 Cu(ClO 4) 2 fragments are linked by pairs of bpds ligands to form a double-stranded chain. The crystal packing evidences polymers of 1 involved in weak H-bonding interactions leading to a 3D supramolecular network. Magnetic study reveals weak antiferromagnetic interactions in both complexes.

The role of solvent in coordination polymers: The structures of catena-[Hg(μ 2-O 2PPh 2) 2] and catena-[Hg(μ 2-O 2PPh 2) 2(NC 5H 5) 2

The novel diphenylphosphinate bridged coordination polymer catena-[Hg(μ 2-O 2PPh 2) 2] was synthesized as a colorless powder from mercury(II) acetate and diphenylphosphinate. Coordinating solvents were used to break the solid-state polymeric chains to allow the crystallization of new polymeric compounds. Crystallization from dimethylsulfoxide/methanol gave the solvent-free polymer catena-[Hg(μ 2-O 2PPh 2) 2] while pyridine/methanol gave the 1:2 Hg:pyridine adduct, catena-[Hg(μ 2-O 2PPh 2) 2(NC 5H 5) 2]. Both have a polymeric chain with two asymmetrically bridging diphenylphosphinate ligands. The latter also has two pyridine molecules coordinated to the Hg center.

Synthesis, crystal structure and properties of a one-dimensional L-valinate bridged coordination polymer: [Cu2(L-val)2(bpy)2] n ·2nClO4·2nH2O

The complex [Cu2(L-val)2(bpy)2] n ·2nClO4·2nH2O (L-val = L-valinate, bpy = 2,2′-bipyridine) has been synthesized and investigated by elemental analysis, IR and UV spectroscopy, DTA–TG analysis and X-ray diffraction methods. The complex crystallizes in the monoclinic space group P21 with two molecules in a unit cell of dimensions a = 10.0954(12), b = 8.1245(9), c = 23.297(3) Å, β = 102.447(2)°, V = 1865.9(4) Å3, D c = 1.614 g/cm3, μ = 1.357 mm−1, F(000) = 932, R = 0.0337, wR = 0.0847 for 7024 unique reflections. Single-crystal structure analysis reveals that cations have a one-dimensional polymeric structure, with two Cu(bpy)2+ units bridged by a carboxylate group of L-valinate. Each Cu2+ ion is in a slightly distorted square-pyramidal geometry, with the bpy(N,N′) and L-val(N,O) acting as bidentate ligands in the equatorial plane and another carboxylate oxygen atom from a symmetry-related neighboring L-valinate ion in the apical position. IR and UV spectra and thermal analysis are in agreement with the crystal structure.

3D Supramolecular Array Assembled by Cross-like Arrangement of 1D Sandwich Mixed Molybdenum−Vanadium Polyoxometalate Bridged Coordination Polymer Chains: Hydrothermal Synthesis and Crystal Structure of {[MoVI5MoV3VIV8O40(PO4)][Ni(en)2]}[Ni(en)2]2·4H2O

A novel organic−inorganic hybrid material constructed from mixed molybdenum−vanadium polyoxoanion clusters and [Ni(en)2]2+ complex groups {[MoVI5MoV3VIV8O40(PO4)][Ni(en)2]}[Ni(en)2]2·4H2O (1) (en = ethylenediamine), has been prepared under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. Complex 1 exhibits an interesting three-dimensional supramolecular array through cross-like arrangement of a one-dimensional coordination polymer anion chain {[MoVI5MoV3VIV8O40(PO4)][Ni(en)2]}4-, which is sandwiched by discrete cation complex fragments [Ni(en)2]2+. It is the first example of a three-dimensional organic/inorganic hybrid polyoxometalate formed by cross-like arrangement of a one-dimensional polyoxometalate bridged coordination polymer chain.