Syntheses,crystal structures,and antimicrobial activities of nickel(II) and cadmium(II) complexes with 4-methylsulfonyl cinnamate and diamines

Two metal complexes, [Ni^II(mscinn)₂(pda)₂] (1) and [Cd^II(mscinn)₂(dmeda)₂·2H₂O] (2) (mscinn?=?4-methylsulfonyl cinnamate, pda?=?propane-1,3-diamine, dmeda?=?N′,N′-dimethylethane-1,2-diamine), were synthesized by reacting 4-methylsulfonyl cinnamate with the diamines and metal salts. Their structures were determined by single-crystal X-ray diffraction analysis. Crystal parameters of 1: C₂₆H₃₈N₄NiO₈S₂, M?=?657.43, monoclinic, P2₁/c, a?=?16.6123(8)?Å, b?=?8.5956(4)?Å, c?=?11.2047(5)?Å, β?=?107.423(1)°, V?=?1526.54(12)?ų, Z?=?2, D _calcd?=?1.430?g?cm^?3, F(000)?=?692, μ?=?0.825?mm^?1, R ₁?=?0.0257, wR ₂?=?0.0669. Crystal data of 2: C₂₈H₄₂CdN₄O₈S_2?·?2(H₂O), M?=?775.24, monoclinic, P2₁/c, a?=?9.8278(4)?Å, b?=?11.6611(5)?Å, c?=?15.3972(7)?Å, β?=?96.195(1)°, V?=?1754.26(13)?ų, Z?=?2, D _calcd?=?1.468?g?cm^?3, F(000)?=?804, μ?=?0.798?mm^?1, R ₁?=?0.0299, wR ₂?=?0.0770. Antimicrobial activities for 1 and 2 against Escherichia coli, Pseudomonas putida, Bacillus subtilis, and Bacillus cereus had better antibacterial activity than their parent carboxylic acid against Gram-positive bacteria (B. subtilis and B. cereus). The cadmium complex of the cinnamate displayed high inhibitory activity with an MIC value of 5?µg?mL^?1 against P. putida, while the nickel complex also exhibited good inhibitory potency with an MIC value of 5?µg?mL^?1 against B. subtilis.     

A 1D coordination polymer {Pb[C6H4(COO)2][phen]} n with strong blue fluorescent emission

The hydrothermal reaction of 1,3-dicyanobenzene, 1,10-phenanthroline (phen) and Pb(CH₃COO)₂ yields a new 1D coordination polymer, {Pb[C₆H₄(COO)₂][phen]} _n . The 1,3-benzenecarboxylate anion found in the final product was generated in situ during the synthesis by hydrolysis of 1,3-dicyanobenzene. X-ray diffraction shows that complex 1 crystallizes in the triclinic system, space group P 1, a?=?7.5442(2)?Å, b?=?9.7962(3)?Å, c?=?13.1505(4)?Å, α?=?69.739(2)?Å, β?=?80.597(2)?Å, γ?=?71.377(2)?Å, v?=?862.48(4)?ų, Z?=?2, D _c?=?2.124 Mg?m^?3. Complex 1 emits strong blue fluorescent light (λem(max)?=?482.4?nm) when excited by UV light in the solid state at room temperature.     

Synthesis,crystal structures and fluorescence of cadmium(II) coordination polymers with derivatives of pyrazine-1,4-dioxide and thiocyanate as mixed-bridging ligands

Two Cd(II) coordination polymers have been synthesized with derivatives of pyrazine-1,4-dioxide and thiocyanate anion as bridging ligands and structurally determined by X-ray crystallography. Complex 1, [Cd(μ_1,3-SCN^?)₂(μ_1,6-L1)] _n (L1?=?2,5-dimethylpyrazine-1,4-dioxide), belongs to the triclinic, space group P 1 with a?=?5.7627(18)?Å, b?=?7.182(2)?Å, c?=?7.509(2)?Å, α?=?74.042(3)°, β?=?84.766(4)°, γ?=?88.162(4)°; complex 2, [Cd₂(μ_1,3-SCN^?)₄(μ₄-L2)] _n (L2?=?2,3,5,6-tetramethylpyrazine-1,4-dioxide), crystallizes in a monoclinic system with space group C2/m with a?=?10.194(4)?Å, b?=?13.491(6)?Å, c?=?8.140(3)?Å, β?=?120.372(4)°. Complex 1 shows a two-dimensional sheet structure, and in a direction the Cd(II) ions were coordinated by μ_1,3-SCN^? forming the one-dimensional chain and the L1 bridging ligand made the chains connect in the c direction leading to formation of a two-dimensional sheet on the ac plane. For 2 the one-dimensional chains in the a axis were constructed by coordination of μ_1,3-SCN^? bridging ligands with the Cd(II) ions, and in b and c directions the chains were joined by L2 bridging ligands leading to a three-dimensional structure. In 2 L2 displays a μ₄-bridging coordination mode. Both complexes exhibit strong fluorescence emission.     

Syntheses,crystal structures and magnetic study of two binuclear manganese(II) complexes with aromatic N-oxide as bridging ligand

Two new binuclear complexes, [Mn₂(μ-dmpo)₂(SCN)₄(H₂O)₂] (1) (where dmpo?=?3,5-dimethylpyridine N-oxide), [Mn₂(μ-po)₂(H₂O)₆I₂]I₂ (2) (where po?=?pyridine N-oxide), have been synthesized and their crystal structures determined by X-ray crystallography. Complexes 1 and 2 crystallize in monoclinic, space group P2₁/c, with unit cell dimensions a?=?8.8836(18)?Å, b?=?15.450(3)?Å, c?=?15.484(3)?Å, β?=?91.020(3)° for 1, and a?=?8.8352(13)?Å, b?=?17.927(3)?Å, c?=?8.3338(12)?Å, β?=?103.765(2)° for 2. In each binuclear complex two Mn(II) were bridged by two 3,5-dimethylpyridine N-oxides or by two pyridine N-oxides and the distances between the bridged Mn(II) ions are 3.599?Å for 1 and 3.552?Å for 2. Variable temperature (4–300?K) magnetic measurements were performed for 1 and the susceptibility data were fitted by using a binuclear Mn(II) magnetic coupling formula producing the 2J?=??2.17?cm^?1.     

Malonato-bridged hexamethylenetetramine coordination polymers containing Mn(II) and Cu(II)

Two malonato-bridged hexamethylenetetramine coordination polymers, M₂(hmt)(H₂O)₂(mal)₂ [hmt?=?hexamethylenetetramine, mal?=?malonate(2-), M?=?Mn (1), Cu (2)] were prepared and structurally characterized. The isostructural complexes are orthorhombic, space group Imm2, with a?=?7.104(1), b?=?15.982(3), c?=?7.702(1)?Å, Z?=?2, D _calc?=?1.862?g?cm^?3(1) and a?=?6.962(3), b?=?15.500(7), c?=?7.627(3)?Å, Z?=?2, D _calc?=?2.047?g?cm^?3for 2. The transition metals are octahedrally coordinated by one nitrogen atom of an hmt ligand and five oxygen atoms of a water molecule and three malonate anions. The latter coordinate in chelating/bis-monodentate mode to give 2D layers with a (4,?4) topology, and which are pillared by bridging bidentate hmt ligands to generate an open 3D framework with channels extending in the [001] direction. Over the temperature range 5–300?K, 2 behaves paramagnetically, following the Curie–Weiss law χ_m(T???θ)?=?4.521(6)?cm³mol^?1K with a Weiss constant θ?=??4.8(2)?K.     

Two binuclear complexes containing the enrofloxacinate anion: Cd2(C19H21N3O3F)4(H2O)2 · 4H2O and Pb2(C19H21N3O3F)4 · 4H2O

The syntheses and crystal structures of the closely related but non-isostructural Cd₂(C₁₉H₂₁N₃O₃F)₄(H₂O)₂?·?4H₂O (1) and Pb₂(C₁₉H₂₁N₃O₃F)₄?·?4H₂O (2) are described, where C₁₉H₂₁N₃O₃F^? is enrofloxacinate (enro). Both compounds contain centrosymmetric, binuclear, neutral complexes incorporating a central diamond-shaped M₂O₂ (M?=?Cd, Pb) structural unit. The Cd²⁺ coordination polyhedron in 1 is a CdO₆ trigonal prism, including one coordinated water. The Pb²⁺ coordination polyhedron in 2 can be described as a very distorted square-based PbO₅ pyramid, although two additional short Pb?···?O (<3.1?Å) contacts are also present. In the crystal of the cadmium complex, O–H?···?O hydrogen bonds lead to a layered structure. In the lead compound, O–H?···?O and O–H?···?N interactions lead to chains in the crystal. Crystal data: 1: C₇₆H₉₆Cd₂F₄N₁₂O₁₈, M _r?=?1766.45, triclinic, P 1, a?=?12.185(2)?Å, b?=?12.306(3)?Å, c?=?14.826(3)?Å, α?=?68.15(3)°, β?=?70.28(3)°, γ?=?86.11(3)°, V?=?1938.2(7)?ų, Z?=?1, T?=?298 K, R(F)?=?0.030, wR(F ²)?=?0.079. 2: C₇₆H₈₈F₄N₁₂O₁₆Pb₂, M _r?=?1920.00, triclinic, P 1, a?=?12.0283(4)?Å, b?=?12.7465(4)?Å, c?=?13.0585(4)?Å, α?=?83.751(1)°, β?=?74.635(1)°, γ?=?81.502(1)°, V?=?1904.3(1)?ų, Z?=?1, T?=?298?K, R(F)?=?0.021, wR(F ²)?=?0.049.     

Hydrothermal synthesis and characterization of two new arsenic–vanadate compounds with the same cluster anion [As8V14O42(H2O)]4−

Two new arsenic–vanadate compounds [Co(C₄H₁₃N₃)₂]₂[As₈V₁₄O₄₂(H₂O)]?·?3.5H₂O (1) and (C₂N₂H₉)₂(C₂N₂H₁₀)[As₈V₁₄O₄₂(H₂O)]?·?2.33H₂O (2) have been hydrothermally synthesized and characterized by X-ray single crystal diffraction, IR spectra and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic space group P ₂(1)/c, a?=?24.649(9)?Å, b?=?13.364(5)?Å, c?=?22.463(8)?Å, β?=?104.008(5)°, V?=?7180(5)?ų, Z?=?4, R ₁?=?0.0787, and wR ₂?=?0.1859. Compound 2 crystallizes in rhombohedral system with space group R3c, a?=?b?=?c?=?22.2405(5)?Å, α?=?β?=?γ?=?110.4030(10)°, V?=?8163.4(3)?ų, Z?=?6, R ₁?=?0.0341 and wR ₂?=?0.0941. The structural analyses show that both compounds have the same discrete cluster anion [As₈V₁₄O₄₂(H₂O)]^4?. Moreover, in 1, the polyanions are connected through van der Waals forces to generate soft channels that are filled by [Co(C₄H₁₃N₃)₂]²⁺ cations and water. In 2, water and organic molecules link cluster anions to create the supramolecular assembly through hydrogen bonding.     

Hydrothermal synthesis,structures and characterization of two new copper(II) triphosphonate compounds

Two copper(II) triphosphonate compounds, Cu[(APTPH₄)(phen)(H₂O)]?·?2.16H₂O (1) and [Cu(APTPH₄)(2,2′-bipy)(H₂O)]?·?2.63H₂O (2), have been prepared by a low temperature hydrothermal reaction from 1-aminopropane-1,1,3-triphosphonic acid (APTPH₆), CuO and a second ligand, phen?=?1,10-phenanthroline, or 2,2′-bipy?=?2,2′-bipyridyl. These two compounds were characterized by single crystal X-ray diffraction, elemental analysis, IR and TG. Crystal data for 1: Monoclinic, space group P2₁ /c, a?=?14.4830(7)?Å, b?=?9.1721(5)?Å, c?=?16.7403(8)?Å, β?=?90.101(2)°. For compound 2: Triclinic, space group P 1, a?=?7.1215(7)?Å, b?=?10.460(2)?Å, c?=?14.671(2)?Å, α?=?82.983(2)°, β?=?83.882(2)°, γ?=?80.617(2)°. In both compounds, each Cu²⁺ ion is five-coordinate with two oxygen atoms from the triphosphonate, two nitrogen atoms from the second ligand and one water molecule, to form a distorted square-pyramidal geometry. Both complexes have 3D supramolecular structures constructed by hydrogen bonds and π–π stacking interactions.     

A (3,9)-connected cadmium 1,2,4-triazolate framework based on a trinuclear inorganic cluster

Hydrothermal reaction of 1,2,4-triazole with CdCl₂?·?2.5H₂O generated a 3-D metal-organic framework, {[Cd₃Cl₂(Trz)₄]?·?H₂O} _n (1) (Trz?=?1,2,4-triazole), which was characterized by elemental analysis, FT-IR, X-ray powder diffraction, X-ray single-crystal diffraction, TG/DTA, and photoluminescence measurements. Compound 1 crystallizes in the orthorhombic system, space group Pnma, a?=?16.906(3)?Å, b?=?8.3151(17)?Å, c?=?13.080(3)?Å, V?=?1838.6(6)?ų, Z?=?4. Cd(1) is coordinated by four nitrogen atoms and one chloride to form a distorted trigonal-bipyramidal geometry. Cd(2) is an octahedron defined by four triazole nitrogen atoms and two chlorides. Two Cd(2) and one Cd(1) are linked by μ ₃-Cl(1) to give a [Cd₃Cl] cluster, which is connected by μ ₂-Cl(2) to generate a 1-D inorganic chain. The 1-D inorganic chains are extended by μ ₃-Trz to form a 2-D hybrid layer in the b, c-plane, which is ultimately linked by residual triazole ligands to give a 3-D framework. The [Cd₃Cl] clusters and the Trz ligands can be regarded as 9- and 3-connected nodes, which lead to an unusual (3,9)-connected net with Schläfli symbol of (4²³?·?6¹³)(4³). The solid 1 exhibits high thermal stability and shows strong blue fluorescence emission at 410?nm in the solid state at ambient temperature.     

Synthesis and characterization of a dinuclear (Hedta)Ru(III) complex

A ruthenium(III) complex containing ethylenediaminetetraacetate (edta), [{Ru(Hedta)}₂(Pyz)]?·?8H₂O (1) (Pyz?=?pyrazine), has been synthesized by the reaction between K[Ru(Hedta)Cl]?·?1.5H₂O and pyrazine. The structure of the complex was determined by single X-ray diffraction. Complex 1 crystallizes in the triclinic space group P 1 with a?=?7.293(9)?Å, b?=?10.575(14)?Å, c?=?12.742(16)?Å, α?=?104.044(19)°, β?=?91.893(19)°, γ?=?93.35(2)°, Z?=?1. The product was also characterized by IR, UV-Vis, EPR spectrum and magnetic techniques.     

A dimeric luminescent lanthanide complex [Eu(PAA)2(phen)(NO3)]2: hydrothermal synthesis,crystal structure and fluorescence

A lanthanide coordination complex [Eu(PAA)₂(phen)(NO₃)]₂ (PAA?=?phenylacetic acid, phen?=?1,10-phenanthroline) has been synthesized by the hydrothermal method. Single crystal X-ray diffractions show that it forms a dimeric molecular structure. The title complex crystallizes in the triclinic system, space group P 1, with lattice parameters a?=?8.9473(8)?Å, b?=?13.3659(12)?Å, c?=?13.4745(12)?Å, α?=?60.7590(10)°, β?=?89.5100(10)°, γ?=?71.9850(10)°, V?=?1317.3(2)?ų, D _c?= 1.675?Mg?m^?3, Z?=?1, F(000)?=?660, GOF?=?1.003, R ₁?=?0.0206, wR ₂?=?0.0575. The fluorescence excitation and emission spectra have been investigated.     

Syntheses,crystal structures and fluorescent properties of four one-dimensional lanthanide coordination polymers with 3-cyanobenzoato

The hydrothermal reactions of Nd(ClO₄)₃·6H₂O, Gd(ClO₄)₃·6H₂O, Dy(ClO₄)₃·6H₂O, Er(ClO₄)₃·6H₂O with 1,3-dicyanobenzene, give rise to four one-dimensional rare earth-based coordination polymers: [M(3-CNC₆H₄COO)₃(H₂O)₂] _n (where M?=?Nd (1), Gd (2), Dy (3), Er (4), 3-CNC₆H₄COO?=?3-cyanobenzoato), respectively. Their solid-state structures have been characterized by X-ray single-crystal diffraction studies. The results show that 1,3-dicyanobenzene hydrolyzed to give 3-cyanobenzoato under hydrothermal condition, and the four complexes are isomorphous. Crystal data for 1: triclinic, space group P-1, a?=?9.4063(19), b?=?11.485(2), c?=?12.616(3)?Å, α?=?66.38(3), β?=?74.01(3), γ?=?86.96(3)°, V?=?1197.9(4)?ų, Z?=?1, D _c?=?1.704?Mg?m^?3; for 2: triclinic, space group P-1, a?=?9.3712(19), b?=?11.446(2), c?=?12.627(3)?Å, α?=?65.86(3), β?=?73.89(3), γ?=?86.84(3)°, V?=?1184.8(4)?ų, Z?=?1, D _c?=?1.759?Mg?m^?3; for 3: triclinic, space group P-1, a?=?9.3425(19), b?=?11.432(2), c?=?12.703(3)?Å, α?=?65.28(3), β?=?73.80(3), γ?=?86.86(3)°, V?=?1180.6(4)?ų, Z?=?1, D _c?=?1.780?Mg?m^?3; for 4: triclinic, space group P-1, a?=?9.3425(19), b?=?11.432(2), c?=?12.703(3)?Å, α?=?65.28(3), β?=?73.80(3), γ?=?86.86(3)°, V?=?1180.6(4)?ų, Z?=?1, D _c?=?1.7794?Mg?m^?3. The fluorescence emission spectra of compounds 1 to 4 are also reported.     

Rheological phase synthesis,characterization and magnetic property of a cobalt(II)diphosphonate

A new Co(II) diphosphonate compound, [Co(HEDPH₂)₂] (4,4′-bipyH₂)?·?H₂O (1) has been successfully obtained by a rheological phase reaction at 80°C. Single-crystal diffraction analysis shows a 1-D chain structure and the 1-D chains are assembled via hydrogen bonds into a 3-D supramolecular structure with channels. The protonated 4,4′-bipy molecules are encapsulated in the channels. Magnetic study shows 1 to exhibit antiferromagnetic interaction in the 1D Co--O--P--O--Co chain. Crystal data for 1: monoclinic, space group Cc, a?=?15.754(6)?Å, b?=?14.457(5)?Å, c?=?10.020(4)?Å, β?=?92.024(6)°, V?=?2280.7(14)?ų, Z?=?4.     

Synthesis,structure and characterization of copper(II) and zinc(II) complexes based on 3-carboxyl-1,2,4-triazole

Two complexes [CuL₂(H₂O)₂] (1) and [ZnL₂(H₂O)₂] (2) (L?=?3-carboxyl-1,2,4-triazole (L)) have been synthesized and characterized by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the monoclinic space group P ₂(1)/n, a?=?8.632(8)?Å, b?=?9.153(8)?Å, c?=?6.991(7)?Å, β?=?94.279(12)°, Z?=?2, R ₁?=?0.0296, wR ₂?=?0.0918. Compound 2 also crystallizes in the monoclinic space group P ₂(1)/n, a?=?4.937(3)?Å, b?=?18.107(10)?Å, c?=?6.344(4)?Å, β?=?106.839(7)°, Z?=?2, R ₁?=?0.0230, wR ₂?=?0.0556. Extensive intermolecular hydrogen bonds assemble 1 and 2 into three-dimensional (3D) supramolecular architectures, with eight-member H-bonded synthons. Compounds 1 and 2 were also characterized by element analysis, FT–IR, luminescence and EPR studies.     

Synthesis and structures of two cobalt complexes [NaCoII(NTA)(H2O)] n and NH4[CoIII(IDA)2] · 2H2O

Two cobalt complexes [NaCo^II(nta)(H₂O)] _n (H₃nta?=?nitrilotriacetic acid) (1) and NH₄[Co^III(ida)₂]?·?2H₂O (H₂ida?=?iminodiacetic acid) (2) have been synthesized and characterized by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the orthorhombic system, space group P2₁2₁2₁ with a?=?7.9770(12)?Å, b?=?9.7613(15)?Å, c?=?12.1945(18)?Å, V?=?949.5(2)?ų, Z?=?4, and R ₁?=?0.0705 for 1597 observed reflections. Compound 2 crystallizes in the monoclinic system, space group P2(1)/c with a?=?5.1801(3)?Å, b?=?11.2073(6)?Å, c?=?12.2891(7)?Å, V?=?707.09(7)?ų, Z?=?2, and R ₁?=?0.0349 for 1143 observed reflections. In compound 1, the Co is coordinated by a nitrogen and five oxygen atoms in a distorted octahedral geometry {CoNO₅}, and the Na is coordinated by one water molecule and four carboxyl oxygen atoms in slightly distorted square pyramidal geometry. The entire structure shows a three-dimensional network. In compound 2, Co atom is equatorially coordinated by two ida ligands in a distorted octahedral geometry {CoN₂O₄}. The discrete [Co(ida)₂]^2? anions are linked by hydrogen bonding to a three-dimensional supramolecular network.     

Synthesis,crystal structures and magnetism of lanthanide(III) binuclear complexes [Ln2(μ1 ,3-CH3CO2)2(SCN−)4L2(H2O)6] (Ln = Gd(III) and Eu(III), L = 4-methylpyridine N-oxide)

Two lanthanide(III) binuclear complexes have been synthesized with acetate as bridging ligand and 4-methylpyridine N-oxide (L), SCN^? and H₂O as terminal ligands and structurally determined by X-ray crystallography. Both crystals [Gd₂(μ_1,3-CH₃CO₂)₂(SCN^?)₄(L)₂(H₂O₆) (1) and [Eu₂(μ_1,3-CH₃CO₂)₂(SCN^?)₄(L)₂(H₂O)₆] (2) belong to monoclinic with space group P2₁/n. The relevant cell parameters are as follows: a?=?9.0034(12)?Å, b?=?15.998(2)?Å, c?=?12.1277(17)?Å, β?=?100.625(2)° for complex 1; and a?=?9.0168(18)?Å, b?=?15.990(3)?Å, c?=?12.142(2)?Å, β?=?100.734(3)° for complex 2; The two lanthanide(III) ions are bridged by two acetate anions forming a binuclear unit, in which L, SCN^? and H₂O as unidentate terminal ligands take part in the coordination. The variable-temperature magnetic susceptibility of 1 was measured in the 4–300?K range; fitting for the susceptibility data reveals that there is no magnetic interaction between the bridged Gd(III) ions.     

Hydrothermal syntheses,crystal structures,and thermal stability of two new 3D open-framework metal(II) phosphonates

This article reports the hydrothermal synthesis and characterization of two new phosphonate compounds NaCo[O₃PCH(OH)CO₂] (1) and NaMn[O₃PCH(OH)CO₂] (2) based on 2-hydroxyphosphonoacetic acid (H₃L). Their structures have been characterized by single-crystal X-ray diffraction as well as with elemental analysis, infrared spectroscopy and thermogravimetric analysis. The two isomorphous compounds crystalline in the orthorhombic, space group Pbca: Crystal data for 1: a?=?10.1827(8)?Å, b?=?9.6673(8)?Å, c?=?10.7853(9)?Å, V?=?1061.70(15)?ų, Z?=?8, R ₁?=?0.0252, wR ₂?=?0.0577; Crystal data for 2: a?=?10.4309(18)?Å, b?=?9.7913(17)?Å, c?=?10.9012(19)?Å, V?=?1113.4(3)?ų, Z?=?8, R ₁?=?0.0194, wR ₂?=?0.0536. In the two compounds, the metal atoms are octahedrally coordinated; all oxygen atoms from the H₃L ligand are involved in coordination. The overall structures can be described as a 3D open framework with channels running along the a axis and the charge-compensating Na⁺ cations being located at the intersections of these channels.     

Solid state structures of the chiral heterobimetallic complexes [Cu(dach)2][Pt(CN)4] · 2H2O, [Ni(dach)3][Pt(CN)4] · 2DMF · H2O,and [Pd(dach)2][Pt(CN)4] · H2O (dach = 1 R , 2 R -diaminocyclohexane)

The chiral dinuclear heterometallic complexes [Cu(dach)₂][Pt(CN)₄]?·?2H₂O (1), [Ni(dach)₃][Pt(CN)₄]?·?2DMF?·?H₂O (2), and [Pd(dach)₄][Pt(CN)₄]?·?H₂O (3) (dach?=?1R,2R-cyclohexanediamine) have been prepared and characterized by X-ray diffraction analysis. Crystal data: 1, monoclinic, P2₁, a?=?8.108(3), b?=?15.552(6), c?=?9.914(4)?Å, β?=?110.931(6)°, V?=?1167.6(8)?ų, Z?=?2, R ₁?=?0.0420, wR ₂?=?0.1122; 2, monoclinic, P2₁, a?=?13.264(11), b?=?9.285(7), c?=?16.211(13)?Å, β?=?111.640(9)°, V?=?1856(3)?ų, Z?=?2, R ₁?=?0.0276, wR ₂?=?0.0698; 3, monoclinic, P2₁, a?=?6.887(2), b?=?12.809(4), c?=?12.975(4)?Å, β?=?94.865(4)°, V?=?1140.6(6)?ų, Z?=?2, R ₁?=?0.057, wR ₂?=?0.156. In complex 1, the Pt and Cu atoms are linked by a CN bridge that presents a very bent C=N–Cu angle [136.8(8)°].     

Synthesis,crystal structure,and catalytic performance of two 3-D supramolecular compounds: (C7N2H7)3(C7N2H6) · PMo12O40 · 2H2O and (C7N2H7)3(C7N2H6)2 · AsMo12O40 · 3H2O

Two organic–inorganic compounds based on Keggin building blocks have been synthesized by hydrothermal methods, (C₇N₂H₇)₃(C₇N₂H₆)?·?PMo₁₂O_40?·?2H₂O (1) and (C₇N₂H₇)₃(C₇N₂H₆)_2?·?AsMo₁₂O_40?·?3H₂O (2) (C₇N₂H₆?=?benzimidazole). Single-crystal X-ray analysis revealed that 1 crystallized in the triclinic system, P-1 space group with a?=?9.8980(4)?Å, b?=?11.2893(4)?Å, c?=?25.8933(9)?Å, α?=?93.307(2)°, β?=?90.630(2)°, γ?=?108.330(2)°, V?=?2740.68(18)?ų, Z?=?2, R ₁(F)?=?0.0740, ωR ₂(F ²)?=?0.1511, and S?=?1.037; 2 crystallized in the triclinic system, P-1 space group with a?=?12.3353(4)?Å, b?=?13.2649(4)?Å, c?=?20.2878(6)?Å, α?=?95.6630(10)°, β?=?100.1720(10)°, γ?=?99.3940(10)°, V?=?3195.72(17)?ų, Z?=?2, R ₁(F)?= 0.0329, ωR₂ (F ²)?=?0.1236, and S?=?1.088. The two compounds show a layer framework constructed from Keggin-polyoxoanion clusters and benzimidazole via hydrogen bonds and π–π stacking interactions, resulting in a 3-D supramolecular network. Both have high catalytic activity for oxidation of methanol. When the initial concentration of the methanol is 5.37?g?m^?3 in air and the flow velocity is 4.51?mL?min^?1, methanol is completely eliminated at 150°C for 1 (160°C for 2).