A three-dimensional zincic molybdenum (V) phosphate with helical channel: Synthesis,structure, and electrochemical properties

A new reduced zincic molybdophosphate, (H₂bpp)₃[Zn₃Mo₁₂^VO₂₄(OH)₆(H₂O)₂(HPO₄)₆(PO₄)₂]·2H₂O 1 (bpp = 1,3-bis(4-pyridyl)propane) has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal space group I 41/a c d with a = 31.8033(4) Å, b = 31.8033(4) Å, c = 34.5593(8) Å, V = 34955.0(10) ų, and Z = 16 and exhibits a 4,6-connected 3-D framework with (3².8⁴)(3⁴.4².8³.9⁵.10) topology. The basic building blocks of [Zn(2)(Mo₆P₄)₂] are linked through [Zn(3)O₆] octahedra and [Zn(1)O₄] tetrahedra to construct 1-D chains along four different directions. Such 1-D chains are further connected by [Zn(1)O₄]²⁺ linkers to form a 3-D intricate framework with helical channels occupied by protonated bpp and water molecules. Additionally, the electrochemical property of the 1-CPE has been studied in detail.     

Hydrothermal synthesis,crystal structure and magnetic properties of a novel nickel carboxylate–phosphonate with a layered structure

Hydrothermal reactions of N-(phosphonomethyl)proline (H₃L) with nickel sulfate hexahydrate resulted in a novel nickel carboxylate–phosphonate: |H₂O|[Ni₃(O₃PCH₂–NC₄H₇–CO₂)₂(H₂O)₄] (complex 1). Single-crystal X-ray diffraction analysis revealed that complex 1 crystallizes in the triclinic space group P-1 (No. 2), with lattice parameters of a = 10.0167(5) Å, b = 10.3882(5) Å, c = 11.9528(5) Å, α = 90.132(3)°, β = 107.246(3)°, γ = 111.158(3)°, V = 1099.39(9) Å³, and Z = 2. Complex 1 features a 2D layered structure. The structure contains alternating Ni-centered octahedra (Ni(1)O₆, Ni(2)O₅N and Ni(3)O₅N) and O₃PC tetrahedra linked to construct a layer with rhombohedral 12-MRs holes. The cyclopentylamine moieties of H₃L were grafted onto the layer through coordination of CPO₃, CO₂ and (CH₂)₂NCH₂ with central nickel atoms. These layers are stacked in an AA sequence, which results in a one-dimensional channel in the [001] direction. Water molecules are located in these channels. Magnetic studies showed that complex 1 exhibits predominantly paramagnetic behavior.     

Organic–inorganic hybrid oxides: Structure and magnetic properties of [{Cu(terpy)}2Mo6O17(H2O)(O3PCH2NH2CH2PO3)2] · H2O,a bimetallic oxide constructed from novel {Mo6O17(H2O)(O3PCH2NH2CH2PO3)2}4− clusters

The hydrothermal reaction of MoO₃, CuSO₄ · 5H₂O, 2,2′:6′:2″-terpyridine (terpy) and bis-N,N-(methylphosphonic acid) amine (H₂O₃PCH₂NHCH₂PO₃H₂) provided blue crystals of the bimetallic oxide [{Cu(terpy)}₂Mo₆O₁₇(H₂O)(O₃PCH₂NH₂CH₂PO₃)₂] · H₂O (1 · H₂O). The three-dimensional structure of 1 is constructed from {Mo₆O₁₇(H₂O)(O₃PCH₂NH₂CH₂PO₃)₂}⁴⁻ clusters linked through {Cu(terpy)}²⁺ subunits. The cluster consists of three pairs of edge-sharing {MoO₆} octahedra linked through corner-sharing interactions into a {Mo₆O₆} ring. One phosphonate ligand spans the diameter of the ring, bridging four molybdenum sites and leaving at a pendant {PO} group at each terminus. The second diphosphonate ligand exploits one {–PO₃} unit to cap the hexamolybdate ring and bridge all six molybdenum sites while the second {–PO₃} terminus bridges two molybdenum sites, leaving a pendant {PO} unit. Crystal data: C₃₄H₄₅Cu₂Mo₆N₈O₃₅P₄: monoclinic, P2₁/n, a = 11.9431(7) Å, b = 17.382(1) Å, c = 27.524(2) Å, β = 90.429(1)°, V = 5713.7(6) Å³, Z = 4, D_calc = 2.270 g cm⁻³, R₁ = 0.0466.     

Synthesis,structure and photocatalytic hydrogen evolution of a silver-linked hexaniobate Lindqvist chain

By using a combination of hydrothermal and diffusional strategies, a one-dimensional polyoxoniobate K₅[H₂AgNb₆O₁₉]·11H₂O (1) has been synthesized. The structure was characterized by single-crystal X-ray diffraction, UV spectroscopy, TG analysis, PXRD and IR spectrum. 1 crystallizes in the hexagonal P63/mmc space group with a = 9.8171(2) Å, c = 16.5442(6) Å, and V = 1380.84(6) Å³. It is the first Ag-containing polyoxoniobate, which consists of [H₂AgNb₆O₁₉]^5 − polyoxoanion and potassium ions. In addition, 1 exhibits the photocatalytic H₂ evolution activity.     

A novel paradodecatungstate-B compound decorated by transition metal copper,Na2Cu5(H2O)24(OH)2[H2W12O42]·10H2O: Synthesis,structure and antitumor activities

A new paradodecatungstate-B compound decorated by transition metal copper, Na₂Cu₅(H₂O)₂₄(OH)₂[H₂W₁₂O₄₂]·10H₂O (1), has been synthesized by convenient aqueous solution method and structurally characterized by single-crystal X-ray diffraction, IR spectrum, elemental analysis and TGA. The compound crystallizes in the triclinic P-1 space group with a = 10.7140(8) Å, b = 12.9476(9) Å, c = 13.6696(10) Å, α = 73.56°, β = 75.73°, γ = 67.69°, V = 1661.8(2) ų and Z = 1. In compound 1, polyanion of [H₂W₁₂O₄₂]^10 − acts as a dodecadentate ligand that links copper and sodium cations, forming a remarkable three-dimensional framework. The experiment of antitumor activities in vitro shows that the title compound exhibits remarkable inhibitory actions on human cervical carcinoma HeLa cells, ovarian carcinoma SKOV-3 cells, hepatoma HepG2 cells and neuroblastoma SHY5Y cells.     

A novel transition-metal-linked hexaniobate cluster with photocatalytic H2 evolution activity

A novel transition-metal (TM) complex based on Lindqvist polyoxoniobate K₁₀[(Nb₆O₁₉)Cr^III(H₂O)₂]₂·28H₂O (1) has been synthesized by a new two-pot synthesis strategy and structurally characterized by single crystal X-ray diffraction analysis, IR spectrum, UV–vis spectroscopy, XRPD and TG analysis. Compound 1 crystallizes in the C2/m space group with a = 32.143(19) Å, b = 10.030(6) Å, c = 12.878(8) Å, β = 110.611(9)°, and V = 3886(4) ų. X-ray structure analysis reveals that polyanion [(Nb₆O₁₉)Cr^III(H₂O)₂]₂^10 − (1a) represents the first example of two nuclear dimeric polyoxoniobate, in which two Lindqvist anions [Nb₆O₁₉]⁸ are sandwiched by two {Cr^III(H₂O)₂} groups. Further, 1 exhibits photocatalytic H₂ evolution activity.     

Synthesis,structure, and adsorption properties of a three-dimensional porous yttrium–organic coordination network

Deprotonation of 4,4′-biphenyldicarboxylic acid (H₂BPDC) with triethylamine followed by the copolymerization with Y(III) in N,N-dimethylformamide (DMF) at room temperature yields a new three-dimensional (3-D) porous metal–organic coordination network, [Y₂(BPDC)₃(DMF)₂(H₂O)₂]_n · (DMF)_n · (H₂O)_n (1). Compound 1 (C_24.50H₁₉N_1.50O₉Y) crystallizes in the triclinic P-1 space group (a = 8.220 (2), b = 13.998 (4), c = 14.212 (4) Å, α = 111.058 (5)°, β = 90.187 (5)°, γ = 94.318 (5)°, V = 1520.9 (7) ų, and Z = 2). X-ray crystallography reveals that 1 consists of a 3-D framework contained open 1-D channels with the dimension of 5 × 10 Å along the crystallographic a axis. The adsorption measurements show that compound 1 can adsorb N₂, Ar and CO₂ into its pores. The adsorption isotherms for MeOH and H₂O were also measured.     

Synthesis,structure and characterization of a new nonlinear optical calcium borate [Ca2B5O9]·[H(OH)2]

A new nonlinear optical crystal [Ca₂B₅O₉]·[H(OH)₂] (1) has been synthesized under hydrothermal condition. Compound 1 crystallizes in the monoclinic space group C2 with lattice constants a = 10.111(2) Å, b = 7.754(11) Å, c = 6.198(14) Å, β = 127.04(3)° and Z = 2. The fundamental building block (FBB) of 1 is a [B₅O₁₂] unit with two BO₃ triangles and three BO₄ tetrahedra. 1 was characterized by single-crystal X-ray diffraction, IR and UV–Vis spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) respectively. Also, powder second harmonic generation (SHG) measurements indicate that 1 is phase matchable and displays a SHG response of about 3.5 times that of KDP (KH₂PO₄).     

Synthesis,structure and fluorescence properties of a uranyl-2,5-pyridinedicarboxylic acid coordination polymer: The missing member of the UO22+-2,n-pyridinedicarboxylic series

A 3D uranium-pyridinedicarboxylate, compound (1) [UO₂(C₇H₃NO₄)], represents the final member of a series of materials incorporating a series of 2,n-pyridinedicarboxylic (pydc) acids (n = 3,4,5,6). The resulting crystal structure [FW = 419.13, monoclinic, P2₁/n, a = 9.0096(3) Å, b = 8.1371(2) Å, c = 11.6954(4) Å, V = 852.45 ų, Z = 4] was determined by single crystal X-ray diffraction and fluorescent properties were investigated. Additionally, the complete series of uranium-2,n-pydc materials was examined on a basis of fluorescent behaviors and architectural similarities.     

An inorganic–organic hybrid material with a novel oxometallic framework: Hydrothermal synthesis and characterization of [Zn3O3(C13H14N2)3]V6O15

A new hybrid material [Zn₃O₃(C₁₃H₁₄N₂)₃]V₆O₁₅ (1) with extended framework structure has been synthesized hydrothermally and characterized by vibrational spectroscopy, thermogravimetry and complete single crystal X-ray diffraction analysis. The compound has a complex three-dimensional covalent framework structure. It exhibits a fully oxidized novel oxometallic framework containing 10-membered {V₄ZnO₅} oxometalate rings and 4,4′-trimethylene dipyridine ligands (C₁₃H₁₄N₂) that connect pairs of crystallographically equivalent zinc atoms. The extended structure of 1 may also be viewed as containing a framework of corner-sharing {VO₄} and {ZnO₂N₂} polyhedra together with 4,4’-trimethylene dipyridine ligands linking zinc centers. The hybrid material is thermally stable up to 323 °C. It contains metal centers and coordination geometry that make it a potentially attractive model compound for investigating the structures of metallo-organic biomolecules by use of solid state NMR spectroscopic techniques. Crystal data for C₃₉H₄₂N₆O₁₈V₆Zn₃: monoclinicic P2₁, a = 10.9894(9) Å, b = 18.1493 (15) Å, c = 13.0903 (11) Å, β = 109.8880(10)°, V = 2455.1(4) Å³, Z = 2, D_calc. = 1.873 Mg/m³.     

(CH3NH3)2[Ge(B4O9)]: An organically-templated chiral borogermanate with second-order nonlinear and ferroelectric properties

An organically-templated chiral borogermanate (CH₃NH₃)₂[Ge(B₄O₉)] (1), has been solvothermally synthesized and characterized by elemental analysis, IR, PXRD, TGA, single-crystal X-ray diffraction and UV–vis spectrum. It crystallized in the monoclinic space group C2 (No. 5) with a = 10.249(1) Å, b = 9.449(1) Å, c = 6.956(2) Å, β = 131.76(2)°, V = 502.43(19) Å³, Z = 2. The structure is constructed by alternate linkage of GeO₄ tetrahedra and B₄O₉ clusters to form a zeotype framework with diamond topology. Four intersecting channels with different sizes are observed. Large circular 10-ring channels are clearly extended along the [001] direction, 9-ring channels are running along the [101], [110], and [112] directions, respectively. Additionally, two pairs of the right- and left-handed channels couple together along the [100] and [010] directions, respectively. The preliminary investigations show that compound 1 exhibits second-harmonic generation (SHG) response and ferroelectric properties.     

A novel lead borate of NaPb4(H2O)(B5O9)2·BO3 with nonlinear optical property

A new mixed metal borate, NaPb₄(H₂O)(B₅O₉)₂·BO₃, with an acentric structure has been successfully made under hydrothermal conditions and structurally characterized by IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction, respectively. The structural analysis shows that 1 crystallizes in the orthorhombic space group Pnn2 (No. 34) with a = 11.3724(5) Å, b = 11.4455(4) Å, c = 6.5578(2) Å and Z = 2. In the structure 1, the structural building unit, B₅O₁₂ cluster, connects adjacent six same ones to form a 3-D oxoboron framework with 8-membered ring (MR) and 10-MR channels along the c-axis. The Pb atoms and coordinated water molecules are located in the 8-MR channels, while the 10-MR channels were occupied by the chains built by Na atoms and the BO₃ groups. Second-harmonic generation (SHG) measurements on the powder samples reveal that 1 exhibits SHG efficiency approximately 2 times that of KH₂PO₄ (KDP). Also it has a UV cutoff edge below 220 nm.     

The first example of extended structure constructed from Knoth-type sandwich POMs and coordination fragments

A novel compound [P₂W₁₈M₃O₆₈][Cu(en)₂]₄·7H₂O·2OH^? (M = 0.5W + 0.5Cu) 1 which contains the first example of extended structure constructed from Knoth-type sandwich polyoxoanions and transition metal coordination complexes has been hydrothermally synthesized and characterized by elemental analysis, IR spectrum, UV–Vis spectrum and single-crystal X-ray diffraction analysis. Crystal data for 1: triclinic, space group, P-1, a = 13.2718(7) Å, b = 13.6432(8) Å, c = 25.7307(15) Å, α = 104.7340(10)°, β = 96.7630(10)°, γ = 90.0330(10)°, V = 4472.2(4) Å³, Z = 2. Structure solution and refinement based on 1090 parameters gave R1 (wR2) = 0.0409 (0.0993).     

Inorganic–organic hybrid material containing β-cage: {[H2(en)]Co2(ox)(V4O12)}n

By using an organic ligand, a new inorganic–organic hybrid compound of cobalt oxalate-vanadate, {[H₂(en)]Co₂(ox)(V₄O₁₂)}_n 1, where en = ethylenediamine, ox = oxalic acid, has been synthesized hydrothermally from V₂O₅,CoCl₂·6H₂O,H₂C₂O₄·2H₂O and en. Crystal data 1, orthorhombic, Cmcm space group, a=11.624(2), b=9.968(2), c=14.900(3) Å, R1=0.0298, wR2=0.1172. Compound 1 possesses a three-dimensional open-framework with β-cage and is an antiferromagnetic matter.     

Room temperature assembly of a uranyl carboxyphosphonate: Synthesis,characterization and UO22+ hydrolysis

A novel 1-dimensional U(VI) phosphonoacetate, UO₂(O₃PCH₂CO₂H)(H₂O)·2H₂O (1), has been synthesized from the room temperature reaction of uranium nitrate and phosphonoacetic acid (H₃PPA) in water. The compound crystallizes in a monoclinic space group (P2₁, a = 8.3517(5) Å, b = 7.0013(4) Å, c = 8.3728(5) Å, β = 107.310(1)°, Z = 2) and exhibits bonding to the UO₂²⁺ through both phosphonate and carboxylate oxygen atoms of the acid unit. The crystal structure, thermal and fluorescent behaviors, and role of UO₂²⁺ hydrolysis in the context of ambient versus hydrothermal syntheses are discussed.     

Synthesis of 1,1′-ferrocene bis(carboxypyrazole) compounds and displacement of the pyrazole ligands

The reaction of 1,1′-ferrocenedicarbonyl chloride with pyrazole or 3,5-dimethyl pyrazole generates novel 1,1′-ferrocene bis(amide) compounds 1 and 2, respectively. The crystal structure of 1 shows that the pyrazole rings are essentially co-planar with each other and with the cyclopentadienyl rings. Attempts to use the complexes as a chelating ligand were unsuccessful. Instead, treatment of 1 or 2 with Mo(CO)₄(pip)₂, pip = piperidine, led to displacement of the pyrazole ligands and formation of the known amide compound, 1,1′-ferrocene bis carbonyl piperidine. Replacement of the pyrazole is ascribed to the weakness of the amide bond caused by the aromaticity of the pyrazole ring. Crystal data for C₁₈H₁₄FeN₄O₂ (1): monoclinic P2(1)/c, a = 13.3907(18) Å, b = 10.2112(14) Å, c = 11.3082(16) Å, β = 105.209(2)°, V = 1492.1(4) Å³, Z = 4.     

An organic–inorganic hybrid nickel-substituted arsenotungstate consisting of three types of polyoxotungstate units

A new organic–inorganic hybrid nickel-substituted arsenotungstate [Na(H₂O)₃]₂[Ni(H₂O)₆]₂[Ni(H₂O)₅]{[Ni₃(dap)(H₂O)₂]₂(H₂W₄O₁₆)}{(α-H₂AsW₆O₂₆)[Ni₆(OH)₂(H₂O)(dap)₂](B-α-HAsW₉O₃₄)}₂·7H₂O (1) (dap = 1,2-diaminopropane) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal data for 1: C₁₈H₁₄₄As₄N₁₂Na₂Ni₂₁O₁₇₆W₃₄, Mr = 11174.92, triclinic, space group P-1, a = 15.004(4) Å, b = 16.357(5) Å, c = 22.070(6) Å, α = 80.458(5)°, β = 79.291(5)°, γ = 72.074(5)°, V = 5030(3) Å³, Z = 1, GOOF = 1.007, R₁ = 0.0703, wR₂ = 0.1670. The skeleton of 1 is a centric nanoscale cluster and is composed of two asymmetric sandwich-type clusters {(α-H₂AsW₆O₂₆)[Ni₆(OH)₂(H₂O)(dap)₂](B-α-AsW₉O₃₄)}^7? linked by a symmetric cluster {[Ni₃(dap)(H₂O)₂]₂(H₂W₄O₁₆)}⁶⁺. Notably, 1 is an interesting polyoxometalate containing the trivacant Keggin [B-α-AsW₉O₃₄]^9?, hexavacant Keggin [α-AsW₆O₂₆]^11? and tetrameric [W₄O₁₆]^8? units. Magnetic measurements indicate that 1 shows the ferromagnetic interactions within Ni^II centers.     

LiBa1.5[B5O8(OH)3]: A new 1-D metal borate chain constructed from B5O9(OH)36 − cluster units

A new mixed metal borate LiBa_1.5[B₅O₈(OH)₃] (1) has been hydrothermally synthesized and structurally characterized by FT-IR spectroscopy, powder X-ray diffraction, single crystal X-ray diffraction, and thermogravimetric analysis, respectively. 1 crystallizes in the monoclinic system, space group C2/c, a = 11.2839(7) Å, b = 7.3974(4) Å, c = 20.7151(13) Å, β = 103.392(6)°, V = 1682.10(17) ų and Z = 8. The structure consists of infinite one-dimensional (1-D) borate chains constructed from B₅O₉(OH)₃^6 − cluster units. These BO chains are further linked by the Ba^2 + and Li⁺ cations to form a 3-D framework.     

(en)Mn2(V2O7): A 3D manganese vanadate built by Mn–O layers and two types of pillars of V2O7 and en bridges

An unexpected 3D manganese vanadate (en)Mn₂(V₂O₇) (1) (en = ethylenediamine) has been hydrothermally obtained by H₂E₂Ge₂O₃ (E = ? CH₂CH₂COO^?) ligands and well-prepared mixture of V–Mn-amine and characterized by IR spectroscopy, elemental analysis, thermal stability and powder X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that the structure is a novel pillared-layer, in which MnO₅N octahedra are corner-linked to form an infinite sheet with 4-membered rings (MRs) and further condensed to the 3D framework. The most prominent feature of 1 is the connection between the sheets via double bridges, namely, inorganic V₂O₇ dimeric units and organic en molecules. It is noteworthy that inorganic and organic double bridges between sheets have not been seen in manganese vanadates.