Open-framework aluminoborates co-templated by two types of primary amines

A series of open-framework aluminoborates (ABOs), [CH(3)NH(3)][(CH(3)CH(2))(2)NH(2)][Al(B(5)O(10))] (1), [CH(3)CH(2)NH(3)][(CH(3)CH(2))(2)NH(2)][Al(B(5)O(10))] (2), [CH(3)CH(2)NH(3)][(CH(3))(2)NH(2)](H(2)O)(0.5)[Al(B(5)O(10))] (3) and [CH(3)NH(3)][CH(3)CH(2)NH(3)](H(2)O)(2)[Al(B(5)O(10))] (4) have been made co-templated by two types of primary amines under solvothermal conditions and characterized by elemental analysis, IR, TGA, UV-Vis, powder XRD, single crystal XRD and NLO determination, respectively. These four ABOs display two structural types: 1, 2 and 3 are isostructural and exhibit CrB(4) topology, showing three different layers along three different directions; while 4 contains 8-, 14-ring layers, which are packed along the [001] direction to form a noncentrosymmetric 3D framework with 8-, 14-ring channels, showing second harmonic generation (SHG) response that is about 0.5 times that of KDP (KH(2)PO(4)). The electronic structure calculations for 1 and 4 also have been performed.     

Two new cobalt-zinc orthophosphate monohydrates: hydrothermal synthesis, crystal structures and thermal investigation

Two new cobalt zinc orthophosphate hydrates with similar chemical formula, (CoxZn(1-x))3(PO4)2.H2O, but different composition and structure, have been prepared by systematic hydrothermal synthesis from the system nCo(CH3COO)2 : (1 -n)Zn(CH(3)COO)2 : 3.5H3PO4 : 2.1(CH3)2NH(CH2)3NH2:144H2O (0 相似文献   

Hydrothermal Syntheses and Characterizations of Two One-dimensional Molybdenum 1,4-Butylenediphosphonates

1 INTRODUCTION Interest in metal phosphonate chemistry has in- creased in recent years, not only because of their rich structural chemistry[1～3] but also owing to their potential applications in catalysis, absorption and intercalation reaction[4～6]. The introduction of a se- cond metal-ligand component as a charge-compen- sating unit and structure-directing component into polyoxomolybdenum/oxovanadium organodi-phos- phonates has provided us a powerful method to syn- thesize this family o…     

Synthesis and structural characterization of 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O and 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O and [Co(dien)(2)][V(3)O(9)].H(2)O templated by cobalt complexes: cooperative organization of the complexes and the inorganic networks

A 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O (1) and two 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O (2) and [Co(dien)(2)][V(3)O(9)].H(2)O (3) have been synthesized hydrothermally from the reaction mixture of V(2)O(5)-H(3)PO(4)-H(3)BO(3)-CoCl(2)-R-H(2)O at 110 degrees C (R: en or dien). The complex cations Co(en)(3)(3+) and Co(dien)(2)(3+) are cooperatively organized in the reaction medium to play a structure-directing role in the formation of the inorganic clusters and chains. The structures are determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, and TG analyses. The structure of 1 contains isolated [V(3)P(3)BO(19)](5)(-) cluster anions, H(2)PO(4)(-) anions, racemic Co(en)(3)(3+) cations, and H(2)O molecules, which form a complex H-bond network. 2 and 3 both contain chains of corner-sharing VO(4) tetrahedra running along the 2(1) screw axis. The complex cations located in the interchain region interact with the chains through H-bonds. 2 is crystallized in an enantiomorphic space group and only one enantiomer of Co(en)(3)(3+) is involved in the structure. Crystal data: 1, monoclinic, C2/c, a = 32.8492(14) A, b = 11.9601(3) A, c = 22.6001(7) A, beta = 108.9630(8) degrees, Z = 8; 2, orthorhombic, P2(1)2(1)2(1), a = 8.1587(16) A, b = 12.675(3) A, c = 18.046(4) A, Z = 4; 3, monoclinic, P2(1)/c, a = 16.1663(10) A, b = 8.7028(3) A, c = 13.9773(5) A, beta = 103.1340(18) degrees, Z = 4.     

Synthesis and characterization of the open-framework barium bisphosphonate [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O

Following the strategy of using polyfunctional phosphonic acids for the synthesis of open-framework metal phosphonates, the phosphonocarboxylic acid (H2O3PCH2)2NCH2C6H4COOH was used in the hydrothermal synthesis of new Ba phosphonates. Its decomposition led to the first open-framework barium phosphonate [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O. The synthesis was also successfully performed using iminobis(methylphosphonic acid), (H2O3PCH2)2NH, as a starting material, and the synthesis was optimized to obtain as a pure material. The reaction setup as well as the pH are the dominant parameters, and only a diffusion-controlled reaction led to the desired compound. The crystal structure was solved from single-crystal data: monoclinic; C2/c; a=2328.7(2), b=1359.95(7), and c=718.62(6) pm; beta=98.732(10) degrees ; V=2249.5(3)x10(6) pm3; Z=4; R1=0.036; and wR2=0.072 (all data). The structure of [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O is built up from BaO8 and BaO10 polyhedra forming BaO chains and layers, respectively. These are connected to a three-dimensional metal-oxygen-metal framework with the iminobis(methylphosphonic acid) formally coating the inner walls of the pores. The one-dimensional pores (3.6x4 A) are filled with H2O molecules that can be thermally removed. Thermogravimetric investigations and temperature-dependent X-ray powder diffraction demonstrate the stability of the crystal structure up to 240 degrees C. The uptake of N,N-dimethylformamide and H2O by dehydrated samples is demonstrated. Furthermore, IR, Raman, and 31P magic-angle-spinning NMR data are also presented.     

A hydrothermal investigation of the 1/2V2O5-H2C2O4/H3PO4/NH4OH system: synthesis and structures of (NH4)VOPO(4).1.5H2O, (NH4)0.5VOPO(4).1.5H2O, (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2](2).3H2O, and (NH4)2[VO(HPO4)]2(C2O4).5H2O

The 1/2V2O5-H2C2O4/H3PO4/NH4OH system was investigated using hydrothermal techniques. Four new phases, (NH4)VOPO(4).1.5H2O (1), (NH4)0.5VOPO(4).1.5H2O (2), (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2.3H2O (3), and (NH4)2[VO(HPO4)]2(C2O4).H2O (4), have been prepared and structurally characterized. Compounds 1 and 2 have layered structures closely related to VOPO(4).2H2O and A0.5VOPO4.yH2O (A = mono- or divalent metals), whereas 3 has a 3D open-framework structure. Compound 4 has a layered structure and contains both oxalate and phosphate anions coordinated to vanadium cations. Crystal data: (NH4)VOPO(4).1.5H2O, tetragonal (I), space group I4/mmm (No. 139), a = 6.3160(5) A, c = 13.540(2) A, Z = 4; (NH4)0.5VOPO(4).1.5H2O, monoclinic, space group P2(1)/m (No. 11), a = 6.9669(6) A, b = 17.663(2) A, c = 8.9304(8) A, beta = 105.347(1) degrees, Z = 8; (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2.3H2O, triclinic, space group P1 (No. 2), a = 10.2523(9) A, b = 12.263(1) A, c = 12.362(1) A, alpha = 69.041(2) degrees, beta = 65.653(2) degrees, gamma = 87.789(2) degrees, Z = 2; (NH4)2[VO(HPO4)]2(C2O4).5H2O, monoclinic (C), space group C2/m (No. 12), a = 17.735(2) A, b = 6.4180(6) A, c = 22.839(2) A, beta = 102.017(2) degrees, Z = 6.     

A novel organic-inorganic hybrid based on an 8-electron-reduced Keggin polymolybdate capped by tetrahedral, trigonal bipyramidal, and octahedral zinc: synthesis and crystal structure of (CH3NH3)(H2bipy)[Zn4(bipy)3(H2O)2MoV8MoVI4O36)(PO4)].4H2O

Hydrothermal reaction of H(3)PO(3), CH(3)NH(2), zinc(II) acetate, 4,4'-bipyridine (bipy), and (NH(4))(6)Mo(7)O(24).4H(2)O at 180 degrees C led to a novel organic-inorganic layered hybrid, [CH(3)NH(3)][H(2)bipy][Zn(4)(bipy)(3)(H(2)O)(2)Mo(V)(8)Mo(VI)O(36)(PO(4))].4H(2)O (1). Its structure was established by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P2(1)/c with cell parameters of a = 17.3032(2), b = 17.8113(3), and c = 23.4597 (4) A, beta = 106.410(1) degrees, V = 6935.6(2) A(3), and Z = 4. The structure of compound 1 features a novel 2D layer built from the 8e-reduced tetracapped Keggin [Zn(4)Mo(12)O(36)(PO(4))](3)(-) anions, which are further interconnected by bridging bipy ligands. The four zinc(II) ions are in tetrahedral, trigonal bipyramidal, and octahedral coordination geometries, respectively.     

Structural diversity of the oxovanadium organodiphosphonate system: a platform for the design of void channels

The hydrothermal reactions of a vanadium source, an appropriate diphosphonate ligand, and water in the presence of HF provide a series of compounds with neutral V-P-O networks as the recurring structural motif. When the {O3P(CH2)(n)PO3}4- diphosphonate tether length n is 2-5, metal-oxide hybrids of type 1, [V2O2(H2O){O3P(CH2)(n)PO3}] x xH2O, are isolated. The type 1 oxides exhibit the prototypical three-dimensional (3-D) "pillared" layer architecture. When n is increased to 6-8, the two-dimensional (2-D) "pillared" slab structure of the type 2 oxides [V2O2(H2O)4{O3P(CH2)6PO3}] is encountered. Further lengthening of the spacer to n = 9 provides another 3-D structure, type 3, constructed from the condensation of pillared slabs to give V-P-O double layers as the network substructure. When organic cations are introduced to provide charge balance for anionic V-P-O networks, oxides of types 4-7 are observed. For spacer length n = 3, a range of organodiammonium cations are accommodated by the same 3-D "pillared" layer oxovanadium diphosphonate framework in the type 4 materials [H3N(CH2)(n)NH3][V4O4(OH)2 {O3P(CH)3PO3}2] x xH2O [n = 2, x = 6 (4a); n = 3, x = 3 (4b); n = 4, x = 2 (4c); n = 5, x = 1 (4d); n = 6, x = 0.5 (4e); n = 7, x = 0 (4f)] and [H3NR]y[V4O4(OH)2 {O3P(CH)3PO3}2] x xH2O [R = -CH2(NH3)CH2CH3, y = 1, x = 0 (4g); R = -CH3, n = 2, x = 3 (4h); R = -CH2CH3, y = 2, x = 1 (4i); R = -CH2CH2CH3, y = 2, x = 0 (4j); cation = [H2N(CH2CH3)2], y = 2, x = 0 (4k)]. These oxides exhibit two distinct interlamellar domains, one occupied by the cations and the second by water of crystallization. Furthermore, as the length of the cation increases, the organodiammonium component spills over into the hydrophilic domain to displace the water of crystallization. When the diphosphonate tether length is increased to n = 5, structure type 5, [H3N(CH2)2NH3][V4O4(OH)2(H2O){O3P(CH2)5PO3}2] x H2O, is obtained. This oxide possesses a 2-D "pillared" network or slab structure, similar in gross profile to that of type 2 oxides and with the cations occupying the interlamellar domain. In contrast, shortening the diphosphonate tether length to n = 2 results in the 3-D oxovanadium organophosphonate structure of the type 7 oxide [H3N(CH2)5NH3][V3O3{O3P(CH2)2PO3}2]. The ethylenediphosphonate ligand does not pillar V-P-O networks in this instance but rather chelates to a vanadium center in the construction of complex polyhedral connectivity of 7. Substitution of piperazinium cations for the simple alkyl chains of types 4, 5, and 7 provides the 2-D pillared layer structure of the type 6 oxides, [H2N(CH2CH2)NH2][V2O2{O3P(CH)(n)PO3H}2] [n = 2 (6a); n = 4 (6b); n = 6 (6c)]. The structural diversity of the system is reflected in the magnetic properties and thermal behavior of the oxides, which are also discussed.     

Evolution of the structural chemistry of vanadium organodiphosphonate networks and frameworks: structural consequences of fluoride incorporation in the development of stable phases with void channels

Hydrothermal reactions of solutions containing a vanadate source, an organodiphosphonate, an organonitrogen component, and HF (V/P/O/F) yield a series of oxyfluorovanadium-diphosphonates with charge-compensation provided by organoammonium cations or hydronium cations. While V/P/O/F networks provide the recurrent structural motif, the linkage between the layers and the details of the polyhedral connectivities within the layers are quite distinct for the five structures of this study. [H2pip][V4F4O2(H2O)2{O3P(CH2)3PO3}2] (1) (pip = piperazine) is a conventional three-dimensional (3D) "pillared" layer structure, whose V/P/O/F networks are buttressed by the propylene chains of the diphosphonate ligands. In contrast, [H2en][V2O2F2(H2O)2{O3P(CH2)4PO3}] (2) and [H2en]2[V6F12(H2O)2{O3P(CH2)5PO3}2 {HO3P(CH2)5PO3H}] (3) are two-dimensional (2D) slablike structures constructed of pairs of V/P/O/F networks sandwiching the pillaring organic tethers of the diphosphonate ligands. Despite the common overall topology, the layer substructures are quite different: isolated {VO5F} octahedra in 2 and chains of corner-sharing {VO(3)F(3)} octahedra in 3. The 3D structure of [H2en]2[V7O6F4(H2O)2{O3P(CH2)2PO3}4].7H2O (4.7H2O) exhibits a layer substructure that contains the ethylene bridges of the diphosphonate ligands and are linked through corner-sharing octahedral {VO6} sites. The connectivity requirements provide large channels that enclose readily removed water of crystallization. The structure of [H3O][V3F2(H2O)2{O3P(CH2)2PO3}2].3.5H2O (5.3.5H2O) is also 3D. Because of the similiarity with 4.7H2O, it exhibits V/P/O/F layers that include the organic tethers of the diphosphonates and are linked through corner-sharing {VO6} octahedra. In contrast to the network substructure of 4.7H2O, which contains binuclear and trinuclear vanadium clusters, the layers of 5.3.5 H2O are constructed from chains of corner-sharing {VO4F2} octahedra. Thermal studies of the open framework materials 4 and 5 reveal that incorporation of fluoride into the inorganic substructures provides robust scaffoldings that retain their crystallinity to 450 degrees C and above. In the case of 4, dehydration does not change the powder X-ray diffraction pattern of the material, which remains substantially unchanged to 450 degrees C. In the case of 5, there are two dehydration steps, that is, the higher temperature process associated with loss of coordinated water. This second dehydration results in structural changes as monitored by powder X-ray diffraction, but this new phase is retained to ca. 450 degrees C. The materials of this study exhibit a range of reduced oxidation states: 1 is mixed valence V(IV)/V(III) while 2 and 4.7H(2)O are exclusively V(IV) and 3 and 5.3.5H2O are exclusively V(III). These oxidation states are reflected in the magnetic properties of the materials. The paramagnetism of 1 arises from the presence of V(III) and V(IV) sites and conforms to the Curie-Weiss law with C = 2.38 em K/(Oe mol) and = -66 K with mu(eff) (300 K) = 4.33 mu(B). Compounds 3-5 exhibit Curie-Weiss law dependence of magnetism on temperature with mu(eff) (300 K) = 5.45 mu(B) for 3 (six V(III) sites), mu(eff) = 4.60 mu(B) for 4 (seven V(IV) sites) and mu(eff) = 4.13 mu(B) for 5 (two V(III) sites). Compound 2 exhibits antiferromagnetic interactions, and the magnetism may be described in terms of the Heisenberg linear antiferromagnetic chain model for V(IV). The effective magnetic moment at 300 K is 2.77 mu(B) (two V(IV) sites).     

A new fluoroaluminophosphate chain with an Al/P ratio of unity

A new compound, Al2P2O8F2.[(CH3)2CHNH2CH2CH2NH2CH(CH3)2] (denoted AlPO-CJ8), with a 1-dimensional fluoroaluminophosphate chain and an Al/P ratio of unity has been synthesized solvothermally by using isopropylamine as an organic additive. It is characterized by X-ray powder diffraction (XRD), inductively coupled plasma (ICP), ion selective electrodes (ISE), and TGA-DTA analyses and structurally determined by single-crystal X-ray diffraction analysis. AlPO-CJ8 crystallizes in the triclinic space group P1 with a = 5.0306(8) A, b = 9.3626(15) A, c = 10.6131(17) A, alpha = 65.949(4) degrees, beta = 88.218(4) degrees, gamma = 77.19 degrees, and Z = 2. Its structure is built up by alternation of tetrahedral PO3(=O) and AlO3F units to form infinite 1-D Al2P2O8F2(2-) macroanionic chains. The inorganic chains are held together by diprotonated N,N'-diisopropylethylenediamine through H-bonds. The organic species N,N'-diisopropylethylenediamine is believed to be formed through solvothermal reaction of the organic additive isopropylamine and the solvent ethylene glycol. The existence of terminal P=O and Al-F bond groups in the 1-D chain indicates that it has potential to further set up higher dimensional networks through condensations.     

Hydrothermal Synthesis and Crystal Structure of a New Sandwich—type Molybdenum Phosphate

1 INTRODUCTION The synthesis of porous and open-framework transition metal phosphates has received great in- terest due to their various compositions and topolo- gyies, as well as their useful properties such as con- trollable size- and shape-selectivity, rigid frame- works and chemical/thermal stability[1]. Of these phosphates constructed from oxometal polyhedra and PO4 tetrahedron, the most interesting is the [MoV6P4X31]n－ (X=O, OH) family with the dimen- sionalities ranging from …     

Template- and pH-directed assembly of diruthenium diphosphonates with different topologies and oxidation states

In the presence of organic templates, six diruthenium diphosphonates, namely, [H3N(CH2)3NH3]2[Ru2(hedp)2] (1), [H3N(CH2)4NH3]2[Ru2(hedp)2].4H2O (2), [H3N(CH2)5NH3]2[Ru2(hedp)2].4H2O (3), [H3N(CH2)3NH3][Ru2(hedp)(hedpH)].H2O (4), [H3N(CH2)4NH3][Ru2(hedpH(0.5))2].2H2O (5), and [H3N(CH2)5NH3]2[Ru2(hedp)2][Ru2(hedpH)2]] (6) [hedp = 1-hydroxyethylidenediphosphonate, CH3C(OH)(PO3)2] have been synthesized under hydrothermal conditions. Compounds 1-3 contain homovalent paddlewheel cores of Ru2(II,II)(hedp)2(4-) that are connected through edge-sharing of the [RuO5Ru] octahedra, resulting in infinite linear chains. Compounds 4-6 contain mixed-valent diruthenium(II,III) phosphonate paddlewheel cores of Ru2(II,III)(hedpH(n))2(3-2n)- that are connected by phosphonate oxygen atoms, forming distorted square-grid layers in 4 and 6 or a kagomé lattice in 5. Both the templates and the pH values are found to play important roles in directing the final products with particular topologies and oxidation states of the diruthenium unit. The magnetic studies show that weak antiferromagentic interactions are propagated between the homovalent diruthenium units in compounds 1-3. For compounds 4-6, weak ferromagnetic interactions are observed.     

Solid state coordination chemistry of the copper(ii)-terpyridine/oxovanadium organophosphonate system: hydrothermal syntheses, structural characterization and magnetic properties

The hydrothermal reactions of CuSO4.5H2O, Na3VO4, 2,2':6':2'-terpyridine (terpy), and the appropriate organophosphonate ligand yield a series of materials of the Cu(ii)-terpy/oxovanadium organophosphonate family. The complexes exhibit distinct structures spanning one-, two- and three-dimensions and exhibiting diverse oxovanadium building blocks. Thus, [{Cu(terpy)}(V2O4)(O3PPh)(HO3PPh)2] (1) is one-dimensional and constructed from binuclear units of corner-sharing V(v) square pyramids. While [{Cu(terpy)}VO(O3PCH2PO3)] (2), [{Cu(terpy)}2(V4O10)(O3PCH2CH2PO3)] (3), and [{Cu(terpy)}(V2O4){O3P(CH2)3PO3}].2.5H(2)O (4.2.5H2O) are similarly one-dimensional, the V/O structural components consist of isolated V(iv) square pyramids, tetranuclear V(v) units of three tetrahedra and one square pyramid in a corner-sharing arrangement, and isolated V(v) tetrahedra and square pyramids, respectively. The second propylenediphosphonate derivative, [{Cu(terpy)}(V2O4){O3P(CH2)3PO3}] (5) is three-dimensional and exhibits isolated V(v) tetrahedra as the vanadate component. The two-dimensional structure of [{Cu(terpy)(H2O)}(V3O6){O3P(CH2)4PO3}] (6) is mixed valence with isolated V(iv) square pyramids and binuclear units of corner-sharing V(v) tetrahedra providing the V/O substructures.     

Concentrated Fluoride-medium Route to Synthesis of One-dimensional Fluoroaluminophosphate Chain (C4H15N3)[AlPO4F2]

A new one-dimensional(1D) fluoroaluminophosphate chain(C 4 H 15 N 3 )[AlPO 4 F 2 ](denoted AlPO-CJ28) was synthesized in the concentrated fluoride synthetic medium with a gel composition of 1.0Al(OPr i ) 3 :1.0H 3 PO 4 : 5.4DETA:1.3HF:2.0H 2 O(DETA=diethylenetriamine). The reagents were mixed directly without introducing addi- tional water solvent. The 1D chain is constructed by alternating AlO 2 F 2 and doubly bridging PO 4 tetrahedra to form the simplest serrate chain. AlPO-CJ28 can be transformed to another 1D aluminophosphate chain AlPO-CSC upon further crystallization at 230 °C.     

IR and raman spectra of two layered aluminium phosphates Co(en)3Al3P4O16.3H2O and

The FT IR and FT Raman spectra of Co(en)3Al3P4O16.3H2O (compound I) and [NH4]3[Co(NH3)6]3[Al2 (PO4)4]2.2H2O (compound II) are recorded and analysed based on the vibrations of Co(en)(3)3+, Co(NH3)(6)3+, NH4, Al-O-P, PO3, PO2 and H2O. The observed splitting of bands indicate that the site symmetry and correlation field effects are appreciable in both the compounds. In compound I, the overtone of CH2 deformation Fermi resonates with its symmetric stretching vibration. The NH4 ion in compound II is not free to rotate in the crystalline lattice. Hydrogen bonding of different groups is also discussed.     

New types of metal squarato-phosphonates: condensation of aminodiphosphonate with squaric acid under hydrothermal conditions

The syntheses and crystal structures of the first copper(I) phosphonate, Cu2(H3L)(bipy)(2).2H2O 1 (H5L = C4HO3N(CH2PO3H2)2), which is also the first example of metal phosphonates formed by a type of organic reaction, and a novel luminescent Mn(II) squarate diphosphonate, {Mn[NH(CH2PO3H)2](H2O)2}2{Mn(C4O4)(H2O)4}.(C4H2O4) 2, have been reported. The structure of 1 features a layer architecture in which the Cu(I) centers are three coordinated, and the newly formed ligand acts as a bidentate metal linker. Compound 2 is composed of 1D chains of Mn[NH(CH2PO3H)2](H2O)2, 1D chains of {Mn(C4O4)(H2O)4}, as well as the neutral squaric acid molecules. These three types of building units are interconnected via hydrogen bonding.     

Structural influences of organonitrogen ligands on vanadium oxide solids. Hydrothermal syntheses and structures of the terpyridine vanadates [V2O4(terpy)2]3[V10O28], [VO2(terpy)][V4O10], and [V9O22(terpy)3

Hydrothermal reactions of the V2O5/2,2':6':2"-terpyridine/ZnO/H2O system under a variety of conditions yielded the organic-inorganic hybrid materials [V2O4(terpy)2]3[V10O28].2H2O (VOXI-10), [VO2(terpy)][V4O10] (VOXI-11), and [V9O22(terpy)3] (VOXI-12). The structure of VOXI-10 consists of discrete binuclear cations [V2O4(terpy)2]2+ and one-dimensional chains [V10O28]6-, constructed of cyclic [V4O12]4- clusters linked through (VO4) tetrahedra. In contrast, the structure of VOXI-11 exhibits discrete mononuclear cations [VO2(terpy)]1+ and a two-dimensional vanadium oxide network, [V4O10]1-. The structure of the oxide layer is constructed from ribbons of edge-sharing square pyramids; adjacent ribbons are connected through corner-sharing interactions into the two-dimensional architecture. VOXI-12 is also a network structure; however, in this case the terpy ligand is incorporated into the two-dimensional oxide network whose unique structure is constructed from cyclic [V6O18]6- clusters and linear (V3O5(terpy)3) moieties of corner-sharing vanadium octahedra. The rings form chains through corner-sharing linkages; adjacent chains are connected through the trinuclear units. Crystal data: VOXI-10, C90H70N18O42V16, triclinic P1, a = 12.2071(7) A, b = 13.8855(8) A, 16.9832(10) A, alpha = 69.584(1) degrees, beta = 71.204(1) degrees, gamma = 84.640(1) degrees, Z = 1; VOXI-11, C15H11N3O12V5, monoclinic, P2(1)/n, a = 7.7771(1) A, b = 10.3595(2) A, c = 25.715(4) A, beta = 92.286(1) degrees, Z = 4; VOXI-12, C45H33N9O22V9, monoclinic C2/c, a = 23.774(2) A, b = 9.4309(6) A, c = 25.380(2) A, beta = 112.047(1) degrees, Z = 4.     

Synthesis of hybrid framework materials under "dry" hydrothermal conditions: crystal structure and magnetic properties of Mn(2)(H(2)PO(4))(2)(C(2)O(4))

An exploration of the manganese oxalate-phosphoric acid-water system under hydrothermal conditions, and using "reagent" quantities only of water, has led to the isolation of a new mixed anion framework material Mn(2)(H(2)PO(4))(2)(C(2)O(4)). This material features continuous chains of cis edge-sharing MnO(6) octahedra, a motif which is unique among mixed phosphate-oxalate materials identified so far. These octahedral chains are linked into a three-dimensional framework via corner-sharing with H(2)PO(4) tetrahedra, with oxalate ions acting as a bis-bidentate ligand in the third direction. Magnetic susceptibility studies show that this material may be modeled as an antiferromagnetic, S = (5)/(2) Heisenberg chain, with weaker coupling between the chains.     

Hydrothermal Synthesis and Structure Characterization of Open-framework Cobalt-tungsten Phosphate[H3NCH2CH2NH3]3[Co3W4P4O28]

A new three-dimensional open-framework cobalt(Ⅱ)-tungsten(Ⅵ) phosphate,[H3NCH2CH2NH3]3·[Co3W4P4O28](1) has been synthesized from the reaction of CoCl2·6H2O,WO3,H3PO4,ethylenediamine and H2O.The title compound was fully characterized by infrared spectroscopy,elemental analysis,magnetic properties,thermogravimetric analysis,XPS and single-crystal X-ray diffraction.The compound crystallized in a tetragonal space group I4(1)/a with a=1.7118(4) nm,c=1.0773(2) nm,V =3.1568(11) nm3,Z =4.     

Synthesis,crystal structure,and solid state NMR spectroscopy of NH(4)[(V(2)O(3))(2)(4,4'-bpy)(2)(H(2)PO(4))(PO(4))(2)].0.5H(2)O,a mixed-valence vanadium(IV,V) phosphate with a pillared layer structure

A mixed-valence vanadium phosphate, NH(4)[(V(2)O(3))(2)(4,4'-bpy)(2)(H(2)PO(4))(PO(4))(2)].0.5H(2)O, has been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group C2/c (No. 15) with a = 12.6354(8) A, b = 9.9786(6) A, c = 23.369(1) A, beta = 92.713(1) degrees, and Z = 4 with R(1) = 0.0389. The structure consists of dimers of edge-sharing vanadium(IV,V) octahedra that are connected by corner-sharing phosphate tetrahedra to form layers in the ab-plane, which are further linked through 4,4'-bipyridine pillars to generate a 3-D framework. Magnetic susceptibility confirms the valence of the vanadium atoms. The (31)P MAS NMR spectrum shows a resonance centered at 80 ppm with a shoulder at ca. 83 ppm in an intensity ratio close to 1:2, which correspond to two distinct P sites. The observed large downfield (31)P NMR shifts can be ascribed to magnetic exchange coupling involving phosphorus atoms. The unpaired electron spin density at the phosphorus nucleus was determined from variable-temperature (31)P NMR spectra. The (1)H MAS NMR spectrum was fitted to six components in accordance with the structure as determined from X-ray diffraction.