Hydrothermal Syntheses and Structural Characterization of Layered Oxovanadium Phosphate Solids Incorporating Organic Cations: [H2N(C4H8)NH2][(VO)4(OH)4(PO4)2] [(NH3C3H6)NH(C2H4)2NH(C3H6NH3)][(VO)5(OH)2(P04)4]·2H2O, [HN(C2H4)3NH]2[(VO)8(HPO4)3(PO4)4(OH)2]·2H2O, and [HN(C2H4)3NH][(VO)3(OH)2(P04)2]

Victoria Soghomonian, Qin Chen, Yiping Zhang, Robert C. Haushalter, J. O’Connor Charles, Cuihong Tao, Jon Zubieta

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Four new two-dimensional vanadium phosphates, [H2N(C4H8)NH2][(VO)4(OH)4(PO4)2] (1), [(NH3C3H6)NH(C2H4)2-NH(C3H6NH3)][(VO)5(OH)2(PO4)4]·2H2O (2), [HN(C2H4)3NH]2[(VO)8(HPO4)3(PO4)4(OH)2]·2H2O (3), and [HN(C2H4)3-NH][(VO)3(OH)2(PO4)2] (4), have been synthesized by exploiting the hydrothermal technique. Compound 1 was synthesized from the reaction of a mixture VCl4, H3PO4, piperazine, tetrabutylammonium hydroxide, and H2O in the mole ratio 1:2.2:1.7:1.2:2830 heated at 200 ·C for 48 h. Phosphate 2 was obtained from the reaction of VCl4, H3PO4, l,4-bis(aminopropyl)piperazine, and water in the mole ratio 1:2.4:6.3:1207 heated for 114 h at 150 ·C. Compounds 3 and 4 were synthesized from the same reactants, VCl4, H3PO4, l,4-diazabicyclo[2.2.2]octane (DABCO), and H2O under different reaction conditions. While the preparation of 3 employed the mole ratio 1:8.0:4.0:1375 and a heating time of 72 h at 200 ·C, the synthesis of 4 required a ratio of 1:6.0:4.0:2268 at 200 ·C for 48 h. While these four materials share a common motif of inorganic V/P/O layers separated by organic cations, each exhibits highly distinctive structural features. Phosphate 1 has discrete binuclear {V2O8} edge-sharing units, which give rise to undulations in the inorganic V/P/O layer; while compound 2 possesses similar {V2O8} units, the distinctive features of isolated VO5 square pyramids and {V2O4P2} intersecting rings are also present. While compounds 3 and 4 have the same template, l,4-diazabicyclo[2.2.2]octane, examination of the inorganic layers reveals different structural motifs. Compound 3 possesses two isolated tetrameric units: one composed of two face-sharing VO6 octahedra, each sharing a corner with a {VO5} square pyramid, while the second consists of two pairs of corner-sharing {VO5} square pyramids, linked by μ4-phosphate groups. In contrast, compound 4 contains binuclear units constructed from face-sharing {VO6} dimers linked by corner-sharing interactions into infinite chains. In addition each binuclear unit of 4 exhibits a corner-sharing interaction with a {VO5} square pyramidal site to produce a ribbon of octahedral-square pyramidal vanadium polyhedra; adjacent ribbons are linked through μ4-phosphate groups. Crystal data are as follows. C4H16N2O16P4V4 (1): blue plates, monoclinic space group P2,1/c (No. 14) with a = 10.682(2) Å, b = 8.991(2) Å, c = 8.951(2) Å, β = 110.41(3)·, V = 805.7(4) Å3, Z = 1; refinement based on 1493 reflections gave a final residual of R = 0.0569. C10H34N4O25P4V5 (2): blue plates, triclinic space group Pi (No. 2) with a = 9.433(3) Å, b = 17.799(3) Å, c = 9.356(1) Å, a = 103.83(1)·, β = 91.80(2)·, γ = 95.90(2)·, V = 1514.7(6) Å3, Z = 2; 3935 reflections, R = 0.052. C12H37N2O40P7V8 (3): blue plates, monoclinic space group P2/n (No. 13) with a = 9.559(2) Å, b = 8.840(2) Å, c = 24.309(5) Å, β = 100.07(2)·, V = 2022.5(7) Å3, Z = 2; 3181 reflections, R = 0.0561. C6H16N2O13P2V3 (4): ink-blue square plates, monoclinic space group P21/n (No. 14) with a = 12.048(2) Å, b = 6.3470(10) Å, c = 20249(4) Å, V = 1493.5(8) Å3, Z = 4; 1846 reflections, R = 0.0567.

Original languageEnglish (US)
Pages (from-to)3509-3519
Number of pages11
JournalInorganic Chemistry
Issue number13
StatePublished - Jun 1 1995

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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