H2N(CH2CH2)2NH 2[(VO)4(H2O)4(HPO4) 2(PO4)2]: An Organically Templated Vanadium Phosphate with One Dimensional {-V-O=V-O-} Chains

Victoria Soghomonian, Robert C. Haushalter, Jon Zubieta, Charles J. O'Connor

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

The new vanadium phosphate H2N(CH2CH2)2NH2[(VO) 4(H2O)4(HPO4)2(PO 4)2], (1) was prepared from the reaction of VCl4:H3PO4:1,4-diaminopiperazine hydrochloride:tetra-n-buytlammonium hydroxide:H2O in a mole ratio of 1:8.9:4.4:5.2:2268 in a sealed glass tube for 3 h at 200 °C. Phosphate 1 crystallizes in the acentric monoclinic space group Im with a = 7.025(1), b = 9.470(2), and c = 16.570(3)Å, β= 96.03(3)°, V = 1096.3 (6) Å3, Z = 2, and R (Rw) = 0.0517 (0.0595) and possesses a three dimensional (3-D) covalently bonded structure comprised of a vanadium phosphate net with occluded organic cations occupying tunnels within the oxide framework. The structure can be qualitatively described as a severely defected VOPO4 structure type, with phosphate 1 displaying several different VO6 environments that can be envisioned as related to the infinite {O=V⋯O}n strings present in VOPO4: (a) infinite 1-D chains of VO6 octahedra sharing opposite vertices with the remaining four vertices connected to {PO4} tetrahedra just as in VOPO4; (b) 1-D chains as in point a but with every other octahedron missing with the distorted octahedral coordination requirements satisfied by the addition of an aquo ligand trans to the V=O group; (c) 1-D chains as in point a but with every other one missing and each V atom coordinated to three aquo ligands; (d) a region that would be occupied by a 1-D chain in VOPO4 but is totally missing and is occupied by the organic dication. As a result, some of the {PO4} tetrahedra are either absent or possess P-OH groups to compensate for the missing V atoms.

Original languageEnglish (US)
Pages (from-to)2826-2830
Number of pages5
JournalInorganic Chemistry
Volume35
Issue number10
StatePublished - Dec 1 1996

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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