(H[sub 2]NC[sub 4]H[sub 8]NH[sub 2])[(VO)[sub 2](PO[sub 4])[sub 2]] and (H[sub 2]NC[sub 4]H[sub 8]NH[sub 2])[sub 2][(VO)[sub 3](HPO[sub 4])[sub 2](PO[sub 4])[sub 2]][center dot]H[sub 2]O: Novel layered vanadium phosphates with distorted and defected VOPO[sub 4] layers

Journal Article · Wed Apr 13 00:00:00 EDT 1994 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00086a021· OSTI ID:7103244

Soghomonian, V; Chen, Qin ^[1]; Haushalter, R C; Zubieta, J ^[2]

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1. Syracuse Univ., NY (United States)
2. NEC Research Institute, Princeton, NJ (United States)

Two new layered vanadium phosphates, (H[sub 2]NC[sub 4]H[sub 8]NH[sub 2])[(VO)[sub 2](PO[sub 4])[sub 2]] (1) and (H[sub 2]NC[sub 4]H[sub 8]NH[sub 2])[sub 2][(VO)[sub 3](HPO[sub 4])[sub 2](PO[sub 4])[sub 2]][center dot]H[sub 2]O (2), have been hydrothermally synthesized under similiar conditions. Compound 1 is synthesized from VCl[sub 4], H[sub 3]PO[sub 4], piperazine, (n-C[sub 4]H[sub 9])[sub 4]NOH, and H[sub 2]O in the mole ratio 1:2.7:2.1:1.2:350 at 200 [degrees]C for 70 h and autogeneous pressure. In contrast, the preparation of 2 required the presence of (CH[sub 3])PO[sub 3]H[sub 2], such that reaction of VCl[sub 4], H[sub 3]PO[sub 4], (CH[sub 3])PO[sub 3]H[sub 2], piperazine (n-C[sub 4]H[sub 9])[sub 4]NOH, and H[sub 2]O in the mole ratio 1:3.5:1.2:3.3:1.2:390 at 200 [degrees]C for 70 h yields 2 in 50% yield, with 1 as the other component. Green plates of compound 1 crystallize in the monoclinic space group P2[sub 1]/c with a = 8.786(2) [angstrom], b = 8.257(2) [angstrom], c = 8.566(2) [angstrom], [beta] = 111.07(3)[degrees], V = 579.9(3) [angstrom][sup [minus]3], Z = 2, and R = 0.0298 whereas blue plates of 2 crystallize in the noncentrosymmetric orthorhombic space group Pna2[sub 1] with a = 14.631(3) [angstrom], b = 8.706(2) [angstrom], c = 17.635(4) [angstrom], V = 2246.3(11) [angstrom][sup [minus]3], Z = 4, and R = 0.0363. Compound 1 has puckered layers containing triangular bipyramidal vanadium(IV) centers. Phosphate 2 has VOPO[sub 4[minus]] like layers with 1/4 of the V(IV) octahedral sites missing which results in unusual edge-sharing involving half the phosphate tetrahedral with the vanadium octahedra and protonation of the remaining phosphate groups to give HPO[sub 4[sup 2[minus]]] residues.

• OSTI ID: 7103244
• Journal Information: Inorganic Chemistry; (United States), Vol. 33:8, Issue 8; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
VANADIUM PHOSPHATES
CRYSTAL STRUCTURE
CHEMICAL REACTION YIELD
CRYSTAL DEFECTS
LAYERS
MONOCLINIC LATTICES
CRYSTAL LATTICES
OXYGEN COMPOUNDS
PHOSPHATES
PHOSPHORUS COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
VANADIUM COMPOUNDS
YIELDS
360602* - Other Materials- Structure & Phase Studies