(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
- Syracuse Univ., NY (United States)
- 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), Journal Name: Inorganic Chemistry; (United States) Journal Issue: 8 Vol. 33:8; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
360602* -- Other Materials-- Structure & Phase Studies
CHEMICAL REACTION YIELD
CRYSTAL DEFECTS
CRYSTAL LATTICES
CRYSTAL STRUCTURE
LAYERS
MONOCLINIC LATTICES
OXYGEN COMPOUNDS
PHOSPHATES
PHOSPHORUS COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
VANADIUM COMPOUNDS
VANADIUM PHOSPHATES
YIELDS