Mm. Borel et al., Complex distribution of diphosphate groups in the structure of V(IV) phosphates A(VO)(3)(P2O7)(2) (A = Sr, Pb, and Ba), CHEM MATER, 11(12), 1999, pp. 3655-3665
New V(IV) diphosphates A(VO)(3)(P2O7)(2) have been synthesized for A = Ba,
Sr, and Pb. Their X-ray diffraction and electron microscopy studies show th
eir complex crystal chemistry. The polycrystalline samples of the Ba, Sr, a
nd Pb phases and the single crystals of Sr and Pb phases exhibit a P2(1)2(1
)2(1)-type structure (called alpha form) similar to that observed for K(VO)
(3)(P2O5)(2). For a single crystal of Ba(VO)(3)(P2O7)(2), a new structural
form, called beta, has been stabilized. It crystallizes in the P11b space g
roup, with cell parameters similar to those of the alpha form. This structu
re, closely related to that of the alpha form, differs from the latter by t
he distribution of the barium cations and the surrounding P2O7 groups. The
HREM study of polycrystalline beta-Ba(VO)(3)(P2O7)(2) shows the great flexi
bility of this structure. It demonstrates the coexistence of the two struct
ures, P2(1)2(1)2(1) and P11b, in many crystallites, in the form of P11b int
ergrowth defects in the P2(1)2(1)2(1) matrix.