Structure of a new high-pressure-high-temperature modification of antimony(III) oxide, γ-Sb2O3, from high-resolution synchrotron powder diffraction data.

A quenchable new high-pressure-high-temperature modification of antimony(III) oxide, γ-Sb(2)O(3), has been obtained at hydrostatic pressures of 9-11 GPa and temperatures of 573-773 K. Its crystal structure has been determined from high-resolution synchrotron powder diffraction data. γ-Sb(2)O(3) consists of three-dimensionally cross-linked infinite chains of SbO(3)E units (E = lone pair) with the chains forming tetragonal rod-packing. The underlying topology of γ-Sb(2)O(3) (3,3T8) is found very rarely in inorganic structures; it is realised only for the polyanion [Si(4)O(4)N(6)](10-) that occurs in the Ce(4)(Si(4)O(4)N(6))O structure type. The structural relation to the two previously known polymorphs of Sb(2)O(3) at ambient pressure, valentinite and senarmontite is discussed.