Crystal chemistry of inorganic compounds based on chains of oxocentered tetrahedra - II. Crystal structure of Cu4O2[(As,V)O-4]Cl

The orthorhombic crystal structure of Cu4O2[(As,V)O-4]Cl, a = 5.440(1) Angs trom, b = 11.154(2) Angstrom, c = 10.333(2) Angstrom, V = 627.0(3) Angstrom (3), Z = 4, Pbcm, has been solved by direct methods and refined to an R(F) index of 0.049 (wR(F-2) = 0.048). The structure is based on unbranched vier er chains (uB, 1(infinity)(1)) [O4Cu8] running parallel to the c axis, whic h are composed of oxocentered tetrahedra [OCu4] Linked via opposite edges. The chains are bent by the large chloride ions in zigzag fashion so that th e periodicity of the chains is equal to four. [(As,V)O-4] groups are locate d between the puckered chains of oxocentered tetrahedra and crosslink them into layers parallel to the (100) plane, which are held together by the CU- O-As/V bonds.