Single-crystal X-ray study of Ba2Cu2Te4O11Br2 and its incommensurately modulated superstructure companion

Compounds containing lone-pair elements such as Te(IV) are very interesting from the structural point of view, as the lone-pair nonbonding regions create low-dimensional geometrical arrangements. We have synthesized two new compounds with these features-Ba(2)Cu(2)Te(4)O(11)Br(2) (I) and Ba(2)Cu(2)Te(4)O(11-delta)(OH)(2delta)Br(2) (II, delta approximately equal to 0.57)-as members of the AE-M-Te-O-X (AE=alkaline-earth metal, M=transition metal, X=halide) family of compounds by solid-state reactions. Preliminary single-crystal X-ray analysis indicated that compound I crystallizes in the orthorhombic system, but attempts at refinement proved unsatisfactory. Closer inspection of the reciprocal lattice revealed systematic, non-crystallographic absences that indicate twinning. The structure is in fact triclinic, space group C_1 (equivalent to P_1), with unit cell parameters (at 120 K) of a=10.9027(9), b=15.0864(7), c=9.379(2) A, beta=106.8947 degrees . It is layered and built from [TeO(3)E] tetrahedra, [TeO(3+1)E] trigonal bipyramids (where E is the lone pair of Te(IV)), [CuO(4)] squares and irregular [BaO(10)Br] polyhedra. The crystal structure of II shows the same basic structure as I but contains additional oxygen, probably in the form of OH groups. The presence of satellites reveals that ordering on this O site creates an incommensurate modulation, primarily affecting Br and Te. The modulated structure of II was solved in the triclinic superspace group X$\bar 1$(alphabetagamma)0 with the vector q approximately equal to1/16 c*.