Synthesis and Structure of a New Quinary Sulfide Halide: LaCa(2)GeS(4)Cl(3).

A new quinary rare earth sulfide-halide compound has been synthesized and its structure determined by single-crystal X-ray diffraction. LaCa(2)GeS(4)Cl(3) crystallizes in the noncentrosymmetric hexagonal space group -P6(3)mc (No. 186) with Z = 2, a = 9.731(1) Å, and c = 6.337(1) Å. Lanthanum and calcium are mixed on a pseudo-trigonal prismatic site, coordinated to three sulfur atoms on one triangular face and three chlorine atoms on the other. Isolated, slightly distorted tetrahedra of GeS(4) are oriented with a tetrahedral 3-fold axis aligned along the crystallographic 3-fold rotation axis. Preliminary optical studies indicate that this material has a useful optical window extending approximately from 0.5 to 10 &mgr;m. Nonlinear optical activity of LaCa(2)GeS(4)Cl(3) is demonstrated by the generation of green light when pumped with a 1.064 &mgr;m Nd:YAG laser.