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The crystal structures of yellow Cu 3 PS 4  and of black Cu 3 SbS 4  were refined from single crystal X-ray diffraction data. Cu 3 PS 4  crystallizes orthorhombic in an ordered wurtzite superstructure type with the space group  Pmn 2 1  (no. 31),  a  = 7.282(1) Å,  b  = 6.339(1) Å,  c  = 6.075(1) Å,  V  = 280.38(8) Å 3 , and  Z  = 2. The refinement converged to  R  = 0.0276, and  wR 2 = 0.0710 for 737 unique reflections and 44 parameters. Cu 3 SbS 4  crystallizes tetragonal in an ordered sphalerite superstructure type with the space group  I 4̅2 m  (no. 121),  a  = 5.391(1) Å,  c  = 10.764(1) Å,  V  = 312.83(9) Å 3 , and  Z  = 2. The refinement converged to  R  = 0.0213, and  wR 2 = 0.0532 for 492 unique reflections and 14 parameters. The crystal structures of the title compounds and related normal tetrahedral structures are discussed with respect to the preference of either hexagonal or cubic packing of the anions.

Refinement of the crystal structures of Cu 3 PS 4 and Cu 3 SbS 4 and a comment on normal tetrahedral structures