Zn3(GaS3)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(3) and three equivalent S(2) atoms to form ZnS4 tetrahedra that share corners with two equivalent Zn(1)S4 tetrahedra, corners with five equivalent Ga(1)S5 trigonal bipyramids, and edges with two equivalent Zn(1)S4 tetrahedra. In the second Zn site, Zn(2) is bonded in a see-saw-like geometry to two equivalent S(1) and two equivalent S(3) atoms. Ga(1) is bonded to one S(2), two equivalent S(1), and two equivalent S(3) atoms to form GaS5 trigonal bipyramids that share corners with five equivalent Zn(1)S4 tetrahedra and edges with two equivalent Ga(1)S5 trigonal bipyramids. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Zn(2) and two equivalent Ga(1) atoms. In the second S site, S(2) is bonded to three equivalent Zn(1) and one Ga(1) atom to form a mixture of edge and corner-sharing SZn3Ga tetrahedra. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one Zn(1), one Zn(2), and two equivalent Ga(1) atoms.
Zn3(GaS3)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(3) and three equivalent S(2) atoms to form ZnS4 tetrahedra that share corners with two equivalent Zn(1)S4 tetrahedra, corners with five equivalent Ga(1)S5 trigonal bipyramids, and edges with two equivalent Zn(1)S4 tetrahedra. The Zn(1)-S(3) bond length is 2.40 Å. There are two shorter (2.45 Å) and one longer (2.50 Å) Zn(1)-S(2) bond length. In the second Zn site, Zn(2) is bonded in a see-saw-like geometry to two equivalent S(1) and two equivalent S(3) atoms. Both Zn(2)-S(1) bond lengths are 2.20 Å. Both Zn(2)-S(3) bond lengths are 2.72 Å. Ga(1) is bonded to one S(2), two equivalent S(1), and two equivalent S(3) atoms to form GaS5 trigonal bipyramids that share corners with five equivalent Zn(1)S4 tetrahedra and edges with two equivalent Ga(1)S5 trigonal bipyramids. The Ga(1)-S(2) bond length is 2.36 Å. There is one shorter (2.32 Å) and one longer (2.38 Å) Ga(1)-S(1) bond length. There is one shorter (2.38 Å) and one longer (2.56 Å) Ga(1)-S(3) bond length. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Zn(2) and two equivalent Ga(1) atoms. In the second S site, S(2) is bonded to three equivalent Zn(1) and one Ga(1) atom to form a mixture of edge and corner-sharing SZn3Ga tetrahedra. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one Zn(1), one Zn(2), and two equivalent Ga(1) atoms.