Ag6Ge(S2Cl)2 is Chalcostibite-derived structured and crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent S(1), one Cl(1), and one Cl(2) atom to form distorted AgS2Cl2 trigonal pyramids that share corners with two equivalent Ge(1)S4 tetrahedra. In the second Ag site, Ag(2) is bonded in a 4-coordinate geometry to one S(1), two equivalent S(2), and one Cl(2) atom. In the third Ag site, Ag(3) is bonded in a 6-coordinate geometry to two equivalent S(1), two equivalent S(3), and two equivalent Cl(1) atoms. In the fourth Ag site, Ag(4) is bonded in a 3-coordinate geometry to one S(1), one S(3), and one Cl(1) atom. Ge(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form GeS4 tetrahedra that share corners with two equivalent Ag(1)S2Cl2 trigonal pyramids. There are three inequivalent S sites. In the first S site, S(2) is bonded in a 5-coordinate geometry to four equivalent Ag(2) and one Ge(1) atom. In the second S site, S(3) is bonded to two equivalent Ag(3), two equivalent Ag(4), and one Ge(1) atom to form distorted corner-sharing SAg4Ge square pyramids. In the third S site, S(1) is bonded in a 4-coordinate geometry to one Ag(1), one Ag(2), one Ag(3), one Ag(4), and one Ge(1) atom. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to one Ag(1), two equivalent Ag(3), and two equivalent Ag(4) atoms. In the second Cl site, Cl(2) is bonded in a trigonal planar geometry to one Ag(1) and two equivalent Ag(2) atoms.
Ag6Ge(S2Cl)2 is Chalcostibite-derived structured and crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent S(1), one Cl(1), and one Cl(2) atom to form distorted AgS2Cl2 trigonal pyramids that share corners with two equivalent Ge(1)S4 tetrahedra. Both Ag(1)-S(1) bond lengths are 2.54 Å. The Ag(1)-Cl(1) bond length is 2.95 Å. The Ag(1)-Cl(2) bond length is 2.56 Å. In the second Ag site, Ag(2) is bonded in a 4-coordinate geometry to one S(1), two equivalent S(2), and one Cl(2) atom. The Ag(2)-S(1) bond length is 2.59 Å. There is one shorter (2.54 Å) and one longer (2.92 Å) Ag(2)-S(2) bond length. The Ag(2)-Cl(2) bond length is 2.66 Å. In the third Ag site, Ag(3) is bonded in a 6-coordinate geometry to two equivalent S(1), two equivalent S(3), and two equivalent Cl(1) atoms. Both Ag(3)-S(1) bond lengths are 3.18 Å. Both Ag(3)-S(3) bond lengths are 2.55 Å. Both Ag(3)-Cl(1) bond lengths are 3.06 Å. In the fourth Ag site, Ag(4) is bonded in a 3-coordinate geometry to one S(1), one S(3), and one Cl(1) atom. The Ag(4)-S(1) bond length is 2.46 Å. The Ag(4)-S(3) bond length is 2.57 Å. The Ag(4)-Cl(1) bond length is 2.72 Å. Ge(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form GeS4 tetrahedra that share corners with two equivalent Ag(1)S2Cl2 trigonal pyramids. The Ge(1)-S(2) bond length is 2.23 Å. The Ge(1)-S(3) bond length is 2.30 Å. Both Ge(1)-S(1) bond lengths are 2.25 Å. There are three inequivalent S sites. In the first S site, S(2) is bonded in a 5-coordinate geometry to four equivalent Ag(2) and one Ge(1) atom. In the second S site, S(3) is bonded to two equivalent Ag(3), two equivalent Ag(4), and one Ge(1) atom to form distorted corner-sharing SAg4Ge square pyramids. In the third S site, S(1) is bonded in a 4-coordinate geometry to one Ag(1), one Ag(2), one Ag(3), one Ag(4), and one Ge(1) atom. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to one Ag(1), two equivalent Ag(3), and two equivalent Ag(4) atoms. In the second Cl site, Cl(2) is bonded in a trigonal planar geometry to one Ag(1) and two equivalent Ag(2) atoms.