K2Ge2S5 crystallizes in the monoclinic C2/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one S(1), one S(4), one S(6), two equivalent S(2), and two equivalent S(3) atoms. In the second K site, K(2) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), one S(5), and two equivalent S(4) atoms. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one S(1), one S(2), one S(3), and one S(6) atom to form corner-sharing GeS4 tetrahedra. In the second Ge site, Ge(2) is bonded to one S(1), one S(2), one S(4), and one S(5) atom to form corner-sharing GeS4 tetrahedra. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted water-like geometry to one K(1), one K(2), one Ge(1), and one Ge(2) atom. In the second S site, S(2) is bonded to one K(2), two equivalent K(1), one Ge(1), and one Ge(2) atom to form distorted SK3Ge2 trigonal bipyramids that share corners with five equivalent S(4)K3Ge trigonal pyramids and  an edgeedge with one S(2)K3Ge2 trigonal bipyramid. In the third S site, S(3) is bonded in a 4-coordinate geometry to one K(2), two equivalent K(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded to one K(1), two equivalent K(2), and one Ge(2) atom to form distorted SK3Ge trigonal pyramids that share corners with five equivalent S(2)K3Ge2 trigonal bipyramids and corners with two equivalent S(4)K3Ge trigonal pyramids. In the fifth S site, S(5) is bonded in a 4-coordinate geometry to two equivalent K(2) and two equivalent Ge(2) atoms. In the sixth S site, S(6) is bonded in a distorted water-like geometry to two equivalent K(1) and two equivalent Ge(1) atoms.
K2Ge2S5 crystallizes in the monoclinic C2/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one S(1), one S(4), one S(6), two equivalent S(2), and two equivalent S(3) atoms. The K(1)-S(1) bond length is 3.55 Å. The K(1)-S(4) bond length is 3.23 Å. The K(1)-S(6) bond length is 3.58 Å. There is one shorter (3.32 Å) and one longer (3.49 Å) K(1)-S(2) bond length. There is one shorter (3.19 Å) and one longer (3.29 Å) K(1)-S(3) bond length. In the second K site, K(2) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), one S(5), and two equivalent S(4) atoms. The K(2)-S(1) bond length is 3.55 Å. The K(2)-S(2) bond length is 3.48 Å. The K(2)-S(3) bond length is 3.23 Å. The K(2)-S(5) bond length is 3.43 Å. There is one shorter (3.19 Å) and one longer (3.27 Å) K(2)-S(4) bond length. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one S(1), one S(2), one S(3), and one S(6) atom to form corner-sharing GeS4 tetrahedra. The Ge(1)-S(1) bond length is 2.26 Å. The Ge(1)-S(2) bond length is 2.26 Å. The Ge(1)-S(3) bond length is 2.12 Å. The Ge(1)-S(6) bond length is 2.24 Å. In the second Ge site, Ge(2) is bonded to one S(1), one S(2), one S(4), and one S(5) atom to form corner-sharing GeS4 tetrahedra. The Ge(2)-S(1) bond length is 2.23 Å. The Ge(2)-S(2) bond length is 2.26 Å. The Ge(2)-S(4) bond length is 2.12 Å. The Ge(2)-S(5) bond length is 2.25 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted water-like geometry to one K(1), one K(2), one Ge(1), and one Ge(2) atom. In the second S site, S(2) is bonded to one K(2), two equivalent K(1), one Ge(1), and one Ge(2) atom to form distorted SK3Ge2 trigonal bipyramids that share corners with five equivalent S(4)K3Ge trigonal pyramids and  an edgeedge with one S(2)K3Ge2 trigonal bipyramid. In the third S site, S(3) is bonded in a 4-coordinate geometry to one K(2), two equivalent K(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded to one K(1), two equivalent K(2), and one Ge(2) atom to form distorted SK3Ge trigonal pyramids that share corners with five equivalent S(2)K3Ge2 trigonal bipyramids and corners with two equivalent S(4)K3Ge trigonal pyramids. In the fifth S site, S(5) is bonded in a 4-coordinate geometry to two equivalent K(2) and two equivalent Ge(2) atoms. In the sixth S site, S(6) is bonded in a distorted water-like geometry to two equivalent K(1) and two equivalent Ge(1) atoms.