K5In4(Ge3As7)2 crystallizes in the monoclinic C2/m space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one As(1), two equivalent As(3), two equivalent As(4), and two equivalent As(6) atoms. In the second K site, K(2) is bonded to two equivalent As(7) and four equivalent As(2) atoms to form distorted KAs6 octahedra that share corners with two equivalent In(2)As4 tetrahedra, corners with four equivalent Ge(2)GeAs3 tetrahedra, edges with two equivalent K(2)As6 octahedra, edges with two equivalent Ge(2)GeAs3 tetrahedra, and edges with four equivalent In(1)As4 tetrahedra. In the third K site, K(3) is bonded in a 7-coordinate geometry to one As(2), two equivalent As(1), two equivalent As(5), and two equivalent As(7) atoms. There are two inequivalent In sites. In the first In site, In(1) is bonded to one As(2), one As(6), and two equivalent As(7) atoms to form InAs4 tetrahedra that share corners with two equivalent In(1)As4 tetrahedra, corners with two equivalent In(2)As4 tetrahedra, corners with two equivalent Ge(2)GeAs3 tetrahedra, and edges with two equivalent K(2)As6 octahedra. In the second In site, In(2) is bonded to one As(1), one As(7), and two equivalent As(3) atoms to form InAs4 tetrahedra that share  a cornercorner with one K(2)As6 octahedra, corners with two equivalent In(1)As4 tetrahedra, corners with two equivalent In(2)As4 tetrahedra, corners with two equivalent Ge(1)GeAs3 tetrahedra, and corners with two equivalent Ge(3)GeAs3 tetrahedra. The corner-sharing octahedral tilt angles are 3°. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one Ge(3), one As(3), and two equivalent As(4) atoms to form GeGeAs3 tetrahedra that share corners with two equivalent As(1)K3InGe2 octahedra,  a cornercorner with one As(4)K2Ge3 square pyramid, corners with two equivalent In(2)As4 tetrahedra, corners with two equivalent Ge(1)GeAs3 tetrahedra, and corners with two equivalent Ge(3)GeAs3 tetrahedra. The corner-sharing octahedral tilt angles are 74°. In the second Ge site, Ge(2) is bonded to one Ge(2), one As(5), and two equivalent As(2) atoms to form GeGeAs3 tetrahedra that share corners with two equivalent K(2)As6 octahedra, corners with two equivalent In(1)As4 tetrahedra, corners with two equivalent Ge(2)GeAs3 tetrahedra, and  an edgeedge with one K(2)As6 octahedra. The corner-sharing octahedral tilt angles are 20°. In the third Ge site, Ge(3) is bonded to one Ge(1), one As(4), and two equivalent As(1) atoms to form GeGeAs3 tetrahedra that share corners with two equivalent As(4)K2Ge3 square pyramids, corners with two equivalent In(2)As4 tetrahedra, corners with two equivalent Ge(1)GeAs3 tetrahedra, corners with two equivalent Ge(3)GeAs3 tetrahedra, and  a cornercorner with one As(3)K2In2Ge trigonal bipyramid. There are seven inequivalent As sites. In the first As site, As(2) is bonded in a 6-coordinate geometry to one K(3), two equivalent K(2), one In(1), and two equivalent Ge(2) atoms. In the second As site, As(3) is bonded to two equivalent K(1), two equivalent In(2), and one Ge(1) atom to form distorted AsK2In2Ge trigonal bipyramids that share corners with two equivalent As(7)K3In3 octahedra, corners with four equivalent As(1)K3InGe2 octahedra, corners with four equivalent As(4)K2Ge3 square pyramids,  a cornercorner with one Ge(3)GeAs3 tetrahedra,  an edgeedge with one As(4)K2Ge3 square pyramid, and edges with two equivalent As(3)K2In2Ge trigonal bipyramids. The corner-sharing octahedral tilt angles range from 37-68°. In the third As site, As(4) is bonded to two equivalent K(1), one Ge(3), and two equivalent Ge(1) atoms to form distorted AsK2Ge3 square pyramids that share  a cornercorner with one Ge(1)GeAs3 tetrahedra, corners with two equivalent Ge(3)GeAs3 tetrahedra, corners with four equivalent As(3)K2In2Ge trigonal bipyramids, edges with two equivalent As(1)K3InGe2 octahedra, edges with two equivalent As(4)K2Ge3 square pyramids, and  an edgeedge with one As(3)K2In2Ge trigonal bipyramid. In the fourth As site, As(5) is bonded in a 5-coordinate geometry to two equivalent K(3), one Ge(2), and two equivalent As(6) atoms. In the fifth As site, As(6) is bonded in a 5-coordinate geometry to two equivalent K(1), one In(1), and two equivalent As(5) atoms. In the sixth As site, As(7) is bonded to one K(2), two equivalent K(3), one In(2), and two equivalent In(1) atoms to form AsK3In3 octahedra that share  a cornercorner with one As(7)K3In3 octahedra, corners with two equivalent As(1)K3InGe2 octahedra, corners with two equivalent As(3)K2In2Ge trigonal bipyramids, edges with two equivalent As(7)K3In3 octahedra, and  a faceface with one As(1)K3InGe2 octahedra. The corner-sharing octahedral tilt angles range from 0-69°. In the seventh As site, As(1) is bonded to one K(1), two equivalent K(3), one In(2), and two equivalent Ge(3) atoms to form distorted AsK3InGe2 octahedra that share corners with two equivalent As(7)K3In3 octahedra, corners with two equivalent Ge(1)GeAs3 tetrahedra, corners with four equivalent As(3)K2In2Ge trigonal bipyramids, edges with two equivalent As(1)K3InGe2 octahedra, edges with two equivalent As(4)K2Ge3 square pyramids, and  a faceface with one As(7)K3In3 octahedra. The corner-sharing octahedral tilt angles are 69°.
K5In4(Ge3As7)2 crystallizes in the monoclinic C2/m space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one As(1), two equivalent As(3), two equivalent As(4), and two equivalent As(6) atoms. The K(1)-As(1) bond length is 3.76 Å. Both K(1)-As(3) bond lengths are 3.49 Å. Both K(1)-As(4) bond lengths are 3.59 Å. Both K(1)-As(6) bond lengths are 3.59 Å. In the second K site, K(2) is bonded to two equivalent As(7) and four equivalent As(2) atoms to form distorted KAs6 octahedra that share corners with two equivalent In(2)As4 tetrahedra, corners with four equivalent Ge(2)GeAs3 tetrahedra, edges with two equivalent K(2)As6 octahedra, edges with two equivalent Ge(2)GeAs3 tetrahedra, and edges with four equivalent In(1)As4 tetrahedra. Both K(2)-As(7) bond lengths are 3.29 Å. All K(2)-As(2) bond lengths are 3.53 Å. In the third K site, K(3) is bonded in a 7-coordinate geometry to one As(2), two equivalent As(1), two equivalent As(5), and two equivalent As(7) atoms. The K(3)-As(2) bond length is 3.86 Å. Both K(3)-As(1) bond lengths are 3.70 Å. Both K(3)-As(5) bond lengths are 3.46 Å. Both K(3)-As(7) bond lengths are 3.40 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to one As(2), one As(6), and two equivalent As(7) atoms to form InAs4 tetrahedra that share corners with two equivalent In(1)As4 tetrahedra, corners with two equivalent In(2)As4 tetrahedra, corners with two equivalent Ge(2)GeAs3 tetrahedra, and edges with two equivalent K(2)As6 octahedra. The In(1)-As(2) bond length is 2.75 Å. The In(1)-As(6) bond length is 2.68 Å. Both In(1)-As(7) bond lengths are 2.65 Å. In the second In site, In(2) is bonded to one As(1), one As(7), and two equivalent As(3) atoms to form InAs4 tetrahedra that share  a cornercorner with one K(2)As6 octahedra, corners with two equivalent In(1)As4 tetrahedra, corners with two equivalent In(2)As4 tetrahedra, corners with two equivalent Ge(1)GeAs3 tetrahedra, and corners with two equivalent Ge(3)GeAs3 tetrahedra. The corner-sharing octahedral tilt angles are 3°. The In(2)-As(1) bond length is 2.77 Å. The In(2)-As(7) bond length is 2.67 Å. Both In(2)-As(3) bond lengths are 2.68 Å. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one Ge(3), one As(3), and two equivalent As(4) atoms to form GeGeAs3 tetrahedra that share corners with two equivalent As(1)K3InGe2 octahedra,  a cornercorner with one As(4)K2Ge3 square pyramid, corners with two equivalent In(2)As4 tetrahedra, corners with two equivalent Ge(1)GeAs3 tetrahedra, and corners with two equivalent Ge(3)GeAs3 tetrahedra. The corner-sharing octahedral tilt angles are 74°. The Ge(1)-Ge(3) bond length is 2.51 Å. The Ge(1)-As(3) bond length is 2.44 Å. Both Ge(1)-As(4) bond lengths are 2.54 Å. In the second Ge site, Ge(2) is bonded to one Ge(2), one As(5), and two equivalent As(2) atoms to form GeGeAs3 tetrahedra that share corners with two equivalent K(2)As6 octahedra, corners with two equivalent In(1)As4 tetrahedra, corners with two equivalent Ge(2)GeAs3 tetrahedra, and  an edgeedge with one K(2)As6 octahedra. The corner-sharing octahedral tilt angles are 20°. The Ge(2)-Ge(2) bond length is 2.52 Å. The Ge(2)-As(5) bond length is 2.54 Å. Both Ge(2)-As(2) bond lengths are 2.52 Å. In the third Ge site, Ge(3) is bonded to one Ge(1), one As(4), and two equivalent As(1) atoms to form GeGeAs3 tetrahedra that share corners with two equivalent As(4)K2Ge3 square pyramids, corners with two equivalent In(2)As4 tetrahedra, corners with two equivalent Ge(1)GeAs3 tetrahedra, corners with two equivalent Ge(3)GeAs3 tetrahedra, and  a cornercorner with one As(3)K2In2Ge trigonal bipyramid. The Ge(3)-As(4) bond length is 2.48 Å. Both Ge(3)-As(1) bond lengths are 2.52 Å. There are seven inequivalent As sites. In the first As site, As(2) is bonded in a 6-coordinate geometry to one K(3), two equivalent K(2), one In(1), and two equivalent Ge(2) atoms. In the second As site, As(3) is bonded to two equivalent K(1), two equivalent In(2), and one Ge(1) atom to form distorted AsK2In2Ge trigonal bipyramids that share corners with two equivalent As(7)K3In3 octahedra, corners with four equivalent As(1)K3InGe2 octahedra, corners with four equivalent As(4)K2Ge3 square pyramids,  a cornercorner with one Ge(3)GeAs3 tetrahedra,  an edgeedge with one As(4)K2Ge3 square pyramid, and edges with two equivalent As(3)K2In2Ge trigonal bipyramids. The corner-sharing octahedral tilt angles range from 37-68°. In the third As site, As(4) is bonded to two equivalent K(1), one Ge(3), and two equivalent Ge(1) atoms to form distorted AsK2Ge3 square pyramids that share  a cornercorner with one Ge(1)GeAs3 tetrahedra, corners with two equivalent Ge(3)GeAs3 tetrahedra, corners with four equivalent As(3)K2In2Ge trigonal bipyramids, edges with two equivalent As(1)K3InGe2 octahedra, edges with two equivalent As(4)K2Ge3 square pyramids, and  an edgeedge with one As(3)K2In2Ge trigonal bipyramid. In the fourth As site, As(5) is bonded in a 5-coordinate geometry to two equivalent K(3), one Ge(2), and two equivalent As(6) atoms. Both As(5)-As(6) bond lengths are 2.54 Å. In the fifth As site, As(6) is bonded in a 5-coordinate geometry to two equivalent K(1), one In(1), and two equivalent As(5) atoms. In the sixth As site, As(7) is bonded to one K(2), two equivalent K(3), one In(2), and two equivalent In(1) atoms to form AsK3In3 octahedra that share  a cornercorner with one As(7)K3In3 octahedra, corners with two equivalent As(1)K3InGe2 octahedra, corners with two equivalent As(3)K2In2Ge trigonal bipyramids, edges with two equivalent As(7)K3In3 octahedra, and  a faceface with one As(1)K3InGe2 octahedra. The corner-sharing octahedral tilt angles range from 0-69°. In the seventh As site, As(1) is bonded to one K(1), two equivalent K(3), one In(2), and two equivalent Ge(3) atoms to form distorted AsK3InGe2 octahedra that share corners with two equivalent As(7)K3In3 octahedra, corners with two equivalent Ge(1)GeAs3 tetrahedra, corners with four equivalent As(3)K2In2Ge trigonal bipyramids, edges with two equivalent As(1)K3InGe2 octahedra, edges with two equivalent As(4)K2Ge3 square pyramids, and  a faceface with one As(7)K3In3 octahedra. The corner-sharing octahedral tilt angles are 69°.