K3AuSe13 crystallizes in the monoclinic P2/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 Se(2), one Se(3), one Se(6), two equivalent Se(1), and two equivalent Se(5) atoms. In the second K site, K(2) is bonded in a 10-coordinate geometry to two equivalent Se(3), four equivalent Se(4), and four equivalent Se(5) atoms. Au(1) is bonded in a square co-planar geometry to two equivalent Se(1) and two equivalent Se(6) atoms. There are seven inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent K(1), one Au(1), and one Se(2) atom to form distorted SeK2AuSe trigonal pyramids that share corners with two equivalent Se(5)K4Se square pyramids, corners with three equivalent Se(1)K2AuSe trigonal pyramids, and  an edgeedge with one Se(5)K4Se square pyramid. In the second Se site, Se(2) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Se(1), and one Se(3) atom. In the third Se site, Se(3) is bonded in a see-saw-like geometry to one K(1), one K(2), one Se(2), and one Se(4) atom. In the fourth Se site, Se(4) is bonded in a 4-coordinate geometry to two equivalent K(2), one Se(3), and one Se(5) atom. In the fifth Se site, Se(5) is bonded to two equivalent K(1), two equivalent K(2), and one Se(4) atom to form distorted SeK4Se square pyramids that share corners with two equivalent Se(5)K4Se square pyramids, corners with two equivalent Se(1)K2AuSe trigonal pyramids, edges with three equivalent Se(5)K4Se square pyramids, and  an edgeedge with one Se(1)K2AuSe trigonal pyramid. In the sixth Se site, Se(6) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Au(1), and one Se(7) atom. In the seventh Se site, Se(7) is bonded in a water-like geometry to two equivalent Se(6) atoms.
K3AuSe13 crystallizes in the monoclinic P2/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 Se(2), one Se(3), one Se(6), two equivalent Se(1), and two equivalent Se(5) atoms. The K(1)-Se(2) bond length is 3.69 Å. The K(1)-Se(3) bond length is 3.55 Å. The K(1)-Se(6) bond length is 3.44 Å. There is one shorter (3.33 Å) and one longer (3.38 Å) K(1)-Se(1) bond length. There is one shorter (3.30 Å) and one longer (3.36 Å) K(1)-Se(5) bond length. In the second K site, K(2) is bonded in a 10-coordinate geometry to two equivalent Se(3), four equivalent Se(4), and four equivalent Se(5) atoms. Both K(2)-Se(3) bond lengths are 3.58 Å. There are two shorter (3.58 Å) and two longer (3.63 Å) K(2)-Se(4) bond lengths. There are two shorter (3.30 Å) and two longer (3.49 Å) K(2)-Se(5) bond lengths. Au(1) is bonded in a square co-planar geometry to two equivalent Se(1) and two equivalent Se(6) atoms. Both Au(1)-Se(1) bond lengths are 2.49 Å. Both Au(1)-Se(6) bond lengths are 2.51 Å. There are seven inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent K(1), one Au(1), and one Se(2) atom to form distorted SeK2AuSe trigonal pyramids that share corners with two equivalent Se(5)K4Se square pyramids, corners with three equivalent Se(1)K2AuSe trigonal pyramids, and  an edgeedge with one Se(5)K4Se square pyramid. The Se(1)-Se(2) bond length is 2.36 Å. In the second Se site, Se(2) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Se(1), and one Se(3) atom. The Se(2)-Se(3) bond length is 2.38 Å. In the third Se site, Se(3) is bonded in a see-saw-like geometry to one K(1), one K(2), one Se(2), and one Se(4) atom. The Se(3)-Se(4) bond length is 2.37 Å. In the fourth Se site, Se(4) is bonded in a 4-coordinate geometry to two equivalent K(2), one Se(3), and one Se(5) atom. The Se(4)-Se(5) bond length is 2.35 Å. In the fifth Se site, Se(5) is bonded to two equivalent K(1), two equivalent K(2), and one Se(4) atom to form distorted SeK4Se square pyramids that share corners with two equivalent Se(5)K4Se square pyramids, corners with two equivalent Se(1)K2AuSe trigonal pyramids, edges with three equivalent Se(5)K4Se square pyramids, and  an edgeedge with one Se(1)K2AuSe trigonal pyramid. In the sixth Se site, Se(6) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one Au(1), and one Se(7) atom. The Se(6)-Se(7) bond length is 2.35 Å. In the seventh Se site, Se(7) is bonded in a water-like geometry to two equivalent Se(6) atoms.