K6NaAu2O8I crystallizes in the monoclinic P2/c space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms. In the second K site, K(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. In the third K site, K(3) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), and two equivalent O(2) atoms. In the fourth K site, K(4) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(4) atoms. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. There are two inequivalent Au sites. In the first Au site, Au(1) is bonded in a linear geometry to two equivalent O(2) atoms. In the second Au site, Au(2) is bonded in a linear geometry to two equivalent O(2) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded to one K(2), one K(3), two equivalent K(1), one Na(1), and one I(1) atom to form OK4NaI octahedra that share  a cornercorner with one O(3)K4NaI octahedra, corners with two equivalent O(2)K4Au2 octahedra, corners with three equivalent O(1)K4NaI octahedra, corners with three equivalent O(4)K4NaI octahedra,  an edgeedge with one O(2)K4Au2 octahedra,  an edgeedge with one O(1)K4NaI octahedra, edges with two equivalent O(3)K4NaI octahedra, faces with two equivalent O(3)K4NaI octahedra, and faces with two equivalent O(4)K4NaI octahedra. The corner-sharing octahedral tilt angles range from 0-58°. In the second O site, O(2) is bonded to one K(1), one K(4), two equivalent K(3), one Au(1), and one Au(2) atom to form distorted OK4Au2 octahedra that share corners with two equivalent O(2)K4Au2 octahedra, corners with two equivalent O(1)K4NaI octahedra, corners with two equivalent O(3)K4NaI octahedra, corners with five equivalent O(4)K4NaI octahedra,  an edgeedge with one O(1)K4NaI octahedra,  an edgeedge with one O(3)K4NaI octahedra, and  a faceface with one O(2)K4Au2 octahedra. The corner-sharing octahedral tilt angles range from 0-65°. In the third O site, O(3) is bonded to one K(2), one K(3), two equivalent K(1), one Na(1), and one I(1) atom to form OK4NaI octahedra that share  a cornercorner with one O(1)K4NaI octahedra, corners with two equivalent O(2)K4Au2 octahedra, corners with two equivalent O(3)K4NaI octahedra, corners with three equivalent O(4)K4NaI octahedra,  an edgeedge with one O(2)K4Au2 octahedra, edges with two equivalent O(1)K4NaI octahedra,  a faceface with one O(3)K4NaI octahedra, faces with two equivalent O(1)K4NaI octahedra, and faces with two equivalent O(4)K4NaI octahedra. The corner-sharing octahedral tilt angles range from 0-63°. In the fourth O site, O(4) is bonded to one K(1), one K(2), one K(3), one K(4), one Na(1), and one I(1) atom to form distorted OK4NaI octahedra that share corners with two equivalent O(4)K4NaI octahedra, corners with three equivalent O(1)K4NaI octahedra, corners with three equivalent O(3)K4NaI octahedra, corners with five equivalent O(2)K4Au2 octahedra,  an edgeedge with one O(4)K4NaI octahedra, faces with two equivalent O(1)K4NaI octahedra, and faces with two equivalent O(3)K4NaI octahedra. The corner-sharing octahedral tilt angles range from 0-65°. I(1) is bonded in an octahedral geometry to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms.
K6NaAu2O8I crystallizes in the monoclinic P2/c space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms. The K(1)-O(2) bond length is 3.07 Å. The K(1)-O(4) bond length is 2.93 Å. There is one shorter (2.68 Å) and one longer (2.75 Å) K(1)-O(1) bond length. There is one shorter (2.64 Å) and one longer (2.70 Å) K(1)-O(3) bond length. In the second K site, K(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. Both K(2)-O(1) bond lengths are 2.75 Å. Both K(2)-O(3) bond lengths are 2.79 Å. Both K(2)-O(4) bond lengths are 2.95 Å. In the third K site, K(3) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), and two equivalent O(2) atoms. The K(3)-O(1) bond length is 2.71 Å. The K(3)-O(3) bond length is 2.73 Å. The K(3)-O(4) bond length is 2.73 Å. There is one shorter (2.66 Å) and one longer (2.91 Å) K(3)-O(2) bond length. In the fourth K site, K(4) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(4) atoms. Both K(4)-O(2) bond lengths are 2.69 Å. Both K(4)-O(4) bond lengths are 2.61 Å. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. Both Na(1)-O(1) bond lengths are 2.49 Å. Both Na(1)-O(3) bond lengths are 2.35 Å. Both Na(1)-O(4) bond lengths are 2.43 Å. There are two inequivalent Au sites. In the first Au site, Au(1) is bonded in a linear geometry to two equivalent O(2) atoms. Both Au(1)-O(2) bond lengths are 2.02 Å. In the second Au site, Au(2) is bonded in a linear geometry to two equivalent O(2) atoms. Both Au(2)-O(2) bond lengths are 2.00 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one K(2), one K(3), two equivalent K(1), one Na(1), and one I(1) atom to form OK4NaI octahedra that share  a cornercorner with one O(3)K4NaI octahedra, corners with two equivalent O(2)K4Au2 octahedra, corners with three equivalent O(1)K4NaI octahedra, corners with three equivalent O(4)K4NaI octahedra,  an edgeedge with one O(2)K4Au2 octahedra,  an edgeedge with one O(1)K4NaI octahedra, edges with two equivalent O(3)K4NaI octahedra, faces with two equivalent O(3)K4NaI octahedra, and faces with two equivalent O(4)K4NaI octahedra. The corner-sharing octahedral tilt angles range from 0-58°. The O(1)-I(1) bond length is 1.90 Å. In the second O site, O(2) is bonded to one K(1), one K(4), two equivalent K(3), one Au(1), and one Au(2) atom to form distorted OK4Au2 octahedra that share corners with two equivalent O(2)K4Au2 octahedra, corners with two equivalent O(1)K4NaI octahedra, corners with two equivalent O(3)K4NaI octahedra, corners with five equivalent O(4)K4NaI octahedra,  an edgeedge with one O(1)K4NaI octahedra,  an edgeedge with one O(3)K4NaI octahedra, and  a faceface with one O(2)K4Au2 octahedra. The corner-sharing octahedral tilt angles range from 0-65°. In the third O site, O(3) is bonded to one K(2), one K(3), two equivalent K(1), one Na(1), and one I(1) atom to form OK4NaI octahedra that share  a cornercorner with one O(1)K4NaI octahedra, corners with two equivalent O(2)K4Au2 octahedra, corners with two equivalent O(3)K4NaI octahedra, corners with three equivalent O(4)K4NaI octahedra,  an edgeedge with one O(2)K4Au2 octahedra, edges with two equivalent O(1)K4NaI octahedra,  a faceface with one O(3)K4NaI octahedra, faces with two equivalent O(1)K4NaI octahedra, and faces with two equivalent O(4)K4NaI octahedra. The corner-sharing octahedral tilt angles range from 0-63°. The O(3)-I(1) bond length is 1.89 Å. In the fourth O site, O(4) is bonded to one K(1), one K(2), one K(3), one K(4), one Na(1), and one I(1) atom to form distorted OK4NaI octahedra that share corners with two equivalent O(4)K4NaI octahedra, corners with three equivalent O(1)K4NaI octahedra, corners with three equivalent O(3)K4NaI octahedra, corners with five equivalent O(2)K4Au2 octahedra,  an edgeedge with one O(4)K4NaI octahedra, faces with two equivalent O(1)K4NaI octahedra, and faces with two equivalent O(3)K4NaI octahedra. The corner-sharing octahedral tilt angles range from 0-65°. The O(4)-I(1) bond length is 1.91 Å. I(1) is bonded in an octahedral geometry to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms.