K5AuAs2 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent K sites. In the first K site, K(1) is bonded to four equivalent As(1) atoms to form distorted KAs4 tetrahedra that share corners with six equivalent K(1)As4 tetrahedra, corners with four equivalent Au(1)K3As2 trigonal bipyramids, and edges with three equivalent K(1)As4 tetrahedra. In the second K site, K(2) is bonded in a distorted trigonal planar geometry to three equivalent As(1) atoms. In the third K site, K(3) is bonded in a trigonal planar geometry to three equivalent Au(1) atoms. Au(1) is bonded to three equivalent K(3) and two equivalent As(1) atoms to form distorted AuK3As2 trigonal bipyramids that share corners with eight equivalent K(1)As4 tetrahedra and corners with six equivalent Au(1)K3As2 trigonal bipyramids. As(1) is bonded in a distorted body-centered cubic geometry to three equivalent K(2), four equivalent K(1), and one Au(1) atom.
K5AuAs2 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent K sites. In the first K site, K(1) is bonded to four equivalent As(1) atoms to form distorted KAs4 tetrahedra that share corners with six equivalent K(1)As4 tetrahedra, corners with four equivalent Au(1)K3As2 trigonal bipyramids, and edges with three equivalent K(1)As4 tetrahedra. There is one shorter (3.28 Å) and three longer (3.58 Å) K(1)-As(1) bond lengths. In the second K site, K(2) is bonded in a distorted trigonal planar geometry to three equivalent As(1) atoms. All K(2)-As(1) bond lengths are 3.35 Å. In the third K site, K(3) is bonded in a trigonal planar geometry to three equivalent Au(1) atoms. All K(3)-Au(1) bond lengths are 3.31 Å. Au(1) is bonded to three equivalent K(3) and two equivalent As(1) atoms to form distorted AuK3As2 trigonal bipyramids that share corners with eight equivalent K(1)As4 tetrahedra and corners with six equivalent Au(1)K3As2 trigonal bipyramids. Both Au(1)-As(1) bond lengths are 2.49 Å. As(1) is bonded in a distorted body-centered cubic geometry to three equivalent K(2), four equivalent K(1), and one Au(1) atom.