K2AsTe2 crystallizes in the orthorhombic Pnma space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one As(2), two equivalent Te(2), and four equivalent Te(1) atoms. In the second K site, K(2) is bonded in a 7-coordinate geometry to one As(1), two equivalent Te(1), and four equivalent Te(2) atoms. In the third K site, K(3) is bonded in a 6-coordinate geometry to two equivalent Te(1) and four equivalent Te(2) atoms. In the fourth K site, K(4) is bonded in a 7-coordinate geometry to one As(2), two equivalent Te(2), and four equivalent Te(1) atoms. There are two inequivalent As sites. In the first As site, As(1) is bonded to one K(2), one As(2), and two equivalent Te(1) atoms to form AsKTe2As trigonal pyramids that share corners with two equivalent Te(1)K6As pentagonal bipyramids. In the second As site, As(2) is bonded to one K(1), one K(4), one As(1), and two equivalent Te(2) atoms to form AsK2Te2As trigonal bipyramids that share corners with two equivalent Te(1)K6As pentagonal bipyramids and edges with four equivalent Te(1)K6As pentagonal bipyramids. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded to one K(2), one K(3), two equivalent K(1), two equivalent K(4), and one As(1) atom to form distorted TeK6As pentagonal bipyramids that share corners with four equivalent Te(1)K6As pentagonal bipyramids,  a cornercorner with one As(2)K2Te2As trigonal bipyramid,  a cornercorner with one As(1)KTe2As trigonal pyramid, edges with two equivalent Te(1)K6As pentagonal bipyramids, edges with two equivalent As(2)K2Te2As trigonal bipyramids, and faces with two equivalent Te(1)K6As pentagonal bipyramids. In the second Te site, Te(2) is bonded in a 7-coordinate geometry to one K(1), one K(4), two equivalent K(2), two equivalent K(3), and one As(2) atom.
K2AsTe2 crystallizes in the orthorhombic Pnma space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one As(2), two equivalent Te(2), and four equivalent Te(1) atoms. The K(1)-As(2) bond length is 3.45 Å. Both K(1)-Te(2) bond lengths are 3.61 Å. There are two shorter (3.68 Å) and two longer (3.82 Å) K(1)-Te(1) bond lengths. In the second K site, K(2) is bonded in a 7-coordinate geometry to one As(1), two equivalent Te(1), and four equivalent Te(2) atoms. The K(2)-As(1) bond length is 3.64 Å. Both K(2)-Te(1) bond lengths are 3.71 Å. There are two shorter (3.61 Å) and two longer (3.73 Å) K(2)-Te(2) bond lengths. In the third K site, K(3) is bonded in a 6-coordinate geometry to two equivalent Te(1) and four equivalent Te(2) atoms. Both K(3)-Te(1) bond lengths are 3.69 Å. There are two shorter (3.46 Å) and two longer (3.52 Å) K(3)-Te(2) bond lengths. In the fourth K site, K(4) is bonded in a 7-coordinate geometry to one As(2), two equivalent Te(2), and four equivalent Te(1) atoms. The K(4)-As(2) bond length is 3.37 Å. Both K(4)-Te(2) bond lengths are 3.85 Å. There are two shorter (3.59 Å) and two longer (3.80 Å) K(4)-Te(1) bond lengths. There are two inequivalent As sites. In the first As site, As(1) is bonded to one K(2), one As(2), and two equivalent Te(1) atoms to form AsKTe2As trigonal pyramids that share corners with two equivalent Te(1)K6As pentagonal bipyramids. The As(1)-As(2) bond length is 2.49 Å. Both As(1)-Te(1) bond lengths are 2.61 Å. In the second As site, As(2) is bonded to one K(1), one K(4), one As(1), and two equivalent Te(2) atoms to form AsK2Te2As trigonal bipyramids that share corners with two equivalent Te(1)K6As pentagonal bipyramids and edges with four equivalent Te(1)K6As pentagonal bipyramids. Both As(2)-Te(2) bond lengths are 2.61 Å. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded to one K(2), one K(3), two equivalent K(1), two equivalent K(4), and one As(1) atom to form distorted TeK6As pentagonal bipyramids that share corners with four equivalent Te(1)K6As pentagonal bipyramids,  a cornercorner with one As(2)K2Te2As trigonal bipyramid,  a cornercorner with one As(1)KTe2As trigonal pyramid, edges with two equivalent Te(1)K6As pentagonal bipyramids, edges with two equivalent As(2)K2Te2As trigonal bipyramids, and faces with two equivalent Te(1)K6As pentagonal bipyramids. In the second Te site, Te(2) is bonded in a 7-coordinate geometry to one K(1), one K(4), two equivalent K(2), two equivalent K(3), and one As(2) atom.