KZrPSe6 crystallizes in the orthorhombic Pmc2_1 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(7), one Se(8), two equivalent Se(10), and two equivalent Se(6) atoms. In the second K site, K(2) is bonded in a 5-coordinate geometry to one Se(3), one Se(4), one Se(9), and two equivalent Se(6) atoms. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 8-coordinate geometry to one Se(12), one Se(6), two equivalent Se(2), two equivalent Se(3), and two equivalent Se(5) atoms. In the second Zr site, Zr(2) is bonded in a 8-coordinate geometry to one Se(1), one Se(10), two equivalent Se(11), two equivalent Se(8), and two equivalent Se(9) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded to one Se(7), one Se(8), and two equivalent Se(1) atoms to form corner-sharing PSe4 tetrahedra. In the second P site, P(2) is bonded to one Se(3), one Se(4), and two equivalent Se(12) atoms to form corner-sharing PSe4 tetrahedra. There are twelve inequivalent Se sites. In the first Se site, Se(1) is bonded in a distorted T-shaped geometry to one Zr(2) and two equivalent P(1) atoms. In the second Se site, Se(2) is bonded in a 4-coordinate geometry to one K(1), two equivalent Zr(1), and one Se(5) atom. In the third Se site, Se(3) is bonded in a rectangular see-saw-like geometry to one K(2), two equivalent Zr(1), and one P(2) atom. In the fourth Se site, Se(4) is bonded in a distorted L-shaped geometry to one K(2) and one P(2) atom. In the fifth Se site, Se(5) is bonded in a 3-coordinate geometry to two equivalent Zr(1) and one Se(2) atom. In the sixth Se site, Se(6) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent K(2), and one Zr(1) atom. In the seventh Se site, Se(7) is bonded in a bent 120 degrees geometry to one K(1) and one P(1) atom. In the eighth Se site, Se(8) is bonded in a distorted rectangular see-saw-like geometry to one K(1), two equivalent Zr(2), and one P(1) atom. In the ninth Se site, Se(9) is bonded in a 4-coordinate geometry to one K(2), two equivalent Zr(2), and one Se(11) atom. In the tenth Se site, Se(10) is bonded in a 3-coordinate geometry to two equivalent K(1) and one Zr(2) atom. In the eleventh Se site, Se(11) is bonded in a distorted L-shaped geometry to two equivalent Zr(2) and one Se(9) atom. In the twelfth Se site, Se(12) is bonded in a distorted T-shaped geometry to one Zr(1) and two equivalent P(2) atoms.
KZrPSe6 crystallizes in the orthorhombic Pmc2_1 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(7), one Se(8), two equivalent Se(10), and two equivalent Se(6) atoms. The K(1)-Se(2) bond length is 3.62 Å. The K(1)-Se(7) bond length is 3.31 Å. The K(1)-Se(8) bond length is 3.68 Å. Both K(1)-Se(10) bond lengths are 3.43 Å. Both K(1)-Se(6) bond lengths are 3.70 Å. In the second K site, K(2) is bonded in a 5-coordinate geometry to one Se(3), one Se(4), one Se(9), and two equivalent Se(6) atoms. The K(2)-Se(3) bond length is 3.40 Å. The K(2)-Se(4) bond length is 3.48 Å. The K(2)-Se(9) bond length is 3.85 Å. Both K(2)-Se(6) bond lengths are 3.30 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 8-coordinate geometry to one Se(12), one Se(6), two equivalent Se(2), two equivalent Se(3), and two equivalent Se(5) atoms. The Zr(1)-Se(12) bond length is 2.96 Å. The Zr(1)-Se(6) bond length is 2.79 Å. Both Zr(1)-Se(2) bond lengths are 2.72 Å. Both Zr(1)-Se(3) bond lengths are 2.83 Å. Both Zr(1)-Se(5) bond lengths are 2.82 Å. In the second Zr site, Zr(2) is bonded in a 8-coordinate geometry to one Se(1), one Se(10), two equivalent Se(11), two equivalent Se(8), and two equivalent Se(9) atoms. The Zr(2)-Se(1) bond length is 2.93 Å. The Zr(2)-Se(10) bond length is 2.71 Å. Both Zr(2)-Se(11) bond lengths are 2.76 Å. Both Zr(2)-Se(8) bond lengths are 2.80 Å. Both Zr(2)-Se(9) bond lengths are 2.85 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one Se(7), one Se(8), and two equivalent Se(1) atoms to form corner-sharing PSe4 tetrahedra. The P(1)-Se(7) bond length is 2.11 Å. The P(1)-Se(8) bond length is 2.33 Å. Both P(1)-Se(1) bond lengths are 2.40 Å. In the second P site, P(2) is bonded to one Se(3), one Se(4), and two equivalent Se(12) atoms to form corner-sharing PSe4 tetrahedra. The P(2)-Se(3) bond length is 2.30 Å. The P(2)-Se(4) bond length is 2.11 Å. Both P(2)-Se(12) bond lengths are 2.38 Å. There are twelve inequivalent Se sites. In the first Se site, Se(1) is bonded in a distorted T-shaped geometry to one Zr(2) and two equivalent P(1) atoms. In the second Se site, Se(2) is bonded in a 4-coordinate geometry to one K(1), two equivalent Zr(1), and one Se(5) atom. The Se(2)-Se(5) bond length is 2.38 Å. In the third Se site, Se(3) is bonded in a rectangular see-saw-like geometry to one K(2), two equivalent Zr(1), and one P(2) atom. In the fourth Se site, Se(4) is bonded in a distorted L-shaped geometry to one K(2) and one P(2) atom. In the fifth Se site, Se(5) is bonded in a 3-coordinate geometry to two equivalent Zr(1) and one Se(2) atom. In the sixth Se site, Se(6) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent K(2), and one Zr(1) atom. In the seventh Se site, Se(7) is bonded in a bent 120 degrees geometry to one K(1) and one P(1) atom. In the eighth Se site, Se(8) is bonded in a distorted rectangular see-saw-like geometry to one K(1), two equivalent Zr(2), and one P(1) atom. In the ninth Se site, Se(9) is bonded in a 4-coordinate geometry to one K(2), two equivalent Zr(2), and one Se(11) atom. The Se(9)-Se(11) bond length is 2.40 Å. In the tenth Se site, Se(10) is bonded in a 3-coordinate geometry to two equivalent K(1) and one Zr(2) atom. In the eleventh Se site, Se(11) is bonded in a distorted L-shaped geometry to two equivalent Zr(2) and one Se(9) atom. In the twelfth Se site, Se(12) is bonded in a distorted T-shaped geometry to one Zr(1) and two equivalent P(2) atoms.