NaCr(PS3)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 5-coordinate geometry to one S(6), two equivalent S(1), and two equivalent S(4) atoms. Cr(1) is bonded to one S(2), one S(6), two equivalent S(3), and two equivalent S(5) atoms to form CrS6 octahedra that share corners with three equivalent P(1)PS3 tetrahedra, corners with three equivalent P(2)PS3 tetrahedra, and edges with two equivalent Cr(1)S6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one P(2), one S(2), one S(4), and one S(5) atom to form distorted PPS3 tetrahedra that share corners with three equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 73-75°. In the second P site, P(2) is bonded to one P(1), one S(1), one S(3), and one S(6) atom to form distorted PPS3 tetrahedra that share corners with three equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 73-74°. There are six inequivalent S sites. In the first S site, S(5) is bonded in a trigonal non-coplanar geometry to two equivalent Cr(1) and one P(1) atom. In the second S site, S(6) is bonded in a distorted T-shaped geometry to one Na(1), one Cr(1), and one P(2) atom. In the third S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one P(2) atom. In the fourth S site, S(2) is bonded in a water-like geometry to one Cr(1) and one P(1) atom. In the fifth S site, S(3) is bonded in a trigonal non-coplanar geometry to two equivalent Cr(1) and one P(2) atom. In the sixth S site, S(4) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one P(1) atom.
NaCr(PS3)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 5-coordinate geometry to one S(6), two equivalent S(1), and two equivalent S(4) atoms. The Na(1)-S(6) bond length is 2.97 Å. There is one shorter (2.96 Å) and one longer (3.11 Å) Na(1)-S(1) bond length. There is one shorter (2.89 Å) and one longer (2.99 Å) Na(1)-S(4) bond length. Cr(1) is bonded to one S(2), one S(6), two equivalent S(3), and two equivalent S(5) atoms to form CrS6 octahedra that share corners with three equivalent P(1)PS3 tetrahedra, corners with three equivalent P(2)PS3 tetrahedra, and edges with two equivalent Cr(1)S6 octahedra. The Cr(1)-S(2) bond length is 2.41 Å. The Cr(1)-S(6) bond length is 2.42 Å. There is one shorter (2.44 Å) and one longer (2.45 Å) Cr(1)-S(3) bond length. There is one shorter (2.44 Å) and one longer (2.45 Å) Cr(1)-S(5) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one P(2), one S(2), one S(4), and one S(5) atom to form distorted PPS3 tetrahedra that share corners with three equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 73-75°. The P(1)-P(2) bond length is 2.22 Å. The P(1)-S(2) bond length is 2.04 Å. The P(1)-S(4) bond length is 1.98 Å. The P(1)-S(5) bond length is 2.13 Å. In the second P site, P(2) is bonded to one P(1), one S(1), one S(3), and one S(6) atom to form distorted PPS3 tetrahedra that share corners with three equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 73-74°. The P(2)-S(1) bond length is 1.98 Å. The P(2)-S(3) bond length is 2.14 Å. The P(2)-S(6) bond length is 2.04 Å. There are six inequivalent S sites. In the first S site, S(5) is bonded in a trigonal non-coplanar geometry to two equivalent Cr(1) and one P(1) atom. In the second S site, S(6) is bonded in a distorted T-shaped geometry to one Na(1), one Cr(1), and one P(2) atom. In the third S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one P(2) atom. In the fourth S site, S(2) is bonded in a water-like geometry to one Cr(1) and one P(1) atom. In the fifth S site, S(3) is bonded in a trigonal non-coplanar geometry to two equivalent Cr(1) and one P(2) atom. In the sixth S site, S(4) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one P(1) atom.