Na2CuSbS3 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(1), two equivalent S(3), and three equivalent S(2) atoms to form distorted NaS6 octahedra that share corners with two equivalent Na(1)S6 octahedra,  a cornercorner with one Na(2)S5 square pyramid, corners with two equivalent Sb(1)CuS3 trigonal pyramids, edges with three equivalent Na(1)S6 octahedra, edges with five equivalent Na(2)S5 square pyramids, and edges with two equivalent Sb(1)CuS3 trigonal pyramids. The corner-sharing octahedral tilt angles are 12°. In the second Na site, Na(2) is bonded to one S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted NaS5 square pyramids that share  a cornercorner with one Na(1)S6 octahedra, corners with two equivalent Na(2)S5 square pyramids, corners with three equivalent Sb(1)CuS3 trigonal pyramids, edges with five equivalent Na(1)S6 octahedra,  an edgeedge with one Na(2)S5 square pyramid, and  an edgeedge with one Sb(1)CuS3 trigonal pyramid. The corner-sharing octahedral tilt angles are 14°. Cu(1) is bonded in a 3-coordinate geometry to one Sb(1), one S(3), and two equivalent S(1) atoms. Sb(1) is bonded to one Cu(1), one S(1), one S(2), and one S(3) atom to form distorted SbCuS3 trigonal pyramids that share  a cornercorner with one S(3)Na4CuSb octahedra, corners with two equivalent Na(1)S6 octahedra, corners with three equivalent Na(2)S5 square pyramids, edges with two equivalent Na(1)S6 octahedra, and  an edgeedge with one Na(2)S5 square pyramid. The corner-sharing octahedral tilt angles range from 1-81°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), two equivalent Cu(1), and one Sb(1) atom. In the second S site, S(2) is bonded to two equivalent Na(2), three equivalent Na(1), and one Sb(1) atom to form SNa5Sb octahedra that share  a cornercorner with one S(3)Na4CuSb octahedra, corners with two equivalent S(2)Na5Sb octahedra, edges with three equivalent S(2)Na5Sb octahedra, and edges with five equivalent S(3)Na4CuSb octahedra. The corner-sharing octahedral tilt angles range from 9-12°. In the third S site, S(3) is bonded to two equivalent Na(1), two equivalent Na(2), one Cu(1), and one Sb(1) atom to form SNa4CuSb octahedra that share  a cornercorner with one S(2)Na5Sb octahedra, corners with two equivalent S(3)Na4CuSb octahedra,  a cornercorner with one Sb(1)CuS3 trigonal pyramid,  an edgeedge with one S(3)Na4CuSb octahedra, and edges with five equivalent S(2)Na5Sb octahedra. The corner-sharing octahedral tilt angles range from 2-9°.
Na2CuSbS3 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(1), two equivalent S(3), and three equivalent S(2) atoms to form distorted NaS6 octahedra that share corners with two equivalent Na(1)S6 octahedra,  a cornercorner with one Na(2)S5 square pyramid, corners with two equivalent Sb(1)CuS3 trigonal pyramids, edges with three equivalent Na(1)S6 octahedra, edges with five equivalent Na(2)S5 square pyramids, and edges with two equivalent Sb(1)CuS3 trigonal pyramids. The corner-sharing octahedral tilt angles are 12°. The Na(1)-S(1) bond length is 2.85 Å. There is one shorter (2.79 Å) and one longer (2.98 Å) Na(1)-S(3) bond length. There are a spread of Na(1)-S(2) bond distances ranging from 2.89-2.97 Å. In the second Na site, Na(2) is bonded to one S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted NaS5 square pyramids that share  a cornercorner with one Na(1)S6 octahedra, corners with two equivalent Na(2)S5 square pyramids, corners with three equivalent Sb(1)CuS3 trigonal pyramids, edges with five equivalent Na(1)S6 octahedra,  an edgeedge with one Na(2)S5 square pyramid, and  an edgeedge with one Sb(1)CuS3 trigonal pyramid. The corner-sharing octahedral tilt angles are 14°. The Na(2)-S(1) bond length is 3.02 Å. There is one shorter (2.81 Å) and one longer (3.09 Å) Na(2)-S(2) bond length. There is one shorter (2.90 Å) and one longer (2.96 Å) Na(2)-S(3) bond length. Cu(1) is bonded in a 3-coordinate geometry to one Sb(1), one S(3), and two equivalent S(1) atoms. The Cu(1)-Sb(1) bond length is 2.76 Å. The Cu(1)-S(3) bond length is 2.25 Å. There is one shorter (2.26 Å) and one longer (2.30 Å) Cu(1)-S(1) bond length. Sb(1) is bonded to one Cu(1), one S(1), one S(2), and one S(3) atom to form distorted SbCuS3 trigonal pyramids that share  a cornercorner with one S(3)Na4CuSb octahedra, corners with two equivalent Na(1)S6 octahedra, corners with three equivalent Na(2)S5 square pyramids, edges with two equivalent Na(1)S6 octahedra, and  an edgeedge with one Na(2)S5 square pyramid. The corner-sharing octahedral tilt angles range from 1-81°. The Sb(1)-S(1) bond length is 2.50 Å. The Sb(1)-S(2) bond length is 2.41 Å. The Sb(1)-S(3) bond length is 2.44 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), two equivalent Cu(1), and one Sb(1) atom. In the second S site, S(2) is bonded to two equivalent Na(2), three equivalent Na(1), and one Sb(1) atom to form SNa5Sb octahedra that share  a cornercorner with one S(3)Na4CuSb octahedra, corners with two equivalent S(2)Na5Sb octahedra, edges with three equivalent S(2)Na5Sb octahedra, and edges with five equivalent S(3)Na4CuSb octahedra. The corner-sharing octahedral tilt angles range from 9-12°. In the third S site, S(3) is bonded to two equivalent Na(1), two equivalent Na(2), one Cu(1), and one Sb(1) atom to form SNa4CuSb octahedra that share  a cornercorner with one S(2)Na5Sb octahedra, corners with two equivalent S(3)Na4CuSb octahedra,  a cornercorner with one Sb(1)CuS3 trigonal pyramid,  an edgeedge with one S(3)Na4CuSb octahedra, and edges with five equivalent S(2)Na5Sb octahedra. The corner-sharing octahedral tilt angles range from 2-9°.