NaCuIn10S16 is Spinel-derived structured and crystallizes in the tetragonal P-4m2 space group. Na(1) is bonded to four equivalent S(4) atoms to form NaS4 tetrahedra that share corners with four equivalent In(2)S6 octahedra and corners with eight equivalent In(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. Cu(1) is bonded to four equivalent S(3) atoms to form CuS4 tetrahedra that share corners with four equivalent In(1)S6 octahedra and corners with eight equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. There are three inequivalent In sites. In the first In site, In(1) is bonded to one S(3), two equivalent S(4), and three equivalent S(1) atoms to form InS6 octahedra that share  a cornercorner with one Cu(1)S4 tetrahedra, corners with two equivalent Na(1)S4 tetrahedra, corners with three equivalent In(3)S4 tetrahedra, edges with two equivalent In(2)S6 octahedra, and edges with four equivalent In(1)S6 octahedra. In the second In site, In(2) is bonded to one S(4), two equivalent S(3), and three equivalent S(2) atoms to form InS6 octahedra that share  a cornercorner with one Na(1)S4 tetrahedra, corners with two equivalent Cu(1)S4 tetrahedra, corners with three equivalent In(3)S4 tetrahedra, edges with two equivalent In(1)S6 octahedra, and edges with four equivalent In(2)S6 octahedra. In the third In site, In(3) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form corner-sharing InS4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-62°. There are four inequivalent S sites. In the first S site, S(1) is bonded to one In(3) and three equivalent In(1) atoms to form a mixture of distorted edge and corner-sharing SIn4 tetrahedra. In the second S site, S(2) is bonded to one In(3) and three equivalent In(2) atoms to form a mixture of distorted edge and corner-sharing SIn4 trigonal pyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Cu(1), one In(1), and two equivalent In(2) atoms. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one In(2), and two equivalent In(1) atoms.
NaCuIn10S16 is Spinel-derived structured and crystallizes in the tetragonal P-4m2 space group. Na(1) is bonded to four equivalent S(4) atoms to form NaS4 tetrahedra that share corners with four equivalent In(2)S6 octahedra and corners with eight equivalent In(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. All Na(1)-S(4) bond lengths are 2.62 Å. Cu(1) is bonded to four equivalent S(3) atoms to form CuS4 tetrahedra that share corners with four equivalent In(1)S6 octahedra and corners with eight equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. All Cu(1)-S(3) bond lengths are 2.37 Å. There are three inequivalent In sites. In the first In site, In(1) is bonded to one S(3), two equivalent S(4), and three equivalent S(1) atoms to form InS6 octahedra that share  a cornercorner with one Cu(1)S4 tetrahedra, corners with two equivalent Na(1)S4 tetrahedra, corners with three equivalent In(3)S4 tetrahedra, edges with two equivalent In(2)S6 octahedra, and edges with four equivalent In(1)S6 octahedra. The In(1)-S(3) bond length is 2.63 Å. Both In(1)-S(4) bond lengths are 2.58 Å. There are two shorter (2.71 Å) and one longer (2.77 Å) In(1)-S(1) bond length. In the second In site, In(2) is bonded to one S(4), two equivalent S(3), and three equivalent S(2) atoms to form InS6 octahedra that share  a cornercorner with one Na(1)S4 tetrahedra, corners with two equivalent Cu(1)S4 tetrahedra, corners with three equivalent In(3)S4 tetrahedra, edges with two equivalent In(1)S6 octahedra, and edges with four equivalent In(2)S6 octahedra. The In(2)-S(4) bond length is 2.57 Å. Both In(2)-S(3) bond lengths are 2.64 Å. There is one shorter (2.67 Å) and two longer (2.74 Å) In(2)-S(2) bond lengths. In the third In site, In(3) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form corner-sharing InS4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-62°. Both In(3)-S(1) bond lengths are 2.57 Å. Both In(3)-S(2) bond lengths are 2.54 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one In(3) and three equivalent In(1) atoms to form a mixture of distorted edge and corner-sharing SIn4 tetrahedra. In the second S site, S(2) is bonded to one In(3) and three equivalent In(2) atoms to form a mixture of distorted edge and corner-sharing SIn4 trigonal pyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Cu(1), one In(1), and two equivalent In(2) atoms. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one In(2), and two equivalent In(1) atoms.