NaCuTiS3 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(2), and three equivalent S(3) atoms. Ti(1) is bonded to one S(2), two equivalent S(3), and three equivalent S(1) atoms to form distorted TiS6 octahedra that share  a cornercorner with one Cu(1)S4 tetrahedra, edges with four equivalent Ti(1)S6 octahedra, and edges with two equivalent Cu(1)S4 tetrahedra. Cu(1) is bonded to one S(3) and three equivalent S(2) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one Ti(1)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1) and three equivalent Ti(1) atoms to form distorted edge-sharing SNa2Ti3 trigonal bipyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Na(1), one Ti(1), and three equivalent Cu(1) atoms. In the third S site, S(3) is bonded in a 6-coordinate geometry to three equivalent Na(1), two equivalent Ti(1), and one Cu(1) atom.
NaCuTiS3 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(2), and three equivalent S(3) atoms. Both Na(1)-S(1) bond lengths are 2.85 Å. Both Na(1)-S(2) bond lengths are 2.96 Å. There are two shorter (3.03 Å) and one longer (3.18 Å) Na(1)-S(3) bond length. Ti(1) is bonded to one S(2), two equivalent S(3), and three equivalent S(1) atoms to form distorted TiS6 octahedra that share  a cornercorner with one Cu(1)S4 tetrahedra, edges with four equivalent Ti(1)S6 octahedra, and edges with two equivalent Cu(1)S4 tetrahedra. The Ti(1)-S(2) bond length is 2.38 Å. Both Ti(1)-S(3) bond lengths are 2.46 Å. There are two shorter (2.48 Å) and one longer (2.53 Å) Ti(1)-S(1) bond length. Cu(1) is bonded to one S(3) and three equivalent S(2) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one Ti(1)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. The Cu(1)-S(3) bond length is 2.24 Å. There are two shorter (2.31 Å) and one longer (2.40 Å) Cu(1)-S(2) bond length. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1) and three equivalent Ti(1) atoms to form distorted edge-sharing SNa2Ti3 trigonal bipyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Na(1), one Ti(1), and three equivalent Cu(1) atoms. In the third S site, S(3) is bonded in a 6-coordinate geometry to three equivalent Na(1), two equivalent Ti(1), and one Cu(1) atom.