Na2TiS2O 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 two equivalent S(1), three equivalent S(2), and one O(1) atom to form distorted NaS5O octahedra that share corners with two equivalent Na(1)S5O octahedra, corners with three equivalent Na(2)S5O octahedra, corners with three equivalent Ti(1)S2O2 tetrahedra, edges with three equivalent Na(1)S5O octahedra, edges with five equivalent Na(2)S5O octahedra, and edges with two equivalent Ti(1)S2O2 tetrahedra. The corner-sharing octahedral tilt angles range from 9-71°. In the second Na site, Na(2) is bonded to two equivalent S(2), three equivalent S(1), and one O(1) atom to form distorted NaS5O octahedra that share corners with two equivalent Na(2)S5O octahedra, corners with three equivalent Na(1)S5O octahedra, corners with three equivalent Ti(1)S2O2 tetrahedra, edges with three equivalent Na(2)S5O octahedra, edges with five equivalent Na(1)S5O octahedra, and edges with two equivalent Ti(1)S2O2 tetrahedra. The corner-sharing octahedral tilt angles range from 6-71°. Ti(1) is bonded to one S(1), one S(2), and two equivalent O(1) atoms to form TiS2O2 tetrahedra that share corners with three equivalent Na(1)S5O octahedra, corners with three equivalent Na(2)S5O octahedra, corners with two equivalent Ti(1)S2O2 tetrahedra, edges with two equivalent Na(1)S5O octahedra, and edges with two equivalent Na(2)S5O octahedra. The corner-sharing octahedral tilt angles range from 13-77°. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1), three equivalent Na(2), and one Ti(1) atom to form distorted SNa5Ti octahedra that share corners with two equivalent S(1)Na5Ti octahedra, corners with three equivalent S(2)Na5Ti octahedra, corners with three equivalent O(1)Na2Ti2 trigonal pyramids, edges with three equivalent S(1)Na5Ti octahedra, edges with five equivalent S(2)Na5Ti octahedra, and edges with two equivalent O(1)Na2Ti2 trigonal pyramids. The corner-sharing octahedral tilt angles range from 6-63°. In the second S site, S(2) is bonded to two equivalent Na(2), three equivalent Na(1), and one Ti(1) atom to form SNa5Ti octahedra that share corners with two equivalent S(2)Na5Ti octahedra, corners with three equivalent S(1)Na5Ti octahedra, corners with three equivalent O(1)Na2Ti2 trigonal pyramids, edges with three equivalent S(2)Na5Ti octahedra, edges with five equivalent S(1)Na5Ti octahedra, and edges with two equivalent O(1)Na2Ti2 trigonal pyramids. The corner-sharing octahedral tilt angles range from 8-63°. O(1) is bonded to one Na(1), one Na(2), and two equivalent Ti(1) atoms to form distorted ONa2Ti2 trigonal pyramids that share corners with three equivalent S(1)Na5Ti octahedra, corners with three equivalent S(2)Na5Ti octahedra, corners with two equivalent O(1)Na2Ti2 trigonal pyramids, edges with two equivalent S(1)Na5Ti octahedra, and edges with two equivalent S(2)Na5Ti octahedra. The corner-sharing octahedral tilt angles range from 15-83°.
Na2TiS2O 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 two equivalent S(1), three equivalent S(2), and one O(1) atom to form distorted NaS5O octahedra that share corners with two equivalent Na(1)S5O octahedra, corners with three equivalent Na(2)S5O octahedra, corners with three equivalent Ti(1)S2O2 tetrahedra, edges with three equivalent Na(1)S5O octahedra, edges with five equivalent Na(2)S5O octahedra, and edges with two equivalent Ti(1)S2O2 tetrahedra. The corner-sharing octahedral tilt angles range from 9-71°. There is one shorter (2.85 Å) and one longer (3.01 Å) Na(1)-S(1) bond length. There are a spread of Na(1)-S(2) bond distances ranging from 2.89-2.99 Å. The Na(1)-O(1) bond length is 2.91 Å. In the second Na site, Na(2) is bonded to two equivalent S(2), three equivalent S(1), and one O(1) atom to form distorted NaS5O octahedra that share corners with two equivalent Na(2)S5O octahedra, corners with three equivalent Na(1)S5O octahedra, corners with three equivalent Ti(1)S2O2 tetrahedra, edges with three equivalent Na(2)S5O octahedra, edges with five equivalent Na(1)S5O octahedra, and edges with two equivalent Ti(1)S2O2 tetrahedra. The corner-sharing octahedral tilt angles range from 6-71°. There is one shorter (2.91 Å) and one longer (2.95 Å) Na(2)-S(2) bond length. There are a spread of Na(2)-S(1) bond distances ranging from 2.84-3.03 Å. The Na(2)-O(1) bond length is 2.49 Å. Ti(1) is bonded to one S(1), one S(2), and two equivalent O(1) atoms to form TiS2O2 tetrahedra that share corners with three equivalent Na(1)S5O octahedra, corners with three equivalent Na(2)S5O octahedra, corners with two equivalent Ti(1)S2O2 tetrahedra, edges with two equivalent Na(1)S5O octahedra, and edges with two equivalent Na(2)S5O octahedra. The corner-sharing octahedral tilt angles range from 13-77°. The Ti(1)-S(1) bond length is 2.24 Å. The Ti(1)-S(2) bond length is 2.25 Å. There is one shorter (1.86 Å) and one longer (1.87 Å) Ti(1)-O(1) bond length. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1), three equivalent Na(2), and one Ti(1) atom to form distorted SNa5Ti octahedra that share corners with two equivalent S(1)Na5Ti octahedra, corners with three equivalent S(2)Na5Ti octahedra, corners with three equivalent O(1)Na2Ti2 trigonal pyramids, edges with three equivalent S(1)Na5Ti octahedra, edges with five equivalent S(2)Na5Ti octahedra, and edges with two equivalent O(1)Na2Ti2 trigonal pyramids. The corner-sharing octahedral tilt angles range from 6-63°. In the second S site, S(2) is bonded to two equivalent Na(2), three equivalent Na(1), and one Ti(1) atom to form SNa5Ti octahedra that share corners with two equivalent S(2)Na5Ti octahedra, corners with three equivalent S(1)Na5Ti octahedra, corners with three equivalent O(1)Na2Ti2 trigonal pyramids, edges with three equivalent S(2)Na5Ti octahedra, edges with five equivalent S(1)Na5Ti octahedra, and edges with two equivalent O(1)Na2Ti2 trigonal pyramids. The corner-sharing octahedral tilt angles range from 8-63°. O(1) is bonded to one Na(1), one Na(2), and two equivalent Ti(1) atoms to form distorted ONa2Ti2 trigonal pyramids that share corners with three equivalent S(1)Na5Ti octahedra, corners with three equivalent S(2)Na5Ti octahedra, corners with two equivalent O(1)Na2Ti2 trigonal pyramids, edges with two equivalent S(1)Na5Ti octahedra, and edges with two equivalent S(2)Na5Ti octahedra. The corner-sharing octahedral tilt angles range from 15-83°.