NaTiS2 is Caswellsilverite-like structured and crystallizes in the trigonal R3m space group. Na(1) is bonded in a 6-coordinate geometry to three equivalent S(1) and three equivalent S(2) atoms. Ti(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form edge-sharing TiS6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Na(1) and three equivalent Ti(1) atoms to form a mixture of face, corner, and edge-sharing SNa3Ti3 octahedra. In the second S site, S(2) is bonded to three equivalent Na(1) and three equivalent Ti(1) atoms to form a mixture of distorted face, corner, and edge-sharing SNa3Ti3 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 0-42°.
NaTiS2 is Caswellsilverite-like structured and crystallizes in the trigonal R3m space group. Na(1) is bonded in a 6-coordinate geometry to three equivalent S(1) and three equivalent S(2) atoms. All Na(1)-S(1) bond lengths are 2.80 Å. All Na(1)-S(2) bond lengths are 2.85 Å. Ti(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form edge-sharing TiS6 octahedra. All Ti(1)-S(1) bond lengths are 2.48 Å. All Ti(1)-S(2) bond lengths are 2.48 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Na(1) and three equivalent Ti(1) atoms to form a mixture of face, corner, and edge-sharing SNa3Ti3 octahedra. In the second S site, S(2) is bonded to three equivalent Na(1) and three equivalent Ti(1) atoms to form a mixture of distorted face, corner, and edge-sharing SNa3Ti3 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 0-42°.