Na2Ti3Cl8 is beta indium sulfide-derived structured and crystallizes in the trigonal R-3m space group. Na(1) is bonded to six equivalent Cl(2) atoms to form distorted NaCl6 pentagonal pyramids that share corners with six equivalent Ti(1)Cl6 octahedra, edges with three equivalent Ti(1)Cl6 octahedra, and edges with three equivalent Na(1)Cl6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 49°. Ti(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form TiCl6 octahedra that share corners with four equivalent Na(1)Cl6 pentagonal pyramids, edges with four equivalent Ti(1)Cl6 octahedra, and edges with two equivalent Na(1)Cl6 pentagonal pyramids. There are two inequivalent Cl sites. In the first Cl site, Cl(2) is bonded to two equivalent Na(1) and two equivalent Ti(1) atoms to form a mixture of corner and edge-sharing ClNa2Ti2 trigonal pyramids. In the second Cl site, Cl(1) is bonded in a distorted T-shaped geometry to three equivalent Ti(1) atoms.
Na2Ti3Cl8 is beta indium sulfide-derived structured and crystallizes in the trigonal R-3m space group. Na(1) is bonded to six equivalent Cl(2) atoms to form distorted NaCl6 pentagonal pyramids that share corners with six equivalent Ti(1)Cl6 octahedra, edges with three equivalent Ti(1)Cl6 octahedra, and edges with three equivalent Na(1)Cl6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 49°. There are three shorter (2.79 Å) and three longer (2.87 Å) Na(1)-Cl(2) bond lengths. Ti(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form TiCl6 octahedra that share corners with four equivalent Na(1)Cl6 pentagonal pyramids, edges with four equivalent Ti(1)Cl6 octahedra, and edges with two equivalent Na(1)Cl6 pentagonal pyramids. Both Ti(1)-Cl(1) bond lengths are 2.56 Å. All Ti(1)-Cl(2) bond lengths are 2.53 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(2) is bonded to two equivalent Na(1) and two equivalent Ti(1) atoms to form a mixture of corner and edge-sharing ClNa2Ti2 trigonal pyramids. In the second Cl site, Cl(1) is bonded in a distorted T-shaped geometry to three equivalent Ti(1) atoms.