Na2TiCl4 crystallizes in the orthorhombic Pbam space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent Cl(1) and four equivalent Cl(2) atoms. Ti(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form edge-sharing TiCl6 octahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1) and two equivalent Ti(1) atoms. In the second Cl site, Cl(2) is bonded to four equivalent Na(1) and one Ti(1) atom to form a mixture of distorted edge and corner-sharing ClNa4Ti trigonal bipyramids.
Na2TiCl4 crystallizes in the orthorhombic Pbam space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent Cl(1) and four equivalent Cl(2) atoms. There is one shorter (2.96 Å) and one longer (3.02 Å) Na(1)-Cl(1) bond length. There are two shorter (2.79 Å) and two longer (2.80 Å) Na(1)-Cl(2) bond lengths. Ti(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form edge-sharing TiCl6 octahedra. Both Ti(1)-Cl(2) bond lengths are 2.55 Å. All Ti(1)-Cl(1) bond lengths are 2.57 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1) and two equivalent Ti(1) atoms. In the second Cl site, Cl(2) is bonded to four equivalent Na(1) and one Ti(1) atom to form a mixture of distorted edge and corner-sharing ClNa4Ti trigonal bipyramids.