Abstract: | Reactions in the CsCl? TiCl3? Ti system afford CsTiCl3 (CsNiCl3 type, a = 7.3086(7) Å, c = 6.0670(8) Å) and the new phase CsTi2Cl7, the structure of which was determined by single crystal X-ray diffraction means (P2/c, Z = 2, a = 7.0076(4) Å, b = 6.2256(4) Å, c = 12.000(2) Å, β = 92.175(6)°, R/Rw = 0.026/0.035 for 1403 reflections, 2Θ ≤ 60°, MoKα). The structure can be generated by condensation of TiCl6 groups first through cis edges to form TiCl2Cl4/2 ribbons and then by interconnection of these with one chlorine per titanium to give layers, viz., Ti(Cl)Cl4/2Cl1/2]?. The remaining, singly bonded chlorine projects into the interlayer region and has a Ti? Cl distance 0.208 Å less than the average for the five, 2.466 Å, reflecting significant pi bonding of the chlorine to titanium. Possible interaction of the d orbitals on adjacent titanium(III) atoms is also considered. |