Structural studies of indium and thallium insertion into the framework of the cluster compound Ti2Nb6Cl14O4

We have investigated the possibility of altering the electronic configurati on of the niobium oxochloride cluster compound Ti2Nb6Cl14O4 (I) by doping t his material with monovalent cations that can fit: into cavities present in its cluster framework. The doping of I with In+ and Tl+ ions resulted in:t he formation of MxTi2Nb6Cl14-xO4+x (M = In, x = 0.10, 0.20, 0.27; M = Tl, x = 0.10, 0.20) in which the M+ ions partially occupy these cavities. The cr ystal structure analysis indicated that the additional charge provided by M + ions is compensated by substitution of chlorine by oxygen, which leads to the cluster electronic configuration being intact. Crystal data: In0.272Ti 2Nb6Cl13.728O4.272, space group C2/c (No.15), a = 12.679(2) Angstrom, b = 1 4.567(2) Angstrom, c = 12.632(3) Angstrom, beta = 95.26(2)degrees, Z = 4; T l0.196Ti2Nb6Cl13.804O4.196, space group C2/c (no. 15), a = 12.732(1) Angstr om, b = 14.607(2) Angstrom, c = 12.662(2) Angstrom, beta = 95.28(1)degrees, Z = 4.