Black single crystals of the new dodecahalogenotrimetallate In(4)Ti(3)Br(12) were obtained by reacting InBr(3) with Ti-wire at 450 °C in a silica tube sealed under vacuum. In(4)Ti(3)Br(12) (Pearson symbol hR57, space group R3m, Z = 3, a = 7.3992(8) Å, c = 36.673(6) Å, 643 refl., 25 param., R(1)(F) = 0.025; wR(2)(F(2)) = 0.046) is a defect variant of a 12 L-perovskite. In(+) cations are 12-fold coordinated in two different ways: In1 as an anticuboctahedron and In2 as a cuboctahedron. In both cases the 5s(2) configuration results in 3 short, 6 medium, and 3 long In-Br distances which might be explained as lone pair effect or second order Jahn-Teller instability. Furthermore there are isolated linear trimers [Ti(3)Br(12)](4-) consisting of facesharing octahedra similar to [Ru(3)Cl(12)](4-). The [Ti(3)Br(12)](4-)-unit has to be described as a mixed-valent d(1)-d(2)-d(1) system. According to magnetic measurements, the Ti-atoms in In(4)Ti(3)Br(12) show strong antiferromagnetic interactions (Θ = -1216(6) K) which might be addressed as weak Ti(3+)-Ti(2+)-Ti(3+) bonds. For comparison, single crystals of K(3)Ti(2)X(9) (X = Cl, Br) were synthesized and their structures refined. The rotation of the Ti(2)X(9)(3-) dimers reduced the symmetry of the well-known Cs(3)Cr(2)Cl(9) type from P6(3)/mmc to P6(3)/m and resulted in the formation of merohedral twins. According to the unit cell volumes In(+) is smaller than K(+) in all cases.
Single crystals of NbO2I were obtained as dark red needles by chemical transport. According to the structure determination (Pnma, a = 20.897(4), b = 3.7654(8), c = 3.9715(8) Å , Z = 4, 619 reflections, 26 variables, R1(F) = 0.0645, wR2(F2) = 0.1597) NbO2I represents a new structure type with 7- coordinated Nb atoms. Pentagonal bipyramids NbO5I2 are connected via the apical O atoms with alternating short and long Nb-O distances (1.79 / 2.20 Å ) to chains and via the three equatorial O atoms to double layers. Between the double layers there are only weak van-der-Waals interactions of the I atoms. NbO2I is the first oxide halide of a transition metal with CN 7. Structurally NbO2I is closely related to UO2Br, but with alternating short and long Nb-O distances as a difference.
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