Modified Tellurium Subhalides in the New Structure Type [Te15X4]n[MOX4]2n (M = Mo, W; X = Cl, Br)

The reactions of Te2Br with MoOBr3, TeCl4 with MoNCl2/MoOCl3, and Te with WBr5/WOBr3 yield black, needle‐like crystals of [Te15X4][MOX4]2 (M = Mo, W; X = Cl, Br). The crystal structure determinations [Te15Br4][MoOBr4]2: monoclinic, Z = 1, C2/m, a = 1595.9(4) pm, b = 403.6(1) pm, c = 1600.4(4) pm, β = 112.02(2)°; [Te15Cl4][MoOCl4]2: C2/m, a = 1535.3(5) pm, b = 402.8(2) pm, c = 1569.6(5) pm, β = 112.02(2)°; [Te15Br4][WOBr4]2: C2, a = 1592.4(4) pm, b = 397.5(1) pm, c = 1593.4(5) pm, β = 111.76(2)° show that all three compounds are isotypic and consist of one‐dimensional ([Te15X4]2+)n and ([MOX4]−)n strands. The structures of the cationic strands are closely related to the tellurium subhalides Te2X (X = Br, I). One of the two rows of halogen atoms that bridges the band of condensed Te6 rings is stripped off, and additionally one Te position has only 75% occupancy which leads to the formula ([Te15X4]2+)n (X = Cl, Br) for the cation. The anionic substructures consist of tetrahalogenooxometalate ions [MOX4]− that are linked by linear oxygen bridges to polymeric strands. The compounds are paramagnetic with one unpaired electron per metal atom indicating oxidation state Mv, and are weak semiconductors.