The mono‐, sesqui‐, and dibromides of indium: InBr, In₂Br₃, and InBr₂

Of the four reduced indium bromides, InBr, In 2 Br 3 , InBr 2 , and In 4 Br 7 , synthesis, crystal growth and structure determination of the first three is reported. InBr (orthorhombic), Cmcm, Z = 4, a = 446.6(1), b = 1236.8(2), c = 473.9(1) pm, V m = 39.42(1) cm 3 mol −1 ) crystallizes with the TlI‐type structure. In 2 Br 3 (orthorhombic, Pnma, Z = 16, a = 1300.6(5), b = 1649.8(5), c = 1289.7(9) pm, V m = 104.16(9) cm 3 mol −1 ), isotypic with Ga 2 Br 3 , is according to In 2 [In 2 Br 6 ] a mixed‐valence In I –In II ‐bromid with eclipsed [In 2 Br 6 ] 2− groups with d(In–In) = 268.8 and 271.6 pm, respectively. InBr 2 (In[InBr 4 ]) is a mixed‐valence In I In III bromide with the GaCl 2 ‐type structure (orthorhombic, Pnna, Z = 8, a = 798.6(2), b = 1038.5(2), c = 1042.5(5) pm, V m = 65.09(4) cm 3 mol −1 ).