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The asymmetric unit of the title compound {(C6H18N2)2[Sb2Br10]·H2O}n, consists of two tetra­methyl­ethylendi­ammonium cations that are located on centres of inversion, as well as one tetra­methyl­ethylendi­ammonium cation, one water mol­ecule, one distorted octahedral [SbBr6]3−anion and one bisphenoidal [SbBr4] anion in general positions. The [SbBr6]3− and [SbBr4] anions are linked together by two long Sb—Br bonds of 3.2709 (8) and 3.5447 (7) Å into {[Sb2Br10]4−}n chains along [001]. One of the three tetra­methyl­ethylendi­ammonium cations is disordered and was refined using a split model (occupancy ratio 0.58:0.42). The cations and the water mol­ecule are connected to the {[Sb2Br10]4−}n polymeric anions by weak N—H ...Br and O(water)—H ...Br hydrogen bonding.

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The asymmetric unit of the title compound, (C7H10NO)2[SnBr6]·2H2O, contains one cation, one half-dianion and one lattice water mol­ecule. The [SnBr6]2− dianion, located on an inversion center, exhibits a highly distorted octa­hedral coordination environment, with Sn—Br bond lengths ranging from 2.2426 (9) to 3.0886 (13) Å. In the crystal, O—H...Br, N—H...Br, N—H...O and C—H...Br hydrogen bonds consolidate the packing, which can be described as consisting of alternating anionic (containing dianions and lattice water mol­ecules) and cationic layers parallel to ab plane.
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