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The dinuclear compound, [Nb2Cl6(C2H6S)1.7(C2H6Se)1.3], features an NbIII=NbIII double bond [2.6878 (5) Å]. The mol­ecule lies on a twofold rotation axis that passes through the middle of this bond as well as through the bridging dimethyl sulfide ligand. The NbIII ion exists in an octa­hedral coordination environment defined by two terminal and two bridging Cl atoms, and (CH3)2Se/(CH3)2S ligands. The (bridging) ligand lying on the twofold rotation axis is an ordered (CH3)2S ligand, whereas the terminal ones on a general position are a mixture of (CH3)2Se and (CH3)2S ligands in a 0.647 (2):0.353 (2) ratio (the methyl C atoms are also disordered).

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The title salt, C20H42N4S22+·2ClO4, was obtained from the reaction of bis­(diethyl­amino)­carbeniumdithio­carboxyl­ate, (Et2N)2C2S2, with Fe(ClO4)2·6H2O in CH2Cl2. The title compound, in which one of the S atoms of (Et2N)2C2S2 is bound to a 1,1-bis­(diethyl­amino)­ethane moiety, has two carbenium C atoms, and the charge compensation is provided by two perchlorate anions. The N2C—CS2 bond length is 1.512 (4) Å, corresponding to a C—C single bond, and the dihedral angle between N2C– and –CS2 planes [72.0 (2)°] is smaller than that of (Et2N)2C2S2 [82.0 (1)°]. The crystal structure features C—H...S hydrogen bonds.
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