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SbCI3, BiCl3 and Na+ Complexes of Maleonitrile-Dithiacrown Ethers: Synthesis, Crystal Structures and DEP-MS Experiments

Drexler, Hans-Joachim, Starke, Ines, Grotjahn, Manuela, Reinke, Helmut, Kleinpeter, Erich, Holdt, Hans-Jürgen
Zeitschrift für Naturforschung B 2014 v.54 no.6 pp. 799-806
acetonitrile, antimony, cations, crystal structure, ethers, oxygen, sodium, stereochemistry, sulfur
The reactions of MlC₃ (M = Sb, Bi) with maleonitrile-dithia-15-crown-5 (mn-15S₂O₃) and maleonitrile-dithia-18-crown-6 (mn-18S₂O₄) in MeCN yielded the complexes [MCl₃(mn-15S₂O₃)] {M = S b (l), Bi(2)} and [MCl₃(mn-18S₂O₄)] {M = Sb(3), Bi(4)}, respectively. The pyramidal MCl₃ units are coordinated very weakly to the three oxygen and two sulphur donor atoms of mn-15S₂O₃ in 1 and 2, and to the four oxygen donor atoms of mn- 18S₂O₄ in 3 and 4. Both mn-15S₂O₃ complexes, 1 and 2, crystallize isotypically in the m onoclinic space group P2(1)/n with four formula units per unit cell, while the isotypic mn-18S₂O₄ complexes, 3 and 4, are triclinic, space group P-1, with two formula units per unit cell. In the SbCl₃ complexes, 1 and 3, the mean contact distances between the Sb centres and the macrocyclic donor atoms are longer than the corresponding distances in their isostructural BiCl₃ analogues, 2 and 4, which may reflect a stereochemical activity of the Sb¹¹¹ lone pair. Under the conditions of DEP-M S experiments with 1 and 3 the monocationic SbCl₂⁺ complexes [SbCl₂(L)]⁺ (L = mn-15S₂O₃, mn-18S₂O₄) were detected. NaSbCl₆ and mn-18S₂O₄ in MeCN furnished the 2:1 complex [Na(mn-18S₂O₄)₂]SbCl₆ {(5)SbCl₆). In the complex cation 5 the sodium atom is coordinated sandwich-like through the eight oxygen atoms of two mn-18S₂O₄ molecules. Compound (5)SbCl₆ crystallize in the triclinic space group P -1 with two formula units per unit cell