Synthesis of Halogen-Substituted [12]Mercuracarborands-4. Crystal Structure of {[(9,12-I2-C2B10H8-1,2-Hg)4]Cl}Na(H2O)n

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The reactions of the dilithium derivatives of 9,12-dihalogen-ortho-carboranes 1,2-Li2-C2B10H8-9,12-X2 (X = Cl, Br, I) with mercury chloride HgCl2 afford a number of complexes of the chloride ion with the halogen derivatives of [12] mercuracarborand-4: {[(9,12-X2-C2B10H8-1,2ʹ-Hg)4]Cl}Na · nH2O. The molecular crystal structure of the complex of the
[12]mercuracarborand-4 octaiodine derivative with the chloride ion is determined by X-ray diffraction. The substituents at the periphery of the mercury-containing macrocycle are found to exert a substantial effect on the macrocycle geometry leading to the transition from the planar to butterfly conformation, whose geometry is predetermined by a set of intermolecular interactions in the crystal.

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K. Suponitsky

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

编辑信件的主要联系方式.
Email: kirshik@yahoo.com
俄罗斯联邦, Moscow

S. Anufriev

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: kirshik@yahoo.com
俄罗斯联邦, Moscow

A. Shmalko

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: kirshik@yahoo.com
俄罗斯联邦, Moscow

I. Sivaev

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: sivaev@ineos.ac.ru
俄罗斯联邦, Moscow

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2. Scheme 1

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3. Fig. 1. General view of the complex {[(9,12-I2-C2B10H8-1,2ʹ-Hg)4]Cl}- in the representation of atoms by ellipsoidal thermal vibrations with 50% probability. Given: numbering only for the symmetry-independent part of the macrocycle (a); side view of the macrocycle (b). The angle φ between the ‘butterfly wings’ is defined as the angle between the planes of the ortho-carborane nuclei drawn through the atoms C(1), C(2), B(9), B(12), Hg(1), Hg(2) (shown as green dashed lines)

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4. Fig. 2. Top left: fragment of the crystal packing of complex III (hydrogen atoms and water molecules are not shown). Top and bottom right: the most tightly bound dimeric associates. Intermolecular contacts are shown as dashed lines and their distances are given in Å

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