Solid State Supramolecular Complexes [Hg6As4](CuX3)2 (X = Cl, Br): One-Dimensional Helical Guest in a Three-Dimensional Host Framework

• Published in: Journal of cluster science 2005-06, Vol.16 (2), p.273-285
• Main Authors: Oleneva, Olga S., Olenev, Andrei V., Dikarev, Evgeny V., Shevelkov, Andrei V.
• Format: Article
• Language: English
• Subjects: Crystal structure; Electrons; Tetrahedra; Unit cell
• ISSN: 1040-7278; 1572-8862
• DOI: 10.1007/s10876-005-4548-y

Two new supramolecular complexes, [Hg6As4](CuBr3)2 (1) and [Hg6As4](CuCl3)2 (2), have been synthesized and their crystal structures have been determined. Compound 1 crystallizes in the monoclinic system, space group I2/a (No. 15), with the unit cell dimensions a = 14.884(3), b = 9.358(2), c = 20.413(4) Å, β=92.88(3)°, and Z = 6. The crystal structure is comprised of the three-dimensional [Hg6As4]4+ polycationic framework hosting one-dimensional 6-step helical (CuBr guest chains built of the [CuBr4] tetrahedra sharing two of their vertexes. The complex 2 exhibits a distorted variant of the same type of crystal structure (space group I2/a, a = 14.690(1), b = 9.1851(7), c = 20.285(1) Å, β=92.170(1), and Z = 6) that is characterized by a multifarious positioning of the guest anions in the cavities of the perfectly ordered [Hg6As4]4+ host framework. Structures of the title supramolecular assemblies and the previously reported silver-containing analogue [Hg6As4](AgCl3)2 are discussed taking into account the principles of host–guest complementarity.