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Crystal Structures of Cs+-Crown Ether Complexes Containing Polynuclear Mercury Iodide Anions

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Abstract

Reactions of CsI and HgI2 with benzo-15-crown-5 (B15C5) and 15-crown-5 (15C5) in an ethanol-acetone mixture produced [Cs(B15C5)2]2[Hg2I6] (1) and {[Cs(15C5)]2[Hg2I6]}n (2), respectively. The structures of the two complexes are quite different. Molar ratios of Cs+ : crown ether are 1 : 2 in 1 and 1 : 1 in 2. Complex 1 consists of two Cs(B15C5) +2 cations and a Hg2I 2-6 anion. Cs+ lies between the two crown-5 ligands, resulting in a sandwich-type cation. Cationic Cs(B15C5) +2 and anionic Hg2I 2-6 are linked together by electrostatic interactions and the complex 1 is an ion pair compound. Complex 2 consists of infinite [Cs(15C5)]2[Hg2I6] units. Each structural unit contains two Cs(15C5)+ cations and a Hg2I 2-6 anion. Cs+ is coordinated by five oxygen atoms of 15C5, three iodine atoms of Hg2I 2-6 , and an iodine atom of Hg2I 2-6 in an adjacent structural unit. The interactions between the Cs+ of Cs(15C5)+ and an I− in Hg2I 2-6 from adjacent structural units polymerize the complex 2, resulting in a one-dimensional network structure. The anions of Hg2I 2-6 in both complexes are similar. The two mercury atoms are linked through two bridging iodine atoms and each mercury is also coordinated by two terminal iodines. Crystal data for 1: space group P21/c (No. 14), a = 12.253(4), b = 20.945(7), c = 16.110(6) Å, β = 111.0(1)°, V = 3860 Å3, Z = 4, R = 0.082 (R w = 0.089). Crystal data for 2: space group P21/c (No. 14), a = 12.157(4), b = 8.546(4), c = 20.666(6) Å, β = 91.54(3)°, V = 2146 Å3, Z = 4, R = 0.034 (R w = 0.048).

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Authors and Affiliations

  1. Department of Chemistry, Zhengzhou University, Zhengzhou, Henan, 450052, P.R. China

    Zhixian Zhou, Hongna Han, Tiesheng Li, Yanjun Xing & Yangjie Wu

  2. Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah, 84602

    Xian Xin Zhang, Reed M. Izatt, N. Kent Dalley & Jerald S. Bradshaw

  3. Chinese Academy of Medical Science, Institute of Material Medica, Beijing, 100050, P.R. China

    Weijie Chai & Cunheng He

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  1. Zhixian Zhou
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  2. Hongna Han
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  3. Tiesheng Li
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  4. Yanjun Xing
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Correspondence to Reed M. Izatt.

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Zhou, Z., Han, H., Li, T. et al. Crystal Structures of Cs+-Crown Ether Complexes Containing Polynuclear Mercury Iodide Anions. Structural Chemistry 10, 177–185 (1999). https://doi.org/10.1023/A:1021832412700

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