Acta Crystallographica Section B

Structural Science

Volume 55, Part 3 (June 1999)

Acta Cryst. (1999). B55, 396-409 [doi:10.1107/S010876819801550X]

Polynuclear chloromercurate(II) systems in their chloropyridinium salts

A. Linden, B. D. James, J. Liesegang and N. Gonis

Abstract: The chloromercurate(II) salts of 2-, 3- and 4-chloropyridine display a variety of anion stoichiometries and structures, including the rare [Hg₃Cl₁₀]^4- stoichiometry. 2-Chloropyridinium trichloromercurate(II), (I), (C₅H₅ClN)[HgCl₃], monoclinic, P2₁/n, a = 9.094 (8), b = 18.143 (4), c = 12.902 (3) Å, [beta] = 106.13 (4)° with Z = 8, has the [HgCl₃]^- stoichiometry, but the anions are infinite chains composed of [HgCl₃]^-, HgCl₂ and Cl^- moieties linked by longer HgCl contacts. Hydrogen bonds link the cations to the formal Cl^- ions. Tetrakis(3-chloropyridinium) decachlorotrimercurate(II), (II), (C₅H₅ClN)₄[Hg₃Cl₁₀], monoclinic, P2₁/n, a = 7.522 (2), b = 28.046 (3), c = 9.165 (2) Å, [beta] = 105.78 (2)° with Z = 2, has the rare [Hg₃Cl₁₀]^4- stoichiometry and contains infinite one-dimensional double-stranded {([HgCl₄]^2-)₂ [HgCl₂]}_n anionic chains made up of linear HgCl₂ and distorted [HgCl₄]^2- entities linked together by longer HgCl contacts. The HgCl₂ moieties are joined by double [HgCl₄]^2- bridges. Hydrogen bonds link the cations to the sides of the anionic columns. Tetrakis(4-chloropyridinium) decachlorotrimercurate(II), (III), (C₅H₅ClN)₄[Hg₃Cl₁₀], triclinic, P1, a = 9.907 (3), b = 13.226 (2), c = 7.282 (2) Å, [alpha] = 84.41 (2), [beta] = 74.81 (2), [bold gamma] = 87.34 (2)° with Z = 1, also has the [Hg₃Cl₁₀]^4- stoichiometry and the same type of {([HgCl₄]^2-)₂[HgCl₂]}_n anionic chains that were found in compound (II), but the formal HgCl₂ and [HgCl₄]^2- moieties are more discrete with much weaker contacts linking the individual units. Bifurcated hydrogen bonds with the cations cross-link the anionic chains to form an infinite two-dimensional network. Second forms of the 3- and 4-chloropyridinium salts were also obtained. 3-Chloropyridinium trichloromercurate(II), (IV), (C₅H₅ClN)[HgCl₃], monoclinic, P2₁/c, a = 7.243 (5), b = 22.145 (8), c = 12.320 (3) Å, [beta] = 99.52 (3)° with Z = 8, has the [HgCl₃]^- stoichiometry, but the anions are infinite chains composed of distorted [Hg₂Cl₆]^2- moieties. Bifurcated hydrogen bonds from the cations cross-link the anionic chains to form infinite two-dimensional layers. Bis(4-chloropyridinium) hexachlorodimercurate(II), (V), (C₅H₅ClN)₂[Hg₂Cl₆], monoclinic, C2/m, a = 13.447 (3), b = 7.534 (2), c = 9.939 (2) Å, [beta] = 97.48 (2)° with Z = 2, contains highly symmetrical discrete [Hg₂Cl₆]^2-anions. Bifurcated hydrogen bonds from the cations interconnect the anions to form infinite one-dimensional chains.

Online 1 June 1999


	Structure factor file (CIF format) (201.6 kbytes) Contains datablock I

	Structure factor file (CIF format) (233.7 kbytes) Contains datablock (II)

	Structure factor file (CIF format) (229.9 kbytes) Contains datablock (III)

	Structure factor file (CIF format) (244.6 kbytes) Contains datablock (IV)

	Structure factor file (CIF format) (67.4 kbytes) Contains datablock V

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