In:
Zeitschrift für Naturforschung B, Walter de Gruyter GmbH, Vol. 38, No. 3 ( 1983-3-1), p. 357-364
Abstract:
The tetrakis (halomercuri) methane dimethylsulfoxide solvates C(HgX) 4 · DMSO (X = Cl and Br) have been prepared. - The crystal structure of the chloro compound C(HgCl) 4 · DMSO has been determined (R = 0.0611 and Rw = 0.0562). The compound crystallizes in space-group P2 1 /n with a = 1854(1) pm, b = 727.3(5) pm, c = 1049.1(6) pm, β = 94.82(3)°, Z = 4; d c = 4.873 g·cm -3 , d 0 = 4.51 g-cm -3 . - The C(HgCl) 4 molecules have C-Hg bond lengths in the range 201.4(26) to 209.9(27) pm (average 207.0 pm), and Hg-Cl bonds between 231.4(9) and 234.2(9) pm (average 233.2 pm). The bond angles Hg-C-Hg vary from 107.3(3) to 111.7(4)° (average 109.5°), and the angles C-Hg-Cl are found within the limits 172.2(24) and 178.3(25)° (mean 174.3°). DMSO molecules (S-O bond 148.6(23)pm) are coordinated via oxygen to two Hg atoms of one C(HgCl) 4 molecule and to one Hg atom of a neighbouring C(HgCl) 4 molecule forming two bifurcated bridges in a dimer [C(HgCl) 4 · DMSO] 2 ; two strong Cl→···Hg and two weak S→···Hg interactions also contribute to this pair formation. The dimeric units are arranged to layers in the planes (100) and (200), such that each C(HgCl) 4 molecule has six C(HgCl) 4 and two DMSO molecules as neighbours; with two C(HgCl) 4 molecules from each adjacent layer, each C(HgCl) 4 molecule achieves a total coordination number of ten. Depending on the van der Waals radius assumed for mercury a packing coefficient 0.640 ≤ k ≤ 0.691 is obtained. - Cryoscopy and vibrational spectrometry suggest monomeric, unperturbed tetrahedral C(HgX) 4 molecules in DMSO solutions.
Type of Medium:
Online Resource
ISSN:
1865-7117
,
0932-0776
DOI:
10.1515/znb-1983-0315
Language:
English
Publisher:
Walter de Gruyter GmbH
Publication Date:
1983
detail.hit.zdb_id:
2078109-X
detail.hit.zdb_id:
124635-5
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