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cis-trans Isomers of PtX4L2 (X=halogen and L=neutral ligand): trans -bis(dimethyl sulfide)tetraiodidoplatinum(IV)

van Rensburg, J. Marthinus Janse; Oskarsson, Åke LU and Roodt, Andreas (2008) In Acta Crystallographica. Section C: Crystal Structure Communications 64. p.40-42
Abstract
The octahedral title complex, [PtI4(C2H6S)2] or trans PtI4(dms)2 (dms is dimethylsulfide), crystallizes in the monoclinic space group P21/n (Z=2) with molecular symmetry Ci, which is the most frequently occurring point group for trans-PtX4L2[56%, 28 structures in the Cambridge Structural Database (CSD) [Allen, 2002, Acta Cryst B58, 380-388]] followed by C1 (22%, 11 structures). The complexes form a puckered pseudo-hexagonal layer in the (10-1) plane, and the layers are stacked with an interplanar distance of 7.10 Å. Density functional theory (DFT) calculations on an isolated complex with the observed parameters as a starting structure converged to C2h. Constraints to Ci on the observed geometry give 3-4 kJ mol-1 higher energy compared with... (More)
The octahedral title complex, [PtI4(C2H6S)2] or trans PtI4(dms)2 (dms is dimethylsulfide), crystallizes in the monoclinic space group P21/n (Z=2) with molecular symmetry Ci, which is the most frequently occurring point group for trans-PtX4L2[56%, 28 structures in the Cambridge Structural Database (CSD) [Allen, 2002, Acta Cryst B58, 380-388]] followed by C1 (22%, 11 structures). The complexes form a puckered pseudo-hexagonal layer in the (10-1) plane, and the layers are stacked with an interplanar distance of 7.10 Å. Density functional theory (DFT) calculations on an isolated complex with the observed parameters as a starting structure converged to C2h. Constraints to Ci on the observed geometry give 3-4 kJ mol-1 higher energy compared with C2h. DFT calculations on [PtCl4(PzH)2] (PzH is pyrazole), reported in the CSD in both the cis and trans forms, show an energy difference of 21 kJ mol-1 in favour of the trans complex. A CSD search for PtX4L2-type complexes, where X is a halogen and L is a ligand with a donor atom from group 14, 15 or 16, indicated a preferred trans geometrical arrangement, with a total fraction of 68%. The dominating crystal packing operators for the trans complexes are an inversion centre combined with a screw axis/glide plane (48%), followed by an inversion centre alone (28 %). (Less)
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organization
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Contribution to journal
publication status
published
subject
keywords
data mining, platinum complexes, crystallography
in
Acta Crystallographica. Section C: Crystal Structure Communications
volume
64
pages
40 - 42
publisher
International Union of Crystallography
external identifiers
  • wos:000252881500016
  • scopus:38749103542
ISSN
0108-2701
DOI
10.1107/S0108270107060799
language
English
LU publication?
yes
id
42ec4aed-1e2f-48f7-918c-40dc60a19823 (old id 937975)
date added to LUP
2008-01-22 17:19:24
date last changed
2017-01-01 06:34:32
@article{42ec4aed-1e2f-48f7-918c-40dc60a19823,
  abstract     = {The octahedral title complex, [PtI4(C2H6S)2] or trans PtI4(dms)2 (dms is dimethylsulfide), crystallizes in the monoclinic space group P21/n (Z=2) with molecular symmetry Ci, which is the most frequently occurring point group for trans-PtX4L2[56%, 28 structures in the Cambridge Structural Database (CSD) [Allen, 2002, Acta Cryst B58, 380-388]] followed by C1 (22%, 11 structures). The complexes form a puckered pseudo-hexagonal layer in the (10-1) plane, and the layers are stacked with an interplanar distance of 7.10 Å. Density functional theory (DFT) calculations on an isolated complex with the observed parameters as a starting structure converged to C2h. Constraints to Ci on the observed geometry give 3-4 kJ mol-1 higher energy compared with C2h. DFT calculations on [PtCl4(PzH)2] (PzH is pyrazole), reported in the CSD in both the cis and trans forms, show an energy difference of 21 kJ mol-1 in favour of the trans complex. A CSD search for PtX4L2-type complexes, where X is a halogen and L is a ligand with a donor atom from group 14, 15 or 16, indicated a preferred trans geometrical arrangement, with a total fraction of 68%. The dominating crystal packing operators for the trans complexes are an inversion centre combined with a screw axis/glide plane (48%), followed by an inversion centre alone (28 %).},
  author       = {van Rensburg, J. Marthinus Janse and Oskarsson, Åke and Roodt, Andreas},
  issn         = {0108-2701},
  keyword      = {data mining,platinum complexes,crystallography},
  language     = {eng},
  pages        = {40--42},
  publisher    = {International Union of Crystallography},
  series       = {Acta Crystallographica. Section C: Crystal Structure Communications},
  title        = {cis-trans Isomers of PtX4L2 (X=halogen and L=neutral ligand): trans -bis(dimethyl sulfide)tetraiodidoplatinum(IV)},
  url          = {http://dx.doi.org/10.1107/S0108270107060799},
  volume       = {64},
  year         = {2008},
}