Cyanocobalt(III) complexes of penta- and tetradentate-coordinated macrocyclic hexaamines

Bernhardt, Paul V. and Kilah, Nathan L. (2005) Cyanocobalt(III) complexes of penta- and tetradentate-coordinated macrocyclic hexaamines. Acta Crystallographica Section C-crystal Structure Communications, 61 5: M245-M249. doi:10.1107/S0108270105009261

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Author Bernhardt, Paul V.
Kilah, Nathan L.
Title Cyanocobalt(III) complexes of penta- and tetradentate-coordinated macrocyclic hexaamines
Journal name Acta Crystallographica Section C-crystal Structure Communications   Check publisher's open access policy
ISSN 0108-2701
Publication date 2005-05
Sub-type Article (original research)
DOI 10.1107/S0108270105009261
Open Access Status File (Publisher version)
Volume 61
Issue 5
Start page M245
End page M249
Total pages 5
Editor Frederiksberg C.
Place of publication Copenhagen
Publisher International Union of Crystallography
Language eng
Abstract The pendent-arm macrocyclic hexaamine trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L) may coordinate in tetra-, penta- or hexadentate modes, depending on the metal ion and the synthetic procedure. We report here the crystal structures of two pseudo-octahedral cobalt(III) complexes of L, namely sodium trans-cyano(trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine)cobalt(III) triperchlorate, Na[Co(CN)(C13H30N6)](ClO4)(3) or Na{trans-[CoL(CN)]}(ClO4)(3), (I), where L is coordinated as a pentadentate ligand, and trans-dicyano(trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine) cobalt (III) trans-dicyano (trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diaminium)cobalt(III) tetraperchlorate tetrahydrate, [Co(CN)(2)(Cl4H32N6)][Co(CN)(2)(Cl4H30N6)](ClO4)(4)•-4H(2)O or trans-[CoL(CN)(2)]trans-[Co(H2L)(CN)(2)] (ClO4)(4)•-4H(2)O, (II), where the ligand binds in a tetradentate mode, with the remaining coordination sites being filled by C-bound cyano ligands. In (I), the secondary amine Co-N bond lengths lie within the range 1.944 (3)-1.969 (3) &ANGS;, while the trans influence of the cyano ligand lengthens the Co-N bond length of the coordinated primary amine [Co-N = 1.986 (3) &ANGS;]. The Co-CN bond length is 1.899 (3) &ANGS;. The complex cations in (11) are each located on centres of symmetry. The Co-N bond lengths in both cations are somewhat longer than in (I) and span a narrow range [1.972 (3)-1.982 (3) &ANGS;]. The two independent Co-CN bond lengths are similar [1.918 (4) and 1.926 (4) &ANGS;] but significantly longer than in the structure of (1), again a consequence of the trans influence of each cyano ligand.
Keyword Crystallography
Q-Index Code C1

Document type: Journal Article
Sub-type: Article (original research)
Collections: Excellence in Research Australia (ERA) - Collection
School of Chemistry and Molecular Biosciences
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Citation counts: TR Web of Science Citation Count  Cited 2 times in Thomson Reuters Web of Science Article | Citations
Scopus Citation Count Cited 2 times in Scopus Article | Citations
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Created: Mon, 13 Aug 2007, 15:12:01 EST