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Issue 16, 2012
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[CoxCu1−x(DDOP)(OH2)(NO3)](NO3): hydrogen bond-driven distortion of cobalt(ii) by solid solution ‘network mismatch’

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Late-first row transition metal nitrate complexes of the tetradentate N-donor ligand cis-3,5-bis[(2-pyridinyleneamino]-trans-hydroxycyclohexane (DDOP) adopt a mono-cationic [M(DDOP)(H2O)(NO3)]+ structure (M = Co, 1; Cu, 2; Zn, 3) in which the DDOP ligand occupies the equatorial plane. The complexes are essentially isostructural and isomorphous, allowing the Co(II) and Cu(II) complexes to co-crystallize in mixed-metal solid solutions with the formula [CoxCu1−x(DDOP)(NO3)(H2O)](NO3), where x = 0.4 (4), 0.1 (5), and 0.7 (6). For 4, structural and magnetochemical analysis indicate that the geometry of the octahedral Co(II) complex distorts to match that of the dominant Jahn–Teller distorted Cu(II) center. Magnetic susceptibility data of octahedral Co(II) are sensitive to ligand geometry distortions and have been analyzed accordingly, comparing 4 to the reference systems 1 and 2. Bond valence calculations have been used to estimate the relative stabilities of the six hydrogen bonded networks, suggesting that the stretching of the Co(II) coordination sphere in 4 is assisted by adoption of the most stable hydrogen bonded network; but that in 6 this is overcome by a higher loading of Co. This family of complexes therefore represent predictable metal-based tectons which can help probe the influence of secondary non-covalent interactions over metal coordination geometries and properties.

Graphical abstract: [CoxCu1−x(DDOP)(OH2)(NO3)](NO3): hydrogen bond-driven distortion of cobalt(ii) by solid solution ‘network mismatch’

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Article information

22 Jan 2012
08 Feb 2012
First published
09 Mar 2012

Dalton Trans., 2012,41, 4927-4934
Article type

[CoxCu1−x(DDOP)(OH2)(NO3)](NO3): hydrogen bond-driven distortion of cobalt(II) by solid solution ‘network mismatch’

J. Fielden, D. Long, M. Speldrich, P. Kögerler and L. Cronin, Dalton Trans., 2012, 41, 4927
DOI: 10.1039/C2DT11055E

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