TY  - JOUR
AU  - Fielden, J.
AU  - Long, D.-L.
AU  - Speldrich, M.
AU  - Kögerler, P.
AU  - Cronin, L.
TI  - [CoxCu1x(DDOP)(OH2)(NO3)](NO3): hydrogen bond-driven distortion of cobalt(II) by solid solution ‘network mismatch’
JO  - Dalton transactions
VL  - 41
SN  - 1477-9226
CY  - London
PB  - Soc.
M1  - PreJuSER-22301
SP  - 4927 - 4934
PY  - 2012
N1  - We thank Claire Besson for suggesting use of the bond-valence method, Georg Seeber for X-ray diffraction data for compound 2, Kevin Lamberts for X-ray diffraction data on the additional solid solutions (ESI) and Geoff Cooper for re-synthesis of 4. JF and DL both acknowledge the EPSRC for funding.
AB  - 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)(H(2)O)(NO(3))](+) 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 [Co(x)Cu(1-x)(DDOP)(NO(3))(H(2)O)](NO(3)), 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 4 in 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.
KW  - J (WoSType)
LB  - PUB:(DE-HGF)16
C6  - pmid:22450432
UR  - <Go to ISI:>//WOS:000302023800030
DO  - DOI:10.1039/c2dt11055e
UR  - https://juser.fz-juelich.de/record/22301
ER  -