Summary
We have carried out low temperature magnetic susceptibility measurements and a redetermination of the crystal and molecular structure of bis(1,5-diazacyclooctane)nickel(II) perchlorate dihydrate from three-dimensional intensity data collected on a CAD4 diffractometer. The structure was refined by full-matrix least-squares to the R value of 6.3% for 1501 observed reflections. The positions of the hydrogen atoms were obtained from the diffraction data. Contrary to our earlier conclusions drawn by inspection of molecular models of bis(diazacyclooctane) complexes, the axial sites in the actual crystal structure are open for ligation. The Ni-N bonds are, however, sterically protected by the coplanar N-H bonds, allowing maximum ligand-field stabilization for the squareplanar geometry around the nickel atom. The observed magnetic transition from a diamagnetic state at room temperature to a paramagnetic state at 78 K is explained on the basis of long-range exchange interactions along sterically unshieldedz axis. The crystal structure is compared with other similar structures.
Similar content being viewed by others
References
G. Maki,J. Chem. Phys., 28, 651 (1938).
H. B. Gray,Transition Met. Chem., 1, 239 (1965).
R. I. Belford, M. Calvin and G. Belford,J. Chem. Phys., 26, 1166 (1965).
D. I. Royer,J. Inorg-.Chem., 11, 151 (1959).
I. M. Procter, B. I. Hathaway and P. Nickolis,J. Chem. Soc. (A), 1678 (1968).
W. K. Musker and M. S. Hussain,Inorg. Chem., 5, 1416 (1966).
W. K. Musker and M. S. Hussain,Inorg. Chem., 8, 528 (1969).
M. S. Hussain,J. Chem. Soc., Dalton Trans., 2545 (1982).
M. S. Hussain,Inorg. Chim. Acta, 69, 227 (1983).
G. D. Khattak, M. S. Hussain, G. W. Hunter and L. E. Wenger,Phys. Status Solidi.(b), 130, 587 (1985).
M. S. Hussain, unpublished results.
S. L. Lawton, TRACERII-Lattice Transformation Cell-Reduction Computer Program (Northwestern Version) April 1967.
G. M. Sheldrick,SHELX76, Programs for Crystal Structure Determination, University of Göttingen, West Germany.
D. T. Cromer and J. B. Mann,Acta Cryst., A24, 3219 (1968).
R. F. Stewart, E. R. Davidson and W. T. Simpson,J. Chem. Phys. 42, 3175 (1965).
D. T. Cromer and D. Liberman,J. Chem. Phys., 53, 1891 (1970).
D. J. Royer, V. H. Schievelbein, A. R. Kalyanaraman and J. A. Bertand,Inorg. Chim. Acta, 6, 307 (1972).
E. D. Steffen and E. D. Stevens,Inorg. Nucl. Chem. Lett., 9, 1011 (1973).
M. S. Hussain and H. Hoppe,Acta Crystallogr., B25, 1866 (1969).
K. M. Diederix, J. P. Groen, T. O. Klaassen, N. J. Poulis and R. L. Carlin,Pysica, 97B, 113 (1979).
S. Arajs and D. S. Miller,J. Applied Phys.,31, 325S (1960).
K. M. Diedrix, H. A. Algra, J. P. Groen, T. O. Klaasen, J. Poulis and R. L. Carlin,Phys. Lett., 60A, 247 (1977).
M. S. Hussain and J. Hwang, unpublished results.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Hussain, M.S., Ahmad, J., Mazhar-ul-Haque et al. The crystal structure and low temperature magnetic susceptibility of square-planar bis(1,5-diazacyclooctane)nickel(II) perchlorate dihydrate. Transition Met Chem 11, 155–159 (1986). https://doi.org/10.1007/BF00637018
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00637018