Low-temperature single-crystal Raman and neutron-diffraction study of the hydrogenous ammonium copper(II) Tutton salt and the deuterated analogue in the metastable state.
Low-temperature (15 K) single-crystal neutron-diffraction structures and Raman spectra of the salts (NX4)2[Cu(OX2)6](SO4)2, where X=H or D, are reported. This study is concerned with the origin of the structural phase change that is known to occur upon deuteration. Data for the deuterated salt were measured in the metastable state, achieved by application of 500 bar of hydrostatic pressure at approximately 303 K followed by cooling to 281 K and the subsequent release of pressure. This allows for the direct comparison between the hydrogenous and deuterated salts, in the same modification, at ambient pressure and low temperature. The Raman spectra provide no intimation of any significant change in the intermolecular bonding. Furthermore, structural differences are few, the largest being for the long Cu-O bond, which is 2.2834(5) and 2.2802(4) A for the hydrogenous and the deuterated salts, respectively. Calorimetric data for the deuterated salt are also presented, providing an estimate of 0.17(2) kJ/mol for the enthalpy difference between the two structural forms at 295.8(5) K. The structural data suggest that substitution of hydrogen for deuterium gives rise to changes in the hydrogen-bonding interactions that result in a slightly reduced force field about the copper(II) center. The small structural differences suggest different relative stabilities for the hydrogenous and deuterated salts, which may be sufficient to stabilize the hydrogenous salt in the anomalous structural form.
Dobe
Christopher
C
Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3000, Bern 9, Switzerland.
Carver
Graham
G
Bürgi
Hans-Beat
HB
Tregenna-Piggott
Philip L W
PL
McIntyre
Garry J
GJ
Augustyniak-Jablokow
Maria A
MA
Riley
Mark J
MJ