The copper sulfate hydration cycle. Crystal structures of CuSO4 (Chalcocyanite), CuSO4·H2O (Poitevinite), CuSO4·3H2O (Bonattite) and CuSO4·5H2O (Chalcanthite) at low temperature using non-spherical atomic scattering factors
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Date
2022
Authors
Ibrahim, Mukaila A.
Boeré, René T.
Journal Title
Journal ISSN
Volume Title
Publisher
Royal Society of Chemistry
Abstract
New structure determinations of CuSO4, CuSO4 H2O, CuSO4 3H2O and CuSO4 5H2O are reported from X-ray
diffraction experiments at 100 (1) K. Combined density functional theory (ORCA) and non-spherical atomic
scattering factor (NoSpherA2) computations enabled a Hirshfeld Atom Refinement (HAR) using custom atom
scattering factors, accurately polarized and charge-compensated atom electron densities and accurate
placement and shapes of the water hydrogen atoms. The results clearly demonstrate that all H atoms are
involved in conventional H-bonding in the structures of the hydrates, contrary to an early X-ray diffraction
determination on CuSO4 3H2O. Comparison to neutron diffraction results demonstrates the efficacy of this
new HAR method. Colour variation in copper sulfates is interpretable by considering the relative number of
sulfato and aqua ligands, given the lower crystal field splitting of the former relative to the latter.
Description
Accepted author manuscript.
Keywords
Crystal structures , Atom scattering , Chalcocyanite , Poitevinite , Bonattite , Chalcanthite
Citation
Ibrahim, M. A., & Boeré, R. T. (2022). The copper sulfate hydration cycle. Crystal structures of CuSO4 (Chalcocyanite), CuSO4·H2O (Poitevinite), CuSO4·3H2O (Bonattite) and CuSO4·5H2O (Chalcanthite) at low temperature using non-spherical atomic scattering factors. New Journal of Chemistry, 46(12), 5479-5488. https://doi.org/10.1039/D2NJ00169A