Origins of contrasting copper coordination geometries in crystalline copper sulfate pentahydrate

Abstract

), with the solution versus gas-phase configurations under debate. The differences are often attributed to the intermolecular interactions between the bulk solvent and the aquated complex, resulting in structures stabilized by extended hydrogen-bonding networks. Yet solution phase systems are difficult to study due to the lack of atomic-level positional details. Crystalline solids are ideal models for comparative study, as they contain fixed structures that can be fully characterized using diffraction techniques. Here, crystalline copper sulfate pentahydrate (CuSO 4 Á5H 2 O), which contains two unique copper-water geometries, was studied in order to elucidate the origin of these contrasting hydrated metal envrionments. A combination of solid-state density functional theory and low-temperature X-ray diffraction was used to probe the electronic origins of this phenomenon. This was accomplished through implementation of crystal orbital overlap population and crystal orbital Hamiltonian population analyses into a developmental version of the CRYSTAL14 software. These new computational methods help highlight the delicate interplay between electronic structure and metal-water geometries.

Pressure-induced non-innocence in bis(1,2-dionedioximato)Pt(ii) complexes: an experimental and theoretical study of their insulator–metal transitions

“…Single point energy calculations were performed on a larger Monkhorst-Pack net of 24 Â 24 Â 24 to compute the densities of states and crystal orbital Hamiltonian populations (COHP). 52 Band structure calculations were performed on a Monkhorst-Pack net of 16 Â 16 Â 16, as no significant improvement was observed on increasing the grid size. Band structures and densities of states (DOS) have been used in combination with crystalline orbitals (CO) and COHP plots to analyse the electronic composition of the bands present in the crystal structures at different pressures.…”

Hydrogen bonding and structural complexity of the Cu3(AsO4)(OH)3 polymorphs (clinoclase, gilmarite): a theoretical study

“…The Peintinger-Oliveira-Bredow split-valence triple-ζ (pob-TZVP) basis sets (Peintinger et al 2013) were used for all atoms along with the hybrid Becke-3-Lee-Yang-Parr (B3LYP) functional, which provides excellent results for copper oxysalt crystals (Ruiz et al 2006;Ruggiero et al 2015;Krivovichev et al 2016a, b). Geometry optimization was initiated with experimental determined crystal-structure models determined for clinoclase and gilmarite by Eby and Hawthorne (1990) and Sarp and Černý (1999), respectively (Tab.…”

Hydrogen bonding system in euchroite, Cu2(AsO4)(OH)(H2O)3: low-temperature crystal-structure refinement and solid-state density functional theory modeling

“…4a). Since gas-phase Cu-H 2 O configurations are always planar (Bryantsev et al 2008), their bending in solid state is usually attributed to the external forces such as a crystalline packing strain and the formation of hydrogen bonds to adjacent anions (Ruggiero et al 2015), which is observed in the crystal structure of euchroite.…”

“…The Peintinger − Oliveira − Bredow split-valence triple-ζ (pob-TZVP) basis sets (Peintinger et al 2013) were used for all atoms along with the hybrid Becke-3 − Lee − Yang − Parr (B3LYP) functional, which provides excellent results for copper oxysalt crystals (Ruiz et al 2006;Ruggiero et al 2015). Geometry optimization was initiated with experimentally determined atomic coordinates and the H atoms were allowed to relax.…”