Compressing arsenic∙∙∙halogen secondary bonds: a high-pressure structural study of arsenic(III)-oxide intercalates with ammonium halides
Abstract
Crystal structures of arsenic(III)-oxide intercalation compounds with ammonium chloride (NH4Cl∙As2O3∙1/2H2O), ammonium bromide (NH4Br∙2As2O3), and ammonium iodide (NH4I∙2As2O3) have been determined under high pressure up to 12, 15 and 11 GPa, respectively. No phase transitions have been observed for the investigated compounds. The compression of arsenic∙∙∙halogen secondary bonds, expressed as penetration indices of the bonds, has been shown to be a linear function of unit-cell volume ratio V/V0, where V0 is unit-cell volume at ambient pressure, with similar slopes as the compression of arsenic∙∙∙oxygen secondary bonds. The behavior of arsenic coordination number, expressed as first-order valence entropy coordination number, at high pressures and the stereoactivity of arsenic lone electron pairs in the studied intercalates are the same as in arsenic(III)-oxide polymorphs – the former decreases linearly with V/V0, while the latter remains unchanged. The high-pressure study lends further support to the fact that the nature of arsenic∙∙∙halogen and arsenic∙∙∙oxygen secondary bonds is the same.