Pressure-induced structural phase transformation in cobalt(II) dicyanamide.

Abstract

In situ synchrotron powder diffraction has been used to probe the pressure-dependent structural properties of the magnetic molecular framework material Co(dca)2 [dca = dicyanamide or N(CN)2(-)]. An orthorhombic (Pmnn) to monoclinic (P2₁/n) transformation to a high-pressure phase, namely γ-Co(dca)2, occurs at 1.1 GPa. Structural determination of γ-Co(dca)2 shows that the rutile-like topology of the pristine material is retained at high pressures, with the lower symmetry allowing a progression of volume-reducing structural distortions. γ-Co(dca)2 was stable at the maximum pressure measured of 4.2 GPa. Both phases were soft, with bulk moduli (B0) for α-Co(dca)2 and γ-Co(dca)2 of 13.15 (18) and 9.0 (6) GPa, respectively. Modest uniaxial negative linear compressibility (K) of the order of -4 TPa(-1) was observed over the entire measured pressure range.