The crystal structure and bonding environment of K2Ca(CO3)2 bütschliite were probed under isothermal compression via Raman spectroscopy to 95 GPa and single crystal and powder X-ray diffraction to 12 and 68 GPa, respectively. A second order Birch-Murnaghan equation of state fit to the X-ray data yields a bulk modulus, \({K}_{0}=46.9\) GPa with an imposed value of \({K}_{0}^{\prime}= 4\) for the ambient pressure phase. Compression of bütschliite is highly anisotropic, with contraction along the c-axis accounting for most of the volume change. Bütschliite undergoes a phase transition to a monoclinic C2/m structure at around 6 GPa, mirroring polymorphism within isostructural borates. A fit to the compression data of the monoclinic phase yields \({V}_{0}=322.2\) Å3 \(,\) \({K}_{0}=24.8\) GPa and \({K}_{0}^{\prime}=4.0\) using a third order fit; the ability to access different compression mechanisms gives rise to a more compressible material than the low-pressure phase. In particular, compression of the C2/m phase involves interlayer displacement and twisting of the [CO3] units, and an increase in coordination number of the K+ ion. Three more phase transitions, at ~ 28, 34, and 37 GPa occur based on the Raman spectra and powder diffraction data: these give rise to new [CO3] bonding environments within the structure.
