Negative Linear Compressibility in Organic Mineral Ammonium Oxalate Monohydrate with Hydrogen Bonding Wine-Rack Motifs

Negative linear compressibility (NLC) is a relatively uncommon phenomenon and rarely studied in organic systems. Here we provide the direct evidence of the persistent NLC in organic mineral ammonium oxalate monohydrate under high pressure using synchrotron X-ray powder diffraction, Raman spectroscopy and density functional theory (DFT) calculation. Synchrotron X-ray powder diffraction measurement reveals that ammonium oxalate monohydrate shows both positive and negative linear compressibility along b-axis before 11.5 GPa. The red shift of the external Raman modes and abnormal changes of several selected internal modes in high-pressure Raman spectra further confirmed the NLC. DFT calculations demonstrate that the N-H···O hydrogen bonding "wine-rack" motifs result in the NLC along b-axis in ammonium oxalate monohydrate. We anticipate the high-pressure study of ammonium oxalate monohydrate may represent a promising strategy for accelerating the pace of exploitation and improvement of NLC materials especially in organic systems.