Uniaxial negative thermal expansion facilitated by weak host–guest interactions

Abstract

A nitromethane solvate of 18-crown-6 was investigated by means of variable-temperature single-crystal X-ray diffraction in response to a report of abnormal unit cell contraction. Exceptionally large positive thermal expansion in two axial directions and negative thermal expansion along the third was confirmed. The underlying mechanism relies exclusively on weak electrostatic interactions to yield a linear thermal expansion coefficient of −129 × 10⁻⁶ K⁻¹, the largest negative value yet observed for an organic inclusion compound.