Partial ordering of tripivaloylmethane at 110 K

Abstract

Tripivaloylmethane [systematic name: 4-(2,2-dimethylpropanoyl)-2,2,6,6-tetramethylheptane-3,5-dione], C(16)H(28)O(3), is known to crystallize at room temperature in the space group R3m with three molecules in the unit cell. The molecules are conformationally chiral and pack so that each molecular site is occupied with equal probability by the two enantiomers. Upon cooling to 110 K, the structure partially orders; two molecules in the unit cell order into two different conformations of opposite chirality, while the third remains disordered. The symmetry of the resulting crystal is P3, with each of the molecules lying about a different threefold rotation axis. This paper describes an unusual case of order-disorder phase transition in which the structure partially orders by changes of molecular conformation in the single crystals. Such behaviour is of interest in the study of phase transitions and molecular motion in the solid state.

Bulk polarity of 3,5,7-trinitro-1-azaadamantane mediated by asymmetric NO2(lone pair)...NO2(π-hole) supramolecular bonding

“…Such a combination of the stacks has precedents for the packing of some C 3v -pyramidal species, for example, tris(3,5dimethylpyrazol-1-yl)methane (Ochando et al, 1997) and tripivaloylmethane (Stilinović & Kaitner, 2008). The present crystal structure extends the family of C 3v -symmetric molecules to trisubstituted adamantanes.…”