Hexamethylenetetramine-tridecanedioic acid (1/1): temperature-induced order-disorder structural phase transitions with phase co-existence.

The cocrystal hexamethylenetetramine-tridecanedioic acid (1/1) (HMT-C13), C 6 H 12 N 4 ·C 13 H 24 O 4 , was investigated by single-crystal X-ray diffraction techniques at several temperatures during cooling and heating processes. Our results show the formation of two crystalline phases, separated by a large temperature phase co-existence between 290 and 340 K. Phase I, stable above 341 K, presents an orthorhombic structure described in the space group Bmmb, with one N 4 (CH 2 ) 6 ·C 13 H 22 O 4 adduct in its asymmetric unit. Phase II, stable below 290 K, presents a monoclinic symmetry described by the space group P2 1 /c, with two N 4 (CH 2 ) 6 ·C 13 H 22 O 4 adducts in its asymmetric unit. The phase co-existence is observed both upon cooling and heating, and seems to be related to a complex domain-growth dynamic within the crystal.