Different forms of antiparallel stacking of hydrogen-bonded antidromic rings in the solid state: polymorphism with virtually the same unit cell and two-dimensional isostructurality with alternating layers.

As a continuation of a systematic structural analysis of 2-hydroxycycloalkanecarboxylic acids and their carboxamide analogs, the effects of antidromic rings [Jeffrey & Saenger (1991). Hydrogen Bonding in Biological Structures. Berlin, Heidelberg: Springer Verlag] upon the layer stacking of cyclopentane and cycloheptane derivatives are compared. Determination of the structure of trans-2-hydroxycycloheptanecarboxylic acid (2) led to the discovery of two polymorphs with virtually the same unit cell [Kalman et al. (2003). J. Am. Chem. Soc. 125, 34-35]. (i) The layer stacking of the antidromic rings for the whole single crystal is antiparallel (2b). (ii) The antidromic rings and the 21 axis are parallel (2a), consequently the domains of the single crystal must be antiparallel. While their polymorphism is solvent-controlled, they illustrate a novel form of two-dimensional isostructurality. Antiparallel layer stacking is again demonstrated by trans-2-hydroxycycloheptanecarboxamide (3) (space group Pbca). It is built up from layers isostructural with those in the homologous trans-2-hydroxycyclopentanecarboxamide (4) [Kalman et al. (2001). Acta Cryst. B57, 539-550], but in this structure (space group Pca21) the layers are stacked in parallel mode. Similar to (2a) and (2b), the antiparallel layer stacking in (3) versus their parallel array in (4) illustrates the two-dimensional isostructurality with alternating layer orientations. Although (3) and (4) display isostructurality, they are not isomorphous.