Supramolecular Alcohol–Amine Crystals and Their Hydrogen-Bond Patterns

Abstract

An analysis of the structures of ®ve new cocrystals with saturated hydrogen bonding between amines and alcohols is presented. These ®ve are all cocrystals with p-phenylenediamine (PDA) and a mono-or diol. The cocrystals are. These crystals have two distinctly different supramolecular hydrogen-bond patterns, when considering only the hydroxyl and amine groups. There are, in addition, variations in the ways covalently bonded crosslinks connect these hydrogen-bond networks. The graph sets of the hydrogen-bond networks of these and other published saturated amine±alcohol crystals are compared and suggestions made on how to present the graph-set descriptions, especially those involving in®nite two-and three-dimensional networks of intersecting chains which are characteristic of most of these materials.

p-Phenylenediamine and its dihydrate: two-dimensional isomorphism and mechanism of the dehydration process, and N—H...N and N—H...π interactions

“…It is well known that both aliphatic and aromatic primary amines cocrystallize easily with a variety of mono-and dialcohols (Ermer & Eling 1994;Hanessian et al, 1994;Loehlin et al, 1998;Loehlin & Okasako, 2007), as predicted from the saturated hydrogen-bond principle introduced by Ermer & Eling (1994). In the complementary alcohol/amine system, the total number of donor H atoms matches the number of acceptor lone pairs, whereas primary amines alone show an excess of donor H atoms and a deficit of hydrogen- The proposed mechanism for the transformation of (I) into (II).…”

Aniline–phenol recognition: from solution through supramolecular synthons to cocrystals

“…Could it be that the very formation of a multi-component crystal is already accompanied in the early stages with a funnelling into a certain pathway that is mediated by Á Á ÁO-HÁ Á ÁN-HÁ Á Á hydrogen bonding? The following observations on the ten tetramer structures (seven single-component and three multicomponent) are relevant: (i) in all three multi-component crystals [CSD refcodes FIDLIO, FIDLOU (Vangala et al, 2004) and SARLEC (Loehlin et al, 1998)], the aniline contains more than one -NH 2 group and/or the phenol contains more than one -OH group; (ii) in five of the seven single-component crystals, Á Á Á interactions (stacking of aromatic rings) are present. With these observations, we attempted to formulate a design strategy for aniline-phenol cocrystals that would lend themselves to NMR study in solution, in order that the presence of large synthons (LSAMs) might be detected in solution prior to crystallization.…”

Hydrogen-bond patterns and the structures of 1,4-cyclohexanediol: 2:1 cis:trans-1,4-cyclohexanediol

“…Hydrogen-bonded ladders have not been addressed in any authoritative way to allow a simple graph-set assignment. In an earlier work (Loehlin et al, 1998) we made some suggestions on how to assign graph sets to ladders. In POVSEY (see Fig.…”

“…a a or " e e). We became interested in this compound in connection with our study of alcohol-amine co-crystals (Loehlin et al, 1998) where we were looking for diols with the C-O orientation of hydroxyls antiparallel. We found that mixed-isomer 1,4-CHD was available from Aldrich.…”