Polysulfonylamines, CXCII. Polynary compounds based upon di(4-fluorobenzenesulfonyl)amine (FAH), 1,1,3-trimethylurea (TrMU) and dimethylamine (Me_2NH): Formation and structures of the cocrystal FAH · TrMU (Z' = 1), the salt Me_2NH_2+ · FA-(Z' = 6) and the salt cocrystal FAH · TrMU · Me_2NH_2 + · FA-(Z' = 1).

摘要

Cocrystallization of di(4-fluorobenzenesulfonyl)amine, (4-F-C_6H_4SO_2)_2NH (= FAH), with 1,3,3-trimethylurea (TrMU) from dichloromethane/petroleum ether afforded the molecular cocrystal FAH · TrMU (1, monoclinic, P2_1, Z' = 1) and the salt cocrystal FAH · TrMU · Me_2NH_2~+ · FA-(2, monoclinic, P2_1, Z' = 1). The minor product 2 resulted from a hydrolysis reaction of TrMU and was obtained by serendipity. The salt component of 2, Me_2NH_2~+ · FA-(3, monoclinic, C_2, Z' = 6), was prepared by metathesis of [Me_2NH_2]Cl with Ag[FA] and is not isomorphous to its previously reported congeners Me_2NH_2 + · (4-X-C_6H_4SO_2)_2N-(4 -7 for X = Cl, Br, I or Me, all monoclinic, Cc, Z' = 1). The three new structures display one-dimensional arrays (catemers) based upon classical two-or three-centre hydrogen bonds that use N-H or N+-H groups as donors and S=O, C=O or N-groups as acceptors. In 1, the catemers consist of alternating FAH and TrMU molecules, in 3 of alternating Me2NH2 + and FA-ions (six independent formula units), in 2 of alternating Me_2NH_2 + and FA-ions (one independent unit) and FAH ? TrMU ? heterodimers acting as side-groups to the ionic polymer. The packings of 1 -3 are completely devoid of short fluorine-oxygen contacts below the van derWaals limit, as are all the known crystal structures containing FAH or FA-entities ("oxophobia" of the C-F groups). The Z' = 6 structure of 3 may be interpreted as a stratagem to avoid short F ? O contacts, in contrast to the Z' = 1 structures of 4 -6, which exhibit hydrogen-bonded ion catemers similar to the catemer of 3, and two halogen bonds C-X ? O=S per formula unit.