Polysulfonylamine, CXCII [1]. Polynäre Verbindungen aus Di(4-fluorbenzolsulfonyl) amin (FAH), 1,1,3-Trimethylharnstoff (TrMU) und Dimethylamin (Me 2 NH): Bildung und Strukturen des Cokristalls FAH·TrMU (Z′ = 1), des Salzes Me 2 NH 2 +·FA– (Z′ = 6) und des Salz-Cokristalls FAH·TrMU·Me 2 NH 2 +·FA– (Z′ = 1). Bemerkungen zur Oxophobie von C–F-Gruppen in Kristallstrukturen / Polysulfonylamines, CXCII. Polynary Compounds Based upon Di(4-fluorobenzenesulfonyl)amine (FAH), 1,1,3-Trimethylurea (TrMU) an

• Published in: Zeitschrift für Naturforschung. B, A journal of chemical sciences Vol. 66; no. 11; pp. 1161 - 1174
• Main Authors: Wölper, Christoph, Rodríguez-Gimeno, Alejandra, Iborra, Katherine Chulvi, Dix, Ina, Freytag, Matthias, Jones, Peter G., Blaschette, Armand
• Format: Journal Article
• Language: English
• Published: 01-11-2011
• ISSN: 0932-0776; 1865-7117
• DOI: 10.1515/znb-2011-1112

Cocrystallization of di(4-fluorobenzenesulfonyl)amine, (4-F-C
6
H
4
SO
2
)
2
NH (= FAH), with 1,3,3- trimethylurea (TrMU) from dichloromethane/petroleum ether afforded the molecular cocrystal FAH・TrMU (1, monoclinic, P2
1
/n, Z′ = 1) and the salt cocrystal FAH・TrMU・Me
2
NH
2
+
・FA
−
(2, monoclinic, P21, Z′ = 1). The minor product 2 resulted from a hydrolysis reaction of TrMU and was obtained by serendipity. The salt component of 2, Me
2
NH
2
+
・FA
−
(3, monoclinic, C2, Z′ = 6), was prepared by metathesis of [Me
2
NH
2
]Cl with Ag[FA] and is not isomorphous to its previously reported congeners Me
2
NH
2
+
・(4-X-C
6
H
4
SO
2
)
2
N
−
(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 Me
2
NH
2
+
and FA
−
ions (six independent formula units), in 2 of alternating Me
2
NH
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
Polysulfonylamine, CXCII [1]. Polynäre Verbindungen aus Di(4-fluorbenzolsulfonyl) amin (FAH), 1,1,3-Trimethylharnstoff (TrMU) und Dimethylamin (Me
2
NH): Bildung und Strukturen des Cokristalls FAH·TrMU (Z′ = 1), des Salzes Me
2
NH
2
+·FA– (Z′ = 6) und des Salz-Cokristalls FAH·TrMU·Me
2
NH
2
+·FA– (Z′ = 1). Bemerkungen zur Oxophobie von C–F-Gruppen in Kristallstrukturen / Polysulfonylamines, CXCII. Polynary Compounds Based upon Di(4-fluorobenzenesulfonyl)amine (FAH), 1,1,3-Trimethylurea (TrMU) and Dimethylamine (Me
2
NH): Formation and Structures of the Cocrystal FAH·TrMU (Z′ = 1), the Salt Me
2
NH
2
+·FA− (Z′ = 6) and the Salt Cocrystal FAH·TrMU·Me2NH2 +·FA− (Z′ = 1). Comments on the Oxophobia of C–F Groups in Crystal Structures