Trifluoromethanesulfonamide: X‐ray single‐crystal determination and quantum chemical calculations

E-ISSN： 1099-1395|28|7|485-489

ISSN： 0894-3230

Source： JOURNAL OF PHYSICAL ORGANIC CHEMISTRY (ELECTRONIC), Vol.28, Iss.7, 2015-07, pp. : 485-489

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Abstract

The X‐ray single‐crystal structure of 1,1,1‐trifluoromethanesulfonamide (triflamide) CF3SO2NH2, which is the ancestor of a large family of its derivatives, has been determined. The crystal structure is composed of infinite layers with an interlayer distance of 3.4 Å. Geometry optimization at the Møller‐Plesset (MP2) and density functional theory (DFT) level showed the calculated bond distances to be, as a rule, longer than the experimental ones. A trial to simulate crystal packing effect on the geometrical parameters by calculating the dimer of triflamide in the gas phase failed – the starting X‐ray geometry of the ‘dimeric’ unit with one NH···O=S H‐bond – was optimized to the cyclic dimer with two H‐bonds. However, when the external (crystal) field effect was simulated using the polarizable continuum model, the experimental geometry of the ‘dimeric’ fragment was satisfactorily reproduced. Calculations of the heptamer cluster having the structure of the hexagon with six triflamide molecules in vertices and one in the middle nicely reproduce the X‐ray structure and brings the geometrical parameters closer to the experiment. Copyright © 2015 John Wiley & Sons, Ltd.