N-(Trimethyl­sil­yl)methane­sulfonamide

Andrew R McWilliams; Sossina Gezahegna; Alan J Lough

doi:10.1107/S1600536810050336

. 2010 Dec 11;67(Pt 1):o93. doi: 10.1107/S1600536810050336

N-(Trimethylsilyl)methanesulfonamide

Andrew R McWilliams ^a,^*, Sossina Gezahegna ^a, Alan J Lough ^b

PMCID: PMC3050205 PMID: 21522802

Abstract

There are two molecules in the asymmetric unit of the title compound, C₄H₁₃NO₂SSi. In the crystal, molecules are linked via intermolecular N—H⋯O hydrogen bonds, forming chains along [001]. The crystal studied was an inversion twin, the refined ratio of twin domains being 0.61 (9):0.39 (9).

Related literature

For the original synthesis of the title compound, see: Roy (1993 ▶). For the synthetic application of the title compound, see: Roy et al. (1993 ▶). For related structures, see: Ni et al. (1995 ▶); Chunechom et al. (1998 ▶).

Experimental

Crystal data

C₄H₁₃NO₂SSi
M _r = 167.30
Monoclinic,
a = 8.2827 (4) Å
b = 10.9513 (5) Å
c = 9.6201 (3) Å
β = 92.536 (2)°
V = 871.75 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 150 K
0.32 × 0.25 × 0.24 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing 1995 ▶) T _min = 0.830, T _max = 0.931
6920 measured reflections
4894 independent reflections
4195 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.094
S = 1.05
4894 reflections
170 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.49 e Å⁻³
Absolute structure: Flack (1983 ▶), 1787 Friedel pairs
Flack parameter: 0.39 (9)

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810050336/si2314sup1.cif

e-67-00o93-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810050336/si2314Isup2.hkl

e-67-00o93-Isup2.hkl^{(239.7KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1B—H1NB⋯O2A	0.81 (2)	2.11 (2)	2.917 (3)	173 (3)
N1A—H1NA⋯O2Bⁱ	0.81 (2)	2.12 (2)	2.925 (3)	177 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

AM would like to thank Ryerson University’s Faculty of Engineering, Architecture and Science for funding.

supplementary crystallographic information

Comment

N-trimethylsilylmethylsulfonamide, a key intermediate in the synthesis of polyoxothiazenes (Roy et al., 1993) and polythionylphosphazenes (Chunechom et al., 1998), was prepared via the reaction of methanesulfonyl chloride and hexamethyldisilazane (Roy, 1993). The asymmetric unit of the title compound, which contains two independent molecules, is shown in Fig. 1. The S—N bond distances in each molecule are intermediate between a typical S—N single bond (1.74 Å) and a typical S=N double bond (1.54 Å), (Ni et al., 1995) suggesting the presence of some π-bonding between the sulfur and nitrogen atoms. The S—N—Si bond angles of 127.83 (14)° and 128.59 (14)Å are larger than might be expected, in terms of hybridization priciples, for either a tetrahedral or trigonal planar geometry about the nitrogen atom. In the crystal structure, molecules are linked via intermolecular N—H···O hydrogen bonds to form one-dimensional chains along [001] (Fig. 2).

Experimental

The title compound was prepared via addition of methanesulfonyl chloride (7 ml, 102.5 mmol) to a three-necked round-bottom flask equipped with a magnetic stirring bar, gas inlet, reflux condenser and a rubber septa under an inert N₂ atmosphere. Hexamethyldisilazane (20 ml, 103.1 mmol) was added drop wise over 10 minutes with stirring at ambient temperatures. The flask was then placed into an oil bath and the reaction mixture heated to 363–373 K to initiate the reaction. The temperature of the oil bath was increased to between 388–393 K and the reaction mixture refluxed at this temperature for 2 h. The reaction mixture was allowed to cool to room temperature and the reaction by-product (Me₃SiCl) was removed in vacuo. The resulting crude white powder was recrystallized from a CH₂Cl₂/Hexane mixture producing colourless crystals. (Yield = 15.6 g, 91%).