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The crystal structure of N-methyl­methanesulfon­amide, C2H7NO2S, which is liquid under ambient conditions, has been determined at low temperature. Both the methyl group and H atom bonded to the amide N atom are in a gauche conformation with respect to the sulfonyl methyl group; the C-N-S-C and H-N-S-C torsion angles are -65.57 (20) and 71 (2)°, respectively. This finding is in contrast to previously published ab initio calculations for this mol­ecule.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802006244/ya6094sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802006244/ya6094Isup2.hkl
Contains datablock I

CCDC reference: 185783

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](N-C) = 0.003 Å
  • R factor = 0.035
  • wR factor = 0.083
  • Data-to-parameter ratio = 11.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Amber Alert Alert Level B:
ABSTM_02 Alert B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75 Tmin and Tmax reported: 0.528 0.963 Tmin' and Tmax expected: 0.729 0.869 RR' = 0.654 Please check that your absorption correction is appropriate. General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.902 Tmax scaled 0.869 Tmin scaled 0.476
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
0 Alert Level C = Please check

Comment top

Calculations performed on simple sulfonamides (Heyd et al., 1997; Liang et al., 1997; Nicholas et al., 1991; Bindal et al., 1990) suggest that two energy minima exist. A pyramidal N atom is calculated, with the global minimum exhibiting both the N—H and N—C bonds eclipsing SO double bonds (Fig. 1a). The second local minimum corresponds to a staggered conformation with both the N—H and N—C bonds in a gauche conformation with respect to the S—C bond (Fig. 1 b).

The energy difference between the two conformers for N-methylmethanesulfonamide has been calculated to be between 6.02 kJ mol-1 at the RHF/6–31G* level (Nicholas et al., 1991) and 11.00 kJ mol-1 at the MP2/6–31+G* level (Liang et al., 1997). Assuming a Boltzmann distribution, the higher energy conformer would be present at about a 7% level at 273 K. Reviews of sulfonamide crystal structures (Bock et al., 1998) retrieved from the Cambridge Structural Database (Allen & Kennard, 1993) show that the staggered conformer (Fig. 1 b) is observed for all unconstrained sulfonamides.

As few crystal structures of simple sulfonamides have been reported, we have undertaken an X-ray diffraction study of the title compound, (I), in order to enable direct comparison with calculated structures. This study shows (Fig. 2) that similar to all previously reported solid state structures of sulfonamides, the molecule of the title compound is in a staggered conformation relative to the S—N bond, with the C1—N2—S3—C4 and H2—N2—S3—C4 torsion angles equal to -65.57 (20) and 71 (2)°, respectively. It should be mentioned, however, that extensive hydrogen bonding and C—H···O contacts may influence which conformer is adopted in the solid state. In the crystal structure of the title compound, there is one symmetry independent hydrogen bond N2—H2···O3Bi [symmetry code: (i) x, 1/2 - y, 1/2 + z] which links the molecules into infinite chains along the c axis of the crystal (Fig. 3 and Table 2). Additionally, there are three independent C—H···O contacts which further link the chains into a three-dimensional network.

No gas-phase electron diffraction studies of N-methylmethanesulfonamide have been reported, and the conformation in solution is also currently unknown. Ga- phase electron diffraction results have been reported for N,N-dimethylmethanesulfonamide by Naumov et al. (1979), where the staggered form was used to model the data. Drawing a distinction between the conformers using electron diffraction data alone may well be very difficult, however.

Experimental top

All reagents were purchased from the Aldrich Chemical Company. The reaction was performed under an inert nitrogen atmosphere. All transfers were accomplished using standard Schlenk line techniques. Tetrahydrofuran (THF) was dried by distillation over sodium/benzophenone. Me(H)NS(O)2Me: to a solution of MeNH2 (105 ml, 2.0 M in THF), cooled to 273 K (H2O ice/EtOH bath), was added dropwise a solution of MeSO2Cl (9.17 g, 0.08 mol) in THF (40 ml) with the rate of addition being controlled so that the temperature of reaction did not exceed 278 K. The addition of MeSO2Cl (THF) was accompanied by the deposition of a voluminous white solid. Upon completion of the addition, the reaction mixture was allowed to warm to room temperature and stirred for 18 h. The reaction mixture was then filtered and the collected solid washed with CHCl3 (3 × 30 ml). The combined filtrate and washings were evaporated to dryness yielding a straw-coloured oil which was fractionally distilled under a reduced pressure. Three fractions were obtained, the third of which collected at 358.0–358.5 K (0.3 mbar) represents the target compound in the form of a pale-yellow slightly viscous liquid. Yield: 4.51 g. 1H NMR: δ, p.p.m. (CDCl3, 360 MHz): 2.837 (d, 3H, –NHCH3); 2.970 (s, 3H, –SO2CH3); 4.685 (b.s, 1H, NH). 13C NMR: δ, p.p.m. (CDCl3, 90.56 MHz): 29.79 (d, 3H, –NHCH3); 39.03 (s, 3H, –SO2CH3). A crystal of N-methylmethanesulfonamide was grown from the polycrystalline sample of the frozen liquid at 240 K in a thin capillary of diameter 0.27 mm according to the method of Boese et al. (1992), using a miniature zone refinement procedure with a focused IR laser beam for producing a local molten zone.

Refinement top

All H-atom positions were located in a difference map and refined, with the N—H and C—H bonds all falling in the range 0.77–0.97 Å.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The two calculated minimum energy conformations of N-methylmethanesulfonamide. The eclipsed structure (a) is associated with the global energy minimum, but the staggered structure (b) is close to that observed in the crystal structure.
[Figure 2] Fig. 2. A view of N-methylmethanesulfonamide. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. A packing plot of N-methylmethanesulfonamide, viewed down the a axis, showing the hydrogen-bonding arrangement.
N-methylmethanesulfonamide top
Crystal data top
C2H7NO2SF(000) = 232
Mr = 109.15Dx = 1.472 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 6.6676 (13) ÅCell parameters from 2057 reflections
b = 8.9717 (18) Åθ = 3.0–26.5°
c = 8.5003 (16) ŵ = 0.52 mm1
β = 104.358 (4)°T = 150 K
V = 492.60 (17) Å3Cylinder, colourless
Z = 40.6 × 0.27 × 0.27 × 0.13 (radius) mm
Data collection top
Bruker CCD area-detector
diffractometer
999 independent reflections
Radiation source: fine-focus sealed tube858 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ϕ and ω scansθmax = 26.4°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.528, Tmax = 0.963k = 811
2683 measured reflectionsl = 1010
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035All H-atom parameters refined
wR(F2) = 0.083 w = 1/[σ2(Fo2) + (0.0508P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max < 0.001
999 reflectionsΔρmax = 0.37 e Å3
84 parametersΔρmin = 0.56 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.029 (5)
Crystal data top
C2H7NO2SV = 492.60 (17) Å3
Mr = 109.15Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.6676 (13) ŵ = 0.52 mm1
b = 8.9717 (18) ÅT = 150 K
c = 8.5003 (16) Å0.6 × 0.27 × 0.27 × 0.13 (radius) mm
β = 104.358 (4)°
Data collection top
Bruker CCD area-detector
diffractometer
999 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
858 reflections with I > 2σ(I)
Tmin = 0.528, Tmax = 0.963Rint = 0.028
2683 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.083All H-atom parameters refined
S = 0.96Δρmax = 0.37 e Å3
999 reflectionsΔρmin = 0.56 e Å3
84 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic)

treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C11.1348 (3)0.3430 (3)0.3115 (3)0.0374 (6)
H111.182 (4)0.369 (3)0.215 (4)0.065 (9)*
H121.241 (4)0.281 (3)0.375 (3)0.057 (8)*
H131.113 (4)0.429 (3)0.371 (3)0.055 (8)*
N20.9466 (3)0.25236 (19)0.2585 (2)0.0265 (4)
H20.917 (4)0.203 (3)0.323 (3)0.043 (8)*
S30.74063 (7)0.33102 (5)0.14873 (5)0.0229 (2)
O3A0.5852 (2)0.21764 (16)0.10885 (18)0.0350 (4)
O3B0.8008 (2)0.40673 (15)0.01798 (16)0.0310 (4)
C40.6575 (3)0.4673 (2)0.2658 (3)0.0295 (5)
H410.769 (3)0.538 (2)0.300 (3)0.029 (6)*
H420.536 (4)0.513 (3)0.200 (3)0.034 (6)*
H430.628 (3)0.423 (2)0.349 (3)0.030 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0230 (11)0.0383 (13)0.0446 (15)0.0015 (10)0.0033 (10)0.0007 (11)
N20.0245 (9)0.0265 (9)0.0276 (10)0.0011 (7)0.0045 (8)0.0035 (7)
S30.0199 (3)0.0266 (3)0.0212 (3)0.00215 (18)0.00295 (19)0.00122 (18)
O3A0.0296 (8)0.0377 (8)0.0348 (9)0.0111 (6)0.0029 (6)0.0059 (7)
O3B0.0315 (8)0.0375 (8)0.0252 (8)0.0016 (6)0.0095 (6)0.0047 (6)
C40.0287 (11)0.0321 (12)0.0287 (12)0.0036 (9)0.0088 (10)0.0011 (9)
Geometric parameters (Å, º) top
C1—N21.469 (3)S3—O3A1.4316 (14)
C1—H110.98 (3)S3—O3B1.4419 (14)
C1—H120.96 (3)S3—C41.751 (2)
C1—H130.95 (3)C4—H410.97 (2)
N2—S31.6185 (17)C4—H420.96 (2)
N2—H20.77 (3)C4—H430.87 (2)
N2—C1—H11107.5 (17)O3B—S3—N2106.93 (9)
N2—C1—H12108.1 (16)O3A—S3—C4108.55 (10)
H11—C1—H12105 (2)O3B—S3—C4107.28 (10)
N2—C1—H13112.4 (16)N2—S3—C4108.64 (10)
H11—C1—H13112 (2)S3—C4—H41107.5 (12)
H12—C1—H13111 (2)S3—C4—H42107.9 (13)
C1—N2—S3118.27 (15)H41—C4—H42111.9 (18)
C1—N2—H2117 (2)S3—C4—H43107.8 (14)
S3—N2—H2109 (2)H41—C4—H43111.8 (18)
O3A—S3—O3B118.41 (9)H42—C4—H43109.9 (19)
O3A—S3—N2106.72 (9)
C1—N2—S3—O3A177.56 (17)C1—N2—S3—C465.6 (2)
C1—N2—S3—O3B49.9 (2)H2—N2—S3—C471 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O3Bi0.77 (3)2.23 (3)2.985 (2)170 (3)
C1—H12···O3Aii0.96 (3)2.64 (3)3.455 (3)144 (2)
C4—H43···O3Ai0.87 (2)2.62 (2)3.491 (3)173.4 (19)
C4—H42···O3Biii0.96 (2)2.63 (2)3.575 (3)169.0 (18)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1, y+1/2, z+1/2; (iii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC2H7NO2S
Mr109.15
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)6.6676 (13), 8.9717 (18), 8.5003 (16)
β (°) 104.358 (4)
V3)492.60 (17)
Z4
Radiation typeMo Kα
µ (mm1)0.52
Crystal size (mm)0.6 × 0.27 × 0.27 × 0.13 (radius)
Data collection
DiffractometerBruker CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.528, 0.963
No. of measured, independent and
observed [I > 2σ(I)] reflections
2683, 999, 858
Rint0.028
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.083, 0.96
No. of reflections999
No. of parameters84
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.37, 0.56

Computer programs: SMART (Siemens, 1995), SMART, SHELXTL (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
C1—N21.469 (3)S3—O3B1.4419 (14)
N2—S31.6185 (17)S3—C41.751 (2)
S3—O3A1.4316 (14)
C1—N2—S3118.27 (15)O3A—S3—C4108.55 (10)
O3A—S3—O3B118.41 (9)O3B—S3—C4107.28 (10)
O3A—S3—N2106.72 (9)N2—S3—C4108.64 (10)
O3B—S3—N2106.93 (9)
C1—N2—S3—O3A177.56 (17)C1—N2—S3—C465.6 (2)
C1—N2—S3—O3B49.9 (2)H2—N2—S3—C471 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O3Bi0.77 (3)2.23 (3)2.985 (2)170 (3)
C1—H12···O3Aii0.96 (3)2.64 (3)3.455 (3)144 (2)
C4—H43···O3Ai0.87 (2)2.62 (2)3.491 (3)173.4 (19)
C4—H42···O3Biii0.96 (2)2.63 (2)3.575 (3)169.0 (18)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1, y+1/2, z+1/2; (iii) x+1, y+1, z.
 

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