2,2-Dimethyl-N-(phenyl­sulfon­yl)acetamide

Abstract

In the title compound, C₁₀H₁₃NO₃S, the N—H and C=O bonds in the SO₂—NH—CO—C segment are anti to each other. The benzene ring and the SO₂—NH—CO—C segment form a dihedral angle of 87.4 (1)°. The crystal packing features inversion-related dimers linked by pairs of N—H⋯O hydrogen bonds.

Related literature

For sulfonamide drugs, see: Maren (1976 ▶). It has been postulated that the propensity for hydrogen bonding in the solid state can give rise to polymorphism due to the presence of various hydrogen-bond donors and acceptors, see: Yang & Guillory (1972 ▶). The hydrogen bonding preferences of sulfon­amides have also been investigated, see: Adsmond & Grant (2001 ▶). The nature and position of substituents play a significant role in the crystal structures of N-(ar­yl)sulfonoamides, see: Gowda et al. (2008a ▶,b ▶,c ▶);

Experimental

Crystal data

• C₁₀H₁₃NO₃S

• M _r = 227.27

• Monoclinic,

• a = 6.1240 (4) Å

• b = 22.201 (2) Å

• c = 8.9192 (9) Å

• β = 106.903 (6)°

• V = 1160.26 (17) ų

• Z = 4

• Cu Kα radiation

• μ = 2.40 mm⁻¹

• T = 299 K

• 0.50 × 0.13 × 0.08 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: none

• 2732 measured reflections

• 2075 independent reflections

• 1755 reflections with I > 2σ(I)

• R _int = 0.047

• 3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

• R[F ² > 2σ(F ²)] = 0.073

• wR(F ²) = 0.213

• S = 1.08

• 2075 reflections

• 140 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.78 e Å⁻³

• Δρ_min = −0.58 e Å⁻³

Data collection: CAD-4-PC (Enraf–Nonius, 1996 ▶); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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
N1—H1N⋯O2i	0.81 (4)	2.12 (5)	2.898 (4)	160 (4)

Symmetry code: (i) .

supplementary crystallographic information

Comment

Sulfonamide drugs that exhibit antibacterial activity contain the sulfanilamide moiety (Maren, 1976). It has been postulated that the propensity for hydrogen bonding in the solid state, due to the presence of various hydrogen bond donors and acceptors, can give rise to polymorphism (Yang & Guillory, 1972). The hydrogen bonding preferences of sulfonamides have also been investigated (Adsmond & Grant, 2001). The nature and position of substituents play a significant role in the crystal structures of N-(aryl)sulfonoamides (Gowda et al., 2008a, b, c).

As part of our substituent effect studies, the structure of (I) has been determined. The N—H and C=O bonds of the SO₂—NH—CO—C segment in (I) are anti to each other (Fig. 1), similar to that observed in N-(phenylsulfonyl)2,2,2-trimethylacetamide (II)(Gowda et al., 2008c), N-(phenylsulfonyl)2,2-dichloroacetamide (III) (Gowda et al., 2008a) and other sulfonoamides (Gowda et al., 2008b). The SO₂—NH—CO—C segment forms a dihedral angle of 87.4 (1)° with the benzene ring, compared to values of 83.2 (1) and 76.0 (1)° (for the two independent molecules of (II)) and 79.8 (1)° in (III). In the crystal the molecules form inversion-related dimers along the c axis, linked by pairs of N—H···O(S) hydrogen bonds (Table 1, Fig.2).

Experimental

The title compound was prepared by refluxing benzenesulfonamide (0.10 mole) with an excess of isobutanoyl chloride (0.20 mole) for about an hour on a water bath. The reaction mixture was cooled and poured into ice cold water. The resulting solid was separated, washed thoroughly with water and dissolved in warm dilute sodium hydrogen carbonate solution. The title compound was reprecipitated by acidifying the filtered solution with glacial acetic acid. It was filtered, dried and recrystallized from ethanol. The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared spectra. Single crystals of the title compound used for X-ray diffraction studies were obtained from a slow evaporation of an ethanolic solution of the compound.

Refinement

The H atom of the NH group was located in a difference map and and its position refined with N—H = 0.81 (4) Å. The other H atoms were positioned with idealized geometry using a riding model with C—H = 0.93–0.98 Å.

All H atoms were refined with isotropic displacement parameters (set to 1.2 times of the U_eq of the parent atom).

Figures

Fig. 1.

Molecular structure of (I), showing the atom labeling scheme. The displacement ellipsoids are drawn at the 50% probability level. The H atoms are represented as small spheres of arbitrary radii.

Fig. 2.

Molecular packing of (I) with hydrogen bonding shown as dashed lines.

Crystal data

C10H13NO3S	F(000) = 480
Mr = 227.27	Dx = 1.301 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 6.1240 (4) Å	θ = 4.0–20.3°
b = 22.201 (2) Å	µ = 2.40 mm−1
c = 8.9192 (9) Å	T = 299 K
β = 106.903 (6)°	Rod, colourless
V = 1160.26 (17) Å3	0.50 × 0.13 × 0.08 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.047
Radiation source: fine-focus sealed tube	θmax = 67.0°, θmin = 4.0°
graphite	h = 0→7
ω/2θ scans	k = −26→4
2732 measured reflections	l = −10→10
2075 independent reflections	3 standard reflections every 120 min
1755 reflections with I > 2σ(I)	intensity decay: 1.0%

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.073	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.213	w = 1/[σ2(Fo2) + (0.1492P)2 + 0.3098P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
2075 reflections	Δρmax = 0.78 e Å−3
140 parameters	Δρmin = −0.58 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.029 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.4133 (5)	0.36281 (13)	0.1597 (3)	0.0566 (7)
C2	0.6038 (6)	0.3479 (2)	0.1164 (5)	0.0806 (10)
H2	0.6706	0.3751	0.0637	0.097*
C3	0.6932 (8)	0.2901 (3)	0.1549 (7)	0.1103 (19)
H3	0.8212	0.2782	0.1263	0.132*
C4	0.5957 (12)	0.2509 (2)	0.2337 (7)	0.117 (2)
H4	0.6587	0.2128	0.2591	0.141*
C5	0.4070 (11)	0.26677 (19)	0.2757 (6)	0.1049 (15)
H5	0.3418	0.2397	0.3297	0.126*
C6	0.3138 (7)	0.32271 (16)	0.2382 (4)	0.0734 (9)
H6	0.1838	0.3337	0.2655	0.088*
C7	0.0475 (5)	0.41022 (15)	−0.1737 (4)	0.0627 (8)
C8	0.0133 (7)	0.42667 (17)	−0.3429 (4)	0.0721 (9)
H8	0.0582	0.4689	−0.3459	0.087*
C9	0.1661 (13)	0.3903 (4)	−0.4061 (7)	0.162 (3)
H9A	0.1324	0.3484	−0.3988	0.194*
H9B	0.3216	0.3980	−0.3470	0.194*
H9C	0.1443	0.4008	−0.5139	0.194*
C10	−0.2332 (10)	0.4217 (3)	−0.4352 (6)	0.123 (2)
H10A	−0.3227	0.4479	−0.3908	0.148*
H10B	−0.2835	0.3809	−0.4321	0.148*
H10C	−0.2514	0.4332	−0.5420	0.148*
N1	0.2199 (5)	0.44210 (13)	−0.0704 (3)	0.0632 (8)
H1N	0.280 (7)	0.4703 (19)	−0.101 (5)	0.076*
O1	0.1032 (5)	0.43906 (11)	0.1775 (3)	0.0754 (7)
O2	0.4768 (5)	0.47818 (11)	0.1727 (3)	0.0779 (8)
O3	−0.0530 (5)	0.37102 (14)	−0.1283 (3)	0.0923 (10)
S1	0.29657 (13)	0.43493 (3)	0.12050 (8)	0.0570 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0624 (17)	0.0556 (16)	0.0489 (15)	−0.0002 (12)	0.0118 (13)	−0.0021 (11)
C2	0.0643 (19)	0.094 (3)	0.084 (2)	−0.0031 (18)	0.0227 (17)	−0.020 (2)
C3	0.074 (3)	0.120 (4)	0.122 (4)	0.030 (3)	0.005 (3)	−0.043 (3)
C4	0.137 (5)	0.080 (3)	0.105 (4)	0.038 (3)	−0.012 (3)	−0.005 (3)
C5	0.144 (4)	0.071 (2)	0.094 (3)	0.014 (3)	0.026 (3)	0.021 (2)
C6	0.090 (2)	0.0648 (19)	0.0673 (19)	0.0021 (17)	0.0261 (17)	0.0103 (15)
C7	0.0627 (17)	0.0669 (18)	0.0547 (17)	−0.0113 (14)	0.0112 (14)	0.0026 (13)
C8	0.083 (2)	0.076 (2)	0.0534 (18)	−0.0139 (17)	0.0147 (16)	−0.0006 (15)
C9	0.184 (7)	0.226 (8)	0.096 (4)	0.083 (6)	0.074 (4)	0.015 (5)
C10	0.113 (4)	0.163 (5)	0.068 (3)	−0.016 (3)	−0.015 (3)	0.003 (3)
N1	0.0731 (17)	0.0619 (16)	0.0497 (14)	−0.0170 (12)	0.0104 (12)	0.0071 (11)
O1	0.0876 (17)	0.0760 (16)	0.0715 (15)	0.0129 (12)	0.0370 (13)	0.0004 (11)
O2	0.0986 (18)	0.0689 (14)	0.0570 (13)	−0.0292 (12)	0.0081 (12)	−0.0041 (10)
O3	0.0977 (19)	0.108 (2)	0.0663 (15)	−0.0501 (16)	0.0162 (13)	0.0048 (13)
S1	0.0701 (6)	0.0519 (5)	0.0477 (5)	−0.0063 (3)	0.0153 (4)	−0.0007 (3)

Geometric parameters (Å, °)

C1—C2	1.372 (5)	C7—C8	1.507 (4)
C1—C6	1.379 (5)	C8—C9	1.466 (7)
C1—S1	1.747 (3)	C8—C10	1.499 (6)
C2—C3	1.400 (7)	C8—H8	0.9800
C2—H2	0.9300	C9—H9A	0.9600
C3—C4	1.361 (8)	C9—H9B	0.9600
C3—H3	0.9300	C9—H9C	0.9600
C4—C5	1.361 (8)	C10—H10A	0.9600
C4—H4	0.9300	C10—H10B	0.9600
C5—C6	1.367 (6)	C10—H10C	0.9600
C5—H5	0.9300	N1—S1	1.637 (3)
C6—H6	0.9300	N1—H1N	0.81 (4)
C7—O3	1.202 (4)	O1—S1	1.420 (3)
C7—N1	1.378 (4)	O2—S1	1.435 (2)
C2—C1—C6	121.7 (3)	C9—C8—H8	107.5
C2—C1—S1	119.7 (3)	C10—C8—H8	107.5
C6—C1—S1	118.6 (3)	C7—C8—H8	107.5
C1—C2—C3	117.1 (4)	C8—C9—H9A	109.5
C1—C2—H2	121.4	C8—C9—H9B	109.5
C3—C2—H2	121.4	H9A—C9—H9B	109.5
C4—C3—C2	121.0 (4)	C8—C9—H9C	109.5
C4—C3—H3	119.5	H9A—C9—H9C	109.5
C2—C3—H3	119.5	H9B—C9—H9C	109.5
C5—C4—C3	120.8 (4)	C8—C10—H10A	109.5
C5—C4—H4	119.6	C8—C10—H10B	109.5
C3—C4—H4	119.6	H10A—C10—H10B	109.5
C4—C5—C6	119.7 (5)	C8—C10—H10C	109.5
C4—C5—H5	120.1	H10A—C10—H10C	109.5
C6—C5—H5	120.1	H10B—C10—H10C	109.5
C5—C6—C1	119.7 (4)	C7—N1—S1	125.3 (2)
C5—C6—H6	120.1	C7—N1—H1N	120 (3)
C1—C6—H6	120.1	S1—N1—H1N	114 (3)
O3—C7—N1	120.9 (3)	O1—S1—O2	118.90 (16)
O3—C7—C8	125.3 (3)	O1—S1—N1	110.43 (16)
N1—C7—C8	113.7 (3)	O2—S1—N1	103.49 (14)
C9—C8—C10	113.7 (5)	O1—S1—C1	108.82 (15)
C9—C8—C7	109.5 (4)	O2—S1—C1	108.49 (16)
C10—C8—C7	110.9 (4)	N1—S1—C1	105.91 (14)
C6—C1—C2—C3	0.2 (5)	O3—C7—N1—S1	−4.4 (5)
S1—C1—C2—C3	178.2 (3)	C8—C7—N1—S1	179.4 (3)
C1—C2—C3—C4	−0.8 (7)	C7—N1—S1—O1	−50.6 (3)
C2—C3—C4—C5	0.6 (8)	C7—N1—S1—O2	−178.9 (3)
C3—C4—C5—C6	0.2 (8)	C7—N1—S1—C1	67.1 (3)
C4—C5—C6—C1	−0.8 (7)	C2—C1—S1—O1	−179.6 (3)
C2—C1—C6—C5	0.6 (6)	C6—C1—S1—O1	−1.4 (3)
S1—C1—C6—C5	−177.5 (3)	C2—C1—S1—O2	−48.8 (3)
O3—C7—C8—C9	−88.9 (6)	C6—C1—S1—O2	129.3 (3)
N1—C7—C8—C9	87.0 (5)	C2—C1—S1—N1	61.7 (3)
O3—C7—C8—C10	37.3 (6)	C6—C1—S1—N1	−120.1 (3)
N1—C7—C8—C10	−146.7 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2i	0.81 (4)	2.12 (5)	2.898 (4)	160 (4)

Symmetry codes: (i) −x+1, −y+1, −z.