N-(4-Bromo­phenyl­sulfon­yl)-2,2,2-tri­methyl­acetamide

Gowda, B.T.; Foro, S.; Nirmala, P.G.; Sowmya, B.P.; Fuess, H.

doi:10.1107/S1600536808019375

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1389

doi:10.1107/S1600536808019375

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N-(4-Bromophenylsulfonyl)-2,2,2-trimethylacetamide

B. Thimme Gowda,^a ^* Sabine Foro,^b P. G. Nirmala,^a B. P. Sowmya ^a and Hartmut Fuess ^b

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 24 June 2008; accepted 25 June 2008; online 5 July 2008)

The conformations of the N—H and C=O bonds in the SO₂—NH—CO—C group of the title compound (N4BPSTMAA), C₁₁H₁₄BrNO₃S, are trans to each other, similar to what is observed in N-(4-chlorophenylsulfonyl)-2,2,2-trimethylacetamide (N4CPSTMAA) and 2,2,2-trimethyl-N-(4-methylphenylsulfonyl)acetamide (N4MPSTMAA). The bond parameters in N4BPSTMAA are similar to those in N4CPSTMAA, N4MPSTMAA, N-aryl-2,2,2-trimethylacetamides and 4-bromobenzenesulfonamide. The benzene ring and the SO₂—NH—CO—C group in N4BPSTMAA form a dihedral angle of 82.8 (1)°, comparable with the values of 82.2 (1)° in N4CPSTMAA and 71.2 (1)° in N4MPSTMAA. N—H⋯O hydrogen bonds form a centrosymmetric ring characterized by an R₂²(8) motif.

Related literature

For related literature, see: Gowda et al. (2003 , 2007 , 2008 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₁H₁₄BrNO₃S
M_r = 320.20
Triclinic, $[P \overline 1]$
a = 6.066 (1) Å
b = 10.858 (1) Å
c = 11.092 (2) Å
α = 68.19 (1)°
β = 78.66 (2)°
γ = 88.10 (2)°
V = 664.40 (17) Å³
Z = 2
Mo Kα radiation
μ = 3.25 mm⁻¹
T = 299 (2) K
0.20 × 0.08 × 0.04 mm

Data collection

Oxford Xcalibur diffractometer with Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.563, T_max = 0.881
6843 measured reflections
2692 independent reflections
1551 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.101
S = 0.97
2692 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.86	2.23	2.982 (3)	146
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808019375/bx2154sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019375/bx2154Isup2.hkl

checkCIF report

Comment top

In the present work, as part of a study of the substituent effects on the solid state geometries of N-(aryl)-sulfonamides and substituted amides, the structure of N-(4-bromophenylsulfonyl)-2,2,2-trimethylacetamide (N4BPSTMAA) has been determined (Gowda et al., 2003, 2007, 2008). The conformations of the N—H and C═O bonds of the SO2—NH—CO—C group in N4CPSTMAA are anti to each other (Fig. 1), similar to that observed in N-(4-chlorophenylsulfonyl)-2,2,2-trimethylacetamide (N4CPSTMAA) and (4-methylphenylsulfonyl)-2,2,2-trimethylacetamide (N4MPSTMAA) (Gowda et al., 2008). The bond parameters in N4BPSTMAA are similar to those in N4CPSTMAA, N4MPSTMAA (Gowda et al., 2008), N-(aryl)-2,2,2-trimethylacetamides (Gowda et al., 2007) and 4-bromobenzenesulfonamide (Gowda et al., 2003). The N—H···O hydrogen bonds form a centrosymmetric macro-ring characterized by R₂²(8) motif (Bernstein et al., 1995) ( Table 1, Fig. 2).

Related literature top

For related literature, see: Gowda et al. (2003, 2007, 2008); Bernstein et al. (1995).

Experimental top

The title compound was prepared by refluxing 4-bromobenzenesulfonamide (0.10 mole) with an excess pivalyl 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 precipitated 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 and NMR spectra. Single crystals of the title compound used for X-ray diffraction studies were obtained from a slow evaporation of an ethanolic solution.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction , 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom labelling scheme. The displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

N-(4-Bromophenylsulfonyl)-2,2,2-trimethylacetamide top

Crystal data top

C₁₁H₁₄BrNO₃S	Z = 2
M_r = 320.20	F(000) = 324
Triclinic, P1	D_x = 1.601 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.066 (1) Å	Cell parameters from 2537 reflections
b = 10.858 (1) Å	θ = 2.3–28.0°
c = 11.092 (2) Å	µ = 3.25 mm⁻¹
α = 68.19 (1)°	T = 299 K
β = 78.66 (2)°	Needle, colourless
γ = 88.10 (2)°	0.20 × 0.08 × 0.04 mm
V = 664.40 (17) Å³

Data collection top

Oxford Xcalibur diffractometer with Sapphire CCD detector	2692 independent reflections
Radiation source: fine-focus sealed tube	1551 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Rotation method data acquisition using ω and ϕ scans	θ_max = 26.4°, θ_min = 2.3°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) (Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm)	h = −7→7
T_min = 0.563, T_max = 0.881	k = −13→13
6843 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0526P)²] where P = (F_o² + 2F_c²)/3
2692 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₁H₁₄BrNO₃S	γ = 88.10 (2)°
M_r = 320.20	V = 664.40 (17) Å³
Triclinic, P1	Z = 2
a = 6.066 (1) Å	Mo Kα radiation
b = 10.858 (1) Å	µ = 3.25 mm⁻¹
c = 11.092 (2) Å	T = 299 K
α = 68.19 (1)°	0.20 × 0.08 × 0.04 mm
β = 78.66 (2)°

Data collection top

Oxford Xcalibur diffractometer with Sapphire CCD detector	2692 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) (Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm)	1551 reflections with I > 2σ(I)
T_min = 0.563, T_max = 0.881	R_int = 0.033
6843 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 0.97	Δρ_max = 0.37 e Å⁻³
2692 reflections	Δρ_min = −0.29 e Å⁻³
154 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

	x	y	z	U_iso*/U_eq
Br1	−0.10728 (8)	−0.00925 (4)	0.21716 (5)	0.0810 (2)
S1	0.28409 (14)	0.35519 (8)	0.47093 (8)	0.0451 (2)
O1	0.4965 (4)	0.3098 (2)	0.5007 (2)	0.0548 (6)
O2	0.1120 (4)	0.3668 (2)	0.5741 (2)	0.0580 (6)
O3	0.5763 (4)	0.4572 (2)	0.2073 (2)	0.0615 (7)
N1	0.3085 (4)	0.5038 (2)	0.3551 (3)	0.0449 (7)
H1N	0.2309	0.5653	0.3720	0.054*
C1	0.1807 (5)	0.2548 (3)	0.3993 (3)	0.0399 (8)
C2	0.2864 (6)	0.1387 (3)	0.4005 (3)	0.0478 (8)
H2	0.4134	0.1145	0.4378	0.057*
C3	0.2013 (6)	0.0601 (3)	0.3458 (3)	0.0513 (9)
H3	0.2703	−0.0176	0.3456	0.062*
C4	0.0124 (6)	0.0983 (3)	0.2914 (3)	0.0487 (9)
C5	−0.0926 (6)	0.2124 (3)	0.2896 (4)	0.0521 (9)
H5	−0.2193	0.2364	0.2520	0.062*
C6	−0.0080 (5)	0.2915 (3)	0.3443 (4)	0.0506 (9)
H6	−0.0778	0.3691	0.3440	0.061*
C7	0.4476 (6)	0.5366 (3)	0.2305 (3)	0.0428 (8)
C8	0.4154 (5)	0.6724 (3)	0.1284 (3)	0.0451 (8)
C9	0.1793 (6)	0.6700 (4)	0.0986 (4)	0.0740 (12)
H9A	0.1665	0.6008	0.0657	0.089*
H9B	0.1552	0.7540	0.0331	0.089*
H9C	0.0686	0.6536	0.1782	0.089*
C10	0.4365 (8)	0.7799 (4)	0.1826 (4)	0.0856 (14)
H10A	0.3232	0.7639	0.2611	0.103*
H10B	0.4169	0.8649	0.1172	0.103*
H10C	0.5828	0.7788	0.2037	0.103*
C11	0.5872 (7)	0.6969 (4)	0.0018 (4)	0.0759 (12)
H11A	0.7360	0.6951	0.0197	0.091*
H11B	0.5660	0.7821	−0.0628	0.091*
H11C	0.5684	0.6290	−0.0318	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1133 (4)	0.0498 (3)	0.0888 (4)	−0.0078 (2)	−0.0360 (3)	−0.0269 (2)
S1	0.0570 (6)	0.0369 (5)	0.0389 (5)	0.0063 (4)	−0.0065 (4)	−0.0130 (4)
O1	0.0597 (15)	0.0513 (14)	0.0543 (15)	0.0087 (12)	−0.0183 (13)	−0.0177 (12)
O2	0.0759 (16)	0.0479 (14)	0.0402 (14)	0.0118 (12)	0.0055 (13)	−0.0145 (11)
O3	0.0650 (16)	0.0606 (16)	0.0540 (16)	0.0187 (14)	−0.0034 (13)	−0.0213 (13)
N1	0.0600 (17)	0.0323 (14)	0.0429 (17)	0.0063 (13)	−0.0063 (14)	−0.0169 (13)
C1	0.0397 (18)	0.0325 (17)	0.0390 (18)	−0.0038 (14)	0.0030 (15)	−0.0084 (14)
C2	0.051 (2)	0.0410 (19)	0.051 (2)	0.0136 (16)	−0.0139 (17)	−0.0153 (16)
C3	0.065 (2)	0.0285 (17)	0.054 (2)	0.0035 (16)	−0.0028 (19)	−0.0118 (16)
C4	0.060 (2)	0.0319 (17)	0.052 (2)	0.0014 (16)	−0.0134 (19)	−0.0121 (16)
C5	0.0446 (19)	0.042 (2)	0.059 (2)	−0.0033 (16)	−0.0081 (17)	−0.0081 (17)
C6	0.048 (2)	0.0362 (18)	0.065 (2)	0.0086 (16)	−0.0116 (19)	−0.0167 (17)
C7	0.045 (2)	0.049 (2)	0.0371 (19)	−0.0025 (17)	−0.0069 (16)	−0.0188 (16)
C8	0.048 (2)	0.0432 (19)	0.0356 (19)	−0.0061 (15)	−0.0020 (16)	−0.0076 (15)
C9	0.063 (3)	0.076 (3)	0.065 (3)	0.001 (2)	−0.021 (2)	−0.002 (2)
C10	0.144 (4)	0.041 (2)	0.070 (3)	−0.005 (2)	−0.029 (3)	−0.016 (2)
C11	0.071 (3)	0.077 (3)	0.057 (3)	−0.001 (2)	0.001 (2)	−0.006 (2)

Geometric parameters (Å, º) top

Br1—C4	1.891 (3)	C5—H5	0.9300
S1—O1	1.420 (2)	C6—H6	0.9300
S1—O2	1.430 (2)	C7—C8	1.524 (5)
S1—N1	1.636 (3)	C8—C11	1.514 (5)
S1—C1	1.760 (3)	C8—C10	1.517 (5)
O3—C7	1.208 (4)	C8—C9	1.535 (5)
N1—C7	1.394 (4)	C9—H9A	0.9600
N1—H1N	0.8600	C9—H9B	0.9600
C1—C6	1.380 (4)	C9—H9C	0.9600
C1—C2	1.392 (4)	C10—H10A	0.9600
C2—C3	1.378 (4)	C10—H10B	0.9600
C2—H2	0.9300	C10—H10C	0.9600
C3—C4	1.380 (5)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.369 (4)	C11—H11C	0.9600
C5—C6	1.381 (4)

O1—S1—O2	118.80 (15)	O3—C7—N1	120.2 (3)
O1—S1—N1	111.33 (14)	O3—C7—C8	124.0 (3)
O2—S1—N1	103.71 (14)	N1—C7—C8	115.7 (3)
O1—S1—C1	108.67 (15)	C11—C8—C10	110.9 (3)
O2—S1—C1	109.40 (15)	C11—C8—C7	109.5 (3)
N1—S1—C1	103.87 (14)	C10—C8—C7	110.3 (3)
C7—N1—S1	123.8 (2)	C11—C8—C9	108.6 (3)
C7—N1—H1N	118.1	C10—C8—C9	110.0 (3)
S1—N1—H1N	118.1	C7—C8—C9	107.6 (3)
C6—C1—C2	120.7 (3)	C8—C9—H9A	109.5
C6—C1—S1	119.2 (2)	C8—C9—H9B	109.5
C2—C1—S1	120.1 (2)	H9A—C9—H9B	109.5
C3—C2—C1	119.4 (3)	C8—C9—H9C	109.5
C3—C2—H2	120.3	H9A—C9—H9C	109.5
C1—C2—H2	120.3	H9B—C9—H9C	109.5
C2—C3—C4	119.1 (3)	C8—C10—H10A	109.5
C2—C3—H3	120.5	C8—C10—H10B	109.5
C4—C3—H3	120.5	H10A—C10—H10B	109.5
C5—C4—C3	122.0 (3)	C8—C10—H10C	109.5
C5—C4—Br1	118.6 (3)	H10A—C10—H10C	109.5
C3—C4—Br1	119.5 (2)	H10B—C10—H10C	109.5
C4—C5—C6	119.2 (3)	C8—C11—H11A	109.5
C4—C5—H5	120.4	C8—C11—H11B	109.5
C6—C5—H5	120.4	H11A—C11—H11B	109.5
C1—C6—C5	119.7 (3)	C8—C11—H11C	109.5
C1—C6—H6	120.1	H11A—C11—H11C	109.5
C5—C6—H6	120.1	H11B—C11—H11C	109.5

O1—S1—N1—C7	55.9 (3)	C3—C4—C5—C6	−0.3 (5)
O2—S1—N1—C7	−175.2 (2)	Br1—C4—C5—C6	179.6 (3)
C1—S1—N1—C7	−60.9 (3)	C2—C1—C6—C5	−0.1 (5)
O1—S1—C1—C6	−170.6 (3)	S1—C1—C6—C5	−179.0 (3)
O2—S1—C1—C6	58.2 (3)	C4—C5—C6—C1	0.2 (5)
N1—S1—C1—C6	−52.0 (3)	S1—N1—C7—O3	−7.6 (4)
O1—S1—C1—C2	10.5 (3)	S1—N1—C7—C8	169.3 (2)
O2—S1—C1—C2	−120.7 (3)	O3—C7—C8—C11	−6.7 (4)
N1—S1—C1—C2	129.1 (3)	N1—C7—C8—C11	176.5 (3)
C6—C1—C2—C3	0.1 (5)	O3—C7—C8—C10	−129.0 (4)
S1—C1—C2—C3	179.0 (3)	N1—C7—C8—C10	54.2 (4)
C1—C2—C3—C4	−0.2 (5)	O3—C7—C8—C9	111.0 (4)
C2—C3—C4—C5	0.3 (5)	N1—C7—C8—C9	−65.7 (4)
C2—C3—C4—Br1	−179.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.86	2.23	2.982 (3)	146

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄BrNO₃S
M_r	320.20
Crystal system, space group	Triclinic, P1
Temperature (K)	299
a, b, c (Å)	6.066 (1), 10.858 (1), 11.092 (2)
α, β, γ (°)	68.19 (1), 78.66 (2), 88.10 (2)
V (Å³)	664.40 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.25
Crystal size (mm)	0.20 × 0.08 × 0.04

Data collection
Diffractometer	Oxford Xcalibur diffractometer with Sapphire CCD detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007) (Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm)
T_min, T_max	0.563, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections	6843, 2692, 1551
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.101, 0.97
No. of reflections	2692
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.29

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction , 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.86	2.23	2.982 (3)	146.2

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions of his research fellowship.

References

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