o-Toluene­sulfonamide: a redetermination

Gowda, B.T.; Foro, S.; Shakuntala, K.; Fuess, H.

doi:10.1107/S1600536809033686

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2258

doi:10.1107/S1600536809033686

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o-Toluenesulfonamide: a redetermination

B. Thimme Gowda,^a ^* Sabine Foro,^b K. Shakuntala ^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 10 August 2009; accepted 24 August 2009; online 29 August 2009)

The structure of the title compound, C₇H₉NO₂S, was previously determined from powder diffraction data [Tremayne, Seaton & Glidewell (2002). Acta Cryst. B58, 823–834]. It has now been refined to a significantly higher precision. The amino N-atom is bent with a C—C—S—N torsion angle of −65.8 (2)deg;. In the crystal, molecules are packed into a three-dimensional framework/supramolecular structure through hydrogen bonds between the two H atoms of the sulfonamide group and sulfonyl O atoms of neighbouring molecules.

Related literature

For our studies of the effect of substituents on the solid state structures of sulfonamides, see: Gowda et al. (2003 , 2009 ); Gowda, Srilatha et al. (2007 ). For the parent benzenesulfonamide, see: Gowda, Nayak et al. (2007 ). For other aryl sulfonamides, see: Gowda et al. (2003, 2009); Gowda, Srilatha et al. (2007); Jones & Weinkauf (1993 ); Kumar et al. (1992 ); O'Connor & Maslen (1965 ). For the powder structure of the title compound, see: Tremayne et al. (2002 ).

Experimental

Crystal data

C₇H₉NO₂S
M_r = 171.21
Tetragonal, I 4₁ /a
a = 18.670 (3) Å
c = 9.057 (1) Å
V = 3157.0 (8) Å³
Z = 16
Cu Kα radiation
μ = 3.24 mm⁻¹
T = 299 K
0.40 × 0.35 × 0.02 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.324, T_max = 0.938
5320 measured reflections
1403 independent reflections
1290 reflections with I > 2σ(I)
R_int = 0.059
3 standard reflections frequency: 120 min intensity decay: 1.5%

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.101
S = 1.07
1403 reflections
108 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O2ⁱ	0.839 (16)	2.193 (18)	3.003 (2)	162 (2)
N1—H12⋯O1ⁱⁱ	0.841 (16)	2.138 (17)	2.964 (2)	167 (2)
Symmetry codes: (i) $[y-{\script{1\over 4}}, -x+{\script{1\over 4}}, -z+{\script{1\over 4}}]$ ; (ii) $[-y+{\script{1\over 4}}, x-{\script{1\over 4}}, z-{\script{1\over 4}}]$ .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809033686/fl2262sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033686/fl2262Isup2.hkl

checkCIF report

Comment top

The chemistry of sulfonamides is of interest as they show distinct physical, chemical and biological properties. Many arylsulfonamides exhibit pharmacological, fungicidal and herbicidal activities. In the present work, the structure of (I) has been determined as part of our work to explore the effect of substituents on the solid state structures of sulfonamides (Gowda et al., 2003, 2009; Gowda, Srilatha et al., 2007).

The structure of (I) solved from X-ray powder data has been reported (Tremayne et al., 2002) and the present single-crystal X-ray study confirms the powder diffraction structural parameters. (I) crystallizes in the tetragonal I 41/a space group, in contrast to the monoclinic Pc space group observed with the parent benzenesulfonamide (BSA)(Gowda, Nayak et al., 2007), the monoclinic cc space group for 2-chlorobenzenesulfonamide (2CBSA)(Gowda et al., 2009), the orthorhombic Pbca space group for both 4-fluorobenzenesulfonamide (Jones & Weinkauf, 1993) and 4-aminobenzenesulfonamide (O'Connor & Maslen, 1965), and the monoclinic P21/n space group for both 4-chlorobenzenesulfonamide and 4-bromobenzenesulfonamide (Gowda et al., 2003), and 4-methylbenzenesulfonamide (Kumar et al., 1992). The orientation of the amino group with respect to the ring is given by the C–C–S–N torsional angle of -65.8 (2)°, compared to the values of -78.1 (10)° for BSA and 64.0 (2)° for 2CBSA. In (I), the molecules are packed into layers paralel to the b-axis through N1—H11···O1(S) and N1—H12···O2(S) intermolecular hydrogen bonding (Table 1 & Fig.2).

Related literature top

For our studies of the effect of substituents on the solid state structures of sulfonamides, see: Gowda et al. (2003, 2009); Gowda, Srilatha et al. (2007). For the parent benzenesulfonamide, see: Gowda, Nayak et al. (2007). For other aryl sulfonamides, see: Gowda et al. (2003, 2009); Gowda, Srilatha et al. (2007); Jones & Weinkauf (1993); Kumar et al. (1992); O'Connor & Maslen (1965). For the powder structure of the title compound, see: Tremayne et al. (2002)

Experimental top

The purity of the commmercial sample (TCI, Tokyo) was checked and characterized by its infrared spectra. The single crystals used in X-ray diffraction studies were grown from ethanol by a slow evaporation of the solvent at room temperature.

Computing details top

Data collection: CAD-4-PC (Enraf–Nonius, 1996); cell refinement: CAD-4-PC (Enraf–Nonius, 1996); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I), showing the atom labelling scheme and displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Molecular packing of (I) with hydrogen bonding shown as dashed lines.

o-Toluenesulfonamide top

Crystal data top

C₇H₉NO₂S	D_x = 1.441 Mg m⁻³
M_r = 171.21	Cu Kα radiation, λ = 1.54180 Å
Tetragonal, I4₁/a	Cell parameters from 25 reflections
Hall symbol: -I 4ad	θ = 4.7–17.9°
a = 18.670 (3) Å	µ = 3.24 mm⁻¹
c = 9.057 (1) Å	T = 299 K
V = 3157.0 (8) Å³	Prism, colourless
Z = 16	0.40 × 0.35 × 0.02 mm
F(000) = 1440

Data collection top

Enraf–Nonius CAD-4 diffractometer	1290 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.059
Graphite monochromator	θ_max = 66.8°, θ_min = 4.7°
ω/2θ scans	h = −22→22
Absorption correction: ψ scan (North et al., 1968)	k = −22→22
T_min = 0.324, T_max = 0.938	l = −10→0
5320 measured reflections	3 standard reflections every 120 min
1403 independent reflections	intensity decay: 1.5%

Refinement top

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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0529P)² + 2.2812P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1403 reflections	Δρ_max = 0.28 e Å⁻³
108 parameters	Δρ_min = −0.41 e Å⁻³
2 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: 0.00227 (18)

Crystal data top

C₇H₉NO₂S	Z = 16
M_r = 171.21	Cu Kα radiation
Tetragonal, I4₁/a	µ = 3.24 mm⁻¹
a = 18.670 (3) Å	T = 299 K
c = 9.057 (1) Å	0.40 × 0.35 × 0.02 mm
V = 3157.0 (8) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1290 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.059
T_min = 0.324, T_max = 0.938	3 standard reflections every 120 min
5320 measured reflections	intensity decay: 1.5%
1403 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	2 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.28 e Å⁻³
1403 reflections	Δρ_min = −0.41 e Å⁻³
108 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
S1	0.13337 (2)	0.12556 (2)	0.26312 (5)	0.0365 (2)
O1	0.20600 (8)	0.10124 (10)	0.24990 (15)	0.0543 (5)
O2	0.11947 (10)	0.20074 (8)	0.25836 (16)	0.0612 (5)
N1	0.09068 (10)	0.08933 (10)	0.13117 (18)	0.0454 (4)
H11	0.0510 (10)	0.1073 (12)	0.108 (3)	0.054*
H12	0.1053 (12)	0.0484 (10)	0.107 (3)	0.054*
C1	0.10065 (9)	0.09226 (9)	0.43325 (19)	0.0329 (4)
C2	0.03095 (11)	0.10630 (10)	0.4810 (2)	0.0395 (5)
C3	0.01179 (12)	0.07885 (12)	0.6185 (2)	0.0522 (5)
H3	−0.0341	0.0873	0.6542	0.063*
C4	0.05868 (14)	0.03960 (13)	0.7032 (2)	0.0575 (6)
H4	0.0441	0.0222	0.7946	0.069*
C5	0.12671 (13)	0.02595 (13)	0.6539 (2)	0.0545 (6)
H5	0.1583	−0.0007	0.7113	0.065*
C6	0.14805 (11)	0.05211 (11)	0.5179 (2)	0.0430 (5)
H6	0.1940	0.0429	0.4832	0.052*
C7	−0.02347 (13)	0.14733 (13)	0.3939 (3)	0.0609 (6)
H7A	−0.0344	0.1218	0.3047	0.073*
H7B	−0.0046	0.1937	0.3695	0.073*
H7C	−0.0663	0.1529	0.4515	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0422 (3)	0.0384 (3)	0.0289 (3)	−0.00894 (17)	−0.00042 (16)	0.00272 (16)
O1	0.0375 (8)	0.0865 (12)	0.0388 (8)	−0.0106 (7)	0.0015 (6)	0.0054 (7)
O2	0.1032 (14)	0.0364 (8)	0.0441 (9)	−0.0154 (8)	0.0039 (8)	0.0066 (6)
N1	0.0483 (10)	0.0500 (10)	0.0378 (9)	0.0088 (8)	−0.0116 (7)	−0.0078 (7)
C1	0.0401 (10)	0.0305 (8)	0.0281 (8)	−0.0057 (7)	−0.0005 (7)	−0.0006 (7)
C2	0.0427 (11)	0.0357 (10)	0.0401 (10)	−0.0035 (8)	0.0019 (8)	−0.0061 (7)
C3	0.0541 (13)	0.0591 (13)	0.0435 (11)	−0.0101 (10)	0.0151 (9)	−0.0081 (9)
C4	0.0769 (16)	0.0612 (14)	0.0345 (10)	−0.0178 (12)	0.0063 (10)	0.0060 (10)
C5	0.0673 (15)	0.0549 (13)	0.0413 (12)	−0.0066 (10)	−0.0086 (10)	0.0160 (9)
C6	0.0445 (11)	0.0439 (11)	0.0405 (10)	−0.0014 (8)	−0.0025 (8)	0.0056 (8)
C7	0.0474 (12)	0.0632 (14)	0.0721 (16)	0.0123 (11)	0.0017 (11)	0.0027 (12)

Geometric parameters (Å, º) top

S1—O2	1.4281 (16)	C3—C4	1.375 (4)
S1—O1	1.4349 (16)	C3—H3	0.9300
S1—N1	1.5877 (17)	C4—C5	1.370 (3)
S1—C1	1.7703 (17)	C4—H4	0.9300
N1—H11	0.839 (16)	C5—C6	1.384 (3)
N1—H12	0.841 (16)	C5—H5	0.9300
C1—C6	1.390 (3)	C6—H6	0.9300
C1—C2	1.396 (3)	C7—H7A	0.9600
C2—C3	1.394 (3)	C7—H7B	0.9600
C2—C7	1.497 (3)	C7—H7C	0.9600

O2—S1—O1	118.70 (11)	C2—C3—H3	119.0
O2—S1—N1	107.74 (10)	C5—C4—C3	120.5 (2)
O1—S1—N1	106.07 (9)	C5—C4—H4	119.8
O2—S1—C1	107.98 (9)	C3—C4—H4	119.8
O1—S1—C1	106.72 (8)	C4—C5—C6	119.4 (2)
N1—S1—C1	109.41 (9)	C4—C5—H5	120.3
S1—N1—H11	117.3 (17)	C6—C5—H5	120.3
S1—N1—H12	114.9 (17)	C5—C6—C1	119.9 (2)
H11—N1—H12	126 (2)	C5—C6—H6	120.1
C6—C1—C2	121.59 (17)	C1—C6—H6	120.1
C6—C1—S1	116.72 (15)	C2—C7—H7A	109.5
C2—C1—S1	121.69 (14)	C2—C7—H7B	109.5
C3—C2—C1	116.55 (19)	H7A—C7—H7B	109.5
C3—C2—C7	119.0 (2)	C2—C7—H7C	109.5
C1—C2—C7	124.44 (19)	H7A—C7—H7C	109.5
C4—C3—C2	122.1 (2)	H7B—C7—H7C	109.5
C4—C3—H3	119.0

O2—S1—C1—C6	−128.04 (16)	S1—C1—C2—C7	2.5 (3)
O1—S1—C1—C6	0.61 (17)	C1—C2—C3—C4	−0.3 (3)
N1—S1—C1—C6	114.96 (15)	C7—C2—C3—C4	178.8 (2)
O2—S1—C1—C2	51.23 (17)	C2—C3—C4—C5	−0.2 (3)
O1—S1—C1—C2	179.89 (15)	C3—C4—C5—C6	0.1 (4)
N1—S1—C1—C2	−65.77 (17)	C4—C5—C6—C1	0.4 (3)
C6—C1—C2—C3	0.9 (3)	C2—C1—C6—C5	−0.9 (3)
S1—C1—C2—C3	−178.38 (14)	S1—C1—C6—C5	178.33 (17)
C6—C1—C2—C7	−178.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O2ⁱ	0.84 (2)	2.19 (2)	3.003 (2)	162 (2)
N1—H12···O1ⁱⁱ	0.84 (2)	2.14 (2)	2.964 (2)	167 (2)

Symmetry codes: (i) y−1/4, −x+1/4, −z+1/4; (ii) −y+1/4, x−1/4, z−1/4.

Experimental details

Crystal data
Chemical formula	C₇H₉NO₂S
M_r	171.21
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	299
a, c (Å)	18.670 (3), 9.057 (1)
V (Å³)	3157.0 (8)
Z	16
Radiation type	Cu Kα
µ (mm⁻¹)	3.24
Crystal size (mm)	0.40 × 0.35 × 0.02

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.324, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	5320, 1403, 1290
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.101, 1.07
No. of reflections	1403
No. of parameters	108
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.41

Computer programs: CAD-4-PC (Enraf–Nonius, 1996), REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O2ⁱ	0.839 (16)	2.193 (18)	3.003 (2)	162 (2)
N1—H12···O1ⁱⁱ	0.841 (16)	2.138 (17)	2.964 (2)	167 (2)

Symmetry codes: (i) y−1/4, −x+1/4, −z+1/4; (ii) −y+1/4, x−1/4, z−1/4.

Acknowledgements

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

References

Enraf–Nonius (1996). CAD-4-PC. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Gowda, B. T., Foro, S., Shakuntala, K. & Fuess, H. (2009). Acta Cryst. E65, o2144. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gowda, B. T., Jyothi, K., Kozisek, J. & Fuess, H. (2003). Z. Naturforsch. Teil A, 58, 656–660. CAS Google Scholar
Gowda, B. T., Nayak, R., Kožíšek, J., Tokarčík, M. & Fuess, H. (2007). Acta Cryst. E63, o2967. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gowda, B. T., Srilatha, Foro, S., Kozisek, J. & Fuess, H. (2007). Z. Naturforsch. Teil A, 62, 417–424. CAS Google Scholar
Jones, P. G. & Weinkauf, A. (1993). Z. Kristallogr. 208, 128–129. CrossRef CAS Google Scholar
Kumar, S. V., Senadhi, S. E. & Rao, L. M. (1992). Z. Kristallogr. 202, 1–6. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
O'Connor, B. H. & Maslen, E. N. (1965). Acta Cryst. 18, 363–366. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (1987). REDU4. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar
Tremayne, M., Seaton, C. C. & Glidewell, C. (2002). Acta Cryst. B58, 823–834. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar