o-Toluene­sulfonamide: a redetermination

Abstract

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,

• a = 18.670 (3) Å

• c = 9.057 (1) Å

• V = 3157.0 (8) ų

• 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[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 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

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—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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The H atoms of the NH₂ group were located in difference map and refined with restrained geometry to 0.86 (2) Å. The other H atoms were positioned with idealized geometry using a riding model [C—H = 0.93–0.96 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 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.

Crystal data

C7H9NO2S	Dx = 1.441 Mg m−3
Mr = 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

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

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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101	w = 1/[σ2(Fo2) + (0.0529P)2 + 2.2812P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
1403 reflections	Δρmax = 0.28 e Å−3
108 parameters	Δρmin = −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)

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
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 (Ų)

	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, °)

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, °)

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.