N,4-Dimethyl-N-(4-nitro­benz­yl)benzene­sulfonamide

Zhu, H.-Y.; Wu, Z.; Jiang, S.

doi:10.1107/S1600536808000330

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 3| March 2008| Page o596

doi:10.1107/S1600536808000330

Open

access

N,4-Dimethyl-N-(4-nitrobenzyl)benzenesulfonamide

Hong-Yuan Zhu,^a ^* Zhou Wu ^a and Shende Jiang ^a

^aSchool of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, People's Republic of China
^*Correspondence e-mail: zhhy93@163.com

(Received 5 December 2007; accepted 5 January 2008; online 15 February 2008)

In the title compound, C₁₅H₁₆N₂O₄S, there is a dihedral angle of 63.30 (8)° between the nitrobenzyl and benzene rings, which are separated by a sulfonamide unit The crystal packing is stabilized by a C—H⋯O interaction.

Related literature

For the use of aromatic nitro and amine compounds as precursors in dye synthesis, see: Lauwiner et al. (1998 ); Yang et al. (2004 ). For the preparation of the title compound, see: Andersen et al. (1988 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₅H₁₆N₂O₄S
M_r = 320.36
Monoclinic, P 2₁ /c
a = 9.5694 (19) Å
b = 6.1335 (12) Å
c = 26.126 (5) Å
β = 100.03 (3)°
V = 1510.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 113 (2) K
0.20 × 0.18 × 0.10 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2003 ) T_min = 0.955, T_max = 0.977
8935 measured reflections
2661 independent reflections
2188 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.123
S = 1.10
2661 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O1ⁱ	0.99	2.32	3.287 (4)	166
Symmetry code: (i) x, y-1, z.

Data collection: CrystalClear (Rigaku, 2003); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808000330/sj2454sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808000330/sj2454Isup2.hkl

checkCIF report

Comment top

Aromatic amines are widely employed for organic synthesis, especially as dye intermediates. One method for preparing aromatic amines is reduction of the corresponding aromatic nitro compound (Lauwiner et al., 1998). In our recent work, the title compound (I), Fig. 1, was reduced to the corresponding aromatic amine for potential use as an intermediate in the synthesis of Acid Blue 264 dye according to Yang et al. (2004).

In (I), all bonds lengths and angles are normal (Allen et al., 1987). The dihedral angle between the two aryl rings is 63.30 (8) Å. The distances of S1—C1 and S1—N1 are 1.762 (3) and 1.637 (2) Å respectively. The neighboring molecules are linked together by weak C—H···O hydrogen bonds, Table 1.

Related literature top

For the use of aromatic nitro and amine compounds as precursors in dye synthesis, see: Lauwiner et al. (1998); Yang et al. (2004). For the preparation of the title compound, see: Andersen et al. (1988). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound (I) was synthesized according to the procedure of Andersen et al. (1988). Colorless single crystals (m.p. 403–404 K) were obtained by slow evaporation of a solution in absolute alcohol.

Computing details top

Data collection: CrystalClear (Rigaku, 2003); cell refinement: CrystalClear (Rigaku, 2003); data reduction: CrystalClear (Rigaku, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top

	Fig. 1. The structure of (I) with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing of (I) with hydrogen bonds drawn as dashed lines.

N,4-Dimethyl-N-(4-nitrobenzyl)benzenesulfonamide top

Crystal data top

C₁₅H₁₆N₂O₄S	F(000) = 672
M_r = 320.36	D_x = 1.409 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 403–404 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.5694 (19) Å	Cell parameters from 3609 reflections
b = 6.1335 (12) Å	θ = 2.2–27.9°
c = 26.126 (5) Å	µ = 0.23 mm⁻¹
β = 100.03 (3)°	T = 113 K
V = 1510.0 (5) Å³	Block, colorless
Z = 4	0.20 × 0.18 × 0.10 mm

Data collection top

Rigaku Saturn diffractometer	2661 independent reflections
Radiation source: fine-focus sealed tube	2188 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2003)	k = −6→7
T_min = 0.955, T_max = 0.977	l = −31→26
8935 measured reflections

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0454P)² + 1.1085P] where P = (F_o² + 2F_c²)/3
2661 reflections	(Δ/σ)_max = 0.001
201 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₁₅H₁₆N₂O₄S	V = 1510.0 (5) Å³
M_r = 320.36	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.5694 (19) Å	µ = 0.23 mm⁻¹
b = 6.1335 (12) Å	T = 113 K
c = 26.126 (5) Å	0.20 × 0.18 × 0.10 mm
β = 100.03 (3)°

Data collection top

Rigaku Saturn diffractometer	2661 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2003)	2188 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.977	R_int = 0.057
8935 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.10	Δρ_max = 0.36 e Å⁻³
2661 reflections	Δρ_min = −0.45 e Å⁻³
201 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	0.12405 (8)	0.46188 (11)	0.13266 (3)	0.0293 (2)
O1	0.0775 (3)	0.6688 (3)	0.14746 (9)	0.0531 (7)
O2	0.2167 (2)	0.4497 (4)	0.09498 (8)	0.0445 (6)
O3	−0.5173 (2)	−0.0352 (3)	−0.10469 (8)	0.0334 (5)
O4	−0.5383 (2)	−0.3199 (3)	−0.05751 (8)	0.0329 (5)
N1	−0.0187 (2)	0.3232 (3)	0.10887 (9)	0.0221 (5)
N2	−0.4801 (2)	−0.1489 (4)	−0.06589 (9)	0.0259 (5)
C1	0.2079 (3)	0.3328 (4)	0.19015 (11)	0.0210 (6)
C2	0.2046 (3)	0.4289 (5)	0.23762 (12)	0.0316 (7)
H2	0.1530	0.5601	0.2395	0.038*
C3	0.2765 (3)	0.3336 (5)	0.28224 (12)	0.0311 (7)
H3	0.2738	0.4004	0.3149	0.037*
C4	0.3529 (3)	0.1419 (4)	0.28053 (11)	0.0251 (6)
C5	0.3516 (3)	0.0458 (4)	0.23231 (12)	0.0285 (7)
H5	0.4007	−0.0878	0.2304	0.034*
C6	0.2809 (3)	0.1393 (4)	0.18703 (11)	0.0264 (6)
H6	0.2823	0.0723	0.1543	0.032*
C7	0.4382 (3)	0.0457 (5)	0.32894 (12)	0.0364 (8)
H7A	0.5367	0.0959	0.3327	0.055*
H7B	0.4356	−0.1137	0.3265	0.055*
H7C	0.3981	0.0922	0.3592	0.055*
C8	−0.1208 (3)	0.2999 (7)	0.14427 (14)	0.0496 (10)
H8A	−0.2139	0.2607	0.1244	0.074*
H8B	−0.1282	0.4381	0.1624	0.074*
H8C	−0.0886	0.1852	0.1697	0.074*
C9	0.0035 (3)	0.1211 (4)	0.08077 (12)	0.0282 (7)
H9A	0.0301	0.0020	0.1062	0.034*
H9B	0.0831	0.1428	0.0616	0.034*
C10	−0.1269 (3)	0.0558 (4)	0.04315 (11)	0.0222 (6)
C11	−0.1885 (3)	−0.1471 (4)	0.04786 (11)	0.0259 (6)
H11	−0.1499	−0.2403	0.0758	0.031*
C12	−0.3050 (3)	−0.2153 (4)	0.01256 (11)	0.0235 (6)
H12	−0.3473	−0.3534	0.0159	0.028*
C13	−0.3577 (3)	−0.0763 (4)	−0.02765 (11)	0.0215 (6)
C14	−0.2999 (3)	0.1272 (4)	−0.03363 (11)	0.0231 (6)
H14	−0.3386	0.2195	−0.0617	0.028*
C15	−0.1842 (3)	0.1921 (4)	0.00249 (11)	0.0223 (6)
H15	−0.1435	0.3317	−0.0006	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0358 (4)	0.0223 (4)	0.0238 (4)	−0.0080 (3)	−0.0117 (3)	0.0051 (3)
O1	0.0816 (18)	0.0182 (11)	0.0437 (16)	0.0046 (10)	−0.0330 (13)	−0.0008 (9)
O2	0.0393 (12)	0.0675 (16)	0.0242 (13)	−0.0274 (11)	−0.0015 (10)	0.0159 (11)
O3	0.0316 (11)	0.0426 (12)	0.0224 (12)	−0.0005 (9)	−0.0054 (9)	0.0013 (9)
O4	0.0290 (11)	0.0425 (12)	0.0269 (12)	−0.0163 (9)	0.0041 (9)	−0.0049 (9)
N1	0.0191 (11)	0.0236 (12)	0.0210 (14)	−0.0015 (9)	−0.0036 (10)	−0.0023 (9)
N2	0.0232 (12)	0.0347 (14)	0.0199 (14)	−0.0022 (10)	0.0039 (10)	−0.0082 (11)
C1	0.0172 (13)	0.0232 (14)	0.0192 (15)	−0.0034 (10)	−0.0060 (11)	0.0046 (11)
C2	0.0344 (16)	0.0269 (15)	0.0291 (18)	0.0094 (12)	−0.0067 (14)	−0.0033 (12)
C3	0.0319 (16)	0.0401 (17)	0.0188 (17)	0.0110 (13)	−0.0027 (13)	−0.0033 (13)
C4	0.0195 (13)	0.0292 (15)	0.0257 (17)	−0.0019 (11)	0.0018 (12)	0.0074 (12)
C5	0.0241 (14)	0.0258 (15)	0.0344 (19)	0.0062 (11)	0.0023 (13)	0.0022 (13)
C6	0.0255 (14)	0.0321 (15)	0.0212 (16)	0.0008 (12)	0.0034 (12)	−0.0032 (12)
C7	0.0321 (16)	0.0421 (18)	0.032 (2)	0.0049 (13)	−0.0044 (14)	0.0127 (14)
C8	0.0212 (16)	0.093 (3)	0.034 (2)	−0.0083 (17)	0.0030 (15)	−0.0152 (19)
C9	0.0248 (15)	0.0227 (14)	0.0340 (19)	0.0016 (11)	−0.0039 (13)	−0.0031 (12)
C10	0.0193 (13)	0.0219 (14)	0.0238 (16)	0.0008 (11)	−0.0006 (12)	−0.0048 (11)
C11	0.0250 (14)	0.0254 (14)	0.0252 (17)	0.0027 (11)	−0.0015 (12)	0.0026 (12)
C12	0.0225 (14)	0.0229 (14)	0.0255 (17)	−0.0025 (11)	0.0051 (12)	−0.0025 (11)
C13	0.0172 (13)	0.0271 (14)	0.0197 (16)	−0.0013 (10)	0.0016 (11)	−0.0069 (11)
C14	0.0219 (14)	0.0267 (14)	0.0202 (16)	0.0007 (11)	0.0025 (12)	0.0023 (11)
C15	0.0212 (14)	0.0194 (13)	0.0259 (17)	−0.0024 (10)	0.0033 (12)	−0.0015 (11)

Geometric parameters (Å, º) top

S1—O1	1.421 (2)	C7—H7A	0.9800
S1—O2	1.437 (2)	C7—H7B	0.9800
S1—N1	1.637 (2)	C7—H7C	0.9800
S1—C1	1.762 (3)	C8—H8A	0.9800
O3—N2	1.231 (3)	C8—H8B	0.9800
O4—N2	1.225 (3)	C8—H8C	0.9800
N1—C8	1.464 (4)	C9—C10	1.502 (4)
N1—C9	1.475 (3)	C9—H9A	0.9900
N2—C13	1.470 (3)	C9—H9B	0.9900
C1—C2	1.378 (4)	C10—C15	1.387 (4)
C1—C6	1.387 (4)	C10—C11	1.392 (4)
C2—C3	1.376 (4)	C11—C12	1.382 (4)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.390 (4)	C12—C13	1.379 (4)
C3—H3	0.9500	C12—H12	0.9500
C4—C5	1.389 (4)	C13—C14	1.385 (4)
C4—C7	1.502 (4)	C14—C15	1.382 (4)
C5—C6	1.381 (4)	C14—H14	0.9500
C5—H5	0.9500	C15—H15	0.9500
C6—H6	0.9500

O1—S1—O2	119.53 (15)	C4—C7—H7C	109.5
O1—S1—N1	106.68 (13)	H7A—C7—H7C	109.5
O2—S1—N1	106.66 (13)	H7B—C7—H7C	109.5
O1—S1—C1	106.68 (14)	N1—C8—H8A	109.5
O2—S1—C1	108.47 (13)	N1—C8—H8B	109.5
N1—S1—C1	108.43 (12)	H8A—C8—H8B	109.5
C8—N1—C9	113.7 (2)	N1—C8—H8C	109.5
C8—N1—S1	114.5 (2)	H8A—C8—H8C	109.5
C9—N1—S1	116.25 (17)	H8B—C8—H8C	109.5
O4—N2—O3	123.8 (2)	N1—C9—C10	112.0 (2)
O4—N2—C13	118.1 (2)	N1—C9—H9A	109.2
O3—N2—C13	118.0 (2)	C10—C9—H9A	109.2
C2—C1—C6	120.6 (3)	N1—C9—H9B	109.2
C2—C1—S1	119.8 (2)	C10—C9—H9B	109.2
C6—C1—S1	119.6 (2)	H9A—C9—H9B	107.9
C3—C2—C1	119.6 (3)	C15—C10—C11	119.3 (2)
C3—C2—H2	120.2	C15—C10—C9	120.9 (2)
C1—C2—H2	120.2	C11—C10—C9	119.8 (2)
C2—C3—C4	121.3 (3)	C12—C11—C10	121.1 (3)
C2—C3—H3	119.3	C12—C11—H11	119.5
C4—C3—H3	119.3	C10—C11—H11	119.5
C5—C4—C3	117.8 (3)	C13—C12—C11	117.9 (2)
C5—C4—C7	121.0 (3)	C13—C12—H12	121.1
C3—C4—C7	121.2 (3)	C11—C12—H12	121.1
C6—C5—C4	121.7 (3)	C12—C13—C14	122.9 (2)
C6—C5—H5	119.1	C12—C13—N2	118.3 (2)
C4—C5—H5	119.1	C14—C13—N2	118.9 (2)
C5—C6—C1	118.8 (3)	C15—C14—C13	118.1 (3)
C5—C6—H6	120.6	C15—C14—H14	121.0
C1—C6—H6	120.6	C13—C14—H14	121.0
C4—C7—H7A	109.5	C14—C15—C10	120.8 (2)
C4—C7—H7B	109.5	C14—C15—H15	119.6
H7A—C7—H7B	109.5	C10—C15—H15	119.6

O1—S1—N1—C8	−56.7 (3)	C2—C1—C6—C5	−0.7 (4)
O2—S1—N1—C8	174.5 (2)	S1—C1—C6—C5	177.0 (2)
C1—S1—N1—C8	57.9 (2)	C8—N1—C9—C10	66.9 (3)
O1—S1—N1—C9	167.4 (2)	S1—N1—C9—C10	−156.8 (2)
O2—S1—N1—C9	38.6 (2)	N1—C9—C10—C15	60.7 (3)
C1—S1—N1—C9	−78.0 (2)	N1—C9—C10—C11	−121.6 (3)
O1—S1—C1—C2	6.3 (3)	C15—C10—C11—C12	0.5 (4)
O2—S1—C1—C2	136.2 (2)	C9—C10—C11—C12	−177.3 (3)
N1—S1—C1—C2	−108.3 (2)	C10—C11—C12—C13	0.3 (4)
O1—S1—C1—C6	−171.4 (2)	C11—C12—C13—C14	−0.6 (4)
O2—S1—C1—C6	−41.4 (2)	C11—C12—C13—N2	179.0 (2)
N1—S1—C1—C6	74.0 (2)	O4—N2—C13—C12	7.1 (4)
C6—C1—C2—C3	1.1 (4)	O3—N2—C13—C12	−172.3 (2)
S1—C1—C2—C3	−176.6 (2)	O4—N2—C13—C14	−173.3 (2)
C1—C2—C3—C4	0.1 (5)	O3—N2—C13—C14	7.3 (4)
C2—C3—C4—C5	−1.6 (4)	C12—C13—C14—C15	0.0 (4)
C2—C3—C4—C7	176.3 (3)	N2—C13—C14—C15	−179.5 (2)
C3—C4—C5—C6	2.0 (4)	C13—C14—C15—C10	0.8 (4)
C7—C4—C5—C6	−175.9 (3)	C11—C10—C15—C14	−1.0 (4)
C4—C5—C6—C1	−0.9 (4)	C9—C10—C15—C14	176.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O1ⁱ	0.99	2.32	3.287 (4)	166

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₆N₂O₄S
M_r	320.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	9.5694 (19), 6.1335 (12), 26.126 (5)
β (°)	100.03 (3)
V (Å³)	1510.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.20 × 0.18 × 0.10

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2003)
T_min, T_max	0.955, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	8935, 2661, 2188
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.123, 1.10
No. of reflections	2661
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.45

Computer programs: CrystalClear (Rigaku, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O1ⁱ	0.99	2.32	3.287 (4)	165.7

Symmetry code: (i) x, y−1, z.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Andersen, K. K., Chumpradit, S. & McIntyre, D. J. (1988). J. Org. Chem. 53, 4667–4675. CrossRef CAS Web of Science Google Scholar
Bruker (1997). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lauwiner, M., Rys, P. & Wissmann, J. (1998). Appl. Catal. A: Gen. 172, 141–148. Google Scholar
Rigaku (2003). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, X. W. & Yang, W. (2004). Shanghai Dyestuffs, 32, 20–30. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 3| March 2008| Page o596

doi:10.1107/S1600536808000330

Open

access