N-(4-Meth­oxy-2-nitro­phen­yl)-N-(methyl­sulfon­yl)acetamide

Zia-ur-Rehman, M.; Sepehrianazar, A.; Ali, M.; Siddiqui, W.A.; Çaylak, N.

doi:10.1107/S1600536809011799

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o941

doi:10.1107/S1600536809011799

Open

access

N-(4-Methoxy-2-nitrophenyl)-N-(methylsulfonyl)acetamide

Muhammad Zia-ur-Rehman,^a ^* Amir Sepehrianazar,^b Muhammad Ali,^c Waseeq Ahmad Siddiqui ^c and Nagihan Çaylak ^d

^aApplied Chemistry Research Centre, PCSIR Laboratories Complex, Lahore 54600, Pakistan, ^bDepartment of Chemical Engineering, Islamic Azad University, Ahar Branch, Ahar-54516, Iran, ^cDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, and ^dDepartment of Physics, Sakarya University, Sakarya, Turkey
^*Correspondence e-mail: rehman_pcsir@hotmail.com

(Received 27 March 2009; accepted 30 March 2009; online 2 April 2009)

In the title compound, C₁₀H₁₂N₂O₆S, the nitro group is twisted slightly out of the plane of the aromatic ring, forming a dihedral angle of 20.79 (1)°. In the crystal, the molecules arrange themselves as a chain along the a axis through intermolecular C—H⋯O interactions.

Related literature

For the synthesis of sulfur-containing heterocyclic compounds, see: Siddiqui et al. (2007 ); Wen et al. (2006 ); Zhang et al. (2006 ). For related structures, see: Zhang et al. (2006); Wen et al. (2005 ); Zia-ur-Rehman et al. (2008 ).

Experimental

Crystal data

C₁₀H₁₂N₂O₆S
M_r = 288.29
Monoclinic, P 2₁ /n
a = 7.1512 (2) Å
b = 15.4303 (5) Å
c = 11.3217 (3) Å
β = 91.769 (2)°
V = 1248.70 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 296 K
0.21 × 0.11 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.958, T_max = 0.974
14122 measured reflections
3102 independent reflections
2101 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.128
S = 1.05
3102 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯O3ⁱ	0.96	2.50	3.453 (3)	169
Symmetry code: (i) x+1, y, z.

Data collection: APEX2 (Bruker, 2007); cell refinement: SMART (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011799/bt2918sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011799/bt2918Isup2.hkl

checkCIF report

Comment top

N-(Substituted phenyl)acetamides are considered as important intermediates in organic synthesis. A large number of heterocyclic compounds such as 2,5-piperazinedione (Wen et al., 2006), (quinolin-8-yloxy) acetamide (Zhang et al., 2006) and 2,2-(1,3,4-thiadiazolyl-2,5-dithio)diacetamide (Wen et al., 2005) are being efficiently synthesized starting from such acetamides. In the present paper, the structure of N-(4-Methoxy-2-nitrophenyl)-N-(methylsulfonyl)acetamide has been determined as part of a research program involving the synthesis and biological evaluation of sulfur containing heterocyclic compounds (Siddiqui et al., 2007).

In the molecule (Fig. 1), the bond lengths and bond angles are similar to those in the related molecules (Wen et al., 2006; Zhang et al., 2006) and are within in normal ranges. The nitro group is slightly twisted out of the plane of the aromatic ring. Each molecule is linked to its neighbour by inter molecular C—H···O interactions forming a chain along the a axis (Table 1 and Fig. 2).

Related literature top

For the synthesis of sulfur-containing heterocyclic compounds, see: Siddiqui et al. (2007); Wen et al. (2006); Zhang et al. (2006). For related structures, see: Zhang et al. (2006); Wen et al. (2005); Zia-ur-Rehman et al. (2008).

Experimental top

A mixture of N-(4-methoxy-2-nitrophenyl)methane sulfonamide (2.462507 g; 10.0 mmoles) and acetic anhydride (10.0 ml) was heated to reflux for half an hour and then poued over crushed ice. Resultant solids were then washed with cold water and dried under reduced pressure. Yellow crystals were obtained by slow evaporation of an ethanolic solution over a period of two days.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SMART (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Perspective view of the crystal packing showing inter molecular C—H···O interactions (dashed lines) along a. H atoms not involved in hydrogen bonding have been omitted for clarity.

N-(4-Methoxy-2-nitrophenyl)-N-(methylsulfonyl)acetamide top

Crystal data top

C₁₀H₁₂N₂O₆S	F(000) = 600
M_r = 288.29	D_x = 1.533 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3173 reflections
a = 7.1512 (2) Å	θ = 2.6–26.8°
b = 15.4303 (5) Å	µ = 0.29 mm⁻¹
c = 11.3217 (3) Å	T = 296 K
β = 91.769 (2)°	Needles, yellow
V = 1248.70 (6) Å³	0.21 × 0.11 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3102 independent reflections
Radiation source: fine-focus sealed tube	2101 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −8→9
T_min = 0.958, T_max = 0.974	k = −20→20
14122 measured reflections	l = −15→15

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0614P)² + 0.2596P] where P = (F_o² + 2F_c²)/3
3102 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₀H₁₂N₂O₆S	V = 1248.70 (6) Å³
M_r = 288.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.1512 (2) Å	µ = 0.29 mm⁻¹
b = 15.4303 (5) Å	T = 296 K
c = 11.3217 (3) Å	0.21 × 0.11 × 0.08 mm
β = 91.769 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3102 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2101 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.974	R_int = 0.042
14122 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.05	Δρ_max = 0.30 e Å⁻³
3102 reflections	Δρ_min = −0.32 e Å⁻³
172 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	0.23442 (8)	0.16533 (4)	0.86323 (4)	0.03679 (18)
O1	0.3919 (3)	0.43383 (14)	0.73036 (15)	0.0788 (7)
O2	0.5342 (3)	0.31646 (11)	0.76949 (14)	0.0535 (5)
O3	0.0897 (2)	0.22746 (11)	0.84351 (15)	0.0493 (4)
O4	0.3188 (2)	0.12704 (11)	0.76361 (13)	0.0489 (4)
O5	0.1853 (2)	0.54616 (10)	1.10272 (14)	0.0473 (4)
O6	0.6008 (3)	0.10620 (12)	0.94545 (17)	0.0634 (5)
N1	0.4337 (3)	0.37563 (12)	0.79726 (15)	0.0390 (4)
N2	0.3979 (2)	0.21872 (11)	0.94551 (14)	0.0353 (4)
C1	0.3511 (3)	0.30400 (13)	0.98604 (17)	0.0311 (4)
C2	0.3598 (3)	0.37840 (13)	0.91680 (16)	0.0296 (4)
C3	0.3029 (3)	0.45779 (13)	0.95680 (17)	0.0334 (5)
H3	0.3089	0.5064	0.9084	0.040*
C4	0.2359 (3)	0.46491 (14)	1.07076 (18)	0.0341 (5)
C5	0.2273 (3)	0.39268 (15)	1.14165 (18)	0.0413 (6)
H5	0.1845	0.3973	1.2181	0.050*
C6	0.2828 (3)	0.31336 (15)	1.09848 (18)	0.0393 (5)
H6	0.2740	0.2647	1.1464	0.047*
C7	0.1573 (4)	0.08423 (16)	0.9575 (2)	0.0538 (7)
H7A	0.2552	0.0425	0.9707	0.081*
H7B	0.0497	0.0561	0.9222	0.081*
H7C	0.1245	0.1095	1.0316	0.081*
C8	0.1068 (4)	0.55680 (17)	1.2166 (2)	0.0525 (7)
H8A	0.0775	0.6168	1.2288	0.079*
H8B	0.1955	0.5379	1.2766	0.079*
H8C	−0.0053	0.5228	1.2209	0.079*
C9	0.5736 (3)	0.18093 (16)	0.97108 (19)	0.0431 (6)
C10	0.7164 (4)	0.23869 (19)	1.0292 (2)	0.0590 (7)
H10A	0.6632	0.2951	1.0409	0.089*
H10B	0.8226	0.2436	0.9798	0.089*
H10C	0.7552	0.2146	1.1042	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0472 (4)	0.0292 (3)	0.0344 (3)	−0.0019 (2)	0.0066 (2)	−0.0012 (2)
O1	0.1238 (19)	0.0701 (14)	0.0443 (10)	0.0384 (13)	0.0293 (11)	0.0251 (10)
O2	0.0705 (12)	0.0439 (10)	0.0476 (9)	0.0051 (9)	0.0257 (8)	−0.0059 (8)
O3	0.0464 (10)	0.0414 (10)	0.0595 (10)	0.0024 (8)	−0.0069 (8)	−0.0045 (8)
O4	0.0640 (11)	0.0455 (10)	0.0378 (8)	−0.0032 (8)	0.0122 (7)	−0.0081 (7)
O5	0.0607 (11)	0.0338 (9)	0.0480 (9)	0.0058 (8)	0.0120 (8)	−0.0095 (7)
O6	0.0757 (14)	0.0435 (11)	0.0705 (12)	0.0253 (10)	−0.0037 (10)	−0.0059 (9)
N1	0.0486 (12)	0.0364 (11)	0.0324 (9)	−0.0029 (9)	0.0081 (8)	0.0001 (8)
N2	0.0418 (11)	0.0276 (10)	0.0367 (9)	0.0042 (8)	0.0042 (7)	−0.0011 (7)
C1	0.0328 (11)	0.0271 (11)	0.0335 (10)	0.0007 (9)	0.0034 (8)	−0.0016 (8)
C2	0.0292 (11)	0.0312 (11)	0.0285 (9)	−0.0022 (9)	0.0037 (7)	−0.0016 (8)
C3	0.0378 (12)	0.0283 (11)	0.0341 (10)	−0.0029 (9)	0.0017 (8)	0.0015 (8)
C4	0.0320 (12)	0.0313 (12)	0.0391 (11)	0.0008 (9)	0.0029 (8)	−0.0084 (9)
C5	0.0494 (14)	0.0428 (14)	0.0324 (10)	−0.0010 (11)	0.0126 (9)	−0.0037 (10)
C6	0.0499 (14)	0.0333 (12)	0.0353 (10)	0.0013 (10)	0.0103 (9)	0.0060 (9)
C7	0.0731 (18)	0.0406 (14)	0.0486 (13)	−0.0138 (13)	0.0156 (12)	0.0016 (11)
C8	0.0554 (16)	0.0489 (15)	0.0540 (14)	0.0012 (12)	0.0161 (12)	−0.0194 (12)
C9	0.0476 (14)	0.0426 (14)	0.0394 (11)	0.0143 (11)	0.0041 (10)	0.0010 (10)
C10	0.0478 (16)	0.0689 (19)	0.0597 (15)	0.0149 (14)	−0.0081 (12)	−0.0093 (14)

Geometric parameters (Å, º) top

S1—O3	1.4234 (17)	C3—H3	0.9300
S1—O4	1.4239 (15)	C4—C5	1.376 (3)
S1—N2	1.6868 (19)	C5—C6	1.381 (3)
S1—C7	1.745 (2)	C5—H5	0.9300
O1—N1	1.207 (2)	C6—H6	0.9300
O2—N1	1.209 (2)	C7—H7A	0.9600
O5—C4	1.357 (2)	C7—H7B	0.9600
O5—C8	1.432 (3)	C7—H7C	0.9600
O6—C9	1.206 (3)	C8—H8A	0.9600
N1—C2	1.469 (2)	C8—H8B	0.9600
N2—C9	1.407 (3)	C8—H8C	0.9600
N2—C1	1.437 (3)	C9—C10	1.493 (3)
C1—C6	1.385 (3)	C10—H10A	0.9600
C1—C2	1.393 (3)	C10—H10B	0.9600
C2—C3	1.372 (3)	C10—H10C	0.9600
C3—C4	1.394 (3)

O3—S1—O4	118.63 (10)	C4—C5—H5	120.2
O3—S1—N2	104.23 (9)	C6—C5—H5	120.2
O4—S1—N2	109.67 (10)	C5—C6—C1	122.1 (2)
O3—S1—C7	109.68 (13)	C5—C6—H6	119.0
O4—S1—C7	109.68 (11)	C1—C6—H6	119.0
N2—S1—C7	103.83 (11)	S1—C7—H7A	109.5
C4—O5—C8	117.47 (18)	S1—C7—H7B	109.5
O2—N1—O1	122.44 (18)	H7A—C7—H7B	109.5
O2—N1—C2	119.68 (18)	S1—C7—H7C	109.5
O1—N1—C2	117.88 (18)	H7A—C7—H7C	109.5
C9—N2—C1	121.94 (18)	H7B—C7—H7C	109.5
C9—N2—S1	120.69 (15)	O5—C8—H8A	109.5
C1—N2—S1	117.36 (14)	O5—C8—H8B	109.5
C6—C1—C2	117.03 (19)	H8A—C8—H8B	109.5
C6—C1—N2	118.78 (18)	O5—C8—H8C	109.5
C2—C1—N2	124.09 (17)	H8A—C8—H8C	109.5
C3—C2—C1	122.09 (17)	H8B—C8—H8C	109.5
C3—C2—N1	116.68 (18)	O6—C9—N2	119.8 (2)
C1—C2—N1	121.22 (18)	O6—C9—C10	124.3 (2)
C2—C3—C4	119.31 (19)	N2—C9—C10	116.0 (2)
C2—C3—H3	120.3	C9—C10—H10A	109.5
C4—C3—H3	120.3	C9—C10—H10B	109.5
O5—C4—C5	125.15 (19)	H10A—C10—H10B	109.5
O5—C4—C3	114.93 (19)	C9—C10—H10C	109.5
C5—C4—C3	119.91 (19)	H10A—C10—H10C	109.5
C4—C5—C6	119.54 (19)	H10B—C10—H10C	109.5

O3—S1—N2—C9	−172.42 (16)	O1—N1—C2—C1	160.0 (2)
O4—S1—N2—C9	−44.42 (19)	C1—C2—C3—C4	0.7 (3)
C7—S1—N2—C9	72.73 (18)	N1—C2—C3—C4	−178.38 (18)
O3—S1—N2—C1	6.58 (17)	C8—O5—C4—C5	−3.8 (3)
O4—S1—N2—C1	134.58 (15)	C8—O5—C4—C3	177.00 (19)
C7—S1—N2—C1	−108.27 (16)	C2—C3—C4—O5	179.21 (19)
C9—N2—C1—C6	−85.2 (3)	C2—C3—C4—C5	−0.1 (3)
S1—N2—C1—C6	95.8 (2)	O5—C4—C5—C6	179.9 (2)
C9—N2—C1—C2	98.7 (2)	C3—C4—C5—C6	−0.9 (3)
S1—N2—C1—C2	−80.3 (2)	C4—C5—C6—C1	1.4 (4)
C6—C1—C2—C3	−0.3 (3)	C2—C1—C6—C5	−0.7 (3)
N2—C1—C2—C3	175.92 (19)	N2—C1—C6—C5	−177.2 (2)
C6—C1—C2—N1	178.73 (19)	C1—N2—C9—O6	172.7 (2)
N2—C1—C2—N1	−5.0 (3)	S1—N2—C9—O6	−8.3 (3)
O2—N1—C2—C3	158.5 (2)	C1—N2—C9—C10	−7.6 (3)
O1—N1—C2—C3	−21.0 (3)	S1—N2—C9—C10	171.38 (17)
O2—N1—C2—C1	−20.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O3ⁱ	0.96	2.50	3.453 (3)	169

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₆S
M_r	288.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.1512 (2), 15.4303 (5), 11.3217 (3)
β (°)	91.769 (2)
V (Å³)	1248.70 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.21 × 0.11 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.958, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	14122, 3102, 2101
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.128, 1.05
No. of reflections	3102
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.32

Computer programs: APEX2 (Bruker, 2007), SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008) and local programs.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O3ⁱ	0.9600	2.5000	3.453 (3)	169.00

Symmetry code: (i) x+1, y, z.

Acknowledgements

The authors are grateful to Pakistan Council of Scientific & Industrial Research Laboratories Complex, Lahore, Pakistan, for the provision of necessary chemicals and facilities.

References

Bruker (2007). APEX2, SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siddiqui, H. L., Zia-ur-Rehman, M., Ahmad, N., Weaver, G. W. & Lucas, P. D. (2007). Chem. Pharm. Bull. 55, 1014–1017178. Web of Science CrossRef PubMed CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wen, Y.-H., Li, X.-M., Xu, L.-L., Tang, X.-F. & Zhang, S.-S. (2006). Acta Cryst. E62, o4427–o4428. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wen, Y.-H., Zhang, S.-S., Yu, B.-H., Li, X.-M. & Liu, Q. (2005). Acta Cryst. E61, o347–o348. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, S.-S., Xu, L.-L., Wen, H.-L., Li, X.-M. & Wen, Y.-H. (2006). Acta Cryst. E62, o3071–o3072. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zia-ur-Rehman, M., Akbar, N., Arshad, M. N. & Khan, I. U. (2008). Acta Cryst. E64, o2092. Web of Science CSD CrossRef IUCr Journals Google Scholar