N-(3-Nitro­phen­yl)methane­sulfonamide

The conformation of the N—H bond is anti to the m-nitro substituent in the structure of the title compound, C₇H₈N₂O₄S. The mol­ecules are linked into centrosymmetric dimers through an N—H...O hydrogen bond.

Key indicators

• Single-crystal X-ray study
• T = 299 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.042
• wR factor = 0.105
• Data-to-parameter ratio = 11.3

checkCIF/PLATON results

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Alert level C
PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) .        100 Ang.
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000)        1000 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          6

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
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   0 ALERT type 5 Informative message, check

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S1. Comment

Methanesulfonanilides are of interest due to their distinct chemical and physical properties. The alkyl sulfonanilido moiety is an important constituent of many biologically significant compounds. The stereochemistry of these molecules, particularly in the vicinity of the phenyl-N—H portion would be of extreme interest in formulating an explanation of their biological activity similar to phenolic derivatives. The biological activity is thought to be due to the hydrogen of the phenyl N—H portion of the sulfonanilide molecules as it can align itself, in relation to a receptor site. Thus the structural studies of sulfonanilides are of interest. In the present work, the structure of N-(3-nitrophenyl)-methanesulfonamde (3NPMSA) has been determined to explore the substituent effects of polar groups on the structures of anilides and sulfonanilides as part of a study on the systematization of the crystal structures of this class of compounds in general (Gowda et al., 2000; Gowda et al., 2007a,b,c). In the structure of 3NPMSA the conformation of the N—H bond is anti to the meta-nitro substituent (Fig.1). The amide hydrogen is thus available to a receptor molecule during biological activity. Selected geometric parameters are shown in Table 1. The molecules are linked into centrosymmetric dimers (Fig. 2) through a N—H···O hydrogen bond (Table 2).

Related literature

For related literature, see: Gowda et al. (2000); Gowda et al. (2007); Gowda et al. (2007a); Gowda et al. (2007b); Jayalakshmi & Gowda (2004).

S2. Experimental

The title compound was prepared according to a literature method (Jayalakshmi & Gowda, 2004). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra (Jayalakshmi & Gowda, 2004). Single crystals of the title compound were

obtained from an ethanolic solution and used for X-ray diffraction studied at room temperature.

S3. Refinement

All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (CH aromatic) or 0.96 Å (CH₃) with U_iso(H) = 1.2 U_eq(C) or U_iso(H) = 1.5 U_eq(C_methyl). The coordinates of the H atom bonded to N were refined with a distance restraint [N–H = 0.86 (1) Å] and U_iso(H) = 1.2 U_eq(N).

Computing details

Data collection: CAD-4-PC (Nonius, 1996); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Molecular structure of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Packing diagram viewed down the axis b

N-(3-nitrophenyl)methanesulfonamide

Crystal data

C7H8N2O4S	Z = 2
Mr = 216.21	F(000) = 224
Triclinic, P1	Dx = 1.592 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54180 Å
a = 6.959 (1) Å	Cell parameters from 25 reflections
b = 8.207 (1) Å	θ = 5.5–25.3°
c = 8.759 (1) Å	µ = 3.18 mm^−1
α = 96.93 (1)°	T = 299 K
β = 111.05 (1)°	Prism, orange
γ = 99.78 (1)°	0.25 × 0.20 × 0.20 mm
V = 451.02 (10) Å^3

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.071
Radiation source: fine-focus sealed tube	θmax = 66.9°, θmin = 5.5°
Graphite monochromator	h = −8→8
ω/2θ scans	k = −9→5
2782 measured reflections	l = −10→10
1611 independent reflections	3 standard reflections every 120 min
1427 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.105	w = 1/[σ^2(Fo^2) + (0.0588P)^2 + 0.0989P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
1611 reflections	Δρmax = 0.49 e Å^−3
143 parameters	Δρmin = −0.49 e Å^−3
1 restraint	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.091 (5)

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
C1	0.0954 (4)	0.8080 (3)	0.6291 (3)	0.0525 (6)
H1A	0.1469	0.9231	0.6882	0.063*
H1B	0.1232	0.7341	0.7074	0.063*
H1C	−0.0542	0.7869	0.5660	0.063*
C6	0.5674 (3)	0.7198 (2)	0.7373 (2)	0.0362 (4)
C7	0.5029 (3)	0.5475 (3)	0.7208 (2)	0.0390 (4)
H7	0.398 (4)	0.479 (3)	0.622 (3)	0.047*
C8	0.6099 (3)	0.4749 (2)	0.8503 (2)	0.0386 (4)
C9	0.7761 (3)	0.5638 (3)	0.9932 (3)	0.0447 (5)
H9	0.838 (4)	0.505 (4)	1.075 (3)	0.054*
C10	0.8369 (3)	0.7366 (3)	1.0067 (3)	0.0501 (5)
H10	0.947 (4)	0.796 (4)	1.100 (4)	0.060*
C11	0.7328 (3)	0.8137 (3)	0.8807 (3)	0.0456 (5)
H11	0.770 (4)	0.938 (4)	0.890 (3)	0.055*
N5	0.4746 (3)	0.8055 (2)	0.6095 (2)	0.0478 (5)
H5N	0.539 (4)	0.9067 (17)	0.621 (3)	0.057*
N12	0.5437 (3)	0.2912 (2)	0.8337 (2)	0.0515 (5)
O3	0.2113 (2)	0.8999 (2)	0.39469 (18)	0.0530 (4)
O4	0.1475 (2)	0.59956 (19)	0.41044 (18)	0.0507 (4)
O13	0.6464 (3)	0.2257 (2)	0.9437 (3)	0.0758 (6)
O14	0.3897 (4)	0.2133 (2)	0.7117 (2)	0.0742 (6)
S2	0.22342 (7)	0.77189 (6)	0.49366 (5)	0.0378 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0592 (13)	0.0449 (12)	0.0550 (12)	0.0107 (10)	0.0241 (10)	0.0113 (10)
C6	0.0321 (9)	0.0376 (10)	0.0367 (9)	0.0036 (7)	0.0118 (7)	0.0111 (8)
C7	0.0412 (10)	0.0353 (10)	0.0350 (9)	0.0021 (8)	0.0117 (8)	0.0062 (8)
C8	0.0439 (10)	0.0349 (10)	0.0435 (10)	0.0106 (8)	0.0225 (8)	0.0115 (8)
C9	0.0390 (10)	0.0542 (12)	0.0437 (11)	0.0151 (9)	0.0142 (8)	0.0192 (9)
C10	0.0378 (10)	0.0538 (13)	0.0434 (11)	0.0019 (9)	0.0022 (9)	0.0091 (10)
C11	0.0384 (10)	0.0386 (11)	0.0479 (11)	−0.0021 (8)	0.0075 (8)	0.0095 (9)
N5	0.0372 (9)	0.0424 (9)	0.0494 (10)	−0.0069 (7)	0.0029 (7)	0.0230 (8)
N12	0.0689 (12)	0.0380 (10)	0.0583 (11)	0.0180 (9)	0.0324 (10)	0.0162 (9)
O3	0.0497 (8)	0.0513 (9)	0.0454 (8)	−0.0002 (7)	0.0041 (6)	0.0257 (7)
O4	0.0506 (8)	0.0392 (8)	0.0468 (8)	−0.0013 (6)	0.0087 (6)	0.0006 (7)
O13	0.0925 (14)	0.0541 (11)	0.0904 (14)	0.0316 (10)	0.0319 (12)	0.0393 (11)
O14	0.1008 (15)	0.0382 (9)	0.0638 (11)	−0.0025 (9)	0.0188 (10)	0.0045 (8)
S2	0.0367 (3)	0.0330 (3)	0.0339 (3)	−0.00126 (19)	0.0055 (2)	0.00977 (19)

Geometric parameters (Å, º)

C1—S2	1.747 (2)	C9—C10	1.387 (3)
C1—H1A	0.9600	C9—H9	0.93 (3)
C1—H1B	0.9600	C10—C11	1.376 (3)
C1—H1C	0.9600	C10—H10	0.91 (3)
C6—C7	1.382 (3)	C11—H11	1.00 (3)
C6—C11	1.387 (3)	N5—S2	1.6293 (17)
C6—N5	1.411 (2)	N5—H5N	0.849 (10)
C7—C8	1.380 (3)	N12—O14	1.216 (3)
C7—H7	0.94 (3)	N12—O13	1.221 (3)
C8—C9	1.375 (3)	O3—S2	1.4351 (15)
C8—N12	1.472 (3)	O4—S2	1.4254 (15)
S2—C1—H1A	109.5	C11—C10—C9	120.5 (2)
S2—C1—H1B	109.5	C11—C10—H10	121.6 (19)
H1A—C1—H1B	109.5	C9—C10—H10	117.9 (19)
S2—C1—H1C	109.5	C10—C11—C6	120.6 (2)
H1A—C1—H1C	109.5	C10—C11—H11	121.9 (15)
H1B—C1—H1C	109.5	C6—C11—H11	117.4 (15)
C7—C6—C11	120.16 (19)	C6—N5—S2	126.27 (13)
C7—C6—N5	122.12 (17)	C6—N5—H5N	116.1 (19)
C11—C6—N5	117.69 (18)	S2—N5—H5N	111.8 (19)
C8—C7—C6	117.54 (18)	O14—N12—O13	123.6 (2)
C8—C7—H7	120.1 (15)	O14—N12—C8	118.38 (19)
C6—C7—H7	122.1 (15)	O13—N12—C8	118.0 (2)
C9—C8—C7	123.82 (19)	O4—S2—O3	118.55 (9)
C9—C8—N12	118.12 (19)	O4—S2—N5	109.14 (10)
C7—C8—N12	118.06 (19)	O3—S2—N5	104.09 (9)
C8—C9—C10	117.39 (19)	O4—S2—C1	108.26 (10)
C8—C9—H9	118.3 (16)	O3—S2—C1	109.55 (12)
C10—C9—H9	124.3 (16)	N5—S2—C1	106.62 (11)
C11—C6—C7—C8	−0.6 (3)	C7—C6—N5—S2	41.2 (3)
N5—C6—C7—C8	177.35 (18)	C11—C6—N5—S2	−140.83 (19)
C6—C7—C8—C9	−0.2 (3)	C9—C8—N12—O14	176.1 (2)
C6—C7—C8—N12	−179.54 (17)	C7—C8—N12—O14	−4.6 (3)
C7—C8—C9—C10	0.5 (3)	C9—C8—N12—O13	−3.6 (3)
N12—C8—C9—C10	179.83 (19)	C7—C8—N12—O13	175.7 (2)
C8—C9—C10—C11	0.0 (4)	C6—N5—S2—O4	−57.2 (2)
C9—C10—C11—C6	−0.8 (4)	C6—N5—S2—O3	175.34 (19)
C7—C6—C11—C10	1.1 (3)	C6—N5—S2—C1	59.6 (2)
N5—C6—C11—C10	−176.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···O3^i	0.85 (1)	2.20 (2)	2.984 (2)	153 (3)

Symmetry code: (i) −x+1, −y+2, −z+1.