N-(4-Nitro­phen­yl)methane­sulfonamide

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

doi:10.1107/S160053680701598X

N-(4-Nitrophenyl)methanesulfonamide

The structure of the title compound (4NPMSA), C₇H₈N₂O₄S, closely resembles those of N-phenylmethanesulfonamide (PMSA) and N-(3-nitrophenyl)methanesulfonamide (4NPMSA), with slightly different geometric parameters. The substitution of a nitro group at the para position of PMSA does not change the space group, unlike the case of meta substitution (3NPMSA), where it changes from monoclinic P2₁/c to triclinic P $\overline{1}$ [Gowda, Foro & Fuess (2007c). Acta Cryst. E63, o2337]. The N—H H atom and the methylsulfonyl group are trans to one another across the plane of the benzene ring. Thus, the amide H atom is available to a receptor molecule during biological activity. An N—H

O hydrogen bond links the molecules into centrosymmetric dimers.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680701598X/lw2006sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680701598X/lw2006Isup2.hkl Contains datablock I

CCDC reference: 614581

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Key indicators

Single-crystal X-ray study
T = 299 K
Mean (C-C) = 0.007 Å
R factor = 0.060
wR factor = 0.182
Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.17
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      1.170
            Tmax scaled      0.911 Tmin scaled      0.640

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

   0 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
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The alkyl sulfonanilide 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, is of interest in explaining their biological activity. This biological activity is thought to be due to the H atom of the phenyl N—H portion of the sulfonanilide molecules, as it can align itself in relation to a receptor site. Therefore, structural studies of sulfonanilides are of interest. In the present work, the structure of the title compound (4NPMSA) has been determined to explore the substituent effects of polar groups on the structures of anilides and sulfonanilides (Gowda et al., 2007a,b; Gowda et al., 2000; Gowda, Kozisek et al., 2007).

The substitution of a nitro group at the para position of N-(phenyl)methanesulfonamide (PMSA) does not change the space group, unlike in the case of meta substitution (3NPMSA), where it changes from monoclinic P21/c (Klug, 1968) to triclinic P1 (Gowda et al., 2007c).

The N—H H atom projects alone on one side of the plane of the phenyl group, while the whole methanesulfonyl group is on the opposite side of the plane (Fig. 1), similar to what was observed in PMSA (Klug, 1968) and 3NPMSA (Gowda et al., 2007c). The amide H atom is thus available to a receptor molecule during biological activity.

An N—H···O hydrogen bond links the molecules of (I) into centrosymmetric dimers (Table 1 and Fig. 2).

Related literature top

For related literature, see: Gowda et al. (2000); Gowda, Kozisek et al., (2007); Gowda et al., (2007a), (2007b), (2007c); Jayalakshmi & Gowda (2004); Klug (1968).

Experimental top

The title compound was prepared according to the literature method of Jayalakshmi & Gowda (2004). The purity of the compound was checked by determining its melting point. It was characterized by recording its IR and NMR spectra (Jayalakshmi & Gowda, 2004). Single crystals of the title compound were obtained by slow evaporation of an ethanolic solution and used for X-ray diffraction studied at room temperature.

Structure description top

An N—H···O hydrogen bond links the molecules of (I) into centrosymmetric dimers (Table 1 and Fig. 2).

For related literature, see: Gowda et al. (2000); Gowda, Kozisek et al., (2007); Gowda et al., (2007a), (2007b), (2007c); Jayalakshmi & Gowda (2004); Klug (1968).

Computing details top

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. A packing diagram, viewed down the axis b

N-(4-Nitrophenyl)methanesulfonamide top

Crystal data top

C₇H₈N₂O₄S	F(000) = 448
M_r = 216.21	D_x = 1.561 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 10.879 (2) Å	θ = 4.3–24.4°
b = 10.336 (2) Å	µ = 3.12 mm⁻¹
c = 8.715 (1) Å	T = 299 K
β = 110.13 (1)°	Laminar, grey
V = 920.1 (3) Å³	0.17 × 0.15 × 0.03 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1149 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 66.9°, θ_min = 4.3°
ω/2θ scans	h = −12→12
Absorption correction: ψ scan (North et al., 1968)	k = −12→1
T_min = 0.547, T_max = 0.778	l = −10→0
1780 measured reflections	3 standard reflections every 120 min
1642 independent reflections	intensity decay: 3.5%

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)] = 0.060	H-atom parameters constrained
wR(F²) = 0.182	w = 1/[σ²(F_o²) + (0.1074P)²] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1642 reflections	Δρ_max = 0.56 e Å⁻³
128 parameters	Δρ_min = −0.61 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0089 (16)

Crystal data top

C₇H₈N₂O₄S	V = 920.1 (3) Å³
M_r = 216.21	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 10.879 (2) Å	µ = 3.12 mm⁻¹
b = 10.336 (2) Å	T = 299 K
c = 8.715 (1) Å	0.17 × 0.15 × 0.03 mm
β = 110.13 (1)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1149 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.035
T_min = 0.547, T_max = 0.778	3 standard reflections every 120 min
1780 measured reflections	intensity decay: 3.5%
1642 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.182	H-atom parameters constrained
S = 1.09	Δρ_max = 0.56 e Å⁻³
1642 reflections	Δρ_min = −0.61 e Å⁻³
128 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
C1	0.6245 (5)	0.4037 (5)	0.4016 (5)	0.0484 (12)
H1A	0.5738	0.3869	0.4705	0.058*
H1B	0.6365	0.4953	0.3951	0.058*
H1C	0.7083	0.3624	0.4465	0.058*
C6	0.2974 (4)	0.4055 (4)	0.1995 (5)	0.0383 (10)
C7	0.2810 (5)	0.2996 (4)	0.2895 (6)	0.0454 (11)
H7	0.3418	0.2326	0.3160	0.054*
C8	0.1728 (5)	0.2953 (5)	0.3392 (6)	0.0486 (12)
H8	0.1603	0.2248	0.3985	0.058*
C9	0.0845 (4)	0.3948 (5)	0.3008 (6)	0.0467 (12)
C10	0.1012 (5)	0.5004 (5)	0.2138 (6)	0.0521 (12)
H10	0.0406	0.5675	0.1892	0.063*
C11	0.2070 (4)	0.5065 (5)	0.1636 (6)	0.0473 (11)
H11	0.2187	0.5781	0.1055	0.057*
N5	0.4013 (4)	0.4164 (4)	0.1407 (5)	0.0429 (9)
H5N	0.3894	0.4683	0.0598	0.051*
N12	−0.0295 (4)	0.3886 (5)	0.3520 (6)	0.0596 (12)
O3	0.6074 (3)	0.3835 (3)	0.0984 (4)	0.0535 (9)
O4	0.5206 (4)	0.2075 (3)	0.2198 (4)	0.0534 (9)
O13	−0.0451 (4)	0.2933 (4)	0.4271 (6)	0.0816 (14)
O14	−0.1055 (4)	0.4809 (5)	0.3203 (6)	0.0847 (14)
S2	0.54234 (11)	0.34283 (10)	0.20640 (13)	0.0386 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.053 (3)	0.055 (3)	0.040 (3)	−0.008 (2)	0.019 (2)	−0.003 (2)
C6	0.039 (2)	0.037 (2)	0.036 (2)	−0.0042 (18)	0.0099 (19)	−0.0023 (18)
C7	0.044 (3)	0.039 (2)	0.056 (3)	0.001 (2)	0.020 (2)	0.008 (2)
C8	0.044 (3)	0.048 (3)	0.057 (3)	−0.008 (2)	0.021 (2)	0.003 (2)
C9	0.037 (2)	0.050 (3)	0.055 (3)	−0.008 (2)	0.017 (2)	−0.009 (2)
C10	0.045 (2)	0.044 (3)	0.069 (3)	0.004 (2)	0.021 (2)	0.005 (2)
C11	0.045 (2)	0.037 (2)	0.059 (3)	0.000 (2)	0.018 (2)	0.008 (2)
N5	0.045 (2)	0.042 (2)	0.046 (2)	0.0050 (17)	0.0208 (18)	0.0135 (17)
N12	0.048 (2)	0.062 (3)	0.074 (3)	−0.015 (2)	0.026 (2)	−0.016 (2)
O3	0.058 (2)	0.065 (2)	0.0493 (19)	0.0109 (17)	0.0337 (17)	0.0111 (16)
O4	0.070 (2)	0.0342 (17)	0.057 (2)	0.0042 (16)	0.0222 (18)	−0.0036 (15)
O13	0.086 (3)	0.066 (3)	0.117 (4)	−0.018 (2)	0.066 (3)	−0.004 (3)
O14	0.051 (2)	0.085 (3)	0.129 (4)	0.006 (2)	0.045 (3)	−0.003 (3)
S2	0.0457 (6)	0.0369 (6)	0.0377 (6)	0.0035 (5)	0.0202 (4)	0.0006 (5)

Geometric parameters (Å, º) top

C1—S2	1.744 (5)	C9—C10	1.377 (7)
C1—H1A	0.9600	C9—N12	1.457 (6)
C1—H1B	0.9600	C10—C11	1.366 (6)
C1—H1C	0.9600	C10—H10	0.9300
C6—C11	1.394 (6)	C11—H11	0.9300
C6—C7	1.394 (6)	N5—S2	1.629 (4)
C6—N5	1.398 (5)	N5—H5N	0.8600
C7—C8	1.388 (7)	N12—O13	1.226 (6)
C7—H7	0.9300	N12—O14	1.230 (6)
C8—C9	1.368 (7)	O3—S2	1.422 (3)
C8—H8	0.9300	O4—S2	1.431 (3)

S2—C1—H1A	109.5	C11—C10—C9	119.9 (5)
S2—C1—H1B	109.5	C11—C10—H10	120.0
H1A—C1—H1B	109.5	C9—C10—H10	120.0
S2—C1—H1C	109.5	C10—C11—C6	120.0 (4)
H1A—C1—H1C	109.5	C10—C11—H11	120.0
H1B—C1—H1C	109.5	C6—C11—H11	120.0
C11—C6—C7	119.9 (4)	C6—N5—S2	128.1 (3)
C11—C6—N5	117.1 (4)	C6—N5—H5N	116.0
C7—C6—N5	123.1 (4)	S2—N5—H5N	116.0
C8—C7—C6	119.2 (4)	O13—N12—O14	122.5 (5)
C8—C7—H7	120.4	O13—N12—C9	119.2 (5)
C6—C7—H7	120.4	O14—N12—C9	118.3 (5)
C9—C8—C7	119.9 (5)	O3—S2—O4	118.5 (2)
C9—C8—H8	120.0	O3—S2—N5	104.6 (2)
C7—C8—H8	120.0	O4—S2—N5	108.9 (2)
C8—C9—C10	121.1 (5)	O3—S2—C1	109.5 (2)
C8—C9—N12	119.5 (5)	O4—S2—C1	108.5 (2)
C10—C9—N12	119.4 (5)	N5—S2—C1	106.2 (2)

C11—C6—C7—C8	1.3 (7)	C11—C6—N5—S2	158.9 (4)
N5—C6—C7—C8	−178.2 (4)	C7—C6—N5—S2	−21.5 (6)
C6—C7—C8—C9	−0.6 (7)	C8—C9—N12—O13	−0.9 (7)
C7—C8—C9—C10	−0.3 (8)	C10—C9—N12—O13	178.7 (5)
C7—C8—C9—N12	179.3 (4)	C8—C9—N12—O14	177.9 (5)
C8—C9—C10—C11	0.4 (8)	C10—C9—N12—O14	−2.4 (7)
N12—C9—C10—C11	−179.3 (5)	C6—N5—S2—O3	177.0 (4)
C9—C10—C11—C6	0.4 (8)	C6—N5—S2—O4	49.4 (4)
C7—C6—C11—C10	−1.3 (7)	C6—N5—S2—C1	−67.2 (4)
N5—C6—C11—C10	178.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···O3ⁱ	0.86	2.07	2.914 (5)	168

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₇H₈N₂O₄S
M_r	216.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	299
a, b, c (Å)	10.879 (2), 10.336 (2), 8.715 (1)
β (°)	110.13 (1)
V (Å³)	920.1 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.12
Crystal size (mm)	0.17 × 0.15 × 0.03

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.547, 0.778
No. of measured, independent and observed [I > 2σ(I)] reflections	1780, 1642, 1149
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.182, 1.09
No. of reflections	1642
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.61

Computer programs: CAD-4-PC (Enraf–Nonius, 1996), CAD-4-PC, REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.