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Acta Cryst. (2008). E64, o2299    [ doi:10.1107/S1600536808035861 ]

1-Methylsulfonyl-4-nitrobenzene

D.-S. Ma

Abstract top

In the title compound, C7H7NO4S, the nitro group is twisted by 10.2 (5) ° out of the plane of the benzene ring. Inversion-related molecules are linked by non-classical C-H...O hydrogen bonds into dimers featuring an R22(10) motif.

Comment top

Simple carboxylic acids containing the nitrophenyl group exhibit a variety of supramolecular aggregation patterns (Glidewell et al., 2002). We had reported the crystal structure of (2-nitrophenylsulfinyl)acetic acid in our previous work (Ma, 2007). In our attempt to synthesize the homologous compound of it, we unexpectedly obtain the title compound, (I), which is prepared by the decarboxylated reaction of (4-nitrophenylsulfonyl)acetic acid.

In (Fig. 1), all bond lengths and angles are normal. The nitro group is twisted out the phenylene ring by 10.2 (5) °.

A centrosymmetric dimer, containing an R22(10) motif, is built up by C—H···O hydrogen bonding interactions between the phenyl and nitryl (Fig.2; table 1).

Related literature top

For the synthesis, see: Nobles & Thompson (1965). For the supramolecular patterns of nitrophenyl compounds, see Glidewell et al. (2002); Ma (2007).

Experimental top

4-Nitrophenylthioacetic acid was prepared by nucleophilic reaction of chloroacetic acid (9.4 g, 0.1 mol) and 4-nitrothiophenol (15.5 g, 0.1 mol) under basic conditions. 4-Nitrophenylthioacetic acid (21.3 g, 0.1 mol) was then oxidized using 30% aqueous hydrogen peroxide (30 ml)in acetic anhydride solution (50 ml) (Nobles et al., 1965). Unexpectedly product was obtained, namely 1-(methylsulfonyl)-4-nitrobenzene, which formed by the (4-nitrophenylsulfonyl)acetic acid decarboxylation under excessive hydrogen peroxide conditions.

Refinement top

All H atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic), Uiso(H) = 1.2Ueq(C); C—H = 0.96 Å (methyl), Uiso(H) = 1.5Ueq(C).

Computing details top

Data collection: RAPID-AUTO (Rigaku Corporation, 1998); cell refinement: RAPID-AUTO (Rigaku Corporation, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level for non-H atoms.
[Figure 2] Fig. 2. A view of the hydrogen-bonded (dashed lines) dimer.
1-Methylsulfonyl-4-nitrobenzene top
Crystal data top
C7H7NO4SF(000) = 416
Mr = 201.20Dx = 1.587 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4509 reflections
a = 6.3765 (13) Åθ = 3.2–27.5°
b = 8.0411 (16) ŵ = 0.36 mm−1
c = 16.426 (3) ÅT = 291 K
β = 91.67 (3)°Block, yellow
V = 841.9 (3) Å30.21 × 0.19 × 0.16 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1933 independent reflections
Radiation source: fine-focus sealed tube1045 reflections with I > 2σ(I)
graphiteRint = 0.042
ω scanθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −8→8
Tmin = 0.926, Tmax = 0.942k = −10→9
7967 measured reflectionsl = −21→20
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0576P)2 + 0.5194P]
where P = (Fo2 + 2Fc2)/3
1933 reflections(Δ/σ)max < 0.001
119 parametersΔρmax = 0.32 e Å−3
6 restraintsΔρmin = −0.45 e Å−3
Crystal data top
C7H7NO4SV = 841.9 (3) Å3
Mr = 201.20Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.3765 (13) ŵ = 0.36 mm−1
b = 8.0411 (16) ÅT = 291 K
c = 16.426 (3) Å0.21 × 0.19 × 0.16 mm
β = 91.67 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1933 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		1045 reflections with I > 2σ(I)
Tmin = 0.926, Tmax = 0.942Rint = 0.042
7967 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.152Δρmax = 0.32 e Å−3
S = 1.12Δρmin = −0.45 e Å−3
1933 reflectionsAbsolute structure: ?
119 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
C10.1240 (5)0.8495 (4)0.09033 (17)0.0426 (7)
C2−0.0744 (5)0.7940 (5)0.1076 (2)0.0546 (9)
H1−0.12680.80940.15930.066*
C3−0.1953 (6)0.7154 (4)0.0478 (2)0.0548 (9)
H2−0.32970.67770.05840.066*
C4−0.1117 (5)0.6945 (4)−0.02732 (18)0.0444 (8)
C50.0841 (5)0.7492 (4)−0.04584 (19)0.0523 (9)
H30.13550.7340−0.09770.063*
C60.2042 (5)0.8273 (4)0.01402 (18)0.0480 (8)
H40.33840.86480.00300.058*
C70.3546 (7)0.7850 (5)0.2321 (2)0.0716 (12)
H50.43920.82780.27670.107*
H60.43420.70530.20240.107*
H70.23200.73230.25280.107*
N1−0.2387 (6)0.6099 (3)−0.09136 (19)0.0586 (8)
O10.4601 (4)1.0152 (3)0.13042 (15)0.0703 (8)
O20.1478 (4)1.0591 (3)0.21070 (16)0.0754 (8)
O3−0.1539 (5)0.5713 (4)−0.15365 (18)0.0873 (10)
O4−0.4225 (5)0.5820 (4)−0.07856 (17)0.0822 (9)
S10.27883 (14)0.94820 (10)0.16746 (5)0.0497 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0461 (18)0.0391 (16)0.0423 (16)0.0029 (13)−0.0008 (13)0.0050 (13)
C20.051 (2)0.068 (2)0.0453 (17)−0.0034 (17)0.0038 (15)0.0008 (16)
C30.046 (2)0.063 (2)0.0553 (19)−0.0115 (17)−0.0019 (16)0.0019 (17)
C40.0487 (19)0.0360 (15)0.0475 (17)0.0011 (14)−0.0129 (14)0.0033 (14)
C50.055 (2)0.061 (2)0.0411 (16)0.0026 (17)−0.0005 (15)−0.0022 (16)
C60.0415 (18)0.0573 (19)0.0452 (17)−0.0024 (15)−0.0016 (14)0.0034 (15)
C70.096 (3)0.065 (2)0.053 (2)−0.004 (2)−0.025 (2)0.0075 (18)
N10.074 (2)0.0427 (15)0.0574 (18)−0.0008 (15)−0.0218 (16)0.0021 (14)
O10.0643 (17)0.0840 (18)0.0619 (14)−0.0326 (14)−0.0080 (12)0.0045 (14)
O20.083 (2)0.0676 (16)0.0756 (17)0.0135 (15)−0.0062 (14)−0.0285 (14)
O30.104 (2)0.086 (2)0.0707 (18)−0.0009 (17)−0.0156 (17)−0.0348 (16)
O40.073 (2)0.093 (2)0.0790 (18)−0.0289 (16)−0.0244 (15)0.0059 (16)
S10.0566 (6)0.0457 (5)0.0461 (5)−0.0040 (4)−0.0074 (4)−0.0011 (4)
Geometric parameters (Å, °) top
C1—C21.378 (5)C5—H30.9300
C1—C61.379 (4)C6—H40.9300
C1—S11.771 (3)C7—S11.747 (4)
C2—C31.384 (5)C7—H50.9600
C2—H10.9300C7—H60.9600
C3—C41.369 (5)C7—H70.9600
C3—H20.9300N1—O31.212 (4)
C4—C51.367 (5)N1—O41.218 (4)
C4—N11.475 (4)O1—S11.427 (3)
C5—C61.380 (4)O2—S11.425 (3)
C2—C1—C6120.8 (3)C5—C6—H4120.2
C2—C1—S1119.6 (2)S1—C7—H5109.5
C6—C1—S1119.6 (2)S1—C7—H6109.5
C1—C2—C3119.8 (3)H5—C7—H6109.5
C1—C2—H1120.1S1—C7—H7109.5
C3—C2—H1120.1H5—C7—H7109.5
C4—C3—C2118.2 (3)H6—C7—H7109.5
C4—C3—H2120.9O3—N1—O4123.6 (3)
C2—C3—H2120.9O3—N1—C4118.1 (3)
C5—C4—C3122.9 (3)O4—N1—C4118.2 (3)
C5—C4—N1118.4 (3)O2—S1—O1118.03 (18)
C3—C4—N1118.6 (3)O2—S1—C7108.81 (19)
C4—C5—C6118.6 (3)O1—S1—C7109.2 (2)
C4—C5—H3120.7O2—S1—C1108.31 (16)
C6—C5—H3120.7O1—S1—C1107.79 (15)
C1—C6—C5119.6 (3)C7—S1—C1103.70 (16)
C1—C6—H4120.2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H2···O4i0.932.653.462 (5)147
Symmetry codes: (i) −x−1, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H2···O4i0.932.653.462 (5)147
Symmetry codes: (i) −x−1, −y+1, −z.
Acknowledgements top

The authors thank Heilongjiang University for supporting this study.

references
References top

Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2002). Acta Cryst. C58, o201–o203.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Ma, D.-S. (2007). Acta Cryst. E63, o658–o659.

Nobles, W. L. & Thompson, B. B. (1965). J. Pharm. Sci. 54, 709–713.

Rigaku Corporation (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.