1-Methyl­sulfon­yl-4-nitro­benzene

Ma, D.-S.

doi:10.1107/S1600536808035861

organic compounds

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Volume 64| Part 12| December 2008| Page o2299

doi:10.1107/S1600536808035861

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1-Methylsulfonyl-4-nitrobenzene

Dong-Sheng Ma ^a ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: hgf1000@163.com

(Received 29 October 2008; accepted 1 November 2008; online 8 November 2008)

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.

Related literature

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

Experimental

Crystal data

C₇H₇NO₄S
M_r = 201.20
Monoclinic, P 2₁ /c
a = 6.3765 (13) Å
b = 8.0411 (16) Å
c = 16.426 (3) Å
β = 91.67 (3)°
V = 841.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 291 (2) K
0.21 × 0.19 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.926, T_max = 0.942
7967 measured reflections
1933 independent reflections
1045 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.152
S = 1.11
1933 reflections
119 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.32 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
C3—H2⋯O4ⁱ	0.93	2.65	3.462 (5)	147
Symmetry code: (i) -x-1, -y+1, -z.

Data collection: RAPID-AUTO (Rigaku Corporation, 1998 ); cell refinement: RAPID-AUTO; 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.

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536808035861/ng2509sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035861/ng2509Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level for non-H atoms.
	Fig. 2. A view of the hydrogen-bonded (dashed lines) dimer.

1-Methylsulfonyl-4-nitrobenzene top

Crystal data top

C₇H₇NO₄S	F(000) = 416
M_r = 201.20	D_x = 1.587 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4509 reflections
a = 6.3765 (13) Å	θ = 3.2–27.5°
b = 8.0411 (16) Å	µ = 0.36 mm⁻¹
c = 16.426 (3) Å	T = 291 K
β = 91.67 (3)°	Block, yellow
V = 841.9 (3) Å³	0.21 × 0.19 × 0.16 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	1933 independent reflections
Radiation source: fine-focus sealed tube	1045 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω scan	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
T_min = 0.926, T_max = 0.942	k = −10→9
7967 measured reflections	l = −21→20

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0576P)² + 0.5194P] where P = (F_o² + 2F_c²)/3
1933 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.32 e Å⁻³
6 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₇H₇NO₄S	V = 841.9 (3) Å³
M_r = 201.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.3765 (13) Å	µ = 0.36 mm⁻¹
b = 8.0411 (16) Å	T = 291 K
c = 16.426 (3) Å	0.21 × 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)
T_min = 0.926, T_max = 0.942	R_int = 0.042
7967 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	6 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.12	Δρ_max = 0.32 e Å⁻³
1933 reflections	Δρ_min = −0.45 e Å⁻³
119 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	0.1240 (5)	0.8495 (4)	0.09033 (17)	0.0426 (7)
C2	−0.0744 (5)	0.7940 (5)	0.1076 (2)	0.0546 (9)
H1	−0.1268	0.8094	0.1593	0.066*
C3	−0.1953 (6)	0.7154 (4)	0.0478 (2)	0.0548 (9)
H2	−0.3297	0.6777	0.0584	0.066*
C4	−0.1117 (5)	0.6945 (4)	−0.02732 (18)	0.0444 (8)
C5	0.0841 (5)	0.7492 (4)	−0.04584 (19)	0.0523 (9)
H3	0.1355	0.7340	−0.0977	0.063*
C6	0.2042 (5)	0.8273 (4)	0.01402 (18)	0.0480 (8)
H4	0.3384	0.8648	0.0030	0.058*
C7	0.3546 (7)	0.7850 (5)	0.2321 (2)	0.0716 (12)
H5	0.4392	0.8278	0.2767	0.107*
H6	0.4342	0.7053	0.2024	0.107*
H7	0.2320	0.7323	0.2528	0.107*
N1	−0.2387 (6)	0.6099 (3)	−0.09136 (19)	0.0586 (8)
O1	0.4601 (4)	1.0152 (3)	0.13042 (15)	0.0703 (8)
O2	0.1478 (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)
S1	0.27883 (14)	0.94820 (10)	0.16746 (5)	0.0497 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0461 (18)	0.0391 (16)	0.0423 (16)	0.0029 (13)	−0.0008 (13)	0.0050 (13)
C2	0.051 (2)	0.068 (2)	0.0453 (17)	−0.0034 (17)	0.0038 (15)	0.0008 (16)
C3	0.046 (2)	0.063 (2)	0.0553 (19)	−0.0115 (17)	−0.0019 (16)	0.0019 (17)
C4	0.0487 (19)	0.0360 (15)	0.0475 (17)	0.0011 (14)	−0.0129 (14)	0.0033 (14)
C5	0.055 (2)	0.061 (2)	0.0411 (16)	0.0026 (17)	−0.0005 (15)	−0.0022 (16)
C6	0.0415 (18)	0.0573 (19)	0.0452 (17)	−0.0024 (15)	−0.0016 (14)	0.0034 (15)
C7	0.096 (3)	0.065 (2)	0.053 (2)	−0.004 (2)	−0.025 (2)	0.0075 (18)
N1	0.074 (2)	0.0427 (15)	0.0574 (18)	−0.0008 (15)	−0.0218 (16)	0.0021 (14)
O1	0.0643 (17)	0.0840 (18)	0.0619 (14)	−0.0326 (14)	−0.0080 (12)	0.0045 (14)
O2	0.083 (2)	0.0676 (16)	0.0756 (17)	0.0135 (15)	−0.0062 (14)	−0.0285 (14)
O3	0.104 (2)	0.086 (2)	0.0707 (18)	−0.0009 (17)	−0.0156 (17)	−0.0348 (16)
O4	0.073 (2)	0.093 (2)	0.0790 (18)	−0.0289 (16)	−0.0244 (15)	0.0059 (16)
S1	0.0566 (6)	0.0457 (5)	0.0461 (5)	−0.0040 (4)	−0.0074 (4)	−0.0011 (4)

Geometric parameters (Å, º) top

C1—C2	1.378 (5)	C5—H3	0.9300
C1—C6	1.379 (4)	C6—H4	0.9300
C1—S1	1.771 (3)	C7—S1	1.747 (4)
C2—C3	1.384 (5)	C7—H5	0.9600
C2—H1	0.9300	C7—H6	0.9600
C3—C4	1.369 (5)	C7—H7	0.9600
C3—H2	0.9300	N1—O3	1.212 (4)
C4—C5	1.367 (5)	N1—O4	1.218 (4)
C4—N1	1.475 (4)	O1—S1	1.427 (3)
C5—C6	1.380 (4)	O2—S1	1.425 (3)

C2—C1—C6	120.8 (3)	C5—C6—H4	120.2
C2—C1—S1	119.6 (2)	S1—C7—H5	109.5
C6—C1—S1	119.6 (2)	S1—C7—H6	109.5
C1—C2—C3	119.8 (3)	H5—C7—H6	109.5
C1—C2—H1	120.1	S1—C7—H7	109.5
C3—C2—H1	120.1	H5—C7—H7	109.5
C4—C3—C2	118.2 (3)	H6—C7—H7	109.5
C4—C3—H2	120.9	O3—N1—O4	123.6 (3)
C2—C3—H2	120.9	O3—N1—C4	118.1 (3)
C5—C4—C3	122.9 (3)	O4—N1—C4	118.2 (3)
C5—C4—N1	118.4 (3)	O2—S1—O1	118.03 (18)
C3—C4—N1	118.6 (3)	O2—S1—C7	108.81 (19)
C4—C5—C6	118.6 (3)	O1—S1—C7	109.2 (2)
C4—C5—H3	120.7	O2—S1—C1	108.31 (16)
C6—C5—H3	120.7	O1—S1—C1	107.79 (15)
C1—C6—C5	119.6 (3)	C7—S1—C1	103.70 (16)
C1—C6—H4	120.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H2···O4ⁱ	0.93	2.65	3.462 (5)	147

Symmetry code: (i) −x−1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₇H₇NO₄S
M_r	201.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	6.3765 (13), 8.0411 (16), 16.426 (3)
β (°)	91.67 (3)
V (Å³)	841.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.21 × 0.19 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.926, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	7967, 1933, 1045
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.152, 1.12
No. of reflections	1933
No. of parameters	119
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.45

Computer programs: RAPID-AUTO (Rigaku Corporation, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H2···O4ⁱ	0.93	2.65	3.462 (5)	146.9

Symmetry code: (i) −x−1, −y+1, −z.

Acknowledgements

The authors thank Heilongjiang University for supporting this study.

References

Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2002). Acta Cryst. C58, o201–o203. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Ma, D.-S. (2007). Acta Cryst. E63, o658–o659. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Rigaku Corporation (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
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