1-Methyl­sulfon­yl-4-nitro­benzene

Abstract

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 R ² ₂(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,

• a = 6.3765 (13) Å

• b = 8.0411 (16) Å

• c = 16.426 (3) Å

• β = 91.67 (3)°

• V = 841.9 (3) ų

• 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[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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).

Experimental

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

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

Figures

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.

Crystal data

C7H7NO4S	F000 = 416
Mr = 201.20	Dx = 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 = 3.2–27.5º
b = 8.0411 (16) Å	µ = 0.36 mm−1
c = 16.426 (3) Å	T = 291 (2) K
β = 91.67 (3)º	Block, yellow
V = 841.9 (3) Å3	0.21 × 0.19 × 0.16 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	1933 independent reflections
Radiation source: fine-focus sealed tube	1045 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.042
T = 291(2) K	θmax = 27.5º
ω scan	θmin = 3.2º
Absorption correction: Multi-scan(ABSCOR; Higashi, 1995)	h = −8→8
Tmin = 0.926, Tmax = 0.942	k = −10→9
7967 measured reflections	l = −21→20

Refinement

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)] = 0.042	H-atom parameters constrained
wR(F2) = 0.152	w = 1/[σ2(Fo2) + (0.0576P)2 + 0.5194P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max < 0.001
1933 reflections	Δρmax = 0.32 e Å−3
119 parameters	Δρmin = −0.45 e Å−3
6 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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	0.1240 (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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) −x−1, −y+1, −z.