Bis(3-nitro­phen­yl) sulfone

Yao, W.; Li, F.-S.; Yu, D.-S.; Liu, M.-J.; Zhu, J.-N.

doi:10.1107/S160053680801917X

organic compounds

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Bis(3-nitrophenyl) sulfone

Wei Yao,^a Fang-Shi Li,^a ^* Da-Sheng Yu,^a Mei-Juan Liu ^a and Jin-Na Zhu ^a

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Xinmofan Road No. 5, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: fangshi.li@njut.edu.cn

(Received 24 June 2008; accepted 24 June 2008; online 5 July 2008)

The asymmetric unit of the title compound, C₁₂H₈N₂O₆S, an important diphenyl sulfone derivative, contains one half-molecule; a mirror plane passes through the SO₂ group. The dihedral angle between the two symmetry-related benzene rings is 40.10 (13)°. An intramolecular C—H⋯O hydrogen bond results in the formation of a five-membered ring, which adopts an envelope conformation.

Related literature

For related literature, see: Ayyangar et al. (1981 ); Amer et al. (1989 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₈N₂O₆S
M_r = 308.27
Orthorhombic, P m n 2₁
a = 20.260 (4) Å
b = 5.9380 (12) Å
c = 5.3770 (11) Å
V = 646.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 294 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.920, T_max = 0.972
1304 measured reflections
674 independent reflections
624 reflections with I > 2σ(I)
R_int = 0.028
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.086
S = 1.00
674 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ), with no Friedel pairs
Flack parameter: −0.11 (15)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O1	0.93	2.58	2.928 (4)	102

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801917X/hk2478sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680801917X/hk2478Isup2.hkl

checkCIF report

Comment top

The title compound, (I), is used for preparing 3,3'-diaminodiphenyl sulfone (Ayyangar et al., 1981). As part of our studies in this area, we report herein the synthesis and crystal structure of (I).

The asymmetric unit of (I) (Fig. 1) contains one half molecule. The bond lengths (Allen et al., 1987) and angles are within normal ranges. The dihedral angle between the two symmetry related bezene rings is 139.90 (13)°. The intramolecular C-H···O hydrogen bond (Table 1) results in the formation of a five-membered non-planar ring: (S/O1/C3/C4/H4A), in which it adopts envelope conformation, with O1 atom displaced by -0.494 (3) Å from the planes of the other ring atoms.

Related literature top

For related literature, see: Ayyangar et al. (1981); Amer et al. (1989). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I), was prepared according to the literature method (Amer et al., 1989). Crystals suitable for X-ray analysis were obtained by dissolving (I) (0.2 g) in dichloroethane (25 ml) and evaporating the solvent slowly at room temperature for about 7 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme [symmetry code: (') -x, y, z]. Hydrogen bonds are shown as dashed lines.

Bis(3-nitrophenyl) sulfone top

Crystal data top

C₁₂H₈N₂O₆S	F(000) = 316
M_r = 308.27	D_x = 1.583 Mg m⁻³
Orthorhombic, Pmn2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac -2	Cell parameters from 25 reflections
a = 20.260 (4) Å	θ = 10–13°
b = 5.9380 (12) Å	µ = 0.28 mm⁻¹
c = 5.3770 (11) Å	T = 294 K
V = 646.9 (2) Å³	Block, light yellow
Z = 2	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	624 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 25.2°, θ_min = 2.0°
ω/2θ scans	h = −24→24
Absorption correction: ψ scan (North et al., 1968)	k = −7→0
T_min = 0.920, T_max = 0.972	l = 0→6
1304 measured reflections	3 standard reflections every 120 min
674 independent reflections	intensity decay: none

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.06P)² + 0.078P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.032	(Δ/σ)_max < 0.001
wR(F²) = 0.086	Δρ_max = 0.25 e Å⁻³
S = 1.00	Δρ_min = −0.22 e Å⁻³
674 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
101 parameters	Extinction coefficient: 0.069 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with no Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.11 (15)
Hydrogen site location: inferred from neighbouring sites

Crystal data top

C₁₂H₈N₂O₆S	V = 646.9 (2) Å³
M_r = 308.27	Z = 2
Orthorhombic, Pmn2₁	Mo Kα radiation
a = 20.260 (4) Å	µ = 0.28 mm⁻¹
b = 5.9380 (12) Å	T = 294 K
c = 5.3770 (11) Å	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	624 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.028
T_min = 0.920, T_max = 0.972	3 standard reflections every 120 min
1304 measured reflections	intensity decay: none
674 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.086	Δρ_max = 0.25 e Å⁻³
S = 1.00	Δρ_min = −0.22 e Å⁻³
674 reflections	Absolute structure: Flack (1983), with no Friedel pairs
101 parameters	Absolute structure parameter: −0.11 (15)

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 > 2sigma(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
S	0.5000	0.08254 (19)	0.9607 (2)	0.0438 (4)
N	0.68253 (13)	0.0542 (4)	0.2895 (5)	0.0422 (6)
O1	0.5000	−0.1563 (5)	0.9183 (9)	0.0626 (12)
O2	0.5000	0.1705 (7)	1.2095 (7)	0.0663 (11)
O3	0.66204 (14)	−0.1343 (4)	0.2403 (5)	0.0660 (8)
O4	0.72681 (13)	0.1460 (4)	0.1767 (5)	0.0599 (7)
C1	0.64732 (14)	0.4956 (5)	0.7589 (8)	0.0451 (8)
H1B	0.6638	0.6351	0.8072	0.054*
C2	0.59364 (14)	0.4066 (5)	0.8822 (7)	0.0410 (7)
H2B	0.5741	0.4842	1.0131	0.049*
C3	0.56929 (13)	0.1978 (5)	0.8063 (5)	0.0347 (7)
C4	0.59799 (14)	0.0791 (4)	0.6139 (6)	0.0341 (6)
H4A	0.5816	−0.0603	0.5648	0.041*
C5	0.65163 (13)	0.1743 (5)	0.4973 (6)	0.0356 (6)
C6	0.67683 (14)	0.3828 (4)	0.5672 (7)	0.0410 (7)
H6A	0.7130	0.4442	0.4852	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0316 (5)	0.0543 (6)	0.0455 (7)	0.000	0.000	0.0169 (6)
N	0.0448 (13)	0.0450 (14)	0.0367 (14)	0.0071 (11)	0.0003 (12)	−0.0003 (11)
O1	0.0408 (17)	0.0472 (16)	0.100 (3)	0.000	0.000	0.032 (2)
O2	0.049 (2)	0.114 (3)	0.0364 (18)	0.000	0.000	0.016 (2)
O3	0.0784 (19)	0.0580 (15)	0.0615 (18)	−0.0025 (12)	0.0081 (16)	−0.0211 (14)
O4	0.0545 (14)	0.0738 (16)	0.0512 (15)	0.0009 (12)	0.0190 (12)	0.0005 (14)
C1	0.0374 (14)	0.0341 (14)	0.064 (2)	−0.0016 (12)	−0.0022 (16)	−0.0079 (16)
C2	0.0370 (15)	0.0400 (15)	0.0460 (17)	0.0078 (12)	−0.0021 (14)	−0.0055 (14)
C3	0.0274 (12)	0.0381 (14)	0.0386 (16)	0.0013 (11)	−0.0031 (12)	0.0081 (13)
C4	0.0341 (13)	0.0323 (12)	0.0359 (16)	−0.0004 (11)	−0.0049 (13)	0.0041 (14)
C5	0.0326 (13)	0.0370 (13)	0.0373 (14)	0.0067 (10)	−0.0038 (13)	0.0026 (13)
C6	0.0353 (14)	0.0364 (14)	0.0511 (19)	−0.0024 (12)	0.0046 (15)	0.0033 (14)

Geometric parameters (Å, º) top

S—O2	1.436 (4)	C1—H1B	0.9300
S—O1	1.437 (3)	C2—C3	1.395 (4)
S—C3	1.769 (3)	C2—H2B	0.9300
S—C3ⁱ	1.769 (3)	C3—C4	1.380 (4)
N—O4	1.212 (4)	C4—C5	1.376 (4)
N—O3	1.223 (3)	C4—H4A	0.9300
N—C5	1.466 (4)	C5—C6	1.391 (4)
C1—C6	1.367 (5)	C6—H6A	0.9300
C1—C2	1.379 (4)

O2—S—O1	120.5 (3)	C3—C2—H2B	120.7
O2—S—C3	107.24 (14)	C4—C3—C2	121.6 (3)
O1—S—C3	107.92 (15)	C4—C3—S	119.2 (2)
O2—S—C3ⁱ	107.24 (14)	C2—C3—S	119.2 (3)
O1—S—C3ⁱ	107.92 (15)	C5—C4—C3	117.7 (3)
C3—S—C3ⁱ	105.06 (18)	C5—C4—H4A	121.2
O4—N—O3	123.7 (3)	C3—C4—H4A	121.2
O4—N—C5	118.6 (3)	C4—C5—C6	122.2 (3)
O3—N—C5	117.7 (3)	C4—C5—N	119.0 (3)
C6—C1—C2	121.3 (3)	C6—C5—N	118.8 (3)
C6—C1—H1B	119.3	C1—C6—C5	118.6 (3)
C2—C1—H1B	119.3	C1—C6—H6A	120.7
C1—C2—C3	118.6 (3)	C5—C6—H6A	120.7
C1—C2—H2B	120.7

C6—C1—C2—C3	−0.4 (5)	S—C3—C4—C5	179.7 (2)
C1—C2—C3—C4	0.6 (5)	C3—C4—C5—C6	−0.1 (4)
C1—C2—C3—S	−179.4 (2)	C3—C4—C5—N	−179.0 (2)
O2—S—C3—C4	152.5 (2)	O4—N—C5—C4	175.0 (3)
O1—S—C3—C4	21.3 (3)	O3—N—C5—C4	−5.2 (4)
C3ⁱ—S—C3—C4	−93.6 (2)	O4—N—C5—C6	−3.9 (4)
O2—S—C3—C2	−27.5 (3)	O3—N—C5—C6	175.9 (3)
O1—S—C3—C2	−158.6 (3)	C2—C1—C6—C5	0.0 (5)
C3ⁱ—S—C3—C2	86.4 (3)	C4—C5—C6—C1	0.3 (5)
C2—C3—C4—C5	−0.3 (4)	N—C5—C6—C1	179.2 (3)

Symmetry code: (i) −x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1	0.93	2.58	2.928 (4)	102

Experimental details

Crystal data
Chemical formula	C₁₂H₈N₂O₆S
M_r	308.27
Crystal system, space group	Orthorhombic, Pmn2₁
Temperature (K)	294
a, b, c (Å)	20.260 (4), 5.9380 (12), 5.3770 (11)
V (Å³)	646.9 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.920, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	1304, 674, 624
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.086, 1.00
No. of reflections	674
No. of parameters	101
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.22
Absolute structure	Flack (1983), with no Friedel pairs
Absolute structure parameter	−0.11 (15)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1	0.93	2.58	2.928 (4)	102.00

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Amer, A., El-Massry, A. M. & Pittman, C. U. (1989). Chem. Scr. 29, 351–352. CAS Google Scholar
Ayyangar, N. R., Lugade, A. G., Nikrad, P. V. & Sharma, V. K. (1981). Synthesis, pp. 640–643. CrossRef Google Scholar
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Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1378

doi:10.1107/S160053680801917X

Open

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