Bis(3-nitro­phen­yl) sulfone

Abstract

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,

• a = 20.260 (4) Å

• b = 5.9380 (12) Å

• c = 5.3770 (11) Å

• V = 646.9 (2) ų

• 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[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 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)

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.

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
C4—H4A⋯O1	0.93	2.58	2.928 (4)	102

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically, with C-H= 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Figures

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.

Crystal data

C12H8N2O6S	F000 = 316
Mr = 308.27	Dx = 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 = 10–13º
b = 5.9380 (12) Å	µ = 0.28 mm−1
c = 5.3770 (11) Å	T = 294 (2) K
V = 646.9 (2) Å3	Block, light yellow
Z = 2	0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.028
Radiation source: fine-focus sealed tube	θmax = 25.2º
Monochromator: graphite	θmin = 2.0º
T = 294(2) K	h = −24→24
ω/2θ scans	k = −7→0
Absorption correction: ψ scan(North et al., 1968)	l = 0→6
Tmin = 0.920, Tmax = 0.972	3 standard reflections
1304 measured reflections	every 120 min
674 independent reflections	intensity decay: none
624 reflections with I > 2σ(I)

Refinement

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.06P)2 + 0.078P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.032	(Δ/σ)max < 0.001
wR(F2) = 0.086	Δρmax = 0.25 e Å−3
S = 1.00	Δρmin = −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	Flack parameter: −0.11 (15)
Hydrogen site location: inferred from neighbouring sites

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 > 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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, y, z.

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