2-(2-Nitro­phenyl­sulfin­yl)acetonitrile

Benmebarek, S.; Boudraa, M.; Bouacida, S.; Merazig, H.

doi:10.1107/S1600536813004832

organic compounds

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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page o432

doi:10.1107/S1600536813004832

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2-(2-Nitrophenylsulfinyl)acetonitrile

Sabrina Benmebarek,^a Mhamed Boudraa,^a Sofiane Bouacida ^a,^b ^* and Hocine Merazig ^a

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Université Mentouri–Constantine, 25000 , Algeria, and ^bDépartement Sciences de la Matière, Faculté des Sciences Exactes et Sciences de la Nature et de la Vie, Université Oum El Bouaghi, Algeria
^*Correspondence e-mail: Bouacida_Sofiane@yahoo.fr

(Received 18 February 2013; accepted 19 February 2013; online 23 February 2013)

In the title compound, C₈H₆N₂O₃S, the dihedral angle between the nitro group and the benzene ring is 6.76 (9)°. The bond-angle sum at the S atom is 308.1°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds to generate (010) sheets. The crystal studied was found to be a racemic twin.

Related literature

For a related structure and background to sulfoxides, see: Benmebarek et al. (2012 ). For related structures see: Yan (2010 ); Kobayashi et al. (2003 ).

Experimental

Crystal data

C₈H₆N₂O₃S
M_r = 210.21
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.4114 (2) Å
b = 10.7602 (4) Å
c = 15.1837 (5) Å
V = 884.11 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 295 K
0.26 × 0.2 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
8401 measured reflections
2348 independent reflections
2222 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.070
S = 1.05
2348 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ), 1379 Friedel pairs
Flack parameter: 0.53 (1)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2ⁱ	0.93	2.41	3.3198 (18)	165
C7—H7A⋯O2ⁱⁱ	0.97	2.50	3.1190 (19)	122
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2011 ); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 2012 ) and DIAMOND (Brandenburg & Berndt, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813004832/hb7044sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813004832/hb7044Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813004832/hb7044Isup3.cml

checkCIF report

Comment top

As part of our ongoing studies on the synthesis, structures and biological activity of organometallic sulfanilamide complexes (Benmebarek et al. 2012), we have synthesized and determined the crystal structure of the title compound, (I). The molecular geometry and the atom-numbering scheme are shown in Fig 1. The bond angle sum at the S atom is 308.1°. The nitro group forms a dihedral angle of 6.76 (9)° with the benzene ring, which is very different to that found in 2-(methylsulfinyl)benzamide (25.6°) (Yan, 2010) and in benzamide (26.3°) (Kobayashi et al., 2003), and similar to chloromethylsulfinyl-2-nitrobenzene (2.7°) (Benmebarek et al., 2012). The crystal structure features C—H···O hydrogen bonds (Fig. 2) forming (010) sheets.

Related literature top

For a related structure and background to sulfoxides, see: Benmebarek et al. (2012). For related structures see: Yan (2010); Kobayashi et al., (2003).

Experimental top

Chloromethylsulfinyl-2-nitrobenzene (2.196 g, 10 mmol) obtained according to established procedures (Benmebarek et al., 2012) and potassium cyanide (0.65 g, 10 mmol) were dissolved in 75 ml aqua ethanol solution (25 ml water + 50 ml ethanol) and refluxed for 3 h under continuous stirring. Then the obtained product was evaporated at room temperature to dryness. The residue was diluted in 50 ml pure ethanol. After a few days, colourless blocks were recovered, as the solvent slowly evaporated.

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: APEX2 (Bruker, 2011); data reduction: APEX2 (Bruker, 2011); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. View of the asymetric unit of, (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Packing diagram of (I) viwed down [100] showing the hydrogen bonding in alterning layers parallel to (010) planes.

2-(2-Nitrophenylsulfinyl)acetonitrile top

Crystal data top

C₈H₆N₂O₃S	F(000) = 432
M_r = 210.21	D_x = 1.579 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6191 reflections
a = 5.4114 (2) Å	θ = 2.7–29.1°
b = 10.7602 (4) Å	µ = 0.35 mm⁻¹
c = 15.1837 (5) Å	T = 295 K
V = 884.11 (5) Å³	Block, colourless
Z = 4	0.26 × 0.2 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	2222 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.016
Graphite monochromator	θ_max = 29.1°, θ_min = 4.0°
ϕ and ω scans	h = −6→7
8401 measured reflections	k = −14→14
2348 independent reflections	l = −20→20

Refinement top

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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0327P)² + 0.2515P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2348 reflections	Δρ_max = 0.21 e Å⁻³
128 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1379 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.53 (1)

Crystal data top

C₈H₆N₂O₃S	V = 884.11 (5) Å³
M_r = 210.21	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.4114 (2) Å	µ = 0.35 mm⁻¹
b = 10.7602 (4) Å	T = 295 K
c = 15.1837 (5) Å	0.26 × 0.2 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	2222 reflections with I > 2σ(I)
8401 measured reflections	R_int = 0.016
2348 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.070	Δρ_max = 0.21 e Å⁻³
S = 1.05	Δρ_min = −0.18 e Å⁻³
2348 reflections	Absolute structure: Flack (1983), 1379 Friedel pairs
128 parameters	Absolute structure parameter: 0.53 (1)
0 restraints

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
S2	0.53769 (6)	0.02767 (3)	0.15053 (2)	0.02770 (9)
O2	0.5137 (2)	−0.06613 (11)	0.22173 (7)	0.0395 (3)
O11	0.4219 (4)	0.16230 (15)	−0.12118 (8)	0.0678 (5)
O12	0.5834 (2)	0.17541 (11)	0.00821 (9)	0.0453 (3)
N1	0.4351 (3)	0.13166 (12)	−0.04412 (9)	0.0352 (3)
N8	−0.0001 (3)	0.12996 (17)	0.28063 (10)	0.0515 (4)
C1	0.2643 (3)	0.03718 (13)	−0.01153 (9)	0.0263 (3)
C2	0.2906 (2)	−0.01016 (12)	0.07377 (8)	0.0235 (2)
C3	0.1293 (3)	−0.10289 (13)	0.10054 (10)	0.0294 (3)
H3	0.1443	−0.137	0.1566	0.035*
C4	−0.0546 (3)	−0.14513 (14)	0.04407 (11)	0.0357 (3)
H4	−0.1622	−0.2071	0.0628	0.043*
C5	−0.0795 (3)	−0.09610 (15)	−0.03950 (11)	0.0376 (3)
H5	−0.2034	−0.125	−0.0767	0.045*
C6	0.0809 (3)	−0.00355 (14)	−0.06796 (9)	0.0343 (3)
H6	0.0651	0.0304	−0.124	0.041*
C7	0.4040 (3)	0.17220 (14)	0.19493 (11)	0.0341 (3)
H7A	0.5225	0.2113	0.234	0.041*
H7B	0.3711	0.2292	0.1468	0.041*
C8	0.1763 (3)	0.14879 (15)	0.24274 (10)	0.0330 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2	0.02549 (15)	0.02869 (16)	0.02891 (16)	0.00442 (13)	−0.00081 (13)	−0.00137 (13)
C1	0.0308 (6)	0.0236 (6)	0.0246 (6)	0.0010 (5)	0.0058 (5)	0.0006 (5)
O2	0.0509 (7)	0.0360 (5)	0.0316 (5)	0.0073 (5)	−0.0070 (5)	0.0061 (4)
C3	0.0344 (7)	0.0242 (6)	0.0296 (7)	−0.0001 (5)	0.0047 (6)	0.0007 (5)
O12	0.0399 (7)	0.0423 (6)	0.0537 (7)	−0.0116 (5)	0.0041 (6)	0.0087 (5)
C5	0.0359 (8)	0.0373 (8)	0.0395 (8)	0.0008 (7)	−0.0071 (7)	−0.0108 (6)
N1	0.0417 (7)	0.0303 (6)	0.0336 (6)	−0.0008 (6)	0.0104 (6)	0.0055 (5)
N8	0.0469 (10)	0.0585 (9)	0.0492 (8)	0.0082 (8)	0.0136 (8)	−0.0025 (7)
C2	0.0249 (6)	0.0216 (6)	0.0241 (6)	0.0019 (5)	0.0024 (5)	−0.0019 (5)
C4	0.0326 (7)	0.0291 (6)	0.0453 (8)	−0.0061 (6)	0.0045 (7)	−0.0038 (6)
C6	0.0440 (8)	0.0347 (7)	0.0244 (6)	0.0065 (6)	−0.0034 (6)	−0.0033 (5)
O11	0.0987 (13)	0.0692 (10)	0.0354 (6)	−0.0252 (9)	0.0125 (8)	0.0169 (6)
C8	0.0360 (8)	0.0329 (7)	0.0299 (7)	0.0085 (6)	−0.0016 (6)	−0.0045 (6)
C7	0.0337 (8)	0.0286 (7)	0.0401 (8)	0.0006 (6)	0.0013 (6)	−0.0080 (6)

Geometric parameters (Å, º) top

S2—O2	1.4846 (11)	C5—C4	1.381 (2)
S2—C2	1.8197 (13)	C5—C6	1.390 (2)
S2—C7	1.8429 (15)	C5—H5	0.93
C1—C6	1.382 (2)	N1—O11	1.2177 (17)
C1—C2	1.3989 (18)	N8—C8	1.133 (2)
C1—N1	1.4606 (18)	C4—H4	0.93
C3—C2	1.3867 (19)	C6—H6	0.93
C3—C4	1.390 (2)	C8—C7	1.452 (2)
C3—H3	0.93	C7—H7A	0.97
O12—N1	1.2235 (19)	C7—H7B	0.97

O2—S2—C2	104.49 (6)	C3—C2—S2	115.83 (10)
O2—S2—C7	105.84 (7)	C1—C2—S2	125.91 (10)
C2—S2—C7	97.74 (7)	C5—C4—C3	120.78 (15)
C6—C1—C2	122.12 (13)	C5—C4—H4	119.6
C6—C1—N1	117.72 (12)	C3—C4—H4	119.6
C2—C1—N1	120.16 (12)	C1—C6—C5	118.86 (13)
C2—C3—C4	120.35 (13)	C1—C6—H6	120.6
C2—C3—H3	119.8	C5—C6—H6	120.6
C4—C3—H3	119.8	N8—C8—C7	179.36 (19)
C4—C5—C6	119.90 (15)	C8—C7—S2	111.69 (11)
C4—C5—H5	120	C8—C7—H7A	109.3
C6—C5—H5	120	S2—C7—H7A	109.3
O11—N1—O12	123.94 (15)	C8—C7—H7B	109.3
O11—N1—C1	118.48 (15)	S2—C7—H7B	109.3
O12—N1—C1	117.58 (12)	H7A—C7—H7B	107.9
C3—C2—C1	117.97 (13)

C6—C1—N1—O11	−6.2 (2)	C7—S2—C2—C3	−102.58 (11)
C2—C1—N1—O11	173.11 (15)	O2—S2—C2—C1	−167.63 (11)
C6—C1—N1—O12	173.76 (14)	C7—S2—C2—C1	83.73 (12)
C2—C1—N1—O12	−7.0 (2)	C6—C5—C4—C3	0.1 (2)
C4—C3—C2—C1	−1.0 (2)	C2—C3—C4—C5	0.2 (2)
C4—C3—C2—S2	−175.24 (11)	C2—C1—C6—C5	−1.2 (2)
C6—C1—C2—C3	1.5 (2)	N1—C1—C6—C5	178.08 (13)
N1—C1—C2—C3	−177.73 (12)	C4—C5—C6—C1	0.3 (2)
C6—C1—C2—S2	175.08 (11)	O2—S2—C7—C8	−42.69 (13)
N1—C1—C2—S2	−4.16 (18)	C2—S2—C7—C8	64.82 (12)
O2—S2—C2—C3	6.06 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.41	3.3198 (18)	165
C7—H7A···O2ⁱⁱ	0.97	2.50	3.1190 (19)	122

Symmetry codes: (i) −x+1/2, −y, z−1/2; (ii) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₆N₂O₃S
M_r	210.21
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	5.4114 (2), 10.7602 (4), 15.1837 (5)
V (Å³)	884.11 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.26 × 0.2 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8401, 2348, 2222
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.070, 1.05
No. of reflections	2348
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.18
Absolute structure	Flack (1983), 1379 Friedel pairs
Absolute structure parameter	0.53 (1)

Computer programs: APEX2 (Bruker, 2011), SIR2002 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.41	3.3198 (18)	165
C7—H7A···O2ⁱⁱ	0.97	2.50	3.1190 (19)	122

Symmetry codes: (i) −x+1/2, −y, z−1/2; (ii) −x+1, y+1/2, −z+1/2.

Acknowledgements

This work is supported by `Unité de recherche de Chimie de l'Environnement et Moléculaire Structurale' (CHEMS), Université de Constantine, Algeria. Thanks are due to MESRS and ATRST (Ministére de l'Enseignement Supérieur et de la Recherche Scientifique et l'Agence thématique de recherche en sciences et technologie, Algérie) via the PNR program for financial support.

References

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