6-Nitro-1,3-benzoxazole-2(3H)-thione

Jebbari, S.; Abdellatif, E.K.; Ahbala, M.; Saadi, M.; El Ammari, L.

doi:10.1107/S2414314619011192

organic compounds

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ISSN: 2414-3146

Volume 4| Part 8| August 2019| x191119

https://doi.org/10.1107/S2414314619011192

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6-Nitro-1,3-benzoxazole-2(3H)-thione

Said Jebbari,^a El Kihel Abdellatif,^a Mustapha Ahbala,^a ^* Mohamed Saadi ^b and Lahcen El Ammari ^b

^aLaboratoire de Chimie Bioorganique, Faculté des Sciences, Université Chouaib Doukkali, BP 20, M-24000 El Jadida, Morocco, and ^bLaboratoire de Chimie Appliquée des Matériaux, Centre des Sciences des Matériaux, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Batouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: m_ahbala@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 9 August 2019; accepted 11 August 2019; online 16 August 2019)

In the title compound, C₇H₄N₂O₃S, the dihedral angle between the fused ring system (r.m.s. deviation = 0.008 Å) and the nitro group at the 6-position is 7.3 (2)°. In the crystal, bifurcated N—H⋯(O,O) hydrogen bonds link the molecules into [010] chains. The chains are cross-linked by π–π stacking interactions to form (001) sheets.

Keywords: enzoxazole derivative; benzoxazole-2-thione; crystal structure.

CCDC reference: 1946542

Structure description

The mono-nitration of some benzimidazole derivatives has been reported (Benchidmi et al., 1995 ; El Kihel et al., 1999 ). In this work, the nitration of benzoxazole-2-thione has been carried out and the crystal structure determined to establish the location of the NO₂ group (the 5- or 6-position) in the product (Fig. 1).

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

The plane of the fused ring system (r.m.s. deviation = 0.008 Å) is slightly inclined to the plane of the nitro group [dihedral angle = 7.3 (2)°]. In the crystal, the molecules are linked by bifurcated N—H⋯(O,O) hydrogen bonds (Table 1) to form [010] chains (Fig. 2). The chains are cross-linked by weak aromatic π–π stacking between the benzene ring and oxazole ring to form (001) sheets, the inter-centroid distance being 3.646 (3) Å (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.84	2.41	3.068 (3)	135
N1—H1⋯O3ⁱ	0.84	2.36	3.137 (3)	154
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
Projection of the title compound structure onto the (100) plane, showing molecules connected by hydrogen bonds (dashed blue lines).

Figure 3
Crystal packing for the title compound showing molecules linked by hydrogen bonds (dashed blue lines) and π–π interactions (green lines).

Synthesis and crystallization

To benzoxazole-2-thione (0.025 mol) in 92% H₂SO₄ (10 ml) was added dropwise with stirring a cooled mixture of 42% HNO₃ (2.5 ml) and 92% H₂SO₄ (1 ml). The resulting mixture was allowed to stand for 1 h at 273–278 K and then poured in an ice–water mixture (50 g – 50 g). After addition of NaCl (10 g), the solution, maintained at 273–283 K, deposited solid material, which was filtered off, washed with cold water and dissolved in hot water. The pH of the resulting solution was adjusted to 7.5–8 with 3 M NH₃. 6-Nitrobenzoxazole-2-thione was filtered off and recrystallized several times from methanol solution to give yellow blocks.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₄N₂O₃S
M_r	196.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	4.576 (4), 15.755 (13), 11.134 (9)
β (°)	100.45 (3)
V (Å³)	789.3 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.38
Crystal size (mm)	0.35 × 0.28 × 0.21

Data collection
Diffractometer	Bruker D8 VENTURE Super DUO
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.668, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	17038, 1870, 1538
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.03
No. of reflections	1870
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.26
Computer programs: APEX3 (Bruker, 2016 ), SAINT (Bruker, 2016), SHELXTL2014 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), WinGX and ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1946542

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619011192/hb4314sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619011192/hb4314Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619011192/hb4314Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXTL2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: WinGX and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).

6-Nitro-1,3-benzoxazole-2(3H)-thione top

Crystal data top

C₇H₄N₂O₃S	F(000) = 400
M_r = 196.18	D_x = 1.651 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.576 (4) Å	Cell parameters from 1870 reflections
b = 15.755 (13) Å	θ = 2.6–27.9°
c = 11.134 (9) Å	µ = 0.38 mm⁻¹
β = 100.45 (3)°	T = 296 K
V = 789.3 (11) Å³	Block, yellow
Z = 4	0.35 × 0.28 × 0.21 mm

Data collection top

Bruker D8 VENTURE Super DUO diffractometer	1870 independent reflections
Radiation source: INCOATEC IµS micro-focus source	1538 reflections with I > 2σ(I)
HELIOS mirror optics monochromator	R_int = 0.032
Detector resolution: 10.4167 pixels mm^-1	θ_max = 27.9°, θ_min = 2.6°
φ and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −20→20
T_min = 0.668, T_max = 0.747	l = −14→14
17038 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0541P)² + 0.3797P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
1870 reflections	Δρ_max = 0.30 e Å⁻³
118 parameters	Δρ_min = −0.26 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	1.18641 (11)	0.72656 (3)	0.51464 (5)	0.05120 (19)
O1	0.8774 (3)	0.58902 (7)	0.44023 (12)	0.0400 (3)
O2	0.2383 (5)	0.33844 (10)	0.26846 (17)	0.0859 (7)
O3	−0.1051 (4)	0.39654 (11)	0.1403 (2)	0.0766 (6)
N1	0.7184 (3)	0.70175 (9)	0.33226 (14)	0.0374 (3)
H1	0.688902	0.753157	0.314460	0.045*
N2	0.1258 (4)	0.40037 (11)	0.21413 (16)	0.0500 (4)
C1	0.9228 (4)	0.67448 (11)	0.42680 (16)	0.0360 (4)
C2	0.6377 (4)	0.56547 (10)	0.35289 (15)	0.0325 (4)
C3	0.5143 (4)	0.48630 (11)	0.33371 (16)	0.0383 (4)
H3	0.586671	0.439175	0.380032	0.046*
C4	0.2721 (4)	0.48278 (11)	0.23917 (17)	0.0379 (4)
C5	0.1602 (4)	0.55204 (13)	0.16860 (18)	0.0429 (4)
H5	−0.004636	0.545447	0.106807	0.051*
C6	0.2929 (4)	0.63094 (12)	0.18979 (18)	0.0425 (4)
H6	0.223268	0.678035	0.142831	0.051*
C7	0.5340 (4)	0.63613 (10)	0.28427 (16)	0.0331 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0455 (3)	0.0438 (3)	0.0604 (4)	−0.0078 (2)	−0.0005 (2)	−0.0129 (2)
O1	0.0442 (7)	0.0267 (6)	0.0445 (7)	0.0005 (5)	−0.0042 (5)	0.0015 (5)
O2	0.1327 (18)	0.0374 (8)	0.0735 (12)	−0.0331 (10)	−0.0189 (11)	0.0090 (8)
O3	0.0572 (10)	0.0574 (10)	0.1077 (15)	−0.0142 (8)	−0.0056 (10)	−0.0284 (10)
N1	0.0369 (8)	0.0232 (6)	0.0508 (9)	0.0024 (6)	0.0043 (6)	0.0038 (6)
N2	0.0596 (11)	0.0418 (9)	0.0495 (10)	−0.0154 (8)	0.0120 (8)	−0.0138 (8)
C1	0.0364 (9)	0.0285 (8)	0.0437 (10)	0.0021 (7)	0.0093 (7)	−0.0027 (7)
C2	0.0345 (8)	0.0279 (8)	0.0343 (8)	0.0019 (6)	0.0044 (7)	−0.0001 (6)
C3	0.0493 (10)	0.0257 (8)	0.0392 (9)	−0.0012 (7)	0.0061 (8)	0.0015 (7)
C4	0.0428 (9)	0.0308 (8)	0.0419 (10)	−0.0062 (7)	0.0125 (8)	−0.0071 (7)
C5	0.0378 (9)	0.0453 (10)	0.0432 (10)	0.0001 (8)	0.0009 (8)	−0.0049 (8)
C6	0.0422 (10)	0.0351 (9)	0.0471 (10)	0.0049 (7)	−0.0005 (8)	0.0053 (8)
C7	0.0332 (8)	0.0248 (7)	0.0418 (9)	0.0023 (6)	0.0078 (7)	0.0015 (6)

Geometric parameters (Å, º) top

S1—C1	1.630 (2)	C2—C3	1.370 (3)
O1—C1	1.375 (2)	C2—C7	1.384 (2)
O1—C2	1.378 (2)	C3—C4	1.384 (3)
O2—N2	1.212 (3)	C3—H3	0.9300
O3—N2	1.217 (3)	C4—C5	1.387 (3)
N1—C1	1.346 (2)	C5—C6	1.385 (3)
N1—C7	1.379 (2)	C5—H5	0.9300
N1—H1	0.8389	C6—C7	1.382 (3)
N2—C4	1.464 (2)	C6—H6	0.9300

C1—O1—C2	107.67 (13)	C2—C3—H3	123.0
C1—N1—C7	110.69 (15)	C4—C3—H3	123.0
C1—N1—H1	123.5	C3—C4—C5	124.17 (17)
C7—N1—H1	124.8	C3—C4—N2	117.11 (17)
O2—N2—O3	122.37 (19)	C5—C4—N2	118.72 (18)
O2—N2—C4	118.72 (19)	C6—C5—C4	120.28 (18)
O3—N2—C4	118.91 (19)	C6—C5—H5	119.9
N1—C1—O1	107.49 (14)	C4—C5—H5	119.9
N1—C1—S1	129.98 (14)	C7—C6—C5	116.58 (17)
O1—C1—S1	122.54 (13)	C7—C6—H6	121.7
C3—C2—O1	127.43 (15)	C5—C6—H6	121.7
C3—C2—C7	123.77 (17)	N1—C7—C6	133.39 (16)
O1—C2—C7	108.80 (15)	N1—C7—C2	105.34 (16)
C2—C3—C4	113.92 (16)	C6—C7—C2	121.27 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.84	2.41	3.068 (3)	135
N1—H1···O3ⁱ	0.84	2.36	3.137 (3)	154

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.

Acknowledgements

The authors thank the Faculty of Science, Mohammed V University in Rabat, Morocco for the X-ray measurements and Chouaib Doukkali University (El Jadida Morocco) for support.

References

Benchidmi, M., El Kihel, A., Essassi, E. M., Knouzi, N., Toupet, L., Danion-Bougot, R. & Carrié, R. (1995). Bull. Soc. Chim. Belg. 104, 605–611. CrossRef CAS Google Scholar
Bruker (2016). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
El Kihel, A., Benchidmi, M., Essassi, E. M. & Danion-Bougot, R. (1999). Synth. Commun. 29, 387–397. CAS Google Scholar
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ISSN: 2414-3146

Volume 4| Part 8| August 2019| x191119

https://doi.org/10.1107/S2414314619011192

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6-Nitro-1,3-benzoxazole-2(3H)-thione

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds