Crystal structure of 2-(3-nitro­phen­yl)-1,3-thia­zolo[4,5-b]pyridine

El-Hiti, G.A.; Smith, K.; Hegazy, A.S.; Ajarim, M.D.; Kariuki, B.M.

doi:10.1107/S2056989015019118

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 11| November 2015| Page o877

https://doi.org/10.1107/S2056989015019118

Open

access

Crystal structure of 2-(3-nitrophenyl)-1,3-thiazolo[4,5-b]pyridine

Gamal A. El-Hiti,^a ^* Keith Smith,^b Amany S. Hegazy,^b Mansour D. Ajarim ^c and Benson M. Kariuki ^b ^*

^aCornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia, ^bSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Wales, and ^cCriminal Evidence, Ministry of Interior, Riyadh 11632, PO Box 86985, Saudi Arabia
^*Correspondence e-mail: gelhiti@ksu.edu.sa, kariukib@cardiff.ac.uk

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 9 October 2015; accepted 10 October 2015; online 24 October 2015)

In the title compound, C₁₂H₇N₃O₂S, the dihedral angle between the planes of the thiazolopyridine ring system (r.m.s. deviation = 0.005 Å) and the benzene ring is 3.94 (6)°. The nitro group is rotated by 7.6 (2)° from its attached ring. In the crystal, extensive aromatic π–π stacking [shortest centroid–centroid separation = 3.5295 (9) Å] links the molecules into (001) sheets.

Keywords: crystal structure; nitrophenyl; thiazolopyridine derivatives; thiazolo[4,5-b]pyridine.

CCDC reference: 1430578

1. Related literature

For a related structure and background references, see: El-Hiti et al. (2015 ). For further synthetic details, see: Smith et al. (1995 ); El-Hiti (2003 ).

2. Experimental

2.1. Crystal data

C₁₂H₇N₃O₂S
M_r = 257.27
Monoclinic, P 2₁ /c
a = 9.5596 (2) Å
b = 9.8733 (2) Å
c = 11.5606 (3) Å
β = 98.122 (2)°
V = 1080.20 (4) Å³
Z = 4
Cu Kα radiation
μ = 2.66 mm⁻¹
T = 296 K
0.36 × 0.24 × 0.03 mm

2.2. Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector
Absorption correction: Gaussian (CrysAlis PRO; Agilent, 2014 ) T_min = 0.883, T_max = 0.986
4063 measured reflections
2104 independent reflections
1930 reflections with I > 2σ(I)
R_int = 0.016

2.3. Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.086
S = 1.06
2104 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001 ).

Supporting information

CCDC reference: 1430578

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015019118/hb7519sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015019118/hb7519Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015019118/hb7519Isup3.cml

checkCIF report

Introduction top

As part of our ongoing studies of thiazolopyridines (El-Hiti et al., 2015), the title compound was prepared by two different processes (El-Hiti, 2003; Smith et al., 1995) and its structure was determined.

Experimental top

Synthesis and crystallization top

2-(3-Nitrophenyl)-1,3-thiazolo[4,5-b]pyridine was obtained in 90% yield from acid hydrolysis (HCl, 5 M) of 3-(diiso-propylaminothiocarbonylthio)-2-(3-nitrophenylcarbonylamino)pyridine under reflux for 5 h (Smith et al., 1995) or in 58% yield from reaction of 3-(diisopropylaminothiocarbonylthio)-2-aminopyridine with 3-nitrobenzoic acid in the presence of phosphorus oxychloride under reflux for 4 h (El-Hiti, 2003). Crystallization of the crude product from chloroform gave the title compound as colourless crystals. The structure of the title compound was elucidated by various spectroscopic and analytical data, which were consistent with those reported (Smith et al., 1995).

Refinement top

H atoms were positioned geometrically and refined using a riding model with U_ĩso(H) constrained to be 1.2 times U_eq for the atom it is bonded to.

Results and discussion top

The asymmetric unit comprises one molecule of C₁₂H₇N₃O₂S (Fig. 1). The phenylthiazolopyridine ring system is flat with a maximum deviation of 0.072 (1)Å from the least squares plane. The nitro group is twisted from this plane by only 7.6 (2)°. In the crystal, extensive π - π overlap occurs between pairs of inversion related molecules with a phenyl to thiazolopyridine centroid distance of 3.47 (2)Å (Fig. 2).

Related literature top

For a related structure and background references, see: El-Hiti et al. (2015). For further synthetic details, see: Smith et al. (1995); El-Hiti (2003).

Structure description top

For a related structure and background references, see: El-Hiti et al. (2015). For further synthetic details, see: Smith et al. (1995); El-Hiti (2003).

Synthesis and crystallization top

Refinement details top

H atoms were positioned geometrically and refined using a riding model with U_ĩso(H) constrained to be 1.2 times U_eq for the atom it is bonded to.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

Figures top

	Fig. 1. The asymmetric unit of C₁₂H₇N₃O₂S with 50% probability displacement ellipsoids for nonhydrogen atoms.
	Fig. 2. A segment of the crystal structure with H atoms omitted for clarity.

2-(3-Nitrophenyl)-1,3-thiazolo[4,5-b]pyridine top

Crystal data top

C₁₂H₇N₃O₂S	F(000) = 528
M_r = 257.27	D_x = 1.582 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 9.5596 (2) Å	Cell parameters from 2610 reflections
b = 9.8733 (2) Å	θ = 5.9–73.8°
c = 11.5606 (3) Å	µ = 2.66 mm⁻¹
β = 98.122 (2)°	T = 296 K
V = 1080.20 (4) Å³	Plate, colourless
Z = 4	0.36 × 0.24 × 0.03 mm

Data collection top

Agilent SuperNova Dual Source diffractometer with an Atlas detector	1930 reflections with I > 2σ(I)
ω scans	R_int = 0.016
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014)	θ_max = 73.8°, θ_min = 5.9°
T_min = 0.883, T_max = 0.986	h = −6→11
4063 measured reflections	k = −12→10
2104 independent reflections	l = −13→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.048P)² + 0.2004P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2104 reflections	Δρ_max = 0.20 e Å⁻³
163 parameters	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₂H₇N₃O₂S	V = 1080.20 (4) Å³
M_r = 257.27	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 9.5596 (2) Å	µ = 2.66 mm⁻¹
b = 9.8733 (2) Å	T = 296 K
c = 11.5606 (3) Å	0.36 × 0.24 × 0.03 mm
β = 98.122 (2)°

Data collection top

Agilent SuperNova Dual Source diffractometer with an Atlas detector	2104 independent reflections
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014)	1930 reflections with I > 2σ(I)
T_min = 0.883, T_max = 0.986	R_int = 0.016
4063 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.06	Δρ_max = 0.20 e Å⁻³
2104 reflections	Δρ_min = −0.27 e Å⁻³
163 parameters

Special details top

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48) Numerical absorption correction based on gaussian integration over a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

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

	x	y	z	U_iso*/U_eq
C1	1.03467 (14)	0.31902 (15)	0.40820 (12)	0.0359 (3)
C2	1.05966 (14)	0.29483 (14)	0.52938 (12)	0.0346 (3)
C3	1.23544 (16)	0.44974 (17)	0.55180 (15)	0.0466 (4)
H3	1.3056	0.4963	0.5999	0.056*
C4	1.21719 (17)	0.48032 (17)	0.43313 (15)	0.0476 (4)
H4	1.2737	0.5453	0.4044	0.057*
C5	1.11469 (16)	0.41357 (17)	0.35833 (14)	0.0446 (3)
H5	1.1001	0.4312	0.2785	0.054*
C6	0.88486 (14)	0.15122 (14)	0.48354 (11)	0.0327 (3)
C7	0.78177 (13)	0.04398 (14)	0.49734 (11)	0.0323 (3)
C8	0.69113 (14)	−0.00588 (14)	0.40184 (12)	0.0338 (3)
H8	0.6911	0.0309	0.3278	0.041*
C9	0.60130 (13)	−0.11128 (14)	0.41963 (12)	0.0342 (3)
C10	0.59533 (15)	−0.16807 (15)	0.52740 (13)	0.0392 (3)
H10	0.5333	−0.2386	0.5365	0.047*
C11	0.68472 (16)	−0.11691 (16)	0.62203 (13)	0.0419 (3)
H11	0.6827	−0.1532	0.6960	0.050*
C12	0.77673 (15)	−0.01253 (16)	0.60750 (12)	0.0381 (3)
H12	0.8362	0.0206	0.6719	0.046*
N1	1.16011 (14)	0.35893 (14)	0.60175 (11)	0.0442 (3)
N2	0.97356 (13)	0.19809 (13)	0.56961 (10)	0.0367 (3)
N3	0.50993 (13)	−0.16657 (14)	0.31766 (11)	0.0420 (3)
O1	0.51160 (13)	−0.11243 (14)	0.22310 (10)	0.0563 (3)
O2	0.43804 (16)	−0.26586 (16)	0.33152 (13)	0.0698 (4)
S1	0.89807 (4)	0.21799 (4)	0.34482 (3)	0.03972 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0339 (7)	0.0341 (7)	0.0386 (7)	0.0002 (5)	0.0009 (5)	−0.0009 (6)
C2	0.0322 (7)	0.0348 (7)	0.0361 (7)	0.0004 (5)	0.0023 (5)	−0.0029 (5)
C3	0.0387 (7)	0.0429 (8)	0.0565 (9)	−0.0067 (6)	0.0004 (6)	−0.0100 (7)
C4	0.0423 (8)	0.0379 (8)	0.0627 (10)	−0.0072 (6)	0.0075 (7)	0.0012 (7)
C5	0.0445 (8)	0.0431 (8)	0.0458 (8)	−0.0041 (6)	0.0048 (6)	0.0068 (6)
C6	0.0318 (6)	0.0337 (7)	0.0322 (6)	0.0021 (5)	0.0037 (5)	−0.0016 (5)
C7	0.0293 (6)	0.0323 (6)	0.0355 (7)	0.0035 (5)	0.0049 (5)	−0.0017 (5)
C8	0.0316 (6)	0.0351 (7)	0.0346 (6)	0.0035 (5)	0.0047 (5)	−0.0004 (5)
C9	0.0279 (6)	0.0342 (7)	0.0398 (7)	0.0040 (5)	0.0024 (5)	−0.0050 (5)
C10	0.0353 (7)	0.0349 (7)	0.0479 (8)	−0.0002 (6)	0.0080 (6)	0.0028 (6)
C11	0.0436 (8)	0.0443 (8)	0.0380 (7)	0.0000 (6)	0.0060 (6)	0.0068 (6)
C12	0.0362 (7)	0.0417 (8)	0.0355 (7)	0.0001 (6)	0.0021 (5)	−0.0002 (6)
N1	0.0410 (6)	0.0476 (7)	0.0420 (7)	−0.0059 (5)	−0.0012 (5)	−0.0079 (6)
N2	0.0358 (6)	0.0401 (6)	0.0335 (6)	−0.0017 (5)	0.0029 (5)	−0.0017 (5)
N3	0.0352 (6)	0.0425 (7)	0.0467 (7)	0.0013 (5)	0.0006 (5)	−0.0082 (6)
O1	0.0582 (7)	0.0652 (8)	0.0421 (6)	−0.0030 (6)	−0.0052 (5)	−0.0054 (6)
O2	0.0684 (8)	0.0638 (9)	0.0724 (9)	−0.0315 (7)	−0.0067 (7)	−0.0050 (7)
S1	0.0419 (2)	0.0429 (2)	0.0323 (2)	−0.00887 (14)	−0.00199 (14)	0.00294 (13)

Geometric parameters (Å, º) top

C1—C5	1.383 (2)	C7—C8	1.3935 (19)
C1—C2	1.408 (2)	C7—C12	1.3974 (19)
C1—S1	1.7224 (14)	C8—C9	1.383 (2)
C2—N1	1.3400 (19)	C8—H8	0.9300
C2—N2	1.3836 (19)	C9—C10	1.375 (2)
C3—N1	1.332 (2)	C9—N3	1.4696 (18)
C3—C4	1.391 (2)	C10—C11	1.385 (2)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.379 (2)	C11—C12	1.380 (2)
C4—H4	0.9300	C11—H11	0.9300
C5—H5	0.9300	C12—H12	0.9300
C6—N2	1.2980 (18)	N3—O1	1.2190 (18)
C6—C7	1.4705 (19)	N3—O2	1.221 (2)
C6—S1	1.7548 (14)

C5—C1—C2	120.20 (13)	C9—C8—C7	118.53 (13)
C5—C1—S1	130.10 (12)	C9—C8—H8	120.7
C2—C1—S1	109.69 (11)	C7—C8—H8	120.7
N1—C2—N2	121.61 (13)	C10—C9—C8	123.22 (13)
N1—C2—C1	123.16 (14)	C10—C9—N3	118.65 (13)
N2—C2—C1	115.23 (12)	C8—C9—N3	118.12 (13)
N1—C3—C4	124.99 (14)	C9—C10—C11	117.85 (13)
N1—C3—H3	117.5	C9—C10—H10	121.1
C4—C3—H3	117.5	C11—C10—H10	121.1
C5—C4—C3	119.56 (15)	C12—C11—C10	120.58 (14)
C5—C4—H4	120.2	C12—C11—H11	119.7
C3—C4—H4	120.2	C10—C11—H11	119.7
C4—C5—C1	116.54 (14)	C11—C12—C7	120.90 (13)
C4—C5—H5	121.7	C11—C12—H12	119.5
C1—C5—H5	121.7	C7—C12—H12	119.5
N2—C6—C7	123.28 (12)	C3—N1—C2	115.53 (14)
N2—C6—S1	116.30 (11)	C6—N2—C2	110.10 (12)
C7—C6—S1	120.37 (10)	O1—N3—O2	123.28 (14)
C8—C7—C12	118.91 (13)	O1—N3—C9	118.36 (13)
C8—C7—C6	121.31 (12)	O2—N3—C9	118.35 (13)
C12—C7—C6	119.76 (12)	C1—S1—C6	88.68 (7)

Experimental details

Crystal data
Chemical formula	C₁₂H₇N₃O₂S
M_r	257.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.5596 (2), 9.8733 (2), 11.5606 (3)
β (°)	98.122 (2)
V (Å³)	1080.20 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.66
Crystal size (mm)	0.36 × 0.24 × 0.03

Data collection
Diffractometer	Agilent SuperNova Dual Source diffractometer with an Atlas detector
Absorption correction	Gaussian (CrysAlis PRO; Agilent, 2014)
T_min, T_max	0.883, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	4063, 2104, 1930
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.086, 1.06
No. of reflections	2104
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.27

Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

Acknowledgements

The authors extend their appreciation to the Criminal Evidence Department, Ministry of Interior, Riyadh, Saudi Arabia, for funding this research and to Cardiff University for continued support.

References

Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Cambridge Soft (2001). CHEMDRAW Ultra. Cambridge Soft Corporation, Cambridge, Massachusetts, USA. Google Scholar
El-Hiti, G. A. (2003). Monatsh. Chem. 134, 837–841. CAS Google Scholar
El-Hiti, G. A., Smith, K., Hegazy, A. S., Ajarim, M. D. & Kariuki, B. M. (2015). Acta Cryst. E71, o866. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Smith, K., Anderson, D. & Matthews, I. (1995). Sulfur Lett. 18, 79–95. CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 11| November 2015| Page o877

https://doi.org/10.1107/S2056989015019118

Open

access