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

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 [pi]-[pi] stacking [shortest centroid-centroid separation = 3.5295 (9) Å] links the mol­ecules into (001) sheets.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.086
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

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Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         18 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1 Note

Alert level G
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         68 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Introduction

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.

S2. Experimental

S2.1. Synthesis and crystallization

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).

S2.2. Refinement

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.

S3. Results and discussion

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

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

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.

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).

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

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 details

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

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

	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

Crystal data

C12H7N3O2S	F(000) = 528
Mr = 257.27	Dx = 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) Å^3	Plate, colourless
Z = 4	0.36 × 0.24 × 0.03 mm

Data collection

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

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.086	w = 1/[σ^2(Fo^2) + (0.048P)^2 + 0.2004P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
2104 reflections	Δρmax = 0.20 e Å^−3
163 parameters	Δρmin = −0.27 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)