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

In the title mol­ecule, C₁₃H₁₀N₂S, the dihedral angle between the planes through the non-H atoms of the methylbenzene and thi­azo­lopyridine groups is 36.61 (5)°. In the crystal, the thi­azo­lopyridine groups of inversion-related mol­ecules overlap, with a minimum ring-centroid separation of 3.6721 (9) Å. Furthermore, the methylbenzene groups from neighbouring mol­ecules inter­act edge-to-face at an angle of 71.66 (5)°. In addition, weak C-H... N hydrogen bonds form chains exending along [100].

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.035
• wR factor = 0.106
• Data-to-parameter ratio = 15.3

checkCIF/PLATON results

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Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3 Report

Alert level G
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         28 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
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   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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S1. Introduction

Various thia­zolo­pyridine derivatives have been synthesised using different synthetic methods (Luo et al., 2015; Chaban et al., 2013; Leysen et al., 1984; Lee et al., 2010; Rao et al., 2009; Johnson et al., 2006; El-Hiti, 2003; Smith et al., 1994, 1995). We have synthesized 2-(2-methyl­phenyl)-1,3-thia­zolo[4,5-b]pyridine in high yield (El-Hiti, 2003; Smith et al., 1995) as a continuation of our research directed towards the development of novel synthetic routes towards heterocyclic derivatives. The X-ray structures for related compounds have been reported previously (El-Hiti et al., 2014, 2015; Yu et al., 2007).

S2. Experimental

S2.1. Synthesis and crystallization

2-(2-Methyl­phenyl)-1,3-thia­zolo[4,5-b]pyridine was obtained in 89% yield from acid hydrolysis of 3-(diiso­propyl­amino­thio­carbonyl­thio)-2-(2-methyl­benzoyl­amino)­pyridine under reflux (Smith et al., 1995) or in 61% yield from the reaction of 3-(diiso­propyl­amino­thio­carbonyl­thio)-2-amino­pyridine with 2-methyl­benzoic acid in the presence of phospho­rus oxychloride under reflux (El-Hiti, 2003). Crystallization from di­ethyl ether gave colourless crystals of the title compound. The NMR and mass spectral data for this compound 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_iso(H) constrained to be 1.2 times U_eq for the atom it is bonded to except for methyl groups where it was 1.5 times with free rotation about the C—C bond.

S3. Comment

The asymmetric unit consists of one molecule of C₁₃H₁₀N₂S (Fig. 1). In the molecule, the angle between the least squares planes through the nonhydrogen atoms of the methyl­phenyl and thia­zolo­pyridine groups is 36.61 (5)°. In the crystal (Fig 2), the thia­zolo­pyridine groups of adjacent inversion-related molecules are parallel and overlap fully with a minimum ring centroid separation of 3.6721 (9) Å between the 5-membered and 6-membered components of the groups (related by -x, -y +1.-z +1) . Methyl­phenyl groups from neighbouring molecules inter­act in an edge-to-face fashion with a dihedral angle between the rings of 71.66 (5)°. A weak inter­molecular C4—H···N2ⁱ contact (Table 1) forms chains of molecules extending along [100].

Related literature

Various thiazolopyridine derivatives have been synthesised using different synthetic methods, see: Luo et al. (2015); Chaban et al. (2013); Leysen et al. (1984); Lee et al. (2010); Rao et al. (2009); Johnson et al. (2006); El-Hiti (2003); Smith et al. (1994, 1995). For the X-ray crystal structures of related compounds, see: El-Hiti et al. (2014; 2015); Yu et al. (2007).

Structure description

Various thia­zolo­pyridine derivatives have been synthesised using different synthetic methods (Luo et al., 2015; Chaban et al., 2013; Leysen et al., 1984; Lee et al., 2010; Rao et al., 2009; Johnson et al., 2006; El-Hiti, 2003; Smith et al., 1994, 1995). We have synthesized 2-(2-methyl­phenyl)-1,3-thia­zolo[4,5-b]pyridine in high yield (El-Hiti, 2003; Smith et al., 1995) as a continuation of our research directed towards the development of novel synthetic routes towards heterocyclic derivatives. The X-ray structures for related compounds have been reported previously (El-Hiti et al., 2014, 2015; Yu et al., 2007).

The asymmetric unit consists of one molecule of C₁₃H₁₀N₂S (Fig. 1). In the molecule, the angle between the least squares planes through the nonhydrogen atoms of the methyl­phenyl and thia­zolo­pyridine groups is 36.61 (5)°. In the crystal (Fig 2), the thia­zolo­pyridine groups of adjacent inversion-related molecules are parallel and overlap fully with a minimum ring centroid separation of 3.6721 (9) Å between the 5-membered and 6-membered components of the groups (related by -x, -y +1.-z +1) . Methyl­phenyl groups from neighbouring molecules inter­act in an edge-to-face fashion with a dihedral angle between the rings of 71.66 (5)°. A weak inter­molecular C4—H···N2ⁱ contact (Table 1) forms chains of molecules extending along [100].

Various thiazolopyridine derivatives have been synthesised using different synthetic methods, see: Luo et al. (2015); Chaban et al. (2013); Leysen et al. (1984); Lee et al. (2010); Rao et al. (2009); Johnson et al. (2006); El-Hiti (2003); Smith et al. (1994, 1995). For the X-ray crystal structures of related compounds, see: El-Hiti et al. (2014; 2015); Yu et al. (2007).

Synthesis and crystallization

2-(2-Methyl­phenyl)-1,3-thia­zolo[4,5-b]pyridine was obtained in 89% yield from acid hydrolysis of 3-(diiso­propyl­amino­thio­carbonyl­thio)-2-(2-methyl­benzoyl­amino)­pyridine under reflux (Smith et al., 1995) or in 61% yield from the reaction of 3-(diiso­propyl­amino­thio­carbonyl­thio)-2-amino­pyridine with 2-methyl­benzoic acid in the presence of phospho­rus oxychloride under reflux (El-Hiti, 2003). Crystallization from di­ethyl ether gave colourless crystals of the title compound. The NMR and mass spectral data for this compound were consistent with those reported (Smith et al., 1995).

Refinement details

H atoms were positioned geometrically and refined using a riding model with U_iso(H) constrained to be 1.2 times U_eq for the atom it is bonded to except for methyl groups where it was 1.5 times with free rotation about the C—C bond.

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: SHELXS2013 (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 C13H10N2O with atom labels and 50% probability displacement ellipsoids for non-hydrogen atoms.
	Fig. 2. The crystal packing viewed along the a axis of the unit cell.

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

Crystal data

C13H10N2S	Dx = 1.348 Mg m^−3
Mr = 226.29	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 3613 reflections
a = 7.6702 (1) Å	θ = 3.8–74.0°
b = 12.6492 (3) Å	µ = 2.33 mm^−1
c = 22.9821 (5) Å	T = 293 K
V = 2229.77 (8) Å^3	Block, colourless
Z = 8	0.26 × 0.17 × 0.05 mm
F(000) = 944

Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas CCD detector	1959 reflections with I > 2σ(I)
ω scans	Rint = 0.019
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	θmax = 74.0°, θmin = 3.9°
Tmin = 0.960, Tmax = 0.989	h = −9→6
7263 measured reflections	k = −12→15
2234 independent reflections	l = −28→27

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0633P)^2 + 0.2883P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
2234 reflections	Δρmax = 0.17 e Å^−3
146 parameters	Δρmin = −0.27 e Å^−3

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.21789 (18)	0.50224 (11)	0.38130 (6)	0.0457 (3)
C2	0.03446 (19)	0.40362 (11)	0.43105 (6)	0.0496 (3)
C3	−0.07616 (19)	0.48902 (12)	0.42082 (6)	0.0527 (3)
C4	−0.1768 (3)	0.31679 (15)	0.48019 (8)	0.0706 (5)
H4	−0.2140	0.2579	0.5010	0.085*
C5	−0.2954 (2)	0.39752 (16)	0.47141 (8)	0.0705 (5)
H5	−0.4082	0.3917	0.4859	0.085*
C6	−0.2461 (2)	0.48645 (16)	0.44130 (8)	0.0670 (4)
H6	−0.3229	0.5422	0.4350	0.080*
C7	0.37539 (18)	0.54080 (11)	0.35116 (6)	0.0470 (3)
C8	0.48582 (19)	0.47301 (13)	0.31980 (6)	0.0527 (3)
C9	0.6265 (2)	0.51824 (15)	0.29070 (7)	0.0644 (4)
H9	0.6997	0.4749	0.2690	0.077*
C10	0.6608 (2)	0.62498 (15)	0.29292 (8)	0.0675 (4)
H10	0.7555	0.6528	0.2728	0.081*
C11	0.5547 (2)	0.69041 (14)	0.32501 (8)	0.0664 (4)
H11	0.5787	0.7623	0.3274	0.080*
C12	0.4124 (2)	0.64853 (12)	0.35362 (7)	0.0563 (4)
H12	0.3399	0.6930	0.3749	0.068*
C13	0.4583 (3)	0.35571 (14)	0.31637 (9)	0.0730 (5)
H13A	0.5337	0.3264	0.2872	0.109*
H13B	0.3391	0.3414	0.3064	0.109*
H13C	0.4845	0.3243	0.3534	0.109*
N1	0.20074 (17)	0.41287 (9)	0.40814 (5)	0.0514 (3)
N2	−0.0128 (2)	0.31754 (12)	0.46089 (7)	0.0659 (4)
S1	0.03278 (5)	0.58334 (3)	0.38069 (2)	0.06317 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0444 (7)	0.0476 (7)	0.0451 (7)	0.0040 (5)	−0.0043 (5)	−0.0027 (5)
C2	0.0486 (8)	0.0529 (8)	0.0471 (7)	0.0024 (6)	0.0008 (6)	−0.0006 (6)
C3	0.0452 (7)	0.0625 (8)	0.0502 (7)	0.0045 (6)	−0.0035 (6)	0.0007 (6)
C4	0.0698 (10)	0.0746 (11)	0.0673 (10)	−0.0082 (8)	0.0169 (8)	0.0047 (8)
C5	0.0526 (9)	0.0951 (13)	0.0637 (9)	−0.0068 (8)	0.0099 (7)	−0.0010 (9)
C6	0.0474 (8)	0.0870 (12)	0.0667 (9)	0.0106 (8)	0.0017 (7)	0.0036 (8)
C7	0.0441 (7)	0.0502 (7)	0.0468 (7)	0.0005 (6)	−0.0055 (5)	0.0007 (5)
C8	0.0497 (7)	0.0567 (8)	0.0517 (8)	0.0026 (6)	−0.0004 (6)	−0.0013 (6)
C9	0.0562 (9)	0.0778 (11)	0.0591 (9)	0.0018 (8)	0.0097 (7)	−0.0019 (8)
C10	0.0600 (9)	0.0795 (11)	0.0630 (9)	−0.0143 (8)	0.0057 (7)	0.0089 (8)
C11	0.0685 (10)	0.0609 (9)	0.0700 (10)	−0.0140 (8)	−0.0009 (8)	0.0052 (8)
C12	0.0555 (8)	0.0530 (8)	0.0605 (8)	−0.0010 (7)	−0.0038 (7)	−0.0009 (6)
C13	0.0769 (12)	0.0564 (9)	0.0856 (12)	0.0054 (8)	0.0211 (9)	−0.0104 (9)
N1	0.0490 (7)	0.0508 (7)	0.0544 (7)	0.0062 (5)	0.0033 (5)	0.0039 (5)
N2	0.0665 (8)	0.0622 (8)	0.0691 (8)	0.0026 (6)	0.0133 (7)	0.0116 (7)
S1	0.0491 (3)	0.0616 (3)	0.0789 (3)	0.01227 (16)	0.00281 (17)	0.01779 (18)

Geometric parameters (Å, º)

C1—N1	1.2944 (18)	C7—C12	1.393 (2)
C1—C7	1.476 (2)	C7—C8	1.404 (2)
C1—S1	1.7518 (14)	C8—C9	1.392 (2)
C2—N2	1.337 (2)	C8—C13	1.501 (2)
C2—N1	1.3848 (19)	C9—C10	1.377 (3)
C2—C3	1.394 (2)	C9—H9	0.9300
C3—C6	1.386 (2)	C10—C11	1.375 (3)
C3—S1	1.7240 (16)	C10—H10	0.9300
C4—N2	1.334 (2)	C11—C12	1.380 (2)
C4—C5	1.382 (3)	C11—H11	0.9300
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.374 (3)	C13—H13A	0.9600
C5—H5	0.9300	C13—H13B	0.9600
C6—H6	0.9300	C13—H13C	0.9600
N1—C1—C7	126.56 (13)	C7—C8—C13	123.08 (14)
N1—C1—S1	115.65 (11)	C10—C9—C8	122.24 (16)
C7—C1—S1	117.79 (10)	C10—C9—H9	118.9
N2—C2—N1	120.92 (13)	C8—C9—H9	118.9
N2—C2—C3	123.54 (14)	C11—C10—C9	119.80 (15)
N1—C2—C3	115.54 (13)	C11—C10—H10	120.1
C6—C3—C2	119.80 (15)	C9—C10—H10	120.1
C6—C3—S1	130.81 (13)	C10—C11—C12	119.51 (16)
C2—C3—S1	109.37 (11)	C10—C11—H11	120.2
N2—C4—C5	124.51 (17)	C12—C11—H11	120.2
N2—C4—H4	117.7	C11—C12—C7	121.16 (16)
C5—C4—H4	117.7	C11—C12—H12	119.4
C6—C5—C4	119.85 (16)	C7—C12—H12	119.4
C6—C5—H5	120.1	C8—C13—H13A	109.5
C4—C5—H5	120.1	C8—C13—H13B	109.5
C5—C6—C3	116.67 (17)	H13A—C13—H13B	109.5
C5—C6—H6	121.7	C8—C13—H13C	109.5
C3—C6—H6	121.7	H13A—C13—H13C	109.5
C12—C7—C8	119.67 (14)	H13B—C13—H13C	109.5
C12—C7—C1	118.11 (13)	C1—N1—C2	110.40 (12)
C8—C7—C1	122.21 (13)	C4—N2—C2	115.61 (15)
C9—C8—C7	117.58 (15)	C3—S1—C1	89.04 (7)
C9—C8—C13	119.33 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N2^i	0.93	2.63	3.371 (2)	137

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