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

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

doi:10.1107/S2056989015006039

organic compounds

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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages o272-o273

https://doi.org/10.1107/S2056989015006039

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

Gamal A. El-Hiti,^a ^* Keith Smith,^b Amany S. Hegazy,^b Saud A. Alanazi ^a 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, and ^bSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Wales
^*Correspondence e-mail: gelhiti@ksu.edu.sa

Edited by G. Smith, Queensland University of Technology, Australia (Received 5 March 2015; accepted 25 March 2015; online 2 April 2015)

In the title molecule, C₉H₁₀N₂S, one of the methyl groups is almost co-planar with the thiazolopyridine rings with a deviation of 0.311 (3) Å from the least-squares plane of the thiazolopyridine group. In the crystal, weak C—H⋯N hydrogen-bonding interactions lead to the formation of chains along [011].

Keywords: crystal structure; thiazolopyridine; hydrogen bonding.

CCDC reference: 1056012

1. Related literature

For related compounds, see: Smith et al. (1994 , 1995 ); El-Hiti (2003 ); Johnson et al. (2006 ); Thomae et al. (2008 ); Rao et al. (2009 ); Lee et al. (2010 ); Luo et al. (2015 ). For the X-ray crystal structures of related compounds, see: Yu et al. (2007 ); El-Hiti et al. (2014 ).

2. Experimental

2.1. Crystal data

C₉H₁₀N₂S
M_r = 178.25
Orthorhombic, P n a 2₁
a = 9.6376 (2) Å
b = 10.1602 (2) Å
c = 8.9254 (2) Å
V = 873.98 (3) Å³
Z = 4
Cu Kα radiation
μ = 2.81 mm⁻¹
T = 150 K
0.23 × 0.20 × 0.14 mm

2.2. Data collection

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ) T_min = 0.897, T_max = 0.940
2848 measured reflections
1366 independent reflections
1351 reflections with I > 2σ(I)
R_int = 0.012

2.3. Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.057
S = 1.08
1366 reflections
111 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯N1ⁱ	0.95	2.51	3.391 (2)	153
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 ).

Supporting information

CCDC reference: 1056012

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015006039/zs2329sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015006039/zs2329Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015006039/zs2329Isup3.cml

checkCIF report

Chemical context top

Thiazolopyridines have been efficiently synthesized and in high yield using different synthetic procedures (Smith et al., 1994, 1995; El-Hiti, 2003; Johnson et al., 2006; Thomae et al., 2008; Rao et al., 2009; Lee et al., 2010; Luo et al., 2015). During our continuing research towards the development of novel synthetic routes for the production of heterocyclic compounds, we have synthesised the title compound 2-(methylethyl)-1,3-thiazolo[4,5-b]pyridine in high yield (Smith et al., 1995). The X-ray structures for related compounds have been reported (Yu et al., 2007; El-Hiti et al., 2014).

Structural commentary top

The asymmetric unit of the title compound consists of a single molecule of C₉H₁₀N₂S (Fig. 1). In the molecule, one of the methyl groups is almost co-planar with the thiazolopyridine ring. The deviations from the least-squares plane of the thiazolopyridine group are 0.311 (3)Å and 1.269 (3)Å for C8 and C9 respectively, corresponding to torsion angles N1—C1—C7—C8 and N1—C1—C7—C9 of 169.47 (19) and -65.9 (3)°, respectively.

Weak C—H···N hydrogen-bonding interactions occur in the structure to form chains along [011] (Fig. 2, Table 1). No π–π interactions are observed in the crystal structure.

Synthesis and crystallization top

2-(1-Methylethyl)-1,3-thiazolo[4,5-b]pyridine was obtained in 98% yield from acid hydrolysis (HCl, 5 M) of 3-(diisopropylaminothiocarbonylthio)-2-(1-methylethylcarbonylamino)pyridine under reflux for 5 h (Smith et al., 1995). Crystallization of the crude product from diethyl ether gave colourless crystals of the title compound. The spectroscopic and analytical data for the title compound were consistent with those reported previously (Smith et al., 1995).

Refinement details top

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. Although not of relevance with this achiral compound, the absolute structure factor (Flack, 1983) was determined as 0.031 (11) for 434 Friedel pairs.

Related literature top

For related compounds, see: Smith et al. (1994, 1995); El-Hiti (2003); Johnson et al. (2006); Thomae et al. (2008); Rao et al. (2009); Lee et al. (2010); Luo et al. (2015). For the X-ray crystal structures of related compounds, see: Yu et al. (2007); El-Hiti et al. (2014).

Structure description top

Weak C—H···N hydrogen-bonding interactions occur in the structure to form chains along [011] (Fig. 2, Table 1). No π–π interactions are observed in the crystal structure.

For related compounds, see: Smith et al. (1994, 1995); El-Hiti (2003); Johnson et al. (2006); Thomae et al. (2008); Rao et al. (2009); Lee et al. (2010); Luo et al. (2015). For the X-ray crystal structures of related compounds, see: Yu et al. (2007); El-Hiti et al. (2014).

Synthesis and crystallization top

Refinement details top

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: 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 top

	Fig. 1. A molecule of C₉H₁₀N₂S with atom labels and 50% probability displacement ellipsoids for non-hydrogen atoms.
	Fig. 2. Crystal structure packing viewed down the c axis with C—H···N interactions shown as dotted lines.

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

Crystal data top

C₉H₁₀N₂S	D_x = 1.355 Mg m⁻³
M_r = 178.25	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pna2₁	Cell parameters from 2276 reflections
a = 9.6376 (2) Å	θ = 6.3–73.8°
b = 10.1602 (2) Å	µ = 2.81 mm⁻¹
c = 8.9254 (2) Å	T = 150 K
V = 873.98 (3) Å³	Block, colourless
Z = 4	0.23 × 0.20 × 0.14 mm
F(000) = 376

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	1366 independent reflections
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source	1351 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.012
Detector resolution: 10.5082 pixels mm^-1	θ_max = 74.0°, θ_min = 6.3°
ω scans	h = −11→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −12→8
T_min = 0.897, T_max = 0.940	l = −10→10
2848 measured reflections

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.057	w = 1/[σ²(F_o²) + (0.0375P)² + 0.1081P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
1366 reflections	Δρ_max = 0.19 e Å⁻³
111 parameters	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₉H₁₀N₂S	V = 873.98 (3) Å³
M_r = 178.25	Z = 4
Orthorhombic, Pna2₁	Cu Kα radiation
a = 9.6376 (2) Å	µ = 2.81 mm⁻¹
b = 10.1602 (2) Å	T = 150 K
c = 8.9254 (2) Å	0.23 × 0.20 × 0.14 mm

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	1366 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	1351 reflections with I > 2σ(I)
T_min = 0.897, T_max = 0.940	R_int = 0.012
2848 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	1 restraint
wR(F²) = 0.057	H-atom parameters constrained
S = 1.08	Δρ_max = 0.19 e Å⁻³
1366 reflections	Δρ_min = −0.20 e Å⁻³
111 parameters

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.

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

	x	y	z	U_iso*/U_eq
C1	0.13501 (18)	0.59856 (18)	0.8660 (2)	0.0227 (4)
C2	0.23657 (17)	0.67547 (17)	1.1015 (2)	0.0208 (3)
C3	0.29550 (18)	0.56187 (17)	1.0365 (2)	0.0203 (3)
C4	0.2865 (2)	0.72261 (17)	1.2365 (3)	0.0257 (4)
H4	0.2483	0.7985	1.2829	0.031*
C5	0.39534 (19)	0.6532 (2)	1.3007 (3)	0.0279 (4)
H5	0.4342	0.6813	1.3931	0.034*
C6	0.44760 (19)	0.54145 (19)	1.2283 (3)	0.0273 (4)
H6	0.5220	0.4959	1.2752	0.033*
C7	0.05003 (18)	0.57871 (19)	0.7259 (3)	0.0271 (4)
H7	0.0177	0.4852	0.7251	0.033*
C8	−0.0783 (2)	0.6663 (2)	0.7204 (3)	0.0365 (5)
H8A	−0.1375	0.6475	0.8070	0.055*
H8B	−0.1299	0.6488	0.6279	0.055*
H8C	−0.0499	0.7589	0.7227	0.055*
C9	0.1411 (2)	0.5992 (3)	0.5875 (3)	0.0421 (6)
H9A	0.1666	0.6923	0.5796	0.063*
H9B	0.0897	0.5727	0.4977	0.063*
H9C	0.2253	0.5457	0.5966	0.063*
N1	0.23563 (16)	0.52156 (16)	0.9037 (2)	0.0241 (3)
N2	0.40055 (14)	0.49434 (16)	1.0985 (2)	0.0254 (4)
S1	0.10273 (4)	0.73079 (4)	0.98822 (7)	0.02515 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0205 (8)	0.0253 (8)	0.0224 (10)	−0.0013 (7)	0.0032 (7)	−0.0026 (8)
C2	0.0212 (8)	0.0210 (7)	0.0203 (9)	−0.0011 (6)	0.0033 (6)	−0.0004 (7)
C3	0.0199 (7)	0.0206 (7)	0.0204 (9)	−0.0026 (6)	0.0032 (6)	−0.0024 (7)
C4	0.0292 (9)	0.0258 (9)	0.0221 (9)	−0.0028 (7)	0.0018 (8)	−0.0061 (8)
C5	0.0302 (9)	0.0353 (11)	0.0184 (9)	−0.0058 (7)	−0.0024 (7)	0.0002 (9)
C6	0.0258 (8)	0.0303 (9)	0.0259 (9)	0.0005 (7)	−0.0035 (8)	0.0042 (8)
C7	0.0266 (8)	0.0293 (9)	0.0254 (9)	−0.0036 (7)	−0.0032 (8)	−0.0030 (8)
C8	0.0293 (9)	0.0428 (12)	0.0374 (13)	0.0037 (9)	−0.0127 (9)	−0.0071 (11)
C9	0.0351 (11)	0.0705 (16)	0.0207 (11)	−0.0072 (11)	−0.0024 (8)	−0.0025 (11)
N1	0.0231 (7)	0.0264 (8)	0.0229 (8)	0.0012 (6)	0.0001 (6)	−0.0067 (7)
N2	0.0238 (8)	0.0239 (7)	0.0284 (9)	0.0024 (6)	−0.0016 (6)	−0.0002 (7)
S1	0.0242 (2)	0.0266 (2)	0.0246 (2)	0.00703 (13)	−0.0007 (2)	−0.0048 (2)

Geometric parameters (Å, º) top

C1—N1	1.291 (2)	C6—N2	1.334 (3)
C1—C7	1.508 (3)	C6—H6	0.9500
C1—S1	1.7585 (19)	C7—C8	1.524 (3)
C2—C4	1.383 (3)	C7—C9	1.530 (3)
C2—C3	1.411 (2)	C7—H7	1.0000
C2—S1	1.7325 (19)	C8—H8A	0.9800
C3—N2	1.342 (2)	C8—H8B	0.9800
C3—N1	1.380 (2)	C8—H8C	0.9800
C4—C5	1.388 (3)	C9—H9A	0.9800
C4—H4	0.9500	C9—H9B	0.9800
C5—C6	1.400 (3)	C9—H9C	0.9800
C5—H5	0.9500

N1—C1—C7	122.91 (17)	C8—C7—C9	111.1 (2)
N1—C1—S1	115.73 (15)	C1—C7—H7	107.6
C7—C1—S1	121.36 (14)	C8—C7—H7	107.6
C4—C2—C3	120.08 (17)	C9—C7—H7	107.6
C4—C2—S1	130.92 (14)	C7—C8—H8A	109.5
C3—C2—S1	108.98 (14)	C7—C8—H8B	109.5
N2—C3—N1	121.16 (16)	H8A—C8—H8B	109.5
N2—C3—C2	123.53 (18)	C7—C8—H8C	109.5
N1—C3—C2	115.30 (16)	H8A—C8—H8C	109.5
C2—C4—C5	116.51 (17)	H8B—C8—H8C	109.5
C2—C4—H4	121.7	C7—C9—H9A	109.5
C5—C4—H4	121.7	C7—C9—H9B	109.5
C4—C5—C6	119.6 (2)	H9A—C9—H9B	109.5
C4—C5—H5	120.2	C7—C9—H9C	109.5
C6—C5—H5	120.2	H9A—C9—H9C	109.5
N2—C6—C5	124.73 (18)	H9B—C9—H9C	109.5
N2—C6—H6	117.6	C1—N1—C3	110.99 (16)
C5—C6—H6	117.6	C6—N2—C3	115.54 (16)
C1—C7—C8	112.90 (18)	C2—S1—C1	89.00 (9)
C1—C7—C9	109.85 (15)

C4—C2—C3—N2	−0.3 (3)	C7—C1—N1—C3	−179.88 (16)
S1—C2—C3—N2	−179.06 (14)	S1—C1—N1—C3	0.6 (2)
C4—C2—C3—N1	178.46 (16)	N2—C3—N1—C1	178.62 (17)
S1—C2—C3—N1	−0.3 (2)	C2—C3—N1—C1	−0.1 (2)
C3—C2—C4—C5	0.4 (3)	C5—C6—N2—C3	0.0 (3)
S1—C2—C4—C5	178.89 (15)	N1—C3—N2—C6	−178.61 (17)
C2—C4—C5—C6	−0.4 (3)	C2—C3—N2—C6	0.1 (3)
C4—C5—C6—N2	0.2 (3)	C4—C2—S1—C1	−178.11 (19)
N1—C1—C7—C8	169.47 (19)	C3—C2—S1—C1	0.50 (14)
S1—C1—C7—C8	−11.0 (2)	N1—C1—S1—C2	−0.64 (15)
N1—C1—C7—C9	−65.9 (3)	C7—C1—S1—C2	179.79 (16)
S1—C1—C7—C9	113.64 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N1ⁱ	0.95	2.51	3.391 (2)	153

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N1ⁱ	0.95	2.51	3.391 (2)	153

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

Footnotes

‡Additional correspondence author, e-mail: kariukib@cardiff.ac.uk.

Acknowledgements

The authors extend their appreciation to the Cornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, for funding this research and to Cardiff University for continued support.

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