Crystal structure of 2-cyclo­hexyl-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/S2056989015019106

organic compounds

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ISSN: 2056-9890

Volume 71| Part 11| November 2015| Page o866

https://doi.org/10.1107/S2056989015019106

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Crystal structure of 2-cyclohexyl-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 17 October 2015)

In the title compound, C₁₂H₁₄N₂S, the cyclohexane ring adopts a chair conformation with the exocyclic C—C bond in an equatorial orientation. The mean plane through the cyclohexane ring (all atoms) is twisted from the thiazolopyridine ring system (r.m.s. deviation = 0.013 Å) by 39.57 (6)°. In the crystal, molecules form (100) sheets, although there are no specific directional interactions between them. The crystal stucture was refined as a two-component perfect twin.

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

CCDC reference: 1430576

1. Related literature

For background to the uses of thiazolopyridine derivatives, see: Leysen et al. (1984 ). For a related structure reported by us and further references, see: El-Hiti et al. (2015 ). For the first report of this compound and spectroscopic data, see: Smith et al. (1995 ).

2. Experimental

2.1. Crystal data

C₁₂H₁₄N₂S
M_r = 218.31
Monoclinic, P 2₁ /n
a = 7.8884 (5) Å
b = 11.8079 (7) Å
c = 12.2134 (6) Å
β = 100.589 (6)°
V = 1118.25 (11) Å³
Z = 4
Cu Kα radiation
μ = 2.29 mm⁻¹
T = 293 K
0.27 × 0.17 × 0.14 mm

2.2. Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ) T_min = 0.592, T_max = 1.000
7328 measured reflections
3913 independent reflections
3429 reflections with I > 2σ(I)
R_int = 0.015

2.3. Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.180
S = 1.03
3913 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.29 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: 1430576

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015019106/hb7518sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015019106/hb7518Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015019106/hb7518Isup3.cml

checkCIF report

Chemical context top

Thiazolopyridine derivatives have been reported to exhibit interesting biological activities (Leysen et al., 1984). As part of our ongoing studies in this area (El-Hiti et al., 2015), we now report the structure of the title compound.

Structural commentary top

The asymmetric unit comprises one molecule of C₁₂H₁₄N₂S (Fig. 1). The cyclohexane ring is in the chair conformation in the molecule. The least squares plane through the cyclohexane ring is twisted from the thiazolopyridine group by 39.57 (6)°. In the crystal structure, the molecular axes are aligned along [001] (Fig. 2).

Synthesis and crystallization top

2-Cyclohexyl-1,3-thiazolo[4,5-b]pyridine was obtained in quantitative yield from acid hydrolysis (HCl, 5 M) of 3-(diisopropylaminothiocarbonylthio)-2-(cyclohexylcarbonylamino)pyridine under reflux for 5 h (Smith et al., 1995). The compound may also be synthesized in 94% yield from acid hydrolysis (5 M HCl, 5 h reflux) of 3-(diisopropylaminothiocarbonylthio)-2-(bis(cyclohexylcarbony)lamino) pyridine (Smith et al., 1995). Crystallization of the crude product from diethyl ether gave the title compound as colourless crystals. Spectroscopic and analytical data are consistent with those reported (Smith et al., 1995).

Refinement details top

The data were twinned and HKLF5 in Shelxl 2013 was used. 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.

Related literature top

For background to the uses of thiazolopyridine derivatives, see: Leysen et al. (1984). For a related structure reported by us and further references, see: El-Hiti et al. (2015). For the first report of this compound and spectroscopic data, see: Smith et al. (1995).

Structure description top

For background to the uses of thiazolopyridine derivatives, see: Leysen et al. (1984). For a related structure reported by us and further references, see: El-Hiti et al. (2015). For the first report of this compound and spectroscopic data, see: Smith et al. (1995).

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: 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 C₁₂H₁₄N₂S with 50% probability displacement ellipsoids for nonhydrogen atoms.
	Fig. 2. Crystal packing viewed along the a axis.

2-Cyclohexyl-1,3-thiazolo[4,5-b]pyridine top

Crystal data top

C₁₂H₁₄N₂S	F(000) = 464
M_r = 218.31	D_x = 1.297 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 7.8884 (5) Å	Cell parameters from 1721 reflections
b = 11.8079 (7) Å	θ = 6.2–73.9°
c = 12.2134 (6) Å	µ = 2.29 mm⁻¹
β = 100.589 (6)°	T = 293 K
V = 1118.25 (11) Å³	Needle, colourless
Z = 4	0.27 × 0.17 × 0.14 mm

Data collection top

Agilent SuperNova Dual Source diffractometer with an Atlas detector	3429 reflections with I > 2σ(I)
ω scans	R_int = 0.015
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	θ_max = 74.2°, θ_min = 5.3°
T_min = 0.592, T_max = 1.000	h = −9→9
7328 measured reflections	k = −14→14
3913 independent reflections	l = −15→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.063	H-atom parameters constrained
wR(F²) = 0.180	w = 1/[σ²(F_o²) + (0.1345P)² + 0.113P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3913 reflections	Δρ_max = 0.30 e Å⁻³
136 parameters	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₂H₁₄N₂S	V = 1118.25 (11) Å³
M_r = 218.31	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 7.8884 (5) Å	µ = 2.29 mm⁻¹
b = 11.8079 (7) Å	T = 293 K
c = 12.2134 (6) Å	0.27 × 0.17 × 0.14 mm
β = 100.589 (6)°

Data collection top

Agilent SuperNova Dual Source diffractometer with an Atlas detector	3913 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	3429 reflections with I > 2σ(I)
T_min = 0.592, T_max = 1.000	R_int = 0.015
7328 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.180	H-atom parameters constrained
S = 1.03	Δρ_max = 0.30 e Å⁻³
3913 reflections	Δρ_min = −0.29 e Å⁻³
136 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) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. 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.

Refinement. Refined as a 2-component perfect twin.

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

	x	y	z	U_iso*/U_eq
C1	0.2814 (3)	0.12366 (19)	0.54649 (18)	0.0467 (5)
C2	0.2459 (3)	0.20807 (19)	0.72356 (18)	0.0467 (5)
C3	0.2223 (4)	0.2609 (2)	0.8209 (2)	0.0561 (6)
H3	0.1818	0.3349	0.8212	0.067*
C4	0.2619 (4)	0.1982 (3)	0.9169 (2)	0.0634 (7)
H4	0.2461	0.2291	0.9844	0.076*
C5	0.3249 (4)	0.0897 (3)	0.9136 (2)	0.0659 (7)
H5	0.3505	0.0501	0.9805	0.079*
C6	0.3115 (3)	0.0972 (2)	0.72741 (18)	0.0472 (5)
C7	0.2823 (3)	0.0976 (2)	0.42621 (18)	0.0501 (5)
H7	0.3994	0.0741	0.4202	0.060*
C8	0.1612 (4)	−0.0018 (2)	0.3883 (2)	0.0616 (7)
H8A	0.1972	−0.0671	0.4350	0.074*
H8B	0.0450	0.0181	0.3967	0.074*
C9	0.1620 (4)	−0.0321 (2)	0.2671 (2)	0.0654 (7)
H9A	0.2758	−0.0588	0.2600	0.079*
H9B	0.0805	−0.0929	0.2443	0.079*
C10	0.1149 (4)	0.0680 (3)	0.1922 (2)	0.0706 (8)
H10A	−0.0030	0.0901	0.1937	0.085*
H10B	0.1218	0.0471	0.1163	0.085*
C11	0.2341 (5)	0.1671 (3)	0.2281 (2)	0.0856 (11)
H11A	0.1964	0.2320	0.1811	0.103*
H11B	0.3501	0.1478	0.2188	0.103*
C12	0.2352 (5)	0.1982 (2)	0.3501 (2)	0.0709 (8)
H12A	0.3176	0.2587	0.3723	0.085*
H12B	0.1220	0.2257	0.3577	0.085*
N1	0.3309 (3)	0.05196 (17)	0.62604 (16)	0.0529 (5)
N2	0.3519 (3)	0.0371 (2)	0.82184 (17)	0.0616 (6)
S1	0.20709 (8)	0.25440 (5)	0.58736 (5)	0.0545 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0509 (11)	0.0426 (11)	0.0457 (11)	−0.0033 (9)	0.0065 (9)	−0.0001 (8)
C2	0.0516 (11)	0.0423 (11)	0.0436 (11)	−0.0036 (9)	0.0021 (8)	−0.0008 (9)
C3	0.0664 (15)	0.0505 (13)	0.0496 (13)	−0.0023 (11)	0.0058 (11)	−0.0090 (10)
C4	0.0767 (17)	0.0704 (18)	0.0419 (12)	−0.0073 (13)	0.0076 (11)	−0.0079 (11)
C5	0.0794 (17)	0.0733 (18)	0.0425 (13)	0.0014 (13)	0.0047 (11)	0.0092 (11)
C6	0.0507 (12)	0.0475 (12)	0.0425 (11)	0.0013 (9)	0.0060 (8)	0.0012 (9)
C7	0.0547 (13)	0.0510 (13)	0.0453 (11)	−0.0017 (9)	0.0107 (9)	−0.0023 (9)
C8	0.0855 (18)	0.0504 (13)	0.0502 (13)	−0.0138 (13)	0.0160 (12)	−0.0044 (10)
C9	0.0846 (18)	0.0552 (15)	0.0563 (15)	−0.0118 (13)	0.0121 (12)	−0.0137 (11)
C10	0.0842 (19)	0.0764 (19)	0.0473 (13)	0.0011 (15)	0.0020 (12)	−0.0089 (13)
C11	0.145 (3)	0.0712 (19)	0.0416 (13)	−0.030 (2)	0.0189 (15)	0.0008 (12)
C12	0.116 (2)	0.0519 (15)	0.0442 (13)	−0.0148 (15)	0.0133 (13)	−0.0002 (11)
N1	0.0672 (12)	0.0472 (10)	0.0450 (10)	0.0074 (9)	0.0121 (8)	0.0036 (8)
N2	0.0795 (14)	0.0581 (13)	0.0467 (11)	0.0120 (11)	0.0104 (9)	0.0103 (9)
S1	0.0753 (5)	0.0424 (4)	0.0425 (4)	0.0053 (2)	0.0017 (3)	0.0013 (2)

Geometric parameters (Å, º) top

C1—N1	1.294 (3)	C7—H7	0.9800
C1—C7	1.502 (3)	C8—C9	1.524 (4)
C1—S1	1.756 (2)	C8—H8A	0.9700
C2—C3	1.385 (3)	C8—H8B	0.9700
C2—C6	1.405 (3)	C9—C10	1.499 (4)
C2—S1	1.724 (2)	C9—H9A	0.9700
C3—C4	1.374 (4)	C9—H9B	0.9700
C3—H3	0.9300	C10—C11	1.515 (4)
C4—C5	1.378 (4)	C10—H10A	0.9700
C4—H4	0.9300	C10—H10B	0.9700
C5—N2	1.332 (3)	C11—C12	1.534 (4)
C5—H5	0.9300	C11—H11A	0.9700
C6—N2	1.342 (3)	C11—H11B	0.9700
C6—N1	1.383 (3)	C12—H12A	0.9700
C7—C12	1.512 (4)	C12—H12B	0.9700
C7—C8	1.530 (3)

N1—C1—C7	123.0 (2)	H8A—C8—H8B	108.0
N1—C1—S1	115.61 (17)	C10—C9—C8	111.3 (2)
C7—C1—S1	121.33 (17)	C10—C9—H9A	109.4
C3—C2—C6	119.8 (2)	C8—C9—H9A	109.4
C3—C2—S1	131.07 (19)	C10—C9—H9B	109.4
C6—C2—S1	109.08 (17)	C8—C9—H9B	109.4
C4—C3—C2	116.4 (2)	H9A—C9—H9B	108.0
C4—C3—H3	121.8	C9—C10—C11	111.2 (2)
C2—C3—H3	121.8	C9—C10—H10A	109.4
C3—C4—C5	120.2 (2)	C11—C10—H10A	109.4
C3—C4—H4	119.9	C9—C10—H10B	109.4
C5—C4—H4	119.9	C11—C10—H10B	109.4
N2—C5—C4	124.9 (2)	H10A—C10—H10B	108.0
N2—C5—H5	117.6	C10—C11—C12	111.0 (3)
C4—C5—H5	117.6	C10—C11—H11A	109.4
N2—C6—N1	121.2 (2)	C12—C11—H11A	109.4
N2—C6—C2	123.3 (2)	C10—C11—H11B	109.4
N1—C6—C2	115.5 (2)	C12—C11—H11B	109.4
C1—C7—C12	113.3 (2)	H11A—C11—H11B	108.0
C1—C7—C8	109.77 (19)	C7—C12—C11	111.5 (3)
C12—C7—C8	110.3 (2)	C7—C12—H12A	109.3
C1—C7—H7	107.8	C11—C12—H12A	109.3
C12—C7—H7	107.8	C7—C12—H12B	109.3
C8—C7—H7	107.8	C11—C12—H12B	109.3
C9—C8—C7	111.1 (2)	H12A—C12—H12B	108.0
C9—C8—H8A	109.4	C1—N1—C6	110.6 (2)
C7—C8—H8A	109.4	C5—N2—C6	115.3 (2)
C9—C8—H8B	109.4	C2—S1—C1	89.19 (10)
C7—C8—H8B	109.4

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₂S
M_r	218.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.8884 (5), 11.8079 (7), 12.2134 (6)
β (°)	100.589 (6)
V (Å³)	1118.25 (11)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.29
Crystal size (mm)	0.27 × 0.17 × 0.14

Data collection
Diffractometer	Agilent SuperNova Dual Source diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014)
T_min, T_max	0.592, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7328, 3913, 3429
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.180, 1.03
No. of reflections	3913
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.29

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

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