2-Propyl-4H-thia­zolo[3,2-a][1,3,5]triazine-4-thione

Yunus, U.; Tahir, M.K.; Bhatti, M.H.; Wong, W.-Y.

doi:10.1107/S1600536808006752

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o722

doi:10.1107/S1600536808006752

Open

access

2-Propyl-4H-thiazolo[3,2-a][1,3,5]triazine-4-thione

Uzma Yunus,^a ^* Muhammad Kalim Tahir,^a Moazzam Hussain Bhatti ^a and Wai-Yeung Wong ^b

^aDepartment of Chemistry, Allama Iqbal Open University, Islamabad, Pakistan, and ^bDepartment of Chemistry, Hong Kong Baptist University, Waterloo Road, Kowloon Tong, Hong Kong
^*Correspondence e-mail: uzma_yunus@yahoo.com

(Received 27 February 2008; accepted 11 March 2008; online 20 March 2008)

In the title compound, C₈H₉N₃S₂, the n-propyl chain is disordered over two orientations (site-occupancy ratio = 0.522:0.478) and is roughly perpendicular to the fused thiazolotriazine system. The angle between the fused ring and the propyl chain is 83.6 (1)° [ 82.2 (1)° for the disordered chain]. The structure is stabilized by C—H⋯N hydrogen bonds.

Related literature

For related literature, see: Jiang et al. (2007 ); Pauling et al. (1960 ); Yunus et al. (2007 ).

Experimental

Crystal data

C₈H₉N₃S₂
M_r = 211.32
Monoclinic, P 2₁ /c
a = 9.3240 (7) Å
b = 14.9973 (11) Å
c = 6.8063 (5) Å
β = 95.505 (1)°
V = 947.37 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 173 (2) K
0.32 × 0.25 × 0.22 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.853, T_max = 0.895
5571 measured reflections
2254 independent reflections
2077 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.068
S = 1.05
2254 reflections
161 parameters
5 restraints
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N2ⁱ	0.95	2.38	3.3261 (16)	171
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808006752/pk2086sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808006752/pk2086Isup2.hkl

checkCIF report

Comment top

We have previously reported the crystal structure of 2-phenyl-4H-thiazolo[3,2,-a]- [1,3,5]triazine-4-thione with a phenyl group attached to the 1,3,5-triazine ring (Yunus et al., 2007). The molecule was essentially planar. In contrast, in the title compound the pendant n-propyl group is almost perpendicular to the fused thiazolo[3,2,-a][1,3,5]triazine ring, which are themselves co-planar (maximum deviation from mean plane is 0.0437 (1) Å from atom C4). The n-propyl chain is disordered over two orientations with a site occupancy ratio of 0.522:0.478 (Jiang et al., 2007). The CN bond distances of the 1,3,5-triazine ring are in the range 1.3191 (15) to 1.4093 (14) Å, in which N1—C5 bond length is slightly longer than that of N2—C5. These values are intermediate between those expected for single and double C—N bonds (1.47 and 1.27 Å, respectively). The C=S bond length of 1.6686 (12) Å is similar to that of the phenyl analog (Yunus et al., 2007) but is slightly longer then the pure double bond distance (1.61 Å) (Pauling 1960). The bond angles and bond lengths in the thiazole ring are within the normal ranges. The crystal structure is stabilized by weak C—H···N hydrogen bonding interactions.

Related literature top

For related literature, see: Jiang et al. (2007); Pauling et al. (1960); Yunus et al. (2007).

Experimental top

A mixture of ammonium thiocyanate (26 mmol) and butyryl chloride (26 mmol) in dry acetone (60 ml) was stirred for 30 min. Then 2-aminothiazole (26 mmol) was added and the reaction mixture was refluxed for 2 h. After cooling, the reaction mixture was poured into acidified cold water. The resulting yellow solid was filtered and washed with cold acetone. Single crystals of the title compound suitable for single-crystal x-ray analysis were obtained by recrystallization of the yellow solid from acetonitrile.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. : A view of the molecular structure. Displacement ellipsoids are drawn at the 50% probability level.

2-Propyl-4H-thiazolo[3,2-a][1,3,5]triazine-4-thione top

Crystal data top

C₈H₉N₃S₂	F(000) = 440
M_r = 211.32	D_x = 1.481 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5571 reflections
a = 9.3240 (7) Å	θ = 2.6–28.3°
b = 14.9973 (11) Å	µ = 0.52 mm⁻¹
c = 6.8063 (5) Å	T = 173 K
β = 95.505 (1)°	Block, pale yellow
V = 947.37 (12) Å³	0.32 × 0.25 × 0.22 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2254 independent reflections
Radiation source: fine-focus sealed tube	2077 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω and ϕ scans	θ_max = 28.3°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −12→12
T_min = 0.853, T_max = 0.895	k = −19→14
5571 measured reflections	l = −9→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0392P)² + 0.2601P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2254 reflections	Δρ_max = 0.32 e Å⁻³
161 parameters	Δρ_min = −0.29 e Å⁻³
5 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0066 (12)

Crystal data top

C₈H₉N₃S₂	V = 947.37 (12) Å³
M_r = 211.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.3240 (7) Å	µ = 0.52 mm⁻¹
b = 14.9973 (11) Å	T = 173 K
c = 6.8063 (5) Å	0.32 × 0.25 × 0.22 mm
β = 95.505 (1)°

Data collection top

Bruker SMART CCD diffractometer	2254 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	2077 reflections with I > 2σ(I)
T_min = 0.853, T_max = 0.895	R_int = 0.016
5571 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	5 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 1.05	Δρ_max = 0.32 e Å⁻³
2254 reflections	Δρ_min = −0.29 e Å⁻³
161 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.20093 (3)	0.710163 (18)	0.27470 (4)	0.02095 (10)
S2	−0.15462 (3)	0.443002 (19)	0.21702 (4)	0.02265 (10)
N1	0.04853 (10)	0.56884 (6)	0.25767 (13)	0.01739 (19)
N2	0.12868 (11)	0.42185 (7)	0.29852 (15)	0.0235 (2)
N3	0.29929 (11)	0.54164 (7)	0.31895 (15)	0.0231 (2)
C1	0.01557 (13)	0.71890 (8)	0.23196 (17)	0.0224 (2)
H1	−0.0344	0.7739	0.2143	0.027*
C2	−0.04951 (12)	0.63902 (8)	0.22664 (17)	0.0211 (2)
H2	−0.1508	0.6311	0.2043	0.025*
C3	0.18861 (12)	0.59613 (7)	0.28536 (15)	0.0185 (2)
C5	0.01588 (12)	0.47711 (7)	0.25939 (15)	0.0187 (2)
C4	0.26174 (14)	0.45502 (8)	0.32834 (18)	0.0259 (3)	0.522 (4)
C6	0.3713 (6)	0.3883 (4)	0.4050 (7)	0.0221 (9)	0.522 (4)
H6A	0.3288	0.3278	0.4003	0.029 (8)*	0.522 (4)
H6B	0.4062	0.4022	0.5436	0.025 (7)*	0.522 (4)
C7	0.4958 (2)	0.39267 (16)	0.2751 (4)	0.0248 (6)	0.522 (4)
H7A	0.5357	0.4539	0.2799	0.021 (7)*	0.522 (4)
H7B	0.5730	0.3517	0.3292	0.036 (8)*	0.522 (4)
C8	0.4516 (9)	0.3679 (6)	0.0614 (6)	0.0357 (13)	0.522 (4)
H8A	0.5357	0.3714	−0.0143	0.030 (8)*	0.522 (4)
H8B	0.3773	0.4093	0.0055	0.045 (10)*	0.522 (4)
H8C	0.4134	0.3070	0.0552	0.061 (12)*	0.522 (4)
C4A	0.26174 (14)	0.45502 (8)	0.32834 (18)	0.0259 (3)	0.478 (4)
C6A	0.3938 (7)	0.3911 (4)	0.3487 (8)	0.0255 (12)	0.478 (4)
H6A1	0.4827	0.4276	0.3621	0.047 (11)*	0.478 (4)
H6A2	0.3913	0.3565	0.4722	0.038 (11)*	0.478 (4)
C7A	0.4034 (3)	0.32554 (16)	0.1781 (4)	0.0247 (7)	0.478 (4)
H7A1	0.4736	0.2781	0.2199	0.036 (9)*	0.478 (4)
H7A2	0.3083	0.2970	0.1461	0.037 (9)*	0.478 (4)
C8A	0.4491 (8)	0.3709 (6)	−0.0056 (8)	0.0320 (11)	0.478 (4)
H8A1	0.4583	0.3263	−0.1087	0.064 (14)*	0.478 (4)
H8A2	0.5420	0.4007	0.0263	0.061 (13)*	0.478 (4)
H8A3	0.3764	0.4152	−0.0528	0.030 (9)*	0.478 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02618 (16)	0.01417 (15)	0.02233 (16)	−0.00294 (10)	0.00150 (11)	0.00001 (9)
S2	0.02469 (16)	0.01845 (15)	0.02542 (16)	−0.00432 (10)	0.00559 (11)	−0.00188 (10)
N1	0.0225 (4)	0.0139 (4)	0.0155 (4)	−0.0004 (3)	0.0008 (3)	0.0001 (3)
N2	0.0307 (5)	0.0151 (4)	0.0231 (5)	0.0010 (4)	−0.0059 (4)	−0.0003 (4)
N3	0.0254 (5)	0.0183 (5)	0.0243 (5)	0.0009 (4)	−0.0051 (4)	−0.0020 (4)
C1	0.0273 (6)	0.0166 (5)	0.0236 (6)	0.0020 (4)	0.0037 (4)	−0.0001 (4)
C2	0.0235 (5)	0.0172 (5)	0.0226 (5)	0.0024 (4)	0.0029 (4)	0.0003 (4)
C3	0.0247 (5)	0.0157 (5)	0.0147 (5)	−0.0022 (4)	0.0000 (4)	−0.0010 (4)
C5	0.0280 (5)	0.0148 (5)	0.0130 (5)	−0.0015 (4)	0.0010 (4)	−0.0015 (4)
C4	0.0301 (6)	0.0183 (5)	0.0266 (6)	0.0025 (4)	−0.0106 (5)	−0.0023 (4)
C6	0.0217 (16)	0.0211 (14)	0.023 (2)	0.0022 (11)	−0.0009 (16)	0.0060 (18)
C7	0.0159 (11)	0.0253 (12)	0.0332 (13)	0.0029 (8)	0.0023 (9)	−0.0008 (9)
C8	0.0347 (17)	0.039 (2)	0.034 (3)	0.0051 (15)	0.006 (3)	−0.009 (3)
C4A	0.0301 (6)	0.0183 (5)	0.0266 (6)	0.0025 (4)	−0.0106 (5)	−0.0023 (4)
C6A	0.032 (3)	0.0196 (16)	0.023 (3)	0.0051 (16)	−0.0085 (19)	0.0019 (19)
C7A	0.0224 (11)	0.0180 (12)	0.0337 (15)	0.0042 (9)	0.0030 (10)	0.0003 (10)
C8A	0.0268 (16)	0.0325 (18)	0.038 (3)	−0.0014 (13)	0.009 (3)	0.004 (3)

Geometric parameters (Å, º) top

S1—C3	1.7161 (11)	C6—H6B	0.9900
S1—C1	1.7299 (13)	C7—C8	1.519 (5)
S2—C5	1.6686 (12)	C7—H7A	0.9900
N1—C3	1.3644 (14)	C7—H7B	0.9900
N1—C2	1.3967 (14)	C8—H8A	0.9800
N1—C5	1.4093 (14)	C8—H8B	0.9800
N2—C4	1.3340 (16)	C8—H8C	0.9800
N2—C5	1.3455 (15)	C6A—C7A	1.531 (6)
N3—C3	1.3191 (15)	C6A—H6A1	0.9900
N3—C4	1.3485 (15)	C6A—H6A2	0.9900
C1—C2	1.3418 (17)	C7A—C8A	1.520 (6)
C1—H1	0.9500	C7A—H7A1	0.9900
C2—H2	0.9500	C7A—H7A2	0.9900
C4—C6	1.488 (6)	C8A—H8A1	0.9800
C6—C7	1.526 (5)	C8A—H8A2	0.9800
C6—H6A	0.9900	C8A—H8A3	0.9800

C3—S1—C1	90.73 (6)	C8—C7—C6	113.1 (4)
C3—N1—C2	113.50 (9)	C8—C7—H7A	109.0
C3—N1—C5	119.76 (9)	C6—C7—H7A	109.0
C2—N1—C5	126.73 (10)	C8—C7—H7B	109.0
C4—N2—C5	119.89 (10)	C6—C7—H7B	109.0
C3—N3—C4	113.74 (10)	H7A—C7—H7B	107.8
C2—C1—S1	112.26 (9)	C7—C8—H8A	109.5
C2—C1—H1	123.9	C7—C8—H8B	109.5
S1—C1—H1	123.9	H8A—C8—H8B	109.5
C1—C2—N1	112.39 (10)	C7—C8—H8C	109.5
C1—C2—H2	123.8	H8A—C8—H8C	109.5
N1—C2—H2	123.8	H8B—C8—H8C	109.5
N3—C3—N1	124.11 (10)	C7A—C6A—H6A1	108.4
N3—C3—S1	124.77 (9)	C7A—C6A—H6A2	108.4
N1—C3—S1	111.11 (8)	H6A1—C6A—H6A2	107.5
N2—C5—N1	115.95 (10)	C8A—C7A—C6A	112.2 (4)
N2—C5—S2	123.99 (9)	C8A—C7A—H7A1	109.2
N1—C5—S2	120.05 (8)	C6A—C7A—H7A1	109.2
N2—C4—N3	126.44 (11)	C8A—C7A—H7A2	109.2
N2—C4—C6	113.6 (3)	C6A—C7A—H7A2	109.2
N3—C4—C6	119.4 (3)	H7A1—C7A—H7A2	107.9
C4—C6—C7	107.7 (3)	C7A—C8A—H8A1	109.5
C4—C6—H6A	110.2	C7A—C8A—H8A2	109.5
C7—C6—H6A	110.2	H8A1—C8A—H8A2	109.5
C4—C6—H6B	110.2	C7A—C8A—H8A3	109.5
C7—C6—H6B	110.2	H8A1—C8A—H8A3	109.5
H6A—C6—H6B	108.5	H8A2—C8A—H8A3	109.5

C3—S1—C1—C2	−0.03 (9)	C4—N2—C5—S2	179.23 (9)
S1—C1—C2—N1	0.23 (13)	C3—N1—C5—N2	3.03 (15)
C3—N1—C2—C1	−0.38 (14)	C2—N1—C5—N2	−178.04 (10)
C5—N1—C2—C1	−179.36 (10)	C3—N1—C5—S2	−177.64 (8)
C4—N3—C3—N1	−1.45 (16)	C2—N1—C5—S2	1.28 (15)
C4—N3—C3—S1	177.43 (9)	C5—N2—C4—N3	−1.78 (19)
C2—N1—C3—N3	179.37 (10)	C5—N2—C4—C6	169.6 (2)
C5—N1—C3—N3	−1.58 (16)	C3—N3—C4—N2	3.24 (19)
C2—N1—C3—S1	0.35 (11)	C3—N3—C4—C6	−167.7 (2)
C5—N1—C3—S1	179.41 (7)	N2—C4—C6—C7	129.4 (3)
C1—S1—C3—N3	−179.19 (10)	N3—C4—C6—C7	−58.6 (4)
C1—S1—C3—N1	−0.19 (8)	C4—C6—C7—C8	−62.5 (5)
C4—N2—C5—N1	−1.48 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N2ⁱ	0.95	2.38	3.3261 (16)	171

Symmetry code: (i) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₉N₃S₂
M_r	211.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	9.3240 (7), 14.9973 (11), 6.8063 (5)
β (°)	95.505 (1)
V (Å³)	947.37 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.32 × 0.25 × 0.22

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.853, 0.895
No. of measured, independent and observed [I > 2σ(I)] reflections	5571, 2254, 2077
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.068, 1.05
No. of reflections	2254
No. of parameters	161
No. of restraints	5
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.29

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N2ⁱ	0.95	2.38	3.3261 (16)	171

Symmetry code: (i) −x, y+1/2, −z+1/2.

Acknowledgements

The authors gratefully acknowledge Allama Iqbal Open University, Islamabad, Pakistan, for providing research facilities.

References

Bruker (1998). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (1999). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Jiang, Y.-P., Qiu, T., Wang, L.-E. & Wang, J.-N. (2007). Acta Cryst. E63, o3096. Web of Science CSD CrossRef IUCr Journals Google Scholar
Pauling, L. (1960). The Nature of the Chemical Bond, 3rd ed. Ithaca: Cornell University Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yunus, U., Tahir, M. K., Bhatti, M. H., Ali, S. & Helliwell, M. (2007). Acta Cryst. E63, o3690. Web of Science CSD CrossRef IUCr Journals Google Scholar