1,3-Thia­zole-4-carbo­nitrile

Fait, M.J.G.; Spannenberg, A.; Kondratenko, E.V.; Linke, D.

doi:10.1107/S2414314621013328

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 6| Part 12| December 2021| x211332

https://doi.org/10.1107/S2414314621013328

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1,3-Thiazole-4-carbonitrile

Martin J. G. Fait,^a Anke Spannenberg,^a Evgenii V. Kondratenko ^a and David Linke ^a ^*

^aLeibniz-Institut für Katalyse e. V., Albert-Einstein-Str. 29a, 18059 Rostock, Germany
^*Correspondence e-mail: david.linke@catalysis.de

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 20 October 2021; accepted 15 December 2021; online 21 December 2021)

The title compound, C₄H₂N₂S, is a 1,3-thiazole substituted in the 4-position by a nitrile group. In the crystal, C—H⋯N hydrogen bonds and aromatic π–π stacking interactions are observed.

Keywords: crystal structure; thiazole; nitrile group; hydrogen bonding; π–π stacking interaction.

CCDC reference: 2128844

Structure description

The title compound, C₄H₂N₂S, consists of a 1,3-thiazole ring substituted in the 4-position by a nitrile group (Fig. 1). The whole molecule is nearly planar with a mean deviation from the best plane defined by all non-hydrogen atoms of 0.005 Å. All bond lengths are in the expected ranges (Allen et al., 1987 ).

Figure 1
Molecular structure of the title compound with atom labelling and displacement ellipsoids drawn at 50% probability level.

In the crystal, weak C—H⋯N hydrogen bonds arising from both C—H groupings build up a wavy layer of molecules in the (011) plane (Table 1, Fig. 2). The layers are stacked in the (100) direction by weak π–π stacking interactions between the 1,3-thiazole rings [centroid–centroid distance = 3.7924 (10) Å, ring slippage = 1.39 Å].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N2ⁱ	0.95	2.59	3.374 (2)	140
C3—H3⋯N1ⁱⁱ	0.95	2.57	3.257 (2)	129
Symmetry codes: (i) ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Packing diagram for the title compound along the a axis. Ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dotted lines.

Synthesis and crystallization

Commercial powder of the title compound (Fluorochem, UK, catalogue No. # 076318) was purified by sublimation at normal pressure on a hot plate set to 55°C. The colourless crystals formed over two days on the covering watch glass. ¹H NMR (300.2 MHz, DMSO-d₆) δ 9.316, 9.310 (J = 1.82 Hz, H3), 8.908, 8.902 (J = 1.84 Hz, H2). ¹³C NMR (75.5 MHz, DMSO-d₆) δ 157.4, 133.6, 125.9, 114.5. The NMR data are consistent with those previously published by Augustine et al. (2009 ).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₄H₂N₂S
M_r	110.14
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	3.7924 (3), 19.8932 (18), 6.3155 (5)
β (°)	91.084 (6)
V (Å³)	476.37 (7)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	4.77
Crystal size (mm)	0.24 × 0.18 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.40, 0.71
No. of measured, independent and observed [I > 2σ(I)] reflections	4709, 854, 783
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.097, 1.09
No. of reflections	854
No. of parameters	64
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.23
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2013 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), XP in SHELXTL (Sheldrick, 2015), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2128844

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314621013328/hb4395sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621013328/hb4395Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314621013328/hb4395Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2015) and Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

1,3-Thiazole-4-carbonitrile top

Crystal data top

C₄H₂N₂S	F(000) = 224
M_r = 110.14	D_x = 1.536 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
a = 3.7924 (3) Å	Cell parameters from 2588 reflections
b = 19.8932 (18) Å	θ = 4.5–66.7°
c = 6.3155 (5) Å	µ = 4.77 mm⁻¹
β = 91.084 (6)°	T = 150 K
V = 476.37 (7) Å³	Plate, colourless
Z = 4	0.24 × 0.18 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	854 independent reflections
Radiation source: microfocus	783 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.040
Detector resolution: 8.3333 pixels mm^-1	θ_max = 66.7°, θ_min = 4.5°
φ and ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −23→23
T_min = 0.40, T_max = 0.71	l = −7→7
4709 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0638P)² + 0.0618P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
854 reflections	Δρ_max = 0.32 e Å⁻³
64 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
C1	0.8382 (4)	0.61784 (9)	0.5796 (3)	0.0306 (4)
C2	0.8897 (5)	0.59416 (9)	0.7795 (3)	0.0360 (4)
H2	0.838664	0.549800	0.825466	0.043*
C3	1.0479 (5)	0.70963 (10)	0.7216 (3)	0.0388 (5)
H3	1.124522	0.755015	0.731394	0.047*
C4	0.6933 (5)	0.57919 (9)	0.4057 (3)	0.0350 (4)
N1	0.9271 (4)	0.68396 (9)	0.5450 (3)	0.0400 (4)
N2	0.5794 (5)	0.54939 (9)	0.2660 (3)	0.0450 (4)
S1	1.06029 (11)	0.65664 (2)	0.93452 (7)	0.0367 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0280 (7)	0.0334 (9)	0.0306 (9)	0.0004 (7)	0.0030 (6)	0.0000 (6)
C2	0.0424 (10)	0.0352 (9)	0.0304 (9)	0.0020 (7)	0.0011 (7)	0.0000 (7)
C3	0.0400 (9)	0.0378 (9)	0.0383 (11)	−0.0060 (7)	−0.0022 (8)	0.0015 (7)
C4	0.0381 (9)	0.0364 (9)	0.0305 (9)	−0.0020 (7)	0.0040 (7)	0.0031 (7)
N1	0.0480 (10)	0.0372 (10)	0.0346 (9)	−0.0069 (6)	−0.0029 (7)	0.0049 (6)
N2	0.0559 (10)	0.0455 (9)	0.0336 (9)	−0.0102 (8)	0.0000 (7)	−0.0022 (7)
S1	0.0380 (3)	0.0426 (3)	0.0294 (3)	0.00213 (16)	−0.0020 (2)	−0.00236 (15)

Geometric parameters (Å, º) top

C1—C2	1.358 (3)	C3—N1	1.302 (3)
C1—N1	1.376 (3)	C3—S1	1.7089 (19)
C1—C4	1.441 (3)	C3—H3	0.9500
C2—S1	1.7024 (19)	C4—N2	1.141 (3)
C2—H2	0.9500

C2—C1—N1	116.58 (16)	N1—C3—S1	115.85 (15)
C2—C1—C4	124.71 (17)	N1—C3—H3	122.1
N1—C1—C4	118.70 (16)	S1—C3—H3	122.1
C1—C2—S1	109.13 (14)	N2—C4—C1	178.96 (19)
C1—C2—H2	125.4	C3—N1—C1	108.81 (16)
S1—C2—H2	125.4	C2—S1—C3	89.62 (9)

N1—C1—C2—S1	−0.4 (2)	C4—C1—N1—C3	179.24 (16)
C4—C1—C2—S1	−179.26 (14)	C1—C2—S1—C3	0.28 (15)
S1—C3—N1—C1	−0.1 (2)	N1—C3—S1—C2	−0.12 (16)
C2—C1—N1—C3	0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N2ⁱ	0.95	2.59	3.374 (2)	140
C3—H3···N1ⁱⁱ	0.95	2.57	3.257 (2)	129

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+3/2, z+1/2.

References

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