(2E)-3-Phenyl­prop-2-en-1-yl thio­cyanate

Khan, E.; Shahzad, A.; Tahir, M.N.; Ateeq, M.

doi:10.1107/S2414314617005491

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 4| April 2017| x170549

https://doi.org/10.1107/S2414314617005491

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(2E)-3-Phenylprop-2-en-1-yl thiocyanate

Ezzat Khan,^a ^* Adnan Shahzad,^b M. Nawaz Tahir ^c and Muhammad Ateeq ^d

^aDepartment of Chemistry, University of Malakand, Pakistan, ^bInstitute of Chemical Sciences, University of Swat, Khyber Pakhtunkhwa, Pakistan, ^cDepartment of Physics, University of Sargodha, Sargodha, Pakistan, and ^dHEJ Research Institute, University of Karachi, Karachi, Pakistan
^*Correspondence e-mail: ekhan@uom.edu.pk

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 21 March 2017; accepted 11 April 2017; online 21 April 2017)

In the title compound, C₁₀H₉NS, the C—S—C bond angle is 99.41 (9)° and the dihedral angle between the trans-alkene fragment and the benzene ring is 16.49 (19)°. In the crystal, inversion dimers linked by pairs of extremely weak C—H⋯N interactions occur, as does a short S⋯N contact [3.2258 (19) Å].

Keywords: crystal structure; cinammyl chloride; ammonium thiocyanate.

CCDC reference: 1543491

Structure description

Alkyl thiocyanates are synthetic precursors for the preparation of sulfur-containing organic compounds such as disulfides (Lu et al., 2014 ) and various heterocyclic compounds (Vikharev et al., 2005 ; Batanero et al., 2002 ). The title compound (Fig. 1) arose during our studies of unsymmetrical thiourea derivatives.

Figure 1
The molecular structure of the title compound, showing 50% displacement ellipsoids.

The C—S—C bond angle is 99.41 (9)° and the dihedral angle between the C2/C3/C4/C5 fragment and the benzene ring is 16.49 (19)°. A quantum-chemical calculation for this molecule (see Supporting information) gave a C—S—C angle of 160.0°. In the crystal, extremely weak C—H⋯N interactions (Table 1) generate inversion dimers with an R₂²(10) motif and short S⋯N contacts [3.2258 (19) Å, compared to a van der Waals radius sum of 3.35 Å] are also observed: these contacts link the dimers into [100] chains (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯N1ⁱ	0.97	2.70	3.652 (2)	167
Symmetry code: (i) -x+2, -y+1, -z+1.

Figure 2
Unit-cell packing diagram (left) and supramolecular chain (right insert) of the title compound showing the C—H⋯N hydrogen bonds and N—S interactions.

Synthesis and crystallization

A round-bottom flask was charged with cinammyl chloride (1 ml, 7.2 mmol) in acetone. The solution was stirred vigorously and NH₄SCN (0.5 g, 7.2 mmol) was added. The reaction mixture was heated to reflux for 30 min and then poured into crushed ice. The solid product was separated and dissolved in CH₂Cl₂. After 24 h, colorless prismatic crystals appeared in solution. Crystals of appropriate quality of the same compound were also obtained from n-hexane solution. A reaction scheme is given in Fig. 3.

Figure 3
Reaction scheme.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₉NS
M_r	175.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	6.0108 (5), 7.9243 (6), 19.8388 (16)
β (°)	94.271 (4)
V (Å³)	942.33 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.29
Crystal size (mm)	0.37 × 0.27 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2005 )
T_min, T_max	0.902, 0.932
No. of measured, independent and observed [I > 2σ(I)] reflections	8591, 2319, 1697
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.112, 1.05
No. of reflections	2319
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.39
Computer programs: APEX2 and SAINT (Bruker, 2007 ), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1543491

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617005491/hb4134sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617005491/hb4134Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617005491/hb4134Isup4.cdx

Quantum-chemical calculations. DOI: https://doi.org/10.1107/S2414314617005491/hb4134sup3.pdf

Supporting information file. DOI: https://doi.org/10.1107/S2414314617005491/hb4134Isup5.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

(2E)-3-Phenylprop-2-en-1-yl thiocyanate top

Crystal data top

C₁₀H₉NS	F(000) = 368
M_r = 175.24	D_x = 1.235 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.0108 (5) Å	Cell parameters from 1697 reflections
b = 7.9243 (6) Å	θ = 2.8–28.4°
c = 19.8388 (16) Å	µ = 0.29 mm⁻¹
β = 94.271 (4)°	T = 296 K
V = 942.33 (13) Å³	Prism, colourless
Z = 4	0.37 × 0.27 × 0.25 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2319 independent reflections
Radiation source: fine-focus sealed tube	1697 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 7.50 pixels mm^-1	θ_max = 28.4°, θ_min = 2.8°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2005)	k = −9→10
T_min = 0.902, T_max = 0.932	l = −26→24
8591 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0412P)² + 0.2661P] where P = (F_o² + 2F_c²)/3
2319 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

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.

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 > σ(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
S1	0.66511 (8)	0.22408 (8)	0.47818 (3)	0.0691 (2)
N1	1.1334 (3)	0.2485 (3)	0.48932 (12)	0.0962 (7)
C1	0.9445 (3)	0.2408 (3)	0.48395 (10)	0.0633 (5)
C2	0.5958 (3)	0.3977 (3)	0.41956 (10)	0.0676 (5)
H2A	0.4348	0.4037	0.4114	0.081*
H2B	0.6457	0.5027	0.4408	0.081*
C3	0.6953 (3)	0.3822 (2)	0.35388 (9)	0.0564 (4)
H3	0.6398	0.3001	0.3236	0.068*
C4	0.8586 (3)	0.4791 (2)	0.33626 (9)	0.0522 (4)
H4	0.9140	0.5571	0.3683	0.063*
C5	0.9632 (3)	0.47826 (19)	0.27201 (8)	0.0465 (4)
C6	0.8665 (3)	0.3994 (2)	0.21446 (9)	0.0534 (4)
H6	0.7302	0.3447	0.2162	0.064*
C7	0.9699 (3)	0.4015 (2)	0.15505 (9)	0.0623 (5)
H7	0.9031	0.3484	0.1169	0.075*
C8	1.1715 (3)	0.4817 (2)	0.15159 (10)	0.0660 (5)
H8	1.2413	0.4825	0.1113	0.079*
C9	1.2691 (3)	0.5602 (2)	0.20754 (11)	0.0650 (5)
H9	1.4057	0.6143	0.2053	0.078*
C10	1.1658 (3)	0.5595 (2)	0.26705 (10)	0.0571 (4)
H10	1.2329	0.6145	0.3047	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0554 (3)	0.0917 (4)	0.0609 (3)	−0.0079 (2)	0.0080 (2)	0.0169 (3)
N1	0.0577 (11)	0.1294 (19)	0.1012 (16)	0.0042 (11)	0.0046 (10)	0.0073 (13)
C1	0.0601 (11)	0.0766 (13)	0.0537 (10)	0.0024 (9)	0.0081 (8)	−0.0006 (9)
C2	0.0608 (11)	0.0811 (14)	0.0625 (11)	0.0112 (10)	0.0148 (8)	0.0083 (10)
C3	0.0561 (10)	0.0601 (11)	0.0533 (10)	0.0004 (8)	0.0049 (7)	0.0036 (8)
C4	0.0591 (10)	0.0442 (9)	0.0529 (10)	0.0018 (7)	0.0015 (7)	−0.0023 (7)
C5	0.0516 (9)	0.0361 (8)	0.0516 (9)	0.0024 (6)	0.0022 (7)	0.0037 (7)
C6	0.0542 (9)	0.0490 (10)	0.0567 (10)	−0.0080 (7)	0.0026 (7)	0.0016 (8)
C7	0.0783 (12)	0.0558 (11)	0.0529 (10)	−0.0051 (9)	0.0046 (9)	−0.0020 (8)
C8	0.0779 (12)	0.0569 (12)	0.0658 (12)	0.0006 (9)	0.0235 (10)	0.0063 (9)
C9	0.0574 (10)	0.0531 (11)	0.0863 (14)	−0.0071 (8)	0.0177 (9)	0.0056 (10)
C10	0.0573 (10)	0.0462 (10)	0.0668 (11)	−0.0056 (8)	−0.0012 (8)	−0.0031 (8)

Geometric parameters (Å, º) top

S1—C1	1.680 (2)	C5—C6	1.390 (2)
S1—C2	1.829 (2)	C6—C7	1.373 (2)
N1—C1	1.134 (2)	C6—H6	0.9300
C2—C3	1.479 (2)	C7—C8	1.374 (3)
C2—H2A	0.9700	C7—H7	0.9300
C2—H2B	0.9700	C8—C9	1.366 (3)
C3—C4	1.313 (2)	C8—H8	0.9300
C3—H3	0.9300	C9—C10	1.374 (3)
C4—C5	1.463 (2)	C9—H9	0.9300
C4—H4	0.9300	C10—H10	0.9300
C5—C10	1.388 (2)

C1—S1—C2	99.41 (9)	C6—C5—C4	122.49 (15)
N1—C1—S1	178.0 (2)	C7—C6—C5	120.76 (16)
C3—C2—S1	114.20 (14)	C7—C6—H6	119.6
C3—C2—H2A	108.7	C5—C6—H6	119.6
S1—C2—H2A	108.7	C6—C7—C8	120.36 (18)
C3—C2—H2B	108.7	C6—C7—H7	119.8
S1—C2—H2B	108.7	C8—C7—H7	119.8
H2A—C2—H2B	107.6	C9—C8—C7	119.79 (18)
C4—C3—C2	123.06 (18)	C9—C8—H8	120.1
C4—C3—H3	118.5	C7—C8—H8	120.1
C2—C3—H3	118.5	C8—C9—C10	120.13 (17)
C3—C4—C5	127.41 (16)	C8—C9—H9	119.9
C3—C4—H4	116.3	C10—C9—H9	119.9
C5—C4—H4	116.3	C9—C10—C5	121.19 (17)
C10—C5—C6	117.75 (16)	C9—C10—H10	119.4
C10—C5—C4	119.76 (15)	C5—C10—H10	119.4

C1—S1—C2—C3	58.62 (17)	C5—C6—C7—C8	0.1 (3)
S1—C2—C3—C4	−108.73 (19)	C6—C7—C8—C9	−0.2 (3)
C2—C3—C4—C5	−177.71 (16)	C7—C8—C9—C10	−0.2 (3)
C3—C4—C5—C10	−164.85 (18)	C8—C9—C10—C5	0.7 (3)
C3—C4—C5—C6	15.7 (3)	C6—C5—C10—C9	−0.9 (3)
C10—C5—C6—C7	0.5 (2)	C4—C5—C10—C9	179.60 (16)
C4—C5—C6—C7	179.97 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···N1ⁱ	0.97	2.70	3.652 (2)	167

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

We are thankful to Professor Dr Muhammad Raza Shah for the EI–MS analysis of the title compound.

Funding information

Funding for this research was provided by: Higher Education Commission Pakistan (Access to the Scientific Instrumentation project).

References

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