(Z)-3-(4-Methyl­phen­yl)-2-(3-thien­yl)acrylonitrile

Cobo, D.; Cobo, J.; Low, J.N.; Glidewell, C.

doi:10.1107/S1600536806042231

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 11| November 2006| Pages o5179-o5180

https://doi.org/10.1107/S1600536806042231

(Z)-3-(4-Methylphenyl)-2-(3-thienyl)acrylonitrile

Debora Cobo,^a Justo Cobo,^b John N. Low ^c and Christopher Glidewell ^d ^*

^aGrupo de Investigación de Compuestos Heterocíclicos, Departamento de Química, Universidad de Valle, AA 25360 Cali, Colombia, ^bDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, ^cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 11 October 2006; accepted 11 October 2006; online 25 October 2006)

In the molecule of the title compound, C₁₄H₁₁NS, the benzene ring is significantly rotated out of the plane of the rest of the molecule. There are no significant direction-specific interactions between the molecules.

Comment

We have recently reported the structures of a number of 3-aryl-2-thienylacrylonitrile derivatives (Cobo et al., 2005 , 2006 ). We report here the structure of the title compound, (I) (Fig. 1), which we compare with that of the phenyl analogue, (II) (Cobo et al., 2006). The molecule of compound (I) is approximately planar apart from the benzene ring, which is significantly rotated out of the plane of the rest of the molecule about the bond C17—C11 (Table 1). The nitrile fragment shows the usual long C—C bond and very short C—N bond, but the rest of the geometry shows no unexpected features. By contrast, the whole molecule of compound (II) is virtually planar, with a C37—C17—C11—C12 torsion angle of only −1.7 (5)°.

In compound (II), the molecules are linked into sheets by a combination of C—H⋯N and C—H⋯π(arene) hydrogen bonds; by contrast, in (I), the shortest non-bonded intermolecular contacts between potential hydrogen-bond donors and acceptors (Table 2) are all too long to be structurally significant, although they involve precisely the same combinations of donors and acceptors as the hydrogen bonds in compound (II). Hence, the introduction of the 4-methyl substituent in compound (I) in place of the 4-H in compound (II) appears to stretch the crystal structure sufficiently to put the corresponding combinations of hydrogen-bond donors and acceptors just out of bonding range.

Figure 1
The molecular structure of (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Experimental

A solution of 3-thiopheneacetonitrile (1 mmol) and potassium tert-butoxide (1 mmol) in anhydrous ethanol (3 ml) was stirred at room temperature for 15 min; a solution of 4-methylbenzaldehyde (1 mmol) in anhydrous ethanol (3 ml) was then added and the mixture was set aside until formation of a precipitate was complete. The resulting solid product was collected by filtration, washed with ethanol, dried and finally recrystallized from dimethylformamide to give colourless crystals of (I) suitable for single-crystal X-ray diffraction (yield 60%; m.p. 365–367 K).

Crystal data

C₁₄H₁₁NS
M_r = 225.30
Monoclinic, P 2₁ /c
a = 13.7415 (3) Å
b = 10.8492 (3) Å
c = 8.0238 (2) Å
β = 106.439 (2)°
V = 1147.32 (5) Å³
Z = 4
D_x = 1.304 Mg m⁻³
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 120 (2) K
Block, colourless
0.50 × 0.25 × 0.25 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.885, T_max = 0.940
15435 measured reflections
2628 independent reflections
2284 reflections with I > 2σ(I)
R_int = 0.027
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.096
S = 1.05
2628 reflections
146 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0499P)² + 0.5552P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C37—C371	1.4444 (18)
C371—N37	1.1499 (18)

C2—C3—C37—C17	176.17 (13)
C3—C37—C17—C11	−177.98 (12)
C37—C17—C11—C12	−26.9 (2)

Table 2
Parameters (Å, °) for short intermolecular contacts

Cg is the centroid of the C11–C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N37ⁱ	0.95	2.75	3.312 (2)	119
C13—H13⋯Cgⁱⁱ	0.95	2.99	3.777 (2)	141
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

All H atoms were treated as riding atoms, with C—H = 0.98 (CH₃) or 0.95 Å (all other H atoms) and U_iso(H) = kU_eq(C), where k = 1.5 for methyl H atoms and 1.2 for all other H atoms.

Data collection: COLLECT (Hooft, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806042231/lh2209sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806042231/lh2209Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

(Z)-3-(4-methylphenyl)-2-(3-thienyl)acrylonitrile top

Crystal data top

C₁₄H₁₁NS	F(000) = 472
M_r = 225.30	D_x = 1.304 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2628 reflections
a = 13.7415 (3) Å	θ = 2.4–27.5°
b = 10.8492 (3) Å	µ = 0.25 mm⁻¹
c = 8.0238 (2) Å	T = 120 K
β = 106.439 (2)°	Block, colourless
V = 1147.32 (5) Å³	0.50 × 0.25 × 0.25 mm
Z = 4

Data collection top

Bruker–Nonius KappaCCD diffractometer	2628 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2284 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 2.4°
φ and ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→14
T_min = 0.885, T_max = 0.940	l = −10→10
15435 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0499P)² + 0.5552P] where P = (F_o² + 2F_c²)/3
2628 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

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

	x	y	z	U_iso*/U_eq
S1	0.33892 (2)	0.22914 (3)	0.23475 (4)	0.02236 (12)
C2	0.45498 (10)	0.19264 (13)	0.37130 (17)	0.0193 (3)
C3	0.51901 (10)	0.29212 (12)	0.40812 (16)	0.0164 (3)
C4	0.47088 (10)	0.40121 (13)	0.32193 (17)	0.0198 (3)
C5	0.37394 (11)	0.37998 (13)	0.22405 (18)	0.0222 (3)
C37	0.62421 (10)	0.28555 (12)	0.52110 (16)	0.0164 (3)
C371	0.65503 (9)	0.16439 (12)	0.59084 (17)	0.0177 (3)
N37	0.67540 (9)	0.06549 (11)	0.63993 (16)	0.0241 (3)
C17	0.69020 (10)	0.38086 (12)	0.55123 (16)	0.0174 (3)
C11	0.79651 (10)	0.38364 (12)	0.65604 (16)	0.0167 (3)
C12	0.83749 (10)	0.30514 (13)	0.79697 (18)	0.0208 (3)
C13	0.93993 (11)	0.30936 (14)	0.88594 (18)	0.0229 (3)
C14	1.00530 (10)	0.39136 (14)	0.83822 (18)	0.0214 (3)
C141	1.11724 (11)	0.39195 (16)	0.9328 (2)	0.0313 (4)
C15	0.96409 (11)	0.47273 (14)	0.70231 (18)	0.0236 (3)
C16	0.86167 (11)	0.46975 (13)	0.61301 (18)	0.0215 (3)
H2	0.4732	0.1124	0.4167	0.023*
H4	0.5030	0.4795	0.3320	0.024*
H5	0.3308	0.4415	0.1576	0.027*
H17	0.6641	0.4565	0.4970	0.021*
H12	0.7946	0.2482	0.8321	0.025*
H13	0.9660	0.2553	0.9813	0.028*
H14A	1.1264	0.3939	1.0584	0.047*
H14B	1.1490	0.4649	0.8985	0.047*
H14C	1.1489	0.3174	0.9029	0.047*
H15	1.0069	0.5313	0.6702	0.028*
H16	0.8353	0.5268	0.5215	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01510 (19)	0.0265 (2)	0.02236 (19)	−0.00323 (12)	0.00024 (14)	0.00062 (13)
C2	0.0159 (6)	0.0206 (7)	0.0203 (6)	−0.0009 (5)	0.0032 (5)	−0.0001 (5)
C3	0.0145 (6)	0.0196 (7)	0.0155 (6)	0.0000 (5)	0.0049 (5)	−0.0010 (5)
C4	0.0190 (6)	0.0191 (7)	0.0201 (6)	0.0007 (5)	0.0036 (5)	0.0003 (5)
C5	0.0202 (7)	0.0236 (7)	0.0213 (6)	0.0029 (5)	0.0031 (5)	0.0021 (5)
C37	0.0153 (6)	0.0182 (6)	0.0156 (6)	0.0006 (5)	0.0044 (5)	−0.0009 (5)
C371	0.0126 (6)	0.0215 (7)	0.0178 (6)	−0.0021 (5)	0.0020 (5)	−0.0032 (5)
N37	0.0217 (6)	0.0206 (6)	0.0273 (6)	−0.0012 (5)	0.0025 (5)	−0.0012 (5)
C17	0.0164 (6)	0.0188 (6)	0.0164 (6)	0.0005 (5)	0.0035 (5)	−0.0007 (5)
C11	0.0155 (6)	0.0177 (6)	0.0168 (6)	−0.0009 (5)	0.0040 (5)	−0.0033 (5)
C12	0.0194 (7)	0.0214 (7)	0.0202 (6)	−0.0053 (5)	0.0035 (5)	0.0007 (5)
C13	0.0216 (7)	0.0221 (7)	0.0208 (6)	0.0001 (5)	−0.0010 (5)	0.0000 (5)
C14	0.0144 (6)	0.0258 (7)	0.0231 (7)	−0.0010 (5)	0.0035 (5)	−0.0080 (5)
C141	0.0142 (7)	0.0421 (9)	0.0345 (8)	−0.0011 (6)	0.0021 (6)	−0.0088 (7)
C15	0.0202 (7)	0.0274 (8)	0.0243 (7)	−0.0080 (5)	0.0082 (6)	−0.0029 (6)
C16	0.0223 (7)	0.0209 (7)	0.0201 (6)	−0.0031 (5)	0.0040 (5)	0.0015 (5)

Geometric parameters (Å, º) top

S1—C2	1.7064 (13)	C11—C12	1.4002 (19)
S1—C5	1.7147 (15)	C11—C16	1.4031 (19)
C2—C3	1.3709 (19)	C12—C13	1.3873 (19)
C2—H2	0.95	C12—H12	0.95
C3—C4	1.4345 (18)	C13—C14	1.393 (2)
C3—C37	1.4748 (17)	C13—H13	0.95
C4—C5	1.3609 (19)	C14—C15	1.393 (2)
C4—H4	0.95	C14—C141	1.5104 (18)
C5—H5	0.95	C141—H14A	0.98
C37—C17	1.3512 (18)	C141—H14B	0.98
C37—C371	1.4444 (18)	C141—H14C	0.98
C371—N37	1.1499 (18)	C15—C16	1.3873 (19)
C17—C11	1.4653 (18)	C15—H15	0.95
C17—H17	0.95	C16—H16	0.95

C2—S1—C5	91.67 (7)	C16—C11—C17	118.33 (12)
C3—C2—S1	112.45 (10)	C13—C12—C11	120.87 (13)
C3—C2—H2	123.8	C13—C12—H12	119.6
S1—C2—H2	123.8	C11—C12—H12	119.6
C2—C3—C4	111.43 (12)	C12—C13—C14	121.27 (13)
C2—C3—C37	123.51 (12)	C12—C13—H13	119.4
C4—C3—C37	125.05 (12)	C14—C13—H13	119.4
C5—C4—C3	112.40 (12)	C15—C14—C13	117.99 (13)
C5—C4—H4	123.8	C15—C14—C141	121.43 (13)
C3—C4—H4	123.8	C13—C14—C141	120.59 (13)
C4—C5—S1	112.05 (11)	C14—C141—H14A	109.5
C4—C5—H5	124.0	C14—C141—H14B	109.5
S1—C5—H5	124.0	H14A—C141—H14B	109.5
C17—C37—C371	121.25 (12)	C14—C141—H14C	109.5
C17—C37—C3	124.36 (12)	H14A—C141—H14C	109.5
C371—C37—C3	114.27 (11)	H14B—C141—H14C	109.5
N37—C371—C37	176.48 (14)	C16—C15—C14	121.19 (13)
C37—C17—C11	128.90 (12)	C16—C15—H15	119.4
C37—C17—H17	115.5	C14—C15—H15	119.4
C11—C17—H17	115.5	C15—C16—C11	120.88 (13)
C12—C11—C16	117.70 (12)	C15—C16—H16	119.6
C12—C11—C17	123.97 (12)	C11—C16—H16	119.6

C5—S1—C2—C3	−0.05 (11)	C37—C17—C11—C12	−26.9 (2)
S1—C2—C3—C4	0.22 (15)	C37—C17—C11—C16	152.97 (14)
S1—C2—C3—C37	−179.23 (10)	C16—C11—C12—C13	−2.6 (2)
C2—C3—C4—C5	−0.33 (17)	C17—C11—C12—C13	177.24 (13)
C37—C3—C4—C5	179.11 (12)	C11—C12—C13—C14	−0.1 (2)
C3—C4—C5—S1	0.29 (15)	C12—C13—C14—C15	2.5 (2)
C2—S1—C5—C4	−0.14 (11)	C12—C13—C14—C141	−178.03 (13)
C2—C3—C37—C17	176.17 (13)	C13—C14—C15—C16	−2.1 (2)
C4—C3—C37—C17	−3.2 (2)	C141—C14—C15—C16	178.38 (13)
C2—C3—C37—C371	0.06 (18)	C14—C15—C16—C11	−0.6 (2)
C4—C3—C37—C371	−179.31 (12)	C12—C11—C16—C15	2.9 (2)
C371—C37—C17—C11	−2.1 (2)	C17—C11—C16—C15	−176.91 (13)
C3—C37—C17—C11	−177.98 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N37ⁱ	0.95	2.75	3.312 (2)	119
C13—H13···Cgⁱⁱ	0.95	2.99	3.777 (2)	141

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

Acknowledgements

X-ray data were collected at the EPSRC National X-ray Crystallography Service, University of Southampton, England. JC and JT thank the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support. DC thanks COLCIENCIAS and UNIVALLE (Universidad del Valle, Colombia) for financial support.

References

Cobo, D., Quiroga, J., Cobo, J., Low, J. N. & Glidewell, C. (2005). Acta Cryst. E61, o3639–o3641. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Cobo, D., Quiroga, J., de la Torre, J. M., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o550–o553. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.