(E)-3-(4-Chloro­phen­yl)-2-(2-thien­yl)acrylonitrile: chains built from C—H⋯N hydrogen bonds

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

doi:10.1107/S1600536805031752

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 11| November 2005| Pages o3639-o3641

https://doi.org/10.1107/S1600536805031752

(E)-3-(4-Chlorophenyl)-2-(2-thienyl)acrylonitrile: chains built from C—H⋯N hydrogen bonds

Debora Cobo,^a Jairo Quiroga,^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 3 October 2005; accepted 5 October 2005; online 12 October 2005)

In the title compound, C₁₃H₈ClNS, the thiophene ring is disordered over two orientations. The molecules are linked into C(5) chains by a single C—H⋯N hydrogen bond.

Comment

The title compound, (I), was prepared for use as an intermediate in the synthesis of new fused heterocyclic systems.

The thiophene rings are disordered over two orientations corresponding to a 180° rotation about the C2—C22 bond (Fig. 1); the two conformers have unequal occupancy, with refined site-occupancy factors for the major and minor conformers of 0.802 (3) and 0.198 (3), respectively. The bond distances show no unexpected values; in particular, the C—N and C—C distances for the nitrile unit (Table 1) are typical, where the mean values (Allen et al., 1987 ) are 1.136 and 1.427 Å, respectively. The bond angles at C2 deviate significantly from regular trigonal geometry, while the C—C—N fragment is not quite linear. While both orientations of the thiophene unit are almost coplanar with the central C=C double bond, the 4-chlorophenyl ring is twisted well out of this plane. Thus, the dihedral angles between the plane of the central space unit C22—C2=C3—C31 and the planes of the adjacent rings are as follows: thiophene ring (major orientation) 5.7 (2)°, thiophene ring (minor orientation) 4.9 (5)° and aryl ring 38.2 (2)°.

The molecules are linked by a single C—H⋯N hydrogen bond (Table 2) into C(5) (Bernstein et al., 1995 ) chains generated by the n-glide planes and running parallel to the [10 $[\overline{1}]$ ] direction (Fig. 2). Two such chains, related to one another by inversion, pass through each unit cell, but there are no direction-specific interactions between adjacent chains: in particular π–π stacking interactions, and C—H⋯π(arene) and C—H⋯π(thiophene) hydrogen bonds are all absent.

Figure 1
The molecule of compound (I)

, showing the atom-labelling scheme for (a) the major conformer and (b) the minor conformer. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
Part of the crystal structure of compound (I)

, showing the formation of a C(5) chain along [10 $[\overline{1}]$ ] generated by the n-glide plane at y = 0.25. For the sake of clarity, H atoms not involved in the motif shown have been omitted, and only the major conformer is shown. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ( $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z) and (− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z), respectively.

Experimental

A solution of 2-thiopheneacetonitrile (2.87 mmol) and potassium tert-butoxide (0.53 mmol) in anhydrous ethanol (3 ml) was stirred at room temperature for 15 min; a solution of 4-chlorobenzaldehyde (2.87 mmol) in anhydrous ethanol (3 ml) was then added. The resulting precipitate was collected by filtration, washed with ethanol, dried and finally crystallized from dimethylformamide to give yellow crystals suitable for single-crystal X-ray diffraction.

Crystal data

C₁₃H₈ClNS
M_r = 245.72
Monoclinic, P 2₁ /n
a = 3.8142 (2) Å
b = 23.6852 (8) Å
c = 12.5319 (5) Å
β = 97.2160 (16)°
V = 1123.17 (8) Å³
Z = 4
D_x = 1.453 Mg m⁻³
Mo Kα radiation
Cell parameters from 2552 reflections
θ = 3.4–27.5°
μ = 0.49 mm⁻¹
T = 120 (2) K
Block, yellow
0.30 × 0.20 × 0.12 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.866, T_max = 0.943
11691 measured reflections
2552 independent reflections
2132 reflections with I > 2σ(I)
R_int = 0.033
θ_max = 27.5°
h = −4 → 4
k = −30 → 25
l = −16 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.094
S = 1.06
2552 reflections
145 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0351P)² + 0.9116P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.55 e Å⁻³
Δρ_min = −1.02 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—N1	1.147 (3)
C1—C2	1.448 (3)
C2—C3	1.346 (3)

N1—C1—C2	176.2 (2)
C1—C2—C3	120.69 (17)
C1—C2—C22	114.88 (15)
C3—C2—C22	124.33 (15)

C3—C2—C22—S21	4.2 (3)
C3—C2—C22—S21A	−177.4 (2)
C2—C3—C31—C32	37.9 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N1ⁱ	0.95	2.53	3.438 (2)	161
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C). It was apparent at an early stage that the thiophene unit was disordered over two sets of sites related by a rotation of 180° about the exocyclic C—C bond; the geometry of the minor orientation was restrained to match that of the major orientation, and the anisotropic displacement parameters for corresponding atoms in the two orientations were constrained to be equal. The deepest hole in the difference map is located 0.33 Å from the minor-occupancy atom S21A.

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/S1600536805031752/lh6521sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805031752/lh6521Isup2.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).

(E)-3-(4-Chlorophenyl)-2-(2-thienyl)acrylonitrile top

Crystal data top

C₁₃H₈ClNS	F(000) = 504
M_r = 245.72	D_x = 1.453 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2552 reflections
a = 3.8142 (2) Å	θ = 3.4–27.5°
b = 23.6852 (8) Å	µ = 0.49 mm⁻¹
c = 12.5319 (5) Å	T = 120 K
β = 97.2160 (16)°	Needle, yellow
V = 1123.17 (8) Å³	0.30 × 0.20 × 0.12 mm
Z = 4

Data collection top

Bruker–Nonius 95mm CCD camera on κ goniostat diffractometer	2552 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	2132 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
φ and ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −30→25
T_min = 0.866, T_max = 0.943	l = −16→16
11691 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0351P)² + 0.9116P] where P = (F_o² + 2F_c²)/3
2552 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.55 e Å⁻³
10 restraints	Δρ_min = −1.02 e Å⁻³

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl34	0.34216 (14)	0.50512 (2)	0.68406 (4)	0.02927 (16)
S21	0.7644 (2)	0.14768 (3)	0.45758 (5)	0.0204 (2)	0.802 (3)
S21A	0.5909 (9)	0.10747 (8)	0.66549 (18)	0.0204 (2)	0.198 (3)
N1	0.3752 (5)	0.22435 (8)	0.80736 (14)	0.0314 (4)
C1	0.4690 (5)	0.22378 (8)	0.72392 (15)	0.0219 (4)
C2	0.5721 (5)	0.21992 (8)	0.61686 (14)	0.0187 (4)
C3	0.5864 (5)	0.26641 (8)	0.55581 (15)	0.0209 (4)
C22	0.6355 (5)	0.16265 (6)	0.58077 (9)	0.0197 (4)
C23	0.5928 (8)	0.11359 (6)	0.63458 (17)	0.0224 (4)	0.802 (3)
C24	0.6664 (9)	0.06308 (5)	0.57986 (16)	0.0224 (4)	0.802 (3)
C25	0.7582 (9)	0.07648 (5)	0.48227 (16)	0.0224 (4)	0.802 (3)
C23A	0.748 (5)	0.1471 (4)	0.4861 (7)	0.0224 (4)	0.198 (3)
C24A	0.773 (4)	0.0881 (4)	0.4667 (8)	0.0224 (4)	0.198 (3)
C25A	0.683 (4)	0.0664 (4)	0.5601 (7)	0.0224 (4)	0.198 (3)
C31	0.5370 (5)	0.32511 (8)	0.58827 (15)	0.0197 (4)
C32	0.6649 (5)	0.34480 (8)	0.69114 (15)	0.0206 (4)
C33	0.6102 (5)	0.40037 (8)	0.71952 (15)	0.0214 (4)
C35	0.3042 (5)	0.41834 (9)	0.54241 (16)	0.0242 (4)
C34	0.4250 (5)	0.43614 (8)	0.64543 (16)	0.0214 (4)
C36	0.3651 (5)	0.36295 (9)	0.51405 (16)	0.0240 (4)
H3	0.6335	0.2606	0.4840	0.025*
H23	0.5187	0.1131	0.7042	0.027*	0.802 (3)
H24	0.6530	0.0259	0.6075	0.027*	0.802 (3)
H25	0.8142	0.0490	0.4319	0.027*	0.802 (3)
H23A	0.8073	0.1743	0.4356	0.027*	0.198 (3)
H24A	0.8360	0.0691	0.4051	0.027*	0.198 (3)
H25A	0.6705	0.0265	0.5671	0.027*	0.198 (3)
H32	0.7899	0.3199	0.7418	0.025*
H33	0.6990	0.4138	0.7892	0.026*
H35	0.1815	0.4436	0.4919	0.029*
H36	0.2885	0.3506	0.4428	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl34	0.0301 (3)	0.0250 (3)	0.0326 (3)	0.0034 (2)	0.0032 (2)	−0.0020 (2)
S21	0.0216 (3)	0.0241 (3)	0.0164 (4)	0.0006 (2)	0.0054 (3)	−0.0021 (3)
S21A	0.0216 (3)	0.0241 (3)	0.0164 (4)	0.0006 (2)	0.0054 (3)	−0.0021 (3)
N1	0.0406 (11)	0.0332 (10)	0.0224 (9)	0.0029 (8)	0.0122 (8)	0.0017 (8)
C1	0.0225 (10)	0.0228 (10)	0.0208 (10)	0.0023 (8)	0.0045 (8)	0.0016 (8)
C2	0.0154 (9)	0.0268 (10)	0.0140 (8)	0.0014 (7)	0.0021 (7)	−0.0008 (7)
C3	0.0192 (9)	0.0284 (10)	0.0153 (9)	−0.0007 (8)	0.0037 (7)	−0.0017 (8)
C22	0.0147 (9)	0.0274 (10)	0.0165 (9)	0.0015 (7)	0.0004 (7)	−0.0010 (8)
C23	0.0249 (7)	0.0234 (7)	0.0188 (8)	−0.0008 (6)	0.0026 (7)	0.0052 (6)
C24	0.0249 (7)	0.0234 (7)	0.0188 (8)	−0.0008 (6)	0.0026 (7)	0.0052 (6)
C25	0.0249 (7)	0.0234 (7)	0.0188 (8)	−0.0008 (6)	0.0026 (7)	0.0052 (6)
C23A	0.0249 (7)	0.0234 (7)	0.0188 (8)	−0.0008 (6)	0.0026 (7)	0.0052 (6)
C24A	0.0249 (7)	0.0234 (7)	0.0188 (8)	−0.0008 (6)	0.0026 (7)	0.0052 (6)
C25A	0.0249 (7)	0.0234 (7)	0.0188 (8)	−0.0008 (6)	0.0026 (7)	0.0052 (6)
C31	0.0174 (9)	0.0253 (10)	0.0174 (9)	−0.0009 (7)	0.0057 (7)	−0.0001 (8)
C32	0.0187 (9)	0.0254 (10)	0.0181 (9)	0.0008 (8)	0.0038 (7)	0.0044 (8)
C33	0.0187 (9)	0.0284 (10)	0.0175 (9)	−0.0018 (8)	0.0039 (7)	−0.0011 (8)
C35	0.0229 (10)	0.0275 (11)	0.0218 (9)	0.0011 (8)	0.0009 (8)	0.0054 (8)
C34	0.0178 (9)	0.0224 (10)	0.0248 (10)	0.0001 (7)	0.0062 (8)	0.0004 (8)
C36	0.0256 (10)	0.0296 (11)	0.0166 (9)	−0.0018 (8)	0.0018 (8)	0.0008 (8)

Geometric parameters (Å, º) top

C1—N1	1.147 (3)	C24A—C25A	1.3622 (11)
C1—C2	1.448 (3)	C24A—H24A	0.95
C2—C3	1.346 (3)	C25A—H25A	0.95
C2—C22	1.460 (2)	C3—C31	1.467 (3)
C22—C23A	1.3620 (11)	C3—H3	0.95
C22—C23	1.3635 (10)	C31—C36	1.395 (3)
C22—S21A	1.7058 (10)	C31—C32	1.400 (3)
C22—S21	1.7151 (9)	C32—C33	1.386 (3)
S21—C25	1.7153	C32—H32	0.95
C23—C24	1.4244 (10)	C33—C34	1.383 (3)
C23—H23	0.95	C33—H33	0.95
C24—C25	1.3516	C35—C34	1.381 (3)
C24—H24	0.95	C35—C36	1.386 (3)
C25—H25	0.95	C35—H35	0.95
S21A—C25A	1.7125 (11)	C34—Cl34	1.744 (2)
C23A—C24A	1.4240 (11)	C36—H36	0.95
C23A—H23A	0.95

N1—C1—C2	176.2 (2)	C25A—C24A—H24A	129.4
C1—C2—C3	120.69 (17)	C23A—C24A—H24A	129.4
C1—C2—C22	114.88 (15)	C24A—C25A—S21A	123.1 (8)
C3—C2—C22	124.33 (15)	C24A—C25A—H25A	118.5
C23A—C22—C23	105.7 (5)	S21A—C25A—H25A	118.5
C23A—C22—C2	127.1 (5)	C2—C3—C31	127.00 (17)
C23—C22—C2	127.15 (12)	C2—C3—H3	116.5
C23A—C22—S21A	113.7 (5)	C31—C3—H3	116.5
C2—C22—S21A	119.07 (12)	C36—C31—C32	118.72 (18)
C23—C22—S21	109.55 (13)	C36—C31—C3	119.34 (17)
C2—C22—S21	123.26 (11)	C32—C31—C3	121.92 (17)
S21A—C22—S21	117.65 (12)	C33—C32—C31	120.42 (18)
C22—S21—C25	91.65 (8)	C33—C32—H32	119.8
C22—C23—C24	115.77 (15)	C31—C32—H32	119.8
C22—C23—H23	122.1	C34—C33—C32	119.33 (18)
C24—C23—H23	122.1	C34—C33—H33	120.3
C25—C24—C23	109.12 (9)	C32—C33—H33	120.3
C25—C24—H24	125.4	C34—C35—C36	118.79 (18)
C23—C24—H24	125.4	C34—C35—H35	120.6
C24—C25—S21	113.90 (6)	C36—C35—H35	120.6
C24—C25—H25	123.0	C35—C34—C33	121.51 (18)
S21—C25—H25	123.0	C35—C34—Cl34	119.64 (15)
C22—S21A—C25A	84.8 (4)	C33—C34—Cl34	118.84 (15)
C22—C23A—C24A	116.7 (8)	C35—C36—C31	121.13 (18)
C22—C23A—H23A	121.7	C35—C36—H36	119.4
C24A—C23A—H23A	121.7	C31—C36—H36	119.4
C25A—C24A—C23A	101.2 (9)

C3—C2—C22—C23A	6.4 (10)	S21—C22—S21A—C25A	−4.4 (7)
C1—C2—C22—C23A	−177.1 (10)	C23—C22—C23A—C24A	2.9 (17)
C3—C2—C22—C23	−173.3 (2)	C2—C22—C23A—C24A	−176.8 (11)
C1—C2—C22—C23	3.2 (3)	S21A—C22—C23A—C24A	6.8 (19)
C1—C2—C22—S21A	−1.0 (3)	S21—C22—C23A—C24A	−151 (11)
C3—C2—C22—S21	4.2 (3)	C22—C23A—C24A—C25A	−2.9 (17)
C3—C2—C22—S21A	−177.4 (2)	C23A—C24A—C25A—S21A	−2.3 (13)
C1—C2—C22—S21	−179.31 (14)	C22—S21A—C25A—C24A	5.1 (9)
C23A—C22—S21—C25	26 (10)	C1—C2—C3—C31	5.9 (3)
C23—C22—S21—C25	−0.2 (2)	C22—C2—C3—C31	−177.85 (18)
C2—C22—S21—C25	−178.08 (19)	C2—C3—C31—C36	−143.7 (2)
S21A—C22—S21—C25	3.55 (17)	C2—C3—C31—C32	37.9 (3)
C23A—C22—C23—C24	−1.1 (8)	C36—C31—C32—C33	2.2 (3)
C2—C22—C23—C24	178.7 (2)	C3—C31—C32—C33	−179.30 (17)
S21A—C22—C23—C24	−157.0 (16)	C31—C32—C33—C34	0.6 (3)
S21—C22—C23—C24	0.9 (4)	C36—C35—C34—C33	1.3 (3)
C22—C23—C24—C25	−1.3 (3)	C36—C35—C34—Cl34	−178.44 (15)
C23—C24—C25—S21	1.13 (13)	C32—C33—C34—C35	−2.4 (3)
C22—S21—C25—C24	−0.59 (9)	C32—C33—C34—Cl34	177.34 (14)
C23A—C22—S21A—C25A	−6.2 (12)	C34—C35—C36—C31	1.6 (3)
C23—C22—S21A—C25A	19.2 (12)	C32—C31—C36—C35	−3.4 (3)
C2—C22—S21A—C25A	177.2 (6)	C3—C31—C36—C35	178.13 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.95	2.53	3.438 (2)	161

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Acknowledgements

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

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