Crystal structure of 2-(4-chloro­phen­yl)-3-(4-meth­oxy­phen­yl)-3-(methyl­sulfanyl)­acrylo­nitrile

Kumar, S.; Hosamani, A.A.; Vinayaka, A.C.; Sadashiva, M.P.; Doreswamy, B.H.

doi:10.1107/S1600536814021576

organic compounds

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Crystal structure of 2-(4-chlorophenyl)-3-(4-methoxyphenyl)-3-(methylsulfanyl)acrylonitrile

Shamantha Kumar,^a Amar A. Hosamani,^b A. C. Vinayaka,^c M. P. Sadashiva ^c and B. H. Doreswamy ^a ^*

^aDepartment of Physics, SJB Institute of Technology, Kengeri, Bangalore 560 060, India, ^bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India, and ^cDepartment of Studies in Chemistry, Manasagangotri, University of Mysore, Mysore 570 006, India
^*Correspondence e-mail: dorephy@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 12 September 2014; accepted 30 September 2014; online 11 October 2014)

In the title compound, C₁₇H₁₄ClNOS, the aromatic rings are inclined to one another by 64.22 (9)°. The acrylonitrile group (C=C—C≡N) is planar to within 0.003 (2) Å, with the S atom and the methyl C atom displaced from this plane by 0.2317 (6) and −0.637 (2) Å, respectively. In the crystal, molecules are linked via pairs of C—H⋯π interactions, forming inversion dimers. There are no other significant intermolecular interactions present.

Keywords: crystal structure; acrylonitrile; C—H⋯π interactions; biological activity; pharmacological activity.

CCDC reference: 1026843

1. Related literature

For the biological and pharmacological activities of acrylonitrile derivatives, see: Boëdec et al. (2008 ); Napolitano et al. (2001 ); Saczewski et al. (2004 ); Sommen et al. (2003 ). For related literature, see: Saufi & Ismail (2002 ); Urska et al. (2003 ).

2. Experimental

2.1. Crystal data

C₁₇H₁₄ClNOS
M_r = 315.81
Monoclinic, P 2₁ /c
a = 8.3060 (4) Å
b = 10.5048 (6) Å
c = 17.9795 (9) Å
β = 100.598 (5)°
V = 1542.00 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

2.2. Data collection

Bruker APEXII CCD area-detector diffractometer
6889 measured reflections
3537 independent reflections
2807 reflections with I > 2σ(I)
R_int = 0.028

2.3. Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.114
S = 1.04
3537 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯Cg1ⁱ	0.93	2.96	3.739 (2)	142
Symmetry code: (i) -x+1, -y+2, -z.

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

Supporting information

CCDC reference: 1026843

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814021576/su2787sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814021576/su2787Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814021576/su2787Isup3.cml

checkCIF report

Related literature top

For the biological and pharmacological activities of acrylonitrile derivatives, see: Boëdec et al. (2008); Napolitano et al. (2001); Saczewski et al. (2004); Sommen et al. (2003). For related literature [on what subjects?], see: Saufi & Ismail (2002); Urska et al. (2003).

Experimental top

To a stirred suspension of NaH (0.45 g, 11.0 mmol, 60% suspension in oil) in dry THF (25 ml), a solution of (4-chloro-phenyl)-acetonitrile (0.75 g, 5.0 mmol) and 4-methoxy-dithiobenzoic acid methyl ester (0.99 g, 5.0 mmol) in dry THF (50 ml) was added drop wise at 273 K under a nitrogen atmosphere. The reaction mixture was stirred at room temperature for 4 h. It was again cooled to 273 K and methyl iodide (1.42 g, 10 mmol) was added drop wise. The reaction mixture was further stirred at room temperature for 4 h and poured into ice cold water (25 ml). The aqueous layer was extracted with CH₂Cl₂ (3 × 10 ml). The combined organic extracts were washed with water (1 × 20 ml), brine (1 × 20 ml), and dried over anhydrous Na₂SO₄. The solvent was evaporated under reduced pressure to give a crude product which was purified by silica gel column using EtOAc:hexane as eluent. Colourless block-like crystals were grown by dissolving the product in absolute ethanol followed by slow evaporation at room temperature.

Structure description top

For the biological and pharmacological activities of acrylonitrile derivatives, see: Boëdec et al. (2008); Napolitano et al. (2001); Saczewski et al. (2004); Sommen et al. (2003). For related literature [on what subjects?], see: Saufi & Ismail (2002); Urska et al. (2003).

Computing details top

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

Figures top

	Fig. 1. A view of the molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view along the b axis of the crystal packing of the title compound.

2-(4-Chlorophenyl)-3-(4-methoxyphenyl)-3-(methylsulfanyl)acrylonitrile top

Crystal data top

C₁₇H₁₄ClNOS	F(000) = 656
M_r = 315.81	D_x = 1.360 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3537 reflections
a = 8.3060 (4) Å	θ = 2.5–27.5°
b = 10.5048 (6) Å	µ = 0.38 mm⁻¹
c = 17.9795 (9) Å	T = 293 K
β = 100.598 (5)°	Block, colourless
V = 1542.00 (14) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	R_int = 0.028
ω and φ scans	θ_max = 27.5°, θ_min = 2.5°
6889 measured reflections	h = −10→6
3537 independent reflections	k = −13→5
2807 reflections with I > 2σ(I)	l = −23→23

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.045P)² + 0.3209P] where P = (F_o² + 2F_c²)/3
3537 reflections	(Δ/σ)_max < 0.001
192 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₇H₁₄ClNOS	V = 1542.00 (14) Å³
M_r = 315.81	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3060 (4) Å	µ = 0.38 mm⁻¹
b = 10.5048 (6) Å	T = 293 K
c = 17.9795 (9) Å	0.30 × 0.25 × 0.20 mm
β = 100.598 (5)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2807 reflections with I > 2σ(I)
6889 measured reflections	R_int = 0.028
3537 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.04	Δρ_max = 0.26 e Å⁻³
3537 reflections	Δρ_min = −0.26 e Å⁻³
192 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
Cl7	−0.19319 (7)	1.21573 (7)	−0.19619 (4)	0.0708 (2)
S12	0.39592 (6)	0.84311 (6)	0.00222 (3)	0.0463 (2)
O20	1.09261 (17)	0.59095 (16)	−0.06455 (9)	0.0603 (6)
N10	0.5710 (2)	0.9039 (2)	−0.25595 (10)	0.0575 (7)
C1	0.2687 (2)	1.09961 (19)	−0.18246 (10)	0.0396 (6)
C2	0.1284 (2)	1.1742 (2)	−0.19521 (11)	0.0463 (6)
C3	−0.0153 (2)	1.1236 (2)	−0.18024 (11)	0.0441 (6)
C4	−0.0223 (2)	1.0011 (2)	−0.15428 (12)	0.0496 (7)
C5	0.1178 (2)	0.9272 (2)	−0.14196 (11)	0.0452 (6)
C6	0.2658 (2)	0.97624 (18)	−0.15536 (9)	0.0347 (5)
C8	0.4179 (2)	0.89756 (18)	−0.14288 (10)	0.0346 (5)
C9	0.5065 (2)	0.8996 (2)	−0.20479 (10)	0.0401 (6)
C11	0.4820 (2)	0.83108 (18)	−0.07963 (10)	0.0353 (5)
C13	0.4464 (3)	0.6919 (2)	0.04764 (12)	0.0570 (8)
C14	0.6374 (2)	0.75884 (19)	−0.07423 (10)	0.0350 (5)
C15	0.7767 (2)	0.7996 (2)	−0.02329 (10)	0.0402 (6)
C16	0.9244 (2)	0.7402 (2)	−0.02164 (11)	0.0443 (6)
C17	0.9379 (2)	0.6388 (2)	−0.06941 (11)	0.0406 (6)
C18	0.8005 (2)	0.5942 (2)	−0.11771 (11)	0.0441 (6)
C19	0.6513 (2)	0.6553 (2)	−0.11980 (11)	0.0429 (6)
C21	1.1194 (3)	0.4982 (3)	−0.11813 (15)	0.0742 (10)
H1	0.36640	1.13300	−0.19230	0.0470*
H2	0.13140	1.25680	−0.21350	0.0550*
H4	−0.12060	0.96800	−0.14510	0.0600*
H5	0.11330	0.84410	−0.12460	0.0540*
H13A	0.40050	0.62460	0.01420	0.0860*
H13B	0.40220	0.68780	0.09330	0.0860*
H13C	0.56320	0.68250	0.05960	0.0860*
H15	0.76880	0.86710	0.00940	0.0480*
H16	1.01650	0.76820	0.01190	0.0530*
H18	0.80790	0.52400	−0.14840	0.0530*
H19	0.55900	0.62580	−0.15260	0.0520*
H21A	1.06080	0.42180	−0.11070	0.1110*
H21B	1.23430	0.47980	−0.11170	0.1110*
H21C	1.08110	0.53000	−0.16830	0.1110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl7	0.0571 (3)	0.0760 (5)	0.0789 (4)	0.0308 (3)	0.0114 (3)	0.0093 (4)
S12	0.0507 (3)	0.0523 (3)	0.0385 (3)	0.0136 (2)	0.0150 (2)	0.0035 (2)
O20	0.0451 (8)	0.0666 (11)	0.0699 (10)	0.0192 (7)	0.0125 (7)	−0.0035 (9)
N10	0.0579 (11)	0.0707 (14)	0.0479 (10)	0.0082 (10)	0.0199 (8)	0.0068 (10)
C1	0.0436 (10)	0.0401 (11)	0.0362 (9)	−0.0011 (8)	0.0104 (8)	0.0014 (9)
C2	0.0594 (12)	0.0383 (11)	0.0421 (10)	0.0073 (9)	0.0120 (9)	0.0045 (9)
C3	0.0447 (10)	0.0491 (12)	0.0376 (10)	0.0149 (9)	0.0049 (8)	−0.0006 (9)
C4	0.0348 (9)	0.0585 (14)	0.0548 (12)	0.0010 (9)	0.0065 (8)	0.0081 (11)
C5	0.0393 (10)	0.0412 (12)	0.0532 (11)	−0.0006 (8)	0.0033 (8)	0.0103 (10)
C6	0.0369 (9)	0.0369 (10)	0.0293 (8)	0.0019 (8)	0.0033 (7)	−0.0004 (8)
C8	0.0344 (9)	0.0353 (10)	0.0336 (9)	−0.0007 (7)	0.0051 (7)	−0.0027 (8)
C9	0.0374 (9)	0.0437 (12)	0.0377 (10)	0.0035 (8)	0.0033 (8)	0.0013 (9)
C11	0.0360 (9)	0.0346 (10)	0.0351 (9)	−0.0002 (7)	0.0064 (7)	−0.0039 (8)
C13	0.0608 (13)	0.0651 (16)	0.0479 (12)	0.0059 (11)	0.0171 (10)	0.0161 (11)
C14	0.0368 (9)	0.0365 (10)	0.0321 (8)	0.0022 (7)	0.0078 (7)	0.0015 (8)
C15	0.0423 (10)	0.0408 (11)	0.0370 (9)	−0.0008 (8)	0.0063 (8)	−0.0078 (9)
C16	0.0358 (9)	0.0521 (13)	0.0437 (10)	−0.0014 (9)	0.0036 (8)	−0.0044 (10)
C17	0.0405 (10)	0.0420 (12)	0.0409 (10)	0.0071 (8)	0.0118 (8)	0.0077 (9)
C18	0.0552 (11)	0.0366 (11)	0.0405 (10)	0.0078 (9)	0.0091 (9)	−0.0052 (9)
C19	0.0434 (10)	0.0434 (12)	0.0396 (10)	0.0022 (9)	0.0013 (8)	−0.0049 (9)
C21	0.0776 (17)	0.0797 (19)	0.0691 (15)	0.0403 (15)	0.0239 (13)	0.0036 (15)

Geometric parameters (Å, º) top

Cl7—C3	1.745 (2)	C15—C16	1.372 (3)
S12—C11	1.7550 (18)	C16—C17	1.386 (3)
S12—C13	1.800 (2)	C17—C18	1.383 (3)
O20—C17	1.368 (2)	C18—C19	1.390 (3)
O20—C21	1.416 (3)	C1—H1	0.9300
N10—C9	1.147 (2)	C2—H2	0.9300
C1—C2	1.388 (3)	C4—H4	0.9300
C1—C6	1.386 (3)	C5—H5	0.9300
C2—C3	1.378 (3)	C13—H13A	0.9600
C3—C4	1.374 (3)	C13—H13B	0.9600
C4—C5	1.382 (3)	C13—H13C	0.9600
C5—C6	1.394 (2)	C15—H15	0.9300
C6—C8	1.492 (2)	C16—H16	0.9300
C8—C9	1.443 (2)	C18—H18	0.9300
C8—C11	1.357 (3)	C19—H19	0.9300
C11—C14	1.485 (2)	C21—H21A	0.9600
C14—C15	1.404 (2)	C21—H21B	0.9600
C14—C19	1.379 (3)	C21—H21C	0.9600

C11—S12—C13	102.71 (10)	C2—C1—H1	119.00
C17—O20—C21	118.21 (17)	C6—C1—H1	119.00
C2—C1—C6	121.16 (16)	C1—C2—H2	121.00
C1—C2—C3	118.77 (19)	C3—C2—H2	121.00
Cl7—C3—C2	119.45 (16)	C3—C4—H4	120.00
Cl7—C3—C4	119.20 (14)	C5—C4—H4	120.00
C2—C3—C4	121.34 (17)	C4—C5—H5	120.00
C3—C4—C5	119.57 (17)	C6—C5—H5	120.00
C4—C5—C6	120.52 (19)	S12—C13—H13A	109.00
C1—C6—C5	118.62 (17)	S12—C13—H13B	109.00
C1—C6—C8	120.12 (15)	S12—C13—H13C	110.00
C5—C6—C8	121.24 (17)	H13A—C13—H13B	109.00
C6—C8—C9	114.44 (15)	H13A—C13—H13C	109.00
C6—C8—C11	127.02 (16)	H13B—C13—H13C	109.00
C9—C8—C11	118.48 (16)	C14—C15—H15	120.00
N10—C9—C8	176.9 (2)	C16—C15—H15	120.00
S12—C11—C8	120.54 (14)	C15—C16—H16	120.00
S12—C11—C14	117.73 (13)	C17—C16—H16	120.00
C8—C11—C14	121.34 (16)	C17—C18—H18	120.00
C11—C14—C15	119.27 (17)	C19—C18—H18	120.00
C11—C14—C19	122.06 (16)	C14—C19—H19	119.00
C15—C14—C19	118.62 (16)	C18—C19—H19	119.00
C14—C15—C16	120.12 (18)	O20—C21—H21A	109.00
C15—C16—C17	120.68 (17)	O20—C21—H21B	110.00
O20—C17—C16	115.16 (16)	O20—C21—H21C	109.00
O20—C17—C18	124.96 (18)	H21A—C21—H21B	109.00
C16—C17—C18	119.88 (17)	H21A—C21—H21C	109.00
C17—C18—C19	119.30 (19)	H21B—C21—H21C	109.00
C14—C19—C18	121.31 (17)

C13—S12—C11—C8	152.50 (16)	C9—C8—C11—S12	170.97 (14)
C13—S12—C11—C14	−34.67 (17)	C9—C8—C11—C14	−1.6 (3)
C21—O20—C17—C18	7.3 (3)	C6—C8—C11—S12	−5.9 (3)
C21—O20—C17—C16	−172.2 (2)	C6—C8—C11—C14	−178.51 (17)
C2—C1—C6—C8	179.37 (17)	S12—C11—C14—C15	−60.3 (2)
C2—C1—C6—C5	0.9 (3)	C8—C11—C14—C19	−65.1 (3)
C6—C1—C2—C3	0.2 (3)	S12—C11—C14—C19	122.17 (18)
C1—C2—C3—Cl7	−179.80 (15)	C8—C11—C14—C15	112.5 (2)
C1—C2—C3—C4	−1.0 (3)	C11—C14—C19—C18	175.46 (18)
C2—C3—C4—C5	0.8 (3)	C15—C14—C19—C18	−2.1 (3)
Cl7—C3—C4—C5	179.59 (16)	C11—C14—C15—C16	−174.94 (18)
C3—C4—C5—C6	0.3 (3)	C19—C14—C15—C16	2.7 (3)
C4—C5—C6—C8	−179.57 (18)	C14—C15—C16—C17	−0.7 (3)
C4—C5—C6—C1	−1.1 (3)	C15—C16—C17—C18	−2.0 (3)
C1—C6—C8—C9	−47.0 (2)	C15—C16—C17—O20	177.50 (18)
C5—C6—C8—C11	−51.5 (3)	O20—C17—C18—C19	−176.86 (19)
C1—C6—C8—C11	130.0 (2)	C16—C17—C18—C19	2.6 (3)
C5—C6—C8—C9	131.45 (18)	C17—C18—C19—C14	−0.5 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···Cg1ⁱ	0.93	2.96	3.739 (2)	142

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···Cg1ⁱ	0.93	2.96	3.739 (2)	142

Symmetry code: (i) −x+1, −y+2, −z.

Acknowledgements

The authors are grateful to the SJB Institute of Technology, Kengeri, Bangalore, for their support.

References

Boëdec, A., Sicard, H., Dessolin, J., Herbette, G., Ingoure, S., Raymond, C., Belmant, C. & Kraus, J. L. (2008). J. Med. Chem. 51, 1747–1754. Web of Science PubMed Google Scholar
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Crystal structure of 2-(4-chloro­phen­yl)-3-(4-meth­­oxy­phen­yl)-3-(methyl­sulfanyl)­acrylo­nitrile

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of 2-(4-chlorophenyl)-3-(4-methoxyphenyl)-3-(methylsulfanyl)acrylonitrile