Crystal structure of methyl (2Z)-3-(4-chloro-phen-yl)-2-[(3-methyl-1H-indol-1-yl)meth-yl]prop-2-enoate.

In the title indole derivative, C20H18ClNO2, the chloro-phenyl ring is almost perpendicular to the indole moiety, making a dihedral angle of 87.6 (1)°. The mol-ecular packing is stabilized by C-H⋯π inter-actions, which form a C(9) chain motif along [10-1]. In addition, there are weak π-π inter-actions [centroid-centroid distance 3.851 (1) Å] between the chains, involving inversion-related chloro-phenyl rings.

Chemical context

Indole derivatives inhibit hepatitis C virus replication through induction of pro-inflammatory cytokines (Lee et al., 2015 ▸) and these derivatives act as a new anti-hepatitis C virus agents (Andreev et al., 2015 ▸). These derivatives also act as potential mushroom tyrosinase inhibitors (Ferro et al., 2015 ▸). Indole derivatives also exhibit anti-proliferative (Parrino et al., 2015 ▸), anti-inflammatory (Chen et al., 2015 ▸) and anti-tumor (Ma et al., 2015 ▸) activities. In view of the many inter­esting applications of indole derivatives, we synthesized the title compound and report herein on its crystal structure.

Structural commentary

The mol­ecular structure of the title compound, (I), is illus­trated in Fig. 1 ▸. The geometry of the indole ring system (N1/C1–C8) in (I) is comparable with those reported for similar structures, namely 1-vinyl-1H-indole-3-carbaldehyde (II) (Selvanayagam et al., 2008 ▸) and methyl (2Z)-2-[(2-formyl-3-methyl-1H-indol-1-yl)meth­yl]-3-(4-meth­oxy­phen­yl)-prop-2-en­oate (III) (Selvanayagam et al., 2014 ▸). The superposition of the indole ring system of (I) with the related reported structures, using Qmol (Gans & Shalloway, 2001 ▸), gives an r.m.s. deviation of 0.025 Å between (I) and (II), and 0.030 Å between (I) and (III); see Fig. 2 ▸. The indole ring system is planar with an r.m.s. deviation of 0.017 Å [maximum deviation of 0.028 (2) Å for atom C3], and the methyl atom C9 deviates by 0.050 (2) Å from its mean plane. The chlorine atom, Cl1, deviates by 0.008 (1) Å from the benzene ring (C15–C20) to which it is attached. This ring is almost perpendicular to the indole ring system, making a dihedral angle of 87.59 (6)°. The sum of the angles at atom N1 of the indole ring (360°) is in accordance with sp 2 hybridization. The widening of the C16—C15—C14 bond angle to 125.2 (1)° is due to the short H⋯H contact (H10B⋯H16 = 2.10 Å). The mean plane of the methyl methacrylate unit [O1/O2/C10–C14; maximum deviation of 0.015 (2) Å for atom O1] is almost planar with the chlrophenyl ring, making a dihedral angle of 18.98 (17)°, but is normal to the indole ring system with a dihedral angle of 89.96 (5)°.

Figure 1

The mol­ecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2

Superposition of (I) (cyan) with the similar reported structures (II) (yellow; Selvanayagam et al., 2008 ▸) and (III) (green; Selvanayagam et al., 2014 ▸).

Supra­molecular features

In the crystal, C—H⋯π inter­actions link the mol­ecules, forming C(9) chains propagating along [10]; see Fig. 3 ▸ and Table 1 ▸. Between the chains there are weak π–π inter­actions involving inversion-related chloro­phenyl rings (C15–C20), stabilizing the mol­ecular packing [centroid-to-centroid distance = 3.851 (1) Å]; see Fig. 4 ▸.

Figure 3

The mol­ecular packing of the title compound, viewed along the b axis. C—H⋯π inter­actions (Table 1 ▸) are shown as dashed lines. For clarity, H atoms not involved in these inter­actions have been omitted.

Table 1

Hydrogen-bond geometry (, )

Cg is the centroid of ring C1C6.

DHA	DH	HA	D A	DHA
C13H13A Cg i	0.96	2.69	3.581(2)	154

Symmetry code: (i) .

Figure 4

Mol­ecular packing of the title compound, showing the π–π inter­actions as dashed lines. For clarity, H atoms not involved in these inter­actions have been omitted.

Synthesis and crystallization

Substituted (Z)-methyl-2-(bromo­meth­yl)-3-phenyl­acrylate (1 mmol), tetra-butyl-ammonium bromide (0.5 mmol), and 50% NaOH (20 ml) were added to a solution of 3-methyl indole (1 mmol) in benzene (55 ml). The mixture was stirred vigorously at room temperature for 5–6 h. The organic layer was separated, washed with water and dried over MgSO4. The solvent was evaporated under reduced pressure (yield: 70%). Suitable crystals were obtained by slow evaporation of a solution of the title compound in methanol at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms were placed in idealized positions and allowed to ride on their parent atoms: C—H = 0.93–0.97 Å, with U iso(H) = 1.5U eq(C) for methyl H atoms and 1.2U eq(C) for other H atoms.

Table 2

Experimental details

Crystal data
Chemical formula	C20H18ClNO2
M r	339.80
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	292
a, b, c ()	9.5867(5), 15.9077(8), 10.8902(6)
()	94.787(1)
V (3)	1654.99(15)
Z	4
Radiation type	Mo K
(mm1)	0.24
Crystal size (mm)	0.20 0.18 0.16
Data collection
Diffractometer	Bruker SMART APEX CCD area detector
No. of measured, independent and observed [I > 2(I)] reflections	19078, 3944, 3313
R int	0.026
(sin /)max (1)	0.661
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.044, 0.127, 1.02
No. of reflections	3944
No. of parameters	219
H-atom treatment	H-atom parameters constrained
max, min (e 3)	0.30, 0.23

Computer programs: SMART and SAINT (Bruker, 2001 ▸), SHELXS1997 (Sheldrick, 2008 ▸), SHELXL2013 (Sheldrick, 2015 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015010002/su5135sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010002/su5135Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015010002/su5135Isup3.cml

CCDC reference: 1402521

Additional supporting information: crystallographic information; 3D view; checkCIF report

C20H18ClNO2	F(000) = 712
Mr = 339.80	Dx = 1.364 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.5867 (5) Å	Cell parameters from 12437 reflections
b = 15.9077 (8) Å	θ = 2.3–27.7°
c = 10.8902 (6) Å	µ = 0.24 mm−1
β = 94.787 (1)°	T = 292 K
V = 1654.99 (15) Å3	Block, colourless
Z = 4	0.20 × 0.18 × 0.16 mm

Bruker SMART APEX CCD area-detector diffractometer	Rint = 0.026
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 2.3°
ω scans	h = −12→12
19078 measured reflections	k = −20→20
3944 independent reflections	l = −14→14
3313 reflections with I > 2σ(I)

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H-atom parameters constrained
wR(F2) = 0.127	w = 1/[σ2(Fo2) + (0.0722P)2 + 0.3404P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.002
3944 reflections	Δρmax = 0.30 e Å−3
219 parameters	Δρmin = −0.23 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	0.85221 (5)	1.06092 (3)	0.06559 (4)	0.05976 (16)
O1	0.23237 (16)	0.66473 (11)	−0.05769 (11)	0.0775 (4)
O2	0.21544 (12)	0.62293 (7)	0.13579 (10)	0.0524 (3)
N1	0.32743 (12)	0.78373 (7)	0.30864 (10)	0.0366 (3)
C1	0.32983 (13)	0.78740 (8)	0.43477 (12)	0.0333 (3)
C2	0.40942 (15)	0.74169 (9)	0.52459 (13)	0.0405 (3)
H2	0.4756	0.7027	0.5035	0.049*
C3	0.38621 (16)	0.75652 (10)	0.64588 (13)	0.0472 (4)
H3	0.4365	0.7262	0.7077	0.057*
C4	0.28848 (17)	0.81630 (11)	0.67783 (13)	0.0487 (4)
H4	0.2759	0.8254	0.7605	0.058*
C5	0.21077 (15)	0.86187 (9)	0.58952 (13)	0.0421 (3)
H5	0.1468	0.9018	0.6120	0.051*
C6	0.22927 (13)	0.84726 (8)	0.46513 (12)	0.0341 (3)
C7	0.16518 (14)	0.87978 (9)	0.35139 (13)	0.0384 (3)
C8	0.22748 (14)	0.83989 (9)	0.25968 (13)	0.0390 (3)
H8	0.2059	0.8491	0.1759	0.047*
C9	0.05055 (18)	0.94375 (11)	0.33648 (17)	0.0551 (4)
H9A	0.0297	0.9559	0.2506	0.083*
H9B	0.0800	0.9943	0.3792	0.083*
H9C	−0.0316	0.9221	0.3701	0.083*
C10	0.41548 (15)	0.72823 (9)	0.24128 (12)	0.0391 (3)
H10A	0.4063	0.6711	0.2708	0.047*
H10B	0.5126	0.7449	0.2578	0.047*
C11	0.37749 (15)	0.73022 (9)	0.10415 (12)	0.0395 (3)
C12	0.26941 (16)	0.67031 (10)	0.05008 (14)	0.0457 (3)
C13	0.1091 (2)	0.56359 (11)	0.0915 (2)	0.0622 (5)
H13A	0.0294	0.5934	0.0543	0.093*
H13B	0.0815	0.5306	0.1592	0.093*
H13C	0.1457	0.5272	0.0316	0.093*
C14	0.43561 (15)	0.78067 (10)	0.02431 (13)	0.0427 (3)
H14	0.4052	0.7706	−0.0577	0.051*
C15	0.53784 (15)	0.84850 (9)	0.04181 (13)	0.0418 (3)
C16	0.57356 (18)	0.89031 (11)	0.15350 (14)	0.0499 (4)
H16	0.5315	0.8742	0.2238	0.060*
C17	0.66983 (18)	0.95481 (11)	0.16082 (15)	0.0516 (4)
H17	0.6930	0.9818	0.2355	0.062*
C18	0.73146 (16)	0.97890 (9)	0.05648 (14)	0.0447 (3)
C19	0.69899 (19)	0.93986 (11)	−0.05510 (15)	0.0521 (4)
H19	0.7414	0.9567	−0.1248	0.063*
C20	0.60262 (18)	0.87549 (11)	−0.06176 (14)	0.0495 (4)
H20	0.5800	0.8492	−0.1371	0.059*

	U11	U22	U33	U12	U13	U23
Cl1	0.0659 (3)	0.0532 (3)	0.0606 (3)	−0.00944 (19)	0.0072 (2)	0.00371 (18)
O1	0.0809 (9)	0.1119 (12)	0.0386 (7)	−0.0357 (9)	−0.0008 (6)	−0.0147 (7)
O2	0.0572 (7)	0.0500 (6)	0.0490 (6)	−0.0075 (5)	−0.0016 (5)	−0.0016 (5)
N1	0.0384 (6)	0.0420 (6)	0.0293 (5)	0.0067 (5)	0.0016 (4)	−0.0017 (4)
C1	0.0341 (6)	0.0353 (6)	0.0304 (6)	−0.0008 (5)	0.0024 (5)	−0.0030 (5)
C2	0.0428 (7)	0.0411 (7)	0.0371 (7)	0.0080 (6)	−0.0005 (6)	−0.0006 (6)
C3	0.0524 (9)	0.0538 (9)	0.0341 (7)	0.0067 (7)	−0.0031 (6)	0.0035 (6)
C4	0.0528 (9)	0.0641 (10)	0.0292 (7)	0.0029 (7)	0.0041 (6)	−0.0049 (6)
C5	0.0407 (7)	0.0468 (8)	0.0394 (7)	0.0032 (6)	0.0070 (6)	−0.0069 (6)
C6	0.0328 (6)	0.0344 (6)	0.0351 (7)	−0.0016 (5)	0.0025 (5)	−0.0014 (5)
C7	0.0360 (7)	0.0397 (7)	0.0390 (7)	0.0028 (5)	0.0013 (5)	0.0002 (6)
C8	0.0391 (7)	0.0446 (7)	0.0324 (7)	0.0043 (6)	−0.0010 (5)	0.0031 (5)
C9	0.0504 (9)	0.0552 (10)	0.0591 (10)	0.0181 (7)	0.0013 (7)	0.0038 (8)
C10	0.0403 (7)	0.0446 (7)	0.0321 (7)	0.0069 (6)	0.0016 (5)	−0.0041 (5)
C11	0.0400 (7)	0.0478 (8)	0.0306 (7)	0.0066 (6)	0.0019 (5)	−0.0069 (6)
C12	0.0450 (8)	0.0538 (9)	0.0384 (8)	0.0033 (7)	0.0034 (6)	−0.0098 (6)
C13	0.0606 (11)	0.0505 (9)	0.0739 (12)	−0.0092 (8)	−0.0043 (9)	−0.0039 (8)
C14	0.0433 (8)	0.0540 (8)	0.0305 (7)	0.0056 (6)	0.0007 (6)	−0.0064 (6)
C15	0.0441 (8)	0.0463 (8)	0.0349 (7)	0.0072 (6)	0.0024 (6)	−0.0006 (6)
C16	0.0583 (9)	0.0570 (9)	0.0357 (8)	−0.0043 (7)	0.0108 (7)	−0.0050 (7)
C17	0.0602 (10)	0.0545 (9)	0.0406 (8)	−0.0044 (7)	0.0075 (7)	−0.0088 (7)
C18	0.0456 (8)	0.0406 (8)	0.0476 (8)	0.0049 (6)	0.0024 (6)	0.0041 (6)
C19	0.0626 (10)	0.0563 (10)	0.0384 (8)	−0.0001 (7)	0.0095 (7)	0.0067 (7)
C20	0.0606 (9)	0.0555 (9)	0.0319 (7)	−0.0002 (7)	0.0015 (6)	−0.0003 (6)

Cl1—C18	1.7417 (16)	C9—H9B	0.9600
O1—C12	1.2007 (19)	C9—H9C	0.9600
O2—C12	1.3370 (19)	C10—C11	1.5077 (18)
O2—C13	1.442 (2)	C10—H10A	0.9700
N1—C1	1.3731 (16)	C10—H10B	0.9700
N1—C8	1.3839 (17)	C11—C14	1.338 (2)
N1—C10	1.4607 (17)	C11—C12	1.492 (2)
C1—C2	1.3940 (19)	C13—H13A	0.9600
C1—C6	1.4138 (18)	C13—H13B	0.9600
C2—C3	1.378 (2)	C13—H13C	0.9600
C2—H2	0.9300	C14—C15	1.460 (2)
C3—C4	1.399 (2)	C14—H14	0.9300
C3—H3	0.9300	C15—C20	1.400 (2)
C4—C5	1.373 (2)	C15—C16	1.403 (2)
C4—H4	0.9300	C16—C17	1.378 (2)
C5—C6	1.4001 (19)	C16—H16	0.9300
C5—H5	0.9300	C17—C18	1.378 (2)
C6—C7	1.4327 (19)	C17—H17	0.9300
C7—C8	1.363 (2)	C18—C19	1.377 (2)
C7—C9	1.497 (2)	C19—C20	1.377 (2)
C8—H8	0.9300	C19—H19	0.9300
C9—H9A	0.9600	C20—H20	0.9300
C12—O2—C13	116.06 (13)	N1—C10—H10B	109.1
C1—N1—C8	108.14 (11)	C11—C10—H10B	109.1
C1—N1—C10	124.46 (11)	H10A—C10—H10B	107.8
C8—N1—C10	127.39 (11)	C14—C11—C12	116.07 (13)
N1—C1—C2	129.96 (12)	C14—C11—C10	125.23 (13)
N1—C1—C6	107.92 (11)	C12—C11—C10	118.67 (13)
C2—C1—C6	122.09 (12)	O1—C12—O2	122.72 (15)
C3—C2—C1	117.42 (13)	O1—C12—C11	124.88 (16)
C3—C2—H2	121.3	O2—C12—C11	112.39 (12)
C1—C2—H2	121.3	O2—C13—H13A	109.5
C2—C3—C4	121.32 (14)	O2—C13—H13B	109.5
C2—C3—H3	119.3	H13A—C13—H13B	109.5
C4—C3—H3	119.3	O2—C13—H13C	109.5
C5—C4—C3	121.33 (13)	H13A—C13—H13C	109.5
C5—C4—H4	119.3	H13B—C13—H13C	109.5
C3—C4—H4	119.3	C11—C14—C15	132.06 (13)
C4—C5—C6	119.00 (13)	C11—C14—H14	114.0
C4—C5—H5	120.5	C15—C14—H14	114.0
C6—C5—H5	120.5	C20—C15—C16	117.42 (15)
C5—C6—C1	118.81 (12)	C20—C15—C14	117.37 (13)
C5—C6—C7	134.17 (13)	C16—C15—C14	125.19 (14)
C1—C6—C7	107.01 (11)	C17—C16—C15	121.12 (15)
C8—C7—C6	106.44 (12)	C17—C16—H16	119.4
C8—C7—C9	126.87 (14)	C15—C16—H16	119.4
C6—C7—C9	126.68 (13)	C18—C17—C16	119.37 (15)
C7—C8—N1	110.49 (12)	C18—C17—H17	120.3
C7—C8—H8	124.8	C16—C17—H17	120.3
N1—C8—H8	124.8	C19—C18—C17	121.42 (15)
C7—C9—H9A	109.5	C19—C18—Cl1	119.23 (12)
C7—C9—H9B	109.5	C17—C18—Cl1	119.34 (12)
H9A—C9—H9B	109.5	C18—C19—C20	118.89 (15)
C7—C9—H9C	109.5	C18—C19—H19	120.6
H9A—C9—H9C	109.5	C20—C19—H19	120.6
H9B—C9—H9C	109.5	C19—C20—C15	121.77 (15)
N1—C10—C11	112.50 (11)	C19—C20—H20	119.1
N1—C10—H10A	109.1	C15—C20—H20	119.1
C11—C10—H10A	109.1
C8—N1—C1—C2	178.13 (14)	C8—N1—C10—C11	−6.0 (2)
C10—N1—C1—C2	−1.0 (2)	N1—C10—C11—C14	92.47 (17)
C8—N1—C1—C6	−0.08 (15)	N1—C10—C11—C12	−89.24 (16)
C10—N1—C1—C6	−179.21 (12)	C13—O2—C12—O1	0.2 (2)
N1—C1—C2—C3	−177.65 (14)	C13—O2—C12—C11	179.53 (13)
C6—C1—C2—C3	0.3 (2)	C14—C11—C12—O1	0.0 (2)
C1—C2—C3—C4	−1.2 (2)	C10—C11—C12—O1	−178.46 (16)
C2—C3—C4—C5	0.7 (3)	C14—C11—C12—O2	−179.30 (13)
C3—C4—C5—C6	0.7 (2)	C10—C11—C12—O2	2.25 (19)
C4—C5—C6—C1	−1.5 (2)	C12—C11—C14—C15	176.82 (14)
C4—C5—C6—C7	177.51 (15)	C10—C11—C14—C15	−4.9 (3)
N1—C1—C6—C5	179.37 (12)	C11—C14—C15—C20	164.77 (16)
C2—C1—C6—C5	1.0 (2)	C11—C14—C15—C16	−17.0 (3)
N1—C1—C6—C7	0.14 (15)	C20—C15—C16—C17	−0.7 (2)
C2—C1—C6—C7	−178.25 (13)	C14—C15—C16—C17	−178.87 (15)
C5—C6—C7—C8	−179.20 (15)	C15—C16—C17—C18	0.3 (3)
C1—C6—C7—C8	−0.14 (15)	C16—C17—C18—C19	0.0 (3)
C5—C6—C7—C9	−0.3 (3)	C16—C17—C18—Cl1	179.55 (13)
C1—C6—C7—C9	178.81 (15)	C17—C18—C19—C20	0.1 (3)
C6—C7—C8—N1	0.09 (16)	Cl1—C18—C19—C20	−179.51 (13)
C9—C7—C8—N1	−178.86 (14)	C18—C19—C20—C15	−0.4 (3)
C1—N1—C8—C7	0.00 (16)	C16—C15—C20—C19	0.7 (2)
C10—N1—C8—C7	179.09 (13)	C14—C15—C20—C19	179.06 (15)
C1—N1—C10—C11	172.92 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···Cgi	0.96	2.69	3.581 (2)	154