(Z)-3-(1H-Indol-3-yl)-2-(4-nitro­phen­yl)acrylonitrile

Qian, B.-H.; Liu, W.-W.; Hu, H.-W.

doi:10.1107/S160053680703632X

(Z)-3-(1H-Indol-3-yl)-2-(4-nitrophenyl)acrylonitrile

The dihedral angle between the indole and benzene ring systems in the title compound, C₁₇H₁₁N₃O₂, is 4.37 (7) °. In the crystal structure, molecules are linked by N—H

N and C—H

O hydrogen bonds, resulting in the formation of layers. These layers are further interconnected through weak offset π–π stacking between the nitrophenyl and indole ring systems, with a centroid-to-centroid distance of 3.766 (2) Å and an interplanar distance of 3.524 Å.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703632X/dn2224sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680703632X/dn2224Isup2.hkl Contains datablock I

CCDC reference: 657860

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Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.003 Å
R factor = 0.045
wR factor = 0.127
Data-to-parameter ratio = 12.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.63 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C7
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.33
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C10    -   C11    ...       1.43 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Owing to the utilization and development of acrylonitrile derivatives in electroluminescence material and medicine domain, the synthesis of such compounds has been a subject of considerable importance in both academic and industrial interest (Mei et al., 2006). Indole and its derivatives are important heterocyclic nitrogen compounds which display a wide range of biological activity. Indole derivatives (Horton et al., 2003) have been used as antitumor (Martino et al., 2004), h5-HT_{2 A} antagonist (Smith et al., 2000), the Agonists of the Somatostatin Receptor (Rohrer et al., 1998) and also as anti-inflammatory activity (Narayana et al., 2005). We report here the X-ray crystal structure of (Z)-2-(4-Nitrophenyl)-3-(3-indole)acrylonitrile, containing indole ring and acrylonitrile structure.

The molecule contains one benzene ring, C12—C17 (denoted A) and one indolizinyl ring C1—C8/N1 (denoted B) (Fig. 1). The dihedral angle between Ring A and B is 4.37 (7)°. The values of C10—C12 [1.477 (3) Å] and C2—C9 [1.433 (3) Å] bond length are shorter than the value for C—C single bond because of conjugation effect. The C9 ═ C10 bond length of 1.350 (3)Å is typical for C=C double bond; it links ring A and B to form a planar structure and extended conjugated system.

The occurrence of N—H···N and C—H···O weak hydrogen bonds results in the formation of layers (Table 1, Fig. 2). These layers are further interconnected through weak offset π···π stacking between nitrophenyl and indolyl rings with a centroid to centroid distance of 3.766 (2)Å and an interplanar distance of 3.524 Å.

Related literature top

For related literature, see: Horton et al. (2003); Martino et al. (2004); Mei et al. (2006); Narayana et al. (2005); Rohrer et al. (1998); Smith et al. (2000).

Experimental top

A solution of 3-indolealdehyde (0.837 g, 5.8 mmol), p-nitrophenyl acetonitrile (0.94 g, 5.8 mmol) in anhydrous methyl hydrate(20 ml) was stirred at 317 K for 0.5 h, the mixture of potassium hydroxide (0.325 g, 5.8 mmol)and methyl hydrate(10 ml) was added slowly, the reaction mass was stirred and kept at 317 K until all the substrate had disappeared (monitored by thin-layer chromatography). The resulting mixture was settled, the title compound was collected by filtration and desiccated in vacuo, the orange_ red single crystals of (I) suitable for x-raycrystallographic analysis were obtained by recrystallization from the mixture of alcohol and acetone.

Structure description top

For related literature, see: Horton et al. (2003); Martino et al. (2004); Mei et al. (2006); Narayana et al. (2005); Rohrer et al. (1998); Smith et al. (2000).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view showing the formation of the layer through N—H···N and C—H···O hydrogen bonds.Hydrogen bonds are indicated by dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) -x, y - 1:2, -z + 3/2; (ii) -x + 1, y - 1/2, -z + 1/2]

(Z)-3-(1H-Indol-3-yl)2-(4-nitrophenyl)acrylonitrile top

Crystal data top

C₁₇H₁₁N₃O₂	F(000) = 600
M_r = 289.29	D_x = 1.375 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1699 reflections
a = 7.6534 (7) Å	θ = 2.7–25.8°
b = 12.7131 (14) Å	µ = 0.09 mm⁻¹
c = 14.3741 (19) Å	T = 298 K
β = 92.329 (2)°	Block, orange-red
V = 1397.4 (3) Å³	0.50 × 0.49 × 0.41 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2457 independent reflections
Radiation source: fine-focus sealed tube	1469 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
φ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→7
T_min = 0.955, T_max = 0.963	k = −15→15
6876 measured reflections	l = −15→17

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0484P)² + 0.4261P] where P = (F_o² + 2F_c²)/3
2457 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₇H₁₁N₃O₂	V = 1397.4 (3) Å³
M_r = 289.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6534 (7) Å	µ = 0.09 mm⁻¹
b = 12.7131 (14) Å	T = 298 K
c = 14.3741 (19) Å	0.50 × 0.49 × 0.41 mm
β = 92.329 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2457 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1469 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.963	R_int = 0.039
6876 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.03	Δρ_max = 0.16 e Å⁻³
2457 reflections	Δρ_min = −0.18 e Å⁻³
199 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
N1	0.1143 (3)	0.27266 (15)	0.69809 (13)	0.0527 (6)
H1	0.0764	0.2570	0.7518	0.063*
N2	0.0515 (3)	0.63722 (16)	0.65436 (15)	0.0609 (6)
N3	0.4362 (3)	0.85849 (16)	0.25503 (15)	0.0540 (6)
O1	0.4104 (3)	0.95193 (13)	0.27196 (13)	0.0740 (6)
O2	0.5065 (3)	0.82885 (14)	0.18492 (13)	0.0743 (6)
C1	0.1351 (3)	0.37147 (17)	0.66547 (17)	0.0500 (6)
H1A	0.1104	0.4327	0.6979	0.060*
C2	0.1985 (3)	0.36808 (16)	0.57694 (15)	0.0389 (5)
C3	0.2169 (3)	0.25839 (17)	0.55554 (15)	0.0420 (6)
C4	0.1630 (3)	0.20133 (17)	0.63242 (16)	0.0467 (6)
C5	0.1642 (4)	0.09230 (19)	0.6352 (2)	0.0669 (8)
H5	0.1279	0.0554	0.6868	0.080*
C6	0.2209 (5)	0.0420 (2)	0.5588 (2)	0.0973 (12)
H6	0.2240	−0.0311	0.5585	0.117*
C7	0.2747 (5)	0.0964 (2)	0.4807 (2)	0.0980 (12)
H7	0.3126	0.0591	0.4296	0.118*
C8	0.2723 (4)	0.20418 (19)	0.47815 (19)	0.0642 (8)
H8	0.3071	0.2403	0.4257	0.077*
C9	0.2462 (3)	0.45127 (16)	0.51569 (15)	0.0394 (6)
H9	0.3063	0.4293	0.4642	0.047*
C10	0.2191 (3)	0.55609 (16)	0.51992 (14)	0.0373 (5)
C11	0.1267 (3)	0.59945 (17)	0.59569 (16)	0.0425 (6)
C12	0.2753 (3)	0.63297 (15)	0.45012 (15)	0.0371 (5)
C13	0.3487 (3)	0.60254 (17)	0.36748 (15)	0.0456 (6)
H13	0.3632	0.5313	0.3553	0.055*
C14	0.4004 (3)	0.67492 (17)	0.30336 (16)	0.0479 (6)
H14	0.4497	0.6530	0.2485	0.057*
C15	0.3787 (3)	0.77990 (17)	0.32110 (15)	0.0429 (6)
C16	0.3045 (4)	0.81272 (18)	0.40089 (18)	0.0628 (8)
H16	0.2884	0.8841	0.4120	0.075*
C17	0.2539 (4)	0.73956 (18)	0.46449 (17)	0.0576 (7)
H17	0.2039	0.7623	0.5188	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0708 (14)	0.0472 (12)	0.0416 (11)	−0.0023 (11)	0.0192 (10)	0.0083 (10)
N2	0.0813 (16)	0.0562 (13)	0.0468 (13)	0.0071 (12)	0.0221 (12)	−0.0053 (11)
N3	0.0631 (14)	0.0485 (13)	0.0515 (13)	0.0008 (11)	0.0158 (11)	0.0109 (11)
O1	0.1092 (16)	0.0399 (10)	0.0750 (13)	−0.0022 (10)	0.0293 (12)	0.0121 (9)
O2	0.0973 (15)	0.0686 (12)	0.0600 (12)	0.0114 (11)	0.0421 (11)	0.0157 (10)
C1	0.0620 (17)	0.0387 (13)	0.0503 (15)	0.0003 (12)	0.0156 (13)	0.0027 (11)
C2	0.0412 (13)	0.0374 (12)	0.0387 (13)	−0.0001 (10)	0.0091 (10)	0.0026 (10)
C3	0.0464 (14)	0.0368 (12)	0.0437 (13)	−0.0009 (11)	0.0113 (11)	0.0025 (11)
C4	0.0523 (15)	0.0392 (12)	0.0492 (15)	−0.0015 (11)	0.0114 (12)	0.0052 (12)
C5	0.095 (2)	0.0410 (14)	0.0665 (18)	−0.0017 (14)	0.0274 (16)	0.0116 (14)
C6	0.167 (4)	0.0342 (15)	0.094 (2)	−0.0020 (18)	0.055 (2)	0.0029 (16)
C7	0.173 (4)	0.0404 (16)	0.085 (2)	0.0000 (19)	0.065 (2)	−0.0074 (16)
C8	0.095 (2)	0.0415 (14)	0.0583 (17)	−0.0034 (14)	0.0312 (15)	0.0034 (12)
C9	0.0429 (14)	0.0381 (12)	0.0380 (12)	−0.0006 (10)	0.0110 (10)	−0.0003 (10)
C10	0.0430 (13)	0.0362 (12)	0.0331 (12)	−0.0010 (10)	0.0086 (10)	−0.0031 (10)
C11	0.0554 (15)	0.0363 (12)	0.0365 (13)	−0.0020 (11)	0.0095 (12)	0.0027 (11)
C12	0.0404 (13)	0.0328 (11)	0.0388 (13)	−0.0008 (10)	0.0077 (10)	−0.0014 (10)
C13	0.0612 (16)	0.0325 (11)	0.0442 (14)	0.0043 (11)	0.0166 (12)	−0.0027 (11)
C14	0.0586 (16)	0.0444 (13)	0.0419 (14)	0.0081 (12)	0.0189 (12)	0.0034 (11)
C15	0.0498 (14)	0.0385 (12)	0.0413 (13)	0.0013 (11)	0.0135 (11)	0.0078 (11)
C16	0.100 (2)	0.0317 (13)	0.0594 (17)	0.0011 (13)	0.0329 (16)	−0.0001 (12)
C17	0.091 (2)	0.0380 (13)	0.0467 (14)	−0.0012 (13)	0.0338 (14)	−0.0036 (12)

Geometric parameters (Å, º) top

N1—C1	1.353 (3)	C7—C8	1.370 (4)
N1—C4	1.371 (3)	C7—H7	0.9300
N1—H1	0.8600	C8—H8	0.9300
N2—C11	1.146 (3)	C9—C10	1.350 (3)
N3—O2	1.221 (2)	C9—H9	0.9300
N3—O1	1.230 (2)	C10—C11	1.433 (3)
N3—C15	1.459 (3)	C10—C12	1.477 (3)
C1—C2	1.381 (3)	C12—C17	1.382 (3)
C1—H1A	0.9300	C12—C13	1.390 (3)
C2—C9	1.433 (3)	C13—C14	1.372 (3)
C2—C3	1.436 (3)	C13—H13	0.9300
C3—C8	1.390 (3)	C14—C15	1.370 (3)
C3—C4	1.398 (3)	C14—H14	0.9300
C4—C5	1.387 (3)	C15—C16	1.366 (3)
C5—C6	1.357 (4)	C16—C17	1.371 (3)
C5—H5	0.9300	C16—H16	0.9300
C6—C7	1.395 (4)	C17—H17	0.9300
C6—H6	0.9300

C1—N1—C4	109.66 (19)	C7—C8—H8	120.7
C1—N1—H1	125.2	C3—C8—H8	120.7
C4—N1—H1	125.2	C10—C9—C2	131.1 (2)
O2—N3—O1	122.7 (2)	C10—C9—H9	114.5
O2—N3—C15	118.7 (2)	C2—C9—H9	114.5
O1—N3—C15	118.5 (2)	C9—C10—C11	119.7 (2)
N1—C1—C2	109.9 (2)	C9—C10—C12	124.95 (19)
N1—C1—H1A	125.0	C11—C10—C12	115.34 (18)
C2—C1—H1A	125.0	N2—C11—C10	177.6 (2)
C1—C2—C9	130.6 (2)	C17—C12—C13	117.1 (2)
C1—C2—C3	105.60 (19)	C17—C12—C10	120.54 (19)
C9—C2—C3	123.73 (19)	C13—C12—C10	122.38 (19)
C8—C3—C4	119.0 (2)	C14—C13—C12	121.7 (2)
C8—C3—C2	133.5 (2)	C14—C13—H13	119.2
C4—C3—C2	107.44 (19)	C12—C13—H13	119.2
N1—C4—C5	130.0 (2)	C15—C14—C13	119.2 (2)
N1—C4—C3	107.35 (19)	C15—C14—H14	120.4
C5—C4—C3	122.6 (2)	C13—C14—H14	120.4
C6—C5—C4	116.7 (3)	C16—C15—C14	120.8 (2)
C6—C5—H5	121.6	C16—C15—N3	119.0 (2)
C4—C5—H5	121.6	C14—C15—N3	120.3 (2)
C5—C6—C7	122.2 (3)	C15—C16—C17	119.4 (2)
C5—C6—H6	118.9	C15—C16—H16	120.3
C7—C6—H6	118.9	C17—C16—H16	120.3
C8—C7—C6	120.8 (3)	C16—C17—C12	121.8 (2)
C8—C7—H7	119.6	C16—C17—H17	119.1
C6—C7—H7	119.6	C12—C17—H17	119.1
C7—C8—C3	118.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.86	2.28	3.048 (3)	149
C8—H8···O2ⁱⁱ	0.93	2.45	3.346 (3)	161

Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₁N₃O₂
M_r	289.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.6534 (7), 12.7131 (14), 14.3741 (19)
β (°)	92.329 (2)
V (Å³)	1397.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.49 × 0.41

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.955, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	6876, 2457, 1469
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.127, 1.03
No. of reflections	2457
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.18

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000) and PLATON (Spek, 2003), SHELXTL.