Ethyl N-(3-cyano-1H-indol-2-yl)form­imidate

Ruchun, Y.; Hui, Z.; BanPeng, C.

doi:10.1107/S1600536813029589

organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Page o1745

doi:10.1107/S1600536813029589

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Ethyl N-(3-cyano-1H-indol-2-yl)formimidate

Yang Ruchun,^a ^* Zhang Hui ^a and Cao BanPeng ^a

^aJiangxi Key Laboratory of Organic Chemistry, Jiangxi Science & Technology Normal University, Nanchang 330013, People's Republic of China
^*Correspondence e-mail: ouyangruchun@aliyun.com

(Received 4 October 2013; accepted 28 October 2013; online 6 November 2013)

In the title compound, C₁₂H₁₁N₃O, the C=N imino bond is in an E conformation. In the crystal, adjacent molecules are linked by N–H⋯N_cyano hydrogen bonds, forming a chain running along [110].

CCDC reference: 968757

Related literature

The starting reactant was synthesized according to a literature method (Yang et al., 2010 ). Introduction of different groups into indole molecules can generate a series of bioactive derivatives, which have been the subject of much attention as anti-cancer drugs (Laird et al., 2000 ; Li et al., 2005 ).

Experimental

Crystal data

C₁₂H₁₁N₃O
M_r = 213.24
Monoclinic, C 2/c
a = 12.7884 (6) Å
b = 8.0546 (6) Å
c = 21.4116 (10) Å
β = 94.069 (4)°
V = 2200.0 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.997, T_max = 0.998
14358 measured reflections
1934 independent reflections
1579 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.110
S = 1.12
1934 reflections
149 parameters
379 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.87 (2)	2.12 (2)	2.9490 (19)	161 (2)
Symmetry code: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 968757

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813029589/ng5344sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813029589/ng5344Isup2.hkl

checkCIF report

Comment top

The indole compounds play an important role in the pharmaceutical and agrochemical industries. Introduction of different groups into indole molecules can generate a series of bioactive derivatives, which have been the subject of much attention in anti-cancer drugs (Laird et al., 2000; Li et al., 2005). In our study, we report an indole compound.

Related literature top

The starting reactant was synthesized according to a literature method (Yang et al., 2010). Introduction of different groups into indole molecules can generate a series of bioactive derivatives, which have been the subject of much attention in anti-cancer drugs (Laird et al., 2000; Li et al., 2005).

Experimental top

The starting reactant 1 was synthesized according to a literature method (Yang et al., 2010).

Synthesis of (2)

2-amino-1H-indole-3-carbonitrile (6.29 g, 40 mmol) was suspended in dry acetonitrile (150 ml). Triethylorthoformate (10.92 ml, 9.73 g, 60 mmol) was added and the mixture was heated at reflux temperature for 1 hour. The dark brown solution was cooled to room temperature and filtered through filter paper. The acetonitrile was removed on a rotoevaporator to afford 2 as a brown solid. ¹H NMR (400 MHz, CDCl₃, TMS): δ 1.41(t, 3H, J=7.2 Hz, OCH₂CH₃), 4.40 (q, 2H, J=7.2 Hz, OCH₂CH₃), 7.20-7.31 (m, 3H, aromatic H), 7.61 (dd, 1H, aromatic H), 8.51 (s, 1H, N=CH) ppm; ¹³C NMR (100 MHz, CDCl₃): δ 14.0, 64.0, 72.7, 111.0, 116.7, 118.9, 122.2, 123.2, 127.5, 132.2, 149.8, 160.7 ppm. Crystals were grown from an acetonitrile solution.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Thermal ellipsoid plot of C₁₂H₁₁N₃O. Ellipsoids are drawn at the 30% probability level and H atoms are represented as small spheres of arbitrary radius.
	Fig. 2. Synthesis method of the title compound.
	Fig. 3. The packing of the title compound, viewed down the c axis. Dashed lines indicate hydrogen bonds.

Ethyl N-(3-cyano-1H-indol-2-yl)formimidate top

Crystal data top

C₁₂H₁₁N₃O	F(000) = 896
M_r = 213.24	D_x = 1.288 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1934 reflections
a = 12.7884 (6) Å	θ = 3.0–26.2°
b = 8.0546 (6) Å	µ = 0.09 mm⁻¹
c = 21.4116 (10) Å	T = 296 K
β = 94.069 (4)°	Block, colorless
V = 2200.0 (2) Å³	0.30 × 0.20 × 0.20 mm
Z = 8

Data collection top

Bruker SMART APEX diffractometer	1934 independent reflections
Radiation source: fine-focus sealed tube	1579 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.997, T_max = 0.998	k = −9→9
14358 measured reflections	l = −25→25

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0524P)² + 0.9005P] where P = (F_o² + 2F_c²)/3
1934 reflections	(Δ/σ)_max < 0.001
149 parameters	Δρ_max = 0.18 e Å⁻³
379 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₂H₁₁N₃O	V = 2200.0 (2) Å³
M_r = 213.24	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 12.7884 (6) Å	µ = 0.09 mm⁻¹
b = 8.0546 (6) Å	T = 296 K
c = 21.4116 (10) Å	0.30 × 0.20 × 0.20 mm
β = 94.069 (4)°

Data collection top

Bruker SMART APEX diffractometer	1934 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1579 reflections with I > 2σ(I)
T_min = 0.997, T_max = 0.998	R_int = 0.031
14358 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	379 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.18 e Å⁻³
1934 reflections	Δρ_min = −0.19 e Å⁻³
149 parameters

Special details top

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.

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 > 2sigma(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	0.49318 (10)	0.29181 (16)	0.48715 (6)	0.0443 (3)
H1	0.5435 (14)	0.348 (2)	0.4722 (8)	0.053*
N2	0.19409 (11)	−0.05378 (19)	0.46004 (7)	0.0594 (4)
N3	0.40141 (10)	0.25137 (15)	0.38870 (6)	0.0452 (3)
O1	0.34656 (11)	0.16502 (16)	0.29081 (6)	0.0700 (4)
C1	0.48809 (11)	0.25080 (18)	0.54931 (7)	0.0421 (4)
C2	0.54626 (13)	0.3073 (2)	0.60195 (8)	0.0529 (4)
H2	0.6022	0.3797	0.5987	0.063*
C3	0.51832 (15)	0.2523 (2)	0.65929 (9)	0.0618 (5)
H3	0.5557	0.2893	0.6955	0.074*
C4	0.43506 (15)	0.1423 (2)	0.66423 (8)	0.0618 (5)
H4	0.4186	0.1061	0.7036	0.074*
C5	0.37706 (13)	0.0865 (2)	0.61200 (8)	0.0525 (4)
H5	0.3214	0.0137	0.6157	0.063*
C6	0.40314 (11)	0.14121 (17)	0.55334 (7)	0.0396 (4)
C7	0.35841 (10)	0.11823 (17)	0.49076 (7)	0.0393 (4)
C8	0.41570 (11)	0.21415 (17)	0.45158 (7)	0.0401 (4)
C9	0.26740 (12)	0.02327 (19)	0.47287 (7)	0.0436 (4)
C10	0.36983 (15)	0.1409 (2)	0.35136 (8)	0.0589 (5)
H10	0.3621	0.0343	0.3670	0.071*
C11	0.35402 (15)	0.3329 (2)	0.26845 (8)	0.0627 (5)
H11A	0.4222	0.3788	0.2814	0.075*
H11B	0.3008	0.4014	0.2857	0.075*
C12	0.33881 (17)	0.3308 (3)	0.19911 (9)	0.0765 (6)
H12A	0.3929	0.2653	0.1823	0.115*
H12B	0.3420	0.4423	0.1834	0.115*
H12C	0.2716	0.2836	0.1867	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0337 (7)	0.0414 (7)	0.0582 (8)	−0.0134 (6)	0.0058 (6)	0.0020 (6)
N2	0.0426 (8)	0.0631 (9)	0.0725 (10)	−0.0232 (7)	0.0051 (6)	0.0006 (7)
N3	0.0391 (7)	0.0447 (7)	0.0523 (8)	−0.0114 (6)	0.0070 (5)	−0.0010 (5)
O1	0.0946 (10)	0.0603 (8)	0.0553 (8)	−0.0194 (7)	0.0057 (7)	−0.0082 (6)
C1	0.0338 (8)	0.0366 (8)	0.0557 (9)	−0.0016 (6)	0.0025 (6)	0.0021 (6)
C2	0.0446 (9)	0.0448 (9)	0.0678 (11)	−0.0089 (8)	−0.0064 (8)	0.0016 (8)
C3	0.0642 (11)	0.0599 (11)	0.0592 (11)	−0.0026 (9)	−0.0107 (8)	−0.0003 (8)
C4	0.0637 (11)	0.0688 (12)	0.0527 (10)	−0.0039 (10)	0.0037 (8)	0.0083 (9)
C5	0.0443 (9)	0.0529 (10)	0.0611 (10)	−0.0072 (8)	0.0083 (7)	0.0083 (8)
C6	0.0300 (7)	0.0342 (7)	0.0547 (9)	−0.0005 (6)	0.0047 (6)	0.0010 (6)
C7	0.0284 (7)	0.0349 (7)	0.0551 (9)	−0.0055 (6)	0.0069 (6)	−0.0008 (6)
C8	0.0322 (7)	0.0337 (7)	0.0548 (9)	−0.0039 (6)	0.0068 (6)	−0.0021 (6)
C9	0.0354 (8)	0.0412 (8)	0.0550 (9)	−0.0062 (7)	0.0087 (6)	0.0015 (7)
C10	0.0729 (12)	0.0487 (9)	0.0563 (11)	−0.0157 (8)	0.0117 (8)	−0.0050 (7)
C11	0.0639 (11)	0.0637 (12)	0.0609 (11)	−0.0036 (9)	0.0071 (8)	0.0010 (8)
C12	0.0734 (13)	0.0910 (15)	0.0636 (12)	0.0029 (12)	−0.0056 (10)	0.0011 (10)

Geometric parameters (Å, º) top

N1—C8	1.3587 (19)	C4—C5	1.373 (2)
N1—C1	1.377 (2)	C4—H4	0.9300
N1—H1	0.866 (18)	C5—C6	1.393 (2)
N2—C9	1.1415 (19)	C5—H5	0.9300
N3—C10	1.244 (2)	C6—C7	1.431 (2)
N3—C8	1.379 (2)	C7—C8	1.387 (2)
O1—C10	1.324 (2)	C7—C9	1.422 (2)
O1—C11	1.440 (2)	C10—H10	0.9300
C1—C2	1.383 (2)	C11—C12	1.484 (3)
C1—C6	1.407 (2)	C11—H11A	0.9700
C2—C3	1.376 (2)	C11—H11B	0.9700
C2—H2	0.9300	C12—H12A	0.9600
C3—C4	1.395 (3)	C12—H12B	0.9600
C3—H3	0.9300	C12—H12C	0.9600

C8—N1—C1	110.41 (12)	C8—C7—C9	126.43 (14)
C8—N1—H1	124.4 (11)	C8—C7—C6	107.52 (12)
C1—N1—H1	124.7 (11)	C9—C7—C6	125.92 (13)
C10—N3—C8	119.12 (14)	N1—C8—N3	119.22 (13)
C10—O1—C11	116.60 (14)	N1—C8—C7	108.23 (13)
N1—C1—C2	130.48 (14)	N3—C8—C7	132.25 (13)
N1—C1—C6	107.42 (13)	N2—C9—C7	178.31 (16)
C2—C1—C6	121.97 (15)	N3—C10—O1	124.39 (16)
C3—C2—C1	117.56 (16)	N3—C10—H10	117.8
C3—C2—H2	121.2	O1—C10—H10	117.8
C1—C2—H2	121.2	O1—C11—C12	108.37 (16)
C2—C3—C4	121.33 (16)	O1—C11—H11A	110.0
C2—C3—H3	119.3	C12—C11—H11A	110.0
C4—C3—H3	119.3	O1—C11—H11B	110.0
C5—C4—C3	121.14 (16)	C12—C11—H11B	110.0
C5—C4—H4	119.4	H11A—C11—H11B	108.4
C3—C4—H4	119.4	C11—C12—H12A	109.5
C4—C5—C6	118.74 (15)	C11—C12—H12B	109.5
C4—C5—H5	120.6	H12A—C12—H12B	109.5
C6—C5—H5	120.6	C11—C12—H12C	109.5
C5—C6—C1	119.25 (14)	H12A—C12—H12C	109.5
C5—C6—C7	134.24 (14)	H12B—C12—H12C	109.5
C1—C6—C7	106.42 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.87 (2)	2.12 (2)	2.9490 (19)	161 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.87 (2)	2.12 (2)	2.9490 (19)	161 (2)

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

Acknowledgements

This work was supported by the Science Fund of the Education Office of Jiangxi (GJJ12583) and the Bureau of Science and Technology of Nanchang City.

References

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