2-(2-Iodo­phen­yl)-1,2,3,4-tetra­hydro­isoquinoline-1-carbonitrile

Ma, Y.; Sun, Y.; Zheng, F.; Sun, W.; Zhou, L.

doi:10.1107/S1600536811015212

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1484

doi:10.1107/S1600536811015212

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2-(2-Iodophenyl)-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile

Yanni Ma,^a Yifang Sun,^b Feng Zheng,^a Wenwen Sun ^a and Le Zhou ^a ^*

^aCollege of Science, Northwest Agriculture and Forest University, Yangling 712100, People's Republic of China, and ^bCollege of Life Science, Northwest Agriculture and Forest University, Yangling 712100, People's Republic of China
^*Correspondence e-mail: zhoulechem@yahoo.com.cn

(Received 8 April 2011; accepted 22 April 2011; online 20 May 2011)

In the title compound, C₁₆H₁₃IN₂, the two benzene rings make a dihedral angle of 67.26 (5)°. The six-membered heterocycle of the tetrahydroisoquinoline unit adopts a half-chair conformation. In the crystal, adjacent molecules are linked by pairs of weak intermolecular C—H⋯N hydrogen bonds, forming inversion dimers. An intramolecular C—H⋯I close contact is also observed.

Related literature

For the synthesis of the title compound, see: Ishii et al. (1985 ). For the biological activity of tetrahydroisoquinoline derivatives, see: Abe et al. (2005 ); Kamal et al. (2011 ); Lane et al. (2006 ); Liu et al. (2009 ); Storch et al. (2002 ); Wright et al. (1990 ).

Experimental

Crystal data

C₁₆H₁₃IN₂
M_r = 360.18
Monoclinic, P 2₁ /n
a = 11.7607 (12) Å
b = 8.4473 (9) Å
c = 15.2601 (15) Å
β = 107.662 (1)°
V = 1444.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.20 mm⁻¹
T = 296 K
0.42 × 0.32 × 0.26 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.458, T_max = 0.598
10311 measured reflections
2689 independent reflections
2359 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.101
S = 1.02
2689 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 1.16 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯N2ⁱ	0.98	2.60	3.418 (5)	141
C7—H7⋯I1	0.98	3.03	3.633 (4)	121
Symmetry code: (i) -x+1, -y+2, -z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015212/is2698sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811015212/is2698Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811015212/is2698Isup3.cml

checkCIF report

Comment top

The tetrahydroisoquinoline derivatives have recently attracted great attention due to their neurotoxicity (Abe et al., 2005; Storch et al., 2002), antitumor activities (Lane et al., 2006; Wright et al., 1990), antimicrobial activity (Kamal et al., 2011; Liu et al., 2009), and so on. With the interests in the synthesis of tetrahydroisoquinoline derivatives with biological activity, we report here the synthesis and crystal structure of the title compound.

As shown in Fig. 1, the molecule of the title compound is built up from one 1-cyan-tetrahydroisoquinoline fragment connected to one 2-iodobenzene ring through the C—N bonds. Benzene C1–C6 and C11–C16 rings are inclined with respect to one another with a dihedral angle of 67.26 (5)°. The conformation of the six-membered ring of tetrahydroisoquinoline fragment is analyzed with respect to the plane formed by C1/C6/C7/C9 and the corresponding deviations of the atoms C8 and N1 are 0.459 (5) and 0.332 (3) Å, respectively. The C—N bonds within the tetrahydroisoquinoline fragment belong to single bond, the inter-ring C—N bond show some π-bond character, while the C—N bond of the cyano is of triple bond character. The important torsion angle which decides the geometry of the title compound is -80.4 (4)° for C12—C11—N1—C7.

In the crystal structure, two adjacent molecules are linked by a weak intermolecular C—H···N hydrogen bond into a dimer. These dimers are further connected by C—I···π interaction into a one-dimension chain along the b axis (Fig. 2). I1 aims at the π-cloud of the neighboring benzene ring C1–C6 (Cg), The I···Cg distance is 3.821 (2) Å with C···Cg of 5.622 (5) Å and C—I···Cg angle of 141.73°. An intramolecular C—H···I hydrogen bond is also observed (Table 1), which further consolidates the crystal packing.

Related literature top

For the synthesis of the title compound, see: Ishii et al. (1985). For the biological activity of tetrahydroisoquinoline derivatives, see: Abe et al. (2005); Kamal et al. (2011); Lane et al. (2006); Liu et al. (2009); Storch et al. (2002); Wright et al. (1990).

Experimental top

The title compound was synthesized according to the literature procedure (Ishii et al., 1985), and the single crystals were obtained from a solution of ethyl acetate by slow evaporation at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. An ORTEP drawing of the title compound, with 30% probability displacement ellipsoids.
	Fig. 2. The one-dimension chain structure of the title compound.

2-(2-Iodophenyl)-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile top

Crystal data top

C₁₆H₁₃IN₂	F(000) = 704
M_r = 360.18	D_x = 1.656 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5815 reflections
a = 11.7607 (12) Å	θ = 2.6–28.1°
b = 8.4473 (9) Å	µ = 2.20 mm⁻¹
c = 15.2601 (15) Å	T = 296 K
β = 107.662 (1)°	Block, colourless
V = 1444.6 (3) Å³	0.42 × 0.32 × 0.26 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2689 independent reflections
Radiation source: fine-focus sealed tube	2359 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.458, T_max = 0.598	k = −10→10
10311 measured reflections	l = −18→18

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0558P)² + 2.5461P] where P = (F_o² + 2F_c²)/3
2689 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 1.16 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

C₁₆H₁₃IN₂	V = 1444.6 (3) Å³
M_r = 360.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.7607 (12) Å	µ = 2.20 mm⁻¹
b = 8.4473 (9) Å	T = 296 K
c = 15.2601 (15) Å	0.42 × 0.32 × 0.26 mm
β = 107.662 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2689 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2359 reflections with I > 2σ(I)
T_min = 0.458, T_max = 0.598	R_int = 0.018
10311 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.02	Δρ_max = 1.16 e Å⁻³
2689 reflections	Δρ_min = −0.51 e Å⁻³
172 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
C1	0.1617 (4)	1.1100 (5)	0.0837 (3)	0.0552 (10)
C2	0.0577 (4)	1.1981 (7)	0.0437 (5)	0.0757 (15)
H2	0.0056	1.2177	0.0778	0.091*
C3	0.0307 (5)	1.2559 (7)	−0.0439 (5)	0.0821 (17)
H3	−0.0380	1.3159	−0.0682	0.098*
C4	0.1052 (5)	1.2253 (7)	−0.0962 (4)	0.0785 (15)
H4	0.0867	1.2636	−0.1560	0.094*
C5	0.2082 (4)	1.1369 (6)	−0.0589 (3)	0.0612 (12)
H5	0.2594	1.1170	−0.0936	0.073*
C6	0.2349 (4)	1.0783 (5)	0.0296 (3)	0.0470 (9)
C7	0.3478 (4)	0.9792 (5)	0.0678 (3)	0.0412 (8)
H7	0.3501	0.9004	0.0213	0.049*
C8	0.3220 (4)	1.0020 (6)	0.2187 (3)	0.0535 (10)
H8A	0.3721	1.0956	0.2282	0.064*
H8B	0.3359	0.9488	0.2774	0.064*
C9	0.1920 (5)	1.0483 (6)	0.1804 (4)	0.0655 (13)
H9A	0.1426	0.9568	0.1815	0.079*
H9B	0.1740	1.1291	0.2194	0.079*
C10	0.4559 (4)	1.0835 (5)	0.0839 (3)	0.0457 (9)
C11	0.4559 (3)	0.7998 (4)	0.1851 (3)	0.0417 (8)
C12	0.4616 (4)	0.6511 (5)	0.1462 (3)	0.0440 (8)
C13	0.5645 (5)	0.5622 (5)	0.1734 (4)	0.0588 (11)
H13	0.5677	0.4651	0.1454	0.071*
C14	0.6628 (4)	0.6160 (6)	0.2419 (3)	0.0622 (12)
H14	0.7324	0.5559	0.2596	0.075*
C15	0.6579 (4)	0.7576 (6)	0.2839 (3)	0.0615 (11)
H15	0.7230	0.7923	0.3317	0.074*
C16	0.5558 (4)	0.8495 (5)	0.2549 (3)	0.0531 (10)
H16	0.5539	0.9469	0.2829	0.064*
I1	0.31094 (3)	0.55223 (3)	0.05008 (2)	0.05981 (15)
N1	0.3511 (3)	0.8951 (4)	0.1520 (2)	0.0425 (7)
N2	0.5385 (4)	1.1593 (5)	0.0987 (3)	0.0632 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.051 (2)	0.047 (2)	0.071 (3)	−0.0028 (19)	0.024 (2)	−0.013 (2)
C2	0.048 (3)	0.070 (3)	0.109 (4)	0.011 (2)	0.025 (3)	−0.021 (3)
C3	0.061 (3)	0.072 (4)	0.099 (4)	0.019 (3)	0.004 (3)	−0.011 (3)
C4	0.075 (3)	0.070 (3)	0.077 (3)	0.013 (3)	0.003 (3)	0.002 (3)
C5	0.060 (3)	0.060 (3)	0.061 (3)	0.005 (2)	0.014 (2)	−0.003 (2)
C6	0.043 (2)	0.038 (2)	0.059 (2)	−0.0019 (16)	0.0148 (18)	−0.0094 (18)
C7	0.0452 (19)	0.0354 (18)	0.047 (2)	−0.0025 (16)	0.0204 (16)	−0.0058 (16)
C8	0.069 (3)	0.049 (2)	0.051 (2)	0.000 (2)	0.031 (2)	−0.010 (2)
C9	0.065 (3)	0.066 (3)	0.082 (3)	0.008 (2)	0.046 (3)	−0.009 (2)
C10	0.046 (2)	0.042 (2)	0.054 (2)	0.0030 (18)	0.0218 (18)	0.0005 (17)
C11	0.051 (2)	0.0360 (19)	0.0430 (19)	−0.0035 (16)	0.0223 (17)	0.0000 (15)
C12	0.053 (2)	0.0389 (19)	0.046 (2)	−0.0035 (17)	0.0227 (17)	−0.0019 (16)
C13	0.073 (3)	0.042 (2)	0.067 (3)	0.008 (2)	0.030 (2)	0.001 (2)
C14	0.058 (3)	0.058 (3)	0.069 (3)	0.014 (2)	0.017 (2)	0.012 (2)
C15	0.057 (3)	0.066 (3)	0.056 (3)	−0.003 (2)	0.010 (2)	0.007 (2)
C16	0.062 (3)	0.048 (2)	0.050 (2)	−0.002 (2)	0.0191 (19)	−0.0051 (19)
I1	0.0717 (2)	0.0453 (2)	0.0607 (2)	−0.01053 (13)	0.01746 (16)	−0.01147 (12)
N1	0.0493 (18)	0.0375 (16)	0.0474 (17)	0.0006 (14)	0.0246 (15)	−0.0060 (14)
N2	0.058 (2)	0.054 (2)	0.082 (3)	−0.010 (2)	0.028 (2)	−0.004 (2)

Geometric parameters (Å, º) top

C1—C6	1.387 (6)	C8—H8A	0.9700
C1—C2	1.403 (7)	C8—H8B	0.9700
C1—C9	1.503 (7)	C9—H9A	0.9700
C2—C3	1.368 (9)	C9—H9B	0.9700
C2—H2	0.9300	C10—N2	1.128 (5)
C3—C4	1.376 (9)	C11—C16	1.390 (6)
C3—H3	0.9300	C11—C12	1.400 (5)
C4—C5	1.390 (7)	C11—N1	1.430 (5)
C4—H4	0.9300	C12—C13	1.377 (6)
C5—C6	1.382 (6)	C12—I1	2.100 (4)
C5—H5	0.9300	C13—C14	1.380 (7)
C6—C7	1.528 (6)	C13—H13	0.9300
C7—N1	1.458 (5)	C14—C15	1.367 (7)
C7—C10	1.505 (6)	C14—H14	0.9300
C7—H7	0.9800	C15—C16	1.386 (7)
C8—N1	1.477 (5)	C15—H15	0.9300
C8—C9	1.513 (7)	C16—H16	0.9300

C6—C1—C2	117.4 (5)	H8A—C8—H8B	108.4
C6—C1—C9	120.8 (4)	C1—C9—C8	112.3 (4)
C2—C1—C9	121.7 (4)	C1—C9—H9A	109.1
C3—C2—C1	121.8 (5)	C8—C9—H9A	109.1
C3—C2—H2	119.1	C1—C9—H9B	109.1
C1—C2—H2	119.1	C8—C9—H9B	109.1
C2—C3—C4	120.0 (5)	H9A—C9—H9B	107.9
C2—C3—H3	120.0	N2—C10—C7	177.7 (5)
C4—C3—H3	120.0	C16—C11—C12	117.3 (4)
C3—C4—C5	119.5 (5)	C16—C11—N1	122.6 (3)
C3—C4—H4	120.3	C12—C11—N1	120.2 (3)
C5—C4—H4	120.3	C13—C12—C11	120.8 (4)
C6—C5—C4	120.3 (5)	C13—C12—I1	118.1 (3)
C6—C5—H5	119.9	C11—C12—I1	120.9 (3)
C4—C5—H5	119.9	C12—C13—C14	120.5 (4)
C5—C6—C1	121.0 (4)	C12—C13—H13	119.8
C5—C6—C7	118.8 (4)	C14—C13—H13	119.8
C1—C6—C7	120.2 (4)	C15—C14—C13	119.9 (4)
N1—C7—C10	110.3 (3)	C15—C14—H14	120.1
N1—C7—C6	113.0 (3)	C13—C14—H14	120.1
C10—C7—C6	109.6 (3)	C14—C15—C16	119.8 (4)
N1—C7—H7	107.9	C14—C15—H15	120.1
C10—C7—H7	107.9	C16—C15—H15	120.1
C6—C7—H7	107.9	C15—C16—C11	121.6 (4)
N1—C8—C9	108.0 (4)	C15—C16—H16	119.2
N1—C8—H8A	110.1	C11—C16—H16	119.2
C9—C8—H8A	110.1	C11—N1—C7	112.0 (3)
N1—C8—H8B	110.1	C11—N1—C8	117.1 (3)
C9—C8—H8B	110.1	C7—N1—C8	111.1 (3)

C6—C1—C2—C3	−2.3 (8)	C16—C11—C12—I1	173.5 (3)
C9—C1—C2—C3	179.2 (5)	N1—C11—C12—I1	−7.4 (5)
C1—C2—C3—C4	1.4 (9)	C11—C12—C13—C14	2.1 (7)
C2—C3—C4—C5	−0.6 (9)	I1—C12—C13—C14	−174.6 (4)
C3—C4—C5—C6	0.8 (8)	C12—C13—C14—C15	0.7 (7)
C4—C5—C6—C1	−1.8 (7)	C13—C14—C15—C16	−2.5 (7)
C4—C5—C6—C7	179.0 (4)	C14—C15—C16—C11	1.5 (7)
C2—C1—C6—C5	2.5 (7)	C12—C11—C16—C15	1.3 (6)
C9—C1—C6—C5	−179.0 (4)	N1—C11—C16—C15	−177.8 (4)
C2—C1—C6—C7	−178.3 (4)	C16—C11—N1—C7	98.6 (4)
C9—C1—C6—C7	0.2 (6)	C12—C11—N1—C7	−80.4 (4)
C5—C6—C7—N1	−166.6 (4)	C16—C11—N1—C8	−31.4 (5)
C1—C6—C7—N1	14.2 (5)	C12—C11—N1—C8	149.5 (4)
C5—C6—C7—C10	70.0 (5)	C10—C7—N1—C11	−58.6 (4)
C1—C6—C7—C10	−109.2 (4)	C6—C7—N1—C11	178.4 (3)
C6—C1—C9—C8	19.0 (6)	C10—C7—N1—C8	74.5 (4)
C2—C1—C9—C8	−162.6 (4)	C6—C7—N1—C8	−48.5 (4)
N1—C8—C9—C1	−51.5 (5)	C9—C8—N1—C11	−161.5 (4)
C16—C11—C12—C13	−3.1 (6)	C9—C8—N1—C7	68.1 (4)
N1—C11—C12—C13	176.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···N2ⁱ	0.98	2.60	3.418 (5)	141
C7—H7···I1	0.98	3.03	3.633 (4)	121

Symmetry code: (i) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃IN₂
M_r	360.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	11.7607 (12), 8.4473 (9), 15.2601 (15)
β (°)	107.662 (1)
V (Å³)	1444.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.20
Crystal size (mm)	0.42 × 0.32 × 0.26

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.458, 0.598
No. of measured, independent and observed [I > 2σ(I)] reflections	10311, 2689, 2359
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.101, 1.02
No. of reflections	2689
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.16, −0.51

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···N2ⁱ	0.98	2.60	3.418 (5)	141
C7—H7···I1	0.98	3.03	3.633 (4)	121

Symmetry code: (i) −x+1, −y+2, −z.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (NNSF; Nos. 30771454, 31000865).

References

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