N-[3-(2-Methyl­phen­yl)isoquinolin-1-yl]formamide

Cui, F.N.; Li, J.Q.; Chen, X.L.; Song, Q.B.

doi:10.1107/S1600536809011714

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o960

doi:10.1107/S1600536809011714

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N-[3-(2-Methylphenyl)isoquinolin-1-yl]formamide

Fu Na Cui,^a Jun Qi Li,^a Xiao Li Chen ^a and Qing Bao Song ^a ^*

^aThe State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: qbsong@zjut.edu.cn

(Received 21 March 2009; accepted 30 March 2009; online 2 April 2009)

The title compound, C₁₇H₁₄N₂O, crystallizes as a cis formamide isomer. The isoquinoline and benzene fragments are nearly perpendicular [dihedral angle = 81.79 (18)°], whereas the formamide group is virtually coplanar with the isoquinoline unit [dihedral angle = 1.66 (15)°]. Intermolecular N—H⋯O hydrogen bonds link molecules into a centrosymmetric dimer.

Related literature

For the cytotoxic activity of arylisoquinolines, see: Cho et al. (2002 , 2003 ). For the synthethic procedures relevant to this work, see: Nunno et al. (2008 ); Tovar & Swager (1999 ); Cho et al. (2002).

Experimental

Crystal data

C₁₇H₁₄N₂O
M_r = 262.30
Triclinic, $[P \overline 1]$
a = 5.3898 (14) Å
b = 11.166 (3) Å
c = 11.899 (3) Å
α = 106.139 (3)°
β = 93.128 (3)°
γ = 103.800 (3)°
V = 662.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.36 × 0.23 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.971, T_max = 0.987
4772 measured reflections
2399 independent reflections
1575 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.124
S = 1.03
2399 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.13 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
N2—H2⋯O1ⁱ	0.86	2.10	2.940 (2)	165
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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/S1600536809011714/gk2201sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011714/gk2201Isup2.hkl

checkCIF report

Comment top

Many of the arylisoquinoline derivatives exhibit potent cytotoxic activities against five different human tumor cell lines (Cho et al., 2002, 2003). The title compound, that belongs to arylisoquinolines, has been synthesized to study its cytotoxic activity and its crystal structure is reported here.

Related literature top

For the cytotoxic activity of arylisoquinolines, see: Cho et al. (2002, 2003). For the synthethic procedures relevant to this work, see: Nunno et al. (2008); Tovar & Swager (1999); Cho et al. (2002).

Experimental top

A 2.5 M solution of n-BuLi in hexanes (54.5 mmol) was added to a solution of the diisopropylamine (59.9 mmol) in THF (5 ml) at 273 K under nitrogen atmosphere. After 10 min, the solution of 2-methylbenzonitrile (36.4 mmol) in THF (5 ml) was added dropwise and the obtained brown reaction mixture was stirred for 1 h, then adding the DMF (18.2 mmol), the mixture was stirred for 2 h at room temperature (Cho et al., 2002; Nunno et al., 2008; Tovar et al., 1999). The mixture was subsequently concentrated under reduced pressure giving the crude product. The residue was recrystallized from ethanol. Colorless crystals of the title compound were obtained by slow evaporation of the solvent after 2 days at room temperature(Yield: 73%, m.p. 401–403 K).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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. View of the molecular structure showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level. H atoms have been omitted for clarity.
	Fig. 2. The molecular packing viewed along the a axis. Hydrogen bonds are shown with dashed lines. H atoms are omitted for clarity.

N-[3-(2-Methylphenyl)isoquinolin-1-yl]formamide top

Crystal data top

C₁₇H₁₄N₂O	Z = 2
M_r = 262.30	F(000) = 276
Triclinic, P1	D_x = 1.315 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.3898 (14) Å	Cell parameters from 1222 reflections
b = 11.166 (3) Å	θ = 3.0–26.0°
c = 11.899 (3) Å	µ = 0.08 mm⁻¹
α = 106.139 (3)°	T = 296 K
β = 93.128 (3)°	Block, colourless
γ = 103.800 (3)°	0.36 × 0.23 × 0.16 mm
V = 662.4 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2399 independent reflections
Radiation source: fine-focus sealed tube	1575 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 0 pixels mm^-1	θ_max = 25.5°, θ_min = 3.0°
ϕ and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −13→13
T_min = 0.971, T_max = 0.987	l = −14→14
4772 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0578P)² + 0.0805P] where P = (F_o² + 2F_c²)/3
2399 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₇H₁₄N₂O	γ = 103.800 (3)°
M_r = 262.30	V = 662.4 (3) Å³
Triclinic, P1	Z = 2
a = 5.3898 (14) Å	Mo Kα radiation
b = 11.166 (3) Å	µ = 0.08 mm⁻¹
c = 11.899 (3) Å	T = 296 K
α = 106.139 (3)°	0.36 × 0.23 × 0.16 mm
β = 93.128 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2399 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1575 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.987	R_int = 0.017
4772 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.03	Δρ_max = 0.13 e Å⁻³
2399 reflections	Δρ_min = −0.19 e Å⁻³
182 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	0.2507 (3)	0.67650 (17)	0.71903 (14)	0.0446 (4)
C2	0.1010 (3)	0.74496 (17)	0.67117 (15)	0.0444 (4)
C4	−0.0799 (4)	0.8081 (2)	0.51425 (18)	0.0651 (6)
H4	−0.1015	0.8032	0.4349	0.078*
C5	−0.1976 (4)	0.8866 (2)	0.59439 (18)	0.0627 (6)
H5	−0.2959	0.9339	0.5681	0.075*
C6	−0.1697 (4)	0.8945 (2)	0.71022 (18)	0.0592 (5)
H6	−0.2504	0.9465	0.7627	0.071*
C7	−0.0188 (3)	0.82420 (18)	0.75214 (15)	0.0481 (5)
C8	0.0201 (4)	0.83123 (19)	0.87248 (16)	0.0550 (5)
H8	−0.0586	0.8820	0.9272	0.066*
C9	0.1717 (4)	0.76428 (18)	0.90878 (15)	0.0485 (5)
C10	0.5217 (4)	0.52789 (19)	0.67853 (16)	0.0551 (5)
H10	0.5431	0.5346	0.7583	0.066*
C11	0.2307 (4)	0.77304 (19)	1.03607 (15)	0.0479 (5)
C12	0.0620 (4)	0.69894 (19)	1.09041 (16)	0.0531 (5)
C13	0.1360 (4)	0.7069 (2)	1.20679 (17)	0.0623 (6)
H13	0.0261	0.6567	1.2437	0.075*
C14	0.3655 (4)	0.7863 (2)	1.26835 (18)	0.0636 (6)
H14	0.4105	0.7889	1.3457	0.076*
C15	0.5290 (4)	0.8620 (2)	1.21612 (18)	0.0662 (6)
H15	0.6831	0.9178	1.2584	0.079*
C16	0.4630 (4)	0.8548 (2)	1.09957 (17)	0.0600 (6)
H16	0.5751	0.9051	1.0635	0.072*
C17	−0.1907 (4)	0.6097 (2)	1.0258 (2)	0.0735 (6)
H17A	−0.3010	0.6596	1.0076	0.110*
H17B	−0.2710	0.5602	1.0746	0.110*
H17C	−0.1617	0.5524	0.9541	0.110*
C18	0.0666 (4)	0.7385 (2)	0.55094 (16)	0.0558 (5)
H18	0.1441	0.6866	0.4966	0.067*
N1	0.2872 (3)	0.68582 (15)	0.83158 (12)	0.0492 (4)
N2	0.3716 (3)	0.59354 (15)	0.64362 (12)	0.0517 (4)
H2	0.3469	0.5844	0.5694	0.062*
O1	0.6325 (3)	0.45974 (14)	0.61283 (11)	0.0655 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0521 (11)	0.0470 (11)	0.0386 (10)	0.0214 (9)	0.0112 (8)	0.0112 (8)
C2	0.0477 (10)	0.0478 (11)	0.0410 (10)	0.0187 (9)	0.0078 (8)	0.0134 (8)
C4	0.0777 (15)	0.0831 (16)	0.0477 (11)	0.0425 (13)	0.0049 (10)	0.0231 (11)
C5	0.0683 (13)	0.0731 (15)	0.0596 (12)	0.0387 (12)	0.0033 (10)	0.0241 (11)
C6	0.0639 (13)	0.0663 (14)	0.0569 (12)	0.0364 (11)	0.0094 (10)	0.0168 (10)
C7	0.0492 (11)	0.0519 (12)	0.0466 (10)	0.0206 (9)	0.0068 (8)	0.0142 (9)
C8	0.0668 (13)	0.0630 (13)	0.0426 (10)	0.0340 (11)	0.0147 (9)	0.0119 (9)
C9	0.0555 (11)	0.0555 (12)	0.0384 (10)	0.0238 (10)	0.0114 (8)	0.0116 (9)
C10	0.0755 (14)	0.0638 (13)	0.0380 (10)	0.0378 (12)	0.0107 (9)	0.0170 (9)
C11	0.0579 (12)	0.0535 (11)	0.0383 (9)	0.0285 (10)	0.0111 (9)	0.0104 (9)
C12	0.0595 (12)	0.0560 (12)	0.0463 (11)	0.0227 (10)	0.0070 (9)	0.0132 (9)
C13	0.0754 (15)	0.0728 (15)	0.0434 (11)	0.0228 (12)	0.0084 (10)	0.0220 (10)
C14	0.0760 (15)	0.0762 (15)	0.0417 (11)	0.0293 (13)	0.0017 (11)	0.0157 (11)
C15	0.0628 (13)	0.0766 (15)	0.0529 (12)	0.0210 (12)	−0.0034 (10)	0.0094 (11)
C16	0.0576 (13)	0.0731 (14)	0.0484 (11)	0.0181 (11)	0.0083 (10)	0.0159 (10)
C17	0.0690 (14)	0.0802 (16)	0.0671 (14)	0.0124 (13)	−0.0022 (11)	0.0239 (12)
C18	0.0651 (13)	0.0687 (14)	0.0419 (10)	0.0332 (11)	0.0089 (9)	0.0163 (10)
N1	0.0622 (10)	0.0564 (10)	0.0363 (8)	0.0285 (8)	0.0113 (7)	0.0140 (7)
N2	0.0707 (11)	0.0640 (10)	0.0326 (8)	0.0390 (9)	0.0089 (7)	0.0153 (7)
O1	0.0930 (11)	0.0775 (10)	0.0454 (7)	0.0555 (9)	0.0183 (7)	0.0194 (7)

Geometric parameters (Å, º) top

C1—N1	1.314 (2)	C10—N2	1.334 (2)
C1—N2	1.406 (2)	C10—H10	0.9300
C1—C2	1.430 (2)	C11—C12	1.390 (3)
C2—C18	1.412 (2)	C11—C16	1.393 (3)
C2—C7	1.412 (2)	C12—C13	1.393 (3)
C4—C18	1.365 (3)	C12—C17	1.500 (3)
C4—C5	1.395 (3)	C13—C14	1.367 (3)
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.354 (3)	C14—C15	1.368 (3)
C5—H5	0.9300	C14—H14	0.9300
C6—C7	1.416 (3)	C15—C16	1.388 (3)
C6—H6	0.9300	C15—H15	0.9300
C7—C8	1.413 (2)	C16—H16	0.9300
C8—C9	1.358 (3)	C17—H17A	0.9600
C8—H8	0.9300	C17—H17B	0.9600
C9—N1	1.369 (2)	C17—H17C	0.9600
C9—C11	1.502 (2)	C18—H18	0.9300
C10—O1	1.218 (2)	N2—H2	0.8600

N1—C1—N2	116.00 (15)	C16—C11—C9	118.94 (17)
N1—C1—C2	124.34 (16)	C11—C12—C13	118.20 (19)
N2—C1—C2	119.66 (15)	C11—C12—C17	121.62 (17)
C18—C2—C7	118.91 (16)	C13—C12—C17	120.16 (19)
C18—C2—C1	124.80 (16)	C14—C13—C12	121.9 (2)
C7—C2—C1	116.28 (15)	C14—C13—H13	119.0
C18—C4—C5	120.80 (19)	C12—C13—H13	119.0
C18—C4—H4	119.6	C13—C14—C15	120.03 (19)
C5—C4—H4	119.6	C13—C14—H14	120.0
C6—C5—C4	120.51 (18)	C15—C14—H14	120.0
C6—C5—H5	119.7	C14—C15—C16	119.5 (2)
C4—C5—H5	119.7	C14—C15—H15	120.2
C5—C6—C7	120.56 (18)	C16—C15—H15	120.2
C5—C6—H6	119.7	C15—C16—C11	120.7 (2)
C7—C6—H6	119.7	C15—C16—H16	119.7
C2—C7—C8	118.35 (16)	C11—C16—H16	119.7
C2—C7—C6	119.00 (16)	C12—C17—H17A	109.5
C8—C7—C6	122.64 (17)	C12—C17—H17B	109.5
C9—C8—C7	120.43 (17)	H17A—C17—H17B	109.5
C9—C8—H8	119.8	C12—C17—H17C	109.5
C7—C8—H8	119.8	H17A—C17—H17C	109.5
C8—C9—N1	122.13 (16)	H17B—C17—H17C	109.5
C8—C9—C11	122.85 (16)	C4—C18—C2	120.22 (18)
N1—C9—C11	115.00 (15)	C4—C18—H18	119.9
O1—C10—N2	124.36 (17)	C2—C18—H18	119.9
O1—C10—H10	117.8	C1—N1—C9	118.43 (15)
N2—C10—H10	117.8	C10—N2—C1	124.96 (15)
C12—C11—C16	119.63 (17)	C10—N2—H2	117.5
C12—C11—C9	121.41 (17)	C1—N2—H2	117.5

N1—C1—C2—C18	178.11 (18)	C9—C11—C12—C13	176.52 (17)
N2—C1—C2—C18	−1.4 (3)	C16—C11—C12—C17	179.84 (18)
N1—C1—C2—C7	−1.8 (3)	C9—C11—C12—C17	−1.9 (3)
N2—C1—C2—C7	178.68 (16)	C11—C12—C13—C14	1.1 (3)
C18—C4—C5—C6	−0.4 (3)	C17—C12—C13—C14	179.6 (2)
C4—C5—C6—C7	0.6 (3)	C12—C13—C14—C15	0.6 (3)
C18—C2—C7—C8	−179.13 (18)	C13—C14—C15—C16	−1.7 (3)
C1—C2—C7—C8	0.8 (3)	C14—C15—C16—C11	1.0 (3)
C18—C2—C7—C6	0.1 (3)	C12—C11—C16—C15	0.7 (3)
C1—C2—C7—C6	−179.99 (17)	C9—C11—C16—C15	−177.58 (18)
C5—C6—C7—C2	−0.4 (3)	C5—C4—C18—C2	0.0 (3)
C5—C6—C7—C8	178.7 (2)	C7—C2—C18—C4	0.1 (3)
C2—C7—C8—C9	0.8 (3)	C1—C2—C18—C4	−179.81 (19)
C6—C7—C8—C9	−178.41 (19)	N2—C1—N1—C9	−179.35 (16)
C7—C8—C9—N1	−1.5 (3)	C2—C1—N1—C9	1.1 (3)
C7—C8—C9—C11	176.90 (18)	C8—C9—N1—C1	0.6 (3)
C8—C9—C11—C12	83.5 (3)	C11—C9—N1—C1	−177.95 (17)
N1—C9—C11—C12	−98.0 (2)	O1—C10—N2—C1	−177.35 (19)
C8—C9—C11—C16	−98.3 (2)	N1—C1—N2—C10	−1.6 (3)
N1—C9—C11—C16	80.3 (2)	C2—C1—N2—C10	177.92 (17)
C16—C11—C12—C13	−1.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.10	2.940 (2)	165

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₄N₂O
M_r	262.30
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.3898 (14), 11.166 (3), 11.899 (3)
α, β, γ (°)	106.139 (3), 93.128 (3), 103.800 (3)
V (Å³)	662.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.36 × 0.23 × 0.16

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.971, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	4772, 2399, 1575
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.124, 1.03
No. of reflections	2399
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.19

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), 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
N2—H2···O1ⁱ	0.86	2.10	2.940 (2)	165.0

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

This work was supported by the Key Discipline of Applied Chemistry, Zhejiang Province, and the State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, People's Republic of China.

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cho, W. J., Kim, E. K., Park, Y., Jeong, E. Y., Kim, T. S., Le, T. N., Kim, D. D. & Lee, E. S. (2002). Bioorg. Med. Chem. 10, 2953–2961. Web of Science CSD CrossRef PubMed CAS Google Scholar
Cho, W. J., Min, S. Y., Le, T. N. & Kim, T. S. (2003). Bioorg. Med. Chem. Lett. 13, 4451–4454. Web of Science CrossRef PubMed CAS Google Scholar
Nunno, L. D., Vitale, P. & Scilimati, A. (2008). Tetrahedron, 64, 11198–11204. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tovar, J. D. & Swager, T. M. (1999). J. Org. Chem. 64, 6499–6505. Web of Science CSD CrossRef CAS Google Scholar