5-Benzyl-5H-pyrido[3,2-b]indole.

The title compound, C(18)H(14)N(2), was prepared by twofold Pd-catalyzed aryl-amination of a cyclic pyrido-benzo-iodo-lium salt. In the crystal, two mol-ecules of 9-benzyl-δ-carboline form centrosymmetrical dimers with distances of 3.651 (2) Å between the centroids of the pyridine rings and 3.961 (2) Å between the centroids of the pyrrole and pyridine rings. The phenyl rings point to the other mol-ecule in the dimer and the carboline core is essentially planar [maximum deviation of 0.027 (2) Å].

Related literature

For δ-Carboline, see: Subbaraju et al. (2004 ▶); Paulo et al. (2000 ▶); Chernyshev et al. (2001 ▶); Namjoshi et al. (2011 ▶); Qu et al. (2009 ▶); Masterova et al. (2008 ▶). For synthetic strategies to carbolines, see: Späth & Eiter (1940 ▶); Sakamoto et al. (1999 ▶); Franck et al. (2008 ▶). For the transition-metal-catalyzed synthesis of carbazoles, see: Letessier (2011 ▶); Nemkovich et al. (2009 ▶). For the transition-metal-catalyzed synthesis of carbolines, see: Nissen et al. (2011 ▶), Dassonneville et al. (2010 ▶). For β-carboline, see: Torreiles et al. (1985 ▶); Love (2006 ▶); Dassonneville et al. (2011 ▶); Nissen & Detert (2011 ▶). For the synthesis of the title compound, see: Letessier & Detert (2011 ▶).

Experimental

Crystal data

C18H14N2

M = 258.1

Monoclinic,

a = 11.295 (4) Å

b = 10.482 (4) Å

c = 11.961 (4) Å

β = 110.387 (11)°

V = 1327.4 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 173 K

0.51 × 0.25 × 0.02 mm

Data collection

Bruker SMART CCD diffractometer

15877 measured reflections

3149 independent reflections

1444 reflections with I > 2σ(I)

R int = 0.128

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.149

S = 0.98

3149 reflections

182 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811032107/bt5607sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811032107/bt5607Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811032107/bt5607Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C18H14N2	F(000) = 544
Mr = 258.1	Dx = 1.293 Mg m−3
Monoclinic, P21/n	Melting point: 415 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 11.295 (4) Å	Cell parameters from 1161 reflections
b = 10.482 (4) Å	θ = 2.6–22.3°
c = 11.961 (4) Å	µ = 0.08 mm−1
β = 110.387 (11)°	T = 173 K
V = 1327.4 (8) Å3	Plate, colourless
Z = 4	0.51 × 0.25 × 0.02 mm

Bruker SMART CCD diffractometer	1444 reflections with I > 2σ(I)
Radiation source: sealed Tube	Rint = 0.128
graphite	θmax = 27.9°, θmin = 2.1°
CCD scan	h = −14→14
15877 measured reflections	k = −13→13
3149 independent reflections	l = −15→15

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055	H-atom parameters constrained
wR(F2) = 0.149	w = 1/[σ2(Fo2) + (0.0558P)2 + 0.2129P] where P = (Fo2 + 2Fc2)/3
S = 0.98	(Δ/σ)max < 0.001
3149 reflections	Δρmax = 0.22 e Å−3
182 parameters	Δρmin = −0.21 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.016 (2)

Experimental. 1H-NMR (400 MHz, CDCl3): δ = 8.59 (dd, J = 4.7 Hz, J = 1.2 Hz, 1H, 2-H), 8.43 (d, J = 7.8 Hz, 1H, 9-H), 7.64 (dd, J = 8.2 Hz, J = 1.2 Hz, 1H, 6-H), 7.53 (td, J = 8.3 Hz, J = 1.2 Hz, 1H, 7-H), 7.42 (d, J = 8.2 Hz, 1H, 6-H), 7.26-7.34 (m, 5H, CH), 7.12 (m, 2H, CH), 5.52 (s, 2H, CH2). 13C-NMR (75 MHz, CDCl3): δ = 141.9 (d, C-2), 141.8 (s, C-9b), 141.4 (s, C-5a), 136.5 (s, C-1), 134.0 (s, C-4a), 128.9 (d, C-2), 127.9 (d, C-7), 127.7 (d, C-4), 126.3 (d, C-3), 122.2 (s, C-9a), 120.9 (d, C-3), 120.1 (d, C-9), 120.0 (d, C-8), 115.8 (d, C-4), 109.2 (d, C-6), 46.5 (t, CH2). IR (neat, ATR): ν = 1621 (w), 1588 (w), 1482 (m), 1451 (m), 1412 (s), 1334 (m), 1318 (s), 1242 (w), 1193 (m), 1115 (w), 1012 (w), 913 (w), 845 (m), 781 (s), 742 (vs), 730 (vs), 721 (vs), 695 (s)cm-1. FD-MS: m/z = 258.1 [C18H14N2]+.

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.

	x	y	z	Uiso*/Ueq
N1	0.74211 (17)	0.47469 (18)	0.17200 (17)	0.0360 (5)
C2	0.7372 (2)	0.4852 (2)	0.2855 (2)	0.0334 (6)
C3	0.8208 (2)	0.5471 (2)	0.3853 (2)	0.0410 (6)
H3	0.8945	0.5885	0.3825	0.049*
C4	0.7916 (3)	0.5456 (2)	0.4876 (2)	0.0468 (7)
H4	0.8463	0.5873	0.5568	0.056*
C5	0.6848 (3)	0.4849 (2)	0.4923 (2)	0.0501 (7)
H5	0.6678	0.4861	0.5647	0.060*
C6	0.6034 (2)	0.4233 (2)	0.3955 (2)	0.0424 (7)
H6	0.5304	0.3817	0.3998	0.051*
C7	0.6295 (2)	0.4231 (2)	0.2914 (2)	0.0356 (6)
C8	0.5662 (2)	0.3720 (2)	0.1737 (2)	0.0365 (6)
N9	0.45662 (19)	0.3047 (2)	0.1336 (2)	0.0488 (6)
C10	0.4201 (2)	0.2725 (3)	0.0174 (3)	0.0514 (8)
H10	0.3436	0.2259	−0.0154	0.062*
C11	0.4853 (3)	0.3021 (2)	−0.0574 (2)	0.0522 (8)
H11	0.4528	0.2755	−0.1384	0.063*
C12	0.5981 (2)	0.3703 (2)	−0.0164 (2)	0.0452 (7)
H12	0.6447	0.3914	−0.0664	0.054*
C13	0.6378 (2)	0.4055 (2)	0.1036 (2)	0.0370 (6)
C14	0.8358 (2)	0.5335 (2)	0.1306 (2)	0.0409 (6)
H14A	0.8610	0.6162	0.1719	0.049*
H14B	0.7963	0.5513	0.0442	0.049*
C15	0.9524 (2)	0.4548 (2)	0.1502 (2)	0.0360 (6)
C16	1.0688 (2)	0.5125 (3)	0.1743 (2)	0.0475 (7)
H16	1.0757	0.6027	0.1820	0.057*
C17	1.1752 (2)	0.4406 (3)	0.1872 (2)	0.0548 (8)
H17	1.2544	0.4817	0.2035	0.066*
C18	1.1675 (3)	0.3100 (3)	0.1769 (2)	0.0583 (8)
H18	1.2407	0.2606	0.1857	0.070*
C19	1.0529 (3)	0.2523 (3)	0.1537 (3)	0.0606 (9)
H19	1.0468	0.1621	0.1471	0.073*
C20	0.9462 (2)	0.3233 (3)	0.1399 (2)	0.0487 (7)
H20	0.8673	0.2815	0.1232	0.058*

	U11	U22	U33	U12	U13	U23
N1	0.0301 (11)	0.0362 (12)	0.0403 (13)	−0.0008 (9)	0.0106 (9)	0.0009 (9)
C2	0.0340 (13)	0.0264 (13)	0.0380 (15)	0.0064 (11)	0.0102 (11)	0.0032 (11)
C3	0.0415 (14)	0.0330 (14)	0.0454 (17)	−0.0039 (12)	0.0113 (12)	0.0013 (12)
C4	0.0553 (17)	0.0366 (16)	0.0437 (17)	−0.0044 (14)	0.0113 (13)	−0.0011 (13)
C5	0.0628 (19)	0.0421 (16)	0.0487 (17)	0.0031 (15)	0.0234 (15)	0.0025 (14)
C6	0.0381 (15)	0.0372 (15)	0.0577 (19)	0.0002 (12)	0.0239 (14)	0.0030 (13)
C7	0.0313 (13)	0.0277 (13)	0.0459 (16)	0.0049 (11)	0.0112 (12)	0.0052 (11)
C8	0.0263 (12)	0.0303 (14)	0.0499 (16)	0.0017 (11)	0.0097 (11)	0.0029 (12)
N9	0.0354 (12)	0.0359 (13)	0.0652 (16)	0.0046 (11)	0.0050 (11)	0.0021 (12)
C10	0.0363 (15)	0.0358 (16)	0.066 (2)	0.0038 (12)	−0.0024 (15)	−0.0015 (14)
C11	0.0535 (18)	0.0396 (17)	0.0447 (17)	0.0077 (15)	−0.0066 (14)	−0.0034 (13)
C12	0.0494 (16)	0.0372 (15)	0.0442 (17)	0.0081 (13)	0.0102 (13)	0.0032 (12)
C13	0.0295 (13)	0.0314 (14)	0.0440 (16)	0.0058 (11)	0.0050 (12)	−0.0006 (12)
C14	0.0408 (14)	0.0394 (15)	0.0438 (16)	−0.0017 (12)	0.0161 (12)	0.0034 (12)
C15	0.0353 (14)	0.0397 (15)	0.0324 (14)	−0.0023 (12)	0.0112 (11)	−0.0013 (11)
C16	0.0444 (16)	0.0535 (17)	0.0422 (16)	−0.0130 (14)	0.0123 (13)	−0.0050 (13)
C17	0.0344 (15)	0.081 (2)	0.0485 (18)	−0.0076 (16)	0.0140 (13)	−0.0022 (16)
C18	0.0416 (17)	0.075 (2)	0.061 (2)	0.0133 (17)	0.0214 (14)	0.0001 (17)
C19	0.0534 (19)	0.0505 (19)	0.084 (2)	0.0045 (15)	0.0321 (17)	−0.0043 (16)
C20	0.0379 (15)	0.0436 (16)	0.0663 (19)	−0.0008 (13)	0.0202 (13)	−0.0050 (14)

N1—C2	1.382 (3)	C11—C12	1.393 (4)
N1—C13	1.383 (3)	C11—H11	0.9500
N1—C14	1.453 (3)	C12—C13	1.395 (3)
C2—C3	1.397 (3)	C12—H12	0.9500
C2—C7	1.403 (3)	C14—C15	1.502 (3)
C3—C4	1.373 (3)	C14—H14A	0.9900
C3—H3	0.9500	C14—H14B	0.9900
C4—C5	1.382 (4)	C15—C16	1.383 (3)
C4—H4	0.9500	C15—C20	1.384 (3)
C5—C6	1.365 (3)	C16—C17	1.380 (4)
C5—H5	0.9500	C16—H16	0.9500
C6—C7	1.376 (3)	C17—C18	1.374 (4)
C6—H6	0.9500	C17—H17	0.9500
C7—C8	1.442 (3)	C18—C19	1.366 (4)
C8—N9	1.358 (3)	C18—H18	0.9500
C8—C13	1.398 (3)	C19—C20	1.376 (4)
N9—C10	1.348 (3)	C19—H19	0.9500
C10—C11	1.378 (4)	C20—H20	0.9500
C10—H10	0.9500
C2—N1—C13	107.80 (19)	C11—C12—C13	115.1 (3)
C2—N1—C14	125.75 (19)	C11—C12—H12	122.4
C13—N1—C14	126.3 (2)	C13—C12—H12	122.4
N1—C2—C3	129.1 (2)	N1—C13—C12	130.5 (2)
N1—C2—C7	110.2 (2)	N1—C13—C8	109.2 (2)
C3—C2—C7	120.8 (2)	C12—C13—C8	120.3 (2)
C4—C3—C2	117.1 (2)	N1—C14—C15	114.7 (2)
C4—C3—H3	121.4	N1—C14—H14A	108.6
C2—C3—H3	121.4	C15—C14—H14A	108.6
C3—C4—C5	121.7 (2)	N1—C14—H14B	108.6
C3—C4—H4	119.1	C15—C14—H14B	108.6
C5—C4—H4	119.1	H14A—C14—H14B	107.6
C6—C5—C4	121.5 (3)	C16—C15—C20	118.0 (2)
C6—C5—H5	119.2	C16—C15—C14	120.7 (2)
C4—C5—H5	119.2	C20—C15—C14	121.2 (2)
C5—C6—C7	118.4 (2)	C17—C16—C15	120.7 (3)
C5—C6—H6	120.8	C17—C16—H16	119.6
C7—C6—H6	120.8	C15—C16—H16	119.6
C6—C7—C2	120.5 (2)	C18—C17—C16	120.6 (3)
C6—C7—C8	133.9 (2)	C18—C17—H17	119.7
C2—C7—C8	105.5 (2)	C16—C17—H17	119.7
N9—C8—C13	124.4 (2)	C19—C18—C17	119.0 (3)
N9—C8—C7	128.3 (2)	C19—C18—H18	120.5
C13—C8—C7	107.4 (2)	C17—C18—H18	120.5
C10—N9—C8	114.1 (2)	C18—C19—C20	120.9 (3)
N9—C10—C11	124.9 (3)	C18—C19—H19	119.6
N9—C10—H10	117.5	C20—C19—H19	119.6
C11—C10—H10	117.5	C19—C20—C15	120.8 (3)
C10—C11—C12	121.1 (3)	C19—C20—H20	119.6
C10—C11—H11	119.4	C15—C20—H20	119.6
C12—C11—H11	119.4
C13—N1—C2—C3	−179.4 (2)	C10—C11—C12—C13	−0.3 (4)
C14—N1—C2—C3	−3.2 (4)	C2—N1—C13—C12	178.9 (2)
C13—N1—C2—C7	−0.1 (2)	C14—N1—C13—C12	2.8 (4)
C14—N1—C2—C7	176.1 (2)	C2—N1—C13—C8	0.1 (2)
N1—C2—C3—C4	178.4 (2)	C14—N1—C13—C8	−176.1 (2)
C7—C2—C3—C4	−0.8 (3)	C11—C12—C13—N1	−178.6 (2)
C2—C3—C4—C5	0.4 (4)	C11—C12—C13—C8	0.2 (3)
C3—C4—C5—C6	0.2 (4)	N9—C8—C13—N1	179.3 (2)
C4—C5—C6—C7	−0.3 (4)	C7—C8—C13—N1	0.0 (3)
C5—C6—C7—C2	−0.2 (4)	N9—C8—C13—C12	0.3 (4)
C5—C6—C7—C8	−178.6 (2)	C7—C8—C13—C12	−179.0 (2)
N1—C2—C7—C6	−178.6 (2)	C2—N1—C14—C15	88.4 (3)
C3—C2—C7—C6	0.7 (4)	C13—N1—C14—C15	−96.1 (3)
N1—C2—C7—C8	0.1 (2)	N1—C14—C15—C16	−146.8 (2)
C3—C2—C7—C8	179.5 (2)	N1—C14—C15—C20	35.9 (3)
C6—C7—C8—N9	−0.8 (4)	C20—C15—C16—C17	0.2 (4)
C2—C7—C8—N9	−179.3 (2)	C14—C15—C16—C17	−177.2 (2)
C6—C7—C8—C13	178.4 (3)	C15—C16—C17—C18	−0.3 (4)
C2—C7—C8—C13	−0.1 (2)	C16—C17—C18—C19	−0.1 (4)
C13—C8—N9—C10	−0.6 (3)	C17—C18—C19—C20	0.5 (4)
C7—C8—N9—C10	178.5 (2)	C18—C19—C20—C15	−0.5 (4)
C8—N9—C10—C11	0.5 (4)	C16—C15—C20—C19	0.2 (4)
N9—C10—C11—C12	−0.1 (4)	C14—C15—C20—C19	177.6 (2)