5-(4-Bromo-phen-yl)-1,2,3,4-tetra-hydro-benzo[a]phenanthridine.

The title compound, C(23)H(18)BrN, was synthesized by the reaction of 4-bromo-benzaldehyde, naphthalen-2-amine and cyclo-hexa-none in tetra-hydro-furan, catalyzed by iodine. The saturated six-membered ring adopts a half-chair conformation, and the four vicinal rings form a helical conformation, which results in a significant deviation from planarity for the pyridine ring. In the crystal, a weak C-H⋯π inter-action occurs, leading to inversion dimers.

Related literature

For background on phenanthridine derivatives, see: Clement et al. (2005 ▶); Hazeldine et al. (2005 ▶); Kock et al. (2005 ▶); Lu et al. (2004 ▶); Vanquelef et al. (2004 ▶); Watanabe et al. (2003 ▶).

Experimental

Crystal data

C23H18BrN

M = 388.29

Triclinic,

a = 5.660 (3) Å

b = 11.596 (6) Å

c = 13.869 (6) Å

α = 78.48 (3)°

β = 78.30 (3)°

γ = 85.15 (3)°

V = 872.5 (8) Å3

Z = 2

Mo Kα radiation

μ = 2.36 mm−1

T = 296 K

0.46 × 0.22 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.365, T max = 0.593 (expected range = 0.432–0.702)

11744 measured reflections

3826 independent reflections

2174 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.164

S = 1.14

3826 reflections

226 parameters

H-atom parameters constrained

Δρmax = 0.94 e Å−3

Δρmin = −1.05 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013713/hb2942sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809013713/hb2942Isup2.hkl

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

C23H18BrN	Z = 2
Mr = 388.29	F(000) = 396
Triclinic, P1	Dx = 1.478 Mg m−3
Hall symbol: -P 1	Melting point = 491–493 K
a = 5.660 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.596 (6) Å	Cell parameters from 3260 reflections
c = 13.869 (6) Å	θ = 2.6–26.1°
α = 78.48 (3)°	µ = 2.36 mm−1
β = 78.30 (3)°	T = 296 K
γ = 85.15 (3)°	Block, colourless
V = 872.5 (8) Å3	0.46 × 0.22 × 0.15 mm

Bruker SMART CCD diffractometer	3826 independent reflections
Radiation source: fine-focus sealed tube	2174 reflections with I > 2σ(I)
graphite	Rint = 0.041
ω scans	θmax = 27.6°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→7
Tmin = 0.365, Tmax = 0.593	k = −13→15
11744 measured reflections	l = −18→18

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.082P)2 + 0.0233P] where P = (Fo2 + 2Fc2)/3
3826 reflections	(Δ/σ)max = 0.001
226 parameters	Δρmax = 0.94 e Å−3
0 restraints	Δρmin = −1.05 e Å−3

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
Br1	0.54047 (10)	−0.03144 (4)	0.75111 (3)	0.0876 (3)
N1	0.2434 (6)	0.4250 (3)	0.39876 (17)	0.0451 (7)
C1	0.4456 (7)	0.3594 (3)	0.3874 (2)	0.0416 (8)
C2	0.6195 (7)	0.3727 (3)	0.2984 (2)	0.0415 (8)
C3	0.5838 (6)	0.4649 (3)	0.2203 (2)	0.0406 (8)
C4	0.3867 (6)	0.5467 (3)	0.23571 (19)	0.0392 (8)
C5	0.2104 (6)	0.5181 (3)	0.32479 (19)	0.0401 (8)
C6	−0.0130 (7)	0.5835 (3)	0.3388 (2)	0.0480 (9)
H6A	−0.1273	0.5609	0.3967	0.058*
C7	−0.0644 (7)	0.6779 (3)	0.2703 (2)	0.0478 (9)
H7A	−0.2165	0.7159	0.2788	0.057*
C8	0.1163 (7)	0.7192 (3)	0.1846 (2)	0.0454 (9)
C9	0.0690 (8)	0.8271 (3)	0.1212 (2)	0.0558 (10)
H9A	−0.0824	0.8656	0.1317	0.067*
C10	0.2477 (8)	0.8748 (3)	0.0442 (3)	0.0571 (11)
H10B	0.2164	0.9446	0.0015	0.068*
C11	0.4733 (8)	0.8188 (4)	0.0305 (2)	0.0582 (11)
H11B	0.5952	0.8525	−0.0203	0.070*
C12	0.5202 (7)	0.7137 (3)	0.0910 (2)	0.0486 (9)
H12A	0.6744	0.6782	0.0805	0.058*
C13	0.3405 (7)	0.6580 (3)	0.1688 (2)	0.0420 (9)
C14	0.7466 (7)	0.4650 (3)	0.1191 (2)	0.0507 (9)
H14C	0.6566	0.4976	0.0666	0.061*
H14D	0.8805	0.5149	0.1121	0.061*
C15	0.8432 (9)	0.3429 (4)	0.1069 (2)	0.0651 (12)
H15C	0.9445	0.3455	0.0411	0.078*
H15D	0.7104	0.2928	0.1124	0.078*
C16	0.9891 (9)	0.2926 (5)	0.1872 (3)	0.0720 (13)
H16C	1.0559	0.2149	0.1781	0.086*
H16D	1.1221	0.3427	0.1814	0.086*
C17	0.8312 (7)	0.2847 (4)	0.2897 (2)	0.0514 (9)
H17A	0.7699	0.2062	0.3105	0.062*
H17B	0.9312	0.2942	0.3365	0.062*
C18	0.4726 (6)	0.2632 (3)	0.47485 (19)	0.0424 (8)
C19	0.6498 (7)	0.2655 (4)	0.5296 (2)	0.0536 (10)
H19A	0.7555	0.3268	0.5114	0.064*
C20	0.6714 (8)	0.1771 (4)	0.6116 (2)	0.0575 (11)
H20B	0.7932	0.1775	0.6476	0.069*
C21	0.5097 (7)	0.0887 (3)	0.6387 (2)	0.0491 (9)
C22	0.3329 (8)	0.0850 (3)	0.5860 (2)	0.0546 (10)
H22A	0.2260	0.0242	0.6048	0.066*
C23	0.3150 (7)	0.1734 (3)	0.5038 (2)	0.0498 (10)
H23B	0.1942	0.1718	0.4676	0.060*

	U11	U22	U33	U12	U13	U23
Br1	0.1254 (6)	0.0660 (4)	0.0680 (3)	−0.0038 (3)	−0.0449 (3)	0.0218 (2)
N1	0.048 (2)	0.0464 (18)	0.0367 (11)	−0.0030 (16)	−0.0065 (11)	0.0014 (11)
C1	0.048 (2)	0.0384 (19)	0.0381 (13)	−0.0051 (18)	−0.0127 (13)	−0.0011 (12)
C2	0.046 (2)	0.0373 (18)	0.0410 (13)	−0.0039 (17)	−0.0133 (14)	−0.0019 (12)
C3	0.047 (2)	0.0366 (19)	0.0374 (12)	−0.0069 (17)	−0.0098 (13)	−0.0003 (12)
C4	0.042 (2)	0.0394 (19)	0.0371 (12)	−0.0066 (17)	−0.0120 (13)	−0.0022 (12)
C5	0.042 (2)	0.0390 (19)	0.0375 (13)	−0.0016 (17)	−0.0085 (13)	−0.0034 (12)
C6	0.049 (3)	0.048 (2)	0.0432 (14)	−0.0004 (19)	−0.0041 (14)	−0.0046 (14)
C7	0.044 (2)	0.043 (2)	0.0577 (17)	0.0109 (18)	−0.0132 (15)	−0.0149 (15)
C8	0.051 (3)	0.042 (2)	0.0450 (14)	−0.0058 (19)	−0.0165 (15)	−0.0041 (13)
C9	0.062 (3)	0.046 (2)	0.0621 (18)	0.004 (2)	−0.0264 (19)	−0.0037 (16)
C10	0.067 (3)	0.042 (2)	0.0589 (18)	0.000 (2)	−0.0223 (19)	0.0058 (16)
C11	0.071 (3)	0.049 (2)	0.0491 (16)	−0.011 (2)	−0.0124 (17)	0.0093 (15)
C12	0.049 (2)	0.046 (2)	0.0462 (15)	−0.0039 (18)	−0.0072 (15)	0.0003 (14)
C13	0.050 (2)	0.0373 (19)	0.0398 (13)	−0.0059 (18)	−0.0155 (14)	−0.0015 (12)
C14	0.057 (3)	0.052 (2)	0.0376 (13)	−0.0010 (19)	−0.0037 (14)	−0.0001 (13)
C15	0.079 (3)	0.061 (3)	0.0465 (16)	0.005 (2)	0.0033 (17)	−0.0091 (16)
C16	0.067 (3)	0.067 (3)	0.067 (2)	0.022 (3)	−0.001 (2)	0.000 (2)
C17	0.051 (3)	0.050 (2)	0.0490 (15)	0.0011 (19)	−0.0090 (15)	−0.0016 (15)
C18	0.045 (2)	0.043 (2)	0.0351 (12)	−0.0014 (17)	−0.0053 (12)	−0.0004 (12)
C19	0.053 (3)	0.059 (2)	0.0483 (15)	−0.014 (2)	−0.0154 (15)	0.0024 (15)
C20	0.062 (3)	0.067 (3)	0.0447 (15)	−0.006 (2)	−0.0224 (16)	−0.0004 (16)
C21	0.057 (2)	0.044 (2)	0.0434 (14)	0.0040 (18)	−0.0151 (15)	0.0017 (14)
C22	0.062 (3)	0.042 (2)	0.0572 (16)	−0.008 (2)	−0.0179 (17)	0.0056 (15)
C23	0.054 (3)	0.046 (2)	0.0487 (14)	−0.0049 (19)	−0.0195 (15)	0.0033 (14)

Br1—C21	1.899 (3)	C12—C13	1.416 (5)
N1—C1	1.320 (5)	C12—H12A	0.9300
N1—C5	1.362 (4)	C14—C15	1.504 (6)
C1—C2	1.404 (5)	C14—H14C	0.9700
C1—C18	1.498 (4)	C14—H14D	0.9700
C2—C3	1.396 (4)	C15—C16	1.515 (6)
C2—C17	1.508 (6)	C15—H15C	0.9700
C3—C4	1.413 (5)	C15—H15D	0.9700
C3—C14	1.514 (5)	C16—C17	1.508 (5)
C4—C5	1.423 (4)	C16—H16C	0.9700
C4—C13	1.469 (4)	C16—H16D	0.9700
C5—C6	1.417 (5)	C17—H17A	0.9700
C6—C7	1.353 (5)	C17—H17B	0.9700
C6—H6A	0.9300	C18—C23	1.373 (5)
C7—C8	1.432 (5)	C18—C19	1.380 (4)
C7—H7A	0.9300	C19—C20	1.389 (5)
C8—C13	1.400 (5)	C19—H19A	0.9300
C8—C9	1.418 (5)	C20—C21	1.376 (5)
C9—C10	1.374 (6)	C20—H20B	0.9300
C9—H9A	0.9300	C21—C22	1.361 (5)
C10—C11	1.378 (6)	C22—C23	1.387 (4)
C10—H10B	0.9300	C22—H22A	0.9300
C11—C12	1.373 (5)	C23—H23B	0.9300
C11—H11B	0.9300
C1—N1—C5	118.9 (3)	C15—C14—H14C	109.3
N1—C1—C2	123.4 (3)	C3—C14—H14C	109.3
N1—C1—C18	115.2 (3)	C15—C14—H14D	109.3
C2—C1—C18	121.3 (3)	C3—C14—H14D	109.3
C3—C2—C1	118.2 (4)	H14C—C14—H14D	108.0
C3—C2—C17	122.8 (3)	C14—C15—C16	109.5 (3)
C1—C2—C17	119.0 (3)	C14—C15—H15C	109.8
C2—C3—C4	119.4 (3)	C16—C15—H15C	109.8
C2—C3—C14	117.4 (3)	C14—C15—H15D	109.8
C4—C3—C14	122.9 (3)	C16—C15—H15D	109.8
C3—C4—C5	117.0 (3)	H15C—C15—H15D	108.2
C3—C4—C13	127.2 (3)	C17—C16—C15	110.2 (4)
C5—C4—C13	115.9 (3)	C17—C16—H16C	109.6
N1—C5—C6	116.8 (3)	C15—C16—H16C	109.6
N1—C5—C4	122.1 (3)	C17—C16—H16D	109.6
C6—C5—C4	121.1 (3)	C15—C16—H16D	109.6
C7—C6—C5	121.7 (3)	H16C—C16—H16D	108.1
C7—C6—H6A	119.2	C2—C17—C16	116.1 (3)
C5—C6—H6A	119.2	C2—C17—H17A	108.3
C6—C7—C8	119.8 (4)	C16—C17—H17A	108.3
C6—C7—H7A	120.1	C2—C17—H17B	108.3
C8—C7—H7A	120.1	C16—C17—H17B	108.3
C13—C8—C9	121.3 (3)	H17A—C17—H17B	107.4
C13—C8—C7	120.1 (3)	C23—C18—C19	119.0 (3)
C9—C8—C7	118.5 (4)	C23—C18—C1	120.2 (3)
C10—C9—C8	119.7 (4)	C19—C18—C1	120.8 (3)
C10—C9—H9A	120.1	C18—C19—C20	120.5 (3)
C8—C9—H9A	120.1	C18—C19—H19A	119.8
C9—C10—C11	119.8 (3)	C20—C19—H19A	119.8
C9—C10—H10B	120.1	C21—C20—C19	118.9 (3)
C11—C10—H10B	120.1	C21—C20—H20B	120.6
C12—C11—C10	120.8 (4)	C19—C20—H20B	120.6
C12—C11—H11B	119.6	C22—C21—C20	121.6 (3)
C10—C11—H11B	119.6	C22—C21—Br1	119.9 (3)
C11—C12—C13	121.9 (4)	C20—C21—Br1	118.5 (2)
C11—C12—H12A	119.1	C21—C22—C23	118.8 (3)
C13—C12—H12A	119.1	C21—C22—H22A	120.6
C8—C13—C12	116.3 (3)	C23—C22—H22A	120.6
C8—C13—C4	120.5 (3)	C18—C23—C22	121.2 (3)
C12—C13—C4	123.0 (3)	C18—C23—H23B	119.4
C15—C14—C3	111.6 (3)	C22—C23—H23B	119.4
C5—N1—C1—C2	−6.8 (4)	C7—C8—C13—C12	−171.1 (3)
C5—N1—C1—C18	176.7 (3)	C9—C8—C13—C4	179.6 (3)
N1—C1—C2—C3	4.2 (5)	C7—C8—C13—C4	4.4 (4)
C18—C1—C2—C3	−179.5 (3)	C11—C12—C13—C8	−3.6 (5)
N1—C1—C2—C17	−173.5 (3)	C11—C12—C13—C4	−178.9 (3)
C18—C1—C2—C17	2.8 (4)	C3—C4—C13—C8	167.9 (3)
C1—C2—C3—C4	5.1 (4)	C5—C4—C13—C8	−10.9 (4)
C17—C2—C3—C4	−177.3 (3)	C3—C4—C13—C12	−16.9 (5)
C1—C2—C3—C14	−169.1 (3)	C5—C4—C13—C12	164.3 (3)
C17—C2—C3—C14	8.5 (5)	C2—C3—C14—C15	25.2 (4)
C2—C3—C4—C5	−11.0 (4)	C4—C3—C14—C15	−148.8 (3)
C14—C3—C4—C5	162.9 (3)	C3—C14—C15—C16	−60.4 (5)
C2—C3—C4—C13	170.1 (3)	C14—C15—C16—C17	61.1 (5)
C14—C3—C4—C13	−16.0 (5)	C3—C2—C17—C16	−6.9 (5)
C1—N1—C5—C6	177.9 (3)	C1—C2—C17—C16	170.7 (3)
C1—N1—C5—C4	0.1 (4)	C15—C16—C17—C2	−27.8 (6)
C3—C4—C5—N1	8.7 (4)	N1—C1—C18—C23	63.7 (4)
C13—C4—C5—N1	−172.3 (3)	C2—C1—C18—C23	−113.0 (4)
C3—C4—C5—C6	−169.0 (3)	N1—C1—C18—C19	−114.0 (4)
C13—C4—C5—C6	10.0 (4)	C2—C1—C18—C19	69.3 (5)
N1—C5—C6—C7	179.7 (3)	C23—C18—C19—C20	1.2 (6)
C4—C5—C6—C7	−2.5 (5)	C1—C18—C19—C20	179.0 (3)
C5—C6—C7—C8	−4.7 (5)	C18—C19—C20—C21	−1.5 (6)
C6—C7—C8—C13	3.6 (5)	C19—C20—C21—C22	1.3 (6)
C6—C7—C8—C9	−171.7 (3)	C19—C20—C21—Br1	−179.8 (3)
C13—C8—C9—C10	−1.6 (5)	C20—C21—C22—C23	−0.7 (6)
C7—C8—C9—C10	173.6 (3)	Br1—C21—C22—C23	−179.6 (3)
C8—C9—C10—C11	−1.5 (5)	C19—C18—C23—C22	−0.7 (6)
C9—C10—C11—C12	2.0 (6)	C1—C18—C23—C22	−178.4 (3)
C10—C11—C12—C13	0.6 (5)	C21—C22—C23—C18	0.4 (6)
C9—C8—C13—C12	4.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Cgi	0.93	2.88	3.620 (14)	137

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯Cgi	0.93	2.88	3.620 (14)	137

Symmetry code: (i) . Cg is the centroid of the 4-bromophenyl ring.