(±)-4a-(4-Nitro­benz­yl)-2,3,4,4a-tetra­hydro-1H-carbazole

Zhou, H.; Ou, S.-Y.; Yan, R.-A.; Liao, X.-J.

doi:10.1107/S1600536811020277

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1573

doi:10.1107/S1600536811020277

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(±)-4a-(4-Nitrobenzyl)-2,3,4,4a-tetrahydro-1H-carbazole

Hua Zhou,^a ^* Shi-Yi Ou,^a Ri-An Yan ^a and Xiao-Jian Liao ^b

^aDepartment of Food Science and Engineering, Jinan University, Guangzhou 510632, People's Republic of China, and ^bDepartment of Chemistry, Jinan University, Guangzhou 510632, People's Republic of China
^*Correspondence e-mail: zhouhua5460@jnu.edu.cn

(Received 8 May 2011; accepted 27 May 2011; online 4 June 2011)

The title molecule, C₁₉H₁₈N₂O₂, is built up from three fused rings, viz. phenyl, pyrrole and cyclohexane, linked to a nitrobenzyl group. The C atom bearing the nitrobenzyl group is chiral and the compound is a racemate (R/S). The dihedral angle between the nitrobenzyl and indole rings is 57.49 (5)°. The cyclohexane ring adopts a slightly distorted chair conformation.

Related literature

For the biocativity of carbazole derivatives, see: Nakahara et al. (2002 ); Yukari et al. (2001 , 2003 ). For crystallographic studies of carbazole derivatives, see: Gunaseelan et al. (2007 ); Murugavel et al. (2008 ).

Experimental

Crystal data

C₁₉H₁₈N₂O₂
M_r = 306.35
Monoclinic, P 2₁ /c
a = 8.7266 (3) Å
b = 16.6916 (6) Å
c = 11.0857 (4) Å
β = 105.790 (4)°
V = 1553.82 (10) Å³
Z = 4
Cu Kα radiation
μ = 0.69 mm⁻¹
T = 295 K
0.5 × 0.4 × 0.3 mm

Data collection

Agilent Xcalibur Sapphire3 Gemini ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.967, T_max = 1.000
4772 measured reflections
2479 independent reflections
2089 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.116
S = 1.04
2479 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811020277/dn2687sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811020277/dn2687Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811020277/dn2687Isup3.cml

checkCIF report

Comment top

Carbazole alkaloids are a class of alkaloids containing a structural moiety of indole. Many of them possess significant bioactivity and some of them are used in medicine (Nakahara et al.2002; Yukari et al.(2001, 2003)). This is the reason why they have attracted our interest.

The molecular structure of the title compound is built up from three fused rings, a phenyl, a pyrrole and a cyclohexane, linked to a nitrobenzyl group (Fig.1). The C1 carbon is chiral and the compound is a racemate (R/S). The dihedral angle between the nitrobenzyl and the indole rings is 57.49 (5)°. Bond lengths and angles agree with related compounds (Gunaseelan et al. (2007); Murugavel et al. (2008)).

Related literature top

For the biocativity of carbazole derivatives, see: Nakahara et al. (2002); Yukari et al. (2001, 2003). For crystallographic studies of carbazole derivatives, see: Gunaseelan et al. (2007); Murugavel et al. (2008).

Experimental top

2-[(4-nitrophenyl)methyl]-Cyclohexanone (0.233 g, 1 mmol) and phenylhydrazine(0.118 g, 1.1 mmol) were added to acetic acid (10 ml). The mixture was stirred at 295 K for 1 h, and ice-water (10 ml) was added. After filtration, the precipitate was collected as a yellow solid. The impure product was dissolved in MeOH at room temperature. Colourless crystals suitable for X-ray analysis (92.6% yield) grew over a period of one week when the solution was exposed to the air. CH&N elemental analysis. Calc. for C₁₉H₁₈N₂O₂: C 74.49, H 5.92, N 9.14, O 10.44%; found: C 74.52, H 5.91, N 9.15%, O 10.45%.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of the title compound in (I) showing the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.

(±)-4a-(4-Nitrobenzyl)-2,3,4,4a-tetrahydro-1H-carbazole top

Crystal data top

C₁₉H₁₈N₂O₂	F(000) = 648
M_r = 306.35	D_x = 1.310 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.5418 Å
a = 8.7266 (3) Å	Cell parameters from 2290 reflections
b = 16.6916 (6) Å	θ = 4.1–63.3°
c = 11.0857 (4) Å	µ = 0.69 mm⁻¹
β = 105.790 (4)°	T = 295 K
V = 1553.82 (10) Å³	Block, colourless
Z = 4	0.5 × 0.4 × 0.3 mm

Data collection top

Agilent Xcalibur Sapphire3 Gemini ultra diffractometer	2479 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	2089 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.016
Detector resolution: 16.0288 pixels mm^-1	θ_max = 63.4°, θ_min = 4.9°
ω scans	h = −9→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −19→15
T_min = 0.967, T_max = 1.000	l = −12→12
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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.053P)² + 0.3423P] where P = (F_o² + 2F_c²)/3
2479 reflections	(Δ/σ)_max < 0.001
208 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₉H₁₈N₂O₂	V = 1553.82 (10) Å³
M_r = 306.35	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 8.7266 (3) Å	µ = 0.69 mm⁻¹
b = 16.6916 (6) Å	T = 295 K
c = 11.0857 (4) Å	0.5 × 0.4 × 0.3 mm
β = 105.790 (4)°

Data collection top

Agilent Xcalibur Sapphire3 Gemini ultra diffractometer	2479 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	2089 reflections with I > 2σ(I)
T_min = 0.967, T_max = 1.000	R_int = 0.016
4772 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.04	Δρ_max = 0.34 e Å⁻³
2479 reflections	Δρ_min = −0.27 e Å⁻³
208 parameters

Special details top

Experimental. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm, CrysAlisPro (Agilent Technologies, 2010)

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
N1	−0.00300 (17)	0.11252 (9)	0.00877 (13)	0.0508 (4)
N2	−0.40823 (18)	−0.06469 (10)	0.32518 (16)	0.0606 (4)
O1	−0.45120 (19)	−0.11644 (11)	0.24495 (19)	0.0981 (6)
O2	−0.4868 (2)	−0.04523 (13)	0.39422 (19)	0.1103 (7)
C2	−0.26031 (19)	−0.02163 (10)	0.33128 (15)	0.0474 (4)
C4	−0.0688 (2)	0.26406 (11)	0.22420 (17)	0.0546 (5)
H4	−0.0133	0.2842	0.3020	0.066*
C5	−0.1638 (2)	−0.04885 (11)	0.26058 (16)	0.0522 (4)
H5	−0.1906	−0.0946	0.2115	0.063*
C6	0.01239 (19)	0.06249 (10)	0.33455 (14)	0.0447 (4)
C7	−0.0266 (2)	−0.00705 (11)	0.26372 (16)	0.0517 (4)
H7	0.0409	−0.0256	0.2178	0.062*
C8	−0.0060 (2)	0.20306 (10)	0.16888 (15)	0.0457 (4)
C9	0.14637 (19)	0.15610 (11)	0.21010 (15)	0.0465 (4)
C10	−0.2232 (2)	0.04547 (11)	0.40556 (16)	0.0512 (4)
H10	−0.2883	0.0621	0.4547	0.061*
C11	−0.0874 (2)	0.08749 (11)	0.40559 (15)	0.0490 (4)
H11	−0.0620	0.1335	0.4542	0.059*
C12	0.2623 (2)	0.05042 (12)	0.08696 (19)	0.0601 (5)
H12A	0.2364	0.0237	0.0063	0.072*
H12B	0.2832	0.0099	0.1521	0.072*
C13	−0.09041 (19)	0.17322 (10)	0.05232 (15)	0.0471 (4)
C14	0.1591 (2)	0.10996 (11)	0.33379 (15)	0.0503 (4)
H14A	0.2492	0.0737	0.3487	0.060*
H14B	0.1803	0.1480	0.4024	0.060*
C15	0.1269 (2)	0.10175 (10)	0.09656 (15)	0.0477 (4)
C16	0.2976 (2)	0.20659 (12)	0.22068 (19)	0.0603 (5)
H16A	0.2777	0.2442	0.1515	0.072*
H16B	0.3214	0.2372	0.2980	0.072*
C17	−0.2169 (2)	0.29487 (12)	0.1613 (2)	0.0623 (5)
H17	−0.2597	0.3370	0.1965	0.075*
C18	−0.3009 (2)	0.26371 (13)	0.04740 (19)	0.0636 (5)
H18	−0.4011	0.2842	0.0079	0.076*
C20	0.4094 (2)	0.10320 (15)	0.1016 (2)	0.0743 (6)
H20A	0.5013	0.0695	0.1060	0.089*
H20B	0.3941	0.1375	0.0286	0.089*
C22	−0.2390 (2)	0.20246 (13)	−0.00932 (17)	0.0588 (5)
H22	−0.2957	0.1817	−0.0864	0.071*
C23	0.4413 (2)	0.15502 (15)	0.2191 (2)	0.0717 (6)
H23A	0.4675	0.1208	0.2926	0.086*
H23B	0.5321	0.1894	0.2230	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0533 (8)	0.0569 (9)	0.0419 (7)	−0.0040 (7)	0.0123 (6)	−0.0011 (6)
N2	0.0532 (9)	0.0588 (10)	0.0678 (10)	−0.0018 (8)	0.0132 (8)	0.0018 (8)
O1	0.0780 (11)	0.0826 (11)	0.1356 (16)	−0.0255 (9)	0.0322 (10)	−0.0397 (11)
O2	0.0896 (12)	0.1405 (18)	0.1213 (14)	−0.0460 (12)	0.0636 (11)	−0.0443 (13)
C2	0.0457 (9)	0.0468 (9)	0.0473 (9)	0.0012 (7)	0.0087 (7)	0.0058 (8)
C4	0.0638 (11)	0.0508 (10)	0.0518 (10)	−0.0033 (9)	0.0201 (8)	−0.0001 (8)
C5	0.0608 (11)	0.0441 (10)	0.0511 (10)	−0.0018 (8)	0.0143 (8)	−0.0053 (8)
C6	0.0473 (9)	0.0479 (9)	0.0363 (8)	0.0040 (7)	0.0070 (7)	0.0062 (7)
C7	0.0590 (11)	0.0489 (10)	0.0510 (10)	0.0048 (8)	0.0214 (8)	−0.0013 (8)
C8	0.0490 (9)	0.0456 (9)	0.0435 (8)	−0.0043 (7)	0.0145 (7)	0.0031 (7)
C9	0.0444 (9)	0.0513 (10)	0.0426 (9)	−0.0050 (7)	0.0097 (7)	−0.0003 (7)
C10	0.0499 (10)	0.0577 (11)	0.0475 (9)	0.0047 (8)	0.0160 (8)	−0.0008 (8)
C11	0.0550 (10)	0.0481 (10)	0.0420 (8)	0.0014 (8)	0.0102 (7)	−0.0042 (7)
C12	0.0594 (11)	0.0656 (12)	0.0577 (11)	0.0043 (9)	0.0203 (9)	−0.0031 (9)
C13	0.0484 (9)	0.0517 (10)	0.0415 (9)	−0.0037 (8)	0.0124 (7)	0.0057 (7)
C14	0.0493 (9)	0.0576 (11)	0.0410 (9)	−0.0017 (8)	0.0070 (7)	0.0018 (8)
C15	0.0491 (9)	0.0507 (10)	0.0445 (9)	−0.0049 (8)	0.0151 (7)	0.0012 (7)
C16	0.0561 (11)	0.0632 (12)	0.0595 (11)	−0.0159 (9)	0.0121 (9)	−0.0002 (9)
C17	0.0689 (12)	0.0556 (11)	0.0716 (12)	0.0104 (9)	0.0346 (10)	0.0123 (10)
C18	0.0522 (11)	0.0729 (13)	0.0675 (12)	0.0094 (10)	0.0196 (9)	0.0230 (11)
C20	0.0561 (12)	0.0945 (16)	0.0787 (14)	0.0032 (11)	0.0295 (10)	0.0032 (12)
C22	0.0514 (10)	0.0734 (13)	0.0487 (10)	−0.0020 (9)	0.0090 (8)	0.0098 (9)
C23	0.0458 (10)	0.0912 (16)	0.0780 (14)	−0.0130 (10)	0.0165 (9)	0.0027 (12)

Geometric parameters (Å, º) top

N1—C13	1.429 (2)	C10—C11	1.377 (2)
N1—C15	1.290 (2)	C11—H11	0.9300
C2—N2	1.463 (2)	C12—H12A	0.9700
C2—C5	1.375 (2)	C12—H12B	0.9700
C2—C10	1.376 (2)	C12—C15	1.487 (2)
N2—O1	1.223 (2)	C12—C20	1.529 (3)
N2—O2	1.203 (2)	C13—C22	1.380 (2)
C4—H4	0.9300	C14—H14A	0.9700
C4—C8	1.377 (2)	C14—H14B	0.9700
C4—C17	1.389 (3)	C16—H16A	0.9700
C5—H5	0.9300	C16—H16B	0.9700
C5—C7	1.378 (2)	C16—C23	1.525 (3)
C6—C7	1.391 (2)	C17—H17	0.9300
C6—C11	1.387 (2)	C17—C18	1.378 (3)
C6—C14	1.508 (2)	C18—H18	0.9300
C7—H7	0.9300	C18—C22	1.384 (3)
C8—C9	1.503 (2)	C20—H20A	0.9700
C8—C13	1.394 (2)	C20—H20B	0.9700
C9—C14	1.550 (2)	C20—C23	1.525 (3)
C9—C15	1.523 (2)	C22—H22	0.9300
C9—C16	1.543 (2)	C23—H23A	0.9700
C10—H10	0.9300	C23—H23B	0.9700

C15—N1—C13	106.51 (14)	C8—C13—N1	111.75 (15)
C5—C2—N2	118.76 (16)	C22—C13—N1	126.84 (16)
C5—C2—C10	121.97 (16)	C22—C13—C8	121.40 (17)
C10—C2—N2	119.26 (16)	C6—C14—C9	114.16 (13)
O1—N2—C2	118.20 (17)	C6—C14—H14A	108.7
O2—N2—C2	119.10 (17)	C6—C14—H14B	108.7
O2—N2—O1	122.58 (18)	C9—C14—H14A	108.7
C8—C4—H4	120.7	C9—C14—H14B	108.7
C8—C4—C17	118.61 (18)	H14A—C14—H14B	107.6
C17—C4—H4	120.7	N1—C15—C9	114.72 (15)
C2—C5—H5	120.6	N1—C15—C12	125.36 (16)
C2—C5—C7	118.76 (16)	C12—C15—C9	119.35 (15)
C7—C5—H5	120.6	C9—C16—H16A	109.1
C7—C6—C14	120.87 (15)	C9—C16—H16B	109.1
C11—C6—C7	118.46 (16)	H16A—C16—H16B	107.9
C11—C6—C14	120.67 (15)	C23—C16—C9	112.31 (17)
C5—C7—C6	120.96 (16)	C23—C16—H16A	109.1
C5—C7—H7	119.5	C23—C16—H16B	109.1
C6—C7—H7	119.5	C4—C17—H17	119.7
C4—C8—C9	132.56 (16)	C18—C17—C4	120.70 (19)
C4—C8—C13	120.21 (16)	C18—C17—H17	119.7
C13—C8—C9	107.22 (14)	C17—C18—H18	119.4
C8—C9—C14	111.88 (13)	C17—C18—C22	121.25 (18)
C8—C9—C15	99.71 (13)	C22—C18—H18	119.4
C8—C9—C16	113.94 (15)	C12—C20—H20A	109.3
C15—C9—C14	113.58 (14)	C12—C20—H20B	109.3
C15—C9—C16	106.80 (14)	H20A—C20—H20B	107.9
C16—C9—C14	110.48 (13)	C23—C20—C12	111.70 (16)
C2—C10—H10	120.7	C23—C20—H20A	109.3
C2—C10—C11	118.51 (16)	C23—C20—H20B	109.3
C11—C10—H10	120.7	C13—C22—C18	117.80 (18)
C6—C11—H11	119.4	C13—C22—H22	121.1
C10—C11—C6	121.29 (16)	C18—C22—H22	121.1
C10—C11—H11	119.4	C16—C23—C20	111.76 (16)
H12A—C12—H12B	108.3	C16—C23—H23A	109.3
C15—C12—H12A	109.9	C16—C23—H23B	109.3
C15—C12—H12B	109.9	C20—C23—H23A	109.3
C15—C12—C20	108.74 (17)	C20—C23—H23B	109.3
C20—C12—H12A	109.9	H23A—C23—H23B	107.9
C20—C12—H12B	109.9

Experimental details

Crystal data
Chemical formula	C₁₉H₁₈N₂O₂
M_r	306.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	8.7266 (3), 16.6916 (6), 11.0857 (4)
β (°)	105.790 (4)
V (Å³)	1553.82 (10)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.5 × 0.4 × 0.3

Data collection
Diffractometer	Agilent Xcalibur Sapphire3 Gemini ultra diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.967, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4772, 2479, 2089
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.580

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.116, 1.04
No. of reflections	2479
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.27

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), publCIF (Westrip, 2010).

Acknowledgements

This work was supported by grants from the National Natural Science Fund (No. 2010 A480005).

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