9-Benzyl-9H-carbazole

Uludağ, N.; Ateş, M.; Tercan, B.; Ermiş, E.; Hökelek, T.

doi:10.1107/S1600536810012444

organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1077

https://doi.org/10.1107/S1600536810012444

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9-Benzyl-9H-carbazole

Nesimi Uludağ,^a Murat Ateş,^a Barış Tercan,^b Emel Ermiş ^c and Tuncer Hökelek ^d ^*

^aNamık Kemal University, Faculty of Arts and Sciences, Department of Chemistry, 59100 Tekirdağ, Turkey, ^bKarabük University, Department of Physics, 78050 Karabük, Turkey, ^cAnadolu University, Faculty of Science, Department of Chemistry, 26470 Yenibağlar, Eskişehir, Turkey, and ^dHacettepe University, Department of Physics, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 26 March 2010; accepted 2 April 2010; online 14 April 2010)

The asymmetric unit of the title compound, C₁₉H₁₅N, contains two crystallographically independent molecules. In both molecules, the planar carbazole moieties [maximum deviations = 0.037 (4) and 0.042 (3) Å] are oriented with respect to the adjacent benzene rings, at dihedral angles of 85.29 (8) and 89.89 (7)°, respectively. In the crystal structure, weak C—H⋯π interactions are observed involving the carbazole rings.

Related literature

For tetrahydrocarbazole systems present in the framework of a number of indole-type alkaloids of biological interest, see: Phillipson & Zenk (1980 ); Saxton (1983 ); Abraham (1975 ). For related structures, see: Hökelek et al. (1994 , 1998 , 1999 , 2004 , 2006 ); Patır et al. (1997 ); Hökelek & Patır (1999 , 2002 ); Çaylak et al. (2007 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₉H₁₅N
M_r = 257.32
Monoclinic, P 2₁ /c
a = 14.9305 (4) Å
b = 5.5612 (2) Å
c = 32.7916 (8) Å
β = 94.518 (3)°
V = 2714.27 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 100 K
0.27 × 0.15 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.981, T_max = 0.990
24870 measured reflections
6816 independent reflections
3384 reflections with I > 2σ(I)
R_int = 0.103

Refinement

R[F² > 2σ(F²)] = 0.076
wR(F²) = 0.210
S = 1.03
6816 reflections
474 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯Cg1′ⁱ	0.97 (4)	2.940 (4)	3.636 (5)	129.46 (5)
C10′—H10C⋯Cg1′ⁱⁱ	0.98 (3)	2.787 (4)	3.700 (5)	154.92 (4)
C4′—H4′⋯Cg3ⁱ	0.99 (4)	2.706 (4)	3.554 (4)	144.36 (5)
Symmetry codes: (i) $[-x, y-{{1\over 2}}, -z+{{1\over 2}}]$ ; (ii) x, y+1, z. Cg1′ and Cg3 are the centroids of the C1′–C4′/C4A′/C9A′ and C5A/C5–C8/C8A rings, respectively.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810012444/xu2745sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012444/xu2745Isup2.hkl

checkCIF report

Comment top

Tetrahydrocarbazole systems are present in the framework of a number of indole-type alkaloids of biological interest (Phillipson & Zenk, 1980; Saxton, 1983; Abraham, 1975). The structures of tricyclic, tetracyclic and pentacyclic ring systems with dithiolane and other substituents of the tetrahydrocarbazole core, have been the subject of much interest in our laboratory. These include 1,2,3,4-tetrahydrocarbazole-1-spiro-2'-[1,3]dithiolane, (II) (Hökelek et al., 1994), N-(2-methoxyethyl)-N-{2,3,4,9-tetrahydrospiro[1H-carbazole-1, 2-(1,3)dithiolane]-4-yl}benzene-sulfonamide, (III) (Patır et al., 1997), spiro[carbazole-1(2H),2'-[1,3]-dithiolan]-4(3H)-one, (IV) (Hökelek et al., 1998), 9-acetonyl-3-ethylidene-1,2,3,4-tetrahydrospiro[carbazole-1,2'-[1,3] dithiolan]-4-one, (V) (Hökelek et al., 1999), N-(2,2-dimethoxyethyl)-N -{9-methoxymethyl-1,2,3,4-tetrahydrospiro[carbazole-1,2'-[1,3]dithiolan] -4-yl}benzamide, (VI) (Hökelek & Patır, 1999), 3a,4,10,10 b-tetrahydro-2H -furo[2,3-a]carbazol-5(3H)-one, (VII) (Çaylak et al., 2007); also the pentacyclic compounds 6-ethyl-4-(2-methoxyethyl)-2,6-methano-5-oxo-hexahydro- pyrrolo(2,3-d)carbazole-1-spiro-2'-(1,3)dithiolane, (VIII) (Hökelek & Patır, 2002), N-(2-benzyloxyethyl)-4,7-dimethyl-6-(1,3-dithiolan-2-yl)-1,2, 3,4,5,6-hexahydro-1,5-methano-2-azocino[4,3-b]indol-2-one, (IX) (Hökelek et al., 2004) and 4-ethyl-6,6-ethylenedithio-2-(2-methoxyethyl)-7-methoxy- methylene-2,3,4,5,6,7-hexahydro-1,5-methano-1H-azocino[4,3-b]indol-3-one, (X) (Hökelek et al., 2006). The title compound, (I), may be considered as a synthetic precursor of tetracyclic indole alkaloids of biological interests. The present study was undertaken to ascertain its crystal structure.

The title compound consists of a carbazole skeleton with a benzyl group. Its asymmetric unit, (Fig. 1), contains two crystallographically independent molecules, where the bond lengths (Allen et al., 1987) and angles are within normal ranges, and generally agree with those in compounds (II)-(X). In all structures atom N9 is substituted.

An examination of the deviations from the least-squares planes through individual rings shows that rings A (C1—C4/C4a/C9a), B (C4a/C5a/C8a/N9/C9a), C (C5a/C5—C8/C8a), D (C11—C16) and A' (C1'-C4'/C4a'/C9a'), B' (C4a'/C5a'/ C8a'/N9'/C9a'), C' (C5a'/C5'-C8'/C8a'), D' (C11'-C16') are planar. The carbazole skeletons, containing the rings A, B, C and A', B', C' are also nearly coplanar [with a maximum deviations of 0.037 (4) and 0.042 (3) Å for atoms C2 and C7', respectively] with dihedral angles of A/B = 1.28 (10), A/C = 1.57 (9), B/C = 0.32 (7) ° and A'/B' = 0.94 (10), A'/C' = 2.37 (10), B'/C' = 1.72 (11) °. Rings D and D' are oriented with respect to the planar carbazole skeletons at dihedral angles of 85.29 (8) and 89.89 (7) °, respectively. Atoms C10 and C10' displaced by -0.109 (3), -0.005 (4) Å and -0.016 (3), -0.098 (3) Å from the planes of the corresponding carbazole skeletons and benzene rings, respectively.

In the crystal structure, three weak C—H···π interactions (Table 1) involving the carbazole rings are observed.

Related literature top

For tetrahydrocarbazole systems present in the framework of a number of indole-type alkaloids of biological interest, see: Phillipson & Zenk (1980); Saxton (1983); Abraham (1975). For related structures, see: Hökelek et al. (1994, 1998, 1999, 2004, 2006); Patır et al. (1997); Hökelek & Patır (1999, 2002); Çaylak et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, (I), sodium hydride (2.38 g, 59.85 mmol) was added to a solution of carbazole (5.00 g, 29.92 mmol) in dry tetrahydrofuran (200 ml) in several portions, and stirred at room temperature for 1 h under argon atmosphere. Then, benzylchloride (5.68 g, 44.88 mmol) was added and stirred at 343 K for 6 h. The reaction mixture was cooled in an ice bath, and hydrochloric acid (10%, 200 ml) was added. After the extraction with dichloromethane (300 ml), the organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated under reduced pressure. The residue was purified by column chromatograpy using silica gel and dichloromethane-petroleum ether (1:1), and the product was recrystallized from diethyl ether and cyclohexane mixture (1:1) (yield; 4.00 g, 80%, m.p. 388 K).

Structure description top

In the crystal structure, three weak C—H···π interactions (Table 1) involving the carbazole rings are observed.

For tetrahydrocarbazole systems present in the framework of a number of indole-type alkaloids of biological interest, see: Phillipson & Zenk (1980); Saxton (1983); Abraham (1975). For related structures, see: Hökelek et al. (1994, 1998, 1999, 2004, 2006); Patır et al. (1997); Hökelek & Patır (1999, 2002); Çaylak et al. (2007). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level.

9-Benzyl-9H-carbazole top

Crystal data top

C₁₉H₁₅N	F(000) = 1088
M_r = 257.32	D_x = 1.259 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1669 reflections
a = 14.9305 (4) Å	θ = 2.5–22.9°
b = 5.5612 (2) Å	µ = 0.07 mm⁻¹
c = 32.7916 (8) Å	T = 100 K
β = 94.518 (3)°	Block, colorless
V = 2714.27 (14) Å³	0.27 × 0.15 × 0.14 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	6816 independent reflections
Radiation source: fine-focus sealed tube	3384 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.103
φ and ω scans	θ_max = 28.4°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −19→18
T_min = 0.981, T_max = 0.990	k = −7→7
24870 measured reflections	l = −42→43

Refinement top

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)] = 0.076	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.210	w = 1/[σ²(F_o²) + (0.0918P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
6816 reflections	Δρ_max = 0.27 e Å⁻³
474 parameters	Δρ_min = −0.26 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: 0.0068 (11)

Crystal data top

C₁₉H₁₅N	V = 2714.27 (14) Å³
M_r = 257.32	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.9305 (4) Å	µ = 0.07 mm⁻¹
b = 5.5612 (2) Å	T = 100 K
c = 32.7916 (8) Å	0.27 × 0.15 × 0.14 mm
β = 94.518 (3)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	6816 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3384 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.990	R_int = 0.103
24870 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	0 restraints
wR(F²) = 0.210	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.27 e Å⁻³
6816 reflections	Δρ_min = −0.26 e Å⁻³
474 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.5696 (2)	0.6160 (7)	0.83884 (11)	0.0399 (9)
H1	0.536 (2)	0.451 (6)	0.8446 (9)	0.042 (9)*
C2	0.5654 (2)	0.7192 (8)	0.80036 (11)	0.0495 (10)
H2	0.524 (2)	0.643 (6)	0.7769 (10)	0.040 (9)*
C3	0.6133 (2)	0.9241 (8)	0.79216 (10)	0.0486 (10)
H3	0.6077	0.9890	0.7659	0.058*
C4	0.6692 (2)	1.0341 (7)	0.82209 (10)	0.0364 (8)
H4	0.702 (2)	1.169 (6)	0.8155 (9)	0.030 (9)*
C4A	0.67613 (19)	0.9336 (6)	0.86118 (9)	0.0286 (7)
C5	0.7898 (2)	1.1740 (6)	0.91002 (10)	0.0286 (7)
H5	0.807 (2)	1.303 (6)	0.8898 (10)	0.052 (10)*
C5A	0.72814 (19)	0.9919 (5)	0.89881 (8)	0.0244 (6)
C6	0.8284 (2)	1.1795 (6)	0.94938 (10)	0.0308 (7)
H6	0.870 (2)	1.308 (6)	0.9577 (9)	0.045 (10)*
C7	0.8064 (2)	1.0064 (6)	0.97798 (10)	0.0294 (7)
H7	0.836 (2)	1.010 (6)	1.0055 (10)	0.037 (9)*
C8	0.7450 (2)	0.8268 (6)	0.96804 (9)	0.0284 (7)
H8	0.727 (2)	0.696 (6)	0.9883 (10)	0.045 (9)*
C8A	0.70640 (19)	0.8208 (5)	0.92781 (9)	0.0243 (6)
N9	0.64413 (16)	0.6597 (4)	0.90964 (7)	0.0263 (6)
C9A	0.62622 (19)	0.7261 (5)	0.86924 (9)	0.0274 (7)
C10	0.5991 (2)	0.4654 (6)	0.92981 (11)	0.0314 (7)
H10A	0.604 (2)	0.313 (6)	0.9142 (9)	0.036 (9)*
H10B	0.632 (2)	0.433 (5)	0.9553 (9)	0.031 (9)*
C11	0.50251 (19)	0.5224 (5)	0.93644 (9)	0.0260 (7)
C12	0.4798 (2)	0.7304 (6)	0.95693 (10)	0.0335 (8)
H12	0.527 (2)	0.852 (6)	0.9672 (10)	0.048 (10)*
C13	0.3908 (2)	0.7795 (6)	0.96297 (10)	0.0348 (8)
H13	0.375 (2)	0.931 (6)	0.9762 (10)	0.052 (10)*
C14	0.3239 (2)	0.6231 (6)	0.94863 (9)	0.0311 (7)
H14	0.263 (3)	0.675 (6)	0.9533 (10)	0.054 (11)*
C15	0.3458 (2)	0.4166 (6)	0.92833 (10)	0.0337 (8)
H15	0.296 (2)	0.295 (6)	0.9180 (9)	0.038 (9)*
C16	0.4348 (2)	0.3666 (6)	0.92232 (10)	0.0305 (7)
H16	0.4532 (19)	0.217 (5)	0.9088 (8)	0.027 (8)*
C1'	0.9099 (2)	0.8115 (6)	0.57706 (9)	0.0291 (7)
H1'	0.865 (2)	0.673 (5)	0.5719 (8)	0.032 (8)*
C2'	0.9229 (2)	0.9787 (6)	0.54711 (10)	0.0333 (8)
H2'	0.883 (2)	0.951 (5)	0.5217 (9)	0.029 (8)*
C3'	0.9879 (2)	1.1600 (6)	0.55305 (10)	0.0345 (8)
H3'	0.998 (2)	1.271 (6)	0.5318 (9)	0.035 (9)*
C4'	1.0415 (2)	1.1763 (6)	0.58923 (10)	0.0294 (7)
H4'	1.085 (3)	1.310 (7)	0.5918 (11)	0.063 (12)*
C4A'	1.02988 (19)	1.0096 (5)	0.61992 (9)	0.0258 (7)
C5'	1.1437 (2)	1.0841 (6)	0.68366 (10)	0.0325 (8)
H5'	1.177 (2)	1.222 (6)	0.6724 (9)	0.041 (9)*
C5A'	1.07331 (19)	0.9688 (5)	0.66042 (9)	0.0258 (7)
C6'	1.1713 (2)	0.9928 (7)	0.72151 (10)	0.0399 (8)
H6'	1.223 (3)	1.067 (7)	0.7361 (11)	0.061 (11)*
C7'	1.1302 (2)	0.7899 (6)	0.73662 (9)	0.0374 (8)
H7'	1.1509	0.7306	0.7622	0.045*
C8'	1.0594 (2)	0.6735 (6)	0.71486 (9)	0.0305 (7)
H8'	1.028 (2)	0.519 (6)	0.7270 (9)	0.043 (9)*
C8A'	1.03215 (19)	0.7642 (5)	0.67661 (8)	0.0249 (7)
N9'	0.96646 (16)	0.6806 (4)	0.64747 (7)	0.0255 (6)
C9A'	0.96460 (19)	0.8272 (5)	0.61347 (9)	0.0258 (7)
C10'	0.9071 (2)	0.4776 (5)	0.65181 (10)	0.0267 (7)
H10C	0.910 (2)	0.373 (6)	0.6277 (10)	0.042 (10)*
H10D	0.932 (2)	0.372 (5)	0.6747 (9)	0.033 (9)*
C11'	0.81229 (19)	0.5454 (5)	0.66032 (8)	0.0241 (6)
C12'	0.7931 (2)	0.7589 (6)	0.67972 (9)	0.0314 (7)
H12'	0.847 (2)	0.884 (6)	0.6895 (9)	0.047 (10)*
C13'	0.7052 (2)	0.8047 (7)	0.68913 (11)	0.0401 (9)
H13'	0.690 (2)	0.951 (6)	0.7018 (9)	0.042 (10)*
C14'	0.6376 (2)	0.6429 (7)	0.67937 (12)	0.0481 (10)
H14'	0.576 (3)	0.680 (7)	0.6901 (12)	0.075 (13)*
C15'	0.6564 (2)	0.4339 (7)	0.65933 (12)	0.0462 (10)
H15'	0.605 (3)	0.327 (6)	0.6506 (10)	0.054 (11)*
C16'	0.7434 (2)	0.3849 (6)	0.64961 (10)	0.0350 (8)
H16'	0.758 (2)	0.242 (6)	0.6364 (10)	0.041 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0220 (17)	0.053 (2)	0.045 (2)	−0.0002 (16)	0.0017 (14)	−0.0173 (18)
C2	0.029 (2)	0.085 (3)	0.034 (2)	0.009 (2)	−0.0012 (16)	−0.015 (2)
C3	0.031 (2)	0.086 (3)	0.0284 (18)	0.015 (2)	0.0033 (15)	0.0019 (19)
C4	0.0239 (18)	0.055 (2)	0.0316 (19)	0.0087 (17)	0.0072 (14)	0.0043 (17)
C4A	0.0183 (15)	0.0393 (18)	0.0288 (17)	0.0061 (14)	0.0056 (12)	−0.0019 (14)
C5	0.0219 (16)	0.0278 (16)	0.0372 (19)	0.0003 (13)	0.0090 (13)	−0.0011 (14)
C5A	0.0196 (15)	0.0290 (15)	0.0254 (15)	0.0057 (13)	0.0075 (12)	0.0015 (13)
C6	0.0225 (17)	0.0326 (17)	0.0379 (19)	−0.0054 (14)	0.0062 (14)	−0.0049 (15)
C7	0.0226 (16)	0.0366 (17)	0.0291 (17)	−0.0006 (14)	0.0024 (13)	−0.0058 (15)
C8	0.0247 (17)	0.0331 (16)	0.0280 (17)	0.0018 (14)	0.0059 (13)	0.0017 (14)
C8A	0.0172 (15)	0.0259 (15)	0.0308 (16)	0.0018 (12)	0.0074 (12)	−0.0026 (13)
N9	0.0188 (13)	0.0243 (12)	0.0358 (15)	−0.0004 (10)	0.0034 (10)	−0.0009 (11)
C9A	0.0153 (15)	0.0365 (17)	0.0305 (17)	0.0066 (13)	0.0030 (12)	−0.0057 (14)
C10	0.0203 (16)	0.0262 (17)	0.048 (2)	−0.0022 (13)	0.0043 (15)	0.0017 (16)
C11	0.0223 (16)	0.0238 (14)	0.0321 (16)	0.0021 (13)	0.0025 (12)	0.0043 (13)
C12	0.0273 (18)	0.0325 (17)	0.0408 (19)	−0.0022 (15)	0.0035 (14)	−0.0034 (15)
C13	0.0306 (19)	0.0331 (18)	0.042 (2)	0.0030 (15)	0.0097 (14)	−0.0013 (16)
C14	0.0210 (17)	0.0367 (18)	0.0360 (18)	0.0040 (15)	0.0046 (13)	0.0088 (15)
C15	0.0236 (17)	0.0416 (19)	0.0357 (18)	−0.0096 (15)	0.0011 (14)	0.0044 (16)
C16	0.0252 (17)	0.0284 (17)	0.0378 (19)	−0.0031 (14)	0.0021 (13)	−0.0021 (14)
C1'	0.0205 (16)	0.0371 (18)	0.0298 (17)	0.0043 (14)	0.0024 (13)	0.0036 (15)
C2'	0.0202 (16)	0.048 (2)	0.0318 (18)	0.0100 (15)	0.0054 (13)	0.0058 (16)
C3'	0.0312 (19)	0.0403 (19)	0.0336 (19)	0.0107 (15)	0.0126 (15)	0.0119 (16)
C4'	0.0245 (17)	0.0282 (16)	0.0376 (19)	0.0042 (14)	0.0154 (14)	0.0013 (14)
C4A'	0.0193 (15)	0.0261 (15)	0.0333 (16)	0.0024 (13)	0.0099 (12)	−0.0013 (13)
C5'	0.0248 (17)	0.0365 (18)	0.0378 (19)	−0.0033 (15)	0.0115 (14)	−0.0101 (15)
C5A'	0.0202 (15)	0.0294 (15)	0.0287 (16)	0.0016 (13)	0.0081 (12)	−0.0049 (13)
C6'	0.0304 (19)	0.054 (2)	0.0357 (19)	−0.0029 (18)	0.0048 (15)	−0.0164 (18)
C7'	0.0321 (19)	0.055 (2)	0.0249 (17)	0.0100 (17)	0.0017 (13)	−0.0072 (16)
C8'	0.0268 (17)	0.0378 (18)	0.0274 (17)	0.0045 (14)	0.0042 (13)	0.0007 (15)
C8A'	0.0199 (15)	0.0291 (16)	0.0263 (16)	0.0024 (13)	0.0060 (12)	−0.0036 (13)
N9'	0.0202 (13)	0.0284 (13)	0.0280 (13)	−0.0010 (11)	0.0030 (10)	0.0035 (11)
C9A'	0.0197 (15)	0.0291 (15)	0.0293 (16)	0.0026 (13)	0.0070 (12)	0.0011 (13)
C10'	0.0214 (16)	0.0252 (15)	0.0344 (18)	−0.0027 (13)	0.0075 (13)	−0.0020 (15)
C11'	0.0229 (15)	0.0278 (15)	0.0219 (15)	0.0012 (13)	0.0041 (12)	0.0057 (13)
C12'	0.0312 (18)	0.0352 (18)	0.0288 (17)	0.0031 (15)	0.0092 (13)	0.0028 (14)
C13'	0.039 (2)	0.043 (2)	0.042 (2)	0.0130 (18)	0.0205 (16)	0.0135 (18)
C14'	0.027 (2)	0.063 (3)	0.056 (2)	0.0101 (19)	0.0134 (17)	0.031 (2)
C15'	0.0245 (19)	0.051 (2)	0.062 (2)	−0.0046 (18)	−0.0030 (17)	0.022 (2)
C16'	0.0276 (18)	0.0325 (18)	0.044 (2)	−0.0049 (15)	−0.0042 (15)	0.0083 (16)

Geometric parameters (Å, º) top

C1—C2	1.383 (5)	C1'—C2'	1.377 (4)
C1—H1	1.07 (3)	C1'—H1'	1.03 (3)
C2—H2	1.04 (3)	C2'—H2'	0.99 (3)
C3—C2	1.383 (6)	C3'—C2'	1.403 (5)
C3—H3	0.9300	C3'—H3'	0.95 (3)
C4—C3	1.380 (5)	C4'—C3'	1.381 (5)
C4—H4	0.93 (3)	C4'—H4'	0.99 (4)
C4A—C4	1.395 (4)	C4A'—C4'	1.389 (4)
C5—H5	1.02 (4)	C4A'—C5A'	1.449 (4)
C5A—C4A	1.442 (4)	C5'—C6'	1.374 (5)
C5A—C5	1.398 (4)	C5'—H5'	1.00 (3)
C6—C5	1.372 (4)	C5A'—C5'	1.404 (4)
C6—C7	1.401 (4)	C6'—H6'	0.97 (4)
C6—H6	0.97 (4)	C7'—C6'	1.394 (5)
C7—H7	0.97 (3)	C7'—H7'	0.9300
C8—C7	1.377 (4)	C8'—C7'	1.387 (4)
C8—H8	1.04 (3)	C8'—H8'	1.07 (3)
C8A—C5A	1.401 (4)	C8A'—C5A'	1.416 (4)
C8A—C8	1.398 (4)	C8A'—C8'	1.383 (4)
N9—C8A	1.391 (4)	N9'—C8A'	1.394 (4)
N9—C9A	1.381 (4)	N9'—C9A'	1.379 (4)
N9—C10	1.458 (4)	N9'—C10'	1.450 (4)
C9A—C1	1.396 (4)	C9A'—C1'	1.395 (4)
C9A—C4A	1.410 (4)	C9A'—C4A'	1.411 (4)
C10—C11	1.509 (4)	C10'—C11'	1.511 (4)
C10—H10A	1.00 (3)	C10'—H10C	0.98 (3)
C10—H10B	0.95 (3)	C10'—H10D	1.00 (3)
C11—C12	1.393 (4)	C11'—C12'	1.388 (4)
C11—C16	1.384 (4)	C11'—C16'	1.386 (4)
C12—H12	1.02 (4)	C12'—C13'	1.395 (4)
C13—C12	1.386 (4)	C12'—H12'	1.09 (3)
C13—H13	0.98 (3)	C13'—H13'	0.95 (3)
C14—C13	1.379 (5)	C14'—C13'	1.371 (5)
C14—C15	1.379 (5)	C14'—C15'	1.375 (6)
C14—H14	0.99 (4)	C14'—H14'	1.03 (4)
C15—C16	1.387 (4)	C15'—H15'	1.00 (4)
C15—H15	1.04 (3)	C16'—C15'	1.388 (5)
C16—H16	0.99 (3)	C16'—H16'	0.94 (3)

C2—C1—C9A	116.8 (4)	C2'—C1'—C9A'	117.5 (3)
C2—C1—H1	122.0 (17)	C2'—C1'—H1'	121.1 (16)
C9A—C1—H1	121.0 (17)	C9A'—C1'—H1'	121.2 (16)
C1—C2—H2	119.3 (18)	C1'—C2'—C3'	121.4 (3)
C3—C2—C1	122.1 (3)	C1'—C2'—H2'	112.6 (17)
C3—C2—H2	118.6 (18)	C3'—C2'—H2'	126.0 (17)
C2—C3—H3	119.3	C2'—C3'—H3'	120.5 (19)
C4—C3—C2	121.3 (3)	C4'—C3'—C2'	121.0 (3)
C4—C3—H3	119.3	C4'—C3'—H3'	118.5 (19)
C3—C4—C4A	118.2 (4)	C3'—C4'—C4A'	118.8 (3)
C3—C4—H4	119.5 (19)	C3'—C4'—H4'	117 (2)
C4A—C4—H4	122.2 (19)	C4A'—C4'—H4'	124 (2)
C4—C4A—C9A	119.9 (3)	C4'—C4A'—C5A'	134.1 (3)
C4—C4A—C5A	133.8 (3)	C4'—C4A'—C9A'	119.7 (3)
C9A—C4A—C5A	106.3 (3)	C9A'—C4A'—C5A'	106.2 (2)
C5A—C5—H5	122 (2)	C5A'—C5'—H5'	121.5 (18)
C6—C5—C5A	118.8 (3)	C6'—C5'—C5A'	118.7 (3)
C6—C5—H5	119 (2)	C6'—C5'—H5'	119.6 (19)
C5—C5A—C4A	133.4 (3)	C5'—C5A'—C4A'	133.5 (3)
C5—C5A—C8A	119.8 (3)	C5'—C5A'—C8A'	119.5 (3)
C8A—C5A—C4A	106.8 (3)	C8A'—C5A'—C4A'	107.1 (2)
C5—C6—C7	120.7 (3)	C5'—C6'—C7'	120.7 (3)
C5—C6—H6	119.5 (19)	C5'—C6'—H6'	117 (2)
C7—C6—H6	119.8 (19)	C7'—C6'—H6'	122 (2)
C6—C7—H7	120 (2)	C6'—C7'—H7'	118.9
C8—C7—C6	121.8 (3)	C8'—C7'—C6'	122.3 (3)
C8—C7—H7	118.5 (19)	C8'—C7'—H7'	118.9
C7—C8—C8A	117.2 (3)	C7'—C8'—H8'	121.4 (17)
C7—C8—H8	124.1 (18)	C8A'—C8'—C7'	117.0 (3)
C8A—C8—H8	118.6 (19)	C8A'—C8'—H8'	121.6 (17)
N9—C8A—C5A	109.2 (2)	N9'—C8A'—C5A'	108.3 (2)
N9—C8A—C8	129.2 (3)	C8'—C8A'—C5A'	121.8 (3)
C8—C8A—C5A	121.6 (3)	C8'—C8A'—N9'	129.9 (3)
C8A—N9—C10	126.8 (3)	C8A'—N9'—C10'	126.5 (2)
C9A—N9—C8A	108.1 (2)	C9A'—N9'—C8A'	109.0 (2)
C9A—N9—C10	124.9 (3)	C9A'—N9'—C10'	124.5 (2)
N9—C9A—C1	128.9 (3)	C1'—C9A'—C4A'	121.6 (3)
N9—C9A—C4A	109.5 (3)	N9'—C9A'—C1'	128.9 (3)
C1—C9A—C4A	121.6 (3)	N9'—C9A'—C4A'	109.5 (2)
N9—C10—C11	112.9 (2)	N9'—C10'—C11'	114.4 (2)
N9—C10—H10B	108.5 (19)	N9'—C10'—H10C	108.6 (19)
N9—C10—H10A	109.9 (18)	N9'—C10'—H10D	109.6 (18)
C11—C10—H10B	110.0 (18)	C11'—C10'—H10C	113.1 (19)
C11—C10—H10A	111.5 (18)	C11'—C10'—H10D	108.0 (18)
H10B—C10—H10A	104 (3)	H10C—C10'—H10D	103 (2)
C12—C11—C10	121.0 (3)	C12'—C11'—C10'	121.9 (3)
C16—C11—C10	120.1 (3)	C16'—C11'—C10'	118.7 (3)
C16—C11—C12	118.9 (3)	C16'—C11'—C12'	119.4 (3)
C11—C12—H12	121.7 (19)	C11'—C12'—C13'	119.3 (3)
C13—C12—C11	120.3 (3)	C11'—C12'—H12'	120.4 (18)
C13—C12—H12	118.0 (19)	C13'—C12'—H12'	120.1 (18)
C12—C13—H13	120 (2)	C12'—C13'—H13'	121 (2)
C14—C13—C12	120.3 (3)	C14'—C13'—C12'	121.1 (4)
C14—C13—H13	120 (2)	C14'—C13'—H13'	118 (2)
C13—C14—C15	119.8 (3)	C13'—C14'—C15'	119.4 (3)
C13—C14—H14	115 (2)	C13'—C14'—H14'	117 (2)
C15—C14—H14	125 (2)	C15'—C14'—H14'	124 (2)
C14—C15—C16	120.1 (3)	C14'—C15'—C16'	120.4 (4)
C14—C15—H15	120.5 (18)	C14'—C15'—H15'	117 (2)
C16—C15—H15	119.3 (18)	C16'—C15'—H15'	122 (2)
C11—C16—C15	120.7 (3)	C11'—C16'—C15'	120.3 (3)
C11—C16—H16	117.0 (17)	C11'—C16'—H16'	118 (2)
C15—C16—H16	122.3 (18)	C15'—C16'—H16'	122 (2)

C9A—C1—C2—C3	−1.1 (5)	C9A'—C1'—C2'—C3'	−0.8 (5)
C4—C3—C2—C1	1.0 (6)	C4'—C3'—C2'—C1'	0.3 (5)
C4A—C4—C3—C2	−0.2 (5)	C4A'—C4'—C3'—C2'	−0.2 (4)
C5A—C4A—C4—C3	177.8 (3)	C5A'—C4A'—C4'—C3'	178.8 (3)
C9A—C4A—C4—C3	−0.5 (5)	C9A'—C4A'—C4'—C3'	0.5 (4)
C5—C5A—C4A—C4	1.2 (6)	C4'—C4A'—C5A'—C5'	0.0 (6)
C5—C5A—C4A—C9A	179.7 (3)	C4'—C4A'—C5A'—C8A'	−178.6 (3)
C8A—C5A—C4A—C4	−179.4 (3)	C9A'—C4A'—C5A'—C5'	178.5 (3)
C8A—C5A—C4A—C9A	−0.9 (3)	C9A'—C4A'—C5A'—C8A'	−0.2 (3)
C8A—C5A—C5—C6	0.6 (4)	C5A'—C5'—C6'—C7'	−0.1 (5)
C4A—C5A—C5—C6	179.9 (3)	C4A'—C5A'—C5'—C6'	−177.8 (3)
C7—C6—C5—C5A	−0.2 (4)	C8A'—C5A'—C5'—C6'	0.7 (4)
C5—C6—C7—C8	−0.7 (5)	C8'—C7'—C6'—C5'	−1.0 (5)
C8A—C8—C7—C6	1.2 (4)	C8A'—C8'—C7'—C6'	1.5 (5)
C8—C8A—C5A—C4A	−179.5 (3)	N9'—C8A'—C5A'—C4A'	0.3 (3)
C8—C8A—C5A—C5	0.0 (4)	N9'—C8A'—C5A'—C5'	−178.5 (3)
N9—C8A—C5A—C4A	0.4 (3)	C8'—C8A'—C5A'—C4A'	178.7 (3)
N9—C8A—C5A—C5	179.9 (2)	C8'—C8A'—C5A'—C5'	−0.1 (4)
N9—C8A—C8—C7	179.2 (3)	N9'—C8A'—C8'—C7'	177.1 (3)
C5A—C8A—C8—C7	−0.8 (4)	C5A'—C8A'—C8'—C7'	−0.9 (4)
C9A—N9—C8A—C5A	0.2 (3)	C9A'—N9'—C8A'—C5A'	−0.3 (3)
C9A—N9—C8A—C8	−179.8 (3)	C9A'—N9'—C8A'—C8'	−178.6 (3)
C10—N9—C8A—C5A	−175.1 (3)	C10'—N9'—C8A'—C8'	3.0 (5)
C10—N9—C8A—C8	4.8 (5)	C10'—N9'—C8A'—C5A'	−178.7 (3)
C8A—N9—C9A—C1	178.6 (3)	C8A'—N9'—C9A'—C1'	179.9 (3)
C8A—N9—C9A—C4A	−0.8 (3)	C8A'—N9'—C9A'—C4A'	0.2 (3)
C10—N9—C9A—C1	−5.9 (5)	C10'—N9'—C9A'—C1'	−1.7 (5)
C10—N9—C9A—C4A	174.7 (3)	C10'—N9'—C9A'—C4A'	178.6 (3)
C8A—N9—C10—C11	104.4 (3)	C8A'—N9'—C10'—C11'	102.9 (3)
C9A—N9—C10—C11	−70.2 (4)	C9A'—N9'—C10'—C11'	−75.2 (4)
N9—C9A—C1—C2	−178.9 (3)	N9'—C9A'—C1'—C2'	−178.5 (3)
C4A—C9A—C1—C2	0.5 (5)	C4A'—C9A'—C1'—C2'	1.1 (4)
N9—C9A—C4A—C4	179.8 (3)	N9'—C9A'—C4A'—C4'	178.7 (2)
N9—C9A—C4A—C5A	1.1 (3)	N9'—C9A'—C4A'—C5A'	0.0 (3)
C1—C9A—C4A—C4	0.3 (4)	C1'—C9A'—C4A'—C4'	−1.0 (4)
C1—C9A—C4A—C5A	−178.4 (3)	C1'—C9A'—C4A'—C5A'	−179.7 (3)
N9—C10—C11—C12	−54.4 (4)	N9'—C10'—C11'—C16'	155.3 (3)
N9—C10—C11—C16	125.9 (3)	N9'—C10'—C11'—C12'	−26.9 (4)
C10—C11—C12—C13	−179.6 (3)	C10'—C11'—C12'—C13'	−175.9 (3)
C16—C11—C12—C13	0.0 (5)	C16'—C11'—C12'—C13'	1.9 (4)
C10—C11—C16—C15	179.8 (3)	C10'—C11'—C16'—C15'	175.8 (3)
C12—C11—C16—C15	0.2 (5)	C12'—C11'—C16'—C15'	−2.0 (5)
C14—C13—C12—C11	−0.2 (5)	C11'—C12'—C13'—C14'	−0.3 (5)
C15—C14—C13—C12	0.2 (5)	C15'—C14'—C13'—C12'	−1.1 (5)
C13—C14—C15—C16	−0.1 (5)	C13'—C14'—C15'—C16'	1.0 (5)
C14—C15—C16—C11	−0.1 (5)	C11'—C16'—C15'—C14'	0.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cg1′ⁱ	0.97 (4)	2.940 (4)	3.636 (5)	129.46 (5)
C10′—H10C···Cg1′ⁱⁱ	0.98 (3)	2.787 (4)	3.700 (5)	154.92 (4)
C4′—H4′···Cg3ⁱ	0.99 (4)	2.706 (4)	3.554 (4)	144.36 (5)

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₅N
M_r	257.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	14.9305 (4), 5.5612 (2), 32.7916 (8)
β (°)	94.518 (3)
V (Å³)	2714.27 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.27 × 0.15 × 0.14

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.981, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	24870, 6816, 3384
R_int	0.103
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.210, 1.03
No. of reflections	6816
No. of parameters	474
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.26

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cg1'ⁱ	0.97 (4)	2.940 (4)	3.636 (5)	129.46 (5)
C10'—H10C···Cg1'ⁱⁱ	0.98 (3)	2.787 (4)	3.700 (5)	154.92 (4)
C4'—H4'···Cg3ⁱ	0.99 (4)	2.706 (4)	3.554 (4)	144.36 (5)

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, y+1, z.

Acknowledgements

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of the X-ray diffractometer.

References

Abraham, D. J. (1975). The Catharanthus Alkaloids, edited by W. I. Taylor & N. R. Fransworth, chs. 7 and 8. New York: Marcel Decker. Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT . Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Çaylak, N., Hökelek, T., Uludağ, N. & Patır, S. (2007). Acta Cryst. E63, o3913–o3914. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Hökelek, T., Gündüz, H., Patır, S. & Uludağ, N. (1998). Acta Cryst. C54, 1297–1299. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T. & Patır, S. (1999). Acta Cryst. C55, 675–677. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T. & Patır, S. (2002). Acta Cryst. E58, o374–o376. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Patır, S., Gülce, A. & Okay, G. (1994). Acta Cryst. C50, 450–453. CSD CrossRef Web of Science IUCr Journals Google Scholar
Hökelek, T., Patır, S. & Uludağ, N. (1999). Acta Cryst. C55, 114–116. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Uludağ, N. & Patır, S. (2004). Acta Cryst. E60, o25–o27. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Uludağ, N. & Patır, S. (2006). Acta Cryst. E62, o791–o793. Web of Science CSD CrossRef IUCr Journals Google Scholar
Patır, S., Okay, G., Gülce, A., Salih, B. & Hökelek, T. (1997). J. Heterocycl. Chem. 34, 1239–1242. CAS Google Scholar
Phillipson, J. D. & Zenk, M. H. (1980). Indole and Biogenetically Related Alkaloids, ch. 3. New York: Academic Press. Google Scholar
Saxton, J. E. (1983). Editor. Heterocyclic Compounds, Vol. 25, The Monoterpenoid Indole Alkaloids, chs. 8 and 11. New York: Wiley. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar