Literature DB >> 21582955

Ethyl 1-oxo-1,2,3,4-tetra-hydro-9H-carbazole-3-carboxyl-ate.

Tuncer Hökelek, Hakan Dal, Barış Tercan, Mustafa Göçmentürk, Yavuz Ergün.

Abstract

The title compound, C(15)H(15)NO(3), contains a carbazole skeleton with an ethoxy-carbonyl group at the 3 position. In the indole ring system, the benzene and pyrrole rings are nearly coplanar, forming a dihedral angle of 1.95 (8)°. The cyclo-hexenone ring has an envelope conformation. In the crystal structure, pairs of strong N-H⋯O hydrogen bonds link the mol-ecules into centrosymmetric dimers with R(2) (2)(10) ring motifs. π-π contacts between parallel pyrrole rings [centroid-centroid distance = 3.776 (2) Å] may further stabilize the structure. A weak C-H⋯π inter-action is also observed.

Entities: Chemical Disease Gene Species

Year: 2009 PMID： 21582955 PMCID： PMC2969242 DOI： 10.1107/S160053680902385X

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For tetrahydrocarbazole derivatives as synthetic precursors of cyclic indole-type alkaloids of biological interest, see: Abraham (1975 ▶); Phillipson & Zenk (1980 ▶); Saxton (1983 ▶). The title compound is used in the synthesis of a precursor for the synthesis of the anti-tumor drug ellipticine (Ergün et al., 2004 ▶). Murraya L. (Rutaceae) is a genus of shrubs or small trees from Southern Asia (Chang, 1977 ▶) from which carbazole alkaloids have been isolated (Chakraborty & Roy, 1991 ▶). For the biological activity of carbazole alkaloids, see: Kondo et al. (1986 ▶); Te Paske et al. (1989a ▶,b ▶). For related structures, see: Çaylak et al. (2007 ▶); Uludağ et al. (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶). For ring-motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C15H15NO3 M = 257.28 Monoclinic, a = 5.6811 (3) Å b = 8.7378 (5) Å c = 24.8310 (14) Å β = 93.208 (4)° V = 1230.69 (12) Å3 Z = 4 Mo Kα radiation μ = 0.10 mm−1 T = 100 K 0.45 × 0.20 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.958, T max = 0.983 9148 measured reflections 3004 independent reflections 2145 reflections with I > 2σ(I) R int = 0.059

Refinement

R[F 2 > 2σ(F 2)] = 0.075 wR(F 2) = 0.221 S = 1.05 3004 reflections 177 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 1.25 e Å−3 Δρmin = −0.42 e Å−3 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 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶). Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902385X/xu2543sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S160053680902385X/xu2543Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₅H₁₅NO₃	F(000) = 544
M_r = 257.28	D_x = 1.389 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3480 reflections
a = 5.6811 (3) Å	θ = 1.6–28.3°
b = 8.7378 (5) Å	µ = 0.10 mm⁻¹
c = 24.8310 (14) Å	T = 100 K
β = 93.208 (4)°	Rod-shaped, colorless
V = 1230.69 (12) Å³	0.45 × 0.20 × 0.15 mm
Z = 4

Bruker Kappa APEXII CCD area-detector diffractometer	3004 independent reflections
Radiation source: fine-focus sealed tube	2145 reflections with I > 2σ(I)
graphite	R_int = 0.059
φ and ω scans	θ_max = 28.3°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −7→7
T_min = 0.958, T_max = 0.983	k = −11→9
9148 measured reflections	l = −32→28

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.221	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.1083P)² + 1.2571P] where P = (F_o² + 2F_c²)/3
3004 reflections	(Δ/σ)_max < 0.001
177 parameters	Δρ_max = 1.25 e Å⁻³
0 restraints	Δρ_min = −0.42 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	U_iso*/U_eq
O1	0.4546 (3)	0.0609 (2)	0.42291 (7)	0.0294 (5)
O2	−0.0619 (5)	0.3051 (4)	0.27554 (9)	0.0775 (11)
O3	−0.2959 (5)	0.4520 (3)	0.32045 (8)	0.0603 (8)
C1	0.2768 (4)	0.1407 (3)	0.42209 (10)	0.0245 (5)
C2	0.1783 (5)	0.2133 (4)	0.37051 (10)	0.0316 (6)
H2A	0.1988	0.1406	0.3405	0.038*
H2B	0.2727	0.3056	0.3634	0.038*
C3	−0.0831 (5)	0.2597 (4)	0.36991 (11)	0.0355 (7)
H3	−0.1758	0.1623	0.3689	0.043*
C4	−0.1525 (4)	0.3454 (3)	0.41897 (10)	0.0263 (6)
H4A	−0.0978	0.4527	0.4171	0.032*
H4B	−0.3264	0.3461	0.4202	0.032*
C4A	−0.0453 (4)	0.2708 (3)	0.46893 (10)	0.0229 (5)
C5	−0.2963 (4)	0.3489 (3)	0.54916 (10)	0.0270 (6)
H5	−0.4152	0.4041	0.5289	0.032*
C5A	−0.1107 (4)	0.2805 (3)	0.52332 (9)	0.0232 (5)
C6	−0.3046 (5)	0.3353 (3)	0.60418 (11)	0.0313 (6)
H6	−0.4315	0.3802	0.6219	0.038*
C7	−0.1266 (5)	0.2553 (3)	0.63473 (10)	0.0314 (6)
H7	−0.1334	0.2502	0.6728	0.038*
C8	0.0550 (5)	0.1850 (3)	0.61069 (10)	0.0283 (6)
H8	0.1737	0.1313	0.6315	0.034*
C8A	0.0608 (4)	0.1948 (3)	0.55452 (10)	0.0243 (5)
N9	0.2174 (4)	0.1343 (3)	0.52100 (8)	0.0240 (5)
H9	0.335 (7)	0.082 (4)	0.5280 (15)	0.050 (11)*
C9A	0.1539 (4)	0.1807 (3)	0.46917 (9)	0.0233 (5)
C10	−0.1422 (5)	0.3404 (4)	0.31657 (11)	0.0343 (7)
C11	−0.3501 (8)	0.5424 (4)	0.27171 (14)	0.0588 (11)
H11A	−0.3926	0.6478	0.2821	0.071*
H11B	−0.2082	0.5483	0.2504	0.071*
C12	−0.5423 (7)	0.4765 (6)	0.23878 (18)	0.0713 (13)
H12A	−0.5770	0.5416	0.2072	0.107*
H12B	−0.6825	0.4693	0.2599	0.107*
H12C	−0.4976	0.3741	0.2269	0.107*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0278 (9)	0.0346 (11)	0.0253 (9)	0.0038 (8)	−0.0018 (7)	0.0018 (8)
O2	0.0752 (18)	0.139 (3)	0.0185 (10)	0.0649 (19)	0.0037 (11)	0.0088 (13)
O3	0.103 (2)	0.0541 (16)	0.0224 (10)	0.0415 (15)	−0.0067 (11)	0.0049 (10)
C1	0.0240 (11)	0.0279 (14)	0.0213 (11)	−0.0035 (10)	−0.0028 (9)	0.0015 (10)
C2	0.0282 (13)	0.0451 (18)	0.0215 (12)	0.0037 (12)	0.0013 (10)	0.0077 (11)
C3	0.0433 (16)	0.0393 (18)	0.0234 (13)	0.0103 (13)	−0.0034 (11)	−0.0001 (11)
C4	0.0259 (12)	0.0319 (15)	0.0211 (11)	0.0004 (11)	0.0000 (9)	0.0074 (10)
C4A	0.0244 (11)	0.0230 (13)	0.0209 (11)	−0.0034 (10)	−0.0032 (9)	0.0035 (9)
C5	0.0274 (12)	0.0279 (14)	0.0254 (12)	−0.0009 (10)	−0.0016 (9)	0.0029 (10)
C5A	0.0267 (12)	0.0223 (13)	0.0200 (11)	−0.0048 (10)	−0.0037 (9)	0.0025 (9)
C6	0.0334 (13)	0.0349 (16)	0.0259 (13)	0.0017 (12)	0.0033 (10)	−0.0001 (11)
C7	0.0415 (15)	0.0333 (16)	0.0193 (11)	−0.0027 (12)	−0.0009 (10)	0.0013 (11)
C8	0.0353 (13)	0.0285 (15)	0.0203 (12)	−0.0019 (11)	−0.0062 (10)	0.0020 (10)
C8A	0.0268 (12)	0.0240 (13)	0.0213 (11)	−0.0033 (10)	−0.0040 (9)	0.0007 (10)
N9	0.0278 (11)	0.0250 (12)	0.0186 (10)	0.0007 (9)	−0.0043 (8)	0.0003 (8)
C9A	0.0274 (12)	0.0237 (13)	0.0183 (11)	−0.0049 (10)	−0.0035 (9)	0.0024 (9)
C10	0.0376 (14)	0.0441 (18)	0.0207 (12)	0.0060 (13)	−0.0035 (10)	0.0014 (11)
C11	0.101 (3)	0.040 (2)	0.0337 (17)	0.013 (2)	−0.0184 (18)	0.0118 (14)
C12	0.053 (2)	0.083 (3)	0.076 (3)	−0.005 (2)	−0.022 (2)	0.041 (2)

O1—C1	1.227 (3)	C6—C5	1.375 (4)
O2—C10	1.180 (3)	C6—H6	0.9500
O3—C10	1.315 (4)	C7—C6	1.415 (4)
O3—C11	1.464 (4)	C7—C8	1.366 (4)
C1—C9A	1.438 (3)	C7—H7	0.9500
C2—C1	1.508 (3)	C8—C8A	1.400 (3)
C2—H2A	0.9900	C8—H8	0.9500
C2—H2B	0.9900	C8A—N9	1.359 (3)
C3—C2	1.539 (4)	C8A—C5A	1.423 (3)
C3—C4	1.501 (4)	N9—H9	0.82 (4)
C3—C10	1.521 (4)	C9A—C4A	1.378 (4)
C3—H3	1.0000	C9A—N9	1.378 (3)
C4—C4A	1.500 (3)	C11—C12	1.446 (6)
C4—H4A	0.9900	C11—H11A	0.9900
C4—H4B	0.9900	C11—H11B	0.9900
C5—C5A	1.399 (4)	C12—H12A	0.9800
C5—H5	0.9500	C12—H12B	0.9800
C5A—C4A	1.423 (3)	C12—H12C	0.9800

C10—O3—C11	116.7 (3)	C5—C6—H6	119.6
O1—C1—C2	121.3 (2)	C7—C6—H6	119.6
O1—C1—C9A	124.2 (2)	C6—C7—H7	119.3
C9A—C1—C2	114.5 (2)	C8—C7—C6	121.5 (2)
C1—C2—C3	115.5 (2)	C8—C7—H7	119.3
C1—C2—H2A	108.4	C7—C8—C8A	118.0 (2)
C1—C2—H2B	108.4	C7—C8—H8	121.0
C3—C2—H2A	108.4	C8A—C8—H8	121.0
C3—C2—H2B	108.4	N9—C8A—C5A	108.9 (2)
H2A—C2—H2B	107.5	N9—C8A—C8	129.8 (2)
C2—C3—H3	106.4	C8—C8A—C5A	121.4 (2)
C4—C3—C2	114.9 (2)	C8A—N9—C9A	108.1 (2)
C4—C3—C10	114.8 (2)	C8A—N9—H9	130 (3)
C4—C3—H3	106.4	C9A—N9—H9	122 (3)
C10—C3—C2	107.3 (2)	N9—C9A—C1	125.0 (2)
C10—C3—H3	106.4	C4A—C9A—N9	110.1 (2)
C3—C4—H4A	109.7	C4A—C9A—C1	124.8 (2)
C3—C4—H4B	109.7	O2—C10—O3	123.2 (3)
C4A—C4—C3	110.0 (2)	O2—C10—C3	123.6 (3)
C4A—C4—H4A	109.7	O3—C10—C3	113.3 (2)
C4A—C4—H4B	109.7	O3—C11—H11A	109.3
H4A—C4—H4B	108.2	O3—C11—H11B	109.3
C5A—C4A—C4	130.1 (2)	C12—C11—O3	111.7 (3)
C9A—C4A—C4	123.2 (2)	C12—C11—H11A	109.3
C9A—C4A—C5A	106.7 (2)	C12—C11—H11B	109.3
C5A—C5—H5	120.4	H11A—C11—H11B	107.9
C6—C5—C5A	119.2 (2)	C11—C12—H12A	109.5
C6—C5—H5	120.4	C11—C12—H12B	109.5
C4A—C5A—C8A	106.1 (2)	C11—C12—H12C	109.5
C5—C5A—C4A	134.8 (2)	H12A—C12—H12B	109.5
C5—C5A—C8A	119.1 (2)	H12A—C12—H12C	109.5
C5—C6—C7	120.8 (3)	H12B—C12—H12C	109.5

C11—O3—C10—O2	−5.3 (5)	C5—C5A—C4A—C4	5.2 (5)
C11—O3—C10—C3	175.9 (3)	C5—C5A—C4A—C9A	−177.5 (3)
C10—O3—C11—C12	88.6 (5)	C8A—C5A—C4A—C4	−176.3 (3)
O1—C1—C9A—N9	−0.6 (4)	C8A—C5A—C4A—C9A	1.0 (3)
O1—C1—C9A—C4A	179.6 (2)	C7—C6—C5—C5A	0.9 (4)
C2—C1—C9A—N9	−176.9 (2)	C8—C7—C6—C5	−2.0 (4)
C2—C1—C9A—C4A	3.2 (4)	C6—C7—C8—C8A	0.2 (4)
C3—C2—C1—O1	158.9 (3)	C7—C8—C8A—N9	−178.9 (3)
C3—C2—C1—C9A	−24.5 (4)	C7—C8—C8A—C5A	2.7 (4)
C4—C3—C2—C1	46.9 (4)	N9—C8A—C5A—C4A	−1.2 (3)
C10—C3—C2—C1	175.9 (2)	N9—C8A—C5A—C5	177.5 (2)
C2—C3—C4—C4A	−44.0 (3)	C8—C8A—C5A—C4A	177.5 (2)
C10—C3—C4—C4A	−169.1 (2)	C8—C8A—C5A—C5	−3.7 (4)
C2—C3—C10—O2	36.0 (5)	C8—C8A—N9—C9A	−177.6 (3)
C2—C3—C10—O3	−145.3 (3)	C5A—C8A—N9—C9A	1.0 (3)
C4—C3—C10—O2	165.0 (3)	C1—C9A—N9—C8A	179.8 (2)
C4—C3—C10—O3	−16.3 (4)	C4A—C9A—N9—C8A	−0.4 (3)
C3—C4—C4A—C5A	−159.6 (3)	N9—C9A—C4A—C4	177.1 (2)
C3—C4—C4A—C9A	23.5 (4)	N9—C9A—C4A—C5A	−0.4 (3)
C6—C5—C5A—C4A	−179.8 (3)	C1—C9A—C4A—C4	−3.1 (4)
C6—C5—C5A—C8A	1.8 (4)	C1—C9A—C4A—C5A	179.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O1ⁱ	0.82 (4)	2.08 (4)	2.834 (3)	154 (4)
C4—H4A···Cg3ⁱⁱ	0.99	2.75	3.727 (3)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9⋯O1ⁱ	0.82 (4)	2.08 (4)	2.834 (3)	154 (4)
C4—H4A⋯Cg3ⁱⁱ	0.99	2.75	3.727 (3)	171

Symmetry codes: (i) ; (ii) . Cg3 is the centroid of the C5A/C5–C8/C8A ring.

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