Methyl 9H-carbazole-9-acetate

He, Y.-J.; Xie, M.-H.; Zou, P.; Liu, Y.-L.; Wang, H.-Y.

doi:10.1107/S1600536809015141

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1136

doi:10.1107/S1600536809015141

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Methyl 9H-carbazole-9-acetate

Yong-Jun He,^a Min-Hao Xie,^a ^* Pei Zou,^a Ya-Ling Liu ^a and Hong-Yong Wang ^a

^aJiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
^*Correspondence e-mail: yongjunhe001@hotmail.com

(Received 21 April 2009; accepted 23 April 2009; online 25 April 2009)

The title compound, C₁₅H₁₃NO₂, was synthesized by N-alkylation of methyl bromoacetate with 9H-carbazole. The carbazole ring system is essentially planar (mean atomic deviation = 0.0346 Å) and makes a dihedral angle of 86.5 (7)° with the methyl acetate group. Weak intermolecular C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

The title compound is an intermediate in the synthesis of -(9-carbazole) acetyl chloride, a novel fluorescence derivatization reagent, see: Xie et al. (2006 ); Bong et al. (1992 ). For bond distances, see: Allen et al. (1987 ). For the synthesis, see: Xie et al. (2006).

Experimental

Crystal data

C₁₅H₁₃NO₂
M_r = 239.26
Monoclinic, P 2₁ /c
a = 10.875 (3) Å
b = 5.8773 (12) Å
c = 18.608 (4) Å
β = 103.599 (3)°
V = 1155.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 93 K
0.43 × 0.33 × 0.27 mm

Data collection

Rigaku SPIDER diffractometer
Absorption correction: none
8735 measured reflections
2615 independent reflections
1587 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.143
S = 1.00
2615 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15B⋯O2ⁱ	0.98	2.43	3.374 (3)	161
Symmetry code: (i) x, y-1, z.

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015141/xu2513sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015141/xu2513Isup2.hkl

checkCIF report

Comment top

The title compound is useful as an intermediate in the synthesis of 2-(9-carbazole) acetyl chloride, a novel fluorescence derivatization reagent (Xie et al., 2006; Bong et al., 1992). We report here the crystal structure of (I), which is of interest to us in the field. The molecular structure of(I) is showed in Fig.1. The bond lengths and angles are within normal ranges (Allen et al., 1987). The carbazole ring system is essentially planar with mean deviation of 0.0346 Å. The methylacetate substituent adopts a fully extended conformation, and its mean plane forms a dihedral angle of 93.5 (7)° with the carbazole mean plane. In the crystal structure weak C—H···O hydrogen bonding in present (Table 1).

Related literature top

The title compound is an intermediate in the synthesis of

2-(9-carbazole) acetyl chloride, a novel fluorescence derivatization reagent, see: Xie et al. (2006); Bong et al. (1992). For bond distances, see: Allen et al. (1987). For the synthesis, see: Xie et al. (2006).

Experimental top

The title compound was prepared by the method reported in literature (Xie et al., 2006). The crystals were obtained by dissolving the title compound (0.1 g) in methanol (20 ml), and evaporating the solvent slowly at room temperature. Colorless prism-shaped crystals were formed after 3 d.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

Methyl 9H-carbazole-9-acetate top

Crystal data top

C₁₅H₁₃NO₂	F(000) = 504
M_r = 239.26	D_x = 1.375 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3382 reflections
a = 10.875 (3) Å	θ = 3.3–27.5°
b = 5.8773 (12) Å	µ = 0.09 mm⁻¹
c = 18.608 (4) Å	T = 93 K
β = 103.599 (3)°	Prism, colorless
V = 1155.9 (5) Å³	0.43 × 0.33 × 0.27 mm
Z = 4

Data collection top

Rigaku SPIDER diffractometer	1587 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.041
Graphite monochromator	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −14→14
8735 measured reflections	k = −7→7
2615 independent reflections	l = −24→20

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0306P)² + 1.86P] where P = (F_o² + 2F_c²)/3
2615 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₅H₁₃NO₂	V = 1155.9 (5) Å³
M_r = 239.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.875 (3) Å	µ = 0.09 mm⁻¹
b = 5.8773 (12) Å	T = 93 K
c = 18.608 (4) Å	0.43 × 0.33 × 0.27 mm
β = 103.599 (3)°

Data collection top

Rigaku SPIDER diffractometer	1587 reflections with I > 2σ(I)
8735 measured reflections	R_int = 0.041
2615 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.00	Δρ_max = 0.33 e Å⁻³
2615 reflections	Δρ_min = −0.36 e Å⁻³
164 parameters

Special details top

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
O1	0.15039 (15)	0.6886 (3)	0.49433 (9)	0.0250 (4)
O2	0.11310 (18)	1.0517 (3)	0.45700 (10)	0.0349 (5)
N1	0.31648 (18)	0.7955 (3)	0.62011 (11)	0.0239 (5)
C1	0.4231 (2)	0.6749 (4)	0.61296 (13)	0.0242 (5)
C2	0.5141 (2)	0.7323 (4)	0.57434 (13)	0.0272 (6)
H2	0.5081	0.8696	0.5468	0.033*
C3	0.6132 (2)	0.5828 (5)	0.57759 (13)	0.0295 (6)
H3	0.6767	0.6191	0.5520	0.035*
C4	0.6228 (2)	0.3793 (5)	0.61751 (13)	0.0290 (6)
H4	0.6912	0.2784	0.6179	0.035*
C5	0.5332 (2)	0.3246 (4)	0.65647 (13)	0.0268 (6)
H5	0.5400	0.1872	0.6840	0.032*
C6	0.4324 (2)	0.4737 (4)	0.65483 (13)	0.0234 (5)
C7	0.3267 (2)	0.4732 (4)	0.68959 (13)	0.0237 (5)
C8	0.2899 (2)	0.3290 (4)	0.74042 (13)	0.0276 (6)
H8	0.3364	0.1942	0.7568	0.033*
C9	0.1848 (2)	0.3858 (5)	0.76644 (14)	0.0309 (6)
H9	0.1602	0.2914	0.8021	0.037*
C10	0.1143 (2)	0.5807 (5)	0.74077 (14)	0.0304 (6)
H10	0.0412	0.6141	0.7585	0.036*
C11	0.1483 (2)	0.7260 (5)	0.69037 (14)	0.0289 (6)
H11	0.0994	0.8574	0.6730	0.035*
C12	0.2565 (2)	0.6735 (4)	0.66592 (13)	0.0247 (5)
C13	0.2590 (2)	0.9803 (4)	0.57265 (13)	0.0263 (6)
H13A	0.3273	1.0713	0.5597	0.032*
H13B	0.2146	1.0802	0.6012	0.032*
C14	0.1662 (2)	0.9128 (4)	0.50173 (13)	0.0230 (5)
C15	0.0599 (2)	0.6135 (4)	0.42803 (13)	0.0284 (6)
H15A	−0.0252	0.6634	0.4301	0.034*
H15B	0.0617	0.4471	0.4250	0.034*
H15C	0.0821	0.6794	0.3844	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0257 (9)	0.0222 (9)	0.0240 (9)	−0.0003 (7)	−0.0001 (7)	0.0000 (7)
O2	0.0394 (11)	0.0295 (10)	0.0297 (10)	0.0044 (8)	−0.0043 (8)	0.0064 (8)
N1	0.0227 (10)	0.0239 (11)	0.0238 (10)	0.0030 (8)	0.0031 (8)	0.0028 (9)
C1	0.0241 (12)	0.0244 (13)	0.0217 (12)	0.0004 (10)	0.0005 (9)	−0.0026 (10)
C2	0.0275 (13)	0.0284 (13)	0.0236 (12)	−0.0001 (11)	0.0021 (10)	0.0023 (10)
C3	0.0298 (13)	0.0358 (15)	0.0233 (12)	−0.0010 (11)	0.0073 (10)	−0.0008 (11)
C4	0.0246 (12)	0.0358 (14)	0.0244 (12)	0.0034 (11)	0.0014 (10)	−0.0012 (11)
C5	0.0253 (12)	0.0237 (13)	0.0279 (13)	0.0033 (10)	−0.0006 (10)	0.0003 (11)
C6	0.0232 (12)	0.0247 (12)	0.0204 (11)	0.0005 (10)	0.0012 (9)	0.0003 (10)
C7	0.0226 (12)	0.0251 (12)	0.0204 (11)	−0.0018 (10)	−0.0007 (9)	0.0004 (10)
C8	0.0273 (13)	0.0290 (13)	0.0237 (12)	−0.0021 (11)	0.0001 (10)	−0.0008 (11)
C9	0.0271 (13)	0.0361 (15)	0.0278 (13)	−0.0034 (12)	0.0031 (10)	0.0010 (12)
C10	0.0246 (12)	0.0402 (16)	0.0258 (13)	−0.0006 (11)	0.0049 (10)	−0.0023 (12)
C11	0.0266 (13)	0.0310 (14)	0.0268 (13)	0.0031 (11)	0.0016 (10)	−0.0032 (11)
C12	0.0244 (12)	0.0244 (13)	0.0226 (12)	−0.0010 (10)	0.0000 (10)	−0.0024 (10)
C13	0.0281 (13)	0.0227 (13)	0.0250 (12)	0.0032 (10)	0.0001 (10)	0.0020 (10)
C14	0.0234 (12)	0.0191 (12)	0.0266 (12)	0.0016 (10)	0.0059 (10)	−0.0003 (10)
C15	0.0258 (12)	0.0310 (13)	0.0249 (12)	−0.0038 (11)	−0.0010 (10)	−0.0034 (11)

Geometric parameters (Å, º) top

O1—C14	1.332 (3)	C7—C8	1.397 (3)
O1—C15	1.454 (3)	C7—C12	1.416 (3)
O2—C14	1.211 (3)	C8—C9	1.383 (3)
N1—C12	1.388 (3)	C8—H8	0.9500
N1—C1	1.392 (3)	C9—C10	1.399 (4)
N1—C13	1.446 (3)	C9—H9	0.9500
C1—C2	1.394 (3)	C10—C11	1.381 (4)
C1—C6	1.407 (3)	C10—H10	0.9500
C2—C3	1.381 (4)	C11—C12	1.393 (3)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.398 (4)	C13—C14	1.514 (3)
C3—H3	0.9500	C13—H13A	0.9900
C4—C5	1.383 (3)	C13—H13B	0.9900
C4—H4	0.9500	C15—H15A	0.9800
C5—C6	1.398 (3)	C15—H15B	0.9800
C5—H5	0.9500	C15—H15C	0.9800
C6—C7	1.445 (3)

C14—O1—C15	115.67 (18)	C8—C9—C10	120.7 (2)
C12—N1—C1	108.52 (19)	C8—C9—H9	119.7
C12—N1—C13	124.4 (2)	C10—C9—H9	119.7
C1—N1—C13	125.0 (2)	C11—C10—C9	121.7 (2)
N1—C1—C2	129.4 (2)	C11—C10—H10	119.1
N1—C1—C6	109.1 (2)	C9—C10—H10	119.1
C2—C1—C6	121.5 (2)	C10—C11—C12	117.8 (2)
C3—C2—C1	117.7 (2)	C10—C11—H11	121.1
C3—C2—H2	121.2	C12—C11—H11	121.1
C1—C2—H2	121.2	N1—C12—C11	129.9 (2)
C2—C3—C4	121.8 (2)	N1—C12—C7	108.9 (2)
C2—C3—H3	119.1	C11—C12—C7	121.2 (2)
C4—C3—H3	119.1	N1—C13—C14	116.1 (2)
C5—C4—C3	120.2 (2)	N1—C13—H13A	108.3
C5—C4—H4	119.9	C14—C13—H13A	108.3
C3—C4—H4	119.9	N1—C13—H13B	108.3
C4—C5—C6	119.3 (2)	C14—C13—H13B	108.3
C4—C5—H5	120.4	H13A—C13—H13B	107.4
C6—C5—H5	120.4	O2—C14—O1	124.5 (2)
C5—C6—C1	119.5 (2)	O2—C14—C13	122.4 (2)
C5—C6—C7	133.7 (2)	O1—C14—C13	113.1 (2)
C1—C6—C7	106.8 (2)	O1—C15—H15A	109.5
C8—C7—C12	119.8 (2)	O1—C15—H15B	109.5
C8—C7—C6	133.5 (2)	H15A—C15—H15B	109.5
C12—C7—C6	106.6 (2)	O1—C15—H15C	109.5
C9—C8—C7	118.8 (2)	H15A—C15—H15C	109.5
C9—C8—H8	120.6	H15B—C15—H15C	109.5
C7—C8—H8	120.6

C12—N1—C1—C2	−178.1 (2)	C6—C7—C8—C9	176.1 (3)
C13—N1—C1—C2	17.5 (4)	C7—C8—C9—C10	1.8 (4)
C12—N1—C1—C6	−0.3 (3)	C8—C9—C10—C11	−1.6 (4)
C13—N1—C1—C6	−164.7 (2)	C9—C10—C11—C12	−0.5 (4)
N1—C1—C2—C3	178.6 (2)	C1—N1—C12—C11	178.8 (2)
C6—C1—C2—C3	1.0 (4)	C13—N1—C12—C11	−16.7 (4)
C1—C2—C3—C4	0.5 (4)	C1—N1—C12—C7	1.0 (3)
C2—C3—C4—C5	−1.3 (4)	C13—N1—C12—C7	165.5 (2)
C3—C4—C5—C6	0.6 (4)	C10—C11—C12—N1	−175.1 (2)
C4—C5—C6—C1	0.8 (4)	C10—C11—C12—C7	2.5 (4)
C4—C5—C6—C7	−178.1 (2)	C8—C7—C12—N1	175.7 (2)
N1—C1—C6—C5	−179.7 (2)	C6—C7—C12—N1	−1.2 (3)
C2—C1—C6—C5	−1.6 (4)	C8—C7—C12—C11	−2.3 (3)
N1—C1—C6—C7	−0.5 (3)	C6—C7—C12—C11	−179.3 (2)
C2—C1—C6—C7	177.6 (2)	C12—N1—C13—C14	−77.4 (3)
C5—C6—C7—C8	3.7 (5)	C1—N1—C13—C14	84.6 (3)
C1—C6—C7—C8	−175.3 (3)	C15—O1—C14—O2	−1.6 (4)
C5—C6—C7—C12	−180.0 (3)	C15—O1—C14—C13	178.6 (2)
C1—C6—C7—C12	1.0 (3)	N1—C13—C14—O2	−179.0 (2)
C12—C7—C8—C9	0.2 (3)	N1—C13—C14—O1	0.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15B···O2ⁱ	0.98	2.43	3.374 (3)	161

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃NO₂
M_r	239.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	93
a, b, c (Å)	10.875 (3), 5.8773 (12), 18.608 (4)
β (°)	103.599 (3)
V (Å³)	1155.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.43 × 0.33 × 0.27

Data collection
Diffractometer	Rigaku SPIDER diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8735, 2615, 1587
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.143, 1.00
No. of reflections	2615
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.36

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15B···O2ⁱ	0.98	2.43	3.374 (3)	161

Symmetry code: (i) x, y−1, z.

Acknowledgements

The authors acknowledge financial support from the Jiangsu Institute of Nuclear Medicine, China.

References

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