2-(Carbazol-9-yl)acetic acid

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

doi:10.1107/S1600536809043463

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2860

https://doi.org/10.1107/S1600536809043463

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2-(Carbazol-9-yl)acetic acid

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

^aJiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
^*Correspondence e-mail: xiemh0704@sina.com

(Received 4 June 2009; accepted 21 October 2009; online 28 October 2009)

In the title compound, C₁₄H₁₁NO₂, the tricyclic aromatic ring system is essentially planar [maximum deviation = 0.025 (2) Å]. The dihedral angle between the two benzene rings is 2.8 (5)°, while the carboxyl group forms a dihedral angle of 88.5 (1)° with the pyrrole ring. Intermolecular O—H⋯O hydrogen bonds may contribute to the overall stabilization of the crystal structure.

Related literature

For the use of the title compound in high-performance liquid chromatography, see: Jinmao et al. (2001 ). For synthesis: Xie et al. (2006 ).

Experimental

Crystal data

C₁₄H₁₁NO₂
M_r = 225.24
Monoclinic, C 2/c
a = 32.067 (19) Å
b = 5.340 (3) Å
c = 13.134 (7) Å
β = 97.756 (8)°
V = 2229 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 93 K
0.40 × 0.30 × 0.08 mm

Data collection

Rigaku SPIDER diffractometer
Absorption correction: none
8360 measured reflections
2534 independent reflections
1749 reflections with I > 2σ(I)
R_int = 0.067

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.093
S = 1.00
2534 reflections
159 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O1ⁱ	0.95 (3)	1.70 (3)	2.645 (2)	171 (2)
Symmetry code: (i) -x+1, -y+1, -z+1.

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: https://doi.org/10.1107/S1600536809043463/cs2123sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809043463/cs2123Isup2.hkl

checkCIF report

Comment top

Carbazoles are ubiquitous structural subunits of numerous naturally occurring compounds as well as synthetic materials. The title molecule (Fig. 1), is useful as an important agent for determination of alcohols by high-performance liquid chromatography with fluorimetric detection after pre-column derivatization (Jinmao et al., 2001; Xie et al., 2006). The crystal structure shows that the tricyclic aromatic ring system is coplanar. The dihedral angle between the two benzene rings is 2.8 (5)°. The pyrrole ring makes dihedral angles of 1.5 (5)° and 1.3 (5)° with the benzene rings, respectively. The pyrrole ring and the carboxylic acid group (O1/C14/O2) are twisted to each other by a torsion angles of 88.5 (1)°. The crystal structure may be stabilized by intermolecular O2–H2O···O1_i [i= 1-x, 1-y, 1-z] hydrogen bonds.

Related literature top

For the use of the title compound as an agent for the determination of alcohols by high-performance liquid chromatography with fluorimetric detection after pre-column derivatization, see: Jinmao et al. (2001). For synthesis: Xie et al. (2006).

Experimental top

The title compound was prepared by a method reported earlier (Xie et al., 2006). The pure product (0.1 g) obtained was dissolved in 50% ethanol (10 ml). The solution was evaporated in air affording colourless platelet crystals suitable for X-ray analysis (yield: 67.2%).

Structure description top

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. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

2-(Carbazol-9-yl)acetic acid top

Crystal data top

C₁₄H₁₁NO₂	F(000) = 944
M_r = 225.24	D_x = 1.343 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2975 reflections
a = 32.067 (19) Å	θ = 3.1–27.5°
b = 5.340 (3) Å	µ = 0.09 mm⁻¹
c = 13.134 (7) Å	T = 93 K
β = 97.756 (8)°	Platelet, colorless
V = 2229 (2) Å³	0.40 × 0.30 × 0.08 mm
Z = 8

Data collection top

Rigaku SPIDER diffractometer	1749 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.067
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −41→41
8360 measured reflections	k = −6→6
2534 independent reflections	l = −17→17

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)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0136P)² + 0.660P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2534 reflections	Δρ_max = 0.22 e Å⁻³
159 parameters	Δρ_min = −0.25 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: 0.0006 (2)

Crystal data top

C₁₄H₁₁NO₂	V = 2229 (2) Å³
M_r = 225.24	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 32.067 (19) Å	µ = 0.09 mm⁻¹
b = 5.340 (3) Å	T = 93 K
c = 13.134 (7) Å	0.40 × 0.30 × 0.08 mm
β = 97.756 (8)°

Data collection top

Rigaku SPIDER diffractometer	1749 reflections with I > 2σ(I)
8360 measured reflections	R_int = 0.067
2534 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.22 e Å⁻³
2534 reflections	Δρ_min = −0.25 e Å⁻³
159 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.45527 (4)	0.3887 (2)	0.43806 (10)	0.0305 (3)
O2	0.48708 (4)	0.7517 (2)	0.40940 (10)	0.0322 (4)
N1	0.38917 (5)	0.4955 (3)	0.28479 (11)	0.0248 (4)
C1	0.39216 (6)	0.3113 (3)	0.21154 (13)	0.0240 (4)
C2	0.42431 (6)	0.2678 (3)	0.15246 (14)	0.0285 (5)
H2	0.4486	0.3715	0.1582	0.034*
C3	0.41955 (6)	0.0674 (3)	0.08487 (14)	0.0309 (5)
H3	0.4411	0.0330	0.0438	0.037*
C4	0.38388 (6)	−0.0852 (4)	0.07555 (14)	0.0303 (5)
H4	0.3814	−0.2204	0.0281	0.036*
C5	0.35211 (6)	−0.0411 (3)	0.13498 (14)	0.0281 (5)
H5	0.3279	−0.1456	0.1287	0.034*
C6	0.35604 (6)	0.1578 (3)	0.20388 (13)	0.0235 (4)
C7	0.33048 (6)	0.2527 (3)	0.27875 (13)	0.0245 (4)
C8	0.29237 (6)	0.1775 (4)	0.30960 (14)	0.0291 (5)
H8	0.2775	0.0374	0.2785	0.035*
C9	0.27678 (6)	0.3113 (4)	0.38653 (15)	0.0338 (5)
H9	0.2510	0.2615	0.4086	0.041*
C10	0.29835 (6)	0.5181 (4)	0.43219 (15)	0.0344 (5)
H10	0.2867	0.6077	0.4841	0.041*
C11	0.33618 (6)	0.5962 (4)	0.40406 (14)	0.0303 (5)
H11	0.3509	0.7360	0.4360	0.036*
C12	0.35197 (6)	0.4611 (3)	0.32662 (14)	0.0255 (4)
C13	0.42069 (6)	0.6818 (3)	0.31517 (14)	0.0277 (5)
H13A	0.4072	0.8275	0.3440	0.033*
H13B	0.4326	0.7395	0.2535	0.033*
C14	0.45600 (6)	0.5897 (4)	0.39346 (14)	0.0257 (4)
H2O	0.5081 (8)	0.687 (4)	0.4603 (19)	0.088 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0316 (8)	0.0297 (8)	0.0293 (8)	−0.0020 (6)	0.0000 (6)	0.0064 (6)
O2	0.0290 (8)	0.0318 (8)	0.0337 (8)	−0.0065 (7)	−0.0034 (6)	0.0074 (7)
N1	0.0252 (9)	0.0249 (9)	0.0238 (9)	−0.0024 (7)	0.0011 (7)	0.0003 (7)
C1	0.0286 (10)	0.0238 (11)	0.0187 (9)	0.0017 (8)	0.0001 (7)	0.0037 (8)
C2	0.0285 (11)	0.0308 (11)	0.0262 (10)	0.0003 (9)	0.0038 (8)	0.0068 (9)
C3	0.0373 (12)	0.0344 (12)	0.0214 (10)	0.0081 (9)	0.0057 (9)	0.0053 (9)
C4	0.0405 (12)	0.0283 (11)	0.0211 (10)	0.0068 (9)	0.0004 (9)	0.0011 (8)
C5	0.0330 (11)	0.0264 (11)	0.0235 (10)	0.0003 (9)	−0.0009 (8)	0.0019 (8)
C6	0.0262 (10)	0.0241 (11)	0.0190 (9)	0.0030 (8)	−0.0018 (7)	0.0031 (8)
C7	0.0252 (10)	0.0259 (10)	0.0210 (10)	0.0022 (8)	−0.0015 (7)	0.0040 (8)
C8	0.0261 (11)	0.0326 (12)	0.0274 (11)	−0.0014 (9)	−0.0004 (8)	0.0034 (9)
C9	0.0287 (11)	0.0460 (14)	0.0270 (11)	0.0019 (10)	0.0047 (8)	0.0056 (10)
C10	0.0354 (12)	0.0405 (13)	0.0275 (11)	0.0080 (10)	0.0043 (9)	−0.0007 (10)
C11	0.0356 (12)	0.0298 (11)	0.0240 (11)	0.0038 (9)	−0.0009 (8)	−0.0005 (9)
C12	0.0266 (10)	0.0269 (11)	0.0220 (10)	0.0015 (8)	−0.0001 (8)	0.0054 (8)
C13	0.0281 (10)	0.0275 (11)	0.0264 (10)	−0.0021 (8)	−0.0005 (8)	0.0033 (8)
C14	0.0282 (11)	0.0273 (11)	0.0221 (10)	−0.0015 (8)	0.0048 (8)	−0.0015 (8)

Geometric parameters (Å, º) top

O1—C14	1.224 (2)	C5—H5	0.9500
O2—C14	1.315 (2)	C6—C7	1.454 (2)
O2—H2O	0.95 (3)	C7—C8	1.397 (2)
N1—C1	1.388 (2)	C7—C12	1.411 (2)
N1—C12	1.391 (2)	C8—C9	1.385 (3)
N1—C13	1.436 (2)	C8—H8	0.9500
C1—C2	1.391 (2)	C9—C10	1.395 (3)
C1—C6	1.412 (2)	C9—H9	0.9500
C2—C3	1.386 (2)	C10—C11	1.379 (3)
C2—H2	0.9500	C10—H10	0.9500
C3—C4	1.397 (3)	C11—C12	1.397 (2)
C3—H3	0.9500	C11—H11	0.9500
C4—C5	1.385 (3)	C13—C14	1.506 (2)
C4—H4	0.9500	C13—H13A	0.9900
C5—C6	1.390 (2)	C13—H13B	0.9900

C14—O2—H2O	109.0 (14)	C9—C8—C7	118.62 (18)
C1—N1—C12	108.85 (15)	C9—C8—H8	120.7
C1—N1—C13	124.87 (16)	C7—C8—H8	120.7
C12—N1—C13	126.21 (16)	C8—C9—C10	121.03 (19)
N1—C1—C2	129.09 (17)	C8—C9—H9	119.5
N1—C1—C6	109.17 (16)	C10—C9—H9	119.5
C2—C1—C6	121.74 (17)	C11—C10—C9	121.81 (19)
C3—C2—C1	117.42 (18)	C11—C10—H10	119.1
C3—C2—H2	121.3	C9—C10—H10	119.1
C1—C2—H2	121.3	C10—C11—C12	117.21 (18)
C2—C3—C4	121.67 (18)	C10—C11—H11	121.4
C2—C3—H3	119.2	C12—C11—H11	121.4
C4—C3—H3	119.2	N1—C12—C11	129.33 (18)
C5—C4—C3	120.51 (18)	N1—C12—C7	108.75 (17)
C5—C4—H4	119.7	C11—C12—C7	121.91 (18)
C3—C4—H4	119.7	N1—C13—C14	113.56 (15)
C4—C5—C6	119.20 (18)	N1—C13—H13A	108.9
C4—C5—H5	120.4	C14—C13—H13A	108.9
C6—C5—H5	120.4	N1—C13—H13B	108.9
C5—C6—C1	119.46 (17)	C14—C13—H13B	108.9
C5—C6—C7	134.18 (18)	H13A—C13—H13B	107.7
C1—C6—C7	106.34 (16)	O1—C14—O2	124.31 (18)
C8—C7—C12	119.41 (18)	O1—C14—C13	123.49 (17)
C8—C7—C6	133.70 (18)	O2—C14—C13	112.19 (16)
C12—C7—C6	106.88 (16)

C12—N1—C1—C2	−177.99 (18)	C12—C7—C8—C9	0.2 (3)
C13—N1—C1—C2	−0.9 (3)	C6—C7—C8—C9	178.84 (18)
C12—N1—C1—C6	1.23 (19)	C7—C8—C9—C10	0.4 (3)
C13—N1—C1—C6	178.30 (15)	C8—C9—C10—C11	−0.9 (3)
N1—C1—C2—C3	179.41 (16)	C9—C10—C11—C12	0.8 (3)
C6—C1—C2—C3	0.3 (3)	C1—N1—C12—C11	178.33 (18)
C1—C2—C3—C4	0.3 (3)	C13—N1—C12—C11	1.3 (3)
C2—C3—C4—C5	−0.6 (3)	C1—N1—C12—C7	−0.6 (2)
C3—C4—C5—C6	0.3 (3)	C13—N1—C12—C7	−177.59 (15)
C4—C5—C6—C1	0.3 (3)	C10—C11—C12—N1	−178.94 (17)
C4—C5—C6—C7	−177.68 (18)	C10—C11—C12—C7	−0.2 (3)
N1—C1—C6—C5	−179.87 (15)	C8—C7—C12—N1	178.71 (15)
C2—C1—C6—C5	−0.6 (3)	C6—C7—C12—N1	−0.3 (2)
N1—C1—C6—C7	−1.38 (19)	C8—C7—C12—C11	−0.3 (3)
C2—C1—C6—C7	177.91 (16)	C6—C7—C12—C11	−179.28 (16)
C5—C6—C7—C8	0.4 (4)	C1—N1—C13—C14	−82.2 (2)
C1—C6—C7—C8	−177.79 (19)	C12—N1—C13—C14	94.4 (2)
C5—C6—C7—C12	179.19 (19)	N1—C13—C14—O1	−9.8 (3)
C1—C6—C7—C12	1.01 (19)	N1—C13—C14—O2	171.34 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O1ⁱ	0.95 (3)	1.70 (3)	2.645 (2)	171 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁NO₂
M_r	225.24
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	93
a, b, c (Å)	32.067 (19), 5.340 (3), 13.134 (7)
β (°)	97.756 (8)
V (Å³)	2229 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.30 × 0.08

Data collection
Diffractometer	Rigaku SPIDER
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8360, 2534, 1749
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.093, 1.00
No. of reflections	2534
No. of parameters	159
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.25

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
O2—H2O···O1ⁱ	0.95 (3)	1.70 (3)	2.645 (2)	171 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The Key Laboratory of Nuclear Medicine of the Ministry Health of China is thanked for supporting this work.

References

Jinmao, Y., Bo, Zh. & Weibing, Zh. (2001). J. Chromatogr. A, 909, 171–182. Web of Science PubMed Google Scholar
Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xie, M. H., Qiu, A. Y., He, Y. J., Wu, J., Zhou, X. Q., Zou, P., Liu, Y. L. & Luo, S. N. (2006). Chin. J. Anal. Chem. 34, S131–134. Web of Science CrossRef CAS Google Scholar