organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

2-(Carbazol-9-yl)acetic acid

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[Jinmao, Y., Bo, Zh. & Weibing, Zh. (2001). J. Chromatogr. A, 909, 171-182.]). For synthesis: Xie et al. (2006[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.]).

[Scheme 1]

Experimental

Crystal data
  • C14H11NO2

  • Mr = 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)

  • Rint = 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

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.25 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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···O1i [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%).

Refinement top

Positional parameters of all the H atoms bonded to C atoms were calculated geometrically and were allowed to ride on the C atoms to which they are bonded,with C—H=0.95 and 0.99 Å for aromatic and methylene and with Uiso(H) = 1.2Ueq(aromatic,methylene) parent atoms. The carboxylic H atom was taken from a differnce density map and refined.

Structure description 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···O1i [i= 1-x, 1-y, 1-z] hydrogen bonds.

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).

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
[Figure 1] 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
C14H11NO2F(000) = 944
Mr = 225.24Dx = 1.343 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2975 reflections
a = 32.067 (19) Åθ = 3.1–27.5°
b = 5.340 (3) ŵ = 0.09 mm1
c = 13.134 (7) ÅT = 93 K
β = 97.756 (8)°Platelet, colorless
V = 2229 (2) Å30.40 × 0.30 × 0.08 mm
Z = 8
Data collection top
Rigaku SPIDER
diffractometer
1749 reflections with I > 2σ(I)
Radiation source: Rotating AnodeRint = 0.067
Graphite monochromatorθmax = 27.5°, θmin = 3.1°
ω scansh = 4141
8360 measured reflectionsk = 66
2534 independent reflectionsl = 1717
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093 w = 1/[σ2(Fo2) + (0.0136P)2 + 0.660P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2534 reflectionsΔρmax = 0.22 e Å3
159 parametersΔρmin = 0.25 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0006 (2)
Crystal data top
C14H11NO2V = 2229 (2) Å3
Mr = 225.24Z = 8
Monoclinic, C2/cMo Kα radiation
a = 32.067 (19) ŵ = 0.09 mm1
b = 5.340 (3) ÅT = 93 K
c = 13.134 (7) Å0.40 × 0.30 × 0.08 mm
β = 97.756 (8)°
Data collection top
Rigaku SPIDER
diffractometer
1749 reflections with I > 2σ(I)
8360 measured reflectionsRint = 0.067
2534 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.22 e Å3
2534 reflectionsΔρmin = 0.25 e Å3
159 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.45527 (4)0.3887 (2)0.43806 (10)0.0305 (3)
O20.48708 (4)0.7517 (2)0.40940 (10)0.0322 (4)
N10.38917 (5)0.4955 (3)0.28479 (11)0.0248 (4)
C10.39216 (6)0.3113 (3)0.21154 (13)0.0240 (4)
C20.42431 (6)0.2678 (3)0.15246 (14)0.0285 (5)
H20.44860.37150.15820.034*
C30.41955 (6)0.0674 (3)0.08487 (14)0.0309 (5)
H30.44110.03300.04380.037*
C40.38388 (6)0.0852 (4)0.07555 (14)0.0303 (5)
H40.38140.22040.02810.036*
C50.35211 (6)0.0411 (3)0.13498 (14)0.0281 (5)
H50.32790.14560.12870.034*
C60.35604 (6)0.1578 (3)0.20388 (13)0.0235 (4)
C70.33048 (6)0.2527 (3)0.27875 (13)0.0245 (4)
C80.29237 (6)0.1775 (4)0.30960 (14)0.0291 (5)
H80.27750.03740.27850.035*
C90.27678 (6)0.3113 (4)0.38653 (15)0.0338 (5)
H90.25100.26150.40860.041*
C100.29835 (6)0.5181 (4)0.43219 (15)0.0344 (5)
H100.28670.60770.48410.041*
C110.33618 (6)0.5962 (4)0.40406 (14)0.0303 (5)
H110.35090.73600.43600.036*
C120.35197 (6)0.4611 (3)0.32662 (14)0.0255 (4)
C130.42069 (6)0.6818 (3)0.31517 (14)0.0277 (5)
H13A0.40720.82750.34400.033*
H13B0.43260.73950.25350.033*
C140.45600 (6)0.5897 (4)0.39346 (14)0.0257 (4)
H2O0.5081 (8)0.687 (4)0.4603 (19)0.088 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0316 (8)0.0297 (8)0.0293 (8)0.0020 (6)0.0000 (6)0.0064 (6)
O20.0290 (8)0.0318 (8)0.0337 (8)0.0065 (7)0.0034 (6)0.0074 (7)
N10.0252 (9)0.0249 (9)0.0238 (9)0.0024 (7)0.0011 (7)0.0003 (7)
C10.0286 (10)0.0238 (11)0.0187 (9)0.0017 (8)0.0001 (7)0.0037 (8)
C20.0285 (11)0.0308 (11)0.0262 (10)0.0003 (9)0.0038 (8)0.0068 (9)
C30.0373 (12)0.0344 (12)0.0214 (10)0.0081 (9)0.0057 (9)0.0053 (9)
C40.0405 (12)0.0283 (11)0.0211 (10)0.0068 (9)0.0004 (9)0.0011 (8)
C50.0330 (11)0.0264 (11)0.0235 (10)0.0003 (9)0.0009 (8)0.0019 (8)
C60.0262 (10)0.0241 (11)0.0190 (9)0.0030 (8)0.0018 (7)0.0031 (8)
C70.0252 (10)0.0259 (10)0.0210 (10)0.0022 (8)0.0015 (7)0.0040 (8)
C80.0261 (11)0.0326 (12)0.0274 (11)0.0014 (9)0.0004 (8)0.0034 (9)
C90.0287 (11)0.0460 (14)0.0270 (11)0.0019 (10)0.0047 (8)0.0056 (10)
C100.0354 (12)0.0405 (13)0.0275 (11)0.0080 (10)0.0043 (9)0.0007 (10)
C110.0356 (12)0.0298 (11)0.0240 (11)0.0038 (9)0.0009 (8)0.0005 (9)
C120.0266 (10)0.0269 (11)0.0220 (10)0.0015 (8)0.0001 (8)0.0054 (8)
C130.0281 (10)0.0275 (11)0.0264 (10)0.0021 (8)0.0005 (8)0.0033 (8)
C140.0282 (11)0.0273 (11)0.0221 (10)0.0015 (8)0.0048 (8)0.0015 (8)
Geometric parameters (Å, º) top
O1—C141.224 (2)C5—H50.9500
O2—C141.315 (2)C6—C71.454 (2)
O2—H2O0.95 (3)C7—C81.397 (2)
N1—C11.388 (2)C7—C121.411 (2)
N1—C121.391 (2)C8—C91.385 (3)
N1—C131.436 (2)C8—H80.9500
C1—C21.391 (2)C9—C101.395 (3)
C1—C61.412 (2)C9—H90.9500
C2—C31.386 (2)C10—C111.379 (3)
C2—H20.9500C10—H100.9500
C3—C41.397 (3)C11—C121.397 (2)
C3—H30.9500C11—H110.9500
C4—C51.385 (3)C13—C141.506 (2)
C4—H40.9500C13—H13A0.9900
C5—C61.390 (2)C13—H13B0.9900
C14—O2—H2O109.0 (14)C9—C8—C7118.62 (18)
C1—N1—C12108.85 (15)C9—C8—H8120.7
C1—N1—C13124.87 (16)C7—C8—H8120.7
C12—N1—C13126.21 (16)C8—C9—C10121.03 (19)
N1—C1—C2129.09 (17)C8—C9—H9119.5
N1—C1—C6109.17 (16)C10—C9—H9119.5
C2—C1—C6121.74 (17)C11—C10—C9121.81 (19)
C3—C2—C1117.42 (18)C11—C10—H10119.1
C3—C2—H2121.3C9—C10—H10119.1
C1—C2—H2121.3C10—C11—C12117.21 (18)
C2—C3—C4121.67 (18)C10—C11—H11121.4
C2—C3—H3119.2C12—C11—H11121.4
C4—C3—H3119.2N1—C12—C11129.33 (18)
C5—C4—C3120.51 (18)N1—C12—C7108.75 (17)
C5—C4—H4119.7C11—C12—C7121.91 (18)
C3—C4—H4119.7N1—C13—C14113.56 (15)
C4—C5—C6119.20 (18)N1—C13—H13A108.9
C4—C5—H5120.4C14—C13—H13A108.9
C6—C5—H5120.4N1—C13—H13B108.9
C5—C6—C1119.46 (17)C14—C13—H13B108.9
C5—C6—C7134.18 (18)H13A—C13—H13B107.7
C1—C6—C7106.34 (16)O1—C14—O2124.31 (18)
C8—C7—C12119.41 (18)O1—C14—C13123.49 (17)
C8—C7—C6133.70 (18)O2—C14—C13112.19 (16)
C12—C7—C6106.88 (16)
C12—N1—C1—C2177.99 (18)C12—C7—C8—C90.2 (3)
C13—N1—C1—C20.9 (3)C6—C7—C8—C9178.84 (18)
C12—N1—C1—C61.23 (19)C7—C8—C9—C100.4 (3)
C13—N1—C1—C6178.30 (15)C8—C9—C10—C110.9 (3)
N1—C1—C2—C3179.41 (16)C9—C10—C11—C120.8 (3)
C6—C1—C2—C30.3 (3)C1—N1—C12—C11178.33 (18)
C1—C2—C3—C40.3 (3)C13—N1—C12—C111.3 (3)
C2—C3—C4—C50.6 (3)C1—N1—C12—C70.6 (2)
C3—C4—C5—C60.3 (3)C13—N1—C12—C7177.59 (15)
C4—C5—C6—C10.3 (3)C10—C11—C12—N1178.94 (17)
C4—C5—C6—C7177.68 (18)C10—C11—C12—C70.2 (3)
N1—C1—C6—C5179.87 (15)C8—C7—C12—N1178.71 (15)
C2—C1—C6—C50.6 (3)C6—C7—C12—N10.3 (2)
N1—C1—C6—C71.38 (19)C8—C7—C12—C110.3 (3)
C2—C1—C6—C7177.91 (16)C6—C7—C12—C11179.28 (16)
C5—C6—C7—C80.4 (4)C1—N1—C13—C1482.2 (2)
C1—C6—C7—C8177.79 (19)C12—N1—C13—C1494.4 (2)
C5—C6—C7—C12179.19 (19)N1—C13—C14—O19.8 (3)
C1—C6—C7—C121.01 (19)N1—C13—C14—O2171.34 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···O1i0.95 (3)1.70 (3)2.645 (2)171 (2)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC14H11NO2
Mr225.24
Crystal system, space groupMonoclinic, C2/c
Temperature (K)93
a, b, c (Å)32.067 (19), 5.340 (3), 13.134 (7)
β (°) 97.756 (8)
V3)2229 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.40 × 0.30 × 0.08
Data collection
DiffractometerRigaku SPIDER
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8360, 2534, 1749
Rint0.067
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.093, 1.00
No. of reflections2534
No. of parameters159
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O2—H2O···O1i0.95 (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

First citationJinmao, Y., Bo, Zh. & Weibing, Zh. (2001). J. Chromatogr. A, 909, 171–182.  Web of Science PubMed Google Scholar
First citationRigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationXie, 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

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ISSN: 2056-9890
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