3-Carb­oxy­methyl-1H-indole-4-carb­oxy­lic acid

Mao, S.

doi:10.1107/S1600536811051865

organic compounds

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Volume 68| Part 1| January 2012| Page o146

doi:10.1107/S1600536811051865

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3-Carboxymethyl-1H-indole-4-carboxylic acid

Shulin Mao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: chmsunbw@seu.edu.cn

(Received 29 November 2011; accepted 1 December 2011; online 17 December 2011)

In the title compound, C₁₁H₉NO₄, the carboxyl group bonded to the six-membered ring lies close to the plane of the 1H-indole ring system [dihedral angle = 13.13 (9)°], whereas the carboxylic acid group linked to the five-membered ring by a methylene bridge is close to perpendicular [78.85 (9)°]. In the crystal, O—H⋯O and N—H⋯O hydrogen bonds link the molecules, generating (110) sheets.

Related literature

For background to indoles as pharmaceuticals, see: Lang et al. (2011 ).

Experimental

Crystal data

C₁₁H₉NO₄
M_r = 219.19
Triclinic, $[P \overline 1]$
a = 5.4573 (11) Å
b = 9.823 (2) Å
c = 9.940 (2) Å
α = 73.90 (3)°
β = 78.57 (3)°
γ = 80.40 (3)°
V = 498.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.30 × 0.23 × 0.20 mm

Data collection

Rigaku SCXmini CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.977, T_max = 0.984
5115 measured reflections
2263 independent reflections
1786 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.132
S = 0.95
2239 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.83	2.6504 (19)	174
O4—H4⋯O3ⁱⁱ	0.82	1.91	2.719 (2)	171
N1—H1B⋯O3ⁱⁱⁱ	0.86	2.38	3.152 (2)	150
Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x, -y+2, -z+2; (iii) -x+1, -y+1, -z+2.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811051865/hb6541sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811051865/hb6541Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811051865/hb6541Isup3.cml

checkCIF report

Related literature top

For background to indoles as pharmaceuticals, see: Lang et al. (2011).

Experimental top

To a solution of the title compound (0.2 g) in methanol (20 ml) by stirred at room temperature and then placed in a dark place. Yellow single crystals were obtained by slow evaporation of the solution over a period of 5 days.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I) with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Packing diagram.

3-Carboxymethyl-1H-indole-4-carboxylic acid top

Crystal data top

C₁₁H₉NO₄	V = 498.3 (2) Å³
M_r = 219.19	Z = 2
Triclinic, P1	F(000) = 228
Hall symbol: -P 1	D_x = 1.461 Mg m⁻³
a = 5.4573 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.823 (2) Å	θ = 3.4–27.4°
c = 9.940 (2) Å	µ = 0.11 mm⁻¹
α = 73.90 (3)°	T = 293 K
β = 78.57 (3)°	Prism, yellow
γ = 80.40 (3)°	0.30 × 0.23 × 0.20 mm

Data collection top

Rigaku SCXmini CCD diffractometer	2263 independent reflections
Radiation source: fine-focus sealed tube	1786 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.4°, θ_min = 3.4°
CCD_Profile_fitting scans	h = −6→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
T_min = 0.977, T_max = 0.984	l = −12→12
5115 measured reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.0712P)² + 0.1712P] where P = (F_o² + 2F_c²)/3
2239 reflections	(Δ/σ)_max = 0.015
147 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₁H₉NO₄	γ = 80.40 (3)°
M_r = 219.19	V = 498.3 (2) Å³
Triclinic, P1	Z = 2
a = 5.4573 (11) Å	Mo Kα radiation
b = 9.823 (2) Å	µ = 0.11 mm⁻¹
c = 9.940 (2) Å	T = 293 K
α = 73.90 (3)°	0.30 × 0.23 × 0.20 mm
β = 78.57 (3)°

Data collection top

Rigaku SCXmini CCD diffractometer	2263 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1786 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.984	R_int = 0.028
5115 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 0.95	Δρ_max = 0.30 e Å⁻³
2239 reflections	Δρ_min = −0.21 e Å⁻³
147 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
O3	0.1544 (2)	0.84288 (12)	0.97213 (13)	0.0443 (3)
O2	0.1686 (3)	0.91438 (13)	0.62549 (15)	0.0579 (4)
O1	0.0340 (3)	0.82135 (14)	0.47736 (16)	0.0648 (5)
H1	−0.0320	0.9036	0.4520	0.097*
O4	0.2593 (3)	1.06204 (12)	0.86103 (17)	0.0588 (4)
H4	0.1255	1.0856	0.9079	0.088*
N1	0.7240 (3)	0.48127 (14)	0.87277 (16)	0.0423 (4)
H1B	0.8103	0.4047	0.9134	0.051*
C3	0.4527 (3)	0.63513 (15)	0.73814 (15)	0.0300 (3)
C11	0.2985 (3)	0.92105 (16)	0.88625 (17)	0.0357 (4)
C9	0.1571 (3)	0.81052 (17)	0.58232 (17)	0.0375 (4)
C4	0.2738 (3)	0.66441 (16)	0.64359 (16)	0.0337 (4)
C2	0.5741 (3)	0.71447 (16)	0.80476 (17)	0.0330 (3)
C8	0.5522 (3)	0.48888 (16)	0.78546 (17)	0.0347 (4)
C7	0.4775 (3)	0.37626 (17)	0.74825 (19)	0.0416 (4)
H7	0.5467	0.2826	0.7820	0.050*
C5	0.2020 (4)	0.55078 (18)	0.60716 (19)	0.0440 (4)
H5	0.0857	0.5703	0.5454	0.053*
C1	0.7343 (3)	0.61564 (19)	0.8840 (2)	0.0423 (4)
H1A	0.8362	0.6374	0.9380	0.051*
C10	0.5422 (3)	0.87055 (16)	0.80186 (19)	0.0375 (4)
H10A	0.5509	0.9260	0.7040	0.045*
H10B	0.6816	0.8894	0.8385	0.045*
C6	0.2990 (4)	0.40813 (18)	0.6605 (2)	0.0463 (4)
H6	0.2424	0.3352	0.6363	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0485 (7)	0.0270 (6)	0.0508 (7)	0.0021 (5)	−0.0007 (6)	−0.0082 (5)
O2	0.0848 (10)	0.0310 (6)	0.0679 (9)	0.0111 (6)	−0.0480 (8)	−0.0141 (6)
O1	0.1008 (12)	0.0354 (7)	0.0696 (9)	0.0118 (7)	−0.0576 (9)	−0.0129 (6)
O4	0.0616 (9)	0.0258 (6)	0.0804 (10)	−0.0021 (6)	0.0096 (7)	−0.0159 (6)
N1	0.0411 (8)	0.0319 (7)	0.0511 (8)	0.0107 (6)	−0.0162 (7)	−0.0083 (6)
C3	0.0320 (7)	0.0255 (7)	0.0294 (7)	0.0008 (6)	−0.0016 (6)	−0.0068 (5)
C11	0.0407 (9)	0.0251 (7)	0.0438 (9)	0.0001 (6)	−0.0134 (7)	−0.0106 (6)
C9	0.0443 (9)	0.0319 (8)	0.0362 (8)	0.0010 (7)	−0.0138 (7)	−0.0064 (6)
C4	0.0388 (8)	0.0274 (7)	0.0333 (8)	−0.0005 (6)	−0.0069 (6)	−0.0061 (6)
C2	0.0302 (7)	0.0313 (8)	0.0372 (8)	0.0007 (6)	−0.0056 (6)	−0.0105 (6)
C8	0.0355 (8)	0.0286 (8)	0.0354 (8)	0.0043 (6)	−0.0041 (6)	−0.0063 (6)
C7	0.0517 (10)	0.0234 (7)	0.0452 (9)	0.0025 (7)	−0.0043 (8)	−0.0076 (6)
C5	0.0546 (10)	0.0338 (8)	0.0481 (10)	−0.0030 (7)	−0.0194 (8)	−0.0112 (7)
C1	0.0378 (9)	0.0411 (9)	0.0494 (10)	0.0038 (7)	−0.0144 (7)	−0.0138 (7)
C10	0.0366 (8)	0.0313 (8)	0.0470 (9)	−0.0034 (6)	−0.0101 (7)	−0.0122 (7)
C6	0.0628 (12)	0.0300 (8)	0.0498 (10)	−0.0063 (8)	−0.0128 (9)	−0.0128 (7)

Geometric parameters (Å, º) top

O3—C11	1.228 (2)	C9—C4	1.483 (2)
O2—C9	1.226 (2)	C4—C5	1.399 (2)
O1—C9	1.321 (2)	C2—C1	1.376 (2)
O1—H1	0.8200	C2—C10	1.507 (2)
O4—C11	1.3255 (19)	C8—C7	1.401 (2)
O4—H4	0.8200	C7—C6	1.375 (3)
N1—C1	1.366 (2)	C7—H7	0.9300
N1—C8	1.379 (2)	C5—C6	1.406 (2)
N1—H1B	0.8600	C5—H5	0.9300
C3—C4	1.428 (2)	C1—H1A	0.9300
C3—C8	1.430 (2)	C10—H10A	0.9700
C3—C2	1.455 (2)	C10—H10B	0.9700
C11—C10	1.512 (2)	C6—H6	0.9300

C9—O1—H1	109.5	N1—C8—C3	108.27 (14)
C11—O4—H4	109.5	C7—C8—C3	123.86 (15)
C1—N1—C8	108.65 (13)	C6—C7—C8	118.15 (15)
C1—N1—H1B	125.7	C6—C7—H7	120.9
C8—N1—H1B	125.7	C8—C7—H7	120.9
C4—C3—C8	116.31 (14)	C4—C5—C6	122.44 (16)
C4—C3—C2	137.91 (14)	C4—C5—H5	118.8
C8—C3—C2	105.78 (13)	C6—C5—H5	118.8
O3—C11—O4	122.70 (15)	N1—C1—C2	111.03 (15)
O3—C11—C10	125.15 (14)	N1—C1—H1A	124.5
O4—C11—C10	112.12 (14)	C2—C1—H1A	124.5
O2—C9—O1	121.54 (15)	C2—C10—C11	114.51 (14)
O2—C9—C4	123.59 (15)	C2—C10—H10A	108.6
O1—C9—C4	114.86 (14)	C11—C10—H10A	108.6
C5—C4—C3	119.06 (14)	C2—C10—H10B	108.6
C5—C4—C9	117.85 (15)	C11—C10—H10B	108.6
C3—C4—C9	123.09 (14)	H10A—C10—H10B	107.6
C1—C2—C3	106.26 (14)	C7—C6—C5	120.11 (16)
C1—C2—C10	122.09 (15)	C7—C6—H6	119.9
C3—C2—C10	131.61 (14)	C5—C6—H6	119.9
N1—C8—C7	127.86 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.83	2.6504 (19)	174
O4—H4···O3ⁱⁱ	0.82	1.91	2.719 (2)	171
N1—H1B···O3ⁱⁱⁱ	0.86	2.38	3.152 (2)	150

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

Experimental details

Crystal data
Chemical formula	C₁₁H₉NO₄
M_r	219.19
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.4573 (11), 9.823 (2), 9.940 (2)
α, β, γ (°)	73.90 (3), 78.57 (3), 80.40 (3)
V (Å³)	498.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.23 × 0.20

Data collection
Diffractometer	Rigaku SCXmini CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.977, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	5115, 2263, 1786
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.132, 0.95
No. of reflections	2239
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.21

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.83	2.6504 (19)	174
O4—H4···O3ⁱⁱ	0.82	1.91	2.719 (2)	171
N1—H1B···O3ⁱⁱⁱ	0.86	2.38	3.152 (2)	150

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

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Lang, L., Wu, J.-L., Shi, L.-J., Xia, C.-G. & Li, F.-W. (2011). Chem. Commun. 47, 12553–12555. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o146

doi:10.1107/S1600536811051865

Open

access