1-Methyl-1,2,3,4-tetra-hydro-carbolin-2-ium-3-carboxyl-ate.

The title compound, C(13)H(14)N(2)O(2), is a natural product isolated from Cicer arietinum L. (chickpea). The benzene ring and pyrrole rings display planar conformations and the piperidine ring has a half-chair conformation. Inter-molecular C-H⋯π inter-actions between a methyl H atom and the pyrrole ring of an adjacent mol-ecule are present in the crystal structure.

Related literature

For the isolation of the title compound as a natural product, see: Kicha et al. (2003 ▶). For the bioactivity of the title compound, see: Adachi et al. (1991 ▶); Ogawa & Adachi (1993 ▶).

Experimental

Crystal data

C13H14N2O2

M = 230.26

Orthorhombic,

a = 4.9772 (8) Å

b = 14.520 (2) Å

c = 15.307 (2) Å

V = 1106.3 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

0.32 × 0.23 × 0.13 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.971, T max = 0.988

5528 measured reflections

1166 independent reflections

880 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.117

S = 1.00

1166 reflections

156 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810002163/pb2017sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002163/pb2017Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H14N2O2	F(000) = 488
Mr = 230.26	Dx = 1.383 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 666 reflections
a = 4.9772 (8) Å	θ = 2.7–18.0°
b = 14.520 (2) Å	µ = 0.10 mm−1
c = 15.307 (2) Å	T = 296 K
V = 1106.3 (3) Å3	Needle, colorless
Z = 4	0.32 × 0.23 × 0.13 mm

Bruker APEXII CCD area-detector diffractometer	1166 independent reflections
Radiation source: fine-focus sealed tube	880 reflections with I > 2σ(I)
graphite	Rint = 0.053
phi and ω scans	θmax = 25.1°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −5→5
Tmin = 0.971, Tmax = 0.988	k = −17→15
5528 measured reflections	l = −16→18

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)] = 0.042	H-atom parameters constrained
wR(F2) = 0.117	w = 1/[σ2(Fo2) + (0.074P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
1166 reflections	Δρmax = 0.22 e Å−3
156 parameters	Δρmin = −0.17 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: 0.026 (6)

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	Uiso*/Ueq
N1	0.3184 (7)	0.56276 (18)	0.71317 (15)	0.0402 (7)
H1	0.2878	0.5045	0.7104	0.048*
N2	−0.0123 (6)	0.67564 (14)	0.90152 (14)	0.0319 (6)
H2A	−0.1486	0.6668	0.9393	0.038*
H2B	0.1421	0.6729	0.9320	0.038*
O2	−0.0135 (5)	0.82385 (13)	1.00915 (13)	0.0390 (6)
O1	−0.2002 (7)	0.91384 (15)	0.90704 (15)	0.0581 (8)
C1	0.4997 (7)	0.6110 (2)	0.66226 (19)	0.0382 (8)
C2	0.6786 (8)	0.5800 (3)	0.59940 (19)	0.0476 (9)
H2	0.6826	0.5183	0.5830	0.057*
C3	0.8495 (8)	0.6429 (3)	0.5621 (2)	0.0539 (11)
H3	0.9745	0.6232	0.5209	0.065*
C4	0.8388 (8)	0.7364 (3)	0.5849 (2)	0.0503 (9)
H4	0.9523	0.7782	0.5574	0.060*
C5	0.6633 (8)	0.7669 (3)	0.6473 (2)	0.0441 (9)
H5	0.6573	0.8290	0.6622	0.053*
C6	0.4939 (7)	0.7043 (2)	0.68836 (19)	0.0348 (7)
C7	0.2982 (7)	0.7105 (2)	0.75634 (17)	0.0343 (8)
C8	0.2132 (7)	0.7924 (2)	0.8087 (2)	0.0369 (8)
H8A	0.1759	0.8437	0.7699	0.044*
H8B	0.3574	0.8105	0.8477	0.044*
C9	−0.0383 (7)	0.7696 (2)	0.86201 (19)	0.0325 (8)
H9	−0.1924	0.7690	0.8222	0.039*
C10	−0.0145 (7)	0.59951 (19)	0.83517 (18)	0.0345 (8)
H10	−0.1902	0.5989	0.8062	0.041*
C11	0.1945 (8)	0.6245 (2)	0.76945 (19)	0.0348 (8)
C12	0.0263 (10)	0.5078 (2)	0.8807 (2)	0.0550 (11)
H12A	0.1971	0.5078	0.9098	0.082*
H12B	0.0219	0.4591	0.8383	0.082*
H12C	−0.1142	0.4986	0.9228	0.082*
C13	−0.0897 (7)	0.8423 (2)	0.9318 (2)	0.0355 (8)

	U11	U22	U33	U12	U13	U23
N1	0.0454 (19)	0.0379 (14)	0.0374 (15)	−0.0017 (15)	0.0046 (15)	−0.0056 (11)
N2	0.0258 (15)	0.0372 (13)	0.0326 (13)	−0.0020 (13)	−0.0009 (14)	−0.0002 (10)
O2	0.0340 (14)	0.0448 (13)	0.0381 (12)	0.0015 (11)	0.0012 (12)	−0.0039 (10)
O1	0.076 (2)	0.0457 (14)	0.0523 (14)	0.0215 (15)	0.0009 (15)	0.0018 (12)
C1	0.035 (2)	0.0501 (19)	0.0292 (16)	0.0034 (19)	−0.0021 (17)	−0.0026 (13)
C2	0.048 (2)	0.061 (2)	0.0336 (17)	0.011 (2)	0.0031 (19)	−0.0081 (17)
C3	0.038 (2)	0.087 (3)	0.037 (2)	0.005 (2)	0.0069 (19)	−0.0038 (19)
C4	0.034 (2)	0.079 (3)	0.0377 (18)	−0.009 (2)	0.0057 (19)	0.0038 (18)
C5	0.038 (2)	0.056 (2)	0.0382 (17)	−0.0014 (19)	0.0014 (18)	0.0012 (15)
C6	0.0291 (18)	0.0470 (18)	0.0283 (14)	0.0000 (17)	−0.0003 (16)	−0.0008 (13)
C7	0.032 (2)	0.0406 (17)	0.0303 (16)	−0.0006 (15)	−0.0002 (16)	−0.0013 (12)
C8	0.033 (2)	0.0390 (17)	0.0383 (16)	−0.0018 (15)	0.0021 (16)	0.0035 (13)
C9	0.026 (2)	0.0388 (17)	0.0324 (15)	0.0009 (14)	0.0005 (15)	0.0017 (13)
C10	0.0354 (19)	0.0374 (17)	0.0306 (16)	−0.0050 (17)	0.0013 (17)	−0.0018 (12)
C11	0.0312 (19)	0.0412 (18)	0.0319 (15)	0.0003 (15)	−0.0038 (15)	−0.0034 (13)
C12	0.073 (3)	0.041 (2)	0.051 (2)	−0.001 (2)	0.009 (2)	0.0002 (15)
C13	0.0307 (19)	0.0395 (18)	0.0363 (18)	−0.0005 (15)	0.0043 (15)	0.0011 (14)

N1—C1	1.383 (4)	C5—C6	1.390 (5)
N1—C11	1.388 (4)	C5—H5	0.9300
N1—H1	0.8600	C6—C7	1.428 (5)
N2—C9	1.498 (4)	C7—C11	1.367 (4)
N2—C10	1.501 (3)	C7—C8	1.495 (4)
N2—H2A	0.9000	C8—C9	1.530 (5)
N2—H2B	0.9000	C8—H8A	0.9700
O2—C13	1.272 (4)	C8—H8B	0.9700
O1—C13	1.234 (4)	C9—C13	1.523 (4)
C1—C2	1.386 (5)	C9—H9	0.9800
C1—C6	1.412 (4)	C10—C11	1.492 (4)
C2—C3	1.373 (5)	C10—C12	1.516 (4)
C2—H2	0.9300	C10—H10	0.9800
C3—C4	1.404 (5)	C12—H12A	0.9600
C3—H3	0.9300	C12—H12B	0.9600
C4—C5	1.368 (5)	C12—H12C	0.9600
C4—H4	0.9300
C1—N1—C11	108.2 (3)	C7—C8—C9	110.2 (3)
C1—N1—H1	125.9	C7—C8—H8A	109.6
C11—N1—H1	125.9	C9—C8—H8A	109.6
C9—N2—C10	113.4 (2)	C7—C8—H8B	109.6
C9—N2—H2A	108.9	C9—C8—H8B	109.6
C10—N2—H2A	108.9	H8A—C8—H8B	108.1
C9—N2—H2B	108.9	N2—C9—C13	111.3 (2)
C10—N2—H2B	108.9	N2—C9—C8	110.0 (3)
H2A—N2—H2B	107.7	C13—C9—C8	111.2 (3)
N1—C1—C2	130.2 (3)	N2—C9—H9	108.1
N1—C1—C6	108.2 (3)	C13—C9—H9	108.1
C2—C1—C6	121.4 (3)	C8—C9—H9	108.1
C3—C2—C1	118.1 (3)	C11—C10—N2	105.8 (2)
C3—C2—H2	121.0	C11—C10—C12	115.5 (3)
C1—C2—H2	121.0	N2—C10—C12	109.5 (2)
C2—C3—C4	121.1 (3)	C11—C10—H10	108.6
C2—C3—H3	119.5	N2—C10—H10	108.6
C4—C3—H3	119.5	C12—C10—H10	108.6
C5—C4—C3	120.8 (4)	C7—C11—N1	109.4 (3)
C5—C4—H4	119.6	C7—C11—C10	125.8 (3)
C3—C4—H4	119.6	N1—C11—C10	124.9 (3)
C4—C5—C6	119.4 (3)	C10—C12—H12A	109.5
C4—C5—H5	120.3	C10—C12—H12B	109.5
C6—C5—H5	120.3	H12A—C12—H12B	109.5
C5—C6—C1	119.1 (3)	C10—C12—H12C	109.5
C5—C6—C7	134.5 (3)	H12A—C12—H12C	109.5
C1—C6—C7	106.3 (3)	H12B—C12—H12C	109.5
C11—C7—C6	107.8 (3)	O1—C13—O2	126.5 (3)
C11—C7—C8	122.8 (3)	O1—C13—C9	116.3 (3)
C6—C7—C8	129.4 (3)	O2—C13—C9	117.2 (3)
C11—N1—C1—C2	177.1 (3)	C10—N2—C9—C8	−67.4 (3)
C11—N1—C1—C6	1.3 (4)	C7—C8—C9—N2	42.5 (3)
N1—C1—C2—C3	−176.0 (3)	C7—C8—C9—C13	166.2 (3)
C6—C1—C2—C3	−0.7 (5)	C9—N2—C10—C11	52.2 (3)
C1—C2—C3—C4	−1.8 (5)	C9—N2—C10—C12	177.2 (3)
C2—C3—C4—C5	2.2 (6)	C6—C7—C11—N1	0.7 (4)
C3—C4—C5—C6	0.0 (6)	C8—C7—C11—N1	−178.1 (3)
C4—C5—C6—C1	−2.4 (5)	C6—C7—C11—C10	179.4 (3)
C4—C5—C6—C7	177.5 (4)	C8—C7—C11—C10	0.6 (5)
N1—C1—C6—C5	179.0 (3)	C1—N1—C11—C7	−1.3 (4)
C2—C1—C6—C5	2.8 (5)	C1—N1—C11—C10	−180.0 (3)
N1—C1—C6—C7	−0.9 (3)	N2—C10—C11—C7	−19.6 (4)
C2—C1—C6—C7	−177.1 (3)	C12—C10—C11—C7	−140.9 (4)
C5—C6—C7—C11	−179.8 (4)	N2—C10—C11—N1	158.9 (3)
C1—C6—C7—C11	0.1 (4)	C12—C10—C11—N1	37.6 (4)
C5—C6—C7—C8	−1.1 (6)	N2—C9—C13—O1	−156.8 (3)
C1—C6—C7—C8	178.8 (3)	C8—C9—C13—O1	80.3 (4)
C11—C7—C8—C9	−12.0 (4)	N2—C9—C13—O2	23.7 (4)
C6—C7—C8—C9	169.5 (3)	C8—C9—C13—O2	−99.2 (3)
C10—N2—C9—C13	168.9 (3)

Cg1 is the centroid of C1/C6/C7/C11/N1 pyrrole ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···Cg1i	0.98	2.69	3.644 (3)	165

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of C1/C6/C7/C11/N1 pyrrole ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯Cg1i	0.98	2.69	3.644 (3)	165

Symmetry code: (i) .