6-Meth-oxy-1-(4-meth-oxy-phen-yl)-1,2,3,4-tetra-hydro-9H-β-carbolin-2-ium acetate.

In the title compound, C(19)H(21)N(2)O(2) (+)·C(2)H(3)O(2) (-), the 1H-indole ring system is essentially planar [maximum deviation = 0.0257 (14) Å] and forms a dihedral angle of 87.92 (7) Å with the benzene ring attached to the tetra-hydro-pyridinium fragment. The tetra-hydro-pyridinium ring adopts a half-chair conformation. In the crystal, cations and anions are linked by inter-ionic N-H⋯O, C-H⋯O and C-H⋯N hydrogen bonds into chains along the a axis.

Related literature

For the biological activity of metal complexes with 6-meth­oxy-1-methyl-4,9-dihydro-3H-pyrido[3,4-b]indole, see: Al-Allaf et al. (1990 ▶); Herraiz et al. (2003 ▶). For a related tetra­chlorido­zincate structure, see: Goh et al. (2012 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C19H21N2O2 +·C2H3O2 −

M = 368.42

Monoclinic,

a = 9.1046 (4) Å

b = 19.8837 (8) Å

c = 12.0856 (5) Å

β = 123.281 (3)°

V = 1829.06 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.28 × 0.24 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.974, T max = 0.985

21273 measured reflections

6211 independent reflections

4350 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.134

S = 1.03

6211 reflections

247 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812016753/rz2738sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812016753/rz2738Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812016753/rz2738Isup3.cml

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

C19H21N2O2+·C2H3O2−	F(000) = 784
Mr = 368.42	Dx = 1.338 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5044 reflections
a = 9.1046 (4) Å	θ = 2.5–31.4°
b = 19.8837 (8) Å	µ = 0.09 mm−1
c = 12.0856 (5) Å	T = 100 K
β = 123.281 (3)°	Block, colourless
V = 1829.06 (15) Å3	0.28 × 0.24 × 0.16 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	6211 independent reflections
Radiation source: fine-focus sealed tube	4350 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
φ and ω scans	θmax = 31.7°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→13
Tmin = 0.974, Tmax = 0.985	k = −25→29
21273 measured reflections	l = −17→17

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0554P)2 + 0.5954P] where P = (Fo2 + 2Fc2)/3
6211 reflections	(Δ/σ)max = 0.001
247 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
O1	0.19801 (14)	0.80635 (6)	−0.51962 (10)	0.0206 (2)
O2	0.79721 (14)	0.79841 (5)	0.61132 (10)	0.0178 (2)
N1	0.53529 (15)	0.91336 (6)	−0.01734 (11)	0.0134 (2)
H2	0.6445	0.9291	0.0400	0.016*
N2	0.21849 (15)	0.94170 (6)	0.07834 (11)	0.0140 (2)
H1	0.1712	0.9749	0.0136	0.017*
H3	0.2114	0.9561	0.1518	0.017*
C1	0.47738 (18)	0.88736 (7)	−0.14119 (13)	0.0130 (3)
C2	0.56016 (19)	0.88480 (7)	−0.20957 (14)	0.0148 (3)
H2A	0.6767	0.9010	−0.1704	0.018*
C3	0.46785 (19)	0.85799 (7)	−0.33659 (14)	0.0153 (3)
H3A	0.5218	0.8559	−0.3851	0.018*
C4	0.29553 (19)	0.83388 (7)	−0.39423 (14)	0.0147 (3)
C5	0.21217 (19)	0.83642 (7)	−0.32661 (14)	0.0146 (3)
H5A	0.0956	0.8201	−0.3663	0.017*
C6	0.30332 (18)	0.86348 (7)	−0.19869 (13)	0.0121 (3)
C7	0.25808 (18)	0.87570 (7)	−0.10371 (13)	0.0134 (3)
C8	0.08984 (18)	0.86327 (8)	−0.11207 (14)	0.0151 (3)
H8A	0.0532	0.8159	−0.1371	0.018*
H8B	−0.0039	0.8926	−0.1808	0.018*
C9	0.11639 (19)	0.87798 (7)	0.02130 (14)	0.0151 (3)
H9A	0.0007	0.8823	0.0103	0.018*
H9B	0.1804	0.8402	0.0828	0.018*
C10	0.40804 (18)	0.93513 (7)	0.12006 (13)	0.0127 (3)
H10A	0.4582	0.9815	0.1352	0.015*
C11	0.40092 (18)	0.90627 (7)	0.00269 (13)	0.0126 (3)
C12	0.2764 (2)	0.80697 (9)	−0.59457 (15)	0.0215 (3)
H12A	0.1941	0.7879	−0.6825	0.032*
H12B	0.3843	0.7801	−0.5489	0.032*
H12C	0.3046	0.8534	−0.6038	0.032*
C13	0.51581 (18)	0.89668 (7)	0.24838 (13)	0.0129 (3)
C14	0.58947 (19)	0.93146 (8)	0.36854 (14)	0.0148 (3)
H14A	0.5734	0.9787	0.3680	0.018*
C15	0.68530 (19)	0.89756 (8)	0.48799 (14)	0.0153 (3)
H15A	0.7354	0.9215	0.5690	0.018*
C16	0.70801 (18)	0.82823 (7)	0.48899 (13)	0.0145 (3)
C17	0.63921 (19)	0.79301 (8)	0.37083 (14)	0.0157 (3)
H17A	0.6572	0.7459	0.3716	0.019*
C18	0.54363 (18)	0.82783 (7)	0.25149 (14)	0.0146 (3)
H18A	0.4965	0.8040	0.1707	0.018*
C19	0.8048 (2)	0.72675 (8)	0.61618 (16)	0.0229 (3)
H19A	0.8605	0.7118	0.7080	0.034*
H19B	0.8737	0.7108	0.5814	0.034*
H19C	0.6855	0.7084	0.5625	0.034*
O3	0.88167 (13)	0.95821 (5)	0.11028 (10)	0.0169 (2)
O4	1.16310 (14)	0.97876 (6)	0.26577 (10)	0.0201 (2)
C20	1.00753 (19)	0.96657 (7)	0.23013 (14)	0.0147 (3)
C21	0.9666 (2)	0.96257 (9)	0.33549 (16)	0.0247 (4)
H21A	1.0766	0.9612	0.4231	0.037*
H21B	0.8984	0.9218	0.3223	0.037*
H21C	0.8984	1.0022	0.3294	0.037*

	U11	U22	U33	U12	U13	U23
O1	0.0193 (5)	0.0309 (6)	0.0152 (5)	−0.0070 (5)	0.0118 (5)	−0.0087 (4)
O2	0.0180 (5)	0.0186 (6)	0.0123 (5)	0.0002 (4)	0.0055 (4)	0.0019 (4)
N1	0.0116 (5)	0.0171 (6)	0.0119 (5)	−0.0026 (5)	0.0068 (5)	−0.0014 (4)
N2	0.0131 (5)	0.0170 (6)	0.0120 (5)	0.0009 (5)	0.0071 (5)	−0.0009 (4)
C1	0.0138 (6)	0.0131 (7)	0.0121 (6)	0.0008 (5)	0.0072 (5)	−0.0006 (5)
C2	0.0129 (6)	0.0167 (7)	0.0166 (7)	−0.0008 (5)	0.0091 (6)	0.0000 (5)
C3	0.0168 (7)	0.0168 (7)	0.0172 (7)	−0.0009 (6)	0.0124 (6)	−0.0006 (5)
C4	0.0160 (6)	0.0158 (7)	0.0135 (6)	−0.0011 (6)	0.0090 (6)	−0.0017 (5)
C5	0.0135 (6)	0.0167 (7)	0.0148 (6)	−0.0014 (5)	0.0085 (6)	−0.0015 (5)
C6	0.0122 (6)	0.0129 (7)	0.0124 (6)	0.0008 (5)	0.0075 (5)	0.0010 (5)
C7	0.0134 (6)	0.0157 (7)	0.0134 (6)	0.0000 (5)	0.0088 (5)	−0.0002 (5)
C8	0.0132 (6)	0.0189 (7)	0.0149 (6)	−0.0029 (5)	0.0088 (5)	−0.0029 (5)
C9	0.0130 (6)	0.0186 (7)	0.0159 (6)	−0.0019 (5)	0.0092 (6)	−0.0020 (5)
C10	0.0118 (6)	0.0144 (7)	0.0128 (6)	−0.0005 (5)	0.0073 (5)	−0.0009 (5)
C11	0.0130 (6)	0.0137 (7)	0.0126 (6)	−0.0002 (5)	0.0081 (5)	0.0004 (5)
C12	0.0241 (8)	0.0294 (9)	0.0168 (7)	−0.0058 (7)	0.0149 (7)	−0.0066 (6)
C13	0.0112 (6)	0.0163 (7)	0.0127 (6)	−0.0008 (5)	0.0077 (5)	0.0005 (5)
C14	0.0151 (6)	0.0146 (7)	0.0159 (6)	−0.0012 (5)	0.0093 (6)	−0.0016 (5)
C15	0.0149 (6)	0.0185 (7)	0.0121 (6)	−0.0037 (5)	0.0072 (5)	−0.0042 (5)
C16	0.0107 (6)	0.0202 (7)	0.0125 (6)	−0.0007 (5)	0.0063 (5)	0.0009 (5)
C17	0.0173 (7)	0.0146 (7)	0.0154 (6)	0.0006 (5)	0.0091 (6)	−0.0004 (5)
C18	0.0160 (6)	0.0155 (7)	0.0124 (6)	−0.0019 (5)	0.0078 (6)	−0.0033 (5)
C19	0.0244 (8)	0.0191 (8)	0.0199 (7)	0.0013 (6)	0.0088 (7)	0.0042 (6)
O3	0.0134 (5)	0.0211 (6)	0.0150 (5)	−0.0002 (4)	0.0071 (4)	−0.0001 (4)
O4	0.0139 (5)	0.0313 (6)	0.0166 (5)	−0.0045 (4)	0.0092 (4)	−0.0069 (4)
C20	0.0152 (6)	0.0157 (7)	0.0152 (6)	0.0003 (5)	0.0097 (6)	−0.0008 (5)
C21	0.0240 (8)	0.0365 (10)	0.0200 (8)	−0.0023 (7)	0.0163 (7)	−0.0010 (7)

O1—C4	1.3811 (17)	C9—H9B	0.9900
O1—C12	1.4283 (17)	C10—C11	1.4982 (18)
O2—C16	1.3708 (17)	C10—C13	1.5108 (19)
O2—C19	1.4263 (19)	C10—H10A	1.0000
N1—C11	1.3784 (17)	C12—H12A	0.9800
N1—C1	1.3855 (17)	C12—H12B	0.9800
N1—H2	0.9001	C12—H12C	0.9800
N2—C9	1.4972 (19)	C13—C18	1.389 (2)
N2—C10	1.5148 (17)	C13—C14	1.4028 (19)
N2—H1	0.9296	C14—C15	1.385 (2)
N2—H3	0.9674	C14—H14A	0.9500
C1—C2	1.3918 (18)	C15—C16	1.393 (2)
C1—C6	1.4182 (19)	C15—H15A	0.9500
C2—C3	1.390 (2)	C16—C17	1.3929 (19)
C2—H2A	0.9500	C17—C18	1.393 (2)
C3—C4	1.406 (2)	C17—H17A	0.9500
C3—H3A	0.9500	C18—H18A	0.9500
C4—C5	1.3882 (18)	C19—H19A	0.9800
C5—C6	1.4001 (19)	C19—H19B	0.9800
C5—H5A	0.9500	C19—H19C	0.9800
C6—C7	1.4371 (18)	O3—C20	1.2717 (17)
C7—C11	1.3707 (19)	O4—C20	1.2573 (17)
C7—C8	1.4993 (19)	C20—C21	1.512 (2)
C8—C9	1.5213 (19)	C21—H21A	0.9800
C8—H8A	0.9900	C21—H21B	0.9800
C8—H8B	0.9900	C21—H21C	0.9800
C9—H9A	0.9900
C4—O1—C12	116.63 (11)	C13—C10—N2	111.40 (11)
C16—O2—C19	117.59 (11)	C11—C10—H10A	107.7
C11—N1—C1	107.65 (11)	C13—C10—H10A	107.7
C11—N1—H2	127.8	N2—C10—H10A	107.7
C1—N1—H2	124.4	C7—C11—N1	110.93 (12)
C9—N2—C10	112.73 (11)	C7—C11—C10	125.72 (12)
C9—N2—H1	109.2	N1—C11—C10	123.06 (12)
C10—N2—H1	105.0	O1—C12—H12A	109.5
C9—N2—H3	109.6	O1—C12—H12B	109.5
C10—N2—H3	110.9	H12A—C12—H12B	109.5
H1—N2—H3	109.2	O1—C12—H12C	109.5
N1—C1—C2	130.25 (13)	H12A—C12—H12C	109.5
N1—C1—C6	108.34 (11)	H12B—C12—H12C	109.5
C2—C1—C6	121.36 (12)	C18—C13—C14	118.77 (13)
C3—C2—C1	118.27 (13)	C18—C13—C10	122.18 (12)
C3—C2—H2A	120.9	C14—C13—C10	119.04 (13)
C1—C2—H2A	120.9	C15—C14—C13	120.61 (14)
C2—C3—C4	120.81 (12)	C15—C14—H14A	119.7
C2—C3—H3A	119.6	C13—C14—H14A	119.7
C4—C3—H3A	119.6	C14—C15—C16	119.76 (13)
O1—C4—C5	115.49 (12)	C14—C15—H15A	120.1
O1—C4—C3	123.33 (12)	C16—C15—H15A	120.1
C5—C4—C3	121.18 (13)	O2—C16—C17	123.73 (13)
C4—C5—C6	118.67 (13)	O2—C16—C15	115.76 (12)
C4—C5—H5A	120.7	C17—C16—C15	120.50 (13)
C6—C5—H5A	120.7	C18—C17—C16	119.06 (14)
C5—C6—C1	119.71 (12)	C18—C17—H17A	120.5
C5—C6—C7	133.71 (13)	C16—C17—H17A	120.5
C1—C6—C7	106.56 (12)	C13—C18—C17	121.27 (13)
C11—C7—C6	106.50 (12)	C13—C18—H18A	119.4
C11—C7—C8	123.00 (12)	C17—C18—H18A	119.4
C6—C7—C8	130.41 (13)	O2—C19—H19A	109.5
C7—C8—C9	109.54 (11)	O2—C19—H19B	109.5
C7—C8—H8A	109.8	H19A—C19—H19B	109.5
C9—C8—H8A	109.8	O2—C19—H19C	109.5
C7—C8—H8B	109.8	H19A—C19—H19C	109.5
C9—C8—H8B	109.8	H19B—C19—H19C	109.5
H8A—C8—H8B	108.2	O4—C20—O3	123.85 (13)
N2—C9—C8	110.37 (11)	O4—C20—C21	118.25 (13)
N2—C9—H9A	109.6	O3—C20—C21	117.90 (13)
C8—C9—H9A	109.6	C20—C21—H21A	109.5
N2—C9—H9B	109.6	C20—C21—H21B	109.5
C8—C9—H9B	109.6	H21A—C21—H21B	109.5
H9A—C9—H9B	108.1	C20—C21—H21C	109.5
C11—C10—C13	116.38 (12)	H21A—C21—H21C	109.5
C11—C10—N2	105.57 (11)	H21B—C21—H21C	109.5
C11—N1—C1—C2	177.32 (15)	C6—C7—C11—N1	−0.96 (16)
C11—N1—C1—C6	−0.18 (15)	C8—C7—C11—N1	−177.99 (13)
N1—C1—C2—C3	−177.32 (14)	C6—C7—C11—C10	173.05 (13)
C6—C1—C2—C3	−0.1 (2)	C8—C7—C11—C10	−4.0 (2)
C1—C2—C3—C4	−0.2 (2)	C1—N1—C11—C7	0.73 (16)
C12—O1—C4—C5	176.19 (13)	C1—N1—C11—C10	−173.47 (13)
C12—O1—C4—C3	−3.9 (2)	C13—C10—C11—C7	108.15 (16)
C2—C3—C4—O1	−179.57 (14)	N2—C10—C11—C7	−15.97 (19)
C2—C3—C4—C5	0.4 (2)	C13—C10—C11—N1	−78.52 (17)
O1—C4—C5—C6	179.77 (13)	N2—C10—C11—N1	157.36 (13)
C3—C4—C5—C6	−0.2 (2)	C11—C10—C13—C18	−26.91 (19)
C4—C5—C6—C1	−0.1 (2)	N2—C10—C13—C18	94.16 (15)
C4—C5—C6—C7	177.79 (15)	C11—C10—C13—C14	153.50 (12)
N1—C1—C6—C5	178.05 (13)	N2—C10—C13—C14	−85.42 (15)
C2—C1—C6—C5	0.3 (2)	C18—C13—C14—C15	−1.2 (2)
N1—C1—C6—C7	−0.39 (15)	C10—C13—C14—C15	178.38 (12)
C2—C1—C6—C7	−178.16 (13)	C13—C14—C15—C16	−0.4 (2)
C5—C6—C7—C11	−177.31 (16)	C19—O2—C16—C17	−6.2 (2)
C1—C6—C7—C11	0.82 (16)	C19—O2—C16—C15	172.50 (13)
C5—C6—C7—C8	−0.6 (3)	C14—C15—C16—O2	−176.91 (12)
C1—C6—C7—C8	177.54 (14)	C14—C15—C16—C17	1.8 (2)
C11—C7—C8—C9	−9.9 (2)	O2—C16—C17—C18	177.02 (13)
C6—C7—C8—C9	173.87 (14)	C15—C16—C17—C18	−1.6 (2)
C10—N2—C9—C8	−69.07 (14)	C14—C13—C18—C17	1.4 (2)
C7—C8—C9—N2	43.56 (16)	C10—C13—C18—C17	−178.14 (13)
C9—N2—C10—C11	51.16 (14)	C16—C17—C18—C13	−0.1 (2)
C9—N2—C10—C13	−76.04 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O3i	0.93	1.86	2.7762 (15)	169
N1—H2···O3	0.90	1.93	2.7895 (19)	160
N2—H3···O4ii	0.97	1.72	2.6800 (18)	171
C9—H9A···O3ii	0.99	2.52	3.285 (2)	134
C10—H10A···N1i	1.00	2.55	3.4038 (19)	143
C15—H15A···O4iii	0.95	2.60	3.5073 (19)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O3i	0.93	1.86	2.7762 (15)	169
N1—H2⋯O3	0.90	1.93	2.7895 (19)	160
N2—H3⋯O4ii	0.97	1.72	2.6800 (18)	171
C9—H9A⋯O3ii	0.99	2.52	3.285 (2)	134
C10—H10A⋯N1i	1.00	2.55	3.4038 (19)	143
C15—H15A⋯O4iii	0.95	2.60	3.5073 (19)	160

Symmetry codes: (i) ; (ii) ; (iii) .