Bis(7-meth-oxy-1-methyl-4,9-dihydro-3H-β-carbolinium) tetra-chloridozincate.

In the title compound, (C(13)H(15)N(2)O)(2)[ZnCl(4)], also known as di(harmalinium) tetra-chloridozincate, the Zn(II) atom is in a distorted tetrahedral coordination of the chlorido ligands. In the cation, the meth-oxy and methyl groups are both coplanar with with rings to which they are attached [maximum deviations of 0.232 (4) and 0.259 (4) Å, respectively]. In the crystal, the alkaloid cations and metal complex anions inter-act by way of N-H⋯Cl hydrogen bonds involving each Cl atom, resulting in a network structure.

Related literature

For the activity of metal complexes with harmaline (7-methoxy-1-methyl-4,9-dihydro-3H-pyrido[3,4-b]indole), see: Al-Allaf et al. (1990 ▶). For the structures of harmaline and related compounds, see: Reimers et al. (1984 ▶); Wouters (1997 ▶); Ferretti et al. (2004 ▶). For zincate anions, see: Ma et al. (2009 ▶).

Experimental

Crystal data

(C13H15N2O)2[ZnCl4]

M = 637.71

Monoclinic,

a = 11.2314 (2) Å

b = 19.1274 (2) Å

c = 13.5614 (2) Å

β = 107.0797 (16)°

V = 2784.87 (7) Å3

Z = 4

Cu Kα radiation

μ = 5.01 mm−1

T = 293 K

0.25 × 0.12 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 ▶) T min = 0.544, T max = 0.644

12418 measured reflections

4954 independent reflections

3724 reflections with I > 2σ(I)

R int = 0.035

3 standard reflections every 100 reflections intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.116

S = 1.04

4954 reflections

334 parameters

H-atom parameters constrained

Δρmax = 0.54 e Å−3

Δρmin = −0.46 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810010822/bv2139sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810010822/bv2139Isup2.hkl

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

(C13H15N2O)2[ZnCl4]	F(000) = 1312
Mr = 637.71	Dx = 1.521 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 11.2314 (2) Å	Cell parameters from 4954 reflections
b = 19.1274 (2) Å	θ = 4.1–71.0°
c = 13.5614 (2) Å	µ = 5.01 mm−1
β = 107.0797 (16)°	T = 293 K
V = 2784.87 (7) Å3	Monoclinic, colourless
Z = 4	0.25 × 0.12 × 0.08 mm

Oxford Diffraction Xcalibur diffractometer	3724 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
graphite	θmax = 71.0°, θmin = 4.1°
heavy atom scans	h = −11→13
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	k = −18→22
Tmin = 0.544, Tmax = 0.644	l = −16→16
12418 measured reflections	3 standard reflections every 120 reflections
4954 independent reflections	intensity decay: none

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0588P)2 + 1.2361P] where P = (Fo2 + 2Fc2)/3
4954 reflections	(Δ/σ)max < 0.001
334 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.46 e Å−3
0 constraints

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Zn1	0.76391 (4)	0.05281 (2)	0.78045 (4)	0.04473 (15)
Cl1	0.80185 (10)	0.14137 (5)	0.68163 (7)	0.0583 (3)
Cl2	0.90754 (9)	−0.03331 (5)	0.80919 (8)	0.0623 (3)
Cl3	0.57608 (8)	0.00479 (5)	0.70451 (9)	0.0678 (3)
Cl4	0.77170 (12)	0.10536 (5)	0.93383 (8)	0.0734 (3)
O1	0.1080 (2)	0.18482 (13)	0.5051 (2)	0.0595 (7)
N1	0.0972 (2)	−0.04362 (13)	0.6637 (2)	0.0402 (6)
H1A	0.0414	−0.0400	0.6953	0.048*
N2	0.2328 (3)	−0.21801 (15)	0.6886 (2)	0.0480 (7)
H2A	0.2367	−0.2566	0.7221	0.058*
C1	0.1660 (3)	−0.10271 (17)	0.6593 (2)	0.0400 (7)
C2	0.1632 (3)	−0.16743 (17)	0.7074 (3)	0.0444 (8)
C3	0.3039 (3)	−0.21253 (19)	0.6142 (3)	0.0540 (9)
H3A	0.2531	−0.2301	0.5482	0.065*
H3B	0.3768	−0.2423	0.6369	0.065*
C4	0.3451 (3)	−0.14021 (19)	0.5997 (3)	0.0508 (9)
H4A	0.4222	−0.1300	0.6529	0.061*
H4B	0.3613	−0.1370	0.5334	0.061*
C5	0.2495 (3)	−0.08782 (17)	0.6044 (2)	0.0390 (7)
C6	0.2285 (3)	−0.01784 (17)	0.5711 (2)	0.0388 (7)
C7	0.2806 (3)	0.02628 (19)	0.5116 (2)	0.0476 (8)
H7A	0.3440	0.0104	0.4860	0.057*
C8	0.2367 (3)	0.0920 (2)	0.4926 (3)	0.0521 (9)
H8A	0.2696	0.1214	0.4526	0.063*
C9	0.1411 (3)	0.11741 (18)	0.5325 (2)	0.0451 (8)
C10	0.0876 (3)	0.07649 (17)	0.5905 (2)	0.0402 (7)
H10A	0.0247	0.0932	0.6161	0.048*
C11	0.1329 (3)	0.00793 (16)	0.6094 (2)	0.0357 (7)
C12	0.0871 (4)	−0.1803 (2)	0.7790 (3)	0.0640 (11)
H12A	0.0985	−0.2277	0.8032	0.096*
H12B	0.0007	−0.1725	0.7433	0.096*
H12C	0.1130	−0.1490	0.8367	0.096*
C13	0.0274 (4)	0.2179 (2)	0.5539 (3)	0.0582 (10)
H13A	0.0111	0.2649	0.5286	0.087*
H13B	0.0661	0.2188	0.6271	0.087*
H13C	−0.0495	0.1925	0.5389	0.087*
N3	0.3936 (3)	0.10991 (15)	0.7707 (2)	0.0473 (7)
H3C	0.4395	0.0784	0.7550	0.057*
N4	0.2175 (3)	0.03927 (17)	0.9329 (2)	0.0573 (8)
H4C	0.2128	0.0035	0.9700	0.069*
O2	0.4732 (3)	0.32178 (13)	0.5990 (2)	0.0626 (7)
C14	0.3153 (3)	0.10024 (18)	0.8312 (2)	0.0437 (8)
C15	0.3010 (3)	0.03874 (19)	0.8826 (3)	0.0482 (8)
C16	0.1328 (5)	0.0970 (2)	0.9292 (4)	0.0863 (15)
H16A	0.0549	0.0866	0.8771	0.104*
H16B	0.1153	0.0994	0.9950	0.104*
C17	0.1742 (4)	0.1655 (2)	0.9072 (3)	0.0649 (11)
H17A	0.2174	0.1882	0.9717	0.078*
H17B	0.1019	0.1937	0.8734	0.078*
C18	0.2582 (3)	0.16256 (18)	0.8406 (2)	0.0442 (8)
C19	0.3027 (3)	0.21319 (18)	0.7847 (2)	0.0422 (7)
C20	0.2842 (3)	0.28532 (19)	0.7657 (3)	0.0495 (8)
H20A	0.2319	0.3102	0.7949	0.059*
C21	0.3427 (3)	0.31842 (18)	0.7049 (3)	0.0508 (9)
H21A	0.3302	0.3661	0.6926	0.061*
C22	0.4230 (3)	0.28139 (18)	0.6597 (3)	0.0474 (8)
C23	0.4460 (3)	0.21113 (18)	0.6765 (3)	0.0462 (8)
H23A	0.4988	0.1870	0.6470	0.055*
C24	0.3857 (3)	0.17796 (17)	0.7401 (2)	0.0418 (7)
C25	0.3748 (4)	−0.0254 (2)	0.8814 (3)	0.0622 (10)
H25A	0.3504	−0.0613	0.9209	0.093*
H25B	0.4618	−0.0154	0.9108	0.093*
H25C	0.3601	−0.0410	0.8115	0.093*
C26	0.5400 (4)	0.2872 (2)	0.5392 (3)	0.0639 (11)
H26A	0.5706	0.3211	0.5003	0.096*
H26B	0.4858	0.2550	0.4929	0.096*
H26C	0.6090	0.2622	0.5841	0.096*

	U11	U22	U33	U12	U13	U23
Zn1	0.0481 (3)	0.0351 (2)	0.0585 (3)	0.0031 (2)	0.0273 (2)	0.0015 (2)
Cl1	0.0841 (6)	0.0390 (5)	0.0623 (5)	−0.0064 (4)	0.0377 (5)	0.0017 (4)
Cl2	0.0606 (5)	0.0537 (5)	0.0827 (6)	0.0188 (4)	0.0365 (5)	0.0093 (5)
Cl3	0.0475 (5)	0.0542 (6)	0.1095 (8)	−0.0051 (4)	0.0350 (5)	−0.0148 (6)
Cl4	0.1199 (9)	0.0529 (6)	0.0611 (5)	0.0163 (6)	0.0481 (6)	0.0022 (5)
O1	0.0744 (17)	0.0393 (14)	0.0765 (17)	0.0082 (13)	0.0404 (15)	0.0158 (13)
N1	0.0428 (14)	0.0343 (15)	0.0504 (15)	−0.0003 (12)	0.0241 (12)	0.0002 (12)
N2	0.0563 (17)	0.0316 (15)	0.0590 (16)	0.0076 (13)	0.0214 (14)	0.0037 (13)
C1	0.0412 (17)	0.0359 (17)	0.0420 (16)	−0.0014 (14)	0.0111 (14)	0.0004 (14)
C2	0.0469 (18)	0.0370 (18)	0.0516 (19)	−0.0035 (16)	0.0179 (15)	−0.0037 (15)
C3	0.050 (2)	0.048 (2)	0.065 (2)	0.0071 (17)	0.0193 (18)	−0.0009 (19)
C4	0.056 (2)	0.046 (2)	0.055 (2)	0.0059 (17)	0.0230 (17)	−0.0025 (17)
C5	0.0387 (16)	0.0397 (18)	0.0395 (16)	−0.0007 (14)	0.0129 (14)	−0.0052 (14)
C6	0.0418 (17)	0.0381 (18)	0.0365 (15)	−0.0017 (14)	0.0117 (13)	−0.0052 (14)
C7	0.0515 (19)	0.051 (2)	0.0470 (18)	0.0020 (17)	0.0254 (16)	0.0018 (17)
C8	0.056 (2)	0.054 (2)	0.0528 (19)	−0.0036 (18)	0.0251 (17)	0.0096 (18)
C9	0.052 (2)	0.0370 (18)	0.0459 (17)	−0.0005 (16)	0.0145 (15)	0.0049 (15)
C10	0.0418 (17)	0.0360 (17)	0.0445 (17)	−0.0007 (14)	0.0154 (14)	0.0003 (14)
C11	0.0390 (16)	0.0323 (16)	0.0364 (15)	−0.0045 (13)	0.0121 (13)	−0.0008 (13)
C12	0.079 (3)	0.041 (2)	0.087 (3)	0.007 (2)	0.048 (2)	0.015 (2)
C13	0.060 (2)	0.046 (2)	0.071 (2)	0.0085 (18)	0.0224 (19)	0.0100 (19)
N3	0.0495 (16)	0.0385 (16)	0.0592 (16)	0.0045 (13)	0.0243 (14)	−0.0017 (14)
N4	0.070 (2)	0.0500 (19)	0.0582 (17)	−0.0025 (16)	0.0281 (16)	0.0031 (15)
O2	0.0742 (17)	0.0449 (15)	0.0789 (17)	−0.0053 (13)	0.0384 (15)	−0.0002 (14)
C14	0.0442 (18)	0.0416 (19)	0.0452 (17)	−0.0028 (15)	0.0127 (15)	−0.0054 (15)
C15	0.053 (2)	0.045 (2)	0.0451 (18)	−0.0054 (16)	0.0107 (16)	−0.0062 (16)
C16	0.096 (3)	0.070 (3)	0.119 (4)	0.004 (3)	0.071 (3)	0.008 (3)
C17	0.072 (3)	0.061 (3)	0.075 (3)	0.007 (2)	0.041 (2)	−0.001 (2)
C18	0.0444 (18)	0.046 (2)	0.0421 (17)	−0.0009 (16)	0.0124 (15)	−0.0087 (15)
C19	0.0414 (17)	0.0404 (18)	0.0440 (17)	0.0019 (14)	0.0114 (14)	−0.0082 (15)
C20	0.051 (2)	0.0395 (19)	0.060 (2)	0.0088 (16)	0.0193 (17)	−0.0090 (17)
C21	0.059 (2)	0.0306 (17)	0.063 (2)	0.0016 (16)	0.0180 (18)	−0.0051 (17)
C22	0.0457 (18)	0.0406 (19)	0.0560 (19)	−0.0041 (16)	0.0155 (16)	−0.0038 (16)
C23	0.0437 (18)	0.0421 (19)	0.0550 (19)	0.0021 (16)	0.0179 (16)	−0.0051 (16)
C24	0.0388 (17)	0.0348 (18)	0.0495 (18)	0.0004 (14)	0.0094 (14)	−0.0061 (15)
C25	0.077 (3)	0.045 (2)	0.068 (2)	0.006 (2)	0.026 (2)	0.0060 (19)
C26	0.069 (3)	0.061 (3)	0.072 (2)	−0.002 (2)	0.037 (2)	0.001 (2)

Zn1—Cl3	2.2536 (10)	C14—C18	1.377 (5)
Zn1—Cl2	2.2580 (10)	C14—C15	1.400 (5)
Zn1—Cl1	2.2765 (9)	C15—C25	1.484 (5)
Zn1—Cl4	2.2885 (10)	C16—C17	1.449 (6)
O1—C9	1.363 (4)	C17—C18	1.487 (5)
O1—C13	1.417 (4)	C18—C19	1.409 (5)
N1—C11	1.359 (4)	C19—C20	1.407 (5)
N1—C1	1.380 (4)	C19—C24	1.422 (4)
N2—C2	1.315 (4)	C20—C21	1.353 (5)
N2—C3	1.463 (4)	C21—C22	1.420 (5)
C1—C5	1.388 (4)	C22—C23	1.375 (5)
C1—C2	1.404 (4)	C23—C24	1.396 (5)
C2—C12	1.491 (5)	N1—H1A	0.86
C3—C4	1.490 (5)	N2—H2A	0.86
C4—C5	1.484 (4)	C3—H3A	0.97
C5—C6	1.410 (5)	C3—H3B	0.97
C6—C7	1.407 (4)	C4—H4A	0.97
C6—C11	1.412 (4)	C4—H4B	0.97
C7—C8	1.348 (5)	C7—H7A	0.93
C8—C9	1.422 (5)	C8—H8A	0.93
C9—C10	1.367 (4)	C10—H10A	0.93
C10—C11	1.403 (4)	C12—H12A	0.96
N3—C24	1.361 (4)	C12—H12B	0.96
N3—C14	1.381 (4)	C12—H12C	0.96
N4—C15	1.312 (5)	C13—H13A	0.96
N4—C16	1.450 (5)	C13—H13B	0.96
O2—C22	1.365 (4)	C13—H13C	0.96
O2—C26	1.420 (4)
Cl3—Zn1—Cl2	107.88 (4)	C19—C18—C17	133.6 (3)
Cl3—Zn1—Cl1	110.26 (4)	C20—C19—C18	135.7 (3)
Cl2—Zn1—Cl1	113.37 (4)	C20—C19—C24	117.8 (3)
Cl3—Zn1—Cl4	112.03 (4)	C18—C19—C24	106.5 (3)
Cl2—Zn1—Cl4	109.20 (4)	C21—C20—C19	119.9 (3)
Cl1—Zn1—Cl4	104.15 (4)	C20—C21—C22	120.9 (3)
C9—O1—C13	117.1 (3)	O2—C22—C23	124.2 (3)
C11—N1—C1	108.2 (2)	O2—C22—C21	113.9 (3)
C2—N2—C3	123.8 (3)	C23—C22—C21	121.9 (3)
N1—C1—C5	109.3 (3)	C22—C23—C24	116.4 (3)
N1—C1—C2	127.8 (3)	N3—C24—C23	128.5 (3)
C5—C1—C2	122.8 (3)	N3—C24—C19	108.4 (3)
N2—C2—C1	117.6 (3)	C23—C24—C19	123.1 (3)
N2—C2—C12	119.5 (3)	C1—N1—H1A	126
C1—C2—C12	122.9 (3)	C11—N1—H1A	126
N2—C3—C4	114.3 (3)	C2—N2—H2A	118
C5—C4—C3	111.4 (3)	C3—N2—H2A	118
C1—C5—C6	106.9 (3)	N2—C3—H3A	109
C1—C5—C4	119.7 (3)	N2—C3—H3B	109
C6—C5—C4	133.0 (3)	C4—C3—H3A	109
C7—C6—C5	134.0 (3)	C4—C3—H3B	109
C7—C6—C11	119.4 (3)	H3A—C3—H3B	108
C5—C6—C11	106.7 (3)	C3—C4—H4A	109
C8—C7—C6	118.6 (3)	C3—C4—H4B	109
C7—C8—C9	121.4 (3)	C5—C4—H4A	109
O1—C9—C10	124.6 (3)	C5—C4—H4B	109
O1—C9—C8	113.3 (3)	H4A—C4—H4B	108
C10—C9—C8	122.1 (3)	C6—C7—H7A	121
C9—C10—C11	116.3 (3)	C8—C7—H7A	121
N1—C11—C10	128.9 (3)	C7—C8—H8A	119
N1—C11—C6	108.8 (3)	C9—C8—H8A	119
C10—C11—C6	122.2 (3)	C9—C10—H10A	122
C24—N3—C14	108.3 (3)	C11—C10—H10A	122
C15—N4—C16	123.4 (3)	C2—C12—H12A	110
C22—O2—C26	117.5 (3)	C2—C12—H12B	109
C18—C14—N3	109.5 (3)	C2—C12—H12C	109
C18—C14—C15	123.8 (3)	H12A—C12—H12B	109
N3—C14—C15	126.5 (3)	H12A—C12—H12C	109
N4—C15—C14	117.1 (3)	H12B—C12—H12C	109
N4—C15—C25	120.0 (3)	O1—C13—H13A	109
C14—C15—C25	122.9 (3)	O1—C13—H13B	109
C17—C16—N4	116.7 (4)	O1—C13—H13C	109
C16—C17—C18	113.0 (3)	H13A—C13—H13B	109
C14—C18—C19	107.3 (3)	H13A—C13—H13C	109
C14—C18—C17	119.0 (3)	H13B—C13—H13C	110
C13—O1—C9—C8	−170.7 (3)	C3—C4—C5—C6	−161.5 (3)
C13—O1—C9—C10	10.7 (4)	C1—C5—C6—C7	−178.5 (3)
C11—N1—C1—C2	177.5 (3)	C1—C5—C6—C11	1.1 (3)
C11—N1—C1—C5	2.0 (3)	C4—C5—C6—C7	8.2 (6)
C1—N1—C11—C6	−1.3 (3)	C4—C5—C6—C11	−172.2 (3)
C1—N1—C11—C10	178.6 (3)	C5—C6—C7—C8	179.2 (3)
C3—N2—C2—C1	−5.5 (5)	C11—C6—C7—C8	−0.4 (4)
C3—N2—C2—C12	175.5 (3)	C5—C6—C11—N1	0.1 (3)
C2—N2—C3—C4	29.2 (5)	C5—C6—C11—C10	−179.83
N1—C1—C2—N2	176.8 (3)	C7—C6—C11—N1	179.8 (3)
N1—C1—C2—C12	−4.2 (6)	C7—C6—C11—C10	−0.2 (4)
C5—C1—C2—N2	−8.3 (5)	C6—C7—C8—C9	0.9 (5)
C5—C1—C2—C12	170.7 (3)	C7—C8—C9—O1	−179.7 (3)
N1—C1—C5—C4	172.5 (3)	C7—C8—C9—C10	−1.1 (5)
N1—C1—C5—C6	−1.9 (3)	O1—C9—C10—C11	179.0 (3)
C2—C1—C5—C4	−3.3 (5)	C8—C9—C10—C11	0.5 (4)
C2—C1—C5—C6	−177.7 (3)	C9—C10—C11—N1	−179.8 (3)
N2—C3—C4—C5	−36.8 (4)	C9—C10—C11—C6	0.1 (4)
C3—C4—C5—C1	25.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2i	0.86	2.45	3.307 (3)	171
N2—H2A···Cl1ii	0.86	2.46	3.299 (3)	166
N3—H3C···Cl3	0.86	2.33	3.183 (3)	173
N4—H4C···Cl4iii	0.86	2.44	3.287 (3)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl2i	0.86	2.45	3.307 (3)	171
N2—H2A⋯Cl1ii	0.86	2.46	3.299 (3)	166
N3—H3C⋯Cl3	0.86	2.33	3.183 (3)	173
N4—H4C⋯Cl4iii	0.86	2.44	3.287 (3)	170

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