Bis(6-meth­oxy-1-methyl-2,3,4,9-tetra­hydro-1H-β-carbolin-2-ium) tetra­chloridozincate(II) dihydrate

Goh, T.B.; Mordi, M.N.; Mansor, S.M.; Rosli, M.M.; Fun, H.-K.

doi:10.1107/S1600536812011130

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m464-m465

doi:10.1107/S1600536812011130

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Bis(6-methoxy-1-methyl-2,3,4,9-tetrahydro-1H-β-carbolin-2-ium) tetrachloridozincate(II) dihydrate

Teik Beng Goh,^a Mohd Nizam Mordi,^a Sharif Mahsufi Mansor,^a Mohd Mustaqim Rosli ^b and Hoong-Kun Fun ^b ^*

^aCentre for Drug Research, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 29 February 2012; accepted 14 March 2012; online 24 March 2012)

The asymmetric unit of the title compound, (C₁₃H₁₇N₂O)₂[ZnCl₄]·2H₂O, contains two tetrahydroharmine cations, one tetrachlorozincate(II) anion and two water molecules. In the cations, the two 1H-indole ring systems are essentially planar, with maximum deviations of 0.016 (2) and 0.018 (2) Å, and both tetrahydropyridinium rings show a half-chair conformation. The Zn^II complex anion has a distorted tetrahedral geometry. In the crystal, intermolecular N—H⋯O, N—H⋯Cl, O—H⋯O, O—H⋯Cl and C—H⋯O hydrogen bonds link the components into a three-dimensional network. A π–π interaction with a centroid–centroid distance of 3.542 (14) Å is also observed.

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 structures of β-carboline and related compounds, see: Anlong et al. (2007 ); Larghi et al. (2005 ); Reimers et al. (1984 ); Wouters (1997 ); Ferretti et al. (2004 ). For a related tetrachloridozincate structure, see: Ma et al. (2009 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

(C₁₃H₁₇N₂O)₂[ZnCl₄]·2H₂O
M_r = 677.77
Monoclinic, P 2₁ /c
a = 7.3319 (1) Å
b = 18.5135 (3) Å
c = 22.0578 (3) Å
β = 91.516 (1)°
V = 2993.06 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.22 mm⁻¹
T = 100 K
0.39 × 0.17 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.648, T_max = 0.876
33557 measured reflections
8753 independent reflections
6404 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.098
S = 1.03
8753 reflections
356 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯Cl3ⁱ	0.90	2.49	3.271 (2)	146
N2A—H2NA⋯Cl4ⁱⁱ	0.80	2.43	3.208 (2)	164
N2A—H3NA⋯O1WBⁱⁱⁱ	0.89	1.92	2.790 (3)	166
N1B—H1NB⋯O1WB	0.92	1.99	2.872 (3)	159
N2B—H2NB⋯Cl1ⁱⁱⁱ	0.86	2.28	3.141 (2)	176
N2B—H3NB⋯Cl3ⁱⁱ	0.92	2.32	3.231 (2)	171
O1WA—H1WA⋯Cl4^iv	0.92	2.42	3.204 (2)	143
O1WA—H2WA⋯O1A^v	0.91	1.89	2.799 (3)	173
O1WB—H1WB⋯O1WA^iv	0.90	1.78	2.672 (3)	175
O1WB—H2WB⋯Cl2	0.91	2.33	3.231 (2)	169
C12B—H12E⋯O1WA^vi	0.98	2.58	3.487 (3)	153
C3B—H3BA⋯O1B^vii	0.95	2.56	3.373 (3)	143
Symmetry codes: (i) x, y-1, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) x+1, y, z; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) -x+1, -y+2, -z.

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812011130/is5085sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011130/is5085Isup2.hkl

checkCIF report

Comment top

The metal complexes of the 6-methoxy-1-methyl-4,9-dihydro-3H-β-carboline and other carboline alkaloids was previously reported to have biological activity (Al-Allaf et al., 1990). It is now well established that these classes of beta carboline alkaloids may occur under mild conditions in foods from a Pictet Spengler condensation of indoleamines such as L-tryptophan and short aliphatic aldehydes (Herraiz et al., 2003). Our present work intend to synthesize the titled compound and prepare it in salt form to investigate its safety and antiproliferative efficacy in cancer cell line.

The asymmetric unit of I contains two tetrahydroharmine cations, one zinc tetrachloride anion and two water molecules (Fig. 1). In these tetrahydroharmine cations, the maximum deviations for the two 1H-indole planes are 0.016 (2) and 0.018 (2) Å, respectively, for molecules A and B. The tetrahydropyridinium rings in both molecules show a half-chair conformation with the puckering parameters Q = 0.488 (3) Å, θ = 48.9 (4)°, φ = 24.3 (4)° for molecule A, and Q = 0.504 (3) Å, θ = 130.7 (3)°, φ = 206.6 (4)° for molecule B. The crystal structure has extensive intermolecular N—H···C, N—H···O, O—H···Cl, O—H···O and C—H···O interactions (Table 1) that link the three components into a three-dimensional network (Fig. 2). A π–π interaction with a centroid-centroid distance of 3.542 (14) Å is observed (Cg1 = N1A—C11A, Cg2 = C1B—C6B, -x, y + 1, -z + 1/2).

Related literature top

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 structures of β-carboline and related compounds, see: Anlong et al. (2007); Larghi et al. (2005); Reimers et al. (1984); Wouters (1997); Ferretti et al. (2004). For a related tetrachloridozincate structure, see: Ma et al. (2009). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

2M solution of hydrochloric acid in methanol was prepared by transferring 1.68 ml of 37% concentrated HCl acid into a 10 ml volumetric flask and was topped up to volume using methanol. The ZnCl₂ (1 mmol, 136 mg) was weighed and 0.50 ml of 2M hydrochloric acid in methanol was added. Sonication was performed to aid dissolution. 6-methoxy-1-methyl-4,9-dihydro-3H-β-carboline (2.5 mmol, 540 mg) was weighed and 0.50 ml HPLC grade methanol was added. The solution was heated on water bath to facilitate dissolution. 0.50 ml of the ZnCl₂ solution in 2M hydrochloric acid was then added to the 6-methoxy-1-methyl-4,9-dihydro-3H-β-carboline solution in methanol dropwise in a glass bottle. The side of the glass bottle was scratched with a small spatula and the bottle was kept in fridge at 4 °C for 5–7 days before yielding the colourless crystals of Bis(6-methoxy-1-methyl-4,9-dihydro-3H-β-carbolinium) tetrachloridozincatedihydrate which were filtered off, washed twice with acetone and air-dried. Crystals of the title compound, suitable to X-ray diffraction analysis, were selected directly from the samples as prepared.

Structure description top

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 structures of β-carboline and related compounds, see: Anlong et al. (2007); Larghi et al. (2005); Reimers et al. (1984); Wouters (1997); Ferretti et al. (2004). For a related tetrachloridozincate structure, see: Ma et al. (2009). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids. Hydrogen atoms are shown as spheres of arbitrary radius.
	Fig. 2. A crystal packing diagram of the title compound. Dashed lines indicate hydrogen bonds. H atoms not involved in the hydrogen bond interactions have been omitted for clarity.

Bis(6-methoxy-1-methyl-2,3,4,9-tetrahydro-1H-β-carbolin-2-ium) tetrachloridozincate(II) dihydrate top

Crystal data top

(C₁₃H₁₇N₂O)₂[ZnCl₄]·2H₂O	F(000) = 1408
M_r = 677.77	D_x = 1.504 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6348 reflections
a = 7.3319 (1) Å	θ = 2.4–30.0°
b = 18.5135 (3) Å	µ = 1.22 mm⁻¹
c = 22.0578 (3) Å	T = 100 K
β = 91.516 (1)°	Block, colourless
V = 2993.06 (8) Å³	0.39 × 0.17 × 0.11 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	8753 independent reflections
Radiation source: fine-focus sealed tube	6404 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
φ and ω scans	θ_max = 30.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
T_min = 0.648, T_max = 0.876	k = −25→26
33557 measured reflections	l = −29→31

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.034P)² + 2.4492P] where P = (F_o² + 2F_c²)/3
8753 reflections	(Δ/σ)_max = 0.001
356 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

(C₁₃H₁₇N₂O)₂[ZnCl₄]·2H₂O	V = 2993.06 (8) Å³
M_r = 677.77	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.3319 (1) Å	µ = 1.22 mm⁻¹
b = 18.5135 (3) Å	T = 100 K
c = 22.0578 (3) Å	0.39 × 0.17 × 0.11 mm
β = 91.516 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	8753 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	6404 reflections with I > 2σ(I)
T_min = 0.648, T_max = 0.876	R_int = 0.060
33557 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.03	Δρ_max = 0.70 e Å⁻³
8753 reflections	Δρ_min = −0.42 e Å⁻³
356 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.26573 (4)	0.962442 (15)	0.338408 (12)	0.01473 (7)
Cl1	−0.01952 (8)	0.92451 (3)	0.36215 (3)	0.01755 (12)
Cl2	0.24649 (10)	0.99951 (4)	0.24105 (3)	0.02531 (15)
Cl3	0.34993 (9)	1.05252 (3)	0.40340 (3)	0.02075 (13)
Cl4	0.47209 (9)	0.87115 (3)	0.34904 (3)	0.02156 (13)
O1A	0.0570 (3)	0.33708 (9)	0.60925 (7)	0.0208 (4)
N1A	0.2953 (3)	0.22751 (11)	0.39336 (9)	0.0168 (4)
H1NA	0.3328	0.1841	0.3806	0.020*
N2A	0.2749 (3)	0.35932 (11)	0.26700 (9)	0.0206 (5)
H2NA	0.3187	0.3633	0.2343	0.025*
H3NA	0.1567	0.3510	0.2614	0.025*
C1A	0.2379 (3)	0.24608 (13)	0.45051 (11)	0.0155 (5)
C2A	0.2228 (3)	0.20436 (13)	0.50269 (11)	0.0176 (5)
H2AA	0.2534	0.1545	0.5027	0.021*
C3A	0.1624 (3)	0.23764 (13)	0.55412 (11)	0.0183 (5)
H3AA	0.1514	0.2104	0.5904	0.022*
C4A	0.1165 (3)	0.31170 (13)	0.55381 (11)	0.0161 (5)
C5A	0.1324 (3)	0.35399 (13)	0.50265 (11)	0.0159 (5)
H5AA	0.1023	0.4039	0.5031	0.019*
C6A	0.1949 (3)	0.32041 (12)	0.44983 (10)	0.0144 (5)
C7A	0.2315 (3)	0.34639 (13)	0.39013 (11)	0.0158 (5)
C8A	0.2124 (4)	0.42097 (13)	0.36420 (11)	0.0185 (5)
H8AA	0.2649	0.4567	0.3932	0.022*
H8AB	0.0817	0.4325	0.3573	0.022*
C9A	0.3114 (4)	0.42501 (14)	0.30467 (12)	0.0238 (6)
H9AA	0.2706	0.4685	0.2819	0.029*
H9AB	0.4442	0.4295	0.3131	0.029*
C10A	0.3524 (4)	0.29054 (14)	0.29338 (11)	0.0207 (5)
H10A	0.4886	0.2933	0.2932	0.025*
C11A	0.2923 (3)	0.28910 (13)	0.35792 (11)	0.0171 (5)
C12A	0.0208 (4)	0.41291 (14)	0.61312 (12)	0.0230 (5)
H12A	−0.0174	0.4248	0.6542	0.034*
H12B	−0.0766	0.4259	0.5838	0.034*
H12C	0.1316	0.4400	0.6040	0.034*
C13A	0.2905 (4)	0.22674 (15)	0.25513 (12)	0.0269 (6)
H13A	0.3437	0.1823	0.2720	0.040*
H13B	0.3306	0.2333	0.2135	0.040*
H13C	0.1571	0.2234	0.2552	0.040*
O1B	0.4468 (3)	0.92386 (9)	−0.07206 (8)	0.0229 (4)
N1B	0.2155 (3)	0.76370 (11)	0.12185 (9)	0.0168 (4)
H1NB	0.1594	0.7771	0.1571	0.020*
N2B	0.2106 (3)	0.56588 (11)	0.09296 (9)	0.0180 (4)
H2NB	0.1558	0.5268	0.1035	0.022*
H3NB	0.3344	0.5618	0.0984	0.022*
C1B	0.2720 (3)	0.81144 (13)	0.07788 (11)	0.0159 (5)
C2B	0.2923 (3)	0.88670 (13)	0.07965 (11)	0.0191 (5)
H2BA	0.2675	0.9133	0.1153	0.023*
C3B	0.3491 (3)	0.92074 (13)	0.02824 (12)	0.0205 (5)
H3BA	0.3615	0.9718	0.0282	0.025*
C4B	0.3893 (3)	0.88144 (13)	−0.02451 (11)	0.0184 (5)
C5B	0.3702 (3)	0.80745 (13)	−0.02703 (11)	0.0164 (5)
H5BA	0.3975	0.7813	−0.0627	0.020*
C6B	0.3089 (3)	0.77191 (12)	0.02494 (11)	0.0147 (5)
C7B	0.2684 (3)	0.69762 (12)	0.03832 (10)	0.0142 (4)
C8B	0.2740 (4)	0.63242 (12)	−0.00178 (11)	0.0169 (5)
H8BA	0.4020	0.6169	−0.0066	0.020*
H8BB	0.2218	0.6443	−0.0424	0.020*
C9B	0.1652 (4)	0.57181 (13)	0.02624 (11)	0.0183 (5)
H9BA	0.0331	0.5814	0.0202	0.022*
H9BB	0.1937	0.5256	0.0060	0.022*
C10B	0.1468 (4)	0.62980 (13)	0.12931 (11)	0.0185 (5)
H10B	0.0104	0.6301	0.1288	0.022*
C11B	0.2120 (3)	0.69530 (12)	0.09674 (11)	0.0151 (5)
C12B	0.4831 (4)	0.88787 (15)	−0.12753 (11)	0.0237 (6)
H12D	0.5254	0.9230	−0.1572	0.036*
H12E	0.3713	0.8647	−0.1431	0.036*
H12F	0.5775	0.8512	−0.1204	0.036*
C13B	0.2165 (4)	0.62126 (15)	0.19426 (11)	0.0264 (6)
H13D	0.1824	0.6638	0.2179	0.040*
H13E	0.3497	0.6165	0.1949	0.040*
H13F	0.1626	0.5780	0.2120	0.040*
O1WA	0.8196 (3)	0.25435 (10)	0.67829 (9)	0.0288 (4)
H1WA	0.7555	0.2236	0.6529	0.043*
H2WA	0.9016	0.2780	0.6552	0.043*
O1WB	0.1004 (3)	0.83525 (10)	0.22985 (8)	0.0238 (4)
H1WB	0.1204	0.8048	0.2610	0.036*
H2WB	0.1576	0.8790	0.2333	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01490 (14)	0.01365 (13)	0.01579 (13)	−0.00034 (11)	0.00312 (10)	−0.00027 (11)
Cl1	0.0148 (3)	0.0147 (3)	0.0234 (3)	−0.0003 (2)	0.0051 (2)	−0.0018 (2)
Cl2	0.0292 (4)	0.0285 (3)	0.0183 (3)	0.0008 (3)	0.0031 (3)	0.0068 (2)
Cl3	0.0213 (3)	0.0158 (3)	0.0253 (3)	−0.0025 (2)	0.0016 (2)	−0.0045 (2)
Cl4	0.0188 (3)	0.0236 (3)	0.0227 (3)	0.0068 (2)	0.0071 (2)	0.0033 (2)
O1A	0.0264 (10)	0.0188 (9)	0.0174 (8)	−0.0001 (7)	0.0028 (7)	−0.0022 (7)
N1A	0.0194 (11)	0.0140 (9)	0.0170 (10)	0.0017 (8)	0.0025 (8)	−0.0022 (8)
N2A	0.0198 (11)	0.0235 (11)	0.0187 (10)	−0.0003 (9)	0.0060 (9)	0.0052 (9)
C1A	0.0131 (11)	0.0148 (11)	0.0188 (11)	−0.0012 (9)	0.0022 (9)	−0.0009 (9)
C2A	0.0180 (12)	0.0133 (11)	0.0216 (12)	−0.0014 (9)	0.0001 (10)	0.0007 (9)
C3A	0.0169 (12)	0.0197 (12)	0.0181 (12)	−0.0028 (10)	−0.0003 (10)	0.0027 (9)
C4A	0.0126 (11)	0.0198 (12)	0.0159 (11)	−0.0026 (9)	−0.0003 (9)	−0.0039 (9)
C5A	0.0131 (11)	0.0149 (11)	0.0197 (11)	0.0003 (9)	−0.0002 (9)	−0.0014 (9)
C6A	0.0131 (11)	0.0138 (11)	0.0162 (11)	−0.0006 (9)	−0.0002 (9)	0.0003 (9)
C7A	0.0133 (11)	0.0157 (11)	0.0184 (11)	0.0000 (9)	0.0014 (9)	0.0007 (9)
C8A	0.0209 (13)	0.0146 (11)	0.0201 (12)	0.0002 (10)	0.0027 (10)	0.0033 (9)
C9A	0.0276 (15)	0.0175 (12)	0.0265 (13)	−0.0042 (11)	0.0062 (11)	0.0026 (10)
C10A	0.0208 (13)	0.0217 (12)	0.0199 (12)	0.0037 (10)	0.0057 (10)	0.0012 (10)
C11A	0.0167 (12)	0.0175 (11)	0.0169 (11)	−0.0006 (9)	0.0003 (9)	0.0019 (9)
C12A	0.0260 (14)	0.0220 (13)	0.0210 (12)	0.0003 (11)	0.0016 (11)	−0.0061 (10)
C13A	0.0337 (16)	0.0270 (14)	0.0200 (13)	0.0043 (12)	0.0016 (11)	−0.0026 (11)
O1B	0.0268 (10)	0.0170 (9)	0.0251 (9)	−0.0034 (8)	0.0033 (8)	0.0067 (7)
N1B	0.0173 (11)	0.0159 (10)	0.0174 (10)	−0.0013 (8)	0.0049 (8)	−0.0034 (8)
N2B	0.0201 (11)	0.0141 (9)	0.0202 (10)	−0.0042 (8)	0.0044 (8)	0.0002 (8)
C1B	0.0120 (11)	0.0157 (11)	0.0199 (12)	−0.0002 (9)	−0.0003 (9)	−0.0020 (9)
C2B	0.0174 (12)	0.0161 (11)	0.0239 (13)	0.0016 (9)	−0.0003 (10)	−0.0051 (10)
C3B	0.0171 (13)	0.0143 (11)	0.0299 (13)	0.0005 (9)	−0.0020 (10)	0.0014 (10)
C4B	0.0135 (11)	0.0170 (11)	0.0246 (12)	−0.0021 (9)	−0.0004 (10)	0.0056 (10)
C5B	0.0127 (11)	0.0179 (11)	0.0186 (11)	−0.0002 (9)	0.0011 (9)	0.0005 (9)
C6B	0.0108 (11)	0.0143 (11)	0.0190 (11)	0.0012 (9)	−0.0001 (9)	0.0005 (9)
C7B	0.0133 (11)	0.0142 (11)	0.0150 (11)	−0.0012 (9)	0.0006 (9)	−0.0015 (9)
C8B	0.0200 (12)	0.0158 (11)	0.0150 (11)	−0.0025 (9)	0.0030 (9)	−0.0004 (9)
C9B	0.0225 (13)	0.0141 (11)	0.0183 (12)	−0.0032 (10)	0.0016 (10)	−0.0026 (9)
C10B	0.0199 (13)	0.0173 (11)	0.0185 (12)	−0.0032 (10)	0.0051 (10)	−0.0022 (9)
C11B	0.0130 (11)	0.0143 (11)	0.0181 (11)	−0.0009 (9)	0.0024 (9)	−0.0015 (9)
C12B	0.0234 (14)	0.0252 (13)	0.0225 (13)	−0.0031 (11)	0.0013 (11)	0.0082 (11)
C13B	0.0355 (16)	0.0261 (14)	0.0179 (12)	−0.0035 (12)	0.0032 (11)	0.0007 (10)
O1WA	0.0327 (12)	0.0249 (10)	0.0289 (10)	−0.0012 (9)	0.0048 (9)	0.0014 (8)
O1WB	0.0274 (10)	0.0238 (9)	0.0202 (9)	−0.0009 (8)	0.0034 (8)	−0.0021 (7)

Geometric parameters (Å, º) top

Zn1—Cl2	2.2554 (7)	O1B—C4B	1.385 (3)
Zn1—Cl3	2.2739 (7)	O1B—C12B	1.425 (3)
Zn1—Cl4	2.2763 (7)	N1B—C11B	1.382 (3)
Zn1—Cl1	2.2802 (6)	N1B—C1B	1.384 (3)
O1A—C4A	1.391 (3)	N1B—H1NB	0.9238
O1A—C12A	1.432 (3)	N2B—C9B	1.504 (3)
N1A—C11A	1.382 (3)	N2B—C10B	1.511 (3)
N1A—C1A	1.383 (3)	N2B—H2NB	0.8624
N1A—H1NA	0.8963	N2B—H3NB	0.9155
N2A—C9A	1.493 (3)	C1B—C2B	1.402 (3)
N2A—C10A	1.505 (3)	C1B—C6B	1.410 (3)
N2A—H2NA	0.8004	C2B—C3B	1.372 (3)
N2A—H3NA	0.8857	C2B—H2BA	0.9500
C1A—C2A	1.393 (3)	C3B—C4B	1.410 (4)
C1A—C6A	1.412 (3)	C3B—H3BA	0.9500
C2A—C3A	1.375 (3)	C4B—C5B	1.378 (3)
C2A—H2AA	0.9500	C5B—C6B	1.406 (3)
C3A—C4A	1.412 (3)	C5B—H5BA	0.9500
C3A—H3AA	0.9500	C6B—C7B	1.439 (3)
C4A—C5A	1.381 (3)	C7B—C11B	1.364 (3)
C5A—C6A	1.408 (3)	C7B—C8B	1.498 (3)
C5A—H5AA	0.9500	C8B—C9B	1.518 (3)
C6A—C7A	1.434 (3)	C8B—H8BA	0.9900
C7A—C11A	1.358 (3)	C8B—H8BB	0.9900
C7A—C8A	1.500 (3)	C9B—H9BA	0.9900
C8A—C9A	1.519 (3)	C9B—H9BB	0.9900
C8A—H8AA	0.9900	C10B—C11B	1.495 (3)
C8A—H8AB	0.9900	C10B—C13B	1.517 (4)
C9A—H9AA	0.9900	C10B—H10B	1.0000
C9A—H9AB	0.9900	C12B—H12D	0.9800
C10A—C11A	1.501 (3)	C12B—H12E	0.9800
C10A—C13A	1.514 (4)	C12B—H12F	0.9800
C10A—H10A	1.0000	C13B—H13D	0.9800
C12A—H12A	0.9800	C13B—H13E	0.9800
C12A—H12B	0.9800	C13B—H13F	0.9800
C12A—H12C	0.9800	O1WA—H1WA	0.9187
C13A—H13A	0.9800	O1WA—H2WA	0.9097
C13A—H13B	0.9800	O1WB—H1WB	0.8973
C13A—H13C	0.9800	O1WB—H2WB	0.9144

Cl2—Zn1—Cl3	112.72 (3)	H13A—C13A—H13C	109.5
Cl2—Zn1—Cl4	110.40 (3)	H13B—C13A—H13C	109.5
Cl3—Zn1—Cl4	108.12 (3)	C4B—O1B—C12B	116.91 (19)
Cl2—Zn1—Cl1	106.12 (3)	C11B—N1B—C1B	107.89 (19)
Cl3—Zn1—Cl1	108.45 (2)	C11B—N1B—H1NB	125.4
Cl4—Zn1—Cl1	111.03 (2)	C1B—N1B—H1NB	124.6
C4A—O1A—C12A	116.52 (19)	C9B—N2B—C10B	113.50 (19)
C11A—N1A—C1A	108.04 (19)	C9B—N2B—H2NB	103.4
C11A—N1A—H1NA	124.2	C10B—N2B—H2NB	111.2
C1A—N1A—H1NA	127.7	C9B—N2B—H3NB	109.1
C9A—N2A—C10A	114.4 (2)	C10B—N2B—H3NB	108.4
C9A—N2A—H2NA	110.9	H2NB—N2B—H3NB	111.2
C10A—N2A—H2NA	105.6	N1B—C1B—C2B	130.5 (2)
C9A—N2A—H3NA	112.3	N1B—C1B—C6B	108.4 (2)
C10A—N2A—H3NA	105.3	C2B—C1B—C6B	121.1 (2)
H2NA—N2A—H3NA	107.8	C3B—C2B—C1B	117.9 (2)
N1A—C1A—C2A	130.4 (2)	C3B—C2B—H2BA	121.0
N1A—C1A—C6A	107.8 (2)	C1B—C2B—H2BA	121.0
C2A—C1A—C6A	121.8 (2)	C2B—C3B—C4B	121.3 (2)
C3A—C2A—C1A	117.9 (2)	C2B—C3B—H3BA	119.3
C3A—C2A—H2AA	121.1	C4B—C3B—H3BA	119.3
C1A—C2A—H2AA	121.1	C5B—C4B—O1B	124.5 (2)
C2A—C3A—C4A	120.9 (2)	C5B—C4B—C3B	121.5 (2)
C2A—C3A—H3AA	119.6	O1B—C4B—C3B	114.0 (2)
C4A—C3A—H3AA	119.6	C4B—C5B—C6B	117.8 (2)
C5A—C4A—O1A	124.2 (2)	C4B—C5B—H5BA	121.1
C5A—C4A—C3A	122.0 (2)	C6B—C5B—H5BA	121.1
O1A—C4A—C3A	113.8 (2)	C5B—C6B—C1B	120.3 (2)
C4A—C5A—C6A	117.5 (2)	C5B—C6B—C7B	133.4 (2)
C4A—C5A—H5AA	121.2	C1B—C6B—C7B	106.3 (2)
C6A—C5A—H5AA	121.2	C11B—C7B—C6B	107.0 (2)
C5A—C6A—C1A	119.9 (2)	C11B—C7B—C8B	123.1 (2)
C5A—C6A—C7A	133.2 (2)	C6B—C7B—C8B	129.8 (2)
C1A—C6A—C7A	106.8 (2)	C7B—C8B—C9B	109.41 (19)
C11A—C7A—C6A	106.9 (2)	C7B—C8B—H8BA	109.8
C11A—C7A—C8A	123.2 (2)	C9B—C8B—H8BA	109.8
C6A—C7A—C8A	129.9 (2)	C7B—C8B—H8BB	109.8
C7A—C8A—C9A	109.5 (2)	C9B—C8B—H8BB	109.8
C7A—C8A—H8AA	109.8	H8BA—C8B—H8BB	108.2
C9A—C8A—H8AA	109.8	N2B—C9B—C8B	110.3 (2)
C7A—C8A—H8AB	109.8	N2B—C9B—H9BA	109.6
C9A—C8A—H8AB	109.8	C8B—C9B—H9BA	109.6
H8AA—C8A—H8AB	108.2	N2B—C9B—H9BB	109.6
N2A—C9A—C8A	111.0 (2)	C8B—C9B—H9BB	109.6
N2A—C9A—H9AA	109.4	H9BA—C9B—H9BB	108.1
C8A—C9A—H9AA	109.4	C11B—C10B—N2B	105.84 (18)
N2A—C9A—H9AB	109.4	C11B—C10B—C13B	115.8 (2)
C8A—C9A—H9AB	109.4	N2B—C10B—C13B	108.6 (2)
H9AA—C9A—H9AB	108.0	C11B—C10B—H10B	108.8
C11A—C10A—N2A	105.33 (19)	N2B—C10B—H10B	108.8
C11A—C10A—C13A	115.0 (2)	C13B—C10B—H10B	108.8
N2A—C10A—C13A	109.9 (2)	C7B—C11B—N1B	110.3 (2)
C11A—C10A—H10A	108.8	C7B—C11B—C10B	126.0 (2)
N2A—C10A—H10A	108.8	N1B—C11B—C10B	123.6 (2)
C13A—C10A—H10A	108.8	O1B—C12B—H12D	109.5
C7A—C11A—N1A	110.4 (2)	O1B—C12B—H12E	109.5
C7A—C11A—C10A	126.2 (2)	H12D—C12B—H12E	109.5
N1A—C11A—C10A	123.4 (2)	O1B—C12B—H12F	109.5
O1A—C12A—H12A	109.5	H12D—C12B—H12F	109.5
O1A—C12A—H12B	109.5	H12E—C12B—H12F	109.5
H12A—C12A—H12B	109.5	C10B—C13B—H13D	109.5
O1A—C12A—H12C	109.5	C10B—C13B—H13E	109.5
H12A—C12A—H12C	109.5	H13D—C13B—H13E	109.5
H12B—C12A—H12C	109.5	C10B—C13B—H13F	109.5
C10A—C13A—H13A	109.5	H13D—C13B—H13F	109.5
C10A—C13A—H13B	109.5	H13E—C13B—H13F	109.5
H13A—C13A—H13B	109.5	H1WA—O1WA—H2WA	107.0
C10A—C13A—H13C	109.5	H1WB—O1WB—H2WB	115.3

C11A—N1A—C1A—C2A	−177.6 (3)	C11B—N1B—C1B—C2B	177.7 (3)
C11A—N1A—C1A—C6A	1.2 (3)	C11B—N1B—C1B—C6B	−1.5 (3)
N1A—C1A—C2A—C3A	179.4 (2)	N1B—C1B—C2B—C3B	−179.1 (3)
C6A—C1A—C2A—C3A	0.7 (4)	C6B—C1B—C2B—C3B	0.0 (4)
C1A—C2A—C3A—C4A	0.3 (4)	C1B—C2B—C3B—C4B	−1.2 (4)
C12A—O1A—C4A—C5A	−3.6 (3)	C12B—O1B—C4B—C5B	1.9 (4)
C12A—O1A—C4A—C3A	175.7 (2)	C12B—O1B—C4B—C3B	−177.7 (2)
C2A—C3A—C4A—C5A	−1.0 (4)	C2B—C3B—C4B—C5B	1.2 (4)
C2A—C3A—C4A—O1A	179.7 (2)	C2B—C3B—C4B—O1B	−179.3 (2)
O1A—C4A—C5A—C6A	179.9 (2)	O1B—C4B—C5B—C6B	−179.5 (2)
C3A—C4A—C5A—C6A	0.7 (4)	C3B—C4B—C5B—C6B	0.0 (4)
C4A—C5A—C6A—C1A	0.2 (3)	C4B—C5B—C6B—C1B	−1.1 (4)
C4A—C5A—C6A—C7A	−178.5 (3)	C4B—C5B—C6B—C7B	177.8 (3)
N1A—C1A—C6A—C5A	−179.9 (2)	N1B—C1B—C6B—C5B	−179.6 (2)
C2A—C1A—C6A—C5A	−0.9 (4)	C2B—C1B—C6B—C5B	1.1 (4)
N1A—C1A—C6A—C7A	−0.9 (3)	N1B—C1B—C6B—C7B	1.2 (3)
C2A—C1A—C6A—C7A	178.1 (2)	C2B—C1B—C6B—C7B	−178.1 (2)
C5A—C6A—C7A—C11A	179.1 (3)	C5B—C6B—C7B—C11B	−179.5 (3)
C1A—C6A—C7A—C11A	0.2 (3)	C1B—C6B—C7B—C11B	−0.4 (3)
C5A—C6A—C7A—C8A	−0.5 (5)	C5B—C6B—C7B—C8B	−2.2 (5)
C1A—C6A—C7A—C8A	−179.3 (2)	C1B—C6B—C7B—C8B	176.8 (2)
C11A—C7A—C8A—C9A	−13.4 (3)	C11B—C7B—C8B—C9B	14.5 (3)
C6A—C7A—C8A—C9A	166.1 (3)	C6B—C7B—C8B—C9B	−162.4 (2)
C10A—N2A—C9A—C8A	−66.4 (3)	C10B—N2B—C9B—C8B	67.6 (3)
C7A—C8A—C9A—N2A	43.0 (3)	C7B—C8B—C9B—N2B	−45.0 (3)
C9A—N2A—C10A—C11A	49.5 (3)	C9B—N2B—C10B—C11B	−49.5 (3)
C9A—N2A—C10A—C13A	174.0 (2)	C9B—N2B—C10B—C13B	−174.4 (2)
C6A—C7A—C11A—N1A	0.5 (3)	C6B—C7B—C11B—N1B	−0.5 (3)
C8A—C7A—C11A—N1A	−179.9 (2)	C8B—C7B—C11B—N1B	−178.0 (2)
C6A—C7A—C11A—C10A	−178.3 (2)	C6B—C7B—C11B—C10B	176.8 (2)
C8A—C7A—C11A—C10A	1.2 (4)	C8B—C7B—C11B—C10B	−0.7 (4)
C1A—N1A—C11A—C7A	−1.1 (3)	C1B—N1B—C11B—C7B	1.3 (3)
C1A—N1A—C11A—C10A	177.8 (2)	C1B—N1B—C11B—C10B	−176.1 (2)
N2A—C10A—C11A—C7A	−18.0 (3)	N2B—C10B—C11B—C7B	17.2 (3)
C13A—C10A—C11A—C7A	−139.1 (3)	C13B—C10B—C11B—C7B	137.5 (3)
N2A—C10A—C11A—N1A	163.3 (2)	N2B—C10B—C11B—N1B	−165.8 (2)
C13A—C10A—C11A—N1A	42.1 (4)	C13B—C10B—C11B—N1B	−45.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···Cl3ⁱ	0.90	2.49	3.271 (2)	146
N2A—H2NA···Cl4ⁱⁱ	0.80	2.43	3.208 (2)	164
N2A—H3NA···O1WBⁱⁱⁱ	0.89	1.92	2.790 (3)	166
N1B—H1NB···O1WB	0.92	1.99	2.872 (3)	159
N2B—H2NB···Cl1ⁱⁱⁱ	0.86	2.28	3.141 (2)	176
N2B—H3NB···Cl3ⁱⁱ	0.92	2.32	3.231 (2)	171
O1WA—H1WA···Cl4^iv	0.92	2.42	3.204 (2)	143
O1WA—H2WA···O1A^v	0.91	1.89	2.799 (3)	173
O1WB—H1WB···O1WA^iv	0.90	1.78	2.672 (3)	175
O1WB—H2WB···Cl2	0.91	2.33	3.231 (2)	169
C12B—H12E···O1WA^vi	0.98	2.58	3.487 (3)	153
C3B—H3BA···O1B^vii	0.95	2.56	3.373 (3)	143

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x+1, −y+1, −z+1; (v) x+1, y, z; (vi) −x+1, y+1/2, −z+1/2; (vii) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	(C₁₃H₁₇N₂O)₂[ZnCl₄]·2H₂O
M_r	677.77
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.3319 (1), 18.5135 (3), 22.0578 (3)
β (°)	91.516 (1)
V (Å³)	2993.06 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.22
Crystal size (mm)	0.39 × 0.17 × 0.11

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.648, 0.876
No. of measured, independent and observed [I > 2σ(I)] reflections	33557, 8753, 6404
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.098, 1.03
No. of reflections	8753
No. of parameters	356
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.42

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···Cl3ⁱ	0.90	2.49	3.271 (2)	146
N2A—H2NA···Cl4ⁱⁱ	0.80	2.43	3.208 (2)	164
N2A—H3NA···O1WBⁱⁱⁱ	0.89	1.92	2.790 (3)	166
N1B—H1NB···O1WB	0.92	1.99	2.872 (3)	159
N2B—H2NB···Cl1ⁱⁱⁱ	0.86	2.28	3.141 (2)	176
N2B—H3NB···Cl3ⁱⁱ	0.92	2.32	3.231 (2)	171
O1WA—H1WA···Cl4^iv	0.92	2.42	3.204 (2)	143
O1WA—H2WA···O1A^v	0.91	1.89	2.799 (3)	173
O1WB—H1WB···O1WA^iv	0.90	1.78	2.672 (3)	175
O1WB—H2WB···Cl2	0.91	2.33	3.231 (2)	169
C12B—H12E···O1WA^vi	0.98	2.58	3.487 (3)	153
C3B—H3BA···O1B^vii	0.95	2.56	3.373 (3)	143

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x+1, −y+1, −z+1; (v) x+1, y, z; (vi) −x+1, y+1/2, −z+1/2; (vii) −x+1, −y+2, −z.

Acknowledgements

This work was supported by USM Research University Grant No. 1001/CDADAH/815020 and the R&D Initiative Fund, Ministry of Science, Technology and Innovation, Malaysia (MOSTI). HKF also thanks Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m464-m465

doi:10.1107/S1600536812011130

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

Bis(6-meth­­oxy-1-methyl-2,3,4,9-tetra­hydro-1H-β-carbolin-2-ium) tetra­chloridozincate(II) dihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Bis(6-methoxy-1-methyl-2,3,4,9-tetrahydro-1H-β-carbolin-2-ium) tetrachloridozincate(II) dihydrate