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Acta Cryst. (2012). E68, m464-m465    [ doi:10.1107/S1600536812011130 ]

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

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

Abstract top

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 ZnII 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 [pi]-[pi] interaction with a centroid-centroid distance of 3.542 (14) Å is also observed.

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.

Refinement top

O and N bound H atoms are located from a difference Fourier map and refined using a riding model. The remaining H atoms were positioned geometrically and refined using a riding model with C—H = 0.95–1.00 Å and Uiso(H) = 1.2 or 1.5Ueq(C-methyl). A rotating group model was applied to the methyl groups.

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
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids. Hydrogen atoms are shown as spheres of arbitrary radius.
[Figure 2] 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]·2H2OF(000) = 1408
Mr = 677.77Dx = 1.504 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6348 reflections
a = 7.3319 (1) Åθ = 2.4–30.0°
b = 18.5135 (3) ŵ = 1.22 mm−1
c = 22.0578 (3) ÅT = 100 K
β = 91.516 (1)°Block, colourless
V = 2993.06 (8) Å30.39 × 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 tube6404 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.060
φ and ω scansθmax = 30.1°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		h = −10→10
Tmin = 0.648, Tmax = 0.876k = −25→26
33557 measured reflectionsl = −29→31
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.034P)2 + 2.4492P]
where P = (Fo2 + 2Fc2)/3
8753 reflections(Δ/σ)max = 0.001
356 parametersΔρmax = 0.70 e Å−3
0 restraintsΔρmin = −0.42 e Å−3
Crystal data top
(C13H17N2O)2[ZnCl4]·2H2OV = 2993.06 (8) Å3
Mr = 677.77Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.3319 (1) ŵ = 1.22 mm−1
b = 18.5135 (3) ÅT = 100 K
c = 22.0578 (3) Å0.39 × 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)
Tmin = 0.648, Tmax = 0.876Rint = 0.060
33557 measured reflectionsθmax = 30.1°
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.098Δρmax = 0.70 e Å−3
S = 1.03Δρmin = −0.42 e Å−3
8753 reflectionsAbsolute structure: ?
356 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Zn10.26573 (4)0.962442 (15)0.338408 (12)0.01473 (7)
Cl1−0.01952 (8)0.92451 (3)0.36215 (3)0.01755 (12)
Cl20.24649 (10)0.99951 (4)0.24105 (3)0.02531 (15)
Cl30.34993 (9)1.05252 (3)0.40340 (3)0.02075 (13)
Cl40.47209 (9)0.87115 (3)0.34904 (3)0.02156 (13)
O1A0.0570 (3)0.33708 (9)0.60925 (7)0.0208 (4)
N1A0.2953 (3)0.22751 (11)0.39336 (9)0.0168 (4)
H1NA0.33280.18410.38060.020*
N2A0.2749 (3)0.35932 (11)0.26700 (9)0.0206 (5)
H2NA0.31870.36330.23430.025*
H3NA0.15670.35100.26140.025*
C1A0.2379 (3)0.24608 (13)0.45051 (11)0.0155 (5)
C2A0.2228 (3)0.20436 (13)0.50269 (11)0.0176 (5)
H2AA0.25340.15450.50270.021*
C3A0.1624 (3)0.23764 (13)0.55412 (11)0.0183 (5)
H3AA0.15140.21040.59040.022*
C4A0.1165 (3)0.31170 (13)0.55381 (11)0.0161 (5)
C5A0.1324 (3)0.35399 (13)0.50265 (11)0.0159 (5)
H5AA0.10230.40390.50310.019*
C6A0.1949 (3)0.32041 (12)0.44983 (10)0.0144 (5)
C7A0.2315 (3)0.34639 (13)0.39013 (11)0.0158 (5)
C8A0.2124 (4)0.42097 (13)0.36420 (11)0.0185 (5)
H8AA0.26490.45670.39320.022*
H8AB0.08170.43250.35730.022*
C9A0.3114 (4)0.42501 (14)0.30467 (12)0.0238 (6)
H9AA0.27060.46850.28190.029*
H9AB0.44420.42950.31310.029*
C10A0.3524 (4)0.29054 (14)0.29338 (11)0.0207 (5)
H10A0.48860.29330.29320.025*
C11A0.2923 (3)0.28910 (13)0.35792 (11)0.0171 (5)
C12A0.0208 (4)0.41291 (14)0.61312 (12)0.0230 (5)
H12A−0.01740.42480.65420.034*
H12B−0.07660.42590.58380.034*
H12C0.13160.44000.60400.034*
C13A0.2905 (4)0.22674 (15)0.25513 (12)0.0269 (6)
H13A0.34370.18230.27200.040*
H13B0.33060.23330.21350.040*
H13C0.15710.22340.25520.040*
O1B0.4468 (3)0.92386 (9)−0.07206 (8)0.0229 (4)
N1B0.2155 (3)0.76370 (11)0.12185 (9)0.0168 (4)
H1NB0.15940.77710.15710.020*
N2B0.2106 (3)0.56588 (11)0.09296 (9)0.0180 (4)
H2NB0.15580.52680.10350.022*
H3NB0.33440.56180.09840.022*
C1B0.2720 (3)0.81144 (13)0.07788 (11)0.0159 (5)
C2B0.2923 (3)0.88670 (13)0.07965 (11)0.0191 (5)
H2BA0.26750.91330.11530.023*
C3B0.3491 (3)0.92074 (13)0.02824 (12)0.0205 (5)
H3BA0.36150.97180.02820.025*
C4B0.3893 (3)0.88144 (13)−0.02451 (11)0.0184 (5)
C5B0.3702 (3)0.80745 (13)−0.02703 (11)0.0164 (5)
H5BA0.39750.7813−0.06270.020*
C6B0.3089 (3)0.77191 (12)0.02494 (11)0.0147 (5)
C7B0.2684 (3)0.69762 (12)0.03832 (10)0.0142 (4)
C8B0.2740 (4)0.63242 (12)−0.00178 (11)0.0169 (5)
H8BA0.40200.6169−0.00660.020*
H8BB0.22180.6443−0.04240.020*
C9B0.1652 (4)0.57181 (13)0.02624 (11)0.0183 (5)
H9BA0.03310.58140.02020.022*
H9BB0.19370.52560.00600.022*
C10B0.1468 (4)0.62980 (13)0.12931 (11)0.0185 (5)
H10B0.01040.63010.12880.022*
C11B0.2120 (3)0.69530 (12)0.09674 (11)0.0151 (5)
C12B0.4831 (4)0.88787 (15)−0.12753 (11)0.0237 (6)
H12D0.52540.9230−0.15720.036*
H12E0.37130.8647−0.14310.036*
H12F0.57750.8512−0.12040.036*
C13B0.2165 (4)0.62126 (15)0.19426 (11)0.0264 (6)
H13D0.18240.66380.21790.040*
H13E0.34970.61650.19490.040*
H13F0.16260.57800.21200.040*
O1WA0.8196 (3)0.25435 (10)0.67829 (9)0.0288 (4)
H1WA0.75550.22360.65290.043*
H2WA0.90160.27800.65520.043*
O1WB0.1004 (3)0.83525 (10)0.22985 (8)0.0238 (4)
H1WB0.12040.80480.26100.036*
H2WB0.15760.87900.23330.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01490 (14)0.01365 (13)0.01579 (13)−0.00034 (11)0.00312 (10)−0.00027 (11)
Cl10.0148 (3)0.0147 (3)0.0234 (3)−0.0003 (2)0.0051 (2)−0.0018 (2)
Cl20.0292 (4)0.0285 (3)0.0183 (3)0.0008 (3)0.0031 (3)0.0068 (2)
Cl30.0213 (3)0.0158 (3)0.0253 (3)−0.0025 (2)0.0016 (2)−0.0045 (2)
Cl40.0188 (3)0.0236 (3)0.0227 (3)0.0068 (2)0.0071 (2)0.0033 (2)
O1A0.0264 (10)0.0188 (9)0.0174 (8)−0.0001 (7)0.0028 (7)−0.0022 (7)
N1A0.0194 (11)0.0140 (9)0.0170 (10)0.0017 (8)0.0025 (8)−0.0022 (8)
N2A0.0198 (11)0.0235 (11)0.0187 (10)−0.0003 (9)0.0060 (9)0.0052 (9)
C1A0.0131 (11)0.0148 (11)0.0188 (11)−0.0012 (9)0.0022 (9)−0.0009 (9)
C2A0.0180 (12)0.0133 (11)0.0216 (12)−0.0014 (9)0.0001 (10)0.0007 (9)
C3A0.0169 (12)0.0197 (12)0.0181 (12)−0.0028 (10)−0.0003 (10)0.0027 (9)
C4A0.0126 (11)0.0198 (12)0.0159 (11)−0.0026 (9)−0.0003 (9)−0.0039 (9)
C5A0.0131 (11)0.0149 (11)0.0197 (11)0.0003 (9)−0.0002 (9)−0.0014 (9)
C6A0.0131 (11)0.0138 (11)0.0162 (11)−0.0006 (9)−0.0002 (9)0.0003 (9)
C7A0.0133 (11)0.0157 (11)0.0184 (11)0.0000 (9)0.0014 (9)0.0007 (9)
C8A0.0209 (13)0.0146 (11)0.0201 (12)0.0002 (10)0.0027 (10)0.0033 (9)
C9A0.0276 (15)0.0175 (12)0.0265 (13)−0.0042 (11)0.0062 (11)0.0026 (10)
C10A0.0208 (13)0.0217 (12)0.0199 (12)0.0037 (10)0.0057 (10)0.0012 (10)
C11A0.0167 (12)0.0175 (11)0.0169 (11)−0.0006 (9)0.0003 (9)0.0019 (9)
C12A0.0260 (14)0.0220 (13)0.0210 (12)0.0003 (11)0.0016 (11)−0.0061 (10)
C13A0.0337 (16)0.0270 (14)0.0200 (13)0.0043 (12)0.0016 (11)−0.0026 (11)
O1B0.0268 (10)0.0170 (9)0.0251 (9)−0.0034 (8)0.0033 (8)0.0067 (7)
N1B0.0173 (11)0.0159 (10)0.0174 (10)−0.0013 (8)0.0049 (8)−0.0034 (8)
N2B0.0201 (11)0.0141 (9)0.0202 (10)−0.0042 (8)0.0044 (8)0.0002 (8)
C1B0.0120 (11)0.0157 (11)0.0199 (12)−0.0002 (9)−0.0003 (9)−0.0020 (9)
C2B0.0174 (12)0.0161 (11)0.0239 (13)0.0016 (9)−0.0003 (10)−0.0051 (10)
C3B0.0171 (13)0.0143 (11)0.0299 (13)0.0005 (9)−0.0020 (10)0.0014 (10)
C4B0.0135 (11)0.0170 (11)0.0246 (12)−0.0021 (9)−0.0004 (10)0.0056 (10)
C5B0.0127 (11)0.0179 (11)0.0186 (11)−0.0002 (9)0.0011 (9)0.0005 (9)
C6B0.0108 (11)0.0143 (11)0.0190 (11)0.0012 (9)−0.0001 (9)0.0005 (9)
C7B0.0133 (11)0.0142 (11)0.0150 (11)−0.0012 (9)0.0006 (9)−0.0015 (9)
C8B0.0200 (12)0.0158 (11)0.0150 (11)−0.0025 (9)0.0030 (9)−0.0004 (9)
C9B0.0225 (13)0.0141 (11)0.0183 (12)−0.0032 (10)0.0016 (10)−0.0026 (9)
C10B0.0199 (13)0.0173 (11)0.0185 (12)−0.0032 (10)0.0051 (10)−0.0022 (9)
C11B0.0130 (11)0.0143 (11)0.0181 (11)−0.0009 (9)0.0024 (9)−0.0015 (9)
C12B0.0234 (14)0.0252 (13)0.0225 (13)−0.0031 (11)0.0013 (11)0.0082 (11)
C13B0.0355 (16)0.0261 (14)0.0179 (12)−0.0035 (12)0.0032 (11)0.0007 (10)
O1WA0.0327 (12)0.0249 (10)0.0289 (10)−0.0012 (9)0.0048 (9)0.0014 (8)
O1WB0.0274 (10)0.0238 (9)0.0202 (9)−0.0009 (8)0.0034 (8)−0.0021 (7)
Geometric parameters (Å, º) top
Zn1—Cl22.2554 (7)O1B—C4B1.385 (3)
Zn1—Cl32.2739 (7)O1B—C12B1.425 (3)
Zn1—Cl42.2763 (7)N1B—C11B1.382 (3)
Zn1—Cl12.2802 (6)N1B—C1B1.384 (3)
O1A—C4A1.391 (3)N1B—H1NB0.9238
O1A—C12A1.432 (3)N2B—C9B1.504 (3)
N1A—C11A1.382 (3)N2B—C10B1.511 (3)
N1A—C1A1.383 (3)N2B—H2NB0.8624
N1A—H1NA0.8963N2B—H3NB0.9155
N2A—C9A1.493 (3)C1B—C2B1.402 (3)
N2A—C10A1.505 (3)C1B—C6B1.410 (3)
N2A—H2NA0.8004C2B—C3B1.372 (3)
N2A—H3NA0.8857C2B—H2BA0.9500
C1A—C2A1.393 (3)C3B—C4B1.410 (4)
C1A—C6A1.412 (3)C3B—H3BA0.9500
C2A—C3A1.375 (3)C4B—C5B1.378 (3)
C2A—H2AA0.9500C5B—C6B1.406 (3)
C3A—C4A1.412 (3)C5B—H5BA0.9500
C3A—H3AA0.9500C6B—C7B1.439 (3)
C4A—C5A1.381 (3)C7B—C11B1.364 (3)
C5A—C6A1.408 (3)C7B—C8B1.498 (3)
C5A—H5AA0.9500C8B—C9B1.518 (3)
C6A—C7A1.434 (3)C8B—H8BA0.9900
C7A—C11A1.358 (3)C8B—H8BB0.9900
C7A—C8A1.500 (3)C9B—H9BA0.9900
C8A—C9A1.519 (3)C9B—H9BB0.9900
C8A—H8AA0.9900C10B—C11B1.495 (3)
C8A—H8AB0.9900C10B—C13B1.517 (4)
C9A—H9AA0.9900C10B—H10B1.0000
C9A—H9AB0.9900C12B—H12D0.9800
C10A—C11A1.501 (3)C12B—H12E0.9800
C10A—C13A1.514 (4)C12B—H12F0.9800
C10A—H10A1.0000C13B—H13D0.9800
C12A—H12A0.9800C13B—H13E0.9800
C12A—H12B0.9800C13B—H13F0.9800
C12A—H12C0.9800O1WA—H1WA0.9187
C13A—H13A0.9800O1WA—H2WA0.9097
C13A—H13B0.9800O1WB—H1WB0.8973
C13A—H13C0.9800O1WB—H2WB0.9144
Cl2—Zn1—Cl3112.72 (3)H13A—C13A—H13C109.5
Cl2—Zn1—Cl4110.40 (3)H13B—C13A—H13C109.5
Cl3—Zn1—Cl4108.12 (3)C4B—O1B—C12B116.91 (19)
Cl2—Zn1—Cl1106.12 (3)C11B—N1B—C1B107.89 (19)
Cl3—Zn1—Cl1108.45 (2)C11B—N1B—H1NB125.4
Cl4—Zn1—Cl1111.03 (2)C1B—N1B—H1NB124.6
C4A—O1A—C12A116.52 (19)C9B—N2B—C10B113.50 (19)
C11A—N1A—C1A108.04 (19)C9B—N2B—H2NB103.4
C11A—N1A—H1NA124.2C10B—N2B—H2NB111.2
C1A—N1A—H1NA127.7C9B—N2B—H3NB109.1
C9A—N2A—C10A114.4 (2)C10B—N2B—H3NB108.4
C9A—N2A—H2NA110.9H2NB—N2B—H3NB111.2
C10A—N2A—H2NA105.6N1B—C1B—C2B130.5 (2)
C9A—N2A—H3NA112.3N1B—C1B—C6B108.4 (2)
C10A—N2A—H3NA105.3C2B—C1B—C6B121.1 (2)
H2NA—N2A—H3NA107.8C3B—C2B—C1B117.9 (2)
N1A—C1A—C2A130.4 (2)C3B—C2B—H2BA121.0
N1A—C1A—C6A107.8 (2)C1B—C2B—H2BA121.0
C2A—C1A—C6A121.8 (2)C2B—C3B—C4B121.3 (2)
C3A—C2A—C1A117.9 (2)C2B—C3B—H3BA119.3
C3A—C2A—H2AA121.1C4B—C3B—H3BA119.3
C1A—C2A—H2AA121.1C5B—C4B—O1B124.5 (2)
C2A—C3A—C4A120.9 (2)C5B—C4B—C3B121.5 (2)
C2A—C3A—H3AA119.6O1B—C4B—C3B114.0 (2)
C4A—C3A—H3AA119.6C4B—C5B—C6B117.8 (2)
C5A—C4A—O1A124.2 (2)C4B—C5B—H5BA121.1
C5A—C4A—C3A122.0 (2)C6B—C5B—H5BA121.1
O1A—C4A—C3A113.8 (2)C5B—C6B—C1B120.3 (2)
C4A—C5A—C6A117.5 (2)C5B—C6B—C7B133.4 (2)
C4A—C5A—H5AA121.2C1B—C6B—C7B106.3 (2)
C6A—C5A—H5AA121.2C11B—C7B—C6B107.0 (2)
C5A—C6A—C1A119.9 (2)C11B—C7B—C8B123.1 (2)
C5A—C6A—C7A133.2 (2)C6B—C7B—C8B129.8 (2)
C1A—C6A—C7A106.8 (2)C7B—C8B—C9B109.41 (19)
C11A—C7A—C6A106.9 (2)C7B—C8B—H8BA109.8
C11A—C7A—C8A123.2 (2)C9B—C8B—H8BA109.8
C6A—C7A—C8A129.9 (2)C7B—C8B—H8BB109.8
C7A—C8A—C9A109.5 (2)C9B—C8B—H8BB109.8
C7A—C8A—H8AA109.8H8BA—C8B—H8BB108.2
C9A—C8A—H8AA109.8N2B—C9B—C8B110.3 (2)
C7A—C8A—H8AB109.8N2B—C9B—H9BA109.6
C9A—C8A—H8AB109.8C8B—C9B—H9BA109.6
H8AA—C8A—H8AB108.2N2B—C9B—H9BB109.6
N2A—C9A—C8A111.0 (2)C8B—C9B—H9BB109.6
N2A—C9A—H9AA109.4H9BA—C9B—H9BB108.1
C8A—C9A—H9AA109.4C11B—C10B—N2B105.84 (18)
N2A—C9A—H9AB109.4C11B—C10B—C13B115.8 (2)
C8A—C9A—H9AB109.4N2B—C10B—C13B108.6 (2)
H9AA—C9A—H9AB108.0C11B—C10B—H10B108.8
C11A—C10A—N2A105.33 (19)N2B—C10B—H10B108.8
C11A—C10A—C13A115.0 (2)C13B—C10B—H10B108.8
N2A—C10A—C13A109.9 (2)C7B—C11B—N1B110.3 (2)
C11A—C10A—H10A108.8C7B—C11B—C10B126.0 (2)
N2A—C10A—H10A108.8N1B—C11B—C10B123.6 (2)
C13A—C10A—H10A108.8O1B—C12B—H12D109.5
C7A—C11A—N1A110.4 (2)O1B—C12B—H12E109.5
C7A—C11A—C10A126.2 (2)H12D—C12B—H12E109.5
N1A—C11A—C10A123.4 (2)O1B—C12B—H12F109.5
O1A—C12A—H12A109.5H12D—C12B—H12F109.5
O1A—C12A—H12B109.5H12E—C12B—H12F109.5
H12A—C12A—H12B109.5C10B—C13B—H13D109.5
O1A—C12A—H12C109.5C10B—C13B—H13E109.5
H12A—C12A—H12C109.5H13D—C13B—H13E109.5
H12B—C12A—H12C109.5C10B—C13B—H13F109.5
C10A—C13A—H13A109.5H13D—C13B—H13F109.5
C10A—C13A—H13B109.5H13E—C13B—H13F109.5
H13A—C13A—H13B109.5H1WA—O1WA—H2WA107.0
C10A—C13A—H13C109.5H1WB—O1WB—H2WB115.3
C11A—N1A—C1A—C2A−177.6 (3)C11B—N1B—C1B—C2B177.7 (3)
C11A—N1A—C1A—C6A1.2 (3)C11B—N1B—C1B—C6B−1.5 (3)
N1A—C1A—C2A—C3A179.4 (2)N1B—C1B—C2B—C3B−179.1 (3)
C6A—C1A—C2A—C3A0.7 (4)C6B—C1B—C2B—C3B0.0 (4)
C1A—C2A—C3A—C4A0.3 (4)C1B—C2B—C3B—C4B−1.2 (4)
C12A—O1A—C4A—C5A−3.6 (3)C12B—O1B—C4B—C5B1.9 (4)
C12A—O1A—C4A—C3A175.7 (2)C12B—O1B—C4B—C3B−177.7 (2)
C2A—C3A—C4A—C5A−1.0 (4)C2B—C3B—C4B—C5B1.2 (4)
C2A—C3A—C4A—O1A179.7 (2)C2B—C3B—C4B—O1B−179.3 (2)
O1A—C4A—C5A—C6A179.9 (2)O1B—C4B—C5B—C6B−179.5 (2)
C3A—C4A—C5A—C6A0.7 (4)C3B—C4B—C5B—C6B0.0 (4)
C4A—C5A—C6A—C1A0.2 (3)C4B—C5B—C6B—C1B−1.1 (4)
C4A—C5A—C6A—C7A−178.5 (3)C4B—C5B—C6B—C7B177.8 (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—C5B1.1 (4)
N1A—C1A—C6A—C7A−0.9 (3)N1B—C1B—C6B—C7B1.2 (3)
C2A—C1A—C6A—C7A178.1 (2)C2B—C1B—C6B—C7B−178.1 (2)
C5A—C6A—C7A—C11A179.1 (3)C5B—C6B—C7B—C11B−179.5 (3)
C1A—C6A—C7A—C11A0.2 (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—C8B176.8 (2)
C11A—C7A—C8A—C9A−13.4 (3)C11B—C7B—C8B—C9B14.5 (3)
C6A—C7A—C8A—C9A166.1 (3)C6B—C7B—C8B—C9B−162.4 (2)
C10A—N2A—C9A—C8A−66.4 (3)C10B—N2B—C9B—C8B67.6 (3)
C7A—C8A—C9A—N2A43.0 (3)C7B—C8B—C9B—N2B−45.0 (3)
C9A—N2A—C10A—C11A49.5 (3)C9B—N2B—C10B—C11B−49.5 (3)
C9A—N2A—C10A—C13A174.0 (2)C9B—N2B—C10B—C13B−174.4 (2)
C6A—C7A—C11A—N1A0.5 (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—C10B176.8 (2)
C8A—C7A—C11A—C10A1.2 (4)C8B—C7B—C11B—C10B−0.7 (4)
C1A—N1A—C11A—C7A−1.1 (3)C1B—N1B—C11B—C7B1.3 (3)
C1A—N1A—C11A—C10A177.8 (2)C1B—N1B—C11B—C10B−176.1 (2)
N2A—C10A—C11A—C7A−18.0 (3)N2B—C10B—C11B—C7B17.2 (3)
C13A—C10A—C11A—C7A−139.1 (3)C13B—C10B—C11B—C7B137.5 (3)
N2A—C10A—C11A—N1A163.3 (2)N2B—C10B—C11B—N1B−165.8 (2)
C13A—C10A—C11A—N1A42.1 (4)C13B—C10B—C11B—N1B−45.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1NA···Cl3i0.902.493.271 (2)146
N2A—H2NA···Cl4ii0.802.433.208 (2)164
N2A—H3NA···O1WBiii0.891.922.790 (3)166
N1B—H1NB···O1WB0.921.992.872 (3)159
N2B—H2NB···Cl1iii0.862.283.141 (2)176
N2B—H3NB···Cl3ii0.922.323.231 (2)171
O1WA—H1WA···Cl4iv0.922.423.204 (2)143
O1WA—H2WA···O1Av0.911.892.799 (3)173
O1WB—H1WB···O1WAiv0.901.782.672 (3)175
O1WB—H2WB···Cl20.912.333.231 (2)169
C12B—H12E···O1WAvi0.982.583.487 (3)153
C3B—H3BA···O1Bvii0.952.563.373 (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.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1NA···Cl3i0.902.493.271 (2)146
N2A—H2NA···Cl4ii0.802.433.208 (2)164
N2A—H3NA···O1WBiii0.891.922.790 (3)166
N1B—H1NB···O1WB0.921.992.872 (3)159
N2B—H2NB···Cl1iii0.862.283.141 (2)176
N2B—H3NB···Cl3ii0.922.323.231 (2)171
O1WA—H1WA···Cl4iv0.922.423.204 (2)143
O1WA—H2WA···O1Av0.911.892.799 (3)173
O1WB—H1WB···O1WAiv0.901.782.672 (3)175
O1WB—H2WB···Cl20.912.333.231 (2)169
C12B—H12E···O1WAvi0.982.583.487 (3)153
C3B—H3BA···O1Bvii0.952.563.373 (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 top

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.

references
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