Bis(7-meth­oxy-1-methyl-4,9-dihydro-3H-β-carbolinium) tetra­chloridozincate

Kadirova, Z.C.; Chepulsky, S.A.; Parpiev, N.A.; Talipov, S.A.; Sharipov, K.T.

doi:10.1107/S1600536810010822

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page m473

doi:10.1107/S1600536810010822

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Bis(7-methoxy-1-methyl-4,9-dihydro-3H-β-carbolinium) tetrachloridozincate

Zukhra Ch. Kadirova,^a ^* Stanislav A. Chepulsky,^b Nusrat A. Parpiev,^b Samat A. Talipov ^c and Khasan T. Sharipov ^a

^aTashkent Chemical-Technological Institute, Navoi St 32, Tashkent 100011, Uzbekistan, ^bNational University of Uzbekistan, Tashkent 100123, Uzbekistan, and ^cInstitute of Biorganic Chemistry, Mirzo-Ulugbek St. 83, Tashkent 100125, Uzbekistan
^*Correspondence e-mail: zuhra_kadirova@yahoo.com

(Received 7 January 2010; accepted 23 March 2010; online 31 March 2010)

In the title compound, (C₁₃H₁₅N₂O)₂[ZnCl₄], also known as di(harmalinium) tetrachloridozincate, the Zn^II atom is in a distorted tetrahedral coordination of the chlorido ligands. In the cation, the methoxy 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 interact 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_r = 637.71
Monoclinic, P 2₁ /c
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 $[Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) 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[F² > 2σ(F²)] = 0.043
wR(F²) = 0.116
S = 1.04
4954 reflections
334 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.46 e Å⁻³

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) x-1, y, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y, -z+2.

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); 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 ).

Supporting information

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

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

checkCIF report

Comment top

The metal complexes of the harmaline (7-methoxy-1-methyl-4,9-dihydro-3H-β-carboline) and other carboline alkaloids have biological activity (Al-Allaf et al. 1990). In this study we synthesized the molecular salt containing a zinc-chlorido complex and harmalinium cations, and report the structure of the title compound, (I).

The molecular structure is shown on Fig.1 and geometrical parameters are available from archived CIF.

Zinc ions are anions [ZnCl₄]^2- have distorted tetragonal configuration (Sutherland et al., 2009) and the valence angles are close to tetrahedral, being in the ranges 104.15 (4)-113.37 (4)°. The Zn—Cl bonds are not equal and values of bond lengths, being in the range 2.2536 (10)-2.2885 (10)Å .

Bond lengths and angles in the cations do not differ from their normal values. The alkaloid molecules are in a protonated form and the proton is localized at the nitrogen atom in the carboline ring as observed previously in structure of harmaline hydrochloride (Ferretti et al., 2004; Wouters, 1997). Protonization leads to a decrease in CH₂— CH₂ and C═N bond lengths in comparison with the harmaline structure (Reimers et al., 1984). In the pyrrole cycle C—NH bond lengths are not equivalent as distinctions are expressed in a greater degree than for the harmaline crystal structure (Reimers et al., 1984). Both methoxy and methyl groups are located in the plane of the pyrrole and benzole rings and the carboline ring has a noncoplanar conformation with the torsion angles shown in the table 1. The sp³-hybridizied carbon atoms in the cycle being displaced from the mean plane of carboline cycle by -0.286 (4), - 0.199 (4), 0.257 (5) and -0.090 (4) Å for C3, C4, C16, C17, respectively.

Unlike the parent harmaline structure (Reimers et al., 1984) in which only one hydrogen bond is present, in case of compound I a network of hydrogen bonds is formed (Fig.2) as in case of harmine hydrochloride where hydrogen bonds are formed between NH-groups as acceptors and chlorine atoms as donors of electrons (Ferretti et al., 2004; Wouters, 1997).

Related literature top

For background to the activity of metal complexes with harmaline (4,9-dihydro-7-methoxy-1-methyl-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 ions, see: Ma et al. (2009).

Experimental top

The ZnCl₂(1 mmol) and harmaline (2.5 mmol) were heated on water bath in 2M solution of hydrochloric acid in ethanol. The resulting solution yielded colourless crystals which were filtered off and washed twice with acetone. Elem. Analysis found: C 49.0, H 4.7, N 8.8, Zn 10.3%; requires: C 49.0, H 4.7, N 8.8, Zn 10.3%. Crystals of the title compound, suitable to X-ray diffraction analysis, were selected directly from the sample as prepared.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); 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).

Figures top

	Fig. 1. A view of the structure of (I), showing the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitary radii.
	Fig. 2. The crystal structure packing scheme showing the hydrogen bonds system.

Bis(7-methoxy-1-methyl-4,9-dihydro-3H-β-carbolinium) tetrachloridozincate top

Crystal data top

(C₁₃H₁₅N₂O)₂[ZnCl₄]	F(000) = 1312
M_r = 637.71	D_x = 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

Data collection top

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

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) = 0.116	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0588P)² + 1.2361P] where P = (F_o² + 2F_c²)/3
4954 reflections	(Δ/σ)_max < 0.001
334 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³
0 constraints

Crystal data top

(C₁₃H₁₅N₂O)₂[ZnCl₄]	V = 2784.87 (7) Å³
M_r = 637.71	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 11.2314 (2) Å	µ = 5.01 mm⁻¹
b = 19.1274 (2) Å	T = 293 K
c = 13.5614 (2) Å	0.25 × 0.12 × 0.08 mm
β = 107.0797 (16)°

Data collection top

Oxford Diffraction Xcalibur diffractometer	3724 reflections with I > 2σ(I)
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	R_int = 0.035
T_min = 0.544, T_max = 0.644	3 standard reflections every 120 reflections
12418 measured reflections	intensity decay: none
4954 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.04	Δρ_max = 0.54 e Å⁻³
4954 reflections	Δρ_min = −0.46 e Å⁻³
334 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) x−1, y, z; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1, −y, −z+2.

Experimental details

Crystal data
Chemical formula	(C₁₃H₁₅N₂O)₂[ZnCl₄]
M_r	637.71
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.2314 (2), 19.1274 (2), 13.5614 (2)
β (°)	107.0797 (16)
V (Å³)	2784.87 (7)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	5.01
Crystal size (mm)	0.25 × 0.12 × 0.08

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)
T_min, T_max	0.544, 0.644
No. of measured, independent and observed [I > 2σ(I)] reflections	12418, 4954, 3724
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.613

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.116, 1.04
No. of reflections	4954
No. of parameters	334
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.46

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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) x−1, y, z; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1, −y, −z+2.

Acknowledgements

This work was supported by a grant from the Fundamental Research Center of Science and Technology, Republic of Uzbekistan (F 3-142).

References

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