Dichloro­{2-[2-(dimethyl­ammonio)­ethyl­imino­meth­yl]-4-nitro­phenolato}­zinc(II) in unsolvated and hemihydrate forms

The two title complexes, [ZnCl₂(C₁₁H₁₅N₃O₃)], (I), and [ZnCl₂(C₁₁H₁₅N₃O₃)]·0.5H₂O, (II), are mononuclear zinc(II) compounds. In both structures, the Zn^II atom is four-coordinated in a tetra­hedral configuration by one imine N atom and one phenolate O atom of a Schiff base, and by two Cl atoms. The structure of each of the two zinc(II) complex molecules of (II) is similar to that of (I). In (I), the mol­ecules are linked through inter­molecular hydrogen bonds, forming a three-dimensional framework. In (II), the solvent water mol­ecules are linked to the zinc(II) moieties through inter­molecular O-H...O and O-H...Cl hydrogen bonds. The mol­ecules in (II) are further linked via other inter­molecular hydrogen bonds, forming a three-dimensional framework.

S1. Comment

Transition metal complexes containing Schiff base ligands have been of great interest for many years (Yamada, 1999). These complexes play an important role in coordination chemistry related to catalysis and enzymatic reactions, magnetism, and molecular architectures (Lacroix, 1996; Goswami & Eichhorn, 1999; Rybak-Akimova et al., 1998). The study of the variety of products in self-assembly processes between labile metal ions and flexible multidentate ligands is an interesting topic in supramolecular chemistry. The balance between the formation of different structures is often subtle. Factors that affect the coordination topology include not only the highly influential factors of metal and ligand coordination preferences, but also solvent-based influences, which have been extensively studied for silver(I) complexes (Smith et al., 1996; Kristiansson, 2001; Nomiya et al., 2000; Wei et al., 1998). However, for zinc(II) complexes, solvent-based influences on the structures have seldom been reported. Thus, more work needs to be performed in order to understand better the controlling effect of solvents on Schiff base zinc(II) complexes, which is now becoming an interesting topic in supramolecular chemistry.

We have focused our attention on the assembly of transition metal ions with flexible ligands, since they can adopt diverse coordination modes according to the geometric needs of the metal ion (You, 2005a,b). In order to investigate the relationship between the solvents used in the syntheses of the complexes and the resulting structures, we report here two novel mononuclear zinc(II) complexes, which have been synthesized in different solvents with the same starting materials.

The two title complexes, (I) and (II), are mononuclear zinc(II) compounds (Fig. 1 and 2). The major difference between the complexes is in the components of the molecules: complex (I), synthesized and crystallized in MeOH solution, has no MeOH molecules in the crystal, while complex (II), synthesized and crystallized in MeOH–H₂O (2:1 v/v) mixed solution, has solvent water molecules in the crystal.

In both structures, the Zn^II atom is four-coordinated in a tetrahedral configuration, by one imine N atom and one phenolate O atom of a Schiff base, and by two Cl atoms. The structure of each zinc moiety of (II) is similar to that of (I). For the two complexes, each ZnONCl₂ coordination forms a slightly distorted tetrahedral geometry, as usually observed in the structures of Zn^II complexes (McCleverty et al., 1980; You et al., 2003), with angles subtended at the Zn^II atom in the range 108.16 (9)–115.52 (9)° for Zn1 in (I), 95.35 (10)–117.09 (8)° for Zn1 in (II), and 95.37 (10)–115.79 (8)° for Zn2 in (II) (Table 1). The average Zn—O bond lengths [1.940 (3) Å in (I) and 1.936 (2) Å in (II)] are comparable with the corresponding values observed in other Schiff base Zn^II complexes (Usman et al., 2003; Erxleben 2001; Chisholm et al., 2001). The mean Zn—N bond lengths [2.031 (3) Å in (I) and 2.016 (3) Å in (II)] are also comparable with the values observed in the above-mentioned complexes.

The dihedral angle between the O1—N1—O2 plane and the phenyl ring in (I) is 8.8 (3)°, which is much bigger than the corresponding values of 6.4 (3)° [for the Zn1 moiety of (II)] and 5.0 (3)° [for the Zn2 moiety of (II)]. This is probably caused by intermolecular hydrogen bonds, which pull the two O atoms of each nitryl in opposite directions with different intensity.

In (I), the molecules are linked via intermolecular N—H···Cl, C—H···O and C—H···Cl hydrogen bonds (Table 2), forming a three-dimensional framework. In (II), the solvent water molecules are linked to the zinc(II) moieties through intermolecular O—H···O and O—H···Cl hydrogen bonds. The molecules in (II) are further linked via intermolecular N—H···Cl, N—H···O, C—H···Cl and C—H···O hydrogen bonds, forming a three-dimensional framework.

In conclusion, the solvents used in the preparation and crystallization of complexes can influence the crystal structures.

S2. Experimental

For the preparation of complex (I), 5-nitrylsalicylaldehyde (0.1 mmol, 20.1 mg) and N,N'-dimethylethane-1,2-diamine (0.1 mmol, 8.8 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature for 10 min to give a yellow solution, to which was added a MeOH solution (5 ml) of ZnCl₂·6H₂O (0.1 mmol, 24.4 mg) with stirring. The mixture was stirred for another 10 min at room temperature. After keeping the filtrate in air for 8 d, colourless needle-shaped crystals of (I) were formed. Complex (II) was prepared by a procedure similar to that described for (I), with ZnCl₂·6H₂O dissolved in distilled water (5 ml), rather than in MeOH. Colourless block-shaped crystals of (II) were obtained after evaporating the solvents from the filtrate in air for 11 days.

S3. Refinement

Atom H3A in (I), and atoms H3A, H6A, H7A and H7B in (II), were located in difference Fourier maps and refined isotropically, with the O—H distance restrained to 0.84 (1) Å, the H···H distance restrained to 1.37 (2) Å, and the N—H distances restrained to 0.90 (1) Å. The other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å, and with U_iso(H) = 1.2 or 1.5U_eq(C). In (I), an unassigned maximum residual density was observed 0.02 Å from atom Zn1. The minimum residual density was observed 1.64 Å from atom H6. In (II), an unassigned maximum residual density was observed 0.98 Å from atom O6. The minimum residual density was observed 1.64 Å from atom Zn1. There are 1463 Friedel pairs in (I).

Computing details

For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

(I) Dichloro{2-[2-(dimethylammonio)ethyliminomethyl]-4-nitrophenolato}zinc(II)

Crystal data

[ZnCl2(C11H15N3O3)]	F(000) = 760
Mr = 373.53	Dx = 1.608 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2733 reflections
a = 7.668 (2) Å	θ = 2.8–23.7°
b = 13.691 (3) Å	µ = 1.95 mm^−1
c = 14.698 (3) Å	T = 298 K
V = 1543.0 (6) Å^3	Needle, colourless
Z = 4	0.20 × 0.08 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3496 independent reflections
Radiation source: fine-focus sealed tube	3088 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.697, Tmax = 0.909	k = −17→12
9727 measured reflections	l = −18→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.03P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3496 reflections	Δρmax = 0.44 e Å^−3
186 parameters	Δρmin = −0.21 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.035 (15)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.07025 (5)	0.09039 (3)	0.42041 (3)	0.04076 (12)
Cl1	−0.11380 (13)	−0.03407 (8)	0.41124 (10)	0.0703 (4)
Cl2	0.00176 (14)	0.20374 (8)	0.52497 (7)	0.0564 (3)
O1	0.7470 (5)	0.2500 (2)	0.0560 (2)	0.0861 (12)
O2	0.8629 (4)	0.1371 (2)	0.1368 (2)	0.0645 (9)
O3	0.1193 (3)	0.1567 (2)	0.30663 (17)	0.0477 (7)
N1	0.7403 (5)	0.1892 (2)	0.1160 (2)	0.0493 (8)
N2	0.3164 (3)	0.0379 (2)	0.43501 (19)	0.0331 (6)
N3	0.4102 (4)	0.11341 (19)	0.61814 (19)	0.0385 (7)
C1	0.4213 (5)	0.1139 (2)	0.2947 (2)	0.0321 (7)
C2	0.2677 (5)	0.1634 (2)	0.2655 (2)	0.0355 (8)
C3	0.2792 (5)	0.2218 (3)	0.1862 (2)	0.0436 (9)
H3	0.1806	0.2550	0.1661	0.052*
C4	0.4314 (6)	0.2308 (3)	0.1384 (2)	0.0437 (9)
H4	0.4366	0.2706	0.0872	0.052*
C5	0.5771 (5)	0.1802 (3)	0.1667 (2)	0.0388 (8)
C6	0.5740 (5)	0.1227 (2)	0.2435 (2)	0.0371 (8)
H6	0.6741	0.0895	0.2614	0.045*
C7	0.4361 (5)	0.0540 (2)	0.3750 (2)	0.0358 (7)
H7	0.5431	0.0238	0.3847	0.043*
C8	0.3617 (5)	−0.0275 (3)	0.5106 (2)	0.0418 (9)
H8A	0.4854	−0.0422	0.5084	0.050*
H8B	0.2982	−0.0884	0.5042	0.050*
C9	0.3182 (5)	0.0186 (2)	0.6008 (2)	0.0408 (9)
H9A	0.1934	0.0297	0.6036	0.049*
H9B	0.3480	−0.0269	0.6489	0.049*
C10	0.3394 (6)	0.1607 (3)	0.7017 (3)	0.0583 (12)
H10A	0.3538	0.1176	0.7526	0.087*
H10B	0.2178	0.1746	0.6932	0.087*
H10C	0.4012	0.2205	0.7129	0.087*
C11	0.6038 (5)	0.1014 (3)	0.6256 (3)	0.0597 (12)
H11A	0.6569	0.1641	0.6351	0.090*
H11B	0.6481	0.0731	0.5705	0.090*
H11C	0.6305	0.0594	0.6760	0.090*
H3A	0.393 (6)	0.154 (3)	0.571 (2)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0344 (2)	0.0444 (2)	0.0435 (2)	0.0021 (2)	0.0015 (2)	0.0011 (2)
Cl1	0.0454 (6)	0.0522 (6)	0.1132 (10)	−0.0086 (5)	−0.0074 (6)	−0.0034 (7)
Cl2	0.0651 (7)	0.0509 (6)	0.0533 (6)	0.0099 (5)	0.0117 (5)	−0.0046 (5)
O1	0.092 (3)	0.086 (2)	0.080 (3)	0.014 (2)	0.037 (2)	0.044 (2)
O2	0.0505 (19)	0.074 (2)	0.069 (2)	0.0095 (17)	0.0214 (16)	0.0046 (17)
O3	0.0390 (15)	0.0623 (17)	0.0419 (15)	0.0106 (13)	0.0018 (12)	0.0098 (13)
N1	0.058 (2)	0.048 (2)	0.0418 (19)	0.0002 (18)	0.0128 (16)	−0.0046 (16)
N2	0.0349 (15)	0.0347 (15)	0.0297 (16)	0.0022 (12)	−0.0012 (12)	0.0002 (12)
N3	0.0473 (19)	0.0326 (17)	0.0355 (16)	−0.0029 (14)	0.0030 (15)	0.0023 (12)
C1	0.0350 (17)	0.0337 (18)	0.0275 (17)	−0.0002 (16)	−0.0040 (15)	−0.0031 (12)
C2	0.040 (2)	0.038 (2)	0.0284 (18)	0.0022 (16)	−0.0014 (16)	−0.0035 (15)
C3	0.048 (2)	0.046 (2)	0.037 (2)	0.0122 (19)	−0.0073 (18)	0.0041 (17)
C4	0.061 (2)	0.042 (2)	0.0289 (18)	−0.003 (2)	−0.002 (2)	0.0042 (15)
C5	0.044 (2)	0.0397 (19)	0.0322 (19)	−0.0040 (18)	0.0039 (18)	−0.0044 (14)
C6	0.0401 (19)	0.0374 (18)	0.0339 (19)	0.0031 (16)	−0.0006 (17)	−0.0036 (14)
C7	0.0348 (18)	0.0358 (18)	0.0367 (19)	0.0072 (16)	−0.0050 (17)	−0.0027 (14)
C8	0.049 (2)	0.038 (2)	0.037 (2)	−0.0037 (18)	0.0003 (17)	0.0069 (16)
C9	0.050 (2)	0.037 (2)	0.035 (2)	−0.0093 (17)	0.0042 (16)	0.0051 (16)
C10	0.072 (3)	0.063 (3)	0.040 (2)	−0.006 (2)	0.007 (2)	−0.014 (2)
C11	0.048 (3)	0.052 (2)	0.080 (3)	−0.007 (2)	0.003 (2)	−0.006 (2)

Geometric parameters (Å, º)

Zn1—O3	1.940 (3)	C3—C4	1.368 (5)
Zn1—N2	2.031 (3)	C3—H3	0.9300
Zn1—Cl1	2.217 (2)	C4—C5	1.379 (5)
Zn1—Cl2	2.246 (2)	C4—H4	0.9300
O1—N1	1.214 (4)	C5—C6	1.376 (5)
O2—N1	1.218 (4)	C6—H6	0.9300
O3—C2	1.292 (4)	C7—H7	0.9300
N1—C5	1.462 (5)	C8—C9	1.506 (5)
N2—C7	1.291 (4)	C8—H8A	0.9700
N2—C8	1.468 (4)	C8—H8B	0.9700
N3—C10	1.490 (5)	C9—H9A	0.9700
N3—C11	1.498 (5)	C9—H9B	0.9700
N3—C9	1.500 (4)	C10—H10A	0.9600
N3—H3A	0.90 (3)	C10—H10B	0.9600
C1—C6	1.396 (5)	C10—H10C	0.9600
C1—C2	1.425 (5)	C11—H11A	0.9600
C1—C7	1.442 (4)	C11—H11B	0.9600
C2—C3	1.417 (5)	C11—H11C	0.9600
O3—Zn1—N2	94.39 (11)	C6—C5—N1	118.7 (4)
O3—Zn1—Cl1	115.52 (9)	C4—C5—N1	119.8 (3)
N2—Zn1—Cl1	109.03 (8)	C5—C6—C1	120.3 (3)
O3—Zn1—Cl2	108.16 (9)	C5—C6—H6	119.8
N2—Zn1—Cl2	112.92 (9)	C1—C6—H6	119.8
Cl1—Zn1—Cl2	115.08 (5)	N2—C7—C1	126.9 (3)
C2—O3—Zn1	127.4 (2)	N2—C7—H7	116.5
O1—N1—O2	123.4 (4)	C1—C7—H7	116.5
O1—N1—C5	117.7 (4)	N2—C8—C9	111.0 (3)
O2—N1—C5	118.9 (3)	N2—C8—H8A	109.4
C7—N2—C8	116.9 (3)	C9—C8—H8A	109.4
C7—N2—Zn1	121.8 (2)	N2—C8—H8B	109.4
C8—N2—Zn1	121.0 (2)	C9—C8—H8B	109.4
C10—N3—C11	110.4 (3)	H8A—C8—H8B	108.0
C10—N3—C9	110.2 (3)	N3—C9—C8	114.1 (3)
C11—N3—C9	112.6 (3)	N3—C9—H9A	108.7
C10—N3—H3A	109 (3)	C8—C9—H9A	108.7
C11—N3—H3A	106 (3)	N3—C9—H9B	108.7
C9—N3—H3A	109 (3)	C8—C9—H9B	108.7
C6—C1—C2	119.3 (3)	H9A—C9—H9B	107.6
C6—C1—C7	115.1 (3)	N3—C10—H10A	109.5
C2—C1—C7	125.5 (3)	N3—C10—H10B	109.5
O3—C2—C3	118.7 (3)	H10A—C10—H10B	109.5
O3—C2—C1	123.6 (3)	N3—C10—H10C	109.5
C3—C2—C1	117.7 (3)	H10A—C10—H10C	109.5
C4—C3—C2	121.8 (3)	H10B—C10—H10C	109.5
C4—C3—H3	119.1	N3—C11—H11A	109.5
C2—C3—H3	119.1	N3—C11—H11B	109.5
C3—C4—C5	119.4 (3)	H11A—C11—H11B	109.5
C3—C4—H4	120.3	N3—C11—H11C	109.5
C5—C4—H4	120.3	H11A—C11—H11C	109.5
C6—C5—C4	121.4 (4)	H11B—C11—H11C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl2^i	0.90 (3)	2.55 (3)	3.344 (3)	148 (4)
C4—H4···O1^ii	0.93	2.57	3.199 (3)	125
C7—H7···Cl1^iii	0.93	2.78	3.695 (3)	170
C8—H8A···O2^iv	0.97	2.57	3.186 (3)	121
C8—H8B···O1^v	0.97	2.41	3.306 (3)	154
C10—H10C···O3^i	0.96	2.39	3.297 (3)	158

Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1/2, −y+1/2, −z; (iii) x+1, y, z; (iv) −x+3/2, −y, z+1/2; (v) −x+1, y−1/2, −z+1/2.

(II) Dichloro{2-[2-(dimethylammonio)ethyliminomethyl]-4-nitrophenolato}zinc(II) hemihydrate

Crystal data

[ZnCl2(C11H15N3O3)]·0.5H2O	Z = 4
Mr = 382.54	F(000) = 780
Triclinic, P1	Dx = 1.608 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.181 (2) Å	Cell parameters from 4057 reflections
b = 12.312 (2) Å	θ = 2.3–25.8°
c = 12.596 (2) Å	µ = 1.90 mm^−1
α = 66.673 (1)°	T = 298 K
β = 70.632 (1)°	Block, colourless
γ = 69.149 (1)°	0.26 × 0.19 × 0.17 mm
V = 1580.5 (4) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	6985 independent reflections
Radiation source: fine-focus sealed tube	5088 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.637, Tmax = 0.738	k = −15→15
13545 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0743P)^2] where P = (Fo^2 + 2Fc^2)/3
6985 reflections	(Δ/σ)max < 0.001
386 parameters	Δρmax = 0.86 e Å^−3
5 restraints	Δρmin = −0.28 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn2	0.70710 (3)	0.78645 (3)	0.57835 (3)	0.03952 (12)
Zn1	0.76514 (3)	0.13805 (3)	0.90574 (3)	0.04175 (12)
Cl1	0.79980 (10)	0.18238 (9)	1.04419 (9)	0.0617 (3)
Cl2	0.57239 (8)	0.20603 (10)	0.89548 (9)	0.0587 (2)
Cl3	0.66807 (10)	0.96400 (9)	0.43463 (9)	0.0616 (3)
Cl4	0.89771 (7)	0.72313 (8)	0.59603 (8)	0.0493 (2)
O1	1.1889 (3)	−0.3795 (3)	0.6410 (3)	0.0851 (10)
O2	1.2074 (3)	−0.2053 (3)	0.5101 (3)	0.0840 (10)
O3	0.8297 (2)	−0.0360 (2)	0.9267 (2)	0.0522 (6)
O4	0.2547 (4)	0.4501 (4)	0.9789 (5)	0.151 (2)
O5	0.2706 (3)	0.3674 (3)	0.8499 (4)	0.1084 (14)
O6	0.6557 (2)	0.6587 (2)	0.5712 (2)	0.0484 (6)
O7	0.1041 (3)	0.1264 (2)	0.8502 (3)	0.0704 (8)
N1	1.1664 (3)	−0.2670 (4)	0.6094 (4)	0.0656 (10)
N2	0.8636 (2)	0.1924 (2)	0.7394 (2)	0.0381 (6)
N3	0.9726 (3)	0.3622 (2)	0.7624 (3)	0.0436 (6)
N4	0.2976 (3)	0.4354 (3)	0.8828 (5)	0.0893 (14)
N5	0.6072 (2)	0.7839 (2)	0.7423 (2)	0.0399 (6)
N6	0.5125 (3)	1.0528 (3)	0.7008 (3)	0.0453 (7)
C1	0.9653 (3)	−0.0166 (3)	0.7353 (3)	0.0395 (7)
C2	0.9092 (3)	−0.0846 (3)	0.8485 (3)	0.0429 (8)
C3	0.9423 (3)	−0.2133 (3)	0.8779 (3)	0.0499 (9)
H3	0.9047	−0.2593	0.9506	0.060*
C4	1.0275 (3)	−0.2721 (3)	0.8030 (4)	0.0536 (9)
H4	1.0493	−0.3572	0.8252	0.064*
C5	1.0813 (3)	−0.2045 (3)	0.6940 (4)	0.0499 (9)
C6	1.0518 (3)	−0.0795 (3)	0.6588 (3)	0.0463 (8)
H6	1.0889	−0.0361	0.5842	0.056*
C7	0.9377 (3)	0.1151 (3)	0.6869 (3)	0.0420 (7)
H7	0.9779	0.1476	0.6094	0.050*
C8	0.8436 (3)	0.3222 (3)	0.6700 (3)	0.0456 (8)
H8A	0.7644	0.3522	0.6521	0.055*
H8B	0.9030	0.3321	0.5955	0.055*
C9	0.8522 (3)	0.3971 (3)	0.7360 (3)	0.0432 (8)
H9A	0.8338	0.4829	0.6891	0.052*
H9B	0.7920	0.3874	0.8100	0.052*
C10	0.9672 (4)	0.4234 (4)	0.8457 (4)	0.0625 (11)
H10A	0.9361	0.5102	0.8134	0.094*
H10B	1.0467	0.4063	0.8567	0.094*
H10C	0.9155	0.3930	0.9206	0.094*
C11	1.0698 (3)	0.3908 (4)	0.6539 (4)	0.0632 (11)
H11A	1.0724	0.3516	0.6003	0.095*
H11B	1.1460	0.3613	0.6759	0.095*
H11C	1.0534	0.4778	0.6158	0.095*
C12	0.5087 (3)	0.6361 (3)	0.7566 (3)	0.0458 (8)
C13	0.5696 (3)	0.6118 (3)	0.6469 (3)	0.0416 (7)
C14	0.5345 (3)	0.5306 (3)	0.6197 (4)	0.0543 (9)
H14	0.5731	0.5140	0.5485	0.065*
C15	0.4455 (4)	0.4753 (3)	0.6944 (4)	0.0604 (11)
H15	0.4237	0.4224	0.6738	0.073*
C16	0.3887 (3)	0.4984 (3)	0.8000 (4)	0.0627 (12)
C17	0.4185 (3)	0.5759 (3)	0.8322 (4)	0.0621 (11)
H17	0.3789	0.5892	0.9047	0.075*
C18	0.5349 (3)	0.7149 (3)	0.7993 (3)	0.0477 (8)
H18	0.4953	0.7157	0.8762	0.057*
C19	0.6312 (3)	0.8462 (3)	0.8073 (3)	0.0480 (8)
H19A	0.7092	0.8035	0.8272	0.058*
H19B	0.5707	0.8436	0.8807	0.058*
C20	0.6296 (3)	0.9782 (3)	0.7348 (3)	0.0448 (8)
H20A	0.6476	1.0153	0.7800	0.054*
H20B	0.6928	0.9799	0.6633	0.054*
C21	0.4105 (3)	1.0587 (4)	0.8041 (4)	0.0680 (11)
H21A	0.3989	0.9782	0.8479	0.102*
H21B	0.3387	1.1122	0.7773	0.102*
H21C	0.4275	1.0897	0.8543	0.102*
C22	0.5220 (4)	1.1783 (3)	0.6219 (4)	0.0647 (11)
H22A	0.5455	1.2159	0.6617	0.097*
H22B	0.4454	1.2266	0.6031	0.097*
H22C	0.5813	1.1731	0.5502	0.097*
H3A	1.000 (4)	0.2802 (11)	0.794 (4)	0.080*
H6A	0.501 (4)	1.015 (4)	0.659 (3)	0.080*
H7A	0.127 (4)	0.101 (3)	0.913 (2)	0.080*
H7B	0.110 (4)	0.068 (2)	0.830 (3)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn2	0.0382 (2)	0.0435 (2)	0.0382 (2)	−0.01468 (16)	−0.00427 (16)	−0.01403 (17)
Zn1	0.0451 (2)	0.0406 (2)	0.0368 (2)	−0.01392 (17)	−0.00631 (17)	−0.00914 (17)
Cl1	0.0752 (7)	0.0669 (6)	0.0550 (6)	−0.0232 (5)	−0.0197 (5)	−0.0228 (5)
Cl2	0.0464 (5)	0.0739 (6)	0.0502 (5)	−0.0099 (4)	−0.0126 (4)	−0.0174 (5)
Cl3	0.0739 (6)	0.0537 (5)	0.0613 (6)	−0.0242 (5)	−0.0318 (5)	−0.0017 (5)
Cl4	0.0387 (4)	0.0583 (5)	0.0479 (5)	−0.0151 (4)	−0.0088 (4)	−0.0121 (4)
O1	0.074 (2)	0.066 (2)	0.125 (3)	0.0144 (16)	−0.037 (2)	−0.056 (2)
O2	0.071 (2)	0.097 (2)	0.093 (3)	−0.0217 (18)	0.0039 (19)	−0.058 (2)
O3	0.0641 (16)	0.0378 (12)	0.0418 (13)	−0.0159 (11)	−0.0014 (12)	−0.0059 (11)
O4	0.131 (4)	0.096 (3)	0.183 (5)	−0.071 (3)	0.093 (4)	−0.068 (3)
O5	0.082 (2)	0.081 (2)	0.161 (4)	−0.052 (2)	−0.034 (2)	−0.004 (2)
O6	0.0564 (14)	0.0536 (14)	0.0428 (13)	−0.0268 (12)	−0.0013 (11)	−0.0197 (11)
O7	0.076 (2)	0.0551 (17)	0.071 (2)	0.0035 (15)	−0.0346 (17)	−0.0140 (15)
N1	0.0456 (19)	0.076 (3)	0.093 (3)	−0.0034 (18)	−0.0214 (19)	−0.050 (2)
N2	0.0411 (14)	0.0335 (13)	0.0378 (14)	−0.0144 (11)	−0.0092 (12)	−0.0046 (11)
N3	0.0501 (16)	0.0331 (14)	0.0449 (16)	−0.0112 (12)	−0.0143 (13)	−0.0060 (13)
N4	0.057 (2)	0.046 (2)	0.140 (4)	−0.0207 (18)	0.002 (3)	−0.017 (2)
N5	0.0371 (14)	0.0397 (15)	0.0412 (15)	−0.0066 (11)	−0.0054 (12)	−0.0168 (12)
N6	0.0467 (16)	0.0465 (16)	0.0500 (17)	−0.0146 (13)	−0.0153 (13)	−0.0164 (14)
C1	0.0400 (17)	0.0372 (17)	0.0427 (18)	−0.0144 (13)	−0.0072 (14)	−0.0118 (14)
C2	0.0464 (19)	0.0404 (18)	0.0458 (19)	−0.0154 (15)	−0.0162 (16)	−0.0091 (15)
C3	0.067 (2)	0.0372 (18)	0.048 (2)	−0.0198 (17)	−0.0240 (18)	−0.0017 (16)
C4	0.062 (2)	0.0373 (19)	0.072 (3)	−0.0057 (17)	−0.035 (2)	−0.0175 (18)
C5	0.0390 (18)	0.051 (2)	0.073 (3)	−0.0047 (16)	−0.0200 (18)	−0.033 (2)
C6	0.0422 (18)	0.051 (2)	0.052 (2)	−0.0178 (16)	−0.0077 (16)	−0.0200 (17)
C7	0.0455 (19)	0.0452 (18)	0.0357 (17)	−0.0204 (15)	−0.0038 (14)	−0.0096 (15)
C8	0.051 (2)	0.0360 (17)	0.0460 (19)	−0.0132 (15)	−0.0190 (16)	−0.0014 (15)
C9	0.0448 (19)	0.0298 (16)	0.049 (2)	−0.0059 (14)	−0.0125 (15)	−0.0079 (14)
C10	0.085 (3)	0.053 (2)	0.058 (2)	−0.022 (2)	−0.024 (2)	−0.0153 (19)
C11	0.052 (2)	0.063 (3)	0.065 (3)	−0.0176 (19)	−0.005 (2)	−0.015 (2)
C12	0.0366 (17)	0.0378 (17)	0.055 (2)	−0.0094 (14)	−0.0013 (15)	−0.0140 (16)
C13	0.0385 (17)	0.0381 (17)	0.0478 (19)	−0.0109 (14)	−0.0160 (15)	−0.0072 (15)
C14	0.062 (2)	0.044 (2)	0.061 (2)	−0.0149 (17)	−0.025 (2)	−0.0101 (18)
C15	0.057 (2)	0.040 (2)	0.087 (3)	−0.0185 (17)	−0.030 (2)	−0.006 (2)
C16	0.0382 (19)	0.0357 (19)	0.098 (3)	−0.0114 (15)	−0.010 (2)	−0.007 (2)
C17	0.048 (2)	0.044 (2)	0.074 (3)	−0.0102 (17)	0.0080 (19)	−0.018 (2)
C18	0.0459 (19)	0.0434 (19)	0.0419 (19)	−0.0096 (15)	0.0048 (15)	−0.0151 (16)
C19	0.052 (2)	0.048 (2)	0.047 (2)	−0.0050 (16)	−0.0144 (16)	−0.0217 (16)
C20	0.0407 (18)	0.0500 (19)	0.052 (2)	−0.0124 (15)	−0.0088 (15)	−0.0253 (17)
C21	0.044 (2)	0.081 (3)	0.074 (3)	−0.011 (2)	−0.007 (2)	−0.029 (2)
C22	0.083 (3)	0.048 (2)	0.069 (3)	−0.025 (2)	−0.028 (2)	−0.0085 (19)

Geometric parameters (Å, º)

Zn1—O3	1.942 (2)	C4—H4	0.9300
Zn1—N2	2.018 (3)	C5—C6	1.366 (5)
Zn1—Cl1	2.219 (2)	C6—H6	0.9300
Zn1—Cl2	2.224 (2)	C7—H7	0.9300
Zn2—O6	1.930 (2)	C8—C9	1.512 (4)
Zn2—N5	2.013 (3)	C8—H8A	0.9700
Zn2—Cl4	2.228 (2)	C8—H8B	0.9700
Zn2—Cl3	2.231 (2)	C9—H9A	0.9700
O1—N1	1.232 (5)	C9—H9B	0.9700
O2—N1	1.222 (5)	C10—H10A	0.9600
O3—C2	1.299 (4)	C10—H10B	0.9600
O4—N4	1.208 (6)	C10—H10C	0.9600
O5—N4	1.242 (5)	C11—H11A	0.9600
O6—C13	1.294 (4)	C11—H11B	0.9600
O7—H7A	0.83 (3)	C11—H11C	0.9600
O7—H7B	0.83 (3)	C12—C17	1.411 (5)
N1—C5	1.466 (5)	C12—C13	1.428 (5)
N2—C7	1.284 (4)	C12—C18	1.443 (5)
N2—C8	1.462 (4)	C13—C14	1.404 (4)
N3—C9	1.486 (4)	C14—C15	1.366 (5)
N3—C10	1.489 (4)	C14—H14	0.9300
N3—C11	1.495 (5)	C15—C16	1.370 (6)
N3—H3A	0.91 (3)	C15—H15	0.9300
N4—C16	1.458 (5)	C16—C17	1.363 (5)
N5—C18	1.282 (4)	C17—H17	0.9300
N5—C19	1.470 (4)	C18—H18	0.9300
N6—C21	1.477 (5)	C19—C20	1.513 (5)
N6—C22	1.491 (4)	C19—H19A	0.9700
N6—C20	1.491 (4)	C19—H19B	0.9700
N6—H6A	0.90 (4)	C20—H20A	0.9700
C1—C6	1.405 (4)	C20—H20B	0.9700
C1—C2	1.420 (5)	C21—H21A	0.9600
C1—C7	1.442 (4)	C21—H21B	0.9600
C2—C3	1.412 (4)	C21—H21C	0.9600
C3—C4	1.359 (5)	C22—H22A	0.9600
C3—H3	0.9300	C22—H22B	0.9600
C4—C5	1.376 (5)	C22—H22C	0.9600
O3—Zn1—N2	95.35 (10)	H8A—C8—H8B	108.0
O3—Zn1—Cl1	110.05 (8)	N3—C9—C8	113.5 (3)
N2—Zn1—Cl1	117.09 (8)	N3—C9—H9A	108.9
O3—Zn1—Cl2	113.05 (8)	C8—C9—H9A	108.9
N2—Zn1—Cl2	107.32 (8)	N3—C9—H9B	108.9
Cl1—Zn1—Cl2	112.85 (4)	C8—C9—H9B	108.9
O6—Zn2—N5	95.37 (10)	H9A—C9—H9B	107.7
O6—Zn2—Cl4	111.84 (8)	N3—C10—H10A	109.5
N5—Zn2—Cl4	105.10 (8)	N3—C10—H10B	109.5
O6—Zn2—Cl3	114.12 (8)	H10A—C10—H10B	109.5
N5—Zn2—Cl3	115.79 (8)	N3—C10—H10C	109.5
Cl4—Zn2—Cl3	113.09 (4)	H10A—C10—H10C	109.5
C2—O3—Zn1	125.9 (2)	H10B—C10—H10C	109.5
C13—O6—Zn2	125.6 (2)	N3—C11—H11A	109.5
H7A—O7—H7B	110 (2)	N3—C11—H11B	109.5
O2—N1—O1	123.3 (4)	H11A—C11—H11B	109.5
O2—N1—C5	118.8 (4)	N3—C11—H11C	109.5
O1—N1—C5	117.8 (4)	H11A—C11—H11C	109.5
C7—N2—C8	117.4 (3)	H11B—C11—H11C	109.5
C7—N2—Zn1	121.8 (2)	C17—C12—C13	118.4 (3)
C8—N2—Zn1	120.5 (2)	C17—C12—C18	116.5 (3)
C9—N3—C10	110.0 (3)	C13—C12—C18	125.0 (3)
C9—N3—C11	113.3 (3)	O6—C13—C14	117.7 (3)
C10—N3—C11	109.9 (3)	O6—C13—C12	124.5 (3)
C9—N3—H3A	112 (3)	C14—C13—C12	117.8 (3)
C10—N3—H3A	109 (3)	C15—C14—C13	122.2 (4)
C11—N3—H3A	102 (3)	C15—C14—H14	118.9
O4—N4—O5	124.0 (4)	C13—C14—H14	118.9
O4—N4—C16	118.9 (5)	C14—C15—C16	119.4 (4)
O5—N4—C16	117.1 (5)	C14—C15—H15	120.3
C18—N5—C19	117.7 (3)	C16—C15—H15	120.3
C18—N5—Zn2	121.9 (2)	C17—C16—C15	121.6 (4)
C19—N5—Zn2	119.6 (2)	C17—C16—N4	118.6 (5)
C21—N6—C22	110.7 (3)	C15—C16—N4	119.8 (4)
C21—N6—C20	113.0 (3)	C16—C17—C12	120.7 (4)
C22—N6—C20	110.1 (3)	C16—C17—H17	119.7
C21—N6—H6A	110 (3)	C12—C17—H17	119.7
C22—N6—H6A	108 (3)	N5—C18—C12	126.7 (3)
C20—N6—H6A	105 (3)	N5—C18—H18	116.6
C6—C1—C2	119.2 (3)	C12—C18—H18	116.6
C6—C1—C7	115.1 (3)	N5—C19—C20	111.4 (3)
C2—C1—C7	125.6 (3)	N5—C19—H19A	109.3
O3—C2—C3	118.0 (3)	C20—C19—H19A	109.3
O3—C2—C1	124.3 (3)	N5—C19—H19B	109.3
C3—C2—C1	117.7 (3)	C20—C19—H19B	109.3
C4—C3—C2	121.9 (3)	H19A—C19—H19B	108.0
C4—C3—H3	119.0	N6—C20—C19	113.7 (3)
C2—C3—H3	119.0	N6—C20—H20A	108.8
C3—C4—C5	119.4 (3)	C19—C20—H20A	108.8
C3—C4—H4	120.3	N6—C20—H20B	108.8
C5—C4—H4	120.3	C19—C20—H20B	108.8
C6—C5—C4	121.8 (3)	H20A—C20—H20B	107.7
C6—C5—N1	118.6 (4)	N6—C21—H21A	109.5
C4—C5—N1	119.5 (3)	N6—C21—H21B	109.5
C5—C6—C1	119.9 (3)	H21A—C21—H21B	109.5
C5—C6—H6	120.0	N6—C21—H21C	109.5
C1—C6—H6	120.0	H21A—C21—H21C	109.5
N2—C7—C1	127.0 (3)	H21B—C21—H21C	109.5
N2—C7—H7	116.5	N6—C22—H22A	109.5
C1—C7—H7	116.5	N6—C22—H22B	109.5
N2—C8—C9	111.5 (3)	H22A—C22—H22B	109.5
N2—C8—H8A	109.3	N6—C22—H22C	109.5
C9—C8—H8A	109.3	H22A—C22—H22C	109.5
N2—C8—H8B	109.3	H22B—C22—H22C	109.5
C9—C8—H8B	109.3
N2—Zn1—O3—C2	−0.5 (3)	C8—N2—C7—C1	−175.8 (3)
Cl1—Zn1—O3—C2	−122.0 (3)	Zn1—N2—C7—C1	−1.9 (5)
Cl2—Zn1—O3—C2	110.8 (3)	C6—C1—C7—N2	−179.0 (3)
N5—Zn2—O6—C13	9.4 (3)	C2—C1—C7—N2	4.0 (5)
Cl4—Zn2—O6—C13	118.1 (2)	C7—N2—C8—C9	−132.0 (3)
Cl3—Zn2—O6—C13	−112.0 (3)	Zn1—N2—C8—C9	54.1 (3)
O3—Zn1—N2—C7	0.3 (3)	C10—N3—C9—C8	−169.7 (3)
Cl1—Zn1—N2—C7	116.0 (2)	C11—N3—C9—C8	66.9 (4)
Cl2—Zn1—N2—C7	−115.9 (2)	N2—C8—C9—N3	61.9 (4)
O3—Zn1—N2—C8	173.9 (2)	Zn2—O6—C13—C14	172.1 (2)
Cl1—Zn1—N2—C8	−70.3 (2)	Zn2—O6—C13—C12	−8.5 (5)
Cl2—Zn1—N2—C8	57.7 (2)	C17—C12—C13—O6	−178.3 (3)
O6—Zn2—N5—C18	−3.5 (3)	C18—C12—C13—O6	−0.6 (5)
Cl4—Zn2—N5—C18	−117.9 (3)	C17—C12—C13—C14	1.0 (5)
Cl3—Zn2—N5—C18	116.6 (3)	C18—C12—C13—C14	178.7 (3)
O6—Zn2—N5—C19	166.1 (2)	O6—C13—C14—C15	179.2 (3)
Cl4—Zn2—N5—C19	51.7 (2)	C12—C13—C14—C15	−0.2 (5)
Cl3—Zn2—N5—C19	−73.8 (2)	C13—C14—C15—C16	−0.5 (6)
Zn1—O3—C2—C3	−177.7 (2)	C14—C15—C16—C17	0.3 (6)
Zn1—O3—C2—C1	2.4 (5)	C14—C15—C16—N4	−177.1 (4)
C6—C1—C2—O3	178.9 (3)	O4—N4—C16—C17	−2.8 (7)
C7—C1—C2—O3	−4.2 (5)	O5—N4—C16—C17	178.5 (4)
C6—C1—C2—C3	−1.0 (5)	O4—N4—C16—C15	174.7 (5)
C7—C1—C2—C3	175.9 (3)	O5—N4—C16—C15	−4.0 (6)
O3—C2—C3—C4	−177.9 (3)	C15—C16—C17—C12	0.6 (6)
C1—C2—C3—C4	2.0 (5)	N4—C16—C17—C12	178.1 (4)
C2—C3—C4—C5	−1.7 (5)	C13—C12—C17—C16	−1.3 (6)
C3—C4—C5—C6	0.3 (5)	C18—C12—C17—C16	−179.1 (4)
C3—C4—C5—N1	−175.3 (3)	C19—N5—C18—C12	−173.2 (3)
O2—N1—C5—C6	−0.6 (5)	Zn2—N5—C18—C12	−3.4 (5)
O1—N1—C5—C6	−177.5 (3)	C17—C12—C18—N5	−175.1 (4)
O2—N1—C5—C4	175.2 (4)	C13—C12—C18—N5	7.2 (6)
O1—N1—C5—C4	−1.7 (5)	C18—N5—C19—C20	−136.7 (3)
C4—C5—C6—C1	0.7 (5)	Zn2—N5—C19—C20	53.3 (3)
N1—C5—C6—C1	176.4 (3)	C21—N6—C20—C19	60.1 (4)
C2—C1—C6—C5	−0.3 (5)	C22—N6—C20—C19	−175.6 (3)
C7—C1—C6—C5	−177.5 (3)	N5—C19—C20—N6	59.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···Cl3^i	0.90 (4)	2.59 (3)	3.299 (3)	137 (3)
N3—H3A···O7^ii	0.91 (3)	1.88 (2)	2.746 (4)	160 (4)
O7—H7A···O3^iii	0.83 (3)	2.03 (3)	2.859 (4)	175 (4)
O7—H7B···Cl1^iii	0.83 (3)	2.85 (3)	3.384 (3)	124 (3)
C7—H7···Cl4^iv	0.93	2.72	3.629 (3)	167
C10—H10B···O5^ii	0.96	2.57	3.525 (7)	171
C19—H19B···Cl2^v	0.97	2.74	3.695 (3)	169
C22—H22B···O6^i	0.96	2.54	3.341 (3)	142
C22—H22C···O2^iv	0.96	2.56	3.232 (7)	127

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