Synthesis, crystal structure, and spectroscopic and thermal properties of the polymeric compound catena-poly[[bis­(2,4-di­chloro­benzoato)zinc(II)]-μ-isonicotinamide]

Zinc(II) carboxyl­ates with O-, S- and N-donor ligands are inter­esting for their structural features, as well as for their anti­bacterial and anti­fungal activities. The one-dimensional zinc(II) coordination complex catena-poly[[bis­(2,4-di­chloro­benzoato-κO)zinc(II)]-μ-isonicotinamide-κ²N¹:O], [Zn(C₇H₃Cl₂O₂)₂(C₆H₆N₂O)]_n, has been prepared and characterized by IR spectroscopy, single-crystal X-ray analysis and thermal analysis. The tetra­hedral ZnO₃N coordination about the Zn^II cation is built up by the N atom of the pyridine ring, an O atom of the carbonyl group of the isonicotinamide ligand and two O atoms of two di­chloro­benzoate ligands. Isonicotinamide serves as a bridge between tetra­hedra, with a Zn...Zn distance of 8.8161 (7) Å. Additionally, π–π inter­actions between the planar benzene rings contribute to the stabilization of the extended structure. The structure is also stabilized by inter­molecular hydrogen bonds between the amino and carboxyl­ate groups of the ligands, forming a two-dimensional network. During thermal decomposition of the complex, isonicotinamide, di­chloro­benzene and carbon dioxide were evolved. The final solid product of the thermal decomposition heated up to 1173 K was metallic zinc.

S1. Introduction

Zinc(II) carboxyl­ates with O-, S- and N-donor ligands are paid attention not only from the point of view of their structural features, but also for their anti­bacterial and anti­fungal activities (Krajníková et al., 2012). It is well known that carboxyl­ates can coordinate to metals via their O atoms. The carboxyl­ate group can bind as a monodentate (syn–syn, syn–anti or anti–anti), bidentate bridging or chelating ligand, which leads to versatile coordination possibilities (Melník et al., 1995). Some isonicotinamide compounds are known for their bio-active, anti­tubercular, anti­pyretic, fibrinolytic and anti­bacterial properties (Ahuja & Prasad, 1976).

There are several zinc(II) complexes with isonicotinamide (inad) for which X-ray data are available. The crystal structure of [Zn(5-Clsalicylate)₂(inad)₂(H₂O)] shows that the Zn^II cation is five-coordinated (Bujdošová et al., 2011). The ZnO₃N₂ inner coordination sphere is built up by two O atoms of monodentate 5-chloro­salicylate ligands, two pyridine N atoms of isonicotinamide ligands and the water O atom. These donor atoms about the Zn^II cation distort the configuration between square-pyramidal and trigonal bipyramidal.

X-ray analysis of [Zn{4-(di­methyl­amino)­benzoate}₂(inad)(H₂O)₂] (Hökelek, Dal et al., 2009a) shows that the Zn^II cation is six-coordinated. The pseudoo­cta­hedral ZnO₅N coordination about the Zn^II cation is formed by the O atoms of the two non-equivalent 4-(di­methyl­amino)­benzoate ligands and the two water molecules, and the pyridine N atom of isonicotinamide.

In [Zn(inad)₂(H₂O)₄](naphthalene-1,5-di­sulfonate)(inad)₂.4H₂O (Zhao et al., 2010) and [Zn(inad)₂(H₂O)₄](3-OH-benzoate)₂.4H₂O (Zaman et al., 2013), the Zn^II cations are also six-coordinated. The ZnO₄N₂ coordination is built up by the O atoms of four water molecules and two N atoms of two isonicotinamide ligands.

In [Zn(4-formyl­benzoate)₂(inad)]_n, the Zn^II cation is tetra­hedrally coordinated (ZnO₃N) by three O atoms from one monodentate and one bidentate benzoate ligand, and the N atom of the pyridine ring of isonicotinamide (Hökelek, Yilmaz et al., 2009).

X-ray analysis of [ZnI₂(inad)₂] (Paşaoğlu et al., 2006) shows that isonicotinamide coordinates via the N-donor atoms of the pyridine rings, and the two I atoms complete the tetra­hedral environment (ZnN₂I₂) about the Zn^II cation.

Several crystal structures of isonicotinamide benzoate complexes with manganese, cobalt and copper (Hökelek, Dal et al. 2009b; Uçar et al., 2007; Moncoľ et al., 2007) are known. In these complexes, isonicotinamide coordinates via the N atom of the pyridine ring.

In [Mn₆(CH₃)₃(acetate)₁₀(inad)₂]_n (Fursova et al., 2013), the isonicotinamide ligands are coordinated to the central atom via the O atom of the –CONH₂ group and via the N atom of the pyridine ring.

Describing the synthesis of the related compound [Zn(2,4-Cl₂C₆H₃COO)₂(inad)]_n, (I), and its thermal, spectroscopic and crystal structure analyses is the aim of this paper.

S2. Experimental

Elemental analysis (C, H, N and Cl) was performed on a Perkin–Elmer 2400 CHN analyser. The content of zinc was determined complexometrically using Complexone III as an agent and Eriochrome black T as an indicator.

The IR spectra were recorded on a Nicolet 6700 FT–IR spectrometer (Thermo Scientific) using KBr pellets (2 mg of sample per 200 mg of KBr) in the range 400–4000 cm^-1.

The thermal measurements of thermogravimetry/differential thermogravimetry (TG/DTG) and differential thermal anaylsis (DTA) were carried out up to 1173 K, at a heating rate of 9 K min^-1 under a nitro­gen atmosphere using a NETZSCH STA 409 PC/PG thermoanalyser (Germany). The sample (amount 22.4 mg) was placed in a ceramic crucible during measurement.

The final solid product of the thermal decomposition was identified with a Philips PW 1730/1050 diffractometer (Germany) in Bragg–Brentano geometry, using β-filtered Co Kα radiation (λ = 1.78892 Å), 40 kV/35 mA, in the range 2–61° in 2θ, with a step of 0.02°.

S2.1. Synthesis and crystallization

Chemicals of analytical grade, i.e. ZnCl₂ (Fluka, Germany), Na₂CO₃ (Centralchem, Slovakia), 2,4-di­chloro­benzoic acid (Aldrich, Germany) and isonicotinamide (Aldrich, Germany), were used.

An aqueous solution (20 ml) of ZnCl₂ (1.36 g, 10 mmol) was added to an aqueous solution (20 ml) of Na₂CO₃ (1.06 g, 10 mmol). The freshly prepared precipitate of ZnCO₃ was purified from sodium chloride by decantation and this water suspension was added to an ethanol solution of 2,4-di­chloro­benzoic acid (3.82 g, 20 mmol). This mixture was stirred for 2 h at room temperature and the excess ZnCO₃ was filtered off using an S4 frit. A methanol solution of isonicotinamide (2.44 g, 20 mmol) was then added dropwise. The reaction mixture was stirred for 2 h at 313 K and the solution was reduced in volume at 343 K in a water bath. The filtrate was left to stand at room temperature. Colourless crystals of (I) were collected by filtration, washed with a small amount of cold methanol and then dried at room temperature. The crystals were separated manually under a microscope. The yield was 65%. Analysis, calculated for C₂₀H₁₂Cl₄N₂O₅Zn: C 42.32, H 2.13, N 4.94, Cl 24.99, Zn 11.53%; found: C 42.39, H 1.89, N 4.90, Cl 24.98; Zn 11.23%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms attached to C atoms were placed at calculated positions, with C—H = 0.93 Å, and refined as riding. The U_iso values of all H atoms were set at 1.2U_eq of their respective parent atoms.

S3. Results and discussion

The title complex crystallizes with a monoclinic lattice in the centrosymmetric space group P2₁/c. The geometry around the Zn^II cation is tetra­hedral (Fig. 1), involving two O atoms from two monodentate 2,4-di­chloro­benzoate ligands, one O atom from the carbonyl group of an inad ligand and one N atom of the pyridine ring of another inad ligand. The inad acts as a µ₂-N:O-bridging ligand, linking the fragments into zigzag chains with a Zn···Zn distance of 8.816 Å; the chains are perpendicular to the b axis (Fig. 2).

The mean Zn—O(carboxyl­ate) bond length of 1.940 Å (Table 2) is shorter than the Zn—O(carbonyl) value of 2.028 (1) Å, and is also shorter than the value of 2.0508 (7) Å found in [Zn(5—Cl-salicylate)₂(inad)₂(H₂O)] (Bujdošová et al., 2011). The Zn—N bond length in (I) of 2.0349 (17) Å is slightly shorter than the values observed for [Zn(5—Cl-salicylate)₂(inad)₂], with an average value of 2.1355 (3) Å (Bujdošová et al., 2011), [Zn(inad)₂(H₂O)₄](1,5-naphthalene­disulfonate)(inad)₂.4H₂O, with an average value of 2.1403 (2) Å (Zhao et al., 2010) and [Zn(inad)₂(H₂O)₄](3-OH-benz)₂.4H₂O, with an average value of 2.117 (2) Å (Zaman et al., 2013). The observed L—Zn—L (L denotes a ligand) bond angles range from 96.20 (6) to 135.20 (7)° (Table 2).

The structure of (I) is stabilized by inter­molecular N—H···O hydrogen bonds between the amide N atom of inad and the carboxyl­ate O atoms of the 2,4-di­chloro­benzoate ligands, forming a two-dimensional network (Table 3 and Fig. 3). The structure of (I) is also stabilized by π–π inter­actions (Fig. 4) between the stacked aromatic rings of the 2,4-di­chloro­benzoate ligands of two adjacent layers, which may contribute to the self-assembly of the structure (Janiak, 2000). The inter­actions between the aromatic rings are evidenced by the Cg4···Cg4^iv distance of 3.7085 (12) Å (Cg4 is the centroid of the C22–C27 ring), and by the angle between the aromatic-ring normal and the vector connecting Cg4 and Cg4^iv of 24.23° [symmetry code: (iv) -x + 1, -y, -z + 1].

The presence of the individual functional groups in (I) was confirmed by IR spectroscopy. Stretching ν(N—H) vibrations of the amino group are observed at 3367 and 3197 cm^-1, and a stretching ν(C—H) vibration of the aromatic ring is assigned at 3068 cm^-1. A deformation out-of-plane γ(C—H) vibration is observed at 864 cm^-1 and a ν(C—Cl) stretching vibration is at 779 cm^-1. The strong absorption band of the stretching inad carbonyl ν(C═O) vibration at 1674 cm^-1 is shifted slightly to a higher wavenumber compared with free isonicotinamide (1666 cm^-1). This can be explained by the fact that, in (I), the O atom of inad is coordinated to the Zn^II cation. The carboxyl­ate groups show two stretching vibrations, i.e. asymmetric ν_as(COO^-) at 1601 cm^-1 and symmetric ν_s(COO^-) at 1374 cm^-1. There is also a deformation δ(COO^-) vibration of the carboxyl­ate group at 679 cm^-1 (Fig. 5). The modes of carboxyl­ate binding were assigned from the IR spectrum using the magnitude of the separation Δ between the carboxyl­ate stretches (Δ_exp = ν_as – ν_s). The following order has been proposed for divalent metal carboxyl­ates (Nakamoto, 1997): Δ (chelating) << Δ (bridging) < Δ (ionic) << Δ (monodentate).

The IR spectrum of the sodium salt of 2,4-di­chloro­benzoic acid shows the asymmetric and symmetric stretching vibrations of the carboxyl­ate group at 1589 and 1398 cm^-1, respectively. The magnitude separation (Δ) of 191 cm^-1 is 36 cm^-1 smaller than that found in (I) of 227 cm^-1. This indicates that the carboxyl­ate groups in Zn^II complex (I) are coordinated via one O atom.

The results of thermogravimetric analysis (TGA) are presented in Fig. 6. It was found that the complex is thermally stable up to 503 K. Above this temperature, one mole of inad and two moles of 1,3-di­chloro­benzene are evolved (the experimental mass loss is 72.95% and the calculated mass loss is 73.32%), which is accompanied by a double endothermic effect at 528 and 568 K. In the IR spectrum of the solid inter­mediate product heated up to 573 K (Fig. 7), the absorption bands of inad are missing [ν(N—H) = 3342 and 3197 cm^-1; υ(C═O) = 1674 cm^-1]. The next step of the thermal decomposition in the temperature range 773–1023 K is the release of two moles of carbon dioxide (the experimental mass loss is 16.26% and the calculated mass loss is 15.51%), which is accompanied by an exothermic effect at 913 K. The final solid product of the thermal decomposition was metallic zinc (the experimental mass loss is 11.47% and the calculated mass loss is 11.52%). The presence of metallic zinc was proven by recording powder diffraction data (Zn 2θ: 43.0240, 46.9317, 52.4526°) (Fig. 8). The obtained result corresponds with the powder pattern for metallic zinc found in the literature (McMurdie et al. 1986). Thus, the following reaction is proposed for the decomposition process:

[Zn(2,4-Cl₂C₆H₃COO)₂(inad)] → inad + 2 Cl₂C₆H₄ + 2 CO₂ + Zn

[Summary/conclusion?]

Computing details

Data collection: COLLECT (Bruker, 2004); cell refinement: DIRAX/LSQ (Duisenberg & Schreurs, 2000); data reduction: EVALCCD (Duisenberg & Schreurs 2000); program(s) used to solve structure: SIR2011 (Burla et al., 2012); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The isonicotinamide ligand is on an inversion centre [symmetry code: (i) x, -y + 3/2, z + 1/2].
	Fig. 2. The zigzag chains in (I). The dashed line indicates the Zn···Zn distance (with its value).
	Fig. 3. The two-dimensional network of N—H···O interactions in (I) (dashed lines). H atoms have been omitted for clarity. [Symmetry codes as in Table 3.]
	Fig. 4. The two-dimensional network of π–π interactions in (I) (dashed lines; Cg4 is the centroid of the C22–C27 ring). H atoms have been omitted for clarity. [Symmetry code: (iv) -x + 1, -y, -z + 1.]
	Fig. 5. The IR spectrum of (I).
	Fig. 6. TG/DTG and DTA curves of (I).
	Fig. 7. The IR spectrum of (I) heated up to 573 K.
	Fig. 8. Powder diffraction profile of (I) heated up to 1173 K.

catena-Poly[[bis(2,4-dichlorobenzoato-κO)zinc(II)]-µ-isonicotinamide-κ²N¹:O]

Crystal data

[Zn(C7H3Cl2O2)2(C6H6N2O)]	F(000) = 1136
Mr = 567.49	Dx = 1.782 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.1540 (13) Å	Cell parameters from 17777 reflections
b = 7.9390 (4) Å	θ = 2.3–27.5°
c = 13.936 (1) Å	µ = 1.70 mm^−1
β = 93.613 (6)°	T = 273 K
V = 2114.9 (2) Å^3	Brick, colourless
Z = 4	0.45 × 0.25 × 0.12 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	4748 independent reflections
Radiation source: fine-focus sealed tube	3932 reflections with I > 2σ(I)
Detector resolution: 9 pixels mm^-1	Rint = 0.025
CCD scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −24→24
Tmin = 0.921, Tmax = 0.937	k = −10→9
17777 measured reflections	l = −16→18

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.067	w = 1/[σ^2(Fo^2) + (0.0298P)^2 + 2.6763P] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max = 0.001
4748 reflections	Δρmax = 0.52 e Å^−3
297 parameters	Δρmin = −0.47 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.25264 (2)	0.40985 (3)	0.40528 (2)	0.01495 (7)
Cl1	0.56541 (3)	−0.36051 (7)	0.39290 (4)	0.02864 (13)
Cl2	0.47759 (3)	0.27108 (6)	0.35049 (4)	0.02272 (12)
Cl3	−0.16163 (3)	0.05905 (7)	0.46020 (5)	0.02992 (13)
Cl4	0.03903 (3)	0.05942 (9)	0.21366 (4)	0.03642 (15)
O1	0.32525 (8)	0.26272 (19)	0.36392 (11)	0.0241 (3)
O2	0.29229 (8)	0.1122 (2)	0.48747 (12)	0.0268 (4)
O3	0.15535 (8)	0.38121 (19)	0.43523 (11)	0.0229 (3)
O4	0.15737 (8)	0.2472 (2)	0.29728 (11)	0.0264 (3)
O5	0.28437 (7)	0.97410 (18)	0.03015 (10)	0.0180 (3)
N1	0.25858 (9)	0.6046 (2)	0.31119 (12)	0.0165 (3)
N2	0.24264 (11)	1.1614 (2)	0.13473 (15)	0.0247 (4)
C1	0.26349 (10)	1.0108 (3)	0.11113 (14)	0.0170 (4)
C2	0.26303 (10)	0.8732 (2)	0.18463 (14)	0.0166 (4)
C3	0.21622 (12)	0.8728 (3)	0.25643 (16)	0.0231 (5)
H3	0.1860	0.9631	0.2635	0.030*
C4	0.21527 (11)	0.7362 (3)	0.31707 (16)	0.0232 (5)
H4	0.1831	0.7351	0.3643	0.030*
C5	0.30463 (11)	0.6066 (3)	0.24265 (15)	0.0212 (4)
H5	0.3353	0.5165	0.2385	0.028*
C6	0.30809 (11)	0.7375 (3)	0.17821 (15)	0.0218 (4)
H6	0.3403	0.7349	0.1310	0.028*
C11	0.33190 (11)	0.1392 (3)	0.42233 (15)	0.0190 (4)
C12	0.39099 (10)	0.0187 (2)	0.40899 (14)	0.0161 (4)
C13	0.38107 (11)	−0.1500 (3)	0.43268 (15)	0.0194 (4)
H13	0.3380	−0.1831	0.4537	0.025*
C14	0.43302 (11)	−0.2697 (3)	0.42591 (15)	0.0202 (4)
H14	0.4250	−0.3819	0.4408	0.026*
C15	0.49713 (11)	−0.2180 (3)	0.39640 (15)	0.0189 (4)
C16	0.50947 (11)	−0.0523 (3)	0.37248 (15)	0.0184 (4)
H16	0.5531	−0.0198	0.3532	0.024*
C17	0.45622 (11)	0.0649 (2)	0.37758 (14)	0.0162 (4)
C21	0.12706 (10)	0.2869 (2)	0.36965 (15)	0.0169 (4)
C22	0.05454 (10)	0.2264 (2)	0.38706 (15)	0.0166 (4)
C23	0.02638 (11)	0.2735 (3)	0.47245 (16)	0.0229 (5)
H23	0.0532	0.3397	0.5158	0.030*
C24	−0.03976 (12)	0.2258 (3)	0.49553 (17)	0.0271 (5)
H24	−0.0575	0.2604	0.5529	0.035*
C25	−0.07901 (11)	0.1258 (3)	0.43187 (17)	0.0227 (4)
C26	−0.05368 (11)	0.0746 (3)	0.34601 (16)	0.0229 (4)
H26	−0.0805	0.0069	0.3036	0.030*
C27	0.01265 (11)	0.1263 (3)	0.32444 (15)	0.0196 (4)
H1	0.2449 (14)	1.241 (4)	0.096 (2)	0.031 (7)*
H2	0.2281 (14)	1.185 (4)	0.191 (2)	0.034 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01660 (12)	0.01490 (11)	0.01367 (12)	0.00014 (8)	0.00339 (8)	0.00041 (9)
Cl1	0.0251 (3)	0.0212 (3)	0.0395 (3)	0.0077 (2)	0.0010 (2)	0.0008 (2)
Cl2	0.0279 (3)	0.0145 (2)	0.0263 (3)	−0.00263 (19)	0.0059 (2)	0.00335 (19)
Cl3	0.0170 (2)	0.0332 (3)	0.0401 (3)	−0.0050 (2)	0.0062 (2)	−0.0007 (2)
Cl4	0.0355 (3)	0.0515 (4)	0.0228 (3)	−0.0115 (3)	0.0067 (2)	−0.0167 (3)
O1	0.0264 (8)	0.0245 (8)	0.0218 (8)	0.0103 (6)	0.0044 (6)	0.0013 (6)
O2	0.0249 (8)	0.0256 (8)	0.0312 (9)	−0.0020 (6)	0.0130 (7)	−0.0064 (7)
O3	0.0177 (7)	0.0291 (8)	0.0222 (8)	−0.0052 (6)	0.0035 (6)	−0.0046 (6)
O4	0.0249 (8)	0.0292 (8)	0.0263 (9)	−0.0036 (7)	0.0112 (7)	−0.0071 (7)
O5	0.0220 (7)	0.0182 (7)	0.0143 (7)	0.0036 (6)	0.0040 (6)	0.0015 (6)
N1	0.0172 (8)	0.0168 (8)	0.0157 (8)	−0.0006 (6)	0.0021 (6)	0.0001 (7)
N2	0.0433 (12)	0.0172 (9)	0.0150 (10)	0.0041 (8)	0.0113 (8)	0.0028 (8)
C1	0.0176 (9)	0.0179 (9)	0.0157 (10)	0.0001 (7)	0.0019 (8)	0.0010 (8)
C2	0.0200 (10)	0.0166 (9)	0.0129 (10)	−0.0016 (7)	−0.0002 (8)	0.0002 (7)
C3	0.0266 (11)	0.0198 (10)	0.0237 (12)	0.0076 (8)	0.0094 (9)	0.0020 (8)
C4	0.0262 (11)	0.0211 (11)	0.0239 (12)	0.0048 (8)	0.0130 (9)	0.0025 (9)
C5	0.0221 (10)	0.0215 (10)	0.0205 (11)	0.0070 (8)	0.0064 (8)	0.0027 (8)
C6	0.0226 (10)	0.0250 (11)	0.0186 (11)	0.0052 (8)	0.0074 (8)	0.0041 (9)
C11	0.0184 (10)	0.0183 (10)	0.0200 (11)	−0.0018 (8)	−0.0010 (8)	−0.0058 (8)
C12	0.0189 (10)	0.0164 (9)	0.0128 (10)	0.0000 (7)	−0.0001 (7)	−0.0012 (7)
C13	0.0198 (10)	0.0218 (10)	0.0164 (10)	−0.0051 (8)	0.0004 (8)	0.0005 (8)
C14	0.0251 (11)	0.0147 (10)	0.0205 (11)	−0.0024 (8)	−0.0012 (8)	0.0025 (8)
C15	0.0202 (10)	0.0170 (10)	0.0190 (11)	0.0030 (8)	−0.0021 (8)	−0.0028 (8)
C16	0.0185 (10)	0.0197 (10)	0.0173 (10)	−0.0011 (8)	0.0032 (8)	−0.0010 (8)
C17	0.0219 (10)	0.0129 (9)	0.0136 (10)	−0.0020 (7)	0.0010 (8)	0.0005 (7)
C21	0.0175 (9)	0.0157 (9)	0.0174 (10)	0.0029 (7)	0.0011 (8)	0.0025 (8)
C22	0.0176 (10)	0.0154 (9)	0.0167 (10)	0.0011 (7)	0.0006 (8)	0.0025 (8)
C23	0.0212 (10)	0.0268 (11)	0.0210 (11)	−0.0044 (8)	0.0035 (8)	−0.0057 (9)
C24	0.0225 (11)	0.0356 (13)	0.0243 (12)	−0.0039 (9)	0.0094 (9)	−0.0073 (10)
C25	0.0155 (10)	0.0223 (11)	0.0304 (12)	0.0002 (8)	0.0023 (8)	0.0023 (9)
C26	0.0202 (10)	0.0231 (11)	0.0247 (12)	−0.0014 (8)	−0.0030 (8)	−0.0016 (9)
C27	0.0209 (10)	0.0201 (10)	0.0178 (11)	0.0018 (8)	0.0015 (8)	−0.0008 (8)

Geometric parameters (Å, º)

Zn1—O1	1.9317 (15)	C4—H4	0.9300
Zn1—O3	1.9486 (15)	C5—C6	1.378 (3)
Zn1—O5^i	2.0280 (14)	C5—H5	0.9300
Zn1—N1	2.0349 (17)	C6—H6	0.9300
Cl1—C15	1.732 (2)	C11—C12	1.502 (3)
Cl2—C17	1.7344 (19)	C12—C13	1.395 (3)
Cl3—C25	1.738 (2)	C12—C17	1.399 (3)
Cl4—C27	1.737 (2)	C13—C14	1.383 (3)
O1—C11	1.276 (3)	C13—H13	0.9300
O2—C11	1.238 (3)	C14—C15	1.382 (3)
O3—C21	1.276 (3)	C14—H14	0.9300
O4—C21	1.236 (3)	C15—C16	1.381 (3)
O5—C1	1.255 (2)	C16—C17	1.386 (3)
O5—Zn1^ii	2.0281 (14)	C16—H16	0.9300
N1—C5	1.340 (3)	C21—C22	1.504 (3)
N1—C4	1.340 (3)	C22—C23	1.388 (3)
N2—C1	1.309 (3)	C22—C27	1.396 (3)
N2—H1	0.83 (3)	C23—C24	1.379 (3)
N2—H2	0.88 (3)	C23—H23	0.9300
C1—C2	1.498 (3)	C24—C25	1.378 (3)
C2—C3	1.385 (3)	C24—H24	0.9300
C2—C6	1.387 (3)	C25—C26	1.380 (3)
C3—C4	1.376 (3)	C26—C27	1.386 (3)
C3—H3	0.9300	C26—H26	0.9300
O1—Zn1—O3	135.20 (7)	C17—C12—C11	124.51 (18)
O1—Zn1—O5^i	110.38 (6)	C14—C13—C12	122.27 (19)
O3—Zn1—O5^i	96.20 (6)	C14—C13—H13	118.9
O1—Zn1—N1	101.34 (7)	C12—C13—H13	118.9
O3—Zn1—N1	108.64 (7)	C15—C14—C13	118.23 (19)
O5^i—Zn1—N1	100.48 (6)	C15—C14—H14	120.9
C11—O1—Zn1	108.62 (13)	C13—C14—H14	120.9
C21—O3—Zn1	106.49 (13)	C14—C15—C16	121.56 (19)
C1—O5—Zn1^ii	124.81 (13)	C14—C15—Cl1	120.10 (16)
C5—N1—C4	118.17 (18)	C16—C15—Cl1	118.31 (16)
C5—N1—Zn1	122.29 (14)	C15—C16—C17	119.32 (19)
C4—N1—Zn1	119.54 (14)	C15—C16—H16	120.3
C1—N2—H1	120.3 (19)	C17—C16—H16	120.3
C1—N2—H2	122.8 (18)	C16—C17—C12	120.96 (18)
H1—N2—H2	117 (3)	C16—C17—Cl2	115.98 (15)
O5—C1—N2	123.88 (19)	C12—C17—Cl2	122.93 (15)
O5—C1—C2	117.47 (17)	O4—C21—O3	122.29 (19)
N2—C1—C2	118.65 (18)	O4—C21—C22	122.43 (19)
C3—C2—C6	118.63 (19)	O3—C21—C22	115.27 (18)
C3—C2—C1	121.81 (18)	C23—C22—C27	116.74 (19)
C6—C2—C1	119.48 (18)	C23—C22—C21	117.71 (18)
C4—C3—C2	118.64 (19)	C27—C22—C21	125.55 (19)
C4—C3—H3	120.7	C24—C23—C22	122.6 (2)
C2—C3—H3	120.7	C24—C23—H23	118.7
N1—C4—C3	123.03 (19)	C22—C23—H23	118.7
N1—C4—H4	118.5	C25—C24—C23	118.7 (2)
C3—C4—H4	118.5	C25—C24—H24	120.7
N1—C5—C6	122.30 (19)	C23—C24—H24	120.7
N1—C5—H5	118.8	C24—C25—C26	121.4 (2)
C6—C5—H5	118.8	C24—C25—Cl3	119.81 (18)
C5—C6—C2	119.21 (19)	C26—C25—Cl3	118.81 (17)
C5—C6—H6	120.4	C25—C26—C27	118.5 (2)
C2—C6—H6	120.4	C25—C26—H26	120.7
O2—C11—O1	124.0 (2)	C27—C26—H26	120.7
O2—C11—C12	118.83 (19)	C26—C27—C22	122.1 (2)
O1—C11—C12	117.14 (18)	C26—C27—Cl4	115.11 (16)
C13—C12—C17	117.63 (18)	C22—C27—Cl4	122.77 (16)
C13—C12—C11	117.83 (18)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4^iii	0.88 (3)	2.12 (3)	2.954 (2)	159 (2)
N2—H1···O2^ii	0.83 (3)	2.16 (3)	2.931 (3)	155 (3)

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