A new one-dimensional Zn^II coordination polymer based on 2-[(1H-imidazol-1-yl)methyl]-1H-benz­imidazole and benzene-1,2-di­carboxyl­ate

Multidentate N-heterocyclic compounds form a variety of metal complexes with many intriguing structures and inter­esting properties. The title coordination polymer, catena-poly[zinc(II)-bis­{[mu]-2-[(1H-imidazol-1-yl)methyl]-1H-benzimid­azole}-[kappa]²N³:N^3';N^3':N³-zinc(II)-bis­([mu]-benzene-1,2-di­carboxyl­ato)-[kappa]²O¹:O²;[kappa]³O¹,O^1':O²], [Zn₂(C₈H₄O₄)₂(C₁₁H₁₀N₄)₂]_n, has been synthesized by the reaction of Zn(NO₃)₂ with 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole (imb) and benzene-1,2-di­carb­oxy­lic acid (H₂bdic) under hydro­thermal conditions. There are two crystallographically distinct imb ligands [imb(A) and imb(B)] in the structure which adopt very similar coordination geometries. The imb(A) ligand bridges two symmetry-related Zn1 ions, yielding a binuclear [(Zn1)₂{imb(A)}₂] unit, and the imb(B) ligand bridges two symmetry-related Zn2 ions resulting in a binuclear [(Zn2)₂{imb(B)}₂] unit. The above-mentioned binuclear units are further connected alternately by pairs of bridging bdic^2- ligands, forming an infinite one-dimensional chain. These one-dimensional chains are further connected through N-H...O hydrogen bonds, leading to a two-dimensional layered structure. In addition, the title polymer exhibits good fluorescence properties in the solid state at room temperature.

S1. Introduction

It is well known that multidentate N-heterocyclic compounds form a variety of metal complexes with many intriguing structures and inter­esting properties. In the last few years, many researchers, including our group, have focused attention on the design and synthesis of metal–organic frameworks (MOFs) based on 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole (imb), since it has three potential N-atom donors and can coordinate to metal ions using monodentate, bidentate–bridging or tridentate–bridging coordination modes in the construction of coordination polymers (Yang et al., 2014; Wang et al., 2014). This ligand can also act as a hydrogen-bonding donor and acceptor in the assembly of supra­molecular structures. In addition, the imb ligand can adopt different coordination geometries owing to the existence of the flexible methyl­ene spacer, resulting in complexes with helical structures. To date, about 40 complexes constructed from the imb ligand have been reported, ranging from zero- to three-dimensional complexes with rich structural diversity. Among the reported imb-based complexes, a few have been obtained using just one type of organic ligand, i.e. imb (Duan et al., 2014; Wang et al., 2010), but most of them are prepared by using mixed ligands of imb and polycarboxyl­ates. The polycarboxyl­ates used include aliphatic carboxyl­ates (Wang et al., 2014; Zhang et al., 2014), benzene-1,2,4,5-tetra­carboxyl­ate (Yang et al., 2014), benzene-1,3,5-tri­carboxyl­ate (Huang, Yang & Meng, 2015), benzene-1,4-di­carboxyl­ate (Wang et al., 2013) and benzene-1,3-di­carboxyl­ate (Huang, Tang, Liu, Su & Meng, 2014). As far as we know, no complex constructed from imb and benzene-1,2-di­carboxyl­ate ligands has been reported previously. In this paper, we have directed our efforts towards the synthesis and characterization of the new one-dimensional coordination polymer [Zn₂(bdic)₂(imb)₂]_n (H₂bdic = benzene-1,2-di­carb­oxy­lic acid), (I). In addition, the IR spectrum, thermostability and fluorescence properties were also investigated.

S2. Experimental

S2.1. Synthesis and crystallization

IR data were recorded on a Bruker TENSOR 27 spectrophotometer with KBr pellets from 400 to 4000 cm^-1. Elemental analyses (C, H and N) were carried out on a FLASH EA 1112 elemental analyser. Thermogravimetric (TG) and differential scanning calorimetry (DSC) analyses were performed by heating the sample from 303 to 1053 K at a rate of 10 K min^-1 in air on a NETZSCH STA 409 PC/PG differential thermal analyser. Steady-state fluorescence measurements were performed using a F-7000 fluorescence spectrophotometer operating at 700 V at room temperature in the solid state. The excitation slit was 5 nm and the emission slit was also 5 nm; the scan speed was 1200 nm min^-1.

2-[(1H-Imidazol-1-yl)methyl]-1H-benzimidazole (imb) was synthesized according to the literature method of Meng et al. (2010) with some modification, i.e. 1H-tetra­zole-1-acetic acid was replaced with 2-(imidazol-1-yl)acetic acid, but the other experimental conditions were left unchanged. A mixture of Zn(NO₃)₂ (0.1 mmol), imb (0.1 mmol), H₂bdic (0.1 mmol), NaOH (0.2 mmol) and H₂O (7 ml) was poured into a Teflon-lined stainless steel reactor (25 ml), which was sealed and heated to 393 K for 72 h. After being cooled to room temperature at a rate of 10 K h^-1, colourless crystals of [Zn₂(bdic)₂(imb)₂]_n suitable for X-ray analysis were obtained, collected by hand, washed with distilled water and dried in air (yield 29 mg, 68% based on Zn). Elemental analysis, calculated for C₃₈H₂₈N₈O₈Zn₂: C 53.35, H 3.30, N 13.10%; found: C 52.85, H 3.34, N 12.90%. IR (KBr disc, ν, cm^-1): 3439 (m), 3140 (m), 1630 (s), 1567 (s), 1488 (m), 1466 (m), 1407 (s), 1382 (s), 1280 (m), 1105 (s), 1086 (s), 1040 (s), 946 (m), 846 (m), 749 (s), 657 (m).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic) or 0.97 (CH₂) and N—H = 0.86 Å. All H atoms were assigned U_iso(H) = 1.2U_eq(C,N).

S3. Comment

The results of X-ray crystallographic analysis reveal that the title polymer, (I), crystallizes in the triclinic space group P1. The asymmetric unit contains two crystallographically distinct Zn^II cations, two crystallographically distinct imb ligands and two crystallographically distinct dianionic bdic^2- ligands. As shown in Fig. 1, each Zn1 ion is coordinated by two N atoms from two symmetry-related imb ligands [denoted imb(A), bright-green colour] and by three O atoms from two crystallographically distinct bdic^2- ligands, and is located in an approximate trigonal–bipyramidal coordination environment, with atoms N4ⁱ, O1 and O5 forming the basal plane [symmetry code: (i) -x + 1, -y + 1, -z] and atoms N1 and O2 occupying the apical positions; the N1—Zn1—O2 bond angle is 154.55 (8)°. The Zn1—N and Zn1—O bond lengths (Table 2) are close to those reported in other Zn^II coordination polymers, i.e. [Zn(adi)_0.5(imb)]_n [H₂adi = adipic acid; Zn—N = 2.008 (3)–2.040 (3) Å; Wang et al., 2014], {[Zn_1.5(btc)(bimt)(H₂O)₃].H₂O.DMF}_n {bimt = 2-[(benzoimidazolyl)methyl]-1H-tetra­zole and H₃btc = benzene-1,3,5-tri­carb­oxy­lic acid; Zn—O = 1.975 (3)–2.128 (3) Å; Liu et al., 2013}, [Zn(ox)(imb)] [H₂ox = oxalic acid; Zn—O = 2.552 (3) Å; Huang, Wang, Li & Meng, 2015] and [Zn₂(mal)₂(imb)₂] [H₂mal = malonic acid; Zn—O = 2.555 (5) Å; Huang, Wang, Li & Meng, 2015]. For each imb(A) ligand coordinating to the Zn1 ion, the dihedral angle between the benzimidazole and imidazole rings is ca 84.7°. The Zn2 ion is located in a regular tetra­hedral geometry and is coordinated by two N atoms from two symmetry-related imb ligands [denoted imb(B), pink colour in Fig. 1] and by two O atoms from two crystallographically distinct bdic^2- ligands. As shown in Table 2, the Zn2—O and Zn2—N bond lengths are close to the Zn1—O and Zn1—N bond lengths. The bond angles around the Zn2 ion range from 94.47 (8) to 124.26 (9)°. For each imb(B) ligand coordinating to the Zn2 ion, the dihedral angle between the benzimidazole and imidazole rings is ca 88.6°.

As shown in Fig. 2, the imb(A) ligands serve as double connectors through two N atoms from the benzimidazole and imidazole rings and bridge two Zn1 ions to afford binuclear [(Zn1)₂{imb(A)}₂] units, with a Zn1···Zn1ⁱ distance of 6.0997 (18) Å [symmetry code: (i) -x + 1, -y + 1, -z]. The imb(B) ligands also bridge two Zn2 ions in a similar way, resulting in binuclear [(Zn2)₂{imb(B)}₂] units, with a Zn2···Zn2^II distance of 6.3985 (18) Å [symmetry code: (ii) -x, -y + 1, -z + 1]. The above-mentioned binuclear units are further connected alternately by pairs of bridging bdic^2- ligands, with a Zn1···Zn2 distance of 5.8670 (15) Å, forming an infinite one-dimensional chain. For one bdic^2- ligand (light-orange colour), the dihedral angles between the mean planes defined by the benzene ring and the carboxyl­ate groups are ca 55.3 and 61.6°, respectively. For the other bdic^2- ligand (turquoise colour), the dihedral angles between the mean planes defined by the benzene ring and the carboxyl­ate groups are ca 7.3 and 69.1°, respectively. As shown in Fig. 3 and Table 3, the one-dimensional chains are further connected through N—H···O hydrogen bonds between the benzimidazole groups and carboxyl­ate groups, leading to a two-dimensional layered structure parallel to the ac plane.

In previous work, we have reported several complexes involving the imb ligand and aliphatic di­carboxyl­ates, including [Cd₂Cl₂(suc)(imb)₂(H₂O)]_n, {[Cd(glu)(imb)].H₂O}_n and {[Cd₂Cl₂(adi)(imb)₂].2H₂O}_n (H₂suc = succinic acid, H₂glu = glutaric acid and H₂adi = adipic acid; Zhang et al., 2014). We have also reported several complexes involving the imb ligand and aromatic polycarboxyl­ates, such as the imb-H₄btec-based complexes (H₄btec = benzene-1,2,4,5-tetra­carb­oxy­lic acid) {[Ni(btec)(Himb)₂(H₂O)₂].6H₂O}_n, {[Cd(btec)_0.5(imb)(H₂O)].1.5H₂O}_n, {[Zn(btec)_0.5(imb)].H₂O}_n and {[Co(btec)_0.5(imb)(H₂O)].1.5H₂O}_n (Yang et al., 2014; Huang, Li & Meng, 2014), the imb-H₃btc-based complexes (H₃btc = benzene-1,3,5-tri­carb­oxy­lic acid) {[Cd(imb)(Hbtc)(CH₃OH)].2H₂O.CH₃OH}_n and {[Zn(imb)(Hbtc)].DMF.5H₂O}_n (Huang, Tang, Liu, Su & Meng, 2014; Huang, Yang & Meng, 2015), the imb-H₂bdic-based complexes (1,3-H₂bdic = benzene-1,3-di­carb­oxy­lic acid) {[Cd(imb)(1,3-bdic)(H₂O)].CH₃OH}_n and {[Cu(imb)(1,3-bdic)].2H₂O}_n (Huang, Tang, Liu, Su & Meng, 2014; Yan et al., 2012), and the 1,4-H₂bdic-based complexes (1,4-H₂bdic = benzene-1,4-di­carb­oxy­lic acid) {[Co(imb)(1,4-bdic)(H₂O)₂].2H₂O}_n and {[Ni(imb)(1,4-bdic)(H₂O)₂].2H₂O}_n (Wang et al., 2013). The results from the structural analyses of these complexes indicate that the nature of the polycarboxyl­ate ligands or of the metal ions strongly influences the architectures of the complexes. Complexes involving the imb ligand and H₄btec (or H₃btc) usually display higher-dimensional structures, and complexes involving the imb ligand and 1,4-H₂bdic (or 1,2-H₂bdic) usually display lower-dimensional structures. We will continue our work on complexes based on the imb ligand and polycarboxyl­ates, and make a systematic investigation of how the metal ions and polycarboxyl­ates influence the structures and properties of the resulting complexes.

In addition, in the complexes involving the imb ligand and 1,3-H₂bdic (or 1,4-H₂bdic), each 1,3-bdic^2- (or 1,4-bdic^2-) ligand bridges two metal ions, forming one-dimensional ···M–bdic–M–bdic··· chains. If the imb ligand also coordinates to metal ions in a bridging mode, then a complex with a higher-dimensional structure will be obtained. When 1,2-H₂bdic is used as the ancillary ligand, it usually coordinates to metal ions in a cis conformation, forming a binuclear [M₂(bdic)₂] unit. If imb ligands also coordinate to the metal ion in a cis conformation, forming another binuclear [M₂(imb)₂] unit, then complexes with lower-dimensional structures will be obtained. This implies that a change in the positions of the carboxyl­ate groups in the benzene ring can lead to complexes with different structures.

The IR spectrum of polymer (I) shows an absorption band at 3439 cm^-1, which can be ascribed to the N—H stretching vibration (Wang et al., 2008). The position of the C═O absorption in free carb­oxy­lic acid occurs at ca 1760–1680 cm^-1. Upon complexation to a Zn^II centre, the characteristic bands of the carboxyl­ate groups appear in the range 1567–1630 cm^-1 for asymmetric stretching and in the range 1382–1407 cm^-1 for symmetric stretching (Nakamoto, 2009). The carboxyl­ate frequencies for the aforementioned stretches appear to be shifted to lower values compared with those of the free aromatic acid, indicating changes in the vibrational status upon coordination. The absorption band at 749 cm^-1 belongs to the characteristic bending vibration of the external plane of a 1,2-disubstituted phenyl ring (Huang, Wang, Li & Meng, 2015).

Thermogravimetric (TG) and differential scanning calorimetry (DSC) analyses of (I) were performed in air. As illustrated in Fig. 4, the TG curve shows that polymer (I) is stable up to 603 K. It then loses weight from 604 to 913 K, corresponding to decomposition of the 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole and benzene-1,2-di­carboxyl­ate ligands. This breakdown process corresponds with a large exothermic peak at 859 K in the DSC curve. Similar cases have been found in other coordination polymers. For example, there is a large exothermic peak at 821 K in the DSC curve of {[Cd(btec)_0.5(imb)(H₂O)].1.5H₂O}_n (Yang et al., 2014) and there is a big exothermic peak at 834 K in the DSC curve of [Zn(bmi)₂(bdc)]_n {bmi = 1-[(benzotriazol-1-yl)methyl]-1H-1,3-imidazole and H₂bdc = benzene-1,4-di­carb­oxy­lic acid; Zhang et al., 2015]. Finally, a plateau occurs from 914 to 1053 K. The residue equals 19.59%, which is attributed to ZnO (calculated 19.03%).

The solid-state photoluminescence of polymer (I) has been investigated at room temperature. As shown in Fig. 5, polymer (I) shows an emission band at 345 nm when excited at 269 nm. To understand the nature of the emission spectra, the luminescence properties of the free ligands were recorded under the same experimental conditions for comparison. The free imb ligand exhibits a photoluminescent peak with a maximum at 310 nm upon excitation at 268 nm, and H₂bdic displays an emission band at 340 nm when excited at 277 nm. Obviously, the emission observed in polymer (I) is neither MLCT (metal-to-ligand charge transfer) nor LMCT (ligand-to-metal charge transfer), since the Zn^II cations are difficult to oxidize or reduce due to the d¹⁰ configuration (Chen et al., 2009). The emission observed in polymer (I) likely originates from intra­ligand transitions of the imb and bdic^2- ligands. The N- and O-atom donors contribute simultaneously to the fluorescence emission of (I).

In summary, the reaction of Zn(NO₃)₂ with 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole (imb) and benzene-1,2-di­carb­oxy­lic acid (H₂bdic) affords polymer (I) under hydro­thermal conditions. The polymer displays a one-dimensional structure in which binuclear [(Zn1)₂{imb(A)}₂] and [(Zn2)₂{imb(B)}₂] units are connected by pairs of bridging bdic^2- ligands. The three-dimensional supra­molecular architecture is produced via hydrogen-bonding inter­actions and van der Waals forces. In addition, polymer (I) exhibits good fluorescence properties in the solid state at room temperature.

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: CrystalClear (Rigaku/MSC, 2004); data reduction: CrystalClear (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The coordination environment of the Zn^II cations in polymer (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x, -y + 1, -z + 1.]
	Fig. 2. A view of the one-dimensional structure of polymer (I). [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x, -y + 1, -z + 1.]
	Fig. 3. The two-dimensional structure of polymer (I), linked by hydrogen bonds (yellow dashed lines). Adjacent chains are shown in different colours.
	Fig. 4. TGA and DSC curves for polymer (I).
	Fig. 5. Solid-state emission spectra for free imb, H2bdic and polymer (I).

catena-Poly[zinc(II)-bis{µ-2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole}-κ²N³:N^3';N^3':N³-zinc(II)-bis(µ-benzene-1,2-dicarboxylato)-κ²O¹:O²;κ³O¹,O^1':O²]

Crystal data

[Zn2(C8H4O4)2(C11H10N4)2]	Z = 2
Mr = 855.42	F(000) = 872
Triclinic, P1	Dx = 1.617 Mg m^−3
a = 9.6810 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.257 (2) Å	Cell parameters from 4499 reflections
c = 18.424 (4) Å	θ = 2.1–27.9°
α = 99.16 (3)°	µ = 1.43 mm^−1
β = 101.87 (3)°	T = 293 K
γ = 94.06 (3)°	Prism, colourless
V = 1757.3 (7) Å^3	0.18 × 0.16 × 0.10 mm

Data collection

Rigaku Saturn diffractometer	8337 independent reflections
Radiation source: fine-focus sealed tube	6362 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm^-1	Rint = 0.032
ω scans	θmax = 27.9°, θmin = 2.1°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	h = −12→12
Tmin = 0.927, Tmax = 1.000	k = −13→13
22128 measured reflections	l = −24→24

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0371P)^2 + 0.1923P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
8337 reflections	Δρmax = 0.57 e Å^−3
505 parameters	Δρmin = −0.34 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Zn1	0.35365 (3)	0.60974 (3)	0.12478 (2)	0.03383 (10)
Zn2	0.20280 (3)	0.42388 (3)	0.38637 (2)	0.03099 (10)
N1	0.2307 (2)	0.6334 (2)	0.02273 (11)	0.0332 (5)
N2	0.0634 (2)	0.6077 (2)	−0.08221 (11)	0.0347 (5)
H2A	0.0006	0.5691	−0.1213	0.042*
N3	0.2404 (2)	0.3568 (2)	−0.09053 (11)	0.0314 (5)
N4	0.4411 (2)	0.3298 (2)	−0.12531 (11)	0.0338 (5)
N5	0.2894 (2)	0.4110 (2)	0.49663 (11)	0.0315 (5)
N6	0.4258 (2)	0.4407 (2)	0.61122 (11)	0.0369 (6)
H6B	0.4754	0.4811	0.6542	0.044*
N7	0.2149 (2)	0.6598 (2)	0.61116 (12)	0.0345 (5)
N8	0.0010 (2)	0.6509 (2)	0.63358 (11)	0.0347 (5)
O1	0.3658 (2)	0.4120 (2)	0.10441 (10)	0.0458 (5)
O2	0.4445 (2)	0.48108 (19)	0.22671 (10)	0.0393 (5)
O3	0.33445 (19)	0.31098 (19)	0.34417 (9)	0.0374 (5)
O4	0.17804 (19)	0.2888 (2)	0.23525 (10)	0.0445 (5)
O5	0.31391 (19)	0.74337 (18)	0.20549 (9)	0.0356 (4)
O6	0.1222 (2)	0.59911 (19)	0.17832 (10)	0.0415 (5)
O7	0.2143 (2)	0.5885 (2)	0.34391 (11)	0.0444 (5)
O8	0.0745 (3)	0.6418 (3)	0.42085 (13)	0.0879 (10)
C1	0.4175 (3)	0.3908 (3)	0.17055 (14)	0.0340 (6)
C2	0.4494 (3)	0.2539 (3)	0.18071 (13)	0.0300 (6)
C3	0.5405 (3)	0.1877 (3)	0.14333 (14)	0.0387 (7)
H3A	0.5716	0.2220	0.1050	0.046*
C4	0.5859 (3)	0.0697 (3)	0.16277 (17)	0.0480 (8)
H4A	0.6498	0.0266	0.1387	0.058*
C5	0.5359 (3)	0.0171 (3)	0.21779 (17)	0.0470 (8)
H5A	0.5663	−0.0616	0.2310	0.056*
C6	0.4412 (3)	0.0807 (3)	0.25344 (15)	0.0377 (7)
H6A	0.4064	0.0436	0.2899	0.045*
C7	0.3972 (3)	0.1993 (3)	0.23553 (13)	0.0285 (6)
C8	0.2927 (3)	0.2709 (3)	0.27323 (14)	0.0304 (6)
C9	0.1925 (3)	0.7043 (3)	0.21472 (13)	0.0294 (6)
C10	0.1251 (3)	0.8000 (3)	0.26420 (13)	0.0278 (6)
C11	0.0880 (3)	0.9138 (3)	0.23651 (16)	0.0397 (7)
H11A	0.1184	0.9322	0.1941	0.048*
C12	0.0078 (3)	0.9999 (3)	0.26986 (18)	0.0516 (8)
H12A	−0.0152	1.0759	0.2504	0.062*
C13	−0.0385 (4)	0.9732 (3)	0.33206 (18)	0.0519 (8)
H13A	−0.0963	1.0289	0.3538	0.062*
C14	0.0016 (3)	0.8629 (3)	0.36236 (16)	0.0441 (7)
H14A	−0.0273	0.8468	0.4055	0.053*
C15	0.0840 (3)	0.7759 (3)	0.32961 (14)	0.0328 (6)
C16	0.1269 (3)	0.6608 (3)	0.36751 (15)	0.0422 (7)
C17	0.3803 (3)	0.3510 (3)	−0.06756 (14)	0.0336 (6)
H17A	0.4279	0.3608	−0.0174	0.040*
C18	0.3343 (3)	0.3231 (3)	−0.18813 (15)	0.0383 (7)
H18A	0.3458	0.3088	−0.2376	0.046*
C19	0.2107 (3)	0.3402 (3)	−0.16744 (14)	0.0407 (7)
H19A	0.1226	0.3407	−0.1991	0.049*
C20	0.1427 (3)	0.3996 (3)	−0.04196 (14)	0.0343 (6)
H20A	0.1721	0.3730	0.0067	0.041*
H20B	0.0474	0.3576	−0.0649	0.041*
C21	0.1439 (3)	0.5463 (3)	−0.03180 (13)	0.0314 (6)
C22	0.0995 (3)	0.7433 (3)	−0.06015 (14)	0.0339 (6)
C23	0.0522 (3)	0.8509 (3)	−0.09138 (15)	0.0442 (7)
H23A	−0.0192	0.8405	−0.1348	0.053*
C24	0.1174 (3)	0.9743 (3)	−0.05417 (17)	0.0516 (8)
H24A	0.0900	1.0491	−0.0736	0.062*
C25	0.2229 (3)	0.9906 (3)	0.01139 (17)	0.0516 (8)
H25A	0.2640	1.0757	0.0345	0.062*
C26	0.2679 (3)	0.8834 (3)	0.04287 (16)	0.0453 (8)
H26A	0.3374	0.8945	0.0872	0.054*
C27	0.2052 (3)	0.7585 (3)	0.00576 (14)	0.0341 (6)
C28	0.0756 (3)	0.6503 (3)	0.58111 (15)	0.0354 (6)
H28A	0.0366	0.6441	0.5300	0.042*
C29	0.0987 (3)	0.6600 (3)	0.70022 (15)	0.0493 (8)
H29A	0.0774	0.6625	0.7474	0.059*
C30	0.2296 (3)	0.6646 (4)	0.68660 (16)	0.0562 (10)
H30A	0.3145	0.6702	0.7220	0.067*
C31	0.3296 (3)	0.6424 (3)	0.57011 (15)	0.0360 (6)
H31A	0.4163	0.6950	0.5992	0.043*
H31B	0.3041	0.6724	0.5222	0.043*
C32	0.3525 (3)	0.4988 (3)	0.55710 (14)	0.0307 (6)
C33	0.4080 (3)	0.3055 (3)	0.58610 (14)	0.0378 (7)
C34	0.4560 (4)	0.2002 (3)	0.61939 (17)	0.0541 (9)
H34A	0.5162	0.2134	0.6669	0.065*
C35	0.4095 (4)	0.0756 (4)	0.57835 (19)	0.0662 (11)
H35A	0.4387	0.0023	0.5988	0.079*
C36	0.3190 (4)	0.0549 (3)	0.50619 (18)	0.0644 (11)
H36A	0.2882	−0.0313	0.4806	0.077*
C37	0.2758 (3)	0.1601 (3)	0.47329 (16)	0.0492 (8)
H37A	0.2180	0.1468	0.4252	0.059*
C38	0.3209 (3)	0.2869 (3)	0.51379 (14)	0.0346 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02674 (17)	0.0483 (2)	0.02584 (17)	0.00777 (14)	0.00593 (12)	0.00311 (14)
Zn2	0.02874 (17)	0.0422 (2)	0.02450 (16)	0.00978 (14)	0.00708 (12)	0.00898 (14)
N1	0.0269 (12)	0.0483 (14)	0.0222 (11)	0.0039 (10)	0.0029 (9)	0.0027 (10)
N2	0.0275 (12)	0.0498 (15)	0.0222 (11)	0.0013 (11)	0.0003 (9)	0.0009 (10)
N3	0.0254 (11)	0.0414 (13)	0.0279 (11)	0.0050 (10)	0.0087 (9)	0.0038 (10)
N4	0.0234 (11)	0.0488 (14)	0.0303 (12)	0.0082 (10)	0.0079 (9)	0.0058 (11)
N5	0.0324 (12)	0.0384 (13)	0.0225 (11)	0.0060 (10)	0.0043 (9)	0.0029 (10)
N6	0.0328 (13)	0.0488 (15)	0.0235 (11)	0.0055 (11)	−0.0008 (9)	−0.0020 (11)
N7	0.0242 (11)	0.0450 (14)	0.0319 (12)	0.0049 (10)	0.0068 (9)	−0.0018 (10)
N8	0.0273 (12)	0.0511 (15)	0.0264 (11)	0.0102 (11)	0.0051 (9)	0.0074 (10)
O1	0.0487 (13)	0.0608 (14)	0.0285 (10)	0.0105 (11)	0.0014 (9)	0.0170 (10)
O2	0.0463 (12)	0.0396 (11)	0.0337 (10)	0.0058 (9)	0.0120 (9)	0.0070 (9)
O3	0.0356 (11)	0.0531 (13)	0.0254 (10)	0.0141 (9)	0.0094 (8)	0.0049 (9)
O4	0.0252 (10)	0.0666 (14)	0.0379 (11)	0.0096 (10)	0.0017 (8)	0.0030 (10)
O5	0.0321 (10)	0.0449 (12)	0.0324 (10)	0.0059 (9)	0.0134 (8)	0.0053 (9)
O6	0.0351 (11)	0.0414 (12)	0.0390 (11)	0.0044 (9)	−0.0011 (9)	−0.0073 (9)
O7	0.0429 (12)	0.0436 (12)	0.0498 (12)	0.0131 (10)	0.0091 (10)	0.0152 (10)
O8	0.163 (3)	0.0796 (18)	0.0559 (15)	0.0580 (19)	0.0674 (17)	0.0404 (14)
C1	0.0280 (14)	0.0474 (18)	0.0283 (14)	0.0038 (12)	0.0074 (11)	0.0102 (13)
C2	0.0284 (13)	0.0385 (16)	0.0206 (12)	0.0047 (12)	0.0031 (10)	0.0005 (11)
C3	0.0427 (17)	0.0478 (18)	0.0247 (14)	0.0010 (14)	0.0125 (12)	−0.0014 (13)
C4	0.0404 (17)	0.0485 (19)	0.0500 (18)	0.0108 (15)	0.0137 (14)	−0.0139 (15)
C5	0.0452 (18)	0.0358 (17)	0.059 (2)	0.0122 (14)	0.0105 (15)	0.0040 (15)
C6	0.0384 (16)	0.0384 (16)	0.0370 (15)	0.0041 (13)	0.0088 (13)	0.0082 (13)
C7	0.0259 (13)	0.0351 (15)	0.0226 (13)	0.0032 (11)	0.0035 (10)	0.0021 (11)
C8	0.0310 (14)	0.0334 (15)	0.0279 (14)	0.0014 (12)	0.0087 (11)	0.0068 (12)
C9	0.0314 (14)	0.0378 (16)	0.0196 (12)	0.0098 (12)	0.0023 (10)	0.0087 (11)
C10	0.0244 (13)	0.0332 (14)	0.0254 (13)	0.0039 (11)	0.0038 (10)	0.0063 (11)
C11	0.0430 (17)	0.0414 (17)	0.0430 (16)	0.0113 (14)	0.0174 (13)	0.0184 (14)
C12	0.063 (2)	0.0382 (18)	0.064 (2)	0.0221 (16)	0.0248 (18)	0.0196 (16)
C13	0.060 (2)	0.0394 (18)	0.064 (2)	0.0207 (16)	0.0285 (17)	0.0045 (16)
C14	0.056 (2)	0.0453 (18)	0.0362 (16)	0.0120 (15)	0.0206 (14)	0.0049 (14)
C15	0.0383 (15)	0.0328 (15)	0.0263 (13)	0.0059 (12)	0.0058 (11)	0.0028 (12)
C16	0.061 (2)	0.0411 (17)	0.0248 (15)	0.0077 (15)	0.0077 (14)	0.0067 (13)
C17	0.0290 (14)	0.0465 (17)	0.0274 (14)	0.0069 (12)	0.0075 (11)	0.0097 (12)
C18	0.0321 (15)	0.0536 (19)	0.0255 (14)	0.0013 (13)	0.0056 (11)	−0.0012 (13)
C19	0.0253 (14)	0.066 (2)	0.0261 (14)	0.0020 (14)	0.0017 (11)	0.0002 (14)
C20	0.0255 (13)	0.0493 (17)	0.0309 (14)	0.0047 (12)	0.0134 (11)	0.0062 (13)
C21	0.0236 (13)	0.0500 (17)	0.0212 (13)	0.0036 (12)	0.0100 (10)	0.0021 (12)
C22	0.0277 (14)	0.0471 (18)	0.0245 (13)	0.0012 (12)	0.0039 (11)	0.0026 (13)
C23	0.0398 (17)	0.058 (2)	0.0307 (15)	0.0079 (15)	−0.0003 (13)	0.0059 (15)
C24	0.055 (2)	0.051 (2)	0.0454 (18)	0.0050 (17)	0.0013 (15)	0.0117 (16)
C25	0.052 (2)	0.047 (2)	0.0458 (18)	−0.0010 (16)	−0.0023 (15)	0.0006 (15)
C26	0.0371 (17)	0.054 (2)	0.0362 (16)	0.0005 (15)	−0.0043 (13)	−0.0003 (15)
C27	0.0281 (14)	0.0483 (18)	0.0243 (13)	0.0045 (13)	0.0042 (11)	0.0039 (13)
C28	0.0261 (14)	0.0522 (18)	0.0288 (14)	0.0069 (13)	0.0056 (11)	0.0097 (13)
C29	0.0335 (16)	0.090 (3)	0.0223 (14)	0.0177 (16)	0.0034 (12)	0.0017 (15)
C30	0.0297 (16)	0.097 (3)	0.0307 (16)	0.0129 (17)	−0.0030 (13)	−0.0108 (16)
C31	0.0267 (14)	0.0416 (17)	0.0394 (15)	0.0030 (12)	0.0110 (12)	0.0016 (13)
C32	0.0227 (13)	0.0430 (16)	0.0265 (13)	0.0038 (12)	0.0080 (10)	0.0032 (12)
C33	0.0364 (16)	0.0477 (18)	0.0273 (14)	0.0080 (13)	0.0020 (12)	0.0058 (13)
C34	0.060 (2)	0.064 (2)	0.0346 (16)	0.0190 (18)	−0.0066 (15)	0.0146 (16)
C35	0.087 (3)	0.053 (2)	0.054 (2)	0.019 (2)	−0.006 (2)	0.0184 (18)
C36	0.093 (3)	0.042 (2)	0.049 (2)	0.0108 (19)	−0.0069 (19)	0.0071 (16)
C37	0.063 (2)	0.0459 (19)	0.0306 (15)	0.0096 (16)	−0.0050 (14)	0.0013 (14)
C38	0.0401 (16)	0.0390 (16)	0.0237 (13)	0.0085 (13)	0.0032 (11)	0.0057 (12)

Geometric parameters (Å, º)

Zn1—O5	1.9747 (19)	C6—C7	1.383 (4)
Zn1—O1	2.019 (2)	C6—H6A	0.9300
Zn1—N4^i	2.037 (2)	C7—C8	1.510 (3)
Zn1—N1	2.068 (2)	C9—C10	1.507 (3)
Zn1—O2	2.5134 (19)	C10—C11	1.387 (4)
Zn1—C1	2.593 (3)	C10—C15	1.397 (3)
Zn2—O3	1.9750 (18)	C11—C12	1.372 (4)
Zn2—O7	1.976 (2)	C11—H11A	0.9300
Zn2—N8^ii	2.003 (2)	C12—C13	1.372 (4)
Zn2—N5	2.061 (2)	C12—H12A	0.9300
N1—C21	1.332 (3)	C13—C14	1.385 (4)
N1—C27	1.395 (3)	C13—H13A	0.9300
N2—C21	1.350 (3)	C14—C15	1.387 (4)
N2—C22	1.384 (3)	C14—H14A	0.9300
N2—H2A	0.8600	C15—C16	1.505 (4)
N3—C17	1.341 (3)	C17—H17A	0.9300
N3—C19	1.367 (3)	C18—C19	1.343 (4)
N3—C20	1.473 (3)	C18—H18A	0.9300
N4—C17	1.315 (3)	C19—H19A	0.9300
N4—C18	1.373 (3)	C20—C21	1.485 (4)
N4—Zn1^i	2.037 (2)	C20—H20A	0.9700
N5—C32	1.322 (3)	C20—H20B	0.9700
N5—C38	1.398 (3)	C22—C23	1.387 (4)
N6—C32	1.346 (3)	C22—C27	1.397 (3)
N6—C33	1.377 (4)	C23—C24	1.379 (4)
N6—H6B	0.8600	C23—H23A	0.9300
N7—C28	1.338 (3)	C24—C25	1.390 (4)
N7—C30	1.360 (3)	C24—H24A	0.9300
N7—C31	1.472 (3)	C25—C26	1.380 (4)
N8—C28	1.320 (3)	C25—H25A	0.9300
N8—C29	1.373 (3)	C26—C27	1.384 (4)
N8—Zn2^ii	2.003 (2)	C26—H26A	0.9300
O1—C1	1.277 (3)	C28—H28A	0.9300
O2—C1	1.244 (3)	C29—C30	1.341 (4)
O3—C8	1.276 (3)	C29—H29A	0.9300
O4—C8	1.227 (3)	C30—H30A	0.9300
O5—C9	1.268 (3)	C31—C32	1.494 (4)
O6—C9	1.247 (3)	C31—H31A	0.9700
O7—C16	1.262 (3)	C31—H31B	0.9700
O8—C16	1.230 (3)	C33—C34	1.386 (4)
C1—C2	1.491 (4)	C33—C38	1.399 (3)
C2—C3	1.378 (3)	C34—C35	1.371 (5)
C2—C7	1.393 (3)	C34—H34A	0.9300
C3—C4	1.391 (4)	C35—C36	1.409 (4)
C3—H3A	0.9300	C35—H35A	0.9300
C4—C5	1.375 (4)	C36—C37	1.369 (4)
C4—H4A	0.9300	C36—H36A	0.9300
C5—C6	1.376 (4)	C37—C38	1.384 (4)
C5—H5A	0.9300	C37—H37A	0.9300
O5—Zn1—O1	137.79 (8)	C13—C12—H12A	120.2
O5—Zn1—N4^i	101.93 (9)	C11—C12—H12A	120.2
O1—Zn1—N4^i	97.76 (9)	C12—C13—C14	119.6 (3)
O5—Zn1—N1	108.78 (8)	C12—C13—H13A	120.2
O1—Zn1—N1	100.20 (9)	C14—C13—H13A	120.2
N4^i—Zn1—N1	107.38 (9)	C13—C14—C15	121.3 (3)
O5—Zn1—O2	86.46 (7)	C13—C14—H14A	119.3
O1—Zn1—O2	57.02 (7)	C15—C14—H14A	119.3
N4^i—Zn1—O2	88.42 (8)	C14—C15—C10	118.9 (2)
N1—Zn1—O2	154.55 (8)	C14—C15—C16	118.0 (2)
O5—Zn1—C1	112.48 (8)	C10—C15—C16	123.2 (2)
O1—Zn1—C1	28.89 (8)	O8—C16—O7	122.8 (3)
N4^i—Zn1—C1	93.20 (9)	O8—C16—C15	117.8 (3)
N1—Zn1—C1	128.34 (9)	O7—C16—C15	119.4 (3)
O2—Zn1—C1	28.13 (7)	N4—C17—N3	111.1 (2)
O3—Zn2—O7	105.78 (8)	N4—C17—H17A	124.5
O3—Zn2—N8^ii	117.31 (9)	N3—C17—H17A	124.5
O7—Zn2—N8^ii	109.02 (9)	C19—C18—N4	109.8 (2)
O3—Zn2—N5	94.47 (8)	C19—C18—H18A	125.1
O7—Zn2—N5	124.26 (9)	N4—C18—H18A	125.1
N8^ii—Zn2—N5	106.08 (9)	C18—C19—N3	106.2 (2)
C21—N1—C27	105.9 (2)	C18—C19—H19A	126.9
C21—N1—Zn1	131.1 (2)	N3—C19—H19A	126.9
C27—N1—Zn1	122.02 (17)	N3—C20—C21	109.3 (2)
C21—N2—C22	108.3 (2)	N3—C20—H20A	109.8
C21—N2—H2A	125.9	C21—C20—H20A	109.8
C22—N2—H2A	125.9	N3—C20—H20B	109.8
C17—N3—C19	107.3 (2)	C21—C20—H20B	109.8
C17—N3—C20	126.0 (2)	H20A—C20—H20B	108.3
C19—N3—C20	125.6 (2)	N1—C21—N2	111.5 (2)
C17—N4—C18	105.6 (2)	N1—C21—C20	125.5 (2)
C17—N4—Zn1^i	125.86 (18)	N2—C21—C20	122.7 (2)
C18—N4—Zn1^i	121.56 (18)	N2—C22—C23	132.5 (2)
C32—N5—C38	105.7 (2)	N2—C22—C27	105.3 (2)
C32—N5—Zn2	134.00 (19)	C23—C22—C27	122.2 (3)
C38—N5—Zn2	118.63 (16)	C24—C23—C22	116.0 (3)
C32—N6—C33	108.4 (2)	C24—C23—H23A	122.0
C32—N6—H6B	125.8	C22—C23—H23A	122.0
C33—N6—H6B	125.8	C23—C24—C25	122.3 (3)
C28—N7—C30	107.0 (2)	C23—C24—H24A	118.9
C28—N7—C31	126.8 (2)	C25—C24—H24A	118.9
C30—N7—C31	125.2 (2)	C26—C25—C24	121.5 (3)
C28—N8—C29	105.6 (2)	C26—C25—H25A	119.3
C28—N8—Zn2^ii	124.12 (18)	C24—C25—H25A	119.3
C29—N8—Zn2^ii	125.57 (19)	C25—C26—C27	117.2 (3)
C1—O1—Zn1	101.33 (18)	C25—C26—H26A	121.4
C1—O2—Zn1	79.49 (15)	C27—C26—H26A	121.4
C8—O3—Zn2	112.55 (17)	C26—C27—N1	130.2 (2)
C9—O5—Zn1	105.99 (17)	C26—C27—C22	120.8 (3)
C16—O7—Zn2	107.33 (19)	N1—C27—C22	109.0 (2)
O2—C1—O1	122.2 (3)	N8—C28—N7	111.1 (2)
O2—C1—C2	118.8 (2)	N8—C28—H28A	124.5
O1—C1—C2	119.1 (2)	N7—C28—H28A	124.5
O2—C1—Zn1	72.38 (15)	C30—C29—N8	109.3 (2)
O1—C1—Zn1	49.79 (14)	C30—C29—H29A	125.4
C2—C1—Zn1	168.69 (18)	N8—C29—H29A	125.4
C3—C2—C7	119.9 (3)	C29—C30—N7	107.0 (2)
C3—C2—C1	121.5 (2)	C29—C30—H30A	126.5
C7—C2—C1	118.2 (2)	N7—C30—H30A	126.5
C2—C3—C4	120.2 (3)	N7—C31—C32	108.9 (2)
C2—C3—H3A	119.9	N7—C31—H31A	109.9
C4—C3—H3A	119.9	C32—C31—H31A	109.9
C5—C4—C3	119.7 (3)	N7—C31—H31B	109.9
C5—C4—H4A	120.1	C32—C31—H31B	109.9
C3—C4—H4A	120.1	H31A—C31—H31B	108.3
C4—C5—C6	120.2 (3)	N5—C32—N6	111.9 (2)
C4—C5—H5A	119.9	N5—C32—C31	125.0 (2)
C6—C5—H5A	119.9	N6—C32—C31	122.5 (2)
C5—C6—C7	120.6 (3)	N6—C33—C34	132.4 (3)
C5—C6—H6A	119.7	N6—C33—C38	105.2 (2)
C7—C6—H6A	119.7	C34—C33—C38	122.4 (3)
C6—C7—C2	119.4 (2)	C35—C34—C33	116.2 (3)
C6—C7—C8	121.8 (2)	C35—C34—H34A	121.9
C2—C7—C8	118.8 (2)	C33—C34—H34A	121.9
O4—C8—O3	124.9 (2)	C34—C35—C36	122.2 (3)
O4—C8—C7	119.7 (2)	C34—C35—H35A	118.9
O3—C8—C7	115.3 (2)	C36—C35—H35A	118.9
O6—C9—O5	122.8 (2)	C37—C36—C35	120.8 (3)
O6—C9—C10	119.7 (2)	C37—C36—H36A	119.6
O5—C9—C10	117.0 (2)	C35—C36—H36A	119.6
C11—C10—C15	118.7 (2)	C36—C37—C38	118.0 (3)
C11—C10—C9	115.6 (2)	C36—C37—H37A	121.0
C15—C10—C9	125.3 (2)	C38—C37—H37A	121.0
C12—C11—C10	121.9 (3)	C37—C38—N5	130.8 (2)
C12—C11—H11A	119.1	C37—C38—C33	120.3 (3)
C10—C11—H11A	119.1	N5—C38—C33	108.8 (2)
C13—C12—C11	119.5 (3)
Zn1—O2—C1—O1	−0.8 (2)	C27—N1—C21—N2	−0.6 (3)
Zn1—O2—C1—C2	177.9 (2)	Zn1—N1—C21—N2	168.03 (16)
Zn1—O1—C1—O2	1.0 (3)	C27—N1—C21—C20	173.6 (2)
Zn1—O1—C1—C2	−177.70 (19)	Zn1—N1—C21—C20	−17.7 (4)
O2—C1—C2—C3	−121.1 (3)	C22—N2—C21—N1	0.4 (3)
O1—C1—C2—C3	57.6 (4)	C22—N2—C21—C20	−174.1 (2)
Zn1—C1—C2—C3	48.6 (11)	N3—C20—C21—N1	−89.8 (3)
O2—C1—C2—C7	51.8 (3)	N3—C20—C21—N2	83.8 (3)
O1—C1—C2—C7	−129.4 (3)	C21—N2—C22—C23	179.0 (3)
Zn1—C1—C2—C7	−138.4 (9)	C21—N2—C22—C27	0.0 (3)
C7—C2—C3—C4	−3.1 (4)	N2—C22—C23—C24	−177.8 (3)
C1—C2—C3—C4	169.7 (2)	C27—C22—C23—C24	1.0 (4)
C2—C3—C4—C5	2.1 (4)	C22—C23—C24—C25	−0.9 (5)
C3—C4—C5—C6	0.1 (4)	C23—C24—C25—C26	−0.1 (5)
C4—C5—C6—C7	−1.3 (4)	C24—C25—C26—C27	1.0 (5)
C5—C6—C7—C2	0.2 (4)	C25—C26—C27—N1	178.3 (3)
C5—C6—C7—C8	179.6 (3)	C25—C26—C27—C22	−0.9 (4)
C3—C2—C7—C6	2.0 (4)	C21—N1—C27—C26	−178.7 (3)
C1—C2—C7—C6	−171.1 (2)	Zn1—N1—C27—C26	11.4 (4)
C3—C2—C7—C8	−177.4 (2)	C21—N1—C27—C22	0.6 (3)
C1—C2—C7—C8	9.5 (3)	Zn1—N1—C27—C22	−169.30 (17)
Zn2—O3—C8—O4	−6.3 (3)	N2—C22—C27—C26	179.0 (3)
Zn2—O3—C8—C7	172.31 (17)	C23—C22—C27—C26	−0.1 (4)
C6—C7—C8—O4	−118.3 (3)	N2—C22—C27—N1	−0.4 (3)
C2—C7—C8—O4	61.1 (3)	C23—C22—C27—N1	−179.5 (2)
C6—C7—C8—O3	63.1 (3)	C29—N8—C28—N7	−0.6 (3)
C2—C7—C8—O3	−117.6 (3)	Zn2^ii—N8—C28—N7	−157.29 (18)
Zn1—O5—C9—O6	1.5 (3)	C30—N7—C28—N8	0.9 (4)
Zn1—O5—C9—C10	−170.02 (16)	C31—N7—C28—N8	170.2 (2)
O6—C9—C10—C11	−105.3 (3)	C28—N8—C29—C30	0.0 (4)
O5—C9—C10—C11	66.5 (3)	Zn2^ii—N8—C29—C30	156.3 (2)
O6—C9—C10—C15	67.1 (3)	N8—C29—C30—N7	0.6 (4)
O5—C9—C10—C15	−121.1 (3)	C28—N7—C30—C29	−0.9 (4)
C15—C10—C11—C12	−2.6 (4)	C31—N7—C30—C29	−170.4 (3)
C9—C10—C11—C12	170.4 (3)	C28—N7—C31—C32	−88.1 (3)
C10—C11—C12—C13	−0.5 (5)	C30—N7—C31—C32	79.3 (3)
C11—C12—C13—C14	2.8 (5)	C38—N5—C32—N6	1.8 (3)
C12—C13—C14—C15	−2.2 (5)	Zn2—N5—C32—N6	−162.81 (18)
C13—C14—C15—C10	−0.9 (4)	C38—N5—C32—C31	−169.5 (2)
C13—C14—C15—C16	178.0 (3)	Zn2—N5—C32—C31	26.0 (4)
C11—C10—C15—C14	3.2 (4)	C33—N6—C32—N5	−1.4 (3)
C9—C10—C15—C14	−169.1 (3)	C33—N6—C32—C31	170.1 (2)
C11—C10—C15—C16	−175.7 (3)	N7—C31—C32—N5	91.7 (3)
C9—C10—C15—C16	12.1 (4)	N7—C31—C32—N6	−78.7 (3)
Zn2—O7—C16—O8	15.9 (4)	C32—N6—C33—C34	−178.0 (3)
Zn2—O7—C16—C15	−164.4 (2)	C32—N6—C33—C38	0.4 (3)
C14—C15—C16—O8	7.5 (4)	N6—C33—C34—C35	176.2 (3)
C10—C15—C16—O8	−173.6 (3)	C38—C33—C34—C35	−2.0 (5)
C14—C15—C16—O7	−172.3 (3)	C33—C34—C35—C36	0.4 (6)
C10—C15—C16—O7	6.6 (4)	C34—C35—C36—C37	1.4 (6)
C18—N4—C17—N3	0.6 (3)	C35—C36—C37—C38	−1.6 (6)
Zn1^i—N4—C17—N3	151.38 (19)	C36—C37—C38—N5	−176.7 (3)
C19—N3—C17—N4	−1.0 (3)	C36—C37—C38—C33	0.1 (5)
C20—N3—C17—N4	−169.8 (2)	C32—N5—C38—C37	175.6 (3)
C17—N4—C18—C19	−0.1 (3)	Zn2—N5—C38—C37	−17.0 (4)
Zn1^i—N4—C18—C19	−152.4 (2)	C32—N5—C38—C33	−1.4 (3)
N4—C18—C19—N3	−0.5 (3)	Zn2—N5—C38—C33	165.96 (18)
C17—N3—C19—C18	0.9 (3)	N6—C33—C38—C37	−176.8 (3)
C20—N3—C19—C18	169.8 (3)	C34—C33—C38—C37	1.8 (5)
C17—N3—C20—C21	86.4 (3)	N6—C33—C38—N5	0.6 (3)
C19—N3—C20—C21	−80.5 (3)	C34—C33—C38—N5	179.2 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O6^iii	0.86	2.03	2.796 (3)	148
N6—H6B···O2^iv	0.86	2.13	2.947 (3)	158

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