An acyl­amide metal–organic framework with an unprecedented four-connecting trinodal topology and amide oxygen coordination

The three-dimensional Zn^II coordination polymer poly[[bis­(μ₂-benzene-1,4-di­carboxyl­ato){μ₄-N¹,N³,N⁵-tris­[(pyridin-3-yl)meth­yl]benzene-1,3,5-tricarboxamide}­dizinc(II)] mono­hy­drate], {[Zn₂(C₈H₄O₄)₂(C₂₇H₂₄N₆O₃)]·H₂O}_n, is characterized by a rare (4,4,4)-connected (4.6².7².8)(4.6².7³)(4².6².7²) topology. The tricarboxamide ligand adopts an un­precedented tetra­dentate coordination mode, with one carboxamide O atom participating in the coordination. The polymer was further characterized by thermogravimetric and solid-state luminescence analysis.

S1. Introduction

The construction of metal–organic frameworks (MOFs) is of current inter­est in the field of supra­molecular chemistry and crystal engineering, and considerable attention has been paid to these compounds due to their potential applications in magnetism, separation, catalysis and ion-exchange, as well as the intriguing variety of their architectures and fascinating new topologies (Suksai et al., 2008; Abdul-Kadir et al., 2011; Wang et al., 2010; Hasegawa et al., 2007; Bae et al., 2009; Long et al., 2009; Gagnon et al., 2011). Currently, the most common approach to building coordination frameworks (MOFs) is a rational combination of a suitable organic ligand and a transition metal with a specific coordination geometry. The organic ligand is significant because changing its structure can lead, for instance, to various inter­esting porous MOFs (Tsai et al., 2010). Therefore, an elaborative design or choice of ligand with appropriate groups is the key for the construction of functional coordination compounds with desired structural and physicochemical properties (Liao et al., 2011).

Among the organic bridging blocks, much attention has been devoted to the use of three-connected centres as basic structural units for the construction of framework materials. Particularly, tripodal ligands such as 1,3,5-tris­[(imidazol-1-yl)methyl]-2,4,6-tri­methyl­benzene, 2,4,6-tri­ethyl-1,3,5-tris­[(pyrazol-1-yl)methyl]­benzene, 1,3,5-tris­[(pyridin-4-yl)methyl]­benzene, 1,3,5-tris­[(imidazol-1-yl)methyl]­benzene etc (Bai et al., 2013; Luo et al., 2012; Wang et al., 2011; Wu et al., 2013), have been broadly used in the construction of MOFs. In this context, the tripodal ligand,N¹,N³,N⁵-tris­[(pyridin-3-yl)methyl]­benzene-1,3,5-tricarboxamide (L) has a remarkable coordinating ability and various coordination modes due to the coordination potential arising from the three pyridine N atoms plus the three carbonyl O atoms (Liao et al., 2010; Gong et al., 2011). In compounds containing L as a ligand, it is common for the pyridine N atoms to participate in the coordination. However, in some reports, the carboxamide O atom coordinates to a metal centre, in various ways (Cheng et al., 2013; Jiao et al., 2012; Zhang et al., 2013; Ma et al., 2011; Cheng et al., 2013; Bai et al., 2013). The results presented here show that not only can the pyridine N atoms participate in coordination but that the carboxamide O atoms can also coordinate. We report a new polymeric framework, namely [Zn₂(BDC)₂(L)]_n (BDC^2- is benzene-1,4-di­carboxyl­ate), (1), in which the L ligand coordinates through a carboxamide O atom. (1) is characterized by an unprecedented trinodal (4,4,4)-connected (4.6².7².8) (4.6²6.7³) (4².6².7²) topology (Blatov & Proserpio, 2008).

S2. Experimental

S2.1. Synthesis and crystallization

Zn(NO₃)₂ (0.2 mmol, 59.50 mg), benzene-1,4-di­carb­oxy­lic acid (H₂BDC; 0.2 mmol, 33.20 mg) and L (0.1 mmol, 43.80 mg) were sealed in a Teflon reactor with di­methyl­formamide (DMF, 4 ml) and H₂O (4 ml), and heated at 388 K for 2 d, followed by cooling to room temperature at a rate of 3 K h^-1. Subsequently, block-shaped colourless crystals of (1) were obtained in 78% yield based on Zn(NO₃)₂.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The C40—O8 group in one of the centrosymmetric terephthalate ligands is disordered over two positions, which were refined using similar-distance and planarity restraints for the disordered atoms and their directly bonded atoms (SADI and FLAT instructions in SHELXL2014; Sheldrick, 2008). The occupation factor of the major orientation of the disordered group refined to 0.507 (2). The Zn complex leaves one centrosymmetric cavity per unit cell of 92 ų and four small but significant peaks of residual electron density remained within the cavity. The SQUEEZE routine of the program PLATON (Spek, 2009) suggested that there were 22 electrons per cavity, or 11 per asymmetric unit. This is consistent with there being one water molecule per asymmetric unit and per formula unit of the Zn complex. The model development was continued using the original reflection data and assigning the four residual electron-density peaks as partially occupied O atoms of a disordered water molecule. These sites were then refined while restraining their occupancies to sum to a total of 1.0. The sum of the occupancies of atom O8A and the two nearest water sites were also restrained to sum to 1.0, to avoid them being simultaneously present in the same asymmetric unit because of impossibly short O8A···O(water) contacts. Pseudo-isotropic restraints were also applied to the anisotropic displacement parameters of the disordered sites of the water molecule and the water H atoms were not included in the model. H atoms bonded to C atoms were placed in calculated positions, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic, and C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methyl­ene groups. H atoms bonded to N atoms were found in difference maps and refined with N—H bond-length restraints of 0.86 (1) Å and with U_iso(H) = 1.2U_eq(N).

S3. Results and discussion

As shown in Fig. 1, the asymmetric unit of (1) consists of two unique Zn^II ions and one L ligand in general positions, and four centrosymmetric BDC^2- ligands. The Zn1 ion presents a distorted o­cta­hedral environment with two chelating BDC^2- ligands, each providng one of the shortest and one of the longest Zn—O bonds in the polyhedron, completed by two pyridine N atoms of two L ligands. The Zn2 ion shows a clear four-coordinated tetra­hedral geometry, defined by two carboxyl­ate O atoms from two BDC^2- ligands, one pyridine N atom from an L ligand and one carboxamide O atom from one L ligand.

The Zn—N coordination distances range from 2.042 (3) to 2.097 (2) Å and the Zn—O coordination distances range from 1.988 (2) to 2.011 (2) Å, with two semicoordinated outlyers [2.444 (2) and 2.565 (2) Å; Table 2]. The L ligand adopts a tetra­dentate coordination mode with one carboxamide O atom participating in the coordination (Fig. 2). To the best of our knowledge, the L ligand is usually tripodal and its coordination via a carboxamide O atom as in (1) is rather unusual (Fig. 2).

A search of the Cambridge Structural Database (Version 5.35, February 2014 update; Allen, 2002) reveals three L-containing complexes involving different metal atoms, viz. Cu (Tzeng et al., 2008), Ag (Fan et al., 2003) and Pb (Shahverdizadeh et al. 2012). In none of these compounds does the L ligand link to the metal centre in the tetra­dentate binding mode seen in (1).

As shown in Figs. 3(a) and 3(b), each L ligand in (1) coordinates to two Zn1 ions and two Zn2 ions, creating a 32-membered (Zn1)₂L₂ ring and a 16-membered (Zn2)₂L₂ ring. Furthermore, by sharing the L ligand, the (Zn1)₂L₂ and (Zn2)₂L₂ rings are connected forming a one-dimensional chain (Fig. 3c). Each one-dimensional chain is in turn connected to six identical one-dimensional chains by BDC^2- ligands.

The benzene rings in the L ligand (ring 1 is C14–C17/C19/C20) and the BDC^2- groups [ring 2 is C5–C7/C5ⁱ–C7ⁱ and ring 3 is C37–C39/C37ⁱⁱ–C39ⁱⁱ; symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x, -y+1, -z+2] are almost parallel [the dihedral angle between the planes of rings 1 and 2 is 0.53 (13)°, and that between the planes of rings 1 and 3 is 0.86 (13)°], with rather short inter­centroid distances [3.853 (2) Å between the centroids of rings 1 and 2, and 3.797 (2) Å between the centroids of rings 1 and 3] suggesting weak π–π inter­actions between the rings (Fig. 4), which can futher stabilize the structure. In addition, there are a number of C—H···π and C—H···O hydrogen-bonding inter­actions (Table 3).

Further insight into the structural properties of (1) can be achieved by topology methods which consist in reducing the multidimensional structure to a simple node-and-linker net. According to these principles, the L ligand is regarded as a 4-connecting node (see Fig. S1c), while the Zn1 ion connects two Zn1 ions and the Zn2 ion links two Zn2 ions though two BDC^2- ligands and two L ligands. The BDC^2- ligands serve as linear linkers and Zn1 and Zn2 serve as two different 4-connecting nodes, showing four connectivity in tetra­hedral geometries (see Figs. S1a and S1b). A topology analysis performed with TOPOS (Blatov & Proserpio, 2008) gave (4.6².7².8)(4.6².7³)(4².6².7²) as the topology symbol, corresponding to a (4,4,4)-connected net (Fig. 5).

There are many (4,4)-connected networks reported in the literature, for example, the distorted non-inter­penetrating coordination polymer [Cu(dps)₂]PF₆ with a (4,4) topology (dps is ????; Ni et al., 2001), the characteristic grid structure of a (4,4) net topology in {[Co(L⁴)₂(H₂O)₂](BF₄)₂.4DMF}_n {L⁴ = 3,5-bis­[4-(imidazol-1-yl)phenyl]-1,2,4-triazol-4-amine; Aijaz, et al., 2010} and [Zn(L⁵)₂(ClO₄)₂] with a (4,4) network [L⁵ = N,N'-bis­(pyridin-4-yl)urea; Kumar et al., 2005], among many examples. However, the connecting mode of compound (1) appears to be comparatively unusual.

Thermogravimetric analysis (TGA) of (1) was carried out under a nitro­gen atmosphere in the temperature range 308–1073 K at a heating rate of 10 K min^-1. As shown in Fig. 6(a), compound (1) is stable to over 743 K, but displays a sharp weight loss from approximately 873 K, indicating decomposition. In addition, the solid-state photoluminescence properties were measured. As shown in Fig. 6(b), an intense emission occurs at 400 nm with the excitation wavelength at 320 nm. Comparatively, the free L ligand shows emission at 428 nm upon excitation at 300–350 nm at room temperature (Tzeng et al., 2008) and free benzene-1,4-di­carb­oxy­lic acid shows an emission at 369 nm with excitation at 331 nm (Guo et al., 2012). Accordingly, the emission in (1) is most likely to originate from the L ligand through a π–π transition, given the significant blue shift (28 nm) on going from L to (1) (Guo et al., 2012).

In summary, the results herein discussed confirm the L ligand to be an excellent polydentate ligand suitable for the construction of coordination polymers with diverse structures.

Related literature

For related literature, see: Abdul-Kadir, Hanton, Sumby & Dastidar (2011); Aijaz et al. (2010); Allen (2002); Bae et al. (2009); Bai et al. (2013); Blatov & Proserpio (2008); Cheng et al. (2013); Fan et al. (2003); Gagnon et al. (2011); Gong et al. (2011); Guo et al. (2012); Hasegawa et al. (2007); Jiao et al. (2012); Kumar et al. (2005); Liao et al. (2010, 2011); Long & Yaghi (2009); Luo et al. (2012); Ma et al. (2011); Ni & Vittal (2001); Shahverdizadeh et al. (2012); Suksai et al. (2008); Tsai et al. (2010); Tzeng et al. (2008); Wang et al. (2010, 2011); Wu et al. (2013); Zhang et al. (2013).

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (1), with displacement ellipsoids drawn at the 30% probability level. Only one of the two disordered C40–O8 groups (unit A) has been shown for clarity. Colour key: Zn light blue, C green, N blue, O red and H pink. [Symmetry codes: (#1) -x+2, -y+2, -z; (#2) -x+3, -y+1, -z+1; (#3) -x+2, -y+1, -z+1; (#4) -x+1, -y+1, -z+2; (#5) -x, -y+1, -z+2; (#6) -x+1, -y+2, -z+1.]
	Fig. 2. The L ligand adopts a tetradentate coordinated mode with one carbonyl O atom participating in the coordination.
	Fig. 3. (a) The 32-membered (Zn1)2L2 ring, (b) the 16-membered (Zn2)2L2 ring and (c) a view of a one-dimensional chain formed by Zn^II ions and L ligands. Generic atom labels without symmetry codes have been used. The green ring is (Zn1)2L2 and the red ring is (Zn2)2L2.
	Fig. 4. A view of π–π interactions between benzene rings of BDC^2- and L ligands. Black dotted line denote π–π interactions. Colour code: Zn light blue, C green, N blue, O red and H pink.
	Fig. 5. Schematic description of the (4,4,4)-connected net with (4.6^2.7^2.8)(4.6^2.7^3)(4^2.6^2.7^2) topology.
	Fig. 6. (a) The TG curve and (b) the solid-state photoluminescence spectrum of compound (1).

Poly[[bis(µ₂-benzene-1,4-dicarboxylato){µ₄-N¹,N³,N⁵-tris[(pyridin-3-yl)methyl]benzene-1,3,5-tricarboxamide}dizinc(II)] 0.22-hydrate]

Crystal data

[Zn2(C8H4O4)2(C27H24N6O3)]·H2O	Z = 2
Mr = 957.50	F(000) = 980
Triclinic, P1	Dx = 1.570 Mg m^−3
a = 10.6904 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.9661 (6) Å	Cell parameters from 8310 reflections
c = 15.2652 (6) Å	θ = 2.3–25.1°
α = 69.182 (2)°	µ = 1.26 mm^−1
β = 72.346 (2)°	T = 296 K
γ = 80.313 (2)°	Block, colorless
V = 2025.33 (14) Å^3	0.20 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	7130 independent reflections
Radiation source: fine-focus sealed tube	5724 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
phi and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −12→12
Tmin = 0.76, Tmax = 0.84	k = −16→16
29300 measured reflections	l = −18→18

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)] = 0.034	Hydrogen site location: mixed
wR(F^2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0449P)^2 + 1.2809P] where P = (Fo^2 + 2Fc^2)/3
7130 reflections	(Δ/σ)max = 0.001
627 parameters	Δρmax = 0.58 e Å^−3
40 restraints	Δρmin = −0.40 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	Occ. (<1)
Zn1	1.21845 (3)	0.86478 (2)	0.30589 (2)	0.03314 (11)
Zn2	0.48414 (3)	0.65771 (3)	0.82277 (2)	0.03682 (11)
C1	1.1352 (3)	0.9086 (2)	0.1523 (2)	0.0384 (7)
C2	1.0659 (3)	0.9565 (2)	0.0725 (2)	0.0330 (6)
C3	1.0602 (3)	0.9017 (2)	0.0144 (2)	0.0361 (7)
H3	1.1004	0.8357	0.0237	0.043*
C4	1.0054 (3)	1.0553 (2)	0.0580 (2)	0.0362 (7)
H4	1.0090	1.0926	0.0969	0.043*
C5	1.0459 (3)	0.5977 (2)	0.4575 (2)	0.0377 (7)
C6	0.9123 (3)	0.5853 (2)	0.4961 (2)	0.0438 (8)
H6	0.8533	0.6427	0.4941	0.053*
C7	1.1338 (3)	0.5118 (2)	0.4624 (2)	0.0425 (7)
H7	1.2238	0.5197	0.4378	0.051*
C8	1.1718 (3)	1.0331 (2)	0.3899 (2)	0.0429 (8)
H8	1.1720	1.0735	0.3266	0.051*
C9	1.1498 (3)	1.0797 (3)	0.4592 (3)	0.0473 (8)
H9	1.1355	1.1507	0.4428	0.057*
C10	1.1492 (3)	1.0207 (3)	0.5528 (3)	0.0465 (8)
H10	1.1330	1.0515	0.6005	0.056*
C11	1.1729 (3)	0.9153 (2)	0.5761 (2)	0.0392 (7)
C12	1.1937 (3)	0.8742 (2)	0.5028 (2)	0.0370 (7)
H12	1.2090	0.8034	0.5176	0.044*
C13	1.0293 (3)	0.7137 (2)	0.7324 (2)	0.0398 (7)
C14	1.0083 (3)	0.6059 (2)	0.7440 (2)	0.0350 (7)
C15	1.1063 (3)	0.5290 (2)	0.7355 (2)	0.0403 (7)
H15	1.1935	0.5421	0.7233	0.048*
C16	1.0760 (3)	0.4320 (2)	0.7450 (2)	0.0370 (7)
C17	0.9465 (3)	0.4121 (2)	0.7648 (2)	0.0341 (6)
H17	0.9257	0.3468	0.7732	0.041*
C18	1.1745 (4)	0.8489 (3)	0.6789 (2)	0.0520 (9)
H18A	1.2590	0.8522	0.6887	0.062*
H18B	1.1073	0.8768	0.7241	0.062*
C19	0.8470 (3)	0.4891 (2)	0.77210 (19)	0.0318 (6)
C20	0.8792 (3)	0.5849 (2)	0.7618 (2)	0.0357 (7)
H20	0.8127	0.6365	0.7669	0.043*
C21	0.7058 (3)	0.4764 (2)	0.7873 (2)	0.0333 (6)
C22	0.5350 (3)	0.3667 (3)	0.8114 (2)	0.0401 (7)
H22A	0.5324	0.3210	0.7768	0.048*
H22B	0.4861	0.4306	0.7859	0.048*
C23	0.5293 (3)	0.6810 (2)	1.0826 (2)	0.0342 (7)
C24	0.6286 (3)	0.7472 (2)	1.0506 (3)	0.0441 (8)
H24	0.6556	0.7651	1.0948	0.053*
C25	0.6873 (3)	0.7863 (3)	0.9519 (3)	0.0500 (9)
H25	0.7544	0.8308	0.9292	0.060*
C26	0.6458 (3)	0.7591 (2)	0.8881 (3)	0.0462 (8)
H26	0.6852	0.7861	0.8219	0.055*
C27	0.4949 (3)	0.6571 (2)	1.0133 (2)	0.0386 (7)
H27	0.4291	0.6120	1.0340	0.046*
C28	1.1895 (3)	0.3554 (3)	0.7282 (2)	0.0451 (8)
C29	1.2734 (3)	0.2086 (3)	0.6761 (3)	0.0608 (11)
H29A	1.3263	0.2544	0.6172	0.073*
H29B	1.2380	0.1613	0.6576	0.073*
C30	1.6383 (3)	0.8522 (3)	0.2585 (3)	0.0431 (8)
C31	1.6789 (3)	0.9307 (3)	0.1747 (3)	0.0579 (10)
H31	1.7665	0.9468	0.1527	0.070*
C32	1.5909 (4)	0.9865 (3)	0.1223 (3)	0.0656 (11)
H32	1.6179	1.0398	0.0646	0.079*
C33	1.4621 (3)	0.9611 (3)	0.1576 (2)	0.0483 (8)
H33	1.4020	0.9987	0.1229	0.058*
C34	1.5080 (3)	0.8309 (2)	0.2880 (2)	0.0349 (7)
H34	1.4800	0.7762	0.3442	0.042*
C35	1.0935 (3)	0.7037 (3)	0.4059 (2)	0.0428 (8)
C36	0.2303 (3)	0.6187 (3)	0.9189 (2)	0.0411 (7)
C37	0.1114 (3)	0.5570 (2)	0.9612 (2)	0.0354 (7)
C38	0.1206 (3)	0.4562 (2)	0.9646 (2)	0.0450 (8)
H38	0.2020	0.4256	0.9407	0.054*
C39	−0.0102 (3)	0.6006 (3)	0.9969 (2)	0.0452 (8)
H39	−0.0185	0.6686	0.9953	0.054*
C41	0.5084 (3)	0.9023 (2)	0.5665 (2)	0.0397 (7)
C42	0.5045 (3)	0.9870 (2)	0.5929 (2)	0.0404 (7)
H42	0.5071	0.9791	0.6555	0.048*
C43	0.5034 (3)	0.9164 (2)	0.4730 (2)	0.0458 (8)
H43	0.5053	0.8594	0.4545	0.055*
N1	1.1930 (2)	0.93073 (19)	0.41118 (18)	0.0357 (6)
N2	1.1523 (3)	0.7428 (2)	0.7009 (2)	0.0444 (6)
H2M	1.216 (2)	0.699 (2)	0.691 (2)	0.053*
N3	0.6709 (2)	0.3869 (2)	0.79423 (19)	0.0377 (6)
H3M	0.728 (2)	0.3358 (17)	0.797 (2)	0.045*
N4	0.5505 (2)	0.69495 (19)	0.91799 (18)	0.0405 (6)
N5	1.1647 (3)	0.2690 (2)	0.7201 (2)	0.0539 (8)
H5M	1.0884 (18)	0.266 (3)	0.714 (3)	0.065*
N6	1.4196 (2)	0.88478 (18)	0.23972 (17)	0.0342 (5)
O1	1.1404 (2)	0.96280 (16)	0.20227 (15)	0.0423 (5)
O2	1.1842 (3)	0.81934 (18)	0.16661 (18)	0.0584 (7)
O3	1.2165 (2)	0.71417 (17)	0.38134 (16)	0.0476 (5)
O4	1.0135 (2)	0.77826 (17)	0.38517 (18)	0.0565 (6)
O5	0.2258 (2)	0.7048 (2)	0.9236 (2)	0.0730 (8)
O6	0.3355 (2)	0.57593 (18)	0.87755 (18)	0.0565 (6)
O7	0.5145 (2)	0.78609 (18)	0.71924 (17)	0.0595 (7)
O9	0.9357 (2)	0.77317 (18)	0.7499 (2)	0.0655 (7)
O10	1.3010 (2)	0.3721 (2)	0.7209 (2)	0.0748 (9)
O11	0.6231 (2)	0.54863 (17)	0.79330 (19)	0.0541 (6)
C40A	0.4877 (4)	0.7961 (3)	0.6430 (3)	0.045 (2)	0.493 (2)
O8A	0.4473 (6)	0.7262 (3)	0.6293 (4)	0.0690 (16)	0.493 (2)
C40B	0.5391 (4)	0.7948 (3)	0.6324 (3)	0.050 (2)	0.507 (2)
O8B	0.5848 (7)	0.7254 (4)	0.5970 (4)	0.094 (2)	0.507 (2)
O91	0.3862 (12)	0.6447 (10)	0.5443 (12)	0.124 (4)	0.313 (2)
O92	0.4001 (14)	0.6143 (12)	0.6174 (11)	0.067 (4)	0.194 (2)
O93	1.4683 (14)	0.5638 (13)	0.4399 (10)	0.125 (5)	0.288 (3)
O94	1.492 (2)	0.4668 (18)	0.4218 (15)	0.127 (7)	0.205 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03373 (19)	0.03127 (19)	0.0359 (2)	−0.00344 (14)	−0.01496 (14)	−0.00725 (15)
Zn2	0.03584 (19)	0.0342 (2)	0.0345 (2)	−0.00206 (15)	−0.00837 (15)	−0.00503 (15)
C1	0.0337 (16)	0.0413 (19)	0.0379 (17)	−0.0031 (14)	−0.0141 (13)	−0.0060 (15)
C2	0.0322 (15)	0.0324 (16)	0.0331 (15)	−0.0041 (12)	−0.0120 (12)	−0.0055 (13)
C3	0.0394 (16)	0.0298 (16)	0.0409 (17)	0.0015 (13)	−0.0174 (13)	−0.0098 (13)
C4	0.0406 (16)	0.0348 (16)	0.0382 (17)	−0.0033 (13)	−0.0164 (13)	−0.0123 (13)
C5	0.0520 (18)	0.0337 (17)	0.0281 (15)	−0.0131 (14)	−0.0106 (13)	−0.0064 (13)
C6	0.0529 (19)	0.0382 (18)	0.0382 (18)	−0.0061 (15)	−0.0101 (15)	−0.0104 (15)
C7	0.0455 (18)	0.0453 (19)	0.0345 (17)	−0.0141 (15)	−0.0064 (14)	−0.0089 (15)
C8	0.0368 (16)	0.0415 (19)	0.0474 (19)	−0.0083 (14)	−0.0107 (14)	−0.0087 (15)
C9	0.0448 (18)	0.0367 (18)	0.063 (2)	−0.0022 (14)	−0.0129 (16)	−0.0213 (17)
C10	0.0403 (17)	0.052 (2)	0.056 (2)	−0.0108 (15)	−0.0071 (15)	−0.0299 (18)
C11	0.0317 (15)	0.0476 (19)	0.0417 (18)	−0.0151 (14)	−0.0060 (13)	−0.0162 (15)
C12	0.0358 (16)	0.0364 (17)	0.0407 (17)	−0.0088 (13)	−0.0105 (13)	−0.0116 (14)
C13	0.0374 (17)	0.0389 (18)	0.0374 (17)	−0.0080 (14)	−0.0086 (13)	−0.0041 (14)
C14	0.0343 (15)	0.0368 (17)	0.0319 (15)	−0.0046 (13)	−0.0086 (12)	−0.0077 (13)
C15	0.0306 (15)	0.050 (2)	0.0421 (18)	−0.0026 (14)	−0.0124 (13)	−0.0147 (15)
C16	0.0319 (15)	0.0417 (18)	0.0423 (17)	0.0047 (13)	−0.0153 (13)	−0.0181 (14)
C17	0.0341 (15)	0.0355 (16)	0.0366 (16)	0.0016 (12)	−0.0127 (13)	−0.0154 (13)
C18	0.055 (2)	0.063 (2)	0.0441 (19)	−0.0314 (18)	−0.0083 (16)	−0.0167 (17)
C19	0.0297 (14)	0.0364 (16)	0.0284 (15)	−0.0021 (12)	−0.0061 (12)	−0.0109 (13)
C20	0.0313 (15)	0.0342 (17)	0.0380 (17)	0.0016 (12)	−0.0078 (12)	−0.0104 (13)
C21	0.0315 (15)	0.0366 (17)	0.0308 (15)	0.0003 (13)	−0.0060 (12)	−0.0127 (13)
C22	0.0354 (16)	0.0497 (19)	0.0437 (18)	−0.0080 (14)	−0.0095 (13)	−0.0237 (15)
C23	0.0290 (14)	0.0332 (16)	0.0439 (17)	0.0000 (12)	−0.0111 (13)	−0.0163 (14)
C24	0.0408 (17)	0.0392 (18)	0.059 (2)	−0.0048 (14)	−0.0179 (16)	−0.0199 (16)
C25	0.0400 (18)	0.0387 (19)	0.069 (2)	−0.0121 (15)	−0.0125 (17)	−0.0122 (18)
C26	0.0411 (18)	0.0392 (18)	0.048 (2)	−0.0099 (15)	−0.0042 (15)	−0.0048 (15)
C27	0.0377 (16)	0.0377 (17)	0.0387 (17)	−0.0122 (13)	−0.0056 (13)	−0.0097 (14)
C28	0.0318 (17)	0.053 (2)	0.059 (2)	0.0067 (15)	−0.0193 (15)	−0.0272 (17)
C29	0.049 (2)	0.072 (3)	0.093 (3)	0.0267 (18)	−0.043 (2)	−0.056 (2)
C30	0.0347 (16)	0.0461 (19)	0.063 (2)	0.0112 (14)	−0.0186 (15)	−0.0368 (18)
C31	0.0300 (17)	0.063 (2)	0.082 (3)	−0.0078 (16)	−0.0067 (17)	−0.029 (2)
C32	0.052 (2)	0.056 (2)	0.068 (3)	−0.0141 (19)	−0.0018 (19)	−0.002 (2)
C33	0.0412 (18)	0.0417 (19)	0.050 (2)	−0.0002 (15)	−0.0133 (15)	−0.0009 (16)
C34	0.0360 (16)	0.0332 (16)	0.0412 (17)	0.0023 (13)	−0.0153 (13)	−0.0168 (14)
C35	0.058 (2)	0.0426 (19)	0.0313 (17)	−0.0138 (17)	−0.0108 (15)	−0.0118 (14)
C36	0.0353 (17)	0.047 (2)	0.0407 (18)	−0.0037 (14)	−0.0117 (14)	−0.0116 (15)
C37	0.0326 (15)	0.0403 (18)	0.0322 (16)	−0.0010 (13)	−0.0101 (12)	−0.0101 (13)
C38	0.0313 (16)	0.0435 (19)	0.054 (2)	0.0034 (14)	−0.0032 (14)	−0.0184 (16)
C39	0.0408 (18)	0.0375 (18)	0.056 (2)	−0.0020 (14)	−0.0064 (15)	−0.0191 (16)
C41	0.0430 (17)	0.0368 (17)	0.0345 (17)	0.0021 (14)	−0.0096 (13)	−0.0084 (14)
C42	0.0454 (18)	0.0462 (19)	0.0293 (16)	−0.0005 (14)	−0.0121 (13)	−0.0114 (14)
C43	0.062 (2)	0.0373 (18)	0.0419 (18)	−0.0014 (15)	−0.0129 (16)	−0.0193 (15)
N1	0.0323 (13)	0.0359 (14)	0.0404 (14)	−0.0074 (11)	−0.0108 (11)	−0.0109 (12)
N2	0.0392 (15)	0.0489 (18)	0.0443 (16)	−0.0129 (12)	−0.0086 (13)	−0.0116 (13)
N3	0.0283 (13)	0.0406 (15)	0.0477 (15)	−0.0007 (11)	−0.0059 (11)	−0.0226 (13)
N4	0.0414 (14)	0.0380 (15)	0.0386 (15)	−0.0087 (12)	−0.0076 (12)	−0.0081 (12)
N5	0.0321 (14)	0.0573 (19)	0.093 (2)	0.0140 (13)	−0.0300 (15)	−0.0452 (17)
N6	0.0329 (13)	0.0308 (13)	0.0395 (14)	0.0012 (10)	−0.0124 (11)	−0.0112 (11)
O1	0.0498 (13)	0.0414 (12)	0.0440 (12)	−0.0014 (10)	−0.0275 (10)	−0.0117 (10)
O2	0.0804 (17)	0.0426 (14)	0.0599 (15)	0.0185 (13)	−0.0438 (14)	−0.0146 (12)
O3	0.0513 (14)	0.0417 (13)	0.0464 (13)	−0.0172 (11)	−0.0096 (11)	−0.0067 (11)
O4	0.0621 (15)	0.0364 (13)	0.0652 (16)	−0.0085 (12)	−0.0171 (13)	−0.0070 (12)
O5	0.0496 (15)	0.0645 (18)	0.108 (2)	−0.0163 (13)	−0.0025 (15)	−0.0412 (17)
O6	0.0345 (12)	0.0540 (15)	0.0698 (16)	−0.0072 (11)	0.0024 (11)	−0.0184 (13)
O7	0.0727 (17)	0.0511 (15)	0.0400 (14)	−0.0048 (13)	−0.0157 (13)	0.0036 (11)
O9	0.0433 (14)	0.0344 (13)	0.104 (2)	−0.0072 (11)	−0.0034 (14)	−0.0167 (14)
O10	0.0324 (13)	0.0747 (19)	0.141 (3)	0.0098 (12)	−0.0328 (15)	−0.0613 (19)
O11	0.0320 (11)	0.0402 (13)	0.0883 (18)	0.0056 (10)	−0.0152 (12)	−0.0228 (13)
C40A	0.040 (5)	0.041 (5)	0.048 (5)	0.009 (3)	−0.010 (3)	−0.014 (4)
O8A	0.086 (4)	0.038 (3)	0.075 (4)	−0.009 (3)	−0.020 (3)	−0.007 (3)
C40B	0.046 (5)	0.046 (5)	0.047 (5)	0.001 (3)	−0.011 (3)	−0.007 (4)
O8B	0.154 (7)	0.046 (3)	0.073 (4)	0.025 (4)	−0.033 (4)	−0.022 (3)
O91	0.092 (7)	0.094 (7)	0.159 (9)	−0.003 (6)	−0.043 (7)	−0.004 (6)
O92	0.060 (5)	0.070 (6)	0.072 (6)	−0.005 (4)	0.000 (4)	−0.036 (4)
O93	0.106 (8)	0.146 (9)	0.115 (8)	−0.033 (7)	−0.036 (6)	−0.017 (7)
O94	0.126 (8)	0.127 (8)	0.127 (8)	−0.008 (5)	−0.033 (5)	−0.040 (5)

Geometric parameters (Å, º)

Zn1—O1	1.9873 (19)	C22—N3	1.454 (4)
Zn1—O2	2.562 (2)	C22—C23^iii	1.500 (4)
Zn1—O3	2.007 (2)	C22—H22A	0.9700
Zn1—O4	2.443 (2)	C22—H22B	0.9700
Zn1—N1	2.051 (2)	C23—C27	1.376 (4)
Zn1—N6	2.099 (2)	C23—C24	1.383 (4)
Zn2—O6	1.911 (2)	C24—C25	1.386 (5)
Zn2—O7	1.920 (2)	C24—H24	0.9300
Zn2—O11	2.012 (2)	C25—C26	1.367 (5)
Zn2—N4	2.043 (3)	C25—H25	0.9300
C1—O2	1.238 (4)	C26—N4	1.336 (4)
C1—O1	1.268 (4)	C26—H26	0.9300
C1—C2	1.511 (4)	C27—N4	1.336 (4)
C2—C3	1.382 (4)	C27—H27	0.9300
C2—C4	1.393 (4)	C28—O10	1.217 (4)
C3—C4^i	1.389 (4)	C28—N5	1.333 (4)
C3—H3	0.9300	C29—N5	1.453 (4)
C4—H4	0.9300	C29—C30^iv	1.519 (4)
C5—C6	1.385 (4)	C29—H29A	0.9700
C5—C7	1.388 (4)	C29—H29B	0.9700
C5—C35	1.501 (4)	C30—C31	1.361 (5)
C6—C7^ii	1.382 (4)	C30—C34	1.377 (4)
C6—H6	0.9300	C31—C32	1.379 (5)
C7—H7	0.9300	C31—H31	0.9300
C8—N1	1.344 (4)	C32—C33	1.375 (5)
C8—C9	1.372 (5)	C32—H32	0.9300
C8—H8	0.9300	C33—N6	1.335 (4)
C9—C10	1.371 (5)	C33—H33	0.9300
C9—H9	0.9300	C34—N6	1.339 (3)
C10—C11	1.384 (5)	C34—H34	0.9300
C10—H10	0.9300	C35—O4	1.244 (4)
C11—C12	1.376 (4)	C35—O3	1.272 (4)
C11—C18	1.517 (4)	C36—O5	1.222 (4)
C12—N1	1.342 (4)	C36—O6	1.278 (4)
C12—H12	0.9300	C36—C37	1.500 (4)
C13—O9	1.216 (4)	C37—C39	1.378 (4)
C13—N2	1.335 (4)	C37—C38	1.379 (4)
C13—C14	1.499 (4)	C38—C39^v	1.389 (4)
C14—C15	1.380 (4)	C38—H38	0.9300
C14—C20	1.385 (4)	C39—H39	0.9300
C15—C16	1.393 (4)	C41—C42	1.370 (4)
C15—H15	0.9300	C41—C43	1.387 (4)
C16—C17	1.379 (4)	C41—C40B	1.527 (5)
C16—C28	1.500 (4)	C41—C40A	1.528 (5)
C17—C19	1.388 (4)	C42—C43^vi	1.374 (4)
C17—H17	0.9300	C42—H42	0.9300
C18—N2	1.442 (4)	C43—H43	0.9300
C18—H18A	0.9700	N2—H2M	0.851 (10)
C18—H18B	0.9700	N3—H3M	0.857 (10)
C19—C20	1.381 (4)	N5—H5M	0.857 (10)
C19—C21	1.487 (4)	O7—C40B	1.236 (4)
C20—H20	0.9300	O7—C40A	1.237 (4)
C21—O11	1.235 (3)	C40A—O8A	1.235 (5)
C21—N3	1.323 (4)	C40B—O8B	1.234 (5)
O1—Zn1—O3	137.31 (9)	C25—C24—H24	120.4
O1—Zn1—N1	107.98 (9)	C26—C25—C24	119.4 (3)
O3—Zn1—N1	102.87 (9)	C26—C25—H25	120.3
O1—Zn1—N6	100.81 (9)	C24—C25—H25	120.3
O3—Zn1—N6	102.76 (9)	N4—C26—C25	122.0 (3)
N1—Zn1—N6	98.97 (9)	N4—C26—H26	119.0
O1—Zn1—O4	90.74 (8)	C25—C26—H26	119.0
O3—Zn1—O4	58.14 (8)	N4—C27—C23	123.8 (3)
N1—Zn1—O4	93.63 (9)	N4—C27—H27	118.1
N6—Zn1—O4	159.30 (9)	C23—C27—H27	118.1
O1—Zn1—O2	56.10 (8)	O10—C28—N5	120.9 (3)
O3—Zn1—O2	87.32 (8)	O10—C28—C16	121.2 (3)
N1—Zn1—O2	161.71 (8)	N5—C28—C16	117.9 (3)
N6—Zn1—O2	93.41 (9)	N5—C29—C30^iv	114.2 (3)
O4—Zn1—O2	78.75 (9)	N5—C29—H29A	108.7
O6—Zn2—O7	131.00 (11)	C30^iv—C29—H29A	108.7
O6—Zn2—O11	98.23 (10)	N5—C29—H29B	108.7
O7—Zn2—O11	110.62 (10)	C30^iv—C29—H29B	108.7
O6—Zn2—N4	116.42 (11)	H29A—C29—H29B	107.6
O7—Zn2—N4	96.66 (11)	C31—C30—C34	117.8 (3)
O11—Zn2—N4	100.60 (10)	C31—C30—C29^iv	123.7 (3)
O2—C1—O1	122.7 (3)	C34—C30—C29^iv	118.4 (3)
O2—C1—C2	119.6 (3)	C30—C31—C32	120.3 (3)
O1—C1—C2	117.7 (3)	C30—C31—H31	119.9
C3—C2—C4	119.6 (3)	C32—C31—H31	119.9
C3—C2—C1	120.1 (3)	C33—C32—C31	118.1 (3)
C4—C2—C1	120.4 (3)	C33—C32—H32	120.9
C2—C3—C4^i	120.3 (3)	C31—C32—H32	120.9
C2—C3—H3	119.9	N6—C33—C32	122.8 (3)
C4^i—C3—H3	119.9	N6—C33—H33	118.6
C3^i—C4—C2	120.2 (3)	C32—C33—H33	118.6
C3^i—C4—H4	119.9	N6—C34—C30	123.3 (3)
C2—C4—H4	119.9	N6—C34—H34	118.3
C6—C5—C7	119.7 (3)	C30—C34—H34	118.3
C6—C5—C35	119.6 (3)	O4—C35—O3	121.6 (3)
C7—C5—C35	120.6 (3)	O4—C35—C5	119.9 (3)
C7^ii—C6—C5	120.3 (3)	O3—C35—C5	118.5 (3)
C7^ii—C6—H6	119.8	O5—C36—O6	122.4 (3)
C5—C6—H6	119.8	O5—C36—C37	121.6 (3)
C6^ii—C7—C5	120.0 (3)	O6—C36—C37	115.9 (3)
C6^ii—C7—H7	120.0	C39—C37—C38	118.4 (3)
C5—C7—H7	120.0	C39—C37—C36	120.5 (3)
N1—C8—C9	121.8 (3)	C38—C37—C36	121.1 (3)
N1—C8—H8	119.1	C37—C38—C39^v	121.1 (3)
C9—C8—H8	119.1	C37—C38—H38	119.5
C10—C9—C8	119.5 (3)	C39^v—C38—H38	119.5
C10—C9—H9	120.2	C37—C39—C38^v	120.5 (3)
C8—C9—H9	120.2	C37—C39—H39	119.7
C9—C10—C11	119.8 (3)	C38^v—C39—H39	119.7
C9—C10—H10	120.1	C42—C41—C43	118.7 (3)
C11—C10—H10	120.1	C42—C41—C40B	120.8 (3)
C12—C11—C10	117.4 (3)	C43—C41—C40B	119.8 (3)
C12—C11—C18	122.0 (3)	C42—C41—C40A	120.8 (3)
C10—C11—C18	120.6 (3)	C43—C41—C40A	119.1 (3)
N1—C12—C11	123.5 (3)	C41—C42—C43^vi	120.0 (3)
N1—C12—H12	118.3	C41—C42—H42	120.0
C11—C12—H12	118.3	C43^vi—C42—H42	120.0
O9—C13—N2	121.2 (3)	C42^vi—C43—C41	121.3 (3)
O9—C13—C14	120.3 (3)	C42^vi—C43—H43	119.4
N2—C13—C14	118.5 (3)	C41—C43—H43	119.4
C15—C14—C20	118.7 (3)	C12—N1—C8	118.0 (3)
C15—C14—C13	125.5 (3)	C12—N1—Zn1	121.8 (2)
C20—C14—C13	115.8 (3)	C8—N1—Zn1	120.1 (2)
C14—C15—C16	120.7 (3)	C13—N2—C18	119.6 (3)
C14—C15—H15	119.6	C13—N2—H2M	119 (2)
C16—C15—H15	119.6	C18—N2—H2M	122 (2)
C17—C16—C15	119.6 (3)	C21—N3—C22	122.8 (2)
C17—C16—C28	123.4 (3)	C21—N3—H3M	119 (2)
C15—C16—C28	117.0 (3)	C22—N3—H3M	117 (2)
C16—C17—C19	120.4 (3)	C27—N4—C26	118.2 (3)
C16—C17—H17	119.8	C27—N4—Zn2	119.6 (2)
C19—C17—H17	119.8	C26—N4—Zn2	122.2 (2)
N2—C18—C11	113.8 (3)	C28—N5—C29	118.7 (3)
N2—C18—H18A	108.8	C28—N5—H5M	117 (3)
C11—C18—H18A	108.8	C29—N5—H5M	118 (3)
N2—C18—H18B	108.8	C33—N6—C34	117.6 (3)
C11—C18—H18B	108.8	C33—N6—Zn1	121.99 (19)
H18A—C18—H18B	107.7	C34—N6—Zn1	119.5 (2)
C20—C19—C17	119.1 (3)	C1—O1—Zn1	103.41 (18)
C20—C19—C21	116.8 (2)	C1—O2—Zn1	77.51 (18)
C17—C19—C21	124.0 (3)	C35—O3—Zn1	99.7 (2)
C19—C20—C14	121.5 (3)	C35—O4—Zn1	80.50 (19)
C19—C20—H20	119.3	C36—O6—Zn2	114.7 (2)
C14—C20—H20	119.3	C40B—O7—Zn2	123.7 (3)
O11—C21—N3	120.9 (3)	C40A—O7—Zn2	118.2 (3)
O11—C21—C19	120.1 (3)	C21—O11—Zn2	172.2 (2)
N3—C21—C19	119.0 (2)	O8A—C40A—O7	123.0 (5)
N3—C22—C23^iii	111.9 (2)	O8A—C40A—C41	122.3 (4)
N3—C22—H22A	109.2	O7—C40A—C41	114.7 (4)
C23^iii—C22—H22A	109.2	C40A—O8A—O92	173.5 (7)
N3—C22—H22B	109.2	O8B—C40B—O7	125.5 (5)
C23^iii—C22—H22B	109.2	O8B—C40B—C41	119.7 (4)
H22A—C22—H22B	107.9	O7—C40B—C41	114.8 (4)
C27—C23—C24	117.4 (3)	O91—O92—O94^ii	86.0 (13)
C27—C23—C22^iii	120.8 (3)	O91—O92—O8A	101.4 (14)
C24—C23—C22^iii	121.7 (3)	O94^ii—O92—O8A	121.7 (12)
C23—C24—C25	119.2 (3)	O93—O94—O92^ii	146.6 (18)
C23—C24—H24	120.4
O2—C1—C2—C3	−1.6 (4)	O6—C36—C37—C38	7.2 (4)
O1—C1—C2—C3	178.5 (3)	C39—C37—C38—C39^v	−0.1 (5)
O2—C1—C2—C4	177.3 (3)	C36—C37—C38—C39^v	−179.4 (3)
O1—C1—C2—C4	−2.7 (4)	C38—C37—C39—C38^v	0.1 (5)
C4—C2—C3—C4^i	0.0 (5)	C36—C37—C39—C38^v	179.4 (3)
C1—C2—C3—C4^i	178.9 (3)	C43—C41—C42—C43^vi	−0.5 (5)
C3—C2—C4—C3^i	0.0 (5)	C40B—C41—C42—C43^vi	170.1 (3)
C1—C2—C4—C3^i	−178.9 (3)	C40A—C41—C42—C43^vi	−166.9 (3)
C7—C5—C6—C7^ii	−1.3 (5)	C42—C41—C43—C42^vi	0.5 (5)
C35—C5—C6—C7^ii	175.3 (3)	C40B—C41—C43—C42^vi	−170.2 (3)
C6—C5—C7—C6^ii	1.3 (5)	C40A—C41—C43—C42^vi	167.1 (3)
C35—C5—C7—C6^ii	−175.2 (3)	C11—C12—N1—C8	0.5 (4)
N1—C8—C9—C10	0.0 (5)	C11—C12—N1—Zn1	−177.9 (2)
C8—C9—C10—C11	1.1 (5)	C9—C8—N1—C12	−0.8 (4)
C9—C10—C11—C12	−1.3 (4)	C9—C8—N1—Zn1	177.7 (2)
C9—C10—C11—C18	179.2 (3)	O9—C13—N2—C18	−5.6 (5)
C10—C11—C12—N1	0.5 (4)	C14—C13—N2—C18	173.2 (3)
C18—C11—C12—N1	−180.0 (3)	C11—C18—N2—C13	−86.5 (4)
O9—C13—C14—C15	−173.5 (3)	O11—C21—N3—C22	−1.5 (4)
N2—C13—C14—C15	7.8 (5)	C19—C21—N3—C22	178.5 (3)
O9—C13—C14—C20	8.7 (4)	C23^iii—C22—N3—C21	−93.5 (3)
N2—C13—C14—C20	−170.1 (3)	C23—C27—N4—C26	0.6 (5)
C20—C14—C15—C16	−0.3 (4)	C23—C27—N4—Zn2	−177.3 (2)
C13—C14—C15—C16	−178.1 (3)	C25—C26—N4—C27	0.2 (5)
C14—C15—C16—C17	−1.1 (4)	C25—C26—N4—Zn2	178.0 (2)
C14—C15—C16—C28	176.2 (3)	O10—C28—N5—C29	−17.1 (5)
C15—C16—C17—C19	2.1 (4)	C16—C28—N5—C29	162.0 (3)
C28—C16—C17—C19	−175.0 (3)	C30^iv—C29—N5—C28	75.4 (5)
C12—C11—C18—N2	−20.9 (4)	C32—C33—N6—C34	−0.8 (5)
C10—C11—C18—N2	158.6 (3)	C32—C33—N6—Zn1	168.3 (3)
C16—C17—C19—C20	−1.6 (4)	C30—C34—N6—C33	1.9 (4)
C16—C17—C19—C21	176.2 (3)	C30—C34—N6—Zn1	−167.5 (2)
C17—C19—C20—C14	0.2 (4)	O2—C1—O1—Zn1	−6.7 (4)
C21—C19—C20—C14	−177.8 (3)	C2—C1—O1—Zn1	173.3 (2)
C15—C14—C20—C19	0.8 (4)	O1—C1—O2—Zn1	5.2 (3)
C13—C14—C20—C19	178.8 (3)	C2—C1—O2—Zn1	−174.8 (3)
C20—C19—C21—O11	−2.3 (4)	O4—C35—O3—Zn1	−3.2 (3)
C17—C19—C21—O11	179.8 (3)	C5—C35—O3—Zn1	174.3 (2)
C20—C19—C21—N3	177.7 (3)	O3—C35—O4—Zn1	2.6 (3)
C17—C19—C21—N3	−0.2 (4)	C5—C35—O4—Zn1	−174.9 (3)
C27—C23—C24—C25	0.5 (4)	O5—C36—O6—Zn2	−0.6 (4)
C22^iii—C23—C24—C25	177.9 (3)	C37—C36—O6—Zn2	179.10 (19)
C23—C24—C25—C26	0.2 (5)	C40B—O7—C40A—O8A	107.2 (3)
C24—C25—C26—N4	−0.5 (5)	Zn2—O7—C40A—O8A	−2.9 (3)
C24—C23—C27—N4	−0.9 (5)	C40B—O7—C40A—C41	−72.9 (2)
C22^iii—C23—C27—N4	−178.3 (3)	Zn2—O7—C40A—C41	177.1 (2)
C17—C16—C28—O10	−172.4 (3)	C42—C41—C40A—O8A	155.3 (4)
C15—C16—C28—O10	10.5 (5)	C43—C41—C40A—O8A	−11.1 (4)
C17—C16—C28—N5	8.6 (5)	C40B—C41—C40A—O8A	−108.6 (3)
C15—C16—C28—N5	−168.5 (3)	C42—C41—C40A—O7	−24.7 (4)
C34—C30—C31—C32	0.3 (5)	C43—C41—C40A—O7	168.9 (3)
C29^iv—C30—C31—C32	−176.0 (3)	C40B—C41—C40A—O7	71.4 (2)
C30—C31—C32—C33	0.7 (6)	C40A—O7—C40B—O8B	−106.8 (3)
C31—C32—C33—N6	−0.4 (6)	Zn2—O7—C40B—O8B	−22.3 (3)
C31—C30—C34—N6	−1.7 (5)	C40A—O7—C40B—C41	73.1 (2)
C29^iv—C30—C34—N6	174.9 (3)	Zn2—O7—C40B—C41	157.6 (2)
C6—C5—C35—O4	−10.8 (4)	C42—C41—C40B—O8B	−156.0 (4)
C7—C5—C35—O4	165.8 (3)	C43—C41—C40B—O8B	14.5 (4)
C6—C5—C35—O3	171.7 (3)	C40A—C41—C40B—O8B	108.2 (3)
C7—C5—C35—O3	−11.8 (4)	C42—C41—C40B—O7	24.1 (4)
O5—C36—C37—C39	7.6 (5)	C43—C41—C40B—O7	−165.4 (3)
O6—C36—C37—C39	−172.2 (3)	C40A—C41—C40B—O7	−71.7 (2)
O5—C36—C37—C38	−173.1 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5M···O4^ii	0.86 (1)	2.40 (2)	3.112 (4)	141 (3)
N3—H3M···O2^ii	0.86 (1)	2.16 (1)	2.982 (3)	161 (3)
N2—H2M···O8A^vii	0.85 (1)	2.41 (3)	3.007 (7)	127 (3)

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