A zinc(II) metal–organic framework with a novel topology formed from 4,4′,4′′-nitrilo­tribenzoate and 4,4′-bi­pyridine ligands

A metal–organic framework with a novel topology, poly[sesqui(μ₂-4,4′-bi­pyridine)­bis­(di­methyl­formamide)­bis­(μ₄-4,4′,4′′-nitrilo­tribenzoato)trizinc(II)], [Zn₃(C₂₁H₁₂NO₆)₂(C₁₀H₈N₂)_1.5(C₃H₇NO)₂]_n, was obtained by the solvothermal method using 4,4′,4′′-nitrilo­tri­benzoic acid and 4,4′-bi­pyridine (bipy). The structure, determined by single-crystal X-ray diffraction analysis, possesses three kinds of crystallographically independent Zn^II cations, as well as binuclear Zn₂(COO)₄(bipy)₂ paddle-wheel clusters, and can be reduced to a novel topology of a (3,3,6)-connected 3-nodal net, with the Schläfli symbol {5.6²}₄{5².6}₄{5⁸.8⁷} according to the topological analysis.

S1. Introduction

Nowadays, the study of metal–organic frameworks (MOFs) is one of the most fascinating fields in materials science and inorganic chemistry because of the versatility of their structures and varieties of their functions, such as catalysis (Yoon et al., 2011), gas adsorption (Suh et al., 2012), electrical conductivity (Talin et al., 2014), luminescence (Cui et al., 2012; Yang et al., 2011) and nonlinear optical materials (Wang et al., 2012). MOFs are usually self-assembled from metal ions and organic ligands, and it is obvious that the organic ligands play a vital role in the design and synthesis of functional MOFs. Such ligands include N- or O-coordinated single ligands and other sufficiently attractive multiple ligands (Robin & Fromm, 2006; Paul et al., 2014; Lee et al., 2011).

Aromatic polycarboxyl­ate ligands, such as 4,4',4''-nitrilo­tri­benzoic acid (H₃TCA), have been used widely in the construction of inter­esting frameworks and functional materials since they have multiple coordination nodes to meet the needs of different metal atoms (Chae et al., 2003; Lee et al., 2005; Koh et al., 2010). Furthermore, multiple ligands which contain different coordinated atoms can result in greater tunability of the structural networks than single ligands (Lee et al., 2011). For a better understanding of the intrinsic coordination of multiple ligands and to explore further their influence on the structure of MOFs, we report here the synthesis and crystal structure of a novel MOF incorporating zinc(II), H₃TCA and 4,4'-bi­pyridine (bipy), namely [Zn₃(TCA)₂(bipy)_1.5(DMF)₂]_n, (I).

S2. Experimental

S2.1. Synthesis and crystallization

4,4',4''-Nitrilo­tri­benzoic acid (H₃TCA) was synthesized according to the literature method of Dapperheld et al. (1991). H₃TCA (0.037 g, 0.10 mmol), Zn(NO₃)₃·6H₂O (0.028 g, 0.10 mmol) and bipy (0.016 g, 0.10 mmol) were dissolved in di­methyl­formamide (DMF; 6 ml). The mixture was sealed and heated to 373 K for 3 d and then cooled to room temperature. Light-yellow rod-like crystals of (I) were collected (yield 39.1%, based on Zn). FT–IR (KBr, ν, cm^-1): 1660 (m), 1592 (vs), 1539 (m), 1506 (m), 1393 (vs), 1312 (vs), 1272 (m), 1170 (s), 1099 (w), 1073 (w), 1013 (w), 853 (m), 819 (w), 780 (vs), 712 (w), 675 (m), 639 (w), 526 (m), 457 (w).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The DMF/H₂O solvent molecules were highly disordered and we were unsuccessful in locating and refining the solvent peaks. The diffuse electron densities resulting from these residual solvent molecules were removed from the data set using the SQUEEZE routine (Spek, 2015) of PLATON (Spek, 2009) and refined further using the data generated. The final formula does not include the contribution of the solvents. The pyridine ring (N2/C6–C10) and two coordinated DMF molecules (O1/N7/C64–C66 and O14/N6/C61–C63) were also highly disordered and a PART instruction was used to obtain two different positions, which were finally refined with an FVAR value of 0.565260 [Please reword without SHELX specific instructions]. All H atoms were placed in geometrically idealized positions and refined using a riding model, with C—H = 0.96 (methyl), 0.93 (benzene) or 0.93 Å (pyridine), and with U_iso(H) = 1.2U_eq(C) for pyridine and benzene H atoms or 1.5U_eq(C) for methyl H atoms.

S3. Results and discussion

Light-yellow crystals of (I) were assembled by the solvothermal method in the presence of di­methyl­formamide (DMF) and water. Single-crystal X-ray diffraction analysis reveals that (I) crystallizes in the triclinic P1 space group. The asymmetric unit contains three crystallographically independent Zn^II cations, two 4,4',4''-nitrilo­tribenzoate (TCA^3-) ligands, one and a half 4,4'-bi­pyridine (bipy) ligands and two coordinated DMF molecules (Fig. 1).

As shown in Fig. 2, atom Zn1 is tetra­coordinated by three O-atom donors from two separate TCA^3- ligands, a DMF molecule in a monodentate coordination mode and a pyridine N-atom donor from a bipy molecule, resulting in a slightly distorted tetra­hedral geometry. The Zn—O(TCA^3-), Zn—O(DMF) and Zn—N(bipy) bond lengths (Table 2) are comparable with reported literature values (Chang et al., 2014; Yang et al.,2010; Mossine et al., 2014; Fang et al., 2006). The X—Zn—X (X is a basal O or N atom) angles in the distorted tetra­hedron range from 96.690 (2) to 136.516 (1)° and the tetra­hedron edge lengths range from 2.9998 (4) to 3.6230 (5) Å.

Inter­estingly, this framework also contains secondary building units (SBUs) of two penta­coordinated Zn2 cations bridged in a paddle-wheel-type configuration, where two Zn2 atoms occupy the equatorial sites of the o­cta­hedron (Köberl et al., 2011; Tan et al., 2012; Song et al., 2012). The binuclear zinc clusters are coordinated by eight carboxyl­ate O-atom donors from four separate TCA^3- ligands in chelating modes and by two pyridine N-atom donors from two different bipy molecules (Table 2).

Atom Zn3 is hexacoordinated by four carboxyl­ate O-atom donors from two separate TCA^3- ligands in chelating modes, by another O-atom donor from a DMF molecule and by a pyridine N-atom donor from a bipy molecule. The Zn—O/N bond lengths (Table 2) are comparable with literature values (Chang et al., 2014; Yang et al., 2010; Mossine et al., 2014; Fang et al., 2006).

The binuclear Zn₂(COO)₄(bipy)₂ clusters and bipy molecules are connected in a head-to-tail fashion into an infinite one-dimensional linear chain, with a cluster separation of 13.9620 (2) Å, which is the basis for the extension of the dimensionality. Meanwhile, each paddle-wheel cluster as a 6-connected SBU coordinates to four 3-connected TCA^3- ligands and two bipy molecules, forming a larger chain structure. As shown in Fig. 3, the bipy ligands (red) link adjacent layers by coordinating to Zn1 atoms, which further aggregates the structure into a two-dimensional supra­molecular framework.

As shown in Figs. 4(a) and 4(b), the two-dimensional networks can also be inter­digitated with each other along the ac plane, which corresponds to the topological structure. Atoms Zn1 and Zn3 and the TCA^3- ligands are considered as 3-connected nodes, while the binuclear Zn₂(COO)₄(bipy)₂ cluster serves as a 6-connected node. Thus, the structure of (I) can be reduced to the new topology of a (3,3,6)-connected 3-nodal net, with the Schläfli symbol {5.6²}₄{5².6}₄{5⁸.8⁷} (see Figs. 4c and 4d), as calculated by the TOPOS software (Blatov, 2006).

In summary, in this work a novel MOF, {[Zn₃(TCA)₂(bipy)_1.5(DMF)₂]·(Solvents)}_n, with a new topology was obtained by the solvothermal method. It possesses three kinds of crystallographically independent Zn^II cations, including binuclear Zn₂(COO)₄(bipy)₂ paddle-wheel clusters. As a result, the two simple ligands may inspire the design of functional MOFs and lay a foundation for our future work.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The asymmetric unit of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms and C-atom labels have been omitted for clarity. [Please provide revised plot with the asymmetric unit fully labelled]
	Fig. 2. The coordination environments of atoms Zn1, Zn2 and Zn3 of (I). [Very similar to Fig. 1; is it needed?]
	Fig. 3. A view of the one-dimensional linear structure and two-dimensional framework of (I).
	Fig. 4. (a) The monolayer structure of (I), along the ac plane. (b) The topological structure of the monolayer. (c) The two-dimensional interdigitated structure along the ac plane. (d) An illustration of the topological structure of (I). [Please provide higher-resolution images for parts (a) and (c)]

Poly[sesqui(µ₂-4,4'-bipyridine)bis(dimethylformamide)bis(µ₄-4,4',4''-nitrilotribenzoato)trizinc(II)]

Crystal data

[Zn3(C21H12NO6)2(C10H8N2)1.5(C3H7NO)2]	Z = 2
Mr = 1325.21	F(000) = 1358
Triclinic, P1	Dx = 0.874 Mg m^−3
a = 13.6198 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.962 (2) Å	Cell parameters from 8006 reflections
c = 26.646 (4) Å	θ = 2.2–23.4°
α = 85.035 (2)°	µ = 0.75 mm^−1
β = 89.776 (2)°	T = 296 K
γ = 86.223 (2)°	Rod, light yellow
V = 5037.1 (12) Å^3	0.24 × 0.22 × 0.19 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	11697 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
φ and ω scans	θmax = 27.5°, θmin = 0.8°
Absorption correction: ψ scan (SADABS; Bruker, 2000)	h = −16→15
Tmin = 0.830, Tmax = 0.872	k = −17→17
39611 measured reflections	l = −33→32
20086 independent reflections

Refinement

Refinement on F^2	319 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.071	H-atom parameters constrained
wR(F^2) = 0.216	w = 1/[σ^2(Fo^2) + (0.1184P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.003
20086 reflections	Δρmax = 1.04 e Å^−3
859 parameters	Δρmin = −1.82 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	Occ. (<1)
C1	1.0975 (4)	0.9884 (4)	0.2840 (2)	0.0695 (14)
H1	1.1443	0.9377	0.2810	0.083*
C2	1.0504 (4)	0.9963 (4)	0.32995 (18)	0.0661 (14)
H2	1.0649	0.9503	0.3567	0.079*
C3	0.9820 (4)	1.0720 (3)	0.33598 (17)	0.0537 (11)
C4	0.9645 (5)	1.1372 (4)	0.2952 (2)	0.0769 (17)
H4	0.9200	1.1901	0.2975	0.092*
C5	1.0137 (4)	1.1242 (4)	0.2505 (2)	0.0758 (16)
H5	1.0006	1.1698	0.2233	0.091*
C6	0.9300 (4)	1.0816 (3)	0.38349 (17)	0.0562 (12)
C7	0.9243 (9)	1.0017 (8)	0.4190 (4)	0.075 (3)	0.575 (2)
H7	0.9549	0.9422	0.4131	0.091*	0.575 (2)
C8	0.8718 (9)	1.0133 (7)	0.4634 (4)	0.076 (3)	0.575 (2)
H8	0.8672	0.9601	0.4866	0.091*	0.575 (2)
C9	0.8479 (10)	1.1710 (7)	0.4439 (4)	0.084 (3)	0.575 (2)
H9	0.8284	1.2317	0.4536	0.101*	0.575 (2)
C10	0.8966 (10)	1.1679 (8)	0.3979 (4)	0.087 (3)	0.575 (2)
H10	0.9057	1.2242	0.3775	0.104*	0.575 (2)
C7'	0.9670 (11)	1.0537 (13)	0.4278 (6)	0.085 (4)	0.425 (2)
H7'	1.0293	1.0223	0.4310	0.102*	0.425 (2)
C8'	0.9105 (14)	1.0724 (15)	0.4712 (6)	0.099 (5)	0.425 (2)
H8'	0.9442	1.0623	0.5017	0.119*	0.425 (2)
C9'	0.7852 (12)	1.1364 (12)	0.4296 (5)	0.082 (4)	0.425 (2)
H9'	0.7219	1.1657	0.4300	0.099*	0.425 (2)
C10'	0.8338 (12)	1.1325 (12)	0.3840 (5)	0.087 (4)	0.425 (2)
H10'	0.8054	1.1618	0.3544	0.104*	0.425 (2)
C11	0.7474 (4)	0.9460 (4)	0.6098 (2)	0.0656 (14)
C12	0.7767 (4)	0.8463 (3)	0.63167 (17)	0.0567 (12)
C13	0.8321 (4)	0.7809 (4)	0.60504 (18)	0.0719 (15)
H13	0.8499	0.7994	0.5721	0.086*
C14	0.8615 (4)	0.6903 (3)	0.62528 (18)	0.0722 (15)
H14	0.8995	0.6486	0.6066	0.087*
C15	0.8337 (4)	0.6615 (3)	0.67431 (16)	0.0591 (13)
C16	0.7778 (4)	0.7256 (4)	0.70131 (17)	0.0695 (15)
H16	0.7578	0.7065	0.7339	0.083*
C17	0.7518 (4)	0.8160 (4)	0.68084 (19)	0.0661 (14)
H17	0.7165	0.8587	0.7002	0.079*
C18	0.8269 (5)	0.2378 (4)	0.58557 (19)	0.0720 (16)
C19	0.8387 (5)	0.3267 (3)	0.61331 (19)	0.0670 (14)
C20	0.9186 (5)	0.3338 (4)	0.6401 (2)	0.0866 (19)
H20	0.9685	0.2849	0.6411	0.104*
C21	0.9297 (5)	0.4145 (4)	0.6674 (2)	0.0835 (18)
H21	0.9871	0.4186	0.6856	0.100*
C22	0.8579 (4)	0.4860 (3)	0.66723 (16)	0.0592 (13)
C23	0.7732 (5)	0.4782 (4)	0.6397 (2)	0.0893 (19)
H23	0.7219	0.5257	0.6395	0.107*
C24	0.7656 (5)	0.3986 (4)	0.6125 (2)	0.0861 (18)
H24	0.7095	0.3942	0.5932	0.103*
C25	0.9709 (3)	0.5129 (3)	0.90358 (15)	0.0428 (10)
C26	0.9504 (3)	0.5261 (3)	0.84824 (15)	0.0425 (9)
C27	0.9684 (4)	0.6094 (3)	0.81923 (17)	0.0582 (12)
H27	0.9968	0.6588	0.8340	0.070*
C28	0.9455 (4)	0.6209 (3)	0.76953 (18)	0.0682 (15)
H28	0.9624	0.6762	0.7504	0.082*
C29	0.8964 (4)	0.5507 (3)	0.74632 (15)	0.0524 (11)
C30	0.8786 (4)	0.4684 (3)	0.77520 (17)	0.0607 (13)
H30	0.8475	0.4201	0.7609	0.073*
C31	0.9056 (4)	0.4554 (3)	0.82499 (16)	0.0553 (12)
H31	0.8937	0.3978	0.8435	0.066*
C32	0.8139 (3)	0.5131 (3)	1.01971 (16)	0.0460 (10)
C33	0.7122 (3)	0.5206 (3)	1.04053 (17)	0.0465 (10)
C34	0.6508 (3)	0.4446 (3)	1.03816 (18)	0.0547 (12)
H34	0.6739	0.3899	1.0230	0.066*
C35	0.5591 (3)	0.4487 (3)	1.05725 (19)	0.0600 (13)
H35	0.5184	0.3990	1.0531	0.072*
C36	0.5241 (3)	0.5268 (3)	1.08328 (18)	0.0529 (11)
C37	0.5867 (3)	0.6015 (3)	1.0858 (2)	0.0629 (14)
H37	0.5655	0.6549	1.1024	0.075*
C38	0.6764 (3)	0.5986 (3)	1.0649 (2)	0.0616 (13)
H38	0.7153	0.6504	1.0669	0.074*
C39	0.2298 (4)	0.8875 (4)	1.1443 (2)	0.0648 (14)
C40	0.2799 (3)	0.7928 (3)	1.13407 (19)	0.0561 (12)
C41	0.3250 (4)	0.7814 (3)	1.08790 (19)	0.0593 (12)
H41	0.3225	0.8329	1.0632	0.071*
C42	0.3730 (3)	0.6956 (3)	1.07803 (18)	0.0557 (12)
H42	0.4011	0.6891	1.0465	0.067*
C43	0.3800 (3)	0.6186 (3)	1.11460 (18)	0.0522 (11)
C44	0.3331 (4)	0.6268 (3)	1.1605 (2)	0.0681 (14)
H44	0.3351	0.5754	1.1852	0.082*
C45	0.2820 (4)	0.7157 (4)	1.1686 (2)	0.0704 (15)
H45	0.2485	0.7213	1.1988	0.085*
C46	0.2456 (4)	0.1806 (3)	1.16346 (18)	0.0521 (11)
C47	0.2944 (3)	0.2725 (3)	1.14869 (17)	0.0498 (11)
C48	0.2476 (3)	0.3442 (3)	1.11651 (17)	0.0473 (10)
H48	0.1851	0.3359	1.1043	0.057*
C49	0.2931 (3)	0.4285 (3)	1.10233 (18)	0.0535 (11)
H49	0.2613	0.4759	1.0804	0.064*
C50	0.3839 (3)	0.4419 (3)	1.12031 (18)	0.0527 (11)
C51	0.4320 (4)	0.3694 (4)	1.1516 (2)	0.0682 (14)
H51	0.4952	0.3771	1.1632	0.082*
C52	0.3863 (3)	0.2861 (4)	1.1657 (2)	0.0636 (13)
H52	0.4188	0.2383	1.1871	0.076*
C56	1.0602 (4)	0.1966 (3)	1.0269 (2)	0.0800 (19)
H56	1.1054	0.2245	1.0462	0.096*
C57	1.0655 (4)	0.0962 (3)	1.0272 (2)	0.0702 (16)
H57	1.1139	0.0591	1.0460	0.084*
C58	0.9997 (3)	0.0528 (2)	0.99990 (15)	0.0403 (9)
C59	0.9313 (4)	0.1132 (3)	0.9735 (2)	0.0724 (17)
H59	0.8849	0.0871	0.9540	0.087*
C60	0.9296 (4)	0.2122 (3)	0.9750 (2)	0.0696 (16)
H60	0.8810	0.2509	0.9573	0.083*
O14	−0.0039 (3)	0.0471 (4)	1.13691 (17)	0.05665 (17)	0.575 (2)
C61	−0.0424 (5)	0.1225 (5)	1.12665 (19)	0.05665 (17)	0.575 (2)
H61	−0.0085	0.1775	1.1295	0.068*	0.575 (2)
C62	−0.1931 (6)	0.2260 (5)	1.0970 (3)	0.05665 (17)	0.575 (2)
H62A	−0.1504	0.2755	1.1035	0.085*	0.575 (2)
H62B	−0.2513	0.2321	1.1172	0.085*	0.575 (2)
H62C	−0.2111	0.2322	1.0620	0.085*	0.575 (2)
C63	−0.1858 (5)	0.0413 (5)	1.1068 (3)	0.05665 (17)	0.575 (2)
H63A	−0.1583	0.0096	1.0789	0.085*	0.575 (2)
H63B	−0.2556	0.0531	1.1022	0.085*	0.575 (2)
H63C	−0.1730	0.0011	1.1375	0.085*	0.575 (2)
N6	−0.1418 (4)	0.1309 (4)	1.10970 (17)	0.05665 (17)	0.575 (2)
N7	0.4615 (6)	1.1508 (4)	0.5010 (3)	0.0982 (7)	0.575 (2)
O1	0.6145 (5)	1.1075 (7)	0.5079 (4)	0.0950 (6)	0.575 (2)
C64	0.5499 (6)	1.1400 (6)	0.5320 (3)	0.0967 (6)	0.575 (2)
H64	0.5545	1.1559	0.5650	0.116*	0.575 (2)
C65	0.3675 (6)	1.1887 (8)	0.5185 (4)	0.1008 (8)	0.575 (2)
H65A	0.3583	1.1651	0.5530	0.151*	0.575 (2)
H65B	0.3159	1.1685	0.4982	0.151*	0.575 (2)
H65C	0.3659	1.2578	0.5159	0.151*	0.575 (2)
C66	0.4678 (7)	1.1209 (8)	0.4485 (3)	0.1003 (8)	0.575 (2)
H66A	0.4038	1.1060	0.4377	0.150*	0.575 (2)
H66B	0.5126	1.0651	0.4477	0.150*	0.575 (2)
H66C	0.4910	1.1726	0.4264	0.150*	0.575 (2)
O14'	0.0037 (4)	−0.0044 (5)	1.1471 (3)	0.05665 (17)	0.425 (2)
N6'	−0.0919 (6)	−0.1225 (5)	1.1278 (2)	0.05665 (17)	0.425 (2)
C61'	−0.0022 (7)	−0.0871 (6)	1.1451 (3)	0.05665 (17)	0.425 (2)
H61'	0.0509	−0.1299	1.1546	0.068*	0.425 (2)
C62'	−0.0990 (8)	−0.2271 (6)	1.1323 (3)	0.05665 (17)	0.425 (2)
H62D	−0.0374	−0.2580	1.1229	0.085*	0.425 (2)
H62E	−0.1502	−0.2433	1.1106	0.085*	0.425 (2)
H62F	−0.1139	−0.2485	1.1666	0.085*	0.425 (2)
C63'	−0.1595 (6)	−0.0420 (6)	1.1087 (3)	0.05665 (17)	0.425 (2)
H63D	−0.1912	−0.0132	1.1365	0.085*	0.425 (2)
H63E	−0.2083	−0.0651	1.0877	0.085*	0.425 (2)
H63F	−0.1234	0.0051	1.0894	0.085*	0.425 (2)
N7'	0.4357 (7)	1.0990 (6)	0.5094 (3)	0.0981 (7)	0.425 (2)
O1'	0.6012 (6)	1.1170 (11)	0.5102 (5)	0.0952 (7)	0.425 (2)
C64'	0.5376 (7)	1.0680 (7)	0.5288 (4)	0.0965 (6)	0.425 (2)
H64'	0.5506	1.0163	0.5528	0.116*	0.425 (2)
C65'	0.3509 (7)	1.0582 (9)	0.5307 (5)	0.1008 (9)	0.425 (2)
H65D	0.2940	1.0824	0.5112	0.151*	0.425 (2)
H65E	0.3428	1.0754	0.5646	0.151*	0.425 (2)
H65F	0.3583	0.9894	0.5307	0.151*	0.425 (2)
C66'	0.4331 (8)	1.1746 (9)	0.4667 (5)	0.0995 (8)	0.425 (2)
H66D	0.3840	1.1619	0.4428	0.149*	0.425 (2)
H66E	0.4963	1.1746	0.4506	0.149*	0.425 (2)
H66F	0.4175	1.2364	0.4790	0.149*	0.425 (2)
N1	1.0781 (3)	1.0514 (3)	0.24378 (14)	0.0547 (10)
N2	0.8276 (4)	1.0986 (3)	0.47397 (14)	0.0603 (10)
N3	0.8668 (4)	0.5660 (3)	0.69583 (14)	0.0702 (12)
N4	0.4301 (3)	0.5300 (3)	1.10522 (16)	0.0604 (11)
N5	0.9953 (3)	0.2532 (2)	1.00092 (13)	0.0419 (8)
O2	0.7863 (3)	0.9696 (2)	0.56683 (13)	0.0738 (10)
O3	0.6916 (4)	0.9997 (3)	0.63188 (16)	0.1009 (14)
O4	0.8949 (4)	0.1780 (3)	0.58218 (15)	0.0989 (14)
O5	0.7436 (3)	0.2279 (3)	0.56677 (15)	0.0869 (12)
O6	0.9862 (2)	0.5879 (2)	0.92502 (10)	0.0509 (7)
O7	0.9706 (2)	0.4304 (2)	0.92470 (11)	0.0575 (8)
O8	0.8600 (2)	0.5892 (2)	1.01408 (13)	0.0593 (8)
O9	0.8494 (2)	0.4319 (2)	1.01005 (12)	0.0553 (8)
O10	0.2204 (3)	0.9549 (3)	1.11119 (16)	0.0743 (10)
O11	0.1943 (3)	0.8961 (3)	1.18808 (16)	0.0877 (12)
O12	0.2863 (3)	0.1169 (2)	1.19227 (14)	0.0710 (10)
O13	0.1611 (2)	0.1699 (2)	1.14417 (12)	0.0576 (8)
Zn1	0.75053 (4)	1.10165 (4)	0.54052 (2)	0.05677 (17)
Zn2	0.99475 (3)	0.39776 (3)	0.99981 (2)	0.03428 (13)
Zn3	0.14112 (4)	0.03622 (4)	1.17412 (2)	0.05665 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.080 (4)	0.059 (3)	0.067 (3)	0.009 (3)	0.013 (3)	−0.001 (3)
C2	0.086 (4)	0.062 (3)	0.049 (3)	0.001 (3)	0.005 (3)	0.002 (2)
C3	0.071 (3)	0.043 (3)	0.048 (3)	−0.006 (2)	0.005 (2)	−0.005 (2)
C4	0.111 (5)	0.055 (3)	0.060 (3)	0.022 (3)	0.022 (3)	0.000 (2)
C5	0.109 (5)	0.051 (3)	0.063 (3)	0.009 (3)	0.024 (3)	0.009 (2)
C6	0.069 (3)	0.051 (3)	0.049 (3)	−0.002 (2)	0.006 (2)	−0.012 (2)
C7	0.102 (7)	0.058 (5)	0.062 (5)	0.016 (5)	0.018 (5)	−0.001 (4)
C8	0.108 (7)	0.056 (5)	0.057 (5)	0.018 (5)	0.019 (5)	0.011 (4)
C9	0.119 (7)	0.052 (5)	0.079 (6)	0.006 (5)	0.031 (6)	−0.005 (5)
C10	0.113 (7)	0.064 (6)	0.080 (6)	0.006 (5)	0.034 (6)	0.000 (5)
C7'	0.071 (7)	0.117 (9)	0.063 (7)	0.001 (7)	0.009 (6)	0.001 (7)
C8'	0.099 (9)	0.127 (10)	0.071 (8)	−0.002 (8)	−0.012 (7)	−0.008 (7)
C9'	0.076 (7)	0.102 (8)	0.064 (7)	0.023 (7)	0.011 (6)	−0.001 (6)
C10'	0.094 (8)	0.100 (8)	0.060 (7)	0.017 (7)	0.007 (6)	0.014 (6)
C11	0.086 (4)	0.052 (3)	0.059 (3)	−0.002 (3)	−0.011 (3)	−0.009 (3)
C12	0.075 (3)	0.049 (3)	0.047 (3)	−0.010 (2)	−0.006 (2)	−0.002 (2)
C13	0.121 (5)	0.051 (3)	0.043 (3)	−0.004 (3)	0.001 (3)	−0.001 (2)
C14	0.123 (5)	0.045 (3)	0.047 (3)	−0.003 (3)	0.006 (3)	−0.003 (2)
C15	0.100 (4)	0.035 (2)	0.042 (2)	0.000 (2)	−0.014 (2)	−0.0047 (19)
C16	0.115 (5)	0.057 (3)	0.036 (2)	0.004 (3)	0.007 (3)	−0.003 (2)
C17	0.080 (4)	0.064 (3)	0.054 (3)	0.003 (3)	0.002 (3)	−0.009 (2)
C18	0.119 (5)	0.050 (3)	0.047 (3)	−0.004 (3)	0.000 (3)	−0.007 (2)
C19	0.103 (4)	0.043 (3)	0.056 (3)	0.000 (3)	−0.011 (3)	−0.010 (2)
C20	0.114 (5)	0.068 (4)	0.077 (4)	0.025 (3)	−0.020 (4)	−0.026 (3)
C21	0.095 (4)	0.086 (4)	0.072 (4)	0.007 (3)	−0.026 (3)	−0.032 (3)
C22	0.093 (4)	0.045 (3)	0.040 (2)	0.001 (3)	−0.009 (2)	−0.009 (2)
C23	0.116 (5)	0.057 (3)	0.097 (5)	0.020 (3)	−0.031 (4)	−0.031 (3)
C24	0.106 (5)	0.068 (4)	0.088 (4)	−0.004 (3)	−0.031 (4)	−0.029 (3)
C25	0.048 (2)	0.036 (2)	0.045 (2)	−0.0019 (19)	−0.0031 (19)	−0.0089 (19)
C26	0.053 (3)	0.033 (2)	0.042 (2)	−0.0038 (18)	−0.0004 (19)	−0.0055 (17)
C27	0.090 (4)	0.038 (2)	0.049 (3)	−0.019 (2)	−0.013 (2)	−0.006 (2)
C28	0.115 (4)	0.044 (3)	0.047 (3)	−0.027 (3)	−0.005 (3)	0.003 (2)
C29	0.084 (3)	0.039 (2)	0.035 (2)	−0.009 (2)	−0.006 (2)	−0.0020 (18)
C30	0.096 (4)	0.039 (2)	0.049 (3)	−0.019 (2)	−0.011 (3)	−0.007 (2)
C31	0.084 (3)	0.039 (2)	0.043 (2)	−0.008 (2)	0.000 (2)	0.0019 (19)
C32	0.047 (3)	0.045 (3)	0.046 (2)	−0.002 (2)	0.0021 (19)	−0.0053 (19)
C33	0.043 (2)	0.038 (2)	0.059 (3)	−0.0065 (19)	0.001 (2)	−0.0045 (19)
C34	0.055 (3)	0.042 (2)	0.070 (3)	−0.010 (2)	0.010 (2)	−0.019 (2)
C35	0.058 (3)	0.041 (3)	0.085 (4)	−0.019 (2)	0.015 (3)	−0.020 (2)
C36	0.048 (3)	0.038 (2)	0.073 (3)	−0.008 (2)	0.006 (2)	−0.005 (2)
C37	0.055 (3)	0.035 (2)	0.103 (4)	−0.009 (2)	0.011 (3)	−0.026 (2)
C38	0.049 (3)	0.044 (3)	0.096 (4)	−0.019 (2)	0.021 (3)	−0.023 (3)
C39	0.057 (3)	0.053 (3)	0.090 (4)	−0.014 (3)	0.006 (3)	−0.030 (3)
C40	0.057 (3)	0.038 (2)	0.077 (3)	−0.012 (2)	0.008 (2)	−0.018 (2)
C41	0.066 (3)	0.046 (3)	0.066 (3)	−0.008 (2)	0.004 (2)	−0.008 (2)
C42	0.055 (3)	0.048 (3)	0.064 (3)	−0.002 (2)	0.010 (2)	−0.011 (2)
C43	0.046 (3)	0.043 (3)	0.070 (3)	−0.007 (2)	0.011 (2)	−0.015 (2)
C44	0.086 (4)	0.039 (3)	0.081 (4)	−0.013 (3)	0.023 (3)	−0.007 (2)
C45	0.082 (4)	0.051 (3)	0.082 (4)	−0.012 (3)	0.030 (3)	−0.026 (3)
C46	0.068 (3)	0.037 (2)	0.052 (3)	−0.009 (2)	0.017 (2)	−0.009 (2)
C47	0.054 (3)	0.041 (2)	0.055 (3)	−0.008 (2)	0.010 (2)	−0.006 (2)
C48	0.046 (2)	0.037 (2)	0.060 (3)	−0.0050 (19)	−0.001 (2)	−0.006 (2)
C49	0.052 (3)	0.037 (2)	0.069 (3)	−0.002 (2)	−0.003 (2)	0.002 (2)
C50	0.046 (3)	0.042 (2)	0.070 (3)	−0.006 (2)	0.011 (2)	−0.006 (2)
C51	0.053 (3)	0.054 (3)	0.096 (4)	−0.015 (2)	−0.014 (3)	0.008 (3)
C52	0.052 (3)	0.060 (3)	0.076 (3)	−0.001 (2)	−0.009 (2)	0.012 (3)
C56	0.101 (4)	0.022 (2)	0.118 (5)	−0.007 (2)	−0.067 (4)	−0.005 (3)
C57	0.089 (4)	0.019 (2)	0.101 (4)	0.005 (2)	−0.050 (3)	0.002 (2)
C58	0.056 (3)	0.0167 (19)	0.048 (2)	−0.0025 (17)	−0.0116 (19)	−0.0021 (16)
C59	0.092 (4)	0.022 (2)	0.105 (4)	−0.003 (2)	−0.053 (3)	−0.012 (2)
C60	0.086 (4)	0.021 (2)	0.101 (4)	−0.002 (2)	−0.053 (3)	−0.001 (2)
O14	0.0716 (4)	0.0410 (3)	0.0603 (3)	−0.0153 (3)	0.0186 (3)	−0.0127 (2)
C61	0.0716 (4)	0.0410 (3)	0.0603 (3)	−0.0153 (3)	0.0186 (3)	−0.0127 (2)
C62	0.0716 (4)	0.0410 (3)	0.0603 (3)	−0.0153 (3)	0.0186 (3)	−0.0127 (2)
C63	0.0716 (4)	0.0410 (3)	0.0603 (3)	−0.0153 (3)	0.0186 (3)	−0.0127 (2)
N6	0.0716 (4)	0.0410 (3)	0.0603 (3)	−0.0153 (3)	0.0186 (3)	−0.0127 (2)
N7	0.0952 (7)	0.0995 (9)	0.0996 (8)	−0.0063 (6)	−0.0019 (5)	−0.0078 (6)
O1	0.0917 (7)	0.0970 (9)	0.0965 (8)	−0.0073 (6)	−0.0037 (5)	−0.0086 (6)
C64	0.0933 (7)	0.0983 (8)	0.0985 (8)	−0.0066 (5)	−0.0018 (5)	−0.0083 (5)
C65	0.0964 (9)	0.1028 (12)	0.1026 (12)	−0.0051 (9)	−0.0010 (9)	−0.0073 (10)
C66	0.0986 (12)	0.1019 (13)	0.1003 (10)	−0.0061 (10)	−0.0029 (8)	−0.0091 (10)
O14'	0.0716 (4)	0.0410 (3)	0.0603 (3)	−0.0153 (3)	0.0186 (3)	−0.0127 (2)
N6'	0.0716 (4)	0.0410 (3)	0.0603 (3)	−0.0153 (3)	0.0186 (3)	−0.0127 (2)
C61'	0.0716 (4)	0.0410 (3)	0.0603 (3)	−0.0153 (3)	0.0186 (3)	−0.0127 (2)
C62'	0.0716 (4)	0.0410 (3)	0.0603 (3)	−0.0153 (3)	0.0186 (3)	−0.0127 (2)
C63'	0.0716 (4)	0.0410 (3)	0.0603 (3)	−0.0153 (3)	0.0186 (3)	−0.0127 (2)
N7'	0.0949 (7)	0.0994 (8)	0.0998 (8)	−0.0068 (5)	−0.0016 (5)	−0.0079 (5)
O1'	0.0920 (7)	0.0971 (9)	0.0967 (9)	−0.0067 (6)	−0.0033 (6)	−0.0086 (6)
C64'	0.0932 (7)	0.0981 (8)	0.0982 (8)	−0.0074 (5)	−0.0022 (5)	−0.0083 (5)
C65'	0.0955 (10)	0.1033 (14)	0.1034 (14)	−0.0070 (11)	−0.0003 (11)	−0.0078 (11)
C66'	0.0974 (11)	0.1009 (12)	0.1000 (11)	−0.0049 (9)	−0.0019 (9)	−0.0075 (8)
N1	0.076 (3)	0.038 (2)	0.052 (2)	−0.0065 (19)	0.0119 (19)	−0.0101 (17)
N2	0.085 (3)	0.049 (2)	0.047 (2)	−0.004 (2)	0.009 (2)	−0.0076 (18)
N3	0.123 (4)	0.046 (2)	0.044 (2)	−0.015 (2)	−0.019 (2)	−0.0084 (18)
N4	0.046 (2)	0.038 (2)	0.099 (3)	−0.0072 (17)	0.021 (2)	−0.009 (2)
N5	0.059 (2)	0.0135 (14)	0.053 (2)	−0.0007 (14)	−0.0111 (17)	−0.0032 (14)
O2	0.114 (3)	0.046 (2)	0.060 (2)	−0.0093 (19)	−0.001 (2)	0.0081 (16)
O3	0.141 (4)	0.073 (3)	0.082 (3)	0.028 (3)	0.012 (3)	0.003 (2)
O4	0.155 (4)	0.060 (2)	0.082 (3)	0.020 (3)	−0.023 (3)	−0.026 (2)
O5	0.115 (3)	0.066 (3)	0.085 (3)	−0.012 (2)	−0.006 (3)	−0.030 (2)
O6	0.065 (2)	0.0456 (17)	0.0428 (16)	−0.0061 (15)	−0.0043 (14)	−0.0074 (13)
O7	0.089 (2)	0.0404 (18)	0.0421 (17)	−0.0018 (16)	−0.0046 (16)	0.0007 (13)
O8	0.0486 (18)	0.0479 (19)	0.082 (2)	−0.0105 (15)	0.0117 (16)	−0.0031 (16)
O9	0.0495 (18)	0.0450 (18)	0.072 (2)	0.0014 (14)	0.0020 (15)	−0.0122 (15)
O10	0.073 (2)	0.045 (2)	0.106 (3)	0.0045 (18)	−0.015 (2)	−0.017 (2)
O11	0.115 (3)	0.056 (2)	0.095 (3)	−0.004 (2)	0.023 (2)	−0.031 (2)
O12	0.083 (2)	0.049 (2)	0.077 (2)	−0.0045 (18)	0.002 (2)	0.0140 (18)
O13	0.066 (2)	0.0439 (18)	0.065 (2)	−0.0143 (16)	0.0052 (17)	−0.0058 (15)
Zn1	0.0839 (4)	0.0422 (3)	0.0447 (3)	−0.0037 (3)	0.0030 (3)	−0.0071 (2)
Zn2	0.0454 (3)	0.0147 (2)	0.0431 (3)	−0.00318 (17)	0.0004 (2)	−0.00419 (17)
Zn3	0.0716 (4)	0.0410 (3)	0.0603 (3)	−0.0153 (3)	0.0186 (3)	−0.0127 (2)

Geometric parameters (Å, º)

C1—N1	1.342 (6)	C44—C45	1.415 (6)
C1—C2	1.390 (7)	C44—H44	0.9300
C1—H1	0.9300	C45—H45	0.9300
C2—C3	1.382 (6)	C46—O12	1.229 (5)
C2—H2	0.9300	C46—O13	1.284 (6)
C3—C4	1.367 (6)	C46—C47	1.505 (6)
C3—C6	1.460 (6)	C46—Zn3	2.539 (5)
C4—C5	1.385 (7)	C47—C52	1.364 (6)
C4—H4	0.9300	C47—C48	1.384 (6)
C5—N1	1.321 (6)	C48—C49	1.390 (6)
C5—H5	0.9300	C48—H48	0.9300
C6—C7'	1.303 (15)	C49—C50	1.357 (6)
C6—C10	1.347 (11)	C49—H49	0.9300
C6—C7	1.405 (11)	C50—C51	1.386 (6)
C6—C10'	1.450 (15)	C50—N4	1.445 (5)
C7—C8	1.395 (13)	C51—C52	1.378 (6)
C7—H7	0.9300	C51—H51	0.9300
C8—N2	1.351 (10)	C52—H52	0.9300
C8—H8	0.9300	C56—N5	1.305 (5)
C9—N2	1.280 (11)	C56—C57	1.398 (6)
C9—C10	1.394 (14)	C56—H56	0.9300
C9—H9	0.9300	C57—C58	1.361 (6)
C10—H10	0.9300	C57—H57	0.9300
C7'—C8'	1.42 (2)	C58—C59	1.369 (6)
C7'—H7'	0.9300	C58—C58^ii	1.473 (7)
C8'—N2	1.168 (18)	C59—C60	1.386 (6)
C8'—H8'	0.9300	C59—H59	0.9300
C9'—N2	1.367 (15)	C60—N5	1.321 (5)
C9'—C10'	1.384 (18)	C60—H60	0.9300
C9'—H9'	0.9300	O14—C61	1.156 (7)
C10'—H10'	0.9300	O14—Zn3	2.204 (5)
C11—O3	1.219 (6)	C61—N6	1.424 (7)
C11—O2	1.285 (6)	C61—H61	0.9300
C11—C12	1.492 (7)	C62—N6	1.471 (7)
C12—C17	1.389 (6)	C62—H62A	0.9600
C12—C13	1.387 (7)	C62—H62B	0.9600
C13—C14	1.366 (7)	C62—H62C	0.9600
C13—H13	0.9300	C63—N6	1.431 (7)
C14—C15	1.392 (6)	C63—H63A	0.9600
C14—H14	0.9300	C63—H63B	0.9600
C15—C16	1.384 (6)	C63—H63C	0.9600
C15—N3	1.449 (6)	N7—C65	1.444 (7)
C16—C17	1.356 (7)	N7—C64	1.455 (8)
C16—H16	0.9300	N7—C66	1.493 (8)
C17—H17	0.9300	O1—C64	1.177 (8)
C18—O4	1.214 (7)	O1—Zn1	2.042 (6)
C18—O5	1.263 (7)	C64—H64	0.9300
C18—C19	1.515 (7)	C65—H65A	0.9600
C19—C20	1.319 (8)	C65—H65B	0.9600
C19—C24	1.366 (7)	C65—H65C	0.9600
C20—C21	1.407 (7)	C66—H66A	0.9600
C20—H20	0.9300	C66—H66B	0.9600
C21—C22	1.351 (7)	C66—H66C	0.9600
C21—H21	0.9300	O14'—C61'	1.168 (8)
C22—C23	1.385 (7)	O14'—Zn3	2.136 (6)
C22—N3	1.417 (6)	N6'—C61'	1.439 (8)
C23—C24	1.389 (7)	N6'—C63'	1.462 (8)
C23—H23	0.9300	N6'—C62'	1.465 (8)
C24—H24	0.9300	C61'—H61'	0.9300
C25—O7	1.238 (5)	C62'—H62D	0.9600
C25—O6	1.264 (5)	C62'—H62E	0.9600
C25—C26	1.495 (6)	C62'—H62F	0.9600
C26—C27	1.375 (6)	C63'—H63D	0.9600
C26—C31	1.385 (6)	C63'—H63E	0.9600
C27—C28	1.355 (6)	C63'—H63F	0.9600
C27—H27	0.9300	N7'—C65'	1.416 (8)
C28—C29	1.408 (6)	N7'—C64'	1.507 (8)
C28—H28	0.9300	N7'—C66'	1.482 (8)
C29—C30	1.361 (6)	O1'—C64'	1.218 (9)
C29—N3	1.401 (5)	O1'—Zn1	2.182 (7)
C30—C31	1.372 (6)	C64'—H64'	0.9300
C30—H30	0.9300	C65'—H65D	0.9600
C31—H31	0.9300	C65'—H65E	0.9600
C32—O9	1.250 (5)	C65'—H65F	0.9600
C32—O8	1.266 (5)	C66'—H66D	0.9600
C32—C33	1.491 (6)	C66'—H66E	0.9600
C33—C38	1.377 (6)	C66'—H66F	0.9600
C33—C34	1.399 (6)	N1—Zn3^iii	2.064 (4)
C34—C35	1.347 (6)	N2—Zn1	2.059 (4)
C34—H34	0.9300	N5—Zn2	2.015 (3)
C35—C36	1.399 (6)	O2—Zn1	1.946 (3)
C35—H35	0.9300	O5—Zn1^iv	1.949 (4)
C36—C37	1.396 (6)	O6—Zn2^v	2.049 (3)
C36—N4	1.404 (5)	O7—Zn2	2.037 (3)
C37—C38	1.340 (6)	O8—Zn2^v	2.029 (3)
C37—H37	0.9300	O9—Zn2	2.028 (3)
C38—H38	0.9300	O10—Zn3^i	2.328 (4)
C39—O10	1.233 (6)	O11—Zn3^i	2.044 (4)
C39—O11	1.274 (6)	O12—Zn3	2.410 (4)
C39—C40	1.493 (6)	O13—Zn3	2.001 (3)
C39—Zn3^i	2.520 (5)	Zn1—O5^i	1.949 (4)
C40—C45	1.353 (7)	Zn2—O8^v	2.029 (3)
C40—C41	1.389 (6)	Zn2—O6^v	2.049 (3)
C41—C42	1.372 (6)	Zn2—Zn2^v	2.8689 (9)
C41—H41	0.9300	Zn3—O11^iv	2.044 (4)
C42—C43	1.386 (6)	Zn3—N1^vi	2.064 (4)
C42—H42	0.9300	Zn3—O10^iv	2.328 (4)
C43—C44	1.388 (6)	Zn3—C39^iv	2.520 (5)
C43—N4	1.414 (5)
N1—C1—C2	122.4 (5)	N5—C56—H56	118.2
N1—C1—H1	118.8	C57—C56—H56	118.2
C2—C1—H1	118.8	C58—C57—C56	119.8 (4)
C3—C2—C1	120.3 (5)	C58—C57—H57	120.1
C3—C2—H2	119.9	C56—C57—H57	120.1
C1—C2—H2	119.9	C57—C58—C59	115.9 (3)
C4—C3—C2	116.9 (4)	C57—C58—C58^ii	121.9 (4)
C4—C3—C6	121.4 (4)	C59—C58—C58^ii	122.2 (5)
C2—C3—C6	121.7 (4)	C58—C59—C60	121.5 (4)
C3—C4—C5	119.6 (5)	C58—C59—H59	119.3
C3—C4—H4	120.2	C60—C59—H59	119.3
C5—C4—H4	120.2	N5—C60—C59	121.8 (4)
N1—C5—C4	124.3 (5)	N5—C60—H60	119.1
N1—C5—H5	117.8	C59—C60—H60	119.1
C4—C5—H5	117.8	C61—O14—Zn3	119.0 (5)
C10—C6—C7	117.0 (7)	O14—C61—N6	119.8 (7)
C7'—C6—C10'	114.9 (9)	O14—C61—H61	120.1
C7'—C6—C3	124.6 (8)	N6—C61—H61	120.1
C10—C6—C3	122.0 (6)	N6—C62—H62A	109.5
C7—C6—C3	120.5 (5)	N6—C62—H62B	109.5
C10'—C6—C3	120.2 (7)	H62A—C62—H62B	109.5
C8—C7—C6	118.7 (8)	N6—C62—H62C	109.5
C8—C7—H7	120.6	H62A—C62—H62C	109.5
C6—C7—H7	120.6	H62B—C62—H62C	109.5
N2—C8—C7	122.7 (8)	N6—C63—H63A	109.5
N2—C8—H8	118.6	N6—C63—H63B	109.5
C7—C8—H8	118.6	H63A—C63—H63B	109.5
N2—C9—C10	126.4 (9)	N6—C63—H63C	109.5
N2—C9—H9	116.8	H63A—C63—H63C	109.5
C10—C9—H9	116.8	H63B—C63—H63C	109.5
C6—C10—C9	118.5 (9)	C61—N6—C63	114.9 (6)
C6—C10—H10	120.7	C61—N6—C62	121.0 (6)
C9—C10—H10	120.7	C63—N6—C62	124.2 (6)
C6—C7'—C8'	118.8 (14)	C65—N7—C64	123.2 (6)
C6—C7'—H7'	120.6	C65—N7—C66	118.2 (6)
C8'—C7'—H7'	120.6	C64—N7—C66	118.6 (6)
N2—C8'—C7'	129.1 (15)	C64—O1—Zn1	115.1 (6)
N2—C8'—H8'	115.5	O1—C64—N7	108.0 (6)
C7'—C8'—H8'	115.5	O1—C64—H64	126.0
N2—C9'—C10'	121.9 (13)	N7—C64—H64	126.0
N2—C9'—H9'	119.0	N7—C65—H65A	109.5
C10'—C9'—H9'	119.0	N7—C65—H65B	109.5
C9'—C10'—C6	118.5 (12)	H65A—C65—H65B	109.5
C9'—C10'—H10'	120.8	N7—C65—H65C	109.5
C6—C10'—H10'	120.8	H65A—C65—H65C	109.5
O3—C11—O2	123.9 (5)	H65B—C65—H65C	109.5
O3—C11—C12	121.4 (5)	N7—C66—H66A	109.5
O2—C11—C12	114.7 (5)	N7—C66—H66B	109.5
C17—C12—C13	116.9 (4)	H66A—C66—H66B	109.5
C17—C12—C11	120.8 (5)	N7—C66—H66C	109.5
C13—C12—C11	122.3 (4)	H66A—C66—H66C	109.5
C14—C13—C12	122.7 (5)	H66B—C66—H66C	109.5
C14—C13—H13	118.7	C61'—O14'—Zn3	115.3 (7)
C12—C13—H13	118.7	C61'—N6'—C63'	110.1 (7)
C13—C14—C15	119.0 (5)	C61'—N6'—C62'	117.0 (8)
C13—C14—H14	120.5	C63'—N6'—C62'	132.8 (8)
C15—C14—H14	120.5	O14'—C61'—N6'	119.9 (9)
C14—C15—C16	119.1 (4)	O14'—C61'—H61'	120.0
C14—C15—N3	118.7 (4)	N6'—C61'—H61'	120.0
C16—C15—N3	122.2 (4)	N6'—C62'—H62D	109.5
C17—C16—C15	120.7 (5)	N6'—C62'—H62E	109.5
C17—C16—H16	119.6	H62D—C62'—H62E	109.5
C15—C16—H16	119.6	N6'—C62'—H62F	109.5
C16—C17—C12	121.5 (5)	H62D—C62'—H62F	109.5
C16—C17—H17	119.2	H62E—C62'—H62F	109.5
C12—C17—H17	119.2	N6'—C63'—H63D	109.5
O4—C18—O5	121.5 (5)	N6'—C63'—H63E	109.5
O4—C18—C19	121.0 (6)	H63D—C63'—H63E	109.5
O5—C18—C19	117.5 (5)	N6'—C63'—H63F	109.5
C20—C19—C24	119.1 (5)	H63D—C63'—H63F	109.5
C20—C19—C18	120.2 (5)	H63E—C63'—H63F	109.5
C24—C19—C18	120.7 (5)	C65'—N7'—C64'	121.9 (6)
C19—C20—C21	121.0 (5)	C65'—N7'—C66'	124.0 (6)
C19—C20—H20	119.5	C64'—N7'—C66'	114.2 (6)
C21—C20—H20	119.5	C64'—O1'—Zn1	120.5 (8)
C22—C21—C20	120.8 (5)	O1'—C64'—N7'	113.6 (7)
C22—C21—H21	119.6	O1'—C64'—H64'	123.2
C20—C21—H21	119.6	N7'—C64'—H64'	123.2
C21—C22—C23	118.5 (5)	N7'—C65'—H65D	109.5
C21—C22—N3	121.2 (5)	N7'—C65'—H65E	109.5
C23—C22—N3	120.2 (5)	H65D—C65'—H65E	109.5
C22—C23—C24	119.3 (5)	N7'—C65'—H65F	109.5
C22—C23—H23	120.4	H65D—C65'—H65F	109.5
C24—C23—H23	120.4	H65E—C65'—H65F	109.5
C19—C24—C23	121.4 (6)	N7'—C66'—H66D	109.5
C19—C24—H24	119.3	N7'—C66'—H66E	109.5
C23—C24—H24	119.3	H66D—C66'—H66E	109.5
O7—C25—O6	125.4 (4)	N7'—C66'—H66F	109.5
O7—C25—C26	117.8 (4)	H66D—C66'—H66F	109.5
O6—C25—C26	116.8 (4)	H66E—C66'—H66F	109.5
C27—C26—C31	117.4 (4)	C5—N1—C1	116.5 (4)
C27—C26—C25	122.5 (4)	C5—N1—Zn3^iii	120.6 (3)
C31—C26—C25	120.0 (4)	C1—N1—Zn3^iii	122.9 (3)
C28—C27—C26	121.3 (4)	C9—N2—C8	115.2 (7)
C28—C27—H27	119.3	C8'—N2—C9'	115.0 (11)
C26—C27—H27	119.3	C8'—N2—Zn1	124.2 (9)
C27—C28—C29	121.3 (4)	C9—N2—Zn1	126.9 (5)
C27—C28—H28	119.4	C8—N2—Zn1	117.4 (5)
C29—C28—H28	119.4	C9'—N2—Zn1	120.6 (7)
C30—C29—N3	121.9 (4)	C29—N3—C22	119.6 (4)
C30—C29—C28	117.1 (4)	C29—N3—C15	120.6 (4)
N3—C29—C28	121.0 (4)	C22—N3—C15	119.3 (4)
C29—C30—C31	121.4 (4)	C36—N4—C43	121.2 (4)
C29—C30—H30	119.3	C36—N4—C50	120.3 (4)
C31—C30—H30	119.3	C43—N4—C50	118.4 (3)
C30—C31—C26	121.4 (4)	C56—N5—C60	117.4 (3)
C30—C31—H31	119.3	C56—N5—Zn2	121.7 (3)
C26—C31—H31	119.3	C60—N5—Zn2	120.9 (3)
O9—C32—O8	124.0 (4)	C11—O2—Zn1	113.7 (3)
O9—C32—C33	118.1 (4)	C18—O5—Zn1^iv	106.6 (4)
O8—C32—C33	117.9 (4)	C25—O6—Zn2^v	128.8 (3)
C38—C33—C34	117.3 (4)	C25—O7—Zn2	123.8 (3)
C38—C33—C32	122.4 (4)	C32—O8—Zn2^v	128.4 (3)
C34—C33—C32	120.3 (4)	C32—O9—Zn2	124.6 (3)
C35—C34—C33	121.6 (4)	C39—O10—Zn3^i	84.1 (3)
C35—C34—H34	119.2	C39—O11—Zn3^i	96.1 (4)
C33—C34—H34	119.2	C46—O12—Zn3	81.5 (3)
C34—C35—C36	120.9 (4)	C46—O13—Zn3	98.9 (3)
C34—C35—H35	119.6	O2—Zn1—O5^i	136.29 (17)
C36—C35—H35	119.6	O2—Zn1—O1	109.0 (3)
C37—C36—C35	116.7 (4)	O5^i—Zn1—O1	99.2 (3)
C37—C36—N4	121.9 (4)	O2—Zn1—N2	97.21 (16)
C35—C36—N4	121.4 (4)	O5^i—Zn1—N2	112.91 (17)
C38—C37—C36	122.0 (4)	O1—Zn1—N2	95.4 (3)
C38—C37—H37	119.0	O2—Zn1—O1'	111.6 (4)
C36—C37—H37	119.0	O5^i—Zn1—O1'	94.7 (4)
C37—C38—C33	121.5 (4)	N2—Zn1—O1'	99.1 (4)
C37—C38—H38	119.3	N5—Zn2—O9	100.62 (13)
C33—C38—H38	119.3	N5—Zn2—O8^v	97.88 (13)
O10—C39—O11	120.5 (5)	O9—Zn2—O8^v	161.34 (12)
O10—C39—C40	121.5 (5)	N5—Zn2—O7	98.21 (13)
O11—C39—C40	118.0 (5)	O9—Zn2—O7	87.29 (13)
O10—C39—Zn3^i	66.8 (3)	O8^v—Zn2—O7	87.66 (14)
O11—C39—Zn3^i	53.8 (3)	N5—Zn2—O6^v	100.14 (13)
C40—C39—Zn3^i	171.8 (4)	O9—Zn2—O6^v	87.48 (12)
C45—C40—C41	118.0 (4)	O8^v—Zn2—O6^v	91.69 (13)
C45—C40—C39	121.8 (5)	O7—Zn2—O6^v	161.55 (12)
C41—C40—C39	120.2 (5)	N5—Zn2—Zn2^v	176.77 (10)
C42—C41—C40	121.2 (5)	O9—Zn2—Zn2^v	82.28 (9)
C42—C41—H41	119.4	O8^v—Zn2—Zn2^v	79.29 (9)
C40—C41—H41	119.4	O7—Zn2—Zn2^v	83.31 (8)
C41—C42—C43	120.5 (4)	O6^v—Zn2—Zn2^v	78.46 (8)
C41—C42—H42	119.7	O13—Zn3—O11^iv	148.95 (15)
C43—C42—H42	119.7	O13—Zn3—N1^vi	105.89 (14)
C42—C43—C44	119.5 (4)	O11^iv—Zn3—N1^vi	97.21 (16)
C42—C43—N4	121.3 (4)	O13—Zn3—O14'	107.8 (2)
C44—C43—N4	119.2 (4)	O11^iv—Zn3—O14'	92.6 (2)
C43—C44—C45	118.0 (5)	N1^vi—Zn3—O14'	89.5 (2)
C43—C44—H44	121.0	O13—Zn3—O14	88.29 (18)
C45—C44—H44	121.0	O11^iv—Zn3—O14	111.72 (19)
C40—C45—C44	122.6 (5)	N1^vi—Zn3—O14	91.93 (17)
C40—C45—H45	118.7	O13—Zn3—O10^iv	97.07 (14)
C44—C45—H45	118.7	O11^iv—Zn3—O10^iv	59.28 (15)
O12—C46—O13	121.0 (4)	N1^vi—Zn3—O10^iv	156.33 (15)
O12—C46—C47	120.9 (5)	O14'—Zn3—O10^iv	88.9 (2)
O13—C46—C47	118.0 (4)	O14—Zn3—O10^iv	94.46 (15)
O12—C46—Zn3	69.9 (3)	O13—Zn3—O12	58.59 (12)
O13—C46—Zn3	51.2 (2)	O11^iv—Zn3—O12	99.75 (15)
C47—C46—Zn3	168.9 (4)	N1^vi—Zn3—O12	94.55 (14)
C52—C47—C48	118.5 (4)	O14'—Zn3—O12	166.4 (2)
C52—C47—C46	121.0 (4)	O14—Zn3—O12	146.76 (17)
C48—C47—C46	120.5 (4)	O10^iv—Zn3—O12	92.51 (13)
C49—C48—C47	120.5 (4)	O13—Zn3—C39^iv	123.62 (17)
C49—C48—H48	119.7	O11^iv—Zn3—C39^iv	30.17 (17)
C47—C48—H48	119.7	N1^vi—Zn3—C39^iv	127.36 (18)
C50—C49—C48	120.3 (4)	O14'—Zn3—C39^iv	91.3 (2)
C50—C49—H49	119.8	O14—Zn3—C39^iv	105.26 (18)
C48—C49—H49	119.8	O10^iv—Zn3—C39^iv	29.13 (15)
C49—C50—C51	119.4 (4)	O12—Zn3—C39^iv	96.47 (14)
C49—C50—N4	119.6 (4)	O13—Zn3—C46	29.99 (14)
C51—C50—N4	121.0 (4)	O11^iv—Zn3—C46	125.23 (17)
C52—C51—C50	119.9 (5)	N1^vi—Zn3—C46	101.95 (14)
C52—C51—H51	120.0	O14'—Zn3—C46	137.8 (2)
C50—C51—H51	120.0	O14—Zn3—C46	118.26 (19)
C47—C52—C51	121.3 (5)	O10^iv—Zn3—C46	95.02 (14)
C47—C52—H52	119.4	O12—Zn3—C46	28.60 (13)
C51—C52—H52	119.4	C39^iv—Zn3—C46	111.76 (16)
N5—C56—C57	123.6 (4)
N1—C1—C2—C3	−1.4 (8)	C43—C44—C45—C40	−2.1 (8)
C1—C2—C3—C4	−0.4 (8)	O12—C46—C47—C52	2.0 (7)
C1—C2—C3—C6	179.1 (5)	O13—C46—C47—C52	−176.4 (4)
C2—C3—C4—C5	1.0 (8)	Zn3—C46—C47—C52	−163.4 (14)
C6—C3—C4—C5	−178.5 (5)	O12—C46—C47—C48	−179.5 (4)
C3—C4—C5—N1	0.1 (10)	O13—C46—C47—C48	2.1 (6)
C4—C3—C6—C7'	−148.4 (11)	Zn3—C46—C47—C48	15.1 (18)
C2—C3—C6—C7'	32.1 (13)	C52—C47—C48—C49	−0.6 (7)
C4—C3—C6—C10	−28.4 (11)	C46—C47—C48—C49	−179.1 (4)
C2—C3—C6—C10	152.1 (9)	C47—C48—C49—C50	−0.7 (7)
C4—C3—C6—C7	159.9 (8)	C48—C49—C50—C51	2.1 (7)
C2—C3—C6—C7	−19.6 (10)	C48—C49—C50—N4	−179.9 (4)
C4—C3—C6—C10'	25.8 (11)	C49—C50—C51—C52	−2.3 (8)
C2—C3—C6—C10'	−153.7 (10)	N4—C50—C51—C52	179.8 (5)
C7'—C6—C7—C8	72.0 (14)	C48—C47—C52—C51	0.5 (7)
C10—C6—C7—C8	9.5 (16)	C46—C47—C52—C51	179.0 (5)
C10'—C6—C7—C8	−38.4 (14)	C50—C51—C52—C47	1.0 (8)
C3—C6—C7—C8	−178.3 (9)	N5—C56—C57—C58	−0.9 (10)
C6—C7—C8—N2	−1.1 (19)	C56—C57—C58—C59	0.0 (8)
C7'—C6—C10—C9	−45.3 (15)	C56—C57—C58—C58^ii	−178.2 (6)
C7—C6—C10—C9	−7.8 (17)	C57—C58—C59—C60	−0.4 (8)
C10'—C6—C10—C9	77.4 (14)	C58^ii—C58—C59—C60	177.8 (6)
C3—C6—C10—C9	−179.8 (10)	C58—C59—C60—N5	1.8 (9)
N2—C9—C10—C6	−3 (2)	Zn3—O14—C61—N6	−170.5 (3)
C10—C6—C7'—C8'	43.7 (18)	O14—C61—N6—C63	−0.2 (3)
C7—C6—C7'—C8'	−84.0 (17)	O14—C61—N6—C62	179.2 (3)
C10'—C6—C7'—C8'	2 (2)	Zn1—O1—C64—N7	172.6 (6)
C3—C6—C7'—C8'	176.4 (13)	C65—N7—C64—O1	179.94 (19)
C6—C7'—C8'—N2	12 (3)	C66—N7—C64—O1	0.2 (3)
N2—C9'—C10'—C6	4 (3)	Zn3—O14'—C61'—N6'	179.4 (4)
C7'—C6—C10'—C9'	−8 (2)	C63'—N6'—C61'—O14'	7.6 (6)
C10—C6—C10'—C9'	−75.9 (17)	C62'—N6'—C61'—O14'	−172.4 (6)
C7—C6—C10'—C9'	37.2 (18)	Zn1—O1'—C64'—N7'	170.2 (6)
C3—C6—C10'—C9'	177.3 (13)	C65'—N7'—C64'—O1'	−172.5 (12)
O3—C11—C12—C17	−8.7 (8)	C66'—N7'—C64'—O1'	7.5 (12)
O2—C11—C12—C17	170.7 (5)	C4—C5—N1—C1	−1.8 (9)
O3—C11—C12—C13	173.4 (6)	C4—C5—N1—Zn3^iii	176.8 (5)
O2—C11—C12—C13	−7.2 (7)	C2—C1—N1—C5	2.4 (8)
C17—C12—C13—C14	0.2 (8)	C2—C1—N1—Zn3^iii	−176.1 (4)
C11—C12—C13—C14	178.1 (5)	C7'—C8'—N2—C9	−57 (2)
C12—C13—C14—C15	1.0 (9)	C7'—C8'—N2—C8	72 (2)
C13—C14—C15—C16	−0.5 (8)	C7'—C8'—N2—C9'	−16 (3)
C13—C14—C15—N3	−178.9 (5)	C7'—C8'—N2—Zn1	169.8 (16)
C14—C15—C16—C17	−1.3 (8)	C10—C9—N2—C8'	51.5 (17)
N3—C15—C16—C17	177.0 (5)	C10—C9—N2—C8	11.4 (19)
C15—C16—C17—C12	2.6 (9)	C10—C9—N2—C9'	−76.3 (16)
C13—C12—C17—C16	−2.0 (8)	C10—C9—N2—Zn1	−177.1 (11)
C11—C12—C17—C16	−180.0 (5)	C7—C8—N2—C8'	−68.7 (16)
O4—C18—C19—C20	−9.5 (9)	C7—C8—N2—C9	−9.0 (17)
O5—C18—C19—C20	169.7 (6)	C7—C8—N2—C9'	41.9 (16)
O4—C18—C19—C24	173.0 (6)	C7—C8—N2—Zn1	178.6 (10)
O5—C18—C19—C24	−7.9 (8)	C10'—C9'—N2—C8'	8 (2)
C24—C19—C20—C21	−0.5 (10)	C10'—C9'—N2—C9	68.1 (17)
C18—C19—C20—C21	−178.1 (5)	C10'—C9'—N2—C8	−42.7 (19)
C19—C20—C21—C22	1.0 (10)	C10'—C9'—N2—Zn1	−177.7 (13)
C20—C21—C22—C23	0.0 (9)	C30—C29—N3—C22	−27.8 (8)
C20—C21—C22—N3	177.9 (5)	C28—C29—N3—C22	152.8 (5)
C21—C22—C23—C24	−1.3 (9)	C30—C29—N3—C15	144.6 (5)
N3—C22—C23—C24	−179.2 (6)	C28—C29—N3—C15	−34.8 (8)
C20—C19—C24—C23	−0.8 (10)	C21—C22—N3—C29	−47.7 (8)
C18—C19—C24—C23	176.7 (6)	C23—C22—N3—C29	130.1 (6)
C22—C23—C24—C19	1.8 (10)	C21—C22—N3—C15	139.7 (6)
O7—C25—C26—C27	−166.3 (4)	C23—C22—N3—C15	−42.5 (8)
O6—C25—C26—C27	14.3 (6)	C14—C15—N3—C29	140.7 (5)
O7—C25—C26—C31	18.1 (6)	C16—C15—N3—C29	−37.6 (8)
O6—C25—C26—C31	−161.3 (4)	C14—C15—N3—C22	−46.8 (7)
C31—C26—C27—C28	−1.6 (7)	C16—C15—N3—C22	134.9 (5)
C25—C26—C27—C28	−177.3 (5)	C37—C36—N4—C43	23.0 (7)
C26—C27—C28—C29	4.2 (8)	C35—C36—N4—C43	−156.2 (5)
C27—C28—C29—C30	−4.0 (8)	C37—C36—N4—C50	−154.9 (5)
C27—C28—C29—N3	175.5 (5)	C35—C36—N4—C50	25.9 (7)
N3—C29—C30—C31	−178.2 (5)	C42—C43—N4—C36	47.6 (7)
C28—C29—C30—C31	1.2 (8)	C44—C43—N4—C36	−135.4 (5)
C29—C30—C31—C26	1.3 (8)	C42—C43—N4—C50	−134.4 (5)
C27—C26—C31—C30	−1.2 (7)	C44—C43—N4—C50	42.5 (7)
C25—C26—C31—C30	174.7 (4)	C49—C50—N4—C36	−124.9 (5)
O9—C32—C33—C38	161.9 (4)	C51—C50—N4—C36	53.0 (7)
O8—C32—C33—C38	−16.4 (7)	C49—C50—N4—C43	57.2 (6)
O9—C32—C33—C34	−14.6 (6)	C51—C50—N4—C43	−124.9 (5)
O8—C32—C33—C34	167.1 (4)	C57—C56—N5—C60	2.2 (9)
C38—C33—C34—C35	2.4 (7)	C57—C56—N5—Zn2	−177.5 (5)
C32—C33—C34—C35	179.1 (5)	C59—C60—N5—C56	−2.6 (8)
C33—C34—C35—C36	−4.4 (8)	C59—C60—N5—Zn2	177.1 (4)
C34—C35—C36—C37	3.5 (8)	O3—C11—O2—Zn1	1.6 (7)
C34—C35—C36—N4	−177.2 (5)	C12—C11—O2—Zn1	−177.8 (3)
C35—C36—C37—C38	−0.8 (8)	O4—C18—O5—Zn1^iv	4.8 (7)
N4—C36—C37—C38	180.0 (5)	C19—C18—O5—Zn1^iv	−174.3 (4)
C36—C37—C38—C33	−1.1 (9)	O7—C25—O6—Zn2^v	−4.9 (7)
C34—C33—C38—C37	0.4 (8)	C26—C25—O6—Zn2^v	174.4 (3)
C32—C33—C38—C37	−176.3 (5)	O6—C25—O7—Zn2	0.3 (6)
O10—C39—C40—C45	−173.3 (5)	C26—C25—O7—Zn2	−179.0 (3)
O11—C39—C40—C45	4.8 (7)	O9—C32—O8—Zn2^v	−11.2 (7)
O10—C39—C40—C41	5.7 (7)	C33—C32—O8—Zn2^v	167.0 (3)
O11—C39—C40—C41	−176.2 (5)	O8—C32—O9—Zn2	15.4 (6)
C45—C40—C41—C42	−2.2 (7)	C33—C32—O9—Zn2	−162.7 (3)
C39—C40—C41—C42	178.8 (4)	O11—C39—O10—Zn3^i	1.7 (5)
C40—C41—C42—C43	−1.7 (7)	C40—C39—O10—Zn3^i	179.7 (4)
C41—C42—C43—C44	3.7 (7)	O10—C39—O11—Zn3^i	−1.9 (5)
C41—C42—C43—N4	−179.3 (4)	C40—C39—O11—Zn3^i	180.0 (4)
C42—C43—C44—C45	−1.9 (7)	O13—C46—O12—Zn3	1.3 (4)
N4—C43—C44—C45	−178.9 (4)	C47—C46—O12—Zn3	−177.0 (4)
C41—C40—C45—C44	4.1 (8)	O12—C46—O13—Zn3	−1.6 (5)
C39—C40—C45—C44	−176.9 (5)	C47—C46—O13—Zn3	176.8 (3)

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