Structural analysis of inter­penetrated methyl-modified MOF-5 and its gas-adsorption properties

The first example of an inter­penetrated methyl-modified MOF-5 with the for­mula Zn₄O(DMBDC)₃(DMF)₂, where DMBDC²⁻ is 2,5-di­methyl­ben­zene-1,4-di­carboxyl­ate and DMF is N,N-di­methyl­formamide (henceforth denoted as Me₂MOF-5-int), namely, poly[tris­(μ₄-2,5-di­methyl­benzene-1,4-di­carboxyl­ato)bis­(N,N-di­methyl­formamide)-μ₄-oxido-tetra­zinc(II)], [Zn₄(C₁₀H₈O₄)₃O(C₃H₇NO)₂]_n, has been obtained from a solvothermal synthesis of 2,5-di­methyl­benzene-1,4-dicarboxylic acid and Zn(NO₃)₂·6H₂O in DMF. A systematic study revealed that the choice of solvent is of critical importance for the synthesis of phase-pure Me₂MOF-5-int, which was thoroughly characterized by single-crystal and powder X-ray diffraction (PXRD), as well as by gas-adsorption analyses. The Brunauer–Emmett–Teller surface area of Me₂MOF-5-int (660 m² g⁻¹), determined by N₂ adsorption, is much lower than that of nonpenetrated Me₂MOF-5 (2420 m² g⁻¹). However, Me₂MOF-5-int displays an H₂ uptake capacity of 1.26 wt% at 77 K and 1.0 bar, which is com­parable to that of non-inter­penetrated Me₂MOF-5 (1.51 wt%).

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

Poly[tris(µ₄-2,5-dimethylbenzene-1,4-dicarboxylato)bis(N,N-dimethylformamide)-µ₄-oxido-tetrazinc(II)]

Crystal data

[Zn4(C10H8O4)3O(C3H7NO)2]	F(000) = 4064
Mr = 1000.16	Dx = 1.584 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.8530 (9) Å	Cell parameters from 6314 reflections
b = 18.5810 (11) Å	θ = 2.5–29.9°
c = 25.3020 (15) Å	µ = 2.33 mm^−1
β = 91.504 (2)°	T = 103 K
V = 8390.5 (8) Å^3	Block, colourless
Z = 8	0.10 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	14438 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.069
φ and ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −22→23
Tmin = 0.883, Tmax = 1.000	k = −23→24
76309 measured reflections	l = −32→32
19165 independent reflections

Refinement

Refinement on F^2	66 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0296P)^2 + 22.8476P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
19165 reflections	Δρmax = 1.23 e Å^−3
1064 parameters	Δρmin = −0.84 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.

Refinement. The diffraction data for Me₂MOF-5-int were collected using a Bruker APEXII diffractometer equipped with an APEX II CCD detector using Mo-Ka radiation (l = 0.71073 Å). The structure was solved using a direct method (SHELXT) and refined by a full-matrix least-squares method on F² for all reflections using the program SHELXL2018 (Sheldrick, 2015b). All hydrogen atoms were placed using AFIX instructions, while all other atoms were refined anisotropically. Supplementary crystallographic data were deposited at the Cambridge Crystallographic Data Centre (CCDC) under reference number CCDC-1972122, and this data can be obtained free of charge at www.ccdc.cam.ac.uk/data_request.cif.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.74714 (12)	0.69517 (12)	0.25161 (9)	0.0064 (5)
Zn1	0.74815 (2)	0.61997 (2)	0.19865 (2)	0.00622 (8)
Zn2	0.83670 (2)	0.69352 (2)	0.29501 (2)	0.00592 (8)
Zn3	0.66094 (2)	0.68483 (2)	0.29543 (2)	0.00663 (8)
Zn4	0.73605 (2)	0.78890 (2)	0.21286 (2)	0.00708 (8)
O2	0.66429 (13)	0.55307 (13)	0.20670 (10)	0.0141 (5)
C1	0.61568 (19)	0.55029 (19)	0.24245 (14)	0.0110 (7)
O3	0.61241 (14)	0.59172 (14)	0.28139 (10)	0.0146 (5)
C2	0.55846 (19)	0.49102 (19)	0.23734 (14)	0.0104 (7)
C3	0.4903 (2)	0.4931 (2)	0.26421 (16)	0.0172 (8)
C4	0.4410 (2)	0.4353 (2)	0.25557 (16)	0.0191 (9)
H39	0.393835	0.436272	0.272144	0.023*
C5	0.45769 (19)	0.3767 (2)	0.22396 (15)	0.0131 (7)
C6	0.5265 (2)	0.3743 (2)	0.19787 (15)	0.0132 (7)
C7	0.5742 (2)	0.4329 (2)	0.20481 (15)	0.0136 (8)
H40	0.619842	0.433335	0.186359	0.016*
C8	0.4663 (3)	0.5534 (3)	0.3002 (2)	0.0411 (14)
H41	0.414272	0.545655	0.310269	0.062*
H42	0.470297	0.599470	0.281692	0.062*
H43	0.498792	0.554026	0.332047	0.062*
C9	0.5499 (2)	0.3136 (2)	0.16181 (17)	0.0227 (9)
H44	0.593852	0.328527	0.142104	0.034*
H45	0.508633	0.302173	0.136953	0.034*
H46	0.562462	0.270994	0.183057	0.034*
O4	0.42034 (13)	0.25573 (14)	0.20743 (11)	0.0156 (5)
C10	0.3989 (2)	0.3181 (2)	0.21972 (14)	0.0130 (7)
O5	0.33259 (13)	0.33477 (14)	0.23001 (11)	0.0158 (6)
O6	0.69154 (14)	0.68903 (14)	0.37151 (10)	0.0156 (6)
C11	0.7537 (2)	0.70385 (19)	0.39331 (14)	0.0113 (7)
O7	0.81628 (14)	0.70118 (15)	0.37056 (10)	0.0165 (6)
C12	0.7559 (2)	0.7260 (2)	0.45050 (14)	0.0142 (8)
C13	0.8237 (2)	0.7172 (2)	0.47887 (15)	0.0173 (8)
H47	0.864989	0.696732	0.461365	0.021*
C14	0.8331 (2)	0.7372 (2)	0.53142 (15)	0.0198 (9)
C15	0.7720 (2)	0.7698 (2)	0.55561 (15)	0.0163 (8)
C16	0.7062 (2)	0.7807 (2)	0.52743 (16)	0.0208 (9)
H48	0.666266	0.804417	0.544440	0.025*
C17	0.6950 (2)	0.7589 (2)	0.47521 (15)	0.0195 (9)
C18	0.6197 (2)	0.7731 (3)	0.44856 (18)	0.0368 (13)
H49	0.588479	0.801254	0.472257	0.055*
H50	0.594878	0.727227	0.440364	0.055*
H51	0.626776	0.800058	0.415783	0.055*
C19	0.9088 (2)	0.7254 (3)	0.55857 (17)	0.0328 (11)
H52	0.907841	0.680500	0.578869	0.049*
H53	0.919924	0.765718	0.582462	0.049*
H54	0.947495	0.722332	0.531913	0.049*
C20	0.77595 (19)	0.7935 (2)	0.61308 (14)	0.0143 (8)
O8	0.74955 (15)	0.85483 (14)	0.62340 (10)	0.0154 (6)
O9	0.80237 (14)	0.75048 (15)	0.64700 (10)	0.0163 (6)
O10	0.82967 (13)	0.84375 (13)	0.23941 (10)	0.0127 (5)
C21	0.89052 (19)	0.83015 (19)	0.26232 (14)	0.0108 (7)
O11	0.90789 (14)	0.77170 (14)	0.28458 (11)	0.0160 (6)
C22	0.94907 (19)	0.88921 (19)	0.26278 (15)	0.0127 (7)
C23	0.93687 (19)	0.9466 (2)	0.22813 (15)	0.0135 (8)
H55	0.892151	0.946577	0.206937	0.016*
C24	0.9859 (2)	1.0037 (2)	0.22272 (15)	0.0138 (8)
C25	1.0512 (2)	1.00305 (19)	0.25513 (14)	0.0124 (7)
C26	1.0625 (2)	0.9470 (2)	0.29099 (16)	0.0185 (8)
H56	1.106037	0.948339	0.313375	0.022*
C27	1.0133 (2)	0.8889 (2)	0.29589 (16)	0.0178 (8)
C28	0.9648 (2)	1.0624 (2)	0.18331 (18)	0.0278 (10)
H57	0.915633	1.051657	0.167022	0.042*
H58	1.002403	1.064671	0.155850	0.042*
H59	0.962663	1.108813	0.201632	0.042*
C29	1.0321 (3)	0.8319 (3)	0.3367 (2)	0.0369 (13)
H60	1.044273	0.786763	0.318878	0.055*
H61	0.988971	0.824429	0.359252	0.055*
H62	1.075261	0.847633	0.358497	0.055*
O12	1.10518 (14)	1.10574 (14)	0.21639 (10)	0.0156 (6)
C30	1.11001 (18)	1.06096 (19)	0.25360 (14)	0.0106 (7)
O13	1.16027 (14)	1.06050 (14)	0.28960 (10)	0.0156 (6)
O14	0.71142 (14)	0.87651 (15)	0.16365 (11)	0.0200 (6)
C31	0.7600 (2)	0.9021 (2)	0.13546 (16)	0.0222 (9)
H63	0.810219	0.886839	0.141723	0.027*
N1	0.7472 (2)	0.9490 (2)	0.09730 (15)	0.0356 (10)
C32	0.8084 (4)	0.9761 (4)	0.0651 (2)	0.0625 (19)
H64	0.856108	0.955917	0.078240	0.094*
H65	0.810261	1.028678	0.067410	0.094*
H66	0.799721	0.961652	0.028197	0.094*
C33	0.6723 (3)	0.9739 (3)	0.0852 (3)	0.0606 (18)
H67	0.654085	0.951783	0.052093	0.091*
H68	0.672625	1.026333	0.081284	0.091*
H69	0.639304	0.960394	0.113882	0.091*
C34	0.5928 (2)	0.7645 (3)	0.14705 (19)	0.0346 (12)
H70	0.603446	0.810790	0.133253	0.052*	0.745 (8)
H71	0.612266	0.784740	0.115785	0.052*	0.255 (8)
N2A	0.5309 (3)	0.7319 (4)	0.1297 (3)	0.0447 (18)	0.745 (8)
N2B	0.5146 (12)	0.7656 (14)	0.1530 (10)	0.057 (3)	0.255 (8)
O15	0.63663 (14)	0.73940 (14)	0.17902 (11)	0.0183 (6)
C35A	0.4848 (4)	0.7595 (5)	0.0867 (3)	0.057 (2)	0.745 (8)
H72	0.442025	0.727294	0.080454	0.085*	0.745 (8)
H73	0.466710	0.807582	0.095773	0.085*	0.745 (8)
H74	0.514462	0.762228	0.054745	0.085*	0.745 (8)
C35B	0.4576 (13)	0.8128 (14)	0.1324 (11)	0.060 (4)	0.255 (8)
H75	0.408698	0.797285	0.144867	0.090*	0.255 (8)
H76	0.467833	0.862000	0.144522	0.090*	0.255 (8)
H77	0.457375	0.811414	0.093672	0.090*	0.255 (8)
C36	0.4981 (4)	0.6781 (5)	0.1634 (4)	0.100 (2)
H78	0.452872	0.658497	0.145983	0.150*	0.745 (8)
H79	0.534284	0.639259	0.169927	0.150*	0.745 (8)
H80	0.484934	0.700149	0.197108	0.150*	0.745 (8)
H81	0.444388	0.670683	0.168357	0.150*	0.255 (8)
H82	0.514127	0.650231	0.132835	0.150*	0.255 (8)
H83	0.526133	0.662223	0.195115	0.150*	0.255 (8)
O16	0.24938 (12)	0.74791 (12)	0.01387 (9)	0.0083 (5)
Zn5	0.24390 (2)	0.66382 (2)	0.06287 (2)	0.01125 (9)
Zn6	0.15880 (2)	0.74767 (2)	−0.02957 (2)	0.01027 (9)
Zn7	0.25138 (2)	0.83523 (2)	0.05389 (2)	0.00887 (9)
Zn8	0.33704 (2)	0.74856 (2)	−0.02806 (2)	0.00890 (9)
O17	0.33585 (15)	0.60670 (15)	0.03966 (11)	0.0222 (6)
C37	0.3876 (2)	0.6116 (2)	0.00808 (16)	0.0181 (8)
O18	0.39698 (16)	0.66344 (16)	−0.02418 (13)	0.0297 (7)
C38	0.4449 (2)	0.5521 (2)	0.00557 (17)	0.0217 (9)
C39	0.4881 (2)	0.5495 (2)	−0.03949 (19)	0.0286 (10)
H31	0.479481	0.584429	−0.066419	0.034*
C40	0.4563 (2)	0.5023 (2)	0.04666 (19)	0.0283 (10)
C41	0.4128 (3)	0.4992 (3)	0.0972 (2)	0.0478 (16)
H1	0.364155	0.476311	0.090112	0.072*
H2	0.405138	0.548123	0.110459	0.072*
H3	0.441109	0.471135	0.123782	0.072*
O19	0.17434 (15)	0.60462 (15)	0.00584 (13)	0.0254 (7)
C42	0.1072 (2)	0.6154 (2)	−0.00806 (16)	0.0208 (9)
O20	0.08075 (15)	0.67533 (15)	−0.02315 (12)	0.0244 (7)
C43	0.0529 (2)	0.5541 (2)	−0.00562 (17)	0.0222 (9)
C44	−0.0169 (2)	0.5684 (2)	0.01477 (19)	0.0299 (11)
H32	−0.028352	0.616534	0.024282	0.036*
C45	−0.0709 (2)	0.5156 (2)	0.0219 (2)	0.0299 (11)
C46	−0.1427 (3)	0.5350 (3)	0.0501 (2)	0.0460 (15)
H4	−0.132054	0.572925	0.076151	0.069*
H5	−0.161773	0.492308	0.068112	0.069*
H6	−0.180301	0.552125	0.024179	0.069*
O21	0.10617 (17)	0.83972 (16)	−0.02433 (13)	0.0318 (8)
O22	0.16034 (16)	0.89177 (16)	0.04551 (12)	0.0283 (7)
C47	0.1111 (2)	0.8881 (2)	0.00957 (15)	0.0145 (8)
C48	0.0543 (2)	0.9477 (2)	0.00687 (15)	0.0149 (8)
C49	0.0587 (2)	1.0089 (2)	0.03908 (16)	0.0169 (8)
C50	0.0035 (2)	1.0602 (2)	0.03106 (15)	0.0157 (8)
H33	0.004853	1.102442	0.052166	0.019*
C51	0.1189 (2)	1.0235 (2)	0.08125 (17)	0.0241 (9)
H7	0.111549	1.071585	0.096153	0.036*
H8	0.168382	1.020894	0.065461	0.036*
H9	0.115650	0.987423	0.109349	0.036*
C52	0.3891 (2)	0.8880 (2)	0.00708 (14)	0.0135 (8)
O23	0.32577 (16)	0.90266 (15)	0.02487 (13)	0.0278 (7)
O24	0.40699 (15)	0.82778 (15)	−0.01117 (12)	0.0239 (7)
C53	0.4456 (2)	0.9469 (2)	0.00561 (15)	0.0140 (8)
C54	0.4414 (2)	1.0086 (2)	0.03722 (15)	0.0164 (8)
C55	0.5030 (2)	0.9398 (2)	−0.03057 (16)	0.0167 (8)
H34	0.504119	0.897645	−0.051739	0.020*
C56	0.3824 (2)	1.0225 (2)	0.07791 (18)	0.0293 (10)
H10	0.397652	1.063502	0.100055	0.044*
H11	0.376920	0.979710	0.100115	0.044*
H12	0.334462	1.033278	0.059882	0.044*
O25	0.26939 (18)	0.83281 (16)	0.12854 (11)	0.0268 (7)
C57	0.2810 (2)	0.7723 (2)	0.15021 (15)	0.0186 (8)
O26	0.30100 (15)	0.71699 (15)	0.12622 (10)	0.0200 (6)
C58	0.2701 (2)	0.7689 (2)	0.20913 (15)	0.0180 (8)
C59	0.2562 (2)	0.8305 (2)	0.23991 (15)	0.0175 (8)
C60	0.2463 (2)	0.8185 (2)	0.29386 (16)	0.0193 (8)
H35	0.235926	0.858505	0.315872	0.023*
C61	0.2508 (2)	0.7510 (2)	0.31650 (15)	0.0187 (8)
C62	0.2630 (2)	0.6901 (2)	0.28556 (16)	0.0228 (9)
C63	0.2721 (2)	0.7009 (2)	0.23201 (16)	0.0212 (9)
H36	0.280086	0.660291	0.210042	0.025*
C64	0.2507 (3)	0.9066 (2)	0.21963 (17)	0.0270 (10)
H13	0.247350	0.939822	0.249533	0.040*
H14	0.205947	0.911450	0.196674	0.040*
H15	0.295350	0.917916	0.199477	0.040*
C65	0.2646 (3)	0.6157 (3)	0.30981 (18)	0.0376 (12)
H16	0.273858	0.579924	0.282274	0.056*
H17	0.216261	0.605735	0.325824	0.056*
H18	0.304561	0.613179	0.337019	0.056*
O27	0.18616 (16)	0.7598 (2)	0.39560 (11)	0.0365 (9)
C66	0.2466 (2)	0.7456 (2)	0.37518 (15)	0.0172 (8)
O28	0.30596 (16)	0.72682 (19)	0.39933 (11)	0.0322 (8)
O29	0.14471 (15)	0.71927 (15)	0.09210 (11)	0.0207 (6)
C67	0.0970 (2)	0.6923 (2)	0.12020 (18)	0.0254 (10)
H37	0.089692	0.641712	0.117972	0.030*
N3	0.0552 (2)	0.7286 (2)	0.15323 (15)	0.0321 (9)
C68	0.0640 (3)	0.8063 (3)	0.1599 (2)	0.0457 (14)
H19	0.100483	0.824196	0.134752	0.069*
H20	0.081818	0.816648	0.196021	0.069*
H21	0.015660	0.830018	0.153245	0.069*
C69	−0.0001 (3)	0.6922 (4)	0.1852 (2)	0.0600 (19)
H22	−0.000632	0.640766	0.176750	0.090*
H23	−0.049827	0.712734	0.177608	0.090*
H24	0.012930	0.698768	0.222768	0.090*
O30	0.22187 (16)	0.58336 (14)	0.11552 (12)	0.0248 (7)
C70	0.2147 (2)	0.5192 (2)	0.10222 (18)	0.0264 (10)
H38	0.205789	0.508132	0.065951	0.032*
N4	0.2191 (2)	0.46582 (19)	0.13698 (16)	0.0287 (9)
C71	0.2095 (3)	0.3913 (3)	0.1203 (2)	0.0484 (15)
H25	0.198825	0.389612	0.082138	0.073*
H26	0.167615	0.369761	0.139035	0.073*
H27	0.255444	0.364268	0.128565	0.073*
C72	0.2363 (3)	0.4816 (3)	0.1922 (2)	0.0411 (13)
H28	0.279217	0.514451	0.194729	0.062*
H29	0.248663	0.436775	0.210961	0.062*
H30	0.192814	0.504119	0.208249	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0066 (11)	0.0057 (11)	0.0068 (11)	−0.0003 (9)	0.0008 (9)	−0.0001 (9)
Zn1	0.00596 (18)	0.00545 (19)	0.00726 (19)	0.00012 (14)	0.00023 (14)	0.00011 (15)
Zn2	0.00573 (18)	0.00479 (19)	0.00723 (19)	0.00042 (14)	0.00003 (14)	−0.00036 (15)
Zn3	0.00547 (18)	0.00563 (19)	0.00885 (19)	0.00000 (14)	0.00136 (14)	−0.00052 (15)
Zn4	0.00609 (18)	0.00507 (19)	0.0100 (2)	−0.00037 (14)	−0.00087 (14)	0.00248 (15)
O2	0.0111 (12)	0.0126 (13)	0.0188 (14)	−0.0068 (10)	0.0032 (10)	−0.0028 (11)
C1	0.0088 (17)	0.0089 (17)	0.0153 (19)	−0.0035 (13)	−0.0018 (14)	0.0062 (14)
O3	0.0172 (13)	0.0110 (13)	0.0158 (14)	−0.0069 (10)	0.0031 (10)	−0.0041 (11)
C2	0.0072 (16)	0.0095 (17)	0.0145 (18)	−0.0013 (13)	−0.0007 (13)	0.0016 (14)
C3	0.0127 (18)	0.0138 (19)	0.025 (2)	−0.0015 (15)	0.0068 (16)	−0.0034 (16)
C4	0.0118 (18)	0.018 (2)	0.028 (2)	−0.0055 (15)	0.0079 (16)	−0.0051 (17)
C5	0.0106 (17)	0.0113 (18)	0.0175 (19)	−0.0041 (14)	0.0001 (14)	0.0012 (15)
C6	0.0119 (17)	0.0120 (18)	0.0156 (19)	−0.0039 (14)	0.0009 (14)	−0.0014 (15)
C7	0.0087 (17)	0.0143 (19)	0.0180 (19)	−0.0025 (14)	0.0014 (14)	−0.0022 (15)
C8	0.023 (2)	0.033 (3)	0.068 (4)	−0.012 (2)	0.024 (2)	−0.032 (3)
C9	0.017 (2)	0.020 (2)	0.031 (2)	−0.0061 (16)	0.0085 (17)	−0.0109 (18)
O4	0.0109 (12)	0.0113 (13)	0.0247 (15)	−0.0040 (10)	0.0044 (10)	−0.0034 (11)
C10	0.0135 (18)	0.0136 (19)	0.0121 (18)	−0.0006 (14)	0.0036 (14)	0.0015 (15)
O5	0.0110 (13)	0.0116 (13)	0.0249 (15)	−0.0029 (10)	0.0030 (11)	0.0041 (11)
O6	0.0148 (13)	0.0220 (15)	0.0102 (13)	−0.0058 (11)	0.0029 (10)	−0.0020 (11)
C11	0.0172 (18)	0.0068 (17)	0.0101 (18)	−0.0007 (14)	0.0010 (14)	0.0009 (14)
O7	0.0159 (13)	0.0258 (15)	0.0078 (13)	0.0048 (11)	0.0020 (10)	−0.0024 (11)
C12	0.0211 (19)	0.0117 (18)	0.0099 (18)	0.0020 (15)	−0.0001 (15)	−0.0016 (14)
C13	0.0191 (19)	0.020 (2)	0.0127 (19)	0.0063 (16)	0.0035 (15)	−0.0024 (16)
C14	0.024 (2)	0.022 (2)	0.0141 (19)	0.0021 (17)	−0.0008 (16)	−0.0024 (16)
C15	0.022 (2)	0.017 (2)	0.0098 (18)	−0.0009 (15)	0.0019 (15)	−0.0006 (15)
C16	0.018 (2)	0.027 (2)	0.018 (2)	0.0065 (17)	0.0056 (16)	−0.0052 (17)
C17	0.0142 (19)	0.029 (2)	0.016 (2)	0.0039 (16)	0.0005 (15)	−0.0053 (17)
C18	0.021 (2)	0.066 (4)	0.024 (2)	0.017 (2)	−0.0060 (18)	−0.013 (2)
C19	0.025 (2)	0.055 (3)	0.018 (2)	0.012 (2)	−0.0017 (18)	−0.010 (2)
C20	0.0101 (17)	0.022 (2)	0.0112 (18)	−0.0056 (15)	0.0022 (14)	−0.0016 (15)
O8	0.0240 (14)	0.0132 (14)	0.0092 (13)	−0.0005 (11)	0.0044 (10)	−0.0023 (10)
O9	0.0170 (13)	0.0215 (15)	0.0105 (13)	0.0025 (11)	0.0016 (10)	−0.0004 (11)
O10	0.0092 (12)	0.0091 (12)	0.0196 (14)	−0.0029 (10)	−0.0025 (10)	0.0012 (10)
C21	0.0113 (17)	0.0091 (18)	0.0120 (18)	−0.0024 (13)	0.0020 (13)	−0.0015 (14)
O11	0.0115 (13)	0.0104 (13)	0.0258 (15)	−0.0059 (10)	−0.0034 (11)	0.0046 (11)
C22	0.0098 (17)	0.0094 (18)	0.0187 (19)	−0.0042 (14)	−0.0004 (14)	−0.0008 (15)
C23	0.0064 (16)	0.0165 (19)	0.0174 (19)	−0.0033 (14)	−0.0047 (14)	0.0024 (15)
C24	0.0150 (18)	0.0111 (18)	0.0152 (19)	−0.0023 (14)	−0.0023 (14)	0.0023 (15)
C25	0.0121 (17)	0.0105 (18)	0.0147 (19)	−0.0028 (14)	0.0019 (14)	−0.0020 (14)
C26	0.0136 (19)	0.017 (2)	0.024 (2)	−0.0051 (15)	−0.0074 (16)	0.0074 (17)
C27	0.0163 (19)	0.014 (2)	0.022 (2)	−0.0065 (15)	−0.0053 (16)	0.0075 (16)
C28	0.019 (2)	0.027 (2)	0.036 (3)	−0.0088 (18)	−0.0121 (18)	0.019 (2)
C29	0.029 (2)	0.032 (3)	0.048 (3)	−0.017 (2)	−0.022 (2)	0.024 (2)
O12	0.0177 (13)	0.0122 (13)	0.0166 (14)	−0.0093 (11)	−0.0041 (11)	0.0057 (11)
C30	0.0059 (16)	0.0097 (17)	0.0163 (19)	−0.0021 (13)	0.0019 (13)	−0.0024 (14)
O13	0.0143 (13)	0.0139 (14)	0.0184 (14)	−0.0083 (11)	−0.0049 (11)	0.0059 (11)
O14	0.0159 (14)	0.0172 (14)	0.0268 (16)	0.0001 (11)	−0.0014 (11)	0.0127 (12)
C31	0.023 (2)	0.022 (2)	0.021 (2)	−0.0051 (17)	−0.0063 (17)	0.0069 (17)
N1	0.045 (2)	0.035 (2)	0.026 (2)	−0.0044 (19)	−0.0036 (18)	0.0211 (18)
C32	0.079 (5)	0.064 (4)	0.045 (4)	−0.023 (4)	0.017 (3)	0.027 (3)
C33	0.066 (4)	0.056 (4)	0.059 (4)	0.007 (3)	−0.018 (3)	0.034 (3)
C34	0.020 (2)	0.052 (3)	0.032 (3)	−0.011 (2)	−0.0105 (19)	0.023 (2)
N2A	0.026 (3)	0.056 (4)	0.051 (4)	−0.021 (3)	−0.027 (3)	0.028 (3)
N2B	0.039 (5)	0.067 (6)	0.065 (6)	−0.018 (5)	−0.025 (5)	0.029 (5)
O15	0.0112 (13)	0.0191 (15)	0.0241 (15)	−0.0021 (11)	−0.0069 (11)	−0.0004 (12)
C35A	0.037 (3)	0.079 (5)	0.053 (4)	−0.017 (3)	−0.029 (3)	0.023 (4)
C35B	0.043 (6)	0.071 (6)	0.066 (6)	−0.010 (6)	−0.014 (5)	0.022 (6)
C36	0.070 (4)	0.114 (5)	0.114 (5)	−0.039 (4)	−0.041 (4)	0.050 (4)
O16	0.0079 (11)	0.0051 (11)	0.0118 (12)	0.0020 (9)	−0.0004 (9)	0.0010 (10)
Zn5	0.0128 (2)	0.0069 (2)	0.0142 (2)	0.00188 (16)	0.00432 (16)	0.00256 (16)
Zn6	0.00918 (19)	0.0091 (2)	0.0125 (2)	−0.00042 (16)	−0.00018 (15)	−0.00198 (17)
Zn7	0.00952 (19)	0.0072 (2)	0.0099 (2)	0.00089 (15)	0.00017 (15)	−0.00070 (16)
Zn8	0.00914 (19)	0.00698 (19)	0.0106 (2)	0.00040 (15)	0.00129 (15)	−0.00027 (16)
O17	0.0209 (15)	0.0167 (15)	0.0298 (16)	0.0124 (11)	0.0121 (12)	0.0066 (12)
C37	0.0155 (19)	0.0124 (19)	0.027 (2)	0.0054 (15)	0.0057 (16)	0.0032 (16)
O18	0.0273 (16)	0.0175 (15)	0.045 (2)	0.0135 (13)	0.0208 (14)	0.0140 (14)
C38	0.019 (2)	0.015 (2)	0.031 (2)	0.0058 (16)	0.0068 (17)	0.0034 (18)
C39	0.026 (2)	0.025 (2)	0.036 (3)	0.0097 (18)	0.0109 (19)	0.010 (2)
C40	0.024 (2)	0.025 (2)	0.037 (3)	0.0116 (18)	0.0145 (19)	0.009 (2)
C41	0.051 (3)	0.053 (4)	0.040 (3)	0.035 (3)	0.021 (3)	0.027 (3)
O19	0.0178 (15)	0.0153 (15)	0.0432 (19)	−0.0030 (12)	−0.0008 (13)	−0.0062 (13)
C42	0.023 (2)	0.018 (2)	0.022 (2)	−0.0064 (17)	0.0027 (16)	−0.0047 (17)
O20	0.0190 (14)	0.0182 (15)	0.0357 (18)	−0.0076 (12)	−0.0056 (12)	0.0041 (13)
C43	0.023 (2)	0.015 (2)	0.030 (2)	−0.0047 (16)	0.0057 (17)	−0.0037 (17)
C44	0.028 (2)	0.019 (2)	0.043 (3)	−0.0052 (18)	0.010 (2)	−0.011 (2)
C45	0.018 (2)	0.023 (2)	0.050 (3)	−0.0063 (18)	0.012 (2)	−0.011 (2)
C46	0.029 (3)	0.034 (3)	0.076 (4)	−0.013 (2)	0.023 (3)	−0.023 (3)
O21	0.0348 (18)	0.0216 (17)	0.0379 (19)	0.0186 (14)	−0.0171 (14)	−0.0120 (14)
O22	0.0243 (16)	0.0225 (16)	0.0373 (18)	0.0151 (13)	−0.0124 (13)	−0.0120 (14)
C47	0.0142 (18)	0.0118 (19)	0.0177 (19)	0.0025 (14)	0.0047 (15)	0.0053 (15)
C48	0.0146 (18)	0.0126 (19)	0.0177 (19)	0.0057 (14)	0.0022 (15)	0.0044 (15)
C49	0.0150 (19)	0.015 (2)	0.021 (2)	0.0018 (15)	−0.0007 (15)	0.0015 (16)
C50	0.0152 (19)	0.0109 (18)	0.021 (2)	0.0019 (15)	0.0003 (15)	−0.0033 (15)
C51	0.023 (2)	0.020 (2)	0.029 (2)	0.0075 (17)	−0.0086 (18)	−0.0072 (18)
C52	0.0143 (18)	0.0126 (19)	0.0134 (18)	−0.0010 (14)	−0.0023 (14)	0.0063 (15)
O23	0.0257 (16)	0.0156 (15)	0.0429 (19)	−0.0103 (12)	0.0141 (14)	−0.0064 (14)
O24	0.0174 (14)	0.0136 (15)	0.0410 (18)	−0.0047 (11)	0.0067 (13)	−0.0061 (13)
C53	0.0150 (18)	0.0100 (18)	0.0169 (19)	−0.0025 (14)	−0.0009 (15)	0.0037 (15)
C54	0.0153 (19)	0.0147 (19)	0.019 (2)	−0.0045 (15)	0.0014 (15)	−0.0003 (16)
C55	0.0182 (19)	0.0104 (18)	0.021 (2)	−0.0045 (15)	0.0013 (16)	−0.0029 (15)
C56	0.025 (2)	0.027 (2)	0.036 (3)	−0.0114 (19)	0.0114 (19)	−0.014 (2)
O25	0.053 (2)	0.0182 (16)	0.0088 (14)	−0.0013 (14)	−0.0037 (13)	0.0004 (12)
C57	0.021 (2)	0.020 (2)	0.014 (2)	−0.0057 (16)	−0.0022 (15)	0.0021 (16)
O26	0.0233 (15)	0.0242 (16)	0.0123 (14)	0.0043 (12)	−0.0019 (11)	−0.0015 (12)
C58	0.022 (2)	0.021 (2)	0.0103 (18)	−0.0028 (16)	−0.0020 (15)	0.0014 (15)
C59	0.0191 (19)	0.020 (2)	0.0134 (19)	0.0002 (16)	−0.0064 (15)	0.0010 (16)
C60	0.024 (2)	0.018 (2)	0.015 (2)	0.0008 (16)	−0.0004 (16)	−0.0025 (16)
C61	0.0199 (19)	0.024 (2)	0.0125 (19)	−0.0010 (17)	0.0003 (15)	−0.0002 (17)
C62	0.032 (2)	0.020 (2)	0.017 (2)	−0.0024 (18)	−0.0017 (17)	0.0047 (17)
C63	0.028 (2)	0.020 (2)	0.015 (2)	−0.0003 (17)	−0.0005 (16)	−0.0021 (17)
C64	0.047 (3)	0.018 (2)	0.016 (2)	−0.001 (2)	−0.0022 (19)	−0.0010 (17)
C65	0.069 (4)	0.024 (3)	0.020 (2)	0.006 (2)	0.002 (2)	0.003 (2)
O27	0.0192 (15)	0.077 (3)	0.0134 (15)	0.0091 (16)	0.0024 (12)	0.0081 (16)
C66	0.021 (2)	0.018 (2)	0.0123 (19)	−0.0005 (16)	0.0000 (15)	0.0049 (16)
O28	0.0236 (16)	0.058 (2)	0.0147 (15)	0.0082 (15)	−0.0026 (12)	−0.0034 (15)
O29	0.0180 (14)	0.0167 (14)	0.0281 (16)	0.0029 (11)	0.0139 (12)	0.0023 (12)
C67	0.020 (2)	0.023 (2)	0.033 (3)	0.0006 (17)	0.0082 (18)	0.0056 (19)
N3	0.026 (2)	0.046 (3)	0.026 (2)	0.0097 (17)	0.0163 (16)	0.0063 (18)
C68	0.036 (3)	0.055 (4)	0.047 (3)	0.008 (3)	0.015 (2)	−0.025 (3)
C69	0.040 (3)	0.086 (5)	0.056 (4)	0.022 (3)	0.035 (3)	0.032 (3)
O30	0.0341 (17)	0.0084 (14)	0.0326 (17)	0.0018 (12)	0.0156 (13)	0.0066 (12)
C70	0.034 (2)	0.017 (2)	0.030 (2)	0.0005 (18)	0.0105 (19)	0.0066 (18)
N4	0.036 (2)	0.0140 (18)	0.037 (2)	0.0014 (16)	0.0071 (17)	0.0058 (16)
C71	0.071 (4)	0.015 (2)	0.059 (4)	−0.004 (2)	0.008 (3)	0.005 (2)
C72	0.063 (4)	0.022 (3)	0.038 (3)	0.001 (2)	0.006 (3)	0.013 (2)

Geometric parameters (Å, º)

O1—Zn2	1.916 (2)	C36—H80	0.9800
O1—Zn3	1.930 (2)	C36—H81	0.9800
O1—Zn1	1.936 (2)	C36—H82	0.9800
O1—Zn4	2.006 (2)	C36—H83	0.9800
Zn1—O2	1.961 (2)	O16—Zn7	1.912 (2)
Zn1—O8^i	1.962 (2)	O16—Zn8	1.914 (2)
Zn1—O13^ii	1.989 (2)	O16—Zn6	1.931 (2)
Zn2—O11	1.953 (2)	O16—Zn5	1.999 (2)
Zn2—O12^ii	1.958 (2)	Zn5—O30	2.047 (3)
Zn2—O7	1.960 (2)	Zn5—O17	2.053 (3)
Zn2—Zn3	3.1424 (5)	Zn5—O26	2.121 (3)
Zn3—O4^iii	1.960 (2)	Zn5—O19	2.177 (3)
Zn3—O3	1.963 (2)	Zn5—O29	2.194 (3)
Zn3—O6	1.989 (3)	Zn6—O20	1.946 (3)
Zn4—O10	2.055 (2)	Zn6—O21	1.958 (3)
Zn4—O14	2.089 (3)	Zn6—O27^i	1.973 (3)
Zn4—O5^iii	2.100 (3)	Zn6—Zn7	3.1073 (6)
Zn4—O15	2.156 (2)	Zn7—O25	1.908 (3)
Zn4—O9^i	2.195 (3)	Zn7—O22	1.942 (3)
O2—C1	1.271 (4)	Zn7—O23	1.981 (3)
C1—O3	1.253 (4)	Zn7—Zn8	3.0656 (6)
C1—C2	1.505 (5)	Zn8—O18	1.911 (3)
C2—C7	1.390 (5)	Zn8—O28^i	1.959 (3)
C2—C3	1.410 (5)	Zn8—O24	1.970 (3)
C3—C4	1.403 (5)	O17—C37	1.240 (4)
C3—C8	1.512 (5)	C37—O18	1.277 (5)
C4—C5	1.388 (5)	C37—C38	1.508 (5)
C4—H39	0.9500	C38—C39	1.395 (6)
C5—C6	1.411 (5)	C38—C40	1.404 (6)
C5—C10	1.513 (5)	C39—C40^iv	1.397 (6)
C6—C7	1.391 (5)	C39—H31	0.9500
C6—C9	1.515 (5)	C40—C41	1.515 (6)
C7—H40	0.9500	C41—H1	0.9800
C8—H41	0.9800	C41—H2	0.9800
C8—H42	0.9800	C41—H3	0.9800
C8—H43	0.9800	O19—C42	1.256 (5)
C9—H44	0.9800	C42—O20	1.265 (5)
C9—H45	0.9800	C42—C43	1.498 (5)
C9—H46	0.9800	C43—C44	1.386 (6)
O4—C10	1.262 (4)	C43—C45^v	1.399 (6)
C10—O5	1.258 (4)	C44—C45	1.390 (6)
O6—C11	1.256 (4)	C44—H32	0.9500
C11—O7	1.271 (4)	C45—C46	1.526 (6)
C11—C12	1.504 (5)	C46—H4	0.9800
C12—C13	1.400 (5)	C46—H5	0.9800
C12—C17	1.408 (5)	C46—H6	0.9800
C13—C14	1.386 (5)	O21—C47	1.243 (5)
C13—H47	0.9500	O22—C47	1.250 (5)
C14—C15	1.403 (5)	C47—C48	1.503 (5)
C14—C19	1.516 (6)	C48—C50^vi	1.399 (5)
C15—C16	1.373 (5)	C48—C49	1.400 (5)
C15—C20	1.519 (5)	C49—C50	1.382 (5)
C16—C17	1.392 (5)	C49—C51	1.518 (5)
C16—H48	0.9500	C50—H33	0.9500
C17—C18	1.511 (5)	C51—H7	0.9800
C18—H49	0.9800	C51—H8	0.9800
C18—H50	0.9800	C51—H9	0.9800
C18—H51	0.9800	C52—O24	1.254 (5)
C19—H52	0.9800	C52—O23	1.258 (5)
C19—H53	0.9800	C52—C53	1.490 (5)
C19—H54	0.9800	C53—C55	1.398 (5)
C20—O9	1.256 (5)	C53—C54	1.401 (5)
C20—O8	1.263 (5)	C54—C55^vii	1.392 (5)
O10—C21	1.244 (4)	C54—C56	1.515 (5)
C21—O11	1.259 (4)	C55—H34	0.9500
C21—C22	1.515 (5)	C56—H10	0.9800
C22—C23	1.394 (5)	C56—H11	0.9800
C22—C27	1.402 (5)	C56—H12	0.9800
C23—C24	1.384 (5)	O25—C57	1.266 (5)
C23—H55	0.9500	C57—O26	1.250 (5)
C24—C25	1.408 (5)	C57—C58	1.510 (5)
C24—C28	1.519 (5)	C58—C63	1.391 (6)
C25—C26	1.392 (5)	C58—C59	1.410 (6)
C25—C30	1.505 (5)	C59—C60	1.399 (5)
C26—C27	1.400 (5)	C59—C64	1.505 (6)
C26—H56	0.9500	C60—C61	1.380 (6)
C27—C29	1.511 (6)	C60—H35	0.9500
C28—H57	0.9800	C61—C62	1.396 (6)
C28—H58	0.9800	C61—C66	1.492 (5)
C28—H59	0.9800	C62—C63	1.384 (6)
C29—H60	0.9800	C62—C65	1.513 (6)
C29—H61	0.9800	C63—H36	0.9500
C29—H62	0.9800	C64—H13	0.9800
O12—C30	1.258 (4)	C64—H14	0.9800
C30—O13	1.262 (4)	C64—H15	0.9800
O14—C31	1.232 (5)	C65—H16	0.9800
C31—N1	1.316 (5)	C65—H17	0.9800
C31—H63	0.9500	C65—H18	0.9800
N1—C33	1.441 (7)	O27—C66	1.237 (5)
N1—C32	1.468 (6)	C66—O28	1.258 (5)
C32—H64	0.9800	O29—C67	1.231 (5)
C32—H65	0.9800	C67—N3	1.321 (5)
C32—H66	0.9800	C67—H37	0.9500
C33—H67	0.9800	N3—C69	1.459 (6)
C33—H68	0.9800	N3—C68	1.461 (7)
C33—H69	0.9800	C68—H19	0.9800
C34—O15	1.204 (5)	C68—H20	0.9800
C34—N2A	1.325 (7)	C68—H21	0.9800
C34—N2B	1.41 (2)	C69—H22	0.9800
C34—H70	0.9500	C69—H23	0.9800
C34—H71	0.9500	C69—H24	0.9800
N2A—C35A	1.440 (8)	O30—C70	1.244 (5)
N2A—C36	1.447 (9)	C70—N4	1.327 (5)
N2B—C35B	1.43 (3)	C70—H38	0.9500
N2B—C36	1.67 (2)	N4—C72	1.453 (6)
C35A—H72	0.9800	N4—C71	1.457 (6)
C35A—H73	0.9800	C71—H25	0.9800
C35A—H74	0.9800	C71—H26	0.9800
C35B—H75	0.9800	C71—H27	0.9800
C35B—H76	0.9800	C72—H28	0.9800
C35B—H77	0.9800	C72—H29	0.9800
C36—H78	0.9800	C72—H30	0.9800
C36—H79	0.9800
Zn2—O1—Zn3	109.58 (11)	H81—C36—H82	109.5
Zn2—O1—Zn1	111.24 (11)	N2B—C36—H83	109.5
Zn3—O1—Zn1	110.35 (11)	H81—C36—H83	109.5
Zn2—O1—Zn4	111.36 (11)	H82—C36—H83	109.5
Zn3—O1—Zn4	107.30 (10)	Zn7—O16—Zn8	106.50 (11)
Zn1—O1—Zn4	106.91 (11)	Zn7—O16—Zn6	107.89 (11)
O1—Zn1—O2	111.38 (10)	Zn8—O16—Zn6	111.66 (12)
O1—Zn1—O8^i	120.00 (10)	Zn7—O16—Zn5	109.60 (11)
O2—Zn1—O8^i	106.35 (11)	Zn8—O16—Zn5	113.76 (11)
O1—Zn1—O13^ii	108.66 (10)	Zn6—O16—Zn5	107.30 (11)
O2—Zn1—O13^ii	105.02 (11)	O16—Zn5—O30	171.05 (10)
O8^i—Zn1—O13^ii	104.26 (11)	O16—Zn5—O17	100.03 (10)
O1—Zn2—O11	116.55 (10)	O30—Zn5—O17	88.71 (11)
O1—Zn2—O12^ii	111.49 (10)	O16—Zn5—O26	94.26 (10)
O11—Zn2—O12^ii	104.50 (11)	O30—Zn5—O26	86.86 (12)
O1—Zn2—O7	112.57 (10)	O17—Zn5—O26	94.87 (11)
O11—Zn2—O7	102.48 (12)	O16—Zn5—O19	91.15 (11)
O12^ii—Zn2—O7	108.47 (11)	O30—Zn5—O19	86.92 (12)
O1—Zn2—Zn3	35.35 (7)	O17—Zn5—O19	89.76 (11)
O11—Zn2—Zn3	133.81 (8)	O26—Zn5—O19	172.16 (11)
O12^ii—Zn2—Zn3	119.38 (8)	O16—Zn5—O29	83.97 (10)
O7—Zn2—Zn3	77.82 (7)	O30—Zn5—O29	87.31 (11)
O1—Zn3—O4^iii	120.84 (10)	O17—Zn5—O29	175.99 (11)
O1—Zn3—O3	109.79 (10)	O26—Zn5—O29	84.42 (11)
O4^iii—Zn3—O3	105.24 (11)	O19—Zn5—O29	90.53 (11)
O1—Zn3—O6	110.45 (10)	O16—Zn6—O20	123.01 (11)
O4^iii—Zn3—O6	101.17 (11)	O16—Zn6—O21	110.83 (11)
O3—Zn3—O6	108.57 (11)	O20—Zn6—O21	104.59 (13)
O1—Zn3—Zn2	35.07 (7)	O16—Zn6—O27^i	108.77 (11)
O4^iii—Zn3—Zn2	134.73 (8)	O20—Zn6—O27^i	103.15 (13)
O3—Zn3—Zn2	118.73 (8)	O21—Zn6—O27^i	104.93 (15)
O6—Zn3—Zn2	75.66 (7)	O16—Zn6—Zn7	35.85 (7)
O1—Zn4—O10	101.64 (9)	O20—Zn6—Zn7	132.40 (9)
O1—Zn4—O14	169.85 (10)	O21—Zn6—Zn7	75.18 (9)
O10—Zn4—O14	88.00 (10)	O27^i—Zn6—Zn7	123.26 (9)
O1—Zn4—O5^iii	93.89 (10)	O25—Zn7—O16	120.30 (11)
O10—Zn4—O5^iii	93.32 (10)	O25—Zn7—O22	103.87 (13)
O14—Zn4—O5^iii	88.65 (11)	O16—Zn7—O22	113.40 (11)
O1—Zn4—O15	83.88 (10)	O25—Zn7—O23	106.53 (13)
O10—Zn4—O15	174.33 (10)	O16—Zn7—O23	110.11 (11)
O14—Zn4—O15	86.42 (10)	O22—Zn7—O23	100.64 (13)
O5^iii—Zn4—O15	87.55 (10)	O25—Zn7—Zn8	125.67 (10)
O1—Zn4—O9^i	91.91 (10)	O16—Zn7—Zn8	36.77 (7)
O10—Zn4—O9^i	87.90 (10)	O22—Zn7—Zn8	129.87 (9)
O14—Zn4—O9^i	85.22 (11)	O23—Zn7—Zn8	74.35 (8)
O5^iii—Zn4—O9^i	173.71 (10)	O25—Zn7—Zn6	137.16 (9)
O15—Zn4—O9^i	90.64 (10)	O16—Zn7—Zn6	36.26 (7)
C1—O2—Zn1	129.6 (2)	O22—Zn7—Zn6	77.31 (9)
O3—C1—O2	125.6 (3)	O23—Zn7—Zn6	115.41 (9)
O3—C1—C2	118.1 (3)	Zn8—Zn7—Zn6	62.040 (13)
O2—C1—C2	116.3 (3)	O18—Zn8—O16	115.55 (11)
C1—O3—Zn3	130.9 (2)	O18—Zn8—O28^i	112.70 (14)
C7—C2—C3	119.8 (3)	O16—Zn8—O28^i	107.81 (11)
C7—C2—C1	118.1 (3)	O18—Zn8—O24	104.85 (13)
C3—C2—C1	122.0 (3)	O16—Zn8—O24	114.05 (11)
C4—C3—C2	116.7 (3)	O28^i—Zn8—O24	101.03 (13)
C4—C3—C8	118.3 (3)	O18—Zn8—Zn7	133.52 (9)
C2—C3—C8	124.9 (3)	O16—Zn8—Zn7	36.73 (7)
C5—C4—C3	123.2 (3)	O28^i—Zn8—Zn7	112.19 (10)
C5—C4—H39	118.4	O24—Zn8—Zn7	77.61 (8)
C3—C4—H39	118.4	C37—O17—Zn5	139.5 (3)
C4—C5—C6	119.8 (3)	O17—C37—O18	125.4 (3)
C4—C5—C10	116.5 (3)	O17—C37—C38	119.4 (3)
C6—C5—C10	123.7 (3)	O18—C37—C38	115.2 (3)
C7—C6—C5	117.0 (3)	C37—O18—Zn8	125.1 (2)
C7—C6—C9	118.8 (3)	C39—C38—C40	120.6 (4)
C5—C6—C9	124.2 (3)	C39—C38—C37	116.8 (4)
C6—C7—C2	123.4 (3)	C40—C38—C37	122.6 (4)
C6—C7—H40	118.3	C38—C39—C40^iv	122.7 (4)
C2—C7—H40	118.3	C38—C39—H31	118.7
C3—C8—H41	109.5	C40^iv—C39—H31	118.7
C3—C8—H42	109.5	C39^iv—C40—C38	116.7 (4)
H41—C8—H42	109.5	C39^iv—C40—C41	117.7 (4)
C3—C8—H43	109.5	C38—C40—C41	125.6 (4)
H41—C8—H43	109.5	C40—C41—H1	109.5
H42—C8—H43	109.5	C40—C41—H2	109.5
C6—C9—H44	109.5	H1—C41—H2	109.5
C6—C9—H45	109.5	C40—C41—H3	109.5
H44—C9—H45	109.5	H1—C41—H3	109.5
C6—C9—H46	109.5	H2—C41—H3	109.5
H44—C9—H46	109.5	C42—O19—Zn5	128.9 (3)
H45—C9—H46	109.5	O19—C42—O20	124.8 (4)
C10—O4—Zn3^viii	113.5 (2)	O19—C42—C43	118.8 (4)
O5—C10—O4	124.7 (3)	O20—C42—C43	116.4 (4)
O5—C10—C5	117.6 (3)	C42—O20—Zn6	111.8 (2)
O4—C10—C5	117.7 (3)	C44—C43—C45^v	120.2 (4)
C10—O5—Zn4^viii	127.8 (2)	C44—C43—C42	117.3 (4)
C11—O6—Zn3	130.6 (2)	C45^v—C43—C42	122.5 (4)
O6—C11—O7	124.7 (3)	C43—C44—C45	123.1 (4)
O6—C11—C12	118.9 (3)	C43—C44—H32	118.5
O7—C11—C12	116.4 (3)	C45—C44—H32	118.5
C11—O7—Zn2	129.2 (2)	C44—C45—C43^v	116.7 (4)
C13—C12—C17	119.4 (3)	C44—C45—C46	119.3 (4)
C13—C12—C11	117.5 (3)	C43^v—C45—C46	123.9 (4)
C17—C12—C11	123.0 (3)	C45—C46—H4	109.5
C14—C13—C12	122.8 (4)	C45—C46—H5	109.5
C14—C13—H47	118.6	H4—C46—H5	109.5
C12—C13—H47	118.6	C45—C46—H6	109.5
C13—C14—C15	117.3 (4)	H4—C46—H6	109.5
C13—C14—C19	118.7 (4)	H5—C46—H6	109.5
C15—C14—C19	124.0 (4)	C47—O21—Zn6	130.7 (3)
C16—C15—C14	120.1 (4)	C47—O22—Zn7	128.3 (3)
C16—C15—C20	118.2 (3)	O21—C47—O22	125.3 (4)
C14—C15—C20	121.7 (3)	O21—C47—C48	117.8 (3)
C15—C16—C17	123.3 (4)	O22—C47—C48	116.9 (3)
C15—C16—H48	118.3	C50^vi—C48—C49	120.9 (3)
C17—C16—H48	118.3	C50^vi—C48—C47	116.0 (3)
C16—C17—C12	117.0 (3)	C49—C48—C47	123.0 (3)
C16—C17—C18	118.5 (4)	C50—C49—C48	116.4 (3)
C12—C17—C18	124.5 (4)	C50—C49—C51	118.0 (4)
C17—C18—H49	109.5	C48—C49—C51	125.6 (3)
C17—C18—H50	109.5	C49—C50—C48^vi	122.7 (4)
H49—C18—H50	109.5	C49—C50—H33	118.7
C17—C18—H51	109.5	C48^vi—C50—H33	118.7
H49—C18—H51	109.5	C49—C51—H7	109.5
H50—C18—H51	109.5	C49—C51—H8	109.5
C14—C19—H52	109.5	H7—C51—H8	109.5
C14—C19—H53	109.5	C49—C51—H9	109.5
H52—C19—H53	109.5	H7—C51—H9	109.5
C14—C19—H54	109.5	H8—C51—H9	109.5
H52—C19—H54	109.5	O24—C52—O23	124.4 (3)
H53—C19—H54	109.5	O24—C52—C53	117.8 (3)
O9—C20—O8	124.6 (3)	O23—C52—C53	117.7 (3)
O9—C20—C15	118.5 (3)	C52—O23—Zn7	127.8 (3)
O8—C20—C15	116.8 (3)	C52—O24—Zn8	125.4 (2)
C20—O8—Zn1^ix	115.5 (2)	C55—C53—C54	120.1 (3)
C20—O9—Zn4^ix	122.0 (2)	C55—C53—C52	117.1 (3)
C21—O10—Zn4	138.1 (2)	C54—C53—C52	122.8 (3)
O10—C21—O11	125.9 (3)	C55^vii—C54—C53	116.5 (3)
O10—C21—C22	116.8 (3)	C55^vii—C54—C56	118.4 (4)
O11—C21—C22	117.4 (3)	C53—C54—C56	125.1 (3)
C21—O11—Zn2	123.3 (2)	C54^vii—C55—C53	123.5 (4)
C23—C22—C27	119.4 (3)	C54^vii—C55—H34	118.3
C23—C22—C21	116.9 (3)	C53—C55—H34	118.3
C27—C22—C21	123.7 (3)	C54—C56—H10	109.5
C24—C23—C22	124.0 (3)	C54—C56—H11	109.5
C24—C23—H55	118.0	H10—C56—H11	109.5
C22—C23—H55	118.0	C54—C56—H12	109.5
C23—C24—C25	116.9 (3)	H10—C56—H12	109.5
C23—C24—C28	118.0 (3)	H11—C56—H12	109.5
C25—C24—C28	125.2 (3)	C57—O25—Zn7	118.1 (3)
C26—C25—C24	119.3 (3)	O26—C57—O25	124.4 (4)
C26—C25—C30	117.5 (3)	O26—C57—C58	119.4 (4)
C24—C25—C30	123.2 (3)	O25—C57—C58	116.1 (4)
C25—C26—C27	123.6 (3)	C57—O26—Zn5	127.7 (3)
C25—C26—H56	118.2	C63—C58—C59	120.7 (4)
C27—C26—H56	118.2	C63—C58—C57	116.5 (4)
C26—C27—C22	116.7 (3)	C59—C58—C57	122.8 (4)
C26—C27—C29	118.2 (3)	C60—C59—C58	115.9 (4)
C22—C27—C29	125.1 (3)	C60—C59—C64	118.3 (4)
C24—C28—H57	109.5	C58—C59—C64	125.7 (4)
C24—C28—H58	109.5	C61—C60—C59	122.9 (4)
H57—C28—H58	109.5	C61—C60—H35	118.6
C24—C28—H59	109.5	C59—C60—H35	118.6
H57—C28—H59	109.5	C60—C61—C62	120.8 (4)
H58—C28—H59	109.5	C60—C61—C66	118.0 (4)
C27—C29—H60	109.5	C62—C61—C66	121.1 (4)
C27—C29—H61	109.5	C63—C62—C61	117.1 (4)
H60—C29—H61	109.5	C63—C62—C65	121.9 (4)
C27—C29—H62	109.5	C61—C62—C65	121.0 (4)
H60—C29—H62	109.5	C62—C63—C58	122.5 (4)
H61—C29—H62	109.5	C62—C63—H36	118.8
C30—O12—Zn2^x	129.4 (2)	C58—C63—H36	118.8
O12—C30—O13	125.3 (3)	C59—C64—H13	109.5
O12—C30—C25	117.3 (3)	C59—C64—H14	109.5
O13—C30—C25	117.4 (3)	H13—C64—H14	109.5
C30—O13—Zn1^x	132.1 (2)	C59—C64—H15	109.5
C31—O14—Zn4	120.3 (3)	H13—C64—H15	109.5
O14—C31—N1	124.7 (4)	H14—C64—H15	109.5
O14—C31—H63	117.6	C62—C65—H16	109.5
N1—C31—H63	117.6	C62—C65—H17	109.5
C31—N1—C33	120.7 (4)	H16—C65—H17	109.5
C31—N1—C32	121.1 (4)	C62—C65—H18	109.5
C33—N1—C32	118.1 (4)	H16—C65—H18	109.5
N1—C32—H64	109.5	H17—C65—H18	109.5
N1—C32—H65	109.5	C66—O27—Zn6^ix	128.8 (3)
H64—C32—H65	109.5	O27—C66—O28	126.1 (4)
N1—C32—H66	109.5	O27—C66—C61	117.9 (3)
H64—C32—H66	109.5	O28—C66—C61	116.0 (3)
H65—C32—H66	109.5	C66—O28—Zn8^ix	127.2 (3)
N1—C33—H67	109.5	C67—O29—Zn5	125.5 (3)
N1—C33—H68	109.5	O29—C67—N3	124.7 (4)
H67—C33—H68	109.5	O29—C67—H37	117.7
N1—C33—H69	109.5	N3—C67—H37	117.7
H67—C33—H69	109.5	C67—N3—C69	121.1 (5)
H68—C33—H69	109.5	C67—N3—C68	121.1 (4)
O15—C34—N2A	124.6 (5)	C69—N3—C68	117.8 (4)
O15—C34—N2B	124.2 (10)	N3—C68—H19	109.5
O15—C34—H70	117.7	N3—C68—H20	109.5
N2A—C34—H70	117.7	H19—C68—H20	109.5
O15—C34—H71	117.9	N3—C68—H21	109.5
N2B—C34—H71	117.9	H19—C68—H21	109.5
C34—N2A—C35A	122.9 (6)	H20—C68—H21	109.5
C34—N2A—C36	117.9 (5)	N3—C69—H22	109.5
C35A—N2A—C36	117.3 (5)	N3—C69—H23	109.5
C34—N2B—C35B	131.9 (19)	H22—C69—H23	109.5
C34—N2B—C36	100.4 (16)	N3—C69—H24	109.5
C35B—N2B—C36	121.8 (17)	H22—C69—H24	109.5
C34—O15—Zn4	128.0 (3)	H23—C69—H24	109.5
N2A—C35A—H72	109.5	C70—O30—Zn5	122.9 (3)
N2A—C35A—H73	109.5	O30—C70—N4	122.2 (4)
H72—C35A—H73	109.5	O30—C70—H38	118.9
N2A—C35A—H74	109.5	N4—C70—H38	118.9
H72—C35A—H74	109.5	C70—N4—C72	119.6 (4)
H73—C35A—H74	109.5	C70—N4—C71	121.0 (4)
N2B—C35B—H75	109.5	C72—N4—C71	119.4 (4)
N2B—C35B—H76	109.5	N4—C71—H25	109.5
H75—C35B—H76	109.5	N4—C71—H26	109.5
N2B—C35B—H77	109.5	H25—C71—H26	109.5
H75—C35B—H77	109.5	N4—C71—H27	109.5
H76—C35B—H77	109.5	H25—C71—H27	109.5
N2A—C36—H78	109.5	H26—C71—H27	109.5
N2A—C36—H79	109.5	N4—C72—H28	109.5
H78—C36—H79	109.5	N4—C72—H29	109.5
N2A—C36—H80	109.5	H28—C72—H29	109.5
H78—C36—H80	109.5	N4—C72—H30	109.5
H79—C36—H80	109.5	H28—C72—H30	109.5
N2B—C36—H81	109.5	H29—C72—H30	109.5
N2B—C36—H82	109.5
Zn1—O2—C1—O3	−0.4 (5)	O15—C34—N2A—C35A	−171.9 (7)
Zn1—O2—C1—C2	−179.3 (2)	O15—C34—N2A—C36	24.4 (12)
O2—C1—O3—Zn3	15.1 (6)	O15—C34—N2B—C35B	153 (2)
C2—C1—O3—Zn3	−166.0 (2)	O15—C34—N2B—C36	−54.8 (19)
O3—C1—C2—C7	−160.8 (3)	N2A—C34—O15—Zn4	−176.8 (6)
O2—C1—C2—C7	18.2 (5)	N2B—C34—O15—Zn4	−129.3 (15)
O3—C1—C2—C3	19.4 (5)	Zn5—O17—C37—O18	−0.9 (7)
O2—C1—C2—C3	−161.6 (3)	Zn5—O17—C37—C38	180.0 (3)
C7—C2—C3—C4	−0.8 (6)	O17—C37—O18—Zn8	4.2 (6)
C1—C2—C3—C4	179.0 (3)	C38—C37—O18—Zn8	−176.7 (3)
C7—C2—C3—C8	−179.4 (4)	O17—C37—C38—C39	162.2 (4)
C1—C2—C3—C8	0.4 (6)	O18—C37—C38—C39	−16.9 (6)
C2—C3—C4—C5	2.3 (6)	O17—C37—C38—C40	−19.2 (6)
C8—C3—C4—C5	−179.0 (4)	O18—C37—C38—C40	161.6 (4)
C3—C4—C5—C6	−1.3 (6)	C40—C38—C39—C40^iv	0.8 (8)
C3—C4—C5—C10	178.7 (4)	C37—C38—C39—C40^iv	179.4 (4)
C4—C5—C6—C7	−1.2 (5)	C39—C38—C40—C39^iv	−0.8 (8)
C10—C5—C6—C7	178.7 (3)	C37—C38—C40—C39^iv	−179.2 (4)
C4—C5—C6—C9	−179.0 (4)	C39—C38—C40—C41	−179.6 (5)
C10—C5—C6—C9	0.9 (6)	C37—C38—C40—C41	2.0 (8)
C5—C6—C7—C2	2.7 (6)	Zn5—O19—C42—O20	51.1 (6)
C9—C6—C7—C2	−179.4 (4)	Zn5—O19—C42—C43	−127.3 (3)
C3—C2—C7—C6	−1.7 (6)	O19—C42—O20—Zn6	6.0 (5)
C1—C2—C7—C6	178.5 (3)	C43—C42—O20—Zn6	−175.6 (3)
Zn3^viii—O4—C10—O5	0.9 (5)	O19—C42—C43—C44	136.6 (4)
Zn3^viii—O4—C10—C5	179.0 (2)	O20—C42—C43—C44	−41.9 (6)
C4—C5—C10—O5	21.8 (5)	O19—C42—C43—C45^v	−42.1 (6)
C6—C5—C10—O5	−158.1 (4)	O20—C42—C43—C45^v	139.4 (5)
C4—C5—C10—O4	−156.4 (4)	C45^v—C43—C44—C45	2.4 (8)
C6—C5—C10—O4	23.7 (5)	C42—C43—C44—C45	−176.3 (4)
O4—C10—O5—Zn4^viii	55.7 (5)	C43—C44—C45—C43^v	−2.3 (8)
C5—C10—O5—Zn4^viii	−122.4 (3)	C43—C44—C45—C46	173.4 (5)
Zn3—O6—C11—O7	−19.8 (5)	Zn6—O21—C47—O22	10.3 (6)
Zn3—O6—C11—C12	160.6 (2)	Zn6—O21—C47—C48	−170.8 (3)
O6—C11—O7—Zn2	13.5 (5)	Zn7—O22—C47—O21	10.6 (6)
C12—C11—O7—Zn2	−166.9 (2)	Zn7—O22—C47—C48	−168.3 (3)
O6—C11—C12—C13	157.5 (4)	O21—C47—C48—C50^vi	5.6 (5)
O7—C11—C12—C13	−22.1 (5)	O22—C47—C48—C50^vi	−175.4 (4)
O6—C11—C12—C17	−26.5 (6)	O21—C47—C48—C49	−172.9 (4)
O7—C11—C12—C17	153.9 (4)	O22—C47—C48—C49	6.1 (6)
C17—C12—C13—C14	2.4 (6)	C50^vi—C48—C49—C50	−0.2 (6)
C11—C12—C13—C14	178.5 (4)	C47—C48—C49—C50	178.3 (3)
C12—C13—C14—C15	−2.4 (6)	C50^vi—C48—C49—C51	−179.7 (4)
C12—C13—C14—C19	−180.0 (4)	C47—C48—C49—C51	−1.2 (6)
C13—C14—C15—C16	0.2 (6)	C48—C49—C50—C48^vi	0.2 (6)
C19—C14—C15—C16	177.6 (4)	C51—C49—C50—C48^vi	179.7 (4)
C13—C14—C15—C20	179.7 (4)	O24—C52—O23—Zn7	24.2 (6)
C19—C14—C15—C20	−2.9 (6)	C53—C52—O23—Zn7	−158.3 (3)
C14—C15—C16—C17	2.1 (7)	O23—C52—O24—Zn8	11.5 (6)
C20—C15—C16—C17	−177.4 (4)	C53—C52—O24—Zn8	−165.9 (2)
C15—C16—C17—C12	−2.0 (6)	O24—C52—C53—C55	20.9 (5)
C15—C16—C17—C18	179.3 (4)	O23—C52—C53—C55	−156.7 (4)
C13—C12—C17—C16	−0.2 (6)	O24—C52—C53—C54	−161.4 (4)
C11—C12—C17—C16	−176.1 (4)	O23—C52—C53—C54	21.0 (5)
C13—C12—C17—C18	178.4 (4)	C55—C53—C54—C55^vii	−0.6 (6)
C11—C12—C17—C18	2.5 (7)	C52—C53—C54—C55^vii	−178.2 (3)
C16—C15—C20—O9	132.6 (4)	C55—C53—C54—C56	−179.7 (4)
C14—C15—C20—O9	−46.9 (5)	C52—C53—C54—C56	2.6 (6)
C16—C15—C20—O8	−44.9 (5)	C54—C53—C55—C54^vii	0.6 (7)
C14—C15—C20—O8	135.6 (4)	C52—C53—C55—C54^vii	178.4 (4)
O9—C20—O8—Zn1^ix	−2.2 (5)	Zn7—O25—C57—O26	19.7 (5)
C15—C20—O8—Zn1^ix	175.1 (2)	Zn7—O25—C57—C58	−160.9 (3)
O8—C20—O9—Zn4^ix	58.0 (5)	O25—C57—O26—Zn5	−59.6 (5)
C15—C20—O9—Zn4^ix	−119.3 (3)	C58—C57—O26—Zn5	121.0 (3)
Zn4—O10—C21—O11	−12.2 (6)	O26—C57—C58—C63	−9.5 (6)
Zn4—O10—C21—C22	167.1 (2)	O25—C57—C58—C63	171.0 (4)
O10—C21—O11—Zn2	−7.8 (5)	O26—C57—C58—C59	172.5 (4)
C22—C21—O11—Zn2	172.9 (2)	O25—C57—C58—C59	−7.0 (6)
O10—C21—C22—C23	−14.0 (5)	C63—C58—C59—C60	1.2 (6)
O11—C21—C22—C23	165.4 (3)	C57—C58—C59—C60	179.1 (4)
O10—C21—C22—C27	165.7 (4)	C63—C58—C59—C64	−178.4 (4)
O11—C21—C22—C27	−15.0 (5)	C57—C58—C59—C64	−0.5 (6)
C27—C22—C23—C24	2.2 (6)	C58—C59—C60—C61	1.0 (6)
C21—C22—C23—C24	−178.2 (3)	C64—C59—C60—C61	−179.4 (4)
C22—C23—C24—C25	−0.9 (6)	C59—C60—C61—C62	−2.5 (6)
C22—C23—C24—C28	−179.9 (4)	C59—C60—C61—C66	174.2 (4)
C23—C24—C25—C26	−1.2 (5)	C60—C61—C62—C63	1.6 (6)
C28—C24—C25—C26	177.8 (4)	C66—C61—C62—C63	−174.9 (4)
C23—C24—C25—C30	179.6 (3)	C60—C61—C62—C65	−177.2 (4)
C28—C24—C25—C30	−1.5 (6)	C66—C61—C62—C65	6.3 (6)
C24—C25—C26—C27	2.1 (6)	C61—C62—C63—C58	0.5 (6)
C30—C25—C26—C27	−178.6 (4)	C65—C62—C63—C58	179.4 (4)
C25—C26—C27—C22	−0.9 (6)	C59—C58—C63—C62	−2.0 (6)
C25—C26—C27—C29	−179.6 (4)	C57—C58—C63—C62	180.0 (4)
C23—C22—C27—C26	−1.2 (6)	Zn6^ix—O27—C66—O28	−4.4 (7)
C21—C22—C27—C26	179.1 (4)	Zn6^ix—O27—C66—C61	175.6 (3)
C23—C22—C27—C29	177.5 (4)	C60—C61—C66—O27	68.7 (5)
C21—C22—C27—C29	−2.2 (7)	C62—C61—C66—O27	−114.6 (5)
Zn2^x—O12—C30—O13	−7.5 (5)	C60—C61—C66—O28	−111.3 (4)
Zn2^x—O12—C30—C25	172.7 (2)	C62—C61—C66—O28	65.4 (5)
C26—C25—C30—O12	170.2 (3)	O27—C66—O28—Zn8^ix	−28.0 (7)
C24—C25—C30—O12	−10.5 (5)	C61—C66—O28—Zn8^ix	152.0 (3)
C26—C25—C30—O13	−9.6 (5)	Zn5—O29—C67—N3	153.2 (3)
C24—C25—C30—O13	169.7 (3)	O29—C67—N3—C69	−179.9 (5)
O12—C30—O13—Zn1^x	−4.7 (6)	O29—C67—N3—C68	−1.4 (7)
C25—C30—O13—Zn1^x	175.0 (2)	Zn5—O30—C70—N4	162.8 (3)
Zn4—O14—C31—N1	168.5 (4)	O30—C70—N4—C72	−3.0 (7)
O14—C31—N1—C33	−0.7 (8)	O30—C70—N4—C71	179.2 (4)
O14—C31—N1—C32	−179.2 (5)

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