A novel three-dimensional zinc(II) coordination polymer based on 3,3′-{[1,3-phenyl­enebis(methyl­ene)]bis­(­oxy)}di­benzoic acid and 1,4-bis­(pyridin-4-yl)benzene: synthesis, crystal structure and photocatalytic properties

A novel three-dimensional (3D) Zn^II coordination polymer, namely, poly[[[1,4-bis­(pyridin-4-yl)benzene](μ₃-3,3′-{[1,3-phenyl­enebis(methyl­ene)]bis­(­oxy)}di­ben­zoato)zinc(II)] 1,4-bis­(pyridin-4-yl)benzene], {[Zn(C₂₂H₁₆O₆)(C₁₆H₁₂N₂)]·C₁₆H₁₂N₂}_n or {[Zn(PMBD)(DPB)]·DPB}_n, 1, where H₂PMBD is 3,3′-{[1,3-phenyl­ene­bis(methyl­ene)]bis­(­oxy)}di­benzoic acid and DPB is 1,4-bis­(pyridin-4-yl)benzene, has been synthesized by self-assembly using zinc nitrate, a semi-rigid di­carb­oxy­lic acid and a nitro­gen-containing ligand. The single-crystal X-ray structure determination indicates that 1 possesses an intriguing 3D architecture with a 4-connected uninodal cds topology, which is constructed from dinuclear {Zn₂} clusters and V-shaped PMBD²⁻ linkers. Compound 1 exhibits excellent photo­catalytic activity on the degradation of the organic dyes Rhodamine B (RhB), Rhodamine 6G (Rh6G) and Methyl Red (MR).

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[[[1,4-bis(pyridin-4-yl)benzene](µ₃-3,3'-{[1,3-phenylenebis(methylene)]bis(oxy)}dibenzoato)zinc(II)] 1,4-bis(pyridin-4-yl)benzene]

Crystal data

[Zn(C22H16O6)(C16H12N2)]·C16H12N2	F(000) = 3760
Mr = 3625.07	Dx = 1.440 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.4164 (10) Å	Cell parameters from 9859 reflections
b = 26.2567 (15) Å	θ = 2.2–27.5°
c = 20.0775 (12) Å	µ = 0.65 mm^−1
β = 114.401 (1)°	T = 296 K
V = 8361.3 (8) Å^3	Block, colourless
Z = 8	0.3 × 0.2 × 0.2 mm

Data collection

Bruker APEX2 CCD area detector diffractometer	9583 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	8739 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 7.9 pixels mm^-1	θmax = 27.5°, θmin = 1.5°
phi and ω scans	h = −21→22
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −34→31
Tmin = 0.829, Tmax = 0.881	l = −26→21
37653 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0333P)^2 + 9.9833P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
9583 reflections	Δρmax = 0.37 e Å^−3
586 parameters	Δρmin = −0.29 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
C15	0.81367 (10)	0.41752 (6)	0.32137 (8)	0.0255 (3)
H15	0.817275	0.428978	0.278924	0.031*
O5	1.39600 (6)	−0.00272 (4)	0.76249 (5)	0.0188 (2)
O4	1.30922 (6)	−0.04495 (4)	0.79732 (5)	0.01826 (19)
C38	1.33078 (8)	−0.02870 (5)	0.74788 (7)	0.0157 (2)
C31	1.12305 (9)	−0.17356 (5)	0.61541 (8)	0.0199 (3)
H31A	1.116915	−0.155842	0.655323	0.024*
H31B	1.176936	−0.191031	0.634713	0.024*
Zn1	0.41417 (2)	0.01605 (2)	0.38555 (2)	0.01290 (5)
O2	0.53048 (6)	−0.01534 (4)	0.43263 (6)	0.0211 (2)
O3	0.37967 (6)	0.04774 (4)	0.46083 (5)	0.01733 (19)
O6	0.79865 (6)	−0.16780 (4)	0.47774 (5)	0.0214 (2)
N1	0.47912 (7)	0.08603 (4)	0.38019 (6)	0.0159 (2)
O7	1.11962 (7)	−0.13813 (4)	0.56051 (5)	0.0241 (2)
C2	0.57800 (9)	0.12981 (5)	0.34587 (8)	0.0182 (3)
H2	0.616342	0.128309	0.324626	0.022*
N2	0.85393 (7)	0.44399 (4)	0.38319 (6)	0.0179 (2)
C30	0.97539 (8)	−0.19614 (5)	0.52765 (7)	0.0172 (3)
H30	0.969526	−0.163434	0.508392	0.021*
C33	1.22262 (8)	−0.08452 (5)	0.65499 (7)	0.0166 (3)
H33	1.222373	−0.104889	0.692791	0.020*
C12	0.75989 (8)	0.35556 (5)	0.37960 (7)	0.0168 (3)
C20	0.72603 (8)	−0.14310 (5)	0.43412 (7)	0.0172 (3)
C3	0.56353 (8)	0.17594 (5)	0.37342 (7)	0.0168 (3)
C29	1.05245 (8)	−0.21146 (5)	0.58147 (7)	0.0176 (3)
C23	0.57754 (8)	−0.08895 (5)	0.35490 (7)	0.0180 (3)
H23	0.528443	−0.070809	0.328433	0.022*
C18	0.62032 (8)	−0.08246 (5)	0.43080 (7)	0.0147 (2)
C19	0.69416 (8)	−0.10909 (5)	0.46987 (7)	0.0156 (2)
H19	0.722553	−0.104264	0.520083	0.019*
C21	0.68340 (9)	−0.15003 (5)	0.35874 (7)	0.0191 (3)
H21	0.704068	−0.172665	0.334474	0.023*
C4	0.50391 (9)	0.17562 (5)	0.40328 (8)	0.0203 (3)
H4	0.491099	0.205508	0.421394	0.024*
C27	0.99512 (10)	−0.29492 (6)	0.58108 (9)	0.0257 (3)
H27	1.002118	−0.328347	0.597884	0.031*
C5	0.46406 (9)	0.13050 (5)	0.40569 (8)	0.0191 (3)
H5	0.424811	0.130989	0.426025	0.023*
C1	0.53522 (8)	0.08627 (5)	0.35018 (7)	0.0176 (3)
H1	0.545824	0.055961	0.331511	0.021*
C6	0.61162 (8)	0.22270 (5)	0.37358 (8)	0.0172 (3)
C37	1.17058 (10)	−0.06513 (6)	0.52624 (8)	0.0259 (3)
H37	1.135871	−0.073155	0.477974	0.031*
C17	0.58694 (8)	−0.04590 (5)	0.47016 (7)	0.0146 (2)
C35	1.27381 (9)	−0.01039 (6)	0.61396 (8)	0.0221 (3)
H35	1.308675	0.018051	0.624481	0.027*
C9	0.70849 (8)	0.30984 (5)	0.37721 (7)	0.0172 (3)
C11	0.63905 (9)	0.23184 (5)	0.31836 (8)	0.0210 (3)
H11	0.625113	0.208897	0.279836	0.025*
C25	0.90665 (8)	−0.22945 (5)	0.50222 (7)	0.0179 (3)
C24	0.82286 (9)	−0.21123 (5)	0.44683 (8)	0.0197 (3)
H24A	0.827269	−0.201664	0.401869	0.024*
H24B	0.781068	−0.238020	0.435876	0.024*
C7	0.63191 (9)	0.25840 (5)	0.42991 (8)	0.0218 (3)
H7	0.613380	0.253425	0.466731	0.026*
C34	1.27419 (8)	−0.04139 (5)	0.67005 (7)	0.0158 (2)
C28	1.06240 (9)	−0.26123 (6)	0.60769 (8)	0.0226 (3)
H28	1.114125	−0.271875	0.643022	0.027*
C13	0.80383 (10)	0.38246 (6)	0.44414 (8)	0.0239 (3)
H13	0.802830	0.371315	0.487737	0.029*
C36	1.22088 (10)	−0.02212 (6)	0.54176 (8)	0.0277 (3)
H36	1.219363	−0.001042	0.504010	0.033*
C8	0.67937 (9)	0.30116 (5)	0.43154 (8)	0.0211 (3)
H8	0.692071	0.324502	0.469462	0.025*
C32	1.17172 (9)	−0.09642 (5)	0.58256 (8)	0.0196 (3)
C22	0.60967 (9)	−0.12281 (6)	0.32013 (8)	0.0207 (3)
H22	0.581420	−0.127483	0.269880	0.025*
C10	0.68670 (9)	0.27454 (5)	0.32003 (8)	0.0210 (3)
H10	0.704394	0.279780	0.282749	0.025*
C14	0.76692 (10)	0.37397 (6)	0.31734 (8)	0.0252 (3)
H14	0.740221	0.357033	0.272978	0.030*
C26	0.91726 (9)	−0.27883 (5)	0.52936 (8)	0.0220 (3)
H26	0.871935	−0.301300	0.512794	0.026*
N4	0.79903 (8)	−0.23284 (5)	0.70823 (7)	0.0257 (3)
C50	0.85285 (9)	−0.14027 (6)	0.66843 (8)	0.0215 (3)
C47	0.88523 (9)	−0.09110 (6)	0.65452 (8)	0.0222 (3)
C54	0.90096 (10)	−0.18468 (6)	0.68200 (9)	0.0267 (3)
H54	0.951992	−0.184620	0.677483	0.032*
C44	0.96207 (9)	0.00122 (6)	0.64278 (8)	0.0237 (3)
N3	1.10247 (10)	0.13806 (6)	0.64963 (9)	0.0398 (4)
C40	0.98507 (10)	0.09615 (7)	0.65914 (9)	0.0308 (3)
H40	0.936743	0.099306	0.667726	0.037*
C46	0.86334 (10)	−0.04513 (6)	0.67659 (9)	0.0276 (3)
H46	0.822588	−0.044771	0.695281	0.033*
C45	0.90130 (10)	0.00008 (6)	0.67114 (9)	0.0289 (3)
H45	0.885954	0.030236	0.686683	0.035*
C39	1.03308 (11)	0.13880 (7)	0.66196 (9)	0.0348 (4)
H39	1.015727	0.169903	0.673168	0.042*
C53	0.87273 (10)	−0.22864 (6)	0.70212 (9)	0.0280 (3)
H53	0.907023	−0.257322	0.712129	0.034*
C51	0.77453 (9)	−0.14451 (6)	0.67193 (8)	0.0226 (3)
H51	0.738471	−0.116629	0.661247	0.027*
C48	0.94202 (11)	−0.08915 (7)	0.62204 (10)	0.0352 (4)
H48	0.955033	−0.118950	0.603885	0.042*
C49	0.97955 (11)	−0.04395 (7)	0.61612 (10)	0.0359 (4)
H49	1.017030	−0.043874	0.593933	0.043*
C52	0.75127 (9)	−0.19068 (6)	0.69147 (8)	0.0236 (3)
H52	0.698753	−0.192578	0.693097	0.028*
C41	1.00881 (9)	0.04862 (6)	0.64351 (8)	0.0254 (3)
C43	1.12482 (14)	0.09243 (8)	0.63400 (13)	0.0494 (5)
H43	1.172948	0.090648	0.624901	0.059*
C42	1.08148 (12)	0.04773 (8)	0.63042 (12)	0.0412 (4)
H42	1.100638	0.017194	0.619336	0.049*
C16	0.84900 (9)	0.42579 (5)	0.44347 (8)	0.0228 (3)
H16	0.877358	0.443104	0.487261	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C15	0.0389 (8)	0.0204 (7)	0.0224 (7)	−0.0114 (6)	0.0179 (6)	−0.0040 (6)
O5	0.0157 (5)	0.0165 (5)	0.0216 (5)	−0.0015 (4)	0.0051 (4)	−0.0014 (4)
O4	0.0182 (5)	0.0210 (5)	0.0156 (4)	−0.0002 (4)	0.0069 (4)	−0.0007 (4)
C38	0.0150 (6)	0.0131 (6)	0.0178 (6)	0.0031 (5)	0.0055 (5)	−0.0010 (5)
C31	0.0203 (7)	0.0191 (7)	0.0185 (6)	−0.0028 (5)	0.0061 (5)	0.0010 (5)
Zn1	0.01350 (8)	0.01059 (8)	0.01435 (8)	−0.00139 (5)	0.00550 (6)	0.00029 (5)
O2	0.0184 (5)	0.0203 (5)	0.0237 (5)	0.0034 (4)	0.0079 (4)	0.0028 (4)
O3	0.0205 (5)	0.0169 (5)	0.0163 (4)	−0.0004 (4)	0.0094 (4)	−0.0008 (4)
O6	0.0191 (5)	0.0226 (5)	0.0197 (5)	0.0049 (4)	0.0052 (4)	−0.0048 (4)
N1	0.0153 (5)	0.0139 (5)	0.0186 (5)	−0.0015 (4)	0.0072 (4)	0.0000 (4)
O7	0.0274 (5)	0.0245 (5)	0.0171 (5)	−0.0123 (4)	0.0058 (4)	−0.0006 (4)
C2	0.0186 (6)	0.0168 (6)	0.0230 (7)	−0.0021 (5)	0.0123 (5)	−0.0016 (5)
N2	0.0192 (5)	0.0140 (5)	0.0203 (6)	−0.0033 (4)	0.0081 (5)	−0.0009 (4)
C30	0.0202 (6)	0.0126 (6)	0.0206 (6)	−0.0007 (5)	0.0102 (5)	−0.0011 (5)
C33	0.0172 (6)	0.0175 (6)	0.0158 (6)	−0.0013 (5)	0.0075 (5)	0.0008 (5)
C12	0.0180 (6)	0.0130 (6)	0.0201 (6)	−0.0026 (5)	0.0084 (5)	−0.0009 (5)
C20	0.0148 (6)	0.0173 (6)	0.0199 (6)	−0.0024 (5)	0.0074 (5)	−0.0006 (5)
C3	0.0175 (6)	0.0143 (6)	0.0195 (6)	−0.0033 (5)	0.0085 (5)	−0.0003 (5)
C29	0.0195 (6)	0.0177 (6)	0.0179 (6)	−0.0016 (5)	0.0101 (5)	−0.0025 (5)
C23	0.0168 (6)	0.0182 (6)	0.0175 (6)	−0.0027 (5)	0.0056 (5)	0.0002 (5)
C18	0.0157 (6)	0.0128 (6)	0.0170 (6)	−0.0041 (5)	0.0082 (5)	−0.0003 (5)
C19	0.0165 (6)	0.0155 (6)	0.0154 (6)	−0.0032 (5)	0.0071 (5)	−0.0007 (5)
C21	0.0203 (6)	0.0206 (7)	0.0180 (6)	−0.0019 (5)	0.0096 (5)	−0.0037 (5)
C4	0.0238 (7)	0.0138 (6)	0.0282 (7)	−0.0020 (5)	0.0155 (6)	−0.0027 (5)
C27	0.0324 (8)	0.0154 (7)	0.0302 (8)	−0.0012 (6)	0.0139 (6)	0.0033 (6)
C5	0.0199 (6)	0.0160 (6)	0.0263 (7)	−0.0020 (5)	0.0145 (6)	−0.0013 (5)
C1	0.0182 (6)	0.0150 (6)	0.0207 (7)	−0.0015 (5)	0.0093 (5)	−0.0020 (5)
C6	0.0182 (6)	0.0130 (6)	0.0225 (7)	−0.0027 (5)	0.0105 (5)	−0.0005 (5)
C37	0.0276 (7)	0.0315 (8)	0.0148 (6)	−0.0086 (6)	0.0049 (6)	0.0003 (6)
C17	0.0131 (6)	0.0117 (6)	0.0200 (6)	−0.0046 (4)	0.0080 (5)	0.0006 (5)
C35	0.0232 (7)	0.0219 (7)	0.0207 (7)	−0.0070 (5)	0.0085 (6)	−0.0003 (5)
C9	0.0183 (6)	0.0131 (6)	0.0199 (6)	−0.0027 (5)	0.0077 (5)	0.0003 (5)
C11	0.0271 (7)	0.0170 (7)	0.0236 (7)	−0.0073 (5)	0.0151 (6)	−0.0060 (5)
C25	0.0189 (6)	0.0190 (7)	0.0186 (6)	−0.0007 (5)	0.0106 (5)	−0.0037 (5)
C24	0.0185 (6)	0.0193 (7)	0.0217 (7)	−0.0009 (5)	0.0086 (5)	−0.0052 (5)
C7	0.0290 (7)	0.0183 (7)	0.0236 (7)	−0.0061 (6)	0.0163 (6)	−0.0025 (5)
C34	0.0142 (6)	0.0172 (6)	0.0166 (6)	−0.0003 (5)	0.0068 (5)	−0.0014 (5)
C28	0.0233 (7)	0.0214 (7)	0.0220 (7)	0.0021 (5)	0.0083 (6)	0.0027 (5)
C13	0.0320 (8)	0.0205 (7)	0.0174 (7)	−0.0090 (6)	0.0084 (6)	0.0011 (5)
C36	0.0333 (8)	0.0298 (8)	0.0182 (7)	−0.0101 (6)	0.0088 (6)	0.0040 (6)
C8	0.0284 (7)	0.0163 (6)	0.0215 (7)	−0.0065 (5)	0.0131 (6)	−0.0049 (5)
C32	0.0186 (6)	0.0202 (7)	0.0195 (7)	−0.0053 (5)	0.0074 (5)	−0.0017 (5)
C22	0.0210 (7)	0.0243 (7)	0.0153 (6)	−0.0025 (5)	0.0060 (5)	−0.0016 (5)
C10	0.0265 (7)	0.0189 (7)	0.0224 (7)	−0.0063 (5)	0.0148 (6)	−0.0023 (5)
C14	0.0369 (8)	0.0206 (7)	0.0207 (7)	−0.0130 (6)	0.0144 (6)	−0.0069 (6)
C26	0.0242 (7)	0.0184 (7)	0.0263 (7)	−0.0054 (5)	0.0135 (6)	−0.0034 (6)
N4	0.0286 (7)	0.0245 (7)	0.0211 (6)	−0.0019 (5)	0.0074 (5)	−0.0041 (5)
C50	0.0220 (7)	0.0264 (7)	0.0158 (6)	−0.0024 (5)	0.0074 (5)	−0.0051 (5)
C47	0.0194 (7)	0.0283 (8)	0.0187 (6)	−0.0029 (5)	0.0077 (5)	−0.0029 (6)
C54	0.0203 (7)	0.0313 (8)	0.0281 (8)	0.0009 (6)	0.0095 (6)	−0.0047 (6)
C44	0.0200 (7)	0.0306 (8)	0.0196 (7)	−0.0031 (6)	0.0071 (6)	0.0013 (6)
N3	0.0383 (8)	0.0370 (8)	0.0415 (9)	−0.0091 (7)	0.0139 (7)	0.0099 (7)
C40	0.0271 (8)	0.0351 (9)	0.0284 (8)	−0.0051 (7)	0.0096 (6)	−0.0015 (7)
C46	0.0256 (7)	0.0286 (8)	0.0359 (8)	−0.0002 (6)	0.0199 (7)	0.0001 (6)
C45	0.0285 (8)	0.0266 (8)	0.0368 (9)	−0.0002 (6)	0.0187 (7)	−0.0014 (7)
C39	0.0339 (9)	0.0329 (9)	0.0311 (9)	−0.0043 (7)	0.0070 (7)	0.0038 (7)
C53	0.0256 (8)	0.0253 (8)	0.0285 (8)	0.0034 (6)	0.0065 (6)	−0.0036 (6)
C51	0.0229 (7)	0.0251 (7)	0.0209 (7)	0.0003 (6)	0.0101 (6)	−0.0041 (6)
C48	0.0390 (9)	0.0314 (9)	0.0477 (10)	−0.0047 (7)	0.0305 (8)	−0.0115 (8)
C49	0.0367 (9)	0.0387 (10)	0.0457 (10)	−0.0077 (7)	0.0304 (8)	−0.0087 (8)
C52	0.0236 (7)	0.0268 (8)	0.0215 (7)	−0.0020 (6)	0.0104 (6)	−0.0055 (6)
C41	0.0222 (7)	0.0329 (8)	0.0187 (7)	−0.0029 (6)	0.0059 (6)	0.0046 (6)
C43	0.0437 (11)	0.0479 (12)	0.0693 (14)	−0.0105 (9)	0.0358 (11)	0.0052 (10)
C42	0.0370 (10)	0.0360 (10)	0.0602 (12)	−0.0037 (8)	0.0298 (9)	0.0025 (9)
C16	0.0284 (7)	0.0179 (7)	0.0175 (6)	−0.0079 (6)	0.0047 (6)	−0.0010 (5)

Geometric parameters (Å, º)

C15—H15	0.9300	C37—H37	0.9300
C15—N2	1.3401 (18)	C37—C36	1.384 (2)
C15—C14	1.387 (2)	C37—C32	1.391 (2)
O5—C38	1.2515 (16)	C35—H35	0.9300
O5—Zn1^i	2.3837 (10)	C35—C34	1.3873 (19)
O4—C38	1.2715 (17)	C35—C36	1.394 (2)
O4—Zn1^i	2.0927 (10)	C9—C8	1.3988 (19)
C38—Zn1^i	2.5581 (13)	C9—C10	1.4004 (19)
C38—C34	1.5005 (18)	C11—H11	0.9300
C31—H31A	0.9700	C11—C10	1.3871 (19)
C31—H31B	0.9700	C25—C24	1.5014 (19)
C31—O7	1.4246 (17)	C25—C26	1.389 (2)
C31—C29	1.5080 (18)	C24—H24A	0.9700
Zn1—O2	2.0234 (10)	C24—H24B	0.9700
Zn1—O3	2.0219 (9)	C7—H7	0.9300
Zn1—N1	2.1836 (11)	C7—C8	1.3865 (19)
Zn1—N2^ii	2.1545 (11)	C28—H28	0.9300
O2—C17	1.2516 (16)	C13—H13	0.9300
O3—C17^iii	1.2627 (16)	C13—C16	1.3865 (19)
O6—C20	1.3684 (16)	C36—H36	0.9300
O6—C24	1.4420 (16)	C8—H8	0.9300
N1—C5	1.3434 (18)	C22—H22	0.9300
N1—C1	1.3434 (17)	C10—H10	0.9300
O7—C32	1.3736 (16)	C14—H14	0.9300
C2—H2	0.9300	C26—H26	0.9300
C2—C3	1.3969 (19)	N4—C53	1.343 (2)
C2—C1	1.3867 (18)	N4—C52	1.341 (2)
N2—C16	1.3364 (18)	C50—C47	1.481 (2)
C30—H30	0.9300	C50—C54	1.395 (2)
C30—C29	1.3900 (19)	C50—C51	1.399 (2)
C30—C25	1.3978 (18)	C47—C46	1.392 (2)
C33—H33	0.9300	C47—C48	1.393 (2)
C33—C34	1.3986 (18)	C54—H54	0.9300
C33—C32	1.3903 (19)	C54—C53	1.379 (2)
C12—C9	1.4863 (18)	C44—C45	1.394 (2)
C12—C13	1.3944 (19)	C44—C49	1.386 (2)
C12—C14	1.392 (2)	C44—C41	1.484 (2)
C20—C19	1.3964 (19)	N3—C39	1.330 (2)
C20—C21	1.3952 (19)	N3—C43	1.337 (3)
C3—C4	1.3971 (19)	C40—H40	0.9300
C3—C6	1.4855 (18)	C40—C39	1.385 (2)
C29—C28	1.393 (2)	C40—C41	1.391 (2)
C23—H23	0.9300	C46—H46	0.9300
C23—C18	1.4029 (18)	C46—C45	1.385 (2)
C23—C22	1.383 (2)	C45—H45	0.9300
C18—C19	1.3873 (18)	C39—H39	0.9300
C18—C17	1.5046 (18)	C53—H53	0.9300
C19—H19	0.9300	C51—H51	0.9300
C21—H21	0.9300	C51—C52	1.385 (2)
C21—C22	1.392 (2)	C48—H48	0.9300
C4—H4	0.9300	C48—C49	1.383 (2)
C4—C5	1.3840 (19)	C49—H49	0.9300
C27—H27	0.9300	C52—H52	0.9300
C27—C28	1.387 (2)	C41—C42	1.395 (2)
C27—C26	1.390 (2)	C43—H43	0.9300
C5—H5	0.9300	C43—C42	1.381 (3)
C1—H1	0.9300	C42—H42	0.9300
C6—C11	1.3973 (19)	C16—H16	0.9300
C6—C7	1.3973 (19)
N2—C15—H15	118.3	C34—C35—C36	119.60 (13)
N2—C15—C14	123.48 (14)	C36—C35—H35	120.2
C14—C15—H15	118.3	C8—C9—C12	120.93 (12)
C38—O5—Zn1^i	83.22 (8)	C8—C9—C10	117.95 (12)
C38—O4—Zn1^i	95.90 (8)	C10—C9—C12	121.11 (12)
O5—C38—O4	122.15 (12)	C6—C11—H11	119.4
O5—C38—Zn1^i	67.72 (7)	C10—C11—C6	121.12 (13)
O5—C38—C34	120.48 (12)	C10—C11—H11	119.4
O4—C38—Zn1^i	54.46 (6)	C30—C25—C24	119.67 (12)
O4—C38—C34	117.37 (12)	C26—C25—C30	119.05 (13)
C34—C38—Zn1^i	171.71 (10)	C26—C25—C24	121.28 (13)
H31A—C31—H31B	108.4	O6—C24—C25	107.49 (11)
O7—C31—H31A	110.0	O6—C24—H24A	110.2
O7—C31—H31B	110.0	O6—C24—H24B	110.2
O7—C31—C29	108.40 (11)	C25—C24—H24A	110.2
C29—C31—H31A	110.0	C25—C24—H24B	110.2
C29—C31—H31B	110.0	H24A—C24—H24B	108.5
O5^iv—Zn1—C38^iv	29.07 (4)	C6—C7—H7	119.6
O4^iv—Zn1—O5^iv	58.69 (3)	C8—C7—C6	120.76 (13)
O4^iv—Zn1—C38^iv	29.63 (4)	C8—C7—H7	119.6
O4^iv—Zn1—N1	86.69 (4)	C33—C34—C38	119.46 (12)
O4^iv—Zn1—N2^ii	93.02 (4)	C35—C34—C38	119.73 (12)
O2—Zn1—O5^iv	95.91 (4)	C35—C34—C33	120.81 (12)
O2—Zn1—O4^iv	154.01 (4)	C29—C28—H28	120.0
O2—Zn1—C38^iv	124.72 (4)	C27—C28—C29	119.97 (14)
O2—Zn1—N1	85.80 (4)	C27—C28—H28	120.0
O2—Zn1—N2^ii	92.12 (4)	C12—C13—H13	119.9
O3—Zn1—O5^iv	151.90 (4)	C16—C13—C12	120.17 (13)
O3—Zn1—O4^iv	93.33 (4)	C16—C13—H13	119.9
O3—Zn1—C38^iv	122.88 (4)	C37—C36—C35	119.99 (14)
O3—Zn1—O2	111.58 (4)	C37—C36—H36	120.0
O3—Zn1—N1	90.60 (4)	C35—C36—H36	120.0
O3—Zn1—N2^ii	94.90 (4)	C9—C8—H8	119.4
N1—Zn1—O5^iv	85.54 (4)	C7—C8—C9	121.21 (13)
N1—Zn1—C38^iv	84.95 (4)	C7—C8—H8	119.4
N2^ii—Zn1—O5^iv	89.61 (4)	O7—C32—C33	124.56 (12)
N2^ii—Zn1—C38^iv	92.08 (4)	O7—C32—C37	115.03 (12)
N2^ii—Zn1—N1	174.50 (4)	C37—C32—C33	120.41 (13)
C17—O2—Zn1	158.18 (9)	C23—C22—C21	121.42 (13)
C17^iii—O3—Zn1	131.30 (9)	C23—C22—H22	119.3
C20—O6—C24	117.17 (11)	C21—C22—H22	119.3
C5—N1—Zn1	121.73 (9)	C9—C10—H10	119.6
C5—N1—C1	117.36 (11)	C11—C10—C9	120.78 (13)
C1—N1—Zn1	120.90 (9)	C11—C10—H10	119.6
C32—O7—C31	117.41 (11)	C15—C14—C12	120.08 (13)
C3—C2—H2	120.0	C15—C14—H14	120.0
C1—C2—H2	120.0	C12—C14—H14	120.0
C1—C2—C3	120.05 (12)	C27—C26—H26	119.8
C15—N2—Zn1^v	122.65 (9)	C25—C26—C27	120.50 (13)
C16—N2—C15	116.65 (12)	C25—C26—H26	119.8
C16—N2—Zn1^v	120.46 (9)	C52—N4—C53	115.24 (14)
C29—C30—H30	119.7	C54—C50—C47	121.38 (13)
C29—C30—C25	120.61 (13)	C54—C50—C51	116.30 (14)
C25—C30—H30	119.7	C51—C50—C47	122.27 (14)
C34—C33—H33	120.6	C46—C47—C50	121.35 (13)
C32—C33—H33	120.6	C46—C47—C48	117.26 (14)
C32—C33—C34	118.90 (12)	C48—C47—C50	121.32 (14)
C13—C12—C9	122.09 (12)	C50—C54—H54	120.0
C14—C12—C9	121.78 (12)	C53—C54—C50	119.92 (14)
C14—C12—C13	116.13 (12)	C53—C54—H54	120.0
O6—C20—C19	115.64 (12)	C45—C44—C41	121.35 (15)
O6—C20—C21	124.71 (12)	C49—C44—C45	117.66 (15)
C21—C20—C19	119.65 (12)	C49—C44—C41	120.96 (14)
C2—C3—C4	116.89 (12)	C39—N3—C43	115.58 (16)
C2—C3—C6	121.58 (12)	C39—C40—H40	119.9
C4—C3—C6	121.48 (12)	C39—C40—C41	120.28 (16)
C30—C29—C31	120.36 (12)	C41—C40—H40	119.9
C30—C29—C28	119.65 (13)	C47—C46—H46	119.5
C28—C29—C31	119.84 (13)	C45—C46—C47	121.04 (14)
C18—C23—H23	120.6	C45—C46—H46	119.5
C22—C23—H23	120.6	C44—C45—H45	119.4
C22—C23—C18	118.82 (13)	C46—C45—C44	121.24 (15)
C23—C18—C17	120.06 (12)	C46—C45—H45	119.4
C19—C18—C23	120.36 (12)	N3—C39—C40	124.08 (18)
C19—C18—C17	119.57 (12)	N3—C39—H39	118.0
C20—C19—H19	119.9	C40—C39—H39	118.0
C18—C19—C20	120.27 (12)	N4—C53—C54	124.40 (14)
C18—C19—H19	119.9	N4—C53—H53	117.8
C20—C21—H21	120.3	C54—C53—H53	117.8
C22—C21—C20	119.47 (13)	C50—C51—H51	120.4
C22—C21—H21	120.3	C52—C51—C50	119.28 (14)
C3—C4—H4	120.3	C52—C51—H51	120.4
C5—C4—C3	119.50 (13)	C47—C48—H48	119.2
C5—C4—H4	120.3	C49—C48—C47	121.60 (16)
C28—C27—H27	119.9	C49—C48—H48	119.2
C28—C27—C26	120.14 (14)	C44—C49—H49	119.5
C26—C27—H27	119.9	C48—C49—C44	120.93 (15)
N1—C5—C4	123.44 (12)	C48—C49—H49	119.5
N1—C5—H5	118.3	N4—C52—C51	124.72 (14)
C4—C5—H5	118.3	N4—C52—H52	117.6
N1—C1—C2	122.73 (12)	C51—C52—H52	117.6
N1—C1—H1	118.6	C40—C41—C44	122.80 (14)
C2—C1—H1	118.6	C40—C41—C42	115.78 (15)
C11—C6—C3	121.15 (12)	C42—C41—C44	121.39 (16)
C11—C6—C7	118.16 (12)	N3—C43—H43	117.7
C7—C6—C3	120.67 (12)	N3—C43—C42	124.63 (18)
C36—C37—H37	119.9	C42—C43—H43	117.7
C36—C37—C32	120.26 (13)	C41—C42—H42	120.2
C32—C37—H37	119.9	C43—C42—C41	119.65 (19)
O2—C17—O3^iii	125.20 (12)	C43—C42—H42	120.2
O2—C17—C18	118.08 (12)	N2—C16—C13	123.45 (13)
O3^iii—C17—C18	116.68 (11)	N2—C16—H16	118.3
C34—C35—H35	120.2	C13—C16—H16	118.3

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