A new Zn^II metallocryptand with unprecedented diflexure helix induced by V-shaped di­imidazole building blocks

Taking advantage of V-shaped ligands, a Zn^II metallocryptand, namely {[Zn₂(didp)₂(m-bdc)₂]}_n, (1) [didp = 2,8-di(1H-imidazol-1-yl)-dibenzo­thio­phene and m-H₂bdc = isophthalic acid], has been hydro­thermally synthesized. Single-crystal X-ray diffraction analysis reveals a 26-membered butterfly-type metallomacrocycle [Zn₂(didp)₂]. One m-bdc²⁻ ligand bridges [Zn₂(didp)₂] units to form a laterally non-symmetric [Zn₂(didp)₂(m-bdc)] metallocryptand with an exo–exo conformation. Another crystallographically independent m-bdc²⁻ functions as a secondary synthon to bridge discrete metallocryptands into a 1D zigzag chain architecture. Undoubtedly, the choice of two matched ligands in this work is crucial for metallocryptand construction and structure expansion. Interestingly, a rare helical chain with two flexures in one single L and/or R strand is observed. Another important feature is the C—O...π interactions, by which the dimensionality extension of (1) can be induced. Fluorescence measurements and density functional theory (DFT) calculations illustrate that the emission of (1) can probably be attributed to ligand-to-ligand charge transfer (LLCT).

Computing details

Data collection: SMART (Bruker, 2008); cell refinement: Bruker SMART; data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Bruker, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: SHELXTL (Bruker, 2008); software used to prepare material for publication: SHELXTL (Bruker, 2008).

(I)

Crystal data

C52H32N8O8S2Zn2	F(000) = 2224
Mr = 1091.71	Dx = 1.560 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.8461 (13) Å	Cell parameters from 8828 reflections
b = 20.359 (3) Å	θ = 2.4–27.2°
c = 29.189 (5) Å	µ = 1.19 mm^−1
β = 94.612 (3)°	T = 293 K
V = 4647.5 (13) Å^3	Block, colourless
Z = 4	0.25 × 0.22 × 0.18 mm

Data collection

Bruker APEX-II CCD diffractometer	8066 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.028
Absorption correction: multi-scan SADABS; Bruker, 2008	θmax = 27.7°, θmin = 1.4°
Tmin = 0.755, Tmax = 0.814	h = −10→9
31577 measured reflections	k = −26→25
10807 independent reflections	l = −36→38

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.070P)^2 + 0.1132P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
10807 reflections	Δρmax = 1.28 e Å^−3
649 parameters	Δρmin = −0.39 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Zn1	0.35966 (4)	0.03133 (2)	0.39527 (2)	0.03881 (9)
Zn2	0.21940 (4)	0.17720 (2)	0.08552 (2)	0.04737 (10)
S1	0.91495 (10)	0.43000 (3)	0.30804 (3)	0.05454 (19)
S2	0.79685 (9)	−0.23573 (3)	0.15215 (2)	0.04759 (17)
O1	0.1771 (2)	0.05273 (10)	0.34737 (5)	0.0493 (5)
O2	0.3569 (2)	0.08826 (11)	0.29806 (6)	0.0569 (5)
O3	−0.1255 (4)	0.12198 (15)	0.11732 (8)	0.0993 (9)
O4	0.1339 (4)	0.15504 (12)	0.14420 (7)	0.0738 (7)
O5	0.2463 (3)	−0.02961 (9)	0.43215 (6)	0.0497 (5)
O6	0.2959 (2)	0.02594 (9)	0.49738 (6)	0.0498 (5)
O7	−0.0866 (2)	−0.22912 (10)	0.42148 (7)	0.0548 (5)
O8	−0.1542 (3)	−0.28049 (10)	0.48192 (7)	0.0698 (6)
N1	0.4757 (3)	0.11547 (10)	0.41465 (7)	0.0387 (5)
N2	0.6170 (2)	0.20721 (10)	0.40527 (6)	0.0350 (4)
N3	0.6395 (3)	0.27561 (12)	0.14692 (7)	0.0482 (6)
N4	0.4498 (3)	0.21643 (13)	0.10585 (7)	0.0506 (6)
N5	0.5388 (3)	−0.02786 (10)	0.36933 (7)	0.0412 (5)
N6	0.6670 (2)	−0.09433 (10)	0.32342 (6)	0.0361 (4)
N7	0.4185 (3)	−0.00892 (11)	0.06894 (7)	0.0464 (5)
N8	0.2891 (3)	0.08710 (12)	0.06313 (7)	0.0546 (6)
C1	0.2123 (3)	0.07614 (12)	0.30883 (8)	0.0399 (6)
C2	0.0596 (3)	0.08804 (12)	0.27469 (8)	0.0378 (5)
C3	0.0879 (3)	0.10482 (11)	0.22975 (8)	0.0399 (6)
H3	0.1992	0.1101	0.2216	0.048*
C4	−0.0475 (4)	0.11373 (12)	0.19706 (9)	0.0453 (6)
C5	−0.2129 (4)	0.10575 (15)	0.20957 (11)	0.0585 (8)
H5	−0.3047	0.1109	0.1876	0.070*
C6	−0.2428 (4)	0.09023 (17)	0.25431 (11)	0.0611 (8)
H6	−0.3543	0.0863	0.2627	0.073*
C7	−0.1064 (4)	0.08062 (14)	0.28642 (10)	0.0514 (7)
H7	−0.1264	0.0690	0.3163	0.062*
C8	−0.0152 (5)	0.13102 (15)	0.14860 (10)	0.0622 (8)
C9	0.2332 (3)	−0.02033 (12)	0.47547 (8)	0.0354 (5)
C10	0.1331 (3)	−0.07262 (11)	0.49774 (7)	0.0299 (5)
C11	0.0608 (3)	−0.12440 (11)	0.47247 (7)	0.0315 (5)
H11	0.0698	−0.1254	0.4409	0.038*
C12	−0.0244 (3)	−0.17462 (11)	0.49259 (8)	0.0335 (5)
C13	−0.0415 (3)	−0.17201 (12)	0.53986 (8)	0.0399 (6)
H13	−0.0978	−0.2056	0.5541	0.048*
C14	0.0249 (3)	−0.11980 (13)	0.56549 (8)	0.0419 (6)
H14	0.0107	−0.1177	0.5968	0.050*
C15	0.1132 (3)	−0.07001 (12)	0.54467 (7)	0.0366 (5)
H15	0.1589	−0.0351	0.5621	0.044*
C16	−0.0931 (3)	−0.23061 (12)	0.46397 (9)	0.0430 (6)
C17	0.4970 (3)	0.14724 (13)	0.45611 (8)	0.0432 (6)
H17	0.4578	0.1324	0.4835	0.052*
C18	0.5838 (3)	0.20338 (13)	0.45086 (8)	0.0438 (6)
H18	0.6154	0.2339	0.4737	0.053*
C19	0.5492 (3)	0.15290 (12)	0.38534 (8)	0.0393 (5)
H19	0.5536	0.1429	0.3544	0.047*
C20	0.6991 (3)	0.25960 (12)	0.38286 (8)	0.0370 (5)
C21	0.7839 (3)	0.30856 (14)	0.40940 (9)	0.0449 (6)
H21	0.7930	0.3051	0.4413	0.054*
C22	0.8541 (3)	0.36181 (13)	0.38890 (10)	0.0492 (7)
H22	0.9096	0.3945	0.4067	0.059*
C23	0.8406 (3)	0.36608 (12)	0.34090 (9)	0.0416 (6)
C24	0.7617 (3)	0.31598 (12)	0.31435 (9)	0.0376 (5)
C25	0.6880 (3)	0.26257 (12)	0.33566 (8)	0.0359 (5)
H25	0.6324	0.2296	0.3182	0.043*
C26	0.7638 (3)	0.32861 (12)	0.26579 (9)	0.0386 (5)
C27	0.8456 (3)	0.38914 (13)	0.25715 (10)	0.0444 (6)
C28	0.8655 (4)	0.40950 (14)	0.21240 (11)	0.0528 (7)
H28	0.9229	0.4484	0.2070	0.063*
C29	0.8001 (4)	0.37192 (14)	0.17669 (11)	0.0526 (7)
H29	0.8108	0.3857	0.1467	0.063*
C30	0.7167 (3)	0.31258 (13)	0.18459 (9)	0.0435 (6)
C31	0.7024 (3)	0.29022 (13)	0.22892 (8)	0.0409 (6)
H31	0.6520	0.2498	0.2339	0.049*
C32	0.6858 (5)	0.2727 (3)	0.10262 (12)	0.0992 (16)
H32	0.7830	0.2913	0.0917	0.119*
C33	0.5676 (5)	0.2385 (3)	0.07825 (11)	0.0966 (15)
H33	0.5656	0.2309	0.0468	0.116*
C34	0.4980 (3)	0.23956 (13)	0.14651 (8)	0.0434 (6)
H34	0.4397	0.2317	0.1725	0.052*
C35	0.6468 (4)	−0.06929 (14)	0.39504 (9)	0.0527 (7)
H35	0.6628	−0.0690	0.4270	0.063*
C36	0.7248 (4)	−0.10964 (15)	0.36800 (9)	0.0541 (7)
H36	0.8036	−0.1421	0.3773	0.065*
C37	0.5551 (3)	−0.04427 (13)	0.32643 (8)	0.0382 (5)
H37	0.4970	−0.0240	0.3012	0.046*
C38	0.7039 (3)	−0.12878 (11)	0.28246 (8)	0.0339 (5)
C39	0.7892 (3)	−0.18894 (12)	0.28643 (9)	0.0419 (6)
H39	0.8240	−0.2052	0.3154	0.050*
C40	0.8223 (3)	−0.22417 (12)	0.24840 (9)	0.0437 (6)
H40	0.8801	−0.2640	0.2513	0.052*
C41	0.7675 (3)	−0.19927 (12)	0.20494 (9)	0.0390 (5)
C42	0.6827 (3)	−0.13846 (11)	0.20070 (8)	0.0337 (5)
C43	0.6525 (3)	−0.10286 (11)	0.23999 (8)	0.0352 (5)
H43	0.5984	−0.0622	0.2376	0.042*
C44	0.6430 (3)	−0.12121 (12)	0.15300 (8)	0.0350 (5)
C45	0.5517 (3)	−0.06715 (12)	0.13480 (8)	0.0384 (5)
H45	0.5114	−0.0354	0.1541	0.046*
C46	0.5221 (3)	−0.06138 (13)	0.08777 (8)	0.0411 (6)
C47	0.5821 (4)	−0.10841 (14)	0.05825 (9)	0.0483 (6)
H47	0.5611	−0.1034	0.0266	0.058*
C48	0.6717 (4)	−0.16196 (14)	0.07552 (9)	0.0467 (6)
H48	0.7137	−0.1930	0.0559	0.056*
C49	0.6988 (3)	−0.16906 (12)	0.12320 (9)	0.0403 (6)
C50	0.2868 (4)	−0.01427 (15)	0.03480 (9)	0.0525 (7)
H50	0.2566	−0.0514	0.0174	0.063*
C51	0.2112 (4)	0.04504 (15)	0.03180 (9)	0.0555 (7)
H51	0.1188	0.0558	0.0112	0.067*
C52	0.4145 (4)	0.05292 (15)	0.08434 (9)	0.0574 (8)
H52	0.4911	0.0698	0.1073	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.05055 (19)	0.03986 (17)	0.02681 (14)	−0.01075 (12)	0.00796 (12)	−0.00022 (11)
Zn2	0.0648 (2)	0.04482 (19)	0.03150 (16)	0.00583 (14)	−0.00233 (13)	0.00894 (12)
S1	0.0513 (4)	0.0319 (3)	0.0819 (5)	−0.0090 (3)	0.0139 (4)	−0.0028 (3)
S2	0.0512 (4)	0.0339 (3)	0.0589 (4)	0.0048 (3)	0.0126 (3)	−0.0098 (3)
O1	0.0590 (12)	0.0613 (12)	0.0276 (8)	−0.0049 (9)	0.0033 (8)	0.0016 (8)
O2	0.0473 (12)	0.0807 (15)	0.0425 (10)	−0.0075 (10)	0.0027 (8)	0.0046 (10)
O3	0.140 (2)	0.107 (2)	0.0452 (13)	−0.0150 (19)	−0.0286 (14)	0.0177 (14)
O4	0.1022 (19)	0.0752 (16)	0.0458 (12)	0.0071 (14)	0.0172 (12)	0.0247 (11)
O5	0.0707 (13)	0.0478 (11)	0.0325 (9)	−0.0153 (9)	0.0159 (8)	0.0010 (8)
O6	0.0588 (12)	0.0423 (11)	0.0481 (10)	−0.0193 (9)	0.0035 (9)	−0.0026 (8)
O7	0.0594 (12)	0.0553 (12)	0.0502 (11)	−0.0105 (9)	0.0062 (9)	−0.0214 (9)
O8	0.0975 (17)	0.0457 (12)	0.0641 (13)	−0.0303 (12)	−0.0065 (12)	0.0044 (10)
N1	0.0425 (12)	0.0405 (11)	0.0331 (10)	−0.0056 (9)	0.0024 (8)	−0.0008 (9)
N2	0.0378 (11)	0.0353 (11)	0.0313 (9)	−0.0022 (8)	−0.0008 (8)	−0.0026 (8)
N3	0.0392 (12)	0.0685 (16)	0.0380 (11)	0.0026 (11)	0.0099 (9)	0.0097 (11)
N4	0.0516 (14)	0.0669 (16)	0.0333 (11)	0.0100 (11)	0.0042 (9)	0.0050 (11)
N5	0.0499 (13)	0.0415 (12)	0.0324 (10)	−0.0074 (9)	0.0044 (9)	0.0004 (9)
N6	0.0365 (11)	0.0386 (11)	0.0327 (10)	−0.0008 (8)	−0.0005 (8)	0.0026 (8)
N7	0.0658 (15)	0.0410 (12)	0.0318 (10)	−0.0017 (11)	0.0002 (10)	0.0010 (9)
N8	0.0808 (18)	0.0436 (13)	0.0373 (11)	0.0038 (12)	−0.0082 (11)	0.0059 (10)
C1	0.0515 (16)	0.0387 (14)	0.0294 (11)	−0.0032 (11)	0.0036 (10)	−0.0057 (10)
C2	0.0478 (14)	0.0318 (12)	0.0342 (12)	−0.0011 (10)	0.0056 (10)	−0.0010 (10)
C3	0.0560 (16)	0.0286 (12)	0.0357 (12)	−0.0032 (10)	0.0071 (11)	0.0021 (10)
C4	0.0663 (18)	0.0297 (13)	0.0391 (13)	−0.0008 (12)	−0.0005 (12)	0.0030 (10)
C5	0.0592 (19)	0.0512 (18)	0.0621 (18)	0.0027 (14)	−0.0131 (14)	0.0031 (14)
C6	0.0473 (17)	0.069 (2)	0.0670 (19)	−0.0008 (14)	0.0060 (14)	0.0072 (16)
C7	0.0555 (17)	0.0538 (17)	0.0462 (15)	−0.0050 (13)	0.0122 (13)	0.0035 (13)
C8	0.097 (3)	0.0461 (17)	0.0427 (16)	0.0072 (17)	−0.0020 (16)	0.0134 (13)
C9	0.0352 (12)	0.0366 (13)	0.0346 (12)	0.0006 (10)	0.0042 (9)	0.0058 (10)
C10	0.0325 (12)	0.0303 (11)	0.0269 (10)	0.0017 (9)	0.0033 (8)	0.0009 (9)
C11	0.0343 (12)	0.0369 (12)	0.0235 (10)	0.0021 (9)	0.0030 (8)	0.0003 (9)
C12	0.0357 (12)	0.0313 (12)	0.0335 (11)	0.0016 (9)	0.0019 (9)	0.0010 (9)
C13	0.0427 (14)	0.0397 (14)	0.0382 (12)	−0.0046 (10)	0.0082 (10)	0.0086 (10)
C14	0.0505 (15)	0.0529 (16)	0.0227 (10)	−0.0017 (12)	0.0070 (10)	0.0019 (10)
C15	0.0435 (13)	0.0379 (13)	0.0284 (11)	−0.0011 (10)	0.0018 (9)	−0.0059 (10)
C16	0.0389 (14)	0.0330 (13)	0.0560 (16)	−0.0003 (10)	−0.0036 (11)	−0.0019 (12)
C17	0.0513 (15)	0.0477 (15)	0.0309 (12)	0.0013 (12)	0.0055 (10)	−0.0018 (11)
C18	0.0562 (16)	0.0447 (15)	0.0304 (11)	−0.0034 (12)	0.0029 (11)	−0.0080 (11)
C19	0.0479 (14)	0.0394 (13)	0.0303 (11)	−0.0097 (11)	0.0018 (10)	−0.0046 (10)
C20	0.0331 (12)	0.0337 (12)	0.0441 (13)	−0.0017 (9)	0.0033 (10)	−0.0035 (10)
C21	0.0435 (15)	0.0500 (16)	0.0411 (13)	−0.0051 (11)	0.0020 (11)	−0.0125 (12)
C22	0.0433 (15)	0.0387 (15)	0.0653 (18)	−0.0078 (11)	0.0029 (13)	−0.0186 (13)
C23	0.0369 (13)	0.0297 (13)	0.0588 (16)	−0.0020 (10)	0.0075 (11)	−0.0055 (11)
C24	0.0310 (12)	0.0332 (13)	0.0483 (14)	−0.0016 (9)	0.0012 (10)	−0.0019 (10)
C25	0.0357 (13)	0.0338 (12)	0.0379 (12)	−0.0058 (9)	0.0012 (10)	−0.0026 (10)
C26	0.0313 (12)	0.0346 (13)	0.0503 (14)	0.0000 (9)	0.0060 (10)	0.0068 (11)
C27	0.0348 (13)	0.0338 (13)	0.0652 (17)	0.0012 (10)	0.0079 (12)	0.0056 (12)
C28	0.0458 (16)	0.0370 (15)	0.077 (2)	0.0026 (12)	0.0171 (14)	0.0206 (14)
C29	0.0472 (16)	0.0486 (17)	0.0637 (18)	0.0096 (12)	0.0147 (13)	0.0229 (14)
C30	0.0326 (13)	0.0500 (16)	0.0485 (14)	0.0065 (11)	0.0059 (11)	0.0132 (12)
C31	0.0339 (13)	0.0418 (14)	0.0468 (13)	−0.0026 (10)	0.0033 (10)	0.0085 (11)
C32	0.082 (3)	0.167 (5)	0.052 (2)	−0.043 (3)	0.0297 (19)	0.003 (2)
C33	0.076 (3)	0.177 (5)	0.0382 (16)	−0.037 (3)	0.0182 (16)	−0.006 (2)
C34	0.0464 (15)	0.0493 (15)	0.0355 (12)	0.0081 (12)	0.0092 (11)	0.0043 (11)
C35	0.074 (2)	0.0533 (17)	0.0297 (12)	−0.0067 (14)	−0.0043 (12)	0.0016 (12)
C36	0.0673 (19)	0.0548 (18)	0.0376 (14)	0.0094 (14)	−0.0124 (13)	0.0018 (13)
C37	0.0429 (14)	0.0433 (14)	0.0288 (11)	−0.0016 (11)	0.0050 (10)	0.0022 (10)
C38	0.0307 (12)	0.0341 (12)	0.0369 (12)	−0.0015 (9)	0.0029 (9)	0.0014 (10)
C39	0.0412 (14)	0.0359 (13)	0.0478 (14)	−0.0008 (10)	−0.0005 (11)	0.0115 (11)
C40	0.0457 (15)	0.0272 (12)	0.0585 (16)	0.0057 (10)	0.0068 (12)	0.0075 (11)
C41	0.0355 (13)	0.0311 (12)	0.0511 (14)	−0.0011 (10)	0.0081 (10)	−0.0025 (11)
C42	0.0330 (12)	0.0278 (12)	0.0405 (12)	−0.0012 (9)	0.0040 (9)	0.0001 (9)
C43	0.0373 (13)	0.0299 (12)	0.0390 (12)	0.0039 (9)	0.0071 (10)	−0.0007 (10)
C44	0.0373 (13)	0.0334 (12)	0.0349 (11)	−0.0001 (10)	0.0074 (9)	−0.0044 (10)
C45	0.0475 (14)	0.0339 (13)	0.0345 (12)	0.0020 (10)	0.0073 (10)	−0.0032 (10)
C46	0.0494 (15)	0.0387 (14)	0.0355 (12)	0.0003 (11)	0.0060 (10)	0.0004 (10)
C47	0.0619 (18)	0.0525 (17)	0.0320 (12)	−0.0062 (13)	0.0126 (11)	−0.0045 (11)
C48	0.0548 (16)	0.0455 (15)	0.0418 (13)	−0.0037 (12)	0.0167 (12)	−0.0133 (12)
C49	0.0391 (13)	0.0363 (13)	0.0469 (14)	−0.0037 (10)	0.0129 (11)	−0.0073 (11)
C50	0.0662 (19)	0.0532 (17)	0.0369 (13)	−0.0084 (14)	−0.0038 (12)	0.0003 (12)
C51	0.0638 (19)	0.0595 (19)	0.0417 (15)	−0.0021 (15)	−0.0043 (13)	0.0047 (13)
C52	0.089 (2)	0.0421 (16)	0.0382 (14)	0.0029 (15)	−0.0129 (14)	0.0004 (12)

Geometric parameters (Å, º)

Zn1—O5	1.9087 (17)	C12—C16	1.488 (3)
Zn1—O1	1.9685 (18)	C13—C14	1.378 (4)
Zn1—N1	2.000 (2)	C13—H13	0.9300
Zn1—N5	2.042 (2)	C14—C15	1.395 (3)
Zn2—O4	1.942 (2)	C14—H14	0.9300
Zn2—N4	2.021 (2)	C15—H15	0.9300
Zn2—N8	2.037 (2)	C16—Zn2^ii	2.522 (3)
Zn2—O8^i	2.172 (2)	C17—C18	1.345 (4)
Zn2—O7^i	2.1751 (19)	C17—H17	0.9300
Zn2—C16^i	2.522 (3)	C18—H18	0.9300
S1—C23	1.745 (3)	C19—H19	0.9300
S1—C27	1.751 (3)	C20—C25	1.375 (3)
S2—C41	1.742 (3)	C20—C21	1.398 (3)
S2—C49	1.745 (3)	C21—C22	1.374 (4)
O1—C1	1.272 (3)	C21—H21	0.9300
O2—C1	1.227 (3)	C22—C23	1.399 (4)
O3—C8	1.220 (4)	C22—H22	0.9300
O4—C8	1.284 (4)	C23—C24	1.395 (3)
O5—C9	1.291 (3)	C24—C25	1.401 (3)
O6—C9	1.220 (3)	C24—C26	1.442 (3)
O7—C16	1.246 (3)	C25—H25	0.9300
O7—Zn2^ii	2.1751 (19)	C26—C31	1.385 (4)
O8—C16	1.255 (3)	C26—C27	1.421 (3)
O8—Zn2^ii	2.172 (2)	C27—C28	1.391 (4)
N1—C19	1.313 (3)	C28—C29	1.360 (4)
N1—C17	1.371 (3)	C28—H28	0.9300
N2—C19	1.340 (3)	C29—C30	1.401 (4)
N2—C18	1.379 (3)	C29—H29	0.9300
N2—C20	1.431 (3)	C30—C31	1.385 (3)
N3—C34	1.330 (3)	C31—H31	0.9300
N3—C32	1.373 (4)	C32—C33	1.321 (5)
N3—C30	1.427 (4)	C32—H32	0.9300
N4—C34	1.304 (3)	C33—H33	0.9300
N4—C33	1.351 (4)	C34—H34	0.9300
N5—C37	1.312 (3)	C35—C36	1.323 (4)
N5—C35	1.375 (4)	C35—H35	0.9300
N6—C37	1.352 (3)	C36—H36	0.9300
N6—C36	1.379 (3)	C37—H37	0.9300
N6—C38	1.436 (3)	C38—C43	1.377 (3)
N7—C52	1.338 (4)	C38—C39	1.396 (3)
N7—C50	1.381 (3)	C39—C40	1.364 (4)
N7—C46	1.425 (3)	C39—H39	0.9300
N8—C52	1.318 (4)	C40—C41	1.401 (3)
N8—C51	1.361 (4)	C40—H40	0.9300
C1—C2	1.515 (3)	C41—C42	1.406 (3)
C2—C7	1.381 (4)	C42—C43	1.393 (3)
C2—C3	1.390 (3)	C42—C44	1.445 (3)
C3—C4	1.382 (4)	C43—H43	0.9300
C3—H3	0.9300	C44—C45	1.395 (3)
C4—C5	1.386 (4)	C44—C49	1.400 (3)
C4—C8	1.499 (4)	C45—C46	1.379 (3)
C5—C6	1.382 (4)	C45—H45	0.9300
C5—H5	0.9300	C46—C47	1.395 (4)
C6—C7	1.379 (4)	C47—C48	1.372 (4)
C6—H6	0.9300	C47—H47	0.9300
C7—H7	0.9300	C48—C49	1.398 (4)
C9—C10	1.501 (3)	C48—H48	0.9300
C10—C11	1.382 (3)	C50—C51	1.345 (4)
C10—C15	1.392 (3)	C50—H50	0.9300
C11—C12	1.378 (3)	C51—H51	0.9300
C11—H11	0.9300	C52—H52	0.9300
C12—C13	1.398 (3)
O5—Zn1—O1	101.47 (8)	C17—C18—N2	107.1 (2)
O5—Zn1—N1	128.27 (8)	C17—C18—H18	126.4
O1—Zn1—N1	107.46 (8)	N2—C18—H18	126.4
O5—Zn1—N5	101.03 (8)	N1—C19—N2	112.1 (2)
O1—Zn1—N5	110.51 (8)	N1—C19—H19	124.0
N1—Zn1—N5	107.40 (8)	N2—C19—H19	124.0
O4—Zn2—N4	101.36 (10)	C25—C20—C21	120.9 (2)
O4—Zn2—N8	101.20 (10)	C25—C20—N2	119.8 (2)
N4—Zn2—N8	101.15 (10)	C21—C20—N2	119.3 (2)
O4—Zn2—O8^i	144.95 (10)	C22—C21—C20	120.7 (2)
N4—Zn2—O8^i	104.44 (9)	C22—C21—H21	119.6
N8—Zn2—O8^i	96.67 (8)	C20—C21—H21	119.6
O4—Zn2—O7^i	95.15 (9)	C21—C22—C23	119.0 (2)
N4—Zn2—O7^i	95.25 (9)	C21—C22—H22	120.5
N8—Zn2—O7^i	153.97 (8)	C23—C22—H22	120.5
O8^i—Zn2—O7^i	59.40 (7)	C24—C23—C22	120.3 (2)
O4—Zn2—C16^i	122.04 (10)	C24—C23—S1	113.1 (2)
N4—Zn2—C16^i	100.08 (9)	C22—C23—S1	126.5 (2)
N8—Zn2—C16^i	126.13 (9)	C23—C24—C25	120.1 (2)
O8^i—Zn2—C16^i	29.84 (8)	C23—C24—C26	112.1 (2)
O7^i—Zn2—C16^i	29.60 (8)	C25—C24—C26	127.8 (2)
C23—S1—C27	90.99 (12)	C20—C25—C24	119.0 (2)
C41—S2—C49	90.71 (12)	C20—C25—H25	120.5
C1—O1—Zn1	120.88 (17)	C24—C25—H25	120.5
C8—O4—Zn2	124.0 (2)	C31—C26—C27	119.0 (2)
C9—O5—Zn1	122.32 (16)	C31—C26—C24	129.2 (2)
C16—O7—Zn2^ii	90.82 (16)	C27—C26—C24	111.7 (2)
C16—O8—Zn2^ii	90.72 (17)	C28—C27—C26	120.8 (3)
C19—N1—C17	105.8 (2)	C28—C27—S1	127.2 (2)
C19—N1—Zn1	121.77 (16)	C26—C27—S1	112.0 (2)
C17—N1—Zn1	132.41 (17)	C29—C28—C27	119.2 (3)
C19—N2—C18	105.8 (2)	C29—C28—H28	120.4
C19—N2—C20	126.5 (2)	C27—C28—H28	120.4
C18—N2—C20	127.6 (2)	C28—C29—C30	120.7 (3)
C34—N3—C32	104.6 (3)	C28—C29—H29	119.6
C34—N3—C30	126.9 (2)	C30—C29—H29	119.6
C32—N3—C30	128.4 (3)	C31—C30—C29	120.7 (3)
C34—N4—C33	105.1 (3)	C31—C30—N3	119.0 (2)
C34—N4—Zn2	126.65 (18)	C29—C30—N3	120.2 (2)
C33—N4—Zn2	126.5 (2)	C26—C31—C30	119.4 (2)
C37—N5—C35	105.1 (2)	C26—C31—H31	120.3
C37—N5—Zn1	128.83 (18)	C30—C31—H31	120.3
C35—N5—Zn1	124.89 (17)	C33—C32—N3	107.6 (3)
C37—N6—C36	106.0 (2)	C33—C32—H32	126.2
C37—N6—C38	126.70 (19)	N3—C32—H32	126.2
C36—N6—C38	127.0 (2)	C32—C33—N4	109.8 (3)
C52—N7—C50	106.3 (2)	C32—C33—H33	125.1
C52—N7—C46	127.2 (2)	N4—C33—H33	125.1
C50—N7—C46	126.1 (2)	N4—C34—N3	112.9 (2)
C52—N8—C51	105.1 (2)	N4—C34—H34	123.6
C52—N8—Zn2	122.29 (19)	N3—C34—H34	123.6
C51—N8—Zn2	131.7 (2)	C36—C35—N5	110.5 (2)
O2—C1—O1	125.0 (2)	C36—C35—H35	124.8
O2—C1—C2	119.9 (2)	N5—C35—H35	124.8
O1—C1—C2	115.1 (2)	C35—C36—N6	106.8 (2)
C7—C2—C3	119.1 (2)	C35—C36—H36	126.6
C7—C2—C1	122.1 (2)	N6—C36—H36	126.6
C3—C2—C1	118.8 (2)	N5—C37—N6	111.6 (2)
C4—C3—C2	120.8 (2)	N5—C37—H37	124.2
C4—C3—H3	119.6	N6—C37—H37	124.2
C2—C3—H3	119.6	C43—C38—C39	121.0 (2)
C3—C4—C5	119.1 (2)	C43—C38—N6	119.9 (2)
C3—C4—C8	120.2 (3)	C39—C38—N6	119.1 (2)
C5—C4—C8	120.6 (3)	C40—C39—C38	121.0 (2)
C6—C5—C4	120.6 (3)	C40—C39—H39	119.5
C6—C5—H5	119.7	C38—C39—H39	119.5
C4—C5—H5	119.7	C39—C40—C41	118.8 (2)
C7—C6—C5	119.6 (3)	C39—C40—H40	120.6
C7—C6—H6	120.2	C41—C40—H40	120.6
C5—C6—H6	120.2	C40—C41—C42	120.5 (2)
C6—C7—C2	120.8 (3)	C40—C41—S2	126.43 (19)
C6—C7—H7	119.6	C42—C41—S2	113.10 (18)
C2—C7—H7	119.6	C43—C42—C41	119.7 (2)
O3—C8—O4	125.4 (3)	C43—C42—C44	129.0 (2)
O3—C8—C4	120.5 (3)	C41—C42—C44	111.3 (2)
O4—C8—C4	114.1 (3)	C38—C43—C42	119.0 (2)
O6—C9—O5	124.5 (2)	C38—C43—H43	120.5
O6—C9—C10	121.6 (2)	C42—C43—H43	120.5
O5—C9—C10	113.9 (2)	C45—C44—C49	119.3 (2)
C11—C10—C15	118.7 (2)	C45—C44—C42	128.5 (2)
C11—C10—C9	121.11 (19)	C49—C44—C42	112.1 (2)
C15—C10—C9	120.2 (2)	C46—C45—C44	119.1 (2)
C12—C11—C10	122.1 (2)	C46—C45—H45	120.4
C12—C11—H11	119.0	C44—C45—H45	120.4
C10—C11—H11	119.0	C45—C46—C47	121.2 (2)
C11—C12—C13	118.7 (2)	C45—C46—N7	119.6 (2)
C11—C12—C16	119.7 (2)	C47—C46—N7	119.1 (2)
C13—C12—C16	121.6 (2)	C48—C47—C46	120.5 (2)
C14—C13—C12	120.2 (2)	C48—C47—H47	119.8
C14—C13—H13	119.9	C46—C47—H47	119.8
C12—C13—H13	119.9	C47—C48—C49	118.7 (2)
C13—C14—C15	120.2 (2)	C47—C48—H48	120.6
C13—C14—H14	119.9	C49—C48—H48	120.6
C15—C14—H14	119.9	C48—C49—C44	121.1 (2)
C10—C15—C14	120.0 (2)	C48—C49—S2	126.0 (2)
C10—C15—H15	120.0	C44—C49—S2	112.85 (19)
C14—C15—H15	120.0	C51—C50—N7	106.1 (3)
O7—C16—O8	118.9 (2)	C51—C50—H50	127.0
O7—C16—C12	119.9 (2)	N7—C50—H50	127.0
O8—C16—C12	121.2 (2)	C50—C51—N8	110.5 (3)
O7—C16—Zn2^ii	59.58 (14)	C50—C51—H51	124.8
O8—C16—Zn2^ii	59.43 (14)	N8—C51—H51	124.8
C12—C16—Zn2^ii	177.79 (18)	N8—C52—N7	112.1 (3)
C18—C17—N1	109.1 (2)	N8—C52—H52	124.0
C18—C17—H17	125.4	N7—C52—H52	124.0
N1—C17—H17	125.4
Zn1—O1—C1—O2	−1.1 (4)	C23—S1—C27—C26	1.4 (2)
Zn1—O1—C1—C2	177.97 (15)	C26—C27—C28—C29	2.4 (4)
O2—C1—C2—C7	−174.3 (3)	S1—C27—C28—C29	−178.7 (2)
O1—C1—C2—C7	6.6 (4)	C27—C28—C29—C30	−1.4 (4)
O2—C1—C2—C3	7.9 (4)	C28—C29—C30—C31	−1.4 (4)
O1—C1—C2—C3	−171.2 (2)	C28—C29—C30—N3	176.1 (2)
C7—C2—C3—C4	−0.3 (4)	C34—N3—C30—C31	31.7 (4)
C1—C2—C3—C4	177.6 (2)	C32—N3—C30—C31	−153.3 (4)
C2—C3—C4—C5	0.0 (4)	C34—N3—C30—C29	−145.9 (3)
C2—C3—C4—C8	−179.3 (2)	C32—N3—C30—C29	29.1 (5)
C3—C4—C5—C6	1.2 (4)	C27—C26—C31—C30	−2.2 (4)
C8—C4—C5—C6	−179.6 (3)	C24—C26—C31—C30	179.4 (2)
C4—C5—C6—C7	−2.0 (5)	C29—C30—C31—C26	3.2 (4)
C5—C6—C7—C2	1.7 (5)	N3—C30—C31—C26	−174.4 (2)
C3—C2—C7—C6	−0.6 (4)	C34—N3—C32—C33	3.0 (5)
C1—C2—C7—C6	−178.4 (3)	C30—N3—C32—C33	−172.9 (4)
Zn2—O4—C8—O3	−3.9 (5)	N3—C32—C33—N4	−3.0 (6)
Zn2—O4—C8—C4	176.07 (18)	C34—N4—C33—C32	1.7 (5)
C3—C4—C8—O3	160.3 (3)	Zn2—N4—C33—C32	167.3 (3)
C5—C4—C8—O3	−18.9 (5)	C33—N4—C34—N3	0.3 (4)
C3—C4—C8—O4	−19.6 (4)	Zn2—N4—C34—N3	−165.25 (19)
C5—C4—C8—O4	161.1 (3)	C32—N3—C34—N4	−2.1 (4)
Zn1—O5—C9—O6	−2.9 (4)	C30—N3—C34—N4	173.9 (2)
Zn1—O5—C9—C10	177.61 (15)	C37—N5—C35—C36	−0.4 (3)
O6—C9—C10—C11	179.2 (2)	Zn1—N5—C35—C36	168.3 (2)
O5—C9—C10—C11	−1.3 (3)	N5—C35—C36—N6	0.1 (3)
O6—C9—C10—C15	−1.5 (4)	C37—N6—C36—C35	0.2 (3)
O5—C9—C10—C15	178.0 (2)	C38—N6—C36—C35	−174.0 (2)
C15—C10—C11—C12	−2.6 (3)	C35—N5—C37—N6	0.5 (3)
C9—C10—C11—C12	176.8 (2)	Zn1—N5—C37—N6	−167.62 (16)
C10—C11—C12—C13	1.6 (3)	C36—N6—C37—N5	−0.4 (3)
C10—C11—C12—C16	−177.3 (2)	C38—N6—C37—N5	173.7 (2)
C11—C12—C13—C14	0.5 (4)	C37—N6—C38—C43	14.6 (3)
C16—C12—C13—C14	179.4 (2)	C36—N6—C38—C43	−172.4 (2)
C12—C13—C14—C15	−1.6 (4)	C37—N6—C38—C39	−164.3 (2)
C11—C10—C15—C14	1.4 (3)	C36—N6—C38—C39	8.7 (4)
C9—C10—C15—C14	−177.9 (2)	C43—C38—C39—C40	−0.8 (4)
C13—C14—C15—C10	0.7 (4)	N6—C38—C39—C40	178.1 (2)
Zn2^ii—O7—C16—O8	4.2 (3)	C38—C39—C40—C41	−0.6 (4)
Zn2^ii—O7—C16—C12	−177.5 (2)	C39—C40—C41—C42	1.1 (4)
Zn2^ii—O8—C16—O7	−4.3 (3)	C39—C40—C41—S2	179.67 (19)
Zn2^ii—O8—C16—C12	177.5 (2)	C49—S2—C41—C40	−177.6 (2)
C11—C12—C16—O7	−6.2 (4)	C49—S2—C41—C42	0.98 (19)
C13—C12—C16—O7	174.8 (2)	C40—C41—C42—C43	−0.2 (3)
C11—C12—C16—O8	172.0 (2)	S2—C41—C42—C43	−178.96 (18)
C13—C12—C16—O8	−7.0 (4)	C40—C41—C42—C44	178.0 (2)
C19—N1—C17—C18	−0.2 (3)	S2—C41—C42—C44	−0.7 (3)
Zn1—N1—C17—C18	−179.22 (19)	C39—C38—C43—C42	1.7 (3)
N1—C17—C18—N2	0.3 (3)	N6—C38—C43—C42	−177.1 (2)
C19—N2—C18—C17	−0.3 (3)	C41—C42—C43—C38	−1.2 (3)
C20—N2—C18—C17	176.8 (2)	C44—C42—C43—C38	−179.1 (2)
C17—N1—C19—N2	0.0 (3)	C43—C42—C44—C45	−6.0 (4)
Zn1—N1—C19—N2	179.15 (16)	C41—C42—C44—C45	176.0 (2)
C18—N2—C19—N1	0.2 (3)	C43—C42—C44—C49	178.0 (2)
C20—N2—C19—N1	−176.9 (2)	C41—C42—C44—C49	−0.1 (3)
C19—N2—C20—C25	11.2 (4)	C49—C44—C45—C46	−1.5 (4)
C18—N2—C20—C25	−165.3 (2)	C42—C44—C45—C46	−177.3 (2)
C19—N2—C20—C21	−171.3 (2)	C44—C45—C46—C47	−0.2 (4)
C18—N2—C20—C21	12.2 (4)	C44—C45—C46—N7	175.5 (2)
C25—C20—C21—C22	1.9 (4)	C52—N7—C46—C45	38.1 (4)
N2—C20—C21—C22	−175.6 (2)	C50—N7—C46—C45	−132.8 (3)
C20—C21—C22—C23	−0.5 (4)	C52—N7—C46—C47	−146.1 (3)
C21—C22—C23—C24	−1.9 (4)	C50—N7—C46—C47	43.0 (4)
C21—C22—C23—S1	178.2 (2)	C45—C46—C47—C48	0.3 (4)
C27—S1—C23—C24	−1.5 (2)	N7—C46—C47—C48	−175.4 (2)
C27—S1—C23—C22	178.4 (2)	C46—C47—C48—C49	1.2 (4)
C22—C23—C24—C25	3.1 (4)	C47—C48—C49—C44	−2.9 (4)
S1—C23—C24—C25	−176.99 (18)	C47—C48—C49—S2	175.6 (2)
C22—C23—C24—C26	−178.7 (2)	C45—C44—C49—C48	3.1 (4)
S1—C23—C24—C26	1.2 (3)	C42—C44—C49—C48	179.6 (2)
C21—C20—C25—C24	−0.7 (4)	C45—C44—C49—S2	−175.62 (19)
N2—C20—C25—C24	176.8 (2)	C42—C44—C49—S2	0.9 (3)
C23—C24—C25—C20	−1.8 (4)	C41—S2—C49—C48	−179.7 (2)
C26—C24—C25—C20	−179.7 (2)	C41—S2—C49—C44	−1.05 (19)
C23—C24—C26—C31	178.4 (2)	C52—N7—C50—C51	−0.1 (3)
C25—C24—C26—C31	−3.6 (4)	C46—N7—C50—C51	172.4 (2)
C23—C24—C26—C27	−0.1 (3)	N7—C50—C51—N8	−0.8 (3)
C25—C24—C26—C27	177.9 (2)	C52—N8—C51—C50	1.3 (3)
C31—C26—C27—C28	−0.6 (4)	Zn2—N8—C51—C50	−167.6 (2)
C24—C26—C27—C28	178.1 (2)	C51—N8—C52—N7	−1.3 (3)
C31—C26—C27—S1	−179.66 (18)	Zn2—N8—C52—N7	168.88 (19)
C24—C26—C27—S1	−1.0 (3)	C50—N7—C52—N8	0.9 (3)
C23—S1—C27—C28	−177.6 (2)	C46—N7—C52—N8	−171.5 (2)

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