Photoluminescence properties of a cationic tri­nuclear zinc(II) complex with the tetradentate Schiff base ligand 6-methyl-2-({[(pyridin-2-yl)meth­yl]imino}­meth­yl)phenolate

Metal complexes with Schiff base ligands have been suggested as potential phosphors in electroluminescent devices. In the title complex, tetra­kis­[6-methyl-2-({[(pyridin-2-yl)meth­yl]imino}­meth­yl)phenolato-1:2κ⁸N,N′,O:O;3:2κ⁸N,N′,O:O]trizinc(II) hexa­fluorido­phosphate methanol monosolvate, [Zn₃(C₁₄H₁₃N₂O)₄](PF₆)₂·CH₃OH, the Zn^II cations adopt both six- and four-coordinate geometries involving the N and O atoms of tetra­dentate 6-methyl-2-({[(pyridin-2-yl)meth­yl]imino}­meth­yl)phenolate ligands. Two terminal Zn^II cations adopt distorted octa­hedral geometries and the central Zn^II cation adopts a distorted tetra­hedral geometry. The O atoms of the phenolate ligands bridge three Zn^II cations, forming a dicationic trinuclear metal cluster. The title complex exhibits a strong emission at 469 nm with a quantum yield of 15.5%.

S1. Introduction

Many Schiff bases containing aromatic rings exhibit fluorescence emission in the blue or blue–green regions at room temperature (Burlov et al., 2014; Satam et al., 2014), and their metal complexes enhance this fluorescence with high photoluminescent quantum yields (PLQYs) due to an increase in the rigidity of the fluorescent ligand (Li et al., 2004). Therefore, metal complexes with Schiff base ligands have been suggested as potential phosphors in electroluminescent devices, such as organic light-emitting devices (OLEDs) or light-emitting electrochemical cells (LECs) (Dumur et al. , 2014). To develop emitting materials, in particular, zinc complexes with Schiff bases have been synthesized and their luminescence properties studied (Das et al., 2013; Gracia-Santos et al., 2009). Recently, we reported neutral dinuclear Zn^II complex with an N,N',O-coordinating Schiff base containing a 2-picolyl group, [Zn₂L₂(CH₃COO)₂]₂, where L = 6-chloro-2-({(E)-[(pyridin-2-yl)methyl]­imino}­methyl)­phenolate, produced by the reaction of HL and zinc(II) acetate (Kim et al., 2013). The complex showed different geometries for the Zn^II atoms and we suggested it as a potential candidate for the emitting material in blue OLEDs. LECs offer more advantages than multilayer OLEDs because LECs consist of a single layer, which can be easily produced from solution (Su et al., 2006). In the present report, the Schiff base molecule 6-methyl-2-({[(pyridin-2-yl)methyl]­imino}­methyl)­phenol (HL1) was prepared and its reaction with zinc(II) acetate yielded the Zn^II precursor complex incorporating L1, which further reacted with NH₄PF₆ to yield a trinuclear cationic Zn^II complex, viz. [Zn₃(L1)₄](PF₆)₂.CH₃OH, (I). Luminescent cationic transition metal complexes can be used as chromo­phosphors in LECs since these cationic metal complexes are intrinsically ionic and no ion-conducting materials in needed in an emitting layer in LECs. The structural and photoluminescence properties of (1) were examined with regard to its being a potential candidate as a fluorescent chromo­phosphor in LECs.

S2. Experimental

UV–visible spectra were recorded on a Jasco V-570 spectrophotometer, and photoluminescence spectra were measured using a Hitachi F-4500 fluorescence spectrophotometer.

S2.1. Synthesis and crystallization

S2.1.1. Preparation of 6-methyl-2-({[(pyridin-2-yl)methyl]­imino}­methyl)­phenol (HL1)

2-Picolyl­amine (0.54 g, 5 mmol) was added to a solution of 2-hy­droxy-3-methyl­benzaldehyde (0.58 g, 5 mmol) in methanol (30 ml) and the resulting solution stirred at 298 K for 3 h. A brown oil was obtained after evaporation (yield 1.09 g, 96%).

S2.1.2. Preparation of the title complex, (I)

A methanol solution (30 ml) of Schiff base molecule HL1 (1.13 g, 5 mmol) was added to a methanol solution (10 ml) of zinc a­ctate (1.095 g, 5 mmol) and the resulting solution stirred at 298 K for 3 h. The brown powder which formed was filtered off and washed with hexane (yield 2.30 g, 66%). Ammonium hexafluoridophosphate (NH₄PF₆; 0.163 g, 1mmol) was added to a methanol solution (30 ml) of the obtained brown Zn^II precursor complex (0.699 g, 1 mmol) and the resulting solution stirred for 3 h. The title trinuclear cluster, (I) was obtained as a white powder. The powder was filtered off and washed with hexane (yield 0.234 g, 17%). Colourless crystals of (I) suitable for X-ray analysis were obtained by recrystallization from a solution in chloro­form–hexane (1:1 v/v) at room temperature.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 and O—H = 0.82 Å, and with 1.5U_eq(C,O) for methyl or hy­droxy atoms or 1.2U_eq(C) otherwise. The maximum and minimum residual electron-density peaks were located at 1.09 and 0.63 Å, respectively, from atoms Zn1 and F81.

S3. Results and discussion

The UV–Vis and photoluminescence (PL) spectra both of the Schiff base molecule 6-methyl-2-({[(pyridin-2-yl)methyl]­imino}­methyl)­phenol (HL1) and its trinuclear Zn^II complex, (I), were investigated in di­methyl­formamide solution (ca 10^-5 M) at room temperature. UV–Vis spectra revealed that there was a strong absorption at 266 nm, whereas complex (I) displayed a strong peak at 269 nm and a weaker absorption at 380 nm. The lower energy absorption at 380 nm was ascribed to a typical spin-allowed metal-to-ligand charge-transfer (MLCT) transition. The PL spectra indicate that the HL1 molecule has a luminescence emission at 356 nm with PLQYs of less than 1%, whereas complex (I) exhibits an emission in the blue region at 469 nm with 15.5% PLQYs. The PLQYs were calculated using 9,10-di­phenyl­anthracene (0.91) as a reference. The emission of complex (I) should probably be assigned to ¹(π–π*) intra­ligand fluorescence (Wang et al., 2007). Compared to free molecule HL1, the emission peak of complex (I) was bathochromically shifted as [to? by?] 113 nm, which is inter­preted as the extended π-conjugation resulting in a decrease of the HOMO–LUMO (HOMO is the highest occupied molecular orbital and LUMO is the lowest unoccupied molecular orbital) energy gap of the complex (Shyamal et al.,2014). It is worth noting that the quantum yield of complex (I) was enhanced up to 15.5% compared with that of free molecule HL1 (<1%). The enhanced luminescence efficiency in complex (I) is attributed to the coordination of the L1 ligands to the Zn^II ions which increase the rigidity of the ligands resulting in decreased radiation-less decay of the intra­ligand exited state (Roy et al., 2015).

The structure of the salt (I) consists of one dicationic trinuclear metal cluster, two PF₆^- anions and one methanol solvent molecule in the lattice. The structural analysis of (I) (Fig. 1 and Table 2) shows that there are two different coordination geometries of the Zn^II atoms in the metal cluster. The outer Zn^II cations are each coordinated by four N atoms and two O atoms of two L1 ligands within a distorted o­cta­hedral geometry (Fig. 2). The Zn—N and Zn—O bond lengths (Table 2) are comparable with those of other Zn complexes (Kim et al., 2013; Yuan et al., 2012). The bond angles around the Zn1 and Zn3 atoms are in the ranges 77.7 (1)–101.7 (2) and 77.1 (2)–105.7 (2)°, respectively. The central Zn2 atom is coordinated by four O atoms of four L1 ligands, forming a distorted tetra­hedral geometry, and these O atoms bridge to the outer Zn^II atoms to form the trinuclear metal cluster. The bond angles around the Zn2 atom (Table 2) deviate greatly from the ideal tetra­hedral value of 109.5 °; however, the Zn2—O bond lengths [1.944 (4)–1.966 (4) Å] are much shorter than those involving the outer Zn^II atoms [Zn1/Zn3—O = 2.124 (4)–2.153 (4) Å]. The dihedral angle between O16/Zn2/O33 and O50/Zn2/O67 planes is 81.06 (14)°. There are no direct inter­actions between two Zn^II metal atoms due to long separations of 3.083 (1) and 3.097 (1) Å. The crystal structure is stabilized by weak van der Waals inter­actions, which link the molecules into a three-dimensional network (Fig. 3). [Mention the hydrogen bonding detailled in Table 3?]

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of the title complex, (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The coordination environments atound the Zn atoms in a trinuclear metal cluster.
	Fig. 3. Part of the crystal structure of the title complex, (I), showing the three-dimensional network of molecules. H atoms have been omitted for clarity.

Tetrakis[6-methyl-2-({[(pyridin-2-yl)methyl]imino}methyl)phenolato-1:2κ⁸N,N',O:O;3:2κ⁸N,N',O:O]trizinc(II) hexafluoridophosphate methanol monosolvate

Crystal data

[Zn3(C14H13N2O)4](PF6)2·CH4O	F(000) = 2888
Mr = 1419.14	Dx = 1.578 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.460 (3) Å	Cell parameters from 3870 reflections
b = 21.116 (4) Å	θ = 2.3–19.9°
c = 19.607 (4) Å	µ = 1.34 mm^−1
β = 94.00 (3)°	T = 173 K
V = 5972 (2) Å^3	Block, colorless
Z = 4	0.13 × 0.11 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer	14777 independent reflections
Radiation source: fine-focus sealed tube	6278 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.118
φ and ω scans	θmax = 28.3°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −18→19
Tmin = 0.828, Tmax = 0.904	k = −27→28
58982 measured reflections	l = −26→26

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.071	H-atom parameters constrained
wR(F^2) = 0.214	w = 1/[σ^2(Fo^2) + (0.0932P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
14777 reflections	Δρmax = 1.24 e Å^−3
790 parameters	Δρmin = −0.57 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
Zn1	0.79162 (5)	0.71368 (3)	0.36056 (3)	0.03344 (19)
N1	0.8594 (4)	0.7172 (2)	0.2670 (2)	0.0409 (13)
C2	0.9066 (5)	0.6691 (3)	0.2408 (3)	0.0462 (17)
H2	0.9113	0.6313	0.2650	0.055*
C3	0.9480 (6)	0.6731 (4)	0.1807 (4)	0.070 (2)
H3	0.9784	0.6386	0.1632	0.084*
C4	0.9431 (7)	0.7297 (5)	0.1470 (4)	0.087 (3)
H4	0.9710	0.7341	0.1059	0.105*
C5	0.8968 (6)	0.7809 (4)	0.1733 (4)	0.068 (2)
H5	0.8934	0.8197	0.1508	0.082*
C6	0.8552 (5)	0.7719 (3)	0.2354 (3)	0.0441 (16)
C7	0.8027 (5)	0.8256 (3)	0.2662 (3)	0.0514 (18)
H7A	0.8413	0.8632	0.2691	0.062*
H7B	0.7477	0.8352	0.2368	0.062*
N8	0.7755 (4)	0.8088 (2)	0.3348 (2)	0.0383 (12)
C9	0.7697 (4)	0.8531 (3)	0.3785 (3)	0.0459 (17)
H9	0.7801	0.8943	0.3642	0.055*
C10	0.7475 (4)	0.8436 (3)	0.4502 (3)	0.0408 (15)
C11	0.7172 (4)	0.7868 (3)	0.4774 (3)	0.0374 (15)
C12	0.7000 (4)	0.7835 (3)	0.5475 (3)	0.0446 (16)
C13	0.7187 (5)	0.8361 (4)	0.5876 (4)	0.060 (2)
H13	0.7113	0.8335	0.6343	0.072*
C14	0.7479 (5)	0.8921 (4)	0.5611 (4)	0.067 (2)
H14	0.7570	0.9273	0.5894	0.080*
C15	0.7637 (5)	0.8967 (3)	0.4932 (4)	0.059 (2)
H15	0.7850	0.9344	0.4756	0.071*
O16	0.7004 (3)	0.73561 (18)	0.43802 (18)	0.0349 (9)
C17	0.6688 (5)	0.7203 (3)	0.5761 (3)	0.0561 (19)
H17A	0.6138	0.7062	0.5503	0.084*
H17B	0.6560	0.7256	0.6231	0.084*
H17C	0.7171	0.6895	0.5728	0.084*
N18	0.9189 (3)	0.7242 (2)	0.4238 (2)	0.0366 (12)
C19	0.9728 (5)	0.7759 (3)	0.4317 (3)	0.0486 (17)
H19	0.9548	0.8119	0.4069	0.058*
C20	1.0527 (4)	0.7793 (3)	0.4737 (3)	0.0424 (16)
H20	1.0891	0.8157	0.4766	0.051*
C21	1.0759 (5)	0.7256 (3)	0.5114 (3)	0.0498 (18)
H21	1.1279	0.7255	0.5421	0.060*
C22	1.0221 (5)	0.6730 (3)	0.5033 (3)	0.0495 (18)
H22	1.0389	0.6366	0.5279	0.059*
C23	0.9438 (4)	0.6722 (3)	0.4596 (3)	0.0366 (15)
C24	0.8856 (4)	0.6143 (3)	0.4497 (3)	0.0401 (15)
H24A	0.9252	0.5780	0.4433	0.048*
H24B	0.8525	0.6069	0.4903	0.048*
N25	0.8189 (3)	0.6207 (2)	0.3904 (2)	0.0365 (12)
C26	0.7952 (4)	0.5727 (3)	0.3540 (3)	0.0420 (16)
H26	0.8262	0.5350	0.3648	0.050*
C27	0.7254 (4)	0.5708 (3)	0.2980 (3)	0.0387 (15)
C28	0.6581 (4)	0.6191 (3)	0.2840 (3)	0.0338 (14)
C29	0.5852 (4)	0.6098 (3)	0.2337 (3)	0.0383 (15)
C30	0.5828 (5)	0.5544 (3)	0.1966 (3)	0.0491 (18)
H30	0.5352	0.5485	0.1628	0.059*
C31	0.6483 (6)	0.5070 (3)	0.2076 (3)	0.0545 (19)
H31	0.6446	0.4701	0.1817	0.065*
C32	0.7188 (5)	0.5153 (3)	0.2574 (3)	0.0462 (17)
H32	0.7633	0.4837	0.2646	0.055*
O33	0.6623 (3)	0.67419 (18)	0.31933 (18)	0.0346 (10)
C34	0.5140 (5)	0.6611 (3)	0.2214 (3)	0.0531 (19)
H34A	0.4637	0.6457	0.1914	0.080*
H34B	0.5419	0.6970	0.2009	0.080*
H34C	0.4908	0.6735	0.2642	0.080*
Zn2	0.58596 (5)	0.70283 (3)	0.39106 (3)	0.03423 (19)
Zn3	0.37979 (5)	0.71103 (3)	0.42360 (3)	0.0355 (2)
N35	0.3122 (3)	0.6627 (2)	0.5047 (2)	0.0381 (12)
C36	0.2519 (4)	0.6139 (3)	0.4966 (3)	0.0433 (16)
H36	0.2398	0.5968	0.4532	0.052*
C37	0.2082 (5)	0.5889 (3)	0.5499 (4)	0.0507 (18)
H37	0.1683	0.5546	0.5428	0.061*
C38	0.2231 (5)	0.6144 (3)	0.6139 (4)	0.0543 (19)
H38	0.1916	0.5989	0.6501	0.065*
C39	0.2852 (5)	0.6631 (3)	0.6237 (3)	0.0487 (17)
H39	0.2973	0.6806	0.6669	0.058*
C40	0.3299 (4)	0.6859 (3)	0.5680 (3)	0.0392 (15)
C41	0.4020 (5)	0.7362 (3)	0.5766 (3)	0.0457 (17)
H41A	0.3791	0.7700	0.6044	0.055*
H41B	0.4569	0.7186	0.6009	0.055*
N42	0.4278 (3)	0.7628 (2)	0.5115 (2)	0.0373 (12)
C43	0.4673 (4)	0.8177 (3)	0.5139 (3)	0.0401 (15)
H43	0.4765	0.8366	0.5567	0.048*
C44	0.4990 (4)	0.8527 (3)	0.4556 (3)	0.0364 (14)
C45	0.5049 (4)	0.8253 (3)	0.3902 (3)	0.0336 (14)
C46	0.5371 (5)	0.8629 (3)	0.3380 (3)	0.0455 (16)
C47	0.5639 (5)	0.9250 (3)	0.3506 (4)	0.0513 (18)
H47	0.5851	0.9496	0.3155	0.062*
C48	0.5592 (5)	0.9510 (3)	0.4161 (4)	0.0499 (18)
H48	0.5781	0.9925	0.4248	0.060*
C49	0.5266 (4)	0.9146 (3)	0.4670 (3)	0.0445 (16)
H49	0.5230	0.9319	0.5103	0.053*
O50	0.4841 (3)	0.76417 (18)	0.37719 (19)	0.0351 (9)
C51	0.5446 (6)	0.8336 (3)	0.2678 (3)	0.059 (2)
H51A	0.5810	0.7957	0.2721	0.089*
H51B	0.5738	0.8632	0.2389	0.089*
H51C	0.4837	0.8236	0.2480	0.089*
N52	0.2718 (3)	0.7736 (2)	0.3802 (3)	0.0409 (13)
C53	0.2604 (5)	0.8345 (3)	0.3977 (4)	0.0476 (17)
H53	0.2959	0.8512	0.4348	0.057*
C54	0.1962 (5)	0.8734 (4)	0.3610 (4)	0.060 (2)
H54	0.1902	0.9157	0.3729	0.072*
C55	0.1417 (6)	0.8480 (4)	0.3068 (4)	0.065 (2)
H55	0.0974	0.8728	0.2827	0.079*
C56	0.1538 (5)	0.7856 (4)	0.2892 (4)	0.063 (2)
H56	0.1194	0.7680	0.2522	0.076*
C57	0.2188 (5)	0.7491 (3)	0.3280 (3)	0.0444 (16)
C58	0.2323 (5)	0.6803 (4)	0.3123 (4)	0.067 (2)
H58A	0.1798	0.6565	0.3269	0.081*
H58B	0.2338	0.6751	0.2632	0.081*
N59	0.3177 (4)	0.6545 (3)	0.3458 (3)	0.0457 (14)
C60	0.3370 (5)	0.5974 (3)	0.3312 (3)	0.0463 (17)
H60	0.2974	0.5774	0.2986	0.056*
C61	0.4145 (5)	0.5607 (3)	0.3603 (3)	0.0437 (16)
C62	0.4864 (5)	0.5839 (3)	0.4052 (3)	0.0397 (15)
C63	0.5581 (5)	0.5435 (3)	0.4317 (3)	0.0425 (16)
C64	0.5545 (5)	0.4795 (3)	0.4124 (4)	0.059 (2)
H64	0.6004	0.4519	0.4299	0.071*
C65	0.4842 (6)	0.4568 (3)	0.3680 (4)	0.068 (2)
H65	0.4845	0.4144	0.3551	0.082*
C66	0.4143 (5)	0.4951 (3)	0.3425 (3)	0.0547 (19)
H66	0.3666	0.4786	0.3135	0.066*
O67	0.4918 (3)	0.64598 (18)	0.42335 (19)	0.0380 (10)
C68	0.6329 (5)	0.5674 (3)	0.4809 (4)	0.0551 (19)
H68A	0.6636	0.6024	0.4609	0.083*
H68B	0.6768	0.5342	0.4916	0.083*
H68C	0.6064	0.5811	0.5220	0.083*
P69	0.23276 (15)	0.60244 (10)	0.10196 (11)	0.0597 (6)
F70	0.2366 (4)	0.5326 (3)	0.1279 (4)	0.155 (3)
F71	0.2338 (4)	0.6694 (2)	0.0648 (4)	0.121 (2)
F72	0.1475 (5)	0.6126 (4)	0.1376 (5)	0.211 (4)
F73	0.3280 (5)	0.5925 (3)	0.0692 (4)	0.158 (3)
F74	0.2923 (6)	0.6305 (5)	0.1620 (3)	0.198 (4)
F75	0.1769 (7)	0.5775 (4)	0.0397 (3)	0.204 (4)
P76	0.06957 (15)	0.48600 (10)	0.35167 (10)	0.0575 (5)
F77	0.0108 (5)	0.4809 (3)	0.4135 (4)	0.184 (4)
F78	0.1364 (4)	0.4333 (3)	0.3850 (3)	0.127 (2)
F79	0.0009 (5)	0.5335 (4)	0.3191 (4)	0.183 (4)
F80	0.1226 (5)	0.4857 (4)	0.2868 (3)	0.146 (3)
F81	0.0150 (6)	0.4296 (4)	0.3190 (5)	0.209 (4)
F82	0.1303 (8)	0.5347 (4)	0.3815 (5)	0.252 (5)
O83	0.0362 (7)	0.4363 (4)	0.1470 (4)	0.129 (3)
H83	0.0480	0.4596	0.1799	0.194*
C84	0.0020 (8)	0.4727 (6)	0.0906 (7)	0.160 (6)
H84A	−0.0438	0.5018	0.1048	0.240*
H84B	−0.0256	0.4452	0.0558	0.240*
H84C	0.0520	0.4957	0.0726	0.240*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0405 (4)	0.0277 (4)	0.0321 (4)	0.0005 (3)	0.0031 (3)	0.0016 (3)
N1	0.047 (3)	0.041 (3)	0.036 (3)	−0.001 (3)	0.006 (2)	0.004 (3)
C2	0.050 (4)	0.041 (4)	0.049 (4)	−0.001 (3)	0.017 (3)	0.000 (3)
C3	0.089 (6)	0.058 (5)	0.069 (5)	−0.010 (4)	0.041 (5)	−0.003 (4)
C4	0.108 (8)	0.093 (7)	0.067 (5)	−0.025 (6)	0.049 (5)	−0.012 (5)
C5	0.105 (7)	0.056 (5)	0.046 (4)	−0.019 (5)	0.022 (4)	0.013 (4)
C6	0.052 (4)	0.043 (4)	0.036 (3)	−0.014 (3)	−0.001 (3)	0.005 (3)
C7	0.071 (5)	0.039 (4)	0.044 (4)	−0.005 (4)	0.004 (4)	0.017 (3)
N8	0.051 (3)	0.027 (3)	0.037 (3)	0.004 (2)	0.002 (2)	0.002 (2)
C9	0.053 (4)	0.024 (3)	0.060 (4)	0.005 (3)	−0.004 (3)	0.000 (3)
C10	0.040 (4)	0.036 (4)	0.045 (4)	0.007 (3)	0.001 (3)	−0.012 (3)
C11	0.039 (4)	0.037 (4)	0.036 (3)	0.008 (3)	−0.004 (3)	−0.006 (3)
C12	0.042 (4)	0.056 (5)	0.036 (3)	0.014 (3)	−0.002 (3)	−0.010 (3)
C13	0.067 (5)	0.067 (6)	0.045 (4)	0.019 (4)	0.000 (4)	−0.023 (4)
C14	0.072 (6)	0.054 (5)	0.073 (5)	0.014 (4)	−0.010 (4)	−0.036 (4)
C15	0.061 (5)	0.052 (5)	0.062 (5)	0.008 (4)	−0.005 (4)	−0.014 (4)
O16	0.038 (2)	0.035 (2)	0.032 (2)	−0.0026 (19)	−0.0024 (18)	−0.0092 (18)
C17	0.062 (5)	0.067 (5)	0.039 (4)	0.007 (4)	0.005 (3)	−0.005 (4)
N18	0.042 (3)	0.031 (3)	0.038 (3)	−0.003 (2)	0.004 (2)	0.002 (2)
C19	0.053 (5)	0.047 (4)	0.047 (4)	0.000 (4)	0.008 (3)	0.002 (3)
C20	0.037 (4)	0.047 (4)	0.043 (4)	−0.012 (3)	0.002 (3)	0.001 (3)
C21	0.036 (4)	0.060 (5)	0.053 (4)	−0.002 (3)	−0.006 (3)	−0.010 (4)
C22	0.043 (4)	0.048 (4)	0.056 (4)	0.009 (3)	−0.004 (4)	0.003 (3)
C23	0.033 (4)	0.040 (4)	0.038 (3)	0.005 (3)	0.005 (3)	−0.002 (3)
C24	0.044 (4)	0.035 (4)	0.041 (3)	0.002 (3)	0.002 (3)	0.007 (3)
N25	0.049 (3)	0.027 (3)	0.034 (3)	0.001 (2)	0.000 (2)	0.001 (2)
C26	0.055 (4)	0.023 (3)	0.049 (4)	0.003 (3)	0.013 (3)	0.002 (3)
C27	0.052 (4)	0.030 (4)	0.034 (3)	−0.005 (3)	0.005 (3)	−0.003 (3)
C28	0.043 (4)	0.029 (3)	0.030 (3)	−0.008 (3)	0.006 (3)	−0.001 (3)
C29	0.050 (4)	0.037 (4)	0.028 (3)	−0.008 (3)	0.005 (3)	−0.002 (3)
C30	0.071 (5)	0.043 (4)	0.033 (3)	−0.019 (4)	0.002 (3)	−0.002 (3)
C31	0.088 (6)	0.032 (4)	0.044 (4)	−0.009 (4)	0.007 (4)	−0.011 (3)
C32	0.072 (5)	0.022 (3)	0.047 (4)	0.000 (3)	0.018 (4)	0.000 (3)
O33	0.043 (3)	0.032 (2)	0.029 (2)	−0.0015 (19)	0.0036 (18)	−0.0062 (18)
C34	0.066 (5)	0.050 (5)	0.042 (4)	0.001 (4)	−0.011 (3)	0.001 (3)
Zn2	0.0379 (4)	0.0325 (4)	0.0324 (3)	0.0004 (3)	0.0031 (3)	−0.0019 (3)
Zn3	0.0383 (4)	0.0325 (4)	0.0356 (4)	0.0008 (3)	0.0017 (3)	−0.0039 (3)
N35	0.041 (3)	0.033 (3)	0.041 (3)	0.000 (2)	0.005 (2)	0.000 (2)
C36	0.041 (4)	0.032 (4)	0.057 (4)	0.003 (3)	0.004 (3)	−0.001 (3)
C37	0.046 (4)	0.029 (4)	0.077 (5)	0.000 (3)	0.006 (4)	0.013 (4)
C38	0.057 (5)	0.049 (5)	0.058 (5)	0.003 (4)	0.013 (4)	0.020 (4)
C39	0.055 (5)	0.046 (4)	0.047 (4)	−0.001 (3)	0.012 (3)	0.008 (3)
C40	0.043 (4)	0.033 (4)	0.042 (4)	0.007 (3)	0.003 (3)	0.004 (3)
C41	0.063 (5)	0.041 (4)	0.033 (3)	−0.002 (3)	0.004 (3)	0.002 (3)
N42	0.041 (3)	0.032 (3)	0.039 (3)	0.003 (2)	0.004 (2)	−0.003 (2)
C43	0.044 (4)	0.040 (4)	0.036 (3)	0.006 (3)	−0.003 (3)	−0.007 (3)
C44	0.039 (4)	0.025 (3)	0.045 (3)	0.005 (3)	0.004 (3)	−0.003 (3)
C45	0.036 (4)	0.027 (3)	0.039 (3)	0.002 (3)	0.004 (3)	0.002 (3)
C46	0.056 (5)	0.034 (4)	0.045 (4)	0.011 (3)	−0.003 (3)	0.003 (3)
C47	0.057 (5)	0.042 (4)	0.056 (4)	0.007 (3)	0.006 (4)	0.011 (3)
C48	0.055 (5)	0.026 (4)	0.068 (5)	0.001 (3)	0.004 (4)	0.007 (3)
C49	0.047 (4)	0.032 (4)	0.054 (4)	0.004 (3)	0.003 (3)	−0.006 (3)
O50	0.041 (3)	0.027 (2)	0.037 (2)	0.0044 (19)	0.0024 (18)	−0.0030 (18)
C51	0.093 (6)	0.051 (5)	0.034 (4)	−0.007 (4)	0.005 (4)	0.005 (3)
N52	0.040 (3)	0.041 (3)	0.042 (3)	−0.001 (2)	0.004 (2)	0.003 (3)
C53	0.043 (4)	0.045 (4)	0.055 (4)	0.003 (3)	0.006 (3)	0.004 (3)
C54	0.057 (5)	0.058 (5)	0.067 (5)	0.014 (4)	0.013 (4)	0.016 (4)
C55	0.062 (6)	0.064 (6)	0.070 (5)	0.017 (4)	0.004 (4)	0.025 (5)
C56	0.057 (5)	0.079 (6)	0.053 (4)	0.008 (4)	0.000 (4)	0.011 (4)
C57	0.049 (4)	0.046 (4)	0.037 (3)	0.002 (3)	−0.002 (3)	0.005 (3)
C58	0.066 (6)	0.058 (5)	0.074 (5)	0.009 (4)	−0.022 (4)	−0.016 (4)
N59	0.046 (4)	0.042 (4)	0.048 (3)	0.000 (3)	−0.005 (3)	−0.002 (3)
C60	0.063 (5)	0.034 (4)	0.042 (4)	−0.010 (3)	0.005 (3)	−0.003 (3)
C61	0.065 (5)	0.030 (4)	0.038 (3)	−0.005 (3)	0.017 (3)	−0.003 (3)
C62	0.053 (4)	0.032 (4)	0.037 (3)	−0.001 (3)	0.019 (3)	0.001 (3)
C63	0.058 (5)	0.029 (4)	0.043 (4)	0.003 (3)	0.020 (3)	0.000 (3)
C64	0.065 (5)	0.045 (5)	0.068 (5)	0.017 (4)	0.016 (4)	0.004 (4)
C65	0.112 (7)	0.027 (4)	0.067 (5)	0.010 (4)	0.011 (5)	−0.018 (4)
C66	0.080 (6)	0.040 (4)	0.043 (4)	−0.002 (4)	−0.001 (4)	−0.013 (3)
O67	0.045 (3)	0.029 (2)	0.041 (2)	0.0034 (19)	0.009 (2)	−0.0007 (19)
C68	0.060 (5)	0.042 (4)	0.064 (5)	0.005 (4)	0.008 (4)	0.017 (4)
P69	0.0568 (14)	0.0609 (14)	0.0607 (12)	0.0013 (10)	−0.0005 (10)	−0.0025 (11)
F70	0.134 (5)	0.115 (5)	0.218 (7)	0.007 (4)	0.040 (5)	0.100 (5)
F71	0.096 (4)	0.069 (4)	0.191 (6)	−0.001 (3)	−0.042 (4)	0.029 (4)
F72	0.124 (6)	0.200 (8)	0.325 (11)	−0.007 (5)	0.140 (7)	−0.099 (8)
F73	0.132 (6)	0.096 (5)	0.258 (9)	0.021 (4)	0.103 (6)	0.057 (5)
F74	0.192 (8)	0.318 (11)	0.079 (4)	−0.126 (8)	−0.029 (5)	−0.003 (6)
F75	0.338 (11)	0.154 (6)	0.105 (5)	−0.157 (7)	−0.081 (6)	0.025 (5)
P76	0.0661 (14)	0.0483 (12)	0.0595 (12)	−0.0011 (10)	0.0135 (10)	0.0038 (10)
F77	0.225 (8)	0.160 (6)	0.187 (7)	0.108 (6)	0.151 (6)	0.104 (6)
F78	0.140 (5)	0.135 (5)	0.106 (4)	0.059 (4)	0.005 (4)	0.021 (4)
F79	0.184 (7)	0.193 (7)	0.181 (7)	0.135 (6)	0.091 (6)	0.120 (6)
F80	0.160 (6)	0.191 (7)	0.093 (4)	0.053 (5)	0.058 (4)	0.017 (4)
F81	0.219 (9)	0.138 (7)	0.256 (10)	−0.059 (6)	−0.072 (8)	−0.027 (7)
F82	0.324 (13)	0.175 (8)	0.246 (10)	−0.154 (9)	−0.060 (9)	−0.064 (7)
O83	0.159 (7)	0.118 (6)	0.110 (6)	−0.024 (6)	0.005 (6)	−0.004 (5)
C84	0.143 (11)	0.157 (12)	0.173 (13)	−0.053 (9)	−0.039 (10)	0.103 (11)

Geometric parameters (Å, º)

Zn1—N25	2.078 (5)	N35—C40	1.342 (7)
Zn1—N8	2.080 (5)	N35—C36	1.351 (8)
Zn1—O16	2.131 (4)	C36—C37	1.365 (9)
Zn1—N1	2.141 (5)	C36—H36	0.9300
Zn1—O33	2.153 (4)	C37—C38	1.367 (9)
Zn1—N18	2.158 (5)	C37—H37	0.9300
Zn1—Zn2	3.0826 (12)	C38—C39	1.369 (9)
N1—C6	1.310 (7)	C38—H38	0.9300
N1—C2	1.345 (8)	C39—C40	1.394 (8)
C2—C3	1.362 (9)	C39—H39	0.9300
C2—H2	0.9300	C40—C41	1.490 (9)
C3—C4	1.365 (11)	C41—N42	1.465 (7)
C3—H3	0.9300	C41—H41A	0.9700
C4—C5	1.390 (11)	C41—H41B	0.9700
C4—H4	0.9300	N42—C43	1.291 (7)
C5—C6	1.407 (9)	C43—C44	1.463 (8)
C5—H5	0.9300	C43—H43	0.9300
C6—C7	1.514 (9)	C44—C49	1.379 (8)
C7—N8	1.472 (7)	C44—C45	1.414 (8)
C7—H7A	0.9700	C45—O50	1.346 (7)
C7—H7B	0.9700	C45—C46	1.401 (8)
N8—C9	1.275 (7)	C46—C47	1.386 (9)
C9—C10	1.477 (9)	C46—C51	1.519 (8)
C9—H9	0.9300	C47—C48	1.402 (9)
C10—C11	1.397 (8)	C47—H47	0.9300
C10—C15	1.413 (9)	C48—C49	1.371 (8)
C11—O16	1.340 (7)	C48—H48	0.9300
C11—C12	1.415 (8)	C49—H49	0.9300
C12—C13	1.376 (9)	C51—H51A	0.9600
C12—C17	1.528 (9)	C51—H51B	0.9600
C13—C14	1.371 (10)	C51—H51C	0.9600
C13—H13	0.9300	N52—C57	1.339 (8)
C14—C15	1.369 (10)	N52—C53	1.344 (8)
C14—H14	0.9300	C53—C54	1.400 (9)
C15—H15	0.9300	C53—H53	0.9300
Zn2—O16	1.963 (4)	C54—C55	1.385 (11)
C17—H17A	0.9600	C54—H54	0.9300
C17—H17B	0.9600	C55—C56	1.377 (10)
C17—H17C	0.9600	C55—H55	0.9300
N18—C23	1.339 (7)	C56—C57	1.398 (9)
N18—C19	1.345 (8)	C56—H56	0.9300
C19—C20	1.372 (9)	C57—C58	1.501 (10)
C19—H19	0.9300	C58—N59	1.464 (8)
C20—C21	1.382 (9)	C58—H58A	0.9700
C20—H20	0.9300	C58—H58B	0.9700
C21—C22	1.360 (9)	N59—C60	1.273 (8)
C21—H21	0.9300	C60—C61	1.447 (9)
C22—C23	1.371 (9)	C60—H60	0.9300
C22—H22	0.9300	C61—C62	1.402 (9)
C23—C24	1.489 (8)	C61—C66	1.430 (9)
C24—N25	1.464 (7)	C62—O67	1.359 (7)
C24—H24A	0.9700	C62—C63	1.414 (9)
C24—H24B	0.9700	C63—C64	1.402 (9)
N25—C26	1.273 (7)	C63—C68	1.487 (9)
C26—C27	1.441 (9)	C64—C65	1.378 (10)
C26—H26	0.9300	C64—H64	0.9300
C27—C32	1.415 (8)	C65—C66	1.361 (10)
C27—C28	1.424 (8)	C65—H65	0.9300
C28—O33	1.354 (6)	C66—H66	0.9300
C28—C29	1.405 (8)	C68—H68A	0.9600
C29—C30	1.377 (8)	C68—H68B	0.9600
C29—C34	1.503 (9)	C68—H68C	0.9600
C30—C31	1.384 (9)	P69—F72	1.475 (6)
C30—H30	0.9300	P69—F75	1.511 (6)
C31—C32	1.372 (10)	P69—F74	1.528 (6)
C31—H31	0.9300	P69—F70	1.560 (6)
C32—H32	0.9300	P69—F73	1.573 (6)
Zn2—O33	1.944 (4)	P69—F71	1.592 (6)
C34—H34A	0.9600	P76—F82	1.448 (6)
C34—H34B	0.9600	P76—F79	1.520 (6)
C34—H34C	0.9600	P76—F80	1.531 (5)
Zn2—O67	1.953 (4)	P76—F77	1.532 (5)
Zn2—O50	1.966 (4)	P76—F81	1.543 (7)
Zn2—Zn3	3.0967 (12)	P76—F78	1.584 (6)
Zn3—N59	2.090 (5)	O83—C84	1.407 (11)
Zn3—N42	2.117 (5)	O83—H83	0.8200
Zn3—O67	2.124 (4)	C84—H84A	0.9600
Zn3—O50	2.134 (4)	C84—H84B	0.9600
Zn3—N52	2.173 (5)	C84—H84C	0.9600
Zn3—N35	2.178 (5)
N25—Zn1—N8	175.0 (2)	N42—Zn3—N35	77.63 (19)
N25—Zn1—O16	96.87 (17)	O67—Zn3—N35	94.59 (17)
N8—Zn1—O16	84.17 (17)	O50—Zn3—N35	157.60 (17)
N25—Zn1—N1	100.63 (19)	N52—Zn3—N35	102.94 (19)
N8—Zn1—N1	79.0 (2)	N59—Zn3—Zn2	100.88 (15)
O16—Zn1—N1	161.17 (18)	N42—Zn3—Zn2	86.06 (13)
N25—Zn1—O33	83.27 (18)	O67—Zn3—Zn2	38.56 (11)
N8—Zn1—O33	101.73 (18)	O50—Zn3—Zn2	38.96 (10)
O16—Zn1—O33	77.71 (14)	N52—Zn3—Zn2	128.97 (13)
N1—Zn1—O33	97.42 (17)	N35—Zn3—Zn2	127.74 (14)
N25—Zn1—N18	78.33 (19)	C40—N35—C36	117.8 (5)
N8—Zn1—N18	96.7 (2)	C40—N35—Zn3	116.0 (4)
O16—Zn1—N18	96.50 (16)	C36—N35—Zn3	126.2 (4)
N1—Zn1—N18	93.81 (19)	N35—C36—C37	122.3 (6)
O33—Zn1—N18	159.93 (17)	N35—C36—H36	118.8
N25—Zn1—Zn2	92.41 (14)	C37—C36—H36	118.8
N8—Zn1—Zn2	91.47 (14)	C36—C37—C38	119.9 (7)
O16—Zn1—Zn2	39.14 (10)	C36—C37—H37	120.1
N1—Zn1—Zn2	132.39 (14)	C38—C37—H37	120.1
O33—Zn1—Zn2	38.69 (10)	C37—C38—C39	119.0 (6)
N18—Zn1—Zn2	133.75 (13)	C37—C38—H38	120.5
C6—N1—C2	119.5 (5)	C39—C38—H38	120.5
C6—N1—Zn1	115.2 (4)	C38—C39—C40	119.0 (7)
C2—N1—Zn1	125.2 (4)	C38—C39—H39	120.5
N1—C2—C3	123.3 (7)	C40—C39—H39	120.5
N1—C2—H2	118.3	N35—C40—C39	122.0 (6)
C3—C2—H2	118.3	N35—C40—C41	116.8 (5)
C2—C3—C4	117.6 (7)	C39—C40—C41	121.2 (6)
C2—C3—H3	121.2	N42—C41—C40	113.2 (5)
C4—C3—H3	121.2	N42—C41—H41A	108.9
C3—C4—C5	120.7 (7)	C40—C41—H41A	108.9
C3—C4—H4	119.7	N42—C41—H41B	108.9
C5—C4—H4	119.7	C40—C41—H41B	108.9
C4—C5—C6	117.6 (7)	H41A—C41—H41B	107.8
C4—C5—H5	121.2	C43—N42—C41	116.8 (5)
C6—C5—H5	121.2	C43—N42—Zn3	127.7 (4)
N1—C6—C5	121.3 (7)	C41—N42—Zn3	115.0 (4)
N1—C6—C7	118.7 (5)	N42—C43—C44	126.0 (6)
C5—C6—C7	120.0 (6)	N42—C43—H43	117.0
N8—C7—C6	110.9 (5)	C44—C43—H43	117.0
N8—C7—H7A	109.5	C49—C44—C45	120.0 (6)
C6—C7—H7A	109.5	C49—C44—C43	117.0 (6)
N8—C7—H7B	109.5	C45—C44—C43	122.9 (5)
C6—C7—H7B	109.5	O50—C45—C46	119.1 (5)
H7A—C7—H7B	108.0	O50—C45—C44	122.5 (5)
C9—N8—C7	118.1 (5)	C46—C45—C44	118.4 (5)
C9—N8—Zn1	123.9 (4)	C47—C46—C45	120.6 (6)
C7—N8—Zn1	115.0 (4)	C47—C46—C51	120.7 (6)
N8—C9—C10	124.6 (6)	C45—C46—C51	118.7 (6)
N8—C9—H9	117.7	C46—C47—C48	120.2 (6)
C10—C9—H9	117.7	C46—C47—H47	119.9
C11—C10—C15	119.8 (6)	C48—C47—H47	119.9
C11—C10—C9	125.1 (5)	C49—C48—C47	119.3 (6)
C15—C10—C9	115.0 (6)	C49—C48—H48	120.3
O16—C11—C10	121.4 (5)	C47—C48—H48	120.3
O16—C11—C12	118.9 (6)	C48—C49—C44	121.5 (6)
C10—C11—C12	119.6 (6)	C48—C49—H49	119.2
C13—C12—C11	118.4 (7)	C44—C49—H49	119.2
C13—C12—C17	123.1 (6)	C45—O50—Zn2	116.7 (3)
C11—C12—C17	118.4 (6)	C45—O50—Zn3	125.4 (3)
C14—C13—C12	122.2 (7)	Zn2—O50—Zn3	98.02 (16)
C14—C13—H13	118.9	C46—C51—H51A	109.5
C12—C13—H13	118.9	C46—C51—H51B	109.5
C15—C14—C13	120.4 (7)	H51A—C51—H51B	109.5
C15—C14—H14	119.8	C46—C51—H51C	109.5
C13—C14—H14	119.8	H51A—C51—H51C	109.5
C14—C15—C10	119.6 (7)	H51B—C51—H51C	109.5
C14—C15—H15	120.2	C57—N52—C53	119.4 (6)
C10—C15—H15	120.2	C57—N52—Zn3	114.9 (4)
C11—O16—Zn2	131.8 (4)	C53—N52—Zn3	125.4 (4)
C11—O16—Zn1	119.4 (4)	N52—C53—C54	121.3 (7)
Zn2—O16—Zn1	97.62 (15)	N52—C53—H53	119.4
C12—C17—H17A	109.5	C54—C53—H53	119.4
C12—C17—H17B	109.5	C55—C54—C53	119.3 (7)
H17A—C17—H17B	109.5	C55—C54—H54	120.4
C12—C17—H17C	109.5	C53—C54—H54	120.4
H17A—C17—H17C	109.5	C56—C55—C54	119.1 (7)
H17B—C17—H17C	109.5	C56—C55—H55	120.5
C23—N18—C19	118.3 (6)	C54—C55—H55	120.5
C23—N18—Zn1	113.9 (4)	C55—C56—C57	118.9 (7)
C19—N18—Zn1	127.9 (4)	C55—C56—H56	120.5
N18—C19—C20	124.6 (6)	C57—C56—H56	120.5
N18—C19—H19	117.7	N52—C57—C56	122.0 (7)
C20—C19—H19	117.7	N52—C57—C58	117.1 (6)
C19—C20—C21	116.1 (6)	C56—C57—C58	120.9 (7)
C19—C20—H20	121.9	N59—C58—C57	112.7 (6)
C21—C20—H20	121.9	N59—C58—H58A	109.0
C22—C21—C20	119.5 (6)	C57—C58—H58A	109.0
C22—C21—H21	120.2	N59—C58—H58B	109.0
C20—C21—H21	120.2	C57—C58—H58B	109.0
C21—C22—C23	121.6 (7)	H58A—C58—H58B	107.8
C21—C22—H22	119.2	C60—N59—C58	116.3 (6)
C23—C22—H22	119.2	C60—N59—Zn3	128.0 (5)
N18—C23—C22	119.8 (6)	C58—N59—Zn3	114.9 (4)
N18—C23—C24	118.4 (6)	N59—C60—C61	126.4 (6)
C22—C23—C24	121.8 (6)	N59—C60—H60	116.8
N25—C24—C23	111.3 (5)	C61—C60—H60	116.8
N25—C24—H24A	109.4	C62—C61—C66	118.8 (7)
C23—C24—H24A	109.4	C62—C61—C60	125.5 (6)
N25—C24—H24B	109.4	C66—C61—C60	115.7 (6)
C23—C24—H24B	109.4	O67—C62—C61	121.9 (6)
H24A—C24—H24B	108.0	O67—C62—C63	117.3 (6)
C26—N25—C24	120.5 (5)	C61—C62—C63	120.8 (6)
C26—N25—Zn1	123.9 (4)	C64—C63—C62	118.0 (7)
C24—N25—Zn1	114.4 (4)	C64—C63—C68	121.0 (6)
N25—C26—C27	126.6 (6)	C62—C63—C68	120.9 (6)
N25—C26—H26	116.7	C65—C64—C63	121.1 (7)
C27—C26—H26	116.7	C65—C64—H64	119.4
C32—C27—C28	117.8 (6)	C63—C64—H64	119.4
C32—C27—C26	117.9 (6)	C66—C65—C64	121.5 (7)
C28—C27—C26	124.1 (5)	C66—C65—H65	119.3
O33—C28—C29	118.9 (5)	C64—C65—H65	119.3
O33—C28—C27	120.8 (5)	C65—C66—C61	119.8 (7)
C29—C28—C27	120.3 (5)	C65—C66—H66	120.1
C30—C29—C28	118.6 (6)	C61—C66—H66	120.1
C30—C29—C34	122.4 (6)	C62—O67—Zn2	122.4 (3)
C28—C29—C34	118.9 (5)	C62—O67—Zn3	126.5 (4)
C29—C30—C31	122.6 (7)	Zn2—O67—Zn3	98.75 (17)
C29—C30—H30	118.7	C63—C68—H68A	109.5
C31—C30—H30	118.7	C63—C68—H68B	109.5
C32—C31—C30	119.1 (6)	H68A—C68—H68B	109.5
C32—C31—H31	120.5	C63—C68—H68C	109.5
C30—C31—H31	120.5	H68A—C68—H68C	109.5
C31—C32—C27	121.5 (6)	H68B—C68—H68C	109.5
C31—C32—H32	119.3	F72—P69—F75	90.9 (6)
C27—C32—H32	119.3	F72—P69—F74	91.3 (5)
C28—O33—Zn2	129.1 (3)	F75—P69—F74	176.4 (4)
C28—O33—Zn1	122.1 (4)	F72—P69—F70	89.7 (4)
Zn2—O33—Zn1	97.47 (16)	F75—P69—F70	86.5 (4)
C29—C34—H34A	109.5	F74—P69—F70	96.3 (5)
C29—C34—H34B	109.5	F72—P69—F73	175.7 (5)
H34A—C34—H34B	109.5	F75—P69—F73	93.3 (5)
C29—C34—H34C	109.5	F74—P69—F73	84.5 (5)
H34A—C34—H34C	109.5	F70—P69—F73	89.7 (3)
H34B—C34—H34C	109.5	F72—P69—F71	97.0 (5)
O33—Zn2—O67	119.14 (16)	F75—P69—F71	87.9 (4)
O33—Zn2—O16	86.94 (16)	F74—P69—F71	89.1 (4)
O67—Zn2—O16	130.43 (16)	F70—P69—F71	171.2 (4)
O33—Zn2—O50	124.23 (16)	F73—P69—F71	84.0 (3)
O67—Zn2—O50	85.26 (16)	F82—P76—F79	93.4 (6)
O16—Zn2—O50	115.57 (17)	F82—P76—F80	90.8 (5)
O33—Zn2—Zn1	43.84 (12)	F79—P76—F80	90.2 (4)
O67—Zn2—Zn1	144.30 (12)	F82—P76—F77	94.9 (6)
O16—Zn2—Zn1	43.25 (11)	F79—P76—F77	89.8 (3)
O50—Zn2—Zn1	130.38 (12)	F80—P76—F77	174.4 (5)
O33—Zn2—Zn3	140.33 (12)	F82—P76—F81	173.5 (7)
O67—Zn2—Zn3	42.69 (11)	F79—P76—F81	92.0 (5)
O16—Zn2—Zn3	132.53 (11)	F80—P76—F81	85.6 (5)
O50—Zn2—Zn3	43.02 (11)	F77—P76—F81	88.8 (5)
Zn1—Zn2—Zn3	172.50 (3)	F82—P76—F78	89.9 (5)
N59—Zn3—N42	171.5 (2)	F79—P76—F78	176.5 (5)
N59—Zn3—O67	85.28 (19)	F80—P76—F78	90.8 (3)
N42—Zn3—O67	97.42 (17)	F77—P76—F78	88.9 (3)
N59—Zn3—O50	105.67 (18)	F81—P76—F78	84.8 (4)
N42—Zn3—O50	82.80 (17)	C84—O83—H83	109.5
O67—Zn3—O50	77.13 (15)	O83—C84—H84A	109.5
N59—Zn3—N52	78.6 (2)	O83—C84—H84B	109.5
N42—Zn3—N52	100.97 (19)	H84A—C84—H84B	109.5
O67—Zn3—N52	156.86 (17)	O83—C84—H84C	109.5
O50—Zn3—N52	91.31 (17)	H84A—C84—H84C	109.5
N59—Zn3—N35	94.2 (2)	H84B—C84—H84C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O83—H83···F80	0.82	2.35	3.112 (10)	154
C36—H36···F82	0.93	2.43	3.230 (10)	145
C41—H41A···F71^i	0.97	2.53	3.140 (9)	121
C58—H58B···F74	0.97	2.40	3.302 (11)	154

Symmetry code: (i) x, −y+3/2, z+1/2.