[5,10,15,20-Tetra­kis­(penta­fluoro­phen­yl)porphyrin­ato]zinc(II) benzene disolvate

Lin, Z.; Li, J.

doi:10.1107/S2414314620008779

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 7| July 2020| x200877

https://doi.org/10.1107/S2414314620008779

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[5,10,15,20-Tetrakis(pentafluorophenyl)porphyrinato]zinc(II) benzene disolvate

Zeyuan Lin ^a and Jianfeng Li ^a ^*

^aCollege of Materials Science and Opto-electronic Technology, CAS Center for Excellence in Topological Quantum Computation & Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Yanqi Lake, Huairou District, Beijing 101408, People's Republic of China
^*Correspondence e-mail: jfli@ucas.ac.cn

Edited by W. Imhof, University Koblenz-Landau, Germany (Received 6 June 2020; accepted 30 June 2020; online 10 July 2020)

Single crystals of the title zinc porphyrinato complex, [Zn(C₄₄H₈F₂₀N₄)]·2C₆H₆, were obtained by the solvent evaporation method. The molecular complex exhibits point group symmetry $[\overline1]$ with the central Zn^II atom located on an inversion centre. The porphyrinato core is approximately planar, and the cation has no other ligating atoms than the four porphyrinato N atoms. π–π interactions between benzene solvent molecules and [Zn(TFPP)] units lead to multilayer packing structures. In addition, intermolecular C—H⋯F hydrogen bonding is observed between [Zn(TFPP)] molecules.

Keywords: crystal structure; zinc porphyrin; hydrogen interaction; π–π interaction.

CCDC reference: 2013055

Structure description

Metalloporphyrin derivatives have been investigated extensively, not only as heme models but also as functional building blocks of molecular materials and devices. Zinc porphyrins have been employed as photosensitizers (Liu et al., 2006 ) and chemical sensors (Wu et al., 2016 ) because of their good photoelectronic and chemical stabilities. In 1995, Gray and co-workers published the first zinc porphyrin crystal structure, (5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato)zinc(II) n-hexane solvate, which crystallizes in the space group P2₁/c and shows a planar conformation of the porphyrin ligand (Birnbaum et al., 1995 ). In this work, a new zinc pentafluorophenyl-porphyrin crystal structure, [Zn(TFPP)]·2C₆H₆ (TFPP is the tetrakis(pentafluorphenyl)porphyrinato ligand), is reported.

The molecular entities of the title compound are shown in Fig. 1. The structural features of the current complex are similar to those of the previously reported [Zn(TFPP)] n-hexane solvate (Birnbaum et al., 1995). As can be seen, the porphyrinato core is approximately planar (r.m.s. deviation = 0.03 Å). Two benzene solvent molecules are found besides the [Zn(TFPP)] units. One of them is found to be disordered (CS1–CS6) over two positions. π–π stacking interactions are observed between the disordered benzene molecules and [Zn(TFPP)] moieties, as illustrated in Fig. 2. The distance between the centroid of the benzene ring (X_cent) and the porphyrinato plane is 3.098 Å, which is consistent with the reported values for related complexes (about 3.33–3.45 Å; Uno et al., 2003 ).

Figure 1
ORTEP diagram of the molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Only one orientation of the disordered solvent benzene molecule (CS1–CS6) is shown. H atoms are omitted for clarity.

Figure 2
Schematic illustration of π–π stacking in the crystal structure of the title compound showing the distance between the centroid of benzene ring (Xcent) and the porphyrinato plane.

Intermolecular non-bonding interactions are also found for the title compound. As given in Fig. 3 and Table 1, the distance between CB3 and F4, HB3 and F4 are 3.276 and 2.36 Å, respectively, being consistent with C–H⋯F hydrogen bonds (3.455 and 2.53 Å, respectively; Thamotharan et al., 2003 ). The packing pattern of the title compound is shown in Fig. 4.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
CB3—HB3⋯F4ⁱ	0.95	2.36	3.276 (2)	163
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 3
C—H⋯F hydrogen bonds in the crystal structure of the title compound.

Figure 4
A view of the packing pattern of the title compound with the unit cell indicated by orange lines. H atoms are omitted for clarity.

Synthesis and crystallization

General Information. All operations were accomplished by standard Schlenk techniques unless otherwise specified. Benzene, which was used for crystallization of the final products, was washed with concentrated sulfuric acid and then with sodium bicarbonate solution at least three times, dried with anhydrous magnesium sulfate and distilled with calcium hydride, sodium and diphenylketone, sequentially under argon atmosphere. The precursor compound H₂(TFPP) was synthesized by the method reported by Lindsey et al. (1987 ).

Synthesis of [5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato]zinc(II) benzene disolvate

H₂(TFPP) (500 mg, 0.51 mmol) and Zn(Ac)₂·2H₂O (2.25 g, 10.26 mmol) were dissolved in 250 ml of CH₃OH and 250 ml of CHCl₃. After the solution had been transferred to a conical flask (1000 ml), it was refluxed under stirring for 4 h under argon. The raw products were washed with deionized water to remove the remaining zinc salts. The organic phases were dried and purified by column chromatography using silica and eluting the product with hexane/dichloromethane (2:1). Red–pink [Zn(TFPP)] powder (yield 489 mg, 0.47 mmol, 91.8%), was obtained after solvent evaporation. Red single crystals of the title compound were grown by slow solvent evaporation of a solution of the title compound in freshly distilled benzene at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. A solvent benzene molecule is observed to be disordered over two positions of equal occupancy (CS1–CS6). These atoms and corresponding bonds were restrained by ISOR and RIGU commands, respectively.

Table 2
Experimental details

Crystal data
Chemical formula	[Zn(C₄₄H₈F₂₀N₄)]·2C₆H₆
M_r	1194.13
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	34.176 (7), 6.3699 (13), 26.382 (5)
β (°)	123.428 (6)
V (Å³)	4793.4 (17)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.64
Crystal size (mm)	0.42 × 0.14 × 0.12

Data collection
Diffractometer	Bruker D8 QUEST System
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.656, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	22042, 5287, 4369
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.645

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.119, 0.91
No. of reflections	5287
No. of parameters	367
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.38
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXT2014/6 (Sheldrick, 2015a ), SHELXL2014/6 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ), Mercury (Macrae et al., 2020 ) and enCIFer (Allen et al., 2004 ).

Structural data

CCDC reference: 2013055

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2414314620008779/im4008sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2414314620008779/im4008Isup3.cdx

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620008779/im4008Isup4.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT2014/6 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: enCIFer (Allen et al., 2004).

[5,10,15,20-Tetrakis(pentafluorophenyl)porphyrinato]zinc(II) benzene disolvate top

Crystal data top

[Zn(C₄₄H₈F₂₀N₄)]·2C₆H₆	F(000) = 2376
M_r = 1194.13	D_x = 1.655 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 34.176 (7) Å	Cell parameters from 9674 reflections
b = 6.3699 (13) Å	θ = 2.9–27.1°
c = 26.382 (5) Å	µ = 0.64 mm⁻¹
β = 123.428 (6)°	T = 100 K
V = 4793.4 (17) Å³	Block, red
Z = 4	0.42 × 0.14 × 0.12 mm

Data collection top

Bruker D8 QUEST System diffractometer	4369 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.044
f\ and ω scans	θ_max = 27.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −42→43
T_min = 0.656, T_max = 0.746	k = −8→8
22042 measured reflections	l = −33→33
5287 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 0.91	(Δ/σ)_max < 0.001
5287 reflections	Δρ_max = 0.38 e Å⁻³
367 parameters	Δρ_min = −0.38 e Å⁻³

Special details top

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. All of hydrogen atoms were placed in calculated positions (C–H = 0.95 Å for aryl hydrogen atoms) and were refined using a riding model with fixed isotropic displacement parameters of U_iso(H) = 1.2U_eq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.000000	0.500000	0.000000	0.01507 (8)
F1	0.12626 (4)	0.03956 (18)	0.20870 (5)	0.0382 (3)
F2	0.20705 (5)	−0.0107 (2)	0.31796 (6)	0.0552 (4)
F3	0.27217 (4)	0.2974 (2)	0.36575 (5)	0.0529 (4)
F4	0.25736 (4)	0.6539 (2)	0.30139 (5)	0.0505 (4)
F5	0.17700 (4)	0.70796 (18)	0.19275 (5)	0.0360 (3)
F6	0.04641 (5)	0.0847 (2)	−0.14163 (6)	0.0527 (3)
F7	0.09198 (7)	0.0230 (3)	−0.19701 (7)	0.0770 (5)
F8	0.15178 (5)	0.3220 (3)	−0.18992 (7)	0.0782 (6)
F9	0.16562 (5)	0.6763 (3)	−0.12718 (7)	0.0732 (5)
F10	0.12069 (5)	0.7385 (2)	−0.07077 (6)	0.0499 (3)
N1	0.01956 (5)	0.4839 (2)	0.08851 (6)	0.0164 (3)
N2	0.06745 (5)	0.4424 (2)	0.02711 (6)	0.0171 (3)
C1	0.14878 (6)	0.3755 (3)	0.19688 (7)	0.0203 (3)
C2	0.15802 (6)	0.1941 (3)	0.23036 (8)	0.0268 (4)
C3	0.19933 (7)	0.1660 (3)	0.28668 (8)	0.0341 (5)
C4	0.23254 (6)	0.3214 (4)	0.31069 (7)	0.0341 (5)
C5	0.22491 (6)	0.5017 (3)	0.27841 (8)	0.0323 (4)
C6	0.18339 (6)	0.5273 (3)	0.22238 (8)	0.0250 (4)
C7	0.08204 (6)	0.4135 (3)	−0.10438 (8)	0.0280 (4)
C8	0.07564 (7)	0.2338 (4)	−0.13712 (9)	0.0373 (5)
C9	0.09912 (9)	0.2002 (4)	−0.16577 (10)	0.0505 (7)
C10	0.12929 (8)	0.3496 (5)	−0.16194 (10)	0.0525 (7)
C11	0.13627 (8)	0.5295 (4)	−0.13032 (10)	0.0488 (7)
C12	0.11267 (7)	0.5597 (4)	−0.10180 (9)	0.0365 (5)
C(A1	−0.00926 (6)	0.5061 (3)	0.10911 (7)	0.0196 (3)
C(A2	0.06336 (6)	0.4409 (3)	0.13817 (7)	0.0179 (3)
C(A3	0.10493 (6)	0.4068 (3)	0.08512 (7)	0.0194 (3)
C(A4	0.08383 (6)	0.4208 (3)	−0.00964 (7)	0.0212 (3)
C(B1	0.01740 (6)	0.4734 (3)	0.17401 (7)	0.0279 (4)
H(B1	0.005686	0.478869	0.199334	0.034*
C(B2	0.06203 (6)	0.4336 (3)	0.19194 (7)	0.0259 (4)
H(B2	0.087686	0.406087	0.232232	0.031*
C(B3	0.14611 (6)	0.3610 (3)	0.08474 (8)	0.0290 (4)
H(B3	0.176594	0.330989	0.119056	0.035*
C(B4	0.13301 (6)	0.3690 (3)	0.02628 (8)	0.0305 (4)
H(B4	0.152511	0.345089	0.011582	0.037*
C(M1	0.10343 (5)	0.4091 (3)	0.13702 (7)	0.0178 (3)
C(M2	0.05699 (6)	0.4455 (3)	−0.07278 (7)	0.0219 (4)
C(S1	0.0408 (4)	0.950 (2)	−0.0123 (6)	0.061 (2)	0.5
H(S1	0.063403	0.919040	−0.021508	0.073*	0.5
C(S2	−0.0044 (4)	1.008 (2)	−0.0588 (6)	0.051 (2)	0.5
H(S2	−0.012183	1.013446	−0.099368	0.061*	0.5
C(S3	−0.0380 (3)	1.0566 (19)	−0.0472 (5)	0.044 (2)	0.5
H(S3	−0.068634	1.098603	−0.078945	0.053*	0.5
C(S7	0.23680 (11)	0.9084 (5)	0.45930 (12)	0.0655 (8)
H(S7	0.227437	1.020489	0.431141	0.079*
C(S8	0.25387 (8)	0.7307 (5)	0.45095 (10)	0.0526 (6)
H(S8	0.256539	0.717365	0.417107	0.063*
C(S9	0.26728 (10)	0.5702 (5)	0.49140 (12)	0.0621 (7)
H(S9	0.279376	0.444178	0.485916	0.075*
C(S4	−0.0252 (4)	1.042 (2)	0.0146 (6)	0.056 (2)	0.5
H(S4	−0.047227	1.073430	0.024683	0.067*	0.5
C(S5	0.0196 (4)	0.981 (2)	0.0585 (6)	0.055 (3)	0.5
H(S5	0.028285	0.968400	0.099303	0.066*	0.5
C(S6	0.0526 (4)	0.938 (2)	0.0447 (6)	0.059 (3)	0.5
H(S6	0.083646	0.900416	0.076063	0.071*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01178 (13)	0.01950 (14)	0.01282 (12)	0.00114 (10)	0.00607 (10)	0.00089 (10)
F1	0.0328 (6)	0.0353 (7)	0.0349 (6)	−0.0018 (5)	0.0113 (5)	0.0102 (5)
F2	0.0484 (8)	0.0659 (9)	0.0353 (7)	0.0174 (7)	0.0130 (6)	0.0308 (6)
F3	0.0218 (6)	0.1041 (11)	0.0158 (5)	0.0120 (7)	−0.0003 (5)	0.0052 (6)
F4	0.0253 (6)	0.0807 (10)	0.0319 (6)	−0.0229 (6)	0.0070 (5)	−0.0161 (6)
F5	0.0313 (6)	0.0373 (6)	0.0319 (6)	−0.0102 (5)	0.0126 (5)	0.0000 (5)
F6	0.0606 (9)	0.0553 (8)	0.0539 (8)	−0.0003 (7)	0.0390 (7)	−0.0154 (7)
F7	0.0994 (14)	0.0922 (13)	0.0626 (10)	0.0365 (10)	0.0592 (10)	−0.0045 (8)
F8	0.0732 (11)	0.1355 (15)	0.0649 (9)	0.0625 (10)	0.0627 (9)	0.0491 (10)
F9	0.0530 (9)	0.1079 (13)	0.0862 (11)	0.0131 (9)	0.0558 (9)	0.0405 (10)
F10	0.0426 (8)	0.0614 (9)	0.0549 (8)	−0.0066 (6)	0.0326 (7)	0.0057 (7)
N1	0.0126 (6)	0.0205 (7)	0.0149 (6)	0.0002 (5)	0.0068 (5)	0.0004 (5)
N2	0.0126 (7)	0.0224 (7)	0.0141 (6)	0.0013 (5)	0.0061 (5)	0.0019 (5)
C1	0.0142 (8)	0.0306 (9)	0.0158 (7)	0.0029 (7)	0.0080 (6)	0.0012 (6)
C2	0.0200 (9)	0.0366 (11)	0.0218 (8)	0.0025 (8)	0.0103 (7)	0.0040 (7)
C3	0.0278 (10)	0.0502 (12)	0.0220 (9)	0.0134 (9)	0.0122 (8)	0.0140 (8)
C4	0.0142 (9)	0.0689 (15)	0.0126 (8)	0.0074 (9)	0.0032 (7)	0.0016 (8)
C5	0.0152 (8)	0.0577 (13)	0.0211 (8)	−0.0088 (9)	0.0083 (7)	−0.0105 (9)
C6	0.0178 (8)	0.0373 (11)	0.0191 (8)	−0.0011 (7)	0.0095 (7)	−0.0007 (7)
C7	0.0191 (9)	0.0490 (11)	0.0184 (8)	0.0120 (8)	0.0118 (7)	0.0094 (8)
C8	0.0342 (11)	0.0547 (13)	0.0280 (10)	0.0143 (10)	0.0203 (9)	0.0055 (9)
C9	0.0555 (15)	0.0727 (17)	0.0333 (11)	0.0347 (13)	0.0308 (11)	0.0130 (11)
C10	0.0469 (14)	0.091 (2)	0.0399 (12)	0.0413 (14)	0.0370 (12)	0.0326 (13)
C11	0.0287 (11)	0.0841 (19)	0.0445 (12)	0.0188 (11)	0.0272 (10)	0.0344 (13)
C12	0.0265 (10)	0.0562 (14)	0.0299 (10)	0.0113 (9)	0.0175 (9)	0.0131 (9)
C(A1	0.0176 (8)	0.0261 (9)	0.0158 (7)	0.0002 (7)	0.0096 (6)	0.0002 (6)
C(A2	0.0152 (8)	0.0211 (8)	0.0146 (7)	−0.0011 (6)	0.0064 (6)	−0.0009 (6)
C(A3	0.0146 (8)	0.0232 (9)	0.0174 (7)	0.0020 (7)	0.0070 (6)	0.0022 (6)
C(A4	0.0170 (8)	0.0288 (9)	0.0192 (8)	0.0039 (7)	0.0108 (7)	0.0027 (7)
C(B1	0.0203 (9)	0.0476 (12)	0.0167 (8)	0.0051 (8)	0.0106 (7)	0.0024 (7)
C(B2	0.0188 (9)	0.0414 (10)	0.0144 (8)	0.0024 (8)	0.0072 (7)	0.0009 (7)
C(B3	0.0157 (9)	0.0482 (12)	0.0207 (8)	0.0095 (8)	0.0084 (7)	0.0069 (8)
C(B4	0.0193 (9)	0.0510 (12)	0.0230 (9)	0.0111 (8)	0.0130 (8)	0.0067 (8)
C(M1	0.0140 (8)	0.0208 (8)	0.0146 (7)	0.0006 (6)	0.0053 (6)	0.0007 (6)
C(M2	0.0179 (8)	0.0319 (10)	0.0185 (8)	0.0029 (7)	0.0117 (7)	0.0021 (7)
C(S1	0.067 (5)	0.021 (3)	0.084 (4)	−0.005 (4)	0.035 (4)	−0.009 (3)
C(S2	0.065 (5)	0.022 (3)	0.058 (4)	−0.010 (4)	0.030 (4)	−0.009 (3)
C(S3	0.048 (5)	0.019 (3)	0.056 (3)	−0.010 (4)	0.022 (3)	0.001 (2)
C(S7	0.075 (2)	0.0692 (19)	0.0419 (14)	−0.0035 (16)	0.0254 (14)	0.0182 (13)
C(S8	0.0390 (13)	0.082 (2)	0.0325 (11)	−0.0139 (13)	0.0172 (10)	0.0024 (12)
C(S9	0.0566 (17)	0.0699 (18)	0.0503 (15)	0.0061 (14)	0.0235 (13)	0.0037 (13)
C(S4	0.065 (5)	0.026 (4)	0.072 (4)	−0.014 (4)	0.035 (4)	−0.007 (3)
C(S5	0.066 (6)	0.023 (4)	0.059 (4)	−0.009 (5)	0.024 (4)	0.000 (3)
C(S6	0.062 (5)	0.024 (3)	0.071 (4)	−0.010 (4)	0.023 (4)	−0.006 (3)

Geometric parameters (Å, º) top

Zn1—N1	2.0470 (13)	C(A1—C(B1	1.444 (2)
Zn1—N1ⁱ	2.0469 (13)	C(A1—C(M2ⁱ	1.397 (2)
Zn1—N2ⁱ	2.0355 (14)	C(A2—C(B2	1.445 (2)
Zn1—N2	2.0354 (14)	C(A2—C(M1	1.401 (2)
F1—C2	1.338 (2)	C(A3—C(B3	1.443 (2)
F2—C3	1.333 (2)	C(A3—C(M1	1.398 (2)
F3—C4	1.342 (2)	C(A4—C(B4	1.441 (2)
F4—C5	1.340 (2)	C(A4—C(M2	1.399 (2)
F5—C6	1.340 (2)	C(B1—H(B1	0.9500
F6—C8	1.336 (3)	C(B1—C(B2	1.349 (3)
F7—C9	1.338 (3)	C(B2—H(B2	0.9500
F8—C10	1.338 (2)	C(B3—H(B3	0.9500
F9—C11	1.340 (3)	C(B3—C(B4	1.350 (2)
F10—C12	1.340 (3)	C(B4—H(B4	0.9500
N1—C(A1	1.370 (2)	C(S1—H(S1	0.9500
N1—C(A2	1.368 (2)	C(S1—C(S2	1.390 (13)
N2—C(A3	1.369 (2)	C(S1—C(S6	1.327 (16)
N2—C(A4	1.368 (2)	C(S2—H(S2	0.9500
C1—C2	1.381 (2)	C(S2—C(S3	1.378 (11)
C1—C6	1.382 (2)	C(S3—H(S3	0.9500
C1—C(M1	1.498 (2)	C(S3—C(S4	1.438 (15)
C2—C3	1.386 (2)	C(S7—H(S7	0.9500
C3—C4	1.370 (3)	C(S7—C(S8	1.345 (4)
C4—C5	1.367 (3)	C(S7—C(S9ⁱⁱ	1.389 (4)
C5—C6	1.383 (2)	C(S8—H(S8	0.9500
C7—C8	1.376 (3)	C(S8—C(S9	1.362 (4)
C7—C12	1.375 (3)	C(S9—H(S9	0.9500
C7—C(M2	1.502 (2)	C(S4—H(S4	0.9500
C8—C9	1.389 (3)	C(S4—C(S5	1.371 (14)
C9—C10	1.366 (4)	C(S5—H(S5	0.9500
C10—C11	1.359 (4)	C(S5—C(S6	1.390 (12)
C11—C12	1.386 (3)	C(S6—H(S6	0.9500

N1ⁱ—Zn1—N1	180.0	C(M1—C(A2—C(B2	125.19 (15)
N2ⁱ—Zn1—N1ⁱ	89.73 (5)	N2—C(A3—C(B3	109.96 (14)
N2ⁱ—Zn1—N1	90.27 (5)	N2—C(A3—C(M1	125.19 (15)
N2—Zn1—N1	89.73 (5)	C(M1—C(A3—C(B3	124.83 (15)
N2—Zn1—N1ⁱ	90.27 (5)	N2—C(A4—C(B4	109.97 (14)
N2—Zn1—N2ⁱ	180.0	N2—C(A4—C(M2	125.22 (15)
C(A1—N1—Zn1	126.40 (10)	C(M2—C(A4—C(B4	124.81 (15)
C(A2—N1—Zn1	126.86 (10)	C(A1—C(B1—H(B1	126.4
C(A2—N1—C(A1	106.70 (12)	C(B2—C(B1—C(A1	107.21 (15)
C(A3—N2—Zn1	127.14 (11)	C(B2—C(B1—H(B1	126.4
C(A4—N2—Zn1	126.56 (11)	C(A2—C(B2—H(B2	126.6
C(A4—N2—C(A3	106.22 (13)	C(B1—C(B2—C(A2	106.90 (14)
C2—C1—C6	116.16 (15)	C(B1—C(B2—H(B2	126.6
C2—C1—C(M1	122.19 (15)	C(A3—C(B3—H(B3	126.6
C6—C1—C(M1	121.64 (15)	C(B4—C(B3—C(A3	106.83 (15)
F1—C2—C1	119.77 (15)	C(B4—C(B3—H(B3	126.6
F1—C2—C3	118.04 (16)	C(A4—C(B4—H(B4	126.5
C1—C2—C3	122.19 (17)	C(B3—C(B4—C(A4	107.01 (15)
F2—C3—C2	120.67 (19)	C(B3—C(B4—H(B4	126.5
F2—C3—C4	119.50 (17)	C(A2—C(M1—C1	116.98 (14)
C4—C3—C2	119.82 (18)	C(A3—C(M1—C1	117.13 (14)
F3—C4—C3	120.24 (19)	C(A3—C(M1—C(A2	125.90 (14)
F3—C4—C5	120.15 (19)	C(A1ⁱ—C(M2—C7	117.14 (14)
C5—C4—C3	119.61 (16)	C(A1ⁱ—C(M2—C(A4	126.41 (15)
F4—C5—C4	119.98 (17)	C(A4—C(M2—C7	116.44 (15)
F4—C5—C6	120.29 (18)	C(S2—C(S1—H(S1	119.6
C4—C5—C6	119.72 (17)	C(S6—C(S1—H(S1	119.6
F5—C6—C1	119.74 (15)	C(S6—C(S1—C(S2	120.8 (10)
F5—C6—C5	117.77 (16)	C(S1—C(S2—H(S2	119.3
C1—C6—C5	122.49 (17)	C(S3—C(S2—C(S1	121.3 (10)
C8—C7—C(M2	121.29 (18)	C(S3—C(S2—H(S2	119.3
C12—C7—C8	116.60 (17)	C(S2—C(S3—H(S3	121.1
C12—C7—C(M2	122.11 (18)	C(S2—C(S3—C(S4	117.7 (9)
F6—C8—C7	119.98 (16)	C(S4—C(S3—H(S3	121.1
F6—C8—C9	118.0 (2)	C(S8—C(S7—H(S7	119.6
C7—C8—C9	122.0 (2)	C(S8—C(S7—C(S9ⁱⁱ	120.8 (3)
F7—C9—C8	120.1 (2)	C(S9ⁱⁱ—C(S7—H(S7	119.6
F7—C9—C10	120.5 (2)	C(S7—C(S8—H(S8	120.3
C10—C9—C8	119.4 (2)	C(S7—C(S8—C(S9	119.5 (2)
F8—C10—C9	120.5 (3)	C(S9—C(S8—H(S8	120.3
F8—C10—C11	119.3 (3)	C(S7ⁱⁱ—C(S9—H(S9	120.1
C11—C10—C9	120.21 (19)	C(S8—C(S9—C(S7ⁱⁱ	119.7 (3)
F9—C11—C10	119.9 (2)	C(S8—C(S9—H(S9	120.1
F9—C11—C12	120.6 (3)	C(S3—C(S4—H(S4	120.7
C10—C11—C12	119.5 (2)	C(S5—C(S4—C(S3	118.6 (8)
F10—C12—C7	120.01 (17)	C(S5—C(S4—H(S4	120.7
F10—C12—C11	117.7 (2)	C(S4—C(S5—H(S5	119.3
C7—C12—C11	122.3 (2)	C(S4—C(S5—C(S6	121.5 (11)
N1—C(A1—C(B1	109.49 (14)	C(S6—C(S5—H(S5	119.3
N1—C(A1—C(M2ⁱ	125.00 (14)	C(S1—C(S6—C(S5	120.1 (11)
C(M2ⁱ—C(A1—C(B1	125.51 (15)	C(S1—C(S6—H(S6	119.9
N1—C(A2—C(B2	109.69 (14)	C(S5—C(S6—H(S6	119.9
N1—C(A2—C(M1	125.11 (14)

Zn1—N1—C(A1—C(B1	177.00 (11)	C7—C8—C9—C10	−0.5 (3)
Zn1—N1—C(A1—C(M2ⁱ	−3.4 (2)	C8—C7—C12—F10	−179.99 (17)
Zn1—N1—C(A2—C(B2	−177.07 (11)	C8—C7—C12—C11	−0.2 (3)
Zn1—N1—C(A2—C(M1	3.0 (2)	C8—C7—C(M2—C(A1ⁱ	−74.3 (2)
Zn1—N2—C(A3—C(B3	176.82 (12)	C8—C7—C(M2—C(A4	104.8 (2)
Zn1—N2—C(A3—C(M1	−1.7 (2)	C8—C9—C10—F8	−179.00 (18)
Zn1—N2—C(A4—C(B4	−176.65 (12)	C8—C9—C10—C11	0.0 (3)
Zn1—N2—C(A4—C(M2	3.5 (3)	C9—C10—C11—F9	−179.4 (2)
F1—C2—C3—F2	0.3 (3)	C9—C10—C11—C12	0.3 (3)
F1—C2—C3—C4	−179.38 (17)	C10—C11—C12—F10	179.60 (19)
F2—C3—C4—F3	−1.2 (3)	C10—C11—C12—C7	−0.2 (3)
F2—C3—C4—C5	179.30 (17)	C12—C7—C8—F6	179.98 (18)
F3—C4—C5—F4	0.9 (3)	C12—C7—C8—C9	0.5 (3)
F3—C4—C5—C6	−178.28 (16)	C12—C7—C(M2—C(A1ⁱ	106.3 (2)
F4—C5—C6—F5	−0.4 (3)	C12—C7—C(M2—C(A4	−74.6 (2)
F4—C5—C6—C1	−179.69 (16)	C(A1—N1—C(A2—C(B2	0.59 (18)
F6—C8—C9—F7	0.4 (3)	C(A1—N1—C(A2—C(M1	−179.32 (16)
F6—C8—C9—C10	−179.91 (19)	C(A1—C(B1—C(B2—C(A2	−0.1 (2)
F7—C9—C10—F8	0.7 (3)	C(A2—N1—C(A1—C(B1	−0.67 (18)
F7—C9—C10—C11	179.8 (2)	C(A2—N1—C(A1—C(M2ⁱ	178.91 (17)
F8—C10—C11—F9	−0.4 (3)	C(A3—N2—C(A4—C(B4	0.3 (2)
F8—C10—C11—C12	179.32 (18)	C(A3—N2—C(A4—C(M2	−179.58 (17)
F9—C11—C12—F10	−0.7 (3)	C(A3—C(B3—C(B4—C(A4	0.3 (2)
F9—C11—C12—C7	179.52 (18)	C(A4—N2—C(A3—C(B3	−0.10 (19)
N1—C(A1—C(B1—C(B2	0.5 (2)	C(A4—N2—C(A3—C(M1	−178.62 (17)
N1—C(A2—C(B2—C(B1	−0.3 (2)	C(B2—C(A2—C(M1—C1	−3.2 (3)
N1—C(A2—C(M1—C1	176.69 (15)	C(B2—C(A2—C(M1—C(A3	177.12 (17)
N1—C(A2—C(M1—C(A3	−3.0 (3)	C(B3—C(A3—C(M1—C1	4.3 (3)
N2—C(A3—C(B3—C(B4	−0.1 (2)	C(B3—C(A3—C(M1—C(A2	−176.03 (17)
N2—C(A3—C(M1—C1	−177.39 (16)	C(B4—C(A4—C(M2—C7	0.5 (3)
N2—C(A3—C(M1—C(A2	2.3 (3)	C(B4—C(A4—C(M2—C(A1ⁱ	179.43 (18)
N2—C(A4—C(B4—C(B3	−0.4 (2)	C(M1—C1—C2—F1	1.5 (2)
N2—C(A4—C(M2—C7	−179.70 (17)	C(M1—C1—C2—C3	−177.79 (16)
N2—C(A4—C(M2—C(A1ⁱ	−0.7 (3)	C(M1—C1—C6—F5	−1.2 (2)
C1—C2—C3—F2	179.67 (17)	C(M1—C1—C6—C5	178.05 (16)
C1—C2—C3—C4	−0.1 (3)	C(M1—C(A2—C(B2—C(B1	179.63 (17)
C2—C1—C6—F5	−179.83 (15)	C(M1—C(A3—C(B3—C(B4	178.40 (18)
C2—C1—C6—C5	−0.5 (3)	C(M2—C7—C8—F6	0.5 (3)
C2—C1—C(M1—C(A2	70.4 (2)	C(M2—C7—C8—C9	−178.91 (18)
C2—C1—C(M1—C(A3	−109.85 (19)	C(M2—C7—C12—F10	−0.5 (3)
C2—C3—C4—F3	178.53 (16)	C(M2—C7—C12—C11	179.22 (17)
C2—C3—C4—C5	−1.0 (3)	C(M2ⁱ—C(A1—C(B1—C(B2	−179.08 (18)
C3—C4—C5—F4	−179.54 (17)	C(M2—C(A4—C(B4—C(B3	179.49 (19)
C3—C4—C5—C6	1.2 (3)	C(S1—C(S2—C(S3—C(S4	−1.3 (19)
C4—C5—C6—F5	178.84 (16)	C(S2—C(S1—C(S6—C(S5	1 (2)
C4—C5—C6—C1	−0.5 (3)	C(S2—C(S3—C(S4—C(S5	0.3 (17)
C6—C1—C2—F1	−179.89 (15)	C(S3—C(S4—C(S5—C(S6	1.2 (19)
C6—C1—C2—C3	0.8 (3)	C(S7—C(S8—C(S9—C(S7ⁱⁱ	0.0 (5)
C6—C1—C(M1—C(A2	−108.05 (19)	C(S9ⁱⁱ—C(S7—C(S8—C(S9	0.0 (5)
C6—C1—C(M1—C(A3	71.7 (2)	C(S4—C(S5—C(S6—C(S1	−2 (2)
C7—C8—C9—F7	179.81 (18)	C(S6—C(S1—C(S2—C(S3	1 (2)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C(B3—H(B3···F4ⁱⁱⁱ	0.95	2.36	3.276 (2)	163

Symmetry code: (iii) −x+1/2, y−1/2, −z+1/2.

Funding information

The authors thank the National Natural Science Foundation of China (grant Nos. 21771176, 21977093 to JL) for support. This work was supported in part by the Strategic Priority Research Program of Chinese Academy of Sciences, grant No. XDB28000000.

References

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