metal-organic compounds
[5,10,15,20-Tetrakis(pentafluorophenyl)porphyrinato]zinc(II) benzene disolvate
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
Single crystals of the title zinc porphyrinato complex, [Zn(C44H8F20N4)]·2C6H6, were obtained by the solvent evaporation method. The molecular complex exhibits symmetry with the central ZnII 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 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 (5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato)zinc(II) n-hexane solvate, which crystallizes in the P21/c and shows a planar conformation of the porphyrin ligand (Birnbaum et al., 1995). In this work, a new zinc pentafluorophenyl-porphyrin [Zn(TFPP)]·2C6H6 (TFPP is the tetrakis(pentafluorphenyl)porphyrinato ligand), is reported.
have been employed as photosensitizers (LiuThe 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 (Xcent) 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).
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.
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 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 . 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.
details are summarized in Table 2Structural data
CCDC reference: 2013055
https://doi.org/10.1107/S2414314620008779/im4008sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI: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
Data collection: APEX2 (Bruker, 2014); cell
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).[Zn(C44H8F20N4)]·2C6H6 | F(000) = 2376 |
Mr = 1194.13 | Dx = 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 |
Bruker D8 QUEST System diffractometer | 4369 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
f\ and ω scans | θmax = 27.3°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −42→43 |
Tmin = 0.656, Tmax = 0.746 | k = −8→8 |
22042 measured reflections | l = −33→33 |
5287 independent reflections |
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(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.91 | (Δ/σ)max < 0.001 |
5287 reflections | Δρmax = 0.38 e Å−3 |
367 parameters | Δρmin = −0.38 e Å−3 |
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 Uiso(H) = 1.2Ueq(C). |
x | y | z | Uiso*/Ueq | 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 |
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) |
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. |
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.
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