research communications
x-solvate (x > 1/2) showing a rare CN5 coordination
of (15,20-bis(2,3,4,5,6-pentafluorophenyl)-5,10-{(pyridine-3,5-diyl)bis[(sulfanediylmethylene)[1,1′-biphenyl]-4′,2-diyl]}porphyrinato)nickel(II) dichloromethaneaOtto-Diels-Institut für Organische Chemie, Christian-Albrechts-Universität Kiel, Otto-Hahn-Platz 4, D-24098 Kiel, Germany, and bInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Str. 2, D-24118 Kiel, Germany
*Correspondence e-mail: rherges@oc.uni-kiel.de
The 63H31F10N5S2)]·xCH2Cl2 (x > 1/2), consists of Ni–porphyrin complexes that are located in general positions and dichloromethane solvent molecules that are disordered around centers of inversion. The NiII ions are in a square-pyramidal (CN5) coordination, with four porphyrin N atoms in the equatorial and a pyridine N atom in the apical position and are shifted out of the porphyrine N4 plane towards the coordinating pyridine N atom. The pyridine substituent is not exactly perpendicular to the N4 plane with an angle of intersection between the planes planes of 80.48 (6)°. The dichloromethane solvent molecules are hydrogen bonded to one of the four porphyrine N atoms. Two complexes are linked into dimers by two symmetry-equivalent C—H⋯S hydrogen bonds. These dimers are closely packed, leading to cavities in which additional dichloromethane solvent molecules are embedded. These solvent molecules are disordered and because no reasonable split model was found, the data were corrected for disordered solvent using the PLATON SQUEEZE routine [Spek (2015). Acta Cryst. C71, 9–18].
of the title compound, [Ni(CCCDC reference: 1942625
1. Chemical context
Nickelporphyrins and their axial coordination have been studied from a number of different viewpoints over the last six decades. Their rich coordination behaviour (Caughey et al., 1962; McLees & Caughey, 1968; Walker et al. 1975), conformations (Jia et al., 1998) and photophysics (Kim et al., 1983; Kim & Holten, 1983) has attracted interest in different fields, including as model compounds for the F430 cofactor (Renner et al., 1991) or heme (Jentzen et al., 1995), for applications in solar energy conversion (Shelby et al., 2014), in hydrogen-evolution (Han et al., 2016) or redox catalysis (Eom et al., 1997) and as responsive MRI contrast agents (Venkataramani et al., 2011; Dommaschk et al., 2014a,b, 2015a,b). Square-planar [coordination number (CN) 4] nickelporphyrins are diamagnetic, (S = 0), low-spin (LS) complexes. Upon coordination of one (CN5) or two (CN6) axial ligands such as pyridine or piperidine, the nickel cation undergoes spin transition to the high-spin (HS) state. This coordination-induced spin-state switch (CISSS) leads to a drastic change in the spectra and properties of the HS complexes. The coordination and decoordination of the axial ligands in solution is a fast dynamic equilibrium (Kadish et al., 2000). Thus, the observed properties are dependent on the speciation in the equilibrium defined by the association constants (K1S, K2; Thies et al., 2010). In these equilibria, the dominating species are the CN4 and CN6 complexes, with the CN5 species only formed by up to 10% of in solution (Kruglik et al., 2003). Thus, the characterization of CN5 nickelporphyrins was restricted to transient UV–vis (Kim et al., 1983) and resonance Raman measurements (Findsen et al., 1986; Kim et al., 1986) so far. Recently, the first exclusively five-coordinate (CN5) nickel porphyrin in solution, including its structure in the crystal phase, were presented (Gutzeit et al., 2019), offering a new approach towards afore-mentioned applications. The axial ligand of the CN5 porphyrin is held in the coordination position by a rigid strap, inducing conformation-dependent spin-state switching. Similar strapped nickelporphyrins showed incomplete axial coordination in solution (Köbke et al., 2019). The title compound (Fig. 1) was obtained as a byproduct in the synthesis of a CN5 porphyrin with a similar structure (Gutzeit et al., 2019) and was metallated under standard conditions. Preorientation of the ligand by the ligand-holding strap should favour Ni coordination. However, 1H NMR spectropscopy (500 MHz, CDCl3, 298 K) indicates incomplete intramolecular coordination (82% CN5 HS, 18% CN4 LS) of the title compound. One application is pH measurements in non-aqueous solutions because coordination and NMR signals are dependent on the protonation state of the pyridine moiety. The NMR spectra revealed an unexpected behaviour of the title compound, because the geminal coupling of the CH2-protons indicates confined movement of the pyridine moiety and hindered ring inversion of the strap (see Figure S1 in the supporting information).
2. Structural commentary
In the 63H31F10N5S2)]·xCH2Cl2 (x > 1/2), the NiII ions are coordinated by the four N atoms of the porphyrine moiety within a square-planar and the Ni coordination is completed by a pyridine N atom in the apical position, leading to a square-pyramidal coordination environment (CN5) (Figs. 1–3). The porphyrine ring plane is not fully planar with maximum deviations of the C atoms from the mean plane of 0.137 (3) Å. The Ni cation is shifted by 0.250 (3) Å out of the N4 plane towards the coordinating pyridine N atom (Fig. 4). The Ni—N bond lengths (Table 1) to the porphyrine N atoms ranges from 2.0350 (17) to 2.0434 (17) Å and are in agreement with values retrieved from literature, indicating that the NiII ion is in the high-spin state (Thies et al., 2010). The Ni—N bond length to the pyridine N atom of 2.1122 (17) Å is significantly longer and agrees well with the 2.11 Å that are observed in the CN5 porphyrin (Gutzeit et al., 2019). Compared to octahedral (CN6) nickelporphyrins with two axial pyridine ligands, the Ni—N distance is shortened by ∼0.10 Å (Thies et al., 2010). The pyridine ring is not exactly perpendicular to the N4 plane (Fig. 4), the angle of intersection between them amounting to 80.48 (6)°, in good agreement with similar complexes (Thies et al., 2010). The tetrafluorophenyl rings are rotated out of the N4 plane by 67.43 (5) and 68.74 (6)°, and the phenyl rings (C39–C44 and C58–C63) by 58.82 (6) and 72.59 (5)°, respectively. The dihedral angles between the biphenyl units amount to 63.02 (9) and 53.45 (8)°.
of the title compound, [Ni(C
|
3. Supramolecular features
In the via centrosymmetric pairs of intermolecular C—H⋯S hydrogen bonds between the porphyrine H atoms and the sulfur atoms (Fig. 5 and Table 2). Between the dimers, cavities are formed that are occupied by the dichloromethane solvent molecules, which are disordered about centers of inversion. These solvent molecules are linked by intermolecular C—H⋯Cl hydrogen bonding to the nitrogen atom N1 of the porphyrine unit that is not shielded by the strap (Fig. 5). The C—H⋯S angle is close to linearity, indicating that this is a relatively strong interaction (Table 2). The dimeric units are packed in such a way that cavities are formed in which additional, completely disordered dichlormethane solvent molecules are embedded, for which no reasonable structure model was found.
of the title compound, the discrete Ni porphyrine complexes are linked into dimers4. Database survey
According to a search of the Cambridge Structural Database (CSD, Version 5.40, update of February 2019; Groom et al., 2016), axial coordination of metal is highly metal dependent. Two examples of CN5 nickelporphyrins are known that have been characterized by single-crystal structure analysis (Kumar & Sankar, 2014; Gutzeit et al., 2019), while zinc almost exclusively form CN5 complexes (Paul et al., 2003; Deutman et al., 2014). The application of strapped for controlling axial coordination is an established approach (Richard et al., 1998) for mimicking heme complexes (Hijazi et al., 2010; Melin et al., 2012; Zhou et al., 2012). With nickel(II) with nitrogen-containing ligands almost exclusively form CN4 (Nurco et al., 2002; Halime et al., 2007; Bediako et al., 2014) or CN6 (Thies et al., 2010; Dommaschk et al., 2014b) complexes, in rare cases a CN6 complex is formed with oxygen-containing ligands (Ozette et al., 1997).
5. Synthesis and crystallization
The freebase porphyrin of the title compound was obtained as a byproduct of a variant of the published procedure (Gutzeit et al., 2019). The compound is synthesized from a linked dialdehyde under acidic conditions through macrocycle condensation with pentafluorophenyldipyrromethane. The reaction was performed under reflux for 17 h before the addition of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). At elevated temperatures, the scrambling mechanism, acidic cleavage and rearrangement of oligopyrrols dominates the product formation, leading to the 5,10-bridged scrambling porphyrin of the title compound. The freebase were separated by (silica gel, dichloromethane and silica gel, toluene) and precipitated from dichloromethane by diffusion of methanol (89 mg, 4.3%).
1H NMR (600 MHz, CDCl3, 298 K, TMS): δ = 8.95 (s, 2 H, Hβ), 8.65 (d, 3J = 4.5 Hz, 2 H, Hβ), 8.63 (s, 2 H, Hβ), 8.54 (d, 3J = 4.5 Hz, 2 H, Hβ), 8.28 (dd, 3J = 7.4 Hz, 4J = 1.0 Hz, 2 H, H-6′), 7.90 (td, 3J = 7.8 Hz, 4J = 1.3 Hz, 2 H, H-4′), 7.80 (dd, 3J = 7.9 Hz, 4J = 1.0 Hz, 2 H, H-3′), 7.75 (td, 3J = 7.5 Hz, 4J = 1.3 Hz, 2 H, H-5′), 7.29 (s, 1 H, H-4′′′), 6.68 (d, 3J = 8.2 Hz, 4 H, H-2′′), 5.81 (d, 3J = 8.2 Hz, 4 H, H-3′′), 3.18 (d, 2J = 14.6 Hz, 2 H, CH2,a), 3.05 (d, 2J = 14.6 Hz, 2 H, CH2,b), −2.80 (s, 2 H, NH) ppm. Unobserved signals: H-2′′′. 13C NMR (151 MHz, CDCl3, 298 K, TMS): δ = 151.8 (C3′′′), 145.1 (C4′′′), 144.7 (C2′), 140.4 (C1′′), 139.9 (C1′), 135.7 (C4′′), 134.7 (C6′), 129.4 (C2′′), 129.3 (C3′), 129.2 (C4′), 127.3 (C3′′), 125.9 (C5′), 121.4 (C5, C10), 101.1 (C15, C20), 40.5 (CH2) ppm. Unobserved signals: C2′′′, Cα, Cβ, C6F5. 19F NMR (471 MHz, CDCl3, 298 K): δ = −136.96 (dd, 3J = 24.4 Hz, 4J = 7.8 Hz, F-ortho), −137.27 (dd, 3J = 24.0 Hz, 4J = 7.8 Hz, F-ortho), −153.03 (t, 3J = 21.0 Hz, F-para), −(162.35–162.62) (m, F-meta) ppm. FT–IR (ATR): ν = 3310.3 (w), 3026.7 (w), 1650.5 (w), 1519.6 (s), 1496.0 (vs), 1474.9 (s), 1440.4 (m), 1393.7 (m), 1349.2 (m), 1266.0 (w), 1126.8 (w), 1042.1 (m), 975.3 (vs), 971.2 (s), 917.3 (vs), 882.7 (m), 837.3 (m), 800.1 (vs), 762.9 (vs), 746.9 (vs), 713.0 (s), 701.2 (vs), 664.7 (s), 650.2 (s), 638.3 (m), 598.1 (m), 553.9 (m), 529.6 (m), 505.2 (m), 460.0 (w), 430.2 (w), 407.2 (m) cm−1. MS (EI): m/z (%) = 1113.20 (100) [M]+, 556.59 (13) [M]2+ u. HRMS (EI) calculated for C63H33F10N5S2: 1113.2018 u, found: 1113.2023 u, dif.: 0.5 ppm.
The nickel cation was introduced under standard conditions (20 mg porphyrin, 80 mg Ni(acac)2, 15 mL toluene, reflux, 23 h) followed by filtration through a silica plug (dichloromethane) (21 mg, 99%). Single crystals were obtained by dissolving the compound in dichloromethane and gas phase diffusion of methanol.
M.p. > 673 K. Decomposition starting from 600 K. 1H NMR (600 MHz, CDCl3, 300 K, TFA): δ = 8.68 (s, 6 H, Hβ), 8.54 (s, 2 H, Hβ), 8.05 (d, 3J = 7.4 Hz, 2 H, H-6′), 7.90–7.84 (m, 3 H, H-4′, H-4′′′), 7.79 (d, 3J = 7.9 Hz, 2 H, H-3′), 7.72 (t, 3J = 7.5 Hz, 2 H, H-5′), 7.52 (d, 4J = 1.3 Hz, 2 H, H-2′′′), 6.73 (d, 3J = 8.3 Hz, 4 H, H-2′′), 6.39 (d, 3J = 8.3 Hz, 4 H, H-3′′), 3.61 (d, 2J = 14.9 Hz, 2 H, CH2,a), 3.56 (d, 2J = 14.9 Hz, 2 H, CH2,b) ppm. 13C NMR (151 MHz, CDCl3, 300 K, TFA): δ = 145.8 (C4′′′), 143.1 (C2′), 141.6 (C1′′), 140.7 (C3′′′), 138.5 (C1′), 137.5 (C2′′′), 135.0 (C6′), 134.2 (Cβ), 133.3 (Cβ), 132.9 (C4′′), 131.6 (Cβ), 130.6 (Cβ), 129.8 (C2′′), 129.6 (C3′), 129.6 (C4′), 128.0 (C3′′), 126.6 (C5′), 38.4 (CH2) ppm. Unobserved signals: Cmeso, Cα, C6F5. 19F NMR (471 MHz, CDCl3, 300 K, TFA): δ = −137.04 (dd, 3J = 23.6 Hz, 4J = 7.4 Hz, F-ortho), −138.11 (dd, 3J = 23.6 Hz, 4J = 6.3 Hz, F-ortho), −152.14 (t, 3J = 20.6 Hz, F-para), −161.67 (td, 3J = 22.0 Hz, 4J = 8.3 Hz, F-meta), −162.01 (td, 3J = 22.2 Hz, 4J = 8.3 Hz, F-meta) ppm. FT–IR (ATR): ν = 3023.7 (w), 2920.4 (w), 2843.3 (w), 2748.1 (w), 1685.6 (s), 1595.8 (m), 1517.3 (m), 1477.2 (s), 1440.8 (m), 1390.9 (m), 1339.2 (m), 1297.2 (m), 1254.9 (m), 1177.5 (m), 1072.9 (m), 984.0 (vs), 949.2 (s), 930.4 (m), 832.6 (s), 815.7 (m), 798.9 (m), 752.5 (vs), 729.9 (s), 700.8 (vs), 655.2 (m), 535.4 (m), 464.7 (m), 441.2 (m), 416.9 (m) cm−1. MS (EI): m/z (%) = 1169.16 (100) [M]+, 1027.11 (5) [M - C5H4NS2]+, 584.54 (12) [M]2+ u. HRMS (EI) calculated for C63H31F10N5NiS2: 1169.1215 u, found: 1169.1159 u, dif.: 4.7 ppm.
6. Refinement
Crystal data, data collection and structure . The C—H hydrogen atoms were located in difference-Fourier maps but were positioned with idealized geometry and refined with isotropic with Uiso(H) = 1.2Ueq(C) using a riding model. After structure using a model with one Ni porphyrine complex and a half dichloromethane solvent molecule disordered about a center of inversion, there was significant residual electron density that definitely corresponded to an additional dichloromethane molecule that was disordered over several orientations. A number of different split models were tried, using restraints for the geometry and for the components of the anisotropic displacement parameters, but no reasonable structure model was found and very large anisotropic displacement parameters were obtained. Therefore, the contribution of this solvent to the electron density was removed with the SQUEEZE (Spek, 2015) routine in PLATON, which leads to a reasonable structure model and very good reliability factors. Their formula mass and unit-cell characteristics were not taken into account during By this procedure, the amount of dichloromethane cannot be determined accurately and there is indication that this position is not fully occupied, which is highly likely because this solvent is very unstable and starts to decompose during the sample preparation.
details are summarized in Table 3Supporting information
CCDC reference: 1942625
https://doi.org/10.1107/S2056989019009836/lh5902sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019009836/lh5902Isup2.hkl
Fig. S1. 1H NMR spectrum of the title compound and its 5,15-strapped isomer showing the splitting of the methylene protons due to geminal coupling. DOI: https://doi.org/10.1107/S2056989019009836/lh5902sup3.tif
Data collection: X-AREA (Stoe & Cie, 2008); cell
X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: XP (Sheldrick, 2008) and DIAMOND (Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).[Ni(C63H31F10N5S2)]·0.5CH2Cl2 | F(000) = 2460 |
Mr = 1213.22 | Dx = 1.449 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.0919 (3) Å | Cell parameters from 55528 reflections |
b = 22.0127 (4) Å | θ = 1.5–27.0° |
c = 17.9648 (3) Å | µ = 0.55 mm−1 |
β = 93.950 (1)° | T = 170 K |
V = 5559.46 (18) Å3 | Block, red |
Z = 4 | 0.12 × 0.10 × 0.07 mm |
Stoe IPDS-2 diffractometer | 10733 reflections with I > 2σ(I) |
ω scans | Rint = 0.041 |
Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie, 2008) | θmax = 27.0°, θmin = 1.5° |
Tmin = 0.855, Tmax = 0.932 | h = −18→18 |
55497 measured reflections | k = −25→28 |
12087 independent reflections | l = −22→22 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.129 | w = 1/[σ2(Fo2) + (0.0758P)2 + 3.7723P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
12087 reflections | Δρmax = 0.66 e Å−3 |
758 parameters | Δρmin = −1.07 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.58798 (2) | 0.71647 (2) | 0.57642 (2) | 0.02141 (8) | |
N1 | 0.59348 (12) | 0.63329 (8) | 0.62668 (9) | 0.0245 (3) | |
N2 | 0.46308 (12) | 0.73353 (8) | 0.62395 (9) | 0.0230 (3) | |
N3 | 0.59565 (12) | 0.80659 (8) | 0.55101 (9) | 0.0233 (3) | |
N4 | 0.72676 (12) | 0.70653 (8) | 0.55409 (10) | 0.0239 (3) | |
C1 | 0.66429 (15) | 0.59083 (9) | 0.62313 (12) | 0.0269 (4) | |
C2 | 0.63488 (17) | 0.53424 (10) | 0.65507 (13) | 0.0334 (5) | |
H2 | 0.6708 | 0.4977 | 0.6592 | 0.040* | |
C3 | 0.54726 (17) | 0.54296 (10) | 0.67780 (13) | 0.0337 (5) | |
H3 | 0.5092 | 0.5137 | 0.7008 | 0.040* | |
C4 | 0.52167 (15) | 0.60528 (9) | 0.66069 (11) | 0.0266 (4) | |
C5 | 0.43626 (15) | 0.63265 (9) | 0.67759 (11) | 0.0267 (4) | |
C6 | 0.41063 (14) | 0.69294 (9) | 0.66208 (11) | 0.0249 (4) | |
C7 | 0.32499 (16) | 0.72149 (10) | 0.68415 (12) | 0.0306 (4) | |
H7 | 0.2770 | 0.7031 | 0.7112 | 0.037* | |
C8 | 0.32589 (15) | 0.77925 (10) | 0.65907 (12) | 0.0301 (4) | |
H8 | 0.2786 | 0.8093 | 0.6651 | 0.036* | |
C9 | 0.41223 (14) | 0.78671 (9) | 0.62136 (11) | 0.0244 (4) | |
C10 | 0.43930 (14) | 0.84098 (9) | 0.58821 (11) | 0.0244 (4) | |
C11 | 0.52614 (14) | 0.84960 (9) | 0.55633 (11) | 0.0246 (4) | |
C12 | 0.55625 (16) | 0.90652 (10) | 0.52642 (13) | 0.0306 (4) | |
H12 | 0.5203 | 0.9430 | 0.5223 | 0.037* | |
C13 | 0.64549 (16) | 0.89808 (10) | 0.50525 (13) | 0.0311 (4) | |
H13 | 0.6846 | 0.9277 | 0.4842 | 0.037* | |
C14 | 0.66991 (14) | 0.83565 (9) | 0.52072 (11) | 0.0255 (4) | |
C15 | 0.75732 (14) | 0.80948 (9) | 0.50740 (12) | 0.0264 (4) | |
C16 | 0.78312 (14) | 0.74944 (9) | 0.52339 (12) | 0.0257 (4) | |
C17 | 0.87512 (16) | 0.72371 (10) | 0.51174 (14) | 0.0327 (5) | |
H17 | 0.9270 | 0.7440 | 0.4914 | 0.039* | |
C18 | 0.87370 (16) | 0.66555 (10) | 0.53515 (14) | 0.0322 (5) | |
H18 | 0.9241 | 0.6370 | 0.5341 | 0.039* | |
C19 | 0.78106 (14) | 0.65502 (9) | 0.56210 (12) | 0.0265 (4) | |
C20 | 0.75174 (15) | 0.60063 (9) | 0.59340 (12) | 0.0266 (4) | |
C21 | 0.36750 (16) | 0.59433 (10) | 0.71663 (12) | 0.0303 (4) | |
C22 | 0.2819 (2) | 0.57573 (13) | 0.68182 (15) | 0.0436 (6) | |
C23 | 0.2180 (2) | 0.53996 (16) | 0.71763 (19) | 0.0602 (8) | |
C24 | 0.2399 (3) | 0.52226 (14) | 0.79003 (19) | 0.0587 (8) | |
C25 | 0.3250 (2) | 0.53948 (12) | 0.82664 (15) | 0.0459 (6) | |
C26 | 0.38710 (17) | 0.57540 (10) | 0.78984 (13) | 0.0341 (5) | |
F1 | 0.25770 (12) | 0.59288 (9) | 0.61162 (9) | 0.0581 (5) | |
F2 | 0.13568 (17) | 0.52346 (14) | 0.68200 (14) | 0.0979 (9) | |
F3 | 0.17864 (18) | 0.48761 (11) | 0.82540 (15) | 0.0909 (8) | |
F4 | 0.34636 (15) | 0.52264 (8) | 0.89743 (10) | 0.0620 (5) | |
F5 | 0.46837 (11) | 0.59194 (7) | 0.82692 (8) | 0.0439 (3) | |
C27 | 0.82125 (15) | 0.54910 (10) | 0.59874 (13) | 0.0305 (4) | |
C28 | 0.86257 (17) | 0.53054 (11) | 0.66689 (15) | 0.0385 (5) | |
C29 | 0.92457 (19) | 0.48197 (13) | 0.67457 (18) | 0.0495 (7) | |
C30 | 0.94680 (18) | 0.45035 (12) | 0.6117 (2) | 0.0512 (7) | |
C31 | 0.90800 (18) | 0.46779 (11) | 0.54311 (18) | 0.0445 (6) | |
C32 | 0.84641 (17) | 0.51655 (10) | 0.53690 (15) | 0.0358 (5) | |
F6 | 0.84195 (12) | 0.56018 (8) | 0.72897 (9) | 0.0525 (4) | |
F7 | 0.96200 (14) | 0.46548 (11) | 0.74156 (13) | 0.0752 (6) | |
F8 | 1.00598 (13) | 0.40282 (8) | 0.61798 (15) | 0.0765 (7) | |
F9 | 0.92962 (13) | 0.43661 (8) | 0.48228 (12) | 0.0625 (5) | |
F10 | 0.81040 (12) | 0.53211 (7) | 0.46861 (9) | 0.0469 (4) | |
C33 | 0.83157 (14) | 0.84931 (9) | 0.47646 (13) | 0.0281 (4) | |
C34 | 0.88260 (16) | 0.88914 (10) | 0.52414 (14) | 0.0329 (5) | |
H34 | 0.8662 | 0.8931 | 0.5743 | 0.040* | |
C35 | 0.95687 (16) | 0.92312 (10) | 0.49967 (15) | 0.0362 (5) | |
H35 | 0.9911 | 0.9502 | 0.5328 | 0.043* | |
C36 | 0.98110 (16) | 0.91751 (11) | 0.42641 (15) | 0.0375 (5) | |
H36 | 1.0326 | 0.9403 | 0.4094 | 0.045* | |
C37 | 0.93014 (16) | 0.87869 (11) | 0.37827 (14) | 0.0358 (5) | |
H37 | 0.9468 | 0.8753 | 0.3281 | 0.043* | |
C38 | 0.85461 (15) | 0.84444 (10) | 0.40201 (13) | 0.0309 (4) | |
C39 | 0.80068 (16) | 0.80206 (11) | 0.35035 (13) | 0.0326 (5) | |
C40 | 0.84598 (18) | 0.75224 (13) | 0.32051 (16) | 0.0447 (6) | |
H40 | 0.9131 | 0.7483 | 0.3283 | 0.054* | |
C41 | 0.79485 (19) | 0.70860 (14) | 0.27980 (17) | 0.0473 (6) | |
H41 | 0.8268 | 0.6744 | 0.2611 | 0.057* | |
C42 | 0.69674 (18) | 0.71422 (12) | 0.26586 (13) | 0.0360 (5) | |
C43 | 0.65239 (18) | 0.76588 (12) | 0.29106 (14) | 0.0384 (5) | |
H43 | 0.5862 | 0.7717 | 0.2794 | 0.046* | |
C44 | 0.70348 (18) | 0.80909 (11) | 0.33306 (14) | 0.0381 (5) | |
H44 | 0.6718 | 0.8440 | 0.3503 | 0.046* | |
C45 | 0.64009 (18) | 0.66380 (12) | 0.22885 (13) | 0.0389 (5) | |
H45A | 0.6730 | 0.6490 | 0.1854 | 0.047* | |
H45B | 0.5771 | 0.6796 | 0.2103 | 0.047* | |
S1 | 0.62357 (4) | 0.60005 (3) | 0.29283 (3) | 0.03453 (13) | |
C46 | 0.54694 (16) | 0.63273 (10) | 0.35631 (12) | 0.0292 (4) | |
C47 | 0.58379 (15) | 0.66201 (9) | 0.42082 (11) | 0.0273 (4) | |
H47 | 0.6505 | 0.6684 | 0.4274 | 0.033* | |
N5 | 0.52841 (12) | 0.68159 (8) | 0.47408 (9) | 0.0257 (3) | |
C48 | 0.43431 (15) | 0.67159 (10) | 0.46450 (12) | 0.0278 (4) | |
H48 | 0.3950 | 0.6848 | 0.5022 | 0.033* | |
C49 | 0.39175 (15) | 0.64277 (10) | 0.40170 (13) | 0.0302 (4) | |
C50 | 0.44935 (16) | 0.62400 (10) | 0.34651 (12) | 0.0307 (4) | |
H50 | 0.4222 | 0.6053 | 0.3024 | 0.037* | |
S2 | 0.26911 (4) | 0.62465 (3) | 0.39663 (3) | 0.03449 (13) | |
C51 | 0.21774 (18) | 0.69105 (12) | 0.34671 (14) | 0.0378 (5) | |
H51A | 0.2489 | 0.6964 | 0.2994 | 0.045* | |
H51B | 0.1491 | 0.6840 | 0.3342 | 0.045* | |
C52 | 0.23014 (16) | 0.74738 (11) | 0.39249 (13) | 0.0338 (5) | |
C53 | 0.16432 (17) | 0.76351 (12) | 0.44322 (15) | 0.0396 (5) | |
H53 | 0.1073 | 0.7407 | 0.4451 | 0.047* | |
C54 | 0.18041 (17) | 0.81234 (12) | 0.49108 (14) | 0.0376 (5) | |
H54 | 0.1339 | 0.8231 | 0.5246 | 0.045* | |
C55 | 0.26431 (15) | 0.84586 (10) | 0.49051 (12) | 0.0293 (4) | |
C56 | 0.32876 (16) | 0.83131 (10) | 0.43773 (12) | 0.0309 (4) | |
H56 | 0.3851 | 0.8547 | 0.4352 | 0.037* | |
C57 | 0.31159 (17) | 0.78307 (11) | 0.38893 (13) | 0.0328 (5) | |
H57 | 0.3557 | 0.7742 | 0.3527 | 0.039* | |
C58 | 0.28648 (15) | 0.89443 (10) | 0.54606 (12) | 0.0281 (4) | |
C59 | 0.22139 (16) | 0.94130 (11) | 0.55572 (13) | 0.0335 (5) | |
H59 | 0.1627 | 0.9417 | 0.5264 | 0.040* | |
C60 | 0.24100 (17) | 0.98704 (11) | 0.60726 (14) | 0.0355 (5) | |
H60 | 0.1957 | 1.0182 | 0.6135 | 0.043* | |
C61 | 0.32663 (18) | 0.98732 (10) | 0.64973 (13) | 0.0343 (5) | |
H61 | 0.3409 | 1.0192 | 0.6844 | 0.041* | |
C62 | 0.39173 (16) | 0.94075 (10) | 0.64144 (12) | 0.0307 (4) | |
H62 | 0.4505 | 0.9410 | 0.6707 | 0.037* | |
C63 | 0.37196 (14) | 0.89351 (9) | 0.59075 (11) | 0.0253 (4) | |
C71 | 0.4950 (5) | 0.4754 (3) | 0.5071 (4) | 0.0610 (16) | 0.5 |
H71A | 0.5180 | 0.4593 | 0.5547 | 0.073* | 0.5 |
H71B | 0.4734 | 0.4420 | 0.4760 | 0.073* | 0.5 |
Cl1 | 0.58828 (19) | 0.51258 (13) | 0.46611 (14) | 0.0832 (6) | 0.5 |
Cl2 | 0.39844 (19) | 0.52500 (13) | 0.51963 (14) | 0.0821 (6) | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.02354 (13) | 0.01875 (13) | 0.02204 (13) | −0.00082 (9) | 0.00226 (9) | 0.00049 (9) |
N1 | 0.0272 (8) | 0.0212 (8) | 0.0254 (8) | 0.0005 (6) | 0.0035 (6) | 0.0012 (6) |
N2 | 0.0256 (8) | 0.0204 (8) | 0.0232 (8) | −0.0005 (6) | 0.0024 (6) | 0.0016 (6) |
N3 | 0.0242 (8) | 0.0214 (8) | 0.0244 (8) | −0.0011 (6) | 0.0026 (6) | 0.0001 (6) |
N4 | 0.0253 (8) | 0.0198 (8) | 0.0267 (8) | −0.0011 (6) | 0.0025 (6) | 0.0002 (6) |
C1 | 0.0308 (10) | 0.0211 (9) | 0.0287 (10) | 0.0019 (8) | 0.0013 (8) | 0.0016 (8) |
C2 | 0.0385 (12) | 0.0221 (10) | 0.0401 (12) | 0.0029 (9) | 0.0082 (9) | 0.0054 (9) |
C3 | 0.0389 (12) | 0.0229 (10) | 0.0402 (12) | 0.0004 (9) | 0.0101 (9) | 0.0057 (9) |
C4 | 0.0314 (10) | 0.0228 (10) | 0.0259 (10) | −0.0017 (8) | 0.0036 (8) | 0.0024 (7) |
C5 | 0.0302 (10) | 0.0252 (10) | 0.0250 (10) | −0.0024 (8) | 0.0042 (8) | 0.0029 (8) |
C6 | 0.0258 (9) | 0.0255 (10) | 0.0237 (9) | −0.0016 (8) | 0.0029 (7) | 0.0005 (7) |
C7 | 0.0302 (10) | 0.0319 (11) | 0.0306 (11) | 0.0008 (8) | 0.0076 (8) | 0.0043 (8) |
C8 | 0.0299 (10) | 0.0300 (11) | 0.0309 (11) | 0.0039 (8) | 0.0062 (8) | 0.0041 (8) |
C9 | 0.0249 (9) | 0.0250 (10) | 0.0232 (9) | 0.0019 (7) | 0.0018 (7) | 0.0008 (7) |
C10 | 0.0260 (9) | 0.0232 (9) | 0.0234 (9) | 0.0020 (7) | −0.0013 (7) | 0.0001 (7) |
C11 | 0.0278 (9) | 0.0220 (9) | 0.0237 (9) | 0.0001 (7) | 0.0004 (7) | 0.0013 (7) |
C12 | 0.0329 (11) | 0.0225 (10) | 0.0366 (11) | 0.0011 (8) | 0.0040 (9) | 0.0042 (8) |
C13 | 0.0317 (11) | 0.0234 (10) | 0.0388 (12) | −0.0007 (8) | 0.0067 (9) | 0.0049 (8) |
C14 | 0.0282 (10) | 0.0219 (9) | 0.0266 (9) | −0.0024 (8) | 0.0025 (8) | 0.0010 (7) |
C15 | 0.0261 (10) | 0.0239 (10) | 0.0293 (10) | −0.0028 (8) | 0.0031 (8) | −0.0004 (8) |
C16 | 0.0246 (9) | 0.0229 (10) | 0.0297 (10) | −0.0017 (7) | 0.0021 (8) | −0.0008 (8) |
C17 | 0.0267 (10) | 0.0275 (11) | 0.0448 (13) | −0.0012 (8) | 0.0090 (9) | 0.0010 (9) |
C18 | 0.0274 (10) | 0.0262 (10) | 0.0436 (12) | 0.0014 (8) | 0.0059 (9) | 0.0008 (9) |
C19 | 0.0263 (9) | 0.0238 (10) | 0.0294 (10) | 0.0010 (8) | 0.0020 (8) | −0.0014 (8) |
C20 | 0.0290 (10) | 0.0219 (9) | 0.0289 (10) | 0.0007 (8) | 0.0013 (8) | −0.0007 (8) |
C21 | 0.0357 (11) | 0.0236 (10) | 0.0328 (11) | −0.0006 (8) | 0.0111 (9) | 0.0038 (8) |
C22 | 0.0456 (14) | 0.0458 (14) | 0.0400 (13) | −0.0156 (11) | 0.0078 (11) | 0.0025 (11) |
C23 | 0.0547 (17) | 0.063 (2) | 0.0640 (19) | −0.0312 (15) | 0.0126 (15) | 0.0021 (15) |
C24 | 0.070 (2) | 0.0452 (16) | 0.0652 (19) | −0.0203 (14) | 0.0326 (16) | 0.0093 (14) |
C25 | 0.0678 (18) | 0.0311 (12) | 0.0417 (14) | 0.0056 (12) | 0.0245 (13) | 0.0116 (10) |
C26 | 0.0410 (12) | 0.0271 (11) | 0.0355 (12) | 0.0046 (9) | 0.0120 (9) | 0.0037 (9) |
F1 | 0.0503 (9) | 0.0797 (13) | 0.0433 (9) | −0.0257 (9) | −0.0047 (7) | 0.0082 (8) |
F2 | 0.0737 (14) | 0.133 (2) | 0.0875 (16) | −0.0721 (15) | 0.0073 (12) | 0.0028 (15) |
F3 | 0.1011 (17) | 0.0806 (15) | 0.0967 (17) | −0.0436 (13) | 0.0481 (14) | 0.0186 (13) |
F4 | 0.0930 (14) | 0.0503 (10) | 0.0458 (9) | 0.0125 (9) | 0.0287 (9) | 0.0241 (8) |
F5 | 0.0466 (8) | 0.0528 (9) | 0.0323 (7) | 0.0078 (7) | 0.0042 (6) | 0.0086 (6) |
C27 | 0.0279 (10) | 0.0218 (10) | 0.0420 (12) | −0.0003 (8) | 0.0034 (8) | 0.0029 (8) |
C28 | 0.0343 (12) | 0.0336 (12) | 0.0467 (14) | −0.0003 (9) | −0.0029 (10) | 0.0032 (10) |
C29 | 0.0332 (12) | 0.0443 (15) | 0.0697 (19) | 0.0029 (11) | −0.0063 (12) | 0.0194 (13) |
C30 | 0.0291 (12) | 0.0299 (12) | 0.096 (2) | 0.0081 (10) | 0.0115 (13) | 0.0120 (14) |
C31 | 0.0328 (12) | 0.0269 (11) | 0.0760 (19) | 0.0002 (9) | 0.0191 (12) | −0.0059 (12) |
C32 | 0.0323 (11) | 0.0262 (11) | 0.0497 (14) | −0.0013 (9) | 0.0091 (10) | 0.0000 (9) |
F6 | 0.0595 (10) | 0.0560 (10) | 0.0401 (8) | 0.0052 (8) | −0.0100 (7) | −0.0004 (7) |
F7 | 0.0563 (11) | 0.0808 (14) | 0.0855 (14) | 0.0171 (10) | −0.0172 (10) | 0.0336 (12) |
F8 | 0.0470 (10) | 0.0427 (10) | 0.141 (2) | 0.0237 (8) | 0.0167 (11) | 0.0210 (11) |
F9 | 0.0545 (10) | 0.0402 (9) | 0.0965 (14) | 0.0060 (7) | 0.0322 (10) | −0.0182 (9) |
F10 | 0.0563 (9) | 0.0444 (8) | 0.0410 (8) | 0.0055 (7) | 0.0109 (7) | −0.0054 (7) |
C33 | 0.0249 (9) | 0.0218 (9) | 0.0380 (11) | 0.0002 (7) | 0.0043 (8) | 0.0032 (8) |
C34 | 0.0315 (11) | 0.0262 (10) | 0.0413 (12) | −0.0014 (8) | 0.0043 (9) | −0.0009 (9) |
C35 | 0.0298 (11) | 0.0248 (10) | 0.0539 (14) | −0.0047 (8) | 0.0008 (10) | 0.0013 (9) |
C36 | 0.0289 (11) | 0.0293 (11) | 0.0547 (15) | −0.0047 (9) | 0.0060 (10) | 0.0089 (10) |
C37 | 0.0322 (11) | 0.0337 (12) | 0.0422 (13) | −0.0013 (9) | 0.0075 (9) | 0.0097 (10) |
C38 | 0.0274 (10) | 0.0260 (10) | 0.0395 (12) | −0.0004 (8) | 0.0042 (8) | 0.0048 (9) |
C39 | 0.0337 (11) | 0.0320 (11) | 0.0329 (11) | −0.0054 (9) | 0.0070 (9) | 0.0045 (9) |
C40 | 0.0305 (12) | 0.0497 (15) | 0.0546 (16) | −0.0042 (11) | 0.0073 (11) | −0.0104 (12) |
C41 | 0.0384 (13) | 0.0499 (16) | 0.0546 (16) | −0.0033 (11) | 0.0101 (11) | −0.0168 (13) |
C42 | 0.0382 (12) | 0.0426 (13) | 0.0275 (11) | −0.0058 (10) | 0.0040 (9) | 0.0019 (9) |
C43 | 0.0364 (12) | 0.0442 (13) | 0.0337 (12) | −0.0003 (10) | −0.0032 (9) | 0.0056 (10) |
C44 | 0.0394 (12) | 0.0348 (12) | 0.0395 (13) | 0.0014 (10) | −0.0009 (10) | 0.0041 (10) |
C45 | 0.0421 (13) | 0.0482 (14) | 0.0265 (11) | −0.0076 (11) | 0.0026 (9) | −0.0026 (10) |
S1 | 0.0375 (3) | 0.0351 (3) | 0.0315 (3) | −0.0020 (2) | 0.0062 (2) | −0.0083 (2) |
C46 | 0.0346 (11) | 0.0272 (10) | 0.0259 (10) | −0.0033 (8) | 0.0040 (8) | −0.0022 (8) |
C47 | 0.0290 (10) | 0.0267 (10) | 0.0262 (10) | −0.0021 (8) | 0.0016 (8) | −0.0006 (8) |
N5 | 0.0298 (9) | 0.0238 (8) | 0.0235 (8) | −0.0022 (7) | 0.0013 (6) | 0.0004 (6) |
C48 | 0.0298 (10) | 0.0263 (10) | 0.0272 (10) | −0.0021 (8) | 0.0025 (8) | −0.0012 (8) |
C49 | 0.0295 (10) | 0.0279 (10) | 0.0330 (11) | −0.0050 (8) | 0.0007 (8) | −0.0005 (8) |
C50 | 0.0353 (11) | 0.0290 (10) | 0.0274 (10) | −0.0042 (9) | −0.0011 (8) | −0.0036 (8) |
S2 | 0.0295 (3) | 0.0330 (3) | 0.0409 (3) | −0.0078 (2) | 0.0016 (2) | −0.0044 (2) |
C51 | 0.0364 (12) | 0.0400 (13) | 0.0359 (12) | −0.0034 (10) | −0.0050 (9) | −0.0057 (10) |
C52 | 0.0337 (11) | 0.0348 (12) | 0.0319 (11) | −0.0006 (9) | −0.0038 (9) | −0.0012 (9) |
C53 | 0.0292 (11) | 0.0410 (13) | 0.0483 (14) | −0.0059 (10) | 0.0012 (10) | −0.0056 (11) |
C54 | 0.0293 (11) | 0.0401 (13) | 0.0437 (13) | 0.0009 (9) | 0.0044 (9) | −0.0044 (10) |
C55 | 0.0292 (10) | 0.0269 (10) | 0.0314 (11) | 0.0030 (8) | −0.0021 (8) | 0.0034 (8) |
C56 | 0.0316 (10) | 0.0309 (11) | 0.0298 (10) | −0.0011 (8) | 0.0000 (8) | 0.0042 (8) |
C57 | 0.0360 (11) | 0.0348 (12) | 0.0275 (10) | −0.0019 (9) | 0.0013 (8) | 0.0008 (9) |
C58 | 0.0292 (10) | 0.0248 (10) | 0.0306 (10) | 0.0023 (8) | 0.0042 (8) | 0.0034 (8) |
C59 | 0.0282 (10) | 0.0329 (11) | 0.0391 (12) | 0.0056 (9) | 0.0002 (9) | 0.0028 (9) |
C60 | 0.0371 (12) | 0.0277 (11) | 0.0426 (13) | 0.0094 (9) | 0.0086 (10) | 0.0027 (9) |
C61 | 0.0437 (13) | 0.0261 (10) | 0.0333 (11) | 0.0045 (9) | 0.0038 (9) | −0.0016 (9) |
C62 | 0.0341 (11) | 0.0274 (10) | 0.0304 (11) | 0.0034 (8) | 0.0002 (8) | 0.0009 (8) |
C63 | 0.0271 (9) | 0.0234 (9) | 0.0259 (10) | 0.0016 (7) | 0.0044 (7) | 0.0029 (7) |
C71 | 0.067 (4) | 0.053 (3) | 0.063 (4) | −0.004 (3) | 0.004 (3) | 0.005 (3) |
Cl1 | 0.0902 (15) | 0.0825 (15) | 0.0762 (13) | −0.0186 (13) | −0.0003 (11) | 0.0025 (12) |
Cl2 | 0.0951 (16) | 0.0745 (14) | 0.0752 (13) | 0.0037 (12) | −0.0048 (11) | −0.0074 (11) |
Ni1—N4 | 2.0350 (17) | C34—H34 | 0.9500 |
Ni1—N3 | 2.0402 (17) | C35—C36 | 1.388 (4) |
Ni1—N1 | 2.0407 (17) | C35—H35 | 0.9500 |
Ni1—N2 | 2.0434 (17) | C36—C37 | 1.381 (4) |
Ni1—N5 | 2.1122 (17) | C36—H36 | 0.9500 |
N1—C4 | 1.365 (3) | C37—C38 | 1.395 (3) |
N1—C1 | 1.372 (3) | C37—H37 | 0.9500 |
N2—C9 | 1.372 (3) | C38—C39 | 1.487 (3) |
N2—C6 | 1.372 (3) | C39—C44 | 1.392 (3) |
N3—C11 | 1.370 (3) | C39—C40 | 1.395 (4) |
N3—C14 | 1.371 (3) | C40—C41 | 1.380 (4) |
N4—C19 | 1.370 (3) | C40—H40 | 0.9500 |
N4—C16 | 1.374 (3) | C41—C42 | 1.393 (4) |
C1—C20 | 1.393 (3) | C41—H41 | 0.9500 |
C1—C2 | 1.444 (3) | C42—C43 | 1.388 (4) |
C2—C3 | 1.341 (3) | C42—C45 | 1.496 (3) |
C2—H2 | 0.9500 | C43—C44 | 1.385 (4) |
C3—C4 | 1.446 (3) | C43—H43 | 0.9500 |
C3—H3 | 0.9500 | C44—H44 | 0.9500 |
C4—C5 | 1.398 (3) | C45—S1 | 1.839 (3) |
C5—C6 | 1.398 (3) | C45—H45A | 0.9900 |
C5—C21 | 1.495 (3) | C45—H45B | 0.9900 |
C6—C7 | 1.440 (3) | S1—C46 | 1.776 (2) |
C7—C8 | 1.349 (3) | C46—C50 | 1.388 (3) |
C7—H7 | 0.9500 | C46—C47 | 1.395 (3) |
C8—C9 | 1.442 (3) | C47—N5 | 1.347 (3) |
C8—H8 | 0.9500 | C47—H47 | 0.9500 |
C9—C10 | 1.399 (3) | N5—C48 | 1.343 (3) |
C10—C11 | 1.399 (3) | C48—C49 | 1.394 (3) |
C10—C63 | 1.498 (3) | C48—H48 | 0.9500 |
C11—C12 | 1.439 (3) | C49—C50 | 1.387 (3) |
C12—C13 | 1.351 (3) | C49—S2 | 1.770 (2) |
C12—H12 | 0.9500 | C50—H50 | 0.9500 |
C13—C14 | 1.439 (3) | S2—C51 | 1.837 (3) |
C13—H13 | 0.9500 | C51—C52 | 1.492 (3) |
C14—C15 | 1.395 (3) | C51—H51A | 0.9900 |
C15—C16 | 1.395 (3) | C51—H51B | 0.9900 |
C15—C33 | 1.501 (3) | C52—C53 | 1.390 (3) |
C16—C17 | 1.443 (3) | C52—C57 | 1.396 (3) |
C17—C18 | 1.348 (3) | C53—C54 | 1.386 (4) |
C17—H17 | 0.9500 | C53—H53 | 0.9500 |
C18—C19 | 1.442 (3) | C54—C55 | 1.394 (3) |
C18—H18 | 0.9500 | C54—H54 | 0.9500 |
C19—C20 | 1.397 (3) | C55—C56 | 1.395 (3) |
C20—C27 | 1.497 (3) | C55—C58 | 1.481 (3) |
C21—C22 | 1.382 (4) | C56—C57 | 1.388 (3) |
C21—C26 | 1.389 (3) | C56—H56 | 0.9500 |
C22—F1 | 1.338 (3) | C57—H57 | 0.9500 |
C22—C23 | 1.387 (4) | C58—C59 | 1.399 (3) |
C23—F2 | 1.336 (4) | C58—C63 | 1.401 (3) |
C23—C24 | 1.372 (5) | C59—C60 | 1.383 (3) |
C24—F3 | 1.344 (3) | C59—H59 | 0.9500 |
C24—C25 | 1.380 (5) | C60—C61 | 1.383 (4) |
C25—F4 | 1.339 (3) | C60—H60 | 0.9500 |
C25—C26 | 1.382 (3) | C61—C62 | 1.390 (3) |
C26—F5 | 1.335 (3) | C61—H61 | 0.9500 |
C27—C28 | 1.381 (3) | C62—C63 | 1.398 (3) |
C27—C32 | 1.388 (3) | C62—H62 | 0.9500 |
C28—F6 | 1.341 (3) | C71—C71i | 1.126 (13) |
C28—C29 | 1.382 (4) | C71—Cl1i | 1.326 (8) |
C29—F7 | 1.331 (3) | C71—Cl2i | 1.607 (8) |
C29—C30 | 1.381 (5) | C71—Cl1 | 1.753 (7) |
C30—F8 | 1.338 (3) | C71—Cl2 | 1.772 (8) |
C30—C31 | 1.368 (5) | C71—H71A | 0.9600 |
C31—F9 | 1.343 (3) | C71—H71B | 0.9599 |
C31—C32 | 1.380 (3) | Cl1—Cl2i | 0.882 (3) |
C32—F10 | 1.339 (3) | Cl1—C71i | 1.326 (8) |
C33—C34 | 1.391 (3) | Cl2—Cl1i | 0.882 (3) |
C33—C38 | 1.402 (3) | Cl2—C71i | 1.607 (8) |
C34—C35 | 1.383 (3) | ||
N4—Ni1—N3 | 89.66 (7) | C34—C35—H35 | 120.2 |
N4—Ni1—N1 | 89.03 (7) | C36—C35—H35 | 120.2 |
N3—Ni1—N1 | 166.05 (7) | C37—C36—C35 | 119.8 (2) |
N4—Ni1—N2 | 165.76 (7) | C37—C36—H36 | 120.1 |
N3—Ni1—N2 | 88.58 (7) | C35—C36—H36 | 120.1 |
N1—Ni1—N2 | 89.29 (7) | C36—C37—C38 | 121.2 (2) |
N4—Ni1—N5 | 96.84 (7) | C36—C37—H37 | 119.4 |
N3—Ni1—N5 | 100.53 (7) | C38—C37—H37 | 119.4 |
N1—Ni1—N5 | 93.42 (7) | C37—C38—C33 | 118.8 (2) |
N2—Ni1—N5 | 97.37 (7) | C37—C38—C39 | 121.1 (2) |
C4—N1—C1 | 106.09 (17) | C33—C38—C39 | 120.09 (19) |
C4—N1—Ni1 | 126.63 (14) | C44—C39—C40 | 118.1 (2) |
C1—N1—Ni1 | 126.60 (14) | C44—C39—C38 | 121.5 (2) |
C9—N2—C6 | 105.94 (16) | C40—C39—C38 | 120.4 (2) |
C9—N2—Ni1 | 127.28 (13) | C41—C40—C39 | 121.0 (2) |
C6—N2—Ni1 | 126.72 (14) | C41—C40—H40 | 119.5 |
C11—N3—C14 | 105.91 (16) | C39—C40—H40 | 119.5 |
C11—N3—Ni1 | 127.38 (13) | C40—C41—C42 | 120.6 (3) |
C14—N3—Ni1 | 126.60 (14) | C40—C41—H41 | 119.7 |
C19—N4—C16 | 106.08 (16) | C42—C41—H41 | 119.7 |
C19—N4—Ni1 | 127.29 (14) | C43—C42—C41 | 118.5 (2) |
C16—N4—Ni1 | 126.52 (14) | C43—C42—C45 | 120.9 (2) |
N1—C1—C20 | 125.30 (19) | C41—C42—C45 | 120.4 (2) |
N1—C1—C2 | 109.85 (18) | C44—C43—C42 | 120.8 (2) |
C20—C1—C2 | 124.85 (19) | C44—C43—H43 | 119.6 |
C3—C2—C1 | 107.04 (19) | C42—C43—H43 | 119.6 |
C3—C2—H2 | 126.5 | C43—C44—C39 | 120.8 (2) |
C1—C2—H2 | 126.5 | C43—C44—H44 | 119.6 |
C2—C3—C4 | 107.00 (19) | C39—C44—H44 | 119.6 |
C2—C3—H3 | 126.5 | C42—C45—S1 | 112.03 (17) |
C4—C3—H3 | 126.5 | C42—C45—H45A | 109.2 |
N1—C4—C5 | 125.35 (19) | S1—C45—H45A | 109.2 |
N1—C4—C3 | 110.00 (18) | C42—C45—H45B | 109.2 |
C5—C4—C3 | 124.64 (19) | S1—C45—H45B | 109.2 |
C4—C5—C6 | 125.46 (19) | H45A—C45—H45B | 107.9 |
C4—C5—C21 | 117.01 (18) | C46—S1—C45 | 101.61 (11) |
C6—C5—C21 | 117.52 (19) | C50—C46—C47 | 118.6 (2) |
N2—C6—C5 | 125.22 (18) | C50—C46—S1 | 120.23 (17) |
N2—C6—C7 | 110.09 (18) | C47—C46—S1 | 120.85 (17) |
C5—C6—C7 | 124.68 (19) | N5—C47—C46 | 122.5 (2) |
C8—C7—C6 | 106.97 (19) | N5—C47—H47 | 118.7 |
C8—C7—H7 | 126.5 | C46—C47—H47 | 118.7 |
C6—C7—H7 | 126.5 | C48—N5—C47 | 118.15 (18) |
C7—C8—C9 | 106.97 (19) | C48—N5—Ni1 | 120.05 (14) |
C7—C8—H8 | 126.5 | C47—N5—Ni1 | 121.32 (14) |
C9—C8—H8 | 126.5 | N5—C48—C49 | 123.0 (2) |
N2—C9—C10 | 125.87 (18) | N5—C48—H48 | 118.5 |
N2—C9—C8 | 110.03 (17) | C49—C48—H48 | 118.5 |
C10—C9—C8 | 124.10 (19) | C50—C49—C48 | 118.3 (2) |
C11—C10—C9 | 124.16 (18) | C50—C49—S2 | 120.91 (17) |
C11—C10—C63 | 118.77 (18) | C48—C49—S2 | 120.56 (17) |
C9—C10—C63 | 117.00 (18) | C49—C50—C46 | 119.5 (2) |
N3—C11—C10 | 125.76 (18) | C49—C50—H50 | 120.3 |
N3—C11—C12 | 110.18 (18) | C46—C50—H50 | 120.3 |
C10—C11—C12 | 124.03 (19) | C49—S2—C51 | 101.32 (11) |
C13—C12—C11 | 106.82 (19) | C52—C51—S2 | 111.40 (17) |
C13—C12—H12 | 126.6 | C52—C51—H51A | 109.3 |
C11—C12—H12 | 126.6 | S2—C51—H51A | 109.3 |
C12—C13—C14 | 106.96 (19) | C52—C51—H51B | 109.3 |
C12—C13—H13 | 126.5 | S2—C51—H51B | 109.3 |
C14—C13—H13 | 126.5 | H51A—C51—H51B | 108.0 |
N3—C14—C15 | 125.62 (19) | C53—C52—C57 | 118.3 (2) |
N3—C14—C13 | 110.08 (18) | C53—C52—C51 | 121.0 (2) |
C15—C14—C13 | 124.29 (19) | C57—C52—C51 | 120.5 (2) |
C16—C15—C14 | 125.19 (19) | C54—C53—C52 | 121.1 (2) |
C16—C15—C33 | 116.82 (18) | C54—C53—H53 | 119.4 |
C14—C15—C33 | 117.93 (18) | C52—C53—H53 | 119.4 |
N4—C16—C15 | 125.76 (18) | C53—C54—C55 | 120.6 (2) |
N4—C16—C17 | 109.77 (18) | C53—C54—H54 | 119.7 |
C15—C16—C17 | 124.46 (19) | C55—C54—H54 | 119.7 |
C18—C17—C16 | 107.14 (19) | C54—C55—C56 | 118.4 (2) |
C18—C17—H17 | 126.4 | C54—C55—C58 | 121.1 (2) |
C16—C17—H17 | 126.4 | C56—C55—C58 | 120.4 (2) |
C17—C18—C19 | 106.90 (19) | C57—C56—C55 | 120.8 (2) |
C17—C18—H18 | 126.6 | C57—C56—H56 | 119.6 |
C19—C18—H18 | 126.6 | C55—C56—H56 | 119.6 |
N4—C19—C20 | 124.95 (19) | C56—C57—C52 | 120.6 (2) |
N4—C19—C18 | 110.11 (18) | C56—C57—H57 | 119.7 |
C20—C19—C18 | 124.92 (19) | C52—C57—H57 | 119.7 |
C1—C20—C19 | 125.50 (19) | C59—C58—C63 | 119.0 (2) |
C1—C20—C27 | 116.76 (18) | C59—C58—C55 | 120.4 (2) |
C19—C20—C27 | 117.69 (18) | C63—C58—C55 | 120.58 (19) |
C22—C21—C26 | 116.7 (2) | C60—C59—C58 | 121.2 (2) |
C22—C21—C5 | 121.9 (2) | C60—C59—H59 | 119.4 |
C26—C21—C5 | 121.3 (2) | C58—C59—H59 | 119.4 |
F1—C22—C21 | 120.0 (2) | C61—C60—C59 | 120.0 (2) |
F1—C22—C23 | 117.8 (3) | C61—C60—H60 | 120.0 |
C21—C22—C23 | 122.2 (3) | C59—C60—H60 | 120.0 |
F2—C23—C24 | 120.5 (3) | C60—C61—C62 | 119.6 (2) |
F2—C23—C22 | 120.1 (3) | C60—C61—H61 | 120.2 |
C24—C23—C22 | 119.4 (3) | C62—C61—H61 | 120.2 |
F3—C24—C23 | 120.0 (3) | C61—C62—C63 | 121.0 (2) |
F3—C24—C25 | 119.7 (3) | C61—C62—H62 | 119.5 |
C23—C24—C25 | 120.3 (2) | C63—C62—H62 | 119.5 |
F4—C25—C24 | 120.5 (2) | C62—C63—C58 | 119.17 (19) |
F4—C25—C26 | 120.3 (3) | C62—C63—C10 | 119.72 (19) |
C24—C25—C26 | 119.2 (3) | C58—C63—C10 | 121.01 (19) |
F5—C26—C25 | 117.9 (2) | C71i—C71—Cl1i | 90.9 (8) |
F5—C26—C21 | 119.9 (2) | C71i—C71—Cl2i | 78.7 (7) |
C25—C26—C21 | 122.2 (2) | Cl1i—C71—Cl2i | 167.9 (6) |
C28—C27—C32 | 116.2 (2) | C71i—C71—Cl1 | 49.1 (6) |
C28—C27—C20 | 121.0 (2) | Cl1i—C71—Cl1 | 140.1 (5) |
C32—C27—C20 | 122.8 (2) | Cl2i—C71—Cl1 | 30.03 (17) |
F6—C28—C27 | 119.4 (2) | C71i—C71—Cl2 | 62.8 (7) |
F6—C28—C29 | 117.7 (2) | Cl1i—C71—Cl2 | 28.7 (2) |
C27—C28—C29 | 122.9 (3) | Cl2i—C71—Cl2 | 141.5 (4) |
F7—C29—C30 | 120.3 (3) | Cl1—C71—Cl2 | 111.7 (4) |
F7—C29—C28 | 120.7 (3) | C71i—C71—H71A | 121.1 |
C30—C29—C28 | 119.1 (3) | Cl1i—C71—H71A | 90.2 |
F8—C30—C31 | 120.2 (3) | Cl2i—C71—H71A | 90.0 |
F8—C30—C29 | 120.0 (3) | Cl1—C71—H71A | 109.2 |
C31—C30—C29 | 119.7 (2) | Cl2—C71—H71A | 109.2 |
F9—C31—C30 | 119.4 (2) | C71i—C71—H71B | 130.2 |
F9—C31—C32 | 120.5 (3) | Cl1i—C71—H71B | 96.4 |
C30—C31—C32 | 120.1 (3) | Cl2i—C71—H71B | 95.1 |
F10—C32—C31 | 118.0 (2) | Cl1—C71—H71B | 109.3 |
F10—C32—C27 | 120.0 (2) | Cl2—C71—H71B | 109.3 |
C31—C32—C27 | 122.0 (2) | H71A—C71—H71B | 108.1 |
C34—C33—C38 | 119.5 (2) | Cl2i—Cl1—C71i | 104.9 (4) |
C34—C33—C15 | 119.0 (2) | Cl2i—Cl1—C71 | 65.8 (3) |
C38—C33—C15 | 121.5 (2) | C71i—Cl1—C71 | 39.9 (5) |
C35—C34—C33 | 121.1 (2) | Cl1i—Cl2—C71i | 84.2 (4) |
C35—C34—H34 | 119.5 | Cl1i—Cl2—C71 | 46.3 (3) |
C33—C34—H34 | 119.5 | C71i—Cl2—C71 | 38.5 (4) |
C34—C35—C36 | 119.6 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···S2i | 0.95 | 3.02 | 3.886 (2) | 153 |
C71—H71B···N1i | 0.96 | 2.61 | 3.555 (8) | 169 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Acknowledgements
We thank Professor Dr. Wolfgang Bensch for access to his experimental facility.
Funding information
The authors gratefully acknowledge financial support by the Deutsche Forschungsgesellschaft within the Sonderforschungsbereich 677.
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