The title compound is a demonstration of hydroboration of ynamines with borandiol ester. The bond lengths of the resulting push–pull olefin are discussed.
Keywords: crystal structure, hydroboration, ynamine, push–pull olefin
Abstract
N-[(Z)-2-(2H-1,3,2-Benzodioxaborol-2-yl)-2-phenylethenyl]-N-(propan-2-yl)aniline, C23H22BNO2, contains a C=C bond that is conjugated with a donor and an acceptor group. An analysis that included similar push–pull olefins revealed that bond lengths in their B—C=C—N core units correlate with the perceived acceptor and donor strength of the groups. The two phenyl groups in the molecule are rotated with respect to the plane that contains the BCCN atoms, and are close enough for significant π-stacking. Definite characterization of the title compound demonstrates, for the first time in a reliable way, that hydroboration of ynamines with borandiol esters is feasible. Compared to olefin hydroboration with borane, the ynamine substrate is activated enough to undergo reaction with the less active hydroboration reagent catecholborane.
Chemical context
Boronic esters are frequently used to transfer organic groups to transition metals, for example in the transmetallation step of the Suzuki–Miyaura reaction. Hydroboration of ynamines with borandiol esters produces amino-functionalized boronic esters in one step and perfect atom economy.
For true ynamines, to the best of our knowledge, only two attempts of such reactions have been reported so far. These either failed (Witulski et al., 2000 ▸) or were reported without reaction details and characterization data (Zhuo et al., 2001 ▸). More recently it was found that the exceptionally active Pier’s borane, HB(C6F5)2, can readily hydroborate l-propynyl-2,2,6,6-tetramethylpiperidine (Wang et al., 2018 ▸). Borandiol esters are expected to be less reactive because the electron deficiency at the boron is reduced by π-donation from the oxygen atoms.
Given the limited precedent for ynamine hydroboration, the more comprehensive literature for enamine hydroboration was consulted (Goralski & Singaram, 2012 ▸; Dembitsky et al., 2002 ▸), as their reactivity is expected to be controlled by similar effects. Compared to simple olefin substrates, conjugation of the C=C bond with nitrogen dictates the regioselectivity and increases the reactivity of enamines. However, the presence of a nitrogen atom in the reactant and product enables the formation of unreactive Lewis acid–base adducts with the hydroborating reagent. Building on the vast knowledge of the reactivity of different borane-amine adducts in hydroboration (Brown & Murray, 1984 ▸; Brown et al., 1999 ▸), a bulky iso-propyl and an phenyl group were selected as substituents for the ynamine nitrogen. The former should weaken adducts for steric reasons, whereas the phenyl group is expected to reduce the nucleophilicity of the nitrogen by conjugation.
Ynamine hydroboration using a borandiol ester was reinvestigated and succeeded for a substrate that follows the developed design principles. The product of such a reaction contains a C=C double bond flanked by both an electron-donating group (EDG), the amine, and an electron-withdrawing group (EWG), the boronate. Therefore it belongs to the class of push–pull (captodative) olefins, which are known to have unusual properties such as weak π-bonds or biradical reactivity (Viehe et al., 1985 ▸).
Structural commentary
The asymmetric unit (Fig. 1 ▸) contains two almost identical (r.m.d.s = 0.11 Å) independent molecules. As judged by the B1—C11—C10—N1 torsion angles of 171.6 (2) and 175.5 (2)°, the central C—C bond is only slightly twisted from planarity. The two phenyl groups in the molecule are rotated, by 43 and 49°, with respect to that plane. The centroids of two phenyl groups in one molecule are on average 3.747 Å apart, which suggests intramolecular π-stacking. The mean distances are 1.521 Å for the B1—C11 bond, 1.365 Å for the C10—N1 bond and 1.369 Å for the central C10—C11 bond.
Figure 1.
The molecular structures of the two independent molecules of the title compound 1 with displacement ellipsoids drawn at the 50% probability level.
Supramolecular features
There is a short intermolecular contact between the boron atom and an aniline ortho-HB1B⋯H9A(1 − x, 1 − y, 
+ z) = 2.771 Å and B1A⋯H5B(1 − x, −y, − + z) = 2.856 Å (ΣrvdW[B,H] = 3.11 Å). The shortest intermolecular distances between the catechol unit and boron are B1A⋯C21B
i = 3.540 (4) Å, B1A⋯C20B
i = 3.686 (4) Å (ΣrvdW[B,C] = 3.68 Å), B1A⋯H21B
i = 3.113 Å and B1A⋯H20B
i = 3.381 Å [symmetry code: (i) + x, 1 − y, z]. In addition there is a short contact between one of the other catechol hydrogen atoms and the meta-carbon of the aniline, H22B⋯C6B(x, 1 + y, z) of 2.877 Å (ΣrvdW[C,H] = 2.97 Å). All of these interactions involve atoms that are part of arenes and could be seen as intermolecular π-stacking.
Methyl hydrogen atoms of the isopropyl group are at van der Waals distances with one of the oxygen atoms [O2A⋯H2BA(1 − x, −y, − + z) = 2.698 Å, O2B⋯H3AB(1 − x, 1 − y, + z) = 2.631 Å, ΣrvdW[O,H] = 2.70 Å] and with one of the anilic meta-H atoms [H8A⋯H2BC(1 − x, −y, − + z) = 2.388 Å, ΣrvdW[H,H] = 2.40 Å]. The nitrogen atom is sterically shielded by surrounding groups and does not have any close intermolecular neighbours.
Database survey
Contributions from the zwitterionic resonance structure −B=C—C=N+ are expected to increase with donor and acceptor group strength. This should be observable as a shortening of the B—C and C—N bonds and an elongation of the C—C bond. Following this idea, bond lengths of 1 were compared to those in the structurally related compounds 2–5 (Table 1 ▸, Fig. 2 ▸). C—N bond lengths are 1.341 Å (4), 1.350 Å (5), 1.362 Å (3), 1.365 Å (1), 1.394 Å (2). These numbers follow the expected N-donor strength, when the latter is estimated by the number of conjugating substituents on the nitrogen: piperidine, diisopropyl > aniline > indole, carbazole. B—C lengths are 1.491 Å (4), 1.513 Å (3), 1.516 Å (5), 1.521 Å (1), 1.537 Å (2). Similarly, these numbers follow the B-acceptor strength: B(C6F5)2 > catecholboryl > pinacolboryl (Adamczyk-Woźniak et al., 2011 ▸). Following this, the zwitterionic resonance structure is most important in 4, which has a strong donor and a strong acceptor. On the other end of the scale lies 2, which has a weak donor and a weak acceptor. The other molecules, including 1, lie between these two extremes.
Table 1. Comparison of bond lengths (in Å) in 1 with those in the similar compounds 2–5 .
Average distances and standard deviations are given whenever there is more than one molecule in the asymmetric unit. Typical bond lengths for vinylboranes and conjugated enamines were obtained from statistical analysis.
| Compound | B—C | C—C | C—N | CCDC |
|---|---|---|---|---|
| 1 | 1.521 (3) | 1.369 (3) | 1.365 (3) | title compound |
| 2 | 1.537 (4) | 1.335 (4) | 1.394 (3) | 861787a |
| 3 | 1.513 (4) | 1.380 (3) | 1.362 (3) | 1529736 |
| 4 | 1.491 (7) | 1.393 (6) | 1.341 (6) | 1843575c |
| 5 | 1.516 (2) | 1.371 (2) | 1.350 (2) | 1997665d |
| Vinyl boronates | 1.561 (15) | 1.341 (12) | – | – |
| Enamines | – | ∼1.34 | ∼1.36 | – |
Figure 2.
Chemical structure of reference compounds. 9-[(E)-2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]-9H-carbazole, 2 (Hatayama & Okuno, 2012 ▸), 3-(2H-1,3,2-benzodioxaborol-2-yl)-1-methyl-1H-indole, 3 (Liu et al., 2017 ▸), 1-{(Z)-2-[bis(pentafluorophenyl)boranyl]prop-1-en-1-yl}-2,2,6,6-tetramethylpiperidine, 4 (Wang et al., 2018 ▸) and N-[(Z)-2-(2H-1,3,2-benzodioxaborol-2-yl)-2-phenylethenyl]-N-(propan-2-yl)propan-2-amine, 5 (CCDC 1997665).
In order to compare with olefins that either have a donor or an acceptor group, the Cambridge Structural Database (CSD, Version 5.41, update of November 2019; Groom et al., 2016 ▸) was searched for vinyl boronates and enamines. Bond-length distributions and the exact query structures are shown in Fig. 3 ▸ and Fig. 4 ▸. The data set for vinyl boronates consists of about 90% of pinacol boronates and contains only a few catechol boronates. Compared with typical bond lengths in this data set, the B—C bond is shorter and the C=C bond is longer in 1–5, which indicates stronger conjugation. The only exception is 2, whose C=C bond is shorter.
Figure 3.
Statistical analysis of B—C and C—C bond lengths in vinyl boronates. The query substructure and restrictions are shown on the left. Problematic or irrelevant structures were removed. The bond distances of reference compounds are marked.
Figure 4.
Statistical analysis of C—C and C—N bond lengths in enamines. The query substructure and restrictions are shown on the left. Problematic or irrelevant structures were removed. The bond distances of reference compounds are marked.
For enamines the C—C bond length has an average of 1.341 Å, which is about 0.025 Å longer than the value of 1.316 (15) Å for regular internal olefins (Allen et al., 2006 ▸). In 1, 3, 4 and 5, the C—C bonds are on average 1.378 Å, and thereby longer than in enamines. C—N bond lengths for enamines are distributed more uniformly than C—C lengths. Inspection of the structures in which C—N distances are longer than 1.39 Å revealed that these structures typically either have a nitrogen whose lone pair is not coplanar with the C=C bond, or a nitrogen that is part of a carbazole or morpholine. As conjugation with the formal double bond between C10 and C11 is absent or reduced in these, only structures with C—N bond lengths below 1.39 Å were used for comparison. The average C—N bond length of about 1.36 Å for that subset is similar to the C—N bond lengths in 1, 3, 4 and 5. Overall, comparison with enamines reveals that C—C bonds are longer in push–pull olefins, whereas C—N bond lengths are unaffected. This suggests that conjugation with the boron affects the C—C bond length more than the C—N bond length.
Synthesis and crystallization
The title compound was prepared by the multi-step sequence shown in Fig. 5 ▸.
Figure 5.
Reaction sequence used for the synthesis of the title compound.
N -isopropyl- N -(phenylethynyl)aniline: In a 100 ml Schlenk flask, 5.8 ml of N-isopropyl amine (40 mmol, 1.0 eq.) were diluted with 40 ml of dry THF. 24.7 ml of a n-BuLi solution in hexanes (1.62 mol l−1, 40 mmol, 1.0 eq.) were added over 5 min at 195 K. A colourless solid formed and after 15 min the suspension was warmed to room temperature over 30 min. Upon addition of 5.69 g of 2-chloroethynylbenzene (96%, 40 mmol, 1.0 eq., prepared according to Li et al., 2014 ▸), the reaction mixture turned black. The sealed Schlenk flask was heated in an oil bath at 338 K (caution: the closed flask may burst if this temperature is exceeded). The reaction progress was monitored by GC–FID. After 6 h the reaction mixture was cooled to room temperature. 100 ml of tert-butyl methyl ether were added, the organic phase washed with ice-cold water (3 × 50 ml), dried with MgSO4 and concentrated on the rotavap. 8.25 g of black viscous liquid were obtained and purified by Kugelrohr distillation (433 K, 0.2 mbar) to yield 6.34 g (purity 83 wt%, yield 56%) of the colourless liquid N-isopropyl-N-(phenylethynyl)aniline. 1H NMR (400 MHz, CDCl3): δ (ppm) = 1.40 (d, 6.5 Hz, 6H, 2 × CH3), 4.10 (hept, 6.4 Hz, 1H, CH of i-Pr), 6.92 (tt, 7.4 Hz, 1.2 Hz, 1H, para-H of aniline), 7.16–7.33 (m, 7H, arene H), 7.38–7.41 (m, 2H, ortho-H of phenyl group). 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) = 20.6 (s, 2 × CH3), 49.6 (s, CH of i-Pr), 72.0 (s, alkynic carbon farther from N), 86.4 (s, alkynic carbon closer to N), 115.5 (s, ortho-C of aniline), 120.8 (s, para-C of aniline), 125.2 (s, ipso-C of phenyl group), 126.2 (s, para-C of phenyl group), 128.4 (s, meta-C of phenyl group), 129.3 (s, meta-C of aniline), 130.2 (s, ortho-C of phenyl group), 144.4 (s, ipso-C of aniline). EI–MS (70 eV) m/z = 236, 235 (M +), 220 (M + − CH3), 194, 193, 192 (M + − C3H7), 165, 117, 115, 90, 89, 77, 63, 51, 43. ATR–IR ν (cm−1)(%T) = 534 (70), 629 (61), 688 (22), 745 (18), 783 (82), 865 (87), 881 (87), 904 (87), 996 (80), 1025 (73), 1056 (66), 1129 (70), 1147 (52), 1170 (67), 1254 (41), 1312 (67), 1348 (77), 1367 (76), 1396 (51), 1490 (38), 1594 (46), 1932 (96), 2217 (38, C≡C-stretch), 2872 (94), 2932 (91), 2976 (80), 3034 (93), 3057 (93).
N -[( Z )-2-(2 H -1,3,2-benzodioxaborol-2-yl)-2-phenylethenyl]- N -(propan-2-yl)aniline: Under a counterflow of argon, 3.08 g of N-isopropyl-N-(phenylethynyl)aniline (13.1 mmol, 1.0 eq.) were placed in an oven-dried 20 ml Schlenk flask with a Young valve. The flask and its contents were purged three times by applying high vacuum followed by flushing with argon. 6.5 ml dry tert-butyl methyl ether were added and the mixture stirred vigorously to ensure mixing of the two liquids. 2.1 ml of catecholborane (19.5 mmol, 1.5 eq.) were added, the flask closed, and the reaction mixture heated to 323 K for 16 h. Cooling to room temperature led to the precipitation of the product. The supernatant was removed and the precipitate recrystallized from 40 ml of tert-butyl methyl ether. X-ray quality crystals were obtained in a yield of 1.88 g (40%). Notes: (a) Schlenk techniques are necessary because ynamines and catecholborane are moisture-sensitive; (b) the reaction also works well in diethyl ether, 1,4-dioxane or THF.
1H NMR (600 MHz, CDCl3): δ (ppm) = 1.34 (d, 6.8 Hz, 6H, CH3 of i-Pr), 3.89 (hept, 6.8 Hz, 1H, CH of i-Pr), 6.77–6.80 (m, 2H, H5 & H9), 6.81–6.85 (m, 2H, H7 & H15), 6.85–6.92 (m, 6H, H6 & H8 & H13 & H14 & H16 & H17), 6.95–6.98 (m, 2H, 2 × catechol-H), 7.11–7.14 (m, 2H, 2 × catechol-H), 7.53 (s, 1H, H10).
13C1H NMR (151 MHz, CDCl3): δ (ppm) = 22.2 (s, C1 & C2), 57.4 (s, C3), 98.1 (br s, C11), 111.7 (s, 2 × catechol-C), 121.8 (s, 2 × catechol-C), 124.3 (s, C15), 124.6 (s, C7), 126.3 (s, C5 & C9), 126.9 (s, C14 & C16), 128.0 (s, C6 & C8), 129.4 (s, C13 & C17), 138.8 (s, C12), 143.3 (s, C4), 144.9 (s, C10), 148.9 (s, C18 & C23). Inverse gated {13}C{1}H} NMR with D1 = 60 s measured to get integrable 13C NMR.
11B NMR (160 MHz, CDCl3): δ (ppm) = 33.2 (s).
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms were positioned geometrically and refined as riding: C—H = 0.95–0.98 Å and U iso(H) = 1.2U eq(C) or 1.5U eq(C-methyl). The absolute structure was not determined because of unreliable Flack and Hooft parameters.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C23H22BNO2 |
| M r | 355.22 |
| Crystal system, space group | Orthorhombic, P c a21 |
| Temperature (K) | 100 |
| a, b, c (Å) | 17.8540 (11), 11.5361 (6), 18.5366 (12) |
| V (Å3) | 3817.9 (4) |
| Z | 8 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.08 |
| Crystal size (mm) | 0.38 × 0.2 × 0.07 |
| Data collection | |
| Diffractometer | Bruker–Nonius Kappa APEXII |
| Absorption correction | Multi-scan (SADABS; Bruker, 2015 ▸) |
| T min, T max | 0.703, 0.733 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 60829, 8781, 7379 |
| R int | 0.047 |
| (sin θ/λ)max (Å−1) | 0.652 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.039, 0.086, 1.03 |
| No. of reflections | 8781 |
| No. of parameters | 491 |
| No. of restraints | 1 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.25, −0.24 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020005289/lh5953sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989020005289/lh5953Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989020005289/lh5953Isup3.cml
CCDC reference: 1997061
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
X-ray services were provided by SMoCC – The Small Molecule Crystallography Center of ETH Zurich. The authors acknowledge Kevin Breitwieser and Nils Trapp for proof-reading the manuscript.
supplementary crystallographic information
Crystal data
| C23H22BNO2 | Dx = 1.236 Mg m−3 |
| Mr = 355.22 | Mo Kα radiation, λ = 0.71073 Å |
| Orthorhombic, Pca21 | Cell parameters from 9981 reflections |
| a = 17.8540 (11) Å | θ = 2.5–26.8° |
| b = 11.5361 (6) Å | µ = 0.08 mm−1 |
| c = 18.5366 (12) Å | T = 100 K |
| V = 3817.9 (4) Å3 | Plate, clear light yellow |
| Z = 8 | 0.38 × 0.2 × 0.07 mm |
| F(000) = 1504 |
Data collection
| Bruker–Nonius Kappa APEXII diffractometer | 8781 independent reflections |
| Radiation source: sealed tube | 7379 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.047 |
| Detector resolution: 8.33 pixels mm-1 | θmax = 27.6°, θmin = 2.8° |
| ω and φ scans | h = −23→23 |
| Absorption correction: multi-scan (SADABS; Bruker, 2015) | k = −14→14 |
| Tmin = 0.703, Tmax = 0.733 | l = −24→24 |
| 60829 measured reflections |
Refinement
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.0401P)2 + 0.7053P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.086 | (Δ/σ)max < 0.001 |
| S = 1.03 | Δρmax = 0.25 e Å−3 |
| 8781 reflections | Δρmin = −0.24 e Å−3 |
| 491 parameters | Absolute structure: Flack x determined using 3185 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
| 1 restraint | Absolute structure parameter: −0.7 (4) |
| Primary atom site location: structure-invariant direct methods |
Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
| Refinement. 8 reflections were omitted (some are equivalents). These were checked visually and are all results of high background around the beamstop (beginning ice formation or crystalline powder covering the sample). 0 1 0 is clearly shadowed by the beamstop. Absolute structure is not claimed due to unreliable Flack and Hooft parameters. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| O1B | 0.18188 (9) | 0.59842 (13) | 0.60028 (9) | 0.0155 (4) | |
| O2B | 0.30086 (9) | 0.67252 (13) | 0.61169 (9) | 0.0158 (4) | |
| N1B | 0.23745 (11) | 0.25154 (16) | 0.65127 (11) | 0.0159 (4) | |
| C1B | 0.10503 (15) | 0.2002 (2) | 0.62440 (14) | 0.0210 (6) | |
| H1BA | 0.0874 | 0.2806 | 0.6251 | 0.032* | |
| H1BB | 0.0642 | 0.1485 | 0.6390 | 0.032* | |
| H1BC | 0.1215 | 0.1800 | 0.5756 | 0.032* | |
| C2B | 0.14877 (15) | 0.2209 (2) | 0.75303 (14) | 0.0205 (6) | |
| H2BA | 0.1928 | 0.2152 | 0.7844 | 0.031* | |
| H2BB | 0.1096 | 0.1686 | 0.7707 | 0.031* | |
| H2BC | 0.1301 | 0.3008 | 0.7533 | 0.031* | |
| C3B | 0.17032 (14) | 0.1869 (2) | 0.67659 (13) | 0.0160 (5) | |
| H3B | 0.1840 | 0.1028 | 0.6776 | 0.019* | |
| C4B | 0.30570 (13) | 0.18933 (19) | 0.64199 (14) | 0.0147 (5) | |
| C5B | 0.32986 (14) | 0.1121 (2) | 0.69452 (14) | 0.0189 (5) | |
| H5B | 0.3009 | 0.1007 | 0.7369 | 0.023* | |
| C6B | 0.39606 (14) | 0.0518 (2) | 0.68521 (16) | 0.0230 (6) | |
| H6B | 0.4126 | −0.0006 | 0.7214 | 0.028* | |
| C7B | 0.43822 (15) | 0.0673 (2) | 0.62365 (16) | 0.0275 (6) | |
| H7B | 0.4841 | 0.0267 | 0.6177 | 0.033* | |
| C8B | 0.41341 (15) | 0.1423 (2) | 0.57066 (15) | 0.0238 (6) | |
| H8B | 0.4420 | 0.1522 | 0.5279 | 0.029* | |
| C9B | 0.34704 (14) | 0.2033 (2) | 0.57938 (14) | 0.0191 (5) | |
| H9B | 0.3301 | 0.2543 | 0.5426 | 0.023* | |
| C10B | 0.23179 (13) | 0.36795 (19) | 0.63924 (13) | 0.0151 (5) | |
| H10B | 0.1820 | 0.3949 | 0.6321 | 0.018* | |
| C11B | 0.28538 (13) | 0.4526 (2) | 0.63563 (13) | 0.0156 (5) | |
| C12B | 0.36555 (13) | 0.4370 (2) | 0.65557 (13) | 0.0142 (5) | |
| C13B | 0.38562 (14) | 0.3878 (2) | 0.72178 (13) | 0.0172 (5) | |
| H13B | 0.3476 | 0.3630 | 0.7541 | 0.021* | |
| C14B | 0.46041 (15) | 0.3748 (2) | 0.74087 (14) | 0.0209 (5) | |
| H14B | 0.4731 | 0.3410 | 0.7860 | 0.025* | |
| C15B | 0.51658 (14) | 0.4110 (2) | 0.69433 (14) | 0.0210 (6) | |
| H15B | 0.5677 | 0.4012 | 0.7071 | 0.025* | |
| C16B | 0.49740 (14) | 0.4614 (2) | 0.62906 (14) | 0.0188 (5) | |
| H16B | 0.5356 | 0.4869 | 0.5972 | 0.023* | |
| C17B | 0.42288 (14) | 0.4749 (2) | 0.60995 (14) | 0.0169 (5) | |
| H17B | 0.4106 | 0.5103 | 0.5652 | 0.020* | |
| C18B | 0.18063 (14) | 0.71629 (19) | 0.58605 (13) | 0.0140 (5) | |
| C19B | 0.12056 (14) | 0.7829 (2) | 0.56544 (13) | 0.0178 (5) | |
| H19B | 0.0715 | 0.7518 | 0.5614 | 0.021* | |
| C20B | 0.13606 (15) | 0.8997 (2) | 0.55079 (14) | 0.0198 (5) | |
| H20B | 0.0966 | 0.9492 | 0.5356 | 0.024* | |
| C21B | 0.20801 (15) | 0.9445 (2) | 0.55794 (13) | 0.0192 (5) | |
| H21B | 0.2165 | 1.0242 | 0.5478 | 0.023* | |
| C22B | 0.26793 (14) | 0.8754 (2) | 0.57958 (13) | 0.0179 (5) | |
| H22B | 0.3171 | 0.9059 | 0.5849 | 0.022* | |
| C23B | 0.25211 (13) | 0.76087 (19) | 0.59287 (13) | 0.0151 (5) | |
| B1B | 0.25681 (15) | 0.5724 (2) | 0.61526 (14) | 0.0149 (6) | |
| O1A | 0.59813 (9) | −0.09865 (13) | 0.40292 (10) | 0.0176 (4) | |
| O2A | 0.71747 (9) | −0.17253 (13) | 0.39845 (9) | 0.0174 (4) | |
| N1A | 0.65302 (11) | 0.24387 (17) | 0.34366 (11) | 0.0161 (4) | |
| C1A | 0.52189 (14) | 0.2942 (2) | 0.37802 (15) | 0.0228 (6) | |
| H1AA | 0.5416 | 0.3104 | 0.4263 | 0.034* | |
| H1AB | 0.5027 | 0.2146 | 0.3764 | 0.034* | |
| H1AC | 0.4813 | 0.3485 | 0.3671 | 0.034* | |
| C2A | 0.58421 (14) | 0.3081 (2) | 0.32256 (14) | 0.0177 (5) | |
| H2A | 0.5976 | 0.3923 | 0.3213 | 0.021* | |
| C3A | 0.55869 (14) | 0.2754 (2) | 0.24731 (15) | 0.0227 (6) | |
| H3AA | 0.5407 | 0.1952 | 0.2473 | 0.034* | |
| H3AB | 0.6008 | 0.2829 | 0.2137 | 0.034* | |
| H3AC | 0.5180 | 0.3272 | 0.2323 | 0.034* | |
| C4A | 0.72025 (13) | 0.3083 (2) | 0.35237 (13) | 0.0139 (5) | |
| C5A | 0.76423 (13) | 0.2910 (2) | 0.41332 (13) | 0.0150 (5) | |
| H5A | 0.7496 | 0.2358 | 0.4487 | 0.018* | |
| C6A | 0.82952 (14) | 0.3543 (2) | 0.42245 (14) | 0.0199 (5) | |
| H6A | 0.8596 | 0.3423 | 0.4640 | 0.024* | |
| C7A | 0.85112 (15) | 0.4353 (2) | 0.37098 (15) | 0.0233 (6) | |
| H7A | 0.8964 | 0.4776 | 0.3768 | 0.028* | |
| C8A | 0.80630 (14) | 0.4541 (2) | 0.31124 (16) | 0.0227 (6) | |
| H8A | 0.8204 | 0.5105 | 0.2765 | 0.027* | |
| C9A | 0.74113 (14) | 0.3912 (2) | 0.30178 (14) | 0.0182 (5) | |
| H9A | 0.7106 | 0.4047 | 0.2607 | 0.022* | |
| C10A | 0.64818 (14) | 0.1276 (2) | 0.35658 (13) | 0.0157 (5) | |
| H10A | 0.5984 | 0.1001 | 0.3624 | 0.019* | |
| C11A | 0.70180 (13) | 0.0433 (2) | 0.36266 (12) | 0.0136 (5) | |
| C12A | 0.78275 (13) | 0.0582 (2) | 0.34518 (13) | 0.0143 (5) | |
| C13A | 0.83799 (13) | 0.0207 (2) | 0.39292 (13) | 0.0159 (5) | |
| H13A | 0.8239 | −0.0154 | 0.4369 | 0.019* | |
| C14A | 0.91359 (14) | 0.0353 (2) | 0.37700 (15) | 0.0184 (5) | |
| H14A | 0.9505 | 0.0104 | 0.4105 | 0.022* | |
| C15A | 0.93517 (15) | 0.0860 (2) | 0.31277 (14) | 0.0209 (6) | |
| H15A | 0.9868 | 0.0967 | 0.3021 | 0.025* | |
| C16A | 0.88076 (14) | 0.1212 (2) | 0.26390 (14) | 0.0209 (6) | |
| H16A | 0.8952 | 0.1549 | 0.2193 | 0.025* | |
| C17A | 0.80555 (14) | 0.1074 (2) | 0.27994 (13) | 0.0166 (5) | |
| H17A | 0.7689 | 0.1317 | 0.2460 | 0.020* | |
| C18A | 0.59638 (14) | −0.2147 (2) | 0.42114 (13) | 0.0155 (5) | |
| C19A | 0.53579 (14) | −0.2820 (2) | 0.43916 (14) | 0.0196 (5) | |
| H19A | 0.4864 | −0.2514 | 0.4402 | 0.024* | |
| C20A | 0.55064 (15) | −0.3974 (2) | 0.45574 (14) | 0.0212 (6) | |
| H20A | 0.5102 | −0.4469 | 0.4685 | 0.025* | |
| C21A | 0.62240 (15) | −0.4420 (2) | 0.45425 (14) | 0.0221 (6) | |
| H21A | 0.6302 | −0.5212 | 0.4661 | 0.027* | |
| C22A | 0.68384 (15) | −0.3727 (2) | 0.43561 (14) | 0.0215 (6) | |
| H22A | 0.7335 | −0.4024 | 0.4346 | 0.026* | |
| C23A | 0.66814 (14) | −0.2591 (2) | 0.41882 (13) | 0.0159 (5) | |
| B1A | 0.67343 (15) | −0.0740 (2) | 0.38806 (15) | 0.0149 (5) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1B | 0.0139 (8) | 0.0119 (8) | 0.0206 (9) | 0.0005 (7) | 0.0001 (7) | 0.0023 (7) |
| O2B | 0.0137 (8) | 0.0144 (8) | 0.0194 (9) | −0.0010 (6) | −0.0018 (7) | 0.0016 (7) |
| N1B | 0.0115 (10) | 0.0142 (9) | 0.0218 (11) | 0.0004 (8) | 0.0030 (8) | 0.0028 (8) |
| C1B | 0.0183 (13) | 0.0203 (12) | 0.0245 (15) | −0.0017 (10) | −0.0016 (11) | −0.0009 (11) |
| C2B | 0.0194 (14) | 0.0215 (13) | 0.0206 (13) | −0.0021 (11) | 0.0031 (11) | 0.0012 (10) |
| C3B | 0.0142 (13) | 0.0135 (11) | 0.0205 (13) | −0.0017 (10) | 0.0030 (10) | 0.0013 (10) |
| C4B | 0.0115 (12) | 0.0112 (10) | 0.0213 (13) | −0.0010 (9) | −0.0012 (10) | −0.0023 (10) |
| C5B | 0.0187 (13) | 0.0162 (12) | 0.0218 (14) | −0.0021 (10) | −0.0029 (10) | 0.0006 (10) |
| C6B | 0.0174 (13) | 0.0157 (12) | 0.0360 (16) | 0.0007 (10) | −0.0082 (12) | 0.0023 (11) |
| C7B | 0.0144 (13) | 0.0196 (12) | 0.0487 (19) | 0.0027 (11) | 0.0015 (13) | −0.0046 (12) |
| C8B | 0.0196 (14) | 0.0191 (13) | 0.0328 (16) | −0.0020 (11) | 0.0108 (11) | −0.0065 (11) |
| C9B | 0.0173 (13) | 0.0168 (12) | 0.0232 (13) | −0.0015 (10) | 0.0015 (10) | −0.0014 (10) |
| C10B | 0.0132 (12) | 0.0174 (11) | 0.0147 (11) | 0.0022 (9) | 0.0007 (9) | 0.0013 (10) |
| C11B | 0.0146 (12) | 0.0169 (11) | 0.0152 (12) | 0.0014 (10) | 0.0027 (10) | 0.0006 (10) |
| C12B | 0.0133 (12) | 0.0120 (11) | 0.0173 (12) | 0.0018 (9) | 0.0002 (10) | −0.0012 (10) |
| C13B | 0.0182 (13) | 0.0161 (12) | 0.0172 (13) | 0.0000 (10) | 0.0021 (10) | −0.0014 (10) |
| C14B | 0.0217 (14) | 0.0217 (13) | 0.0195 (13) | 0.0023 (11) | −0.0053 (11) | 0.0007 (11) |
| C15B | 0.0143 (13) | 0.0208 (12) | 0.0281 (15) | 0.0023 (10) | −0.0057 (11) | −0.0022 (11) |
| C16B | 0.0144 (12) | 0.0178 (12) | 0.0244 (14) | −0.0007 (10) | 0.0032 (10) | −0.0005 (10) |
| C17B | 0.0177 (12) | 0.0163 (11) | 0.0169 (12) | 0.0007 (10) | 0.0008 (10) | 0.0008 (10) |
| C18B | 0.0171 (12) | 0.0124 (11) | 0.0124 (11) | −0.0024 (10) | 0.0031 (9) | 0.0000 (9) |
| C19B | 0.0140 (13) | 0.0202 (13) | 0.0191 (13) | 0.0031 (10) | 0.0011 (10) | 0.0001 (10) |
| C20B | 0.0236 (14) | 0.0186 (12) | 0.0171 (13) | 0.0061 (11) | 0.0014 (11) | 0.0014 (10) |
| C21B | 0.0277 (14) | 0.0125 (11) | 0.0172 (13) | 0.0003 (11) | 0.0044 (11) | −0.0002 (10) |
| C22B | 0.0217 (13) | 0.0174 (11) | 0.0147 (12) | −0.0032 (10) | 0.0000 (10) | −0.0025 (9) |
| C23B | 0.0158 (12) | 0.0167 (11) | 0.0127 (11) | 0.0028 (10) | −0.0025 (9) | −0.0023 (10) |
| B1B | 0.0128 (13) | 0.0191 (13) | 0.0129 (13) | −0.0004 (11) | 0.0016 (11) | −0.0006 (11) |
| O1A | 0.0134 (9) | 0.0138 (8) | 0.0258 (10) | −0.0012 (7) | 0.0003 (7) | 0.0027 (7) |
| O2A | 0.0139 (9) | 0.0146 (8) | 0.0237 (10) | −0.0005 (7) | 0.0028 (7) | 0.0023 (7) |
| N1A | 0.0116 (10) | 0.0147 (10) | 0.0220 (11) | 0.0002 (8) | −0.0036 (8) | 0.0030 (8) |
| C1A | 0.0161 (13) | 0.0221 (13) | 0.0304 (15) | 0.0042 (11) | 0.0001 (11) | 0.0005 (12) |
| C2A | 0.0128 (12) | 0.0150 (11) | 0.0251 (14) | 0.0015 (10) | −0.0032 (10) | 0.0033 (10) |
| C3A | 0.0154 (14) | 0.0273 (14) | 0.0254 (14) | 0.0027 (11) | −0.0061 (11) | 0.0047 (11) |
| C4A | 0.0121 (12) | 0.0119 (11) | 0.0175 (12) | 0.0009 (9) | 0.0005 (10) | −0.0018 (9) |
| C5A | 0.0157 (12) | 0.0142 (10) | 0.0151 (12) | 0.0010 (9) | 0.0010 (10) | −0.0004 (9) |
| C6A | 0.0160 (12) | 0.0214 (12) | 0.0223 (14) | 0.0021 (10) | −0.0038 (10) | −0.0035 (11) |
| C7A | 0.0155 (13) | 0.0179 (12) | 0.0366 (16) | −0.0054 (11) | 0.0001 (12) | −0.0006 (11) |
| C8A | 0.0198 (14) | 0.0182 (12) | 0.0300 (15) | −0.0014 (11) | 0.0034 (11) | 0.0066 (11) |
| C9A | 0.0175 (13) | 0.0173 (12) | 0.0198 (13) | 0.0018 (10) | −0.0009 (10) | 0.0033 (10) |
| C10A | 0.0129 (12) | 0.0171 (12) | 0.0172 (12) | −0.0036 (10) | −0.0012 (9) | 0.0010 (10) |
| C11A | 0.0125 (12) | 0.0146 (11) | 0.0138 (12) | 0.0000 (9) | −0.0014 (9) | 0.0005 (9) |
| C12A | 0.0143 (12) | 0.0123 (11) | 0.0164 (12) | −0.0009 (9) | 0.0007 (10) | −0.0042 (10) |
| C13A | 0.0162 (12) | 0.0143 (11) | 0.0170 (13) | 0.0002 (10) | 0.0011 (10) | 0.0002 (10) |
| C14A | 0.0140 (12) | 0.0166 (12) | 0.0247 (14) | 0.0000 (10) | −0.0032 (10) | −0.0033 (10) |
| C15A | 0.0152 (13) | 0.0220 (12) | 0.0255 (14) | −0.0017 (10) | 0.0056 (11) | −0.0028 (11) |
| C16A | 0.0229 (14) | 0.0215 (13) | 0.0182 (13) | −0.0034 (11) | 0.0064 (11) | 0.0000 (11) |
| C17A | 0.0165 (12) | 0.0167 (12) | 0.0166 (12) | −0.0003 (10) | −0.0014 (10) | −0.0008 (10) |
| C18A | 0.0185 (13) | 0.0154 (11) | 0.0127 (12) | −0.0018 (10) | −0.0012 (9) | 0.0004 (9) |
| C19A | 0.0151 (13) | 0.0228 (13) | 0.0211 (13) | −0.0022 (11) | −0.0002 (10) | 0.0028 (11) |
| C20A | 0.0236 (14) | 0.0209 (13) | 0.0190 (13) | −0.0103 (11) | −0.0021 (11) | 0.0036 (10) |
| C21A | 0.0294 (15) | 0.0155 (12) | 0.0215 (13) | −0.0025 (11) | −0.0005 (11) | 0.0047 (10) |
| C22A | 0.0216 (14) | 0.0191 (12) | 0.0237 (14) | 0.0030 (11) | −0.0002 (11) | 0.0019 (11) |
| C23A | 0.0137 (12) | 0.0178 (12) | 0.0164 (12) | −0.0037 (10) | 0.0009 (10) | 0.0009 (10) |
| B1A | 0.0126 (13) | 0.0177 (13) | 0.0143 (13) | −0.0006 (11) | 0.0002 (11) | −0.0026 (11) |
Geometric parameters (Å, º)
| O1B—C18B | 1.385 (3) | O1A—C18A | 1.382 (3) |
| O1B—B1B | 1.399 (3) | O1A—B1A | 1.402 (3) |
| O2B—C23B | 1.385 (3) | O2A—C23A | 1.384 (3) |
| O2B—B1B | 1.398 (3) | O2A—B1A | 1.396 (3) |
| N1B—C3B | 1.488 (3) | N1A—C2A | 1.487 (3) |
| N1B—C4B | 1.425 (3) | N1A—C4A | 1.421 (3) |
| N1B—C10B | 1.365 (3) | N1A—C10A | 1.365 (3) |
| C1B—H1BA | 0.9800 | C1A—H1AA | 0.9800 |
| C1B—H1BB | 0.9800 | C1A—H1AB | 0.9800 |
| C1B—H1BC | 0.9800 | C1A—H1AC | 0.9800 |
| C1B—C3B | 1.523 (4) | C1A—C2A | 1.523 (4) |
| C2B—H2BA | 0.9800 | C2A—H2A | 1.0000 |
| C2B—H2BB | 0.9800 | C2A—C3A | 1.515 (4) |
| C2B—H2BC | 0.9800 | C3A—H3AA | 0.9800 |
| C2B—C3B | 1.520 (3) | C3A—H3AB | 0.9800 |
| C3B—H3B | 1.0000 | C3A—H3AC | 0.9800 |
| C4B—C5B | 1.389 (3) | C4A—C5A | 1.390 (3) |
| C4B—C9B | 1.385 (4) | C4A—C9A | 1.390 (3) |
| C5B—H5B | 0.9500 | C5A—H5A | 0.9500 |
| C5B—C6B | 1.382 (3) | C5A—C6A | 1.386 (3) |
| C6B—H6B | 0.9500 | C6A—H6A | 0.9500 |
| C6B—C7B | 1.379 (4) | C6A—C7A | 1.390 (4) |
| C7B—H7B | 0.9500 | C7A—H7A | 0.9500 |
| C7B—C8B | 1.382 (4) | C7A—C8A | 1.383 (4) |
| C8B—H8B | 0.9500 | C8A—H8A | 0.9500 |
| C8B—C9B | 1.387 (4) | C8A—C9A | 1.382 (4) |
| C9B—H9B | 0.9500 | C9A—H9A | 0.9500 |
| C10B—H10B | 0.9500 | C10A—H10A | 0.9500 |
| C10B—C11B | 1.369 (3) | C10A—C11A | 1.370 (3) |
| C11B—C12B | 1.489 (3) | C11A—C12A | 1.491 (3) |
| C11B—B1B | 1.521 (4) | C11A—B1A | 1.519 (3) |
| C12B—C13B | 1.399 (3) | C12A—C13A | 1.394 (3) |
| C12B—C17B | 1.398 (3) | C12A—C17A | 1.397 (3) |
| C13B—H13B | 0.9500 | C13A—H13A | 0.9500 |
| C13B—C14B | 1.389 (4) | C13A—C14A | 1.392 (3) |
| C14B—H14B | 0.9500 | C14A—H14A | 0.9500 |
| C14B—C15B | 1.387 (4) | C14A—C15A | 1.381 (4) |
| C15B—H15B | 0.9500 | C15A—H15A | 0.9500 |
| C15B—C16B | 1.385 (4) | C15A—C16A | 1.389 (4) |
| C16B—H16B | 0.9500 | C16A—H16A | 0.9500 |
| C16B—C17B | 1.386 (3) | C16A—C17A | 1.385 (3) |
| C17B—H17B | 0.9500 | C17A—H17A | 0.9500 |
| C18B—C19B | 1.374 (3) | C18A—C19A | 1.372 (3) |
| C18B—C23B | 1.382 (3) | C18A—C23A | 1.381 (3) |
| C19B—H19B | 0.9500 | C19A—H19A | 0.9500 |
| C19B—C20B | 1.401 (3) | C20A—H20A | 0.9500 |
| C20B—H20B | 0.9500 | C20A—C21A | 1.381 (4) |
| C20B—C21B | 1.391 (4) | C21A—H21A | 0.9500 |
| C21B—H21B | 0.9500 | C21A—C22A | 1.401 (4) |
| C21B—C22B | 1.393 (4) | C22A—H22A | 0.9500 |
| C22B—H22B | 0.9500 | C22A—C23A | 1.375 (3) |
| C22B—C23B | 1.374 (3) | ||
| C18B—O1B—B1B | 105.28 (18) | C18A—O1A—B1A | 105.46 (18) |
| C23B—O2B—B1B | 105.43 (18) | C23A—O2A—B1A | 105.50 (18) |
| C4B—N1B—C3B | 118.34 (18) | C4A—N1A—C2A | 117.83 (18) |
| C10B—N1B—C3B | 119.02 (19) | C10A—N1A—C2A | 118.9 (2) |
| C10B—N1B—C4B | 122.6 (2) | C10A—N1A—C4A | 123.2 (2) |
| H1BA—C1B—H1BB | 109.5 | H1AA—C1A—H1AB | 109.5 |
| H1BA—C1B—H1BC | 109.5 | H1AA—C1A—H1AC | 109.5 |
| H1BB—C1B—H1BC | 109.5 | H1AB—C1A—H1AC | 109.5 |
| C3B—C1B—H1BA | 109.5 | C2A—C1A—H1AA | 109.5 |
| C3B—C1B—H1BB | 109.5 | C2A—C1A—H1AB | 109.5 |
| C3B—C1B—H1BC | 109.5 | C2A—C1A—H1AC | 109.5 |
| H2BA—C2B—H2BB | 109.5 | N1A—C2A—C1A | 111.9 (2) |
| H2BA—C2B—H2BC | 109.5 | N1A—C2A—H2A | 107.0 |
| H2BB—C2B—H2BC | 109.5 | N1A—C2A—C3A | 111.5 (2) |
| C3B—C2B—H2BA | 109.5 | C1A—C2A—H2A | 107.0 |
| C3B—C2B—H2BB | 109.5 | C3A—C2A—C1A | 112.1 (2) |
| C3B—C2B—H2BC | 109.5 | C3A—C2A—H2A | 107.0 |
| N1B—C3B—C1B | 111.5 (2) | C2A—C3A—H3AA | 109.5 |
| N1B—C3B—C2B | 111.6 (2) | C2A—C3A—H3AB | 109.5 |
| N1B—C3B—H3B | 107.2 | C2A—C3A—H3AC | 109.5 |
| C1B—C3B—H3B | 107.2 | H3AA—C3A—H3AB | 109.5 |
| C2B—C3B—C1B | 111.9 (2) | H3AA—C3A—H3AC | 109.5 |
| C2B—C3B—H3B | 107.2 | H3AB—C3A—H3AC | 109.5 |
| C5B—C4B—N1B | 120.3 (2) | C5A—C4A—N1A | 119.6 (2) |
| C9B—C4B—N1B | 119.9 (2) | C5A—C4A—C9A | 119.7 (2) |
| C9B—C4B—C5B | 119.8 (2) | C9A—C4A—N1A | 120.6 (2) |
| C4B—C5B—H5B | 120.0 | C4A—C5A—H5A | 120.1 |
| C6B—C5B—C4B | 120.1 (2) | C6A—C5A—C4A | 119.9 (2) |
| C6B—C5B—H5B | 120.0 | C6A—C5A—H5A | 120.1 |
| C5B—C6B—H6B | 119.8 | C5A—C6A—H6A | 119.9 |
| C7B—C6B—C5B | 120.3 (2) | C5A—C6A—C7A | 120.3 (2) |
| C7B—C6B—H6B | 119.8 | C7A—C6A—H6A | 119.9 |
| C6B—C7B—H7B | 120.2 | C6A—C7A—H7A | 120.2 |
| C6B—C7B—C8B | 119.7 (2) | C8A—C7A—C6A | 119.6 (2) |
| C8B—C7B—H7B | 120.2 | C8A—C7A—H7A | 120.2 |
| C7B—C8B—H8B | 119.7 | C7A—C8A—H8A | 119.8 |
| C7B—C8B—C9B | 120.5 (2) | C9A—C8A—C7A | 120.4 (2) |
| C9B—C8B—H8B | 119.7 | C9A—C8A—H8A | 119.8 |
| C4B—C9B—C8B | 119.6 (2) | C4A—C9A—H9A | 120.0 |
| C4B—C9B—H9B | 120.2 | C8A—C9A—C4A | 120.1 (2) |
| C8B—C9B—H9B | 120.2 | C8A—C9A—H9A | 120.0 |
| N1B—C10B—H10B | 114.4 | N1A—C10A—H10A | 114.0 |
| N1B—C10B—C11B | 131.2 (2) | N1A—C10A—C11A | 131.9 (2) |
| C11B—C10B—H10B | 114.4 | C11A—C10A—H10A | 114.0 |
| C10B—C11B—C12B | 125.0 (2) | C10A—C11A—C12A | 125.3 (2) |
| C10B—C11B—B1B | 115.2 (2) | C10A—C11A—B1A | 115.1 (2) |
| C12B—C11B—B1B | 119.6 (2) | C12A—C11A—B1A | 119.5 (2) |
| C13B—C12B—C11B | 120.9 (2) | C13A—C12A—C11A | 120.8 (2) |
| C17B—C12B—C11B | 121.1 (2) | C13A—C12A—C17A | 118.0 (2) |
| C17B—C12B—C13B | 118.0 (2) | C17A—C12A—C11A | 121.2 (2) |
| C12B—C13B—H13B | 119.6 | C12A—C13A—H13A | 119.5 |
| C14B—C13B—C12B | 120.9 (2) | C14A—C13A—C12A | 120.9 (2) |
| C14B—C13B—H13B | 119.6 | C14A—C13A—H13A | 119.5 |
| C13B—C14B—H14B | 119.9 | C13A—C14A—H14A | 119.8 |
| C15B—C14B—C13B | 120.3 (2) | C15A—C14A—C13A | 120.3 (2) |
| C15B—C14B—H14B | 119.9 | C15A—C14A—H14A | 119.8 |
| C14B—C15B—H15B | 120.3 | C14A—C15A—H15A | 120.3 |
| C16B—C15B—C14B | 119.4 (2) | C14A—C15A—C16A | 119.4 (2) |
| C16B—C15B—H15B | 120.3 | C16A—C15A—H15A | 120.3 |
| C15B—C16B—H16B | 119.7 | C15A—C16A—H16A | 119.9 |
| C15B—C16B—C17B | 120.5 (2) | C17A—C16A—C15A | 120.3 (2) |
| C17B—C16B—H16B | 119.7 | C17A—C16A—H16A | 119.9 |
| C12B—C17B—H17B | 119.5 | C12A—C17A—H17A | 119.5 |
| C16B—C17B—C12B | 120.9 (2) | C16A—C17A—C12A | 121.0 (2) |
| C16B—C17B—H17B | 119.5 | C16A—C17A—H17A | 119.5 |
| C19B—C18B—O1B | 127.9 (2) | C19A—C18A—O1A | 128.7 (2) |
| C19B—C18B—C23B | 122.6 (2) | C19A—C18A—C23A | 122.0 (2) |
| C23B—C18B—O1B | 109.4 (2) | C23A—C18A—O1A | 109.3 (2) |
| C18B—C19B—H19B | 122.0 | C18A—C19A—H19A | 121.8 |
| C18B—C19B—C20B | 115.9 (2) | C18A—C19A—C20A | 116.4 (2) |
| C20B—C19B—H19B | 122.0 | C20A—C19A—H19A | 121.8 |
| C19B—C20B—H20B | 119.3 | C19A—C20A—H20A | 119.0 |
| C21B—C20B—C19B | 121.4 (2) | C21A—C20A—C19A | 121.9 (2) |
| C21B—C20B—H20B | 119.3 | C21A—C20A—H20A | 119.0 |
| C20B—C21B—H21B | 119.2 | C20A—C21A—H21A | 119.4 |
| C20B—C21B—C22B | 121.6 (2) | C20A—C21A—C22A | 121.3 (2) |
| C22B—C21B—H21B | 119.2 | C22A—C21A—H21A | 119.4 |
| C21B—C22B—H22B | 121.8 | C21A—C22A—H22A | 122.0 |
| C23B—C22B—C21B | 116.4 (2) | C23A—C22A—C21A | 116.1 (2) |
| C23B—C22B—H22B | 121.8 | C23A—C22A—H22A | 122.0 |
| C18B—C23B—O2B | 109.24 (19) | C18A—C23A—O2A | 109.3 (2) |
| C22B—C23B—O2B | 128.6 (2) | C22A—C23A—O2A | 128.3 (2) |
| C22B—C23B—C18B | 122.1 (2) | C22A—C23A—C18A | 122.4 (2) |
| O1B—B1B—C11B | 124.4 (2) | O1A—B1A—C11A | 124.2 (2) |
| O2B—B1B—O1B | 110.6 (2) | O2A—B1A—O1A | 110.4 (2) |
| O2B—B1B—C11B | 125.0 (2) | O2A—B1A—C11A | 125.5 (2) |
| O1B—C18B—C19B—C20B | −176.7 (2) | O1A—C18A—C19A—C20A | −179.5 (2) |
| O1B—C18B—C23B—O2B | 0.0 (3) | O1A—C18A—C23A—O2A | −0.5 (3) |
| O1B—C18B—C23B—C22B | 177.9 (2) | O1A—C18A—C23A—C22A | 178.9 (2) |
| N1B—C4B—C5B—C6B | 179.9 (2) | N1A—C4A—C5A—C6A | −179.4 (2) |
| N1B—C4B—C9B—C8B | −179.9 (2) | N1A—C4A—C9A—C8A | 179.4 (2) |
| N1B—C10B—C11B—C12B | −9.7 (4) | N1A—C10A—C11A—C12A | −9.7 (4) |
| N1B—C10B—C11B—B1B | 175.5 (2) | N1A—C10A—C11A—B1A | 171.6 (2) |
| C3B—N1B—C4B—C5B | −45.6 (3) | C2A—N1A—C4A—C5A | 132.7 (2) |
| C3B—N1B—C4B—C9B | 132.5 (2) | C2A—N1A—C4A—C9A | −45.1 (3) |
| C3B—N1B—C10B—C11B | 159.6 (3) | C2A—N1A—C10A—C11A | 165.3 (2) |
| C4B—N1B—C3B—C1B | −123.7 (2) | C4A—N1A—C2A—C1A | −120.9 (2) |
| C4B—N1B—C3B—C2B | 110.3 (2) | C4A—N1A—C2A—C3A | 112.7 (2) |
| C4B—N1B—C10B—C11B | −19.1 (4) | C4A—N1A—C10A—C11A | −17.5 (4) |
| C4B—C5B—C6B—C7B | −0.4 (4) | C4A—C5A—C6A—C7A | 0.1 (4) |
| C5B—C4B—C9B—C8B | −1.8 (4) | C5A—C4A—C9A—C8A | 1.6 (4) |
| C5B—C6B—C7B—C8B | −1.0 (4) | C5A—C6A—C7A—C8A | 1.3 (4) |
| C6B—C7B—C8B—C9B | 1.0 (4) | C6A—C7A—C8A—C9A | −1.3 (4) |
| C7B—C8B—C9B—C4B | 0.5 (4) | C7A—C8A—C9A—C4A | −0.1 (4) |
| C9B—C4B—C5B—C6B | 1.8 (4) | C9A—C4A—C5A—C6A | −1.6 (4) |
| C10B—N1B—C3B—C1B | 57.5 (3) | C10A—N1A—C2A—C1A | 56.4 (3) |
| C10B—N1B—C3B—C2B | −68.4 (3) | C10A—N1A—C2A—C3A | −69.9 (3) |
| C10B—N1B—C4B—C5B | 133.1 (2) | C10A—N1A—C4A—C5A | −44.5 (3) |
| C10B—N1B—C4B—C9B | −48.8 (3) | C10A—N1A—C4A—C9A | 137.6 (2) |
| C10B—C11B—C12B—C13B | −50.5 (3) | C10A—C11A—C12A—C13A | 132.2 (3) |
| C10B—C11B—C12B—C17B | 131.9 (3) | C10A—C11A—C12A—C17A | −49.3 (3) |
| C10B—C11B—B1B—O1B | −0.5 (4) | C10A—C11A—B1A—O1A | 1.7 (4) |
| C10B—C11B—B1B—O2B | 176.9 (2) | C10A—C11A—B1A—O2A | −179.8 (2) |
| C11B—C12B—C13B—C14B | −179.0 (2) | C11A—C12A—C13A—C14A | −179.5 (2) |
| C11B—C12B—C17B—C16B | 179.3 (2) | C11A—C12A—C17A—C16A | 179.9 (2) |
| C12B—C11B—B1B—O1B | −175.6 (2) | C12A—C11A—B1A—O1A | −177.2 (2) |
| C12B—C11B—B1B—O2B | 1.7 (4) | C12A—C11A—B1A—O2A | 1.4 (4) |
| C12B—C13B—C14B—C15B | 0.2 (4) | C12A—C13A—C14A—C15A | −1.0 (4) |
| C13B—C12B—C17B—C16B | 1.6 (3) | C13A—C12A—C17A—C16A | −1.6 (3) |
| C13B—C14B—C15B—C16B | 0.8 (4) | C13A—C14A—C15A—C16A | −0.6 (4) |
| C14B—C15B—C16B—C17B | −0.5 (4) | C14A—C15A—C16A—C17A | 1.1 (4) |
| C15B—C16B—C17B—C12B | −0.6 (4) | C15A—C16A—C17A—C12A | 0.1 (4) |
| C17B—C12B—C13B—C14B | −1.3 (3) | C17A—C12A—C13A—C14A | 2.0 (3) |
| C18B—O1B—B1B—O2B | 1.1 (3) | C18A—O1A—B1A—O2A | −1.2 (3) |
| C18B—O1B—B1B—C11B | 178.7 (2) | C18A—O1A—B1A—C11A | 177.5 (2) |
| C18B—C19B—C20B—C21B | −0.9 (4) | C18A—C19A—C20A—C21A | 0.1 (4) |
| C19B—C18B—C23B—O2B | −177.8 (2) | C19A—C18A—C23A—O2A | 179.4 (2) |
| C19B—C18B—C23B—C22B | 0.1 (4) | C19A—C18A—C23A—C22A | −1.2 (4) |
| C19B—C20B—C21B—C22B | 0.3 (4) | C19A—C20A—C21A—C22A | −0.2 (4) |
| C20B—C21B—C22B—C23B | 0.5 (4) | C20A—C21A—C22A—C23A | −0.3 (4) |
| C21B—C22B—C23B—O2B | 176.8 (2) | C21A—C22A—C23A—O2A | −179.7 (2) |
| C21B—C22B—C23B—C18B | −0.7 (4) | C21A—C22A—C23A—C18A | 1.0 (4) |
| C23B—O2B—B1B—O1B | −1.1 (3) | C23A—O2A—B1A—O1A | 1.0 (3) |
| C23B—O2B—B1B—C11B | −178.7 (2) | C23A—O2A—B1A—C11A | −177.8 (2) |
| C23B—C18B—C19B—C20B | 0.7 (4) | C23A—C18A—C19A—C20A | 0.6 (4) |
| B1B—O1B—C18B—C19B | 177.0 (2) | B1A—O1A—C18A—C19A | −178.8 (3) |
| B1B—O1B—C18B—C23B | −0.6 (3) | B1A—O1A—C18A—C23A | 1.0 (3) |
| B1B—O2B—C23B—C18B | 0.7 (3) | B1A—O2A—C23A—C18A | −0.3 (3) |
| B1B—O2B—C23B—C22B | −177.1 (2) | B1A—O2A—C23A—C22A | −179.7 (3) |
| B1B—C11B—C12B—C13B | 124.1 (3) | B1A—C11A—C12A—C13A | −49.1 (3) |
| B1B—C11B—C12B—C17B | −53.5 (3) | B1A—C11A—C12A—C17A | 129.4 (2) |
Funding Statement
This work was funded by Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung grant .
References
- Adamczyk-Woźniak, A., Jakubczyk, M., Sporzyński, A. & Żukowska, G. (2011). Inorg. Chem. Commun. 14, 1753–1755.
- Allen, F. H., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (2006). International Tables for Crystallography, Vol C, pp. 796–811. Chester: IUCr.
- Brown, H. C. & Murray, L. T. (1984). Inorg. Chem. 23, 2746–2753.
- Brown, H. C., Zaidlewicz, M., Dalvi, P. V., Narasimhan, S. & Mukhopadhyay, A. (1999). Organometallics, 18, 1305–1309.
- Buker (2015). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
- Dembitsky, V. M., Tolstikov, G. A. & Srebnik, M. (2002). Eurasian Chem.-Technol. J. 4, 153–167.
- Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.
- Goralski, C. T. & Singaram, B. (2012). ARKIVOC, 2012, 88–113.
- Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [DOI] [PMC free article] [PubMed]
- Hatayama, Y. & Okuno, T. (2012). Acta Cryst. E68, o84. [DOI] [PMC free article] [PubMed]
- Li, M., Li, Y., Zhao, B., Liang, F. & Jin, L.-Y. (2014). RSC Adv. 4, 30046–30049.
- Liu, Y.-L., Kehr, G., Daniliuc, C. G. & Erker, G. (2017). Chem. Eur. J. 23, 12141–12144. [DOI] [PubMed]
- Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.
- Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.
- Viehe, H. G., Janousek, Z., Merényi, R. & Stella, L. (1985). Acc. Chem. Res. 18, 148–154.
- Wang, L., Jian, Z., Daniliuc, C. G., Kehr, G. & Erker, G. (2018). Dalton Trans. 47, 10853–10856. [DOI] [PubMed]
- Witulski, B., Buschmann, N. & Bergsträsser, U. (2000). Tetrahedron, 56, 8473–8480.
- Zhuo, J.-C., Soloway, A. H., Barnum, B. A. & Tjarks, W. (2001). Frontiers in Neutron Capture Therapy, edited by M. F. Hawthorne, K. Shelly & R. J. Wiersema, pp. 785–790. New York: Kluwer Academic/Plenum Publishers.
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020005289/lh5953sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989020005289/lh5953Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989020005289/lh5953Isup3.cml
CCDC reference: 1997061
Additional supporting information: crystallographic information; 3D view; checkCIF report