research communications
H-carbazole
and luminescence properties of 2-[(2′,6′-dimethoxy-2,3′-bipyridin-6-yl)oxy]-9-(pyridin-2-yl)-9aDepartment of Food and Nutrition, Kyungnam College of Information and Technology, Busan 47011, Republic of Korea, bResearch Institute of Natural Science, Gyeongsang National University, Jinju 52828, Republic of Korea, and cDivision of Science Education & Department of Chemistry, Kangwon National University, Chuncheon 24341, Republic of Korea
*Correspondence e-mail: kangy@kangwon.ac.kr
In the title compound, C29H22N4O3, the carbazole system forms a dihedral angle of 68.45 (3)° with the mean plane of the bipyridine ring system. The bipyridine ring system, with two methoxy substituents, is approximately planar (r.m.s. deviation = 0.0670 Å), with a dihedral angle of 7.91 (13)° between the planes of the two pyridine rings. Intramolecular C—H⋯O/N hydrogen bonds may promote the planarity of the bipyridyl ring system. In the pyridyl-substituted carbazole fragment, the pyridine ring is tilted by 56.65 (4)° with respect to the mean plane of the carbazole system (r.m.s. deviation = 0.0191 Å). In the crystal, adjacent molecules are connected via C—H⋯O/N hydrogen bonds and C—H⋯π interactions, resulting in the formation of a three-dimensional (3D) supramolecular network. In addition, the 3D structure contains intermolecular π–π stacking interactions, with centroid–centroid distances of 3.5634 (12) Å between pyridine rings. The title compound exhibits a high energy gap (3.48 eV) and triplet energy (2.64 eV), indicating that it could be a suitable host material in organic light-emitting diode (OLED) applications.
1. Chemical context
Carbazole-based organic small molecules have recently attracted much interest as organic light-emitting diodes (OLEDs) because of their high stability to the redox process, as well as their high triplet energy (ET ≃ 3.0 eV) (Krucaite & Grigalevicius, 2019). In particular, organic compounds bearing a carbazole group have been widely used as host materials for phosphorescent organic light-emitting diodes (PhOLEDs) due to their high thermal stability and excellent hole-transporting properties (Yang et al., 2018). Moreover, a number of carbazole-based compounds have been developed as ligands to coordinate with heavy transition-metal ions, such as PdII and PtII (Fleetham et al., 2017). Although there are a number of carbazole-based organic compounds, examples linking a bipyridine to a carbazole unit are still rare. Based on previous reports, bipyridine also possesses a high triplet energy and a stable chelated coordination mode with respect to transition-metal ions, which makes it a suitable ligand for developing blue phosphorescent metal complexes (Zaen et al., 2019). Despite this advantage, reports of crystal structures of carbazole derivatives are still scarce. This prompted us to investigate the of carbazole derivatives bearing the bipyridine group. Herein, we describe the molecular and crystal structures of 2-[(2′,6′-dimethoxy-2,3′-bipyridin-6-yl)oxy]-9-(pyridin-2-yl)-9H-carbazole, which can act as a potential tetradentate ligand for various transition-metal ions. In addition, the luminescence properties of the title compound were examined via photophysical analysis.
2. Structural commentary
Fig. 1 illustrates the molecular structure of the title compound, in which the dihedral angle between the planes of the bipyridine (N3/C18–C27/N4) and carbazole (N2/C6–C17) moieties connected by atom O1 is 68.45 (3)°. In the pyridyl-substituted carbazole unit, the pyridine ring (N1/C1–C5) forms a dihedral angle of 56.65 (4)° with the carbazole ring system. The two pyridine rings in the bipyridine ring system, with two methoxy substituents, are approximately coplanar, making a dihedral angle of 7.91 (13)°. Short intramolecular C—H⋯O and C—H⋯N contacts (Table 1), forming S(6) and S(5) rings, respectively, may contribute to the planarity of the bipyridyl ring system (r.m.s. deviation = 0.0670 Å).
3. Supramolecular features
In the crystal, adjacent molecules are connected by weak C—H⋯O/N hydrogen bonds and C—H⋯π interactions (Table 1 and yellow and black dashed lines in Fig. 2), forming a three-dimensional (3D) supramolecular network. In addition, the 3D structure is stabilized by π–π stacking interactions (green dashed lines in Fig. 2), with a centroid–centroid distance of 3.5634 (12) Å for Cg3⋯Cg4(x, −y + , z − ), where Cg3 and Cg4 are the centroids of the N3- and N4-containing pyridine rings, respectively.
4. Luminescence properties
The photophysical properties of the title compound were analyzed using UV–Vis and shows the absorption, solution PL and low-temperature (77 K) PL spectra of the title compound. The compound showed a strong absorption of the carbazole unit above 300 nm and of the bipyridine unit connected to carbazole below 300 nm (Belletête et al., 2004). The emission spectra were obtained under excitation at 280 nm. The title compound displays a narrow emission band, with λmax = 364 nm, at ambient temperature. However, a broad emission, with λmax = 470 nm, was observed at 77 K. The energy difference between the vibrationally relaxed ground and excited states, E0–0, which is defined as the crossing point of the appropriate absorption and emission spectra, is approximately 3.68 eV. The of the UV–Vis spectrum was 356 nm, which corresponded to an energy gap at 3.48 eV. The triplet energy of the title compound was 2.64 eV, which could be calculated from the phosphorescent emission maximum (470 nm) of the PL spectrum at 77 K. This value was high enough to suggest the use of the host material as a green phosphorescent dopant. The triplet energy of the tris(2-phenylpyridinato-κ2C2,N)iridium(III), or Ir(ppy)3, dopant is 2.40 eV and effective from the title compound to the Ir(ppy)3 dopant is expected. Consequently, strong absorption and a high energy gap and triplet energy make the title compound a suitable host material in organic light-emitting diode (OLED) applications.
(PL) measurements. Fig. 35. Synthesis and crystallization
All experiments were performed under a dry N2 atmosphere using standard Schlenk techniques. All solvents used in this study were freshly distilled over appropriate drying reagents prior to use. All starting materials were commercially purchased and used without further purification. The 1H NMR spectrum was recorded on a JEOL 400 MHz spectrometer. The two starting materials, i.e. 6-bromo-2′,6′-dimethoxy-2,3′-bipyridine and 9-(pyridin-2-yl)-9H-carbazol-2-ol, were synthesized according to a slight modification of a previous synthetic methodology reported by our group (Park et al., 2018; Fleetham et al., 2016). Details of the synthetic procedures and reagents are presented in Fig. 4.
To a 100 ml Schlenk flask were added 9-(pyridin-2-yl)-9H-carbazol-2-ol (1.0 g, 3.84 mmol), 6-bromo-2′,6′-dimethoxy-2,3′-bipyridine (1.36 g, 4.61 mmol), CuI (0.073 mg, 0.384 mmol), 2-picolinic acid (0.094 g, 0.758 mmol) and K3PO4 (1.63 g, 7.68 mmol). The flask was evacuated and backfilled with nitrogen and then dimethyl sulfoxide (DMSO; 15 ml) was then added under an N2 atmosphere. The reaction mixture was stirred at 368–378 K still under nitrogen for 3 d. After cooling to room temperature, the mixture was poured into water (100 ml) and extracted with ethyl acetate (50 ml × 3). The combined organic layer was dried with anhydrous Na2SO4 and concentrated under reduced pressure. Purification by (dichloromethane–hexane 1:10 and then 1:3 v/v) afforded the desired product as a white solid (yield 1.3 g, 72%). Colourless crystals of X-ray quality were obtained by slow evaporation of a dichloromethane–hexane solution (1:1 v/v) of the title compound. 1H NMR (400 MHz, CDCl3): δ 8.66 (ddd, J = 5.6, 2.0, 0.8 Hz, 1H), 8.21 (d, J = 8.0 Hz, 1H), 8.08 (s, 1H), 8.01 (s, 1H), 7.86 (td, J = 7.6, 1.6 Hz, 1H), 7.82 (d, J = 8.4 Hz, 1H), 7.79 (d, J = 8.0 Hz, 1H), 7.72 (d, J = 2.0 Hz, 1H), 7.67 (t, J = 8.0 Hz, 1H), 7.62 (dd, J = 8.0, 0.8 Hz, 1H), 7.42 (td, J = 7.6, 1.2 Hz, 1H), 7.32 (td, J = 7.6, 0.8 Hz, 1H), 7.27 (td, J = 5.0, 1.2 Hz, 1H), 7.15 (dd, J = 7.6, 1.6 Hz, 1H), 6.71 (d, J = 8.4 Hz, 1H), 6.30 (d, J = 8.8 Hz, 1H), 4.02 (s, 3H), 3.93 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 163.4, 163.0, 160.1, 153.2, 152.2, 151.7, 149.7, 142.4, 140.4, 140.0, 139.8, 138.7, 125.9, 124.2, 121.5, 121.3, 121.2, 120.9, 120.0, 119.1, 118.3, 115.1, 113.4, 111.2, 108.3, 104.4, 101.8, 53.8, 53.6; HRMS (EI): found m/z 474.
6. Refinement
Crystal data, data collection and structure . All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for Csp2 H atoms, and with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms.
details are summarized in Table 2
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Supporting information
https://doi.org/10.1107/S2056989019013549/fy2142sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019013549/fy2142Isup2.hkl
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).C29H22N4O3 | F(000) = 992 |
Mr = 474.50 | Dx = 1.385 Mg m−3 |
Monoclinic, Ia | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6979 (1) Å | Cell parameters from 6053 reflections |
b = 23.6702 (3) Å | θ = 2.2–28.3° |
c = 9.9229 (2) Å | µ = 0.09 mm−1 |
β = 92.9125 (5)° | T = 173 K |
V = 2274.87 (6) Å3 | Block, colourless |
Z = 4 | 0.53 × 0.46 × 0.12 mm |
Bruker APEXII CCD diffractometer | 4943 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.020 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | θmax = 28.4°, θmin = 1.7° |
Tmin = 0.710, Tmax = 0.746 | h = −12→12 |
10918 measured reflections | k = −31→31 |
5179 independent reflections | l = −13→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.0404P)2 + 0.7038P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
5179 reflections | Δρmax = 0.21 e Å−3 |
328 parameters | Δρmin = −0.19 e Å−3 |
2 restraints | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0062 (6) |
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 | ||
O1 | 0.16676 (16) | 0.24337 (6) | 0.28067 (15) | 0.0285 (3) | |
O2 | −0.27313 (17) | 0.33138 (6) | 0.70330 (18) | 0.0382 (4) | |
O3 | −0.43670 (17) | 0.15756 (6) | 0.82051 (17) | 0.0358 (4) | |
N1 | 0.3339 (2) | 0.06572 (7) | 0.02064 (19) | 0.0287 (4) | |
N2 | 0.30895 (18) | 0.04679 (7) | 0.24867 (18) | 0.0270 (4) | |
N3 | −0.00057 (17) | 0.25161 (7) | 0.43700 (18) | 0.0244 (3) | |
N4 | −0.35398 (18) | 0.24417 (7) | 0.75714 (19) | 0.0273 (4) | |
C1 | 0.3152 (3) | 0.05001 (10) | −0.1083 (2) | 0.0344 (5) | |
H1 | 0.3516 | 0.0737 | −0.1752 | 0.041* | |
C2 | 0.2465 (3) | 0.00167 (10) | −0.1504 (2) | 0.0360 (5) | |
H2 | 0.2399 | −0.0086 | −0.2431 | 0.043* | |
C3 | 0.1874 (3) | −0.03137 (10) | −0.0545 (3) | 0.0379 (5) | |
H3 | 0.1378 | −0.0646 | −0.0801 | 0.045* | |
C4 | 0.2016 (3) | −0.01536 (9) | 0.0794 (2) | 0.0353 (5) | |
H4 | 0.1594 | −0.0365 | 0.1475 | 0.042* | |
C5 | 0.2793 (2) | 0.03247 (8) | 0.1115 (2) | 0.0246 (4) | |
C6 | 0.3774 (2) | 0.01129 (8) | 0.3428 (2) | 0.0261 (4) | |
C7 | 0.4216 (2) | −0.04424 (9) | 0.3285 (2) | 0.0305 (4) | |
H7 | 0.4050 | −0.0642 | 0.2462 | 0.037* | |
C8 | 0.4904 (2) | −0.06934 (9) | 0.4381 (2) | 0.0331 (5) | |
H8 | 0.5208 | −0.1073 | 0.4311 | 0.040* | |
C9 | 0.5164 (3) | −0.04006 (10) | 0.5592 (2) | 0.0356 (5) | |
H9 | 0.5633 | −0.0584 | 0.6333 | 0.043* | |
C10 | 0.4742 (2) | 0.01540 (9) | 0.5717 (2) | 0.0319 (5) | |
H10 | 0.4937 | 0.0355 | 0.6534 | 0.038* | |
C11 | 0.4030 (2) | 0.04161 (8) | 0.4635 (2) | 0.0253 (4) | |
C12 | 0.3469 (2) | 0.09767 (8) | 0.44159 (19) | 0.0231 (4) | |
C13 | 0.3371 (2) | 0.14504 (8) | 0.5239 (2) | 0.0259 (4) | |
H13 | 0.3741 | 0.1443 | 0.6144 | 0.031* | |
C14 | 0.2730 (2) | 0.19313 (8) | 0.4724 (2) | 0.0263 (4) | |
H14 | 0.2648 | 0.2256 | 0.5277 | 0.032* | |
C15 | 0.2203 (2) | 0.19380 (8) | 0.3386 (2) | 0.0243 (4) | |
C16 | 0.2283 (2) | 0.14802 (8) | 0.2536 (2) | 0.0240 (4) | |
H16 | 0.1920 | 0.1493 | 0.1629 | 0.029* | |
C17 | 0.2923 (2) | 0.09974 (8) | 0.3073 (2) | 0.0232 (4) | |
C18 | 0.0820 (2) | 0.27662 (8) | 0.3548 (2) | 0.0239 (4) | |
C19 | 0.0883 (2) | 0.33456 (9) | 0.3325 (2) | 0.0309 (5) | |
H19 | 0.1491 | 0.3506 | 0.2708 | 0.037* | |
C20 | 0.0015 (2) | 0.36732 (9) | 0.4049 (2) | 0.0347 (5) | |
H20 | 0.0019 | 0.4072 | 0.3941 | 0.042* | |
C21 | −0.0865 (2) | 0.34265 (9) | 0.4935 (2) | 0.0299 (5) | |
H21 | −0.1461 | 0.3653 | 0.5440 | 0.036* | |
C22 | −0.0865 (2) | 0.28402 (8) | 0.5075 (2) | 0.0238 (4) | |
C23 | −0.1789 (2) | 0.25192 (8) | 0.5941 (2) | 0.0251 (4) | |
C24 | −0.2697 (2) | 0.27479 (8) | 0.6851 (2) | 0.0261 (4) | |
C25 | −0.3517 (2) | 0.18857 (9) | 0.7446 (2) | 0.0301 (4) | |
C26 | −0.2677 (3) | 0.16054 (10) | 0.6591 (3) | 0.0431 (6) | |
H26 | −0.2689 | 0.1205 | 0.6519 | 0.052* | |
C27 | −0.1815 (3) | 0.19309 (9) | 0.5844 (3) | 0.0374 (5) | |
H27 | −0.1222 | 0.1749 | 0.5245 | 0.045* | |
C28 | −0.3786 (3) | 0.35291 (10) | 0.7870 (3) | 0.0458 (6) | |
H28A | −0.3613 | 0.3930 | 0.8061 | 0.069* | |
H28B | −0.3770 | 0.3317 | 0.8719 | 0.069* | |
H28C | −0.4693 | 0.3486 | 0.7398 | 0.069* | |
C29 | −0.5206 (3) | 0.18868 (10) | 0.9090 (3) | 0.0366 (5) | |
H29A | −0.5724 | 0.1623 | 0.9634 | 0.055* | |
H29B | −0.5854 | 0.2125 | 0.8555 | 0.055* | |
H29C | −0.4616 | 0.2125 | 0.9686 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0366 (8) | 0.0230 (7) | 0.0266 (7) | 0.0077 (6) | 0.0087 (6) | 0.0039 (6) |
O2 | 0.0429 (9) | 0.0230 (7) | 0.0510 (10) | −0.0008 (6) | 0.0243 (8) | −0.0039 (7) |
O3 | 0.0361 (8) | 0.0275 (8) | 0.0446 (10) | −0.0009 (6) | 0.0100 (8) | 0.0102 (7) |
N1 | 0.0347 (9) | 0.0247 (8) | 0.0272 (9) | −0.0012 (7) | 0.0062 (7) | −0.0023 (7) |
N2 | 0.0367 (10) | 0.0195 (8) | 0.0249 (9) | 0.0020 (7) | 0.0032 (7) | −0.0003 (6) |
N3 | 0.0248 (8) | 0.0212 (8) | 0.0275 (8) | 0.0015 (6) | 0.0032 (7) | 0.0005 (6) |
N4 | 0.0247 (9) | 0.0268 (8) | 0.0306 (9) | 0.0009 (7) | 0.0032 (7) | 0.0034 (7) |
C1 | 0.0435 (13) | 0.0330 (11) | 0.0272 (11) | 0.0016 (10) | 0.0085 (9) | −0.0003 (9) |
C2 | 0.0410 (13) | 0.0362 (12) | 0.0303 (11) | 0.0063 (10) | −0.0024 (10) | −0.0106 (9) |
C3 | 0.0409 (13) | 0.0272 (11) | 0.0448 (14) | −0.0027 (9) | −0.0062 (11) | −0.0101 (9) |
C4 | 0.0420 (13) | 0.0277 (11) | 0.0364 (12) | −0.0074 (9) | 0.0034 (10) | −0.0005 (9) |
C5 | 0.0278 (10) | 0.0206 (9) | 0.0254 (10) | 0.0023 (7) | 0.0025 (8) | −0.0029 (7) |
C6 | 0.0282 (10) | 0.0245 (9) | 0.0262 (10) | 0.0008 (8) | 0.0072 (8) | 0.0032 (7) |
C7 | 0.0367 (11) | 0.0240 (9) | 0.0314 (11) | 0.0010 (8) | 0.0094 (9) | −0.0002 (8) |
C8 | 0.0342 (11) | 0.0248 (10) | 0.0413 (12) | 0.0050 (8) | 0.0116 (9) | 0.0054 (9) |
C9 | 0.0386 (12) | 0.0349 (11) | 0.0337 (12) | 0.0095 (9) | 0.0047 (10) | 0.0104 (9) |
C10 | 0.0346 (11) | 0.0351 (11) | 0.0265 (10) | 0.0070 (9) | 0.0055 (9) | 0.0045 (8) |
C11 | 0.0247 (10) | 0.0254 (9) | 0.0264 (10) | 0.0022 (7) | 0.0078 (8) | 0.0023 (8) |
C12 | 0.0227 (9) | 0.0248 (9) | 0.0222 (9) | 0.0009 (7) | 0.0048 (7) | 0.0019 (7) |
C13 | 0.0276 (9) | 0.0288 (10) | 0.0215 (9) | 0.0012 (8) | 0.0034 (7) | −0.0012 (8) |
C14 | 0.0291 (10) | 0.0236 (9) | 0.0268 (10) | 0.0007 (8) | 0.0064 (8) | −0.0039 (8) |
C15 | 0.0238 (9) | 0.0217 (9) | 0.0283 (10) | 0.0009 (7) | 0.0088 (8) | 0.0019 (7) |
C16 | 0.0249 (9) | 0.0243 (9) | 0.0231 (9) | −0.0010 (7) | 0.0043 (7) | 0.0006 (7) |
C17 | 0.0248 (9) | 0.0220 (9) | 0.0233 (9) | −0.0024 (7) | 0.0058 (8) | −0.0015 (7) |
C18 | 0.0256 (9) | 0.0227 (9) | 0.0235 (9) | 0.0039 (8) | 0.0016 (8) | −0.0004 (7) |
C19 | 0.0330 (11) | 0.0242 (10) | 0.0364 (12) | 0.0018 (8) | 0.0099 (9) | 0.0067 (8) |
C20 | 0.0398 (12) | 0.0203 (9) | 0.0448 (13) | 0.0048 (9) | 0.0109 (10) | 0.0036 (9) |
C21 | 0.0297 (10) | 0.0243 (10) | 0.0364 (12) | 0.0059 (8) | 0.0096 (9) | −0.0003 (8) |
C22 | 0.0223 (9) | 0.0221 (9) | 0.0269 (10) | 0.0016 (7) | −0.0002 (8) | 0.0006 (7) |
C23 | 0.0226 (9) | 0.0228 (9) | 0.0300 (10) | 0.0025 (7) | 0.0018 (8) | 0.0030 (8) |
C24 | 0.0246 (9) | 0.0242 (9) | 0.0294 (10) | 0.0011 (7) | 0.0014 (8) | 0.0016 (8) |
C25 | 0.0270 (10) | 0.0275 (10) | 0.0359 (11) | −0.0003 (8) | 0.0025 (9) | 0.0070 (9) |
C26 | 0.0481 (15) | 0.0218 (10) | 0.0613 (17) | 0.0015 (10) | 0.0208 (13) | 0.0050 (10) |
C27 | 0.0407 (12) | 0.0241 (10) | 0.0489 (14) | 0.0037 (9) | 0.0182 (11) | 0.0004 (9) |
C28 | 0.0540 (15) | 0.0298 (11) | 0.0565 (16) | 0.0028 (11) | 0.0298 (13) | −0.0055 (11) |
C29 | 0.0359 (12) | 0.0377 (12) | 0.0370 (12) | −0.0085 (10) | 0.0090 (10) | 0.0034 (10) |
O1—C18 | 1.378 (2) | C10—H10 | 0.9500 |
O1—C15 | 1.395 (2) | C11—C12 | 1.446 (3) |
O2—C24 | 1.352 (2) | C12—C13 | 1.393 (3) |
O2—C28 | 1.443 (3) | C12—C17 | 1.409 (3) |
O3—C25 | 1.360 (3) | C13—C14 | 1.383 (3) |
O3—C29 | 1.431 (3) | C13—H13 | 0.9500 |
N1—C5 | 1.327 (3) | C14—C15 | 1.398 (3) |
N1—C1 | 1.335 (3) | C14—H14 | 0.9500 |
N2—C17 | 1.395 (2) | C15—C16 | 1.378 (3) |
N2—C6 | 1.399 (3) | C16—C17 | 1.393 (3) |
N2—C5 | 1.417 (3) | C16—H16 | 0.9500 |
N3—C18 | 1.312 (3) | C18—C19 | 1.391 (3) |
N3—C22 | 1.353 (3) | C19—C20 | 1.373 (3) |
N4—C25 | 1.322 (3) | C19—H19 | 0.9500 |
N4—C24 | 1.328 (3) | C20—C21 | 1.386 (3) |
C1—C2 | 1.379 (3) | C20—H20 | 0.9500 |
C1—H1 | 0.9500 | C21—C22 | 1.395 (3) |
C2—C3 | 1.379 (4) | C21—H21 | 0.9500 |
C2—H2 | 0.9500 | C22—C23 | 1.482 (3) |
C3—C4 | 1.382 (3) | C23—C27 | 1.396 (3) |
C3—H3 | 0.9500 | C23—C24 | 1.402 (3) |
C4—C5 | 1.388 (3) | C25—C26 | 1.377 (3) |
C4—H4 | 0.9500 | C26—C27 | 1.380 (3) |
C6—C7 | 1.392 (3) | C26—H26 | 0.9500 |
C6—C11 | 1.407 (3) | C27—H27 | 0.9500 |
C7—C8 | 1.380 (3) | C28—H28A | 0.9800 |
C7—H7 | 0.9500 | C28—H28B | 0.9800 |
C8—C9 | 1.399 (3) | C28—H28C | 0.9800 |
C8—H8 | 0.9500 | C29—H29A | 0.9800 |
C9—C10 | 1.382 (3) | C29—H29B | 0.9800 |
C9—H9 | 0.9500 | C29—H29C | 0.9800 |
C10—C11 | 1.393 (3) | ||
C18—O1—C15 | 118.70 (15) | C16—C15—O1 | 116.16 (18) |
C24—O2—C28 | 116.72 (17) | C16—C15—C14 | 122.88 (18) |
C25—O3—C29 | 116.20 (17) | O1—C15—C14 | 120.73 (17) |
C5—N1—C1 | 116.50 (19) | C15—C16—C17 | 116.67 (18) |
C17—N2—C6 | 108.79 (16) | C15—C16—H16 | 121.7 |
C17—N2—C5 | 126.41 (16) | C17—C16—H16 | 121.7 |
C6—N2—C5 | 124.30 (16) | C16—C17—N2 | 129.49 (18) |
C18—N3—C22 | 118.47 (17) | C16—C17—C12 | 121.93 (18) |
C25—N4—C24 | 118.63 (19) | N2—C17—C12 | 108.51 (16) |
N1—C1—C2 | 124.2 (2) | N3—C18—O1 | 118.27 (17) |
N1—C1—H1 | 117.9 | N3—C18—C19 | 125.21 (19) |
C2—C1—H1 | 117.9 | O1—C18—C19 | 116.49 (19) |
C3—C2—C1 | 118.2 (2) | C20—C19—C18 | 116.1 (2) |
C3—C2—H2 | 120.9 | C20—C19—H19 | 121.9 |
C1—C2—H2 | 120.9 | C18—C19—H19 | 121.9 |
C2—C3—C4 | 118.9 (2) | C19—C20—C21 | 120.5 (2) |
C2—C3—H3 | 120.5 | C19—C20—H20 | 119.7 |
C4—C3—H3 | 120.5 | C21—C20—H20 | 119.7 |
C3—C4—C5 | 118.1 (2) | C20—C21—C22 | 119.04 (19) |
C3—C4—H4 | 120.9 | C20—C21—H21 | 120.5 |
C5—C4—H4 | 120.9 | C22—C21—H21 | 120.5 |
N1—C5—C4 | 123.9 (2) | N3—C22—C21 | 120.63 (19) |
N1—C5—N2 | 116.24 (18) | N3—C22—C23 | 114.54 (16) |
C4—C5—N2 | 119.80 (19) | C21—C22—C23 | 124.80 (18) |
C7—C6—N2 | 129.6 (2) | C27—C23—C24 | 114.82 (19) |
C7—C6—C11 | 121.8 (2) | C27—C23—C22 | 118.74 (19) |
N2—C6—C11 | 108.61 (17) | C24—C23—C22 | 126.41 (18) |
C8—C7—C6 | 117.7 (2) | N4—C24—O2 | 116.67 (18) |
C8—C7—H7 | 121.1 | N4—C24—C23 | 124.05 (18) |
C6—C7—H7 | 121.1 | O2—C24—C23 | 119.27 (18) |
C7—C8—C9 | 121.5 (2) | N4—C25—O3 | 118.2 (2) |
C7—C8—H8 | 119.3 | N4—C25—C26 | 123.4 (2) |
C9—C8—H8 | 119.3 | O3—C25—C26 | 118.41 (19) |
C10—C9—C8 | 120.4 (2) | C25—C26—C27 | 117.1 (2) |
C10—C9—H9 | 119.8 | C25—C26—H26 | 121.4 |
C8—C9—H9 | 119.8 | C27—C26—H26 | 121.4 |
C9—C10—C11 | 119.4 (2) | C26—C27—C23 | 121.9 (2) |
C9—C10—H10 | 120.3 | C26—C27—H27 | 119.0 |
C11—C10—H10 | 120.3 | C23—C27—H27 | 119.0 |
C10—C11—C6 | 119.22 (19) | O2—C28—H28A | 109.5 |
C10—C11—C12 | 133.8 (2) | O2—C28—H28B | 109.5 |
C6—C11—C12 | 106.95 (17) | H28A—C28—H28B | 109.5 |
C13—C12—C17 | 119.52 (18) | O2—C28—H28C | 109.5 |
C13—C12—C11 | 133.37 (18) | H28A—C28—H28C | 109.5 |
C17—C12—C11 | 107.10 (17) | H28B—C28—H28C | 109.5 |
C14—C13—C12 | 119.24 (19) | O3—C29—H29A | 109.5 |
C14—C13—H13 | 120.4 | O3—C29—H29B | 109.5 |
C12—C13—H13 | 120.4 | H29A—C29—H29B | 109.5 |
C13—C14—C15 | 119.76 (18) | O3—C29—H29C | 109.5 |
C13—C14—H14 | 120.1 | H29A—C29—H29C | 109.5 |
C15—C14—H14 | 120.1 | H29B—C29—H29C | 109.5 |
C5—N1—C1—C2 | −1.4 (3) | C6—N2—C17—C16 | −178.7 (2) |
N1—C1—C2—C3 | 3.2 (4) | C5—N2—C17—C16 | 9.2 (3) |
C1—C2—C3—C4 | −1.1 (4) | C6—N2—C17—C12 | −1.7 (2) |
C2—C3—C4—C5 | −2.3 (4) | C5—N2—C17—C12 | −173.88 (18) |
C1—N1—C5—C4 | −2.4 (3) | C13—C12—C17—C16 | 0.0 (3) |
C1—N1—C5—N2 | 175.06 (19) | C11—C12—C17—C16 | 179.17 (18) |
C3—C4—C5—N1 | 4.3 (3) | C13—C12—C17—N2 | −177.21 (18) |
C3—C4—C5—N2 | −173.1 (2) | C11—C12—C17—N2 | 2.0 (2) |
C17—N2—C5—N1 | 51.1 (3) | C22—N3—C18—O1 | −178.41 (17) |
C6—N2—C5—N1 | −119.9 (2) | C22—N3—C18—C19 | −0.6 (3) |
C17—N2—C5—C4 | −131.3 (2) | C15—O1—C18—N3 | −34.5 (3) |
C6—N2—C5—C4 | 57.7 (3) | C15—O1—C18—C19 | 147.49 (19) |
C17—N2—C6—C7 | −177.0 (2) | N3—C18—C19—C20 | 0.9 (3) |
C5—N2—C6—C7 | −4.6 (3) | O1—C18—C19—C20 | 178.79 (19) |
C17—N2—C6—C11 | 0.8 (2) | C18—C19—C20—C21 | −0.4 (4) |
C5—N2—C6—C11 | 173.16 (18) | C19—C20—C21—C22 | −0.4 (4) |
N2—C6—C7—C8 | 178.5 (2) | C18—N3—C22—C21 | −0.3 (3) |
C11—C6—C7—C8 | 1.0 (3) | C18—N3—C22—C23 | 178.03 (17) |
C6—C7—C8—C9 | −0.6 (3) | C20—C21—C22—N3 | 0.8 (3) |
C7—C8—C9—C10 | −0.5 (4) | C20—C21—C22—C23 | −177.4 (2) |
C8—C9—C10—C11 | 1.3 (4) | N3—C22—C23—C27 | −7.2 (3) |
C9—C10—C11—C6 | −1.0 (3) | C21—C22—C23—C27 | 171.1 (2) |
C9—C10—C11—C12 | −179.1 (2) | N3—C22—C23—C24 | 174.66 (18) |
C7—C6—C11—C10 | −0.2 (3) | C21—C22—C23—C24 | −7.0 (3) |
N2—C6—C11—C10 | −178.16 (18) | C25—N4—C24—O2 | −178.53 (19) |
C7—C6—C11—C12 | 178.39 (19) | C25—N4—C24—C23 | 1.0 (3) |
N2—C6—C11—C12 | 0.4 (2) | C28—O2—C24—N4 | −6.9 (3) |
C10—C11—C12—C13 | −4.2 (4) | C28—O2—C24—C23 | 173.6 (2) |
C6—C11—C12—C13 | 177.6 (2) | C27—C23—C24—N4 | −0.6 (3) |
C10—C11—C12—C17 | 176.8 (2) | C22—C23—C24—N4 | 177.60 (19) |
C6—C11—C12—C17 | −1.4 (2) | C27—C23—C24—O2 | 178.9 (2) |
C17—C12—C13—C14 | 0.4 (3) | C22—C23—C24—O2 | −2.9 (3) |
C11—C12—C13—C14 | −178.5 (2) | C24—N4—C25—O3 | 178.91 (18) |
C12—C13—C14—C15 | −0.6 (3) | C24—N4—C25—C26 | −1.0 (4) |
C18—O1—C15—C16 | 141.73 (19) | C29—O3—C25—N4 | −0.6 (3) |
C18—O1—C15—C14 | −43.6 (3) | C29—O3—C25—C26 | 179.2 (2) |
C13—C14—C15—C16 | 0.3 (3) | N4—C25—C26—C27 | 0.5 (4) |
C13—C14—C15—O1 | −174.02 (18) | O3—C25—C26—C27 | −179.4 (2) |
O1—C15—C16—C17 | 174.71 (16) | C25—C26—C27—C23 | −0.1 (4) |
C14—C15—C16—C17 | 0.1 (3) | C24—C23—C27—C26 | 0.1 (4) |
C15—C16—C17—N2 | 176.29 (19) | C22—C23—C27—C26 | −178.2 (2) |
C15—C16—C17—C12 | −0.3 (3) |
Cg1 is the centroid of the C12–C17 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O3i | 0.95 | 2.50 | 3.429 (3) | 165 |
C21—H21···O2 | 0.95 | 2.20 | 2.839 (3) | 123 |
C27—H27···N3 | 0.95 | 2.35 | 2.720 (3) | 102 |
C29—H29A···N1ii | 0.98 | 2.54 | 3.442 (3) | 154 |
C8—H8···Cg1iii | 0.95 | 2.76 | 3.426 (2) | 128 |
C28—H28C···Cg1iv | 0.98 | 2.89 | 3.485 (3) | 120 |
Symmetry codes: (i) x+1/2, −y, z−1; (ii) x−1, y, z+1; (iii) x+1/2, −y, z; (iv) x−1, −y+1/2, z+1/2. |
Funding information
Funding for this research was provided by: Funding for this research was provided by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2016R1D1A1B01012630 and 2018R1D1A3A03000716). This study was also supported by 2018 Research Grant (PoINT) from Kangwon National University.
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