Tuning the energy level of TAPC: crystal structure and photophysical and electrochemical properties of 4,4′-(cyclo­hexane-1,1-di­yl)bis­[N,N-bis­(4-meth­oxy­phen­yl)aniline]

Lee, S.; Kwak, S.; Lee, K.; Kim, B.G.; Kim, M.; Wang, D.H.; Han, W.-S.

doi:10.1107/S2053229619007101

Tuning the energy level of TAPC: crystal structure and photophysical and electrochemical properties of 4,4′-(cyclohexane-1,1-diyl)bis[N,N-bis(4-methoxyphenyl)aniline]

S. Lee, S. Kwak, K. Lee, B. G. Kim, M. Kim, D. H. Wang and W.-S. Han

The energy level of a hole-transporting material (HTM) in organic electronics, such as organic light-emitting diodes (OLEDs) and perovskite solar cells (PSCs), is important for device efficiency. In this regard, we prepared 4,4′-(cyclohexane-1,1-diyl)bis[N,N-bis(4-methoxyphenyl)aniline] (TAPC-OMe), C₄₆H₄₆N₂O₄, to tune the energy level of 4,4′-(cyclohexane-1,1-diyl)bis[N,N-bis(4-methylphenyl)aniline] (TAPC), which is a well-known HTM commonly used in OLED applications. A systematic characterization of TAPC-OMe, including ¹H and ¹³C NMR, elemental analysis, UV–Vis absorption, fluorescence emission, density functional theory (DFT) calculations and single-crystal X-ray diffraction, was performed. TAPC-OMe crystallized in the triclinic space group P $\overline{1}$ , with two molecules in the asymmetric unit. The dihedral angles between the central amine triangular planes and those of the phenyl groups varied from 26.56 (9) to 60.34 (8)° due to the steric hindrance of the central cyclohexyl ring. This arrangement might be induced by weak hydrogen bonds and C—H

π(Ph) interactions in the extended structure. The emission maxima of TAPC-OMe showed a significant bathochomic shift compared to that of TAPC. A strong dependency of the oxidation potentials on the nature of the electron-donating ability of substituents was confirmed by comparing oxidation potentials with known Hammett parameters (σ).

Keywords: energy level tuning; hydrogen-bonding interaction; steady-state photophysics; crystal structure; hole-transporting material; DFT calculations.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229619007101/qp3026sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619007101/qp3026Isup2.hkl Contains datablock I
	Chemdraw file https://doi.org/10.1107/S2053229619007101/qp3026Isup3.cdx Supplementary material
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229619007101/qp3026sup4.pdf Fully labelled ellipsoid plot (50%)

CCDC references: 1916470; 1923103; 1923104

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b) and WinGX (Farrugia, 2012); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

4,4'-(Cyclohexane-1,1-diyl)bis[N,N-bis(4-methoxyphenyl)aniline] top

Crystal data top

C₄₆H₄₆N₂O₄	Z = 4
M_r = 690.85	F(000) = 1472
Triclinic, P1	D_x = 1.214 Mg m⁻³
a = 13.1586 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.1881 (6) Å	Cell parameters from 9815 reflections
c = 23.6681 (12) Å	θ = 2.3–26.1°
α = 84.996 (2)°	µ = 0.08 mm⁻¹
β = 88.444 (2)°	T = 223 K
γ = 67.500 (2)°	Block, colourless
V = 3780.1 (3) Å³	0.33 × 0.20 × 0.15 mm

Data collection top

PHOTON 100 CMOS diffractometer	11070 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.098
Absorption correction: multi-scan Bruker SADABS	θ_max = 28.6°, θ_min = 2.1°
	h = −17→17
140302 measured reflections	k = −17→17
19056 independent reflections	l = −31→31

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.070	H-atom parameters constrained
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.026P)² + 1.7687P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
19056 reflections	Δρ_max = 0.21 e Å⁻³
954 parameters	Δρ_min = −0.18 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The raw area detector data frames were reduced and corrected for absorption effects using SAINT-Plus and SADABS programs (Bruker, 2012). The final unit-cell parameters were determined by least-squares refinement of the obtained data set. The diffraction data and unit-cell parameters were consistent with the assigned space groups and the structures were solved by direct methods with SHELXT. Subsequent difference Fourier calculations and full-matrix least-squares refinement against |F²| were also performed with SHELXL-2014 using WinGX (Farrugia, 2012).

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.29687 (12)	0.79952 (14)	0.28460 (7)	0.0649 (5)
O2	0.72837 (14)	0.15426 (13)	0.52119 (8)	0.0671 (5)
O3	1.61679 (15)	−0.14167 (13)	0.45235 (7)	0.0672 (5)
O4	1.61965 (13)	0.20105 (12)	0.09193 (6)	0.0543 (4)
N1	0.69772 (13)	0.53305 (14)	0.38672 (8)	0.0472 (5)
N2	1.44091 (16)	0.24259 (15)	0.30853 (8)	0.0618 (6)
C1	1.08524 (14)	0.63988 (15)	0.36702 (8)	0.0323 (4)
C2	1.10713 (16)	0.68287 (16)	0.42191 (9)	0.0399 (5)
H2A	1.111495	0.628803	0.453857	0.048*
H2B	1.178289	0.690606	0.418996	0.048*
C3	1.01793 (19)	0.79356 (17)	0.43374 (10)	0.0524 (6)
H3A	0.946877	0.785846	0.437964	0.063*
H3B	1.034749	0.816900	0.469316	0.063*
C4	1.0107 (2)	0.87979 (18)	0.38589 (12)	0.0640 (7)
H4A	0.951312	0.949598	0.393386	0.077*
H4B	1.079840	0.891755	0.383571	0.077*
C5	0.98901 (19)	0.84330 (17)	0.33029 (11)	0.0566 (6)
H5A	0.989732	0.897510	0.299365	0.068*
H5B	0.915875	0.839892	0.331157	0.068*
C6	1.07509 (16)	0.73066 (16)	0.31898 (9)	0.0426 (5)
H6A	1.146709	0.736823	0.313772	0.051*
H6B	1.056146	0.708499	0.283555	0.051*
C7	0.98037 (14)	0.61433 (14)	0.37241 (8)	0.0298 (4)
C8	0.90974 (15)	0.63161 (15)	0.32705 (8)	0.0338 (4)
H8	0.924839	0.662838	0.292206	0.041*
C9	0.81815 (15)	0.60480 (15)	0.33100 (8)	0.0366 (5)
H9	0.773005	0.617051	0.298967	0.044*
C10	0.79206 (15)	0.56004 (15)	0.38166 (9)	0.0358 (5)
C11	0.86167 (15)	0.54166 (16)	0.42739 (8)	0.0389 (5)
H11	0.846085	0.510968	0.462275	0.047*
C12	0.95376 (15)	0.56768 (15)	0.42261 (8)	0.0354 (4)
H12	1.000010	0.553367	0.454377	0.043*
C13	0.59644 (15)	0.60285 (16)	0.36087 (8)	0.0361 (4)
C14	0.57022 (16)	0.71482 (16)	0.35031 (9)	0.0418 (5)
H14	0.620647	0.745063	0.360357	0.050*
C15	0.47099 (16)	0.78323 (17)	0.32518 (9)	0.0459 (5)
H15	0.454747	0.859063	0.317979	0.055*
C16	0.39633 (16)	0.73979 (18)	0.31082 (9)	0.0437 (5)
C17	0.42084 (16)	0.62837 (18)	0.32163 (9)	0.0445 (5)
H17	0.369557	0.598673	0.312261	0.053*
C18	0.52015 (15)	0.56041 (17)	0.34611 (9)	0.0406 (5)
H18	0.536358	0.484507	0.352880	0.049*
C19	0.2643 (2)	0.9152 (2)	0.27728 (14)	0.0919 (10)
H19A	0.261030	0.943802	0.313958	0.138*
H19B	0.192291	0.947678	0.259330	0.138*
H19C	0.317153	0.933385	0.253530	0.138*
C20	0.70515 (15)	0.43498 (16)	0.42011 (9)	0.0393 (5)
C21	0.64051 (16)	0.43946 (17)	0.46778 (9)	0.0434 (5)
H21	0.590398	0.507884	0.478138	0.052*
C22	0.64915 (17)	0.34438 (18)	0.50010 (10)	0.0473 (5)
H22	0.604646	0.348100	0.532217	0.057*
C23	0.72335 (17)	0.24331 (17)	0.48532 (9)	0.0450 (5)
C24	0.78786 (18)	0.23845 (17)	0.43799 (10)	0.0493 (6)
H24	0.838409	0.170203	0.427664	0.059*
C25	0.77786 (17)	0.33425 (17)	0.40585 (10)	0.0469 (5)
H25	0.821794	0.330422	0.373490	0.056*
C26	0.8018 (2)	0.04926 (19)	0.50746 (13)	0.0743 (8)
H26A	0.780624	0.033559	0.471289	0.111*
H26B	0.799171	−0.006045	0.536672	0.111*
H26C	0.875877	0.048126	0.504981	0.111*
C27	1.18139 (14)	0.53386 (15)	0.35298 (8)	0.0325 (4)
C28	1.26694 (16)	0.47427 (16)	0.39042 (9)	0.0390 (5)
H28	1.267293	0.498994	0.426457	0.047*
C29	1.35217 (17)	0.37884 (16)	0.37590 (9)	0.0445 (5)
H29	1.409245	0.340598	0.402093	0.053*
C30	1.35411 (17)	0.33961 (16)	0.32368 (9)	0.0448 (5)
C31	1.26922 (17)	0.39829 (18)	0.28585 (9)	0.0469 (5)
H31	1.268986	0.373258	0.249884	0.056*
C32	1.18513 (16)	0.49297 (17)	0.30043 (9)	0.0409 (5)
H32	1.128491	0.531137	0.273990	0.049*
C33	1.48225 (18)	0.14680 (17)	0.34698 (9)	0.0481 (5)
C34	1.41327 (19)	0.10638 (18)	0.37749 (10)	0.0527 (6)
H34	1.336734	0.144159	0.373723	0.063*
C35	1.4546 (2)	0.01079 (18)	0.41377 (10)	0.0530 (6)
H35	1.406382	−0.014604	0.435004	0.064*
C36	1.5664 (2)	−0.04636 (17)	0.41841 (9)	0.0488 (6)
C37	1.63579 (19)	−0.00734 (19)	0.38746 (11)	0.0577 (6)
H37	1.712249	−0.046661	0.390151	0.069*
C38	1.59446 (19)	0.08869 (19)	0.35256 (10)	0.0577 (6)
H38	1.643064	0.115018	0.332321	0.069*
C39	1.5484 (3)	−0.1911 (2)	0.48165 (11)	0.0796 (9)
H39A	1.504441	−0.143072	0.509457	0.119*
H39B	1.594162	−0.261514	0.500660	0.119*
H39C	1.500239	−0.202289	0.454653	0.119*
C40	1.48256 (17)	0.23636 (17)	0.25246 (9)	0.0447 (5)
C41	1.51219 (17)	0.31878 (17)	0.22644 (9)	0.0458 (5)
H41	1.502148	0.381210	0.245760	0.055*
C42	1.55633 (16)	0.31135 (17)	0.17255 (9)	0.0415 (5)
H42	1.574848	0.368777	0.155177	0.050*
C43	1.57294 (15)	0.21900 (16)	0.14450 (9)	0.0389 (5)
C44	1.54264 (17)	0.13673 (17)	0.16960 (9)	0.0450 (5)
H44	1.552885	0.074324	0.150212	0.054*
C45	1.49745 (17)	0.14545 (17)	0.22291 (10)	0.0485 (6)
H45	1.476385	0.089138	0.239518	0.058*
C46	1.6375 (2)	0.2896 (2)	0.06160 (10)	0.0635 (7)
H46A	1.569425	0.354114	0.059318	0.095*
H46B	1.662437	0.270017	0.023648	0.095*
H46C	1.693019	0.305579	0.080991	0.095*
O5	1.12359 (13)	0.19155 (12)	0.41889 (7)	0.0559 (4)
O6	1.05328 (18)	−0.06571 (14)	0.06266 (8)	0.0853 (6)
O7	0.24612 (14)	0.15309 (13)	0.01423 (7)	0.0591 (4)
O8	−0.21741 (11)	0.77909 (13)	0.20637 (7)	0.0595 (4)
N3	0.92144 (16)	0.27167 (14)	0.20693 (9)	0.0596 (6)
N4	0.19134 (13)	0.53427 (14)	0.11754 (8)	0.0485 (5)
C51	0.56159 (14)	0.66782 (15)	0.12301 (8)	0.0335 (4)
C52	0.54510 (16)	0.75951 (16)	0.16271 (9)	0.0426 (5)
H52A	0.524007	0.736797	0.200258	0.051*
H52B	0.615331	0.767826	0.166900	0.051*
C53	0.45793 (18)	0.87118 (17)	0.14192 (11)	0.0540 (6)
H53A	0.385751	0.865660	0.141875	0.065*
H53B	0.454853	0.925921	0.168080	0.065*
C54	0.4827 (2)	0.90921 (18)	0.08268 (11)	0.0626 (7)
H54A	0.422237	0.977547	0.069330	0.075*
H54B	0.550009	0.924285	0.083512	0.075*
C55	0.49717 (18)	0.82181 (17)	0.04246 (10)	0.0518 (6)
H55A	0.517561	0.845517	0.004955	0.062*
H55B	0.427293	0.812624	0.038564	0.062*
C56	0.58576 (16)	0.71194 (16)	0.06379 (9)	0.0403 (5)
H56A	0.656333	0.720625	0.065170	0.048*
H56B	0.592830	0.657497	0.036719	0.048*
C57	0.65970 (15)	0.56337 (15)	0.14506 (8)	0.0332 (4)
C58	0.66719 (15)	0.52495 (16)	0.20204 (9)	0.0391 (5)
H58	0.612560	0.564479	0.227076	0.047*
C59	0.75229 (16)	0.43068 (17)	0.22293 (9)	0.0435 (5)
H59	0.754834	0.407088	0.261697	0.052*
C60	0.83441 (16)	0.37025 (16)	0.18697 (10)	0.0437 (5)
C61	0.82810 (16)	0.40785 (16)	0.13038 (9)	0.0443 (5)
H61	0.882996	0.368582	0.105390	0.053*
C62	0.74229 (15)	0.50237 (16)	0.10988 (9)	0.0394 (5)
H62	0.739908	0.525852	0.071108	0.047*
C63	0.96889 (16)	0.25608 (16)	0.26147 (9)	0.0437 (5)
C64	0.99140 (16)	0.33782 (16)	0.28457 (9)	0.0421 (5)
H64	0.972471	0.406862	0.264015	0.051*
C65	1.04095 (16)	0.32077 (16)	0.33703 (9)	0.0400 (5)
H65	1.054314	0.378119	0.352152	0.048*
C66	1.07083 (16)	0.21938 (16)	0.36725 (9)	0.0406 (5)
C67	1.04754 (19)	0.13775 (17)	0.34502 (10)	0.0535 (6)
H67	1.067017	0.068669	0.365599	0.064*
C68	0.99638 (19)	0.15547 (17)	0.29334 (11)	0.0551 (6)
H68	0.979712	0.099068	0.279313	0.066*
C69	1.1411 (2)	0.27492 (19)	0.44580 (10)	0.0573 (6)
H69A	1.183217	0.306539	0.421068	0.086*
H69B	1.181305	0.243630	0.480989	0.086*
H69C	1.070719	0.331896	0.453848	0.086*
C70	0.95951 (18)	0.18392 (16)	0.17081 (10)	0.0479 (5)
C71	1.06767 (19)	0.13777 (19)	0.15544 (12)	0.0624 (7)
H71	1.118517	0.163975	0.169313	0.075*
C72	1.1034 (2)	0.0531 (2)	0.11979 (12)	0.0660 (7)
H72	1.178182	0.021086	0.110223	0.079*
C73	1.0289 (2)	0.01641 (18)	0.09861 (10)	0.0575 (6)
C74	0.9200 (2)	0.06215 (18)	0.11398 (11)	0.0599 (7)
H74	0.868922	0.036853	0.099545	0.072*
C75	0.88575 (18)	0.14408 (17)	0.15010 (10)	0.0519 (6)
H75	0.811562	0.173619	0.160965	0.062*
C76A	1.197 (4)	−0.114 (4)	0.053 (2)	0.096 (11)	0.23 (6)
H76A	1.218809	−0.173181	0.027673	0.144*	0.23 (6)
H76B	1.216800	−0.054760	0.036540	0.144*	0.23 (6)
H76C	1.233599	−0.142334	0.089281	0.144*	0.23 (6)
C76B	1.156 (2)	−0.1159 (9)	0.0437 (6)	0.092 (5)	0.77 (6)
H76D	1.156996	−0.171336	0.018931	0.139*	0.77 (6)
H76E	1.178936	−0.062118	0.022792	0.139*	0.77 (6)
H76F	1.204922	−0.150822	0.075591	0.139*	0.77 (6)
C77	0.46162 (14)	0.63472 (14)	0.12144 (8)	0.0312 (4)
C78	0.44299 (15)	0.58360 (16)	0.07628 (8)	0.0364 (5)
H78	0.491915	0.570768	0.045591	0.044*
C79	0.35514 (15)	0.55077 (16)	0.07470 (9)	0.0395 (5)
H79	0.344786	0.517633	0.042922	0.047*
C80	0.28231 (15)	0.56628 (16)	0.11951 (9)	0.0384 (5)
C81	0.30205 (16)	0.61340 (17)	0.16600 (9)	0.0410 (5)
H81	0.255781	0.622020	0.197703	0.049*
C82	0.38868 (15)	0.64780 (16)	0.16634 (8)	0.0384 (5)
H82	0.398734	0.681251	0.198061	0.046*
C83	0.20350 (15)	0.43862 (16)	0.08990 (9)	0.0399 (5)
C84	0.28086 (16)	0.33737 (17)	0.10893 (9)	0.0442 (5)
H84	0.326100	0.331846	0.140058	0.053*
C85	0.29250 (18)	0.24447 (17)	0.08286 (9)	0.0467 (5)
H85	0.346130	0.176183	0.096104	0.056*
C86	0.22626 (17)	0.25032 (17)	0.03739 (9)	0.0422 (5)
C87	0.14907 (17)	0.35053 (19)	0.01793 (10)	0.0505 (6)
H87	0.103382	0.355796	−0.012953	0.061*
C88	0.13883 (17)	0.44408 (18)	0.04411 (10)	0.0508 (6)
H88	0.086567	0.512703	0.030258	0.061*
C89	0.1809 (3)	0.1556 (2)	−0.03294 (12)	0.0824 (9)
H89A	0.105005	0.175335	−0.021262	0.124*
H89B	0.207579	0.083462	−0.047485	0.124*
H89C	0.185603	0.209574	−0.062368	0.124*
C90	0.08712 (15)	0.59971 (16)	0.13867 (9)	0.0387 (5)
C91	0.01306 (15)	0.55199 (16)	0.15644 (9)	0.0394 (5)
H91	0.032101	0.476097	0.154250	0.047*
C92	−0.08817 (16)	0.61499 (17)	0.17727 (9)	0.0413 (5)
H92	−0.138507	0.582084	0.188036	0.050*
C93	−0.11649 (15)	0.72556 (17)	0.18250 (9)	0.0413 (5)
C94	−0.04438 (16)	0.77429 (17)	0.16460 (10)	0.0478 (5)
H94	−0.063263	0.849947	0.167545	0.057*
C95	0.05609 (16)	0.71151 (17)	0.14225 (10)	0.0477 (5)
H95	0.104253	0.745684	0.129221	0.057*
C96	−0.2481 (2)	0.8910 (2)	0.21539 (14)	0.0848 (9)
H96A	−0.193077	0.899503	0.238838	0.127*
H96B	−0.318675	0.917022	0.234349	0.127*
H96C	−0.253874	0.933482	0.179211	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0325 (8)	0.0709 (12)	0.0757 (12)	−0.0057 (8)	−0.0087 (8)	0.0122 (9)
O2	0.0686 (11)	0.0462 (10)	0.0795 (12)	−0.0194 (8)	−0.0005 (9)	0.0199 (9)
O3	0.0896 (13)	0.0489 (10)	0.0580 (11)	−0.0233 (9)	−0.0152 (9)	0.0121 (8)
O4	0.0664 (10)	0.0523 (10)	0.0437 (9)	−0.0208 (8)	0.0079 (8)	−0.0133 (7)
N1	0.0299 (9)	0.0457 (10)	0.0660 (13)	−0.0187 (8)	−0.0072 (8)	0.0185 (9)
N2	0.0665 (13)	0.0410 (11)	0.0517 (12)	0.0048 (9)	0.0236 (10)	0.0063 (9)
C1	0.0313 (10)	0.0298 (10)	0.0379 (11)	−0.0147 (8)	0.0017 (8)	−0.0009 (8)
C2	0.0393 (11)	0.0374 (11)	0.0489 (13)	−0.0208 (9)	0.0006 (9)	−0.0055 (9)
C3	0.0550 (14)	0.0422 (13)	0.0666 (16)	−0.0232 (11)	0.0057 (12)	−0.0185 (11)
C4	0.0597 (15)	0.0315 (12)	0.103 (2)	−0.0201 (11)	0.0083 (14)	−0.0090 (13)
C5	0.0553 (14)	0.0323 (12)	0.0797 (18)	−0.0177 (11)	0.0017 (12)	0.0134 (12)
C6	0.0399 (11)	0.0386 (12)	0.0526 (13)	−0.0212 (9)	0.0030 (10)	0.0078 (10)
C7	0.0309 (10)	0.0237 (9)	0.0337 (11)	−0.0096 (8)	0.0017 (8)	−0.0013 (8)
C8	0.0351 (10)	0.0348 (11)	0.0321 (11)	−0.0152 (8)	0.0011 (8)	0.0029 (8)
C9	0.0352 (10)	0.0399 (11)	0.0343 (11)	−0.0144 (9)	−0.0060 (8)	0.0011 (9)
C10	0.0284 (10)	0.0329 (10)	0.0456 (12)	−0.0127 (8)	−0.0010 (9)	0.0044 (9)
C11	0.0385 (11)	0.0434 (12)	0.0356 (11)	−0.0192 (9)	−0.0006 (9)	0.0099 (9)
C12	0.0344 (10)	0.0383 (11)	0.0337 (11)	−0.0150 (9)	−0.0048 (8)	0.0034 (9)
C13	0.0289 (10)	0.0393 (11)	0.0385 (12)	−0.0124 (9)	0.0017 (8)	0.0014 (9)
C14	0.0360 (11)	0.0408 (12)	0.0493 (13)	−0.0147 (9)	−0.0002 (9)	−0.0079 (10)
C15	0.0402 (12)	0.0368 (12)	0.0540 (14)	−0.0075 (10)	0.0045 (10)	−0.0051 (10)
C16	0.0291 (10)	0.0537 (14)	0.0405 (12)	−0.0083 (10)	0.0030 (9)	0.0012 (10)
C17	0.0321 (11)	0.0601 (15)	0.0452 (13)	−0.0229 (10)	0.0011 (9)	0.0002 (11)
C18	0.0363 (11)	0.0417 (12)	0.0455 (13)	−0.0179 (9)	0.0024 (9)	0.0010 (10)
C19	0.0488 (16)	0.075 (2)	0.119 (3)	0.0085 (14)	−0.0102 (16)	0.0165 (18)
C20	0.0292 (10)	0.0377 (11)	0.0508 (13)	−0.0149 (9)	−0.0056 (9)	0.0083 (10)
C21	0.0317 (11)	0.0369 (12)	0.0573 (14)	−0.0095 (9)	0.0021 (10)	0.0014 (10)
C22	0.0392 (12)	0.0494 (13)	0.0509 (14)	−0.0168 (10)	0.0049 (10)	0.0064 (11)
C23	0.0424 (12)	0.0400 (12)	0.0530 (14)	−0.0188 (10)	−0.0067 (10)	0.0106 (10)
C24	0.0463 (13)	0.0353 (12)	0.0623 (15)	−0.0115 (10)	0.0026 (11)	−0.0039 (11)
C25	0.0403 (12)	0.0479 (13)	0.0516 (14)	−0.0172 (10)	0.0080 (10)	−0.0002 (11)
C26	0.0809 (19)	0.0393 (14)	0.097 (2)	−0.0200 (13)	−0.0188 (16)	0.0147 (14)
C27	0.0300 (10)	0.0329 (10)	0.0377 (11)	−0.0162 (8)	0.0035 (8)	0.0002 (9)
C28	0.0424 (11)	0.0375 (11)	0.0357 (12)	−0.0144 (9)	0.0006 (9)	0.0006 (9)
C29	0.0406 (12)	0.0380 (12)	0.0450 (13)	−0.0067 (9)	−0.0001 (10)	0.0100 (10)
C30	0.0439 (12)	0.0364 (12)	0.0456 (13)	−0.0076 (10)	0.0118 (10)	0.0014 (10)
C31	0.0468 (13)	0.0516 (13)	0.0400 (13)	−0.0151 (11)	0.0059 (10)	−0.0110 (10)
C32	0.0350 (11)	0.0443 (12)	0.0406 (12)	−0.0121 (9)	−0.0004 (9)	−0.0034 (10)
C33	0.0514 (13)	0.0365 (12)	0.0462 (13)	−0.0070 (10)	0.0084 (10)	0.0013 (10)
C34	0.0467 (13)	0.0461 (13)	0.0564 (15)	−0.0086 (11)	0.0082 (11)	−0.0034 (11)
C35	0.0649 (16)	0.0459 (13)	0.0501 (14)	−0.0245 (12)	0.0097 (12)	−0.0013 (11)
C36	0.0659 (15)	0.0374 (12)	0.0406 (13)	−0.0172 (11)	−0.0064 (11)	−0.0002 (10)
C37	0.0489 (14)	0.0500 (14)	0.0664 (17)	−0.0115 (11)	−0.0067 (12)	0.0040 (12)
C38	0.0505 (14)	0.0519 (15)	0.0653 (17)	−0.0164 (12)	0.0079 (12)	0.0060 (12)
C39	0.133 (3)	0.0565 (17)	0.0518 (16)	−0.0414 (17)	0.0009 (17)	0.0091 (13)
C40	0.0418 (12)	0.0349 (12)	0.0462 (13)	−0.0036 (9)	0.0079 (10)	0.0004 (10)
C41	0.0530 (13)	0.0354 (12)	0.0448 (13)	−0.0113 (10)	0.0044 (10)	−0.0087 (10)
C42	0.0455 (12)	0.0395 (12)	0.0397 (12)	−0.0165 (9)	0.0018 (9)	−0.0030 (10)
C43	0.0346 (11)	0.0404 (12)	0.0370 (12)	−0.0084 (9)	−0.0012 (9)	−0.0056 (9)
C44	0.0442 (12)	0.0353 (12)	0.0519 (14)	−0.0101 (10)	−0.0036 (10)	−0.0079 (10)
C45	0.0452 (12)	0.0358 (12)	0.0596 (15)	−0.0121 (10)	0.0034 (11)	0.0036 (11)
C46	0.0793 (18)	0.0625 (16)	0.0432 (14)	−0.0222 (14)	0.0102 (12)	−0.0026 (12)
O5	0.0713 (11)	0.0392 (9)	0.0529 (10)	−0.0181 (8)	−0.0155 (8)	0.0095 (7)
O6	0.1173 (17)	0.0497 (11)	0.0643 (12)	−0.0015 (11)	0.0026 (12)	−0.0183 (9)
O7	0.0768 (11)	0.0527 (10)	0.0554 (10)	−0.0306 (9)	−0.0109 (8)	−0.0130 (8)
O8	0.0362 (8)	0.0610 (11)	0.0690 (11)	−0.0034 (7)	0.0032 (7)	−0.0134 (8)
N3	0.0645 (13)	0.0341 (10)	0.0662 (14)	0.0005 (9)	−0.0255 (10)	−0.0133 (9)
N4	0.0298 (9)	0.0445 (11)	0.0753 (14)	−0.0161 (8)	0.0074 (9)	−0.0200 (9)
C51	0.0298 (10)	0.0313 (10)	0.0394 (11)	−0.0110 (8)	0.0001 (8)	−0.0056 (9)
C52	0.0386 (11)	0.0400 (12)	0.0525 (14)	−0.0165 (9)	−0.0009 (10)	−0.0131 (10)
C53	0.0521 (14)	0.0352 (12)	0.0734 (17)	−0.0121 (10)	−0.0010 (12)	−0.0183 (11)
C54	0.0653 (16)	0.0328 (12)	0.084 (2)	−0.0124 (11)	−0.0046 (14)	−0.0012 (12)
C55	0.0546 (14)	0.0390 (12)	0.0578 (15)	−0.0153 (10)	−0.0020 (11)	0.0057 (11)
C56	0.0378 (11)	0.0350 (11)	0.0490 (13)	−0.0157 (9)	0.0017 (9)	0.0002 (9)
C57	0.0315 (10)	0.0316 (10)	0.0393 (12)	−0.0144 (8)	−0.0013 (8)	−0.0056 (9)
C58	0.0317 (10)	0.0409 (12)	0.0437 (13)	−0.0125 (9)	0.0030 (9)	−0.0051 (9)
C59	0.0450 (12)	0.0426 (12)	0.0424 (13)	−0.0170 (10)	−0.0064 (10)	0.0026 (10)
C60	0.0415 (12)	0.0288 (11)	0.0572 (15)	−0.0085 (9)	−0.0114 (10)	−0.0054 (10)
C61	0.0400 (12)	0.0369 (12)	0.0507 (14)	−0.0069 (9)	0.0020 (10)	−0.0125 (10)
C62	0.0397 (11)	0.0358 (11)	0.0399 (12)	−0.0107 (9)	−0.0010 (9)	−0.0064 (9)
C63	0.0408 (11)	0.0303 (11)	0.0548 (14)	−0.0069 (9)	−0.0085 (10)	−0.0047 (10)
C64	0.0489 (12)	0.0273 (10)	0.0464 (13)	−0.0114 (9)	−0.0038 (10)	0.0031 (9)
C65	0.0451 (12)	0.0292 (10)	0.0461 (13)	−0.0153 (9)	−0.0011 (10)	0.0000 (9)
C66	0.0393 (11)	0.0312 (11)	0.0472 (13)	−0.0103 (9)	−0.0020 (10)	0.0036 (9)
C67	0.0623 (15)	0.0258 (11)	0.0684 (17)	−0.0149 (10)	−0.0123 (12)	0.0114 (11)
C68	0.0604 (14)	0.0283 (11)	0.0770 (18)	−0.0169 (10)	−0.0166 (13)	−0.0017 (11)
C69	0.0653 (16)	0.0529 (15)	0.0527 (15)	−0.0217 (12)	−0.0079 (12)	−0.0010 (12)
C70	0.0477 (13)	0.0313 (11)	0.0569 (15)	−0.0052 (10)	−0.0126 (11)	−0.0054 (10)
C71	0.0489 (14)	0.0463 (14)	0.089 (2)	−0.0145 (11)	−0.0105 (13)	−0.0065 (13)
C72	0.0510 (15)	0.0506 (15)	0.083 (2)	−0.0061 (12)	0.0141 (14)	−0.0045 (14)
C73	0.0765 (18)	0.0336 (12)	0.0493 (15)	−0.0061 (12)	−0.0001 (13)	−0.0042 (11)
C74	0.0636 (16)	0.0368 (13)	0.0739 (18)	−0.0109 (11)	−0.0205 (13)	−0.0087 (12)
C75	0.0433 (12)	0.0355 (12)	0.0690 (16)	−0.0050 (10)	−0.0085 (11)	−0.0087 (11)
C76A	0.055 (16)	0.073 (13)	0.13 (2)	0.014 (12)	0.024 (14)	−0.040 (13)
C76B	0.115 (11)	0.065 (3)	0.077 (5)	−0.013 (5)	0.047 (6)	−0.012 (3)
C77	0.0287 (9)	0.0259 (9)	0.0361 (11)	−0.0072 (8)	−0.0024 (8)	−0.0018 (8)
C78	0.0339 (10)	0.0394 (11)	0.0366 (11)	−0.0142 (9)	0.0059 (8)	−0.0079 (9)
C79	0.0388 (11)	0.0412 (12)	0.0418 (12)	−0.0169 (9)	−0.0009 (9)	−0.0124 (9)
C80	0.0279 (10)	0.0350 (11)	0.0511 (13)	−0.0102 (8)	0.0015 (9)	−0.0054 (9)
C81	0.0355 (11)	0.0483 (13)	0.0410 (12)	−0.0172 (9)	0.0087 (9)	−0.0102 (10)
C82	0.0375 (11)	0.0437 (12)	0.0343 (11)	−0.0142 (9)	−0.0008 (9)	−0.0106 (9)
C83	0.0300 (10)	0.0413 (12)	0.0512 (13)	−0.0158 (9)	0.0014 (9)	−0.0091 (10)
C84	0.0412 (12)	0.0482 (13)	0.0434 (13)	−0.0164 (10)	−0.0116 (10)	−0.0039 (10)
C85	0.0504 (13)	0.0379 (12)	0.0476 (13)	−0.0120 (10)	−0.0119 (10)	−0.0011 (10)
C86	0.0448 (12)	0.0449 (13)	0.0422 (13)	−0.0225 (10)	−0.0018 (10)	−0.0055 (10)
C87	0.0392 (12)	0.0615 (15)	0.0489 (14)	−0.0155 (11)	−0.0136 (10)	−0.0082 (12)
C88	0.0381 (12)	0.0457 (13)	0.0590 (15)	−0.0046 (10)	−0.0102 (11)	−0.0041 (11)
C89	0.117 (2)	0.086 (2)	0.0669 (19)	−0.0594 (19)	−0.0229 (17)	−0.0180 (16)
C90	0.0302 (10)	0.0371 (11)	0.0471 (13)	−0.0109 (9)	−0.0029 (9)	−0.0032 (9)
C91	0.0369 (11)	0.0357 (11)	0.0463 (13)	−0.0143 (9)	−0.0026 (9)	−0.0035 (9)
C92	0.0347 (11)	0.0473 (13)	0.0438 (13)	−0.0178 (10)	0.0005 (9)	−0.0029 (10)
C93	0.0284 (10)	0.0492 (13)	0.0384 (12)	−0.0061 (9)	−0.0078 (9)	−0.0020 (10)
C94	0.0389 (12)	0.0322 (11)	0.0652 (15)	−0.0060 (9)	−0.0090 (10)	−0.0005 (10)
C95	0.0360 (11)	0.0404 (12)	0.0672 (16)	−0.0165 (10)	0.0006 (10)	0.0016 (11)
C96	0.0551 (16)	0.0635 (18)	0.112 (3)	0.0072 (14)	0.0032 (16)	−0.0233 (17)

Geometric parameters (Å, º) top

O1—C16	1.374 (2)	O6—C76B	1.34 (2)
O1—C19	1.413 (3)	O6—C73	1.371 (3)
O2—C23	1.369 (2)	O6—C76A	1.76 (5)
O2—C26	1.412 (3)	O7—C86	1.368 (2)
O3—C36	1.371 (3)	O7—C89	1.417 (3)
O3—C39	1.433 (3)	O8—C93	1.376 (2)
O4—C43	1.371 (2)	O8—C96	1.407 (3)
O4—C46	1.410 (3)	N3—C63	1.413 (3)
N1—C10	1.416 (2)	N3—C60	1.417 (3)
N1—C13	1.416 (2)	N3—C70	1.424 (3)
N1—C20	1.427 (2)	N4—C80	1.417 (2)
N2—C30	1.418 (3)	N4—C90	1.417 (2)
N2—C40	1.419 (3)	N4—C83	1.424 (3)
N2—C33	1.421 (3)	C51—C77	1.539 (2)
C1—C2	1.538 (3)	C51—C52	1.542 (3)
C1—C27	1.540 (2)	C51—C56	1.543 (3)
C1—C7	1.540 (2)	C51—C57	1.545 (3)
C1—C6	1.547 (3)	C52—C53	1.529 (3)
C2—C3	1.526 (3)	C52—H52A	0.9800
C2—H2A	0.9800	C52—H52B	0.9800
C2—H2B	0.9800	C53—C54	1.517 (3)
C3—C4	1.511 (3)	C53—H53A	0.9800
C3—H3A	0.9800	C53—H53B	0.9800
C3—H3B	0.9800	C54—C55	1.512 (3)
C4—C5	1.510 (3)	C54—H54A	0.9800
C4—H4A	0.9800	C54—H54B	0.9800
C4—H4B	0.9800	C55—C56	1.525 (3)
C5—C6	1.525 (3)	C55—H55A	0.9800
C5—H5A	0.9800	C55—H55B	0.9800
C5—H5B	0.9800	C56—H56A	0.9800
C6—H6A	0.9800	C56—H56B	0.9800
C6—H6B	0.9800	C57—C62	1.386 (3)
C7—C8	1.385 (3)	C57—C58	1.391 (3)
C7—C12	1.388 (2)	C58—C59	1.379 (3)
C8—C9	1.379 (3)	C58—H58	0.9400
C8—H8	0.9400	C59—C60	1.392 (3)
C9—C10	1.383 (3)	C59—H59	0.9400
C9—H9	0.9400	C60—C61	1.381 (3)
C10—C11	1.381 (3)	C61—C62	1.382 (3)
C11—C12	1.380 (3)	C61—H61	0.9400
C11—H11	0.9400	C62—H62	0.9400
C12—H12	0.9400	C63—C64	1.380 (3)
C13—C14	1.383 (3)	C63—C68	1.390 (3)
C13—C18	1.388 (3)	C64—C65	1.378 (3)
C14—C15	1.385 (3)	C64—H64	0.9400
C14—H14	0.9400	C65—C66	1.378 (3)
C15—C16	1.375 (3)	C65—H65	0.9400
C15—H15	0.9400	C66—C67	1.375 (3)
C16—C17	1.380 (3)	C67—C68	1.371 (3)
C17—C18	1.379 (3)	C67—H67	0.9400
C17—H17	0.9400	C68—H68	0.9400
C18—H18	0.9400	C69—H69A	0.9700
C19—H19A	0.9700	C69—H69B	0.9700
C19—H19B	0.9700	C69—H69C	0.9700
C19—H19C	0.9700	C70—C71	1.370 (3)
C20—C25	1.372 (3)	C70—C75	1.385 (3)
C20—C21	1.386 (3)	C71—C72	1.386 (3)
C21—C22	1.378 (3)	C71—H71	0.9400
C21—H21	0.9400	C72—C73	1.371 (4)
C22—C23	1.385 (3)	C72—H72	0.9400
C22—H22	0.9400	C73—C74	1.378 (3)
C23—C24	1.378 (3)	C74—C75	1.367 (3)
C24—C25	1.379 (3)	C74—H74	0.9400
C24—H24	0.9400	C75—H75	0.9400
C25—H25	0.9400	C76A—H76A	0.9700
C26—H26A	0.9700	C76A—H76B	0.9700
C26—H26B	0.9700	C76A—H76C	0.9700
C26—H26C	0.9700	C76B—H76D	0.9700
C27—C28	1.388 (3)	C76B—H76E	0.9700
C27—C32	1.391 (3)	C76B—H76F	0.9700
C28—C29	1.391 (3)	C77—C78	1.387 (3)
C28—H28	0.9400	C77—C82	1.389 (3)
C29—C30	1.377 (3)	C78—C79	1.383 (3)
C29—H29	0.9400	C78—H78	0.9400
C30—C31	1.386 (3)	C79—C80	1.385 (3)
C31—C32	1.378 (3)	C79—H79	0.9400
C31—H31	0.9400	C80—C81	1.387 (3)
C32—H32	0.9400	C81—C82	1.379 (3)
C33—C34	1.377 (3)	C81—H81	0.9400
C33—C38	1.383 (3)	C82—H82	0.9400
C34—C35	1.391 (3)	C83—C88	1.376 (3)
C34—H34	0.9400	C83—C84	1.379 (3)
C35—C36	1.374 (3)	C84—C85	1.374 (3)
C35—H35	0.9400	C84—H84	0.9400
C36—C37	1.376 (3)	C85—C86	1.382 (3)
C37—C38	1.377 (3)	C85—H85	0.9400
C37—H37	0.9400	C86—C87	1.372 (3)
C38—H38	0.9400	C87—C88	1.388 (3)
C39—H39A	0.9700	C87—H87	0.9400
C39—H39B	0.9700	C88—H88	0.9400
C39—H39C	0.9700	C89—H89A	0.9700
C40—C41	1.381 (3)	C89—H89B	0.9700
C40—C45	1.387 (3)	C89—H89C	0.9700
C41—C42	1.383 (3)	C90—C95	1.381 (3)
C41—H41	0.9400	C90—C91	1.387 (3)
C42—C43	1.379 (3)	C91—C92	1.377 (3)
C42—H42	0.9400	C91—H91	0.9400
C43—C44	1.376 (3)	C92—C93	1.376 (3)
C44—C45	1.375 (3)	C92—H92	0.9400
C44—H44	0.9400	C93—C94	1.375 (3)
C45—H45	0.9400	C94—C95	1.383 (3)
C46—H46A	0.9700	C94—H94	0.9400
C46—H46B	0.9700	C95—H95	0.9400
C46—H46C	0.9700	C96—H96A	0.9700
O5—C66	1.372 (2)	C96—H96B	0.9700
O5—C69	1.411 (3)	C96—H96C	0.9700

C16—O1—C19	117.5 (2)	C93—O8—C96	118.12 (19)
C23—O2—C26	117.67 (19)	C63—N3—C60	122.79 (17)
C36—O3—C39	117.9 (2)	C63—N3—C70	119.17 (17)
C43—O4—C46	117.15 (17)	C60—N3—C70	118.01 (18)
C10—N1—C13	121.34 (16)	C80—N4—C90	121.33 (16)
C10—N1—C20	118.71 (15)	C80—N4—C83	118.86 (16)
C13—N1—C20	119.93 (15)	C90—N4—C83	119.64 (16)
C30—N2—C40	120.03 (17)	C77—C51—C52	112.89 (15)
C30—N2—C33	121.53 (17)	C77—C51—C56	111.37 (15)
C40—N2—C33	118.24 (17)	C52—C51—C56	106.29 (16)
C2—C1—C27	111.62 (15)	C77—C51—C57	106.47 (14)
C2—C1—C7	110.74 (15)	C52—C51—C57	108.91 (15)
C27—C1—C7	107.94 (14)	C56—C51—C57	110.95 (15)
C2—C1—C6	106.31 (15)	C53—C52—C51	113.94 (17)
C27—C1—C6	108.30 (15)	C53—C52—H52A	108.8
C7—C1—C6	111.94 (15)	C51—C52—H52A	108.8
C3—C2—C1	112.53 (17)	C53—C52—H52B	108.8
C3—C2—H2A	109.1	C51—C52—H52B	108.8
C1—C2—H2A	109.1	H52A—C52—H52B	107.7
C3—C2—H2B	109.1	C54—C53—C52	111.65 (19)
C1—C2—H2B	109.1	C54—C53—H53A	109.3
H2A—C2—H2B	107.8	C52—C53—H53A	109.3
C4—C3—C2	110.55 (19)	C54—C53—H53B	109.3
C4—C3—H3A	109.5	C52—C53—H53B	109.3
C2—C3—H3A	109.5	H53A—C53—H53B	108.0
C4—C3—H3B	109.5	C55—C54—C53	110.29 (19)
C2—C3—H3B	109.5	C55—C54—H54A	109.6
H3A—C3—H3B	108.1	C53—C54—H54A	109.6
C5—C4—C3	110.31 (18)	C55—C54—H54B	109.6
C5—C4—H4A	109.6	C53—C54—H54B	109.6
C3—C4—H4A	109.6	H54A—C54—H54B	108.1
C5—C4—H4B	109.6	C54—C55—C56	111.20 (19)
C3—C4—H4B	109.6	C54—C55—H55A	109.4
H4A—C4—H4B	108.1	C56—C55—H55A	109.4
C4—C5—C6	111.40 (19)	C54—C55—H55B	109.4
C4—C5—H5A	109.3	C56—C55—H55B	109.4
C6—C5—H5A	109.3	H55A—C55—H55B	108.0
C4—C5—H5B	109.3	C55—C56—C51	113.40 (17)
C6—C5—H5B	109.3	C55—C56—H56A	108.9
H5A—C5—H5B	108.0	C51—C56—H56A	108.9
C5—C6—C1	113.61 (17)	C55—C56—H56B	108.9
C5—C6—H6A	108.8	C51—C56—H56B	108.9
C1—C6—H6A	108.8	H56A—C56—H56B	107.7
C5—C6—H6B	108.8	C62—C57—C58	116.82 (17)
C1—C6—H6B	108.8	C62—C57—C51	122.69 (17)
H6A—C6—H6B	107.7	C58—C57—C51	120.48 (17)
C8—C7—C12	115.93 (17)	C59—C58—C57	122.03 (19)
C8—C7—C1	122.28 (16)	C59—C58—H58	119.0
C12—C7—C1	121.73 (16)	C57—C58—H58	119.0
C9—C8—C7	122.56 (18)	C58—C59—C60	120.4 (2)
C9—C8—H8	118.7	C58—C59—H59	119.8
C7—C8—H8	118.7	C60—C59—H59	119.8
C8—C9—C10	120.63 (18)	C61—C60—C59	118.08 (18)
C8—C9—H9	119.7	C61—C60—N3	120.2 (2)
C10—C9—H9	119.7	C59—C60—N3	121.7 (2)
C11—C10—C9	117.77 (17)	C60—C61—C62	121.01 (19)
C11—C10—N1	120.77 (18)	C60—C61—H61	119.5
C9—C10—N1	121.46 (18)	C62—C61—H61	119.5
C12—C11—C10	120.94 (18)	C61—C62—C57	121.7 (2)
C12—C11—H11	119.5	C61—C62—H62	119.2
C10—C11—H11	119.5	C57—C62—H62	119.2
C11—C12—C7	122.16 (18)	C64—C63—C68	117.7 (2)
C11—C12—H12	118.9	C64—C63—N3	122.03 (19)
C7—C12—H12	118.9	C68—C63—N3	120.23 (19)
C14—C13—C18	118.27 (18)	C65—C64—C63	121.67 (19)
C14—C13—N1	121.16 (18)	C65—C64—H64	119.2
C18—C13—N1	120.57 (18)	C63—C64—H64	119.2
C13—C14—C15	121.20 (19)	C66—C65—C64	119.82 (19)
C13—C14—H14	119.4	C66—C65—H65	120.1
C15—C14—H14	119.4	C64—C65—H65	120.1
C16—C15—C14	119.8 (2)	O5—C66—C67	115.82 (18)
C16—C15—H15	120.1	O5—C66—C65	125.13 (19)
C14—C15—H15	120.1	C67—C66—C65	119.0 (2)
O1—C16—C15	124.6 (2)	C68—C67—C66	121.1 (2)
O1—C16—C17	115.71 (19)	C68—C67—H67	119.5
C15—C16—C17	119.70 (19)	C66—C67—H67	119.5
C18—C17—C16	120.35 (19)	C67—C68—C63	120.6 (2)
C18—C17—H17	119.8	C67—C68—H68	119.7
C16—C17—H17	119.8	C63—C68—H68	119.7
C17—C18—C13	120.71 (19)	O5—C69—H69A	109.5
C17—C18—H18	119.6	O5—C69—H69B	109.5
C13—C18—H18	119.6	H69A—C69—H69B	109.5
O1—C19—H19A	109.5	O5—C69—H69C	109.5
O1—C19—H19B	109.5	H69A—C69—H69C	109.5
H19A—C19—H19B	109.5	H69B—C69—H69C	109.5
O1—C19—H19C	109.5	C71—C70—C75	118.7 (2)
H19A—C19—H19C	109.5	C71—C70—N3	121.7 (2)
H19B—C19—H19C	109.5	C75—C70—N3	119.6 (2)
C25—C20—C21	118.75 (19)	C70—C71—C72	121.1 (2)
C25—C20—N1	120.32 (19)	C70—C71—H71	119.4
C21—C20—N1	120.93 (18)	C72—C71—H71	119.4
C22—C21—C20	120.50 (19)	C73—C72—C71	119.4 (2)
C22—C21—H21	119.7	C73—C72—H72	120.3
C20—C21—H21	119.7	C71—C72—H72	120.3
C21—C22—C23	120.1 (2)	C72—C73—O6	125.3 (2)
C21—C22—H22	120.0	C72—C73—C74	119.8 (2)
C23—C22—H22	120.0	O6—C73—C74	115.0 (2)
O2—C23—C24	124.8 (2)	C75—C74—C73	120.4 (2)
O2—C23—C22	115.6 (2)	C75—C74—H74	119.8
C24—C23—C22	119.63 (19)	C73—C74—H74	119.8
C23—C24—C25	119.7 (2)	C74—C75—C70	120.5 (2)
C23—C24—H24	120.2	C74—C75—H75	119.7
C25—C24—H24	120.2	C70—C75—H75	119.7
C20—C25—C24	121.4 (2)	O6—C76A—H76A	109.5
C20—C25—H25	119.3	O6—C76A—H76B	109.5
C24—C25—H25	119.3	H76A—C76A—H76B	109.5
O2—C26—H26A	109.5	O6—C76A—H76C	109.5
O2—C26—H26B	109.5	H76A—C76A—H76C	109.5
H26A—C26—H26B	109.5	H76B—C76A—H76C	109.5
O2—C26—H26C	109.5	O6—C76B—H76D	109.5
H26A—C26—H26C	109.5	O6—C76B—H76E	109.5
H26B—C26—H26C	109.5	H76D—C76B—H76E	109.5
C28—C27—C32	116.58 (18)	O6—C76B—H76F	109.5
C28—C27—C1	123.54 (17)	H76D—C76B—H76F	109.5
C32—C27—C1	119.88 (17)	H76E—C76B—H76F	109.5
C27—C28—C29	121.56 (19)	C78—C77—C82	115.95 (17)
C27—C28—H28	119.2	C78—C77—C51	121.61 (16)
C29—C28—H28	119.2	C82—C77—C51	122.33 (17)
C30—C29—C28	120.91 (19)	C79—C78—C77	122.50 (18)
C30—C29—H29	119.5	C79—C78—H78	118.8
C28—C29—H29	119.5	C77—C78—H78	118.8
C29—C30—C31	118.16 (19)	C78—C79—C80	120.58 (18)
C29—C30—N2	121.2 (2)	C78—C79—H79	119.7
C31—C30—N2	120.6 (2)	C80—C79—H79	119.7
C32—C31—C30	120.7 (2)	C79—C80—C81	117.74 (18)
C32—C31—H31	119.7	C79—C80—N4	120.62 (18)
C30—C31—H31	119.7	C81—C80—N4	121.64 (18)
C31—C32—C27	122.12 (19)	C82—C81—C80	120.86 (18)
C31—C32—H32	118.9	C82—C81—H81	119.6
C27—C32—H32	118.9	C80—C81—H81	119.6
C34—C33—C38	118.2 (2)	C81—C82—C77	122.30 (18)
C34—C33—N2	121.8 (2)	C81—C82—H82	118.9
C38—C33—N2	120.0 (2)	C77—C82—H82	118.9
C33—C34—C35	121.3 (2)	C88—C83—C84	118.28 (19)
C33—C34—H34	119.3	C88—C83—N4	121.45 (19)
C35—C34—H34	119.3	C84—C83—N4	120.26 (19)
C36—C35—C34	119.6 (2)	C85—C84—C83	120.67 (19)
C36—C35—H35	120.2	C85—C84—H84	119.7
C34—C35—H35	120.2	C83—C84—H84	119.7
O3—C36—C35	125.0 (2)	C84—C85—C86	120.7 (2)
O3—C36—C37	115.6 (2)	C84—C85—H85	119.6
C35—C36—C37	119.4 (2)	C86—C85—H85	119.6
C36—C37—C38	120.7 (2)	O7—C86—C87	125.01 (19)
C36—C37—H37	119.6	O7—C86—C85	115.74 (19)
C38—C37—H37	119.6	C87—C86—C85	119.2 (2)
C37—C38—C33	120.7 (2)	C86—C87—C88	119.6 (2)
C37—C38—H38	119.6	C86—C87—H87	120.2
C33—C38—H38	119.6	C88—C87—H87	120.2
O3—C39—H39A	109.5	C83—C88—C87	121.5 (2)
O3—C39—H39B	109.5	C83—C88—H88	119.3
H39A—C39—H39B	109.5	C87—C88—H88	119.3
O3—C39—H39C	109.5	O7—C89—H89A	109.5
H39A—C39—H39C	109.5	O7—C89—H89B	109.5
H39B—C39—H39C	109.5	H89A—C89—H89B	109.5
C41—C40—C45	118.2 (2)	O7—C89—H89C	109.5
C41—C40—N2	121.1 (2)	H89A—C89—H89C	109.5
C45—C40—N2	120.6 (2)	H89B—C89—H89C	109.5
C40—C41—C42	121.3 (2)	C95—C90—C91	118.14 (18)
C40—C41—H41	119.3	C95—C90—N4	121.70 (18)
C42—C41—H41	119.3	C91—C90—N4	120.16 (18)
C43—C42—C41	119.4 (2)	C92—C91—C90	120.47 (19)
C43—C42—H42	120.3	C92—C91—H91	119.8
C41—C42—H42	120.3	C90—C91—H91	119.8
O4—C43—C44	115.66 (18)	C93—C92—C91	120.77 (19)
O4—C43—C42	124.46 (19)	C93—C92—H92	119.6
C44—C43—C42	119.88 (19)	C91—C92—H92	119.6
C45—C44—C43	120.3 (2)	C94—C93—O8	124.8 (2)
C45—C44—H44	119.9	C94—C93—C92	119.43 (18)
C43—C44—H44	119.9	O8—C93—C92	115.73 (19)
C44—C45—C40	120.8 (2)	C93—C94—C95	119.7 (2)
C44—C45—H45	119.6	C93—C94—H94	120.1
C40—C45—H45	119.6	C95—C94—H94	120.1
O4—C46—H46A	109.5	C90—C95—C94	121.40 (19)
O4—C46—H46B	109.5	C90—C95—H95	119.3
H46A—C46—H46B	109.5	C94—C95—H95	119.3
O4—C46—H46C	109.5	O8—C96—H96A	109.5
H46A—C46—H46C	109.5	O8—C96—H96B	109.5
H46B—C46—H46C	109.5	H96A—C96—H96B	109.5
C66—O5—C69	118.06 (16)	O8—C96—H96C	109.5
C76B—O6—C73	121.1 (12)	H96A—C96—H96C	109.5
C73—O6—C76A	106 (2)	H96B—C96—H96C	109.5
C86—O7—C89	117.62 (19)

C27—C1—C2—C3	174.64 (16)	C56—C51—C52—C53	54.3 (2)
C7—C1—C2—C3	−65.1 (2)	C57—C51—C52—C53	173.86 (17)
C6—C1—C2—C3	56.7 (2)	C51—C52—C53—C54	−56.0 (2)
C1—C2—C3—C4	−60.1 (2)	C52—C53—C54—C55	54.3 (3)
C2—C3—C4—C5	57.1 (3)	C53—C54—C55—C56	−55.6 (3)
C3—C4—C5—C6	−55.1 (3)	C54—C55—C56—C51	58.6 (2)
C4—C5—C6—C1	55.9 (2)	C77—C51—C56—C55	67.8 (2)
C2—C1—C6—C5	−54.8 (2)	C52—C51—C56—C55	−55.6 (2)
C27—C1—C6—C5	−174.88 (17)	C57—C51—C56—C55	−173.80 (17)
C7—C1—C6—C5	66.2 (2)	C77—C51—C57—C62	104.6 (2)
C2—C1—C7—C8	144.75 (17)	C52—C51—C57—C62	−133.36 (19)
C27—C1—C7—C8	−92.8 (2)	C56—C51—C57—C62	−16.7 (2)
C6—C1—C7—C8	26.3 (2)	C77—C51—C57—C58	−73.9 (2)
C2—C1—C7—C12	−38.3 (2)	C52—C51—C57—C58	48.1 (2)
C27—C1—C7—C12	84.2 (2)	C56—C51—C57—C58	164.73 (17)
C6—C1—C7—C12	−156.71 (17)	C62—C57—C58—C59	−0.1 (3)
C12—C7—C8—C9	0.2 (3)	C51—C57—C58—C59	178.53 (18)
C1—C7—C8—C9	177.33 (17)	C57—C58—C59—C60	−0.1 (3)
C7—C8—C9—C10	0.9 (3)	C58—C59—C60—C61	0.3 (3)
C8—C9—C10—C11	−1.1 (3)	C58—C59—C60—N3	−178.48 (19)
C8—C9—C10—N1	179.32 (18)	C63—N3—C60—C61	145.8 (2)
C13—N1—C10—C11	139.7 (2)	C70—N3—C60—C61	−36.3 (3)
C20—N1—C10—C11	−38.4 (3)	C63—N3—C60—C59	−35.4 (3)
C13—N1—C10—C9	−40.8 (3)	C70—N3—C60—C59	142.4 (2)
C20—N1—C10—C9	141.2 (2)	C59—C60—C61—C62	−0.5 (3)
C9—C10—C11—C12	0.3 (3)	N3—C60—C61—C62	178.38 (19)
N1—C10—C11—C12	179.90 (18)	C60—C61—C62—C57	0.3 (3)
C10—C11—C12—C7	0.8 (3)	C58—C57—C62—C61	0.0 (3)
C8—C7—C12—C11	−1.0 (3)	C51—C57—C62—C61	−178.62 (18)
C1—C7—C12—C11	−178.15 (17)	C60—N3—C63—C64	−41.9 (3)
C10—N1—C13—C14	−26.7 (3)	C70—N3—C63—C64	140.3 (2)
C20—N1—C13—C14	151.3 (2)	C60—N3—C63—C68	139.3 (2)
C10—N1—C13—C18	154.10 (19)	C70—N3—C63—C68	−38.6 (3)
C20—N1—C13—C18	−27.8 (3)	C68—C63—C64—C65	1.0 (3)
C18—C13—C14—C15	−0.6 (3)	N3—C63—C64—C65	−177.9 (2)
N1—C13—C14—C15	−179.78 (19)	C63—C64—C65—C66	1.1 (3)
C13—C14—C15—C16	0.6 (3)	C69—O5—C66—C67	−174.7 (2)
C19—O1—C16—C15	−6.9 (3)	C69—O5—C66—C65	5.5 (3)
C19—O1—C16—C17	174.5 (2)	C64—C65—C66—O5	177.85 (19)
C14—C15—C16—O1	−178.41 (19)	C64—C65—C66—C67	−1.9 (3)
C14—C15—C16—C17	0.1 (3)	O5—C66—C67—C68	−179.1 (2)
O1—C16—C17—C18	177.87 (18)	C65—C66—C67—C68	0.7 (3)
C15—C16—C17—C18	−0.8 (3)	C66—C67—C68—C63	1.4 (4)
C16—C17—C18—C13	0.8 (3)	C64—C63—C68—C67	−2.2 (3)
C14—C13—C18—C17	−0.1 (3)	N3—C63—C68—C67	176.6 (2)
N1—C13—C18—C17	179.11 (19)	C63—N3—C70—C71	−57.9 (3)
C10—N1—C20—C25	−60.9 (3)	C60—N3—C70—C71	124.2 (2)
C13—N1—C20—C25	121.0 (2)	C63—N3—C70—C75	122.6 (2)
C10—N1—C20—C21	118.2 (2)	C60—N3—C70—C75	−55.4 (3)
C13—N1—C20—C21	−59.9 (3)	C75—C70—C71—C72	0.2 (4)
C25—C20—C21—C22	−0.1 (3)	N3—C70—C71—C72	−179.4 (2)
N1—C20—C21—C22	−179.28 (19)	C70—C71—C72—C73	1.4 (4)
C20—C21—C22—C23	0.4 (3)	C71—C72—C73—O6	179.4 (2)
C26—O2—C23—C24	−2.7 (3)	C71—C72—C73—C74	−1.5 (4)
C26—O2—C23—C22	179.1 (2)	C76B—O6—C73—C72	−1.9 (7)
C21—C22—C23—O2	177.85 (19)	C76A—O6—C73—C72	2.3 (14)
C21—C22—C23—C24	−0.4 (3)	C76B—O6—C73—C74	178.9 (6)
O2—C23—C24—C25	−178.1 (2)	C76A—O6—C73—C74	−176.9 (14)
C22—C23—C24—C25	0.0 (3)	C72—C73—C74—C75	0.2 (4)
C21—C20—C25—C24	−0.3 (3)	O6—C73—C74—C75	179.4 (2)
N1—C20—C25—C24	178.9 (2)	C73—C74—C75—C70	1.4 (4)
C23—C24—C25—C20	0.3 (3)	C71—C70—C75—C74	−1.5 (4)
C2—C1—C27—C28	11.0 (2)	N3—C70—C75—C74	178.0 (2)
C7—C1—C27—C28	−110.9 (2)	C52—C51—C77—C78	157.98 (17)
C6—C1—C27—C28	127.67 (19)	C56—C51—C77—C78	38.5 (2)
C2—C1—C27—C32	−169.30 (17)	C57—C51—C77—C78	−82.6 (2)
C7—C1—C27—C32	68.8 (2)	C52—C51—C77—C82	−26.1 (2)
C6—C1—C27—C32	−52.6 (2)	C56—C51—C77—C82	−145.58 (18)
C32—C27—C28—C29	0.3 (3)	C57—C51—C77—C82	93.4 (2)
C1—C27—C28—C29	180.00 (17)	C82—C77—C78—C79	2.2 (3)
C27—C28—C29—C30	−0.5 (3)	C51—C77—C78—C79	178.38 (18)
C28—C29—C30—C31	0.5 (3)	C77—C78—C79—C80	−1.2 (3)
C28—C29—C30—N2	179.80 (19)	C78—C79—C80—C81	−1.3 (3)
C40—N2—C30—C29	−141.4 (2)	C78—C79—C80—N4	179.00 (18)
C33—N2—C30—C29	43.8 (3)	C90—N4—C80—C79	−140.6 (2)
C40—N2—C30—C31	37.9 (3)	C83—N4—C80—C79	34.7 (3)
C33—N2—C30—C31	−136.9 (2)	C90—N4—C80—C81	39.7 (3)
C29—C30—C31—C32	−0.3 (3)	C83—N4—C80—C81	−145.0 (2)
N2—C30—C31—C32	−179.6 (2)	C79—C80—C81—C82	2.7 (3)
C30—C31—C32—C27	0.1 (3)	N4—C80—C81—C82	−177.59 (19)
C28—C27—C32—C31	−0.1 (3)	C80—C81—C82—C77	−1.7 (3)
C1—C27—C32—C31	−179.83 (18)	C78—C77—C82—C81	−0.8 (3)
C30—N2—C33—C34	46.6 (3)	C51—C77—C82—C81	−176.90 (18)
C40—N2—C33—C34	−128.4 (2)	C80—N4—C83—C88	−120.0 (2)
C30—N2—C33—C38	−136.4 (2)	C90—N4—C83—C88	55.4 (3)
C40—N2—C33—C38	48.6 (3)	C80—N4—C83—C84	60.3 (3)
C38—C33—C34—C35	1.1 (4)	C90—N4—C83—C84	−124.3 (2)
N2—C33—C34—C35	178.1 (2)	C88—C83—C84—C85	−0.3 (3)
C33—C34—C35—C36	−1.6 (4)	N4—C83—C84—C85	179.40 (19)
C39—O3—C36—C35	5.6 (3)	C83—C84—C85—C86	−0.6 (3)
C39—O3—C36—C37	−174.6 (2)	C89—O7—C86—C87	−1.0 (3)
C34—C35—C36—O3	−179.6 (2)	C89—O7—C86—C85	−179.3 (2)
C34—C35—C36—C37	0.7 (3)	C84—C85—C86—O7	179.08 (19)
O3—C36—C37—C38	−179.0 (2)	C84—C85—C86—C87	0.7 (3)
C35—C36—C37—C38	0.8 (4)	O7—C86—C87—C88	−178.1 (2)
C36—C37—C38—C33	−1.3 (4)	C85—C86—C87—C88	0.0 (3)
C34—C33—C38—C37	0.4 (4)	C84—C83—C88—C87	1.0 (3)
N2—C33—C38—C37	−176.7 (2)	N4—C83—C88—C87	−178.6 (2)
C30—N2—C40—C41	49.9 (3)	C86—C87—C88—C83	−0.9 (3)
C33—N2—C40—C41	−135.1 (2)	C80—N4—C90—C95	24.6 (3)
C30—N2—C40—C45	−131.9 (2)	C83—N4—C90—C95	−150.7 (2)
C33—N2—C40—C45	43.1 (3)	C80—N4—C90—C91	−155.4 (2)
C45—C40—C41—C42	−0.5 (3)	C83—N4—C90—C91	29.3 (3)
N2—C40—C41—C42	177.76 (19)	C95—C90—C91—C92	−0.3 (3)
C40—C41—C42—C43	−1.1 (3)	N4—C90—C91—C92	179.70 (19)
C46—O4—C43—C44	171.35 (19)	C90—C91—C92—C93	−2.0 (3)
C46—O4—C43—C42	−9.2 (3)	C96—O8—C93—C94	−2.6 (3)
C41—C42—C43—O4	−177.57 (19)	C96—O8—C93—C92	176.8 (2)
C41—C42—C43—C44	1.9 (3)	C91—C92—C93—C94	2.6 (3)
O4—C43—C44—C45	178.46 (18)	C91—C92—C93—O8	−176.92 (18)
C42—C43—C44—C45	−1.0 (3)	O8—C93—C94—C95	178.7 (2)
C43—C44—C45—C40	−0.6 (3)	C92—C93—C94—C95	−0.8 (3)
C41—C40—C45—C44	1.3 (3)	C91—C90—C95—C94	2.1 (3)
N2—C40—C45—C44	−176.9 (2)	N4—C90—C95—C94	−177.9 (2)
C77—C51—C52—C53	−68.1 (2)	C93—C94—C95—C90	−1.6 (3)

Summary of the short contacts in the crystal packing structure of TAPC-OMe top

Atoms	Distance (Å)	Atoms	Distance (Å)
Hydrogen bonds
C26—H···O5	2.415	C82—H···O1	2.689
C6—H···O1	2.478	C95—H···O6	2.868
C52—H···O8	2.475

C—H···π(Ph) interactions
C39—H···π(C35)	2.822	C8—H···π(C93)	2.661
C39—H···π(C14)	2.778	C65—H···π(C32)	2.883
C69—H···π(C28)	2.859	C82—H···π(C16)	2.838
C69—H···π(C29)	2.883	C2—H···π(C22)	2.884
C8—H···π(C92)	2.870

Distances were calculated by using the Mercury program (Macrae et al., 2008).

Photophysical and electrochemical properties of TAPC and TAPC-OMe top

	Abs. (nm)^a	Em. (nm)^a	Stokes shift (nm)	PLQY (%)^b	E_ox (V)^c	Hammett parameter (σ)^d	HOMO (eV)>^e	LUMO (eV)^f	Band Gap (eV)^g
TAPC	308	374	66	2.4	0.61	CH₃ = -0.17	-5.30	-1.88	3.42
TAPC-OMe	306	392	86	1.4	0.46	OMe = -0.27	-4.85	-1.56	3.29

Notes: (a) Measured in 5 µM dichloromethane solution. (b) PLQY were measured by using anthracene as a reference compound (Melhuish, 1961). (c) Measured in 2 mM dichloromethane solution containing n-Bu₄NPF₆ as an electrolyte. (d) Parameters were obtained from the reference (Hansch et al., 1991). (e) EQUATION; a correction value of 0.11 V was used for TAPC (reported value of E_HOMO = -5.3 eV) (Zhang et al., 1999). (f) EQUATION. (g) Calculated from the onset point in the UV–Vis spectra.

Selected electronic transitions from the TD-DFT calculation for TAPC and two symmetry-independent molecules of TAPC-OMe top

	Wavelength (nm)	Osc. strength	Major contributions
TAPC	324	0.4716	HOMO → L+2 (44%), H-1 → L+1 (19%), HOMO → LUMO (18%), HOMO → L+1 (12%),
TAPC-OMe, Molecule 1	328	0.5877	HOMO → L+2 (78%), H-1 → LUMO (5%), H-1 → L+3 (5%)
TAPC-OMe, Molecule 2	321	0.5019	HOMO → L+2 (90%), H-1 → L+1 (2%), H-1 → L+8 (3%)

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Tuning the energy level of TAPC: crystal structure and photophysical and electrochemical properties of 4,4′-(cyclo­hexane-1,1-di­yl)bis­[N,N-bis­(4-meth­oxy­phen­yl)aniline]

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Tuning the energy level of TAPC: crystal structure and photophysical and electrochemical properties of 4,4′-(cyclohexane-1,1-diyl)bis[N,N-bis(4-methoxyphenyl)aniline]