organic compounds
(4Z,5E,9E,10Z)-N4,N5,N9,N10-Tetrakis(2,6-diisopropylphenyl)pyrene-4,5,9,10-tetraimine
a105 E. 24th St., Austin, TX 78704, USA
*Correspondence e-mail: acowley@cm.utexas.edu
The title molecule, C64H74N4, consists of a pyrene backbone with imine moieties located on the 4-, 5-, 9-, and 10-positions of the ring system. The on these are sterically bulky 2,6-diisopropylphenyl units. As a consequence, the backbone itself is twisted, with an angle of 15.29 (6)° between the mean planes (r.m.s. deviations = 0.006 and 0.009 Å) of the phenyl units. The N=C—C=N units are significantly twisted and feature torsion angles of −48.8 (2) and −46.3 (3)°. The non-planarity of the backbone and short C—N distances [ranging from 1.281 (2) to 1.285 (2) Å] indicate the lack of conjugation in the molecule and double-bond nature of the Weak intramolecular and intermolecular C—H⋯π interactions are observed.
Keywords: crystal structure; pyrene; imine; single-crystal X-ray.
CCDC reference: 1470114
Structure description
Imine–metal complexes have been widely studied as ligands in organometallic catalysts (Xing et al., 2014; Song et al., 2013; Zhao et al., 2015; Gao et al., 2012). In addition, the syntheses and structures of a variety of phenanthrene-based imine complexes have been reported (Cherkasov et al., 2012) and the of the asymmetric (Z)-N-{(E)-10-[(2,6-diisopropylphenyl)imino]-9,10-dihydrophenanthren-9-ylidene}-2,6-dimethylaniline complex has been reported by Li et al. (2012). Our lab has been active in the study of bis-imino acenaphenthene-based complexes due to the unique redox characteristics of the ligand. Herein is reported the structure of a sterically hindered diimine molecule based on the pyrene backbone (Figs. 1 and 2). The structure shows a twisted rather than planar backbone, indicating the lack of conjugation across the ring system. The adopt an E–Z, E–Z conformation with relatively large torsion angles across the N—C—C—N fragments.
There are three weak intramolecular C—H⋯π interactions observed (Table 1), one between the pyrene backbone and phenyl imine substituents, and two between isopropyl H atoms and neighboring phenyl substituents. In the crystal, a weak C—H⋯π interaction links inversion-related molecules.
Synthesis and crystallization
Pyrene-4,5,9,10-tetraone was synthesized according to literature procedures (Hu et al., 2005). 2,6-Diisopropylaniline was purchased from Sigma Aldrich and purified by distillation under vacuum. TiCl4 was purchased as a 1 M solution in DCM and used as received. The tetraone (52.3 mg; 0.2 mmol) and aniline (0.4375 g; 2.5 mmol) were added to a Schlenk flask and pumped under vacuum for one h. To this, 100 ml of dry toluene was added via cannulation. To this, 0.4 ml of 1.0 M TiCl4 was added via syringe. This was allowed to continue overnight, followed by careful neutralization of excess TiCl4 by hydrolysis with 20 mL of deionized water. This mixture was washed three times with toluene (50 mL) to extract the product. The resulting organic solution was then washed three times with water (50 mL) and the aqueous layers discarded. The resulting organic solution was then dried over magnesium sulfate and excess toluene solvent removed in vacuo, leaving a crude product with excess aniline oil. The oil was removed by additional washing in acetonitrile and crystals were produced by slow evaporation of a of the product in dichloromethane (yield: 62.5 mg; 0.07 mmol; 35%).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1470114
10.1107/S2414314616004843/lh4003sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616004843/lh4003Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616004843/lh4003Isup3.cml
Imine metal complexes have been widely studied as ligands in organometallic catalysts (Xing et al., 2014; Song et al., 2013; Zhao et al., 2015; Gao et al., 2012). In addition, the syntheses and structures of a variety of phenanthrene based imine complexes have been reported (Cherkasov et al., 2012) and the
of the asymmetric (Z)—N-{(E)-10-[(2,6-Diisopropylphenyl)- imino]-9,10-dihydrophenanthren-9-ylidene}-2,6-dimethylaniline complex has been reported by Li et al. (2012). Our lab has been active in the study of bis-imino acenaphenthene based complexes due to the unique redox characteristics of the ligand. Herein is reported the structure of a sterically hindered diimine molecule based on the pyrene backbone. The structure shows a twisted rather than planar backbone, indicating the lack of conjugation across the ring system. The adopt an E—Z, E—Z conformation with relatively large torsion angles across the N–C–C–N fragments.Pyrene-4,5,9,10-tetraone was synthesized according to literature procedures (Hu et al., 2005). 2,6-diisopropylaniline was purchased from Sigma Aldrich and purified by distillation under vacuum. TiCl4 was purchased as a 1 M solution in DCM and used as received. The tetraone (52.3 mg; 0.2 mmol) and aniline (0.4375 g; 2.5 mmol) were added to a Schlenk flask and pumped under vacuum for one hour. To this, 100 mL of dry toluene was added via cannulation. To this, 0.4 mL of 1.0 M TiCl4 was added via syringe. This
was allowed to continue overnight, followed by careful neutralization of excess TiCl4 with 20 mL of deionized water. The solution was washed three times with toluene and aqueous layers discarded. This was further washed with three aliquots (50 mL) of water and dried of magnesium sulfate. The organic solvent was removed in vacuo, leaving a crude product with excell aniline oil. The oil was removed by additional washing in acetonitrile. Crystals were afforded by slow evaporation of a of the product in DCM.Crystal data, data collection and structure
details are summarized in Table 1. All C and N atoms were refined anisotripically without restraint. H atoms were placed in calculated postions with C–H = 0.93-0.96Å and included in the in a riding-model approximation with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl).Pyrene-4,5,9,10-tetraone was synthesized according to literature procedures (Hu et al., 2005). 2,6-Diisopropylaniline was purchased from Sigma Aldrich and purified by distillation under vacuum. TiCl4 was purchased as a 1 M solution in DCM and used as received. The tetraone (52.3 mg; 0.2 mmol) and aniline (0.4375 g; 2.5 mmol) were added to a Schlenk flask and pumped under vacuum for one hour. To this, 100 ml of dry toluene was added via cannulation. To this, 0.4 ml of 1.0 M TiCl4 was added via syringe. This
was allowed to continue overnight, followed by careful neutralization of excess TiCl4 by hydrolysis with 20 mL of deionized water. This mixture was washed three times with toluene (50 mL) to extract the product. The resulting organic solution was then washed three times with water (50 mL) and the aqueous layers discarded. The resulting organic solution was then dried over magnesium sulfate and excess toluene solvent removed in vacuo, leaving a crude product with excess aniline oil. The oil was removed by additional washing in acetonitrile and crystals were produced by slow evaporation of a of the product in dichloromethane (yield: 62.5 mg; 0.07 mmol; 35%).Imine–metal complexes have been widely studied as ligands in organometallic catalysts (Xing et al., 2014; Song et al., 2013; Zhao et al., 2015; Gao et al., 2012). In addition, the syntheses and structures of a variety of phenanthrene-based imine complexes have been reported (Cherkasov et al., 2012) and the
of the asymmetric (Z)-N-{(E)-10-[(2,6-diisopropylphenyl)imino]-9,10-dihydrophenanthren-9-ylidene}-2,6-dimethylaniline complex has been reported by Li et al. (2012). Our lab has been active in the study of bis-imino acenaphenthene-based complexes due to the unique redox characteristics of the ligand. Herein is reported the structure of a sterically hindered diimine molecule based on the pyrene backbone (Figs. 1 and 2). The structure shows a twisted rather than planar backbone, indicating the lack of conjugation across the ring system. The adopt an E–Z, E–Z conformation with relatively large torsion angles across the N—C—C—N fragments.There are three weak intramolecular C—H···π interactions observed (Table 1), one between the pyrene backbone and phenyl imine substituents, and two between isopropyl H atoms and neighboring phenyl substituents. In the crystal, a weak C—H···π interaction links inversion-related molecules.
Data collection: CrystalClear (Rigaku, 2008); cell
CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2015 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010) and WinGX (Farrugia, 2012).Fig. 1. The molecular structure of the title compound, shown with 50% probability ellipsoids for non-H atoms. For clarity, the H atoms and the isopropyl groups have been removed. | |
Fig. 2. Alternative view of the title compound, shown with 50% probability ellipsoids for non-H atoms. For clarity, the H atoms and the isopropyl groups have been removed. |
C64H74N4 | F(000) = 1944 |
Mr = 899.27 | Dx = 1.074 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71075 Å |
a = 14.527 (4) Å | Cell parameters from 12747 reflections |
b = 10.721 (3) Å | θ = 1.5–31.8° |
c = 36.004 (10) Å | µ = 0.06 mm−1 |
β = 97.459 (3)° | T = 223 K |
V = 5560 (3) Å3 | Chip, red |
Z = 4 | 0.30 × 0.28 × 0.25 mm |
Rigaku SCXMini diffractometer | 12755 independent reflections |
Radiation source: fine-focus sealed tube | 9576 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 1.5° |
dtprofit.ref scans | h = −18→18 |
Absorption correction: multi-scan (ABSCOR; Higashi, 2001) | k = −13→13 |
Tmin = 0.875, Tmax = 1.000 | l = −46→46 |
55003 measured reflections |
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)] = 0.064 | H-atom parameters constrained |
wR(F2) = 0.175 | w = 1/[σ2(Fo2) + (0.0719P)2 + 1.9541P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
12755 reflections | Δρmax = 0.29 e Å−3 |
630 parameters | Δρmin = −0.26 e Å−3 |
0 restraints | Extinction correction: SHELXL2015 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0022 (4) |
C64H74N4 | V = 5560 (3) Å3 |
Mr = 899.27 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.527 (4) Å | µ = 0.06 mm−1 |
b = 10.721 (3) Å | T = 223 K |
c = 36.004 (10) Å | 0.30 × 0.28 × 0.25 mm |
β = 97.459 (3)° |
Rigaku SCXMini diffractometer | 12755 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 2001) | 9576 reflections with I > 2σ(I) |
Tmin = 0.875, Tmax = 1.000 | Rint = 0.049 |
55003 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.175 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.29 e Å−3 |
12755 reflections | Δρmin = −0.26 e Å−3 |
630 parameters |
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. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.49832 (11) | 0.51934 (15) | 0.12003 (4) | 0.0277 (3) | |
C2 | 0.48073 (11) | 0.50049 (16) | 0.07841 (5) | 0.0284 (3) | |
C3 | 0.41788 (11) | 0.39395 (16) | 0.06713 (4) | 0.0287 (3) | |
C4 | 0.42666 (12) | 0.32550 (17) | 0.03492 (5) | 0.0339 (4) | |
H4 | 0.4710 | 0.3481 | 0.0197 | 0.041* | |
C5 | 0.36908 (13) | 0.22307 (17) | 0.02536 (5) | 0.0371 (4) | |
H5 | 0.3760 | 0.1766 | 0.0041 | 0.045* | |
C6 | 0.30148 (13) | 0.19055 (17) | 0.04757 (5) | 0.0352 (4) | |
H6 | 0.2634 | 0.1222 | 0.0411 | 0.042* | |
C7 | 0.29020 (11) | 0.25977 (16) | 0.07959 (5) | 0.0305 (4) | |
C8 | 0.21651 (11) | 0.22783 (16) | 0.10310 (5) | 0.0318 (4) | |
C9 | 0.18629 (11) | 0.33671 (16) | 0.12526 (5) | 0.0313 (4) | |
C10 | 0.26231 (11) | 0.41920 (16) | 0.14303 (5) | 0.0314 (4) | |
C11 | 0.25731 (12) | 0.48532 (18) | 0.17612 (5) | 0.0378 (4) | |
H11 | 0.2056 | 0.4761 | 0.1886 | 0.045* | |
C12 | 0.32859 (13) | 0.56458 (19) | 0.19062 (5) | 0.0398 (4) | |
H12 | 0.3239 | 0.6087 | 0.2125 | 0.048* | |
C13 | 0.40675 (12) | 0.57830 (17) | 0.17261 (5) | 0.0346 (4) | |
H13 | 0.4540 | 0.6321 | 0.1824 | 0.042* | |
C14 | 0.41470 (11) | 0.51166 (16) | 0.13989 (5) | 0.0289 (3) | |
C15 | 0.34171 (11) | 0.43211 (15) | 0.12454 (4) | 0.0282 (3) | |
C16 | 0.34973 (11) | 0.36087 (15) | 0.09003 (4) | 0.0279 (3) | |
C17 | 0.61232 (11) | 0.52544 (16) | 0.17381 (5) | 0.0305 (4) | |
C18 | 0.65262 (12) | 0.63428 (17) | 0.19052 (5) | 0.0336 (4) | |
C19 | 0.68610 (13) | 0.63059 (19) | 0.22873 (5) | 0.0410 (4) | |
H19 | 0.7121 | 0.7019 | 0.2405 | 0.049* | |
C20 | 0.68105 (14) | 0.5223 (2) | 0.24931 (5) | 0.0458 (5) | |
H20 | 0.7036 | 0.5212 | 0.2747 | 0.055* | |
C21 | 0.64232 (14) | 0.4153 (2) | 0.23205 (5) | 0.0433 (5) | |
H21 | 0.6394 | 0.3432 | 0.2462 | 0.052* | |
C22 | 0.60764 (12) | 0.41313 (17) | 0.19406 (5) | 0.0351 (4) | |
C23 | 0.65868 (13) | 0.75380 (18) | 0.16818 (5) | 0.0390 (4) | |
H23 | 0.6312 | 0.7373 | 0.1423 | 0.047* | |
C24 | 0.60355 (17) | 0.8601 (2) | 0.18337 (7) | 0.0585 (6) | |
H24A | 0.5399 | 0.8354 | 0.1828 | 0.088* | |
H24B | 0.6069 | 0.9330 | 0.1681 | 0.088* | |
H24C | 0.6294 | 0.8785 | 0.2087 | 0.088* | |
C25 | 0.75956 (15) | 0.7927 (2) | 0.16737 (6) | 0.0518 (5) | |
H25A | 0.7888 | 0.8069 | 0.1925 | 0.078* | |
H25B | 0.7614 | 0.8680 | 0.1531 | 0.078* | |
H25C | 0.7919 | 0.7278 | 0.1560 | 0.078* | |
C26 | 0.56948 (13) | 0.29313 (18) | 0.17513 (6) | 0.0395 (4) | |
H26 | 0.5170 | 0.3162 | 0.1565 | 0.047* | |
C27 | 0.64194 (18) | 0.2308 (2) | 0.15424 (8) | 0.0658 (7) | |
H27A | 0.6646 | 0.2900 | 0.1376 | 0.099* | |
H27B | 0.6143 | 0.1615 | 0.1401 | 0.099* | |
H27C | 0.6926 | 0.2018 | 0.1719 | 0.099* | |
C28 | 0.5334 (2) | 0.1993 (3) | 0.20199 (8) | 0.0752 (8) | |
H28A | 0.5844 | 0.1679 | 0.2190 | 0.113* | |
H28B | 0.5033 | 0.1314 | 0.1879 | 0.113* | |
H28C | 0.4898 | 0.2399 | 0.2159 | 0.113* | |
C29 | 0.57577 (12) | 0.66810 (16) | 0.06262 (5) | 0.0313 (4) | |
C30 | 0.53572 (13) | 0.78722 (17) | 0.06514 (5) | 0.0380 (4) | |
C31 | 0.59601 (15) | 0.89013 (19) | 0.06964 (6) | 0.0439 (5) | |
H31 | 0.5713 | 0.9696 | 0.0714 | 0.053* | |
C32 | 0.69093 (15) | 0.87621 (19) | 0.07145 (6) | 0.0462 (5) | |
H32 | 0.7294 | 0.9458 | 0.0741 | 0.055* | |
C33 | 0.72863 (14) | 0.7581 (2) | 0.06927 (5) | 0.0439 (5) | |
H33 | 0.7927 | 0.7494 | 0.0708 | 0.053* | |
C34 | 0.67281 (12) | 0.65180 (18) | 0.06483 (5) | 0.0355 (4) | |
C35 | 0.71522 (14) | 0.5223 (2) | 0.06276 (6) | 0.0447 (5) | |
H35 | 0.6664 | 0.4611 | 0.0654 | 0.054* | |
C36 | 0.7492 (2) | 0.4998 (3) | 0.02474 (7) | 0.0849 (10) | |
H36A | 0.6970 | 0.4998 | 0.0054 | 0.127* | |
H36B | 0.7802 | 0.4206 | 0.0250 | 0.127* | |
H36C | 0.7915 | 0.5648 | 0.0200 | 0.127* | |
C37 | 0.79362 (16) | 0.5003 (3) | 0.09455 (7) | 0.0621 (6) | |
H37A | 0.8439 | 0.5563 | 0.0919 | 0.093* | |
H37B | 0.8150 | 0.4157 | 0.0936 | 0.093* | |
H37C | 0.7713 | 0.5150 | 0.1181 | 0.093* | |
C38 | 0.43110 (14) | 0.8061 (2) | 0.06214 (7) | 0.0497 (5) | |
H38 | 0.4031 | 0.7251 | 0.0665 | 0.060* | |
C39 | 0.40294 (19) | 0.8972 (3) | 0.09120 (8) | 0.0752 (8) | |
H39A | 0.4269 | 0.8688 | 0.1158 | 0.113* | |
H39B | 0.3365 | 0.9019 | 0.0890 | 0.113* | |
H39C | 0.4278 | 0.9783 | 0.0870 | 0.113* | |
C40 | 0.39214 (18) | 0.8485 (3) | 0.02283 (8) | 0.0814 (9) | |
H40A | 0.4213 | 0.9252 | 0.0171 | 0.122* | |
H40B | 0.3264 | 0.8611 | 0.0216 | 0.122* | |
H40C | 0.4042 | 0.7858 | 0.0050 | 0.122* | |
C41 | 0.11614 (14) | 0.07997 (17) | 0.12561 (6) | 0.0431 (5) | |
C42 | 0.14708 (16) | 0.0448 (2) | 0.16259 (7) | 0.0508 (5) | |
C43 | 0.07912 (18) | 0.0067 (2) | 0.18480 (8) | 0.0623 (7) | |
H43 | 0.0971 | −0.0157 | 0.2096 | 0.075* | |
C44 | −0.01338 (18) | 0.0019 (2) | 0.17045 (9) | 0.0668 (8) | |
H44 | −0.0574 | −0.0205 | 0.1858 | 0.080* | |
C45 | −0.04085 (17) | 0.0303 (2) | 0.13339 (9) | 0.0645 (7) | |
H45 | −0.1033 | 0.0234 | 0.1238 | 0.077* | |
C46 | 0.02251 (14) | 0.0690 (2) | 0.10983 (7) | 0.0529 (6) | |
C47 | 0.24984 (17) | 0.0398 (2) | 0.17811 (7) | 0.0598 (6) | |
H47 | 0.2847 | 0.0760 | 0.1592 | 0.072* | |
C48 | 0.2740 (2) | 0.1124 (4) | 0.21356 (10) | 0.0971 (11) | |
H48A | 0.2531 | 0.1969 | 0.2097 | 0.146* | |
H48B | 0.3400 | 0.1114 | 0.2205 | 0.146* | |
H48C | 0.2442 | 0.0753 | 0.2332 | 0.146* | |
C49 | 0.2818 (3) | −0.0966 (3) | 0.18420 (11) | 0.1078 (13) | |
H49A | 0.3479 | −0.0988 | 0.1911 | 0.162* | |
H49B | 0.2655 | −0.1429 | 0.1615 | 0.162* | |
H49C | 0.2519 | −0.1329 | 0.2039 | 0.162* | |
C50 | −0.00859 (16) | 0.0977 (3) | 0.06890 (8) | 0.0675 (7) | |
H50 | 0.0453 | 0.1274 | 0.0576 | 0.081* | |
C51 | −0.0829 (2) | 0.1989 (3) | 0.06418 (12) | 0.1088 (13) | |
H51A | −0.1371 | 0.1702 | 0.0743 | 0.163* | |
H51B | −0.0988 | 0.2174 | 0.0380 | 0.163* | |
H51C | −0.0596 | 0.2728 | 0.0772 | 0.163* | |
C52 | −0.0476 (3) | −0.0191 (3) | 0.04723 (10) | 0.0965 (10) | |
H52A | 0.0019 | −0.0769 | 0.0451 | 0.145* | |
H52B | −0.0758 | 0.0048 | 0.0227 | 0.145* | |
H52C | −0.0933 | −0.0580 | 0.0605 | 0.145* | |
C53 | 0.06311 (12) | 0.46672 (17) | 0.13839 (6) | 0.0380 (4) | |
C54 | 0.01332 (13) | 0.45625 (19) | 0.16917 (6) | 0.0422 (4) | |
C55 | −0.01907 (15) | 0.5656 (2) | 0.18385 (8) | 0.0575 (6) | |
H55 | −0.0503 | 0.5616 | 0.2048 | 0.069* | |
C56 | −0.00538 (17) | 0.6805 (2) | 0.16772 (9) | 0.0669 (7) | |
H56 | −0.0261 | 0.7527 | 0.1783 | 0.080* | |
C57 | 0.03855 (15) | 0.6884 (2) | 0.13618 (8) | 0.0597 (6) | |
H57 | 0.0452 | 0.7659 | 0.1252 | 0.072* | |
C58 | 0.07356 (13) | 0.58199 (19) | 0.12018 (6) | 0.0449 (5) | |
C59 | −0.00367 (13) | 0.33123 (19) | 0.18684 (6) | 0.0434 (5) | |
H59 | 0.0224 | 0.2662 | 0.1721 | 0.052* | |
C60 | 0.04326 (18) | 0.3211 (3) | 0.22711 (7) | 0.0658 (7) | |
H60A | 0.1091 | 0.3306 | 0.2276 | 0.099* | |
H60B | 0.0301 | 0.2410 | 0.2371 | 0.099* | |
H60C | 0.0201 | 0.3855 | 0.2420 | 0.099* | |
C61 | −0.10869 (15) | 0.3066 (2) | 0.18514 (7) | 0.0587 (6) | |
H61A | −0.1358 | 0.3687 | 0.1996 | 0.088* | |
H61B | −0.1184 | 0.2254 | 0.1952 | 0.088* | |
H61C | −0.1373 | 0.3104 | 0.1596 | 0.088* | |
C62 | 0.11638 (14) | 0.5925 (2) | 0.08387 (7) | 0.0504 (5) | |
H62 | 0.1510 | 0.5153 | 0.0811 | 0.061* | |
C63 | 0.04002 (19) | 0.6008 (3) | 0.05049 (8) | 0.0797 (8) | |
H63A | 0.0014 | 0.5279 | 0.0499 | 0.120* | |
H63B | 0.0677 | 0.6058 | 0.0277 | 0.120* | |
H63C | 0.0030 | 0.6738 | 0.0529 | 0.120* | |
C64 | 0.18473 (19) | 0.7004 (3) | 0.08374 (9) | 0.0724 (8) | |
H64A | 0.1525 | 0.7779 | 0.0855 | 0.109* | |
H64B | 0.2124 | 0.6987 | 0.0609 | 0.109* | |
H64C | 0.2323 | 0.6925 | 0.1047 | 0.109* | |
N1 | 0.58376 (9) | 0.52720 (13) | 0.13434 (4) | 0.0301 (3) | |
N2 | 0.51647 (10) | 0.56282 (13) | 0.05351 (4) | 0.0314 (3) | |
N3 | 0.18357 (10) | 0.11668 (14) | 0.10194 (4) | 0.0379 (4) | |
N4 | 0.09839 (10) | 0.35489 (14) | 0.12354 (4) | 0.0355 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0269 (8) | 0.0274 (8) | 0.0290 (8) | −0.0020 (6) | 0.0045 (6) | 0.0005 (6) |
C2 | 0.0239 (8) | 0.0328 (8) | 0.0291 (8) | 0.0006 (6) | 0.0052 (6) | 0.0013 (6) |
C3 | 0.0272 (8) | 0.0320 (9) | 0.0266 (8) | −0.0004 (6) | 0.0025 (6) | 0.0029 (6) |
C4 | 0.0354 (9) | 0.0377 (10) | 0.0294 (9) | −0.0043 (7) | 0.0071 (7) | 0.0006 (7) |
C5 | 0.0465 (10) | 0.0352 (9) | 0.0304 (9) | −0.0041 (8) | 0.0081 (8) | −0.0023 (7) |
C6 | 0.0391 (9) | 0.0303 (9) | 0.0359 (9) | −0.0053 (7) | 0.0035 (7) | −0.0001 (7) |
C7 | 0.0287 (8) | 0.0311 (9) | 0.0318 (9) | −0.0001 (7) | 0.0043 (7) | 0.0044 (7) |
C8 | 0.0279 (8) | 0.0324 (9) | 0.0350 (9) | −0.0025 (7) | 0.0039 (7) | 0.0022 (7) |
C9 | 0.0279 (8) | 0.0325 (9) | 0.0343 (9) | −0.0012 (7) | 0.0073 (7) | 0.0045 (7) |
C10 | 0.0267 (8) | 0.0321 (9) | 0.0359 (9) | 0.0000 (7) | 0.0063 (7) | 0.0001 (7) |
C11 | 0.0292 (9) | 0.0459 (11) | 0.0402 (10) | −0.0002 (8) | 0.0115 (7) | −0.0034 (8) |
C12 | 0.0361 (9) | 0.0484 (11) | 0.0359 (10) | 0.0000 (8) | 0.0090 (8) | −0.0094 (8) |
C13 | 0.0306 (9) | 0.0395 (10) | 0.0341 (9) | −0.0025 (7) | 0.0054 (7) | −0.0052 (7) |
C14 | 0.0243 (8) | 0.0343 (9) | 0.0281 (8) | 0.0005 (6) | 0.0035 (6) | 0.0026 (7) |
C15 | 0.0262 (8) | 0.0293 (8) | 0.0291 (8) | 0.0003 (6) | 0.0041 (6) | 0.0028 (6) |
C16 | 0.0262 (8) | 0.0285 (8) | 0.0288 (8) | 0.0006 (6) | 0.0025 (6) | 0.0037 (6) |
C17 | 0.0241 (8) | 0.0376 (9) | 0.0297 (8) | 0.0004 (7) | 0.0031 (6) | 0.0000 (7) |
C18 | 0.0290 (8) | 0.0381 (9) | 0.0330 (9) | −0.0013 (7) | 0.0020 (7) | −0.0017 (7) |
C19 | 0.0404 (10) | 0.0438 (11) | 0.0373 (10) | −0.0033 (8) | −0.0009 (8) | −0.0052 (8) |
C20 | 0.0488 (11) | 0.0546 (12) | 0.0313 (9) | 0.0025 (9) | −0.0048 (8) | 0.0014 (9) |
C21 | 0.0451 (11) | 0.0452 (11) | 0.0382 (10) | 0.0032 (9) | −0.0006 (8) | 0.0097 (8) |
C22 | 0.0301 (9) | 0.0376 (10) | 0.0373 (9) | 0.0008 (7) | 0.0027 (7) | 0.0021 (7) |
C23 | 0.0415 (10) | 0.0385 (10) | 0.0361 (10) | −0.0081 (8) | 0.0018 (8) | −0.0013 (8) |
C24 | 0.0597 (14) | 0.0387 (11) | 0.0781 (16) | 0.0006 (10) | 0.0125 (12) | 0.0065 (11) |
C25 | 0.0497 (12) | 0.0643 (14) | 0.0414 (11) | −0.0186 (11) | 0.0056 (9) | −0.0056 (10) |
C26 | 0.0365 (10) | 0.0354 (10) | 0.0452 (11) | −0.0004 (8) | −0.0002 (8) | 0.0048 (8) |
C27 | 0.0604 (15) | 0.0536 (14) | 0.0872 (19) | −0.0082 (11) | 0.0236 (13) | −0.0212 (13) |
C28 | 0.095 (2) | 0.0570 (15) | 0.0794 (19) | −0.0236 (14) | 0.0319 (16) | −0.0015 (13) |
C29 | 0.0337 (9) | 0.0347 (9) | 0.0260 (8) | −0.0053 (7) | 0.0060 (7) | 0.0030 (7) |
C30 | 0.0403 (10) | 0.0359 (10) | 0.0392 (10) | −0.0028 (8) | 0.0101 (8) | 0.0045 (8) |
C31 | 0.0550 (12) | 0.0354 (10) | 0.0432 (11) | −0.0054 (9) | 0.0129 (9) | −0.0004 (8) |
C32 | 0.0527 (12) | 0.0428 (11) | 0.0437 (11) | −0.0188 (9) | 0.0090 (9) | −0.0021 (9) |
C33 | 0.0363 (10) | 0.0544 (12) | 0.0413 (11) | −0.0126 (9) | 0.0064 (8) | 0.0006 (9) |
C34 | 0.0324 (9) | 0.0417 (10) | 0.0329 (9) | −0.0041 (8) | 0.0068 (7) | 0.0004 (7) |
C35 | 0.0343 (10) | 0.0482 (12) | 0.0518 (12) | 0.0001 (8) | 0.0063 (8) | 0.0006 (9) |
C36 | 0.107 (2) | 0.092 (2) | 0.0540 (15) | 0.0527 (19) | 0.0045 (15) | −0.0058 (14) |
C37 | 0.0494 (13) | 0.0716 (16) | 0.0642 (15) | 0.0124 (12) | 0.0028 (11) | 0.0099 (12) |
C38 | 0.0418 (11) | 0.0391 (11) | 0.0702 (14) | 0.0037 (9) | 0.0143 (10) | 0.0066 (10) |
C39 | 0.0639 (16) | 0.092 (2) | 0.0724 (18) | 0.0221 (15) | 0.0203 (13) | −0.0010 (15) |
C40 | 0.0537 (15) | 0.116 (3) | 0.0720 (18) | 0.0201 (16) | −0.0011 (13) | −0.0130 (17) |
C41 | 0.0406 (10) | 0.0294 (9) | 0.0630 (13) | −0.0035 (8) | 0.0206 (9) | 0.0035 (9) |
C42 | 0.0530 (12) | 0.0405 (11) | 0.0640 (14) | −0.0004 (9) | 0.0274 (11) | 0.0076 (10) |
C43 | 0.0716 (16) | 0.0459 (13) | 0.0778 (17) | −0.0033 (11) | 0.0415 (14) | 0.0100 (11) |
C44 | 0.0644 (15) | 0.0380 (12) | 0.110 (2) | −0.0085 (11) | 0.0553 (16) | −0.0005 (13) |
C45 | 0.0450 (12) | 0.0430 (12) | 0.111 (2) | −0.0094 (10) | 0.0317 (14) | 0.0022 (13) |
C46 | 0.0382 (11) | 0.0375 (11) | 0.0859 (17) | −0.0055 (9) | 0.0190 (11) | 0.0022 (11) |
C47 | 0.0591 (14) | 0.0753 (17) | 0.0482 (13) | 0.0044 (12) | 0.0192 (11) | 0.0159 (12) |
C48 | 0.078 (2) | 0.104 (3) | 0.112 (3) | −0.0106 (19) | 0.0232 (19) | −0.031 (2) |
C49 | 0.103 (3) | 0.098 (3) | 0.113 (3) | 0.046 (2) | −0.022 (2) | −0.023 (2) |
C50 | 0.0380 (12) | 0.0681 (16) | 0.095 (2) | −0.0067 (11) | 0.0022 (12) | 0.0140 (14) |
C51 | 0.095 (2) | 0.079 (2) | 0.140 (3) | 0.0176 (19) | −0.032 (2) | −0.005 (2) |
C52 | 0.116 (3) | 0.074 (2) | 0.101 (3) | −0.0035 (19) | 0.022 (2) | −0.0123 (18) |
C53 | 0.0244 (8) | 0.0344 (9) | 0.0555 (11) | −0.0022 (7) | 0.0070 (8) | −0.0006 (8) |
C54 | 0.0287 (9) | 0.0413 (10) | 0.0585 (12) | −0.0031 (8) | 0.0131 (8) | −0.0022 (9) |
C55 | 0.0453 (12) | 0.0497 (13) | 0.0836 (17) | −0.0031 (10) | 0.0313 (12) | −0.0075 (12) |
C56 | 0.0530 (14) | 0.0407 (12) | 0.114 (2) | 0.0018 (10) | 0.0372 (14) | −0.0095 (13) |
C57 | 0.0443 (12) | 0.0361 (11) | 0.103 (2) | 0.0007 (9) | 0.0272 (12) | 0.0060 (11) |
C58 | 0.0283 (9) | 0.0387 (10) | 0.0690 (14) | −0.0016 (8) | 0.0117 (9) | 0.0054 (9) |
C59 | 0.0388 (10) | 0.0439 (11) | 0.0500 (11) | −0.0009 (8) | 0.0149 (9) | 0.0027 (9) |
C60 | 0.0584 (14) | 0.0793 (18) | 0.0592 (15) | 0.0043 (13) | 0.0055 (11) | 0.0046 (13) |
C61 | 0.0427 (12) | 0.0576 (14) | 0.0776 (16) | −0.0086 (10) | 0.0148 (11) | 0.0158 (12) |
C62 | 0.0392 (11) | 0.0470 (12) | 0.0667 (14) | −0.0006 (9) | 0.0128 (10) | 0.0155 (10) |
C63 | 0.0599 (16) | 0.098 (2) | 0.0799 (19) | −0.0061 (15) | 0.0019 (14) | 0.0099 (17) |
C64 | 0.0633 (16) | 0.0670 (17) | 0.090 (2) | −0.0177 (13) | 0.0231 (14) | 0.0145 (14) |
N1 | 0.0270 (7) | 0.0328 (7) | 0.0302 (7) | −0.0024 (6) | 0.0030 (5) | 0.0004 (6) |
N2 | 0.0291 (7) | 0.0342 (8) | 0.0312 (7) | −0.0024 (6) | 0.0054 (6) | 0.0024 (6) |
N3 | 0.0331 (8) | 0.0346 (8) | 0.0470 (9) | −0.0040 (6) | 0.0094 (7) | 0.0022 (7) |
N4 | 0.0291 (7) | 0.0343 (8) | 0.0443 (9) | −0.0019 (6) | 0.0096 (6) | 0.0039 (7) |
C1—N1 | 1.283 (2) | C36—H36B | 0.9600 |
C1—C14 | 1.490 (2) | C36—H36C | 0.9600 |
C1—C2 | 1.501 (2) | C37—H37A | 0.9600 |
C2—N2 | 1.281 (2) | C37—H37B | 0.9600 |
C2—C3 | 1.486 (2) | C37—H37C | 0.9600 |
C3—C4 | 1.392 (2) | C38—C40 | 1.524 (4) |
C3—C16 | 1.414 (2) | C38—C39 | 1.526 (3) |
C4—C5 | 1.396 (2) | C38—H38 | 0.9800 |
C4—H4 | 0.9300 | C39—H39A | 0.9600 |
C5—C6 | 1.389 (3) | C39—H39B | 0.9600 |
C5—H5 | 0.9300 | C39—H39C | 0.9600 |
C6—C7 | 1.398 (2) | C40—H40A | 0.9600 |
C6—H6 | 0.9300 | C40—H40B | 0.9600 |
C7—C16 | 1.407 (2) | C40—H40C | 0.9600 |
C7—C8 | 1.488 (2) | C41—C42 | 1.401 (3) |
C8—N3 | 1.283 (2) | C41—C46 | 1.409 (3) |
C8—C9 | 1.511 (2) | C41—N3 | 1.434 (2) |
C9—N4 | 1.285 (2) | C42—C43 | 1.409 (3) |
C9—C10 | 1.492 (2) | C42—C47 | 1.525 (3) |
C10—C11 | 1.396 (2) | C43—C44 | 1.377 (4) |
C10—C15 | 1.412 (2) | C43—H43 | 0.9300 |
C11—C12 | 1.388 (3) | C44—C45 | 1.376 (4) |
C11—H11 | 0.9300 | C44—H44 | 0.9300 |
C12—C13 | 1.386 (2) | C45—C46 | 1.393 (3) |
C12—H12 | 0.9300 | C45—H45 | 0.9300 |
C13—C14 | 1.395 (2) | C46—C50 | 1.516 (4) |
C13—H13 | 0.9300 | C47—C48 | 1.497 (4) |
C14—C15 | 1.416 (2) | C47—C49 | 1.541 (4) |
C15—C16 | 1.476 (2) | C47—H47 | 0.9800 |
C17—C18 | 1.405 (2) | C48—H48A | 0.9600 |
C17—C22 | 1.414 (2) | C48—H48B | 0.9600 |
C17—N1 | 1.428 (2) | C48—H48C | 0.9600 |
C18—C19 | 1.399 (3) | C49—H49A | 0.9600 |
C18—C23 | 1.522 (3) | C49—H49B | 0.9600 |
C19—C20 | 1.384 (3) | C49—H49C | 0.9600 |
C19—H19 | 0.9300 | C50—C51 | 1.524 (4) |
C20—C21 | 1.388 (3) | C50—C52 | 1.544 (4) |
C20—H20 | 0.9300 | C50—H50 | 0.9800 |
C21—C22 | 1.395 (3) | C51—H51A | 0.9600 |
C21—H21 | 0.9300 | C51—H51B | 0.9600 |
C22—C26 | 1.526 (3) | C51—H51C | 0.9600 |
C23—C25 | 1.528 (3) | C52—H52A | 0.9600 |
C23—C24 | 1.534 (3) | C52—H52B | 0.9600 |
C23—H23 | 0.9800 | C52—H52C | 0.9600 |
C24—H24A | 0.9600 | C53—C54 | 1.404 (3) |
C24—H24B | 0.9600 | C53—C58 | 1.416 (3) |
C24—H24C | 0.9600 | C53—N4 | 1.434 (2) |
C25—H25A | 0.9600 | C54—C55 | 1.393 (3) |
C25—H25B | 0.9600 | C54—C59 | 1.517 (3) |
C25—H25C | 0.9600 | C55—C56 | 1.387 (3) |
C26—C27 | 1.525 (3) | C55—H55 | 0.9300 |
C26—C28 | 1.534 (3) | C56—C57 | 1.376 (4) |
C26—H26 | 0.9800 | C56—H56 | 0.9300 |
C27—H27A | 0.9600 | C57—C58 | 1.403 (3) |
C27—H27B | 0.9600 | C57—H57 | 0.9300 |
C27—H27C | 0.9600 | C58—C62 | 1.523 (3) |
C28—H28A | 0.9600 | C59—C60 | 1.524 (3) |
C28—H28B | 0.9600 | C59—C61 | 1.542 (3) |
C28—H28C | 0.9600 | C59—H59 | 0.9800 |
C29—C30 | 1.411 (3) | C60—H60A | 0.9600 |
C29—C34 | 1.412 (2) | C60—H60B | 0.9600 |
C29—N2 | 1.432 (2) | C60—H60C | 0.9600 |
C30—C31 | 1.405 (3) | C61—H61A | 0.9600 |
C30—C38 | 1.523 (3) | C61—H61B | 0.9600 |
C31—C32 | 1.380 (3) | C61—H61C | 0.9600 |
C31—H31 | 0.9300 | C62—C64 | 1.525 (3) |
C32—C33 | 1.386 (3) | C62—C63 | 1.529 (4) |
C32—H32 | 0.9300 | C62—H62 | 0.9800 |
C33—C34 | 1.395 (3) | C63—H63A | 0.9600 |
C33—H33 | 0.9300 | C63—H63B | 0.9600 |
C34—C35 | 1.525 (3) | C63—H63C | 0.9600 |
C35—C37 | 1.524 (3) | C64—H64A | 0.9600 |
C35—C36 | 1.533 (3) | C64—H64B | 0.9600 |
C35—H35 | 0.9800 | C64—H64C | 0.9600 |
C36—H36A | 0.9600 | ||
N1—C1—C14 | 128.11 (15) | H37A—C37—H37B | 109.5 |
N1—C1—C2 | 116.12 (14) | C35—C37—H37C | 109.5 |
C14—C1—C2 | 115.35 (14) | H37A—C37—H37C | 109.5 |
N2—C2—C3 | 120.00 (15) | H37B—C37—H37C | 109.5 |
N2—C2—C1 | 126.64 (15) | C30—C38—C40 | 110.63 (18) |
C3—C2—C1 | 113.30 (13) | C30—C38—C39 | 113.0 (2) |
C4—C3—C16 | 120.04 (15) | C40—C38—C39 | 110.2 (2) |
C4—C3—C2 | 120.91 (15) | C30—C38—H38 | 107.6 |
C16—C3—C2 | 119.04 (15) | C40—C38—H38 | 107.6 |
C3—C4—C5 | 120.21 (16) | C39—C38—H38 | 107.6 |
C3—C4—H4 | 119.9 | C38—C39—H39A | 109.5 |
C5—C4—H4 | 119.9 | C38—C39—H39B | 109.5 |
C6—C5—C4 | 120.08 (17) | H39A—C39—H39B | 109.5 |
C6—C5—H5 | 120.0 | C38—C39—H39C | 109.5 |
C4—C5—H5 | 120.0 | H39A—C39—H39C | 109.5 |
C5—C6—C7 | 120.58 (16) | H39B—C39—H39C | 109.5 |
C5—C6—H6 | 119.7 | C38—C40—H40A | 109.5 |
C7—C6—H6 | 119.7 | C38—C40—H40B | 109.5 |
C6—C7—C16 | 119.69 (15) | H40A—C40—H40B | 109.5 |
C6—C7—C8 | 121.11 (15) | C38—C40—H40C | 109.5 |
C16—C7—C8 | 119.20 (15) | H40A—C40—H40C | 109.5 |
N3—C8—C7 | 119.21 (16) | H40B—C40—H40C | 109.5 |
N3—C8—C9 | 127.02 (15) | C42—C41—C46 | 122.31 (19) |
C7—C8—C9 | 113.73 (14) | C42—C41—N3 | 118.64 (18) |
N4—C9—C10 | 127.31 (16) | C46—C41—N3 | 118.8 (2) |
N4—C9—C8 | 116.52 (15) | C41—C42—C43 | 117.1 (2) |
C10—C9—C8 | 115.76 (14) | C41—C42—C47 | 122.38 (18) |
C11—C10—C15 | 119.27 (15) | C43—C42—C47 | 120.4 (2) |
C11—C10—C9 | 123.30 (15) | C44—C43—C42 | 121.3 (3) |
C15—C10—C9 | 117.41 (15) | C44—C43—H43 | 119.4 |
C12—C11—C10 | 120.86 (16) | C42—C43—H43 | 119.4 |
C12—C11—H11 | 119.6 | C45—C44—C43 | 120.1 (2) |
C10—C11—H11 | 119.6 | C45—C44—H44 | 119.9 |
C13—C12—C11 | 120.35 (17) | C43—C44—H44 | 119.9 |
C13—C12—H12 | 119.8 | C44—C45—C46 | 121.7 (2) |
C11—C12—H12 | 119.8 | C44—C45—H45 | 119.2 |
C12—C13—C14 | 120.20 (16) | C46—C45—H45 | 119.2 |
C12—C13—H13 | 119.9 | C45—C46—C41 | 117.3 (2) |
C14—C13—H13 | 119.9 | C45—C46—C50 | 121.0 (2) |
C13—C14—C15 | 119.88 (15) | C41—C46—C50 | 121.68 (19) |
C13—C14—C1 | 122.62 (15) | C48—C47—C42 | 113.8 (2) |
C15—C14—C1 | 117.50 (15) | C48—C47—C49 | 109.8 (3) |
C10—C15—C14 | 119.42 (15) | C42—C47—C49 | 110.3 (2) |
C10—C15—C16 | 120.33 (15) | C48—C47—H47 | 107.5 |
C14—C15—C16 | 120.23 (14) | C42—C47—H47 | 107.5 |
C7—C16—C3 | 119.35 (15) | C49—C47—H47 | 107.5 |
C7—C16—C15 | 120.71 (14) | C47—C48—H48A | 109.5 |
C3—C16—C15 | 119.94 (15) | C47—C48—H48B | 109.5 |
C18—C17—C22 | 122.11 (16) | H48A—C48—H48B | 109.5 |
C18—C17—N1 | 117.78 (15) | C47—C48—H48C | 109.5 |
C22—C17—N1 | 119.83 (15) | H48A—C48—H48C | 109.5 |
C19—C18—C17 | 118.03 (17) | H48B—C48—H48C | 109.5 |
C19—C18—C23 | 120.47 (16) | C47—C49—H49A | 109.5 |
C17—C18—C23 | 121.50 (15) | C47—C49—H49B | 109.5 |
C20—C19—C18 | 120.95 (18) | H49A—C49—H49B | 109.5 |
C20—C19—H19 | 119.5 | C47—C49—H49C | 109.5 |
C18—C19—H19 | 119.5 | H49A—C49—H49C | 109.5 |
C19—C20—C21 | 119.98 (18) | H49B—C49—H49C | 109.5 |
C19—C20—H20 | 120.0 | C46—C50—C51 | 111.8 (3) |
C21—C20—H20 | 120.0 | C46—C50—C52 | 111.7 (2) |
C20—C21—C22 | 121.77 (18) | C51—C50—C52 | 108.2 (2) |
C20—C21—H21 | 119.1 | C46—C50—H50 | 108.4 |
C22—C21—H21 | 119.1 | C51—C50—H50 | 108.4 |
C21—C22—C17 | 117.13 (17) | C52—C50—H50 | 108.4 |
C21—C22—C26 | 121.07 (17) | C50—C51—H51A | 109.5 |
C17—C22—C26 | 121.77 (16) | C50—C51—H51B | 109.5 |
C18—C23—C25 | 111.20 (16) | H51A—C51—H51B | 109.5 |
C18—C23—C24 | 111.62 (16) | C50—C51—H51C | 109.5 |
C25—C23—C24 | 110.51 (17) | H51A—C51—H51C | 109.5 |
C18—C23—H23 | 107.8 | H51B—C51—H51C | 109.5 |
C25—C23—H23 | 107.8 | C50—C52—H52A | 109.5 |
C24—C23—H23 | 107.8 | C50—C52—H52B | 109.5 |
C23—C24—H24A | 109.5 | H52A—C52—H52B | 109.5 |
C23—C24—H24B | 109.5 | C50—C52—H52C | 109.5 |
H24A—C24—H24B | 109.5 | H52A—C52—H52C | 109.5 |
C23—C24—H24C | 109.5 | H52B—C52—H52C | 109.5 |
H24A—C24—H24C | 109.5 | C54—C53—C58 | 122.16 (18) |
H24B—C24—H24C | 109.5 | C54—C53—N4 | 118.22 (16) |
C23—C25—H25A | 109.5 | C58—C53—N4 | 119.47 (17) |
C23—C25—H25B | 109.5 | C55—C54—C53 | 117.78 (19) |
H25A—C25—H25B | 109.5 | C55—C54—C59 | 120.21 (18) |
C23—C25—H25C | 109.5 | C53—C54—C59 | 121.99 (17) |
H25A—C25—H25C | 109.5 | C56—C55—C54 | 121.0 (2) |
H25B—C25—H25C | 109.5 | C56—C55—H55 | 119.5 |
C27—C26—C22 | 110.83 (16) | C54—C55—H55 | 119.5 |
C27—C26—C28 | 109.8 (2) | C57—C56—C55 | 120.5 (2) |
C22—C26—C28 | 113.91 (18) | C57—C56—H56 | 119.7 |
C27—C26—H26 | 107.3 | C55—C56—H56 | 119.7 |
C22—C26—H26 | 107.3 | C56—C57—C58 | 121.4 (2) |
C28—C26—H26 | 107.3 | C56—C57—H57 | 119.3 |
C26—C27—H27A | 109.5 | C58—C57—H57 | 119.3 |
C26—C27—H27B | 109.5 | C57—C58—C53 | 116.94 (19) |
H27A—C27—H27B | 109.5 | C57—C58—C62 | 120.17 (19) |
C26—C27—H27C | 109.5 | C53—C58—C62 | 122.84 (18) |
H27A—C27—H27C | 109.5 | C54—C59—C60 | 112.61 (19) |
H27B—C27—H27C | 109.5 | C54—C59—C61 | 110.40 (17) |
C26—C28—H28A | 109.5 | C60—C59—C61 | 110.10 (18) |
C26—C28—H28B | 109.5 | C54—C59—H59 | 107.9 |
H28A—C28—H28B | 109.5 | C60—C59—H59 | 107.9 |
C26—C28—H28C | 109.5 | C61—C59—H59 | 107.9 |
H28A—C28—H28C | 109.5 | C59—C60—H60A | 109.5 |
H28B—C28—H28C | 109.5 | C59—C60—H60B | 109.5 |
C30—C29—C34 | 121.68 (16) | H60A—C60—H60B | 109.5 |
C30—C29—N2 | 119.16 (15) | C59—C60—H60C | 109.5 |
C34—C29—N2 | 118.80 (16) | H60A—C60—H60C | 109.5 |
C31—C30—C29 | 117.52 (17) | H60B—C60—H60C | 109.5 |
C31—C30—C38 | 120.37 (18) | C59—C61—H61A | 109.5 |
C29—C30—C38 | 122.10 (17) | C59—C61—H61B | 109.5 |
C32—C31—C30 | 121.65 (19) | H61A—C61—H61B | 109.5 |
C32—C31—H31 | 119.2 | C59—C61—H61C | 109.5 |
C30—C31—H31 | 119.2 | H61A—C61—H61C | 109.5 |
C31—C32—C33 | 119.72 (18) | H61B—C61—H61C | 109.5 |
C31—C32—H32 | 120.1 | C58—C62—C64 | 113.4 (2) |
C33—C32—H32 | 120.1 | C58—C62—C63 | 110.09 (18) |
C32—C33—C34 | 121.63 (18) | C64—C62—C63 | 111.1 (2) |
C32—C33—H33 | 119.2 | C58—C62—H62 | 107.3 |
C34—C33—H33 | 119.2 | C64—C62—H62 | 107.3 |
C33—C34—C29 | 117.80 (18) | C63—C62—H62 | 107.3 |
C33—C34—C35 | 121.10 (17) | C62—C63—H63A | 109.5 |
C29—C34—C35 | 121.10 (16) | C62—C63—H63B | 109.5 |
C37—C35—C34 | 111.79 (18) | H63A—C63—H63B | 109.5 |
C37—C35—C36 | 110.53 (19) | C62—C63—H63C | 109.5 |
C34—C35—C36 | 111.44 (18) | H63A—C63—H63C | 109.5 |
C37—C35—H35 | 107.6 | H63B—C63—H63C | 109.5 |
C34—C35—H35 | 107.6 | C62—C64—H64A | 109.5 |
C36—C35—H35 | 107.6 | C62—C64—H64B | 109.5 |
C35—C36—H36A | 109.5 | H64A—C64—H64B | 109.5 |
C35—C36—H36B | 109.5 | C62—C64—H64C | 109.5 |
H36A—C36—H36B | 109.5 | H64A—C64—H64C | 109.5 |
C35—C36—H36C | 109.5 | H64B—C64—H64C | 109.5 |
H36A—C36—H36C | 109.5 | C1—N1—C17 | 122.66 (14) |
H36B—C36—H36C | 109.5 | C2—N2—C29 | 122.49 (14) |
C35—C37—H37A | 109.5 | C8—N3—C41 | 121.07 (16) |
C35—C37—H37B | 109.5 | C9—N4—C53 | 120.64 (15) |
N1—C1—C2—N2 | −48.8 (2) | C34—C29—C30—C38 | 178.96 (17) |
C14—C1—C2—N2 | 138.04 (17) | N2—C29—C30—C38 | 5.9 (3) |
N1—C1—C2—C3 | 128.57 (16) | C29—C30—C31—C32 | 0.2 (3) |
C14—C1—C2—C3 | −44.60 (19) | C38—C30—C31—C32 | −178.28 (19) |
N2—C2—C3—C4 | 28.3 (2) | C30—C31—C32—C33 | −0.8 (3) |
C1—C2—C3—C4 | −149.28 (16) | C31—C32—C33—C34 | 0.7 (3) |
N2—C2—C3—C16 | −153.03 (16) | C32—C33—C34—C29 | −0.1 (3) |
C1—C2—C3—C16 | 29.4 (2) | C32—C33—C34—C35 | −179.54 (18) |
C16—C3—C4—C5 | −0.8 (3) | C30—C29—C34—C33 | −0.6 (3) |
C2—C3—C4—C5 | 177.87 (16) | N2—C29—C34—C33 | 172.46 (16) |
C3—C4—C5—C6 | 1.3 (3) | C30—C29—C34—C35 | 178.89 (17) |
C4—C5—C6—C7 | 0.1 (3) | N2—C29—C34—C35 | −8.1 (2) |
C5—C6—C7—C16 | −2.0 (3) | C33—C34—C35—C37 | 49.3 (3) |
C5—C6—C7—C8 | 178.46 (16) | C29—C34—C35—C37 | −130.14 (19) |
C6—C7—C8—N3 | 22.8 (3) | C33—C34—C35—C36 | −74.9 (3) |
C16—C7—C8—N3 | −156.74 (16) | C29—C34—C35—C36 | 105.6 (2) |
C6—C7—C8—C9 | −155.04 (16) | C31—C30—C38—C40 | 79.0 (3) |
C16—C7—C8—C9 | 25.4 (2) | C29—C30—C38—C40 | −99.4 (2) |
N3—C8—C9—N4 | −46.3 (3) | C31—C30—C38—C39 | −45.1 (3) |
C7—C8—C9—N4 | 131.38 (16) | C29—C30—C38—C39 | 136.5 (2) |
N3—C8—C9—C10 | 140.50 (18) | C46—C41—C42—C43 | −5.0 (3) |
C7—C8—C9—C10 | −41.8 (2) | N3—C41—C42—C43 | −178.65 (19) |
N4—C9—C10—C11 | 37.2 (3) | C46—C41—C42—C47 | 171.5 (2) |
C8—C9—C10—C11 | −150.49 (17) | N3—C41—C42—C47 | −2.2 (3) |
N4—C9—C10—C15 | −141.28 (18) | C41—C42—C43—C44 | 1.3 (3) |
C8—C9—C10—C15 | 31.1 (2) | C47—C42—C43—C44 | −175.3 (2) |
C15—C10—C11—C12 | 1.0 (3) | C42—C43—C44—C45 | 2.4 (4) |
C9—C10—C11—C12 | −177.43 (17) | C43—C44—C45—C46 | −2.5 (4) |
C10—C11—C12—C13 | −0.8 (3) | C44—C45—C46—C41 | −1.0 (3) |
C11—C12—C13—C14 | −0.5 (3) | C44—C45—C46—C50 | 178.9 (2) |
C12—C13—C14—C15 | 1.5 (3) | C42—C41—C46—C45 | 4.9 (3) |
C12—C13—C14—C1 | −177.92 (17) | N3—C41—C46—C45 | 178.52 (19) |
N1—C1—C14—C13 | 37.8 (3) | C42—C41—C46—C50 | −175.1 (2) |
C2—C1—C14—C13 | −149.99 (16) | N3—C41—C46—C50 | −1.4 (3) |
N1—C1—C14—C15 | −141.67 (18) | C41—C42—C47—C48 | 127.0 (3) |
C2—C1—C14—C15 | 30.5 (2) | C43—C42—C47—C48 | −56.6 (3) |
C11—C10—C15—C14 | 0.1 (2) | C41—C42—C47—C49 | −109.0 (3) |
C9—C10—C15—C14 | 178.56 (15) | C43—C42—C47—C49 | 67.3 (3) |
C11—C10—C15—C16 | 178.48 (16) | C45—C46—C50—C51 | 57.7 (3) |
C9—C10—C15—C16 | −3.0 (2) | C41—C46—C50—C51 | −122.4 (3) |
C13—C14—C15—C10 | −1.3 (2) | C45—C46—C50—C52 | −63.7 (3) |
C1—C14—C15—C10 | 178.19 (15) | C41—C46—C50—C52 | 116.2 (3) |
C13—C14—C15—C16 | −179.73 (15) | C58—C53—C54—C55 | −5.8 (3) |
C1—C14—C15—C16 | −0.2 (2) | N4—C53—C54—C55 | 178.76 (19) |
C6—C7—C16—C3 | 2.4 (2) | C58—C53—C54—C59 | 175.47 (18) |
C8—C7—C16—C3 | −177.99 (15) | N4—C53—C54—C59 | 0.0 (3) |
C6—C7—C16—C15 | −177.48 (15) | C53—C54—C55—C56 | 2.2 (3) |
C8—C7—C16—C15 | 2.1 (2) | C59—C54—C55—C56 | −179.0 (2) |
C4—C3—C16—C7 | −1.1 (2) | C54—C55—C56—C57 | 1.7 (4) |
C2—C3—C16—C7 | −179.76 (15) | C55—C56—C57—C58 | −2.2 (4) |
C4—C3—C16—C15 | 178.85 (15) | C56—C57—C58—C53 | −1.2 (3) |
C2—C3—C16—C15 | 0.2 (2) | C56—C57—C58—C62 | 176.1 (2) |
C10—C15—C16—C7 | −14.3 (2) | C54—C53—C58—C57 | 5.3 (3) |
C14—C15—C16—C7 | 164.07 (15) | N4—C53—C58—C57 | −179.36 (18) |
C10—C15—C16—C3 | 165.74 (15) | C54—C53—C58—C62 | −171.93 (18) |
C14—C15—C16—C3 | −15.8 (2) | N4—C53—C58—C62 | 3.4 (3) |
C22—C17—C18—C19 | −2.1 (3) | C55—C54—C59—C60 | −62.9 (3) |
N1—C17—C18—C19 | −176.02 (15) | C53—C54—C59—C60 | 115.8 (2) |
C22—C17—C18—C23 | 178.90 (16) | C55—C54—C59—C61 | 60.6 (3) |
N1—C17—C18—C23 | 5.0 (2) | C53—C54—C59—C61 | −120.7 (2) |
C17—C18—C19—C20 | 1.1 (3) | C57—C58—C62—C64 | 46.7 (3) |
C23—C18—C19—C20 | −179.91 (18) | C53—C58—C62—C64 | −136.2 (2) |
C18—C19—C20—C21 | 0.0 (3) | C57—C58—C62—C63 | −78.5 (3) |
C19—C20—C21—C22 | −0.1 (3) | C53—C58—C62—C63 | 98.6 (2) |
C20—C21—C22—C17 | −0.9 (3) | C14—C1—N1—C17 | 2.3 (3) |
C20—C21—C22—C26 | 177.08 (18) | C2—C1—N1—C17 | −169.90 (15) |
C18—C17—C22—C21 | 2.0 (3) | C18—C17—N1—C1 | −113.95 (19) |
N1—C17—C22—C21 | 175.80 (16) | C22—C17—N1—C1 | 72.0 (2) |
C18—C17—C22—C26 | −175.96 (16) | C3—C2—N2—C29 | 178.53 (15) |
N1—C17—C22—C26 | −2.2 (2) | C1—C2—N2—C29 | −4.3 (3) |
C19—C18—C23—C25 | 62.7 (2) | C30—C29—N2—C2 | −86.7 (2) |
C17—C18—C23—C25 | −118.32 (19) | C34—C29—N2—C2 | 100.1 (2) |
C19—C18—C23—C24 | −61.2 (2) | C7—C8—N3—C41 | 176.58 (16) |
C17—C18—C23—C24 | 117.8 (2) | C9—C8—N3—C41 | −5.9 (3) |
C21—C22—C26—C27 | −98.8 (2) | C42—C41—N3—C8 | −82.3 (2) |
C17—C22—C26—C27 | 79.0 (2) | C46—C41—N3—C8 | 103.8 (2) |
C21—C22—C26—C28 | 25.5 (3) | C10—C9—N4—C53 | 2.6 (3) |
C17—C22—C26—C28 | −156.6 (2) | C8—C9—N4—C53 | −169.70 (15) |
C34—C29—C30—C31 | 0.5 (3) | C54—C53—N4—C9 | −114.88 (19) |
N2—C29—C30—C31 | −172.49 (16) | C58—C53—N4—C9 | 69.6 (2) |
Cg1, Cg2 and Cg3 are the centroids of the C29–C34, C53–C58 and C41–C46 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···Cg1i | 0.93 | 2.61 | 3.327 (2) | 134 |
C11—H11···Cg2 | 0.93 | 2.93 | 3.469 (2) | 118 |
C23—H23···Cg1 | 0.98 | 2.73 | 3.613 (2) | 149 |
C59—H59···Cg3 | 0.98 | 2.64 | 3.571 (2) | 158 |
Symmetry code: (i) −x, −y, −z. |
Cg1, Cg2 and Cg3 are the centroids of the C29–C34, C53–C58 and C41–C46 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···Cg1i | 0.93 | 2.61 | 3.327 (2) | 134 |
C11—H11···Cg2 | 0.93 | 2.93 | 3.469 (2) | 118 |
C23—H23···Cg1 | 0.98 | 2.73 | 3.613 (2) | 149 |
C59—H59···Cg3 | 0.98 | 2.64 | 3.571 (2) | 158 |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C64H74N4 |
Mr | 899.27 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 223 |
a, b, c (Å) | 14.527 (4), 10.721 (3), 36.004 (10) |
β (°) | 97.459 (3) |
V (Å3) | 5560 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.06 |
Crystal size (mm) | 0.30 × 0.28 × 0.25 |
Data collection | |
Diffractometer | Rigaku SCXMini |
Absorption correction | Multi-scan (ABSCOR; Higashi, 2001) |
Tmin, Tmax | 0.875, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 55003, 12755, 9576 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.175, 1.06 |
No. of reflections | 12755 |
No. of parameters | 630 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.26 |
Computer programs: CrystalClear (Rigaku, 2008), SIR97 (Altomare et al., 1999), SHELXL2015 (Sheldrick, 2015), Mercury (Macrae et al., 2006), publCIF (Westrip, 2010) and WinGX (Farrugia, 2012).
Acknowledgements
The present work was supported by the Robert A. Welch Foundation (grant F-0003).
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