Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110045725/su3052sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110045725/su3052Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110045725/su3052IIsup3.hkl |
CCDC references: 781692; 781693
The starting benzoins (IVa) (Breuer & Zincke, 1879) and (IVb) (Hahn et al., 1981) were synthesized via benzoin condensation from the corresponding benzaldehydes following the described procedures.
The bis(keto esters) (IIIa) and (IIIb) were synthesized as follows. To a refluxing solution of the corresponding benzoin (IVa) or (IVb) (20 mmol) and isophthaloyl dichloride (V) (2.03 g, 10 mmol) in dry toluene (20 ml, dried over sodium and freshly distilled before use), triethylamine (15 ml, 0.11 mol, dried over potassium hydroxide) was slowly added over a period of 3 h. After evaporation of the solvent, ethanol (10 ml) was added to the oily residue and the mixture stirred for 2 h. The solid which formed was collected and crystallized. For (IIIa), benzoin (IVa) (4.24 g, 20 mmol) was reacted; crystallization from 1,4-dioxane yielded a colourless powder (yield 40%; m.p. 440 K). For (IIIb), benzoin (IVb) (6.44 g, 20 mmol) was reacted; crystallization from 1,4-dioxane yielded a colourless powder; (yield 96%; m.p. 421 K).
The title bis-oxazoles (I) and (II) were synthesized as follows. The corresponding bis(keto ester) (IIIa) or (IIIb) (7.5 mmol) and ammonium acetate (3.46 g, 45 mmol) were dissolved in concentrated acetic acid (55.0 ml) and refluxed for 3.5 h. After cooling of the reaction mixture to room temperature, the precipitate which formed was collected, neutralized with aqueous sodium hydrogen carbonate, washed several times with water, dried and crystallized. For (I), compound (IIIa) (4.16 g) was used for the reaction; crystallization from 1,4-dioxane–acetonitrile (1:1, v/v) yielded colourless crystals (yield 88%; m.p. 476. For (II), compound (IIIb) (5.84 g) was used for the reaction; crystallization from 1,4-dioxane yielded a colourless powder (yield 93%; m.p. 585 K). [How were X-ray quality crystals obtained?]
Spectroscopic and other synthetic details for compounds (I) and (II) are available in the archived CIF.
H atoms were positioned geometrically and treated as riding, with C—H = 0.95 (aromatic) or 0.98 Å (aliphatic), and with Uiso(H) = kUeq(C), where k = 1.2 for aromatic H or k = 1.5 for aliphatic H.
For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C36H24N2O2 | F(000) = 2160 |
Mr = 516.57 | Dx = 1.300 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 7424 reflections |
a = 7.1523 (2) Å | θ = 2.6–30.8° |
b = 20.0145 (5) Å | µ = 0.08 mm−1 |
c = 36.8669 (8) Å | T = 153 K |
V = 5277.5 (2) Å3 | Prism, colourless |
Z = 8 | 0.48 × 0.34 × 0.17 mm |
Nonius Kappa APEXII CCD area-detector diffractometer | 10121 independent reflections |
Radiation source: fine-focus sealed tube | 5826 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
ϕ and ω scans | θmax = 33.3°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→11 |
Tmin = 0.962, Tmax = 0.986 | k = −30→30 |
80848 measured reflections | l = −56→56 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0842P)2] where P = (Fo2 + 2Fc2)/3 |
10121 reflections | (Δ/σ)max < 0.001 |
361 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C36H24N2O2 | V = 5277.5 (2) Å3 |
Mr = 516.57 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.1523 (2) Å | µ = 0.08 mm−1 |
b = 20.0145 (5) Å | T = 153 K |
c = 36.8669 (8) Å | 0.48 × 0.34 × 0.17 mm |
Nonius Kappa APEXII CCD area-detector diffractometer | 10121 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5826 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.986 | Rint = 0.062 |
80848 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.41 e Å−3 |
10121 reflections | Δρmin = −0.31 e Å−3 |
361 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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. All hydrogen atoms were included in the model in calculated positions and were refined as constrained to bonding atoms. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.34070 (12) | 0.12975 (5) | 0.29797 (2) | 0.0324 (2) | |
O2 | 0.29345 (12) | 0.06978 (5) | 0.12887 (2) | 0.0304 (2) | |
N1 | 0.24955 (14) | 0.04610 (5) | 0.26334 (3) | 0.0267 (2) | |
N2 | 0.34600 (13) | 0.16563 (5) | 0.10057 (3) | 0.0285 (2) | |
C1 | 0.31167 (16) | 0.10727 (7) | 0.26429 (3) | 0.0303 (3) | |
C2 | 0.23881 (16) | 0.02530 (6) | 0.29929 (3) | 0.0284 (3) | |
C3 | 0.29325 (16) | 0.07742 (6) | 0.32092 (3) | 0.0269 (3) | |
C4 | 0.16978 (18) | −0.04266 (6) | 0.30701 (4) | 0.0303 (3) | |
C5 | 0.0115 (2) | −0.06538 (7) | 0.28874 (4) | 0.0400 (3) | |
H5 | −0.0478 | −0.0373 | 0.2714 | 0.048* | |
C6 | −0.0605 (2) | −0.12849 (8) | 0.29553 (5) | 0.0502 (4) | |
H6 | −0.1684 | −0.1434 | 0.2829 | 0.060* | |
C7 | 0.0245 (2) | −0.16981 (8) | 0.32072 (5) | 0.0501 (4) | |
H7 | −0.0260 | −0.2127 | 0.3257 | 0.060* | |
C8 | 0.1828 (2) | −0.14840 (8) | 0.33853 (4) | 0.0459 (4) | |
H8 | 0.2415 | −0.1768 | 0.3557 | 0.055* | |
C9 | 0.2576 (2) | −0.08535 (7) | 0.33152 (4) | 0.0376 (3) | |
H9 | 0.3686 | −0.0715 | 0.3435 | 0.045* | |
C10 | 0.30172 (15) | 0.09160 (6) | 0.35982 (3) | 0.0256 (2) | |
C11 | 0.24179 (16) | 0.04549 (7) | 0.38594 (4) | 0.0299 (3) | |
H11 | 0.1939 | 0.0034 | 0.3785 | 0.036* | |
C12 | 0.25203 (17) | 0.06099 (7) | 0.42252 (4) | 0.0344 (3) | |
H12 | 0.2132 | 0.0290 | 0.4400 | 0.041* | |
C13 | 0.31812 (18) | 0.12244 (8) | 0.43388 (4) | 0.0383 (3) | |
H13 | 0.3237 | 0.1330 | 0.4590 | 0.046* | |
C14 | 0.37598 (19) | 0.16821 (7) | 0.40815 (4) | 0.0391 (3) | |
H14 | 0.4216 | 0.2106 | 0.4157 | 0.047* | |
C15 | 0.36829 (18) | 0.15319 (7) | 0.37157 (4) | 0.0331 (3) | |
H15 | 0.4089 | 0.1853 | 0.3543 | 0.040* | |
C16 | 0.35126 (15) | 0.14939 (6) | 0.23308 (3) | 0.0245 (2) | |
C17 | 0.41817 (17) | 0.21441 (7) | 0.23720 (3) | 0.0292 (3) | |
H17 | 0.4362 | 0.2324 | 0.2608 | 0.035* | |
C18 | 0.45837 (17) | 0.25270 (6) | 0.20688 (4) | 0.0310 (3) | |
H18 | 0.5052 | 0.2968 | 0.2098 | 0.037* | |
C19 | 0.43095 (17) | 0.22726 (6) | 0.17239 (3) | 0.0299 (3) | |
H19 | 0.4587 | 0.2538 | 0.1517 | 0.036* | |
C20 | 0.36241 (15) | 0.16247 (6) | 0.16802 (3) | 0.0252 (2) | |
C21 | 0.32302 (15) | 0.12367 (6) | 0.19838 (3) | 0.0251 (2) | |
H21 | 0.2767 | 0.0795 | 0.1954 | 0.030* | |
C22 | 0.33530 (16) | 0.13538 (7) | 0.13163 (3) | 0.0290 (3) | |
C23 | 0.31078 (15) | 0.11652 (6) | 0.07465 (3) | 0.0276 (3) | |
C24 | 0.27644 (15) | 0.05765 (7) | 0.09200 (3) | 0.0274 (3) | |
C25 | 0.32032 (15) | 0.13378 (6) | 0.03597 (3) | 0.0262 (2) | |
C26 | 0.25072 (17) | 0.19505 (7) | 0.02390 (4) | 0.0315 (3) | |
H26 | 0.1941 | 0.2248 | 0.0407 | 0.038* | |
C27 | 0.2632 (2) | 0.21307 (7) | −0.01227 (4) | 0.0378 (3) | |
H27 | 0.2138 | 0.2546 | −0.0202 | 0.045* | |
C28 | 0.34776 (19) | 0.17035 (7) | −0.03688 (4) | 0.0375 (3) | |
H28 | 0.3570 | 0.1828 | −0.0617 | 0.045* | |
C29 | 0.41888 (17) | 0.10962 (7) | −0.02544 (4) | 0.0336 (3) | |
H29 | 0.4775 | 0.0806 | −0.0423 | 0.040* | |
C30 | 0.40454 (16) | 0.09117 (7) | 0.01070 (3) | 0.0304 (3) | |
H30 | 0.4523 | 0.0492 | 0.0184 | 0.036* | |
C31 | 0.22631 (15) | −0.01121 (6) | 0.08223 (3) | 0.0277 (3) | |
C32 | 0.13254 (16) | −0.02558 (7) | 0.04994 (3) | 0.0297 (3) | |
H32 | 0.1048 | 0.0094 | 0.0334 | 0.036* | |
C33 | 0.07970 (17) | −0.09039 (7) | 0.04186 (4) | 0.0344 (3) | |
H33 | 0.0163 | −0.0997 | 0.0198 | 0.041* | |
C34 | 0.11886 (19) | −0.14184 (7) | 0.06584 (4) | 0.0396 (3) | |
H34 | 0.0809 | −0.1862 | 0.0604 | 0.048* | |
C35 | 0.21382 (19) | −0.12813 (8) | 0.09778 (4) | 0.0406 (3) | |
H35 | 0.2429 | −0.1634 | 0.1141 | 0.049* | |
C36 | 0.26673 (18) | −0.06315 (7) | 0.10610 (4) | 0.0341 (3) | |
H36 | 0.3307 | −0.0541 | 0.1281 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0335 (4) | 0.0368 (5) | 0.0270 (5) | 0.0004 (4) | 0.0023 (4) | 0.0018 (4) |
O2 | 0.0317 (4) | 0.0364 (5) | 0.0231 (5) | 0.0032 (4) | −0.0019 (3) | −0.0047 (4) |
N1 | 0.0318 (5) | 0.0264 (5) | 0.0220 (5) | 0.0033 (4) | 0.0055 (4) | 0.0011 (4) |
N2 | 0.0277 (4) | 0.0379 (6) | 0.0198 (5) | 0.0030 (4) | −0.0023 (4) | −0.0051 (4) |
C1 | 0.0272 (5) | 0.0398 (8) | 0.0240 (6) | 0.0067 (5) | 0.0035 (4) | 0.0029 (6) |
C2 | 0.0313 (5) | 0.0290 (6) | 0.0249 (6) | 0.0059 (5) | 0.0040 (5) | 0.0003 (5) |
C3 | 0.0262 (5) | 0.0304 (6) | 0.0242 (6) | 0.0033 (4) | 0.0027 (4) | 0.0033 (5) |
C4 | 0.0391 (6) | 0.0260 (6) | 0.0259 (6) | 0.0066 (5) | 0.0053 (5) | −0.0031 (5) |
C5 | 0.0511 (8) | 0.0317 (7) | 0.0372 (8) | 0.0004 (6) | −0.0044 (6) | −0.0026 (6) |
C6 | 0.0611 (9) | 0.0352 (8) | 0.0543 (10) | −0.0064 (7) | −0.0007 (8) | −0.0064 (7) |
C7 | 0.0663 (10) | 0.0257 (7) | 0.0583 (11) | 0.0016 (7) | 0.0147 (8) | −0.0028 (7) |
C8 | 0.0617 (9) | 0.0311 (7) | 0.0448 (9) | 0.0186 (7) | 0.0127 (7) | 0.0067 (7) |
C9 | 0.0435 (7) | 0.0336 (8) | 0.0358 (8) | 0.0127 (6) | 0.0045 (6) | 0.0003 (6) |
C10 | 0.0232 (5) | 0.0305 (6) | 0.0231 (6) | 0.0032 (4) | 0.0002 (4) | 0.0000 (5) |
C11 | 0.0288 (5) | 0.0325 (7) | 0.0283 (7) | −0.0012 (5) | 0.0032 (5) | −0.0009 (5) |
C12 | 0.0320 (6) | 0.0458 (8) | 0.0255 (7) | 0.0047 (6) | 0.0043 (5) | 0.0020 (6) |
C13 | 0.0367 (6) | 0.0507 (9) | 0.0275 (7) | 0.0079 (6) | −0.0042 (5) | −0.0083 (6) |
C14 | 0.0426 (7) | 0.0359 (8) | 0.0387 (8) | 0.0012 (6) | −0.0064 (6) | −0.0103 (6) |
C15 | 0.0352 (6) | 0.0300 (7) | 0.0340 (7) | −0.0003 (5) | −0.0009 (5) | −0.0010 (6) |
C16 | 0.0243 (5) | 0.0271 (6) | 0.0222 (6) | 0.0023 (4) | 0.0012 (4) | −0.0008 (5) |
C17 | 0.0323 (5) | 0.0317 (7) | 0.0235 (6) | 0.0008 (5) | 0.0002 (5) | −0.0068 (5) |
C18 | 0.0363 (6) | 0.0259 (6) | 0.0310 (7) | −0.0036 (5) | 0.0008 (5) | −0.0031 (5) |
C19 | 0.0330 (6) | 0.0306 (7) | 0.0261 (7) | 0.0012 (5) | 0.0012 (5) | 0.0033 (5) |
C20 | 0.0240 (5) | 0.0299 (6) | 0.0217 (6) | 0.0036 (4) | −0.0010 (4) | −0.0027 (5) |
C21 | 0.0253 (5) | 0.0252 (6) | 0.0247 (6) | 0.0006 (4) | −0.0008 (4) | −0.0027 (5) |
C22 | 0.0258 (5) | 0.0362 (7) | 0.0250 (6) | 0.0041 (5) | −0.0025 (4) | −0.0061 (5) |
C23 | 0.0257 (5) | 0.0349 (7) | 0.0222 (6) | 0.0039 (5) | −0.0025 (4) | −0.0033 (5) |
C24 | 0.0256 (5) | 0.0368 (7) | 0.0198 (6) | 0.0047 (5) | −0.0028 (4) | −0.0065 (5) |
C25 | 0.0258 (5) | 0.0303 (6) | 0.0225 (6) | −0.0016 (5) | −0.0023 (4) | −0.0023 (5) |
C26 | 0.0348 (6) | 0.0270 (6) | 0.0327 (7) | −0.0050 (5) | 0.0012 (5) | −0.0023 (5) |
C27 | 0.0450 (7) | 0.0287 (7) | 0.0396 (8) | −0.0066 (6) | 0.0012 (6) | 0.0081 (6) |
C28 | 0.0432 (7) | 0.0423 (8) | 0.0270 (7) | −0.0121 (6) | 0.0021 (5) | 0.0063 (6) |
C29 | 0.0328 (6) | 0.0424 (8) | 0.0255 (7) | −0.0034 (5) | 0.0019 (5) | −0.0027 (6) |
C30 | 0.0294 (5) | 0.0364 (7) | 0.0254 (7) | 0.0026 (5) | −0.0020 (5) | −0.0024 (5) |
C31 | 0.0270 (5) | 0.0326 (7) | 0.0235 (6) | 0.0032 (5) | 0.0016 (4) | −0.0020 (5) |
C32 | 0.0300 (5) | 0.0322 (7) | 0.0268 (7) | 0.0036 (5) | −0.0008 (5) | −0.0021 (5) |
C33 | 0.0321 (6) | 0.0372 (7) | 0.0338 (7) | −0.0001 (5) | −0.0005 (5) | −0.0067 (6) |
C34 | 0.0370 (6) | 0.0327 (7) | 0.0491 (9) | −0.0025 (6) | 0.0045 (6) | −0.0048 (7) |
C35 | 0.0422 (7) | 0.0372 (8) | 0.0424 (9) | 0.0013 (6) | 0.0024 (6) | 0.0100 (7) |
C36 | 0.0352 (6) | 0.0381 (8) | 0.0290 (7) | −0.0001 (5) | −0.0014 (5) | 0.0031 (6) |
O1—C1 | 1.3367 (15) | C16—C17 | 1.3949 (17) |
O1—C3 | 1.3887 (15) | C17—C18 | 1.3854 (18) |
O2—C22 | 1.3505 (16) | C17—H17 | 0.9500 |
O2—C24 | 1.3860 (14) | C18—C19 | 1.3839 (18) |
N1—C1 | 1.3029 (17) | C18—H18 | 0.9500 |
N1—C2 | 1.3912 (16) | C19—C20 | 1.3955 (18) |
N2—C22 | 1.2974 (16) | C19—H19 | 0.9500 |
N2—C23 | 1.3940 (16) | C20—C21 | 1.3910 (17) |
C1—C16 | 1.4544 (17) | C20—C22 | 1.4600 (17) |
C2—C3 | 1.3697 (18) | C21—H21 | 0.9500 |
C2—C4 | 1.4749 (18) | C23—C24 | 1.3630 (18) |
C3—C10 | 1.4632 (17) | C23—C25 | 1.4688 (17) |
C4—C9 | 1.3929 (19) | C24—C31 | 1.4690 (17) |
C4—C5 | 1.3935 (19) | C25—C26 | 1.3963 (18) |
C5—C6 | 1.387 (2) | C25—C30 | 1.3993 (17) |
C5—H5 | 0.9500 | C26—C27 | 1.384 (2) |
C6—C7 | 1.384 (2) | C26—H26 | 0.9500 |
C6—H6 | 0.9500 | C27—C28 | 1.386 (2) |
C7—C8 | 1.377 (2) | C27—H27 | 0.9500 |
C7—H7 | 0.9500 | C28—C29 | 1.384 (2) |
C8—C9 | 1.395 (2) | C28—H28 | 0.9500 |
C8—H8 | 0.9500 | C29—C30 | 1.3862 (18) |
C9—H9 | 0.9500 | C29—H29 | 0.9500 |
C10—C15 | 1.3907 (18) | C30—H30 | 0.9500 |
C10—C11 | 1.4009 (18) | C31—C36 | 1.3926 (18) |
C11—C12 | 1.3857 (19) | C31—C32 | 1.3963 (17) |
C11—H11 | 0.9500 | C32—C33 | 1.3834 (18) |
C12—C13 | 1.383 (2) | C32—H32 | 0.9500 |
C12—H12 | 0.9500 | C33—C34 | 1.386 (2) |
C13—C14 | 1.382 (2) | C33—H33 | 0.9500 |
C13—H13 | 0.9500 | C34—C35 | 1.387 (2) |
C14—C15 | 1.383 (2) | C34—H34 | 0.9500 |
C14—H14 | 0.9500 | C35—C36 | 1.389 (2) |
C15—H15 | 0.9500 | C35—H35 | 0.9500 |
C16—C21 | 1.3937 (16) | C36—H36 | 0.9500 |
C1—O1—C3 | 105.91 (10) | C19—C18—H18 | 119.7 |
C22—O2—C24 | 105.27 (10) | C17—C18—H18 | 119.7 |
C1—N1—C2 | 105.93 (10) | C18—C19—C20 | 119.85 (12) |
C22—N2—C23 | 105.39 (11) | C18—C19—H19 | 120.1 |
N1—C1—O1 | 113.22 (11) | C20—C19—H19 | 120.1 |
N1—C1—C16 | 126.14 (12) | C21—C20—C19 | 119.81 (11) |
O1—C1—C16 | 120.63 (12) | C21—C20—C22 | 120.34 (11) |
C3—C2—N1 | 108.13 (11) | C19—C20—C22 | 119.85 (11) |
C3—C2—C4 | 133.25 (12) | C20—C21—C16 | 120.19 (11) |
N1—C2—C4 | 118.58 (11) | C20—C21—H21 | 119.9 |
C2—C3—O1 | 106.80 (11) | C16—C21—H21 | 119.9 |
C2—C3—C10 | 136.91 (12) | N2—C22—O2 | 113.60 (11) |
O1—C3—C10 | 116.17 (11) | N2—C22—C20 | 129.04 (13) |
C9—C4—C5 | 118.66 (13) | O2—C22—C20 | 117.36 (11) |
C9—C4—C2 | 122.69 (12) | C24—C23—N2 | 108.67 (11) |
C5—C4—C2 | 118.65 (12) | C24—C23—C25 | 131.87 (12) |
C6—C5—C4 | 120.78 (14) | N2—C23—C25 | 119.43 (11) |
C6—C5—H5 | 119.6 | C23—C24—O2 | 107.05 (11) |
C4—C5—H5 | 119.6 | C23—C24—C31 | 137.71 (12) |
C7—C6—C5 | 120.13 (16) | O2—C24—C31 | 115.23 (11) |
C7—C6—H6 | 119.9 | C26—C25—C30 | 118.46 (12) |
C5—C6—H6 | 119.9 | C26—C25—C23 | 119.96 (11) |
C8—C7—C6 | 119.68 (15) | C30—C25—C23 | 121.53 (11) |
C8—C7—H7 | 120.2 | C27—C26—C25 | 120.85 (13) |
C6—C7—H7 | 120.2 | C27—C26—H26 | 119.6 |
C7—C8—C9 | 120.56 (15) | C25—C26—H26 | 119.6 |
C7—C8—H8 | 119.7 | C26—C27—C28 | 119.88 (13) |
C9—C8—H8 | 119.7 | C26—C27—H27 | 120.1 |
C4—C9—C8 | 120.15 (14) | C28—C27—H27 | 120.1 |
C4—C9—H9 | 119.9 | C29—C28—C27 | 120.18 (13) |
C8—C9—H9 | 119.9 | C29—C28—H28 | 119.9 |
C15—C10—C11 | 118.33 (12) | C27—C28—H28 | 119.9 |
C15—C10—C3 | 119.43 (12) | C28—C29—C30 | 120.00 (13) |
C11—C10—C3 | 122.23 (12) | C28—C29—H29 | 120.0 |
C12—C11—C10 | 120.35 (13) | C30—C29—H29 | 120.0 |
C12—C11—H11 | 119.8 | C29—C30—C25 | 120.62 (13) |
C10—C11—H11 | 119.8 | C29—C30—H30 | 119.7 |
C13—C12—C11 | 120.80 (13) | C25—C30—H30 | 119.7 |
C13—C12—H12 | 119.6 | C36—C31—C32 | 119.00 (12) |
C11—C12—H12 | 119.6 | C36—C31—C24 | 119.65 (11) |
C12—C13—C14 | 118.96 (13) | C32—C31—C24 | 121.32 (12) |
C12—C13—H13 | 120.5 | C33—C32—C31 | 120.53 (13) |
C14—C13—H13 | 120.5 | C33—C32—H32 | 119.7 |
C13—C14—C15 | 120.89 (13) | C31—C32—H32 | 119.7 |
C13—C14—H14 | 119.6 | C32—C33—C34 | 120.28 (13) |
C15—C14—H14 | 119.6 | C32—C33—H33 | 119.9 |
C14—C15—C10 | 120.67 (13) | C34—C33—H33 | 119.9 |
C14—C15—H15 | 119.7 | C33—C34—C35 | 119.57 (13) |
C10—C15—H15 | 119.7 | C33—C34—H34 | 120.2 |
C21—C16—C17 | 119.63 (11) | C35—C34—H34 | 120.2 |
C21—C16—C1 | 118.95 (11) | C34—C35—C36 | 120.42 (14) |
C17—C16—C1 | 121.42 (11) | C34—C35—H35 | 119.8 |
C18—C17—C16 | 119.95 (12) | C36—C35—H35 | 119.8 |
C18—C17—H17 | 120.0 | C35—C36—C31 | 120.19 (13) |
C16—C17—H17 | 120.0 | C35—C36—H36 | 119.9 |
C19—C18—C17 | 120.56 (12) | C31—C36—H36 | 119.9 |
C2—N1—C1—O1 | −1.05 (13) | C18—C19—C20—C22 | −179.37 (11) |
C2—N1—C1—C16 | 178.05 (11) | C19—C20—C21—C16 | 0.20 (16) |
C3—O1—C1—N1 | 0.37 (13) | C22—C20—C21—C16 | 179.20 (10) |
C3—O1—C1—C16 | −178.79 (10) | C17—C16—C21—C20 | 0.39 (16) |
C1—N1—C2—C3 | 1.31 (13) | C1—C16—C21—C20 | −179.02 (10) |
C1—N1—C2—C4 | 179.25 (10) | C23—N2—C22—O2 | −0.73 (13) |
N1—C2—C3—O1 | −1.11 (12) | C23—N2—C22—C20 | 179.11 (11) |
C4—C2—C3—O1 | −178.62 (12) | C24—O2—C22—N2 | 0.12 (12) |
N1—C2—C3—C10 | 174.37 (12) | C24—O2—C22—C20 | −179.74 (9) |
C4—C2—C3—C10 | −3.1 (2) | C21—C20—C22—N2 | 172.30 (11) |
C1—O1—C3—C2 | 0.48 (12) | C19—C20—C22—N2 | −8.70 (18) |
C1—O1—C3—C10 | −176.08 (9) | C21—C20—C22—O2 | −7.86 (15) |
C3—C2—C4—C9 | −48.2 (2) | C19—C20—C22—O2 | 171.14 (10) |
N1—C2—C4—C9 | 134.51 (13) | C22—N2—C23—C24 | 1.07 (12) |
C3—C2—C4—C5 | 132.56 (15) | C22—N2—C23—C25 | −177.39 (10) |
N1—C2—C4—C5 | −44.75 (16) | N2—C23—C24—O2 | −1.01 (12) |
C9—C4—C5—C6 | 1.8 (2) | C25—C23—C24—O2 | 177.18 (11) |
C2—C4—C5—C6 | −178.93 (13) | N2—C23—C24—C31 | 177.95 (12) |
C4—C5—C6—C7 | 0.1 (2) | C25—C23—C24—C31 | −3.9 (2) |
C5—C6—C7—C8 | −1.1 (2) | C22—O2—C24—C23 | 0.56 (11) |
C6—C7—C8—C9 | 0.3 (2) | C22—O2—C24—C31 | −178.66 (9) |
C5—C4—C9—C8 | −2.6 (2) | C24—C23—C25—C26 | 142.41 (13) |
C2—C4—C9—C8 | 178.13 (12) | N2—C23—C25—C26 | −39.56 (16) |
C7—C8—C9—C4 | 1.6 (2) | C24—C23—C25—C30 | −40.06 (18) |
C2—C3—C10—C15 | −179.87 (13) | N2—C23—C25—C30 | 137.98 (12) |
O1—C3—C10—C15 | −4.69 (15) | C30—C25—C26—C27 | 0.55 (18) |
C2—C3—C10—C11 | −1.0 (2) | C23—C25—C26—C27 | 178.16 (11) |
O1—C3—C10—C11 | 174.19 (10) | C25—C26—C27—C28 | −0.84 (19) |
C15—C10—C11—C12 | −1.02 (17) | C26—C27—C28—C29 | 0.3 (2) |
C3—C10—C11—C12 | −179.91 (11) | C27—C28—C29—C30 | 0.4 (2) |
C10—C11—C12—C13 | 1.17 (18) | C28—C29—C30—C25 | −0.70 (18) |
C11—C12—C13—C14 | −0.66 (19) | C26—C25—C30—C29 | 0.22 (17) |
C12—C13—C14—C15 | 0.0 (2) | C23—C25—C30—C29 | −177.35 (11) |
C13—C14—C15—C10 | 0.1 (2) | C23—C24—C31—C36 | 157.10 (13) |
C11—C10—C15—C14 | 0.39 (18) | O2—C24—C31—C36 | −23.99 (15) |
C3—C10—C15—C14 | 179.31 (11) | C23—C24—C31—C32 | −25.2 (2) |
N1—C1—C16—C21 | −0.41 (17) | O2—C24—C31—C32 | 153.68 (10) |
O1—C1—C16—C21 | 178.63 (10) | C36—C31—C32—C33 | 0.32 (18) |
N1—C1—C16—C17 | −179.82 (11) | C24—C31—C32—C33 | −177.36 (11) |
O1—C1—C16—C17 | −0.78 (17) | C31—C32—C33—C34 | 0.20 (19) |
C21—C16—C17—C18 | −0.82 (17) | C32—C33—C34—C35 | −0.9 (2) |
C1—C16—C17—C18 | 178.58 (11) | C33—C34—C35—C36 | 1.1 (2) |
C16—C17—C18—C19 | 0.66 (18) | C34—C35—C36—C31 | −0.6 (2) |
C17—C18—C19—C20 | −0.07 (18) | C32—C31—C36—C35 | −0.12 (18) |
C18—C19—C20—C21 | −0.36 (17) | C24—C31—C36—C35 | 177.60 (12) |
C52H56N2O2 | Z = 2 |
Mr = 740.99 | F(000) = 796 |
Triclinic, P1 | Dx = 1.150 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.3121 (3) Å | Cell parameters from 5548 reflections |
b = 11.1215 (3) Å | θ = 2.2–23.1° |
c = 19.8676 (6) Å | µ = 0.07 mm−1 |
α = 91.593 (2)° | T = 153 K |
β = 96.918 (2)° | Rod, colourless |
γ = 108.463 (2)° | 0.32 × 0.18 × 0.17 mm |
V = 2140.25 (11) Å3 |
Nonius Kappa APEXII CCD area-detector diffractometer | 9309 independent reflections |
Radiation source: fine-focus sealed tube | 5281 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ϕ and ω scans | θmax = 27.1°, θmin = 1.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.978, Tmax = 0.988 | k = −12→14 |
33601 measured reflections | l = −24→25 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.180 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0935P)2 + 0.1269P] where P = (Fo2 + 2Fc2)/3 |
9309 reflections | (Δ/σ)max < 0.001 |
517 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C52H56N2O2 | γ = 108.463 (2)° |
Mr = 740.99 | V = 2140.25 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.3121 (3) Å | Mo Kα radiation |
b = 11.1215 (3) Å | µ = 0.07 mm−1 |
c = 19.8676 (6) Å | T = 153 K |
α = 91.593 (2)° | 0.32 × 0.18 × 0.17 mm |
β = 96.918 (2)° |
Nonius Kappa APEXII CCD area-detector diffractometer | 9309 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5281 reflections with I > 2σ(I) |
Tmin = 0.978, Tmax = 0.988 | Rint = 0.044 |
33601 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.180 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.36 e Å−3 |
9309 reflections | Δρmin = −0.33 e Å−3 |
517 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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. All hydrogen atoms were included in the model in calculated positions and were refined as constrained to bonding atoms. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.83424 (16) | 0.85485 (15) | 0.83529 (7) | 0.0402 (4) | |
O2 | 1.05893 (16) | 0.72394 (15) | 1.04366 (7) | 0.0399 (4) | |
N1 | 0.62161 (17) | 0.74679 (17) | 0.78981 (8) | 0.0282 (4) | |
N2 | 0.95520 (17) | 0.55194 (16) | 1.09409 (8) | 0.0273 (4) | |
C1 | 0.7218 (2) | 0.7551 (2) | 0.83829 (11) | 0.0358 (5) | |
C2 | 0.6708 (2) | 0.8511 (2) | 0.75225 (10) | 0.0326 (5) | |
C3 | 0.8022 (2) | 0.9171 (2) | 0.77938 (10) | 0.0314 (5) | |
C4 | 0.5756 (2) | 0.8775 (2) | 0.69765 (10) | 0.0308 (5) | |
C5 | 0.5737 (2) | 1.0004 (2) | 0.68927 (11) | 0.0362 (6) | |
H5 | 0.6383 | 1.0689 | 0.7174 | 0.043* | |
C6 | 0.4795 (2) | 1.0246 (2) | 0.64081 (11) | 0.0376 (6) | |
H6 | 0.4816 | 1.1099 | 0.6358 | 0.045* | |
C7 | 0.3810 (2) | 0.9273 (2) | 0.59884 (11) | 0.0345 (5) | |
C8 | 0.3841 (2) | 0.8046 (2) | 0.60785 (11) | 0.0377 (6) | |
H8 | 0.3194 | 0.7358 | 0.5799 | 0.045* | |
C9 | 0.4783 (2) | 0.7798 (2) | 0.65609 (11) | 0.0358 (5) | |
H9 | 0.4766 | 0.6946 | 0.6610 | 0.043* | |
C10 | 0.9090 (2) | 1.0297 (2) | 0.76183 (10) | 0.0300 (5) | |
C11 | 0.9171 (2) | 1.0597 (2) | 0.69467 (11) | 0.0349 (5) | |
H11 | 0.8526 | 1.0063 | 0.6593 | 0.042* | |
C12 | 1.0184 (2) | 1.1666 (2) | 0.67884 (11) | 0.0350 (5) | |
H12 | 1.0205 | 1.1857 | 0.6326 | 0.042* | |
C13 | 1.1169 (2) | 1.2470 (2) | 0.72816 (11) | 0.0318 (5) | |
C14 | 1.1082 (2) | 1.2146 (2) | 0.79541 (11) | 0.0348 (5) | |
H14 | 1.1740 | 1.2668 | 0.8307 | 0.042* | |
C15 | 1.0070 (2) | 1.1093 (2) | 0.81203 (11) | 0.0330 (5) | |
H15 | 1.0041 | 1.0907 | 0.8583 | 0.040* | |
C16 | 0.7180 (2) | 0.6676 (2) | 0.89161 (10) | 0.0304 (5) | |
C17 | 0.6016 (2) | 0.5617 (2) | 0.89216 (11) | 0.0356 (5) | |
H17 | 0.5236 | 0.5482 | 0.8586 | 0.043* | |
C18 | 0.5997 (2) | 0.4764 (2) | 0.94143 (11) | 0.0391 (6) | |
H18 | 0.5201 | 0.4041 | 0.9416 | 0.047* | |
C19 | 0.7122 (2) | 0.4952 (2) | 0.99051 (11) | 0.0371 (6) | |
H19 | 0.7101 | 0.4357 | 1.0241 | 0.045* | |
C20 | 0.8286 (2) | 0.6010 (2) | 0.99074 (10) | 0.0291 (5) | |
C21 | 0.8309 (2) | 0.6868 (2) | 0.94161 (10) | 0.0301 (5) | |
H21 | 0.9102 | 0.7595 | 0.9419 | 0.036* | |
C22 | 0.9465 (2) | 0.6225 (2) | 1.04322 (11) | 0.0339 (5) | |
C23 | 1.0824 (2) | 0.6134 (2) | 1.13200 (10) | 0.0313 (5) | |
C24 | 1.1471 (2) | 0.7181 (2) | 1.10085 (10) | 0.0312 (5) | |
C25 | 1.1193 (2) | 0.5675 (2) | 1.19792 (10) | 0.0298 (5) | |
C26 | 1.1773 (2) | 0.6547 (2) | 1.25391 (11) | 0.0349 (5) | |
H26 | 1.1949 | 0.7428 | 1.2485 | 0.042* | |
C27 | 1.2093 (2) | 0.6145 (2) | 1.31696 (11) | 0.0377 (6) | |
H27 | 1.2494 | 0.6760 | 1.3541 | 0.045* | |
C28 | 1.1846 (2) | 0.4865 (2) | 1.32767 (11) | 0.0349 (5) | |
C29 | 1.1253 (2) | 0.4004 (2) | 1.27197 (12) | 0.0370 (6) | |
H29 | 1.1070 | 0.3123 | 1.2774 | 0.044* | |
C30 | 1.0919 (2) | 0.4400 (2) | 1.20809 (11) | 0.0336 (5) | |
H30 | 1.0498 | 0.3786 | 1.1711 | 0.040* | |
C31 | 1.2817 (2) | 0.8175 (2) | 1.11332 (10) | 0.0309 (5) | |
C32 | 1.2990 (2) | 0.9367 (2) | 1.08924 (10) | 0.0343 (5) | |
H32 | 1.2217 | 0.9546 | 1.0660 | 0.041* | |
C33 | 1.4265 (2) | 1.0299 (2) | 1.09846 (11) | 0.0367 (6) | |
H33 | 1.4352 | 1.1103 | 1.0809 | 0.044* | |
C34 | 1.5423 (2) | 1.0095 (2) | 1.13264 (11) | 0.0333 (5) | |
C35 | 1.5236 (2) | 0.8901 (2) | 1.15750 (11) | 0.0355 (5) | |
H35 | 1.6005 | 0.8730 | 1.1815 | 0.043* | |
C36 | 1.3970 (2) | 0.7961 (2) | 1.14828 (11) | 0.0342 (5) | |
H36 | 1.3883 | 0.7158 | 1.1659 | 0.041* | |
C37 | 0.2715 (3) | 0.9561 (3) | 0.54876 (12) | 0.0452 (6) | |
C38 | 0.3321 (4) | 1.0767 (3) | 0.51368 (18) | 0.0863 (11) | |
H38A | 0.4064 | 1.0680 | 0.4895 | 0.130* | |
H38B | 0.3691 | 1.1489 | 0.5477 | 0.130* | |
H38C | 0.2599 | 1.0910 | 0.4812 | 0.130* | |
C39 | 0.1619 (3) | 0.9722 (5) | 0.58915 (18) | 0.1198 (18) | |
H39A | 0.0968 | 1.0025 | 0.5600 | 0.180* | |
H39B | 0.2056 | 1.0341 | 0.6279 | 0.180* | |
H39C | 0.1124 | 0.8903 | 0.6057 | 0.180* | |
C40 | 0.2093 (5) | 0.8527 (4) | 0.49367 (18) | 0.1103 (16) | |
H40A | 0.1431 | 0.8763 | 0.4615 | 0.165* | |
H40B | 0.1616 | 0.7737 | 0.5135 | 0.165* | |
H40C | 0.2822 | 0.8400 | 0.4697 | 0.165* | |
C41 | 1.2305 (2) | 1.3656 (2) | 0.71170 (11) | 0.0369 (6) | |
C42 | 1.3724 (3) | 1.3496 (3) | 0.73211 (14) | 0.0531 (7) | |
H42A | 1.4449 | 1.4249 | 0.7212 | 0.080* | |
H42B | 1.3771 | 1.2742 | 0.7071 | 0.080* | |
H42C | 1.3856 | 1.3395 | 0.7810 | 0.080* | |
C43 | 1.2240 (3) | 1.4837 (3) | 0.75056 (16) | 0.0612 (8) | |
H43A | 1.1355 | 1.4967 | 0.7359 | 0.092* | |
H43B | 1.2996 | 1.5580 | 0.7412 | 0.092* | |
H43C | 1.2327 | 1.4720 | 0.7994 | 0.092* | |
C44 | 1.2183 (3) | 1.3883 (3) | 0.63572 (13) | 0.0559 (7) | |
H44A | 1.1275 | 1.3964 | 0.6207 | 0.084* | |
H44B | 1.2289 | 1.3164 | 0.6099 | 0.084* | |
H44C | 1.2906 | 1.4665 | 0.6281 | 0.084* | |
C45 | 1.2151 (3) | 0.4456 (3) | 1.39873 (12) | 0.0467 (7) | |
C46 | 1.2037 (4) | 0.3060 (3) | 1.39892 (16) | 0.0840 (11) | |
H46A | 1.1101 | 0.2537 | 1.3796 | 0.126* | |
H46B | 1.2235 | 0.2844 | 1.4457 | 0.126* | |
H46C | 1.2702 | 0.2898 | 1.3716 | 0.126* | |
C47 | 1.3602 (3) | 0.5257 (4) | 1.43140 (16) | 0.0933 (13) | |
H47A | 1.4286 | 0.5106 | 1.4049 | 0.140* | |
H47B | 1.3768 | 0.5019 | 1.4780 | 0.140* | |
H47C | 1.3682 | 0.6159 | 1.4322 | 0.140* | |
C48 | 1.1112 (3) | 0.4692 (3) | 1.44168 (13) | 0.0675 (9) | |
H48A | 1.1184 | 0.5593 | 1.4424 | 0.101* | |
H48B | 1.1308 | 0.4463 | 1.4882 | 0.101* | |
H48C | 1.0176 | 0.4173 | 1.4220 | 0.101* | |
C49 | 1.6858 (2) | 1.1096 (2) | 1.14201 (12) | 0.0413 (6) | |
C50 | 1.6824 (3) | 1.2354 (3) | 1.1145 (2) | 0.0779 (10) | |
H50A | 1.6481 | 1.2221 | 1.0657 | 0.117* | |
H50B | 1.7758 | 1.2971 | 1.1216 | 0.117* | |
H50C | 1.6213 | 1.2679 | 1.1384 | 0.117* | |
C51 | 1.7458 (3) | 1.1313 (3) | 1.21720 (14) | 0.0735 (10) | |
H51A | 1.6862 | 1.1626 | 1.2429 | 0.110* | |
H51B | 1.8384 | 1.1942 | 1.2226 | 0.110* | |
H51C | 1.7514 | 1.0511 | 1.2344 | 0.110* | |
C52 | 1.7798 (3) | 1.0608 (3) | 1.10285 (14) | 0.0592 (8) | |
H52A | 1.7818 | 0.9788 | 1.1190 | 0.089* | |
H52B | 1.8733 | 1.1220 | 1.1102 | 0.089* | |
H52C | 1.7446 | 1.0502 | 1.0542 | 0.089* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0444 (10) | 0.0429 (10) | 0.0336 (9) | 0.0143 (9) | 0.0040 (7) | 0.0095 (7) |
O2 | 0.0394 (9) | 0.0456 (10) | 0.0303 (9) | 0.0094 (8) | 0.0000 (7) | 0.0035 (7) |
N1 | 0.0306 (10) | 0.0327 (10) | 0.0227 (9) | 0.0119 (8) | 0.0026 (7) | 0.0082 (8) |
N2 | 0.0311 (10) | 0.0310 (10) | 0.0191 (9) | 0.0103 (8) | −0.0006 (7) | 0.0020 (7) |
C1 | 0.0434 (14) | 0.0341 (13) | 0.0341 (13) | 0.0149 (12) | 0.0129 (11) | 0.0087 (10) |
C2 | 0.0370 (13) | 0.0358 (13) | 0.0265 (11) | 0.0138 (11) | 0.0038 (9) | 0.0037 (10) |
C3 | 0.0381 (13) | 0.0348 (13) | 0.0251 (11) | 0.0169 (11) | 0.0031 (9) | 0.0070 (10) |
C4 | 0.0284 (12) | 0.0355 (13) | 0.0277 (11) | 0.0088 (10) | 0.0043 (9) | 0.0052 (10) |
C5 | 0.0330 (13) | 0.0332 (13) | 0.0385 (13) | 0.0084 (11) | −0.0028 (10) | −0.0009 (10) |
C6 | 0.0375 (13) | 0.0337 (13) | 0.0416 (14) | 0.0126 (11) | 0.0014 (11) | 0.0057 (11) |
C7 | 0.0316 (12) | 0.0424 (14) | 0.0296 (12) | 0.0122 (11) | 0.0037 (9) | 0.0040 (10) |
C8 | 0.0348 (13) | 0.0379 (14) | 0.0345 (13) | 0.0063 (11) | −0.0029 (10) | −0.0005 (11) |
C9 | 0.0371 (13) | 0.0273 (12) | 0.0401 (13) | 0.0076 (11) | 0.0016 (10) | 0.0037 (10) |
C10 | 0.0316 (12) | 0.0310 (12) | 0.0286 (12) | 0.0127 (10) | 0.0011 (9) | 0.0050 (9) |
C11 | 0.0352 (13) | 0.0383 (14) | 0.0274 (12) | 0.0091 (11) | −0.0026 (9) | 0.0019 (10) |
C12 | 0.0342 (12) | 0.0408 (14) | 0.0281 (12) | 0.0103 (11) | 0.0004 (9) | 0.0078 (10) |
C13 | 0.0298 (12) | 0.0359 (13) | 0.0308 (12) | 0.0130 (11) | 0.0013 (9) | 0.0034 (10) |
C14 | 0.0348 (13) | 0.0365 (14) | 0.0311 (12) | 0.0120 (11) | −0.0048 (10) | 0.0006 (10) |
C15 | 0.0366 (13) | 0.0374 (13) | 0.0261 (11) | 0.0145 (11) | 0.0009 (10) | 0.0054 (10) |
C16 | 0.0326 (12) | 0.0311 (12) | 0.0272 (11) | 0.0090 (10) | 0.0054 (9) | 0.0042 (9) |
C17 | 0.0300 (12) | 0.0406 (14) | 0.0318 (12) | 0.0072 (11) | −0.0003 (9) | 0.0004 (10) |
C18 | 0.0336 (13) | 0.0344 (13) | 0.0402 (14) | −0.0010 (11) | 0.0028 (10) | 0.0050 (11) |
C19 | 0.0445 (14) | 0.0339 (13) | 0.0306 (12) | 0.0082 (12) | 0.0065 (10) | 0.0087 (10) |
C20 | 0.0284 (11) | 0.0309 (12) | 0.0257 (11) | 0.0070 (10) | 0.0020 (9) | 0.0018 (9) |
C21 | 0.0278 (11) | 0.0304 (12) | 0.0270 (11) | 0.0024 (10) | 0.0034 (9) | 0.0027 (9) |
C22 | 0.0323 (12) | 0.0380 (14) | 0.0291 (12) | 0.0097 (11) | 0.0008 (9) | −0.0016 (10) |
C23 | 0.0344 (12) | 0.0354 (13) | 0.0230 (11) | 0.0111 (11) | 0.0009 (9) | −0.0003 (9) |
C24 | 0.0323 (12) | 0.0383 (13) | 0.0217 (11) | 0.0115 (11) | −0.0010 (9) | −0.0003 (9) |
C25 | 0.0275 (11) | 0.0337 (13) | 0.0267 (11) | 0.0083 (10) | 0.0023 (9) | 0.0026 (10) |
C26 | 0.0403 (13) | 0.0297 (13) | 0.0317 (12) | 0.0077 (11) | 0.0027 (10) | 0.0039 (10) |
C27 | 0.0419 (14) | 0.0421 (15) | 0.0252 (12) | 0.0101 (12) | −0.0011 (10) | 0.0002 (10) |
C28 | 0.0354 (13) | 0.0412 (14) | 0.0327 (12) | 0.0172 (11) | 0.0071 (10) | 0.0111 (11) |
C29 | 0.0404 (13) | 0.0294 (13) | 0.0455 (14) | 0.0145 (11) | 0.0113 (11) | 0.0101 (11) |
C30 | 0.0315 (12) | 0.0344 (13) | 0.0337 (12) | 0.0090 (11) | 0.0047 (10) | 0.0014 (10) |
C31 | 0.0348 (12) | 0.0343 (13) | 0.0219 (11) | 0.0086 (11) | 0.0044 (9) | 0.0027 (9) |
C32 | 0.0361 (13) | 0.0398 (14) | 0.0281 (12) | 0.0132 (11) | 0.0048 (10) | 0.0076 (10) |
C33 | 0.0419 (14) | 0.0343 (13) | 0.0357 (13) | 0.0124 (12) | 0.0100 (10) | 0.0107 (10) |
C34 | 0.0363 (13) | 0.0354 (13) | 0.0276 (12) | 0.0093 (11) | 0.0075 (9) | 0.0037 (10) |
C35 | 0.0342 (13) | 0.0397 (14) | 0.0309 (12) | 0.0109 (11) | 0.0006 (10) | 0.0050 (10) |
C36 | 0.0382 (13) | 0.0325 (13) | 0.0305 (12) | 0.0098 (11) | 0.0024 (10) | 0.0061 (10) |
C37 | 0.0433 (14) | 0.0576 (17) | 0.0357 (14) | 0.0203 (13) | −0.0024 (11) | 0.0056 (12) |
C38 | 0.091 (3) | 0.081 (2) | 0.087 (2) | 0.035 (2) | −0.0179 (19) | 0.036 (2) |
C39 | 0.064 (2) | 0.253 (6) | 0.076 (2) | 0.096 (3) | 0.0118 (18) | 0.040 (3) |
C40 | 0.148 (4) | 0.092 (3) | 0.076 (2) | 0.051 (3) | −0.073 (2) | −0.017 (2) |
C41 | 0.0336 (13) | 0.0374 (14) | 0.0389 (13) | 0.0104 (11) | 0.0038 (10) | 0.0070 (11) |
C42 | 0.0372 (14) | 0.0580 (18) | 0.0599 (17) | 0.0099 (13) | 0.0036 (12) | 0.0100 (14) |
C43 | 0.0595 (18) | 0.0410 (16) | 0.082 (2) | 0.0080 (14) | 0.0274 (16) | 0.0038 (15) |
C44 | 0.0508 (16) | 0.0583 (18) | 0.0507 (16) | 0.0057 (14) | 0.0052 (13) | 0.0199 (14) |
C45 | 0.0538 (16) | 0.0615 (18) | 0.0365 (14) | 0.0323 (14) | 0.0104 (12) | 0.0191 (12) |
C46 | 0.134 (3) | 0.092 (3) | 0.060 (2) | 0.077 (2) | 0.026 (2) | 0.0410 (18) |
C47 | 0.067 (2) | 0.149 (4) | 0.060 (2) | 0.035 (2) | −0.0140 (17) | 0.041 (2) |
C48 | 0.090 (2) | 0.093 (2) | 0.0416 (16) | 0.052 (2) | 0.0247 (15) | 0.0299 (16) |
C49 | 0.0348 (13) | 0.0436 (15) | 0.0415 (14) | 0.0050 (12) | 0.0089 (11) | 0.0095 (11) |
C50 | 0.0430 (17) | 0.0443 (18) | 0.138 (3) | 0.0008 (15) | 0.0101 (18) | 0.0296 (19) |
C51 | 0.0547 (18) | 0.085 (2) | 0.0472 (17) | −0.0239 (17) | 0.0059 (14) | −0.0052 (16) |
C52 | 0.0433 (16) | 0.081 (2) | 0.0546 (17) | 0.0181 (16) | 0.0149 (13) | 0.0184 (15) |
O1—C1 | 1.336 (3) | C31—C32 | 1.388 (3) |
O1—C3 | 1.386 (2) | C31—C36 | 1.394 (3) |
O2—C22 | 1.337 (3) | C32—C33 | 1.380 (3) |
O2—C24 | 1.384 (2) | C32—H32 | 0.9500 |
N1—C1 | 1.303 (3) | C33—C34 | 1.387 (3) |
N1—C2 | 1.388 (3) | C33—H33 | 0.9500 |
N2—C22 | 1.308 (3) | C34—C35 | 1.394 (3) |
N2—C23 | 1.386 (3) | C34—C49 | 1.530 (3) |
C1—C16 | 1.454 (3) | C35—C36 | 1.378 (3) |
C2—C4 | 1.474 (3) | C35—H35 | 0.9500 |
C3—C2 | 1.356 (3) | C36—H36 | 0.9500 |
C3—C10 | 1.465 (3) | C37—C40 | 1.492 (4) |
C4—C5 | 1.387 (3) | C37—C39 | 1.514 (4) |
C4—C9 | 1.389 (3) | C37—C38 | 1.517 (4) |
C5—C6 | 1.377 (3) | C38—H38A | 0.9800 |
C5—H5 | 0.9500 | C38—H38B | 0.9800 |
C6—C7 | 1.395 (3) | C38—H38C | 0.9800 |
C6—H6 | 0.9500 | C39—H39A | 0.9800 |
C7—C8 | 1.391 (3) | C39—H39B | 0.9800 |
C7—C37 | 1.530 (3) | C39—H39C | 0.9800 |
C8—C9 | 1.378 (3) | C40—H40A | 0.9800 |
C8—H8 | 0.9500 | C40—H40B | 0.9800 |
C9—H9 | 0.9500 | C40—H40C | 0.9800 |
C10—C11 | 1.390 (3) | C41—C43 | 1.529 (4) |
C10—C15 | 1.393 (3) | C41—C44 | 1.534 (3) |
C11—C12 | 1.384 (3) | C41—C42 | 1.537 (3) |
C11—H11 | 0.9500 | C42—H42A | 0.9800 |
C12—C13 | 1.389 (3) | C42—H42B | 0.9800 |
C12—H12 | 0.9500 | C42—H42C | 0.9800 |
C13—C14 | 1.399 (3) | C43—H43A | 0.9800 |
C13—C41 | 1.535 (3) | C43—H43B | 0.9800 |
C14—C15 | 1.379 (3) | C43—H43C | 0.9800 |
C14—H14 | 0.9500 | C44—H44A | 0.9800 |
C15—H15 | 0.9500 | C44—H44B | 0.9800 |
C16—C17 | 1.392 (3) | C44—H44C | 0.9800 |
C16—C21 | 1.393 (3) | C45—C46 | 1.520 (4) |
C17—H17 | 0.9500 | C45—C48 | 1.527 (4) |
C18—C17 | 1.379 (3) | C45—C47 | 1.531 (4) |
C18—H18 | 0.9500 | C46—H46A | 0.9800 |
C19—C18 | 1.380 (3) | C46—H46B | 0.9800 |
C19—H19 | 0.9500 | C46—H46C | 0.9800 |
C20—C19 | 1.389 (3) | C47—H47A | 0.9800 |
C20—C22 | 1.456 (3) | C47—H47B | 0.9800 |
C21—C20 | 1.380 (3) | C47—H47C | 0.9800 |
C21—H21 | 0.9500 | C48—H48A | 0.9800 |
C23—C25 | 1.470 (3) | C48—H48B | 0.9800 |
C24—C23 | 1.354 (3) | C48—H48C | 0.9800 |
C24—C31 | 1.462 (3) | C49—C50 | 1.526 (4) |
C25—C30 | 1.380 (3) | C49—C52 | 1.527 (4) |
C25—C26 | 1.396 (3) | C49—C51 | 1.528 (3) |
C26—C27 | 1.379 (3) | C50—H50A | 0.9800 |
C26—H26 | 0.9500 | C50—H50B | 0.9800 |
C27—C28 | 1.392 (3) | C50—H50C | 0.9800 |
C27—H27 | 0.9500 | C51—H51A | 0.9800 |
C28—C29 | 1.386 (3) | C51—H51B | 0.9800 |
C28—C45 | 1.522 (3) | C51—H51C | 0.9800 |
C29—C30 | 1.395 (3) | C52—H52A | 0.9800 |
C29—H29 | 0.9500 | C52—H52B | 0.9800 |
C30—H30 | 0.9500 | C52—H52C | 0.9800 |
C1—O1—C3 | 105.71 (17) | C33—C34—C49 | 123.1 (2) |
C1—N1—C2 | 105.28 (18) | C35—C34—C49 | 120.2 (2) |
C2—C3—O1 | 106.79 (19) | C36—C35—C34 | 122.0 (2) |
C2—C3—C10 | 135.0 (2) | C36—C35—H35 | 119.0 |
O1—C3—C10 | 118.18 (18) | C34—C35—H35 | 119.0 |
C3—C2—N1 | 108.86 (18) | C35—C36—C31 | 120.7 (2) |
C3—C2—C4 | 132.1 (2) | C35—C36—H36 | 119.6 |
C4—C5—H5 | 119.5 | C31—C36—H36 | 119.6 |
C4—C5—H5 | 119.5 | C40—C37—C39 | 110.4 (3) |
C5—C4—C9 | 117.7 (2) | C40—C37—C38 | 106.2 (3) |
C5—C4—C2 | 120.9 (2) | C39—C37—C38 | 109.4 (3) |
C9—C4—C2 | 121.3 (2) | C40—C37—C7 | 111.9 (2) |
C6—C5—C4 | 121.0 (2) | C39—C37—C7 | 107.2 (2) |
C6—C5—H5 | 119.5 | C38—C37—C7 | 111.7 (2) |
C5—C6—C7 | 121.8 (2) | C37—C38—H38A | 109.5 |
C5—C6—H6 | 119.1 | C37—C38—H38B | 109.5 |
C7—C6—H6 | 119.1 | H38A—C38—H38B | 109.5 |
C8—C7—C6 | 116.5 (2) | C37—C38—H38C | 109.5 |
C8—C7—C37 | 122.8 (2) | H38A—C38—H38C | 109.5 |
C6—C7—C37 | 120.6 (2) | H38B—C38—H38C | 109.5 |
C9—C8—C7 | 122.0 (2) | C37—C39—H39A | 109.5 |
C9—C8—H8 | 119.0 | C37—C39—H39B | 109.5 |
C7—C8—H8 | 119.0 | H39A—C39—H39B | 109.5 |
C8—C9—C4 | 120.9 (2) | C37—C39—H39C | 109.5 |
C8—C9—H9 | 119.5 | H39A—C39—H39C | 109.5 |
C4—C9—H9 | 119.5 | H39B—C39—H39C | 109.5 |
N1—C2—C4 | 118.79 (19) | C37—C40—H40A | 109.5 |
N1—C1—O1 | 113.34 (19) | C37—C40—H40B | 109.5 |
N1—C1—C16 | 125.7 (2) | H40A—C40—H40B | 109.5 |
O1—C1—C16 | 121.0 (2) | C37—C40—H40C | 109.5 |
C10—C11—H11 | 119.7 | H40A—C40—H40C | 109.5 |
C10—C15—H15 | 119.6 | H40B—C40—H40C | 109.5 |
C11—C10—C15 | 117.9 (2) | C43—C41—C44 | 107.8 (2) |
C11—C10—C3 | 121.23 (19) | C43—C41—C13 | 110.30 (19) |
C11—C12—C13 | 122.3 (2) | C44—C41—C13 | 112.57 (19) |
C11—C12—H12 | 118.8 | C43—C41—C42 | 109.2 (2) |
C12—C11—C10 | 120.6 (2) | C44—C41—C42 | 107.4 (2) |
C12—C11—H11 | 119.7 | C13—C41—C42 | 109.4 (2) |
C12—C13—C14 | 116.3 (2) | C41—C42—H42A | 109.5 |
C12—C13—C41 | 123.18 (19) | C41—C42—H42B | 109.5 |
C13—C14—H14 | 119.0 | H42A—C42—H42B | 109.5 |
C13—C12—H12 | 118.8 | C41—C42—H42C | 109.5 |
C14—C15—C10 | 120.8 (2) | H42A—C42—H42C | 109.5 |
C14—C15—H15 | 119.6 | H42B—C42—H42C | 109.5 |
C14—C13—C41 | 120.53 (19) | C41—C43—H43A | 109.5 |
C15—C10—C3 | 120.89 (19) | C41—C43—H43B | 109.5 |
C15—C14—C13 | 122.0 (2) | H43A—C43—H43B | 109.5 |
C15—C14—H14 | 119.0 | C41—C43—H43C | 109.5 |
C17—C16—C21 | 119.26 (19) | H43A—C43—H43C | 109.5 |
C17—C16—C1 | 119.9 (2) | H43B—C43—H43C | 109.5 |
C21—C16—C1 | 120.8 (2) | C41—C44—H44A | 109.5 |
C20—C21—C16 | 120.6 (2) | C41—C44—H44B | 109.5 |
C20—C21—H21 | 119.7 | H44A—C44—H44B | 109.5 |
C16—C21—H21 | 119.7 | C41—C44—H44C | 109.5 |
C21—C20—C19 | 119.6 (2) | H44A—C44—H44C | 109.5 |
C21—C20—C22 | 120.2 (2) | H44B—C44—H44C | 109.5 |
C19—C20—C22 | 120.1 (2) | C46—C45—C28 | 112.7 (2) |
C18—C19—C20 | 120.0 (2) | C46—C45—C48 | 108.7 (2) |
C18—C19—H19 | 120.0 | C28—C45—C48 | 108.0 (2) |
C20—C19—H19 | 120.0 | C46—C45—C47 | 108.8 (2) |
C17—C18—C19 | 120.6 (2) | C28—C45—C47 | 110.2 (2) |
C17—C18—H18 | 119.7 | C48—C45—C47 | 108.3 (3) |
C19—C18—H18 | 119.7 | C45—C46—H46A | 109.5 |
C18—C17—C16 | 119.9 (2) | C45—C46—H46B | 109.5 |
C18—C17—H17 | 120.0 | H46A—C46—H46B | 109.5 |
C16—C17—H17 | 120.0 | C45—C46—H46C | 109.5 |
C22—O2—C24 | 105.53 (17) | H46A—C46—H46C | 109.5 |
C22—N2—C23 | 105.33 (18) | H46B—C46—H46C | 109.5 |
N2—C22—O2 | 113.20 (18) | C45—C47—H47A | 109.5 |
N2—C22—C20 | 126.3 (2) | C45—C47—H47B | 109.5 |
O2—C22—C20 | 120.44 (19) | H47A—C47—H47B | 109.5 |
C23—C24—O2 | 107.22 (18) | C45—C47—H47C | 109.5 |
C23—C24—C31 | 135.4 (2) | H47A—C47—H47C | 109.5 |
O2—C24—C31 | 117.38 (18) | H47B—C47—H47C | 109.5 |
C24—C23—N2 | 108.70 (18) | C45—C48—H48A | 109.5 |
C24—C23—C25 | 131.2 (2) | C45—C48—H48B | 109.5 |
N2—C23—C25 | 119.76 (19) | H48A—C48—H48B | 109.5 |
C30—C25—C26 | 117.93 (19) | C45—C48—H48C | 109.5 |
C30—C25—C23 | 122.7 (2) | H48A—C48—H48C | 109.5 |
C26—C25—C23 | 119.3 (2) | H48B—C48—H48C | 109.5 |
C27—C26—C25 | 120.8 (2) | C50—C49—C52 | 108.0 (2) |
C27—C26—H26 | 119.6 | C50—C49—C51 | 109.5 (2) |
C25—C26—H26 | 119.6 | C52—C49—C51 | 108.7 (2) |
C26—C27—C28 | 121.9 (2) | C50—C49—C34 | 111.8 (2) |
C26—C27—H27 | 119.1 | C52—C49—C34 | 108.5 (2) |
C28—C27—H27 | 119.1 | C51—C49—C34 | 110.11 (19) |
C29—C28—C27 | 116.9 (2) | C49—C50—H50A | 109.5 |
C29—C28—C45 | 122.8 (2) | C49—C50—H50B | 109.5 |
C27—C28—C45 | 120.2 (2) | H50A—C50—H50B | 109.5 |
C28—C29—C30 | 121.7 (2) | C49—C50—H50C | 109.5 |
C28—C29—H29 | 119.2 | H50A—C50—H50C | 109.5 |
C30—C29—H29 | 119.2 | H50B—C50—H50C | 109.5 |
C25—C30—C29 | 120.8 (2) | C49—C51—H51A | 109.5 |
C25—C30—H30 | 119.6 | C49—C51—H51B | 109.5 |
C29—C30—H30 | 119.6 | H51A—C51—H51B | 109.5 |
C32—C31—C36 | 117.6 (2) | C49—C51—H51C | 109.5 |
C32—C31—C24 | 120.5 (2) | H51A—C51—H51C | 109.5 |
C36—C31—C24 | 121.9 (2) | H51B—C51—H51C | 109.5 |
C33—C32—C31 | 121.1 (2) | C49—C52—H52A | 109.5 |
C33—C32—H32 | 119.5 | C49—C52—H52B | 109.5 |
C31—C32—H32 | 119.5 | H52A—C52—H52B | 109.5 |
C32—C33—C34 | 121.9 (2) | C49—C52—H52C | 109.5 |
C32—C33—H33 | 119.1 | H52A—C52—H52C | 109.5 |
C34—C33—H33 | 119.1 | H52B—C52—H52C | 109.5 |
C33—C34—C35 | 116.6 (2) | ||
C1—O1—C3—C2 | 0.5 (2) | C22—C20—C19—C18 | 178.8 (2) |
C1—O1—C3—C10 | −178.09 (19) | C20—C19—C18—C17 | 0.3 (4) |
O1—C3—C2—N1 | −1.2 (2) | C19—C18—C17—C16 | 0.1 (4) |
C10—C3—C2—N1 | 177.0 (2) | C21—C16—C17—C18 | −0.7 (3) |
O1—C3—C2—C4 | 172.4 (2) | C1—C16—C17—C18 | 177.9 (2) |
C10—C3—C2—C4 | −9.3 (4) | C23—N2—C22—O2 | 1.4 (2) |
C1—N1—C2—C3 | 1.5 (2) | C23—N2—C22—C20 | −176.8 (2) |
C1—N1—C2—C4 | −173.15 (19) | C24—O2—C22—N2 | −0.7 (2) |
C2—N1—C1—O1 | −1.2 (2) | C24—O2—C22—C20 | 177.62 (19) |
C2—N1—C1—C16 | 179.0 (2) | C21—C20—C22—N2 | 176.9 (2) |
C3—O1—C1—N1 | 0.4 (3) | C19—C20—C22—N2 | −2.0 (3) |
C3—O1—C1—C16 | −179.7 (2) | C21—C20—C22—O2 | −1.2 (3) |
C2—C3—C10—C11 | −30.7 (4) | C19—C20—C22—O2 | 179.8 (2) |
O1—C3—C10—C11 | 147.5 (2) | C22—O2—C24—C23 | −0.3 (2) |
C2—C3—C10—C15 | 150.2 (3) | C22—O2—C24—C31 | 178.63 (19) |
O1—C3—C10—C15 | −31.7 (3) | O2—C24—C23—N2 | 1.1 (2) |
C15—C10—C11—C12 | −1.0 (3) | C31—C24—C23—N2 | −177.5 (2) |
C3—C10—C11—C12 | 179.8 (2) | O2—C24—C23—C25 | −172.3 (2) |
C10—C11—C12—C13 | 1.1 (4) | C31—C24—C23—C25 | 9.0 (5) |
C11—C12—C13—C14 | −0.4 (3) | C22—N2—C23—C24 | −1.6 (2) |
C11—C12—C13—C41 | 179.7 (2) | C22—N2—C23—C25 | 172.8 (2) |
C12—C13—C14—C15 | −0.4 (3) | C23—C24—C31—C32 | −154.4 (3) |
C41—C13—C14—C15 | 179.6 (2) | O2—C24—C31—C32 | 27.1 (3) |
C13—C14—C15—C10 | 0.4 (3) | C23—C24—C31—C36 | 26.8 (4) |
C11—C10—C15—C14 | 0.3 (3) | O2—C24—C31—C36 | −151.7 (2) |
C3—C10—C15—C14 | 179.4 (2) | C36—C31—C32—C33 | 1.2 (3) |
C12—C13—C41—C43 | 123.3 (2) | C24—C31—C32—C33 | −177.6 (2) |
C14—C13—C41—C43 | −56.7 (3) | C31—C32—C33—C34 | −0.7 (3) |
C12—C13—C41—C44 | 2.8 (3) | C32—C33—C34—C35 | −0.2 (3) |
C14—C13—C41—C44 | −177.2 (2) | C32—C33—C34—C49 | 178.3 (2) |
C12—C13—C41—C42 | −116.5 (2) | C33—C34—C35—C36 | 0.6 (3) |
C14—C13—C41—C42 | 63.5 (3) | C49—C34—C35—C36 | −177.9 (2) |
C3—C2—C4—C5 | −36.5 (4) | C34—C35—C36—C31 | −0.1 (3) |
N1—C2—C4—C5 | 136.6 (2) | C32—C31—C36—C35 | −0.9 (3) |
C3—C2—C4—C9 | 148.2 (2) | C24—C31—C36—C35 | 177.9 (2) |
N1—C2—C4—C9 | −38.7 (3) | C33—C34—C49—C50 | 4.5 (3) |
C9—C4—C5—C6 | −0.8 (3) | C35—C34—C49—C50 | −177.0 (2) |
C2—C4—C5—C6 | −176.2 (2) | C33—C34—C49—C52 | −114.5 (2) |
C4—C5—C6—C7 | 1.0 (4) | C35—C34—C49—C52 | 63.9 (3) |
C5—C6—C7—C8 | −0.9 (3) | C33—C34—C49—C51 | 126.6 (3) |
C5—C6—C7—C37 | 175.9 (2) | C35—C34—C49—C51 | −55.0 (3) |
C6—C7—C8—C9 | 0.7 (3) | C24—C23—C25—C30 | −144.6 (2) |
C37—C7—C8—C9 | −176.0 (2) | N2—C23—C25—C30 | 42.5 (3) |
C7—C8—C9—C4 | −0.6 (4) | C24—C23—C25—C26 | 39.2 (4) |
C5—C4—C9—C8 | 0.6 (3) | N2—C23—C25—C26 | −133.7 (2) |
C2—C4—C9—C8 | 176.1 (2) | C30—C25—C26—C27 | 1.6 (3) |
C8—C7—C37—C40 | −23.1 (4) | C23—C25—C26—C27 | 178.0 (2) |
C6—C7—C37—C40 | 160.4 (3) | C25—C26—C27—C28 | −0.5 (4) |
C8—C7—C37—C39 | 98.1 (3) | C26—C27—C28—C29 | −0.4 (3) |
C6—C7—C37—C39 | −78.4 (3) | C26—C27—C28—C45 | −177.1 (2) |
C8—C7—C37—C38 | −142.1 (3) | C27—C28—C29—C30 | 0.0 (3) |
C6—C7—C37—C38 | 41.4 (3) | C45—C28—C29—C30 | 176.7 (2) |
N1—C1—C16—C17 | 2.3 (3) | C26—C25—C30—C29 | −2.0 (3) |
O1—C1—C16—C17 | −177.5 (2) | C23—C25—C30—C29 | −178.2 (2) |
N1—C1—C16—C21 | −179.1 (2) | C28—C29—C30—C25 | 1.2 (3) |
O1—C1—C16—C21 | 1.0 (3) | C29—C28—C45—C46 | 12.6 (3) |
C17—C16—C21—C20 | 0.8 (3) | C27—C28—C45—C46 | −170.8 (2) |
C1—C16—C21—C20 | −177.7 (2) | C29—C28—C45—C48 | −107.5 (3) |
C16—C21—C20—C19 | −0.4 (3) | C27—C28—C45—C48 | 69.0 (3) |
C16—C21—C20—C22 | −179.4 (2) | C29—C28—C45—C47 | 134.4 (3) |
C21—C20—C19—C18 | −0.2 (3) | C27—C28—C45—C47 | −49.1 (3) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C36H24N2O2 | C52H56N2O2 |
Mr | 516.57 | 740.99 |
Crystal system, space group | Orthorhombic, Pbca | Triclinic, P1 |
Temperature (K) | 153 | 153 |
a, b, c (Å) | 7.1523 (2), 20.0145 (5), 36.8669 (8) | 10.3121 (3), 11.1215 (3), 19.8676 (6) |
α, β, γ (°) | 90, 90, 90 | 91.593 (2), 96.918 (2), 108.463 (2) |
V (Å3) | 5277.5 (2) | 2140.25 (11) |
Z | 8 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.07 |
Crystal size (mm) | 0.48 × 0.34 × 0.17 | 0.32 × 0.18 × 0.17 |
Data collection | ||
Diffractometer | Nonius Kappa APEXII CCD area-detector diffractometer | Nonius Kappa APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.962, 0.986 | 0.978, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 80848, 10121, 5826 | 33601, 9309, 5281 |
Rint | 0.062 | 0.044 |
(sin θ/λ)max (Å−1) | 0.772 | 0.641 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.156, 0.99 | 0.057, 0.180, 1.02 |
No. of reflections | 10121 | 9309 |
No. of parameters | 361 | 517 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.31 | 0.36, −0.33 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXTL (Sheldrick, 2008).
Planes | (I) | (II) |
A/B | 46.1 (1) | 39.6 (1) |
A'/B' | 40.5 (1) | 42.6 (1) |
A/C | 5.5 (1) | 31.3 (1) |
A'/C' | 25.1 (1) | 27.1 (1) |
A/D | 2.3 (1) | 2.3 (2) |
A'/D' | 8.2 (1) | 3.5 (2) |
B/C | 50.3 (1) | 54.4 (1) |
B'/C' | 51.3 (1) | 54.2 (1) |
Symmetry | H···A | D···A | D-H···A | |
C5—H5···N1 | -1/2+x, y, 1/2-z | 2.556 | 3.489 (1) | 167.5 |
C15—H15···O1 | x, y, z | 2.405 | 2.761 (1) | 101.8 |
C29—H29···centroid(C') | 1-x, -y, -z | 2.759 | 3.486 (1) | 134.0 |
C33—H33···centroid(B') | -x, -y, -z | 2.808 | 3.550 (1) | 135.6 |
Symmetry | H···A | D···A | D-H···A | |
C51—H51A···centroid(B) | 2-x, 2-y, 2-z | 2.88 | 3.691 (2) | 141.2 |
C26—H26···centroid(C) | 2-x, 2-y, 2-z | 2.87 | 3.470 (2) | 122.3 |
C43—H43A···centroid(B) | 2-x, 2-y, 2-z | 2.89 | 3.810 (2) | 157.2 |
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Owing to the highly fluorescent behaviour emanating from their structure, aryl-substituted oxazoles are an interesting class of compounds (Wiley, 1945). Derived from this property, some 2,5-diaryloxazoles have found commercial application as solutes in liquid scintillators (Bell & Hayes, 1958). A well known representative of this compound type is 1,4-bis(5-phenyloxazol-2-yl)benzene, usually termed POPOP (Hayes et al., 1955). Other arylene- and heteroarylene-bridged bis-oxazoles or bisbenzoxazoles behave as brightening agents (Schinzel et al., 1987) or as efficient ligands for metal-ion complexation (Singh et al., 2008; Drew et al., 2004; Rüttimann et al., 1992). In view of these potential applications, the new title compounds, (I) and (II), featuring m-phenylene-bridged bis-oxazole derivatives with different aryl substituents in the 4- and 5-positions of the oxazole units, have been synthesized and their crystal structures are reported here.
Perspective views of the molecular structures of (I) and (II) are shown in Fig. 1. The conformations of the molecules of (I) and (II) may be described by the relevant interplanar angles between the ring fragments (Table 1; ring definitions in Fig. 1).
The crystal structure of bis-oxazole (I) shows bond distances within the oxazole rings which permit exact distinction between N and O [C1—N1 = 1.303 (2) Å and C1—O1 = 1.337 (2) Å for ring A; C22—N2 = 1.297 (2) Å and C22—O2 = 1.350 (2) Å for ring A'], so that the molecule adopts a conformation with an anti arrangement of identical heteroatoms (Fig. 1a). The central tricyclic part of the molecule is not perfectly planar; the oxazole rings are inclined to the phenylene unit at angles of 2.3 (1)° for A/D and 8.2 (1)° for A'/D'. Except for phenyl ring C, the other peripheral phenyl rings are considerably twisted with reference to the oxazole unit to which they are bound. The dihedral angles formed by the pairs of terminal rings are 50.3 (1)° for B/C and 51.3 (1)° for B'/C'.
The crystal structure of (I) is characterized by a columnar packing of molecules in direction of the a axis. As displayed in Fig. 2, extensive π–π interaction (Dance, 2004; Janiak, 2000) between phenyl ring C and oxazole ring A' occurs along the stacking axis of molecules. The closest distances between the centroids of interacting rings vary from 3.558 (3) Å at (x+1/2, y, -z+1/2) to 3.597 (3) Å at (x-1/2, y, -z+1/2). The molecular stacking following from that seems to be stabilized as well by additional π–π interactions between A and D at (x-1/2, y, -z+1/2), with a centroid–distance of 3.615 (3)Å. Only one of the N atoms participates in hydrogen bonding (H5···N1 = 2.56 Å and C5—H5···N1 = 168°). Further details of the C—H···N. C—H···O and C–H···π interactions are given in Table 2.
In bis-oxazole (II), the presence of the bulky tert-butyl residues markedly changes the molecular conformation and the packing behaviour of the molecules in the crystal structure compared with (I). The m-phenylenebis-oxazole fragment of (II) is approximately planar, with the largest atomic distance from its mean plane being 0.055 (2) Å for atom C23. Without exception, and thus most markedly differing from (I), all the peripheral aryl rings show a distinct twist with reference to the oxazole unit to which they are bound. The dihedral angles formed by the pairs of terminal aryl rings are 54.4 (1) and 54.2 (1)° for B/C and B'/C', respectively. Moreover, unlike in (I), identical heteroatoms of the heterocyclic rings adopt a syn arrangement, so that in the solid state the molecule has pseudo-mirror symmetry (point group Cs), with atoms C18 and C21 lying in the pseudo-symmetry plane.
The steric requirement of the tert-butyl substituents drastically reduces the extent of intermolecular interaction, which is restricted to a few C—Hπ contacts (Nishio, 2004) listed in Table 3. Hence, the crystal structure is stabilized by van der Waals forces rather than directed non-covalent bonding. As shown in the crystal packing diagram (Fig. 3), the crystal structure of (II) is composed of weakly bound dimers centred about an inversion centre.
In summary, the most remarkable distinguishing feature between the crystal structures of (I) and (II) is the different molecular conformations with respect to the orientation of the O and N atoms of the oxazole units: anti in (I) and syn in (II). This might be a result of the long-range π-stacking interaction between the molecules in the structure of (I), whereas the bulky tert-butyl groups of (II) prevent extensive π-stacking but cause the molecules to associate into weakly bound dimers centred about an inversion centre, with the hetero atoms in a syn conformation. Moreover, compared with the almost flat structure of crystalline POPOP (Schindler et al., 2010), which makes efficient conjugation of the π-systems very likely, the molecular conformations of (I) and (II) are much more twisted, in particular with respect to the peripheral aryl–oxazole bonds. This could be one of the reasons contributing to the lack of fluorescence of bis-oxazoles (I) and (II) in the solid state, while POPOP is highly fluorescent.