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The crystal structure of morphine bis­(1-naph­tho­ate) [or 7,8-di­de­hydro-4,5-epoxy-17-methyl­morphinan-2,6-diyl bis­(naph­thal­ene-1-carboxyl­ate)], C39H31NO5, determined at 123 K, shows extensive C—H...π interactions in the crystal lattice. Of particular interest is an intramolecular C—H...π interaction within the unit cell between the two naphthoyl groups. Comparison of the opiate scaffolds of morphine bis­(1-naph­tho­ate) and morphine shows only a small increase in strain due to the steric bulk of the naphthoyl groups. The crystal packing shows distinct areas of packing for the naphthalene/aromatic groups and the opiate backbone. Extensive inter- and intramolecular C—H...π interactions lead to a densely packed aromatic region in the crystal lattice.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103015622/gd1262sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103015622/gd1262Isup2.hkl
Contains datablock I

CCDC reference: 221070

Comment top

Opiate-derived compounds have been widely investigated for their medicinal properties (Schmidhammer, 1998; Rawal, 1999). During our research on the development of modified and improved synthetic pathways to pharmaceutical opiates, we have encountered problems with opiate products binding to various transition metals. In particular, FeII and FeIII in the Polonoski reaction and MnO2 in oxidation protocols have been especially problematic. The improved work-up procedures we have used to tackle this problem include competitive binding (Scammells et al., 2002) and ionic liquid extraction (Singer & Scammells, 2001). When using morphine as a starting material in opiate synthesis it is usual to protect either one or both of the hydroxyl groups. Our latest approach to inhibit binding of the opiate to the transition metal is by applying suitable protecting group methodology.

We reasoned that the O atoms of the phenol, ether and hydroxy groups (3-, 4/5- and 6-positions, respectively) of morphine and related opiates may be responsible for these interactions with transition metal ions. As a result, we were interested in employing a protecting group that addressed this issue, and we chose to investigate protection of the 3- and 6-OH group by the 1-naphthoyl group. This group not only reduces the electron density of the O atom in the 3- and 6-positions (via its electron-withdrawing resonance effect) but also supplies considerable steric bulk to further inhibit binding of transition metals to the opiate pocket. However, because of the close spatial proximity of the two alcohol groups of morphine-derived opiates, we were interested in determining the orientations of the ester groups and which of the ester groups would be more distorted from its normal position. Other properties we were hoping to affect were polarity and solubility, in particular the ease of purification of the opiate intermediates by improved column chromatography characteristics and the ease of crystallization of the product from related opiate by-products.

In the title compound, (I) (Fig. 1), the phenol naphthalenecarboxylate group (Nap1) is in an orientation favouring intramolecular C—H···π interactions (Table 1) with the naphthalenecarboxylate group attached to the secondary alcohol (Nap2). The distance between the Nap1 and Nap2 planes and the interplanar angle [65.22 (6) °] can be interpreted as a C—H···π non-bonding interaction.

Intermolecular C—H···π interactions between this molecule and its closest neighbours are also present in the crystal lattice. (Fig. 2 and Table 1). There are extensive intra- and intermolecular C—H···π interactions within the crystal lattice. The interactions involving atoms C3 and C37 generate a ladder along [100] while that involving atom C22 generates a spiral chain along [100].

Several crystal structures of benzoyl-protected phenols have been solved, the simplest being phenol benzoylate (Shibakami & Sekiya, 1995). The angle between the phenol C—O bond and the benzene ring in phenol benzoylate is 3.3°, which is similar to the angle for the analogous bond in (I) [5.1 (s.u. value?) °]. The dihedral angle between the phenol aromatic ring and the carboxy group is 63.3° in phenol benzoylate [cf.76.7 (4)° for the dihedral angle C1—C2—O2—C18 in (I)]. The dihedral angle between the benzoyl aromatic ring and the carboxy group in phenol benzoylate is 8.8° [cf. values in (I) of O3—C18—C19—C20 = 41.6 (4) and O5—C29—C30—C31 = 25.7 (4)°].

Several properties of (I) were affected by the presence of the large naphthoyl-protecting groups [cf. codeine methyl ether (CME) or morphine]. (I) was considerably less polar than CME or morphine, and purification of (I) by column chromatography was successful using 10% methanol in dichloromethane. In this solvent system, morphine and CME had an Rf value of 0.0. Compound (I) also has a much lower solubility than morphine or CME in methanol and thus has the potential for facile purification of the desired opiate product from by-products during further synthesis.

This work has demonstrated that the bulky naphthoyl group can be attached to the morphine scaffold to give morphine di-(naphthalene-1-carboxylate), which has significantly different physical properties to related opiates. Intramolecular C—H···π non-bonding interactions are present in the unit cell, as well as extensive intermolecular C—H···π interactions within the crystal lattice.

Experimental top

Compound (I) was prepared by stirring (-)-morphine and 1-naphthoyl chloride together at room temperature in pyridine for 16 h, and then heating the mixture at 333 K for 4 h. The crude product was purified by column chromatography in order to remove a small amount of morphine mono-(naphthalene-1-carboxylate). Prism-like crystals of (I) were grown by slow evaporation of a methanol solution (m.p. 462.5–464 K).

Refinement top

The Flack (1983) test results were ambiguous so the Friedel pairs were merged and the absolute structure was assigned by reference to (-)-morphine.

Computing details top

Data collection: Collect (Nonius, 1997–2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. ORTEP-3 (Farrugia, 1997) view of (I). Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The C—H···π interactions in (I). Molecules are labelled by symmetry operator.
(I) top
Crystal data top
C39H31NO5Dx = 1.306 Mg m3
Mr = 593.67Melting point = 189.5–191 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 20348 reflections
a = 7.8435 (1) Åθ = 3.5–27.9°
b = 9.7218 (2) ŵ = 0.09 mm1
c = 39.5921 (9) ÅT = 123 K
V = 3019.0 (1) Å3Prismatic, colourless
Z = 40.22 × 0.18 × 0.15 mm
F(000) = 1248
Data collection top
Nonius KappaCCD
diffractometer
2498 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.068
Horizonally mounted graphite crystal monochromatorθmax = 27.9°, θmin = 3.7°
Detector resolution: 9 pixels mm-1h = 1010
CCD rotation images, thick slices scansk = 127
20279 measured reflectionsl = 5232
4065 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.112 w = 1/[σ2(Fo2) + (0.0421P)2 + 0.662P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
4065 reflectionsΔρmax = 0.23 e Å3
407 parametersΔρmin = 0.25 e Å3
0 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods
Crystal data top
C39H31NO5V = 3019.0 (1) Å3
Mr = 593.67Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.8435 (1) ŵ = 0.09 mm1
b = 9.7218 (2) ÅT = 123 K
c = 39.5921 (9) Å0.22 × 0.18 × 0.15 mm
Data collection top
Nonius KappaCCD
diffractometer
2498 reflections with I > 2σ(I)
20279 measured reflectionsRint = 0.068
4065 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.112H-atom parameters constrained
S = 1.03Δρmax = 0.23 e Å3
4065 reflectionsΔρmin = 0.25 e Å3
407 parametersAbsolute structure: Flack (1983)
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.0284 (4)0.0096 (3)0.36308 (8)0.0258 (7)
C20.0132 (4)0.0184 (3)0.39621 (8)0.0298 (8)
C30.1789 (5)0.0061 (3)0.40675 (9)0.0338 (8)
H30.20870.01000.42970.041*
C40.3019 (4)0.0534 (3)0.38452 (8)0.0320 (8)
H40.41570.06590.39210.038*
C50.2594 (4)0.0832 (3)0.35084 (8)0.0281 (8)
C60.0918 (4)0.0648 (3)0.34178 (8)0.0250 (7)
C70.0140 (4)0.0841 (3)0.30730 (8)0.0257 (7)
C80.1393 (4)0.0154 (3)0.31061 (8)0.0271 (8)
H80.23860.02260.29780.032*
C90.0998 (4)0.1631 (3)0.29781 (8)0.0277 (8)
H90.16310.17750.27620.033*
C100.0841 (4)0.1943 (4)0.29157 (8)0.0297 (8)
H100.12130.28680.29380.036*
C110.1980 (4)0.0998 (4)0.28306 (8)0.0297 (8)
H110.31150.12740.27810.036*
C120.1521 (4)0.0495 (3)0.28112 (8)0.0270 (8)
H120.10670.06960.25800.032*
C130.3036 (4)0.1471 (3)0.28833 (8)0.0307 (8)
H130.39260.12650.27100.037*
C140.3870 (4)0.1197 (4)0.32353 (8)0.0328 (8)
H14A0.45060.20280.33060.039*
H14B0.46990.04350.32130.039*
C150.0426 (4)0.2335 (3)0.30211 (9)0.0306 (8)
H15A0.12800.25790.31950.037*
H15B0.09740.24260.27970.037*
C160.1065 (4)0.3320 (3)0.30431 (9)0.0346 (9)
H16A0.14810.33580.32790.042*
H16B0.06840.42540.29780.042*
C170.3848 (5)0.3896 (4)0.28184 (9)0.0448 (10)
H17A0.43120.39910.30470.067*
H17B0.47500.35840.26650.067*
H17C0.34120.47870.27420.067*
C180.2301 (4)0.0021 (4)0.42977 (8)0.0311 (8)
C190.3634 (4)0.0738 (3)0.44873 (8)0.0294 (8)
C200.4162 (4)0.1987 (4)0.43702 (9)0.0361 (9)
H200.36020.23930.41820.043*
C210.5529 (5)0.2678 (4)0.45255 (10)0.0426 (10)
H210.58990.35390.44390.051*
C220.6327 (5)0.2124 (4)0.47998 (10)0.0455 (10)
H220.72450.26020.49030.055*
C230.5793 (4)0.0836 (4)0.49308 (9)0.0355 (8)
C240.6603 (5)0.0242 (4)0.52175 (10)0.0473 (11)
H240.75240.07110.53220.057*
C250.6083 (5)0.0979 (5)0.53431 (10)0.0491 (11)
H250.66540.13670.55320.059*
C260.4712 (5)0.1672 (4)0.51968 (10)0.0441 (10)
H260.43360.25170.52910.053*
C270.3898 (4)0.1147 (4)0.49171 (9)0.0367 (9)
H270.29760.16380.48180.044*
C280.4426 (4)0.0120 (3)0.47759 (8)0.0291 (8)
C290.3269 (4)0.2904 (3)0.32364 (8)0.0282 (8)
C300.3655 (4)0.4028 (3)0.34800 (8)0.0274 (8)
C310.2400 (4)0.4973 (3)0.35490 (8)0.0304 (8)
H310.13050.48590.34510.036*
C320.2699 (4)0.6103 (4)0.37609 (9)0.0310 (8)
H320.18130.67470.38030.037*
C330.4246 (4)0.6281 (3)0.39064 (9)0.0329 (8)
H330.44310.70450.40520.039*
C340.5590 (4)0.5342 (3)0.38447 (8)0.0280 (8)
C350.7207 (4)0.5515 (4)0.40014 (9)0.0334 (9)
H350.73980.62900.41430.040*
C360.8487 (4)0.4590 (4)0.39526 (9)0.0353 (9)
H360.95610.47160.40590.042*
C370.8205 (4)0.3448 (4)0.37436 (9)0.0352 (9)
H370.91020.28060.37090.042*
C380.6671 (4)0.3235 (4)0.35878 (9)0.0314 (8)
H380.65160.24450.34500.038*
C390.5307 (4)0.4181 (4)0.36301 (8)0.0262 (7)
N10.2455 (3)0.2886 (3)0.28206 (7)0.0329 (7)
O10.1801 (3)0.0174 (2)0.34684 (5)0.0300 (5)
O20.1054 (3)0.0819 (2)0.41801 (5)0.0341 (6)
O30.2301 (3)0.1242 (3)0.42426 (6)0.0460 (7)
O40.1569 (3)0.2668 (2)0.32179 (6)0.0298 (6)
O50.4283 (3)0.2277 (3)0.30652 (6)0.0401 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0264 (16)0.0238 (18)0.0271 (18)0.0034 (15)0.0010 (14)0.0003 (16)
C20.0347 (19)0.0275 (19)0.0270 (18)0.0030 (16)0.0069 (15)0.0042 (16)
C30.045 (2)0.032 (2)0.0240 (18)0.0026 (18)0.0028 (16)0.0039 (16)
C40.0306 (18)0.033 (2)0.033 (2)0.0008 (16)0.0040 (15)0.0024 (16)
C50.0289 (17)0.0274 (18)0.0280 (19)0.0003 (16)0.0006 (15)0.0011 (16)
C60.0242 (16)0.0243 (18)0.0265 (18)0.0030 (15)0.0000 (14)0.0011 (15)
C70.0212 (15)0.0302 (19)0.0256 (18)0.0012 (15)0.0019 (14)0.0030 (16)
C80.0230 (16)0.0324 (19)0.0257 (17)0.0032 (15)0.0026 (14)0.0027 (16)
C90.0267 (17)0.032 (2)0.0245 (18)0.0033 (16)0.0009 (15)0.0048 (15)
C100.0285 (17)0.033 (2)0.0271 (19)0.0056 (16)0.0022 (16)0.0028 (16)
C110.0249 (17)0.038 (2)0.0264 (19)0.0017 (16)0.0018 (14)0.0049 (17)
C120.0242 (16)0.035 (2)0.0222 (17)0.0013 (15)0.0024 (13)0.0002 (15)
C130.0274 (17)0.038 (2)0.0269 (19)0.0016 (16)0.0040 (15)0.0007 (16)
C140.0252 (17)0.040 (2)0.033 (2)0.0041 (16)0.0020 (15)0.0006 (17)
C150.0312 (18)0.033 (2)0.028 (2)0.0044 (16)0.0010 (15)0.0033 (16)
C160.041 (2)0.031 (2)0.032 (2)0.0012 (17)0.0044 (17)0.0046 (16)
C170.048 (2)0.048 (2)0.038 (2)0.017 (2)0.0068 (19)0.0009 (19)
C180.0362 (19)0.032 (2)0.0255 (18)0.0056 (18)0.0011 (15)0.0015 (17)
C190.0306 (17)0.0278 (19)0.0297 (19)0.0040 (16)0.0049 (15)0.0056 (16)
C200.042 (2)0.035 (2)0.031 (2)0.0018 (18)0.0067 (17)0.0045 (17)
C210.044 (2)0.040 (2)0.044 (2)0.0066 (19)0.0122 (19)0.002 (2)
C220.038 (2)0.047 (3)0.052 (3)0.0063 (19)0.004 (2)0.015 (2)
C230.0310 (18)0.040 (2)0.036 (2)0.0044 (18)0.0014 (16)0.0098 (18)
C240.045 (2)0.052 (3)0.044 (2)0.010 (2)0.016 (2)0.019 (2)
C250.056 (3)0.049 (3)0.042 (2)0.021 (2)0.014 (2)0.011 (2)
C260.056 (2)0.036 (2)0.041 (2)0.007 (2)0.002 (2)0.0030 (19)
C270.039 (2)0.034 (2)0.037 (2)0.0044 (18)0.0042 (18)0.0043 (17)
C280.0285 (16)0.0283 (19)0.0306 (19)0.0028 (16)0.0011 (15)0.0088 (16)
C290.0238 (16)0.031 (2)0.030 (2)0.0015 (16)0.0025 (15)0.0001 (16)
C300.0271 (17)0.0257 (18)0.0293 (19)0.0052 (15)0.0032 (14)0.0041 (16)
C310.0257 (16)0.033 (2)0.0322 (19)0.0007 (16)0.0003 (15)0.0043 (17)
C320.0303 (18)0.028 (2)0.035 (2)0.0016 (16)0.0041 (16)0.0003 (16)
C330.038 (2)0.0234 (19)0.037 (2)0.0020 (17)0.0041 (17)0.0033 (16)
C340.0275 (17)0.029 (2)0.0271 (18)0.0062 (16)0.0031 (14)0.0030 (16)
C350.0325 (19)0.033 (2)0.034 (2)0.0078 (16)0.0005 (16)0.0048 (17)
C360.0283 (18)0.039 (2)0.038 (2)0.0067 (17)0.0015 (16)0.0009 (18)
C370.0249 (17)0.037 (2)0.043 (2)0.0024 (16)0.0012 (17)0.0039 (19)
C380.0283 (17)0.029 (2)0.037 (2)0.0051 (16)0.0037 (16)0.0007 (16)
C390.0232 (16)0.0289 (19)0.0264 (18)0.0050 (15)0.0043 (14)0.0031 (16)
N10.0337 (15)0.0358 (18)0.0290 (16)0.0081 (14)0.0057 (14)0.0021 (14)
O10.0253 (11)0.0385 (14)0.0261 (13)0.0021 (11)0.0030 (10)0.0017 (11)
O20.0414 (14)0.0319 (13)0.0290 (13)0.0061 (12)0.0095 (11)0.0042 (11)
O30.0536 (17)0.0326 (15)0.0519 (17)0.0070 (13)0.0204 (14)0.0111 (13)
O40.0237 (11)0.0326 (13)0.0331 (14)0.0035 (10)0.0019 (10)0.0051 (11)
O50.0272 (12)0.0499 (16)0.0433 (15)0.0001 (12)0.0035 (12)0.0151 (13)
Geometric parameters (Å, º) top
C1—C61.374 (4)C18—O31.206 (4)
C1—O11.378 (4)C18—O21.357 (4)
C1—C21.379 (4)C18—C191.484 (5)
C2—C31.385 (5)C19—C201.363 (5)
C2—O21.411 (4)C19—C281.433 (5)
C3—C41.385 (5)C20—C211.407 (5)
C3—H30.9500C20—H200.9500
C4—C51.404 (4)C21—C221.365 (5)
C4—H40.9500C21—H210.9500
C5—C61.374 (4)C22—C231.418 (5)
C5—C141.515 (4)C22—H220.9500
C6—C71.507 (4)C23—C281.418 (5)
C7—C151.532 (4)C23—C241.423 (5)
C7—C121.536 (4)C24—C251.349 (5)
C7—C81.549 (4)C24—H240.9500
C8—O11.470 (4)C25—C261.395 (5)
C8—C91.555 (5)C25—H250.9500
C8—H81.0000C26—C271.376 (5)
C9—O41.456 (4)C26—H260.9500
C9—C101.494 (4)C27—C281.414 (5)
C9—H91.0000C27—H270.9500
C10—C111.326 (4)C29—O51.210 (4)
C10—H100.9500C29—O41.355 (4)
C11—C121.497 (5)C29—C301.488 (4)
C11—H110.9500C30—C311.374 (4)
C12—C131.547 (4)C30—C391.433 (4)
C12—H121.0000C31—C321.402 (5)
C13—N11.471 (4)C31—H310.9500
C13—C141.562 (4)C32—C331.354 (5)
C13—H131.0000C32—H320.9500
C14—H14A0.9900C33—C341.416 (5)
C14—H14B0.9900C33—H330.9500
C15—C161.514 (5)C34—C351.422 (5)
C15—H15A0.9900C34—C391.430 (4)
C15—H15B0.9900C35—C361.362 (5)
C16—N11.464 (4)C35—H350.9500
C16—H16A0.9900C36—C371.402 (5)
C16—H16B0.9900C36—H360.9500
C17—N11.469 (4)C37—C381.368 (5)
C17—H17A0.9800C37—H370.9500
C17—H17B0.9800C38—C391.421 (5)
C17—H17C0.9800C38—H380.9500
C6—C1—O1112.4 (3)N1—C17—H17C109.5
C6—C1—C2119.9 (3)H17A—C17—H17C109.5
O1—C1—C2127.7 (3)H17B—C17—H17C109.5
C1—C2—C3118.3 (3)O3—C18—O2122.0 (3)
C1—C2—O2120.8 (3)O3—C18—C19125.5 (3)
C3—C2—O2120.6 (3)O2—C18—C19112.4 (3)
C4—C3—C2121.3 (3)C20—C19—C28120.9 (3)
C4—C3—H3119.4C20—C19—C18119.0 (3)
C2—C3—H3119.4C28—C19—C18120.0 (3)
C3—C4—C5120.5 (3)C19—C20—C21120.6 (4)
C3—C4—H4119.8C19—C20—H20119.7
C5—C4—H4119.8C21—C20—H20119.7
C6—C5—C4116.6 (3)C22—C21—C20120.6 (4)
C6—C5—C14118.4 (3)C22—C21—H21119.7
C4—C5—C14124.7 (3)C20—C21—H21119.7
C5—C6—C1123.2 (3)C21—C22—C23120.3 (4)
C5—C6—C7127.4 (3)C21—C22—H22119.9
C1—C6—C7109.1 (3)C23—C22—H22119.9
C6—C7—C15110.9 (3)C28—C23—C22119.9 (3)
C6—C7—C12107.3 (3)C28—C23—C24118.9 (4)
C15—C7—C12108.8 (3)C22—C23—C24121.2 (4)
C6—C7—C899.2 (2)C25—C24—C23121.1 (4)
C15—C7—C8112.2 (2)C25—C24—H24119.5
C12—C7—C8117.9 (3)C23—C24—H24119.5
O1—C8—C7105.1 (2)C24—C25—C26120.3 (4)
O1—C8—C9110.4 (2)C24—C25—H25119.9
C7—C8—C9113.2 (3)C26—C25—H25119.9
O1—C8—H8109.3C27—C26—C25120.9 (4)
C7—C8—H8109.3C27—C26—H26119.6
C9—C8—H8109.3C25—C26—H26119.6
O4—C9—C10105.3 (3)C26—C27—C28120.3 (3)
O4—C9—C8111.5 (2)C26—C27—H27119.9
C10—C9—C8115.7 (3)C28—C27—H27119.9
O4—C9—H9108.0C27—C28—C23118.6 (3)
C10—C9—H9108.0C27—C28—C19123.6 (3)
C8—C9—H9108.0C23—C28—C19117.8 (3)
C11—C10—C9123.5 (3)O5—C29—O4122.1 (3)
C11—C10—H10118.2O5—C29—C30126.8 (3)
C9—C10—H10118.2O4—C29—C30111.0 (3)
C10—C11—C12121.5 (3)C31—C30—C39119.7 (3)
C10—C11—H11119.2C31—C30—C29118.3 (3)
C12—C11—H11119.2C39—C30—C29121.9 (3)
C11—C12—C7110.3 (3)C30—C31—C32121.6 (3)
C11—C12—C13113.6 (3)C30—C31—H31119.2
C7—C12—C13106.4 (2)C32—C31—H31119.2
C11—C12—H12108.8C33—C32—C31120.3 (3)
C7—C12—H12108.8C33—C32—H32119.8
C13—C12—H12108.8C31—C32—H32119.8
N1—C13—C12107.8 (2)C32—C33—C34120.7 (3)
N1—C13—C14116.1 (3)C32—C33—H33119.6
C12—C13—C14112.4 (3)C34—C33—H33119.6
N1—C13—H13106.7C33—C34—C35120.8 (3)
C12—C13—H13106.7C33—C34—C39119.7 (3)
C14—C13—H13106.7C35—C34—C39119.4 (3)
C5—C14—C13113.6 (3)C36—C35—C34121.2 (3)
C5—C14—H14A108.8C36—C35—H35119.4
C13—C14—H14A108.8C34—C35—H35119.4
C5—C14—H14B108.8C35—C36—C37119.4 (3)
C13—C14—H14B108.9C35—C36—H36120.3
H14A—C14—H14B107.7C37—C36—H36120.3
C16—C15—C7111.6 (3)C38—C37—C36121.7 (3)
C16—C15—H15A109.3C38—C37—H37119.2
C7—C15—H15A109.3C36—C37—H37119.2
C16—C15—H15B109.3C37—C38—C39120.7 (3)
C7—C15—H15B109.3C37—C38—H38119.6
H15A—C15—H15B108.0C39—C38—H38119.6
N1—C16—C15111.0 (3)C38—C39—C34117.6 (3)
N1—C16—H16A109.4C38—C39—C30124.4 (3)
C15—C16—H16A109.4C34—C39—C30118.0 (3)
N1—C16—H16B109.4C16—N1—C17111.4 (3)
C15—C16—H16B109.4C16—N1—C13113.5 (3)
H16A—C16—H16B108.0C17—N1—C13113.3 (3)
N1—C17—H17A109.5C1—O1—C8105.4 (2)
N1—C17—H17B109.5C18—O2—C2115.0 (3)
H17A—C17—H17B109.5C29—O4—C9117.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AH···AD···AD—H···A
C3—H3···Cg2i2.983.711 (4)135
C21—H21···Cg12.803.512 (4)132
C22—H22···Cg2ii2.943.873 (4)166
C37—H37···Cg3iii3.073.690 (4)124
Symmetry codes: (i) x+1, y, z; (ii) x1/2, y+1/2, z+1; (iii) x1, y, z.

Experimental details

Crystal data
Chemical formulaC39H31NO5
Mr593.67
Crystal system, space groupOrthorhombic, P212121
Temperature (K)123
a, b, c (Å)7.8435 (1), 9.7218 (2), 39.5921 (9)
V3)3019.0 (1)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.22 × 0.18 × 0.15
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
20279, 4065, 2498
Rint0.068
(sin θ/λ)max1)0.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.112, 1.03
No. of reflections4065
No. of parameters407
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.25
Absolute structureFlack (1983)

Computer programs: Collect (Nonius, 1997–2000), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AH···AD···AD—H···A
C3—H3···Cg2i2.983.711 (4)135
C21—H21···Cg12.803.512 (4)132
C22—H22···Cg2ii2.943.873 (4)166
C37—H37···Cg3iii3.073.690 (4)124
Symmetry codes: (i) x+1, y, z; (ii) x1/2, y+1/2, z+1; (iii) x1, y, z.
 

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