organic papers
o792
Chabaudet al. C18H23NO6 doi:10.1107/S1600536805005404 Acta Cryst.(2005). E61, o792–o794
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
Phenacyl (2
S
,4
S
)-1-
tert
-butoxycarbonyl-4-hydroxyprolinate
Pauline Chabaud,aMonica Worf,aJe´roˆme Courcambeck,b Michel Camploaand Ge´rard Pe`pea*
aGCOM2 UMR-CNRS 6114, Universite´
d’Aix-Marseille II, Campus de Luminy, Case 901, 13288 Marseille Cedex 9, France, and
bGenoScience, 23 Rue de Friedland, 13006
Marseille, France
Correspondence e-mail: pepe@luminy.univ-mrs.fr
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C–C) = 0.004 A˚
Rfactor = 0.042
wRfactor = 0.139 Data-to-parameter ratio = 7.8
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain – all rights reserved
The title compound, C18H23NO6, is a 4-hydroxyproline
derivative of the type found in many compounds with biological activity. The crystal structure involves an inter-molecular O—H O hydrogen bond, linking molecules into a chain along a screw axis.
Comment
Proline and its 4-substituted derivatives are important amino acids in many naturally occurring bioactive peptides, such as gramicidin (Tamaki et al., 1985), and have been extensively used in the pharmaceutical industry as angiotensin-converting enzyme (ACE) inhibitors, including Captopril (Ondettiet al., 1977) and Enalapril (Patchett et al., 1980). Moreover, the hydroxyproline scaffold offers three points of attachment (the amine, the hydroxyl and the carboxyl groups), making it a good candidate for library production (Vergnonet al., 2004). We present here the structure of the title compound, (4).
In the crystal structure of (4), an intermolecular hydrogen bond is observed between hydroxyl group O27 and carbonyl atom O33 [O27—H27 = 0.92 (5) A˚ , H27 O33i= 1.82 (5) A˚ , O27 O33i= 2.733 (3) A˚ and O27—H27 O33i = 169 (5); symmetry code: (i)x+1
2,y+ 1
2,z+ 1].
Experimental
In the reaction scheme, the steps are as follows: (a) Cs2CO3, MeOH,
H2O then CH3I, dimethylformamide (DMF), 24 h, room
tempera-ture; (b) PPh3, diisopropylazodicarboxylate (DIAD), HCO2H,
tetrahydrofuran (THF), 16 h, room temperature; (c) NaOH, H2O,
THF, 3 h, 273 K then room temperature; (d) Cs2CO3, MeOH, H2O
then phenacyl bromide (PacBr), DMF, 30 min, room temperature. Commercially available reagents and solvents were used as received. Anhydrous solvents were distilled; THF was purified by distillation over sodium and benzophenone. Flash column chromatography was performed on silica gel (40–60mm)
purchased from Merck. 1H NMR spectra were recorded at 250 MHz on a Bruker instrument and chemical shifts are reported as(p.p.m., internal reference trimethylsilane). Low-resolution mass spectra were acquired using a Jeol DX-100 instrument with positive mode fast atom bombardment (FAB), with 4-nitrobenzyl alcohol as matrix. Optical rotations were measured on a Perkin–Elmer 241 polarimeter in a 10 cm cell.
(2S,4R)-N-tert-butoxycarbonyl-4-hydroxyproline (5.92 g, 25.6 mmol, 1 equivalent) was dissolved in water (7 ml) and methanol (52 ml), and a 20% aqueous solution of Cs2CO3was
added until the pH was 7. The solvents were then evaporated under reduced pressure and the remaining residue was dissolved in anhydrous DMF (65 ml) under argon. To this solution was added methyl iodide (2.55 ml, 41.0 mol, 1.6 equivalents) and the resulting mixture was stirred for 24 h at room temperature. The reaction was quenched by addition of brine (65 ml) and then extracted with EtOAc (3
65 ml). The combined organic layers were successively washed with water (5 65 ml), a saturated aqueous solution of NaHCO3(130 ml) and brine (130 ml). They were dried over
anhydrous MgSO4and concentrated under reduced pressure.
Compound (1) was obtained as a yellow oil (5.70 g, 91%) and was used directly for the next step.
To a solution of (1) (5.64 g, 23.0 mmol, 1 equivalent), triphenylphosphine (12.1 g, 45.9 mmol, 2 equivalents) and formic acid (1.75 ml, 45.9 mmol, 2 equivalents) in anhydrous THF (60 ml) under argon was added dropwise a 40% solution of diisopropylazodicarboxylate (8.91 ml, 45.9 mmol, 2 equivalents) in THF. The resulting mixture was stirred for 16 h at room temperature and then quenched with a saturated aqueous solution of NaHCO3(250 ml). After extraction with
EtOAc (3100 ml), the combined organic layers were dried over anhydrous MgSO4 and concentrated under reduced
pressure. The crude product was purified by flash column chromatography (cyclohexane–EtOAc, 7:3) and compound
(2) [Rf = 0.26 (cyclohexane–EtOAc, 7:3)] was obtained,
together with diisopropyl-1,2-hydrazine dicarboxylate and triphenylphosphine.
This mixture (about 15 g) was used directly for the sapon-ification step. It was dissolved in THF (60 ml) and a solution of 1NNaOH (75.8 ml, 75.8 mmol) was added dropwise at 273 K The mixture was stirred for 3 h at room temperature and then neutralized with 1N HCl (20 ml). The solution was then concentrated under reduced pressure and the resulting residue was dissolved in water (40 ml). It was washed with EtOAc (2
100 ml), acidified to pH 2 with 1NHCl, and finally extracted with EtOAc (6130 ml). The combined organic layers were dried over anhydrous MgSO4and evaporated to dryness. The
crude product was recrystallized (EtOAc–cyclohexane) to obtain compound (3) (2.46 g, 46%) as a white powder.
To a solution of (3) (1.54 g, 6.64 mmol, 1 equivalent) in MeOH (27 ml) was added a solution of Cs2CO3 (1.09 g,
3.32 mmol, 0.5 equivalents) in water (17 ml) at 273 K. The solvents were evaporated under reduced pressure and the remaining residue dissolved in anhydrous DMF (33 ml) under argon. Phenacyl bromide (1.32 g, 6.64 mmol, 1 equivalent) was added dropwise at 273 K and the resulting mixture was stirred at room temperature for 30 min. It was filtered and the filtrate was evaporated. The resulting oil was dissolved in EtOAc (100 ml) and successively washed with water (535 ml) and a saturated aqueous solution of NaHCO3 (2 30 ml), dried
over anhydrous MgSO4, and evaporated to dryness. The crude
product was purified by flash column chromatography on silica gel (cyclohexane–EtOAc 1:1 to 3:7) and the title compound, (4) (2.21 g, 95%), was obtained as a white solid. It was dissolved in ethyl acetate and colourless crystals (cube-shaped) were obtained withn-hexane as precipitant.
Spectroscopic analysis (atom numbers as in Fig. 1, with H atoms following sequentially in the same scheme):1H NMR (CDCl3,, p.p.m.): 7.92 (2H,d,J= 8.0 Hz, H9), 7.62 (1H,t,J=
8.4 Hz, H5), 7.50 (2H,t,J= 6.5 Hz, H7), 5.57 and 5.32 (1H, AB system,JAB= 16.5 Hz, H14), 5.42 (1H, s, H14), 4.53 (1H,m,
H25), 4.44 (1H,m, H20), 3.40 to 3.80 (2H,m, H28), 2.48 (2H,
m, H22), 1.47 and 1.45 (9H, 2s, H36, H44, H40);13C NMR (CDCl3, , p.p.m.): 192.03 and 191.90 (C12), 173.42 (C18),
154.31 and 153.47 (C32), 134.00 (C11), 133.55 (C5), 128.71 (C9), 127.61 (C3), 80.22 (C35), 70.98 and 69.98 (C25), 66.25 and 65.98 (C14), 57.76 and 57.54 (C20), 55.82 and 55.34 (C28), 38.99 and 38.14 (C22), 28.14 (C36, C44, C40); FAB+, NBA: 350 (M+1H)+;RF= 0.19 (cyclohexane–EtOAc, 1:1), []D
25
(c1.02, CHCl3=47.1); m.p. 431 K.
Crystal data
C18H23NO6 Mr= 349.37
Orthorhombic,P212121
a= 9.653 (2) A˚
b= 9.780 (2) A˚
c= 19.179 (4) A˚
V= 1810.6 (6) A˚3 Z= 4
Dx= 1.282 Mg m 3
MoKradiation Cell parameters from 7664
reflections
= 3.8–26.6 = 0.10 mm1 T= 293 (2) K Cube, colourless 0.30.30.3 mm
organic papers
Acta Cryst.(2005). E61, o792–o794 Chabaudet al. C
[image:2.610.49.294.71.238.2]18H23NO6
o793
Figure 1
Data collection
Nonius KappaCDD area-detector diffractometer
’scans
Absorption correction: none 13 679 measured reflections 2006 independent reflections
1811 reflections withI> 2(I)
Rint= 0.038
max= 26.6 h=12!12
k=12!12
l=22!22
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.042 wR(F2) = 0.139 S= 0.90 2006 reflections 257 parameters
H atoms treated by a mixture of independent and constrained refinement
w= 1/[2
(Fo2) + (0.1P)2
+ 0.053P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.13 e A˚
3
min=0.13 e A˚
3
Extinction correction:SHELXL97
(Sheldrick, 1997)
Extinction coefficient: 0.22 (6)
The hydroxy H atom was located in a difference map and refined freely. Other H atoms were positioned geometrically and refined as riding, with C—H = 0.93–0.98 A˚ and freely refinedUisovalues, except
that Uiso(H) was fixed at 0.15 A˚ 2
for the tert-butyl group. In the absence of significant anomalous scattering effects, Friedel pairs were merged. The absolute configuration is assumed from the synthesis.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve
structure:SIR97(Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication:PLATON(Spek, 2003).
References
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999).J. Appl. Cryst.32, 115–119.
Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
Nonius (1998).COLLECT. Nonius BV, Delft, The Netherlands.
Ondetti, M. A., Rubin, B. & Cushman, D. W. (1977).Science,196, 441–444. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.
Patchett, A. A., Harris, E., Tristram, E. W., Wyvratt, M. J., Wu, M. T., Taub, D., Peterson, E. R., Ikeler, T. J., ten Broeke J., Payne, L. G., Ondeyka, D. L., Thorsett, E. D., Greenlee, W. J., Lohr, N. S., Hoffsommer, R. D., Joshua, H., Ruyle, W. V., Rothrock, J. W., Aster, S. D., Maycock, A. L., Robinson, F. M., Hirschmann, R., Sweet, C. S., Ulm, E. H., Gross, D. M., Vassil, T. C. & Stone, C. A. (1980).Nature,288, 280–283.
Sheldrick, G. M. (1997).SHELXL97. University of Go¨ttingen, Germany. Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.
Tamaki, M., Okitsu, T., Araki, M., Sakamoto, H., Takimoto, M. & Muramastu, I. (1985).Bull. Soc. Chem. Soc. Jpn,58, 531–535.
Vergnon, A. L., Pottorf, R. S. & Player, M. R. (2004).J. Combinat. Chem.6, 91–98.
organic papers
o794
Chabaudet al. Csupporting information
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Acta Cryst. (2005). E61, o792–o794
supporting information
Acta Cryst. (2005). E61, o792–o794 [https://doi.org/10.1107/S1600536805005404]
Phenacyl (2
S
,4
S
)-1-
tert
-butoxycarbonyl-4-hydroxyprolinate
Pauline Chabaud, Monica Worf, J
é
r
ô
me Courcambeck, Michel Camplo and G
é
rard P
è
pe
Phenylacyl (2S,4S)-1-tert-butoxycarbonyl-4-hydroxyprolinate
Crystal data C18H23NO6
Mr = 349.37
Orthorhombic, P212121
a = 9.653 (2) Å b = 9.780 (2) Å c = 19.179 (4) Å V = 1810.6 (6) Å3
Z = 4 F(000) = 744
Dx = 1.282 Mg m−3
Melting point: 431 K
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 7664 reflections θ = 3.8–26.6°
µ = 0.10 mm−1
T = 293 K Cube, colourless 0.3 × 0.3 × 0.3 mm
Data collection
Nonius KappaCDD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ scans
13679 measured reflections 2006 independent reflections
1811 reflections with I > 2σ(I) Rint = 0.038
θmax = 26.6°, θmin = 3.8°
h = −12→12 k = −12→12 l = −22→22
Refinement Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.042
wR(F2) = 0.139
S = 0.90 2006 reflections 257 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(F
o2) + (0.1P)2 + 0.053P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.13 e Å−3
Δρmin = −0.13 e Å−3
Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.22 (6)
Special details
supporting information
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Acta Cryst. (2005). E61, o792–o794
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)
x y z Uiso*/Ueq
C1 0.4868 (3) 0.0482 (2) −0.01239 (13) 0.0546 (6)
H2 0.5728 0.0333 0.0081 0.063 (8)*
C3 0.4597 (3) −0.0043 (3) −0.07765 (15) 0.0646 (7)
H4 0.5273 −0.0536 −0.1014 0.086 (11)*
C5 0.3305 (3) 0.0171 (3) −0.10766 (15) 0.0672 (7)
H6 0.3106 −0.0200 −0.1512 0.065 (8)*
C7 0.2328 (3) 0.0924 (3) −0.07337 (15) 0.0614 (6)
H8 0.1472 0.1080 −0.0942 0.079 (10)*
C9 0.2599 (2) 0.1458 (2) −0.00783 (13) 0.0532 (5)
H1 0.1926 0.1968 0.0152 0.060 (7)*
C11 0.3870 (2) 0.1230 (2) 0.02320 (11) 0.0458 (5) C12 0.4236 (2) 0.1763 (2) 0.09350 (11) 0.0476 (5) O13 0.5248 (2) 0.1379 (2) 0.12459 (10) 0.0720 (6) C14 0.3296 (3) 0.2843 (3) 0.12552 (12) 0.0548 (6)
H15 0.3182 0.3595 0.0930 0.078 (10)*
H16 0.2390 0.2452 0.1345 0.061 (8)*
O17 0.3872 (2) 0.33398 (17) 0.18896 (8) 0.0566 (5) C18 0.3718 (2) 0.2516 (2) 0.24463 (10) 0.0467 (5)
O19 0.3072 (2) 0.1478 (2) 0.24393 (9) 0.0680 (6)
C20 0.4544 (2) 0.3088 (2) 0.30516 (10) 0.0472 (5)
H21 0.4719 0.4066 0.2982 0.046 (6)*
C22 0.5910 (3) 0.2319 (3) 0.31411 (12) 0.0603 (6)
H23 0.5824 0.1380 0.2985 0.081 (10)*
H24 0.6648 0.2759 0.2882 0.097 (12)*
C25 0.6184 (2) 0.2384 (3) 0.39200 (12) 0.0525 (6)
H26 0.6554 0.3286 0.4042 0.041 (6)*
O27 0.7136 (2) 0.1362 (2) 0.41147 (11) 0.0756 (7)
H27 0.724 (5) 0.139 (5) 0.459 (3) 0.112 (14)*
C28 0.4754 (2) 0.2214 (2) 0.42329 (11) 0.0512 (5)
H29 0.4524 0.1256 0.4292 0.070 (8)*
H30 0.4688 0.2671 0.4681 0.067 (8)*
N31 0.38526 (19) 0.2859 (2) 0.37192 (9) 0.0491 (5) C32 0.2633 (2) 0.3437 (2) 0.38851 (10) 0.0496 (5) O33 0.21212 (19) 0.3396 (2) 0.44657 (9) 0.0679 (6) O34 0.20672 (17) 0.4024 (2) 0.33270 (9) 0.0619 (5) C35 0.0774 (2) 0.4815 (3) 0.33630 (14) 0.0567 (6) C36 −0.0411 (3) 0.3930 (4) 0.3582 (2) 0.0909 (11)
H37 −0.1265 0.4414 0.3513 0.150*
H38 −0.0314 0.3698 0.4066 0.150*
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Acta Cryst. (2005). E61, o792–o794
C40 0.0970 (5) 0.5977 (4) 0.3858 (3) 0.132 (2)
H41 0.0087 0.6374 0.3966 0.150*
H42 0.1555 0.6655 0.3647 0.150*
H43 0.1395 0.5648 0.4278 0.150*
C44 0.0606 (5) 0.5244 (6) 0.2609 (3) 0.1201 (18)
H45 −0.0200 0.5813 0.2565 0.150*
H46 0.0501 0.4447 0.2322 0.150*
H47 0.1410 0.5746 0.2464 0.150*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C1 0.0557 (12) 0.0550 (11) 0.0531 (12) 0.0078 (10) −0.0005 (10) 0.0024 (9) C3 0.0763 (16) 0.0583 (13) 0.0592 (15) 0.0082 (12) 0.0055 (12) −0.0110 (10) C5 0.0861 (19) 0.0591 (13) 0.0563 (14) −0.0056 (13) −0.0123 (12) −0.0130 (11) C7 0.0610 (13) 0.0612 (12) 0.0620 (14) −0.0038 (11) −0.0147 (11) −0.0021 (11) C9 0.0491 (10) 0.0559 (11) 0.0546 (12) −0.0004 (9) −0.0047 (9) 0.0002 (9) C11 0.0511 (10) 0.0423 (9) 0.0440 (10) −0.0037 (8) 0.0004 (8) 0.0033 (7) C12 0.0462 (10) 0.0527 (11) 0.0439 (10) −0.0016 (9) −0.0023 (8) 0.0086 (8) O13 0.0608 (10) 0.0991 (14) 0.0560 (10) 0.0187 (10) −0.0154 (8) −0.0042 (10) C14 0.0641 (14) 0.0610 (12) 0.0392 (10) 0.0083 (11) −0.0107 (9) −0.0002 (9) O17 0.0713 (10) 0.0587 (9) 0.0398 (8) −0.0011 (8) −0.0072 (7) 0.0012 (6) C18 0.0435 (10) 0.0589 (11) 0.0379 (10) 0.0000 (9) 0.0036 (8) −0.0002 (8) O19 0.0703 (11) 0.0841 (12) 0.0495 (9) −0.0277 (11) −0.0014 (8) 0.0032 (8) C20 0.0453 (10) 0.0582 (11) 0.0379 (10) 0.0003 (9) 0.0025 (8) −0.0027 (8) C22 0.0454 (11) 0.0868 (17) 0.0486 (13) 0.0108 (11) −0.0005 (9) −0.0080 (11) C25 0.0439 (10) 0.0649 (12) 0.0487 (12) 0.0051 (10) −0.0087 (8) −0.0098 (9) O27 0.0672 (11) 0.1005 (15) 0.0591 (11) 0.0347 (12) −0.0172 (9) −0.0169 (10) C28 0.0529 (11) 0.0594 (11) 0.0414 (11) 0.0026 (10) −0.0050 (9) 0.0009 (9) N31 0.0450 (9) 0.0646 (10) 0.0376 (9) 0.0061 (8) 0.0006 (7) −0.0005 (7) C32 0.0462 (10) 0.0645 (12) 0.0381 (11) 0.0009 (10) 0.0014 (8) −0.0053 (8) O33 0.0542 (9) 0.1065 (14) 0.0429 (9) 0.0074 (10) 0.0096 (7) −0.0018 (9) O34 0.0480 (8) 0.0910 (13) 0.0467 (9) 0.0198 (9) 0.0030 (7) 0.0023 (8) C35 0.0384 (10) 0.0593 (12) 0.0723 (15) 0.0027 (10) −0.0013 (10) −0.0030 (11) C36 0.0527 (14) 0.092 (2) 0.128 (3) −0.0134 (15) −0.0049 (17) 0.006 (2) C40 0.090 (2) 0.078 (2) 0.226 (6) 0.018 (2) −0.040 (3) −0.066 (3) C44 0.072 (2) 0.174 (4) 0.114 (3) 0.043 (3) 0.002 (2) 0.061 (3)
Geometric parameters (Å, º)
C1—C3 1.378 (4) C22—H24 0.970
C1—C11 1.389 (3) C25—O27 1.408 (3)
C1—H2 0.930 C25—C28 1.514 (3)
C3—C5 1.389 (4) C25—H26 0.980
C3—H4 0.930 O27—H27 0.92 (5)
C5—C7 1.366 (4) C28—N31 1.458 (3)
C5—H6 0.930 C28—H29 0.970
supporting information
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Acta Cryst. (2005). E61, o792–o794
C7—H8 0.930 N31—C32 1.344 (3)
C9—C11 1.383 (3) C32—O33 1.219 (3)
C9—H1 0.930 C32—O34 1.332 (3)
C11—C12 1.488 (3) O34—C35 1.470 (3)
C12—O13 1.204 (3) C35—C40 1.492 (5)
C12—C14 1.522 (3) C35—C36 1.495 (4)
C14—O17 1.423 (3) C35—C44 1.514 (5)
C14—H15 0.970 C36—H37 0.960
C14—H16 0.970 C36—H38 0.960
O17—C18 1.346 (3) C36—H39 0.960
C18—O19 1.191 (3) C40—H41 0.960
C18—C20 1.516 (3) C40—H42 0.960
C20—N31 1.461 (3) C40—H43 0.960
C20—C22 1.527 (3) C44—H45 0.960
C20—H21 0.980 C44—H46 0.960
C22—C25 1.518 (3) C44—H47 0.960
C22—H23 0.970
C3—C1—C11 120.8 (2) O27—C25—C22 110.2 (2)
C3—C1—H2 119.6 C28—C25—C22 103.10 (17)
C11—C1—H2 119.6 O27—C25—H26 109.7
C1—C3—C5 119.3 (2) C28—C25—H26 109.7
C1—C3—H4 120.3 C22—C25—H26 109.7
C5—C3—H4 120.3 C25—O27—H27 108 (3)
C7—C5—C3 120.1 (2) N31—C28—C25 103.22 (17)
C7—C5—H6 119.9 N31—C28—H29 111.1
C3—C5—H6 119.9 C25—C28—H29 111.1
C5—C7—C9 120.6 (2) N31—C28—H30 111.1
C5—C7—H8 119.7 C25—C28—H30 111.1
C9—C7—H8 119.7 H29—C28—H30 109.1
C11—C9—C7 119.8 (2) C32—N31—C28 123.00 (18)
C11—C9—H1 120.1 C32—N31—C20 122.89 (18)
C7—C9—H1 120.1 C28—N31—C20 112.69 (17)
C9—C11—C1 119.3 (2) O33—C32—O34 125.6 (2)
C9—C11—C12 123.0 (2) O33—C32—N31 123.9 (2)
C1—C11—C12 117.7 (2) O34—C32—N31 110.52 (18)
O13—C12—C11 122.1 (2) C32—O34—C35 122.51 (18)
O13—C12—C14 120.0 (2) O34—C35—C40 108.8 (2)
C11—C12—C14 117.84 (18) O34—C35—C36 111.0 (2)
O17—C14—C12 110.41 (19) C40—C35—C36 111.1 (4)
O17—C14—H15 109.6 O34—C35—C44 101.1 (2)
C12—C14—H15 109.6 C40—C35—C44 114.2 (4)
O17—C14—H16 109.6 C36—C35—C44 110.3 (3)
C12—C14—H16 109.6 C35—C36—H37 109.5
H15—C14—H16 108.1 C35—C36—H38 109.5
C18—O17—C14 115.52 (18) H37—C36—H38 109.5
O19—C18—O17 123.97 (19) C35—C36—H39 109.5
supporting information
sup-5
Acta Cryst. (2005). E61, o792–o794
O17—C18—C20 109.18 (18) H38—C36—H39 109.5
N31—C20—C18 111.97 (18) C35—C40—H41 109.5
N31—C20—C22 102.73 (17) C35—C40—H42 109.5
C18—C20—C22 110.99 (17) H41—C40—H42 109.5
N31—C20—H21 110.3 C35—C40—H43 109.5
C18—C20—H21 110.3 H41—C40—H43 109.5
C22—C20—H21 110.3 H42—C40—H43 109.5
C25—C22—C20 103.90 (18) C35—C44—H45 109.5
C25—C22—H23 111.0 C35—C44—H46 109.5
C20—C22—H23 111.0 H45—C44—H46 109.5
C25—C22—H24 111.0 C35—C44—H47 109.5
C20—C22—H24 111.0 H45—C44—H47 109.5
H23—C22—H24 109.0 H46—C44—H47 109.5