organic papers
o2582
Kolevet al. C20H23NO4 doi:10.1107/S1600536805022129 Acta Cryst.(2005). E61, o2582–o2584
Acta Crystallographica Section E Structure Reports
Online
ISSN 1600-5368
6-
O
-Acetylcodeine
Tsonko Kolev,aRumyana Bakalska,bBoris Shivachevaand Rosica Petrovaa*
aBulgarian Academy of Sciences, Institute of
Organic Chemistry, Acad G. Bonchev Street, Building 9, 1113 Sofia, Bulgaria, and bUniversity of Plovdiv, Department of Organic
Chemistry, 24 Tzar Assen Street, 4000 Plovdiv, Bulgaria
Correspondence e-mail: [email protected]
Key indicators Single-crystal X-ray study T= 290 K
Mean(C–C) = 0.006 A˚ Rfactor = 0.049 wRfactor = 0.126 Data-to-parameter ratio = 8.5
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 (systematic name: 6-acetoxy-4,5 -epoxy-3-methoxy-17-methyl-morphin-7-ene), C20H23NO4,
crystal-lizes with one molecule in the asymmetric unit. The molecular structure exhibits features typical of morphine derivatives with a T configuration. The three-dimensional packing is
stabilized by intermolecular C—H N and C—H
inter-actions.
Comment
6-O-Acetylcodeine, (I), was synthesized as a part of our study on opium alkaloids. The transformation of morphine deriva-tives into different metabolites is a matter of practical interest for detecting opiates in blood or urine. Although the studied compound has long been known as a urinary marker to detect the use of street heroin, its crystal structure has not been reported in the literature until now.
The molecule of (I) has the characteristic T-shape of clas-sical opiates, with a dihedral angle between the mean planes of theA/B/CandD/Erings (see scheme) of 80.56 (8); the rings
are denoted following commonly used nomenclature for opiates. The main structural features of the molecule are very close to those of codeine, heroin and morphine (Canfieldet al., 1979, 1987; Gylbert, 1973). The ring fusions and conformations are similar to those previously reported for morphine deriv-atives (Gelders & de Ranter, 1979; Petrickova et al., 2002; Moodyet al., 1997). Aromatic ringAis planar,Bis close to an
envelope, C and D assume half-chair conformations and E
assumes a chair form (Table 1). The conformation about the single C—C bonds within the rings is staggered, except for those along the C5—C6 bond which is eclipsed, with an O2—
C5—C6—O3 torsion angle of 0.8 (5)(Moss, 1996).
The three-dimensional arrangement of the molecules is shown in Fig. 2. Two distinct types of weak interactions are
observed (Table 2); C5—H5 N1 contacts connect molecules
along theaaxis to form chains, while C—HA contacts link
the chains along thebaxis. The angle between the normal to
the plane of the aromatic unit and the line linking C20 and the centroid of the ring (Cg1) is 7.35 (15).
An independent structure determination of 6-O
-acetyl-codeine is reported in the preceding paper (Sonaret al., 2005).
Experimental
Compound (I) was synthesized according to Huang et al. (1999). Crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethyl acetate solution at room temperature.
Crystal data
C20H23NO4 Mr= 341.39
Orthorhombic,P212121 a= 8.628 (2) A˚
b= 12.727 (2) A˚
c= 15.4842 (19) A˚
V= 1700.3 (5) A˚3
Z= 4
Dx= 1.334 Mg m
3
MoKradiation Cell parameters from 22
reflections
= 18.3–19.7
= 0.09 mm1
T= 290 (2) K Prism, colorless 0.250.250.25 mm
Data collection
Enraf–Nonius CAD-4 diffractometer Non–profiled!/2scans 4181 measured reflections 1928 independent reflections 1093 reflections withI> 2(I)
Rint= 0.077
max= 26.0 h= 0!10
k= 0!15
l=19!19 3 standard reflections
frequency: 120 min intensity decay: 5%
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.049 wR(F2) = 0.126 S= 0.98 1928 reflections 226 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0562P)2]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.20 e A˚
3
[image:2.610.315.566.73.242.2]min=0.19 e A˚3
Table 1
Selected torsion angles ().
O2—C4—C12—C13 4.3 (5) C13—C5—O2—C4 32.5 (4) C13—C5—C6—C7 4.8 (5) C5—C6—O3—C19 76.4 (5) C6—C7—C8—C14 1.0 (8) C7—C8—C14—C13 24.8 (6) C14—C9—N1—C16 62.5 (4) C14—C9—C10—C11 37.8 (6)
C10—C11—C12—C13 6.8 (7) C4—C12—C13—C5 23.3 (5) C11—C12—C13—C15 86.5 (5) C15—C13—C14—C9 64.5 (4) C13—C15—C16—N1 51.2 (5) O4—C19—O3—C6 11.8 (7) C20—C19—O3—C6 166.1 (4)
Table 2
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
C5—H5 N1i
0.98 2.42 3.363 (5) 163 C20—H20C Cg1ii 0.96 2.52 3.421 (2) 157 Symmetry codes: (i)xþ1
2;yþ 1
2;zþ1; (ii)xþ2;yþ 1 2;zþ
1
2.Cg1 is the centroid
of ringA
H atoms were placed in idealized positions (C—H = 0.93–0.98 A˚ ) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). In the absence of significant anomalous scattering effects, Friedel pairs were merged.
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement:CAD-4 EXPRESS; data reduction:XCAD4(Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97
(Sheldrick, 1997); program(s) used to refine structure:SHELXL97
(Sheldrick, 1997); molecular graphics: ORTEP3 for Windows
(Farrugia, 1997) andMERCURY(Version 1.3; Bruno et al., 2002); software used to prepare material for publication:WinGX(Farrugia, 1999).
organic papers
Acta Cryst.(2005). E61, o2582–o2584 Kolevet al. C
20H23NO4
o2583
Figure 1
The molecular structure of (I), showing the atom-numbering scheme and 50% probability displacement ellipsoids.
Figure 2
The packing of the 6-O-acetylcodeine molecules. The dotted lines indicate C—H N interactions. [Symmetry codes: (i)1
2+x, 1y, 1z;
(ii) 2x,1 2+y,
[image:2.610.315.565.289.536.2]TK thanks the DAAD and the Alexander von Humboldt Foundation for a grant within the priority programme (Stability Pact for South-Eastern Europe). This work has been supported by the Bulgarian National Fund of Scientific Research (contracts Nos. X-1213 and F-1212).
References
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002).Acta Cryst.B58, 389–397.
Canfield, D., Barrick, J. & Giessen, B. C. (1979).Acta Cryst.B35, 2806–2809. Canfield, D., Barrick, J. & Giessent, B. C. (1987).Acta Cryst.C43, 977–979. Enraf–Nonius (1994).CAD-4 EXPRESS. Enraf–Nonius, Delft, The
Nether-lands.
Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838.
Gelders, Y. G. & de Ranter, C. J. (1979).Acta Cryst.B35, 1111–1116. Gylbert, L. (1973).Acta Cryst.B29, 1630–1635.
Harms, K. & Wocadlo, S. (1995).XCAD4. University of Marburg, Germany. Huang, B., Lu, Y., Ji, B. & Christodoulou, A. P. (1999). US Patent No. 6 008
355.
Moody, P. C. E., Shikotra, N., French, C. E., Bruce, N. C. & Scrutton, N. S. (1997).Acta Cryst.D53, 619–621.
Moss, G. P. (1996).Pure Appl. Chem.68, 2193–2222.
Petrickova, H., Jegorov, A., Husak, M. & Cisarova, I. (2002).Acta Cryst.A58
(Supplement), C-126.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Go¨ttingen, Germany.
Sonar, V. N., Parkin, S. & Crooks, P. A. (2005).Acta Cryst. E61, o2579– o2581.
organic papers
o2584
Kolevet al. Csupporting information
sup-1 Acta Cryst. (2005). E61, o2582–o2584
supporting information
Acta Cryst. (2005). E61, o2582–o2584 [https://doi.org/10.1107/S1600536805022129]
6-
O
-Acetylcodeine
Tsonko Kolev, Rumyana Bakalska, Boris Shivachev and Rosica Petrova
6α-acetoxy-4,5α-epoxy-3-methoxy-17-methyl-morphin-7-ene
Crystal data
C20H23NO4
Mr = 341.39
Orthorhombic, P212121 Hall symbol: P 2ac 2ab a = 8.628 (2) Å b = 12.727 (2) Å c = 15.4842 (19) Å V = 1700.3 (5) Å3
Z = 4 F(000) = 728
Dx = 1.334 Mg m−3 Melting point = 405–406 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 22 reflections θ = 18.3–19.7°
µ = 0.09 mm−1
T = 290 K Prism, colorles 0.25 × 0.25 × 0.25 mm
Data collection
Enraf–Nonius CAD-4 diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
non–profiled ω/2θ scans 4181 measured reflections 1928 independent reflections 1093 reflections with I > 2σ(I)
Rint = 0.077
θmax = 26.0°, θmin = 2.1°
h = 0→10 k = 0→15 l = −19→19
3 standard reflections every 120 min intensity decay: 5%
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.049
wR(F2) = 0.126
S = 0.98 1928 reflections 226 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-atom parameters constrained w = 1/[σ2(F
o2) + (0.0562P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001
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sup-2 Acta Cryst. (2005). E61, o2582–o2584
Special details
Experimental. Spectroscopic analysis: IR (KBr pellet, cm-1). The ν
C—H vibrations of the aromatic ring (A) appears at 3065w and 3024m. The bend at 3000 was assigned to the νC—H of double C—C bond. The middle intensity bands between 2961 and 2811 are attributed to νC—H vibrations of methine, methilene. The very strong band at 1735 was ascribed to νC=O of the acetyl group. The middle band at 1617 is attributed to νC=C bond. The band at 1609 belongs to 8a radial vibration of aromatic ring A. The bands at 1504 an 1449 could be attributed to 19a and 19b vibrations of the aromatic ring. The series of very strong bands between 1202 and 1234 can be assigned to different νC—O vibrations. The bands between 821 and 741 could be attributed to out-of-plane C—H vibrations of aromatic ring.
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)
x y z Uiso*/Ueq
C1 0.6225 (6) 0.3247 (4) 0.1383 (3) 0.0483 (12)
H1 0.5502 0.3233 0.0938 0.058*
C2 0.7799 (5) 0.3328 (4) 0.1186 (3) 0.0473 (12)
H2 0.8102 0.3344 0.0610 0.057*
C3 0.8914 (5) 0.3385 (4) 0.1818 (3) 0.0439 (11) C4 0.8413 (5) 0.3333 (3) 0.2660 (2) 0.0370 (10) C5 0.8181 (5) 0.3677 (4) 0.4090 (3) 0.0400 (11)
H5 0.8542 0.3394 0.4643 0.048*
C6 0.8011 (5) 0.4887 (4) 0.4152 (3) 0.0466 (12)
H6 0.8361 0.5108 0.4726 0.056*
C7 0.6423 (5) 0.5318 (4) 0.4006 (3) 0.0484 (12)
H7 0.6329 0.6041 0.3933 0.058*
C8 0.5146 (5) 0.4752 (4) 0.3975 (3) 0.0476 (12)
H8 0.4208 0.5098 0.3890 0.057*
C9 0.3877 (5) 0.3035 (4) 0.3535 (3) 0.0447 (12)
H9 0.2883 0.3352 0.3696 0.054*
C10 0.4069 (5) 0.3193 (4) 0.2553 (3) 0.0456 (12)
H10A 0.3505 0.2640 0.2257 0.055*
H10B 0.3596 0.3857 0.2394 0.055*
C11 0.5721 (5) 0.3189 (3) 0.2236 (2) 0.0396 (11) C12 0.6867 (5) 0.3202 (3) 0.2853 (2) 0.0353 (10) C13 0.6682 (5) 0.3110 (4) 0.3811 (2) 0.0377 (11) C14 0.5126 (5) 0.3586 (4) 0.4068 (3) 0.0446 (12)
H14 0.4942 0.3421 0.4677 0.054*
C15 0.6655 (5) 0.1945 (3) 0.4083 (3) 0.0459 (12)
H15A 0.7613 0.1610 0.3906 0.055*
H15B 0.6583 0.1899 0.4707 0.055*
C16 0.5293 (6) 0.1374 (4) 0.3679 (3) 0.0517 (13)
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H16B 0.5219 0.0673 0.3921 0.062*
C17 0.2511 (6) 0.1353 (5) 0.3509 (3) 0.0714 (17)
H17A 0.1580 0.1742 0.3622 0.107*
H17B 0.2458 0.0685 0.3796 0.107*
H17C 0.2619 0.1245 0.2899 0.107*
C18 1.1006 (6) 0.3568 (7) 0.0835 (3) 0.113 (3)
H19A 1.2114 0.3635 0.0829 0.170*
H19B 1.0549 0.4177 0.0572 0.170*
H19C 1.0709 0.2952 0.0517 0.170*
C19 1.0504 (6) 0.5448 (4) 0.3678 (4) 0.0550 (13) C20 1.1353 (6) 0.5749 (4) 0.2888 (3) 0.0673 (16)
H20A 1.0627 0.5894 0.2434 0.101*
H20B 1.2022 0.5184 0.2716 0.101*
H20C 1.1962 0.6365 0.3001 0.101*
N1 0.3838 (4) 0.1937 (3) 0.3830 (2) 0.0490 (10) O1 1.0489 (4) 0.3480 (3) 0.16893 (19) 0.0593 (10) O2 0.9292 (3) 0.3416 (2) 0.34055 (16) 0.0445 (8) O3 0.8967 (4) 0.5397 (3) 0.3518 (2) 0.0510 (8) O4 1.1055 (4) 0.5238 (4) 0.4367 (3) 0.0827 (13)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
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sup-4 Acta Cryst. (2005). E61, o2582–o2584
Geometric parameters (Å, º)
C1—C11 1.392 (6) C10—H10B 0.9700
C1—C2 1.396 (6) C11—C12 1.374 (5)
C1—H1 0.9300 C12—C13 1.497 (5)
C2—C3 1.374 (6) C13—C14 1.526 (6)
C2—H2 0.9300 C13—C15 1.541 (6)
C3—C4 1.376 (6) C14—H14 0.9800
C3—O1 1.379 (5) C15—C16 1.517 (6)
C4—C12 1.377 (6) C15—H15A 0.9700
C4—O2 1.385 (4) C15—H15B 0.9700
C5—O2 1.467 (5) C16—N1 1.464 (6)
C5—C13 1.542 (6) C16—H16A 0.9700
C5—C6 1.550 (6) C16—H16B 0.9700
C5—H5 0.9800 C17—N1 1.453 (6)
C6—O3 1.437 (5) C17—H17A 0.9600
C6—C7 1.493 (6) C17—H17B 0.9600
C6—H6 0.9800 C17—H17C 0.9600
C7—C8 1.318 (7) C18—O1 1.401 (5)
C7—H7 0.9300 C18—H19A 0.9600
C8—C14 1.491 (7) C18—H19B 0.9600
C8—H8 0.9300 C18—H19C 0.9600
C9—N1 1.471 (6) C19—O4 1.198 (6)
C9—C14 1.527 (6) C19—O3 1.350 (6)
C9—C10 1.543 (6) C19—C20 1.476 (7)
C9—H9 0.9800 C20—H20A 0.9600
C10—C11 1.508 (5) C20—H20B 0.9600
C10—H10A 0.9700 C20—H20C 0.9600
C11—C1—C2 121.0 (4) C14—C13—C15 107.3 (4)
C11—C1—H1 119.5 C12—C13—C5 98.7 (3)
C2—C1—H1 119.5 C14—C13—C5 118.6 (3)
C3—C2—C1 121.9 (4) C15—C13—C5 112.7 (4)
C3—C2—H2 119.0 C8—C14—C13 111.1 (4)
C1—C2—H2 119.0 C8—C14—C9 114.4 (4)
C2—C3—C4 116.9 (4) C13—C14—C9 107.3 (3)
C2—C3—O1 126.3 (4) C8—C14—H14 107.9
C4—C3—O1 116.8 (4) C13—C14—H14 107.9
C3—C4—C12 121.0 (4) C9—C14—H14 107.9
C3—C4—O2 127.9 (4) C16—C15—C13 111.1 (4)
C12—C4—O2 111.1 (3) C16—C15—H15A 109.4
O2—C5—C13 103.9 (3) C13—C15—H15A 109.4
O2—C5—C6 109.3 (3) C16—C15—H15B 109.4
C13—C5—C6 113.8 (4) C13—C15—H15B 109.4
O2—C5—H5 109.9 H15A—C15—H15B 108.0
C13—C5—H5 109.9 N1—C16—C15 111.3 (4)
C6—C5—H5 109.9 N1—C16—H16A 109.4
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sup-5 Acta Cryst. (2005). E61, o2582–o2584
O3—C6—C5 110.7 (4) N1—C16—H16B 109.4
C7—C6—C5 116.3 (4) C15—C16—H16B 109.4
O3—C6—H6 108.2 H16A—C16—H16B 108.0
C7—C6—H6 108.2 N1—C17—H17A 109.5
C5—C6—H6 108.2 N1—C17—H17B 109.5
C8—C7—C6 124.9 (5) H17A—C17—H17B 109.5
C8—C7—H7 117.6 N1—C17—H17C 109.5
C6—C7—H7 117.6 H17A—C17—H17C 109.5
C7—C8—C14 123.4 (5) H17B—C17—H17C 109.5
C7—C8—H8 118.3 O1—C18—H19A 109.5
C14—C8—H8 118.3 O1—C18—H19B 109.5
N1—C9—C14 106.5 (4) H19A—C18—H19B 109.5
N1—C9—C10 115.6 (4) O1—C18—H19C 109.5
C14—C9—C10 113.4 (4) H19A—C18—H19C 109.5
N1—C9—H9 106.9 H19B—C18—H19C 109.5
C14—C9—H9 106.9 O4—C19—O3 122.9 (5)
C10—C9—H9 106.9 O4—C19—C20 126.8 (5)
C11—C10—C9 114.9 (3) O3—C19—C20 110.3 (5)
C11—C10—H10A 108.5 C19—C20—H20A 109.5
C9—C10—H10A 108.5 C19—C20—H20B 109.5
C11—C10—H10B 108.5 H20A—C20—H20B 109.5
C9—C10—H10B 108.5 C19—C20—H20C 109.5
H10A—C10—H10B 107.5 H20A—C20—H20C 109.5
C12—C11—C1 115.7 (4) H20B—C20—H20C 109.5
C12—C11—C10 117.0 (3) C17—N1—C16 111.7 (4)
C1—C11—C10 127.1 (4) C17—N1—C9 113.5 (4)
C11—C12—C4 123.2 (4) C16—N1—C9 113.3 (4)
C11—C12—C13 127.7 (4) C3—O1—C18 117.2 (4)
C4—C12—C13 109.1 (4) C4—O2—C5 105.1 (3)
C12—C13—C14 108.7 (4) C19—O3—C6 117.3 (4)
C12—C13—C15 110.4 (4)
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sup-6 Acta Cryst. (2005). E61, o2582–o2584
C3—C4—C12—C13 176.7 (4) C4—C12—C13—C5 23.3 (5) C6—C5—O2—C4 −89.3 (4) C4—C12—C13—C14 147.6 (4) C13—C5—O2—C4 32.5 (4) C4—C12—C13—C15 −95.0 (5) O2—C5—C6—O3 0.8 (5) C11—C12—C13—C5 −155.3 (5) O2—C5—C6—C7 120.4 (4) C11—C12—C13—C14 −30.9 (6) C13—C5—C6—O3 −114.7 (4) C11—C12—C13—C15 86.5 (5) C13—C5—C6—C7 4.8 (5) C5—C13—C14—C8 40.8 (5) O2—C5—C13—C12 −33.0 (4) C5—C13—C14—C9 166.5 (4) O2—C5—C13—C14 −150.1 (4) C12—C13—C14—C8 −70.8 (5) O2—C5—C13—C15 83.4 (4) C12—C13—C14—C9 54.9 (5) C6—C5—C13—C12 85.7 (4) C15—C13—C14—C8 169.8 (4) C6—C5—C13—C14 −31.3 (5) C15—C13—C14—C9 −64.5 (4) C6—C5—C13—C15 −157.8 (4) C5—C13—C15—C16 −171.0 (3) C5—C6—O3—C19 −76.4 (5) C12—C13—C15—C16 −61.7 (5) C7—C6—O3—C19 157.5 (4) C14—C13—C15—C16 56.6 (5) O3—C6—C7—C8 134.4 (5) C13—C15—C16—N1 −51.2 (5) C5—C6—C7—C8 11.8 (7) C15—C16—N1—C9 55.2 (5) C6—C7—C8—C14 −1.0 (8) C15—C16—N1—C17 −175.1 (4) C7—C8—C14—C9 −146.5 (4) O4—C19—O3—C6 −11.8 (7) C7—C8—C14—C13 −24.8 (6) C20—C19—O3—C6 166.1 (4)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
C5—H5···N1i 0.98 2.42 3.363 (5) 163
C20—H20C···Cg1ii 0.96 2.52 3.421 (2) 157
