7α-Methoxy­carbonyl-6,7,8,14-tetra­hydro-6,14-endo-ethenothebaine

Odabaşoğlu, M.; Yavuz, S.; Pamir, Ö.; Yıldırır, Y.; Büyükgüngör, O.

doi:10.1107/S1600536809009362

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o864

doi:10.1107/S1600536809009362

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7α-Methoxycarbonyl-6,7,8,14-tetrahydro-6,14-endo-ethenothebaine

Mustafa Odabaşoğlu,^a Serkan Yavuz,^b Özgür Pamir,^b Yılmaz Yıldırır ^b and Orhan Büyükgüngör ^c ^*

^aChemistry Program, Denizli Higher Vocational School, Pamukkale University, TR-20159 Kınıklı, Denizli, Turkey, ^bDepartment of Chemistry, Faculty of Arts and Science, Gazi University, Ankara, Turkey, and ^cDepartment of Physics, Faculty of Arts and Science, Ondokuz Mayıs University, TR-55139 Kurupelit Samsun, Turkey
^*Correspondence e-mail: orhanb@omu.edu.tr

(Received 26 February 2009; accepted 13 March 2009; online 25 March 2009)

In the molecule of the title compound, C₂₃H₂₇NO₅, the furan ring adopts an envelope conformation. Intramolecular C—H⋯O interactions result in the formation of S(5) and S(6) motifs. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds link the molecules through C(6) and C(8) chains along the [100] and [010] directions, generating a two-dimensional network.

Related literature

For general background, see: Casy & Parfitt (1986 ); Lenz et al. (1986 ); Schmidhammer, (1998 ); Maat et al. (1999 ); Lewis (1985 ). For a related structure, see: Bentley & Hardy (1967 ). For bond-length data, see: Allen et al. (1987 ). For ring-puckering parameters, see: Cremer & Pople (1975 ). For ring motifs, see: Bernstein et al. (1995 ); Etter (1990 ).

Experimental

Crystal data

C₂₃H₂₇NO₅
M_r = 397.46
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.5604 (2) Å
b = 10.4082 (3) Å
c = 29.1382 (11) Å
V = 1989.61 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.39 × 0.35 × 0.31 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ) T_min = 0.966, T_max = 0.984
27330 measured reflections
2467 independent reflections
2300 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.085
S = 1.06
2467 reflections
262 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O2	0.96	2.34	3.002 (3)	125
C12—H12B⋯O4	0.97	2.46	2.899 (2)	107
C15—H15⋯O4ⁱ	0.98	2.53	3.483 (2)	165
C17—H17C⋯O2ⁱⁱ	0.96	2.62	3.533 (3)	158
Symmetry codes: (i) x+1, y, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809009362/hk2636sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809009362/hk2636Isup2.hkl

checkCIF report

Comment top

Morphine alkaloids and related semisynthetic derivatives are the most important groups of non-endogenous opioid-receptor ligands. They can possess both agonist and antagonist properties. Thus, some of them are used as effective analgesics for the treatment of moderate to severe pain or as opioid antagonists for the treatment of narcotic overdosage or opioid addiction; others are used as intermediate products in research (Casy & Parfitt, 1986; Lenz et al., 1986; Schmidhammer, 1998).

Thebaine readily undergoes Diels–Alder reactions with various dienophiles to give the adducts. The diene system of thebaine could potentially be attacked from both faces, but reactions with dienophiles always occur from the same face as the nitrogen bridge (upper face) due to the nitrogen bridge causing the lower face to be hindered through concealment inside a concave system (Maat et al., 1999). The nature of a substituent in positions 7,8 of morphinane alkaloids is among the most important factors affecting their biological activity (Lenz et al., 1986). For instance, the opioid analgesic buprenorphine, ethorphine possesses a pharmacological profile interesting for development of antinarcotics (Lewis, 1985). In view of the importance of the morphine alkaloids, we report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings C (C1–C6), D (O2/C5/C6/C11/C15) and E (C4/C5/C8–C11) adopt envelope conformations with C5, C15 and C10 atoms displaced by 0.118 (3), -0.172 (3) and -0.809 (3) Å from the planes of the other ring atoms, respectively. Rings A (N1/C9–C11/C21/C22), B (C10/C12–C14/C19/C20), F (C10–C15) and G (C10/C11/C14/C15/C19/C20) are not planar, having total puckering amplitudes, Q_T, of 0.604 (2), 0.820 (2), 1.047 (2) and 0.942 Å and chair, boat, boat and boat conformations [ϕ = 78.15 (3) and θ = 9.43 (3)° (for ring A), ϕ = 3.08 (3) and θ = 87.76 (3)° (for ring B), ϕ = 155.88 (3) and θ = 152.64 (3)° (for ring F) and ϕ = -82.44 (3) and θ = 148.46 (3)° (for ring G)] (Cremer & Pople, 1975). The intramolecular C—H···O interactions (Table 1) result in the formations of five- and six-membered rings H (O4/C12/C13/C16/H12B) and I (O1/O2/C1/C6/C7/H7A). Ring H adopts envelope conformation with O4 atom displaced by 0.536 (4) Å from the plane of the other ring atoms, while ring I has twisted conformation. The intramolecular interactions result in the formations of S(5) and S(6) motifs (Bernstein et al., 1995; Etter, 1990) (Fig. 2).

In the crystal structure, weak intermolecular C—H···O hydrogen bonds (Table 1) link the molecules through C(6) and C(8) chains (Bernstein et al., 1995; Etter, 1990) nearly along the [100] and [010] directions (Figs. 2 and 3), generating a three-dimensional network (Fig. 4).

Related literature top

For general background, see: Casy & Parfitt (1986); Lenz et al. (1986); Schmidhammer, (1998); Maat et al. (1999); Lewis (1985). For a related structure, see: Bentley & Hardy (1967). For bond-length data, see: Allen et al. (1987). For ring-puckering parameters, see: Cremer & Pople (1975). For ring motifs, see: Bernstein et al. (1995); Etter (1990).

Experimental top

The title compound was prepared according to the literature method (Bentley & Hardy, 1967). Thebaine (1.50 g, 4.82 mmol) and methyl acrylate (2.55 ml, 28.3 mmol) were refluxed in benzene (50 ml) for 8 h. After cooling to room temperature, the reaction mixture was concentrated in vacuo. The mixture was centrifuged, and then the title compound was obtained as colorless prisms. It was washed with cold methanol, and recrystallized from methanol.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level.
	Fig. 2. A partial packing diagram of the title compound, showing the formation of C(6) chain with S(5) and S(6) motifs along the [100] direction. H atoms not involved in hydrogen bonding have been omitted. Hydrogen bonds are shown as dashed lines [symmetry code: (i) x + 1, y, z].
	Fig. 3. A partial packing diagram of the title compound, showing the formation of C(8) chain along the [010] direction. H atoms not involved in hydrogen bonding have been omitted. Hydrogen bonds are shown as dashed lines [symmetry code: (i) x - 1, y + 1/2, z].
	Fig. 4. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

7α-Methoxycarbonyl-6,7,8,14-tetrahydro-6,14-endo-ethenothebaine top

Crystal data top

C₂₃H₂₇NO₅	F(000) = 848
M_r = 397.46	D_x = 1.327 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 27330 reflections
a = 6.5604 (2) Å	θ = 1.4–27.3°
b = 10.4082 (3) Å	µ = 0.09 mm⁻¹
c = 29.1382 (11) Å	T = 296 K
V = 1989.61 (11) Å³	Prism, colourless
Z = 4	0.39 × 0.35 × 0.31 mm

Data collection top

Stoe IPDS II diffractometer	2467 independent reflections
Radiation source: fine-focus sealed tube	2300 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scan rotation method	θ_max = 26.8°, θ_min = 1.4°
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	h = −8→8
T_min = 0.966, T_max = 0.984	k = −12→13
27330 measured reflections	l = −36→36

Refinement top

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0516P)² + 0.2082P] where P = (F_o² + 2F_c²)/3
2467 reflections	(Δ/σ)_max = 0.001
262 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₂₃H₂₇NO₅	V = 1989.61 (11) Å³
M_r = 397.46	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.5604 (2) Å	µ = 0.09 mm⁻¹
b = 10.4082 (3) Å	T = 296 K
c = 29.1382 (11) Å	0.39 × 0.35 × 0.31 mm

Data collection top

Stoe IPDS II diffractometer	2467 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	2300 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.984	R_int = 0.037
27330 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.06	Δρ_max = 0.14 e Å⁻³
2467 reflections	Δρ_min = −0.14 e Å⁻³
262 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.9853 (3)	0.82364 (14)	0.58760 (5)	0.0549 (4)
O2	0.9330 (2)	0.60075 (12)	0.65159 (4)	0.0386 (3)
O3	0.6842 (2)	0.59127 (12)	0.73570 (4)	0.0395 (3)
O4	0.2507 (2)	0.38987 (17)	0.74242 (5)	0.0535 (4)
O5	0.4979 (2)	0.37509 (14)	0.79459 (4)	0.0460 (3)
N1	0.6584 (3)	0.16016 (16)	0.58745 (5)	0.0444 (4)
C1	0.9098 (3)	0.70471 (19)	0.57577 (7)	0.0435 (5)
C2	0.8226 (4)	0.6904 (2)	0.53244 (7)	0.0521 (5)
H2	0.8344	0.7572	0.5114	0.063*
C3	0.7190 (4)	0.5803 (2)	0.51963 (6)	0.0503 (5)
H3	0.6560	0.5766	0.4911	0.060*
C4	0.7078 (3)	0.47442 (19)	0.54914 (6)	0.0415 (4)
C5	0.8120 (3)	0.48664 (17)	0.59018 (6)	0.0353 (4)
C6	0.8950 (3)	0.60011 (19)	0.60527 (6)	0.0375 (4)
C7	1.1676 (5)	0.8241 (3)	0.61339 (10)	0.0721 (7)
H7A	1.1464	0.7790	0.6417	0.087*
H7B	1.2068	0.9112	0.6198	0.087*
H7C	1.2735	0.7825	0.5962	0.087*
C8	0.5653 (4)	0.3625 (2)	0.54286 (6)	0.0484 (5)
H8A	0.6178	0.3088	0.5184	0.058*
H8B	0.4341	0.3953	0.5330	0.058*
C9	0.5316 (3)	0.27660 (19)	0.58627 (6)	0.0410 (4)
H9	0.3887	0.2491	0.5862	0.049*
C10	0.5680 (3)	0.35311 (17)	0.63073 (6)	0.0337 (4)
C11	0.7950 (3)	0.39378 (17)	0.62929 (6)	0.0328 (4)
C12	0.5280 (3)	0.28000 (17)	0.67567 (6)	0.0385 (4)
H12A	0.6025	0.1995	0.6755	0.046*
H12B	0.3838	0.2607	0.6784	0.046*
C13	0.5970 (3)	0.36300 (17)	0.71682 (6)	0.0346 (4)
H13	0.7151	0.3225	0.7315	0.042*
C14	0.6587 (3)	0.50225 (16)	0.69954 (5)	0.0325 (4)
C15	0.8520 (3)	0.48032 (16)	0.67040 (6)	0.0320 (4)
H15	0.9566	0.4380	0.6890	0.038*
C16	0.4276 (3)	0.37757 (17)	0.75171 (6)	0.0373 (4)
C17	0.3443 (4)	0.3871 (2)	0.82992 (7)	0.0582 (6)
H17A	0.2733	0.4671	0.8262	0.070*
H17B	0.4082	0.3850	0.8595	0.070*
H17C	0.2493	0.3173	0.8274	0.070*
C18	0.8627 (4)	0.5760 (2)	0.76315 (7)	0.0531 (5)
H18A	0.8614	0.4926	0.7772	0.064*
H18B	0.8652	0.6409	0.7865	0.064*
H18C	0.9815	0.5841	0.7441	0.064*
C19	0.4885 (3)	0.54957 (17)	0.66960 (6)	0.0348 (4)
H19	0.4201	0.6261	0.6754	0.042*
C20	0.4425 (3)	0.47512 (18)	0.63434 (6)	0.0366 (4)
H20	0.3410	0.4960	0.6133	0.044*
C21	0.9344 (3)	0.27647 (18)	0.62531 (6)	0.0398 (4)
H21A	1.0739	0.3051	0.6211	0.048*
H21B	0.9282	0.2277	0.6536	0.048*
C22	0.8753 (3)	0.1899 (2)	0.58551 (7)	0.0478 (5)
H22A	0.9064	0.2324	0.5567	0.057*
H22B	0.9535	0.1109	0.5869	0.057*
C23	0.5999 (4)	0.0659 (2)	0.55288 (8)	0.0594 (6)
H23A	0.4611	0.0401	0.5578	0.071*
H23B	0.6873	−0.0078	0.5551	0.071*
H23C	0.6127	0.1032	0.5229	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0602 (10)	0.0446 (7)	0.0601 (9)	−0.0062 (7)	−0.0022 (8)	0.0136 (7)
O2	0.0409 (7)	0.0403 (7)	0.0345 (6)	−0.0067 (6)	−0.0023 (5)	0.0046 (5)
O3	0.0414 (7)	0.0397 (7)	0.0374 (6)	0.0075 (6)	−0.0061 (6)	−0.0074 (5)
O4	0.0400 (8)	0.0721 (10)	0.0485 (7)	0.0135 (7)	0.0066 (6)	0.0086 (7)
O5	0.0502 (8)	0.0562 (8)	0.0317 (6)	−0.0020 (7)	0.0068 (6)	−0.0015 (6)
N1	0.0515 (10)	0.0427 (9)	0.0390 (8)	−0.0005 (8)	0.0022 (8)	−0.0086 (7)
C1	0.0426 (11)	0.0426 (10)	0.0454 (10)	−0.0006 (9)	0.0052 (8)	0.0082 (8)
C2	0.0590 (13)	0.0576 (12)	0.0398 (10)	0.0047 (12)	0.0044 (10)	0.0176 (9)
C3	0.0566 (12)	0.0632 (13)	0.0310 (8)	0.0078 (11)	−0.0025 (9)	0.0083 (8)
C4	0.0438 (11)	0.0509 (11)	0.0299 (8)	0.0059 (9)	−0.0008 (8)	0.0013 (8)
C5	0.0328 (9)	0.0427 (9)	0.0305 (8)	0.0023 (8)	0.0022 (7)	0.0042 (7)
C6	0.0323 (9)	0.0463 (10)	0.0338 (8)	0.0017 (8)	0.0015 (7)	0.0046 (7)
C7	0.0646 (16)	0.0618 (15)	0.0900 (19)	−0.0224 (14)	−0.0152 (15)	0.0162 (14)
C8	0.0557 (12)	0.0555 (12)	0.0339 (9)	0.0004 (11)	−0.0091 (9)	−0.0025 (8)
C9	0.0395 (10)	0.0471 (10)	0.0363 (9)	−0.0033 (8)	−0.0033 (8)	−0.0044 (8)
C10	0.0321 (8)	0.0382 (9)	0.0307 (8)	−0.0007 (7)	0.0004 (7)	−0.0010 (7)
C11	0.0330 (9)	0.0383 (9)	0.0271 (7)	0.0032 (7)	−0.0010 (7)	0.0019 (7)
C12	0.0416 (10)	0.0356 (9)	0.0384 (9)	−0.0028 (8)	0.0065 (8)	−0.0018 (7)
C13	0.0359 (9)	0.0366 (9)	0.0313 (8)	0.0051 (8)	0.0026 (7)	0.0025 (7)
C14	0.0361 (9)	0.0328 (8)	0.0287 (8)	0.0028 (7)	−0.0010 (7)	−0.0011 (6)
C15	0.0305 (8)	0.0344 (8)	0.0311 (8)	0.0007 (7)	−0.0032 (7)	0.0034 (7)
C16	0.0424 (10)	0.0347 (9)	0.0347 (9)	0.0030 (8)	0.0044 (8)	0.0033 (7)
C17	0.0666 (15)	0.0672 (14)	0.0408 (10)	−0.0003 (13)	0.0186 (11)	−0.0031 (10)
C18	0.0519 (12)	0.0616 (13)	0.0457 (10)	0.0102 (11)	−0.0151 (10)	−0.0155 (9)
C19	0.0326 (9)	0.0346 (8)	0.0372 (9)	0.0050 (7)	0.0003 (7)	0.0027 (7)
C20	0.0296 (9)	0.0433 (9)	0.0370 (8)	0.0018 (8)	−0.0030 (7)	0.0037 (8)
C21	0.0350 (9)	0.0441 (9)	0.0403 (9)	0.0059 (8)	−0.0006 (8)	−0.0020 (8)
C22	0.0493 (12)	0.0492 (11)	0.0449 (10)	0.0089 (9)	0.0036 (9)	−0.0088 (9)
C23	0.0730 (16)	0.0523 (13)	0.0527 (12)	−0.0053 (12)	0.0027 (12)	−0.0173 (10)

Geometric parameters (Å, º) top

C1—O1	1.377 (3)	C13—C14	1.587 (2)
C1—C6	1.390 (3)	C13—H13	0.9800
C1—C2	1.394 (3)	C14—O3	1.413 (2)
C2—C3	1.383 (3)	C14—C19	1.500 (2)
C2—H2	0.9300	C14—C15	1.542 (2)
C3—C4	1.400 (3)	C15—O2	1.468 (2)
C3—H3	0.9300	C15—H15	0.9800
C4—C5	1.383 (2)	C16—O4	1.199 (2)
C4—C8	1.505 (3)	C16—O5	1.332 (2)
C5—C6	1.373 (3)	C17—O5	1.446 (2)
C5—C11	1.499 (2)	C17—H17A	0.9600
C6—O2	1.373 (2)	C17—H17B	0.9600
C7—O1	1.412 (3)	C17—H17C	0.9600
C7—H7A	0.9600	C18—O3	1.427 (2)
C7—H7B	0.9600	C18—H18A	0.9600
C7—H7C	0.9600	C18—H18B	0.9600
C8—C9	1.565 (3)	C18—H18C	0.9600
C8—H8A	0.9700	C19—C20	1.322 (3)
C8—H8B	0.9700	C19—H19	0.9300
C9—N1	1.470 (3)	C20—H20	0.9300
C9—C10	1.539 (2)	C21—C22	1.519 (3)
C9—H9	0.9800	C21—H21A	0.9700
C10—C20	1.517 (2)	C21—H21B	0.9700
C10—C12	1.537 (2)	C22—N1	1.457 (3)
C10—C11	1.549 (3)	C22—H22A	0.9700
C11—C21	1.530 (2)	C22—H22B	0.9700
C11—C15	1.545 (2)	C23—N1	1.458 (3)
C12—C13	1.546 (2)	C23—H23A	0.9600
C12—H12A	0.9700	C23—H23B	0.9600
C12—H12B	0.9700	C23—H23C	0.9600
C13—C16	1.514 (2)

O1—C1—C6	125.05 (18)	C14—C13—H13	109.3
O1—C1—C2	118.06 (18)	O3—C14—C19	107.84 (14)
C6—C1—C2	116.58 (19)	O3—C14—C15	114.23 (15)
C3—C2—C1	122.32 (18)	C19—C14—C15	109.89 (13)
C3—C2—H2	118.8	O3—C14—C13	113.10 (13)
C1—C2—H2	118.8	C19—C14—C13	107.12 (15)
C2—C3—C4	120.79 (18)	C15—C14—C13	104.43 (13)
C2—C3—H3	119.6	O2—C15—C14	112.14 (13)
C4—C3—H3	119.6	O2—C15—C11	107.22 (13)
C5—C4—C3	115.65 (19)	C14—C15—C11	108.33 (14)
C5—C4—C8	118.90 (16)	O2—C15—H15	109.7
C3—C4—C8	124.56 (17)	C14—C15—H15	109.7
C6—C5—C4	123.50 (17)	C11—C15—H15	109.7
C6—C5—C11	109.92 (15)	O4—C16—O5	123.30 (18)
C4—C5—C11	124.16 (17)	O4—C16—C13	124.74 (17)
O2—C6—C5	113.03 (16)	O5—C16—C13	111.95 (16)
O2—C6—C1	126.25 (18)	O5—C17—H17A	109.5
C5—C6—C1	120.22 (17)	O5—C17—H17B	109.5
O1—C7—H7A	109.5	H17A—C17—H17B	109.5
O1—C7—H7B	109.5	O5—C17—H17C	109.5
H7A—C7—H7B	109.5	H17A—C17—H17C	109.5
O1—C7—H7C	109.5	H17B—C17—H17C	109.5
H7A—C7—H7C	109.5	O3—C18—H18A	109.5
H7B—C7—H7C	109.5	O3—C18—H18B	109.5
C4—C8—C9	115.59 (15)	H18A—C18—H18B	109.5
C4—C8—H8A	108.4	O3—C18—H18C	109.5
C9—C8—H8A	108.4	H18A—C18—H18C	109.5
C4—C8—H8B	108.4	H18B—C18—H18C	109.5
C9—C8—H8B	108.4	C20—C19—C14	115.44 (16)
H8A—C8—H8B	107.4	C20—C19—H19	122.3
N1—C9—C10	108.61 (15)	C14—C19—H19	122.3
N1—C9—C8	114.22 (17)	C19—C20—C10	114.87 (16)
C10—C9—C8	111.27 (15)	C19—C20—H20	122.6
N1—C9—H9	107.5	C10—C20—H20	122.6
C10—C9—H9	107.5	C22—C21—C11	112.26 (16)
C8—C9—H9	107.5	C22—C21—H21A	109.2
C20—C10—C12	105.24 (14)	C11—C21—H21A	109.2
C20—C10—C9	114.03 (15)	C22—C21—H21B	109.2
C12—C10—C9	115.75 (15)	C11—C21—H21B	109.2
C20—C10—C11	107.15 (14)	H21A—C21—H21B	107.9
C12—C10—C11	108.81 (15)	N1—C22—C21	110.23 (17)
C9—C10—C11	105.52 (15)	N1—C22—H22A	109.6
C5—C11—C21	114.36 (15)	C21—C22—H22A	109.6
C5—C11—C15	101.29 (14)	N1—C22—H22B	109.6
C21—C11—C15	112.32 (14)	C21—C22—H22B	109.6
C5—C11—C10	105.56 (14)	H22A—C22—H22B	108.1
C21—C11—C10	111.03 (15)	N1—C23—H23A	109.5
C15—C11—C10	111.77 (14)	N1—C23—H23B	109.5
C10—C12—C13	109.52 (14)	H23A—C23—H23B	109.5
C10—C12—H12A	109.8	N1—C23—H23C	109.5
C13—C12—H12A	109.8	H23A—C23—H23C	109.5
C10—C12—H12B	109.8	H23B—C23—H23C	109.5
C13—C12—H12B	109.8	C22—N1—C23	111.90 (18)
H12A—C12—H12B	108.2	C22—N1—C9	112.11 (17)
C16—C13—C12	111.21 (16)	C23—N1—C9	112.95 (17)
C16—C13—C14	107.99 (14)	C1—O1—C7	116.17 (18)
C12—C13—C14	109.82 (13)	C6—O2—C15	107.29 (14)
C16—C13—H13	109.3	C14—O3—C18	116.21 (15)
C12—C13—H13	109.3	C16—O5—C17	115.13 (17)

O1—C1—C2—C3	−171.3 (2)	C16—C13—C14—C19	−72.07 (17)
C6—C1—C2—C3	2.5 (3)	C12—C13—C14—C19	49.36 (19)
C1—C2—C3—C4	−3.8 (4)	C16—C13—C14—C15	171.38 (14)
C2—C3—C4—C5	−2.2 (3)	C12—C13—C14—C15	−67.18 (17)
C2—C3—C4—C8	166.8 (2)	O3—C14—C15—O2	−55.46 (18)
C3—C4—C5—C6	10.0 (3)	C19—C14—C15—O2	65.87 (18)
C8—C4—C5—C6	−159.66 (19)	C13—C14—C15—O2	−179.52 (13)
C3—C4—C5—C11	170.57 (18)	O3—C14—C15—C11	−173.59 (13)
C8—C4—C5—C11	0.9 (3)	C19—C14—C15—C11	−52.26 (18)
C4—C5—C6—O2	160.73 (17)	C13—C14—C15—C11	62.35 (16)
C11—C5—C6—O2	−2.2 (2)	C5—C11—C15—O2	−10.94 (17)
C4—C5—C6—C1	−11.7 (3)	C21—C11—C15—O2	111.52 (16)
C11—C5—C6—C1	−174.64 (17)	C10—C11—C15—O2	−122.92 (14)
O1—C1—C6—O2	6.9 (3)	C5—C11—C15—C14	110.28 (15)
C2—C1—C6—O2	−166.41 (19)	C21—C11—C15—C14	−127.26 (15)
O1—C1—C6—C5	178.25 (19)	C10—C11—C15—C14	−1.70 (18)
C2—C1—C6—C5	4.9 (3)	C12—C13—C16—O4	−37.8 (3)
C5—C4—C8—C9	6.1 (3)	C14—C13—C16—O4	82.8 (2)
C3—C4—C8—C9	−162.6 (2)	C12—C13—C16—O5	142.17 (16)
C4—C8—C9—N1	−97.5 (2)	C14—C13—C16—O5	−97.26 (17)
C4—C8—C9—C10	25.9 (3)	O3—C14—C19—C20	−178.76 (16)
N1—C9—C10—C20	−178.89 (16)	C15—C14—C19—C20	56.2 (2)
C8—C9—C10—C20	54.6 (2)	C13—C14—C19—C20	−56.72 (19)
N1—C9—C10—C12	−56.6 (2)	C14—C19—C20—C10	1.0 (2)
C8—C9—C10—C12	176.87 (18)	C12—C10—C20—C19	59.6 (2)
N1—C9—C10—C11	63.79 (18)	C9—C10—C20—C19	−172.53 (17)
C8—C9—C10—C11	−62.8 (2)	C11—C10—C20—C19	−56.2 (2)
C6—C5—C11—C21	−112.91 (18)	C5—C11—C21—C22	−66.6 (2)
C4—C5—C11—C21	84.3 (2)	C15—C11—C21—C22	178.70 (16)
C6—C5—C11—C15	8.13 (19)	C10—C11—C21—C22	52.7 (2)
C4—C5—C11—C15	−154.69 (18)	C11—C21—C22—N1	−50.8 (2)
C6—C5—C11—C10	124.75 (16)	C21—C22—N1—C23	−173.61 (17)
C4—C5—C11—C10	−38.1 (2)	C21—C22—N1—C9	58.3 (2)
C20—C10—C11—C5	−55.15 (18)	C10—C9—N1—C22	−66.6 (2)
C12—C10—C11—C5	−168.46 (14)	C8—C9—N1—C22	58.2 (2)
C9—C10—C11—C5	66.73 (17)	C10—C9—N1—C23	165.85 (17)
C20—C10—C11—C21	−179.60 (13)	C8—C9—N1—C23	−69.3 (2)
C12—C10—C11—C21	67.09 (18)	C6—C1—O1—C7	45.0 (3)
C9—C10—C11—C21	−57.73 (18)	C2—C1—O1—C7	−141.8 (2)
C20—C10—C11—C15	54.12 (18)	C5—C6—O2—C15	−5.3 (2)
C12—C10—C11—C15	−59.19 (17)	C1—C6—O2—C15	166.61 (18)
C9—C10—C11—C15	175.99 (14)	C14—C15—O2—C6	−108.49 (15)
C20—C10—C12—C13	−60.31 (19)	C11—C15—O2—C6	10.29 (18)
C9—C10—C12—C13	172.82 (16)	C19—C14—O3—C18	−168.91 (17)
C11—C10—C12—C13	54.25 (19)	C15—C14—O3—C18	−46.5 (2)
C10—C12—C13—C16	126.85 (16)	C13—C14—O3—C18	72.8 (2)
C10—C12—C13—C14	7.4 (2)	O4—C16—O5—C17	0.6 (3)
C16—C13—C14—O3	46.6 (2)	C13—C16—O5—C17	−179.37 (16)
C12—C13—C14—O3	168.04 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O2	0.96	2.34	3.002 (3)	125
C12—H12B···O4	0.97	2.46	2.899 (2)	107
C15—H15···O4ⁱ	0.98	2.53	3.483 (2)	165
C17—H17C···O2ⁱⁱ	0.96	2.62	3.533 (3)	158

Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂₃H₂₇NO₅
M_r	397.46
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	6.5604 (2), 10.4082 (3), 29.1382 (11)
V (Å³)	1989.61 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.39 × 0.35 × 0.31

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.966, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	27330, 2467, 2300
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.634

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.085, 1.06
No. of reflections	2467
No. of parameters	262
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.14

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O2	0.96	2.34	3.002 (3)	125.4
C12—H12B···O4	0.97	2.46	2.899 (2)	107.2
C15—H15···O4ⁱ	0.98	2.53	3.483 (2)	164.7
C17—H17C···O2ⁱⁱ	0.96	2.62	3.533 (3)	158.2

Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+3/2.

Acknowledgements

The authors gratefully acknowledge financial support from the Scientific and Technical Research Council of Turkey (TUBITAK, Project No. 107 T676). We also thank the Turkish Grain Board (TMO) for the supply of thebaine.

References

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