6α-Acet­oxy-4,5α-ep­oxy-3-meth­oxy-17-meth­ylmorphin-7-ene

Crystals of the title compound, which is also commonly known as 6-O-acetyl­codeine, C₂₀H₂₃NO₄, were obtained by acetyl­ation of codeine and subsequent crystallization of the product from eth­yl acetate. The atoms of the benzene ring are nearly coplanar, whereas the five-memberedring is distorted. The ethanamine ring has a typical chair form conformation, while the cyclohexene ring is in a twisted boat form.

Key indicators

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.047
• wR factor = 0.112
• Data-to-parameter ratio = 7.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............      24.99 Deg.

Alert level C
STRVA01_ALERT_2_C           Chirality of atom sites is inverted?
           From the CIF: _refine_ls_abs_structure_Flack    2.000
           From the CIF: _refine_ls_abs_structure_Flack_su    2.000
PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ...       2.00
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       2.00
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.35
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          6

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           24.99
           From the CIF: _reflns_number_total               1683
           Count of symmetry unique reflns         1681
           Completeness (_total/calc)            100.12%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         2
           Fraction of Friedel pairs measured     0.001
           Are heavy atom types Z>Si present         no

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and local procedures.

6α-Acetoxy-4,5α-epoxy-3-methoxy-17-methyl-morphin-7-ene

Crystal data

C20H23NO4	F(000) = 728
Mr = 341.39	Dx = 1.374 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2134 reflections
a = 8.6588 (4) Å	θ = 1.0–27.5°
b = 12.3368 (7) Å	µ = 0.10 mm^−1
c = 15.4441 (9) Å	T = 90 K
V = 1649.77 (15) Å^3	Irregular fragment, colorless
Z = 4	0.25 × 0.15 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer	1116 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.074
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
Detector resolution: 18 pixels mm^-1	h = −10→10
ω scans at fixed χ = 55°	k = −14→14
2902 measured reflections	l = −18→18
1683 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0595P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.002
1683 reflections	Δρmax = 0.22 e Å^−3
229 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 2 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.6277 (5)	0.3238 (3)	0.6390 (3)	0.0209 (10)
H1	0.5549	0.3212	0.5930	0.025*
C2	0.7851 (5)	0.3297 (3)	0.6203 (3)	0.0217 (10)
H2	0.8176	0.3286	0.5616	0.026*
O3	1.0536 (3)	0.3441 (2)	0.67238 (16)	0.0240 (8)
C3	0.8955 (5)	0.3373 (3)	0.6849 (3)	0.0195 (10)
O4	0.9288 (3)	0.3454 (2)	0.84450 (17)	0.0210 (7)
C4	0.8426 (5)	0.3361 (3)	0.7692 (2)	0.0184 (10)
C5	0.8166 (4)	0.3746 (3)	0.9121 (3)	0.0201 (11)
H5	0.8516	0.3462	0.9694	0.024*
O6	0.8980 (3)	0.5506 (2)	0.85046 (17)	0.0233 (7)
C6	0.8021 (4)	0.5005 (4)	0.9158 (3)	0.0203 (11)
H6	0.8389	0.5253	0.9739	0.024*
C7	0.6444 (5)	0.5460 (4)	0.9010 (3)	0.0235 (11)
H7	0.6359	0.6222	0.8937	0.028*
C8	0.5148 (5)	0.4882 (4)	0.8973 (3)	0.0226 (11)
H8	0.4200	0.5250	0.8878	0.027*
C9	0.3861 (5)	0.3107 (3)	0.8539 (3)	0.0209 (10)
H9	0.2850	0.3448	0.8692	0.025*
C10	0.4096 (4)	0.3249 (3)	0.7545 (2)	0.0214 (10)
H10A	0.3517	0.2669	0.7242	0.026*
H10B	0.3641	0.3951	0.7368	0.026*
C11	0.5761 (4)	0.3215 (3)	0.7243 (3)	0.0197 (10)
C12	0.6882 (5)	0.3243 (3)	0.7876 (3)	0.0191 (10)
C13	0.6669 (4)	0.3169 (3)	0.8841 (2)	0.0180 (10)
C14	0.5125 (5)	0.3686 (3)	0.9074 (3)	0.0216 (11)
H14	0.4922	0.3526	0.9698	0.026*
C15	0.6617 (5)	0.1971 (3)	0.9123 (3)	0.0220 (11)
H15A	0.7590	0.1609	0.8950	0.026*
H15B	0.6531	0.1931	0.9761	0.026*
C16	0.5261 (5)	0.1383 (4)	0.8715 (3)	0.0229 (11)
H16A	0.5452	0.1293	0.8087	0.028*
H16B	0.5166	0.0653	0.8975	0.028*
N17	0.3815 (4)	0.1979 (3)	0.8842 (2)	0.0220 (9)
C17	0.2487 (4)	0.1377 (4)	0.8515 (3)	0.0302 (12)
H17A	0.1548	0.1809	0.8595	0.045*
H17B	0.2388	0.0693	0.8833	0.045*
H17C	0.2632	0.1224	0.7898	0.045*
C18	1.1055 (5)	0.3535 (5)	0.5859 (3)	0.0436 (14)
H18A	1.0768	0.2881	0.5536	0.065*
H18B	1.2180	0.3619	0.5853	0.065*
H18C	1.0575	0.4170	0.5589	0.065*
O19	1.1091 (3)	0.5338 (3)	0.9356 (2)	0.0337 (8)
C19	1.0517 (5)	0.5514 (3)	0.8661 (3)	0.0252 (11)
C20	1.1357 (5)	0.5753 (3)	0.7839 (3)	0.0273 (11)
H20A	1.2317	0.6140	0.7970	0.041*
H20B	1.0705	0.6203	0.7465	0.041*
H20C	1.1599	0.5072	0.7542	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.020 (2)	0.025 (3)	0.017 (2)	0.005 (2)	−0.006 (2)	−0.005 (2)
C2	0.029 (2)	0.023 (3)	0.013 (2)	−0.001 (2)	0.004 (2)	−0.001 (2)
O3	0.0168 (16)	0.0364 (19)	0.0189 (16)	0.0001 (15)	0.0032 (14)	0.0026 (15)
C3	0.016 (2)	0.016 (2)	0.026 (2)	0.000 (2)	0.002 (2)	−0.003 (2)
O4	0.0177 (16)	0.0267 (17)	0.0185 (15)	−0.0015 (14)	0.0007 (14)	−0.0015 (14)
C4	0.024 (2)	0.017 (2)	0.014 (2)	0.000 (2)	−0.004 (2)	0.001 (2)
C5	0.018 (2)	0.028 (3)	0.015 (2)	0.002 (2)	0.004 (2)	−0.002 (2)
O6	0.0202 (16)	0.0280 (17)	0.0216 (16)	−0.0014 (15)	0.0041 (14)	0.0042 (15)
C6	0.018 (2)	0.027 (3)	0.016 (2)	0.002 (2)	0.000 (2)	0.003 (2)
C7	0.027 (2)	0.025 (3)	0.018 (2)	0.002 (2)	0.003 (2)	0.000 (2)
C8	0.021 (2)	0.031 (3)	0.016 (2)	0.004 (2)	−0.004 (2)	−0.003 (2)
C9	0.019 (2)	0.023 (2)	0.020 (2)	−0.001 (2)	−0.001 (2)	0.000 (2)
C10	0.019 (2)	0.023 (2)	0.023 (2)	0.000 (2)	0.003 (2)	−0.001 (2)
C11	0.022 (2)	0.017 (2)	0.020 (2)	0.001 (2)	0.001 (2)	0.000 (2)
C12	0.019 (2)	0.015 (2)	0.024 (2)	0.003 (2)	0.001 (2)	0.000 (2)
C13	0.014 (2)	0.024 (3)	0.016 (2)	0.001 (2)	0.0002 (19)	−0.001 (2)
C14	0.024 (2)	0.025 (3)	0.016 (2)	−0.003 (2)	−0.001 (2)	0.002 (2)
C15	0.023 (2)	0.023 (2)	0.020 (2)	0.001 (2)	−0.002 (2)	0.001 (2)
C16	0.026 (2)	0.024 (2)	0.019 (2)	−0.002 (2)	−0.001 (2)	0.002 (2)
N17	0.020 (2)	0.023 (2)	0.023 (2)	−0.0041 (18)	−0.0034 (18)	0.0004 (17)
C17	0.028 (3)	0.034 (3)	0.029 (3)	−0.002 (2)	−0.004 (2)	0.003 (2)
C18	0.024 (3)	0.081 (4)	0.026 (3)	0.002 (3)	0.009 (2)	0.009 (3)
O19	0.0246 (17)	0.047 (2)	0.0296 (18)	−0.0058 (17)	−0.0085 (16)	0.0053 (16)
C19	0.023 (3)	0.016 (2)	0.037 (3)	−0.001 (2)	0.000 (2)	−0.004 (2)
C20	0.022 (2)	0.026 (3)	0.034 (3)	0.001 (2)	0.006 (2)	0.002 (2)

Geometric parameters (Å, º)

C1—C11	1.392 (6)	C10—C11	1.516 (5)
C1—C2	1.396 (5)	C10—H10A	0.9900
C1—H1	0.9500	C10—H10B	0.9900
C2—C3	1.385 (5)	C11—C12	1.377 (5)
C2—H2	0.9500	C12—C13	1.505 (6)
O3—C3	1.385 (5)	C13—C14	1.524 (6)
O3—C18	1.413 (5)	C13—C15	1.542 (5)
C3—C4	1.381 (5)	C14—H14	1.0000
O4—C4	1.387 (4)	C15—C16	1.516 (5)
O4—C5	1.471 (4)	C15—H15A	0.9900
C4—C12	1.374 (6)	C15—H15B	0.9900
C5—C13	1.541 (6)	C16—N17	1.465 (5)
C5—C6	1.558 (6)	C16—H16A	0.9900
C5—H5	1.0000	C16—H16B	0.9900
O6—C19	1.353 (5)	N17—C17	1.460 (5)
O6—C6	1.446 (4)	C17—H17A	0.9800
C6—C7	1.495 (6)	C17—H17B	0.9800
C6—H6	1.0000	C17—H17C	0.9800
C7—C8	1.331 (6)	C18—H18A	0.9800
C7—H7	0.9500	C18—H18B	0.9800
C8—C14	1.484 (6)	C18—H18C	0.9800
C8—H8	0.9500	O19—C19	1.203 (5)
C9—N17	1.469 (5)	C19—C20	1.492 (6)
C9—C14	1.546 (6)	C20—H20A	0.9800
C9—C10	1.559 (5)	C20—H20B	0.9800
C9—H9	1.0000	C20—H20C	0.9800
C11—C1—C2	120.7 (4)	C11—C12—C13	127.9 (4)
C11—C1—H1	119.7	C12—C13—C14	108.4 (3)
C2—C1—H1	119.7	C12—C13—C5	98.4 (3)
C3—C2—C1	122.0 (4)	C14—C13—C5	118.5 (3)
C3—C2—H2	119.0	C12—C13—C15	110.0 (3)
C1—C2—H2	119.0	C14—C13—C15	108.0 (3)
C3—O3—C18	116.8 (3)	C5—C13—C15	112.9 (3)
C4—C3—C2	116.7 (4)	C8—C14—C13	112.3 (4)
C4—C3—O3	117.4 (4)	C8—C14—C9	114.4 (4)
C2—C3—O3	125.9 (4)	C13—C14—C9	107.6 (3)
C4—O4—C5	105.0 (3)	C8—C14—H14	107.4
C12—C4—C3	121.2 (4)	C13—C14—H14	107.4
C12—C4—O4	111.1 (3)	C9—C14—H14	107.4
C3—C4—O4	127.6 (4)	C16—C15—C13	111.3 (3)
O4—C5—C13	104.1 (3)	C16—C15—H15A	109.4
O4—C5—C6	108.9 (3)	C13—C15—H15A	109.4
C13—C5—C6	113.8 (3)	C16—C15—H15B	109.4
O4—C5—H5	110.0	C13—C15—H15B	109.4
C13—C5—H5	110.0	H15A—C15—H15B	108.0
C6—C5—H5	110.0	N17—C16—C15	111.5 (3)
C19—O6—C6	116.3 (3)	N17—C16—H16A	109.3
O6—C6—C7	104.9 (3)	C15—C16—H16A	109.3
O6—C6—C5	110.8 (3)	N17—C16—H16B	109.3
C7—C6—C5	116.2 (3)	C15—C16—H16B	109.3
O6—C6—H6	108.2	H16A—C16—H16B	108.0
C7—C6—H6	108.2	C17—N17—C16	111.8 (3)
C5—C6—H6	108.2	C17—N17—C9	113.1 (3)
C8—C7—C6	125.1 (4)	C16—N17—C9	114.2 (3)
C8—C7—H7	117.4	N17—C17—H17A	109.5
C6—C7—H7	117.4	N17—C17—H17B	109.5
C7—C8—C14	122.7 (4)	H17A—C17—H17B	109.5
C7—C8—H8	118.6	N17—C17—H17C	109.5
C14—C8—H8	118.6	H17A—C17—H17C	109.5
N17—C9—C14	106.6 (3)	H17B—C17—H17C	109.5
N17—C9—C10	115.1 (3)	O3—C18—H18A	109.5
C14—C9—C10	112.5 (3)	O3—C18—H18B	109.5
N17—C9—H9	107.4	H18A—C18—H18B	109.5
C14—C9—H9	107.4	O3—C18—H18C	109.5
C10—C9—H9	107.4	H18A—C18—H18C	109.5
C11—C10—C9	115.0 (3)	H18B—C18—H18C	109.5
C11—C10—H10A	108.5	O19—C19—O6	124.4 (4)
C9—C10—H10A	108.5	O19—C19—C20	126.5 (4)
C11—C10—H10B	108.5	O6—C19—C20	109.2 (4)
C9—C10—H10B	108.5	C19—C20—H20A	109.5
H10A—C10—H10B	107.5	C19—C20—H20B	109.5
C12—C11—C1	116.4 (4)	H20A—C20—H20B	109.5
C12—C11—C10	116.9 (3)	C19—C20—H20C	109.5
C1—C11—C10	126.5 (4)	H20A—C20—H20C	109.5
C4—C12—C11	122.8 (4)	H20B—C20—H20C	109.5
C4—C12—C13	109.3 (4)
C11—C1—C2—C3	−2.2 (7)	C4—C12—C13—C14	147.3 (3)
C1—C2—C3—C4	1.5 (6)	C11—C12—C13—C14	−32.1 (6)
C1—C2—C3—O3	−179.7 (4)	C4—C12—C13—C5	23.3 (4)
C18—O3—C3—C4	−175.4 (4)	C11—C12—C13—C5	−156.0 (4)
C18—O3—C3—C2	5.8 (6)	C4—C12—C13—C15	−94.8 (4)
C2—C3—C4—C12	2.0 (6)	C11—C12—C13—C15	85.8 (5)
O3—C3—C4—C12	−176.9 (4)	O4—C5—C13—C12	−33.0 (4)
C2—C3—C4—O4	−178.1 (4)	C6—C5—C13—C12	85.3 (4)
O3—C3—C4—O4	3.0 (6)	O4—C5—C13—C14	−149.4 (3)
C5—O4—C4—C12	−18.1 (4)	C6—C5—C13—C14	−31.0 (5)
C5—O4—C4—C3	162.1 (4)	O4—C5—C13—C15	82.9 (4)
C4—O4—C5—C13	32.5 (4)	C6—C5—C13—C15	−158.7 (4)
C4—O4—C5—C6	−89.2 (4)	C7—C8—C14—C13	−24.3 (6)
C19—O6—C6—C7	159.2 (4)	C7—C8—C14—C9	−147.2 (4)
C19—O6—C6—C5	−74.6 (4)	C12—C13—C14—C8	−71.0 (4)
O4—C5—C6—O6	2.0 (4)	C5—C13—C14—C8	39.9 (5)
C13—C5—C6—O6	−113.5 (3)	C15—C13—C14—C8	169.9 (3)
O4—C5—C6—C7	121.6 (4)	C12—C13—C14—C9	55.7 (4)
C13—C5—C6—C7	6.0 (6)	C5—C13—C14—C9	166.6 (4)
O6—C6—C7—C8	132.7 (4)	C15—C13—C14—C9	−63.4 (4)
C5—C6—C7—C8	10.0 (6)	N17—C9—C14—C8	−169.4 (3)
C6—C7—C8—C14	−0.3 (7)	C10—C9—C14—C8	63.6 (5)
N17—C9—C10—C11	−84.3 (5)	N17—C9—C14—C13	65.2 (4)
C14—C9—C10—C11	38.1 (5)	C10—C9—C14—C13	−61.9 (5)
C2—C1—C11—C12	−0.7 (6)	C12—C13—C15—C16	−62.0 (5)
C2—C1—C11—C10	174.4 (4)	C14—C13—C15—C16	56.2 (4)
C9—C10—C11—C12	−10.2 (6)	C5—C13—C15—C16	−170.8 (3)
C9—C10—C11—C1	174.7 (4)	C13—C15—C16—N17	−50.5 (4)
C3—C4—C12—C11	−5.1 (6)	C15—C16—N17—C17	−175.3 (4)
O4—C4—C12—C11	175.0 (4)	C15—C16—N17—C9	54.6 (4)
C3—C4—C12—C13	175.5 (4)	C14—C9—N17—C17	169.2 (3)
O4—C4—C12—C13	−4.4 (5)	C10—C9—N17—C17	−65.3 (5)
C1—C11—C12—C4	4.3 (6)	C14—C9—N17—C16	−61.4 (4)
C10—C11—C12—C4	−171.3 (4)	C10—C9—N17—C16	64.1 (4)
C1—C11—C12—C13	−176.4 (4)	C6—O6—C19—O19	−15.4 (6)
C10—C11—C12—C13	8.0 (6)	C6—O6—C19—C20	163.6 (3)