6-O-Acetyl­codeine

The title compound (systematic name: 6α-acet­oxy-4,5α-ep­oxy-3-meth­oxy-17-meth­yl-morphin-7-ene), C₂₀H₂₃NO₄, crystallizes 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...π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 290 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.049
• wR factor = 0.126
• Data-to-parameter ratio = 8.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.20 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.54 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         O1
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           26.01
           From the CIF: _reflns_number_total               1928
           Count of symmetry unique reflns         1928
           Completeness (_total/calc)            100.00%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 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
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

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: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Version 1.3; Bruno et al., 2002); software used to prepare material for publication: WinGX (Farrugia, 1999).

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

Crystal data

C20H23NO4	Dx = 1.334 Mg m^−3
Mr = 341.39	Melting point = 405–406 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 22 reflections
a = 8.628 (2) Å	θ = 18.3–19.7°
b = 12.727 (2) Å	µ = 0.09 mm^−1
c = 15.4842 (19) Å	T = 290 K
V = 1700.3 (5) Å^3	Prism, colorles
Z = 4	0.25 × 0.25 × 0.25 mm
F(000) = 728

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.077
Radiation source: fine-focus sealed tube	θmax = 26.0°, θmin = 2.1°
Graphite monochromator	h = 0→10
non–profiled ω/2θ scans	k = 0→15
4181 measured reflections	l = −19→19
1928 independent reflections	3 standard reflections every 120 min
1093 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0562P)^2] where P = (Fo^2 + 2Fc^2)/3
1928 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

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 ν_C—H of double C—C bond. The middle intensity bands between 2961 and 2811 are attributed to ν_C—H vibrations of methine, methilene. The very strong band at 1735 was ascribed to ν_C=O of the acetyl group. The middle band at 1617 is attributed to ν_C=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 ν_C—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 (Ų)

	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)
H16A	0.5464	0.1306	0.3062	0.062*
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.050 (3)	0.064 (3)	0.031 (2)	0.005 (3)	−0.007 (2)	0.005 (2)
C2	0.052 (3)	0.065 (3)	0.025 (2)	0.006 (3)	0.004 (2)	−0.001 (2)
C3	0.041 (3)	0.053 (3)	0.038 (2)	0.005 (3)	0.003 (2)	−0.002 (2)
C4	0.039 (3)	0.045 (3)	0.0275 (19)	0.009 (2)	−0.004 (2)	0.002 (2)
C5	0.036 (3)	0.063 (3)	0.0212 (19)	0.005 (2)	0.0028 (19)	−0.001 (2)
C6	0.047 (3)	0.061 (3)	0.032 (2)	0.001 (3)	−0.001 (2)	−0.002 (2)
C7	0.045 (3)	0.051 (3)	0.049 (3)	0.008 (3)	0.006 (2)	−0.004 (2)
C8	0.037 (3)	0.066 (3)	0.039 (2)	0.007 (3)	0.002 (2)	−0.010 (2)
C9	0.032 (2)	0.065 (3)	0.037 (2)	0.001 (2)	0.005 (2)	−0.002 (2)
C10	0.040 (3)	0.058 (3)	0.039 (2)	−0.001 (3)	−0.004 (2)	0.002 (2)
C11	0.043 (3)	0.047 (3)	0.029 (2)	0.004 (2)	−0.004 (2)	−0.002 (2)
C12	0.039 (3)	0.038 (2)	0.029 (2)	0.004 (2)	0.0005 (19)	−0.0011 (18)
C13	0.035 (2)	0.052 (3)	0.0257 (19)	0.003 (2)	−0.0005 (19)	0.0003 (19)
C14	0.041 (3)	0.059 (3)	0.034 (2)	0.002 (2)	0.005 (2)	−0.004 (2)
C15	0.045 (3)	0.057 (3)	0.036 (2)	0.003 (3)	−0.001 (2)	0.006 (2)
C16	0.063 (3)	0.049 (3)	0.043 (2)	−0.005 (3)	0.001 (3)	0.003 (2)
C17	0.055 (4)	0.090 (4)	0.070 (4)	−0.024 (3)	−0.004 (3)	0.001 (3)
C18	0.053 (4)	0.239 (9)	0.048 (3)	0.001 (5)	0.017 (3)	0.027 (5)
C19	0.049 (3)	0.051 (3)	0.065 (3)	0.001 (3)	0.002 (3)	0.005 (3)
C20	0.055 (3)	0.063 (3)	0.084 (4)	0.002 (3)	0.018 (3)	0.015 (3)
N1	0.043 (2)	0.064 (3)	0.041 (2)	−0.007 (2)	0.0013 (18)	−0.0004 (19)
O1	0.0383 (18)	0.101 (3)	0.0390 (17)	0.004 (2)	0.0098 (15)	0.0068 (19)
O2	0.0371 (18)	0.061 (2)	0.0358 (16)	0.0061 (16)	0.0032 (13)	−0.0018 (15)
O3	0.0388 (19)	0.061 (2)	0.0531 (19)	−0.0020 (17)	0.0007 (16)	0.0095 (16)
O4	0.052 (2)	0.125 (4)	0.071 (3)	−0.013 (2)	−0.013 (2)	0.016 (2)

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
O3—C6—C7	104.9 (4)	C15—C16—H16A	109.4
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)
C11—C1—C2—C3	−2.0 (8)	C10—C9—N1—C16	64.5 (5)
C2—C1—C11—C10	174.3 (5)	C10—C9—N1—C17	−64.4 (5)
C2—C1—C11—C12	−0.8 (8)	C14—C9—N1—C16	−62.5 (4)
C1—C2—C3—O1	−179.1 (5)	C14—C9—N1—C17	168.7 (4)
C1—C2—C3—C4	1.6 (7)	N1—C9—C10—C11	−85.6 (5)
C2—C3—O1—C18	2.6 (8)	C14—C9—C10—C11	37.8 (6)
C4—C3—O1—C18	−178.0 (5)	N1—C9—C14—C8	−169.5 (4)
O1—C3—C4—O2	3.4 (7)	N1—C9—C14—C13	66.8 (4)
O1—C3—C4—C12	−177.8 (4)	C10—C9—C14—C8	62.2 (5)
C2—C3—C4—O2	−177.2 (4)	C10—C9—C14—C13	−61.5 (5)
C2—C3—C4—C12	1.7 (7)	C9—C10—C11—C1	175.7 (4)
C3—C4—O2—C5	160.7 (4)	C9—C10—C11—C12	−9.2 (6)
C12—C4—O2—C5	−18.2 (5)	C1—C11—C12—C4	4.1 (7)
O2—C4—C12—C11	174.3 (4)	C1—C11—C12—C13	−177.6 (4)
O2—C4—C12—C13	−4.3 (5)	C10—C11—C12—C4	−171.5 (4)
C3—C4—C12—C11	−4.7 (7)	C10—C11—C12—C13	6.8 (7)
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···N1^i	0.98	2.42	3.363 (5)	163
C20—H20C···Cg1^ii	0.96	2.52	3.421 (2)	157

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