7,8-Dide­hydro-4,5-epoxy-17-methyl­morphinan-6-yl naphthalene-1-carboxyl­ate

Gathergood, N.; Scammells, P.J.; Fallon, G.D.

doi:10.1107/S1600536803025121

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7,8-Didehydro-4,5-epoxy-17-methylmorphinan-6-yl naphthalene-1-carboxylate

N. Gathergood, P. J. Scammells and G. D. Fallon

The crystal structure of morphine 3-(1-naphthoate), (or 7,8-didehydro-4,5-epoxy-17-methylmorphinan-6-yl naphthalene-1-carboxylate), C₂₈H₂₅NO₄, was determined at 123 K. An intramolecular hydrogen bond exists between the secondary alcohol and the naphthoate group. Within the crystal structure, there is no significant π–π stacking, but there are significant intermolecular C—H

π interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803025121/lh6134sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803025121/lh6134Isup2.hkl Contains datablock I

CCDC reference: 227879

checkCIF report

Key indicators

Single-crystal X-ray study
T = 123 K
Mean (C-C) = 0.003 Å
R factor = 0.036
wR factor = 0.082
Data-to-parameter ratio = 9.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.99

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           28.28
           From the CIF: _reflns_number_total               2909
           Count of symmetry unique reflns         2953
           Completeness (_total/calc)             98.51%
           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
   1 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
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: COLLECT (Nonius BV, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; 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); software used to prepare material for publication: WinGX (Farrugia, 1999).

7,8-didehydro-4,5-epoxy-17-methylmorphinan-6-(naphthalene-1-carboxylate) top

Crystal data top

C₂₈H₂₅NO₄	F(000) = 464
M_r = 439.49	D_x = 1.325 Mg m⁻³
Monoclinic, P2₁	Melting point = 443–445 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 12.7421 (2) Å	Cell parameters from 14873 reflections
b = 7.1908 (1) Å	θ = 2.8–28.3°
c = 12.9536 (3) Å	µ = 0.09 mm⁻¹
β = 111.900 (1)°	T = 123 K
V = 1101.23 (4) Å³	Acicular, colourless
Z = 2	0.24 × 0.20 × 0.12 mm

Data collection top

Nonius KappaCCD diffractometer	2423 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.044
Horizonally mounted graphite crystal monochromator	θ_max = 28.3°, θ_min = 2.8°
Detector resolution: 9 pixels mm^-1	h = −16→16
CCD rotation images, thick slices scans	k = −9→9
14873 measured reflections	l = −17→17
2909 independent reflections

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0416P)² + 0.1452P] where P = (F_o² + 2F_c²)/3
2909 reflections	(Δ/σ)_max = 0.002
300 parameters	Δρ_max = 0.19 e Å⁻³
1 restraint	Δρ_min = −0.20 e Å⁻³

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.

The absolute structure cannot be reliably determined therefore Friedel pairs have been merged.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.97625 (15)	0.5834 (3)	0.80473 (14)	0.0197 (4)
C2	0.95002 (15)	0.6995 (3)	0.87606 (15)	0.0217 (4)
C3	1.03452 (17)	0.7424 (3)	0.97782 (15)	0.0246 (4)
H3	1.0170	0.8178	1.0294	0.030*
C4	1.14411 (16)	0.6770 (3)	1.00531 (15)	0.0243 (4)
H4	1.2013	0.7128	1.0738	0.029*
C5	1.17139 (15)	0.5579 (3)	0.93257 (15)	0.0213 (4)
C6	1.08361 (15)	0.5091 (3)	0.83582 (14)	0.0180 (4)
C7	1.09088 (15)	0.3931 (3)	0.74229 (14)	0.0196 (4)
C8	0.98416 (16)	0.4608 (3)	0.64533 (15)	0.0215 (4)
H8	0.9469	0.3528	0.5969	0.026*
C9	1.00760 (16)	0.6150 (3)	0.57366 (14)	0.0243 (4)
H9	1.0198	0.5501	0.5108	0.029*
C10	1.11380 (16)	0.7231 (3)	0.63347 (15)	0.0258 (4)
H10	1.1150	0.8526	0.6196	0.031*
C11	1.20582 (17)	0.6431 (3)	0.70494 (16)	0.0269 (4)
H11	1.2729	0.7143	0.7381	0.032*
C12	1.20539 (16)	0.4407 (3)	0.73428 (16)	0.0238 (4)
H12	1.2150	0.3639	0.6740	0.029*
C13	1.29713 (16)	0.3860 (3)	0.84632 (17)	0.0261 (4)
H13	1.3718	0.4161	0.8415	0.031*
C14	1.28953 (16)	0.4995 (3)	0.94609 (16)	0.0274 (4)
H14A	1.3217	0.4235	1.0145	0.033*
H14B	1.3369	0.6123	0.9566	0.033*
C15	1.08588 (17)	0.1840 (3)	0.76422 (16)	0.0255 (4)
H15A	1.0153	0.1564	0.7766	0.031*
H15B	1.0839	0.1137	0.6978	0.031*
C16	1.18642 (18)	0.1202 (3)	0.86447 (17)	0.0300 (5)
H16A	1.1805	0.1712	0.9331	0.036*
H16B	1.1861	−0.0172	0.8692	0.036*
C17	1.39082 (19)	0.1051 (4)	0.94437 (18)	0.0410 (6)
H17A	1.3874	−0.0310	0.9408	0.061*
H17B	1.3917	0.1466	1.0168	0.061*
H17C	1.4597	0.1477	0.9349	0.061*
C18	0.79496 (15)	0.8781 (3)	0.75925 (15)	0.0224 (4)
C19	0.67468 (16)	0.9225 (3)	0.73928 (15)	0.0235 (4)
C20	0.61200 (17)	0.7891 (3)	0.76669 (17)	0.0306 (5)
H20	0.6470	0.6765	0.8007	0.037*
C21	0.49613 (19)	0.8184 (4)	0.7446 (2)	0.0398 (6)
H21	0.4533	0.7250	0.7629	0.048*
C22	0.44587 (18)	0.9796 (4)	0.69729 (19)	0.0386 (6)
H22	0.3679	0.9979	0.6834	0.046*
C23	0.50686 (17)	1.1216 (4)	0.66800 (16)	0.0304 (5)
C24	0.45392 (19)	1.2879 (4)	0.61676 (19)	0.0372 (5)
H24	0.3758	1.3056	0.6022	0.045*
C25	0.51224 (19)	1.4235 (4)	0.58763 (18)	0.0391 (6)
H25	0.4750	1.5340	0.5525	0.047*
C26	0.62925 (19)	1.3980 (4)	0.61029 (18)	0.0363 (5)
H26	0.6705	1.4930	0.5910	0.044*
C27	0.68311 (17)	1.2393 (3)	0.65931 (17)	0.0294 (5)
H27	0.7615	1.2256	0.6741	0.035*
C28	0.62430 (16)	1.0943 (3)	0.68863 (16)	0.0251 (4)
N1	1.29231 (14)	0.1822 (3)	0.85621 (14)	0.0296 (4)
O1	0.90821 (10)	0.5354 (2)	0.69825 (10)	0.0220 (3)
O2	0.91084 (12)	0.7307 (2)	0.52420 (11)	0.0329 (4)
H2	0.8902	0.7733	0.5740	0.049*
O3	0.83989 (11)	0.7679 (2)	0.85129 (11)	0.0253 (3)
O4	0.84723 (11)	0.9268 (2)	0.70298 (11)	0.0284 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0219 (9)	0.0190 (10)	0.0191 (9)	−0.0015 (8)	0.0087 (8)	0.0027 (8)
C2	0.0228 (9)	0.0206 (9)	0.0244 (9)	0.0033 (8)	0.0118 (8)	0.0033 (8)
C3	0.0346 (10)	0.0212 (10)	0.0219 (9)	0.0034 (9)	0.0150 (8)	−0.0008 (8)
C4	0.0289 (10)	0.0227 (10)	0.0190 (9)	−0.0006 (9)	0.0062 (8)	−0.0012 (8)
C5	0.0242 (9)	0.0186 (9)	0.0208 (9)	0.0014 (8)	0.0079 (8)	0.0021 (8)
C6	0.0223 (9)	0.0148 (9)	0.0189 (8)	−0.0018 (8)	0.0099 (7)	0.0013 (7)
C7	0.0231 (9)	0.0181 (9)	0.0187 (8)	−0.0006 (8)	0.0091 (7)	−0.0019 (8)
C8	0.0252 (9)	0.0202 (9)	0.0208 (8)	−0.0005 (8)	0.0106 (7)	−0.0037 (8)
C9	0.0284 (10)	0.0274 (10)	0.0180 (8)	0.0034 (9)	0.0097 (8)	0.0014 (8)
C10	0.0320 (10)	0.0228 (10)	0.0269 (10)	−0.0030 (9)	0.0161 (9)	0.0001 (9)
C11	0.0250 (10)	0.0286 (11)	0.0300 (10)	−0.0039 (9)	0.0136 (9)	0.0027 (9)
C12	0.0247 (10)	0.0247 (10)	0.0257 (9)	0.0031 (9)	0.0137 (8)	0.0013 (9)
C13	0.0216 (9)	0.0288 (11)	0.0294 (10)	0.0040 (9)	0.0112 (8)	0.0009 (9)
C14	0.0198 (9)	0.0293 (11)	0.0283 (10)	0.0013 (9)	0.0033 (8)	−0.0019 (9)
C15	0.0314 (11)	0.0185 (10)	0.0270 (10)	−0.0008 (9)	0.0115 (8)	−0.0008 (9)
C16	0.0406 (12)	0.0207 (10)	0.0296 (10)	0.0054 (10)	0.0141 (9)	0.0018 (9)
C17	0.0423 (13)	0.0388 (13)	0.0369 (12)	0.0179 (12)	0.0089 (10)	0.0018 (11)
C18	0.0240 (9)	0.0194 (9)	0.0238 (9)	−0.0001 (8)	0.0091 (8)	−0.0026 (8)
C19	0.0232 (9)	0.0247 (10)	0.0242 (9)	0.0003 (9)	0.0108 (8)	−0.0027 (9)
C20	0.0282 (10)	0.0320 (11)	0.0341 (11)	0.0004 (10)	0.0147 (9)	0.0012 (10)
C21	0.0296 (11)	0.0466 (15)	0.0495 (13)	−0.0026 (11)	0.0218 (10)	0.0056 (12)
C22	0.0227 (10)	0.0537 (16)	0.0424 (12)	0.0035 (11)	0.0156 (10)	0.0030 (12)
C23	0.0265 (10)	0.0385 (12)	0.0273 (10)	0.0039 (10)	0.0112 (8)	−0.0025 (10)
C24	0.0299 (11)	0.0462 (14)	0.0357 (11)	0.0108 (11)	0.0123 (9)	0.0008 (11)
C25	0.0409 (13)	0.0368 (13)	0.0356 (12)	0.0140 (12)	0.0098 (10)	0.0035 (11)
C26	0.0364 (12)	0.0328 (12)	0.0372 (12)	0.0015 (11)	0.0107 (10)	0.0032 (11)
C27	0.0259 (10)	0.0272 (11)	0.0322 (10)	0.0006 (9)	0.0075 (9)	0.0010 (9)
C28	0.0225 (9)	0.0289 (11)	0.0229 (9)	0.0020 (9)	0.0074 (8)	−0.0031 (9)
N1	0.0299 (9)	0.0277 (9)	0.0306 (9)	0.0111 (8)	0.0108 (7)	0.0028 (8)
O1	0.0196 (6)	0.0252 (7)	0.0212 (6)	−0.0011 (6)	0.0074 (5)	−0.0025 (6)
O2	0.0333 (8)	0.0370 (9)	0.0267 (7)	0.0083 (7)	0.0093 (6)	0.0097 (7)
O3	0.0243 (7)	0.0276 (8)	0.0276 (7)	0.0060 (6)	0.0136 (6)	0.0031 (6)
O4	0.0275 (7)	0.0277 (8)	0.0346 (7)	0.0019 (7)	0.0170 (6)	0.0051 (7)

Geometric parameters (Å, º) top

C1—O1	1.372 (2)	C15—C16	1.516 (3)
C1—C2	1.376 (3)	C15—H15A	0.9900
C1—C6	1.381 (2)	C15—H15B	0.9900
C2—C3	1.390 (3)	C16—N1	1.462 (3)
C2—O3	1.406 (2)	C16—H16A	0.9900
C3—C4	1.388 (3)	C16—H16B	0.9900
C3—H3	0.9500	C17—N1	1.455 (3)
C4—C5	1.410 (3)	C17—H17A	0.9800
C4—H4	0.9500	C17—H17B	0.9800
C5—C6	1.378 (3)	C17—H17C	0.9800
C5—C14	1.509 (3)	C18—O4	1.208 (2)
C6—C7	1.502 (2)	C18—O3	1.367 (2)
C7—C15	1.536 (3)	C18—C19	1.491 (3)
C7—C12	1.540 (3)	C19—C20	1.377 (3)
C7—C8	1.546 (3)	C19—C28	1.433 (3)
C8—O1	1.480 (2)	C20—C21	1.411 (3)
C8—C9	1.545 (3)	C20—H20	0.9500
C8—H8	1.0000	C21—C22	1.355 (4)
C9—O2	1.426 (2)	C21—H21	0.9500
C9—C10	1.501 (3)	C22—C23	1.418 (3)
C9—H9	1.0000	C22—H22	0.9500
C10—C11	1.324 (3)	C23—C24	1.411 (4)
C10—H10	0.9500	C23—C28	1.432 (3)
C11—C12	1.504 (3)	C24—C25	1.362 (4)
C11—H11	0.9500	C24—H24	0.9500
C12—C13	1.537 (3)	C25—C26	1.420 (3)
C12—H12	1.0000	C25—H25	0.9500
C13—N1	1.474 (3)	C26—C27	1.360 (3)
C13—C14	1.562 (3)	C26—H26	0.9500
C13—H13	1.0000	C27—C28	1.416 (3)
C14—H14A	0.9900	C27—H27	0.9500
C14—H14B	0.9900	O2—H2	0.8400

O1—C1—C2	127.39 (16)	H14A—C14—H14B	107.6
O1—C1—C6	112.44 (15)	C16—C15—C7	112.01 (17)
C2—C1—C6	120.07 (16)	C16—C15—H15A	109.2
C1—C2—C3	118.37 (17)	C7—C15—H15A	109.2
C1—C2—O3	122.05 (16)	C16—C15—H15B	109.2
C3—C2—O3	119.51 (16)	C7—C15—H15B	109.2
C4—C3—C2	121.14 (17)	H15A—C15—H15B	107.9
C4—C3—H3	119.4	N1—C16—C15	110.68 (16)
C2—C3—H3	119.4	N1—C16—H16A	109.5
C3—C4—C5	120.65 (17)	C15—C16—H16A	109.5
C3—C4—H4	119.7	N1—C16—H16B	109.5
C5—C4—H4	119.7	C15—C16—H16B	109.5
C6—C5—C4	116.33 (17)	H16A—C16—H16B	108.1
C6—C5—C14	118.11 (17)	N1—C17—H17A	109.5
C4—C5—C14	125.14 (17)	N1—C17—H17B	109.5
C5—C6—C1	123.13 (17)	H17A—C17—H17B	109.5
C5—C6—C7	126.97 (17)	N1—C17—H17C	109.5
C1—C6—C7	109.39 (15)	H17A—C17—H17C	109.5
C6—C7—C15	112.05 (15)	H17B—C17—H17C	109.5
C6—C7—C12	106.01 (15)	O4—C18—O3	123.25 (16)
C15—C7—C12	109.64 (16)	O4—C18—C19	126.59 (17)
C6—C7—C8	100.37 (15)	O3—C18—C19	110.15 (15)
C15—C7—C8	111.98 (16)	C20—C19—C28	120.98 (18)
C12—C7—C8	116.34 (15)	C20—C19—C18	117.65 (19)
O1—C8—C9	108.95 (16)	C28—C19—C18	121.31 (17)
O1—C8—C7	105.49 (13)	C19—C20—C21	120.5 (2)
C9—C8—C7	113.94 (15)	C19—C20—H20	119.8
O1—C8—H8	109.4	C21—C20—H20	119.8
C9—C8—H8	109.4	C22—C21—C20	120.1 (2)
C7—C8—H8	109.4	C22—C21—H21	119.9
O2—C9—C10	113.09 (17)	C20—C21—H21	119.9
O2—C9—C8	111.10 (15)	C21—C22—C23	121.5 (2)
C10—C9—C8	113.60 (15)	C21—C22—H22	119.2
O2—C9—H9	106.1	C23—C22—H22	119.2
C10—C9—H9	106.1	C24—C23—C22	121.50 (19)
C8—C9—H9	106.1	C24—C23—C28	119.1 (2)
C11—C10—C9	121.94 (19)	C22—C23—C28	119.4 (2)
C11—C10—H10	119.0	C25—C24—C23	121.5 (2)
C9—C10—H10	119.0	C25—C24—H24	119.2
C10—C11—C12	120.73 (19)	C23—C24—H24	119.2
C10—C11—H11	119.6	C24—C25—C26	119.3 (2)
C12—C11—H11	119.6	C24—C25—H25	120.3
C11—C12—C13	114.39 (18)	C26—C25—H25	120.3
C11—C12—C7	108.97 (17)	C27—C26—C25	120.9 (2)
C13—C12—C7	106.59 (15)	C27—C26—H26	119.6
C11—C12—H12	108.9	C25—C26—H26	119.6
C13—C12—H12	108.9	C26—C27—C28	121.17 (19)
C7—C12—H12	108.9	C26—C27—H27	119.4
N1—C13—C12	107.15 (17)	C28—C27—H27	119.4
N1—C13—C14	115.47 (18)	C27—C28—C23	118.00 (19)
C12—C13—C14	112.80 (16)	C27—C28—C19	124.48 (17)
N1—C13—H13	107.0	C23—C28—C19	117.51 (18)
C12—C13—H13	107.0	C17—N1—C16	112.07 (18)
C14—C13—H13	107.0	C17—N1—C13	113.29 (19)
C5—C14—C13	114.61 (16)	C16—N1—C13	112.27 (16)
C5—C14—H14A	108.6	C1—O1—C8	106.24 (13)
C13—C14—H14A	108.6	C9—O2—H2	109.5
C5—C14—H14B	108.6	C18—O3—C2	117.36 (14)
C13—C14—H14B	108.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4	0.84	2.23	3.067 (2)	171
C3—H3···Cg1ⁱ	0.95	2.70	3.577 (2)	154
C16—H16b···Cg1ⁱⁱ	0.99	3.14	4.004 (2)	146
C14—H14a···Cg2ⁱⁱⁱ	0.99	3.24	4.068 (2)	143
C25—H25···Cg3^iv	0.95	2.84	3.643 (3)	143

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

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