O-Benzoyl­naltrexone

Yang, R.; Wang, G.-H.; Liu, X.-L.; Wang, D.; Li, X.

doi:10.1107/S1600536813016036

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page o1107

https://doi.org/10.1107/S1600536813016036

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O-Benzoylnaltrexone

Rui Yang,^a Guo-Hai Wang,^a Xia-Li Liu,^a Dong Wang ^a and Xiang Li ^b ^*

^aDepartment of Pharmacology, Technical Center, Jiangsu Nhwa Pharma Corporation, Zhongshan Road No. 289, Xuzhou 221009, People's Republic of China, and ^bKey Laboratory of Coal Processing and Efficient Utilization, (Ministry of Education), China University of Mining & Technology, Xuzhou 221116, Jiangsu, People's Republic of China
^*Correspondence e-mail: lix911@126.com

(Received 17 April 2013; accepted 9 June 2013; online 15 June 2013)

In the title compound, C₂₇H₂₇NO₅ (systematic name: 17-cyclopropylmethyl-14-hydroxy-6-oxo-4,5-epoxymorphinan-6-yl benzoate), which is the benzoate ester of the opioid receptor antagonist naltrexone, the dihedral angle between the two phenyl rings is 77.1 (1)°. In the crystal, a weak aromatic C—H⋯O_carboxyl hydrogen bond involving the benzoate groups of adjacent molecules gives rise to a chain extending along the a-axis direction. The known absolute configuration for the molecule was inferred from a previous naltrexone structure.

Related literature

For chemical properties of naltrexone, see: Fernando et al. (2008 ); Beznischenko et al. (2007 ). For related structures, see: Ledain et al. (1992 ); Li et al. (2012 ).

Experimental

Crystal data

C₂₇H₂₇NO₅
M_r = 445.50
Monoclinic, P 2₁
a = 7.8890 (16) Å
b = 8.6620 (17) Å
c = 16.629 (3) Å
β = 102.24 (3)°
V = 1110.5 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (CAD-4 EXPRESS; Enraf–Nonius, 1994 ) T_min = 0.973, T_max = 0.991
4421 measured reflections
4083 independent reflections
2611 reflections with I > 2σ(I)
R_int = 0.030
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.180
S = 1.00
4083 reflections
301 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ), 1886 Friedel pairs
Flack parameter: 0.04 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C24—H24A⋯O5ⁱ	0.93	2.54	3.453 (7)	168
Symmetry code: (i) x+1, y, z.

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, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ) and ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813016036/zs2258sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813016036/zs2258Isup2.hkl

checkCIF report

Comment top

The title compound C₂₇H₂₇NO₅ is the benzoate ester of the opioid receptor antagonist naltrexone and is important as an intermediate for the preparation N-methylnaltrexone bromide. It is used for the treatment of a number of diseases which are related to abnormal release of endogenous opium (Beznischenko et al., 2007). The structures of a number of derivatives of naltrexone are known, e.g. naltrexone hydrochloride dihydrate (Ledain et al., 1992) and methylnaltrexone hydrobromide methanol monosolvate (Li et al., 2012). In the title compound, the known absolute configuration for the molecule was inferred from a previous naltrexone structure (Li et al., 2012).

In the crystal, a weak aromatic C—H···O_carboxyl hydrogen bond involving the benzoate moieties of adjacent molecules (Table 1) gives a one-dimensional chain extending along the a axial direction. Present also in the structure is an intramolecular O2—H···N interaction.

Related literature top

For chemical properties of naltrexone, see: Fernando et al. (2008); Beznischenko et al. (2007). For related structures, see: Ledain et al. (1992); Li et al. (2012).

Experimental top

The title compound was prepared from 2.0 g (5.9 mmol) of naltrexone ([5α]-17-(cyclopropylmethyl-4,5-epoxy-3,14-dihydroxymorphinan-6-one)), 0.60 g of triethylamine and 16 ml of dichloromethane which were were successively introduced into a 100 ml reactor equipped with a condenser and a mechanical stirrer. After the solid had dissolved, benzoyl chloride (0.85 g, 6 mmol) was added over a 10 minute period at 20 °C and the reaction medium was refluxed for 2 h. The dichloromethane was removed under vacuum and the solid was recrystallized from ethanol, giving the pure title compound.

Structure description top

For chemical properties of naltrexone, see: Fernando et al. (2008); Beznischenko et al. (2007). For related structures, see: Ledain et al. (1992); Li et al. (2012).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Molecular configuration and atom numbering scheme for the title compound, with displacement parameters drawn at the 40% probability level.

17-Cyclopropylmethyl-14-hydroxy-6-oxo-4,5-epoxymorphinan-6-yl benzoate top

Crystal data top

C₂₇H₂₇NO₅	F(000) = 472
M_r = 445.50	D_x = 1.332 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 7.8890 (16) Å	θ = 9–12°
b = 8.6620 (17) Å	µ = 0.09 mm⁻¹
c = 16.629 (3) Å	T = 293 K
β = 102.24 (3)°	Block, colorless
V = 1110.5 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	2611 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 25.4°, θ_min = 1.3°
ω/2θ scans	h = 0→9
Absorption correction: ψ scan (CAD-4 EXPRESS; Enraf–Nonius, 1994)	k = −10→10
T_min = 0.973, T_max = 0.991	l = −20→19
4421 measured reflections	3 standard reflections every 200 reflections
4083 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.067	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.180	w = 1/[σ²(F_o²) + (0.095P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
4083 reflections	Δρ_max = 0.23 e Å⁻³
301 parameters	Δρ_min = −0.23 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1886 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (2)

Crystal data top

C₂₇H₂₇NO₅	V = 1110.5 (4) Å³
M_r = 445.50	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.8890 (16) Å	µ = 0.09 mm⁻¹
b = 8.6620 (17) Å	T = 293 K
c = 16.629 (3) Å	0.30 × 0.20 × 0.10 mm
β = 102.24 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2611 reflections with I > 2σ(I)
Absorption correction: ψ scan (CAD-4 EXPRESS; Enraf–Nonius, 1994)	R_int = 0.030
T_min = 0.973, T_max = 0.991	3 standard reflections every 200 reflections
4421 measured reflections	intensity decay: 1%
4083 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.180	Δρ_max = 0.23 e Å⁻³
S = 1.00	Δρ_min = −0.23 e Å⁻³
4083 reflections	Absolute structure: Flack (1983), 1886 Friedel pairs
301 parameters	Absolute structure parameter: 0.04 (2)
1 restraint

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
N	0.2654 (5)	0.1880 (4)	0.6679 (2)	0.0435 (9)
O2	0.3797 (4)	0.2516 (4)	0.53015 (19)	0.0510 (9)
H2A	0.284 (7)	0.255 (8)	0.544 (4)	0.076*
O1	0.9546 (5)	0.4322 (5)	0.5720 (2)	0.0767 (12)
O3	0.8160 (4)	0.5154 (3)	0.7024 (2)	0.0534 (9)
O4	1.0794 (4)	0.4753 (4)	0.8555 (2)	0.0543 (9)
O5	0.9070 (5)	0.6447 (5)	0.8988 (3)	0.0809 (13)
C1	0.6515 (6)	0.1322 (5)	0.5711 (3)	0.0460 (12)
H1A	0.6060	0.0460	0.5358	0.055*
H1B	0.7364	0.0922	0.6173	0.055*
C2	0.7392 (7)	0.2459 (6)	0.5232 (3)	0.0565 (13)
H2B	0.8310	0.1930	0.5036	0.068*
H2C	0.6550	0.2812	0.4754	0.068*
C3	0.8144 (7)	0.3834 (6)	0.5732 (3)	0.0531 (13)
C4	0.7009 (6)	0.4580 (6)	0.6267 (3)	0.0513 (12)
H4A	0.6374	0.5451	0.5969	0.062*
C5	0.5727 (6)	0.3498 (5)	0.6553 (3)	0.0432 (11)
C6	0.5069 (5)	0.2075 (5)	0.6020 (3)	0.0376 (10)
C7	0.4182 (6)	0.1033 (5)	0.6559 (3)	0.0419 (11)
H7A	0.3753	0.0126	0.6226	0.050*
C8	0.5416 (6)	0.0425 (5)	0.7345 (3)	0.0444 (11)
H8A	0.4735	0.0151	0.7746	0.053*
H8B	0.5975	−0.0507	0.7208	0.053*
C9	0.6798 (6)	0.1565 (5)	0.7733 (3)	0.0405 (10)
C10	0.6907 (5)	0.2929 (5)	0.7329 (3)	0.0390 (10)
C11	0.8196 (6)	0.3975 (5)	0.7578 (3)	0.0437 (11)
C12	0.9405 (6)	0.3749 (6)	0.8295 (3)	0.0485 (12)
C13	0.9307 (6)	0.2405 (6)	0.8727 (3)	0.0554 (13)
H13A	1.0107	0.2228	0.9215	0.067*
C14	0.8052 (6)	0.1324 (6)	0.8448 (3)	0.0506 (12)
H14A	0.8038	0.0413	0.8743	0.061*
C15	0.4194 (6)	0.4364 (5)	0.6763 (3)	0.0497 (12)
H15A	0.4620	0.5205	0.7137	0.060*
H15B	0.3495	0.4804	0.6265	0.060*
C16	0.3093 (6)	0.3310 (5)	0.7155 (3)	0.0495 (12)
H16A	0.3710	0.3053	0.7707	0.059*
H16B	0.2032	0.3841	0.7197	0.059*
C17	0.1400 (6)	0.0976 (5)	0.7005 (3)	0.0492 (12)
H17A	0.0418	0.1631	0.7035	0.059*
H17B	0.1929	0.0660	0.7561	0.059*
C18	0.0748 (6)	−0.0432 (5)	0.6513 (3)	0.0465 (11)
H18A	0.0414	−0.0291	0.5915	0.056*
C19	−0.0330 (7)	−0.1532 (6)	0.6878 (4)	0.0650 (15)
H19A	−0.0513	−0.1308	0.7425	0.078*
H19B	−0.1307	−0.2015	0.6512	0.078*
C20	0.1424 (7)	−0.1989 (6)	0.6801 (4)	0.0617 (14)
H20A	0.1524	−0.2752	0.6386	0.074*
H20B	0.2318	−0.2044	0.7300	0.074*
C21	1.0464 (7)	0.6142 (6)	0.8869 (3)	0.0485 (12)
C22	1.2002 (6)	0.7137 (6)	0.9061 (3)	0.0442 (11)
C23	1.3556 (6)	0.6722 (6)	0.8883 (3)	0.0517 (12)
H23A	1.3666	0.5779	0.8632	0.062*
C24	1.4963 (7)	0.7707 (7)	0.9079 (3)	0.0631 (15)
H24A	1.6025	0.7417	0.8968	0.076*
C25	1.4796 (8)	0.9124 (8)	0.9439 (4)	0.0750 (17)
H25A	1.5730	0.9803	0.9555	0.090*
C26	1.3254 (8)	0.9509 (8)	0.9622 (4)	0.0793 (18)
H26A	1.3145	1.0444	0.9881	0.095*
C27	1.1857 (7)	0.8539 (6)	0.9430 (3)	0.0604 (14)
H27B	1.0802	0.8829	0.9549	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.043 (2)	0.037 (2)	0.050 (2)	−0.0027 (17)	0.0110 (18)	−0.0051 (18)
O2	0.0522 (19)	0.054 (2)	0.0395 (17)	−0.0002 (18)	−0.0069 (16)	0.0060 (15)
O1	0.066 (2)	0.093 (3)	0.073 (3)	−0.024 (2)	0.020 (2)	0.003 (2)
O3	0.061 (2)	0.0400 (18)	0.0533 (19)	−0.0179 (16)	−0.0021 (16)	0.0009 (16)
O4	0.0430 (19)	0.063 (2)	0.055 (2)	−0.0057 (17)	0.0040 (16)	−0.0182 (17)
O5	0.057 (2)	0.081 (3)	0.111 (3)	−0.012 (2)	0.033 (2)	−0.040 (3)
C1	0.055 (3)	0.044 (3)	0.037 (2)	−0.007 (2)	0.007 (2)	−0.002 (2)
C2	0.066 (3)	0.064 (3)	0.044 (3)	−0.006 (3)	0.020 (2)	0.003 (3)
C3	0.055 (3)	0.058 (3)	0.044 (3)	−0.004 (3)	0.008 (2)	0.021 (2)
C4	0.054 (3)	0.045 (3)	0.049 (3)	−0.012 (2)	−0.002 (2)	0.010 (2)
C5	0.047 (3)	0.033 (2)	0.046 (3)	−0.003 (2)	0.003 (2)	0.003 (2)
C6	0.038 (2)	0.036 (2)	0.037 (2)	0.0006 (19)	0.0028 (19)	0.0057 (19)
C7	0.045 (3)	0.039 (2)	0.041 (2)	0.002 (2)	0.008 (2)	−0.001 (2)
C8	0.050 (3)	0.037 (2)	0.047 (3)	−0.004 (2)	0.011 (2)	0.004 (2)
C9	0.043 (3)	0.043 (3)	0.034 (2)	−0.002 (2)	0.007 (2)	0.002 (2)
C10	0.042 (2)	0.036 (2)	0.038 (2)	−0.002 (2)	0.005 (2)	−0.006 (2)
C11	0.052 (3)	0.038 (3)	0.041 (3)	−0.003 (2)	0.010 (2)	−0.007 (2)
C12	0.037 (3)	0.059 (3)	0.044 (3)	−0.004 (2)	−0.002 (2)	−0.012 (2)
C13	0.052 (3)	0.071 (4)	0.038 (3)	0.002 (3)	−0.001 (2)	0.005 (3)
C14	0.050 (3)	0.057 (3)	0.042 (3)	−0.004 (3)	0.004 (2)	0.012 (2)
C15	0.055 (3)	0.033 (2)	0.057 (3)	−0.003 (2)	0.002 (2)	−0.007 (2)
C16	0.051 (3)	0.042 (3)	0.055 (3)	0.002 (2)	0.009 (2)	−0.011 (2)
C17	0.046 (3)	0.048 (3)	0.057 (3)	−0.001 (2)	0.017 (2)	−0.005 (2)
C18	0.053 (3)	0.041 (3)	0.045 (3)	−0.005 (2)	0.010 (2)	0.002 (2)
C19	0.066 (4)	0.057 (3)	0.074 (4)	−0.011 (3)	0.018 (3)	0.001 (3)
C20	0.077 (4)	0.045 (3)	0.065 (3)	0.001 (3)	0.019 (3)	0.005 (2)
C21	0.044 (3)	0.059 (3)	0.043 (3)	−0.001 (2)	0.011 (2)	−0.008 (2)
C22	0.037 (2)	0.061 (3)	0.034 (2)	−0.005 (2)	0.0051 (19)	−0.001 (2)
C23	0.048 (3)	0.061 (3)	0.043 (3)	0.001 (3)	0.003 (2)	0.003 (2)
C24	0.046 (3)	0.090 (4)	0.054 (3)	−0.001 (3)	0.011 (2)	0.006 (3)
C25	0.068 (4)	0.085 (5)	0.068 (4)	−0.026 (3)	0.006 (3)	−0.003 (3)
C26	0.087 (4)	0.072 (4)	0.079 (4)	−0.023 (4)	0.019 (4)	−0.029 (3)
C27	0.059 (3)	0.059 (3)	0.064 (3)	−0.007 (3)	0.015 (3)	−0.014 (3)

Geometric parameters (Å, º) top

N—C17	1.453 (6)	C11—C12	1.374 (6)
N—C7	1.460 (6)	C12—C13	1.378 (7)
N—C16	1.471 (5)	C13—C14	1.370 (7)
O2—C6	1.440 (5)	C13—H13A	0.9300
O2—H2A	0.84 (5)	C14—H14A	0.9300
O1—C3	1.188 (6)	C15—C16	1.501 (7)
O3—C11	1.372 (5)	C15—H15A	0.9700
O3—C4	1.473 (6)	C15—H15B	0.9700
O4—C21	1.358 (6)	C16—H16A	0.9700
O4—C12	1.394 (5)	C16—H16B	0.9700
O5—C21	1.187 (6)	C17—C18	1.498 (7)
C1—C6	1.496 (6)	C17—H17A	0.9700
C1—C2	1.522 (6)	C17—H17B	0.9700
C1—H1A	0.9700	C18—C19	1.490 (7)
C1—H1B	0.9700	C18—C20	1.491 (7)
C2—C3	1.501 (7)	C18—H18A	0.9800
C2—H2B	0.9700	C19—C20	1.471 (7)
C2—H2C	0.9700	C19—H19A	0.9700
C3—C4	1.534 (7)	C19—H19B	0.9700
C4—C5	1.527 (6)	C20—H20A	0.9700
C4—H4A	0.9800	C20—H20B	0.9700
C5—C10	1.505 (6)	C21—C22	1.467 (6)
C5—C15	1.526 (6)	C22—C23	1.369 (6)
C5—C6	1.542 (6)	C22—C27	1.376 (7)
C6—C7	1.541 (6)	C23—C24	1.383 (7)
C7—C8	1.547 (6)	C23—H23A	0.9300
C7—H7A	0.9800	C24—C25	1.384 (9)
C8—C9	1.510 (6)	C24—H24A	0.9300
C8—H8A	0.9700	C25—C26	1.357 (8)
C8—H8B	0.9700	C25—H25A	0.9300
C9—C10	1.371 (6)	C26—C27	1.369 (8)
C9—C14	1.393 (6)	C26—H26A	0.9300
C10—C11	1.359 (6)	C27—H27B	0.9300

C17—N—C7	115.3 (4)	C14—C13—C12	121.2 (4)
C17—N—C16	110.7 (3)	C14—C13—H13A	119.4
C7—N—C16	112.9 (3)	C12—C13—H13A	119.4
C6—O2—H2A	107 (4)	C13—C14—C9	121.2 (5)
C11—O3—C4	104.1 (3)	C13—C14—H14A	119.4
C21—O4—C12	118.0 (4)	C9—C14—H14A	119.4
C6—C1—C2	111.2 (4)	C16—C15—C5	111.1 (4)
C6—C1—H1A	109.4	C16—C15—H15A	109.4
C2—C1—H1A	109.4	C5—C15—H15A	109.4
C6—C1—H1B	109.4	C16—C15—H15B	109.4
C2—C1—H1B	109.4	C5—C15—H15B	109.4
H1A—C1—H1B	108.0	H15A—C15—H15B	108.0
C3—C2—C1	113.2 (4)	N—C16—C15	111.7 (4)
C3—C2—H2B	108.9	N—C16—H16A	109.3
C1—C2—H2B	108.9	C15—C16—H16A	109.3
C3—C2—H2C	108.9	N—C16—H16B	109.3
C1—C2—H2C	108.9	C15—C16—H16B	109.3
H2B—C2—H2C	107.8	H16A—C16—H16B	107.9
O1—C3—C2	122.3 (5)	N—C17—C18	114.7 (4)
O1—C3—C4	121.3 (5)	N—C17—H17A	108.6
C2—C3—C4	116.4 (4)	C18—C17—H17A	108.6
O3—C4—C5	105.7 (4)	N—C17—H17B	108.6
O3—C4—C3	107.9 (4)	C18—C17—H17B	108.6
C5—C4—C3	115.4 (4)	H17A—C17—H17B	107.6
O3—C4—H4A	109.2	C19—C18—C20	59.1 (3)
C5—C4—H4A	109.2	C19—C18—C17	117.3 (4)
C3—C4—H4A	109.2	C20—C18—C17	120.2 (4)
C10—C5—C15	109.9 (4)	C19—C18—H18A	116.1
C10—C5—C4	97.9 (3)	C20—C18—H18A	116.1
C15—C5—C4	112.2 (4)	C17—C18—H18A	116.1
C10—C5—C6	107.6 (3)	C20—C19—C18	60.5 (3)
C15—C5—C6	109.8 (4)	C20—C19—H19A	117.7
C4—C5—C6	118.5 (4)	C18—C19—H19A	117.7
O2—C6—C1	106.2 (3)	C20—C19—H19B	117.7
O2—C6—C7	108.4 (3)	C18—C19—H19B	117.7
C1—C6—C7	114.7 (3)	H19A—C19—H19B	114.8
O2—C6—C5	110.8 (3)	C19—C20—C18	60.4 (3)
C1—C6—C5	110.9 (4)	C19—C20—H20A	117.7
C7—C6—C5	105.9 (3)	C18—C20—H20A	117.7
N—C7—C6	106.0 (3)	C19—C20—H20B	117.7
N—C7—C8	116.5 (4)	C18—C20—H20B	117.7
C6—C7—C8	114.1 (3)	H20A—C20—H20B	114.9
N—C7—H7A	106.6	O5—C21—O4	121.4 (5)
C6—C7—H7A	106.6	O5—C21—C22	125.8 (5)
C8—C7—H7A	106.6	O4—C21—C22	112.7 (4)
C9—C8—C7	114.0 (4)	C23—C22—C27	119.4 (5)
C9—C8—H8A	108.8	C23—C22—C21	122.4 (5)
C7—C8—H8A	108.8	C27—C22—C21	118.2 (4)
C9—C8—H8B	108.8	C22—C23—C24	119.9 (5)
C7—C8—H8B	108.8	C22—C23—H23A	120.1
H8A—C8—H8B	107.7	C24—C23—H23A	120.1
C10—C9—C14	116.2 (4)	C23—C24—C25	120.2 (5)
C10—C9—C8	118.0 (4)	C23—C24—H24A	119.9
C14—C9—C8	125.8 (4)	C25—C24—H24A	119.9
C11—C10—C9	123.0 (4)	C26—C25—C24	119.1 (6)
C11—C10—C5	109.3 (4)	C26—C25—H25A	120.4
C9—C10—C5	127.6 (4)	C24—C25—H25A	120.4
C10—C11—O3	112.5 (4)	C25—C26—C27	120.8 (6)
C10—C11—C12	120.5 (4)	C25—C26—H26A	119.6
O3—C11—C12	126.9 (4)	C27—C26—H26A	119.6
C11—C12—C13	117.8 (4)	C26—C27—C22	120.4 (5)
C11—C12—O4	122.4 (4)	C26—C27—H27B	119.8
C13—C12—O4	119.5 (4)	C22—C27—H27B	119.8

C6—C1—C2—C3	59.3 (6)	C6—C5—C10—C11	146.1 (4)
C1—C2—C3—O1	135.8 (5)	C15—C5—C10—C9	87.6 (5)
C1—C2—C3—C4	−44.0 (6)	C4—C5—C10—C9	−155.2 (5)
C11—O3—C4—C5	29.6 (5)	C6—C5—C10—C9	−31.9 (6)
C11—O3—C4—C3	−94.4 (4)	C9—C10—C11—O3	172.3 (4)
O1—C3—C4—O3	−34.1 (6)	C5—C10—C11—O3	−5.9 (5)
C2—C3—C4—O3	145.7 (4)	C9—C10—C11—C12	−4.6 (7)
O1—C3—C4—C5	−152.0 (5)	C5—C10—C11—C12	177.3 (4)
C2—C3—C4—C5	27.8 (6)	C4—O3—C11—C10	−15.1 (5)
O3—C4—C5—C10	−31.1 (4)	C4—O3—C11—C12	161.6 (5)
C3—C4—C5—C10	88.0 (4)	C10—C11—C12—C13	2.8 (7)
O3—C4—C5—C15	84.3 (4)	O3—C11—C12—C13	−173.6 (4)
C3—C4—C5—C15	−156.6 (4)	C10—C11—C12—O4	177.0 (4)
O3—C4—C5—C6	−146.1 (4)	O3—C11—C12—O4	0.6 (7)
C3—C4—C5—C6	−27.0 (6)	C21—O4—C12—C11	74.5 (6)
C2—C1—C6—O2	64.0 (5)	C21—O4—C12—C13	−111.5 (5)
C2—C1—C6—C7	−176.4 (4)	C11—C12—C13—C14	0.3 (7)
C2—C1—C6—C5	−56.5 (5)	O4—C12—C13—C14	−174.0 (4)
C10—C5—C6—O2	174.4 (3)	C12—C13—C14—C9	−2.0 (8)
C15—C5—C6—O2	54.8 (5)	C10—C9—C14—C13	0.4 (7)
C4—C5—C6—O2	−75.9 (5)	C8—C9—C14—C13	176.6 (5)
C10—C5—C6—C1	−68.0 (4)	C10—C5—C15—C16	−64.0 (5)
C15—C5—C6—C1	172.4 (4)	C4—C5—C15—C16	−171.9 (4)
C4—C5—C6—C1	41.7 (5)	C6—C5—C15—C16	54.2 (5)
C10—C5—C6—C7	57.1 (4)	C17—N—C16—C15	−172.2 (4)
C15—C5—C6—C7	−62.5 (4)	C7—N—C16—C15	56.8 (5)
C4—C5—C6—C7	166.7 (4)	C5—C15—C16—N	−49.4 (5)
C17—N—C7—C6	166.1 (4)	C7—N—C17—C18	−55.6 (5)
C16—N—C7—C6	−65.2 (4)	C16—N—C17—C18	174.6 (4)
C17—N—C7—C8	−65.8 (5)	N—C17—C18—C19	171.0 (4)
C16—N—C7—C8	62.9 (5)	N—C17—C18—C20	102.6 (5)
O2—C6—C7—N	−52.4 (4)	C17—C18—C19—C20	−110.6 (5)
C1—C6—C7—N	−170.8 (4)	C17—C18—C20—C19	105.6 (5)
C5—C6—C7—N	66.5 (4)	C12—O4—C21—O5	6.6 (7)
O2—C6—C7—C8	178.1 (4)	C12—O4—C21—C22	−175.6 (4)
C1—C6—C7—C8	59.7 (5)	O5—C21—C22—C23	−178.1 (5)
C5—C6—C7—C8	−62.9 (4)	O4—C21—C22—C23	4.3 (6)
N—C7—C8—C9	−88.2 (5)	O5—C21—C22—C27	1.6 (8)
C6—C7—C8—C9	35.8 (5)	O4—C21—C22—C27	−176.1 (4)
C7—C8—C9—C10	−5.0 (6)	C27—C22—C23—C24	0.3 (7)
C7—C8—C9—C14	178.9 (4)	C21—C22—C23—C24	180.0 (4)
C14—C9—C10—C11	2.9 (7)	C22—C23—C24—C25	−1.2 (7)
C8—C9—C10—C11	−173.6 (4)	C23—C24—C25—C26	2.1 (8)
C14—C9—C10—C5	−179.3 (4)	C24—C25—C26—C27	−2.1 (10)
C8—C9—C10—C5	4.2 (7)	C25—C26—C27—C22	1.3 (9)
C15—C5—C10—C11	−94.4 (4)	C23—C22—C27—C26	−0.3 (8)
C4—C5—C10—C11	22.8 (5)	C21—C22—C27—C26	180.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N	0.84 (6)	2.18 (7)	2.691 (5)	120 (5)
C24—H24A···O5ⁱ	0.93	2.54	3.453 (7)	168

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₇H₂₇NO₅
M_r	445.50
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	7.8890 (16), 8.6620 (17), 16.629 (3)
β (°)	102.24 (3)
V (Å³)	1110.5 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (CAD-4 EXPRESS; Enraf–Nonius, 1994)
T_min, T_max	0.973, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	4421, 4083, 2611
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.180, 1.00
No. of reflections	4083
No. of parameters	301
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.23
Absolute structure	Flack (1983), 1886 Friedel pairs
Absolute structure parameter	0.04 (2)

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005) and ORTEPIII (Burnett & Johnson, 1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C24—H24A···O5ⁱ	0.93	2.54	3.453 (7)	168

Symmetry code: (i) x+1, y, z.

References

Beznischenko, A. O., Makhankova, V. G., Kokozay, V. N., Zubatyuk, R. I. & Shishkin, O. V. (2007). Inorg. Chim. Acta, 10, 1325–1329. CAS Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Fernando, S.-D., Fernando, L., Francesc, L., Miguel, J. & Catalina, R.-P. (2008). Cryst. Growth Des. 8, 3219–3232. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Ledain, A. C., Madsen, B. W., Skelton, B. W. & White, A. H. (1992). Aust. J. Chem. 45, 835–840. CSD CrossRef Google Scholar
Li, G., Cai, X., Zheng, Z., Zhou, X. & Li, S. (2012). Acta Cryst. E68, o827. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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