5α-Acetamido-6β-hydr­oxy-17-oxoandrostan-3β-yl acetate

Pinto, R.M.A.; Ramos Silva, M.; Matos Beja, A.; Salvador, J.A.R.; Paixão, J.A.

doi:10.1107/S1600536807029893

5α-Acetamido-6β-hydroxy-17-oxoandrostan-3β-yl acetate

R. M. A. Pinto, M. Ramos Silva, A. Matos Beja, J. A. R. Salvador and J. A. Paixão

Using a method developed by our group, we prepared, by a one-step reaction, the title N-acetylated hydroxyaminoandrostane, C₂₃H₃₅NO₅, from the corresponding 5β,6β-epoxy steroid. The stereoselective nucleophilic attack of acetonitrile to the α-face of the steroid nucleus at position 5 is unequivocally demonstrated by X-ray crystallographic analysis. Intermolecular O—H

O hydrogen bonds are present in the crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029893/bt2399sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029893/bt2399Isup2.hkl Contains datablock I

CCDC reference: 655042

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Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.034
wR factor = 0.098
Data-to-parameter ratio = 8.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C3A
PLAT420_ALERT_2_C D-H Without Acceptor       N5     -   H5     ...          ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          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           25.47
           From the CIF: _reflns_number_total               2192
           Count of symmetry unique reflns         2190
           Completeness (_total/calc)            100.09%
           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
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C6     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C9     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C10    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C13    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C14    = .          S
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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

  11 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
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Using a method developed by our group (Pinto et al., 2006) we prepared, by a one-step reaction, the N-acetylated-hydroxy-amino-androstane (I) from the corresponding 5β,6β-epoxysteroid. The steroselective nucleophilic attack of acetonitrile to the α-face of steroid nucleus at C5 is unequivocally demonstrated by X-ray crystallography.

The conformations of the six-membered rings are close to a chair form, as shown by the Cremer & Pople (1975) puckring parameters [ring A: Q= 0.586 (3) Å, θ = 7.9 (3)° and φ = 260 (2)°; ring B: Q= 0.562 (3) Å, θ = 2.7 (3)° and φ = 238 (6)°; ring C: Q= 0.580 (3) Å, θ = 5.4 (3)° and φ = 269 (3)°]. The D-ring has a C14 envelope conformation with puckering parameters q₂ = 0.580 (3)Å and φ₂ = 209.2 (4)°. All rings of the molecule are fused trans. The acetoxy group at C3 is equatorial to the A ring, and both substituents at the B ring are axial.

The molecules are hydrogen-bonded in infinite chains running parallel to the b axis through the hydroxyl group at C6, acting as donor towards the carbonyl O atom of the D ring.

The anistropic displacement tensor of the O3B atom is strongly anisotropic, suggesting a strong amplitude of vibration of this atom perpendicular to the mean plane of the acetoxy group.

Related literature top

For vicinal amino alcohols see Bergmeier (2000). For androstanes with 2-amino-3-ol functionality see Tuba et al. (2002) and Gyermek (2005). For compounds inhibiting the proliferation of leukemia cells see He & Jiang (1999) and He & Na (2001), and for the preparation of vic-hydroxyacylamino steroids see Vincze et al. (1996). For related literature, see: Cremer & Pople (1975); Pinto et al. (2006); Salvador et al. (1996).

Experimental top

5β,6β-Epoxy-17-oxoandrostan-3β-yl acetate was easily prepared from commercially available dehydroepiandrosterone acetate by epoxidation with KMnO₄/Fe₂(SO₄)₃nH₂O (Salvador et al., 1996).

Synthesis of 5α-acetamido-6β-hydroxy-17-oxoandrostan-3β-yl acetate (I) was efficiently accomplished by nucleophilic ring opening of the 5β,6β-epoxysteroid catalysed by BiBr₃ in acetonitrile (Pinto et al., 2006). The product of this reaction was isolated in 86% yield and identified as the title compound (I) from IR, ¹H and ¹³C NMR spectroscopy data (Pinto et al., 2006). Recrystallization from ethyl acetate at room temperature gave colorless single crystals suitable for X-ray analysis.

Structure description top

The molecules are hydrogen-bonded in infinite chains running parallel to the b axis through the hydroxyl group at C6, acting as donor towards the carbonyl O atom of the D ring.

The anistropic displacement tensor of the O3B atom is strongly anisotropic, suggesting a strong amplitude of vibration of this atom perpendicular to the mean plane of the acetoxy group.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: PLATON (Spek, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. ORTEPII (Johnson, 1976) plot of the title compound. Displacement ellipsoids are drawn at the 50% level.

5α-Acetamido-6β-hydroxy-17-oxoandrostan-3β-yl acetate top

Crystal data top

C₂₃H₃₅NO₅	F(000) = 440
M_r = 405.52	D_x = 1.216 Mg m⁻³
Monoclinic, P2₁	Melting point: 507 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 8.660 (3) Å	Cell parameters from 25 reflections
b = 9.423 (3) Å	θ = 7.9–13.3°
c = 13.973 (2) Å	µ = 0.09 mm⁻¹
β = 104.00 (2)°	T = 293 K
V = 1106.4 (5) Å³	Prism, colourless
Z = 2	0.42 × 0.20 × 0.17 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.024
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 2.4°
Graphite monochromator	h = −10→10
profile data from ω–2θ scans	k = 0→11
3483 measured reflections	l = 0→16
2192 independent reflections	3 standard reflections every 300 min
1883 reflections with I > 2σ(I)	intensity decay: 9.2%

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0652P)² + 0.0914P] where P = (F_o² + 2F_c²)/3
2192 reflections	(Δ/σ)_max < 0.001
267 parameters	Δρ_max = 0.18 e Å⁻³
1 restraint	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₃H₃₅NO₅	V = 1106.4 (5) Å³
M_r = 405.52	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.660 (3) Å	µ = 0.09 mm⁻¹
b = 9.423 (3) Å	T = 293 K
c = 13.973 (2) Å	0.42 × 0.20 × 0.17 mm
β = 104.00 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.024
3483 measured reflections	3 standard reflections every 300 min
2192 independent reflections	intensity decay: 9.2%
1883 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.034	1 restraint
wR(F²) = 0.098	H-atom parameters constrained
S = 1.03	Δρ_max = 0.18 e Å⁻³
2192 reflections	Δρ_min = −0.18 e Å⁻³
267 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
C1	−0.1925 (3)	0.6556 (3)	0.19050 (17)	0.0422 (5)
H1A	−0.2369	0.7358	0.2182	0.051*
H1B	−0.1785	0.6837	0.1263	0.051*
C2	−0.3100 (3)	0.5315 (3)	0.17750 (19)	0.0496 (6)
H2A	−0.3373	0.5133	0.2397	0.059*
H2B	−0.4068	0.5575	0.1295	0.059*
C3	−0.2429 (3)	0.3969 (3)	0.14364 (18)	0.0461 (6)
H3	−0.2379	0.4068	0.0746	0.055*
C4	−0.0795 (3)	0.3591 (3)	0.20714 (17)	0.0413 (5)
H4A	−0.0382	0.2771	0.1795	0.050*
H4B	−0.0880	0.3350	0.2732	0.050*
C5	0.0352 (3)	0.4848 (2)	0.21202 (16)	0.0369 (5)
C6	0.2071 (3)	0.4441 (2)	0.26681 (16)	0.0391 (5)
H6	0.2446	0.3703	0.2284	0.047*
C7	0.3188 (3)	0.5697 (3)	0.27595 (17)	0.0407 (5)
H7A	0.3306	0.5950	0.2108	0.049*
H7B	0.4227	0.5420	0.3153	0.049*
C8	0.2619 (3)	0.7002 (3)	0.32298 (17)	0.0364 (5)
H8	0.2591	0.6765	0.3908	0.044*
C9	0.0917 (3)	0.7437 (2)	0.26546 (16)	0.0342 (5)
H9	0.0982	0.7647	0.1978	0.041*
C10	−0.0284 (2)	0.6185 (3)	0.25829 (16)	0.0367 (5)
C11	0.0374 (3)	0.8822 (3)	0.30685 (18)	0.0412 (5)
H11A	−0.0640	0.9111	0.2648	0.049*
H11B	0.0210	0.8634	0.3719	0.049*
C12	0.1558 (3)	1.0047 (3)	0.31421 (18)	0.0442 (5)
H12A	0.1626	1.0332	0.2486	0.053*
H12B	0.1195	1.0856	0.3457	0.053*
C13	0.3196 (3)	0.9583 (3)	0.37413 (16)	0.0394 (5)
C14	0.3717 (2)	0.8260 (3)	0.32554 (16)	0.0373 (5)
H14	0.3651	0.8515	0.2567	0.045*
C15	0.5498 (3)	0.8126 (3)	0.37556 (19)	0.0470 (6)
H15A	0.5661	0.7693	0.4402	0.056*
H15B	0.6050	0.7572	0.3356	0.056*
C16	0.6055 (3)	0.9679 (3)	0.3833 (2)	0.0540 (7)
H16A	0.6812	0.9847	0.4458	0.065*
H16B	0.6558	0.9910	0.3303	0.065*
C17	0.4570 (3)	1.0565 (3)	0.37548 (16)	0.0442 (6)
C19	−0.0502 (3)	0.5862 (3)	0.36241 (17)	0.0450 (6)
H19A	−0.1069	0.6628	0.3838	0.068*
H19B	0.0522	0.5759	0.4074	0.068*
H19C	−0.1096	0.4999	0.3609	0.068*
C18	0.3203 (3)	0.9363 (3)	0.48361 (17)	0.0516 (6)
H18A	0.4266	0.9161	0.5206	0.077*
H18B	0.2518	0.8583	0.4895	0.077*
H18C	0.2827	1.0209	0.5089	0.077*
O17	0.4532 (2)	1.1856 (2)	0.37299 (15)	0.0592 (5)
O6	0.2078 (2)	0.3868 (2)	0.36148 (12)	0.0502 (4)
H6A	0.2764	0.3251	0.3757	0.075*
N5	0.0466 (2)	0.5232 (2)	0.11079 (12)	0.0375 (4)
H5	0.0289	0.6107	0.0943	0.045*
C5A	0.0811 (3)	0.4375 (3)	0.04173 (17)	0.0418 (5)
C5B	0.1138 (4)	0.5119 (3)	−0.04541 (19)	0.0613 (8)
H5B1	0.1887	0.4577	−0.0710	0.092*
H5B2	0.1574	0.6041	−0.0259	0.092*
H5B3	0.0166	0.5219	−0.0954	0.092*
O5	0.0876 (3)	0.3078 (2)	0.04790 (15)	0.0663 (6)
O3A	−0.3466 (2)	0.2780 (2)	0.15344 (13)	0.0534 (5)
O3B	−0.4874 (4)	0.3024 (3)	−0.0007 (2)	0.1098 (11)
C3A	−0.4650 (3)	0.2446 (3)	0.0767 (2)	0.0562 (7)
C3B	−0.5640 (3)	0.1271 (4)	0.1004 (2)	0.0636 (7)
H3B1	−0.6710	0.1366	0.0612	0.095*
H3B2	−0.5641	0.1311	0.1690	0.095*
H3B3	−0.5209	0.0379	0.0863	0.095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0371 (11)	0.0423 (14)	0.0472 (12)	0.0075 (10)	0.0101 (9)	0.0009 (11)
C2	0.0364 (11)	0.0528 (16)	0.0584 (14)	0.0017 (12)	0.0093 (10)	0.0014 (13)
C3	0.0449 (13)	0.0456 (14)	0.0477 (13)	−0.0075 (11)	0.0111 (10)	0.0015 (11)
C4	0.0470 (12)	0.0346 (12)	0.0430 (12)	0.0013 (10)	0.0124 (10)	0.0009 (10)
C5	0.0404 (11)	0.0334 (12)	0.0369 (11)	0.0031 (9)	0.0094 (9)	0.0004 (9)
C6	0.0436 (12)	0.0317 (12)	0.0418 (12)	0.0110 (10)	0.0098 (9)	−0.0015 (10)
C7	0.0345 (10)	0.0403 (13)	0.0456 (12)	0.0092 (10)	0.0067 (9)	−0.0027 (10)
C8	0.0361 (11)	0.0353 (12)	0.0372 (11)	0.0084 (10)	0.0077 (9)	−0.0003 (9)
C9	0.0357 (10)	0.0325 (11)	0.0347 (10)	0.0062 (9)	0.0088 (8)	−0.0009 (9)
C10	0.0357 (10)	0.0355 (11)	0.0391 (11)	0.0055 (10)	0.0095 (8)	−0.0004 (9)
C11	0.0360 (11)	0.0379 (12)	0.0485 (12)	0.0101 (10)	0.0078 (9)	−0.0065 (11)
C12	0.0418 (12)	0.0369 (13)	0.0507 (13)	0.0089 (10)	0.0053 (10)	−0.0062 (11)
C13	0.0407 (12)	0.0363 (12)	0.0380 (11)	0.0094 (10)	0.0035 (9)	−0.0046 (10)
C14	0.0381 (11)	0.0382 (12)	0.0343 (11)	0.0046 (10)	0.0062 (9)	−0.0034 (10)
C15	0.0370 (11)	0.0471 (14)	0.0542 (14)	0.0098 (11)	0.0056 (10)	−0.0055 (12)
C16	0.0397 (12)	0.0499 (15)	0.0676 (16)	0.0000 (12)	0.0036 (11)	−0.0063 (13)
C17	0.0467 (13)	0.0432 (14)	0.0382 (11)	0.0015 (11)	0.0015 (10)	−0.0061 (10)
C19	0.0480 (12)	0.0454 (14)	0.0457 (12)	0.0032 (11)	0.0191 (10)	0.0005 (11)
C18	0.0584 (14)	0.0527 (15)	0.0427 (13)	0.0046 (13)	0.0104 (10)	−0.0105 (12)
O17	0.0611 (11)	0.0375 (10)	0.0738 (12)	0.0001 (9)	0.0063 (9)	−0.0050 (9)
O6	0.0572 (10)	0.0440 (10)	0.0459 (9)	0.0116 (8)	0.0057 (7)	0.0097 (8)
N5	0.0450 (10)	0.0308 (10)	0.0371 (9)	0.0045 (8)	0.0109 (7)	0.0009 (8)
C5A	0.0461 (13)	0.0361 (14)	0.0447 (12)	0.0014 (10)	0.0134 (10)	−0.0055 (10)
C5B	0.093 (2)	0.0482 (16)	0.0485 (14)	0.0068 (15)	0.0286 (14)	−0.0020 (13)
O5	0.1023 (15)	0.0348 (11)	0.0745 (13)	0.0041 (10)	0.0460 (11)	−0.0049 (9)
O3A	0.0525 (9)	0.0529 (11)	0.0524 (10)	−0.0122 (9)	0.0081 (8)	0.0028 (9)
O3B	0.1223 (18)	0.111 (2)	0.0716 (13)	−0.0607 (19)	−0.0249 (13)	0.0291 (16)
C3A	0.0540 (14)	0.0500 (16)	0.0595 (16)	−0.0062 (13)	0.0038 (12)	0.0006 (14)
C3B	0.0577 (15)	0.0591 (18)	0.0717 (18)	−0.0146 (15)	0.0112 (13)	−0.0009 (15)

Geometric parameters (Å, º) top

C1—C2	1.532 (4)	C12—H12B	0.9700
C1—C10	1.545 (3)	C13—C17	1.504 (4)
C1—H1A	0.9700	C13—C14	1.538 (3)
C1—H1B	0.9700	C13—C18	1.542 (3)
C2—C3	1.517 (4)	C14—C15	1.537 (3)
C2—H2A	0.9700	C14—H14	0.9800
C2—H2B	0.9700	C15—C16	1.536 (4)
C3—O3A	1.463 (3)	C15—H15A	0.9700
C3—C4	1.520 (3)	C15—H15B	0.9700
C3—H3	0.9800	C16—C17	1.515 (4)
C4—C5	1.537 (3)	C16—H16A	0.9700
C4—H4A	0.9700	C16—H16B	0.9700
C4—H4B	0.9700	C17—O17	1.217 (3)
C5—N5	1.486 (3)	C19—H19A	0.9600
C5—C6	1.548 (3)	C19—H19B	0.9600
C5—C10	1.575 (3)	C19—H19C	0.9600
C6—O6	1.427 (3)	C18—H18A	0.9600
C6—C7	1.515 (3)	C18—H18B	0.9600
C6—H6	0.9800	C18—H18C	0.9600
C7—C8	1.531 (3)	O6—H6A	0.8200
C7—H7A	0.9700	N5—C5A	1.346 (3)
C7—H7B	0.9700	N5—H5	0.8600
C8—C14	1.515 (3)	C5A—O5	1.226 (3)
C8—C9	1.554 (3)	C5A—C5B	1.490 (4)
C8—H8	0.9800	C5B—H5B1	0.9600
C9—C11	1.546 (3)	C5B—H5B2	0.9600
C9—C10	1.560 (3)	C5B—H5B3	0.9600
C9—H9	0.9800	O3A—C3A	1.330 (3)
C10—C19	1.542 (3)	O3B—C3A	1.184 (4)
C11—C12	1.531 (3)	C3A—C3B	1.486 (4)
C11—H11A	0.9700	C3B—H3B1	0.9600
C11—H11B	0.9700	C3B—H3B2	0.9600
C12—C13	1.526 (3)	C3B—H3B3	0.9600
C12—H12A	0.9700

C2—C1—C10	112.70 (19)	C13—C12—H12A	109.7
C2—C1—H1A	109.1	C11—C12—H12A	109.7
C10—C1—H1A	109.1	C13—C12—H12B	109.7
C2—C1—H1B	109.1	C11—C12—H12B	109.7
C10—C1—H1B	109.1	H12A—C12—H12B	108.2
H1A—C1—H1B	107.8	C17—C13—C12	117.2 (2)
C3—C2—C1	112.46 (18)	C17—C13—C14	100.86 (18)
C3—C2—H2A	109.1	C12—C13—C14	108.86 (18)
C1—C2—H2A	109.1	C17—C13—C18	104.90 (19)
C3—C2—H2B	109.1	C12—C13—C18	111.24 (19)
C1—C2—H2B	109.1	C14—C13—C18	113.5 (2)
H2A—C2—H2B	107.8	C8—C14—C15	120.1 (2)
O3A—C3—C2	108.76 (18)	C8—C14—C13	113.26 (17)
O3A—C3—C4	105.8 (2)	C15—C14—C13	103.60 (18)
C2—C3—C4	112.7 (2)	C8—C14—H14	106.3
O3A—C3—H3	109.8	C15—C14—H14	106.3
C2—C3—H3	109.8	C13—C14—H14	106.3
C4—C3—H3	109.8	C16—C15—C14	102.54 (19)
C3—C4—C5	110.2 (2)	C16—C15—H15A	111.3
C3—C4—H4A	109.6	C14—C15—H15A	111.3
C5—C4—H4A	109.6	C16—C15—H15B	111.3
C3—C4—H4B	109.6	C14—C15—H15B	111.3
C5—C4—H4B	109.6	H15A—C15—H15B	109.2
H4A—C4—H4B	108.1	C17—C16—C15	105.8 (2)
N5—C5—C4	109.63 (18)	C17—C16—H16A	110.6
N5—C5—C6	104.71 (17)	C15—C16—H16A	110.6
C4—C5—C6	111.37 (18)	C17—C16—H16B	110.6
N5—C5—C10	107.85 (17)	C15—C16—H16B	110.6
C4—C5—C10	110.37 (17)	H16A—C16—H16B	108.7
C6—C5—C10	112.67 (17)	O17—C17—C13	126.8 (2)
O6—C6—C7	110.97 (18)	O17—C17—C16	124.7 (3)
O6—C6—C5	109.90 (17)	C13—C17—C16	108.5 (2)
C7—C6—C5	111.45 (18)	C10—C19—H19A	109.5
O6—C6—H6	108.1	C10—C19—H19B	109.5
C7—C6—H6	108.1	H19A—C19—H19B	109.5
C5—C6—H6	108.1	C10—C19—H19C	109.5
C6—C7—C8	113.49 (17)	H19A—C19—H19C	109.5
C6—C7—H7A	108.9	H19B—C19—H19C	109.5
C8—C7—H7A	108.9	C13—C18—H18A	109.5
C6—C7—H7B	108.9	C13—C18—H18B	109.5
C8—C7—H7B	108.9	H18A—C18—H18B	109.5
H7A—C7—H7B	107.7	C13—C18—H18C	109.5
C14—C8—C7	111.91 (16)	H18A—C18—H18C	109.5
C14—C8—C9	108.50 (18)	H18B—C18—H18C	109.5
C7—C8—C9	110.71 (18)	C6—O6—H6A	109.5
C14—C8—H8	108.5	C5A—N5—C5	127.9 (2)
C7—C8—H8	108.5	C5A—N5—H5	116.1
C9—C8—H8	108.5	C5—N5—H5	116.1
C11—C9—C8	111.45 (17)	O5—C5A—N5	124.2 (2)
C11—C9—C10	113.83 (17)	O5—C5A—C5B	120.8 (2)
C8—C9—C10	111.59 (17)	N5—C5A—C5B	115.0 (2)
C11—C9—H9	106.5	C5A—C5B—H5B1	109.5
C8—C9—H9	106.5	C5A—C5B—H5B2	109.5
C10—C9—H9	106.5	H5B1—C5B—H5B2	109.5
C19—C10—C1	108.57 (18)	C5A—C5B—H5B3	109.5
C19—C10—C9	108.71 (18)	H5B1—C5B—H5B3	109.5
C1—C10—C9	111.61 (18)	H5B2—C5B—H5B3	109.5
C19—C10—C5	111.37 (19)	C3A—O3A—C3	118.5 (2)
C1—C10—C5	106.89 (17)	O3B—C3A—O3A	123.5 (3)
C9—C10—C5	109.71 (16)	O3B—C3A—C3B	124.8 (3)
C12—C11—C9	113.71 (17)	O3A—C3A—C3B	111.7 (2)
C12—C11—H11A	108.8	C3A—C3B—H3B1	109.5
C9—C11—H11A	108.8	C3A—C3B—H3B2	109.5
C12—C11—H11B	108.8	H3B1—C3B—H3B2	109.5
C9—C11—H11B	108.8	C3A—C3B—H3B3	109.5
H11A—C11—H11B	107.7	H3B1—C3B—H3B3	109.5
C13—C12—C11	109.83 (19)	H3B2—C3B—H3B3	109.5

C10—C1—C2—C3	−53.3 (3)	C4—C5—C10—C9	178.40 (16)
C1—C2—C3—O3A	168.00 (18)	C6—C5—C10—C9	53.2 (2)
C1—C2—C3—C4	51.0 (3)	C8—C9—C11—C12	52.5 (3)
O3A—C3—C4—C5	−173.44 (17)	C10—C9—C11—C12	179.75 (18)
C2—C3—C4—C5	−54.7 (3)	C9—C11—C12—C13	−54.5 (3)
C3—C4—C5—N5	−58.5 (2)	C11—C12—C13—C17	170.42 (19)
C3—C4—C5—C6	−173.89 (19)	C11—C12—C13—C14	56.8 (2)
C3—C4—C5—C10	60.2 (2)	C11—C12—C13—C18	−68.9 (3)
N5—C5—C6—O6	−172.27 (18)	C7—C8—C14—C15	−55.9 (3)
C4—C5—C6—O6	−53.9 (2)	C9—C8—C14—C15	−178.35 (19)
C10—C5—C6—O6	70.8 (2)	C7—C8—C14—C13	−178.94 (17)
N5—C5—C6—C7	64.3 (2)	C9—C8—C14—C13	58.6 (2)
C4—C5—C6—C7	−177.31 (18)	C17—C13—C14—C8	174.28 (17)
C10—C5—C6—C7	−52.7 (2)	C12—C13—C14—C8	−61.8 (2)
O6—C6—C7—C8	−69.0 (2)	C18—C13—C14—C8	62.7 (3)
C5—C6—C7—C8	53.8 (3)	C17—C13—C14—C15	42.5 (2)
C6—C7—C8—C14	−176.75 (17)	C12—C13—C14—C15	166.5 (2)
C6—C7—C8—C9	−55.6 (3)	C18—C13—C14—C15	−69.1 (2)
C14—C8—C9—C11	−52.3 (2)	C8—C14—C15—C16	−167.0 (2)
C7—C8—C9—C11	−175.51 (18)	C13—C14—C15—C16	−39.4 (2)
C14—C8—C9—C10	179.18 (17)	C14—C15—C16—C17	20.7 (3)
C7—C8—C9—C10	56.0 (2)	C12—C13—C17—O17	33.8 (4)
C2—C1—C10—C19	−63.4 (3)	C14—C13—C17—O17	151.8 (3)
C2—C1—C10—C9	176.77 (18)	C18—C13—C17—O17	−90.1 (3)
C2—C1—C10—C5	56.8 (2)	C12—C13—C17—C16	−147.7 (2)
C11—C9—C10—C19	−60.0 (2)	C14—C13—C17—C16	−29.7 (2)
C8—C9—C10—C19	67.3 (2)	C18—C13—C17—C16	88.4 (2)
C11—C9—C10—C1	59.8 (2)	C15—C16—C17—O17	−175.6 (3)
C8—C9—C10—C1	−173.03 (17)	C15—C16—C17—C13	5.8 (3)
C11—C9—C10—C5	178.04 (16)	C4—C5—N5—C5A	−53.0 (3)
C8—C9—C10—C5	−54.8 (2)	C6—C5—N5—C5A	66.5 (3)
N5—C5—C10—C19	177.75 (18)	C10—C5—N5—C5A	−173.3 (2)
C4—C5—C10—C19	58.0 (2)	C5—N5—C5A—O5	10.5 (4)
C6—C5—C10—C19	−67.2 (2)	C5—N5—C5A—C5B	−168.9 (2)
N5—C5—C10—C1	59.3 (2)	C2—C3—O3A—C3A	91.2 (3)
C4—C5—C10—C1	−60.4 (2)	C4—C3—O3A—C3A	−147.5 (2)
C6—C5—C10—C1	174.38 (18)	C3—O3A—C3A—O3B	3.2 (5)
N5—C5—C10—C9	−61.9 (2)	C3—O3A—C3A—C3B	−176.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O17ⁱ	0.82	2.03	2.823 (3)	164

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₂₃H₃₅NO₅
M_r	405.52
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	8.660 (3), 9.423 (3), 13.973 (2)
β (°)	104.00 (2)
V (Å³)	1106.4 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.42 × 0.20 × 0.17

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3483, 2192, 1883
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.098, 1.03
No. of reflections	2192
No. of parameters	267
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.18

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CAD-4 Software, PLATON (Spek, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.