(1S,1′S,2′R,4a'S,9a'S,9b'R)-1′-Acet­yloxy-2,4′-dioxo-2′,4′,4a',7′,8′,9′,9a',9b'-octa­hydro-1′H,2H-spiro­[ace­naphthyl­ene-1,5′-pyrano[4,3-a]pyrrolizin]-2′-ylmethyl acetate

Santhiya, S.; Naga Siva Rao, J.; Raghunathan, R.; Latha, N.; Lakshmi, S.

doi:10.1107/S1600536813026111

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1601

doi:10.1107/S1600536813026111

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(1S,1′S,2′R,4a'S,9a'S,9b'R)-1′-Acetyloxy-2,4′-dioxo-2′,4′,4a',7′,8′,9′,9a',9b'-octahydro-1′H,2H-spiro[acenaphthylene-1,5′-pyrano[4,3-a]pyrrolizin]-2′-ylmethyl acetate

S. Santhiya,^a J. Naga Siva Rao,^b R. Raghunathan,^b N. Latha ^a and S. Lakshmi ^a ^*

^aResearch Department of Physics, SDNB Vaishnav College for Women, Chennai 600 004, India, and ^bDepartment of Organic Chemistry, University of Madras, Guindy, Chennai 600 025, India
^*Correspondence e-mail: lakssdnbvc@gmail.com

(Received 27 August 2013; accepted 21 September 2013; online 2 October 2013)

In the title compound C₂₆H₂₅NO₇, the mean plane through the lactone-substituted ring of the pyrrolizidine moiety forms dihedral angles of 78.46 (6) and 58.28 (8)° with the acenaphthylene moiety and the sugar based-lactone ring, respectively. The sum of the angles at the the N atom of the pyrrolizidine ring (335.0°) is in accordance with sp³ hybridization. Some atoms of the acetate group are disordered and were refined using a split model [occupancy ratio 0.673 (10):0.327 (10)].

CCDC reference: 962560

Related literature

For the importance of pyrrolidine and pyrrolizidine compounds and background to this work, see: Boido et al. (1994 ); Cravotto et al. (2001 ); Gershbein (1975 ); Govind et al. (2003 ); Jellimann et al. (2000 ); Nishimura et al. (1985 ); Selvanayagam et al. (2004 ); Usha et al. (2005 ).

Experimental

Crystal data

C₂₆H₂₅NO₇
M_r = 463.47
Tetragonal, P 4₃ 2₁ 2
a = 13.6792 (3) Å
c = 24.9625 (13) Å
V = 4671.0 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.30 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.902, T_max = 0.976
21173 measured reflections
4010 independent reflections
2923 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.104
S = 1.06
4010 reflections
367 parameters
138 restraints
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 962560

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813026111/nc2316sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813026111/nc2316Isup2.hkl

checkCIF report

Comment top

Synthesis of polycyclic compounds incorporating pyrrolidine and pyrrolizidine rings has been the center of attraction for the past several decades since it constitutes significant class of substances with highly pronounced biological activities (Nishimura et al.,1985). Pyrrolizidine alkaloids represent a group of compounds present in a variety of plants throughout the world (Usha et al., 2005). Acenaphthylene derivatives are found to have high κ-opioid receptor affinity and selectivity (Selvanayagam et al., 2004). These derivatives are used as new conformationally restricted ligands for melatonin receptors (Jellimann et al., 2000), liver regeneration (Gershbein et al., 1975) and antitumoral agents (Boido et al., 1994). Spiro compounds are often encountered in pharmacologically relevant alkaloids (Cravotto et al., 2001). In view of the important biological activities, the structure determination of the title compound was undertaken (Fig.1).

The lactone substituted ring of the pyrrolizidine moiety [C12/N1/C16—C18] forms dihedral angles of 78.46 (6)°, 58.28 (8)° with the acenaphthylene moiety [C12/C1—C11] and sugar based-lactone ring [C18/C17/C21/C20/O2/C19] respectively. The sum of the angles at nitrogen atom of the pyrrolizidine ring [335.01 (0.6)°] is in accordance with sp³ hybridization (Govind et al.,2003).

Related literature top

For the importance of pyrrolidine and pyrrolizidine compounds and background to this work, see: Boido et al. (1994); Cravotto et al. (2001); Gershbein (1975); Govind et al. (2003); Jellimann et al. (2000); Nishimura et al. (1985); Selvanayagam et al. (2004); Usha et al. (2005).

Experimental top

To a solution of acenaphthoquinone (1 equiv) and proline (1.4 equiv) in dry toluene, α,β- unsaturated sugar lactone was added under nitrogen atmosphere. The solution was refluxed for 10 h until the reaction was complete which was monitored by TLC. The solvent was evaporated under reduced pressure and the residue was extracted with dichloromethane and water. The organic layer was dried with anhydrous sodium sulfate and concentrated in vacuo. The crude product was purified by column chromatography using hexane/EtOAc (8:2) as an eluent. Crystals were obtained by slow evaporation of the solvent.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound with the numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius and disordering is shown with full and open bonds.

(1S,1'S,2'R,4a'S,9a'S,9b'R)-1'-Acetyloxy-2,4'-dioxo-2',4',4a',7',8',9',9a',9b'-octahydro-1'H,2H-spiro[acenaphthylene-1,5'-pyrano[4,3-a]pyrrolizin]-2'-ylmethyl acetate top

Crystal data top

C₂₆H₂₅NO₇	D_x = 1.318 Mg m⁻³
M_r = 463.47	Melting point: 481.15 K
Tetragonal, P4₃2₁2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P4nw2abw	Cell parameters from 5405 reflections
a = 13.6792 (3) Å	θ = 2.2–22.2°
c = 24.9625 (13) Å	µ = 0.10 mm⁻¹
V = 4671.0 (3) Å³	T = 295 K
Z = 8	Block, yellow
F(000) = 1952	0.30 × 0.30 × 0.25 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4010 independent reflections
Radiation source: fine-focus sealed tube	2923 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω and ϕ scan	θ_max = 25.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −16→16
T_min = 0.902, T_max = 0.976	k = −11→16
21173 measured reflections	l = −27→28

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)] = 0.042	H-atom parameters constrained
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.0494P)² + 0.438P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
4010 reflections	Δρ_max = 0.24 e Å⁻³
367 parameters	Δρ_min = −0.12 e Å⁻³
138 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0038 (5)

Crystal data top

C₂₆H₂₅NO₇	Z = 8
M_r = 463.47	Mo Kα radiation
Tetragonal, P4₃2₁2	µ = 0.10 mm⁻¹
a = 13.6792 (3) Å	T = 295 K
c = 24.9625 (13) Å	0.30 × 0.30 × 0.25 mm
V = 4671.0 (3) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	4010 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2923 reflections with I > 2σ(I)
T_min = 0.902, T_max = 0.976	R_int = 0.034
21173 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	138 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.06	Δρ_max = 0.24 e Å⁻³
4010 reflections	Δρ_min = −0.12 e Å⁻³
367 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	Occ. (<1)
C1	0.49450 (18)	0.37963 (17)	0.34572 (10)	0.0529 (6)
C2	0.52973 (19)	0.38194 (18)	0.40078 (10)	0.0567 (7)
C3	0.5995 (2)	0.4377 (2)	0.42606 (12)	0.0727 (8)
H3	0.6377	0.4823	0.4073	0.087*
C4	0.6103 (2)	0.4243 (3)	0.48143 (14)	0.0894 (10)
H4	0.6574	0.4609	0.4994	0.107*
C5	0.5552 (3)	0.3604 (3)	0.51006 (13)	0.0843 (9)
H5	0.5649	0.3551	0.5468	0.101*
C6	0.4840 (2)	0.3023 (2)	0.48530 (10)	0.0650 (7)
C7	0.4197 (2)	0.2338 (2)	0.50876 (12)	0.0785 (9)
H7	0.4215	0.2233	0.5456	0.094*
C8	0.3560 (2)	0.1837 (2)	0.47842 (11)	0.0763 (8)
H8	0.3157	0.1380	0.4949	0.092*
C9	0.3474 (2)	0.19735 (19)	0.42248 (11)	0.0660 (7)
H9	0.3017	0.1621	0.4028	0.079*
C10	0.40725 (18)	0.26315 (17)	0.39801 (9)	0.0522 (6)
C11	0.47403 (18)	0.31481 (17)	0.42968 (9)	0.0538 (6)
C12	0.41909 (17)	0.29582 (17)	0.34043 (9)	0.0508 (6)
C13	0.4556 (3)	0.1226 (2)	0.31434 (13)	0.0898 (10)
H13A	0.3875	0.1058	0.3201	0.108*
H13B	0.4939	0.1007	0.3448	0.108*
C14	0.4941 (3)	0.0793 (2)	0.26195 (13)	0.0945 (11)
H14A	0.5650	0.0791	0.2612	0.113*
H14B	0.4704	0.0131	0.2567	0.113*
C15	0.4528 (3)	0.1477 (2)	0.22047 (12)	0.0893 (10)
H15A	0.3920	0.1224	0.2061	0.107*
H15B	0.4987	0.1568	0.1913	0.107*
C16	0.4355 (2)	0.24436 (19)	0.25035 (10)	0.0639 (7)
H16	0.4763	0.2958	0.2346	0.077*
C17	0.33003 (19)	0.28012 (19)	0.25462 (9)	0.0587 (7)
H17	0.2867	0.2230	0.2540	0.070*
C18	0.32353 (17)	0.32766 (17)	0.31052 (9)	0.0505 (6)
H18	0.2686	0.2968	0.3292	0.061*
C19	0.30811 (17)	0.43601 (18)	0.31357 (10)	0.0532 (6)
C20	0.34631 (19)	0.44821 (18)	0.21942 (9)	0.0567 (6)
H20	0.4167	0.4371	0.2235	0.068*
C21	0.2963 (2)	0.3508 (2)	0.21183 (9)	0.0607 (7)
H21	0.2252	0.3589	0.2135	0.073*
C22	0.33054 (19)	0.5216 (2)	0.17621 (10)	0.0660 (7)
H22A	0.3560	0.5847	0.1873	0.079*
H22B	0.3646	0.5016	0.1439	0.079*
N1	0.46742 (16)	0.22513 (15)	0.30539 (8)	0.0636 (6)
O1	0.51791 (14)	0.43233 (14)	0.30886 (7)	0.0734 (6)
O2	0.30863 (12)	0.49008 (12)	0.26880 (6)	0.0599 (4)
O3	0.29131 (15)	0.47673 (14)	0.35530 (7)	0.0734 (5)
O5	0.22688 (12)	0.52899 (14)	0.16582 (7)	0.0674 (5)
O4	0.32451 (17)	0.31189 (15)	0.16054 (7)	0.0873 (7)
O6	0.2533 (3)	0.5940 (6)	0.08779 (18)	0.108 (2)	0.673 (10)
C23	0.1979 (6)	0.5579 (7)	0.1189 (2)	0.066 (2)	0.673 (10)
C24	0.0924 (7)	0.5520 (13)	0.1066 (6)	0.082 (3)	0.673 (10)
H24A	0.0823	0.5635	0.0691	0.123*	0.673 (10)
H24B	0.0579	0.6005	0.1270	0.123*	0.673 (10)
H24C	0.0685	0.4882	0.1158	0.123*	0.673 (10)
O6'	0.2525 (6)	0.5122 (12)	0.0794 (3)	0.101 (4)	0.327 (10)
C23'	0.1997 (12)	0.5354 (18)	0.1156 (4)	0.073 (4)	0.327 (10)
C24'	0.0906 (13)	0.540 (3)	0.1196 (11)	0.072 (5)	0.327 (10)
H24D	0.0625	0.4829	0.1039	0.109*	0.327 (10)
H24E	0.0674	0.5973	0.1009	0.109*	0.327 (10)
H24F	0.0718	0.5444	0.1566	0.109*	0.327 (10)
O7	0.1627 (7)	0.3021 (9)	0.1393 (4)	0.114 (3)	0.673 (10)
C25	0.2479 (7)	0.2915 (16)	0.1279 (5)	0.105 (3)	0.673 (10)
C26	0.2787 (9)	0.2525 (11)	0.0740 (5)	0.143 (4)	0.673 (10)
H26A	0.3158	0.1936	0.0787	0.215*	0.673 (10)
H26B	0.3182	0.3003	0.0560	0.215*	0.673 (10)
H26C	0.2217	0.2388	0.0528	0.215*	0.673 (10)
O7'	0.1851 (18)	0.3144 (19)	0.1230 (9)	0.122 (5)	0.327 (10)
C25'	0.2665 (17)	0.282 (3)	0.1209 (12)	0.112 (4)	0.327 (10)
C26'	0.3264 (19)	0.2324 (18)	0.0783 (9)	0.119 (6)	0.327 (10)
H26D	0.2952	0.1724	0.0680	0.178*	0.327 (10)
H26E	0.3905	0.2186	0.0921	0.178*	0.327 (10)
H26F	0.3318	0.2745	0.0477	0.178*	0.327 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0599 (16)	0.0540 (15)	0.0449 (16)	0.0000 (11)	0.0005 (12)	0.0049 (12)
C2	0.0620 (16)	0.0603 (16)	0.0476 (16)	0.0012 (12)	−0.0052 (13)	−0.0022 (12)
C3	0.0722 (19)	0.081 (2)	0.065 (2)	−0.0042 (15)	−0.0190 (15)	−0.0035 (15)
C4	0.093 (2)	0.097 (3)	0.078 (3)	−0.0003 (19)	−0.0338 (19)	−0.0095 (19)
C5	0.104 (3)	0.095 (2)	0.0541 (19)	0.026 (2)	−0.0200 (18)	−0.0050 (17)
C6	0.083 (2)	0.0668 (17)	0.0449 (17)	0.0219 (14)	−0.0037 (15)	0.0061 (14)
C7	0.105 (2)	0.084 (2)	0.0463 (18)	0.0269 (18)	0.0066 (18)	0.0209 (16)
C8	0.100 (2)	0.0702 (19)	0.059 (2)	0.0063 (16)	0.0176 (17)	0.0228 (16)
C9	0.0806 (19)	0.0600 (17)	0.0573 (18)	−0.0029 (13)	0.0101 (14)	0.0101 (13)
C10	0.0684 (16)	0.0467 (14)	0.0416 (15)	0.0005 (11)	0.0042 (12)	0.0068 (11)
C11	0.0700 (16)	0.0531 (14)	0.0382 (15)	0.0124 (12)	0.0000 (12)	0.0057 (11)
C12	0.0618 (15)	0.0496 (14)	0.0410 (15)	−0.0057 (11)	0.0025 (11)	0.0001 (11)
C13	0.120 (3)	0.066 (2)	0.084 (2)	0.0018 (17)	0.0054 (19)	−0.0087 (17)
C14	0.128 (3)	0.0651 (19)	0.091 (2)	0.0087 (19)	0.010 (2)	−0.0184 (18)
C15	0.113 (3)	0.082 (2)	0.072 (2)	0.0072 (19)	0.0118 (18)	−0.0235 (17)
C16	0.083 (2)	0.0637 (17)	0.0446 (17)	−0.0005 (13)	0.0097 (13)	−0.0034 (12)
C17	0.0706 (17)	0.0619 (16)	0.0438 (16)	−0.0159 (12)	0.0010 (12)	−0.0035 (12)
C18	0.0568 (15)	0.0555 (15)	0.0392 (15)	−0.0135 (10)	0.0036 (11)	0.0000 (11)
C19	0.0559 (15)	0.0629 (17)	0.0409 (16)	−0.0026 (11)	−0.0021 (12)	0.0011 (13)
C20	0.0592 (15)	0.0716 (17)	0.0392 (15)	−0.0074 (12)	0.0031 (11)	0.0029 (12)
C21	0.0710 (17)	0.0756 (18)	0.0357 (15)	−0.0145 (14)	−0.0006 (12)	−0.0027 (13)
C22	0.0589 (17)	0.0831 (19)	0.0559 (17)	−0.0138 (13)	−0.0011 (13)	0.0119 (14)
N1	0.0864 (16)	0.0562 (14)	0.0481 (14)	0.0016 (11)	0.0048 (11)	−0.0009 (10)
O1	0.0849 (13)	0.0802 (13)	0.0552 (12)	−0.0292 (10)	−0.0069 (10)	0.0176 (10)
O2	0.0759 (12)	0.0608 (11)	0.0430 (10)	−0.0020 (8)	−0.0031 (8)	0.0035 (8)
O3	0.1011 (14)	0.0731 (12)	0.0459 (11)	0.0151 (10)	0.0021 (9)	−0.0077 (10)
O5	0.0635 (12)	0.0933 (13)	0.0453 (11)	−0.0059 (9)	−0.0001 (9)	0.0081 (9)
O4	0.1211 (18)	0.1029 (16)	0.0377 (12)	−0.0152 (13)	−0.0072 (11)	−0.0139 (11)
O6	0.092 (3)	0.157 (5)	0.075 (3)	0.024 (3)	0.018 (2)	0.060 (3)
C23	0.075 (3)	0.080 (5)	0.042 (3)	0.012 (3)	0.002 (3)	0.001 (2)
C24	0.082 (4)	0.087 (5)	0.076 (7)	0.001 (3)	−0.015 (4)	0.002 (6)
O6'	0.096 (5)	0.158 (9)	0.050 (4)	0.004 (5)	0.015 (4)	0.012 (5)
C23'	0.069 (6)	0.101 (8)	0.049 (6)	−0.010 (5)	0.000 (5)	0.001 (5)
C24'	0.083 (7)	0.089 (10)	0.046 (8)	0.010 (7)	−0.036 (6)	−0.015 (8)
O7	0.144 (5)	0.126 (4)	0.072 (5)	−0.050 (3)	−0.041 (4)	0.001 (4)
C25	0.165 (7)	0.095 (6)	0.054 (5)	−0.022 (6)	−0.024 (6)	−0.010 (4)
C26	0.214 (10)	0.159 (8)	0.056 (5)	0.001 (8)	−0.032 (6)	−0.027 (5)
O7'	0.186 (12)	0.110 (8)	0.071 (10)	−0.011 (9)	−0.041 (8)	−0.007 (7)
C25'	0.179 (8)	0.098 (7)	0.058 (7)	−0.028 (7)	−0.022 (7)	0.003 (6)
C26'	0.210 (16)	0.106 (9)	0.040 (7)	0.004 (11)	−0.027 (10)	−0.021 (6)

Geometric parameters (Å, º) top

C1—O1	1.212 (3)	C17—H17	0.9800
C1—C2	1.457 (3)	C18—C19	1.499 (3)
C1—C12	1.548 (3)	C18—H18	0.9800
C2—C3	1.375 (4)	C19—O3	1.203 (3)
C2—C11	1.394 (3)	C19—O2	1.340 (3)
C3—C4	1.402 (4)	C20—O2	1.454 (3)
C3—H3	0.9300	C20—C22	1.490 (3)
C4—C5	1.357 (5)	C20—C21	1.509 (4)
C4—H4	0.9300	C20—H20	0.9800
C5—C6	1.401 (4)	C21—O4	1.439 (3)
C5—H5	0.9300	C21—H21	0.9800
C6—C11	1.405 (3)	C22—O5	1.445 (3)
C6—C7	1.412 (4)	C22—H22A	0.9700
C7—C8	1.343 (4)	C22—H22B	0.9700
C7—H7	0.9300	O5—C23	1.299 (6)
C8—C9	1.414 (4)	O5—C23'	1.310 (9)
C8—H8	0.9300	O4—C25'	1.333 (10)
C9—C10	1.362 (3)	O4—C25	1.356 (7)
C9—H9	0.9300	O6—C23	1.192 (7)
C10—C11	1.400 (3)	C23—C24	1.477 (7)
C10—C12	1.514 (3)	C24—H24A	0.9600
C12—N1	1.462 (3)	C24—H24B	0.9600
C12—C18	1.567 (3)	C24—H24C	0.9600
C13—N1	1.429 (4)	O6'—C23'	1.199 (9)
C13—C14	1.529 (4)	C23'—C24'	1.498 (10)
C13—H13A	0.9700	C24'—H24D	0.9600
C13—H13B	0.9700	C24'—H24E	0.9600
C14—C15	1.505 (4)	C24'—H24F	0.9600
C14—H14A	0.9700	O7—C25	1.210 (8)
C14—H14B	0.9700	C25—C26	1.508 (8)
C15—C16	1.537 (4)	C26—H26A	0.9600
C15—H15A	0.9700	C26—H26B	0.9600
C15—H15B	0.9700	C26—H26C	0.9600
C16—N1	1.465 (3)	O7'—C25'	1.199 (10)
C16—C17	1.527 (4)	C25'—C26'	1.504 (10)
C16—H16	0.9800	C26'—H26D	0.9600
C17—C21	1.513 (3)	C26'—H26E	0.9600
C17—C18	1.542 (3)	C26'—H26F	0.9600

O1—C1—C2	128.0 (2)	C16—C17—C18	104.6 (2)
O1—C1—C12	123.5 (2)	C21—C17—H17	108.3
C2—C1—C12	108.5 (2)	C16—C17—H17	108.3
C3—C2—C11	120.5 (2)	C18—C17—H17	108.3
C3—C2—C1	132.4 (3)	C19—C18—C17	118.1 (2)
C11—C2—C1	107.0 (2)	C19—C18—C12	111.59 (18)
C2—C3—C4	116.9 (3)	C17—C18—C12	105.41 (19)
C2—C3—H3	121.5	C19—C18—H18	107.1
C4—C3—H3	121.5	C17—C18—H18	107.1
C5—C4—C3	123.0 (3)	C12—C18—H18	107.1
C5—C4—H4	118.5	O3—C19—O2	117.9 (2)
C3—C4—H4	118.5	O3—C19—C18	121.9 (2)
C4—C5—C6	121.3 (3)	O2—C19—C18	120.2 (2)
C4—C5—H5	119.4	O2—C20—C22	107.3 (2)
C6—C5—H5	119.4	O2—C20—C21	107.08 (18)
C5—C6—C11	115.7 (3)	C22—C20—C21	116.0 (2)
C5—C6—C7	128.8 (3)	O2—C20—H20	108.8
C11—C6—C7	115.5 (3)	C22—C20—H20	108.8
C8—C7—C6	120.6 (3)	C21—C20—H20	108.8
C8—C7—H7	119.7	O4—C21—C20	108.5 (2)
C6—C7—H7	119.7	O4—C21—C17	108.0 (2)
C7—C8—C9	122.9 (3)	C20—C21—C17	109.7 (2)
C7—C8—H8	118.5	O4—C21—H21	110.2
C9—C8—H8	118.5	C20—C21—H21	110.2
C10—C9—C8	118.7 (3)	C17—C21—H21	110.2
C10—C9—H9	120.6	O5—C22—C20	108.6 (2)
C8—C9—H9	120.6	O5—C22—H22A	110.0
C9—C10—C11	118.2 (2)	C20—C22—H22A	110.0
C9—C10—C12	133.3 (2)	O5—C22—H22B	110.0
C11—C10—C12	108.51 (19)	C20—C22—H22B	110.0
C2—C11—C10	113.4 (2)	H22A—C22—H22B	108.3
C2—C11—C6	122.6 (2)	C13—N1—C12	120.3 (2)
C10—C11—C6	124.0 (2)	C13—N1—C16	106.8 (2)
N1—C12—C10	114.91 (19)	C12—N1—C16	107.92 (19)
N1—C12—C1	103.87 (19)	C19—O2—C20	119.44 (19)
C10—C12—C1	102.06 (19)	C23—O5—C23'	14.1 (14)
N1—C12—C18	106.01 (17)	C23—O5—C22	118.9 (4)
C10—C12—C18	116.43 (19)	C23'—O5—C22	117.1 (7)
C1—C12—C18	113.00 (19)	C25'—O4—C25	14.2 (14)
N1—C13—C14	102.0 (2)	C25'—O4—C21	127.9 (12)
N1—C13—H13A	111.4	C25—O4—C21	113.8 (5)
C14—C13—H13A	111.4	O6—C23—O5	121.3 (7)
N1—C13—H13B	111.4	O6—C23—C24	120.6 (7)
C14—C13—H13B	111.4	O5—C23—C24	117.9 (7)
H13A—C13—H13B	109.2	O6'—C23'—O5	122.1 (12)
C15—C14—C13	102.6 (3)	O6'—C23'—C24'	131.5 (16)
C15—C14—H14A	111.2	O5—C23'—C24'	102.8 (13)
C13—C14—H14A	111.2	C23'—C24'—H24D	109.5
C15—C14—H14B	111.2	C23'—C24'—H24E	109.5
C13—C14—H14B	111.2	H24D—C24'—H24E	109.5
H14A—C14—H14B	109.2	C23'—C24'—H24F	109.5
C14—C15—C16	105.0 (2)	H24D—C24'—H24F	109.5
C14—C15—H15A	110.7	H24E—C24'—H24F	109.5
C16—C15—H15A	110.7	O7—C25—O4	125.4 (8)
C14—C15—H15B	110.7	O7—C25—C26	121.5 (8)
C16—C15—H15B	110.7	O4—C25—C26	113.2 (8)
H15A—C15—H15B	108.8	O7'—C25'—O4	114 (2)
N1—C16—C17	105.9 (2)	O7'—C25'—C26'	134.7 (18)
N1—C16—C15	104.8 (2)	O4—C25'—C26'	109.8 (16)
C17—C16—C15	117.1 (2)	C25'—C26'—H26D	109.5
N1—C16—H16	109.6	C25'—C26'—H26E	109.5
C17—C16—H16	109.6	H26D—C26'—H26E	109.5
C15—C16—H16	109.6	C25'—C26'—H26F	109.5
C21—C17—C16	116.3 (2)	H26D—C26'—H26F	109.5
C21—C17—C18	110.6 (2)	H26E—C26'—H26F	109.5

O1—C1—C2—C3	−3.5 (5)	N1—C12—C18—C17	−6.9 (2)
C12—C1—C2—C3	176.4 (3)	C10—C12—C18—C17	−136.1 (2)
O1—C1—C2—C11	173.5 (3)	C1—C12—C18—C17	106.2 (2)
C12—C1—C2—C11	−6.6 (3)	C17—C18—C19—O3	171.5 (2)
C11—C2—C3—C4	−0.7 (4)	C12—C18—C19—O3	−66.2 (3)
C1—C2—C3—C4	176.0 (3)	C17—C18—C19—O2	−5.7 (3)
C2—C3—C4—C5	−0.5 (5)	C12—C18—C19—O2	116.7 (2)
C3—C4—C5—C6	0.8 (5)	O2—C20—C21—O4	174.2 (2)
C4—C5—C6—C11	0.1 (4)	C22—C20—C21—O4	54.5 (3)
C4—C5—C6—C7	−179.0 (3)	O2—C20—C21—C17	−67.9 (3)
C5—C6—C7—C8	−179.5 (3)	C22—C20—C21—C17	172.3 (2)
C11—C6—C7—C8	1.5 (4)	C16—C17—C21—O4	48.0 (3)
C6—C7—C8—C9	−1.5 (5)	C18—C17—C21—O4	167.1 (2)
C7—C8—C9—C10	1.0 (4)	C16—C17—C21—C20	−70.2 (3)
C8—C9—C10—C11	−0.5 (4)	C18—C17—C21—C20	49.0 (3)
C8—C9—C10—C12	179.6 (3)	O2—C20—C22—O5	−69.4 (3)
C3—C2—C11—C10	−179.3 (2)	C21—C20—C22—O5	50.2 (3)
C1—C2—C11—C10	3.3 (3)	C14—C13—N1—C12	165.8 (2)
C3—C2—C11—C6	1.6 (4)	C14—C13—N1—C16	42.5 (3)
C1—C2—C11—C6	−175.8 (2)	C10—C12—N1—C13	32.2 (3)
C9—C10—C11—C2	−178.4 (2)	C1—C12—N1—C13	142.8 (3)
C12—C10—C11—C2	1.5 (3)	C18—C12—N1—C13	−97.9 (3)
C9—C10—C11—C6	0.7 (4)	C10—C12—N1—C16	154.9 (2)
C12—C10—C11—C6	−179.4 (2)	C1—C12—N1—C16	−94.5 (2)
C5—C6—C11—C2	−1.3 (4)	C18—C12—N1—C16	24.9 (2)
C7—C6—C11—C2	177.9 (2)	C17—C16—N1—C13	97.3 (2)
C5—C6—C11—C10	179.7 (3)	C15—C16—N1—C13	−27.0 (3)
C7—C6—C11—C10	−1.1 (4)	C17—C16—N1—C12	−33.3 (2)
C9—C10—C12—N1	−73.7 (4)	C15—C16—N1—C12	−157.7 (2)
C11—C10—C12—N1	106.4 (2)	O3—C19—O2—C20	168.5 (2)
C9—C10—C12—C1	174.6 (3)	C18—C19—O2—C20	−14.3 (3)
C11—C10—C12—C1	−5.3 (3)	C22—C20—O2—C19	175.71 (19)
C9—C10—C12—C18	51.1 (4)	C21—C20—O2—C19	50.5 (3)
C11—C10—C12—C18	−128.8 (2)	C20—C22—O5—C23	−154.5 (5)
O1—C1—C12—N1	67.3 (3)	C20—C22—O5—C23'	−138.6 (12)
C2—C1—C12—N1	−112.6 (2)	C20—C21—O4—C25'	−126 (3)
O1—C1—C12—C10	−173.0 (2)	C17—C21—O4—C25'	115 (3)
C2—C1—C12—C10	7.2 (3)	C20—C21—O4—C25	−123.5 (11)
O1—C1—C12—C18	−47.1 (3)	C17—C21—O4—C25	117.6 (11)
C2—C1—C12—C18	133.0 (2)	C23'—O5—C23—O6	−99 (4)
N1—C13—C14—C15	−41.0 (3)	C22—O5—C23—O6	−13.0 (10)
C13—C14—C15—C16	24.4 (3)	C23'—O5—C23—C24	85 (5)
C14—C15—C16—N1	0.1 (3)	C22—O5—C23—C24	171.8 (9)
C14—C15—C16—C17	−116.8 (3)	C23—O5—C23'—O6'	119 (6)
N1—C16—C17—C21	149.9 (2)	C22—O5—C23'—O6'	18 (3)
C15—C16—C17—C21	−93.8 (3)	C23—O5—C23'—C24'	−80 (4)
N1—C16—C17—C18	27.6 (2)	C22—O5—C23'—C24'	179.3 (14)
C15—C16—C17—C18	143.9 (2)	C25'—O4—C25—O7	171 (15)
C21—C17—C18—C19	−12.9 (3)	C21—O4—C25—O7	−1 (3)
C16—C17—C18—C19	113.0 (2)	C25'—O4—C25—C26	−9 (12)
C21—C17—C18—C12	−138.4 (2)	C21—O4—C25—C26	178.9 (10)
C16—C17—C18—C12	−12.4 (2)	C25—O4—C25'—O7'	12 (9)
N1—C12—C18—C19	−136.3 (2)	C21—O4—C25'—O7'	20 (6)
C10—C12—C18—C19	94.5 (2)	C25—O4—C25'—C26'	−180 (16)
C1—C12—C18—C19	−23.2 (3)	C21—O4—C25'—C26'	−171.1 (14)

Experimental details

Crystal data
Chemical formula	C₂₆H₂₅NO₇
M_r	463.47
Crystal system, space group	Tetragonal, P4₃2₁2
Temperature (K)	295
a, c (Å)	13.6792 (3), 24.9625 (13)
V (Å³)	4671.0 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.30 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.902, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	21173, 4010, 2923
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.104, 1.06
No. of reflections	4010
No. of parameters	367
No. of restraints	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.12

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2009).

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Boido, A., Vazzana, I. & Sparatore, F. (1994). Il Farmaco, 49, 97–104. CAS PubMed Web of Science Google Scholar
Bruker (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cravotto, G., Giovenzana, G. B., Pilati, T., Sisti, M. & Palmisano, G. (2001). J. Org. Chem. 66, 8447–8453. Web of Science CSD CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gershbein, L. L. (1975). Res. Commun. Chem. Pathol. Pharmacol. 11, 445–466. PubMed CAS Web of Science Google Scholar
Govind, M. M., Selvanayagam, S., Velmurugan, D., Ravikumar, K., Sridhar, G. & Raghunathan, R. (2003). Acta Cryst. E59, o1680–o1681. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Jellimann, C., Allainmat, M., Andrieux, J., Kloubert, S., Boutin, J. A., Nicolas, J. P., Bennejean, C., Delagrange, P. & Langlois, M. (2000). J. Med. Chem. 43, 4051–4062. Web of Science CrossRef PubMed CAS Google Scholar
Nishimura, Y., Kondo, S. & Umezawa, H. (1985). J. Org. Chem. 50, 5210–5214. CrossRef CAS Web of Science Google Scholar
Selvanayagam, S., Velmurugan, D., Ravikumar, K., Jayashankaran, J., Durga, R. R. & Raghunathan, R. (2004). Acta Cryst. E60, o2216–o2218. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Usha, G., Selvanayagam, S., Velmurugan, D., Ravikumar, K., Durga, R. R. & Raghunathan, R. (2005). Acta Cryst. E61, o2267–o2269. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

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