Kallolide A acetate pyrazoline.

IN THE CRYSTAL STRUCTURE OF KALLOLIDE A ACETATE PYRAZOLINE [SYSTEMATIC NAME: 7-methyl-16-oxo-4,10-bis-(prop-1-en-2-yl)-17,18-dioxa-14,15-diaza-tetra-cyclo-[9.4.2.1(6,9).0(1,12)]octa-deca-6,8,14-trien-5-yl acetate], C(23)H(28)N(2)O(5), there is a 12-member-ed carbon macrocyclic structure. In addition, there is a tris-ubstituted furan ring, an approximately planar γ-lactone ring [maximum deviation of 0.057 (3) Å] and a pyraz-oline ring, the latter in an envelope conformation. The pyrazoline and the γ-lactone rings are fused in a cis configuration. In the crystal, mol-ecules are linked by weak C-H⋯O inter-actions, forming a two-dimensional network parallel to (001). An intra-molecular C-H⋯O hydrogen bond is also present.

Related literature

For information on West Indies sea plumes, see: Bayer (1961 ▶); Lasker & Coffroth (1983 ▶); Humman (1996 ▶); Sánchez et al. (1998 ▶); Williams & Vennam (2001 ▶). For complete background to the natural product chemistry of the Gorgonian genus Pseudopterogorgia, see: Marrero et al. (2010 ▶). For species of Pseudopterogorgia, see: Yoshioka (1997 ▶); Sánchez et al. (2003 ▶); Sánchez & Lasker (2003 ▶). For the biological activity of diterpenoids from Pseudopterogorgia, see: Heckrodt & Mulzer (2005 ▶). For more information on the pseudoterane-type of diterpenes, see: Bundurraga & Fenical (1982 ▶); Look et al. (1985 ▶); Williams et al. (1987b ▶); Rodríguez & Soto (1996 ▶); Marrero et al. (2006 ▶). For bioactive diterpenes isolated from Pseudopterogorgia kallos, see: Marrero et al. (2003a ▶,b ▶, 2004a ▶,b ▶, 2005 ▶). For biosynthetic relationship studies between cembrane- and pseudopterane-type diterpenes, see: Rodríguez & Shi (1998 ▶); Yang et al. (2010 ▶); Li & Pattenden (2011 ▶). For information on gersolane-type diterpenes and biosynthetic relationship studies between cembrane- and gersolane-type diterpenes, see: Williams et al. (1987a ▶); Rodríguez et al. (1998 ▶). For complete background to the chemistry of furan­ocembranoids, pseudopteranes, gersolanes and related compounds, see: Roethle & Trauner (2008 ▶). For the synthesis of kallolide A and kallolide A acetate, see: Marshall & Liao (1998 ▶).

Experimental

Crystal data

C23H28N2O5

M = 412.47

Orthorhombic,

a = 10.593 (6) Å

b = 12.426 (7) Å

c = 17.099 (10) Å

V = 2251 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 298 K

0.40 × 0.30 × 0.10 mm

Data collection

Bruker SMART 1K CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T min = 0.966, T max = 0.992

14038 measured reflections

2583 independent reflections

2160 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.118

S = 1.13

2583 reflections

276 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.23 e Å−3

Data collection: SMART-NT (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b ▶); molecular graphics: SHELXTL (Sheldrick, 2008b ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811051890/wn2456sup1.cif

Supplementary material file. DOI: 10.1107/S1600536811051890/wn2456Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811051890/wn2456Isup3.hkl

Supplementary material file. DOI: 10.1107/S1600536811051890/wn2456Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C23H28N2O5	F(000) = 880
Mr = 412.47	Dx = 1.217 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9306 reflections
a = 10.593 (6) Å	θ = 2.3–26.7°
b = 12.426 (7) Å	µ = 0.09 mm−1
c = 17.099 (10) Å	T = 298 K
V = 2251 (2) Å3	Block, colourless
Z = 4	0.40 × 0.30 × 0.10 mm

Bruker SMART 1K CCD diffractometer	2583 independent reflections
Radiation source: fine-focus sealed tube	2160 reflections with I > 2σ(I)
graphite	Rint = 0.041
φ and ω scans	θmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −11→13
Tmin = 0.966, Tmax = 0.992	k = −15→15
14038 measured reflections	l = −21→21

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)] = 0.047	H-atom parameters constrained
wR(F2) = 0.118	w = 1/[σ2(Fo2) + (0.0552P)2 + 0.3145P] where P = (Fo2 + 2Fc2)/3
S = 1.13	(Δ/σ)max < 0.001
2583 reflections	Δρmax = 0.35 e Å−3
276 parameters	Δρmin = −0.23 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.061 (4)

Experimental. IR(neat) νmax 3078, 2969, 2944, 2927, 1764, 1728, 1642, 1375, 1251, 1227, 907, 810 cm-1; 1H NMR (300 MHz, DMSO-d6) δ 3.10 (1H, dd, J = 11.0, 9.0 Hz, H-2),5.60 (1H, d, J = 11.7 Hz, H-2), 6.23 (1H, s, H-5), 3.89 (1H, d, J = 2.7 Hz, H-7), 4.59 (1H, m, H-8)a, 2.11 (1H, br dd, J = 6.3, 5.7 Hz, H-9), 2.48 (1H, m, H-11a)b, 0.81 (1H, dd, J = 14.1, 5.7 Hz), 1.31 (1H,m,H-12a), 0.30 (1H, dd, J = 13.8, 13.5 Hz, H-12b), 4.88 (1H,vd, J = 1.2 Hz, H-14a), 4.51 (1H, s, H-14b), 1.77 (3H, s, H-15), 2.00 (3H, s, H-16), 5.08 (1H, d, J = 2.1 Hz, H-18a), 4.93 (1H, s, H-18b), 1.63 (3H, s, H-19), 1.94 (3H, s, H-22), 5.17 (1H, d, J = 18.6 Hz, H-23a), 5.62 (1H, dd, J = 18.9 Hz, H-23b)a (a values are interchangeable, b proton signal peak overlap with solvent). 13C NMR (DMSO-d6, 75 MHz) δ 48.4 (CH, C-1), 66.5 (CH, C-2), 146.5 (C, C-3), 122.4 (C, C4), 114.4 (CH, C-5), 152.5 (C, C-6), 46.0 (CH, C-7), 84.6 (CH, C-8), 36.7 (CH, C-9), 105.7 (C, C-10), 26.6 (CH2, C-11), 25.1 (CH2, C-12), 143.9 (C, C-13), 114.4 (CH2, C-14), 21.8 (CH3, C-15), 9.7 (CH3, C-16), 143.3 (C, C-17), 115.5 (CH2, C-18), 17.9 (CH3, C-19), 172.9 (C, C-10), 170.1 (C, C-21), 21.1 (CH3, C-22), 86.2 (CH2, C-23); LREI-MS m/z [M]+; 412(6.4), 384 (19), 370 (15), 342 (9), 231 (7), 214 (13), 178 (11), 165 (23), 164 (100), 163 (87), 135 (28); HREI-MS m/z [M]+ calcd for C23H28N2O5 412.1998 found 412.2003.

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.

	x	y	z	Uiso*/Ueq
O2	0.85009 (16)	0.35559 (14)	0.16945 (10)	0.0506 (4)
O1	0.59698 (18)	0.25015 (14)	0.22854 (11)	0.0564 (5)
C3	0.7288 (2)	0.39670 (19)	0.17940 (15)	0.0474 (6)
C9	1.0882 (3)	0.4597 (2)	0.24459 (17)	0.0586 (7)
H9	1.0151	0.5047	0.2316	0.070*
O5	0.4266 (2)	0.3406 (2)	0.1863 (2)	0.1156 (11)
O3	1.0951 (2)	0.27160 (17)	0.20733 (13)	0.0696 (6)
C20	1.0579 (3)	0.2727 (2)	0.28330 (18)	0.0629 (8)
C11	0.9562 (3)	0.4146 (2)	0.37422 (16)	0.0629 (8)
H11A	0.9813	0.4790	0.4023	0.076*
H11B	0.9513	0.3568	0.4122	0.076*
O4	1.0311 (3)	0.19117 (16)	0.31793 (15)	0.0867 (8)
C6	0.9085 (3)	0.4155 (2)	0.11168 (14)	0.0526 (6)
C2	0.6586 (3)	0.35346 (19)	0.24830 (14)	0.0486 (6)
H2	0.5943	0.4056	0.2645	0.058*
C1	0.7473 (3)	0.3298 (2)	0.31789 (14)	0.0517 (6)
H1	0.8090	0.2763	0.3003	0.062*
C10	1.0619 (3)	0.3868 (2)	0.31621 (17)	0.0576 (7)
N2	1.2578 (3)	0.4666 (3)	0.3389 (2)	0.0925 (10)
C12	0.8225 (3)	0.4334 (2)	0.34163 (15)	0.0553 (7)
H12A	0.8291	0.4796	0.2961	0.066*
H12B	0.7739	0.4720	0.3807	0.066*
C4	0.7090 (3)	0.4796 (2)	0.12735 (14)	0.0555 (7)
C5	0.8259 (3)	0.4905 (2)	0.08522 (15)	0.0620 (8)
H5	0.8421	0.5407	0.0462	0.074*
C8	1.1207 (3)	0.3803 (3)	0.17747 (19)	0.0647 (8)
H8	1.2113	0.3859	0.1667	0.078*
N1	1.1882 (3)	0.3930 (2)	0.36229 (18)	0.0823 (9)
C7	1.0488 (3)	0.3979 (3)	0.09993 (17)	0.0652 (8)
H7	1.0808	0.4662	0.0792	0.078*
C23	1.2011 (3)	0.5276 (3)	0.2723 (2)	0.0832 (10)
H23A	1.2621	0.5365	0.2305	0.100*
H23B	1.1733	0.5982	0.2894	0.100*
C21	0.4806 (3)	0.2569 (3)	0.19643 (19)	0.0699 (8)
C13	0.6784 (3)	0.2824 (2)	0.38899 (16)	0.0685 (9)
C16	0.5932 (4)	0.5490 (3)	0.1176 (2)	0.0900 (12)
H16A	0.5250	0.5194	0.1477	0.135*
H16B	0.5697	0.5511	0.0634	0.135*
H16C	0.6111	0.6206	0.1354	0.135*
C15	0.5551 (4)	0.3321 (3)	0.41338 (19)	0.0872 (11)
H15A	0.4911	0.3143	0.3758	0.131*
H15B	0.5643	0.4089	0.4161	0.131*
H15C	0.5312	0.3049	0.4638	0.131*
C22	0.4304 (4)	0.1483 (3)	0.1731 (2)	0.0971 (13)
H22A	0.3673	0.1257	0.2099	0.146*
H22B	0.4982	0.0970	0.1725	0.146*
H22C	0.3936	0.1528	0.1219	0.146*
C17	1.0837 (4)	0.3138 (4)	0.03873 (19)	0.0848 (11)
C19	1.0205 (7)	0.2132 (4)	0.0357 (3)	0.135 (2)
H19A	1.0489	0.1736	−0.0092	0.202*
H19B	0.9311	0.2249	0.0319	0.202*
H19C	1.0387	0.1730	0.0823	0.202*
C14	0.7312 (5)	0.2005 (3)	0.4285 (2)	0.1048 (14)
H14A	0.6914	0.1727	0.4725	0.126*
H14B	0.8076	0.1716	0.4118	0.126*
C18	1.1806 (6)	0.3379 (6)	−0.0128 (3)	0.191 (3)
H18A	1.2052	0.2878	−0.0502	0.229*
H18B	1.2210	0.4043	−0.0100	0.229*

	U11	U22	U33	U12	U13	U23
O2	0.0472 (9)	0.0503 (9)	0.0543 (10)	0.0012 (8)	−0.0055 (8)	0.0105 (8)
O1	0.0550 (11)	0.0550 (10)	0.0590 (10)	−0.0065 (9)	−0.0097 (9)	0.0015 (8)
C3	0.0486 (13)	0.0441 (12)	0.0495 (13)	0.0021 (11)	−0.0095 (11)	−0.0005 (11)
C9	0.0533 (15)	0.0518 (14)	0.0706 (16)	−0.0075 (13)	−0.0157 (14)	0.0067 (13)
O5	0.0589 (14)	0.0964 (19)	0.192 (3)	0.0018 (14)	−0.0418 (19)	−0.001 (2)
O3	0.0711 (13)	0.0584 (12)	0.0792 (14)	0.0083 (11)	−0.0173 (12)	−0.0034 (10)
C20	0.0616 (18)	0.0524 (16)	0.0748 (19)	0.0048 (14)	−0.0254 (15)	0.0057 (14)
C11	0.083 (2)	0.0551 (16)	0.0502 (14)	−0.0120 (15)	−0.0210 (14)	0.0033 (13)
O4	0.1109 (19)	0.0470 (11)	0.1021 (16)	−0.0006 (12)	−0.0299 (15)	0.0179 (11)
C6	0.0571 (15)	0.0547 (14)	0.0460 (13)	−0.0065 (13)	−0.0059 (12)	0.0063 (12)
C2	0.0500 (13)	0.0472 (12)	0.0488 (13)	−0.0001 (12)	−0.0041 (11)	−0.0012 (11)
C1	0.0610 (15)	0.0471 (13)	0.0469 (13)	−0.0039 (12)	−0.0069 (12)	0.0030 (11)
C10	0.0609 (16)	0.0500 (14)	0.0620 (16)	−0.0036 (12)	−0.0251 (14)	0.0059 (12)
N2	0.078 (2)	0.090 (2)	0.109 (2)	−0.0219 (18)	−0.0372 (18)	0.0025 (18)
C12	0.0708 (18)	0.0495 (14)	0.0457 (12)	−0.0050 (13)	−0.0063 (13)	0.0004 (11)
C4	0.0660 (17)	0.0563 (14)	0.0443 (12)	0.0099 (14)	−0.0104 (12)	0.0017 (11)
C5	0.081 (2)	0.0597 (16)	0.0455 (13)	−0.0025 (16)	−0.0075 (14)	0.0129 (12)
C8	0.0509 (15)	0.0694 (18)	0.0738 (19)	−0.0056 (14)	−0.0058 (14)	0.0060 (15)
N1	0.0778 (19)	0.0810 (18)	0.0882 (19)	−0.0025 (16)	−0.0410 (16)	0.0061 (16)
C7	0.0586 (17)	0.0775 (19)	0.0594 (16)	−0.0087 (15)	−0.0001 (13)	0.0094 (15)
C23	0.076 (2)	0.0747 (19)	0.099 (2)	−0.0248 (19)	−0.024 (2)	0.0073 (19)
C21	0.0514 (16)	0.082 (2)	0.0764 (19)	−0.0127 (16)	−0.0093 (15)	0.0080 (17)
C13	0.086 (2)	0.0729 (18)	0.0464 (14)	−0.0235 (18)	−0.0050 (15)	0.0042 (14)
C16	0.104 (3)	0.089 (2)	0.077 (2)	0.043 (2)	−0.007 (2)	0.0167 (19)
C15	0.094 (3)	0.106 (3)	0.0609 (18)	−0.026 (2)	0.0143 (18)	−0.0068 (18)
C22	0.092 (3)	0.099 (3)	0.101 (3)	−0.040 (2)	−0.030 (2)	0.010 (2)
C17	0.069 (2)	0.123 (3)	0.0621 (18)	0.005 (2)	0.0067 (17)	−0.0059 (19)
C19	0.178 (6)	0.116 (4)	0.110 (3)	−0.003 (4)	0.035 (4)	−0.032 (3)
C14	0.131 (4)	0.107 (3)	0.076 (2)	−0.023 (3)	−0.009 (2)	0.041 (2)
C18	0.154 (5)	0.275 (8)	0.143 (5)	−0.080 (6)	0.086 (4)	−0.082 (5)

O2—C6	1.383 (3)	C4—C5	1.439 (4)
O2—C3	1.393 (3)	C4—C16	1.509 (4)
O1—C21	1.353 (4)	C5—H5	0.9300
O1—C2	1.479 (3)	C8—C7	1.545 (4)
C3—C4	1.378 (4)	C8—H8	0.9800
C3—C2	1.493 (4)	C7—C17	1.524 (5)
C9—C23	1.539 (4)	C7—H7	0.9800
C9—C10	1.549 (4)	C23—H23A	0.9700
C9—C8	1.552 (4)	C23—H23B	0.9700
C9—H9	0.9800	C21—C22	1.505 (5)
O5—C21	1.200 (4)	C13—C14	1.343 (5)
O3—C20	1.358 (4)	C13—C15	1.504 (5)
O3—C8	1.470 (4)	C16—H16A	0.9600
C20—O4	1.207 (4)	C16—H16B	0.9600
C20—C10	1.526 (4)	C16—H16C	0.9600
C11—C10	1.535 (5)	C15—H15A	0.9600
C11—C12	1.540 (4)	C15—H15B	0.9600
C11—H11A	0.9700	C15—H15C	0.9600
C11—H11B	0.9700	C22—H22A	0.9600
C6—C5	1.356 (4)	C22—H22B	0.9600
C6—C7	1.516 (4)	C22—H22C	0.9600
C2—C1	1.544 (3)	C17—C18	1.386 (6)
C2—H2	0.9800	C17—C19	1.419 (6)
C1—C13	1.536 (4)	C19—H19A	0.9600
C1—C12	1.567 (4)	C19—H19B	0.9600
C1—H1	0.9800	C19—H19C	0.9600
C10—N1	1.555 (4)	C14—H14A	0.9300
N2—N1	1.241 (4)	C14—H14B	0.9300
N2—C23	1.493 (5)	C18—H18A	0.9300
C12—H12A	0.9700	C18—H18B	0.9300
C12—H12B	0.9700
C6—O2—C3	107.6 (2)	C7—C8—C9	115.8 (2)
C21—O1—C2	116.2 (2)	O3—C8—H8	108.2
C4—C3—O2	109.6 (2)	C7—C8—H8	108.2
C4—C3—C2	134.7 (2)	C9—C8—H8	108.2
O2—C3—C2	115.1 (2)	N2—N1—C10	112.6 (3)
C23—C9—C10	102.5 (2)	C6—C7—C17	115.3 (3)
C23—C9—C8	113.8 (3)	C6—C7—C8	113.0 (2)
C10—C9—C8	104.7 (2)	C17—C7—C8	111.9 (3)
C23—C9—H9	111.7	C6—C7—H7	105.2
C10—C9—H9	111.7	C17—C7—H7	105.2
C8—C9—H9	111.7	C8—C7—H7	105.2
C20—O3—C8	112.1 (2)	N2—C23—C9	105.6 (2)
O4—C20—O3	122.0 (3)	N2—C23—H23A	110.6
O4—C20—C10	127.3 (3)	C9—C23—H23A	110.6
O3—C20—C10	110.7 (3)	N2—C23—H23B	110.6
C10—C11—C12	118.1 (2)	C9—C23—H23B	110.6
C10—C11—H11A	107.8	H23A—C23—H23B	108.8
C12—C11—H11A	107.8	O5—C21—O1	123.1 (3)
C10—C11—H11B	107.8	O5—C21—C22	124.9 (3)
C12—C11—H11B	107.8	O1—C21—C22	112.0 (3)
H11A—C11—H11B	107.1	C14—C13—C15	122.3 (3)
C5—C6—O2	108.6 (2)	C14—C13—C1	119.4 (3)
C5—C6—C7	133.5 (3)	C15—C13—C1	118.3 (3)
O2—C6—C7	117.1 (2)	C4—C16—H16A	109.5
O1—C2—C3	110.6 (2)	C4—C16—H16B	109.5
O1—C2—C1	106.24 (18)	H16A—C16—H16B	109.5
C3—C2—C1	111.9 (2)	C4—C16—H16C	109.5
O1—C2—H2	109.3	H16A—C16—H16C	109.5
C3—C2—H2	109.3	H16B—C16—H16C	109.5
C1—C2—H2	109.3	C13—C15—H15A	109.5
C13—C1—C2	113.2 (2)	C13—C15—H15B	109.5
C13—C1—C12	110.6 (2)	H15A—C15—H15B	109.5
C2—C1—C12	110.7 (2)	C13—C15—H15C	109.5
C13—C1—H1	107.4	H15A—C15—H15C	109.5
C2—C1—H1	107.4	H15B—C15—H15C	109.5
C12—C1—H1	107.4	C21—C22—H22A	109.5
C20—C10—C11	115.3 (3)	C21—C22—H22B	109.5
C20—C10—C9	104.9 (2)	H22A—C22—H22B	109.5
C11—C10—C9	120.7 (2)	C21—C22—H22C	109.5
C20—C10—N1	104.9 (2)	H22A—C22—H22C	109.5
C11—C10—N1	106.8 (2)	H22B—C22—H22C	109.5
C9—C10—N1	102.5 (2)	C18—C17—C19	121.1 (5)
N1—N2—C23	112.4 (3)	C18—C17—C7	117.9 (5)
C11—C12—C1	115.9 (2)	C19—C17—C7	121.0 (3)
C11—C12—H12A	108.3	C17—C19—H19A	109.5
C1—C12—H12A	108.3	C17—C19—H19B	109.5
C11—C12—H12B	108.3	H19A—C19—H19B	109.5
C1—C12—H12B	108.3	C17—C19—H19C	109.5
H12A—C12—H12B	107.4	H19A—C19—H19C	109.5
C3—C4—C5	105.2 (2)	H19B—C19—H19C	109.5
C3—C4—C16	128.5 (3)	C13—C14—H14A	120.0
C5—C4—C16	126.2 (3)	C13—C14—H14B	120.0
C6—C5—C4	108.9 (2)	H14A—C14—H14B	120.0
C6—C5—H5	125.5	C17—C18—H18A	120.0
C4—C5—H5	125.5	C17—C18—H18B	120.0
O3—C8—C7	109.7 (2)	H18A—C18—H18B	120.0
O3—C8—C9	106.6 (2)
C6—O2—C3—C4	1.6 (3)	C2—C3—C4—C16	−8.9 (5)
C6—O2—C3—C2	−170.6 (2)	O2—C6—C5—C4	0.2 (3)
C8—O3—C20—O4	179.1 (3)	C7—C6—C5—C4	−168.9 (3)
C8—O3—C20—C10	−3.5 (3)	C3—C4—C5—C6	0.7 (3)
C3—O2—C6—C5	−1.1 (3)	C16—C4—C5—C6	178.4 (3)
C3—O2—C6—C7	170.1 (2)	C20—O3—C8—C7	−129.1 (3)
C21—O1—C2—C3	−87.0 (3)	C20—O3—C8—C9	−2.9 (3)
C21—O1—C2—C1	151.3 (2)	C23—C9—C8—O3	119.0 (3)
C4—C3—C2—O1	106.3 (3)	C10—C9—C8—O3	7.9 (3)
O2—C3—C2—O1	−84.0 (2)	C23—C9—C8—C7	−118.6 (3)
C4—C3—C2—C1	−135.4 (3)	C10—C9—C8—C7	130.2 (3)
O2—C3—C2—C1	34.2 (3)	C23—N2—N1—C10	−0.7 (4)
O1—C2—C1—C13	−57.6 (3)	C20—C10—N1—N2	122.8 (3)
C3—C2—C1—C13	−178.4 (2)	C11—C10—N1—N2	−114.3 (3)
O1—C2—C1—C12	177.6 (2)	C9—C10—N1—N2	13.5 (4)
C3—C2—C1—C12	56.7 (3)	C5—C6—C7—C17	−99.1 (4)
O4—C20—C10—C11	−39.2 (4)	O2—C6—C7—C17	92.5 (3)
O3—C20—C10—C11	143.7 (2)	C5—C6—C7—C8	130.4 (3)
O4—C20—C10—C9	−174.4 (3)	O2—C6—C7—C8	−38.0 (4)
O3—C20—C10—C9	8.4 (3)	O3—C8—C7—C6	74.9 (3)
O4—C20—C10—N1	78.0 (4)	C9—C8—C7—C6	−45.8 (4)
O3—C20—C10—N1	−99.2 (3)	O3—C8—C7—C17	−57.2 (3)
C12—C11—C10—C20	−74.1 (3)	C9—C8—C7—C17	−178.0 (3)
C12—C11—C10—C9	53.6 (3)	N1—N2—C23—C9	−12.6 (4)
C12—C11—C10—N1	169.9 (2)	C10—C9—C23—N2	19.6 (3)
C23—C9—C10—C20	−128.7 (3)	C8—C9—C23—N2	−92.8 (3)
C8—C9—C10—C20	−9.6 (3)	C2—O1—C21—O5	−2.4 (5)
C23—C9—C10—C11	99.1 (3)	C2—O1—C21—C22	175.7 (3)
C8—C9—C10—C11	−141.8 (2)	C2—C1—C13—C14	137.6 (3)
C23—C9—C10—N1	−19.3 (3)	C12—C1—C13—C14	−97.6 (3)
C8—C9—C10—N1	99.8 (2)	C2—C1—C13—C15	−44.3 (3)
C10—C11—C12—C1	76.3 (3)	C12—C1—C13—C15	80.6 (3)
C13—C1—C12—C11	85.8 (3)	C6—C7—C17—C18	136.5 (5)
C2—C1—C12—C11	−147.9 (2)	C8—C7—C17—C18	−92.6 (5)
O2—C3—C4—C5	−1.4 (3)	C6—C7—C17—C19	−44.7 (5)
C2—C3—C4—C5	168.6 (3)	C8—C7—C17—C19	86.2 (5)
O2—C3—C4—C16	−178.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O5i	0.98	2.37	3.281 (4)	154.
C9—H9···O4ii	0.98	2.52	3.319 (4)	139.
C16—H16A···O5	0.96	2.54	3.347 (5)	142.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O5i	0.98	2.37	3.281 (4)	154
C9—H9⋯O4ii	0.98	2.52	3.319 (4)	139
C16—H16A⋯O5	0.96	2.54	3.347 (5)	142

Symmetry codes: (i) ; (ii) .