Rotenone [alpha]-oxime

The structure determination of the title compound, rotenone [alpha]-oxime [systematic name: 1,2,12,12a-tetra­hydro-8,9-di­meth­oxy-2-(1-methyl­ethenyl)-[1]­benzo­py­rano­[3,4-b]­furo­[2,3-h][1]benzo­pyran-6(6H)-one oxime], C₂₃H₂₃NO₆, confirms that the mol­ecule has an approximately V-shaped structure. One of the rings has a typical cyclo­hexene-like monoplanar conformation and the central ring adopts a 1,2-diplanar conformation.

S1. Comment

Rotenone, a naturally occurring heterocyclic compound with inhibitory effects on oxidative phosphorylation and mitosis, is obtained from the roots of the legumes Derris elliptical and D. malaccensis in Malaysia, and D. Uruco and Lonchocarpus utilis in South America (McEwen et al., 1979; Ware, 1983). Rotenone is a widely used pesticide (Carson, 1962; Gosalvenz, 1983; Haley, 1978), and together with other botanical pesticides (e.g. pyrethrum, sabadilla, nicotine and ryania), it is a valuable alternative to the synthetic pesticides in use today. Some insects have developed resistance in response to the heavy use of synthetic pesticides. In contrast, botanical pesticides exert their action through a variety of biochemical lesions and, therefore, can control neurotoxicant resistant insects. Additionally, as naturally occurring substances, botanical pesticides appear to be metabolized to less toxic derivatives. For rotenone, these are the polar rotenolones and hydroxyrotenone (Fukami et al., 1967). It photochemically decomposes to form over 20 degradation products, including rotenoids, rotenolones and rotenonone, and their expoxides (Carson, 1962; Engstrom-Heg et al., 1979; Fukami et., 1967; Gosalvez, 1983; Haley, 1978; Newsome et al., 1980; O'Brine, 1967).

Rotenone is biochemically very active, exerting its effects mainly by blocking oxidative phosphorylation and/or mitosis in cells through apparently separate pathways (Loffler et al., 1982). Information on the mode of action and selectivity of rotenone is important so that it can be used safely and efficiently. Since the three-dimensional structure of most biologically active molecules plays a role in governing their interactions and activities, in the course of a systematic study of the relation between structure and bioactivity of rotenone, we have isolated the title compound, rotenone-α-oxime, (I), C₂₃H₂₃NO₆, and we report here its preparation and structure.

Fig. 1 shows the molecule with the atom-numbering scheme. Except for the isopropenyl group, the non-H atoms lie close to the plane of aromatic rings I and IV, resulting in an approximately V-shaped molecule with an angle of 78.7° between the planes of rings I and IV. Ring II has a typical cyclohexene-like monoplanar conformation (Bucourt, 1974), with torsion angles, proceeding anticlockwise? (see Fig. 1) around the ring starting from the C14—C13—03—C12 angle, of −10.0 (4), −36.4 (4), −55.2 (4), 46.4 (3), 23.2 (4) and 4.3 (5)°. Ring III adopts a 1,2-diplanar conformation (Bucourt, 1974), with torsion angles, proceeding anticlockwise? (see Fig. 1) starting with the C2—C3—O1—C4 angle, of −46.4 (3), 20.6 (4), 1.4 (5), 9.9 (4), 34.7 (4), −52.6 (3)°. The torsion angles in the five-membered ring, V, proceeding anticlockwise? (see Fig. 1) from the C8—C9—C10—C11 angle, are −13.1 (3), 18.9 (3), 18.7 (3), 10.9 (4) and 1.9 (4)°, indicating an envelope conformation (Bucourt, 1974) with the isopropenyl group in an equatorial position, as proposed previously by Büchi, et al. (1961) and Carlson et al. (1973). The methoxyl groups are noncoplanar with ring I; the angles between the plane of ring I and planes C20—O5—C17 and C19—O4—C16 are 12.5 and 73.1°, respectively.

The packing of (I) is shown in a stereo diagram in Fig. 2. The molecules are able to fit together tightly, maximizing intermolecular interaction through hydrogen bonds between the hydroxyl group of the rotenone-α-oxime group and the O atom of ring V [O6—O2ⁱ = 2.997 (4) Å, O6—H20 = 0.820 Å, H20—O2ⁱ = 2.197 Å, O6—H20—O2ⁱ = 165.1°; symmetry codes: (i) −x + 3/2,-y + 1,z + 1/2].

S2. Experimental

Rotenone (5 g), hydroxylamine hydrochloride (5 g) and sodium acetate (6 g) in ethyl alcohol (200 cm³) were refluxed for 10 h, and then water was added until crystallization commenced. The resulting rotenone-oxime was crystallized from alcohol, and a single-crystal suitable for X-ray analysis was recrystallized from ethyl alcohol after two months.

S3. Refinement

The absolute structure of (I) was not determined. The initial material, rotenone, was the basis of the configuration (Rossi et al., 1988). Atoms C22 and C23 of the isopropenyl group were disordered; the occupancy factors for atoms C22 and C23 were accordingly reduced and their secondary positions, C22' and C23', were included. The occupancy factors for C22/C23 and C22'/C23' were 0.667 and 1/3, respectively. H-atom occupancy factors were consistent with those of the corresponding C atoms.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998) and SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the structure of (I), showing the atom-numbering scheme (Bruker, 1998). Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. A perspective view of the molecular packing of rotenone-α-oxime, viewed along the a axis

1,2,12,12a-tetrahydro-8,9-dimethoxy-2-(1-methylethenyl)- [1]benzopyrano[3,4-b]furo[2,3-h][1]benzopyran-6(6H)-one oxime

Crystal data

C23H23NO6	Dx = 1.354 Mg m^−3
Mr = 409.42	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 2303 reflections
a = 9.3994 (10) Å	θ = 5.1–44.3°
b = 14.4249 (15) Å	µ = 0.10 mm^−1
c = 14.8129 (15) Å	T = 293 K
V = 2008.4 (4) Å^3	Block, colourless
Z = 4	0.58 × 0.40 × 0.36 mm
F(000) = 864

Data collection

CCD area detector diffractometer	4704 independent reflections
Radiation source: fine-focus sealed tube	2808 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ϕ and ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements) SADABS absorption based on ϕ and ω scans (Bruker, 1998)	h = −12→12
Tmin = 0.865, Tmax = 1.000	k = −19→19
12340 measured reflections	l = −10→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.176	H-atom parameters constrained
S = 0.92	Calculated w = 1/[σ^2(Fo^2) + (0.0983P)^2] where P = (Fo^2 + 2Fc^2)/3
4704 reflections	(Δ/σ)max = 0.006
277 parameters	Δρmax = 0.45 e Å^−3
29 restraints	Δρmin = −0.52 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.6503 (2)	0.23309 (13)	0.40322 (14)	0.0414 (5)
O2	0.4105 (3)	0.42961 (16)	0.20925 (16)	0.0578 (7)
O3	0.6491 (3)	0.10248 (14)	0.55298 (15)	0.0474 (6)
O4	0.4778 (3)	0.36803 (18)	0.79789 (15)	0.0575 (7)
O5	0.3752 (3)	0.19250 (17)	0.80945 (16)	0.0591 (7)
O6	0.9159 (4)	0.4260 (3)	0.6143 (3)	0.1151 (13)
H6A	0.9562	0.4723	0.6336	0.173*
N1	0.8257 (3)	0.45078 (19)	0.54257 (18)	0.0504 (8)
C1	0.7683 (3)	0.3842 (2)	0.5071 (2)	0.0387 (7)
C2	0.7814 (3)	0.2848 (2)	0.5396 (2)	0.0400 (7)
C3	0.7751 (4)	0.2172 (2)	0.4598 (2)	0.0400 (7)
C4	0.6219 (3)	0.3223 (2)	0.38031 (19)	0.0350 (7)
C5	0.6752 (4)	0.3992 (2)	0.4291 (2)	0.0400 (8)
C6	0.6347 (4)	0.4882 (2)	0.4015 (2)	0.0525 (9)
H6	0.6698	0.5391	0.4329	0.063*
C7	0.5452 (4)	0.5028 (2)	0.3298 (2)	0.0578 (10)
H7	0.5192	0.5624	0.3124	0.069*
C8	0.4942 (4)	0.4251 (2)	0.2839 (2)	0.0455 (8)
C9	0.5322 (3)	0.3365 (2)	0.3080 (2)	0.0398 (7)
C10	0.4700 (4)	0.2713 (2)	0.2392 (2)	0.0463 (8)
H10A	0.4217	0.2197	0.2679	0.056*
H10B	0.5427	0.2476	0.1988	0.056*
C11	0.3649 (4)	0.3343 (2)	0.1888 (2)	0.0518 (9)
C12	0.7646 (4)	0.1198 (2)	0.4931 (2)	0.0441 (8)
H12A	0.7557	0.0789	0.4415	0.053*
H12B	0.8525	0.1042	0.5238	0.053*
C13	0.6131 (3)	0.1715 (2)	0.61266 (19)	0.0363 (7)
C14	0.6674 (3)	0.2598 (2)	0.60868 (19)	0.0368 (7)
C15	0.6176 (3)	0.3242 (2)	0.6713 (2)	0.0402 (7)
H15	0.6520	0.3847	0.6690	0.048*
C16	0.5197 (4)	0.3016 (2)	0.7363 (2)	0.0429 (8)
C17	0.4687 (4)	0.2100 (2)	0.7409 (2)	0.0448 (8)
C18	0.5135 (4)	0.1458 (2)	0.6784 (2)	0.0413 (7)
H18	0.4775	0.0858	0.6798	0.050*
C19	0.3383 (4)	0.4028 (3)	0.7860 (3)	0.0732 (12)
H19A	0.3315	0.4322	0.7280	0.110*
H19B	0.3176	0.4472	0.8325	0.110*
H19C	0.2713	0.3527	0.7893	0.110*
C20	0.3421 (5)	0.0970 (3)	0.8281 (3)	0.0711 (12)
H20A	0.3045	0.0683	0.7747	0.107*
H20B	0.2728	0.0939	0.8756	0.107*
H20C	0.4269	0.0651	0.8465	0.107*
C21	0.3621 (5)	0.3226 (3)	0.0903 (2)	0.0650 (11)
C22	0.4512 (16)	0.3683 (13)	0.0332 (14)	0.140 (7)	0.67
H22A	0.5149	0.4128	0.0594	0.080*	0.67
H22B	0.4484	0.3602	−0.0311	0.080*	0.67
C22'	0.479 (4)	0.328 (3)	0.038 (3)	0.140 (7)	0.33
H22C	0.5688	0.3483	0.0620	0.080*	0.33
H22D	0.4690	0.3184	−0.0260	0.080*	0.33
C23	0.2313 (13)	0.2932 (11)	0.0563 (9)	0.206 (8)	0.67
H23D	0.2334	0.2861	−0.0081	0.080*	0.67
H23E	0.1988	0.2367	0.0836	0.080*	0.67
H23F	0.1678	0.3428	0.0720	0.080*	0.67
C23'	0.2866 (17)	0.2443 (12)	0.0591 (15)	0.206 (8)	0.33
H23A	0.2913	0.2424	−0.0057	0.080*	0.33
H23B	0.3222	0.1871	0.0833	0.080*	0.33
H23C	0.1896	0.2527	0.0776	0.080*	0.33
H2	0.9019	0.2781	0.5679	0.120*
H3	0.8720	0.2201	0.4226	0.120*
H11	0.2701	0.3299	0.2074	0.120*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0562 (14)	0.0328 (11)	0.0350 (11)	−0.0007 (10)	−0.0055 (10)	0.0016 (9)
O2	0.0777 (17)	0.0505 (14)	0.0450 (14)	0.0066 (13)	−0.0133 (13)	0.0076 (11)
O3	0.0639 (16)	0.0364 (11)	0.0418 (13)	0.0019 (11)	0.0094 (11)	0.0008 (10)
O4	0.0607 (16)	0.0722 (16)	0.0397 (13)	−0.0004 (13)	0.0083 (12)	−0.0148 (11)
O5	0.0664 (16)	0.0624 (15)	0.0483 (14)	−0.0036 (13)	0.0214 (13)	0.0106 (12)
O6	0.145 (3)	0.096 (3)	0.104 (3)	−0.015 (2)	−0.003 (3)	−0.014 (2)
N1	0.066 (2)	0.0467 (16)	0.0386 (16)	−0.0062 (15)	−0.0174 (15)	−0.0058 (13)
C1	0.0428 (19)	0.0373 (17)	0.0361 (17)	−0.0032 (14)	0.0055 (15)	−0.0050 (14)
C2	0.0397 (18)	0.0419 (17)	0.0383 (17)	−0.0002 (14)	0.0035 (15)	0.0010 (14)
C3	0.0450 (19)	0.0392 (17)	0.0359 (17)	0.0017 (14)	0.0000 (15)	−0.0001 (14)
C4	0.0429 (17)	0.0342 (15)	0.0280 (15)	0.0007 (13)	0.0073 (13)	0.0018 (12)
C5	0.0514 (19)	0.0348 (16)	0.0338 (17)	0.0002 (14)	0.0075 (15)	0.0051 (13)
C6	0.072 (3)	0.0371 (18)	0.048 (2)	−0.0015 (17)	−0.0037 (19)	−0.0037 (15)
C7	0.089 (3)	0.0357 (18)	0.048 (2)	0.0100 (19)	−0.001 (2)	0.0060 (16)
C8	0.057 (2)	0.0463 (19)	0.0331 (16)	0.0023 (16)	0.0008 (16)	0.0061 (14)
C9	0.0472 (18)	0.0384 (16)	0.0336 (16)	−0.0022 (14)	0.0077 (15)	0.0005 (13)
C10	0.064 (2)	0.0430 (18)	0.0318 (16)	−0.0031 (16)	0.0043 (16)	0.0029 (14)
C11	0.059 (2)	0.058 (2)	0.0389 (18)	−0.0035 (18)	−0.0027 (17)	0.0060 (16)
C12	0.049 (2)	0.0417 (18)	0.0416 (19)	0.0037 (15)	0.0028 (16)	0.0000 (15)
C13	0.0426 (17)	0.0377 (16)	0.0287 (15)	0.0018 (14)	−0.0023 (14)	0.0041 (13)
C14	0.0411 (18)	0.0395 (17)	0.0298 (15)	0.0044 (14)	−0.0015 (14)	−0.0008 (13)
C15	0.0454 (18)	0.0426 (17)	0.0326 (16)	0.0003 (14)	−0.0031 (14)	−0.0001 (14)
C16	0.0462 (18)	0.054 (2)	0.0290 (15)	0.0012 (16)	0.0000 (15)	−0.0077 (14)
C17	0.0399 (18)	0.061 (2)	0.0332 (16)	−0.0011 (16)	0.0070 (15)	0.0077 (15)
C18	0.050 (2)	0.0363 (16)	0.0381 (16)	0.0004 (14)	0.0012 (16)	0.0067 (13)
C19	0.061 (3)	0.069 (3)	0.089 (3)	0.013 (2)	−0.001 (2)	−0.026 (2)
C20	0.078 (3)	0.072 (3)	0.063 (3)	−0.003 (2)	0.013 (2)	0.023 (2)
C21	0.083 (3)	0.077 (3)	0.036 (2)	−0.008 (2)	−0.009 (2)	0.0046 (19)
C22	0.130 (8)	0.252 (19)	0.039 (3)	−0.078 (10)	−0.005 (6)	0.018 (9)
C22'	0.130 (8)	0.252 (19)	0.039 (3)	−0.078 (10)	−0.005 (6)	0.018 (9)
C23	0.261 (14)	0.30 (2)	0.061 (4)	−0.091 (15)	−0.010 (8)	0.010 (9)
C23'	0.261 (14)	0.30 (2)	0.061 (4)	−0.091 (15)	−0.010 (8)	0.010 (9)

Geometric parameters (Å, º)

O1—C4	1.357 (3)	C13—C18	1.401 (4)
O1—C3	1.460 (4)	C14—C15	1.394 (4)
O2—C8	1.358 (4)	C15—C16	1.372 (4)
O2—C11	1.472 (4)	C15—H15	0.9300
O3—C13	1.374 (4)	C16—C17	1.408 (5)
O3—C12	1.423 (4)	C17—C18	1.375 (5)
O4—C16	1.380 (4)	C18—H18	0.9300
O4—C19	1.414 (4)	C19—H19A	0.9599
O5—C17	1.366 (4)	C19—H19B	0.9600
O5—C20	1.439 (5)	C19—H19C	0.9600
O6—N1	1.406 (4)	C20—H20A	0.9599
O6—H6A	0.8200	C20—H20B	0.9601
N1—C1	1.221 (4)	C20—H20C	0.9600
C1—C5	1.465 (4)	C21—C22'	1.351 (10)
C1—C2	1.517 (4)	C21—C22	1.361 (8)
C2—C14	1.525 (4)	C21—C23'	1.412 (9)
C2—C3	1.534 (4)	C21—C23	1.395 (9)
C2—H2	1.2107	C22—C22'	0.65 (5)
C3—C12	1.492 (4)	C22—H22A	0.9600
C3—H3	1.0655	C22—H22B	0.9600
C4—C9	1.379 (4)	C22—H22C	1.2196
C4—C5	1.416 (4)	C22—H22D	1.1467
C5—C6	1.401 (4)	C22'—H22A	1.3116
C6—C7	1.371 (5)	C22'—H22B	1.1608
C6—H6	0.9300	C22'—H22C	0.9600
C7—C8	1.397 (5)	C22'—H22D	0.9599
C7—H7	0.9301	C23—C23'	0.88 (3)
C8—C9	1.373 (4)	C23—H23D	0.9600
C9—C10	1.505 (4)	C23—H23E	0.9600
C10—C11	1.536 (5)	C23—H23F	0.9600
C10—H10A	0.9699	C23—H23A	1.3029
C10—H10B	0.9699	C23—H23C	0.7708
C11—C21	1.469 (5)	C23'—H23D	1.2659
C11—H11	0.9345	C23'—H23E	0.9082
C12—H12A	0.9700	C23'—H23A	0.9599
C12—H12B	0.9701	C23'—H23B	0.9600
C13—C14	1.373 (4)	C23'—H23C	0.9599
C4—O1—C3	116.8 (2)	O5—C20—H20C	109.5
C8—O2—C11	107.0 (2)	H20A—C20—H20C	109.5
C13—O3—C12	117.5 (2)	H20B—C20—H20C	109.5
C16—O4—C19	115.4 (3)	C22'—C21—C22	28 (2)
C17—O5—C20	117.3 (3)	C22'—C21—C23'	105 (2)
N1—O6—H6A	109.5	C22—C21—C23'	119.6 (14)
C1—N1—O6	113.1 (3)	C22'—C21—C23	122 (3)
N1—C1—C5	119.2 (3)	C22—C21—C23	117.8 (13)
N1—C1—C2	124.8 (3)	C23'—C21—C23	36.4 (12)
C5—C1—C2	116.0 (3)	C22'—C21—C11	123 (3)
C1—C2—C14	112.3 (3)	C22—C21—C11	123.4 (12)
C1—C2—C3	110.6 (3)	C23'—C21—C11	115.2 (9)
C14—C2—C3	109.8 (2)	C23—C21—C11	114.1 (7)
C1—C2—H2	105.2	C22'—C22—C21	75.4 (16)
C14—C2—H2	114.0	C22'—C22—H22A	107.8
C3—C2—H2	104.5	C21—C22—H22A	117.2
O1—C3—C12	106.5 (3)	C22'—C22—H22B	90.3
O1—C3—C2	112.0 (2)	C21—C22—H22B	122.7
C12—C3—C2	110.2 (3)	H22A—C22—H22B	120.0
O1—C3—H3	112.6	C22'—C22—H22C	51.4
C12—C3—H3	105.3	C21—C22—H22C	103.0
C2—C3—H3	110.0	H22A—C22—H22C	56.7
O1—C4—C9	117.2 (3)	H22B—C22—H22C	110.1
O1—C4—C5	123.0 (3)	C22'—C22—H22D	56.8
C9—C4—C5	119.8 (3)	C21—C22—H22D	105.1
C6—C5—C4	118.2 (3)	H22A—C22—H22D	129.6
C6—C5—C1	121.9 (3)	H22B—C22—H22D	33.8
C4—C5—C1	119.9 (3)	H22C—C22—H22D	89.2
C7—C6—C5	122.3 (3)	C22—C22'—C21	77.0 (15)
C7—C6—H6	118.9	C22—C22'—H22A	44.2
C5—C6—H6	118.8	C21—C22'—H22A	96.8
C6—C7—C8	117.6 (3)	C22—C22'—H22B	55.8
C6—C7—H7	121.2	C21—C22'—H22B	108.8
C8—C7—H7	121.2	H22A—C22'—H22B	84.3
O2—C8—C9	114.0 (3)	C22—C22'—H22C	96.8
O2—C8—C7	123.8 (3)	C21—C22'—H22C	121.1
C9—C8—C7	122.1 (3)	H22A—C22'—H22C	52.9
C8—C9—C4	120.0 (3)	H22B—C22'—H22C	115.0
C8—C9—C10	107.7 (3)	C22—C22'—H22D	88.8
C4—C9—C10	132.1 (3)	C21—C22'—H22D	118.4
C9—C10—C11	102.1 (3)	H22A—C22'—H22D	113.4
C9—C10—H10A	111.4	H22B—C22'—H22D	33.3
C11—C10—H10A	111.5	H22C—C22'—H22D	120.0
C9—C10—H10B	111.3	C23'—C23—C21	72.9 (11)
C11—C10—H10B	111.2	C23'—C23—H23D	87.0
H10A—C10—H10B	109.3	C21—C23—H23D	111.9
O2—C11—C21	108.5 (3)	C23'—C23—H23E	59.0
O2—C11—C10	105.3 (3)	C21—C23—H23E	112.8
C21—C11—C10	115.2 (3)	H23D—C23—H23E	109.5
O2—C11—H11	106.3	C23'—C23—H23F	163.0
C21—C11—H11	105.6	C21—C23—H23F	103.6
C10—C11—H11	115.4	H23D—C23—H23F	109.5
O3—C12—C3	115.0 (3)	H23E—C23—H23F	109.5
O3—C12—H12A	108.6	C23'—C23—H23A	47.5
C3—C12—H12A	108.5	C21—C23—H23A	92.5
O3—C12—H12B	108.5	H23D—C23—H23A	39.7
C3—C12—H12B	108.5	H23E—C23—H23A	87.5
H12A—C12—H12B	107.6	H23F—C23—H23A	149.1
O3—C13—C14	123.6 (3)	C23'—C23—H23C	70.9
O3—C13—C18	114.9 (3)	C21—C23—H23C	122.1
C14—C13—C18	121.5 (3)	H23D—C23—H23C	109.7
C13—C14—C15	117.7 (3)	H23E—C23—H23C	12.1
C13—C14—C2	120.6 (3)	H23F—C23—H23C	98.6
C15—C14—C2	121.6 (3)	H23A—C23—H23C	94.7
C16—C15—C14	122.2 (3)	C23—C23'—C21	70.7 (10)
C16—C15—H15	118.8	C23—C23'—H23D	49.2
C14—C15—H15	119.0	C21—C23'—H23D	94.3
C15—C16—O4	119.4 (3)	C23—C23'—H23E	65.0
C15—C16—C17	119.1 (3)	C21—C23'—H23E	115.0
O4—C16—C17	121.5 (3)	H23D—C23'—H23E	90.8
O5—C17—C18	125.0 (3)	C23—C23'—H23A	90.2
O5—C17—C16	115.3 (3)	C21—C23'—H23A	109.1
C18—C17—C16	119.7 (3)	H23D—C23'—H23A	41.1
C17—C18—C13	119.7 (3)	H23E—C23'—H23A	115.9
C17—C18—H18	120.1	C23—C23'—H23B	156.2
C13—C18—H18	120.2	C21—C23'—H23B	112.9
O4—C19—H19A	109.3	H23D—C23'—H23B	147.2
O4—C19—H19B	109.6	H23E—C23'—H23B	93.6
H19A—C19—H19B	109.5	H23A—C23'—H23B	109.5
O4—C19—H19C	109.5	C23—C23'—H23C	49.4
H19A—C19—H19C	109.5	C21—C23'—H23C	106.4
H19B—C19—H19C	109.5	H23D—C23'—H23C	77.9
O5—C20—H20A	109.5	H23E—C23'—H23C	15.8
O5—C20—H20B	109.4	H23A—C23'—H23C	109.5
H20A—C20—H20B	109.5	H23B—C23'—H23C	109.5
O6—N1—C1—C5	−177.8 (3)	C12—O3—C13—C14	10.0 (4)
O6—N1—C1—C2	4.4 (5)	C12—O3—C13—C18	−171.0 (3)
N1—C1—C2—C14	89.4 (4)	O3—C13—C14—C15	177.5 (3)
C5—C1—C2—C14	−88.4 (3)	C18—C13—C14—C15	−1.4 (4)
N1—C1—C2—C3	−147.5 (3)	O3—C13—C14—C2	−4.3 (5)
C5—C1—C2—C3	34.7 (4)	C18—C13—C14—C2	176.8 (3)
C4—O1—C3—C12	167.0 (2)	C1—C2—C14—C13	146.8 (3)
C4—O1—C3—C2	46.4 (3)	C3—C2—C14—C13	23.2 (4)
C1—C2—C3—O1	−52.6 (3)	C1—C2—C14—C15	−35.1 (4)
C14—C2—C3—O1	72.0 (3)	C3—C2—C14—C15	−158.6 (3)
C1—C2—C3—C12	−170.9 (3)	C13—C14—C15—C16	1.1 (5)
C14—C2—C3—C12	−46.4 (3)	C2—C14—C15—C16	−177.1 (3)
C3—O1—C4—C9	161.9 (3)	C14—C15—C16—O4	178.2 (3)
C3—O1—C4—C5	−20.6 (4)	C14—C15—C16—C17	0.8 (5)
O1—C4—C5—C6	−177.6 (3)	C19—O4—C16—C15	107.7 (4)
C9—C4—C5—C6	−0.2 (4)	C19—O4—C16—C17	−74.9 (4)
O1—C4—C5—C1	1.4 (5)	C20—O5—C17—C18	12.3 (5)
C9—C4—C5—C1	178.8 (3)	C20—O5—C17—C16	−167.9 (3)
N1—C1—C5—C6	−8.8 (5)	C15—C16—C17—O5	177.8 (3)
C2—C1—C5—C6	169.2 (3)	O4—C16—C17—O5	0.4 (5)
N1—C1—C5—C4	172.2 (3)	C15—C16—C17—C18	−2.4 (5)
C2—C1—C5—C4	−9.9 (4)	O4—C16—C17—C18	−179.8 (3)
C4—C5—C6—C7	0.4 (5)	O5—C17—C18—C13	−178.1 (3)
C1—C5—C6—C7	−178.6 (3)	C16—C17—C18—C13	2.1 (5)
C5—C6—C7—C8	0.0 (5)	O3—C13—C18—C17	−179.2 (3)
C11—O2—C8—C9	10.9 (4)	C14—C13—C18—C17	−0.2 (5)
C11—O2—C8—C7	−172.7 (3)	O2—C11—C21—C22'	64 (2)
C6—C7—C8—O2	−176.8 (3)	C10—C11—C21—C22'	−54 (2)
C6—C7—C8—C9	−0.7 (5)	O2—C11—C21—C22	30.9 (9)
O2—C8—C9—C4	177.3 (3)	C10—C11—C21—C22	−86.8 (9)
C7—C8—C9—C4	0.9 (5)	O2—C11—C21—C23'	−164.4 (10)
O2—C8—C9—C10	1.9 (4)	C10—C11—C21—C23'	77.9 (11)
C7—C8—C9—C10	−174.5 (3)	O2—C11—C21—C23	−124.1 (8)
O1—C4—C9—C8	177.1 (3)	C10—C11—C21—C23	118.1 (9)
C5—C4—C9—C8	−0.4 (4)	C23'—C21—C22—C22'	−65 (8)
O1—C4—C9—C10	−8.7 (5)	C23—C21—C22—C22'	−106 (7)
C5—C4—C9—C10	173.7 (3)	C11—C21—C22—C22'	99 (8)
C8—C9—C10—C11	−13.1 (3)	C23'—C21—C22'—C22	125 (7)
C4—C9—C10—C11	172.3 (3)	C23—C21—C22'—C22	90 (7)
C8—O2—C11—C21	−142.6 (3)	C11—C21—C22'—C22	−99 (7)
C8—O2—C11—C10	−18.7 (3)	C22'—C21—C23—C23'	72 (3)
C9—C10—C11—O2	18.9 (3)	C22—C21—C23—C23'	103 (2)
C9—C10—C11—C21	138.4 (3)	C11—C21—C23—C23'	−100 (2)
C13—O3—C12—C3	−36.4 (4)	C22'—C21—C23'—C23	−123 (3)
O1—C3—C12—O3	−66.4 (3)	C22—C21—C23'—C23	−98 (2)
C2—C3—C12—O3	55.2 (4)	C11—C21—C23'—C23	97 (2)