Methyl 2,3,6-tri-O-benzoyl-4-deoxy-4-methoxy­amino-[alpha]-D-gluco­pyran­oside

The crystalline-state conformation of the title compound, C₂₉H₂₉NO₉, has been established unequivocally. The R absolute configuration is observed at the 4-methoxy­amino moiety and the pyranose ring adopts essentially a perfect ⁴C₁ chair. The torsion angle of the exocyclic hydroxy­methyl group is shown to be gauche-gauche with respect to O1 and C4, respectively. The conformation along the methoxy­amino bond is consistent with that observed for calicheamicin [gamma]₁^I.

S1. Comment

Hydroxylamine-substituted sugars are found in an important class of antitumor antibiotic, such as calicheamicin or esperamicin that cleaves DNA specifically (Nicolaou & Dai, 1991). Conformational study has demonstrated a key role for this unusual N—O linkage in maintaining the oligosaccharide core in the minor groove of the DNA (Walker et al., 1994). In this context, the structure of sugars containing the hydroxylamine linkage, such as the title compound, (I), are of interest to assess and validate the latter theoretical studies. Reduction of methyl 2,3,6-tri-O-benzoyl-4-deoxy-4-methoxyimino-α-D-xylo-hexopyranoside with NaBH₃CN at pH = 3 afforded a mixture of the corresponding gluco- and galacto-methoxyamino diastereoisomers. Recrystallization of the mixture from diethyl ether/petroleum ether allowed the separation of each epimer. The structure of (I) displays interatomic bond distances and angles (Table 1) in good agreement with those given by Allen et al. (1987). The configuration at C4 is R, which implies the gluco configuration. The ring adops a quasi-perfect ⁴C₁ chair conformation, as defined by the Cremer & Pople (1975) parameters, Q = 0.593 (3) Å, Θ = 2.6 (2)° and Φ₂ = 195 (4)°. This conformation is also adopted in solution, as outlined by the large values of the coupling constant (~10 Hz) in NMR. The exocyclic hydroxymethyl group adopted a staggered gg conformation [ω = O5—C5—C6—O6 = -70.1 (2)°, C4—C5—C6—O6 = -52.5 (2)°], which is the conformation usually observed in other structures containing gluco residues (Marchessault & Pérez, 1979).

The α (C3—C4—N4—O4) and β (C22—O4—N4—C4) torsion angles have values of -51.6 (2) and -160.6 (2)°, respectively, close to those of the global minimum calculated by Walker et al. (1994). However, the β value is decreased in comparison with the value of -120° calculated by Walker et al. (1994) in monosaccharide, as well as in comparison with the value of -134° reported by Lee et al. (1987) for the crystal structure of calicheamicin γ₁^I derivative. Moreover, NMR measurements in chloroform indicated a small value of ³J'_4,NH (2.1 Hz) for the hydroxylamino H atom, which is consistent with an average conformation in which the hydroxylamine H atom is gauche to the C4 H atom.

Two kinds of hydrogen bonds co-exist in the stucture. The first assumes the crystal packing, forming an infinite chain of molecules running along the b axis. The second is intramolecular, linking the N4 atom to the benzoyl O3 atom. The hydrogen-bond details are given in Table 2.

Related literature

For related literature, see: Allen et al. (1987); Borch et al. (1971); Cremer & Pople (1975); Lee et al. (1987); Marchessault & Pérez (1979); Nicolaou & Dai (1991); Tronchet et al. (1989); Walker et al. (1994).

S2. Experimental

The title compound was prepared after reduction of methyl 2,3,6-tri-O-benzoyl-4-deoxy-4-methoxyimino-α-D-xylo-hexopyranoside (Tronchet et al., 1989) using sodium cyanoborohydride (Borch et al., 1971) with careful control of pH (optimum value = 3). The corresponding gluco- and galacto-methoxyamino diastereoisomers were separated by liquid chromatography and recrystallization was from diethyl ether/petroleum ether (m.p. 396 K). ¹H NMR (300 MHz, CDCl₃, p.p.m.): δ 8.12–7.34 (m, 15H, aromatic H), 6.17 (t, 1H, ³J_2,3 = ³J_3,4 = 10.0 Hz, H3), 5.91 (d, 1H, ³J_4,NH = 2.1 Hz, H21), 5.20 (dd, 1H, ³J_1,2 = 3.6 Hz, H2), 5.16 (d, 1H, H1), 4.76–4.72 (m, 2H, H6, H7), 4.42 (td, 1H, ³J_5,6 = 3.6 Hz, ³J_4,5 = 10.3 Hz, H5), 3.51 (s, 3H, H8, H9, H10), 3.44 (s, 3H, H22, H23, H24) 3.19 (bt, 1H, H4); ¹³C NMR (p.p.m): δ 166.7 (C═O), 166.2 (C═O), 166.0 (C═O), 133.4 [aromatic C (C_ar)], 133.3 (C_ar), 130.1 (C_ar), 129.9 (C_ar), 129.7 (C_ar), 129.3 (C_ar), 128.6 (C_ar), 128.5 (C_ar), 97.2 (C1), 73.3 (C2), 67.8 (C3), 67.3 (C5), 64.3 (C6), 62.9 (C22), 61.4 (C4), 55.6 (C7).

S3. Refinement

The s.u. of the y coordinate of the O1 atom is not given since this parameter must be fixed in the P2₁ space group. We measured 11 Friedels pairs since the h limits were from -11 to 11. H atoms were located from a difference map but were not refined (N—H = 0.91 Å and C—H = 0.94–1.06 Å).

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992-1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.

Figures

Fig. 1. ORTEPII (Johnson, 1976) molecular diagram of the title compound. Displacement ellipsoids are shown at the 40% probability level.

(I)

Crystal data

C29H29NO9	F(000) = 564
Mr = 535.55	Dx = 1.284 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.7107 Å
a = 8.026 (2) Å	Cell parameters from 24 reflections
b = 12.359 (3) Å	θ = 10.2–13.3°
c = 14.056 (3) Å	µ = 0.10 mm^−1
β = 96.63 (2)°	T = 293 K
V = 1384.9 (5) Å^3	Monoclinic prism, colorless
Z = 2	0.35 × 0.30 × 0.29 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.015
Radiation source: X-ray tube	θmax = 30.0°, θmin = 2.2°
Graphite monochromator	h = −11→11
ω scans	k = 0→17
4363 measured reflections	l = 0→19
4225 independent reflections	2 standard reflections every 120 reflections
3518 reflections with I > 0.05σ(I)	intensity decay: 4.2%

Refinement

Refinement on F	0 restraints
Least-squares matrix: full	0 constraints
R[F^2 > 2σ(F^2)] = 0.068	H-atom parameters not refined
wR(F^2) = 0.040	Weighting scheme based on measured s.u.'s w = 1/[σ^2(Fo) + 0.00008|Fo|^2]
S = 1.90	(Δ/σ)max = 0.022
3518 reflections	Δρmax = 0.16 e Å^−3
351 parameters	Δρmin = −0.20 e Å^−3

Special details

Refinement. The decay correction has been applied. H atoms have been located by difference-Fourier syntheses

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.5814 (1)	0.2268	0.54634 (9)	0.0658 (4)
O2	0.3181 (2)	0.1688 (1)	0.41260 (9)	0.0611 (4)
O3	0.0850 (1)	0.3243 (1)	0.46179 (8)	0.0557 (3)
O4	0.2644 (2)	0.5096 (1)	0.6053 (1)	0.0839 (5)
O5	0.4243 (2)	0.1894 (1)	0.67208 (9)	0.0659 (4)
O6	0.2258 (2)	0.2590 (1)	0.81754 (9)	0.0793 (5)
O7	0.2091 (2)	0.0041 (1)	0.4192 (1)	0.0867 (5)
O8	0.2176 (2)	0.4078 (2)	0.3499 (1)	0.0841 (5)
O9	0.2720 (3)	0.3301 (2)	0.9620 (1)	0.1271 (7)
N4	0.1551 (2)	0.4329 (2)	0.6445 (1)	0.0695 (5)
C1	0.4522 (3)	0.1654 (2)	0.5771 (1)	0.0629 (6)
C2	0.2928 (2)	0.1888 (2)	0.5107 (1)	0.0557 (5)
C3	0.2428 (2)	0.3051 (2)	0.5202 (1)	0.0524 (5)
C4	0.2167 (2)	0.3263 (2)	0.6238 (1)	0.0560 (5)
C5	0.3794 (2)	0.2999 (2)	0.6870 (1)	0.0610 (6)
C6	0.3719 (3)	0.3175 (2)	0.7915 (1)	0.0757 (7)
C7	0.7427 (3)	0.2016 (2)	0.5953 (2)	0.0921 (8)
C8	0.2657 (2)	0.0737 (2)	0.3738 (1)	0.0587 (6)
C9	0.2868 (2)	0.0672 (2)	0.2716 (1)	0.0585 (5)
C10	0.3621 (3)	0.1485 (2)	0.2250 (1)	0.0774 (7)
C11	0.3851 (3)	0.1371 (2)	0.1300 (2)	0.1010 (9)
C12	0.3311 (3)	0.0472 (3)	0.0814 (2)	0.107 (1)
C13	0.2542 (3)	−0.0332 (2)	0.1261 (2)	0.0966 (9)
C14	0.2326 (3)	−0.0244 (2)	0.2212 (2)	0.0777 (7)
C15	0.0904 (2)	0.3769 (2)	0.3779 (1)	0.0601 (6)
C16	−0.0787 (2)	0.3888 (2)	0.3238 (1)	0.0581 (5)
C17	−0.2247 (2)	0.3869 (2)	0.3665 (1)	0.0639 (6)
C18	−0.3773 (3)	0.3985 (2)	0.3117 (2)	0.0797 (7)
C19	−0.3855 (3)	0.4098 (3)	0.2156 (2)	0.111 (1)
C20	−0.2420 (4)	0.4085 (4)	0.1723 (2)	0.146 (1)
C21	−0.0898 (3)	0.4006 (3)	0.2265 (2)	0.112 (1)
C22	0.2431 (3)	0.6103 (2)	0.6494 (2)	0.1023 (9)
C23	0.1875 (3)	0.2736 (2)	0.9056 (2)	0.0825 (8)
C24	0.0341 (3)	0.2145 (2)	0.9234 (2)	0.0852 (8)
C25	−0.0146 (4)	0.2180 (3)	1.0146 (2)	0.134 (1)
C26	−0.1551 (4)	0.1584 (4)	1.0330 (2)	0.156 (1)
C27	−0.2445 (4)	0.1023 (4)	0.9636 (3)	0.159 (1)
C28	−0.1994 (4)	0.1008 (4)	0.8735 (3)	0.160 (1)
C29	−0.0588 (4)	0.1556 (3)	0.8544 (2)	0.117 (1)
H1	0.4757	0.0817	0.5807	0.076*
H2	0.1931	0.1395	0.5280	0.067*
H3	0.3239	0.3557	0.4990	0.063*
H4	0.1294	0.2687	0.6433	0.067*
H5	0.4737	0.3507	0.6684	0.075*
H6	0.4761	0.2774	0.8276	0.094*
H7	0.3454	0.3972	0.8044	0.094*
H8	0.7486	0.2259	0.6600	0.111*
H9	0.7603	0.1254	0.5954	0.111*
H10	0.8288	0.2360	0.5647	0.111*
H11	0.3969	0.2129	0.2587	0.092*
H12	0.4387	0.1934	0.0980	0.121*
H13	0.3455	0.0398	0.0154	0.126*
H14	0.2136	−0.0962	0.0914	0.114*
H15	0.1786	−0.0817	0.2532	0.092*
H16	−0.2182	0.3771	0.4342	0.076*
H17	−0.4779	0.3979	0.3419	0.093*
H18	−0.4903	0.4196	0.1778	0.131*
H19	−0.2442	0.4158	0.1040	0.179*
H20	0.0127	0.4042	0.1976	0.132*
H21	0.0552	0.4392	0.6074	0.084*
H22	0.2562	0.6016	0.7177	0.122*
H23	0.3200	0.6613	0.6314	0.122*
H24	0.1290	0.6372	0.6311	0.122*
H25	0.0492	0.2634	1.0630	0.158*
H26	−0.1833	0.1623	1.0979	0.190*
H27	−0.3395	0.0654	0.9797	0.189*
H28	−0.2594	0.0575	0.8260	0.190*
H29	−0.0208	0.1535	0.7927	0.139*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0539 (7)	0.0685 (9)	0.0760 (8)	0.0034 (7)	0.0113 (6)	0.0104 (7)
O2	0.0713 (8)	0.0544 (8)	0.0601 (7)	−0.0096 (7)	0.0177 (6)	−0.0067 (6)
O3	0.0473 (6)	0.0663 (8)	0.0545 (7)	−0.0050 (6)	0.0096 (5)	0.0073 (7)
O4	0.099 (1)	0.0622 (9)	0.095 (1)	0.0017 (9)	0.0331 (8)	−0.0067 (8)
O5	0.0741 (8)	0.0618 (8)	0.0616 (7)	−0.0012 (7)	0.0065 (6)	0.0104 (7)
O6	0.0895 (9)	0.093 (1)	0.0578 (7)	−0.0114 (9)	0.0181 (7)	−0.0032 (8)
O7	0.118 (1)	0.0729 (9)	0.0685 (9)	−0.0392 (9)	0.0081 (8)	0.0021 (8)
O8	0.0592 (8)	0.108 (1)	0.0881 (9)	−0.0051 (8)	0.0239 (7)	0.0355 (9)
O9	0.167 (2)	0.148 (2)	0.070 (1)	−0.026 (2)	0.027 (1)	−0.018 (1)
N4	0.062 (1)	0.072 (1)	0.077 (1)	0.0025 (9)	0.0186 (8)	−0.002 (1)
C1	0.073 (1)	0.053 (1)	0.065 (1)	0.004 (1)	0.013 (1)	0.004 (1)
C2	0.058 (1)	0.053 (1)	0.057 (1)	−0.0077 (9)	0.0121 (8)	−0.0004 (9)
C3	0.0465 (9)	0.056 (1)	0.055 (1)	−0.0027 (9)	0.0073 (8)	0.0008 (9)
C4	0.053 (1)	0.059 (1)	0.058 (1)	−0.003 (1)	0.0134 (8)	0.000 (1)
C5	0.061 (1)	0.061 (1)	0.060 (1)	−0.003 (1)	0.0072 (9)	0.002 (1)
C6	0.079 (1)	0.088 (2)	0.060 (1)	−0.009 (1)	0.006 (1)	−0.001 (1)
C7	0.064 (1)	0.105 (2)	0.105 (2)	0.016 (1)	0.001 (1)	0.011 (2)
C8	0.051 (1)	0.054 (1)	0.069 (1)	−0.005 (1)	−0.0025 (9)	−0.001 (1)
C9	0.053 (1)	0.062 (1)	0.059 (1)	0.001 (1)	0.0000 (9)	−0.004 (1)
C10	0.084 (1)	0.086 (2)	0.063 (1)	−0.019 (1)	0.010 (1)	−0.007 (1)
C11	0.123 (2)	0.112 (2)	0.071 (1)	−0.027 (2)	0.022 (1)	0.001 (1)
C12	0.113 (2)	0.144 (3)	0.066 (1)	−0.018 (2)	0.016 (1)	−0.023 (2)
C13	0.108 (2)	0.103 (2)	0.077 (1)	−0.018 (2)	0.009 (1)	−0.031 (1)
C14	0.081 (1)	0.074 (2)	0.077 (1)	−0.010 (1)	0.006 (1)	−0.011 (1)
C15	0.061 (1)	0.059 (1)	0.062 (1)	0.003 (1)	0.0168 (9)	0.007 (1)
C16	0.060 (1)	0.056 (1)	0.060 (1)	0.005 (1)	0.0110 (8)	0.009 (1)
C17	0.060 (1)	0.062 (1)	0.071 (1)	0.000 (1)	0.0114 (9)	−0.012 (1)
C18	0.057 (1)	0.070 (1)	0.112 (2)	0.006 (1)	0.005 (1)	−0.013 (1)
C19	0.091 (2)	0.114 (2)	0.118 (2)	0.026 (2)	−0.026 (2)	0.019 (2)
C20	0.120 (2)	0.229 (4)	0.085 (2)	0.022 (3)	−0.010 (2)	0.066 (2)
C21	0.085 (2)	0.176 (3)	0.076 (1)	0.022 (2)	0.011 (1)	0.050 (2)
C22	0.105 (2)	0.069 (2)	0.133 (2)	−0.004 (2)	0.016 (2)	−0.023 (2)
C23	0.105 (2)	0.088 (2)	0.055 (1)	0.012 (1)	0.013 (1)	0.004 (1)
C24	0.101 (2)	0.088 (2)	0.072 (1)	0.026 (1)	0.030 (1)	0.021 (1)
C25	0.133 (2)	0.184 (3)	0.094 (2)	0.012 (2)	0.057 (1)	0.010 (2)
C26	0.139 (2)	0.232 (5)	0.111 (2)	0.018 (3)	0.070 (2)	0.032 (3)
C27	0.149 (2)	0.178 (4)	0.167 (3)	−0.007 (3)	0.086 (2)	0.026 (3)
C28	0.147 (2)	0.184 (4)	0.163 (3)	−0.053 (3)	0.076 (2)	−0.003 (3)
C29	0.123 (2)	0.133 (3)	0.104 (2)	−0.020 (2)	0.045 (2)	0.003 (2)

Geometric parameters (Å, º)

O1—C1	1.393 (2)	C10—H11	0.95
O2—C2	1.438 (2)	C11—C12	1.349 (4)
O3—C3	1.447 (2)	C11—H12	0.96
O4—N4	1.443 (2)	C12—C13	1.361 (4)
O5—C1	1.411 (2)	C12—H13	0.95
O5—C5	1.433 (2)	C13—C14	1.372 (3)
O6—C6	1.459 (3)	C13—H14	0.96
C1—C2	1.521 (3)	C14—H15	0.97
N4—C4	1.449 (3)	C15—C16	1.485 (2)
C2—C3	1.503 (3)	C16—C17	1.377 (3)
C3—C4	1.517 (2)	C16—C21	1.368 (3)
C4—C5	1.528 (3)	C17—C18	1.377 (3)
C5—C6	1.493 (3)	C17—H16	0.95
O1—C7	1.429 (2)	C18—C19	1.353 (3)
O2—C8	1.343 (2)	C18—H17	0.95
O3—C15	1.352 (2)	C19—C20	1.363 (4)
O4—C22	1.410 (3)	C19—H18	0.95
O6—C23	1.321 (2)	C20—C21	1.366 (4)
O7—C8	1.192 (2)	C20—H19	0.96
O8—C15	1.198 (2)	C21—H20	0.96
O9—C23	1.206 (3)	C22—H22	0.96
N4—H21	0.91	C22—H23	0.94
C1—H1	1.05	C22—H24	0.98
C2—H2	1.06	C23—C24	1.477 (3)
C3—H3	0.97	C24—C25	1.382 (3)
C4—H4	1.06	C24—C29	1.364 (4)
C5—H5	1.04	C25—C26	1.397 (5)
C6—H6	1.05	C25—H25	0.98
C6—H7	1.03	C26—C27	1.335 (5)
C7—H8	0.95	C26—H26	0.97
C7—H9	0.95	C27—C28	1.357 (4)
C7—H10	0.95	C27—H27	0.94
C8—C9	1.468 (2)	C28—C29	1.369 (4)
C9—C10	1.377 (3)	C28—H28	0.94
C9—C14	1.379 (3)	C29—H29	0.95
C10—C11	1.376 (3)
N4—O4—C22	107.6 (2)	C10—C11—C12	120.2 (2)
C1—O5—C5	114.1 (1)	C10—C11—H12	120.0
C6—O6—C23	116.6 (2)	C12—C11—H12	119.8
O4—N4—C4	106.5 (1)	C11—C12—C13	120.3 (2)
O1—C1—O5	112.6 (2)	C11—C12—H13	120.2
O1—C1—C2	108.1 (1)	C13—C12—H13	119.5
O5—C1—C2	109.1 (2)	C12—C13—C14	120.5 (2)
O2—C2—C1	110.7 (1)	C12—C13—H14	120.3
O2—C2—C3	108.6 (1)	C14—C13—H14	119.2
C1—C2—C3	109.9 (2)	C9—C14—C13	119.8 (2)
O3—C3—C2	109.3 (1)	C9—C14—H15	119.5
O3—C3—C4	107.9 (1)	C13—C14—H15	120.7
C2—C3—C4	108.6 (2)	O3—C15—O8	123.7 (2)
N4—C4—C3	116.0 (2)	O3—C15—C16	112.0 (2)
N4—C4—C5	111.5 (2)	O8—C15—C16	124.3 (2)
C3—C4—C5	108.5 (1)	C15—C16—C17	123.3 (2)
O5—C5—C4	109.4 (2)	C15—C16—C21	118.2 (2)
O5—C5—C6	108.8 (2)	C17—C16—C21	118.5 (2)
C4—C5—C6	114.3 (2)	C16—C17—C18	120.1 (2)
O6—C6—C5	107.4 (2)	C16—C17—H16	119.1
C1—O1—C7	113.4 (2)	C18—C17—H16	120.9
C2—O2—C8	117.8 (1)	C17—C18—C19	120.5 (2)
C3—O3—C15	117.4 (1)	C17—C18—H17	119.6
O4—N4—H21	105.1	C19—C18—H17	119.9
C4—N4—H21	105.2	C18—C19—C20	119.9 (2)
O1—C1—H1	114.5	C18—C19—H18	120.7
O5—C1—H1	102.0	C20—C19—H18	119.4
C2—C1—H1	110.5	C19—C20—C21	120.0 (2)
O2—C2—H2	108.4	C19—C20—H19	121.6
C1—C2—H2	110.8	C21—C20—H19	118.4
C3—C2—H2	108.3	C16—C21—C20	121.1 (2)
O3—C3—H3	107.1	C16—C21—H20	117.9
C2—C3—H3	113.1	C20—C21—H20	121.0
C4—C3—H3	110.7	O4—C22—H22	109.7
N4—C4—H4	108.0	O4—C22—H23	111.0
C3—C4—H4	107.5	O4—C22—H24	109.9
C5—C4—H4	104.6	H22—C22—H23	110.2
O5—C5—H5	109.6	H22—C22—H24	106.9
C4—C5—H5	108.8	H23—C22—H24	108.9
C6—C5—H5	105.8	O6—C23—O9	121.4 (2)
O6—C6—H6	105.3	O6—C23—C24	112.4 (2)
O6—C6—H7	104.0	O9—C23—C24	126.2 (2)
C5—C6—H6	106.6	C23—C24—C25	118.2 (2)
C5—C6—H7	110.2	C23—C24—C29	122.7 (2)
H6—C6—H7	122.4	C25—C24—C29	119.1 (3)
O1—C7—H8	109.4	C24—C25—C26	118.4 (3)
O1—C7—H9	110.0	C24—C25—H25	118.8
O1—C7—H10	110.4	C26—C25—H25	122.8
H8—C7—H9	108.7	C25—C26—C27	121.0 (3)
H8—C7—H10	109.4	C25—C26—H26	115.5
H9—C7—H10	108.9	C27—C26—H26	123.4
O2—C8—O7	122.3 (2)	C26—C27—C28	120.7 (4)
O2—C8—C9	112.3 (2)	C26—C27—H27	117.3
O7—C8—C9	125.4 (2)	C28—C27—H27	122.0
C8—C9—C10	122.1 (2)	C27—C28—C29	119.4 (4)
C8—C9—C14	118.9 (2)	C27—C28—H28	119.9
C10—C9—C14	119.0 (2)	C29—C28—H28	120.4
C9—C10—C11	120.2 (2)	C24—C29—C28	121.3 (3)
C9—C10—H11	119.5	C24—C29—H29	117.2
C11—C10—H11	120.3	C28—C29—H29	121.5
O1—C1—O5—C5	60.0 (2)	C1—C2—C3—C4	−58.6 (2)
O1—C1—C2—O2	55.3 (2)	C2—O2—C8—C9	175.5 (1)
O1—C1—C2—C3	−64.6 (2)	C2—C1—O1—C7	−172.4 (2)
O2—C2—C1—O5	178.0 (1)	C2—C1—O5—C5	−59.9 (2)
O2—C2—C3—O3	62.7 (2)	C2—C3—O3—C15	−103.4 (2)
O2—C2—C3—C4	−179.8 (1)	C2—C3—C4—C5	58.2 (2)
O2—C8—C9—C10	3.8 (3)	C3—O3—C15—C16	178.5 (2)
O2—C8—C9—C14	−177.6 (2)	C3—C2—O2—C8	−140.9 (2)
O3—C3—C2—C1	−176.1 (1)	C3—C4—C5—C6	179.8 (2)
O3—C3—C4—N4	−57.0 (2)	C4—N4—O4—C22	−161.6 (2)
O3—C3—C4—C5	176.6 (2)	C4—C3—O3—C15	138.6 (2)
O3—C15—C16—C17	23.9 (3)	C5—C6—O6—C23	−173.3 (2)
O3—C15—C16—C21	−155.1 (2)	C6—O6—C23—C24	177.7 (2)
O4—N4—C4—C3	−51.6 (2)	C8—C9—C10—C11	177.5 (2)
O4—N4—C4—C5	73.2 (2)	C8—C9—C14—C13	−178.7 (2)
O5—C1—O1—C7	67.1 (2)	C9—C10—C11—C12	1.3 (4)
O5—C1—C2—C3	58.1 (2)	C9—C14—C13—C12	1.0 (4)
O5—C5—C4—N4	173.1 (1)	C10—C9—C14—C13	0.0 (3)
O5—C5—C4—C3	−57.9 (2)	C10—C11—C12—C13	−0.3 (5)
O5—C5—C6—O6	−70.1 (2)	C11—C10—C9—C14	−1.1 (3)
O6—C6—C5—C4	52.5 (2)	C11—C12—C13—C14	−0.8 (4)
O6—C23—C24—C25	176.4 (2)	C15—C16—C17—C18	179.9 (2)
O6—C23—C24—C29	−2.3 (3)	C15—C16—C21—C20	177.9 (3)
O7—C8—O2—C2	−4.5 (3)	C16—C17—C18—C19	1.3 (4)
O7—C8—C9—C10	−176.2 (2)	C16—C21—C20—C19	3.1 (6)
O7—C8—C9—C14	2.4 (3)	C17—C16—C21—C20	−1.2 (5)
O8—C15—O3—C3	0.2 (3)	C17—C18—C19—C20	0.7 (5)
O8—C15—C16—C17	−157.8 (2)	C18—C17—C16—C21	−1.0 (4)
O8—C15—C16—C21	23.1 (4)	C18—C19—C20—C21	−2.9 (6)
O9—C23—O6—C6	−1.9 (3)	C23—C24—C25—C26	−177.1 (3)
O9—C23—C24—C25	−4.0 (4)	C23—C24—C29—C28	179.3 (3)
O9—C23—C24—C29	177.2 (3)	C24—C25—C26—C27	−2.4 (6)
N4—C4—C3—C2	−175.4 (2)	C24—C29—C28—C27	−2.2 (6)
N4—C4—C5—C6	50.9 (2)	C25—C24—C29—C28	0.6 (5)
C1—O5—C5—C4	60.6 (2)	C25—C26—C27—C28	0.9 (7)
C1—O5—C5—C6	−173.9 (2)	C26—C25—C24—C29	1.6 (5)
C1—C2—O2—C8	98.3 (2)	C26—C27—C28—C29	1.4 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H21···O3	0.91	2.53	2.895 (2)	105
N4—H21···O7^i	0.91	2.26	3.085 (2)	151

Symmetry code: (i) −x, y+1/2, −z+1.