9-(2-Methoxy­benzyl­idene)-6-(2-methoxy­phenyl)-4,8-di­phenyl-2-oxa-3,7-di­aza­spiro­[4.4]­nona-3,7-dien-1-one

The title compound, C₃₃H₂₆N₂O₄, is derived from an unexpected spiran synthesis. Its crystal structure has been determined at room temperature. The skeleton is composed of a spiro­[4.4] system formed by an isoxazolone and a substituted pyrroline ring obtained by a series of tandem reactions. The carbonyl exocyclic bond angles [121.9 (2) and 129.9 (2)°] of the isox­azol­one ring show the usual asymmetry.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.041
• wR factor = 0.097
• Data-to-parameter ratio = 17.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



GOODF_01  Alert C The least squares goodness of fit parameter lies
          outside the range 0.80 <> 2.00
          Goodness of fit given =      0.716


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The formation of the title compound, (I), has been interpreted, like the p-MeC₆H₄– derivative (Bruno et al., 2001a), as the unexpected product of a series of tandem reactions involving Michael- and retro-Michael reactions, C-alkylation, aldol addition and diastereospecific cyclization (Risitano et al., 2001).

The stereochemistry of the C═C double bond and of the tetrahedral C atoms of the product could not easily be established by any spectral technique. The structure at the solid state has been unambiguously determined by X-ray diffraction diffraction.

The title compound is very similar to the already reported p-Me derivative (Bruno et al., 2001a), obtained by the similar reaction with the same N-ylide. The molecular skeleton is a spiro[4.4] system constituted by an isoxazolone and a three-substituted pyrroline ring. The two chiral C atoms, the spiro center C1 and the pyrroline C4 atom, have the same configuration (R,R in Fig. 1). Due to the crystallographic centre of symmetry, the crystal is the racemic mixture of both enhantiomers.

The geometric values of the two similar compounds are comparable within the experimental error and are in good agreement with the known data (Bertolasi et al., 1994; Brehm et al., 1992). The carbonyl group shows almost the same asymmetry, in agreement with the other known carbonyl groups (Allen et al., 1991) and cumarine derivatives (Bruno et al., 2001b). Both compounds have the isoxazolone linked through the C2 atom to a phenyl group.

Although the torsion angles defining the orientation of phenyl with respect to the eterocyclic ring are very different [N1—C2—C14—C15 = 0.6 (3) versus -32.1 (5)° of the p-tolyl derivative] the C2—C14 bond distances are almost equal. The largest discrepancy between the two similar structures is observed for the C6—C26—C27—C28 torsion angle. Due to steric interactions, the methoxy groups are differently oriented with respect to the phenyl to which are bonded [C13—O3—C12—C7 = 179.4 (2)°, while C33—O4—C32—C27 = -163.8 (2)°]. Weak intra- and intermolecular hydrogen-bond interactions determine the crystal packing and the relative orientations of substituents with respect to the single spiranic fragment.

S2. Experimental

The title compound was obtained as a single diastereomer from 4-arylmethyleneisoxazol-5-one and in situ prepared N-ylide (Risitano et al., 1997).

S3. Refinement

Reflection intensities were evaluated by profile fitting of a 96-steps peak scan among 2θ shells procedure (Diamond, 1969) and then corrected for Lorentz–polarization effects. Standard uncertainties σ(I) were estimated from counting statistics. H atoms were located in idealized positions and allowed to ride on their parent C atoms with isotropic displacement parameters related to the refined values of their corresponding parent atoms.

Computing details

Data collection: P3/V (Siemens,1989); cell refinement: P3/V; data reduction: SHELXTL-Plus (Sheldrick, 1990); program(s) used to solve structure: SIR92 (Altomare, 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XPW (Siemens, 1996); software used to prepare material for publication: PARST97 (Nardelli, 1995) and SHELXL97.

Figures

Fig. 1. Perspective view of compound (I) with the atomic numbering scheme. The non-H-atom displacement ellipsoids ate at the 30% probability level.

9-(2-Methoxy-benzylidene)-6-(2-methoxy-phenyl)-4,8-diphenyl-2-oxa- 3,7-diazaspiro[4.4]nona-3,7-dien-1-one

Crystal data

C33H26N2O4	Z = 2
Mr = 514.56	F(000) = 540
Triclinic, P1	Dx = 1.300 Mg m^−3
a = 9.127 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.450 (3) Å	Cell parameters from 33 reflections
c = 14.632 (3) Å	θ = 6.0–12.9°
α = 99.172 (19)°	µ = 0.09 mm^−1
β = 101.131 (17)°	T = 293 K
γ = 101.239 (18)°	Irregular, colourless
V = 1314.6 (5) Å^3	0.17 × 0.13 × 0.10 mm

Data collection

Siemens P4 diffractometer	Rint = 0.032
Radiation source: fine-focus sealed tube	θmax = 27.6°, θmin = 2.0°
Graphite monochromator	h = 0→11
ω–2θ scans	k = −13→13
6449 measured reflections	l = −19→18
6067 independent reflections	3 standard reflections every 197 reflections
2324 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0434P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.72	(Δ/σ)max < 0.001
6067 reflections	Δρmax = 0.14 e Å^−3
353 parameters	Δρmin = −0.12 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0066 (10)

Special details

Experimental. All calculations were performed on a µ-VAX 3400 and on a DEC-alpha 3000/400.

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
O1	−0.10977 (17)	0.19704 (15)	0.05703 (10)	0.0697 (4)
O2	0.06428 (19)	0.08620 (16)	0.10916 (11)	0.0778 (5)
O3	−0.44275 (16)	0.06542 (16)	0.18440 (11)	0.0767 (5)
O4	0.13162 (16)	0.62202 (13)	0.38007 (11)	0.0627 (4)
N1	−0.1893 (2)	0.28770 (18)	0.09999 (12)	0.0623 (5)
N2	−0.01940 (19)	0.05973 (15)	0.33299 (11)	0.0522 (5)
C1	−0.0554 (2)	0.20630 (18)	0.22057 (13)	0.0427 (5)
C2	−0.1566 (2)	0.29628 (19)	0.19064 (14)	0.0472 (5)
C3	−0.0222 (2)	0.1529 (2)	0.12636 (15)	0.0546 (6)
C4	−0.1401 (2)	0.08823 (18)	0.26221 (13)	0.0465 (5)
H4A	−0.2103	0.1237	0.2968	0.056*
C5	0.1027 (2)	0.15468 (18)	0.35306 (13)	0.0438 (5)
C6	0.0927 (2)	0.26075 (18)	0.29690 (13)	0.0416 (5)
C7	−0.2340 (2)	−0.03312 (19)	0.18993 (14)	0.0502 (5)
C8	−0.1717 (3)	−0.1378 (2)	0.16066 (17)	0.0764 (7)
H8A	−0.0686	−0.1329	0.1857	0.092*
C9	−0.2581 (4)	−0.2496 (3)	0.0953 (2)	0.1033 (10)
H9A	−0.2135	−0.3189	0.0758	0.124*
C10	−0.4097 (4)	−0.2574 (3)	0.0596 (2)	0.1042 (10)
H10A	−0.4689	−0.3329	0.0157	0.125*
C11	−0.4760 (3)	−0.1553 (3)	0.08741 (18)	0.0842 (8)
H11A	−0.5796	−0.1618	0.0626	0.101*
C12	−0.3888 (3)	−0.0427 (2)	0.15233 (16)	0.0594 (6)
C13	−0.5991 (3)	0.0641 (3)	0.1489 (2)	0.1016 (9)
H13A	−0.6206	0.1455	0.1775	0.122*
H13B	−0.6633	−0.0101	0.1640	0.122*
H13C	−0.6192	0.0558	0.0811	0.122*
C14	−0.2262 (2)	0.38041 (18)	0.25122 (15)	0.0484 (5)
C15	−0.3275 (3)	0.4497 (2)	0.21214 (18)	0.0766 (7)
H15A	−0.3502	0.4449	0.1467	0.092*
C16	−0.3958 (3)	0.5264 (3)	0.2692 (3)	0.0960 (10)
H16A	−0.4638	0.5729	0.2418	0.115*
C17	−0.3644 (3)	0.5347 (2)	0.3659 (2)	0.0851 (8)
H17A	−0.4125	0.5847	0.4038	0.102*
C18	−0.2614 (3)	0.4686 (2)	0.40581 (19)	0.0758 (7)
H18A	−0.2376	0.4749	0.4713	0.091*
C19	−0.1932 (3)	0.3928 (2)	0.34877 (16)	0.0621 (6)
H19A	−0.1229	0.3488	0.3767	0.075*
C20	0.2378 (2)	0.15512 (17)	0.42693 (13)	0.0435 (5)
C21	0.3866 (2)	0.19547 (19)	0.41597 (15)	0.0546 (6)
H21A	0.4024	0.2241	0.3609	0.066*
C22	0.5108 (2)	0.1935 (2)	0.48570 (17)	0.0656 (7)
H22A	0.6098	0.2197	0.4771	0.079*
C23	0.4892 (3)	0.1531 (2)	0.56798 (17)	0.0685 (7)
H23A	0.5732	0.1537	0.6157	0.082*
C24	0.3423 (3)	0.1118 (2)	0.57934 (15)	0.0615 (6)
H24A	0.3271	0.0829	0.6344	0.074*
C25	0.2183 (2)	0.11304 (17)	0.50995 (14)	0.0509 (5)
H25A	0.1197	0.0852	0.5186	0.061*
C26	0.1870 (2)	0.38002 (18)	0.31301 (13)	0.0476 (5)
H26A	0.2679	0.4026	0.3666	0.057*
C27	0.1740 (2)	0.48004 (19)	0.25258 (15)	0.0488 (5)
C28	0.1902 (2)	0.4540 (2)	0.15946 (16)	0.0660 (6)
H28A	0.2097	0.3729	0.1348	0.079*
C29	0.1778 (3)	0.5481 (3)	0.10244 (18)	0.0778 (7)
H29A	0.1879	0.5301	0.0399	0.093*
C30	0.1504 (3)	0.6678 (3)	0.1399 (2)	0.0799 (8)
H30A	0.1410	0.7306	0.1020	0.096*
C31	0.1365 (2)	0.6964 (2)	0.23166 (18)	0.0678 (7)
H31A	0.1197	0.7787	0.2562	0.081*
C32	0.1475 (2)	0.6025 (2)	0.28819 (16)	0.0534 (6)
C33	0.0652 (3)	0.7288 (2)	0.41123 (17)	0.0815 (8)
H33A	0.0604	0.7320	0.4765	0.122*
H33C	−0.0366	0.7150	0.3726	0.122*
H33D	0.1270	0.8115	0.4056	0.122*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0692 (11)	0.0961 (12)	0.0420 (9)	0.0187 (10)	0.0065 (8)	0.0176 (8)
O2	0.0702 (11)	0.0891 (12)	0.0728 (12)	0.0252 (10)	0.0191 (9)	0.0017 (9)
O3	0.0398 (9)	0.0899 (12)	0.0910 (12)	0.0117 (9)	−0.0002 (9)	0.0142 (10)
O4	0.0714 (11)	0.0528 (9)	0.0639 (10)	0.0198 (8)	0.0061 (8)	0.0172 (8)
N1	0.0555 (12)	0.0834 (13)	0.0501 (12)	0.0187 (11)	0.0043 (10)	0.0263 (10)
N2	0.0473 (11)	0.0515 (10)	0.0534 (11)	0.0050 (9)	−0.0001 (9)	0.0209 (8)
C1	0.0385 (11)	0.0499 (11)	0.0393 (11)	0.0091 (9)	0.0035 (9)	0.0160 (9)
C2	0.0390 (12)	0.0538 (12)	0.0451 (12)	0.0035 (10)	−0.0010 (10)	0.0220 (10)
C3	0.0454 (14)	0.0619 (14)	0.0494 (14)	0.0053 (12)	0.0036 (12)	0.0090 (11)
C4	0.0404 (12)	0.0490 (12)	0.0467 (12)	0.0054 (10)	0.0005 (10)	0.0179 (10)
C5	0.0428 (12)	0.0437 (11)	0.0437 (12)	0.0084 (10)	0.0049 (10)	0.0140 (9)
C6	0.0389 (12)	0.0428 (11)	0.0417 (11)	0.0084 (9)	0.0042 (9)	0.0123 (9)
C7	0.0427 (13)	0.0465 (12)	0.0531 (13)	0.0009 (10)	−0.0025 (11)	0.0140 (10)
C8	0.0692 (17)	0.0556 (15)	0.0890 (18)	0.0135 (14)	−0.0092 (15)	0.0045 (13)
C9	0.116 (3)	0.0648 (18)	0.107 (2)	0.0165 (18)	−0.006 (2)	−0.0032 (17)
C10	0.110 (3)	0.073 (2)	0.087 (2)	−0.0171 (19)	−0.017 (2)	−0.0099 (16)
C11	0.0605 (17)	0.089 (2)	0.0777 (18)	−0.0130 (16)	−0.0094 (15)	0.0132 (16)
C12	0.0466 (14)	0.0621 (15)	0.0586 (14)	−0.0035 (12)	0.0003 (12)	0.0152 (12)
C13	0.0485 (16)	0.144 (3)	0.110 (2)	0.0258 (17)	0.0029 (16)	0.0354 (19)
C14	0.0402 (12)	0.0450 (11)	0.0604 (14)	0.0078 (10)	0.0063 (11)	0.0211 (10)
C15	0.0726 (17)	0.0775 (16)	0.0789 (17)	0.0307 (15)	−0.0030 (15)	0.0226 (14)
C16	0.0678 (19)	0.0796 (19)	0.139 (3)	0.0383 (16)	0.004 (2)	0.016 (2)
C17	0.0696 (19)	0.0610 (16)	0.128 (3)	0.0144 (14)	0.0401 (19)	0.0101 (17)
C18	0.093 (2)	0.0602 (15)	0.0859 (18)	0.0224 (15)	0.0390 (16)	0.0205 (14)
C19	0.0717 (17)	0.0591 (14)	0.0653 (16)	0.0242 (13)	0.0220 (13)	0.0224 (12)
C20	0.0421 (12)	0.0380 (11)	0.0462 (12)	0.0065 (9)	−0.0005 (10)	0.0126 (9)
C21	0.0505 (14)	0.0588 (13)	0.0568 (14)	0.0135 (11)	0.0057 (12)	0.0255 (11)
C22	0.0425 (14)	0.0680 (15)	0.0871 (18)	0.0117 (11)	0.0045 (13)	0.0321 (14)
C23	0.0550 (16)	0.0624 (14)	0.0770 (17)	0.0052 (12)	−0.0157 (13)	0.0300 (13)
C24	0.0647 (16)	0.0606 (14)	0.0550 (14)	0.0064 (12)	−0.0015 (13)	0.0281 (11)
C25	0.0457 (13)	0.0465 (12)	0.0564 (13)	0.0034 (10)	0.0022 (11)	0.0194 (10)
C26	0.0448 (12)	0.0482 (12)	0.0461 (12)	0.0087 (10)	−0.0005 (10)	0.0152 (10)
C27	0.0408 (12)	0.0475 (12)	0.0523 (13)	0.0016 (10)	−0.0001 (10)	0.0177 (10)
C28	0.0644 (16)	0.0661 (15)	0.0627 (16)	0.0021 (12)	0.0095 (13)	0.0221 (13)
C29	0.0784 (19)	0.0881 (19)	0.0638 (16)	−0.0014 (15)	0.0134 (14)	0.0354 (15)
C30	0.0794 (19)	0.0803 (19)	0.0777 (19)	0.0048 (15)	−0.0002 (15)	0.0489 (16)
C31	0.0657 (16)	0.0562 (14)	0.0778 (18)	0.0078 (12)	−0.0008 (14)	0.0320 (13)
C32	0.0451 (13)	0.0532 (13)	0.0559 (14)	0.0033 (11)	−0.0022 (11)	0.0210 (11)
C33	0.0901 (19)	0.0718 (16)	0.0862 (19)	0.0351 (15)	0.0136 (15)	0.0147 (14)

Geometric parameters (Å, º)

O1—C3	1.364 (2)	C9—C10	1.364 (4)
O1—N1	1.440 (2)	C10—C11	1.371 (4)
O2—C3	1.187 (2)	C11—C12	1.381 (3)
O3—C12	1.369 (3)	C14—C15	1.377 (3)
O3—C13	1.417 (2)	C14—C19	1.380 (3)
O4—C32	1.367 (2)	C15—C16	1.382 (3)
O4—C33	1.425 (2)	C16—C17	1.373 (4)
N1—C2	1.287 (2)	C17—C18	1.368 (3)
N2—C5	1.289 (2)	C18—C19	1.376 (3)
N2—C4	1.470 (2)	C20—C25	1.387 (2)
C1—C2	1.498 (2)	C20—C21	1.389 (3)
C1—C3	1.512 (3)	C21—C22	1.377 (3)
C1—C6	1.520 (2)	C22—C23	1.374 (3)
C1—C4	1.594 (2)	C23—C24	1.376 (3)
C2—C14	1.466 (3)	C24—C25	1.370 (3)
C4—C7	1.503 (3)	C26—C27	1.480 (2)
C5—C20	1.473 (2)	C27—C32	1.388 (3)
C5—C6	1.488 (2)	C27—C28	1.389 (3)
C6—C26	1.327 (2)	C28—C29	1.395 (3)
C7—C8	1.374 (3)	C29—C30	1.372 (3)
C7—C12	1.392 (3)	C30—C31	1.363 (3)
C8—C9	1.376 (3)	C31—C32	1.386 (3)
C3—O1—N1	109.45 (16)	C10—C11—C12	119.9 (3)
C12—O3—C13	118.61 (19)	O3—C12—C11	124.8 (2)
C32—O4—C33	117.50 (16)	O3—C12—C7	115.1 (2)
C2—N1—O1	108.89 (16)	C11—C12—C7	120.1 (2)
C5—N2—C4	110.15 (14)	C15—C14—C19	117.7 (2)
C2—C1—C3	100.42 (15)	C15—C14—C2	120.7 (2)
C2—C1—C6	120.68 (16)	C19—C14—C2	121.53 (17)
C3—C1—C6	110.80 (16)	C14—C15—C16	120.6 (2)
C2—C1—C4	112.84 (15)	C17—C16—C15	120.7 (2)
C3—C1—C4	110.79 (16)	C18—C17—C16	119.3 (3)
C6—C1—C4	101.51 (13)	C17—C18—C19	119.8 (2)
N1—C2—C14	119.84 (17)	C18—C19—C14	121.8 (2)
N1—C2—C1	112.62 (19)	C25—C20—C21	118.10 (18)
C14—C2—C1	127.38 (17)	C25—C20—C5	119.96 (18)
O2—C3—O1	121.9 (2)	C21—C20—C5	121.94 (18)
O2—C3—C1	129.93 (19)	C22—C21—C20	120.8 (2)
O1—C3—C1	108.16 (18)	C23—C22—C21	120.2 (2)
N2—C4—C7	113.56 (15)	C22—C23—C24	119.5 (2)
N2—C4—C1	105.44 (14)	C25—C24—C23	120.4 (2)
C7—C4—C1	115.81 (16)	C24—C25—C20	120.9 (2)
N2—C5—C20	121.16 (16)	C6—C26—C27	125.27 (18)
N2—C5—C6	114.44 (16)	C32—C27—C28	118.59 (18)
C20—C5—C6	124.40 (18)	C32—C27—C26	120.73 (19)
C26—C6—C5	127.72 (17)	C28—C27—C26	120.67 (19)
C26—C6—C1	127.28 (16)	C27—C28—C29	120.7 (2)
C5—C6—C1	104.89 (16)	C30—C29—C28	119.0 (2)
C8—C7—C12	118.3 (2)	C31—C30—C29	121.3 (2)
C8—C7—C4	121.70 (19)	C30—C31—C32	119.8 (2)
C12—C7—C4	119.97 (19)	O4—C32—C31	123.5 (2)
C7—C8—C9	121.7 (2)	O4—C32—C27	115.87 (17)
C10—C9—C8	119.1 (3)	C31—C32—C27	120.6 (2)
C9—C10—C11	120.8 (3)
C3—O1—N1—C2	−1.8 (2)	C10—C11—C12—O3	179.4 (2)
O1—N1—C2—C14	−178.58 (16)	C10—C11—C12—C7	−0.4 (4)
O1—N1—C2—C1	−2.8 (2)	C8—C7—C12—O3	−179.8 (2)
C3—C1—C2—N1	5.7 (2)	C4—C7—C12—O3	1.5 (3)
C6—C1—C2—N1	127.63 (19)	C8—C7—C12—C11	0.1 (3)
C4—C1—C2—N1	−112.26 (19)	C4—C7—C12—C11	−178.6 (2)
C3—C1—C2—C14	−178.88 (18)	N1—C2—C14—C15	0.6 (3)
C6—C1—C2—C14	−57.0 (3)	C1—C2—C14—C15	−174.53 (19)
C4—C1—C2—C14	63.1 (2)	N1—C2—C14—C19	−179.57 (19)
N1—O1—C3—O2	−173.32 (19)	C1—C2—C14—C19	5.3 (3)
N1—O1—C3—C1	5.5 (2)	C19—C14—C15—C16	−1.4 (3)
C2—C1—C3—O2	172.1 (2)	C2—C14—C15—C16	178.4 (2)
C6—C1—C3—O2	43.5 (3)	C14—C15—C16—C17	−0.2 (4)
C4—C1—C3—O2	−68.4 (3)	C15—C16—C17—C18	1.6 (4)
C2—C1—C3—O1	−6.5 (2)	C16—C17—C18—C19	−1.3 (4)
C6—C1—C3—O1	−135.18 (16)	C17—C18—C19—C14	−0.4 (3)
C4—C1—C3—O1	112.95 (17)	C15—C14—C19—C18	1.7 (3)
C5—N2—C4—C7	141.90 (18)	C2—C14—C19—C18	−178.12 (19)
C5—N2—C4—C1	14.1 (2)	N2—C5—C20—C25	−38.8 (3)
C2—C1—C4—N2	−149.07 (16)	C6—C5—C20—C25	140.34 (19)
C3—C1—C4—N2	99.23 (17)	N2—C5—C20—C21	140.5 (2)
C6—C1—C4—N2	−18.48 (18)	C6—C5—C20—C21	−40.4 (3)
C2—C1—C4—C7	84.5 (2)	C25—C20—C21—C22	0.0 (3)
C3—C1—C4—C7	−27.2 (2)	C5—C20—C21—C22	−179.28 (18)
C6—C1—C4—C7	−144.93 (16)	C20—C21—C22—C23	−0.9 (3)
C4—N2—C5—C20	175.92 (17)	C21—C22—C23—C24	1.4 (3)
C4—N2—C5—C6	−3.3 (2)	C22—C23—C24—C25	−1.1 (3)
N2—C5—C6—C26	167.00 (19)	C23—C24—C25—C20	0.3 (3)
C20—C5—C6—C26	−12.2 (3)	C21—C20—C25—C24	0.3 (3)
N2—C5—C6—C1	−9.4 (2)	C5—C20—C25—C24	179.59 (18)
C20—C5—C6—C1	171.37 (17)	C5—C6—C26—C27	177.86 (19)
C2—C1—C6—C26	−34.5 (3)	C1—C6—C26—C27	−6.5 (3)
C3—C1—C6—C26	82.2 (2)	C6—C26—C27—C32	116.8 (2)
C4—C1—C6—C26	−160.08 (19)	C6—C26—C27—C28	−64.1 (3)
C2—C1—C6—C5	141.88 (17)	C32—C27—C28—C29	−1.0 (3)
C3—C1—C6—C5	−101.35 (17)	C26—C27—C28—C29	179.9 (2)
C4—C1—C6—C5	16.34 (18)	C27—C28—C29—C30	0.5 (3)
N2—C4—C7—C8	−31.9 (3)	C28—C29—C30—C31	0.6 (4)
C1—C4—C7—C8	90.4 (2)	C29—C30—C31—C32	−1.1 (4)
N2—C4—C7—C12	146.80 (18)	C33—O4—C32—C31	15.4 (3)
C1—C4—C7—C12	−91.0 (2)	C33—O4—C32—C27	−163.81 (18)
C12—C7—C8—C9	0.5 (4)	C30—C31—C32—O4	−178.5 (2)
C4—C7—C8—C9	179.2 (2)	C30—C31—C32—C27	0.6 (3)
C7—C8—C9—C10	−0.8 (4)	C28—C27—C32—O4	179.66 (18)
C8—C9—C10—C11	0.4 (5)	C26—C27—C32—O4	−1.3 (3)
C9—C10—C11—C12	0.1 (4)	C28—C27—C32—C31	0.4 (3)
C13—O3—C12—C11	−0.4 (3)	C26—C27—C32—C31	179.5 (2)
C13—O3—C12—C7	179.44 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O3	0.98	2.32	2.725 (2)	103
C8—H8A···O2	0.93	2.87	3.148 (3)	98
C8—H8A···N2	0.93	2.61	2.902 (3)	99
C15—H15A···N1	0.93	2.51	2.810 (3)	99
C25—H25A···N2	0.93	2.71	2.936 (3)	94
C13—H13A···O2^i	0.96	2.77	3.076 (3)	100
C30—H30A···O1^ii	0.93	2.54	3.396 (3)	153

Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z.