Ethyl 3-phenyl-4-[(Z)-3-phenyl­acrylo­yl] 5-(3,4,5-trimethoxy­phen­yl)pyrrolidine-2-carboxyl­ate

In the title compound, C₃₁H₃₃NO₆, the pyrrolidine ring adopts an envelope conformation. The mol­ecular structure is stabilized by an intra­molecular N—H...O hydrogen bond which generates an S(5) motif. The crystal packing is stabilized by C—H...O inter­molecular hydrogen bonds and C—H...π inter­actions. Inter­molecular C—H...O inter­actions are involved in the formation of dimers which are connected into a zigzag chain running along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.036
• wR factor = 0.099
• Data-to-parameter ratio = 9.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.93 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.67 Ratio
PLAT352_ALERT_3_C Short   N-H Bond (0.87A)   N1     -   H1     ...       0.74 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.42
           From the CIF: _reflns_number_total               3169
           Count of symmetry unique reflns         3175
           Completeness (_total/calc)             99.81%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2     ...          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     ...          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4     ...          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5     ...          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   7 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Pyrrolidine derivatives are present in a large number of biologically active natural products and numerous therapeutic agents. Radical cyclizations have emerged as a useful synthetic tool and have been reported in the synthesis of alkaloids and related pyrrolidinic compounds via the generation and trapping of nitrogen-centred radicals e.g. aminyl, iminyl, amidyl radicals etc. (Esker & Newcomb, 1993; Fallis & Brinza, 1997; Bowman et al., 1996; Guindon et al., 2001). However, no reports about the capture of neutral alkyl-oxyaminyl radicals by a multiple function have been published up to date for the preparation of fused pyrrolidine derivatives. In view of this biological importance, the crystal structure of the title compound has been determined and the results are presented here.

In the molecule of the title compound (Fig.1), the least-squares plane of the phenyl ring B lies almost perpendicular (86.4 (2)°) to the least-squares plane of the pyrrolidine ring A, whereas the least-squares plane of the trimethoxy phenyl ring C makes an angle of [60.0 (1)°]with the least-squares plane of the pyrrolidine ring A. The pyrrolidine ring A adopts an envelope conformation, with an approxymate C2 axis running through N1 and the centre of the C3—C4 bond. The puckering parameters (Cremer & Pople, 1975) q₂=0.395 (3)Å and ϕ=30.2 (4)°, and the smallest displacement asymmetry parameter(Nardelli, 1983) Δ_s(C2)=7.7 (2)°. The C16—C17—O3—C21 [-7.3 (3)] and C20—C19—O5—C23 [-0.5 (4)] torsional angles indicate that the two methoxy substitutions are essentially coplanor with the attached ring.

The molecular structure is stabilized by intramolecular N—H···O hydrogen bond which generates an S(5) motif (Fig. 2) (Bernstein et al., 1995). The refined N1—H1 distance is to short and its closure to the O1 atom which generates an hydrogen bond. The sum of the angles at donar atom N1 (335.7°) of the pyrrolidine ring is accordance with sp³ hybridization. The crystal packing is stabilized by C—H···O intermolecular hydrogen bonds and the C—H···π interactions. The molecules at (x, y, z) and (2 - x, 1 - y, z) are linked by C11—H11···O4 hydrogen bonds into cyclic centrosymmetric R₂²(24) dimers. The dimers are linked by the C12—H12···O3 hydrogen bond (Table 2.) forming C(12) zigzag chains running along the b axis directions. The dimers chains are cross-linked via C—H···π interactions involving the C9/C10/C11/C12/C13/C14 (centroid Cg2) and C15/C16/C17/C18/C19/C20 ring (Cg3) respectively (Table 2.).

Related literature

For related literature, see: Bernstein et al. (1995); Bowman et al. (1996); Cremer & Pople (1975); Esker & Newcomb (1993); Fallis & Brinza (1997); Guindon et al. (2001); Nardelli (1983, 1995).

S2. Experimental

To a solution of ethyl {[(1E)-(3,4,5-trimethoxyphenyl)methylene]amino} acetate (1 mmol) in dry acetonitrile (10 ml), triethylamine (1 mmol), (1E,4E,6Z)-4-benzylidene-1,7-diphenylhepta-1,6-diene-3,5-diones and then lithium bromide (0.1 equiv) were added. After the completion of the reaction as determined by TLC, the reaction mixture was filtered through a celite pad, washed with saturated aqueous solution of NH₄Cl and then extracted with CH₂Cl₂ (2x20 ml). The combined organic layers were washed with brine, dried (MgSO₄) filtered and the solvent evaporated in vacuo. The residue was purified by column chromatography on silica gel (100–200 mesh) with petroleum ether/ethyl acetate (4:1) to afford the cycloadduct, which was recrystallized in etanol.

S3. Refinement

The authors have located and refined the N—H hydrogen atom whereas the remaining three types of carbons, namely methane, methylene and methyl atoms are fixed.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997) and ORTEP-3 (Farrugia (1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).

Figures

Fig. 1. The molecular configuration and atom numbering scheme for (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Ethyl 3-phenyl-4-[(Z)-3-phenylacryloyl]5-(3,4,5-trimethoxyphenyl)-πyrrolidine-2-carboxylate

Crystal data

C31H33NO6	F(000) = 1096
Mr = 515.58	Dx = 1.259 Mg m^−3
Orthorhombic, p21212	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: p 2 2ab	Cell parameters from 10259 reflections
a = 13.7016 (5) Å	θ = 1.7–26.4°
b = 23.1680 (9) Å	µ = 0.09 mm^−1
c = 8.5695 (2) Å	T = 293 K
V = 2720.29 (16) Å^3	Block, colourless
Z = 4	0.26 × 0.15 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	3169 independent reflections
Radiation source: fine-focus sealed tube	2587 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 26.4°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.984, Tmax = 0.987	k = −28→23
16299 measured reflections	l = −10→6

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0555P)^2 + 0.2508P] where P = (Fo^2 + 2Fc^2)/3
3169 reflections	(Δ/σ)max = 0.003
347 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.16 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
O1	0.7792 (2)	0.47852 (9)	1.0428 (2)	0.0840 (7)
O2	0.68258 (16)	0.54921 (9)	0.9537 (2)	0.0722 (6)
O3	1.02935 (12)	0.26874 (7)	0.6449 (2)	0.0499 (4)
O4	1.08272 (11)	0.26970 (8)	0.3478 (2)	0.0539 (4)
O5	1.04771 (14)	0.36179 (8)	0.1643 (2)	0.0598 (5)
O6	0.69787 (16)	0.38770 (8)	0.7157 (2)	0.0675 (5)
N1	0.87654 (17)	0.47263 (11)	0.7542 (3)	0.0509 (5)
C2	0.87626 (16)	0.46216 (10)	0.5862 (3)	0.0421 (5)
H2	0.9017	0.4970	0.5356	0.051*
C3	0.76499 (16)	0.45786 (9)	0.5451 (3)	0.0383 (5)
H3	0.7538	0.4671	0.4349	0.046*
C4	0.71835 (16)	0.50404 (10)	0.6518 (2)	0.0400 (5)
H4	0.6607	0.4871	0.7015	0.048*
C5	0.79778 (17)	0.51404 (10)	0.7806 (3)	0.0433 (5)
H5	0.8244	0.5530	0.7668	0.052*
C6	0.7546 (2)	0.51027 (11)	0.9420 (3)	0.0546 (6)
C7	0.6255 (3)	0.55091 (17)	1.0957 (4)	0.0875 (11)
H7A	0.6635	0.5672	1.1803	0.105*
H7B	0.6051	0.5123	1.1251	0.105*
C8	0.5384 (3)	0.5879 (2)	1.0622 (5)	0.1124 (15)
H8A	0.4983	0.5904	1.1538	0.169*
H8B	0.5014	0.5712	0.9784	0.169*
H8C	0.5596	0.6258	1.0327	0.169*
C9	0.68751 (16)	0.55851 (10)	0.5691 (3)	0.0410 (5)
C10	0.75296 (18)	0.59451 (10)	0.4952 (3)	0.0466 (5)
H10	0.8189	0.5850	0.4963	0.056*
C11	0.7239 (2)	0.64415 (11)	0.4199 (3)	0.0574 (7)
H11	0.7698	0.6675	0.3708	0.069*
C12	0.6273 (2)	0.65901 (12)	0.4174 (4)	0.0659 (8)
H12	0.6073	0.6926	0.3674	0.079*
C13	0.5600 (2)	0.62392 (13)	0.4894 (4)	0.0744 (9)
H13	0.4943	0.6338	0.4877	0.089*
C14	0.58979 (18)	0.57397 (12)	0.5644 (4)	0.0599 (7)
H14	0.5436	0.5505	0.6122	0.072*
C15	0.93748 (15)	0.41216 (9)	0.5320 (3)	0.0401 (5)
C16	0.95837 (15)	0.36506 (9)	0.6259 (3)	0.0407 (5)
H16	0.9406	0.3653	0.7307	0.049*
C17	1.00602 (15)	0.31734 (10)	0.5633 (3)	0.0412 (5)
C18	1.03315 (15)	0.31654 (10)	0.4065 (3)	0.0429 (5)
C19	1.01529 (16)	0.36484 (11)	0.3146 (3)	0.0454 (6)
C20	0.96761 (15)	0.41252 (10)	0.3775 (3)	0.0435 (5)
H20	0.9559	0.4448	0.3156	0.052*
C21	1.0141 (2)	0.26865 (12)	0.8091 (3)	0.0572 (7)
H21A	1.0337	0.2321	0.8513	0.086*
H21B	0.9462	0.2750	0.8308	0.086*
H21C	1.0522	0.2988	0.8560	0.086*
C22	1.0267 (2)	0.23402 (11)	0.2476 (4)	0.0610 (7)
H22A	1.0663	0.2027	0.2107	0.091*
H22B	1.0040	0.2563	0.1604	0.091*
H22C	0.9717	0.2189	0.3039	0.091*
C23	1.0310 (3)	0.40979 (14)	0.0675 (3)	0.0833 (10)
H23A	1.0574	0.4024	−0.0343	0.125*
H23B	1.0621	0.4432	0.1114	0.125*
H23C	0.9621	0.4166	0.0593	0.125*
C24	0.72643 (16)	0.39775 (10)	0.5840 (3)	0.0433 (5)
C25	0.72722 (17)	0.35096 (10)	0.4693 (3)	0.0473 (6)
H25	0.7119	0.3143	0.5061	0.057*
C26	0.74747 (17)	0.35534 (10)	0.3189 (3)	0.0450 (5)
H26	0.7599	0.3920	0.2796	0.054*
C27	0.75193 (16)	0.30645 (10)	0.2085 (3)	0.0438 (5)
C28	0.75992 (19)	0.24969 (11)	0.2593 (3)	0.0526 (6)
H28	0.7620	0.2419	0.3657	0.063*
C29	0.7649 (2)	0.20470 (12)	0.1539 (4)	0.0616 (7)
H29	0.7715	0.1669	0.1893	0.074*
C30	0.7601 (2)	0.21589 (12)	−0.0037 (4)	0.0605 (7)
H30	0.7620	0.1856	−0.0748	0.073*
C31	0.7524 (2)	0.27172 (14)	−0.0558 (3)	0.0618 (7)
H31	0.7494	0.2793	−0.1622	0.074*
C32	0.74900 (19)	0.31668 (12)	0.0500 (3)	0.0524 (6)
H32	0.7447	0.3544	0.0138	0.063*
H1	0.862 (3)	0.4483 (17)	0.805 (5)	0.110 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.129 (2)	0.0714 (15)	0.0512 (11)	0.0143 (14)	0.0021 (13)	0.0141 (11)
O2	0.0975 (15)	0.0689 (13)	0.0503 (11)	0.0204 (12)	0.0185 (11)	−0.0080 (10)
O3	0.0598 (9)	0.0385 (9)	0.0515 (9)	0.0078 (8)	−0.0067 (8)	0.0020 (8)
O4	0.0515 (9)	0.0497 (10)	0.0606 (10)	0.0134 (8)	−0.0014 (8)	−0.0164 (9)
O5	0.0742 (11)	0.0552 (11)	0.0500 (10)	0.0065 (9)	0.0178 (9)	0.0007 (9)
O6	0.1046 (15)	0.0447 (10)	0.0531 (11)	−0.0130 (10)	0.0171 (11)	0.0020 (9)
N1	0.0611 (12)	0.0451 (13)	0.0466 (12)	0.0108 (11)	−0.0109 (11)	−0.0087 (11)
C2	0.0440 (11)	0.0335 (12)	0.0489 (13)	−0.0003 (10)	−0.0007 (10)	−0.0027 (11)
C3	0.0463 (11)	0.0329 (11)	0.0357 (11)	0.0016 (9)	0.0004 (9)	−0.0036 (10)
C4	0.0457 (11)	0.0334 (11)	0.0409 (11)	−0.0011 (9)	0.0052 (10)	−0.0031 (11)
C5	0.0572 (13)	0.0330 (12)	0.0397 (11)	0.0023 (10)	−0.0045 (10)	−0.0042 (10)
C6	0.0824 (17)	0.0386 (14)	0.0429 (12)	−0.0047 (14)	−0.0018 (14)	−0.0071 (12)
C7	0.108 (3)	0.094 (3)	0.0614 (18)	−0.008 (2)	0.0295 (19)	−0.0241 (19)
C8	0.090 (2)	0.137 (4)	0.110 (3)	0.004 (3)	0.031 (2)	−0.039 (3)
C9	0.0434 (11)	0.0353 (12)	0.0444 (12)	0.0047 (10)	−0.0033 (10)	−0.0099 (10)
C10	0.0427 (10)	0.0439 (13)	0.0532 (13)	0.0063 (11)	−0.0013 (11)	0.0035 (11)
C11	0.0661 (15)	0.0476 (15)	0.0585 (16)	0.0043 (13)	−0.0100 (14)	0.0046 (13)
C12	0.0730 (17)	0.0481 (16)	0.0764 (19)	0.0198 (14)	−0.0202 (16)	0.0020 (15)
C13	0.0505 (14)	0.068 (2)	0.105 (2)	0.0266 (15)	−0.0127 (16)	−0.0096 (19)
C14	0.0446 (12)	0.0558 (16)	0.079 (2)	0.0034 (12)	0.0020 (13)	−0.0058 (16)
C15	0.0365 (10)	0.0331 (12)	0.0509 (13)	−0.0020 (9)	−0.0006 (10)	−0.0064 (11)
C16	0.0419 (10)	0.0386 (12)	0.0416 (12)	−0.0003 (10)	−0.0009 (9)	−0.0041 (11)
C17	0.0374 (10)	0.0373 (12)	0.0488 (13)	−0.0004 (9)	−0.0056 (10)	−0.0034 (11)
C18	0.0391 (10)	0.0384 (12)	0.0510 (13)	0.0030 (9)	0.0005 (10)	−0.0082 (11)
C19	0.0423 (11)	0.0469 (14)	0.0471 (13)	−0.0012 (11)	0.0022 (10)	−0.0047 (12)
C20	0.0431 (11)	0.0378 (12)	0.0497 (13)	−0.0008 (10)	0.0026 (10)	0.0032 (11)
C21	0.0624 (15)	0.0550 (16)	0.0542 (15)	0.0077 (13)	−0.0009 (13)	0.0077 (13)
C22	0.0674 (16)	0.0441 (14)	0.0714 (17)	−0.0020 (13)	0.0028 (14)	−0.0134 (15)
C23	0.131 (3)	0.065 (2)	0.0543 (17)	−0.003 (2)	0.0280 (19)	0.0057 (16)
C24	0.0512 (12)	0.0355 (12)	0.0431 (13)	0.0000 (10)	−0.0023 (10)	−0.0036 (11)
C25	0.0560 (13)	0.0320 (12)	0.0539 (15)	−0.0063 (10)	0.0016 (11)	−0.0008 (11)
C26	0.0469 (11)	0.0387 (13)	0.0492 (13)	−0.0035 (11)	−0.0061 (11)	−0.0010 (11)
C27	0.0395 (10)	0.0443 (13)	0.0476 (13)	−0.0002 (10)	−0.0058 (10)	−0.0084 (11)
C28	0.0613 (14)	0.0509 (15)	0.0457 (13)	0.0019 (12)	−0.0031 (12)	−0.0061 (12)
C29	0.0691 (16)	0.0427 (14)	0.0731 (18)	0.0015 (13)	−0.0032 (15)	−0.0092 (14)
C30	0.0605 (15)	0.0591 (18)	0.0619 (16)	−0.0034 (14)	0.0045 (13)	−0.0246 (15)
C31	0.0634 (15)	0.078 (2)	0.0441 (13)	−0.0018 (15)	0.0003 (13)	−0.0139 (14)
C32	0.0569 (13)	0.0491 (14)	0.0513 (14)	−0.0013 (12)	0.0010 (12)	−0.0028 (12)

Geometric parameters (Å, º)

O1—C6	1.183 (3)	C12—H12	0.9300
O2—C6	1.341 (3)	C13—C14	1.385 (4)
O2—C7	1.447 (4)	C13—H13	0.9300
O3—C17	1.363 (3)	C14—H14	0.9300
O3—C21	1.422 (3)	C15—C16	1.386 (3)
O4—C18	1.375 (3)	C15—C20	1.387 (3)
O4—C22	1.418 (3)	C16—C17	1.392 (3)
O5—C19	1.364 (3)	C16—H16	0.9300
O5—C23	1.406 (3)	C17—C18	1.395 (3)
O6—C24	1.217 (3)	C18—C19	1.390 (3)
N1—C2	1.460 (3)	C19—C20	1.392 (3)
N1—C5	1.462 (3)	C20—H20	0.9300
N1—H1	0.74 (4)	C21—H21A	0.9600
C2—C15	1.504 (3)	C21—H21B	0.9600
C2—C3	1.568 (3)	C21—H21C	0.9600
C2—H2	0.9800	C22—H22A	0.9600
C3—C24	1.526 (3)	C22—H22B	0.9600
C3—C4	1.546 (3)	C22—H22C	0.9600
C3—H3	0.9800	C23—H23A	0.9600
C4—C9	1.508 (3)	C23—H23B	0.9600
C4—C5	1.567 (3)	C23—H23C	0.9600
C4—H4	0.9800	C24—C25	1.463 (3)
C5—C6	1.508 (3)	C25—C26	1.322 (3)
C5—H5	0.9800	C25—H25	0.9300
C6—O1	1.183 (3)	C26—C27	1.477 (3)
C7—C8	1.497 (5)	C26—H26	0.9300
C7—H7A	0.9700	C27—C32	1.379 (3)
C7—H7B	0.9700	C27—C28	1.390 (3)
C8—H8A	0.9600	C28—C29	1.381 (4)
C8—H8B	0.9600	C28—H28	0.9300
C8—H8C	0.9600	C29—C30	1.376 (4)
C9—C10	1.379 (3)	C29—H29	0.9300
C9—C14	1.387 (3)	C30—C31	1.372 (4)
C10—C11	1.378 (3)	C30—H30	0.9300
C10—H10	0.9300	C31—C32	1.382 (4)
C11—C12	1.368 (4)	C31—H31	0.9300
C11—H11	0.9300	C32—H32	0.9300
C12—C13	1.375 (4)
C6—O2—C7	118.6 (3)	C9—C14—H14	119.5
C17—O3—C21	118.31 (19)	C16—C15—C20	119.9 (2)
C18—O4—C22	114.44 (18)	C16—C15—C2	122.8 (2)
C19—O5—C23	117.6 (2)	C20—C15—C2	117.1 (2)
C2—N1—C5	105.1 (2)	C15—C16—C17	119.9 (2)
C2—N1—H1	117 (3)	C15—C16—H16	120.1
C5—N1—H1	103 (3)	C17—C16—H16	120.1
N1—C2—C15	115.5 (2)	O3—C17—C16	124.6 (2)
N1—C2—C3	103.58 (19)	O3—C17—C18	114.9 (2)
C15—C2—C3	115.09 (18)	C16—C17—C18	120.5 (2)
N1—C2—H2	107.4	O4—C18—C19	121.0 (2)
C15—C2—H2	107.4	O4—C18—C17	119.6 (2)
C3—C2—H2	107.4	C19—C18—C17	119.2 (2)
C24—C3—C4	111.05 (18)	O5—C19—C18	115.8 (2)
C24—C3—C2	110.20 (18)	O5—C19—C20	124.0 (2)
C4—C3—C2	103.00 (17)	C18—C19—C20	120.1 (2)
C24—C3—H3	110.8	C15—C20—C19	120.3 (2)
C4—C3—H3	110.8	C15—C20—H20	119.8
C2—C3—H3	110.8	C19—C20—H20	119.8
C9—C4—C3	114.66 (17)	O3—C21—H21A	109.5
C9—C4—C5	113.70 (19)	O3—C21—H21B	109.5
C3—C4—C5	103.41 (17)	H21A—C21—H21B	109.5
C9—C4—H4	108.3	O3—C21—H21C	109.5
C3—C4—H4	108.3	H21A—C21—H21C	109.5
C5—C4—H4	108.3	H21B—C21—H21C	109.5
N1—C5—C6	113.2 (2)	O4—C22—H22A	109.5
N1—C5—C4	107.86 (18)	O4—C22—H22B	109.5
C6—C5—C4	111.4 (2)	H22A—C22—H22B	109.5
N1—C5—H5	108.1	O4—C22—H22C	109.5
C6—C5—H5	108.1	H22A—C22—H22C	109.5
C4—C5—H5	108.1	H22B—C22—H22C	109.5
O1—C6—O2	125.1 (3)	O5—C23—H23A	109.5
O1—C6—O2	125.1 (3)	O5—C23—H23B	109.5
O1—C6—C5	126.4 (3)	H23A—C23—H23B	109.5
O1—C6—C5	126.4 (3)	O5—C23—H23C	109.5
O2—C6—C5	108.6 (2)	H23A—C23—H23C	109.5
O2—C7—C8	106.6 (3)	H23B—C23—H23C	109.5
O2—C7—H7A	110.4	O6—C24—C25	118.9 (2)
C8—C7—H7A	110.4	O6—C24—C3	119.2 (2)
O2—C7—H7B	110.4	C25—C24—C3	121.8 (2)
C8—C7—H7B	110.4	C26—C25—C24	126.8 (2)
H7A—C7—H7B	108.6	C26—C25—H25	116.6
C7—C8—H8A	109.5	C24—C25—H25	116.6
C7—C8—H8B	109.5	C25—C26—C27	125.0 (2)
H8A—C8—H8B	109.5	C25—C26—H26	117.5
C7—C8—H8C	109.5	C27—C26—H26	117.5
H8A—C8—H8C	109.5	C32—C27—C28	118.3 (2)
H8B—C8—H8C	109.5	C32—C27—C26	119.9 (2)
C10—C9—C14	117.3 (2)	C28—C27—C26	121.9 (2)
C10—C9—C4	122.7 (2)	C29—C28—C27	120.9 (2)
C14—C9—C4	120.0 (2)	C29—C28—H28	119.6
C11—C10—C9	122.2 (2)	C27—C28—H28	119.6
C11—C10—H10	118.9	C30—C29—C28	119.8 (3)
C9—C10—H10	118.9	C30—C29—H29	120.1
C12—C11—C10	119.8 (3)	C28—C29—H29	120.1
C12—C11—H11	120.1	C31—C30—C29	120.0 (3)
C10—C11—H11	120.1	C31—C30—H30	120.0
C11—C12—C13	119.5 (3)	C29—C30—H30	120.0
C11—C12—H12	120.2	C30—C31—C32	120.0 (3)
C13—C12—H12	120.2	C30—C31—H31	120.0
C12—C13—C14	120.3 (2)	C32—C31—H31	120.0
C12—C13—H13	119.8	C27—C32—C31	121.0 (3)
C14—C13—H13	119.8	C27—C32—H32	119.5
C13—C14—C9	120.9 (3)	C31—C32—H32	119.5
C13—C14—H14	119.5
C5—N1—C2—C15	−168.34 (19)	N1—C2—C15—C20	−157.7 (2)
C5—N1—C2—C3	−41.5 (2)	C3—C2—C15—C20	81.6 (3)
N1—C2—C3—C24	−80.9 (2)	C20—C15—C16—C17	−2.6 (3)
C15—C2—C3—C24	46.2 (3)	C2—C15—C16—C17	172.7 (2)
N1—C2—C3—C4	37.6 (2)	C21—O3—C17—C16	−7.3 (3)
C15—C2—C3—C4	164.70 (19)	C21—O3—C17—C18	173.1 (2)
C24—C3—C4—C9	−136.9 (2)	C15—C16—C17—O3	−179.51 (19)
C2—C3—C4—C9	105.1 (2)	C15—C16—C17—C18	0.1 (3)
C24—C3—C4—C5	98.7 (2)	C22—O4—C18—C19	−76.5 (3)
C2—C3—C4—C5	−19.2 (2)	C22—O4—C18—C17	107.8 (3)
C2—N1—C5—C6	153.2 (2)	O3—C17—C18—O4	−2.2 (3)
C2—N1—C5—C4	29.4 (3)	C16—C17—C18—O4	178.11 (19)
C9—C4—C5—N1	−130.0 (2)	O3—C17—C18—C19	−177.99 (19)
C3—C4—C5—N1	−5.0 (2)	C16—C17—C18—C19	2.4 (3)
C9—C4—C5—C6	105.2 (2)	C23—O5—C19—C18	180.0 (2)
C3—C4—C5—C6	−129.9 (2)	C23—O5—C19—C20	−0.5 (4)
O1—O1—C6—O2	0.0 (7)	O4—C18—C19—O5	1.5 (3)
O1—O1—C6—C5	0.0 (7)	C17—C18—C19—O5	177.2 (2)
C7—O2—C6—O1	−4.2 (4)	O4—C18—C19—C20	−178.04 (19)
C7—O2—C6—O1	−4.2 (4)	C17—C18—C19—C20	−2.4 (3)
C7—O2—C6—C5	175.8 (2)	C16—C15—C20—C19	2.6 (3)
N1—C5—C6—O1	0.8 (4)	C2—C15—C20—C19	−173.0 (2)
C4—C5—C6—O1	122.6 (3)	O5—C19—C20—C15	−179.6 (2)
N1—C5—C6—O1	0.8 (4)	C18—C19—C20—C15	−0.1 (3)
C4—C5—C6—O1	122.6 (3)	C4—C3—C24—O6	−27.1 (3)
N1—C5—C6—O2	−179.2 (2)	C2—C3—C24—O6	86.3 (3)
C4—C5—C6—O2	−57.4 (3)	C4—C3—C24—C25	155.9 (2)
C6—O2—C7—C8	−167.3 (3)	C2—C3—C24—C25	−90.7 (3)
C3—C4—C9—C10	−63.0 (3)	O6—C24—C25—C26	173.6 (3)
C5—C4—C9—C10	55.7 (3)	C3—C24—C25—C26	−9.4 (4)
C3—C4—C9—C14	116.6 (2)	C24—C25—C26—C27	177.0 (2)
C5—C4—C9—C14	−124.7 (2)	C25—C26—C27—C32	163.6 (3)
C14—C9—C10—C11	0.3 (4)	C25—C26—C27—C28	−17.0 (4)
C4—C9—C10—C11	179.9 (2)	C32—C27—C28—C29	0.1 (4)
C9—C10—C11—C12	0.2 (4)	C26—C27—C28—C29	−179.4 (2)
C10—C11—C12—C13	−0.5 (5)	C27—C28—C29—C30	−1.2 (4)
C11—C12—C13—C14	0.2 (5)	C28—C29—C30—C31	1.3 (5)
C12—C13—C14—C9	0.3 (5)	C29—C30—C31—C32	−0.3 (5)
C10—C9—C14—C13	−0.5 (4)	C28—C27—C32—C31	1.0 (4)
C4—C9—C14—C13	179.8 (2)	C26—C27—C32—C31	−179.5 (2)
N1—C2—C15—C16	26.9 (3)	C30—C31—C32—C27	−0.9 (4)
C3—C2—C15—C16	−93.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.74 (4)	2.44 (4)	2.813 (3)	113 (4)
C11—H11···O4^i	0.93	2.50	3.374 (3)	157
C12—H12···O3^ii	0.93	2.57	3.370 (3)	144
C7—H7A···Cg2^iii	0.97	2.85	3.683 (4)	145
C10—H10···Cg3^i	0.93	2.92	3.701 (3)	142

Symmetry codes: (i) −x+2, −y+1, z; (ii) −x+3/2, y+1/2, −z+1; (iii) x, y, z+1.