5′′-Benzyl­idene-1′′-methyl-4′,5′-diphenyl-1H-indole-3-spiro-2′-pyrrolidine-3′-spiro-3′′-piperidine-2,4′′-dione

Kumar, B.R.; Pandiarajan, S.; Ramakrishnan, V.; Kumar, R.R.; Perumal, S.

doi:10.1107/S1600536807025822

5′′-Benzylidene-1′′-methyl-4′,5′-diphenyl-1H-indole-3-spiro-2′-pyrrolidine-3′-spiro-3′′-piperidine-2,4′′-dione

B. R. Kumar, S. Pandiarajan, V. Ramakrishnan, R. R. Kumar and S. Perumal

In the title compound, C₃₅H₃₄N₁₀O₂S₂, the six-membered heterocyclic ring adopts a half-chair conformation, while the pyrrolidine five-membered ring exists in an envelope conformation. However the other five-membered ring in the oxindole maintains planarity. In the crystal structure, molecules form N—H

O hydrogen-bonded dimers around inversion centres. The structure is further stabilized by a C—H

π interaction.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025822/sj2320sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025822/sj2320Isup2.hkl Contains datablock I

CCDC reference: 654963

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.005 Å
R factor = 0.051
wR factor = 0.143
Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT601_ALERT_2_A Structure Contains Solvent Accessible VOIDS of .     264.00 A   3

Author Response: The problem of the disordered solvent molecule is resolved using the Squeeze program. The disordered solvent may be ethanol moiety which is used for crystallization. See experimental section.


Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         46 Perc.
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.76 Ratio
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3A    ...          ?

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT793_ALERT_1_G Check the Absolute Configuration of C1     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C2     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C3     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C4     = ...          R

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

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

1,3-Dipolar cycloadditions are versatile synthetic strategies employed for the construction of five-membered heterocycles (Jiang et al., 2006). 1,3-dipolar cycloadditions of azomethine ylides to alkenes afford pyrrolidines, which exhibit important biological properties (Lundahl et al.,1972). The extensive use of isatin as a precursor for 1,3-dipolar cycloadditions stems from the fact that it generates a wide variety of azomethine ylides with primary and secondary amines, These can be trapped with suitable dipolarophiles (Cravotto et al., 2001). The piperidone sub-structure is a versatile entity in synthetic organic chemistry due to its pharmacological properties. Such compounds display potent cytotoxicity towards human Molt 4/C8 and CEM T-lymphocytes as well as murine P388 and L1210 leukemic cells and spasmolytic activities (Dimmock et al., 2003; Abignente & Biniecka-Picazio, 1977). We report here the synthesis and structure of a novel spiropyrrolidine, the title compound (I), Fig. 1.

The slightly distorted half-chair conformation of the piperidin-4-one ring is confirmed by the puckering analysis [q₂ = 0.312 (1) Å, φ₂ = 230 (2) °, q₃ = -0.449 (1) Å; Cremer & Pople, 1975] (Fig. 1). Also, the 5-membered ring is in an envelope conformation with the puckering values of q₂ = 0.427 (2) Å, φ₂ = 329 (2)°. The benzene ring fused to the 5-membered ring is oriented with an angle of 80.4 (1)°. The two phenyl rings (C23—C28 and C29—C34) subtend angles of 27.9 (2) and 85.8 (1)° with the methylidenephenyl ring (C17—C22) attached to the 6-membered ring.

In the crystal structure, molecules dimerize through the N—H···O hydrogen bonds around an inversion centre (Fig. 2). The crystal is further stabilized by C—H···π interactions between H31 and the C17—C22 benzene ring (centroid Cg1) (Table 1).

Related literature top

For general background, see: Jiang et al. (2006); Lundahl et al. (1972); Cravotto et al. (2001); Dimmock et al. (2003); Abignente & Biniecka-Picazio (1977). For puckering analysis of heterocyclic rings, see: Cremer & Pople (1975).

Experimental top

1-Methyl-3,5-bis[(E)-phenylmethylidene]tetrahydro-4(1H)-pyridinone (1 mmol), isatin (1 mmol) and benzyl amine (1 mmol) were mixed well in a tube and kept over a water bath at 85–90^o C for 10–15 s until the mixture becomes a viscous paste to ensure thorough mixing and left aside for 10 min at ambient temperature. After completion of the reaction (TLC), the viscous paste was recrystallized from ethanol to obtain pure crystals of the title compound.

Structure description top

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL/PC (Bruker, 2000); program(s) used to refine structure: SHELXTL/PC; molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL/PC.

Figures top

	Fig. 1. The molecular structure of the title compound (I) with the numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. Crystal packing for (I) viewed down the a-axis. H bonds are drawn as dashed lines.

5''-Benzylidene-1''-methyl-4',5'-diphenyl-1H-indole-3-spiro-2'-pyrrolidine-3'-spiro-3''-piperidine-2,4''-dione top

Crystal data top

C₃₅H₃₁N₃O₂	Z = 2
M_r = 525.63	F(000) = 556
Triclinic, P1	D_x = 1.118 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.194 (4) Å	Cell parameters from 25 reflections
b = 10.681 (5) Å	θ = 9.1–12.7°
c = 15.352 (8) Å	µ = 0.07 mm⁻¹
α = 80.76 (4)°	T = 293 K
β = 80.31 (2)°	Block, colourless
γ = 72.71 (5)°	0.25 × 0.21 × 0.18 mm
V = 1562.4 (13) Å³

Data collection top

Nonius MACH3 sealed-tube diffractometer	2506 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 25.0°, θ_min = 2.0°
ω/2θ scans	h = −1→12
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
T_min = 0.968, T_max = 0.995	l = −18→18
6511 measured reflections	3 standard reflections every 60 min
5494 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 0.89	w = 1/[σ²(F_o²) + (0.0742P)²] where P = (F_o² + 2F_c²)/3
5494 reflections	(Δ/σ)_max < 0.001
363 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₃₅H₃₁N₃O₂	γ = 72.71 (5)°
M_r = 525.63	V = 1562.4 (13) Å³
Triclinic, P1	Z = 2
a = 10.194 (4) Å	Mo Kα radiation
b = 10.681 (5) Å	µ = 0.07 mm⁻¹
c = 15.352 (8) Å	T = 293 K
α = 80.76 (4)°	0.25 × 0.21 × 0.18 mm
β = 80.31 (2)°

Data collection top

Nonius MACH3 sealed-tube diffractometer	2506 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.020
T_min = 0.968, T_max = 0.995	3 standard reflections every 60 min
6511 measured reflections	intensity decay: none
5494 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 0.89	Δρ_max = 0.26 e Å⁻³
5494 reflections	Δρ_min = −0.22 e Å⁻³
363 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.7418 (3)	0.2828 (2)	0.35142 (15)	0.0446 (6)
C2	0.7663 (3)	0.0554 (2)	0.40313 (16)	0.0474 (7)
H2	0.6821	0.0705	0.4462	0.057*
C3	0.7292 (3)	0.0721 (2)	0.30834 (16)	0.0446 (6)
H3	0.8171	0.0436	0.2699	0.053*
C4	0.6756 (3)	0.2245 (2)	0.28475 (16)	0.0446 (6)
C5	0.5182 (3)	0.2759 (2)	0.29432 (18)	0.0534 (7)
H5A	0.4825	0.2424	0.2509	0.064*
H5B	0.4789	0.2462	0.3533	0.064*
C6	0.5102 (3)	0.4660 (3)	0.18724 (19)	0.0614 (8)
H6A	0.4952	0.5609	0.1810	0.074*
H6B	0.4461	0.4484	0.1539	0.074*
C7	0.6546 (3)	0.4031 (2)	0.14835 (17)	0.0532 (7)
C8	0.7281 (3)	0.2684 (2)	0.18842 (17)	0.0501 (7)
C9	0.7272 (4)	0.4596 (3)	0.08092 (19)	0.0683 (9)
H9	0.8160	0.4074	0.0640	0.082*
C10	0.6297 (3)	0.3648 (2)	0.41871 (18)	0.0495 (7)
C11	0.7583 (3)	0.5007 (2)	0.34650 (17)	0.0501 (7)
C12	0.8105 (4)	0.6082 (3)	0.3224 (2)	0.0679 (8)
H12	0.7677	0.6873	0.3463	0.081*
C13	0.9275 (4)	0.5945 (3)	0.2620 (2)	0.0828 (10)
H13	0.9637	0.6663	0.2439	0.099*
C14	0.9937 (4)	0.4764 (4)	0.2270 (2)	0.0793 (9)
H14	1.0732	0.4696	0.1861	0.095*
C15	0.9413 (3)	0.3688 (3)	0.25317 (19)	0.0648 (8)
H15	0.9869	0.2886	0.2314	0.078*
C16	0.8218 (3)	0.3812 (2)	0.31119 (16)	0.0467 (7)
C17	0.6895 (4)	0.5905 (3)	0.02937 (19)	0.0708 (9)
C18	0.7963 (5)	0.6480 (4)	−0.0052 (2)	0.1059 (13)
H18	0.8864	0.6036	0.0057	0.127*
C19	0.7696 (6)	0.7709 (4)	−0.0559 (3)	0.1232 (17)
H19	0.8415	0.8088	−0.0781	0.148*
C20	0.6374 (7)	0.8359 (4)	−0.0729 (3)	0.1199 (17)
H20	0.6196	0.9175	−0.1075	0.144*
C21	0.5315 (5)	0.7812 (4)	−0.0390 (3)	0.1031 (13)
H21	0.4417	0.8266	−0.0501	0.124*
C22	0.5567 (4)	0.6586 (3)	0.0116 (2)	0.0843 (11)
H22	0.4838	0.6220	0.0336	0.101*
C23	0.8664 (3)	−0.0761 (2)	0.42894 (17)	0.0485 (7)
C24	0.8285 (3)	−0.1674 (3)	0.4941 (2)	0.0679 (8)
H24	0.7399	−0.1471	0.5254	0.081*
C25	0.9218 (4)	−0.2906 (3)	0.5138 (2)	0.0793 (10)
H25	0.8946	−0.3513	0.5583	0.095*
C26	1.0515 (4)	−0.3227 (3)	0.4690 (2)	0.0732 (9)
H26	1.1123	−0.4057	0.4815	0.088*
C27	1.0917 (3)	−0.2317 (3)	0.4053 (2)	0.0748 (9)
H27	1.1811	−0.2519	0.3751	0.090*
C28	0.9998 (3)	−0.1098 (3)	0.3856 (2)	0.0642 (8)
H28	1.0286	−0.0489	0.3420	0.077*
C29	0.6387 (3)	−0.0084 (2)	0.29153 (17)	0.0471 (7)
C30	0.6614 (3)	−0.0580 (3)	0.21036 (19)	0.0621 (8)
H30	0.7315	−0.0409	0.1671	0.075*
C31	0.5803 (4)	−0.1329 (3)	0.1932 (2)	0.0823 (10)
H31	0.5965	−0.1660	0.1388	0.099*
C32	0.4765 (4)	−0.1580 (3)	0.2564 (3)	0.0885 (11)
H32	0.4216	−0.2075	0.2447	0.106*
C33	0.4539 (4)	−0.1109 (3)	0.3358 (2)	0.0861 (10)
H33	0.3834	−0.1283	0.3787	0.103*
C34	0.5342 (3)	−0.0373 (3)	0.3538 (2)	0.0681 (8)
H34	0.5176	−0.0064	0.4090	0.082*
C35	0.3367 (3)	0.4792 (3)	0.3149 (2)	0.0911 (11)
H35A	0.3223	0.4527	0.3778	0.137*
H35B	0.2763	0.4508	0.2857	0.137*
H35C	0.3169	0.5736	0.3042	0.137*
N1	0.4800 (2)	0.41942 (19)	0.28030 (15)	0.0553 (6)
N2	0.6481 (2)	0.48676 (19)	0.41089 (14)	0.0534 (6)
H2A	0.5978	0.5482	0.4420	0.064*
N3	0.8292 (2)	0.16302 (18)	0.39558 (14)	0.0521 (6)
H3A	0.9061	0.1571	0.4142	0.063*
O1	0.8263 (2)	0.19800 (18)	0.14694 (12)	0.0719 (6)
O2	0.5457 (2)	0.32358 (17)	0.47439 (12)	0.0623 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0525 (16)	0.0346 (14)	0.0450 (15)	−0.0081 (12)	−0.0037 (13)	−0.0104 (11)
C2	0.0566 (17)	0.0362 (14)	0.0483 (15)	−0.0070 (13)	−0.0072 (13)	−0.0125 (11)
C3	0.0507 (16)	0.0352 (13)	0.0445 (14)	−0.0039 (12)	−0.0028 (12)	−0.0139 (11)
C4	0.0500 (17)	0.0328 (13)	0.0490 (15)	−0.0051 (12)	−0.0046 (13)	−0.0132 (11)
C5	0.0594 (19)	0.0430 (15)	0.0569 (16)	−0.0081 (14)	−0.0092 (14)	−0.0131 (12)
C6	0.074 (2)	0.0427 (16)	0.067 (2)	−0.0064 (15)	−0.0240 (17)	−0.0074 (14)
C7	0.072 (2)	0.0441 (16)	0.0438 (16)	−0.0110 (15)	−0.0142 (15)	−0.0074 (13)
C8	0.0634 (19)	0.0365 (14)	0.0490 (16)	−0.0078 (14)	−0.0070 (14)	−0.0124 (12)
C9	0.097 (2)	0.0515 (18)	0.0545 (18)	−0.0143 (17)	−0.0146 (18)	−0.0060 (14)
C10	0.0620 (18)	0.0371 (15)	0.0455 (15)	−0.0046 (13)	−0.0096 (14)	−0.0084 (12)
C11	0.0649 (19)	0.0403 (15)	0.0470 (16)	−0.0123 (14)	−0.0164 (15)	−0.0055 (12)
C12	0.087 (2)	0.0459 (17)	0.077 (2)	−0.0211 (17)	−0.0241 (19)	−0.0044 (15)
C13	0.094 (3)	0.075 (2)	0.094 (3)	−0.050 (2)	−0.018 (2)	0.003 (2)
C14	0.076 (2)	0.088 (3)	0.083 (2)	−0.040 (2)	−0.0053 (19)	−0.010 (2)
C15	0.065 (2)	0.066 (2)	0.0660 (19)	−0.0185 (17)	−0.0067 (17)	−0.0156 (15)
C16	0.0540 (17)	0.0400 (15)	0.0464 (15)	−0.0114 (13)	−0.0081 (14)	−0.0076 (12)
C17	0.111 (3)	0.0475 (18)	0.0534 (18)	−0.020 (2)	−0.013 (2)	−0.0044 (14)
C18	0.130 (3)	0.067 (2)	0.098 (3)	−0.021 (2)	0.018 (3)	0.009 (2)
C19	0.168 (5)	0.074 (3)	0.109 (3)	−0.037 (3)	0.009 (3)	0.018 (2)
C20	0.194 (5)	0.064 (3)	0.090 (3)	−0.026 (3)	−0.026 (3)	0.016 (2)
C21	0.161 (4)	0.071 (3)	0.081 (3)	−0.025 (3)	−0.056 (3)	0.007 (2)
C22	0.128 (3)	0.063 (2)	0.069 (2)	−0.026 (2)	−0.044 (2)	0.0035 (17)
C23	0.0549 (18)	0.0354 (14)	0.0537 (16)	−0.0028 (13)	−0.0144 (14)	−0.0119 (13)
C24	0.076 (2)	0.0466 (17)	0.077 (2)	−0.0122 (16)	−0.0164 (17)	0.0030 (16)
C25	0.101 (3)	0.052 (2)	0.087 (2)	−0.022 (2)	−0.034 (2)	0.0125 (17)
C26	0.077 (2)	0.0435 (18)	0.100 (3)	0.0014 (17)	−0.039 (2)	−0.0192 (18)
C27	0.074 (2)	0.054 (2)	0.090 (2)	0.0014 (18)	−0.0168 (19)	−0.0219 (18)
C28	0.068 (2)	0.0442 (17)	0.0727 (19)	−0.0004 (15)	−0.0106 (17)	−0.0113 (14)
C29	0.0611 (18)	0.0312 (13)	0.0478 (15)	−0.0086 (13)	−0.0090 (14)	−0.0070 (11)
C30	0.085 (2)	0.0437 (16)	0.0569 (17)	−0.0112 (15)	−0.0152 (16)	−0.0089 (13)
C31	0.120 (3)	0.062 (2)	0.075 (2)	−0.023 (2)	−0.033 (2)	−0.0225 (17)
C32	0.115 (3)	0.063 (2)	0.109 (3)	−0.043 (2)	−0.044 (3)	−0.004 (2)
C33	0.108 (3)	0.085 (2)	0.085 (3)	−0.058 (2)	−0.016 (2)	−0.004 (2)
C34	0.085 (2)	0.0649 (19)	0.0622 (19)	−0.0303 (18)	−0.0074 (18)	−0.0134 (15)
C35	0.062 (2)	0.075 (2)	0.115 (3)	0.0094 (18)	0.001 (2)	−0.019 (2)
N1	0.0521 (15)	0.0398 (13)	0.0667 (16)	0.0008 (11)	−0.0059 (12)	−0.0130 (11)
N2	0.0724 (16)	0.0319 (12)	0.0531 (13)	−0.0044 (11)	−0.0087 (12)	−0.0156 (10)
N3	0.0548 (14)	0.0348 (12)	0.0692 (15)	−0.0068 (10)	−0.0222 (12)	−0.0086 (10)
O1	0.0881 (15)	0.0495 (11)	0.0595 (12)	−0.0009 (11)	0.0131 (12)	−0.0109 (10)
O2	0.0826 (15)	0.0434 (11)	0.0538 (12)	−0.0135 (10)	0.0120 (11)	−0.0147 (9)

Geometric parameters (Å, º) top

C1—N3	1.462 (3)	C17—C18	1.393 (5)
C1—C16	1.511 (3)	C18—C19	1.390 (5)
C1—C10	1.561 (3)	C18—H18	0.9300
C1—C4	1.606 (3)	C19—C20	1.367 (6)
C2—N3	1.455 (3)	C19—H19	0.9300
C2—C23	1.509 (3)	C20—C21	1.365 (6)
C2—C3	1.534 (3)	C20—H20	0.9300
C2—H2	0.9800	C21—C22	1.387 (4)
C3—C29	1.509 (4)	C21—H21	0.9300
C3—C4	1.558 (3)	C22—H22	0.9300
C3—H3	0.9800	C23—C24	1.371 (4)
C4—C5	1.523 (3)	C23—C28	1.379 (4)
C4—C8	1.534 (3)	C24—C25	1.397 (4)
C5—N1	1.454 (3)	C24—H24	0.9300
C5—H5A	0.9700	C25—C26	1.356 (4)
C5—H5B	0.9700	C25—H25	0.9300
C6—N1	1.448 (3)	C26—C27	1.366 (4)
C6—C7	1.490 (4)	C26—H26	0.9300
C6—H6A	0.9700	C27—C28	1.382 (4)
C6—H6B	0.9700	C27—H27	0.9300
C7—C9	1.338 (4)	C28—H28	0.9300
C7—C8	1.496 (4)	C29—C34	1.379 (4)
C8—O1	1.210 (3)	C29—C30	1.389 (3)
C9—C17	1.468 (4)	C30—C31	1.387 (4)
C9—H9	0.9300	C30—H30	0.9300
C10—O2	1.230 (3)	C31—C32	1.369 (5)
C10—N2	1.354 (3)	C31—H31	0.9300
C11—C12	1.378 (4)	C32—C33	1.351 (5)
C11—N2	1.393 (3)	C32—H32	0.9300
C11—C16	1.397 (3)	C33—C34	1.375 (4)
C12—C13	1.368 (4)	C33—H33	0.9300
C12—H12	0.9300	C34—H34	0.9300
C13—C14	1.387 (4)	C35—N1	1.455 (3)
C13—H13	0.9300	C35—H35A	0.9600
C14—C15	1.383 (4)	C35—H35B	0.9600
C14—H14	0.9300	C35—H35C	0.9600
C15—C16	1.368 (4)	N2—H2A	0.8600
C15—H15	0.9300	N3—H3A	0.8600
C17—C22	1.383 (4)

N3—C1—C16	112.0 (2)	C18—C17—C9	117.2 (3)
N3—C1—C10	112.3 (2)	C19—C18—C17	120.8 (4)
C16—C1—C10	100.90 (19)	C19—C18—H18	119.6
N3—C1—C4	102.18 (17)	C17—C18—H18	119.6
C16—C1—C4	117.40 (19)	C20—C19—C18	119.8 (5)
C10—C1—C4	112.6 (2)	C20—C19—H19	120.1
N3—C2—C23	111.4 (2)	C18—C19—H19	120.1
N3—C2—C3	99.96 (19)	C21—C20—C19	120.1 (4)
C23—C2—C3	113.86 (19)	C21—C20—H20	120.0
N3—C2—H2	110.4	C19—C20—H20	120.0
C23—C2—H2	110.4	C20—C21—C22	120.7 (4)
C3—C2—H2	110.4	C20—C21—H21	119.7
C29—C3—C2	117.1 (2)	C22—C21—H21	119.7
C29—C3—C4	116.4 (2)	C17—C22—C21	120.3 (4)
C2—C3—C4	103.98 (18)	C17—C22—H22	119.8
C29—C3—H3	106.2	C21—C22—H22	119.8
C2—C3—H3	106.2	C24—C23—C28	117.5 (3)
C4—C3—H3	106.2	C24—C23—C2	121.9 (3)
C5—C4—C8	106.4 (2)	C28—C23—C2	120.5 (2)
C5—C4—C3	113.4 (2)	C23—C24—C25	120.6 (3)
C8—C4—C3	111.58 (19)	C23—C24—H24	119.7
C5—C4—C1	112.41 (18)	C25—C24—H24	119.7
C8—C4—C1	109.30 (19)	C26—C25—C24	120.9 (3)
C3—C4—C1	103.79 (19)	C26—C25—H25	119.6
N1—C5—C4	108.6 (2)	C24—C25—H25	119.6
N1—C5—H5A	110.0	C25—C26—C27	119.2 (3)
C4—C5—H5A	110.0	C25—C26—H26	120.4
N1—C5—H5B	110.0	C27—C26—H26	120.4
C4—C5—H5B	110.0	C26—C27—C28	120.1 (3)
H5A—C5—H5B	108.4	C26—C27—H27	119.9
N1—C6—C7	113.2 (2)	C28—C27—H27	119.9
N1—C6—H6A	108.9	C23—C28—C27	121.7 (3)
C7—C6—H6A	108.9	C23—C28—H28	119.2
N1—C6—H6B	108.9	C27—C28—H28	119.2
C7—C6—H6B	108.9	C34—C29—C30	117.5 (3)
H6A—C6—H6B	107.8	C34—C29—C3	123.1 (2)
C9—C7—C6	124.9 (3)	C30—C29—C3	119.4 (2)
C9—C7—C8	116.3 (3)	C31—C30—C29	120.6 (3)
C6—C7—C8	118.7 (2)	C31—C30—H30	119.7
O1—C8—C7	121.3 (2)	C29—C30—H30	119.7
O1—C8—C4	121.5 (2)	C32—C31—C30	120.0 (3)
C7—C8—C4	117.3 (2)	C32—C31—H31	120.0
C7—C9—C17	130.5 (3)	C30—C31—H31	120.0
C7—C9—H9	114.7	C33—C32—C31	119.9 (3)
C17—C9—H9	114.7	C33—C32—H32	120.0
O2—C10—N2	125.2 (2)	C31—C32—H32	120.0
O2—C10—C1	126.3 (2)	C32—C33—C34	120.5 (3)
N2—C10—C1	108.3 (2)	C32—C33—H33	119.7
C12—C11—N2	128.4 (3)	C34—C33—H33	119.7
C12—C11—C16	121.8 (3)	C33—C34—C29	121.4 (3)
N2—C11—C16	109.7 (2)	C33—C34—H34	119.3
C13—C12—C11	117.6 (3)	C29—C34—H34	119.3
C13—C12—H12	121.2	N1—C35—H35A	109.5
C11—C12—H12	121.2	N1—C35—H35B	109.5
C12—C13—C14	121.7 (3)	H35A—C35—H35B	109.5
C12—C13—H13	119.1	N1—C35—H35C	109.5
C14—C13—H13	119.1	H35A—C35—H35C	109.5
C15—C14—C13	119.9 (3)	H35B—C35—H35C	109.5
C15—C14—H14	120.1	C6—N1—C5	110.8 (2)
C13—C14—H14	120.1	C6—N1—C35	111.5 (2)
C16—C15—C14	119.5 (3)	C5—N1—C35	112.8 (2)
C16—C15—H15	120.2	C10—N2—C11	111.9 (2)
C14—C15—H15	120.2	C10—N2—H2A	124.1
C15—C16—C11	119.4 (2)	C11—N2—H2A	124.1
C15—C16—C1	131.4 (2)	C2—N3—C1	109.5 (2)
C11—C16—C1	109.1 (2)	C2—N3—H3A	125.2
C22—C17—C18	118.3 (3)	C1—N3—H3A	125.2
C22—C17—C9	124.6 (3)

N3—C2—C3—C29	−170.15 (19)	N3—C1—C16—C15	53.8 (3)
C23—C2—C3—C29	71.0 (3)	C10—C1—C16—C15	173.4 (3)
N3—C2—C3—C4	−40.2 (2)	C4—C1—C16—C15	−63.9 (4)
C23—C2—C3—C4	−159.1 (2)	N3—C1—C16—C11	−122.9 (2)
C29—C3—C4—C5	29.9 (3)	C10—C1—C16—C11	−3.3 (3)
C2—C3—C4—C5	−100.5 (2)	C4—C1—C16—C11	119.4 (2)
C29—C3—C4—C8	−90.3 (3)	C7—C9—C17—C22	−31.2 (5)
C2—C3—C4—C8	139.3 (2)	C7—C9—C17—C18	150.1 (3)
C29—C3—C4—C1	152.1 (2)	C22—C17—C18—C19	0.3 (5)
C2—C3—C4—C1	21.8 (2)	C9—C17—C18—C19	179.1 (3)
N3—C1—C4—C5	127.7 (2)	C17—C18—C19—C20	−0.6 (6)
C16—C1—C4—C5	−109.5 (2)	C18—C19—C20—C21	1.0 (7)
C10—C1—C4—C5	7.0 (3)	C19—C20—C21—C22	−1.0 (6)
N3—C1—C4—C8	−114.4 (2)	C18—C17—C22—C21	−0.4 (5)
C16—C1—C4—C8	8.5 (3)	C9—C17—C22—C21	−179.0 (3)
C10—C1—C4—C8	125.0 (2)	C20—C21—C22—C17	0.7 (5)
N3—C1—C4—C3	4.8 (2)	N3—C2—C23—C24	134.2 (3)
C16—C1—C4—C3	127.6 (2)	C3—C2—C23—C24	−113.7 (3)
C10—C1—C4—C3	−115.9 (2)	N3—C2—C23—C28	−47.4 (3)
C8—C4—C5—N1	−63.1 (2)	C3—C2—C23—C28	64.8 (3)
C3—C4—C5—N1	173.8 (2)	C28—C23—C24—C25	−1.3 (4)
C1—C4—C5—N1	56.5 (3)	C2—C23—C24—C25	177.2 (3)
N1—C6—C7—C9	−151.3 (3)	C23—C24—C25—C26	−0.2 (5)
N1—C6—C7—C8	26.5 (3)	C24—C25—C26—C27	1.6 (5)
C9—C7—C8—O1	−22.9 (4)	C25—C26—C27—C28	−1.5 (5)
C6—C7—C8—O1	159.1 (3)	C24—C23—C28—C27	1.3 (4)
C9—C7—C8—C4	155.9 (2)	C2—C23—C28—C27	−177.2 (3)
C6—C7—C8—C4	−22.1 (3)	C26—C27—C28—C23	0.0 (5)
C5—C4—C8—O1	−142.5 (3)	C2—C3—C29—C34	35.1 (3)
C3—C4—C8—O1	−18.3 (3)	C4—C3—C29—C34	−88.8 (3)
C1—C4—C8—O1	95.9 (3)	C2—C3—C29—C30	−144.0 (2)
C5—C4—C8—C7	38.8 (3)	C4—C3—C29—C30	92.1 (3)
C3—C4—C8—C7	162.9 (2)	C34—C29—C30—C31	0.5 (4)
C1—C4—C8—C7	−82.9 (3)	C3—C29—C30—C31	179.7 (3)
C6—C7—C9—C17	0.3 (5)	C29—C30—C31—C32	0.3 (5)
C8—C7—C9—C17	−177.6 (3)	C30—C31—C32—C33	−0.6 (5)
N3—C1—C10—O2	−53.5 (3)	C31—C32—C33—C34	0.2 (5)
C16—C1—C10—O2	−172.9 (2)	C32—C33—C34—C29	0.6 (5)
C4—C1—C10—O2	61.1 (3)	C30—C29—C34—C33	−0.9 (4)
N3—C1—C10—N2	121.2 (2)	C3—C29—C34—C33	179.9 (3)
C16—C1—C10—N2	1.8 (3)	C7—C6—N1—C5	−51.3 (3)
C4—C1—C10—N2	−124.2 (2)	C7—C6—N1—C35	−177.8 (2)
N2—C11—C12—C13	174.7 (3)	C4—C5—N1—C6	72.6 (3)
C16—C11—C12—C13	0.1 (4)	C4—C5—N1—C35	−161.7 (2)
C11—C12—C13—C14	−1.2 (5)	O2—C10—N2—C11	175.0 (2)
C12—C13—C14—C15	0.1 (5)	C1—C10—N2—C11	0.3 (3)
C13—C14—C15—C16	2.1 (5)	C12—C11—N2—C10	−177.6 (3)
C14—C15—C16—C11	−3.1 (4)	C16—C11—N2—C10	−2.5 (3)
C14—C15—C16—C1	−179.5 (3)	C23—C2—N3—C1	167.17 (19)
C12—C11—C16—C15	2.0 (4)	C3—C2—N3—C1	46.5 (2)
N2—C11—C16—C15	−173.4 (2)	C16—C1—N3—C2	−158.78 (19)
C12—C11—C16—C1	179.2 (2)	C10—C1—N3—C2	88.6 (2)
N2—C11—C16—C1	3.7 (3)	C4—C1—N3—C2	−32.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.86	2.10	2.950 (3)	170
C31—H31···Cg1ⁱⁱ	0.93	2.85	3.778 (5)	175

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

Experimental details

Crystal data
Chemical formula	C₃₅H₃₁N₃O₂
M_r	525.63
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.194 (4), 10.681 (5), 15.352 (8)
α, β, γ (°)	80.76 (4), 80.31 (2), 72.71 (5)
V (Å³)	1562.4 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.25 × 0.21 × 0.18

Data collection
Diffractometer	Nonius MACH3 sealed-tube
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.968, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	6511, 5494, 2506
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.143, 0.89
No. of reflections	5494
No. of parameters	363
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.22

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXTL/PC (Bruker, 2000), SHELXTL/PC, PLATON (Spek, 2003).