8-[(E)-4-Methoxy­benzyl­idene]-4-(4-methoxy­phen­yl)-3-(3-phenyl-1,2,4-oxadiazol-5-yl)-5,6,7,8-tetra­hydro-4H-chromen-2-ylamine

Srinivasan, N.; Nandhini, M.S.; Ranjithkumar, R.; Perumal, S.; Krishnakumar, R.V.

doi:10.1107/S1600536807038093

8-[(E)-4-Methoxybenzylidene]-4-(4-methoxyphenyl)-3-(3-phenyl-1,2,4-oxadiazol-5-yl)-5,6,7,8-tetrahydro-4H-chromen-2-ylamine

N. Srinivasan, M. S. Nandhini, R. Ranjithkumar, S. Perumal and R. V. Krishnakumar

The molecular conformation of the title compound, C₃₂H₂₉N₃O₄, is influenced by an intramolecular N—H

N hydrogen bond. Molecules are linked by N—H

O and C—H

O hydrogen bonds, generating sheets parallel to (001). In addition, a π–π stacking interaction (centroid–centroid distance = 4.038 Å) between the phenyl rings attached to the oxadiazole ring in adjacent molecules, and a C—H

π interaction involving the oxadiazole ring are also found to stabilize the crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038093/cf2131sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038093/cf2131Isup2.hkl Contains datablock I

CCDC reference: 660244

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.002 Å
R factor = 0.054
wR factor = 0.178
Data-to-parameter ratio = 26.5

checkCIF/PLATON results

No syntax errors found



Alert level A
DIFF020_ALERT_1_A  _diffrn_standards_interval_count and
            _diffrn_standards_interval_time are missing. Number of measurements
            between standards or time (min) between standards.

Alert level C
DIFMX01_ALERT_2_C  The maximum difference density is > 0.1*ZMAX*0.75
            _refine_diff_density_max given =      0.600
            Test value =      0.600
DIFMX02_ALERT_1_C  The maximum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.

Alert level G
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
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   3 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
   0 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

The title compound, (I) (Fig. 1), belongs to an important class of organic molecules that have been found to display photoluminiscent properties (Yang et al., 2007). Precise X-ray crystallographic investigations on such compounds are expected to provide insights for modelling and fabrication of organic light-emitting diodes.

An analysis of the puckering amplitudes (Cremer & Pople, 1975) indicates that the pyran ring adopts a boat conformation [Q = 0.164 (1) Å, θ = 103.8 (5)° and φ = 357.9 (5)°] and the six-membered ring fused to it adopts an envelope conformation [Q = 0.444 (2) Å, θ = 129.3 (2)° and φ = 56.0 (3)°], but deviations from planarity in this fused ring system are small.

The title molecule may be thought of as made up of four ring systems: the 5,6,7,8-tetrahydro-4H-chromen-2-ψlamine (A), 3-phenyl-1,2,4-oxadiazol-5-yl) (B), (4-methoxyphenyl)methylidene (C), and 4-(4-methoxyphenyl) (D). B, C and D make dihedral angles of 19.5 (1)°, 44.2 (1)° and 88.0 (1)°, respectively, with the mean plane of ring system A.

The conformation of the molecule is influenced by an intramolecular N—H···N hydrogen bond. Molecules are linked by N—H···O and C—H···O hydrogen bonds, generating sheets parallel to (001) (Fig.2). In addition, a π-π stacking interaction (centroid-centroid distance 4.038 Å) between phenyl rings attached to the oxadiazole ring in adjacent molecules, and a C—H···π interaction involving the oxadiazole ring are also found to stabilize the crystal structure.

Related literature top

For related literature, see: Yang et al. (2007); Cremer & Pople (1975).

Experimental top

A mixture of 2-amino-4-(4-methoxyphenyl)-8-[(E)-(4-methoxyphenyl)methylidene]-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile (0.2 g, 5 mmol) and N-hydroxybenzenecarboximidoyl chloride (0.080 g, 5 mmol) was dissolved in benzene (15 ml). A solution of triethylamine (0.05 g, 5 mmol) in benzene (2 ml) was added dropwise to the above mixture, which was refluxed until the reaction was complete (about 5 h). Triethylamine hydrochloride was filtered off, the solvent removed in vacuo and the residue purified by column chromatography with silica gel, using petroleum ether:ethyl acetate (90:10 v/v) as eluant, to obtain the pure product as a pale-yellow solid (yield 52%). The compound was recrystallized from ethyl acetate to obtain suitable crystals for X-ray crystallographic study.

Structure description top

For related literature, see: Yang et al. (2007); Cremer & Pople (1975).

Computing details top

Data collection: APEX2 (Bruker, 2004a); cell refinement: SAINT (Bruker, 2004b); data reduction: SAINT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms. The intramolecular hydrogen bond is shown as a dashed line.
	Fig. 2. The packing of (I), viewed down the a axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

8-[(E)-4-Methoxybenzylidene]-4-(4-Methoxyphenyl)-3- (3-phenyl-1,2,4-oxadiazol-5-yl)-5,6,7,8-tetrahydro-4H-chromen-2-amine top

Crystal data top

C₃₂H₂₉N₃O₄	Z = 2
M_r = 519.58	F(000) = 548
Triclinic, P1	D_x = 1.301 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.5014 (3) Å	Cell parameters from 4468 reflections
b = 11.3187 (4) Å	θ = 3–29°
c = 11.6458 (4) Å	µ = 0.09 mm⁻¹
α = 91.07 (2)°	T = 298 K
β = 98.45 (2)°	Block, colourless
γ = 104.10 (3)°	0.30 × 0.20 × 0.15 mm
V = 1325.8 (2) Å³

Data collection top

Bruker Kappa APEXII diffractometer	9546 independent reflections
Radiation source: fine-focus sealed tube	6512 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω and φ scans	θ_max = 32.7°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −15→15
T_min = 0.98, T_max = 0.99	k = −17→17
36723 measured reflections	l = −17→17

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.088P)² + 0.2805P] where P = (F_o² + 2F_c²)/3
9546 reflections	(Δ/σ)_max < 0.001
360 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₃₂H₂₉N₃O₄	γ = 104.10 (3)°
M_r = 519.58	V = 1325.8 (2) Å³
Triclinic, P1	Z = 2
a = 10.5014 (3) Å	Mo Kα radiation
b = 11.3187 (4) Å	µ = 0.09 mm⁻¹
c = 11.6458 (4) Å	T = 298 K
α = 91.07 (2)°	0.30 × 0.20 × 0.15 mm
β = 98.45 (2)°

Data collection top

Bruker Kappa APEXII diffractometer	9546 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	6512 reflections with I > 2σ(I)
T_min = 0.98, T_max = 0.99	R_int = 0.025
36723 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.178	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.60 e Å⁻³
9546 reflections	Δρ_min = −0.32 e Å⁻³
360 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
O1	0.44750 (9)	−0.06770 (9)	0.74873 (8)	0.0453 (2)
O31	0.77429 (10)	0.29001 (9)	0.69489 (8)	0.0445 (2)
O8	0.03663 (13)	−0.70140 (10)	1.00681 (11)	0.0603 (3)
O4	1.11417 (11)	−0.09930 (11)	0.60871 (11)	0.0586 (3)
N21	0.39565 (13)	0.05173 (14)	0.61084 (12)	0.0553 (4)
N32	0.78419 (13)	0.39013 (11)	0.62222 (11)	0.0476 (3)
N34	0.59051 (11)	0.25039 (10)	0.56538 (9)	0.0386 (2)
C2	0.49210 (13)	0.03321 (12)	0.69183 (11)	0.0389 (3)
C3	0.61886 (12)	0.10433 (11)	0.71726 (10)	0.0357 (2)
C4	0.72111 (12)	0.06893 (11)	0.80595 (10)	0.0336 (2)
H4	0.7668	0.1409	0.8575	0.040*
C5	0.65386 (12)	−0.02897 (11)	0.87854 (10)	0.0352 (2)
C6	0.52803 (12)	−0.09250 (11)	0.84756 (10)	0.0359 (2)
C7	0.45949 (13)	−0.19525 (12)	0.90757 (11)	0.0379 (3)
C8	0.33702 (13)	−0.26063 (12)	0.86451 (11)	0.0402 (3)
H8	0.2957	−0.2324	0.7982	0.048*
C81	0.25958 (13)	−0.37157 (12)	0.90901 (11)	0.0392 (3)
C82	0.25819 (14)	−0.39269 (13)	1.02612 (12)	0.0432 (3)
H82	0.3073	−0.3323	1.0816	0.052*
C83	0.18564 (14)	−0.50118 (13)	1.06275 (12)	0.0444 (3)
H83	0.1872	−0.5132	1.1417	0.053*
C84	0.11123 (14)	−0.59097 (12)	0.98113 (13)	0.0443 (3)
C85	0.10668 (17)	−0.57044 (14)	0.86384 (13)	0.0519 (3)
H85	0.0543	−0.6296	0.8086	0.062*
C86	0.17943 (15)	−0.46289 (13)	0.82911 (12)	0.0479 (3)
H86	0.1752	−0.4505	0.7501	0.058*
C87	0.0408 (2)	−0.72963 (17)	1.12512 (17)	0.0662 (5)
H87A	−0.0156	−0.8094	1.1304	0.099*
H87B	0.0104	−0.6704	1.1667	0.099*
H87C	0.1304	−0.7282	1.1585	0.099*
C33	0.67314 (13)	0.36061 (11)	0.54936 (11)	0.0380 (3)
C35	0.65582 (12)	0.21169 (11)	0.65603 (10)	0.0354 (2)
C331	0.64071 (14)	0.43903 (12)	0.45653 (11)	0.0415 (3)
C332	0.53368 (18)	0.39616 (16)	0.37008 (14)	0.0571 (4)
H332	0.4821	0.3166	0.3697	0.068*
C333	0.5029 (2)	0.4720 (2)	0.28346 (16)	0.0708 (5)
H333	0.4310	0.4428	0.2248	0.085*
C334	0.5776 (2)	0.58886 (19)	0.28403 (16)	0.0721 (6)
H334	0.5559	0.6396	0.2265	0.087*
C335	0.6838 (3)	0.63113 (17)	0.36871 (17)	0.0753 (6)
H335	0.7350	0.7107	0.3683	0.090*
C336	0.7166 (2)	0.55744 (14)	0.45519 (15)	0.0607 (4)
H336	0.7897	0.5872	0.5126	0.073*
C41	0.82502 (11)	0.02492 (10)	0.74932 (9)	0.0320 (2)
C42	0.96020 (12)	0.07784 (12)	0.78085 (12)	0.0401 (3)
H42	0.9883	0.1428	0.8363	0.048*
C43	1.05339 (13)	0.03552 (13)	0.73117 (13)	0.0444 (3)
H43	1.1433	0.0729	0.7525	0.053*
C44	1.01362 (13)	−0.06205 (12)	0.65001 (11)	0.0397 (3)
C45	0.87972 (13)	−0.11618 (13)	0.61681 (12)	0.0428 (3)
H45	0.8520	−0.1814	0.5616	0.051*
C46	0.78722 (12)	−0.07194 (12)	0.66695 (11)	0.0399 (3)
H46	0.6972	−0.1085	0.6445	0.048*
C47	1.0822 (2)	−0.2066 (2)	0.5367 (2)	0.0774 (6)
H47A	1.1619	−0.2209	0.5144	0.116*
H47B	1.0225	−0.1980	0.4684	0.116*
H47C	1.0404	−0.2742	0.5780	0.116*
C9	0.54074 (16)	−0.22266 (16)	1.01766 (13)	0.0523 (4)
H9A	0.5236	−0.1779	1.0831	0.063*
H9B	0.5124	−0.3090	1.0301	0.063*
C10	0.68687 (16)	−0.18972 (15)	1.01387 (15)	0.0548 (4)
H10A	0.7059	−0.2426	0.9557	0.066*
H10B	0.7340	−0.2031	1.0886	0.066*
C11	0.73658 (14)	−0.05845 (13)	0.98560 (11)	0.0449 (3)
H11A	0.7334	−0.0052	1.0508	0.054*
H11B	0.8284	−0.0439	0.9733	0.054*
H21A	0.3161 (19)	0.0034 (17)	0.6047 (16)	0.052 (5)*
H21B	0.4161 (19)	0.1154 (18)	0.5695 (17)	0.062 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0373 (5)	0.0480 (5)	0.0464 (5)	0.0050 (4)	0.0002 (4)	0.0211 (4)
O31	0.0475 (5)	0.0386 (5)	0.0433 (5)	0.0055 (4)	0.0015 (4)	0.0116 (4)
O8	0.0689 (7)	0.0408 (6)	0.0675 (7)	0.0025 (5)	0.0165 (6)	0.0148 (5)
O4	0.0440 (6)	0.0663 (7)	0.0713 (7)	0.0176 (5)	0.0213 (5)	−0.0014 (6)
N21	0.0359 (6)	0.0623 (8)	0.0633 (8)	0.0075 (6)	−0.0017 (5)	0.0321 (7)
N32	0.0554 (7)	0.0369 (6)	0.0473 (6)	0.0061 (5)	0.0052 (5)	0.0129 (5)
N34	0.0392 (5)	0.0367 (5)	0.0426 (5)	0.0127 (4)	0.0084 (4)	0.0121 (4)
C2	0.0370 (6)	0.0418 (6)	0.0407 (6)	0.0136 (5)	0.0074 (5)	0.0150 (5)
C3	0.0362 (6)	0.0361 (6)	0.0376 (5)	0.0128 (5)	0.0081 (4)	0.0105 (4)
C4	0.0340 (5)	0.0325 (5)	0.0345 (5)	0.0087 (4)	0.0043 (4)	0.0055 (4)
C5	0.0364 (6)	0.0373 (6)	0.0336 (5)	0.0114 (5)	0.0065 (4)	0.0086 (4)
C6	0.0357 (6)	0.0392 (6)	0.0348 (5)	0.0123 (5)	0.0060 (4)	0.0110 (4)
C7	0.0388 (6)	0.0394 (6)	0.0385 (5)	0.0122 (5)	0.0102 (5)	0.0129 (5)
C8	0.0410 (6)	0.0411 (6)	0.0400 (6)	0.0107 (5)	0.0086 (5)	0.0117 (5)
C81	0.0380 (6)	0.0387 (6)	0.0436 (6)	0.0112 (5)	0.0111 (5)	0.0089 (5)
C82	0.0454 (7)	0.0424 (7)	0.0417 (6)	0.0079 (5)	0.0118 (5)	0.0036 (5)
C83	0.0462 (7)	0.0469 (7)	0.0432 (6)	0.0121 (6)	0.0152 (5)	0.0107 (5)
C84	0.0442 (7)	0.0372 (6)	0.0549 (7)	0.0124 (5)	0.0140 (6)	0.0118 (5)
C85	0.0598 (9)	0.0421 (7)	0.0488 (7)	0.0047 (6)	0.0062 (6)	0.0024 (6)
C86	0.0530 (8)	0.0470 (8)	0.0417 (6)	0.0081 (6)	0.0073 (6)	0.0073 (5)
C87	0.0737 (11)	0.0546 (9)	0.0768 (11)	0.0158 (8)	0.0301 (9)	0.0286 (8)
C33	0.0454 (7)	0.0339 (6)	0.0386 (5)	0.0135 (5)	0.0121 (5)	0.0073 (4)
C35	0.0379 (6)	0.0349 (6)	0.0371 (5)	0.0128 (5)	0.0102 (4)	0.0068 (4)
C331	0.0538 (8)	0.0373 (6)	0.0392 (6)	0.0178 (6)	0.0138 (5)	0.0104 (5)
C332	0.0573 (9)	0.0574 (9)	0.0564 (8)	0.0152 (7)	0.0049 (7)	0.0186 (7)
C333	0.0736 (12)	0.0860 (14)	0.0563 (9)	0.0305 (10)	0.0006 (8)	0.0231 (9)
C334	0.1074 (16)	0.0712 (12)	0.0546 (9)	0.0462 (12)	0.0230 (10)	0.0308 (8)
C335	0.1195 (18)	0.0459 (9)	0.0628 (10)	0.0222 (10)	0.0159 (11)	0.0226 (8)
C336	0.0854 (12)	0.0396 (8)	0.0526 (8)	0.0092 (8)	0.0062 (8)	0.0120 (6)
C41	0.0304 (5)	0.0316 (5)	0.0330 (5)	0.0067 (4)	0.0032 (4)	0.0068 (4)
C42	0.0340 (6)	0.0356 (6)	0.0456 (6)	0.0016 (5)	0.0019 (5)	−0.0024 (5)
C43	0.0285 (6)	0.0460 (7)	0.0537 (7)	0.0013 (5)	0.0041 (5)	0.0018 (6)
C44	0.0355 (6)	0.0438 (7)	0.0421 (6)	0.0115 (5)	0.0100 (5)	0.0075 (5)
C45	0.0395 (6)	0.0431 (7)	0.0435 (6)	0.0079 (5)	0.0046 (5)	−0.0066 (5)
C46	0.0289 (5)	0.0435 (7)	0.0429 (6)	0.0035 (5)	0.0014 (4)	−0.0028 (5)
C47	0.0719 (12)	0.0823 (14)	0.0883 (14)	0.0314 (10)	0.0278 (11)	−0.0169 (11)
C9	0.0508 (8)	0.0572 (9)	0.0478 (7)	0.0111 (7)	0.0053 (6)	0.0230 (6)
C10	0.0484 (8)	0.0567 (9)	0.0569 (8)	0.0132 (7)	−0.0020 (6)	0.0207 (7)
C11	0.0419 (7)	0.0503 (8)	0.0391 (6)	0.0081 (6)	−0.0003 (5)	0.0131 (5)

Geometric parameters (Å, º) top

O1—C2	1.3499 (15)	C87—H87A	0.960
O1—C6	1.4001 (14)	C87—H87B	0.960
O31—C35	1.3493 (16)	C87—H87C	0.960
O31—N32	1.4198 (14)	C33—C331	1.4655 (17)
O8—C84	1.3680 (17)	C331—C332	1.377 (2)
O8—C87	1.417 (2)	C331—C336	1.384 (2)
O4—C44	1.3721 (16)	C332—C333	1.389 (2)
O4—C47	1.404 (2)	C332—H332	0.930
N21—C2	1.3377 (17)	C333—C334	1.363 (3)
N21—H21A	0.872 (19)	C333—H333	0.930
N21—H21B	0.88 (2)	C334—C335	1.358 (3)
N32—C33	1.3038 (18)	C334—H334	0.930
N34—C35	1.3144 (16)	C335—C336	1.378 (2)
N34—C33	1.3686 (17)	C335—H335	0.930
C2—C3	1.3641 (18)	C336—H336	0.930
C3—C35	1.4213 (17)	C41—C46	1.3843 (17)
C3—C4	1.5097 (16)	C41—C42	1.3903 (16)
C4—C5	1.5070 (16)	C42—C43	1.3807 (19)
C4—C41	1.5290 (16)	C42—H42	0.930
C4—H4	0.980	C43—C44	1.3812 (19)
C5—C6	1.3344 (17)	C43—H43	0.930
C5—C11	1.5029 (17)	C44—C45	1.3834 (18)
C6—C7	1.4593 (16)	C45—C46	1.3885 (18)
C7—C8	1.3364 (19)	C45—H45	0.930
C7—C9	1.5134 (18)	C46—H46	0.930
C8—C81	1.4688 (18)	C47—H47A	0.960
C8—H8	0.930	C47—H47B	0.960
C81—C82	1.3907 (18)	C47—H47C	0.960
C81—C86	1.3972 (19)	C9—C10	1.496 (2)
C82—C83	1.3892 (19)	C9—H9A	0.970
C82—H82	0.930	C9—H9B	0.970
C83—C84	1.380 (2)	C10—C11	1.510 (2)
C83—H83	0.930	C10—H10A	0.970
C84—C85	1.386 (2)	C10—H10B	0.970
C85—C86	1.373 (2)	C11—H11A	0.970
C85—H85	0.930	C11—H11B	0.970
C86—H86	0.930

C2—O1—C6	118.98 (10)	O31—C35—C3	117.70 (11)
C35—O31—N32	106.29 (10)	C332—C331—C336	119.16 (14)
C84—O8—C87	118.35 (14)	C332—C331—C33	120.40 (13)
C44—O4—C47	118.78 (13)	C336—C331—C33	120.43 (14)
C2—N21—H21A	119.3 (12)	C331—C332—C333	119.83 (17)
C2—N21—H21B	116.8 (13)	C331—C332—H332	120.1
H21A—N21—H21B	123.8 (18)	C333—C332—H332	120.1
C33—N32—O31	103.40 (10)	C334—C333—C332	120.35 (19)
C35—N34—C33	103.05 (11)	C334—C333—H333	119.8
N21—C2—O1	110.65 (12)	C332—C333—H333	119.8
N21—C2—C3	126.55 (12)	C335—C334—C333	119.95 (16)
O1—C2—C3	122.79 (11)	C335—C334—H334	120.0
C2—C3—C35	119.00 (11)	C333—C334—H334	120.0
C2—C3—C4	121.30 (10)	C334—C335—C336	120.72 (18)
C35—C3—C4	119.66 (11)	C334—C335—H335	119.6
C5—C4—C3	110.09 (10)	C336—C335—H335	119.6
C5—C4—C41	109.71 (9)	C335—C336—C331	119.98 (18)
C3—C4—C41	112.14 (9)	C335—C336—H336	120.0
C5—C4—H4	108.3	C331—C336—H336	120.0
C3—C4—H4	108.3	C46—C41—C42	117.73 (11)
C41—C4—H4	108.3	C46—C41—C4	120.73 (10)
C6—C5—C11	120.25 (11)	C42—C41—C4	121.51 (10)
C6—C5—C4	122.33 (10)	C43—C42—C41	121.06 (12)
C11—C5—C4	117.34 (11)	C43—C42—H42	119.5
C5—C6—O1	122.04 (11)	C41—C42—H42	119.5
C5—C6—C7	125.61 (11)	C42—C43—C44	120.28 (12)
O1—C6—C7	112.33 (10)	C42—C43—H43	119.9
C8—C7—C6	121.52 (11)	C44—C43—H43	119.9
C8—C7—C9	124.10 (12)	O4—C44—C43	115.64 (12)
C6—C7—C9	114.34 (11)	O4—C44—C45	124.51 (12)
C7—C8—C81	128.01 (12)	C43—C44—C45	119.84 (12)
C7—C8—H8	116.0	C44—C45—C46	119.15 (12)
C81—C8—H8	116.0	C44—C45—H45	120.4
C82—C81—C86	116.71 (12)	C46—C45—H45	120.4
C82—C81—C8	124.79 (12)	C41—C46—C45	121.92 (11)
C86—C81—C8	118.49 (12)	C41—C46—H46	119.0
C83—C82—C81	122.04 (13)	C45—C46—H46	119.0
C83—C82—H82	119.0	O4—C47—H47A	109.5
C81—C82—H82	119.0	O4—C47—H47B	109.5
C84—C83—C82	119.50 (13)	H47A—C47—H47B	109.5
C84—C83—H83	120.2	O4—C47—H47C	109.5
C82—C83—H83	120.2	H47A—C47—H47C	109.5
O8—C84—C83	124.69 (13)	H47B—C47—H47C	109.5
O8—C84—C85	115.64 (14)	C10—C9—C7	112.95 (12)
C83—C84—C85	119.65 (13)	C10—C9—H9A	109.0
C86—C85—C84	120.07 (14)	C7—C9—H9A	109.0
C86—C85—H85	120.0	C10—C9—H9B	109.0
C84—C85—H85	120.0	C7—C9—H9B	109.0
C85—C86—C81	121.94 (13)	H9A—C9—H9B	107.8
C85—C86—H86	119.0	C9—C10—C11	112.05 (13)
C81—C86—H86	119.0	C9—C10—H10A	109.2
O8—C87—H87A	109.5	C11—C10—H10A	109.2
O8—C87—H87B	109.5	C9—C10—H10B	109.2
H87A—C87—H87B	109.5	C11—C10—H10B	109.2
O8—C87—H87C	109.5	H10A—C10—H10B	107.9
H87A—C87—H87C	109.5	C5—C11—C10	111.05 (11)
H87B—C87—H87C	109.5	C5—C11—H11A	109.4
N32—C33—N34	114.88 (11)	C10—C11—H11A	109.4
N32—C33—C331	122.32 (12)	C5—C11—H11B	109.4
N34—C33—C331	122.79 (12)	C10—C11—H11B	109.4
N34—C35—O31	112.37 (11)	H11A—C11—H11B	108.0
N34—C35—C3	129.92 (12)

C35—O31—N32—C33	−0.30 (14)	C35—N34—C33—C331	−179.71 (11)
C6—O1—C2—N21	−170.98 (12)	C33—N34—C35—O31	−1.31 (14)
C6—O1—C2—C3	8.5 (2)	C33—N34—C35—C3	177.36 (12)
N21—C2—C3—C35	1.9 (2)	N32—O31—C35—N34	1.06 (14)
O1—C2—C3—C35	−177.52 (12)	N32—O31—C35—C3	−177.79 (10)
N21—C2—C3—C4	−176.10 (14)	C2—C3—C35—N34	−8.7 (2)
O1—C2—C3—C4	4.5 (2)	C4—C3—C35—N34	169.25 (12)
C2—C3—C4—C5	−15.19 (16)	C2—C3—C35—O31	169.87 (11)
C35—C3—C4—C5	166.86 (11)	C4—C3—C35—O31	−12.13 (17)
C2—C3—C4—C41	107.26 (13)	N32—C33—C331—C332	169.18 (14)
C35—C3—C4—C41	−70.69 (14)	N34—C33—C331—C332	−9.9 (2)
C3—C4—C5—C6	14.83 (16)	N32—C33—C331—C336	−11.4 (2)
C41—C4—C5—C6	−109.04 (13)	N34—C33—C331—C336	169.55 (14)
C3—C4—C5—C11	−168.57 (11)	C336—C331—C332—C333	−0.3 (3)
C41—C4—C5—C11	67.56 (14)	C33—C331—C332—C333	179.13 (15)
C11—C5—C6—O1	179.78 (12)	C331—C332—C333—C334	−0.4 (3)
C4—C5—C6—O1	−3.72 (19)	C332—C333—C334—C335	0.9 (3)
C11—C5—C6—C7	−2.0 (2)	C333—C334—C335—C336	−0.6 (3)
C4—C5—C6—C7	174.50 (11)	C334—C335—C336—C331	−0.2 (3)
C2—O1—C6—C5	−8.98 (19)	C332—C331—C336—C335	0.6 (3)
C2—O1—C6—C7	172.59 (11)	C33—C331—C336—C335	−178.82 (16)
C5—C6—C7—C8	−173.88 (13)	C5—C4—C41—C46	65.67 (14)
O1—C6—C7—C8	4.48 (18)	C3—C4—C41—C46	−56.99 (15)
C5—C6—C7—C9	3.84 (19)	C5—C4—C41—C42	−112.39 (12)
O1—C6—C7—C9	−177.80 (12)	C3—C4—C41—C42	124.95 (12)
C6—C7—C8—C81	174.63 (12)	C46—C41—C42—C43	0.33 (19)
C9—C7—C8—C81	−2.9 (2)	C4—C41—C42—C43	178.45 (12)
C7—C8—C81—C82	38.2 (2)	C41—C42—C43—C44	−1.0 (2)
C7—C8—C81—C86	−142.75 (15)	C47—O4—C44—C43	172.53 (16)
C86—C81—C82—C83	2.8 (2)	C47—O4—C44—C45	−6.7 (2)
C8—C81—C82—C83	−178.13 (13)	C42—C43—C44—O4	−178.05 (13)
C81—C82—C83—C84	−0.7 (2)	C42—C43—C44—C45	1.2 (2)
C87—O8—C84—C83	−3.7 (2)	O4—C44—C45—C46	178.47 (13)
C87—O8—C84—C85	177.81 (15)	C43—C44—C45—C46	−0.7 (2)
C82—C83—C84—O8	179.65 (13)	C42—C41—C46—C45	0.16 (19)
C82—C83—C84—C85	−1.9 (2)	C4—C41—C46—C45	−177.97 (12)
O8—C84—C85—C86	−179.22 (14)	C44—C45—C46—C41	0.0 (2)
C83—C84—C85—C86	2.2 (2)	C8—C7—C9—C10	147.76 (15)
C84—C85—C86—C81	0.1 (2)	C6—C7—C9—C10	−29.89 (19)
C82—C81—C86—C85	−2.5 (2)	C7—C9—C10—C11	54.36 (19)
C8—C81—C86—C85	178.36 (14)	C6—C5—C11—C10	25.58 (18)
O31—N32—C33—N34	−0.52 (15)	C4—C5—C11—C10	−151.09 (12)
O31—N32—C33—C331	−179.68 (11)	C9—C10—C11—C5	−51.22 (18)
C35—N34—C33—N32	1.14 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21B···N34	0.88 (2)	2.087 (19)	2.7650 (18)	133.7 (17)
C42—H42···O8ⁱ	0.93	2.54	3.4594 (18)	170
N21—H21A···O4ⁱⁱ	0.872 (19)	2.16 (2)	3.0291 (18)	171.8 (17)
C47—H47A···Cgⁱⁱⁱ	0.96	2.59	3.489 (2)	156

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

Experimental details

Crystal data
Chemical formula	C₃₂H₂₉N₃O₄
M_r	519.58
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	10.5014 (3), 11.3187 (4), 11.6458 (4)
α, β, γ (°)	91.07 (2), 98.45 (2), 104.10 (3)
V (Å³)	1325.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.15

Data collection
Diffractometer	Bruker Kappa APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.98, 0.99
No. of measured, independent and observed [I > 2σ(I)] reflections	36723, 9546, 6512
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.759

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.178, 1.03
No. of reflections	9546
No. of parameters	360
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.32

Computer programs: APEX2 (Bruker, 2004a), SAINT (Bruker, 2004b), SAINT, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.