7-[(3,5-Di-tert-butyl-2-hy­droxy­benzyl­idene)amino]-4-methyl-2H-chromen-2-one

Aazam, E.S.; Büyükgüngör, O.

doi:10.1107/S1600536810036743

7-[(3,5-Di-tert-butyl-2-hydroxybenzylidene)amino]-4-methyl-2H-chromen-2-one

The title compound, C₂₅H₂₉NO₃, is a Schiff base derivative of coumarin 120. There are two structurally similar but crystallographically independent molecules in the asymmetric unit. Both molecules exist in E configurations with respect to the C=N double bonds. The dihedral angles between the coumarin and 3,5-di-tert-butyl-2-hydroxybenzylidene ring planes are 4.62 (7) and 14.62 (7)° for the two molecules. Intramolecular O—H

N hydrogen bonding involving the O—H groups and the azomethine N atoms generate S(6) rings. In the crystal structure, independent molecules are linked by C—H

π interactions, with groups of four molecules stacked along the c axis.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810036743/sj5038sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810036743/sj5038Isup2.hkl Contains datablock I

CCDC reference: 797786

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.005 Å
R factor = 0.055
wR factor = 0.146
Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low ....         38 Perc.

Author Response: We are aware of the low quality of the data. But unfortunately, the crystals were small (0.05 x 0.20 x 0.32) and not of good quality. While in normal circumstances we use 1 minute exposure, 6 minutes exposure time was applied for this data. It is therefore unlikely that to re-measure the crystal data will improve the data.


Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C11    --  C12     ..       6.62 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C11    --  C13     ..       5.98 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C32    --  C33     ..       5.37 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C36    --  C37     ..       6.82 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C36    --  C38     ..       5.40 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C36
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          5
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         34

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         84

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   9 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 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

Comment top

Coumarin-derived Schiff bases are regarded as "privileged ligands" due to their ability to form complexes with different transition metals that can act as catalysts for many different reactions (Youssef et al., 2009). They have been found to exhibit biological and plant regulating activities (Kulkarni et al., 2009; Youssef et al., 2009). They can also act as anti-inflammatory and analgesic agents (Ronad et al., 2008). Several reports of their applications as dyes and fluorescent agents have appeared (Kachkovski et al., 2004; Creaven et al., 2009).

In a continuation of our interest in the synthesis, crystal structure elucidation (Aazam et al., 2006, 2008, 2010), biological activity and photophysical properties of Schiff-base ligands incorporating a coumarin moiety and their metal complexes (El Husseiny et al., 2008), we report here the crystal structure of a newly synthesized coumarin Schiff base derived from 7-amino-4-methyl coumarin and 3,5-di-t-butyl-2-hydroxybenzaldehyde.

The asymmetric unit of the title compound (Fig. 1) consists of two crystallographically independent molecules, A and B (Honda et al. ,1996). The two independent molecules differ in planarity, where molecule A is more planar than molecule B, having dihedral angles between the coumarin and 3,5-di-tert-butyl- 2-hydroxybenzylidene ring planes of 4.64 (7)° and 14.62 (7)° for molecule A and B respectively. The planarity of both molecules is greater than that of the related 4-methyl-7-(salicylideneamino)coumarin Schiff base where the corresponding dihedral angle was 24.0 (1)° (Aazam et al., 2006). The greater planarity of the title compound may explain the higher fluorescence quantum yield of 0.53 observed (compared with Φ_f = 0.43 for 4-methyl-7-(salicylideneamino) coumarin in DMSO).

The terminal C=O bond distances of 1.203 (4)Å and 1.209 (4)Å agree with 1.2119 (15)Å found in the related compound 4-methyl-7-(salicylideneamino) coumarin (Aazam et al.2006), but are shorter than that of 1.3040 (17)Å found in 8-[(1E)-1-(2-Aminophenyliminio)ethyl]-2-oxo-2H-chromen-7-olate (Aazam et al., 2010). Intramolecular O—H···N hydrogen bonding involving the O–H groups and the azomethine N atoms generate S(6) rings (Bernstein et al., 1995). In the crystal structure, the independent molecules are linked by C—H···π interactions, with groups of four molecules stacked along the c axis (Fig. 2).

Related literature top

For the chemistry and catalytic properties of coumarin-derived Schiff base complexes, see: Youssef et al. (2009). For their biological and pharmacological properties, see: Kulkarni et al. (2009); Youssef et al. (2009); Ronad et al. (2008). For their applications as dyes and fluorescent agents, see: Kachkovski et al. (2004); Creaven et al. (2009). For related structures, see: Honda et al. (1996); Aazam et al. (2006, 2008, 2010); El Husseiny et al. (2008). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

3,5-di-tertbutyl-2-hydroxybenzaldehyde (0.26 g, 1.50 mmol) in 20 ml of absolute ethanol was added to a warm solution of 7-amino-4-methyl coumarin (0.35 g, 1.5 mmol) in 30 ml of absolute ethanol. The mixture was refluxed for 3 hrs upon which a yellow solution was formed. The solvent was pumped off by rotary evaporation leaving behind an orange solid shown to be pure by NMR spectroscopy. The product was recrystallized from chloroform by slow evaporation forming orange needles. Yield (68%, 0.4 g, 1.02 mmol).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of molecule of molecule A and B. Displacement ellipsoids are drawn at the 30% probability level. Intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 2. The packing diagram of the title compound, with displacement ellipsoids displayed at the 30% probability level. The t-butyl substituents on the benzene ring and H atoms not involved in C—H···π interactions (shown as dashed lines) have been omitted for clarity.

7-[(3,5-Di-tert-butyl-2-hydroxybenzylidene)amino]-4-methyl-2H- chromen-2-one top

Crystal data top

C₂₅H₂₉NO₃	F(000) = 1680
M_r = 391.49	D_x = 1.190 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 15467 reflections
a = 17.6067 (14) Å	θ = 1.2–26.2°
b = 9.6853 (5) Å	µ = 0.08 mm⁻¹
c = 27.237 (3) Å	T = 296 K
β = 109.832 (6)°	Plate, light brown
V = 4369.2 (6) Å³	0.32 × 0.20 × 0.05 mm
Z = 8

Data collection top

Stoe IPDS 2 diffractometer	3118 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.072
Graphite monochromator	θ_max = 25.7°, θ_min = 1.2°
rotation method scans	h = −21→21
29259 measured reflections	k = −11→11
8242 independent reflections	l = −32→32

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 0.84	w = 1/[σ²(F_o²) + (0.0578P)²] where P = (F_o² + 2F_c²)/3
8242 reflections	(Δ/σ)_max < 0.001
524 parameters	Δρ_max = 0.31 e Å⁻³
84 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₅H₂₉NO₃	V = 4369.2 (6) Å³
M_r = 391.49	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.6067 (14) Å	µ = 0.08 mm⁻¹
b = 9.6853 (5) Å	T = 296 K
c = 27.237 (3) Å	0.32 × 0.20 × 0.05 mm
β = 109.832 (6)°

Data collection top

Stoe IPDS 2 diffractometer	3118 reflections with I > 2σ(I)
29259 measured reflections	R_int = 0.072
8242 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	84 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 0.84	Δρ_max = 0.31 e Å⁻³
8242 reflections	Δρ_min = −0.18 e Å⁻³
524 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	0.71746 (19)	0.2973 (3)	0.62303 (13)	0.0465 (9)
C2	0.7896 (2)	0.2190 (3)	0.64044 (13)	0.0472 (9)
C3	0.8653 (2)	0.2821 (3)	0.65273 (13)	0.0479 (9)
C4	0.8651 (2)	0.4252 (3)	0.64687 (14)	0.0555 (10)
H4	0.9147	0.4694	0.6546	0.067*
C5	0.7956 (2)	0.5068 (3)	0.63012 (14)	0.0503 (9)
C6	0.7225 (2)	0.4405 (4)	0.61833 (13)	0.0503 (9)
H6	0.6752	0.4923	0.6069	0.060*
C7	0.9434 (2)	0.1987 (3)	0.66976 (15)	0.0552 (10)
C8	0.9451 (2)	0.1059 (4)	0.62451 (17)	0.0831 (13)
H8A	0.9417	0.1621	0.5948	0.100*
H8B	0.9001	0.0435	0.6156	0.100*
H8C	0.9945	0.0541	0.6348	0.100*
C9	0.9506 (2)	0.1101 (4)	0.71730 (16)	0.0850 (13)
H9A	0.9057	0.0476	0.7091	0.102*
H9B	0.9507	0.1684	0.7458	0.102*
H9C	1.0000	0.0584	0.7270	0.102*
C10	1.0184 (2)	0.2909 (4)	0.68392 (17)	0.0779 (12)
H10A	1.0193	0.3507	0.7122	0.093*
H10B	1.0169	0.3454	0.6542	0.093*
H10C	1.0660	0.2343	0.6943	0.093*
C11	0.8004 (2)	0.6645 (4)	0.62607 (17)	0.0633 (11)
C12	0.7749 (3)	0.7289 (4)	0.66932 (17)	0.0899 (14)
H12A	0.8105	0.6982	0.7027	0.108*
H12B	0.7206	0.7013	0.6650	0.108*
H12C	0.7774	0.8277	0.6674	0.108*
C13	0.8853 (3)	0.7151 (5)	0.6345 (2)	0.1178 (18)
H13A	0.9045	0.6754	0.6086	0.141*
H13B	0.9202	0.6880	0.6686	0.141*
H13C	0.8851	0.8139	0.6317	0.141*
C14	0.7431 (3)	0.7135 (4)	0.57389 (16)	0.0835 (13)
H14A	0.6890	0.6867	0.5703	0.100*
H14B	0.7581	0.6728	0.5463	0.100*
H14C	0.7460	0.8123	0.5720	0.100*
C15	0.6386 (2)	0.2320 (4)	0.60526 (13)	0.0487 (9)
H15	0.5923	0.2859	0.5927	0.058*
C16	0.5586 (2)	0.0272 (3)	0.58550 (13)	0.0476 (9)
C17	0.4838 (2)	0.0864 (4)	0.55885 (14)	0.0556 (10)
H17	0.4784	0.1818	0.5557	0.067*
C18	0.4178 (2)	0.0014 (4)	0.53712 (14)	0.0536 (10)
H18	0.3679	0.0415	0.5197	0.064*
C19	0.4233 (2)	−0.1423 (4)	0.54042 (13)	0.0475 (9)
C20	0.4982 (2)	−0.1965 (3)	0.56716 (13)	0.0484 (9)
C21	0.5650 (2)	−0.1151 (4)	0.59003 (14)	0.0530 (9)
H21	0.6143	−0.1556	0.6085	0.064*
C22	0.3565 (2)	−0.2352 (4)	0.51815 (13)	0.0500 (9)
C23	0.3719 (2)	−0.3718 (4)	0.52296 (15)	0.0629 (11)
H23	0.3290	−0.4321	0.5085	0.075*
C24	0.4500 (2)	−0.4303 (4)	0.54877 (14)	0.0625 (11)
C25	0.2738 (2)	−0.1795 (4)	0.49157 (14)	0.0658 (11)
H25A	0.2740	−0.1219	0.4629	0.079*
H25B	0.2574	−0.1261	0.5159	0.079*
H25C	0.2368	−0.2546	0.4787	0.079*
N1	0.63226 (16)	0.0999 (3)	0.60680 (11)	0.0507 (8)
O1	0.78494 (14)	0.0796 (2)	0.64396 (10)	0.0644 (7)
H1A	0.7374	0.0565	0.6357	0.097*
O2	0.46800 (18)	−0.5512 (3)	0.55272 (12)	0.0875 (10)
O3	0.51209 (14)	−0.3380 (2)	0.57174 (10)	0.0606 (7)
C26	0.67182 (18)	0.1911 (3)	0.36205 (12)	0.0424 (8)
C27	0.7414 (2)	0.2736 (3)	0.38276 (13)	0.0479 (9)
C28	0.81763 (19)	0.2128 (3)	0.40647 (13)	0.0478 (9)
C29	0.8196 (2)	0.0694 (4)	0.40745 (13)	0.0520 (9)
H29	0.8696	0.0273	0.4229	0.062*
C30	0.7525 (2)	−0.0166 (3)	0.38701 (13)	0.0466 (9)
C31	0.6791 (2)	0.0473 (3)	0.36445 (13)	0.0482 (9)
H31	0.6331	−0.0066	0.3504	0.058*
C32	0.89406 (19)	0.3001 (4)	0.43076 (15)	0.0557 (10)
C33	0.9692 (2)	0.2112 (4)	0.45430 (18)	0.0809 (13)
H33A	0.9765	0.1531	0.4277	0.097*
H33B	0.9628	0.1550	0.4816	0.097*
H33C	1.0155	0.2697	0.4684	0.097*
C34	0.8854 (2)	0.3901 (4)	0.47456 (16)	0.0741 (12)
H34A	0.8778	0.3323	0.5011	0.089*
H34B	0.8396	0.4499	0.4608	0.089*
H34C	0.9333	0.4446	0.4893	0.089*
C35	0.9091 (2)	0.3908 (4)	0.38876 (16)	0.0744 (12)
H35A	0.8636	0.4506	0.3737	0.089*
H35B	0.9163	0.3332	0.3620	0.089*
H35C	0.9567	0.4455	0.4043	0.089*
C36	0.7602 (2)	−0.1747 (4)	0.39020 (15)	0.0548 (10)
C37	0.8450 (3)	−0.2233 (4)	0.4182 (2)	0.1033 (16)
H37A	0.8633	−0.1883	0.4532	0.124*
H37B	0.8798	−0.1904	0.4002	0.124*
H37C	0.8460	−0.3224	0.4190	0.124*
C38	0.7046 (3)	−0.2350 (4)	0.41652 (17)	0.0836 (13)
H38A	0.6499	−0.2097	0.3972	0.100*
H38B	0.7193	−0.1998	0.4515	0.100*
H38C	0.7095	−0.3338	0.4176	0.100*
C39	0.7345 (3)	−0.2358 (4)	0.33471 (16)	0.0851 (13)
H39A	0.7690	−0.2006	0.3169	0.102*
H39B	0.6796	−0.2103	0.3159	0.102*
H39C	0.7388	−0.3346	0.3368	0.102*
C40	0.59273 (19)	0.2538 (4)	0.33832 (13)	0.0492 (9)
H40	0.5476	0.1978	0.3246	0.059*
C41	0.5103 (2)	0.4573 (3)	0.31500 (13)	0.0483 (9)
C42	0.4340 (2)	0.3969 (4)	0.29606 (14)	0.0549 (10)
H42	0.4285	0.3014	0.2958	0.066*
C43	0.3672 (2)	0.4796 (4)	0.27784 (13)	0.0550 (10)
H43	0.3166	0.4380	0.2653	0.066*
C44	0.3715 (2)	0.6238 (4)	0.27722 (13)	0.0467 (9)
C45	0.4483 (2)	0.6801 (3)	0.29646 (14)	0.0495 (9)
C46	0.5164 (2)	0.5999 (4)	0.31460 (14)	0.0542 (10)
H46	0.5670	0.6415	0.3267	0.065*
C47	0.3032 (2)	0.7170 (4)	0.25793 (13)	0.0527 (9)
C48	0.3177 (3)	0.8536 (4)	0.26011 (15)	0.0642 (11)
H48	0.2738	0.9128	0.2475	0.077*
C49	0.3967 (3)	0.9138 (4)	0.28057 (15)	0.0608 (10)
C50	0.2196 (2)	0.6579 (4)	0.23672 (15)	0.0687 (11)
H50A	0.2094	0.6025	0.2631	0.082*
H50B	0.2150	0.6016	0.2068	0.082*
H50C	0.1810	0.7316	0.2267	0.082*
N2	0.58451 (16)	0.3866 (3)	0.33607 (11)	0.0516 (8)
O4	0.73564 (13)	0.4132 (2)	0.38099 (9)	0.0616 (7)
H4A	0.6884	0.4357	0.3664	0.092*
O5	0.41309 (18)	1.0345 (3)	0.28431 (11)	0.0795 (9)
O6	0.46070 (14)	0.8222 (2)	0.29799 (10)	0.0615 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.046 (2)	0.045 (2)	0.048 (2)	−0.0058 (17)	0.0157 (16)	−0.0017 (17)
C2	0.051 (2)	0.037 (2)	0.053 (2)	−0.0006 (16)	0.0169 (18)	0.0018 (16)
C3	0.050 (2)	0.041 (2)	0.054 (2)	−0.0001 (16)	0.0187 (17)	0.0008 (17)
C4	0.052 (2)	0.046 (2)	0.068 (3)	−0.0034 (18)	0.0206 (19)	0.0006 (19)
C5	0.048 (2)	0.040 (2)	0.061 (2)	−0.0013 (17)	0.0180 (18)	0.0041 (18)
C6	0.048 (2)	0.047 (2)	0.055 (2)	0.0013 (17)	0.0165 (17)	0.0039 (18)
C7	0.049 (2)	0.044 (2)	0.070 (3)	0.0044 (17)	0.0160 (18)	0.004 (2)
C8	0.073 (3)	0.071 (2)	0.105 (3)	0.009 (2)	0.031 (2)	−0.011 (2)
C9	0.069 (2)	0.082 (3)	0.094 (3)	0.007 (2)	0.014 (2)	0.022 (2)
C10	0.056 (2)	0.068 (2)	0.103 (3)	0.002 (2)	0.018 (2)	0.000 (2)
C11	0.057 (2)	0.041 (2)	0.093 (3)	0.0015 (18)	0.027 (2)	0.015 (2)
C12	0.109 (3)	0.052 (2)	0.091 (3)	0.004 (2)	0.011 (2)	0.000 (2)
C13	0.090 (3)	0.068 (3)	0.189 (4)	−0.011 (2)	0.039 (3)	0.030 (3)
C14	0.106 (3)	0.059 (2)	0.085 (3)	0.008 (2)	0.032 (2)	0.018 (2)
C15	0.044 (2)	0.051 (2)	0.050 (2)	−0.0001 (17)	0.0161 (17)	−0.0006 (18)
C16	0.041 (2)	0.050 (2)	0.051 (2)	−0.0034 (17)	0.0148 (16)	−0.0006 (18)
C17	0.057 (2)	0.044 (2)	0.067 (3)	0.0048 (18)	0.0220 (19)	0.0015 (19)
C18	0.041 (2)	0.057 (2)	0.061 (2)	0.0024 (18)	0.0146 (18)	−0.0032 (19)
C19	0.045 (2)	0.051 (2)	0.047 (2)	−0.0041 (17)	0.0162 (17)	−0.0020 (17)
C20	0.053 (2)	0.042 (2)	0.051 (2)	−0.0045 (18)	0.0192 (18)	0.0023 (18)
C21	0.045 (2)	0.054 (2)	0.056 (2)	0.0016 (18)	0.0116 (17)	0.0024 (19)
C22	0.049 (2)	0.060 (2)	0.042 (2)	−0.0094 (18)	0.0159 (17)	−0.0056 (18)
C23	0.066 (3)	0.060 (3)	0.060 (3)	−0.023 (2)	0.018 (2)	−0.008 (2)
C24	0.071 (3)	0.053 (3)	0.058 (3)	−0.012 (2)	0.015 (2)	−0.003 (2)
C25	0.058 (2)	0.078 (2)	0.062 (2)	−0.010 (2)	0.0209 (18)	−0.012 (2)
N1	0.0504 (18)	0.0427 (18)	0.058 (2)	−0.0060 (14)	0.0171 (14)	−0.0006 (15)
O1	0.0574 (16)	0.0368 (14)	0.091 (2)	−0.0038 (12)	0.0151 (14)	0.0042 (13)
O2	0.104 (2)	0.0444 (17)	0.106 (3)	−0.0065 (16)	0.0258 (19)	0.0004 (16)
O3	0.0566 (16)	0.0443 (14)	0.0735 (18)	−0.0036 (12)	0.0125 (13)	0.0014 (13)
C26	0.0369 (19)	0.047 (2)	0.041 (2)	−0.0025 (16)	0.0111 (15)	0.0019 (16)
C27	0.053 (2)	0.039 (2)	0.050 (2)	0.0032 (17)	0.0146 (18)	0.0027 (17)
C28	0.0397 (19)	0.046 (2)	0.055 (2)	−0.0021 (16)	0.0128 (16)	0.0017 (17)
C29	0.044 (2)	0.050 (2)	0.056 (2)	0.0050 (17)	0.0088 (17)	0.0042 (18)
C30	0.044 (2)	0.0399 (19)	0.051 (2)	0.0024 (16)	0.0105 (16)	0.0009 (17)
C31	0.051 (2)	0.042 (2)	0.050 (2)	−0.0052 (17)	0.0156 (17)	−0.0020 (17)
C32	0.039 (2)	0.053 (2)	0.069 (3)	−0.0025 (17)	0.0116 (18)	0.002 (2)
C33	0.055 (2)	0.069 (2)	0.104 (3)	−0.007 (2)	0.007 (2)	0.005 (2)
C34	0.063 (2)	0.071 (2)	0.081 (3)	−0.021 (2)	0.016 (2)	−0.010 (2)
C35	0.064 (2)	0.073 (2)	0.089 (3)	−0.012 (2)	0.029 (2)	0.004 (2)
C36	0.053 (2)	0.046 (2)	0.062 (3)	0.0054 (18)	0.0156 (19)	0.0056 (19)
C37	0.087 (3)	0.058 (2)	0.140 (4)	0.006 (2)	0.006 (3)	0.009 (2)
C38	0.103 (3)	0.057 (2)	0.096 (3)	−0.003 (2)	0.042 (2)	0.004 (2)
C39	0.109 (3)	0.065 (2)	0.085 (3)	0.003 (2)	0.037 (2)	−0.001 (2)
C40	0.044 (2)	0.054 (2)	0.047 (2)	−0.0025 (17)	0.0110 (16)	−0.0019 (18)
C41	0.046 (2)	0.047 (2)	0.048 (2)	0.0016 (17)	0.0110 (17)	0.0017 (17)
C42	0.053 (2)	0.046 (2)	0.061 (2)	0.0044 (18)	0.0130 (18)	0.0003 (18)
C43	0.049 (2)	0.055 (2)	0.058 (3)	0.0004 (19)	0.0145 (19)	0.0001 (19)
C44	0.046 (2)	0.051 (2)	0.042 (2)	0.0050 (17)	0.0138 (17)	0.0016 (17)
C45	0.055 (2)	0.040 (2)	0.055 (2)	0.0025 (18)	0.0209 (18)	0.0015 (17)
C46	0.041 (2)	0.057 (2)	0.062 (3)	−0.0017 (18)	0.0142 (18)	0.002 (2)
C47	0.049 (2)	0.067 (3)	0.042 (2)	0.0101 (19)	0.0150 (17)	0.0022 (19)
C48	0.074 (3)	0.062 (3)	0.060 (3)	0.023 (2)	0.027 (2)	0.014 (2)
C49	0.074 (3)	0.054 (2)	0.057 (3)	0.009 (2)	0.025 (2)	0.006 (2)
C50	0.057 (2)	0.078 (2)	0.067 (2)	0.017 (2)	0.0163 (19)	0.002 (2)
N2	0.0433 (17)	0.0456 (18)	0.061 (2)	0.0070 (14)	0.0115 (14)	0.0054 (15)
O4	0.0467 (15)	0.0432 (15)	0.0863 (19)	0.0006 (12)	0.0115 (13)	0.0039 (13)
O5	0.104 (2)	0.0458 (17)	0.090 (2)	0.0101 (15)	0.0349 (18)	0.0071 (15)
O6	0.0628 (17)	0.0441 (15)	0.0746 (19)	0.0052 (13)	0.0194 (14)	0.0014 (13)

Geometric parameters (Å, º) top

C1—C6	1.398 (5)	C26—C31	1.398 (5)
C1—C2	1.417 (4)	C26—C27	1.410 (4)
C1—C15	1.452 (4)	C26—C40	1.454 (4)
C2—O1	1.358 (4)	C27—O4	1.356 (4)
C2—C3	1.399 (4)	C27—C28	1.406 (4)
C3—C4	1.395 (5)	C28—C29	1.390 (5)
C3—C7	1.526 (4)	C28—C32	1.536 (5)
C4—C5	1.397 (4)	C29—C30	1.398 (4)
C4—H4	0.9300	C29—H29	0.9300
C5—C6	1.375 (4)	C30—C31	1.375 (4)
C5—C11	1.536 (5)	C30—C36	1.537 (5)
C6—H6	0.9300	C31—H31	0.9300
C7—C9	1.522 (5)	C32—C33	1.525 (5)
C7—C10	1.531 (5)	C32—C34	1.526 (5)
C7—C8	1.533 (5)	C32—C35	1.535 (5)
C8—H8A	0.9600	C33—H33A	0.9600
C8—H8B	0.9600	C33—H33B	0.9600
C8—H8C	0.9600	C33—H33C	0.9600
C9—H9A	0.9600	C34—H34A	0.9600
C9—H9B	0.9600	C34—H34B	0.9600
C9—H9C	0.9600	C34—H34C	0.9600
C10—H10A	0.9600	C35—H35A	0.9600
C10—H10B	0.9600	C35—H35B	0.9600
C10—H10C	0.9600	C35—H35C	0.9600
C11—C14	1.513 (5)	C36—C37	1.503 (5)
C11—C13	1.515 (5)	C36—C38	1.513 (5)
C11—C12	1.529 (6)	C36—C39	1.541 (5)
C12—H12A	0.9600	C37—H37A	0.9600
C12—H12B	0.9600	C37—H37B	0.9600
C12—H12C	0.9600	C37—H37C	0.9600
C13—H13A	0.9600	C38—H38A	0.9600
C13—H13B	0.9600	C38—H38B	0.9600
C13—H13C	0.9600	C38—H38C	0.9600
C14—H14A	0.9600	C39—H39A	0.9600
C14—H14B	0.9600	C39—H39B	0.9600
C14—H14C	0.9600	C39—H39C	0.9600
C15—N1	1.286 (4)	C40—N2	1.294 (4)
C15—H15	0.9300	C40—H40	0.9300
C16—C21	1.384 (5)	C41—C46	1.386 (5)
C16—C17	1.393 (4)	C41—C42	1.394 (5)
C16—N1	1.416 (4)	C41—N2	1.413 (4)
C17—C18	1.382 (5)	C42—C43	1.369 (4)
C17—H17	0.9300	C42—H42	0.9300
C18—C19	1.396 (5)	C43—C44	1.399 (5)
C18—H18	0.9300	C43—H43	0.9300
C19—C20	1.376 (5)	C44—C45	1.386 (5)
C19—C22	1.442 (5)	C44—C47	1.453 (4)
C20—C21	1.378 (4)	C45—C46	1.372 (4)
C20—O3	1.390 (4)	C45—O6	1.392 (4)
C21—H21	0.9300	C46—H46	0.9300
C22—C23	1.348 (5)	C47—C48	1.344 (5)
C22—C25	1.489 (5)	C47—C50	1.500 (5)
C23—C24	1.432 (5)	C48—C49	1.434 (5)
C23—H23	0.9300	C48—H48	0.9300
C24—O2	1.208 (4)	C49—O5	1.201 (4)
C24—O3	1.386 (4)	C49—O6	1.385 (4)
C25—H25A	0.9600	C50—H50A	0.9600
C25—H25B	0.9600	C50—H50B	0.9600
C25—H25C	0.9600	C50—H50C	0.9600
O1—H1A	0.8200	O4—H4A	0.8200

C6—C1—C2	119.0 (3)	C31—C26—C27	119.5 (3)
C6—C1—C15	119.0 (3)	C31—C26—C40	119.7 (3)
C2—C1—C15	121.7 (3)	C27—C26—C40	120.8 (3)
O1—C2—C3	119.6 (3)	O4—C27—C28	118.8 (3)
O1—C2—C1	119.1 (3)	O4—C27—C26	120.5 (3)
C3—C2—C1	121.3 (3)	C28—C27—C26	120.7 (3)
C4—C3—C2	116.2 (3)	C29—C28—C27	116.2 (3)
C4—C3—C7	121.8 (3)	C29—C28—C32	121.9 (3)
C2—C3—C7	121.9 (3)	C27—C28—C32	121.9 (3)
C3—C4—C5	124.5 (3)	C28—C29—C30	125.1 (3)
C3—C4—H4	117.7	C28—C29—H29	117.4
C5—C4—H4	117.7	C30—C29—H29	117.4
C6—C5—C4	117.4 (3)	C31—C30—C29	116.7 (3)
C6—C5—C11	121.2 (3)	C31—C30—C36	121.7 (3)
C4—C5—C11	121.5 (3)	C29—C30—C36	121.6 (3)
C5—C6—C1	121.6 (3)	C30—C31—C26	121.8 (3)
C5—C6—H6	119.2	C30—C31—H31	119.1
C1—C6—H6	119.2	C26—C31—H31	119.1
C9—C7—C3	111.3 (3)	C33—C32—C34	107.2 (3)
C9—C7—C10	107.4 (3)	C33—C32—C35	107.0 (3)
C3—C7—C10	112.3 (3)	C34—C32—C35	110.1 (3)
C9—C7—C8	109.6 (3)	C33—C32—C28	112.2 (3)
C3—C7—C8	109.1 (3)	C34—C32—C28	110.2 (3)
C10—C7—C8	107.1 (3)	C35—C32—C28	110.0 (3)
C7—C8—H8A	109.5	C32—C33—H33A	109.5
C7—C8—H8B	109.5	C32—C33—H33B	109.5
H8A—C8—H8B	109.5	H33A—C33—H33B	109.5
C7—C8—H8C	109.5	C32—C33—H33C	109.5
H8A—C8—H8C	109.5	H33A—C33—H33C	109.5
H8B—C8—H8C	109.5	H33B—C33—H33C	109.5
C7—C9—H9A	109.5	C32—C34—H34A	109.5
C7—C9—H9B	109.5	C32—C34—H34B	109.5
H9A—C9—H9B	109.5	H34A—C34—H34B	109.5
C7—C9—H9C	109.5	C32—C34—H34C	109.5
H9A—C9—H9C	109.5	H34A—C34—H34C	109.5
H9B—C9—H9C	109.5	H34B—C34—H34C	109.5
C7—C10—H10A	109.5	C32—C35—H35A	109.5
C7—C10—H10B	109.5	C32—C35—H35B	109.5
H10A—C10—H10B	109.5	H35A—C35—H35B	109.5
C7—C10—H10C	109.5	C32—C35—H35C	109.5
H10A—C10—H10C	109.5	H35A—C35—H35C	109.5
H10B—C10—H10C	109.5	H35B—C35—H35C	109.5
C14—C11—C13	110.5 (4)	C37—C36—C38	109.2 (3)
C14—C11—C12	108.6 (3)	C37—C36—C30	113.2 (3)
C13—C11—C12	106.5 (4)	C38—C36—C30	110.6 (3)
C14—C11—C5	110.1 (3)	C37—C36—C39	106.7 (3)
C13—C11—C5	112.8 (3)	C38—C36—C39	107.1 (3)
C12—C11—C5	108.2 (3)	C30—C36—C39	109.7 (3)
C11—C12—H12A	109.5	C36—C37—H37A	109.5
C11—C12—H12B	109.5	C36—C37—H37B	109.5
H12A—C12—H12B	109.5	H37A—C37—H37B	109.5
C11—C12—H12C	109.5	C36—C37—H37C	109.5
H12A—C12—H12C	109.5	H37A—C37—H37C	109.5
H12B—C12—H12C	109.5	H37B—C37—H37C	109.5
C11—C13—H13A	109.5	C36—C38—H38A	109.5
C11—C13—H13B	109.5	C36—C38—H38B	109.5
H13A—C13—H13B	109.5	H38A—C38—H38B	109.5
C11—C13—H13C	109.5	C36—C38—H38C	109.5
H13A—C13—H13C	109.5	H38A—C38—H38C	109.5
H13B—C13—H13C	109.5	H38B—C38—H38C	109.5
C11—C14—H14A	109.5	C36—C39—H39A	109.5
C11—C14—H14B	109.5	C36—C39—H39B	109.5
H14A—C14—H14B	109.5	H39A—C39—H39B	109.5
C11—C14—H14C	109.5	C36—C39—H39C	109.5
H14A—C14—H14C	109.5	H39A—C39—H39C	109.5
H14B—C14—H14C	109.5	H39B—C39—H39C	109.5
N1—C15—C1	120.4 (3)	N2—C40—C26	120.7 (3)
N1—C15—H15	119.8	N2—C40—H40	119.6
C1—C15—H15	119.8	C26—C40—H40	119.6
C21—C16—C17	119.3 (3)	C46—C41—C42	118.9 (3)
C21—C16—N1	115.0 (3)	C46—C41—N2	115.0 (3)
C17—C16—N1	125.6 (3)	C42—C41—N2	126.1 (3)
C18—C17—C16	119.1 (3)	C43—C42—C41	119.4 (4)
C18—C17—H17	120.4	C43—C42—H42	120.3
C16—C17—H17	120.4	C41—C42—H42	120.3
C17—C18—C19	122.4 (3)	C42—C43—C44	123.0 (4)
C17—C18—H18	118.8	C42—C43—H43	118.5
C19—C18—H18	118.8	C44—C43—H43	118.5
C20—C19—C18	116.6 (3)	C45—C44—C43	116.0 (3)
C20—C19—C22	118.9 (3)	C45—C44—C47	118.3 (3)
C18—C19—C22	124.5 (3)	C43—C44—C47	125.7 (3)
C19—C20—C21	122.6 (3)	C46—C45—C44	122.3 (3)
C19—C20—O3	122.1 (3)	C46—C45—O6	116.1 (3)
C21—C20—O3	115.2 (3)	C44—C45—O6	121.6 (3)
C20—C21—C16	119.9 (3)	C45—C46—C41	120.4 (3)
C20—C21—H21	120.1	C45—C46—H46	119.8
C16—C21—H21	120.1	C41—C46—H46	119.8
C23—C22—C19	117.6 (3)	C48—C47—C44	118.3 (4)
C23—C22—C25	122.3 (3)	C48—C47—C50	122.7 (3)
C19—C22—C25	120.1 (3)	C44—C47—C50	119.0 (3)
C22—C23—C24	124.4 (4)	C47—C48—C49	124.2 (4)
C22—C23—H23	117.8	C47—C48—H48	117.9
C24—C23—H23	117.8	C49—C48—H48	117.9
O2—C24—O3	116.2 (4)	O5—C49—O6	116.7 (4)
O2—C24—C23	127.4 (4)	O5—C49—C48	127.1 (4)
O3—C24—C23	116.4 (4)	O6—C49—C48	116.2 (3)
C22—C25—H25A	109.5	C47—C50—H50A	109.5
C22—C25—H25B	109.5	C47—C50—H50B	109.5
H25A—C25—H25B	109.5	H50A—C50—H50B	109.5
C22—C25—H25C	109.5	C47—C50—H50C	109.5
H25A—C25—H25C	109.5	H50A—C50—H50C	109.5
H25B—C25—H25C	109.5	H50B—C50—H50C	109.5
C15—N1—C16	124.0 (3)	C40—N2—C41	125.0 (3)
C2—O1—H1A	109.5	C27—O4—H4A	109.5
C24—O3—C20	120.5 (3)	C49—O6—C45	121.4 (3)

C6—C1—C2—O1	−178.6 (3)	C31—C26—C27—O4	−179.8 (3)
C15—C1—C2—O1	−4.6 (5)	C40—C26—C27—O4	0.2 (5)
C6—C1—C2—C3	−0.2 (5)	C31—C26—C27—C28	−1.0 (5)
C15—C1—C2—C3	173.8 (3)	C40—C26—C27—C28	178.9 (3)
O1—C2—C3—C4	178.4 (3)	O4—C27—C28—C29	179.5 (3)
C1—C2—C3—C4	0.0 (5)	C26—C27—C28—C29	0.7 (5)
O1—C2—C3—C7	0.4 (5)	O4—C27—C28—C32	0.6 (5)
C1—C2—C3—C7	−177.9 (3)	C26—C27—C28—C32	−178.2 (3)
C2—C3—C4—C5	0.3 (5)	C27—C28—C29—C30	−0.1 (5)
C7—C3—C4—C5	178.3 (3)	C32—C28—C29—C30	178.8 (3)
C3—C4—C5—C6	−0.5 (6)	C28—C29—C30—C31	−0.2 (5)
C3—C4—C5—C11	178.3 (4)	C28—C29—C30—C36	−179.5 (4)
C4—C5—C6—C1	0.3 (5)	C29—C30—C31—C26	−0.1 (5)
C11—C5—C6—C1	−178.5 (4)	C36—C30—C31—C26	179.2 (4)
C2—C1—C6—C5	0.1 (5)	C27—C26—C31—C30	0.7 (5)
C15—C1—C6—C5	−174.1 (3)	C40—C26—C31—C30	−179.3 (3)
C4—C3—C7—C9	125.7 (4)	C29—C28—C32—C33	0.8 (5)
C2—C3—C7—C9	−56.5 (5)	C27—C28—C32—C33	179.7 (3)
C4—C3—C7—C10	5.3 (5)	C29—C28—C32—C34	−118.6 (4)
C2—C3—C7—C10	−176.9 (3)	C27—C28—C32—C34	60.3 (5)
C4—C3—C7—C8	−113.3 (4)	C29—C28—C32—C35	119.8 (4)
C2—C3—C7—C8	64.6 (4)	C27—C28—C32—C35	−61.3 (4)
C6—C5—C11—C14	−49.3 (5)	C31—C30—C36—C37	−177.7 (4)
C4—C5—C11—C14	132.0 (4)	C29—C30—C36—C37	1.5 (5)
C6—C5—C11—C13	−173.3 (4)	C31—C30—C36—C38	−54.7 (5)
C4—C5—C11—C13	8.0 (6)	C29—C30—C36—C38	124.6 (4)
C6—C5—C11—C12	69.2 (5)	C31—C30—C36—C39	63.2 (5)
C4—C5—C11—C12	−109.5 (4)	C29—C30—C36—C39	−117.5 (4)
C6—C1—C15—N1	176.7 (3)	C31—C26—C40—N2	179.4 (4)
C2—C1—C15—N1	2.7 (5)	C27—C26—C40—N2	−0.5 (5)
C21—C16—C17—C18	−0.6 (5)	C46—C41—C42—C43	−0.3 (5)
N1—C16—C17—C18	175.7 (3)	N2—C41—C42—C43	178.5 (3)
C16—C17—C18—C19	−0.6 (6)	C41—C42—C43—C44	0.0 (6)
C17—C18—C19—C20	0.8 (6)	C42—C43—C44—C45	−0.1 (5)
C17—C18—C19—C22	−179.6 (3)	C42—C43—C44—C47	179.3 (3)
C18—C19—C20—C21	0.3 (5)	C43—C44—C45—C46	0.7 (5)
C22—C19—C20—C21	−179.4 (3)	C47—C44—C45—C46	−178.8 (3)
C18—C19—C20—O3	−177.9 (3)	C43—C44—C45—O6	−180.0 (3)
C22—C19—C20—O3	2.5 (5)	C47—C44—C45—O6	0.6 (5)
C19—C20—C21—C16	−1.5 (6)	C44—C45—C46—C41	−1.0 (6)
O3—C20—C21—C16	176.8 (3)	O6—C45—C46—C41	179.6 (3)
C17—C16—C21—C20	1.6 (5)	C42—C41—C46—C45	0.8 (5)
N1—C16—C21—C20	−175.0 (3)	N2—C41—C46—C45	−178.1 (3)
C20—C19—C22—C23	−2.7 (5)	C45—C44—C47—C48	−0.6 (5)
C18—C19—C22—C23	177.6 (4)	C43—C44—C47—C48	−180.0 (4)
C20—C19—C22—C25	176.6 (3)	C45—C44—C47—C50	179.7 (3)
C18—C19—C22—C25	−3.1 (5)	C43—C44—C47—C50	0.3 (5)
C19—C22—C23—C24	0.2 (6)	C44—C47—C48—C49	−0.3 (6)
C25—C22—C23—C24	−179.1 (3)	C50—C47—C48—C49	179.4 (3)
C22—C23—C24—O2	−177.2 (4)	C47—C48—C49—O5	−178.6 (4)
C22—C23—C24—O3	2.6 (6)	C47—C48—C49—O6	1.2 (6)
C1—C15—N1—C16	−173.4 (3)	C26—C40—N2—C41	−178.4 (3)
C21—C16—N1—C15	178.4 (4)	C46—C41—N2—C40	−177.2 (4)
C17—C16—N1—C15	2.0 (6)	C42—C41—N2—C40	3.9 (6)
O2—C24—O3—C20	176.9 (4)	O5—C49—O6—C45	178.6 (4)
C23—C24—O3—C20	−2.9 (5)	C48—C49—O6—C45	−1.2 (5)
C19—C20—O3—C24	0.5 (5)	C46—C45—O6—C49	179.8 (3)
C21—C20—O3—C24	−177.8 (3)	C44—C45—O6—C49	0.4 (5)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C26–C31 and C1–C6 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.82	1.80	2.538 (4)	149
O4—H4A···N2	0.82	1.80	2.537 (4)	149
C25—H25B···Cg1	0.96	2.73	3.536 (4)	143
C50—H50A···Cg2ⁱ	0.96	2.80	3.571 (4)	138
C50—H50B···Cg1ⁱⁱ	0.96	2.91	3.569 (4)	136

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

Experimental details

Crystal data
Chemical formula	C₂₅H₂₉NO₃
M_r	391.49
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	17.6067 (14), 9.6853 (5), 27.237 (3)
β (°)	109.832 (6)
V (Å³)	4369.2 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.32 × 0.20 × 0.05

Data collection
Diffractometer	Stoe IPDS 2 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	29259, 8242, 3118
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.146, 0.84
No. of reflections	8242
No. of parameters	524
No. of restraints	84
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.18

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).