3,5-Bis­[4-(diethyl­amino)­benzyl­idene]-1-methyl-4-piperidone and 3,5-bis[4-(diethyl­amino)­cinnamyl­idene]-1-methyl-4-piperidone: prospective biophotonic materials

The structures of 3,5-bis­[4-(diethyl­amino)­benzyl­idene]-1-methyl-4-piperidone, C₂₈H₃₇N₃O, (I), and 3,5-bis­[4-(diethyl­amino)­cinnamyl­idene]-1-methyl-4-piperidone, C₃₂H₄₁N₃O, (II), have been characterized. Because of conjugation between donor and acceptor parts, the central heterocycles (including the carbonyl group) in (I) and (II) are flattened and exhibit a `sofa' conformation, with a deviation of the N atom from the planar fragment. The dihedral angles between the planar part of the heterocycle and the two almost flat fragments that include a phenyl ring and bridging atoms are 23.2 (1) and 11.2 (1)° in (I), and 11.8 (1) and 8.7 (2)° in (II). One- and two-photon absorption of light and the fluorescence of (I) and (II) have also been characterized.

S1. Comment

In the course of an investigation of non-linear optical organic compounds, in particular, those with two-photon absorption (TPA) properties, several compounds with the general structure D—π—A—π—D were synthesized. The structure, TPA properties and fluorescence activities of two of these compounds have been characterized. Comparison of these structures with analogous compounds found in the literature has shown that their molecules are very similar to the thoroughly investigated group of compounds used as anticancer agents (Jia et al., 1988; Jia et al., 1989; Dimmock et al., 1992a; Dimmock et al., 1992b; Dimmock et al., 1994a; Dimmock et al., 1994b; Dimmock et al., 2001). The combination of these two remarkable features suggests the prospect of their application as agents for localization of cancer cells with two-photon exited fluorescence and as potential agents for photodynamic treatment of cancer.

We describe here the synthesis, structure and properties of 3,5-bis(4'-diethylaminophenylidene)-1-methyl-4-piperidone, (I) (Fig. 1), and 3,5-bis(4'-diethylaminocinnamylidene)-1-methyl-4-piperidone, (II) (Fig. 2), which contain two diethylaminophenyl donor groups connected to a central acceptor 1-methylpiperidone ring via conjugated bridges of different lengths.

In both compounds, the central heterocycle adopts a `sofa' conformation (one atom deviates from the plane, which includes five other atoms). The mean deviation of atoms C2–C6 from the mean-square plane of these five atoms in (I) is 0.030 (1) Å, while the deviation of atom N1 from this plane is −0.724 (1) Å. In (II), the corresponding deviations are 0.015 (2) Å (C2–C6) and 0.681 (2) Å (N1). The positions of atoms C2–C6 in flattened fragments in (I) and (II) are a result of conjugation in the dienone fragments with donor groups. Atom N1 in the piperidone ring has a pyramidal coordination, with the sum of the bond angles equal to 331.1 (2)° for (I) and 330.8 (2)° for (II). In both compounds, the methyl group on atom N1 occupies an equatorial position. The bond-length distribution in the π-conjugated bridges definitely shows an alternation of single C—C and double C═C bond lengths (Tables 1 and 2) with standard values (Allen et al., 1987).

Both (I) and (II) can be formally divided into three almost planar fragments (see Scheme); the first includes the planar part of acceptor heterocycle A, while the second, B, and third, C, include almost planar fragments that consist of a Ph ring and bridging atoms. In (I), the dihedral angles between rings A and B, and between rings A and C, are 23.2 (1) and 11.2 (1)° respectively. The corresponding angles in (II) are 11.8 (1) (for A/B) and 8.7 (2)° (for A/C). Thus the molecule of (I) is slightly less planar than that of (II). This might be related to the presence in (I) of short intramolecular H2A···H24A and H6B···H13A contacts, with distances of 2.10 and 2.20 Å, respectively, that are somewhat shorter than the sum of the van der Waals radii of the H atoms (Rowlend & Taylor, 1996).

In both compounds, one of the diethylamine substituents is disordered. In the molecule of (I), only one ethyl branch of this substituent is disordered, and occupancy refinement suggests a 2:1 ratio of atoms C25/C25A to C26/C26A. In (II), two branches of one diethylamine substituent are disordered, with a relative occupancy of 1:1 for atoms C29–C32 and C29A–C32A. According to the literature, such an effect is common for many molecules bearing a diethylamine group (Suchod & Baldeck, 1995; Kliegel et al., 1998).

Molecules in the crystal of (I) are organized in layers normal to the (1 0 − 4) direction, and within each layer, molecules are packed in a parquet-like manner (Fig. 3). In (II), all long molecular axes are parallel to the crystallographic c axis (Fig. 4). On the other hand, the relative orientations of the mean molecular planes are different; in the environment of a reference molecule, three neighboring molecules are approximately parallel and four molecules are approximately perpendicular to the reference molecule (Fig. 5).

Compound (I) demonstrated a relatively strong fluorescence, which is yellow in color, while being pumped with IR radiation. The coefficient of the two-photon absorption and the molecular cross section of TPA are 3.9 (1) cm GW^_1 and 1490 (50) x 10⁻⁵⁰ cm⁴ s photon⁻¹ molecule⁻¹. Compound (II) produced a weaker fluorescence. The TPA coefficient for (II) is 6.6 (2) cm GW⁻¹ and the TPA cross section is 2550 (70) x 10⁻⁵⁰ cm⁴ s photon⁻¹ molecule⁻¹. For both synthesized compounds, the TPA cross sections are one order of magnitude greater than those of Rhodamine B (Xu & Webb, 1996), the conventional dye used as a benchmark in evaluation of the efficiency of TPA absorbers. Detailed results of spectral properties and the structure–properties relations of these compounds will be published elsewhere. The present results indicate that the synthesized compounds can be potentially used as optical limiters and two-photon fluorescent labels in microscopy and bioresearch.

S2. Experimental

Compounds (I) and (II) were obtained according to literature procedures (Dimmock et al., 1992a). The precipitates were isolated and recrystallized from tetrahydrofurane [m.p. 472 K and yield 76% for (I), and m.p. 449 K and yield 71% for (II)]. Crystals were obtained by isothermic evaporation of ethanol solutions of (I) and (II).

Computing details

Data collection: Enraf–Nonius CAD-4 (Enraf–Nonuis, 1989) for (I); SMART (Bruker, 1998) for (II). Cell refinement: Enraf–Nonius CAD-4 for (I); SMART for (II). Data reduction: SHELXTL-Plus (Sheldrick, 1994) for (I); SAINT (Bruker, 1998) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: SHELXTL-Plus for (I); SHELXTL (Bruker, 1998) for (II). Software used to prepare material for publication: SHELXL97 for (I); SHELXTL for (II).

Figures

	Fig. 1. : View of the molecule of (I), with the atom-numbering scheme. Non-H atoms are shown with thermal ellipsoids drawn at the 50% probability level. For clarity, H atoms are drawn as circles of arbitrary small radii. Only one set of disordered positions is shown for each of the ethyl groups.
	Fig. 2. : View of the molecule of (II), with the atom-numbering scheme. Non-H atoms are shown with thermal ellipsoids drawn at the 50% probability level. For clarity, H atoms are drawn as circles of arbitrary small radii. Only one set of disordered positions is shown for each of the ethyl groups.
	Fig. 3. : Projection of the crystal packing of (I) along the a axis.
	Fig. 4. : Projection of the crystal packing of (II) along the b axis.
	Fig. 5. : Projection of the crystal packing of (II) along the c axis.

(I)

Crystal data

C28H37N3O	F(000) = 936
Mr = 431.61	Dx = 1.149 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.2260 (18) Å	Cell parameters from 24 reflections
b = 16.181 (3) Å	θ = 11–12°
c = 16.862 (3) Å	µ = 0.07 mm^−1
β = 97.55 (3)°	T = 298 K
V = 2495.4 (9) Å^3	Prism, orange
Z = 4	0.50 × 0.40 × 0.30 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.020
Radiation source: fine-focus sealed tube	θmax = 27.0°, θmin = 1.8°
Graphite monochromator	h = 0→11
θ/2θ scans	k = 0→20
5646 measured reflections	l = −21→21
5319 independent reflections	3 standard reflections every 97 reflections
2701 reflections with I > 2σ(I)	intensity decay: 3%

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H-atom parameters constrained
S = 1.19	w = 1/[σ^2(Fo^2) + (0.05P)^2] where P = (Fo^2 + 2Fc^2)/3
5319 reflections	(Δ/σ)max < 0.001
313 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.20 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. All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H distances of 0.93 Å for aromatic H atoms, 0.97 Å for CH₂ and 0.96 Å for CH₃ groups.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.83458 (15)	0.50112 (9)	0.41861 (10)	0.0779 (5)
N1	0.56783 (16)	0.30942 (9)	0.38437 (9)	0.0509 (4)
N2	−0.00216 (18)	0.66852 (11)	0.24463 (10)	0.0642 (5)
N3	1.3021 (2)	0.09895 (12)	0.62789 (13)	0.0859 (6)
C1	0.4683 (2)	0.23929 (13)	0.37497 (14)	0.0672 (6)
H1A	0.3931	0.2494	0.3310	0.101*
H1B	0.4247	0.2319	0.4231	0.101*
H1C	0.5214	0.1903	0.3645	0.101*
C2	0.6856 (2)	0.29469 (11)	0.44949 (11)	0.0509 (5)
H2A	0.7332	0.2427	0.4406	0.061*
H2B	0.6450	0.2905	0.4996	0.061*
C3	0.79545 (18)	0.36280 (11)	0.45511 (10)	0.0446 (4)
C4	0.74725 (19)	0.44494 (11)	0.42398 (12)	0.0503 (5)
C5	0.58755 (19)	0.45836 (11)	0.40005 (11)	0.0473 (4)
C6	0.48998 (19)	0.38474 (11)	0.39977 (12)	0.0530 (5)
H6A	0.4539	0.3804	0.4511	0.064*
H6B	0.4065	0.3916	0.3589	0.064*
C7	0.5445 (2)	0.53478 (12)	0.37740 (11)	0.0507 (5)
H7A	0.6202	0.5730	0.3799	0.061*
C8	0.40107 (19)	0.56881 (11)	0.34968 (11)	0.0482 (5)
C9	0.3927 (2)	0.64056 (12)	0.30380 (12)	0.0560 (5)
H9A	0.4791	0.6669	0.2957	0.067*
C10	0.2622 (2)	0.67437 (12)	0.26982 (12)	0.0575 (5)
H10A	0.2626	0.7220	0.2390	0.069*
C11	0.1292 (2)	0.63796 (12)	0.28104 (11)	0.0519 (5)
C12	0.1358 (2)	0.56881 (12)	0.33159 (11)	0.0537 (5)
H12A	0.0493	0.5450	0.3432	0.064*
C13	0.2663 (2)	0.53563 (12)	0.36418 (11)	0.0520 (5)
H13A	0.2660	0.4895	0.3971	0.062*
C14	−0.0105 (3)	0.73233 (14)	0.18330 (13)	0.0697 (6)
H14A	−0.0942	0.7212	0.1436	0.084*
H14B	0.0764	0.7292	0.1567	0.084*
C15	−0.0235 (4)	0.81809 (16)	0.21457 (16)	0.1007 (9)
H15A	−0.0332	0.8565	0.1708	0.151*
H15B	0.0624	0.8313	0.2509	0.151*
H15C	−0.1081	0.8216	0.2421	0.151*
C16	−0.1404 (2)	0.63388 (15)	0.25995 (14)	0.0712 (6)
H16A	−0.2137	0.6772	0.2542	0.085*
H16B	−0.1306	0.6146	0.3149	0.085*
C17	−0.1928 (3)	0.5636 (2)	0.2055 (2)	0.1145 (10)
H17A	−0.2898	0.5481	0.2146	0.172*
H17B	−0.1283	0.5173	0.2163	0.172*
H17C	−0.1941	0.5806	0.1509	0.172*
C18	0.93712 (18)	0.35634 (11)	0.48708 (11)	0.0476 (4)
H18A	0.9901	0.4051	0.4856	0.057*
C19	1.02165 (19)	0.28738 (11)	0.52331 (10)	0.0458 (4)
C20	1.1744 (2)	0.29593 (12)	0.53474 (11)	0.0540 (5)
H20A	1.2151	0.3450	0.5193	0.065*
C21	1.2660 (2)	0.23474 (12)	0.56788 (13)	0.0620 (5)
H21A	1.3665	0.2434	0.5742	0.074*
C22	1.2120 (2)	0.16009 (12)	0.59223 (12)	0.0587 (5)
C23	1.0604 (2)	0.15082 (13)	0.58078 (12)	0.0621 (5)
H23A	1.0199	0.1013	0.5952	0.075*
C24	0.9694 (2)	0.21293 (12)	0.54877 (11)	0.0577 (5)
H24A	0.8689	0.2047	0.5440	0.069*
C25	1.4573 (6)	0.1180 (3)	0.6607 (4)	0.0789 (12)	0.67
H25A	1.4868	0.0850	0.7081	0.095*	0.67
H25B	1.4668	0.1759	0.6752	0.095*	0.67
C26	1.5534 (10)	0.0982 (5)	0.5969 (5)	0.126 (2)	0.67
H26A	1.6542	0.1040	0.6189	0.189*	0.67
H26B	1.5313	0.1355	0.5527	0.189*	0.67
H26C	1.5354	0.0424	0.5787	0.189*	0.67
C25A	1.4547 (11)	0.0917 (5)	0.6014 (9)	0.072 (2)	0.33
H25C	1.4771	0.0345	0.5905	0.086*	0.33
H25D	1.4608	0.1242	0.5536	0.086*	0.33
C26A	1.5556 (18)	0.1237 (7)	0.6692 (11)	0.125 (5)	0.33
H26D	1.6470	0.1380	0.6514	0.188*	0.33
H26E	1.5717	0.0821	0.7100	0.188*	0.33
H26F	1.5139	0.1719	0.6905	0.188*	0.33
C27	1.2459 (3)	0.01878 (15)	0.64660 (16)	0.0842 (8)
H27A	1.1587	0.0269	0.6721	0.101*
H27B	1.3180	−0.0083	0.6851	0.101*
C28	1.2093 (4)	−0.03735 (18)	0.5768 (2)	0.1254 (12)
H28A	1.1695	−0.0880	0.5943	0.188*
H28B	1.2962	−0.0490	0.5531	0.188*
H28C	1.1386	−0.0112	0.5380	0.188*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0403 (8)	0.0568 (8)	0.1295 (14)	−0.0077 (7)	−0.0160 (8)	0.0244 (9)
N1	0.0353 (8)	0.0489 (9)	0.0658 (10)	−0.0037 (7)	−0.0031 (7)	−0.0068 (8)
N2	0.0463 (10)	0.0768 (12)	0.0673 (11)	0.0139 (9)	−0.0012 (8)	0.0168 (9)
N3	0.0595 (12)	0.0672 (12)	0.1259 (17)	0.0090 (10)	−0.0072 (11)	0.0339 (12)
C1	0.0469 (12)	0.0593 (12)	0.0922 (16)	−0.0134 (10)	−0.0026 (11)	−0.0116 (11)
C2	0.0390 (10)	0.0490 (11)	0.0630 (11)	−0.0027 (8)	0.0003 (9)	0.0001 (9)
C3	0.0323 (9)	0.0476 (10)	0.0525 (10)	−0.0018 (8)	0.0000 (7)	−0.0021 (8)
C4	0.0346 (10)	0.0455 (11)	0.0675 (12)	−0.0073 (9)	−0.0051 (9)	0.0038 (9)
C5	0.0327 (9)	0.0500 (11)	0.0567 (11)	−0.0019 (8)	−0.0031 (8)	0.0003 (9)
C6	0.0331 (10)	0.0569 (12)	0.0669 (12)	−0.0035 (9)	−0.0008 (8)	0.0001 (10)
C7	0.0352 (10)	0.0533 (11)	0.0605 (12)	−0.0031 (9)	−0.0053 (8)	−0.0024 (9)
C8	0.0381 (10)	0.0499 (11)	0.0542 (11)	0.0028 (8)	−0.0025 (8)	−0.0019 (9)
C9	0.0413 (11)	0.0545 (12)	0.0698 (12)	−0.0014 (9)	−0.0025 (9)	0.0017 (10)
C10	0.0527 (12)	0.0510 (11)	0.0667 (13)	0.0057 (9)	0.0002 (10)	0.0069 (10)
C11	0.0420 (11)	0.0578 (12)	0.0545 (11)	0.0107 (9)	0.0015 (8)	−0.0005 (10)
C12	0.0366 (10)	0.0641 (12)	0.0601 (12)	0.0075 (9)	0.0054 (9)	0.0047 (10)
C13	0.0434 (11)	0.0561 (11)	0.0559 (11)	0.0073 (9)	0.0045 (9)	0.0079 (9)
C14	0.0611 (14)	0.0819 (16)	0.0643 (13)	0.0234 (12)	0.0017 (10)	0.0157 (12)
C15	0.134 (3)	0.0798 (18)	0.0915 (19)	0.0342 (17)	0.0279 (17)	0.0164 (14)
C16	0.0410 (12)	0.0890 (16)	0.0814 (15)	0.0163 (12)	0.0001 (10)	0.0125 (13)
C17	0.082 (2)	0.126 (3)	0.129 (3)	−0.0117 (18)	−0.0088 (18)	−0.014 (2)
C18	0.0381 (10)	0.0444 (10)	0.0582 (11)	−0.0014 (8)	−0.0009 (8)	−0.0015 (9)
C19	0.0378 (10)	0.0464 (10)	0.0517 (10)	−0.0001 (8)	0.0000 (8)	−0.0009 (8)
C20	0.0411 (11)	0.0497 (11)	0.0685 (12)	−0.0017 (9)	−0.0027 (9)	0.0057 (9)
C21	0.0382 (11)	0.0564 (12)	0.0885 (14)	0.0025 (10)	−0.0029 (10)	0.0090 (11)
C22	0.0530 (12)	0.0549 (12)	0.0660 (13)	0.0081 (10)	−0.0003 (10)	0.0116 (10)
C23	0.0528 (13)	0.0539 (12)	0.0778 (14)	−0.0071 (10)	0.0018 (10)	0.0161 (10)
C24	0.0409 (11)	0.0617 (13)	0.0688 (13)	−0.0032 (9)	0.0005 (9)	0.0102 (10)
C25	0.069 (3)	0.078 (3)	0.085 (4)	0.018 (3)	−0.009 (3)	0.017 (3)
C26	0.092 (4)	0.139 (5)	0.153 (6)	0.033 (4)	0.042 (5)	0.045 (5)
C25A	0.064 (6)	0.056 (4)	0.096 (8)	0.015 (4)	0.009 (6)	0.011 (5)
C26A	0.071 (7)	0.099 (7)	0.192 (16)	0.014 (6)	−0.036 (10)	−0.014 (8)
C27	0.0833 (17)	0.0684 (16)	0.0964 (18)	0.0095 (13)	−0.0049 (14)	0.0306 (14)
C28	0.157 (3)	0.0771 (18)	0.135 (3)	0.013 (2)	−0.008 (2)	−0.0026 (19)

Geometric parameters (Å, º)

O1—C4	1.226 (2)	C15—H15A	0.9600
N1—C1	1.455 (2)	C15—H15B	0.9600
N1—C6	1.455 (2)	C15—H15C	0.9600
N1—C2	1.459 (2)	C16—C17	1.501 (4)
N2—C11	1.376 (2)	C16—H16A	0.9700
N2—C16	1.447 (3)	C16—H16B	0.9700
N2—C14	1.456 (3)	C17—H17A	0.9600
N3—C22	1.379 (2)	C17—H17B	0.9600
N3—C27	1.447 (3)	C17—H17C	0.9600
N3—C25	1.497 (7)	C18—C19	1.450 (2)
N3—C25A	1.536 (13)	C18—H18A	0.9300
C1—H1A	0.9600	C19—C24	1.386 (3)
C1—H1B	0.9600	C19—C20	1.404 (3)
C1—H1C	0.9600	C20—C21	1.372 (3)
C2—C3	1.492 (2)	C20—H20A	0.9300
C2—H2A	0.9700	C21—C22	1.389 (3)
C2—H2B	0.9700	C21—H21A	0.9300
C3—C18	1.351 (2)	C22—C23	1.394 (3)
C3—C4	1.476 (2)	C23—C24	1.374 (3)
C4—C5	1.492 (2)	C23—H23A	0.9300
C5—C7	1.339 (2)	C24—H24A	0.9300
C5—C6	1.493 (3)	C25—C26	1.514 (9)
C6—H6A	0.9700	C25—H25A	0.9700
C6—H6B	0.9700	C25—H25B	0.9700
C7—C8	1.453 (3)	C26—H26A	0.9600
C7—H7A	0.9300	C26—H26B	0.9600
C8—C9	1.392 (3)	C26—H26C	0.9600
C8—C13	1.405 (3)	C25A—C26A	1.470 (17)
C9—C10	1.377 (3)	C25A—H25C	0.9700
C9—H9A	0.9300	C25A—H25D	0.9700
C10—C11	1.396 (3)	C26A—H26D	0.9600
C10—H10A	0.9300	C26A—H26E	0.9600
C11—C12	1.403 (3)	C26A—H26F	0.9600
C12—C13	1.367 (3)	C27—C28	1.490 (4)
C12—H12A	0.9300	C27—H27A	0.9700
C13—H13A	0.9300	C27—H27B	0.9700
C14—C15	1.495 (3)	C28—H28A	0.9600
C14—H14A	0.9700	C28—H28B	0.9600
C14—H14B	0.9700	C28—H28C	0.9600
C1—N1—C6	110.69 (15)	H15A—C15—H15B	109.5
C1—N1—C2	110.57 (15)	C14—C15—H15C	109.5
C6—N1—C2	109.79 (14)	H15A—C15—H15C	109.5
C11—N2—C16	121.74 (17)	H15B—C15—H15C	109.5
C11—N2—C14	122.19 (17)	N2—C16—C17	113.9 (2)
C16—N2—C14	115.85 (16)	N2—C16—H16A	108.8
C22—N3—C27	121.71 (19)	C17—C16—H16A	108.8
C22—N3—C25	120.4 (2)	N2—C16—H16B	108.8
C27—N3—C25	117.2 (2)	C17—C16—H16B	108.8
C22—N3—C25A	116.8 (4)	H16A—C16—H16B	107.7
C27—N3—C25A	111.3 (3)	C16—C17—H17A	109.5
N1—C1—H1A	109.5	C16—C17—H17B	109.5
N1—C1—H1B	109.5	H17A—C17—H17B	109.5
H1A—C1—H1B	109.5	C16—C17—H17C	109.5
N1—C1—H1C	109.5	H17A—C17—H17C	109.5
H1A—C1—H1C	109.5	H17B—C17—H17C	109.5
H1B—C1—H1C	109.5	C3—C18—C19	131.79 (17)
N1—C2—C3	111.08 (15)	C3—C18—H18A	114.1
N1—C2—H2A	109.4	C19—C18—H18A	114.1
C3—C2—H2A	109.4	C24—C19—C20	115.24 (17)
N1—C2—H2B	109.4	C24—C19—C18	127.58 (17)
C3—C2—H2B	109.4	C20—C19—C18	117.18 (16)
H2A—C2—H2B	108.0	C21—C20—C19	122.55 (18)
C18—C3—C4	116.23 (16)	C21—C20—H20A	118.7
C18—C3—C2	125.59 (16)	C19—C20—H20A	118.7
C4—C3—C2	118.17 (15)	C20—C21—C22	121.50 (19)
O1—C4—C3	121.59 (16)	C20—C21—H21A	119.3
O1—C4—C5	120.50 (16)	C22—C21—H21A	119.3
C3—C4—C5	117.91 (15)	N3—C22—C21	122.27 (19)
C7—C5—C4	117.20 (16)	N3—C22—C23	121.30 (19)
C7—C5—C6	125.44 (16)	C21—C22—C23	116.41 (17)
C4—C5—C6	117.29 (16)	C24—C23—C22	121.71 (18)
N1—C6—C5	110.94 (15)	C24—C23—H23A	119.1
N1—C6—H6A	109.5	C22—C23—H23A	119.1
C5—C6—H6A	109.5	C23—C24—C19	122.56 (18)
N1—C6—H6B	109.5	C23—C24—H24A	118.7
C5—C6—H6B	109.5	C19—C24—H24A	118.7
H6A—C6—H6B	108.0	N3—C25—C26	108.4 (8)
C5—C7—C8	131.72 (18)	N3—C25—H25A	110.0
C5—C7—H7A	114.1	C26—C25—H25A	110.0
C8—C7—H7A	114.1	N3—C25—H25B	110.0
C9—C8—C13	115.44 (16)	C26—C25—H25B	110.0
C9—C8—C7	118.50 (17)	H25A—C25—H25B	108.4
C13—C8—C7	126.06 (17)	C26A—C25A—N3	104.9 (16)
C10—C9—C8	123.01 (18)	C26A—C25A—H25C	110.8
C10—C9—H9A	118.5	N3—C25A—H25C	110.8
C8—C9—H9A	118.5	C26A—C25A—H25D	110.8
C9—C10—C11	120.79 (18)	N3—C25A—H25D	110.8
C9—C10—H10A	119.6	H25C—C25A—H25D	108.8
C11—C10—H10A	119.6	C25A—C26A—H26D	109.5
N2—C11—C10	121.72 (18)	C25A—C26A—H26E	109.5
N2—C11—C12	121.54 (18)	H26D—C26A—H26E	109.5
C10—C11—C12	116.74 (16)	C25A—C26A—H26F	109.5
C13—C12—C11	121.55 (18)	H26D—C26A—H26F	109.5
C13—C12—H12A	119.2	H26E—C26A—H26F	109.5
C11—C12—H12A	119.2	N3—C27—C28	115.1 (2)
C12—C13—C8	122.23 (18)	N3—C27—H27A	108.5
C12—C13—H13A	118.9	C28—C27—H27A	108.5
C8—C13—H13A	118.9	N3—C27—H27B	108.5
N2—C14—C15	114.02 (18)	C28—C27—H27B	108.5
N2—C14—H14A	108.7	H27A—C27—H27B	107.5
C15—C14—H14A	108.7	C27—C28—H28A	109.5
N2—C14—H14B	108.7	C27—C28—H28B	109.5
C15—C14—H14B	108.7	H28A—C28—H28B	109.5
H14A—C14—H14B	107.6	C27—C28—H28C	109.5
C14—C15—H15A	109.5	H28A—C28—H28C	109.5
C14—C15—H15B	109.5	H28B—C28—H28C	109.5
C1—N1—C2—C3	175.02 (16)	C11—N2—C14—C15	−94.9 (3)
C6—N1—C2—C3	−62.6 (2)	C16—N2—C14—C15	90.4 (3)
N1—C2—C3—C18	−155.29 (17)	C11—N2—C16—C17	−88.7 (3)
N1—C2—C3—C4	25.2 (2)	C14—N2—C16—C17	86.1 (2)
C18—C3—C4—O1	8.6 (3)	C4—C3—C18—C19	179.44 (18)
C2—C3—C4—O1	−171.88 (18)	C2—C3—C18—C19	−0.1 (3)
C18—C3—C4—C5	−170.57 (16)	C3—C18—C19—C24	−14.1 (3)
C2—C3—C4—C5	9.0 (3)	C3—C18—C19—C20	166.15 (19)
O1—C4—C5—C7	−3.8 (3)	C24—C19—C20—C21	0.7 (3)
C3—C4—C5—C7	175.30 (17)	C18—C19—C20—C21	−179.52 (18)
O1—C4—C5—C6	173.43 (19)	C19—C20—C21—C22	0.0 (3)
C3—C4—C5—C6	−7.4 (2)	C27—N3—C22—C21	−174.5 (2)
C1—N1—C6—C5	−173.42 (16)	C25—N3—C22—C21	15.6 (4)
C2—N1—C6—C5	64.22 (19)	C25A—N3—C22—C21	−32.3 (6)
C7—C5—C6—N1	148.72 (18)	C27—N3—C22—C23	7.4 (3)
C4—C5—C6—N1	−28.3 (2)	C25—N3—C22—C23	−162.6 (3)
C4—C5—C7—C8	178.84 (19)	C25A—N3—C22—C23	149.6 (6)
C6—C5—C7—C8	1.8 (3)	C20—C21—C22—N3	−177.9 (2)
C5—C7—C8—C9	−157.1 (2)	C20—C21—C22—C23	0.3 (3)
C5—C7—C8—C13	22.4 (3)	N3—C22—C23—C24	176.9 (2)
C13—C8—C9—C10	−4.4 (3)	C21—C22—C23—C24	−1.4 (3)
C7—C8—C9—C10	175.16 (18)	C22—C23—C24—C19	2.3 (3)
C8—C9—C10—C11	0.9 (3)	C20—C19—C24—C23	−1.8 (3)
C16—N2—C11—C10	−176.3 (2)	C18—C19—C24—C23	178.44 (18)
C14—N2—C11—C10	9.3 (3)	C22—N3—C25—C26	−94.1 (4)
C16—N2—C11—C12	3.5 (3)	C27—N3—C25—C26	95.5 (4)
C14—N2—C11—C12	−170.92 (18)	C25A—N3—C25—C26	3.3 (6)
C9—C10—C11—N2	−176.94 (19)	C22—N3—C25A—C26A	107.1 (7)
C9—C10—C11—C12	3.3 (3)	C27—N3—C25A—C26A	−106.9 (6)
N2—C11—C12—C13	176.27 (18)	C25—N3—C25A—C26A	0.5 (6)
C10—C11—C12—C13	−4.0 (3)	C22—N3—C27—C28	75.6 (3)
C11—C12—C13—C8	0.4 (3)	C25—N3—C27—C28	−114.1 (4)
C9—C8—C13—C12	3.7 (3)	C25A—N3—C27—C28	−68.5 (6)
C7—C8—C13—C12	−175.80 (18)

(II)

Crystal data

C32H41N3O	Dx = 1.132 Mg m^−3
Mr = 483.68	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 320 reflections
a = 20.5823 (18) Å	θ = 4–24°
c = 26.794 (4) Å	µ = 0.07 mm^−1
V = 11351 (2) Å^3	T = 110 K
Z = 16	Plate, red
F(000) = 4192	0.50 × 0.40 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2493 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.045
Graphite monochromator	θmax = 26.0°, θmin = 2.0°
ϕ and ω scans	h = −25→24
22604 measured reflections	k = −19→25
5553 independent reflections	l = −11→33

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.191	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.08P)^2] where P = (Fo^2 + 2Fc^2)/3
5553 reflections	(Δ/σ)max = 0.001
368 parameters	Δρmax = 0.42 e Å^−3
8 restraints	Δρmin = −0.29 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. All disordered C-atoms of diethylamino groups were refined anisotropically with constrained distances: C—N (1.450 Å) and C—C (1.520 Å), and with e.s.d.'s 0.007 Å. All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H distances of 0.95 Å for aromatic H atoms, 0.99 Å for CH₂ and 0.98 Å for CH₃ groups.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.35517 (10)	0.30070 (10)	0.62231 (6)	0.0590 (6)
N1	0.30430 (11)	0.11093 (11)	0.62037 (8)	0.0508 (6)
N2	0.34562 (11)	0.19024 (10)	1.00866 (7)	0.0480 (6)
N3	0.34354 (18)	0.19317 (16)	0.23522 (10)	0.0914 (11)
C1	0.27647 (16)	0.04557 (15)	0.62012 (11)	0.0652 (9)
H1A	0.2907	0.0221	0.6500	0.098*
H1B	0.2911	0.0223	0.5903	0.098*
H1C	0.2289	0.0486	0.6199	0.098*
C2	0.28424 (14)	0.14733 (15)	0.57638 (10)	0.0546 (8)
H2A	0.2365	0.1532	0.5770	0.066*
H2B	0.2954	0.1222	0.5460	0.066*
C3	0.31641 (13)	0.21236 (14)	0.57410 (10)	0.0468 (7)
C4	0.33092 (14)	0.24548 (15)	0.62171 (9)	0.0469 (7)
C5	0.31706 (13)	0.21074 (13)	0.66848 (9)	0.0443 (7)
C6	0.28442 (14)	0.14547 (13)	0.66528 (9)	0.0486 (7)
H6A	0.2959	0.1193	0.6950	0.058*
H6B	0.2367	0.1514	0.6650	0.058*
C7	0.33456 (13)	0.23820 (13)	0.71192 (9)	0.0451 (7)
H7A	0.3557	0.2791	0.7092	0.054*
C8	0.32594 (13)	0.21469 (13)	0.76169 (9)	0.0436 (7)
H8A	0.3030	0.1752	0.7667	0.052*
C9	0.34907 (12)	0.24652 (13)	0.80133 (9)	0.0419 (7)
H9A	0.3718	0.2855	0.7938	0.050*
C10	0.34490 (12)	0.23091 (12)	0.85398 (9)	0.0383 (6)
C11	0.37974 (13)	0.26889 (12)	0.88780 (9)	0.0440 (7)
H11A	0.4038	0.3049	0.8755	0.053*
C12	0.38071 (13)	0.25621 (13)	0.93848 (9)	0.0464 (7)
H12A	0.4056	0.2830	0.9601	0.056*
C13	0.34492 (13)	0.20377 (12)	0.95823 (9)	0.0415 (7)
C14	0.31001 (12)	0.16589 (13)	0.92412 (9)	0.0413 (7)
H14A	0.2857	0.1299	0.9361	0.050*
C15	0.30992 (12)	0.17919 (13)	0.87394 (9)	0.0423 (7)
H15A	0.2853	0.1523	0.8522	0.051*
C16	0.38314 (15)	0.23057 (14)	1.04330 (10)	0.0567 (8)
H16A	0.4255	0.2414	1.0279	0.068*
H16B	0.3917	0.2055	1.0741	0.068*
C17	0.34838 (16)	0.29233 (16)	1.05657 (11)	0.0688 (9)
H17A	0.3753	0.3178	1.0795	0.103*
H17B	0.3069	0.2819	1.0726	0.103*
H17C	0.3403	0.3176	1.0262	0.103*
C18	0.29842 (14)	0.14636 (14)	1.03042 (10)	0.0536 (8)
H18A	0.2586	0.1467	1.0097	0.064*
H18B	0.2866	0.1623	1.0641	0.064*
C19	0.32310 (15)	0.07714 (14)	1.03463 (12)	0.0660 (9)
H19A	0.2879	0.0489	1.0462	0.099*
H19B	0.3592	0.0756	1.0585	0.099*
H19C	0.3382	0.0623	1.0019	0.099*
C20	0.33294 (14)	0.24138 (15)	0.53120 (10)	0.0574 (8)
H20A	0.3523	0.2831	0.5344	0.069*
C21	0.32549 (14)	0.21820 (15)	0.48105 (10)	0.0547 (8)
H21A	0.3042	0.1778	0.4758	0.066*
C22	0.34709 (18)	0.25093 (16)	0.44180 (11)	0.0763 (11)
H22A	0.3674	0.2912	0.4493	0.092*
C23	0.34446 (19)	0.23455 (17)	0.38917 (11)	0.0734 (10)
C24	0.3742 (3)	0.2736 (2)	0.35438 (15)	0.188 (3)
H24A	0.3958	0.3117	0.3655	0.226*
C25	0.3742 (3)	0.2599 (2)	0.30441 (14)	0.182 (3)
H25A	0.3965	0.2883	0.2823	0.218*
C26	0.34301 (19)	0.20675 (17)	0.28524 (12)	0.0769 (11)
C27	0.31253 (16)	0.16920 (17)	0.31937 (12)	0.0744 (11)
H27A	0.2894	0.1321	0.3081	0.089*
C28	0.31351 (15)	0.18238 (17)	0.36986 (11)	0.0678 (10)
H28A	0.2916	0.1536	0.3919	0.081*
C29	0.3427 (3)	0.2448 (4)	0.1979 (2)	0.090 (3)	0.50
H29A	0.3242	0.2855	0.2114	0.109*	0.50
H29B	0.3181	0.2317	0.1677	0.109*	0.50
C30	0.4146 (4)	0.2515 (4)	0.1871 (3)	0.070 (3)	0.50
H30A	0.4215	0.2877	0.1639	0.105*	0.50
H30B	0.4308	0.2112	0.1721	0.105*	0.50
H30C	0.4380	0.2601	0.2183	0.105*	0.50
C31	0.3207 (3)	0.1321 (4)	0.2157 (3)	0.073 (3)	0.50
H31A	0.3371	0.0982	0.2386	0.087*	0.50
H31B	0.3436	0.1256	0.1836	0.087*	0.50
C32	0.2493 (3)	0.1156 (8)	0.2058 (4)	0.189 (8)	0.50
H32A	0.2426	0.0688	0.2100	0.284*	0.50
H32B	0.2379	0.1282	0.1716	0.284*	0.50
H32C	0.2217	0.1393	0.2294	0.284*	0.50
C29A	0.3958 (4)	0.2210 (4)	0.2023 (3)	0.095 (4)	0.50
H29C	0.3996	0.1941	0.1718	0.114*	0.50
H29D	0.4378	0.2191	0.2201	0.114*	0.50
C30A	0.3824 (7)	0.2896 (4)	0.1875 (3)	0.115 (4)	0.50
H30D	0.4131	0.3030	0.1615	0.172*	0.50
H30E	0.3872	0.3180	0.2167	0.172*	0.50
H30F	0.3379	0.2930	0.1747	0.172*	0.50
C31A	0.2880 (4)	0.1667 (3)	0.2108 (4)	0.124 (6)	0.50
H31C	0.2812	0.1879	0.1781	0.149*	0.50
H31D	0.2486	0.1732	0.2314	0.149*	0.50
C32A	0.3013 (6)	0.0960 (4)	0.2041 (3)	0.098 (3)	0.50
H32D	0.3362	0.0902	0.1797	0.146*	0.50
H32E	0.2619	0.0742	0.1921	0.146*	0.50
H32F	0.3144	0.0771	0.2361	0.146*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0762 (15)	0.0624 (15)	0.0383 (11)	−0.0079 (12)	−0.0021 (10)	−0.0011 (10)
N1	0.0500 (15)	0.0511 (16)	0.0515 (15)	−0.0016 (12)	−0.0013 (11)	−0.0104 (12)
N2	0.0643 (16)	0.0453 (15)	0.0345 (13)	−0.0121 (12)	0.0002 (11)	0.0043 (10)
N3	0.142 (3)	0.093 (3)	0.0388 (17)	−0.030 (2)	0.0048 (18)	−0.0157 (16)
C1	0.068 (2)	0.058 (2)	0.070 (2)	−0.0005 (17)	0.0035 (17)	−0.0143 (16)
C2	0.0492 (19)	0.074 (2)	0.0404 (16)	0.0003 (16)	−0.0030 (13)	−0.0127 (15)
C3	0.0458 (18)	0.0552 (19)	0.0395 (16)	0.0050 (15)	−0.0049 (13)	−0.0063 (13)
C4	0.0501 (18)	0.0484 (19)	0.0422 (16)	0.0018 (15)	−0.0036 (13)	−0.0025 (14)
C5	0.0426 (17)	0.0498 (18)	0.0404 (16)	0.0042 (14)	−0.0041 (12)	−0.0024 (13)
C6	0.0479 (18)	0.0557 (19)	0.0421 (16)	−0.0010 (15)	−0.0056 (13)	−0.0048 (13)
C7	0.0468 (18)	0.0486 (18)	0.0399 (16)	0.0020 (14)	−0.0009 (13)	0.0018 (13)
C8	0.0451 (17)	0.0432 (17)	0.0424 (16)	−0.0002 (13)	−0.0027 (13)	0.0009 (13)
C9	0.0441 (17)	0.0411 (16)	0.0406 (16)	0.0008 (13)	−0.0022 (12)	0.0012 (12)
C10	0.0399 (16)	0.0371 (16)	0.0380 (14)	0.0042 (13)	−0.0021 (12)	−0.0003 (12)
C11	0.0550 (19)	0.0355 (16)	0.0414 (16)	−0.0039 (14)	0.0008 (13)	0.0049 (12)
C12	0.0595 (19)	0.0443 (18)	0.0354 (15)	−0.0064 (15)	−0.0069 (13)	−0.0003 (12)
C13	0.0471 (17)	0.0384 (17)	0.0390 (15)	0.0035 (13)	−0.0001 (12)	0.0018 (12)
C14	0.0421 (17)	0.0411 (16)	0.0408 (15)	−0.0036 (13)	0.0012 (12)	0.0036 (12)
C15	0.0397 (16)	0.0444 (17)	0.0430 (16)	−0.0007 (13)	−0.0048 (13)	0.0001 (13)
C16	0.076 (2)	0.060 (2)	0.0334 (15)	−0.0052 (17)	0.0009 (15)	0.0049 (14)
C17	0.076 (2)	0.078 (2)	0.0523 (19)	−0.0097 (19)	−0.0003 (16)	−0.0093 (17)
C18	0.060 (2)	0.061 (2)	0.0397 (16)	−0.0033 (16)	0.0024 (13)	0.0053 (14)
C19	0.065 (2)	0.062 (2)	0.071 (2)	−0.0041 (17)	0.0024 (17)	0.0194 (17)
C20	0.072 (2)	0.060 (2)	0.0401 (17)	0.0080 (17)	−0.0082 (15)	−0.0069 (14)
C21	0.062 (2)	0.060 (2)	0.0424 (17)	0.0083 (16)	−0.0056 (14)	−0.0081 (15)
C22	0.124 (3)	0.064 (2)	0.0407 (19)	−0.013 (2)	−0.0016 (18)	−0.0094 (16)
C23	0.113 (3)	0.065 (2)	0.0415 (19)	−0.014 (2)	0.0016 (18)	−0.0115 (16)
C24	0.409 (10)	0.111 (4)	0.045 (2)	−0.141 (5)	0.027 (4)	−0.019 (2)
C25	0.384 (9)	0.117 (4)	0.043 (2)	−0.133 (5)	0.029 (4)	−0.022 (2)
C26	0.109 (3)	0.079 (3)	0.0429 (19)	−0.019 (2)	0.0045 (18)	−0.0134 (17)
C27	0.077 (3)	0.094 (3)	0.051 (2)	−0.033 (2)	0.0145 (17)	−0.0244 (18)
C28	0.068 (2)	0.087 (3)	0.0487 (19)	−0.0253 (19)	0.0123 (16)	−0.0142 (17)
C29	0.085 (6)	0.119 (8)	0.068 (6)	0.048 (6)	−0.044 (5)	−0.041 (6)
C30	0.126 (9)	0.049 (6)	0.033 (4)	−0.027 (5)	−0.014 (4)	−0.002 (4)
C31	0.077 (6)	0.097 (7)	0.044 (4)	−0.058 (6)	0.029 (4)	−0.053 (5)
C32	0.083 (8)	0.301 (17)	0.185 (12)	−0.100 (9)	0.058 (8)	−0.187 (12)
C29A	0.170 (11)	0.077 (7)	0.039 (5)	−0.053 (7)	0.018 (5)	0.000 (4)
C30A	0.213 (14)	0.073 (7)	0.059 (5)	−0.028 (8)	−0.007 (7)	−0.002 (5)
C31A	0.234 (17)	0.067 (7)	0.072 (7)	0.038 (9)	0.058 (9)	0.017 (5)
C32A	0.169 (12)	0.050 (5)	0.074 (6)	0.025 (6)	0.004 (6)	−0.002 (4)

Geometric parameters (Å, º)

O1—C4	1.241 (3)	C18—C19	1.517 (4)
N1—C6	1.456 (3)	C18—H18A	0.9900
N1—C2	1.456 (3)	C18—H18B	0.9900
N1—C1	1.462 (4)	C19—H19A	0.9800
N2—C13	1.380 (3)	C19—H19B	0.9800
N2—C18	1.449 (3)	C19—H19C	0.9800
N2—C16	1.465 (3)	C20—C21	1.434 (4)
N3—C26	1.369 (4)	C20—H20A	0.9500
N3—C31A	1.426 (7)	C21—C22	1.326 (4)
N3—C31	1.441 (6)	C21—H21A	0.9500
N3—C29	1.460 (6)	C22—C23	1.451 (4)
N3—C29A	1.504 (6)	C22—H22A	0.9500
C1—H1A	0.9800	C23—C28	1.352 (4)
C1—H1B	0.9800	C23—C24	1.375 (5)
C1—H1C	0.9800	C24—C25	1.368 (5)
C2—C3	1.495 (4)	C24—H24A	0.9500
C2—H2A	0.9900	C25—C26	1.369 (5)
C2—H2B	0.9900	C25—H25A	0.9500
C3—C20	1.339 (4)	C26—C27	1.352 (4)
C3—C4	1.477 (4)	C27—C28	1.380 (4)
C4—C5	1.471 (4)	C27—H27A	0.9500
C5—C7	1.343 (3)	C28—H28A	0.9500
C5—C6	1.505 (4)	C29—C30	1.514 (6)
C6—H6A	0.9900	C29—H29A	0.9900
C6—H6B	0.9900	C29—H29B	0.9900
C7—C8	1.430 (3)	C30—H30A	0.9800
C7—H7A	0.9500	C30—H30B	0.9800
C8—C9	1.336 (3)	C30—H30C	0.9800
C8—H8A	0.9500	C31—C32	1.531 (6)
C9—C10	1.450 (3)	C31—H31A	0.9900
C9—H9A	0.9500	C31—H31B	0.9900
C10—C15	1.392 (4)	C32—H32A	0.9800
C10—C11	1.395 (3)	C32—H32B	0.9800
C11—C12	1.383 (3)	C32—H32C	0.9800
C11—H11A	0.9500	C29A—C30A	1.493 (6)
C12—C13	1.410 (3)	C29A—H29C	0.9900
C12—H12A	0.9500	C29A—H29D	0.9900
C13—C14	1.400 (3)	C30A—H30D	0.9800
C14—C15	1.372 (3)	C30A—H30E	0.9800
C14—H14A	0.9500	C30A—H30F	0.9800
C15—H15A	0.9500	C31A—C32A	1.491 (6)
C16—C17	1.501 (4)	C31A—H31C	0.9900
C16—H16A	0.9900	C31A—H31D	0.9900
C16—H16B	0.9900	C32A—H32D	0.9800
C17—H17A	0.9800	C32A—H32E	0.9800
C17—H17B	0.9800	C32A—H32F	0.9800
C17—H17C	0.9800
C6—N1—C2	109.8 (2)	C16—C17—H17C	109.5
C6—N1—C1	110.0 (2)	H17A—C17—H17C	109.5
C2—N1—C1	111.0 (2)	H17B—C17—H17C	109.5
C13—N2—C18	120.8 (2)	N2—C18—C19	113.0 (2)
C13—N2—C16	120.8 (2)	N2—C18—H18A	109.0
C18—N2—C16	116.9 (2)	C19—C18—H18A	109.0
C26—N3—C31A	121.4 (5)	N2—C18—H18B	109.0
C26—N3—C31	122.1 (4)	C19—C18—H18B	109.0
C31A—N3—C31	40.3 (4)	H18A—C18—H18B	107.8
C26—N3—C29	121.5 (4)	C18—C19—H19A	109.5
C31A—N3—C29	87.4 (5)	C18—C19—H19B	109.5
C31—N3—C29	112.4 (6)	H19A—C19—H19B	109.5
C26—N3—C29A	120.1 (4)	C18—C19—H19C	109.5
C31A—N3—C29A	116.7 (6)	H19A—C19—H19C	109.5
C31—N3—C29A	110.6 (5)	H19B—C19—H19C	109.5
C29—N3—C29A	47.8 (4)	C3—C20—C21	129.0 (3)
N1—C1—H1A	109.5	C3—C20—H20A	115.5
N1—C1—H1B	109.5	C21—C20—H20A	115.5
H1A—C1—H1B	109.5	C22—C21—C20	122.6 (3)
N1—C1—H1C	109.5	C22—C21—H21A	118.7
H1A—C1—H1C	109.5	C20—C21—H21A	118.7
H1B—C1—H1C	109.5	C21—C22—C23	129.8 (3)
N1—C2—C3	111.6 (2)	C21—C22—H22A	115.1
N1—C2—H2A	109.3	C23—C22—H22A	115.1
C3—C2—H2A	109.3	C28—C23—C24	114.5 (3)
N1—C2—H2B	109.3	C28—C23—C22	125.1 (3)
C3—C2—H2B	109.3	C24—C23—C22	120.4 (3)
H2A—C2—H2B	108.0	C25—C24—C23	122.9 (4)
C20—C3—C4	119.0 (3)	C25—C24—H24A	118.5
C20—C3—C2	123.2 (3)	C23—C24—H24A	118.5
C4—C3—C2	117.9 (2)	C24—C25—C26	122.1 (4)
O1—C4—C5	120.8 (2)	C24—C25—H25A	118.9
O1—C4—C3	121.0 (3)	C26—C25—H25A	118.9
C5—C4—C3	118.2 (3)	C27—C26—C25	114.9 (3)
C7—C5—C4	118.8 (3)	C27—C26—N3	123.3 (3)
C7—C5—C6	123.0 (2)	C25—C26—N3	121.8 (3)
C4—C5—C6	118.2 (2)	C26—C27—C28	123.0 (3)
N1—C6—C5	110.9 (2)	C26—C27—H27A	118.5
N1—C6—H6A	109.5	C28—C27—H27A	118.5
C5—C6—H6A	109.5	C23—C28—C27	122.6 (3)
N1—C6—H6B	109.5	C23—C28—H28A	118.7
C5—C6—H6B	109.5	C27—C28—H28A	118.7
H6A—C6—H6B	108.0	N3—C29—C30	100.7 (6)
C5—C7—C8	129.2 (3)	N3—C29—H29A	111.6
C5—C7—H7A	115.4	C30—C29—H29A	111.6
C8—C7—H7A	115.4	N3—C29—H29B	111.6
C9—C8—C7	122.1 (3)	C30—C29—H29B	111.6
C9—C8—H8A	119.0	H29A—C29—H29B	109.4
C7—C8—H8A	119.0	N3—C31—C32	124.7 (10)
C8—C9—C10	130.1 (3)	N3—C31—H31A	106.1
C8—C9—H9A	115.0	C32—C31—H31A	106.1
C10—C9—H9A	115.0	N3—C31—H31B	106.1
C15—C10—C11	116.4 (2)	C32—C31—H31B	106.1
C15—C10—C9	125.0 (2)	H31A—C31—H31B	106.3
C11—C10—C9	118.5 (2)	N3—C29A—C30A	112.6 (8)
C12—C11—C10	122.6 (2)	N3—C29A—H29C	109.1
C12—C11—H11A	118.7	C30A—C29A—H29C	109.1
C10—C11—H11A	118.7	N3—C29A—H29D	109.1
C11—C12—C13	120.4 (2)	C30A—C29A—H29D	109.1
C11—C12—H12A	119.8	H29C—C29A—H29D	107.8
C13—C12—H12A	119.8	C29A—C30A—H30D	109.5
N2—C13—C14	122.2 (2)	C29A—C30A—H30E	109.5
N2—C13—C12	121.1 (2)	H30D—C30A—H30E	109.5
C14—C13—C12	116.7 (2)	C29A—C30A—H30F	109.5
C15—C14—C13	122.0 (2)	H30D—C30A—H30F	109.5
C15—C14—H14A	119.0	H30E—C30A—H30F	109.5
C13—C14—H14A	119.0	N3—C31A—C32A	106.3 (8)
C14—C15—C10	121.9 (2)	N3—C31A—H31C	110.5
C14—C15—H15A	119.1	C32A—C31A—H31C	110.5
C10—C15—H15A	119.1	N3—C31A—H31D	110.5
N2—C16—C17	112.2 (2)	C32A—C31A—H31D	110.5
N2—C16—H16A	109.2	H31C—C31A—H31D	108.7
C17—C16—H16A	109.2	C31A—C32A—H32D	109.5
N2—C16—H16B	109.2	C31A—C32A—H32E	109.5
C17—C16—H16B	109.2	H32D—C32A—H32E	109.5
H16A—C16—H16B	107.9	C31A—C32A—H32F	109.5
C16—C17—H17A	109.5	H32D—C32A—H32F	109.5
C16—C17—H17B	109.5	H32E—C32A—H32F	109.5
H17A—C17—H17B	109.5
C6—N1—C2—C3	62.5 (3)	C4—C3—C20—C21	178.2 (3)
C1—N1—C2—C3	−175.6 (2)	C2—C3—C20—C21	−1.3 (5)
N1—C2—C3—C20	146.7 (3)	C3—C20—C21—C22	−176.6 (3)
N1—C2—C3—C4	−32.8 (3)	C20—C21—C22—C23	179.2 (3)
C20—C3—C4—O1	3.4 (4)	C21—C22—C23—C28	5.4 (7)
C2—C3—C4—O1	−177.1 (3)	C21—C22—C23—C24	−175.3 (5)
C20—C3—C4—C5	−175.3 (2)	C28—C23—C24—C25	−1.7 (9)
C2—C3—C4—C5	4.1 (4)	C22—C23—C24—C25	178.9 (6)
O1—C4—C5—C7	−3.8 (4)	C23—C24—C25—C26	1.4 (11)
C3—C4—C5—C7	175.0 (2)	C24—C25—C26—C27	0.1 (9)
O1—C4—C5—C6	176.8 (3)	C24—C25—C26—N3	−179.5 (6)
C3—C4—C5—C6	−4.4 (4)	C31A—N3—C26—C27	37.5 (7)
C2—N1—C6—C5	−62.4 (3)	C31—N3—C26—C27	−10.4 (7)
C1—N1—C6—C5	175.2 (2)	C29—N3—C26—C27	145.6 (5)
C7—C5—C6—N1	−146.3 (3)	C29A—N3—C26—C27	−158.1 (5)
C4—C5—C6—N1	33.0 (3)	C31A—N3—C26—C25	−143.0 (6)
C4—C5—C7—C8	179.3 (2)	C31—N3—C26—C25	169.2 (6)
C6—C5—C7—C8	−1.4 (5)	C29—N3—C26—C25	−34.9 (7)
C5—C7—C8—C9	176.7 (3)	C29A—N3—C26—C25	21.5 (7)
C7—C8—C9—C10	179.5 (2)	C25—C26—C27—C28	−1.2 (6)
C8—C9—C10—C15	−5.1 (4)	N3—C26—C27—C28	178.4 (4)
C8—C9—C10—C11	172.9 (3)	C24—C23—C28—C27	0.6 (6)
C15—C10—C11—C12	0.7 (4)	C22—C23—C28—C27	179.9 (4)
C9—C10—C11—C12	−177.5 (2)	C26—C27—C28—C23	0.9 (6)
C10—C11—C12—C13	−0.9 (4)	C26—N3—C29—C30	95.4 (6)
C18—N2—C13—C14	−15.1 (4)	C31A—N3—C29—C30	−139.0 (6)
C16—N2—C13—C14	179.5 (2)	C31—N3—C29—C30	−106.6 (6)
C18—N2—C13—C12	166.1 (2)	C29A—N3—C29—C30	−8.5 (6)
C16—N2—C13—C12	0.7 (4)	C26—N3—C31—C32	82.1 (12)
C11—C12—C13—N2	179.7 (2)	C31A—N3—C31—C32	−20.1 (9)
C11—C12—C13—C14	0.8 (4)	C29—N3—C31—C32	−75.8 (10)
N2—C13—C14—C15	−179.4 (2)	C29A—N3—C31—C32	−127.5 (10)
C12—C13—C14—C15	−0.6 (4)	C26—N3—C29A—C30A	−80.8 (9)
C13—C14—C15—C10	0.4 (4)	C31A—N3—C29A—C30A	84.4 (9)
C11—C10—C15—C14	−0.5 (4)	C31—N3—C29A—C30A	128.1 (8)
C9—C10—C15—C14	177.6 (2)	C29—N3—C29A—C30A	26.1 (7)
C13—N2—C16—C17	80.0 (3)	C26—N3—C31A—C32A	−102.1 (7)
C18—N2—C16—C17	−86.0 (3)	C31—N3—C31A—C32A	2.0 (6)
C13—N2—C18—C19	94.8 (3)	C29—N3—C31A—C32A	132.1 (8)
C16—N2—C18—C19	−99.2 (3)	C29A—N3—C31A—C32A	92.9 (8)