N-[(2-Phenyl-2H-1,2,3-triazol-4-yl)­methyl­ene]-2-(2-(2-phenyl-2H-1,2,3-triazol-4-yl)-3-{2-[(2-phenyl-2H-1,2,3-triazol-4-yl)methyl­eneamino]eth­yl}­imidazolidin-1-yl)ethanamine

The reaction of 2-phenyl-2H-1,2,3-triazole-4-carbaldehyde with triethylenetetramine leads to the formation of a new binucleating ligand, viz. the title compound, C₃₃H₃₃N₁₃, demonstrating that this structure has the potential for more flexible rational design and tailoring. The title mol­ecule is rendered quite rigid by the formation of a five-membered imidazolidine ring and there are four independent instances of [pi]-[pi] inter­actions. Both sides of each of the three aromatic arms take part in these inter­actions, forming a neat three-dimensional array structure.

S1. Comment

The field of binucleating ligands and their metal complexes has been receiving considerable attention in recent years because of their importance in bioinorganic chemistry, molecular magnetism and catalysis (Nanda et al., 2006; Fondo et al., 2005). In the past decade, nitrogenous heterocyclic Schiff bases have gained more and more recognition because they may act as a polydentate ligand and present a variety of coordination modes (Drabent et al., 2004). Our interest in metal complexes with heterocyclic Schiff bases (Wang et al., 2001; Feng et al., 2007, 2008) has led us to prepare a new symmetrical binucleating ligand, (I), and we report here its structure.

A view of (I) is shown in Fig. 1, and selected bond lengths and angles are listed in Table 1. The molecular skeleton of the title compound contains an imidazolidine ring that adopts an envelope conformation. The N4—C10—C11—N5 and N6—C14—C15—N7 fragments both adopt gauche conformations [N4—C10—C11—N5 = -65.0 (2)° and N6—C14—C15—N7 = 65.9 (2)°]. The C1–C8/N1–N3 and C17–C24/N8–N10 ring systems are nearly coplanar, the dihedral angle between them being 5.90 (s.u. value?)°. Overall, the molecular structure resembles a Y. The C9═N4 and C16═N7 distances (Table 1) correspond to a formal C═N double bond (Yang et al., 1995). The C—C and C—N distances within the saturated imidazolidine ring (N5/C12/C13/N6/C25) are in the 1.452 (2)–1.492 (3) Å range. Similar behaviour is found for [Ag(µ₃-hmt)(p-nba)].2.5H₂O (1.457–1.496 Å; hmt is hexamethylenetetramine; p-nba is 4-nitrobenzoate; Mukhopadhyay et al., 2001).

No classical hydrogen bonding is observed in the crystal structure. However, there exist strong intermolecular aromatic π–π interactions between the adjacent molecules resulting in a highly ordered packing, as shown in Fig. 2. Both sides of each of the three aromatic arms take part in these interactions to form a very neat (and no doubt favourable) three-dimensional array structure. There are four independent instances of π–π interactions in this novel structure. The face-to-face distances between the adjacent (exactly) parallel aromatic surfaces (d₁ and d₄) are 3.85 (1) and 3.41 (8)Å. The interactions d₂ and d₃ are between nonparallel planes. The maximum and minimum distances between interacting atoms from plane 2 to plane 3 are 3.942 (2) and 3.398 (3)Å. Its average value is 3.68Å. The corresponding values from atoms of plane 3 to plane 4 are 3.842 (3), 3.335 (2) and 3.54Å, respectively, indicating significant π–π stacking interaction.

Related literature

For related literature, see: Drabent et al. (2004); Feng et al. (2007, 2008); Fondo et al. (2005); Mukhopadhyay et al. (2001); Nanda et al. (2006); Wang et al. (2001); Yang et al. (1995).

S2. Experimental

The title compound was synthesized by refluxing 2-phenyl-2H-1,2,3-triazole-4-carbaldehyde (3 mmol) and triethylenetetramine (1 mmol) in 40 ml of ethanol in the presence of glacial acetic acid (2 ml). The mixture was refluxed for 4 h under magnetic stirring. After cooling to room temperature, a white powdery product was obtained (yield 85%, m.p. 381.0–381.4 K). The colorless filtrate was allowed to evaporate slowly, affording X-ray quality crystals of the title compound. Analysis calculated for C₃₃H₃₃N₁₃: C 64.80, H 5.44, N 29.77%; found: C 64.92, H 5.47, N 29.93%. IR (KBr pellet, cm^-1): 3443 (b), 2922 (s), 2882 (s), 2826 (s), 1654 (vs), 1595 (vs), 1497 (s), 1346 (s), 752 (s).

S3. Refinement

H atoms were positioned geometrically, with C—H distances of 0.95–0.98 Å, and refined as riding, with U_iso(H) values of 1.2U_eq(C).

Computing details

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Perspective view along the a axis showing the three-dimensional supramolecular array in (I) and the intermolecular π–π stacking interactions.

N-[(2-Phenyl-2H-1,2,3-triazol-4-yl)methylene]-2-(2-(2-phenyl-2H-1,2,3- triazol-4-yl)-3-{2-[(2-phenyl-2H-1,2,3-triazol-4- yl)methyleneamino]ethyl}imidazolidin-1-yl)ethanamine

Crystal data

C33H33N13	F(000) = 644
Mr = 611.72	Dx = 1.264 Mg m^−3
Triclinic, P1	Melting point = 381.0–381.4 K
a = 7.7473 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.350 (3) Å	Cell parameters from 7072 reflections
c = 17.211 (4) Å	θ = 3.0–27.5°
α = 87.487 (5)°	µ = 0.08 mm^−1
β = 82.227 (5)°	T = 293 K
γ = 80.247 (5)°	Needle, colorless
V = 1607.7 (6) Å^3	0.42 × 0.35 × 0.14 mm
Z = 2

Data collection

Rigaku R-AXIS Spider diffractometer	7203 independent reflections
Radiation source: fine-focus sealed tube	3365 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995)	h = −10→9
Tmin = 0.967, Tmax = 0.989	k = −16→13
15461 measured reflections	l = −22→22

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.186	w = 1/[σ^2(Fo^2) + (0.0954P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.003
7203 reflections	Δρmax = 0.23 e Å^−3
416 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (2)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.2570 (2)	0.64280 (15)	0.29745 (11)	0.0749 (5)
N2	0.4313 (2)	0.64132 (14)	0.28887 (11)	0.0719 (5)
N3	0.5224 (3)	0.55686 (16)	0.32562 (13)	0.0859 (6)
N4	0.0459 (2)	0.44129 (16)	0.40981 (11)	0.0739 (5)
N5	−0.0578 (2)	0.27374 (13)	0.32005 (9)	0.0606 (4)
N6	0.00592 (19)	0.16426 (12)	0.21458 (9)	0.0579 (4)
N7	0.2345 (2)	0.09230 (15)	0.06853 (11)	0.0694 (5)
N8	0.6916 (3)	0.23691 (17)	−0.00767 (13)	0.0915 (7)
N9	0.5886 (2)	0.32226 (14)	−0.03821 (11)	0.0695 (5)
N10	0.4169 (2)	0.31615 (14)	−0.02812 (10)	0.0683 (5)
N11	0.4736 (3)	0.11312 (17)	0.33388 (14)	0.0946 (7)
N12	0.4070 (2)	0.02547 (14)	0.36276 (10)	0.0645 (5)
N13	0.2371 (2)	0.02825 (13)	0.35609 (10)	0.0617 (4)
C1	0.6973 (3)	0.7100 (2)	0.23488 (17)	0.0943 (8)
H1B	0.7641	0.6488	0.2560	0.113*
C2	0.7791 (4)	0.7890 (3)	0.19350 (19)	0.1037 (9)
H2A	0.9016	0.7818	0.1872	0.124*
C3	0.6811 (4)	0.8782 (2)	0.16151 (16)	0.0924 (8)
H3B	0.7366	0.9314	0.1332	0.111*
C4	0.5012 (4)	0.8888 (2)	0.17128 (16)	0.0909 (8)
H4B	0.4349	0.9494	0.1493	0.109*
C5	0.4167 (3)	0.8113 (2)	0.21294 (15)	0.0819 (7)
H5A	0.2941	0.8192	0.2195	0.098*
C6	0.5163 (3)	0.72206 (18)	0.24479 (13)	0.0711 (6)
C7	0.2338 (3)	0.55468 (18)	0.34225 (13)	0.0695 (6)
C8	0.3976 (3)	0.5025 (2)	0.35915 (15)	0.0812 (7)
H8B	0.4172	0.4386	0.3896	0.097*
C9	0.0635 (3)	0.5213 (2)	0.36404 (14)	0.0749 (6)
H9A	−0.0348	0.5600	0.3437	0.090*
C10	−0.1256 (3)	0.4072 (2)	0.42568 (14)	0.0798 (7)
H10B	−0.2083	0.4529	0.3955	0.096*
H10C	−0.1702	0.4156	0.4809	0.096*
C11	−0.1082 (3)	0.2889 (2)	0.40376 (13)	0.0763 (6)
H11B	−0.0201	0.2445	0.4319	0.092*
H11C	−0.2200	0.2637	0.4195	0.092*
C12	−0.2001 (3)	0.30932 (19)	0.27247 (13)	0.0735 (6)
H12A	−0.2037	0.3859	0.2564	0.088*
H12B	−0.3133	0.3007	0.3017	0.088*
C13	−0.1592 (3)	0.23736 (19)	0.20275 (14)	0.0737 (6)
H13B	−0.2533	0.1954	0.2001	0.088*
H13C	−0.1440	0.2808	0.1547	0.088*
C14	0.0257 (3)	0.05643 (17)	0.18121 (13)	0.0692 (6)
H14A	−0.0818	0.0261	0.1966	0.083*
H14B	0.1215	0.0081	0.2022	0.083*
C15	0.0636 (3)	0.06014 (19)	0.09281 (13)	0.0733 (6)
H15A	0.0622	−0.0117	0.0725	0.088*
H15B	−0.0274	0.1123	0.0716	0.088*
C16	0.2415 (3)	0.18389 (18)	0.03470 (13)	0.0684 (6)
H16A	0.1373	0.2283	0.0244	0.082*
C17	0.4072 (3)	0.22177 (18)	0.01149 (12)	0.0677 (6)
C18	0.5768 (3)	0.1737 (2)	0.02308 (16)	0.0882 (8)
H18A	0.6059	0.1066	0.0488	0.106*
C19	0.6585 (3)	0.41100 (17)	−0.07889 (13)	0.0679 (6)
C20	0.5479 (3)	0.49047 (18)	−0.11569 (13)	0.0740 (6)
H20A	0.4286	0.4865	−0.1136	0.089*
C21	0.6171 (3)	0.5752 (2)	−0.15532 (15)	0.0828 (7)
H21A	0.5432	0.6290	−0.1802	0.099*
C22	0.7922 (4)	0.5826 (2)	−0.15909 (16)	0.0890 (7)
H22A	0.8373	0.6406	−0.1862	0.107*
C23	0.8995 (4)	0.5032 (2)	−0.12239 (18)	0.0995 (9)
H23A	1.0189	0.5072	−0.1248	0.119*
C24	0.8336 (3)	0.4169 (2)	−0.08165 (17)	0.0928 (8)
H24A	0.9076	0.3636	−0.0564	0.111*
C25	0.0096 (2)	0.16039 (16)	0.29910 (12)	0.0588 (5)
H25A	−0.0704	0.1121	0.3246	0.071*
C26	0.1910 (2)	0.12383 (17)	0.31993 (12)	0.0613 (5)
C27	0.3358 (3)	0.1752 (2)	0.30729 (18)	0.0966 (9)
H27A	0.3375	0.2441	0.2834	0.116*
C28	0.5110 (3)	−0.06550 (17)	0.39783 (12)	0.0649 (6)
C29	0.4362 (3)	−0.15426 (19)	0.42628 (14)	0.0800 (7)
H29A	0.3175	−0.1556	0.4236	0.096*
C30	0.5398 (4)	−0.2420 (2)	0.45909 (16)	0.0938 (8)
H30A	0.4902	−0.3029	0.4782	0.113*
C31	0.7130 (4)	−0.2404 (2)	0.46378 (16)	0.0981 (9)
H31A	0.7813	−0.2994	0.4865	0.118*
C32	0.7847 (4)	−0.1527 (3)	0.4352 (2)	0.1221 (12)
H32A	0.9036	−0.1519	0.4376	0.146*
C33	0.6840 (3)	−0.0631 (2)	0.40207 (19)	0.1092 (10)
H33A	0.7344	−0.0024	0.3831	0.131*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0704 (12)	0.0749 (12)	0.0754 (13)	0.0076 (9)	−0.0185 (9)	−0.0056 (10)
N2	0.0751 (12)	0.0651 (11)	0.0734 (12)	0.0065 (9)	−0.0237 (9)	−0.0061 (9)
N3	0.0799 (13)	0.0751 (13)	0.0994 (16)	0.0083 (11)	−0.0295 (11)	0.0077 (11)
N4	0.0726 (12)	0.0766 (13)	0.0719 (13)	−0.0005 (9)	−0.0182 (9)	−0.0128 (10)
N5	0.0558 (9)	0.0678 (10)	0.0575 (11)	−0.0052 (8)	−0.0101 (7)	−0.0033 (8)
N6	0.0539 (9)	0.0601 (10)	0.0599 (10)	−0.0064 (7)	−0.0119 (7)	−0.0031 (8)
N7	0.0694 (11)	0.0701 (11)	0.0666 (12)	−0.0057 (9)	−0.0083 (8)	−0.0024 (9)
N8	0.0762 (13)	0.0865 (14)	0.1087 (17)	−0.0012 (11)	−0.0257 (11)	0.0255 (12)
N9	0.0700 (11)	0.0675 (11)	0.0690 (12)	−0.0022 (9)	−0.0150 (9)	0.0034 (9)
N10	0.0700 (11)	0.0696 (11)	0.0639 (11)	−0.0047 (9)	−0.0119 (8)	−0.0020 (9)
N11	0.0685 (12)	0.0927 (14)	0.1307 (19)	−0.0306 (11)	−0.0347 (11)	0.0440 (14)
N12	0.0594 (10)	0.0672 (11)	0.0700 (11)	−0.0163 (8)	−0.0155 (8)	0.0108 (9)
N13	0.0559 (9)	0.0658 (10)	0.0642 (11)	−0.0116 (8)	−0.0108 (7)	0.0045 (8)
C1	0.0816 (17)	0.0949 (19)	0.109 (2)	−0.0046 (14)	−0.0362 (15)	0.0081 (16)
C2	0.0826 (17)	0.117 (2)	0.118 (2)	−0.0230 (17)	−0.0334 (16)	0.0071 (19)
C3	0.103 (2)	0.0915 (18)	0.0907 (19)	−0.0264 (16)	−0.0282 (15)	−0.0022 (15)
C4	0.1001 (19)	0.0820 (17)	0.0883 (19)	−0.0036 (14)	−0.0196 (15)	0.0026 (14)
C5	0.0816 (15)	0.0756 (15)	0.0827 (17)	0.0071 (12)	−0.0165 (12)	0.0023 (13)
C6	0.0806 (14)	0.0678 (14)	0.0651 (14)	−0.0021 (11)	−0.0207 (11)	−0.0085 (11)
C7	0.0755 (14)	0.0664 (13)	0.0643 (14)	0.0044 (11)	−0.0191 (10)	−0.0084 (11)
C8	0.0757 (15)	0.0730 (14)	0.0912 (18)	0.0076 (12)	−0.0246 (13)	0.0067 (13)
C9	0.0718 (14)	0.0790 (15)	0.0697 (15)	0.0109 (12)	−0.0209 (11)	−0.0112 (12)
C10	0.0699 (14)	0.1016 (18)	0.0652 (15)	−0.0020 (12)	−0.0084 (11)	−0.0195 (13)
C11	0.0728 (13)	0.0934 (17)	0.0603 (14)	−0.0100 (12)	−0.0036 (10)	−0.0042 (12)
C12	0.0626 (12)	0.0821 (15)	0.0731 (15)	0.0030 (11)	−0.0158 (10)	−0.0076 (12)
C13	0.0602 (12)	0.0846 (15)	0.0753 (15)	0.0013 (11)	−0.0192 (10)	−0.0093 (12)
C14	0.0699 (12)	0.0645 (13)	0.0769 (16)	−0.0177 (10)	−0.0122 (11)	−0.0102 (11)
C15	0.0746 (14)	0.0748 (14)	0.0731 (16)	−0.0125 (11)	−0.0144 (11)	−0.0129 (11)
C16	0.0707 (13)	0.0709 (14)	0.0621 (13)	−0.0013 (11)	−0.0154 (10)	−0.0043 (11)
C17	0.0725 (14)	0.0684 (13)	0.0602 (13)	−0.0018 (11)	−0.0132 (10)	−0.0020 (11)
C18	0.0777 (16)	0.0836 (16)	0.101 (2)	−0.0063 (13)	−0.0203 (13)	0.0254 (15)
C19	0.0755 (14)	0.0685 (13)	0.0582 (13)	−0.0066 (11)	−0.0093 (10)	−0.0028 (10)
C20	0.0788 (14)	0.0751 (15)	0.0677 (15)	−0.0074 (12)	−0.0152 (11)	−0.0006 (12)
C21	0.0916 (17)	0.0804 (16)	0.0764 (17)	−0.0117 (13)	−0.0174 (13)	0.0081 (13)
C22	0.0959 (18)	0.0866 (17)	0.0838 (18)	−0.0171 (15)	−0.0099 (14)	0.0072 (14)
C23	0.0795 (16)	0.106 (2)	0.112 (2)	−0.0216 (15)	−0.0105 (15)	0.0151 (17)
C24	0.0746 (16)	0.0955 (18)	0.107 (2)	−0.0092 (14)	−0.0181 (13)	0.0180 (16)
C25	0.0523 (10)	0.0641 (12)	0.0614 (13)	−0.0131 (9)	−0.0093 (8)	0.0048 (10)
C26	0.0566 (11)	0.0663 (13)	0.0625 (13)	−0.0148 (9)	−0.0108 (9)	0.0088 (10)
C27	0.0684 (14)	0.0916 (17)	0.137 (2)	−0.0273 (13)	−0.0392 (14)	0.0526 (17)
C28	0.0636 (12)	0.0716 (13)	0.0586 (13)	−0.0049 (10)	−0.0147 (9)	0.0064 (10)
C29	0.0728 (14)	0.0829 (16)	0.0800 (16)	−0.0065 (12)	−0.0080 (11)	0.0148 (13)
C30	0.0960 (19)	0.0878 (17)	0.0894 (19)	0.0011 (14)	−0.0107 (14)	0.0235 (14)
C31	0.104 (2)	0.0917 (19)	0.092 (2)	0.0092 (16)	−0.0275 (15)	0.0147 (15)
C32	0.0818 (18)	0.125 (2)	0.162 (3)	−0.0101 (18)	−0.0505 (19)	0.046 (2)
C33	0.0757 (16)	0.114 (2)	0.145 (3)	−0.0261 (15)	−0.0426 (16)	0.050 (2)

Geometric parameters (Å, º)

N1—C7	1.329 (3)	C11—H11B	0.9700
N1—N2	1.336 (2)	C11—H11C	0.9700
N2—N3	1.342 (2)	C12—C13	1.492 (3)
N2—C6	1.423 (3)	C12—H12A	0.9700
N3—C8	1.324 (3)	C12—H12B	0.9700
N4—C9	1.251 (3)	C13—H13B	0.9700
N4—C10	1.448 (3)	C13—H13C	0.9700
N5—C25	1.452 (2)	C14—C15	1.510 (3)
N5—C11	1.453 (3)	C14—H14A	0.9700
N5—C12	1.458 (2)	C14—H14B	0.9700
N6—C14	1.449 (3)	C15—H15A	0.9700
N6—C25	1.457 (2)	C15—H15B	0.9700
N6—C13	1.469 (2)	C16—C17	1.440 (3)
N7—C16	1.255 (3)	C16—H16A	0.9300
N7—C15	1.449 (3)	C17—C18	1.384 (3)
N8—C18	1.324 (3)	C18—H18A	0.9300
N8—N9	1.343 (2)	C19—C24	1.366 (3)
N9—N10	1.332 (2)	C19—C20	1.380 (3)
N9—C19	1.420 (3)	C20—C21	1.370 (3)
N10—C17	1.332 (3)	C20—H20A	0.9300
N11—N12	1.326 (2)	C21—C22	1.368 (3)
N11—C27	1.327 (3)	C21—H21A	0.9300
N12—N13	1.331 (2)	C22—C23	1.365 (3)
N12—C28	1.429 (2)	C22—H22A	0.9300
N13—C26	1.327 (2)	C23—C24	1.382 (3)
C1—C6	1.373 (3)	C23—H23A	0.9300
C1—C2	1.374 (4)	C24—H24A	0.9300
C1—H1B	0.9300	C25—C26	1.488 (3)
C2—C3	1.367 (3)	C25—H25A	0.9800
C2—H2A	0.9300	C26—C27	1.368 (3)
C3—C4	1.365 (4)	C27—H27A	0.9300
C3—H3B	0.9300	C28—C33	1.357 (3)
C4—C5	1.372 (3)	C28—C29	1.367 (3)
C4—H4B	0.9300	C29—C30	1.382 (3)
C5—C6	1.373 (3)	C29—H29A	0.9300
C5—H5A	0.9300	C30—C31	1.359 (4)
C7—C8	1.385 (3)	C30—H30A	0.9300
C7—C9	1.445 (3)	C31—C32	1.345 (4)
C8—H8B	0.9300	C31—H31A	0.9300
C9—H9A	0.9300	C32—C33	1.389 (3)
C10—C11	1.505 (3)	C32—H32A	0.9300
C10—H10B	0.9700	C33—H33A	0.9300
C10—H10C	0.9700
C7—N1—N2	104.15 (17)	C12—C13—H13C	110.8
N1—N2—N3	114.59 (19)	H13B—C13—H13C	108.8
N1—N2—C6	123.61 (16)	N6—C14—C15	112.17 (17)
N3—N2—C6	121.80 (19)	N6—C14—H14A	109.2
C8—N3—N2	103.05 (18)	C15—C14—H14A	109.2
C9—N4—C10	118.7 (2)	N6—C14—H14B	109.2
C25—N5—C11	113.68 (15)	C15—C14—H14B	109.2
C25—N5—C12	105.22 (16)	H14A—C14—H14B	107.9
C11—N5—C12	114.60 (15)	N7—C15—C14	110.22 (18)
C14—N6—C25	113.17 (15)	N7—C15—H15A	109.6
C14—N6—C13	114.57 (16)	C14—C15—H15A	109.6
C25—N6—C13	105.04 (15)	N7—C15—H15B	109.6
C16—N7—C15	119.08 (19)	C14—C15—H15B	109.6
C18—N8—N9	102.89 (19)	H15A—C15—H15B	108.1
N10—N9—N8	114.72 (18)	N7—C16—C17	121.6 (2)
N10—N9—C19	122.96 (16)	N7—C16—H16A	119.2
N8—N9—C19	122.32 (19)	C17—C16—H16A	119.2
C17—N10—N9	104.19 (16)	N10—C17—C18	107.9 (2)
N12—N11—C27	102.46 (17)	N10—C17—C16	122.02 (19)
N11—N12—N13	115.10 (15)	C18—C17—C16	130.0 (2)
N11—N12—C28	122.23 (17)	N8—C18—C17	110.3 (2)
N13—N12—C28	122.67 (17)	N8—C18—H18A	124.9
C26—N13—N12	103.98 (15)	C17—C18—H18A	124.9
C6—C1—C2	119.5 (2)	C24—C19—C20	120.6 (2)
C6—C1—H1B	120.3	C24—C19—N9	120.03 (19)
C2—C1—H1B	120.3	C20—C19—N9	119.3 (2)
C3—C2—C1	120.3 (3)	C21—C20—C19	118.9 (2)
C3—C2—H2A	119.9	C21—C20—H20A	120.6
C1—C2—H2A	119.9	C19—C20—H20A	120.6
C4—C3—C2	119.7 (3)	C22—C21—C20	121.5 (2)
C4—C3—H3B	120.2	C22—C21—H21A	119.2
C2—C3—H3B	120.2	C20—C21—H21A	119.2
C3—C4—C5	121.1 (2)	C23—C22—C21	118.8 (2)
C3—C4—H4B	119.5	C23—C22—H22A	120.6
C5—C4—H4B	119.5	C21—C22—H22A	120.6
C4—C5—C6	118.8 (2)	C22—C23—C24	121.1 (3)
C4—C5—H5A	120.6	C22—C23—H23A	119.5
C6—C5—H5A	120.6	C24—C23—H23A	119.5
C1—C6—C5	120.7 (2)	C19—C24—C23	119.1 (2)
C1—C6—N2	119.55 (19)	C19—C24—H24A	120.4
C5—C6—N2	119.7 (2)	C23—C24—H24A	120.4
N1—C7—C8	108.2 (2)	N5—C25—N6	102.03 (14)
N1—C7—C9	123.20 (19)	N5—C25—C26	111.88 (17)
C8—C7—C9	128.6 (2)	N6—C25—C26	112.15 (16)
N3—C8—C7	110.0 (2)	N5—C25—H25A	110.2
N3—C8—H8B	125.0	N6—C25—H25A	110.2
C7—C8—H8B	125.0	C26—C25—H25A	110.2
N4—C9—C7	121.1 (2)	N13—C26—C27	107.84 (18)
N4—C9—H9A	119.4	N13—C26—C25	122.28 (18)
C7—C9—H9A	119.4	C27—C26—C25	129.88 (19)
N4—C10—C11	109.13 (18)	N11—C27—C26	110.6 (2)
N4—C10—H10B	109.9	N11—C27—H27A	124.7
C11—C10—H10B	109.9	C26—C27—H27A	124.7
N4—C10—H10C	109.9	C33—C28—C29	120.58 (19)
C11—C10—H10C	109.9	C33—C28—N12	119.5 (2)
H10B—C10—H10C	108.3	C29—C28—N12	119.93 (19)
N5—C11—C10	112.00 (18)	C28—C29—C30	119.0 (2)
N5—C11—H11B	109.2	C28—C29—H29A	120.5
C10—C11—H11B	109.2	C30—C29—H29A	120.5
N5—C11—H11C	109.2	C31—C30—C29	120.9 (3)
C10—C11—H11C	109.2	C31—C30—H30A	119.5
H11B—C11—H11C	107.9	C29—C30—H30A	119.5
N5—C12—C13	105.61 (15)	C32—C31—C30	119.3 (2)
N5—C12—H12A	110.6	C32—C31—H31A	120.3
C13—C12—H12A	110.6	C30—C31—H31A	120.3
N5—C12—H12B	110.6	C31—C32—C33	121.1 (3)
C13—C12—H12B	110.6	C31—C32—H32A	119.4
H12A—C12—H12B	108.7	C33—C32—H32A	119.4
N6—C13—C12	104.87 (16)	C28—C33—C32	119.1 (3)
N6—C13—H13B	110.8	C28—C33—H33A	120.5
C12—C13—H13B	110.8	C32—C33—H33A	120.5
N6—C13—H13C	110.8
C7—N1—N2—N3	0.1 (2)	N9—N10—C17—C16	179.86 (19)
C7—N1—N2—C6	−179.7 (2)	N7—C16—C17—N10	176.4 (2)
N1—N2—N3—C8	0.0 (3)	N7—C16—C17—C18	−3.1 (4)
C6—N2—N3—C8	179.8 (2)	N9—N8—C18—C17	−0.6 (3)
C18—N8—N9—N10	0.2 (3)	N10—C17—C18—N8	0.8 (3)
C18—N8—N9—C19	−179.0 (2)	C16—C17—C18—N8	−179.7 (2)
N8—N9—N10—C17	0.3 (3)	N10—N9—C19—C24	174.6 (2)
C19—N9—N10—C17	179.44 (19)	N8—N9—C19—C24	−6.3 (3)
C27—N11—N12—N13	0.0 (3)	N10—N9—C19—C20	−5.7 (3)
C27—N11—N12—C28	179.5 (2)	N8—N9—C19—C20	173.4 (2)
N11—N12—N13—C26	0.5 (3)	C24—C19—C20—C21	0.3 (4)
C28—N12—N13—C26	−179.03 (19)	N9—C19—C20—C21	−179.5 (2)
C6—C1—C2—C3	−0.9 (5)	C19—C20—C21—C22	0.0 (4)
C1—C2—C3—C4	0.4 (5)	C20—C21—C22—C23	0.1 (4)
C2—C3—C4—C5	0.2 (4)	C21—C22—C23—C24	−0.3 (5)
C3—C4—C5—C6	−0.2 (4)	C20—C19—C24—C23	−0.5 (4)
C2—C1—C6—C5	0.9 (4)	N9—C19—C24—C23	179.2 (2)
C2—C1—C6—N2	−178.8 (3)	C22—C23—C24—C19	0.6 (5)
C4—C5—C6—C1	−0.3 (4)	C11—N5—C25—N6	166.08 (15)
C4—C5—C6—N2	179.4 (2)	C12—N5—C25—N6	39.89 (18)
N1—N2—C6—C1	−175.7 (2)	C11—N5—C25—C26	−73.9 (2)
N3—N2—C6—C1	4.4 (3)	C12—N5—C25—C26	159.96 (17)
N1—N2—C6—C5	4.5 (3)	C14—N6—C25—N5	−165.61 (15)
N3—N2—C6—C5	−175.3 (2)	C13—N6—C25—N5	−39.93 (19)
N2—N1—C7—C8	−0.1 (2)	C14—N6—C25—C26	74.5 (2)
N2—N1—C7—C9	−177.4 (2)	C13—N6—C25—C26	−159.81 (17)
N2—N3—C8—C7	0.0 (3)	N12—N13—C26—C27	−0.8 (3)
N1—C7—C8—N3	0.1 (3)	N12—N13—C26—C25	178.94 (18)
C9—C7—C8—N3	177.2 (2)	N5—C25—C26—N13	133.9 (2)
C10—N4—C9—C7	−176.1 (2)	N6—C25—C26—N13	−112.1 (2)
N1—C7—C9—N4	−176.1 (2)	N5—C25—C26—C27	−46.4 (3)
C8—C7—C9—N4	7.2 (4)	N6—C25—C26—C27	67.5 (3)
C9—N4—C10—C11	122.2 (2)	N12—N11—C27—C26	−0.5 (3)
C25—N5—C11—C10	163.14 (17)	N13—C26—C27—N11	0.8 (3)
C12—N5—C11—C10	−75.8 (2)	C25—C26—C27—N11	−178.8 (2)
N4—C10—C11—N5	−65.0 (2)	N11—N12—C28—C33	0.0 (4)
C25—N5—C12—C13	−24.7 (2)	N13—N12—C28—C33	179.4 (2)
C11—N5—C12—C13	−150.31 (19)	N11—N12—C28—C29	−179.6 (2)
C14—N6—C13—C12	149.58 (18)	N13—N12—C28—C29	−0.1 (3)
C25—N6—C13—C12	24.8 (2)	C33—C28—C29—C30	−0.3 (4)
N5—C12—C13—N6	−0.1 (2)	N12—C28—C29—C30	179.2 (2)
C25—N6—C14—C15	−166.82 (16)	C28—C29—C30—C31	0.5 (4)
C13—N6—C14—C15	72.8 (2)	C29—C30—C31—C32	−0.8 (5)
C16—N7—C15—C14	−111.9 (2)	C30—C31—C32—C33	1.0 (5)
N6—C14—C15—N7	65.9 (2)	C29—C28—C33—C32	0.5 (5)
C15—N7—C16—C17	178.0 (2)	N12—C28—C33—C32	−179.0 (3)
N9—N10—C17—C18	−0.6 (2)	C31—C32—C33—C28	−0.8 (5)