N,N'-Dicyclo­hexyl-N-[4-(1H-indol-3-yl)butano­yl]urea

The title compound, C₂₅H₃₅N₃O₂, is a novel urea derivative. Pairs of inter­molecular N-H...O hydrogen bonds join the mol­ecules into centrosymmetric R₂²(12) and R₂²(18) dimeric rings, which are alternately linked into one-dimensional polymeric chains along the [010] direction. The parallel chains are connected via C-H...O hydrogen bonds to generate a two-dimensional framework structure parallel to the (001) plane. The title compound was also modelled by solid-state density functional theory (DFT) calculations. A comparison of the mol­ecular conformation and hydrogen-bond geometry obtained from the X-ray structure analysis and the theoretical study clearly indicates that the DFT calculation agrees closely with the X-ray structure.

S1. Comment

In the molecular recognition and self-assembly process, relatively simple building blocks recognize one another, associate, and form one-, two- and three-dimensional supramolecular frameworks. The phenomenon of specific recognition is facilitated by a combination of different noncovalent interactions, which include electrostatic interactions, hydrogen bonds, hydrophobic interactions and aromatic stacking interactions. The overall combination of various molecular forces, which are quite weak individually, results in the process of self-organization from simple blocks into complex supramolecular structures. In this context, substituted ureas having multiple hydrogen-bonding potential are of considerable current interest (Allen et al., 1997; Gale & Quesada,2006; Custelcean, 2008). Several urea derivatives have been found to contain a one-dimensional α-network, which in turn is linked to form two-dimensional β-sheets through N—H···O hydrogen bonds. Many of these compounds also exhibit a wide range of biological activities as herbicides, pesticides and fungicides (Bessard & Crettaz, 2000; Sun & Zhang, 2006).

As part of an ongoing programme on the synthesis and structural characterization of novel urea derivatives, we synthesized N,N'-dicyclohexyl-N-[4-(3-indolyl)butanoyl]urea, (I), designed for self-complexation, and the crystal structure of (I) was established by single-crystal X-ray analysis. Since the positions of H atoms in molecular systems are usually determined with limited accuracy by an X-ray study, a solid-state density functional theory (DFT) calculation has been performed for a better understanding of the intra- and intermolecular hydrogen-bond geometry in the title compound. The advantage of the DFT method over X-ray structure refinement is that the positions of the H atoms are optimized simultaneously along with the positions of the non-H atoms, thus providing a more reliable hydrogen-bond geometry.

The asymmetric unit of (I) (Fig. 1) consists of a planar indoline group (C1–C8/N1), with an r.m.s. deviation of 0.013 Å, and a dicyclohexylurea unit joined through a butanoyl chain. The two cyclohexyl groups are in a syn–syn conformation with respect to the urea group; the O2—C13—N3—C14 and O2—C13—N2—C20 torsion angles are 4.5 (2) and 48.7 (1)°, respectively. The extended molecular conformation of (I) is indicated by the C9—C10—C11—C12 torsion angle of -174.9 (2)°. Each of the cyclohexyl groups in (I) adopts a chair conformation, with ring-puckering parameters (Cremer & Pople, 1975) Q, θ and ϕ of 0.569 (2) Å, 180.0 (2)° and 344 (53)°, respectively, for the C14—C19 ring, and 0.579 (2) Å, 2.9 (2)° and 54 (3)°, respectively, for the C20–C25 ring. The two carbonyl groups in the N-acylurido unit, are twisted substantially at the central atom N2, with a dihedral angle of 58.3 (1)° between the O1/C12/N2 and N2/C13/O2 planes, which increases the distance between atoms O1 and N3. Therefore, as expected, no intramolecular N3—H3N···O1 hydrogen bond is formed.

The observed bond distances from the X-ray analysis are in accord with the corresponding values reported for other dicyclohexylurea derivaties (Gallagher et al., 1999; Sun & Zhang, 2006; Wu et al., 2006). The shortening of the N3—C13 and N2—C12 bond lengths with the corresponding lengthening of the N2—C13 bond distance (Table 1) can be attributed to π-conjugation in the O1/C12/N2/C13 and O2/C13/N3/C14 fragments of the molecule.

The molecules of (I) are linked by a combination of N—H···O and C—H···O hydrogen bonds (Table 2) into a two-dimensional framework, whose formation is readily analyzed in terms of substructures of lower dimensionality with finite zero-dimensional dimeric units as the building blocks within the structure. A pair of intermolecular N3—H3N···O1 hydrogen bonds with the urea atom N3 in the molecule at (x, y, z) acting as a donor to the butanoyl atom O1 in the molecule at (1 - x, 1 - y, 1 - z) generates a centrosymmetric R₂²(12) dimeric ring (A) centered at (1/2, 1/2, 1/2). Similarly, a pair of intermolecular N1—H1N···O1 hydrogen bonds in (I) interconnects two molecules at (x, y, z) and (1 - x, -y, 1 - z), producing a centrosymmetric R₂²(18) dimeric ring (B) centered at (1/2, 0, 1/2). The R₂²(12) and R₂²(18) rings are alternately linked into an infinite one-dimensional ABAB··· polymeric chain propagating along the [010] direction (Fig. 2). Adjacent one-dimensional chains are connected via pairs of C11—H11A···O2 hydrogen bonds producing R₂²(12) motifs, which propagate along the [100] direction. The combination of [010] and [100] chains suffices to generate a continuous two-dimensional framework structure (Fig. 3).

Solid-state DFT calculations have been performed using the Dmol³ code (Delly, 1996, 1998) of the Materials Studio system of programs (Accelrys Inc., Princeton, New Jersey, USA) in the framework of a generalized-gradient approximation. The starting atomic coordinates were taken from the final X-ray refinement cycle. Since the resulting molecular geometry depends on the choice of functionals, theoretical calculations were carried out with the BLYP (Becke, 1988; Lee et al., 1988) and HCTH (Hamprecht et al., 1998; Boese et al., 2000; Boese & Handy, 2001) levels of theory using the numeric DNP basis set. The cell parameters were kept fixed during the DFT calculations. Different functionals describe different classes of molecules with varying degrees of accuracy. Between the two functionals used for the DFT calculation, the results with the HCTH functional agree more closely with the X-ray analysis of the title compound. A comparison of the molecular conformation of (I) as established by the X-ray study and quantum mechanical calculations shows an excellent agreement (Fig. 4); the r.m.s. deviation between the coordinates obtained by geometry optimization and X-ray structure analysis is 0.013 Å. The elongation of the DFT-calculated N2—C13 bond length compared with the N2—C12 and N3—C13 bond distances is consistent with the X-ray analysis of the title compound. The calculated O···H distances (1.831–1.898 Å) in (I) lie in the range of normal N—H···O hydrogen bonds (Lyssenko & Antipin, 2006). The geometries of the hydrogen bonds (Table 2) calculated from the DFT method closely resemble those obtained from the X-ray analysis (X—H bond lengths normalized to neutron distances), with the formation of characteristic R₂²(12) and R₂²(18) rings, polymeric chains and finally a two-dimensional supramolecular assembly.

It is of interest to compare briefly the supramolecular structure of (I) with those of other N,N'-disubstituted ureas (Custelcean, 2008). Disubstituted urea derivatives tend to form one-dimensional hydrogen-bonded chains by employing their two NH H-atom donors and the C═O acceptors. The NH H atoms normally adopt an anti conformation with respect to the carbonyl group and form three-center bonds to the urea carbonyl groups. The resulting hydrogen-bonded motif can be described by using the graph set notations (Etter, 1990) as C(4)[R₂¹(6)] (Chang et al., 1993; Hollingsworth et al., 1994). Bulky substituents at the urea N atoms of (I), however, prohibit the formation of short NH···O—C interactions, and consequently the urea planes are twisted relative to one another. The propensity of ureas to form hydrogen-bonded chains and cyclic dimers has been utilized in the design of two-dimensional layered networks (Kane et al., 1995; Wu et al., 2006). In the structure of (I), a two-dimensional supramolecular network based on cyclic R₂²(12) and R₂²(18) motifs has been established from NH(urea)···O—C(butanoyl), NH(indonyl)···O—C(butanoyl) and CH(butanoyl)···O—C(urea) interactions.

Related literature

For related literature, see: Allen et al. (1997); Becke (1988); Bessard & Crettaz (2000); Boese & Handy (2001); Boese et al. (2000); Chang et al. (1993); Cremer & Pople (1975); Custelcean (2008); Delly (1996, 1998); Etter (1990); Gale & &Quesada (2006); Gallagher et al. (1999); Hamprecht et al. (1998); Hollingsworth et al. (1994); Kane et al. (1995); Lee et al. (1988); Lyssenko & Antipin (2006); Sun & Zhang (2006); Wu et al. (2006).

S2. Experimental

A suspension of indole-3-butyric acid (1.02 g, 5 mmol) and dicyclohexyl diimide (1.03 g, 5 mmol) in dry benzene (20 ml) was refluxed for 3 h using a Dean–Stark water separator. Removal of the solvent in vacuo afforded a colorless crystalline solid, which was recrystallized from an acetone/n-hexane mixture (1:1, v/v) to obtain diffraction quality single crystals of the title compound (yield 0.48 g, 23.5%; m.p. 413 K). Analysis found: C 73.38, H 8.55, N 10.30%; calculated for C₂₅H₃₅N₃O₂: C 73.31, H 8.61, N 10.26%. 1H NMR (δ, CDCl3): 1.23 (m, 11H, –NH—C₆H₁₁), 1.74 (m, 11H, –CO—N(C₆H₁₁)—CO–), 2.07 (m, 2H, –CH₂—CH₂—CH₂), 2.45 (2H, t, J = 7.2 Hz, –H₂C—CH₂—CO–), 2.84 (2H, t, J =7.2 Hz, In—CH₂—CH₂–), 6.78(1H, br s, –CO—NH—C₆H₁₁), 7.01 (1H, br s, C₂—H), 7.11 (1H, t, J = 7.5 Hz, C₆—H), 7.19 (1H, t, J = 7.5 Hz, C₅—H), 7.36 (1H, d, J = 8.1 Hz, C₇—H), 7.60 (1H, d, J =7.8 Hz, C₄—H), 8.02 (1H, br s,-NH).

S3. Refinement

The NH H-atom positions obtained from a difference Fourier map were refined freely, while the C-bound H atoms were placed in idealized positions using the riding method, with bond distances ranging from 0.93 to 0.98 Å and U_iso(H) set to 1.5U_eq of the parent atoms.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 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), CAMERON (Watkin et al., 1993) and DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PARST95 (Nardelli, 1995).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of (I), showing the combination of R2^2(12) and R2^2(18) rings forming a one-dimensional chain running along the [010] direction. For the sake of clarity, the cyclohexyl groups and H atoms not involved in the hydrogen bonding shown have been omitted. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1, -y, -z + 1.]
	Fig. 3. Part of the crystal structure of (I), showing the generation of the two-dimensional framework structure. For the sake of clarity, the cyclohexyl groups and H atoms not involved in the motif shown have been omitted. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1, -y, -z + 1; (iii) -x, -y + 1, -z + 1.]
	Fig. 4. Comparison of the molecular conformation of (I) as established from the X-ray study (solid line) and the solid-state DFT calculation (dotted line).

N,N'-Dicyclohexyl-N-[4-(1H-indol-3-yl)butanoyl]urea

Crystal data

C25H35N3O2	Z = 2
Mr = 409.56	F(000) = 444
Triclinic, P1	Dx = 1.198 Mg m^−3
Hall symbol: -P 1	Melting point: 413 K
a = 8.4655 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.5938 (9) Å	Cell parameters from 3416 reflections
c = 13.0982 (11) Å	θ = 2.5–26.4°
α = 68.331 (2)°	µ = 0.08 mm^−1
β = 86.752 (1)°	T = 100 K
γ = 72.289 (1)°	Block, colourless
V = 1135.83 (16) Å^3	0.50 × 0.46 × 0.40 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3945 independent reflections
Radiation source: fine-focus sealed tube	3297 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
phi and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→10
Tmin = 0.964, Tmax = 0.975	k = −13→12
5965 measured reflections	l = −15→15

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0586P)^2 + 0.0945P] where P = (Fo^2 + 2Fc^2)/3
3945 reflections	(Δ/σ)max < 0.001
279 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.19 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.

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

	x	y	z	Uiso*/Ueq
O1	0.46973 (10)	0.40938 (8)	0.39263 (7)	0.0190 (2)
O2	−0.02179 (11)	0.65368 (9)	0.44284 (7)	0.0244 (2)
N1	0.46139 (14)	−0.19502 (11)	0.68548 (9)	0.0233 (3)
H1N	0.4674 (18)	−0.2477 (15)	0.6501 (12)	0.033 (4)*
N2	0.25303 (12)	0.56892 (9)	0.41176 (8)	0.0168 (2)
N3	0.17758 (14)	0.63388 (10)	0.56127 (8)	0.0186 (2)
H3N	0.285 (2)	0.6184 (13)	0.5732 (11)	0.029 (4)*
C1	0.41374 (16)	−0.06108 (12)	0.63931 (11)	0.0213 (3)
H1	0.3766	−0.0120	0.5661	0.032*
C2	0.42848 (15)	−0.01032 (12)	0.71573 (10)	0.0191 (3)
C3	0.49089 (16)	−0.11968 (12)	0.81649 (10)	0.0209 (3)
C4	0.53704 (17)	−0.13317 (13)	0.92220 (11)	0.0277 (3)
H4	0.5270	−0.0600	0.9388	0.042*
C5	0.59779 (19)	−0.25669 (14)	1.00162 (12)	0.0339 (4)
H5	0.6304	−0.2663	1.0717	0.051*
C6	0.61093 (18)	−0.36773 (14)	0.97821 (12)	0.0331 (4)
H6	0.6499	−0.4497	1.0335	0.050*
C7	0.56724 (17)	−0.35793 (13)	0.87492 (11)	0.0280 (3)
H7	0.5761	−0.4318	0.8596	0.042*
C8	0.50929 (16)	−0.23344 (12)	0.79425 (11)	0.0223 (3)
C9	0.38932 (16)	0.13055 (12)	0.70050 (10)	0.0211 (3)
H9A	0.4632	0.1379	0.7501	0.032*
H9B	0.2765	0.1611	0.7206	0.032*
C10	0.40632 (16)	0.21821 (11)	0.58322 (10)	0.0193 (3)
H10A	0.3329	0.2111	0.5331	0.029*
H10B	0.5194	0.1890	0.5630	0.029*
C11	0.36375 (15)	0.36062 (11)	0.57135 (10)	0.0179 (3)
H11A	0.2544	0.3877	0.5977	0.027*
H11B	0.4435	0.3692	0.6163	0.027*
C12	0.36594 (15)	0.44787 (11)	0.45302 (10)	0.0162 (3)
C13	0.12324 (15)	0.62092 (11)	0.47405 (10)	0.0176 (3)
C14	0.06160 (15)	0.68236 (12)	0.63386 (10)	0.0197 (3)
H14	−0.0396	0.6590	0.6310	0.030*
C15	0.13549 (17)	0.61622 (14)	0.75174 (10)	0.0259 (3)
H15A	0.2398	0.6333	0.7559	0.039*
H15B	0.1582	0.5227	0.7749	0.039*
C16	0.01626 (19)	0.66619 (16)	0.82869 (12)	0.0354 (4)
H16A	−0.0832	0.6407	0.8305	0.053*
H16B	0.0683	0.6266	0.9027	0.053*
C17	−0.0311 (2)	0.81354 (16)	0.79141 (13)	0.0428 (4)
H17A	0.0666	0.8385	0.7969	0.064*
H17B	−0.1114	0.8428	0.8394	0.064*
C18	−0.10494 (19)	0.87931 (15)	0.67327 (13)	0.0375 (4)
H18A	−0.1284	0.9729	0.6502	0.056*
H18B	−0.2090	0.8618	0.6694	0.056*
C19	0.01357 (17)	0.83041 (13)	0.59549 (12)	0.0272 (3)
H19A	−0.0394	0.8695	0.5218	0.041*
H19B	0.1128	0.8564	0.5930	0.041*
C20	0.24072 (16)	0.64480 (12)	0.29130 (9)	0.0187 (3)
H20	0.3520	0.6200	0.2649	0.028*
C21	0.19015 (16)	0.79120 (12)	0.26508 (10)	0.0211 (3)
H21A	0.2664	0.8106	0.3042	0.032*
H21B	0.0794	0.8203	0.2888	0.032*
C22	0.19309 (18)	0.86252 (13)	0.14124 (11)	0.0287 (3)
H22A	0.1584	0.9558	0.1243	0.043*
H22B	0.3056	0.8373	0.1188	0.043*
C23	0.0780 (2)	0.83058 (13)	0.07727 (11)	0.0337 (4)
H23A	−0.0359	0.8634	0.0944	0.051*
H23B	0.0861	0.8737	−0.0010	0.051*
C24	0.12258 (19)	0.68427 (13)	0.10549 (11)	0.0309 (3)
H24A	0.2309	0.6535	0.0793	0.046*
H24B	0.0420	0.6667	0.0682	0.046*
C25	0.12559 (17)	0.61045 (13)	0.22940 (10)	0.0243 (3)
H25A	0.0141	0.6326	0.2541	0.036*
H25B	0.1635	0.5174	0.2453	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0197 (5)	0.0162 (5)	0.0220 (5)	−0.0042 (4)	0.0013 (4)	−0.0092 (4)
O2	0.0181 (5)	0.0285 (5)	0.0261 (5)	−0.0042 (4)	−0.0016 (4)	−0.0113 (4)
N1	0.0292 (6)	0.0161 (6)	0.0271 (6)	−0.0076 (5)	0.0017 (5)	−0.0105 (5)
N2	0.0195 (5)	0.0141 (5)	0.0161 (5)	−0.0033 (4)	0.0000 (4)	−0.0060 (4)
N3	0.0163 (6)	0.0192 (6)	0.0214 (6)	−0.0033 (4)	0.0004 (4)	−0.0103 (5)
C1	0.0235 (7)	0.0161 (7)	0.0227 (7)	−0.0062 (5)	−0.0003 (5)	−0.0049 (5)
C2	0.0202 (7)	0.0151 (6)	0.0209 (6)	−0.0050 (5)	0.0028 (5)	−0.0060 (5)
C3	0.0211 (7)	0.0179 (7)	0.0220 (7)	−0.0054 (5)	0.0057 (5)	−0.0066 (5)
C4	0.0346 (8)	0.0250 (8)	0.0224 (7)	−0.0071 (6)	0.0051 (6)	−0.0097 (6)
C5	0.0386 (9)	0.0338 (9)	0.0214 (7)	−0.0071 (7)	0.0035 (6)	−0.0047 (6)
C6	0.0331 (8)	0.0219 (8)	0.0297 (8)	−0.0028 (6)	0.0047 (6)	0.0019 (6)
C7	0.0287 (8)	0.0160 (7)	0.0338 (8)	−0.0047 (6)	0.0081 (6)	−0.0058 (6)
C8	0.0220 (7)	0.0173 (7)	0.0266 (7)	−0.0060 (5)	0.0059 (6)	−0.0077 (6)
C9	0.0248 (7)	0.0171 (7)	0.0216 (7)	−0.0059 (5)	0.0019 (5)	−0.0078 (5)
C10	0.0213 (7)	0.0149 (7)	0.0215 (7)	−0.0045 (5)	0.0004 (5)	−0.0073 (5)
C11	0.0178 (6)	0.0155 (6)	0.0205 (6)	−0.0038 (5)	−0.0011 (5)	−0.0074 (5)
C12	0.0165 (6)	0.0144 (6)	0.0213 (6)	−0.0059 (5)	−0.0018 (5)	−0.0091 (5)
C13	0.0190 (7)	0.0125 (6)	0.0198 (6)	−0.0044 (5)	0.0018 (5)	−0.0047 (5)
C14	0.0187 (7)	0.0204 (7)	0.0220 (7)	−0.0059 (5)	0.0043 (5)	−0.0105 (6)
C15	0.0253 (7)	0.0302 (8)	0.0241 (7)	−0.0071 (6)	0.0016 (6)	−0.0134 (6)
C16	0.0328 (8)	0.0514 (10)	0.0282 (8)	−0.0113 (7)	0.0050 (6)	−0.0234 (7)
C17	0.0368 (9)	0.0589 (11)	0.0522 (10)	−0.0137 (8)	0.0134 (8)	−0.0445 (9)
C18	0.0332 (8)	0.0284 (8)	0.0562 (10)	−0.0049 (7)	0.0117 (7)	−0.0265 (8)
C19	0.0258 (7)	0.0207 (7)	0.0364 (8)	−0.0058 (6)	0.0059 (6)	−0.0134 (6)
C20	0.0235 (7)	0.0150 (6)	0.0151 (6)	−0.0032 (5)	−0.0002 (5)	−0.0051 (5)
C21	0.0248 (7)	0.0159 (7)	0.0220 (7)	−0.0041 (5)	−0.0013 (5)	−0.0075 (5)
C22	0.0398 (9)	0.0160 (7)	0.0235 (7)	−0.0029 (6)	0.0006 (6)	−0.0040 (6)
C23	0.0485 (9)	0.0227 (8)	0.0210 (7)	0.0001 (7)	−0.0080 (7)	−0.0055 (6)
C24	0.0436 (9)	0.0248 (8)	0.0215 (7)	−0.0032 (6)	−0.0082 (6)	−0.0100 (6)
C25	0.0308 (8)	0.0188 (7)	0.0235 (7)	−0.0051 (6)	−0.0036 (6)	−0.0092 (6)

Geometric parameters (Å, º)

O1—C12	1.2409 (14)	C14—C15	1.5187 (17)
O2—C13	1.2154 (15)	C14—C19	1.5250 (17)
N1—C8	1.3709 (17)	C14—H14	0.9800
N1—C1	1.3758 (16)	C15—C16	1.5265 (19)
N1—H1N	0.882 (16)	C15—H15A	0.9700
N2—C12	1.3629 (15)	C15—H15B	0.9700
N2—C13	1.4474 (15)	C16—C17	1.519 (2)
N2—C20	1.4874 (15)	C16—H16A	0.9700
N3—C13	1.3295 (16)	C16—H16B	0.9700
N3—C14	1.4619 (16)	C17—C18	1.521 (2)
N3—H3N	0.885 (15)	C17—H17A	0.9700
C1—C2	1.3630 (18)	C17—H17B	0.9700
C1—H1	0.9300	C18—C19	1.5265 (19)
C2—C3	1.4367 (17)	C18—H18A	0.9700
C2—C9	1.5016 (16)	C18—H18B	0.9700
C3—C4	1.3995 (18)	C19—H19A	0.9700
C3—C8	1.4150 (18)	C19—H19B	0.9700
C4—C5	1.3819 (19)	C20—C21	1.5252 (16)
C4—H4	0.9300	C20—C25	1.5265 (17)
C5—C6	1.401 (2)	C20—H20	0.9800
C5—H5	0.9300	C21—C22	1.5274 (17)
C6—C7	1.378 (2)	C21—H21A	0.9700
C6—H6	0.9300	C21—H21B	0.9700
C7—C8	1.3935 (18)	C22—C23	1.526 (2)
C7—H7	0.9300	C22—H22A	0.9700
C9—C10	1.5246 (17)	C22—H22B	0.9700
C9—H9A	0.9700	C23—C24	1.5230 (18)
C9—H9B	0.9700	C23—H23A	0.9700
C10—C11	1.5280 (16)	C23—H23B	0.9700
C10—H10A	0.9700	C24—C25	1.5273 (18)
C10—H10B	0.9700	C24—H24A	0.9700
C11—C12	1.5088 (16)	C24—H24B	0.9700
C11—H11A	0.9700	C25—H25A	0.9700
C11—H11B	0.9700	C25—H25B	0.9700
C8—N1—C1	108.57 (11)	C16—C15—H15A	109.5
C8—N1—H1N	125.4 (10)	C14—C15—H15B	109.5
C1—N1—H1N	125.8 (10)	C16—C15—H15B	109.5
C12—N2—C13	124.00 (10)	H15A—C15—H15B	108.1
C12—N2—C20	118.97 (10)	C17—C16—C15	111.34 (12)
C13—N2—C20	116.14 (9)	C17—C16—H16A	109.4
C13—N3—C14	121.10 (11)	C15—C16—H16A	109.4
C13—N3—H3N	119.7 (9)	C17—C16—H16B	109.4
C14—N3—H3N	119.0 (9)	C15—C16—H16B	109.4
C2—C1—N1	110.61 (12)	H16A—C16—H16B	108.0
C2—C1—H1	124.7	C16—C17—C18	111.05 (12)
N1—C1—H1	124.7	C16—C17—H17A	109.4
C1—C2—C3	106.15 (11)	C18—C17—H17A	109.4
C1—C2—C9	128.10 (11)	C16—C17—H17B	109.4
C3—C2—C9	125.74 (11)	C18—C17—H17B	109.4
C4—C3—C8	118.73 (12)	H17A—C17—H17B	108.0
C4—C3—C2	134.23 (12)	C17—C18—C19	111.28 (12)
C8—C3—C2	107.00 (11)	C17—C18—H18A	109.4
C5—C4—C3	119.14 (13)	C19—C18—H18A	109.4
C5—C4—H4	120.4	C17—C18—H18B	109.4
C3—C4—H4	120.4	C19—C18—H18B	109.4
C4—C5—C6	120.99 (13)	H18A—C18—H18B	108.0
C4—C5—H5	119.5	C14—C19—C18	110.64 (11)
C6—C5—H5	119.5	C14—C19—H19A	109.5
C7—C6—C5	121.35 (13)	C18—C19—H19A	109.5
C7—C6—H6	119.3	C14—C19—H19B	109.5
C5—C6—H6	119.3	C18—C19—H19B	109.5
C6—C7—C8	117.62 (13)	H19A—C19—H19B	108.1
C6—C7—H7	121.2	N2—C20—C21	112.03 (9)
C8—C7—H7	121.2	N2—C20—C25	111.79 (10)
N1—C8—C7	130.21 (12)	C21—C20—C25	111.43 (10)
N1—C8—C3	107.65 (11)	N2—C20—H20	107.1
C7—C8—C3	122.14 (12)	C21—C20—H20	107.1
C2—C9—C10	113.52 (10)	C25—C20—H20	107.1
C2—C9—H9A	108.9	C20—C21—C22	109.36 (10)
C10—C9—H9A	108.9	C20—C21—H21A	109.8
C2—C9—H9B	108.9	C22—C21—H21A	109.8
C10—C9—H9B	108.9	C20—C21—H21B	109.8
H9A—C9—H9B	107.7	C22—C21—H21B	109.8
C9—C10—C11	111.69 (10)	H21A—C21—H21B	108.3
C9—C10—H10A	109.3	C23—C22—C21	111.00 (11)
C11—C10—H10A	109.3	C23—C22—H22A	109.4
C9—C10—H10B	109.3	C21—C22—H22A	109.4
C11—C10—H10B	109.3	C23—C22—H22B	109.4
H10A—C10—H10B	107.9	C21—C22—H22B	109.4
C12—C11—C10	111.13 (10)	H22A—C22—H22B	108.0
C12—C11—H11A	109.4	C24—C23—C22	111.36 (11)
C10—C11—H11A	109.4	C24—C23—H23A	109.4
C12—C11—H11B	109.4	C22—C23—H23A	109.4
C10—C11—H11B	109.4	C24—C23—H23B	109.4
H11A—C11—H11B	108.0	C22—C23—H23B	109.4
O1—C12—N2	119.73 (11)	H23A—C23—H23B	108.0
O1—C12—C11	120.16 (10)	C23—C24—C25	111.49 (11)
N2—C12—C11	120.11 (10)	C23—C24—H24A	109.3
O2—C13—N3	125.15 (11)	C25—C24—H24A	109.3
O2—C13—N2	120.18 (11)	C23—C24—H24B	109.3
N3—C13—N2	114.60 (10)	C25—C24—H24B	109.3
N3—C14—C15	109.96 (10)	H24A—C24—H24B	108.0
N3—C14—C19	111.25 (10)	C20—C25—C24	110.65 (11)
C15—C14—C19	111.73 (11)	C20—C25—H25A	109.5
N3—C14—H14	107.9	C24—C25—H25A	109.5
C15—C14—H14	107.9	C20—C25—H25B	109.5
C19—C14—H14	107.9	C24—C25—H25B	109.5
C14—C15—C16	110.68 (11)	H25A—C25—H25B	108.1
C14—C15—H15A	109.5
C8—N1—C1—C2	−0.31 (15)	C10—C11—C12—N2	143.14 (11)
N1—C1—C2—C3	0.50 (14)	C14—N3—C13—O2	4.45 (18)
N1—C1—C2—C9	−179.73 (12)	C14—N3—C13—N2	−178.61 (10)
C1—C2—C3—C4	177.51 (14)	C12—N2—C13—O2	−120.32 (13)
C9—C2—C3—C4	−2.3 (2)	C20—N2—C13—O2	48.75 (15)
C1—C2—C3—C8	−0.49 (14)	C12—N2—C13—N3	62.58 (14)
C9—C2—C3—C8	179.73 (12)	C20—N2—C13—N3	−128.35 (11)
C8—C3—C4—C5	−0.48 (19)	C13—N3—C14—C15	145.83 (11)
C2—C3—C4—C5	−178.30 (13)	C13—N3—C14—C19	−89.84 (13)
C3—C4—C5—C6	−1.1 (2)	N3—C14—C15—C16	179.74 (10)
C4—C5—C6—C7	1.4 (2)	C19—C14—C15—C16	55.68 (14)
C5—C6—C7—C8	0.0 (2)	C14—C15—C16—C17	−55.71 (15)
C1—N1—C8—C7	−179.94 (13)	C15—C16—C17—C18	55.99 (16)
C1—N1—C8—C3	−0.01 (14)	C16—C17—C18—C19	−55.91 (16)
C6—C7—C8—N1	178.31 (13)	N3—C14—C19—C18	−178.94 (11)
C6—C7—C8—C3	−1.61 (19)	C15—C14—C19—C18	−55.61 (14)
C4—C3—C8—N1	−178.05 (11)	C17—C18—C19—C14	55.43 (16)
C2—C3—C8—N1	0.31 (14)	C12—N2—C20—C21	−148.53 (11)
C4—C3—C8—C7	1.88 (19)	C13—N2—C20—C21	41.82 (13)
C2—C3—C8—C7	−179.75 (12)	C12—N2—C20—C25	85.57 (13)
C1—C2—C9—C10	−27.51 (18)	C13—N2—C20—C25	−84.08 (12)
C3—C2—C9—C10	152.22 (12)	N2—C20—C21—C22	175.58 (10)
C2—C9—C10—C11	179.46 (10)	C25—C20—C21—C22	−58.32 (14)
C9—C10—C11—C12	−174.86 (10)	C20—C21—C22—C23	57.75 (14)
C13—N2—C12—O1	177.57 (10)	C21—C22—C23—C24	−56.38 (16)
C20—N2—C12—O1	8.79 (15)	C22—C23—C24—C25	54.40 (16)
C13—N2—C12—C11	−1.90 (16)	N2—C20—C25—C24	−176.96 (10)
C20—N2—C12—C11	−170.68 (10)	C21—C20—C25—C24	56.81 (14)
C10—C11—C12—O1	−36.33 (14)	C23—C24—C25—C20	−54.30 (15)