1-[2-(2,6-Diisopropyl­anilino)-1-naph­th­yl]isoquinoline

The mol­ecule of the title compound, C₃₁H₃₀N₂, contains a single intra­molecular hydrogen bond, in contrast with the related N-methyl compound which exists as hydrogen-bonded dimers in the solid state [Cortright, Huffman, Yoder, Coalter & Johnston (2004). Organometallics, 23, 2238-2250]. Application of the density functional theory programs CASTEP and DMol³ allows accurate assignment of the location of the H atoms in the structure.

S1. Comment

The 1-isoquinolyl-2-aminonaphthalene (IAN) ligands were developed by Johnston and co-workers (Cortright & Johnston, 2002; Cortright, Yoder & Johnston, 2004). Ligands of this type are bidentate, having one amine and one imine-equivalent coordinating group, and they are axially chiral, as in the classic BINOL-derived family [Define BINOL?], since rotation about the naphthyl–isoquinolyl linkage is restricted by the H atoms β to this bond. Formation of a metal complex from an IAN ligand leads to the formation of a six-membered chelate ring with the metal in the centre.

These IAN ligands have been applied to the coordination of zirconium and aluminium with the resulting complexes used in a variety of transformations, including olefin polymerisation and addition of diethylzinc to benzaldehyde (Cortright, Huffman et al., 2004; Cortright, Coalter et al., 2004). However, most of this work was carried out with ligands in which the R group of the amine N atom (Fig. 1) was small, for example methyl [ligand (I)]. Intrigued by the possibility that increasing the bulk of the R group could improve catalytic activity, we have investigated the use of the title compound, (II), containing the bulky 2,6-diisopropylphenyl group on the amine N atom. This molecule has been reported by Johnston and co-workers (Cortright, Huffman et al., 2004) but not pursued in a catalytic context.

Synthesis of (II) followed the literature route, after which X-ray quality crystals could be obtained from a concentrated dichloromethane solution. The structure of (II) (Fig. 2) reveals that the molecule exists as a monomer in the solid state with a single intramolecular hydrogen bond. This is in sharp contrast with the reported structure for (I) (Cortright, Huffman et al., 2004), which exists a hydrogen-bonded dimer in the solid state. The dimer contains two non-symmetry-related molecules, and exhibits one shorter and one longer hydrogen bond (N···H distances 2.051 and 2.246 Å, respectively). The intramolecular N···H distance in (II) (2.51 Å) is significantly longer, suggesting a much less favourable interaction. Presumably, the additional steric requirement of the bulky aryl group prevents the formation of an intermolecular hydrogen bond.

Reaction of (II) with BuLi followed by MeMgCl in tetrahydrofuran yields a material which gives satisfactory spectroscopic data to confirm the loss of methane and formation of a mono-ligand complex. At present, we have been unable to grow X-ray quality crystals of this material to confirm this assignment. However, a similar reaction with AlEt₃ does not lead to the loss of an alkyl group, although the spectroscopic data do suggest that an adduct is formed. It therefore seems that the additional bulk of the aryl group severely hinders deprotonation of the amine group in (II) compared with the more reactive (I).

H atoms have low scattering power, the electron density associated with the atom is not usually centred at the nucleus, and H atoms tend to have higher librational amplitudes than other nuclei (Sheldrick, 1997). As a result, the placement of H atoms in X-ray structures is usually carried out by applying a riding model based on established geometric parameters. The combination of structural data from X-ray diffraction with ab initio calculations can be used to provide reliable H-atom positions (Milman & Winkler, 2001). Compound (II) was an attractive target to investigate the application of this approach to the location of the H atoms, as it presents H atoms with a number of different bonding modes, including hydrogen-bonding, in a well defined structure.

The density functional theory (DFT) programs CASTEP (Clark et al., 2005) and DMol³ (Delley, 2000), as implemented in Materials Studio (Accelrys, 2009), were used to perform these calculations. The lattice parameters were not varied as the experimentally determined parameters are sufficiently accurate. A comparison of an all-electron (DMol³) and a pseudopotential (CASTEP) approach provides additional confidence that the DFT results for this crystal structure do not depend on the implementation details of a particular DFT technique.

Initial comparison of the fractional coordinates of selected heavy atoms indicates the high accuracy of their experimentally determined positions (Table 3). Overlaying the experimentally determined structure (light shading/green) with the DMol³ (dark shading/blue) and CASTEP (mid-shading/red) optimized structures illustrates the accuracy of the heavy-atom positions and the displacement of the H atoms (Fig. 3). Analysis of the lengths of bonds to H atoms shows that, as expected, both theoretical methods calculate the positions of the H atoms at greater distances from the heavy atoms than the riding-model positions (Table 4). Looking at the average differences between the experimental and calculated values (Table 5), it is clear that both DFT methods give very similar results. Both methods show the greatest variation between computation and experiment for aromatic C—H positions, with the single N—H (which was located experimentally and restrained) giving the closest agreement between DFT and X-ray locations.

By combining DFT methods with experimental locations for non-H atoms, a model for (II) which locates the H atoms accurately is available. This provides a useful alternative to more difficult to access methods for accurate H-atom location in solids for which X-ray quality single crystals are available.

Related literature

For related literature, see: Accelrys (2009); Clark et al. (2005); Cortright & Johnston (2002); Cortright, Coalter, Pink & Johnston (2004); Cortright, Huffman, Yoder, Coalter & Johnston (2004); Cortright, Yoder & Johnston (2004); Delley (2000); Milman & Winkler (2001); Perdew et al. (1996); Sheldrick (1997).

S2. Experimental

Compound (II) was prepared by the literature method of Cortright, Huffman et al. (2004). Crystals of (II) suitable for X-ray diffraction studies were grown from a concentrated dichloromethane solution.

S3. Refinement

All H atoms were treated as riding, with C—H distances of 0.95 (aromatic), 0.98 (methyl) or 1.00 Å (aliphatic CH) and N—H = 0.88 Å, and with U_iso(H) = kU_eq(carrier), where k = 1.5 for methyl groups and 1.2 otherwise. The isopropyl group C26/C27/C28 was disordered over two sites. The anisotropic displacement parameters for corresponding partial occupancy atoms were constrained to be the same. The corresponding bonded distances and 1,3 non-bonded distances in the two disorder components were restrained to be the same; the final site occupancies were 0.73 (3) and 0.27 (3).

CASTEP geometry optimization was performed using the generalized gradient corrected (GGA) exchange-correlation function of Perdew, Burke and Ernzerhof (PBE) (Perdew et al., 1996). Ultrasoft pseudopotentials were used for all elements. The plane-wave basis set cutoff used was 310 eV. A single Γ point was used for Brillouin zone sampling; this setting is sufficiently accurate for such a large unit cell of an insulating material. The Broyden–Fletcher–Goldfarb–Shanno (BFGS) algorithm was used for the geometry optimization of the internal degrees of freedom. Calculations were considered converged when the maximum force on atoms was less than 0.01 eV Å^-1, the energy change was less than 5 × 10 ^-6 eV per atom and the maximum atomic displacement was less than 5 × 10 ^-4 Å.

DMol³ geometry optimization also used the GGA PBE function with an all-electron core treatment and the double numerical plus polarization (DNP) basis set for atomic orbitals. Calculations were considered converged when the maximum force on atoms was less than 0.002 Ha Å^-1, the energy change was less than 1 × 10^-5 Ha per atom and the maximum atomic displacement was less than 0.005 Å.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).

Figures

	Fig. 1. The general structure of the IAN ligand family. For (I), R = Me, and for (II), R = 2,6-iPrC6H3.
	Fig. 2. The structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level, and H atoms except H2 and the minor component of the disordered isopropyl group have been omitted for clarity. The dashed lines indicate the intramolecular hydrogen bond.
	Fig. 3. An overlay of the experimental structure of (II) (light shading; green in the electronic version of the journal) with that calculated using the Dmol^3 (dark shading; blue in the electronic version of the journal) and CASTEP (mid-shading; red in the electronic version of the journal) methods.

1-[2-(2,6-Diisopropylanilino)-1-naphthyl]isoquinoline

Crystal data

C31H30N2	F(000) = 920
Mr = 430.57	Dx = 1.169 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3905 reflections
a = 9.0996 (10) Å	θ = 4.1–34.0°
b = 11.2154 (12) Å	µ = 0.07 mm^−1
c = 23.974 (3) Å	T = 140 K
V = 2446.7 (5) Å^3	Block, yellow
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection

Oxford Xcalibur 3 CCD area-detector diffractometer	1584 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.178
Graphite monochromator	θmax = 25.5°, θmin = 4.1°
Detector resolution: 16.0050 pixels mm^-1	h = −11→11
ω and ϕ scans	k = −13→13
28412 measured reflections	l = −29→29
2579 independent reflections

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0422P)^2] where P = (Fo^2 + 2Fc^2)/3
2579 reflections	(Δ/σ)max < 0.001
311 parameters	Δρmax = 0.15 e Å^−3
3 restraints	Δρmin = −0.17 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
C1	0.6327 (4)	0.6452 (3)	0.17455 (15)	0.0305 (9)
C2	0.6973 (4)	0.7245 (3)	0.21135 (14)	0.0243 (9)
C3	0.8049 (4)	0.8138 (3)	0.19018 (14)	0.0263 (9)
C4	0.8489 (5)	0.9849 (3)	0.14025 (15)	0.0380 (11)
H4	0.8115	1.0483	0.1181	0.046*
C5	0.9937 (4)	0.9833 (3)	0.15055 (16)	0.0358 (10)
H5	1.0551	1.0449	0.1365	0.043*
C6	1.0541 (4)	0.8899 (3)	0.18219 (15)	0.0299 (9)
C7	0.9566 (4)	0.8009 (3)	0.20172 (13)	0.0263 (9)
C8	1.0144 (4)	0.7035 (4)	0.23134 (15)	0.0363 (10)
H8	0.9508	0.6422	0.2443	0.044*
C9	1.1613 (4)	0.6966 (4)	0.24152 (16)	0.0438 (11)
H9	1.1993	0.6307	0.2617	0.053*
C10	1.2564 (4)	0.7850 (4)	0.22270 (17)	0.0474 (12)
H10	1.3585	0.7790	0.2305	0.057*
C11	1.2052 (4)	0.8789 (4)	0.19360 (16)	0.0437 (11)
H11	1.2716	0.9381	0.1807	0.052*
C12	0.6601 (4)	0.7185 (3)	0.26886 (14)	0.0277 (9)
C13	0.5649 (4)	0.6294 (3)	0.28855 (15)	0.0308 (9)
C14	0.5069 (4)	0.5463 (3)	0.24944 (17)	0.0337 (9)
H14	0.4436	0.4845	0.2620	0.040*
C15	0.5407 (4)	0.5540 (3)	0.19454 (15)	0.0327 (10)
H15	0.5017	0.4970	0.1692	0.039*
C16	0.5285 (4)	0.6231 (4)	0.34589 (15)	0.0381 (11)
H16	0.4644	0.5621	0.3587	0.046*
C17	0.5842 (4)	0.7032 (4)	0.38272 (16)	0.0433 (11)
H17	0.5591	0.6985	0.4211	0.052*
C18	0.6787 (4)	0.7927 (4)	0.36368 (16)	0.0420 (11)
H18	0.7168	0.8492	0.3894	0.050*
C19	0.7174 (4)	0.8004 (4)	0.30888 (15)	0.0346 (10)
H19	0.7833	0.8611	0.2972	0.041*
C20	0.6060 (4)	0.5731 (3)	0.07651 (15)	0.0321 (9)
C21	0.6945 (5)	0.4797 (3)	0.05829 (16)	0.0426 (11)
C22	0.6369 (5)	0.4056 (4)	0.01707 (18)	0.0532 (12)
H22	0.6936	0.3404	0.0037	0.064*
C23	0.4995 (6)	0.4254 (4)	−0.00452 (17)	0.0564 (13)
H23	0.4628	0.3744	−0.0329	0.068*
C24	0.4145 (5)	0.5180 (4)	0.01429 (18)	0.0538 (13)
H24	0.3195	0.5301	−0.0011	0.065*
C25	0.4655 (5)	0.5944 (4)	0.05551 (17)	0.0413 (11)
C26	0.3704 (5)	0.6960 (4)	0.07618 (18)	0.0563 (13)	0.73 (3)
H26	0.4003	0.7104	0.1157	0.068*	0.73 (3)
C27	0.2068 (12)	0.668 (2)	0.0777 (9)	0.090 (4)	0.73 (3)
H27A	0.1688	0.6632	0.0395	0.135*	0.73 (3)
H27B	0.1550	0.7307	0.0981	0.135*	0.73 (3)
H27C	0.1914	0.5912	0.0965	0.135*	0.73 (3)
C28	0.4021 (17)	0.8118 (10)	0.0449 (6)	0.086 (4)	0.73 (3)
H28A	0.5080	0.8279	0.0456	0.129*	0.73 (3)
H28B	0.3496	0.8777	0.0629	0.129*	0.73 (3)
H28C	0.3691	0.8042	0.0062	0.129*	0.73 (3)
C26X	0.3704 (5)	0.6960 (4)	0.07618 (18)	0.0563 (13)	0.27 (3)
H26X	0.4174	0.7394	0.1079	0.068*	0.27 (3)
C27X	0.218 (3)	0.650 (7)	0.091 (3)	0.090 (4)	0.27 (3)
H27D	0.1826	0.5967	0.0618	0.135*	0.27 (3)
H27E	0.1505	0.7170	0.0956	0.135*	0.27 (3)
H27F	0.2236	0.6055	0.1266	0.135*	0.27 (3)
C28X	0.357 (5)	0.775 (3)	0.0239 (10)	0.086 (4)	0.27 (3)
H28D	0.4549	0.8043	0.0133	0.129*	0.27 (3)
H28E	0.2929	0.8430	0.0320	0.129*	0.27 (3)
H28F	0.3158	0.7283	−0.0068	0.129*	0.27 (3)
C29	0.8446 (5)	0.4574 (4)	0.08287 (18)	0.0560 (13)
H29	0.8823	0.5345	0.0982	0.067*
C30	0.8361 (6)	0.3682 (6)	0.1305 (2)	0.094 (2)
H30A	0.7720	0.3996	0.1599	0.140*
H30B	0.9348	0.3548	0.1457	0.140*
H30C	0.7962	0.2926	0.1166	0.140*
C31	0.9543 (5)	0.4122 (4)	0.0401 (2)	0.0658 (14)
H31A	0.9226	0.3341	0.0263	0.099*
H31B	1.0513	0.4048	0.0575	0.099*
H31C	0.9598	0.4686	0.0090	0.099*
N1	0.6639 (3)	0.6530 (3)	0.11774 (12)	0.0363 (8)
H1	0.7228	0.7104	0.1065	0.044*
N2	0.7514 (3)	0.9019 (3)	0.15934 (12)	0.0341 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.032 (2)	0.036 (2)	0.023 (2)	−0.0008 (19)	0.0039 (17)	0.0043 (18)
C2	0.020 (2)	0.029 (2)	0.024 (2)	0.0004 (16)	0.0008 (16)	0.0005 (18)
C3	0.038 (2)	0.025 (2)	0.0160 (18)	−0.0015 (19)	0.0058 (17)	−0.0060 (17)
C4	0.056 (3)	0.030 (2)	0.027 (2)	0.005 (2)	0.007 (2)	0.0078 (19)
C5	0.043 (3)	0.028 (2)	0.036 (2)	−0.0116 (19)	0.004 (2)	0.000 (2)
C6	0.034 (2)	0.032 (2)	0.024 (2)	−0.006 (2)	0.0024 (18)	−0.0034 (18)
C7	0.032 (2)	0.026 (2)	0.0208 (19)	−0.0007 (19)	0.0002 (16)	−0.0041 (17)
C8	0.034 (2)	0.044 (3)	0.031 (2)	−0.001 (2)	0.0024 (19)	0.007 (2)
C9	0.039 (3)	0.054 (3)	0.039 (2)	0.006 (2)	0.000 (2)	0.012 (2)
C10	0.031 (2)	0.067 (3)	0.044 (3)	0.001 (2)	−0.002 (2)	0.007 (3)
C11	0.045 (3)	0.052 (3)	0.035 (2)	−0.015 (2)	0.002 (2)	−0.003 (2)
C12	0.030 (2)	0.030 (2)	0.023 (2)	0.0050 (18)	−0.0013 (17)	0.0027 (18)
C13	0.032 (2)	0.032 (2)	0.029 (2)	0.0023 (19)	0.0018 (17)	0.0034 (19)
C14	0.031 (2)	0.036 (2)	0.035 (2)	−0.0061 (18)	0.0032 (17)	0.0047 (19)
C15	0.037 (2)	0.035 (2)	0.027 (2)	−0.0023 (19)	−0.0028 (18)	−0.0047 (18)
C16	0.031 (2)	0.055 (3)	0.028 (2)	−0.002 (2)	0.0098 (18)	0.005 (2)
C17	0.050 (3)	0.060 (3)	0.020 (2)	0.002 (2)	0.0040 (19)	0.004 (2)
C18	0.049 (3)	0.050 (3)	0.027 (2)	0.001 (2)	−0.004 (2)	−0.008 (2)
C19	0.035 (2)	0.037 (2)	0.032 (2)	0.001 (2)	−0.0018 (19)	0.002 (2)
C20	0.047 (3)	0.030 (2)	0.019 (2)	−0.008 (2)	0.0001 (19)	0.0006 (18)
C21	0.071 (3)	0.035 (2)	0.022 (2)	−0.005 (2)	−0.005 (2)	−0.002 (2)
C22	0.083 (4)	0.041 (3)	0.036 (3)	0.002 (3)	0.000 (3)	−0.001 (2)
C23	0.091 (4)	0.051 (3)	0.028 (2)	−0.014 (3)	−0.012 (3)	−0.005 (2)
C24	0.065 (3)	0.061 (3)	0.035 (3)	−0.009 (3)	−0.019 (2)	0.005 (3)
C25	0.055 (3)	0.044 (3)	0.025 (2)	−0.006 (2)	−0.004 (2)	0.004 (2)
C26	0.063 (3)	0.064 (3)	0.043 (3)	0.007 (3)	−0.011 (2)	−0.004 (3)
C27	0.057 (4)	0.129 (11)	0.084 (12)	0.008 (5)	−0.015 (4)	−0.048 (8)
C28	0.154 (10)	0.050 (6)	0.054 (8)	0.036 (6)	0.009 (7)	0.007 (5)
C26X	0.063 (3)	0.064 (3)	0.043 (3)	0.007 (3)	−0.011 (2)	−0.004 (3)
C27X	0.057 (4)	0.129 (11)	0.084 (12)	0.008 (5)	−0.015 (4)	−0.048 (8)
C28X	0.154 (10)	0.050 (6)	0.054 (8)	0.036 (6)	0.009 (7)	0.007 (5)
C29	0.071 (3)	0.051 (3)	0.046 (3)	0.012 (2)	−0.009 (3)	−0.010 (2)
C30	0.084 (4)	0.152 (6)	0.045 (3)	0.041 (4)	0.010 (3)	0.033 (4)
C31	0.077 (4)	0.060 (3)	0.061 (3)	0.015 (3)	0.001 (3)	0.009 (3)
N1	0.045 (2)	0.038 (2)	0.0263 (18)	−0.0112 (16)	0.0059 (15)	−0.0007 (15)
N2	0.044 (2)	0.034 (2)	0.0243 (17)	0.0044 (17)	0.0052 (15)	0.0038 (16)

Geometric parameters (Å, º)

C1—C2	1.384 (5)	C20—C25	1.395 (5)
C1—N1	1.394 (4)	C20—N1	1.434 (4)
C1—C15	1.406 (5)	C21—C22	1.394 (5)
C2—C12	1.421 (4)	C21—C29	1.509 (6)
C2—C3	1.489 (5)	C22—C23	1.371 (6)
C3—N2	1.326 (4)	C22—H22	0.9500
C3—C7	1.416 (5)	C23—C24	1.371 (6)
C4—C5	1.341 (5)	C23—H23	0.9500
C4—N2	1.365 (5)	C24—C25	1.388 (6)
C4—H4	0.9500	C24—H24	0.9500
C5—C6	1.404 (5)	C25—C26	1.513 (6)
C5—H5	0.9500	C26—C27	1.522 (9)
C6—C11	1.408 (5)	C26—C28	1.528 (8)
C6—C7	1.415 (5)	C26—H26	1.0000
C7—C8	1.405 (5)	C27—H27A	0.9800
C8—C9	1.361 (5)	C27—H27B	0.9800
C8—H8	0.9500	C27—H27C	0.9800
C9—C10	1.391 (6)	C28—H28A	0.9800
C9—H9	0.9500	C28—H28B	0.9800
C10—C11	1.346 (5)	C28—H28C	0.9800
C10—H10	0.9500	C27X—H27D	0.9800
C11—H11	0.9500	C27X—H27E	0.9800
C12—C13	1.404 (5)	C27X—H27F	0.9800
C12—C19	1.427 (5)	C28X—H28D	0.9800
C13—C16	1.416 (5)	C28X—H28E	0.9800
C13—C14	1.423 (5)	C28X—H28F	0.9800
C14—C15	1.354 (5)	C29—C31	1.517 (6)
C14—H14	0.9500	C29—C30	1.520 (6)
C15—H15	0.9500	C29—H29	1.0000
C16—C17	1.358 (5)	C30—H30A	0.9800
C16—H16	0.9500	C30—H30B	0.9800
C17—C18	1.398 (5)	C30—H30C	0.9800
C17—H17	0.9500	C31—H31A	0.9800
C18—C19	1.363 (5)	C31—H31B	0.9800
C18—H18	0.9500	C31—H31C	0.9800
C19—H19	0.9500	N1—H1	0.8800
C20—C21	1.391 (5)
C2—C1—N1	119.7 (3)	C18—C19—H19	119.6
C2—C1—C15	120.2 (3)	C12—C19—H19	119.6
N1—C1—C15	120.0 (3)	C21—C20—C25	123.1 (4)
C1—C2—C12	119.1 (3)	C21—C20—N1	118.3 (3)
C1—C2—C3	119.6 (3)	C25—C20—N1	118.6 (4)
C12—C2—C3	121.3 (3)	C20—C21—C22	117.0 (4)
N2—C3—C7	122.9 (3)	C20—C21—C29	121.8 (4)
N2—C3—C2	116.7 (3)	C22—C21—C29	121.2 (4)
C7—C3—C2	120.4 (3)	C23—C22—C21	120.9 (4)
C5—C4—N2	124.6 (4)	C23—C22—H22	119.5
C5—C4—H4	117.7	C21—C22—H22	119.5
N2—C4—H4	117.7	C22—C23—C24	120.9 (4)
C4—C5—C6	119.6 (4)	C22—C23—H23	119.6
C4—C5—H5	120.2	C24—C23—H23	119.6
C6—C5—H5	120.2	C23—C24—C25	120.9 (4)
C5—C6—C11	123.6 (4)	C23—C24—H24	119.6
C5—C6—C7	117.3 (3)	C25—C24—H24	119.6
C11—C6—C7	119.1 (4)	C24—C25—C20	117.2 (4)
C8—C7—C6	118.8 (3)	C24—C25—C26	120.5 (4)
C8—C7—C3	122.9 (3)	C20—C25—C26	122.3 (4)
C6—C7—C3	118.3 (3)	C25—C26—C27	114.2 (12)
C9—C8—C7	120.1 (4)	C25—C26—C28	111.8 (5)
C9—C8—H8	119.9	C27—C26—C28	111.9 (8)
C7—C8—H8	119.9	C25—C26—H26	106.1
C8—C9—C10	120.9 (4)	C27—C26—H26	106.1
C8—C9—H9	119.6	C28—C26—H26	106.1
C10—C9—H9	119.6	H27D—C27X—H27E	109.5
C11—C10—C9	120.7 (4)	H27D—C27X—H27F	109.5
C11—C10—H10	119.7	H27E—C27X—H27F	109.5
C9—C10—H10	119.7	H28D—C28X—H28E	109.5
C10—C11—C6	120.5 (4)	H28D—C28X—H28F	109.5
C10—C11—H11	119.7	H28E—C28X—H28F	109.5
C6—C11—H11	119.7	C21—C29—C31	112.8 (4)
C13—C12—C2	120.5 (3)	C21—C29—C30	110.9 (4)
C13—C12—C19	117.2 (3)	C31—C29—C30	108.7 (4)
C2—C12—C19	122.3 (3)	C21—C29—H29	108.1
C12—C13—C16	120.4 (3)	C31—C29—H29	108.1
C12—C13—C14	118.2 (3)	C30—C29—H29	108.1
C16—C13—C14	121.4 (3)	C29—C30—H30A	109.5
C15—C14—C13	121.0 (4)	C29—C30—H30B	109.5
C15—C14—H14	119.5	H30A—C30—H30B	109.5
C13—C14—H14	119.5	C29—C30—H30C	109.5
C14—C15—C1	120.8 (4)	H30A—C30—H30C	109.5
C14—C15—H15	119.6	H30B—C30—H30C	109.5
C1—C15—H15	119.6	C29—C31—H31A	109.5
C17—C16—C13	120.7 (4)	C29—C31—H31B	109.5
C17—C16—H16	119.6	H31A—C31—H31B	109.5
C13—C16—H16	119.6	C29—C31—H31C	109.5
C16—C17—C18	119.5 (4)	H31A—C31—H31C	109.5
C16—C17—H17	120.3	H31B—C31—H31C	109.5
C18—C17—H17	120.3	C1—N1—C20	124.0 (3)
C19—C18—C17	121.3 (4)	C1—N1—H1	118.0
C19—C18—H18	119.4	C20—N1—H1	118.0
C17—C18—H18	119.4	C3—N2—C4	117.2 (3)
C18—C19—C12	120.9 (4)
N1—C1—C2—C12	177.6 (3)	N1—C1—C15—C14	−178.8 (4)
C15—C1—C2—C12	−5.1 (5)	C12—C13—C16—C17	0.3 (6)
N1—C1—C2—C3	−2.7 (5)	C14—C13—C16—C17	−179.8 (3)
C15—C1—C2—C3	174.6 (3)	C13—C16—C17—C18	−0.1 (6)
C1—C2—C3—N2	70.8 (4)	C16—C17—C18—C19	−0.7 (6)
C12—C2—C3—N2	−109.5 (4)	C17—C18—C19—C12	1.2 (6)
C1—C2—C3—C7	−107.4 (4)	C13—C12—C19—C18	−1.0 (5)
C12—C2—C3—C7	72.3 (4)	C2—C12—C19—C18	179.6 (4)
N2—C4—C5—C6	1.2 (6)	C25—C20—C21—C22	0.0 (5)
C4—C5—C6—C11	178.0 (4)	N1—C20—C21—C22	−178.2 (3)
C4—C5—C6—C7	0.1 (5)	C25—C20—C21—C29	−178.5 (4)
C5—C6—C7—C8	177.1 (3)	N1—C20—C21—C29	3.3 (5)
C11—C6—C7—C8	−0.8 (5)	C20—C21—C22—C23	0.5 (6)
C5—C6—C7—C3	−2.5 (5)	C29—C21—C22—C23	179.1 (4)
C11—C6—C7—C3	179.6 (3)	C21—C22—C23—C24	−0.7 (7)
N2—C3—C7—C8	−175.8 (3)	C22—C23—C24—C25	0.3 (7)
C2—C3—C7—C8	2.3 (5)	C23—C24—C25—C20	0.3 (6)
N2—C3—C7—C6	3.8 (5)	C23—C24—C25—C26	−179.7 (4)
C2—C3—C7—C6	−178.1 (3)	C21—C20—C25—C24	−0.4 (6)
C6—C7—C8—C9	1.0 (5)	N1—C20—C25—C24	177.8 (3)
C3—C7—C8—C9	−179.4 (4)	C21—C20—C25—C26	179.5 (4)
C7—C8—C9—C10	−0.3 (6)	N1—C20—C25—C26	−2.2 (6)
C8—C9—C10—C11	−0.5 (6)	C24—C25—C26—C27	34.8 (10)
C9—C10—C11—C6	0.7 (6)	C20—C25—C26—C27	−145.2 (9)
C5—C6—C11—C10	−177.8 (4)	C24—C25—C26—C28	−93.6 (9)
C7—C6—C11—C10	0.0 (6)	C20—C25—C26—C28	86.4 (9)
C1—C2—C12—C13	3.3 (5)	C20—C21—C29—C31	−144.7 (4)
C3—C2—C12—C13	−176.3 (3)	C22—C21—C29—C31	36.8 (6)
C1—C2—C12—C19	−177.3 (3)	C20—C21—C29—C30	93.1 (5)
C3—C2—C12—C19	3.1 (5)	C22—C21—C29—C30	−85.4 (5)
C2—C12—C13—C16	179.7 (3)	C2—C1—N1—C20	178.2 (3)
C19—C12—C13—C16	0.2 (5)	C15—C1—N1—C20	0.8 (5)
C2—C12—C13—C14	−0.3 (5)	C21—C20—N1—C1	−98.9 (4)
C19—C12—C13—C14	−179.7 (3)	C25—C20—N1—C1	82.8 (4)
C12—C13—C14—C15	−1.0 (5)	C7—C3—N2—C4	−2.6 (5)
C16—C13—C14—C15	179.1 (4)	C2—C3—N2—C4	179.3 (3)
C13—C14—C15—C1	−0.7 (6)	C5—C4—N2—C3	0.0 (5)
C2—C1—C15—C14	3.9 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2	0.88	2.51	3.070 (4)	122