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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110018433/gd3345sup1.cif
Contains datablocks global, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110018433/gd3345IIsup2.hkl
Contains datablock II

CCDC reference: 782543

Comment top

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 top

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).

Experimental top

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.

Refinement top

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 Uiso(H) = kUeq(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 top

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 top
[Figure 1] Fig. 1. The general structure of the IAN ligand family. For (I), R = Me, and for (II), R = 2,6-iPrC6H3.
[Figure 2] 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.
[Figure 3] 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 Dmol3 (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 top
Crystal data top
C31H30N2F(000) = 920
Mr = 430.57Dx = 1.169 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3905 reflections
a = 9.0996 (10) Åθ = 4.1–34.0°
b = 11.2154 (12) ŵ = 0.07 mm1
c = 23.974 (3) ÅT = 140 K
V = 2446.7 (5) Å3Block, yellow
Z = 40.30 × 0.10 × 0.10 mm
Data collection top
Oxford Xcalibur 3 CCD area-detector
diffractometer
1584 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray SourceRint = 0.178
Graphite monochromatorθmax = 25.5°, θmin = 4.1°
Detector resolution: 16.0050 pixels mm-1h = 1111
ω and ϕ scansk = 1313
28412 measured reflectionsl = 2929
2579 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 0.95 w = 1/[σ2(Fo2) + (0.0422P)2]
where P = (Fo2 + 2Fc2)/3
2579 reflections(Δ/σ)max < 0.001
311 parametersΔρmax = 0.15 e Å3
3 restraintsΔρmin = 0.17 e Å3
Crystal data top
C31H30N2V = 2446.7 (5) Å3
Mr = 430.57Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 9.0996 (10) ŵ = 0.07 mm1
b = 11.2154 (12) ÅT = 140 K
c = 23.974 (3) Å0.30 × 0.10 × 0.10 mm
Data collection top
Oxford Xcalibur 3 CCD area-detector
diffractometer
1584 reflections with I > 2σ(I)
28412 measured reflectionsRint = 0.178
2579 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0563 restraints
wR(F2) = 0.101H-atom parameters constrained
S = 0.95Δρmax = 0.15 e Å3
2579 reflectionsΔρmin = 0.17 e Å3
311 parameters
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.6327 (4)0.6452 (3)0.17455 (15)0.0305 (9)
C20.6973 (4)0.7245 (3)0.21135 (14)0.0243 (9)
C30.8049 (4)0.8138 (3)0.19018 (14)0.0263 (9)
C40.8489 (5)0.9849 (3)0.14025 (15)0.0380 (11)
H40.81151.04830.11810.046*
C50.9937 (4)0.9833 (3)0.15055 (16)0.0358 (10)
H51.05511.04490.13650.043*
C61.0541 (4)0.8899 (3)0.18219 (15)0.0299 (9)
C70.9566 (4)0.8009 (3)0.20172 (13)0.0263 (9)
C81.0144 (4)0.7035 (4)0.23134 (15)0.0363 (10)
H80.95080.64220.24430.044*
C91.1613 (4)0.6966 (4)0.24152 (16)0.0438 (11)
H91.19930.63070.26170.053*
C101.2564 (4)0.7850 (4)0.22270 (17)0.0474 (12)
H101.35850.77900.23050.057*
C111.2052 (4)0.8789 (4)0.19360 (16)0.0437 (11)
H111.27160.93810.18070.052*
C120.6601 (4)0.7185 (3)0.26886 (14)0.0277 (9)
C130.5649 (4)0.6294 (3)0.28855 (15)0.0308 (9)
C140.5069 (4)0.5463 (3)0.24944 (17)0.0337 (9)
H140.44360.48450.26200.040*
C150.5407 (4)0.5540 (3)0.19454 (15)0.0327 (10)
H150.50170.49700.16920.039*
C160.5285 (4)0.6231 (4)0.34589 (15)0.0381 (11)
H160.46440.56210.35870.046*
C170.5842 (4)0.7032 (4)0.38272 (16)0.0433 (11)
H170.55910.69850.42110.052*
C180.6787 (4)0.7927 (4)0.36368 (16)0.0420 (11)
H180.71680.84920.38940.050*
C190.7174 (4)0.8004 (4)0.30888 (15)0.0346 (10)
H190.78330.86110.29720.041*
C200.6060 (4)0.5731 (3)0.07651 (15)0.0321 (9)
C210.6945 (5)0.4797 (3)0.05829 (16)0.0426 (11)
C220.6369 (5)0.4056 (4)0.01707 (18)0.0532 (12)
H220.69360.34040.00370.064*
C230.4995 (6)0.4254 (4)0.00452 (17)0.0564 (13)
H230.46280.37440.03290.068*
C240.4145 (5)0.5180 (4)0.01429 (18)0.0538 (13)
H240.31950.53010.00110.065*
C250.4655 (5)0.5944 (4)0.05551 (17)0.0413 (11)
C260.3704 (5)0.6960 (4)0.07618 (18)0.0563 (13)0.73 (3)
H260.40030.71040.11570.068*0.73 (3)
C270.2068 (12)0.668 (2)0.0777 (9)0.090 (4)0.73 (3)
H27A0.16880.66320.03950.135*0.73 (3)
H27B0.15500.73070.09810.135*0.73 (3)
H27C0.19140.59120.09650.135*0.73 (3)
C280.4021 (17)0.8118 (10)0.0449 (6)0.086 (4)0.73 (3)
H28A0.50800.82790.04560.129*0.73 (3)
H28B0.34960.87770.06290.129*0.73 (3)
H28C0.36910.80420.00620.129*0.73 (3)
C26X0.3704 (5)0.6960 (4)0.07618 (18)0.0563 (13)0.27 (3)
H26X0.41740.73940.10790.068*0.27 (3)
C27X0.218 (3)0.650 (7)0.091 (3)0.090 (4)0.27 (3)
H27D0.18260.59670.06180.135*0.27 (3)
H27E0.15050.71700.09560.135*0.27 (3)
H27F0.22360.60550.12660.135*0.27 (3)
C28X0.357 (5)0.775 (3)0.0239 (10)0.086 (4)0.27 (3)
H28D0.45490.80430.01330.129*0.27 (3)
H28E0.29290.84300.03200.129*0.27 (3)
H28F0.31580.72830.00680.129*0.27 (3)
C290.8446 (5)0.4574 (4)0.08287 (18)0.0560 (13)
H290.88230.53450.09820.067*
C300.8361 (6)0.3682 (6)0.1305 (2)0.094 (2)
H30A0.77200.39960.15990.140*
H30B0.93480.35480.14570.140*
H30C0.79620.29260.11660.140*
C310.9543 (5)0.4122 (4)0.0401 (2)0.0658 (14)
H31A0.92260.33410.02630.099*
H31B1.05130.40480.05750.099*
H31C0.95980.46860.00900.099*
N10.6639 (3)0.6530 (3)0.11774 (12)0.0363 (8)
H10.72280.71040.10650.044*
N20.7514 (3)0.9019 (3)0.15934 (12)0.0341 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.032 (2)0.036 (2)0.023 (2)0.0008 (19)0.0039 (17)0.0043 (18)
C20.020 (2)0.029 (2)0.024 (2)0.0004 (16)0.0008 (16)0.0005 (18)
C30.038 (2)0.025 (2)0.0160 (18)0.0015 (19)0.0058 (17)0.0060 (17)
C40.056 (3)0.030 (2)0.027 (2)0.005 (2)0.007 (2)0.0078 (19)
C50.043 (3)0.028 (2)0.036 (2)0.0116 (19)0.004 (2)0.000 (2)
C60.034 (2)0.032 (2)0.024 (2)0.006 (2)0.0024 (18)0.0034 (18)
C70.032 (2)0.026 (2)0.0208 (19)0.0007 (19)0.0002 (16)0.0041 (17)
C80.034 (2)0.044 (3)0.031 (2)0.001 (2)0.0024 (19)0.007 (2)
C90.039 (3)0.054 (3)0.039 (2)0.006 (2)0.000 (2)0.012 (2)
C100.031 (2)0.067 (3)0.044 (3)0.001 (2)0.002 (2)0.007 (3)
C110.045 (3)0.052 (3)0.035 (2)0.015 (2)0.002 (2)0.003 (2)
C120.030 (2)0.030 (2)0.023 (2)0.0050 (18)0.0013 (17)0.0027 (18)
C130.032 (2)0.032 (2)0.029 (2)0.0023 (19)0.0018 (17)0.0034 (19)
C140.031 (2)0.036 (2)0.035 (2)0.0061 (18)0.0032 (17)0.0047 (19)
C150.037 (2)0.035 (2)0.027 (2)0.0023 (19)0.0028 (18)0.0047 (18)
C160.031 (2)0.055 (3)0.028 (2)0.002 (2)0.0098 (18)0.005 (2)
C170.050 (3)0.060 (3)0.020 (2)0.002 (2)0.0040 (19)0.004 (2)
C180.049 (3)0.050 (3)0.027 (2)0.001 (2)0.004 (2)0.008 (2)
C190.035 (2)0.037 (2)0.032 (2)0.001 (2)0.0018 (19)0.002 (2)
C200.047 (3)0.030 (2)0.019 (2)0.008 (2)0.0001 (19)0.0006 (18)
C210.071 (3)0.035 (2)0.022 (2)0.005 (2)0.005 (2)0.002 (2)
C220.083 (4)0.041 (3)0.036 (3)0.002 (3)0.000 (3)0.001 (2)
C230.091 (4)0.051 (3)0.028 (2)0.014 (3)0.012 (3)0.005 (2)
C240.065 (3)0.061 (3)0.035 (3)0.009 (3)0.019 (2)0.005 (3)
C250.055 (3)0.044 (3)0.025 (2)0.006 (2)0.004 (2)0.004 (2)
C260.063 (3)0.064 (3)0.043 (3)0.007 (3)0.011 (2)0.004 (3)
C270.057 (4)0.129 (11)0.084 (12)0.008 (5)0.015 (4)0.048 (8)
C280.154 (10)0.050 (6)0.054 (8)0.036 (6)0.009 (7)0.007 (5)
C26X0.063 (3)0.064 (3)0.043 (3)0.007 (3)0.011 (2)0.004 (3)
C27X0.057 (4)0.129 (11)0.084 (12)0.008 (5)0.015 (4)0.048 (8)
C28X0.154 (10)0.050 (6)0.054 (8)0.036 (6)0.009 (7)0.007 (5)
C290.071 (3)0.051 (3)0.046 (3)0.012 (2)0.009 (3)0.010 (2)
C300.084 (4)0.152 (6)0.045 (3)0.041 (4)0.010 (3)0.033 (4)
C310.077 (4)0.060 (3)0.061 (3)0.015 (3)0.001 (3)0.009 (3)
N10.045 (2)0.038 (2)0.0263 (18)0.0112 (16)0.0059 (15)0.0007 (15)
N20.044 (2)0.034 (2)0.0243 (17)0.0044 (17)0.0052 (15)0.0038 (16)
Geometric parameters (Å, º) top
C1—C21.384 (5)C20—C251.395 (5)
C1—N11.394 (4)C20—N11.434 (4)
C1—C151.406 (5)C21—C221.394 (5)
C2—C121.421 (4)C21—C291.509 (6)
C2—C31.489 (5)C22—C231.371 (6)
C3—N21.326 (4)C22—H220.9500
C3—C71.416 (5)C23—C241.371 (6)
C4—C51.341 (5)C23—H230.9500
C4—N21.365 (5)C24—C251.388 (6)
C4—H40.9500C24—H240.9500
C5—C61.404 (5)C25—C261.513 (6)
C5—H50.9500C26—C271.522 (9)
C6—C111.408 (5)C26—C281.528 (8)
C6—C71.415 (5)C26—H261.0000
C7—C81.405 (5)C27—H27A0.9800
C8—C91.361 (5)C27—H27B0.9800
C8—H80.9500C27—H27C0.9800
C9—C101.391 (6)C28—H28A0.9800
C9—H90.9500C28—H28B0.9800
C10—C111.346 (5)C28—H28C0.9800
C10—H100.9500C27X—H27D0.9800
C11—H110.9500C27X—H27E0.9800
C12—C131.404 (5)C27X—H27F0.9800
C12—C191.427 (5)C28X—H28D0.9800
C13—C161.416 (5)C28X—H28E0.9800
C13—C141.423 (5)C28X—H28F0.9800
C14—C151.354 (5)C29—C311.517 (6)
C14—H140.9500C29—C301.520 (6)
C15—H150.9500C29—H291.0000
C16—C171.358 (5)C30—H30A0.9800
C16—H160.9500C30—H30B0.9800
C17—C181.398 (5)C30—H30C0.9800
C17—H170.9500C31—H31A0.9800
C18—C191.363 (5)C31—H31B0.9800
C18—H180.9500C31—H31C0.9800
C19—H190.9500N1—H10.8800
C20—C211.391 (5)
C2—C1—N1119.7 (3)C18—C19—H19119.6
C2—C1—C15120.2 (3)C12—C19—H19119.6
N1—C1—C15120.0 (3)C21—C20—C25123.1 (4)
C1—C2—C12119.1 (3)C21—C20—N1118.3 (3)
C1—C2—C3119.6 (3)C25—C20—N1118.6 (4)
C12—C2—C3121.3 (3)C20—C21—C22117.0 (4)
N2—C3—C7122.9 (3)C20—C21—C29121.8 (4)
N2—C3—C2116.7 (3)C22—C21—C29121.2 (4)
C7—C3—C2120.4 (3)C23—C22—C21120.9 (4)
C5—C4—N2124.6 (4)C23—C22—H22119.5
C5—C4—H4117.7C21—C22—H22119.5
N2—C4—H4117.7C22—C23—C24120.9 (4)
C4—C5—C6119.6 (4)C22—C23—H23119.6
C4—C5—H5120.2C24—C23—H23119.6
C6—C5—H5120.2C23—C24—C25120.9 (4)
C5—C6—C11123.6 (4)C23—C24—H24119.6
C5—C6—C7117.3 (3)C25—C24—H24119.6
C11—C6—C7119.1 (4)C24—C25—C20117.2 (4)
C8—C7—C6118.8 (3)C24—C25—C26120.5 (4)
C8—C7—C3122.9 (3)C20—C25—C26122.3 (4)
C6—C7—C3118.3 (3)C25—C26—C27114.2 (12)
C9—C8—C7120.1 (4)C25—C26—C28111.8 (5)
C9—C8—H8119.9C27—C26—C28111.9 (8)
C7—C8—H8119.9C25—C26—H26106.1
C8—C9—C10120.9 (4)C27—C26—H26106.1
C8—C9—H9119.6C28—C26—H26106.1
C10—C9—H9119.6H27D—C27X—H27E109.5
C11—C10—C9120.7 (4)H27D—C27X—H27F109.5
C11—C10—H10119.7H27E—C27X—H27F109.5
C9—C10—H10119.7H28D—C28X—H28E109.5
C10—C11—C6120.5 (4)H28D—C28X—H28F109.5
C10—C11—H11119.7H28E—C28X—H28F109.5
C6—C11—H11119.7C21—C29—C31112.8 (4)
C13—C12—C2120.5 (3)C21—C29—C30110.9 (4)
C13—C12—C19117.2 (3)C31—C29—C30108.7 (4)
C2—C12—C19122.3 (3)C21—C29—H29108.1
C12—C13—C16120.4 (3)C31—C29—H29108.1
C12—C13—C14118.2 (3)C30—C29—H29108.1
C16—C13—C14121.4 (3)C29—C30—H30A109.5
C15—C14—C13121.0 (4)C29—C30—H30B109.5
C15—C14—H14119.5H30A—C30—H30B109.5
C13—C14—H14119.5C29—C30—H30C109.5
C14—C15—C1120.8 (4)H30A—C30—H30C109.5
C14—C15—H15119.6H30B—C30—H30C109.5
C1—C15—H15119.6C29—C31—H31A109.5
C17—C16—C13120.7 (4)C29—C31—H31B109.5
C17—C16—H16119.6H31A—C31—H31B109.5
C13—C16—H16119.6C29—C31—H31C109.5
C16—C17—C18119.5 (4)H31A—C31—H31C109.5
C16—C17—H17120.3H31B—C31—H31C109.5
C18—C17—H17120.3C1—N1—C20124.0 (3)
C19—C18—C17121.3 (4)C1—N1—H1118.0
C19—C18—H18119.4C20—N1—H1118.0
C17—C18—H18119.4C3—N2—C4117.2 (3)
C18—C19—C12120.9 (4)
N1—C1—C2—C12177.6 (3)N1—C1—C15—C14178.8 (4)
C15—C1—C2—C125.1 (5)C12—C13—C16—C170.3 (6)
N1—C1—C2—C32.7 (5)C14—C13—C16—C17179.8 (3)
C15—C1—C2—C3174.6 (3)C13—C16—C17—C180.1 (6)
C1—C2—C3—N270.8 (4)C16—C17—C18—C190.7 (6)
C12—C2—C3—N2109.5 (4)C17—C18—C19—C121.2 (6)
C1—C2—C3—C7107.4 (4)C13—C12—C19—C181.0 (5)
C12—C2—C3—C772.3 (4)C2—C12—C19—C18179.6 (4)
N2—C4—C5—C61.2 (6)C25—C20—C21—C220.0 (5)
C4—C5—C6—C11178.0 (4)N1—C20—C21—C22178.2 (3)
C4—C5—C6—C70.1 (5)C25—C20—C21—C29178.5 (4)
C5—C6—C7—C8177.1 (3)N1—C20—C21—C293.3 (5)
C11—C6—C7—C80.8 (5)C20—C21—C22—C230.5 (6)
C5—C6—C7—C32.5 (5)C29—C21—C22—C23179.1 (4)
C11—C6—C7—C3179.6 (3)C21—C22—C23—C240.7 (7)
N2—C3—C7—C8175.8 (3)C22—C23—C24—C250.3 (7)
C2—C3—C7—C82.3 (5)C23—C24—C25—C200.3 (6)
N2—C3—C7—C63.8 (5)C23—C24—C25—C26179.7 (4)
C2—C3—C7—C6178.1 (3)C21—C20—C25—C240.4 (6)
C6—C7—C8—C91.0 (5)N1—C20—C25—C24177.8 (3)
C3—C7—C8—C9179.4 (4)C21—C20—C25—C26179.5 (4)
C7—C8—C9—C100.3 (6)N1—C20—C25—C262.2 (6)
C8—C9—C10—C110.5 (6)C24—C25—C26—C2734.8 (10)
C9—C10—C11—C60.7 (6)C20—C25—C26—C27145.2 (9)
C5—C6—C11—C10177.8 (4)C24—C25—C26—C2893.6 (9)
C7—C6—C11—C100.0 (6)C20—C25—C26—C2886.4 (9)
C1—C2—C12—C133.3 (5)C20—C21—C29—C31144.7 (4)
C3—C2—C12—C13176.3 (3)C22—C21—C29—C3136.8 (6)
C1—C2—C12—C19177.3 (3)C20—C21—C29—C3093.1 (5)
C3—C2—C12—C193.1 (5)C22—C21—C29—C3085.4 (5)
C2—C12—C13—C16179.7 (3)C2—C1—N1—C20178.2 (3)
C19—C12—C13—C160.2 (5)C15—C1—N1—C200.8 (5)
C2—C12—C13—C140.3 (5)C21—C20—N1—C198.9 (4)
C19—C12—C13—C14179.7 (3)C25—C20—N1—C182.8 (4)
C12—C13—C14—C151.0 (5)C7—C3—N2—C42.6 (5)
C16—C13—C14—C15179.1 (4)C2—C3—N2—C4179.3 (3)
C13—C14—C15—C10.7 (6)C5—C4—N2—C30.0 (5)
C2—C1—C15—C143.9 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N20.882.513.070 (4)122

Experimental details

Crystal data
Chemical formulaC31H30N2
Mr430.57
Crystal system, space groupOrthorhombic, P212121
Temperature (K)140
a, b, c (Å)9.0996 (10), 11.2154 (12), 23.974 (3)
V3)2446.7 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.30 × 0.10 × 0.10
Data collection
DiffractometerOxford Xcalibur 3 CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
28412, 2579, 1584
Rint0.178
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.101, 0.95
No. of reflections2579
No. of parameters311
No. of restraints3
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.17

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis PRO (Oxford Diffraction, 2010), SIR92 (Altomare et al., 1993), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).

Selected bond lengths (Å) top
C1—N11.394 (4)C4—N21.365 (5)
C3—N21.326 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N20.882.513.070 (4)122.3
Fractional coordinates of selected heavy atoms. top
AtomExperimental (x, y, z)CASTEP (x, y, z)DMol3 (x, y, z)
N1(0.3355, 0.3474, 0.8822)(0.3445, 0.3495, 0.8821)(0.3371, 0.3484, 0.8822)
N2(0.2487, 0.0978, 0.8408)(0.2509, 0.1019, 0.8435)(0.2466, 0.0994, 0.8431)
C1(0.3672, 0.3546, 0.8257)(0.3717, 0.3579, 0.8255)(0.3664, 0.3566, 0.8256)
C2(0.3028, 0.2755, 0.7889)(0.3061, 0.2768, 0.7884)(0.3026, 0.2746, 0.7884)
C3(0.1955, 0.1863, 0.8097)(0.1989, 0.1888, 0.8105)0.1950, 0.1862, 0.8103)
C20(0.3942, 0.4267, 0.9234)(0.4006, 0.4294, 0.9235)(0.3956, 0.4279, 0.9234)
C—H and N—H bond lengths (Å) in (II) from X-ray experiment and DFT calculations. top
BondCASTEPDMol3
Aryl C—H
C4—H41.0931.092
C5—H51.0911.091
C8—H81.0901.090
C9—H91.0901.089
C10—H101.0901.089
C11—H111.0891.089
C14—H141.0911.091
C15—H151.0901.090
C16—H161.0931.092
C17—H171.0891.088
C18—H181.0911.091
C19—H191.0911.091
C22—H221.0911.090
C23—H231.0901.090
C24—H241.0901.090
Methine C—H
C26-H261.1021.100
C29-H291.1001.099
Methyl C—H
C27—H27A1.0981.098
C27—H27B1.0981.097
C27—H27C1.0981.098
C28—H28A1.1011.101
C28—H28B1.1001.099
C28—H28C1.0971.097
C30—H30A1.0991.098
C30—H30B1.0991.099
C30—H30C1.0981.097
C31—H31A1.1011.100
C31—H31B1.1001.099
C31—H31C1.1001.099
N—H
N1—H11.0251.019
Riding-model distances: aryl C—H = 0.95Å, methyl C—H = 0.98Å, methine C—H = 1.00Å and N—H 0.88 Å.
Difference between experimental and calculated values (%) top
CASTEPDMol3
Aryl C—H14.114.1
Methyl C—H11.911.8
Methine C—H10.210.0
N—H10.59.9
 

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