Wave-like structure in 3-(4,6-diamino-1,3,5-triazin-2-yl)-2-naphthonitrile

In the title compound, C₁₄H₁₀N₆, which crystallizes with Z′ = 2 in the C2/c space group, the mol­ecules are linked by N—H...N hydrogen bonds into chains, which are arranged in a wave-like form stabilized by aromatic π–π stacking inter­actions. This work demonstrates the usefulness of aromatic triazine derivatives in crystal engineering.

S1. Comment

A productive strategy in crystal engineering utilizes molecules which can form multiple interactions with their neighbours (Wuest, 2005). Hydrogen bonds are widely used as the principal interactions in this strategy since they are directional and relatively strong (Moulton & Zaworotko, 2001; Seiter, 2002). Many different self-complementary hydrogen-bonding groups can be used to control association in crystal engineering and to produce different arrangements, such as chains, sheets, ribbons, tapes, rosettes etc., having predictable structural features (Desiraju, 1990, 2002). Several studies have demonstrated the usefulness of melamine and its organic and inorganic complexes or salts in crystal engineering (Whitesides et al. 1995; Janczak & Perpétuo, 2001, 2002, 2003, 2004, 2008; Perpétuo & Janczak, 2003, 2005, 2007), since their components contain complementary arrays of hydrogen-bonding sites. While π–π interactions are intermolecular forces whose nature is still a matter of discussion (Hunter & Sanders, 1990; Janiak, 2000; Cozzi et al. 2003; Kobayashi & Saigo, 2005), in general, two aromatic rings are arranged in a face-to-face orientation with a distance of 3.2–3.8 Å between the planes of the rings.

In an effort to engineer expanded versions of the structures formed during the transformation of the cyano group in dicyanobenzene isomers in the presence of cyanoguanidine (Janczak & Kubiak, 2005a,b), we have replaced the phenyl rings with naphthyl systems, using 2,3-dicyanonaphthalene, and we have investigated the role of π–π stacking interactions in the organization and stabilization of the resulting structures. We present here the crystal structure of one of these, the title compound, (I).

Compound (I) crystallizes with Z' = 2 and the two independent molecules, M1 and M2, are linked by N—H···N hydrogen bonds (Table 2) into a dimeric unit (Fig. 1). These units are linked by further N—H···N hydrogen bonds to form a zigzag chain (Fig. 3a). Although the bond lengths and angles in the two independent molecules are very similar, their conformations differ in the rotation angle of the triazine ring relative to the naphthalene ring around the inter-ring bond. The dihedral angles between the planes of triazine and naphthalene rings are 27.0 (2) and 10.7 (2)° in molecules M1 and M2, respectively. The rotation is caused by an interaction of the highly polar C≡N group with the triazine ring.

The gas-phase geometry obtained by ab initio molecular orbital calculations at the B3LYP/6–31+G^* level (GAUSSIAN98; Frisch et al., 1998) confirms the non-planar conformation (Fig. 2). The calculated dihedral angle between the planes of the triazine and naphthalene rings, 14.7°, represents a global minimum on the potential energy surface (PES). During rotation of the triazine ring relative to naphthalene around the inter-ring bond from 0 to 360°, four equivalent minima and two pairs of maxima are found. The minima are observed at rotation angles of ±14.7° and (180±14.7)° (165.3 and 194.7°), while the maxima are observed at 0° (and 180°) with a barrier energy of ~5.85 kJ mol^-1, and at 90° (and 270°) with a barrier energy of ~14.35 kJ mol^-1.

The difference between the barrier energy of the conformation at 0 and 90° (ΔE = 8.5 kJ mol^-1) can be attributed to the π-delocalization energy of the π electrons along the inter-ring bond. At a rotation angle of 90° (rings perpendicular), delocalization of the π electrons between the rings is impossible due to the symmetry of the orbitals. The lengthening of the inter-ring bond, from 1.488 Å for the most stable conformation to 1.511 Å for a rotation angle of 90°, supports this fact. The estimated energy of molecule M1 in the conformation as present in the crystal structure is greater by ~6.75 kJ mol^-1, while for the second molecule it is greater only by ~1.85 kJ mol^-1. The differences between the energies of the molecules in the crystal structure and in the gas phase (obtained by molecular orbital calculations) are compensated for by π–π interactions between the aromatic rings in the crystal structure.

Considering both conformations of the independent molecules M1 and M2 in the crystal structure of (I) (Fig. 1, Table 1) and in the gas-phase conformation (Fig. 2) in more detail, besides the main difference mentioned above in the rotation angle of the rings, several other differences can also be found. For example, the C—C≡N angle in molecule M1 [173.9 (2)°] is closer to 180° than that in molecule M2 [167.7 (2)°]. These values correlate well with the rotation angles of the triazine ring in relation to the naphthalene ring. The greater rotation angle around the inter-ring C—C bond lengthens the distance between the polar C≡N group and the triazine ring and results in a decrease in the repulsion between the substituents at positions 2 and 3 in the naphthalene ring.

In the dimer unit formed by the independent molecules M1 and M2 (Fig. 1), the two triazine rings are not coplanar; the dihedral angle between their planes is 22.6 (1)°. Dimers related by a c-glide plane interact via two pairs of N—H···N hydrogen bonds, forming infinite chains along the c axis (Fig. 3a). There is no hydrogen bonding between the chains, and the chains interact only via van der Waals forces and π–π stacking interactions. Although the triazine rings each contain one potential hydrogen-bonding site (atoms N1 and N21), these sites are inactive due to steric hindrance from the cyano groups.

The various chains along [001] form a wave-like architecture (Fig. 3b) with a distance of ca 3.45 Å between adjacent aromatic ring systems, consistent with the occurrence of π–π stacking interactions, since this distance is comparable with the sum of the van der Waals radii of two C atoms in an aromatic ring system (Pauling, 1967). The sheets of the wave-like structure lie parallel to the (010) plane (Fig. 3b).

Our observations underscore the potential utility of (I) in crystal engineering. The amine groups can donate hydrogen bonds to the N atoms of neighbouring triazine rings, which act as acceptors, thus forming a characteristic dimeric motif. The dimeric motif containing hydrogen-bonding active sites can interact with neighbouring molecules via two pairs of N—H···N hydrogen bonds, favouring the formation of one-dimensional-polymers. In the absence of hydrogen bonds between these one-dimensional-polymers, π–π interactions between offset aromatic rings stabilize the overall structure.

Related literature

For related literature, see: Cozzi et al. (2003); Desiraju (1990, 2002); Frisch (1998); Hunter & Sanders (1990); Janczak & Kubiak (2005a, 2005b); Janczak & Perpétuo (2001, 2002, 2003, 2004, 2008); Janiak (2000); Kobayashi & Saigo (2005); Moulton & Zaworotko (2001); Pauling (1967); Perpétuo & Janczak (2003, 2005, 2007); Seiter (2002); Whitesides et al. (1995); Wuest (2005).

S2. Experimental

2,3-Dicyanonaphthalene (99% purity) and cyanoguanidine (99% purity) were purchased from Sigma–Aldrich. They were mixed together in a 1:1 molar ratio and the mixture was pressed into pellets. The pellets were inserted into an evacuated glass ampoule and annealed in the temperature gradient ?–? K [Please give values for temperature gradient]. Crystals of 2-(4,6-diamino-1,3,5-triazin-2-yl)-3-naphthonitrile, (I), were formed in the low-temperature zone during migration from the high-temperature zone at which the compound is formed (Janczak & Kubiak, 2005a,b). Elemental analysis, found: C 64.21, N 32.00, H 3.79%; calculated for C₁₄H₁₀N₆: C 64.11, N 32.05, H 3.84%.

S3. Refinement

The H atoms were treated as riding atoms in geometrically idealized positions with distances C—H = 0.93 Å and N—H = 0.86 Å, with U_iso=1.2U_eq(parent).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The independent components of compound (I), showing the atom-labelling scheme and the hydrogen bonds within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 2. Results of the optimized molecular orbital calculations (B3LYP/6–31+G* level) for (I) (Å, °).
	Fig. 3. (a) A view of the N—H···N hydrogen-bonded chains of (I), which exhibit R2^2(8) topology. (b) The wave-like structure in the crystal structure of (I). For the sake of clarity, H atoms bonded to C atoms have been omitted.

3-(4,6-diamino-1,3,5-triazin-2-yl)-2-naphthonitrile

Crystal data

C14H10N6	F(000) = 2176
Mr = 262.28	Dx = 1.417 Mg m^−3 Dm = 1.41 Mg m^−3 Dm measured by flotation
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1203 reflections
a = 35.798 (7) Å	θ = 2.9–28.0°
b = 7.319 (1) Å	µ = 0.09 mm^−1
c = 21.459 (4) Å	T = 295 K
β = 118.96 (3)°	Paralellepiped, colourless
V = 4919 (2) Å^3	0.32 × 0.26 × 0.18 mm
Z = 16

Data collection

Kuma KM-4 with CCD area-detector diffractometer	5875 independent reflections
Radiation source: fine-focus sealed tube	3357 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 1024x1024 with blocks 2x2 pixels mm^-1	θmax = 28.0°, θmin = 2.9°
ω–scan	h = −46→47
Absorption correction: analytical face-indexed (SHELXTL; Sheldrick, 2008)	k = −9→8
Tmin = 0.974, Tmax = 0.981	l = −27→28
27666 measured reflections

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)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0055P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.002
5875 reflections	Δρmax = 0.23 e Å^−3
362 parameters	Δρmin = −0.24 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: 0.000643 (13)

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	0.24088 (5)	−0.0920 (2)	0.36585 (8)	0.0428 (4)
N2	0.16587 (5)	−0.0631 (3)	0.32362 (8)	0.0436 (4)
N3	0.19370 (4)	−0.0352 (2)	0.24293 (7)	0.0409 (4)
N4	0.21289 (5)	−0.1033 (3)	0.44220 (8)	0.0545 (5)
H4A	0.1916	−0.0994	0.4505	0.065*
H4B	0.2384	−0.1183	0.4768	0.065*
N5	0.12212 (5)	−0.0133 (3)	0.20440 (8)	0.0590 (6)
H5A	0.1005	−0.0139	0.2118	0.071*
H5B	0.1183	0.0032	0.1620	0.071*
N6	0.33079 (7)	0.1134 (4)	0.46499 (10)	0.0747 (7)
C1	0.34280 (6)	0.0222 (3)	0.32101 (12)	0.0554 (6)
H1	0.3696	0.0619	0.3557	0.066*
C2	0.31020 (6)	0.0096 (3)	0.33764 (10)	0.0433 (5)
C3	0.26894 (5)	−0.0503 (3)	0.28489 (9)	0.0384 (4)
C4	0.26267 (6)	−0.0921 (3)	0.21832 (10)	0.0449 (5)
H4	0.2357	−0.1300	0.1837	0.054*
C5	0.29570 (7)	−0.0799 (3)	0.20034 (11)	0.0514 (6)
C6	0.28874 (9)	−0.1225 (4)	0.13115 (13)	0.0526 (7)
H6	0.2617	−0.1571	0.0958	0.065*
C7	0.32178 (13)	−0.1126 (5)	0.11631 (19)	0.0641 (11)
H7	0.3172	−0.1410	0.0709	0.089*
C8	0.36263 (12)	−0.0600 (5)	0.1694 (2)	0.0779 (12)
H8	0.3850	−0.0552	0.1589	0.101*
C9	0.36997 (9)	−0.0161 (5)	0.23543 (18)	0.0669 (10)
H9	0.3973	0.0193	0.2697	0.083*
C10	0.33665 (7)	−0.0233 (3)	0.25343 (13)	0.0567 (6)
C11	0.31975 (6)	0.0652 (3)	0.40836 (11)	0.0512 (6)
C12	0.23228 (5)	−0.0616 (3)	0.29931 (9)	0.0378 (4)
C13	0.20624 (6)	−0.0861 (3)	0.37555 (9)	0.0412 (5)
C14	0.16155 (5)	−0.0379 (3)	0.25874 (9)	0.0416 (5)
N21	0.06563 (5)	0.0934 (3)	0.42305 (7)	0.0420 (4)
N22	0.13485 (4)	−0.0428 (2)	0.47121 (7)	0.0408 (4)
N23	0.10629 (4)	0.0448 (2)	0.54784 (7)	0.0393 (4)
N24	0.09287 (5)	0.0056 (3)	0.35111 (8)	0.0593 (6)
H24A	0.1127	−0.0414	0.3444	0.071*
H24B	0.0696	0.0440	0.3154	0.071*
N25	0.17220 (5)	−0.0912 (3)	0.59144 (8)	0.0514 (5)
H25A	0.1922	−0.1397	0.5857	0.062*
H25B	0.1748	−0.0839	0.6334	0.062*
N26	−0.03217 (6)	0.1319 (4)	0.30228 (9)	0.0725 (7)
C21	−0.03870 (6)	0.2784 (3)	0.44141 (10)	0.0434 (5)
H21	−0.0648	0.2985	0.4008	0.052*
C22	−0.00531 (5)	0.2085 (3)	0.43414 (9)	0.0387 (4)
C23	0.03541 (5)	0.1792 (3)	0.49551 (9)	0.0364 (4)
C24	0.03951 (6)	0.2220 (3)	0.56061 (9)	0.0429 (5)
H24	0.0660	0.2056	0.6009	0.052*
C25	0.00547 (6)	0.2899 (3)	0.56967 (9)	0.0421 (5)
C26	0.00936 (7)	0.3294 (4)	0.63708 (11)	0.0601 (7)
H26	0.0353	0.3103	0.6782	0.072*
C27	−0.02471 (8)	0.3955 (4)	0.64224 (13)	0.0709 (8)
H27	−0.0217	0.4209	0.6869	0.085*
C28	−0.06406 (7)	0.4255 (4)	0.58130 (13)	0.0627 (7)
H28	−0.0869	0.4713	0.5857	0.075*
C29	−0.06891 (7)	0.3884 (3)	0.51653 (12)	0.0521 (6)
H29	−0.0953	0.4080	0.4764	0.062*
C210	−0.03451 (6)	0.3201 (3)	0.50836 (10)	0.0407 (5)
C211	−0.01620 (6)	0.1632 (3)	0.36179 (10)	0.0492 (5)
C212	0.07168 (5)	0.1017 (3)	0.48856 (9)	0.0360 (4)
C213	0.09817 (5)	0.0186 (3)	0.41668 (9)	0.0404 (5)
C214	0.13691 (5)	−0.0271 (3)	0.53504 (9)	0.0387 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0310 (7)	0.0648 (12)	0.0361 (8)	0.0009 (8)	0.0189 (6)	0.0031 (8)
N2	0.0302 (7)	0.0707 (13)	0.0340 (8)	−0.0007 (8)	0.0187 (6)	−0.0022 (8)
N3	0.0290 (7)	0.0645 (12)	0.0311 (7)	−0.0007 (8)	0.0161 (6)	−0.0025 (7)
N4	0.0368 (8)	0.0960 (16)	0.0352 (8)	0.0048 (9)	0.0209 (7)	0.0075 (9)
N5	0.0272 (8)	0.1163 (18)	0.0338 (8)	0.0001 (10)	0.0151 (6)	−0.0016 (9)
N6	0.0628 (12)	0.1080 (19)	0.0539 (12)	−0.0209 (13)	0.0288 (10)	−0.0155 (12)
C1	0.0355 (10)	0.0742 (17)	0.0616 (13)	−0.0006 (11)	0.0275 (9)	0.0109 (12)
C2	0.0320 (9)	0.0559 (14)	0.0445 (10)	0.0039 (9)	0.0205 (8)	0.0086 (9)
C3	0.0309 (9)	0.0495 (13)	0.0390 (9)	0.0043 (9)	0.0202 (7)	0.0056 (8)
C4	0.0414 (10)	0.0558 (14)	0.0436 (10)	0.0061 (10)	0.0254 (8)	0.0037 (9)
C5	0.0622 (13)	0.0536 (14)	0.0575 (12)	0.0138 (11)	0.0442 (11)	0.0093 (10)
C6	0.0677 (19)	0.0524 (18)	0.0571 (15)	0.0132 (15)	0.0424 (15)	0.0089 (13)
C7	0.068 (3)	0.062 (2)	0.066 (2)	0.014 (2)	0.040 (2)	0.0106 (19)
C8	0.079 (3)	0.078 (3)	0.072 (3)	0.0040 (19)	0.047 (3)	0.0160 (19)
C9	0.0660 (18)	0.065 (3)	0.0700 (18)	0.0024 (18)	0.0420 (19)	0.0143 (19)
C10	0.0547 (12)	0.0653 (16)	0.0705 (14)	0.0053 (12)	0.0415 (11)	0.0039 (12)
C11	0.0344 (9)	0.0695 (16)	0.0488 (12)	−0.0055 (10)	0.0195 (9)	0.0018 (11)
C12	0.0309 (8)	0.0513 (13)	0.0345 (9)	−0.0007 (9)	0.0186 (7)	−0.0016 (8)
C13	0.0332 (9)	0.0581 (14)	0.0355 (9)	−0.0019 (9)	0.0192 (7)	−0.0002 (8)
C14	0.0296 (8)	0.0625 (14)	0.0345 (9)	−0.0022 (9)	0.0171 (7)	−0.0051 (9)
N21	0.0317 (7)	0.0628 (12)	0.0331 (8)	0.0051 (8)	0.0170 (6)	0.0024 (7)
N22	0.0300 (7)	0.0641 (12)	0.0311 (7)	0.0018 (8)	0.0170 (6)	0.0022 (7)
N23	0.0285 (7)	0.0607 (11)	0.0305 (7)	−0.0010 (7)	0.0157 (6)	−0.0014 (7)
N24	0.0485 (8)	0.0930 (17)	0.0415 (8)	0.0193 (10)	0.0210 (7)	0.0094 (9)
N25	0.0352 (8)	0.0856 (14)	0.0325 (8)	0.0126 (9)	0.0158 (7)	0.0048 (8)
N26	0.0426 (9)	0.127 (2)	0.0391 (10)	0.0062 (11)	0.0129 (8)	−0.0198 (11)
C21	0.0313 (9)	0.0568 (14)	0.0406 (10)	0.0027 (9)	0.0162 (8)	−0.0022 (9)
C22	0.0336 (9)	0.0507 (13)	0.0339 (9)	0.0024 (9)	0.0149 (8)	−0.0054 (8)
C23	0.0292 (8)	0.0458 (12)	0.0358 (9)	−0.0033 (8)	0.0171 (7)	−0.0020 (8)
C24	0.0316 (9)	0.0611 (14)	0.0355 (9)	−0.0037 (9)	0.0158 (8)	−0.0040 (9)
C25	0.0399 (10)	0.0526 (13)	0.0407 (10)	−0.0069 (9)	0.0251 (8)	−0.0070 (9)
C26	0.0557 (12)	0.084 (2)	0.0476 (11)	−0.0083 (13)	0.0277 (10)	−0.0130 (12)
C27	0.0697 (15)	0.095 (2)	0.0682 (14)	−0.0047 (15)	0.0469 (13)	−0.0195 (14)
C28	0.0570 (13)	0.0817 (19)	0.0691 (14)	0.0034 (13)	0.0461 (12)	−0.0088 (13)
C29	0.0427 (11)	0.0630 (15)	0.0589 (12)	0.0033 (11)	0.0312 (10)	−0.0033 (11)
C210	0.0365 (9)	0.0460 (12)	0.0457 (10)	−0.0028 (9)	0.0248 (8)	−0.0028 (9)
C211	0.0397 (9)	0.0643 (17)	0.0409 (11)	0.0019 (10)	0.0150 (8)	−0.0088 (10)
C212	0.0320 (8)	0.0442 (12)	0.0331 (8)	−0.0051 (8)	0.0159 (7)	−0.0028 (8)
C213	0.0356 (9)	0.0524 (14)	0.0381 (9)	0.0109 (9)	0.0204 (7)	0.0020 (9)
C214	0.0314 (8)	0.0517 (13)	0.0343 (9)	−0.0037 (9)	0.0160 (7)	−0.0001 (8)

Geometric parameters (Å, º)

N1—C12	1.325 (2)	N21—C212	1.316 (2)
N1—C13	1.352 (2)	N21—C213	1.351 (2)
N2—C14	1.337 (2)	N22—C214	1.340 (2)
N2—C13	1.340 (2)	N22—C213	1.343 (2)
N3—C12	1.337 (2)	N23—C212	1.341 (2)
N3—C14	1.347 (2)	N23—C214	1.357 (2)
N4—C13	1.337 (2)	N24—C213	1.329 (2)
N4—H4A	0.8600	N24—H24A	0.8600
N4—H4B	0.8600	N24—H24B	0.8600
N5—C14	1.337 (2)	N25—C214	1.340 (2)
N5—H5A	0.8600	N25—H25A	0.8600
N5—H5B	0.8600	N25—H25B	0.8600
N6—C11	1.136 (3)	N26—C211	1.141 (2)
C1—C2	1.378 (2)	C21—C22	1.375 (2)
C1—C10	1.397 (3)	C21—C210	1.404 (2)
C1—H1	0.9300	C21—H21	0.9300
C2—C3	1.425 (3)	C22—C23	1.429 (2)
C2—C11	1.443 (3)	C22—C211	1.444 (2)
C3—C4	1.369 (3)	C23—C24	1.368 (2)
C3—C12	1.488 (2)	C23—C212	1.488 (2)
C4—C5	1.412 (3)	C24—C25	1.412 (3)
C4—H4	0.9300	C24—H24	0.9300
C5—C10	1.413 (3)	C25—C26	1.414 (2)
C5—C6	1.415 (3)	C25—C210	1.414 (3)
C6—C7	1.366 (4)	C26—C27	1.364 (3)
C6—H6	0.9300	C26—H26	0.9300
C7—C8	1.402 (5)	C27—C28	1.398 (3)
C7—H7	0.9300	C27—H27	0.9300
C8—C9	1.349 (4)	C28—C29	1.342 (3)
C8—H8	0.9300	C28—H28	0.9300
C9—C10	1.420 (3)	C29—C210	1.415 (3)
C9—H9	0.9300	C29—H29	0.9300
C12—N1—C13	114.13 (15)	C212—N21—C213	115.00 (15)
C14—N2—C13	114.67 (15)	C214—N22—C213	114.09 (15)
C12—N3—C14	113.74 (15)	C212—N23—C214	113.13 (14)
C13—N4—H4A	120.0	C213—N24—H24A	120.0
C13—N4—H4B	120.0	C213—N24—H24B	120.0
H4A—N4—H4B	120.0	H24A—N24—H24B	120.0
C14—N5—H5A	120.0	C214—N25—H25A	120.0
C14—N5—H5B	120.0	C214—N25—H25B	120.0
H5A—N5—H5B	120.0	H25A—N25—H25B	120.0
C2—C1—C10	121.7 (2)	C22—C21—C210	121.92 (17)
C2—C1—H1	119.2	C22—C21—H21	119.0
C10—C1—H1	119.2	C210—C21—H21	119.0
C1—C2—C3	119.68 (18)	C21—C22—C23	120.29 (16)
C1—C2—C11	117.03 (19)	C21—C22—C211	114.23 (16)
C3—C2—C11	123.26 (16)	C23—C22—C211	125.43 (16)
C4—C3—C2	118.72 (16)	C24—C23—C22	117.62 (16)
C4—C3—C12	119.29 (17)	C24—C23—C212	121.48 (16)
C2—C3—C12	121.95 (16)	C22—C23—C212	120.90 (15)
C3—C4—C5	122.35 (19)	C23—C24—C25	123.21 (17)
C3—C4—H4	118.8	C23—C24—H24	118.4
C5—C4—H4	118.8	C25—C24—H24	118.4
C4—C5—C10	118.41 (19)	C24—C25—C26	123.25 (18)
C4—C5—C6	121.8 (2)	C24—C25—C210	118.50 (16)
C10—C5—C6	119.8 (2)	C26—C25—C210	118.25 (18)
C7—C6—C5	120.0 (3)	C27—C26—C25	120.4 (2)
C7—C6—H6	120.0	C27—C26—H26	119.8
C5—C6—H6	120.0	C25—C26—H26	119.8
C6—C7—C8	120.2 (3)	C26—C27—C28	120.9 (2)
C6—C7—H7	119.9	C26—C27—H27	119.5
C8—C7—H7	119.9	C28—C27—H27	119.5
C9—C8—C7	120.9 (2)	C29—C28—C27	120.2 (2)
C9—C8—H8	119.5	C29—C28—H28	119.9
C7—C8—H8	119.5	C27—C28—H28	119.9
C8—C9—C10	121.0 (3)	C28—C29—C210	121.0 (2)
C8—C9—H9	119.5	C28—C29—H29	119.5
C10—C9—H9	119.5	C210—C29—H29	119.5
C1—C10—C5	119.13 (18)	C21—C210—C25	118.43 (16)
C1—C10—C9	122.8 (2)	C21—C210—C29	122.37 (18)
C5—C10—C9	118.0 (2)	C25—C210—C29	119.19 (17)
N6—C11—C2	173.9 (2)	N26—C211—C22	167.7 (2)
N1—C12—N3	126.72 (16)	N21—C212—N23	126.70 (16)
N1—C12—C3	117.74 (16)	N21—C212—C23	115.11 (15)
N3—C12—C3	115.52 (15)	N23—C212—C23	118.18 (15)
N4—C13—N2	117.57 (16)	N24—C213—N22	118.44 (16)
N4—C13—N1	117.39 (16)	N24—C213—N21	116.61 (16)
N2—C13—N1	125.04 (16)	N22—C213—N21	124.95 (15)
N2—C14—N5	117.86 (16)	N22—C214—N25	116.99 (16)
N2—C14—N3	125.60 (16)	N22—C214—N23	126.13 (16)
N5—C14—N3	116.54 (16)	N25—C214—N23	116.87 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N22	0.86	2.32	3.171 (2)	172
N5—H5B···N23^i	0.86	2.30	3.132 (2)	163
N24—H24A···N2	0.86	2.16	2.984 (2)	161
N24—H24B···N26^ii	0.86	2.30	3.078 (3)	150
N25—H25B···N3^iii	0.86	2.28	3.096 (2)	158

Symmetry codes: (i) x, −y, z−1/2; (ii) −x, y, −z+1/2; (iii) x, −y, z+1/2.