N-(2-Amino­benz­yl)-N,N-bis­(quinolin-2-ylmeth­yl)amine

The title new diquinaldine derivative, C₂₇H₂₄N₄, forms mol­ecular assemblies organized by inter­molecular quinoline [pi]-[pi] stacking [3.356 (3) and 3.440 (3) Å] and both inter- and intra­molecular N-H...N hydrogen bonds [3.039 (3)-3.104 (3) Å and 129 (2)-172 (2)°]. The combination of such inter­actions provides readily definable contacts that propagate along each crystallographic axis.

S1. Comment

Different types of arene–arene non-covalent interactions lead to fascinating molecular architectures and supramolecular structure in solids. We have recently shown by NMR spectroscopy (Mitra, Seaton, Assarpour & Williamson et al., 1998; Mitra, Seaton, Capitani & Assarpour, 1998) that such interactions can also be a prevelant theme in solutions. In our continuing study of π–π interactions and their effect on ¹H NMR spectra, we wanted to study the consequence of interactions between aromatic and heteroaromatic groups. To this end we synthesized a molecule that contains both arene and quinoline components. 2-Aminobenzylamine is an interesting molecule that consists of two amino groups that have different reactivity profiles. Selective N-alkylation of the benzylic amine with two equivalents of 2-(bromomethyl)quinoline gave the title compound, (I).

The molecular conformation of (I), as it exists in the crystal, is influenced by several close intramolecular contacts. As shown in Fig. 1, the anilino H4B atom participtes in a bifurcated contact with nearby tertiary amino (N1) and quinoline (N3) acceptor groups (Table 1). This hydrogen-bond motif results in the anilino and quinoline fragments adopting a roughly planar alignment with an interplanar angle of 16.66 (8)°. Selected geometric parameters are given in Table 2.

Inspection of the crystal structure reveals translationally related molecules linked by N–H···N hydrogen bonds to form a catemeric motif along the b axis (Fig. 2). These molecular assemblies, described by C(9) graph-set notation (Bernstein et al., 1995), result from the association of neighboring anilino (H4A) and quinoline (N2) groups. Another noteworthy feature of this structure is the contribution of π–π interactions to the crystal packing. As shown in Fig. 2, each of the quinoline groups forms centrosymmetric dimeric motifs [for example quinoline(N3)–quinoline(N3ⁱ) = 3.356 (3) Å and quinoline(N2)–quinoline(N2ⁱⁱ) = 3.440 (3) Å)] that link the hydrogen-bonded molecular chains along the a and c axes. Since molecules of (I) contain two nearly orthogonally positioned quinoline fragments [the interplanar angle is 81.75 (4)°], the combination of such π–π interactions and hydrogen bonds provides readily definable contacts that contribute to the overall three-dimensional organization.

S2. Experimental

2-(Bromomethyl)quinoline (0.222 g, 1.0 mmol) was reacted with 2-aminobenzylamine (0.0.061 g, 0.5 mmol) in CH₃CN (5 ml) in the presence of anhydrous K₂CO₃ (0.152 g, 1.1 mmol) under N₂ at room temperature for 16 h. The reaction mixture was concentrated under reduced pressure and directly chromatographed by flash column chromatography (SiO₂ gel) using a solvent gradient from 5 to 10% MeOH/CH₂Cl₂. Fractions containing the pure product were combined, concentrated under reduced pressure and recrystallized from CHCl₃/n-heptane to give (I) (0.110 g, 55% yield) as a white powder (m.p. 473–476 K). UV–Vis [MeOH; λ_max; nm; (ε)]: 232?(56200), 303?(6570), 316?(6940). IR (KBr; cm^-1): 3351, 3186, 1602, 1565, 743. ¹H NMR (0.005 M in CDCl₃); δ 3.82 (s, 2H, benzyl-CH₂), 4.01 (s, 4H, quinolyl-CH₂), 5.20 (br s, 2H, NH₂), 6.64 (t, J = 7.5 Hz, H-5'), 6.66 (d, J = 6.9 Hz, 1H, H-3'), 7.07 (t, J = 7.5 Hz, 1H, H-4'), 7.11 (d, J = 7.5 Hz, 1H, H-6'), 7.50 (m, 2H, H-6), 7.51 (d, J = 8.1 Hz, 2H, H-3'), 7.69, (ddd, 2H, J = 8.3, 6.9 and 1.4 Hz, 2H, H-7), 7.75 (d, J = 8.1 Hz, 2H, H-5), 8.04 (d, J = 8.1 Hz, 2H, H-4), 8.06 (d, J = 8.3 Hz, 2H, H-8). ¹³C NMR (CDCl₃): δ 159.2 (C2), 147.6 (C8a), 147.0 (C2'), 136.3 (C4), 131.5 (C6'), 129.4 (C7), 128.9 (C8), 128.6 (C4'), 127.5 (C5), 127.3 (C4a), 126.2 (C6), 122.2 (C1'), 121.3 (C3), 117.1 (C5'),115.4 (C3'), 60.9 (CH₂), 58.4 (CH_2').

S3. Refinement

The anilino H atoms (H4A and H4B) were located in a difference density map and their parameters were refined freely. The remaining H atoms were treated as riding, with C—H distances of 0.95 (aromatic) and 0.99 Å (CH₂) [U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2002) and XPREP (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED.

Figures

	Fig. 1. The molecular structure and labeling scheme of (I) (50% probability displacement elipsoids), showing an intramolecular bifurcated interaction (dotted line).
	Fig. 2. A view of the packing of (I), showing the catemeric hydrogen-bond network and π-stacking of the quinoline fragments. H atoms have been omitted for clarity. [Symmetry codes: (i) -x, 1 - y, -z; (ii) 1 - x, 2 - y, -z; (iii) x, y - 1, z.]

N-(2-Aminobenzyl)-N,N-bis(quinolin-2-ylmethyl)amine

Crystal data

C27H24N4	F(000) = 856
Mr = 404.50	Dx = 1.282 Mg m^−3
MonoclinicP21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3239 reflections
a = 12.4071 (16) Å	θ = 5.5–53.8°
b = 7.9834 (10) Å	µ = 0.08 mm^−1
c = 21.376 (3) Å	T = 100 K
β = 98.041 (2)°	Transparent needle, colorless
V = 2096.5 (5) Å^3	0.38 × 0.04 × 0.03 mm
Z = 4

Data collection

Bruker APEX-II CCD area-detector diffractometer	4699 independent reflections
Radiation source: fine-focus sealed tube	3089 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
φ and ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→15
Tmin = 0.971, Tmax = 0.998	k = −10→10
14852 measured reflections	l = −27→27

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0569P)^2 + 0.5447P] where P = (Fo^2 + 2Fc^2)/3
4699 reflections	(Δ/σ)max < 0.001
288 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.23 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
N1	0.31203 (14)	0.81463 (19)	0.17491 (7)	0.0167 (4)
N2	0.38292 (14)	1.1433 (2)	0.07494 (8)	0.0177 (4)
N3	0.15326 (14)	0.5904 (2)	0.12313 (7)	0.0178 (4)
N4	0.37564 (16)	0.4398 (2)	0.16790 (9)	0.0232 (4)
C1	0.38390 (18)	0.9509 (2)	0.16202 (9)	0.0181 (5)
H1A	0.4602	0.9206	0.1780	0.022*
H1B	0.3653	1.0530	0.1845	0.022*
C2	0.37363 (17)	0.9863 (2)	0.09240 (9)	0.0176 (5)
C3	0.35704 (17)	0.8517 (2)	0.04863 (9)	0.0200 (5)
H3	0.3491	0.7403	0.0630	0.024*
C4	0.35267 (17)	0.8846 (2)	−0.01413 (10)	0.0193 (5)
H4	0.3431	0.7957	−0.0439	0.023*
C5	0.36232 (16)	1.0511 (2)	−0.03495 (9)	0.0176 (5)
C6	0.35938 (17)	1.0952 (3)	−0.09919 (10)	0.0213 (5)
H6	0.3494	1.0105	−0.1307	0.026*
C7	0.37071 (18)	1.2578 (3)	−0.11648 (10)	0.0226 (5)
H7	0.3684	1.2862	−0.1598	0.027*
C8	0.38581 (18)	1.3835 (3)	−0.06998 (10)	0.0233 (5)
H8	0.3940	1.4967	−0.0823	0.028*
C9	0.38884 (18)	1.3458 (2)	−0.00765 (10)	0.0212 (5)
H9	0.3983	1.4325	0.0231	0.025*
C10	0.37789 (16)	1.1778 (2)	0.01157 (9)	0.0181 (5)
C11	0.19838 (17)	0.8672 (2)	0.16677 (9)	0.0175 (5)
H11A	0.1907	0.9682	0.1396	0.021*
H11B	0.1793	0.8996	0.2086	0.021*
C12	0.11772 (17)	0.7377 (2)	0.13815 (9)	0.0176 (5)
C13	0.00605 (18)	0.7839 (3)	0.12818 (10)	0.0209 (5)
H13	−0.0160	0.8912	0.1408	0.025*
C14	−0.06876 (18)	0.6731 (3)	0.10046 (10)	0.0232 (5)
H14	−0.1436	0.7028	0.0931	0.028*
C15	−0.03476 (18)	0.5131 (2)	0.08251 (9)	0.0192 (5)
C16	−0.10710 (18)	0.3892 (3)	0.05350 (10)	0.0234 (5)
H16	−0.1826	0.4134	0.0438	0.028*
C17	−0.06929 (19)	0.2366 (3)	0.03951 (10)	0.0239 (5)
H17	−0.1185	0.1539	0.0207	0.029*
C18	0.04253 (18)	0.1998 (3)	0.05268 (10)	0.0231 (5)
H18	0.0682	0.0924	0.0425	0.028*
C19	0.11492 (18)	0.3178 (2)	0.08011 (9)	0.0193 (5)
H19	0.1903	0.2919	0.0885	0.023*
C20	0.07766 (17)	0.4762 (2)	0.09564 (9)	0.0184 (5)
C21	0.34498 (17)	0.7398 (2)	0.23747 (9)	0.0185 (5)
H21A	0.2882	0.6599	0.2465	0.022*
H21B	0.3500	0.8293	0.2698	0.022*
C22	0.45217 (18)	0.6499 (2)	0.24264 (9)	0.0185 (5)
C23	0.46258 (18)	0.5027 (2)	0.20754 (9)	0.0193 (5)
C24	0.56236 (18)	0.4168 (3)	0.21622 (10)	0.0218 (5)
H24	0.5696	0.3157	0.1937	0.026*
C25	0.65032 (19)	0.4772 (3)	0.25708 (10)	0.0244 (5)
H25	0.7176	0.4185	0.2619	0.029*
C26	0.64041 (18)	0.6235 (3)	0.29100 (10)	0.0231 (5)
H26	0.7004	0.6652	0.3192	0.028*
C27	0.54226 (18)	0.7071 (3)	0.28319 (10)	0.0219 (5)
H27	0.5359	0.8074	0.3063	0.026*
H4A	0.383 (2)	0.344 (3)	0.1418 (13)	0.050 (8)*
H4B	0.321 (2)	0.519 (3)	0.1520 (12)	0.045 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0181 (10)	0.0139 (8)	0.0180 (9)	0.0001 (7)	0.0022 (7)	0.0021 (7)
N2	0.0177 (10)	0.0162 (9)	0.0194 (9)	0.0007 (7)	0.0030 (7)	0.0011 (7)
N3	0.0206 (10)	0.0155 (9)	0.0178 (9)	0.0000 (7)	0.0038 (7)	0.0014 (7)
N4	0.0238 (11)	0.0163 (9)	0.0282 (11)	0.0030 (8)	−0.0014 (8)	−0.0050 (8)
C1	0.0218 (12)	0.0129 (10)	0.0198 (11)	−0.0007 (9)	0.0036 (9)	−0.0005 (8)
C2	0.0161 (11)	0.0173 (10)	0.0196 (11)	0.0008 (8)	0.0030 (8)	−0.0015 (8)
C3	0.0226 (13)	0.0150 (10)	0.0227 (11)	−0.0018 (9)	0.0037 (9)	−0.0004 (8)
C4	0.0190 (12)	0.0171 (10)	0.0217 (11)	−0.0018 (9)	0.0029 (9)	−0.0059 (8)
C5	0.0129 (11)	0.0189 (10)	0.0209 (11)	−0.0006 (8)	0.0020 (8)	−0.0006 (8)
C6	0.0170 (12)	0.0256 (11)	0.0211 (11)	−0.0011 (9)	0.0022 (9)	−0.0028 (9)
C7	0.0210 (12)	0.0283 (12)	0.0187 (11)	0.0010 (10)	0.0028 (9)	0.0035 (9)
C8	0.0249 (13)	0.0184 (11)	0.0269 (12)	0.0039 (9)	0.0045 (10)	0.0061 (9)
C9	0.0240 (13)	0.0147 (10)	0.0249 (12)	0.0025 (9)	0.0039 (9)	−0.0003 (8)
C10	0.0146 (11)	0.0195 (11)	0.0204 (11)	0.0010 (9)	0.0026 (8)	−0.0002 (8)
C11	0.0188 (12)	0.0131 (10)	0.0208 (11)	0.0025 (8)	0.0034 (9)	−0.0027 (8)
C12	0.0214 (12)	0.0169 (10)	0.0150 (10)	0.0030 (9)	0.0039 (8)	0.0025 (8)
C13	0.0216 (12)	0.0171 (10)	0.0244 (11)	0.0035 (9)	0.0051 (9)	−0.0003 (8)
C14	0.0183 (12)	0.0235 (11)	0.0282 (12)	0.0028 (9)	0.0045 (9)	−0.0002 (9)
C15	0.0198 (12)	0.0198 (11)	0.0181 (11)	0.0005 (9)	0.0027 (9)	0.0029 (8)
C16	0.0169 (12)	0.0272 (12)	0.0255 (12)	−0.0008 (9)	0.0005 (9)	0.0028 (9)
C17	0.0266 (13)	0.0203 (11)	0.0233 (12)	−0.0075 (10)	−0.0017 (9)	−0.0019 (9)
C18	0.0289 (14)	0.0163 (10)	0.0239 (12)	0.0000 (9)	0.0026 (10)	−0.0021 (9)
C19	0.0187 (12)	0.0185 (10)	0.0201 (11)	0.0027 (9)	0.0003 (9)	0.0018 (8)
C20	0.0229 (13)	0.0173 (10)	0.0149 (10)	−0.0026 (9)	0.0027 (9)	0.0012 (8)
C21	0.0222 (12)	0.0165 (10)	0.0177 (11)	0.0007 (9)	0.0059 (9)	0.0003 (8)
C22	0.0249 (13)	0.0153 (10)	0.0160 (10)	0.0015 (9)	0.0056 (9)	0.0041 (8)
C23	0.0231 (12)	0.0177 (10)	0.0179 (11)	0.0001 (9)	0.0054 (9)	0.0039 (8)
C24	0.0263 (13)	0.0179 (11)	0.0218 (11)	0.0008 (9)	0.0056 (9)	0.0016 (8)
C25	0.0230 (13)	0.0263 (12)	0.0241 (12)	0.0062 (10)	0.0041 (9)	0.0054 (9)
C26	0.0212 (13)	0.0252 (11)	0.0214 (11)	0.0006 (9)	−0.0020 (9)	0.0031 (9)
C27	0.0293 (13)	0.0189 (11)	0.0173 (11)	0.0001 (9)	0.0030 (9)	0.0008 (8)

Geometric parameters (Å, º)

N1—C1	1.457 (3)	C11—H11B	0.9900
N1—C11	1.458 (3)	C12—C13	1.421 (3)
N1—C21	1.469 (2)	C13—C14	1.357 (3)
N2—C2	1.317 (2)	C13—H13	0.9500
N2—C10	1.375 (3)	C14—C15	1.415 (3)
N3—C12	1.311 (3)	C14—H14	0.9500
N3—C20	1.379 (3)	C15—C20	1.415 (3)
N4—C23	1.370 (3)	C15—C16	1.419 (3)
N4—H4A	0.96 (3)	C16—C17	1.354 (3)
N4—H4B	0.95 (3)	C16—H16	0.9500
C1—C2	1.502 (3)	C17—C18	1.408 (3)
C1—H1A	0.9900	C17—H17	0.9500
C1—H1B	0.9900	C18—C19	1.375 (3)
C2—C3	1.421 (3)	C18—H18	0.9500
C3—C4	1.361 (3)	C19—C20	1.402 (3)
C3—H3	0.9500	C19—H19	0.9500
C4—C5	1.412 (3)	C21—C22	1.502 (3)
C4—H4	0.9500	C21—H21A	0.9900
C5—C10	1.412 (3)	C21—H21B	0.9900
C5—C6	1.413 (3)	C22—C27	1.392 (3)
C6—C7	1.362 (3)	C22—C23	1.410 (3)
C6—H6	0.9500	C23—C24	1.405 (3)
C7—C8	1.407 (3)	C24—C25	1.386 (3)
C7—H7	0.9500	C24—H24	0.9500
C8—C9	1.362 (3)	C25—C26	1.389 (3)
C8—H8	0.9500	C25—H25	0.9500
C9—C10	1.415 (3)	C26—C27	1.378 (3)
C9—H9	0.9500	C26—H26	0.9500
C11—C12	1.508 (3)	C27—H27	0.9500
C11—H11A	0.9900
C1—N1—C11	111.7 (2)	C13—C12—C11	117.43 (18)
C1—N1—C21	112.1 (2)	C14—C13—C12	119.30 (19)
C11—N1—C21	111.5 (2)	C14—C13—H13	120.3
C2—N2—C10	118.43 (17)	C12—C13—H13	120.3
C12—N3—C20	117.73 (18)	C13—C14—C15	119.7 (2)
C23—N4—H4A	121.1 (16)	C13—C14—H14	120.2
C23—N4—H4B	115.9 (15)	C15—C14—H14	120.2
H4A—N4—H4B	116 (2)	C20—C15—C14	117.20 (19)
N1—C1—C2	111.00 (16)	C20—C15—C16	119.18 (19)
N1—C1—H1A	109.4	C14—C15—C16	123.6 (2)
C2—C1—H1A	109.4	C17—C16—C15	120.4 (2)
N1—C1—H1B	109.4	C17—C16—H16	119.8
C2—C1—H1B	109.4	C15—C16—H16	119.8
H1A—C1—H1B	108.0	C16—C17—C18	120.4 (2)
N2—C2—C3	122.90 (18)	C16—C17—H17	119.8
N2—C2—C1	117.44 (17)	C18—C17—H17	119.8
C3—C2—C1	119.64 (17)	C19—C18—C17	120.6 (2)
C4—C3—C2	119.03 (18)	C19—C18—H18	119.7
C4—C3—H3	120.5	C17—C18—H18	119.7
C2—C3—H3	120.5	C18—C19—C20	120.1 (2)
C3—C4—C5	119.94 (18)	C18—C19—H19	119.9
C3—C4—H4	120.0	C20—C19—H19	119.9
C5—C4—H4	120.0	N3—C20—C19	118.05 (19)
C4—C5—C10	117.47 (18)	N3—C20—C15	122.67 (18)
C4—C5—C6	123.30 (19)	C19—C20—C15	119.28 (19)
C10—C5—C6	119.22 (18)	N1—C21—C22	113.08 (16)
C7—C6—C5	120.77 (19)	N1—C21—H21A	109.0
C7—C6—H6	119.6	C22—C21—H21A	109.0
C5—C6—H6	119.6	N1—C21—H21B	109.0
C6—C7—C8	119.78 (19)	C22—C21—H21B	109.0
C6—C7—H7	120.1	H21A—C21—H21B	107.8
C8—C7—H7	120.1	C27—C22—C23	118.6 (2)
C9—C8—C7	121.09 (19)	C27—C22—C21	120.98 (18)
C9—C8—H8	119.5	C23—C22—C21	120.35 (18)
C7—C8—H8	119.5	N4—C23—C24	120.37 (19)
C8—C9—C10	120.22 (19)	N4—C23—C22	120.8 (2)
C8—C9—H9	119.9	C24—C23—C22	118.78 (19)
C10—C9—H9	119.9	C25—C24—C23	121.0 (2)
N2—C10—C5	122.21 (18)	C25—C24—H24	119.5
N2—C10—C9	118.88 (18)	C23—C24—H24	119.5
C5—C10—C9	118.91 (18)	C24—C25—C26	120.2 (2)
N1—C11—C12	115.26 (16)	C24—C25—H25	119.9
N1—C11—H11A	108.5	C26—C25—H25	119.9
C12—C11—H11A	108.5	C27—C26—C25	119.0 (2)
N1—C11—H11B	108.5	C27—C26—H26	120.5
C12—C11—H11B	108.5	C25—C26—H26	120.5
H11A—C11—H11B	107.5	C26—C27—C22	122.36 (19)
N3—C12—C13	123.39 (19)	C26—C27—H27	118.8
N3—C12—C11	119.17 (19)	C22—C27—H27	118.8
C11—N1—C1—C2	−73.2 (2)	C12—C13—C14—C15	0.6 (3)
C21—N1—C1—C2	160.86 (16)	C13—C14—C15—C20	0.9 (3)
C10—N2—C2—C3	−1.0 (3)	C13—C14—C15—C16	179.8 (2)
C10—N2—C2—C1	177.59 (18)	C20—C15—C16—C17	1.1 (3)
N1—C1—C2—N2	145.02 (19)	C14—C15—C16—C17	−177.8 (2)
N1—C1—C2—C3	−36.4 (3)	C15—C16—C17—C18	−1.0 (3)
N2—C2—C3—C4	1.4 (3)	C16—C17—C18—C19	0.2 (3)
C1—C2—C3—C4	−177.1 (2)	C17—C18—C19—C20	0.4 (3)
C2—C3—C4—C5	−1.3 (3)	C12—N3—C20—C19	−179.28 (18)
C3—C4—C5—C10	0.9 (3)	C12—N3—C20—C15	0.9 (3)
C3—C4—C5—C6	179.5 (2)	C18—C19—C20—N3	179.93 (18)
C4—C5—C6—C7	−179.0 (2)	C18—C19—C20—C15	−0.3 (3)
C10—C5—C6—C7	−0.4 (3)	C14—C15—C20—N3	−1.7 (3)
C5—C6—C7—C8	0.2 (3)	C16—C15—C20—N3	179.31 (18)
C6—C7—C8—C9	−0.3 (3)	C14—C15—C20—C19	178.49 (18)
C7—C8—C9—C10	0.7 (3)	C16—C15—C20—C19	−0.5 (3)
C2—N2—C10—C5	0.5 (3)	C1—N1—C21—C22	−66.8 (2)
C2—N2—C10—C9	−179.39 (19)	C11—N1—C21—C22	167.12 (16)
C4—C5—C10—N2	−0.5 (3)	N1—C21—C22—C27	114.6 (2)
C6—C5—C10—N2	−179.18 (19)	N1—C21—C22—C23	−67.1 (2)
C4—C5—C10—C9	179.45 (19)	C27—C22—C23—N4	178.78 (19)
C6—C5—C10—C9	0.7 (3)	C21—C22—C23—N4	0.4 (3)
C8—C9—C10—N2	179.0 (2)	C27—C22—C23—C24	1.9 (3)
C8—C9—C10—C5	−0.9 (3)	C21—C22—C23—C24	−176.47 (18)
C1—N1—C11—C12	142.47 (17)	N4—C23—C24—C25	−178.7 (2)
C21—N1—C11—C12	−91.2 (2)	C22—C23—C24—C25	−1.8 (3)
C20—N3—C12—C13	0.7 (3)	C23—C24—C25—C26	1.0 (3)
C20—N3—C12—C11	−178.46 (17)	C24—C25—C26—C27	−0.2 (3)
N1—C11—C12—N3	0.3 (3)	C25—C26—C27—C22	0.3 (3)
N1—C11—C12—C13	−178.89 (17)	C23—C22—C27—C26	−1.2 (3)
N3—C12—C13—C14	−1.5 (3)	C21—C22—C27—C26	177.18 (19)
C11—C12—C13—C14	177.66 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···N3	0.95 (3)	2.17 (3)	3.039 (3)	152 (2)
N4—H4B···N1	0.95 (3)	2.42 (3)	3.104 (3)	129 (2)
N4—H4A···N2^i	0.96 (3)	2.15 (3)	3.100 (2)	172 (2)

Symmetry code: (i) x, y−1, z.