1,6,7,12,13,18-Hexa­aza­tri­naphthyl­ene tetra­chloro­form solvate

The title compound, 1,6,7,12,13,18-hexa­aza­tri­naphthyl­ene (HATN) tetra­chloro­form solvate, C₂₄H₁₂N₆·4CH₃Cl, belongs to a series of planar bridging ligands with an extensive delocalized π-electron system. The planar mol­ecules pack in pairs with a π–π stacking of a symmetry-related quinoline moiety and are surounded by solvent mol­ecules of chloro­form. The latter are involved in C—H...N contacts with the six pyrazine N atoms.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.036
• wR factor = 0.064
• Data-to-parameter ratio = 15.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



GOODF_01  Alert B The least squares goodness of fit parameter lies
          outside the range 0.60 <> 4.00
          Goodness of fit given =      0.569

RINTA_01  Alert B The value of Rint is greater than 0.15
          Rint given   0.168

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and _chemical_formula_moiety. This is
          usually due to the moiety formula being in the wrong format.
          Atom count from _chemical_formula_sum:   C28 H16 Cl12 N6
          Atom count from _chemical_formula_moiety:C28 H20 Cl8 N6


 0 Alert Level A = Potentially serious problem

 2 Alert Level B = Potential problem

 0 Alert Level C = Please check

---

S1. Comment

Hexaazatrinaphthalene (HATN) is one of a series of compounds which contain three sites for possible bidentate coordination to a metal center. It is thought that delocalization of the π-electron system may provide facile electronic communication between coordinated metal centers leading to interesting physical properties. The parent compound of this series, 1,4,5,8,9,12-hexaazatriphenylene (HAT), has recently been reported to form a robust (10,3)-a network containing chiral micropres on coordinating Ag^I (Abrahams at al., 1998). The chemistry of ruthenium(II) (Kirsch-De Mesmaeker et al., 1989; Rutherford et al., 1997) and mixed Ru^II/Os^II (Rutherford et al., 1998) complexes of HAT have also been studied. The hexaphenyl derivative of HAT has been used to form a number of capped polymetallic complexes with copper(I) and silver(I) (Baxter, Lehn, Baum et al., 1993; Baxter, Lehn, Baum & Fenske, 1999; Baxter, Lehn, Kneisel et al., 1999). The synthesis of a number of HAT derivatives have been reported (Rademacher et al., 1994) and the crystal structure of HAT-hexacarboxamide was published in 1996 (Beeson et al., 1996). The crystal structures of a number of mono- and binuclear Pd^II and Re^I complexes with the hexamethyl derivative of HATN have been reported (Catalano et al., 1994). Two trinuclear copper(I) complexes were recently synthesized (Okubo et al., 1999) using the HAT–hexacarbonitrile anion, which was prepared electrolytically. The complexes were found to exhibit anion-trapping behaviour in the solid state and in solution.

The title compound, (I), crystallizes with four molecules of CHCl₃ per molecule of HATN. The molecule is planar with a maxium deviation for atom N3 of 0.034 Å from the best least-squares plane through all of the non-H atoms comprising the molecule (Fig. 1). The pattern of bond distances and angles in HATN does not suggest a regular delocalized congujated system as observed in HAT–hexacarboxamide (Beeson et al., 1996). The central six-membered ring has three short fused bonds C1—C2, C3—C4 and C5—C6 [average value 1.425 (2) Å] and three long non-fused bonds C2—C3, C4—C5 and C6—C1 [average value 1.479 (2) Å]. The same pattern was observed in HAT–hexacarboxamide (Beeson et al., 1996) but with slightly shorter distances, i.e. 1.405 (10) Å and 1.457 (6) Å, respectively. The remainder of the carbon–carbon bonds have an average value of 1.42 (1) Å except two bonds in the outer fused benzene rings. Surprisingly, here the average value is 1.351 (2) Å for bonds C8—C9, C10—C11, C14—C15, C16—C17, C20—C21 and C22—C23.

In the crystal the HATN molecules stack in pairs, related by a center of symmetry. These `dimers' stack up the a axis and are surounded by solvent molecules of chloroform (Fig. 2). Each pyrazine N atom is involved in a C—H···N contact with the chloroform solvent molecules. Details are given in Table 2. The symmetry-related quinoline moieties involving atoms N1/N2/C1/C7–C12/C2 [symmetry code: 1 - x, 1 - y, 1 - z], are overlapped with an average non-bonded interatomic distance of 3.66 (1) Å. This is larger than the expected van der Waals separation of ca 3.2 Å for π-complexation of aromatic rings. In contrast, it was found that molecules of HAT–hexacarboxamide (Beeson et al., 1996) also stack in pairs but with an average separation of 3.31 (9) Å, indicating the presence of π-complexation.

S2. Experimental

Hexaketocyclohexane octahydrate (1.0 g, 3.20 mmol) and 1,2-phenylenediamine (1.14 g, 10.5 mmol) were added to 200 ml of absolute ethanol. The reaction mixture was refluxed for 12 h after which the solution was cooled to room temperature. The pale-orange precipitate formed was filtered off and dried under vacuum. Recrystallization from CHCl₃ gave extremely thin orange plate-like crystals.

S3. Refinement

The R_int value is rather high which is probably due to the poor quality of the crystal and its thinness. Less than one third of the unique reflections can be considered to be observed and the observed reflections to parameter ratio is only 4.3. The aromatic H atoms were placed in calculated positions and treated as riding atoms using SHELXL97 default parameters. The CHCl₃ H atoms were located from Fourier difference maps and refined isotropically.

Computing details

Data collection: EXPOSE (Stoe, 2000); cell refinement: CELL (Stoe, 2000); data reduction: INTEGRATE (Stoe, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON99 (Spek, 1990); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. PLATON (Spek, 1990) plot of (I) (displacement ellipsoids at the 50% probability level).
	Fig. 2. Packing diagram of the title compound viewed down the b axis, showing the CHCl3 solvent molecules between pairs of HATN molecules and the C–H···N interactions.

(I)

Crystal data

C24H12N6·4CH2Cl2	F(000) = 1720
Mr = 861.87	Dx = 1.665 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.1170 (13) Å	Cell parameters from 4774 reflections
b = 11.6285 (6) Å	θ = 2.0–25.9°
c = 19.9737 (16) Å	µ = 1.00 mm^−1
β = 101.624 (10)°	T = 223 K
V = 3439.1 (4) Å^3	Plate, orange
Z = 4	0.35 × 0.15 × 0.10 mm

Data collection

STOE IPDS diffractometer	1836 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.168
Graphite monochromator	θmax = 25.9°, θmin = 2.0°
Detector resolution: 0.81 pixels mm^-1	h = −18→18
ϕ oscillation scans	k = −14→13
26548 measured reflections	l = −24→24
6626 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 0.57	w = 1/[σ^2(Fo^2) + (0.0002P)^2] where P = (Fo^2 + 2Fc^2)/3
6626 reflections	(Δ/σ)max = 0.003
431 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.24 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	0.3994 (2)	0.3252 (4)	0.45947 (17)	0.0282 (11)
N2	0.4092 (2)	0.5338 (4)	0.38857 (17)	0.0276 (10)
N3	0.4669 (2)	0.5341 (4)	0.26793 (17)	0.0279 (10)
N4	0.5205 (2)	0.3247 (4)	0.21489 (18)	0.0280 (11)
N5	0.5068 (3)	0.1231 (4)	0.28136 (18)	0.0265 (11)
N6	0.4454 (3)	0.1240 (4)	0.40601 (19)	0.0300 (11)
C1	0.4275 (3)	0.3290 (4)	0.4004 (2)	0.0230 (12)
C2	0.4321 (3)	0.4345 (5)	0.3652 (2)	0.0238 (13)
C3	0.4644 (3)	0.4347 (5)	0.2994 (2)	0.0259 (13)
C4	0.4907 (3)	0.3289 (5)	0.2729 (2)	0.0247 (13)
C5	0.4842 (3)	0.2196 (5)	0.3091 (2)	0.0264 (13)
C6	0.4530 (3)	0.2202 (5)	0.3718 (2)	0.0233 (12)
C7	0.3770 (3)	0.4266 (5)	0.4850 (2)	0.0283 (13)
C8	0.3483 (3)	0.4279 (5)	0.5487 (2)	0.0369 (15)
H8	0.3452	0.3591	0.5728	0.044*
C9	0.3256 (3)	0.5290 (6)	0.5741 (2)	0.0432 (16)
H9	0.3070	0.5300	0.6162	0.052*
C10	0.3295 (3)	0.6330 (5)	0.5384 (2)	0.0399 (15)
H10	0.3134	0.7023	0.5571	0.048*
C11	0.3560 (3)	0.6338 (5)	0.4777 (2)	0.0367 (15)
H11	0.3575	0.7035	0.4542	0.044*
C12	0.3814 (3)	0.5309 (5)	0.4494 (2)	0.0280 (12)
C13	0.4973 (3)	0.5312 (5)	0.2072 (2)	0.0280 (13)
C14	0.5020 (3)	0.6343 (5)	0.1710 (2)	0.0369 (15)
H14	0.4843	0.7041	0.1880	0.044*
C15	0.5320 (3)	0.6326 (5)	0.1119 (2)	0.0381 (15)
H15	0.5339	0.7013	0.0873	0.046*
C16	0.5608 (3)	0.5277 (5)	0.0862 (2)	0.0374 (15)
H16	0.5828	0.5282	0.0454	0.045*
C17	0.5568 (3)	0.4275 (5)	0.1197 (2)	0.0355 (15)
H17	0.5752	0.3588	0.1018	0.043*
C18	0.5250 (3)	0.4258 (5)	0.1816 (2)	0.0267 (13)
C19	0.4998 (3)	0.0243 (5)	0.3153 (2)	0.0295 (13)
C20	0.5237 (3)	−0.0822 (5)	0.2899 (2)	0.0342 (14)
H20	0.5435	−0.0844	0.2482	0.041*
C21	0.5186 (3)	−0.1809 (5)	0.3247 (2)	0.0371 (14)
H21	0.5348	−0.2509	0.3070	0.045*
C22	0.4891 (3)	−0.1796 (5)	0.3870 (2)	0.0369 (14)
H22	0.4863	−0.2488	0.4108	0.044*
C23	0.4646 (3)	−0.0801 (5)	0.4133 (3)	0.0355 (14)
H23	0.4443	−0.0810	0.4547	0.043*
C24	0.4695 (3)	0.0250 (5)	0.3790 (2)	0.0262 (13)
C31	0.2832 (4)	0.6825 (5)	0.2673 (3)	0.0392 (16)
H31	0.338 (3)	0.667 (4)	0.287 (2)	0.049 (18)*
Cl31	0.23065 (9)	0.54928 (13)	0.24764 (8)	0.0568 (4)
Cl32	0.28716 (10)	0.76000 (14)	0.19267 (7)	0.0589 (5)
Cl33	0.22771 (10)	0.76198 (15)	0.32036 (7)	0.0634 (5)
C41	0.4534 (4)	0.0932 (5)	0.1037 (3)	0.0569 (18)
H41	0.454 (3)	0.124 (4)	0.154 (3)	0.083 (19)*
Cl41	0.40452 (12)	0.19691 (17)	0.04394 (8)	0.0847 (6)
Cl42	0.38381 (13)	−0.02646 (18)	0.09672 (8)	0.0969 (6)
Cl43	0.56067 (12)	0.0580 (2)	0.09175 (9)	0.1032 (8)
C51	0.2667 (4)	0.0902 (5)	0.4851 (2)	0.0421 (15)
H51	0.331 (3)	0.133 (4)	0.4715 (19)	0.043 (14)*
Cl51	0.21582 (12)	−0.01231 (16)	0.42567 (7)	0.0825 (6)
Cl52	0.29716 (10)	0.02419 (17)	0.56579 (7)	0.0765 (6)
Cl53	0.18975 (10)	0.20203 (14)	0.48962 (7)	0.0623 (5)
C61	0.7089 (4)	0.1680 (4)	0.2435 (2)	0.0341 (14)
H61	0.644 (3)	0.164 (4)	0.231 (2)	0.061 (18)*
Cl61	0.75584 (10)	0.23592 (14)	0.18163 (7)	0.0588 (5)
Cl62	0.74293 (10)	0.02317 (13)	0.25315 (8)	0.0554 (4)
Cl63	0.73841 (11)	0.23977 (14)	0.32198 (7)	0.0641 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.027 (3)	0.035 (3)	0.023 (2)	0.001 (2)	0.0065 (19)	−0.001 (2)
N2	0.032 (3)	0.032 (3)	0.021 (2)	0.001 (2)	0.0112 (18)	0.000 (2)
N3	0.030 (2)	0.024 (3)	0.029 (2)	−0.003 (2)	0.0055 (19)	0.005 (2)
N4	0.032 (3)	0.029 (3)	0.027 (2)	−0.001 (2)	0.014 (2)	0.004 (2)
N5	0.029 (3)	0.023 (3)	0.028 (2)	0.000 (2)	0.007 (2)	−0.001 (2)
N6	0.037 (3)	0.023 (3)	0.032 (3)	0.000 (2)	0.011 (2)	−0.003 (2)
C1	0.026 (3)	0.023 (4)	0.021 (3)	−0.001 (2)	0.005 (2)	−0.001 (2)
C2	0.017 (3)	0.021 (4)	0.031 (3)	0.003 (3)	0.001 (2)	−0.004 (3)
C3	0.033 (3)	0.023 (4)	0.024 (3)	0.005 (3)	0.010 (2)	−0.001 (2)
C4	0.019 (3)	0.024 (4)	0.032 (3)	−0.002 (2)	0.008 (2)	0.001 (2)
C5	0.023 (3)	0.031 (4)	0.025 (3)	−0.001 (3)	0.006 (2)	−0.001 (3)
C6	0.020 (3)	0.022 (4)	0.026 (3)	−0.004 (2)	0.000 (2)	0.002 (2)
C7	0.028 (3)	0.030 (4)	0.029 (3)	0.000 (3)	0.010 (2)	−0.004 (3)
C8	0.048 (4)	0.039 (4)	0.026 (3)	0.000 (3)	0.014 (3)	0.001 (3)
C9	0.057 (4)	0.051 (5)	0.027 (3)	0.000 (3)	0.018 (3)	−0.006 (3)
C10	0.048 (4)	0.036 (4)	0.040 (3)	0.002 (3)	0.019 (3)	−0.012 (3)
C11	0.042 (4)	0.036 (4)	0.035 (3)	−0.004 (3)	0.016 (3)	−0.005 (3)
C12	0.034 (3)	0.021 (4)	0.029 (3)	−0.004 (3)	0.007 (2)	−0.006 (3)
C13	0.030 (3)	0.033 (4)	0.022 (3)	−0.005 (3)	0.007 (2)	−0.002 (3)
C14	0.051 (4)	0.023 (4)	0.039 (3)	−0.003 (3)	0.016 (3)	0.007 (3)
C15	0.042 (4)	0.043 (5)	0.030 (3)	0.004 (3)	0.010 (3)	0.010 (3)
C16	0.035 (3)	0.055 (5)	0.025 (3)	0.006 (3)	0.012 (2)	0.009 (3)
C17	0.037 (3)	0.049 (5)	0.024 (3)	−0.001 (3)	0.016 (3)	−0.001 (3)
C18	0.027 (3)	0.028 (4)	0.026 (3)	−0.001 (3)	0.007 (2)	0.002 (3)
C19	0.023 (3)	0.029 (4)	0.037 (3)	−0.001 (3)	0.007 (2)	0.005 (3)
C20	0.039 (4)	0.027 (4)	0.036 (3)	−0.001 (3)	0.008 (3)	−0.006 (3)
C21	0.043 (4)	0.021 (4)	0.046 (3)	−0.001 (3)	0.006 (3)	0.003 (3)
C22	0.045 (4)	0.018 (4)	0.047 (3)	−0.001 (3)	0.008 (3)	0.007 (3)
C23	0.041 (4)	0.028 (4)	0.040 (3)	−0.002 (3)	0.016 (3)	0.008 (3)
C24	0.025 (3)	0.028 (4)	0.025 (3)	0.000 (3)	0.006 (2)	0.001 (3)
C31	0.041 (4)	0.036 (4)	0.041 (3)	−0.004 (3)	0.008 (3)	−0.002 (3)
Cl31	0.0549 (11)	0.0387 (11)	0.0712 (9)	−0.0071 (8)	−0.0007 (8)	−0.0025 (9)
Cl32	0.0648 (11)	0.0558 (13)	0.0574 (10)	0.0074 (9)	0.0155 (8)	0.0210 (9)
Cl33	0.0703 (11)	0.0659 (14)	0.0552 (10)	0.0200 (10)	0.0152 (8)	−0.0128 (9)
C41	0.076 (5)	0.062 (5)	0.033 (3)	−0.018 (4)	0.013 (3)	−0.006 (3)
Cl41	0.0939 (14)	0.0822 (16)	0.0742 (11)	−0.0152 (12)	0.0075 (10)	0.0135 (10)
Cl42	0.1248 (16)	0.0756 (16)	0.0979 (13)	−0.0355 (14)	0.0406 (12)	−0.0031 (11)
Cl43	0.0674 (13)	0.150 (2)	0.0898 (14)	0.0051 (13)	0.0093 (10)	−0.0476 (13)
C51	0.045 (4)	0.042 (4)	0.043 (3)	−0.007 (3)	0.017 (3)	−0.005 (3)
Cl51	0.1141 (14)	0.0657 (15)	0.0626 (10)	0.0028 (12)	0.0059 (10)	−0.0261 (10)
Cl52	0.0567 (10)	0.1175 (18)	0.0513 (9)	−0.0028 (11)	0.0015 (8)	0.0233 (10)
Cl53	0.0645 (11)	0.0586 (13)	0.0671 (10)	0.0014 (9)	0.0210 (8)	−0.0083 (8)
C61	0.041 (4)	0.033 (4)	0.030 (3)	0.007 (3)	0.011 (3)	−0.002 (3)
Cl61	0.0773 (11)	0.0550 (13)	0.0534 (9)	−0.0044 (9)	0.0356 (8)	0.0076 (8)
Cl62	0.0696 (10)	0.0359 (10)	0.0615 (8)	0.0108 (9)	0.0152 (7)	0.0048 (9)
Cl63	0.0858 (12)	0.0661 (14)	0.0402 (9)	0.0137 (10)	0.0119 (8)	−0.0156 (8)

Geometric parameters (Å, º)

N1—C1	1.332 (5)	C15—C16	1.426 (7)
N1—C7	1.355 (6)	C15—H15	0.9400
N2—C2	1.318 (5)	C16—C17	1.350 (7)
N2—C12	1.364 (5)	C16—H16	0.9400
N3—C3	1.319 (6)	C17—C18	1.415 (6)
N3—C13	1.382 (5)	C17—H17	0.9400
N4—C4	1.325 (5)	C19—C20	1.412 (7)
N4—C18	1.360 (6)	C19—C24	1.437 (5)
N5—C5	1.327 (6)	C20—C21	1.352 (7)
N5—C19	1.348 (6)	C20—H20	0.9400
N6—C6	1.327 (6)	C21—C22	1.405 (6)
N6—C24	1.352 (6)	C21—H21	0.9400
C1—C2	1.423 (6)	C22—C23	1.351 (7)
C1—C6	1.472 (6)	C22—H22	0.9400
C2—C3	1.491 (6)	C23—C24	1.410 (6)
C3—C4	1.428 (6)	C23—H23	0.9400
C4—C5	1.475 (6)	C31—Cl33	1.742 (5)
C5—C6	1.425 (6)	C31—Cl31	1.750 (6)
C7—C8	1.423 (6)	C31—Cl32	1.754 (5)
C7—C12	1.414 (6)	C31—H31	0.87 (4)
C8—C9	1.352 (7)	C41—Cl43	1.735 (6)
C8—H8	0.9400	C41—Cl41	1.753 (6)
C9—C10	1.410 (7)	C41—Cl42	1.733 (6)
C9—H9	0.9400	C41—H41	1.06 (5)
C10—C11	1.352 (6)	C51—Cl51	1.747 (5)
C10—H10	0.9400	C51—Cl52	1.761 (5)
C11—C12	1.409 (6)	C51—Cl53	1.759 (5)
C11—H11	0.9400	C51—H51	1.17 (4)
C13—C14	1.409 (6)	C61—Cl61	1.734 (5)
C13—C18	1.422 (6)	C61—Cl62	1.760 (5)
C14—C15	1.347 (6)	C61—Cl63	1.753 (5)
C14—H14	0.9400	C61—H61	0.96 (4)
C1—N1—C7	116.9 (4)	C17—C16—C15	120.9 (5)
C2—N2—C12	116.4 (4)	C17—C16—H16	119.6
C3—N3—C13	116.3 (4)	C15—C16—H16	119.6
C4—N4—C18	117.0 (5)	C16—C17—C18	120.1 (5)
C5—N5—C19	117.3 (4)	C16—C17—H17	119.9
C6—N6—C24	116.9 (4)	C18—C17—H17	119.9
N1—C1—C2	121.5 (5)	N4—C18—C17	119.9 (5)
N1—C1—C6	118.0 (5)	N4—C18—C13	121.5 (4)
C2—C1—C6	120.4 (4)	C17—C18—C13	118.6 (5)
N2—C2—C1	122.5 (4)	N5—C19—C20	121.0 (5)
N2—C2—C3	117.9 (5)	N5—C19—C24	120.8 (5)
C1—C2—C3	119.6 (5)	C20—C19—C24	118.2 (5)
N3—C3—C4	122.8 (4)	C21—C20—C19	121.0 (5)
N3—C3—C2	117.8 (5)	C21—C20—H20	119.5
C4—C3—C2	119.4 (5)	C19—C20—H20	119.5
N4—C4—C3	121.7 (5)	C20—C21—C22	120.4 (5)
N4—C4—C5	117.7 (5)	C20—C21—H21	119.8
C3—C4—C5	120.7 (5)	C22—C21—H21	119.8
N5—C5—C6	122.0 (5)	C23—C22—C21	120.9 (5)
N5—C5—C4	118.4 (4)	C23—C22—H22	119.5
C6—C5—C4	119.6 (5)	C21—C22—H22	119.5
N6—C6—C5	121.8 (5)	C22—C23—C24	120.6 (5)
N6—C6—C1	117.9 (4)	C22—C23—H23	119.7
C5—C6—C1	120.3 (5)	C24—C23—H23	119.7
N1—C7—C8	119.3 (5)	N6—C24—C23	120.0 (4)
N1—C7—C12	121.1 (4)	N6—C24—C19	121.2 (5)
C8—C7—C12	119.6 (5)	C23—C24—C19	118.8 (5)
C9—C8—C7	119.4 (5)	Cl33—C31—Cl31	110.7 (3)
C9—C8—H8	120.3	Cl33—C31—Cl32	110.4 (3)
C7—C8—H8	120.3	Cl31—C31—Cl32	110.8 (3)
C8—C9—C10	121.1 (5)	Cl33—C31—H31	111 (3)
C8—C9—H9	119.5	Cl31—C31—H31	105 (3)
C10—C9—H9	119.5	Cl32—C31—H31	108 (3)
C11—C10—C9	120.6 (5)	Cl43—C41—Cl41	110.2 (3)
C11—C10—H10	119.7	Cl43—C41—Cl42	111.6 (4)
C9—C10—H10	119.7	Cl41—C41—Cl42	109.4 (3)
C10—C11—C12	120.6 (5)	Cl43—C41—H41	112 (3)
C10—C11—H11	119.7	Cl41—C41—H41	109 (3)
C12—C11—H11	119.7	Cl42—C41—H41	104 (3)
N2—C12—C11	119.6 (5)	Cl51—C51—Cl52	108.8 (3)
N2—C12—C7	121.6 (5)	Cl51—C51—Cl53	109.5 (3)
C11—C12—C7	118.8 (4)	Cl52—C51—Cl53	109.2 (3)
N3—C13—C14	119.3 (5)	Cl51—C51—H51	114 (2)
N3—C13—C18	120.7 (5)	Cl52—C51—H51	108.6 (19)
C14—C13—C18	120.0 (4)	Cl53—C51—H51	107 (2)
C15—C14—C13	119.9 (5)	Cl61—C61—Cl62	111.2 (3)
C15—C14—H14	120.1	Cl61—C61—Cl63	110.7 (3)
C13—C14—H14	120.1	Cl62—C61—Cl63	110.0 (3)
C14—C15—C16	120.6 (5)	Cl61—C61—H61	112 (3)
C14—C15—H15	119.7	Cl62—C61—H61	104 (3)
C16—C15—H15	119.7	Cl63—C61—H61	108 (3)
C7—N1—C1—C2	−1.1 (6)	C8—C9—C10—C11	0.0 (8)
C7—N1—C1—C6	179.5 (4)	C9—C10—C11—C12	−0.8 (8)
C12—N2—C2—C1	0.7 (6)	C2—N2—C12—C11	179.9 (4)
C12—N2—C2—C3	−178.9 (4)	C2—N2—C12—C7	−0.4 (6)
N1—C1—C2—N2	0.0 (7)	C10—C11—C12—N2	−179.1 (4)
C6—C1—C2—N2	179.4 (4)	C10—C11—C12—C7	1.2 (7)
N1—C1—C2—C3	179.6 (4)	N1—C7—C12—N2	−0.7 (7)
C6—C1—C2—C3	−1.0 (6)	C8—C7—C12—N2	179.5 (4)
C13—N3—C3—C4	−0.4 (6)	N1—C7—C12—C11	179.0 (4)
C13—N3—C3—C2	179.9 (4)	C8—C7—C12—C11	−0.8 (7)
N2—C2—C3—N3	−1.0 (6)	C3—N3—C13—C14	−179.8 (4)
C1—C2—C3—N3	179.4 (4)	C3—N3—C13—C18	−0.7 (6)
N2—C2—C3—C4	179.3 (4)	N3—C13—C14—C15	179.7 (4)
C1—C2—C3—C4	−0.3 (6)	C18—C13—C14—C15	0.6 (7)
C18—N4—C4—C3	0.0 (6)	C13—C14—C15—C16	−1.3 (7)
C18—N4—C4—C5	179.1 (4)	C14—C15—C16—C17	1.5 (7)
N3—C3—C4—N4	0.8 (7)	C15—C16—C17—C18	−0.9 (7)
C2—C3—C4—N4	−179.5 (4)	C4—N4—C18—C17	179.5 (4)
N3—C3—C4—C5	−178.2 (4)	C4—N4—C18—C13	−1.2 (6)
C2—C3—C4—C5	1.4 (6)	C16—C17—C18—N4	179.5 (4)
C19—N5—C5—C6	−0.5 (7)	C16—C17—C18—C13	0.2 (7)
C19—N5—C5—C4	−179.7 (4)	N3—C13—C18—N4	1.5 (7)
N4—C4—C5—N5	−1.1 (6)	C14—C13—C18—N4	−179.4 (4)
C3—C4—C5—N5	177.9 (4)	N3—C13—C18—C17	−179.1 (4)
N4—C4—C5—C6	179.7 (4)	C14—C13—C18—C17	0.0 (7)
C3—C4—C5—C6	−1.3 (6)	C5—N5—C19—C20	−179.1 (4)
C24—N6—C6—C5	0.6 (7)	C5—N5—C19—C24	−0.4 (6)
C24—N6—C6—C1	−179.8 (4)	N5—C19—C20—C21	178.5 (5)
N5—C5—C6—N6	0.4 (7)	C24—C19—C20—C21	−0.2 (7)
C4—C5—C6—N6	179.6 (4)	C19—C20—C21—C22	0.1 (7)
N5—C5—C6—C1	−179.2 (4)	C20—C21—C22—C23	0.5 (7)
C4—C5—C6—C1	−0.1 (6)	C21—C22—C23—C24	−0.9 (7)
N1—C1—C6—N6	0.9 (6)	C6—N6—C24—C23	178.9 (4)
C2—C1—C6—N6	−178.4 (4)	C6—N6—C24—C19	−1.5 (6)
N1—C1—C6—C5	−179.4 (4)	C22—C23—C24—N6	−179.6 (5)
C2—C1—C6—C5	1.2 (6)	C22—C23—C24—C19	0.7 (7)
C1—N1—C7—C8	−178.8 (4)	N5—C19—C24—N6	1.4 (7)
C1—N1—C7—C12	1.5 (6)	C20—C19—C24—N6	−179.9 (4)
N1—C7—C8—C9	−179.8 (5)	N5—C19—C24—C23	−178.9 (4)
C12—C7—C8—C9	0.0 (7)	C20—C19—C24—C23	−0.2 (6)
C7—C8—C9—C10	0.4 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C31—H31···N2	0.87 (4)	2.60 (4)	3.260 (7)	134 (4)
C31—H31···N3	0.87 (4)	2.57 (5)	3.268 (7)	138 (4)
C41—H41···N5	1.06 (5)	2.51 (5)	3.493 (6)	154 (4)
C51—H51···N1	1.17 (4)	2.50 (4)	3.489 (6)	141 (3)
C51—H51···N6	1.17 (4)	2.37 (4)	3.415 (6)	147 (3)
C61—H61···N4	0.96 (4)	2.62 (5)	3.332 (7)	132 (4)
C61—H61···N5	0.96 (4)	2.53 (5)	3.333 (7)	141 (4)