5-Nitro-2,3-bis(2-pyridyl)­quinoxaline

In the crystal structure of the title compound, C₁₈H₁₁N₅O₂, two crystallographically independent mol­ecules having the same composition and cis–cis conformation (arrangement of the pyridyl rings) are observed. A C—H...N hydrogen bond links the centrosymmetrically related mol­ecules into a discrete pair [C...N = 3.462 (4) Å], and the structure is stabilized further by π–π-stacking interactions between aromatic rings from two adjacent dimers.

S1. Comment

Polypyridyl bridging ligands have attracted much attention as building blocks for supramolecular assemblies in recent years (Leininger et al., 2000; Bu et al., 2001). Some of the polypyridyl compounds have also been actively studied, such as 2,3-bis(2-pyridyl)quinoxaline and its derivatives which represent an important class of chelating agents, because of the potential functionality of their metal complexes as molecular devices and DNA probes (Holmlin & Barton 1995; Balzani et al., 1998a; Balzani et al., 1998b). In our efforts to systematically investigate the syntheses, molecular structures and coordination chemistry of such compounds, we have reported the crystal structures of 5,6-bis(2-pyridyl)-2,3-pyrazine-dicarbonitrile (Du et al., 2001), and? the so-called proton-sponge compounds 2,3-di-2-pyridinio-5,8-dimethoxyquinoxaline dinitrate (Liu et al., 2001) and 2,3-di-2-pyridinio-5-nitroquinoxaline diperchlorate (Xu et al., 2002). In this contribution, we report the synthesis and crystal structure of the title compound, (I), namely 2,3-di-2-pyridyl-5-nitroquinoxaline.

Compound (I) consists of a quinoxaline ring substituted with two pyridyl rings and a nitro group. Theoretically, such compounds have the potential to generate three possible configurations under appropriate conditions (referring to the relation of the pyridyl N atoms to the central quinoxaline ring) as depicted in Fig. 1, viz. cis–cis, cis–trans and trans–trans. The crystal structure of the title compound contains two symmetry-independent molecules, A and B, that have the same composition. Note that the two molecules have the unexpected cis–cis conformational arrangement of the pyridyl rings (Figs. 2a and 2 b); the favored orientation of the pyridyl rings is such that their N atoms face one another. We have recently reported a novel box-like dinuclear Ag^I complex of the title compound (I), in which (I) takes the cis–trans configuration (Liu & Du, 2002), that is, the configuration of (I) is spontaneously converted when coordinated to an Ag^I center. In addition, in the crystal structure of the N-protonated perchlorate of the title compound (Xu et al., 2002), the unexpected trans–trans configuration is observed.

In the structure of (I), two pyridyl rings within the same molecule are not coplanar with one another or with the quinoxaline ring due to steric hindrance between the pyridyl ring H atoms. The dihedral angles of the pyridyl rings are 60.3 (4) and 110.1 (4)° in the two independent molecules, respectively. The N_py···N_py separation is 3.048 (3) Å for molecule A and 3.191 (5) Å for molecule B. In fact, the existence of the adjacent pyridine substituents causes a substantial out-of-plane twist, even in the quinoxaline rings [C11A—C2A—C3A—C16A = 21.5 (3)° and C11B—C2B—C3B—C16B = −19.9 (3)°]. In the quinoxaline rings, the mean deviations from the best-fit planes describing the rings are 0.0697 (3) and 0.0572 (4) Å for molecules A and B, respectively. The quinoxaline rings make dihedral angles with the two pyridyl rings of 36.8 (2) and 39.8 (4)° in molecule A, and 146.1 (4) and 54.3 (3)° in molecule B. The N2A—C3A, N1A—C2A, N2B—C3B and N1B—C2B bond distances (mean 1.316 Å) are noticeably shorter than the N2A—C4A, N1A—C9A, N2B—C4B and N1B—C9B distances (mean 1.369 Å), which is typical for the structural geometry of the quinoxaline system (Rasmussen et al., 1990). All N—C bond lengths are well within the range of values normally considered standard for C—N single (1.47 Å) and C=N double bonds (1.28 Å).

There exists a single directed intermolecular C18A—H18A···N4Bⁱ(i = −x + 1, −y + 1, −z + 1) weak interaction [C···N = 3.462 (4) Å and C18A—H18A···N4Bⁱ = 167.2°], which links molecule A and an adjacent centrosymmetrically related molecule B' to form a dimer (Table 2). Furthermore, the neighboring B molecules in the structure show a substantial π–π-stacking interaction (as depicted in Fig. 3), which further stabilizes the crystal structure. The closest approach between the quinoxaline systems is 3.4 Å, with the molecular stack stretching along the a direction. Examination of the structure with PLATON (Spek, 2003) showed that there were no solvent-accessible voids in the crystal lattice of (I).

S2. Experimental

The title compound was synthesized and purified, according to the method described by Xu et al. (2002), by the reaction of 1-nitro-2,3-phenylenediamine and 2,2'-pyridil (yield 80%). The spectral and elemental analysis data are satisfactory. ¹H NMR (400 MHz, CDCl₃): 7.24–7.30 (m, 2H), 7.85–7.90 (m, 3H), 8.00 (d, 1H, J = 8.0 Hz), 8.22 (t, 2H, J = 6.8 Hz), 8.28 (d, 1H, J = 8.0 Hz), 8.39 (d, 1H, J = 4.0 Hz), 8.43 (d, 1H, J = 8.8 Hz). Analysis calculated for C₃₆H₂₂N₁₀O₄: C 65.64, H 3.37, N 18.23%. Found: C 65.55, H 3.64, N 18.26%. Light-yellow cubic single crystals of (I) suitable for X-ray diffraction were obtained by recrystallized from hot C₂H₅OH solution.

S3. Refinement

H atoms were placed in calculated positions and included in the final refinement in a riding model approximation, with displacement parameters derived from the parent C atoms.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998).

Figures

Chart I Fig. 1 The three possible of configurations of (I) and its derivatives. Fig. 2 ORTEPII (Johnson, 1976) views of the two independent molecules of (I), with displacement ellipsoids shown at the 30% probability level. Fig. 3 A view of the hydrogen bonding and π–π-stacking interactions in the unit cell of (I).

2,3-Bis(2-pyridyl)-5-nitroquinoxaline

Crystal data

C18H11N5O2	Z = 4
Mr = 329.32	F(000) = 680
Triclinic, P1	Dx = 1.383 Mg m^−3
a = 10.942 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.630 (4) Å	Cell parameters from 6571 reflections
c = 12.906 (4) Å	θ = 1.6–25.0°
α = 104.615 (6)°	µ = 0.10 mm^−1
β = 93.419 (6)°	T = 293 K
γ = 93.292 (6)°	Block, light yellow
V = 1581.9 (9) Å^3	0.30 × 0.25 × 0.20 mm

Data collection

BRUKER SMART 1000 diffractometer	3032 reflections with I > 2σ(I)
ω scans	Rint = 0.020
Absorption correction: multi-scan [SAINT (Bruker, 1998) and SADABS (Sheldrick, 1997)]	θmax = 25.0°
Tmin = 0.972, Tmax = 0.981	h = −13→10
6614 measured reflections	k = −13→13
5555 independent reflections	l = −15→15

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.046	w = 1/[σ^2(Fo^2) + (0.04008P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.108	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.16 e Å^−3
5555 reflections	Δρmin = −0.21 e Å^−3
451 parameters

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. Full-MATRIX

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1A	0.4294 (2)	0.6747 (2)	1.08972 (19)	0.1115 (9)
O2A	0.5001 (3)	0.8310 (2)	1.21246 (17)	0.1377 (11)
O1B	0.1138 (2)	0.74721 (19)	0.62915 (15)	0.0843 (6)
O2B	0.06350 (19)	0.90419 (18)	0.74291 (14)	0.0912 (7)
N5A	0.69236 (19)	0.72762 (17)	0.69946 (15)	0.0575 (5)
N4A	0.44151 (19)	0.65551 (16)	0.57717 (14)	0.0540 (5)
N2A	0.50281 (18)	0.75969 (17)	0.91000 (14)	0.0518 (5)
N1A	0.37466 (17)	0.88717 (16)	0.78519 (14)	0.0488 (5)
N3A	0.4451 (3)	0.7826 (3)	1.1257 (2)	0.0884 (8)
N5B	−0.1694 (2)	0.68801 (19)	0.20064 (18)	0.0688 (6)
N4B	0.0942 (2)	0.66360 (19)	0.10761 (17)	0.0722 (7)
N2B	0.02787 (17)	0.79157 (16)	0.43310 (15)	0.0480 (5)
N1B	0.13996 (17)	0.91742 (16)	0.30006 (14)	0.0454 (5)
N3B	0.1023 (2)	0.8542 (2)	0.65775 (17)	0.0637 (6)
C20A	0.7932 (3)	0.6752 (3)	0.6662 (2)	0.0773 (8)
H20A	0.8371	0.7046	0.6178	0.093*
C19A	0.8362 (3)	0.5812 (3)	0.6986 (3)	0.0909 (10)
H19A	0.9066	0.5472	0.6720	0.109*
C18A	0.7733 (3)	0.5377 (2)	0.7714 (3)	0.0846 (9)
H18A	0.8009	0.4743	0.7958	0.101*
C17A	0.6685 (3)	0.5897 (2)	0.8076 (2)	0.0653 (7)
H17A	0.6239	0.5620	0.8567	0.078*
C16A	0.6307 (2)	0.6842 (2)	0.76925 (17)	0.0468 (6)
C3A	0.5223 (2)	0.74853 (18)	0.80856 (17)	0.0425 (6)
C2A	0.4487 (2)	0.80544 (19)	0.74314 (17)	0.0430 (6)
C11A	0.44550 (19)	0.77232 (19)	0.62358 (16)	0.0402 (5)
C15A	0.4420 (2)	0.8578 (2)	0.56684 (17)	0.0469 (6)
H15A	0.4453	0.9383	0.6023	0.056*
C14A	0.4335 (2)	0.8214 (2)	0.45626 (19)	0.0551 (7)
H14A	0.4308	0.8771	0.4158	0.066*
C13A	0.4291 (2)	0.7030 (2)	0.40711 (19)	0.0641 (7)
H13A	0.4236	0.6764	0.3326	0.077*
C12A	0.4329 (3)	0.6235 (2)	0.46985 (19)	0.0657 (8)
H12A	0.4292	0.5426	0.4356	0.079*
C9A	0.3632 (2)	0.9095 (2)	0.89369 (18)	0.0504 (6)
C8A	0.2934 (2)	1.0035 (2)	0.94439 (19)	0.0622 (7)
H8A	0.2584	1.0517	0.9050	0.075*
C7A	0.2778 (2)	1.0231 (3)	1.0506 (2)	0.0734 (8)
H7A	0.2324	1.0853	1.0839	0.088*
C6A	0.3289 (3)	0.9512 (3)	1.1105 (2)	0.0741 (9)
H6A	0.3174	0.9653	1.1834	0.089*
C5A	0.3959 (3)	0.8598 (3)	1.0623 (2)	0.0668 (8)
C4A	0.4190 (2)	0.8380 (2)	0.95236 (17)	0.0523 (6)
C20B	−0.2706 (3)	0.6166 (3)	0.1665 (3)	0.0940 (11)
H20B	−0.3177	0.6261	0.1072	0.113*
C19B	−0.3093 (4)	0.5295 (4)	0.2142 (4)	0.1198 (16)
H19B	−0.3804	0.4810	0.1869	0.144*
C18B	−0.2428 (4)	0.5144 (3)	0.3021 (4)	0.1093 (14)
H18B	−0.2681	0.4561	0.3357	0.131*
C17B	−0.1367 (3)	0.5881 (2)	0.3404 (2)	0.0782 (9)
H17B	−0.0891	0.5807	0.4002	0.094*
C16B	−0.1040 (2)	0.6729 (2)	0.2865 (2)	0.0538 (7)
C3B	0.0024 (2)	0.76154 (19)	0.32819 (18)	0.0451 (6)
C2B	0.0666 (2)	0.8208 (2)	0.25985 (17)	0.0434 (6)
C11B	0.0606 (2)	0.7737 (2)	0.14047 (18)	0.0485 (6)
C15B	0.0304 (2)	0.8431 (2)	0.07255 (19)	0.0630 (7)
H15B	0.0079	0.9202	0.0996	0.076*
C14B	0.0340 (3)	0.7967 (3)	−0.0359 (2)	0.0775 (8)
H14B	0.0119	0.8411	−0.0838	0.093*
C13B	0.0703 (3)	0.6851 (3)	−0.0721 (2)	0.0879 (10)
H13B	0.0761	0.6522	−0.1450	0.105*
C12B	0.0982 (3)	0.6223 (3)	0.0012 (3)	0.0964 (11)
H12B	0.1217	0.5453	−0.0245	0.116*
C9B	0.1589 (2)	0.95605 (19)	0.40967 (17)	0.0429 (6)
C8B	0.2310 (2)	1.0631 (2)	0.45571 (18)	0.0501 (6)
H8B	0.2640	1.1076	0.4121	0.060*
C7B	0.2522 (2)	1.1012 (2)	0.56463 (19)	0.0544 (6)
H7B	0.2975	1.1732	0.5952	0.065*
C6B	0.2064 (2)	1.0329 (2)	0.63080 (19)	0.0555 (7)
H6B	0.2213	1.0596	0.7050	0.067*
C5B	0.1407 (2)	0.9281 (2)	0.58696 (18)	0.0484 (6)
C4B	0.1098 (2)	0.8871 (2)	0.47499 (17)	0.0436 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.120 (2)	0.1233 (19)	0.1060 (19)	−0.0156 (18)	0.0065 (15)	0.0629 (18)
O2A	0.180 (3)	0.183 (3)	0.0498 (13)	−0.019 (2)	−0.0197 (15)	0.0432 (16)
O1B	0.1088 (17)	0.0803 (14)	0.0773 (14)	0.0128 (13)	0.0129 (12)	0.0424 (12)
O2B	0.1076 (17)	0.1253 (17)	0.0522 (12)	0.0214 (14)	0.0310 (11)	0.0357 (12)
N1A	0.0521 (13)	0.0506 (12)	0.0409 (11)	0.0015 (10)	0.0067 (9)	0.0066 (9)
N2A	0.0525 (13)	0.0602 (13)	0.0431 (12)	−0.0083 (11)	0.0014 (10)	0.0171 (10)
N3A	0.088 (2)	0.132 (3)	0.0522 (17)	−0.015 (2)	0.0086 (14)	0.040 (2)
N4A	0.0805 (16)	0.0410 (12)	0.0393 (12)	0.0015 (11)	0.0008 (10)	0.0095 (10)
N5A	0.0540 (14)	0.0601 (13)	0.0623 (13)	0.0113 (11)	0.0116 (11)	0.0196 (11)
N1B	0.0468 (12)	0.0514 (12)	0.0404 (11)	0.0024 (10)	0.0084 (9)	0.0152 (10)
N2B	0.0464 (12)	0.0534 (12)	0.0491 (12)	0.0041 (10)	0.0112 (10)	0.0204 (10)
N3B	0.0592 (15)	0.0895 (18)	0.0508 (14)	0.0116 (14)	0.0063 (11)	0.0320 (14)
N4B	0.0973 (18)	0.0649 (15)	0.0534 (14)	0.0237 (14)	0.0169 (13)	0.0071 (12)
N5B	0.0498 (14)	0.0714 (15)	0.0719 (16)	−0.0090 (13)	0.0001 (12)	−0.0019 (13)
C20A	0.063 (2)	0.094 (2)	0.082 (2)	0.0262 (18)	0.0163 (16)	0.0274 (18)
C19A	0.073 (2)	0.102 (3)	0.099 (2)	0.039 (2)	0.0042 (19)	0.021 (2)
C18A	0.092 (3)	0.067 (2)	0.093 (2)	0.0276 (19)	−0.024 (2)	0.0200 (18)
C17A	0.075 (2)	0.0604 (17)	0.0621 (17)	0.0034 (16)	−0.0088 (15)	0.0223 (14)
C16A	0.0520 (15)	0.0460 (14)	0.0408 (13)	−0.0008 (12)	−0.0075 (12)	0.0118 (12)
C3A	0.0474 (15)	0.0398 (13)	0.0386 (13)	−0.0073 (11)	0.0003 (11)	0.0099 (11)
C2A	0.0454 (15)	0.0400 (13)	0.0423 (13)	−0.0037 (12)	0.0059 (11)	0.0094 (11)
C11A	0.0413 (14)	0.0419 (14)	0.0396 (13)	0.0030 (11)	0.0070 (10)	0.0136 (11)
C15A	0.0501 (15)	0.0441 (14)	0.0494 (15)	0.0056 (12)	0.0111 (11)	0.0153 (12)
C14A	0.0623 (17)	0.0607 (17)	0.0522 (16)	0.0131 (14)	0.0120 (13)	0.0288 (14)
C13A	0.092 (2)	0.0596 (17)	0.0417 (15)	0.0086 (16)	0.0067 (14)	0.0140 (14)
C12A	0.104 (2)	0.0416 (15)	0.0466 (16)	0.0022 (15)	−0.0038 (15)	0.0048 (13)
C9A	0.0473 (15)	0.0598 (16)	0.0407 (14)	−0.0046 (13)	0.0065 (12)	0.0078 (13)
C8A	0.0548 (17)	0.0715 (18)	0.0512 (16)	−0.0004 (14)	0.0108 (13)	−0.0017 (14)
C7A	0.0559 (18)	0.089 (2)	0.0586 (18)	−0.0115 (16)	0.0150 (15)	−0.0098 (17)
C6A	0.0556 (19)	0.114 (3)	0.0421 (16)	−0.0208 (18)	0.0147 (14)	0.0036 (18)
C5A	0.0599 (18)	0.097 (2)	0.0436 (16)	−0.0179 (17)	0.0073 (13)	0.0237 (16)
C4A	0.0473 (16)	0.0685 (17)	0.0379 (14)	−0.0146 (14)	0.0058 (12)	0.0112 (13)
C20B	0.063 (2)	0.085 (2)	0.111 (3)	−0.0129 (19)	−0.0011 (19)	−0.011 (2)
C19B	0.070 (3)	0.084 (3)	0.183 (5)	−0.020 (2)	0.024 (3)	−0.003 (3)
C18B	0.100 (3)	0.060 (2)	0.169 (4)	−0.016 (2)	0.060 (3)	0.023 (3)
C17B	0.078 (2)	0.0569 (17)	0.104 (2)	−0.0023 (16)	0.0396 (18)	0.0235 (17)
C16B	0.0480 (16)	0.0485 (15)	0.0615 (17)	−0.0008 (13)	0.0211 (13)	0.0048 (14)
C3B	0.0424 (14)	0.0474 (14)	0.0489 (15)	0.0087 (12)	0.0116 (11)	0.0155 (12)
C2B	0.0403 (14)	0.0464 (14)	0.0463 (14)	0.0065 (12)	0.0080 (11)	0.0152 (12)
C11B	0.0456 (15)	0.0545 (16)	0.0455 (14)	−0.0012 (12)	0.0107 (11)	0.0124 (13)
C15B	0.077 (2)	0.0630 (17)	0.0524 (16)	0.0052 (15)	0.0050 (14)	0.0207 (14)
C14B	0.085 (2)	0.100 (2)	0.0482 (18)	−0.005 (2)	−0.0022 (15)	0.0259 (17)
C13B	0.096 (3)	0.113 (3)	0.0430 (17)	−0.004 (2)	0.0086 (17)	0.0006 (19)
C12B	0.135 (3)	0.079 (2)	0.068 (2)	0.023 (2)	0.023 (2)	−0.0020 (19)
C9B	0.0405 (14)	0.0470 (14)	0.0434 (14)	0.0063 (11)	0.0081 (11)	0.0138 (12)
C8B	0.0480 (15)	0.0535 (16)	0.0518 (16)	0.0046 (13)	0.0086 (12)	0.0177 (13)
C7B	0.0489 (16)	0.0537 (16)	0.0572 (16)	0.0053 (13)	0.0038 (12)	0.0075 (14)
C6B	0.0521 (16)	0.0704 (18)	0.0434 (14)	0.0138 (14)	0.0044 (12)	0.0108 (14)
C5B	0.0484 (15)	0.0579 (16)	0.0450 (15)	0.0093 (13)	0.0105 (12)	0.0216 (13)
C4B	0.0373 (14)	0.0521 (15)	0.0445 (14)	0.0087 (12)	0.0089 (11)	0.0159 (12)

Geometric parameters (Å, º)

O1A—N3A	1.221 (3)	C13A—H13A	0.9300
O2A—N3A	1.224 (3)	C12A—H12A	0.9300
N1A—C2A	1.317 (3)	C9A—C4A	1.400 (3)
N1A—C9A	1.373 (3)	C9A—C8A	1.415 (3)
N2A—C3A	1.314 (3)	C8A—C7A	1.355 (3)
N2A—C4A	1.368 (3)	C8A—H8A	0.9300
N3A—C5A	1.463 (4)	C7A—C6A	1.392 (4)
N4A—C11A	1.336 (2)	C7A—H7A	0.9300
N4A—C12A	1.336 (3)	C6A—C5A	1.365 (4)
N5A—C16A	1.336 (3)	C6A—H6A	0.9300
N5A—C20A	1.332 (3)	C5A—C4A	1.417 (3)
O1B—N3B	1.222 (2)	C20B—C19B	1.371 (5)
O2B—N3B	1.220 (2)	C20B—H20B	0.9300
N1B—C2B	1.314 (3)	C19B—C18B	1.365 (5)
N1B—C9B	1.371 (3)	C19B—H19B	0.9300
N2B—C3B	1.318 (3)	C18B—C17B	1.390 (4)
N2B—C4B	1.362 (3)	C18B—H18B	0.9300
N3B—C5B	1.466 (3)	C17B—C16B	1.385 (3)
N4B—C11B	1.324 (3)	C17B—H17B	0.9300
N4B—C12B	1.340 (3)	C16B—C3B	1.488 (3)
N5B—C16B	1.338 (3)	C3B—C2B	1.440 (3)
N5B—C20B	1.328 (3)	C2B—C11B	1.495 (3)
C20A—C19A	1.363 (4)	C11B—C15B	1.371 (3)
C20A—H20A	0.9300	C15B—C14B	1.370 (3)
C19A—C18A	1.375 (4)	C15B—H15B	0.9300
C19A—H19A	0.9300	C14B—C13B	1.355 (4)
C18A—C17A	1.378 (4)	C14B—H14B	0.9300
C18A—H18A	0.9300	C13B—C12B	1.364 (4)
C17A—C16A	1.387 (3)	C13B—H13B	0.9300
C17A—H17A	0.9300	C12B—H12B	0.9300
C16A—C3A	1.486 (3)	C9B—C8B	1.408 (3)
C3A—C2A	1.436 (3)	C9B—C4B	1.410 (3)
C2A—C11A	1.491 (3)	C8B—C7B	1.364 (3)
C11A—C15A	1.376 (3)	C8B—H8B	0.9300
C15A—C14A	1.378 (3)	C7B—C6B	1.400 (3)
C15A—H15A	0.9300	C7B—H7B	0.9300
C14A—C13A	1.359 (3)	C6B—C5B	1.351 (3)
C14A—H14A	0.9300	C6B—H6B	0.9300
C13A—C12A	1.375 (3)	C5B—C4B	1.416 (3)
O1A—N3A—O2A	123.8 (3)	C7A—C6A—H6A	120.0
C2A—N1A—C9A	117.2 (2)	C6A—C5A—C4A	121.7 (3)
C3A—N2A—C4A	116.7 (2)	C6A—C5A—N3A	119.1 (3)
C11A—N4A—C12A	116.4 (2)	C4A—C5A—N3A	119.2 (3)
C16A—N5A—C20A	116.9 (2)	N2A—C4A—C9A	122.0 (2)
O1B—N3B—O2B	124.1 (2)	N2A—C4A—C5A	120.7 (3)
C2B—N1B—C9B	117.69 (19)	C9A—C4A—C5A	116.8 (3)
C3B—N2B—C4B	117.38 (19)	N5B—C20B—C19B	123.3 (4)
C11B—N4B—C12B	115.5 (2)	N5B—C20B—H20B	118.4
C16B—N5B—C20B	117.0 (3)	C19B—C20B—H20B	118.4
O1A—N3A—C5A	118.9 (3)	C18B—C19B—C20B	119.7 (4)
O2A—N3A—C5A	117.3 (3)	C18B—C19B—H19B	120.2
O2B—N3B—C5B	117.7 (2)	C20B—C19B—H19B	120.2
O1B—N3B—C5B	118.2 (2)	C19B—C18B—C17B	118.6 (4)
N5A—C20A—C19A	124.3 (3)	C19B—C18B—H18B	120.7
N5A—C20A—H20A	117.8	C17B—C18B—H18B	120.7
C19A—C20A—H20A	117.8	C16B—C17B—C18B	117.8 (3)
C20A—C19A—C18A	118.5 (3)	C16B—C17B—H17B	121.1
C20A—C19A—H19A	120.8	C18B—C17B—H17B	121.1
C18A—C19A—H19A	120.8	N5B—C16B—C17B	123.6 (3)
C19A—C18A—C17A	118.8 (3)	N5B—C16B—C3B	115.3 (2)
C19A—C18A—H18A	120.6	C17B—C16B—C3B	120.8 (3)
C17A—C18A—H18A	120.6	N2B—C3B—C2B	121.2 (2)
C18A—C17A—C16A	118.7 (3)	N2B—C3B—C16B	116.3 (2)
C18A—C17A—H17A	120.7	C2B—C3B—C16B	122.2 (2)
C16A—C17A—H17A	120.7	N1B—C2B—C3B	121.3 (2)
N5A—C16A—C17A	122.7 (2)	N1B—C2B—C11B	115.77 (19)
N5A—C16A—C3A	115.4 (2)	C3B—C2B—C11B	122.8 (2)
C17A—C16A—C3A	121.7 (2)	N4B—C11B—C15B	123.8 (2)
N2A—C3A—C2A	121.0 (2)	N4B—C11B—C2B	114.3 (2)
N2A—C3A—C16A	116.4 (2)	C15B—C11B—C2B	121.8 (2)
C2A—C3A—C16A	122.35 (19)	C14B—C15B—C11B	118.8 (3)
N1A—C2A—C3A	121.74 (19)	C14B—C15B—H15B	120.6
N1A—C2A—C11A	115.4 (2)	C11B—C15B—H15B	120.6
C3A—C2A—C11A	122.8 (2)	C13B—C14B—C15B	118.9 (3)
N4A—C11A—C15A	123.5 (2)	C13B—C14B—H14B	120.6
N4A—C11A—C2A	115.35 (19)	C15B—C14B—H14B	120.6
C15A—C11A—C2A	121.1 (2)	C14B—C13B—C12B	118.3 (3)
C11A—C15A—C14A	118.5 (2)	C14B—C13B—H13B	120.9
C11A—C15A—H15A	120.8	C12B—C13B—H13B	120.9
C14A—C15A—H15A	120.8	N4B—C12B—C13B	124.7 (3)
C13A—C14A—C15A	119.2 (2)	N4B—C12B—H12B	117.7
C13A—C14A—H14A	120.4	C13B—C12B—H12B	117.7
C15A—C14A—H14A	120.4	N1B—C9B—C8B	119.2 (2)
C14A—C13A—C12A	118.6 (2)	N1B—C9B—C4B	120.1 (2)
C14A—C13A—H13A	120.7	C8B—C9B—C4B	120.6 (2)
C12A—C13A—H13A	120.7	C7B—C8B—C9B	119.7 (2)
N4A—C12A—C13A	123.8 (2)	C7B—C8B—H8B	120.2
N4A—C12A—H12A	118.1	C9B—C8B—H8B	120.2
C13A—C12A—H12A	118.1	C8B—C7B—C6B	120.6 (2)
N1A—C9A—C4A	119.7 (2)	C8B—C7B—H7B	119.7
N1A—C9A—C8A	119.4 (2)	C6B—C7B—H7B	119.7
C4A—C9A—C8A	120.9 (2)	C5B—C6B—C7B	120.0 (2)
C7A—C8A—C9A	119.7 (3)	C5B—C6B—H6B	120.0
C7A—C8A—H8A	120.1	C7B—C6B—H6B	120.0
C9A—C8A—H8A	120.1	C6B—C5B—C4B	122.0 (2)
C8A—C7A—C6A	120.8 (3)	C6B—C5B—N3B	118.7 (2)
C8A—C7A—H7A	119.6	C4B—C5B—N3B	119.3 (2)
C6A—C7A—H7A	119.6	N2B—C4B—C9B	121.3 (2)
C5A—C6A—C7A	120.0 (3)	N2B—C4B—C5B	121.6 (2)
C5A—C6A—H6A	120.0	C9B—C4B—C5B	116.9 (2)
C16A—N5A—C20A—C19A	0.2 (4)	C16B—N5B—C20B—C19B	−0.4 (4)
N5A—C20A—C19A—C18A	−0.9 (5)	N5B—C20B—C19B—C18B	0.7 (6)
C20A—C19A—C18A—C17A	0.9 (4)	C20B—C19B—C18B—C17B	−0.4 (6)
C19A—C18A—C17A—C16A	−0.2 (4)	C19B—C18B—C17B—C16B	−0.2 (5)
C20A—N5A—C16A—C17A	0.6 (3)	C20B—N5B—C16B—C17B	−0.2 (4)
C20A—N5A—C16A—C3A	177.2 (2)	C20B—N5B—C16B—C3B	−174.7 (2)
C18A—C17A—C16A—N5A	−0.6 (4)	C18B—C17B—C16B—N5B	0.5 (4)
C18A—C17A—C16A—C3A	−176.9 (2)	C18B—C17B—C16B—C3B	174.8 (2)
C4A—N2A—C3A—C2A	−6.9 (3)	C4B—N2B—C3B—C2B	5.3 (3)
C4A—N2A—C3A—C16A	167.49 (19)	C4B—N2B—C3B—C16B	−168.56 (19)
N5A—C16A—C3A—N2A	−142.2 (2)	N5B—C16B—C3B—N2B	145.6 (2)
C17A—C16A—C3A—N2A	34.4 (3)	C17B—C16B—C3B—N2B	−29.1 (3)
N5A—C16A—C3A—C2A	32.1 (3)	N5B—C16B—C3B—C2B	−28.2 (3)
C17A—C16A—C3A—C2A	−151.3 (2)	C17B—C16B—C3B—C2B	157.1 (2)
C9A—N1A—C2A—C3A	−5.0 (3)	C9B—N1B—C2B—C3B	3.7 (3)
C9A—N1A—C2A—C11A	172.03 (19)	C9B—N1B—C2B—C11B	−172.9 (2)
N2A—C3A—C2A—N1A	12.4 (3)	N2B—C3B—C2B—N1B	−9.8 (3)
C16A—C3A—C2A—N1A	−161.7 (2)	C16B—C3B—C2B—N1B	163.8 (2)
N2A—C3A—C2A—C11A	−164.4 (2)	N2B—C3B—C2B—C11B	166.6 (2)
C16A—C3A—C2A—C11A	21.5 (3)	C16B—C3B—C2B—C11B	−19.9 (3)
C12A—N4A—C11A—C15A	−0.5 (3)	C12B—N4B—C11B—C15B	0.5 (4)
C12A—N4A—C11A—C2A	177.0 (2)	C12B—N4B—C11B—C2B	−175.3 (2)
N1A—C2A—C11A—N4A	−135.0 (2)	N1B—C2B—C11B—N4B	120.3 (2)
C3A—C2A—C11A—N4A	41.9 (3)	C3B—C2B—C11B—N4B	−56.3 (3)
N1A—C2A—C11A—C15A	42.5 (3)	N1B—C2B—C11B—C15B	−55.6 (3)
C3A—C2A—C11A—C15A	−140.6 (2)	C3B—C2B—C11B—C15B	127.9 (3)
N4A—C11A—C15A—C14A	0.2 (3)	N4B—C11B—C15B—C14B	0.5 (4)
C2A—C11A—C15A—C14A	−177.1 (2)	C2B—C11B—C15B—C14B	176.0 (2)
C11A—C15A—C14A—C13A	−0.1 (3)	C11B—C15B—C14B—C13B	−1.7 (4)
C15A—C14A—C13A—C12A	0.2 (4)	C15B—C14B—C13B—C12B	2.0 (5)
C11A—N4A—C12A—C13A	0.6 (4)	C11B—N4B—C12B—C13B	−0.2 (5)
C14A—C13A—C12A—N4A	−0.5 (4)	C14B—C13B—C12B—N4B	−1.1 (5)
C2A—N1A—C9A—C4A	−6.5 (3)	C2B—N1B—C9B—C8B	−176.23 (19)
C2A—N1A—C9A—C8A	174.5 (2)	C2B—N1B—C9B—C4B	5.7 (3)
N1A—C9A—C8A—C7A	177.5 (2)	N1B—C9B—C8B—C7B	−178.8 (2)
C4A—C9A—C8A—C7A	−1.6 (4)	C4B—C9B—C8B—C7B	−0.8 (3)
C9A—C8A—C7A—C6A	−0.5 (4)	C9B—C8B—C7B—C6B	2.1 (3)
C8A—C7A—C6A—C5A	0.1 (4)	C8B—C7B—C6B—C5B	0.1 (3)
C7A—C6A—C5A—C4A	2.2 (4)	C7B—C6B—C5B—C4B	−3.8 (3)
C7A—C6A—C5A—N3A	−177.8 (2)	C7B—C6B—C5B—N3B	175.3 (2)
O1A—N3A—C5A—C4A	−48.9 (4)	O1B—N3B—C5B—C4B	43.2 (3)
O1A—N3A—C5A—C6A	131.2 (3)	O1B—N3B—C5B—C6B	−135.8 (2)
O2A—N3A—C5A—C4A	131.1 (3)	O2B—N3B—C5B—C6B	42.4 (3)
O2A—N3A—C5A—C6A	−48.9 (4)	O2B—N3B—C5B—C4B	−138.5 (2)
C3A—N2A—C4A—C9A	−4.7 (3)	C3B—N2B—C4B—C9B	4.2 (3)
C3A—N2A—C4A—C5A	−177.3 (2)	C3B—N2B—C4B—C5B	178.4 (2)
N1A—C9A—C4A—N2A	11.8 (3)	N1B—C9B—C4B—N2B	−10.1 (3)
C8A—C9A—C4A—N2A	−169.1 (2)	C8B—C9B—C4B—N2B	171.85 (19)
N1A—C9A—C4A—C5A	−175.3 (2)	N1B—C9B—C4B—C5B	175.40 (19)
C8A—C9A—C4A—C5A	3.7 (3)	C8B—C9B—C4B—C5B	−2.6 (3)
C6A—C5A—C4A—N2A	168.8 (2)	C6B—C5B—C4B—N2B	−169.5 (2)
N3A—C5A—C4A—N2A	−11.1 (4)	N3B—C5B—C4B—N2B	11.5 (3)
C6A—C5A—C4A—C9A	−4.1 (4)	C6B—C5B—C4B—C9B	5.0 (3)
N3A—C5A—C4A—C9A	176.0 (2)	N3B—C5B—C4B—C9B	−174.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C18A—H18A···N4B^i	0.93	2.55	3.462 (4)	167

Symmetry code: (i) −x+1, −y+1, −z+1.