Bis[[mu]-N,N'-bis­(quinolin-8-yl)pyridine-2,6-dicarboxamido]­dizinc(II) dichloro­methane disolvate

The title compound, [Zn₂(C₂₅H₁₅N₅O₂)₂]·2CH₂Cl₂, is a dinuclear double-helical complex which lies on a crystallographic twofold axis. In the complex, both ligands are partitioned into two tridentate domains which allow each ligand to bridge both metal centres. Each Zn^II atom is six-coordinated in a distorted octa­hedral environment formed by two amide N atoms, two quinoline N atoms and two pyridine N atoms from two different ligand mol­ecules, with the central pyridine ring, unusually, bridging two Zn^II atoms. The deprotonated ligand is not planar, the amide side chains being considerably twisted out from the plane of the central pyridine ring.

S1. Comment

The design and construction of double- and triple-helical complexes has attracted intense interest, not only for their fascinating structural and superstructural diversity (Piguet et al., 1997; Elsevier et al., 2003), but also for their potential applications in medicinal chemistry (Richards & Rodger, 2007), nonlinear optics (Serrano & Sierra, 2003), asymmetric catalysis (Yeung et al., 2008) and luminescence (Riis-Johannessen et al., 2009). Since the early pioneering work of Lehn and co-workers on double-helical Cu^I complexes (Sleiman et al., 1995), a wide range of multidentate ligands have been developed for the formation of helicates. Notable examples include the O,O-donor biscatecholates (Albrecht & Schneider, 2002), the all-N-donor mixed pyridyl–thiazole ligands (Rice et al., 2001), the N,O-donor pyrazole–phenol ligands (Ronson et al., 2006) and the mixed N,N/N,O-donor pyridyl–benzimidazole/amide ligands (Piguet et al., 1997). Depending on the carefully designed ligands and the versatile coordination geometries of the chosen metal, a large number of polynuclear metal clusters with magnetic, optical or electronic properties have been synthesized. The synthesis of ligands based on 2,6-disubstituted pyridine has attracted a great deal of attention. In particular, diamides incorporating an –NH—CO–pyridine–CO—NH– core are versatile ligands, and a number of novel architectures such as helicates, cages, pockets and rotaxanes have recently been prepared (Lincheneau et al., 2010; Pan et al., 2010; Miyagawa et al., 2010). However, no dinuclear double-helical complex based on N,N'-bis(quinolin-8-yl)pyridine-2,6-dicarboxamide (H₂L) has been reported to date. In this paper, we describe the synthesis of the title novel dinuclear Zn^II double helicate, [Zn₂L₂].2CH₂Cl₂, (I), by the reaction of H₂L with Zn(OAc)₂.2H₂O. The compound has been characterized by elemental analysis, ¹H and ¹³C{H} NMR and IR spectroscopies, and X-ray single-crystal analysis.

The molecular structure of (I) is depicted in Fig. 1, and selected bond lengths and angles are listed in Table 1. Complex (I) is a dinuclear double helicate and there is only half a [Zn₂L₂] unit in the asymmetric unit, with the other half related to it by a crystallographic twofold axis. The Zn^II atom in the dimeric complex is coordinated to two amide N atoms [N2 and N4ⁱ; symmetry code: (i) -x + 1, y, -z + 1/2], two quinoline N atoms (N1 and N5ⁱ) and two pyridine N atoms (N3 and N3ⁱ) from two different ligand molecules. Each Zn^II atom has a distorted octahedral configuration, the r.m.s. deviation from the mean N1/N2/N3/N4ⁱ basal plane being 0.0383 (6) Å. The apical positions at Zn1 are occupied by atoms N3ⁱ and N5ⁱ, and atom Zn1 deviates from the basal plane by a distance of 0.1485 (13) Å towards apical atom N5 [N5ⁱ?]. Thus, the dimer is made up of two octahedra which are joined at a common edge, with the two bridging pyridine N atoms shared equally between the two Zn^II atoms. Most of the bond angles at Zn deviate considerably from the ideal values of 90 and 180°, as can be seen from Table 1. The Zn—N bond lengths [1.987 (3)–2.560 (3) Å] are close to those reported for a dinuclear zinc(II) complex of 2,6-diacetylpyridine bis(2-pyridylhydrazone) (Wester & Palenik, 1976). Due to the bridging nature of the pyridine (py) N atoms, the Zn—N_py distances are relatively long, with Zn1—N3 = 2.449 (3) and Zn1—N3ⁱ = 2.560 (3) Å, while the remaining four Zn—N distances average 2.05 Å. As a consequence of the central bridging N_py atoms in the [Zn(µ-N₂)Zn]⁴⁺ core, the Zn1···Zn1ⁱ separation within the binuclear unit is 3.445 (2) Å, which is short compared with other Zn^II-containing helicates (Horn et al., 2003; Ronson et al., 2005), and the Zn—N_py—Zn bridging angle is 86.91 (12)°.

Interestingly, in contrast with the previously reported free ligand H₂L (Meghdadi et al., 2008), striking changes have taken place in the conformation of the anion L. In H₂L, the central pyridine ring is oriented at dihedral angles of 8.90 (4) and 28.67 (4)° with respect to the two planar quinolyl ring systems, and the quinolyl rings themselves are oriented at a dihedral angle of 24.68 (3)° (Meghdadi et al., 2008), while in complex (I), the amide side chains are definitely twisted out of the plane of the central pyridine ring by considerable amounts. The dihedal angles between the central pyridine ring and the two quinolyl rings of (I) are 38.61 (16) and 41.72 (16)°, and the quinolyl rings are inclined at 69.63 (11)° with respect to each other. The lack of planarity of the amide is obviously related to its cocoordinating behaviour.

Related literature

For related literature, see: Albrecht & Schneider (2002); Elsevier et al. (2003); Horn et al. (2003); Lincheneau et al. (2010); Meghdadi et al. (2008); Miyagawa et al. (2010); Pan et al. (2010); Piguet et al. (1997); Rice et al. (2001); Richards & Rodger (2007); Riis-Johannessen, Bernardinelle, Filincuk, Clifford, Favera & Piguet (2009); Ronson et al. (2005, 2006); Serrano & Sierra (2003); Sleiman et al. (1995); Wester & Palenik (1976); Yeung et al. (2008).

S2. Experimental

To a solution of pyridine-2,6-dicarboxylic acid (1.67 g, 0.01 mmol) in pyridine (5 ml) was added 8-aminoquinoline (2.88 g, 0.02 mmol) and the resulting solution warmed with stirring for 30 min. Triphenylphosphite (6.2 g, 0.02 mmol) was added slowly and the mixture was stirred at 393 K for 10 h. On cooling to room temperature, the white precipitate which had formed was filtered off and recrystallized from chloroform to afford H₂L (yield 7.02 g, 16.75 mmol, 84%). Spectroscopic analysis: ¹H NMR (300 MHz, DMSO-d₆, δ, p.p.m.): 12.18 (s, 2 H), 8.92 (dd, 2H), 8.57–8.54 (m, 2H), 8.50–8.42 (m, 3H), 8.26 (dd, 2H), 7.84–7.81 (m, 2H), 7.76–7.71 (m, 2H), 7.55 (q, 2H); IR (KBr, ν, cm^-1): 3322, 3298, 1684, 1544, 1490, 1428, 1328, 1149, 1068, 1000, 890, 826, 794, 751, 709, 679, 604. Elemental analysis, calculated for C₂₅H₁₇N₅O₂: C 71.59, H 4.09, N 16.70%; found: C 71.33, H 4.06, N 16.53%.

A mixture of H₂L (0.3355 g, 0.80 mmol) and Zn(OAc)₂.2H₂O (0.1758 g, 0.80 mmol) in ethanol (Volume?) was refluxed for 6 h. The resulting precipitate was filtered off, washed with chloroform and then ethanol, and finally dried in air. Recrystallization from CH₂Cl₂ yielded yellow crystals of (I) suitable for X-ray diffraction upon slow evaporation. Spectroscopic analysis: ¹H NMR (500 MHz, DMSO-d₆, δ, p.p.m.): 8.87 (d, 4H), 8.35 (d, 4H), 7.71 (d, 4H), 7.62 (t, 4H), 7.52 (d, 4H), 7.36–7.33 (m, 2H), 7.28–7.23 (m, 8H); ¹³C{H}NMR (500 MHz, DMSO-d₆, δ, p.p.m.): 202.1, 165.9, 155.4, 145.7, 142.1, 139.6, 139.4, 129.0, 128.4, 123.1, 121.5, 120.9, 119.4; IR (KBr, ν, cm^-1): 3425, 1612, 1581, 1500, 1463, 1413, 1390, 1350, 1317, 1271, 1238, 1158, 1082, 965, 829, 758, 609. Elemental analysis, calculated for C₅₀H₃₀N₁₀O₄Zn₂: C 62.19, H 3.13, N 14.50%; found: C 61.94, H 3.09, N 14.32%.

S3. Refinement

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å and with U_iso(H) = 1.2U_eq(C). The two CH₂Cl₂ solvent molecules are disordered and were refined with split occupancies of 0.41 (2)/0.59 (2) (C26/C26'), 0.43 (3)/0.57 (3) (Cl1/Cl1') and 0.43 (3)/0.57 (3) (Cl2/Cl2').

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The Zn^II coordination environments in (I). Displacement ellipsoids are drawn at the 30% probability level. H atoms and the solvent have been omitted for clarity. Atoms labelled with the suffix A and unlabelled atoms are at the symmetry position (-x + 1, y, -z + 1/2).

Bis[µ-N,N'-bis(quinolin-8-yl)pyridine-2,6- dicarboxamido]dizinc(II) dichloromethane disolvate

Crystal data

[Zn2(C25H15N5O2)2]·2CH2Cl2	F(000) = 2304
Mr = 1135.43	Dx = 1.541 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 24.458 (5) Å	θ = 9–13°
b = 13.672 (3) Å	µ = 1.26 mm^−1
c = 16.588 (3) Å	T = 293 K
β = 118.07 (3)°	Block, yellow
V = 4894 (2) Å^3	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	2882 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 25.3°, θmin = 1.8°
ω/2θ scans	h = 0→29
Absorption correction: ψ scan (CAD-4 EXPRESS; Enraf–Nonius, 1994)	k = 0→16
Tmin = 0.642, Tmax = 0.778	l = −19→17
4554 measured reflections	3 standard reflections every 200 reflections
4445 independent reflections	intensity decay: 1%

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)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.133	w = 1/[σ^2(Fo^2) + (0.0627P)^2 + 2.753P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
4445 reflections	Δρmax = 0.26 e Å^−3
354 parameters	Δρmin = −0.72 e Å^−3
36 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: 0.0038 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Zn1	0.56600 (2)	0.31851 (3)	0.35422 (3)	0.0404 (2)
O1	0.48505 (16)	0.5766 (2)	0.3733 (2)	0.0651 (10)
O2	0.40496 (16)	0.0851 (2)	0.2802 (2)	0.0589 (9)
N1	0.65441 (17)	0.3768 (3)	0.3838 (2)	0.0447 (9)
N2	0.55081 (16)	0.4600 (2)	0.3626 (2)	0.0406 (9)
N3	0.45588 (15)	0.3287 (3)	0.3124 (2)	0.0388 (8)
N4	0.42696 (15)	0.1824 (2)	0.1846 (2)	0.0370 (8)
N5	0.42606 (16)	0.2418 (2)	0.0313 (2)	0.0391 (8)
C1	0.7051 (2)	0.3303 (4)	0.3951 (3)	0.0608 (14)
H1	0.7055	0.2623	0.3962	0.073*
C2	0.7574 (3)	0.3794 (5)	0.4052 (4)	0.0843 (19)
H2	0.7921	0.3447	0.4122	0.101*
C3	0.7575 (3)	0.4785 (5)	0.4048 (5)	0.089 (2)
H3	0.7928	0.5119	0.4128	0.107*
C4	0.7050 (3)	0.5314 (4)	0.3924 (4)	0.0668 (15)
C5	0.7009 (3)	0.6345 (5)	0.3898 (5)	0.091 (2)
H5	0.7344	0.6720	0.3963	0.109*
C6	0.6486 (3)	0.6781 (4)	0.3781 (4)	0.0870 (19)
H6	0.6463	0.7460	0.3756	0.104*
C7	0.5972 (3)	0.6246 (4)	0.3696 (4)	0.0654 (15)
H7	0.5620	0.6577	0.3625	0.078*
C8	0.5981 (2)	0.5233 (3)	0.3715 (3)	0.0452 (11)
C9	0.6535 (2)	0.4763 (3)	0.3834 (3)	0.0479 (11)
C10	0.4991 (2)	0.4925 (3)	0.3632 (3)	0.0471 (11)
C11	0.4556 (2)	0.4104 (3)	0.3568 (3)	0.0421 (11)
C12	0.4184 (2)	0.4206 (4)	0.3984 (3)	0.0604 (14)
H12	0.4179	0.4789	0.4269	0.072*
C13	0.3825 (3)	0.3433 (4)	0.3971 (4)	0.0675 (15)
H13	0.3578	0.3484	0.4258	0.081*
C14	0.3830 (2)	0.2579 (4)	0.3532 (3)	0.0563 (13)
H14	0.3594	0.2042	0.3526	0.068*
C15	0.41951 (19)	0.2542 (3)	0.3100 (3)	0.0378 (10)
C16	0.41766 (19)	0.1636 (3)	0.2563 (3)	0.0404 (10)
C17	0.42596 (18)	0.1085 (3)	0.1253 (3)	0.0372 (10)
C18	0.4263 (2)	0.0090 (3)	0.1375 (3)	0.0503 (12)
H18	0.4262	−0.0157	0.1896	0.060*
C19	0.4268 (2)	−0.0558 (3)	0.0722 (3)	0.0555 (13)
H19	0.4278	−0.1227	0.0829	0.067*
C20	0.4259 (2)	−0.0242 (3)	−0.0057 (3)	0.0543 (13)
H20	0.4259	−0.0691	−0.0478	0.065*
C21	0.4250 (2)	0.0771 (3)	−0.0229 (3)	0.0431 (11)
C22	0.4247 (2)	0.1169 (4)	−0.1011 (3)	0.0550 (13)
H22	0.4239	0.0756	−0.1463	0.066*
C23	0.4257 (3)	0.2157 (4)	−0.1111 (3)	0.0601 (14)
H23	0.4260	0.2424	−0.1625	0.072*
C24	0.4263 (2)	0.2758 (3)	−0.0431 (3)	0.0496 (12)
H24	0.4269	0.3432	−0.0503	0.060*
C25	0.42546 (18)	0.1430 (3)	0.0431 (3)	0.0354 (10)
C26	0.7690 (9)	0.5005 (14)	0.2014 (18)	0.101 (8)	0.416 (19)
H26A	0.8096	0.5300	0.2368	0.122*	0.416 (19)
H26B	0.7545	0.4757	0.2428	0.122*	0.416 (19)
C26'	0.7687 (7)	0.5169 (12)	0.1361 (13)	0.105 (5)	0.584 (19)
H26C	0.8087	0.5462	0.1527	0.126*	0.584 (19)
H26D	0.7465	0.5111	0.0700	0.126*	0.584 (19)
Cl1	0.7713 (6)	0.4105 (11)	0.1325 (13)	0.145 (5)	0.416 (19)
Cl2	0.7167 (6)	0.5842 (10)	0.1245 (9)	0.119 (3)	0.416 (19)
Cl1'	0.7798 (4)	0.3965 (7)	0.1868 (8)	0.149 (3)	0.584 (19)
Cl2'	0.7266 (5)	0.5934 (8)	0.1732 (11)	0.158 (3)	0.584 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0482 (3)	0.0322 (3)	0.0456 (3)	0.0022 (3)	0.0260 (2)	−0.0005 (2)
O1	0.074 (2)	0.0413 (19)	0.088 (3)	0.0068 (17)	0.045 (2)	−0.0130 (18)
O2	0.087 (3)	0.0471 (19)	0.059 (2)	−0.0122 (18)	0.047 (2)	0.0032 (16)
N1	0.044 (2)	0.042 (2)	0.046 (2)	−0.0010 (18)	0.0202 (19)	−0.0054 (17)
N2	0.045 (2)	0.0335 (19)	0.044 (2)	−0.0007 (17)	0.0205 (18)	−0.0054 (16)
N3	0.041 (2)	0.044 (2)	0.0282 (18)	0.0068 (17)	0.0139 (16)	0.0050 (16)
N4	0.045 (2)	0.0346 (18)	0.0380 (19)	−0.0046 (17)	0.0245 (17)	−0.0014 (16)
N5	0.045 (2)	0.037 (2)	0.039 (2)	−0.0032 (17)	0.0219 (18)	−0.0007 (16)
C1	0.044 (3)	0.063 (3)	0.063 (3)	0.002 (3)	0.015 (2)	−0.007 (3)
C2	0.050 (4)	0.099 (5)	0.103 (5)	0.000 (3)	0.035 (3)	−0.012 (4)
C3	0.059 (4)	0.097 (5)	0.112 (5)	−0.030 (4)	0.040 (4)	−0.018 (4)
C4	0.062 (4)	0.068 (4)	0.072 (4)	−0.023 (3)	0.033 (3)	−0.008 (3)
C5	0.093 (5)	0.071 (4)	0.122 (6)	−0.042 (4)	0.061 (5)	−0.016 (4)
C6	0.112 (5)	0.046 (3)	0.118 (5)	−0.022 (4)	0.066 (5)	−0.005 (3)
C7	0.089 (4)	0.042 (3)	0.075 (4)	−0.011 (3)	0.047 (3)	−0.007 (3)
C8	0.061 (3)	0.036 (2)	0.040 (3)	−0.005 (2)	0.026 (2)	−0.004 (2)
C9	0.054 (3)	0.050 (3)	0.041 (3)	−0.012 (2)	0.023 (2)	−0.008 (2)
C10	0.064 (3)	0.035 (2)	0.041 (3)	0.007 (2)	0.023 (2)	−0.004 (2)
C11	0.040 (3)	0.044 (3)	0.038 (2)	0.008 (2)	0.016 (2)	−0.004 (2)
C12	0.065 (3)	0.068 (3)	0.061 (3)	0.007 (3)	0.040 (3)	−0.012 (3)
C13	0.072 (4)	0.080 (4)	0.074 (4)	0.005 (3)	0.053 (3)	−0.003 (3)
C14	0.059 (3)	0.062 (3)	0.057 (3)	−0.003 (3)	0.034 (3)	−0.001 (3)
C15	0.039 (2)	0.045 (2)	0.029 (2)	0.001 (2)	0.016 (2)	0.0057 (19)
C16	0.040 (2)	0.039 (3)	0.042 (2)	−0.001 (2)	0.020 (2)	0.005 (2)
C17	0.034 (2)	0.035 (2)	0.042 (3)	−0.0049 (19)	0.018 (2)	−0.0017 (18)
C18	0.058 (3)	0.044 (3)	0.056 (3)	−0.002 (2)	0.033 (3)	0.003 (2)
C19	0.068 (3)	0.035 (3)	0.070 (4)	−0.005 (2)	0.038 (3)	−0.006 (2)
C20	0.054 (3)	0.045 (3)	0.068 (3)	−0.008 (2)	0.033 (3)	−0.025 (3)
C21	0.038 (2)	0.045 (3)	0.047 (3)	−0.006 (2)	0.020 (2)	−0.009 (2)
C22	0.057 (3)	0.065 (3)	0.048 (3)	−0.005 (3)	0.029 (3)	−0.013 (3)
C23	0.082 (4)	0.062 (3)	0.050 (3)	−0.007 (3)	0.042 (3)	−0.002 (3)
C24	0.064 (3)	0.045 (3)	0.048 (3)	−0.005 (2)	0.033 (3)	0.000 (2)
C25	0.030 (2)	0.036 (2)	0.038 (2)	−0.0024 (18)	0.0152 (19)	−0.0052 (18)
C26	0.096 (13)	0.095 (15)	0.092 (17)	0.009 (11)	0.027 (11)	0.006 (11)
C26'	0.105 (11)	0.136 (14)	0.096 (12)	0.012 (9)	0.065 (9)	0.023 (10)
Cl1	0.111 (6)	0.152 (8)	0.177 (10)	−0.016 (5)	0.070 (8)	−0.041 (8)
Cl2	0.103 (5)	0.115 (5)	0.119 (7)	0.006 (4)	0.035 (6)	0.022 (5)
Cl1'	0.107 (3)	0.142 (5)	0.157 (7)	0.013 (3)	0.030 (5)	−0.002 (5)
Cl2'	0.123 (5)	0.165 (5)	0.182 (9)	0.017 (4)	0.068 (7)	0.021 (7)

Geometric parameters (Å, º)

Zn1—N2	1.987 (3)	C8—C9	1.426 (6)
Zn1—N4^i	2.003 (3)	C10—C11	1.515 (6)
Zn1—N5^i	2.097 (3)	C11—C12	1.384 (6)
Zn1—N1	2.134 (4)	C12—C13	1.368 (7)
Zn1—N3	2.449 (3)	C12—H12	0.9300
Zn1—N3^i	2.560 (3)	C13—C14	1.380 (7)
O1—C10	1.235 (5)	C13—H13	0.9300
O2—C16	1.233 (5)	C14—C15	1.385 (6)
N1—C1	1.325 (6)	C14—H14	0.9300
N1—C9	1.361 (6)	C15—C16	1.513 (6)
N2—C10	1.344 (5)	C17—C18	1.375 (6)
N2—C8	1.396 (5)	C17—C25	1.437 (5)
N3—C11	1.340 (5)	C18—C19	1.403 (6)
N3—C15	1.340 (5)	C18—H18	0.9300
N4—C16	1.338 (5)	C19—C20	1.353 (6)
N4—C17	1.403 (5)	C19—H19	0.9300
N4—Zn1^i	2.003 (3)	C20—C21	1.412 (6)
N5—C24	1.321 (5)	C20—H20	0.9300
N5—C25	1.366 (5)	C21—C22	1.403 (6)
N5—Zn1^i	2.097 (3)	C21—C25	1.415 (6)
C1—C2	1.384 (7)	C22—C23	1.362 (7)
C1—H1	0.9300	C22—H22	0.9300
C2—C3	1.355 (8)	C23—C24	1.391 (6)
C2—H2	0.9300	C23—H23	0.9300
C3—C4	1.402 (8)	C24—H24	0.9300
C3—H3	0.9300	C26—Cl1	1.70 (3)
C4—C5	1.413 (8)	C26—Cl2	1.74 (3)
C4—C9	1.414 (6)	C26—H26A	0.9700
C5—C6	1.339 (8)	C26—H26B	0.9700
C5—H5	0.9300	C26'—Cl2'	1.77 (2)
C6—C7	1.402 (7)	C26'—Cl1'	1.81 (2)
C6—H6	0.9300	C26'—H26C	0.9700
C7—C8	1.386 (6)	C26'—H26D	0.9700
C7—H7	0.9300
N2—Zn1—N4^i	166.94 (13)	N2—C10—C11	112.8 (4)
N2—Zn1—N5^i	111.37 (14)	N3—C11—C12	122.1 (4)
N4^i—Zn1—N5^i	80.88 (13)	N3—C11—C10	118.1 (4)
N2—Zn1—N1	79.79 (14)	C12—C11—C10	119.7 (4)
N4^i—Zn1—N1	100.94 (13)	C13—C12—C11	118.9 (5)
N5^i—Zn1—N1	109.06 (14)	C13—C12—H12	120.5
N2—Zn1—N3	75.39 (13)	C11—C12—H12	120.5
N4^i—Zn1—N3	102.19 (13)	C12—C13—C14	119.8 (5)
N5^i—Zn1—N3	84.59 (12)	C12—C13—H13	120.1
N1—Zn1—N3	154.75 (13)	C14—C13—H13	120.1
N2—Zn1—N3^i	94.10 (13)	C13—C14—C15	118.2 (5)
N4^i—Zn1—N3^i	73.09 (12)	C13—C14—H14	120.9
N5^i—Zn1—N3^i	152.66 (12)	C15—C14—H14	120.9
N1—Zn1—N3^i	84.39 (12)	N3—C15—C14	122.5 (4)
N3—Zn1—N3^i	92.74 (11)	N3—C15—C16	118.4 (4)
C1—N1—C9	119.5 (4)	C14—C15—C16	119.1 (4)
C1—N1—Zn1	129.2 (3)	O2—C16—N4	128.9 (4)
C9—N1—Zn1	111.1 (3)	O2—C16—C15	117.8 (4)
C10—N2—C8	122.0 (4)	N4—C16—C15	113.2 (3)
C10—N2—Zn1	122.0 (3)	C18—C17—N4	127.8 (4)
C8—N2—Zn1	116.0 (3)	C18—C17—C25	117.5 (4)
C11—N3—C15	118.4 (4)	N4—C17—C25	114.7 (3)
C11—N3—Zn1	100.4 (3)	C17—C18—C19	120.9 (4)
C15—N3—Zn1	126.3 (3)	C17—C18—H18	119.6
C16—N4—C17	122.1 (3)	C19—C18—H18	119.6
C16—N4—Zn1^i	122.8 (3)	C20—C19—C18	122.2 (4)
C17—N4—Zn1^i	114.8 (2)	C20—C19—H19	118.9
C24—N5—C25	119.2 (4)	C18—C19—H19	118.9
C24—N5—Zn1^i	129.1 (3)	C19—C20—C21	119.9 (4)
C25—N5—Zn1^i	111.5 (3)	C19—C20—H20	120.1
N1—C1—C2	122.4 (5)	C21—C20—H20	120.1
N1—C1—H1	118.8	C22—C21—C20	124.0 (4)
C2—C1—H1	118.8	C22—C21—C25	117.6 (4)
C3—C2—C1	119.1 (6)	C20—C21—C25	118.3 (4)
C3—C2—H2	120.4	C23—C22—C21	120.3 (4)
C1—C2—H2	120.4	C23—C22—H22	119.9
C2—C3—C4	120.9 (6)	C21—C22—H22	119.9
C2—C3—H3	119.6	C22—C23—C24	118.8 (5)
C4—C3—H3	119.6	C22—C23—H23	120.6
C3—C4—C5	124.5 (5)	C24—C23—H23	120.6
C3—C4—C9	116.8 (5)	N5—C24—C23	123.1 (4)
C5—C4—C9	118.7 (6)	N5—C24—H24	118.5
C6—C5—C4	119.9 (6)	C23—C24—H24	118.5
C6—C5—H5	120.1	N5—C25—C21	121.0 (4)
C4—C5—H5	120.1	N5—C25—C17	117.7 (4)
C5—C6—C7	122.2 (6)	C21—C25—C17	121.2 (4)
C5—C6—H6	118.9	Cl1—C26—Cl2	103 (2)
C7—C6—H6	118.9	Cl1—C26—H26A	111.1
C8—C7—C6	120.9 (6)	Cl2—C26—H26A	111.1
C8—C7—H7	119.5	Cl1—C26—H26B	111.1
C6—C7—H7	119.5	Cl2—C26—H26B	111.1
C7—C8—N2	127.9 (5)	H26A—C26—H26B	109.1
C7—C8—C9	117.3 (5)	Cl2'—C26'—Cl1'	111.1 (14)
N2—C8—C9	114.9 (4)	Cl2'—C26'—H26C	109.4
N1—C9—C4	121.3 (5)	Cl1'—C26'—H26C	109.4
N1—C9—C8	117.7 (4)	Cl2'—C26'—H26D	109.4
C4—C9—C8	121.0 (5)	Cl1'—C26'—H26D	109.4
O1—C10—N2	129.2 (4)	H26C—C26'—H26D	108.0
O1—C10—C11	117.9 (4)
N2—Zn1—N1—C1	178.8 (4)	C8—N2—C10—O1	−1.9 (7)
N4^i—Zn1—N1—C1	−14.5 (4)	Zn1—N2—C10—O1	175.4 (4)
N5^i—Zn1—N1—C1	69.5 (4)	C8—N2—C10—C11	−177.5 (4)
N3—Zn1—N1—C1	−170.6 (3)	Zn1—N2—C10—C11	−0.2 (5)
N3^i—Zn1—N1—C1	−86.0 (4)	C15—N3—C11—C12	−1.1 (6)
N2—Zn1—N1—C9	−6.4 (3)	Zn1—N3—C11—C12	−142.6 (4)
N4^i—Zn1—N1—C9	160.4 (3)	C15—N3—C11—C10	177.1 (4)
N5^i—Zn1—N1—C9	−115.6 (3)	Zn1—N3—C11—C10	35.5 (4)
N3—Zn1—N1—C9	4.3 (5)	O1—C10—C11—N3	154.7 (4)
N3^i—Zn1—N1—C9	88.8 (3)	N2—C10—C11—N3	−29.2 (5)
N4^i—Zn1—N2—C10	95.1 (7)	O1—C10—C11—C12	−27.1 (7)
N5^i—Zn1—N2—C10	−63.8 (3)	N2—C10—C11—C12	149.0 (4)
N1—Zn1—N2—C10	−170.4 (3)	N3—C11—C12—C13	2.5 (7)
N3—Zn1—N2—C10	14.2 (3)	C10—C11—C12—C13	−175.7 (4)
N3^i—Zn1—N2—C10	106.0 (3)	C11—C12—C13—C14	−1.2 (8)
N4^i—Zn1—N2—C8	−87.4 (7)	C12—C13—C14—C15	−1.2 (8)
N5^i—Zn1—N2—C8	113.6 (3)	C11—N3—C15—C14	−1.5 (6)
N1—Zn1—N2—C8	7.0 (3)	Zn1—N3—C15—C14	129.1 (4)
N3—Zn1—N2—C8	−168.3 (3)	C11—N3—C15—C16	177.4 (3)
N3^i—Zn1—N2—C8	−76.5 (3)	Zn1—N3—C15—C16	−52.0 (5)
N2—Zn1—N3—C11	−26.2 (3)	C13—C14—C15—N3	2.6 (7)
N4^i—Zn1—N3—C11	167.0 (3)	C13—C14—C15—C16	−176.2 (4)
N5^i—Zn1—N3—C11	87.6 (3)	C17—N4—C16—O2	−3.1 (7)
N1—Zn1—N3—C11	−37.0 (4)	Zn1^i—N4—C16—O2	170.0 (4)
N3^i—Zn1—N3—C11	−119.7 (2)	C17—N4—C16—C15	−178.9 (3)
N2—Zn1—N3—C15	−163.4 (3)	Zn1^i—N4—C16—C15	−5.8 (5)
N4^i—Zn1—N3—C15	29.8 (3)	N3—C15—C16—O2	153.1 (4)
N5^i—Zn1—N3—C15	−49.7 (3)	C14—C15—C16—O2	−28.1 (6)
N1—Zn1—N3—C15	−174.3 (3)	N3—C15—C16—N4	−30.6 (5)
N3^i—Zn1—N3—C15	103.0 (3)	C14—C15—C16—N4	148.3 (4)
C9—N1—C1—C2	−1.0 (7)	C16—N4—C17—C18	−11.8 (7)
Zn1—N1—C1—C2	173.5 (4)	Zn1^i—N4—C17—C18	174.5 (4)
N1—C1—C2—C3	0.9 (9)	C16—N4—C17—C25	169.2 (4)
C1—C2—C3—C4	−1.3 (10)	Zn1^i—N4—C17—C25	−4.5 (4)
C2—C3—C4—C5	−179.1 (6)	N4—C17—C18—C19	−178.3 (4)
C2—C3—C4—C9	1.8 (9)	C25—C17—C18—C19	0.7 (7)
C3—C4—C5—C6	−179.7 (6)	C17—C18—C19—C20	−1.2 (8)
C9—C4—C5—C6	−0.6 (9)	C18—C19—C20—C21	0.6 (8)
C4—C5—C6—C7	1.0 (11)	C19—C20—C21—C22	179.3 (5)
C5—C6—C7—C8	−1.0 (10)	C19—C20—C21—C25	0.3 (7)
C6—C7—C8—N2	−179.0 (5)	C20—C21—C22—C23	−178.1 (5)
C6—C7—C8—C9	0.6 (7)	C25—C21—C22—C23	0.9 (7)
C10—N2—C8—C7	−9.5 (7)	C21—C22—C23—C24	−0.7 (8)
Zn1—N2—C8—C7	173.0 (4)	C25—N5—C24—C23	0.3 (7)
C10—N2—C8—C9	170.9 (4)	Zn1^i—N5—C24—C23	174.6 (4)
Zn1—N2—C8—C9	−6.6 (5)	C22—C23—C24—N5	0.1 (8)
C1—N1—C9—C4	1.6 (7)	C24—N5—C25—C21	0.0 (6)
Zn1—N1—C9—C4	−173.8 (4)	Zn1^i—N5—C25—C21	−175.3 (3)
C1—N1—C9—C8	−179.7 (4)	C24—N5—C25—C17	179.3 (4)
Zn1—N1—C9—C8	4.8 (5)	Zn1^i—N5—C25—C17	4.0 (5)
C3—C4—C9—N1	−2.0 (7)	C22—C21—C25—N5	−0.5 (6)
C5—C4—C9—N1	178.8 (5)	C20—C21—C25—N5	178.5 (4)
C3—C4—C9—C8	179.4 (5)	C22—C21—C25—C17	−179.8 (4)
C5—C4—C9—C8	0.2 (8)	C20—C21—C25—C17	−0.8 (6)
C7—C8—C9—N1	−178.9 (4)	C18—C17—C25—N5	−179.0 (4)
N2—C8—C9—N1	0.7 (6)	N4—C17—C25—N5	0.1 (5)
C7—C8—C9—C4	−0.3 (7)	C18—C17—C25—C21	0.3 (6)
N2—C8—C9—C4	179.4 (4)	N4—C17—C25—C21	179.4 (4)

Symmetry code: (i) −x+1, y, −z+1/2.