Concerted coordination and hydrogen-bonding network of the 1,4-di-4-pyrid­yl-2,3-diaza-1,3-butadiene [Zn(MeOH)₂(H₂O)₂](ClO₄)₂ 3:1 complex

In the title compound, diaqua­bis(1,4-di-4-pyrid­yl-2,3-diaza-1,3-butadiene)dimethanolzinc(II) bis­(perchlorate) 1,4-di-4-pyrid­yl-2,3-diaza-1,3-butadiene methanol 1.72-solvate 1.28-hydrate, [Zn(C₁₂H₁₀N₄)₂(CH₄O)₂(H₂O)₂](ClO₄)₂·C₁₂H₁₀N₄·1.72CH₄O·1.28H₂O, determined at ca 110 K, the Zn cation and the extended dipyridyl ligand both lie across inversion centres in space group P. The structure consists of a network arrangement of the constituent species stabilized by a combination of coordination, hydrogen bonding and π–π forces. Uncoordinated methanol and water solvent mol­ecules occupy the otherwise void spaces within and between the networks.

S1. Comment

We have been exploring the coordination chemistry of a large series of polyimine ligands with transition metal ions (Patra & Goldberg, 2002, 2003a,b) and with metalloporphyrins (Diskin-Posner, Patra & Goldberg, 2002, 2001). Tailored derivatives of the 4,4'-bipyridyl-type ligands with various spacers between the bipyridyl functions are very effective in the formation of diverse architectures via coordination through metal ion connectors (e.g. Co, Ni, Mn, Zn, Ag and Pb). Such ligands are also excellent proton acceptors in hydrogen bonding (through their N-atom sites), in the presence of strong proton-donating agents.

We refer here to the 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene ligand (L), and its hydrogen bonding and coordination to [Zn(H₂O)₂(MeOH)₂]²⁺ cations, affording self-assembled two-dimensional networks. Another important feature of L is its aromatic nature, with delocalized π electrons, preserving the planar geometry of this ligand both in its coordination polymers or oligomers with various transition metals and as a free non-coordinated species in its protonated or base forms (Kennedy & Waterson, 2003; Ciurtin et al., 2001).

The title compound, (I) (Fig. 1), consists of the octahedral [Zn(H₂O)₂(MeOH)₂(L)₂]²⁺ dication, two perchlorate anions and another ligand species hydrogen bonded to the water ligands. The dication and the extended bipyridyl moieties reside on crystallographic inversion centres. The crystal structure is a solvate incorporating additional molecules of methanol and water, not bound to the metal centre, in the unit cell.

The solvated zinc ion [labelled hereafter as Zn(s)] coordinates at trans-related sites to two molecules of the ligand [Zn—N = 2.120 (2) Å], forming a linear L–Zn(s)–L oligomer. Adjacent units of the latter are aligned parallel to one another in an offset manner along the long molecular axis, in such a way that the pyridyl ends of one trimer hydrogen bond to the Zn-bound water ligands of two adjacent L–Zn(s)–L trimers [O···N = 2.798 (3) Å; Fig. 2]. The double chains thus formed propagate along the [11–1] axis through the crystal. The overlapping planar ligand segments of neighbouring oligomers in these double chains further interact with one another through π–π interactions, as indicated by the very close interligand spacing. The mean interplanar distance between the parallel stacked pyridyl rings [N2/C3–C7 and C12–C14/N15/C16/C17 at (1 − x, 2 − y, 1 − z)] is 3.369 (7) Å, the shortest atom-to-atom distance between these two rings being 3.252 (3) Å (Fig. 3). The overlapping pyridyl rings are nearly parallel to each other, the angle between their normals being 5.6 (2)°. The third ligand moiety provides a bridging unit between different double chains by hydrogen bonding through its N-atom sites on both sides, accepting the second H atom of the zinc-bound water ligands [O···N = 2.773 (3) Å].

The binding pattern described above results in a supramolecularly assembled network in the form of a nearly square grid (Fig. 2). The van der Waals width of the void space in the grid is about 8 Å, sizeable enough to accommodate the perchlorate anions and additional methanol and water solvent molecules. The zinc-bound methanol ligands hydrogen bond to the lattice-occluded solvent [represented by O34, O36 (methanol) and O38 (water) in Table 2], the latter lying also within a hydrogen-bonding distances from the perchlorate anions. The network arrays stack in the crystal along the [111] axis. The crystal packing of (I) viewed down the a axis is shown in Fig. 4, illustrating the inclusion of the perchlorate anions and disordered solvent molecules in channel voids propagating through the crystal. A space-filling illustration of the channel structure down a, excluding these species, is presented in Fig. 5. This structure illustrates nicely the high versatility of bipyridyl ligands in the construction of hybrid organic–inorganic supramolecular assemblies.

S2. Experimental

The title compound was synthesized by reacting stoichiometric amounts of zinc perchlorate hexahydrate with L dissolved in hot methanol, followed by crystallization by slow cooling.

S3. Refinement

The perchlorate anion exhibits very wide-amplitude displacement, indicative of partial rotational disorder that could not be resolved. The content and structure of the crystallization solvent could not be determined precisely from the diffraction data, owing to severe positional disorder and fractional occupancies at each site. The approximate unit-cell content, which best fits the diffraction data, was assessed as 1.72 molecules of methanol and 1.28 molecules of water distributed randomly in the crystal within and between the self-assembled networks. The O34/C35 and O36/C37 fragments represent methanol species with 36 and 50% occupancy, respectively. Atom O38 (nearly coinciding with the position of O34) represents a water molecule with 64% occupancy. These solvent species are located near and disordered about the inversion centre. According to this model O34/C35 (methanol) and O38 (water) are randomly distributed in the crystal at the same site in different unit cells. The coinciding position of these two species results from the hydrogen bonding of either one to the Zn-bound methanol ligand O19/H19. The apparent disorder of the solvent species seems to have a negligible effect on the precise characterization of the network structure. H atoms were placed at idealized positions; those attached to C atoms were refined using a riding model with fixed displacement parameters. The displacement parameters of the H atoms of the Zn-coordinated methanol and aqua groups were allowed to refine freely. H atoms of the water solvent molecules could not be located. The relatively high residual density should be attributed to the unresolved solvent.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and DS ViwerPro 5.0 (Accelrys, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are shown at the 50% probability level at ca 110 K. The large displacement parameters of the perchlorate and solvent species indicate unresolved disorder.
	Fig. 2. An illustration of the intermolecular network arrangement. Hydrogen bonds are indicated by thin lines. The double chains with π–π stacked ligand species extend horizontally along the [11–1] axis of the crystal. Adjacent double chains in this network are displaced with respect to one another along the [2–10] axis. The perchlorate and solvent species have been omitted for clarity. All non-C atoms are denoted by crossed circles.
	Fig. 3. The overlap between two ligands related by inversion at (1/2, 1, 1/2), with a mean interplanar distance of 3.369 (7) Å between the pyridyl rings. Atomic labels with symmetry `_2' relate to atoms located at (1 − x, 2 − y, 1 − z). Atom N2 of each ligand coordinates directly to the Zn atom, while atom N15 of each ligand hydrogen bonds to the zinc-bound water ligand O18 (Fig. 2).
	Fig. 4. The crystal packing viewed down the a axis of the crystals, showing the anion and disordered solvent moieties accommodated in channel voids propagating through the supramolecular networks. Atoms of the perchlorate anions are denoted by crossed circles; those of the O36/C37 methanol and O38 water groups are represented by open circles (methanol group O34/C35, which nearly coincides with O38, has been omitted for clarity). The cntents of more than one unit cell are shown.
	Fig. 5. Space-filling perspective of the channel structure formed by the stacked network arrays (excluding the perchlorate ions and the disordered solvent molecules, which accommodate the channel voids), viewed approximately down the a axis.

diaquadimethanolbis(1,4-di-4-pyridyl-2,3-diaza-1,3-butadiene)zinc(II) bis(perchlorate) 1,4-di-4-pyridyl-2,3-diaza-1,3-butadiene methanol 1.72-solvate 1.28-hydrate

Crystal data

[Zn(C12H10N4)(CH4O)2(H2O)2](ClO4)2·C12H10N4·1.72CH4O·1.28H2O	Z = 1
Mr = 1073.28	F(000) = 558
Triclinic, P1	Dx = 1.471 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4170 (2) Å	Cell parameters from 4290 reflections
b = 10.8320 (2) Å	θ = 2.7–27.0°
c = 13.1410 (3) Å	µ = 0.70 mm^−1
α = 67.8390 (8)°	T = 110 K
β = 81.3040 (9)°	Prism, yellow
γ = 78.3160 (9)°	0.30 × 0.20 × 0.15 mm
V = 1211.56 (4) Å^3

Data collection

Nonius KappaCCD diffractometer	5216 independent reflections
Radiation source: fine-focus sealed tube	4492 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 56 microns pixels mm^-1	θmax = 27.0°, θmin = 2.7°
1° ϕ and ω scans	h = 0→12
Absorption correction: multi-scan (Blessing, 1995)	k = −13→13
Tmin = 0.818, Tmax = 0.903	l = −16→16
10055 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full with fixed elements per cycle	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.053P)^2 + 2.505P] where P = (Fo^2 + 2Fc^2)/3
5216 reflections	(Δ/σ)max = 0.028
347 parameters	Δρmax = 0.92 e Å^−3
2 restraints	Δρmin = −1.17 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.

The perchlorate anion suffers from partial rotational disorder.

Fragments O34—C35 and O36—C37 represent methanol species with 36% and 50% occupancy, respectively. Based on earlier refinement calculations, showing an occupancy of 1.0 at the O34 site, it was assumed that at this site water (O38) and methanol are randomly distributed in the crystal. O38 thus refined with occupancy of 64%. In this interpretation of the refinement calculations, the nearly coinciding positions of O34(methanol) and O38(water) result from their H-bonding to OH(19), the Zn-bound methanol ligand. O34—C35 and O38 were refined in alternating cycles of the least-squares calculations, due to very high correlations between their respective atomic parameters.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.0000	0.5000	1.0000	0.01552 (13)
N2	0.1802 (2)	0.5559 (2)	0.88446 (18)	0.0171 (4)
C3	0.2435 (3)	0.6585 (3)	0.8805 (2)	0.0190 (5)
H3	0.2119	0.6983	0.9349	0.023*
C4	0.3517 (3)	0.7085 (3)	0.8014 (2)	0.0213 (6)
H4	0.3947	0.7802	0.8023	0.026*
C5	0.3975 (3)	0.6524 (3)	0.7197 (2)	0.0192 (5)
C6	0.3335 (3)	0.5446 (3)	0.7245 (2)	0.0208 (5)
H6	0.3630	0.5026	0.6713	0.025*
C7	0.2269 (3)	0.4999 (3)	0.8077 (2)	0.0194 (5)
H7	0.1846	0.4260	0.8107	0.023*
C8	0.5078 (3)	0.7051 (3)	0.6298 (2)	0.0231 (6)
H8	0.5374	0.6651	0.5754	0.028*
N9	0.5636 (3)	0.8055 (3)	0.6256 (2)	0.0266 (5)
N10	0.6671 (3)	0.8429 (3)	0.5344 (2)	0.0275 (6)
C11	0.7084 (3)	0.9527 (3)	0.5244 (2)	0.0269 (6)
H11	0.6693	0.9959	0.5757	0.032*
C12	0.8158 (3)	1.0129 (3)	0.4344 (2)	0.0224 (6)
C13	0.8697 (3)	0.9608 (3)	0.3514 (2)	0.0268 (6)
H13	0.8386	0.8828	0.3513	0.032*
C14	0.9690 (3)	1.0244 (3)	0.2696 (2)	0.0267 (6)
H14	1.0060	0.9874	0.2140	0.032*
N15	1.0165 (3)	1.1359 (2)	0.2643 (2)	0.0246 (5)
C16	0.9650 (3)	1.1846 (3)	0.3445 (2)	0.0246 (6)
H16	0.9979	1.2630	0.3424	0.029*
C17	0.8661 (3)	1.1267 (3)	0.4308 (2)	0.0242 (6)
H17	0.8333	1.1642	0.4866	0.029*
O18	0.09854 (19)	0.29692 (18)	1.04860 (15)	0.0189 (4)
H18A	0.2019	0.2624	1.0448	0.069 (15)*
H18B	0.0699	0.2410	1.1233	0.063 (14)*
O19	0.1074 (2)	0.5314 (2)	1.12069 (16)	0.0226 (4)
H19	0.0802	0.5859	1.1677	0.075 (15)*
C20	0.2362 (3)	0.4483 (3)	1.1695 (3)	0.0316 (7)
H20A	0.2639	0.4833	1.2212	0.047*
H20B	0.3154	0.4493	1.1116	0.047*
H20C	0.2175	0.3556	1.2090	0.047*
N21	0.6061 (3)	0.8020 (3)	0.9622 (2)	0.0250 (5)
C22	0.5713 (3)	0.9210 (3)	0.8823 (3)	0.0255 (6)
H22	0.6459	0.9575	0.8283	0.031*
C23	0.4312 (3)	0.9942 (3)	0.8741 (2)	0.0246 (6)
H23	0.4110	1.0786	0.8159	0.030*
C24	0.3213 (3)	0.9416 (3)	0.9527 (2)	0.0218 (6)
C25	0.3576 (3)	0.8173 (3)	1.0367 (2)	0.0231 (6)
H25	0.2857	0.7783	1.0922	0.028*
C26	0.4995 (3)	0.7524 (3)	1.0376 (3)	0.0254 (6)
H26	0.5230	0.6678	1.0948	0.031*
C27	0.1710 (3)	1.0152 (3)	0.9462 (2)	0.0245 (6)
H27	0.1506	1.1046	0.8946	0.029*
N28	0.0683 (3)	0.9581 (3)	1.0103 (2)	0.0276 (5)
Cl29	0.34389 (10)	0.69878 (9)	0.35758 (7)	0.0402 (2)
O30	0.3120 (5)	0.6298 (4)	0.4711 (2)	0.0845 (13)
O31	0.4802 (6)	0.7404 (5)	0.3404 (4)	0.123 (2)
O32	0.3480 (4)	0.6154 (3)	0.2971 (2)	0.0593 (8)
O33	0.2406 (7)	0.8140 (5)	0.3142 (3)	0.148 (3)
O34	−0.0038 (7)	0.6851 (6)	0.2390 (7)	0.045 (2)	0.36
C35	−0.037 (2)	0.6052 (16)	0.3599 (10)	0.088 (5)	0.36
H35A	0.0167	0.6316	0.4046	0.132*	0.36
H35B	−0.0078	0.5086	0.3735	0.132*	0.36
H35C	−0.1417	0.6238	0.3797	0.132*	0.36
O36	0.1813 (7)	0.3859 (6)	0.5492 (5)	0.0616 (19)	0.50
C37	0.0695 (14)	0.4938 (15)	0.5779 (12)	0.148 (9)	0.50
H37A	−0.0237	0.4606	0.6041	0.222*	0.50
H37B	0.0567	0.5759	0.5122	0.222*	0.50
H37C	0.1036	0.5141	0.6358	0.222*	0.50
O38	0.0060 (4)	0.6780 (4)	0.2555 (3)	0.0433 (9)	0.64

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0122 (2)	0.0183 (2)	0.0138 (2)	−0.00359 (15)	0.00155 (15)	−0.00361 (17)
N2	0.0140 (10)	0.0191 (10)	0.0149 (10)	−0.0031 (8)	0.0007 (8)	−0.0027 (9)
C3	0.0158 (12)	0.0227 (13)	0.0173 (13)	−0.0041 (10)	0.0004 (10)	−0.0058 (11)
C4	0.0178 (13)	0.0233 (13)	0.0211 (14)	−0.0066 (10)	0.0001 (10)	−0.0051 (11)
C5	0.0126 (12)	0.0225 (13)	0.0151 (12)	−0.0009 (10)	−0.0007 (10)	0.0004 (10)
C6	0.0186 (13)	0.0225 (13)	0.0179 (13)	0.0006 (10)	0.0011 (10)	−0.0062 (11)
C7	0.0187 (13)	0.0184 (12)	0.0182 (13)	−0.0027 (10)	0.0012 (10)	−0.0046 (11)
C8	0.0167 (13)	0.0259 (14)	0.0190 (13)	−0.0020 (11)	0.0019 (10)	−0.0014 (11)
N9	0.0192 (12)	0.0336 (13)	0.0183 (12)	−0.0079 (10)	0.0054 (9)	−0.0005 (10)
N10	0.0209 (12)	0.0346 (14)	0.0197 (12)	−0.0115 (10)	0.0061 (10)	−0.0008 (11)
C11	0.0183 (13)	0.0333 (16)	0.0203 (14)	−0.0037 (12)	0.0004 (11)	−0.0007 (12)
C12	0.0143 (12)	0.0251 (14)	0.0194 (13)	−0.0031 (10)	−0.0013 (10)	0.0011 (11)
C13	0.0270 (15)	0.0280 (15)	0.0229 (14)	−0.0098 (12)	−0.0005 (12)	−0.0041 (12)
C14	0.0262 (15)	0.0293 (15)	0.0205 (14)	−0.0071 (12)	0.0024 (11)	−0.0045 (12)
N15	0.0196 (11)	0.0244 (12)	0.0214 (12)	−0.0053 (9)	0.0003 (9)	0.0015 (10)
C16	0.0190 (13)	0.0227 (13)	0.0267 (15)	−0.0048 (11)	−0.0030 (11)	−0.0018 (12)
C17	0.0188 (13)	0.0269 (14)	0.0211 (14)	−0.0002 (11)	−0.0019 (11)	−0.0038 (12)
O18	0.0145 (9)	0.0178 (9)	0.0192 (9)	−0.0018 (7)	0.0022 (7)	−0.0025 (8)
O19	0.0180 (9)	0.0316 (11)	0.0209 (10)	−0.0012 (8)	−0.0044 (8)	−0.0128 (9)
C20	0.0274 (16)	0.0328 (16)	0.0380 (18)	0.0028 (13)	−0.0163 (13)	−0.0150 (14)
N21	0.0159 (11)	0.0311 (13)	0.0306 (13)	−0.0007 (10)	−0.0004 (10)	−0.0162 (11)
C22	0.0189 (13)	0.0336 (16)	0.0279 (15)	−0.0068 (12)	0.0022 (11)	−0.0155 (13)
C23	0.0224 (14)	0.0279 (14)	0.0255 (15)	−0.0043 (11)	−0.0035 (11)	−0.0109 (12)
C24	0.0169 (13)	0.0271 (14)	0.0259 (14)	−0.0012 (11)	−0.0037 (11)	−0.0149 (12)
C25	0.0161 (13)	0.0299 (14)	0.0239 (14)	−0.0024 (11)	−0.0006 (11)	−0.0113 (12)
C26	0.0191 (13)	0.0300 (15)	0.0266 (15)	−0.0013 (11)	−0.0024 (11)	−0.0106 (12)
C27	0.0196 (14)	0.0283 (14)	0.0274 (15)	0.0004 (11)	−0.0053 (11)	−0.0127 (12)
N28	0.0155 (12)	0.0324 (13)	0.0331 (14)	0.0040 (10)	−0.0042 (10)	−0.0128 (11)
Cl29	0.0533 (5)	0.0366 (4)	0.0275 (4)	0.0104 (4)	−0.0082 (4)	−0.0149 (3)
O30	0.147 (4)	0.065 (2)	0.0256 (15)	−0.003 (2)	−0.0041 (19)	−0.0070 (15)
O31	0.178 (5)	0.108 (3)	0.089 (3)	−0.104 (4)	−0.061 (3)	0.019 (3)
O32	0.071 (2)	0.081 (2)	0.0426 (16)	−0.0272 (17)	−0.0014 (14)	−0.0352 (16)
O33	0.193 (5)	0.104 (3)	0.056 (2)	0.106 (4)	0.012 (3)	−0.002 (2)
O34	0.023 (3)	0.032 (3)	0.099 (6)	0.002 (3)	−0.016 (3)	−0.043 (4)
C35	0.105 (13)	0.078 (10)	0.087 (12)	−0.040 (10)	0.035 (10)	−0.039 (10)
O36	0.072 (4)	0.051 (3)	0.067 (4)	−0.034 (3)	0.051 (3)	−0.035 (3)
C37	0.100 (12)	0.26 (2)	0.068 (9)	−0.087 (15)	−0.018 (8)	−0.002 (12)
O38	0.048 (2)	0.058 (2)	0.0291 (19)	−0.0050 (19)	0.0029 (17)	−0.0255 (19)

Geometric parameters (Å, º)

Zn1—O18	2.0977 (18)	O18—H18A	0.9702
Zn1—O18^i	2.0977 (18)	O18—H18B	0.9703
Zn1—N2^i	2.120 (2)	O19—C20	1.432 (4)
Zn1—N2	2.120 (2)	O19—H19	0.9813
Zn1—O19^i	2.1642 (19)	C20—H20A	0.9800
Zn1—O19	2.1642 (19)	C20—H20B	0.9800
N2—C7	1.341 (3)	C20—H20C	0.9800
N2—C3	1.345 (3)	N21—C22	1.336 (4)
C3—C4	1.375 (4)	N21—C26	1.340 (4)
C3—H3	0.9500	C22—C23	1.391 (4)
C4—C5	1.397 (4)	C22—H22	0.9500
C4—H4	0.9500	C23—C24	1.391 (4)
C5—C6	1.397 (4)	C23—H23	0.9500
C5—C8	1.470 (4)	C24—C25	1.398 (4)
C6—C7	1.380 (4)	C24—C27	1.475 (4)
C6—H6	0.9500	C25—C26	1.378 (4)
C7—H7	0.9500	C25—H25	0.9500
C8—N9	1.279 (4)	C26—H26	0.9500
C8—H8	0.9500	C27—N28	1.276 (4)
N9—N10	1.412 (3)	C27—H27	0.9500
N10—C11	1.279 (4)	N28—N28^ii	1.415 (5)
C11—C12	1.474 (4)	Cl29—O32	1.402 (3)
C11—H11	0.9500	Cl29—O33	1.403 (4)
C12—C17	1.390 (4)	Cl29—O31	1.405 (5)
C12—C13	1.395 (4)	Cl29—O30	1.410 (3)
C13—C14	1.379 (4)	O34—C35	1.514 (9)
C13—H13	0.9500	C35—H35A	0.9800
C14—N15	1.345 (4)	C35—H35B	0.9800
C14—H14	0.9500	C35—H35C	0.9800
N15—C16	1.336 (4)	O36—C37	1.526 (9)
C16—C17	1.389 (4)	C37—H37A	0.9800
C16—H16	0.9500	C37—H37B	0.9800
C17—H17	0.9500	C37—H37C	0.9800
O18—Zn1—O18^i	180.0	N15—C16—C17	123.4 (3)
O18—Zn1—N2^i	89.85 (8)	N15—C16—H16	118.3
O18^i—Zn1—N2^i	90.15 (8)	C17—C16—H16	118.3
O18—Zn1—N2	90.15 (8)	C16—C17—C12	119.0 (3)
O18^i—Zn1—N2	89.85 (8)	C16—C17—H17	120.5
N2^i—Zn1—N2	180.00 (11)	C12—C17—H17	120.5
O18—Zn1—O19^i	88.77 (7)	Zn1—O18—H18A	127.1
O18^i—Zn1—O19^i	91.23 (7)	Zn1—O18—H18B	115.2
N2^i—Zn1—O19^i	88.80 (8)	H18A—O18—H18B	100.1
N2—Zn1—O19^i	91.20 (8)	C20—O19—Zn1	124.83 (17)
O18—Zn1—O19	91.23 (7)	C20—O19—H19	99.5
O18^i—Zn1—O19	88.77 (7)	Zn1—O19—H19	134.6
N2^i—Zn1—O19	91.20 (8)	O19—C20—H20A	109.5
N2—Zn1—O19	88.80 (8)	O19—C20—H20B	109.5
O19^i—Zn1—O19	179.999 (1)	H20A—C20—H20B	109.5
C7—N2—C3	117.7 (2)	O19—C20—H20C	109.5
C7—N2—Zn1	122.20 (18)	H20A—C20—H20C	109.5
C3—N2—Zn1	119.86 (18)	H20B—C20—H20C	109.5
N2—C3—C4	123.1 (3)	C22—N21—C26	117.5 (2)
N2—C3—H3	118.4	N21—C22—C23	123.2 (3)
C4—C3—H3	118.4	N21—C22—H22	118.4
C3—C4—C5	119.1 (3)	C23—C22—H22	118.4
C3—C4—H4	120.5	C24—C23—C22	118.8 (3)
C5—C4—H4	120.5	C24—C23—H23	120.6
C6—C5—C4	118.0 (2)	C22—C23—H23	120.6
C6—C5—C8	120.1 (3)	C23—C24—C25	118.1 (3)
C4—C5—C8	121.9 (3)	C23—C24—C27	120.5 (3)
C7—C6—C5	119.0 (3)	C25—C24—C27	121.4 (3)
C7—C6—H6	120.5	C26—C25—C24	118.8 (3)
C5—C6—H6	120.5	C26—C25—H25	120.6
N2—C7—C6	123.1 (3)	C24—C25—H25	120.6
N2—C7—H7	118.4	N21—C26—C25	123.6 (3)
C6—C7—H7	118.4	N21—C26—H26	118.2
N9—C8—C5	119.4 (3)	C25—C26—H26	118.2
N9—C8—H8	120.3	N28—C27—C24	119.6 (3)
C5—C8—H8	120.3	N28—C27—H27	120.2
C8—N9—N10	111.9 (3)	C24—C27—H27	120.2
C11—N10—N9	110.7 (3)	C27—N28—N28^ii	111.6 (3)
N10—C11—C12	120.8 (3)	O32—Cl29—O33	107.4 (3)
N10—C11—H11	119.6	O32—Cl29—O31	108.5 (3)
C12—C11—H11	119.6	O33—Cl29—O31	107.8 (4)
C17—C12—C13	118.0 (3)	O32—Cl29—O30	111.1 (2)
C17—C12—C11	119.2 (3)	O33—Cl29—O30	112.3 (2)
C13—C12—C11	122.8 (3)	O31—Cl29—O30	109.6 (3)
C14—C13—C12	119.0 (3)	O36—C37—H37A	109.5
C14—C13—H13	120.5	O36—C37—H37B	109.5
C12—C13—H13	120.5	H37A—C37—H37B	109.5
N15—C14—C13	123.5 (3)	O36—C37—H37C	109.5
N15—C14—H14	118.2	H37A—C37—H37C	109.5
C13—C14—H14	118.2	H37B—C37—H37C	109.5
C16—N15—C14	117.1 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O18—H18A···N21^iii	0.97	1.80	2.773 (3)	180
O18—H18B···N15^iv	0.97	1.83	2.798 (3)	180
O19—H19···O34^v	0.98	1.69	2.653 (7)	167
O19···O38^v	?	?	2.752 (7)	?
O36···O30	?	?	2.904 (7)	?
O36···O34^vi	?	?	2.937 (8)	?
O36···O38^vi	?	?	2.937 (7)	?

Symmetry codes: (iii) −x+1, −y+1, −z+2; (iv) x−1, y−1, z+1; (v) x, y, z+1; (vi) −x, −y+1, −z+1.