Two tetra­nuclear zinc clusters, [Zn₄(μ₃-OEt)₂(μ₂-MalO)₄Et₂] and [Zn₄(μ₃-GueO)₂(μ₂-GueO)₂(μ₂-MalO)₂(MalO)₂]·2C₇H₈, containing defective dicubane core geometries (MalOH is maltol and GueOH is guethol)

The zinc alkoxide molecules in di-μ₃-ethano­lato-diethyl­tetra­kis­(μ₂-2-methyl-4-oxo-4H-pyran-3-olato-κ³O³,O⁴:O³)tetra­zinc(II), [Zn₄(C₂H₅)₂(C₂H₅O)₂(C₆H₅O₃)₄], (I), and bis­(μ₃-2-eth­oxy­phe­nolato-κ⁴O¹,O²:O¹:O¹)bis­(μ₂-2-eth­oxy­phenolato-κ³O¹,O²:O¹)bis­(μ₂-2-methyl-4-oxo-4H-pyran-3-olato-κ³O³,O⁴:O³)bis­(2-methyl-4-oxo-4H-pyran-3-olato-κ²O³,O⁴)tetra­zinc(II) toluene disolvate, [Zn₄(C₆H₅O₃)₄(C₈H₉O₂)₄]·2C₇H₈, (II), lie on crystallographic centres of inversion. The asymmetric units of (I) and (II) contain half of the tetra­meric unit and additionally one mol­ecule of toluene for (II). The Zn^II atoms are four- and six-coordinated in distorted tetra­hedral and octa­hedral geometries for (I), and six-coordinated in a dis­torted octa­hedral environment for (II). The Zn^II atoms in both compounds are arranged in a defect dicubane Zn₄O₆ core structure composed of two EtZnO₃ tetra­hedra and ZnO₆ octa­hedra for (I), and of four ZnO₆ octa­hedra for (II), sharing common corners. The maltolate ligands exist mostly in a μ₂-bridging mode, while the guetholate ligands prefer a higher coordination mode and act as μ₃- and μ₂-bridges.

S1. Comment

Alkoxo zinc complexes have been used as initiators for the ring-opening polymeryzation of cyclic esters (Chamberlain et al., 2001), as electroluminescent compounds for light-emitting diodes (Kajii et al., 2001) and as precursors for the preparation of high-purity zinc oxide employed in numerous applications (Wang, 2004). It was previously mentioned (Boyle et al., 2004) that the arrangement of the central core of zinc alkoxy and alkyl alkoxy precursors affects the morphology of nanoparticles, which will ultimately dictate the electrical and optical properties of the final devices. We report herein the synthesis and structural characteristics of new tetranuclear [Zn₄(R)₂(OR)₆] and [Zn₄(OR)₈] precursors of ZnO based on defective dicubane-like cores, which were not yet used for such purposes. This work also includes research on the formation of alkoxides by the action of dioxygen on alkyl zinc compounds (Lewiński et al., 2003; Grévy, 2011) as a new very attractive way for the preparation of `Zn(R)(OR)' precursors of ZnO nanoparticles. In our work, we decided to use maltol (MalOH; 3-hydroxy-2-methyl-4H-pyran-4-one) and guethol (GueOH; 3-ethoxy-4-hydroxybenzaldehyde) as ligands due to their commercial availability, low cost and human-friendly nature, approved by the US Food and Drug Administration (Bauer et al., 2001). Moreover, previous work has shown that maltol is a very attractive ligand which is easily deprotonated to give an O,O'-bidentate chelating system for complexation with a number of biologically active metal ions to form thermodynamic stable and neutrally charged complexes. For instance, metal–maltolate complexes, such as [Fe(MalO)₃] (Ahmet et al., 1988), [Al(MalO)₃] (Finnegan et al., 1986; Nelson et al., 1988; Yu et al., 2002), [Ga(MalO)₃] (Bernstein et al., 2000; Chitambar et al., 2007) and [VO(MalO)₂] (Thompson et al., 2003, 2004; Saatchi et al., 2005), have found numerous medical applications as metallotherapeutic drugs and metal-based diagnostic agents (Thompson et al., 2006).

The structure of the tetranuclear compound [Zn₄(µ₃-OEt)₂(µ₂-MalO)₄Et₂], (I), with the atom-numbering scheme, is shown in Fig. 1. Selected bond lengths and angles are listed in Table 1. The molecular structure of (I) exists as a centrosymmetric cluster, which contains two types of environmentally different Zn^II centres. The Zn^II ions and the bridging alkoxide groups are arranged in a double-open face-shared dicubane-like core with two missing vertices similar to that observed in the structure of the previously published conformational isomer [Zn₄(µ₃-OEt)₂(µ₂-MalO)₄Et₂].C₇H₈, (I') (Petrus & Sobota, 2012). Atoms Zn1 and Zn2 are linked through a µ₃-OEt bridge via atom O15, which also connects to Zn2ⁱ [Symmetry code: (i) -x+1, -y+1, -z+1] to form a Zn₃ triangle with Zn···Zn nonbonding distances significantly different (shorter by 0.15 and 0.13 Å for Zn1···Zn2 and Zn2···Zn2ⁱ, and longer by 0.12 Å for Zn1···Zn2ⁱ) than those reported for (I'), presumably because of the absence of toluene molecules in the lattice, which, through C—H···O hydrogen bonds, could stabilize the Zn₄ cage at a higher level of regularity. Very different values of the Zn—O bond lengths within the Zn₂O₂ diamond cores indicate a high deformation of the central core geometry, with minimum and maximum deviations of 5.2 and 7.7% from the average Zn—O bond length. While for (I'), the deformation does not exceed 1.7 (minimun) and 2.5% (maximum). The Zn1 ion is coordinated in a tetrahedral manner to one ethyl, one ethanolate and two maltolate ligands in a monodentate coordination mode through atoms O3 and O9ⁱ. The Zn1—O3 and Zn1—O15 bond lengths are in the expected range for a four-coordinate Zn^II center, whilst significant bond elongation is observed for Zn1—O9, i.e. by about 0.17 Å (Table 1). The terminal Zn1—C1 bond lenght is slightly longer (ca 0.1 Å) than observed in the structure of ZnEt₂ (Bacsa et al., 2011). A considerable deviation from the ideal tetrahedral geometry is mainly evident in the bond angles around the Zn1 center (Table 1), accomplished by a dihedral angle of 84 (2)° between the O3/Zn1/O9ⁱ and C1/Zn1/O15 planes. The Zn2 ion is six-coordinated by two ethanolate and two maltolate ligands in a bidentate chelating mode through the O atoms of alkoxy and carbonyl groups, forming five-membered Zn2/O3/C3/C4/O4 and Zn2/O9/C9/C10/O10 chelate rings. The first of these metallacycles is twisted about the Zn2—O4 bond, while the second is planar, with a largest displacement from the least-squares plane of 0.035 (2) Å for atom O10. The environment of the Zn2 atom can be considered as an octahedron distorted towards a trigonal prism, as confirmed by the shape measure parameter S(Oh) = 12.27 (Alvarez et al., 2002). One of the maltolate ligands occupies two positions in the equatorial plane via atoms O3 and O4, while the second ligand has alkoxo atom O9 positioned equatorially and keto atom O10 positioned axially. The Zn2—O bond lengths involving maltolate O atoms show a clear division into two distinct categories, the first involving keto (longer by ca 0.08–0.09 Å) and the second involving alkoxo donor sets, quite different than in the structure of (I') with a high compatibility of both types of bonds. The Zn2—µ₃O distances clearly show bond elongation in the axial plane of the molecule. Distortion from an ideal octahedral environment is clearly evident in the nonlinear transoid angles, supported by cisoid angles deviating significantly from 90° (Table 1). The crystal packing is stabilized by weak π–π stacking and C—H···O interactions (Table 2).

The X-ray structure determination revealed that [Zn₄(µ₃-GueO)₂(µ₂-GueO)₂(µ₂-MalO)₂(MalO)₂].2C₇H₈, (II), is also a tetramer, in which the two ethyl and two ethanolate groups, presented in (I), are replaced by four 2-ethoxyphenolate ligands. The structure of (II), with the atom-numbering scheme, is shown in Fig. 2. Selected bond lengths and angles are listed in Table 3. The molecular structure of (II) exists as a centrosymmetric zinc cluster containing a Zn₄O₆ `double-open' face-shared dicubane core, in which the metal ions are held together by four µ₂ and two µ₃ alkoxo O atoms. The phenolate O atoms of four guetholate ligands act as two µ₃- and two µ₂-O bridges, as opposed to the maltolate O atoms in (I) which act as two µ₂-O bridges. The Zn^II ions in (II) form six-coordinated distorted octahedra with O₆ donor sets. The deformation of the coordination geometry around the Zn^II centers were analyzed in terms of the continuous shape measures. The departure from an ideal octahedron is larger for the coordination environment around Zn2, as confirmed by the metric shape parameters S(Oh) = 4.78 for Zn1 and 8.55 for Zn2. Furthermore, the alkoxo O atoms of the maltolate ligands are in cis positions in contrast to the trans positions in (I). The Zn—O bond lengths within the Zn₂O₂ cores demonstrate much higher regularity of a central core geometry in comparison with (I). Moreover, all five-membered Zn₂O₂C₂ metallacycles in (II) have a conformation based on an envelope on the Zn position. The differences between Zn—O(alkoxo) and Zn—O(keto/ether) bond lengths of the two chelating ligands (except µ₂-MalO) are even more apparent than in the structure of (I), indicating a significant deformation of the polyhedral geometry outside the Zn₄ cage. Complex (II) shows hydrogen-bonding interactions between the tetranuclear units and the adjacent molecules to link them into extended chains (Table 4).

The double-open dicubane-like core is a common structural motif in metal coordination chemistry, found frequently in many coordination compounds (Pradeep et al., 2006; Mandal & Ray, 2007; Delferro et al., 2010; Jerzykiewicz et al., 2010; Costes et al., 2011), including (I) and (II). However, this kind of structural disposition for a zinc tetramer is not very common, as illustrated by the fact that only nine tetramers of this type have been so far reported and solid-state characterized: [Zn₄(µ₃-OPh)₂(µ₂-pa)₄(Ph)₂] [where paH = pivaloylacetone; Cambridge Structural Database (CSD; Allen, 2002) refcode CINHIQ; Boersma et al., 1974], [Zn₄(µ₃-OMe)₂(µ₂-pa)₄Et₂] (FOFTUP; Dekker et al., 1987), [Zn₄(µ₃-OMe)₂(µ₂-acac)₄(acac)₂] (Hacac = acetylacetone; EKOSIG; Seisenbaeva et al., 2003), [Zn₄(µ₃-azol)₂(µ₂-azol)₂(OOEt)₂Et₂] (azolH = 1-aziridineethanol; EMEYAW; Lewiński et al., 2003), [Zn₄(µ₃-OQ)₂(µ₂-OQ)₄(OAc)₂].MeOH (HOQ = 8-hydroxyquinoline; XELBOG; Xu et al., 2005), [Zn₄(µ₃-OQ)₂(µ₂-OQ)₄(OAc)₂].2H₂O (BOWHOL; Sattarzadeh et al., 2009), [Zn₄(µ₃-OMe)₂(µ₂-ON^R)₄(Me)₂] {HON^R = 2-[3-(heptaisobutyloctasilsesquioxanyl)propyliminomethyl]phenol; ILIWEG; Di Iulio et al., 2010}, [Zn₄(µ₃-OEt)₂(µ₂-O,N^R)₄Et₂] (ILIWIK; Di Iulio et al., 2010) and the aforementioned [Zn₄(µ₃-OEt)₂(µ₂-MalO)₄Et₂].C₇H₈ (Petrus & Sobota, 2012).

Among the examples cited above and the title zinc tetramers, we can distinguish two distinct classes of compounds. The first comprises alkylzinc alkoxides of general formula [Zn₄(µ₃-OR')₂(µ₂-O,X')₄(R)₂] (R = Me, Et, Ph; OR' = OMe, OEt, OPh; O,X' = O,O' or O,N' chelating donor ligands) [CINHIQ, FOFTUP, ILIWEG, ILIWIK, (I') and (I)], containing terminally coordinated alkyl groups on the external RZnO₃ tetrahedra, and two octahedra with ZnO₆ [CINHIQ, FOFTUP, (I') and (I)] or ZnO₄N₂ (ILIWEG and ILIWIK) topology. Similar to these, Lewiński et al. (2003) have reported a zinc alkylperoxide with µ₂-OOEt bridges (EMEYAW). The second group consists of alkoxides of type [Zn₄(µ₃-OR'/O,X')₂(µ₂-O,X')₄(O,X')₂] (OR' = OMe) [BOWHOL, EKOSIG, XELBOG and (II)], containing four octahedra in ZnO₆ [EKOSIG and (II)] or two pairs in ZnO₄N₂ and ZnO₅N (BOWHOL and XELBOG) environment.

In order to visualize the differences in the construction of the tetrameric unit in (I) and (II), an overlay of their core structures is shown in Fig. 3. In both cases, the two open cubanes are related by a crystallographic centre of inversion located at the centroid of the Zn2—µ₃O—Zn2ⁱ—µ₃Oⁱ face. Thus, the vertices of the common face of the dicubane unit are occupied by the Zn2 and Zn2ⁱ ions, being doubly bridged through alkoxo O atoms located on the other two vertices. These O atoms act as triple bridges since they are also linked to Zn1 and Zn1ⁱ atoms along the edges of both cubic subunits. The external vertices of the defective dicubanes are defined by Zn1 and Zn1ⁱ ions, supported by four doubly-bridged alkoxo O atoms. The dihedral angles between the planes defined by the atoms of the Zn₂O₂ faces are smaller than the ideal value of 90° for perfect double-open dicubane geometry, as shown in Fig. 3.

In order to compare the core structures of (I) and (II) with previously published Zn₄O₆ defective dicubanes, we have introduced the connectivity parameters d(1–2), d(1–2ⁱ), d(2–2ⁱ), d(1–1ⁱ), θ, θⁱ, σ, σⁱ and ϕ (Serna et al., 2000, 2010), which are summarized in Table 5. In the present classification system, d denotes the distance between Zn atoms, and θ, θⁱ, σ, σⁱ and ϕ denote Zn—O—Zn angles within the tetrameric unit; details are given in the legend of Table 5. Within the connectivity parameters for all nine compounds (Table 5), we cannot find specific unique parameters that are distinctive of each group. The only regular feature repeated in both class is that the ϕ angle is generally close to 99°. However, compounds (I) and (II), as well as compound (I'), show significant deviation from this value, viz. from 5 to 13° (Table 5). In addition, it is worth noting that (I) shows large deviations in the values of the d parameters in comparison with other compounds.

Related literature

For related literature, see: Ahmet et al. (1988); Allen (2002); Alvarez et al. (2002); Bacsa et al. (2011); Bauer et al. (2001); Bernstein et al. (2000); Boersma et al. (1974); Boyle et al. (2004); Chamberlain et al. (2001); Chitambar et al. (2007); Costes et al. (2011); Dekker et al. (1987); Delferro et al. (2010); Di Iulio, Jones, Mahon & Apperley (2010); Finnegan et al. (1986); Grévy (2011); Jerzykiewicz et al. (2010); Kajii et al. (2001); Lewiński et al. (2003); Mandal & Ray (2007); Nelson et al. (1988); Petrus & Sobota (2012); Pradeep et al. (2006); Saatchi et al. (2005); Sattarzadeh et al. (2009); Seisenbaeva et al. (2003); Serna et al. (2000, 2010); Thompson et al. (2003, 2004, 2006); Wang (2004); Xu et al. (2005); Yu et al. (2002).

S2. Experimental

All syntheses were performed under a dry N₂ atmosphere using standard Schlenk techniques. Reagents were purified by standard methods, i.e. toluene was distilled from Na and guethol was distilled from CaO. Maltol, guethol and ZnEt₂ were purchased from Aldrich. The method used for the synthesis of (I) is easier and simpler than previously published in our work (Petrus & Sobota, 2012). For the preparation of (I), ZnEt₂ (15.86 ml, 15.86 mmol) was added dropwise to a solution of MalOH (2 g, 15.86 mmol) in toluene (200 ml) at 273 K and the resulting mixture exposed to an excess of dry oxygen for 10 min. After oxygenation, excess O₂ was removed and the system was flow by nitrogen. The orange mixture was stirred for a further 1 h and allowed to warm to room temperature. After 2 h, the volume was reduced to 100 ml. Colourless crystals were obtained by slow evaporation from the mother liquor (yield 2.42 g, 67%). Analysis calculated for C₃₂H₄₀O₁₄Zn₄: C 42.22, H 4.43%; found: C 42.30, H 4.50%.

For the synthesis of (II), GueOH (0.55 ml, 4.40 mmol) was added to a solution of (I) (1 g, 1.10 mmol) in toluene (100 ml). The resulting mixture was stirred at room temperature for 1 h, and thereafter refluxed for 12 h. Next the volume was reduced to 60 ml. Colourless crystals were obtained by slow evaporation from the mother liquor (yield 1.25 g, 87%). Analysis calculated for C₃₂H₄₀O₁₄Zn₄: C 51.32, H 4.31%; found: C 51.55, H 4.36%.

S3. Refinement

Both crystals showed weak reflections, especially at high diffraction angle, so these were omitted from the refinements for θ > 27. All non-H atoms, excluding the atoms of disordered ethyl group of the aromatic ligand (C19A—C20A, C19B—C20B and C19C—C20C) and the toluene molecule (C29A–C35A and C29B–C35B) in (II), were refined anisotropically. In (I), the ethyl and ethanolate groups are disordered in two positions, with refined site-occupancy factors of 0.582 (15):0.418 (15) and 0.513 (8):0.487 (8), respectively. In (II), the ethyl group of one of the GueO ligands is disordered over three positions and was refined isotropically with occupation factors in the ratio 0.449 (15):0.365 (16):0.186 (14). The toluene molecule is disordered over two positions and was refined isotropically with occupation factors in the ratio 0.531 (9):0.469 (9). The phenyl ring of the disordered solvent molecule was constrained as a rigid hexagon, with C—C distances of 1.39 Å. Additionally, atom C31B was given the same U_iso value as atom C32B. All H atoms were positioned geometrically and treated as riding on their parent atoms, with C—H = 0.95 Å for aromatic, 0.98 Å for methyl and 0.99 Å for methylene H atoms, with U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) otherwise.

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure and atom-numbering schemes for [Zn4(µ3-OEt)2(µ2-MalO)4Et2], (I). Displacement ellipsoids are drawn at the 20% probability level. The second disorder components of the ethyl and ethanolate groups are drawn as dashed lines. H atoms have been omitted for clarity. [Symmetry code: (i) -x+1, -y+1, -z+1.]
	Fig. 2. The molecular structure and atom-numbering schemes for [Zn4(µ3-GueO)2(µ2-GueO)2(µ2-MalO)2(MalO)2].2C7H8, (II). Displacement ellipsoids are drawn at the 20% probability level. The disorder components of the ethyl group of the GueO ligand and the toluene solvent molecule are drawn as dashed lines or open bonds. H atoms, as well as the labels of the disordered toluene molecules (C29A–C35A and C29B–C35B), have been omitted for clarity. [Symmetry code: (i) -x+1, -y+1, -z+1.]
	Fig. 3. An overlay of the central cores of (I) (black) and (II) (white). (Software used for visualization: AMIRA; Stalling et al., 2005). [Symmetry code: (i) -x+1, -y+1, -z+1.]

(I) di-µ₃-ethanolato-diethyltetrakis(µ₂-2-methyl-4-oxo-4H-pyran-3- olato-κ³O³,O⁴:O³)tetrazinc(II)

Crystal data

[Zn4(C2H5)2(C2H5O)2(C6H5O3)4]	F(000) = 928
Mr = 910.20	Dx = 1.681 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6719 reflections
a = 9.851 (2) Å	θ = 3.0–28.0°
b = 18.828 (2) Å	µ = 2.70 mm^−1
c = 10.721 (3) Å	T = 100 K
β = 115.26 (2)°	Plate, colourless
V = 1798.3 (7) Å^3	0.37 × 0.22 × 0.16 mm
Z = 2

Data collection

Kuma KM-4 CCD κ-geometry diffractometer	3778 independent reflections
Radiation source: fine-focus sealed tube	2953 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω scans	θmax = 27.0°, θmin = 3.0°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2007)	h = −12→12
Tmin = 0.499, Tmax = 0.646	k = −24→14
11678 measured reflections	l = −12→12

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) = 0.098	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0632P)^2] where P = (Fo^2 + 2Fc^2)/3
3778 reflections	(Δ/σ)max = 0.001
248 parameters	Δρmax = 1.07 e Å^−3
0 restraints	Δρmin = −0.43 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	Occ. (<1)
Zn1	0.67689 (4)	0.413106 (18)	0.72023 (4)	0.03172 (12)
Zn2	0.37495 (4)	0.456431 (16)	0.49952 (4)	0.02778 (12)
C1	0.8234 (4)	0.3819 (2)	0.9141 (4)	0.0561 (11)
H1A	0.7780	0.3895	0.9796	0.067*	0.582 (15)
H1B	0.8467	0.3307	0.9142	0.067*	0.582 (15)
H1C	0.8315	0.4217	0.9772	0.067*	0.418 (15)
H1D	0.7752	0.3421	0.9405	0.067*	0.418 (15)
C2A	0.9529 (8)	0.4216 (9)	0.9535 (8)	0.081 (5)	0.582 (15)
H2A	1.0243	0.4076	1.0465	0.122*	0.582 (15)
H2B	0.9287	0.4721	0.9531	0.122*	0.582 (15)
H2C	0.9976	0.4133	0.8888	0.122*	0.582 (15)
C2B	0.9667 (11)	0.3608 (8)	0.9425 (11)	0.055 (3)	0.418 (15)
H2D	1.0194	0.3481	1.0402	0.082*	0.418 (15)
H2E	1.0199	0.3998	0.9219	0.082*	0.418 (15)
H2F	0.9634	0.3195	0.8856	0.082*	0.418 (15)
O3	0.4944 (2)	0.36549 (10)	0.5894 (2)	0.0349 (5)
C3	0.4468 (4)	0.30895 (16)	0.5025 (4)	0.0377 (8)
O4	0.2576 (2)	0.37831 (11)	0.3454 (3)	0.0367 (5)
C4	0.3186 (4)	0.31885 (16)	0.3687 (4)	0.0396 (8)
C5	0.2712 (4)	0.25959 (19)	0.2712 (5)	0.0523 (10)
H5	0.1914	0.2647	0.1819	0.063*
C6	0.3444 (5)	0.1978 (2)	0.3122 (6)	0.0610 (13)
H6	0.3176	0.1594	0.2488	0.073*
O7	0.4543 (3)	0.18798 (13)	0.4397 (4)	0.0603 (8)
C7	0.5058 (4)	0.24318 (17)	0.5361 (5)	0.0496 (10)
C8	0.6249 (5)	0.22151 (19)	0.6764 (5)	0.0666 (13)
H8A	0.6647	0.2639	0.7334	0.100*
H8B	0.7064	0.1967	0.6651	0.100*
H8C	0.5804	0.1898	0.7214	0.100*
O9	0.2689 (2)	0.55201 (10)	0.4431 (2)	0.0301 (5)
C9	0.1937 (3)	0.56435 (15)	0.5187 (3)	0.0265 (6)
O10	0.2580 (2)	0.45165 (10)	0.6263 (2)	0.0328 (5)
C10	0.1916 (3)	0.50809 (16)	0.6172 (3)	0.0294 (6)
C11	0.1103 (3)	0.52080 (19)	0.6975 (4)	0.0360 (7)
H11	0.1066	0.4867	0.7613	0.043*
C12	0.0413 (3)	0.58171 (19)	0.6787 (4)	0.0421 (9)
H12	−0.0144	0.5913	0.7305	0.051*
O13	0.0443 (2)	0.63315 (12)	0.5881 (3)	0.0428 (6)
C13	0.1215 (3)	0.62466 (16)	0.5082 (4)	0.0352 (7)
C14	0.1131 (4)	0.68768 (17)	0.4136 (5)	0.0568 (11)
H14A	0.0298	0.6804	0.3226	0.085*
H14B	0.2074	0.6911	0.4039	0.085*
H14C	0.0969	0.7317	0.4540	0.085*
O15	0.5592 (2)	0.50125 (9)	0.6610 (2)	0.0278 (4)
C15	0.5506 (4)	0.54704 (16)	0.7726 (4)	0.0389 (8)
H15A	0.5284	0.5960	0.7357	0.047*	0.513 (8)
H15B	0.4624	0.5308	0.7865	0.047*	0.513 (8)
H15C	0.4586	0.5763	0.7306	0.047*	0.487 (8)
H15D	0.6372	0.5800	0.8054	0.047*	0.487 (8)
C16A	0.6732 (8)	0.5514 (4)	0.9051 (8)	0.048 (2)	0.513 (8)
H16A	0.6473	0.5836	0.9636	0.072*	0.513 (8)
H16B	0.7617	0.5697	0.8960	0.072*	0.513 (8)
H16C	0.6951	0.5041	0.9471	0.072*	0.513 (8)
C16B	0.5490 (8)	0.5060 (3)	0.9098 (7)	0.0353 (19)	0.487 (8)
H16D	0.5426	0.5414	0.9741	0.053*	0.487 (8)
H16E	0.6414	0.4783	0.9557	0.053*	0.487 (8)
H16F	0.4621	0.4742	0.8802	0.053*	0.487 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0325 (2)	0.02425 (19)	0.0408 (2)	0.00634 (14)	0.01794 (17)	0.00767 (15)
Zn2	0.02649 (19)	0.01765 (17)	0.0448 (2)	0.00345 (12)	0.02055 (16)	0.00275 (14)
C1	0.048 (2)	0.062 (2)	0.060 (3)	0.0200 (19)	0.025 (2)	0.025 (2)
C2A	0.026 (4)	0.157 (14)	0.050 (5)	0.001 (5)	0.006 (3)	0.006 (6)
C2B	0.048 (6)	0.057 (8)	0.050 (6)	−0.007 (5)	0.011 (4)	0.009 (5)
O3	0.0304 (11)	0.0160 (9)	0.0603 (15)	0.0025 (8)	0.0213 (10)	0.0026 (10)
C3	0.0353 (17)	0.0226 (15)	0.066 (2)	0.0010 (13)	0.0318 (17)	0.0023 (15)
O4	0.0277 (11)	0.0240 (11)	0.0630 (16)	−0.0017 (8)	0.0237 (11)	−0.0031 (10)
C4	0.0392 (18)	0.0220 (15)	0.071 (3)	−0.0055 (13)	0.0360 (18)	−0.0083 (16)
C5	0.047 (2)	0.036 (2)	0.083 (3)	−0.0105 (16)	0.036 (2)	−0.0155 (19)
C6	0.071 (3)	0.0285 (19)	0.104 (4)	−0.0129 (19)	0.057 (3)	−0.027 (2)
O7	0.0529 (17)	0.0255 (12)	0.105 (2)	0.0007 (11)	0.0356 (17)	−0.0090 (14)
C7	0.049 (2)	0.0209 (15)	0.093 (3)	−0.0005 (14)	0.043 (2)	0.0006 (18)
C8	0.047 (2)	0.0271 (18)	0.125 (4)	0.0102 (16)	0.035 (2)	0.022 (2)
O9	0.0279 (11)	0.0220 (10)	0.0487 (14)	0.0071 (8)	0.0242 (10)	0.0055 (9)
C9	0.0177 (13)	0.0261 (14)	0.0337 (17)	0.0017 (11)	0.0089 (12)	−0.0037 (13)
O10	0.0265 (11)	0.0276 (11)	0.0481 (14)	0.0017 (8)	0.0195 (10)	0.0062 (10)
C10	0.0191 (13)	0.0332 (16)	0.0339 (17)	−0.0034 (12)	0.0094 (12)	−0.0060 (13)
C11	0.0229 (15)	0.0507 (19)	0.0349 (18)	−0.0039 (14)	0.0127 (13)	−0.0063 (16)
C12	0.0237 (16)	0.056 (2)	0.049 (2)	−0.0008 (15)	0.0179 (15)	−0.0157 (18)
O13	0.0254 (11)	0.0433 (13)	0.0633 (16)	0.0048 (10)	0.0222 (11)	−0.0114 (12)
C13	0.0257 (15)	0.0314 (16)	0.048 (2)	0.0012 (12)	0.0156 (14)	−0.0117 (14)
C14	0.052 (2)	0.0256 (17)	0.102 (3)	0.0125 (16)	0.042 (2)	0.003 (2)
O15	0.0265 (10)	0.0198 (9)	0.0428 (12)	0.0023 (8)	0.0201 (9)	0.0007 (9)
C15	0.0432 (19)	0.0290 (16)	0.058 (2)	−0.0044 (14)	0.0349 (18)	−0.0095 (15)
C16A	0.042 (4)	0.062 (5)	0.050 (5)	−0.005 (3)	0.029 (4)	−0.020 (4)
C16B	0.042 (4)	0.031 (4)	0.040 (4)	−0.002 (3)	0.025 (3)	−0.008 (3)

Geometric parameters (Å, º)

Zn1—C1	2.047 (4)	C8—H8A	0.9800
Zn1—O3	1.962 (2)	C8—H8B	0.9800
Zn1—O9^i	2.141 (2)	C8—H8C	0.9800
Zn1—O15	1.968 (2)	O9—C9	1.331 (4)
Zn2—O3	2.068 (2)	O9—Zn1^i	2.141 (2)
Zn2—O4	2.145 (2)	C9—C13	1.319 (4)
Zn2—O9	2.039 (2)	C9—C10	1.502 (4)
Zn2—O10	2.126 (2)	O10—C10	1.230 (3)
Zn2—O15	2.079 (2)	C10—C11	1.424 (4)
Zn2—O15^i	2.229 (2)	C11—C12	1.304 (5)
C1—C2B	1.370 (12)	C11—H11	0.9500
C1—C2A	1.381 (11)	C12—O13	1.381 (4)
C1—H1A	0.9900	C12—H12	0.9500
C1—H1B	0.9900	O13—C13	1.376 (4)
C1—H1C	0.9900	C13—C14	1.540 (5)
C1—H1D	0.9900	C14—H14A	0.9800
C2A—H2A	0.9800	C14—H14B	0.9800
C2A—H2B	0.9800	C14—H14C	0.9800
C2A—H2C	0.9800	O15—C15	1.507 (4)
C2B—H2D	0.9800	O15—Zn2^i	2.229 (2)
C2B—H2E	0.9800	C15—C16A	1.421 (8)
C2B—H2F	0.9800	C15—C16B	1.667 (7)
O3—C3	1.359 (4)	C15—H15A	0.9900
C3—C7	1.350 (4)	C15—H15B	0.9900
C3—C4	1.464 (5)	C15—H15C	0.9900
O4—C4	1.244 (4)	C15—H15D	0.9900
C4—C5	1.462 (5)	C16A—H16A	0.9800
C5—C6	1.340 (6)	C16A—H16B	0.9800
C5—H5	0.9500	C16A—H16C	0.9800
C6—O7	1.346 (6)	C16B—H16D	0.9800
C6—H6	0.9500	C16B—H16E	0.9800
O7—C7	1.399 (5)	C16B—H16F	0.9800
C7—C8	1.516 (6)
C1—Zn1—O9^i	127.25 (13)	C6—C5—C4	117.7 (4)
O3—Zn1—C1	128.92 (14)	C6—C5—H5	121.1
O3—Zn1—O9^i	91.59 (9)	C4—C5—H5	121.1
O3—Zn1—O15	85.46 (8)	C5—C6—O7	122.7 (4)
O15—Zn1—C1	129.28 (14)	C5—C6—H6	118.7
O15—Zn1—O9^i	78.19 (8)	O7—C6—H6	118.7
O3—Zn2—O4	78.68 (9)	C6—O7—C7	121.9 (3)
O3—Zn2—O10	91.31 (8)	C3—C7—O7	120.3 (4)
O3—Zn2—O15	80.04 (8)	C3—C7—C8	125.0 (4)
O3—Zn2—O15^i	111.14 (8)	O7—C7—C8	114.6 (3)
O4—Zn2—O15^i	83.62 (8)	C7—C8—H8A	109.5
O9—Zn2—O3	170.61 (9)	C7—C8—H8B	109.5
O9—Zn2—O4	109.72 (9)	H8A—C8—H8B	109.5
O9—Zn2—O10	82.98 (8)	C7—C8—H8C	109.5
O9—Zn2—O15	92.50 (8)	H8A—C8—H8C	109.5
O9—Zn2—O15^i	74.74 (7)	H8B—C8—H8C	109.5
O10—Zn2—O4	101.70 (8)	C9—O9—Zn2	108.77 (18)
O10—Zn2—O15^i	157.55 (7)	C9—O9—Zn1^i	147.41 (18)
O15—Zn2—O4	155.76 (7)	Zn2—O9—Zn1^i	103.77 (8)
O15—Zn2—O10	90.22 (8)	C13—C9—O9	121.2 (3)
O15—Zn2—O15^i	93.39 (8)	C13—C9—C10	119.9 (3)
O3—Zn1—Zn2	42.88 (6)	O9—C9—C10	118.9 (2)
O15—Zn1—Zn2	43.21 (6)	C10—O10—Zn2	109.14 (19)
C1—Zn1—Zn2	154.94 (12)	O10—C10—C11	121.0 (3)
O9^i—Zn1—Zn2	77.42 (6)	O10—C10—C9	119.9 (3)
O9—Zn2—Zn2^i	80.34 (6)	C11—C10—C9	119.1 (3)
O3—Zn2—Zn2^i	98.64 (6)	C12—C11—C10	116.4 (3)
O15—Zn2—Zn2^i	48.81 (6)	C12—C11—H11	121.8
O10—Zn2—Zn2^i	134.38 (6)	C10—C11—H11	121.8
O4—Zn2—Zn2^i	123.88 (6)	C11—C12—O13	124.0 (3)
O15^i—Zn2—Zn2^i	44.58 (5)	C11—C12—H12	118.0
O9—Zn2—Zn1	132.85 (6)	O13—C12—H12	118.0
O3—Zn2—Zn1	40.21 (6)	C13—O13—C12	122.7 (2)
O15—Zn2—Zn1	40.40 (5)	C9—C13—O13	117.9 (3)
O10—Zn2—Zn1	96.26 (6)	C9—C13—C14	126.5 (3)
O4—Zn2—Zn1	116.46 (6)	O13—C13—C14	115.6 (3)
O15^i—Zn2—Zn1	100.83 (6)	C13—C14—H14A	109.5
Zn2^i—Zn2—Zn1	66.80 (2)	C13—C14—H14B	109.5
C2B—C1—C2A	50.0 (5)	H14A—C14—H14B	109.5
C2B—C1—Zn1	121.4 (5)	C13—C14—H14C	109.5
C2A—C1—Zn1	108.3 (5)	H14A—C14—H14C	109.5
C2B—C1—H1A	128.2	H14B—C14—H14C	109.5
C2A—C1—H1A	110.0	C15—O15—Zn1	116.81 (19)
Zn1—C1—H1A	110.0	C15—O15—Zn2	124.64 (17)
C2B—C1—H1B	60.1	Zn1—O15—Zn2	96.39 (8)
C2A—C1—H1B	110.0	C15—O15—Zn2^i	122.84 (16)
Zn1—C1—H1B	110.0	Zn1—O15—Zn2^i	103.03 (8)
H1A—C1—H1B	108.4	Zn2—O15—Zn2^i	86.61 (8)
C2B—C1—H1C	107.0	C16A—C15—O15	121.0 (4)
C2A—C1—H1C	65.5	C16A—C15—C16B	57.9 (4)
Zn1—C1—H1C	107.0	O15—C15—C16B	117.4 (3)
H1A—C1—H1C	48.4	C16A—C15—H15A	107.1
H1B—C1—H1C	141.8	O15—C15—H15A	107.1
C2B—C1—H1D	107.0	C16B—C15—H15A	134.4
C2A—C1—H1D	144.6	C16A—C15—H15B	107.1
Zn1—C1—H1D	107.0	O15—C15—H15B	107.1
H1A—C1—H1D	59.4	C16B—C15—H15B	52.1
H1B—C1—H1D	53.4	H15A—C15—H15B	106.8
H1C—C1—H1D	106.7	C16A—C15—H15C	130.2
C1—C2A—H2A	109.5	O15—C15—H15C	107.9
C1—C2A—H2B	109.5	C16B—C15—H15C	107.9
H2A—C2A—H2B	109.5	H15A—C15—H15C	45.3
C1—C2A—H2C	109.5	H15B—C15—H15C	63.2
H2A—C2A—H2C	109.5	C16A—C15—H15D	51.1
H2B—C2A—H2C	109.5	O15—C15—H15D	107.9
C1—C2B—H2D	109.5	C16B—C15—H15D	107.9
C1—C2B—H2E	109.5	H15A—C15—H15D	64.5
H2D—C2B—H2E	109.5	H15B—C15—H15D	144.9
C1—C2B—H2F	109.5	H15C—C15—H15D	107.2
H2D—C2B—H2F	109.5	C15—C16A—H16A	109.5
H2E—C2B—H2F	109.5	C15—C16A—H16B	109.5
C3—O3—Zn1	142.24 (19)	H16A—C16A—H16B	109.5
C3—O3—Zn2	111.56 (19)	C15—C16A—H16C	109.5
Zn1—O3—Zn2	96.91 (8)	H16A—C16A—H16C	109.5
C7—C3—O3	123.5 (3)	H16B—C16A—H16C	109.5
C7—C3—C4	118.1 (3)	C15—C16B—H16D	109.5
O3—C3—C4	118.2 (3)	C15—C16B—H16E	109.5
C4—O4—Zn2	114.0 (2)	H16D—C16B—H16E	109.5
O4—C4—C5	124.3 (4)	C15—C16B—H16F	109.5
O4—C4—C3	116.9 (3)	H16D—C16B—H16F	109.5
C5—C4—C3	118.8 (3)	H16E—C16B—H16F	109.5
O3—Zn1—Zn2—O9	170.82 (12)	C6—O7—C7—C3	−0.8 (5)
O15—Zn1—Zn2—O9	3.27 (12)	C6—O7—C7—C8	177.2 (3)
C1—Zn1—Zn2—O9	87.9 (3)	O15—Zn2—O9—C9	−85.37 (18)
O9^i—Zn1—Zn2—O9	−82.78 (10)	O10—Zn2—O9—C9	4.55 (18)
O15—Zn1—Zn2—O3	−167.55 (13)	O4—Zn2—O9—C9	104.51 (18)
C1—Zn1—Zn2—O3	−82.9 (3)	O15^i—Zn2—O9—C9	−178.20 (19)
O9^i—Zn1—Zn2—O3	106.39 (11)	Zn2^i—Zn2—O9—C9	−132.83 (18)
O3—Zn1—Zn2—O15	167.55 (13)	Zn1—Zn2—O9—C9	−87.49 (18)
C1—Zn1—Zn2—O15	84.6 (3)	O15—Zn2—O9—Zn1^i	96.63 (10)
O9^i—Zn1—Zn2—O15	−86.06 (10)	O10—Zn2—O9—Zn1^i	−173.45 (10)
O3—Zn1—Zn2—O10	84.60 (11)	O4—Zn2—O9—Zn1^i	−73.49 (10)
O15—Zn1—Zn2—O10	−82.95 (10)	O15^i—Zn2—O9—Zn1^i	3.79 (8)
C1—Zn1—Zn2—O10	1.7 (3)	Zn2^i—Zn2—O9—Zn1^i	49.17 (7)
O9^i—Zn1—Zn2—O10	−169.00 (7)	Zn1—Zn2—O9—Zn1^i	94.51 (10)
O3—Zn1—Zn2—O4	−21.81 (12)	Zn2—O9—C9—C13	176.2 (2)
O15—Zn1—Zn2—O4	170.65 (11)	Zn1^i—O9—C9—C13	−7.4 (5)
C1—Zn1—Zn2—O4	−104.7 (3)	Zn2—O9—C9—C10	−3.9 (3)
O9^i—Zn1—Zn2—O4	84.59 (9)	Zn1^i—O9—C9—C10	172.5 (2)
O3—Zn1—Zn2—O15^i	−110.02 (11)	O9—Zn2—O10—C10	−4.9 (2)
O15—Zn1—Zn2—O15^i	82.43 (11)	O3—Zn2—O10—C10	167.6 (2)
C1—Zn1—Zn2—O15^i	167.1 (3)	O15—Zn2—O10—C10	87.6 (2)
O9^i—Zn1—Zn2—O15^i	−3.63 (7)	O4—Zn2—O10—C10	−113.7 (2)
O3—Zn1—Zn2—Zn2^i	−139.46 (10)	O15^i—Zn2—O10—C10	−11.9 (3)
O15—Zn1—Zn2—Zn2^i	52.99 (9)	Zn2^i—Zn2—O10—C10	64.2 (2)
C1—Zn1—Zn2—Zn2^i	137.6 (3)	Zn1—Zn2—O10—C10	127.61 (19)
O9^i—Zn1—Zn2—Zn2^i	−33.07 (5)	Zn2—O10—C10—C11	−176.6 (2)
O3—Zn1—C1—C2B	111.4 (7)	Zn2—O10—C10—C9	4.3 (3)
O15—Zn1—C1—C2B	−126.7 (7)	C13—C9—C10—O10	179.5 (3)
O9^i—Zn1—C1—C2B	−19.8 (8)	O9—C9—C10—O10	−0.4 (4)
Zn2—Zn1—C1—C2B	171.6 (7)	C13—C9—C10—C11	0.4 (4)
O3—Zn1—C1—C2A	165.2 (6)	O9—C9—C10—C11	−179.5 (3)
O15—Zn1—C1—C2A	−72.9 (7)	O10—C10—C11—C12	−178.8 (3)
O9^i—Zn1—C1—C2A	34.0 (7)	C9—C10—C11—C12	0.3 (4)
Zn2—Zn1—C1—C2A	−134.6 (6)	C10—C11—C12—O13	−0.5 (5)
O15—Zn1—O3—C3	148.1 (3)	C11—C12—O13—C13	0.0 (5)
C1—Zn1—O3—C3	−73.1 (4)	O9—C9—C13—O13	179.0 (3)
O9^i—Zn1—O3—C3	70.1 (3)	C10—C9—C13—O13	−0.9 (4)
Zn2—Zn1—O3—C3	139.6 (4)	O9—C9—C13—C14	−0.5 (5)
O15—Zn1—O3—Zn2	8.52 (9)	C10—C9—C13—C14	179.6 (3)
C1—Zn1—O3—Zn2	147.30 (16)	C12—O13—C13—C9	0.7 (4)
O9^i—Zn1—O3—Zn2	−69.50 (9)	C12—O13—C13—C14	−179.7 (3)
O15—Zn2—O3—C3	−162.9 (2)	O3—Zn1—O15—C15	125.75 (18)
O10—Zn2—O3—C3	107.14 (19)	C1—Zn1—O15—C15	−12.8 (2)
O4—Zn2—O3—C3	5.46 (18)	O9^i—Zn1—O15—C15	−141.66 (19)
O15^i—Zn2—O3—C3	−73.07 (19)	Zn2—Zn1—O15—C15	134.2 (2)
Zn2^i—Zn2—O3—C3	−117.54 (18)	O3—Zn1—O15—Zn2	−8.47 (9)
Zn1—Zn2—O3—C3	−154.7 (2)	C1—Zn1—O15—Zn2	−146.99 (15)
O15—Zn2—O3—Zn1	−8.16 (8)	O9^i—Zn1—O15—Zn2	84.12 (9)
O10—Zn2—O3—Zn1	−98.15 (10)	O3—Zn1—O15—Zn2^i	−96.45 (10)
O4—Zn2—O3—Zn1	160.17 (10)	C1—Zn1—O15—Zn2^i	125.03 (16)
O15^i—Zn2—O3—Zn1	81.64 (10)	O9^i—Zn1—O15—Zn2^i	−3.86 (8)
Zn2^i—Zn2—O3—Zn1	37.17 (8)	Zn2—Zn1—O15—Zn2^i	−87.98 (10)
Zn1—O3—C3—C7	44.1 (5)	O9—Zn2—O15—C15	53.4 (2)
Zn2—O3—C3—C7	−179.8 (3)	O3—Zn2—O15—C15	−120.9 (2)
Zn1—O3—C3—C4	−139.9 (3)	O10—Zn2—O15—C15	−29.6 (2)
Zn2—O3—C3—C4	−3.7 (3)	O4—Zn2—O15—C15	−149.7 (2)
O9—Zn2—O4—C4	177.1 (2)	O15^i—Zn2—O15—C15	128.3 (2)
O3—Zn2—O4—C4	−7.3 (2)	Zn2^i—Zn2—O15—C15	128.3 (2)
O15—Zn2—O4—C4	21.7 (3)	Zn1—Zn2—O15—C15	−129.0 (2)
O10—Zn2—O4—C4	−96.3 (2)	O9—Zn2—O15—Zn1	−177.60 (8)
O15^i—Zn2—O4—C4	105.8 (2)	O3—Zn2—O15—Zn1	8.13 (8)
Zn2^i—Zn2—O4—C4	85.6 (2)	O10—Zn2—O15—Zn1	99.42 (8)
Zn1—Zn2—O4—C4	6.9 (2)	O4—Zn2—O15—Zn1	−20.8 (2)
Zn2—O4—C4—C5	−172.0 (3)	O15^i—Zn2—O15—Zn1	−102.75 (9)
Zn2—O4—C4—C3	7.4 (3)	Zn2^i—Zn2—O15—Zn1	−102.75 (9)
C7—C3—C4—O4	173.6 (3)	O9—Zn2—O15—Zn2^i	−74.85 (7)
O3—C3—C4—O4	−2.7 (4)	O3—Zn2—O15—Zn2^i	110.88 (8)
C7—C3—C4—C5	−7.0 (5)	O10—Zn2—O15—Zn2^i	−157.83 (7)
O3—C3—C4—C5	176.7 (3)	O4—Zn2—O15—Zn2^i	82.0 (2)
O4—C4—C5—C6	−177.8 (3)	O15^i—Zn2—O15—Zn2^i	0.0
C3—C4—C5—C6	2.8 (5)	Zn1—Zn2—O15—Zn2^i	102.75 (9)
C4—C5—C6—O7	2.5 (6)	Zn1—O15—C15—C16A	33.4 (5)
C5—C6—O7—C7	−3.8 (6)	Zn2—O15—C15—C16A	153.5 (4)
O3—C3—C7—O7	−178.0 (3)	Zn2^i—O15—C15—C16A	−95.4 (5)
C4—C3—C7—O7	5.9 (5)	Zn1—O15—C15—C16B	−33.9 (4)
O3—C3—C7—C8	4.2 (5)	Zn2—O15—C15—C16B	86.1 (4)
C4—C3—C7—C8	−171.8 (3)	Zn2^i—O15—C15—C16B	−162.7 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O10^ii	0.95	2.40	3.342 (4)	169
C8—H8A···O3	0.98	2.58	2.974 (4)	104
C12—H12···O4^iii	0.95	2.25	2.942 (4)	129
C15—H15B···O10	0.99	2.51	3.184 (4)	126

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

(II) bis(µ₃-2-ethoxyphenolato-κ⁴O¹,O²:O¹: O¹)bis(µ₂-2-ethoxyphenolato-κ³O¹,O²: O¹)bis(µ₂-2-methyl-4-oxo-4H-pyran-3-olato- κ³O³,O⁴:O³)bis(2-methyl-4-oxo-4H- pyran-3-olato-κ²O³,O⁴)tetrazinc(II) toluene disolvate

Crystal data

[Zn4(C6H5O3)4(C8H9O2)4]·2C7H8	Z = 1
Mr = 1494.78	F(000) = 772
Triclinic, P1	Dx = 1.559 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.715 (3) Å	Cell parameters from 6166 reflections
b = 12.578 (3) Å	θ = 2.8–28.0°
c = 12.794 (4) Å	µ = 1.57 mm^−1
α = 92.97 (3)°	T = 100 K
β = 110.48 (3)°	Plate, colourless
γ = 97.61 (3)°	0.26 × 0.18 × 0.10 mm
V = 1592.1 (9) Å^3

Data collection

Kuma KM-4 CCD κ-geometry diffractometer	6742 independent reflections
Radiation source: fine-focus sealed tube	4717 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 27.0°, θmin = 2.8°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2007)	h = −13→13
Tmin = 0.718, Tmax = 0.857	k = −16→16
12797 measured reflections	l = −16→16

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0878P)^2] where P = (Fo^2 + 2Fc^2)/3
6742 reflections	(Δ/σ)max = 0.001
405 parameters	Δρmax = 0.87 e Å^−3
1 restraint	Δρmin = −0.52 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	Occ. (<1)
Zn1	0.60621 (4)	0.60550 (3)	0.35835 (3)	0.03244 (14)
Zn2	0.34994 (4)	0.50106 (3)	0.41584 (3)	0.03083 (14)
O1	0.7067 (3)	0.7149 (2)	0.3035 (2)	0.0511 (8)
C1	0.6550 (5)	0.7112 (4)	0.1965 (3)	0.0477 (11)
O2	0.5008 (3)	0.5597 (2)	0.1839 (3)	0.0563 (8)
C2	0.5486 (5)	0.6279 (4)	0.1323 (4)	0.0490 (11)
C3	0.4968 (6)	0.6292 (4)	0.0121 (4)	0.0624 (14)
H3	0.4240	0.5755	−0.0330	0.075*
C4	0.5488 (6)	0.7033 (4)	−0.0357 (4)	0.0748 (16)
H4	0.5148	0.6999	−0.1152	0.090*
O5	0.6491 (4)	0.7847 (3)	0.0236 (3)	0.0812 (12)
C5	0.7017 (6)	0.7882 (4)	0.1390 (4)	0.0649 (14)
C6	0.8058 (7)	0.8849 (5)	0.1929 (5)	0.101 (2)
H6A	0.7727	0.9312	0.2380	0.151*
H6B	0.8241	0.9251	0.1348	0.151*
H6C	0.8890	0.8622	0.2413	0.151*
O7	0.4300 (3)	0.64291 (19)	0.3763 (2)	0.0332 (6)
C7	0.3617 (4)	0.7227 (3)	0.3860 (3)	0.0322 (8)
O8	0.1997 (3)	0.5915 (2)	0.4082 (2)	0.0393 (6)
C8	0.2366 (4)	0.6892 (3)	0.4023 (3)	0.0371 (9)
C9	0.1601 (4)	0.7732 (3)	0.4111 (4)	0.0456 (10)
H9	0.0758	0.7565	0.4206	0.055*
C10	0.2107 (5)	0.8760 (3)	0.4056 (4)	0.0497 (11)
H10	0.1594	0.9307	0.4111	0.060*
O11	0.3264 (3)	0.9051 (2)	0.3932 (2)	0.0457 (7)
C11	0.4039 (4)	0.8287 (3)	0.3830 (3)	0.0367 (9)
C12	0.5325 (5)	0.8772 (3)	0.3720 (4)	0.0504 (11)
H12A	0.5980	0.8275	0.3944	0.076*
H12B	0.5684	0.9454	0.4206	0.076*
H12C	0.5157	0.8907	0.2939	0.076*
O13	0.2820 (3)	0.37145 (19)	0.47503 (19)	0.0331 (6)
C13	0.1777 (4)	0.3009 (3)	0.4052 (3)	0.0327 (8)
O14	0.2099 (3)	0.3983 (2)	0.2630 (2)	0.0419 (7)
C14	0.1368 (4)	0.3128 (3)	0.2893 (3)	0.0377 (9)
C15	0.0300 (4)	0.2422 (4)	0.2122 (3)	0.0480 (11)
H15	0.0013	0.2514	0.1345	0.058*
C16	−0.0339 (4)	0.1585 (4)	0.2496 (4)	0.0523 (11)
H16	−0.1064	0.1093	0.1970	0.063*
C17	0.0054 (4)	0.1451 (3)	0.3617 (4)	0.0458 (10)
H17	−0.0402	0.0871	0.3859	0.055*
C18	0.1120 (4)	0.2161 (3)	0.4404 (3)	0.0349 (8)
H18	0.1393	0.2062	0.5178	0.042*
C19A	0.2289 (14)	0.3916 (9)	0.1554 (9)	0.037 (3)*	0.449 (15)
H19A	0.2081	0.3154	0.1226	0.045*	0.449 (15)
H19B	0.3240	0.4194	0.1666	0.045*	0.449 (15)
C20A	0.1396 (15)	0.4553 (12)	0.0790 (14)	0.083 (5)*	0.449 (15)
H20A	0.1526	0.4510	0.0069	0.125*	0.449 (15)
H20B	0.1610	0.5307	0.1117	0.125*	0.449 (15)
H20C	0.0455	0.4269	0.0674	0.125*	0.449 (15)
C19B	0.178 (2)	0.4317 (16)	0.1493 (16)	0.059 (6)*	0.365 (16)
H19C	0.2219	0.5067	0.1526	0.071*	0.365 (16)
H19D	0.0789	0.4282	0.1123	0.071*	0.365 (16)
C20B	0.229 (2)	0.3550 (15)	0.0840 (18)	0.094 (7)*	0.365 (16)
H20D	0.2072	0.3742	0.0071	0.142*	0.365 (16)
H20E	0.1855	0.2809	0.0823	0.142*	0.365 (16)
H20F	0.3269	0.3603	0.1204	0.142*	0.365 (16)
C19C	0.177 (4)	0.395 (3)	0.142 (3)	0.038 (7)*	0.186 (14)
H19E	0.0839	0.4083	0.1031	0.046*	0.186 (14)
H19F	0.1870	0.3240	0.1103	0.046*	0.186 (14)
C20C	0.278 (4)	0.483 (3)	0.131 (3)	0.078 (12)*	0.186 (14)
H20G	0.2655	0.4858	0.0519	0.117*	0.186 (14)
H20H	0.3691	0.4688	0.1726	0.117*	0.186 (14)
H20I	0.2653	0.5518	0.1622	0.117*	0.186 (14)
O21	0.5266 (2)	0.45997 (18)	0.40162 (19)	0.0290 (5)
C21	0.5523 (4)	0.3671 (3)	0.3585 (3)	0.0322 (8)
O22	0.7396 (3)	0.4760 (2)	0.3459 (2)	0.0402 (6)
C22	0.6689 (4)	0.3732 (3)	0.3307 (3)	0.0356 (9)
C23	0.7061 (4)	0.2817 (3)	0.2945 (3)	0.0430 (10)
H23	0.7857	0.2864	0.2770	0.052*
C24	0.6260 (5)	0.1824 (3)	0.2838 (3)	0.0474 (11)
H24	0.6513	0.1188	0.2592	0.057*
C25	0.5116 (4)	0.1758 (3)	0.3082 (3)	0.0401 (9)
H25	0.4564	0.1077	0.2990	0.048*
C26	0.4748 (4)	0.2680 (3)	0.3468 (3)	0.0340 (8)
H26	0.3957	0.2623	0.3651	0.041*
C27	0.8752 (4)	0.4920 (3)	0.3463 (3)	0.0412 (9)
H27A	0.9202	0.4310	0.3783	0.049*
H27B	0.9264	0.5590	0.3947	0.049*
C28	0.8772 (4)	0.4998 (4)	0.2305 (3)	0.0480 (11)
H28A	0.8290	0.5579	0.1973	0.072*
H28B	0.8331	0.4313	0.1841	0.072*
H28C	0.9709	0.5153	0.2343	0.072*
C29A	0.8042 (9)	0.0513 (6)	0.8963 (8)	0.097 (4)*	0.531 (9)
C30A	0.8697 (8)	0.1478 (7)	0.8787 (8)	0.073 (3)*	0.531 (9)
H30A	0.9400	0.1474	0.8497	0.087*	0.531 (9)
C31A	0.8325 (10)	0.2449 (6)	0.9037 (9)	0.107 (5)*	0.531 (9)
H31A	0.8773	0.3109	0.8917	0.128*	0.531 (9)
C32A	0.7297 (10)	0.2455 (6)	0.9462 (9)	0.123 (5)*	0.531 (9)
H32A	0.7042	0.3119	0.9633	0.148*	0.531 (9)
C33A	0.6641 (8)	0.1490 (7)	0.9638 (7)	0.075 (3)*	0.531 (9)
H33A	0.5938	0.1494	0.9929	0.090*	0.531 (9)
C34A	0.7013 (8)	0.0519 (6)	0.9389 (7)	0.076 (3)*	0.531 (9)
H34A	0.6565	−0.0141	0.9509	0.091*	0.531 (9)
C35A	0.814 (2)	−0.0486 (15)	0.8732 (16)	0.164 (8)*	0.531 (9)
H35A	0.7511	−0.0968	0.8962	0.246*	0.531 (9)
H35B	0.9066	−0.0607	0.9137	0.246*	0.531 (9)
H35C	0.7925	−0.0636	0.7923	0.246*	0.531 (9)
C29B	0.7086 (7)	0.0975 (6)	0.9330 (8)	0.087 (4)*	0.469 (9)
C30B	0.7754 (9)	0.0156 (5)	0.9132 (8)	0.062 (3)*	0.469 (9)
H30B	0.7444	−0.0570	0.9205	0.075*	0.469 (9)
C31B	0.8877 (10)	0.0399 (7)	0.8829 (9)	0.105 (4)*	0.469 (9)
H31B	0.9333	−0.0160	0.8693	0.126*	0.469 (9)
C32B	0.9331 (9)	0.1461 (8)	0.8723 (9)	0.105 (4)*	0.469 (9)
H32B	1.0098	0.1628	0.8515	0.126*	0.469 (9)
C33B	0.8663 (10)	0.2280 (6)	0.8920 (9)	0.082 (4)*	0.469 (9)
H33B	0.8973	0.3006	0.8848	0.099*	0.469 (9)
C34B	0.7541 (8)	0.2037 (6)	0.9224 (7)	0.052 (3)*	0.469 (9)
H34B	0.7084	0.2597	0.9359	0.063*	0.469 (9)
C35B	0.607 (2)	0.0537 (15)	0.9670 (16)	0.143 (8)*	0.469 (9)
H35D	0.5589	0.1107	0.9816	0.215*	0.469 (9)
H35E	0.6449	0.0195	1.0358	0.215*	0.469 (9)
H35F	0.5433	−0.0005	0.9080	0.215*	0.469 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0365 (3)	0.0325 (2)	0.0261 (2)	0.00093 (18)	0.01030 (18)	0.00287 (17)
Zn2	0.0329 (3)	0.0286 (2)	0.0287 (2)	0.00260 (17)	0.00901 (18)	0.00351 (17)
O1	0.0548 (19)	0.0466 (17)	0.0428 (17)	−0.0005 (14)	0.0093 (14)	0.0056 (13)
C1	0.060 (3)	0.050 (3)	0.027 (2)	0.016 (2)	0.0049 (19)	0.0018 (18)
O2	0.063 (2)	0.0503 (18)	0.0469 (18)	−0.0061 (16)	0.0142 (16)	0.0023 (14)
C2	0.057 (3)	0.049 (3)	0.043 (2)	0.002 (2)	0.022 (2)	0.010 (2)
C3	0.079 (4)	0.057 (3)	0.037 (2)	−0.005 (3)	0.009 (2)	0.006 (2)
C4	0.092 (4)	0.071 (4)	0.045 (3)	−0.006 (3)	0.011 (3)	0.002 (3)
O5	0.104 (3)	0.074 (2)	0.051 (2)	−0.015 (2)	0.019 (2)	0.0199 (18)
C5	0.080 (4)	0.061 (3)	0.043 (3)	−0.009 (3)	0.016 (3)	0.010 (2)
C6	0.103 (5)	0.093 (5)	0.079 (4)	−0.033 (4)	0.016 (4)	0.013 (4)
O7	0.0356 (15)	0.0272 (13)	0.0352 (14)	0.0055 (11)	0.0104 (11)	0.0058 (10)
C7	0.038 (2)	0.0312 (19)	0.0256 (17)	0.0098 (16)	0.0067 (15)	0.0043 (14)
O8	0.0354 (15)	0.0388 (15)	0.0429 (15)	0.0064 (12)	0.0125 (12)	0.0086 (12)
C8	0.038 (2)	0.041 (2)	0.0274 (19)	0.0072 (18)	0.0058 (16)	0.0034 (16)
C9	0.038 (2)	0.051 (3)	0.050 (2)	0.018 (2)	0.015 (2)	0.008 (2)
C10	0.050 (3)	0.043 (2)	0.061 (3)	0.024 (2)	0.019 (2)	0.008 (2)
O11	0.0515 (19)	0.0326 (14)	0.0499 (17)	0.0147 (13)	0.0117 (14)	0.0048 (12)
C11	0.043 (2)	0.0313 (19)	0.0323 (19)	0.0121 (17)	0.0070 (17)	0.0046 (15)
C12	0.054 (3)	0.030 (2)	0.063 (3)	0.0033 (19)	0.017 (2)	0.0049 (19)
O13	0.0359 (15)	0.0315 (13)	0.0251 (12)	−0.0037 (11)	0.0061 (11)	0.0003 (10)
C13	0.030 (2)	0.0284 (18)	0.0353 (19)	0.0048 (15)	0.0077 (16)	−0.0038 (15)
O14	0.0497 (17)	0.0435 (16)	0.0266 (13)	0.0023 (13)	0.0083 (12)	0.0044 (11)
C14	0.033 (2)	0.041 (2)	0.034 (2)	0.0083 (17)	0.0047 (16)	0.0010 (17)
C15	0.039 (2)	0.056 (3)	0.036 (2)	0.002 (2)	0.0008 (18)	−0.0022 (19)
C16	0.041 (3)	0.050 (3)	0.050 (3)	−0.005 (2)	0.004 (2)	−0.013 (2)
C17	0.039 (2)	0.036 (2)	0.057 (3)	−0.0033 (17)	0.015 (2)	−0.0023 (19)
C18	0.031 (2)	0.034 (2)	0.040 (2)	0.0036 (16)	0.0135 (17)	0.0002 (16)
O21	0.0355 (14)	0.0220 (12)	0.0281 (12)	0.0042 (10)	0.0102 (11)	0.0004 (10)
C21	0.040 (2)	0.0309 (19)	0.0247 (17)	0.0099 (16)	0.0081 (16)	0.0042 (14)
O22	0.0428 (17)	0.0344 (14)	0.0443 (16)	0.0019 (12)	0.0185 (13)	0.0032 (12)
C22	0.040 (2)	0.036 (2)	0.0298 (19)	0.0055 (17)	0.0124 (17)	0.0047 (15)
C23	0.046 (3)	0.042 (2)	0.045 (2)	0.0106 (19)	0.020 (2)	0.0054 (18)
C24	0.065 (3)	0.035 (2)	0.047 (2)	0.019 (2)	0.022 (2)	0.0029 (18)
C25	0.047 (3)	0.0288 (19)	0.042 (2)	0.0032 (17)	0.0135 (19)	0.0021 (16)
C26	0.037 (2)	0.0316 (19)	0.0319 (19)	0.0042 (16)	0.0114 (16)	0.0048 (15)
C27	0.031 (2)	0.049 (2)	0.041 (2)	0.0041 (18)	0.0096 (17)	0.0107 (18)
C28	0.037 (2)	0.066 (3)	0.043 (2)	0.007 (2)	0.0170 (19)	0.012 (2)

Geometric parameters (Å, º)

Zn1—O1	1.945 (3)	C19B—C20B	1.52 (3)
Zn1—O2	2.126 (3)	C19B—H19C	0.9900
Zn1—O7	2.090 (3)	C19B—H19D	0.9900
Zn1—O13^i	2.030 (2)	C20B—H20D	0.9800
Zn1—O21	2.099 (2)	C20B—H20E	0.9800
Zn1—O22	2.339 (3)	C20B—H20F	0.9800
Zn2—O7	2.042 (2)	C19C—C20C	1.49 (5)
Zn2—O8	2.069 (3)	C19C—H19E	0.9900
Zn2—O13	1.990 (2)	C19C—H19F	0.9900
Zn2—O14	2.217 (3)	C20C—H20G	0.9800
Zn2—O21	2.092 (3)	C20C—H20H	0.9800
Zn2—O21^i	2.234 (3)	C20C—H20I	0.9800
O1—C1	1.280 (5)	O21—C21	1.367 (4)
C1—C5	1.390 (6)	O21—Zn2^i	2.234 (3)
C1—C2	1.419 (6)	C21—C26	1.373 (5)
O2—C2	1.270 (5)	C21—C22	1.408 (5)
C2—C3	1.443 (6)	O22—C22	1.377 (4)
C3—C4	1.309 (7)	O22—C27	1.438 (5)
C3—H3	0.9500	C22—C23	1.375 (5)
C4—O5	1.354 (6)	C23—C24	1.390 (6)
C4—H4	0.9500	C23—H23	0.9500
O5—C5	1.380 (6)	C24—C25	1.361 (6)
C5—C6	1.488 (7)	C24—H24	0.9500
C6—H6A	0.9800	C25—C26	1.394 (5)
C6—H6B	0.9800	C25—H25	0.9500
C6—H6C	0.9800	C26—H26	0.9500
O7—C7	1.343 (4)	C27—C28	1.497 (5)
C7—C11	1.356 (5)	C27—H27A	0.9900
C7—C8	1.440 (5)	C27—H27B	0.9900
O8—C8	1.255 (5)	C28—H28A	0.9800
C8—C9	1.443 (6)	C28—H28B	0.9800
C9—C10	1.350 (6)	C28—H28C	0.9800
C9—H9	0.9500	C29A—C35A	1.303 (19)
C10—O11	1.312 (5)	C29A—C30A	1.3900
C10—H10	0.9500	C29A—C34A	1.3900
O11—C11	1.380 (5)	C30A—C31A	1.3900
C11—C12	1.487 (6)	C30A—H30A	0.9500
C12—H12A	0.9800	C31A—C32A	1.3900
C12—H12B	0.9800	C31A—H31A	0.9500
C12—H12C	0.9800	C32A—C33A	1.3900
O13—C13	1.338 (4)	C32A—H32A	0.9500
O13—Zn1^i	2.030 (2)	C33A—C34A	1.3900
C13—C18	1.381 (5)	C33A—H33A	0.9500
C13—C14	1.414 (5)	C34A—H34A	0.9500
O14—C14	1.371 (5)	C35A—H35A	0.9800
O14—C19A	1.460 (11)	C35A—H35B	0.9800
O14—C19C	1.46 (3)	C35A—H35C	0.9800
O14—C19B	1.471 (19)	C29B—C35B	1.37 (2)
C14—C15	1.387 (5)	C29B—C30B	1.3900
C15—C16	1.377 (6)	C29B—C34B	1.3900
C15—H15	0.9500	C30B—C31B	1.3900
C16—C17	1.373 (6)	C30B—H30B	0.9500
C16—H16	0.9500	C31B—C32B	1.3900
C17—C18	1.395 (5)	C31B—H31B	0.9500
C17—H17	0.9500	C32B—C33B	1.3900
C18—H18	0.9500	C32B—H32B	0.9500
C19A—C20A	1.46 (2)	C33B—C34B	1.3900
C19A—H19A	0.9900	C33B—H33B	0.9500
C19A—H19B	0.9900	C34B—H34B	0.9500
C20A—H20A	0.9800	C35B—H35D	0.9800
C20A—H20B	0.9800	C35B—H35E	0.9800
C20A—H20C	0.9800	C35B—H35F	0.9800
O1—Zn1—O2	82.41 (12)	C20A—C19A—H19A	109.8
O1—Zn1—O7	116.58 (12)	O14—C19A—H19B	109.8
O1—Zn1—O13^i	100.45 (11)	C20A—C19A—H19B	109.8
O1—Zn1—O21	164.48 (12)	H19A—C19A—H19B	108.2
O1—Zn1—O22	93.23 (12)	C19A—C20A—H20A	109.5
O2—Zn1—O22	85.32 (12)	C19A—C20A—H20B	109.5
O7—Zn1—O2	90.60 (12)	H20A—C20A—H20B	109.5
O7—Zn1—O21	77.98 (10)	C19A—C20A—H20C	109.5
O7—Zn1—O22	149.13 (9)	H20A—C20A—H20C	109.5
O13^i—Zn1—O2	171.50 (11)	H20B—C20A—H20C	109.5
O13^i—Zn1—O7	95.18 (10)	O14—C19B—C20B	107.4 (15)
O13^i—Zn1—O21	82.60 (10)	O14—C19B—H19C	110.2
O13^i—Zn1—O22	86.53 (10)	C20B—C19B—H19C	110.2
O21—Zn1—O2	92.56 (11)	O14—C19B—H19D	110.2
O21—Zn1—O22	71.67 (9)	C20B—C19B—H19D	110.2
O7—Zn2—O8	80.02 (10)	H19C—C19B—H19D	108.5
O7—Zn2—O14	111.16 (10)	C19B—C20B—H20D	109.5
O7—Zn2—O21	79.22 (10)	C19B—C20B—H20E	109.5
O7—Zn2—O21^i	92.66 (10)	H20D—C20B—H20E	109.5
O8—Zn2—O14	89.48 (11)	C19B—C20B—H20F	109.5
O8—Zn2—O21	159.09 (10)	H20D—C20B—H20F	109.5
O8—Zn2—O21^i	98.31 (10)	H20E—C20B—H20F	109.5
O13—Zn2—O7	172.54 (9)	O14—C19C—C20C	103 (2)
O13—Zn2—O8	99.01 (11)	O14—C19C—H19E	111.1
O13—Zn2—O14	76.16 (10)	C20C—C19C—H19E	111.1
O13—Zn2—O21	101.90 (10)	O14—C19C—H19F	111.1
O13—Zn2—O21^i	80.14 (10)	C20C—C19C—H19F	111.1
O14—Zn2—O21^i	155.94 (9)	H19E—C19C—H19F	109.1
O21—Zn2—O14	95.70 (10)	C19C—C20C—H20G	109.5
O21—Zn2—O21^i	85.12 (10)	C19C—C20C—H20H	109.5
O1—Zn1—Zn2^i	136.92 (9)	H20G—C20C—H20H	109.5
O13^i—Zn1—Zn2^i	37.75 (7)	C19C—C20C—H20I	109.5
O7—Zn1—Zn2^i	84.82 (7)	H20G—C20C—H20I	109.5
O21—Zn1—Zn2^i	44.90 (7)	H20H—C20C—H20I	109.5
O2—Zn1—Zn2^i	137.24 (9)	C21—O21—Zn2	131.5 (2)
O22—Zn1—Zn2^i	77.79 (7)	C21—O21—Zn1	116.8 (2)
O13—Zn2—Zn1^i	38.64 (7)	Zn2—O21—Zn1	100.39 (10)
O7—Zn2—Zn1^i	134.19 (8)	C21—O21—Zn2^i	111.6 (2)
O8—Zn2—Zn1^i	102.84 (8)	Zn2—O21—Zn2^i	94.89 (10)
O21—Zn2—Zn1^i	93.42 (7)	Zn1—O21—Zn2^i	93.57 (10)
O14—Zn2—Zn1^i	114.56 (7)	O21—C21—C26	123.5 (3)
O21^i—Zn2—Zn1^i	41.54 (6)	O21—C21—C22	117.8 (3)
C1—O1—Zn1	110.8 (3)	C26—C21—C22	118.6 (3)
O1—C1—C5	121.2 (4)	C22—O22—C27	120.0 (3)
O1—C1—C2	121.1 (4)	C22—O22—Zn1	111.2 (2)
C5—C1—C2	117.6 (4)	C27—O22—Zn1	128.7 (2)
C2—O2—Zn1	107.0 (3)	C23—C22—O22	125.2 (4)
O2—C2—C1	118.3 (4)	C23—C22—C21	120.9 (4)
O2—C2—C3	124.0 (4)	O22—C22—C21	113.9 (3)
C1—C2—C3	117.6 (4)	C22—C23—C24	119.3 (4)
C4—C3—C2	120.9 (5)	C22—C23—H23	120.4
C4—C3—H3	119.6	C24—C23—H23	120.4
C2—C3—H3	119.6	C25—C24—C23	120.4 (4)
C3—C4—O5	122.7 (5)	C25—C24—H24	119.8
C3—C4—H4	118.6	C23—C24—H24	119.8
O5—C4—H4	118.6	C24—C25—C26	120.5 (4)
C4—O5—C5	118.9 (4)	C24—C25—H25	119.8
O5—C5—C1	122.2 (4)	C26—C25—H25	119.8
O5—C5—C6	112.9 (4)	C21—C26—C25	120.3 (4)
C1—C5—C6	124.9 (5)	C21—C26—H26	119.8
C5—C6—H6A	109.5	C25—C26—H26	119.8
C5—C6—H6B	109.5	O22—C27—C28	111.6 (3)
H6A—C6—H6B	109.5	O22—C27—H27A	109.3
C5—C6—H6C	109.5	C28—C27—H27A	109.3
H6A—C6—H6C	109.5	O22—C27—H27B	109.3
H6B—C6—H6C	109.5	C28—C27—H27B	109.3
C7—O7—Zn2	111.6 (2)	H27A—C27—H27B	108.0
C7—O7—Zn1	145.2 (2)	C27—C28—H28A	109.5
Zn2—O7—Zn1	102.39 (11)	C27—C28—H28B	109.5
O7—C7—C11	124.6 (4)	H28A—C28—H28B	109.5
O7—C7—C8	115.2 (3)	C27—C28—H28C	109.5
C11—C7—C8	120.1 (3)	H28A—C28—H28C	109.5
C8—O8—Zn2	111.5 (3)	H28B—C28—H28C	109.5
O8—C8—C7	120.0 (3)	C35A—C29A—C30A	131.5 (10)
O8—C8—C9	123.6 (4)	C35A—C29A—C34A	108.4 (10)
C7—C8—C9	116.4 (4)	C30A—C29A—C34A	120.0
C10—C9—C8	118.6 (4)	C29A—C30A—C31A	120.0
C10—C9—H9	120.7	C29A—C30A—H30A	120.0
C8—C9—H9	120.7	C31A—C30A—H30A	120.0
O11—C10—C9	124.1 (4)	C32A—C31A—C30A	120.0
O11—C10—H10	118.0	C32A—C31A—H31A	120.0
C9—C10—H10	118.0	C30A—C31A—H31A	120.0
C10—O11—C11	120.3 (3)	C31A—C32A—C33A	120.0
C7—C11—O11	120.5 (4)	C31A—C32A—H32A	120.0
C7—C11—C12	127.0 (4)	C33A—C32A—H32A	120.0
O11—C11—C12	112.4 (3)	C34A—C33A—C32A	120.0
C11—C12—H12A	109.5	C34A—C33A—H33A	120.0
C11—C12—H12B	109.5	C32A—C33A—H33A	120.0
H12A—C12—H12B	109.5	C33A—C34A—C29A	120.0
C11—C12—H12C	109.5	C33A—C34A—H34A	120.0
H12A—C12—H12C	109.5	C29A—C34A—H34A	120.0
H12B—C12—H12C	109.5	C29A—C35A—H35A	109.5
C13—O13—Zn2	118.9 (2)	C29A—C35A—H35B	109.5
C13—O13—Zn1^i	137.3 (2)	H35A—C35A—H35B	109.5
Zn2—O13—Zn1^i	103.60 (11)	C29A—C35A—H35C	109.5
O13—C13—C18	123.4 (3)	H35A—C35A—H35C	109.5
O13—C13—C14	117.5 (3)	H35B—C35A—H35C	109.5
C18—C13—C14	119.1 (3)	C35B—C29B—C30B	108.7 (10)
C14—O14—C19A	119.6 (5)	C35B—C29B—C34B	131.2 (10)
C14—O14—C19C	111.1 (13)	C30B—C29B—C34B	120.0
C14—O14—C19B	123.8 (9)	C31B—C30B—C29B	120.0
C14—O14—Zn2	111.5 (2)	C31B—C30B—H30B	120.0
C19A—O14—Zn2	124.4 (5)	C29B—C30B—H30B	120.0
C19C—O14—Zn2	137.4 (13)	C32B—C31B—C30B	120.0
C19B—O14—Zn2	123.3 (8)	C32B—C31B—H31B	120.0
O14—C14—C15	124.9 (4)	C30B—C31B—H31B	120.0
O14—C14—C13	114.5 (3)	C31B—C32B—C33B	120.0
C15—C14—C13	120.6 (4)	C31B—C32B—H32B	120.0
C16—C15—C14	119.1 (4)	C33B—C32B—H32B	120.0
C16—C15—H15	120.4	C34B—C33B—C32B	120.0
C14—C15—H15	120.4	C34B—C33B—H33B	120.0
C17—C16—C15	121.0 (4)	C32B—C33B—H33B	120.0
C17—C16—H16	119.5	C33B—C34B—C29B	120.0
C15—C16—H16	119.5	C33B—C34B—H34B	120.0
C16—C17—C18	120.4 (4)	C29B—C34B—H34B	120.0
C16—C17—H17	119.8	C29B—C35B—H35D	109.5
C18—C17—H17	119.8	C29B—C35B—H35E	109.5
C13—C18—C17	119.8 (4)	H35D—C35B—H35E	109.5
C13—C18—H18	120.1	C29B—C35B—H35F	109.5
C17—C18—H18	120.1	H35D—C35B—H35F	109.5
O14—C19A—C20A	109.5 (10)	H35E—C35B—H35F	109.5
O14—C19A—H19A	109.8
O13^i—Zn1—O1—C1	177.3 (3)	C19B—O14—C14—C15	5.0 (11)
O7—Zn1—O1—C1	−81.5 (3)	Zn2—O14—C14—C15	171.7 (3)
O21—Zn1—O1—C1	77.2 (5)	C19A—O14—C14—C13	149.4 (6)
O2—Zn1—O1—C1	5.4 (3)	C19C—O14—C14—C13	170.5 (19)
O22—Zn1—O1—C1	90.2 (3)	C19B—O14—C14—C13	−174.4 (9)
Zn2^i—Zn1—O1—C1	165.7 (2)	Zn2—O14—C14—C13	−7.6 (4)
Zn1—O1—C1—C5	173.9 (4)	O13—C13—C14—O14	−1.0 (5)
Zn1—O1—C1—C2	−6.6 (5)	C18—C13—C14—O14	−178.9 (3)
O1—Zn1—O2—C2	−3.7 (3)	O13—C13—C14—C15	179.6 (3)
O7—Zn1—O2—C2	113.1 (3)	C18—C13—C14—C15	1.7 (6)
O21—Zn1—O2—C2	−168.9 (3)	O14—C14—C15—C16	179.1 (4)
O22—Zn1—O2—C2	−97.6 (3)	C13—C14—C15—C16	−1.6 (6)
Zn2^i—Zn1—O2—C2	−163.9 (2)	C14—C15—C16—C17	0.8 (7)
Zn1—O2—C2—C1	1.4 (5)	C15—C16—C17—C18	−0.3 (7)
Zn1—O2—C2—C3	−175.4 (4)	O13—C13—C18—C17	−178.9 (4)
O1—C1—C2—O2	3.5 (7)	C14—C13—C18—C17	−1.2 (6)
C5—C1—C2—O2	−176.9 (5)	C16—C17—C18—C13	0.5 (6)
O1—C1—C2—C3	−179.5 (4)	C14—O14—C19A—C20A	103.7 (9)
C5—C1—C2—C3	0.1 (7)	C19C—O14—C19A—C20A	33 (4)
O2—C2—C3—C4	178.4 (5)	C19B—O14—C19A—C20A	−3.7 (19)
C1—C2—C3—C4	1.6 (8)	Zn2—O14—C19A—C20A	−102.4 (10)
C2—C3—C4—O5	−2.7 (9)	C14—O14—C19B—C20B	−78.5 (16)
C3—C4—O5—C5	1.9 (9)	C19A—O14—C19B—C20B	13.6 (14)
C4—O5—C5—C1	−0.2 (8)	C19C—O14—C19B—C20B	−28 (6)
C4—O5—C5—C6	−177.0 (6)	Zn2—O14—C19B—C20B	116.3 (13)
O1—C1—C5—O5	178.9 (5)	C14—O14—C19C—C20C	−172 (2)
C2—C1—C5—O5	−0.7 (8)	C19A—O14—C19C—C20C	−54 (4)
O1—C1—C5—C6	−4.7 (9)	C19B—O14—C19C—C20C	51 (5)
C2—C1—C5—C6	175.7 (6)	Zn2—O14—C19C—C20C	5 (4)
O8—Zn2—O7—C7	11.2 (2)	O13—Zn2—O21—C21	45.8 (3)
O21—Zn2—O7—C7	−171.3 (2)	O7—Zn2—O21—C21	−141.7 (3)
O14—Zn2—O7—C7	96.7 (2)	O8—Zn2—O21—C21	−134.8 (3)
O21^i—Zn2—O7—C7	−86.8 (2)	O14—Zn2—O21—C21	−31.2 (3)
Zn1^i—Zn2—O7—C7	−87.1 (2)	O21^i—Zn2—O21—C21	124.7 (3)
O8—Zn2—O7—Zn1	−176.61 (12)	Zn1^i—Zn2—O21—C21	83.9 (3)
O21—Zn2—O7—Zn1	0.90 (9)	O13—Zn2—O21—Zn1	−173.37 (9)
O14—Zn2—O7—Zn1	−91.09 (12)	O7—Zn2—O21—Zn1	−0.89 (9)
O21^i—Zn2—O7—Zn1	85.42 (11)	O8—Zn2—O21—Zn1	6.0 (3)
Zn1^i—Zn2—O7—Zn1	85.14 (12)	O14—Zn2—O21—Zn1	109.61 (10)
O1—Zn1—O7—C7	−19.3 (4)	O21^i—Zn2—O21—Zn1	−94.54 (11)
O13^i—Zn1—O7—C7	85.1 (4)	Zn1^i—Zn2—O21—Zn1	−135.28 (8)
O21—Zn1—O7—C7	166.4 (4)	O13—Zn2—O21—Zn2^i	−78.83 (10)
O2—Zn1—O7—C7	−101.1 (4)	O7—Zn2—O21—Zn2^i	93.65 (10)
O22—Zn1—O7—C7	177.0 (3)	O8—Zn2—O21—Zn2^i	100.5 (3)
Zn2^i—Zn1—O7—C7	121.4 (4)	O14—Zn2—O21—Zn2^i	−155.85 (9)
O1—Zn1—O7—Zn2	173.39 (11)	O21^i—Zn2—O21—Zn2^i	0.0
O13^i—Zn1—O7—Zn2	−82.19 (12)	Zn1^i—Zn2—O21—Zn2^i	−40.74 (7)
O21—Zn1—O7—Zn2	−0.90 (9)	O1—Zn1—O21—C21	−11.8 (5)
O2—Zn1—O7—Zn2	91.58 (12)	O13^i—Zn1—O21—C21	−114.2 (2)
O22—Zn1—O7—Zn2	9.7 (2)	O7—Zn1—O21—C21	148.8 (2)
Zn2^i—Zn1—O7—Zn2	−45.84 (9)	O2—Zn1—O21—C21	58.8 (2)
Zn2—O7—C7—C11	168.9 (3)	O22—Zn1—O21—C21	−25.5 (2)
Zn1—O7—C7—C11	2.2 (6)	Zn2^i—Zn1—O21—C21	−116.4 (3)
Zn2—O7—C7—C8	−10.3 (4)	O1—Zn1—O21—Zn2	−159.7 (4)
Zn1—O7—C7—C8	−176.9 (3)	O13^i—Zn1—O21—Zn2	97.81 (11)
O13—Zn2—O8—C8	161.9 (2)	O7—Zn1—O21—Zn2	0.88 (9)
O7—Zn2—O8—C8	−10.6 (2)	O2—Zn1—O21—Zn2	−89.20 (13)
O21—Zn2—O8—C8	−17.5 (4)	O22—Zn1—O21—Zn2	−173.41 (12)
O14—Zn2—O8—C8	−122.2 (3)	Zn2^i—Zn1—O21—Zn2	95.63 (11)
O21^i—Zn2—O8—C8	80.6 (3)	O1—Zn1—O21—Zn2^i	104.7 (4)
Zn1^i—Zn2—O8—C8	122.7 (2)	O13^i—Zn1—O21—Zn2^i	2.18 (9)
Zn2—O8—C8—C7	8.5 (4)	O7—Zn1—O21—Zn2^i	−94.76 (10)
Zn2—O8—C8—C9	−171.3 (3)	O2—Zn1—O21—Zn2^i	175.17 (11)
O7—C7—C8—O8	1.2 (5)	O22—Zn1—O21—Zn2^i	90.96 (10)
C11—C7—C8—O8	−178.0 (3)	Zn2—O21—C21—C26	−21.9 (5)
O7—C7—C8—C9	−179.0 (3)	Zn1—O21—C21—C26	−157.7 (3)
C11—C7—C8—C9	1.8 (5)	Zn2^i—O21—C21—C26	96.3 (4)
O8—C8—C9—C10	178.7 (4)	Zn2—O21—C21—C22	161.8 (2)
C7—C8—C9—C10	−1.1 (6)	Zn1—O21—C21—C22	25.9 (4)
C8—C9—C10—O11	−0.4 (7)	Zn2^i—O21—C21—C22	−80.0 (3)
C9—C10—O11—C11	1.1 (6)	O1—Zn1—O22—C22	−153.4 (2)
O7—C7—C11—O11	179.7 (3)	O13^i—Zn1—O22—C22	106.4 (2)
C8—C7—C11—O11	−1.2 (5)	O7—Zn1—O22—C22	12.1 (3)
O7—C7—C11—C12	−2.0 (6)	O21—Zn1—O22—C22	23.0 (2)
C8—C7—C11—C12	177.1 (4)	O2—Zn1—O22—C22	−71.3 (2)
C10—O11—C11—C7	−0.2 (5)	Zn2^i—Zn1—O22—C22	69.2 (2)
C10—O11—C11—C12	−178.8 (4)	O1—Zn1—O22—C27	23.1 (3)
O8—Zn2—O13—C13	76.2 (3)	O13^i—Zn1—O22—C27	−77.2 (3)
O21—Zn2—O13—C13	−104.0 (3)	O7—Zn1—O22—C27	−171.5 (3)
O14—Zn2—O13—C13	−11.0 (2)	O21—Zn1—O22—C27	−160.5 (3)
O21^i—Zn2—O13—C13	173.1 (3)	O2—Zn1—O22—C27	105.2 (3)
Zn1^i—Zn2—O13—C13	175.5 (3)	Zn2^i—Zn1—O22—C27	−114.3 (3)
O8—Zn2—O13—Zn1^i	−99.32 (12)	C27—O22—C22—C23	−12.9 (5)
O21—Zn2—O13—Zn1^i	80.45 (12)	Zn1—O22—C22—C23	163.9 (3)
O14—Zn2—O13—Zn1^i	173.46 (13)	C27—O22—C22—C21	165.5 (3)
O21^i—Zn2—O13—Zn1^i	−2.38 (10)	Zn1—O22—C22—C21	−17.6 (4)
Zn2—O13—C13—C18	−171.5 (3)	O21—C21—C22—C23	175.3 (3)
Zn1^i—O13—C13—C18	2.0 (6)	C26—C21—C22—C23	−1.2 (5)
Zn2—O13—C13—C14	10.7 (4)	O21—C21—C22—O22	−3.2 (5)
Zn1^i—O13—C13—C14	−175.8 (3)	C26—C21—C22—O22	−179.7 (3)
O13—Zn2—O14—C14	9.9 (2)	O22—C22—C23—C24	179.3 (4)
O7—Zn2—O14—C14	−168.6 (2)	C21—C22—C23—C24	1.0 (6)
O8—Zn2—O14—C14	−89.5 (2)	C22—C23—C24—C25	0.4 (6)
O21—Zn2—O14—C14	110.8 (2)	C23—C24—C25—C26	−1.5 (6)
O21^i—Zn2—O14—C14	20.0 (4)	O21—C21—C26—C25	−176.3 (3)
Zn1^i—Zn2—O14—C14	14.4 (3)	C22—C21—C26—C25	0.1 (5)
O13—Zn2—O14—C19A	−145.9 (6)	C24—C25—C26—C21	1.3 (6)
O7—Zn2—O14—C19A	35.6 (6)	C22—O22—C27—C28	88.4 (4)
O8—Zn2—O14—C19A	114.7 (6)	Zn1—O22—C27—C28	−87.8 (4)
O21—Zn2—O14—C19A	−45.0 (6)	C35A—C29A—C30A—C31A	174.9 (15)
O21^i—Zn2—O14—C19A	−135.8 (6)	C34A—C29A—C30A—C31A	0.0
Zn1^i—Zn2—O14—C19A	−141.4 (6)	C29A—C30A—C31A—C32A	0.0
O13—Zn2—O14—C19C	−168 (3)	C30A—C31A—C32A—C33A	0.0
O7—Zn2—O14—C19C	14 (3)	C31A—C32A—C33A—C34A	0.0
O8—Zn2—O14—C19C	93 (3)	C32A—C33A—C34A—C29A	0.0
O21—Zn2—O14—C19C	−67 (3)	C35A—C29A—C34A—C33A	−176.0 (12)
O21^i—Zn2—O14—C19C	−158 (3)	C30A—C29A—C34A—C33A	0.0
Zn1^i—Zn2—O14—C19C	−163 (3)	C35B—C29B—C30B—C31B	−176.9 (11)
O13—Zn2—O14—C19B	176.7 (9)	C34B—C29B—C30B—C31B	0.0
O7—Zn2—O14—C19B	−1.8 (9)	C29B—C30B—C31B—C32B	0.0
O8—Zn2—O14—C19B	77.3 (9)	C30B—C31B—C32B—C33B	0.0
O21—Zn2—O14—C19B	−82.4 (9)	C31B—C32B—C33B—C34B	0.0
O21^i—Zn2—O14—C19B	−173.2 (9)	C32B—C33B—C34B—C29B	0.0
Zn1^i—Zn2—O14—C19B	−178.8 (9)	C35B—C29B—C34B—C33B	176.1 (14)
C19A—O14—C14—C15	−31.2 (8)	C30B—C29B—C34B—C33B	0.0
C19C—O14—C14—C15	−10.1 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O1	0.98	2.43	3.224 (6)	137
C18—H18···O1^i	0.95	2.37	3.173 (5)	142
C28—H28C···O8^ii	0.98	2.69	3.408 (5)	131

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