A three-dimensional coordination polymer based on the Zn₄(μ₃-OH)₂ unit: poly[[(μ₄-benzene-1,4-di­carboxyl­ato)bis­(μ₃-benzene-1,4-di­carboxyl­ato)bis­(μ₃-hydroxido)bis(1,10-phenanthroline-5,6-dione)tetra­zinc] dihydrate]

The title compound, {[Zn₄(C₈H₄O₄)₃(OH)₂(C₁₂H₆N₂O₂)₂]·2H₂O}_n, has been prepared hydro­thermally by the reaction of Zn(NO₃)₂·6H₂O with benzene-1,4-di­carb­oxy­lic acid (H₂bdc) and 1,10-phenanthroline-5,6-dione (pdon) in H₂O. In the crystal structure, a tetra­nuclear Zn₄(OH)₂ fragment is located on a crystallographic inversion centre which relates two subunits, each containing a [ZnN₂O₄] octa­hedron and a [ZnO₄] tetra­hedron bridged by a μ₃-OH group. The pdon ligand chelates to zinc through its two N atoms to form part of the [ZnN₂O₄] octa­hedron. The two crystallographically independent bdc²⁻ ligands are fully deprotonated and adopt μ₃-κO:κO′:κO′′ and μ₄-κO:κO′:κO′′:κO′′′ coordination modes, bridging three or four Zn^II cations, respectively, from two Zn₄(OH)₂ units. The Zn₄(OH)₂ fragment connects six neighbouring tetra­nuclear units through four μ₃-bdc²⁻ and two μ₄-bdc²⁻ ligands, forming a three-dimensional framework with uninodal 6-connected α-Po topology, in which the tetra­nuclear Zn₄(OH)₂ units are considered as 6-connected nodes and the bdc²⁻ ligands act as linkers. The uncoordinated water mol­ecules are located on opposite sides of the Zn₄(OH)₂ unit and are connected to it through hydrogen-bonding inter­actions involving hydroxide and carboxyl­ate groups. The structure is further stabilized by extensive π–π inter­actions between the pdon and μ₄-bdc²⁻ ligands.

S1. Introduction

Three-dimensional coordination polymers (CPs) have attracted considerable inter­est in recent years as a result of their novel architectures and diverse topologies, as well as their potential applications in gas storage, separation, sensing and catalysis (Férey, 2008; Long & Yaghi, 2009; Zhou et al., 2012). The use of polynuclear metal clusters as secondary building units (SBUs) to bind organic linkers is a promising synthetic strategy for CPs. Simple connections between inorganic SBUs and organic linkers can produce CPs with varied networks and properties (O'Keeffe et al., 2008; Fang et al., 2011; Cook et al., 2013; Li et al., 2013). Aromatic polycarboxyl­ates are frequently used for this strategy because they have rigid organic skeletons, excellent coordination capability and flexible coordination patterns (Férey, 2008; Long & Yaghi, 2009; Zhou et al., 2012). Recent studies show that the use of mixed ligands is an effective approach for building novel CPs with diverse topological networks (Chen & Tong, 2007; Cui et al., 2012; Suh et al., 2012). In the light of this consideration, our current synthetic strategy is to construct new CPs by combining benzene-1,4-di­carb­oxy­lic acid (H₂bdc) and 1,10-phenanthroline-5,6-dione (pdon) ligands. It is well known that the rigid H₂bdc molecule can act as a versatile bridging ligand to ligate various metal ions. The neutral pdon ligand, possessing both ketone and imine groups, has attracted attention as a chelating ligand in transition metal complexes with potentially useful functional properties, such as in catalysis, sensing and nonlinear optics (Shavaleev et al., 2003; Larsson & Öhrström, 2004). In the study reported herein, we explore the self-assembly of Zn^II, H₂bdc and pdon under hydro­thermal conditions, isolating and characterizing a novel three-dimensional coordination polymer, viz. {[Zn₄(bdc)₃(OH)₂(pdon)₂]·2H₂O}_n, (I).

S2. Experimental

S2.1. Synthesis and crystallization

A mixture of Zn(NO₃)₂·6H₂O (0.0469 g, 0.16 mmol), H₂bdc (0.0163 g, 0.10 mmol), pdon (0.0218 g, 0.10 mmol) and H₂O (3 ml) was heated in a 23 ml Teflon reactor at 413 K for 3 d, followed by slow cooling to room temperature at a rate of 10 K h^-1. The resulting pale-yellow block-shaped crystals of (I) were washed with water and dried in air (yield 0.028 g, 68%).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C atoms and to atom O7 were placed at calculated positions and refined using a riding-model approximation, with C—H = 0.93 Å and O—H = 0.98 Å, and with U_iso(H) = 1.2U_eq(C,O). The H atoms on atom O10 could not be located in difference maps. Additional free water molecules were present and were highly disordered, and attempts to locate and refine these water molecules were unsuccessful. The diffuse electron densities resulting from these residual water molecules were removed using the SQUEEZE routine (Spek, 2015) of PLATON (Spek, 2009). The formula and related intrinsic properties given in the CIF reflect the presence of the two H atoms bonded to atom O10 but do not include what is possibly, consistent with the results of SQUEEZE, a single molecule of water per asymmetric unit.

S3. Results and discussion

The asymmetric unit of (I) consists of two independent Zn^II cations, one 1,10-phenanthroline-5,6-dione (pdon) ligand, one and a half units of the benzene-1,4-di­carboxyl­ate (bdc^2-) anion, one hydroxide anion and one uncoordinated water molecule. One bdc^2- ligand (denoted bdc-1) sits astride a crystallographic inversion centre. The second independent bdc^2- ligand (denoted bdc-2), as well as the two Zn^II cations, the pdon ligand, a hydroxide anion and a water molecule, all lie on general positions.

As shown in Fig. 1, atom Zn1 is six-coordinated by two N atoms from one pdon ligand, by one carboxyl­ate O atom each from one bdc-1 and one bdc-2 ligand, and by two hydroxide O atoms, forming a slightly distorted o­cta­hedron. Atom Zn2 is coordinated tetra­hedrally by one hydroxide O atom and by three carboxyl­ate O atoms from one bdc-1 and two bdc-2 ligands. Both crystallographically independent bdc^2- ligands are fully (i.e. doubly) deprotonated and adopt µ₃-κO:κO':κO'' (bdc-2) and µ₄-κO:κO':κO'':κO''' (bdc-1) coordination modes, bridging three or four Zn^II cations from two Zn₄(OH)₂ secondary building units (SBUs) (see below), respectively. The dihedral angles between the planes of the carboxyl­ate groups at bdc-2 and their adjacent benzene ring are 5.2 (3) and 3.5 (2)°, while the unique dihedral angle for the bdc-1 ligand is 6.5 (5)°. The pdon ligand chelates the Zn1 centre through its two N atoms. The Zn—O bond lengths in the Zn1-centred o­cta­hedron are slightly longer than those of the Zn2-based tetra­hedron (Table 2). The hydroxide ligand in (I) bridges three Zn^II cations, i.e. one Zn2 centre and the inversion-related Zn1 and Zn1ⁱ [Fig. 2; symmetry code: (i) -x, -y + 1, -z + 1] to form an OH-centred triangular Zn₃(µ₃-OH) unit. Two Zn₃(µ₃-OH) units share a Zn1—Zn1ⁱ edge, forming a tetra­nuclear Zn₄(OH)₂ SBU (Fig. 2) which sits across the inversion centre. The four Zn^II cations lie in the same plane, from which the two hydroxide O7 congeners deviate by 0.675 (4) Å on opposite sides.

In (I), both of the independent bdc^2- units are connected to two Zn₄(OH)₂ SBUs, although the coordination modes of the bdc^2- ligands are different from each other. The tetra­nuclear Zn₄(OH)₂ SBU connects to six neighbouring congeners through four bdc-1 and two bdc-2 ligands, forming a three-dimensional framework (Fig. 3). To simplify this structure, each Zn₄(OH)₂ SBU was treated as a 6-connected node and both bdc^2- ligands were treated as linkers. The whole framework of (I) can then be topologically represented as a uninodal 6-connected α-Po network with a Schläfli symbol of 4¹².6³ (Fig. 3). This network was also identified as a pcu net according to the RCSR symbol (O'Keeffe et al., 2008; Alexandrov et al., 2011; Blatov et al., 2004). The empty spaces of the three-dimensional framework are inter­laced with an equivalent framework to form a twofold inter­penetrating network.

Uncoordinated water molecules (O10) are located on both sides of the Zn₄(OH)₂ fragment, and connect with it through hydrogen-bonding inter­actions involving carboxyl­ate atom O2 and the O7 hydroxide group [O10···O2 = 2.764 (7) Å and O10···O7 = 3.049 (7) Å]. The structure of (I) is further stabilized by weak π–π stacking inter­actions between the benzene rings of the pdon and bdc-2 ligands, with Cg1···Cg2^v = 3.764 (4) Å [Cg1 and Cg2 are the centroids of the C4–C7/C11/C12 (denoted R1) and C13–C18 (R2) rings, respectively; symmetry code: (v) -x + 1/2, -y + 1, z - 1/2]. The perpendicular distances from Cg1 to the plane of R2^v and from Cg2^v to R1 are 3.434 (3) and 3.475 (3) Å, respectively. Furthermore, there are numerous π–π contacts involving the carboxyl­ate groups of the bdc-2 ligands and the pyridine rings of the pdon ligands, with C···C and C···O distances shorter than 3.4 Å (Fig. 4).

In conclusion, we have synthesized a new Zn^II coordination polymer based on benzene-1,4-di­carb­oxy­lic acid and 1,10-phenanthroline-5,6-dione. Single-crystal X-ray diffraction analysis reveals that the compound possesses a three-dimensional network structure with a uninodal 6-connected α-Po topology. This coordination polymer is reinforced by π–π stacking inter­actions.

Computing details

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear (Rigaku, 2001); data reduction: CrystalClear (Rigaku, 2001); 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 coordination environments of atoms Zn1 and Zn2 in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms bonded to C atoms have been omitted for clarity. [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) x, -y + 1/2, z - 1/2; (iii) -x + 1, -y + 1, -z + 1.]
	Fig. 2. The coordination environment of the tetranuclear Zn4(OH)2 secondary building unit. H atoms bonded to C atoms have been omitted for clarity. [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) x, -y + 1/2, z - 1/2.]
	Fig. 3. (Left) A perspective view of (I) along the a axis, showing the twofold interpenetrating frameworks. (Right) A diagram of the 6-connected pcu network, in which the Zn4(OH)2 units are considered as 6-connected nodes and the bdc ligands act as linkers. The H atoms, chelating pdon ligands and water molecules have been omitted for clarity.
	Fig. 4. A view of the aromatic π–π stacking interactions between the pdon and bdc-2 ligands in (I), with olive-green ring centroids and turquoise Cg1···Cg2 vectors. C···C and C···O distances shorter than 3.4 Å, involving the carboxylate groups of the bdc-2 ligands and the pyridine rings of the pdon ligands, are drawn as green dashed lines. H atoms have been omitted.

Poly[[(µ₄-benzene-1,4-dicarboxylato)bis(µ₃-benzene-1,4-dicarboxylato)bis(µ₃-hydroxido)bis(1,10-phenanthroline-5,6-dione)tetrazinc] dihydrate]

Crystal data

[Zn2(C8H4O4)1.5(OH)(C12H6N2O2)]·H2O	F(000) = 2504
Mr = 622.12	Dx = 1.628 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 16246 reflections
a = 13.870 (3) Å	θ = 3.0–27.5°
b = 19.023 (4) Å	µ = 1.95 mm^−1
c = 19.238 (4) Å	T = 293 K
V = 5076.1 (18) Å^3	Block, pale yellow
Z = 8	0.32 × 0.18 × 0.14 mm

Data collection

Rigaku Mercury CCD area-detector diffractometer	4420 independent reflections
Radiation source: fine-focus sealed tube	4234 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
Detector resolution: 28.5714 pixels mm^-1	θmax = 25.0°, θmin = 3.1°
ω scans	h = 0→16
Absorption correction: multi-scan ?	k = 0→22
Tmin = 0.574, Tmax = 0.772	l = 0→22
40123 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: mixed
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0149P)^2 + 22.8916P] where P = (Fo^2 + 2Fc^2)/3
4420 reflections	(Δ/σ)max = 0.001
343 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.31 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
Zn1	0.09564 (4)	0.51621 (3)	0.45568 (3)	0.02866 (16)
Zn2	0.13548 (4)	0.39678 (3)	0.56744 (3)	0.02884 (16)
C1	0.1227 (5)	0.6608 (3)	0.5365 (3)	0.0578 (18)
H1A	0.1165	0.6334	0.5762	0.069*
C2	0.1386 (6)	0.7320 (4)	0.5445 (5)	0.082 (3)
H2A	0.1451	0.7522	0.5883	0.099*
C3	0.1444 (6)	0.7720 (4)	0.4849 (5)	0.078 (2)
H3A	0.1534	0.8203	0.4883	0.093*
C4	0.1369 (5)	0.7412 (3)	0.4202 (4)	0.0598 (18)
C5	0.1437 (6)	0.7836 (4)	0.3541 (5)	0.077 (2)
C6	0.1463 (5)	0.7447 (4)	0.2838 (4)	0.067 (2)
C7	0.1380 (4)	0.6672 (3)	0.2858 (3)	0.0506 (16)
C8	0.1442 (5)	0.6275 (4)	0.2241 (3)	0.064 (2)
H8A	0.1516	0.6498	0.1813	0.077*
C9	0.1393 (6)	0.5565 (4)	0.2278 (3)	0.076 (2)
H9A	0.1444	0.5292	0.1879	0.091*
C10	0.1265 (5)	0.5252 (4)	0.2926 (3)	0.0584 (18)
H10A	0.1227	0.4764	0.2945	0.070*
C11	0.1258 (4)	0.6311 (3)	0.3489 (3)	0.0362 (12)
C12	0.1241 (4)	0.6686 (3)	0.4161 (3)	0.0391 (13)
C13	0.0889 (5)	0.1823 (3)	0.7995 (3)	0.0545 (17)
H13A	0.0767	0.1356	0.7884	0.065*
C14	0.0943 (5)	0.2322 (3)	0.7467 (3)	0.0560 (17)
H14A	0.0887	0.2183	0.7005	0.067*
C15	0.1078 (4)	0.3019 (3)	0.7627 (3)	0.0361 (12)
C16	0.1161 (5)	0.3209 (3)	0.8323 (3)	0.0481 (15)
H16A	0.1237	0.3681	0.8436	0.058*
C17	0.1133 (5)	0.2716 (3)	0.8853 (3)	0.0462 (15)
H17A	0.1193	0.2857	0.9313	0.055*
C18	0.1017 (4)	0.2014 (3)	0.8692 (3)	0.0346 (12)
C19	0.1029 (4)	0.1466 (3)	0.9258 (3)	0.0364 (12)
C20	0.1140 (4)	0.3556 (3)	0.7051 (3)	0.0408 (13)
C21	0.4022 (4)	0.4856 (3)	0.5084 (3)	0.0345 (11)
C22	0.4333 (4)	0.5402 (3)	0.4663 (4)	0.0580 (19)
H22A	0.3882	0.5678	0.4432	0.070*
C23	0.5294 (4)	0.5540 (3)	0.4580 (4)	0.0554 (18)
H23A	0.5486	0.5906	0.4292	0.066*
C24	0.2969 (4)	0.4711 (3)	0.5151 (3)	0.0316 (11)
N1	0.1157 (3)	0.6291 (2)	0.4746 (2)	0.0396 (11)
N2	0.1194 (3)	0.5610 (2)	0.3525 (2)	0.0374 (11)
O1	0.1127 (3)	0.3322 (2)	0.6431 (2)	0.0523 (11)
O2	0.1206 (4)	0.4185 (2)	0.7205 (2)	0.0700 (14)
O3	0.1170 (3)	0.16730 (19)	0.98773 (18)	0.0435 (10)
O4	0.0904 (3)	0.08377 (19)	0.90803 (18)	0.0424 (9)
O5	0.2720 (2)	0.42453 (19)	0.55980 (19)	0.0394 (9)
O6	0.2413 (3)	0.5058 (2)	0.4773 (2)	0.0451 (10)
O7	0.0555 (2)	0.48098 (17)	0.55627 (16)	0.0281 (7)
H7	0.0749	0.5162	0.5907	0.034*
O8	0.1496 (6)	0.8481 (3)	0.3550 (4)	0.127 (3)
O9	0.1551 (4)	0.7782 (3)	0.2290 (3)	0.097 (2)
O10	0.1301 (5)	0.5589 (3)	0.6839 (3)	0.108 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0281 (3)	0.0305 (3)	0.0274 (3)	0.0008 (2)	0.0023 (2)	0.0021 (2)
Zn2	0.0307 (3)	0.0312 (3)	0.0246 (3)	−0.0005 (2)	0.0016 (2)	0.0030 (2)
C1	0.067 (5)	0.057 (4)	0.050 (4)	−0.018 (3)	0.005 (3)	−0.016 (3)
C2	0.093 (6)	0.064 (5)	0.089 (6)	−0.030 (4)	0.017 (5)	−0.043 (5)
C3	0.082 (6)	0.039 (4)	0.112 (7)	−0.015 (4)	0.021 (5)	−0.023 (4)
C4	0.055 (4)	0.034 (3)	0.090 (5)	−0.006 (3)	0.018 (4)	0.002 (4)
C5	0.074 (5)	0.044 (4)	0.114 (7)	−0.016 (4)	0.008 (5)	0.016 (4)
C6	0.047 (4)	0.057 (4)	0.099 (6)	−0.003 (3)	0.009 (4)	0.037 (4)
C7	0.037 (3)	0.055 (4)	0.060 (4)	−0.003 (3)	0.003 (3)	0.025 (3)
C8	0.055 (4)	0.091 (6)	0.046 (4)	−0.001 (4)	0.005 (3)	0.028 (4)
C9	0.113 (7)	0.079 (5)	0.036 (4)	−0.002 (5)	0.012 (4)	0.001 (4)
C10	0.089 (5)	0.053 (4)	0.033 (3)	−0.005 (4)	0.009 (3)	0.001 (3)
C11	0.026 (3)	0.038 (3)	0.044 (3)	−0.001 (2)	0.003 (2)	0.011 (3)
C12	0.027 (3)	0.035 (3)	0.055 (4)	0.001 (2)	0.008 (2)	0.009 (3)
C13	0.090 (5)	0.032 (3)	0.042 (3)	−0.009 (3)	−0.011 (3)	0.001 (3)
C14	0.097 (5)	0.043 (4)	0.028 (3)	−0.005 (3)	−0.008 (3)	0.003 (3)
C15	0.039 (3)	0.038 (3)	0.032 (3)	0.000 (2)	0.001 (2)	0.009 (2)
C16	0.075 (5)	0.034 (3)	0.036 (3)	−0.002 (3)	0.002 (3)	0.002 (3)
C17	0.075 (5)	0.034 (3)	0.030 (3)	0.000 (3)	0.003 (3)	0.001 (2)
C18	0.039 (3)	0.033 (3)	0.031 (3)	0.002 (2)	0.002 (2)	0.011 (2)
C19	0.035 (3)	0.037 (3)	0.038 (3)	−0.003 (2)	0.004 (2)	0.007 (3)
C20	0.030 (3)	0.044 (3)	0.048 (4)	−0.001 (2)	−0.001 (2)	0.013 (3)
C21	0.028 (3)	0.037 (3)	0.038 (3)	0.005 (2)	0.000 (2)	0.004 (2)
C22	0.030 (3)	0.066 (4)	0.078 (5)	0.004 (3)	−0.006 (3)	0.042 (4)
C23	0.028 (3)	0.060 (4)	0.078 (5)	−0.003 (3)	−0.001 (3)	0.035 (4)
C24	0.030 (3)	0.033 (3)	0.032 (3)	0.004 (2)	0.003 (2)	−0.001 (2)
N1	0.043 (3)	0.033 (3)	0.043 (3)	−0.008 (2)	0.003 (2)	−0.006 (2)
N2	0.040 (3)	0.037 (3)	0.035 (2)	−0.004 (2)	0.005 (2)	0.007 (2)
O1	0.075 (3)	0.050 (2)	0.032 (2)	−0.003 (2)	0.004 (2)	0.0148 (19)
O2	0.109 (4)	0.043 (3)	0.057 (3)	−0.012 (3)	−0.008 (3)	0.019 (2)
O3	0.060 (3)	0.040 (2)	0.030 (2)	−0.0013 (19)	−0.0023 (18)	0.0056 (17)
O4	0.058 (3)	0.034 (2)	0.035 (2)	−0.0047 (18)	0.0007 (18)	0.0095 (17)
O5	0.0281 (19)	0.045 (2)	0.045 (2)	−0.0014 (16)	0.0026 (16)	0.0124 (19)
O6	0.0230 (18)	0.059 (3)	0.053 (2)	−0.0023 (18)	−0.0002 (17)	0.018 (2)
O7	0.0281 (17)	0.0305 (18)	0.0257 (17)	0.0012 (14)	0.0004 (14)	−0.0008 (15)
O8	0.170 (7)	0.048 (3)	0.164 (7)	−0.013 (4)	0.033 (6)	0.031 (4)
O9	0.094 (4)	0.079 (4)	0.119 (5)	−0.001 (3)	0.011 (4)	0.059 (4)
O10	0.176 (7)	0.061 (3)	0.086 (4)	0.001 (4)	−0.034 (4)	0.009 (3)

Geometric parameters (Å, º)

Zn1—O6	2.071 (4)	C11—C12	1.477 (8)
Zn1—O7^i	2.109 (3)	C12—N1	1.358 (7)
Zn1—O4^ii	2.113 (3)	C13—C14	1.392 (8)
Zn1—O7	2.122 (3)	C13—C18	1.399 (7)
Zn1—N2	2.185 (4)	C13—H13A	0.9300
Zn1—N1	2.195 (4)	C14—C15	1.375 (8)
Zn2—O1	1.931 (4)	C14—H14A	0.9300
Zn2—O7	1.960 (3)	C15—C16	1.392 (7)
Zn2—O5	1.971 (3)	C15—C20	1.508 (7)
Zn2—O3^ii	1.976 (4)	C16—C17	1.386 (7)
C1—N1	1.337 (7)	C16—H16A	0.9300
C1—C2	1.382 (9)	C17—C18	1.380 (7)
C1—H1A	0.9300	C17—H17A	0.9300
C2—C3	1.379 (11)	C18—C19	1.508 (7)
C2—H2A	0.9300	C19—O4	1.256 (6)
C3—C4	1.380 (10)	C19—O3	1.270 (6)
C3—H3A	0.9300	C20—O2	1.236 (7)
C4—C12	1.396 (8)	C20—O1	1.274 (7)
C4—C5	1.508 (10)	C21—C23^iii	1.374 (7)
C5—O8	1.230 (8)	C21—C22	1.386 (8)
C5—C6	1.542 (11)	C21—C24	1.493 (7)
C6—O9	1.239 (8)	C22—C23	1.367 (8)
C6—C7	1.478 (9)	C22—H22A	0.9300
C7—C11	1.406 (8)	C23—C21^iii	1.374 (7)
C7—C8	1.410 (9)	C23—H23A	0.9300
C8—C9	1.354 (10)	C24—O6	1.250 (6)
C8—H8A	0.9300	C24—O5	1.281 (6)
C9—C10	1.393 (9)	O3—Zn2^iv	1.976 (4)
C9—H9A	0.9300	O4—Zn1^iv	2.113 (3)
C10—N2	1.343 (7)	O7—Zn1^i	2.109 (3)
C10—H10A	0.9300	O7—H7	0.9800
C11—N2	1.338 (6)
O6—Zn1—O7^i	173.30 (14)	N1—C12—C11	117.4 (5)
O6—Zn1—O4^ii	92.00 (16)	C4—C12—C11	121.6 (5)
O7^i—Zn1—O4^ii	86.62 (14)	C14—C13—C18	121.1 (5)
O6—Zn1—O7	92.46 (13)	C14—C13—H13A	119.5
O7^i—Zn1—O7	81.17 (13)	C18—C13—H13A	119.5
O4^ii—Zn1—O7	95.87 (14)	C15—C14—C13	120.1 (5)
O6—Zn1—N2	94.16 (15)	C15—C14—H14A	120.0
O7^i—Zn1—N2	92.33 (14)	C13—C14—H14A	120.0
O4^ii—Zn1—N2	87.84 (16)	C14—C15—C16	118.5 (5)
O7—Zn1—N2	172.29 (15)	C14—C15—C20	119.8 (5)
O6—Zn1—N1	86.38 (17)	C16—C15—C20	121.7 (5)
O7^i—Zn1—N1	96.83 (15)	C17—C16—C15	122.0 (5)
O4^ii—Zn1—N1	163.13 (16)	C17—C16—H16A	119.0
O7—Zn1—N1	100.98 (15)	C15—C16—H16A	119.0
N2—Zn1—N1	75.54 (17)	C18—C17—C16	119.6 (5)
O1—Zn2—O7	120.67 (16)	C18—C17—H17A	120.2
O1—Zn2—O5	112.56 (17)	C16—C17—H17A	120.2
O7—Zn2—O5	108.46 (14)	C17—C18—C13	118.7 (5)
O1—Zn2—O3^ii	99.86 (17)	C17—C18—C19	120.4 (5)
O7—Zn2—O3^ii	110.23 (15)	C13—C18—C19	120.9 (5)
O5—Zn2—O3^ii	103.41 (16)	O4—C19—O3	124.9 (5)
N1—C1—C2	123.6 (7)	O4—C19—C18	117.4 (5)
N1—C1—H1A	118.2	O3—C19—C18	117.7 (5)
C2—C1—H1A	118.2	O2—C20—O1	124.3 (5)
C3—C2—C1	117.2 (7)	O2—C20—C15	119.0 (5)
C3—C2—H2A	121.4	O1—C20—C15	116.7 (5)
C1—C2—H2A	121.4	C23^iii—C21—C22	118.1 (5)
C2—C3—C4	120.8 (6)	C23^iii—C21—C24	122.3 (5)
C2—C3—H3A	119.6	C22—C21—C24	119.7 (5)
C4—C3—H3A	119.6	C23—C22—C21	121.1 (5)
C3—C4—C12	118.7 (7)	C23—C22—H22A	119.5
C3—C4—C5	121.9 (6)	C21—C22—H22A	119.5
C12—C4—C5	119.4 (7)	C22—C23—C21^iii	120.8 (5)
O8—C5—C4	121.7 (8)	C22—C23—H23A	119.6
O8—C5—C6	119.3 (8)	C21^iii—C23—H23A	119.6
C4—C5—C6	119.0 (6)	O6—C24—O5	126.1 (5)
O9—C6—C7	122.9 (8)	O6—C24—C21	117.1 (4)
O9—C6—C5	120.1 (7)	O5—C24—C21	116.8 (4)
C7—C6—C5	117.0 (6)	C1—N1—C12	118.8 (5)
C11—C7—C8	118.3 (6)	C1—N1—Zn1	126.7 (4)
C11—C7—C6	121.2 (6)	C12—N1—Zn1	114.5 (4)
C8—C7—C6	120.5 (6)	C11—N2—C10	117.2 (5)
C9—C8—C7	119.1 (6)	C11—N2—Zn1	116.5 (4)
C9—C8—H8A	120.5	C10—N2—Zn1	126.3 (4)
C7—C8—H8A	120.5	C20—O1—Zn2	118.8 (4)
C8—C9—C10	118.8 (7)	C19—O3—Zn2^iv	123.8 (3)
C8—C9—H9A	120.6	C19—O4—Zn1^iv	137.2 (3)
C10—C9—H9A	120.6	C24—O5—Zn2	119.6 (3)
N2—C10—C9	124.0 (6)	C24—O6—Zn1	140.3 (3)
N2—C10—H10A	118.0	Zn2—O7—Zn1^i	126.52 (16)
C9—C10—H10A	118.0	Zn2—O7—Zn1	102.09 (14)
N2—C11—C7	122.7 (5)	Zn1^i—O7—Zn1	98.83 (13)
N2—C11—C12	115.7 (5)	Zn2—O7—H7	109.2
C7—C11—C12	121.5 (5)	Zn1^i—O7—H7	109.2
N1—C12—C4	120.8 (6)	Zn1—O7—H7	109.2

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