A novel one-dimensional zinc coordination polymer containing 4-methyl­benzoate and 4,4-bipyridine

The title compound, catena-poly[[tris­([mu]-4-methyl­benzoato)-[kappa]²O:O;[kappa]⁴O:O'-(4-methyl­benzoato-[kappa]²O,O')dizinc(II)]-[mu]-4,4'-bipyridine-[kappa]²N:N'], [Zn₂(C₈H₇O₂)₄(C₁₀H₈N₂)]_n, is a novel coordination polymer. The asymmetric unit contains two unique Zn^II ions, four 4-methyl­benzoate ligands and one 4,4'-bipyridine (4,4'-bpy) ligand, all in general positions. The four 4-methyl­benzoate ligands link the two Zn^II centres to form a dinuclear unit, with a Zn...Zn separation of 3.188 (2) Å, which can be regarded as a supra­molecular secondary building unit (SBU). These SBUs are further bridged by 4,4'-bpy ligands, forming a novel one-dimensional infinite chain. There are [pi]-[pi] stacking inter­actions between the benzene rings of the 4-methyl­benzoate ligands and the pyridyl rings of the 4,4'-bpy ligands, leading to the formation of a corrugated layer. These layers are further assembled via C-H...O hydrogen bonds into a three-dimensional supra­molecular network structure. Coordination polymers such as the title compound are of inter­est for their potential applications as functional materials.

S1. Comment

Much research in recent years has focused on the design and synthesis of new, potentially multifunctional, coordination polymers with useful structure-derived properties, such as porosity, gas storage and ion exchange, or other physical properties such as magnetism and photoluminescence (Shi et al., 2004; Seo et al., 2000; Kitaura et al., 2002; Rowsell et al., 2004; Gheorghe et al., 2003). Many of the reported works are based on the use of mixed functional organic ligands containing N and/or O donor atoms to bind to d-block transition metal ions (Janiak, 1997; Kleij et al., 2005; Eddaoudi et al., 2000; Murugavel et al., 2002). The selection of organic ligands is of great importance in the construction of specfic supramolecular networks with useful physicochemical properties and intriguing structural topologies (Zhang et al., 2005; Zhao et al., 2003; Ren et al., 2003; Gu et al., 2006; Shibasaki et al., 2002; Sabatini et al., 1993). As is well known, 4,4'-bpy (bipyridine) ligands may act in bidentate bridging or monodentate terminal modes, leading to the formation of a variety of one-dimensional chain, two-dimensional layer and three-dimensional network motifs (Biradha et al., 2006). The 4-methylbenzoate ligand with versatile binding and coordination modes can also be used to construct multinuclear structures (Aliaga et al., 2001; Brown et al., 1993). Polynuclear d-block metal complexes have been found to exhibit interesting structural motifs and photoluminescence (Fu et al., 2002; Harvey & Gray, 1988; Ma et al., 1998; Kyle et al., 1991; Henary et al., 1989; Ford et al., 1999). On the basis of these considerations, we chose 4-methylbenzoic acid, 4,4'-bpy and Zn^II as our building blocks. A novel one-dimensional coordination framework, (I), resulted from the hydrothermal treatment of ZnCl₂ with 4-methylbenzoic acid and 4,4'-bpy in alkaline aqueous solution.

The asymmetric unit contains two unique Zn^II ions, four 4-methylbenzoate ligands and one 4,4'-bpy ligand (Fig. 1). Of the two metal centres, Zn2 can be described as having a distorted octahedral coordination geometry formed by five carboxylate O donors of four 4-methylbenzoate ligands, and one N donor of a 4,4'-bpy ligand, while Zn1 is penta-coordinated by four O donors of three 4-methylbenzoate ligands and one N donor of the 4,4'-bpy ligand in a distorted square-pyramidal coordination geometry (Table 1). One Zn—O distance on each metal centre is distinctly longer than the others, but still within the range of a significant interaction (Addison et al., 1971; Guilera et al., 1999). The four 4-methylbenzoate ligands link the two zinc ions to construct a dinuclear zinc building block with a separation of 3.188 (2) Å, which can be regarded as a supramolecular SBU or knot. The construction of the knot is similar to that of the Zn₂(acetate)₄ unit in the infinite chains of that structure (Lee et al., 2004). Unlike the symmetrical paddlewheel arrangement typically observed in M₂(carboxylate)₄ dimers, in (I) two of the 4-methylbenzoate ligands bridge the Zn atoms through separate O atoms, one bridges through a single O atom, and one chelates a single Zn atom only. Each 4,4'-bpy ligand bridges two neighbouring SBUs to form a one-dimensional infinite chain along the c axis of the unit cell (Fig. 2). The distance between two knots is 14.2238 (4) Å, which is equal to the unit length of the c axis. The π–π stacking interactions and intra/intermolecular hydrogen bonds (Table 2) between carboxyl O atoms of 4-methylbenzoate ligands and 4,4'-bpy ligands assemble neighbouring chains into a corrugated layer in the bc plane (Fig. 3). The centroid-to-centroid distances between the phenyl rings of 4-methylbenzoate and the pyridyl rings of 4,4'-bpy belonging to adjacent chains are 3.686 (2) and 3.697 (2) Å, respectively, thus indicating weak π–π stacking contacts (Wu et al., 2003; Pan & Xu, 2004; Li et al., 2005; Deisenhofer & Michel, 1998). Moveover, hydrogen-bonding interactions (Table 2) between methyl groups and carboxyl O atoms of 4-methylbenzoate ligands lead to the formation of a three-dimensional supramolecular network structure.

The overall structural motif in (I) is unprecedented, differing from those described in the review by Biradha et al. (2006). Besides (I), there are only two coordination polymer structures containing 4,4'-bpy and 4-methylbenzoate, in which the neighbouring lanthanide ions are linked together by two bridging–chelating carboxylic groups of 4-methylbenzoate, and the 4,4'-bpy is uncoordinated (Li et al., 2004, 2006). Hydrogen bonds formed between the N atoms from uncoordinated 4,4'-bpy molecules and the O atoms from coordinated 4-methylbenzoate and included water molecules help to stabilize these structures.

Related literature

For related literature, see: Addison et al. (1971); Aliaga et al. (2001); Biradha et al. (2006); Brown et al. (1993); Deisenhofer et al. (1998); Eddaoudi et al. (2000); Ford et al. (1999); Fu et al. (2002); Gheorghe et al. (2003); Gu & Xue (2006); Guilera & Steed (1999); Harvey & Gray (1988); Henary & Zink (1989); Janiak (1997); Kitaura et al. (2002); Kleij et al. (2005); Kyle et al. (1991); Lee et al. (2004); Li et al. (2006); Li et al. (2005); Li et al. (2004); Ma et al. (1998); Murugavel et al. (2002); Pan & Xu (2004); Ren et al. (2003); Rowsell et al. (2004); Sabatini et al. (1993); Seo et al. (2000); Shi et al. (2004); Shibasaki & Yoshikawa (2002); Wu et al. (2003); Zhang et al. (2005); Zhao et al. (2003)

S2. Experimental

A mixture of zinc chloride (0.136 g, 1 mmol), 4-methylbenzoic acid (0.136 g, 1 mmol), 4,4'-bipyridine (0.156 g, 1 mmol), NaOH (0.06 g, 1.5 mmol) and H₂O (12 ml) was placed in a 23 ml Teflon reactor, which was heated to 433 K for 3 d and then cooled to room temperature at a rate of 10 K h^-1. The crystals obtained were washed with water and dried in air (yield 0.37 g, 90.2%).

S3. Refinement

Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93–0.96 Å and U_iso(H) = 1.2 U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. View of the asymmetric unit of (I) (H atoms are omitted for clarity). Symmetry code: (i) x, y, z - 1.
	Fig. 2. View of one infinite chain running parallel to the c axis.
	Fig. 3. View of a corrugated layer in the bc plane (left) and ab plane (right).

catena-Poly[[tris(µ-4-methylbenzoato)-κ²O:O;κ⁴O:O'-(4-methylbenzoato- κ²O,O')dizinc(II)]-µ-4,4'-bipyridine-κ-N:N']

Crystal data

[Zn2(C8H7O2)4(C10H8N2)]	F(000) = 1704
Mr = 827.47	Dx = 1.423 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3600 reflections
a = 12.3661 (3) Å	θ = 1.4–28°
b = 22.0755 (6) Å	µ = 1.30 mm^−1
c = 14.2238 (4) Å	T = 296 K
β = 95.997 (2)°	Block, colorless
V = 3861.67 (18) Å^3	0.30 × 0.26 × 0.20 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	6946 independent reflections
Radiation source: fine-focus sealed tube	4275 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
ϕ and ω scans	θmax = 25.2°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.697, Tmax = 0.781	k = −26→26
30933 measured reflections	l = −16→17

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0357P)^2] where P = (Fo^2 + 2Fc^2)/3
6946 reflections	(Δ/σ)max = 0.001
491 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.40 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
C1	0.5188 (3)	0.16030 (17)	1.1211 (3)	0.0456 (9)
H1	0.5547	0.1904	1.0907	0.055*
C2	0.5201 (3)	0.16303 (16)	1.2173 (3)	0.0456 (9)
H2	0.5567	0.1944	1.2506	0.055*
C3	0.4670 (3)	0.11904 (15)	1.2656 (2)	0.0362 (9)
C4	0.4149 (3)	0.07329 (16)	1.2101 (3)	0.0431 (9)
H4	0.3788	0.0425	1.2388	0.052*
C5	0.4164 (3)	0.07323 (16)	1.1141 (3)	0.0444 (9)
H5	0.3804	0.0423	1.0791	0.053*
C6	0.4694 (3)	0.11998 (15)	1.3693 (3)	0.0371 (9)
C7	0.5125 (3)	0.16835 (17)	1.4227 (3)	0.0533 (10)
H7	0.5382	0.2022	1.3931	0.064*
C8	0.5171 (3)	0.16610 (17)	1.5200 (3)	0.0587 (11)
H8	0.5457	0.1994	1.5540	0.070*
C9	0.4400 (3)	0.07367 (18)	1.5167 (3)	0.0515 (10)
H9	0.4139	0.0406	1.5481	0.062*
C10	0.4312 (3)	0.07215 (16)	1.4188 (3)	0.0492 (10)
H10	0.3995	0.0389	1.3865	0.059*
C11	0.6750 (3)	0.14395 (19)	0.9131 (3)	0.0480 (10)
C12	0.7931 (3)	0.13249 (17)	0.9095 (3)	0.0433 (9)
C13	0.8675 (3)	0.17885 (17)	0.9283 (3)	0.0556 (11)
H13	0.8439	0.2167	0.9462	0.067*
C14	0.9761 (3)	0.1693 (2)	0.9206 (3)	0.0690 (13)
H14	1.0244	0.2015	0.9309	0.083*
C15	1.0152 (3)	0.1135 (2)	0.8982 (3)	0.0656 (13)
C16	0.9414 (3)	0.06684 (19)	0.8841 (3)	0.0691 (13)
H16	0.9659	0.0282	0.8715	0.083*
C17	0.8316 (3)	0.07638 (18)	0.8882 (3)	0.0586 (11)
H17	0.7832	0.0444	0.8763	0.070*
C18	1.1340 (3)	0.1035 (2)	0.8850 (4)	0.1043 (19)
H18A	1.1743	0.1398	0.9013	0.156*
H18B	1.1405	0.0934	0.8202	0.156*
H18C	1.1623	0.0709	0.9250	0.156*
C19	0.3767 (3)	0.20266 (16)	0.7983 (3)	0.0437 (9)
C20	0.2977 (3)	0.25141 (16)	0.7656 (3)	0.0447 (9)
C21	0.2443 (3)	0.28415 (17)	0.8291 (3)	0.0603 (11)
H21	0.2529	0.2739	0.8929	0.072*
C22	0.1780 (3)	0.3322 (2)	0.7983 (4)	0.0765 (14)
H22	0.1430	0.3541	0.8420	0.092*
C23	0.1627 (3)	0.3482 (2)	0.7044 (4)	0.0739 (14)
C24	0.2135 (3)	0.31359 (19)	0.6403 (3)	0.0685 (13)
H24	0.2019	0.3224	0.5762	0.082*
C25	0.2813 (3)	0.26608 (17)	0.6708 (3)	0.0545 (10)
H25	0.3160	0.2439	0.6272	0.065*
C26	0.0961 (4)	0.4035 (2)	0.6708 (4)	0.114 (2)
H26A	0.0643	0.4211	0.7232	0.171*
H26B	0.0396	0.3916	0.6230	0.171*
H26C	0.1425	0.4327	0.6451	0.171*
C27	0.3784 (3)	0.02390 (16)	0.8020 (3)	0.0422 (9)
C28	0.3076 (3)	−0.02960 (15)	0.7796 (3)	0.0427 (9)
C29	0.2654 (3)	−0.06246 (17)	0.8503 (3)	0.0540 (10)
H29	0.2787	−0.0496	0.9127	0.065*
C30	0.2047 (3)	−0.11336 (18)	0.8299 (3)	0.0642 (12)
H30	0.1780	−0.1346	0.8789	0.077*
C31	0.1822 (3)	−0.13391 (18)	0.7390 (4)	0.0637 (12)
C32	0.2227 (3)	−0.10052 (19)	0.6673 (3)	0.0655 (12)
H32	0.2080	−0.1131	0.6048	0.079*
C33	0.2837 (3)	−0.04951 (17)	0.6873 (3)	0.0532 (10)
H33	0.3095	−0.0278	0.6383	0.064*
C34	0.1202 (4)	−0.19240 (19)	0.7165 (4)	0.1032 (18)
H34A	0.1707	−0.2250	0.7118	0.155*
H34B	0.0753	−0.1881	0.6576	0.155*
H34C	0.0752	−0.2010	0.7660	0.155*
C35	0.7217 (3)	0.1042 (2)	0.6754 (3)	0.0507 (10)
C36	0.8346 (3)	0.10411 (18)	0.6456 (3)	0.0548 (11)
C37	0.8885 (3)	0.1575 (2)	0.6357 (3)	0.0813 (15)
H37	0.8542	0.1941	0.6458	0.098*
C38	0.9939 (4)	0.1574 (2)	0.6108 (4)	0.1052 (19)
H38	1.0286	0.1942	0.6030	0.126*
C39	1.0480 (4)	0.1049 (3)	0.5972 (4)	0.0849 (16)
C40	0.9932 (4)	0.0517 (2)	0.6073 (4)	0.0932 (16)
H40	1.0278	0.0151	0.5980	0.112*
C41	0.8871 (3)	0.0511 (2)	0.6309 (3)	0.0752 (13)
H41	0.8516	0.0144	0.6368	0.090*
C42	1.1664 (4)	0.1054 (2)	0.5742 (4)	0.125 (2)
H42A	1.1828	0.1442	0.5485	0.187*
H42B	1.1765	0.0743	0.5288	0.187*
H42C	1.2139	0.0981	0.6309	0.187*
N1	0.4679 (2)	0.11609 (13)	1.0683 (2)	0.0410 (7)
N2	0.4833 (2)	0.11935 (13)	1.5685 (2)	0.0462 (8)
O1	0.60770 (19)	0.10158 (11)	0.87928 (18)	0.0526 (7)
O2	0.6418 (2)	0.19093 (12)	0.94713 (19)	0.0632 (8)
O3	0.4408 (2)	0.18473 (11)	0.74200 (18)	0.0548 (7)
O4	0.37398 (18)	0.18349 (11)	0.88151 (18)	0.0505 (7)
O5	0.38816 (17)	0.04283 (10)	0.88602 (17)	0.0476 (6)
O6	0.42509 (18)	0.04670 (10)	0.73573 (17)	0.0509 (7)
O7	0.67889 (19)	0.15390 (12)	0.69576 (17)	0.0533 (7)
O8	0.67044 (19)	0.05532 (12)	0.67936 (17)	0.0576 (7)
Zn1	0.46827 (3)	0.116784 (17)	0.92731 (3)	0.04154 (15)
Zn2	0.53210 (3)	0.112299 (18)	0.71601 (3)	0.04317 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.053 (2)	0.047 (2)	0.037 (3)	0.0022 (19)	0.0111 (19)	0.004 (2)
C2	0.052 (2)	0.039 (2)	0.046 (3)	0.0023 (18)	0.0092 (19)	−0.002 (2)
C3	0.039 (2)	0.037 (2)	0.032 (2)	0.0053 (16)	0.0026 (17)	0.0010 (18)
C4	0.047 (2)	0.049 (2)	0.034 (2)	−0.0024 (18)	0.0067 (18)	0.009 (2)
C5	0.048 (2)	0.051 (2)	0.035 (2)	−0.0015 (19)	0.0085 (18)	0.000 (2)
C6	0.043 (2)	0.040 (2)	0.028 (2)	0.0051 (17)	0.0040 (17)	−0.0005 (18)
C7	0.083 (3)	0.044 (2)	0.033 (3)	−0.004 (2)	0.001 (2)	0.004 (2)
C8	0.089 (3)	0.045 (2)	0.040 (3)	−0.002 (2)	−0.004 (2)	0.002 (2)
C9	0.057 (3)	0.062 (3)	0.037 (3)	−0.011 (2)	0.014 (2)	0.004 (2)
C10	0.060 (2)	0.051 (2)	0.037 (3)	−0.011 (2)	0.0050 (19)	−0.004 (2)
C11	0.051 (3)	0.064 (3)	0.031 (2)	−0.003 (2)	0.0078 (19)	0.005 (2)
C12	0.041 (2)	0.052 (2)	0.036 (2)	−0.0014 (18)	0.0014 (18)	0.0038 (19)
C13	0.049 (3)	0.058 (3)	0.061 (3)	0.000 (2)	0.009 (2)	−0.005 (2)
C14	0.044 (3)	0.070 (3)	0.093 (4)	−0.014 (2)	0.004 (2)	−0.008 (3)
C15	0.042 (3)	0.082 (3)	0.073 (3)	−0.002 (2)	0.004 (2)	−0.012 (3)
C16	0.051 (3)	0.066 (3)	0.090 (4)	0.006 (2)	0.006 (2)	−0.018 (3)
C17	0.047 (3)	0.056 (3)	0.072 (3)	−0.011 (2)	0.007 (2)	−0.012 (2)
C18	0.047 (3)	0.126 (4)	0.140 (5)	0.000 (3)	0.011 (3)	−0.037 (4)
C19	0.040 (2)	0.043 (2)	0.049 (3)	−0.0039 (18)	0.004 (2)	0.003 (2)
C20	0.039 (2)	0.045 (2)	0.050 (3)	−0.0041 (18)	0.0018 (19)	0.003 (2)
C21	0.051 (3)	0.066 (3)	0.065 (3)	0.015 (2)	0.012 (2)	0.005 (2)
C22	0.066 (3)	0.078 (3)	0.086 (4)	0.022 (3)	0.011 (3)	−0.003 (3)
C23	0.053 (3)	0.056 (3)	0.109 (5)	0.005 (2)	−0.004 (3)	0.011 (3)
C24	0.064 (3)	0.065 (3)	0.073 (3)	−0.002 (2)	−0.011 (3)	0.020 (3)
C25	0.051 (3)	0.052 (3)	0.059 (3)	0.000 (2)	−0.002 (2)	0.005 (2)
C26	0.090 (4)	0.078 (3)	0.170 (6)	0.033 (3)	−0.003 (4)	0.035 (4)
C27	0.035 (2)	0.043 (2)	0.049 (3)	0.0046 (17)	0.003 (2)	0.005 (2)
C28	0.039 (2)	0.046 (2)	0.043 (3)	0.0021 (17)	0.0050 (18)	−0.001 (2)
C29	0.056 (3)	0.058 (3)	0.049 (3)	−0.012 (2)	0.008 (2)	0.002 (2)
C30	0.068 (3)	0.066 (3)	0.060 (3)	−0.018 (2)	0.016 (2)	0.008 (3)
C31	0.062 (3)	0.054 (3)	0.074 (4)	−0.013 (2)	0.004 (3)	−0.008 (3)
C32	0.066 (3)	0.076 (3)	0.052 (3)	−0.009 (2)	−0.001 (2)	−0.017 (3)
C33	0.053 (3)	0.058 (3)	0.048 (3)	−0.006 (2)	0.006 (2)	0.000 (2)
C34	0.109 (4)	0.072 (3)	0.128 (5)	−0.037 (3)	0.010 (3)	−0.022 (3)
C35	0.048 (3)	0.068 (3)	0.036 (3)	−0.007 (2)	0.0054 (19)	0.002 (2)
C36	0.050 (3)	0.064 (3)	0.052 (3)	−0.007 (2)	0.014 (2)	−0.006 (2)
C37	0.062 (3)	0.068 (3)	0.120 (4)	−0.007 (2)	0.036 (3)	−0.008 (3)
C38	0.073 (4)	0.091 (4)	0.159 (6)	−0.025 (3)	0.047 (4)	−0.004 (4)
C39	0.054 (3)	0.117 (4)	0.087 (4)	0.006 (3)	0.023 (3)	0.007 (4)
C40	0.069 (3)	0.094 (4)	0.122 (5)	0.018 (3)	0.039 (3)	−0.008 (4)
C41	0.071 (3)	0.066 (3)	0.092 (4)	0.000 (2)	0.027 (3)	−0.006 (3)
C42	0.061 (3)	0.171 (6)	0.150 (6)	0.001 (3)	0.049 (3)	0.005 (4)
N1	0.0422 (18)	0.0465 (18)	0.0346 (19)	0.0050 (15)	0.0057 (14)	0.0014 (16)
N2	0.057 (2)	0.049 (2)	0.034 (2)	0.0011 (16)	0.0100 (15)	−0.0011 (17)
O1	0.0412 (15)	0.0707 (18)	0.0472 (17)	−0.0065 (13)	0.0105 (12)	−0.0058 (14)
O2	0.0589 (18)	0.0706 (19)	0.062 (2)	0.0067 (15)	0.0151 (14)	−0.0105 (16)
O3	0.0608 (17)	0.0567 (16)	0.0492 (18)	0.0142 (13)	0.0165 (14)	0.0023 (14)
O4	0.0496 (16)	0.0565 (16)	0.0462 (18)	0.0099 (12)	0.0092 (13)	0.0103 (14)
O5	0.0499 (16)	0.0545 (16)	0.0400 (17)	−0.0037 (12)	0.0119 (12)	−0.0025 (14)
O6	0.0547 (16)	0.0554 (16)	0.0430 (17)	−0.0135 (13)	0.0065 (13)	0.0052 (13)
O7	0.0542 (16)	0.0624 (17)	0.0448 (17)	−0.0011 (14)	0.0123 (13)	−0.0046 (15)
O8	0.0560 (17)	0.0604 (17)	0.0577 (19)	−0.0109 (14)	0.0120 (14)	0.0016 (15)
Zn1	0.0441 (3)	0.0487 (3)	0.0327 (3)	0.0023 (2)	0.0084 (2)	0.0017 (2)
Zn2	0.0467 (3)	0.0480 (3)	0.0364 (3)	−0.0015 (2)	0.0119 (2)	−0.0001 (2)

Geometric parameters (Å, º)

C1—N1	1.346 (4)	C24—H24	0.9300
C1—C2	1.368 (5)	C25—H25	0.9300
C1—H1	0.9300	C26—H26A	0.9600
C2—C3	1.393 (5)	C26—H26B	0.9600
C2—H2	0.9300	C26—H26C	0.9600
C3—C4	1.397 (4)	C27—O5	1.260 (4)
C3—C6	1.473 (5)	C27—O6	1.261 (4)
C4—C5	1.367 (4)	C27—C28	1.485 (5)
C4—H4	0.9300	C28—C29	1.385 (4)
C5—N1	1.346 (4)	C28—C33	1.386 (5)
C5—H5	0.9300	C29—C30	1.366 (5)
C6—C10	1.380 (4)	C29—H29	0.9300
C6—C7	1.384 (4)	C30—C31	1.371 (6)
C7—C8	1.381 (5)	C30—H30	0.9300
C7—H7	0.9300	C31—C32	1.394 (6)
C8—N2	1.332 (4)	C31—C34	1.519 (5)
C8—H8	0.9300	C32—C33	1.369 (5)
C9—N2	1.328 (4)	C32—H32	0.9300
C9—C10	1.385 (5)	C33—H33	0.9300
C9—H9	0.9300	C34—H34A	0.9600
C10—H10	0.9300	C34—H34B	0.9600
C11—O2	1.233 (4)	C34—H34C	0.9600
C11—O1	1.310 (4)	C35—O8	1.255 (4)
C11—C12	1.488 (5)	C35—O7	1.266 (4)
C12—C17	1.372 (5)	C35—C36	1.500 (5)
C12—C13	1.384 (5)	C36—C41	1.364 (5)
C13—C14	1.375 (5)	C36—C37	1.369 (5)
C13—H13	0.9300	C37—C38	1.387 (6)
C14—C15	1.373 (5)	C37—H37	0.9300
C14—H14	0.9300	C38—C39	1.364 (6)
C15—C16	1.378 (5)	C38—H38	0.9300
C15—C18	1.516 (5)	C39—C40	1.371 (6)
C16—C17	1.381 (5)	C39—C42	1.532 (6)
C16—H16	0.9300	C40—C41	1.387 (6)
C17—H17	0.9300	C40—H40	0.9300
C18—H18A	0.9600	C41—H41	0.9300
C18—H18B	0.9600	C42—H42A	0.9600
C18—H18C	0.9600	C42—H42B	0.9600
C19—O3	1.248 (4)	C42—H42C	0.9600
C19—O4	1.261 (4)	Zn1—N1	2.007 (3)
C19—C20	1.495 (5)	Zn1—O1	1.949 (2)
C20—C21	1.378 (5)	Zn1—O2	2.690 (2)
C20—C25	1.381 (5)	Zn1—O4	1.948 (2)
C21—C22	1.384 (5)	Zn1—O5	1.967 (2)
C21—H21	0.9300	Zn2—N2^i	2.128 (3)
C22—C23	1.375 (6)	Zn2—O1	2.423 (3)
C22—H22	0.9300	Zn2—O3	2.014 (2)
C23—C24	1.390 (6)	Zn2—O6	2.001 (2)
C23—C26	1.521 (6)	Zn2—O7	2.081 (2)
C24—C25	1.383 (5)	Zn2—O8	2.229 (2)
N1—C1—C2	123.1 (3)	C29—C28—C33	117.5 (4)
N1—C1—H1	118.5	C29—C28—C27	121.3 (4)
C2—C1—H1	118.5	C33—C28—C27	121.2 (4)
C1—C2—C3	120.4 (4)	C30—C29—C28	121.1 (4)
C1—C2—H2	119.8	C30—C29—H29	119.4
C3—C2—H2	119.8	C28—C29—H29	119.4
C2—C3—C4	116.0 (3)	C29—C30—C31	121.7 (4)
C2—C3—C6	121.5 (3)	C29—C30—H30	119.1
C4—C3—C6	122.4 (3)	C31—C30—H30	119.1
C5—C4—C3	120.7 (3)	C30—C31—C32	117.5 (4)
C5—C4—H4	119.6	C30—C31—C34	121.9 (4)
C3—C4—H4	119.6	C32—C31—C34	120.5 (4)
N1—C5—C4	122.6 (3)	C33—C32—C31	121.0 (4)
N1—C5—H5	118.7	C33—C32—H32	119.5
C4—C5—H5	118.7	C31—C32—H32	119.5
C10—C6—C7	116.3 (3)	C32—C33—C28	121.1 (4)
C10—C6—C3	121.9 (3)	C32—C33—H33	119.4
C7—C6—C3	121.8 (3)	C28—C33—H33	119.4
C8—C7—C6	119.7 (4)	C31—C34—H34A	109.5
C8—C7—H7	120.2	C31—C34—H34B	109.5
C6—C7—H7	120.2	H34A—C34—H34B	109.5
N2—C8—C7	124.3 (4)	C31—C34—H34C	109.5
N2—C8—H8	117.8	H34A—C34—H34C	109.5
C7—C8—H8	117.8	H34B—C34—H34C	109.5
N2—C9—C10	124.1 (3)	O8—C35—O7	120.6 (3)
N2—C9—H9	118.0	O8—C35—C36	120.1 (4)
C10—C9—H9	118.0	O7—C35—C36	119.3 (4)
C6—C10—C9	119.9 (3)	C41—C36—C37	118.5 (4)
C6—C10—H10	120.0	C41—C36—C35	121.1 (4)
C9—C10—H10	120.0	C37—C36—C35	120.4 (4)
O2—C11—O1	121.3 (3)	C36—C37—C38	120.4 (4)
O2—C11—C12	121.7 (4)	C36—C37—H37	119.8
O1—C11—C12	117.0 (4)	C38—C37—H37	119.8
C17—C12—C13	118.1 (3)	C39—C38—C37	121.7 (4)
C17—C12—C11	121.7 (3)	C39—C38—H38	119.1
C13—C12—C11	120.2 (3)	C37—C38—H38	119.1
C14—C13—C12	120.5 (4)	C38—C39—C40	117.3 (4)
C14—C13—H13	119.8	C38—C39—C42	121.1 (5)
C12—C13—H13	119.8	C40—C39—C42	121.5 (5)
C15—C14—C13	121.8 (4)	C39—C40—C41	121.5 (4)
C15—C14—H14	119.1	C39—C40—H40	119.2
C13—C14—H14	119.1	C41—C40—H40	119.2
C14—C15—C16	117.4 (4)	C36—C41—C40	120.5 (4)
C14—C15—C18	121.9 (4)	C36—C41—H41	119.7
C16—C15—C18	120.6 (4)	C40—C41—H41	119.7
C15—C16—C17	121.3 (4)	C39—C42—H42A	109.5
C15—C16—H16	119.4	C39—C42—H42B	109.5
C17—C16—H16	119.4	H42A—C42—H42B	109.5
C12—C17—C16	120.8 (4)	C39—C42—H42C	109.5
C12—C17—H17	119.6	H42A—C42—H42C	109.5
C16—C17—H17	119.6	H42B—C42—H42C	109.5
C15—C18—H18A	109.5	C5—N1—C1	117.2 (3)
C15—C18—H18B	109.5	C5—N1—Zn1	122.7 (3)
H18A—C18—H18B	109.5	C1—N1—Zn1	120.1 (2)
C15—C18—H18C	109.5	C9—N2—C8	115.6 (3)
H18A—C18—H18C	109.5	C9—N2—Zn2^ii	123.2 (2)
H18B—C18—H18C	109.5	C8—N2—Zn2^ii	119.6 (3)
O3—C19—O4	125.2 (4)	C11—O1—Zn1	107.5 (2)
O3—C19—C20	117.9 (4)	C11—O1—Zn2	116.7 (2)
O4—C19—C20	116.9 (3)	Zn1—O1—Zn2	92.99 (10)
C21—C20—C25	119.0 (4)	C19—O3—Zn2	140.8 (3)
C21—C20—C19	121.1 (4)	C19—O4—Zn1	119.6 (2)
C25—C20—C19	119.8 (4)	C27—O5—Zn1	123.6 (2)
C20—C21—C22	120.2 (4)	C27—O6—Zn2	139.0 (2)
C20—C21—H21	119.9	C35—O7—Zn2	92.3 (2)
C22—C21—H21	119.9	C35—O8—Zn2	85.9 (2)
C23—C22—C21	121.5 (4)	O4—Zn1—O1	122.25 (11)
C23—C22—H22	119.3	O4—Zn1—O5	105.21 (10)
C21—C22—H22	119.3	O1—Zn1—O5	100.88 (10)
C22—C23—C24	117.9 (4)	O4—Zn1—N1	106.03 (11)
C22—C23—C26	121.8 (5)	O1—Zn1—N1	116.34 (11)
C24—C23—C26	120.2 (5)	O5—Zn1—N1	103.79 (11)
C25—C24—C23	120.8 (4)	O6—Zn2—O3	99.05 (10)
C25—C24—H24	119.6	O6—Zn2—O7	159.70 (10)
C23—C24—H24	119.6	O3—Zn2—O7	100.89 (10)
C20—C25—C24	120.4 (4)	O6—Zn2—N2^i	93.87 (11)
C20—C25—H25	119.8	O3—Zn2—N2^i	90.93 (10)
C24—C25—H25	119.8	O7—Zn2—N2^i	89.59 (11)
C23—C26—H26A	109.5	O6—Zn2—O8	99.17 (9)
C23—C26—H26B	109.5	O3—Zn2—O8	161.78 (10)
H26A—C26—H26B	109.5	O7—Zn2—O8	60.97 (10)
C23—C26—H26C	109.5	N2^i—Zn2—O8	87.49 (10)
H26A—C26—H26C	109.5	O6—Zn2—O1	89.40 (9)
H26B—C26—H26C	109.5	O3—Zn2—O1	93.97 (9)
O5—C27—O6	124.8 (3)	O7—Zn2—O1	85.47 (9)
O5—C27—C28	117.6 (3)	N2^i—Zn2—O1	173.62 (9)
O6—C27—C28	117.6 (4)	O8—Zn2—O1	86.58 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O8^iii	0.93	2.40	3.328 (5)	172
C4—H4···O8^iii	0.93	2.56	3.462 (4)	165
C1—H1···O2	0.93	2.41	3.111 (5)	133
C18—H18A···O4^iv	0.96	2.69	3.458 (5)	137

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