Isomerism in double-pillared-layer coordination polymers – structures and photoreactivity

The existence of isomerism in coordination polymeric structures offers opportunities to understand structure–function relationships. Herein the serendipitous isolation is reported of two isomeric double-pillared-layer coordination polymeric structures arising from two different types of carboxyl­ate bonding of benzene-1,4-di­carboxyl­ate ligands to zinc(II), which constitutes a new type of structural isomerism. The different bonding modes not only alter the shape and size of the pores, but also the nature of interpenetration and photoreactivity. Although two trans,cis,trans-bpeb ligands with conjugated olefin bonds are aligned in close proximity in both of the structures, one isomer undergoes a double [2 + 2] cyclo­addition reaction and the second isomer only offers an incomplete single cyclo­addition product. This work demonstrates how small changes in the structural connectivity can have an impact on the overall structural, physical and chemical properties of such materials.

1. Introduction

Recent advances in the design and construction of a wide variety of highly crystalline coordination polymers (CPs) and metal–organic frameworks (MOFs) are mainly based on the self-assembly of these compounds in a one-pot crystallization process (Steed & Atwood, 2009; Ramanan & Whittingham, 2006). Researchers seek to engineer, fine tune and control the chemical composition, dimensionality, connectivity, topology, interpenetration, pore size and shape of these solid-state materials in order to vary their physical and chemical properties for various applications (Kitagawa et al., 2004; Horike et al., 2009; Long & Yaghi, 2009; Zhou et al., 2012; Janiak, 2003; Moulton & Zaworotko, 2001; Zaworotko, 2001; Zhang et al., 2008). In other words, the solid-state properties are dictated by the molecular packing, which in turn is influenced by crystallization conditions. The crystallization conditions may yield not only different polymorphs but also isomeric products. In the multi-dimensional coordination polymeric structures, various types of structural and stereoisomerism are possible that are similar to those encountered in discrete molecules, in addition to supramolecular isomerism (Moulton & Zaworotko, 2001; Zaworotko, 2001; Zhang et al., 2008; Guillerm et al., 2014). These isomers provide opportunities to improve our understanding of the structure–function relationship in these polymeric materials. In this respect, new types of isomerism in CPs and MOFs have been discovered to yield interesting solid properties (Blake, 2001; Barnett et al., 2012; Hu et al., 2012; Panda et al., 2013; Poplaukhin & Tiekink, 2010; Manna et al., 2008; Karmakar et al., 2017).

Carboxylates are known to have a variety of bonding modes to the metal centres (Guo et al., 2013). Dicarboxylate spacer ligands such as the 1,4-benzenedicarboxylate anion can connect metal ions in three different ways using their chelating and bridging abilities, as shown in Fig. 1(a). These three types of bonding modes can generate two structural isomers while maintaining the same (4,4) connectivity as shown in Figs. 1(b) and 1(c) (Gong et al., 2013; Park et al., 2017). It may be noted that the isomer containing both type-I and type-II di­carboxyl­ate linkages in the [M₂(di­carboxyl­ate)₂] layer (Fig. 1b) has an ideal rectangular shape with mm symmetry. The second isomer with type-III linkages has the shape of an ideal square with fourfold rotational symmetry in the [M₂(dicarboxylate)₂] building block, as displayed in Fig. 1(c).

Figure 1 (a) Three types of connectivities of bdc in the chelating and bridging modes. Two structural isomers in the double-pillared-layer structure [M2(di­carboxyl­ate)2(pillar)2]. (b) The (4,4) `rectangular' net has an idealized local mm symmetry with type-I and type-II linkages. (c) The (4,4) `square' net has an idealized local fourfold rotational symmetry with type-III connectivity of di­carboxyl­ates. A rhombus-shaped net is also possible for type-III linkages. The axial positions are occupied by di­pyridyl pillar ligands, which have been omitted for clarity.

Synthesis and isolation of these two closely related structural isomers are challenging. Furthermore, they are expected to form concomitantly in one synthesis. These two types of connectivities have been reported recently for dicarboxylates with different chemical compositions (Gong et al., 2013; Park et al., 2017). To the best of our knowledge, such structural isomerism has not yet been documented in metal complexes or CPs with the same chemical formula.

The influence of the single- and double-pillared-layer structures on the physical properties and chemical reactivities has been investigated (Takashima et al., 2011; Mahata et al., 2006; Kitaura et al., 2002, 2003; Kitagawa & Matsuda, 2007; Sato et al., 2010; Park, Medishetty et al., 2014; Park et al., 2015; Chun et al., 2005; Seo et al., 2009; Maji et al., 2004; Henke et al., 2012). Supramolecular isomers with different dimensionalities and topologies have been shown to possess different physical properties (Moulton & Zaworotko, 2001; Zaworotko, 2001). Since the two structural isomers described here have the same topology and differ only in their dicarboxylate bonding modes, it is interesting to investigate their properties. During our attempts to grow higher quality single crystals suitable for X-ray intensity data collection, we isolated a double-pillared-layer coordination polymeric structure with the molecular formula {Zn₂(bpeb)₂(bdc)₂] {bdc = 1,4-benzenedicarboxylate, bpeb = 1,4-bis[2-(4-pyridyl)ethenyl]benzene}, when dimethylformamide (DMF) was used as one of the solvents. When DMF was replaced by dimethylacetamide (DMA), we were able to isolate two structural isomers formed concomitantly in a one-pot synthesis as major and minor products. Of these two isomers exhibiting twofold interpenetration, one has parallel and the other has perpendicular interpenetration with respect to the bpeb pillar ligands. As these pillar ligands have olefin bonds arranged in close proximity, it gives an opportunity to investigate the [2 + 2] cycloaddition photoreactivity in these two supramolecular isomers. Further photoluminescent properties were also recorded and discussed in this report.

2. Results and discussion

The single crystals of [Zn₂(bpeb)₂(bdc)₂]·2DMF·2H₂O·0.5DMSO (1) were obtained from Zn(NO₃)₂·6H₂O, H₂bdc and bpeb in a 1:1:1 molar ratio in a mixture of DMF, dimethyl sulfoxide (DMSO) and water along with a few drops of NaOH solution heated at 393 K for 48 h. When DMF was replaced by DMA, a similar solvothermal synthesis yielded the supra­molecular isomers of [Zn₂(bpeb)₂(bdc)₂]·2DMA·2H₂O (2) and [Zn₂(bpeb)₂(bdc)₂]·DMA (3) concomitantly. Plate-like yellow crystals of (2) were the major product, whereas pale-yellow rod-shaped crystals of (3) were the minor product (less than 1%) in this reaction. We were unable to obtain (3) in larger quantities by changing the experimental conditions. The solid-state structures determined from single-crystal X-ray diffraction techniques are described below.

The asymmetric unit of (1), which crystallized in P2₁/c with Z = 4, has a formula unit in which both bpeb ligands are disordered, see Fig. 2(a). Interestingly, each bpeb ligand has both trans,trans,trans (all-trans) and trans,cis,trans conformations in the ratio of 60:40, respectively. The dinuclear repeating unit consists of two Zn^II atoms bridged by two carboxyl­ate groups; each Zn^II is chelated by a carboxylate group (Fig. 2b). The bridging carboxyl­ates have a syn-anti-μ₂-η¹:η¹ bonding mode observed from the two sets of Zn—O—C angles [128.9 (3)° and 128.4 (3)°; 150.2 (3)° and 148.1 (3)°]. The [Zn₂(O₂C—C)₂] is roughly planar. The exo-carboxylate groups in the para positions of the bdc ligands are connected to generate a (4,4) layer structure of [Zn₂(bdc)₂]. In fact, the Zn—bpeb—Zn distance and the diagonal distances between the centres of the Zn₂ dimer in the Zn₂(bdc)₂ rhomboidal ring are the a, b and c unit-cell lengths. Furthermore, a closer examination reveals that each bdc has type-III carboxylate bonding. The (4,4) grid is rhombus-shaped as a result of the symmetrical bonding, with the dimensions 12.530 × 12.554 Å and an angle of 79°. The axial positions of the highly distorted octahedral Zn^II centres are occupied by the nitrogen atoms of the bpeb ligands. The bpeb ligands are acting like pillars, connecting the [Zn₂(bdc)₂] layers through pyridyl groups to produce double-pillared-layer structures with primitive cubic unit (pcu) topology (Fig. 2c). The structure is doubly interpenetrated as a result of the large empty space. It may be noted that a pair of bpeb pillars from the neighbouring pcu unit penetrate each rhomboidal ring in the [Zn₂(bdc)₂] layer, thus forming a twofold parallel interpenetration as displayed in Fig. 2(c). The empty cavity generated by the bpeb ligands is filled by the double interpenetration. The total potential solvent area volume in (1), calculated using PLATON (Spek, 2009), is 1633 ų, which is 26.8% of the unit-cell volume 6094.6 ų.

Figure 2 (a) The (4,4) net formed by Zn2(bdc)2 in (1). (b) Single pcu unit showing the orientations of the bpeb pillars. (c) Twofold parallel interpenetration of the pcu units. For clarity, the disorder and hydrogen atoms are not shown.

Compound (2) was the major product of the crystallization using DMA in the solvothermal reaction and crystallized in the orthorhombic space group Pcca (No. 54) with Z = 4 (Fig. S2 in the supporting information). The asymmetric unit has half of the formula unit, i.e. [Zn(bpeb)(bdc)]. In this structure, the middle ring (C8–C15) of the bpeb is disordered and hence a mixture of all-trans and trans,cis,trans conformations are present (Fig. S2a). Otherwise, the structural description is very similar to that of (1) with type-III bonding of the bdc ligand as well as twofold parallel interpenetration (Fig. S2d). However, the Zn—bpeb—Zn distance and the diagonal distances between the centres of the Zn₂ dimer in the Zn₂(bdc)₂ rhomboidal ring are the b, a and c unit-cell lengths. The total potential solvent area volume in (2), calculated using PLATON (Spek, 2009), is 1912 ų, which is 30.6% of the unit-cell volume 6247.5 ų.

The minor product (3) crystallized in the monoclinic space group C2/c with Z = 8 (Fig. 3). The asymmetric unit contains the building unit [Zn₂(bpeb)₂(bdc)₂]. In this `no disorder' structure, both bpeb have trans,cis,trans conformations (Fig. 3b). Furthermore, two types of bdc bonding, namely type-I and type-II, are present in the [Zn₂(bdc)₂] layer (Fig. 3a), resulting in a parallelogram-shaped (4,4) grid with the dimensions 14.948  × 10.159 Å and an angle of 77.1°. The overall connectivity has pcu topology (Fig. 3c) similar to (1) and (2). This also has twofold interpenetration, but the [Zn₂(bpeb)₂(bdc)₂] units are normal with respect to each other as shown in Fig. 3(c). This could be attributed to insufficient space for the two bpeb pillars to interpenetrate the (4,4) net. On the other hand, the void formed by Zn—bpeb—Zn and Zn-(type-II) bdc—Zn with the dimensions 20.127 × 14.948 Å is sufficient to form a twofold perpendicular interpenetration. The total potential solvent area volume in (3), calculated using PLATON (Spek, 2009), is 2769.2 ų, which is 24.3% of the unit-cell volume 11 388.7 ų, indicating that this structure is more efficiently packed than (2).

Figure 3 (a) The (4,4) net formed by Zn2(bdc)2 in (3). (b) Single pcu unit showing the orientations of the bpeb pillars. (c) Twofold perpendicular interpenetration of the pcu units. For clarity, the hydrogen atoms are not shown.

In the double-pillared-layer structures, the two Zn^II centres assist in bringing the axial bpeb pillar ligands closer such that the olefin pairs satisfy Schmidt's conditions for a [2 + 2] photo­cyclo­addition reaction (Schmidt, 1971). Interestingly, the two disordered bpeb ligands in (1) adopt a mixture of all-trans and trans,cis,trans-conformation (Fig. 2b). Nonetheless, the six-membered rings in the two bpeb ligands are aligned in a face-to-face manner with a separation in the range 3.572–4.150 Å. The centres of the two olefin pairs are also separated by a distance in the range 3.854–4.006 Å, which is congenial for double [2 + 2] cyclo­addition reactions. However, because of the presence of mixed conformations in the disordered ligands, it was difficult to predict a priori the outcome of the photoreaction under UV light.

The ¹H NMR spectrum of solid (1) was collected after irradiation under UV light for 48 h and dissolution in DMSO-d₆ aided by a drop of HNO₃; it showed the appearance of cyclo­butane peaks at 4.9–4.6 and 5.3–5.20 p.p.m. along with other peaks attributed to the aromatic protons in the region 7.7–8.9 p.p.m. (Fig. S14). Although ¹H NMR data indicated double dimerization, the nature of the product was not clear. To investigate the solid-state structure of the photo-irradiated product of (1), named (4), we attempted to obtain single crystals of product (4) at the end of the cyclo­addition reaction and eventually succeeded.

The single-crystal X-ray crystallographic analysis of [Zn₂(tppcp)(bdc)₂] (4) [tppcp = tetrakis­(4-pyridyl)-1,2,9,10-diethano­[2.2]para­cyclo­phane, Fig. 4a)] proved the quantitative photo cyclo­addition of the trans,cis,trans-bpeb pairs (Fig. 4b). Obviously the partially disordered all-trans conformation had changed to the trans,cis,trans conformation under UV light. Interestingly the space group changed to Pcca with Z = 4 and the asymmetric unit contained half of the unit-cell formula. The double [2 + 2] cyclo­addition product tppcp is disordered due to the presence of a centre of inversion at the centre of the ligand structure. Furthermore, the Zn—(tppcp)—Zn distance and diagonal distances between the centres of the Zn₂ dimer in the Zn₂(bdc)₂ rhomboidal ring are the b, a and c unit-cell lengths. Therefore, the packing is very similar to that of (2).

Figure 4 (a) Structure of the double-dimerized photoproduct of bpeb pairs, namely, tppcp. (b) A portion of the structure of (4) showing the double-dimerized photoproduct of trans,cis,trans-bpeb pairs. For clarity, the disorder and hydrogen atoms are not shown.

In (2), both the bpeb pairs have a disordered mixture of all-trans and trans,cis,trans conformations similar to (1). The olefin bonds in these bpeb pairs were separated by 3.544 and 3.728 Å, hence (2) is also expected to be photoreactive. The photoreactivity of (2) was investigated under UV light. Solid (2) was irradiated under UV light for 48 h; the irradiated product (5) was dissolved in DMSO-d₆ aided by of a drop of HNO₃ to obtain an ¹H NMR spectrum, which showed the appearance of cyclo­butane peaks at 4.6–4.9 p.p.m. along with other peaks attributed to aromatic protons in the region 7.7–8.9 p.p.m. (Fig. S15). In order to gain more insight into the nature of the photoproduct, we attempted a single-crystal-to-single-crystal (SCSC) reaction under UV light and succeeded.

As proven by single-crystal X-ray crystallography, the space group (Pcca) of the photoproduct [Zn₂(tppcp)(bdc)₂] (5) was retained from (2). Although the quality of the structure was poor, it was found to be isotypical to that of (4). The quantitative photocyclo­addition of the trans,cis,trans-bpeb pairs was observed. It is interesting to find that both (1) and (2) crystallized in two different space groups, yet gave isotypical photoproducts (4) and (5). It is noted that the double dimerization in bpeb has been reported in both organic compounds and MOFs, but arising only from all-trans-bpeb pairs (Papaefstathiou et al., 2005; Friščič & MacGillivray, 2003; Liu et al., 2010).

Finally, the solid-state photoreactivity of (3) was examined under UV light. The bpeb pairs have trans,cis,trans conformation, arranged in an approximately face-to-face manner with an interplanar angle of 11.4°. This was also expected to be photoreactive as the olefin bonds in these bpeb pairs were separated by 3.938 and 3.927 Å. Solid (3) was irradiated under UV light for 48 h and the irradiated product (6) was treated under similar conditons to (1) in order to obtain an ¹H NMR spectrum. It showed the appearance of cyclo­butane peaks at 5.08 and 4.86 p.p.m. along with other peaks attributed to aromatic protons in the region 7.7–8.9 p.p.m. (Fig. S16). There were a number of unreacted olefin groups indicated by the presence of peaks at 7.62 and 8.00 p.p.m.. It appears that (3) undergoes an incomplete [2 + 2] cyclo­addition reaction.

In order to gain more insight into the nature of the above photoproduct, we attempted an SCSC reaction under UV light. and we were able to get single crystals of the partially photodimerized product. X-ray crystallographic analysis of (6) shows that the cyclo­butane ring was formed between one of the two bpeb pairs, as shown in Fig. 5. Furthermore, only partial dimerization (38.9%) occurred in this crystal. Prolonged UV irradiation only destroyed the single crystals. We were unable to confirm whether complete dimerization of the single olefin pairs is possible in (3), resulting from a lack of suitable single crystals and the scarcity of the compound. Such photodimerization of single olefin pairs in bpeb has been reported before (Friščić & MacGillivray, 2006). It is evident that the photoreactive behaviour of (3) is completely different from that of (1) and (2). The packing in (3) is more efficient than in (2), as shown by the respective void volumes [30.6% in (2) versus 24.3% in (3). This indicates that the bpeb pairs in (3) do not have enough free volume to undergo double dimerization as in (1) or (2) and provides an explanation for the inability of (3) to remian as a single crystal after quantitative single dimerization. This is also supported by non-parallel orientations of the central phenyl­ene rings (interplanar angle, 29.9°) of the bpeb pairs in (3).

Figure 5 (a) The structural diagram of the monocyclized bpeb pairs in (6). (b) A portion of the structure of (6) showing the monocyclized bpeb pairs as the pillar in the photoproduct of (3). For clarity, the disorder and hydrogen atoms are not shown.

3. Conclusions

In summary, we have serendipitously isolated two structural isomers as a result of the different bonding modes of carboxyl­ates in the bdc ligands present in the double-pillared-layer coordination polymers. We were able to synthesize one of the isomers (1) exclusively, but only a small quantity of the second isomer (3). These isomers are expected to have similar energies and are likely to be kinetic products. The MOF with diamondoid topology reported previously is also a supramolecular isomer to (1)-(3), this could be considered as the thermodynamic product (Park, Chanthapally et al., 2014; Park et al. 2016). We have not found suitable experimental conditions to synthesize (3) exclusively despite many attempts. The isolation of energetically similar isomers can be compared with discovering new polymorphs of organic crystals (Haleblian & McCrone, 1969; Bernstein, 2002). These new types of structural isomers have a different packing efficiency, nature of interpenetration and photoreactivity. The two pillared trans,cis,trans-bpeb ligands with conjugated olefin bonds are closely aligned to each other in both structures. The isomers (1) and (2) can undergo face-to-face double [2 + 2] cyclo­addition reactions and the isomer (3) yields only the partial single cyclo­addition product, (6). These results highlight how small structural differences can influence the overall structural, physical and chemical properties. Perpendicular interpenetration observed in (3) seems to be more efficient for crystal packing, but this is not congenial for face-to-face double dimerization of the bpeb pairs. This work highlights the possibility of fine tuning the packing and photoreactivity of CPs and MOFs through structural isomerism.

4. Experimental

4.1. General

All the chemicals were reagent grade and were used without further purification. The bpeb ligand was synthesized by the reported procedure (Gutov et al., 2009). Elemental analyses were carried out using a LECO CHNS-932 elemental analyser. The infrared (IR) spectra (4000–400 cm^-1) were recorded on a Thermo Fisher Scientific Nicolet iS 10 F T-IR spectrometer using KBr pellets. Thermogravimetric analyses (TGA) were performed under a nitro­gen atmosphere with a heating rate of 5 K min⁻¹ using a TA Instruments TGA-Q50 thermogravimetric analyser. For the TGA analysis, drying the product at 343 K for 24 h led to the loss of guest water molecules. The solid-state emission spectra were obtained from a Shimadzu RF-5301PC, using powder samples packed between glass slides in air at room temperature (296 K) using an excitation wavelength of 360 nm. Powder X-ray diffraction (PXRD) patterns were recorded on a D8 DISCOVER with GADDS (Bruker AXS) with graphite-monochromated Cu Kα radiation (λ = 1.54056 Å) at room temperature (296 K). The UV–vis spectra were recorded on a Shimadzu UV-3600 UV-VIS-NIR spectrometer. The UV irradiation experiments were carried out on a LUZCHEM UV reactor with an 8 W dark-blue phosphor lamp (300–400 nm).

4.2. Preparation of [Zn₂(bpeb)₂(bdc)₂]·2DMF·2H₂O·0.5DMSO (1)

A mixture of bpeb (20.2 mg, 0.071 mmol), H₂bdc (12.0 mg, 0.072 mmol) and Zn(NO₃)₂·4H₂O (18.6 mg, 0.071 mmol) dissolved in DMF (3 ml), H₂O (1 ml) and DMSO (0.5 ml) were placed in a 10 ml glass tube, and then 3–4 drops of 0.1 M NaOH were added. The tube was sealed and kept at 393 K for 48 h, followed by cooling to room temperature (296 K) over 8 h. Pale-yellow block-shaped crystals of (1) suitable for X-ray analysis were obtained (yield 45%). Analysis, calculated for [C₆₃H₆₁N₆O_12.5S_0.5Zn₂]: C, 60.58; H, 4.92; N, 6.73; S, 1.28%; found: C, 60.45; H, 4.63; N, 6.66; S, 1.47%; IR (KBr pellet) 3447, 3051, 2926, 2838, 1676, 1605, 1501, 1429, 1385, 1257, 1220, 1132, 1092, 1067, 1017, 970, 875, 835, 750 and 659 cm⁻¹.

4.3. Preparation of a mixture of [Zn₂(bpeb)₂(bdc)₂]·2DMA ·2H₂O (2) and [Zn₂(bpeb)₂(bdc)₂]·DMA (3)

A mixture of bpeb (19.9 mg, 0.070 mmol), H₂bdc (11.8 mg, 0.071 mmol) and Zn(NO₃)₂·4H₂O (18.8 mg, 0.072 mmol) dissolved in DMA (3 ml), H₂O (1 ml) and DMSO (0.5 ml) were placed in a 10 ml glass tube, and then 3–4 drops of 0.1 M NaOH were added. The tube was sealed and kept at 393 K for 48 h, followed by cooling to room temperature (296 K) over 8 h. Pale-yellow plate-shaped crystals (2) (major) and pale-yellow rod-shaped crystals (3) (as a minor product, less than ~1% yield) suitable for X-ray analysis were obtained. For (2): analysis, calculated for [C₆₄H₆₂N₆O₁₂Zn₂]: C, 62.09; H, 5.05; N, 6.79%; found: C, 62.15; H, 5.02; N, 7.21%; IR (KBr pellet) 3026, 2884, 2821, 1637, 1609, 1508, 1388, 1224, 1036, 954, 869, 840, 752 and 664 cm⁻¹. For (3): IR (KBr pellet) 3033, 2895, 1631, 1543, 1388, 1237, 1073, 949, 830, 751, 715 and 668 cm⁻¹. (3) was produced only in very low yield, hence no analytical or IR data could be obtained for this compound.

4.4. Preparation of [Zn₂(tppcp)(bdc)₂]·1.6DMF·2.8H₂O·0.2DMSO (4)

(4) was obtained by UV irradiation of the single crystals of (1) for 48 h. Analysis, calculated for [C_61.2H₅₈N_5.6O_12.6S_0.2Zn₂]: C, 60.71; H, 4.83; N, 6.48; S, 0.53%; found: C, 60.95; H, 4.72; N, 6.19; S, 0.49%; IR (KBr pellet) 3447, 3045, 2946, 2883, 1674, 1616, 1542, 1507, 1387, 1224, 1093, 1071, 830, 751 and 669 cm⁻¹.

4.5. Preparation of [Zn₂(tppcp)(bdc)₂]·2DMA·2H₂O (5) and [Zn₂(bpeb)_0.6(bpbpvpcb)_0.4(bdc)₂]·DMA (6)

(5) and (6) were obtained by UV irradiation of the single crystals of (2) and (3) for 48 h, respectively. For (5): analysis, calculated for [C_62.8H_61.5N_5.7O_12.8Zn₂]: C, 61.24; H, 5.03; N, 6.48; found: C, 61.11; H, 4.79; N, 6.17%; IR (KBr pellet) 3447, 3044, 2943, 1618, 1501, 1388, 1224, 1071, 1016, 928, 829, 751, 706 and 669 cm⁻¹. For (6): IR (KBr pellet) 3051, 2932, 1605, 1524, 1375, 1237, 1073, 949, 830, 751, 715 and 668 cm⁻¹. (6) was produced only in very low yield, hence no analytical or IR data could be obtained for this compound.

4.6. X-ray crystallographic analysis

Crystal data for (1) were collected at 100 K and (2)-(6) were collected at 173 K on a Bruker SMART APEX II ULTRA diffractometer equipped with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) generated by a rotating anode (Table 1). The preliminary cell parameters for the compounds were obtained from a least-squares refinement (from 36 collected frames). Data collection, data reduction and absorption correction were carried out using the software package of APEX2 (Bruker, 2008). All of the calculations for the structure determination were carried out using the SHELXTL package (Bruker, 2001). Relevant crystal data collection and refinement data for the crystal structures of (1)–(6) are summarized in Table S1.

Table 1
Crystallographic data and refinement parameters of (1)-(6)

	(1) CCDC 1558995	(2) CCDC 1558996	(3) CCDC 1558997
Formula	C56H40N4O8Zn2	C56H40N4O8Zn2	C56H40N4O8Zn2
Formula weight	1027.66	1027.66	1027.66
Temperature (K)	100	173	173
Crystal system	Monoclinic	Orthorhombic	Monoclinic
Space group	P21/c	Pcca	C2/c
a (Å)	20.3028 (9)	19.490 (3)	27.5072 (12)
b (Å)	19.3686 (9)	20.220 (3)	29.3890 (14)
c (Å)	15.9389 (7)	15.854 (2)	14.9485 (7)
β (°)	103.500 (2)	90	109.537 (2)
V (Å^3)	6094.6 (5)	6247.8 (15)	11388.7 (9)
Z	4	4	8
Dcalc(g cm^−3)	1.120	1.093	1.199
μ (mm^−1)	0.835	0.815	0.894
2θmax (°)	52	52	52
Reflections collected	128744	49542	55236
Independent reflections	11944 (Rint = 0.0378)	5982 (Rint = 0.1052)	14223 (Rint = 0.0878)
Goodness-of-fit on F^2	1.176	1.083	1.094
R1, wR2 [I > 2σ(I)]	0.0719, 0.1571	0.1233, 0.3828	0.0434, 0.1265
R1, wR2 (all data)	0.0804, 0.1606	0.1673, 0.3555	0.0593, 0.1325

	(4) CCDC 1558998	(5) CCDC 1558999	(6) CCDC 1559000
Formula	C56H40N4O8Zn2	C56H40N4O8Zn2	C56H40N4O8Zn2
Formula weight	1027.66	1027.66	1027.66
Temperature (K)	173	173	173
Crystal system	Orthorhombic	Orthorhombic	Monoclinic
Space group	Pcca	Pcca	C2/c
a (Å)	20.030 (3)	20.0663 (6)	27.430 (2)
b (Å)	20.005 (3)	19.9342 (7)	29.305 (2)
c (Å)	15.145 (2)	14.8166 (5)	14.9087 (11)
β (°)	90	90	107.070 (5)
V (Å^3)	6068.8 (14)	5926.7 (3)	11456.2 (16)
Z	4	4	8
Dcalc(g (cm^−3)	1.125	1.152	1.192
μ (mm^−1-1)	0.839	0.859	0.889
2θmax (°)	52.	52.	53.
Reflections collected	46693	64566	50356
Independent reflections	5979 (Rint = 0.0739)	5651 (Rint = 0.1189)	11878 (Rint = 0.0918)
Goodness-of-fit on F^2	1.115	1.027	1.035
R1, wR2 [I > 2σ(I)]	0.0731, 0.2166	0.1094, 0.3151	0.0862, 0.2151
R1, wR2 (all data)	0.0.0993, 0.2313	0.1736, 0.3466	0.1439, 0.2377

5. Related literature

The following references are cited in the supporting information: Balamurugan et al. (2012); Elacqua et al. (2009); Spek (2015); Horner & Hünig (1982); Peedikakkal & Vittal (2008); Peedikakkal et al. (2010).

Supporting information

Computing details

Data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2014); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

(1)

Crystal data

C56H40N4O8Zn2	F(000) = 2112
Mr = 1027.66	Dx = 1.120 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.3028 (9) Å	Cell parameters from 9779 reflections
b = 19.3686 (9) Å	θ = 2.3–28.2°
c = 15.9389 (7) Å	µ = 0.84 mm^−1
β = 103.500 (2)°	T = 100 K
V = 6094.6 (5) Å^3	Block, pale_yellow
Z = 4	0.31 × 0.25 × 0.19 mm

Data collection

Bruker D8 Venture diffractometer	10294 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.038
Absorption correction: multi-scan SADABS (Sheldrick, 2011)	θmax = 26.0°, θmin = 2.1°
Tmin = 0.688, Tmax = 0.746	h = −25→25
128744 measured reflections	k = −23→23
11944 independent reflections	l = −19→19

Refinement

Refinement on F^2	56 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.072	H-atom parameters constrained
wR(F^2) = 0.161	w = 1/[σ^2(Fo^2) + (0.0319P)^2 + 24.952P] where P = (Fo^2 + 2Fc^2)/3
S = 1.18	(Δ/σ)max = 0.001
11944 reflections	Δρmax = 1.67 e Å^−3
817 parameters	Δρmin = −0.56 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Our initial attempt to refine the structure using the normal data was not satisfactory and hence the data were SQUEEZED. O4 was disordered with occupancies fixed at 0.6 and 0.4. Anisotropic thermal parameters were refined for these two O atoms without any restraints/constraints. The two bpeb ligands were disordered. Two disorder components were included and a common occupancy was refined to 0.605 (6). Anisotropic thermal parameters were refined for all the non-hydrogen atoms in the major component. Soft constraints like FLAT SAME were used for some of the phenyl and pyridyl rings. For the non-hydrogen atoms in the minor disorder, only isotropic thermal parameter could be refined after all the options tried. Again, FLAT and SAME were used to retain a reasonably ideal geometry of few phenyl and pyridyl rings. The agreement factors are much better for this data as compared to the normal data.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.83225 (2)	0.44184 (2)	0.63870 (3)	0.02214 (13)
Zn2	0.81884 (2)	0.55904 (2)	0.83594 (3)	0.02146 (12)
O1	0.82995 (17)	0.54032 (15)	0.6033 (2)	0.0381 (8)
O2	0.79866 (16)	0.59234 (18)	0.7127 (2)	0.0377 (8)
O3	0.8232 (2)	0.8448 (2)	0.3830 (4)	0.0789 (17)
O4	0.8256 (4)	0.9034 (4)	0.4865 (5)	0.0385 (17)	0.6
O4A	0.8096 (8)	0.9119 (6)	0.5190 (8)	0.049 (3)	0.4
O5	0.81994 (17)	0.46003 (15)	0.8719 (2)	0.0371 (8)
O6	0.84739 (17)	0.40779 (18)	0.7610 (2)	0.0398 (8)
O7	0.8215 (2)	0.1502 (2)	1.0832 (4)	0.0719 (15)
O8	0.8360 (3)	0.0910 (2)	0.9703 (4)	0.0917 (19)
N1	0.7208 (10)	0.4465 (9)	0.6250 (10)	0.031 (3)	0.605 (6)
C1	0.6942 (9)	0.3906 (9)	0.6755 (11)	0.043 (4)	0.605 (6)
H1	0.7247	0.3577	0.7076	0.051*	0.605 (6)
C2	0.6296 (6)	0.3873 (9)	0.6752 (9)	0.040 (3)	0.605 (6)
H2	0.6131	0.3473	0.6982	0.048*	0.605 (6)
C3	0.5839 (7)	0.4404 (8)	0.6425 (9)	0.042 (3)	0.605 (6)
C4	0.6111 (5)	0.4914 (7)	0.6018 (9)	0.044 (3)	0.605 (6)
H4	0.5836	0.5288	0.5757	0.053*	0.605 (6)
C5	0.6778 (8)	0.4888 (7)	0.5985 (10)	0.045 (3)	0.605 (6)
H5	0.6926	0.5271	0.5704	0.054*	0.605 (6)
C6	0.5142 (5)	0.4465 (8)	0.6460 (6)	0.052 (3)	0.605 (6)
H6	0.4901	0.4856	0.6187	0.062*	0.605 (6)
C7	0.4813 (5)	0.4034 (7)	0.6831 (6)	0.048 (3)	0.605 (6)
H7	0.5059	0.3647	0.7108	0.058*	0.605 (6)
C8	0.4085 (4)	0.4084 (7)	0.6869 (6)	0.049 (3)	0.605 (6)
C9	0.3825 (5)	0.3541 (7)	0.7317 (7)	0.061 (3)	0.605 (6)
H9	0.4117	0.3184	0.7592	0.073*	0.605 (6)
C10	0.3147 (5)	0.3541 (6)	0.7350 (6)	0.057 (3)	0.605 (6)
H10	0.2979	0.3179	0.7644	0.069*	0.605 (6)
C11	0.2708 (5)	0.4068 (7)	0.6952 (6)	0.053 (3)	0.605 (6)
C12	0.2969 (5)	0.4597 (7)	0.6532 (7)	0.057 (3)	0.605 (6)
H12	0.2686	0.4969	0.6281	0.069*	0.605 (6)
C13	0.3648 (5)	0.4579 (7)	0.6481 (7)	0.064 (3)	0.605 (6)
H13	0.3809	0.4929	0.6161	0.077*	0.605 (6)
C14	0.2001 (4)	0.4054 (6)	0.7003 (5)	0.053 (3)	0.605 (6)
H14	0.1868	0.3691	0.7328	0.064*	0.605 (6)
C15	0.1543 (5)	0.4486 (6)	0.6647 (6)	0.044 (2)	0.605 (6)
H15	0.1690	0.4865	0.6358	0.052*	0.605 (6)
N2	−0.0630 (11)	0.4460 (6)	0.6508 (10)	0.026 (3)	0.605 (6)
C16	−0.0175 (7)	0.3994 (7)	0.6993 (9)	0.034 (3)	0.605 (6)
H16	−0.0356	0.3652	0.7302	0.040*	0.605 (6)
C17	0.0515 (5)	0.3984 (7)	0.7067 (7)	0.038 (3)	0.605 (6)
H17	0.0786	0.3644	0.7416	0.046*	0.605 (6)
C18	0.0814 (6)	0.4466 (6)	0.6634 (6)	0.033 (2)	0.605 (6)
C19	0.0381 (5)	0.4937 (6)	0.6150 (9)	0.032 (2)	0.605 (6)
H19	0.0561	0.5283	0.5845	0.038*	0.605 (6)
C20	−0.0297 (7)	0.4927 (7)	0.6094 (10)	0.031 (3)	0.605 (6)
H20	−0.0564	0.5268	0.5742	0.037*	0.605 (6)
N3	0.7070 (5)	0.5613 (6)	0.8221 (7)	0.020 (2)	0.605 (6)
C21	0.6715 (5)	0.6141 (6)	0.7798 (7)	0.033 (2)	0.605 (6)
H21	0.6938	0.6466	0.7515	0.040*	0.605 (6)
C22	0.6057 (5)	0.6224 (7)	0.7762 (7)	0.043 (2)	0.605 (6)
H22	0.5818	0.6595	0.7438	0.051*	0.605 (6)
C23	0.5719 (4)	0.5777 (6)	0.8189 (6)	0.0323 (19)	0.605 (6)
C24	0.6102 (5)	0.5260 (7)	0.8646 (8)	0.055 (3)	0.605 (6)
H24	0.5902	0.4943	0.8967	0.066*	0.605 (6)
C25	0.6776 (7)	0.5200 (7)	0.8642 (10)	0.055 (4)	0.605 (6)
H25	0.7033	0.4838	0.8963	0.066*	0.605 (6)
C26	0.5004 (4)	0.5901 (7)	0.8174 (6)	0.044 (2)	0.605 (6)
H26	0.4808	0.6299	0.7866	0.052*	0.605 (6)
C27	0.4605 (6)	0.5537 (11)	0.8525 (9)	0.070 (5)	0.605 (6)
H27	0.4801	0.5137	0.8827	0.083*	0.605 (6)
C28	0.3903 (4)	0.5658 (5)	0.8521 (5)	0.050 (3)	0.605 (6)
C29	0.3534 (4)	0.6241 (6)	0.8174 (5)	0.057 (3)	0.605 (6)
H29	0.3759	0.6607	0.7957	0.068*	0.605 (6)
C30	0.2841 (4)	0.6300 (7)	0.8139 (6)	0.064 (4)	0.605 (6)
H30	0.2605	0.6704	0.7901	0.077*	0.605 (6)
C31	0.2501 (5)	0.5785 (6)	0.8440 (5)	0.061 (4)	0.605 (6)
C32	0.2867 (6)	0.5217 (7)	0.8810 (7)	0.064 (4)	0.605 (6)
H32	0.2645	0.4866	0.9056	0.077*	0.605 (6)
C33	0.3555 (5)	0.5146 (7)	0.8834 (7)	0.062 (3)	0.605 (6)
H33	0.3786	0.4738	0.9069	0.074*	0.605 (6)
C34	0.1771 (4)	0.5874 (6)	0.8342 (5)	0.052 (3)	0.605 (6)
H34	0.1578	0.6285	0.8063	0.062*	0.605 (6)
C35	0.1387 (5)	0.5482 (5)	0.8577 (6)	0.047 (2)	0.605 (6)
H35	0.1593	0.5068	0.8831	0.056*	0.605 (6)
N4	−0.0713 (8)	0.5562 (6)	0.8478 (8)	0.025 (3)	0.605 (6)
C36	−0.0421 (6)	0.6044 (7)	0.8070 (8)	0.029 (3)	0.605 (6)
H36	−0.0697	0.6400	0.7762	0.035*	0.605 (6)
C37	0.0250 (5)	0.6040 (6)	0.8082 (7)	0.032 (3)	0.605 (6)
H37	0.0432	0.6385	0.7777	0.038*	0.605 (6)
C38	0.0671 (6)	0.5531 (6)	0.8540 (6)	0.032 (2)	0.605 (6)
C39	0.0356 (5)	0.5040 (6)	0.8947 (8)	0.031 (3)	0.605 (6)
H39	0.0616	0.4677	0.9263	0.038*	0.605 (6)
C40	−0.0304 (7)	0.5073 (6)	0.8902 (9)	0.028 (3)	0.605 (6)
H40	−0.0498	0.4725	0.9189	0.033*	0.605 (6)
N1Z	0.7253 (14)	0.4391 (15)	0.6393 (15)	0.019 (5)*	0.395 (6)
C1Z	0.6966 (18)	0.4017 (15)	0.6636 (17)	0.040 (7)*	0.395 (6)
H1Z	0.7187	0.3592	0.6817	0.048*	0.395 (6)
C2Z	0.6218 (17)	0.4083 (13)	0.673 (2)	0.051 (8)*	0.395 (6)
H2Z	0.6026	0.3784	0.7082	0.061*	0.395 (6)
C3Z	0.5876 (14)	0.4603 (12)	0.6269 (16)	0.038 (6)*	0.395 (6)
C4Z	0.6165 (11)	0.5049 (11)	0.5782 (12)	0.038 (5)*	0.395 (6)
H4Z	0.5899	0.5389	0.5427	0.045*	0.395 (6)
C5Z	0.6854 (11)	0.4989 (10)	0.5822 (12)	0.024 (4)*	0.395 (6)
H5Z	0.7077	0.5298	0.5517	0.029*	0.395 (6)
C6Z	0.5132 (9)	0.4694 (9)	0.6208 (12)	0.047 (5)*	0.395 (6)
H6Z	0.4899	0.5022	0.5801	0.056*	0.395 (6)
C7Z	0.4783 (11)	0.4367 (10)	0.6659 (13)	0.051 (5)*	0.395 (6)
H7Z	0.5018	0.4014	0.7022	0.061*	0.395 (6)
C8Z	0.4066 (9)	0.4466 (7)	0.6689 (9)	0.042 (4)*	0.395 (6)
C9Z	0.3761 (8)	0.3960 (8)	0.7099 (9)	0.048 (4)*	0.395 (6)
H9Z	0.4025	0.3585	0.7378	0.057*	0.395 (6)
C10Z	0.3086 (7)	0.3997 (7)	0.7107 (8)	0.033 (3)*	0.395 (6)
H10Z	0.2890	0.3651	0.7395	0.040*	0.395 (6)
C11Z	0.2686 (7)	0.4543 (6)	0.6690 (8)	0.027 (3)*	0.395 (6)
C12Z	0.3010 (7)	0.5050 (8)	0.6293 (10)	0.051 (4)*	0.395 (6)
H12Z	0.2749	0.5426	0.6011	0.061*	0.395 (6)
C13Z	0.3687 (8)	0.5022 (9)	0.6299 (11)	0.058 (4)*	0.395 (6)
H13Z	0.3892	0.5379	0.6039	0.069*	0.395 (6)
C14Z	0.1979 (6)	0.4602 (6)	0.6605 (7)	0.028 (2)*	0.395 (6)
H14Z	0.1765	0.4985	0.6282	0.033*	0.395 (6)
C15Z	0.1551 (7)	0.4155 (8)	0.6945 (9)	0.035 (3)*	0.395 (6)
H15Z	0.1749	0.3769	0.7278	0.042*	0.395 (6)
N2Z	−0.0560 (16)	0.4376 (9)	0.6590 (15)	0.016 (4)*	0.395 (6)
C16Z	−0.0262 (10)	0.3854 (9)	0.7013 (12)	0.018 (4)*	0.395 (6)
H16Z	−0.0517	0.3521	0.7239	0.021*	0.395 (6)
C17Z	0.0447 (9)	0.3777 (7)	0.7139 (11)	0.022 (4)*	0.395 (6)
H17Z	0.0667	0.3392	0.7453	0.027*	0.395 (6)
C18Z	0.0821 (9)	0.4260 (7)	0.6809 (9)	0.018 (3)*	0.395 (6)
C19Z	0.0469 (10)	0.4813 (11)	0.6367 (12)	0.027 (5)*	0.395 (6)
H19Z	0.0700	0.5167	0.6139	0.033*	0.395 (6)
C20Z	−0.0242 (11)	0.4839 (11)	0.6261 (13)	0.019 (5)*	0.395 (6)
H20Z	−0.0490	0.5207	0.5941	0.022*	0.395 (6)
N3Z	0.7198 (11)	0.5526 (13)	0.8313 (16)	0.037 (6)*	0.395 (6)
C21Z	0.6682 (11)	0.5900 (10)	0.7793 (14)	0.041 (6)*	0.395 (6)
H21Z	0.6820	0.6178	0.7373	0.050*	0.395 (6)
C22Z	0.5972 (12)	0.5941 (11)	0.7775 (17)	0.060 (7)*	0.395 (6)
H22Z	0.5674	0.6250	0.7406	0.072*	0.395 (6)
C23Z	0.5750 (11)	0.5488 (9)	0.8350 (12)	0.039 (5)*	0.395 (6)
C24Z	0.6203 (9)	0.5042 (8)	0.8833 (11)	0.037 (4)*	0.395 (6)
H24Z	0.6055	0.4724	0.9204	0.044*	0.395 (6)
C25Z	0.6872 (11)	0.5046 (10)	0.8792 (13)	0.037 (5)*	0.395 (6)
H25Z	0.7152	0.4698	0.9111	0.045*	0.395 (6)
C26Z	0.4979 (12)	0.5554 (12)	0.8316 (14)	0.065 (6)*	0.395 (6)
H26Z	0.4729	0.5900	0.7955	0.079*	0.395 (6)
C27Z	0.4710 (18)	0.5226 (16)	0.868 (2)	0.095 (12)*	0.395 (6)
H27Z	0.4976	0.4889	0.9041	0.115*	0.395 (6)
C28Z	0.3938 (10)	0.5243 (8)	0.8692 (10)	0.053 (4)*	0.395 (6)
C29Z	0.3543 (10)	0.5730 (10)	0.8254 (11)	0.069 (5)*	0.395 (6)
H29Z	0.3734	0.6060	0.7939	0.082*	0.395 (6)
C30Z	0.2828 (10)	0.5772 (10)	0.8243 (12)	0.071 (5)*	0.395 (6)
H30Z	0.2548	0.6123	0.7930	0.085*	0.395 (6)
C31Z	0.2576 (9)	0.5281 (8)	0.8707 (11)	0.041 (4)*	0.395 (6)
C32Z	0.2992 (7)	0.4778 (8)	0.9142 (10)	0.046 (3)*	0.395 (6)
H32Z	0.2809	0.4429	0.9439	0.055*	0.395 (6)
C33Z	0.3701 (8)	0.4770 (9)	0.9157 (11)	0.061 (4)*	0.395 (6)
H33Z	0.3994	0.4438	0.9489	0.074*	0.395 (6)
C34Z	0.1848 (6)	0.5299 (6)	0.8738 (7)	0.027 (2)*	0.395 (6)
H34Z	0.1706	0.4953	0.9080	0.032*	0.395 (6)
C35Z	0.1333 (8)	0.5778 (8)	0.8312 (9)	0.036 (3)*	0.395 (6)
H35Z	0.1457	0.6144	0.7983	0.043*	0.395 (6)
N4Z	−0.0781 (12)	0.5644 (10)	0.8375 (12)	0.015 (4)*	0.395 (6)
C36Z	−0.0525 (10)	0.6166 (10)	0.8028 (12)	0.022 (5)*	0.395 (6)
H36Z	−0.0827	0.6519	0.7758	0.026*	0.395 (6)
C37Z	0.0172 (9)	0.6238 (8)	0.8030 (11)	0.022 (4)*	0.395 (6)
H37Z	0.0330	0.6640	0.7798	0.027*	0.395 (6)
C38Z	0.0613 (11)	0.5717 (8)	0.8371 (10)	0.019 (4)*	0.395 (6)
C39Z	0.0357 (10)	0.5189 (10)	0.8778 (13)	0.032 (5)*	0.395 (6)
H39Z	0.0647	0.4836	0.9071	0.039*	0.395 (6)
C40Z	−0.0344 (12)	0.5179 (13)	0.8756 (13)	0.026 (6)*	0.395 (6)
H40Z	−0.0509	0.4808	0.9038	0.031*	0.395 (6)
C41	0.8141 (2)	0.5920 (2)	0.6407 (3)	0.0261 (9)
C42	0.8130 (2)	0.6603 (2)	0.5955 (2)	0.0221 (8)
C43	0.8113 (2)	0.7222 (2)	0.6393 (3)	0.0300 (9)
H43	0.8088	0.7221	0.6980	0.036*
C44	0.8134 (2)	0.7845 (2)	0.5958 (3)	0.0396 (12)
H44	0.8126	0.8270	0.6252	0.048*
C45	0.8167 (2)	0.7843 (2)	0.5095 (3)	0.0372 (11)
C46	0.8177 (2)	0.7225 (2)	0.4673 (3)	0.0350 (10)
H46	0.8188	0.7225	0.4080	0.042*
C47	0.8171 (2)	0.6606 (2)	0.5098 (3)	0.0291 (9)
H47	0.8194	0.6183	0.4805	0.035*
C48	0.8202 (3)	0.8516 (3)	0.4612 (5)	0.062 (2)
C49	0.83203 (19)	0.4079 (2)	0.8321 (3)	0.0242 (8)
C50	0.82906 (19)	0.3392 (2)	0.8760 (3)	0.0214 (8)
C51	0.8212 (2)	0.3376 (2)	0.9595 (3)	0.0301 (9)
H51	0.8161	0.3795	0.9883	0.036*
C52	0.8206 (3)	0.2751 (2)	1.0013 (3)	0.0374 (11)
H52	0.8154	0.2742	1.0590	0.045*
C53	0.8278 (2)	0.2138 (2)	0.9593 (3)	0.0357 (11)
C54	0.8344 (3)	0.2155 (2)	0.8750 (3)	0.0386 (11)
H54	0.8378	0.1735	0.8455	0.046*
C55	0.8362 (2)	0.2773 (2)	0.8334 (3)	0.0318 (10)
H55	0.8421	0.2781	0.7760	0.038*
C56	0.8280 (2)	0.1454 (3)	1.0058 (5)	0.0573 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0301 (3)	0.0138 (2)	0.0250 (2)	−0.00096 (18)	0.01170 (19)	−0.00135 (18)
Zn2	0.0292 (3)	0.0148 (2)	0.0227 (2)	−0.00016 (18)	0.01069 (18)	−0.00091 (17)
O1	0.0436 (19)	0.0156 (14)	0.063 (2)	0.0039 (13)	0.0271 (17)	0.0091 (14)
O2	0.0347 (18)	0.049 (2)	0.0309 (16)	0.0044 (15)	0.0106 (14)	0.0153 (15)
O3	0.053 (3)	0.077 (3)	0.118 (4)	0.021 (2)	0.042 (3)	0.078 (3)
O4	0.044 (4)	0.018 (4)	0.052 (5)	0.001 (3)	0.009 (4)	0.008 (4)
O4A	0.094 (11)	0.012 (4)	0.042 (7)	−0.003 (5)	0.018 (6)	−0.004 (4)
O5	0.047 (2)	0.0170 (15)	0.054 (2)	0.0007 (13)	0.0253 (16)	0.0060 (14)
O6	0.045 (2)	0.046 (2)	0.0342 (17)	0.0055 (16)	0.0213 (15)	0.0188 (15)
O7	0.043 (2)	0.059 (3)	0.127 (4)	0.0237 (19)	0.047 (3)	0.067 (3)
O8	0.097 (4)	0.016 (2)	0.138 (5)	−0.004 (2)	−0.020 (3)	0.022 (2)
N1	0.044 (6)	0.026 (7)	0.020 (6)	0.000 (4)	0.002 (5)	−0.001 (5)
C1	0.038 (6)	0.053 (8)	0.036 (6)	−0.018 (5)	0.007 (4)	0.022 (5)
C2	0.021 (5)	0.054 (9)	0.046 (6)	0.001 (6)	0.009 (4)	0.000 (6)
C3	0.034 (6)	0.050 (8)	0.041 (6)	−0.010 (6)	0.009 (5)	−0.010 (6)
C4	0.023 (5)	0.046 (7)	0.061 (8)	0.007 (5)	0.002 (5)	0.011 (6)
C5	0.045 (7)	0.032 (6)	0.060 (8)	−0.009 (5)	0.016 (6)	0.010 (5)
C6	0.031 (5)	0.094 (9)	0.027 (5)	0.006 (5)	0.002 (4)	0.012 (6)
C7	0.028 (5)	0.081 (9)	0.033 (5)	−0.003 (5)	0.003 (4)	−0.015 (5)
C8	0.023 (4)	0.080 (8)	0.047 (5)	−0.013 (5)	0.016 (4)	−0.017 (5)
C9	0.025 (4)	0.107 (10)	0.055 (6)	−0.023 (5)	0.018 (4)	−0.015 (6)
C10	0.035 (5)	0.087 (8)	0.054 (6)	−0.019 (5)	0.018 (4)	−0.015 (6)
C11	0.031 (5)	0.095 (9)	0.035 (5)	−0.012 (5)	0.012 (4)	−0.018 (5)
C12	0.026 (5)	0.097 (10)	0.048 (6)	−0.007 (5)	0.005 (4)	−0.009 (6)
C13	0.021 (5)	0.104 (10)	0.069 (7)	−0.003 (5)	0.016 (5)	−0.019 (7)
C14	0.027 (5)	0.100 (8)	0.030 (4)	−0.013 (5)	0.002 (3)	−0.025 (5)
C15	0.045 (6)	0.056 (6)	0.034 (4)	−0.009 (5)	0.017 (4)	−0.019 (4)
N2	0.033 (7)	0.021 (5)	0.025 (5)	0.009 (4)	0.009 (4)	−0.001 (3)
C16	0.037 (6)	0.027 (6)	0.040 (6)	−0.003 (5)	0.016 (4)	−0.002 (5)
C17	0.026 (5)	0.039 (7)	0.049 (6)	−0.002 (5)	0.011 (4)	−0.012 (5)
C18	0.047 (6)	0.028 (5)	0.026 (5)	−0.013 (5)	0.012 (4)	−0.011 (4)
C19	0.028 (5)	0.035 (6)	0.037 (7)	−0.010 (4)	0.014 (5)	−0.006 (5)
C20	0.034 (6)	0.027 (6)	0.035 (7)	−0.006 (4)	0.014 (5)	0.008 (5)
N3	0.007 (4)	0.032 (5)	0.020 (4)	0.004 (4)	0.002 (3)	−0.009 (3)
C21	0.027 (5)	0.024 (5)	0.047 (6)	0.003 (4)	0.004 (3)	0.003 (4)
C22	0.031 (5)	0.050 (7)	0.049 (6)	0.004 (5)	0.012 (4)	0.003 (5)
C23	0.026 (4)	0.047 (6)	0.023 (4)	−0.001 (4)	0.004 (3)	−0.002 (4)
C24	0.031 (6)	0.060 (7)	0.077 (8)	0.014 (5)	0.018 (5)	0.034 (6)
C25	0.036 (6)	0.053 (7)	0.076 (9)	0.014 (5)	0.013 (5)	0.036 (6)
C26	0.011 (4)	0.074 (8)	0.046 (5)	0.005 (4)	0.008 (3)	−0.001 (5)
C27	0.029 (5)	0.136 (16)	0.049 (6)	−0.018 (8)	0.020 (5)	−0.047 (9)
C28	0.014 (4)	0.092 (9)	0.039 (5)	0.006 (5)	−0.003 (3)	−0.019 (5)
C29	0.025 (4)	0.102 (9)	0.045 (5)	0.000 (5)	0.011 (4)	−0.018 (5)
C30	0.016 (4)	0.122 (11)	0.052 (6)	0.011 (5)	0.001 (4)	−0.033 (6)
C31	0.024 (5)	0.130 (12)	0.030 (4)	0.006 (6)	0.008 (4)	−0.028 (6)
C32	0.040 (7)	0.118 (12)	0.036 (5)	−0.022 (7)	0.011 (5)	−0.012 (6)
C33	0.026 (5)	0.095 (9)	0.066 (7)	0.000 (5)	0.012 (5)	−0.003 (6)
C34	0.030 (5)	0.101 (8)	0.025 (4)	−0.030 (5)	0.006 (3)	−0.023 (5)
C35	0.067 (7)	0.033 (5)	0.035 (5)	0.004 (5)	0.000 (4)	−0.019 (4)
N4	0.029 (6)	0.017 (5)	0.024 (5)	0.009 (4)	−0.003 (4)	0.005 (3)
C36	0.022 (5)	0.029 (6)	0.035 (5)	0.008 (4)	0.005 (4)	0.005 (4)
C37	0.035 (6)	0.022 (5)	0.041 (5)	−0.006 (5)	0.014 (4)	−0.003 (5)
C38	0.032 (5)	0.038 (6)	0.023 (5)	0.008 (5)	−0.001 (4)	−0.009 (4)
C39	0.042 (6)	0.018 (5)	0.028 (5)	0.007 (4)	−0.004 (4)	0.003 (4)
C40	0.037 (6)	0.016 (5)	0.023 (5)	0.007 (4)	−0.009 (4)	0.010 (4)
C41	0.020 (2)	0.024 (2)	0.037 (2)	0.0031 (16)	0.0115 (17)	0.0104 (18)
C42	0.024 (2)	0.0184 (19)	0.0236 (19)	−0.0025 (15)	0.0043 (16)	0.0017 (15)
C43	0.038 (2)	0.025 (2)	0.024 (2)	0.0067 (18)	0.0012 (18)	−0.0030 (17)
C44	0.042 (3)	0.017 (2)	0.050 (3)	0.0041 (19)	−0.008 (2)	−0.003 (2)
C45	0.028 (2)	0.023 (2)	0.055 (3)	−0.0044 (18)	−0.003 (2)	0.017 (2)
C46	0.038 (3)	0.037 (3)	0.032 (2)	0.001 (2)	0.013 (2)	0.012 (2)
C47	0.038 (2)	0.023 (2)	0.028 (2)	−0.0003 (18)	0.0109 (18)	−0.0012 (17)
C48	0.022 (3)	0.036 (3)	0.114 (6)	−0.007 (2)	−0.010 (3)	0.042 (4)
C49	0.0160 (19)	0.024 (2)	0.034 (2)	0.0000 (15)	0.0077 (16)	0.0048 (17)
C50	0.0187 (19)	0.0191 (19)	0.026 (2)	−0.0036 (15)	0.0052 (15)	0.0009 (15)
C51	0.043 (3)	0.018 (2)	0.031 (2)	0.0009 (18)	0.0110 (19)	0.0032 (17)
C52	0.047 (3)	0.038 (3)	0.029 (2)	0.003 (2)	0.011 (2)	0.015 (2)
C53	0.027 (2)	0.021 (2)	0.057 (3)	−0.0034 (17)	0.004 (2)	0.014 (2)
C54	0.046 (3)	0.017 (2)	0.050 (3)	−0.0019 (19)	0.005 (2)	−0.0030 (19)
C55	0.034 (2)	0.029 (2)	0.033 (2)	0.0071 (19)	0.0088 (19)	−0.0034 (18)
C56	0.023 (3)	0.042 (3)	0.102 (5)	−0.003 (2)	0.005 (3)	0.044 (3)

Geometric parameters (Å, º)

Zn1—O7^i	1.980 (4)	N4—C36	1.351 (15)
Zn1—O1	1.986 (3)	N4—Zn2^vi	2.195 (16)
Zn1—O6	2.013 (3)	C36—C37	1.358 (15)
Zn1—N2^ii	2.09 (2)	C37—C38	1.395 (13)
Zn1—N1Z	2.17 (3)	C38—C39	1.388 (14)
Zn1—N2Z^ii	2.22 (3)	C39—C40	1.326 (15)
Zn1—N1	2.223 (19)	N1Z—C1Z	1.06 (3)
Zn2—N3Z	2.00 (2)	N1Z—C5Z	1.58 (3)
Zn2—O5	2.000 (3)	C1Z—C2Z	1.57 (5)
Zn2—O3^iii	2.001 (4)	C2Z—C3Z	1.34 (3)
Zn2—O2	2.017 (3)	C3Z—C4Z	1.38 (3)
Zn2—N4Z^ii	2.09 (2)	C3Z—C6Z	1.50 (3)
Zn2—N4^ii	2.195 (16)	C4Z—C5Z	1.39 (3)
Zn2—N3	2.230 (10)	C6Z—C7Z	1.29 (3)
Zn2—O4^iii	2.481 (8)	C7Z—C8Z	1.48 (3)
O1—C41	1.244 (5)	C8Z—C13Z	1.384 (18)
O2—C41	1.258 (5)	C8Z—C9Z	1.400 (17)
O3—C48	1.269 (9)	C9Z—C10Z	1.376 (19)
O3—Zn2^iv	2.001 (4)	C10Z—C11Z	1.403 (15)
O4—O4A	0.693 (10)	C11Z—C12Z	1.411 (16)
O4—C48	1.078 (10)	C11Z—C14Z	1.414 (19)
O4—Zn2^iv	2.481 (8)	C12Z—C13Z	1.373 (19)
O4A—C48	1.534 (13)	C14Z—C15Z	1.420 (18)
O5—C49	1.246 (5)	C15Z—C18Z	1.46 (2)
O6—C49	1.242 (5)	N2Z—C20Z	1.29 (3)
O7—C56	1.273 (8)	N2Z—C16Z	1.29 (2)
O7—Zn1^v	1.980 (4)	N2Z—Zn1^vi	2.22 (3)
O8—C56	1.226 (8)	C16Z—C17Z	1.41 (2)
N1—C5	1.20 (2)	C17Z—C18Z	1.386 (15)
N1—C1	1.52 (2)	C18Z—C19Z	1.385 (16)
C1—C2	1.31 (2)	C19Z—C20Z	1.41 (3)
C2—C3	1.40 (2)	N3Z—C21Z	1.38 (3)
C3—C4	1.366 (19)	N3Z—C25Z	1.46 (3)
C3—C6	1.434 (16)	C21Z—C22Z	1.44 (3)
C4—C5	1.368 (19)	C22Z—C23Z	1.42 (3)
C6—C7	1.296 (17)	C23Z—C24Z	1.36 (2)
C7—C8	1.497 (13)	C23Z—C26Z	1.56 (3)
C8—C13	1.354 (17)	C24Z—C25Z	1.37 (3)
C8—C9	1.438 (16)	C26Z—C27Z	1.09 (4)
C9—C10	1.388 (12)	C27Z—C28Z	1.57 (4)
C10—C11	1.407 (16)	C28Z—C29Z	1.325 (19)
C11—C12	1.393 (16)	C28Z—C33Z	1.337 (19)
C11—C14	1.456 (13)	C29Z—C30Z	1.45 (2)
C12—C13	1.402 (14)	C30Z—C31Z	1.376 (19)
C14—C15	1.281 (15)	C31Z—C32Z	1.367 (17)
C15—C18	1.475 (14)	C31Z—C34Z	1.49 (2)
N2—C20	1.385 (18)	C32Z—C33Z	1.433 (19)
N2—C16	1.391 (19)	C34Z—C35Z	1.443 (18)
N2—Zn1^vi	2.09 (2)	C35Z—C38Z	1.49 (3)
C16—C17	1.379 (16)	N4Z—C40Z	1.31 (2)
C17—C18	1.384 (13)	N4Z—C36Z	1.32 (2)
C18—C19	1.373 (14)	N4Z—Zn2^vi	2.09 (2)
C19—C20	1.358 (16)	C36Z—C37Z	1.42 (2)
N3—C25	1.277 (18)	C37Z—C38Z	1.375 (16)
N3—C21	1.339 (16)	C38Z—C39Z	1.376 (18)
C21—C22	1.334 (14)	C39Z—C40Z	1.42 (3)
C22—C23	1.379 (16)	C41—C42	1.506 (5)
C23—C24	1.368 (15)	C42—C47	1.388 (6)
C23—C26	1.466 (11)	C42—C43	1.391 (6)
C24—C25	1.376 (17)	C43—C44	1.396 (6)
C26—C27	1.30 (2)	C44—C45	1.393 (7)
C27—C28	1.441 (14)	C45—C46	1.375 (7)
C28—C33	1.377 (13)	C45—C48	1.524 (6)
C28—C29	1.396 (12)	C46—C47	1.378 (6)
C29—C30	1.399 (10)	C49—C50	1.512 (5)
C30—C31	1.362 (14)	C50—C51	1.377 (6)
C31—C32	1.381 (13)	C50—C55	1.402 (6)
C31—C34	1.463 (12)	C51—C52	1.384 (6)
C32—C33	1.395 (13)	C52—C53	1.387 (7)
C34—C35	1.209 (14)	C53—C54	1.382 (7)
C35—C38	1.445 (16)	C53—C56	1.518 (6)
N4—C40	1.334 (14)	C54—C55	1.374 (6)
O7^i—Zn1—O1	138.2 (2)	C36—N4—Zn2^vi	119.5 (9)
O7^i—Zn1—O6	96.6 (2)	N4—C36—C37	122.7 (12)
O1—Zn1—O6	125.28 (15)	C36—C37—C38	120.1 (10)
O7^i—Zn1—N2^ii	94.6 (4)	C39—C38—C37	115.8 (10)
O1—Zn1—N2^ii	86.8 (3)	C39—C38—C35	120.3 (9)
O6—Zn1—N2^ii	90.1 (4)	C37—C38—C35	123.8 (11)
O7^i—Zn1—N1Z	88.5 (8)	C40—C39—C38	120.8 (10)
O1—Zn1—N1Z	93.9 (8)	C39—C40—N4	124.2 (13)
O6—Zn1—N1Z	85.1 (6)	C1Z—N1Z—C5Z	117 (3)
O7^i—Zn1—N2Z^ii	92.0 (6)	C1Z—N1Z—Zn1	131 (3)
O1—Zn1—N2Z^ii	91.8 (4)	C5Z—N1Z—Zn1	111.0 (16)
O6—Zn1—N2Z^ii	85.8 (5)	N1Z—C1Z—C2Z	128 (3)
N1Z—Zn1—N2Z^ii	170.9 (8)	C3Z—C2Z—C1Z	113 (3)
O7^i—Zn1—N1	89.4 (5)	C2Z—C3Z—C4Z	123 (3)
O1—Zn1—N1	88.7 (5)	C2Z—C3Z—C6Z	121 (3)
O6—Zn1—N1	91.7 (4)	C4Z—C3Z—C6Z	116 (2)
N2^ii—Zn1—N1	175.4 (6)	C3Z—C4Z—C5Z	118 (2)
N3Z—Zn2—O5	83.9 (7)	C4Z—C5Z—N1Z	117.7 (17)
N3Z—Zn2—O3^iii	91.6 (7)	C7Z—C6Z—C3Z	125.6 (19)
O5—Zn2—O3^iii	142.0 (2)	C6Z—C7Z—C8Z	128.9 (17)
N3Z—Zn2—O2	90.6 (7)	C13Z—C8Z—C9Z	119.7 (17)
O5—Zn2—O2	124.86 (14)	C13Z—C8Z—C7Z	122.3 (14)
O3^iii—Zn2—O2	92.8 (2)	C9Z—C8Z—C7Z	118.0 (14)
N3Z—Zn2—N4Z^ii	178.4 (9)	C10Z—C9Z—C8Z	121.2 (14)
O5—Zn2—N4Z^ii	95.7 (5)	C9Z—C10Z—C11Z	120.2 (13)
O3^iii—Zn2—N4Z^ii	89.6 (6)	C10Z—C11Z—C12Z	117.2 (14)
O2—Zn2—N4Z^ii	88.4 (5)	C10Z—C11Z—C14Z	124.6 (13)
O5—Zn2—N4^ii	90.5 (3)	C12Z—C11Z—C14Z	118.1 (10)
O3^iii—Zn2—N4^ii	92.0 (4)	C13Z—C12Z—C11Z	122.8 (14)
O2—Zn2—N4^ii	93.6 (3)	C12Z—C13Z—C8Z	118.9 (15)
O5—Zn2—N3	89.4 (3)	C11Z—C14Z—C15Z	127.8 (12)
O3^iii—Zn2—N3	88.5 (3)	C14Z—C15Z—C18Z	123.2 (13)
O2—Zn2—N3	85.8 (3)	C20Z—N2Z—C16Z	123 (3)
N4^ii—Zn2—N3	179.2 (5)	C20Z—N2Z—Zn1^vi	120.6 (17)
N3Z—Zn2—O4^iii	83.2 (7)	C16Z—N2Z—Zn1^vi	116.4 (16)
O5—Zn2—O4^iii	90.6 (2)	N2Z—C16Z—C17Z	119.7 (19)
O3^iii—Zn2—O4^iii	51.5 (2)	C18Z—C17Z—C16Z	120.4 (14)
O2—Zn2—O4^iii	143.3 (2)	C19Z—C18Z—C17Z	116.8 (16)
N4Z^ii—Zn2—O4^iii	98.3 (6)	C19Z—C18Z—C15Z	124.7 (15)
N4^ii—Zn2—O4^iii	95.6 (4)	C17Z—C18Z—C15Z	118.5 (13)
N3—Zn2—O4^iii	85.1 (3)	C18Z—C19Z—C20Z	118.7 (16)
C41—O1—Zn1	128.9 (3)	N2Z—C20Z—C19Z	121.5 (19)
C41—O2—Zn2	148.1 (3)	C21Z—N3Z—C25Z	106.0 (19)
C48—O3—Zn2^iv	105.3 (4)	C21Z—N3Z—Zn2	127.2 (18)
O4A—O4—C48	118.5 (18)	C25Z—N3Z—Zn2	126.7 (16)
O4A—O4—Zn2^iv	136.4 (17)	N3Z—C21Z—C22Z	131 (2)
C48—O4—Zn2^iv	86.1 (6)	C23Z—C22Z—C21Z	115 (2)
O4—O4A—C48	38.2 (12)	C24Z—C23Z—C22Z	118.9 (18)
C49—O5—Zn2	128.4 (3)	C24Z—C23Z—C26Z	127.7 (17)
C49—O6—Zn1	150.2 (3)	C22Z—C23Z—C26Z	113 (2)
C56—O7—Zn1^v	110.0 (4)	C23Z—C24Z—C25Z	120.9 (17)
C5—N1—C1	110.7 (16)	C24Z—C25Z—N3Z	127.1 (18)
C5—N1—Zn1	134.6 (13)	C27Z—C26Z—C23Z	124 (3)
C1—N1—Zn1	113.5 (11)	C26Z—C27Z—C28Z	128 (3)
C2—C1—N1	120.7 (16)	C29Z—C28Z—C33Z	122 (2)
C1—C2—C3	122.7 (15)	C29Z—C28Z—C27Z	119.4 (19)
C4—C3—C2	113.6 (11)	C33Z—C28Z—C27Z	118.7 (17)
C4—C3—C6	118.1 (14)	C28Z—C29Z—C30Z	121.8 (18)
C2—C3—C6	128.3 (14)	C31Z—C30Z—C29Z	116.9 (16)
C3—C4—C5	120.4 (12)	C32Z—C31Z—C30Z	120.0 (18)
N1—C5—C4	131.0 (14)	C32Z—C31Z—C34Z	120.1 (12)
C7—C6—C3	125.7 (13)	C30Z—C31Z—C34Z	119.9 (15)
C6—C7—C8	126.6 (12)	C31Z—C32Z—C33Z	121.1 (15)
C13—C8—C9	117.9 (10)	C28Z—C33Z—C32Z	118.2 (16)
C13—C8—C7	125.1 (11)	C35Z—C34Z—C31Z	128.0 (12)
C9—C8—C7	117.0 (11)	C34Z—C35Z—C38Z	122.2 (14)
C10—C9—C8	120.1 (12)	C40Z—N4Z—C36Z	116 (2)
C9—C10—C11	120.8 (11)	C40Z—N4Z—Zn2^vi	122.7 (15)
C12—C11—C10	118.6 (10)	C36Z—N4Z—Zn2^vi	121.7 (15)
C12—C11—C14	122.0 (12)	N4Z—C36Z—C37Z	124.4 (17)
C10—C11—C14	119.4 (10)	C38Z—C37Z—C36Z	119.1 (16)
C11—C12—C13	120.0 (12)	C37Z—C38Z—C39Z	116.6 (18)
C8—C13—C12	122.6 (12)	C37Z—C38Z—C35Z	118.3 (14)
C15—C14—C11	125.9 (11)	C39Z—C38Z—C35Z	124.9 (16)
C14—C15—C18	127.7 (11)	C38Z—C39Z—C40Z	119.1 (16)
C20—N2—C16	110.7 (16)	N4Z—C40Z—C39Z	124.9 (19)
C20—N2—Zn1^vi	125.5 (11)	O1—C41—O2	126.1 (4)
C16—N2—Zn1^vi	123.7 (10)	O1—C41—C42	117.0 (4)
C17—C16—N2	126.0 (12)	O2—C41—C42	116.9 (4)
C16—C17—C18	120.2 (11)	C47—C42—C43	120.3 (4)
C19—C18—C17	115.5 (10)	C47—C42—C41	118.5 (4)
C19—C18—C15	120.0 (9)	C43—C42—C41	121.1 (4)
C17—C18—C15	124.4 (11)	C42—C43—C44	119.2 (4)
C20—C19—C18	122.3 (11)	C45—C44—C43	120.1 (4)
C19—C20—N2	125.3 (14)	C46—C45—C44	119.7 (4)
C25—N3—C21	118.7 (11)	C46—C45—C48	119.3 (5)
C25—N3—Zn2	121.6 (10)	C44—C45—C48	121.0 (5)
C21—N3—Zn2	118.8 (8)	C45—C46—C47	120.9 (4)
C22—C21—N3	122.0 (11)	C46—C47—C42	119.7 (4)
C21—C22—C23	120.8 (10)	O4—C48—O3	116.1 (7)
C24—C23—C22	115.8 (9)	O4—C48—C45	128.3 (8)
C24—C23—C26	124.5 (11)	O3—C48—C45	115.3 (6)
C22—C23—C26	119.6 (10)	O4—C48—O4A	23.4 (7)
C23—C24—C25	120.1 (10)	O3—C48—O4A	135.6 (6)
N3—C25—C24	122.4 (12)	C45—C48—O4A	108.6 (7)
C27—C26—C23	128.4 (13)	O6—C49—O5	125.9 (4)
C26—C27—C28	128.8 (17)	O6—C49—C50	117.7 (4)
C33—C28—C29	116.9 (9)	O5—C49—C50	116.3 (4)
C33—C28—C27	118.2 (12)	C51—C50—C55	119.8 (4)
C29—C28—C27	124.8 (12)	C51—C50—C49	119.5 (4)
C28—C29—C30	121.6 (10)	C55—C50—C49	120.6 (4)
C31—C30—C29	120.9 (11)	C50—C51—C52	120.1 (4)
C30—C31—C32	117.8 (10)	C51—C52—C53	120.2 (4)
C30—C31—C34	117.4 (9)	C54—C53—C52	119.6 (4)
C32—C31—C34	124.7 (10)	C54—C53—C56	120.4 (5)
C31—C32—C33	121.7 (11)	C52—C53—C56	120.0 (5)
C28—C33—C32	121.0 (10)	C55—C54—C53	120.6 (4)
C35—C34—C31	127.1 (12)	C54—C55—C50	119.6 (4)
C34—C35—C38	131.4 (12)	O8—C56—O7	124.4 (5)
C40—N4—C36	116.3 (15)	O8—C56—C53	120.7 (6)
C40—N4—Zn2^vi	124.1 (10)	O7—C56—C53	114.8 (6)

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x+1, y, z; (iii) x, −y+3/2, z+1/2; (iv) x, −y+3/2, z−1/2; (v) x, −y+1/2, z+1/2; (vi) x−1, y, z.

 

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Crystal data

C56H40N4O8Zn2	Dx = 1.093 Mg m^−3
Mr = 1027.66	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pcca	Cell parameters from 7985 reflections
a = 19.490 (3) Å	θ = 2.3–21.6°
b = 20.220 (3) Å	µ = 0.82 mm^−1
c = 15.854 (2) Å	T = 173 K
V = 6247.8 (15) Å^3	Plate, yellow
Z = 4	0.20 × 0.15 × 0.08 mm
F(000) = 2112

Data collection

Bruker APEX-II CCD diffractometer	3603 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.105
Absorption correction: multi-scan SADABS (Sheldrick, 2010)	θmax = 26.0°, θmin = 1.9°
Tmin = 0.861, Tmax = 0.931	h = −23→21
49542 measured reflections	k = −24→12
5982 independent reflections	l = −16→19

Refinement

Refinement on F^2	68 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.123	H-atom parameters constrained
wR(F^2) = 0.383	w = 1/[σ^2(Fo^2) + (0.1884P)^2 + 22.1646P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
5982 reflections	Δρmax = 1.45 e Å^−3
246 parameters	Δρmin = −1.02 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. It was not possible to locate the solvents in the lattice and the agreement factors were still unreasonably high (R1 = 0.2065) we have Squeezed the data.The bpeb ligand was disordered. Only the disorder component in the middle of the ligand (C8 to C15) was resolved. Two models were included and refined. Hard constraints were used to hold the geometry close to ideal. Only common isotropic thermal parameters were refined for each group of disorder. A common occupancy factor of the two disorder components were refined to 0.611 (17). From this data only the connectivity could be confirmed beyond any doubt and the bond distances and angles should be treated with caution.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.43808 (5)	0.32954 (5)	0.35173 (5)	0.0496 (4)
O1	0.5342 (3)	0.3326 (3)	0.3893 (5)	0.0791 (19)
O2	0.5880 (4)	0.3246 (4)	0.2725 (4)	0.088 (2)
O3	0.8426 (5)	0.3252 (4)	0.6037 (8)	0.122 (4)
O4	0.8996 (5)	0.3278 (4)	0.4963 (8)	0.119 (4)
N1	0.4428 (3)	0.2256 (3)	0.3529 (4)	0.070 (2)
C1	0.3984 (4)	0.1898 (4)	0.3017 (5)	0.110 (4)
H1	0.3656	0.2123	0.2678	0.133*
C2	0.4018 (6)	0.1212 (4)	0.3001 (6)	0.124 (5)
H2	0.3715	0.0967	0.2651	0.148*
C3	0.4498 (6)	0.0883 (3)	0.3496 (7)	0.165 (9)
C4	0.4942 (5)	0.1241 (4)	0.4008 (7)	0.142 (6)
H4	0.5270	0.1016	0.4347	0.170*
C5	0.4908 (4)	0.1927 (4)	0.4024 (5)	0.100 (4)
H5	0.5211	0.2171	0.4374	0.120*
C6	0.4614 (14)	0.0140 (8)	0.3592 (15)	0.203 (10)*
H6	0.5011	0.0025	0.3907	0.244*
C7	0.4308 (10)	−0.0299 (9)	0.3351 (16)	0.223 (12)*
H7	0.3895	−0.0187	0.3067	0.268*
C8	0.4451 (8)	−0.1031 (4)	0.3408 (12)	0.115 (4)*	0.611 (18)
C9	0.3951 (7)	−0.1453 (5)	0.3089 (12)	0.115 (4)*	0.611 (18)
H9	0.3549	−0.1276	0.2835	0.138*	0.611 (18)
C10	0.4038 (8)	−0.2134 (5)	0.3142 (12)	0.115 (4)*	0.611 (18)
H10	0.3696	−0.2422	0.2924	0.138*	0.611 (18)
C11	0.4626 (8)	−0.2393 (4)	0.3513 (12)	0.115 (4)*	0.611 (18)
C12	0.5126 (7)	−0.1972 (6)	0.3831 (11)	0.115 (4)*	0.611 (18)
H12	0.5527	−0.2149	0.4085	0.138*	0.611 (18)
C13	0.5038 (7)	−0.1291 (5)	0.3779 (12)	0.115 (4)*	0.611 (18)
H13	0.5380	−0.1002	0.3997	0.138*	0.611 (18)
C14	0.4706 (11)	−0.3129 (8)	0.3584 (14)	0.115 (4)*	0.611 (18)
H14	0.5098	−0.3287	0.3876	0.138*	0.611 (18)
C15	0.4342 (8)	−0.3513 (7)	0.3321 (10)	0.115 (4)*	0.611 (18)
H15	0.3962	−0.3323	0.3033	0.138*	0.611 (18)
C8A	0.4192 (12)	−0.1047 (5)	0.3290 (19)	0.120 (6)*	0.389 (18)
C9A	0.3621 (11)	−0.1316 (6)	0.2891 (18)	0.120 (6)*	0.389 (18)
H9A	0.3276	−0.1033	0.2668	0.144*	0.389 (18)
C10A	0.3555 (11)	−0.1998 (7)	0.2817 (17)	0.120 (6)*	0.389 (18)
H10A	0.3165	−0.2181	0.2545	0.144*	0.389 (18)
C11A	0.4060 (12)	−0.2411 (5)	0.3143 (19)	0.120 (6)*	0.389 (18)
C12A	0.4630 (12)	−0.2143 (7)	0.3542 (19)	0.120 (6)*	0.389 (18)
H12A	0.4975	−0.2425	0.3764	0.144*	0.389 (18)
C13A	0.4696 (11)	−0.1461 (7)	0.3615 (19)	0.120 (6)*	0.389 (18)
H13A	0.5087	−0.1277	0.3888	0.144*	0.389 (18)
C14A	0.3972 (15)	−0.3155 (9)	0.307 (2)	0.120 (6)*	0.389 (18)
H14A	0.3573	−0.3319	0.2800	0.144*	0.389 (18)
C15A	0.4342 (8)	−0.3513 (7)	0.3321 (10)	0.120 (6)*	0.389 (18)
H15A	0.4738	−0.3325	0.3574	0.144*	0.389 (18)
N2	0.4338 (4)	−0.5692 (4)	0.3437 (4)	0.065 (2)
C16	0.3808 (5)	−0.5309 (5)	0.2928 (5)	0.072 (3)
H16	0.3462	−0.5543	0.2629	0.087*
C17	0.3822 (6)	−0.4649 (5)	0.2895 (6)	0.076 (3)
H17	0.3481	−0.4430	0.2571	0.091*
C18	0.4322 (6)	−0.4253 (5)	0.3322 (6)	0.082 (3)
C19	0.4831 (6)	−0.4584 (5)	0.3794 (6)	0.079 (3)
H19	0.5173	−0.4324	0.4063	0.094*
C20	0.4862 (5)	−0.5244 (5)	0.3887 (6)	0.071 (3)
H20	0.5208	−0.5435	0.4231	0.086*
C21	0.5877 (5)	0.3271 (4)	0.3480 (5)	0.0508 (19)
C22	0.6548 (4)	0.3250 (3)	0.3920 (4)	0.0398 (16)
C23	0.7173 (5)	0.3269 (5)	0.3496 (6)	0.064 (2)
H23	0.7174	0.3284	0.2897	0.077*
C24	0.7785 (5)	0.3266 (4)	0.3919 (7)	0.071 (3)
H24	0.8205	0.3278	0.3617	0.085*
C25	0.7783 (5)	0.3245 (4)	0.4782 (7)	0.065 (3)
C26	0.7186 (6)	0.3239 (4)	0.5216 (6)	0.073 (3)
H26	0.7192	0.3229	0.5815	0.088*
C27	0.6576 (5)	0.3248 (4)	0.4796 (5)	0.056 (2)
H27	0.6160	0.3253	0.5109	0.067*
C28	0.8434 (7)	0.3261 (5)	0.5294 (13)	0.104 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0365 (6)	0.0764 (7)	0.0360 (6)	0.0008 (4)	0.0013 (4)	−0.0022 (4)
O1	0.040 (4)	0.106 (5)	0.092 (5)	0.012 (3)	−0.009 (4)	−0.003 (4)
O2	0.099 (6)	0.118 (6)	0.047 (4)	−0.004 (4)	−0.027 (4)	0.013 (3)
O3	0.109 (8)	0.088 (6)	0.168 (10)	0.011 (4)	−0.106 (8)	−0.005 (6)
O4	0.059 (6)	0.098 (6)	0.199 (11)	−0.006 (4)	−0.044 (6)	0.023 (6)
N1	0.056 (5)	0.094 (6)	0.059 (5)	0.007 (4)	0.004 (4)	−0.003 (4)
C1	0.154 (14)	0.093 (9)	0.085 (9)	−0.029 (8)	−0.008 (9)	−0.016 (6)
C2	0.158 (15)	0.103 (11)	0.111 (11)	−0.019 (9)	0.004 (10)	−0.033 (8)
C3	0.24 (2)	0.076 (10)	0.18 (2)	0.007 (12)	0.087 (16)	−0.003 (11)
C4	0.173 (17)	0.090 (10)	0.163 (16)	−0.001 (10)	−0.045 (13)	0.004 (9)
C5	0.098 (10)	0.088 (8)	0.113 (10)	−0.002 (7)	−0.003 (8)	0.009 (7)
N2	0.073 (6)	0.084 (5)	0.038 (4)	0.003 (4)	0.019 (4)	0.000 (3)
C16	0.090 (8)	0.081 (7)	0.045 (5)	0.007 (5)	0.019 (5)	−0.010 (4)
C17	0.102 (9)	0.067 (6)	0.058 (6)	0.009 (5)	0.004 (6)	−0.002 (4)
C18	0.104 (9)	0.090 (7)	0.051 (6)	0.011 (7)	0.025 (6)	0.002 (5)
C19	0.098 (9)	0.078 (7)	0.060 (6)	0.001 (6)	0.028 (6)	0.000 (5)
C20	0.074 (7)	0.082 (7)	0.058 (5)	0.010 (5)	0.014 (5)	−0.011 (5)
C21	0.047 (5)	0.054 (5)	0.051 (5)	−0.004 (4)	−0.010 (4)	0.002 (4)
C22	0.043 (4)	0.043 (4)	0.033 (4)	−0.004 (3)	0.000 (3)	0.003 (3)
C23	0.038 (5)	0.100 (7)	0.055 (5)	−0.006 (4)	0.006 (4)	0.004 (4)
C24	0.046 (5)	0.073 (6)	0.094 (8)	0.003 (4)	0.005 (5)	0.016 (5)
C25	0.048 (6)	0.056 (5)	0.092 (8)	0.003 (4)	−0.024 (5)	0.006 (4)
C26	0.082 (7)	0.093 (7)	0.045 (5)	−0.003 (6)	−0.027 (5)	−0.007 (4)
C27	0.045 (5)	0.067 (5)	0.055 (5)	−0.002 (4)	0.002 (4)	−0.004 (4)
C28	0.058 (8)	0.061 (6)	0.194 (15)	−0.011 (5)	−0.083 (10)	0.018 (8)

Geometric parameters (Å, º)

Zn1—O1	1.966 (6)	C12—C13	1.3900
Zn1—O3^i	1.992 (8)	C14—C15	1.132 (19)
Zn1—O2^ii	2.036 (6)	C15—C18	1.497 (15)
Zn1—N2^iii	2.053 (8)	C8A—C9A	1.3900
Zn1—N1	2.104 (5)	C8A—C13A	1.3900
O1—C21	1.237 (11)	C9A—C10A	1.3900
O2—C21	1.198 (10)	C10A—C11A	1.3900
O2—Zn1^ii	2.036 (6)	C11A—C12A	1.3900
O3—C28	1.18 (2)	C11A—C14A	1.517 (17)
O3—Zn1^iv	1.992 (8)	C12A—C13A	1.3900
O4—C28	1.215 (19)	C14A—C15A	1.10 (2)
N1—C1	1.3900	C15A—C18	1.497 (15)
N1—C5	1.3900	N2—C16	1.523 (10)
C1—C2	1.3900	N2—C20	1.540 (10)
C2—C3	1.3900	N2—Zn1^v	2.053 (8)
C3—C4	1.3900	C16—C17	1.336 (12)
C3—C6	1.527 (17)	C17—C18	1.432 (14)
C4—C5	1.3900	C18—C19	1.411 (14)
C6—C7	1.14 (2)	C19—C20	1.344 (13)
C7—C8	1.509 (16)	C21—C22	1.482 (11)
C7—C8A	1.533 (16)	C22—C27	1.389 (11)
C8—C9	1.3900	C22—C23	1.392 (11)
C8—C13	1.3900	C23—C24	1.368 (13)
C9—C10	1.3900	C24—C25	1.369 (15)
C10—C11	1.3900	C25—C26	1.352 (14)
C11—C12	1.3900	C25—C28	1.506 (13)
C11—C14	1.499 (16)	C26—C27	1.363 (13)
O1—Zn1—O3^i	141.6 (5)	C9A—C8A—C7	122.2 (7)
O1—Zn1—O2^ii	122.1 (3)	C13A—C8A—C7	117.8 (7)
O3^i—Zn1—O2^ii	96.2 (5)	C8A—C9A—C10A	120.0
O1—Zn1—N2^iii	91.5 (3)	C11A—C10A—C9A	120.0
O3^i—Zn1—N2^iii	91.6 (3)	C12A—C11A—C10A	120.0
O2^ii—Zn1—N2^iii	88.8 (3)	C12A—C11A—C14A	120.7 (8)
O1—Zn1—N1	89.3 (3)	C10A—C11A—C14A	119.3 (7)
O3^i—Zn1—N1	89.7 (3)	C13A—C12A—C11A	120.0
O2^ii—Zn1—N1	88.3 (3)	C12A—C13A—C8A	120.0
N2^iii—Zn1—N1	177.0 (2)	C15A—C14A—C11A	123.7 (18)
C21—O1—Zn1	129.8 (7)	C14A—C15A—C18	130.2 (17)
C21—O2—Zn1^ii	164.4 (8)	C16—N2—C20	113.4 (7)
C28—O3—Zn1^iv	110.0 (11)	C16—N2—Zn1^v	124.6 (6)
C1—N1—C5	120.0	C20—N2—Zn1^v	122.1 (6)
C1—N1—Zn1	119.2 (4)	C17—C16—N2	120.9 (9)
C5—N1—Zn1	120.8 (4)	C16—C17—C18	123.7 (10)
C2—C1—N1	120.0	C19—C18—C17	117.7 (10)
C1—C2—C3	120.0	C19—C18—C15	117.2 (11)
C4—C3—C2	120.0	C17—C18—C15	125.2 (11)
C4—C3—C6	111.2 (12)	C19—C18—C15A	117.2 (11)
C2—C3—C6	128.8 (12)	C17—C18—C15A	125.2 (11)
C3—C4—C5	120.0	C20—C19—C18	124.0 (11)
C4—C5—N1	120.0	C19—C20—N2	120.3 (9)
C7—C6—C3	131 (3)	O2—C21—O1	122.4 (9)
C6—C7—C8	131 (2)	O2—C21—C22	117.8 (9)
C6—C7—C8A	150 (2)	O1—C21—C22	119.8 (8)
C9—C8—C13	120.0	C27—C22—C23	116.6 (8)
C9—C8—C7	116.8 (7)	C27—C22—C21	120.4 (7)
C13—C8—C7	123.2 (7)	C23—C22—C21	122.9 (7)
C10—C9—C8	120.0	C24—C23—C22	121.8 (8)
C9—C10—C11	120.0	C23—C24—C25	119.2 (9)
C10—C11—C12	120.0	C26—C25—C24	120.7 (9)
C10—C11—C14	119.4 (7)	C26—C25—C28	116.8 (12)
C12—C11—C14	120.5 (7)	C24—C25—C28	122.4 (12)
C11—C12—C13	120.0	C25—C26—C27	120.1 (9)
C12—C13—C8	120.0	C26—C27—C22	121.6 (9)
C15—C14—C11	126.1 (17)	O3—C28—O4	116.3 (10)
C14—C15—C18	134.6 (17)	O3—C28—C25	121.9 (16)
C9A—C8A—C13A	120.0	O4—C28—C25	121.8 (18)

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

 

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Crystal data

C56H40N4O8Zn2	F(000) = 4224
Mr = 1027.66	Dx = 1.199 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.5072 (12) Å	Cell parameters from 9884 reflections
b = 29.3890 (14) Å	θ = 2.2–27.7°
c = 14.9485 (7) Å	µ = 0.89 mm^−1
β = 109.537 (2)°	T = 173 K
V = 11388.7 (9) Å^3	Block, yellow
Z = 8	0.70 × 0.38 × 0.20 mm

Data collection

Bruker APEX-II CCD diffractometer	10607 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.045
Absorption correction: multi-scan SADABS (Sheldrick, 2014)	θmax = 28.4°, θmin = 2.0°
Tmin = 0.601, Tmax = 0.848	h = −36→36
55236 measured reflections	k = −39→38
14223 independent reflections	l = −19→19

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.133	w = 1/[σ^2(Fo^2) + (0.0743P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
14223 reflections	Δρmax = 0.63 e Å^−3
631 parameters	Δρmin = −0.49 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Initially normal data were used to refine the structure. Due to problems in idenditifying the electron densities and refining the atoms we used squeeze program. Further all the other data in this series were squeezed. For uniformity, this data were also squeezed.

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

	x	y	z	Uiso*/Ueq
Zn1	0.36217 (2)	0.12686 (2)	0.35512 (2)	0.02048 (8)
Zn2	0.37649 (2)	0.11015 (2)	0.63940 (2)	0.01875 (8)
O1	0.33304 (6)	0.14731 (7)	0.20868 (13)	0.0385 (4)
O2	0.39216 (7)	0.09401 (6)	0.24723 (12)	0.0329 (4)
O3	0.31877 (6)	0.17322 (5)	0.39355 (12)	0.0266 (4)
O4	0.31991 (5)	0.14291 (5)	0.53128 (12)	0.0241 (3)
O5	0.41238 (6)	0.09576 (5)	0.46907 (12)	0.0290 (4)
O6	0.42133 (6)	0.06354 (5)	0.60787 (13)	0.0271 (4)
O7	0.40158 (9)	0.09983 (8)	0.78483 (15)	0.0511 (6)
O8	0.34472 (8)	0.15447 (10)	0.75038 (16)	0.0674 (7)
N1	0.42369 (7)	0.17652 (6)	0.37377 (15)	0.0260 (4)
C1	0.47128 (9)	0.16381 (8)	0.3797 (2)	0.0333 (6)
H1	0.4789	0.1322	0.3836	0.040*
C2	0.51014 (9)	0.19367 (9)	0.3805 (2)	0.0368 (6)
H2	0.5431	0.1826	0.3833	0.044*
C3	0.50063 (9)	0.24001 (9)	0.37722 (19)	0.0348 (6)
C4	0.45182 (10)	0.25308 (9)	0.3744 (2)	0.0408 (7)
H4	0.4436	0.2845	0.3735	0.049*
C5	0.41515 (10)	0.22124 (8)	0.3728 (2)	0.0342 (6)
H5	0.3821	0.2315	0.3709	0.041*
C6	0.53845 (11)	0.27479 (10)	0.3751 (2)	0.0439 (7)
H6A	0.5293	0.3054	0.3822	0.053*
C7	0.58392 (10)	0.26858 (10)	0.3644 (2)	0.0459 (7)
H7A	0.5944	0.2381	0.3600	0.055*
C8	0.61944 (10)	0.30488 (11)	0.3587 (2)	0.0443 (7)
C9	0.66457 (11)	0.29549 (11)	0.3417 (3)	0.0727 (13)
H9	0.6731	0.2648	0.3337	0.087*
C10	0.69787 (11)	0.33001 (12)	0.3360 (3)	0.0733 (13)
H10	0.7285	0.3224	0.3233	0.088*
C11	0.68747 (11)	0.37510 (10)	0.3484 (2)	0.0462 (7)
C12	0.64192 (16)	0.38415 (12)	0.3637 (4)	0.0780 (14)
H12	0.6330	0.4149	0.3704	0.094*
C13	0.60913 (15)	0.35041 (12)	0.3695 (3)	0.0790 (14)
H13	0.5783	0.3583	0.3812	0.095*
C14	0.72338 (11)	0.41180 (10)	0.3432 (2)	0.0468 (7)
H14	0.7538	0.4031	0.3309	0.056*
C15	0.71647 (11)	0.45546 (10)	0.3542 (2)	0.0452 (7)
H15	0.6858	0.4635	0.3663	0.054*
N2	0.81127 (7)	0.56947 (7)	0.34426 (14)	0.0261 (4)
C16	0.82737 (9)	0.52686 (8)	0.33915 (19)	0.0307 (5)
H16	0.8603	0.5228	0.3328	0.037*
C17	0.79923 (9)	0.48869 (9)	0.3425 (2)	0.0353 (6)
H17	0.8130	0.4593	0.3396	0.042*
C18	0.75037 (10)	0.49317 (9)	0.35015 (19)	0.0362 (6)
C19	0.73360 (10)	0.53800 (10)	0.3552 (2)	0.0420 (7)
H19	0.7007	0.5433	0.3609	0.050*
C20	0.76451 (9)	0.57414 (9)	0.3520 (2)	0.0355 (6)
H20	0.7520	0.6040	0.3553	0.043*
N3	0.42792 (6)	0.16464 (6)	0.64022 (14)	0.0213 (4)
C21	0.47581 (8)	0.15703 (8)	0.63891 (17)	0.0243 (5)
H21	0.4879	0.1265	0.6444	0.029*
C22	0.50808 (8)	0.19083 (8)	0.63009 (17)	0.0261 (5)
H22	0.5413	0.1835	0.6278	0.031*
C23	0.49221 (8)	0.23587 (8)	0.62457 (18)	0.0287 (5)
C24	0.44270 (8)	0.24372 (8)	0.62699 (19)	0.0300 (5)
H24	0.4298	0.2739	0.6227	0.036*
C25	0.41264 (8)	0.20806 (8)	0.63551 (18)	0.0256 (5)
H25	0.3793	0.2144	0.6382	0.031*
C26	0.52495 (9)	0.27387 (9)	0.6173 (2)	0.0352 (6)
H26	0.5090	0.3027	0.5993	0.042*
C27	0.57527 (9)	0.27102 (9)	0.6340 (2)	0.0377 (6)
H27	0.5908	0.2420	0.6513	0.045*
C28	0.60936 (9)	0.30867 (9)	0.6281 (2)	0.0375 (6)
C29	0.66197 (10)	0.30145 (9)	0.6551 (2)	0.0446 (7)
H29	0.6755	0.2723	0.6781	0.053*
C30	0.69534 (10)	0.33562 (9)	0.6494 (2)	0.0447 (7)
H30	0.7312	0.3295	0.6671	0.054*
C31	0.67706 (10)	0.37887 (10)	0.6182 (2)	0.0423 (7)
C32	0.62364 (11)	0.38644 (10)	0.5922 (3)	0.0520 (9)
H32	0.6103	0.4160	0.5723	0.062*
C33	0.59052 (10)	0.35219 (10)	0.5950 (3)	0.0508 (8)
H33	0.5545	0.3579	0.5744	0.061*
C34	0.71308 (10)	0.41438 (9)	0.6139 (2)	0.0408 (7)
H34	0.7481	0.4055	0.6283	0.049*
C35	0.70242 (9)	0.45771 (9)	0.5921 (2)	0.0393 (7)
H35	0.6673	0.4669	0.5726	0.047*
N4	0.81727 (7)	0.55927 (6)	0.61949 (15)	0.0258 (4)
C36	0.82726 (9)	0.51506 (8)	0.6118 (2)	0.0305 (5)
H36	0.8611	0.5066	0.6150	0.037*
C37	0.79081 (9)	0.48115 (8)	0.5995 (2)	0.0323 (6)
H37	0.7997	0.4503	0.5933	0.039*
C38	0.74135 (9)	0.49230 (8)	0.59617 (19)	0.0298 (5)
C39	0.73097 (9)	0.53843 (9)	0.6023 (2)	0.0349 (6)
H39	0.6974	0.5479	0.5988	0.042*
C40	0.76929 (9)	0.57021 (9)	0.6135 (2)	0.0324 (6)
H40	0.7611	0.6014	0.6172	0.039*
C41	0.36413 (9)	0.12113 (9)	0.18884 (18)	0.0285 (5)
C42	0.36743 (9)	0.12382 (8)	0.09027 (17)	0.0247 (5)
C43	0.39878 (9)	0.09375 (8)	0.06325 (18)	0.0284 (5)
H43	0.4187	0.0719	0.1072	0.034*
C44	0.34010 (9)	0.15683 (9)	0.02763 (19)	0.0326 (6)
H44	0.3194	0.1780	0.0466	0.039*
C45	0.30855 (7)	0.17317 (7)	0.46960 (17)	0.0206 (4)
C46	0.27828 (7)	0.21343 (7)	0.48507 (16)	0.0198 (4)
C47	0.25822 (8)	0.24497 (8)	0.41405 (17)	0.0231 (5)
H47	0.2639	0.2415	0.3551	0.028*
C48	0.27035 (8)	0.21811 (7)	0.57225 (17)	0.0226 (5)
H48	0.2842	0.1965	0.6214	0.027*
C49	0.43006 (7)	0.06596 (7)	0.53053 (17)	0.0208 (5)
C50	0.46643 (7)	0.03150 (7)	0.51475 (17)	0.0201 (4)
C51	0.47184 (8)	0.02826 (7)	0.42561 (17)	0.0218 (5)
H51	0.4527	0.0477	0.3753	0.026*
C52	0.49439 (8)	0.00372 (7)	0.58868 (17)	0.0232 (5)
H52	0.4905	0.0065	0.6492	0.028*
C53	0.37308 (11)	0.12767 (11)	0.8070 (2)	0.0434 (8)
C54	0.37310 (9)	0.12799 (9)	0.90839 (18)	0.0307 (6)
C55	0.40116 (9)	0.09554 (9)	0.97197 (19)	0.0315 (6)
H55	0.4221	0.0745	0.9531	0.038*
C56	0.34310 (9)	0.15882 (9)	0.9363 (2)	0.0363 (6)
H56	0.3244	0.1815	0.8932	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02228 (13)	0.02142 (14)	0.02110 (15)	0.00133 (9)	0.01174 (11)	−0.00148 (11)
Zn2	0.02133 (12)	0.01782 (13)	0.02088 (15)	0.00067 (9)	0.01206 (11)	−0.00013 (10)
O1	0.0343 (9)	0.0550 (12)	0.0317 (10)	−0.0019 (8)	0.0186 (8)	−0.0105 (9)
O2	0.0417 (9)	0.0364 (10)	0.0231 (9)	−0.0053 (8)	0.0141 (8)	0.0032 (8)
O3	0.0329 (8)	0.0233 (8)	0.0310 (10)	0.0075 (6)	0.0203 (8)	0.0009 (7)
O4	0.0234 (7)	0.0205 (7)	0.0299 (9)	0.0030 (6)	0.0110 (7)	0.0019 (7)
O5	0.0305 (8)	0.0249 (8)	0.0294 (10)	0.0082 (7)	0.0069 (8)	−0.0005 (8)
O6	0.0310 (8)	0.0208 (8)	0.0394 (10)	0.0014 (6)	0.0251 (8)	−0.0004 (8)
O7	0.0788 (14)	0.0570 (13)	0.0314 (11)	−0.0300 (12)	0.0369 (11)	−0.0139 (10)
O8	0.0540 (13)	0.113 (2)	0.0343 (13)	−0.0098 (14)	0.0136 (11)	0.0251 (14)
N1	0.0300 (9)	0.0236 (10)	0.0281 (11)	−0.0028 (8)	0.0147 (9)	−0.0017 (9)
C1	0.0314 (12)	0.0238 (12)	0.0477 (17)	−0.0012 (9)	0.0173 (12)	0.0001 (12)
C2	0.0292 (12)	0.0341 (14)	0.0487 (18)	−0.0055 (10)	0.0151 (12)	−0.0005 (13)
C3	0.0395 (13)	0.0348 (14)	0.0336 (15)	−0.0116 (11)	0.0167 (12)	−0.0038 (12)
C4	0.0514 (15)	0.0246 (12)	0.0559 (19)	−0.0056 (11)	0.0307 (15)	−0.0015 (13)
C5	0.0374 (12)	0.0267 (12)	0.0461 (17)	0.0009 (10)	0.0240 (13)	0.0004 (12)
C6	0.0515 (16)	0.0348 (15)	0.0520 (19)	−0.0179 (12)	0.0260 (15)	−0.0038 (14)
C7	0.0452 (15)	0.0436 (16)	0.0444 (18)	−0.0193 (13)	0.0092 (14)	0.0055 (14)
C8	0.0439 (15)	0.0463 (17)	0.0412 (17)	−0.0192 (13)	0.0121 (14)	0.0052 (14)
C9	0.0379 (15)	0.0436 (18)	0.132 (4)	−0.0048 (13)	0.022 (2)	0.021 (2)
C10	0.0346 (15)	0.052 (2)	0.131 (4)	−0.0090 (14)	0.024 (2)	0.019 (2)
C11	0.0457 (15)	0.0441 (16)	0.0452 (18)	−0.0219 (13)	0.0105 (14)	0.0006 (15)
C12	0.091 (3)	0.0450 (19)	0.130 (4)	−0.0337 (19)	0.079 (3)	−0.024 (2)
C13	0.086 (3)	0.055 (2)	0.128 (4)	−0.0330 (19)	0.078 (3)	−0.029 (2)
C14	0.0378 (14)	0.0485 (18)	0.0518 (19)	−0.0172 (13)	0.0118 (14)	0.0053 (16)
C15	0.0466 (15)	0.0466 (17)	0.0486 (19)	−0.0228 (13)	0.0241 (15)	−0.0071 (15)
N2	0.0279 (9)	0.0268 (10)	0.0257 (11)	−0.0052 (8)	0.0116 (9)	−0.0026 (9)
C16	0.0264 (11)	0.0323 (13)	0.0349 (15)	−0.0053 (9)	0.0124 (11)	−0.0031 (12)
C17	0.0344 (12)	0.0305 (13)	0.0398 (16)	−0.0057 (10)	0.0108 (12)	0.0004 (12)
C18	0.0394 (13)	0.0411 (15)	0.0306 (14)	−0.0157 (11)	0.0149 (12)	−0.0047 (13)
C19	0.0343 (13)	0.0471 (16)	0.0520 (19)	−0.0122 (12)	0.0244 (14)	−0.0116 (15)
C20	0.0313 (12)	0.0384 (14)	0.0409 (16)	−0.0060 (10)	0.0177 (12)	−0.0081 (13)
N3	0.0215 (8)	0.0225 (9)	0.0202 (10)	−0.0012 (7)	0.0074 (8)	−0.0003 (8)
C21	0.0233 (10)	0.0227 (11)	0.0255 (12)	−0.0020 (8)	0.0065 (10)	−0.0041 (10)
C22	0.0223 (10)	0.0297 (12)	0.0265 (13)	−0.0028 (9)	0.0087 (10)	−0.0022 (11)
C23	0.0259 (11)	0.0320 (12)	0.0275 (13)	−0.0080 (9)	0.0080 (10)	0.0001 (11)
C24	0.0283 (11)	0.0222 (11)	0.0385 (15)	−0.0015 (9)	0.0098 (11)	0.0007 (11)
C25	0.0227 (10)	0.0248 (11)	0.0296 (13)	−0.0011 (9)	0.0091 (10)	0.0001 (10)
C26	0.0350 (12)	0.0283 (13)	0.0438 (16)	−0.0064 (10)	0.0150 (12)	0.0057 (12)
C27	0.0345 (12)	0.0323 (13)	0.0461 (17)	−0.0093 (11)	0.0134 (13)	0.0054 (13)
C28	0.0305 (12)	0.0330 (13)	0.0470 (17)	−0.0091 (10)	0.0102 (12)	0.0081 (13)
C29	0.0326 (13)	0.0313 (14)	0.068 (2)	−0.0043 (11)	0.0152 (14)	0.0094 (15)
C30	0.0299 (12)	0.0371 (15)	0.065 (2)	−0.0057 (11)	0.0130 (14)	0.0101 (15)
C31	0.0356 (13)	0.0384 (15)	0.0525 (19)	−0.0124 (11)	0.0139 (14)	0.0052 (14)
C32	0.0344 (14)	0.0370 (15)	0.083 (3)	−0.0041 (11)	0.0171 (16)	0.0187 (17)
C33	0.0286 (12)	0.0478 (17)	0.076 (2)	−0.0034 (12)	0.0177 (15)	0.0181 (17)
C34	0.0306 (12)	0.0405 (15)	0.0497 (18)	−0.0095 (11)	0.0114 (13)	0.0088 (14)
C35	0.0297 (12)	0.0349 (14)	0.0548 (19)	−0.0079 (11)	0.0159 (13)	0.0055 (14)
N4	0.0248 (9)	0.0221 (9)	0.0337 (12)	0.0006 (7)	0.0140 (9)	0.0036 (9)
C36	0.0297 (11)	0.0246 (12)	0.0413 (15)	−0.0017 (9)	0.0172 (12)	0.0020 (11)
C37	0.0321 (12)	0.0234 (11)	0.0450 (16)	−0.0010 (9)	0.0178 (12)	0.0034 (12)
C38	0.0292 (11)	0.0294 (12)	0.0320 (14)	−0.0064 (9)	0.0118 (11)	0.0053 (11)
C39	0.0237 (11)	0.0346 (13)	0.0490 (17)	−0.0006 (10)	0.0156 (12)	0.0094 (13)
C40	0.0296 (11)	0.0290 (12)	0.0451 (16)	0.0027 (9)	0.0213 (12)	0.0055 (12)
C41	0.0300 (11)	0.0356 (13)	0.0239 (13)	−0.0115 (10)	0.0143 (11)	−0.0076 (11)
C42	0.0276 (11)	0.0284 (12)	0.0221 (12)	−0.0047 (9)	0.0135 (10)	−0.0013 (10)
C43	0.0364 (12)	0.0258 (12)	0.0257 (13)	0.0002 (10)	0.0141 (11)	0.0020 (11)
C44	0.0312 (12)	0.0357 (14)	0.0339 (15)	0.0034 (10)	0.0149 (11)	−0.0003 (12)
C45	0.0179 (9)	0.0186 (10)	0.0257 (12)	0.0013 (8)	0.0078 (9)	−0.0011 (10)
C46	0.0191 (9)	0.0200 (10)	0.0220 (11)	0.0013 (8)	0.0091 (9)	−0.0008 (9)
C47	0.0257 (10)	0.0263 (11)	0.0201 (12)	0.0053 (9)	0.0116 (9)	−0.0002 (10)
C48	0.0261 (10)	0.0223 (11)	0.0217 (12)	0.0043 (8)	0.0110 (10)	0.0031 (10)
C49	0.0163 (9)	0.0183 (10)	0.0285 (12)	−0.0028 (8)	0.0084 (9)	−0.0060 (10)
C50	0.0190 (9)	0.0177 (10)	0.0268 (12)	−0.0008 (8)	0.0117 (9)	−0.0027 (10)
C51	0.0243 (10)	0.0204 (10)	0.0227 (12)	0.0041 (8)	0.0105 (9)	0.0028 (10)
C52	0.0287 (11)	0.0232 (11)	0.0235 (12)	0.0014 (9)	0.0163 (10)	0.0001 (10)
C53	0.0447 (15)	0.066 (2)	0.0187 (13)	−0.0306 (14)	0.0094 (12)	0.0055 (14)
C54	0.0337 (12)	0.0390 (14)	0.0221 (13)	−0.0138 (10)	0.0128 (11)	−0.0015 (11)
C55	0.0369 (12)	0.0336 (13)	0.0296 (14)	−0.0043 (10)	0.0187 (12)	−0.0038 (12)
C56	0.0347 (12)	0.0419 (15)	0.0300 (14)	0.0013 (11)	0.0076 (12)	0.0127 (13)

Geometric parameters (Å, º)

Zn1—O3	2.0175 (15)	C19—C20	1.371 (3)
Zn1—O5	2.0176 (17)	N3—C25	1.338 (3)
Zn1—O1	2.150 (2)	N3—C21	1.343 (3)
Zn1—N2^i	2.1631 (18)	C21—C22	1.368 (3)
Zn1—N1	2.1810 (18)	C22—C23	1.387 (3)
Zn1—O2	2.2590 (17)	C23—C24	1.394 (3)
Zn1—C41	2.510 (3)	C23—C26	1.461 (3)
Zn2—O6	2.0022 (15)	C24—C25	1.367 (3)
Zn2—O4	2.0686 (16)	C26—C27	1.325 (3)
Zn2—O7	2.071 (2)	C27—C28	1.472 (3)
Zn2—N3	2.1342 (17)	C28—C29	1.382 (3)
Zn2—N4^i	2.1572 (18)	C28—C33	1.406 (4)
Zn2—O8	2.487 (3)	C29—C30	1.382 (3)
Zn2—C53	2.590 (3)	C30—C31	1.389 (4)
O1—C41	1.257 (3)	C31—C32	1.406 (4)
O2—C41	1.242 (3)	C31—C34	1.455 (3)
O3—C45	1.259 (3)	C32—C33	1.368 (4)
O4—C45	1.243 (3)	C34—C35	1.323 (4)
O5—C49	1.245 (3)	C35—C38	1.463 (3)
O6—C49	1.259 (3)	N4—C40	1.332 (3)
O7—C53	1.252 (4)	N4—C36	1.341 (3)
O8—C53	1.226 (4)	N4—Zn2^ii	2.1571 (18)
N1—C5	1.334 (3)	C36—C37	1.382 (3)
N1—C1	1.336 (3)	C37—C38	1.384 (3)
C1—C2	1.380 (3)	C38—C39	1.395 (3)
C2—C3	1.385 (4)	C39—C40	1.376 (3)
C3—C4	1.383 (3)	C41—C42	1.508 (3)
C3—C6	1.467 (3)	C42—C44	1.383 (3)
C4—C5	1.370 (3)	C42—C43	1.386 (3)
C6—C7	1.325 (4)	C43—C55^iii	1.389 (3)
C7—C8	1.468 (4)	C44—C56^iii	1.396 (4)
C8—C9	1.376 (4)	C45—C46	1.508 (3)
C8—C13	1.388 (5)	C46—C47	1.378 (3)
C9—C10	1.388 (4)	C46—C48	1.398 (3)
C10—C11	1.381 (5)	C47—C48^iv	1.395 (3)
C11—C12	1.373 (5)	C48—C47^iv	1.394 (3)
C11—C14	1.482 (4)	C49—C50	1.497 (3)
C12—C13	1.362 (4)	C50—C52	1.382 (3)
C14—C15	1.316 (4)	C50—C51	1.393 (3)
C15—C18	1.463 (3)	C51—C52^v	1.387 (3)
N2—C20	1.336 (3)	C52—C51^v	1.387 (3)
N2—C16	1.339 (3)	C53—C54	1.516 (4)
N2—Zn1^ii	2.1630 (18)	C54—C56	1.381 (4)
C16—C17	1.373 (3)	C54—C55	1.385 (4)
C17—C18	1.393 (3)	C55—C43^vi	1.389 (3)
C18—C19	1.406 (4)	C56—C44^vi	1.396 (4)
O3—Zn1—O5	111.64 (7)	C16—C17—C18	119.8 (2)
O3—Zn1—O1	92.66 (7)	C17—C18—C19	115.8 (2)
O5—Zn1—O1	154.57 (7)	C17—C18—C15	125.3 (3)
O3—Zn1—N2^i	96.78 (7)	C19—C18—C15	118.9 (2)
O5—Zn1—N2^i	87.33 (7)	C20—C19—C18	120.3 (2)
O1—Zn1—N2^i	97.47 (7)	N2—C20—C19	123.3 (2)
O3—Zn1—N1	91.11 (7)	C25—N3—C21	116.78 (19)
O5—Zn1—N1	84.97 (7)	C25—N3—Zn2	121.29 (14)
O1—Zn1—N1	87.25 (7)	C21—N3—Zn2	121.78 (15)
N2^i—Zn1—N1	170.58 (7)	N3—C21—C22	123.5 (2)
O3—Zn1—O2	152.13 (7)	C21—C22—C23	119.8 (2)
O5—Zn1—O2	95.67 (7)	C22—C23—C24	116.5 (2)
O1—Zn1—O2	59.56 (7)	C22—C23—C26	123.0 (2)
N2^i—Zn1—O2	89.71 (7)	C24—C23—C26	120.5 (2)
N1—Zn1—O2	85.66 (7)	C25—C24—C23	120.1 (2)
O3—Zn1—C41	122.54 (8)	N3—C25—C24	123.2 (2)
O5—Zn1—C41	124.78 (8)	C27—C26—C23	124.7 (2)
O1—Zn1—C41	30.06 (7)	C26—C27—C28	126.0 (3)
N2^i—Zn1—C41	95.81 (7)	C29—C28—C33	118.0 (2)
N1—Zn1—C41	84.19 (7)	C29—C28—C27	119.5 (2)
O2—Zn1—C41	29.59 (7)	C33—C28—C27	122.5 (2)
O6—Zn2—O4	119.75 (7)	C30—C29—C28	121.5 (3)
O6—Zn2—O7	97.56 (9)	C29—C30—C31	120.8 (2)
O4—Zn2—O7	141.97 (8)	C30—C31—C32	117.7 (2)
O6—Zn2—N3	93.17 (6)	C30—C31—C34	119.7 (2)
O4—Zn2—N3	88.81 (6)	C32—C31—C34	122.6 (3)
O7—Zn2—N3	96.68 (7)	C33—C32—C31	121.3 (3)
O6—Zn2—N4^i	89.40 (7)	C32—C33—C28	120.6 (2)
O4—Zn2—N4^i	83.04 (7)	C35—C34—C31	127.1 (3)
O7—Zn2—N4^i	90.83 (8)	C34—C35—C38	124.0 (2)
N3—Zn2—N4^i	171.67 (7)	C40—N4—C36	117.1 (2)
O6—Zn2—O8	153.78 (8)	C40—N4—Zn2^ii	121.85 (16)
O4—Zn2—O8	86.39 (7)	C36—N4—Zn2^ii	121.09 (14)
O7—Zn2—O8	56.26 (8)	N4—C36—C37	123.4 (2)
N3—Zn2—O8	89.04 (7)	C36—C37—C38	119.6 (2)
N4^i—Zn2—O8	92.15 (7)	C37—C38—C39	116.6 (2)
O6—Zn2—C53	126.03 (10)	C37—C38—C35	122.3 (2)
O4—Zn2—C53	113.71 (9)	C39—C38—C35	121.0 (2)
O7—Zn2—C53	28.49 (9)	C40—C39—C38	120.2 (2)
N3—Zn2—C53	94.80 (8)	N4—C40—C39	123.1 (2)
N4^i—Zn2—C53	90.07 (8)	O2—C41—O1	122.6 (2)
O8—Zn2—C53	27.86 (9)	O2—C41—C42	119.6 (2)
C41—O1—Zn1	91.02 (16)	O1—C41—C42	117.8 (2)
C41—O2—Zn1	86.47 (14)	O2—C41—Zn1	63.94 (13)
C45—O3—Zn1	126.04 (14)	O1—C41—Zn1	58.92 (13)
C45—O4—Zn2	148.13 (14)	C42—C41—Zn1	172.85 (17)
C49—O5—Zn1	158.45 (15)	C44—C42—C43	120.0 (2)
C49—O6—Zn2	119.95 (14)	C44—C42—C41	120.1 (2)
C53—O7—Zn2	99.41 (19)	C43—C42—C41	119.9 (2)
C53—O8—Zn2	80.8 (2)	C42—C43—C55^iii	120.0 (2)
C5—N1—C1	116.2 (2)	C42—C44—C56^iii	119.7 (2)
C5—N1—Zn1	122.11 (15)	O4—C45—O3	126.4 (2)
C1—N1—Zn1	121.51 (16)	O4—C45—C46	117.5 (2)
N1—C1—C2	124.2 (2)	O3—C45—C46	116.03 (19)
C1—C2—C3	119.3 (2)	C47—C46—C48	120.32 (19)
C4—C3—C2	116.4 (2)	C47—C46—C45	120.6 (2)
C4—C3—C6	119.6 (2)	C48—C46—C45	119.1 (2)
C2—C3—C6	124.0 (2)	C46—C47—C48^iv	120.7 (2)
C5—C4—C3	120.8 (2)	C47^iv—C48—C46	119.0 (2)
N1—C5—C4	123.1 (2)	O5—C49—O6	124.77 (19)
C7—C6—C3	127.7 (3)	O5—C49—C50	118.5 (2)
C6—C7—C8	125.4 (3)	O6—C49—C50	116.7 (2)
C9—C8—C13	116.5 (3)	C52—C50—C51	121.04 (19)
C9—C8—C7	121.6 (3)	C52—C50—C49	119.7 (2)
C13—C8—C7	121.9 (3)	C51—C50—C49	119.2 (2)
C8—C9—C10	121.3 (3)	C52^v—C51—C50	119.0 (2)
C11—C10—C9	121.5 (3)	C50—C52—C51^v	120.0 (2)
C12—C11—C10	116.7 (3)	O8—C53—O7	123.2 (3)
C12—C11—C14	121.9 (3)	O8—C53—C54	118.3 (3)
C10—C11—C14	121.3 (3)	O7—C53—C54	118.5 (3)
C13—C12—C11	122.0 (3)	O8—C53—Zn2	71.39 (18)
C12—C13—C8	121.9 (3)	O7—C53—Zn2	52.10 (15)
C15—C14—C11	125.2 (3)	C54—C53—Zn2	168.7 (2)
C14—C15—C18	127.8 (3)	C56—C54—C55	119.8 (2)
C20—N2—C16	116.6 (2)	C56—C54—C53	120.4 (3)
C20—N2—Zn1^ii	122.08 (17)	C55—C54—C53	119.7 (2)
C16—N2—Zn1^ii	121.01 (15)	C54—C55—C43^vi	120.1 (2)
N2—C16—C17	124.1 (2)	C54—C56—C44^vi	120.3 (2)

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

 

(4)

Crystal data

C56H40N4O8Zn2	Dx = 1.125 Mg m^−3
Mr = 1027.66	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pcca	Cell parameters from 9984 reflections
a = 20.030 (3) Å	θ = 2.3–27.3°
b = 20.005 (3) Å	µ = 0.84 mm^−1
c = 15.145 (2) Å	T = 173 K
V = 6068.8 (14) Å^3	Block, red
Z = 4	0.46 × 0.41 × 0.30 mm
F(000) = 2112

Data collection

Bruker APEX-II CCD diffractometer	3975 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.074
Absorption correction: multi-scan SADABS (Sheldrick, 2011)	θmax = 26.0°, θmin = 2.0°
Tmin = 0.703, Tmax = 0.801	h = −24→24
46693 measured reflections	k = −24→24
5979 independent reflections	l = −18→18

Refinement

Refinement on F^2	440 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.073	H-atom parameters constrained
wR(F^2) = 0.231	w = 1/[σ^2(Fo^2) + (0.1154P)^2 + 7.2582P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
5979 reflections	Δρmax = 0.91 e Å^−3
294 parameters	Δρmin = −0.72 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Crystallized in the orthorhombic space group Pcca with Z = 4. The asymmetric unit contains half of the formula unit. The dimer formed by dimerization of trans,cis,trans-bpeb disordered due to crystallographic centre of inversion. Due to this disorder soft constraints (FLAT, SAME, SADI) were used to retain the geometry of molecule. Only isotropic thermal parameter could be refined for these bpeb-dimer fragment. Again one DMF was disordered by crystallographic inversion centre. The rest of the electron densities were too complicated to resolve. Hence they were assigned as O atoms of water molecules. They could as well be highly disordered DMF.[Zn2(bdc)2(dimer)].DMF.6.5H2O. For uniformity, the referee suggested to squeeze the data and hence squeezed. The agreement factors of the squeezed better than the unsqueezed data.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.43270 (3)	0.66969 (2)	0.85781 (3)	0.0250 (2)
O1	0.52593 (15)	0.67007 (14)	0.9065 (2)	0.0355 (8)
O2	0.57615 (18)	0.67078 (17)	0.7764 (2)	0.0449 (9)
O3	0.8303 (2)	0.67234 (15)	1.1227 (3)	0.0521 (11)
O4	0.8841 (2)	0.67063 (16)	0.9961 (3)	0.0565 (11)
N1	0.4379 (6)	0.5644 (5)	0.8558 (8)	0.024 (4)*	0.5
C1	0.4867 (6)	0.5310 (5)	0.8977 (8)	0.034 (4)*	0.5
H1	0.5149	0.5556	0.9363	0.041*	0.5
C2	0.4988 (5)	0.4633 (4)	0.8886 (7)	0.029 (3)*	0.5
H2A	0.5336	0.4426	0.9212	0.035*	0.5
C3	0.4601 (5)	0.4260 (4)	0.8318 (7)	0.024 (2)*	0.5
C4	0.4064 (6)	0.4579 (4)	0.7932 (7)	0.030 (3)*	0.5
H4	0.3767	0.4339	0.7560	0.037*	0.5
C5	0.3963 (6)	0.5258 (5)	0.8095 (9)	0.033 (4)*	0.5
H5	0.3571	0.5459	0.7861	0.039*	0.5
C6	0.4863 (5)	0.3575 (4)	0.8109 (6)	0.033 (2)*	0.5
H6	0.5062	0.3358	0.8642	0.040*	0.5
C7	0.4391 (5)	0.3084 (5)	0.7602 (6)	0.043 (2)*	0.5
H7	0.3970	0.3321	0.7435	0.052*	0.5
C8	0.4224 (5)	0.2409 (5)	0.8006 (7)	0.051 (3)*	0.5
C9	0.4677 (6)	0.2060 (4)	0.8435 (6)	0.041 (2)*	0.5
H9	0.5039	0.2299	0.8690	0.049*	0.5
C10	0.4669 (6)	0.1379 (5)	0.8546 (7)	0.059 (3)*	0.5
H10	0.4991	0.1165	0.8909	0.071*	0.5
C11	0.4195 (7)	0.1021 (6)	0.8128 (10)	0.079 (4)*	0.5
C12	0.3664 (7)	0.1385 (5)	0.7824 (9)	0.073 (4)*	0.5
H12	0.3265	0.1159	0.7664	0.087*	0.5
C13	0.3694 (7)	0.2077 (5)	0.7745 (9)	0.079 (4)*	0.5
H13	0.3327	0.2312	0.7498	0.095*	0.5
C14	0.4371 (8)	0.0329 (8)	0.7736 (10)	0.108 (6)*	0.5
H14	0.3942	0.0089	0.7618	0.129*	0.5
C15	0.4872 (8)	−0.0191 (7)	0.8174 (10)	0.103 (6)*	0.5
H15	0.5116	0.0024	0.8676	0.123*	0.5
N2	0.4371 (5)	−0.2216 (4)	0.8662 (7)	0.027 (3)*	0.5
C16	0.3959 (6)	−0.1848 (5)	0.8195 (8)	0.045 (3)*	0.5
H16	0.3607	−0.2070	0.7893	0.054*	0.5
C17	0.4001 (7)	−0.1157 (6)	0.8108 (11)	0.084 (5)*	0.5
H17	0.3668	−0.0909	0.7804	0.101*	0.5
C18	0.4543 (6)	−0.0853 (5)	0.8480 (9)	0.058 (4)*	0.5
C19	0.4928 (6)	−0.1198 (5)	0.9043 (9)	0.058 (4)*	0.5
H19	0.5261	−0.0978	0.9383	0.070*	0.5
C20	0.4830 (6)	−0.1884 (5)	0.9119 (9)	0.041 (3)*	0.5
H20	0.5105	−0.2127	0.9516	0.050*	0.5
N3	0.5710 (6)	0.5599 (6)	0.6504 (8)	0.031 (5)*	0.5
C21	0.5219 (6)	0.5235 (5)	0.6137 (8)	0.038 (5)*	0.5
H21	0.4923	0.5442	0.5731	0.046*	0.5
C22	0.5134 (6)	0.4561 (5)	0.6339 (8)	0.040 (3)*	0.5
H22	0.4785	0.4316	0.6063	0.048*	0.5
C23	0.5551 (5)	0.4247 (4)	0.6936 (7)	0.033 (3)*	0.5
C24	0.6073 (6)	0.4620 (5)	0.7256 (8)	0.036 (3)*	0.5
H24	0.6403	0.4414	0.7615	0.043*	0.5
C25	0.6122 (6)	0.5296 (5)	0.7058 (8)	0.026 (3)*	0.5
H25	0.6465	0.5551	0.7331	0.031*	0.5
C26	0.5369 (5)	0.3566 (4)	0.7298 (6)	0.038 (2)*	0.5
H26	0.5784	0.3321	0.7471	0.045*	0.5
C27	0.4897 (5)	0.3085 (5)	0.6782 (6)	0.049 (3)*	0.5
H27	0.4694	0.3320	0.6265	0.059*	0.5
C28	0.5137 (7)	0.2388 (6)	0.6514 (9)	0.073 (4)*	0.5
C29	0.5648 (8)	0.2054 (7)	0.6847 (12)	0.099 (6)*	0.5
H29	0.6006	0.2289	0.7118	0.119*	0.5
C30	0.5661 (9)	0.1352 (8)	0.6801 (15)	0.126 (8)*	0.5
H30	0.6059	0.1125	0.6963	0.151*	0.5
C31	0.5126 (9)	0.0986 (7)	0.6532 (12)	0.106 (6)*	0.5
C32	0.4692 (10)	0.1341 (8)	0.6038 (14)	0.139 (7)*	0.5
H32	0.4394	0.1115	0.5653	0.166*	0.5
C33	0.4680 (8)	0.2029 (7)	0.6086 (11)	0.102 (5)*	0.5
H33	0.4326	0.2260	0.5799	0.122*	0.5
C34	0.4806 (8)	0.0313 (7)	0.6838 (9)	0.094 (5)*	0.5
H34	0.4560	0.0088	0.6347	0.113*	0.5
C35	0.5328 (8)	−0.0178 (7)	0.7296 (10)	0.107 (6)*	0.5
H35	0.5749	0.0074	0.7423	0.129*	0.5
N4	0.5664 (5)	−0.2225 (5)	0.6544 (7)	0.036 (3)*	0.5
C36	0.6065 (5)	−0.1894 (5)	0.7073 (8)	0.039 (3)*	0.5
H36	0.6414	−0.2130	0.7361	0.047*	0.5
C37	0.5999 (6)	−0.1224 (5)	0.7227 (9)	0.054 (3)*	0.5
H37	0.6314	−0.1010	0.7600	0.065*	0.5
C38	0.5507 (7)	−0.0856 (6)	0.6874 (10)	0.071 (4)*	0.5
C39	0.5090 (7)	−0.1163 (6)	0.6309 (10)	0.063 (4)*	0.5
H39	0.4745	−0.0925	0.6015	0.076*	0.5
C40	0.5186 (7)	−0.1851 (5)	0.6172 (9)	0.052 (4)*	0.5
H40	0.4886	−0.2070	0.5782	0.062*	0.5
C41	0.5766 (2)	0.67179 (19)	0.8582 (3)	0.0286 (11)
C42	0.6429 (2)	0.67537 (18)	0.9037 (3)	0.0260 (9)
C43	0.6469 (3)	0.6791 (2)	0.9952 (3)	0.0380 (11)
H43	0.6069	0.6816	1.0289	0.046*
C44	0.7073 (3)	0.6794 (2)	1.0380 (3)	0.0410 (12)
H44	0.7088	0.6828	1.1005	0.049*
C45	0.7657 (2)	0.67477 (19)	0.9908 (4)	0.0361 (11)
C46	0.7626 (2)	0.6705 (2)	0.8997 (3)	0.0361 (11)
H46	0.8027	0.6667	0.8666	0.043*
C47	0.7017 (3)	0.6716 (2)	0.8560 (3)	0.0353 (11)
H47	0.7004	0.6697	0.7933	0.042*
C48	0.8319 (3)	0.6726 (2)	1.0396 (4)	0.0469 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0203 (3)	0.0253 (3)	0.0296 (3)	0.0000 (2)	0.0023 (2)	0.00168 (18)
O1	0.0140 (16)	0.0446 (18)	0.048 (2)	−0.0013 (13)	0.0009 (16)	0.0029 (14)
O2	0.037 (2)	0.067 (2)	0.0299 (17)	0.0076 (17)	−0.0089 (16)	−0.0097 (15)
O3	0.054 (3)	0.0392 (19)	0.063 (2)	0.0023 (17)	−0.033 (2)	0.0006 (16)
O4	0.029 (2)	0.046 (2)	0.094 (3)	0.0004 (16)	−0.024 (2)	0.0005 (19)
C41	0.023 (3)	0.027 (2)	0.036 (3)	0.0016 (18)	−0.008 (2)	−0.0027 (18)
C42	0.018 (2)	0.025 (2)	0.035 (2)	−0.0003 (17)	−0.0058 (19)	−0.0030 (17)
C43	0.025 (3)	0.051 (3)	0.038 (3)	0.005 (2)	0.003 (2)	−0.004 (2)
C44	0.035 (3)	0.047 (3)	0.041 (3)	0.007 (2)	−0.015 (2)	−0.003 (2)
C45	0.024 (3)	0.027 (2)	0.057 (3)	−0.0028 (19)	−0.014 (2)	0.003 (2)
C46	0.023 (3)	0.033 (2)	0.053 (3)	0.0020 (19)	0.003 (2)	0.000 (2)
C47	0.026 (3)	0.048 (3)	0.032 (2)	−0.004 (2)	0.000 (2)	0.000 (2)
C48	0.031 (3)	0.023 (2)	0.086 (4)	−0.001 (2)	−0.020 (3)	0.001 (2)

Geometric parameters (Å, º)

Zn1—O1	2.008 (3)	C16—C17	1.391 (11)
Zn1—O2^i	2.040 (3)	C17—C18	1.366 (12)
Zn1—O3^ii	2.073 (4)	C18—C19	1.341 (12)
Zn1—N1	2.110 (10)	C19—C20	1.391 (10)
Zn1—O4^ii	2.418 (4)	N3—C25	1.324 (11)
Zn1—C48^ii	2.548 (6)	N3—C21	1.344 (11)
O1—C41	1.253 (6)	C21—C22	1.392 (11)
O2—C41	1.239 (5)	C22—C23	1.384 (11)
O2—Zn1^i	2.040 (3)	C23—C24	1.372 (11)
O3—C48	1.259 (7)	C23—C26	1.513 (10)
O3—Zn1^iii	2.073 (4)	C24—C25	1.389 (10)
O4—C48	1.237 (7)	C26—C27	1.559 (11)
O4—Zn1^iii	2.418 (4)	C27—C28	1.530 (12)
N1—C5	1.336 (11)	C28—C29	1.322 (12)
N1—C1	1.344 (11)	C28—C33	1.332 (12)
C1—C2	1.382 (10)	C29—C30	1.407 (13)
C2—C3	1.378 (11)	C30—C31	1.360 (13)
C3—C4	1.381 (11)	C31—C32	1.348 (13)
C3—C6	1.501 (9)	C31—C34	1.562 (13)
C4—C5	1.395 (10)	C32—C33	1.380 (13)
C6—C7	1.565 (11)	C34—C35	1.593 (13)
C6—C26	1.591 (10)	C35—C38	1.543 (13)
C7—C8	1.521 (11)	N4—C36	1.313 (11)
C7—C27	1.603 (11)	N4—C40	1.340 (11)
C8—C13	1.313 (11)	C36—C37	1.367 (10)
C8—C9	1.316 (11)	C37—C38	1.341 (12)
C9—C10	1.373 (11)	C38—C39	1.343 (12)
C10—C11	1.347 (12)	C39—C40	1.406 (11)
C11—C12	1.369 (12)	C41—C42	1.497 (6)
C11—C14	1.547 (13)	C42—C47	1.384 (7)
C12—C13	1.391 (12)	C42—C43	1.390 (6)
C14—C15	1.590 (14)	C43—C44	1.373 (7)
C14—C34	1.615 (13)	C44—C45	1.374 (8)
C15—C18	1.552 (13)	C45—C46	1.383 (7)
C15—C35	1.613 (13)	C45—C48	1.518 (7)
N2—C16	1.313 (11)	C46—C47	1.389 (7)
N2—C20	1.328 (10)	C48—Zn1^iii	2.548 (6)
O1—Zn1—O2^i	116.53 (14)	N2—C20—C19	123.2 (10)
O1—Zn1—O3^ii	150.21 (16)	C25—N3—C21	117.9 (11)
O2^i—Zn1—O3^ii	93.19 (16)	N3—C21—C22	121.7 (11)
O1—Zn1—N1	87.9 (3)	C23—C22—C21	120.6 (10)
O2^i—Zn1—N1	90.0 (3)	C24—C23—C22	116.4 (8)
O3^ii—Zn1—N1	94.4 (3)	C24—C23—C26	123.1 (9)
O1—Zn1—O4^ii	92.18 (15)	C22—C23—C26	120.0 (9)
O2^i—Zn1—O4^ii	151.26 (15)	C23—C24—C25	120.5 (10)
O3^ii—Zn1—O4^ii	58.07 (16)	N3—C25—C24	122.6 (11)
N1—Zn1—O4^ii	92.4 (3)	C23—C26—C27	121.3 (9)
O1—Zn1—C48^ii	120.85 (18)	C23—C26—C6	115.0 (8)
O2^i—Zn1—C48^ii	122.58 (19)	C27—C26—C6	90.5 (6)
O3^ii—Zn1—C48^ii	29.39 (18)	C28—C27—C26	120.3 (9)
N1—Zn1—C48^ii	94.1 (4)	C28—C27—C7	113.8 (9)
O4^ii—Zn1—C48^ii	28.68 (17)	C26—C27—C7	89.8 (5)
C41—O1—Zn1	122.7 (3)	C29—C28—C33	116.5 (12)
C41—O2—Zn1^i	175.5 (4)	C29—C28—C27	127.0 (12)
C48—O3—Zn1^iii	96.7 (4)	C33—C28—C27	113.9 (11)
C48—O4—Zn1^iii	81.5 (4)	C28—C29—C30	119.9 (14)
C5—N1—C1	114.5 (10)	C31—C30—C29	122.5 (15)
C5—N1—Zn1	123.7 (8)	C32—C31—C30	113.0 (14)
C1—N1—Zn1	121.7 (8)	C32—C31—C34	110.8 (14)
N1—C1—C2	124.5 (11)	C30—C31—C34	134.3 (15)
C3—C2—C1	119.7 (9)	C31—C32—C33	120.5 (14)
C2—C3—C4	116.8 (7)	C28—C33—C32	123.4 (13)
C2—C3—C6	115.4 (8)	C31—C34—C35	113.0 (13)
C4—C3—C6	127.3 (9)	C31—C34—C14	117.0 (14)
C3—C4—C5	119.3 (9)	C35—C34—C14	90.0 (6)
N1—C5—C4	124.4 (11)	C38—C35—C34	120.9 (14)
C3—C6—C7	117.6 (9)	C38—C35—C15	117.3 (14)
C3—C6—C26	113.3 (8)	C34—C35—C15	89.8 (6)
C7—C6—C26	90.0 (6)	C36—N4—C40	114.4 (10)
C8—C7—C6	119.5 (8)	N4—C36—C37	122.6 (10)
C8—C7—C27	116.9 (8)	C38—C37—C36	122.8 (11)
C6—C7—C27	89.8 (5)	C37—C38—C39	117.4 (10)
C13—C8—C9	116.0 (10)	C37—C38—C35	119.2 (11)
C13—C8—C7	120.3 (9)	C39—C38—C35	121.4 (12)
C9—C8—C7	121.2 (9)	C38—C39—C40	117.1 (11)
C8—C9—C10	125.3 (10)	N4—C40—C39	125.6 (12)
C11—C10—C9	118.6 (11)	O2—C41—O1	125.3 (4)
C10—C11—C12	115.0 (11)	O2—C41—C42	117.9 (4)
C10—C11—C14	119.7 (12)	O1—C41—C42	116.8 (4)
C12—C11—C14	121.6 (11)	C47—C42—C43	118.3 (4)
C11—C12—C13	121.7 (11)	C47—C42—C41	120.7 (4)
C8—C13—C12	120.8 (11)	C43—C42—C41	120.9 (4)
C11—C14—C15	124.7 (13)	C44—C43—C42	121.4 (5)
C11—C14—C34	117.6 (14)	C43—C44—C45	120.3 (4)
C15—C14—C34	89.9 (6)	C44—C45—C46	118.9 (4)
C18—C15—C14	114.4 (14)	C44—C45—C48	119.5 (5)
C18—C15—C35	120.1 (14)	C46—C45—C48	121.6 (5)
C14—C15—C35	90.2 (7)	C45—C46—C47	121.0 (5)
C16—N2—C20	115.8 (9)	C42—C47—C46	119.9 (4)
N2—C16—C17	124.8 (11)	O4—C48—O3	123.7 (5)
C18—C17—C16	116.8 (12)	O4—C48—C45	118.6 (6)
C19—C18—C17	119.4 (10)	O3—C48—C45	117.7 (5)
C19—C18—C15	112.6 (11)	O4—C48—Zn1^iii	69.8 (3)
C17—C18—C15	126.5 (12)	O3—C48—Zn1^iii	53.9 (3)
C18—C19—C20	118.6 (10)	C45—C48—Zn1^iii	171.6 (5)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) x−1/2, y, −z+2; (iii) x+1/2, y, −z+2.

 

(5)

Crystal data

C56H40N4O8Zn2	Dx = 1.152 Mg m^−3
Mr = 1027.66	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pcca	Cell parameters from 9896 reflections
a = 20.0663 (6) Å	θ = 2.3–26.4°
b = 19.9342 (7) Å	µ = 0.86 mm^−1
c = 14.8166 (5) Å	T = 173 K
V = 5926.7 (3) Å^3	Plate, yellow
Z = 4	0.14 × 0.10 × 0.07 mm
F(000) = 2112

Data collection

Bruker APEX-II CCD diffractometer	3043 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.119
Absorption correction: multi-scan SADABS (Sheldrick, 2012)	θmax = 26.0°, θmin = 2.0°
Tmin = 0.888, Tmax = 0.965	h = −24→24
64566 measured reflections	k = −23→22
5651 independent reflections	l = −17→18

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.109	w = 1/[σ^2(Fo^2) + (0.1667P)^2 + 25.0974P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.347	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.90 e Å^−3
5651 reflections	Δρmin = −0.62 e Å^−3
295 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
440 restraints	Extinction coefficient: 0.00009 (12)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.43536 (4)	0.66393 (5)	0.86152 (6)	0.0481 (4)
O1	0.5286 (3)	0.6667 (3)	0.9082 (4)	0.0653 (16)
O2	0.5750 (3)	0.6654 (5)	0.7752 (5)	0.100 (3)
O3	0.8356 (3)	0.6657 (4)	1.1149 (6)	0.091 (2)
O4	0.8874 (3)	0.6652 (3)	0.9852 (6)	0.091 (2)
N1	0.4377 (9)	0.5542 (8)	0.8686 (13)	0.060 (8)*	0.5
C1	0.4903 (8)	0.5237 (8)	0.8992 (12)	0.047 (6)*	0.5
H1	0.5208	0.5502	0.9328	0.056*	0.5
C2	0.5065 (10)	0.4579 (8)	0.8883 (14)	0.073 (7)*	0.5
H2A	0.5464	0.4401	0.9130	0.088*	0.5
C3	0.4633 (8)	0.4183 (8)	0.8405 (13)	0.058 (5)*	0.5
C4	0.4056 (9)	0.4478 (9)	0.8074 (13)	0.060 (5)*	0.5
H4	0.3730	0.4228	0.7752	0.072*	0.5
C5	0.3984 (13)	0.5148 (10)	0.824 (2)	0.126 (15)*	0.5
H5	0.3596	0.5352	0.7992	0.151*	0.5
C6	0.4903 (11)	0.3506 (9)	0.8117 (15)	0.088 (7)*	0.5
H6	0.5095	0.3269	0.8652	0.106*	0.5
C7	0.4416 (12)	0.2991 (14)	0.7553 (18)	0.142 (12)*	0.5
H7	0.4006	0.3217	0.7319	0.171*	0.5
C8	0.4260 (15)	0.2328 (11)	0.8054 (19)	0.110 (9)*	0.5
C9	0.4636 (15)	0.1945 (16)	0.855 (2)	0.19 (2)*	0.5
H9	0.4968	0.2180	0.8883	0.226*	0.5
C10	0.4637 (16)	0.1265 (16)	0.869 (2)	0.128 (10)*	0.5
H10	0.4936	0.1045	0.9088	0.154*	0.5
C11	0.416 (3)	0.0931 (17)	0.819 (4)	0.42 (7)*	0.5
C12	0.3713 (19)	0.1313 (19)	0.770 (3)	0.215 (19)*	0.5
H12	0.3343	0.1106	0.7411	0.258*	0.5
C13	0.3807 (18)	0.1989 (18)	0.763 (3)	0.25 (2)*	0.5
H13	0.3516	0.2231	0.7244	0.299*	0.5
C14	0.451 (4)	0.050 (3)	0.747 (5)	0.52 (8)*	0.5
H14	0.4085	0.0352	0.7188	0.618*	0.5
C15	0.458 (4)	−0.020 (2)	0.808 (4)	0.26 (3)*	0.5
H15	0.4845	−0.0005	0.8590	0.314*	0.5
N2	0.4366 (7)	−0.2265 (7)	0.8650 (10)	0.041 (4)*	0.5
C16	0.3878 (11)	−0.1918 (13)	0.8316 (19)	0.119 (12)*	0.5
H16	0.3500	−0.2163	0.8116	0.143*	0.5
C17	0.3850 (17)	−0.1233 (15)	0.822 (3)	0.27 (3)*	0.5
H17	0.3475	−0.1019	0.7957	0.326*	0.5
C18	0.4389 (17)	−0.0869 (14)	0.853 (3)	0.20 (3)*	0.5
C19	0.4937 (11)	−0.1221 (9)	0.8850 (15)	0.087 (7)*	0.5
H19	0.5348	−0.1005	0.8983	0.104*	0.5
C20	0.4851 (10)	−0.1898 (9)	0.8966 (16)	0.080 (8)*	0.5
H20	0.5179	−0.2124	0.9313	0.097*	0.5
N3	0.5640 (7)	0.5577 (7)	0.6508 (12)	0.037 (5)*	0.5
C21	0.5187 (10)	0.5165 (8)	0.6206 (13)	0.075 (9)*	0.5
H21	0.4849	0.5362	0.5844	0.090*	0.5
C22	0.5132 (10)	0.4491 (8)	0.6335 (14)	0.062 (5)*	0.5
H22	0.4799	0.4232	0.6041	0.074*	0.5
C23	0.5588 (9)	0.4204 (8)	0.6920 (14)	0.072 (6)*	0.5
C24	0.6110 (9)	0.4600 (8)	0.7212 (14)	0.066 (6)*	0.5
H24	0.6454	0.4426	0.7585	0.079*	0.5
C25	0.6107 (7)	0.5249 (7)	0.6940 (12)	0.037 (4)*	0.5
H25	0.6496	0.5500	0.7081	0.044*	0.5
C26	0.5450 (13)	0.3504 (11)	0.7280 (17)	0.121 (9)*	0.5
H26	0.5878	0.3304	0.7500	0.145*	0.5
C27	0.5011 (14)	0.2916 (14)	0.676 (2)	0.156 (12)*	0.5
H27	0.4837	0.3103	0.6184	0.187*	0.5
C28	0.5338 (18)	0.2218 (14)	0.657 (2)	0.128 (12)*	0.5
C29	0.5796 (18)	0.1781 (18)	0.679 (3)	0.72 (15)*	0.5
H29	0.6191	0.1958	0.7049	0.865*	0.5
C30	0.578 (2)	0.1098 (16)	0.668 (3)	0.164 (18)*	0.5
H30	0.6144	0.0820	0.6831	0.196*	0.5
C31	0.519 (3)	0.0840 (19)	0.635 (4)	0.27 (3)*	0.5
C32	0.470 (2)	0.127 (3)	0.605 (4)	0.30 (3)*	0.5
H32	0.4303	0.1115	0.5771	0.362*	0.5
C33	0.4824 (19)	0.194 (2)	0.618 (3)	0.25 (3)*	0.5
H33	0.4495	0.2238	0.5956	0.303*	0.5
C34	0.497 (4)	0.014 (2)	0.667 (3)	0.33 (4)*	0.5
H34	0.4679	−0.0081	0.6206	0.396*	0.5
C35	0.522 (5)	−0.042 (3)	0.743 (4)	0.81 (12)*	0.5
H35	0.5636	−0.0236	0.7715	0.972*	0.5
N4	0.5694 (18)	−0.2312 (15)	0.646 (2)	0.17 (2)*	0.5
C36	0.6030 (12)	−0.1964 (12)	0.7042 (19)	0.103 (9)*	0.5
H36	0.6366	−0.2192	0.7373	0.124*	0.5
C37	0.5941 (13)	−0.1292 (12)	0.7226 (19)	0.120 (9)*	0.5
H37	0.6206	−0.1066	0.7663	0.144*	0.5
C38	0.5452 (15)	−0.0963 (12)	0.675 (2)	0.111 (11)*	0.5
C39	0.508 (3)	−0.131 (2)	0.612 (5)	0.55 (9)*	0.5
H39	0.4730	−0.1103	0.5785	0.662*	0.5
C40	0.524 (2)	−0.197 (2)	0.603 (4)	0.28 (4)*	0.5
H40	0.4985	−0.2214	0.5599	0.333*	0.5
C41	0.5789 (4)	0.6670 (4)	0.8546 (6)	0.054 (2)
C42	0.6448 (3)	0.6686 (4)	0.8998 (6)	0.049 (2)
C43	0.6503 (4)	0.6678 (5)	0.9920 (6)	0.073 (3)
H43	0.6111	0.6666	1.0278	0.087*
C44	0.7115 (5)	0.6686 (6)	1.0335 (7)	0.088 (3)
H44	0.7142	0.6706	1.0975	0.106*
C45	0.7696 (4)	0.6667 (4)	0.9821 (7)	0.062 (2)
C46	0.7647 (4)	0.6670 (4)	0.8914 (7)	0.059 (2)
H46	0.8040	0.6676	0.8556	0.070*
C47	0.7020 (4)	0.6667 (5)	0.8497 (6)	0.066 (3)
H47	0.6992	0.6651	0.7858	0.079*
C48	0.8366 (5)	0.6644 (5)	1.0297 (9)	0.078 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0239 (5)	0.0662 (7)	0.0543 (6)	−0.0003 (4)	0.0028 (4)	0.0026 (5)
O1	0.027 (3)	0.091 (5)	0.078 (4)	−0.005 (3)	−0.004 (3)	0.000 (3)
O2	0.057 (4)	0.184 (9)	0.058 (4)	0.007 (4)	−0.018 (3)	−0.030 (5)
O3	0.053 (4)	0.112 (6)	0.107 (6)	0.008 (4)	−0.039 (4)	−0.014 (5)
O4	0.038 (4)	0.096 (5)	0.140 (7)	−0.006 (3)	−0.014 (4)	0.005 (5)
C41	0.040 (4)	0.061 (6)	0.060 (6)	0.001 (4)	−0.011 (4)	−0.012 (5)
C42	0.029 (4)	0.057 (5)	0.062 (5)	0.002 (4)	−0.003 (3)	−0.003 (4)
C43	0.036 (4)	0.129 (9)	0.054 (5)	0.010 (5)	−0.002 (4)	0.009 (6)
C44	0.045 (5)	0.154 (11)	0.065 (6)	0.000 (6)	−0.015 (5)	0.005 (6)
C45	0.032 (4)	0.070 (6)	0.085 (7)	0.004 (4)	−0.010 (4)	0.001 (5)
C46	0.027 (4)	0.061 (6)	0.089 (7)	0.004 (4)	0.012 (4)	−0.008 (5)
C47	0.037 (4)	0.093 (7)	0.067 (6)	−0.006 (4)	−0.004 (4)	−0.014 (5)
C48	0.038 (5)	0.067 (7)	0.129 (10)	−0.019 (5)	−0.020 (6)	−0.005 (7)

Geometric parameters (Å, º)

Zn1—O1	1.996 (5)	C16—C17	1.373 (17)
Zn1—O3^i	2.033 (7)	C17—C18	1.380 (18)
Zn1—O2^ii	2.036 (7)	C18—C19	1.387 (17)
Zn1—N1	2.189 (16)	C19—C20	1.372 (16)
Zn1—O4^i	2.466 (8)	N3—C21	1.305 (14)
Zn1—C48^i	2.555 (11)	N3—C25	1.309 (12)
O1—C41	1.283 (10)	C21—C22	1.362 (15)
O2—C41	1.180 (10)	C22—C23	1.384 (16)
O2—Zn1^ii	2.036 (7)	C23—C24	1.382 (16)
O3—C48	1.263 (13)	C23—C26	1.520 (19)
O3—Zn1^iii	2.033 (7)	C24—C25	1.355 (14)
O4—C48	1.214 (13)	C26—C27	1.65 (2)
O4—Zn1^iii	2.466 (8)	C27—C28	1.57 (2)
N1—C5	1.298 (14)	C28—C29	1.306 (16)
N1—C1	1.299 (13)	C28—C33	1.308 (16)
C1—C2	1.360 (14)	C29—C30	1.370 (17)
C2—C3	1.370 (16)	C30—C31	1.377 (18)
C3—C4	1.389 (16)	C31—C32	1.378 (18)
C3—C6	1.514 (18)	C31—C34	1.54 (2)
C4—C5	1.365 (15)	C32—C33	1.367 (17)
C6—C7	1.64 (2)	C34—C35	1.66 (2)
C6—C26	1.66 (2)	C35—C38	1.54 (2)
C7—C8	1.55 (2)	N4—C36	1.301 (15)
C7—C27	1.68 (2)	N4—C40	1.303 (16)
C8—C13	1.295 (16)	C36—C37	1.379 (16)
C8—C9	1.302 (16)	C37—C38	1.377 (17)
C9—C10	1.370 (17)	C38—C39	1.379 (18)
C10—C11	1.384 (18)	C39—C40	1.365 (17)
C11—C12	1.381 (18)	C41—C42	1.484 (11)
C11—C14	1.54 (2)	C42—C47	1.367 (11)
C12—C13	1.365 (17)	C42—C43	1.370 (11)
C14—C15	1.66 (2)	C43—C44	1.373 (13)
C14—C34	1.67 (2)	C44—C45	1.393 (13)
C15—C18	1.55 (2)	C45—C46	1.348 (12)
C15—C35	1.67 (2)	C45—C48	1.518 (12)
N2—C16	1.298 (15)	C46—C47	1.402 (11)
N2—C20	1.303 (14)	C48—Zn1^iii	2.555 (10)
O1—Zn1—O3^i	149.7 (3)	N2—C20—C19	127.0 (16)
O1—Zn1—O2^ii	116.1 (3)	C21—N3—C25	110.6 (14)
O3^i—Zn1—O2^ii	94.0 (3)	N3—C21—C22	129.1 (17)
O1—Zn1—N1	89.5 (5)	C21—C22—C23	116.2 (15)
O3^i—Zn1—N1	91.8 (5)	C24—C23—C22	117.5 (14)
O2^ii—Zn1—N1	93.7 (6)	C24—C23—C26	123.5 (16)
O1—Zn1—O4^i	92.7 (3)	C22—C23—C26	118.6 (18)
O3^i—Zn1—O4^i	57.1 (3)	C25—C24—C23	116.6 (15)
O2^ii—Zn1—O4^i	151.1 (3)	N3—C25—C24	128.7 (15)
N1—Zn1—O4^i	88.6 (5)	C23—C26—C27	126 (2)
O1—Zn1—C48^i	120.6 (3)	C23—C26—C6	112 (2)
O3^i—Zn1—C48^i	29.2 (3)	C27—C26—C6	89.6 (7)
O2^ii—Zn1—C48^i	123.2 (4)	C28—C27—C26	119 (3)
N1—Zn1—C48^i	89.4 (6)	C28—C27—C7	120 (3)
O4^i—Zn1—C48^i	27.9 (3)	C26—C27—C7	89.7 (7)
C41—O1—Zn1	121.5 (6)	C29—C28—C33	112 (2)
C41—O2—Zn1^ii	177.8 (7)	C29—C28—C27	147 (3)
C48—O3—Zn1^iii	99.0 (7)	C33—C28—C27	97 (3)
C48—O4—Zn1^iii	80.1 (7)	C28—C29—C30	128 (2)
C5—N1—C1	112.9 (16)	C29—C30—C31	116 (2)
C5—N1—Zn1	124.5 (14)	C30—C31—C32	119 (2)
C1—N1—Zn1	120.2 (12)	C30—C31—C34	118 (5)
N1—C1—C2	127.2 (17)	C32—C31—C34	118 (5)
C1—C2—C3	117.8 (16)	C33—C32—C31	116 (2)
C2—C3—C4	117.7 (14)	C28—C33—C32	128 (2)
C2—C3—C6	115.7 (15)	C31—C34—C35	137 (6)
C4—C3—C6	125.2 (16)	C31—C34—C14	89 (4)
C5—C4—C3	116.1 (15)	C35—C34—C14	88.6 (10)
N1—C5—C4	128.2 (19)	C38—C35—C34	97 (4)
C3—C6—C7	119 (2)	C38—C35—C15	142 (8)
C3—C6—C26	116.7 (18)	C34—C35—C15	88.7 (10)
C7—C6—C26	90.6 (7)	C36—N4—C40	114 (2)
C8—C7—C6	114 (2)	N4—C36—C37	125.8 (19)
C8—C7—C27	114 (3)	C38—C37—C36	117.0 (17)
C6—C7—C27	89.3 (7)	C37—C38—C39	120 (2)
C13—C8—C9	112 (2)	C37—C38—C35	102 (3)
C13—C8—C7	111 (3)	C39—C38—C35	129 (5)
C9—C8—C7	131 (3)	C40—C39—C38	115 (2)
C8—C9—C10	132 (2)	N4—C40—C39	129 (2)
C9—C10—C11	113.4 (19)	O2—C41—O1	124.4 (8)
C12—C11—C10	118 (2)	O2—C41—C42	120.7 (8)
C12—C11—C14	104 (4)	O1—C41—C42	114.9 (8)
C10—C11—C14	109 (5)	C47—C42—C43	118.3 (7)
C13—C12—C11	120 (2)	C47—C42—C41	120.1 (8)
C8—C13—C12	125 (2)	C43—C42—C41	121.5 (8)
C11—C14—C15	97 (4)	C42—C43—C44	121.2 (9)
C11—C14—C34	171 (6)	C43—C44—C45	120.2 (9)
C15—C14—C34	88.8 (10)	C46—C45—C44	118.9 (8)
C18—C15—C14	160 (6)	C46—C45—C48	121.8 (9)
C18—C15—C35	102 (5)	C44—C45—C48	119.3 (9)
C14—C15—C35	88.5 (10)	C45—C46—C47	120.3 (8)
C16—N2—C20	113.7 (16)	C42—C47—C46	120.9 (8)
N2—C16—C17	126.8 (19)	O4—C48—O3	123.7 (10)
C16—C17—C18	117 (2)	O4—C48—C45	119.5 (11)
C17—C18—C19	118 (2)	O3—C48—C45	116.7 (10)
C17—C18—C15	121 (4)	O4—C48—Zn1^iii	72.0 (6)
C19—C18—C15	113 (4)	O3—C48—Zn1^iii	51.8 (5)
C20—C19—C18	116.1 (17)	C45—C48—Zn1^iii	168.4 (9)

Symmetry codes: (i) x−1/2, y, −z+2; (ii) −x+1, y, −z+3/2; (iii) x+1/2, y, −z+2.

 

(6)

Crystal data

C56H40N4O8Zn2	F(000) = 4224
Mr = 1027.66	Dx = 1.192 Mg m^−3
Monoclinic, C2/c	Mo Kαlpha radiation, λ = 0.71073 Å
a = 27.430 (2) Å	Cell parameters from 5473 reflections
b = 29.305 (2) Å	θ = 2.2–28.3°
c = 14.9087 (11) Å	µ = 0.89 mm^−1
β = 107.070 (5)°	T = 173 K
V = 11456.2 (16) Å^3	Plate, yellow
Z = 8	0.45 × 0.13 × 0.08 mm

Data collection

Bruker APEX-II CCD diffractometer	6657 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.092
Absorption correction: multi-scan SADABS (Sheldrick, 2011)	θmax = 26.5°, θmin = 1.4°
Tmin = 0.702, Tmax = 0.937	h = −30→34
50356 measured reflections	k = −36→32
11878 independent reflections	l = −18→18

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.086	w = 1/[σ^2(Fo^2) + (0.1042P)^2 + 43.8779P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.238	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.73 e Å^−3
11878 reflections	Δρmin = −0.71 e Å^−3
605 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
85 restraints	Extinction coefficient: 0.00013 (5)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Initially refinement was attempted with normal data with R(int) = 0.1078. Due to high agreement factors and problem in completing satisfactory refinements of the structural model, SQUEEZEd data was used. The refinement is marred by the disorder created by the partial dimerization. Only one of the two olefin bonds was found to form cyclobutane ring. The dimerized fragment (C8a - C40a) was included in the refinement. A common occupancy factor was refined to 0.610 (6). Only isotropic thermal parameters were refined for these "disordered" fragments, as anisotropic refinement failed. Even though the geometry of the rings were confined to hexagon using FLAT, SADI and SAME options they were not strictly maintained in some cases. However, the agreement factors are better than the unsqueezed data and hence reported here. Although the bond distances and angles are not very accurate for a detailed comparison, partial single dimerization photoreaction is proved beyond any doubt.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.35888 (3)	0.11982 (3)	0.36020 (5)	0.0497 (3)
Zn2	0.38071 (3)	0.11393 (2)	0.64715 (5)	0.0352 (2)
O1	0.40609 (17)	0.09055 (16)	0.4745 (3)	0.0568 (13)
O2	0.42725 (15)	0.06664 (13)	0.6188 (3)	0.0417 (10)
O3	0.31447 (17)	0.16602 (15)	0.3973 (3)	0.0527 (12)
O4	0.32509 (16)	0.14580 (14)	0.5441 (3)	0.0455 (10)
O5	0.33097 (19)	0.13939 (18)	0.2168 (3)	0.0649 (14)
O6	0.39190 (18)	0.08752 (16)	0.2499 (3)	0.0569 (12)
O7	0.3465 (2)	0.1621 (3)	0.7626 (4)	0.096 (2)
O8	0.4033 (2)	0.10638 (19)	0.7890 (3)	0.0759 (17)
N1	0.4192 (2)	0.17021 (19)	0.3738 (4)	0.0543 (15)
C1	0.4678 (3)	0.1593 (3)	0.3806 (5)	0.0586 (18)
H1	0.4763	0.1278	0.3848	0.070*
C2	0.5052 (3)	0.1885 (3)	0.3819 (5)	0.069 (2)
H2	0.5384	0.1774	0.3861	0.083*
C3	0.4961 (4)	0.2347 (3)	0.3771 (6)	0.077 (2)
C4	0.4484 (4)	0.2469 (3)	0.3765 (7)	0.099 (3)
H4	0.4407	0.2783	0.3798	0.118*
C5	0.4104 (4)	0.2150 (3)	0.3712 (6)	0.079 (2)
H5	0.3768	0.2255	0.3656	0.095*
C6	0.5330 (4)	0.2700 (4)	0.3732 (8)	0.114 (4)
H6	0.5234	0.3007	0.3800	0.137*
C7	0.5794 (4)	0.2635 (4)	0.3608 (7)	0.107 (3)
H7	0.5896	0.2330	0.3537	0.128*
C8	0.6158 (5)	0.3008 (4)	0.3575 (6)	0.055 (3)*	0.610 (6)
C9	0.6619 (7)	0.2899 (7)	0.3382 (13)	0.115 (6)*	0.610 (6)
H9	0.6707	0.2593	0.3292	0.138*	0.610 (6)
C10	0.6954 (8)	0.3277 (7)	0.3325 (15)	0.145 (8)*	0.610 (6)
H10	0.7244	0.3219	0.3115	0.174*	0.610 (6)
C11	0.6862 (6)	0.3734 (6)	0.3575 (13)	0.094 (5)*	0.610 (6)
C12	0.6356 (6)	0.3813 (5)	0.3608 (11)	0.083 (5)*	0.610 (6)
H12	0.6235	0.4119	0.3534	0.100*	0.610 (6)
C13	0.6003 (10)	0.3457 (8)	0.3747 (19)	0.186 (13)*	0.610 (6)
H13	0.5707	0.3519	0.3931	0.224*	0.610 (6)
C14	0.7212 (7)	0.4077 (6)	0.3465 (12)	0.101 (5)*	0.610 (6)
H14	0.7520	0.3985	0.3348	0.122*	0.610 (6)
C15	0.7120 (7)	0.4524 (6)	0.3522 (11)	0.115 (6)*	0.610 (6)
H15	0.6794	0.4606	0.3572	0.138*	0.610 (6)
N2	0.8119 (4)	0.5678 (4)	0.3481 (6)	0.049 (3)*	0.610 (6)
C16	0.8284 (6)	0.5229 (4)	0.3546 (8)	0.062 (4)*	0.610 (6)
H16	0.8633	0.5175	0.3606	0.075*	0.610 (6)
C17	0.7979 (5)	0.4855 (5)	0.3529 (8)	0.068 (4)*	0.610 (6)
H17	0.8116	0.4557	0.3527	0.082*	0.610 (6)
C18	0.7486 (5)	0.4907 (5)	0.3515 (9)	0.078 (4)*	0.610 (6)
C19	0.7293 (8)	0.5341 (7)	0.3433 (12)	0.129 (8)*	0.610 (6)
H19	0.6946	0.5393	0.3398	0.155*	0.610 (6)
C20	0.7607 (7)	0.5699 (7)	0.3403 (12)	0.114 (9)*	0.610 (6)
H20	0.7455	0.5994	0.3319	0.137*	0.610 (6)
N3	0.43078 (19)	0.16878 (16)	0.6424 (3)	0.0371 (11)
C21	0.4780 (2)	0.1614 (2)	0.6374 (4)	0.0398 (14)
H21	0.4900	0.1309	0.6409	0.048*
C22	0.5101 (2)	0.1961 (2)	0.6272 (4)	0.0444 (15)
H22	0.5431	0.1889	0.6229	0.053*
C23	0.4949 (3)	0.2409 (2)	0.6234 (4)	0.0527 (18)
C24	0.4455 (3)	0.2483 (2)	0.6277 (5)	0.0566 (19)
H24	0.4325	0.2785	0.6246	0.068*
C25	0.4156 (2)	0.2121 (2)	0.6363 (4)	0.0466 (16)
H25	0.3819	0.2183	0.6380	0.056*
C26	0.5259 (3)	0.2795 (3)	0.6151 (6)	0.081 (3)
H26	0.5099	0.3079	0.5938	0.098*
C27	0.5774 (3)	0.2761 (3)	0.6371 (5)	0.078 (3)
H27	0.5929	0.2472	0.6544	0.094*
C28	0.6100 (6)	0.3155 (6)	0.6350 (6)	0.063 (5)*	0.610 (6)
C29	0.6617 (6)	0.3078 (5)	0.6653 (10)	0.058 (4)*	0.610 (6)
H29	0.6737	0.2783	0.6873	0.070*	0.610 (6)
C30	0.6964 (5)	0.3409 (5)	0.6650 (10)	0.065 (4)*	0.610 (6)
H30	0.7320	0.3351	0.6852	0.079*	0.610 (6)
C31	0.6770 (4)	0.3832 (4)	0.6337 (10)	0.060 (3)*	0.610 (6)
C32	0.6266 (5)	0.3933 (5)	0.6072 (11)	0.079 (4)*	0.610 (6)
H32	0.6147	0.4228	0.5844	0.095*	0.610 (6)
C33	0.5936 (5)	0.3599 (5)	0.6143 (10)	0.068 (4)*	0.610 (6)
H33	0.5587	0.3671	0.6050	0.082*	0.610 (6)
C34	0.7145 (5)	0.4190 (4)	0.6294 (9)	0.071 (4)*	0.610 (6)
H34	0.7491	0.4099	0.6413	0.085*	0.610 (6)
C35	0.7035 (6)	0.4632 (4)	0.6100 (9)	0.083 (4)*	0.610 (6)
H35	0.6689	0.4726	0.5921	0.100*	0.610 (6)
N4	0.8204 (3)	0.5619 (3)	0.6264 (6)	0.034 (3)*	0.610 (6)
C36	0.8290 (4)	0.5182 (4)	0.6224 (7)	0.042 (3)*	0.610 (6)
H36	0.8619	0.5081	0.6222	0.051*	0.610 (6)
C37	0.7923 (6)	0.4873 (6)	0.6185 (10)	0.054 (6)*	0.610 (6)
H37	0.8004	0.4558	0.6176	0.064*	0.610 (6)
C38	0.7453 (5)	0.4991 (4)	0.6159 (8)	0.053 (3)*	0.610 (6)
C39	0.7367 (4)	0.5439 (4)	0.6221 (8)	0.045 (3)*	0.610 (6)
H39	0.7036	0.5540	0.6207	0.054*	0.610 (6)
C40	0.7738 (4)	0.5749 (4)	0.6304 (9)	0.039 (4)*	0.610 (6)
H40	0.7673	0.6061	0.6391	0.047*	0.610 (6)
C41	0.4294 (2)	0.06515 (17)	0.5374 (4)	0.0317 (12)
C42	0.30854 (19)	0.17142 (19)	0.4763 (4)	0.0335 (13)
C43	0.2559 (2)	0.2402 (2)	0.4140 (4)	0.0372 (14)
H43	0.2594	0.2331	0.3540	0.045*
C44	0.27810 (19)	0.21240 (18)	0.4886 (3)	0.0283 (12)
C45	0.2715 (2)	0.2216 (2)	0.5756 (4)	0.0373 (14)
H45	0.2856	0.2019	0.6274	0.045*
C46	0.4977 (2)	0.00602 (19)	0.5898 (4)	0.0339 (13)
H46	0.4958	0.0100	0.6519	0.041*
C47	0.46626 (19)	0.03103 (16)	0.5179 (4)	0.0266 (11)
C48	0.4681 (2)	0.02454 (19)	0.4264 (4)	0.0348 (13)
H48	0.4459	0.0411	0.3760	0.042*
C49	0.3636 (2)	0.1148 (2)	0.1958 (4)	0.0486 (16)
C50	0.3750 (3)	0.1331 (3)	0.8143 (5)	0.063 (2)
C51	0.3402 (2)	0.1538 (2)	0.0395 (4)	0.0448 (15)
H51	0.3189	0.1735	0.0618	0.054*
C52	0.3687 (2)	0.1203 (2)	0.0975 (4)	0.0376 (14)
C53	0.3995 (2)	0.0918 (2)	0.0649 (4)	0.0377 (14)
H53	0.4189	0.0688	0.1045	0.045*
C54	0.4020 (2)	0.0967 (2)	0.9744 (4)	0.0435 (15)
H54	0.4236	0.0772	0.9522	0.052*
C55	0.3737 (2)	0.1296 (2)	0.9156 (4)	0.0425 (15)
C56	0.3433 (2)	0.1583 (2)	0.9473 (4)	0.0496 (17)
H56	0.3242	0.1813	0.9072	0.060*
C8A	0.615 (3)	0.311 (3)	0.365 (2)	0.34 (5)*	0.390 (6)
C9A	0.6585 (8)	0.2936 (7)	0.3977 (14)	0.072 (6)*	0.390 (6)
H9A	0.6653	0.2622	0.4118	0.086*	0.390 (6)
C10A	0.6939 (8)	0.3272 (6)	0.4100 (13)	0.063 (5)*	0.390 (6)
H10A	0.7295	0.3216	0.4250	0.076*	0.390 (6)
C11A	0.6732 (8)	0.3701 (6)	0.3985 (14)	0.058 (5)*	0.390 (6)
C12A	0.6241 (15)	0.3820 (13)	0.349 (4)	0.38 (6)*	0.390 (6)
H12A	0.6141	0.4125	0.3307	0.461*	0.390 (6)
C13A	0.5912 (9)	0.3460 (8)	0.3272 (18)	0.078 (7)*	0.390 (6)
H13A	0.5564	0.3471	0.2908	0.094*	0.390 (6)
C14A	0.7164 (8)	0.4069 (6)	0.4474 (12)	0.072 (6)*	0.390 (6)
H14A	0.7502	0.3993	0.4388	0.086*	0.390 (6)
C15A	0.7026 (8)	0.4589 (6)	0.4303 (12)	0.074 (6)*	0.390 (6)
H15A	0.6666	0.4629	0.3902	0.089*	0.390 (6)
N2A	0.8022 (5)	0.5558 (5)	0.3554 (8)	0.034 (4)*	0.390 (6)
C16A	0.8155 (7)	0.5150 (6)	0.3701 (10)	0.045 (5)*	0.390 (6)
H16A	0.8482	0.5065	0.3662	0.054*	0.390 (6)
C17A	0.7847 (6)	0.4812 (5)	0.3921 (10)	0.045 (4)*	0.390 (6)
H17A	0.7976	0.4510	0.4031	0.054*	0.390 (6)
C18A	0.7379 (6)	0.4895 (6)	0.3983 (11)	0.057 (5)*	0.390 (6)
C19A	0.7286 (7)	0.5333 (6)	0.3840 (12)	0.051 (5)*	0.390 (6)
H19A	0.6960	0.5433	0.3862	0.061*	0.390 (6)
C20A	0.7607 (7)	0.5673 (7)	0.3659 (14)	0.049 (5)*	0.390 (6)
H20A	0.7508	0.5985	0.3619	0.059*	0.390 (6)
C28A	0.6152 (9)	0.3119 (8)	0.6185 (8)	0.057 (7)*	0.390 (6)
C29A	0.6676 (8)	0.3036 (7)	0.6431 (14)	0.050 (6)*	0.390 (6)
H29A	0.6814	0.2751	0.6683	0.060*	0.390 (6)
C30A	0.6991 (8)	0.3387 (7)	0.6293 (16)	0.067 (7)*	0.390 (6)
H30A	0.7348	0.3331	0.6488	0.080*	0.390 (6)
C31A	0.6831 (6)	0.3814 (6)	0.5896 (14)	0.056 (5)*	0.390 (6)
C32A	0.6298 (7)	0.3861 (7)	0.5625 (15)	0.066 (6)*	0.390 (6)
H32A	0.6159	0.4139	0.5334	0.079*	0.390 (6)
C33A	0.5960 (6)	0.3532 (5)	0.5750 (12)	0.041 (4)*	0.390 (6)
H33A	0.5603	0.3586	0.5543	0.049*	0.390 (6)
C34A	0.7188 (8)	0.4110 (6)	0.5558 (13)	0.066 (5)*	0.390 (6)
H34A	0.7546	0.4066	0.5964	0.080*	0.390 (6)
C35A	0.7064 (9)	0.4628 (6)	0.5412 (12)	0.078 (6)*	0.390 (6)
H35A	0.6738	0.4720	0.5533	0.093*	0.390 (6)
N4A	0.8257 (6)	0.5652 (5)	0.6546 (10)	0.038 (4)*	0.390 (6)
C36A	0.7752 (11)	0.5722 (10)	0.6161 (15)	0.112 (17)*	0.390 (6)
H36A	0.7642	0.6030	0.6119	0.134*	0.390 (6)
C37A	0.7352 (8)	0.5378 (6)	0.5800 (13)	0.062 (6)*	0.390 (6)
H37A	0.7006	0.5466	0.5538	0.074*	0.390 (6)
C38A	0.7492 (6)	0.4921 (5)	0.5850 (10)	0.032 (4)*	0.390 (6)
C39A	0.8008 (9)	0.4828 (9)	0.6188 (15)	0.057 (11)*	0.390 (6)
H39A	0.8133	0.4526	0.6184	0.068*	0.390 (6)
C40A	0.8357 (6)	0.5207 (5)	0.6551 (11)	0.028 (4)*	0.390 (6)
H40A	0.8703	0.5125	0.6830	0.034*	0.390 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0631 (5)	0.0617 (5)	0.0292 (4)	0.0353 (4)	0.0215 (3)	0.0027 (3)
Zn2	0.0431 (4)	0.0339 (4)	0.0357 (4)	0.0114 (3)	0.0227 (3)	0.0030 (3)
O1	0.052 (3)	0.063 (3)	0.051 (3)	0.036 (2)	0.009 (2)	−0.003 (2)
O2	0.053 (3)	0.037 (2)	0.049 (3)	0.0067 (19)	0.038 (2)	−0.0021 (19)
O3	0.063 (3)	0.065 (3)	0.038 (2)	0.037 (2)	0.028 (2)	0.003 (2)
O4	0.047 (3)	0.045 (3)	0.048 (3)	0.012 (2)	0.020 (2)	0.008 (2)
O5	0.071 (3)	0.097 (4)	0.037 (3)	0.024 (3)	0.033 (2)	−0.003 (3)
O6	0.072 (3)	0.069 (3)	0.030 (2)	0.014 (3)	0.016 (2)	0.011 (2)
O7	0.083 (4)	0.166 (6)	0.040 (3)	−0.012 (4)	0.020 (3)	0.041 (4)
O8	0.113 (5)	0.088 (4)	0.051 (3)	−0.038 (3)	0.063 (3)	−0.015 (3)
N1	0.064 (4)	0.058 (4)	0.049 (3)	0.017 (3)	0.029 (3)	−0.005 (3)
C1	0.065 (5)	0.056 (4)	0.055 (4)	0.009 (4)	0.020 (4)	−0.001 (3)
C2	0.071 (6)	0.073 (6)	0.058 (5)	−0.006 (4)	0.010 (4)	0.007 (4)
C3	0.089 (7)	0.067 (6)	0.067 (6)	0.003 (5)	0.014 (5)	0.006 (4)
C4	0.137 (10)	0.051 (5)	0.134 (9)	0.012 (6)	0.080 (8)	0.014 (5)
C5	0.096 (7)	0.066 (6)	0.089 (6)	0.023 (5)	0.048 (5)	0.015 (5)
C6	0.081 (7)	0.122 (9)	0.145 (11)	−0.022 (7)	0.044 (7)	−0.012 (8)
C7	0.118 (9)	0.090 (7)	0.100 (8)	−0.016 (7)	0.014 (7)	0.002 (6)
N3	0.050 (3)	0.036 (3)	0.025 (2)	0.007 (2)	0.010 (2)	0.001 (2)
C21	0.047 (4)	0.044 (4)	0.026 (3)	0.002 (3)	0.007 (3)	−0.004 (3)
C22	0.038 (3)	0.052 (4)	0.040 (4)	0.003 (3)	0.008 (3)	−0.001 (3)
C23	0.053 (5)	0.051 (4)	0.044 (4)	−0.008 (3)	−0.001 (3)	−0.001 (3)
C24	0.048 (4)	0.034 (4)	0.075 (5)	0.006 (3)	−0.002 (4)	−0.003 (3)
C25	0.046 (4)	0.043 (4)	0.048 (4)	0.009 (3)	0.008 (3)	0.001 (3)
C26	0.056 (5)	0.078 (6)	0.100 (7)	−0.016 (4)	0.006 (5)	0.021 (5)
C27	0.082 (6)	0.069 (5)	0.070 (5)	−0.019 (5)	0.000 (5)	0.014 (4)
C41	0.025 (3)	0.025 (3)	0.049 (4)	−0.003 (2)	0.018 (3)	−0.004 (3)
C42	0.022 (3)	0.038 (3)	0.039 (3)	0.007 (2)	0.007 (2)	0.002 (3)
C43	0.032 (3)	0.054 (4)	0.030 (3)	0.011 (3)	0.014 (2)	−0.001 (3)
C44	0.026 (3)	0.042 (3)	0.021 (3)	0.005 (2)	0.014 (2)	−0.001 (2)
C45	0.041 (3)	0.044 (3)	0.029 (3)	0.010 (3)	0.015 (3)	0.007 (3)
C46	0.044 (3)	0.038 (3)	0.028 (3)	0.001 (3)	0.022 (3)	0.000 (2)
C47	0.028 (3)	0.023 (3)	0.034 (3)	−0.002 (2)	0.016 (2)	−0.008 (2)
C48	0.040 (3)	0.038 (3)	0.029 (3)	0.005 (3)	0.013 (2)	0.001 (2)
C49	0.048 (4)	0.066 (4)	0.036 (3)	0.012 (3)	0.020 (3)	−0.008 (3)
C50	0.062 (5)	0.097 (6)	0.035 (4)	−0.036 (5)	0.021 (4)	0.001 (4)
C51	0.046 (4)	0.055 (4)	0.041 (3)	0.010 (3)	0.024 (3)	−0.004 (3)
C52	0.028 (3)	0.054 (4)	0.032 (3)	0.005 (3)	0.011 (2)	−0.001 (3)
C53	0.043 (3)	0.038 (3)	0.033 (3)	0.006 (3)	0.012 (3)	0.003 (3)
C54	0.052 (4)	0.045 (4)	0.043 (4)	−0.010 (3)	0.028 (3)	−0.004 (3)
C55	0.036 (3)	0.060 (4)	0.034 (3)	−0.003 (3)	0.013 (3)	−0.003 (3)
C56	0.055 (4)	0.050 (4)	0.043 (4)	0.014 (3)	0.012 (3)	0.025 (3)

Geometric parameters (Å, º)

Zn1—N2^i	1.970 (12)	C32—C33	1.360 (16)
Zn1—O3	2.004 (4)	C34—C35	1.342 (13)
Zn1—O1	2.005 (4)	C35—C38	1.539 (19)
Zn1—O5	2.128 (4)	N4—C36	1.308 (12)
Zn1—N1	2.183 (6)	N4—C40	1.351 (13)
Zn1—O6	2.301 (4)	N4—Zn2^ii	2.202 (10)
Zn1—N2A^i	2.424 (16)	C36—C37	1.342 (17)
Zn1—C49	2.497 (6)	C37—C38	1.325 (16)
Zn2—O2	2.011 (4)	C38—C39	1.341 (14)
Zn2—O8	2.034 (5)	C39—C40	1.342 (14)
Zn2—O4	2.045 (4)	C41—C47	1.509 (7)
Zn2—N4A^i	2.102 (16)	C42—C44	1.504 (7)
Zn2—N3	2.129 (5)	C43—C44	1.368 (7)
Zn2—N4^i	2.202 (10)	C43—C45^iii	1.383 (8)
O1—C41	1.221 (7)	C44—C45	1.389 (7)
O2—C41	1.233 (6)	C45—C43^iii	1.383 (8)
O3—C42	1.246 (7)	C46—C48^iv	1.368 (7)
O4—C42	1.234 (6)	C46—C47	1.374 (7)
O5—C49	1.258 (7)	C47—C48	1.393 (7)
O6—C49	1.235 (7)	C48—C46^iv	1.368 (7)
O7—C50	1.254 (10)	C49—C52	1.521 (8)
O8—C50	1.237 (10)	C50—C55	1.525 (9)
N1—C5	1.335 (9)	C51—C52	1.387 (8)
N1—C1	1.346 (9)	C51—C56^v	1.408 (8)
C1—C2	1.332 (10)	C52—C53	1.374 (8)
C2—C3	1.374 (11)	C53—C54^v	1.379 (8)
C3—C4	1.353 (12)	C54—C55	1.378 (9)
C3—C6	1.461 (13)	C54—C53^vi	1.379 (8)
C4—C5	1.384 (12)	C55—C56	1.363 (9)
C6—C7	1.354 (11)	C56—C51^vi	1.408 (8)
C7—C8	1.490 (18)	C8A—C9A	1.25 (4)
C7—C8A	1.70 (11)	C8A—C13A	1.26 (4)
C8—C9	1.41 (2)	C9A—C10A	1.36 (3)
C8—C13	1.43 (2)	C10A—C11A	1.37 (2)
C9—C10	1.46 (2)	C11A—C12A	1.38 (3)
C10—C11	1.432 (19)	C11A—C14A	1.61 (3)
C11—C12	1.421 (18)	C12A—C13A	1.37 (3)
C11—C14	1.43 (2)	C14A—C15A	1.574 (18)
C12—C13	1.48 (2)	C14A—C34A	1.601 (18)
C14—C15	1.340 (14)	C15A—C18A	1.50 (3)
C15—C18	1.51 (2)	C15A—C35A	1.629 (18)
N2—C20	1.376 (18)	N2A—C20A	1.240 (19)
N2—C16	1.388 (15)	N2A—C16A	1.249 (18)
N2—Zn1^ii	1.970 (12)	N2A—Zn1^ii	2.424 (16)
C16—C17	1.372 (17)	C16A—C17A	1.40 (2)
C17—C18	1.356 (16)	C17A—C18A	1.334 (19)
C18—C19	1.368 (17)	C18A—C19A	1.314 (19)
C19—C20	1.37 (2)	C19A—C20A	1.41 (2)
N3—C25	1.332 (7)	C28A—C29A	1.40 (2)
N3—C21	1.336 (7)	C28A—C33A	1.40 (2)
C21—C22	1.383 (8)	C29A—C30A	1.40 (2)
C22—C23	1.373 (9)	C30A—C31A	1.40 (2)
C23—C24	1.394 (9)	C31A—C32A	1.40 (2)
C23—C26	1.442 (10)	C31A—C34A	1.50 (3)
C24—C25	1.370 (9)	C32A—C33A	1.39 (2)
C26—C27	1.357 (10)	C34A—C35A	1.557 (18)
C27—C28	1.47 (2)	C35A—C38A	1.45 (3)
C27—C28A	1.56 (3)	N4A—C40A	1.332 (19)
C28—C29	1.376 (16)	N4A—C36A	1.35 (2)
C28—C33	1.380 (16)	N4A—Zn2^ii	2.102 (16)
C29—C30	1.358 (16)	C36A—C37A	1.47 (3)
C30—C31	1.376 (14)	C37A—C38A	1.39 (2)
C31—C32	1.356 (14)	C38A—C39A	1.38 (2)
C31—C34	1.483 (18)	C39A—C40A	1.46 (3)
N2^i—Zn1—O3	96.5 (3)	C30—C31—C34	116.6 (11)
N2^i—Zn1—O1	89.4 (3)	C31—C32—C33	117.8 (13)
O3—Zn1—O1	110.35 (17)	C32—C33—C28	121.0 (14)
N2^i—Zn1—O5	94.8 (3)	C35—C34—C31	125.2 (13)
O3—Zn1—O5	91.52 (17)	C34—C35—C38	122.1 (13)
O1—Zn1—O5	157.15 (17)	C36—N4—C40	117.5 (10)
N2^i—Zn1—N1	171.9 (3)	C36—N4—Zn2^ii	123.1 (7)
O3—Zn1—N1	91.3 (2)	C40—N4—Zn2^ii	118.7 (7)
O1—Zn1—N1	85.8 (2)	N4—C36—C37	121.3 (12)
O5—Zn1—N1	87.2 (2)	C38—C37—C36	122.5 (15)
N2^i—Zn1—O6	90.1 (3)	C37—C38—C39	116.2 (14)
O3—Zn1—O6	150.87 (17)	C37—C38—C35	121.7 (12)
O1—Zn1—O6	98.03 (16)	C39—C38—C35	122.0 (11)
O5—Zn1—O6	59.59 (16)	C38—C39—C40	121.6 (11)
N1—Zn1—O6	84.13 (18)	C39—C40—N4	120.6 (11)
O3—Zn1—N2A^i	95.4 (3)	O1—C41—O2	124.6 (5)
O1—Zn1—N2A^i	86.7 (3)	O1—C41—C47	119.1 (5)
O5—Zn1—N2A^i	98.1 (3)	O2—C41—C47	116.2 (5)
N1—Zn1—N2A^i	171.3 (3)	O4—C42—O3	125.4 (5)
O6—Zn1—N2A^i	92.5 (3)	O4—C42—C44	118.0 (5)
N2^i—Zn1—C49	94.9 (3)	O3—C42—C44	116.6 (5)
O3—Zn1—C49	121.42 (19)	C44—C43—C45^iii	121.2 (5)
O1—Zn1—C49	127.06 (19)	C43—C44—C45	119.7 (5)
O5—Zn1—C49	30.24 (18)	C43—C44—C42	120.5 (5)
N1—Zn1—C49	82.8 (2)	C45—C44—C42	119.9 (5)
O6—Zn1—C49	29.49 (17)	C43^iii—C45—C44	119.1 (5)
N2A^i—Zn1—C49	98.2 (3)	C48^iv—C46—C47	121.2 (5)
O2—Zn2—O8	97.2 (2)	C46—C47—C48	119.7 (5)
O2—Zn2—O4	122.43 (17)	C46—C47—C41	120.4 (5)
O8—Zn2—O4	139.7 (2)	C48—C47—C41	119.9 (5)
O2—Zn2—N4A^i	93.0 (4)	C46^iv—C48—C47	119.1 (5)
O8—Zn2—N4A^i	82.9 (4)	O6—C49—O5	124.4 (6)
O4—Zn2—N4A^i	87.8 (4)	O6—C49—C52	118.7 (5)
O2—Zn2—N3	93.31 (17)	O5—C49—C52	116.9 (6)
O8—Zn2—N3	96.54 (18)	O6—C49—Zn1	66.4 (3)
O4—Zn2—N3	88.66 (17)	O5—C49—Zn1	58.4 (3)
O2—Zn2—N4^i	89.5 (2)	C52—C49—Zn1	170.2 (5)
O8—Zn2—N4^i	93.3 (3)	O8—C50—O7	125.2 (7)
O4—Zn2—N4^i	81.2 (2)	O8—C50—C55	117.3 (7)
N3—Zn2—N4^i	169.3 (2)	O7—C50—C55	117.5 (8)
C41—O1—Zn1	167.3 (4)	C52—C51—C56^v	119.4 (5)
C41—O2—Zn2	116.7 (4)	C53—C52—C51	120.1 (5)
C42—O3—Zn1	127.2 (4)	C53—C52—C49	121.1 (5)
C42—O4—Zn2	155.1 (4)	C51—C52—C49	118.8 (5)
C49—O5—Zn1	91.3 (4)	C52—C53—C54^v	119.6 (6)
C49—O6—Zn1	84.1 (4)	C55—C54—C53^vi	121.0 (6)
C50—O8—Zn2	102.8 (5)	C56—C55—C54	120.0 (6)
C5—N1—C1	113.8 (7)	C56—C55—C50	119.8 (6)
C5—N1—Zn1	122.4 (6)	C54—C55—C50	120.2 (6)
C1—N1—Zn1	123.7 (5)	C55—C56—C51^vi	119.9 (6)
C2—C1—N1	126.2 (7)	C9A—C8A—C13A	145 (10)
C1—C2—C3	120.2 (8)	C9A—C8A—C7	99 (5)
C4—C3—C2	114.9 (9)	C13A—C8A—C7	115 (6)
C4—C3—C6	119.6 (9)	C8A—C9A—C10A	108 (5)
C2—C3—C6	125.5 (9)	C9A—C10A—C11A	113.1 (19)
C3—C4—C5	122.2 (9)	C10A—C11A—C12A	127 (3)
N1—C5—C4	122.3 (8)	C10A—C11A—C14A	109.5 (16)
C7—C6—C3	126.6 (11)	C12A—C11A—C14A	123 (2)
C6—C7—C8	124.5 (11)	C13A—C12A—C11A	114 (3)
C6—C7—C8A	116.0 (13)	C8A—C13A—C12A	107 (5)
C9—C8—C13	125.0 (17)	C15A—C14A—C34A	91.6 (12)
C9—C8—C7	119.3 (12)	C15A—C14A—C11A	117.8 (16)
C13—C8—C7	115.6 (13)	C34A—C14A—C11A	108.3 (15)
C8—C9—C10	117.3 (16)	C18A—C15A—C14A	118.9 (16)
C11—C10—C9	122.1 (18)	C18A—C15A—C35A	115.3 (14)
C12—C11—C10	114.3 (17)	C14A—C15A—C35A	87.8 (12)
C12—C11—C14	125.7 (15)	C20A—N2A—C16A	118.0 (19)
C10—C11—C14	116.7 (16)	C20A—N2A—Zn1^ii	112.9 (11)
C11—C12—C13	125.1 (17)	C16A—N2A—Zn1^ii	125.7 (12)
C8—C13—C12	112.6 (18)	N2A—C16A—C17A	123.5 (17)
C15—C14—C11	122.2 (17)	C18A—C17A—C16A	122.9 (16)
C14—C15—C18	126.1 (17)	C19A—C18A—C17A	108.4 (18)
C20—N2—C16	110.6 (15)	C19A—C18A—C15A	121.4 (16)
C20—N2—Zn1^ii	126.7 (11)	C17A—C18A—C15A	129.6 (15)
C16—N2—Zn1^ii	122.4 (9)	C18A—C19A—C20A	128.2 (18)
C17—C16—N2	124.9 (13)	N2A—C20A—C19A	118.7 (17)
C18—C17—C16	120.6 (13)	C29A—C28A—C33A	119 (2)
C17—C18—C19	117.6 (16)	C28A—C29A—C30A	117.8 (19)
C17—C18—C15	125.4 (14)	C31A—C30A—C29A	126.1 (19)
C19—C18—C15	116.9 (14)	C30A—C31A—C32A	112.4 (19)
C20—C19—C18	119.1 (19)	C30A—C31A—C34A	120.3 (16)
C19—C20—N2	126.8 (19)	C32A—C31A—C34A	124.9 (16)
C25—N3—C21	116.1 (5)	C33A—C32A—C31A	124.9 (17)
C25—N3—Zn2	122.0 (4)	C32A—C33A—C28A	119.2 (18)
C21—N3—Zn2	121.7 (4)	C31A—C34A—C35A	118.2 (16)
N3—C21—C22	123.1 (6)	C31A—C34A—C14A	117.2 (16)
C23—C22—C21	120.9 (6)	C35A—C34A—C14A	89.4 (12)
C22—C23—C24	115.8 (6)	C38A—C35A—C34A	113.7 (16)
C22—C23—C26	125.1 (7)	C38A—C35A—C15A	107.6 (14)
C24—C23—C26	119.1 (7)	C34A—C35A—C15A	91.2 (12)
C25—C24—C23	120.1 (6)	C40A—N4A—C36A	109 (2)
N3—C25—C24	124.1 (6)	C40A—N4A—Zn2^ii	121.1 (11)
C27—C26—C23	121.3 (8)	C36A—N4A—Zn2^ii	122.5 (13)
C26—C27—C28	122.4 (9)	N4A—C36A—C37A	128 (2)
C29—C28—C33	117.7 (17)	C38A—C37A—C36A	118 (2)
C29—C28—C27	116.2 (12)	C39A—C38A—C37A	117 (2)
C33—C28—C27	125.8 (13)	C39A—C38A—C35A	130.9 (16)
C30—C29—C28	122.5 (14)	C37A—C38A—C35A	111.9 (15)
C29—C30—C31	116.3 (13)	C38A—C39A—C40A	118 (2)
C32—C31—C30	123.7 (14)	N4A—C40A—C39A	129.1 (17)
C32—C31—C34	119.7 (11)

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

 

(xtl4_sqd)

Crystal data

C56H40N4O8Zn2	Dx = 1.125 Mg m^−3
Mr = 1027.66	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pcca	Cell parameters from 9984 reflections
a = 20.030 (3) Å	θ = 2.3–27.3°
b = 20.005 (3) Å	µ = 0.84 mm^−1
c = 15.145 (2) Å	T = 173 K
V = 6068.8 (14) Å^3	Block, red
Z = 4	0.46 × 0.41 × 0.30 mm
F(000) = 2112

Data collection

Bruker APEX-II CCD diffractometer	3975 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.074
Absorption correction: multi-scan SADABS (Sheldrick, 2011)	θmax = 26.0°, θmin = 2.0°
Tmin = 0.703, Tmax = 0.801	h = −24→24
46693 measured reflections	k = −24→24
5979 independent reflections	l = −18→18

Refinement

Refinement on F^2	440 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.073	H-atom parameters constrained
wR(F^2) = 0.231	w = 1/[σ^2(Fo^2) + (0.1154P)^2 + 7.2582P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
5979 reflections	Δρmax = 0.91 e Å^−3
294 parameters	Δρmin = −0.72 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Crystallized in the orthorhombic space group Pcca with Z = 4. The asymmetric unit contains half of the formula unit. The dimer formed by dimerization of trans,cis,trans-bpeb disordered due to crystallographic centre of inversion. Due to this disorder soft constraints (FLAT, SAME, SADI) were used to retain the geometry of molecule. Only isotropic thermal parameter could be refined for these bpeb-dimer fragment. Again one DMF was disordered by crystallographic inversion centre. The rest of the electron densities were too complicated to resolve. Hence they were assigned as O atoms of water molecules. They could as well be highly disordered DMF.[Zn2(bdc)2(dimer)].DMF.6.5H2O. For uniformity, the referee suggested to squeeze the data and hence squeezed. The agreement factors of the squeezed better than the unsqueezed data.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.43270 (3)	0.66969 (2)	0.85781 (3)	0.0250 (2)
O1	0.52593 (15)	0.67007 (14)	0.9065 (2)	0.0355 (8)
O2	0.57615 (18)	0.67078 (17)	0.7764 (2)	0.0449 (9)
O3	0.8303 (2)	0.67234 (15)	1.1227 (3)	0.0521 (11)
O4	0.8841 (2)	0.67063 (16)	0.9961 (3)	0.0565 (11)
N1	0.4379 (6)	0.5644 (5)	0.8558 (8)	0.024 (4)*	0.5
C1	0.4867 (6)	0.5310 (5)	0.8977 (8)	0.034 (4)*	0.5
H1	0.5149	0.5556	0.9363	0.041*	0.5
C2	0.4988 (5)	0.4633 (4)	0.8886 (7)	0.029 (3)*	0.5
H2A	0.5336	0.4426	0.9212	0.035*	0.5
C3	0.4601 (5)	0.4260 (4)	0.8318 (7)	0.024 (2)*	0.5
C4	0.4064 (6)	0.4579 (4)	0.7932 (7)	0.030 (3)*	0.5
H4	0.3767	0.4339	0.7560	0.037*	0.5
C5	0.3963 (6)	0.5258 (5)	0.8095 (9)	0.033 (4)*	0.5
H5	0.3571	0.5459	0.7861	0.039*	0.5
C6	0.4863 (5)	0.3575 (4)	0.8109 (6)	0.033 (2)*	0.5
H6	0.5062	0.3358	0.8642	0.040*	0.5
C7	0.4391 (5)	0.3084 (5)	0.7602 (6)	0.043 (2)*	0.5
H7	0.3970	0.3321	0.7435	0.052*	0.5
C8	0.4224 (5)	0.2409 (5)	0.8006 (7)	0.051 (3)*	0.5
C9	0.4677 (6)	0.2060 (4)	0.8435 (6)	0.041 (2)*	0.5
H9	0.5039	0.2299	0.8690	0.049*	0.5
C10	0.4669 (6)	0.1379 (5)	0.8546 (7)	0.059 (3)*	0.5
H10	0.4991	0.1165	0.8909	0.071*	0.5
C11	0.4195 (7)	0.1021 (6)	0.8128 (10)	0.079 (4)*	0.5
C12	0.3664 (7)	0.1385 (5)	0.7824 (9)	0.073 (4)*	0.5
H12	0.3265	0.1159	0.7664	0.087*	0.5
C13	0.3694 (7)	0.2077 (5)	0.7745 (9)	0.079 (4)*	0.5
H13	0.3327	0.2312	0.7498	0.095*	0.5
C14	0.4371 (8)	0.0329 (8)	0.7736 (10)	0.108 (6)*	0.5
H14	0.3942	0.0089	0.7618	0.129*	0.5
C15	0.4872 (8)	−0.0191 (7)	0.8174 (10)	0.103 (6)*	0.5
H15	0.5116	0.0024	0.8676	0.123*	0.5
N2	0.4371 (5)	−0.2216 (4)	0.8662 (7)	0.027 (3)*	0.5
C16	0.3959 (6)	−0.1848 (5)	0.8195 (8)	0.045 (3)*	0.5
H16	0.3607	−0.2070	0.7893	0.054*	0.5
C17	0.4001 (7)	−0.1157 (6)	0.8108 (11)	0.084 (5)*	0.5
H17	0.3668	−0.0909	0.7804	0.101*	0.5
C18	0.4543 (6)	−0.0853 (5)	0.8480 (9)	0.058 (4)*	0.5
C19	0.4928 (6)	−0.1198 (5)	0.9043 (9)	0.058 (4)*	0.5
H19	0.5261	−0.0978	0.9383	0.070*	0.5
C20	0.4830 (6)	−0.1884 (5)	0.9119 (9)	0.041 (3)*	0.5
H20	0.5105	−0.2127	0.9516	0.050*	0.5
N3	0.5710 (6)	0.5599 (6)	0.6504 (8)	0.031 (5)*	0.5
C21	0.5219 (6)	0.5235 (5)	0.6137 (8)	0.038 (5)*	0.5
H21	0.4923	0.5442	0.5731	0.046*	0.5
C22	0.5134 (6)	0.4561 (5)	0.6339 (8)	0.040 (3)*	0.5
H22	0.4785	0.4316	0.6063	0.048*	0.5
C23	0.5551 (5)	0.4247 (4)	0.6936 (7)	0.033 (3)*	0.5
C24	0.6073 (6)	0.4620 (5)	0.7256 (8)	0.036 (3)*	0.5
H24	0.6403	0.4414	0.7615	0.043*	0.5
C25	0.6122 (6)	0.5296 (5)	0.7058 (8)	0.026 (3)*	0.5
H25	0.6465	0.5551	0.7331	0.031*	0.5
C26	0.5369 (5)	0.3566 (4)	0.7298 (6)	0.038 (2)*	0.5
H26	0.5784	0.3321	0.7471	0.045*	0.5
C27	0.4897 (5)	0.3085 (5)	0.6782 (6)	0.049 (3)*	0.5
H27	0.4694	0.3320	0.6265	0.059*	0.5
C28	0.5137 (7)	0.2388 (6)	0.6514 (9)	0.073 (4)*	0.5
C29	0.5648 (8)	0.2054 (7)	0.6847 (12)	0.099 (6)*	0.5
H29	0.6006	0.2289	0.7118	0.119*	0.5
C30	0.5661 (9)	0.1352 (8)	0.6801 (15)	0.126 (8)*	0.5
H30	0.6059	0.1125	0.6963	0.151*	0.5
C31	0.5126 (9)	0.0986 (7)	0.6532 (12)	0.106 (6)*	0.5
C32	0.4692 (10)	0.1341 (8)	0.6038 (14)	0.139 (7)*	0.5
H32	0.4394	0.1115	0.5653	0.166*	0.5
C33	0.4680 (8)	0.2029 (7)	0.6086 (11)	0.102 (5)*	0.5
H33	0.4326	0.2260	0.5799	0.122*	0.5
C34	0.4806 (8)	0.0313 (7)	0.6838 (9)	0.094 (5)*	0.5
H34	0.4560	0.0088	0.6347	0.113*	0.5
C35	0.5328 (8)	−0.0178 (7)	0.7296 (10)	0.107 (6)*	0.5
H35	0.5749	0.0074	0.7423	0.129*	0.5
N4	0.5664 (5)	−0.2225 (5)	0.6544 (7)	0.036 (3)*	0.5
C36	0.6065 (5)	−0.1894 (5)	0.7073 (8)	0.039 (3)*	0.5
H36	0.6414	−0.2130	0.7361	0.047*	0.5
C37	0.5999 (6)	−0.1224 (5)	0.7227 (9)	0.054 (3)*	0.5
H37	0.6314	−0.1010	0.7600	0.065*	0.5
C38	0.5507 (7)	−0.0856 (6)	0.6874 (10)	0.071 (4)*	0.5
C39	0.5090 (7)	−0.1163 (6)	0.6309 (10)	0.063 (4)*	0.5
H39	0.4745	−0.0925	0.6015	0.076*	0.5
C40	0.5186 (7)	−0.1851 (5)	0.6172 (9)	0.052 (4)*	0.5
H40	0.4886	−0.2070	0.5782	0.062*	0.5
C41	0.5766 (2)	0.67179 (19)	0.8582 (3)	0.0286 (11)
C42	0.6429 (2)	0.67537 (18)	0.9037 (3)	0.0260 (9)
C43	0.6469 (3)	0.6791 (2)	0.9952 (3)	0.0380 (11)
H43	0.6069	0.6816	1.0289	0.046*
C44	0.7073 (3)	0.6794 (2)	1.0380 (3)	0.0410 (12)
H44	0.7088	0.6828	1.1005	0.049*
C45	0.7657 (2)	0.67477 (19)	0.9908 (4)	0.0361 (11)
C46	0.7626 (2)	0.6705 (2)	0.8997 (3)	0.0361 (11)
H46	0.8027	0.6667	0.8666	0.043*
C47	0.7017 (3)	0.6716 (2)	0.8560 (3)	0.0353 (11)
H47	0.7004	0.6697	0.7933	0.042*
C48	0.8319 (3)	0.6726 (2)	1.0396 (4)	0.0469 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0203 (3)	0.0253 (3)	0.0296 (3)	0.0000 (2)	0.0023 (2)	0.00168 (18)
O1	0.0140 (16)	0.0446 (18)	0.048 (2)	−0.0013 (13)	0.0009 (16)	0.0029 (14)
O2	0.037 (2)	0.067 (2)	0.0299 (17)	0.0076 (17)	−0.0089 (16)	−0.0097 (15)
O3	0.054 (3)	0.0392 (19)	0.063 (2)	0.0023 (17)	−0.033 (2)	0.0006 (16)
O4	0.029 (2)	0.046 (2)	0.094 (3)	0.0004 (16)	−0.024 (2)	0.0005 (19)
C41	0.023 (3)	0.027 (2)	0.036 (3)	0.0016 (18)	−0.008 (2)	−0.0027 (18)
C42	0.018 (2)	0.025 (2)	0.035 (2)	−0.0003 (17)	−0.0058 (19)	−0.0030 (17)
C43	0.025 (3)	0.051 (3)	0.038 (3)	0.005 (2)	0.003 (2)	−0.004 (2)
C44	0.035 (3)	0.047 (3)	0.041 (3)	0.007 (2)	−0.015 (2)	−0.003 (2)
C45	0.024 (3)	0.027 (2)	0.057 (3)	−0.0028 (19)	−0.014 (2)	0.003 (2)
C46	0.023 (3)	0.033 (2)	0.053 (3)	0.0020 (19)	0.003 (2)	0.000 (2)
C47	0.026 (3)	0.048 (3)	0.032 (2)	−0.004 (2)	0.000 (2)	0.000 (2)
C48	0.031 (3)	0.023 (2)	0.086 (4)	−0.001 (2)	−0.020 (3)	0.001 (2)

Geometric parameters (Å, º)

Zn1—O1	2.008 (3)	C16—C17	1.391 (11)
Zn1—O2^i	2.040 (3)	C17—C18	1.366 (12)
Zn1—O3^ii	2.073 (4)	C18—C19	1.341 (12)
Zn1—N1	2.110 (10)	C19—C20	1.391 (10)
Zn1—O4^ii	2.418 (4)	N3—C25	1.324 (11)
Zn1—C48^ii	2.548 (6)	N3—C21	1.344 (11)
O1—C41	1.253 (6)	C21—C22	1.392 (11)
O2—C41	1.239 (5)	C22—C23	1.384 (11)
O2—Zn1^i	2.040 (3)	C23—C24	1.372 (11)
O3—C48	1.259 (7)	C23—C26	1.513 (10)
O3—Zn1^iii	2.073 (4)	C24—C25	1.389 (10)
O4—C48	1.237 (7)	C26—C27	1.559 (11)
O4—Zn1^iii	2.418 (4)	C27—C28	1.530 (12)
N1—C5	1.336 (11)	C28—C29	1.322 (12)
N1—C1	1.344 (11)	C28—C33	1.332 (12)
C1—C2	1.382 (10)	C29—C30	1.407 (13)
C2—C3	1.378 (11)	C30—C31	1.360 (13)
C3—C4	1.381 (11)	C31—C32	1.348 (13)
C3—C6	1.501 (9)	C31—C34	1.562 (13)
C4—C5	1.395 (10)	C32—C33	1.380 (13)
C6—C7	1.565 (11)	C34—C35	1.593 (13)
C6—C26	1.591 (10)	C35—C38	1.543 (13)
C7—C8	1.521 (11)	N4—C36	1.313 (11)
C7—C27	1.603 (11)	N4—C40	1.340 (11)
C8—C13	1.313 (11)	C36—C37	1.367 (10)
C8—C9	1.316 (11)	C37—C38	1.341 (12)
C9—C10	1.373 (11)	C38—C39	1.343 (12)
C10—C11	1.347 (12)	C39—C40	1.406 (11)
C11—C12	1.369 (12)	C41—C42	1.497 (6)
C11—C14	1.547 (13)	C42—C47	1.384 (7)
C12—C13	1.391 (12)	C42—C43	1.390 (6)
C14—C15	1.590 (14)	C43—C44	1.373 (7)
C14—C34	1.615 (13)	C44—C45	1.374 (8)
C15—C18	1.552 (13)	C45—C46	1.383 (7)
C15—C35	1.613 (13)	C45—C48	1.518 (7)
N2—C16	1.313 (11)	C46—C47	1.389 (7)
N2—C20	1.328 (10)	C48—Zn1^iii	2.548 (6)
O1—Zn1—O2^i	116.53 (14)	N2—C20—C19	123.2 (10)
O1—Zn1—O3^ii	150.21 (16)	C25—N3—C21	117.9 (11)
O2^i—Zn1—O3^ii	93.19 (16)	N3—C21—C22	121.7 (11)
O1—Zn1—N1	87.9 (3)	C23—C22—C21	120.6 (10)
O2^i—Zn1—N1	90.0 (3)	C24—C23—C22	116.4 (8)
O3^ii—Zn1—N1	94.4 (3)	C24—C23—C26	123.1 (9)
O1—Zn1—O4^ii	92.18 (15)	C22—C23—C26	120.0 (9)
O2^i—Zn1—O4^ii	151.26 (15)	C23—C24—C25	120.5 (10)
O3^ii—Zn1—O4^ii	58.07 (16)	N3—C25—C24	122.6 (11)
N1—Zn1—O4^ii	92.4 (3)	C23—C26—C27	121.3 (9)
O1—Zn1—C48^ii	120.85 (18)	C23—C26—C6	115.0 (8)
O2^i—Zn1—C48^ii	122.58 (19)	C27—C26—C6	90.5 (6)
O3^ii—Zn1—C48^ii	29.39 (18)	C28—C27—C26	120.3 (9)
N1—Zn1—C48^ii	94.1 (4)	C28—C27—C7	113.8 (9)
O4^ii—Zn1—C48^ii	28.68 (17)	C26—C27—C7	89.8 (5)
C41—O1—Zn1	122.7 (3)	C29—C28—C33	116.5 (12)
C41—O2—Zn1^i	175.5 (4)	C29—C28—C27	127.0 (12)
C48—O3—Zn1^iii	96.7 (4)	C33—C28—C27	113.9 (11)
C48—O4—Zn1^iii	81.5 (4)	C28—C29—C30	119.9 (14)
C5—N1—C1	114.5 (10)	C31—C30—C29	122.5 (15)
C5—N1—Zn1	123.7 (8)	C32—C31—C30	113.0 (14)
C1—N1—Zn1	121.7 (8)	C32—C31—C34	110.8 (14)
N1—C1—C2	124.5 (11)	C30—C31—C34	134.3 (15)
C3—C2—C1	119.7 (9)	C31—C32—C33	120.5 (14)
C2—C3—C4	116.8 (7)	C28—C33—C32	123.4 (13)
C2—C3—C6	115.4 (8)	C31—C34—C35	113.0 (13)
C4—C3—C6	127.3 (9)	C31—C34—C14	117.0 (14)
C3—C4—C5	119.3 (9)	C35—C34—C14	90.0 (6)
N1—C5—C4	124.4 (11)	C38—C35—C34	120.9 (14)
C3—C6—C7	117.6 (9)	C38—C35—C15	117.3 (14)
C3—C6—C26	113.3 (8)	C34—C35—C15	89.8 (6)
C7—C6—C26	90.0 (6)	C36—N4—C40	114.4 (10)
C8—C7—C6	119.5 (8)	N4—C36—C37	122.6 (10)
C8—C7—C27	116.9 (8)	C38—C37—C36	122.8 (11)
C6—C7—C27	89.8 (5)	C37—C38—C39	117.4 (10)
C13—C8—C9	116.0 (10)	C37—C38—C35	119.2 (11)
C13—C8—C7	120.3 (9)	C39—C38—C35	121.4 (12)
C9—C8—C7	121.2 (9)	C38—C39—C40	117.1 (11)
C8—C9—C10	125.3 (10)	N4—C40—C39	125.6 (12)
C11—C10—C9	118.6 (11)	O2—C41—O1	125.3 (4)
C10—C11—C12	115.0 (11)	O2—C41—C42	117.9 (4)
C10—C11—C14	119.7 (12)	O1—C41—C42	116.8 (4)
C12—C11—C14	121.6 (11)	C47—C42—C43	118.3 (4)
C11—C12—C13	121.7 (11)	C47—C42—C41	120.7 (4)
C8—C13—C12	120.8 (11)	C43—C42—C41	120.9 (4)
C11—C14—C15	124.7 (13)	C44—C43—C42	121.4 (5)
C11—C14—C34	117.6 (14)	C43—C44—C45	120.3 (4)
C15—C14—C34	89.9 (6)	C44—C45—C46	118.9 (4)
C18—C15—C14	114.4 (14)	C44—C45—C48	119.5 (5)
C18—C15—C35	120.1 (14)	C46—C45—C48	121.6 (5)
C14—C15—C35	90.2 (7)	C45—C46—C47	121.0 (5)
C16—N2—C20	115.8 (9)	C42—C47—C46	119.9 (4)
N2—C16—C17	124.8 (11)	O4—C48—O3	123.7 (5)
C18—C17—C16	116.8 (12)	O4—C48—C45	118.6 (6)
C19—C18—C17	119.4 (10)	O3—C48—C45	117.7 (5)
C19—C18—C15	112.6 (11)	O4—C48—Zn1^iii	69.8 (3)
C17—C18—C15	126.5 (12)	O3—C48—Zn1^iii	53.9 (3)
C18—C19—C20	118.6 (10)	C45—C48—Zn1^iii	171.6 (5)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) x−1/2, y, −z+2; (iii) x+1/2, y, −z+2.