Exploitation of knowledge databases in the synthesis of zinc(II) malonates with photo-sensitive and photo-insensitive N,N′-containing linkers

Photoinitiated solid-state reactions are known to affect the physical properties of coordination polymers, such as fluorescence and sorption behaviour, and also afford extraordinary architectures (e.g. three-periodic structures with polyorganic ligands). However, the construction of novel photo-sensitive coordination polymers requires an understanding of the factors which govern the mutual disposition of reactive fragments. A series of zinc(II) malonate complexes with 1,2-bis(pyridin-4-yl)ethylene and its photo-insensitive analogues has been synthesized for the purpose of systematic analysis of their underlying nets and mutual disposition of N-donor ligands. The application of a big data-set analysis for the prediction of a variety of possible complex compositions, coordination environments and networks for a four-component system has been demonstrated for the first time. Seven of the nine compounds possess one of the highly probable topologies for their underlying nets; in addition, two novel closely related four-coordinated networks were obtained. Complexes containing 1,2-bis(pyridin-4-yl)ethylene and 1,2-bis(pyridin-4-yl)ethane form isoreticular compounds more readily than those with 4,4′-bipyridine and 1,2-bis(pyridin-4-yl)ethylene. The effects of the precursor, either zinc(II) nitrate or zinc(II) acetate, on the composition and dimensionality of the resulting architecture are discussed. For three of the four novel complexes containing 1,2-bis(pyridin-4-yl)ethylene, the single-crystal-to-single-crystal [2 + 2] cycloaddition reactions were carried out. UV irradiation of these crystals afforded either the 0D→1D or the 3D→3D transformations, with and without network changes. One of the two 3D→3D transformations was accompanied by solvent (H₂O) cleavage.

1. Introduction

Topotactic reactions in the crystals of coordination compounds may proceed keeping (e.g. 1D→1D, 2D→2D or 3D→3D) or changing (e.g. 0D→1D, 0D→2D, 1D→2D or 2D→3D, including transformations from interpenetrated to non-interpenetrated architectures) the periodicity of the complexes (Vittal, 2007; Vittal & Quah, 2017; Huang et al., 2017). Solid-state reactions involve atomic and molecular movement, which can be accompanied by changes in the properties of a compound such as fluorescence (Papaefstathiou et al., 2004), luminescence (Hu et al., 2015), sorption (Sato et al., 2012) and others. However, the number of types of thermoinitiated topotactic reactions greatly exceeds that of photoinitiated reactions. For example, in the review by Vittal (2007) only examples of 0D→1D, 1D→1D and 2D→3D transformations are given; since that time, few examples of 1D→3D (Ou et al., 2012), 1D→2D (Hu et al., 2015) and 3D→3D (Mir et al., 2010; Liu et al., 2010; Michaelides et al., 2011; Li et al., 2014) reactions have been published. We consider the insufficient investigation of photoinitiated reactions a result of the factors that govern the mutual disposition of reactive fragments, which are not well understood. With regards to metal complexes, mainly hydrogen bonds (Peedikakkal & Vittal, 2008) and metallophilic interactions (Georgiev et al., 2010; Chu et al., 2005; Schmidbaur & Schier, 2012) were used to carry out 0D→1D transformations, or in some cases, planar chelate (Papaefstathiou et al., 2004, 2005) and bridging (Mir et al., 2010; Sato et al., 2012; Nagarathinam & Vittal, 2006; Chanthapally et al., 2013; Toh et al., 2005) carboxylate anions were applied to fix the photo-sensitive species in reactive positions for intramolecular 1D→1D or 2D→2D reactions. For example, 1D coordination polymers with ladder-type structures are characterized by close and parallel orientation of the double bonds in photoreactive spacer ligands (depicted in black in Fig. 1) if the bridging ligands (shown in red) facilitate the shortening of the metal–metal distances. Solid-state photodimerization in zinc(II) carboxylates containing 1,2-bis(pyridin-4-yl)ethylene (bpe) was carried out (Toh et al., 2005; Papaefstathiou et al., 2005); the bridging carboxylate groups make the distance between Zn centers as short as 3.82–3.85 Å. The reduction in distance between opposite linkers is chemically driven and can be carried out for other coordination polymer nets (see the square-planar and honeycomb nets in Fig. 1).

Figure 1 Schematic representation of a ladder [4^4(0,2)], a square-planar (sql) and a honeycomb (hcb) net and the shortening of the distance between opposite sides of tetragonal and hexagonal polygons in the case of inequivalent linkers (short edges are red). Herein, the notation of nets is given in accordance with the literature (O'Keeffe et al., 2008; Blatov et al., 2009).

In our opinion, recent progress in reticular chemistry and data analysis of coordination polymers allows new directions for developing the syntheses of coordination polymers with a desired mutual disposition of photo-sensitive species. The reticular chemistry approach (Yaghi et al., 2003; Furukawa et al., 2013) to photoactive materials can be based on the replacement of a photo-insensitive ligand with its photo-sensitive analogue in architectures with desired disposition of reactive fragments. In this case, a chemist should determine which ligands form an isoreticular series. An expert system based on the analysis of all X-rayed compounds allows prediction of the most abundant compositions and architectures of coordination polymers, even for insufficiently explored mixtures (Alexandrov et al., 2011, 2015a,b; Mitina & Blatov, 2013; Schoedel & Zaworotko, 2014), but cannot predict which of all the possible architectures will form and how 1D and 2D polymers will be situated with respect to each other. Nevertheless, despite various coordination numbers, coordination environments and complex compositions, similar networks can be obtained; also 2D nets such as honeycomb or square-planar (Fig. 1) and 3D nets such as diamond or primitive-cubic appear much more often than nets with the same connectivity of nodes, making the synthesis of architectures with the desired disposition of ligands possible.

Herein, we discuss the results of our investigation, which aimed to reveal the effectiveness of the reticular chemistry approach and expert system predictions for the construction of zinc(II) coordination polymers with photo-sensitive bpe linkers situated in reactive positions. Zinc(II) aqueous solutions were used because zinc can have various coordination numbers. Photo-insensitive 4,4′-bipyridine (bipy) and 1,2-bis(pyridin-4-yl)ethane (bpa) were used as analogues of bpe to reveal if these ligands could form isoreticular series. We assumed that not only bridging monocarboxylates, but also short bridging dicarboxylate anions are able to distort networks and shorten the distance between the nitrogen-containing ligands (Fig. 1). Thus, dimethylmalonate (Me₂mal) and diethylmalonate (Et₂mal) anions (An) were used, as these fix the Zn:An ratio to 1:1 (to decrease the number of symmetrically independent anions in the unit cell) and have less coordination modes than the malonate anion (Gogoleva et al., 2017).

2. Results and discussion

2.1. Knowledge-based prediction of complex composition, periodicity and topology in Zn^II:L:An²⁻:H₂O mixtures

An algorithm for the estimation of the most abundant nets of coordination polymers has been described in recent papers (Mitina & Blatov, 2013; Alexandrov et al., 2015a,b; Shevchenko et al., 2017). It is based on the analysis of crystallographic databases to reveal possible coordination numbers and coordination polyhedra of a given metal atom, ratio of cations, anions and neutral ligands which depend on the coordination number, and possible coordination modes of all ligands. Moreover, the probability of the occurrence of a particular motif can be estimated if the number of X-rayed representatives in a mixture is large enough. Let us take Zn^II:L:An²⁻:H₂O mixtures as an example (L = bipy, bpe or bpa; An = Me₂mal or Et₂mal). The Cambridge Structural Database (Groom & Allen, 2014; Groom et al., 2016) contains data for only 12 compounds constructed of zinc(II), 4,4′-bipyridine or its analogues and malonate derivatives (see Table S1 in the supporting information). Eleven of the compounds form an isoreticular series with ins topology and a parallel orientation of the N,N′-containing linkers and long intermolecular distances between their centers (≃ 7.5 Å). Although this net seems to be inappropriate for the construction of photo-sensitive coordination polymers, we expected that the other architectures with close disposition of neutral linkers can appear in this system. In order to reveal all possible motifs in this system and estimate the probability of their occurrence, we examined the data for the crystal structures of similar compounds. Distribution of zinc(II) coordination numbers and the compositions of coordination polyhedra have been obtained from 1473 complexes containing both zinc(II) and a bipy, bpe or bpa ligand. Among them, 220 compounds containing 298 symmetrically independent bpe ligands (the target photo-sensitive ligand) were used to determine the possible coordination modes of this linker and the probable Zn:L ratios. Finally, 54 zinc(II) malonates were analyzed to estimate the distribution of coordination modes of the anion. Both bpe and the An group are able to crystallize as non-coordinated species or terminal ligands, but this is a rare case more typical for acidic solutions. The other coordination modes found are depicted in Fig. 2 (cases of terminal anion ligands have not been depicted).

Figure 2 Coordination modes and their associated probabilities of occurrence for bpe or malonate anion and its derivatives in zinc(II) complexes.

Coordination modes are denoted in accordance with the nomenclature described by Serezhkin et al. (2009). Each ligand L is designated by one of the letters M, B, T or K depending on the number of donor atoms connected to the metal (1, 2, 3 or 4, respectively). The total number of metal atoms coordinated by the ligand (ν) is given as upper index in the form of the string mbtk where each integer m, b, t, k is equal to the number of metal atoms coordinated by one, two, three or four donor atoms; ν = m + b + t + k. The coordination mode of the ligand is represented by the symbol L^mbtk, and the local topology of the complex group is written as coordination formula (CF) A_nL1_mL2_k… where A denotes a metal atom, for example, zinc(II), n is the number of metal atoms in a polynuclear unit, and L1, L2… designate the coordination modes of ligands. This compact nomenclature allows us to easily distinguish different types of bridge or chelate ligands, in order to calculate the coordination number of a metal atom and the composition of its coordination polyhedron (see supporting information for details). Based on the coordination formula, further possible structural motifs can be proposed using reported correlations between coordination formulas of complexes and the topologies of coordination polymers (Mitina & Blatov, 2013; Alexandrov et al., 2015a,b; Shevchenko et al., 2017).

Further analysis of complexes obtained from Zn^II:L:An²⁻:H₂O mixtures will be limited to those containing: (i) at least one nitrogen atom coordinated to a zinc(II) atom; (ii) a zinc(II) atom with a coordination number of 4, 5 or 6; (iii) a Zn^II:L ratio equal to 2:1, 1:1 or 1:2; (iv) Zn^II:An²⁻ = 1:1 or Zn^II:HAn⁻ = 1:2. Additional requirements include: (v) if the number of independent zinc atoms or ligands (A, An or L) is equal to 2, both species should have the same coordination mode; (vi) water molecules act as terminal (M¹) ligands only. The first requirement (i) is needed to control the disposition of nitrogen-containing ligands. The restrictions (ii) and (iii) are true for 98% of all Zn^II:L complexes and 86% of Zn^II:bpe or bpa complexes, respectively. From requirement (v), it follows that zinc(II) in [Zn₂L(HAn)₄(H₂O)_x] and [Zn₂LAn₂(H₂O)_x] complexes have an even number of nitrogen atoms and [ZnL₂An(H₂O)_x] complexes have an odd number of nitrogen atoms in the coordination polyhedron. The full table of the complexes which satisfy the above criteria, including their coordination formulas and possible nets is given in the supplementary information (Table S2). In Fig. 3, predictions of the most probable complexes are derived from the following facts: 92% of bpe molecules in zinc complexes act as bridging (B²) ligands; HAn⁻ tends to act as a terminal ligand or counterion in contrast with An²⁻, which have bridge (B²), chelate (B⁰¹) or bridge-chelate (B¹¹, T¹¹, T²¹, K²¹) coordination modes mainly (Fig. 2). Note, that anions in the B², B¹¹ and T¹¹ or T²¹ and K²¹ coordination modes bind two or three metal atoms in a similar disposition; thus, they form similar complexes, and often similar networks. Fig. 3 contains the most expected architectures for these complexes, either discrete complexes (for example, dimers of the [Zn₂L(H₂O)_6+2x]⁴⁺ composition), or coordination polymers (one-, two- or three-periodic). Note that polymers can have various L:Zn ratios and CFs, but still produce the same topology of the underlying net. For example, both [Zn₂LAn₂(H₂O)_2+2x] and [ZnLAn(H₂O)_x] complexes with CFs, A₂B²B²₂M¹_2+2x and AB²B²M¹_x (x = 0, 1 or 2), respectively, can belong to the set of the one-periodic ladder 4⁴(0,2) or two-periodic square-planar sql architectures.

Figure 3 The family of the most probable complexes and their coordination formulas in the Zn^II:L:An^2− (or HAn^−):H2O mixtures as well as the most probable nets (depicted in Figs. 1 and 4) found for these coordination formulas. CP: coordination polyhedron; CF: coordination formula; CN: coordination number; D: dimensionality of a network; Examples: synthesized compounds which have the topology of the underlying net are given at the left column.

As shown by Fig. 3, discrete complexes or complexes with simple chain structures are mainly found in acidic solutions (corresponding chemical formulas are marked in red). Similar architectures are typical for complexes with chelate (B⁰¹) anions, as these do not act as linkers. The complexes containing bridge (B²) anions and 4,4′-bipyridine analogues are able to give one-, two- and three-periodic coordination polymers, including the widespread chain (2C-1), ladder [4⁴(0,2)], sql, hcb, dia and cds nets [see Mitina & Blatov (2013) and Alexandrov et al. (2011) for the analysis of the distribution of two- and three-periodic nets]. A characteristic feature of these nets and the neb and zst networks is that all ligands including the anions act as linkers. Nets such as ins require an anion to connect three zinc atoms in order to have the T²¹ or K²¹ coordination mode. As illustrated in Figs. 1 and 4, nets including ladder 4⁴(0,2), sql, hcb, ins, cds and zst allow realisation of close and parallel disposition between linkers if the net is distorted by some short linkers. For dia and neb nets, close disposition within the net is hardly possible, although it can appear between parallel linkers from interpenetrated nets. To summarise, there is a high probability of two- and three-periodic ladder architectures with parallel orientation of ethenyl groups in Zn^II:R₂mal²⁻:bpe:H₂O mixtures, because the malonate anion and its alkyl derivatives favour close disposition of zinc(II) cations and all ligands connected with them.

Figure 4 Selected 1D, 2D and 3D underlying nets derived for zinc(II) malonates.

The validity of above approach is verified by the fact that a number of previously obtained zinc(II) dicarboxylates containing 4,4′-bipyridine and its analogues are characterized by the above CFs and have one of the proposed topologies (Table S2). Moreover, a number of zinc(II) nitrate (Peedikakkal & Vittal, 2008), monocarboxylate (Toh et al., 2005; Chanthapally et al., 2014) or dicarboxylate (Mir et al., 2010; Sato et al., 2012; Ou et al., 2011, 2012; Hu et al., 2015) complexes with bpe have the above topologies and are known to undergo solid-state photochemical [2 + 2] cycloadditions. Particularly, dicarboxylates with the compositions: [Zn(bpe)(muco)]·DMF·H₂O and [Zn(bpe)(1,4-bdc)]·DMF (Mir et al., 2010), [Zn₂(bpe)(1,2-bdc)₂] (Ou et al., 2011), [Zn(bpe)(moip)]·DMF (Sato et al., 2012), [Zn(bpe)₂(1,2-chdc)(H₂O)₂] (Ou et al., 2012) and [Zn(bpe)(L)(H₂O)] (Hu et al., 2015) are characterized by their CF and net, respectively, AB²K²¹/fet, A₂B²B¹¹₂/4⁴(0,2), AB²K²¹/3,5L2, AM¹₂B₂M′¹₂/2C-1 and AM¹B²M′¹/2C-1 {H₂muco = trans,trans-muconic acid, H₂bdc = benzene dicarboxylic acid; H₂moip = 5-methoxy­isophthalatic acid; H₂chdc = cyclohexanedicarboxylate; H₂L = 4,4′-[1,2-phenylenebis(methylene)bis(oxy)]dibenzoic acid}.

2.2. Synthesis

The reaction of zinc(II) nitrate or zinc(II) acetate with dimethylmalonic or diethylmalonic acid in the presence of a nitrogen-containing ligand such as bipy, bpe or bpa afforded nine novel compounds (Figs. 5, 6). Synthesis was carried out by the slow mixing of solutions. Attempts to use a direct synthesis (mixing the reagents in an appropriate solvent) as well as the use of solvothermal methods were unsuccessful, since in both cases we failed to obtain single crystals suitable for X-ray diffraction. The results obtained indicate that the initial zinc(II) salt source can affect the chemical composition of precipitate complexes. All acidic salts and hence, the cationic complexes, were obtained from zinc(II) nitrate. However, starting from zinc(II) acetate, anhydrous neutral complexes more readily formed. Only bpa-containing mixtures (for both Me₂mal²⁻ and Et₂mal²⁻) and the Zn^II:bipy:Me₂mal²⁻ gave the same products regardless of the cation source.

2.3. Crystallography

Compounds obtained were characterized by means of single-crystal and powder X-ray diffraction techniques. Powder X-ray diffraction confirmed that the samples were phase pure and consisted mainly of the above reaction products (see supporting information). Single-crystal XRD confirmed the validity of our proposal about possible Zn^II:L:An²⁻ ratios and coordination formulas. Only [Zn₂(bipy)₃(Et₂mal)₂] (5) has an unexpected 2:3:2 ratio with two different coordination modes of the bipy ligands, but even in this case the complex can be regarded as an analogue of the [Zn₂LAn₂(H₂O)₂] complex with the A₂B²B²₂M¹₂ CF. Four of the nine complexes obtained [(2), (4), (7), (9)] have the ratio Zn^II:L:An²⁻ = 1:1:1 with ligands and anions in bridge mode (and the CF = AB²B²). Among these, only [Zn(bpe)(Me₂mal)]·H₂O (2) and [Zn(bpa)(Me₂mal)]·H₂O (4) are isostructural (Table S3) and have the same underlying net; however, the networks of (7) and (9) differ in the disposition of neutral linkers (see below). In [Zn(bpe)(HMe₂mal)₂] (3) and [Zn(bipy)(H₂O)₄](HEt₂mal)₂·bipy·2H₂O (6) an anion is protonated, so the Zn^II:L:HAn⁻ ratio is equal to 1:1:2, and only a neutral N,N′-containing ligand acts as a linker, while the anion is a terminal ligand or counterion (the CFs are: AB²M¹₂ and AB²M¹₄, respectively). In [Zn(bpe)₂(H₂O)₄](HEt₂mal)₂ (8) the anion is also protonated and acts as a counterion, but the ratio Zn^II:L = 1:2 and the CF = AM¹₂M′¹₄ to give the discrete complex only. At last, [Zn₂(bipy)(Me₂mal)₂(H₂O)₂] (1) belongs to the family of complexes with Zn^II:L:An²⁻ = 2:1:2 with the A₂B²K²¹₂M¹₂ CF. Note that all these CFs are among the most expected for Zn^II:L:An²⁻:H₂O mixtures (Fig. 3).

The discrete [Zn(bpe)₂(H₂O)₄](HEt₂mal)₂ (8) complex can be regarded as representative of the family of O—H⋯N bonded compounds with parallel and close orientation of the neighbouring bpe or bipy molecules (Table S2). Similar to its nitrate-containing analogue, [Zn(bpe)₂(H₂O)₄](NO₃)₂·8/3H₂O·2/3bpe (Peedikakkal & Vittal, 2008), it readily undergoes the [2 + 2] cycloaddition 0D→1D photoreaction to give a coordination polymer (see §2.4 for details).

[Zn(bpe)(HMe₂mal)₂] (3) and [Zn(bipy)(H₂O)₄](HEt₂mal)₂·bipy·2H₂O (6) are simple chains with CFs AB²M¹₂ and AB²M¹₄, respectively (Fig. 7). As zinc(II) has tetrahedral and octahedral coordination in these complexes, the chains are zigzag and linear, respectively. The chains of [ZnL(H₂O)₄] composition are always linear with nitrogen atoms of the two linkers situated in the apical position of octahedral zinc(II); the coordinated water molecules are involved in hydrogen bonding with counterions or solvent molecules, which separate L from one another. Thus, in such systems photoreactions would be possible if either both L and the counterion are UV-sensitive and are situated in positions appropriate for a [2 + 2] cycloaddition reaction, or additional photoreactive L molecules are stabilized by O—H⋯N hydrogen bonds in reactive positions with coordinated ones. The head-to-tail packing of zigzag chains of the [ZnLAn₂] composition is not forbidden in general; there are a few examples with bipy ligands and close parallel disposition of planar ligands [see Mulijanto et al. (2017) for example of photoreactive zigzag chains], but it requires small or linear anions. Bulky anions typically prevent packing of bipy and its analogues in reactive positions, as in the case of (3).

Figure 7 Fragment of [Zn(bpe)(HMe2mal)2] (3) [r(Zn–Zn) = 13.5 Å, ∠(Zn–Zn–Zn) = 108°] and [Zn(bipy)(H2O)4](HEt2mal)2·bipy·2H2O (6) [r(Zn–Zn) = 11.4 Å, ∠(Zn–Zn–Zn) = 180°] chains.

[Zn₂(bipy)₃(Et₂mal)₂] (5) represents layered complexes and has the hcb network topology (Fig. 8). The layer is almost planar with terminal bipy ligands situated on both sides of the layer. The anions connect the metal atoms in a zigzag chain with r(Zn⋯Zn) = 5.4 Å and ∠(Zn–Zn–Zn) = 99°; the chains are further bonded by bipy ligands to the hcb net with the distance between metal atoms equal to 11.1 Å. Thus, the net is distorted as four of the six sides of the hexagons are shorter than the other two. This shortening makes the distance between parallel bipy ligands as short as 5.5 Å, but it is still too long to allow the occurrence of a photoreaction for a hypothetical bpe analogue. Note that for the sql network found in [Zn(bipy)(Ph(CH₂)₃mal)(H₂O)]·4H₂O (Gao et al., 2012) with a bridge-chelate Ph(CH₂)₃mal anion, this distance is shorter (4.8 Å). Terminal bipy ligands in (5) are directed towards the centres of six-membered cycles of (5) sheets, so the layers are packed in a way that also prevents close packing of bridge bipy ligands from neighbouring layers. In the case of less bulky terminal ligands, for example, for tetracoordinated zinc(II) atoms in [Zn₂(bpa)₃(tpp)₂]ClO₄ (Dias de Souza et al., 2015) [tpp = 3-(2-thienyl)propanoato] bpa ligands are situated in stacks with closest C–C distances of 4.9 Å, affected by the repulsion from hydrogen atoms of ethane moieties. One can propose fewer restrictions in the case of planar bpe ligands and the possibility of [2 + 2] cycloaddition reactions for bpe analogues.

Figure 8 Fragment of the crystal packing in [Zn2(bipy)3(Me2mal)2] (5) and [Zn(bipy)(Ph(CH2)3mal)(H2O)]·4H2O (Gao et al., 2012) and the underlying nets depicted in black (for bipy linkers) and red (for anions). Hydrogen atoms, terminal ligands and solvent molecules have been omitted.

The other coordination polymers synthesized are 3D networks. Complex [Zn₂(bipy)(Me₂mal)₂(H₂O)₂] (1) belongs to the family of zinc(II) malonates with the A₂B²K²¹₂M¹₂ CF. Note, that 11 of the 12 previously reported zinc(II) complexes with bipy, bpa or bpe and malonate derivatives have the same CF and form as the ins 3,4-coordinated net (e.g. it contains two nodes, one node is the anion connected with three metal atoms, and the four-coordinated node is zinc connected with four neighbours – here, three anions and one zinc atom through a bridge L). The ideal ins net occurs in the orthorhombic Pnnm space group with the longest crystal parameter twice the length of the shortest one. Among the 11 reported and the new zinc(II) malonate complexes containing bipy and its analogues and ins architecture, only [Zn₂(bipy)(Me₂mal)₂(H₂O)₂] (1), [Zn₂(bipy)(cbdc)₂(H₂O)₂] [(Zhang et al. (2014) cbdc = cyclobutane-1,1-dicarboxylato] and [Zn₂(bpa)(Memal)₂(H₂O)₂] (Déniz et al., 2012) crystallize in the same Pnnm space group and similar crystal parameters; thus, (1) can be regarded as isostructural with [Zn₂(bipy)(cbdc)₂(H₂O)₂] (Zhang et al., 2014) and [Zn₂(bpa)(Memal)₂(H₂O)₂] (Déniz et al., 2012). At the same time, despite the fact that other complexes crystallize in P2₁/n, Pna2₁ or Pnn2 space groups, their crystal parameters are all close to 7.2, 7.4 and 21.0 Å, respectively, and the distortion of the network accounted for by the various substituents at the malonate anion and elongation of the L linker is insignificant. The net can be regarded as a combination of [ZnAn(H₂O)] layers with the AK²¹M¹ CF and hcb topology, connected through L linkers that bridge between zinc(II) atoms from neighbouring sheets (Fig. 9). The coordination mode of the anion does not affect the Zn–Zn interatomic distances; in (1) these are ∼5.4 Å as in complex (5) described previously. The length of a linker affects only the distance between layers, the Zn–Zn distance in bipy-containing compounds is ∼11.5 Å and that in bpe and bpa-containing compounds is ∼13.5 Å. As N,N′-containing ligands are not perpendicular to the [ZnAn(H₂O)] layers, the distance between them is longer than 5.4 Å and varies from 7.1 to 7.5 Å. To sum up, the family of [Zn₂LAn₂(H₂O)₂] complexes forms an isoreticular series for a variety of ligands [L = bipy, bpe, bpa and 4,4′-(propane-1,3-diyl)bipyridine; An = mal, Memal, Me₂mal, cyclobutane­dicarboxylate (cbdc)].

Figure 9 Fragment of the crystal packing in [Zn2(bipy)(Me2mal)2(H2O)2] (1) (top) and the underlying net (bottom) depicted in blue (for bipy linkers) and red (for anions). Hydrogen atoms have been omitted.

At the same time, reactions of zinc(II) acetate with Me₂mal or Et₂mal in the presence of bpe and bpa, but not bipy, afforded complexes [Zn(bpe)(Me₂mal)]·H₂O (2) and [Zn(bpa)(Me₂mal)]·H₂O (4) or [Zn(bpe)(Et₂mal)] (7) and [Zn(bpa)(Et₂mal)]·0.38H₂O (9), having the same CF. As the CF AB²B² allows a variety of architectures, similar networks were expected only for isostructural (2) and (4). Indeed, these realize the zst topology of the underlying net which can be regarded as a parallel packing of zigzag [ZnAn] chains connected by neutral bpe or bpa linkers with water molecules situated in the pores of the net (Fig. 10). Again, the anions fix the distance between zinc(II) atoms within the [ZnAn] chains as short as 5.8 Å; the length of a neutral linker defines the distance between the chains (13.3 Å). The fact that the linkers are not parallel allows rather tight packing of nitrogen-containing ligands so that a [2 + 2] cycloaddition reaction successfully occurred in (2) (see §2.4). In [Zn(bpa)(Et₂mal)] (9) the same parallel zigzag [ZnAn] chains with r(Zn–Zn) = 5.4 Å are revealed, which are connected by bridging bpa ligands, but the disposition of the bpa molecules in the network differs from that in the zst net (Fig. 10). In fact, we synthesized a new, previously unreported 4-c net with the point symbol (6⁵.8), registered at ToposPro TTD collection as igc1 (see supporting information for Systre input files for this, and all the other nets).

Figure 10 Fragment of the crystal packing in [Zn(bpe)(Me2mal)]·H2O (2) and [Zn(bpa)(Et2mal)]·0.38H2O (9) and their underlying nets depicted in black (for bpa and bpe linkers) and red (for anions). Hydrogen atoms have beem omitted.

Complex [Zn(bpe)(Et₂mal)]·0.25bpe (7) crystallizes in the Cmcm space group for which automatic determination of net topology is restricted by the presence of numerous symmetry elements [for example, zinc(II) is eight-coordinated with all positions only half-occupied]. Careful analysis of the net assuming P1 symmetry allowed us to restore connectivity of a network for a coordination polymer with the [Zn(bpe)(Et₂mal)] composition, zinc(II) in tetrahedral ZnN₂O₂ environment and bridge bpe and Et₂mal linkers, and to estimate net architecture. Surprisingly, (7) also has a 4-coordinated (6⁵.8) topology very similar with igc1, but the number of zinc(II) atoms in the fifth and other coordination spheres differs from that in igc1. Close disposition of coordinated and co-crystallized bpe ligands allows their packing in reactive positions, although strong disorder does not allow prediction of which of the two tpcb stereoisomers can be obtained in this crystal.

Thus, eight of the nine novel compounds are characterized by one of the most expected compositions and ligand connectivities, and seven also have one of the highly probable topologies of the underlying net. This means that previously reported crystallographic data can be used to assume the most abundant architectures of complexes crystallized in complex reaction mixtures. It was demonstrated that bpe and bpa ligands in zinc(II) complexes with malonate derivatives form isoreticular series more readily than their bipy analogues. Initially, these results appear to contradict the results obtained by Kim et al. (2017), who studied zinc(II) alkane (or alkene)-dicarboxylates with bpe and bpa and found only few isoreticular compounds. But the absence of isoreticularity was associated with various coordination modes of anions; so for dicarboxylate anions which have only a small number of coordination modes, one can expect isoreticular complexes with bpa and bpe.

Regarding the effects of the zinc(II) precursors, one can propose that starting from zinc(II) nitrate, zinc(II)–aqua complexes with nitrogen-containing ligands and acidic salts (which act as counterions or terminal ligands) form more readily. Conversely, using [Zn(CH₃COO)₂(H₂O)₂] as a precursor would likely produce networks constructed of [ZnAn] chains or layers connected by nitrogen-containing linkers, probably because An is able to replace acetate ions in the coordination sphere of a zinc(II) atom. The other part of the coordination sphere of a zinc(II) atom can contain neutral water as well as N,N′-containing ligands. Although the distance between metal atoms in the [ZnAn] chain is not very small (ca 5 Å), various types of connections between the chains sometimes allow close packing of bpe ligands in reactive positions for post-synthetic modification by means of photoinitiated reactions.

2.4. Single-crystal-to-single-crystal [2 + 2] cycloaddition reactions

Three of the four bpe-containing compounds have a close disposition of the bpe ligands; these were attested to undergo a solid-state photoinitiated [2 + 2] cycloaddition reaction. Their single crystals were irradiated with a Xe lamp and then analyzed by means of single-crystal XRD. Bulk samples were investigated using powder XRD and ¹H NMR. All three methods confirmed that compounds had undergone solid-state reactions.

2.4.1. Complex (2)

Mutual disposition of bpe ligands in (2) is not very efficient for a [2 + 2] cycloaddition reaction (Figs. 10, 11); neither of the two ligands are coplanar, no ethylene fragments are parallel, the distances between the carbon atoms of the ethylene groups are equal to 3.9 and 4.4 Å. At the same time, powder XRD (Fig. 12) clearly indicates that UV irradiation affects the structure and a solid-state reaction has taken place. UV irradiation of a single crystal under N₂ flow for 4 h did not affect the structure; thus, the same single crystal was irradiated in air at room temperature for a further 8 h. In this case, reflection intensities changed dramatically, so that the structure could be obtained using synchrotron radiation only. XRD revealed the reasons for the varied behaviour of the sample at low temperatures in air. During irradiation in air, the sample was also heated and the quantity of water molecules in the crystal structure decreased. The absence of a proportion of water molecules could affect the mutual disposition of the bpe molecules in the coordination polymer and could promote the photoinitiated [2 + 2] cycloaddition reaction. Loss of solvent molecules followed by other single-crystal-to-single-crystal (SCSC) reactions was previously observed in other zinc(II) carboxylates (Ou et al., 2011; Li et al., 2014), so this reaction is a new example of a two-step SCSC process. The reaction proceeded with a change in space group (P2₁/c → Pnna) and despite the loss of solvent, incurred a 1.5% increase in cell volume. The number of water molecules in the reaction product obtained by free refinement of the occupancy of a water oxygen is equal to 0.25 [per zinc(II) atom]; thus, one can hardly expect full conversion of bpe molecules. Indeed, the refinement of the occupancies of carbon atoms gives the ratio of one molecule of the rtct isomer of tetrakis(4-pyridyl)cyclobutane (tpcb) per two molecules of bpe and the composition of the complex obtained by an SCSC two-step process [Zn(bpe)(Me₂mal)]₂[Zn₂(tpcb)(Me₂mal)₂]·H₂O. ¹H NMR data (Fig. S15) also provides evidence that the reaction product contains only the rtct isomer as proposed from the preorganization of ligands within the crystal (Fig. 10). Both ¹H NMR and PXRD data (Fig. S6) indicate that the conversion of the bpe molecules in the sample was unfinished.

Figure 12 Powder XRD data for (2), (7) and (8) before irradiation (blue) and after irradiation for 6 h (red).

As the initial complex and reaction product are both three-periodic polymers, the photoinitiated process in (2) is of the 3D→3D type. At the same time, the reaction product contains the K⁴ ligand instead of two B² ligands; thus, the change in the network is also of interest. Assuming full conversion of the polymer to [Zn₂(tpcb)(Me₂mal)₂]·0.5H₂O, we estimated the topology of the irradiated sample to be the 4,4,4-coordinated net with the point symbol {4·6⁴·8}{6⁵·8}{4³·6³} (Fig. 11). This is also a novel net that has not been seen before.

Figure 11 Fragment of crystal packing in [Zn(bpe)(Me2mal)]·H2O (2), the underlying net and the hypothetical underlying net of [Zn2(tpcb)(Me2mal)2]·0.5H2O.

2.4.2. Complex (7)

A crystal of (7) underwent a Cmcm → Pbcn transfer in an SCSC manner after irradiation for 6 h with a 0.9% decrease in cell volume. PXRD indicates total conversion of the bulk sample; ¹H NMR revealed that the sample contains both rctt-tetrakis(4-pyridyl)cyclobutane as the major reaction product and trace amounts (<5%) of the rtct isomer (Fig. S16). Single-crystal XRD of the irradiated crystal showed that the reaction product is fully occupied and ordered in contrast with the initial compound, and indeed contains a 3D coordination polymer with the [Zn(bpe)_0.75(tpcb)_0.25(Et₂mal)] composition, the AB²B² CF and the net topology proposed for (7) (registered as igc2). The net is depicted in Fig. 13; it can also be described, again, as parallel packing of the [Zn(Et₂mal)] zigzag chains connected to hcb layers by one of the two independent bpe molecules. These layers are further connected to the igc2 net by means of bridge ligands (these positions are shared with bpe and tpcb molecules). Only XRD analysis of the reaction product allowed us to undoubtedly reveal the presence of co-crystallized bpe molecules in the pores of the initial complex (7), because these are highly disordered in the Cmcm space group. The disorder does not allow the mutual disposition of coordinated and co-crystallized bpe molecules to be confirmed and hence an estimation of which of the two tpcb isomers should form more readily. But based on ¹H NMR data, one can propose that there exists some pedal-like motion prior to photodimerization, as both isomers appear in this spectrum (but only the rctt isomer was found as a single crystal). As the reaction occurred between the coordinated and co-crystallized bpe molecules, the coordination network remained unchanged.

Figure 13 Fragment of the crystal packing in [Zn(bpe)(Et2mal)]·0.25bpe (7) (top) and its underlying net (bottom).

2.4.3. Complex (8)

The parallel orientations of the discrete [Zn(bpe)₂(H₂O)₄]²⁺ complexes in (8) are stabilized by intermolecular O—H⋯N bonds (Fig. 14). The mean planes of bpe ligands are parallel and the distance between equivalent atoms is equal to 3.7366 (3) Å. Being constructed from 1,4-bis(pyridin-4-yl)buta-1,3-diene or 1,4-bis(pyridin-4-yl)buta-1,3-diyne, such architectures could give a 0D→2D photoreaction with metal–organopolymeric coordination networks. In this case only a 0D→1D [2 + 2] cycloaddition occurred during UV irradiation. Mutual disposition of bpe ligands in (8) allows the rctt tpcb to act as a bridge ligand, and the [Zn₂(tpcb)(H₂O)₈]⁴⁺ chain is the only reaction product. The reaction proceeds in an SCSC manner so that the resulting structure is also suitable for single-crystal XRD. XRD data indicates that after irradiation for 3 h the single crystal contained 15% of initial substance. Further irradiation of the same single crystal does not change the conversion rate. The geometry of the chain (linear, zigzag or random, see Fig. 14) can not be evaluated, because the cyclobutane ring is probably equally disordered over two sites by symmetry. The presence of both bpe and rctt tpcb molecules was also demonstrated by powder XRD (Fig. S13) and ¹H NMR data (Fig. S17).

Figure 14 H-bonded layers in (8) and possible coordination polymers obtained after UV irradiation of a single crystal of (8).

To sum up, we succeeded in carrying out the [2 + 2] cycloaddition reactions in an SCSC manner for three of the four novel compounds obtained from Zn^II:bpe:Me₂mal (or Et₂mal):H₂O mixtures.

3. Conclusions

We analyzed the crystal structures of previously reported zinc(II) complexes with N,N′-containing bidentate linkers in order to establish the possible coordination architectures of zinc(II) malonate complexes with 1,2-bis(pyridin-4-yl)ethylene and its photo-insensitive analogues. Nine novel compounds obtained from Zn^II:bpe:Me₂mal(or Et₂mal):H₂O mixtures have highly probable compositions, zinc(II) environments and ligand connectivities, estimated from previously reported crystallographic data for zinc(II) complexes. Seven complexes also have one of the highly expected topologies of underlying nets and two form novel networks. A series of isoreticular coordination polymers containing malonate derivatives and analogues of 4,4′-bipyridine were found. 1,2-Bis(pyridin-4-yl)ethane was found to be a better analogue of 1,2-bis(pyridin-4-yl)ethylene than 4,4′-bipyridine. We found that zinc(II) acetate readily forms the target 2D and 3D architectures, whereas zinc(II) nitrate solutions produced aqua complexes and complexes with acidic malonates. Replacement of the acetate groups in the zinc(II) coordination sphere will most likely result in the formation of neutral [ZnAn] architectures with relatively short Zn^II–Zn^II distances, followed by the interaction with nitrogen-containing linkers. As these linkers are longer than bridging anions, the [ZnAn] chains can be connected by neutral linkers in numerous ways to obtain polymers with parallel or interwoven orientation of the latter.

Three of the four novel complexes containing 1,2-bis(pyridin-4-yl)ethylene were found to have close packing of ethylene groups (<4.2 Å). We succeeded in carrying out a photoinitiated [2 + 2] cycloaddition reaction for these compounds in an SCSC manner. The UV irradiation of the crystals of {[Zn(bpe)(Me₂mal)]·H₂O}_n, {[Zn(bpe)(Et₂mal)]·0.25bpe}_n and [Zn(H₂O)₄(bpe)₂](HEt₂mal)₂ afforded the 3D→3D (with network change), 3D→3D (with a constant net topology) and 0D→1D transformations with formation of {[Zn(bpe)(Me₂mal)]₂[Zn₂(tpcb)(Me₂mal)₂]·H₂O}_n, [Zn(bpe)_0.75(tpcb)_0.25(Et₂mal)]_n and {[Zn(H₂O)₄(bpe)₂]_0.15[Zn(H₂O)₄(tpcb)]_0.85(HEt₂mal)₄}_n, respectively. Overall, we think that our study provides a foundation for future development in the application of reticular synthesis as well as a big data analysis for a synthetic approach to photoreactive coordination polymers.

Supporting information

Computing details

Data collection: Bruker APEX2 for (3). Cell refinement: Bruker SAINT for (3). Data reduction: Bruker SAINT for (3). Program(s) used to solve structure: ShelXT (Sheldrick, 2015) for (1), (2), (7), (8a); SHELXS97 (Sheldrick, 1990) for (3). Program(s) used to refine structure: XL (Sheldrick, 2008) for (1), (2), (2a), (4), (5), (6), (7), (8), (8a), (9); SHELXL97 (Sheldrick, 1997) for (3); SHELXL2014 (Sheldrick, 2014) for (7a). Molecular graphics: Olex2 (Dolomanov et al., 2009) for (1), (2), (2a), (4), (5), (6), (7), (8), (8a), (9); Bruker SHELXTL for (3). Software used to prepare material for publication: Olex2 (Dolomanov et al., 2009) for (1), (2), (2a), (4), (5), (6), (7), (8), (8a), (9); Bruker SHELXTL for (3).

Catena(bis(mu3-dimethylmalonato-O,O',O'',O''')-(mu2-4,4'-bipyridine-N,N') -diaqua-dizinc(II)) (1)

Crystal data

0.5(C40H48N4O20Zn4)	Dx = 1.840 Mg m^−3
Mr = 583.15	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnnm	Cell parameters from 1788 reflections
a = 7.4159 (16) Å	θ = 3.0–28.8°
b = 19.318 (4) Å	µ = 2.34 mm^−1
c = 7.3457 (16) Å	T = 120 K
V = 1052.3 (4) Å^3	Prism, colourless
Z = 2	0.15 × 0.11 × 0.08 mm
F(000) = 596

Data collection

Bruker APEX-II CCD diffractometer	1859 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.094
Absorption correction: multi-scan SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0889 before and 0.0679 after correction. The Ratio of minimum to maximum transmission is 0.8205. The λ/2 correction factor is 0.00150.	θmax = 36.7°, θmin = 2.1°
Tmin = 0.282, Tmax = 0.344	h = −12→10
15845 measured reflections	k = −31→31
2674 independent reflections	l = −12→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.066	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.145	w = 1/[σ^2(Fo^2) + (0.020P)^2 + 6.2P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2674 reflections	Δρmax = 0.83 e Å^−3
103 parameters	Δρmin = −2.18 e Å^−3
0 restraints

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	0.48860 (7)	0.71895 (3)	0.5000	0.01475 (13)
O1	0.6379 (3)	0.77397 (11)	0.6902 (3)	0.0183 (4)
O2	0.8680 (3)	0.83692 (12)	0.7860 (3)	0.0191 (5)
O3	0.2611 (5)	0.78321 (18)	0.5000	0.0195 (6)
H3A	0.2649	0.8098	0.4078	0.029*	0.5
H3B	0.2603	0.8074	0.5966	0.029*	0.5
N1	0.6867 (6)	0.6378 (2)	0.5000	0.0257 (10)
C6	0.9875 (6)	0.5963 (2)	0.5000	0.0166 (7)
C1	0.7510 (5)	0.82253 (15)	0.6715 (4)	0.0159 (6)
C5	0.8601 (7)	0.6481 (2)	0.5000	0.0185 (8)
H5	0.9016	0.6947	0.5000	0.022*
C2	0.7438 (8)	0.8683 (2)	0.5000	0.0199 (9)
C3	0.8969 (10)	0.9197 (3)	0.5000	0.0348 (15)
H3D	0.8814	0.9522	0.6013	0.052*	0.5
H3E	0.8971	0.9453	0.3848	0.052*	0.5
H3C	1.0116	0.8951	0.5139	0.052*	0.5
C4	0.5635 (9)	0.9070 (3)	0.5000	0.0296 (13)
H4B	0.4648	0.8739	0.4833	0.044*	0.5
H4A	0.5622	0.9407	0.4004	0.044*	0.5
H4C	0.5482	0.9311	0.6163	0.044*	0.5
C9	0.6360 (9)	0.5732 (3)	0.4329 (9)	0.0168 (11)	0.5
H9	0.5170	0.5670	0.3879	0.020*	0.5
C8	0.7538 (9)	0.5182 (3)	0.4302 (9)	0.0157 (11)	0.5
H8	0.7255	0.4760	0.3701	0.019*	0.5
C7	0.9349 (7)	0.5290 (3)	0.5306 (8)	0.0145 (11)*	0.5
H6	1.103 (10)	0.608 (3)	0.538 (12)	0.022*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0153 (2)	0.0134 (2)	0.0156 (2)	0.0025 (2)	0.000	0.000
O1	0.0246 (12)	0.0148 (9)	0.0155 (10)	−0.0011 (9)	−0.0014 (9)	0.0031 (8)
O2	0.0220 (12)	0.0182 (10)	0.0172 (11)	−0.0018 (9)	−0.0003 (9)	0.0016 (8)
O3	0.0236 (17)	0.0217 (15)	0.0132 (13)	0.0070 (14)	0.000	0.000
N1	0.0154 (19)	0.0125 (16)	0.049 (3)	0.0026 (14)	0.000	0.000
C6	0.0122 (19)	0.0152 (16)	0.0225 (19)	−0.0022 (15)	0.000	0.000
C1	0.0239 (15)	0.0111 (11)	0.0126 (12)	0.0027 (11)	0.0027 (11)	−0.0017 (9)
C5	0.018 (2)	0.0136 (18)	0.024 (2)	−0.0003 (15)	0.000	0.000
C2	0.037 (3)	0.0097 (16)	0.0127 (18)	0.0002 (17)	0.000	0.000
C3	0.069 (5)	0.015 (2)	0.020 (2)	−0.016 (3)	0.000	0.000
C4	0.055 (4)	0.018 (2)	0.017 (2)	0.018 (2)	0.000	0.000
C9	0.014 (3)	0.015 (2)	0.021 (3)	−0.001 (2)	0.001 (2)	−0.001 (2)
C8	0.014 (3)	0.013 (2)	0.020 (3)	0.001 (2)	0.000 (2)	−0.0007 (19)

Geometric parameters (Å, º)

Zn1—O1	2.076 (2)	C5—H5	0.9500
Zn1—O1^i	2.076 (2)	C2—C1^i	1.540 (4)
Zn1—O2^ii	2.106 (2)	C2—C3	1.509 (8)
Zn1—O2^iii	2.106 (2)	C2—C4	1.532 (8)
Zn1—O3	2.095 (3)	C3—H3D	0.9800
Zn1—N1	2.149 (4)	C3—H3E	0.9800
O1—C1	1.266 (4)	C3—H3C	0.9800
O2—Zn1^iv	2.106 (2)	C4—H4B	0.9800
O2—C1	1.240 (4)	C4—H4A	0.9800
O3—H3A	0.8500	C4—H4C	0.9800
O3—H3B	0.8499	C9—H9	0.9500
N1—C5	1.301 (7)	C9—C8	1.375 (9)
N1—C9	1.393 (7)	C8—H8	0.9500
C6—C5	1.377 (6)	C8—C7	1.546 (8)
C6—C7^i	1.376 (7)	C7—C7^v	1.547 (11)
C6—C7	1.376 (7)	C7—C7^vi	1.480 (11)
C6—H6	0.93 (7)	C7—C7^i	0.450 (11)
C1—C2	1.540 (4)
O1—Zn1—O1^i	84.61 (13)	C1^i—C2—C1	109.8 (3)
O1—Zn1—O2^ii	89.23 (9)	C3—C2—C1	110.6 (3)
O1^i—Zn1—O2^ii	172.48 (10)	C3—C2—C1^i	110.6 (3)
O1^i—Zn1—O2^iii	89.23 (9)	C3—C2—C4	109.6 (4)
O1—Zn1—O2^iii	172.48 (10)	C4—C2—C1^i	108.1 (3)
O1—Zn1—O3	97.25 (10)	C4—C2—C1	108.1 (3)
O1^i—Zn1—O3	97.25 (10)	C2—C3—H3D	109.5
O1—Zn1—N1	90.51 (11)	C2—C3—H3E	109.5
O1^i—Zn1—N1	90.51 (11)	C2—C3—H3C	109.5
O2^iii—Zn1—O2^ii	96.55 (14)	H3D—C3—H3E	109.5
O2^iii—Zn1—N1	85.20 (10)	H3D—C3—H3C	109.5
O2^ii—Zn1—N1	85.20 (10)	H3E—C3—H3C	109.5
O3—Zn1—O2^ii	87.80 (10)	C2—C4—H4B	109.5
O3—Zn1—O2^iii	87.80 (10)	C2—C4—H4A	109.5
O3—Zn1—N1	169.48 (15)	C2—C4—H4C	109.5
C1—O1—Zn1	131.3 (2)	H4B—C4—H4A	109.5
C1—O2—Zn1^iv	133.5 (2)	H4B—C4—H4C	109.5
Zn1—O3—H3A	109.3	H4A—C4—H4C	109.5
Zn1—O3—H3B	109.3	N1—C9—H9	119.1
H3A—O3—H3B	109.5	C8—C9—N1	121.7 (6)
C5—N1—Zn1	124.3 (3)	C8—C9—H9	119.1
C5—N1—C9	113.9 (4)	C9—C8—H8	122.0
C9—N1—Zn1	118.0 (4)	C9—C8—C7	116.1 (5)
C5—C6—H6	117 (4)	C7—C8—H8	122.0
C7—C6—C5	119.5 (4)	C6—C7—C8	107.2 (4)
C7^i—C6—C5	119.5 (4)	C6—C7—C7^vi	122.0 (6)
C7—C6—C7^i	18.8 (5)	C6—C7—C7^v	117.4 (6)
C7^i—C6—H6	123 (4)	C8—C7—C7^v	107.8 (6)
C7—C6—H6	116 (4)	C7^i—C7—C6	80.6 (2)
O1—C1—C2	119.4 (3)	C7^vi—C7—C8	117.7 (5)
O2—C1—O1	123.8 (3)	C7^i—C7—C8	61.5 (3)
O2—C1—C2	116.8 (3)	C7^vi—C7—C7^v	16.9 (4)
N1—C5—C6	124.5 (4)	C7^i—C7—C7^vi	89.995 (4)
N1—C5—H5	117.8	C7^i—C7—C7^v	73.1 (4)
C6—C5—H5	117.8
Zn1—O1—C1—O2	−157.7 (2)	C5—C6—C7—C8	39.3 (5)
Zn1—O1—C1—C2	23.6 (4)	C5—C6—C7—C7^i	95.39 (17)
Zn1^iv—O2—C1—O1	21.1 (5)	C5—C6—C7—C7^v	160.7 (5)
Zn1^iv—O2—C1—C2	−160.2 (3)	C5—C6—C7—C7^vi	179.43 (12)
Zn1—N1—C5—C6	180.0	C9—N1—C5—C6	−22.8 (3)
Zn1—N1—C9—C8	−179.1 (5)	C9—C8—C7—C6	−37.8 (7)
O1—C1—C2—C1^i	−54.2 (6)	C9—C8—C7—C7^v	−165.0 (6)
O1—C1—C2—C3	−176.5 (4)	C9—C8—C7—C7^vi	−180.0 (5)
O1—C1—C2—C4	63.6 (4)	C9—C8—C7—C7^i	−106.5 (6)
O2—C1—C2—C1^i	127.1 (3)	C7—C6—C5—N1	−10.8 (3)
O2—C1—C2—C3	4.8 (5)	C7^i—C6—C5—N1	10.8 (3)
O2—C1—C2—C4	−115.2 (4)	C7^i—C6—C7—C8	−56.1 (4)
N1—C9—C8—C7	8.6 (9)	C7^i—C6—C7—C7^vi	84.0 (2)
C5—N1—C9—C8	22.1 (7)	C7^i—C6—C7—C7^v	65.3 (6)

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

Catena((mu-Dimethylmalonato-O,O')(mu-1,2-bis(4-pyridine)ethylene)- zinc(II) monohydrate) (2)

Crystal data

C17H16N2O4Zn·H2O	F(000) = 816
Mr = 395.70	Dx = 1.568 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.2852 (11) Å	Cell parameters from 3437 reflections
b = 10.4999 (14) Å	θ = 2.2–29.7°
c = 21.684 (3) Å	µ = 1.50 mm^−1
β = 117.282 (3)°	T = 120 K
V = 1676.5 (4) Å^3	Prism, colourless
Z = 4	0.53 × 0.49 × 0.26 mm

Data collection

Bruker SMART APEX CCD area detector diffractometer	5502 independent reflections
Radiation source: sealed tube	4217 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
Detector resolution: 8 pixels mm^-1	θmax = 31.5°, θmin = 2.1°
phi and ω scans	h = −12→12
Absorption correction: multi-scan SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0774 before and 0.0550 after correction. The Ratio of minimum to maximum transmission is 0.8648. The λ/2 correction factor is 0.00150.	k = −15→15
Tmin = 0.645, Tmax = 0.746	l = −31→31
19935 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.015P)^2 + 5.230P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
5502 reflections	Δρmax = 1.03 e Å^−3
236 parameters	Δρmin = −0.76 e Å^−3
2 restraints

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
Zn1	−0.94010 (4)	0.49185 (3)	0.31425 (2)	0.01124 (8)
O1	−0.8734 (2)	0.39897 (18)	0.25040 (10)	0.0144 (4)
O2	−0.6245 (3)	0.36734 (19)	0.34889 (11)	0.0198 (4)
O3	−0.8462 (3)	0.1389 (2)	0.14612 (11)	0.0208 (4)
O4	−0.8486 (3)	0.09836 (18)	0.24633 (10)	0.0143 (4)
N1	−0.7705 (3)	0.6292 (2)	0.37554 (12)	0.0125 (4)
N2	−0.9770 (3)	0.3528 (2)	0.37174 (12)	0.0127 (4)
C1	−0.7703 (4)	0.7452 (3)	0.34932 (15)	0.0157 (5)
H1	−0.8330	0.7562	0.3004	0.019*
C2	−0.6838 (4)	0.8485 (3)	0.38977 (15)	0.0157 (5)
H2	−0.6864	0.9287	0.3690	0.019*
C3	−0.5919 (4)	0.8345 (3)	0.46196 (15)	0.0147 (5)
C4	−0.5915 (4)	0.7137 (3)	0.48878 (15)	0.0172 (5)
H4	−0.5303	0.6997	0.5375	0.021*
C5	−0.6798 (4)	0.6150 (3)	0.44448 (15)	0.0156 (5)
H5	−0.6763	0.5330	0.4636	0.019*
C6	−0.5022 (4)	0.9398 (3)	0.50943 (15)	0.0164 (5)
H6	−0.4420	0.9210	0.5576	0.020*
C7	−1.0104 (4)	0.0627 (2)	0.50265 (17)	0.0174 (5)
H7	−1.0342	0.0909	0.5393	0.021*
C8	−1.0034 (4)	0.3796 (3)	0.42709 (15)	0.0158 (5)
H8	−1.0156	0.4662	0.4370	0.019*
C9	−1.0135 (4)	0.2866 (3)	0.47005 (15)	0.0174 (5)
H9	−1.0301	0.3097	0.5091	0.021*
C10	−0.9993 (4)	0.1592 (3)	0.45620 (15)	0.0149 (5)
C11	−0.9765 (4)	0.1314 (2)	0.39780 (15)	0.0151 (5)
H11	−0.9703	0.0454	0.3854	0.018*
C12	−0.9631 (4)	0.2291 (2)	0.35818 (14)	0.0143 (5)
H12	−0.9433	0.2086	0.3195	0.017*
C13	−0.7163 (4)	0.3485 (2)	0.28622 (14)	0.0134 (5)
C14	−0.6478 (4)	0.2628 (2)	0.24587 (15)	0.0145 (5)
C15	−0.7922 (4)	0.1602 (2)	0.20837 (15)	0.0136 (5)
C16	−0.6169 (4)	0.3444 (3)	0.19418 (17)	0.0236 (6)
H16A	−0.7289	0.3903	0.1644	0.035*
H16B	−0.5825	0.2897	0.1655	0.035*
H16C	−0.5195	0.4058	0.2193	0.035*
C17	−0.4709 (4)	0.1971 (3)	0.29533 (18)	0.0246 (7)
H17A	−0.3792	0.2616	0.3214	0.037*
H17B	−0.4276	0.1444	0.2686	0.037*
H17C	−0.4923	0.1432	0.3277	0.037*
O5	−0.6585 (3)	0.4538 (3)	0.57415 (13)	0.0329 (6)
H5A	−0.575 (5)	0.499 (4)	0.605 (2)	0.076 (17)*
H5B	−0.697 (6)	0.421 (4)	0.601 (2)	0.070 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01379 (13)	0.00727 (12)	0.01406 (14)	−0.00049 (12)	0.00760 (11)	0.00000 (12)
O1	0.0151 (9)	0.0127 (8)	0.0170 (10)	0.0019 (7)	0.0088 (8)	−0.0015 (7)
O2	0.0198 (10)	0.0199 (10)	0.0165 (10)	−0.0008 (8)	0.0057 (8)	−0.0031 (8)
O3	0.0230 (10)	0.0231 (10)	0.0216 (11)	−0.0050 (8)	0.0149 (9)	−0.0076 (9)
O4	0.0148 (9)	0.0122 (8)	0.0167 (10)	−0.0027 (7)	0.0079 (8)	−0.0013 (7)
N1	0.0112 (10)	0.0104 (9)	0.0155 (11)	−0.0008 (8)	0.0059 (9)	−0.0015 (8)
N2	0.0135 (10)	0.0107 (9)	0.0149 (11)	0.0002 (8)	0.0074 (9)	0.0006 (8)
C1	0.0159 (12)	0.0144 (12)	0.0166 (13)	−0.0014 (10)	0.0074 (11)	−0.0009 (10)
C2	0.0168 (12)	0.0108 (11)	0.0184 (14)	−0.0017 (10)	0.0073 (11)	−0.0014 (10)
C3	0.0144 (12)	0.0136 (11)	0.0173 (13)	−0.0016 (10)	0.0083 (11)	−0.0026 (10)
C4	0.0190 (13)	0.0164 (12)	0.0153 (13)	−0.0007 (10)	0.0071 (11)	0.0005 (10)
C5	0.0164 (12)	0.0117 (11)	0.0175 (13)	−0.0005 (10)	0.0067 (11)	0.0004 (10)
C6	0.0182 (12)	0.0161 (12)	0.0141 (14)	−0.0031 (11)	0.0068 (11)	−0.0040 (10)
C7	0.0221 (13)	0.0158 (12)	0.0190 (13)	−0.0001 (11)	0.0135 (11)	0.0037 (11)
C8	0.0222 (13)	0.0116 (11)	0.0176 (13)	0.0001 (10)	0.0125 (11)	−0.0005 (10)
C9	0.0237 (14)	0.0147 (12)	0.0188 (14)	−0.0004 (10)	0.0140 (12)	−0.0006 (10)
C10	0.0150 (12)	0.0128 (11)	0.0181 (14)	−0.0003 (9)	0.0086 (11)	0.0028 (10)
C11	0.0196 (13)	0.0094 (11)	0.0197 (14)	−0.0004 (10)	0.0118 (11)	0.0009 (10)
C12	0.0175 (12)	0.0130 (11)	0.0165 (13)	−0.0012 (10)	0.0113 (11)	−0.0008 (10)
C13	0.0159 (12)	0.0091 (10)	0.0164 (13)	−0.0035 (9)	0.0085 (10)	−0.0019 (9)
C14	0.0139 (11)	0.0116 (11)	0.0221 (14)	0.0001 (9)	0.0116 (11)	−0.0015 (10)
C15	0.0123 (11)	0.0100 (11)	0.0207 (14)	0.0020 (9)	0.0094 (11)	−0.0005 (10)
C16	0.0297 (16)	0.0184 (13)	0.0348 (18)	−0.0049 (12)	0.0252 (15)	−0.0033 (13)
C17	0.0112 (12)	0.0195 (13)	0.0370 (19)	0.0015 (10)	0.0059 (13)	−0.0053 (13)
O5	0.0298 (13)	0.0455 (15)	0.0271 (13)	−0.0132 (11)	0.0163 (11)	−0.0027 (11)

Geometric parameters (Å, º)

Zn1—O1	1.9684 (19)	C7—C7^iv	1.339 (5)
Zn1—O4^i	1.9832 (19)	C7—H7	0.9500
Zn1—N1	2.027 (2)	C7—C10	1.461 (4)
Zn1—N2	2.032 (2)	C8—H8	0.9500
O1—C13	1.285 (3)	C8—C9	1.378 (4)
O2—C13	1.232 (3)	C9—H9	0.9500
O3—C15	1.232 (3)	C9—C10	1.387 (4)
O4—Zn1^ii	1.9832 (19)	C10—C11	1.394 (4)
O4—C15	1.292 (3)	C11—H11	0.9500
N1—C1	1.345 (3)	C11—C12	1.375 (4)
N1—C5	1.339 (4)	C12—H12	0.9500
N2—C8	1.345 (3)	C13—C14	1.534 (4)
N2—C12	1.348 (3)	C14—C15	1.537 (4)
C1—H1	0.9500	C14—C16	1.523 (4)
C1—C2	1.372 (4)	C14—C17	1.528 (4)
C2—H2	0.9500	C16—H16A	0.9800
C2—C3	1.400 (4)	C16—H16B	0.9800
C3—C4	1.395 (4)	C16—H16C	0.9800
C3—C6	1.460 (4)	C17—H17A	0.9800
C4—H4	0.9500	C17—H17B	0.9800
C4—C5	1.374 (4)	C17—H17C	0.9800
C5—H5	0.9500	O5—H5A	0.850 (3)
C6—C6^iii	1.335 (5)	O5—H5B	0.850 (3)
C6—H6	0.9500
O1—Zn1—O4^i	105.12 (8)	C8—C9—H9	120.0
O1—Zn1—N1	118.68 (8)	C8—C9—C10	120.0 (3)
O1—Zn1—N2	104.19 (9)	C10—C9—H9	120.0
O4^i—Zn1—N1	99.75 (9)	C9—C10—C7	118.8 (3)
O4^i—Zn1—N2	118.44 (8)	C9—C10—C11	117.3 (2)
N1—Zn1—N2	111.28 (9)	C11—C10—C7	124.0 (2)
C13—O1—Zn1	108.20 (17)	C10—C11—H11	120.2
C15—O4—Zn1^ii	109.18 (17)	C12—C11—C10	119.7 (2)
C1—N1—Zn1	120.15 (19)	C12—C11—H11	120.2
C5—N1—Zn1	121.26 (18)	N2—C12—C11	122.9 (2)
C5—N1—C1	117.6 (2)	N2—C12—H12	118.5
C8—N2—Zn1	121.93 (18)	C11—C12—H12	118.5
C8—N2—C12	117.5 (2)	O1—C13—C14	115.7 (2)
C12—N2—Zn1	120.45 (18)	O2—C13—O1	122.9 (2)
N1—C1—H1	118.4	O2—C13—C14	121.4 (2)
N1—C1—C2	123.2 (3)	C13—C14—C15	108.1 (2)
C2—C1—H1	118.4	C16—C14—C13	108.7 (2)
C1—C2—H2	120.4	C16—C14—C15	111.0 (2)
C1—C2—C3	119.3 (3)	C16—C14—C17	109.9 (2)
C3—C2—H2	120.4	C17—C14—C13	110.6 (2)
C2—C3—C6	123.3 (2)	C17—C14—C15	108.6 (2)
C4—C3—C2	117.2 (2)	O3—C15—O4	123.5 (2)
C4—C3—C6	119.4 (3)	O3—C15—C14	120.7 (2)
C3—C4—H4	120.1	O4—C15—C14	115.9 (2)
C5—C4—C3	119.7 (3)	C14—C16—H16A	109.5
C5—C4—H4	120.1	C14—C16—H16B	109.5
N1—C5—C4	122.9 (3)	C14—C16—H16C	109.5
N1—C5—H5	118.5	H16A—C16—H16B	109.5
C4—C5—H5	118.5	H16A—C16—H16C	109.5
C3—C6—H6	117.4	H16B—C16—H16C	109.5
C6^iii—C6—C3	125.3 (3)	C14—C17—H17A	109.5
C6^iii—C6—H6	117.4	C14—C17—H17B	109.5
C7^iv—C7—H7	117.6	C14—C17—H17C	109.5
C7^iv—C7—C10	124.8 (4)	H17A—C17—H17B	109.5
C10—C7—H7	117.6	H17A—C17—H17C	109.5
N2—C8—H8	118.7	H17B—C17—H17C	109.5
N2—C8—C9	122.7 (2)	H5A—O5—H5B	97 (4)
C9—C8—H8	118.7
Zn1—O1—C13—O2	−5.1 (3)	C2—C3—C6—C6^iii	0.6 (6)
Zn1—O1—C13—C14	175.30 (17)	C3—C4—C5—N1	−1.0 (4)
Zn1^ii—O4—C15—O3	−10.2 (3)	C4—C3—C6—C6^iii	−177.8 (4)
Zn1^ii—O4—C15—C14	170.93 (17)	C5—N1—C1—C2	−0.7 (4)
Zn1—N1—C1—C2	168.2 (2)	C6—C3—C4—C5	178.3 (3)
Zn1—N1—C5—C4	−167.3 (2)	C7^iv—C7—C10—C9	−176.4 (4)
Zn1—N2—C8—C9	−174.4 (2)	C7^iv—C7—C10—C11	4.1 (6)
Zn1—N2—C12—C11	176.2 (2)	C7—C10—C11—C12	−178.4 (3)
O1—C13—C14—C15	−54.9 (3)	C8—N2—C12—C11	0.6 (4)
O1—C13—C14—C16	65.7 (3)	C8—C9—C10—C7	180.0 (3)
O1—C13—C14—C17	−173.6 (2)	C8—C9—C10—C11	−0.5 (4)
O2—C13—C14—C15	125.6 (3)	C9—C10—C11—C12	2.1 (4)
O2—C13—C14—C16	−113.9 (3)	C10—C11—C12—N2	−2.2 (4)
O2—C13—C14—C17	6.8 (3)	C12—N2—C8—C9	1.1 (4)
N1—C1—C2—C3	−0.5 (4)	C13—C14—C15—O3	130.3 (3)
N2—C8—C9—C10	−1.1 (5)	C13—C14—C15—O4	−50.7 (3)
C1—N1—C5—C4	1.5 (4)	C16—C14—C15—O3	11.2 (3)
C1—C2—C3—C4	1.0 (4)	C16—C14—C15—O4	−169.9 (2)
C1—C2—C3—C6	−177.5 (3)	C17—C14—C15—O3	−109.7 (3)
C2—C3—C4—C5	−0.2 (4)	C17—C14—C15—O4	69.3 (3)

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

Catena((mu-Dimethylmalonato-O,O')(mu-1,2-bis(4-pyridine)ethylene-N,N')- zinc(II) (mu-Dimethylmalonato-O,O')(mu-4-tetrakis(4- pyridyl)cyclobutane-N,N',N'',N''')- zinc(II) hydrate) (2a)

Crystal data

0.25(C68H64N8O16Zn4)·0.25(H2O)	Dx = 1.492 Mg m^−3
Mr = 382.69	Synchrotron radiation, λ = 0.9699 Å
Orthorhombic, Pnna	Cell parameters from 259 reflections
a = 8.3000 (17) Å	θ = 4.8–37.2°
b = 10.400 (2) Å	µ = 3.32 mm^−1
c = 19.740 (4) Å	T = 100 K
V = 1704.0 (6) Å^3	Prism, colourless
Z = 4	0.53 × 0.49 × 0.26 mm
F(000) = 788

Data collection

Mar CCD diffractometer	976 reflections with I > 2σ(I)
φ scans	Rint = 0.087
Absorption correction: multi-scan SCALA	θmax = 38.5°, θmin = 4.5°
Tmin = 0.645, Tmax = 0.746	h = −8→8
10296 measured reflections	k = −10→13
1696 independent reflections	l = −24→25

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.093	w = 1/[σ^2(Fo^2) + (0.020P)^2 + 10.P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.214	(Δ/σ)max = 0.009
S = 1.05	Δρmax = 0.63 e Å^−3
1696 reflections	Δρmin = −0.89 e Å^−3
117 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
30 restraints	Extinction coefficient: 0.0051 (16)

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	0.7500	0.5000	0.31652 (6)	0.0717 (6)
O1	0.6078 (7)	0.4026 (4)	0.2549 (3)	0.0662 (14)
O2	0.4889 (9)	0.3567 (6)	0.3529 (4)	0.112 (2)
N1	0.6406 (10)	0.6421 (6)	0.3741 (3)	0.083 (2)
C1	0.625 (2)	0.766 (2)	0.3554 (12)	0.063 (3)*	0.5
H1	0.6612	0.7859	0.3109	0.076*	0.5
C2	0.5654 (19)	0.8684 (16)	0.3916 (8)	0.055 (2)*	0.5
H2	0.5728	0.9531	0.3739	0.066*	0.5
C3	0.498 (2)	0.8484 (15)	0.4505 (8)	0.063 (3)*	0.5
C4	0.501 (2)	0.7187 (16)	0.4738 (8)	0.069 (3)*	0.5
H4	0.4694	0.6987	0.5188	0.083*	0.5
C5	0.550 (2)	0.6223 (17)	0.4303 (8)	0.067 (3)*	0.5
H5	0.5190	0.5367	0.4405	0.081*	0.5
C7	0.4990 (12)	0.3427 (7)	0.2913 (5)	0.081 (2)
C8	0.3904 (18)	0.2500	0.2500	0.096 (4)
O3	0.2500	0.5000	0.4246 (13)	0.080 (10)	0.25
H3A	0.3021	0.4881	0.3881	0.120*	0.25
H3B	0.1816	0.4400	0.4297	0.120*	0.25
C1A	0.669 (3)	0.767 (2)	0.3537 (12)	0.063 (3)*	0.5
H1A	0.7171	0.7855	0.3112	0.076*	0.5
C5A	0.622 (2)	0.6133 (17)	0.4430 (8)	0.067 (3)*	0.5
H5A	0.6351	0.5275	0.4586	0.081*	0.5
C2A	0.6279 (19)	0.8570 (16)	0.3958 (8)	0.055 (2)*	0.5
H2A	0.6261	0.9435	0.3803	0.066*	0.5
C3A	0.586 (2)	0.8310 (15)	0.4636 (7)	0.063 (3)*	0.5
C4A	0.587 (2)	0.7069 (15)	0.4868 (9)	0.069 (3)*	0.5
H4A	0.5631	0.6879	0.5328	0.083*	0.5
C1AA	0.5025 (18)	0.9385 (13)	0.5064 (8)	0.060 (4)*	0.5
C0AA	0.348 (3)	0.930 (3)	0.4872 (14)	0.067 (8)*	0.25
C2AA	0.661 (4)	0.923 (3)	0.5234 (15)	0.073 (9)*	0.25
C9B	0.312 (3)	0.327 (2)	0.1861 (9)	0.095 (6)*	0.5
H9BA	0.2399	0.3942	0.2029	0.143*	0.5
H9BB	0.2517	0.2668	0.1577	0.143*	0.5
H9BC	0.3987	0.3663	0.1593	0.143*	0.5
C9A	0.264 (2)	0.3292 (17)	0.2230 (9)	0.085 (5)*	0.5
H9AA	0.2402	0.3992	0.2547	0.127*	0.5
H9AB	0.1665	0.2770	0.2164	0.127*	0.5
H9AC	0.2976	0.3653	0.1794	0.127*	0.5
H1AA	0.478 (4)	0.886 (11)	0.543 (4)	0.25 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.1002 (13)	0.0486 (8)	0.0663 (9)	−0.0004 (7)	0.000	0.000
O1	0.072 (4)	0.041 (2)	0.085 (3)	0.003 (2)	0.007 (3)	0.001 (2)
O2	0.133 (6)	0.078 (4)	0.125 (5)	−0.002 (4)	0.050 (4)	0.008 (4)
N1	0.114 (7)	0.069 (4)	0.065 (4)	0.000 (4)	0.019 (4)	−0.005 (3)
C7	0.077 (6)	0.044 (4)	0.123 (5)	0.003 (4)	0.024 (4)	0.005 (4)
C8	0.094 (5)	0.078 (5)	0.117 (5)	0.000	0.000	0.002 (4)
O3	0.08 (3)	0.13 (3)	0.036 (13)	0.02 (3)	0.000	0.000

Geometric parameters (Å, º)

Zn1—O1^i	1.975 (5)	C1A—H1A	0.9500
Zn1—O1	1.975 (5)	C1A—C2A	1.30 (3)
Zn1—N1	2.073 (7)	C5A—H5A	0.9500
Zn1—N1^i	2.073 (7)	C5A—C4A	1.33 (2)
O1—C7	1.311 (10)	C2A—H2A	0.9500
O2—C7	1.228 (11)	C2A—C3A	1.41 (2)
N1—C1	1.35 (2)	C3A—C4A	1.37 (2)
N1—C5	1.355 (18)	C3A—C1AA	1.56 (2)
N1—C1A	1.38 (2)	C3A—C2AA	1.64 (3)
N1—C5A	1.402 (17)	C4A—H4A	0.9500
C1—H1	0.9500	C1AA—C1AA^iii	1.30 (3)
C1—C2	1.37 (3)	C1AA—C0AA^iii	1.85 (3)
C2—H2	0.9500	C1AA—C0AA	1.34 (2)
C2—C3	1.31 (2)	C1AA—C2AA	1.37 (3)
C3—C4	1.43 (2)	C1AA—H1AA	0.93 (2)
C3—C1AA	1.45 (2)	C0AA—C1AA^iii	1.85 (3)
C3—C0AA	1.67 (3)	C0AA—C2AA^iii	1.55 (4)
C4—H4	0.9500	C0AA—C2AA^iv	1.57 (5)
C4—C5	1.38 (2)	C2AA—C0AA^iii	1.55 (4)
C5—H5	0.9500	C2AA—C0AA^v	1.57 (5)
C7—C8	1.551 (12)	C9B—H9BA	0.9800
C8—C7^ii	1.551 (12)	C9B—H9BB	0.9800
C8—C9B	1.628 (15)	C9B—H9BC	0.9800
C8—C9A	1.439 (14)	C9A—H9AA	0.9800
O3—H3A	0.8500	C9A—H9AB	0.9800
O3—H3B	0.8498	C9A—H9AC	0.9800
O1^i—Zn1—O1	103.9 (3)	C4A—C3A—C2AA	107.9 (16)
O1^i—Zn1—N1	103.5 (2)	C1AA—C3A—C2AA	50.4 (10)
O1—Zn1—N1	116.2 (3)	C5A—C4A—C3A	118.3 (16)
O1—Zn1—N1^i	103.5 (2)	C5A—C4A—H4A	120.9
O1^i—Zn1—N1^i	116.2 (3)	C3A—C4A—H4A	120.9
N1—Zn1—N1^i	113.6 (4)	C3—C1AA—C0AA^iii	123.2 (14)
C7—O1—Zn1	108.5 (6)	C3—C1AA—H1AA	102 (9)
C1—N1—Zn1	125.0 (11)	C3A—C1AA—C0AA^iii	105.7 (13)
C1—N1—C5	108.5 (13)	C3A—C1AA—H1AA	95 (9)
C5—N1—Zn1	125.7 (9)	C1AA^iii—C1AA—C3	119.1 (19)
C1A—N1—Zn1	115.8 (10)	C1AA^iii—C1AA—C3A	127.7 (19)
C1A—N1—C5A	120.2 (13)	C1AA^iii—C1AA—C0AA	89 (2)
C5A—N1—Zn1	115.3 (8)	C1AA^iii—C1AA—C0AA^iii	46.3 (11)
N1—C1—H1	115.4	C1AA^iii—C1AA—C2AA	101 (2)
N1—C1—C2	129.2 (19)	C1AA^iii—C1AA—H1AA	136 (10)
C2—C1—H1	115.4	C0AA—C1AA—C3	73.6 (13)
C1—C2—H2	120.2	C0AA—C1AA—C3A	102.9 (15)
C3—C2—C1	119.7 (17)	C0AA—C1AA—C0AA^iii	135.1 (14)
C3—C2—H2	120.1	C0AA—C1AA—C2AA	169 (2)
C2—C3—C4	115.5 (14)	C0AA—C1AA—H1AA	88.6 (17)
C2—C3—C1AA	124.4 (15)	C0AA^iii—C1AA—H1AA	122 (6)
C2—C3—C0AA	128.6 (16)	C2AA—C1AA—C3	97.7 (15)
C4—C3—C1AA	111.5 (13)	C2AA—C1AA—C3A	67.8 (13)
C4—C3—C0AA	110.7 (16)	C2AA—C1AA—C0AA^iii	55.0 (17)
C1AA—C3—C0AA	50.2 (9)	C2AA—C1AA—H1AA	86.9 (17)
C3—C4—H4	120.3	C3—C0AA—C1AA^iii	84.6 (15)
C5—C4—C3	119.5 (15)	C1AA—C0AA—C3	56.2 (13)
C5—C4—H4	120.3	C1AA—C0AA—C1AA^iii	44.9 (14)
N1—C5—C4	124.2 (16)	C1AA—C0AA—C2AA^iii	91 (2)
N1—C5—H5	117.9	C1AA—C0AA—C2AA^iv	171 (3)
C4—C5—H5	117.9	C2AA^iv—C0AA—C3	131 (2)
O1—C7—C8	114.0 (8)	C2AA^iii—C0AA—C3	119 (2)
O2—C7—O1	122.3 (9)	C2AA^iv—C0AA—C1AA^iii	135.0 (19)
O2—C7—C8	123.7 (8)	C2AA^iii—C0AA—C1AA^iii	46.4 (11)
C7^ii—C8—C7	109.0 (11)	C2AA^iii—C0AA—C2AA^iv	88.8 (17)
C7—C8—C9B	109.4 (9)	C1AA—C2AA—C3A	61.7 (14)
C7^ii—C8—C9B	97.5 (8)	C1AA—C2AA—C0AA^v	156 (3)
C9A—C8—C7	105.3 (8)	C1AA—C2AA—C0AA^iii	78.6 (18)
C9A—C8—C7^ii	125.9 (8)	C0AA^iii—C2AA—C3A	117 (2)
H3A—O3—H3B	109.5	C0AA^v—C2AA—C3A	108 (2)
N1—C1A—H1A	121.7	C0AA^iii—C2AA—C0AA^v	89.1 (19)
C2A—C1A—N1	116.6 (19)	C8—C9B—H9BA	109.5
C2A—C1A—H1A	121.7	C8—C9B—H9BB	109.5
N1—C5A—H5A	120.1	C8—C9B—H9BC	109.5
C4A—C5A—N1	119.8 (15)	H9BA—C9B—H9BB	109.5
C4A—C5A—H5A	120.1	H9BA—C9B—H9BC	109.5
C1A—C2A—H2A	118.9	H9BB—C9B—H9BC	109.5
C1A—C2A—C3A	122.2 (17)	C8—C9A—H9AA	109.5
C3A—C2A—H2A	118.9	C8—C9A—H9AB	109.5
C2A—C3A—C1AA	119.1 (14)	C8—C9A—H9AC	109.5
C2A—C3A—C2AA	118.3 (17)	H9AA—C9A—H9AB	109.5
C4A—C3A—C2A	119.7 (15)	H9AA—C9A—H9AC	109.5
C4A—C3A—C1AA	119.9 (14)	H9AB—C9A—H9AC	109.5
Zn1—O1—C7—O2	4.3 (10)	C5A—N1—C1A—C2A	−21 (2)
Zn1—O1—C7—C8	−173.5 (6)	C2A—C3A—C4A—C5A	−3 (3)
Zn1—N1—C1—C2	−175.0 (15)	C2A—C3A—C1AA—C3	66.8 (19)
Zn1—N1—C5—C4	168.9 (13)	C2A—C3A—C1AA—C1AA^iii	−17 (3)
Zn1—N1—C1A—C2A	−167.5 (14)	C2A—C3A—C1AA—C0AA	82 (2)
Zn1—N1—C5A—C4A	165.3 (13)	C2A—C3A—C1AA—C0AA^iii	−63.5 (19)
O1—C7—C8—C7^ii	52.5 (5)	C2A—C3A—C1AA—C2AA	−104 (2)
O1—C7—C8—C9B	−52.9 (13)	C2A—C3A—C2AA—C1AA	105.7 (19)
O1—C7—C8—C9A	−84.9 (12)	C2A—C3A—C2AA—C0AA^v	−51 (3)
O2—C7—C8—C7^ii	−125.2 (10)	C2A—C3A—C2AA—C0AA^iii	48 (3)
O2—C7—C8—C9B	129.3 (12)	C3A—C1AA—C0AA—C3	−7.7 (12)
O2—C7—C8—C9A	97.3 (12)	C3A—C1AA—C0AA—C1AA^iii	−129 (2)
N1—C1—C2—C3	−7 (3)	C3A—C1AA—C0AA—C2AA^iii	−132.0 (18)
N1—C1A—C2A—C3A	12 (3)	C3A—C1AA—C2AA—C0AA^iii	130 (2)
N1—C5A—C4A—C3A	−7 (3)	C3A—C1AA—C2AA—C0AA^v	70 (6)
C1—N1—C5—C4	−21 (2)	C4A—C3A—C1AA—C3	−100 (2)
C1—N1—C1A—C2A	62 (6)	C4A—C3A—C1AA—C1AA^iii	176 (2)
C1—N1—C5A—C4A	2 (2)	C4A—C3A—C1AA—C0AA	−85 (2)
C1—C2—C3—C4	3 (3)	C4A—C3A—C1AA—C0AA^iii	129.8 (17)
C1—C2—C3—C1AA	148.0 (17)	C4A—C3A—C1AA—C2AA	89 (2)
C1—C2—C3—C0AA	−149 (2)	C4A—C3A—C2AA—C1AA	−114.4 (18)
C2—C3—C4—C5	−10 (3)	C4A—C3A—C2AA—C0AA^v	89 (2)
C2—C3—C1AA—C3A	−81 (2)	C4A—C3A—C2AA—C0AA^iii	−172 (2)
C2—C3—C1AA—C1AA^iii	35 (3)	C1AA—C3—C4—C5	−158.7 (15)
C2—C3—C1AA—C0AA	114 (2)	C1AA—C3—C0AA—C1AA^iii	37.5 (14)
C2—C3—C1AA—C0AA^iii	−19 (2)	C1AA—C3—C0AA—C2AA^iv	−173 (4)
C2—C3—C1AA—C2AA	−72 (2)	C1AA—C3—C0AA—C2AA^iii	70 (2)
C2—C3—C0AA—C1AA	−106 (2)	C1AA—C3A—C4A—C5A	163.9 (15)
C2—C3—C0AA—C1AA^iii	−69 (2)	C1AA—C3A—C2AA—C0AA^iii	−58 (2)
C2—C3—C0AA—C2AA^iii	−36 (3)	C1AA—C3A—C2AA—C0AA^v	−156 (3)
C2—C3—C0AA—C2AA^iv	81 (3)	C1AA^iii—C1AA—C0AA—C3	120.9 (18)
C3—C4—C5—N1	20 (3)	C1AA^iii—C1AA—C0AA—C2AA^iii	−4 (2)
C3—C1AA—C0AA—C1AA^iii	−120.9 (18)	C1AA^iii—C1AA—C2AA—C3A	−126.3 (19)
C3—C1AA—C0AA—C2AA^iii	−124 (2)	C1AA^iii—C1AA—C2AA—C0AA^v	−57 (6)
C3—C1AA—C2AA—C3A	−4.5 (13)	C1AA^iii—C1AA—C2AA—C0AA^iii	4 (2)
C3—C1AA—C2AA—C0AA^iii	125.4 (18)	C0AA—C3—C4—C5	147.2 (18)
C3—C1AA—C2AA—C0AA^v	65 (6)	C0AA—C3—C1AA—C3A	165 (2)
C4—C3—C1AA—C3A	65.4 (18)	C0AA—C3—C1AA—C1AA^iii	−79 (2)
C4—C3—C1AA—C1AA^iii	−178.7 (19)	C0AA—C3—C1AA—C0AA^iii	−133.7 (17)
C4—C3—C1AA—C0AA^iii	126.7 (18)	C0AA—C3—C1AA—C2AA	173 (2)
C4—C3—C1AA—C0AA	−99.6 (19)	C0AA^iii—C1AA—C0AA—C3	120.9 (18)
C4—C3—C1AA—C2AA	74 (2)	C0AA^iii—C1AA—C0AA—C1AA^iii	−0.002 (3)
C4—C3—C0AA—C1AA^iii	138.7 (14)	C0AA^iii—C1AA—C0AA—C2AA^iii	−4 (2)
C4—C3—C0AA—C1AA	101.2 (17)	C0AA^iii—C1AA—C2AA—C3A	−130 (2)
C4—C3—C0AA—C2AA^iv	−72 (3)	C0AA—C1AA—C2AA—C3A	31 (13)
C4—C3—C0AA—C2AA^iii	171.4 (19)	C0AA—C1AA—C2AA—C0AA^v	101 (12)
C5—N1—C1—C2	15 (3)	C0AA—C1AA—C2AA—C0AA^iii	161 (11)
C5—N1—C1A—C2A	10 (2)	C0AA^iii—C1AA—C2AA—C0AA^v	−60 (5)
C5—N1—C5A—C4A	−75 (3)	C2AA—C3A—C4A—C5A	−142.0 (19)
C1A—N1—C1—C2	−118 (8)	C2AA—C3A—C1AA—C3	171 (3)
C1A—N1—C5—C4	−8 (2)	C2AA—C3A—C1AA—C1AA^iii	87 (3)
C1A—N1—C5A—C4A	19 (2)	C2AA—C3A—C1AA—C0AA^iii	40.7 (18)
C1A—C2A—C3A—C4A	0 (3)	C2AA—C3A—C1AA—C0AA	−174 (2)
C1A—C2A—C3A—C1AA	−167.0 (17)	C2AA—C1AA—C0AA—C3	−37 (12)
C1A—C2A—C3A—C2AA	135 (2)	C2AA—C1AA—C0AA—C1AA^iii	−158 (13)
C5A—N1—C1—C2	−13 (3)	C2AA—C1AA—C0AA—C2AA^iii	−162 (11)
C5A—N1—C5—C4	93 (3)

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

Catena(Bis(hydrogen dimethylmalonato-O,O')(mu-1,2-bis(4-pyridine)ethylene)- zinc(II)) (3)

Crystal data

C22H24N2O8Zn	F(000) = 1056
Mr = 509.80	Dx = 1.609 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.0211 (8) Å	Cell parameters from 3576 reflections
b = 5.8795 (2) Å	θ = 2.5–28.2°
c = 21.7192 (12) Å	µ = 1.22 mm^−1
β = 113.890 (1)°	T = 150 K
V = 2104.10 (17) Å^3	Prismatic, colourless
Z = 4	0.10 × 0.10 × 0.10 mm

Data collection

Bruker APEX-II CCD diffractometer	2296 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
Graphite monochromator	θmax = 28.2°, θmin = 2.1°
φ and ω scans	h = −23→22
6512 measured reflections	k = −7→7
2562 independent reflections	l = −28→28

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ^2(Fo^2) + (0.030P)^2] where P = (Fo^2 + 2Fc^2)/3
2562 reflections	(Δ/σ)max < 0.001
150 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.54 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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Zn1	0.0000	0.82335 (4)	0.2500	0.01101 (9)
N1	0.00568 (8)	1.0352 (2)	0.17759 (6)	0.0123 (3)
O1	0.08734 (7)	0.61376 (18)	0.30587 (5)	0.0151 (2)
O2	0.16496 (7)	0.89240 (19)	0.29766 (6)	0.0181 (3)
O3	0.24613 (7)	0.4995 (2)	0.26976 (5)	0.0196 (3)
H3A	0.2784	0.4620	0.2537	0.029*
O4	0.34389 (7)	0.3769 (2)	0.36617 (6)	0.0253 (3)
C1	0.15637 (9)	0.7056 (3)	0.32068 (7)	0.0122 (3)
C2	0.23108 (9)	0.5817 (3)	0.37167 (7)	0.0128 (3)
C3	0.28031 (9)	0.4747 (3)	0.33595 (8)	0.0147 (3)
C4	0.20756 (11)	0.3911 (3)	0.40851 (8)	0.0202 (4)
H4A	0.1740	0.2822	0.3763	0.030*
H4B	0.1782	0.4544	0.4328	0.030*
H4C	0.2557	0.3173	0.4395	0.030*
C5	0.28512 (11)	0.7582 (3)	0.42226 (8)	0.0208 (4)
H5A	0.3321	0.6839	0.4548	0.031*
H5B	0.2551	0.8292	0.4448	0.031*
H5C	0.3019	0.8715	0.3988	0.031*
C6	−0.03558 (10)	0.9967 (3)	0.11115 (7)	0.0145 (3)
H6A	−0.0670	0.8658	0.0977	0.017*
C7	−0.03327 (10)	1.1419 (3)	0.06242 (8)	0.0157 (3)
H7A	−0.0626	1.1086	0.0171	0.019*
C8	0.01346 (9)	1.3403 (3)	0.08138 (7)	0.0131 (3)
C9	0.05635 (10)	1.3791 (3)	0.15019 (8)	0.0142 (3)
H9A	0.0884	1.5084	0.1651	0.017*
C10	0.05089 (10)	1.2243 (3)	0.19585 (7)	0.0138 (3)
H10A	0.0800	1.2525	0.2415	0.017*
C11	0.01970 (9)	1.5065 (3)	0.03347 (7)	0.0142 (3)
H11A	0.0537	1.6308	0.0510	0.017*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01226 (14)	0.01073 (14)	0.00925 (13)	0.000	0.00354 (10)	0.000
N1	0.0129 (6)	0.0127 (6)	0.0110 (6)	0.0011 (5)	0.0047 (5)	0.0005 (5)
O1	0.0117 (6)	0.0143 (6)	0.0159 (5)	0.0005 (4)	0.0022 (5)	−0.0003 (4)
O2	0.0180 (6)	0.0172 (6)	0.0191 (6)	0.0033 (5)	0.0075 (5)	0.0072 (5)
O3	0.0172 (6)	0.0264 (7)	0.0155 (6)	0.0079 (5)	0.0071 (5)	−0.0012 (5)
O4	0.0175 (7)	0.0318 (7)	0.0243 (6)	0.0123 (5)	0.0060 (5)	0.0063 (5)
C1	0.0128 (8)	0.0157 (8)	0.0086 (7)	0.0026 (6)	0.0046 (6)	−0.0021 (6)
C2	0.0120 (8)	0.0133 (8)	0.0116 (7)	0.0010 (6)	0.0033 (6)	0.0010 (6)
C3	0.0136 (8)	0.0118 (8)	0.0171 (8)	0.0000 (6)	0.0048 (7)	0.0013 (6)
C4	0.0205 (9)	0.0211 (9)	0.0181 (8)	0.0030 (7)	0.0069 (7)	0.0085 (7)
C5	0.0178 (9)	0.0209 (9)	0.0173 (8)	−0.0006 (7)	0.0005 (7)	−0.0029 (7)
C6	0.0147 (8)	0.0143 (8)	0.0135 (7)	−0.0027 (6)	0.0046 (6)	−0.0018 (6)
C7	0.0152 (8)	0.0194 (9)	0.0093 (7)	−0.0022 (6)	0.0017 (6)	−0.0005 (6)
C8	0.0119 (8)	0.0144 (8)	0.0120 (7)	0.0021 (6)	0.0038 (6)	0.0023 (6)
C9	0.0146 (8)	0.0125 (8)	0.0136 (7)	−0.0020 (6)	0.0037 (6)	−0.0009 (6)
C10	0.0147 (8)	0.0141 (8)	0.0101 (7)	0.0002 (6)	0.0024 (6)	−0.0003 (6)
C11	0.0146 (8)	0.0128 (8)	0.0143 (7)	−0.0015 (6)	0.0051 (7)	0.0010 (6)

Geometric parameters (Å, º)

Zn1—O1^i	1.9802 (11)	C1—C2	1.537 (2)
Zn1—O1	1.9802 (11)	C2—C4	1.533 (2)
Zn1—N1^i	2.0410 (12)	C2—C3	1.530 (2)
Zn1—N1	2.0410 (12)	C2—C5	1.538 (2)
N1—C10	1.340 (2)	C6—C7	1.373 (2)
N1—C6	1.3481 (19)	C7—C8	1.400 (2)
O1—C1	1.2722 (19)	C8—C9	1.395 (2)
O2—C1	1.2422 (18)	C8—C11	1.465 (2)
O3—C3	1.3230 (18)	C9—C10	1.378 (2)
O4—C3	1.2104 (19)	C11—C11^ii	1.337 (3)
O1^i—Zn1—O1	103.03 (6)	C3—C2—C1	110.36 (12)
O1^i—Zn1—N1^i	125.21 (5)	C4—C2—C5	110.44 (13)
O1—Zn1—N1^i	100.55 (5)	C3—C2—C5	108.06 (13)
O1^i—Zn1—N1	100.55 (5)	C1—C2—C5	108.15 (13)
O1—Zn1—N1	125.20 (5)	O4—C3—O3	124.30 (14)
N1^i—Zn1—N1	104.77 (7)	O4—C3—C2	122.42 (14)
C10—N1—C6	117.50 (13)	O3—C3—C2	113.28 (12)
C10—N1—Zn1	119.51 (10)	N1—C6—C7	123.01 (14)
C6—N1—Zn1	122.97 (10)	C6—C7—C8	119.59 (14)
C1—O1—Zn1	110.12 (10)	C7—C8—C9	117.22 (14)
O2—C1—O1	122.82 (14)	C7—C8—C11	123.87 (14)
O2—C1—C2	119.57 (13)	C9—C8—C11	118.91 (14)
O1—C1—C2	117.55 (13)	C10—C9—C8	119.53 (14)
C4—C2—C3	107.68 (13)	N1—C10—C9	123.15 (14)
C4—C2—C1	112.08 (13)	C11^ii—C11—C8	125.06 (18)

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

Catena((mu-Dimethylmalonato-O,O')(mu-1,2-bis(4-pyridine)ethane)- zinc(II) monohydrate) (4)

Crystal data

C17H18N2O4Zn·H2O	F(000) = 824
Mr = 397.72	Dx = 1.555 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.4434 (14) Å	Cell parameters from 6048 reflections
b = 10.3811 (18) Å	θ = 2.2–32.5°
c = 21.551 (4) Å	µ = 1.48 mm^−1
β = 115.928 (4)°	T = 120 K
V = 1698.8 (5) Å^3	Prism, colourless
Z = 4	0.32 × 0.21 × 0.12 mm

Data collection

Bruker APEX-II CCD diffractometer	6155 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.053
Absorption correction: multi-scan SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1119 before and 0.0553 after correction. The Ratio of minimum to maximum transmission is 0.6759. The λ/2 correction factor is 0.00150.	θmax = 36.6°, θmin = 2.1°
Tmin = 0.505, Tmax = 0.747	h = −14→13
25908 measured reflections	k = −17→17
7954 independent reflections	l = −35→30

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.070	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.153	w = 1/[σ^2(Fo^2) + (0.015P)^2 + 10.514P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
7954 reflections	Δρmax = 3.12 e Å^−3
232 parameters	Δρmin = −0.76 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.

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

	x	y	z	Uiso*/Ueq
Zn1	0.93529 (4)	0.99201 (3)	0.18412 (2)	0.01237 (7)
O1	1.1408 (3)	1.09609 (19)	0.24444 (11)	0.0159 (4)
O1W	0.3397 (4)	1.0421 (3)	0.07546 (15)	0.0359 (6)
H1WA	0.4179	0.9927	0.1040	0.054*
H1WB	0.3218	1.0708	0.1088	0.056 (18)*
O2	1.1499 (3)	1.1371 (2)	0.14514 (12)	0.0230 (4)
O3	1.1298 (3)	1.39758 (19)	0.25125 (11)	0.0153 (4)
O4	1.3705 (3)	1.3659 (2)	0.34743 (12)	0.0235 (5)
N1	0.7723 (3)	1.1293 (2)	0.12343 (13)	0.0147 (4)
N2	0.9791 (3)	0.8503 (2)	0.12841 (12)	0.0143 (4)
C6	0.6759 (4)	1.1088 (3)	0.05607 (16)	0.0185 (5)
H6	0.6720	1.0243	0.0385	0.022*
C7	0.5821 (4)	1.2050 (3)	0.01100 (15)	0.0185 (5)
H7	0.5170	1.1870	−0.0368	0.022*
C8	0.5834 (4)	1.3288 (3)	0.03604 (15)	0.0157 (5)
C9	0.6829 (4)	1.3497 (3)	0.10608 (15)	0.0174 (5)
H9	0.6877	1.4327	0.1253	0.021*
C10	0.7751 (4)	1.2479 (3)	0.14758 (15)	0.0178 (5)
H10	0.8436	1.2632	0.1955	0.021*
C11	0.4803 (4)	1.4321 (3)	−0.01388 (14)	0.0179 (5)
H11A	0.3533	1.4152	−0.0292	0.021*
H11B	0.5036	1.4261	−0.0550	0.021*
C1	1.2006 (4)	1.1570 (3)	0.20696 (16)	0.0158 (5)
C2	1.3448 (4)	1.2562 (3)	0.24496 (16)	0.0158 (5)
C3	1.2810 (4)	1.3456 (2)	0.28576 (15)	0.0150 (5)
C5	1.3826 (5)	1.3372 (3)	0.1941 (2)	0.0268 (7)
H5A	1.4214	1.2810	0.1668	0.040*
H5B	1.4754	1.3998	0.2194	0.040*
H5C	1.2754	1.3828	0.1632	0.040*
C4	1.5111 (4)	1.1854 (3)	0.2935 (2)	0.0266 (7)
H4A	1.4855	1.1327	0.3258	0.040*
H4B	1.6031	1.2482	0.3194	0.040*
H4C	1.5516	1.1298	0.2666	0.040*
C16	1.0019 (4)	0.8737 (3)	0.07214 (16)	0.0200 (5)
H16	0.9969	0.9604	0.0572	0.024*
C15	1.0323 (5)	0.7776 (3)	0.03456 (16)	0.0205 (6)
H15	1.0453	0.7981	−0.0059	0.025*
C14	1.0439 (4)	0.6511 (3)	0.05628 (15)	0.0165 (5)
C13	1.0196 (4)	0.6267 (3)	0.11478 (15)	0.0160 (5)
H13	1.0266	0.5411	0.1314	0.019*
C12	0.9850 (4)	0.7273 (3)	0.14860 (15)	0.0155 (5)
H12	0.9647	0.7091	0.1877	0.019*
C17	1.0795 (4)	0.5439 (3)	0.01764 (17)	0.0198 (5)
H17A	1.1806	0.4924	0.0501	0.024*
H17B	1.1121	0.5808	−0.0176	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01432 (13)	0.00861 (11)	0.01454 (14)	0.00037 (10)	0.00664 (10)	0.00017 (10)
O1	0.0163 (9)	0.0140 (8)	0.0173 (9)	−0.0024 (7)	0.0073 (7)	−0.0006 (7)
O1W	0.0326 (14)	0.0485 (17)	0.0303 (14)	0.0136 (12)	0.0170 (12)	0.0026 (12)
O2	0.0244 (11)	0.0285 (11)	0.0195 (11)	−0.0034 (9)	0.0127 (9)	−0.0046 (9)
O3	0.0150 (9)	0.0146 (8)	0.0172 (9)	0.0016 (7)	0.0079 (7)	−0.0010 (7)
O4	0.0214 (10)	0.0248 (11)	0.0189 (11)	0.0008 (8)	0.0040 (9)	−0.0027 (8)
N1	0.0143 (10)	0.0121 (9)	0.0167 (11)	0.0004 (7)	0.0059 (8)	0.0007 (7)
N2	0.0161 (10)	0.0129 (9)	0.0141 (10)	−0.0011 (7)	0.0069 (8)	−0.0007 (7)
C6	0.0202 (13)	0.0149 (11)	0.0167 (13)	0.0001 (9)	0.0047 (10)	−0.0006 (9)
C7	0.0201 (13)	0.0164 (11)	0.0138 (12)	0.0006 (9)	0.0028 (10)	0.0002 (9)
C8	0.0151 (11)	0.0147 (10)	0.0161 (12)	0.0017 (9)	0.0057 (9)	0.0026 (9)
C9	0.0197 (12)	0.0138 (10)	0.0154 (12)	0.0033 (9)	0.0047 (10)	0.0005 (9)
C10	0.0205 (12)	0.0159 (11)	0.0122 (12)	0.0044 (9)	0.0026 (10)	0.0000 (9)
C11	0.0176 (12)	0.0172 (11)	0.0129 (13)	0.0029 (9)	0.0013 (10)	0.0027 (9)
C1	0.0142 (11)	0.0121 (10)	0.0238 (14)	0.0017 (8)	0.0107 (10)	0.0001 (9)
C2	0.0143 (11)	0.0116 (10)	0.0232 (13)	−0.0001 (8)	0.0099 (10)	−0.0011 (9)
C3	0.0142 (11)	0.0116 (10)	0.0207 (13)	−0.0013 (8)	0.0091 (10)	0.0008 (9)
C5	0.0347 (18)	0.0173 (12)	0.041 (2)	−0.0030 (12)	0.0279 (16)	−0.0001 (12)
C4	0.0151 (12)	0.0206 (13)	0.0381 (19)	0.0030 (10)	0.0060 (13)	−0.0022 (12)
C16	0.0286 (15)	0.0161 (11)	0.0189 (13)	−0.0003 (10)	0.0136 (12)	−0.0002 (9)
C15	0.0298 (15)	0.0178 (12)	0.0179 (14)	−0.0025 (11)	0.0142 (12)	−0.0019 (10)
C14	0.0178 (12)	0.0176 (11)	0.0155 (12)	−0.0026 (9)	0.0085 (10)	−0.0041 (9)
C13	0.0187 (12)	0.0122 (10)	0.0183 (13)	0.0003 (9)	0.0093 (10)	−0.0014 (9)
C12	0.0188 (12)	0.0134 (10)	0.0144 (12)	0.0000 (9)	0.0074 (10)	−0.0002 (8)
C17	0.0212 (13)	0.0196 (12)	0.0228 (14)	−0.0026 (10)	0.0137 (11)	−0.0075 (10)

Geometric parameters (Å, º)

Zn1—O1	1.974 (2)	C11—H11A	0.9900
Zn1—O3^i	1.968 (2)	C11—H11B	0.9900
Zn1—N1	2.015 (2)	C1—C2	1.530 (4)
Zn1—N2	2.032 (2)	C2—C3	1.529 (4)
O1—C1	1.290 (4)	C2—C5	1.523 (4)
O1W—H1WA	0.8499	C2—C4	1.523 (4)
O1W—H1WB	0.8498	C5—H5A	0.9800
O2—C1	1.226 (4)	C5—H5B	0.9800
O3—Zn1^ii	1.968 (2)	C5—H5C	0.9800
O3—C3	1.282 (3)	C4—H4A	0.9800
O4—C3	1.226 (4)	C4—H4B	0.9800
N1—C6	1.335 (4)	C4—H4C	0.9800
N1—C10	1.333 (4)	C16—H16	0.9500
N2—C16	1.330 (4)	C16—C15	1.378 (4)
N2—C12	1.343 (3)	C15—H15	0.9500
C6—H6	0.9500	C15—C14	1.384 (4)
C6—C7	1.376 (4)	C14—C13	1.387 (4)
C7—H7	0.9500	C14—C17	1.497 (4)
C7—C8	1.392 (4)	C13—H13	0.9500
C8—C9	1.387 (4)	C13—C12	1.376 (4)
C8—C11	1.499 (4)	C12—H12	0.9500
C9—H9	0.9500	C17—C17^iv	1.523 (6)
C9—C10	1.383 (4)	C17—H17A	0.9900
C10—H10	0.9500	C17—H17B	0.9900
C11—C11^iii	1.511 (6)
O1—Zn1—N1	101.23 (9)	C5—C2—C3	108.4 (2)
O1—Zn1—N2	116.78 (9)	C5—C2—C4	109.9 (3)
O3^i—Zn1—O1	104.11 (9)	C4—C2—C1	108.8 (2)
O3^i—Zn1—N1	119.25 (10)	C4—C2—C3	110.4 (3)
O3^i—Zn1—N2	103.71 (9)	O3—C3—C2	115.7 (3)
N1—Zn1—N2	112.17 (10)	O4—C3—O3	122.8 (3)
C1—O1—Zn1	109.15 (19)	O4—C3—C2	121.5 (3)
H1WA—O1W—H1WB	88.3	C2—C5—H5A	109.5
C3—O3—Zn1^ii	108.34 (18)	C2—C5—H5B	109.5
C6—N1—Zn1	120.78 (19)	C2—C5—H5C	109.5
C10—N1—Zn1	120.6 (2)	H5A—C5—H5B	109.5
C10—N1—C6	118.0 (2)	H5A—C5—H5C	109.5
C16—N2—Zn1	122.84 (19)	H5B—C5—H5C	109.5
C16—N2—C12	118.0 (2)	C2—C4—H4A	109.5
C12—N2—Zn1	119.2 (2)	C2—C4—H4B	109.5
N1—C6—H6	118.6	C2—C4—H4C	109.5
N1—C6—C7	122.7 (3)	H4A—C4—H4B	109.5
C7—C6—H6	118.6	H4A—C4—H4C	109.5
C6—C7—H7	120.3	H4B—C4—H4C	109.5
C6—C7—C8	119.4 (3)	N2—C16—H16	118.6
C8—C7—H7	120.3	N2—C16—C15	122.8 (3)
C7—C8—C11	118.6 (3)	C15—C16—H16	118.6
C9—C8—C7	117.7 (3)	C16—C15—H15	120.3
C9—C8—C11	123.7 (3)	C16—C15—C14	119.5 (3)
C8—C9—H9	120.4	C14—C15—H15	120.3
C10—C9—C8	119.1 (3)	C15—C14—C13	117.7 (3)
C10—C9—H9	120.4	C15—C14—C17	121.3 (3)
N1—C10—C9	123.0 (3)	C13—C14—C17	121.1 (3)
N1—C10—H10	118.5	C14—C13—H13	120.2
C9—C10—H10	118.5	C12—C13—C14	119.5 (3)
C8—C11—C11^iii	115.2 (3)	C12—C13—H13	120.2
C8—C11—H11A	108.5	N2—C12—C13	122.5 (3)
C8—C11—H11B	108.5	N2—C12—H12	118.8
C11^iii—C11—H11A	108.5	C13—C12—H12	118.8
C11^iii—C11—H11B	108.5	C14—C17—C17^iv	112.0 (3)
H11A—C11—H11B	107.5	C14—C17—H17A	109.2
O1—C1—C2	115.6 (3)	C14—C17—H17B	109.2
O2—C1—O1	123.5 (3)	C17^iv—C17—H17A	109.2
O2—C1—C2	120.9 (3)	C17^iv—C17—H17B	109.2
C3—C2—C1	108.6 (2)	H17A—C17—H17B	107.9
C5—C2—C1	110.8 (3)
Zn1—O1—C1—O2	−9.1 (3)	C7—C8—C11—C11^iii	−167.1 (3)
Zn1—O1—C1—C2	172.08 (18)	C8—C9—C10—N1	−0.4 (5)
Zn1^ii—O3—C3—O4	−6.5 (3)	C9—C8—C11—C11^iii	11.9 (5)
Zn1^ii—O3—C3—C2	173.83 (18)	C10—N1—C6—C7	0.8 (5)
Zn1—N1—C6—C7	−170.7 (2)	C11—C8—C9—C10	−179.2 (3)
Zn1—N1—C10—C9	171.5 (2)	C1—C2—C3—O3	−52.3 (3)
Zn1—N2—C16—C15	179.7 (2)	C1—C2—C3—O4	128.1 (3)
Zn1—N2—C12—C13	−177.9 (2)	C5—C2—C3—O3	68.2 (3)
O1—C1—C2—C3	−51.4 (3)	C5—C2—C3—O4	−111.5 (3)
O1—C1—C2—C5	−170.4 (2)	C4—C2—C3—O3	−171.4 (2)
O1—C1—C2—C4	68.8 (3)	C4—C2—C3—O4	8.9 (4)
O2—C1—C2—C3	129.7 (3)	C16—N2—C12—C13	2.3 (4)
O2—C1—C2—C5	10.7 (4)	C16—C15—C14—C13	1.6 (5)
O2—C1—C2—C4	−110.1 (3)	C16—C15—C14—C17	−179.1 (3)
N1—C6—C7—C8	−1.3 (5)	C15—C14—C13—C12	0.1 (4)
N2—C16—C15—C14	−1.4 (5)	C15—C14—C17—C17^iv	−111.3 (4)
C6—N1—C10—C9	0.1 (5)	C14—C13—C12—N2	−2.1 (5)
C6—C7—C8—C9	1.0 (5)	C13—C14—C17—C17^iv	68.0 (5)
C6—C7—C8—C11	−180.0 (3)	C12—N2—C16—C15	−0.5 (5)
C7—C8—C9—C10	−0.2 (5)	C17—C14—C13—C12	−179.3 (3)

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

Catena((mu-4,4'-bipyridine-N,N')-bis(4,4'-bipyridine)-bis(mu-diethylmalonato- O,O')-dizinc(II) dihydrate) (5)

Crystal data

C22H22N3O4Zn·H2O	F(000) = 988
Mr = 475.81	Dx = 1.457 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.1832 (8) Å	Cell parameters from 1045 reflections
b = 8.2422 (6) Å	θ = 1.9–29.8°
c = 23.8320 (17) Å	µ = 1.17 mm^−1
β = 99.143 (2)°	T = 120 K
V = 2168.8 (3) Å^3	Plate, colourless
Z = 4	0.42 × 0.3 × 0.06 mm

Data collection

Bruker Smart 1000 CCD area detector diffractometer	Rint = 0.073
Absorption correction: multi-scan SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0782 before and 0.0561 after correction. The Ratio of minimum to maximum transmission is 0.7883. The λ/2 correction factor is 0.00150.	θmax = 30.9°, θmin = 1.7°
Tmin = 0.266, Tmax = 0.337	h = −16→16
23649 measured reflections	k = −10→11
6785 independent reflections	l = −34→34
4755 reflections with I > 2σ(I)

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.040P)^2 + 0.049P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.002
6785 reflections	Δρmax = 0.44 e Å^−3
282 parameters	Δρmin = −0.45 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.

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

	x	y	z	Uiso*/Ueq
Zn1	0.55981 (2)	1.07828 (3)	0.32295 (2)	0.01347 (8)
O1	0.40162 (14)	0.9860 (2)	0.29564 (7)	0.0183 (4)
O2	0.39039 (15)	0.8722 (2)	0.37964 (6)	0.0191 (4)
O3	0.40734 (14)	0.6410 (2)	0.25283 (7)	0.0192 (4)
O4	0.25504 (16)	0.7449 (2)	0.19360 (6)	0.0216 (4)
N1	0.54097 (17)	1.2356 (2)	0.38710 (7)	0.0145 (4)
N2	0.68235 (17)	0.9047 (2)	0.35533 (8)	0.0152 (4)
N3	1.13460 (19)	0.3168 (3)	0.45195 (8)	0.0221 (5)
C1	0.3570 (2)	0.8853 (3)	0.32768 (9)	0.0151 (5)
C2	0.2565 (2)	0.7787 (3)	0.29519 (9)	0.0145 (4)
C3	0.3072 (2)	0.7194 (3)	0.24272 (9)	0.0150 (5)
C4	0.1430 (2)	0.8849 (3)	0.27774 (10)	0.0227 (5)
H4A	0.1626	0.9707	0.2516	0.027*
H4B	0.0782	0.8167	0.2566	0.027*
C5	0.0948 (3)	0.9647 (4)	0.32718 (11)	0.0356 (7)
H5A	0.0243	1.0317	0.3126	0.053*
H5B	0.1581	1.0330	0.3484	0.053*
H5C	0.0711	0.8808	0.3524	0.053*
C6	0.2323 (2)	0.6314 (3)	0.33109 (10)	0.0209 (5)
H6A	0.3095	0.5727	0.3427	0.025*
H6B	0.2044	0.6705	0.3661	0.025*
C7	0.1389 (3)	0.5127 (4)	0.30110 (12)	0.0361 (7)
H7A	0.1624	0.4793	0.2649	0.054*
H7B	0.0593	0.5654	0.2939	0.054*
H7C	0.1348	0.4172	0.3252	0.054*
C8	0.5393 (2)	1.1797 (3)	0.43963 (10)	0.0248 (6)
H8	0.5488	1.0664	0.4462	0.030*
C9	0.5245 (3)	1.2789 (3)	0.48484 (10)	0.0251 (6)
H9	0.5249	1.2338	0.5216	0.030*
C10	0.50890 (19)	1.4444 (3)	0.47632 (9)	0.0123 (4)
C11	0.5118 (2)	1.5022 (3)	0.42168 (10)	0.0202 (5)
H11	0.5026	1.6149	0.4139	0.024*
C12	0.5282 (2)	1.3955 (3)	0.37879 (10)	0.0204 (5)
H12	0.5306	1.4376	0.3419	0.024*
C13	0.7726 (2)	0.9390 (3)	0.39812 (10)	0.0189 (5)
H13	0.7751	1.0438	0.4148	0.023*
C14	0.8615 (2)	0.8290 (3)	0.41876 (9)	0.0173 (5)
H14	0.9229	0.8581	0.4494	0.021*
C15	0.8614 (2)	0.6751 (3)	0.39468 (9)	0.0141 (4)
C16	0.7680 (2)	0.6403 (3)	0.34990 (10)	0.0173 (5)
H16	0.7642	0.5371	0.3319	0.021*
C17	0.6813 (2)	0.7565 (3)	0.33190 (10)	0.0181 (5)
H17	0.6182	0.7304	0.3016	0.022*
C18	0.9562 (2)	0.5515 (3)	0.41538 (9)	0.0153 (5)
C19	0.9348 (2)	0.3868 (3)	0.40522 (10)	0.0192 (5)
H19	0.8588	0.3507	0.3856	0.023*
C20	1.0253 (2)	0.2766 (3)	0.42392 (10)	0.0221 (5)
H20	1.0089	0.1649	0.4164	0.027*
C21	1.1532 (2)	0.4748 (3)	0.46210 (10)	0.0213 (5)
H21	1.2297	0.5069	0.4823	0.026*
C22	1.0687 (2)	0.5954 (3)	0.44516 (9)	0.0185 (5)
H22	1.0873	0.7060	0.4537	0.022*
O1W	1.25043 (19)	−0.0116 (3)	0.47018 (8)	0.0402 (5)
H1WA	1.2508	0.0895	0.4633	0.060*
H1WB	1.2753	−0.0344	0.4393	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01846 (14)	0.01146 (14)	0.01061 (12)	0.00119 (11)	0.00266 (9)	−0.00037 (10)
O1	0.0204 (8)	0.0182 (9)	0.0166 (8)	−0.0027 (7)	0.0036 (7)	0.0025 (7)
O2	0.0231 (9)	0.0207 (9)	0.0129 (8)	−0.0009 (7)	0.0007 (7)	−0.0005 (6)
O3	0.0181 (8)	0.0234 (9)	0.0160 (8)	0.0035 (7)	0.0027 (7)	−0.0054 (7)
O4	0.0299 (10)	0.0220 (10)	0.0129 (8)	0.0053 (8)	0.0029 (7)	−0.0003 (7)
N1	0.0189 (10)	0.0126 (10)	0.0123 (9)	−0.0007 (8)	0.0035 (7)	−0.0005 (7)
N2	0.0172 (9)	0.0128 (10)	0.0157 (9)	0.0008 (8)	0.0035 (7)	0.0017 (8)
N3	0.0252 (11)	0.0245 (12)	0.0175 (10)	0.0096 (9)	0.0058 (9)	0.0055 (9)
C1	0.0144 (11)	0.0162 (12)	0.0161 (10)	0.0055 (9)	0.0064 (9)	−0.0011 (9)
C2	0.0154 (11)	0.0183 (12)	0.0104 (10)	0.0008 (9)	0.0040 (8)	0.0000 (8)
C3	0.0170 (11)	0.0133 (12)	0.0155 (10)	−0.0050 (9)	0.0051 (9)	−0.0004 (9)
C4	0.0182 (12)	0.0319 (15)	0.0180 (11)	0.0058 (11)	0.0031 (9)	0.0000 (10)
C5	0.0278 (14)	0.058 (2)	0.0225 (13)	0.0183 (14)	0.0071 (11)	−0.0029 (13)
C6	0.0232 (12)	0.0227 (13)	0.0176 (11)	−0.0064 (10)	0.0058 (10)	0.0026 (10)
C7	0.0407 (17)	0.0390 (18)	0.0288 (15)	−0.0207 (14)	0.0062 (13)	0.0025 (13)
C8	0.0469 (17)	0.0108 (12)	0.0179 (12)	0.0036 (11)	0.0093 (11)	0.0006 (9)
C9	0.0474 (17)	0.0167 (13)	0.0131 (11)	0.0015 (12)	0.0109 (11)	0.0007 (9)
C10	0.0117 (10)	0.0120 (12)	0.0131 (10)	0.0009 (8)	0.0016 (8)	−0.0010 (8)
C11	0.0352 (14)	0.0094 (12)	0.0166 (11)	0.0037 (10)	0.0059 (10)	0.0016 (9)
C12	0.0333 (14)	0.0140 (13)	0.0147 (11)	0.0019 (10)	0.0061 (10)	−0.0001 (9)
C13	0.0252 (12)	0.0150 (13)	0.0163 (11)	−0.0016 (10)	0.0028 (9)	−0.0013 (9)
C14	0.0200 (12)	0.0156 (12)	0.0148 (11)	−0.0008 (10)	−0.0014 (9)	0.0002 (9)
C15	0.0164 (11)	0.0129 (11)	0.0133 (10)	−0.0018 (9)	0.0035 (8)	0.0013 (8)
C16	0.0200 (12)	0.0139 (12)	0.0175 (11)	0.0004 (9)	0.0014 (9)	−0.0024 (9)
C17	0.0195 (12)	0.0173 (13)	0.0166 (11)	0.0021 (10)	0.0001 (9)	−0.0012 (9)
C18	0.0165 (11)	0.0172 (13)	0.0127 (10)	0.0011 (9)	0.0038 (8)	−0.0001 (8)
C19	0.0210 (12)	0.0186 (13)	0.0175 (11)	0.0031 (10)	0.0020 (9)	−0.0015 (9)
C20	0.0268 (13)	0.0197 (13)	0.0203 (12)	0.0049 (11)	0.0050 (10)	0.0014 (10)
C21	0.0157 (11)	0.0305 (15)	0.0179 (11)	0.0014 (10)	0.0034 (9)	0.0055 (10)
C22	0.0189 (11)	0.0223 (13)	0.0151 (10)	−0.0004 (10)	0.0046 (9)	0.0002 (9)
O1W	0.0533 (13)	0.0445 (13)	0.0231 (10)	0.0205 (11)	0.0075 (9)	0.0035 (9)

Geometric parameters (Å, º)

Zn1—O1	1.9407 (16)	C7—H7B	0.9800
Zn1—O3^i	1.9683 (15)	C7—H7C	0.9800
Zn1—N1	2.0407 (18)	C8—H8	0.9500
Zn1—N2	2.0455 (19)	C8—C9	1.384 (3)
Zn1—C3^i	2.599 (2)	C9—H9	0.9500
O1—C1	1.281 (3)	C9—C10	1.385 (3)
O2—C1	1.240 (3)	C10—C10^iii	1.492 (4)
O3—Zn1^ii	1.9683 (15)	C10—C11	1.392 (3)
O3—C3	1.282 (3)	C11—H11	0.9500
O4—C3	1.240 (3)	C11—C12	1.382 (3)
N1—C8	1.337 (3)	C12—H12	0.9500
N1—C12	1.338 (3)	C13—H13	0.9500
N2—C13	1.346 (3)	C13—C14	1.378 (3)
N2—C17	1.342 (3)	C14—H14	0.9500
N3—C20	1.338 (3)	C14—C15	1.392 (3)
N3—C21	1.336 (3)	C15—C16	1.399 (3)
C1—C2	1.535 (3)	C15—C18	1.497 (3)
C2—C3	1.533 (3)	C16—H16	0.9500
C2—C4	1.544 (3)	C16—C17	1.382 (3)
C2—C6	1.534 (3)	C17—H17	0.9500
C3—Zn1^ii	2.599 (2)	C18—C19	1.394 (3)
C4—H4A	0.9900	C18—C22	1.390 (3)
C4—H4B	0.9900	C19—H19	0.9500
C4—C5	1.521 (3)	C19—C20	1.380 (3)
C5—H5A	0.9800	C20—H20	0.9500
C5—H5B	0.9800	C21—H21	0.9500
C5—H5C	0.9800	C21—C22	1.387 (3)
C6—H6A	0.9900	C22—H22	0.9500
C6—H6B	0.9900	O1W—H1WA	0.8495
C6—C7	1.524 (3)	O1W—H1WB	0.8496
C7—H7A	0.9800
O1—Zn1—O3^i	95.07 (7)	C6—C7—H7A	109.5
O1—Zn1—N1	107.65 (7)	C6—C7—H7B	109.5
O1—Zn1—N2	111.88 (7)	C6—C7—H7C	109.5
O1—Zn1—C3^i	123.50 (7)	H7A—C7—H7B	109.5
O3^i—Zn1—N1	125.25 (7)	H7A—C7—H7C	109.5
O3^i—Zn1—N2	108.56 (7)	H7B—C7—H7C	109.5
O3^i—Zn1—C3^i	28.58 (7)	N1—C8—H8	118.4
N1—Zn1—N2	107.72 (7)	N1—C8—C9	123.2 (2)
N1—Zn1—C3^i	107.70 (7)	C9—C8—H8	118.4
N2—Zn1—C3^i	97.29 (7)	C8—C9—H9	120.2
C1—O1—Zn1	118.33 (15)	C8—C9—C10	119.7 (2)
C3—O3—Zn1^ii	104.16 (14)	C10—C9—H9	120.2
C8—N1—Zn1	120.09 (16)	C9—C10—C10^iii	121.5 (2)
C8—N1—C12	117.5 (2)	C9—C10—C11	116.9 (2)
C12—N1—Zn1	122.45 (15)	C11—C10—C10^iii	121.5 (2)
C13—N2—Zn1	121.05 (16)	C10—C11—H11	120.0
C17—N2—Zn1	121.21 (15)	C12—C11—C10	120.0 (2)
C17—N2—C13	117.5 (2)	C12—C11—H11	120.0
C21—N3—C20	115.8 (2)	N1—C12—C11	122.7 (2)
O1—C1—C2	113.14 (19)	N1—C12—H12	118.6
O2—C1—O1	124.6 (2)	C11—C12—H12	118.6
O2—C1—C2	122.2 (2)	N2—C13—H13	118.5
C1—C2—C4	108.43 (19)	N2—C13—C14	123.0 (2)
C3—C2—C1	104.97 (17)	C14—C13—H13	118.5
C3—C2—C4	110.86 (18)	C13—C14—H14	120.0
C3—C2—C6	108.85 (19)	C13—C14—C15	119.9 (2)
C6—C2—C1	110.59 (18)	C15—C14—H14	120.0
C6—C2—C4	112.86 (19)	C14—C15—C16	116.9 (2)
O3—C3—Zn1^ii	47.26 (10)	C14—C15—C18	122.0 (2)
O3—C3—C2	115.64 (19)	C16—C15—C18	121.1 (2)
O4—C3—Zn1^ii	74.68 (13)	C15—C16—H16	120.1
O4—C3—O3	121.9 (2)	C17—C16—C15	119.8 (2)
O4—C3—C2	122.4 (2)	C17—C16—H16	120.1
C2—C3—Zn1^ii	162.81 (16)	N2—C17—C16	122.8 (2)
C2—C4—H4A	108.7	N2—C17—H17	118.6
C2—C4—H4B	108.7	C16—C17—H17	118.6
H4A—C4—H4B	107.6	C19—C18—C15	120.8 (2)
C5—C4—C2	114.4 (2)	C22—C18—C15	121.8 (2)
C5—C4—H4A	108.7	C22—C18—C19	117.3 (2)
C5—C4—H4B	108.7	C18—C19—H19	120.4
C4—C5—H5A	109.5	C20—C19—C18	119.2 (2)
C4—C5—H5B	109.5	C20—C19—H19	120.4
C4—C5—H5C	109.5	N3—C20—C19	124.3 (2)
H5A—C5—H5B	109.5	N3—C20—H20	117.8
H5A—C5—H5C	109.5	C19—C20—H20	117.8
H5B—C5—H5C	109.5	N3—C21—H21	117.7
C2—C6—H6A	108.6	N3—C21—C22	124.6 (2)
C2—C6—H6B	108.6	C22—C21—H21	117.7
H6A—C6—H6B	107.6	C18—C22—H22	120.6
C7—C6—C2	114.5 (2)	C21—C22—C18	118.8 (2)
C7—C6—H6A	108.6	C21—C22—H22	120.6
C7—C6—H6B	108.6	H1WA—O1W—H1WB	92.1

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

Catena((mu-4,4'-bipyridine-N,N')-tetraaqua-zinc(II) bis(hydrogen diethylmalonate) 4,4'-bipyridine dihydrate) (6)

Crystal data

C10H16N2O4Zn·2(C7H11O4)·C10H8N2·2(H2O)	F(000) = 1696
Mr = 804.15	Dx = 1.398 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.6008 (12) Å	Cell parameters from 5437 reflections
b = 11.4154 (6) Å	θ = 2.6–30.8°
c = 17.1552 (9) Å	µ = 0.71 mm^−1
β = 120.308 (1)°	T = 120 K
V = 3821.1 (4) Å^3	Prism, colourless
Z = 4	0.46 × 0.28 × 0.13 mm

Data collection

Apex diffractometer	7041 independent reflections
Radiation source: sealed tube	5947 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 8 pixels mm^-1	θmax = 33.7°, θmin = 2.1°
ω and φ scans	h = −34→34
Absorption correction: multi-scan SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0902 before and 0.0395 after correction. The Ratio of minimum to maximum transmission is 0.7615. The λ/2 correction factor is 0.00150.	k = −16→17
Tmin = 0.569, Tmax = 0.747	l = −26→26
27960 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.0381P)^2 + 1.5P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.003
7041 reflections	Δρmax = 0.40 e Å^−3
264 parameters	Δρmin = −0.48 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.

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

	x	y	z	Uiso*/Ueq
Zn01	0.5000	0.50576 (2)	0.7500	0.00949 (4)
O1	0.39286 (4)	0.50282 (6)	0.69252 (5)	0.01661 (13)
H1A	0.3831	0.4978	0.7342	0.025*
O2	0.49360 (4)	0.50676 (6)	0.62313 (5)	0.01307 (12)
N1	0.5000	0.69336 (9)	0.7500	0.01285 (19)
N2	0.5000	1.31620 (9)	0.7500	0.01197 (19)
C1	0.53773 (5)	0.75450 (8)	0.82635 (6)	0.01454 (16)
H1	0.5648	0.7125	0.8809	0.017*
C2	0.53916 (5)	0.87602 (8)	0.82961 (6)	0.01326 (16)
H2	0.5664	0.9155	0.8853	0.016*
C3	0.5000	0.93979 (10)	0.7500	0.0105 (2)
C4	0.5000	1.07006 (10)	0.7500	0.0102 (2)
C5	0.55048 (4)	1.13361 (7)	0.82320 (6)	0.01220 (15)
H5	0.5853	1.0941	0.8747	0.015*
C6	0.54905 (5)	1.25513 (8)	0.81957 (6)	0.01258 (15)
H6A	0.5845	1.2972	0.8687	0.015*
O3	0.30082 (4)	0.52454 (9)	0.51908 (5)	0.0315 (2)
O4	0.37280 (4)	0.53617 (8)	0.46724 (5)	0.02105 (15)
O5	0.22393 (4)	0.51049 (7)	0.20547 (5)	0.02523 (17)
O6	0.33422 (4)	0.52650 (8)	0.30713 (5)	0.02193 (15)
C12	0.31291 (5)	0.52573 (9)	0.45617 (6)	0.01627 (17)
C13	0.25152 (5)	0.51348 (8)	0.35960 (6)	0.01417 (16)
C14	0.26932 (5)	0.51707 (8)	0.28417 (7)	0.01620 (17)
C15	0.21685 (6)	0.39422 (10)	0.35339 (7)	0.0242 (2)
H15A	0.1985	0.3954	0.3950	0.029*
H15B	0.1776	0.3846	0.2913	0.029*
C16	0.26404 (9)	0.28906 (11)	0.37610 (11)	0.0411 (3)
H16A	0.2840	0.2888	0.3370	0.062*
H16B	0.2378	0.2169	0.3666	0.062*
H16C	0.3008	0.2937	0.4394	0.062*
C17	0.20103 (6)	0.61447 (11)	0.34263 (7)	0.0243 (2)
H17A	0.1618	0.6081	0.2802	0.029*
H17B	0.1830	0.6056	0.3843	0.029*
C18	0.23249 (9)	0.73569 (12)	0.35544 (11)	0.0420 (3)
H18A	0.2527	0.7440	0.3168	0.063*
H18B	0.2682	0.7460	0.4188	0.063*
H18C	0.1969	0.7952	0.3390	0.063*
N3	0.52216 (4)	0.69808 (7)	1.06187 (6)	0.01772 (16)
C7	0.46550 (5)	0.73724 (9)	0.98863 (7)	0.02024 (19)
H7	0.4308	0.6820	0.9528	0.024*
C8	0.45456 (5)	0.85357 (8)	0.96213 (7)	0.01927 (19)
H8	0.4131	0.8765	0.9099	0.023*
C9	0.50467 (4)	0.93690 (8)	1.01258 (6)	0.01306 (16)
C10	0.56427 (5)	0.89601 (8)	1.08791 (7)	0.01839 (18)
H10	0.6004	0.9487	1.1241	0.022*
C11	0.57047 (5)	0.77753 (8)	1.10972 (7)	0.01971 (19)
H11	0.6114	0.7517	1.1616	0.024*
O7	0.67465 (4)	0.99993 (8)	1.01633 (5)	0.02724 (19)
H7A	0.7092	0.9914	1.0097	0.041*
H7B	0.6879	1.0030	1.0723	0.041*
H2A	0.5069 (8)	0.4526 (15)	0.6084 (10)	0.031 (4)*
H1B	0.3627 (8)	0.5081 (11)	0.6355 (11)	0.023 (4)*
H2B	0.4565 (8)	0.5229 (12)	0.5777 (11)	0.024 (4)*
H6	0.3583 (10)	0.5308 (17)	0.3669 (14)	0.058 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn01	0.01092 (7)	0.00652 (6)	0.00916 (7)	0.000	0.00367 (5)	0.000
O1	0.0113 (3)	0.0269 (4)	0.0106 (3)	0.0020 (2)	0.0047 (2)	0.0020 (3)
O2	0.0150 (3)	0.0118 (3)	0.0102 (3)	0.0026 (2)	0.0047 (2)	−0.0006 (2)
N1	0.0160 (5)	0.0086 (4)	0.0132 (5)	0.000	0.0068 (4)	0.000
N2	0.0132 (5)	0.0082 (4)	0.0132 (5)	0.000	0.0056 (4)	0.000
C1	0.0197 (4)	0.0088 (3)	0.0132 (4)	−0.0003 (3)	0.0069 (3)	0.0005 (3)
C2	0.0169 (4)	0.0092 (3)	0.0121 (4)	−0.0008 (3)	0.0061 (3)	−0.0002 (3)
C3	0.0116 (5)	0.0083 (5)	0.0135 (5)	0.000	0.0078 (4)	0.000
C4	0.0116 (5)	0.0081 (5)	0.0119 (5)	0.000	0.0067 (4)	0.000
C5	0.0128 (4)	0.0092 (3)	0.0131 (4)	0.0004 (3)	0.0054 (3)	0.0005 (3)
C6	0.0132 (4)	0.0095 (3)	0.0122 (4)	−0.0003 (3)	0.0043 (3)	0.0000 (3)
O3	0.0165 (4)	0.0672 (6)	0.0097 (3)	−0.0007 (4)	0.0059 (3)	−0.0016 (3)
O4	0.0115 (3)	0.0356 (4)	0.0132 (3)	−0.0010 (3)	0.0042 (3)	0.0007 (3)
O5	0.0216 (4)	0.0416 (5)	0.0104 (3)	−0.0055 (3)	0.0065 (3)	−0.0032 (3)
O6	0.0163 (3)	0.0370 (4)	0.0148 (3)	−0.0020 (3)	0.0096 (3)	−0.0023 (3)
C12	0.0130 (4)	0.0235 (4)	0.0100 (4)	0.0003 (3)	0.0041 (3)	−0.0006 (3)
C13	0.0113 (4)	0.0219 (4)	0.0083 (4)	0.0004 (3)	0.0042 (3)	−0.0004 (3)
C14	0.0165 (4)	0.0205 (4)	0.0126 (4)	−0.0014 (3)	0.0081 (3)	−0.0018 (3)
C15	0.0252 (5)	0.0296 (5)	0.0179 (5)	−0.0105 (4)	0.0110 (4)	−0.0029 (4)
C16	0.0606 (9)	0.0232 (6)	0.0446 (8)	−0.0035 (6)	0.0303 (7)	0.0002 (5)
C17	0.0209 (5)	0.0365 (6)	0.0159 (4)	0.0114 (4)	0.0095 (4)	0.0046 (4)
C18	0.0587 (9)	0.0269 (6)	0.0474 (8)	0.0156 (6)	0.0319 (7)	0.0043 (6)
N3	0.0200 (4)	0.0139 (3)	0.0214 (4)	−0.0004 (3)	0.0121 (3)	0.0020 (3)
C7	0.0221 (5)	0.0140 (4)	0.0204 (5)	−0.0041 (3)	0.0076 (4)	−0.0001 (3)
C8	0.0205 (5)	0.0145 (4)	0.0161 (4)	−0.0032 (3)	0.0043 (4)	0.0018 (3)
C9	0.0147 (4)	0.0126 (4)	0.0139 (4)	−0.0013 (3)	0.0086 (3)	0.0009 (3)
C10	0.0145 (4)	0.0152 (4)	0.0210 (5)	−0.0018 (3)	0.0056 (4)	0.0019 (3)
C11	0.0169 (4)	0.0153 (4)	0.0229 (5)	0.0009 (3)	0.0071 (4)	0.0045 (3)
O7	0.0190 (4)	0.0495 (6)	0.0127 (3)	0.0028 (3)	0.0077 (3)	−0.0005 (3)

Geometric parameters (Å, º)

Zn01—O1^i	2.1040 (7)	O6—H6	0.89 (2)
Zn01—O1	2.1040 (7)	C12—C13	1.5392 (13)
Zn01—O2^i	2.1072 (7)	C13—C14	1.5374 (14)
Zn01—O2	2.1072 (7)	C13—C15	1.5474 (14)
Zn01—N1	2.1416 (11)	C13—C17	1.5430 (14)
Zn01—N2^ii	2.1639 (10)	C15—H15A	0.9900
O1—H1A	0.8501	C15—H15B	0.9900
O1—H1B	0.867 (16)	C15—C16	1.5203 (19)
O2—H2A	0.783 (16)	C16—H16A	0.9800
O2—H2B	0.828 (16)	C16—H16B	0.9800
N1—C1^i	1.3425 (10)	C16—H16C	0.9800
N1—C1	1.3425 (10)	C17—H17A	0.9900
N2—Zn01^iii	2.1639 (10)	C17—H17B	0.9900
N2—C6^i	1.3431 (10)	C17—C18	1.5202 (19)
N2—C6	1.3431 (10)	C18—H18A	0.9800
C1—H1	0.9500	C18—H18B	0.9800
C1—C2	1.3881 (12)	C18—H18C	0.9800
C2—H2	0.9500	N3—C7	1.3395 (13)
C2—C3	1.3994 (10)	N3—C11	1.3355 (13)
C3—C2^i	1.3994 (11)	C7—H7	0.9500
C3—C4	1.4872 (17)	C7—C8	1.3848 (13)
C4—C5	1.3995 (10)	C8—H8	0.9500
C4—C5^i	1.3995 (10)	C8—C9	1.3955 (13)
C5—H5	0.9500	C9—C9^iv	1.4880 (18)
C5—C6	1.3882 (12)	C9—C10	1.3948 (13)
C6—H6A	0.9500	C10—H10	0.9500
O3—C12	1.2398 (12)	C10—C11	1.3914 (13)
O4—C12	1.2740 (12)	C11—H11	0.9500
O5—C14	1.2177 (12)	O7—H7A	0.8494
O6—C14	1.3171 (12)	O7—H7B	0.8500
O1^i—Zn01—O1	178.18 (4)	C12—C13—C17	108.32 (8)
O1^i—Zn01—O2^i	93.04 (3)	C14—C13—C12	115.28 (8)
O1—Zn01—O2^i	86.97 (3)	C14—C13—C15	107.70 (8)
O1^i—Zn01—O2	86.97 (3)	C14—C13—C17	107.71 (8)
O1—Zn01—O2	93.04 (3)	C17—C13—C15	110.11 (9)
O1—Zn01—N1	90.913 (19)	O5—C14—O6	121.64 (9)
O1^i—Zn01—N1	90.912 (19)	O5—C14—C13	119.98 (9)
O1^i—Zn01—N2^ii	89.088 (19)	O6—C14—C13	118.38 (8)
O1—Zn01—N2^ii	89.087 (19)	C13—C15—H15A	108.7
O2^i—Zn01—O2	179.38 (4)	C13—C15—H15B	108.7
O2^i—Zn01—N1	89.689 (18)	H15A—C15—H15B	107.6
O2—Zn01—N1	89.688 (18)	C16—C15—C13	114.31 (10)
O2^i—Zn01—N2^ii	90.311 (18)	C16—C15—H15A	108.7
O2—Zn01—N2^ii	90.312 (18)	C16—C15—H15B	108.7
N1—Zn01—N2^ii	180.0	C15—C16—H16A	109.5
Zn01—O1—H1A	109.5	C15—C16—H16B	109.5
Zn01—O1—H1B	126.3 (11)	C15—C16—H16C	109.5
H1A—O1—H1B	124.2	H16A—C16—H16B	109.5
Zn01—O2—H2A	119.5 (11)	H16A—C16—H16C	109.5
Zn01—O2—H2B	118.9 (10)	H16B—C16—H16C	109.5
H2A—O2—H2B	104.1 (14)	C13—C17—H17A	108.8
C1—N1—Zn01	121.32 (5)	C13—C17—H17B	108.8
C1^i—N1—Zn01	121.32 (5)	H17A—C17—H17B	107.7
C1^i—N1—C1	117.36 (11)	C18—C17—C13	113.91 (10)
C6—N2—Zn01^iii	121.27 (5)	C18—C17—H17A	108.8
C6^i—N2—Zn01^iii	121.27 (5)	C18—C17—H17B	108.8
C6—N2—C6^i	117.46 (10)	C17—C18—H18A	109.5
N1—C1—H1	118.3	C17—C18—H18B	109.5
N1—C1—C2	123.31 (9)	C17—C18—H18C	109.5
C2—C1—H1	118.3	H18A—C18—H18B	109.5
C1—C2—H2	120.3	H18A—C18—H18C	109.5
C1—C2—C3	119.35 (8)	H18B—C18—H18C	109.5
C3—C2—H2	120.3	C11—N3—C7	116.61 (8)
C2—C3—C2^i	117.31 (11)	N3—C7—H7	118.1
C2^i—C3—C4	121.34 (5)	N3—C7—C8	123.76 (9)
C2—C3—C4	121.34 (5)	C8—C7—H7	118.1
C5^i—C4—C3	121.22 (5)	C7—C8—H8	120.1
C5—C4—C3	121.22 (5)	C7—C8—C9	119.70 (9)
C5^i—C4—C5	117.56 (11)	C9—C8—H8	120.1
C4—C5—H5	120.4	C8—C9—C9^iv	121.88 (10)
C6—C5—C4	119.19 (8)	C10—C9—C8	116.65 (9)
C6—C5—H5	120.4	C10—C9—C9^iv	121.47 (10)
N2—C6—C5	123.27 (8)	C9—C10—H10	120.2
N2—C6—H6A	118.4	C11—C10—C9	119.57 (9)
C5—C6—H6A	118.4	C11—C10—H10	120.2
C14—O6—H6	106.9 (13)	N3—C11—C10	123.69 (9)
O3—C12—O4	123.75 (9)	N3—C11—H11	118.2
O3—C12—C13	117.46 (9)	C10—C11—H11	118.2
O4—C12—C13	118.79 (8)	H7A—O7—H7B	109.5
C12—C13—C15	107.70 (8)
Zn01—N1—C1—C2	−179.79 (7)	C12—C13—C14—O5	−178.47 (9)
Zn01^iii—N2—C6—C5	178.87 (7)	C12—C13—C14—O6	1.98 (13)
N1—C1—C2—C3	−0.41 (13)	C12—C13—C15—C16	−57.70 (12)
C1^i—N1—C1—C2	0.21 (7)	C12—C13—C17—C18	57.41 (12)
C1—C2—C3—C2^i	0.19 (6)	C14—C13—C15—C16	67.21 (12)
C1—C2—C3—C4	−179.81 (6)	C14—C13—C17—C18	−67.88 (12)
C2^i—C3—C4—C5^i	15.64 (6)	C15—C13—C14—O5	61.29 (12)
C2—C3—C4—C5^i	−164.36 (6)	C15—C13—C14—O6	−118.25 (10)
C2—C3—C4—C5	15.65 (6)	C15—C13—C17—C18	174.94 (9)
C2^i—C3—C4—C5	−164.35 (6)	C17—C13—C14—O5	−57.44 (12)
C3—C4—C5—C6	178.96 (6)	C17—C13—C14—O6	123.02 (10)
C4—C5—C6—N2	2.22 (13)	C17—C13—C15—C16	−175.61 (10)
C5^i—C4—C5—C6	−1.03 (6)	N3—C7—C8—C9	0.68 (17)
C6^i—N2—C6—C5	−1.13 (7)	C7—N3—C11—C10	0.73 (16)
O3—C12—C13—C14	179.26 (9)	C7—C8—C9—C9^iv	−179.61 (11)
O3—C12—C13—C15	−60.50 (12)	C7—C8—C9—C10	0.54 (14)
O3—C12—C13—C17	58.56 (12)	C8—C9—C10—C11	−1.07 (14)
O4—C12—C13—C14	−0.89 (13)	C9^iv—C9—C10—C11	179.08 (11)
O4—C12—C13—C15	119.34 (10)	C9—C10—C11—N3	0.45 (17)
O4—C12—C13—C17	−121.60 (10)	C11—N3—C7—C8	−1.30 (16)

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

Catena((mu-1,2-bis(4-pyridine)ethylene-N,N')- (mu-diethylmalonato-O,O')-zinc(II) 1,2-bis(4-pyridine)ethylene solvate) (7)

Crystal data

C19H20N2O4Zn·0.25(C12H10N2)	Dx = 1.247 Mg m^−3
Mr = 451.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Cmcm	Cell parameters from 3505 reflections
a = 9.8266 (5) Å	θ = 2.3–25.9°
b = 22.0654 (12) Å	µ = 1.05 mm^−1
c = 22.1641 (11) Å	T = 120 K
V = 4805.8 (4) Å^3	Prism, colourless
Z = 8	0.43 × 0.29 × 0.21 mm
F(000) = 1872

Data collection

Bruker Smart 1000 CCD area detector diffractometer	2496 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
phi and ω scans	θmax = 29.2°, θmin = 2.1°
Absorption correction: multi-scan SADABS	h = −13→12
Tmin = 0.786, Tmax = 0.903	k = −30→30
22224 measured reflections	l = −30→30
3498 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.060P)^2 + 15.P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.008
3498 reflections	Δρmax = 0.97 e Å^−3
209 parameters	Δρmin = −1.03 e Å^−3
7 restraints

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	0.0000	0.20100 (2)	0.45562 (2)	0.01418 (14)
C12A	0.4323 (9)	0.1899 (4)	0.2500	0.0235 (12)	0.5
H12A	0.3787	0.1909	0.2154	0.028*	0.25
C12B	0.5000	0.1899 (4)	0.2785 (4)	0.0235 (12)	0.5
H12B	0.5884	0.1907	0.2935	0.028*	0.25
C6	−0.4331 (5)	0.0000	0.5000	0.0297 (6)
H6	−0.3699	−0.0301	0.5088	0.036*	0.5
N1	0.1477 (5)	0.1936 (2)	0.3925 (2)	0.0240 (11)	0.5
N2	−0.1398 (5)	0.1346 (2)	0.4648 (2)	0.0202 (10)	0.5
C1	−0.2696 (6)	0.1493 (2)	0.4768 (3)	0.0221 (12)	0.5
H1	−0.2939	0.1910	0.4775	0.027*	0.5
C2	−0.3685 (7)	0.1071 (3)	0.4882 (3)	0.0297 (6)	0.5
H2	−0.4588	0.1196	0.4970	0.036*	0.5
C3	−0.3360 (7)	0.0455 (3)	0.4867 (3)	0.0297 (6)	0.5
C4	−0.2009 (7)	0.0298 (3)	0.4741 (3)	0.0297 (6)	0.5
H4	−0.1741	−0.0115	0.4729	0.036*	0.5
C5	−0.1068 (6)	0.0752 (2)	0.4633 (3)	0.0256 (13)	0.5
H5	−0.0155	0.0642	0.4545	0.031*	0.5
C7	0.1175 (8)	0.1961 (3)	0.3331 (3)	0.0394 (18)	0.5
H7	0.0244	0.1987	0.3218	0.047*	0.5
C8	0.2122 (11)	0.1953 (4)	0.2890 (4)	0.063 (3)	0.5
H8	0.1857	0.1975	0.2478	0.075*	0.5
C9	0.3522 (11)	0.1909 (3)	0.3049 (5)	0.065 (3)	0.5
C10	0.3813 (8)	0.1894 (4)	0.3652 (5)	0.063 (3)	0.5
H10	0.4735	0.1868	0.3778	0.075*	0.5
C11	0.2792 (7)	0.1917 (3)	0.4082 (4)	0.0404 (18)	0.5
H11	0.3030	0.1918	0.4497	0.048*	0.5
O1	0.1012 (4)	0.27557 (17)	0.44104 (17)	0.0191 (8)	0.5
O2	0.1908 (5)	0.23148 (19)	0.35935 (19)	0.0294 (10)	0.5
O3	0.4079 (4)	0.28894 (16)	0.46641 (17)	0.0189 (8)	0.5
O4	0.3348 (4)	0.38364 (17)	0.48120 (19)	0.0236 (9)	0.5
C13	0.1817 (6)	0.2745 (3)	0.3956 (2)	0.0198 (11)	0.5
C14	0.2702 (6)	0.3316 (3)	0.3891 (2)	0.0211 (12)	0.5
C15	0.3426 (6)	0.3373 (2)	0.4505 (2)	0.0185 (11)	0.5
C16	0.3819 (7)	0.3236 (3)	0.3404 (3)	0.0312 (15)	0.5
H16A	0.4318	0.2855	0.3485	0.037*	0.5
H16B	0.3375	0.3195	0.3005	0.037*	0.5
C17	0.4826 (11)	0.3747 (3)	0.3373 (3)	0.0574 (17)	0.5
H17A	0.5495	0.3664	0.3056	0.086*	0.5
H17B	0.4347	0.4126	0.3281	0.086*	0.5
H17C	0.5292	0.3786	0.3762	0.086*	0.5
C18	0.1772 (7)	0.3859 (3)	0.3770 (3)	0.0317 (15)	0.5
H18A	0.2334	0.4230	0.3746	0.038*	0.5
H18B	0.1138	0.3906	0.4114	0.038*	0.5
C19	0.0945 (9)	0.3796 (4)	0.3188 (4)	0.0574 (17)	0.5
H19A	0.0371	0.4156	0.3135	0.086*	0.5
H19B	0.1565	0.3759	0.2844	0.086*	0.5
H19C	0.0369	0.3435	0.3212	0.086*	0.5
N3	0.0595 (12)	0.5320 (8)	0.1540 (8)	0.060*	0.125
C12	0.0692 (11)	0.5361 (9)	0.2140 (8)	0.060*	0.125
H12	−0.0122	0.5360	0.2372	0.072*	0.125
C1A	0.1929 (10)	0.5406 (9)	0.2441 (7)	0.060*	0.125
H1A	0.1950	0.5443	0.2867	0.072*	0.125
C1B	0.3142 (11)	0.5396 (4)	0.2112 (5)	0.060*	0.125
C1C	0.3030 (13)	0.5369 (8)	0.1482 (5)	0.060*	0.125
H1C	0.3823	0.5378	0.1237	0.072*	0.125
C1D	0.1755 (14)	0.5330 (10)	0.1221 (7)	0.060*	0.125
H1D	0.1698	0.5310	0.0793	0.072*	0.125
C1E	0.4442 (10)	0.5412 (4)	0.2436 (4)	0.060*	0.125
H1E	0.4409	0.5472	0.2860	0.072*	0.125
N9	0.9521 (12)	0.5441 (7)	0.3081 (8)	0.060*	0.125
C1F	0.9424 (10)	0.5399 (10)	0.2480 (8)	0.060*	0.125
C1G	0.8187 (11)	0.5355 (10)	0.2180 (7)	0.060*	0.125
H1G	0.8166	0.5318	0.1753	0.072*	0.125
C1H	0.6974 (11)	0.5364 (4)	0.2508 (5)	0.060*	0.125
C1I	0.7086 (12)	0.5391 (7)	0.3138 (5)	0.060*	0.125
H1I	0.6293	0.5382	0.3383	0.072*	0.125
C1J	0.8361 (13)	0.5430 (9)	0.3400 (7)	0.060*	0.125
H1J	0.8419	0.5451	0.3827	0.072*	0.125
C1K	0.5675 (11)	0.5349 (4)	0.2184 (4)	0.060*	0.125
H1K	0.5708	0.5288	0.1760	0.072*	0.125

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0111 (2)	0.0144 (2)	0.0171 (2)	0.000	0.000	−0.00118 (18)
C12A	0.016 (4)	0.029 (3)	0.026 (4)	0.000 (3)	0.000	0.000
C12B	0.016 (4)	0.029 (3)	0.026 (4)	0.000 (3)	0.000	0.000
C6	0.0224 (14)	0.0169 (12)	0.0500 (16)	0.000	0.000	0.0026 (12)
N1	0.020 (3)	0.026 (2)	0.026 (2)	0.003 (2)	0.012 (2)	0.001 (2)
N2	0.015 (2)	0.014 (2)	0.032 (3)	−0.0019 (18)	0.000 (2)	−0.0032 (18)
C1	0.016 (3)	0.012 (2)	0.038 (3)	−0.001 (2)	0.004 (2)	−0.002 (2)
C2	0.0224 (14)	0.0169 (12)	0.0500 (16)	0.000	0.000	0.0026 (12)
C3	0.0224 (14)	0.0169 (12)	0.0500 (16)	0.000	0.000	0.0026 (12)
C4	0.0224 (14)	0.0169 (12)	0.0500 (16)	0.000	0.000	0.0026 (12)
C5	0.014 (3)	0.017 (3)	0.046 (4)	−0.001 (2)	0.001 (3)	−0.006 (2)
C7	0.045 (5)	0.051 (4)	0.022 (3)	0.000 (4)	0.013 (3)	−0.003 (3)
C8	0.092 (8)	0.059 (5)	0.037 (4)	0.001 (5)	0.044 (5)	−0.006 (4)
C9	0.090 (8)	0.031 (4)	0.073 (6)	0.005 (4)	0.069 (6)	0.006 (4)
C10	0.029 (4)	0.043 (5)	0.116 (9)	0.009 (3)	0.043 (5)	0.020 (5)
C11	0.017 (3)	0.049 (4)	0.054 (4)	0.006 (3)	0.019 (3)	0.015 (3)
O1	0.017 (2)	0.0172 (17)	0.024 (2)	−0.0010 (16)	−0.0008 (16)	0.0006 (15)
O2	0.041 (3)	0.024 (2)	0.023 (2)	−0.007 (2)	−0.001 (2)	−0.0047 (18)
O3	0.019 (2)	0.0174 (18)	0.0202 (19)	−0.0006 (15)	−0.0029 (15)	0.0004 (14)
O4	0.026 (2)	0.0156 (18)	0.029 (2)	−0.0019 (16)	−0.0026 (18)	−0.0026 (16)
C13	0.019 (3)	0.020 (3)	0.020 (3)	0.001 (2)	−0.005 (2)	0.001 (2)
C14	0.023 (3)	0.021 (3)	0.019 (3)	−0.005 (2)	−0.003 (2)	0.003 (2)
C15	0.017 (3)	0.017 (2)	0.021 (3)	−0.002 (2)	0.001 (2)	0.005 (2)
C16	0.036 (4)	0.041 (4)	0.016 (3)	−0.008 (3)	0.005 (3)	−0.002 (2)
C17	0.064 (5)	0.057 (3)	0.050 (3)	0.002 (4)	−0.017 (4)	0.009 (2)
C18	0.038 (4)	0.022 (3)	0.035 (3)	0.002 (3)	−0.012 (3)	0.006 (3)
C19	0.064 (5)	0.057 (3)	0.050 (3)	0.002 (4)	−0.017 (4)	0.009 (2)

Geometric parameters (Å, º)

Zn1—N1	2.023 (5)	C14—C16	1.549 (8)
Zn1—N2	2.018 (5)	C14—C18	1.531 (8)
Zn1—O1	1.949 (4)	C16—H16A	0.9900
C12A—C12A^i	1.331 (18)	C16—H16B	0.9900
C12A—H12A	0.9301	C16—C17	1.501 (3)
C12A—C12B	0.918 (8)	C17—H17A	0.9800
C12A—C12B^ii	0.918 (8)	C17—H17B	0.9800
C12B—C12A^i	0.918 (8)	C17—H17C	0.9800
C12B—C12B^ii	1.264 (18)	C18—H18A	0.9900
C12B—H12B	0.9300	C18—H18B	0.9900
C6—C6^iii	1.314 (9)	C18—C19	1.532 (10)
C6—H6	0.9300	C19—H19A	0.9800
C6—C3	1.417 (7)	C19—H19B	0.9800
N1—C7	1.349 (8)	C19—H19C	0.9800
N1—C11	1.340 (9)	N3—C12	1.3376
N2—C1	1.343 (7)	N3—C1D	1.3418
N2—C5	1.351 (7)	C12—H12	0.9500
C1—H1	0.9500	C12—C1A	1.3895
C1—C2	1.370 (8)	C1A—H1A	0.9500
C2—H2	0.9500	C1A—C1B	1.3963
C2—C3	1.396 (8)	C1B—C1C	1.4015
C3—C4	1.400 (9)	C1B—C1E	1.4661
C4—H4	0.9500	C1C—H1C	0.9500
C4—C5	1.384 (8)	C1C—C1D	1.3840
C5—H5	0.9500	C1D—H1D	0.9500
C7—H7	0.9500	C1E—H1E	0.9500
C7—C8	1.351 (10)	C1E—C1K	1.3413
C8—H8	0.9500	N9—C1F	1.3376
C8—C9	1.423 (15)	N9—C1J	1.3415
C9—C10	1.368 (15)	C1F—C1G	1.3894
C10—H10	0.9500	C1G—H1G	0.9500
C10—C11	1.384 (10)	C1G—C1H	1.3963
C11—H11	0.9500	C1H—C1I	1.4019
O1—C13	1.280 (7)	C1H—C1K	1.4657
O2—C13	1.248 (7)	C1I—H1I	0.9500
O3—C15	1.295 (6)	C1I—C1J	1.3840
O4—C15	1.230 (7)	C1J—H1J	0.9500
C13—C14	1.537 (8)	C1K—H1K	0.9500
C14—C15	1.542 (8)
N2—Zn1—N1	120.0 (2)	O4—C15—C14	121.9 (5)
C12A^i—C12A—H12A	124.5	C14—C16—H16A	108.7
C12B—C12A—C12A^i	43.5 (6)	C14—C16—H16B	108.7
C12B^ii—C12A—C12A^i	43.5 (6)	H16A—C16—H16B	107.6
C12B^ii—C12A—H12A	81.0	C17—C16—C14	114.4 (6)
C12B—C12A—H12A	168.0	C17—C16—H16A	108.7
C12B—C12A—C12B^ii	87.0 (12)	C17—C16—H16B	108.7
C12A—C12B—C12A^i	93.0 (12)	C16—C17—H17A	109.5
C12A—C12B—C12B^ii	46.5 (6)	C16—C17—H17B	109.5
C12A^i—C12B—C12B^ii	46.5 (6)	C16—C17—H17C	109.5
C12A^i—C12B—H12B	64.4	H17A—C17—H17B	109.5
C12A—C12B—H12B	157.4	H17A—C17—H17C	109.5
C12B^ii—C12B—H12B	110.9	H17B—C17—H17C	109.5
C6^iii—C6—H6	131.9	C14—C18—H18A	108.9
C6^iii—C6—C3	132.4 (3)	C14—C18—H18B	108.9
C3—C6—H6	95.7	C14—C18—C19	113.1 (6)
C7—N1—Zn1	120.9 (5)	H18A—C18—H18B	107.8
C11—N1—Zn1	121.0 (5)	C19—C18—H18A	108.9
C11—N1—C7	117.8 (6)	C19—C18—H18B	108.9
C1—N2—Zn1	119.4 (4)	C18—C19—H19A	109.5
C1—N2—C5	117.8 (5)	C18—C19—H19B	109.5
C5—N2—Zn1	122.6 (4)	C18—C19—H19C	109.5
N2—C1—H1	118.4	H19A—C19—H19B	109.5
N2—C1—C2	123.2 (5)	H19A—C19—H19C	109.5
C2—C1—H1	118.4	H19B—C19—H19C	109.5
C1—C2—H2	120.2	C12—N3—C1D	117.6
C1—C2—C3	119.6 (6)	N3—C12—H12	118.5
C3—C2—H2	120.2	N3—C12—C1A	122.9
C2—C3—C6	122.0 (5)	C1A—C12—H12	118.5
C2—C3—C4	117.6 (6)	C12—C1A—H1A	120.1
C4—C3—C6	120.4 (5)	C12—C1A—C1B	119.7
C3—C4—H4	120.4	C1B—C1A—H1A	120.1
C5—C4—C3	119.3 (6)	C1A—C1B—C1C	116.9
C5—C4—H4	120.4	C1A—C1B—C1E	119.2
N2—C5—C4	122.5 (6)	C1C—C1B—C1E	123.9
N2—C5—H5	118.7	C1B—C1C—H1C	120.3
C4—C5—H5	118.7	C1D—C1C—C1B	119.4
N1—C7—H7	118.2	C1D—C1C—H1C	120.3
N1—C7—C8	123.6 (8)	N3—C1D—C1C	123.3
C8—C7—H7	118.2	N3—C1D—H1D	118.3
C7—C8—H8	120.4	C1C—C1D—H1D	118.3
C7—C8—C9	119.2 (8)	C1B—C1E—H1E	117.3
C9—C8—H8	120.4	C1K—C1E—C1B	125.5
C10—C9—C8	116.5 (7)	C1K—C1E—H1E	117.3
C9—C10—H10	119.3	C1F—N9—C1J	117.6
C9—C10—C11	121.4 (9)	N9—C1F—C1G	122.9
C11—C10—H10	119.3	C1F—C1G—H1G	120.1
N1—C11—C10	121.4 (8)	C1F—C1G—C1H	119.7
N1—C11—H11	119.3	C1H—C1G—H1G	120.1
C10—C11—H11	119.3	C1G—C1H—C1I	116.9
C13—O1—Zn1	115.5 (3)	C1G—C1H—C1K	119.2
O1—C13—C14	114.2 (5)	C1I—C1H—C1K	123.9
O2—C13—O1	124.4 (5)	C1H—C1I—H1I	120.3
O2—C13—C14	121.4 (5)	C1J—C1I—C1H	119.4
C13—C14—C15	104.2 (4)	C1J—C1I—H1I	120.3
C13—C14—C16	112.0 (5)	N9—C1J—C1I	123.3
C15—C14—C16	107.3 (5)	N9—C1J—H1J	118.4
C18—C14—C13	108.6 (5)	C1I—C1J—H1J	118.4
C18—C14—C15	111.4 (5)	C1E—C1K—C1H	125.5
C18—C14—C16	113.0 (5)	C1E—C1K—H1K	117.3
O3—C15—C14	113.7 (5)	C1H—C1K—H1K	117.3
O4—C15—O3	124.4 (5)
Zn1—N1—C7—C8	175.7 (6)	C13—C14—C16—C17	−172.7 (6)
Zn1—N1—C11—C10	−177.0 (5)	C13—C14—C18—C19	−61.2 (7)
Zn1—N2—C1—C2	−174.9 (5)	C15—C14—C16—C17	−58.9 (7)
Zn1—N2—C5—C4	175.0 (5)	C15—C14—C18—C19	−175.4 (6)
Zn1—O1—C13—O2	5.1 (7)	C16—C14—C15—O3	−64.7 (6)
Zn1—O1—C13—C14	−174.2 (3)	C16—C14—C15—O4	116.9 (6)
C12A^i—C12A—C12B—C12B^ii	−0.1 (16)	C16—C14—C18—C19	63.7 (7)
C12B^ii—C12A—C12B—C12A^i	0.1 (16)	C18—C14—C15—O3	171.2 (5)
C6^iii—C6—C3—C2	20.6 (9)	C18—C14—C15—O4	−7.3 (8)
C6^iii—C6—C3—C4	−162.4 (4)	C18—C14—C16—C17	64.3 (7)
C6—C3—C4—C5	−177.7 (6)	N3—C12—C1A—C1B	−1.3
N1—C7—C8—C9	0.6 (13)	C12—N3—C1D—C1C	1.4
N2—C1—C2—C3	−0.8 (10)	C12—C1A—C1B—C1C	3.0
C1—N2—C5—C4	−0.5 (9)	C12—C1A—C1B—C1E	−176.9
C1—C2—C3—C6	177.9 (6)	C1A—C1B—C1C—C1D	−2.5
C1—C2—C3—C4	0.7 (10)	C1A—C1B—C1E—C1K	173.4
C2—C3—C4—C5	−0.6 (10)	C1B—C1C—C1D—N3	0.4
C3—C4—C5—N2	0.4 (10)	C1B—C1E—C1K—C1H	180.0
C5—N2—C1—C2	0.7 (9)	C1C—C1B—C1E—C1K	−6.4
C7—N1—C11—C10	−3.0 (10)	C1D—N3—C12—C1A	−0.9
C7—C8—C9—C10	−1.6 (12)	C1E—C1B—C1C—C1D	177.3
C8—C9—C10—C11	0.4 (12)	N9—C1F—C1G—C1H	1.2
C9—C10—C11—N1	2.0 (12)	C1F—N9—C1J—C1I	−1.4
C11—N1—C7—C8	1.7 (11)	C1F—C1G—C1H—C1I	−2.9
O1—C13—C14—C15	54.7 (6)	C1F—C1G—C1H—C1K	176.9
O1—C13—C14—C16	170.4 (5)	C1G—C1H—C1I—C1J	2.5
O1—C13—C14—C18	−64.1 (6)	C1G—C1H—C1K—C1E	−173.4
O2—C13—C14—C15	−124.7 (6)	C1H—C1I—C1J—N9	−0.4
O2—C13—C14—C16	−9.0 (8)	C1I—C1H—C1K—C1E	6.4
O2—C13—C14—C18	116.5 (6)	C1J—N9—C1F—C1G	1.0
C13—C14—C15—O3	54.3 (6)	C1K—C1H—C1I—C1J	−177.3
C13—C14—C15—O4	−124.2 (6)

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

Catena(tris(mu-1,2-bis(4-pyridine)ethylene-N,N')-(mu-tetrakis(4-pyridyl) cyclobutane-N,N')-tetrakis(mu-diethylmalonato-O,O')-tetrazinc(II) (7a)

Crystal data

C22H22.5N2.5O4Zn	Dx = 1.259 Mg m^−3
Mr = 451.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 3429 reflections
a = 9.845 (8) Å	θ = 2.1–25.0°
b = 22.082 (17) Å	µ = 1.06 mm^−1
c = 21.905 (17) Å	T = 120 K
V = 4762 (6) Å^3	Prism, yellow
Z = 8	0.43 × 0.29 × 0.21 mm
F(000) = 1872

Data collection

Bruker Apex II CCD area detector diffractometer	Rint = 0.202
Absorption correction: multi-scan SADABS	θmax = 30.7°, θmin = 1.9°
Tmin = 0.786, Tmax = 0.903	h = −14→13
40353 measured reflections	k = −31→31
7285 independent reflections	l = −31→31
3089 reflections with I > 2σ(I)

Refinement

Refinement on F^2	21 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.114	H-atom parameters constrained
wR(F^2) = 0.237	w = 1/[σ^2(Fo^2) + (0.030P)^2 + 41.9P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
7285 reflections	Δρmax = 1.29 e Å^−3
252 parameters	Δρmin = −0.76 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.49767 (10)	0.29677 (3)	0.45425 (3)	0.0378 (2)
O1	0.5885 (5)	0.2874 (2)	0.53270 (18)	0.0413 (12)
O2	0.6572 (6)	0.3834 (2)	0.5198 (2)	0.0488 (13)
O3	0.8978 (5)	0.2784 (2)	0.55856 (18)	0.0412 (12)
O4	0.8130 (6)	0.2327 (2)	0.6410 (2)	0.0540 (14)
N1	0.3596 (6)	0.3641 (3)	0.4636 (2)	0.0392 (14)
N2	0.6445 (7)	0.3064 (3)	0.3905 (3)	0.0484 (16)
N3	0.577 (2)	0.4977 (10)	0.2855 (13)	0.194 (7)	0.5
C24	0.691 (3)	0.4994 (10)	0.3231 (9)	0.194 (7)	0.5
H24	0.6863	0.5190	0.3607	0.233*	0.5
C25	0.811 (2)	0.4719 (12)	0.3046 (13)	0.194 (7)	0.5
H25	0.8869	0.4731	0.3297	0.233*	0.5
C21	0.817 (2)	0.4427 (11)	0.2484 (14)	0.194 (7)	0.5
C22	0.704 (3)	0.4410 (10)	0.2108 (9)	0.194 (7)	0.5
H22	0.7079	0.4214	0.1733	0.233*	0.5
C23	0.583 (2)	0.4684 (11)	0.2294 (12)	0.194 (7)	0.5
H23	0.5074	0.4673	0.2042	0.233*	0.5
C1	0.6503 (8)	0.3360 (3)	0.5494 (3)	0.0418 (17)
C2	0.7220 (8)	0.3305 (3)	0.6122 (3)	0.0446 (19)
C3	0.8173 (8)	0.2764 (3)	0.6052 (3)	0.0420 (18)
C4	0.6097 (9)	0.3187 (4)	0.6597 (3)	0.064 (3)
H4A	0.5671	0.2802	0.6504	0.077*
H4B	0.6515	0.3152	0.6996	0.077*
C5	0.4995 (13)	0.3671 (5)	0.6628 (4)	0.099 (4)
H5A	0.4600	0.3724	0.6231	0.148*
H5B	0.5387	0.4047	0.6761	0.148*
H5C	0.4304	0.3547	0.6911	0.148*
C6	0.8068 (10)	0.3867 (4)	0.6267 (4)	0.065 (3)
H6A	0.8688	0.3939	0.5931	0.078*
H6B	0.7465	0.4213	0.6294	0.078*
C7	0.8882 (13)	0.3826 (5)	0.6853 (4)	0.100 (4)
H7A	0.9442	0.3470	0.6843	0.150*
H7B	0.8274	0.3804	0.7194	0.150*
H7C	0.9446	0.4179	0.6892	0.150*
C8	0.2304 (8)	0.3495 (3)	0.4769 (3)	0.0446 (18)
H8	0.2064	0.3088	0.4783	0.054*
C9	0.1312 (8)	0.3927 (3)	0.4886 (3)	0.0495 (19)
H9	0.0433	0.3807	0.4984	0.059*
C10	0.1639 (8)	0.4544 (3)	0.4856 (3)	0.0476 (19)
C11	0.2969 (8)	0.4689 (3)	0.4711 (4)	0.0489 (19)
H11	0.3232	0.5092	0.4677	0.059*
C12	0.3900 (8)	0.4235 (3)	0.4615 (3)	0.0451 (18)
H12	0.4792	0.4345	0.4531	0.054*
C13	0.0661 (8)	0.5031 (4)	0.4966 (4)	0.0546 (19)
H13	0.1006	0.5423	0.4990	0.066*
C14	0.7735 (9)	0.3125 (4)	0.4048 (4)	0.062 (2)
H14	0.7977	0.3128	0.4458	0.074*
C15	0.8750 (10)	0.3185 (4)	0.3611 (4)	0.072 (3)
H15	0.9655	0.3225	0.3726	0.086*
C16	0.8372 (11)	0.3185 (4)	0.2992 (4)	0.071 (2)
C17	0.7072 (11)	0.3089 (6)	0.2858 (4)	0.100 (4)
H17	0.6808	0.3053	0.2452	0.121*
C18	0.6134 (11)	0.3044 (5)	0.3304 (4)	0.084 (3)
H18	0.5228	0.2997	0.3193	0.100*
C19	0.9383 (11)	0.3272 (5)	0.2426 (6)	0.098 (4)
H19	0.9160	0.3032	0.2064	0.117*
C20	0.936 (4)	0.4026 (16)	0.2324 (18)	0.194 (7)	0.5
H20	0.9592	0.4104	0.1896	0.233*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0446 (4)	0.0454 (4)	0.0233 (3)	0.0029 (5)	0.0033 (4)	0.0033 (3)
O1	0.062 (3)	0.041 (3)	0.021 (2)	0.001 (3)	0.001 (2)	0.0019 (19)
O2	0.065 (4)	0.041 (3)	0.040 (3)	0.001 (3)	−0.004 (3)	0.001 (2)
O3	0.056 (3)	0.054 (3)	0.0137 (19)	−0.003 (3)	−0.003 (2)	−0.0005 (19)
O4	0.074 (4)	0.063 (3)	0.025 (2)	0.006 (3)	−0.003 (3)	0.004 (2)
N1	0.060 (4)	0.049 (3)	0.009 (2)	0.000 (3)	0.008 (2)	0.005 (2)
N2	0.050 (4)	0.067 (4)	0.028 (3)	−0.003 (4)	0.010 (3)	0.002 (3)
N3	0.199 (17)	0.207 (15)	0.177 (15)	0.078 (13)	0.025 (13)	0.031 (12)
C24	0.199 (17)	0.207 (15)	0.177 (15)	0.078 (13)	0.025 (13)	0.031 (12)
C25	0.199 (17)	0.207 (15)	0.177 (15)	0.078 (13)	0.025 (13)	0.031 (12)
C21	0.199 (17)	0.207 (15)	0.177 (15)	0.078 (13)	0.025 (13)	0.031 (12)
C22	0.199 (17)	0.207 (15)	0.177 (15)	0.078 (13)	0.025 (13)	0.031 (12)
C23	0.199 (17)	0.207 (15)	0.177 (15)	0.078 (13)	0.025 (13)	0.031 (12)
C1	0.062 (5)	0.037 (4)	0.027 (3)	0.005 (4)	−0.003 (3)	−0.005 (3)
C2	0.063 (5)	0.049 (4)	0.021 (3)	0.002 (4)	−0.008 (3)	−0.005 (3)
C3	0.055 (5)	0.043 (4)	0.028 (3)	−0.001 (4)	−0.016 (3)	−0.003 (3)
C4	0.071 (6)	0.102 (7)	0.019 (3)	0.015 (6)	0.004 (4)	−0.005 (4)
C5	0.104 (8)	0.146 (10)	0.045 (5)	0.051 (9)	0.010 (6)	0.000 (6)
C6	0.092 (7)	0.056 (5)	0.048 (5)	0.007 (5)	−0.018 (5)	−0.009 (4)
C7	0.143 (11)	0.090 (8)	0.066 (6)	−0.005 (8)	−0.058 (7)	−0.018 (6)
C8	0.054 (5)	0.033 (4)	0.047 (4)	0.001 (4)	0.007 (4)	0.005 (3)
C9	0.043 (5)	0.050 (5)	0.055 (5)	0.008 (4)	0.010 (4)	0.003 (4)
C10	0.056 (5)	0.041 (4)	0.046 (4)	0.009 (4)	0.004 (4)	0.007 (3)
C11	0.052 (5)	0.039 (4)	0.056 (5)	0.001 (4)	−0.005 (4)	0.011 (4)
C12	0.044 (4)	0.044 (4)	0.047 (4)	−0.002 (4)	−0.001 (4)	0.014 (3)
C13	0.062 (5)	0.037 (4)	0.064 (5)	0.001 (5)	0.002 (6)	0.001 (3)
C14	0.050 (5)	0.084 (7)	0.050 (4)	0.002 (5)	0.014 (4)	−0.005 (4)
C15	0.058 (5)	0.084 (7)	0.074 (5)	−0.001 (5)	0.026 (4)	−0.008 (5)
C16	0.087 (5)	0.070 (6)	0.055 (4)	0.000 (5)	0.036 (4)	−0.005 (4)
C17	0.084 (5)	0.180 (13)	0.038 (4)	−0.014 (6)	0.027 (4)	0.000 (5)
C18	0.069 (6)	0.151 (10)	0.031 (4)	−0.010 (6)	0.012 (4)	−0.001 (5)
C19	0.115 (10)	0.094 (7)	0.085 (8)	−0.012 (7)	−0.061 (7)	0.007 (7)
C20	0.199 (17)	0.207 (15)	0.177 (15)	0.078 (13)	0.025 (13)	0.031 (12)

Geometric parameters (Å, º)

Zn1—O1	1.948 (4)	C5—H5C	0.9600
Zn1—O3^i	1.950 (5)	C6—H6A	0.9700
Zn1—N1	2.025 (6)	C6—H6B	0.9700
Zn1—N2	2.022 (6)	C6—C7	1.515 (11)
O1—C1	1.285 (8)	C7—H7A	0.9600
O2—C1	1.234 (8)	C7—H7B	0.9600
O3—Zn1^ii	1.950 (5)	C7—H7C	0.9600
O3—C3	1.294 (8)	C8—H8	0.9300
O4—C3	1.244 (8)	C8—C9	1.389 (10)
N1—C8	1.344 (9)	C9—H9	0.9300
N1—C12	1.346 (9)	C9—C10	1.402 (10)
N2—C14	1.314 (10)	C10—C11	1.386 (11)
N2—C18	1.353 (10)	C10—C13	1.463 (11)
N3—C24	1.3900	C11—H11	0.9300
N3—C23	1.3900	C11—C12	1.374 (10)
C24—H24	0.9300	C12—H12	0.9300
C24—C25	1.3900	C13—C13^iii	1.317 (15)
C25—H25	0.9300	C13—H13	0.9300
C25—C21	1.3900	C14—H14	0.9300
C21—C22	1.3900	C14—C15	1.390 (11)
C21—C20	1.51 (4)	C15—H15	0.9300
C22—H22	0.9300	C15—C16	1.406 (13)
C22—C23	1.3900	C16—C17	1.330 (14)
C23—H23	0.9300	C16—C19	1.601 (15)
C1—C2	1.551 (9)	C17—H17	0.9300
C2—C3	1.527 (10)	C17—C18	1.347 (12)
C2—C4	1.540 (11)	C18—H18	0.9300
C2—C6	1.529 (11)	C19—C19^iv	1.26 (2)
C4—H4A	0.9700	C19—H19	0.9800
C4—H4B	0.9700	C19—C20	1.68 (3)
C4—C5	1.524 (13)	C20—C20^iv	1.48 (7)
C5—H5A	0.9600	C20—H20	0.9800
C5—H5B	0.9600
O1—Zn1—O3^i	105.57 (19)	H6A—C6—H6B	107.6
O1—Zn1—N1	107.3 (2)	C7—C6—C2	114.6 (8)
O1—Zn1—N2	107.0 (2)	C7—C6—H6A	108.6
O3^i—Zn1—N1	107.5 (2)	C7—C6—H6B	108.6
O3^i—Zn1—N2	110.5 (2)	C6—C7—H7A	109.5
N2—Zn1—N1	118.2 (2)	C6—C7—H7B	109.5
C1—O1—Zn1	112.3 (4)	C6—C7—H7C	109.5
C3—O3—Zn1^ii	113.1 (4)	H7A—C7—H7B	109.5
C8—N1—Zn1	118.8 (5)	H7A—C7—H7C	109.5
C8—N1—C12	116.8 (7)	H7B—C7—H7C	109.5
C12—N1—Zn1	124.3 (5)	N1—C8—H8	118.6
C14—N2—Zn1	122.4 (5)	N1—C8—C9	122.8 (7)
C14—N2—C18	117.0 (7)	C9—C8—H8	118.6
C18—N2—Zn1	120.5 (6)	C8—C9—H9	120.1
C24—N3—C23	120.0	C8—C9—C10	119.8 (7)
N3—C24—H24	120.0	C10—C9—H9	120.1
C25—C24—N3	120.0	C9—C10—C13	123.8 (8)
C25—C24—H24	120.0	C11—C10—C9	116.9 (7)
C24—C25—H25	120.0	C11—C10—C13	119.4 (7)
C24—C25—C21	120.0	C10—C11—H11	120.1
C21—C25—H25	120.0	C12—C11—C10	119.8 (7)
C25—C21—C20	121 (3)	C12—C11—H11	120.1
C22—C21—C25	120.0	N1—C12—C11	123.9 (7)
C22—C21—C20	118 (3)	N1—C12—H12	118.0
C21—C22—H22	120.0	C11—C12—H12	118.0
C21—C22—C23	120.0	C10—C13—H13	116.9
C23—C22—H22	120.0	C13^iii—C13—C10	126.3 (11)
N3—C23—H23	120.0	C13^iii—C13—H13	116.9
C22—C23—N3	120.0	N2—C14—H14	118.7
C22—C23—H23	120.0	N2—C14—C15	122.7 (8)
O1—C1—C2	113.7 (6)	C15—C14—H14	118.7
O2—C1—O1	125.7 (6)	C14—C15—H15	120.9
O2—C1—C2	120.6 (7)	C14—C15—C16	118.2 (9)
C3—C2—C1	104.6 (5)	C16—C15—H15	120.9
C3—C2—C4	112.2 (7)	C15—C16—C19	125.6 (9)
C3—C2—C6	108.7 (7)	C17—C16—C15	117.9 (8)
C4—C2—C1	106.6 (6)	C17—C16—C19	116.5 (9)
C6—C2—C1	111.6 (6)	C16—C17—H17	119.6
C6—C2—C4	112.9 (7)	C16—C17—C18	120.7 (10)
O3—C3—C2	115.3 (6)	C18—C17—H17	119.6
O4—C3—O3	123.1 (7)	N2—C18—H18	118.4
O4—C3—C2	121.5 (7)	C17—C18—N2	123.2 (10)
C2—C4—H4A	108.5	C17—C18—H18	118.4
C2—C4—H4B	108.5	C16—C19—H19	115.1
H4A—C4—H4B	107.5	C16—C19—C20	102.4 (17)
C5—C4—C2	115.0 (8)	C19^iv—C19—C16	113.7 (14)
C5—C4—H4A	108.5	C19^iv—C19—H19	115.1
C5—C4—H4B	108.5	C19^iv—C19—C20	92.7 (13)
C4—C5—H5A	109.5	C20—C19—H19	115.1
C4—C5—H5B	109.5	C21—C20—C19	124 (3)
C4—C5—H5C	109.5	C21—C20—H20	107.4
H5A—C5—H5B	109.5	C19—C20—H20	107.4
H5A—C5—H5C	109.5	C20^iv—C20—C21	123 (4)
H5B—C5—H5C	109.5	C20^iv—C20—C19	85.3 (13)
C2—C6—H6A	108.6	C20^iv—C20—H20	107.4
C2—C6—H6B	108.6

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

(1,2-Bis(4-pyridine)ethylene-N)-tetraaqua-zinc(II) bis(hydrogen diethylmalonate) (8)

Crystal data

C24H28N4O4Zn·2(C7H10O4)	F(000) = 860
Mr = 818.17	Dx = 1.371 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 22.881 (2) Å	Cell parameters from 1056 reflections
b = 6.8976 (6) Å	θ = 2.0–34.0°
c = 14.1573 (12) Å	µ = 0.69 mm^−1
β = 117.532 (2)°	T = 120 K
V = 1981.3 (3) Å^3	Prism, colourless
Z = 2	0.7 × 0.52 × 0.23 mm

Data collection

Bruker SMART APEX CCD area detector diffractometer	4490 independent reflections
Radiation source: sealed tube	3929 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 8 pixels mm^-1	θmax = 34.6°, θmin = 1.9°
ω and φ scans	h = −36→35
Absorption correction: multi-scan SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1120 before and 0.0465 after correction. The Ratio of minimum to maximum transmission is 0.8858. The λ/2 correction factor is 0.00150.	k = −10→11
Tmin = 0.662, Tmax = 0.747	l = −22→22
17312 measured reflections

Refinement

Refinement on F^2	19 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.132	w = 1/[σ^2(Fo^2) + (0.062P)^2 + 3.868P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
4490 reflections	Δρmax = 2.14 e Å^−3
182 parameters	Δρmin = −1.68 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.5000	0.5000	0.5000	0.01227 (9)
O1	0.45049 (5)	0.27783 (16)	0.53642 (8)	0.01614 (19)
H1A	0.4736	0.1809	0.5702	0.024*
H1B	0.4259	0.2976	0.5658	0.024*
N1	0.41966 (8)	0.5000	0.34231 (13)	0.0140 (3)
N2	0.03474 (9)	0.5000	−0.31163 (14)	0.0180 (3)
C9	0.13980 (10)	0.5000	−0.10457 (15)	0.0140 (3)
C2	0.30291 (10)	0.5000	0.22963 (15)	0.0149 (3)
H2	0.2599	0.5000	0.2239	0.018*
C007	0.42808 (10)	0.5000	0.25486 (16)	0.0155 (3)
H007	0.4717	0.5000	0.2632	0.019*
C10	0.07443 (10)	0.5000	−0.12304 (17)	0.0190 (4)
H10	0.0645	0.5000	−0.0649	0.023*
C6	0.19314 (10)	0.5000	0.00450 (15)	0.0158 (3)
H6	0.1816	0.5000	0.0609	0.019*
C4	0.37599 (10)	0.5000	0.15287 (16)	0.0169 (3)
H4	0.3842	0.5000	0.0930	0.020*
C3	0.31128 (10)	0.5000	0.13812 (15)	0.0143 (3)
C1	0.35734 (10)	0.5000	0.32830 (16)	0.0153 (3)
H1	0.3506	0.5000	0.3896	0.018*
C8	0.15071 (10)	0.5000	−0.19365 (16)	0.0178 (4)
H8	0.1944	0.5000	−0.1853	0.021*
O2	0.11947 (12)	0.1572 (3)	0.3637 (2)	0.0661 (6)
C5	0.25706 (10)	0.5000	0.03022 (16)	0.0183 (4)
H5	0.2682	0.5000	−0.0267	0.022*
C7	0.09753 (11)	0.5000	−0.29392 (17)	0.0202 (4)
H7	0.1059	0.5000	−0.3537	0.024*
C11	0.02424 (10)	0.5000	−0.22623 (17)	0.0194 (4)
H11	−0.0200	0.5000	−0.2372	0.023*
C12	0.13389 (16)	0.0000	0.3397 (3)	0.0423 (8)
C15	0.2804 (2)	0.0368 (7)	0.4335 (4)	0.0432 (15)	0.5
H15A	0.3198	0.1182	0.4684	0.065*	0.5
H15B	0.2590	0.0266	0.4793	0.065*	0.5
H15C	0.2931	−0.0927	0.4211	0.065*	0.5
O4	0.19689 (15)	0.1340 (4)	0.1532 (2)	0.0309 (6)	0.5
C13	0.1708 (2)	0.0000	0.2724 (3)	0.0660 (12)
O3	0.15242 (19)	0.2993 (5)	0.2354 (3)	0.0448 (8)	0.5
C14	0.2421 (2)	0.1099 (6)	0.3480 (4)	0.0341 (9)	0.5
H14A	0.2658	0.1238	0.3050	0.041*	0.5
H14B	0.2319	0.2425	0.3629	0.041*	0.5
C16	0.17333 (18)	0.1370 (5)	0.2144 (3)	0.0245 (6)	0.5
C17	0.1360 (3)	0.2053 (7)	0.1868 (4)	0.0399 (10)	0.5
H17A	0.1372	0.3206	0.2293	0.048*	0.5
H17B	0.1616	0.2344	0.1479	0.048*	0.5
C18	0.0658 (3)	0.1561 (9)	0.1091 (5)	0.0553 (14)	0.5
H18A	0.0456	0.2662	0.0612	0.083*	0.5
H18B	0.0652	0.0422	0.0673	0.083*	0.5
H18C	0.0410	0.1280	0.1484	0.083*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01073 (14)	0.01526 (15)	0.01057 (14)	0.000	0.00473 (11)	0.000
O1	0.0133 (4)	0.0188 (5)	0.0172 (4)	0.0012 (3)	0.0078 (4)	0.0046 (4)
N1	0.0130 (7)	0.0162 (7)	0.0125 (7)	0.000	0.0055 (6)	0.000
N2	0.0145 (7)	0.0213 (8)	0.0151 (7)	0.000	0.0043 (6)	0.000
C9	0.0135 (8)	0.0137 (8)	0.0130 (7)	0.000	0.0046 (6)	0.000
C2	0.0121 (7)	0.0184 (8)	0.0134 (7)	0.000	0.0053 (6)	0.000
C007	0.0134 (8)	0.0191 (8)	0.0137 (8)	0.000	0.0059 (6)	0.000
C10	0.0157 (8)	0.0268 (10)	0.0154 (8)	0.000	0.0081 (7)	0.000
C6	0.0159 (8)	0.0178 (8)	0.0120 (7)	0.000	0.0051 (6)	0.000
C4	0.0156 (8)	0.0226 (9)	0.0127 (8)	0.000	0.0068 (7)	0.000
C3	0.0137 (8)	0.0155 (8)	0.0118 (7)	0.000	0.0044 (6)	0.000
C1	0.0131 (8)	0.0198 (9)	0.0126 (7)	0.000	0.0055 (6)	0.000
C8	0.0137 (8)	0.0267 (10)	0.0123 (8)	0.000	0.0053 (7)	0.000
O2	0.0781 (12)	0.0570 (11)	0.1101 (15)	0.0156 (10)	0.0834 (12)	0.0184 (11)
C5	0.0159 (8)	0.0249 (10)	0.0125 (8)	0.000	0.0053 (7)	0.000
C7	0.0158 (8)	0.0307 (11)	0.0129 (8)	0.000	0.0057 (7)	0.000
C11	0.0137 (8)	0.0247 (10)	0.0183 (9)	0.000	0.0062 (7)	0.000
C12	0.0302 (13)	0.071 (2)	0.0407 (15)	0.000	0.0292 (13)	0.000
C15	0.0364 (19)	0.041 (4)	0.055 (2)	0.0050 (17)	0.0241 (18)	0.0089 (19)
O4	0.0389 (14)	0.0317 (13)	0.0357 (14)	0.0011 (11)	0.0288 (12)	0.0064 (11)
C13	0.0405 (16)	0.127 (3)	0.0504 (17)	0.000	0.0377 (15)	0.000
O3	0.0614 (18)	0.0302 (14)	0.0658 (19)	0.0119 (13)	0.0488 (16)	0.0119 (14)
C14	0.038 (2)	0.0290 (17)	0.053 (2)	−0.0132 (15)	0.0364 (19)	−0.0143 (17)
C16	0.0311 (16)	0.0179 (13)	0.0366 (17)	0.0041 (12)	0.0259 (15)	0.0082 (12)
C17	0.051 (3)	0.029 (2)	0.057 (3)	0.001 (2)	0.039 (2)	0.010 (2)
C18	0.057 (3)	0.056 (3)	0.064 (3)	0.023 (3)	0.038 (3)	0.026 (3)

Geometric parameters (Å, º)

Zn1—O1^i	2.1066 (10)	C8—H8	0.9500
Zn1—O1	2.1066 (10)	C8—C7	1.378 (3)
Zn1—O1^ii	2.1066 (10)	O2—C12	1.226 (2)
Zn1—O1^iii	2.1066 (10)	C5—H5	0.9500
Zn1—N1^i	2.1376 (17)	C7—H7	0.9500
Zn1—N1	2.1376 (17)	C11—H11	0.9500
O1—H1A	0.8494	C12—O2^iv	1.226 (2)
O1—H1B	0.8509	C12—C13	1.538 (4)
N1—C007	1.338 (3)	C15—H15A	0.9800
N1—C1	1.346 (3)	C15—H15B	0.9800
N2—C7	1.339 (3)	C15—H15C	0.9800
N2—C11	1.337 (3)	C15—C14	1.228 (7)
C9—C10	1.394 (3)	O4—C16	1.214 (4)
C9—C6	1.460 (3)	C13—C14	1.663 (6)
C9—C8	1.394 (3)	C13—C16	1.271 (4)
C2—H2	0.9500	C13—C16^iv	1.271 (4)
C2—C3	1.394 (3)	C13—C17	1.794 (5)
C2—C1	1.376 (3)	O3—C16	1.305 (5)
C007—H007	0.9500	C14—H14A	0.9900
C007—C4	1.384 (3)	C14—H14B	0.9900
C10—H10	0.9500	C16—C16^iv	1.890 (7)
C10—C11	1.379 (3)	C17—H17A	0.9900
C6—H6	0.9500	C17—H17B	0.9900
C6—C5	1.334 (3)	C17—C18	1.507 (8)
C4—H4	0.9500	C18—H18A	0.9800
C4—C3	1.397 (3)	C18—H18B	0.9800
C3—C5	1.456 (3)	C18—H18C	0.9800
C1—H1	0.9500
O1^i—Zn1—O1^ii	86.65 (6)	C6—C5—C3	125.55 (19)
O1^i—Zn1—O1^iii	93.35 (6)	C6—C5—H5	117.2
O1^ii—Zn1—O1^iii	180.00 (5)	C3—C5—H5	117.2
O1^i—Zn1—O1	180.0	N2—C7—C8	123.6 (2)
O1^ii—Zn1—O1	93.35 (6)	N2—C7—H7	118.2
O1^iii—Zn1—O1	86.65 (6)	C8—C7—H7	118.2
O1—Zn1—N1^i	92.55 (4)	N2—C11—C10	123.3 (2)
O1—Zn1—N1	87.45 (4)	N2—C11—H11	118.4
O1^iii—Zn1—N1	92.55 (4)	C10—C11—H11	118.4
O1^i—Zn1—N1^i	87.45 (4)	O2—C12—O2^iv	124.3 (3)
O1^ii—Zn1—N1	87.45 (4)	O2^iv—C12—C13	117.85 (14)
O1^i—Zn1—N1	92.55 (4)	O2—C12—C13	117.85 (14)
O1^iii—Zn1—N1^i	87.45 (4)	H15A—C15—H15B	109.5
O1^ii—Zn1—N1^i	92.55 (4)	H15A—C15—H15C	109.5
N1^i—Zn1—N1	180.0	H15B—C15—H15C	109.5
Zn1—O1—H1A	116.4	C14—C15—H15A	109.5
Zn1—O1—H1B	123.7	C14—C15—H15B	109.5
H1A—O1—H1B	103.4	C14—C15—H15C	109.5
C007—N1—Zn1	122.97 (13)	C12—C13—C14	104.9 (3)
C007—N1—C1	117.37 (17)	C12—C13—C17	102.7 (2)
C1—N1—Zn1	119.67 (13)	C14—C13—C17	94.1 (2)
C11—N2—C7	117.14 (18)	C16—C13—C12	127.0 (2)
C10—C9—C6	119.88 (18)	C16^iv—C13—C12	127.0 (2)
C8—C9—C10	117.10 (18)	C16^iv—C13—C16	96.1 (4)
C8—C9—C6	123.02 (18)	C15—C14—C13	119.2 (4)
C3—C2—H2	120.2	C15—C14—H14A	107.5
C1—C2—H2	120.2	C15—C14—H14B	107.5
C1—C2—C3	119.65 (18)	C13—C14—H14A	107.5
N1—C007—H007	118.6	C13—C14—H14B	107.5
N1—C007—C4	122.85 (18)	H14A—C14—H14B	107.0
C4—C007—H007	118.6	O4—C16—C13	128.0 (3)
C9—C10—H10	120.2	O4—C16—O3	120.5 (3)
C11—C10—C9	119.63 (19)	O4—C16—C16^iv	89.0 (2)
C11—C10—H10	120.2	C13—C16—O3	111.1 (3)
C9—C6—H6	117.8	C13—C16—C16^iv	42.0 (2)
C5—C6—C9	124.32 (19)	O3—C16—C16^iv	149.1 (2)
C5—C6—H6	117.8	C13—C17—H17A	110.1
C007—C4—H4	120.1	C13—C17—H17B	110.1
C007—C4—C3	119.89 (18)	H17A—C17—H17B	108.5
C3—C4—H4	120.1	C18—C17—C13	107.8 (4)
C2—C3—C4	116.90 (18)	C18—C17—H17A	110.1
C2—C3—C5	123.94 (18)	C18—C17—H17B	110.1
C4—C3—C5	119.15 (18)	C17—C18—H18A	109.5
N1—C1—C2	123.34 (18)	C17—C18—H18B	109.5
N1—C1—H1	118.3	C17—C18—H18C	109.5
C2—C1—H1	118.3	H18A—C18—H18B	109.5
C9—C8—H8	120.3	H18A—C18—H18C	109.5
C7—C8—C9	119.33 (19)	H18B—C18—H18C	109.5
C7—C8—H8	120.3
Zn1—N1—C007—C4	180.000 (1)	O2—C12—C13—C16	−20.5 (6)
Zn1—N1—C1—C2	180.000 (1)	O2—C12—C13—C16^iv	−157.9 (4)
N1—C007—C4—C3	0.000 (1)	O2—C12—C13—C17	−35.2 (4)
C9—C10—C11—N2	0.000 (1)	O2^iv—C12—C13—C17	143.2 (3)
C9—C6—C5—C3	180.000 (1)	C7—N2—C11—C10	0.000 (1)
C9—C8—C7—N2	0.000 (1)	C11—N2—C7—C8	0.000 (1)
C2—C3—C5—C6	0.000 (1)	C12—C13—C14—C15	62.5 (4)
C007—N1—C1—C2	0.000 (1)	C12—C13—C16—O4	−172.5 (4)
C007—C4—C3—C2	0.000 (1)	C12—C13—C16—O3	14.1 (6)
C007—C4—C3—C5	180.000 (1)	C12—C13—C16—C16^iv	−147.0 (7)
C10—C9—C6—C5	180.000 (1)	C12—C13—C17—C18	−69.8 (4)
C10—C9—C8—C7	0.000 (1)	C14—C13—C16—O4	89.5 (5)
C6—C9—C10—C11	180.000 (1)	C14—C13—C16—O3	−83.9 (4)
C6—C9—C8—C7	180.000 (1)	C14—C13—C16—C16^iv	114.9 (3)
C4—C3—C5—C6	180.000 (1)	C14—C13—C17—C18	−176.0 (4)
C3—C2—C1—N1	0.000 (1)	C16—C13—C14—C15	−172.3 (4)
C1—N1—C007—C4	0.000 (1)	C16^iv—C13—C14—C15	−82.4 (5)
C1—C2—C3—C4	0.000 (1)	C16^iv—C13—C16—O4	−25.4 (7)
C1—C2—C3—C5	180.000 (1)	C16^iv—C13—C16—O3	161.2 (3)
C8—C9—C10—C11	0.000 (1)	C16—C13—C17—C18	136.0 (7)
C8—C9—C6—C5	0.000 (1)	C16^iv—C13—C17—C18	65.7 (5)
O2—C12—C13—C14	62.6 (4)	C17—C13—C14—C15	166.8 (4)
O2^iv—C12—C13—C14	−119.0 (3)	C17—C13—C16—O4	−140.3 (9)
O2^iv—C12—C13—C16	157.9 (4)	C17—C13—C16—O3	46.3 (5)
O2^iv—C12—C13—C16^iv	20.5 (6)	C17—C13—C16—C16^iv	−114.9 (5)

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

Catena(1,2-Bis(4-pyridine)ethylene-N)-tetraaqua-zinc(II) (mu-tetrakis(4-pyridyl) cyclobutane-N,N')-tetraaqua-zinc(II) tetrakis(hydrogen diethylmalonate) (8a)

Crystal data

C24H28N4O4Zn·2(C7H10O4)	F(000) = 1720
Mr = 818.17	Dx = 1.357 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 26.8028 (19) Å	Cell parameters from 3655 reflections
b = 6.8933 (5) Å	θ = 2.9–30.4°
c = 23.0690 (17) Å	µ = 0.68 mm^−1
β = 110.021 (1)°	T = 120 K
V = 4004.6 (5) Å^3	Prism, colourless
Z = 4	0.68 × 0.35 × 0.19 mm

Data collection

Bruker APEX-II CCD diffractometer	3847 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.050
Absorption correction: multi-scan SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0672 before and 0.0464 after correction. The Ratio of minimum to maximum transmission is 0.8717. The λ/2 correction factor is 0.00150.	θmax = 30.6°, θmin = 1.6°
Tmin = 0.294, Tmax = 0.337	h = −38→38
25740 measured reflections	k = −9→9
6154 independent reflections	l = −33→32

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.176	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.004
6154 reflections	Δρmax = 0.67 e Å^−3
314 parameters	Δρmin = −0.36 e Å^−3
4 restraints

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	0.5000	0.23830 (6)	0.7500	0.02879 (14)
O1	0.51742 (6)	0.4635 (2)	0.81741 (7)	0.0307 (4)
H1A	0.5371	0.5579	0.8152	0.046*
H2A	0.4722	0.0419	0.6454	0.046*
O2	0.48368 (6)	0.0135 (2)	0.68364 (7)	0.0297 (3)
H1B	0.5312	0.4281	0.8547	0.045*
H2B	0.4623	−0.0758	0.6849	0.045*
N1	0.90202 (9)	0.2388 (3)	0.69058 (11)	0.0379 (5)
N2	0.57948 (8)	0.2402 (3)	0.75156 (10)	0.0337 (5)
C3	0.68433 (10)	0.2406 (4)	0.75657 (15)	0.0483 (8)
C4	0.64288 (9)	0.2442 (3)	0.70038 (12)	0.0309 (5)
H4	0.6501	0.2473	0.6628	0.037*
C5	0.59137 (9)	0.2433 (3)	0.69966 (11)	0.0248 (4)
H5	0.5632	0.2449	0.6610	0.030*
C6	0.67224 (9)	0.2380 (3)	0.81005 (12)	0.0282 (5)
H6	0.6997	0.2360	0.8492	0.034*
C7	0.62015 (9)	0.2382 (4)	0.80567 (12)	0.0369 (6)
H7	0.6121	0.2368	0.8427	0.044*
C9	0.84809 (9)	0.2369 (4)	0.75403 (13)	0.0393 (6)
H9A	0.8441	0.1907	0.7910	0.047*	0.5
H9B	0.8444	0.2775	0.7917	0.047*	0.5
C10	0.89589 (9)	0.2362 (3)	0.74590 (11)	0.0286 (5)
H10	0.9269	0.2336	0.7816	0.034*
C12	0.85795 (10)	0.2422 (3)	0.64121 (12)	0.0337 (5)
H12	0.8596	0.2077	0.6020	0.040*	0.5
H12A	0.8605	0.2779	0.6026	0.040*	0.5
C1	0.7357 (6)	0.229 (2)	0.7377 (7)	0.028 (3)	0.15
H1	0.7650	0.1925	0.7713	0.034*	0.15
C2	0.7490 (5)	0.255 (2)	0.6882 (6)	0.021 (3)	0.15
H2	0.7255	0.2422	0.6479	0.025*	0.15
C8	0.80423 (17)	0.3102 (7)	0.7046 (2)	0.0291 (10)	0.5
C11	0.8102 (3)	0.2947 (9)	0.6462 (3)	0.0374 (16)	0.5
H11	0.7808	0.3210	0.6099	0.045*	0.5
C1A	0.73825 (16)	0.1287 (7)	0.7659 (2)	0.0180 (9)	0.425
C2A	0.75346 (17)	0.0784 (7)	0.7086 (2)	0.0205 (9)	0.425
C1B	0.74020 (17)	0.3549 (7)	0.7705 (2)	0.0184 (9)	0.425
C2B	0.75539 (17)	0.4041 (7)	0.7128 (2)	0.0196 (9)	0.425
C8A	0.80292 (17)	0.1723 (8)	0.7020 (2)	0.0314 (10)	0.5
C11A	0.8078 (2)	0.1950 (9)	0.6438 (3)	0.0343 (13)	0.5
H11A	0.7780	0.1790	0.6072	0.041*	0.5
O3	0.44581 (12)	0.0755 (4)	0.56611 (9)	0.0843 (9)
O4	0.42720 (10)	0.3866 (3)	0.56501 (9)	0.0619 (6)
O5	0.36894 (12)	0.5459 (3)	0.47242 (11)	0.0877 (10)
O6	0.33078 (8)	0.3856 (3)	0.38680 (9)	0.0548 (5)
C13	0.46833 (15)	0.2919 (5)	0.43629 (17)	0.0596 (9)
H13A	0.4897	0.2440	0.4123	0.089*
H13B	0.4914	0.3155	0.4789	0.089*
H13C	0.4508	0.4131	0.4181	0.089*
C14	0.42708 (13)	0.1430 (4)	0.43556 (12)	0.0489 (7)
H14A	0.4453	0.0212	0.4538	0.059*
H14B	0.4053	0.1154	0.3921	0.059*
C15	0.38980 (13)	0.2027 (4)	0.47064 (12)	0.0401 (6)
C16	0.34843 (16)	0.0433 (5)	0.46342 (16)	0.0711 (11)
H16A	0.3669	−0.0794	0.4804	0.085*
H16B	0.3287	0.0228	0.4190	0.085*
C17	0.30851 (17)	0.0915 (7)	0.49628 (19)	0.0997 (16)
H17A	0.2869	0.2034	0.4762	0.150*
H17B	0.3279	0.1222	0.5397	0.150*
H17C	0.2854	−0.0206	0.4938	0.150*
C18	0.42391 (14)	0.2234 (4)	0.53964 (13)	0.0447 (7)
C19	0.36029 (11)	0.3871 (4)	0.44027 (13)	0.0439 (6)
H1AA	0.7573 (11)	0.2369 (9)	0.7908 (11)	0.053*	0.85
H2BA	0.7254 (18)	0.390 (11)	0.6748 (17)	0.053*	0.425
H2AA	0.7257 (19)	0.094 (10)	0.6688 (15)	0.053*	0.425

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01270 (18)	0.0517 (3)	0.0239 (2)	0.000	0.00879 (13)	0.000
O1	0.0253 (8)	0.0408 (9)	0.0278 (8)	−0.0026 (7)	0.0114 (6)	0.0014 (7)
O2	0.0220 (7)	0.0403 (9)	0.0271 (8)	−0.0043 (6)	0.0088 (6)	0.0012 (7)
N1	0.0259 (10)	0.0548 (14)	0.0332 (11)	−0.0017 (9)	0.0104 (9)	−0.0027 (9)
N2	0.0145 (8)	0.0597 (14)	0.0278 (10)	−0.0028 (8)	0.0083 (7)	−0.0051 (9)
C3	0.0144 (10)	0.084 (2)	0.0488 (17)	0.0070 (12)	0.0134 (11)	0.0134 (14)
C4	0.0214 (10)	0.0374 (13)	0.0386 (13)	0.0048 (9)	0.0165 (9)	0.0037 (10)
C5	0.0185 (9)	0.0288 (11)	0.0287 (11)	−0.0024 (8)	0.0102 (8)	−0.0025 (8)
C6	0.0159 (9)	0.0273 (11)	0.0379 (12)	0.0006 (8)	0.0049 (9)	0.0026 (9)
C7	0.0183 (10)	0.0637 (17)	0.0283 (12)	−0.0018 (10)	0.0075 (9)	−0.0043 (11)
C9	0.0168 (10)	0.0690 (19)	0.0312 (13)	0.0015 (11)	0.0071 (9)	0.0080 (12)
C10	0.0194 (10)	0.0342 (12)	0.0298 (11)	−0.0007 (8)	0.0054 (8)	−0.0021 (9)
C12	0.0342 (13)	0.0366 (13)	0.0289 (12)	0.0009 (10)	0.0091 (10)	0.0014 (9)
C1	0.014 (6)	0.039 (9)	0.024 (7)	−0.010 (6)	−0.005 (5)	0.005 (7)
C2	0.011 (5)	0.032 (7)	0.019 (6)	−0.009 (5)	0.004 (4)	−0.002 (6)
C8	0.014 (2)	0.035 (2)	0.036 (3)	0.0003 (17)	0.0051 (18)	0.018 (2)
C11	0.029 (3)	0.042 (3)	0.031 (3)	−0.011 (3)	−0.003 (2)	0.012 (3)
C1A	0.0095 (19)	0.022 (2)	0.022 (2)	0.0003 (16)	0.0045 (17)	−0.002 (2)
C2A	0.010 (2)	0.025 (2)	0.025 (2)	0.0011 (17)	0.0041 (17)	−0.0012 (18)
C1B	0.011 (2)	0.022 (2)	0.021 (2)	0.0033 (16)	0.0054 (17)	0.0020 (18)
C2B	0.013 (2)	0.025 (2)	0.022 (2)	−0.0004 (17)	0.0075 (17)	0.0021 (19)
C8A	0.018 (2)	0.040 (3)	0.034 (3)	0.002 (2)	0.0071 (19)	−0.012 (2)
C11A	0.022 (3)	0.050 (4)	0.028 (3)	−0.004 (3)	0.005 (2)	−0.001 (3)
O3	0.142 (3)	0.0678 (16)	0.0306 (11)	0.0345 (16)	0.0127 (13)	0.0077 (11)
O4	0.0854 (17)	0.0611 (14)	0.0339 (11)	0.0042 (12)	0.0136 (11)	−0.0144 (10)
O5	0.135 (2)	0.0511 (14)	0.0605 (15)	0.0369 (15)	0.0120 (15)	−0.0186 (11)
O6	0.0552 (12)	0.0633 (14)	0.0436 (11)	0.0087 (10)	0.0139 (10)	0.0036 (10)
C13	0.067 (2)	0.071 (2)	0.054 (2)	0.0111 (17)	0.0373 (18)	0.0003 (16)
C14	0.075 (2)	0.0419 (15)	0.0282 (13)	0.0210 (14)	0.0155 (13)	−0.0027 (11)
C15	0.0587 (18)	0.0339 (13)	0.0278 (13)	−0.0009 (12)	0.0148 (12)	−0.0002 (10)
C16	0.097 (3)	0.063 (2)	0.053 (2)	−0.035 (2)	0.0253 (19)	−0.0045 (16)
C17	0.084 (3)	0.136 (4)	0.085 (3)	−0.047 (3)	0.037 (2)	0.009 (3)
C18	0.0581 (19)	0.0520 (17)	0.0263 (13)	0.0043 (13)	0.0172 (13)	−0.0007 (11)
C19	0.0454 (16)	0.0509 (16)	0.0384 (14)	0.0108 (13)	0.0182 (12)	−0.0007 (12)

Geometric parameters (Å, º)

Zn1—O1^i	2.1330 (17)	C1—C2	1.32 (2)
Zn1—O1	2.1330 (17)	C2—H2	0.9301
Zn1—O2	2.1160 (16)	C2—H2BA	1.11 (7)
Zn1—O2^i	2.1160 (16)	C2—H2AA	1.28 (7)
Zn1—N2	2.1183 (19)	C8—C11	1.416 (9)
Zn1—N2^i	2.1183 (19)	C8—C2B	1.528 (6)
O1—H1A	0.8493	C11—H11	0.9500
O1—H1B	0.8479	C1A—C2A	1.551 (7)
O2—H2A	0.8515	C1A—H1AA	0.972 (5)
O2—H2B	0.8495	C2A—C8A	1.529 (7)
N1—C10	1.341 (3)	C2A—H2AA	0.969 (5)
N1—C12	1.331 (3)	C1B—C2B	1.556 (6)
N2—C5	1.340 (3)	C2B—H2BA	0.970 (5)
N2—C7	1.347 (3)	C8A—C11A	1.401 (8)
C3—C4	1.389 (4)	C11A—H11A	0.9500
C3—C6	1.379 (4)	O3—C18	1.230 (4)
C3—C1	1.581 (17)	O4—C18	1.257 (3)
C3—C1A	1.586 (5)	O5—C19	1.298 (4)
C3—C1B	1.624 (5)	O6—C19	1.216 (3)
C4—H4	0.9500	C13—H13A	0.9800
C4—C5	1.375 (3)	C13—H13B	0.9800
C5—H5	0.9500	C13—H13C	0.9800
C6—H6	0.9500	C13—C14	1.504 (5)
C6—C7	1.365 (3)	C14—H14A	0.9900
C7—H7	0.9500	C14—H14B	0.9900
C9—H9A	0.9500	C14—C15	1.541 (4)
C9—H9B	0.9500	C15—C16	1.529 (4)
C9—C10	1.357 (3)	C15—C18	1.547 (4)
C9—C8	1.421 (5)	C15—C19	1.534 (4)
C9—C8A	1.452 (5)	C16—H16A	0.9900
C10—H10	0.9500	C16—H16B	0.9900
C12—H12	0.9500	C16—C17	1.545 (5)
C12—H12A	0.9500	C17—H17A	0.9800
C12—C11	1.372 (8)	C17—H17B	0.9800
C12—C11A	1.405 (7)	C17—H17C	0.9800
C1—H1	0.9302
O1—Zn1—O1^i	86.59 (9)	C1—C2—H2BA	93 (4)
O2—Zn1—O1^i	93.79 (6)	C1—C2—H2AA	87 (3)
O2^i—Zn1—O1^i	179.29 (5)	H2—C2—H2BA	71.1
O2—Zn1—O1	179.29 (5)	H2—C2—H2AA	59.0
O2^i—Zn1—O1	93.79 (6)	H2BA—C2—H2AA	118 (3)
O2—Zn1—O2^i	85.84 (9)	C9—C8—C2B	124.1 (4)
O2—Zn1—N2^i	91.99 (7)	C11—C8—C9	113.9 (4)
O2^i—Zn1—N2	91.99 (7)	C11—C8—C2B	122.0 (4)
O2^i—Zn1—N2^i	88.53 (7)	C12—C11—C8	120.8 (5)
O2—Zn1—N2	88.53 (7)	C12—C11—H11	119.6
N2^i—Zn1—O1^i	90.88 (7)	C8—C11—H11	119.6
N2^i—Zn1—O1	88.60 (7)	C3—C1A—H1AA	88.7 (18)
N2—Zn1—O1	90.88 (7)	C2A—C1A—C3	119.1 (4)
N2—Zn1—O1^i	88.60 (7)	C2A—C1A—H1AA	116 (3)
N2—Zn1—N2^i	179.29 (11)	C1A—C2A—H2AA	116 (4)
Zn1—O1—H1A	120.0	C8A—C2A—C1A	118.7 (4)
Zn1—O1—H1B	116.2	C8A—C2A—H2AA	106 (4)
H1A—O1—H1B	102.5	C2B—C1B—C3	115.5 (4)
Zn1—O2—H2A	119.5	C8—C2B—C1B	119.9 (4)
Zn1—O2—H2B	118.7	C8—C2B—H2BA	109 (4)
H2A—O2—H2B	101.2	C1B—C2B—H2BA	112 (4)
C12—N1—C10	116.9 (2)	C9—C8A—C2A	123.6 (4)
C5—N2—Zn1	122.02 (16)	C11A—C8A—C9	115.6 (4)
C5—N2—C7	117.6 (2)	C11A—C8A—C2A	120.7 (4)
C7—N2—Zn1	120.37 (16)	C12—C11A—H11A	120.9
C4—C3—C1	103.7 (6)	C8A—C11A—C12	118.1 (5)
C4—C3—C1A	122.4 (3)	C8A—C11A—H11A	120.9
C4—C3—C1B	124.4 (3)	H13A—C13—H13B	109.5
C6—C3—C4	118.5 (2)	H13A—C13—H13C	109.5
C6—C3—C1	137.7 (6)	H13B—C13—H13C	109.5
C6—C3—C1A	110.7 (3)	C14—C13—H13A	109.5
C6—C3—C1B	108.3 (3)	C14—C13—H13B	109.5
C3—C4—H4	120.3	C14—C13—H13C	109.5
C5—C4—C3	119.4 (2)	C13—C14—H14A	108.6
C5—C4—H4	120.3	C13—C14—H14B	108.6
N2—C5—C4	122.3 (2)	C13—C14—C15	114.7 (2)
N2—C5—H5	118.9	H14A—C14—H14B	107.6
C4—C5—H5	118.9	C15—C14—H14A	108.6
C3—C6—H6	120.6	C15—C14—H14B	108.6
C7—C6—C3	118.8 (2)	C14—C15—C18	107.7 (3)
C7—C6—H6	120.6	C16—C15—C14	109.1 (2)
N2—C7—C6	123.5 (2)	C16—C15—C18	109.2 (2)
N2—C7—H7	118.3	C16—C15—C19	107.7 (3)
C6—C7—H7	118.3	C19—C15—C14	107.9 (2)
C10—C9—H9A	121.6	C19—C15—C18	115.1 (2)
C10—C9—H9B	121.8	C15—C16—H16A	109.0
C10—C9—C8	116.9 (3)	C15—C16—H16B	109.0
C10—C9—C8A	116.4 (3)	C15—C16—C17	113.0 (3)
C8—C9—H9A	121.6	H16A—C16—H16B	107.8
C8A—C9—H9B	121.8	C17—C16—H16A	109.0
N1—C10—C9	124.1 (2)	C17—C16—H16B	109.0
N1—C10—H10	118.0	C16—C17—H17A	109.5
C9—C10—H10	118.0	C16—C17—H17B	109.5
N1—C12—H12	119.6	C16—C17—H17C	109.5
N1—C12—H12A	118.6	H17A—C17—H17B	109.5
N1—C12—C11	120.9 (4)	H17A—C17—H17C	109.5
N1—C12—C11A	122.8 (3)	H17B—C17—H17C	109.5
C11—C12—H12	119.6	O3—C18—O4	124.4 (3)
C11A—C12—H12A	118.6	O3—C18—C15	116.6 (2)
C3—C1—H1	110.4	O4—C18—C15	119.0 (3)
C2—C1—C3	138.6 (12)	O5—C19—C15	118.3 (3)
C2—C1—H1	111.0	O6—C19—O5	120.9 (3)
C1—C2—H2	124.0	O6—C19—C15	120.7 (3)
Zn1—N2—C5—C4	−179.89 (16)	C11—C8—C2B—C1B	158.1 (5)
Zn1—N2—C7—C6	179.56 (18)	C1A—C3—C4—C5	144.7 (3)
N1—C12—C11—C8	−12.3 (7)	C1A—C3—C6—C7	−148.8 (3)
N1—C12—C11A—C8A	9.9 (7)	C1A—C3—C1—C2	143 (3)
C3—C4—C5—N2	0.4 (3)	C1A—C3—C1B—C2B	86.7 (4)
C3—C6—C7—N2	0.2 (4)	C1A—C2A—C8A—C9	27.0 (7)
C3—C1A—C2A—C8A	115.3 (4)	C1A—C2A—C8A—C11A	−155.2 (5)
C3—C1B—C2B—C8	−114.7 (4)	C2A—C8A—C11A—C12	−166.4 (4)
C4—C3—C6—C7	0.3 (4)	C1B—C3—C4—C5	−144.0 (3)
C4—C3—C1—C2	15 (2)	C1B—C3—C6—C7	149.1 (3)
C4—C3—C1A—C2A	20.2 (5)	C1B—C3—C1—C2	−112 (2)
C4—C3—C1B—C2B	−23.2 (5)	C1B—C3—C1A—C2A	−93.0 (5)
C5—N2—C7—C6	−0.4 (4)	C2B—C8—C11—C12	168.3 (4)
C6—C3—C4—C5	−0.6 (4)	C8A—C9—C10—N1	21.2 (4)
C6—C3—C1—C2	−169.2 (14)	C8A—C9—C8—C11	−73.7 (6)
C6—C3—C1A—C2A	167.8 (3)	C8A—C9—C8—C2B	108.2 (6)
C6—C3—C1B—C2B	−169.7 (3)	C11A—C12—C11—C8	90.5 (10)
C7—N2—C5—C4	0.1 (3)	C13—C14—C15—C16	177.2 (3)
C9—C8—C11—C12	−9.8 (7)	C13—C14—C15—C18	−64.4 (3)
C9—C8—C2B—C1B	−24.0 (7)	C13—C14—C15—C19	60.4 (3)
C9—C8A—C11A—C12	11.6 (7)	C14—C15—C16—C17	−179.1 (3)
C10—N1—C12—C11	17.7 (4)	C14—C15—C18—O3	−63.4 (4)
C10—N1—C12—C11A	−16.3 (4)	C14—C15—C18—O4	117.2 (3)
C10—C9—C8—C11	25.7 (5)	C14—C15—C19—O5	−115.3 (3)
C10—C9—C8—C2B	−152.3 (4)	C14—C15—C19—O6	62.5 (4)
C10—C9—C8A—C2A	151.9 (4)	C16—C15—C18—O3	55.0 (4)
C10—C9—C8A—C11A	−26.0 (6)	C16—C15—C18—O4	−124.4 (3)
C12—N1—C10—C9	−0.1 (3)	C16—C15—C19—O5	127.0 (3)
C1—C3—C4—C5	176.4 (6)	C16—C15—C19—O6	−55.2 (4)
C1—C3—C6—C7	−175.4 (9)	C18—C15—C16—C17	63.4 (4)
C1—C3—C1A—C2A	−44.4 (10)	C18—C15—C19—O5	4.9 (4)
C1—C3—C1B—C2B	46.7 (10)	C18—C15—C19—O6	−177.3 (3)
C8—C9—C10—N1	−22.3 (4)	C19—C15—C16—C17	−62.2 (4)
C8—C9—C8A—C2A	−107.3 (6)	C19—C15—C18—O3	176.3 (3)
C8—C9—C8A—C11A	74.8 (6)	C19—C15—C18—O4	−3.1 (4)
C11—C12—C11A—C8A	−85.6 (10)

Symmetry code: (i) −x+1, y, −z+3/2.

(9)

Crystal data

C19H22N2O4Zn·0.38(H2O)	Dx = 1.368 Mg m^−3
Mr = 414.51	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, C2221	Cell parameters from 4172 reflections
a = 24.662 (3) Å	θ = 2.5–25.7°
b = 37.180 (5) Å	µ = 1.25 mm^−1
c = 8.7826 (12) Å	T = 120 K
V = 8053.0 (19) Å^3	Prism, colourless
Z = 16	0.53 × 0.15 × 0.14 mm
F(000) = 3452

Data collection

Bruker APEX-II CCD diffractometer	7821 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.103
Absorption correction: multi-scan SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1078 before and 0.0719 after correction. The Ratio of minimum to maximum transmission is 0.7779. The λ/2 correction factor is 0.00150.	θmax = 30.7°, θmin = 2.2°
Tmin = 0.262, Tmax = 0.337	h = −35→35
41027 measured reflections	k = −53→52
12430 independent reflections	l = −12→12

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.065	w = 1/[σ^2(Fo^2) + (0.048P)^2 + 17.P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.150	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 1.26 e Å^−3
12430 reflections	Δρmin = −1.12 e Å^−3
461 parameters	Absolute structure: Refined as an inversion twin.
14 restraints	Absolute structure parameter: 0.01 (2)

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. Refined as a 2-component inversion twin.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.43029 (4)	0.5000	1.5000	0.0198 (2)
Zn2	0.24034 (3)	0.29141 (2)	0.40389 (8)	0.02010 (17)
Zn3	0.0000	0.45663 (3)	−0.7500	0.0318 (3)
O1	0.40948 (19)	0.56008 (12)	1.3003 (5)	0.0246 (10)
O2	0.48008 (18)	0.53367 (12)	1.4095 (6)	0.0258 (10)
O3	0.0937 (3)	0.44142 (13)	−0.9269 (7)	0.0454 (15)
O4	0.0524 (2)	0.48994 (13)	−0.8352 (6)	0.0378 (14)
O5	0.1350 (2)	0.28996 (14)	0.5611 (6)	0.0389 (13)
O6	0.19739 (18)	0.25184 (12)	0.4812 (5)	0.0227 (10)
O7	0.1970 (2)	0.23265 (12)	0.8134 (5)	0.0247 (10)
O8	0.1823 (2)	0.17826 (12)	0.7204 (5)	0.0278 (11)
N1	0.3857 (2)	0.47416 (15)	1.3405 (6)	0.0211 (12)
N2	0.2641 (2)	0.32361 (14)	0.5766 (6)	0.0239 (12)
N3	0.1946 (2)	0.31490 (15)	0.2403 (6)	0.0240 (12)
N4	0.0349 (3)	0.42720 (16)	−0.5861 (7)	0.0318 (14)
C1	0.4018 (3)	0.47491 (19)	1.1948 (8)	0.0258 (15)
H1	0.4305	0.4863	1.1723	0.031*
C2	0.3735 (3)	0.45780 (18)	1.0795 (8)	0.0289 (16)
H2	0.3848	0.4589	0.9882	0.035*
C3	0.3270 (3)	0.43899 (18)	1.1132 (9)	0.0288 (16)
C4	0.3110 (3)	0.4375 (2)	1.2647 (9)	0.0323 (17)
H4	0.2827	0.4258	1.2899	0.039*
C5	0.3415 (3)	0.45506 (19)	1.3745 (7)	0.0274 (15)
H5	0.3317	0.4536	1.4671	0.033*
C6	0.2974 (3)	0.41908 (19)	0.9913 (9)	0.0348 (17)
H6A	0.2951	0.4322	0.9123	0.042*
H6B	0.2654	0.4143	1.0213	0.042*
C7	0.3263 (3)	0.38462 (18)	0.9523 (8)	0.0292 (16)
H7A	0.3592	0.3895	0.9324	0.035*
H7B	0.3261	0.3711	1.0304	0.035*
C8	0.2968 (3)	0.35223 (19)	0.5536 (8)	0.0287 (16)
H8	0.3058	0.3577	0.4631	0.034*
C9	0.3162 (3)	0.37281 (18)	0.6716 (8)	0.0267 (15)
H9	0.3362	0.3909	0.6530	0.032*
C10	0.3033 (3)	0.36415 (19)	0.8218 (8)	0.0259 (15)
C11	0.2695 (3)	0.33485 (18)	0.8438 (8)	0.0279 (16)
H11	0.2603	0.3288	0.9334	0.033*
C12	0.2508 (3)	0.31545 (17)	0.7197 (7)	0.0267 (15)
H12	0.2300	0.2976	0.7354	0.032*
C13	0.1888 (3)	0.3499 (2)	0.2248 (9)	0.0378 (19)
H13	0.2059	0.3637	0.2854	0.045*
C14	0.1565 (3)	0.3651 (2)	0.1156 (9)	0.039 (2)
H14	0.1540	0.3878	0.1103	0.047*
C15	0.1285 (5)	0.3444 (3)	0.0157 (12)	0.0634 (14)
C16	0.1373 (5)	0.3084 (3)	0.0294 (11)	0.0634 (14)
H16	0.1219	0.2941	−0.0322	0.076*
C17	0.1704 (4)	0.2949 (3)	0.1396 (10)	0.0634 (14)
H17	0.1754	0.2723	0.1429	0.076*
C18	0.0941 (4)	0.3604 (3)	−0.1073 (11)	0.0634 (14)
H18A	0.0713	0.3448	−0.1372	0.076*
H18B	0.0765	0.3781	−0.0711	0.076*
C19	0.1264 (4)	0.3727 (3)	−0.2388 (11)	0.0634 (14)
H19A	0.1419	0.3547	−0.2792	0.076*
H19B	0.1510	0.3869	−0.2074	0.076*
C20	0.0373 (3)	0.4399 (2)	−0.4429 (8)	0.0336 (18)
H20	0.0210	0.4594	−0.4222	0.040*
C21	0.0647 (3)	0.4228 (2)	−0.3297 (8)	0.040 (2)
H21	0.0642	0.4313	−0.2400	0.048*
C22	0.0931 (4)	0.3918 (2)	−0.3593 (9)	0.044 (2)
C23	0.0895 (4)	0.3784 (2)	−0.5069 (10)	0.053 (3)
H23	0.1054	0.3589	−0.5306	0.064*
C24	0.0605 (4)	0.3969 (2)	−0.6129 (9)	0.053 (3)
H24	0.0587	0.3882	−0.7023	0.063*
C25	0.4588 (3)	0.55774 (17)	1.3230 (7)	0.0217 (14)
C26	0.5000	0.5827 (2)	1.2500	0.024 (2)
C27	0.5252 (3)	0.60542 (19)	1.3765 (9)	0.0332 (17)
H27A	0.5415	0.5915	1.4381	0.040*
H27B	0.5487	0.6193	1.3372	0.040*
C28	0.4849 (3)	0.6281 (2)	1.4657 (10)	0.049 (2)
H28A	0.4695	0.6429	1.4060	0.074*
H28B	0.5015	0.6395	1.5353	0.074*
H28C	0.4611	0.6145	1.5057	0.074*
C29	0.0894 (3)	0.4739 (2)	−0.9141 (10)	0.0378 (18)
C30	0.1277 (5)	0.5000	−1.0000	0.047 (3)
C31	0.1669 (7)	0.5223 (4)	−0.921 (2)	0.038 (3)*	0.5
H31A	0.1511	0.5343	−0.8511	0.046*	0.5
H31B	0.1812	0.5371	−0.9826	0.046*	0.5
C32	0.2111 (8)	0.4983 (6)	−0.850 (3)	0.067 (4)*	0.5
H32A	0.2349	0.4935	−0.9170	0.100*	0.5
H32B	0.1969	0.4789	−0.8182	0.100*	0.5
H32C	0.2259	0.5093	−0.7760	0.100*	0.5
C33	0.1537 (3)	0.25975 (18)	0.5528 (8)	0.0236 (14)
C34	0.1274 (3)	0.22746 (19)	0.6306 (8)	0.0248 (15)
C35	0.1719 (2)	0.21020 (18)	0.7251 (7)	0.0208 (13)
C36	0.0819 (3)	0.2380 (2)	0.7366 (9)	0.042 (2)
H36A	0.0543	0.2436	0.6837	0.050*
H36B	0.0914	0.2566	0.7862	0.050*
C37	0.0658 (4)	0.2085 (3)	0.8494 (11)	0.072 (3)
H37A	0.0597	0.1891	0.8013	0.108*
H37B	0.0374	0.2148	0.8970	0.108*
H37C	0.0915	0.2052	0.9125	0.108*
C38	0.1078 (3)	0.20186 (18)	0.5053 (9)	0.0326 (16)
H38A	0.1354	0.1930	0.4614	0.039*
H38B	0.0907	0.1846	0.5472	0.039*
C39	0.0717 (3)	0.2182 (2)	0.3858 (9)	0.043 (2)
H39A	0.0609	0.2018	0.3252	0.064*
H39B	0.0893	0.2339	0.3362	0.064*
H39C	0.0444	0.2279	0.4282	0.064*
O1W	0.0190 (5)	0.3067 (3)	0.5654 (19)	0.069 (4)	0.5
H1WA	−0.0056	0.3056	0.6331	0.104*	0.5
H1WB	0.0061	0.3160	0.4846	0.104*	0.5
O2W	−0.0014 (15)	0.3165 (6)	0.300 (3)	0.069 (4)	0.25
H2W	−0.0224	0.3040	0.2444	0.104*	0.5
C31A	0.1567 (7)	0.5181 (4)	−0.8547 (18)	0.038 (3)*	0.5
H31C	0.1776	0.5347	−0.8867	0.046*	0.5
H31D	0.1324	0.5280	−0.8007	0.046*	0.5
C32A	0.1902 (8)	0.4931 (6)	−0.751 (3)	0.067 (4)*	0.5
H32D	0.1702	0.4887	−0.6563	0.100*	0.5
H32E	0.2250	0.5045	−0.7272	0.100*	0.5
H32F	0.1966	0.4702	−0.8032	0.100*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0225 (5)	0.0238 (5)	0.0129 (5)	0.000	0.000	−0.0020 (4)
Zn2	0.0252 (4)	0.0205 (3)	0.0146 (3)	−0.0010 (3)	−0.0019 (3)	0.0003 (3)
Zn3	0.0529 (8)	0.0266 (6)	0.0160 (5)	0.000	−0.0115 (5)	0.000
O1	0.024 (3)	0.026 (2)	0.024 (2)	−0.001 (2)	0.003 (2)	−0.002 (2)
O2	0.029 (3)	0.030 (2)	0.019 (2)	−0.001 (2)	−0.001 (2)	0.003 (2)
O3	0.061 (4)	0.025 (3)	0.050 (4)	0.011 (3)	−0.012 (3)	0.001 (3)
O4	0.056 (4)	0.030 (3)	0.028 (3)	0.003 (3)	−0.007 (3)	0.000 (2)
O5	0.041 (3)	0.022 (2)	0.053 (4)	0.006 (2)	−0.010 (2)	−0.001 (3)
O6	0.021 (2)	0.026 (2)	0.021 (2)	−0.0012 (19)	0.000 (2)	0.004 (2)
O7	0.029 (3)	0.027 (2)	0.018 (2)	0.001 (2)	0.000 (2)	−0.0015 (19)
O8	0.037 (3)	0.021 (2)	0.026 (3)	−0.001 (2)	0.001 (2)	−0.0010 (19)
N1	0.023 (3)	0.026 (3)	0.014 (3)	−0.002 (2)	0.001 (2)	−0.003 (2)
N2	0.031 (3)	0.025 (3)	0.016 (3)	−0.005 (3)	−0.002 (2)	0.000 (2)
N3	0.028 (3)	0.028 (3)	0.016 (3)	0.000 (2)	−0.004 (2)	0.001 (2)
N4	0.049 (4)	0.027 (3)	0.020 (3)	0.001 (3)	−0.008 (3)	−0.004 (3)
C1	0.032 (4)	0.027 (3)	0.018 (3)	−0.001 (3)	−0.001 (3)	−0.001 (3)
C2	0.048 (5)	0.026 (3)	0.012 (3)	−0.001 (3)	−0.002 (3)	−0.005 (3)
C3	0.032 (4)	0.025 (3)	0.029 (4)	0.005 (3)	−0.010 (3)	−0.008 (3)
C4	0.023 (4)	0.043 (4)	0.032 (4)	−0.009 (3)	−0.005 (3)	−0.006 (3)
C5	0.034 (4)	0.031 (4)	0.017 (3)	−0.002 (3)	0.003 (3)	0.000 (3)
C6	0.035 (4)	0.037 (4)	0.032 (4)	−0.002 (3)	−0.012 (4)	−0.009 (4)
C7	0.031 (4)	0.030 (4)	0.026 (3)	0.001 (3)	−0.005 (3)	−0.002 (3)
C8	0.038 (4)	0.032 (4)	0.017 (3)	−0.007 (3)	−0.001 (3)	0.003 (3)
C9	0.033 (4)	0.019 (3)	0.027 (4)	−0.010 (3)	−0.002 (3)	−0.004 (3)
C10	0.027 (4)	0.029 (4)	0.022 (3)	−0.005 (3)	−0.007 (3)	−0.003 (3)
C11	0.038 (4)	0.029 (4)	0.016 (3)	−0.004 (3)	−0.003 (3)	−0.002 (3)
C12	0.033 (4)	0.027 (3)	0.020 (3)	−0.006 (3)	−0.004 (3)	−0.004 (3)
C13	0.047 (5)	0.029 (4)	0.037 (4)	0.003 (4)	−0.022 (4)	−0.007 (3)
C14	0.049 (5)	0.031 (4)	0.037 (5)	0.014 (4)	−0.014 (4)	0.001 (3)
C15	0.093 (4)	0.049 (2)	0.048 (3)	0.001 (2)	−0.044 (3)	0.008 (2)
C16	0.093 (4)	0.049 (2)	0.048 (3)	0.001 (2)	−0.044 (3)	0.008 (2)
C17	0.093 (4)	0.049 (2)	0.048 (3)	0.001 (2)	−0.044 (3)	0.008 (2)
C18	0.093 (4)	0.049 (2)	0.048 (3)	0.001 (2)	−0.044 (3)	0.008 (2)
C19	0.093 (4)	0.049 (2)	0.048 (3)	0.001 (2)	−0.044 (3)	0.008 (2)
C20	0.043 (5)	0.041 (4)	0.017 (3)	0.011 (4)	−0.005 (3)	0.002 (3)
C21	0.050 (5)	0.051 (5)	0.017 (3)	0.022 (4)	−0.005 (3)	−0.003 (3)
C22	0.051 (5)	0.060 (6)	0.021 (4)	0.024 (5)	−0.003 (4)	0.006 (4)
C23	0.089 (8)	0.043 (5)	0.027 (4)	0.026 (5)	−0.008 (5)	−0.003 (4)
C24	0.097 (8)	0.046 (5)	0.016 (4)	0.015 (5)	−0.018 (4)	−0.005 (3)
C25	0.028 (4)	0.020 (3)	0.017 (3)	−0.001 (3)	0.002 (3)	−0.003 (3)
C26	0.030 (5)	0.020 (4)	0.023 (5)	0.000	0.000 (4)	0.000
C27	0.033 (4)	0.025 (3)	0.041 (5)	−0.003 (3)	0.003 (3)	−0.010 (3)
C28	0.045 (5)	0.051 (5)	0.050 (6)	0.004 (4)	−0.007 (4)	−0.026 (4)
C29	0.042 (5)	0.030 (4)	0.041 (5)	0.003 (3)	−0.017 (4)	−0.001 (4)
C30	0.031 (6)	0.028 (5)	0.084 (10)	0.000	0.000	−0.004 (7)
C33	0.024 (4)	0.026 (3)	0.021 (3)	−0.001 (3)	−0.003 (3)	0.000 (3)
C34	0.018 (3)	0.029 (3)	0.027 (4)	0.001 (3)	0.003 (3)	−0.001 (3)
C35	0.021 (3)	0.026 (3)	0.015 (3)	−0.006 (3)	0.005 (2)	0.001 (3)
C36	0.026 (4)	0.070 (6)	0.030 (4)	0.006 (4)	0.005 (3)	0.000 (4)
C37	0.049 (5)	0.098 (7)	0.069 (6)	0.011 (6)	0.028 (5)	0.027 (6)
C38	0.036 (4)	0.029 (4)	0.033 (4)	−0.005 (3)	−0.006 (4)	0.002 (3)
C39	0.037 (4)	0.056 (5)	0.035 (4)	−0.006 (4)	−0.010 (4)	−0.002 (4)
O1W	0.057 (6)	0.052 (5)	0.098 (7)	0.002 (5)	0.015 (5)	0.008 (5)
O2W	0.057 (6)	0.052 (5)	0.098 (7)	0.002 (5)	0.015 (5)	0.008 (5)

Geometric parameters (Å, º)

Zn1—O2^i	1.925 (5)	C18—H18B	0.8500
Zn1—O2	1.925 (5)	C18—C19	1.476 (14)
Zn1—N1^i	2.024 (5)	C19—H19A	0.8500
Zn1—N1	2.024 (5)	C19—H19B	0.8500
Zn2—O6	1.936 (4)	C19—C22	1.517 (11)
Zn2—O7^ii	1.955 (5)	C20—H20	0.8500
Zn2—N2	2.019 (5)	C20—C21	1.360 (10)
Zn2—N3	2.025 (6)	C21—H21	0.8500
Zn3—O4	1.941 (6)	C21—C22	1.371 (11)
Zn3—O4^iii	1.940 (6)	C22—C23	1.392 (11)
Zn3—N4^iii	2.003 (6)	C23—H23	0.8500
Zn3—N4	2.003 (6)	C23—C24	1.361 (11)
O1—C25	1.235 (8)	C24—H24	0.8500
O2—C25	1.286 (8)	C25—C26	1.517 (9)
O3—C29	1.219 (9)	C26—C25^v	1.517 (9)
O4—C29	1.290 (10)	C26—C27^v	1.528 (8)
O5—C33	1.216 (8)	C26—C27	1.528 (8)
O6—C33	1.282 (8)	C27—H27A	0.8500
O7—Zn2^iv	1.955 (5)	C27—H27B	0.8500
O7—C35	1.296 (8)	C27—C28	1.520 (10)
O8—C35	1.216 (8)	C28—H28A	0.8501
N1—C1	1.340 (8)	C28—H28B	0.8501
N1—C5	1.333 (9)	C28—H28C	0.8501
N2—C8	1.351 (9)	C29—C30	1.550 (11)
N2—C12	1.334 (8)	C30—C29^vi	1.550 (11)
N3—C13	1.316 (9)	C30—C31	1.452 (18)
N3—C17	1.301 (10)	C30—C31^vi	1.452 (18)
N4—C20	1.345 (9)	C30—C31A	1.610 (15)
N4—C24	1.312 (10)	C30—C31A^vi	1.610 (15)
C1—H1	0.8500	C31—H31A	0.8500
C1—C2	1.384 (9)	C31—H31B	0.8500
C2—H2	0.8500	C31—C32	1.54 (3)
C2—C3	1.375 (10)	C32—H32A	0.8501
C3—C4	1.389 (11)	C32—H32B	0.8501
C3—C6	1.493 (10)	C32—H32C	0.8501
C4—H4	0.8500	C33—C34	1.526 (10)
C4—C5	1.388 (10)	C34—C35	1.519 (9)
C5—H5	0.8500	C34—C36	1.510 (10)
C6—H6A	0.8500	C34—C38	1.533 (10)
C6—H6B	0.8500	C36—H36A	0.8500
C6—C7	1.506 (10)	C36—H36B	0.8500
C7—H7A	0.8500	C36—C37	1.532 (12)
C7—H7B	0.8500	C37—H37A	0.8501
C7—C10	1.489 (9)	C37—H37B	0.8501
C8—H8	0.8500	C37—H37C	0.8501
C8—C9	1.374 (9)	C38—H38A	0.8500
C9—H9	0.8500	C38—H38B	0.8500
C9—C10	1.395 (10)	C38—C39	1.504 (10)
C10—C11	1.385 (9)	C39—H39A	0.8501
C11—H11	0.8500	C39—H39B	0.8501
C11—C12	1.386 (9)	C39—H39C	0.8501
C12—H12	0.8500	O1W—H1WA	0.8505
C13—H13	0.8500	O1W—H1WB	0.8502
C13—C14	1.368 (10)	O2W—O2W^vii	0.88 (6)
C14—H14	0.8500	O2W—H2W	0.8502
C14—C15	1.356 (12)	C31A—H31C	0.8500
C15—C16	1.361 (13)	C31A—H31D	0.8500
C15—C18	1.496 (11)	C31A—C32A	1.542 (19)
C16—H16	0.8500	C32A—H32D	0.9800
C16—C17	1.362 (11)	C32A—H32E	0.9800
C17—H17	0.8500	C32A—H32F	0.9800
C18—H18A	0.8500
O2^i—Zn1—O2	100.7 (3)	C22—C21—H21	119.7
O2—Zn1—N1^i	108.9 (2)	C21—C22—C19	122.5 (8)
O2^i—Zn1—N1	108.9 (2)	C21—C22—C23	116.5 (7)
O2—Zn1—N1	111.7 (2)	C23—C22—C19	121.0 (8)
O2^i—Zn1—N1^i	111.7 (2)	C22—C23—H23	120.4
N1—Zn1—N1^i	114.1 (3)	C24—C23—C22	119.3 (8)
O6—Zn2—O7^ii	103.15 (19)	C24—C23—H23	120.4
O6—Zn2—N2	110.2 (2)	N4—C24—C23	124.3 (8)
O6—Zn2—N3	105.8 (2)	N4—C24—H24	117.8
O7^ii—Zn2—N2	110.3 (2)	C23—C24—H24	117.8
O7^ii—Zn2—N3	110.5 (2)	O1—C25—O2	123.1 (6)
N2—Zn2—N3	116.0 (2)	O1—C25—C26	123.2 (6)
O4^iii—Zn3—O4	100.7 (3)	O2—C25—C26	113.6 (6)
O4^iii—Zn3—N4^iii	109.9 (2)	C25—C26—C25^v	104.7 (7)
O4—Zn3—N4^iii	111.0 (2)	C25—C26—C27	107.6 (4)
O4—Zn3—N4	109.9 (2)	C25—C26—C27^v	111.9 (4)
O4^iii—Zn3—N4	111.0 (2)	C25^v—C26—C27	111.9 (4)
N4—Zn3—N4^iii	113.7 (3)	C25^v—C26—C27^v	107.6 (4)
C25—O2—Zn1	115.9 (4)	C27—C26—C27^v	112.7 (8)
C29—O4—Zn3	112.5 (5)	C26—C27—H27A	108.6
C33—O6—Zn2	117.2 (4)	C26—C27—H27B	108.6
C35—O7—Zn2^iv	109.0 (4)	H27A—C27—H27B	107.6
C1—N1—Zn1	119.3 (5)	C28—C27—C26	114.6 (6)
C5—N1—Zn1	122.8 (4)	C28—C27—H27A	108.6
C5—N1—C1	117.9 (6)	C28—C27—H27B	108.6
C8—N2—Zn2	121.9 (4)	C27—C28—H28A	109.5
C12—N2—Zn2	120.1 (4)	C27—C28—H28B	109.5
C12—N2—C8	117.8 (6)	C27—C28—H28C	109.5
C13—N3—Zn2	124.1 (5)	H28A—C28—H28B	109.5
C17—N3—Zn2	119.4 (5)	H28A—C28—H28C	109.5
C17—N3—C13	116.4 (7)	H28B—C28—H28C	109.5
C20—N4—Zn3	119.9 (5)	O3—C29—O4	124.7 (8)
C24—N4—Zn3	123.1 (5)	O3—C29—C30	121.4 (8)
C24—N4—C20	116.6 (7)	O4—C29—C30	113.8 (6)
N1—C1—H1	118.7	C29—C30—C29^vi	104.8 (9)
N1—C1—C2	122.6 (7)	C29—C30—C31A	98.4 (7)
C2—C1—H1	118.7	C29^vi—C30—C31A^vi	98.4 (7)
C1—C2—H2	120.1	C29^vi—C30—C31A	113.3 (7)
C3—C2—C1	119.8 (7)	C29—C30—C31A^vi	113.3 (7)
C3—C2—H2	120.1	C31—C30—C29^vi	106.4 (7)
C2—C3—C4	117.7 (6)	C31^vi—C30—C29^vi	122.0 (8)
C2—C3—C6	120.4 (7)	C31—C30—C29	122.0 (8)
C4—C3—C6	121.8 (7)	C31^vi—C30—C29	106.4 (7)
C3—C4—H4	120.3	C31^vi—C30—C31	96.6 (16)
C5—C4—C3	119.5 (7)	C31A^vi—C30—C31A	127.3 (15)
C5—C4—H4	120.3	C30—C31—H31A	109.8
N1—C5—C4	122.6 (6)	C30—C31—H31B	109.8
N1—C5—H5	118.7	C30—C31—C32	109.4 (14)
C4—C5—H5	118.7	H31A—C31—H31B	108.2
C3—C6—H6A	109.5	C32—C31—H31A	109.8
C3—C6—H6B	109.5	C32—C31—H31B	109.8
C3—C6—C7	110.7 (6)	C31—C32—H32A	109.5
H6A—C6—H6B	108.1	C31—C32—H32B	109.5
C7—C6—H6A	109.5	C31—C32—H32C	109.5
C7—C6—H6B	109.5	H32A—C32—H32B	109.5
C6—C7—H7A	108.4	H32A—C32—H32C	109.5
C6—C7—H7B	108.4	H32B—C32—H32C	109.5
H7A—C7—H7B	107.5	O5—C33—O6	124.0 (7)
C10—C7—C6	115.4 (6)	O5—C33—C34	122.6 (6)
C10—C7—H7A	108.4	O6—C33—C34	113.4 (6)
C10—C7—H7B	108.4	C33—C34—C38	107.5 (6)
N2—C8—H8	118.9	C35—C34—C33	105.6 (5)
N2—C8—C9	122.3 (6)	C35—C34—C38	111.0 (6)
C9—C8—H8	118.9	C36—C34—C33	112.8 (6)
C8—C9—H9	119.8	C36—C34—C35	108.1 (6)
C8—C9—C10	120.3 (6)	C36—C34—C38	111.7 (6)
C10—C9—H9	119.8	O7—C35—C34	113.6 (6)
C9—C10—C7	121.5 (6)	O8—C35—O7	123.3 (6)
C11—C10—C7	121.6 (6)	O8—C35—C34	123.1 (6)
C11—C10—C9	116.8 (6)	C34—C36—H36A	108.8
C10—C11—H11	120.0	C34—C36—H36B	108.8
C12—C11—C10	120.0 (6)	C34—C36—C37	113.8 (7)
C12—C11—H11	120.0	H36A—C36—H36B	107.7
N2—C12—C11	122.7 (6)	C37—C36—H36A	108.8
N2—C12—H12	118.6	C37—C36—H36B	108.8
C11—C12—H12	118.6	C36—C37—H37A	109.5
N3—C13—H13	118.5	C36—C37—H37B	109.5
N3—C13—C14	122.9 (7)	C36—C37—H37C	109.5
C14—C13—H13	118.5	H37A—C37—H37B	109.5
C13—C14—H14	119.5	H37A—C37—H37C	109.5
C15—C14—C13	121.1 (8)	H37B—C37—H37C	109.5
C15—C14—H14	119.5	C34—C38—H38A	108.3
C14—C15—C16	114.7 (8)	C34—C38—H38B	108.3
C14—C15—C18	122.0 (8)	H38A—C38—H38B	107.4
C16—C15—C18	123.1 (9)	C39—C38—C34	115.9 (6)
C15—C16—H16	119.3	C39—C38—H38A	108.3
C17—C16—C15	121.5 (9)	C39—C38—H38B	108.3
C17—C16—H16	119.3	C38—C39—H39A	109.5
N3—C17—C16	123.2 (9)	C38—C39—H39B	109.5
N3—C17—H17	118.4	C38—C39—H39C	109.5
C16—C17—H17	118.4	H39A—C39—H39B	109.5
C15—C18—H18A	109.1	H39A—C39—H39C	109.5
C15—C18—H18B	109.1	H39B—C39—H39C	109.5
H18A—C18—H18B	107.8	H1WA—O1W—H1WB	109.7
C19—C18—C15	112.5 (9)	O2W^vii—O2W—H2W	58.5
C19—C18—H18A	109.1	C30—C31A—H31C	108.1
C19—C18—H18B	109.1	C30—C31A—H31D	108.1
C18—C19—H19A	108.9	H31C—C31A—H31D	107.3
C18—C19—H19B	108.9	C32A—C31A—C30	117.0 (13)
C18—C19—C22	113.5 (9)	C32A—C31A—H31C	108.1
H19A—C19—H19B	107.7	C32A—C31A—H31D	108.1
C22—C19—H19A	108.9	C31A—C32A—H32D	109.5
C22—C19—H19B	108.9	C31A—C32A—H32E	109.5
N4—C20—H20	118.6	C31A—C32A—H32F	109.5
N4—C20—C21	122.7 (7)	H32D—C32A—H32E	109.5
C21—C20—H20	118.6	H32D—C32A—H32F	109.5
C20—C21—H21	119.7	H32E—C32A—H32F	109.5
C20—C21—C22	120.5 (7)
Zn1—O2—C25—O1	1.5 (8)	C6—C7—C10—C11	−99.6 (9)
Zn1—O2—C25—C26	−177.8 (4)	C7—C10—C11—C12	−177.1 (7)
Zn1—N1—C1—C2	179.8 (5)	C8—N2—C12—C11	−0.6 (10)
Zn1—N1—C5—C4	179.8 (5)	C8—C9—C10—C7	176.3 (7)
Zn2—O6—C33—O5	7.9 (9)	C8—C9—C10—C11	−1.5 (11)
Zn2—O6—C33—C34	−170.9 (4)	C9—C10—C11—C12	0.7 (11)
Zn2^iv—O7—C35—O8	9.9 (7)	C10—C11—C12—N2	0.3 (11)
Zn2^iv—O7—C35—C34	−171.5 (4)	C12—N2—C8—C9	−0.2 (11)
Zn2—N2—C8—C9	−175.4 (6)	C13—N3—C17—C16	−4.6 (15)
Zn2—N2—C12—C11	174.7 (6)	C13—C14—C15—C16	−2.9 (16)
Zn2—N3—C13—C14	−178.3 (6)	C13—C14—C15—C18	−178.4 (10)
Zn2—N3—C17—C16	177.5 (9)	C14—C15—C16—C17	2.4 (18)
Zn3—O4—C29—O3	−4.6 (10)	C14—C15—C18—C19	79.1 (13)
Zn3—O4—C29—C30	172.9 (5)	C15—C16—C17—N3	1.5 (19)
Zn3—N4—C20—C21	−173.9 (7)	C15—C18—C19—C22	−175.2 (8)
Zn3—N4—C24—C23	172.5 (8)	C16—C15—C18—C19	−95.9 (14)
O1—C25—C26—C25^v	−127.7 (7)	C17—N3—C13—C14	4.0 (13)
O1—C25—C26—C27^v	−11.4 (9)	C18—C15—C16—C17	177.7 (11)
O1—C25—C26—C27	113.0 (7)	C18—C19—C22—C21	60.7 (13)
O2—C25—C26—C25^v	51.6 (4)	C18—C19—C22—C23	−118.8 (11)
O2—C25—C26—C27^v	167.9 (6)	C19—C22—C23—C24	−178.2 (10)
O2—C25—C26—C27	−67.7 (7)	C20—N4—C24—C23	−1.5 (15)
O3—C29—C30—C29^vi	126.9 (9)	C20—C21—C22—C19	177.0 (9)
O3—C29—C30—C31	−112.5 (11)	C20—C21—C22—C23	−3.4 (14)
O3—C29—C30—C31^vi	−3.5 (12)	C21—C22—C23—C24	2.3 (15)
O3—C29—C30—C31A^vi	20.7 (13)	C22—C23—C24—N4	0.1 (17)
O3—C29—C30—C31A	−116.2 (10)	C24—N4—C20—C21	0.3 (13)
O4—C29—C30—C29^vi	−50.6 (5)	C25^v—C26—C27—C28	−173.8 (6)
O4—C29—C30—C31	70.0 (12)	C25—C26—C27—C28	−59.2 (8)
O4—C29—C30—C31^vi	179.0 (9)	C27^v—C26—C27—C28	64.7 (6)
O4—C29—C30—C31A^vi	−156.8 (9)	C29—C30—C31—C32	67.8 (17)
O4—C29—C30—C31A	66.3 (10)	C29^vi—C30—C31—C32	−172.4 (12)
O5—C33—C34—C35	−126.8 (7)	C29^vi—C30—C31A—C32A	172.8 (13)
O5—C33—C34—C36	−9.0 (10)	C29—C30—C31A—C32A	62.6 (16)
O5—C33—C34—C38	114.6 (7)	C31^vi—C30—C31—C32	−46.3 (11)
O6—C33—C34—C35	52.1 (7)	C31—C30—C31A—C32A	−110 (3)
O6—C33—C34—C36	169.9 (6)	C31^vi—C30—C31A—C32A	−48.0 (17)
O6—C33—C34—C38	−66.5 (7)	C33—C34—C35—O7	51.5 (7)
N1—C1—C2—C3	−0.3 (11)	C33—C34—C35—O8	−129.8 (6)
N2—C8—C9—C10	1.3 (11)	C33—C34—C36—C37	−163.2 (7)
N3—C13—C14—C15	−0.2 (15)	C33—C34—C38—C39	−53.5 (8)
N4—C20—C21—C22	2.2 (14)	C35—C34—C36—C37	−46.8 (9)
C1—N1—C5—C4	−2.7 (10)	C35—C34—C38—C39	−168.6 (6)
C1—C2—C3—C4	−1.3 (10)	C36—C34—C35—O7	−69.4 (7)
C1—C2—C3—C6	−177.3 (6)	C36—C34—C35—O8	109.3 (7)
C2—C3—C4—C5	0.8 (11)	C36—C34—C38—C39	70.7 (9)
C2—C3—C6—C7	76.4 (9)	C38—C34—C35—O7	167.8 (5)
C3—C4—C5—N1	1.2 (11)	C38—C34—C35—O8	−13.5 (9)
C3—C6—C7—C10	−174.5 (7)	C38—C34—C36—C37	75.6 (9)
C4—C3—C6—C7	−99.5 (8)	C31A—C30—C31—C32	77 (3)
C5—N1—C1—C2	2.3 (10)	C31A^vi—C30—C31—C32	−67.2 (15)
C6—C3—C4—C5	176.8 (7)	C31A^vi—C30—C31A—C32A	−65.3 (14)
C6—C7—C10—C9	82.8 (9)

Symmetry codes: (i) x, −y+1, −z+3; (ii) −x+1/2, −y+1/2, z−1/2; (iii) −x, y, −z−3/2; (iv) −x+1/2, −y+1/2, z+1/2; (v) −x+1, y, −z+5/2; (vi) x, −y+1, −z−2; (vii) −x, y, −z+1/2.