Assembly of Zn^II and Cd^II coordination polymers based on a flexible multi­carboxyl­ate ligand and nitrogen-containing auxiliary ligands through a mixed-ligand synthetic strategy: syntheses, structures and fluorescence properties

The structures of coordination polymers are strongly influenced by the organic ligands and metal ions used for their construction, so it is important to choose suitable ligands and metal ions and appropriate synthetic processes. Two novel d¹⁰ coordination polymers, namely poly[[diaquabis(2,2′-bi­pyridine)[μ₄-4,4′-(1,4-phenylenedioxy)bis(benzene-1,2-dicarboxyl­ato)]dizinc(II)] di­hydrate], {[Zn₂(C₂₂H₁₀O₁₀)(C₁₀H₈N₂)₂(H₂O)₂]·2H₂O}_n, (1), and poly[[diaquabis(1,10-phen­an­throline)[μ₄-4,4′-(1,4-phenylenedioxy)bis(benzene-1,2-dicarboxyl­ato)]dicad­mium(II)] di­methyl­formamide disolvate], {[Cd₂(C₂₂H₁₀O₁₀)(C₁₂H₈N₂)₂(H₂O)₂]·2C₃H₇NO}_n, (2), have been synthesized from 4,4′-(1,4-phenylenedioxy)bis(benzene-1,2-dicarboxylic acid) (H₄L) and two different N-containing auxiliary ligands through a mixed-ligand synthetic strategy under a solvothermal environment. The structures were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis and IR spectroscopy. Compounds (1) and (2) both present one-dimensional chain structures and two-dimensional supra­molecular layer structures constructed by weak hydrogen bonds. It is inter­esting to note that the carboxyl­ate ligands reveal stable trans configurations in both compounds. The fluorescence properties of (1) and (2) in the solid state were also investigated.

S1. Introduction

In the past 12 years, numerous coordination polymers (CPs) have been designed and constructed due to their novel structures and elegant topologies, as well as their potential applications in gas storage and separation (Li et al., 2012; Noro et al., 2013; Peng et al., 2014), catalysis (Cui et al., 2003; Chen et al., 2012), chemical sensors (Hu et al., 2014; Chen et al., 2009, 2013), magnetism (Wriedt et al., 2013; Liu et al., 2014) and luminescent materials (Cui et al., 2012; Qi et al., 2013). By surveying the various structures of CPs, one can clearly see that they are strongly influenced by the organic ligands and metal ions used, so it is important to choose suitable ligands and metal ions and appropriate synthetic processes to construct CPs. Inspired by the above-mentioned previous works, we selected benzene-1,4-bis­(4-oxy-1,2-benzene­dicarb­oxy­lic acid) (H₄L) as the main ligand, two N-containing auxiliary ligands (2,2'-bi­pyridine and 1,10-phenanthroline) and Zn^II and Cd^II salts to construct CPs. The flexible -O- groups and multi­carboxyl groups allow H₄L to adjust itself to varying geometric requirements and chelate more metal ions, which may produce more inter­esting structures beyond what are currently known (Cui et al., 2010; Han et al., 2013). Due to the good aromatic conjugation properties of the chosen ligands and the high complexation properties of d¹⁰ metal ions, such d¹⁰ metal-based complexes always have good fluorescence properties and can be good candidates for optical materials (Tian et al., 2014; Hu et al., 2015). Based on this consideration, we synthesized the two title CPs, {[Zn₂(C₂₂H₁₀O₁₀)(C₁₀H₈N₂)₂(H₂O)₂].2H₂O}_n, (1), and {[Cd₂(C₂₂H₁₀O₁₀)(C₁₂H₈N₂)₂(H₂O)₂].2C₃H₇NO}_n, (2). Herein, we report the syntheses, crystal structures and fluorescence properties of (1) and (2).

S2. Experimental

Benzene-1,4-bis­(4-oxy-1,2-benzene­dicarb­oxy­lic acid) was synthesized according to the previously reported procedure (Cao et al., 2012). All other reagents and solvents used in the experiment were purchased commercially and used without further purification. Elemental analyses were carried out on a Perkin–Elmer 240 elemental analyser. Powder X-ray diffraction measurements were performed with a Bruker D8 Advance instrument. Simulated PXRD spectra were generated using the Mercury program (Macrae et al., 2008). IR spectra were recorded on a Nicolet 330 FT–IR spectrometer with KBr pellets in the range 4000–400 cm^-1. Thermogravimetric analyses (TGA) were performed on a Perkin–Elmer TGA 7 analyser with a heating rate of 10 K min^-1 under a nitro­gen stream. Fluorescence spectra were measured on an Hitachi F-7000 fluorescence spectrophotometer.

S2.1. Synthesis and crystallization

S2.1.1. Preparation of (1)

Preparation of {[Zn₂(C₂₂H₁₀O₁₀)(C₁₀H₈N₂)₂(H₂O)₂].2H₂O}_n, (1) H₄L (21.9 mg, 0.05 mmol), ZnCl₂ (13.6 mg, 0.10 mmol) and 2,2'-bi­pyridine (15.6 mg, 0.10 mmol) were dissolved in DMF–H₂O (1:1 v/v, 8 ml; DMF is di­methyl­formamide). The mixture was placed in a tightly capped 20 ml glass vial under ultrasonic irradiation for 10 min, and then heated at 353 K for 3 d and then slowly cooled to room temperature at a rate of 10 K h^-1. Colourless crystals of (1) were collected in 40% yield (based on Zn). Elemental analysis (%) for C₂₁H₁₇N₂O₇Zn (M_r = 474.74), calculated/found (%): C 53.13/53.15, H 3.61/3.63, N 5.90/5.87. IR (KBr, ν, cm^-1): 3490 (m), 1588 (s), 1491 (m), 1395 (m), 1258 (m), 1227 (s), 1178 (m), 1025 (w), 769 (m), 657 (w).

S2.1.2. Preparation of (2)

Preparation of {[Cd₂(C₂₂H₁₀O₁₀)(C₁₂H₈N₂)₂(H₂O)₂].2C₃H₇NO}_n, (2) H₄L (21.9 mg, 0.05 mmol), CdCl₂.2.5H₂O (22.8 mg, 0.10 mmol) and 1,10-phenanthroline (18.0 mg, 0.10 mmol) were dissolved in DMF–C₂H₅OH–H₂O (5:2:1 v/v/v, 8 ml). The mixture was placed in a tightly capped 20 ml glass vial under ultrasonic irradiation for 10 min, and then heated at 353 K for 3 d and then slowly cooled to room temperature at a rate of 10 K h^-1. Colourless crystals of (2) were collected in 36% yield (based on Cd). Elemental analysis (%) for C₂₆H₂₂N₃O₇Cd (M_r = 600.87), calculated/found (%): C 51.97/52.02, H 3.69/3.67, N 6.99//6.95. IR (KBr, ν, cm^-1): 3417 (m), 1667 (s), 1588 (s), 1556 (s), 1402 (s), 1218 (s), 1098 (w), 945 (w), 850 (m), 737 (m).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, and with C—H = 0.96 Å and U_iso(H) = 1.2U_eq(C) for the methyl H atoms of DMF.

S3. Results and discussion

S3.1. Description of the structures

Single-crystal X-ray diffraction reveals that complexes (1) and (2) crystallize in the same crystal system (triclinic) and space group (P\<img height=12 src="/home/sf/Desktop/publcif/symbols/bar1.png">). The asymmetric unit of (1) contains one Zn^II cation, one half of a fully deprotonated H₄L ligand, one 2,2'-di­pyridyl ligand, one coordinated water molecule and one free water molecule. The coordination environment of the Zn^II cation is shown in Fig. 1. The Zn^II cation is penta­coordinated by two carboxyl­ate O atoms originating from two different L^4- ligands [Zn1—O3(-x, -y, -z) = 1.962 (2) Å, Zn1—O4 = 1.956 (2) Å], two N atoms from the 2,2'-di­pyridyl ligand [Zn1—N1 = 2.135 (3) Åand Zn1—N2 = 2.088 (2) Å] and one O atom from the coordinated water molecule [Zn1—O6 = 2.139 (2) Å]. The coordination geometry of Zn^II can be treated as a distorted quadrangular pyramid [Square pyramid?]. A binuclear building block is obtained through the connection of two crystallographically equivalent Zn^II cations and four carboxyl­ate groups. These units are linked to each other and generate an infinite one-dimensional zig-zag chain (Fig. 2). These one-dimensional chains are parallel to each other and further connected by inter­molecular hydrogen bonds [O7—H7A···O2(1 + x, y, z) and O7—H7B···O5; details in Table 2] to form a two-dimensional supra­molecular layer structure (Fig. 3).

The asymmetric unit of (2) contains one half of a fully deprotonated H₄L ligand, one 1,10-phenanthroline ligand, one coordinated water molecule and one free DMF molecule. As shown in Fig. 4, the central Cd^II cation is heptacoordinated by four carboxyl­ate O atoms originating from two different L^4- ligands [Cd1—O2 = 2.318 (2) Å, Cd1—O3 = 2.475 (3) Å, Cd1—O4(1 - x, -y, 1 - z) = 2.443 (2) Å and Cd1—O5(1 - x, -y, 1 - z) = 2.429 (2) Å], two N atoms from the 1,10-phenanthroline ligand [Cd1—N1 = 2.355 (3) Å and Cd1—N2 = 2.399 (3) Å] and one O atom from the coordinated water molecule [Cd1—O1 = 2.329 (2) Å]. The coordination geometry of the Cd^II cation can be treated as a distorted penta­gonal bipyramid. The construction of one-dimensional chains (Fig. 5) and two-dimensional supra­molecular layers (Fig. 6) are similar to the modes observed in (1). The inter­molecular hydrogen bonds are shown in Table 3. Besides the hydrogen-bonding inter­actions, there are several aromatic π-stacking inter­actions. Face-to-face π–π stacking is observed between 1,10-phenanthroline frames and is characterized by a centroid-to-centroid distance of ~3.4601 (3)–3.6307 (3)Å as calculated by the software PLATON (Spek, 2009).

S3.2. Fluorescence properties

The fluorescence properties of (1) and (2) were investigated in the solid state at 298 K. As depicted in Fig. 7, (1) and (2) exhibit fluorescence emission at ca 428 and 417 nm (excited at 330 nm), respectively. In order to understand the nature of the emission peaks, the fluorescence properties of the free ligand were measured. The results reveal that the ligand H₄L shows emission at 425 nm (excited at 330 nm), which can be attributed to intra­ligand π \rarr π* or n \rarr π* electronic transitions. As we know, d¹⁰ metal ions are difficult to oxidize or reduce due to their electronic configuration, so they neither offer electrons to the ligand, nor accept electrons from the ligand. Thus, the emission of the two compounds can be attributed to intra­ligand and/or ligand-to-ligand transition (LLCT), rather than ligand-to-metal (LMCT) or metal-to-ligand (MLCT) (Wen et al., 2007; Zhang et al., 2010). The small blue shift of the emission peak of (2) may be ascribed to the increase in conjugation upon metal coordination (Ma et al., 2013; Huang et al., 2013).

S3.3. Powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA)

The purities of the synthesized crystals were proved by their PXRD patterns. In Fig. 8, the as-synthesized PXRD patterns of both (1) and (2) agree well with the simulated patterns. The different intensities may be due to the preferred orientations of the powder samples.

The stabilities of (1) and (2) were measured by TGA and the experimental results are in agreement with the calculated data. As shown in Fig. 9, for (1) the first weight loss of 3.84% (calculated 3.79%) at 323 to 403 K corresponds to the loss of the free water molecule and the second loss of 3.74% (calculated 3.79%) at 403 to 543 K corresponds to the loss of the coordinated water molecule, and then the organic ligands are gradually decomposed. For (2), the first weight loss of 15.09% (calculated 15.15%) at 323 to 543 K corresponds to the loss of the DMF and coordinated water molecules, then the organic ligands are gradually decomposed.

S3.4. Conclusions

In conclusion, two new Zn^II- and Cd^II-based coordination polymers were constructed with the flexible benzene-1,4-bis­(4-oxy-1,2-benzene­dicarb­oxy­lic acid) (H₄L) ligand and two different N-containing auxiliary ligands through a mixed-ligand synthetic strategy under the solvothermal method. It is important to note that the carboxyl­ate ligands are divided into two parts by a centre of inversion. These two complexes present different two-dimensional layer structures, and their fluorescence properties indicate that (1) and (2) may be good candidates for optical materials. Furthermore, hydrogen-bonding inter­actions play an important role in the construction of their two-dimensional layer frameworks.

Structure description

In the past 12 years, numerous coordination polymers (CPs) have been designed and constructed due to their novel structures and elegant topologies, as well as their potential applications in gas storage and separation (Li et al., 2012; Noro et al., 2013; Peng et al., 2014), catalysis (Cui et al., 2003; Chen et al., 2012), chemical sensors (Hu et al., 2014; Chen et al., 2009, 2013), magnetism (Wriedt et al., 2013; Liu et al., 2014) and luminescent materials (Cui et al., 2012; Qi et al., 2013). By surveying the various structures of CPs, one can clearly see that they are strongly influenced by the organic ligands and metal ions used, so it is important to choose suitable ligands and metal ions and appropriate synthetic processes to construct CPs. Inspired by the above-mentioned previous works, we selected benzene-1,4-bis­(4-oxy-1,2-benzene­dicarb­oxy­lic acid) (H₄L) as the main ligand, two N-containing auxiliary ligands (2,2'-bi­pyridine and 1,10-phenanthroline) and Zn^II and Cd^II salts to construct CPs. The flexible -O- groups and multi­carboxyl groups allow H₄L to adjust itself to varying geometric requirements and chelate more metal ions, which may produce more inter­esting structures beyond what are currently known (Cui et al., 2010; Han et al., 2013). Due to the good aromatic conjugation properties of the chosen ligands and the high complexation properties of d¹⁰ metal ions, such d¹⁰ metal-based complexes always have good fluorescence properties and can be good candidates for optical materials (Tian et al., 2014; Hu et al., 2015). Based on this consideration, we synthesized the two title CPs, {[Zn₂(C₂₂H₁₀O₁₀)(C₁₀H₈N₂)₂(H₂O)₂].2H₂O}_n, (1), and {[Cd₂(C₂₂H₁₀O₁₀)(C₁₂H₈N₂)₂(H₂O)₂].2C₃H₇NO}_n, (2). Herein, we report the syntheses, crystal structures and fluorescence properties of (1) and (2).

Benzene-1,4-bis­(4-oxy-1,2-benzene­dicarb­oxy­lic acid) was synthesized according to the previously reported procedure (Cao et al., 2012). All other reagents and solvents used in the experiment were purchased commercially and used without further purification. Elemental analyses were carried out on a Perkin–Elmer 240 elemental analyser. Powder X-ray diffraction measurements were performed with a Bruker D8 Advance instrument. Simulated PXRD spectra were generated using the Mercury program (Macrae et al., 2008). IR spectra were recorded on a Nicolet 330 FT–IR spectrometer with KBr pellets in the range 4000–400 cm^-1. Thermogravimetric analyses (TGA) were performed on a Perkin–Elmer TGA 7 analyser with a heating rate of 10 K min^-1 under a nitro­gen stream. Fluorescence spectra were measured on an Hitachi F-7000 fluorescence spectrophotometer.

Preparation of {[Zn₂(C₂₂H₁₀O₁₀)(C₁₀H₈N₂)₂(H₂O)₂].2H₂O}_n, (1) H₄L (21.9 mg, 0.05 mmol), ZnCl₂ (13.6 mg, 0.10 mmol) and 2,2'-bi­pyridine (15.6 mg, 0.10 mmol) were dissolved in DMF–H₂O (1:1 v/v, 8 ml; DMF is di­methyl­formamide). The mixture was placed in a tightly capped 20 ml glass vial under ultrasonic irradiation for 10 min, and then heated at 353 K for 3 d and then slowly cooled to room temperature at a rate of 10 K h^-1. Colourless crystals of (1) were collected in 40% yield (based on Zn). Elemental analysis (%) for C₂₁H₁₇N₂O₇Zn (M_r = 474.74), calculated/found (%): C 53.13/53.15, H 3.61/3.63, N 5.90/5.87. IR (KBr, ν, cm^-1): 3490 (m), 1588 (s), 1491 (m), 1395 (m), 1258 (m), 1227 (s), 1178 (m), 1025 (w), 769 (m), 657 (w).

Preparation of {[Cd₂(C₂₂H₁₀O₁₀)(C₁₂H₈N₂)₂(H₂O)₂].2C₃H₇NO}_n, (2) H₄L (21.9 mg, 0.05 mmol), CdCl₂.2.5H₂O (22.8 mg, 0.10 mmol) and 1,10-phenanthroline (18.0 mg, 0.10 mmol) were dissolved in DMF–C₂H₅OH–H₂O (5:2:1 v/v/v, 8 ml). The mixture was placed in a tightly capped 20 ml glass vial under ultrasonic irradiation for 10 min, and then heated at 353 K for 3 d and then slowly cooled to room temperature at a rate of 10 K h^-1. Colourless crystals of (2) were collected in 36% yield (based on Cd). Elemental analysis (%) for C₂₆H₂₂N₃O₇Cd (M_r = 600.87), calculated/found (%): C 51.97/52.02, H 3.69/3.67, N 6.99//6.95. IR (KBr, ν, cm^-1): 3417 (m), 1667 (s), 1588 (s), 1556 (s), 1402 (s), 1218 (s), 1098 (w), 945 (w), 850 (m), 737 (m).

Single-crystal X-ray diffraction reveals that complexes (1) and (2) crystallize in the same crystal system (triclinic) and space group (P\<img height=12 src="/home/sf/Desktop/publcif/symbols/bar1.png">). The asymmetric unit of (1) contains one Zn^II cation, one half of a fully deprotonated H₄L ligand, one 2,2'-di­pyridyl ligand, one coordinated water molecule and one free water molecule. The coordination environment of the Zn^II cation is shown in Fig. 1. The Zn^II cation is penta­coordinated by two carboxyl­ate O atoms originating from two different L^4- ligands [Zn1—O3(-x, -y, -z) = 1.962 (2) Å, Zn1—O4 = 1.956 (2) Å], two N atoms from the 2,2'-di­pyridyl ligand [Zn1—N1 = 2.135 (3) Åand Zn1—N2 = 2.088 (2) Å] and one O atom from the coordinated water molecule [Zn1—O6 = 2.139 (2) Å]. The coordination geometry of Zn^II can be treated as a distorted quadrangular pyramid [Square pyramid?]. A binuclear building block is obtained through the connection of two crystallographically equivalent Zn^II cations and four carboxyl­ate groups. These units are linked to each other and generate an infinite one-dimensional zig-zag chain (Fig. 2). These one-dimensional chains are parallel to each other and further connected by inter­molecular hydrogen bonds [O7—H7A···O2(1 + x, y, z) and O7—H7B···O5; details in Table 2] to form a two-dimensional supra­molecular layer structure (Fig. 3).

The asymmetric unit of (2) contains one half of a fully deprotonated H₄L ligand, one 1,10-phenanthroline ligand, one coordinated water molecule and one free DMF molecule. As shown in Fig. 4, the central Cd^II cation is heptacoordinated by four carboxyl­ate O atoms originating from two different L^4- ligands [Cd1—O2 = 2.318 (2) Å, Cd1—O3 = 2.475 (3) Å, Cd1—O4(1 - x, -y, 1 - z) = 2.443 (2) Å and Cd1—O5(1 - x, -y, 1 - z) = 2.429 (2) Å], two N atoms from the 1,10-phenanthroline ligand [Cd1—N1 = 2.355 (3) Å and Cd1—N2 = 2.399 (3) Å] and one O atom from the coordinated water molecule [Cd1—O1 = 2.329 (2) Å]. The coordination geometry of the Cd^II cation can be treated as a distorted penta­gonal bipyramid. The construction of one-dimensional chains (Fig. 5) and two-dimensional supra­molecular layers (Fig. 6) are similar to the modes observed in (1). The inter­molecular hydrogen bonds are shown in Table 3. Besides the hydrogen-bonding inter­actions, there are several aromatic π-stacking inter­actions. Face-to-face π–π stacking is observed between 1,10-phenanthroline frames and is characterized by a centroid-to-centroid distance of ~3.4601 (3)–3.6307 (3)Å as calculated by the software PLATON (Spek, 2009).

The fluorescence properties of (1) and (2) were investigated in the solid state at 298 K. As depicted in Fig. 7, (1) and (2) exhibit fluorescence emission at ca 428 and 417 nm (excited at 330 nm), respectively. In order to understand the nature of the emission peaks, the fluorescence properties of the free ligand were measured. The results reveal that the ligand H₄L shows emission at 425 nm (excited at 330 nm), which can be attributed to intra­ligand π \rarr π* or n \rarr π* electronic transitions. As we know, d¹⁰ metal ions are difficult to oxidize or reduce due to their electronic configuration, so they neither offer electrons to the ligand, nor accept electrons from the ligand. Thus, the emission of the two compounds can be attributed to intra­ligand and/or ligand-to-ligand transition (LLCT), rather than ligand-to-metal (LMCT) or metal-to-ligand (MLCT) (Wen et al., 2007; Zhang et al., 2010). The small blue shift of the emission peak of (2) may be ascribed to the increase in conjugation upon metal coordination (Ma et al., 2013; Huang et al., 2013).

The purities of the synthesized crystals were proved by their PXRD patterns. In Fig. 8, the as-synthesized PXRD patterns of both (1) and (2) agree well with the simulated patterns. The different intensities may be due to the preferred orientations of the powder samples.

The stabilities of (1) and (2) were measured by TGA and the experimental results are in agreement with the calculated data. As shown in Fig. 9, for (1) the first weight loss of 3.84% (calculated 3.79%) at 323 to 403 K corresponds to the loss of the free water molecule and the second loss of 3.74% (calculated 3.79%) at 403 to 543 K corresponds to the loss of the coordinated water molecule, and then the organic ligands are gradually decomposed. For (2), the first weight loss of 15.09% (calculated 15.15%) at 323 to 543 K corresponds to the loss of the DMF and coordinated water molecules, then the organic ligands are gradually decomposed.

In conclusion, two new Zn^II- and Cd^II-based coordination polymers were constructed with the flexible benzene-1,4-bis­(4-oxy-1,2-benzene­dicarb­oxy­lic acid) (H₄L) ligand and two different N-containing auxiliary ligands through a mixed-ligand synthetic strategy under the solvothermal method. It is important to note that the carboxyl­ate ligands are divided into two parts by a centre of inversion. These two complexes present different two-dimensional layer structures, and their fluorescence properties indicate that (1) and (2) may be good candidates for optical materials. Furthermore, hydrogen-bonding inter­actions play an important role in the construction of their two-dimensional layer frameworks.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, and with C—H = 0.96 Å and U_iso(H) = 1.2U_eq(C) for the methyl H atoms of DMF.

Computing details

For both compounds, data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The coordination environment of the Zn^II cation in (1), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. Colour code: Zn cyan, C black, O red and N blue. [Symmetry codes: (i) -x, -y, -z; (ii) -1 - x, -1 - y, 1 - z.]
	Fig. 2. The infinite one-dimensional chain of (1). H atoms have been omitted for clarity.
	Fig. 3. The two-dimensional supramolecular layer structure of (1) and the hydrogen-bonding interactions (dashed lines). H atoms except for thos on the free water molecules have been omitted for clarity.
	Fig. 4. The coordination environment of the Cd^II cation in (2), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. Color code: Cd cyan, C black, O red and N blue. [Symmetry codes: (i) 1 - x, -y, 1 - z; (ii) 1 - x, -1 - y, -z.]
	Fig. 5. The infinite one-dimensional chain of (2).
	Fig. 6. The two-dimensional supramolecular layer structure of (2) and the hydrogen-bonding interactions (dashed lines). H atoms except for those on the coordinated water molecules have been omitted for clarity.
	Fig. 7. The fluorescence emission spectra for the free ligand (black), complex (1) (blue) and complex (2) (red) in the solid state (excited at 330 nm).
	Fig. 8. PXRD patterns of (1) and (2). The simulated profiles are shown in red and the as-synthesized profiles in black.
	Fig. 9. The TGA curves for (1) (black) and (2) (red).

(1) Poly[[diaqua[µ₄-4,4'-(1,4-phenylenedioxy)bis(benzene-1,2-dicarboxylato)]bis(2,2'-bipyridine)dizinc(II)] monohydrate]

Crystal data

[Zn2(C22H10O10)(C10H8N2)2(H2O)2]·2H2O	Z = 1
Mr = 949.48	F(000) = 486
Triclinic, P1	Dx = 1.600 Mg m^−3
a = 9.5585 (5) Å	Mo Kα radiation, λ = 0.71065 Å
b = 10.0434 (4) Å	Cell parameters from 7054 reflections
c = 10.6027 (5) Å	θ = 1.9–25.7°
α = 92.365 (4)°	µ = 1.30 mm^−1
β = 94.032 (4)°	T = 293 K
γ = 103.509 (4)°	Block, colourless
V = 985.50 (8) Å^3	0.31 × 0.27 × 0.25 mm

Data collection

Agilent SuperNova Eos CCD area-detector diffractometer	3596 independent reflections
Radiation source: fine-focus sealed tube	3170 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
CCD scans	θmax = 25.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.690, Tmax = 0.738	k = −11→12
6965 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0558P)^2 + 1.1217P] where P = (Fo^2 + 2Fc^2)/3
3596 reflections	(Δ/σ)max < 0.001
284 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.52 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Zn1	0.16277 (4)	0.21682 (4)	0.09447 (4)	0.03887 (15)
N1	−0.0146 (3)	0.3069 (3)	0.1240 (3)	0.0341 (6)
N2	0.2641 (3)	0.4232 (2)	0.1371 (2)	0.0319 (5)
O1	−0.2254 (3)	−0.3489 (4)	0.5831 (3)	0.0731 (10)
O2	−0.2835 (2)	−0.0912 (2)	0.1618 (2)	0.0417 (5)
O3	−0.1125 (3)	−0.1859 (2)	0.0887 (2)	0.0411 (5)
O4	0.0790 (2)	0.0706 (2)	0.2025 (2)	0.0380 (5)
O5	0.2641 (3)	−0.0199 (3)	0.2605 (3)	0.0555 (7)
O6	0.3639 (2)	0.1589 (2)	0.0892 (2)	0.0404 (5)
H6A	0.3768	0.1325	0.0124	0.061*
H6B	0.3660	0.0913	0.1377	0.061*
C1	0.4055 (4)	0.4765 (3)	0.1343 (3)	0.0406 (7)
H1	0.4652	0.4177	0.1186	0.049*
C2	0.4666 (4)	0.6149 (4)	0.1537 (4)	0.0503 (9)
H2	0.5654	0.6490	0.1505	0.060*
C3	0.3787 (5)	0.7010 (4)	0.1778 (4)	0.0576 (10)
H3	0.4173	0.7949	0.1914	0.069*
C4	0.2325 (4)	0.6480 (4)	0.1820 (4)	0.0505 (9)
H4	0.1715	0.7051	0.1991	0.061*
C5	0.1782 (4)	0.5072 (3)	0.1600 (3)	0.0352 (7)
C6	0.0220 (4)	0.4405 (3)	0.1610 (3)	0.0349 (7)
C7	−0.0789 (4)	0.5087 (4)	0.1992 (4)	0.0530 (10)
H7	−0.0518	0.6015	0.2246	0.064*
C8	−0.2201 (4)	0.4370 (5)	0.1992 (5)	0.0620 (11)
H8	−0.2894	0.4811	0.2254	0.074*
C9	−0.2590 (4)	0.3001 (4)	0.1605 (4)	0.0559 (10)
H9	−0.3543	0.2503	0.1592	0.067*
C10	−0.1524 (4)	0.2391 (4)	0.1237 (4)	0.0461 (8)
H10	−0.1776	0.1465	0.0974	0.055*
C11	0.1370 (3)	−0.0127 (3)	0.2623 (3)	0.0354 (7)
C12	0.0381 (4)	−0.1067 (3)	0.3425 (3)	0.0337 (7)
C13	−0.1087 (3)	−0.1519 (3)	0.3068 (3)	0.0327 (7)
C14	−0.1998 (4)	−0.2314 (3)	0.3871 (3)	0.0408 (8)
H14	−0.2985	−0.2594	0.3648	0.049*
C15	−0.1418 (4)	−0.2678 (4)	0.4997 (3)	0.0485 (9)
C16	0.0025 (4)	−0.2256 (4)	0.5344 (3)	0.0486 (9)
H16	0.0403	−0.2518	0.6101	0.058*
C17	0.0925 (4)	−0.1438 (3)	0.4572 (3)	0.0428 (8)
H17	0.1904	−0.1133	0.4823	0.051*
O7	0.5799 (6)	0.0449 (8)	0.3618 (7)	0.144 (2)
H7A	0.5892	0.0131	0.2881	0.216*
H7B	0.4939	0.0143	0.3808	0.216*
C18	−0.1743 (3)	−0.1373 (3)	0.1764 (3)	0.0334 (7)
C19	−0.3639 (5)	−0.4234 (4)	0.5388 (4)	0.0564 (10)
C20	−0.3831 (5)	−0.5576 (5)	0.4922 (4)	0.0621 (11)
H20	−0.3040	−0.5962	0.4875	0.074*
C21	−0.4797 (5)	−0.3655 (5)	0.5475 (4)	0.0639 (11)
H21	−0.4661	−0.2754	0.5798	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0388 (2)	0.0299 (2)	0.0463 (2)	0.00327 (16)	0.00882 (17)	0.00229 (16)
N1	0.0322 (13)	0.0263 (13)	0.0443 (15)	0.0055 (11)	0.0085 (11)	0.0049 (11)
N2	0.0333 (13)	0.0244 (12)	0.0361 (13)	0.0015 (10)	0.0066 (10)	0.0026 (10)
O1	0.0616 (19)	0.091 (2)	0.0476 (16)	−0.0260 (17)	0.0072 (13)	0.0303 (15)
O2	0.0379 (13)	0.0420 (13)	0.0449 (13)	0.0073 (11)	0.0088 (10)	0.0045 (10)
O3	0.0473 (14)	0.0435 (13)	0.0343 (12)	0.0143 (11)	0.0059 (10)	−0.0006 (10)
O4	0.0350 (12)	0.0285 (11)	0.0517 (13)	0.0053 (9)	0.0134 (10)	0.0139 (10)
O5	0.0390 (14)	0.0585 (17)	0.0752 (19)	0.0157 (12)	0.0173 (13)	0.0333 (14)
O6	0.0324 (12)	0.0373 (12)	0.0516 (14)	0.0062 (10)	0.0083 (10)	0.0078 (10)
C1	0.0351 (17)	0.0357 (17)	0.0480 (19)	0.0016 (14)	0.0079 (14)	−0.0002 (14)
C2	0.0386 (19)	0.041 (2)	0.063 (2)	−0.0085 (16)	0.0064 (17)	0.0008 (17)
C3	0.062 (3)	0.0258 (17)	0.076 (3)	−0.0085 (17)	0.012 (2)	−0.0013 (17)
C4	0.056 (2)	0.0260 (17)	0.068 (2)	0.0038 (16)	0.0156 (19)	−0.0004 (16)
C5	0.0408 (18)	0.0263 (15)	0.0375 (16)	0.0034 (13)	0.0096 (13)	0.0041 (12)
C6	0.0379 (17)	0.0270 (15)	0.0403 (16)	0.0068 (13)	0.0082 (13)	0.0064 (12)
C7	0.049 (2)	0.0373 (19)	0.077 (3)	0.0162 (17)	0.0140 (19)	−0.0008 (18)
C8	0.044 (2)	0.061 (3)	0.089 (3)	0.026 (2)	0.016 (2)	0.004 (2)
C9	0.0309 (18)	0.061 (3)	0.076 (3)	0.0082 (17)	0.0089 (18)	0.014 (2)
C10	0.0350 (18)	0.0339 (18)	0.067 (2)	0.0023 (14)	0.0053 (16)	0.0081 (16)
C11	0.0354 (17)	0.0264 (15)	0.0416 (17)	0.0007 (13)	0.0068 (13)	0.0024 (13)
C12	0.0401 (17)	0.0219 (14)	0.0377 (16)	0.0028 (13)	0.0091 (13)	0.0020 (12)
C13	0.0391 (17)	0.0230 (14)	0.0335 (15)	−0.0001 (12)	0.0101 (13)	0.0021 (12)
C14	0.0397 (18)	0.0382 (18)	0.0392 (18)	−0.0037 (14)	0.0104 (14)	0.0039 (14)
C15	0.059 (2)	0.043 (2)	0.0357 (18)	−0.0060 (17)	0.0119 (16)	0.0107 (15)
C16	0.055 (2)	0.049 (2)	0.0360 (18)	0.0002 (17)	0.0028 (16)	0.0112 (15)
C17	0.0424 (19)	0.0363 (18)	0.0450 (19)	−0.0003 (15)	0.0036 (15)	0.0039 (14)
O7	0.094 (3)	0.175 (6)	0.158 (5)	0.041 (4)	−0.011 (3)	−0.063 (5)
C18	0.0349 (17)	0.0201 (14)	0.0411 (17)	−0.0042 (12)	0.0100 (13)	0.0042 (12)
C19	0.059 (2)	0.059 (2)	0.045 (2)	−0.007 (2)	0.0174 (18)	0.0204 (18)
C20	0.061 (3)	0.063 (3)	0.064 (3)	0.012 (2)	0.023 (2)	0.019 (2)
C21	0.076 (3)	0.052 (2)	0.060 (3)	0.003 (2)	0.018 (2)	0.011 (2)

Geometric parameters (Å, º)

Zn1—O4	1.956 (2)	C6—C7	1.380 (5)
Zn1—O3^i	1.962 (2)	C7—C8	1.373 (6)
Zn1—N2	2.088 (2)	C7—H7	0.9300
Zn1—N1	2.135 (3)	C8—C9	1.375 (6)
Zn1—O6	2.139 (2)	C8—H8	0.9300
N1—C10	1.334 (4)	C9—C10	1.376 (5)
N1—C6	1.339 (4)	C9—H9	0.9300
N2—C5	1.334 (4)	C10—H10	0.9300
N2—C1	1.335 (4)	C11—C12	1.507 (4)
O1—C15	1.392 (4)	C12—C17	1.388 (5)
O1—C19	1.397 (5)	C12—C13	1.390 (5)
O2—C18	1.241 (4)	C13—C14	1.398 (4)
O3—C18	1.275 (4)	C13—C18	1.504 (4)
O3—Zn1^i	1.962 (2)	C14—C15	1.381 (5)
O4—C11	1.273 (4)	C14—H14	0.9300
O5—C11	1.235 (4)	C15—C16	1.363 (5)
O6—H6A	0.8714	C16—C17	1.382 (5)
O6—H6B	0.8711	C16—H16	0.9300
C1—C2	1.377 (5)	C17—H17	0.9300
C1—H1	0.9300	O7—H7A	0.8499
C2—C3	1.368 (6)	O7—H7B	0.8498
C2—H2	0.9300	C19—C21	1.372 (7)
C3—C4	1.378 (6)	C19—C20	1.383 (6)
C3—H3	0.9300	C20—C21^ii	1.384 (6)
C4—C5	1.391 (5)	C20—H20	0.9300
C4—H4	0.9300	C21—C20^ii	1.384 (6)
C5—C6	1.489 (4)	C21—H21	0.9300
O4—Zn1—O3^i	117.65 (10)	C7—C8—C9	120.0 (4)
O4—Zn1—N2	131.44 (10)	C7—C8—H8	120.0
O3^i—Zn1—N2	109.45 (10)	C9—C8—H8	120.0
O4—Zn1—N1	88.55 (9)	C8—C9—C10	117.9 (4)
O3^i—Zn1—N1	93.31 (10)	C8—C9—H9	121.0
N2—Zn1—N1	77.29 (10)	C10—C9—H9	121.0
O4—Zn1—O6	94.56 (9)	N1—C10—C9	122.9 (3)
O3^i—Zn1—O6	94.74 (10)	N1—C10—H10	118.6
N2—Zn1—O6	92.70 (10)	C9—C10—H10	118.6
N1—Zn1—O6	168.83 (10)	O5—C11—O4	125.7 (3)
C10—N1—C6	118.8 (3)	O5—C11—C12	119.5 (3)
C10—N1—Zn1	125.7 (2)	O4—C11—C12	114.8 (3)
C6—N1—Zn1	115.0 (2)	C17—C12—C13	119.1 (3)
C5—N2—C1	118.7 (3)	C17—C12—C11	119.7 (3)
C5—N2—Zn1	116.5 (2)	C13—C12—C11	121.1 (3)
C1—N2—Zn1	124.6 (2)	C12—C13—C14	120.0 (3)
C15—O1—C19	118.5 (3)	C12—C13—C18	123.1 (3)
C18—O3—Zn1^i	131.6 (2)	C14—C13—C18	116.3 (3)
C11—O4—Zn1	130.4 (2)	C15—C14—C13	119.4 (3)
Zn1—O6—H6A	110.8	C15—C14—H14	120.3
Zn1—O6—H6B	110.5	C13—C14—H14	120.3
H6A—O6—H6B	108.2	C16—C15—C14	120.9 (3)
N2—C1—C2	122.8 (3)	C16—C15—O1	116.6 (3)
N2—C1—H1	118.6	C14—C15—O1	122.5 (3)
C2—C1—H1	118.6	C15—C16—C17	120.0 (3)
C3—C2—C1	118.5 (3)	C15—C16—H16	120.0
C3—C2—H2	120.8	C17—C16—H16	120.0
C1—C2—H2	120.8	C16—C17—C12	120.6 (3)
C2—C3—C4	119.7 (3)	C16—C17—H17	119.7
C2—C3—H3	120.2	C12—C17—H17	119.7
C4—C3—H3	120.2	H7A—O7—H7B	109.5
C3—C4—C5	118.6 (4)	O2—C18—O3	126.0 (3)
C3—C4—H4	120.7	O2—C18—C13	120.9 (3)
C5—C4—H4	120.7	O3—C18—C13	112.9 (3)
N2—C5—C4	121.7 (3)	C21—C19—C20	120.7 (4)
N2—C5—C6	115.7 (3)	C21—C19—O1	120.0 (4)
C4—C5—C6	122.6 (3)	C20—C19—O1	119.2 (4)
N1—C6—C7	121.7 (3)	C19—C20—C21^ii	119.9 (4)
N1—C6—C5	115.0 (3)	C19—C20—H20	120.0
C7—C6—C5	123.3 (3)	C21^ii—C20—H20	120.0
C8—C7—C6	118.8 (4)	C19—C21—C20^ii	119.3 (4)
C8—C7—H7	120.6	C19—C21—H21	120.3
C6—C7—H7	120.6	C20^ii—C21—H21	120.3
O4—Zn1—N1—C10	−42.2 (3)	C5—C6—C7—C8	−178.6 (4)
O3^i—Zn1—N1—C10	75.5 (3)	C6—C7—C8—C9	−0.5 (7)
N2—Zn1—N1—C10	−175.3 (3)	C7—C8—C9—C10	0.5 (7)
O6—Zn1—N1—C10	−148.5 (4)	C6—N1—C10—C9	−0.5 (6)
O4—Zn1—N1—C6	129.3 (2)	Zn1—N1—C10—C9	170.7 (3)
O3^i—Zn1—N1—C6	−113.1 (2)	C8—C9—C10—N1	0.0 (6)
N2—Zn1—N1—C6	−3.9 (2)	Zn1—O4—C11—O5	−2.3 (5)
O6—Zn1—N1—C6	22.9 (6)	Zn1—O4—C11—C12	176.6 (2)
O4—Zn1—N2—C5	−76.9 (3)	O5—C11—C12—C17	34.5 (5)
O3^i—Zn1—N2—C5	88.6 (2)	O4—C11—C12—C17	−144.5 (3)
N1—Zn1—N2—C5	−0.4 (2)	O5—C11—C12—C13	−148.8 (3)
O6—Zn1—N2—C5	−175.4 (2)	O4—C11—C12—C13	32.3 (4)
O4—Zn1—N2—C1	107.9 (3)	C17—C12—C13—C14	1.2 (5)
O3^i—Zn1—N2—C1	−86.6 (3)	C11—C12—C13—C14	−175.6 (3)
N1—Zn1—N2—C1	−175.6 (3)	C17—C12—C13—C18	−169.7 (3)
O6—Zn1—N2—C1	9.4 (3)	C11—C12—C13—C18	13.5 (5)
O3^i—Zn1—O4—C11	107.4 (3)	C12—C13—C14—C15	−2.0 (5)
N2—Zn1—O4—C11	−88.1 (3)	C18—C13—C14—C15	169.4 (3)
N1—Zn1—O4—C11	−159.7 (3)	C13—C14—C15—C16	1.0 (6)
O6—Zn1—O4—C11	9.6 (3)	C13—C14—C15—O1	−178.7 (4)
C5—N2—C1—C2	−0.2 (5)	C19—O1—C15—C16	−163.6 (4)
Zn1—N2—C1—C2	174.9 (3)	C19—O1—C15—C14	16.2 (6)
N2—C1—C2—C3	0.5 (6)	C14—C15—C16—C17	0.8 (6)
C1—C2—C3—C4	−0.1 (6)	O1—C15—C16—C17	−179.4 (4)
C2—C3—C4—C5	−0.7 (6)	C15—C16—C17—C12	−1.6 (6)
C1—N2—C5—C4	−0.6 (5)	C13—C12—C17—C16	0.6 (5)
Zn1—N2—C5—C4	−176.1 (3)	C11—C12—C17—C16	177.5 (3)
C1—N2—C5—C6	179.7 (3)	Zn1^i—O3—C18—O2	−3.4 (5)
Zn1—N2—C5—C6	4.2 (4)	Zn1^i—O3—C18—C13	171.5 (2)
C3—C4—C5—N2	1.0 (6)	C12—C13—C18—O2	−132.2 (3)
C3—C4—C5—C6	−179.3 (3)	C14—C13—C18—O2	56.6 (4)
C10—N1—C6—C7	0.5 (5)	C12—C13—C18—O3	52.7 (4)
Zn1—N1—C6—C7	−171.6 (3)	C14—C13—C18—O3	−118.5 (3)
C10—N1—C6—C5	179.2 (3)	C15—O1—C19—C21	−89.6 (5)
Zn1—N1—C6—C5	7.1 (4)	C15—O1—C19—C20	93.4 (5)
N2—C5—C6—N1	−7.6 (4)	C21—C19—C20—C21^ii	0.6 (7)
C4—C5—C6—N1	172.7 (3)	O1—C19—C20—C21^ii	177.5 (3)
N2—C5—C6—C7	171.2 (3)	C20—C19—C21—C20^ii	−0.6 (7)
C4—C5—C6—C7	−8.5 (5)	O1—C19—C21—C20^ii	−177.5 (3)
N1—C6—C7—C8	0.0 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O2^i	0.87	1.98	2.7307 (1)	144
O6—H6B···O5	0.87	1.92	2.6731 (1)	144
O7—H7A···O2^iii	0.85	2.26	3.0082 (2)	148
O7—H7B···O5	0.85	2.40	3.0430 (2)	133

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

(2) Poly[[diaquabis(1,10-phenanthroline)[µ₄-4,4'-(1,4-phenylenedioxy)bis(benzene-1,2-dicarboxylato)]dicadmium(II)] dimethylformamide monosolvate]

Crystal data

[Cd2(C22H10O10)(C12H8N2)2(H2O)2]·2C3H7NO	Z = 1
Mr = 1201.74	F(000) = 606
Triclinic, P1	Dx = 1.669 Mg m^−3
a = 6.8275 (4) Å	Cu Kα radiation, λ = 1.54184 Å
b = 12.7613 (7) Å	Cell parameters from 4665 reflections
c = 14.8770 (11) Å	θ = 2.0–35.1°
α = 106.134 (6)°	µ = 7.78 mm^−1
β = 101.602 (6)°	T = 250 K
γ = 97.496 (5)°	Block, colourless
V = 1195.55 (13) Å^3	0.27 × 0.24 × 0.22 mm

Data collection

Agilent SuperNova Eos CCD area-detector diffractometer	4256 independent reflections
Radiation source: fine-focus sealed tube	3854 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
CCD scans	θmax = 67.1°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→8
Tmin = 0.228, Tmax = 0.279	k = −11→15
8401 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0305P)^2 + 1.1118P] where P = (Fo^2 + 2Fc^2)/3
4256 reflections	(Δ/σ)max = 0.001
336 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.81 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cd1	0.20594 (3)	0.165959 (17)	0.488435 (15)	0.02344 (8)
N1	0.2289 (4)	0.3270 (2)	0.44005 (19)	0.0232 (6)
N2	0.1619 (4)	0.3200 (2)	0.61328 (19)	0.0256 (6)
N3	0.5730 (5)	0.1050 (3)	0.1438 (2)	0.0412 (8)
O1	−0.1467 (4)	0.11438 (19)	0.45922 (17)	0.0339 (6)
H1B	−0.1733	0.1016	0.5090	0.041*
H1C	−0.1861	0.0536	0.4129	0.041*
O2	0.2720 (5)	−0.0069 (2)	0.41562 (18)	0.0471 (7)
O3	0.1480 (4)	0.07496 (19)	0.31257 (18)	0.0418 (6)
O4	0.6732 (3)	−0.11028 (18)	0.36908 (16)	0.0277 (5)
O5	0.4485 (4)	−0.21767 (19)	0.40961 (16)	0.0310 (5)
O6	0.2079 (4)	−0.3696 (2)	0.01024 (17)	0.0415 (7)
O7	0.3215 (6)	0.1864 (4)	0.0877 (4)	0.1068 (17)
C1	0.1273 (5)	0.3160 (3)	0.6970 (2)	0.0335 (8)
H1	0.0961	0.2468	0.7055	0.040*
C2	0.1356 (6)	0.4113 (3)	0.7728 (3)	0.0395 (9)
H2	0.1110	0.4055	0.8306	0.047*
C3	0.1805 (5)	0.5134 (3)	0.7608 (3)	0.0379 (9)
H3	0.1906	0.5777	0.8113	0.045*
C4	0.2113 (5)	0.5209 (3)	0.6723 (3)	0.0302 (8)
C5	0.2442 (5)	0.6238 (3)	0.6512 (3)	0.0389 (9)
H5	0.2512	0.6901	0.6989	0.047*
C6	0.2650 (5)	0.6266 (3)	0.5639 (3)	0.0354 (9)
H6	0.2835	0.6946	0.5520	0.042*
C7	0.2594 (5)	0.5269 (3)	0.4889 (3)	0.0280 (7)
C8	0.2825 (5)	0.5265 (3)	0.3975 (3)	0.0344 (8)
H8	0.3036	0.5930	0.3832	0.041*
C9	0.2738 (5)	0.4277 (3)	0.3292 (3)	0.0339 (8)
H9	0.2856	0.4259	0.2676	0.041*
C10	0.2471 (5)	0.3294 (3)	0.3533 (2)	0.0296 (7)
H10	0.2417	0.2626	0.3064	0.036*
C11	0.2319 (4)	0.4239 (2)	0.5073 (2)	0.0228 (7)
C12	0.2023 (4)	0.4213 (2)	0.6000 (2)	0.0223 (7)
C13	0.2116 (5)	−0.0060 (3)	0.3308 (2)	0.0262 (7)
C14	0.2141 (5)	−0.1058 (2)	0.2498 (2)	0.0229 (7)
C15	0.3450 (5)	−0.1789 (2)	0.2610 (2)	0.0207 (6)
C16	0.3476 (5)	−0.2680 (2)	0.1812 (2)	0.0238 (7)
H16	0.4364	−0.3163	0.1880	0.029*
C17	0.2172 (5)	−0.2837 (3)	0.0925 (2)	0.0277 (7)
C18	0.0816 (5)	−0.2135 (3)	0.0809 (2)	0.0268 (7)
H18	−0.0092	−0.2263	0.0215	0.032*
C19	0.0841 (5)	−0.1246 (3)	0.1590 (2)	0.0276 (7)
H19	−0.0029	−0.0757	0.1511	0.033*
C20	0.4978 (5)	−0.1657 (2)	0.3547 (2)	0.0230 (7)
C21	0.3610 (5)	−0.4325 (3)	0.0102 (2)	0.0298 (8)
C22	0.3247 (5)	−0.5338 (3)	0.0258 (2)	0.0339 (8)
H22	0.2064	−0.5559	0.0433	0.041*
C23	0.5343 (5)	−0.3973 (3)	−0.0154 (3)	0.0343 (8)
H23	0.5569	−0.3285	−0.0257	0.041*
C24	0.3942 (7)	0.1347 (4)	0.1389 (3)	0.0517 (11)
H24	0.3168	0.1143	0.1783	0.062*
C25	0.6430 (8)	0.0433 (5)	0.2069 (5)	0.083 (2)
H25A	0.5583	0.0445	0.2514	0.124*
H25B	0.7815	0.0765	0.2423	0.124*
H25C	0.6360	−0.0322	0.1694	0.124*
C26	0.7060 (9)	0.1303 (5)	0.0844 (4)	0.0736 (15)
H26A	0.6388	0.1654	0.0412	0.110*
H26B	0.7372	0.0626	0.0477	0.110*
H26C	0.8300	0.1795	0.1252	0.110*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02953 (13)	0.01776 (12)	0.02156 (12)	0.00860 (9)	0.00474 (9)	0.00324 (8)
N1	0.0192 (13)	0.0221 (13)	0.0293 (14)	0.0067 (10)	0.0063 (11)	0.0086 (11)
N2	0.0234 (13)	0.0237 (13)	0.0269 (14)	0.0048 (11)	0.0051 (11)	0.0042 (11)
N3	0.0434 (19)	0.0447 (18)	0.0413 (19)	0.0063 (15)	0.0180 (15)	0.0183 (15)
O1	0.0367 (13)	0.0263 (12)	0.0332 (13)	−0.0013 (10)	0.0094 (11)	0.0036 (10)
O2	0.079 (2)	0.0369 (14)	0.0239 (13)	0.0310 (14)	0.0083 (13)	0.0018 (11)
O3	0.0641 (18)	0.0250 (12)	0.0354 (14)	0.0216 (12)	0.0110 (13)	0.0034 (11)
O4	0.0276 (12)	0.0243 (11)	0.0262 (12)	0.0015 (9)	0.0016 (10)	0.0052 (9)
O5	0.0341 (13)	0.0297 (12)	0.0270 (12)	0.0019 (10)	0.0033 (10)	0.0104 (10)
O6	0.0415 (15)	0.0423 (14)	0.0258 (13)	0.0267 (12)	−0.0056 (11)	−0.0113 (11)
O7	0.083 (3)	0.124 (4)	0.161 (5)	0.042 (3)	0.030 (3)	0.110 (4)
C1	0.0317 (18)	0.040 (2)	0.0305 (19)	0.0097 (16)	0.0100 (15)	0.0116 (16)
C2	0.037 (2)	0.054 (2)	0.0233 (18)	0.0153 (18)	0.0055 (16)	0.0043 (17)
C3	0.0333 (19)	0.041 (2)	0.0269 (18)	0.0146 (16)	0.0012 (15)	−0.0075 (16)
C4	0.0175 (16)	0.0271 (17)	0.037 (2)	0.0068 (13)	−0.0004 (14)	0.0006 (15)
C5	0.0269 (18)	0.0208 (16)	0.052 (2)	0.0070 (14)	−0.0064 (17)	−0.0048 (16)
C6	0.0205 (17)	0.0177 (16)	0.060 (3)	0.0036 (13)	0.0001 (17)	0.0073 (16)
C7	0.0130 (14)	0.0235 (16)	0.044 (2)	0.0047 (12)	−0.0012 (14)	0.0105 (15)
C8	0.0206 (16)	0.0360 (19)	0.050 (2)	0.0034 (14)	0.0037 (16)	0.0242 (17)
C9	0.0295 (18)	0.046 (2)	0.035 (2)	0.0114 (16)	0.0114 (16)	0.0217 (17)
C10	0.0263 (17)	0.0311 (17)	0.0319 (18)	0.0085 (14)	0.0067 (14)	0.0096 (14)
C11	0.0127 (14)	0.0220 (15)	0.0322 (17)	0.0026 (12)	0.0024 (12)	0.0087 (13)
C12	0.0152 (14)	0.0204 (15)	0.0272 (16)	0.0050 (12)	0.0026 (12)	0.0021 (13)
C13	0.0242 (16)	0.0230 (16)	0.0298 (18)	0.0047 (13)	0.0085 (14)	0.0044 (13)
C14	0.0265 (16)	0.0208 (15)	0.0237 (16)	0.0075 (13)	0.0095 (13)	0.0068 (13)
C15	0.0207 (15)	0.0195 (14)	0.0204 (15)	0.0016 (12)	0.0067 (12)	0.0038 (12)
C16	0.0242 (16)	0.0193 (15)	0.0261 (16)	0.0090 (12)	0.0045 (13)	0.0032 (13)
C17	0.0279 (17)	0.0251 (16)	0.0237 (16)	0.0089 (13)	0.0032 (14)	−0.0017 (13)
C18	0.0260 (17)	0.0316 (17)	0.0199 (16)	0.0111 (14)	0.0026 (13)	0.0033 (13)
C19	0.0273 (17)	0.0268 (16)	0.0299 (18)	0.0140 (14)	0.0069 (14)	0.0072 (14)
C20	0.0271 (17)	0.0151 (14)	0.0230 (16)	0.0048 (12)	0.0045 (13)	0.0007 (12)
C21	0.0320 (18)	0.0271 (16)	0.0206 (16)	0.0149 (14)	−0.0016 (14)	−0.0060 (13)
C22	0.0304 (18)	0.042 (2)	0.0259 (18)	0.0080 (15)	0.0062 (15)	0.0045 (15)
C23	0.037 (2)	0.0263 (17)	0.0327 (19)	0.0083 (15)	−0.0005 (16)	0.0047 (14)
C24	0.052 (3)	0.045 (2)	0.064 (3)	0.013 (2)	0.014 (2)	0.024 (2)
C25	0.050 (3)	0.116 (5)	0.119 (5)	0.026 (3)	0.024 (3)	0.090 (4)
C26	0.084 (4)	0.073 (4)	0.078 (4)	0.013 (3)	0.046 (3)	0.029 (3)

Geometric parameters (Å, º)

Cd1—O2	2.318 (2)	C6—C7	1.430 (5)
Cd1—O1	2.329 (2)	C6—H6	0.9300
Cd1—N1	2.355 (3)	C7—C8	1.400 (5)
Cd1—N2	2.399 (3)	C7—C11	1.412 (4)
Cd1—O5^i	2.429 (2)	C8—C9	1.368 (5)
Cd1—O4^i	2.443 (2)	C8—H8	0.9300
Cd1—O3	2.475 (3)	C9—C10	1.396 (5)
N1—C10	1.330 (4)	C9—H9	0.9300
N1—C11	1.353 (4)	C10—H10	0.9300
N2—C1	1.326 (4)	C11—C12	1.442 (5)
N2—C12	1.363 (4)	C13—C14	1.495 (4)
N3—C24	1.319 (5)	C14—C15	1.393 (4)
N3—C25	1.435 (5)	C14—C19	1.398 (4)
N3—C26	1.454 (5)	C15—C16	1.402 (4)
O1—H1B	0.8500	C15—C20	1.516 (4)
O1—H1C	0.8500	C16—C17	1.382 (4)
O2—C13	1.250 (4)	C16—H16	0.9300
O3—C13	1.247 (4)	C17—C18	1.388 (4)
O4—C20	1.253 (4)	C18—C19	1.375 (4)
O4—Cd1^i	2.442 (2)	C18—H18	0.9300
O5—C20	1.255 (4)	C19—H19	0.9300
O5—Cd1^i	2.429 (2)	C21—C23	1.373 (5)
O6—C17	1.382 (4)	C21—C22	1.376 (5)
O6—C21	1.398 (4)	C22—C23^ii	1.390 (5)
O7—C24	1.213 (5)	C22—H22	0.9300
C1—C2	1.396 (5)	C23—C22^ii	1.390 (5)
C1—H1	0.9300	C23—H23	0.9300
C2—C3	1.368 (6)	C24—H24	0.9300
C2—H2	0.9300	C25—H25A	0.9600
C3—C4	1.400 (5)	C25—H25B	0.9600
C3—H3	0.9300	C25—H25C	0.9600
C4—C12	1.404 (4)	C26—H26A	0.9600
C4—C5	1.434 (5)	C26—H26B	0.9600
C5—C6	1.344 (6)	C26—H26C	0.9600
C5—H5	0.9300
O2—Cd1—O1	98.17 (10)	C7—C8—H8	120.3
O2—Cd1—N1	129.62 (9)	C8—C9—C10	119.1 (3)
O1—Cd1—N1	100.26 (8)	C8—C9—H9	120.5
O2—Cd1—N2	158.99 (9)	C10—C9—H9	120.5
O1—Cd1—N2	83.18 (8)	N1—C10—C9	123.0 (3)
N1—Cd1—N2	70.07 (9)	N1—C10—H10	118.5
O2—Cd1—O5^i	88.87 (9)	C9—C10—H10	118.5
O1—Cd1—O5^i	153.56 (8)	N1—C11—C7	122.1 (3)
N1—Cd1—O5^i	94.53 (8)	N1—C11—C12	118.7 (3)
N2—Cd1—O5^i	81.44 (9)	C7—C11—C12	119.2 (3)
O2—Cd1—O4^i	79.86 (8)	N2—C12—C4	122.1 (3)
O1—Cd1—O4^i	102.10 (8)	N2—C12—C11	117.9 (3)
N1—Cd1—O4^i	139.32 (8)	C4—C12—C11	120.0 (3)
N2—Cd1—O4^i	79.37 (8)	O3—C13—O2	121.8 (3)
O5^i—Cd1—O4^i	53.92 (7)	O3—C13—C14	119.7 (3)
O2—Cd1—O3	54.03 (8)	O2—C13—C14	118.5 (3)
O1—Cd1—O3	84.67 (9)	C15—C14—C19	118.9 (3)
N1—Cd1—O3	81.60 (9)	C15—C14—C13	122.3 (3)
N2—Cd1—O3	146.47 (9)	C19—C14—C13	118.7 (3)
O5^i—Cd1—O3	119.33 (9)	C14—C15—C16	119.8 (3)
O4^i—Cd1—O3	133.86 (8)	C14—C15—C20	124.1 (3)
C10—N1—C11	118.4 (3)	C16—C15—C20	116.0 (3)
C10—N1—Cd1	124.7 (2)	C17—C16—C15	119.6 (3)
C11—N1—Cd1	116.9 (2)	C17—C16—H16	120.2
C1—N2—C12	118.6 (3)	C15—C16—H16	120.2
C1—N2—Cd1	125.6 (2)	C18—C17—O6	115.2 (3)
C12—N2—Cd1	115.3 (2)	C18—C17—C16	121.2 (3)
C24—N3—C25	121.0 (4)	O6—C17—C16	123.6 (3)
C24—N3—C26	122.2 (4)	C19—C18—C17	118.7 (3)
C25—N3—C26	116.8 (4)	C19—C18—H18	120.6
Cd1—O1—H1B	108.1	C17—C18—H18	120.6
Cd1—O1—H1C	108.1	C18—C19—C14	121.7 (3)
H1B—O1—H1C	107.4	C18—C19—H19	119.2
C13—O2—Cd1	95.7 (2)	C14—C19—H19	119.2
C13—O3—Cd1	88.4 (2)	O4—C20—O5	123.4 (3)
C20—O4—Cd1^i	91.00 (18)	O4—C20—C15	117.6 (3)
C20—O5—Cd1^i	91.58 (18)	O5—C20—C15	118.7 (3)
C17—O6—C21	119.2 (2)	C23—C21—C22	121.6 (3)
N2—C1—C2	122.7 (3)	C23—C21—O6	119.1 (3)
N2—C1—H1	118.6	C22—C21—O6	118.9 (3)
C2—C1—H1	118.6	C21—C22—C23^ii	119.6 (3)
C3—C2—C1	119.0 (4)	C21—C22—H22	120.2
C3—C2—H2	120.5	C23^ii—C22—H22	120.2
C1—C2—H2	120.5	C21—C23—C22^ii	118.8 (3)
C2—C3—C4	119.9 (3)	C21—C23—H23	120.6
C2—C3—H3	120.0	C22^ii—C23—H23	120.6
C4—C3—H3	120.0	O7—C24—N3	125.9 (5)
C3—C4—C12	117.6 (3)	O7—C24—H24	117.0
C3—C4—C5	123.6 (3)	N3—C24—H24	117.0
C12—C4—C5	118.8 (3)	N3—C25—H25A	109.5
C6—C5—C4	121.5 (3)	N3—C25—H25B	109.5
C6—C5—H5	119.3	H25A—C25—H25B	109.5
C4—C5—H5	119.3	N3—C25—H25C	109.5
C5—C6—C7	121.2 (3)	H25A—C25—H25C	109.5
C5—C6—H6	119.4	H25B—C25—H25C	109.5
C7—C6—H6	119.4	N3—C26—H26A	109.5
C8—C7—C11	117.9 (3)	N3—C26—H26B	109.5
C8—C7—C6	122.9 (3)	H26A—C26—H26B	109.5
C11—C7—C6	119.2 (3)	N3—C26—H26C	109.5
C9—C8—C7	119.5 (3)	H26A—C26—H26C	109.5
C9—C8—H8	120.3	H26B—C26—H26C	109.5
O2—Cd1—N1—C10	13.5 (3)	Cd1—N1—C11—C12	−5.6 (4)
O1—Cd1—N1—C10	−96.2 (3)	C8—C7—C11—N1	0.5 (4)
N2—Cd1—N1—C10	−175.0 (3)	C6—C7—C11—N1	−178.8 (3)
O5^i—Cd1—N1—C10	105.8 (3)	C8—C7—C11—C12	−178.4 (3)
O4^i—Cd1—N1—C10	141.3 (2)	C6—C7—C11—C12	2.4 (4)
O3—Cd1—N1—C10	−13.2 (2)	C1—N2—C12—C4	1.0 (5)
O2—Cd1—N1—C11	−163.7 (2)	Cd1—N2—C12—C4	−171.0 (2)
O1—Cd1—N1—C11	86.6 (2)	C1—N2—C12—C11	−177.7 (3)
N2—Cd1—N1—C11	7.8 (2)	Cd1—N2—C12—C11	10.4 (3)
O5^i—Cd1—N1—C11	−71.4 (2)	C3—C4—C12—N2	1.1 (5)
O4^i—Cd1—N1—C11	−35.9 (3)	C5—C4—C12—N2	−176.8 (3)
O3—Cd1—N1—C11	169.6 (2)	C3—C4—C12—C11	179.7 (3)
O2—Cd1—N2—C1	−19.3 (4)	C5—C4—C12—C11	1.8 (4)
O1—Cd1—N2—C1	75.7 (3)	N1—C11—C12—N2	−3.4 (4)
N1—Cd1—N2—C1	179.3 (3)	C7—C11—C12—N2	175.5 (3)
O5^i—Cd1—N2—C1	−82.7 (3)	N1—C11—C12—C4	177.9 (3)
O4^i—Cd1—N2—C1	−28.0 (3)	C7—C11—C12—C4	−3.2 (4)
O3—Cd1—N2—C1	145.2 (3)	Cd1—O3—C13—O2	−1.3 (4)
O2—Cd1—N2—C12	152.0 (3)	Cd1—O3—C13—C14	177.9 (3)
O1—Cd1—N2—C12	−113.0 (2)	Cd1—O2—C13—O3	1.4 (4)
N1—Cd1—N2—C12	−9.4 (2)	Cd1—O2—C13—C14	−177.8 (2)
O5^i—Cd1—N2—C12	88.6 (2)	O3—C13—C14—C15	156.0 (3)
O4^i—Cd1—N2—C12	143.3 (2)	O2—C13—C14—C15	−24.7 (5)
O3—Cd1—N2—C12	−43.5 (3)	O3—C13—C14—C19	−22.2 (5)
O1—Cd1—O2—C13	76.5 (2)	O2—C13—C14—C19	157.0 (3)
N1—Cd1—O2—C13	−34.1 (3)	C19—C14—C15—C16	1.4 (5)
N2—Cd1—O2—C13	168.8 (2)	C13—C14—C15—C16	−176.9 (3)
O5^i—Cd1—O2—C13	−129.0 (2)	C19—C14—C15—C20	177.9 (3)
O4^i—Cd1—O2—C13	177.5 (2)	C13—C14—C15—C20	−0.3 (5)
O3—Cd1—O2—C13	−0.7 (2)	C14—C15—C16—C17	−1.2 (5)
O2—Cd1—O3—C13	0.7 (2)	C20—C15—C16—C17	−178.0 (3)
O1—Cd1—O3—C13	−103.4 (2)	C21—O6—C17—C18	168.9 (3)
N1—Cd1—O3—C13	155.4 (2)	C21—O6—C17—C16	−12.4 (5)
N2—Cd1—O3—C13	−172.49 (19)	C15—C16—C17—C18	−0.8 (5)
O5^i—Cd1—O3—C13	64.9 (2)	C15—C16—C17—O6	−179.4 (3)
O4^i—Cd1—O3—C13	−1.7 (3)	O6—C17—C18—C19	−178.7 (3)
C12—N2—C1—C2	−1.7 (5)	C16—C17—C18—C19	2.5 (5)
Cd1—N2—C1—C2	169.4 (3)	C17—C18—C19—C14	−2.3 (5)
N2—C1—C2—C3	0.2 (6)	C15—C14—C19—C18	0.4 (5)
C1—C2—C3—C4	1.9 (5)	C13—C14—C19—C18	178.7 (3)
C2—C3—C4—C12	−2.5 (5)	Cd1^i—O4—C20—O5	2.6 (3)
C2—C3—C4—C5	175.3 (3)	Cd1^i—O4—C20—C15	−171.3 (2)
C3—C4—C5—C6	−177.3 (3)	Cd1^i—O5—C20—O4	−2.7 (3)
C12—C4—C5—C6	0.4 (5)	Cd1^i—O5—C20—C15	171.2 (2)
C4—C5—C6—C7	−1.3 (5)	C14—C15—C20—O4	−90.0 (4)
C5—C6—C7—C8	−179.4 (3)	C16—C15—C20—O4	86.6 (3)
C5—C6—C7—C11	−0.2 (5)	C14—C15—C20—O5	95.7 (4)
C11—C7—C8—C9	1.3 (5)	C16—C15—C20—O5	−87.6 (4)
C6—C7—C8—C9	−179.5 (3)	C17—O6—C21—C23	−87.8 (4)
C7—C8—C9—C10	−1.6 (5)	C17—O6—C21—C22	99.0 (4)
C11—N1—C10—C9	1.5 (5)	C23—C21—C22—C23^ii	−0.2 (6)
Cd1—N1—C10—C9	−175.6 (2)	O6—C21—C22—C23^ii	172.9 (3)
C8—C9—C10—N1	0.2 (5)	C22—C21—C23—C22^ii	0.1 (6)
C10—N1—C11—C7	−1.9 (4)	O6—C21—C23—C22^ii	−172.9 (3)
Cd1—N1—C11—C7	175.6 (2)	C25—N3—C24—O7	−179.7 (6)
C10—N1—C11—C12	177.0 (3)	C26—N3—C24—O7	−1.2 (8)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O2^iii	0.85	1.99	2.7853 (2)	156
O1—H1C···O4^iv	0.85	2.03	2.7836 (2)	147

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