Two-dimensional Zn^II and one-dimensional Co^II coordination polymers based on benzene-1,4-di­carboxyl­ate and pyridine ligands

Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxyl­ate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene-1,4-di­carb­oxy­lic acid (H₂BDC) and pyridine (py) with Zn^II or Co^II yielded two new coordination polymers, namely, poly[(μ₄-benzene-1,4-di­carboxyl­ato-κ⁴O:O′:O′′:O′′′)(pyridine-κN)zinc(II)], [Zn(C₈H₄O₂)(C₅H₅N)]_n, (I), and catena-poly[aqua­(μ₃-benzene-1,4-di­carboxyl­ato-κ³O:O′:O′′)bis­(pyri­dine-κN)cobalt(II)], [Co(C₈H₄O₂)(C₅H₅N)₂(H₂O)]_n, (II). In compound (I), the Zn^II cation is five-coordinated by four carboxyl­ate O atoms from four BDC²⁻ ligands and one pyridine N atom in a distorted square-pyramidal coordination geometry. Four carboxyl­ate groups bridge two Zn^II ions to form centrosymmetric paddle-wheel-like Zn₂(μ₂-COO)₄ units, which are linked by the benzene rings of the BDC²⁻ ligands to generate a two-dimensional layered structure. The two-dimensional layer is extended into a three-dimensional supra­molecular structure with the help of π–π stacking inter­actions between the aromatic rings. Compound (II) has a one-dimensional double-chain structure based on Co₂(μ₂-COO)₂ units. The Co^II cations are bridged by BDC²⁻ ligands and are octa­hedrally coordinated by three carboxyl­ate O atoms from three BDC²⁻ ligands, one water O atom and two pyridine N atoms. Inter­chain O—H...O hydrogen-bonding inter­actions link these chains to form a three-dimensional supra­molecular architecture.

S1. Introduction

Coordination polymers constructed from metal ions and organic ligands, emerging as a new class of functional materials, have attracted considerable attention owing to their diverse structural topologies and potential applications in gas storage, molecular magnets, photoluminescence and catalysis (Eddaoudi et al., 2001; Cui et al., 2012; Allendorf et al., 2009; Wang et al., 2008). As the key components for the coordination polymers, the organic ligands play a vital role in functional coordination polymers. Among the various ligands, those containing carboxyl­ate groups are among the most extensively studied because of their versatile coordination modes (Yaghi et al., 1997; Lin et al., 2007). Benzene-1,4-di­carb­oxy­lic acid (H₂BDC) can exhibit ten coordination modes through its four carboxyl­ate O atoms (see Scheme 2). Although many coordination polymers have been reported to date, new compounds based on H₂BDC are observed regularly (Liu et al., 2014; Song et al., 2012). Coordination polymers with a single H₂BDC ligand commonly show three-dimensional structures, due to the two carboxyl­ate groups being arranged in the para positions the central benzene, and structural robustness (Liu et al., 2014). Moreover, many coordination polymers with H₂BDC and N-containing ligands displaying diverse structures have been documented (Tao et al., 2000; Li et al., 2010). If a ligand with one donor atom is incorporated as a terminal ligand in the M–H₂BDC system (M is a metal ion), low-dimensional structures can be obtained. For example, H₂BDC has been used in the construction of discrete molecular triangles due to its rigid linear character, which has potential applications in catalysts and molecular sensors (Cotton et al., 2004;). Moreover, two-dimensional compounds with flexible porous characters exhibit framework structure changes during the adsorption process, which would be the key to fine-tuning of the gas-adsorption performance of porous coordination polymers (Tanaka et al., 2008).

In this contribution, we employed pyridine (py) as the terminal ligand and benzene-1,4-di­carboxyl­ate (BDC^2-) as bridging ligand to constructe coordination polymers with inter­esting structural features, namely, catena-poly[(µ₄-benzene-1,4-di­carboxyl­ato)(pyridine)­zinc(II)], (I), and poly[aqua­(µ₃-benzene-1,4-di­carboxyl­ato)bis­(pyridine)­cobalt(II)], (II).

S2. Experimental

S2.1. Synthesis, crystallization and IR data

An aqueous solution (2 ml) of Zn(CH₃COO)₂.2H₂O (21.9 mg, 0.10 mmol) was added to a di­methyl sulfoxide solution (4 ml) of benzene-1,4-di­carb­oxy­lic acid (16.6 mg, 0.10 mmol) and pyridine (2 ml). The resulting mixture was transfered into a 25 ml Parr Teflon-lined stainless steel vessel. The vessel was sealed and heated to 373 K. The temperature was maintained for 2 d and the mixture was then allowed to cool naturally, giving colourless crystals [yield 37%, based on Zn(CH₃COO)₂.2H₂O]. IR (KBr pellet, ν, cm^-1): 3419, 1609, 1585, 1550, 1504, 1487, 1450, 1400, 1379, 1309, 1215, 1151, 1066, 1047, 1019, 879, 848, 837, 761, 749, 738, 705, 642, 587, 564. For the synthesis of (II), Co(CH₃COO)₂.4H₂O (24.9 mg, 0.10 mmol) was used instead of Zn(CH₃COO)₂.2H₂O. Using the same method as for the preparation of (I), suitable dark-red crystals of (II) were obtained [yield 49%, based on Co(CH₃COO)₂.4H₂O]. IR (KBr pellet, ν, cm^-1): 3231, 1602, 1551, 1446, 1378, 1217, 1153, 1112, 1092, 1070, 1040, 1014, 893, 755, 698, 634, 510, 503.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C atoms were placed in calculated positions and treated using a riding-model approximation, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). Water H atoms were located in a difference map and refined with O—H = 0.85 Å and U_iso(H) = 1.5U_eq(O).

S3. Results and discussion

Compound (I) crystallizes in the monoclinic space group P2₁/n and the asymmetric unit contains one Zn^II cation, one dianionic BDC^2- ligand and one py ligand. As depicted in Fig. 1, the coordination of the Zn1 cation is composed of four carboxyl­ate O atoms (O1, O2ⁱⁱⁱ, O4ⁱⁱ and O3ⁱ; see Fig. 1 for symmetry codes) from four BDC^2- ligands and one pyridine N atom in a distorted square-pyramidal geometry. The four O atoms form the basal square plane and the N atom takes up the apical position. The angles around the Zn^II centre (Table 2) are indicative of a distorted [ZnO₄N] square pyramid. The terminal py molecule binds in a monodentate manner to a Zn^II ion and the BDC^2- ligand adopts a tetra­dentate bridging coordination mode through its four monodentate carboxyl­ate O atoms [see (a) in Scheme 12]. As shown in Fig. 1, four carboxyl­ate groups bridge two Zn^II ions to give a centrosymmetric paddle-wheel-like Zn₂(µ₂-COO)₄ unit with two py molecules located at the axial positions and a Zn···Zn separation of 2.9883 (5) Å. The dinuclear Zn₂(µ2-COO)₄(py)₂ units are linked by the benzene rings of BDC^2- ligands to generate a two-dimensional network featuring nanosized square cavities, as depicted in Fig. 2. The two-dimensional layer extends along the (101) direction, with Zn···Zn separations are 10.72 (3) and 11.09 (3) Å in a square cavity. These two-dimensional layers are stacked along the (101) direction to form the three-dimensional crystal packing (Fig. 3). As shown in Fig. 4, in the crystal packing, the py ligands of adjacent layers protrude into the square cavities of the two-dimensional layer. Inter­layer π–π stacking inter­actions are observed between benzene and pyridine rings and between pyridine rings (Figs. 3 and 4), which are arranged in an offset fashion; the dihedral angles are 22.86 (1) and 0°, respectively, and centroid-to-centroid distances are 3.89 (1) and 3.75 (2) Å , respectively.

One-dimensional Co^II coordination polymer (II) crystallizes in the monoclinic space group C2/c. The asymmetric unit consists of one Co^II atom, one BDC^2- ligand, one coordinated water molecule and two py ligands. As shown in Fig. 5, the central Co^II cation is six-coordinated by three carboxyl­ate O atoms (O1, O2ⁱⁱ and O3ⁱ; see Fig. 5 for symmetry codes) from three BDC^2- ligands, one water O atom and two N atoms from two py ligands. The Co1 ion is located in an approximate o­cta­hedral coordination environment (see Table 2 for geometric parameters), with four O atoms forming the basal plane and two pyridine N atoms occupying the apical positions. The Co—O/N bond lengths (Table 3) are comparable with the values in related Co^II compounds (Kumar & Doctorovich, 2012; Groeneman et al., 1999 ). The py and water molecules serve as terminal ligands, coordination in a monodentate manner to the Co^II centre. The BDC^2- ligand bridges three Co^II ions through three monodentate carboxyl­ate O atoms [see (b) in Scheme 2]. A pair of µ₂-carboxyl­ate groups bridge two Co^II ions to give a centrosymmetric Co₂(µ₂-COO)₂ unit, with a Co···Co separation of 4.702 (1) Å (Fig. 5). The Co₂(µ₂-COO)₂ units are linked by the benzene rings of BDC^2- ligands to form a one-dimensional double-chain structure propagating along the (110) direction (Fig. 6). The chain is reinforced by an O1W—H1W···O4ⁱ hydrogen bond between the coordinated water molecule and a carboxyl­ate O atom (see Fig. 6 and Table 4 for geometry details and symmetry code). Within the chain, the benzene rings of the BDC^2- ligands are parallel and the closest centroid-to-centroid distance of the benzene rings is 5.15 (3) Å. Neighbouring one-dimensional chains inter­act with each other through an O1W—H2W···O4ⁱⁱⁱ hydrogen bond (Fig. 7 and Table 4). As described above, the chain runs along the (110) direction and neighbouring chains which are connected by hydrogen bonds propagate along the (110) direction (Fig. 7). The one-dimensional chains are connected by inter­chain hydrogen bonds to give a three-dimensional supra­molecular framework (Fig. 8).

It is inter­esting that compound (I) with its two-dimensional layered structure and compound (II) with its one-dimensional chain structure have been obtained under simliar reaction conditions with only different metal ions. The result indicates that the structures exhibit different dimensionality depending on the nature of the metal ions. Furthermore, the terminal py ligands occupy the axial positions of the paddle-wheel Zn₂(/m₂-COO)₄ units in the two-dimensional layer of (I), which terminate the extension of the two-dimensional Zn–BDC layer into a three-dimensional framework through coordination bonds. For (II), the terminal py and water ligands block the one-dimensional Zn–BDC chain extending into a higher dimensional architecture. To our knowledge, only three Zn^II compunds based on BDC^2- and py mixed ligands have been documented to date. {[Zn(BDC)(py)₂(H₂O)₂].2py.2H₂O}_n, with o­cta­hedral Zn centres (Ohmura et al., 2003), and [Zn(BDC)(py)(H₂O)]_n, with tetra­hedral Zn centres (Wang et al., 2002; Kim et al., 2010), possess one-dimensional chains wherein the single Zn^II centres are bridged by bidentate BDC^2- ligands. The three-dimensional structure of {[Zn₃(BDC)₃(py)₂].(1,4-dioxane)}_n features linear trinuclear zinc clusters with py molecules capping the ends of the Zn₃ unit (He et al., 2006). The BDC^2- ligands exhibit two different tetra­dentate coordination modes, i.e. with four monodentate carboxyl­ate O atoms or with two bidentate carboxyl­ate O atoms.

Three Co^II compounds incorporating BDC^2- and py mixed ligands have been reported previously. Two have the same formula, i.e. {[Co(BDC)(py)₂(H₂O)₂].2py.2H₂O}_n (Kumar & Doctorovich, 2012; Groeneman et al., 1999), and display similar one-dimesional chain structures wherein the BDC^2- ligands link the Co^II ions. However, they crystallize in different space groups, namely with P2₁/n and P2₁/c. The third compound, {[Co₂(BDC)₂(py)₄].py.2DMF}_n (DMF is di­methyl­formamide), is a two-dimensional network based on the dinuclear Co₂(µ₂-COO)₂ unit (Shi et al., 2003), featuring rhomboid cavities occulded by the solvate py molecules, with the DMF solvent molecules are located in the spaces between the two-dimesional layers. The Co^II ions in all these compounds, together with compound (II), display six-coordinated o­cta­hedral coordination enviroments. However, compound (II) with its double chain structure is totally different from the three previously reported structures.

Compound (I) exhibits a broad photoluminescence emission centred at 434 nm with a shoulder peak at 470 nm upon excitation at 338 nm (Fig. 9). It has been reported that free H₂BDC exhibits a broad photoluminescence emission centred at 382 nm upon excitation at 314 nm (Song et al., 2012). The emission peak at 334 nm can be assigned to an intra-ligand fluorescence emission. Compared with the emission of free H₂BDC, a bathochromic shift was observed in the emssion spectrum of compound (I), which resulted from the coordination of Zn^II cations. The lower energy (470 nm) emission of compound (I) can be tentatively assigned to oxygen and nitro­gen to zinc ligand-to-metal charge-transfer (LMCT) transitions, which is similar to what if found in other Zn^II compounds (Zheng & Chen, 2004).

Structure description

Coordination polymers constructed from metal ions and organic ligands, emerging as a new class of functional materials, have attracted considerable attention owing to their diverse structural topologies and potential applications in gas storage, molecular magnets, photoluminescence and catalysis (Eddaoudi et al., 2001; Cui et al., 2012; Allendorf et al., 2009; Wang et al., 2008). As the key components for the coordination polymers, the organic ligands play a vital role in functional coordination polymers. Among the various ligands, those containing carboxyl­ate groups are among the most extensively studied because of their versatile coordination modes (Yaghi et al., 1997; Lin et al., 2007). Benzene-1,4-di­carb­oxy­lic acid (H₂BDC) can exhibit ten coordination modes through its four carboxyl­ate O atoms (see Scheme 2). Although many coordination polymers have been reported to date, new compounds based on H₂BDC are observed regularly (Liu et al., 2014; Song et al., 2012). Coordination polymers with a single H₂BDC ligand commonly show three-dimensional structures, due to the two carboxyl­ate groups being arranged in the para positions the central benzene, and structural robustness (Liu et al., 2014). Moreover, many coordination polymers with H₂BDC and N-containing ligands displaying diverse structures have been documented (Tao et al., 2000; Li et al., 2010). If a ligand with one donor atom is incorporated as a terminal ligand in the M–H₂BDC system (M is a metal ion), low-dimensional structures can be obtained. For example, H₂BDC has been used in the construction of discrete molecular triangles due to its rigid linear character, which has potential applications in catalysts and molecular sensors (Cotton et al., 2004;). Moreover, two-dimensional compounds with flexible porous characters exhibit framework structure changes during the adsorption process, which would be the key to fine-tuning of the gas-adsorption performance of porous coordination polymers (Tanaka et al., 2008).

In this contribution, we employed pyridine (py) as the terminal ligand and benzene-1,4-di­carboxyl­ate (BDC^2-) as bridging ligand to constructe coordination polymers with inter­esting structural features, namely, catena-poly[(µ₄-benzene-1,4-di­carboxyl­ato)(pyridine)­zinc(II)], (I), and poly[aqua­(µ₃-benzene-1,4-di­carboxyl­ato)bis­(pyridine)­cobalt(II)], (II).

Compound (I) crystallizes in the monoclinic space group P2₁/n and the asymmetric unit contains one Zn^II cation, one dianionic BDC^2- ligand and one py ligand. As depicted in Fig. 1, the coordination of the Zn1 cation is composed of four carboxyl­ate O atoms (O1, O2ⁱⁱⁱ, O4ⁱⁱ and O3ⁱ; see Fig. 1 for symmetry codes) from four BDC^2- ligands and one pyridine N atom in a distorted square-pyramidal geometry. The four O atoms form the basal square plane and the N atom takes up the apical position. The angles around the Zn^II centre (Table 2) are indicative of a distorted [ZnO₄N] square pyramid. The terminal py molecule binds in a monodentate manner to a Zn^II ion and the BDC^2- ligand adopts a tetra­dentate bridging coordination mode through its four monodentate carboxyl­ate O atoms [see (a) in Scheme 12]. As shown in Fig. 1, four carboxyl­ate groups bridge two Zn^II ions to give a centrosymmetric paddle-wheel-like Zn₂(µ₂-COO)₄ unit with two py molecules located at the axial positions and a Zn···Zn separation of 2.9883 (5) Å. The dinuclear Zn₂(µ2-COO)₄(py)₂ units are linked by the benzene rings of BDC^2- ligands to generate a two-dimensional network featuring nanosized square cavities, as depicted in Fig. 2. The two-dimensional layer extends along the (101) direction, with Zn···Zn separations are 10.72 (3) and 11.09 (3) Å in a square cavity. These two-dimensional layers are stacked along the (101) direction to form the three-dimensional crystal packing (Fig. 3). As shown in Fig. 4, in the crystal packing, the py ligands of adjacent layers protrude into the square cavities of the two-dimensional layer. Inter­layer π–π stacking inter­actions are observed between benzene and pyridine rings and between pyridine rings (Figs. 3 and 4), which are arranged in an offset fashion; the dihedral angles are 22.86 (1) and 0°, respectively, and centroid-to-centroid distances are 3.89 (1) and 3.75 (2) Å , respectively.

One-dimensional Co^II coordination polymer (II) crystallizes in the monoclinic space group C2/c. The asymmetric unit consists of one Co^II atom, one BDC^2- ligand, one coordinated water molecule and two py ligands. As shown in Fig. 5, the central Co^II cation is six-coordinated by three carboxyl­ate O atoms (O1, O2ⁱⁱ and O3ⁱ; see Fig. 5 for symmetry codes) from three BDC^2- ligands, one water O atom and two N atoms from two py ligands. The Co1 ion is located in an approximate o­cta­hedral coordination environment (see Table 2 for geometric parameters), with four O atoms forming the basal plane and two pyridine N atoms occupying the apical positions. The Co—O/N bond lengths (Table 3) are comparable with the values in related Co^II compounds (Kumar & Doctorovich, 2012; Groeneman et al., 1999 ). The py and water molecules serve as terminal ligands, coordination in a monodentate manner to the Co^II centre. The BDC^2- ligand bridges three Co^II ions through three monodentate carboxyl­ate O atoms [see (b) in Scheme 2]. A pair of µ₂-carboxyl­ate groups bridge two Co^II ions to give a centrosymmetric Co₂(µ₂-COO)₂ unit, with a Co···Co separation of 4.702 (1) Å (Fig. 5). The Co₂(µ₂-COO)₂ units are linked by the benzene rings of BDC^2- ligands to form a one-dimensional double-chain structure propagating along the (110) direction (Fig. 6). The chain is reinforced by an O1W—H1W···O4ⁱ hydrogen bond between the coordinated water molecule and a carboxyl­ate O atom (see Fig. 6 and Table 4 for geometry details and symmetry code). Within the chain, the benzene rings of the BDC^2- ligands are parallel and the closest centroid-to-centroid distance of the benzene rings is 5.15 (3) Å. Neighbouring one-dimensional chains inter­act with each other through an O1W—H2W···O4ⁱⁱⁱ hydrogen bond (Fig. 7 and Table 4). As described above, the chain runs along the (110) direction and neighbouring chains which are connected by hydrogen bonds propagate along the (110) direction (Fig. 7). The one-dimensional chains are connected by inter­chain hydrogen bonds to give a three-dimensional supra­molecular framework (Fig. 8).

It is inter­esting that compound (I) with its two-dimensional layered structure and compound (II) with its one-dimensional chain structure have been obtained under simliar reaction conditions with only different metal ions. The result indicates that the structures exhibit different dimensionality depending on the nature of the metal ions. Furthermore, the terminal py ligands occupy the axial positions of the paddle-wheel Zn₂(/m₂-COO)₄ units in the two-dimensional layer of (I), which terminate the extension of the two-dimensional Zn–BDC layer into a three-dimensional framework through coordination bonds. For (II), the terminal py and water ligands block the one-dimensional Zn–BDC chain extending into a higher dimensional architecture. To our knowledge, only three Zn^II compunds based on BDC^2- and py mixed ligands have been documented to date. {[Zn(BDC)(py)₂(H₂O)₂].2py.2H₂O}_n, with o­cta­hedral Zn centres (Ohmura et al., 2003), and [Zn(BDC)(py)(H₂O)]_n, with tetra­hedral Zn centres (Wang et al., 2002; Kim et al., 2010), possess one-dimensional chains wherein the single Zn^II centres are bridged by bidentate BDC^2- ligands. The three-dimensional structure of {[Zn₃(BDC)₃(py)₂].(1,4-dioxane)}_n features linear trinuclear zinc clusters with py molecules capping the ends of the Zn₃ unit (He et al., 2006). The BDC^2- ligands exhibit two different tetra­dentate coordination modes, i.e. with four monodentate carboxyl­ate O atoms or with two bidentate carboxyl­ate O atoms.

Three Co^II compounds incorporating BDC^2- and py mixed ligands have been reported previously. Two have the same formula, i.e. {[Co(BDC)(py)₂(H₂O)₂].2py.2H₂O}_n (Kumar & Doctorovich, 2012; Groeneman et al., 1999), and display similar one-dimesional chain structures wherein the BDC^2- ligands link the Co^II ions. However, they crystallize in different space groups, namely with P2₁/n and P2₁/c. The third compound, {[Co₂(BDC)₂(py)₄].py.2DMF}_n (DMF is di­methyl­formamide), is a two-dimensional network based on the dinuclear Co₂(µ₂-COO)₂ unit (Shi et al., 2003), featuring rhomboid cavities occulded by the solvate py molecules, with the DMF solvent molecules are located in the spaces between the two-dimesional layers. The Co^II ions in all these compounds, together with compound (II), display six-coordinated o­cta­hedral coordination enviroments. However, compound (II) with its double chain structure is totally different from the three previously reported structures.

Compound (I) exhibits a broad photoluminescence emission centred at 434 nm with a shoulder peak at 470 nm upon excitation at 338 nm (Fig. 9). It has been reported that free H₂BDC exhibits a broad photoluminescence emission centred at 382 nm upon excitation at 314 nm (Song et al., 2012). The emission peak at 334 nm can be assigned to an intra-ligand fluorescence emission. Compared with the emission of free H₂BDC, a bathochromic shift was observed in the emssion spectrum of compound (I), which resulted from the coordination of Zn^II cations. The lower energy (470 nm) emission of compound (I) can be tentatively assigned to oxygen and nitro­gen to zinc ligand-to-metal charge-transfer (LMCT) transitions, which is similar to what if found in other Zn^II compounds (Zheng & Chen, 2004).

Synthesis and crystallization

An aqueous solution (2 ml) of Zn(CH₃COO)₂.2H₂O (21.9 mg, 0.10 mmol) was added to a di­methyl sulfoxide solution (4 ml) of benzene-1,4-di­carb­oxy­lic acid (16.6 mg, 0.10 mmol) and pyridine (2 ml). The resulting mixture was transfered into a 25 ml Parr Teflon-lined stainless steel vessel. The vessel was sealed and heated to 373 K. The temperature was maintained for 2 d and the mixture was then allowed to cool naturally, giving colourless crystals [yield 37%, based on Zn(CH₃COO)₂.2H₂O]. IR (KBr pellet, ν, cm^-1): 3419, 1609, 1585, 1550, 1504, 1487, 1450, 1400, 1379, 1309, 1215, 1151, 1066, 1047, 1019, 879, 848, 837, 761, 749, 738, 705, 642, 587, 564. For the synthesis of (II), Co(CH₃COO)₂.4H₂O (24.9 mg, 0.10 mmol) was used instead of Zn(CH₃COO)₂.2H₂O. Using the same method as for the preparation of (I), suitable dark-red crystals of (II) were obtained [yield 49%, based on Co(CH₃COO)₂.4H₂O]. IR (KBr pellet, ν, cm^-1): 3231, 1602, 1551, 1446, 1378, 1217, 1153, 1112, 1092, 1070, 1040, 1014, 893, 755, 698, 634, 510, 503.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C atoms were placed in calculated positions and treated using a riding-model approximation, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). Water H atoms were located in a difference map and refined with O—H = 0.85 Å and U_iso(H) = 1.5U_eq(O).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and the paddle-wheel Zn2(µ2-COO)4 unit. All H atoms have been omitted for clarity. [Symmetry codes: (i) -x + 1/2, y - 1/2, -z + 3/2; (ii) x + 1/2, -y + 1/2, z - 1/2; (iii) -x + 1, -y, -z + 1.]
	Fig. 2. A view of two-dimensional layer in (I), showing the nanosized square cavities.
	Fig. 3. A view of the three-dimensional supramolecular framework of (I) along the a axis. The dashed lines indicate the π–π stacking interactions between the layers.
	Fig. 4. A view of the π–π stacking interactions (dashed lines) between the aromatic rings from neighbouring layers in (I).
	Fig. 5. The structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. All H atoms have been omitted for clarity, except for H atoms attached to the O atoms, which are shown as small spheres of arbitrary radii. [Symmetry codes: (i) x + 1/2, y - 1/2, z; (ii) -x + 1/2, -y + 1/2, -z + 1.]
	Fig. 6. A perspective view of the one-dimensional double chain of (II), showing the dinuclear Co2(µ2-COO)2 unit. [Symmetry codes: (i) -x + 1/2, -y + 1/2, -z + 1; (ii) x + 1/2, y - 1/2, z.]
	Fig. 7. A perspective view of the hydrogen-bonding interactions (dashed lines) between the chains in (II). [Symmetry code: (iii) -x, y, -z + 1/2.]
	Fig. 8. A view of the three-dimensional supramolecular framework of (II) along the b axis. Only the interchain hydrogen bonds (dashed lines) are shown.
	Fig. 9. The photoluminescence spectrum for (I).

(I) Poly[(µ₄-benzene-1,4-dicarboxylato-κ⁴O:O':O'':O''')(pyridine-κN)zinc(II)]

Crystal data

[Zn(C8H4O2)(C5H5N)]	F(000) = 624
Mr = 308.58	Dx = 1.672 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.3974 (8) Å	Cell parameters from 3341 reflections
b = 16.5945 (19) Å	θ = 2.4–27.1°
c = 10.3281 (12) Å	µ = 2.01 mm^−1
β = 104.815 (1)°	T = 296 K
V = 1225.7 (2) Å^3	Block, colourless
Z = 4	0.15 × 0.10 × 0.08 mm

Data collection

Bruker APEXII area-detector diffractometer	2810 independent reflections
Radiation source: fine-focus sealed tube	2309 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.752, Tmax = 0.856	k = −21→21
11645 measured reflections	l = −13→13

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.065	w = 1/[σ^2(Fo^2) + (0.0301P)^2 + 0.5535P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
2810 reflections	Δρmax = 0.35 e Å^−3
172 parameters	Δρmin = −0.38 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	0.31816 (3)	0.00733 (2)	0.39643 (2)	0.01573 (8)
O1	0.2815 (2)	0.08334 (9)	0.54514 (15)	0.0271 (4)
O2	0.5593 (2)	0.07959 (9)	0.69491 (15)	0.0282 (4)
O3	0.2800 (2)	0.41553 (9)	1.00948 (15)	0.0281 (4)
O4	0.0023 (2)	0.40783 (9)	0.86118 (17)	0.0312 (4)
N1	0.0969 (2)	0.03959 (10)	0.24232 (17)	0.0213 (4)
C1	0.3390 (3)	0.17793 (12)	0.7210 (2)	0.0192 (4)
C2	0.1500 (3)	0.19416 (12)	0.7052 (2)	0.0247 (5)
H2A	0.0602	0.1606	0.6521	0.030*
C3	0.0953 (3)	0.26003 (12)	0.7681 (2)	0.0247 (5)
H3A	−0.0312	0.2706	0.7568	0.030*
C4	0.2282 (3)	0.31049 (12)	0.8482 (2)	0.0210 (4)
C5	0.4170 (3)	0.29396 (12)	0.8648 (2)	0.0234 (5)
H5A	0.5069	0.3272	0.9184	0.028*
C6	0.4715 (3)	0.22803 (12)	0.8018 (2)	0.0234 (5)
H6A	0.5980	0.2172	0.8137	0.028*
C7	0.3984 (3)	0.10813 (11)	0.6479 (2)	0.0202 (4)
C8	0.1657 (3)	0.38364 (11)	0.9115 (2)	0.0212 (4)
C9	−0.0760 (3)	0.01499 (13)	0.2408 (2)	0.0272 (5)
H9A	−0.0926	−0.0161	0.3119	0.033*
C10	−0.2305 (4)	0.03371 (17)	0.1386 (3)	0.0413 (6)
H10A	−0.3485	0.0150	0.1400	0.050*
C11	−0.2065 (4)	0.08052 (17)	0.0349 (3)	0.0496 (8)
H11A	−0.3083	0.0939	−0.0355	0.060*
C12	−0.0307 (4)	0.10744 (17)	0.0360 (3)	0.0484 (7)
H12A	−0.0122	0.1398	−0.0329	0.058*
C13	0.1183 (4)	0.08587 (14)	0.1408 (2)	0.0339 (6)
H13A	0.2373	0.1040	0.1410	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01813 (13)	0.01276 (12)	0.01667 (13)	0.00021 (9)	0.00509 (9)	0.00052 (9)
O1	0.0298 (9)	0.0256 (8)	0.0254 (8)	0.0020 (6)	0.0063 (7)	−0.0112 (6)
O2	0.0288 (9)	0.0265 (8)	0.0287 (9)	0.0099 (7)	0.0062 (7)	−0.0080 (7)
O3	0.0348 (9)	0.0212 (7)	0.0278 (9)	0.0051 (6)	0.0073 (7)	−0.0083 (6)
O4	0.0290 (9)	0.0257 (8)	0.0399 (10)	0.0089 (7)	0.0107 (8)	−0.0090 (7)
N1	0.0240 (10)	0.0205 (8)	0.0194 (9)	0.0023 (7)	0.0058 (8)	0.0010 (7)
C1	0.0249 (11)	0.0160 (9)	0.0182 (10)	0.0034 (8)	0.0081 (9)	−0.0014 (8)
C2	0.0246 (12)	0.0211 (10)	0.0279 (12)	0.0001 (9)	0.0057 (9)	−0.0069 (9)
C3	0.0207 (11)	0.0231 (10)	0.0317 (12)	0.0045 (9)	0.0093 (9)	−0.0052 (9)
C4	0.0263 (12)	0.0163 (9)	0.0222 (11)	0.0042 (8)	0.0094 (9)	−0.0015 (8)
C5	0.0261 (11)	0.0203 (10)	0.0229 (11)	−0.0006 (9)	0.0047 (9)	−0.0065 (8)
C6	0.0198 (11)	0.0224 (10)	0.0280 (12)	0.0047 (8)	0.0059 (9)	−0.0034 (9)
C7	0.0278 (12)	0.0149 (9)	0.0214 (11)	0.0006 (8)	0.0126 (9)	−0.0003 (8)
C8	0.0288 (12)	0.0144 (9)	0.0247 (11)	0.0022 (8)	0.0147 (9)	0.0000 (8)
C9	0.0245 (12)	0.0293 (11)	0.0278 (12)	0.0011 (9)	0.0068 (10)	−0.0005 (9)
C10	0.0264 (14)	0.0511 (16)	0.0414 (16)	0.0051 (12)	−0.0003 (12)	−0.0036 (13)
C11	0.0465 (18)	0.0529 (17)	0.0376 (16)	0.0138 (14)	−0.0108 (13)	0.0030 (13)
C12	0.067 (2)	0.0468 (17)	0.0272 (14)	0.0070 (14)	0.0040 (14)	0.0168 (12)
C13	0.0400 (15)	0.0353 (13)	0.0265 (12)	−0.0023 (11)	0.0086 (11)	0.0073 (10)

Geometric parameters (Å, º)

Zn1—O3^i	2.0378 (14)	C2—C3	1.384 (3)
Zn1—N1	2.0412 (18)	C2—H2A	0.9300
Zn1—O4^ii	2.0550 (15)	C3—C4	1.391 (3)
Zn1—O2^iii	2.0565 (14)	C3—H3A	0.9300
Zn1—O1	2.0584 (14)	C4—C5	1.391 (3)
Zn1—Zn1^iii	2.9883 (5)	C4—C8	1.506 (3)
O1—C7	1.254 (3)	C5—C6	1.384 (3)
O2—C7	1.258 (2)	C5—H5A	0.9300
O2—Zn1^iii	2.0565 (14)	C6—H6A	0.9300
O3—C8	1.258 (3)	C9—C10	1.378 (3)
O3—Zn1^iv	2.0378 (14)	C9—H9A	0.9300
O4—C8	1.254 (3)	C10—C11	1.371 (4)
O4—Zn1^v	2.0549 (14)	C10—H10A	0.9300
N1—C9	1.339 (3)	C11—C12	1.372 (4)
N1—C13	1.341 (3)	C11—H11A	0.9300
C1—C6	1.389 (3)	C12—C13	1.380 (3)
C1—C2	1.392 (3)	C12—H12A	0.9300
C1—C7	1.508 (3)	C13—H13A	0.9300
O3^i—Zn1—N1	104.80 (7)	C3—C4—C8	119.64 (19)
O3^i—Zn1—O4^ii	158.38 (6)	C6—C5—C4	120.1 (2)
N1—Zn1—O4^ii	96.77 (7)	C6—C5—H5A	120.0
O3^i—Zn1—O2^iii	86.96 (6)	C4—C5—H5A	120.0
N1—Zn1—O2^iii	100.71 (7)	C5—C6—C1	120.7 (2)
O4^ii—Zn1—O2^iii	90.54 (7)	C5—C6—H6A	119.7
O3^i—Zn1—O1	88.36 (6)	C1—C6—H6A	119.7
N1—Zn1—O1	100.88 (7)	O1—C7—O2	125.64 (18)
O4^ii—Zn1—O1	86.11 (6)	O1—C7—C1	116.72 (18)
O2^iii—Zn1—O1	158.40 (6)	O2—C7—C1	117.64 (18)
C7—O1—Zn1	129.67 (14)	O4—C8—O3	125.26 (18)
C7—O2—Zn1^iii	124.87 (13)	O4—C8—C4	116.65 (19)
C8—O3—Zn1^iv	116.77 (14)	O3—C8—C4	118.10 (19)
C8—O4—Zn1^v	139.34 (14)	N1—C9—C10	122.8 (2)
C9—N1—C13	118.0 (2)	N1—C9—H9A	118.6
C9—N1—Zn1	120.14 (15)	C10—C9—H9A	118.6
C13—N1—Zn1	121.90 (16)	C11—C10—C9	118.6 (3)
C6—C1—C2	119.18 (18)	C11—C10—H10A	120.7
C6—C1—C7	120.66 (19)	C9—C10—H10A	120.7
C2—C1—C7	120.14 (18)	C10—C11—C12	119.3 (2)
C3—C2—C1	120.2 (2)	C10—C11—H11A	120.4
C3—C2—H2A	119.9	C12—C11—H11A	120.4
C1—C2—H2A	119.9	C11—C12—C13	119.2 (3)
C2—C3—C4	120.5 (2)	C11—C12—H12A	120.4
C2—C3—H3A	119.8	C13—C12—H12A	120.4
C4—C3—H3A	119.8	N1—C13—C12	122.1 (2)
C5—C4—C3	119.32 (18)	N1—C13—H13A	119.0
C5—C4—C8	121.00 (19)	C12—C13—H13A	119.0

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

(II) catena-Poly[aqua(µ₃-benzene-1,4-dicarboxylato-κ³O:O':O'')bis(pyridine-κN)cobalt(II)]

Crystal data

[Co(C8H4O4)(C5H5N)2(H2O)]	F(000) = 1640
Mr = 399.26	Dx = 1.541 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.8487 (11) Å	Cell parameters from 4453 reflections
b = 8.9363 (5) Å	θ = 2.5–27.2°
c = 20.7360 (11) Å	µ = 1.03 mm^−1
β = 117.032 (1)°	T = 293 K
V = 3441.3 (3) Å^3	Prism, red
Z = 8	0.20 × 0.18 × 0.08 mm

Data collection

Bruker APEXII area-detector diffractometer	3843 independent reflections
Radiation source: fine-focus sealed tube	3306 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ω scans	θmax = 27.4°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −26→20
Tmin = 0.821, Tmax = 0.922	k = −11→10
9923 measured reflections	l = −23→26

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.072	w = 1/[σ^2(Fo^2) + (0.0385P)^2 + 2.2146P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
3843 reflections	Δρmax = 0.35 e Å^−3
235 parameters	Δρmin = −0.23 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
Co1	0.26189 (2)	0.17750 (2)	0.39693 (2)	0.01908 (8)
O1	0.16985 (6)	0.28302 (13)	0.38684 (6)	0.0267 (3)
O1W	0.21784 (6)	0.21354 (13)	0.28269 (6)	0.0284 (3)
H1W	0.2408	0.1575	0.2672	0.043*
H2W	0.2091	0.2986	0.2622	0.043*
O2	0.19925 (6)	0.38425 (14)	0.49514 (6)	0.0254 (2)
O3	−0.15237 (6)	0.57903 (14)	0.38964 (6)	0.0304 (3)
O4	−0.19237 (6)	0.48980 (14)	0.27752 (6)	0.0333 (3)
N1	0.20131 (7)	−0.03183 (16)	0.36720 (7)	0.0270 (3)
N2	0.32758 (7)	0.38054 (17)	0.42352 (8)	0.0286 (3)
C1	0.07750 (8)	0.39708 (17)	0.40482 (8)	0.0200 (3)
C2	0.05977 (8)	0.5058 (2)	0.44202 (9)	0.0292 (4)
H2A	0.0958	0.5519	0.4824	0.035*
C3	−0.01156 (9)	0.5453 (2)	0.41883 (9)	0.0304 (4)
H3A	−0.0229	0.6186	0.4438	0.036*
C4	−0.06648 (8)	0.47754 (18)	0.35890 (8)	0.0218 (3)
C5	−0.04863 (8)	0.3730 (2)	0.32016 (9)	0.0274 (4)
H5A	−0.0845	0.3299	0.2786	0.033*
C6	0.02284 (9)	0.3330 (2)	0.34341 (9)	0.0279 (4)
H6A	0.0343	0.2621	0.3175	0.033*
C7	0.15505 (8)	0.35096 (17)	0.43153 (8)	0.0195 (3)
C8	−0.14354 (8)	0.51734 (18)	0.33966 (8)	0.0225 (3)
C9	0.13727 (10)	−0.0395 (3)	0.30935 (11)	0.0436 (5)
H9A	0.1157	0.0489	0.2858	0.052*
C10	0.10157 (14)	−0.1722 (3)	0.28274 (13)	0.0607 (7)
H10A	0.0573	−0.1730	0.2416	0.073*
C11	0.13216 (15)	−0.3040 (3)	0.31772 (14)	0.0606 (7)
H11A	0.1092	−0.3952	0.3008	0.073*
C12	0.19671 (15)	−0.2967 (3)	0.37758 (16)	0.0638 (7)
H12A	0.2186	−0.3833	0.4029	0.077*
C13	0.22946 (11)	−0.1598 (2)	0.40045 (13)	0.0453 (5)
H13A	0.2738	−0.1569	0.4415	0.054*
C14	0.35479 (11)	0.4243 (2)	0.37921 (11)	0.0420 (5)
H14A	0.3424	0.3706	0.3368	0.050*
C15	0.40012 (13)	0.5448 (3)	0.39352 (13)	0.0576 (6)
H15A	0.4172	0.5725	0.3609	0.069*
C16	0.41985 (14)	0.6238 (3)	0.45638 (13)	0.0597 (7)
H16A	0.4509	0.7052	0.4674	0.072*
C17	0.39288 (12)	0.5804 (2)	0.50277 (12)	0.0504 (6)
H17A	0.4053	0.6317	0.5459	0.060*
C18	0.34689 (10)	0.4591 (2)	0.48428 (10)	0.0348 (4)
H18A	0.3285	0.4307	0.5157	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01420 (11)	0.02272 (12)	0.02113 (12)	0.00372 (8)	0.00874 (9)	−0.00107 (8)
O1	0.0180 (5)	0.0376 (7)	0.0255 (6)	0.0093 (5)	0.0107 (5)	−0.0020 (5)
O1W	0.0295 (6)	0.0308 (6)	0.0266 (6)	0.0102 (5)	0.0141 (5)	0.0055 (5)
O2	0.0183 (6)	0.0338 (6)	0.0209 (6)	0.0048 (5)	0.0061 (5)	0.0005 (5)
O3	0.0180 (6)	0.0468 (8)	0.0266 (6)	0.0100 (5)	0.0101 (5)	−0.0053 (5)
O4	0.0195 (6)	0.0423 (7)	0.0311 (6)	0.0055 (5)	0.0055 (5)	−0.0125 (6)
N1	0.0233 (7)	0.0275 (7)	0.0299 (7)	0.0002 (6)	0.0119 (6)	−0.0021 (6)
N2	0.0266 (7)	0.0288 (7)	0.0314 (8)	−0.0015 (6)	0.0141 (6)	−0.0024 (6)
C1	0.0155 (7)	0.0251 (8)	0.0209 (7)	0.0039 (6)	0.0095 (6)	0.0013 (6)
C2	0.0184 (8)	0.0351 (10)	0.0298 (9)	0.0024 (7)	0.0072 (7)	−0.0120 (7)
C3	0.0218 (8)	0.0343 (9)	0.0338 (9)	0.0047 (7)	0.0116 (7)	−0.0126 (8)
C4	0.0175 (7)	0.0255 (8)	0.0235 (8)	0.0041 (6)	0.0103 (6)	−0.0001 (6)
C5	0.0180 (8)	0.0358 (9)	0.0252 (8)	0.0022 (7)	0.0071 (7)	−0.0098 (7)
C6	0.0230 (8)	0.0340 (9)	0.0278 (8)	0.0058 (7)	0.0126 (7)	−0.0096 (7)
C7	0.0173 (7)	0.0196 (8)	0.0231 (8)	0.0036 (6)	0.0104 (6)	0.0032 (6)
C8	0.0181 (7)	0.0225 (8)	0.0270 (8)	0.0031 (6)	0.0102 (6)	−0.0011 (6)
C9	0.0333 (10)	0.0466 (12)	0.0404 (11)	−0.0071 (9)	0.0074 (9)	0.0057 (9)
C10	0.0518 (14)	0.0741 (18)	0.0418 (12)	−0.0329 (13)	0.0088 (11)	−0.0062 (12)
C11	0.0780 (18)	0.0432 (14)	0.0695 (17)	−0.0314 (12)	0.0415 (15)	−0.0206 (12)
C12	0.0650 (16)	0.0288 (11)	0.090 (2)	−0.0015 (10)	0.0292 (15)	0.0043 (12)
C13	0.0378 (11)	0.0307 (10)	0.0571 (13)	0.0008 (8)	0.0125 (10)	0.0043 (9)
C14	0.0480 (12)	0.0467 (12)	0.0364 (10)	−0.0155 (9)	0.0238 (9)	−0.0063 (9)
C15	0.0704 (16)	0.0595 (15)	0.0535 (13)	−0.0310 (13)	0.0376 (13)	−0.0072 (11)
C16	0.0661 (16)	0.0503 (14)	0.0625 (15)	−0.0319 (12)	0.0292 (13)	−0.0103 (12)
C17	0.0606 (14)	0.0437 (13)	0.0443 (12)	−0.0168 (10)	0.0217 (11)	−0.0164 (10)
C18	0.0393 (10)	0.0315 (10)	0.0377 (10)	−0.0006 (8)	0.0211 (8)	−0.0023 (8)

Geometric parameters (Å, º)

Co1—O3^i	2.0588 (11)	C3—H3A	0.9300
Co1—O1	2.0615 (11)	C4—C5	1.388 (2)
Co1—O2^ii	2.0787 (11)	C4—C8	1.511 (2)
Co1—O1W	2.1403 (11)	C5—C6	1.388 (2)
Co1—N1	2.1833 (14)	C5—H5A	0.9300
Co1—N2	2.1876 (15)	C6—H6A	0.9300
O1—C7	1.2581 (18)	C9—C10	1.375 (3)
O1W—H1W	0.8500	C9—H9A	0.9300
O1W—H2W	0.8500	C10—C11	1.378 (4)
O2—C7	1.2540 (18)	C10—H10A	0.9300
O2—Co1^ii	2.0788 (11)	C11—C12	1.356 (4)
O3—C8	1.2591 (18)	C11—H11A	0.9300
O3—Co1^iii	2.0588 (11)	C12—C13	1.376 (3)
O4—C8	1.2509 (19)	C12—H12A	0.9300
N1—C13	1.327 (2)	C13—H13A	0.9300
N1—C9	1.331 (2)	C14—C15	1.373 (3)
N2—C18	1.335 (2)	C14—H14A	0.9300
N2—C14	1.339 (2)	C15—C16	1.371 (3)
C1—C6	1.389 (2)	C15—H15A	0.9300
C1—C2	1.391 (2)	C16—C17	1.373 (3)
C1—C7	1.509 (2)	C16—H16A	0.9300
C2—C3	1.385 (2)	C17—C18	1.381 (3)
C2—H2A	0.9300	C17—H17A	0.9300
C3—C4	1.389 (2)	C18—H18A	0.9300
O3^i—Co1—O1	170.84 (5)	C6—C5—H5A	120.0
O3^i—Co1—O2^ii	92.23 (4)	C1—C6—C5	121.04 (15)
O1—Co1—O2^ii	96.90 (4)	C1—C6—H6A	119.5
O3^i—Co1—O1W	86.16 (4)	C5—C6—H6A	119.5
O1—Co1—O1W	84.69 (4)	O2—C7—O1	125.47 (14)
O2^ii—Co1—O1W	173.07 (5)	O2—C7—C1	118.29 (13)
O3^i—Co1—N1	91.33 (5)	O1—C7—C1	116.24 (13)
O1—Co1—N1	88.34 (5)	O4—C8—O3	125.39 (14)
O2^ii—Co1—N1	88.22 (5)	O4—C8—C4	119.69 (14)
O1W—Co1—N1	85.08 (5)	O3—C8—C4	114.92 (13)
O3^i—Co1—N2	84.72 (5)	N1—C9—C10	123.0 (2)
O1—Co1—N2	95.36 (5)	N1—C9—H9A	118.5
O2^ii—Co1—N2	93.20 (5)	C10—C9—H9A	118.5
O1W—Co1—N2	93.37 (5)	C9—C10—C11	119.3 (2)
N1—Co1—N2	175.84 (5)	C9—C10—H10A	120.4
C7—O1—Co1	132.42 (10)	C11—C10—H10A	120.4
Co1—O1W—H1W	107.3	C12—C11—C10	118.1 (2)
Co1—O1W—H2W	125.1	C12—C11—H11A	121.0
H1W—O1W—H2W	111.6	C10—C11—H11A	121.0
C7—O2—Co1^ii	144.09 (11)	C11—C12—C13	119.2 (2)
C8—O3—Co1^iii	134.77 (10)	C11—C12—H12A	120.4
C13—N1—C9	116.74 (17)	C13—C12—H12A	120.4
C13—N1—Co1	121.97 (12)	N1—C13—C12	123.7 (2)
C9—N1—Co1	120.88 (13)	N1—C13—H13A	118.2
C18—N2—C14	117.01 (16)	C12—C13—H13A	118.2
C18—N2—Co1	124.04 (12)	N2—C14—C15	123.04 (19)
C14—N2—Co1	118.77 (12)	N2—C14—H14A	118.5
C6—C1—C2	118.85 (14)	C15—C14—H14A	118.5
C6—C1—C7	121.31 (14)	C14—C15—C16	119.3 (2)
C2—C1—C7	119.84 (14)	C14—C15—H15A	120.4
C3—C2—C1	119.99 (15)	C16—C15—H15A	120.4
C3—C2—H2A	120.0	C17—C16—C15	118.6 (2)
C1—C2—H2A	120.0	C17—C16—H16A	120.7
C2—C3—C4	121.19 (15)	C15—C16—H16A	120.7
C2—C3—H3A	119.4	C16—C17—C18	118.8 (2)
C4—C3—H3A	119.4	C16—C17—H17A	120.6
C5—C4—C3	118.83 (14)	C18—C17—H17A	120.6
C5—C4—C8	122.54 (14)	N2—C18—C17	123.25 (18)
C3—C4—C8	118.60 (14)	N2—C18—H18A	118.4
C4—C5—C6	120.02 (15)	C17—C18—H18A	118.4
C4—C5—H5A	120.0
C6—C1—C2—C3	1.8 (3)	C5—C4—C8—O4	−20.0 (2)
C7—C1—C2—C3	−178.17 (16)	C3—C4—C8—O4	161.76 (16)
C1—C2—C3—C4	0.4 (3)	C5—C4—C8—O3	160.81 (16)
C2—C3—C4—C5	−2.8 (3)	C3—C4—C8—O3	−17.4 (2)
C2—C3—C4—C8	175.53 (16)	C13—N1—C9—C10	−1.8 (3)
C3—C4—C5—C6	2.9 (3)	Co1—N1—C9—C10	170.87 (18)
C8—C4—C5—C6	−175.33 (16)	N1—C9—C10—C11	1.2 (4)
C2—C1—C6—C5	−1.7 (3)	C9—C10—C11—C12	0.2 (4)
C7—C1—C6—C5	178.31 (16)	C10—C11—C12—C13	−0.9 (4)
C4—C5—C6—C1	−0.7 (3)	C9—N1—C13—C12	1.1 (3)
Co1^ii—O2—C7—O1	−100.7 (2)	Co1—N1—C13—C12	−171.5 (2)
Co1^ii—O2—C7—C1	80.2 (2)	C11—C12—C13—N1	0.2 (4)
Co1—O1—C7—O2	8.3 (2)	C18—N2—C14—C15	−0.6 (3)
Co1—O1—C7—C1	−172.59 (10)	Co1—N2—C14—C15	−175.96 (18)
C6—C1—C7—O2	−163.23 (15)	N2—C14—C15—C16	1.0 (4)
C2—C1—C7—O2	16.7 (2)	C14—C15—C16—C17	−0.6 (4)
C6—C1—C7—O1	17.6 (2)	C15—C16—C17—C18	−0.1 (4)
C2—C1—C7—O1	−162.40 (15)	C14—N2—C18—C17	−0.2 (3)
Co1^iii—O3—C8—O4	−6.3 (3)	Co1—N2—C18—C17	174.89 (16)
Co1^iii—O3—C8—C4	172.82 (11)	C16—C17—C18—N2	0.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O4^i	0.85	1.99	2.7743 (16)	153
O1W—H2W···O4^iv	0.85	1.86	2.7079 (17)	177

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