Supra­molecular architectures in Co^II and Cu^II complexes with thio­phene-2-carboxyl­ate and 2-amino-4,6-di­meth­oxy­pyrimidine ligands

The coordination chemistry of mixed-ligand complexes continues to be an active area of research since these compounds have a wide range of applications. Many coordination polymers and metal–organic framworks are emerging as novel functional materials. Amino­pyrimidine and its derivatives are flexible ligands with versatile binding and coordination modes which have been proven to be useful in the construction of organic–inorganic hybrid materials and coordination polymers. Thio­phene­carb­oxy­lic acid, its derivatives and their complexes exhibit pharmacological properties. Cobalt(II) and copper(II) complexes of thio­phene­carboxyl­ate have many biological applications, for example, as anti­fungal and anti­tumor agents. Two new cobalt(II) and copper(II) complexes incorporating thio­phene-2-carboxyl­ate (2-TPC) and 2-amino-4,6-di­meth­oxy­pyrimidine (OMP) ligands have been synthesized and characterized by X-ray diffraction studies, namely (2-amino-4,6-di­meth­oxy­pyrimidine-κN)aqua­chlorido­(thio­phene-2-carboxyl­ato-κO)cobalt(II) monohydrate, [Co(C₅H₃O₂S)Cl(C₆H₉N₃O₂)(H₂O)]·H₂O, (I), and catena-poly[copper(II)-tetra­kis­(μ-thio­phene-2-car­box­yl­ato-κ²O:O′)-copper(II)-(μ-2-amino-4,6-di­meth­oxy­pyrimidine-κ²N¹:N³)], [Cu₂(C₅H₃O₂S)₄(C₆H₉N₃O₂)]_n, (II). In (I), the Co^II ion has a distorted tetra­hedral coordination environment involving one O atom from a monodentate 2-TPC ligand, one N atom from an OMP ligand, one chloride ligand and one O atom of a water mol­ecule. An additional water mol­ecule is present in the asymmetric unit. The amino group of the coordinated OMP mol­ecule and the coordinated carboxyl­ate O atom of the 2-TPC ligand form an inter­ligand N—H...O hydrogen bond, generating an S(6) ring motif. The pyrimidine mol­ecules also form a base pair [R₂²(8) motif] via a pair of N—H...N hydrogen bonds. These inter­actions, together with O—H...O and O—H...Cl hydrogen bonds and π–π stacking inter­actions, generate a three-dimensional supra­molecular architecture. The one-dimensional coordination polymer (II) contains the classical paddle-wheel [Cu₂(CH₃COO)₄(H₂O)₂] unit, where each carboxylate group of four 2-TPC ligands bridges two square-pyramidally coordinated Cu^II ions and the apically coordinated OMP ligands bridge the dinuclear copper units. Each dinuclear copper unit has a crystallographic inversion centre, whereas the bridging OMP ligand has crystallographic twofold symmetry. The one-dimensional polymeric chains self-assemble via N—H...O, π–π and C—H...π inter­actions, generating a three-dimensional supra­molecular architecture.

S1. Introduction

The coordination chemistry of mixed-ligand (more than one type of ligand) complexes continues to be an active area of research since these compounds have a wide range of applications (Suntharalingam et al., 2014; Timmons & Symes, 2015; Paine & Que, 2014). Such complexes are good models for metal centres in biology with respect to materials chemistry (Molčanov et al., 2013; Liu et al., 2015; Soayed et al., 2013; Mongey et al., 1997; Malik et al., 1977), and research in this field generates knowledge which is useful in the design of not only discrete coordination motifs, but also coordination polymers and metal–organic frameworks (MOFs). Many coordination polymers and MOFs are emerging as novel functional materials (Moulton &Zaworotko, 2001; Zhang et al., 2007). The discrete coordination/coordination polymers/MOFs further self-assemble via a variety of noncovalent inter­actions, generating supra­molecular architectures (Cook et al., 2013; Amo-Ochoa & Zamora, 2014). Several mixed-ligand complexes and supra­molecular architectures have already been reported by our groups (Hemamalini et al., 2006; Jenniefer & Mu­thiah, 2013; Jenniefer & Mu­thiah, 2014; Perdih, 2012; Koleša-Dobravc et al.,2015). In this work, two well studied and versatile ligands (the carboxyl­ate and amino­pyrimidine groups) have been used. The carboxyl­ate group and amino­pyrimdines are biologically important ligands. They are components of many biomolecules and drugs (Schmidt et al., 1977; Hunt et al., 1980; Ballatore et al., 2013). Amino­pyrimidine and its derivatives are flexible ligands with versatile binding and coordination modes which have been proven to be useful in the construction of organic–inorganic hybrid materials and coordination polymers (Feeder et al., 2001). Thio­phene­carb­oxy­lic acid, its derivatives and their complexes have received considerable attention because of their pharmacological properties and numerous applications, such as the preparation of DNA hybridization indicators, single-molecule magnets, photoluminescence materials and the treatment of osteoporosis as inhibitors of bone resorption in the tissue culture (Bharti et al., 2003; Fang et al. 1971; Taş et al.,2014; Boulsourani et al., 2011). Studies of cobalt(II) and copper(II) complexes of thio­phene­carboxyl­ate have received a continuing high level of attention in recent years due to their many biological applications, for example, as anti­fungal and anti­tumor agents (Teotonio et al., 2004; Demessence et al., 2006, 2007). In addition, thio­phene and pyrimidine groups can be involved in π–π stacking inter­actions. In the present study, we discuss the two new cobalt(II) and copper(II) complexes incorporating thio­phene-2-carboxyl­ate (2-TPC) and 2-amino-4,6-di­meth­oxy­pyrimidine ligands, namely, (2-amino-4,6-di­meth­oxy­pyrimidine-κN)aqua­chlorido(thio­phene-2-carboxyl­ato-κO)cobalt(II) monohydrate, (I), and catena-poly[copper(II)-tetra­kis(µ-thio­phene-2-carboxyl­ato-κ²O:O')-copper(II)-(µ-2-amino-4,6-di­meth­oxy­pyrimidine- κ²N¹:N³)], (II), and analyze the coordination modes, hydrogen-bond patterns, supra­molecular architectures and π–π stacking inter­actions (see Scheme 1).

S2. Experimental

S2.1. Synthesis and crystallization

S2.1.1. Preparation of [Co(2-TPC)Cl(OMP)(H\\\\\\\\\\\\\\\~2\\\\\\\\\\\\\\\Õ)]\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\·H\\\\\\\\\\\\\\\~2\\\\\\\\\\\\\\\Õ, (I)

A solution of CoCl₂·6H₂O (0.0538 g) in methanol (15 ml) was stirred over a hot plate magnetic stirrer for half an hour and thio­phene-2-carb­oxy­lic acid (0.0640 g) dissolved in hot water (10 ml) was added. The mixture was stirred for an additional 2 h. A light-red solution was formed. OMP (0.038 g) was dissolved in hot water (10 ml) and added to the reaction mixture. The mixture was stirred for 3 h and the resulting light-red solution was kept at room temperature for slow evaporation. After a few days, violet-coloured crystals of (I) were obtained.

S2.1.2. Preparation of [Cu\\\\\\\\\\\\\\\~2\\\\\\\\\\\\\\\~(2-TPC)\\\\\\\\\\\\\\\~4\\\\\\\\\\\\\\\~(OMP)]\\\\\\\\\\\\\\\~n\\\\\\\\\\\\\\\~, (II)

A solution of Cu(NO₃)₂·3H₂O (0.046 g) in methanol (15 ml) was stirred over a hot plate magnetic stirrer for half an hour and thio­phene-2-carb­oxy­lic acid (0.0640 g) dissolved in hot water (10 ml) was added. The mixture was stirred for additional 2 h. A green solution was formed. OMP (0.038 g) was dissolved in hot water (10 ml) and added to the reaction mixture. The mixture was stirred for 3 h and the resulting blue–green solution was kept at room temperature for slow evaporation. After a few days, blue crystals of (II) were obtained.

S2.2. Refinement

Crystal data, data collection and structure refinement details for (I) and (II) are summarized in Table 1. H atoms were located readily in difference Fourier maps and were, in most cases, subsequently treated as riding atoms in geometrically idealized positions, with U_iso(H) = kU_eq(N,C), where k = 1.5 for methyl group and 1.2 for all other H atoms. In (I), H atoms attached to water O atoms were refined fixing bond lengths with U_iso(H) = 1.5U_eq(O). The S1 and C3 atoms of the thio­phene ring of compound (I) were treated as disordered over two positions, with a refined occupancy ratio of 0.633 (4):0.367 (4). The S1 and C7 atoms, as well as the S2 and C12 atoms of the thio­phene rings, of compound (II) were treated as disordered over two positions, with refined occupancy ratios of 0.372 (4):0.628 (4) and 0.594 (5):0.406 (5), respectively.

S3. Results and discussion

S3.1. Structure description of [Co(2-TPC)Cl(OMP)(H\\\\\\\\\\\\\\\~2\\\\\\\\\\\\\\\Õ)]\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\·H\\\\\\\\\\\\\\\~2\\\\\\\\\\\\\\\Õ, (I)

The Co^II ion in (I) has a distorted tetra­hedral coordination environment involving one O atom from a monodentate thio­phene-2-carboxyl­ate (2-TPC) ligand, one N atom from a 2-amino-4,6-di­meth­oxy­pyrimidine (OMP) ligand, one chloride ligand and one O atom of a water molecule. Furthermore, one water molecule is present in the crystal lattice (Fig. 1). The bond lengths [Co1—O1 = 1.9646 (14) Å, Co1—O5 = 1.9625 (16) Å, Co1—N1 = 2.0564 (14) Å and Co1—Cl1 = 2.2585 (6) Å] agree with those reported in the literature (Taş et al., 2014; Pike et al., 2006; Song et al., 2005; Demessence et al., 2007).The amino group of the coordinated OMP molecule and the coordinated carboxyl­ate O atom of the 2-TPC ligand form an inter­ligand N—H···O hydrogen bond, generating an S(6) ring motif. This type of inter­ligand hydrogen bond is characteristic of many metal complexes of amino­pyrimidine/amino­purines (Mu­thiah et al., 1983, 2001; Karthikeyan et al., 2010). The structure has a combination of O—H···O and O—H···Cl inter­actions between the coordinated and uncoordinated water molecule, as well as the coordinated chloride ligand and coordinated carboxyl­ate group. A supra­molecular ladder is formed by O5—H5A···O6, O5—H5B···O6 and O6—H6B···Cl hydrogen-bonded R₄⁴(12) and R₂⁴(12) ring motifs involving the metal ion, the coordinated chloride ion, the coordinated water molecules and the uncoordinated water molecules and this is shown schematically in Fig. 2(a). This motif as observed in the crystal lattice is shown in Fig. 2(b) (Hemamalini et al., 2006; Prabakaran et al., 2000; Jenniefer & Mu­thiah, 2014). Another supra­molecular ladder is formed by two R₄⁴(16) ring motifs involving O5—H5B···O6, O6—H6B···Cl and O6—H6A···O2 hydrogen bonds, made up of metal ions, carboxyl­ate groups, chloride ions and both types of (coordinated and uncoordinated) water molecules. This scheme is shown in Fig. 3(a). This motif as observed in the lattice is shown in Fig. 3(b). In addition, the OMP ligands also form base pairs [R₂²(8) motif] via a pair of N2—H2A···N3 hydrogen bonds (Fig. 4a) (Albada et al., 2002). All these inter­actions, together with π–π stacking inter­actions (Fig. 4a), generate the three-dimensional supra­molecular architecture (Fig. 4b). Stacking inter­actions are observed involving symmetry-related OMP and 2-TPC ligands, with centroid-to-centroid distance of Cg1···Cg3ⁱ = 3.740 (3) Å, Cg1···Cg3ⁱⁱ = 3.544 (3) Å, Cg2···Cg3ⁱ = 3.719 (5) Å and Cg2—Cg3ⁱⁱ = 3.550 (5) Å [Cg1, Cg2 and Cg3 are the centroids of the ???, ??? and ??? rings, respectively; symmetry code: (i) x-1, y-1, z; (ii) x, y-1, z]. Similar values were also observed for amino­pyrimidine–thio­phene­carboxyl­ate inter­actions (Rajam et al., 2015).

S3.2. Structure description of [Cu\\\\\\\\\\\\\\\~2\\\\\\\\\\\\\\\~(2-TPC)\\\\\\\\\\\\\\\~4\\\\\\\\\\\\\\\~(OMP)]\\\\\\\\\\\\\\\~n\\\\\\\\\\\\\\\~, (II)

In compound (II), the Cu^II ion has a coordination geometry similar to the classical [Cu₂(CH₃COO)₄(H₂O)₂] paddle-wheel, where each of the carboxyl­ate groups bridges two Cu^II ions. But in compound (II), instead of water molecules, the OMP ligand bridges the dimeric Cu^II units, generating a one-dimensional coordination polymer (Fig. 5). The square-pyramidal coordination polyhedron of the each Cu^II ion is coordinated by four different O atoms from the carboxyl­ate groups of four 2-TPC ligands which occupy the equatorial positions. In the axial sites of the dimers, the OMP ligands extend the structure into a one-dimensional chain. The dinuclear Cu^II unit has crystallographic inversion symmetry and the OMP bridging ligand has twofold rotation symmetry. The Cu—O and Cu—N bond lengths [Cu1—O1 = 1.9661 (17) Å, Cu1b—O2 = 1.9546 (16) Å, Cu1—O3 = 1.9587 (16) Å and Cu1b—O4 = 1.9752 (16) Å, and Cu1—N1 = 2.3024 (17) Å and Cu1b—N1a = 2.3024 (17) Å; symmetry codes: (a) ???; (b) -x, -y+1, -z] are in good agreement with those found in other copper thio­phene­carboxyl­ate and amino­pyrimidine complexes (Jenniefer & Mu­thiah, 2013; Taş et al., 2014; Blake et al., 2002; Smith et al.,1991; Kuchtanin et al. 2013; Marques et al., 2011). The dimeric Cu—Cu units are further connected by the OMP ligand, thus generating a one-dimensional linear chain, with a Cu1···Cu1b separation of 2.7411 (5) Å. These values are in a good agreement with copper(II) carboxyl­ate paddle-wheel structures (Gomathi & Mu­thiah, 2013; Jenniefer & Mu­thiah, 2013; Blake et al., 2002; Smith et al., 1991; Kuchtanin et al., 2013; Paredes-Garcia et al., 2013; Lu, 2003). Along the coordination polymer, the N···N width of the bridging-spacer pyrimidine ligand is 2.4162 (2) Å, leading to a Cu···Cu separation of 6.4918 (4) Å (Fig. 6a). A comparison of these parameters in various coordination polymers is given in Table 4. The one-dimensional chains are further assembled to form a two-dimensional supra­molecular sheet (Fig. 6b). These sheets are inter­connected by inter-chain hydrogen bonds between the amine N atom of the amino­pyrimdine and thio­phene­carboxyl­ate O atoms via (N2—H2A···.O4 and N2—H2B···O4) hydrogen bonds (Jenniefer & Mu­thiah, 2013; Smith et al., 1991), and π–π and C—H···π inter­actions. The stacking inter­actions involving the symmetry-related OMP and 2-TPC molecules, with centroid-to-centroid distances of Cg2···Cg2ⁱ = 3.793 (6) Å, Cg2···Cg4ⁱ = 3.773 (8) Å and Cg4···Cg4ⁱ = 3.759 (10) Å [Cg2 and Cg4 are the centroids of the ??? and ??? rings, respectively; symmetry code: (i) -x+1/2, -y+3/2, -z] and C—H···π inter­actions of C4—H4A···Cg2ⁱⁱ = 2.94 Å and C4—H4A···Cg4ⁱⁱ = 2.91 Å [symmetry code: (ii) -x, -y+2,-z] (Fig. 7a). The polymeric chains self-assemble via N—H···.O, π–π and C—H···π inter­actions, and generate a three-dimensional supra­molecular architecture (Fig. 7b).

In conclusion, cobalt and copper thio­phene-2-carboxyl­ate complexes with 2-amino-4,6-di­meth­oxy­pyrimidine have been synthesized and characterized by X-ray crystallography. In compound (1), the Co^II ion has a distorted tetra­hedral coordination geometry made up of two ladder motifs (involving O—H···O and O—H···Cl hydrogen bonds) present in the lattice in addition to pyrimidine–pyrimidine base pairs graph-set notation R₂²(8) (via a pair of N—H···N hydrogen bonds). The crystal structure is further stabilized by π–π stacking inter­actions. The coordinated chloride ion and the coordinated/uncoordinated water molecules play a major role in building up a supra­molecular architecture. In compound (II), the Cu^II atom has a coordination geometry similar to the classical paddle-wheel [Cu₂(CH₃COO)₄(H₂O)₂]. In the complex, the OMP bridges the dimeric copper units, generating a one-dimensional coordination polymer. Furthermore, the one-dimensional chains are self-assembled to form two-dimensional supra­molecular sheets. These supra­molecular sheets are inter­connected by N—H···.O, π–π and C—H···π inter­actions. The identification of such hydrogen bonding and supra­molecular patterns will help us to design and construct novel potential functional materials. The coordination polymers observed in (II) have a striking resemblance to the motif observed in two crystal structures involving pyrimidine, namely catena-poly[[tetra­kis(µ-acetato-κ²O:O)dicopper(II)]-µ-2-amino­pyrimidine-κ²N:N] (Blake et al., 2002) and catena-poly[(2-amino­pyrimidine-κ²N,N')tetra­kis(µ-ethano­ato-κ²O:O)dicopper(II)] (Smith et al., 1991). This is significant from the point of view of crystal engineering.

Structure description

The coordination chemistry of mixed-ligand (more than one type of ligand) complexes continues to be an active area of research since these compounds have a wide range of applications (Suntharalingam et al., 2014; Timmons & Symes, 2015; Paine & Que, 2014). Such complexes are good models for metal centres in biology with respect to materials chemistry (Molčanov et al., 2013; Liu et al., 2015; Soayed et al., 2013; Mongey et al., 1997; Malik et al., 1977), and research in this field generates knowledge which is useful in the design of not only discrete coordination motifs, but also coordination polymers and metal–organic frameworks (MOFs). Many coordination polymers and MOFs are emerging as novel functional materials (Moulton &Zaworotko, 2001; Zhang et al., 2007). The discrete coordination/coordination polymers/MOFs further self-assemble via a variety of noncovalent inter­actions, generating supra­molecular architectures (Cook et al., 2013; Amo-Ochoa & Zamora, 2014). Several mixed-ligand complexes and supra­molecular architectures have already been reported by our groups (Hemamalini et al., 2006; Jenniefer & Mu­thiah, 2013; Jenniefer & Mu­thiah, 2014; Perdih, 2012; Koleša-Dobravc et al.,2015). In this work, two well studied and versatile ligands (the carboxyl­ate and amino­pyrimidine groups) have been used. The carboxyl­ate group and amino­pyrimdines are biologically important ligands. They are components of many biomolecules and drugs (Schmidt et al., 1977; Hunt et al., 1980; Ballatore et al., 2013). Amino­pyrimidine and its derivatives are flexible ligands with versatile binding and coordination modes which have been proven to be useful in the construction of organic–inorganic hybrid materials and coordination polymers (Feeder et al., 2001). Thio­phene­carb­oxy­lic acid, its derivatives and their complexes have received considerable attention because of their pharmacological properties and numerous applications, such as the preparation of DNA hybridization indicators, single-molecule magnets, photoluminescence materials and the treatment of osteoporosis as inhibitors of bone resorption in the tissue culture (Bharti et al., 2003; Fang et al. 1971; Taş et al.,2014; Boulsourani et al., 2011). Studies of cobalt(II) and copper(II) complexes of thio­phene­carboxyl­ate have received a continuing high level of attention in recent years due to their many biological applications, for example, as anti­fungal and anti­tumor agents (Teotonio et al., 2004; Demessence et al., 2006, 2007). In addition, thio­phene and pyrimidine groups can be involved in π–π stacking inter­actions. In the present study, we discuss the two new cobalt(II) and copper(II) complexes incorporating thio­phene-2-carboxyl­ate (2-TPC) and 2-amino-4,6-di­meth­oxy­pyrimidine ligands, namely, (2-amino-4,6-di­meth­oxy­pyrimidine-κN)aqua­chlorido(thio­phene-2-carboxyl­ato-κO)cobalt(II) monohydrate, (I), and catena-poly[copper(II)-tetra­kis(µ-thio­phene-2-carboxyl­ato-κ²O:O')-copper(II)-(µ-2-amino-4,6-di­meth­oxy­pyrimidine- κ²N¹:N³)], (II), and analyze the coordination modes, hydrogen-bond patterns, supra­molecular architectures and π–π stacking inter­actions (see Scheme 1).

A solution of CoCl₂·6H₂O (0.0538 g) in methanol (15 ml) was stirred over a hot plate magnetic stirrer for half an hour and thio­phene-2-carb­oxy­lic acid (0.0640 g) dissolved in hot water (10 ml) was added. The mixture was stirred for an additional 2 h. A light-red solution was formed. OMP (0.038 g) was dissolved in hot water (10 ml) and added to the reaction mixture. The mixture was stirred for 3 h and the resulting light-red solution was kept at room temperature for slow evaporation. After a few days, violet-coloured crystals of (I) were obtained.

A solution of Cu(NO₃)₂·3H₂O (0.046 g) in methanol (15 ml) was stirred over a hot plate magnetic stirrer for half an hour and thio­phene-2-carb­oxy­lic acid (0.0640 g) dissolved in hot water (10 ml) was added. The mixture was stirred for additional 2 h. A green solution was formed. OMP (0.038 g) was dissolved in hot water (10 ml) and added to the reaction mixture. The mixture was stirred for 3 h and the resulting blue–green solution was kept at room temperature for slow evaporation. After a few days, blue crystals of (II) were obtained.

The Co^II ion in (I) has a distorted tetra­hedral coordination environment involving one O atom from a monodentate thio­phene-2-carboxyl­ate (2-TPC) ligand, one N atom from a 2-amino-4,6-di­meth­oxy­pyrimidine (OMP) ligand, one chloride ligand and one O atom of a water molecule. Furthermore, one water molecule is present in the crystal lattice (Fig. 1). The bond lengths [Co1—O1 = 1.9646 (14) Å, Co1—O5 = 1.9625 (16) Å, Co1—N1 = 2.0564 (14) Å and Co1—Cl1 = 2.2585 (6) Å] agree with those reported in the literature (Taş et al., 2014; Pike et al., 2006; Song et al., 2005; Demessence et al., 2007).The amino group of the coordinated OMP molecule and the coordinated carboxyl­ate O atom of the 2-TPC ligand form an inter­ligand N—H···O hydrogen bond, generating an S(6) ring motif. This type of inter­ligand hydrogen bond is characteristic of many metal complexes of amino­pyrimidine/amino­purines (Mu­thiah et al., 1983, 2001; Karthikeyan et al., 2010). The structure has a combination of O—H···O and O—H···Cl inter­actions between the coordinated and uncoordinated water molecule, as well as the coordinated chloride ligand and coordinated carboxyl­ate group. A supra­molecular ladder is formed by O5—H5A···O6, O5—H5B···O6 and O6—H6B···Cl hydrogen-bonded R₄⁴(12) and R₂⁴(12) ring motifs involving the metal ion, the coordinated chloride ion, the coordinated water molecules and the uncoordinated water molecules and this is shown schematically in Fig. 2(a). This motif as observed in the crystal lattice is shown in Fig. 2(b) (Hemamalini et al., 2006; Prabakaran et al., 2000; Jenniefer & Mu­thiah, 2014). Another supra­molecular ladder is formed by two R₄⁴(16) ring motifs involving O5—H5B···O6, O6—H6B···Cl and O6—H6A···O2 hydrogen bonds, made up of metal ions, carboxyl­ate groups, chloride ions and both types of (coordinated and uncoordinated) water molecules. This scheme is shown in Fig. 3(a). This motif as observed in the lattice is shown in Fig. 3(b). In addition, the OMP ligands also form base pairs [R₂²(8) motif] via a pair of N2—H2A···N3 hydrogen bonds (Fig. 4a) (Albada et al., 2002). All these inter­actions, together with π–π stacking inter­actions (Fig. 4a), generate the three-dimensional supra­molecular architecture (Fig. 4b). Stacking inter­actions are observed involving symmetry-related OMP and 2-TPC ligands, with centroid-to-centroid distance of Cg1···Cg3ⁱ = 3.740 (3) Å, Cg1···Cg3ⁱⁱ = 3.544 (3) Å, Cg2···Cg3ⁱ = 3.719 (5) Å and Cg2—Cg3ⁱⁱ = 3.550 (5) Å [Cg1, Cg2 and Cg3 are the centroids of the ???, ??? and ??? rings, respectively; symmetry code: (i) x-1, y-1, z; (ii) x, y-1, z]. Similar values were also observed for amino­pyrimidine–thio­phene­carboxyl­ate inter­actions (Rajam et al., 2015).

In compound (II), the Cu^II ion has a coordination geometry similar to the classical [Cu₂(CH₃COO)₄(H₂O)₂] paddle-wheel, where each of the carboxyl­ate groups bridges two Cu^II ions. But in compound (II), instead of water molecules, the OMP ligand bridges the dimeric Cu^II units, generating a one-dimensional coordination polymer (Fig. 5). The square-pyramidal coordination polyhedron of the each Cu^II ion is coordinated by four different O atoms from the carboxyl­ate groups of four 2-TPC ligands which occupy the equatorial positions. In the axial sites of the dimers, the OMP ligands extend the structure into a one-dimensional chain. The dinuclear Cu^II unit has crystallographic inversion symmetry and the OMP bridging ligand has twofold rotation symmetry. The Cu—O and Cu—N bond lengths [Cu1—O1 = 1.9661 (17) Å, Cu1b—O2 = 1.9546 (16) Å, Cu1—O3 = 1.9587 (16) Å and Cu1b—O4 = 1.9752 (16) Å, and Cu1—N1 = 2.3024 (17) Å and Cu1b—N1a = 2.3024 (17) Å; symmetry codes: (a) ???; (b) -x, -y+1, -z] are in good agreement with those found in other copper thio­phene­carboxyl­ate and amino­pyrimidine complexes (Jenniefer & Mu­thiah, 2013; Taş et al., 2014; Blake et al., 2002; Smith et al.,1991; Kuchtanin et al. 2013; Marques et al., 2011). The dimeric Cu—Cu units are further connected by the OMP ligand, thus generating a one-dimensional linear chain, with a Cu1···Cu1b separation of 2.7411 (5) Å. These values are in a good agreement with copper(II) carboxyl­ate paddle-wheel structures (Gomathi & Mu­thiah, 2013; Jenniefer & Mu­thiah, 2013; Blake et al., 2002; Smith et al., 1991; Kuchtanin et al., 2013; Paredes-Garcia et al., 2013; Lu, 2003). Along the coordination polymer, the N···N width of the bridging-spacer pyrimidine ligand is 2.4162 (2) Å, leading to a Cu···Cu separation of 6.4918 (4) Å (Fig. 6a). A comparison of these parameters in various coordination polymers is given in Table 4. The one-dimensional chains are further assembled to form a two-dimensional supra­molecular sheet (Fig. 6b). These sheets are inter­connected by inter-chain hydrogen bonds between the amine N atom of the amino­pyrimdine and thio­phene­carboxyl­ate O atoms via (N2—H2A···.O4 and N2—H2B···O4) hydrogen bonds (Jenniefer & Mu­thiah, 2013; Smith et al., 1991), and π–π and C—H···π inter­actions. The stacking inter­actions involving the symmetry-related OMP and 2-TPC molecules, with centroid-to-centroid distances of Cg2···Cg2ⁱ = 3.793 (6) Å, Cg2···Cg4ⁱ = 3.773 (8) Å and Cg4···Cg4ⁱ = 3.759 (10) Å [Cg2 and Cg4 are the centroids of the ??? and ??? rings, respectively; symmetry code: (i) -x+1/2, -y+3/2, -z] and C—H···π inter­actions of C4—H4A···Cg2ⁱⁱ = 2.94 Å and C4—H4A···Cg4ⁱⁱ = 2.91 Å [symmetry code: (ii) -x, -y+2,-z] (Fig. 7a). The polymeric chains self-assemble via N—H···.O, π–π and C—H···π inter­actions, and generate a three-dimensional supra­molecular architecture (Fig. 7b).

In conclusion, cobalt and copper thio­phene-2-carboxyl­ate complexes with 2-amino-4,6-di­meth­oxy­pyrimidine have been synthesized and characterized by X-ray crystallography. In compound (1), the Co^II ion has a distorted tetra­hedral coordination geometry made up of two ladder motifs (involving O—H···O and O—H···Cl hydrogen bonds) present in the lattice in addition to pyrimidine–pyrimidine base pairs graph-set notation R₂²(8) (via a pair of N—H···N hydrogen bonds). The crystal structure is further stabilized by π–π stacking inter­actions. The coordinated chloride ion and the coordinated/uncoordinated water molecules play a major role in building up a supra­molecular architecture. In compound (II), the Cu^II atom has a coordination geometry similar to the classical paddle-wheel [Cu₂(CH₃COO)₄(H₂O)₂]. In the complex, the OMP bridges the dimeric copper units, generating a one-dimensional coordination polymer. Furthermore, the one-dimensional chains are self-assembled to form two-dimensional supra­molecular sheets. These supra­molecular sheets are inter­connected by N—H···.O, π–π and C—H···π inter­actions. The identification of such hydrogen bonding and supra­molecular patterns will help us to design and construct novel potential functional materials. The coordination polymers observed in (II) have a striking resemblance to the motif observed in two crystal structures involving pyrimidine, namely catena-poly[[tetra­kis(µ-acetato-κ²O:O)dicopper(II)]-µ-2-amino­pyrimidine-κ²N:N] (Blake et al., 2002) and catena-poly[(2-amino­pyrimidine-κ²N,N')tetra­kis(µ-ethano­ato-κ²O:O)dicopper(II)] (Smith et al., 1991). This is significant from the point of view of crystal engineering.

Refinement details

Crystal data, data collection and structure refinement details for (I) and (II) are summarized in Table 1. H atoms were located readily in difference Fourier maps and were, in most cases, subsequently treated as riding atoms in geometrically idealized positions, with U_iso(H) = kU_eq(N,C), where k = 1.5 for methyl group and 1.2 for all other H atoms. In (I), H atoms attached to water O atoms were refined fixing bond lengths with U_iso(H) = 1.5U_eq(O). The S1 and C3 atoms of the thio­phene ring of compound (I) were treated as disordered over two positions, with a refined occupancy ratio of 0.633 (4):0.367 (4). The S1 and C7 atoms, as well as the S2 and C12 atoms of the thio­phene rings, of compound (II) were treated as disordered over two positions, with refined occupancy ratios of 0.372 (4):0.628 (4) and 0.594 (5):0.406 (5), respectively.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997). Program(s) used to solve structure: SIR92 (Altomare et al., 1999 for (I); SIR97 (Altomare et al., 1999) for (II). For both compounds, program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The asymmetric unit of compound (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines represent hydrogen bonds. Disordered positions have been omitted for clarity.
	Fig. 2. (a) Schematic representation of a supramolecular ladder motif formed by hydrogen-bonded rings involving metal ions, coordinated chloride ions, coordinated water molecules and uncoordinated water molecules. (b) This motif as observed in the crystal lattice. Purple dashed lines indicate hydrogen bonds. The thiophene carboxylate pyrimidine ligands and H atoms not involved in hydrogen bonding have been omitted for clarity. The symmetry codes are as given in Table 2.
	Fig. 3. (a) Supramolecular ladder motif formed by hydrogen-bonded rings involving metal ions, carboxylate groups, coordinated chloride ions, coordinated water molecules and uncoordinated water molecules is schematically. (b) This motif as observed in the crystal lattice: The pyrimidine ligand and H atoms not involved in hydrogen bonding have been omitted for clarity. The symmetry codes are as given in Table 2.
	Fig. 4. (a) A view of primidine–pyrimidine base pairs and π–π stacking interactions (disordered positions have been omitted for clarity). (b) A view of three-dimensional supramolecular structures. Hydrogen bonds are drawn as light-blue dashed lines (disordered positions have been omitted for clarity). The symmetry codes are as given in Table 2.
	Fig. 5. A view of the molecule in the crystal structure. H atoms and disordered positions have been omitted for clarity. [Symmetry codes: (a) -x, y, -z+1/2; (b) -x, -y+1, -z; (c) x, -y+1, +z-1/2.]
	Fig. 6. Views of (a) the one-dimensional zigzag chain and (b) the supramolecular two-dimensional layers (disordered positions have been omitted for clarity). The symmetry codes are as given in Table 3.
	Fig. 7. Views of (a) the C—H···π and π–π stacking interactions between the one-dimensional chains, and (b) the three-dimensional architecture (disordered positions have been are omitted for clarity).

(I) (2-Amino-4,6-dimethoxypyrimidine-κN)aquachlorido(thiophene-2-carboxylato-κO)cobalt(II) monohydrate

Crystal data

[Co(C5H3O2S)Cl(C6H9N3O2)(H2O)]·H2O	Z = 2
Mr = 412.71	F(000) = 422
Triclinic, P1	Dx = 1.673 Mg m^−3
a = 7.2407 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9326 (2) Å	Cell parameters from 3665 reflections
c = 15.0550 (5) Å	θ = 1.0–27.5°
α = 92.932 (2)°	µ = 1.37 mm^−1
β = 102.406 (2)°	T = 293 K
γ = 102.727 (2)°	Prism, blue
V = 819.37 (4) Å^3	0.20 × 0.12 × 0.05 mm

Data collection

Nonius KappaCCD area-detector diffractometer	3734 independent reflections
Radiation source: fine-focus sealed tube	3189 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
Detector resolution: 0.055 pixels mm^-1	θmax = 27.4°, θmin = 3.5°
ω scans	h = −9→9
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −10→10
Tmin = 0.771, Tmax = 0.935	l = −19→19
6722 measured reflections

Refinement

Refinement on F^2	4 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.079	w = 1/[σ^2(Fo^2) + (0.0392P)^2 + 0.177P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3734 reflections	Δρmax = 0.27 e Å^−3
241 parameters	Δρmin = −0.45 e Å^−3

Special details

Experimental. 184 frames in 4 sets of ω scans. Rotation/frame = 2.0 °. Crystal-detector distance = 25.0 mm. Measuring time = 80 s/°.

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)
Co1	0.75721 (4)	0.33220 (3)	0.32164 (2)	0.03194 (9)
Cl1	1.05509 (7)	0.27480 (7)	0.34781 (4)	0.04599 (13)
S1A	0.3369 (4)	−0.1561 (4)	0.11849 (17)	0.0418 (5)	0.633 (4)
C3A	0.3398 (19)	−0.3302 (15)	0.2552 (8)	0.048 (4)	0.633 (4)
H3A	0.3651	−0.3608	0.3147	0.057*	0.633 (4)
S1B	0.3363 (8)	−0.3454 (6)	0.2757 (4)	0.0390 (9)	0.367 (4)
C3B	0.336 (3)	−0.186 (3)	0.1344 (12)	0.062 (7)	0.367 (4)
H3B	0.3575	−0.0987	0.0962	0.075*	0.367 (4)
N1	0.7570 (2)	0.51860 (18)	0.23161 (10)	0.0275 (3)
N2	0.5639 (2)	0.3516 (2)	0.10003 (11)	0.0391 (4)
H2A	0.5124	0.3396	0.0423	0.047*
H2B	0.5442	0.2648	0.1315	0.047*
N3	0.7001 (2)	0.63589 (19)	0.08811 (10)	0.0325 (3)
O1	0.5657 (2)	0.13248 (17)	0.24773 (10)	0.0431 (3)
O2	0.5911 (2)	−0.00443 (19)	0.37263 (10)	0.0505 (4)
O3	0.9335 (2)	0.67430 (16)	0.35958 (8)	0.0358 (3)
O4	0.8251 (2)	0.90964 (17)	0.07066 (9)	0.0422 (3)
O5	0.6559 (3)	0.4086 (2)	0.42371 (12)	0.0550 (4)
H5A	0.664 (5)	0.511 (3)	0.438 (2)	0.083*
H5B	0.586 (4)	0.345 (4)	0.451 (2)	0.083*
C1	0.5287 (3)	−0.0037 (2)	0.28937 (13)	0.0356 (4)
C2	0.4079 (3)	−0.1618 (2)	0.23155 (13)	0.0327 (4)
C4	0.2281 (3)	−0.4484 (3)	0.17815 (18)	0.0523 (6)
H4	0.1683	−0.5643	0.1797	0.063*
C5	0.2238 (3)	−0.3636 (3)	0.10238 (18)	0.0541 (6)
H5	0.1606	−0.4191	0.0444	0.065*
C6	0.6748 (2)	0.5056 (2)	0.14080 (12)	0.0290 (3)
C7	0.8636 (2)	0.6772 (2)	0.26996 (11)	0.0269 (3)
C8	0.8943 (3)	0.8205 (2)	0.22267 (12)	0.0288 (3)
H8	0.9664	0.9294	0.2505	0.035*
C9	0.8079 (3)	0.7885 (2)	0.12941 (12)	0.0297 (3)
C10	1.0560 (3)	0.8313 (3)	0.41224 (13)	0.0421 (5)
H10A	1.1706	0.8666	0.3890	0.063*
H10B	1.0928	0.8104	0.4751	0.063*
H10C	0.9861	0.9214	0.4077	0.063*
C11	0.9367 (4)	1.0825 (2)	0.10631 (15)	0.0459 (5)
H11A	0.8751	1.1310	0.1485	0.069*
H11B	0.9436	1.1537	0.0569	0.069*
H11C	1.0657	1.0780	0.1373	0.069*
O6	0.3876 (2)	0.2640 (2)	0.51582 (11)	0.0459 (3)
H6A	0.401 (4)	0.183 (3)	0.5458 (19)	0.069*
H6B	0.287 (3)	0.236 (4)	0.4748 (17)	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.04099 (15)	0.02731 (13)	0.02565 (14)	0.00634 (10)	0.00462 (10)	0.00657 (9)
Cl1	0.0456 (3)	0.0442 (3)	0.0470 (3)	0.0149 (2)	0.0023 (2)	0.0118 (2)
S1A	0.0418 (7)	0.0456 (9)	0.0322 (6)	0.0046 (5)	0.0024 (5)	0.0011 (7)
C3A	0.051 (3)	0.056 (5)	0.040 (5)	0.019 (3)	0.011 (3)	0.007 (3)
S1B	0.0398 (11)	0.0272 (9)	0.044 (2)	0.0012 (7)	0.0049 (11)	0.0035 (12)
C3B	0.053 (7)	0.059 (9)	0.086 (14)	0.008 (5)	0.040 (8)	0.021 (6)
N1	0.0323 (7)	0.0241 (7)	0.0238 (7)	0.0055 (5)	0.0025 (6)	0.0044 (5)
N2	0.0507 (9)	0.0292 (8)	0.0282 (8)	0.0018 (7)	−0.0026 (7)	0.0039 (6)
N3	0.0403 (8)	0.0307 (7)	0.0234 (7)	0.0066 (6)	0.0016 (6)	0.0057 (6)
O1	0.0533 (8)	0.0286 (7)	0.0397 (8)	0.0003 (6)	0.0026 (6)	0.0095 (6)
O2	0.0685 (10)	0.0380 (8)	0.0342 (8)	−0.0011 (7)	0.0023 (7)	0.0066 (6)
O3	0.0500 (8)	0.0286 (6)	0.0214 (6)	0.0018 (5)	−0.0007 (5)	0.0051 (5)
O4	0.0613 (9)	0.0313 (7)	0.0279 (7)	0.0025 (6)	0.0043 (6)	0.0116 (5)
O5	0.0809 (12)	0.0329 (8)	0.0587 (10)	0.0045 (8)	0.0414 (9)	0.0057 (7)
C1	0.0382 (10)	0.0284 (9)	0.0383 (11)	0.0049 (7)	0.0074 (8)	0.0064 (8)
C2	0.0314 (9)	0.0293 (9)	0.0364 (10)	0.0054 (7)	0.0075 (7)	0.0033 (7)
C4	0.0509 (12)	0.0338 (10)	0.0695 (16)	0.0005 (9)	0.0196 (11)	−0.0026 (10)
C5	0.0435 (12)	0.0563 (14)	0.0518 (14)	0.0003 (10)	0.0050 (10)	−0.0153 (11)
C6	0.0318 (8)	0.0292 (8)	0.0256 (8)	0.0088 (7)	0.0041 (7)	0.0038 (7)
C7	0.0312 (8)	0.0278 (8)	0.0214 (8)	0.0075 (6)	0.0046 (6)	0.0043 (6)
C8	0.0328 (8)	0.0252 (8)	0.0268 (8)	0.0048 (6)	0.0053 (7)	0.0036 (6)
C9	0.0341 (9)	0.0293 (8)	0.0260 (8)	0.0081 (7)	0.0058 (7)	0.0087 (7)
C10	0.0555 (12)	0.0350 (10)	0.0255 (9)	−0.0009 (9)	0.0000 (8)	−0.0016 (8)
C11	0.0700 (14)	0.0282 (9)	0.0362 (11)	0.0043 (9)	0.0115 (10)	0.0101 (8)
O6	0.0494 (9)	0.0447 (8)	0.0389 (8)	0.0054 (7)	0.0043 (6)	0.0122 (7)

Geometric parameters (Å, º)

Co1—O5	1.9625 (16)	O2—C1	1.238 (2)
Co1—O1	1.9646 (14)	O3—C7	1.339 (2)
Co1—N1	2.0564 (14)	O3—C10	1.441 (2)
Co1—Cl1	2.2585 (6)	O4—C9	1.343 (2)
S1A—C5	1.649 (4)	O4—C11	1.439 (2)
S1A—C2	1.675 (3)	O5—H5A	0.817 (18)
C3A—C2	1.410 (11)	O5—H5B	0.819 (18)
C3A—C4	1.425 (12)	C1—C2	1.474 (3)
C3A—H3A	0.9300	C4—C5	1.352 (4)
S1B—C4	1.593 (6)	C4—H4	0.9300
S1B—C2	1.657 (6)	C5—H5	0.9300
C3B—C2	1.431 (18)	C7—C8	1.374 (2)
C3B—C5	1.462 (19)	C8—C9	1.394 (2)
C3B—H3B	0.9300	C8—H8	0.9300
N1—C7	1.348 (2)	C10—H10A	0.9600
N1—C6	1.358 (2)	C10—H10B	0.9600
N2—C6	1.339 (2)	C10—H10C	0.9600
N2—H2A	0.8600	C11—H11A	0.9600
N2—H2B	0.8600	C11—H11B	0.9600
N3—C9	1.326 (2)	C11—H11C	0.9600
N3—C6	1.340 (2)	O6—H6A	0.814 (17)
O1—C1	1.283 (2)	O6—H6B	0.827 (17)
O5—Co1—O1	109.43 (7)	C1—C2—S1A	119.56 (16)
O5—Co1—N1	107.80 (6)	C5—C4—C3A	108.5 (5)
O1—Co1—N1	101.58 (6)	C5—C4—S1B	119.5 (3)
O5—Co1—Cl1	120.36 (6)	C5—C4—H4	125.8
O1—Co1—Cl1	109.14 (5)	C3A—C4—H4	125.8
N1—Co1—Cl1	106.84 (4)	C4—C5—C3B	105.6 (7)
C5—S1A—C2	92.3 (2)	C4—C5—S1A	116.2 (2)
C2—C3A—C4	112.7 (8)	C4—C5—H5	121.9
C2—C3A—H3A	123.7	S1A—C5—H5	121.9
C4—C3A—H3A	123.7	N2—C6—N3	117.22 (16)
C4—S1B—C2	93.1 (3)	N2—C6—N1	118.32 (15)
C2—C3B—C5	112.0 (12)	N3—C6—N1	124.44 (15)
C2—C3B—H3B	124.0	O3—C7—N1	110.50 (14)
C5—C3B—H3B	124.0	O3—C7—C8	125.41 (15)
C7—N1—C6	116.09 (14)	N1—C7—C8	124.09 (15)
C7—N1—Co1	113.24 (11)	C7—C8—C9	114.17 (15)
C6—N1—Co1	130.61 (11)	C7—C8—H8	122.9
C6—N2—H2A	120.0	C9—C8—H8	122.9
C6—N2—H2B	120.0	N3—C9—O4	112.03 (15)
H2A—N2—H2B	120.0	N3—C9—C8	124.41 (15)
C9—N3—C6	116.73 (15)	O4—C9—C8	123.56 (16)
C1—O1—Co1	115.22 (12)	O3—C10—H10A	109.5
C7—O3—C10	118.75 (14)	O3—C10—H10B	109.5
C9—O4—C11	118.10 (15)	H10A—C10—H10B	109.5
Co1—O5—H5A	122 (2)	O3—C10—H10C	109.5
Co1—O5—H5B	125 (2)	H10A—C10—H10C	109.5
H5A—O5—H5B	112 (3)	H10B—C10—H10C	109.5
O2—C1—O1	122.72 (17)	O4—C11—H11A	109.5
O2—C1—C2	121.55 (17)	O4—C11—H11B	109.5
O1—C1—C2	115.73 (17)	H11A—C11—H11B	109.5
C3A—C2—C1	130.2 (5)	O4—C11—H11C	109.5
C3B—C2—C1	128.5 (8)	H11A—C11—H11C	109.5
C3B—C2—S1B	109.8 (8)	H11B—C11—H11C	109.5
C1—C2—S1B	121.7 (2)	H6A—O6—H6B	110 (3)
C3A—C2—S1A	110.2 (5)
Co1—O1—C1—O2	8.0 (3)	C2—C3B—C5—C4	−0.6 (15)
Co1—O1—C1—C2	−171.39 (12)	C2—S1A—C5—C4	1.1 (3)
C4—C3A—C2—C1	−179.2 (4)	C9—N3—C6—N2	179.07 (16)
C4—C3A—C2—S1A	−0.8 (10)	C9—N3—C6—N1	−2.4 (3)
C5—C3B—C2—C1	178.9 (6)	C7—N1—C6—N2	−178.52 (16)
C5—C3B—C2—S1B	−0.9 (16)	Co1—N1—C6—N2	4.6 (2)
O2—C1—C2—C3A	1.3 (8)	C7—N1—C6—N3	3.0 (2)
O1—C1—C2—C3A	−179.3 (7)	Co1—N1—C6—N3	−173.90 (13)
O2—C1—C2—C3B	−175.5 (11)	C10—O3—C7—N1	178.35 (16)
O1—C1—C2—C3B	3.9 (11)	C10—O3—C7—C8	−1.8 (3)
O2—C1—C2—S1B	4.3 (4)	C6—N1—C7—O3	178.75 (14)
O1—C1—C2—S1B	−176.3 (3)	Co1—N1—C7—O3	−3.80 (18)
O2—C1—C2—S1A	−176.9 (2)	C6—N1—C7—C8	−1.1 (2)
O1—C1—C2—S1A	2.5 (3)	Co1—N1—C7—C8	176.39 (13)
C4—S1B—C2—C3B	1.7 (10)	O3—C7—C8—C9	179.06 (16)
C4—S1B—C2—C1	−178.14 (19)	N1—C7—C8—C9	−1.2 (3)
C5—S1A—C2—C3A	−0.1 (6)	C6—N3—C9—O4	179.65 (15)
C5—S1A—C2—C1	178.48 (17)	C6—N3—C9—C8	−0.1 (3)
C2—C3A—C4—C5	1.5 (10)	C11—O4—C9—N3	179.30 (17)
C2—S1B—C4—C5	−2.2 (4)	C11—O4—C9—C8	−0.9 (3)
S1B—C4—C5—C3B	2.0 (9)	C7—C8—C9—N3	1.8 (3)
C3A—C4—C5—S1A	−1.7 (6)	C7—C8—C9—O4	−177.95 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3^i	0.86	2.27	3.078 (2)	157
N2—H2B···O1	0.86	2.08	2.891 (2)	157
O5—H5A···O6^ii	0.82 (2)	2.02 (3)	2.813 (2)	164 (3)
O5—H5B···O6	0.82 (3)	1.92 (2)	2.711 (3)	161 (3)
O6—H6A···O2^iii	0.82 (3)	1.92 (3)	2.732 (2)	171 (3)
O6—H6B···Cl1^iv	0.83 (2)	2.34 (2)	3.1142 (17)	156 (3)

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

(II) catena-Poly[copper(II)-tetrakis(µ-thiophene-2-carboxylato-κ²O:O')-copper(II)-(µ-2-amino-4,6-dimethoxypyrimidine-κ²N¹:N³)]

Crystal data

[Cu2(C5H3O2S)4(C6H9N3O2)]	F(000) = 1600
Mr = 790.78	Dx = 1.718 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.5881 (4) Å	Cell parameters from 3683 reflections
b = 10.1091 (3) Å	θ = 0.4–27.5°
c = 17.5284 (4) Å	µ = 1.73 mm^−1
β = 111.847 (2)°	T = 293 K
V = 3057.19 (14) Å^3	Plate, green
Z = 4	0.20 × 0.15 × 0.04 mm

Data collection

Nonius KappaCCD area-detector diffractometer	3495 independent reflections
Radiation source: fine-focus sealed tube	2788 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 0.055 pixels mm^-1	θmax = 27.5°, θmin = 3.7°
ω scans	h = −23→24
Absorption correction: multi-scan SCALEPACK (Otwinowski & Minor, 1997)	k = −13→13
Tmin = 0.724, Tmax = 0.934	l = −22→22
6750 measured reflections

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.0421P)^2 + 1.960P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
3495 reflections	Δρmax = 0.40 e Å^−3
244 parameters	Δρmin = −0.41 e Å^−3

Special details

Experimental. 216 frames in 5 sets of ω scans. Rotation/frame = 2.0 °. Crystal-detector distance = 28.0 mm. Measuring time = 140 s/°.

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)
Cu1	0.00419 (2)	0.57539 (3)	0.06651 (2)	0.02952 (10)
S1A	0.2327 (4)	0.3342 (7)	0.2344 (4)	0.0526 (12)	0.372 (4)
C7A	0.2231 (17)	0.202 (3)	0.1094 (18)	0.078 (10)	0.372 (4)
H7A	0.2051	0.1667	0.0566	0.093*	0.372 (4)
S1B	0.2277 (3)	0.1871 (4)	0.1020 (3)	0.0632 (8)	0.628 (4)
C7B	0.2438 (8)	0.3101 (15)	0.2269 (10)	0.0408 (19)	0.628 (4)
H7B	0.2363	0.3686	0.2642	0.049*	0.628 (4)
S2A	0.1411 (3)	0.7579 (6)	−0.1467 (4)	0.0655 (9)	0.594 (5)
C12A	0.1728 (12)	0.8723 (16)	−0.0115 (11)	0.067 (4)	0.594 (5)
H12B	0.1768	0.8921	0.0417	0.080*	0.594 (5)
S2B	0.1696 (5)	0.8945 (7)	0.0069 (5)	0.0733 (15)	0.406 (5)
C12B	0.146 (2)	0.771 (3)	−0.1285 (17)	0.086 (10)	0.406 (5)
H12A	0.1289	0.7091	−0.1709	0.103*	0.406 (5)
O1	0.09355 (10)	0.4623 (2)	0.12613 (10)	0.0482 (4)
O2	0.08668 (10)	0.34258 (19)	0.01621 (10)	0.0505 (4)
O3	0.07431 (10)	0.68588 (18)	0.03368 (10)	0.0457 (4)
O4	0.06310 (10)	0.56831 (18)	−0.07797 (10)	0.0469 (4)
O5	0.01328 (12)	0.86722 (17)	0.11957 (10)	0.0502 (4)
N1	0.00267 (10)	0.68131 (18)	0.18218 (10)	0.0324 (4)
N2	0.0000	0.4891 (3)	0.2500	0.0600 (10)
H2A	−0.0016	0.4465	0.2918	0.072*	0.5
H2B	0.0016	0.4465	0.2082	0.072*	0.5
C1	0.0000	0.6204 (3)	0.2500	0.0362 (7)
C2	0.00504 (13)	0.8131 (2)	0.18517 (13)	0.0364 (5)
C3	0.0000	0.8863 (3)	0.2500	0.0413 (8)
H3	0.0000	0.9783	0.2500	0.050*
C4	0.0327 (2)	1.0041 (3)	0.1226 (2)	0.0679 (9)
H4A	−0.0099	1.0562	0.1242	0.102*
H4B	0.0433	1.0269	0.0746	0.102*
H4C	0.0778	1.0212	0.1709	0.102*
C5	0.11759 (12)	0.3752 (2)	0.09023 (14)	0.0363 (5)
C6	0.18917 (13)	0.3049 (2)	0.13996 (16)	0.0420 (6)
C8	0.2988 (2)	0.1600 (4)	0.1855 (3)	0.0902 (13)
H8	0.3347	0.0962	0.1849	0.108*
C9	0.30166 (17)	0.2305 (4)	0.2485 (3)	0.0883 (14)
H9	0.3418	0.2213	0.2993	0.106*
C10	0.08662 (12)	0.6657 (2)	−0.03087 (13)	0.0352 (5)
C11	0.13244 (15)	0.7657 (3)	−0.05444 (16)	0.0435 (6)
C13	0.2085 (3)	0.9512 (4)	−0.0560 (3)	0.0907 (14)
H13	0.2367	1.0287	−0.0378	0.109*
C14	0.1937 (3)	0.8929 (4)	−0.1278 (3)	0.0876 (12)
H14	0.2124	0.9271	−0.1661	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03063 (15)	0.03413 (16)	0.02377 (14)	−0.00160 (11)	0.01009 (10)	−0.00019 (11)
S1A	0.038 (2)	0.074 (3)	0.0437 (17)	0.0139 (14)	0.0129 (14)	0.0110 (19)
C7A	0.059 (12)	0.10 (2)	0.045 (8)	0.019 (10)	−0.010 (8)	0.001 (10)
S1B	0.0523 (13)	0.0470 (10)	0.083 (2)	0.0103 (9)	0.0162 (12)	−0.0118 (10)
C7B	0.027 (3)	0.058 (5)	0.044 (4)	0.020 (2)	0.019 (2)	0.005 (3)
S2A	0.0894 (18)	0.0677 (17)	0.0576 (15)	−0.0249 (14)	0.0484 (13)	−0.0008 (14)
C12A	0.083 (5)	0.061 (7)	0.080 (9)	−0.020 (4)	0.058 (6)	−0.021 (5)
S2B	0.099 (3)	0.057 (2)	0.088 (3)	−0.041 (2)	0.0619 (18)	−0.0233 (18)
C12B	0.099 (12)	0.067 (9)	0.09 (2)	−0.041 (8)	0.033 (11)	−0.017 (10)
O1	0.0447 (9)	0.0619 (12)	0.0337 (9)	0.0162 (8)	0.0095 (7)	0.0042 (8)
O2	0.0451 (9)	0.0508 (11)	0.0430 (10)	0.0134 (8)	0.0018 (8)	−0.0039 (8)
O3	0.0551 (10)	0.0472 (10)	0.0461 (9)	−0.0165 (8)	0.0319 (8)	−0.0101 (8)
O4	0.0578 (11)	0.0545 (11)	0.0340 (9)	−0.0233 (8)	0.0237 (8)	−0.0085 (8)
O5	0.0840 (13)	0.0395 (10)	0.0374 (9)	−0.0015 (9)	0.0345 (9)	0.0047 (8)
N1	0.0379 (9)	0.0341 (10)	0.0254 (8)	0.0005 (8)	0.0122 (7)	0.0008 (7)
N2	0.129 (3)	0.0305 (16)	0.0274 (14)	0.000	0.0365 (18)	0.000
C1	0.0427 (17)	0.0393 (17)	0.0240 (14)	0.000	0.0096 (13)	0.000
C2	0.0435 (12)	0.0380 (12)	0.0303 (11)	0.0020 (10)	0.0168 (9)	0.0039 (9)
C3	0.061 (2)	0.0302 (16)	0.0384 (18)	0.000	0.0254 (16)	0.000
C4	0.113 (3)	0.0447 (17)	0.0607 (18)	−0.0035 (17)	0.0491 (19)	0.0102 (14)
C5	0.0304 (10)	0.0366 (12)	0.0397 (12)	−0.0014 (9)	0.0104 (10)	0.0093 (10)
C6	0.0317 (11)	0.0394 (13)	0.0520 (14)	0.0018 (10)	0.0121 (10)	0.0139 (11)
C8	0.054 (2)	0.060 (2)	0.154 (4)	0.0223 (17)	0.035 (2)	0.032 (3)
C9	0.0376 (16)	0.121 (4)	0.088 (3)	0.0025 (19)	0.0012 (17)	0.057 (3)
C10	0.0335 (11)	0.0370 (12)	0.0354 (11)	−0.0022 (9)	0.0133 (9)	0.0039 (10)
C11	0.0515 (14)	0.0402 (14)	0.0492 (14)	−0.0067 (11)	0.0309 (12)	−0.0003 (11)
C13	0.121 (3)	0.058 (2)	0.134 (4)	−0.040 (2)	0.094 (3)	−0.025 (2)
C14	0.130 (3)	0.062 (2)	0.108 (3)	−0.020 (2)	0.087 (3)	0.002 (2)

Geometric parameters (Å, º)

Cu1—O2^i	1.9545 (16)	O2—C5	1.252 (3)
Cu1—O3	1.9587 (16)	O2—Cu1^i	1.9546 (16)
Cu1—O1	1.9661 (17)	O3—C10	1.252 (3)
Cu1—O4^i	1.9752 (16)	O4—C10	1.255 (3)
Cu1—N1	2.3024 (17)	O4—Cu1^i	1.9752 (16)
Cu1—Cu1^i	2.7412 (5)	O5—C2	1.333 (3)
S1A—C6	1.577 (8)	O5—C4	1.426 (3)
S1A—C9	1.603 (2)	N1—C2	1.333 (3)
C7A—C6	1.42 (3)	N1—C1	1.356 (2)
C7A—C8	1.59 (3)	N2—C1	1.328 (5)
C7A—H7A	0.9300	N2—H2A	0.8600
S1B—C8	1.589 (7)	N2—H2B	0.8600
S1B—C6	1.651 (5)	C1—N1^ii	1.356 (2)
C7B—C9	1.282 (11)	C2—C3	1.388 (3)
C7B—C6	1.485 (17)	C3—C2^ii	1.388 (3)
C7B—H7B	0.9300	C3—H3	0.9300
S2A—C14	1.639 (7)	C4—H4A	0.9600
S2A—C11	1.685 (5)	C4—H4B	0.9600
C12A—C11	1.367 (15)	C4—H4C	0.9600
C12A—C13	1.440 (16)	C5—C6	1.474 (3)
C12A—H12B	0.9300	C8—C9	1.298 (6)
S2B—C13	1.632 (7)	C8—H8	0.9300
S2B—C11	1.666 (6)	C9—H9	0.9300
C12B—C11	1.42 (2)	C10—C11	1.476 (3)
C12B—C14	1.51 (3)	C13—C14	1.322 (5)
C12B—H12A	0.9300	C13—H13	0.9300
O1—C5	1.258 (3)	C14—H14	0.9300
O2^i—Cu1—O3	91.49 (8)	O5—C2—C3	123.5 (2)
O2^i—Cu1—O1	165.21 (7)	N1—C2—C3	123.6 (2)
O3—Cu1—O1	87.97 (8)	C2^ii—C3—C2	115.6 (3)
O2^i—Cu1—O4^i	88.99 (8)	C2^ii—C3—H3	122.2
O3—Cu1—O4^i	164.81 (7)	C2—C3—H3	122.2
O1—Cu1—O4^i	87.72 (8)	O5—C4—H4A	109.5
O2^i—Cu1—N1	99.53 (7)	O5—C4—H4B	109.5
O3—Cu1—N1	102.78 (7)	H4A—C4—H4B	109.5
O1—Cu1—N1	95.00 (7)	O5—C4—H4C	109.5
O4^i—Cu1—N1	92.11 (7)	H4A—C4—H4C	109.5
O2^i—Cu1—Cu1^i	81.08 (5)	H4B—C4—H4C	109.5
O3—Cu1—Cu1^i	84.29 (5)	O2—C5—O1	126.3 (2)
O1—Cu1—Cu1^i	84.16 (5)	O2—C5—C6	116.8 (2)
O4^i—Cu1—Cu1^i	80.79 (5)	O1—C5—C6	116.9 (2)
N1—Cu1—Cu1^i	172.87 (5)	C7A—C6—C5	124.1 (11)
C6—S1A—C9	96.1 (3)	C5—C6—C7B	135.4 (4)
C6—C7A—C8	104.9 (17)	C7A—C6—S1A	114.0 (11)
C6—C7A—H7A	127.5	C5—C6—S1A	121.9 (2)
C8—C7A—H7A	127.5	C5—C6—S1B	122.7 (3)
C8—S1B—C6	95.2 (3)	C7B—C6—S1B	101.8 (4)
C9—C7B—C6	117.3 (10)	C9—C8—S1B	116.4 (3)
C9—C7B—H7B	121.4	C9—C8—C7A	108.0 (11)
C6—C7B—H7B	121.4	C9—C8—H8	126.0
C14—S2A—C11	91.7 (4)	C7A—C8—H8	126.0
C11—C12A—C13	114.1 (9)	C7B—C9—C8	109.3 (8)
C11—C12A—H12B	123.0	C8—C9—S1A	116.8 (4)
C13—C12A—H12B	123.0	C8—C9—H9	121.6
C13—S2B—C11	91.2 (3)	S1A—C9—H9	121.6
C11—C12B—C14	109.0 (19)	O3—C10—O4	125.9 (2)
C11—C12B—H12A	125.5	O3—C10—C11	117.4 (2)
C14—C12B—H12A	125.5	O4—C10—C11	116.7 (2)
C5—O1—Cu1	121.92 (15)	C12A—C11—C10	129.9 (6)
C5—O2—Cu1^i	126.43 (16)	C12B—C11—C10	127.0 (13)
C10—O3—Cu1	122.57 (15)	C12B—C11—S2B	113.0 (14)
C10—O4—Cu1^i	126.11 (15)	C10—C11—S2B	119.9 (3)
C2—O5—C4	118.4 (2)	C12A—C11—S2A	109.6 (7)
C2—N1—C1	115.5 (2)	C10—C11—S2A	120.5 (3)
C2—N1—Cu1	119.22 (15)	C14—C13—C12A	107.1 (6)
C1—N1—Cu1	125.27 (17)	C14—C13—S2B	119.9 (4)
C1—N2—H2A	120.0	C14—C13—H13	126.5
C1—N2—H2B	120.0	C12A—C13—H13	126.5
H2A—N2—H2B	120.0	C13—C14—C12B	106.6 (10)
N2—C1—N1^ii	117.00 (15)	C13—C14—S2A	117.5 (3)
N2—C1—N1	117.00 (15)	C13—C14—H14	121.3
N1^ii—C1—N1	126.0 (3)	S2A—C14—H14	121.3
O5—C2—N1	112.9 (2)
C2—N1—C1—N2	−177.99 (14)	C6—S1B—C8—C9	0.8 (4)
Cu1—N1—C1—N2	1.57 (15)	C6—C7A—C8—C9	2 (2)
C2—N1—C1—N1^ii	2.01 (14)	C6—C7B—C9—C8	0.1 (15)
Cu1—N1—C1—N1^ii	−178.44 (15)	S1B—C8—C9—C7B	−0.6 (10)
C4—O5—C2—N1	−167.1 (2)	C7A—C8—C9—S1A	0.2 (13)
C4—O5—C2—C3	12.4 (3)	C6—S1A—C9—C8	−2.1 (6)
C1—N1—C2—O5	175.41 (16)	Cu1—O3—C10—O4	−7.3 (3)
Cu1—N1—C2—O5	−4.2 (3)	Cu1—O3—C10—C11	172.19 (16)
C1—N1—C2—C3	−4.2 (3)	Cu1^i—O4—C10—O3	3.3 (4)
Cu1—N1—C2—C3	176.24 (13)	Cu1^i—O4—C10—C11	−176.19 (16)
O5—C2—C3—C2^ii	−177.3 (3)	C13—C12A—C11—C10	−177.8 (6)
N1—C2—C3—C2^ii	2.24 (16)	C13—C12A—C11—S2A	2.4 (17)
Cu1^i—O2—C5—O1	3.9 (4)	C14—C12B—C11—C10	177.9 (9)
Cu1^i—O2—C5—C6	−175.84 (16)	C14—C12B—C11—S2B	2 (3)
Cu1—O1—C5—O2	−5.1 (3)	O3—C10—C11—C12A	9.0 (12)
Cu1—O1—C5—C6	174.63 (15)	O4—C10—C11—C12A	−171.5 (12)
C8—C7A—C6—C5	179.5 (7)	O3—C10—C11—C12B	−172.6 (18)
C8—C7A—C6—S1A	−3 (2)	O4—C10—C11—C12B	6.9 (18)
O2—C5—C6—C7A	−1.7 (16)	O3—C10—C11—S2B	3.4 (5)
O1—C5—C6—C7A	178.6 (16)	O4—C10—C11—S2B	−177.0 (4)
O2—C5—C6—C7B	180.0 (10)	O3—C10—C11—S2A	−171.3 (3)
O1—C5—C6—C7B	0.2 (10)	O4—C10—C11—S2A	8.3 (4)
O2—C5—C6—S1A	−178.5 (4)	C13—S2B—C11—C12B	−3.9 (17)
O1—C5—C6—S1A	1.7 (5)	C13—S2B—C11—C10	179.5 (3)
O2—C5—C6—S1B	−0.7 (4)	C14—S2A—C11—C12A	−1.5 (10)
O1—C5—C6—S1B	179.5 (3)	C14—S2A—C11—C10	178.7 (3)
C9—C7B—C6—C5	179.8 (6)	C11—C12A—C13—C14	−2.2 (17)
C9—C7B—C6—S1B	0.5 (14)	C11—S2B—C13—C14	5.9 (7)
C9—S1A—C6—C7A	3.3 (15)	S2B—C13—C14—C12B	−5.6 (15)
C9—S1A—C6—C5	−179.5 (3)	C12A—C13—C14—S2A	1.1 (11)
C8—S1B—C6—C5	179.9 (2)	C11—C12B—C14—C13	2 (2)
C8—S1B—C6—C7B	−0.7 (7)	C11—S2A—C14—C13	0.2 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O4^i	0.86	2.15	2.8588 (18)	139

Symmetry code: (i) −x, −y+1, −z.