Crystal structure of aquabis[4-(methylsulfanyl)benzoato-κO](1,10-phenanthroline-κ2 N,N′)copper(II) monohydrate

In a hydrated CuII complex with 1,10-phenanthroline and 4-(methylsulfanyl)benzoate ligands, a three-dimensional supramolecular network is formed through weak intermolecular C—H⋯O and C—H⋯S interactions and π-stacking between the planes of phenanthroline and the aromatic rings of symmetry-related 4-(methylsulfanyl)benzoate ligands.


Chemical context
There are numerous reasons for the rapidly increasing interest in the design and synthesis of metal-organic frameworks based on transition metal carboxylate ligands. Not only do they often display fascinating structures in crystal engineering, but also have value due to their potential applications, including as homogeneous catalysts for various oxidation reactions (Bilgrien et al., 1987;Zhang et al., 2011), elucidation of electrical conductivity (Campbell et al., 2015;Talin et al., 2014), and as attractive molecular magnetic materials (Kitagawa et al., 2004;Janiak et al., 2003). Transition metal complexes with thiol groups in their periphery are likely to play a vital role in the development of advanced functional materials because the functionalized thiomethyl groups around the periphery of the complex may provide binding sites for the surfaces of some specific materials, such as gold, silver, or palladium (Naitabdi et al., 2005;Jiang et al., 2014). As part of the above-mentioned systematic investigations, we report here the crystal structure of the title compound, Cu(OOCPhSCH 3 ) 2 (N 2 C 12 H 12 )ÁH 2 O (I).

Structure commentary
In (I), the central Cu II atom has a slightly distorted squarepyramidal coordination geometry (Fig. 1). The equatorial ISSN 2056-9890 plane is formed by two nitrogen atoms from the 1,10phenanthroline ligand, one oxygen atom from the carboxylate group of a 4-(methylsulfanyl)benzoate anion and one water oxygen atom, whereas the apical position is occupied by a carboxylate O atom from the second anion. The average Cu-N bond length is 2.014 (6) Å , the Cu-O(carboxylate) bond length is 1.945 (2) Å , while the Cu-O(water) is 1.953 (2) Å . The apical Cu-O distance is 2.301 (2) Å . Two intramolecular hydrogen bonds involving the coordinating water molecule, O5-H5AÁ Á ÁO3 and O5-H5BÁ Á ÁO1, are observed (Table 1).

Figure 3
Projection along the c axis of the three-dimensional framework in (I), showing the cavities. H atoms and water molecules have been omitted for clarity.

Synthesis and Crystallization
Copper(II) acetate monohydrate (0.1997 g, 1 mmol) in H 2 O (10 mL) was added to a stirred solution of the sodium salt of 4-(methylsulfanyl)benzoic acid (0.19 g, 1 mmol) in H 2 O (10 mL) and phenanthroline (0.18 g, 1 mmol) in anhydrous alcohol (10 mL). The mixture was then stirred for two h, and then filtrated. Single crystals of the title complex were obtained by slow evaporation of this filtrate.

Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2. Carbon-bound H atoms were positioned geometrically, with C-H = 0.97 Å for methylene and 0.93 Å for aromatic, and refined using a riding model, with U iso (H) = 1.2 U eq (C). The water H atoms were located from difference maps and refined with d(O-H) = 0.79 Å and U iso (H) = 1.5U eq (O) for the coordinating water molecule, and with d(O-H) = 0.85 Å and U iso (H) = 1.5U eq (O) for the solvent water molecule. The hydroxyl H atom was positioned geometrically and freely refined.

Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 )