Aqua[1-(1,10-phenanthrolin-2-yl-κ2 N,N′)-1H-pyrazol-3-amine-κN 2](sulfato-κO)copper(II) methanol monosolvate dihydrate

In the title compound, [Cu(SO4)(C15H11N5)(H2O)]·CH3OH·2H2O, the CuII ion is in a distorted square-pyramidal geometry, in which three N atoms from the chelating 1-(1,10-phenanthrolin-2-yl)-1H-pyrazol-3-amine ligand and one O atom from a sulfate anion define the basal plane and the O atom from the coordinating water molecule is located at the apex. In the crystal, hydrogen-bonding interactions involving the coordinating and solvent water molecules, the methanol solvent molecule and the amine group (one with an intramolecular interaction to one of the sulfate O atoms) of the complex are observed. π–π interactions between symmetry-related phenantroline moieties, with a shortest centroid–centroid interaction of 3.573 (2)°, are also present.

In the title compound, [Cu(SO 4 )(C 15 H 11 N 5 )(H 2 O)]ÁCH 3 OHÁ-2H 2 O, the Cu II ion is in a distorted square-pyramidal geometry, in which three N atoms from the chelating 1-(1,10-phenanthrolin-2-yl)-1H-pyrazol-3-amine ligand and one O atom from a sulfate anion define the basal plane and the O atom from the coordinating water molecule is located at the apex. In the crystal, hydrogen-bonding interactions involving the coordinating and solvent water molecules, the methanol solvent molecule and the amine group (one with an intramolecular interaction to one of the sulfate O atoms) of the complex are observed.interactions between symmetryrelated phenantroline moieties, with a shortest centroidcentroid interaction of 3.573 (2) , are also present.

Related literature
For related structures, see: Li et al. (2011a,b).
been reported with these types of derivatives as ligands, e.g. Li et al. (2011a,b) for closely related Cu II complexes. To the best of our knowledge, there is no report for a complex with 1-(1,10-phenanthrolin-9-yl)-1H-pyrazol-3-amine as ligand.
Herein we report the crystal of the solvated title complex, (I).
The molecular structure of (I) is shown in Fig. 1. The Cu II ion is is a distorted square-pyramidal coordination geometry with the O atom of the water molecule at the apex and three N atoms from the ligand and one O atoms from the sulfate anion in the basal plane. The non-hydrogen atoms from the 1-(1,10-phenanthrolin-9-yl)-1H-pyrazol-3-amine ligand make an approximate plane within 0.074 Å (rms deviation) with a maximum deviation of 0.145 (3) Å for the N5 atom.
In the crystal, the uncoordinated water molecules, the methanol molecule and the metal complex are connected to each other by hydrogen bonding interactions as shown in Table 2 and Figure 2. The coordinating water molecule and the solvent water molecule (O5-H4···O7 and O5-H5···O8) interact, as well as the solvent water molecules with the methanol molecule (O7-H6···O6 and O8-H17···O6). The solvent water molecules are also donors to the free sulfate O atoms of the complex (O7-H7···O4; O8-H18···O2). The complex is also connected via its amine function as donor molecule to an the adjacent complex (N5-H5···O2).There is also an intramolecular hydrogen bond in the complex, which involves the amine group and the O atom from sulfate anion (N5-H5A···O4).
π-π interactions between symmetry-related phenantroline moieties with a shortest centroid to centroid interaction of 3.573 (2) Å may consolidate the crystal packing.

Experimental
A 10 mL methanol solution of 1-(1,10-phenanthrolin-9-yl)-1H-pyrazol-3-amine (0.0549 g, 0.21 mmol) was added into a 10 mL water solution containing CuSO 4 . 5H 2 O (0.0549 g, 0.22 mmol), and the resulting solution was stirred for a few minutes. Yellow single crystals were obtained after the filtrate had been allowed to stand at room temperature for about one week.

Refinement
The positions of the H atoms of the water molecule and hydroxyl group were located in a difference map; other H atoms were placed in calculated positions. All H atoms were refined as riding with C-H = 0.96 Å, U iso = 1.5U eq (C) for methyl group; C-H = 0.93 Å, U iso = 1.2U eq (C) for aromatic groups; N-H = 0.86 Å, U iso = 1.2U eq (N); O-H = 0.84-0.90 Å, U iso = 1.5U eq (O).

Figure 1
The asymmetric unit of the title compound with displacement ellipsoids shown at the 30% probability level.  Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Refinement. Refinement of 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 > 2sigma(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.