Tris(1,10-phenanthroline-κ2 N,N′)ruthenium(II) bis(perchlorate)

The asymmetric unit of the title compound, [Ru(C12H8N2)3](ClO4)2, contains one octahedrally coordinated RuII cation of the ruthenium-phenanthroline complex and three differently occupied perchlorate anions: two, denoted A and B, are located on the twofold axis while another, denoted C, is positioned in the proximity of the twofold screw axis. Perchlorate anions B and C are severely disordered. The occupancies of the two major conformers of anion B refined to 0.302 (6) and 0.198 (6). Perchlorate ion C was modeled in two alternate conformations which refined to occupancies of 0.552 (10) and 0.448 (10).

The asymmetric unit of the title compound, [Ru(C 12 H 8 N 2 ) 3 ](ClO 4 ) 2 , contains one octahedrally coordinated Ru II cation of the ruthenium-phenanthroline complex and three differently occupied perchlorate anions: two, denoted A and B, are located on the twofold axis while another, denoted C, is positioned in the proximity of the twofold screw axis. Perchlorate anions B and C are severely disordered. The occupancies of the two major conformers of anion B refined to 0.302 (6) and 0.198 (6). Perchlorate ion C was modeled in two alternate conformations which refined to occupancies of 0.552 (10) and 0.448 (10).

Experimental
Crystal data [Ru(C 12 (Juris et al., 1988). These compounds reveal also other interesting properties due to their redox (Plonska et al., 2002;Winkler et al., 2006) and magnetic properties (Miyasaka et al., 2001), excited-state reactivity (D′Angelantonio et al., 1991), and emission and lifetime characteristics (Juris et al., 1988;Balzani et al., 1996). A high photostability, long excited-state lifetimes and high quantum yields of luminescence, enabled to use them as oxygen optical sensors (Mills et al., 1997). A binding of these complexes to calf thymus DNA has been also investigated (Yang et al., 1997).
The asymmetric unit contains one divalent cation of the ruthenium-phenanthroline complex and three differently occupied perchlorate anions (Fig. 1). The half-ion of perchlorate A is located on the twofold axis and the complete anion is generated by the symmetry operation. Perchlorate anions, B and C are disordered and each one of them is modeled in two alternative conformations. The occupancy of two major conformers is refined to 0.302 (6) and 0.198 (6) or 0.552 (10) and 0.448 (10) for anion B or C, respectively. Conformers of perchlorate ion B are located on the twofold axis.

Experimental
The transition metal complex salt, [Ru II (phen) 3 ](ClO 4 ) 2 was prepared according to the procedure described by Burstall et al., 1952 and was recrystallized from methanol.

Refinement
The solvent/anion region is highly disordered and the final difference minimum and maximum (-1.15 and 2.62 e Å -3 ) indicate an its imperfect modeling. The highest difference peak corresponds to solvent accessible void in the crystal lattice. The disordered perchlorate anion B and C are modeled in two alternative conformations with geometric restraints (DFIX and SADI instructions). Additionally, displacement parameter restraints (DELU and ISOR instructions) are applied for anion B. Due to a serious disorder of perchlorate anion C, its oxygen atoms are refined isotropically. All H atoms were located in electron density difference maps. C-bonded hydrogen atoms were constrained to idealized positions with C-H distances fixed at 0.95 Å and 1.2U eq (C).

Crystal data
[Ru (C 12  T min = 0.859, T max = 1.000 28067 measured reflections 6867 independent reflections 5365 reflections with I > 2σ(I) 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.