Bis[bis(4,4′-dimethyl-2,2′-bipyridine)(10,11,12,13-tetrahydrodipyrido[3,2-a:2′,3′-c]phenazine)ruthenium(II)] tetrakis(perchlorate) acetonitrile disolvate monohydrate

The asymmetric unit of the title compound, [Ru(C12H12N2)2(C18H14N4)]2(ClO4)4·2CH3CN·H2O, contains two RuII complex cations, four perchlorate counter-anions, two uncoordinated acetonitrile molecules and one water molecule. The RuII ions are chelated by one 10,11,12,13-tetrahydrodipyrido[3,2-a:2′,3′-c]phenazine (dpqc) and two 4,4′-dimethyl-2,2′-bipyridine (dmb) ligands in a distorted octahedral geometry. The uncoordinated water molecule is disordered over three positions, with occupancy factors of 0.398 (9), 0.312 (8) and 0.290 (8). A supramolecular structure is formed by weak π–π interactions between neighbouring molecules, with face-to-face distances of 3.51 (1) Å [centroid–centroid distance 3.81 (1) Å].

supplementary materials sup-2 The complex 2[Ru(dmb) 2 (dpqc)].4(ClO 4 ).2CH 3 CN.H 2 O was synthesized by a modified method respect of Pellegrini, et al., 2003. A mixture of cis-[Ru(dmb) 2 Cl 2 ].2H 2 O (0.288 g, 0.5 mmol) and dpqc (0.161 g, 0.5 mmol) in EtOH (40 cm 3 ) was refluxed under argon for 8 h to give a clear red solution. Upon cooling, a red precipitate was obtained by dropwise addition of saturated aqueous NaClO 4 solution. The crude product was purified by column chromatography on neutral alumina with CH 3 CN-toluene (3:1, v/v) as eluent. The mainly brown red band was collected. The solvent was removed under reduced pressure and a red powder was obtained. Yield: 62%. Anal. Calcd (%) for C 44 H 42 N 9 Cl 2 O 8.5 Ru: C 52.59,H 4.21,N 12.55%. Found (%): C 52.57,H 4.22,N 12.56; Red single crystals of the complex suitable for an X-ray crystallographic study was grown from acetonitrile and ethanol(v:v 1:1) at room temperature.

Refinement
In the asymmetric unit there is one water molecule disordered into three different sites with occupancy factors of 0.398 (9), 0.312 (8) and 0.290 (8), respectively.
C-H's were positioned geometrically and allowed to ride, with C-H = 0.95 (CH), 0.99 (CH2) and 0.98 (CH3) Å and with Uiso(H) = 1.2 (1.5 for methyl)Ueq(C). H atoms of water molecules were determined based on difference Fourier maps and possible hydrogen bonding scheme and allowed to ride with Uiso(H) = 1.2Ueq(O). The highest residual electron density was found 0.42 Å from C4 and the deepest hole 0.76 Å from H69. Fig. 1. A view of the title compound showing the atom-numbering scheme and displacement ellipsoids drawn at 30% probability level, for the sake of clarity, the H atoms have been omitted. Fig. 2. A view of the π-π interactions between neighbouring molecules. All H atoms have been omitted for clarity. ( i) 1+x,y,z, ii) -1+x,y,z ).

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.
Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 11.8722 (0.0072) x + 4.5367 (0.0201) y + 1.8609 (0.0347) z = 11.2527 (0.0245) 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 Rfactors(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.
In the asymmetric unit there are one disordered water molecules. They occupy three different positions and theirs site occupancy factors were refined with free variable and validated as theirs site occupancy factors are 0.398 (9), 0.312 (8) and 0.290 (8) for O1W, O2W and O3W, respectively.
H atoms on C atoms were positioned geometrically and refined as riding atoms, with C-H = 0.95 (CH), 0.99 (CH 2 ) and 0.98 (CH 3 ) Å and with Uiso(H) = 1.2 (1.5 for methyl)Ueq(C). H atoms of water molecules were determined based on difference Fourier maps and possible hydrogen bonding scheme and refined as riding, with Uiso(H) = 1.2Ueq(O). The highest residual electron density was found 0.42 Å from C4 and the deepest hole 0.76 Å from H69.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 )
x y z U iso */U eq Occ. (