Journal of Chemical Crystallography, Vol. 26, No. 1, 1996 A hydrogen-bonded dichloromethane-perchlorate-water channel in the crystal structure of cis-[Ru(bpy)2{PPh- (o-tolyl)2}Cl+][CIO4-]'CH2CI2"H20 Melvyn Rowen Churchill, tl)* Lynn M. Krajkowski, (1) My Hang Vo Huynh, (1) and Kenneth J. Takeuchi (~) Received November 6, 1995 The complex cis-[Ru(bpy)2 { PPh(o-tolyl)2 } CI +][CIO4- ] crystallized from a solution in dichlor- omethane as the dichloromethane-water solvate. The structure was refined to R = 4.5% for those 2433 reflections with IFol > 6cr(lFol). The octahedral Ru(II) cation is associated with metal-ligand distances as follows: Ru-CI = 2.434(3),~, Ru-PPh(o-tol)2 = 2.382(2),~, and Ru-N = 2.037(7) - 2.088(7),~. The structure is stabilized by a hydrogen-bonded CH2C12" 9 "C104-- 9 "H20 channel which incorporates adventitious water of crystallization. KEY WORDS: Ruthenium(ll); bipyridyl; phenyldi(o-tolyl)phosphine; solvate; hydrogen bonding; crys- tal structure. Introduction In the course of the study on the steric properties of a series of cations of the type [Ru(bpy)2(PRR2')CI § (where R,R' = Me, Ph, o-tolyl, etc), we have encoun- tered some very interesting solvates. We have pre- viously reported a structural study of the mixed toluene/dichloromethane solvate cis-[Ru(bpy)2(PPh3) Cl+][C104-].(toluene).--0.5(CH2C12) l and we now report the synthesis and crystal structure of an unusual mixed dichloromethane/water solvate, cis-[Ru(b- PY )2 { PPh(o-tolyl )2 } C1+] [CIO4- ]" (CH2C12)'(H20). Experimental Synthetic route The species cis-[Ru(bpy)2(Cl)2].2H20 (1) was prepared by the literature procedure. 2 The complex t) Department of Chemistry, Natural Sciences & Mathematics Com- plex, North Campus, University at Buffalo, State University of New York, Buffalo, New York 14260-3000. * To whom correspondence should be addressed. 67 cis- [Ru(bpy)z(C1) { P(C6Hs) (o-C6H4CH3) 2 } ] (CIO4) - 0.2C6H14 was prepared by the following preparation as a modification of a previously reported general reac- tion scheme. 2 Complex 1 (521 mg, 1 mmol) and 3.00 equiv, of P(C6Hs)(o-tolyl)2 were added to 100 mL of a nitrogen-deaerated ethanol-water mixture (80/20 v/v) and heated to reflux for 10 h. The solution was reduced to dryness; 50 mL of water and an excess of sodium perchlorate were then added to induce precipi- tation of the perchlorate salt. The red-orange solid was collected by suction filtration, air-dried and then dried in vacuo overnight. Purification was achieved by col- umn chromatography with basic alumina using 0.5% of methanol in methylene chloride as an eluent. The first red-orange band to elute was collected, and the solvent was removed with a rotary evaporator. The product was redissolved in minimal amount of methyl- ene chloride and titurated into hexanes. The microcrys- talline complex was collected by suction filtration, air- dried, and then dried in a vacuum oven overnight. Yield: 0.342 g (40.0%). Anal. Calcd for C40H35N4PRuC1204"0.2C6HI4: C 57.81; H 4.45. Found: C 57.46; H 4.75. UV-vis data (CH2C12) km~x. nm (e, M -I cm-l): 468 (7400); 335 (7300); 295 (40000). I074-1542,~6/0100-0067509.50/0 9 1996 Plenum Publishing Coqx~ulion