The title compound, [Ru(C13H11N4S)2(C15H8N2)2], has C2
symmetry, with bidentate 2,2'-bipyridyl ligands dictating a cis
geometry around the RuII center. The monodentate S-bonded
dithizone ligands are almost planar, except for one of the
phenyl rings, which is twisted by 34.2 (4)&amp;#x00B0 from the N/N/C(S)/
N/N plane. The RuÐS bond length is 2.4140 (13) &amp;#x00C5, and the
RuÐN bond lengths are 2.048 (4) and 2.074 (4) &amp;#x00C5

NC DOCKS at The University of North Carolina at Greensboro

Walsh, Jerome "Jerry"

English

The University of North Carolina at Greensboro

metal-organic compoundsm268 # 2003 International Union of Crystallography DOI: 10.1107/S0108270103009338 Acta Cryst. (2003). C59, m268±m270A ruthenium complex with 1,5-di-phenyl-3-thiocarbazone (dithizone)as monodentate ligands: bis(2,20-bipyridyl-j2N,N0)bis(dithizonato-jS)-ruthenium(II)Gary L. Seamans,a Jerry L. Walsh,a* Mariusz Krawiecb andWilliam T. PenningtonbaDepartment of Chemistry and Biochemistry, The University of North Carolina atGreensboro, NC 27402-6170, USA, and bDepartment of Chemistry, ClemsonUniversity, SC 29631-0973, USACorrespondence e-mail: jlwalsh@uncg.eduReceived 12 March 2003Accepted 28 April 2003Online 11 June 2003The title compound, [Ru(C13H11N4S)2(C15H8N2)2], has C2symmetry, with bidentate 2,20-bipyridyl ligands dictating a cisgeometry around the RuII center. The monodentate S-bondeddithizone ligands are almost planar, except for one of thephenyl rings, which is twisted by 34.2 (4) from the N/N/C(S)/N/N plane. The RuÐS bond length is 2.4140 (13) AÊ , and theRuÐN bond lengths are 2.048 (4) and 2.074 (4) AÊ .CommentVery few X-ray structural reports have described eitherdithizone (H2dtz; Harrow®eld et al., 1983a,b; Kong & Wong,1999; Ortner & Abram, 1999; Mawby & Irving, 1972; Niven etal., 1982; Harding, 1958; Math & Freiser, 1970, 1971; Irving &Irving, 1986) or its oxidation product, 2,3-diphenyl-tetrazolium-5-thiolate (tet; Walsh et al., 1998; Liu & Zubieta,1989; Kozarek & Fernando, 1972) as ligands in transition metalcomplexes. The structure of [Ru(tpy)(bpy)(tet)](ClO4)2 (tpy is2,20:60,20-terpyridyl and bpy is 2,20-bipyridyl) involves mono-dentate coordination of the tet ligand through the S atom(Walsh et al., 1998). Bond distances and angles are consistentwith the tet ligand having delocalized mesoionic character(Liu & Zubieta, 1989; Kushi & Fernando, 1970). Because ofthe nature of the redox chemistry of the tet ligand whilecoordinated to the ruthenium center (Seamans & Walsh,2003), the synthesis of ruthenium±dithizone complexes withmonodentate ligands and the preparation of crystals suitablefor structural characterization were attempted. A directanalog of the tet complex, viz. [Ru(tpy)(bpy)(Hdtz)]ClO4, wasprepared, but suitable crystals could not be obtained. Subse-quently, [Ru(bpy)2(Hdtz)2], (I), was prepared and its struc-ture, the ®rst of a monomeric transition metal complex with amonodentate dithizonate ligand, is reported here (Fig. 1 andTable 1). Other examples of monodentate binding of dithizonehave involved a main group metal (Harrow®eld et al., 1983b)and bridging ligands (Kong & Wong, 1999).The ruthenium center exhibits the typical characteristics ofcis-Ru(bpy)2 complexes, with an NÐRuÐN bite angle close to80 (Table 1). The N6ÐRu1ÐN6i angle is 173.7 (2) and theN5ÐRu1ÐN5i angle is 86.2 (2) [symmetry code: (i) 1 ÿ x, y,12 ÿ z]. The atoms of the planar bpy ligands show an r.m.s. out-of-plane deviation of 0.0288 AÊ .In the title complex, the negatively charged dithizonateligand exhibits monodentate coordination through the S atom,with an Ru1ÐS1ÐC1 bond angle of 106.74 (18). Unlike thetrans±cis structure of S-methyldithizone (Preuss & Gieren,1975), which contains a ®ve-membered hydrogen-bonded ring,the structure of (I) is trans±trans about the N atoms, with nohydrogen bonding to the H atom attached to atom N2. Thisstructure is similar to that of a monodentate Hdtzÿ ligand inan indium complex (Harrow®eld et al., 1983b), a bridgingmonodentate Hdtzÿ ligand in an osmium cluster (Kong &Wong, 1999) and the iodine adduct of dithizone (Herbstein &Acta Crystallographica Section CCrystal StructureCommunicationsISSN 0108-2701Figure 1A view of the title ruthenium complex, with displacement ellipsoidsdrawn at the 30% probability level.Made available courtesy of International Union of Crystallography: http://www.iucr.org/ ***Reprinted with permission. No further reproduction is authorized without written permission from International Union of Crystallography. This version of the document is not the version of record. Figures and/or pictures may be missing from this format of the document.*** Schwotzer, 1982, 1984). Bidentate coordination of Hdtzÿligands usually occurs in a similar trans±trans fashion. Thedithizonate unit is nearly planar (Table 2), except for the twistof the C8±C13 phenyl ring out of the plane of the C/N/N/C(S)/N/N/C moiety by 34.2 (4); the C2±C7 phenyl ring is twistedonly 3.9 (4) out of the C/N/N/C(S)/N/N/C plane. The phenylrings of coordinated dithizone ligands have been observed tobe coplanar with the N/N/C(S)/N/N plane (Harding, 1958;Mawbry & Irving, 1972; Math & Freiser, 1971; Laing, 1977) ortwisted at some angle (Laing et al., 1971; Math & Freiser,1970). The latter cases are often the result of steric effects, butsteric effects do not appear to be a major factor leading tonon-planarity in the present case. Packing effects may beinvolved.The bonding in dithizone (H2dtz) and the deprotonateddithizonate anion (Hdtzÿ) is illustrated in the Scheme below.Structure F is expected to be the dominant form of thedithizonate ion in (I). In (I), the C1ÐS1 bond length of1.737 (5) AÊ is only slightly shorter than the CÐS bond lengthsin thiolate±ruthenium complexes (1.78 AÊ ; Shiu et al., 2002)and slightly longer than the CÐS bond lengths in ruthenium±thione complexes (1.67 AÊ ; Bellucci & Cini, 1999), indicatingconsiderable single-bond character in the CÐS bond.Delocalization in the N/N/C(S)/N/N framework, including acontribution from structure G, could provide some double-bond character, thus decreasing the CÐS bond length.The bond distances (Table 1) in the N/N/C/N/N moiety areconsistent with the dithizone bonding shown in structure F.The long N1ÐN2 [1.343 (6) AÊ ], short N1ÐC1 [1.310 (7) AÊ ],long C1ÐN3 [1.412 (7) AÊ ] and short N3ÐN4 [1.256 (6) AÊ ]distances are as predicted (Ortner & Abram, 1999; Liu &Zubieta, 1989). In typical bidentate dithizonate coordination,the complementary CÐN and NÐN bonds on opposite sidesof the C S unit differ in length by 0.01±0.06 AÊ . The titlecomplex shows the greatest long±short distinction of anydithizonate±metal complex, with characteristics similar toS-methyldithizone (Preuss & Gieren, 1975) and the mono-dentate dithizonate ligand in In(Hdtz)3 (Harrow®eld et al.,1983b).In spite of the sp3-hybridized N2 atom in structure F, theC2±C7 phenyl ring is nearly coplanar with the C/N/N/C(S)/N/N/C moiety, with an angle of 3.9 (4) between the planes,which suggests that structure E may provide some contribu-tion to the electronic nature and structure of the molecule.ExperimentalAcetonitrile (16 ml) and ethanol (8 ml) were added to a round-bottomed ¯ask (100 ml) and the ¯ask was purged with N2. To thesolution were added [Ru(bpy)2(tet)2](ClO4)2 (215 mg, 0.192 mmol)and hydrazine monohydrate (20 ml, 0.41 mol), and the resultingsolution was stirred overnight. Ethanol (5 ml) was added and thesolution was rotary evaporated until the desired compound precipi-tated. The product was collected by ®ltration and washed withethanol and diethyl ether. The solid was chromatographed on analumina column and reprecipitated to produce dark-red crystals(yield 160 mg, 0.173 mmol, 90%). Analysis calculated forC46H38N12RuS2: C 59.79, H 4.15, N 18.19%; found: C 59.53, H 4.13, N18.01%. Crystals suitable for X-ray analysis were grown by vapordiffusion of diethyl ether into a solution of (I) in acetone and ethanol.Crystal data[Ru(C13H11N4S)2(C15H8N2)2]Mr = 924.07Monoclinic, C2=ca = 18.831 (5) AÊb = 16.423 (4) AÊc = 14.650 (4) AÊ = 98.107 (6)V = 4485.3 (19) AÊ 3Z = 4Dx = 1.368 Mg mÿ3Mo K radiationCell parameters from 12 728re¯ections = 2.4±26.4 = 0.49 mmÿ1T = 300 (2) KPrism, dark red0.50  0.15  0.15 mmData collectionMercury CCD diffractometer! scansAbsorption correction: multi-scan(Jacobson, 1998)Tmin = 0.766, Tmax = 0.92921 449 measured re¯ections4596 independent re¯ections3497 re¯ections with I > 2(I )Rint = 0.083max = 26.4h = ÿ23! 23k = ÿ20! 20l = ÿ16! 18Re®nementRe®nement on F 2R[F 2 > 2(F 2)] = 0.071wR(F 2) = 0.139S = 1.084596 re¯ections276 parametersH-atom parameters constrainedw = 1/[2(F 2o) + (0.0377P)2+ 13.5485P]where P = (F 2o + 2F2c )/3(/)max < 0.001max = 0.42 e AÊÿ3min = ÿ0.26 e AÊ ÿ3Acta Cryst. (2003). C59, m268±m270 Gary L. Seamans et al.  [Ru(C13H11N4S)2(C15H8N2)2] m269metal-organic compoundsTable 1Selected geometric parameters (AÊ , ).Ru1ÐN6 2.048 (4)Ru1ÐN5 2.074 (4)Ru1ÐS1 2.4140 (13)S1ÐC1 1.737 (5)N1ÐC1 1.310 (7)N1ÐN2 1.343 (6)N2ÐC2 1.385 (7)N3ÐN4 1.256 (6)N3ÐC1 1.412 (7)N4ÐC8 1.436 (7)N6ÐRu1ÐN6i 173.7 (2)N6ÐRu1ÐN5 78.51 (16)N5iÐRu1ÐN5 86.2 (2)N6ÐRu1ÐS1 96.83 (11)N6iÐRu1ÐS1 87.93 (11)N5iÐRu1ÐS1 96.10 (10)N5ÐRu1ÐS1 175.04 (12)S1iÐRu1ÐS1 81.93 (6)C1ÐS1ÐRu1 106.74 (18)C1ÐN1ÐN2 115.5 (5)N1ÐN2ÐC2 121.7 (5)N4ÐN3ÐC1 113.9 (5)N3ÐN4ÐC8 113.8 (5)C14ÐN5ÐC18 119.7 (4)C14ÐN5ÐRu1 125.6 (4)C18ÐN5ÐRu1 114.5 (3)C23ÐN6ÐC19 118.2 (4)C23ÐN6ÐRu1 125.4 (3)C19ÐN6ÐRu1 116.5 (3)N1ÐC1ÐN3 108.9 (5)N1ÐC1ÐS1 126.2 (4)N3ÐC1ÐS1 125.0 (4)C1ÐN1ÐN2ÐC2 178.9 (5)C1ÐN3ÐN4ÐC8 177.6 (5)N2ÐN1ÐC1ÐN3 ÿ179.4 (4)N2ÐN1ÐC1ÐS1 0.5 (7)N4ÐN3ÐC1ÐN1 171.3 (5)N4ÐN3ÐC1ÐS1 ÿ8.6 (7)Ru1ÐS1ÐC1ÐN1 102.0 (5)Ru1ÐS1ÐC1ÐN3 ÿ78.1 (5)N1ÐN2ÐC2ÐC7 ÿ1.2 (8)N1ÐN2ÐC2ÐC3 ÿ178.9 (5)N3ÐN4ÐC8ÐC9 154.5 (6)N3ÐN4ÐC8ÐC13 ÿ25.1 (9)Symmetry code: (i) 1ÿ x; y; 12ÿ z.metal-organic compoundsm270 Gary L. Seamans et al.  [Ru(C13H11N4S)2(C15H8N2)2] Acta Cryst. (2003). C59, m268±m270H atoms were placed in idealized positions and were allowed toride on their parent atoms, with CÐH distances of 0.93 AÊ foraromatic H atoms and an H2ÐN2 distance of 0.86 AÊ . The Uiso(H)parameters were taken to be 1.2Ueq of the parent C or N atom. Thereare four small voids of about 104 AÊ 3 in each unit cell in the re®nedstructure. These voids, which constitute approximately 9.2% of thetotal volume of the unit cell, probably contain disordered solventmolecules. However, no atoms could be located in the voids from thedifference Fourier map. Instead, a disordered solvent correctionbased on the SQUEEZE algorithm (van der Sluis & Spek, 1990) inPLATON (Spek, 2003) was applied to account for the extra electrondensity in the voids. SQUEEZE located two additional electrons pervoid. After applying the disordered solvent correction, the minimumresidual electron density changed fromÿ0.60 toÿ0.26 e AÊ ÿ3, and themaximum electron density was reduced from 1.26 to 0.42 e AÊ ÿ3; wRimproved from 0.163 to 0.139.Data collection: CrystalClear (Rigaku Corporation, 1998±2001);cell re®nement: CrystalClear; data reduction: CrystalClear;program(s) used to solve structure: SHELXS97 (Sheldrick, 1990);program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997);molecular graphics: SHELXL97; software used to prepare materialfor publication: SHELXL97 and PLATON (Spek, 2003).MK and WTP thank the National Science Foundation andClemson University for funding (grant No. CHE-9808165).Supplementary data for this paper are available from the IUCr electronicarchives (Reference: FG1686). Services for accessing these data aredescribed at the back of the journal.ReferencesBellucci, C. & Cini, R. (1999). J. Inorg. Biochem. 76, 243±250.Harding, M. M. (1958). J. Chem. Soc. pp. 4136±4143.Harrow®eld, J. M., Pakawatchai, C. & White, A. H. (1983a). Aust. J. Chem. 36,825±831.Harrow®eld, J. M., Pakawatchai, C. & White, A. H. (1983b). J. Chem. Soc.Dalton Trans. pp. 1109±1113.Herbstein, F. H. & Schwotzer, W. (1982). Angew. Chem. Int. Ed. Engl. 21, 219.Herbstein, F. H. & Schwotzer, W. (1984). J. Am. Chem. Soc. 106, 2367±2373.Irving, A. & Irving, H. M. N. H. (1986). J. Crystallogr. Spectrosc. Res. 16, 495±505.Jacobson, R. A. (1998). REQABS. Version 1.1. Molecular Structure Corpor-ation, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.Kong, F.-S. & Wong, W.-T. (1999). J. Chem. Soc. Dalton Trans. pp. 2497±2510.Kozarek, W. J. & Fernando, Q. (1972). J. Chem. Soc. Chem. Commun. pp. 604±605.Kushi, Y. & Fernando, Q. (1970). J. Am. Chem. Soc. 92, 1965±1968.Laing, M. (1977). J. Chem. Soc. Perkin Trans. 2, pp. 1248±1252.Laing, M., Sommerville, P. & Alsop, P. A. J. (1971). J. Chem. Soc. A, pp. 1247±1251.Liu, S. & Zubieta, J. (1989). Polyhedron, 8, 677±688.Math, K. S. & Freiser, H. (1970). J. Chem. Soc. Chem. Commun. pp. 110±111.Math, K. S. & Freiser, H. (1971). Talanta, 18, 435±437.Mawbry, A. & Irving, H. M. N. H. (1972). J. Inorg. Nucl. Chem. 34, 109±115.Niven, M. L., Irving, H. M. N. H., Nassimbeni, L. R. & Hutton, A. T. (1982).Acta Cryst. B38, 2140±2145.Ortner, K. & Abram, U. (1999). Polyhedron, 18, 749±754.Preuss, J. & Gieren, A. (1975). Acta Cryst. B31, 1276±1282.Rigaku Corporation (1998±2001). CrystalClear. Version 1.3 SP1. RigakuCorporation, Tokyo, Japan.Seamans, G. L. & Walsh, J. L. (2003). In preparation.Sheldrick, G. M. (1990). Acta Cryst. A46, 467±473.Sheldrick, G. M. (1997). SHELXL97. University of GoÈ ttingen, Germany.Shiu, K.-B., Chen, J.-Y., Lee, G.-H., Liao, F.-L., Ko, B.-T., Wang, Y., Wang, S.-L.& Lin, C.-C. (2002). J. Organomet. Chem. 658, 117±125.Sluis, P. van der & Spek, A. L. (1990). Acta Cryst. A46, 194±201.Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.Walsh, J. L., McCrackin, R. & McPhail, A. T. (1998). Polyhedron, 17, 3221±3226.Table 2Angles between least-square planes.Plane 1 Plane 2 Angle ()S1/N1/N2/N3/N4/C1/C2/C8 C2/C3/C4/C5/C6/C7 3.32r.m.s. deviation = 0.0362 AÊ r.m.s. deviation = 0.0071 AÊS1/N1/N2/N3/N4/C1/C2/C8 C8/C9/C10/C11/C12/C13 35.30r.m.s. deviation = 0.0362 AÊ r.m.s. deviation = 0.0119 AÊ

A ruthenium complex with 1,5-di- phenyl-3-thiocarbazone (dithizone) as monodentate ligands: bis(2,2'- bipyridyl-&#x03BA2N,N')bis(dithizonato-&#x03BAS)- ruthenium(II)

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A ruthenium complex with 1,5-di- phenyl-3-thiocarbazone (dithizone) as monodentate ligands: bis(2,2'- bipyridyl-<i>&#x03BA</i><sup>2</sup>N,N')bis(dithizonato-<i>&#x03BA</i>S)- ruthenium(II)

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