science 580 • rprd y iig 5 g 015 ml o NiCl of mmol) (0.105 mg 25 mixing by prepared islig n prpit aon o C (43 g 020 ml in mmol) 0.210 mg, (64.3 CQ of amount appropriate an dissolving chemicals wereusedasreceived. All Lachema. from received were compounds all of preparation the in used p.a.) (DMF), dimethylformamide and 96%, (, solvents as well as %, Sigma 99 acid, from acetic purum, received hydroxide, potassium and was Aldrich %, 95 Clioquinol, Lachema. from (p.a.) codn t [1, 0 wtr ouin f PdCl of solution water % 40 [11], to according A perfect example of ligand modification is substitution of Cl of substitution is modification ligand of example perfect A planar [M(CQ) growth oftumors[9]. the inhibits and cells cancer against toxic is CQ that found been has it Moreover, 8]. [7, diseases Parkinson’s and Alzheimer’s of treatment the in results encouraging very providing is iron, and copper, as such ions, metal chelate to ability its to due recently and years many for agent antimicrobial an as used been has CQ CQ). (clioquinol, 8-ol are inactive[6]. be active against colorectal carcinoma, whereas cisplatin or carboplatin to oxaliplatin enhances what 1,2-diaminocyclohexane, by substituted example of ligand substitution is oxaliplatin, where ammine ligands are positive Another [5]. carboplatin with treatment cancer the in proven also was nephrotoxicity and neuro- Decreased cisplatin [4]. both carboplatin for and spectrum activity same the with lines cell cancer resulted in decreased toxicity of carboplatin in what the treatment of carboplatin, several in present ligand 1,1-cyclobutanedicarboxylate by Preparation ofcomplexes Experimental part Introduction of these complexes was presented on poster at 54 at poster on presented was complexes these of N- and O-donor atoms are present like in carboplatin. Brief description already beenpublished[10]. n cm 5 in should be mentioned that meantime the properties of [Ni(CQ) and biological activity of all three complexes are presented. However, it spectra IR analyses, thermal structures, crystal of description detailed Chemical Engineers (SiTPChem) in Lublin, Poland. In this paper, more of the Polish Chemical Society (PTChem) and the Polish Association of coordinated Cl coordinated whereas drug, this of activity the for responsible are cisplatin in Pt(II) atom to bound ligands Ammine agents. anticancer potential new of development the in role key a is what Pt(II), to coordinated ligands of many limitations these analogues of cisplatin have been synthesized by changing Toovercome the character 2]. [1, drug this to resistance drug, has a number of side effects and moreover, cancer cells can have [Ni(CQ) Interesting biological activity of CQ motivated us to prepare square- In our work we have used another ligand, 5-chloro-7-iodo-quinolin- ToK used we study under complexes prepare anticancer used widely and potent most the of one as Cisplatin, Please citeas:CHEMIK2012,66,6,575-584 Chemistry, of Institute Chemistry, Inorganic of Department P. - J.ŠafárikUniversityinKošice POTOČŇÁK Ivan VRANEC, Peter [M(CQ) CQ =clioquinol)–analoguesofcarboplatin 3 f tao wt a ouin f Q Ti ws rprd by prepared was This CQ. of solution a with ethanol of 2 ) - bis(5-chloro-7-iodoquinolin-8-olato)nickel(II) was bis(5-chloro-7-iodoquinolin-8-olato)nickel(II) - (1) ] 2 - ] complexes (M = Ni(II), Pd(II) and Pt(II)), in which two anions are responsible for the toxicity of cisplatin [3]. cisplatin of toxicity the for responsible are anions 2 ] complexes (M = Ni, Pd and Pt, ] complexes(M=Ni,PdandPt, 2 [PtCl 2 th n NiCl and 2 ∙6H Annual Meeting Annual 4 ] synthesized ] 2 dissolved O - anions 2 2 ∙6H ] have 2 O ethanolic solution prepared from 0.2 cm an with filled was tube the of part upper the Finally,capillary. the in interface diffusion a creating solution CQ the onto dripped carefully were mixture (1:1) ethanol:DMF of drops Few tube. test the of part mother liqueur. Calc. for C filtered off and dried on air. Crystals of CQ arose after few days in the of precipitate red occurred the and hours 24 for refluxed was the solution to modify the value of pH to 6-7. Afterwards, this solution to added was (1:1) acid acetic diluted of drop one stirring of minutes was prepared by dissolving K dissolving by prepared was (8 cm (8 was which tube, test in capillary.a creating thus part, middle the in narrowed diffusion solution DMF A of method the by prepared was FCHPT STUinBratislava,Slovakia. Elemental Analyzer Flash EA 1112 from Thermo Finnigan Company at 9 °C/min. Elemental analyses of C, H and N were measured on CHNS was rate heating The holders. sample as cups ceramic with samples the of mg 19.5 – 15.9 using system, analysis thermal PC/PG STA409 TG-DTA curves of the samples in air were recorded using a NETZSCH H, 1.00;N,3.48.Found:C,26.89;H, 1.33;N,4.13%. (19 mg PdCl­ C of product aqueous KOH solution, molar ratio CQ:KOH = 2:1. Brown crystalline H, 1.13;N,3.92.Found:C,30.60;H, 1.02;N,4.46%. 8 cm 8 taoi slto (0 cm (30 solution ethanolic X–ray datacollectionandstructurerefinement techniques Physico-chemical C, 32.63;H, 1.07;N,4.12%. graphics. performed using SHELXL97. DIAMOND [14] was used for molecular parent C atoms with The C–H distances of 0.93 atoms. Å. A geometric analysis non-H was all H atoms were placed in for calculated positions and refined riding on their refined were parameters displacement Anisotropic [13]. SHELXL97 using syntheses Fourier subsequent and SHELXS97with method direct the correction by solved was structure The [12]. and absorption reduction data refinement, cell was for RED used Crysalis while collection data for used was CCD Crysalis detector. CCD Sapphire2 a with equipped diffractometer Xcalibur2 range 4000 – 400 cm the in ThermoNicolet from spectrophotometer FT-IRAVATAR 330 and dried on air. Calc. for C a slow diffusion, orange to red needle-like crystals of oue f itle wtr 2 cm (2 water distilled of volume 18 H [Pt(CQ) [Pd(CQ) The crystal structures were determined using an Oxford Diffraction an on recorded were complexes the of spectra infrared The 8 3 N 3 DMF. The solution of CQ was first deprotonated using 1 cm 1 using deprotonated first was CQ of DMF.solution The ) of CQ (98.1 mg CQ, 0.321 mmol) was added into the lower the into added was mmol) 0.321 CQ, mg (98.1 CQ of ) 2 Cl 2 I was filtered off and dried in air after few days. Calc. for Calc. days. few after air in dried and off filtered was 1 2 2 2 2 O , 0.107 mmol) and 8 cm ) - bis(5-chloro-7-iodoquinolin-8-olato)platinum(II) bis(5-chloro-7-iodoquinolin-8-olato)platinum(II) - (3) ] ) - bis(5-chloro-7-iodoquinolin-8-olato)palladium(II) bis(5-chloro-7-iodoquinolin-8-olato)palladium(II) - (2) ] 2 Ni (667.67 g·mol -1 using KBr discs of the samples. The simultaneous 3 18 18 o C (8 m; .0 ml. fe few After mmol). 0.60 mg; (180 CQ of ) H H 2 [PtCl 8 8 N N –1 2 2

3 Cl Cl ): C, 32.38; H, 1.21; N, 4.19. Found: ad iig hs ouin ih an with solution this mixing and ) 4 2 ] (60 mg; 0.15 mmol) in a minimal a in mmol) 0.15 mg; (60 ] 2 3 I I of 96% ethanol. After a month of 2 2 O O nr 6/2012 •tom 66 2 2 3 Pd (715.36 g·mol Pt (804.06 g·mol 40% water solution of PdCl 2 were filtered off –1 –1 ): C, 26.89; ): C, 30.22; was 3 2 3

compounds was evaluated in the concentration range of 128 – 8 μg.cm tested of activity to proportional compound. was mm, in measured zone, a by inoculated firstly was which agar, Mueller-Hinton the into disc paper the from cultivation a medium. in diluted furthermore and DMSO in dissolved were tests were used in the liquid Mueller-Hinton agar. Tested compounds Olomouc, Czech Republic at room temperature using a CoK diffractometer X´Pert PRO MPD (PANalytical) at Palacký University in group was first deprotonated using water solution ofpotassium hydroxide. solution water using deprotonated first hydroxyl was group CQ’s mixture. ethanol-DMF the in temperature room hand, when preparing [Pt(CQ) preparing when hand, of crystals preparing in resulted what tube, test the FullProf softwarepackage[15]. using calculated were parameters cell Unit method. reflectance a by rsne f Q n l cmons Te rprd opee were [M(CQ) complexes formula expected of prepared The compounds. all in CQ of presence precipitation ofPtO. the avoid to acid acetic diluted of amount small a contain to had hours in order to gain the product. Moreover, the reaction mixture 24 for refluxed was mixture reaction the and temperature higher eemnd s 0 bceil tan rwh niiin fe 2 and 24 48 hours. after inhibition growth strain bacterial % was 90 which as (MIC), determined concentration inhibition minimal a as was expressed compounds tested of efficiency Antibacterial Germany). MRX, at 37°C for 48 hours and evaluated spectrophotometrically (Dynatech, (TPP, Switzerland), together with bacterial strains. Tests were realized tested compounds were inserted into the holes of microtitration plate before testing. agar Subsequently, blood a on hours 18 for cultivated were strains Bacterial Infrared spectroscopy Syntheses Discussion ofresults Biological activity Powder diffraction prepare monocrystals of [Pd(CQ) of monocrystals prepare 2 as of precipitation yellow a (20°C), temperature normal a at working different completely complex, When ones. platinum than Pt(II) reactive more much are salts palladium the of preparation to nlss ee efre atr eiyn te uiy f h prepared complexes underamicroscope. the of purity the verifying after performed were analyses and faecalis, is summarizedin Table 1. shown in Figure 1, and the proposed are assignment of complexes the individual prepared bands three all of spectra FT-IR The compounds. all in CQ of presence the confirm to used was which spectroscopy, against complexes prepared occurred, thus we had to slow down the reaction in order to order in reaction the down slow to had we thus occurred, In the case of the microdilution test, the efficiency of the tested the of efficiency the test, microdilution the of case the In In the disc diffusion test, compounds under study were diffused rprto o te [Pd(CQ) the of Preparation Results of IR spectroscopy and elemental analysis confirmed the confirmed analysis elemental and spectroscopy IR of Results The prepared complexes were initially characterized by infrared by characterized initially were complexes prepared The [Ni(CQ) of Preparation of activity antimicrobial and antibacterial of evaluation the For The powder diffraction data for a strains bacterial crusei Candida ails subtilis, Bacillus nr 6/2012 •tom 66 bacterial strain. The extent of the disc inhibition disc the of extent The strain. bacterial suspension of bacterial strains was prepared and suooa aeruginosa, Pseudomonas 2 ] (M = Pd or Pt). All physico-chemical physico-chemical All Pt). or Pd = (M ] 2 cmlx (1 complex ] tpyoocs aureus, Staphylococcus 2 ] complex (3 complex ] 2 2 - 3 1 - were collected on a powder ] by a diffusion in the narrowed the in diffusion a by ] cmlx s (2 is complex ] disc diffusion and microdilution and diffusion disc ws efre at performed was ) ), we had to work at work to had we ), 2 add albicans Candida . On the other the On . , comparing ), Enterococcus a radiation –3 .

at 3448 cm 3448 at affected by the coordination of CQ in complexes. The medium band thephenolic OH group and pyridine C=N group to as these are the most corresponding bands the only discuss we therefore, [20]; individual bands in the IR spectrum of CQ was published aselsewhere of assignment , The [16÷22]. molecules halogen-substituted two these of and consists CQ pyridine as well as (8-HQ) 8-hydroxyquinoline of derivatives complex, Cu IR its CQ, the of on spectra literature available of basis the on assign to able were ν (OH) vibration in 5-chloro-7-bromo-8-hydroxyquinoline is found is 5-chloro-7-bromo-8-hydroxyquinoline in vibration (OH) Unassigned vibrations Breathing ν(C–H) ν(C=N) β(C ν(C ν(C=C) β(O–H) ν(O–H) β(CNC) δ(O–H) β(C–H) ν(C–O) β(CCC) γ(C–H) ν(C–C) ν(C γ(CCC) Wavenumbers (cm From the huge amount of bands we list only those which we which those only list we bands of amount huge the From 5 5 7 –X) –X) –I) ar -1 is associated with the O–H stretching vibration. The vibration. stretching O–H the with associated is ofclioquinol(CQ)anditscomplexes 1-3 3448 m,br 1635 vw 1202 vs 1332 vs 1395 vs 1489 vs 1576 m 1084 w 1043 w 1137 w 1238 w 1502 w 1605 w 3070 w 1272 s 1371 s 1460 s 955 vs 717 m 729 m 877 m 564 m 599 w 616 w 849 w 499 w 784 s 808 s CQ - - -1 ) andassignmentofthevibrationalspectra [Ni(CQ) 1203 vw 3055 vw 3068 vw 1366 vs 1447 vs 1486 vs 1117 m 1045 w 1133 w 1218 w 1243 w 1394 w 1584 w 448 vw 1545 s 652 m 765 m 774 w 691 w 717 w 807 w 856 w 867 w 511 w 981 w 600 w (1) - - - - 2 ] [Pd(CQ) 1201 vw 1276 vw 1591 vw 3050 vw 3066 vw 1360 vs 1441 vs 1114 m 1549 m 1045 w 1133 w 1215 w 1247 w 1255 w 1389 w 1578 w 1485 s 760 m 771 w 652 w 683 w 716 w 805 w 853 w 869 w 494 w 979 w 593 w (2) - - - - - 2 ] [Pt(CQ) 1197 vw 1217 vw 1280 vw 3055 vw 3070 vw 1362 vs 1442 vs 1117 m 1552 m 1049 w 1130 w 1244 w 1255 w 1308 w 1393 w 1581 w 1488 s 764 m 649 w 687 w 720 w 805 w 854 w 869 w 502 w 985 w 596 w (3) ------• 581 Table 1 2 ]

science science 582 • vibration occur as weak bands in the interval of 869 – 805 cm 805 – 869 of interval the in bands weak as occur vibration found this band in CQ at 3068 cm 3068 at CQ in band this found rings; corresponding band in the IR spectra of spectra IR the in band corresponding rings; 2 720 – 649 cm of bands weak Three decreases theelectronicdensityofring[22]. which bond, M–N the in atom nitrogen the of character donor the to to lower wavenumbers in the complexes of CQ[20]andalsootherdihalogenated verified by C–O stretching vibrationalso in theis rangecomplexes of 1117prepared – 1114the cm in CQ of presence The vibrations. 1133 – 1130 cm 1130 – 1133 in-plane of bands which is of medium intensity in the IR spectra of all complexes. Weak present in the 1591 – intensity 1485 different of cm bands Few vibrations. stretching aromatic C–H at a somewhat higher frequency (3625 cm etr. h asgmn o te = srthn vbain at vibration stretching C=N the 1460 cm of assignment The centers. of CQ, in which the deprotonated O atom is one of the coordinating vibration. The a to attributed be should that assignment incorrect an be bands observed in the range of 3070 – 3050 cm 3050 – 3070 of range the in observed bands is CQ, all the bands found in these spectra prove its presence. Weak n h rne f 34 19 cm 1197 – 1394 of range the in weak band observed at 774 and 771 cm 771 and 774 at observed band weak vibration is observed between 985 and 979 cm r wa ad hy cu a 60 53 cm 593 – 600 at occur they and weak are by and rings aromatic and atom between vibration stretching by proved also is CQ observed in the interval of 1447 – 1441 cm 1441 – 1447 of interval the in observed is vibrations stretching C=N of band strong very one and vibrations , respectively may be attributed to breathing vibrations of aromatic Fig 1.FT-IR spectraofpreparedcomplexes (1–3)inthespectral 8-hydroxyquinoline derivatives [21]. The Because in all three prepared [M(CQ) -1 in CQ is supported by previous investigations of IR spectra -1 interval. Except the ν (OH) band is not present in the metallic complexes -1 and 1049 – 1045 cm 1045 – 1049 and b C) irtos r peet n h itras of intervals the in present are vibrations (CH) b range1800–400cm (CCl) vibrations. Intensities of these bands these of Intensities vibrations. (CCl) b CC vbain ae bevd n the in observed are vibrations (CCC) -1 interval correspond to C=C stretching -1 r asge t CC stretching C–C to assigned are -1 ν ; however, we consider that tohowever, that ; consider we (CCl) vibration the presence of -1 1–3, a fact that can be related -1 2 and weak C–Cl stretching C–Cl weak and -1 ] complexes the only ligand in the IR spectra of spectra IR the in ) [21]. Other authors [20] -1 -1 ν(C=N) band is displaced . Several bands, presentbands, Several . -1 n 51 44 cm 494 – 511 and -1 . Out-of-plane 3 was not observed. not was -1 are assigned to assigned are ν -1 γ 1 . The. (CH) (CH) and -1 -1 , ,

at 448 cm 448 at Out-of-plane respectively. Thermal decomposition hc rvae ta te ae tbe p o 3°. hi thermal Their with exothermicprocesses. 230°C. to up associated steps distinguishable hardly stable two of consist decompositions are they that revealed which tp cnetd ih xtemc rcse, o, oee we however too, thermal of products processes, intermediate respective identify to unable exothermic were with connected steps distinguishable hardly two of consists decomposition Its concept. this of decompositions thermal as hypothetical not presentinthespectraof2 10.7 %for1,calculated26.3%,found26.63). found %, 11.2 (calculated PtO and NiO is decomposition thermal the for % 53.2 (calculated CQ molecules of residual both of release a with connected is respectively 470–720°C of %, 44.8 and % 53.4 of loss weight observed an with °C range 400–590 and temperature the in step exothermic Another for % 38.0 (calculated unit formula one from This respectively.molecule iodine an %, of release 29.0 a to corresponds and probably loss % weight 35.4 of loss weight total a with °C 375 – 230 and °C 470 – 280 of range temperature the in observed Fig. 2.TGanddifferentialthermalanalysis(DTA) curvesof1(up) and 3(down)Themostprobablethermaldecompositionschemes At the TG curve of analysis, thermal by characterized were complexes prepared All oee, hs cee f h teml eopsto i only is decomposition thermal the of scheme this However, -1 was observed in observed was 1 and for 1and3are: γ (CCC) vibration of very weak intensity intensity weak very of vibration (CCC) 3 (Fig. 2) two exothermic processes are 1 and 44.2 % for % 44.2 and 1 and3 , however bands of this vibration are vibration this of bands however , . nr 6/2012 •tom 66 can not be described by described be not can 2 and 31.6 % for % 31.6 and 1 ). Final product of product Final 3). 3).

ig n te u tm s .0 Å [3) Mlcls of Molecules [23]). Å) 3.407 is atom Cu the and ring aromatic the of (Cg) centroid the between distance the and Å 3.316 h dsac bten aall en lns f [Pd(CQ) of planes mean parallel between distance The Å. 3.401(1) is atom Ni the and ring aromatic the of Cg the between aromatic rings of adjacent molecules in the [Cu(CQ) the in molecules adjacent of rings aromatic bonds inaromaticrings[24,25,27]. distances (X = Cl or bond I) are close to the values for corresponding C–X single whereas [24÷26], molecules 8-HQ halogen-substituted and phenyl rings have expected values for complexes containing other 0.014(8) Å for C9 in mean plane of the whole CQ molecule is the 0.012(2) for from N1 deviation atom in largest (the planar themselves are molecules CQ 87.04(10)°, respectively (86.31° and 83.88° for Cu complex [23]). The and 83.2(2)° of Pd) and Ni = (M angle N1–M–O1 by confirmed is 2 in atoms central the around geometry square-planar Deformed sequence. same the in metals these of radius covalent increasing by (M = Ni, Cu and Pd) in the sequence Ni < Cu < Pd can be explained 1.974(15) Å, respectively) [23]. An increase of M–O and M–N distances Structural analysis (17.1 %)andobservedweightsofresidualproduct(17.0%). calculated the by evidenced is PdO.This is decomposition thermal of product final the and decomposition any the during in steps independent of released is molecule CQ whole no that Nevertheless, say certainly fragments. can we reasonable any with correspond not did decomposition according to the observed weight losses because these [M(CQ) two and adjacent centroids create a perfect atoms line which makes an angle with the Pd or Ni the Moreover molecules. of stacks to give rise interactions Such Å. 3.410(2) is atom Pd the and ring aromatic in as same the is part, andnitrogenatoms(N1)fromthepyridinepartofCQ. phenolic CQ the of deprotonation after coordinate to ready is which (O1), oxygen by way same the in coordinated chelate are molecules CQ Both ligands. anionic as CQ of molecules deprotonated two and consist of neutral molecules containing Ni(II) or Pd(II) as central atoms therefore their structures are shown in Figure 3. These two complexes previously studied square-planar [Cu(CQ) square-planar studied previously in Ni1–N1 and 1.998(6) Å, respectively) in the [Cu(CQ) neatos ewe tee oeue, o. h dsac between distance parallel mean planes The of [Ni(CQ) too. molecules, these between interactions similar observed we thus and complex, Cu(II) the coplanar,in as such itne ewe prle ma pae o [Cu(CQ) of planes mean parallel between distance Symmetry transformationsusedtogenerateequivalentatoms: ogrne neatos ee on bten abn tm of atoms carbon between found were interactions Long-range h vle o P1O ad d–1 itne (.9() and Å (1.990(5) distances Pd1–N1 and Pd1–O1 of values The [Ni(CQ) Fig. 3.Structureof1and2(M=NiorPd,respectively). 2 ] (M = Ni or Pd) plane of 78.8° or 76.2°, respectively (76.2° in 2 2 ad [Pd(CQ) and (1) ] ] complex [23]) what indicate possible semi coordination nr 6/2012 •tom 66 (3.340 Å) and the distance between the Cg of the of Cg the between distance the and Å) (3.340 1 1812 Å n 1832 Å rsetvl) and respectively), Å, 1.883(2) and Å (1.851(2) 1 2). C–C and C–N(O) bond distances within pyridine i =–1–x,y1z 2 are slightly longer comparing to Ni1–O1 2 ] molecules is 3.340 Å and the distance 2 cmlxs r isostructural; are complexes (2) ] 2 ] complex (1.919(6) Å and Å (1.919(6) complex ] 2 2 ] complex (the complex ] mlcls is molecules ] and 1 2 molecules ] and 1 are 2 1 and

Biological activity NT –nottested NT –nottested in Table 2. that all three complexes are isostructural with lattice constants shown of powder diffractograms the from found been has it Nevertheless, yet. solved not been has structure crystal its therefore and powder microcrystalline in Tables 3and4. The results of antibacterial and antimicrobial used activity of commonly two antibacterial and and antimicrobial agents, CQ cephalosporin and with amphotericin. compared and evaluated was 1 of activity antimicrobial and antibacterial Nevertheless, evaluated. be activity. anticancer activity,biological of tests the not in could used activity solvent their a their follow to was However, aim because these complexes are practically insoluble our in DMSO, thus and agents f i r d tm cn e osdrd s + wt a elongated an with 4+2 as considered be tetragonal bipyramidalcoordinationpolyhedron(Fig.4). can atoms Pd number or coordination Ni the of Thus molecules. CQ neighboring the of shown by dashed lines. Octahedral environment around central atoms Cephalosporin Amphotericin [Ni(CQ­ Cephalosporin Amphotericin [Ni(CQ­ Compound [Pd(CQ) [Ni(CQ) [Pt(CQ) Compound Fig. 4.Stackingofthemoleculesin1and2.π–interactionsare Antimicrobial activitydeterminationexpressed asadiameterof Antibacterial activity(microdilutiontest)expressed asminimal Lattice constantsof1-3calculatedfrompowderdiffractograms Complex h [Pt(CQ) The Complexes CQ CQ ) 2 ) ] (1) 2 2 2 2 ] (1) ] (3) ] (1) ] (2) S. aureus NT 24 and 2 S. aureus 7 7 4.7587(2) 4.7591(2) 4.7817(2) 2 >128 >128 1-3 inhibition concentration(μg.cm ws rprd ny n fr of form a in only prepared was (3) complex ] a [Å] NT 8 E. faecalis by the LeBail (profile matching) approximation matching) (profile LeBail the by have been prepared as potential anticancer potential as prepared been have 3 NT NT inhibition zone(mm) 10 9 E. faecalis 10.8324(9) 10.8256(6) 10.9378(3) >128 >128 is suggested b [Å] NT NT B. subtilis NT 21 11 9 P. aeruginosa 18.3461(5) 18.6671(2) 18.0618(9) P. aeruginosa c [Å] NT 24 8 8 NT 24 8 7 C. albicans –3 91.740(6) 90.975(3) 91.988(4) ) >128 C. albicans NT 0.5 β [°] 1 are summarized 64 NT 16 7 7 C. crusei C. crusei V [Å 945.3 961.5 944.1 • 583 Table 3 Table 2 Table 4 NT 0.5 64 16 NT 11 7 7 3 ]

science science 584 • anionic ligands. Square-planar [M(CQ) Square-planar ligands. anionic as CQ of molecules deprotonated coordinated N,O-chelate two and formed by neutral molecules containing Ni(II) or Pd(II) as central atoms Crystal structuresof1and2solvedbymonocrystalX-ray analysisare by elemental analysis which confirmed composition of the complexes. and molecules CQ of presence the proved which spectroscopy IR the in a moderately acidic solution. The complexes were characterized by by and diffusion slow a simple mixing of solutions, respectively, a by temperature room at prepared were 1 complexes While different. be to had reaction the of rates the general the complexes these prepare to Although solutions), corresponding same the of the (mixing (3)). was complexes Pt(II) three all and of preparation (2) the of procedure Pd(II) (1), Ni(II) = (M oxides. Due to the insolubility of insolubility the to Due oxides. MO respective are decompositions thermal the of products final the hardly distinguishable steps associated with exothermic processes and two of consist decompositions thermal Their ( 3). °C 230 and (2) (1), 260 280 to up stable are they that revealed which analysis, thermal with Literature testing ofbiologicalactivity. for Košice P.in from University Sabol Šafárik Dr.Marián J. and diffractograms powder the of evaluating with help for Košice in Sciences of Academy Slovak from Dr.Kavečanský measurements, Viktor analysis thermal the for Košice in The 27/2011/CH. P.from prof.Zeleňák to Vladimír grateful very are authors PF University Šafárik J. VVGS grant University P.J. Šafárik internal the by and ITMS26220120005 No. contract the under grant, fond) development regional Acknowledgement Summary andconclusions opee w hv peae tre [M(CQ) three prepared have we complexes matching) approximation that [Pt(CQ) that approximation matching) of diffractograms powder the from found been has It polyhedra. coordination bipyramidal tetragonal elongated atoms. Thus their coordination numbers can be considered as 4+2 with Pd or Ni to coordinated semi are molecules adjacent of atoms carbon interactions these to due and interactions range long by together held 1. 9. 8. 7. 6. 5. 4. 3. 2. and C.crusei. against mainly active is complex The tested. be could 1 This work was supported by the ERDF EU (European Union European Union (European EU ERDF the by supported was work This An planar square of activity biological a follow to aim the With of theantibioticclioquinol. Cancer. Res. 2005,65,3389. W.Ding VaughtB., Liu Q., YamauchiJ.L., H.,S.E.: Lind for Parkinson’s disease.Neuron2003,37,899. therapy novel a vivo: in MPTP-inducedneurotoxicity prevents chelation iron J.K.: Andersen A.I., Bush A., R. Cherny L., by Viswanath V., R., Jacobs, R., Boonplueang Yang J.Q.: L., Beal Mo M.F., J., KumarDiMonte D., Volitaskis S., F., YantiriI., Rajagopalan Eller D., Kaur disease withclioquinol,Dement.Geriatr. Cogn. Disord.2001,12,408. Sjögren M., Wallin A., Xilinas M., Gottfries C.G.: KarlssonI.,W., M., Lehmann Jonsson ReglandB., K., Blennow I., Abedini tin clinicalactivity:areview. Crit.Rev. Oncol.-Hematol.2000, Misset J.L., Bleiberg H. Sutherland, W. Bekradda M., Cvitkovic E.: xenografts. AnticancerRes. 1994, carcinoma ovarian human and plasmacytoma and leukaemia murine sistant -re- and platinum-sensitive in vivo in drugs platinum to sensitivity termining P.,Goddard L.R.: Kelland M., Valenti 1998, 34,1522. update. an and perspective historical an therapy: cancer R.: Canetta D., Lebwohl and currentstatusofDNAbinding.Met.IonsBiol.Syst.1996,32,641. Bloemink M.J., Reedijk J.: lecules. Cancer. Res. 1995,55,2761. Harrap K.R.: on mechanismsofacquiredresistance.CancerCells1990,2 and 1 drews P. A., Howell, S. B.: . All three prepared complexes were characterized by characterized were complexes prepared three All 2. Initiatives with platinum- and -based antitumor mo Cisplatin and derived anticancer drugs: Mechanism lncl eeomn o paiu cmlxs in complexes platinum of development Clinical Cellular pharmacology of cisplatin: perspectives and 2 14, 1065. The role of glutathione (GSH) in de- in (GSH) glutathione of role The 2 2 only the biological activity of activity biological the only 3 ] molecules are coplanar and coplanar are molecules ] ) is isostructural is (3) complex ] 3 was prepared under reflux 1-3 Genetic or pharmacological or Genetic by the LeBail (profile LeBail the by Treatment of Alzheimer’s Anticancer activityAnticancer Eur. J. of Cancer of Eur.J. 2 complexes ] , 35. P.aeruginosa 35, 75. Oxalipla- and 2 - -

27. 26. 25. 24. 23. 22. 21. 20. 19. 18. 17. 16. 15. 14. 13. 12. 11. 10. and postersatnationalinternational conferences. He is the author of 77 articles in scientific CC journalsproperties. andmagnetic 70 communications interesting or activity anticancer exhibiting complexes of chemistry coordination and crystallography interests: Research Košice. in He currently works for the Faculty of Sciences, Pavol Jozef Šafárik University respectively. 2003, and 1997 in awarded were Bratislava) Technologyin of leadership work (Faculty of Chemical and Food Technology, Slovak University ences, Pavol Jozef Šafárik University in Košice (1989). His doctoral thesis and posters atnationalandinternationalconferences. and communications 6 and journals scientific in articles 3 of author the is He agents. anticancer of chemistry coordination and crystallography interests: the Institute of Inorganic Chemistry,at P.J.student PhD. a currently Šafárik University in is Košice. ResearchHe (2009). Košice in University Šafárik Jozef phosphine)palladium(II). Gniewek A., Ziolkowski J.J., Lis T.:Lis J.J., Ziolkowski A., Gniewek Chem. 2006,16,4389. polymers. fluorene–iridium(III) main-chain from prepared WPLEDs E.J.W.:List K., Mereiter R., Saf S., Sax S., Eder S., Kappaun logr. Sect.C:Cryst.Struct.Commun.1987,43,39. of bis(5,7-dichloro-8-quinolinolato-N,O)bis(pyridine)nickel(II). Garcia-Granda S., Beurskens P.T., Behm H.J.J., Gomez-Beltran F.: Cryst. Struct.Commun.1986,42,33. lato-N,O)bis(pyridine)nickel(II)–pyridine dihydrate, Acta Crystallogr. Sect. C: S., Gomez-Beltran F.:Garcia-Granda plexes. Inorg.Chem.2004,43,3795. Com- Copper(II) and Zinc(II) Its of Characterization Structural Metabolism: Metal Brain with Interfering Specifically Disease Alzheimer’s for Drug a nol, Vaira M.D., Bazzicalupi C., Orioli P., Messori L., Bruni B., Zatta P.: nated Oxines.Monatsh.Chem.1997, ozlzBr AC, aa E.J.: Baran A.C., González-Baró droxyquinoline, Spectrochim.ActaPart A2009,72,783. 7-bromo-5-chloro-8-hy on studies DFT and initio ab investigations, scopic Arjunan V., Mohanb S., Ravindranc P.,C.V.:Ravindranc Mythilid S., V.,Mohanb Arjunan quinol anditsCu(II)complex.J.Raman Spectrosc.2007,38,373. TorreS., WagnerCalvo C.C., E.J.: Baran M.H., to thePhenol-PyrazineComplex.J.Mol.Spectrosc.1997,183,245. Application and Derivatives Phenol-OH(OD) of Spectra Near-Infrared the in Rospenk M., Leroux N., Zeegers-Huyskens T.: derivatives. Khim.Geterotsikl.Soed.1991,1381. a]pyrimidinium 9-oxypyrido Kovaĺchukova O.V.: S.B., Gashev B.E., Zajcev M.I., Palomino Leon Phone: +42155234 2335 E-mail: [email protected] Sci- of Faculty the RNDr.from doc. graduated - PhD, POTOČŇÁK Ivan E-mail: [email protected] Pavol Sciences, of Faculty the from graduated Sc.D., – VRANEC Peter Khim. Geterotsikl.Soed.1971,1535. derivatives. their and 4-oxyisoquinoline 3-oxyquinoline, of structures and tra Zajcev B.E., Andronova N.A., Djumaev K.M., Smirnov L.D.: Academia, Praha. D.: Papoušek M., Horák Commission onPowder Diffraction(IUCr),Newsletter2001,26,12. J.: Recent Rodríguez-Carvajal of Developments the Program FULLPROF, in Impact GbR. Brandenburg K.: DIAMOND (Release 2.1e) 2000, Bonn, Germany, Crystal University ofGöttingen. Germany, Göttingen, 1997, SHELXL97 and SHELXS97 G.M.: Sheldrick Oxford DiffractionLtd.. UK, Oxford, 2004, RED Crysalis and CCD Crysalis Diffraction, Oxford Keller R.N.: 2011, DOI:10.1007/s00706-011-0678-0. row transition metal coordination compounds with clioquinol. Monats. Chem. first the of properties thermal and spectroscopic, structure, Crystal I: gands. P.:Vranec PotočňákI., 62, m1428. Inorganic Syntheses,vol.II,NewYork –London, 1946,247. Synthesis, electronic structure and absorption spectra of [1,2- Low-dimensional compounds containing bioactive li- bioactive containing compounds Low-dimensional ca rs. et E Src. e. nie 2006, Online Rep. Struct. E: Sect. Cryst. Acta nrčreá pkr a spektra Infračervená xvndu(V Cmlxs f Haloge- of Complexes Oxovanadium(IV) trans-Iodo­ Structure of bis(5-chloro-8-quinolino 128, 323. nr 6/2012 •tom 66 Assignment Assignment of the Vibrations (p Nikitin S.V., Smirnov L.D., L.D., Smirnov S.V., Nikitin Vibrational spectra of clio of spectra Vibrational -iodo­ 1976, molekul struktura phen­ Vibrational spectro Vibrational yl)bis­ Infrared spec- Acta Crystal- Slugovc, Ch., Slugovc, (triphenyl­ Structure J. Mater.J. Clioqui- - - - -