The syn theses of diaquabis (3-hydroxyflavonato) cobalt(II) and bis(pyridine) bis (3hydroxyflavonato)

cobalt(II) are described. Results from infrared spectra clearly

show that the 3-hydroxyflavonato anion forms a chelate through the 3-hydroxy

4-keto groups. The electronic spectra of both complexes indicate that cobalt(II)

has an octahedral geometry. Quantitative analyses of the isolated products gave

good agreement with calculated values. Magnetic moment measurements show

that both compounds are high spin £ cobalt(II) complexes. The powder

diffraction pattern of the pyridine adduct gave almost 1:1 correspondence with

tTans-bis (pyridine) bis (3-hydroxyflavonato) nickel (II) which has an octahedral

geometry. Therefore, it is highly likely that bis(pyridine)bis(3hydroxyflavonato)

cobalt(II) is octahedrally co-ordinated with two chelating 3-hydroxyflavonato

anions and two pyridine molecules occupying tTans positions

D. A., Rice

Yang, Farina

Universiti Putra Malaysia Institutional Repository

Pertanika J. Sci. & Techno!. 3(2): 211-219 (1995)ISSN: 0128-7680© Penerbit Universiti Pertanian MalaysiaSynthesis and Characterisation of Cobalt(II)Complexes of 3-HydroxyflavoneYang Farina and D.A. Rice'Department of ChemistryFaculty of Physical and Applied SciencesUniversiti K.ebangsaan Malaysia43600 Bangi, Selangor, MalaysialDepartment of ChemistryFaculty of ScienceUniversity of Reading, Reading, EnglandReceived 30 June 1994ABSTRAKSintesis diakuabis(3-hidroksiflavonato) kobalt(II) dan bis (piridina) bis (3-hidroksiflavonato) kobalt(II) dilaporkan. Hasil spektrum inframerahmenunjukkan yang ligan 3-hidroksiflavonato membentuk kelat dengan kobalt(II)melalui kumpulan 3-hidroksi dan 4-keto. Spektrum elektronik kedua-duakompleks pula memberi gambaran yang kobalt(II) membentuk kompleksoktahedron. Analisis kuantitatif kompleks yang diasingkan memberi padananyang baik dengan nilai jangkaan. Pengukuran momen magnet menunjukkanyang kedua-dua kompleks adalah kompleks kobalt(II), d7berspin tinggi. Corakberaluan serbuk sinar-X bagi aduk piridina hampir meberi padanan 1:1 dengancorak belauan serbuk sinar-X bagi trans-bis (piridi na) bis (3-hidroksiflavonato) nikel (II) yang mempunyai geometri oktahedron. Dengandemikian boleh disimpulkan yang bis(piridina) bis(3-hidroksiflavonato) kobalt(II)juga berkoordinat secara oktahedron dengan dua anion 3-hidroksiflavonmembentuk kelat dan dua molekul piridina berada dalam kedudukan tTans.ABSTRACTThe syn theses of diaquabis (3-hydroxyflavonato) cobalt (II) and bis(pyridine) bis (3-hydroxyflavonato)cobalt(II) are described. Results from infrared spectra clearlyshow that the 3-hydroxyflavonato anion forms a chelate through the 3-hydroxy4-keto groups. The electronic spectra of both complexes indicate that cobalt(II)has an octahedral geometry. Quantitative analyses of the isolated products gavegood agreement with calculated values. Magnetic moment measurements showthat both compounds are high spin £ cobalt(II) complexes. The powderdiffraction pattern of the pyridine adduct gave almost 1:1 correspondence withtTans-bis (pyridine) bis (3-hydroxyflavonato) nickel (II) which has an octahedralgeometry. Therefore, it is highly likely that bis(pyridine)bis(3-hydroxyflavonato) cobalt(II) is octahedrally co-ordinated with two chelating 3-hydroxyflavonato anions and two pyridine molecules occupying tTans positions.Keywords: cobalt(ll) complex, 3-hydroxyflavonatoYang Farina and D.A. RiceINTRODUCTIONFlavonoids belong to a large group of compounds which occur naturallyin plants (Harborne et al. 1975). Flavonoids have a basic skeleton structureas shown in Fig. 1. Ring B may be either saturated or unsaturated.Flavonoids with an unsaturated B ring and a keto group in the 4 positionare called flavones. Flavones with a hydroxyl group in the 3 position arecollectively known as flavonols. Flavonols with hydroxy groups in otherpositions are found in practically all plants (Herrmann 1976). For exam-ple, quercetin and kaempferol occur in the skin of apples and pears(Herrmann 1976). Cobalt can also be found in a variety of plants, but theexact mechanism by which cobalt is taken up by plants in not thoroughlyunderstood (Farago 1981). However, it is likely that cobalt forms acomplex when it gets into the plant system (Skaar et al. 1973). Sinceflavonols are widespread in plants it is possible that cobalt could formcomplexes with this class of compounds.Fig. 1Complex formation between 3-hydroxyflavone and aluminium (III) chlo-ride was studied spectrometrically by Jurd and Geissman (1956). Like manyother flavonols, the complexing capability of 3-hydroxyflavone is also dem-onstrated by its wide use as an analytical reagent. The reagent 3-hydroxyflavonehas been used for the fluorimentric determination of metals (Katyal andPrakash 1977; Cabrera-Martin et al. 1986). To date, the only complexes of 3-hydroxyflavone that have been isolated are a series of air-stable organotinderivatives (Blunden and Smith 1982) and chelates with copper(I) (Speieret al. 1990) and copper (II) (Balogh-Hergovich et al. 1991). The crystalstructure of trans-bis (pyridine) bis (3-hydroxyflavonate) nickel (II) has beenelucidated (Yang Farina et al. 1995). Nickel(II) is hexacoordinated and thegeometry surrounding the metal centre is close to an octahedron. The metalcentre is bound to two chelating bidentate 3-hydroxyflavonato anions andtwo pyridine molecules whtich occupy trans positions.212 Pertanika J. Sci. & Technol. Vol. 3 No.2, 1995Synthesis and Characterisation of Cobalt(II) complexes of 3-HydroxyflavoneSince all flavonols contain the 3-hydroxy-4-keto group, it was thuslogical to study the complex formation capability of this site. We thereforedecided to look at the complex formation between cobalt(II) and 3-hydroxyflavone by synthesizing and characterizing such complexes.MATERIALS AND METHODSCommercial grade 3-hydroxyflavone (flvH) and analar grade cobalt(II)chloride hexahydrate were supplied by Aldrich Chemicals and Fisonsrespectively. Commercial grade triethlyamine (Et3N) and pyridine (py)were purchased from BDH and used without further purification.Elemental C, H, and N analyses were made on an F and M scientific185C analyser at the University of Reading, England. The quantitativedeterminations for cobalt were obtained using a Perkin-Elmer 272 atomicabsorption spectrophotometer at = 240.7 nm. The infrared spectra wererecorded from mulls in hexachlorobut-1,3-diene (4000-2500 and 1600-1200 cm· l ) and nujol (2500-1600 and 1200AOOcm" between KBr platesusing a Perkin-Elmer 983 grating spectrophotometer. The magnetic mo-ment of the complexes was calculated at room temperature on a Faradaybalance using Hg[Co(NCS)4]2 (Xg = 16.44 X 10.6 cgs units) as calibrant.The diffuse reflectance spectra of solid samples were measured from50000-5000 cm'l on a Beckman Acta MIV spectrophotometer. The X-raypowder patterns were determined on a Philips X-ray.diffractometer (PW30j1320) using filtered CooK 00 radiation (A =1.7902 A).All preparations were carried out under an atmosphere of nitrogenusing thoroughly deoxygenated solutions.SYNTHESIS OF DlAQUABI(3-HYDROXYFLAVONATO )COBALT(II)[Co(H20 2)2(flv)2] Cobalt(II) chloride (0.2 g, 1 mmo1) was dissolved inethanol (20 ml). This mixture was added to a lemon-yellow ethanolicsolution of 3-hydroxyflavone (0.5 g, 2 mmol) and triethylamine (0.3 ml, 2mmol). Initially the mixture turned brown, but on further stirring a brownprecipitate was formed. The resulting mixture was then subjected toheating under reflux (79°C) for 30 minutes. Upon cooling the brown solidwas isolated by filtration, washed with ethanol (2 x 5 ml) and dried in avacuum desiccator over phosphorous pentoxide, yield = 0.5 g (88%).SYNTHESIS OF BIS(PYRIDINE)BIS(3-HYDROXYFLAVONATO)COBALT(II)[Co(pY)2(flv)2] This complex was prepared by heating under reflux (116°C)a mixture of [Co(H20 2)2(flv)2] and excess pyridine. Upon cooling browncrystals were deposited. Recrystallization from hot acetonitrile affordedbrown single crystals.Pertanika J. Sci. & Techno!. Vo!. 3 No.2, 1995 213Yang Farina and D.A. RiceRESULTS AND DISCUSSIONElemental analyses for both complexes are presented in Table 1. The datashowed good agreement with proposed formulae. The addition oftriethylamine to 3-hydroxyflavone resulted in the abstraction of the acidicproton to give the triethylammonium salt of 3-hydroxyflavone as the inter-mediate. Addition of cobalt(II) chloride hexahydrate gave the bis chelatewith two water molecules still attached to the metal centre. A side productin this reaction is triethylammonium chloride which is soluble in ethanol.Hence simple filtration and washing with ethanol gave diaquabis(3-hydroxyflavonato)cobalt(II). The complex [Co(H20)2(flv)2] gave negativeresults when tested for the presence of chloride ions. A reaction involvinga stoichiometric ratio of 3:1, hydroxyflavonato anion: cobalt(II) was carried outin an attempt to prepare [E~NH] [Co (flv) 3]' However the product isolated gaveidentical results to those of [Co(H20)2(flv)2]' The reaction between[Co (HP)2 (flv) 2] and pyridine gave the substitution product [Co(py\(flV)2]which was easily purified by recrystallization from hot acetonitrile. A simpleoutline of the reaction mechanism is given in Scheme 1.2-+o~Co CI,. 6H,O2 --py2EtJ NHCIScheme 1. Reaction layoutThe infrared spectra of the complexes were compared to those of thefree ligand. The infrared data of [Co (HP)/flV)2] and [Co(pY)2(flv)2] arepresented in Table 2. Generally, upon complex formation, major changesoccurred in the 4000-3000 and 1650-1500 cm,j regions. The infraredspectrum of the free ligand showed that v(O-H) appeared as a strongbroad peak at 3215 cm'l. As expected, this peak disappeared when theligand formed complexes with cobalt(II). However, the presence of water214 Pertanika J. Sci. & Techno!. Va!. 3 No.2, 1995Synthesis and Characterisation of Cobalt(II) complexes of 3-HydroxyflavoneTABLE 1Analytical results for cobalt(II) 3-hydroxyflavonato complexesCompound %C %H %N %Co[Co(HP)2(flv)2] 63.93 3.73 10.40(63.28) (3.89) (10.35)[Co (py) 2(flv) 2] 69.60 4.21 4.16 8.00(69.47) (4.08) (4.05) (8.52)Calculated values are given in parentheses.in [Co(H20 2)2(flv)2] was detected by a broad peak due to v(O-H) at 3450em'] and a weak 8(O-H) at 1682 em']. The C=C ring stretching vibrationsof the free ligand occur at 1627, 1611 and 1563 em'], while v(C=O) issuperimposed upon the peak at 1611cm] Oose et at. 1974). Complexformation in both compounds is clearly shown by shifts in v(C=C) andv(C=O) vibrations. The ring stretching vibrations appeared at 1613, 1591and 1570 em] in 1 while in [Co(pY)2(flv») the peaks are located at 1614,1590 and 1568 cm l . The intensity of the peaks at 1613 and 1614 cm l isweaker than the same peak in the free ligand since the carbonyl strectchingwavenumber is now lowered to 1545 and 1547 cm l in [Co(H20)2(flv)2]and (CO(PY2)2(flv)2] respectively. The lowering of the carbonyl; stretchindicates that the strength of the c=o bond is weakened because the oxygenatom is also bonded to cobalt (II) , thus reducing the electron densitybetween oxygen and carbon. This observation is in accordance with thosereported by other workers Oose et at. 1974; Blunden and Smith 1982). Thelowering of the carbonyl stretch coupled with the absence of v(O-H) clearlyindicates that the cobalt(II) anion is attached to both 4-keto and 3-hydroxygroups. Therefore it can be induced that the 3-hydroxyflavonato anion formsa chelate with cobalt(II). The infrared spectrum of [Co(pY)2(flv)2] containsadditional peaks of medium intensities centred at 748 and 702 em] whichwere assigned to pyridine, C-H out of plane deformation bands.The magnetic moments of [CoHP)2(flv)2]and [Co (PY)2 (flv) 2] at 293 Kwere measured to be 4.67 and 4.98 BM respectively and are comparable tothe magnetic moment of other high spin d7 octahedral complexes such as[Co(H20)2(sal)2] (sal=salicylaldehydato anion), which has a value of 4.74BM (Cotton and Holm 1960). Octahedral cobalt(III) complexes on theother hand, being d6 are usually low spin because of the inert t2/ configu-ration. However, the hexafluorocobaltate anionic complex, [CoF6P' is para-magnetic and has a magnetic moment of about 5.4 BM. Therefore it can beconcluded that both complexes are high spin cobalt(II) complexes since ahigh spin cobalt(III) complex should give a much higher magnetic moment.Pertanika J. Sci. & Techno!. Vo!. 3 No.2, 1995 215Yang Farina and D.A. RiceTABLE 2Infrared data of [CO(HP)2(flv)2] and [Co(pY)2(flv)2]3423(b,m)3095(w)1682(b, w)1613(m)1519(s)1570(m)1545 (vs)1505(s)1487(vs)1461 (s)1440(m)1420 (vs)1359(m)1325(m)1313(m)1299(m)1253(m)1220(sh, s)1185(w)1154(s)1118(m)1076(w)1035(w)1027(w)1004(w)998(w)924(w)910(m)769(m)755 (s)719(w)712(w)688(m)676(m)664(m)537(w)485(w)3087(w)3069(m)3034(w)1614(m)1590(s)1568(s)1547(vs)1515(s)1483(s)1465 (sh, s)1442(sh, s)1413 (vs)1358(m)1321(s)1312(m)1297(m)1253(m)1215 (sh,vs)1180(m)1150(s)1114(m)1099(m)1072(m)1059(m)1035(m)1005(m)995(w)945(w)918 (w)908(m)768(m)757(m)748(s)717(w)702(sh, m)688(m)662(m)529(w)486(m)vs = very strong; s = strong; m = medium; w = weak;sh = shoulder; b = broad.The reflectance spectrum of 3-hydroxyflavone contained two peaks at7300 and 9000 cm-1 which are due to the third v(C-H) overtone band.Hence when examining the electronic spectra of these 3-hydroxyflavonatocomplexes, bands which should appear in the region 6000-10000 cm-Icannot be accurately assigned as these bands will overlap with the absorp-tion caused by the G-H overtone band. In the spectra of these complexes,peaks which appear above 20000 cm-1 are the result of charge transferprocesses, which are strong in intensity, thereby engulfing the peaks dueto electronic transition. In the electronic spectra of high spin cobalt(II)216 Pertanika J. Sci. & TeChno!. Vo!. 3 No.2, 1995Synthesis and Characterisation of Cobalt(II) complexes of 3-Hydroxyflavoneoctahedral complexes, the 4Azg level is usually close to the 4TJg(P) level,hence the transitions from the lower 4TIg(F) level to these two upper levelsare close together. For example, in the complex [Co(dmso)6]2+ (dmso =dimethyl sulphoxide) there were two peaks at 14600 and 18700 cm-Icorresponding to the transitions described above (Elder 1968). The peaksobserved in the 10000-20000 cm-I region are given the appropriate assign-ments as shown in Table 3. In the reflectance spectrum of [Co(H20)2(flv)2]there were two peaks at 14300 and 17400 cm-I which can be ascribed to the4T1iF) -7 4Azg and 4TJg -7 4T1/P) transitions respectively. In the analogouspyridine adduct, these transitions appeared at 14300 and 17500 cm l .These transitions are comparable to those reported for [Co (dmso) 6]2+ andtherefore it is likely that [Co(HP)/flv)2] and [Co(pY)2(flv)2] are octahe-dral complexes.TABLE 3Electronic transitions of [Co(H20)2(flv)2] and[Co(PY)2(flv)2] observed between 10000-20000 cm-1Compound Wavenumber(cm- I ) Assignments[CO(HP)2(flv)2] 14300 4T (F) -7 4A19 2g17400 4T (F)-74T1/P>19[Co(PY)2(flv)2] 14300 4T (F) -7 4AIg 2g17500 4T (F) -7 4T1g(p)IgThe d-spacings for [Co (py) 2(flv) 2] and the analogous nickel (II)complex, [Ni(py) 2(flv) 2] are given in Table 4. Comparison between thetwo sets of data clearly show that [Co(pY)2(flv)2] is isomorphous with thenickel complex because the d-spacings gave almost 1:1 correspondence.Therefore, it can be concluded that the cobalt complexes have the samestructure as the nickel complex. This is not surprising since many cobalt(ll)complexes have been found to be isostructural with the analogous nickel(ll)compounds (Hashagen and Fackler 1965; Buchanan et al. 1979). Thisfeature is due to the equality of the ionic radii of cobalt(ll) and nickel(lI)which is 0.78 Afor both metal ions.CONCLUSIONThe reaction between the 3--hydroxyflavonato anion and cobalt(lI) chloridehexahydrate gave rise to diaquabis (3--hydroxyflavonato) cobalt (II) . Treat-Pertanika J. Sci. & Techno!. Vol. 3 No.2, 1995 217Yang Farina and D.A. RiceTABLE 4d-Spacings for [Co(PY)2(flv)2] dan [Ni(PY)2(flv)2][Co (PY) 2(flv) 2] [Ni (PY) 2 (flv\]dA I dA9.17 vs 9.17 vs7.61 w 7.72 w7.09 w 7.24 w5.59 w 5.64 w5.36 ill 5.39 w4.93 w 4.95 ill4.80 ill 4.79 w4.32 w 4.30 w4.07 ill 4.08 ill3.92 ill 3.96 ill3.83 w . 3.81 w3.68 w 3.68 w3.50 w 3.54 w3.35 w 3.38 wment of the water adduct with pyridine gave bis(pyridine)bis(3-hydroxyflavonato) cobalt(II). In both complexes the anion is chelated to themetal ion through the 3-hydroxy and 4-keto groupings as demonstrated bythe infrared spectra. Results of diffuse reflectance spectra indicate that bothcomplexes are octahedral in nature and magnetic moment measurementsshow that they are cobalt(II) complexes with a high spin d7 configuration.Results of X-ray powder diffraction studies imply that bis(pyridine)bis(3-hydroxyflavonato)cobalt(II) has the same structure as the correspondingnickel (II) complex. Therefore we can deduce that the geometry surround-ing the cobalt(II) ion in [Co (py) 2(flv) 2] is an octahedron and the pyridinemolecules like the nickel complex also occupy trans positions.REFERENCESBALOGH-HERGOVlCH, E., G. SPEIER and G. ARGAY. The oxygenation of copper(I) and copper(II) flavonolate complexes. The crystal structure and molecular structure ofbis(flavonolato)copper(II).j. Chern. Soc. Chern. Commun.551-552.BLUNDEN, SJ. and J.P. SMITH. 1982. Synthesis and spectroscopic studies of organotinderivatives of3-hydroxyflavone.j. Organomet. Chern. 226: 157-163.BUCHANAN, R.M., BJ. FITZGERALD and C.G. PIERPO T. 1979. Semiquinone radical anion co-ordination to divalent cobalt and nickel. Structural features of the bis(3,5-di-tert-l,2-semiquinone) coba1t(II) tetramer. Inorg. Chern. 18: 3439-3444.218 Pertanika J. Sci. & Techno!. Vo!. 3 No.2, 1995Synthesis and Characterisation of Cobalt(II) complexes of 3-HydroxyflavoneCABRERA-MARTIN, A.,j.S. DURAND and S. RUBIO-BARROSO. 1986. Fluorometric determinationof chromium at low levels with 3-hydroxyflavone and determination of chromium atlow levels wilh 3-hydroxyflavone and application of the method to steels. Anal. Chim.Acta 183: 263-267.COTTON, F.A and R.H. HOLM. 1960. Magnetic investigations of spin-free cobaltous com-plexes. 1Il. On the existence of planar complexes.J Am. Chern. Soc. 82: 2979-2983.ELDER, R.C. 1968. Base adducts of bis(2,4-pentanedionato)cobalt(1I). The crystal andmolecular structure of trans-bis (2,4-pen tanedionato) dipyridine cobalt(II),Co(AA)2(pY)2.Inorg. Chem. 7: 1117-1123.FARAGO, M.E. 1981. Metal tolerant plants. Coord. Chem. Rev. 36: 155-182.HARBONE,j.B., T J. MABRY and H. MABRY. 1975. TheFlavonoids. London: Chapman and Hall,HASHAGEN,J.T. and j.P. FACKLER,J r. 1965. Base adducts of f3-ketoenola tes. 111. Complexes ofcobalt (11) .]. Am. Chem. Soc. 87: 2821-2824.HERRMANN, K 1976. Flavonols and flavones in food plants: a review.]. Food Technol 24: 433-448.JOSE, C.l., P.S. PHADKE andA.Y. RAMA RAo. 1974. Infrared spectra offlavones and isoflavones:effect of iodine and boron trifluoride on carbonyl fraquencies. Spec. Chim. Acta 30A:1199-1206.JURD, L. and T.A. GEISSMAN. 1956. Absorption spectra of metal complexes of flavonoidcompounds.]. Organomet. Chern. 21: 1395-1401.KATYAL, M. and S. PRAKASH. 1977. Analytical reactions of hydroxyflavones. Talanta 24: 367-375.SKAAR, H., E. OPHUS and B.M. GULLVAG. 1973. Lead accumulation within nuclei ofmoss leaf.cells. Nature (London). 241: 215-216.SPEIER, G., E. FDu)p and L. PARKANYi. 1990. Chelated flavonol co-ordination inflavonolatobis (triphenylphosphine) copper (I).]. Chern. Soc. Chern. Commun. 512-513.YANG FARINA, BOHAR! M. YAMIN, HOONG-KuN FUN, BOON-CHUAN YIP and SIANG-GUAN TEOH. 1995.trans- [Bis (3-hydroxy-2-phenyl-4H-benzopyran-4- onato) bis (pyridine) nickel (11)] ActaCryst. C51 [in press].Pertanika J. Sci. & Techno!. Vo!. 3 No.2, 1995 219

Synthesis and Characterisation of Cobalt(II)

Complexes of 3-Hydroxyflavone

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Synthesis and Characterisation of Cobalt(II) Complexes of 3-Hydroxyflavone

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