Indian Journal of ChemistryVol. 31A, January 1992, pp. 58-60

Complexes of chromium(III), cobalt(II),nickel(II), copper(II) & molybdenum(VI)

with indane 1,3-dione-2-isonicotinoylhydrazone

Sayaji Rao & K Hussain Reddy"

Department of Chemistry, Sri Krishnadevaraya UniversityAnantapur 515003

Received 3 May 1991; revised and accepted 19 September 1991

A new hydrazone derivative of indane 1,2,3-trione hasbeen synthesized and characterized as indane 1,3-dione-2-isonicotinoylhydrazone (UH). Complexes of IIH withchromium(III), cobalt(II), nickel(II), copper(II), palladi-um(II) and molybdenum(VI) have been prepared andcharacterized on the basis of elemental analysis, conduc-tivity, magnetic, electronic and infrared spectral studies.IR spectral studies suggest that IIH acts as bidentate li-gand in all complexes, the bonding sites being the enolicoxygen and azomethine nitrogen atoms.

Hydrazone derivatives containing additional donorsites such as :: C = 0 and heterocyclic nitrogen haveinteresting ligational features I. In continuation ofour earlier studies:' - \I on ninhydrin derivatives, weconsidered it worthwhile to prepare transition metalcomplexes of indane 1,3-dione- 2-isonicotinoyl-hydrazone (IIH), a derivative of ninhydrin and bio-logically active isonicotinic acid hydrazide'.

llH

In this note the results of the synthesis and struc-tural characterization of chromium(III), cobalttll),nickeltll), copperfll), palladium(Il) and molybde-num(VI) complexes with the first hydrazone deriva-tive of ninhydrin are described.

Synthesis of indane 1,3-dione-2-isonicotinoyl-hydrazone(/lH) .

It was prepared by refluxing equimolar amountsof ninhydrin and isonicotinic acid hydrazide in 1:1aqueous methanolic medium for 30 min. The yellowcolourcd precipitate was filtered off, washed withmethanol and hot water and dried in vacuo; yield72%; m.p. 209-21O°C. Identity of IIH was con-

firmed by elemental analysis [Found: C, 63.40; H,3.30 and N, 14.65%; calc. for ClsH9N303:C, 64.52;H, 3.22, and N, 15.05%), infrared spectra [1705(vC =°of indane moiety); 1680 (vC =°of amidogroup); 3340 and 3210 (vNH) and 1590 cm-1

(v : C = N - of azomethine group)), NMR spectra(0) [pyridyli-il-l), 8.20(d), 7.01(d), 6.18(d); indane(4H) 6.45(s) and amido NH, 5.65(s)) and massspectra [78(CsHsN) and 76(C6HS))'

Synthesis of the complexesMetal salt (2.5 mmol) dissolved in the minimum

amount of water was added to a solution of indane1,3-dione- 2-isonicotinoylhydrazone (5 rnmol) in1:1 dimethylformamide (DMF )-methanol solventmedium. Then a few drops of 1M sodium hydroxidein methanol were added and contents refluxed for2 hr. On cooling, the product separated out; it wasfiltered in vacuo, washed with hot water, methanoland finally dried at 80°C for 2 hr. Yield and analyti-cal data are given in Table 1.

The metal salts CrCI3.6HzO; CoClz.6HzO;NiClz.6H20, CuCI2.2HzO; PdCl2 and (NH4)M0024.4H20 used were of AR grade. All the chem-icals used in this study were BDH reagents or rea-gents of equivalent quality.

Molar conductances of the complexes in DMFsolutions (- 10-3 M) were measured with a Sys-tronic 303, direct reading conductivity bridge. Mag-netic susceptibility measurements were carried outusing a vibrating sample magnetometer (VSM) op-erating at field strength of 3 KG to 8 KG at roomtemperature. Electronic spectra were recorded on aCarl Zeiss DMR-21 recording spectrophotometerin solid state in the region 185-1200 nm. IR spectrawere obtained in the range 4000 to 180 em - I on aPerkin Elmer 983 G infrared spectrophotometer inKBr discs. IH NMR spectra were recorded in d(.,-DMSO medium on Varian XL-300 spectrometer atroom temperature.

Results and DiscussionAnalytical data (Table 1) indicate the formation of

1:2 (M:IIH) complexes of molecular formula[M(IIH}z(H20lz). All the complexes decompose inthe 220-320°C temperature range. All complexesare insoluble in water and common organic solventsbut soluble in DMF or DMSO and these are foundto be nonelectrolytes in former solvent. Insufficientsolubility of these complexes in suitable solventsprecluded the determination of molecular weights.

NOTES 59

Table I-Colour, yield melting points, magnetic moment and analytical data of transition metal complexes of indane1,3-dione- 2-isonicotinoylhydrazone(IIH)

Complex Colour m.p.,(°C) fief!. Found(Calc.), %(Yield,%) (BM)

C H N

[Cr(IlHhClH~Ol Yellow 320 3.60 56.55 2.80 11.10(65) (54.43 ) (2.73) (12.69)

[Co(IlH)2(H2Ohl Brown 318 2.72 56.45 2.85 10.64(70) (55.30) (3.07) (12.90)

[Ni(IIHh(HP)21 Deep-red 315 3.90 53.40 3.17 12.75(72) (55.32) (3.07) (12.91 )

[Cu(IIHh(H2Obl Brown 221 2.09 56.50 3.10 12.75(73) (54.91) (3.05) (12.82)

[Pd(IlHhl Parrot-green 235 Diamag. 5l.97 2.33 12.61(70) (54.34) (2.41) (12.68)

[Mo02(IIH)21 Grey 280 Diamag. 56.50 2.57 12.05(63) (52.63) (2.33) (12.28)

Table 2- Electronic spectral data and ligand field parameters of[Ni~(H20hl complex

Spectral data Observed Calculated 14.15

80501428520830

1311022005

731± 11750.70580501.63

23.0

v]B35bVh*

B35**lODqV2/V1

LFSE(kcal/rnol)

"Difference in the observed and calculated value of frequencies"Ratio of free ion and of complex.

80501.77

The chromium(III) complex shows a magneticmoment value of 3.6 B M Three bands are ob-served at 12195,23250 and 35570 ern -I in its elec-tronic spectrum corresponding to 4~ (F)-+4~g{F);4A2g(F) -+ 4 T.,g(F) and 4A2iFi -+ 4 T.,/P) transitionsrespectively in favour of octahedral geometry!".

The (,ueff.l value (2.72 B M) of cobalt complex isinconsistent with octahedral" coordination. How-ever, the lowering in magnetic moment value of thiscomplex may be attributed to the contribution oflow and high spin states of cobalt(II} or a dimericstructure'", This complex shows two bands at 23810and 16805 em - I assignable to 4T.,JF} -+4 T.,iP} (v3)and 4T.,g(F)-+4~g(F)(V2) transitions respectively inoctahedral field!'. The electronic repulsion parame-ter (B) and 10 Dq are found to be 737 and 6950em - I, respectively. The ratios of v2 to VI and LFSE

are 2.42 and 19.8 kcal mol-I as required for octahe-dral cobalt complex!".

The magnetic moment of nickel(II) complex isfound to be 3.9 B.M in favour of octahedral geome-try with 3~g ground state 13. Bands at 10640( VI)'16130( v2} and 26315( v3} are attributable to3~iF}-+3~g(F); 3~g(F}-+3T.,g(F) and3~g(F} -+ 3 T.,g{P) transitions respectively. The spec-tral data were used to compute ligand field parame-ters". The value ofB35 and 10 Dqwere used to cal-culate v2 and/or V3 and results are given in Table 2.The electronic spectral data together with reportedmagnetic moment values suggest an octahedralgeometry for the present nickel(II} complex 13.10.

The magnetic moment value of copper{II} com-plex is found to be 2.09 B.M., slightly higher thanthe magnetic moment value normally observed forcopper(II} complexes. The magnetic moment of thiscomplex indicates no metal-metal interaction. Astrong band at 15380 em - I in the electronic spec-trum of copper complex has been assigned to2 Eg -+ 2 ~g transition indicating the presence of cop-per in an octahedral field 17. 18.

Palladium complex is found to be diamagnetic atroom temperature. Three bands have been ob-served in the electronic spectrum at 16660,24390and 34480 cm - I. The first low energy spin-allowedband has been assigned to a IA1g -+ !~g transition, si-milar tv the assignment by Jorgensen for PdCI~-{ref. 19}. The bathochromic shift is expected beca-use of the spectrochemical difference between theIIH and Cl-. The second and third bands are spinallowed transitions which may be due to IAlg -+ IBIg

and IAIg -+ IEIg transitions, respectively.Molybdenum complex is found to be diamagnetic

60 INDIAN J CHEM, SEe. A, JANUARY 1992

as expected for hexavalent molybdenum. The elec-tronic spectrum of this complex exhibits a band at410 nm (24390 em - 1)with low molar extinction co-efficient. As the optical density value is low and asthere is no evidence for any d-d transitions over thevisible range, this complex could be Mo(VI) spe-cies?", rather than Mo(V).

Infrared spectral studiesIn the infrared spectrum of ligand (IIH) two

vC =0 frequencies are observed at 1705 and1680 cm - 1 attributable2.8.9.19.2oto C =0 of indaneand amido groups respectively present in the ligand.The appearance of latter band in the IR spectrum ofligand indicates that IIH remains in thione form atleast in the solid state. In all complexes the formerband is not shifted suggesting non-participation ofindane oxygen in coordination. The amido vC = 0band disappears in the IR spectra of all complexes,and instead a new band due to vC - 0 is observedaround 1095 em - 1 indicating enolization of IIH inthe presence of metal ion and under the reactionconditions employed in the preparation of metalcomplexes. The enolization+ of ligand in the metalchelate is supported by the fact that the broad peaksat 3340 and 3210 ern -I in ligand spectrum due toNH s.tretching disappear in all complexes.

A strong band observed in the IR spectrum of IlHat 1590 cm -I due to azomethine group shifts ( -10 cm - I) to lower frequency indicating the partici-pation of azomethine nitrogen atom in complex for-mation24.25• A strong band at 1545 cm-I in ligandspectrum is assigned to delocalized - C =N - pres-ent in isonicotinic ring of IIH. This band is not af-fected in spectra of all complexes indicating thenon-participation of ring nitrogen atom in coordina-tion.

A strong band at 925 em - 1 corresponds to transdioxomolybdenum group present in Mo complex.In all complexes (except Pd and Mo), bands due tocoordinated water molecules26 - 28are observed inthe regions 3215-3260, 1290, 880 and 760 cm-Iattributable to OH stretching, bending, rocking andwagging vibrations respectively. In chromium com-plexCr -:-Cl vibration is also found at 310 em -I.

The coordination of IIH through azomethine ni-trogen and enolic oxygen is further corroborated bybands observed around 430 (vM - 0) and360 nm : 1 (vM - N) in far IR spectra" of all metalchelates.

ESR spectrum of copper complex shows twopeaks at 2.33 and 2.09 corresponding to &1and g.lrespectively.

On the basis of elemental analysis, conductivity,magnetic moment, electronic and infrared spectralstudies, octahedral structure is assigned to chrom-ium, cobalt, nickel and copper complexes while asquare planar structure is suggested for the palladi-urn complex.

AcknowledgementThe authors thank the authorities of CDRI, Luck-

now and RSIC, Bombay for providing elemental an-alysis and spectral data respectively.

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