INDIAN J. CHEM., VOL. 21A, MAY 1982

I

type. This is also expected due to the presence ofdonor atoms of unequal field strengths.

Based on these studies the structure (1) may beproposed for the complexes.

The authors are thankful to the CSIR, New Delhifor financial assistance and RSIC, IIT Madras forspectral measurements.

References

1. AGGRAWAL, R. C., PRASAD, T. & YADAV, B. N., J. inorgnucl. Chem., 37 (1975), 899.

2. TEOTIA, M. P., SINGH, ISHWAR & RANA, V. B., Transitionmet. Chem., 4 (1981), 60.

3. RANA, V. B., GURTU, J. N. & TEOTIA, M. P., J. inorg.nucl. Chem., 42 (1980), 331.

4. SRIVASTAVA, A. K., RANA, V. B., MOHAN, M., SWAMI,M. P. & JAIN, P. C., J. inorg, nucl. Chem., 37 (1975),723.

5. JOHNSON, M. F. & FORSBERG, J. H., Inorg, Chem., 11(1972), 2683.

6. GATTERMAN, L. & WIELAND, H., Laboratory methods ofof organic chemistry (McMilan, New York), 1943, 144.

7. SACCONI, L., Z. anorg. allg. Chem., 275 (1953), 249.8. MOELLER, T. & KRAMERS, H. E., J. phys, Chem.,48 (1944),

395.9. GEARY, W. J., Coord. chem. Rev.,7 (1971), 81.

10. NAGAKO, K., KIEOSHITA, H. & HIRAKAWA, A., Chem.pharm. Bull., 12 (1964), 1198.

11. SAHNI, S. K., SANGAL, S. K. GUPTA, S. P. & RANA, V. B.,J. inorg; nucl. Chem., 39 (1977), 1098.

12. BIRADAR, N. S. & KULKARNI, V. H., J. inorg. nucl. Chem.,33 (1971), 2451.

13. RAo, C. N. R., Chemical applications of infrared spectro-scopy (Academic Press, New York), 1967, 758.

14. BRAIBANTI, A. B., DALLAVALLE, F., PELLiNGHAL, M. A.& LAPORATTI, E., Inorg, Chem., 7 (196&), 1430.

15. NAKAMOTO, K., Infrared spectra of inorganic and coor-dination compounds (Wiley Interscience, New York),1970, 167.

16. FERRARO, J.R., BASILE, J. H. & KAVOCIE, D. L., Inorg.Chem., 5 (1966), 371.

17. YOST, D. M., RUSSEL, H. & GARNER, C. S. S., Rareearth elements and their compounds (Wiley, New York),1947, Chap. 2.

18. SINHA, S. P., Spectrochim. Acta, 22 (1966), 57.19. SELBIN, J. AHMED, N. & BHACCA, N., Inorg, Chem., 19

(1970), 1383.20. DICKE, G. H., Spectra and energy levels of rare earth ions

ill crystals (Interscience, New York), 1968, 135.21. RANA, V. B. &. SAHNI, S. K., J. inorg. nucl. Chem., 19

(1977), 2271.

530

Complexes of Titanium, Tin & Zirconium Tetra-chlorides with Phenazone & Amidopyrinet

B. P. RAJELA·Defence Materials and Stores Research and Development

Establishment, Post Box No. 320, Kanpur 208013

and

S. C. JAINChemistry Division, Bhabha Atomic Research Centre, Trombay,

Bombay 400 085

Received 13 October 1980; revised 28 July 1981; rerevised andaccepted 19 November 1981

Complexes of TiCI., SnCI. and ZrCI. with phenazone (Phena)and amidopynne (Ampy) have been synthesized. While Phensforms both 1 : 1 and 1 : 2 adducts, only 1 : 1 adducts are obtainedwith Ampy. Reaction of MCI •.Ampy (wltere M = Ti or Sn)with BBr3 gives bromine substituted adducts of the type MDr,.Ampy.2BBr". The compounds have been characterised on thebasis of analytical and spectral data.

COMPLEXES of amides, imidesvs and lactams+!having two possible donors, oxygen and nitrogen

have been extensively studied with group (IV) hali-des1,2. However, very little is known about theligating behaviour of phenazone (phenz, I) andamidopyrine CAmpy, II) which have more than onenitrogen atom and a carbonyl oxygen as potentialdonor sites. We report here the preparation andcharacterisation of the complexes of TiCI4, SnCI4and ZrCl4 with Phenz and Ampy. We have alsobrominated the TiCl4.Ampy and SnCl4.Ampy com-

\H3 }H3C-N

II \C N

H •••.. "c/ 'C6HS

IIo

(I)

plexes using excess BBra with a view to investigatingthe ligating behaviour of the ring nitro gens.

All the preparations were carried out inside a drybox continuously flushed with dry nitrogen as repor-ted earlier", The Lewis acids, TiCI4, SnCI« andZlCl4 were purified by appropriate methodss,The ligands Phenz and Ampy (Aldrich Chemicals)were used as such. BBr3 was prepared by theliterature method". Benzene, carbon tetrachlorideand methylene chloride used as solvents werepurified and rendered anhydrous by conventionalmethods.

The general method of preparation involved mixingof metal halides and ligand solutions with constantstirring. In the case of ZrCl4 which is not soluble

tDMSRDE Communication No. 1042; work reported hereforms part of the Ph.D. Thesis of B.P. Hajela, Kanpur Univer-sity, Kanpur, 1976.

in inert solvents, a suspension of ZrCl4 was addedto an excess of ligand solution and the contentsstirred for several days at room temperature. Ineach case powdery product was obtained which wasfiltered, washed with the solvent and dried in vacuo.The preparative details regarding the amounts ofthe reactants taken and the solvent used are givenbelow:

Ligand 1.33 g (0.007 mol), TiCl41.71 g(0.009 mol) each dissolved in 20 mlbenzene;

SnC/4.2Phenz : Ligand 1.85 g (0.01 mol), SnCl41.33 g (0.004 mol) each dissolvedin 20 ml benzene;

TiCl4.Ampy Ligand 1.80 g (0.008 mol), TiCl42.94 g (0.015 mol) each dissolved in20 ml methylene chloride;

SnCI4.Ampy: Ligand 1.84 g (0.008 mol), SnC144.46 g (0.017 mol) each dissolvedin 20 ml benzene;

ZrC/4.Ampy: Ligand 1.42 g (0.006 mol), ZrCl41.37 g (0.006 mol) each in 20 mlmethylene chloride;

TiBr4.Ampy.2BBra and SnBr4• Ampy. 2BBra - Toabout 1 g of the chloro adduct liquid BBra wasadded dropwise till the evolution of BCl3 stoppedand the excess BBra formed a slurry with the pro-duct. After refluxing the reaction mixture underdry nitrogen for about ""I hr. the excess BBra waspumped out through a liquid air trap.

The infrared spectra (4000-650 em-s) were re-corded on a Perkin-Elmer spectrophotometer model21 in nujol mulls using sodium chloride optics.Molecular weight determination and conductivitymeasurements could not be carried out due to poorsolubility of the complexes in inert organic solvents.The analytical results (Table 1) show that whilePhenz forms both 1:1 and 1:2 adducts, Ampy givesonly 1:1 adducts.

TiC/4.Phenz and SnC/4.2Phenz - Phenazone hasthree donor sites; two nitrogen atoms and onecarbonyl oxygen. Thus, there are several possiblestructures for the adduct TiCI4.Phenz. If Phenzacts as a monodentate ligand, titanium would ex-hibit a coordination number of five in a monomericform or a coordination number of six in the dimericform involving chlorine bridging. However, ifPhenz acts as a bidentate ligand then it can eitherchelate forming (less likely) a strained 4-memberedring or it can bridge two metal atoms coordinatingthrough the carbonyl oxygen and one of the twonitrogens depending on their basicities. This wouldimpart a linear or cyclic polymeric structure to theadduct and satisfy the most common coordinationnumber six for titanium.

The IR spectrumt of TiCl4.Phenz shows twobands at 1548 and 1565 which for the free ligandappear at 1675 and 1630 respectively. These bandscan be assigned to v (C=O) and v(C=C) respec-

tIR "malt in cm-1 throughout the note.

NOTES

TABLE 1- ANALYTICAL RESULTS OF PHENZ AND AMPYCOMPLEXI:.S

Metal HalogenCompounds Colour m.p.,oC (%)t (%)*

Calc. Calc.(Found) (Found)

TiCI •.Phenz Orange 112-14 12.68 37.53(13.2) (37.3)

SnCI,.2Phenz White 73-75 18.64 22.26(19.1) (22.7)

TiCI,.Ampy Orange 178-80 11.38 33.68(11.6) (32.9)

SnCl4.Ampy White 298-300 24.14 2&.&0(23.7) (2&.6)

ZrCI,.Ampy Cream-yellow 26&-70 19.64 30.53

(19.1) (30.4)TiBr •.Ampy.2BBr3 Red 117-1& 4.35 72.65

(4.4) (72.2)SnBr •.Ampy.2BBr. Pale-yellow 12&.30 10.2 6&.6

(9.9) (6&.4)

tDetermined gravimetrically as oxides.*Precipitated as silver halides and estimated gravimetrically.

tively, Bathochromic shift of the order of 127 inthe v(C=O) suggests the involvement of the car-bonyl groups in coordinationt-t=. Two more bandsat 1323 and 1304 for the free ligand appear marked-ly shifted for the 1:1 adducts but remain almostunaffected for the 1:2 adduct. These bands can beassigned to v(C-N)9. In such a situation in the 1:1adduct the ligand molecule Seems to bridge twotitanium atoms coordinating through the carbonyloxygen and through the nitrogen with methyl subs-tituent group. Among the two ring nitrogens theone bonded to electron withdrawing phenyl groupis expected to be less basic than the nitrogen attachedto electron releasing methyl group. However, fromthe present data it is not possible to ascertain thelinear or cyclic nature of the complex.

In the case of SnCl4.2Phenz the structural assign-ment can be explained by assuming coordinationnumber six for tin where the ligand molecule acts asmonodentate only. The IR spectrum of the com-pound shows the v(C=O) band at 1550 shifted by-125 as compared to the position in the free ligand.The v (C-N) bands at 1323 and 1304 for the freeligand are almost unaffected on coordination andappear at 1320 and 1299 for the compound. Thisstrongly suggests the monodentate nature of theligand in the I -:2 adduct where carbonyl oxygenonly coordinates to the tin atom.

Compounds MC/4.Ampy (M=Ti, Sn or Zr) - Thereaction of Ampy(II) with TiCI4, SnCI4 or ZrCl4gives 1:1 adducts. The spectrum of the free liganddisplays three medium to strong bands at 1600,1625 and 1668. As a result of complexation the twohigher energy bands are considerably lowered whilethe one at 1600 remains unaffected. The band at1668 in Ampy can be assigned to v(C=O). It islowered by 90-100 cm-1 in the spectra of the com-plexes indicating the coordination of the carbonyl--"oxygen. Another major difference in the spectraof the ligand and those of the complexes can be

531

INDIAN J. CHEM., VOL. 21A, MAY 1982

observed in the -v(C-N) region. The two bands at1342 and 1315 in the ligand are assigned to v(C-N);these shift to 1320 and 1260 in the spectra of com-plexes indicating coordination of the nitrogen ofthe dimethyl group.

Compounds TiBr4.Ampy.2BBra and SnBr 4, Ampy.2BBra - These compounds were obtained by thereaction of compounds MC14.Ampy (M=Ti or Sn)with BBra. It is interesting to note that while allthe four chlorine atoms get replaced by bromine,additional two molecules of BBra get bonded to thetetrabromo complex resulting in the formation ofcompounds of the type MBr4.Ampy.2BBr3• HereBBr3 seems to serve two functions i.e. (i) it acts asa brominating agent and (ii) it also acts as a Lewisacid where two molecules of BBr3 coordinate withtwo available ring nitrogens on the ligand molecule.

The IR spectra of these bromo complexes in theregion of v(C=O) and v(C-N) are similar to thoseof the parent chloro compounds.

It is interesting to observe that a medium bandat 1090 for the ligand appears as an unshifted weak.band in MCI4.Ampy, but the same band shifts andsplits into two bands at 1050 and 1040 in spectraof the bromo complexes. If the band at 1090 isassociated with v(N-N) then the lowering and split-ting of the band is not surprising as the coordinationof BBra molecules will considerably affect thev (N-N).

The most striking differences in the spectra ofthe bromo adducts as compared to the originalchloro adducts appear in the region 960 to 800.Another medium band at 960 appearing in the bromoadducts neither appears in the spectrum of freeligand nor in the spectra of chloro adducts. It is,therefore, reasonable to assume that this band isassociated with the coordination of BBrs. Vibra-tional frequencies '12, Vaand v. are reportedw tobe IR active for BBra which appear at 375, 820 and150 respectively. The band at 760 can be attributedto the combination band arising due to Va + '14'Another medium-strong band at 840 appears onlyin the spectra of bromo adducts. The IR bands inthe 886-840 region can be assigned to VB-N frequ-encies. Jain and Ra04 have also assigned a band at790 to v B-N mode.

We thank Dr. J. N. Nanda, former Director,DRL (M) (now DMSRDE), Kanpur for encourage-ment.

References

1. JAIN, S. C. & RIvEST, R., J. inorg. nuc/. cu«. 29 (1967),2787.

2. JAIN, S. C. & RIvEST, R., J. inorg, nuc/. Chem.,31 (1969),399.

3. BoHUNOVSKY,0., JAIN, S. C. & RIVEST,R., Can. J. Chem.,47 (1969), 1689.

4. JAIN, S. C. & RAO, G. S., J. Indian chem. Soc., 53 (1976), 25.S. JAIN, S. C. & RIVEST,R., Can. J. Chem., 40 (l96~), 22-",3.6. JAIN, S. C. & RIVEST, R., ce« J. Chem., 41 (1963), 2130.7. AHUJA, H. S., KHAN, I. A.. KUNTE, P. P. & RAo, G. S.,

BARC Report. No. 1 (1972), 174.8. JAIN, S. C., GILL, M. S. & RAO, G. S., J. Indian chem. ss«:

53 (1976), 537.

532

9. JAIN, S. C. & RIVEST, R., Can. J. Chem., 45 (1967), 139.10. JAIN, S. C. & HAJELA,B. P., Indian J. Chem., 12 (1974)

843.11. NAKAMOTO,K., Infrared spectra of inorganic and coordina-

tion compounds (John Wiley, New York), (1962), 90.

Synthesis of Schiff Base Derived from 2,4-Dihydro-xyacetophenone & Ethanolamine & Structural Studiesof Its Chelates with Cu(II), Ni(Il), Co(D) & Fe(lll)t

VlLAS RANBAORE,V. J. TYAGARAJU,VASUDHAATRE &M. C. GANl'RKAR·

Department of Chemistry, Osmania University,Hyderabad 5()()007

Received 6 August 1981; revised 20 October 1981; accepted14 December 1981

Complexes of 1 : 1 stoichiometry of Fe(lIl), Co((]), Ni(Il)and Cu(Il) with the schiff base derived from 2,4-Wbydroxyaceto-phenone and ethanolamine have been prepared and characteri1:ed.The metal to ligand ratio is 1 :1 in all chelates. Cu(II) andFe(III) complexes are suggested to have polynuclear and binuclearstructures respectively, with oxygen bridges in an octahedral geo-metry. Co((]) and Ni(IJ) complexes have been assigned thetrigonal bipyramidal and tetrahedral geometries. Cu(Il) andFe(IIO complexes have low magnetic moments as compared tospin only values, due to antiferromagnetic interaction in solidstate.

SCHIFF bases derived from simple aromaticaldehydes and ethanolamine act either as

bidentate or tridentate with different metals. Forexample, Nehydroxyethylsalicylideneimine hasbeen reported! as bidentate in Cu(lI), Fe(IU) com-plexes whereas in Ni(II) chelate it is shown 2 to actas a tridentate with oxygen of the alcoholic hydroxylalso participating in coordination without deproto-nation. Recently boron" and vanadyl- chelates "Ofschiff base derived from o-hydroxyacetophenone andaminoalcohols have been studied. Complexes ofresacetophenone thiosemicarbozone" etc. havebeen studied but no attempt has been made to syn-thesize and study the complexing behaviour of theschiff base resulting from resacetophenone (2, 4-dihydroxyacetophenone) and ethanolamine. Inthis note we report the synthesis of this schiff base(RETA) and its complexing behaviour towardsFe(III), Co(II), Ni(I1) and Cu(II). Azomethinecompounds of resacetophenone such as hydrazonesare reported to be physiologically active. Preli-minary screening of the presently synthesizedchelates shows them to be physiologically active.

All the solvents and reagents used were of ARgrade. Magnetic susceptibilities were determinedat room temperature using Faraday technique.The metal estimation were done following standardprocedures 7•

For the preparation of the schiff base, a solutionof ethanolamine (0.1 mol) was added to a solution

tPresented at the Annual Convention of Chemists 1980, .held in Bombay.