Singh, P. P.

Agrawal, O. P.

Singh, M. K.

English

SampleData used in this investigation were acquired from a Portuguese identified skeletal collection, the Coimbra Identified Skeletal Collection (CISC, University of Coimbra, Portugal), comprising 364 individuals (166 females and 198 males). The source of the raw data was the original data set made available by Maria Augusta Neto (1957). Only data from complete left radii were retrieved. Ages at death ranged from 17 to 96 years. Individuals in this sample were born between 1833 and 1918, and died between 1910 and 1936.Data collection Ten measurements (in mm) of the radius were selected, including the maximum length (MLR), minimum circumference in the proximal diaphysis (MCPDR), minimum circumference in the distal diaphysis (MCDDR), transverse diameter of the head (TDHR), sagittal diameter of the head (SDHR), head circumference (HCR), neck circumference (NCR), transverse diameter of the shaft (TDSR), sagittal diameter of the shaft (SDSR), and the inferior epiphysis width (IEWR). All measurements were obtained according to Martin (1928), except the minimum circumference in the proximal diaphysis, defined by Fischer (1906).THIS DATASET IS ARCHIVED AT DANS/EASY, BUT NOT ACCESSIBLE HERE. TO VIEW A LIST OF FILES AND ACCESS THE FILES IN THIS DATASET CLICK ON THE DOI-LINK ABOV

Curate, F (via Mendeley Data)

Electronic Archiving System

Osteometric measurements of the radius in the Coimbra Identified Skeletal Collection

Sample
Data used in this investigation were acquired from a Portuguese identified skeletal collection, the Coimbra Identified Skeletal Collection (CISC, University of Coimbra, Portugal), comprising 364 individuals (166 females and 198 males). The source of the raw data was the original data set made available by Maria Augusta Neto (1957). Only data from complete left radii were retrieved. Ages at death ranged from 17 to 96 years. Individuals in this sample were born between 1833 and 1918, and died between 1910 and 1936.

Data collection 
Ten measurements (in mm) of the radius were selected, including the maximum length (MLR), minimum circumference in the proximal diaphysis (MCPDR), minimum circumference in the distal diaphysis (MCDDR), transverse diameter of the head (TDHR), sagittal diameter of the head (SDHR), head circumference (HCR), neck circumference (NCR), transverse diameter of the shaft (TDSR), sagittal diameter of the shaft (SDSR), and the inferior epiphysis width (IEWR). All measurements were obtained according to Martin (1928), except the minimum circumference in the proximal diaphysis, defined by Fischer (1906)

NOPR

Indian .Journal of ChemistryVol. 16A. December 1977. pp. 1045-1047Studies on z-Thiazolidinethione, 2,4-Thiazolidinedione &z-Imidazolidinethione Complexes of Co(ll), Ni(II), Cd(II) & Zn(II)ThiocyanatesP. P. SINGH, O. P. AGRAWAL* & M. K. SINGHChemistry Department, M.L.K. College, Balrampur 271201Received 6 January 1977; accepted 1 July 1977Complexes of the type M(NCS)2.2L[M=Co(II), Ni(II), Zn(II), Cd(II) and L=thiazolidine-thione (tat), thiazolidinedione (tzd) and imidazolidinethione (izt)] have been synthesized andcharacterized on the basis of infrared and electronic spectral, molar conductance and magneticmoment studies. These studies indicate that thiocyanate is N-bonded in all the cases exceptin Ni(II) complexes where it is bridged. The site of bonding in tzt complexes is imino nitrogen,in tzd complexes carbonyl oxygen and in izt complexes thlocarbonyl sulphur. The log K valuesof the complexes have also been determined colorimetrically.THE bonding behaviours of 2-thiazolidincthione(tzt}, 2,4-thiazolidinedione (tzd), 2-imidazo-lidinethione (izt) and ethylene monothio-carbonate towards Sn(lV), Ti(IV) , Fe(II), Co(II)and Ni(JI) halides have been recently studied>".In this paper we present the results of our studyon the complexes of these ligands with Co] II), Ni( II),Zn(II) and Cd(JI) thiocyanates. While undertakingthese studies we had two main interests, (i) to seewhether the site of bonding in these ligands changeson change of the anions from halides to thiocyanateand (ii) whether the M-NCS bond in the metal thio-cyanates changes to M-SCN on complex formation.Materials and MethodsReagent grade solvents were dried and purifiedbefore use. Metal nitrates [Metal = Co(II), Zn(II),Cd (II) and Ni(II)] and KNCS (AHa Inorganics Inc.& BDH) were used as such. 2-Thiazolidinethione(tzt), 2,4-thiazolidinediorie (tzd) and 2-imiclazolidine-thione (izt) were obtained from Eastman OrganicChemicals and used after recrystallization fromethanol.Preparation of complexes - The metal thiocyanateswere prepared by the reaction of KNCS and thecorresponding metal nitrates in ethanol. Thecomplexes were prepared by stirring the ligand andthe metal thiocyanate, in 1:2 molar ratio, indichloroethane for 48 hr. The solid comnlexeswere separated by filtration and dried in vacuo.All the complexes were recrystallized from acetone.Most of these complexes are soluble in acetoneand ethanol, have sharp melting points and arenon-conducting. These properties indicate thatthey are molecular addition compounds.Infrared spectra of the Iigands and complexeswere recorded as nujol mull on a Perkin-Elmer spec-trophotometer model 621 equipped with CsI optics.Spectra of the ligands were recorded in chloroformsolution also.*Chemistry Department, Delhi College of Engineering,Delhi 6.Electronic absorption sj'ectra of the complexeswere recorded in the region 400-1700 11m on aCary-14 spectrophotometer using acetone as thesolvent.Magnetic susceptibility measurements were carriedout using Gouy's method with Hg[Co(NCS)4i as thestandard. The diamagnetic corrections wereapplieds-".The molar conductance measurements of thecomplexes were carried out employing philips con-ductivity meter type CDC-l14.Log K values were obtained colorimetrically usingKlett-Summerson photocolorirneter.The complexes were analysed gravimetrically forCo, Zn and Cd as their anthranilate and nickelas dimethylglyoxirnate, Nitrogen was estimatedby Kjeldahl's method and sulphur as bariumsulphate. For this purpose a weighed quantity ofthe complex was fused with sodium peroxide in anickel crucible, the mass extracted with distilledwater and treated with dilute hydrochloric acid.To this barium chloride solution was added care-fully to get the precipitate of barium sulphate. Theanalytical results are recorded in Table 1.Results and DiscussionThe comparison of infrared spectra of the ligandsand their complexes indicates that the site of bondingin tzt and tzd complexes are the imino nitrogenand the carbonyl oxygen respectively in agreementwith their behaviour towarc's Sn(IV), Ti(IV) andCo (II) ha lidesv ", In tzt complexes, vNH modeshifts downwards by ,....,200 ern? while IlNH modeshifts upwards by 65-100 cm! from their free ligandpositions in chloroform, In tzd complexes, NHmodes remain more or less unaffected while '1C=O(sym and asym) show a downward shift of ,....,50crrr ", In the case of izt complexes there is no shiftin v~-H and oN-H frequencies which indicates thatthe coordination does not occur through imino nitro-gen. A band at 1270 crrr ' assigned to mixed bands['1(C=S)+o(NCS)]8 shows a negative shift of 75 crrr?1045INDIAN J. CHEM., VOL. 15A, DECEMBER 1977TABLE 1 - ANALYTICALAND MAGNETICMOMENTDATA OF THE COMPLEXES.Complexes Colour m.p. Found (calc.), % fl.eff(0C) (B.M.)Metal N SNi(NCS) a- 2tzt Yellow-green 270 (d) 14·7 13·1 46·1 3·23(14'3) (13-6) (46'5)Co(NCS) •.2tzt Blue 15·0 13·0 46·8 4·67(14'3) (13'6) (46'5)Cd(NCS) •.2tzt White 23·8 12·5 40·5(24·0) (12·0) (41,1)Ni(NCS) a-2tzd Yellow-green 270 (d) 13-9 14·0 31'6 3·47(14-4) (13'7) (31'3)Co(NCS) a- 2tzd Blue 15·0 14·0 31·7 4·50(14-4) (13'7) (32'3)Cd(NCS) a-2tzd White 23·8 12·5 28·2(24'2) (12'1) (27,7)Ni(NCS) •.2tzt Yellow-green 225 16·4 22'9 33·3 3·29(16'0) (22'5) (33'7)Co(NCS) a- 2izt Blue 245 16·6 22·0 33·1 4·52(16,0) (22'5) (33'7)Zn(NCS) a- 2izt White 16·5 21·2 32·9(17-0) (21'8) (33'3)Cd(NCS) a- 2izt White 25·6 19·9 39·0(26'0) (19'5) (39'6)*Molar conductance values of the complexes were in the range 30-36 ohm:" em! mole=t.which indicates that coordination takes place throughsulphur atom of the C=S group. The changes inthe stretching frequencies of v(C-N) +3(NCN) oncoordination are also indicative of bonding throughsulphur. The presence of bands around 285-275crrr+, which are assigned to v(M-S)5, also supportsbonding through sulphur. This approach is inaccordance with the results of Carlin's" work onethylenethiourea complexes of Co(II). The siteof bonding in the present complexes of izt issulphur in contrast to imino nitrogen in the caseof complexes with Sn(IV) and Ti(IV)2. The diffe-rence in behaviour is perhaps due to the differencein softness of the metals; Sn(IV) and Ti(IV) halidesare hard acids while Co(II), Ni(II), Zn(II) and Cd(II)thiocyanates are either the borderline cases or softacids. Therefore, izt coordinates through its hardbase end (-NH) to Sn(IV) and Ti(IV) and throughits soft base end (C=S) to Co(II), Ni(II), Zn(II)and Cd(II). However, a similar change in site ofbonding does not occur in tzt on change in Lewisacid. The thiocarbonyl group of tzt is perhaps aweaker donor as compared to thiocarbonyl groupof izt, unable to bring about a change in the site ofcoordination on changing the Lewis acid.The presence of v(C-N) and 3(NCS) bands around2040-2090 and 440-500 em"! respectively in infraredspectra indicates that thiocyanate is N-bonded inZn(II), Cd (II) and Co(II) complexes. In Ni(II)complexes vC-N occurs around 2100-2160 crrr+indicating the bridged nature of thiocyanate group.The values of softness of metals calculated fromKlopmau's equat iont'' were found to be: Cd(-3·12),Zn( -2·22),Co( -2'07)andNi( -1,52). Cadmium beingthe most soft metal it should have linked to theS-end of -SCN group, but it linked through its N-end.This change may be due to the change in ligandll,12.The softness of nickel perhaps equally suits boththe ends of thiocyanates and it prefers to form1046TABLE 2 - SELECTEDBANDS AND SPECTRALPARAMETERSComplex v.(cm-I) V3(em-l) Dq B' [3Co(NCS) •.2tzt 7,300 16,100 465 670 0·70};i(NCS) •.2tzt 16.100 27,800 980 968 0·93Ni(NCS) a- 2tzd 16,400 28,600 990 1020 0·98TABLE 3 - LOG J{ VALUES OF THE COMPLEXESComplexes D-V log K*(C=O) ----------------(crrr") Calc·tzd Obs.ua Obs·tzt ObS·iztNi(};CS) •.2L 50 7·39 6·87 6·89 6·87Cd(NCS) •.2L 75 6·34Co(NCS) •.2L 90 5·72 6·18 6·25 6·32FeCI2·2L 85 6·12 6'41 6·30 6-47SnCl •.2L 94 5·54TiCI,.2L 105 5·08FeBr2·2L 95 5·50 5·99 6·18 6·43CoCI2·2L 6·35 6·40 6·39CoI,.2L 6·07 6·12 4·85NiCI,.2L 6·37 6·29 6·41NiI2·2L 6·33 6·05 6·10*Observed values were obtained calorimetrically.bridged complexesw?", However, it readily changesto N-bonding on change of environment, and alarge number of such cases are reported in theliterature18-2o.The electronic spectra of Co(II) and Ni(II)complexes were recorded in acetone solution andin mull. The positions of spectral peaks in boththe phases are the same which indicates that solvo-lysis does not take place. The positions of thesepeaks along with their assignments and spectralparameters derived from V2 and va21are included inTable 2.SINGH et al.: Co(II). Ni(II). Cd(II) & Zn(II) COMPLEXESSpectral and magnetic moment values indicatethat the complexes of the type Co(NCS)a.2L aretetrahedral and Ni(NCS)2.2L octahedral.Relation between !1v (C=O) and stability constant(log K) - Since the site of bonding in tzd complexesis carbonyl oxygen, we have calculated the log Kvalues of the complexes using the following eqna-tion22: Log K = 0·042 v(C=0)-64·428.The calculated values (Table 3) are in goodagreement with the previously reported= log Kvalues of tzd complexes.On plotting a graph between log K values and !1v(C=O) values of the ligands a straight line wasobtained, This graph may be useful in evaluatingthe approximate log K values of the complexes if!1v (C=O) value is known22.In the cases of tst and izt complexes. the coor-dination site is imino nitrogen and thiocarbonylsulphur respectively, hence the above equation isnot applicable for calculation of log K values.We have, however, determined their log K valuescolorimetrically, and the values are presented inTable 3.The sequence of stabilities of the complexes withrespect to different ligands is as follows:Fortzt: Ni (NCS)z>CoClz> FeClz >NiC12 >CO(NCS)2>FeBf2>CoIz'For tzd: Ni(NCS)2>FeCI2>NiCl2>CoClz>Nilz>Co(NCS)2>CoI2>FeBr2·For izt: Ni(NCS}z>FeC12>FeBr2>NiCI2>CoClz>Co(NCS)z>NiIz>CoIz·It is interesting to note that the sequence of Lewisacids differs with respect to each of the ligand andit is difficult to propose any definite order ofacceptor strength of Lewis acids. In contrast, theacceptor strength of metal ions is well established'"in terms of Irving Williams series.AcknowledgementThe authors gratefully acknowledge the financialsupport of UGC, New Delhi, and the instrumenta-tion facilities provided by Concordia UniversityMontreal.References1. SINGH, P. P., AGRAWAL, O. P. & GUPTA, A. K., Inorg,chim. Acta, 18 (1976). 19.2. SINGH, P. P. & PANDE, I. M., J. inorg. nuci. Chem., 34(1972), 591.3. SINGH, P. P. & RIVEST, R., Can. J. Chem., 46 (1968),2361-4. FILLIPPO, D. DE & PRETTI, C., J. chem, Soc. (A), (1970),1904.5. ADAMS, D. M. & CORNELL, J. B., J. chem. Soc., (A),(1967), 884.6. FIGGIS, B. N. & NYHOLM, R. S., J. chem. Soc., (1958),4190.7. FIGGIS, B. N., LEWIS, J. & WILKINS, R. C., Modern co-ordination chemistry (Interscience, New York), 1960,403.8. ELMORE, D. T., J. chem. Soc., (1958), 3489.9. CARLIN, R. L. & HOLT (Jr) S. L., Inorg. Chem.,2 (1963),849.10. KLOPMAN, G., J. Am. chem. Soc., 90 (1968), 223.11. TURCO, A. & PECILE, C., Nature, 191 (1961), 66.12. BERTINI, I. & SABITINI, A., Lnorg, cu«, 5 (1966),1025.13. NELSON, S. M. & SHEPHARD, T. M., J. inorg. nucl. Chem.,27 (1965), 213,14. CLARK, R. J, H, & WILLIAMS, c. S,' Sbectrochim. Acta,22 (1966), 108.15. AHUJA, I. S. & GARG, A., J. inorg. nucl, Chem., 34 (1972).1929.16. KING, H. C. s.. KOROS, E. & NELSON, S. M., Nature,(1962), 196; 572.17. PORAI KOSHITS, M. A. & TISCHENKO, G. N., Kristallogra-fiya, 4 (1959), 239.18. COOK, R. C. & BURMEISTER, J. L., J. organomet. Chem.,63 (1973), 471.19. EpPs, L. A. & MARAILLY, L. G., Inorg. Chem., 7 (1973),1514.20. BUCKINGHAM,D. A., GREASER, I. 1. & SARGESON,A. M.•Inorg. Chem., 9 (1970), 655.21. TANABE, Y. & SUGANO, S., J. phys. Soc. Japan, 9(1954), 753.22. SINGH, P. P. & PANDE, I. M., J. inorg. nucl, Chem., 34(1972), 1139.23. IRVING, H. & VVILLIAMS,R. J. P., Nature, 162 (1948).746; J. chem. Soc., (1953). 3192.1047