Aggarwal, R. C.

Singh, N. K.

English

Defence Science Journal

ACYL HYDRAZINE COMPLEXES OF SOME BIRST ROW TRAnSITION META.L (If) - PICRATES Banaras Hindu University, yaranasi (Received 26 June 1976; revised 22 December 1976) Cationic complexes of the types [M(BH),  (H,O)J (Picrate), [ Y = M n ( I I ) ,  Fe(II),Co(II) Xi(l1) or 5(11) and or Zn(II)] ,  [Mja(r9B), (Picrate),[WU=Ni{I!?) or Molar conduct an^^^ of the complexessho~ that they are 1 : 2 electrolytes. Magnetic and electronic spectral studies indicate that Cu(II)  comp- lexes ere square planar, whereas those of dlw(II) ,  Fe(II) ,  Co(I l )  and Ni ( I I )  are spin-free octahedral. Compositions andinfrared spectra of the complexes suggest that acyl hydrazines act as a neutral bidentate ligands coordinating via oarbonyl oxygen and primary amine nitrogen. Where possible spectral parameters such as 10 Dq, B', /3, p and A' have been evaluated from the magnetic and electronic spectral data. The values of 10 Dp and B suggest a place between water and ammonia for the liganda in the speotrochemical series and the above parameters also indicate that SH exerts a stronger ligand field than BH. Acyl hydrazines as ligands have attracted the attention of several investigators 1-4. Dutta Ahmad & Chaudhari have shown that acetyl and benzoyl hydrazines act as monodentate ligands towards transition metal ions and coordinate in the 'imidol' foim via the nitrogen of the - NH group6. But more recently Aloock et. a1.6 and Iskandar & coworkers7 have suggested that these and some other acyl hydrazines enter into bonding in the 'keto' form and function as bidentate ligands coordinating through carbopyl oxygen and terminal nitrogen. In view of the controversy in theliterature regarding the mode of bonding of the mono- acyl hydrazines in their transition metal complexes it was thought of interest to investigate themode of bond- ing and stereochemistry of benzoyl and salicylyl hydrazines complexes of some first row transition metal (11) picrates and the results obtained are described in the present communication. ' The complexes are of in- terest to Defence as explosives and detonators. All the chemicals used were of BDH or equivalent quality. Solvents were purified and made anhydrous employing the standard procedures. Metal pictrates were 'prepared as described earlier*. Benzoyl hydrar zine (BH) end salicylyl hydrazine (SH) were prepared by following the literature procedures9 a 10. Preparation and analysis of the complexes [N(BH), (H20),] (Picrate),, [ M ~ ( B H ) , I  (pi& ate),. 2Ba0 and [Cu(BH),] (Picrate), were prepared by mixing the aqueous solutions of metal picrates and BH in h1:3 molar ratio. All the complexes were preci- pitated immediately. They were filtered, washed with water and dried in vacuo. [CO(BH)~] (PicraEe),.H,O, [N~(BH) , ) '  (Picrate),. HzO, [ i i  (SH),] (Picrate),, [Co(SH), (H,O),] (Pinnte), and [pe(SH), (H20),] (Picrate), were prepared by reactingan ethanolic solution of the metal picrates and the ligan& in- 1:3 molar ratio. The complexes were precipitated by concentrating the reaction mixtures and then treating them with water. They were filtered, washed with water and dried in vacuo. [Nn(BH), (H,O),(Pi~rate)~] [Zn (BE)*] (Picrate)*, [ M ~ ( ~ S H ) ,  (HzO).] (Pimate),, [Cu(SH)pl ( P i ~ r a t e ) ~  and [Zn(SH),] (Picrate), were prepared by mixing the ethanolic solutions of the metal picrate and the ligand in - 1:3 molpr ratio. The reaction mixtures were refluxed for + hr. and concelltrated on a water bath. The complexes which separated on cooling were filtered, washed with cold ethanol and dried as before. All the soluble complexes were recr~stallised from ethanol or acetone. The complexes were analysed for metal and nitrogen as described earliers. Hydrazine was estimated volumetricallyll with KIO, after submitting thesomplexes to acid hydrolysis for + 2 hr. The water content in the hydrated complexes was estimated by flnding out the loss in weight suffered on heating at 110-150~~  for c? 3 hr. The analytical data are given in Table 1. DEE. Sor. J., VOL. 26, OCTOBER 1976 I Equipment~s and the methods employed for measuring molar conductance, magnetic susceptibility, electronic and infrared spectra were the same as used in our previous studies8. The pertinent experimental data are given in Tables 1-3. The values of the spectral parameters 10 Dq, B', j3 & Po were calculated as described by Lever1,. D I S C U S S I O N  A11 the complexes under the present investigation melt in the range 110-210°C and explode when heat- ed at - 250°C. They are insoluble in water and-organic solvents such as, chloroform, benzene, carbon tetra- chloride etc., but are soluble in methanol, ethanol and acetone. Molar conductances of the complexes in methanol and molecular weights of the soluble complexes in ethanol show them tb be 1 : 2 electrolytes. The loss of water at - 150°C from [ML2(H,0),] (Picrate), type of complexes (with change in colour) andat  - 110°C from the other hydrated complexes indicate th8t the wat er molecules are coordinated h he former complexes and are held in the lattice in others. ANALYTIOAL RESULTS, XOLAB CONDUOTAXCES, MOLEOULAB WEIGHTS, MELTING POINTS AND MAGNETIO MOMENTB OE THE COMPLEXES Complex Molar oonduc- tmce Colour Metal N,H, H,O m.p. at lb-JM p eff Mol.weight (%I (%I - (%I in HeOH (B.N.) in EtOH (") ((han.mb08, mole) - *) - [,&fn(BH), (H,O),] (Piorate), Yellow 7.37 7.70 40 70 120 196 6-12 '- (6.71) (7- 81) (4.39) [Fe(BH), (H,O),] (Picrate), Yellowish 7.70 7.12 4.52 116 21: 5.08 268.0 green (6- 82) (7.80) (4.39) (373- 3)  Yellow [Ni(BH),  (H,O),] (Piorate), Yellowish 7-09 .8.10 5.00 175 218 3.13 - grsen (7.17) (74 70) (4.37) [Cu(BH) J (Picrate), Green 7.86 17-83* 146 174 1-80 - ( 8.03) (17- 68) [Zn(BH), (HaO)J (Picrate), Yellow 7.40 7. 60 4.30 190 210 Diamag. 281d8 (7.84) (7.72) (4.34) (278.3) [Mn(BH),] (Piorate),. 2Ha0 Yellow 5-85 9.73 3.50 115 220 6.17 - (6- 76) (10.06) (3.77) [Co(BH) J (Picrate),.fl,O ' Dull-rdd 6-43 10.60 2.00 165 198 4-65 320.6 (6.27) (10.20) (1- 92) (313.3) [Ni(BH),fl(Picrate),. H& Yellowish 6.06 9.80 9-97 215 193 3- 07 - green (6.23) (10922) (9- 92) [Zn(BH)J (Piorate),. H,O Yellow 6.80 9.43 2.03 145 198 Diamag - (6.90) (10- 14) (1-901 [,@n(SH), (H,O)*] (Picrate), Yellow 6- 33 7.51 4- 40 135-40 216 6.13 - (6.46) (7.52) (4.23) [Fe(SH), (H,O)J (Picrate), Brown 6.95 7-05 4.15 130.32 204 5.60 279.4 (6.55) (7.27) (4.23) (284*0) [Co(SH), (H,O),] (picrate), Yellow 8-83 7.67 4.10 170-75 199 . 4.75 - (6.90) (7-48) (4.21) [Ni(SH),] (Piorate) a [Cu(SEI);J (Picrate), Yellowish 6.68 9-37 - 180 203 3.06 - (6- 04) (9- 88) green Green 7.67 7-  66 - 145 192 1.88 - (7.71) (7.76) [Zn(SH),] (Picrate), Yellow 6.81 9.44 - 140-46 200 Diamag. - (6.65) - (9.82) -- Caloulated values are given in'parentheses. Mol. wt. given in parenthesea are apparent values expected for 1 : 2 electrolytes. *Represente nitrogen analysis. ' AUU~RWAL & S m a ~  : Complexes of Firat Row Transition Metal Picrates - Compound Medium Bands (om-1) Assignments B a o v l  hvdrazine Ethanol 44400 (8136) x+* v - Selioylyl hydrazine Ethanol Nujol [Fe(BH), (li,O),I (Picrate), Ethanol 14600 (86), 6Tas-2"flg (D) 2W00 (16000), 27780 (28MH)). L 43000 (36600) Ethanol [OO(BH)~  (H,O)a] (Picrate), Ethanol 8930 (6.26) 26000 (16600), 27780 (24000) ' T q 4 T u  (PI 42600 (40600) [CO(AYH), (HsO),1 (Picrate), Ethanol 9000 (6:26), 19400 (31) 26000 (13600), 27780 (19600), 4Tllrt'T~~ ( F ) ,  ' T ~ Q  (PIL 32260 (17000), 42660 (37000) [Ni(BH),  (HsO)al (Picrate), - Acetone Ethanol [Ni(BH),] (Picrate) 1. HaO Acetone Ethanol [Ni(SH)J (Picra k) ,  Nujol [Cu(BH) J (Picrate) Nujol [CdSH)J  (Picrate), Nujol - I - valueb are given in parenthems. L= lntraligand transitions. BH( KBr) - 3285, 3110 - 1664 1612 886 - - - BB(CH C N )  + 3360 - 1672 1634 --. - - - [ d l n ( ~ & ) ,  (H,O),] ( P i ~ d e ) ~  3600m,3600m 33208,3250m 1653m 1640s 1610 912 - 3366m. 336Om 3200 490 340 [Fe(SH)# (H,O),] (Picrate), 3616,33408 %is, 3245 TCO~SHI. (H,0).1 (Picrate). 3466. 3386s 3310. 3266 DEP. SOI. J., VOL. 20, OOTOBEB 1976 Magnetic data of Table 1 show that Zn(II)  complexes are diamagnetic as expected for a dl0 electron configuration of the metal ion. The corrected magnetic moments of Mn(II) ,  Fe(II) ,  Co(I1) and N i ( I I )  complexes suggest an ~ctahedral arrangement of the ligands around the central metal ions 13. The magnetic moments of [Cu(BH)2] (Picrate), and [& (SH),] (Picrate), are close to those of Cec(II) square planar complexes14. Electronic Spectral Studies The U.V. spectrum of BH in ethanol gives a band at 44400 cm-1 (cm,,=8136) while that of SH in the same solvent yields two bands at 33000 and 41320 cm-l with ern,, values of 5000 and 7800 respectively. The nujol spectrum of 8H also yields two bands at 31750 and 41300 cm-1. The 44400and 41300 cm-1 bands of BH and SH respectively appear to be due to a -t a* transition of : C s O  group in resonance with benzene ring while the 33000 cm-l band of 8H may be attributed to the phenolic group 15 .  It may be point- ed out that the n + a* transitions expected fdr these compounds have not been observed presumably because of their occurrence in the same region as the more intense T + a* bandsla. The U.V. spectra of benzoyl hydrazine complexesin ethanol show two bands in 27780-28170 and 42550- 44050 cm-l regions and a shoulder around 25000 cm-l with ern,, values in the ranges 27000-31000, 35000- 46500 and 16000-21800 respectively. The position and intensity of these bands suggest that they may be assigned to a'+ a* transition and intramolecular charge-transfer transition of the bonding a-electrons of the phenolic group to a vacant energy level of the nitrogroups17. The 42550-44050 cm-1 band in the complexes is presumably due to the coupling of 41320-41665 cm-I band of the metal picrate8 and 44400 cm-I band of BH. As expected the intensity of this band increases on complex formation. Of the salicylyl hydrazine complexes studied in the ,present investigation, only Co(II)  a id  Pe(1I) com- plexes are suBciently soluble in common organic solvents to permit the recording of their solution spectra. The ethanolic solution spectra of Fe(I1) and Co(II)-SAY complexes in U.V. region yield three bands in 27780- 27930,32260-32250 and 42550 om-1 regions and a shoulder at 25000 cm-1 with c i a ,  values in the ranges 19650-23200, 16000-17000, 35200-37000 and 13503 respectively. As discussed above these bands may be assigned to intraligand transitions. - . The visible region spectrum of [Fe(BH),(H,O),] ( P i c ~ a t e ) ~  in ethanol shows one band at 14600 cm-1 (e,,,=85) which may be assigned to 5T2g+6Eg (D) transition in octahedral environment of the metal ion18 Thus the 10 Dq and LFSE values are 14600 cm-l and 16.64 kcal/mole respectively. The d-d transition band of [Fe (SH)2 (H20)2]  (Picrate), appears to have submerged under the high intensity intraligand band. The spectra of [Co(BH), (H20)2]   pic rate)^ and [CO(SH),(H,O)~] (Picrate), show a broad band a t  8930 and 9000 cm-1 respectively with the same amax value, 6.25. Co(II)-SH complex shows an additional band at 19400 cm-1 (em,,=31). The band found around 9000 cm-l is characteristic of octahedral cobalt (11) complexes and may be assigned to 4Tlg + 4T29 (F) transition. The broadening of this band suggests some tetragonal distortion in the above complexes7. Assignment of the second band in Co(II)-SH complex to 4T1,+4Tg (P) transition leads to 10 Dp. and B' values of 10120 and- 770 cm-1 respectively. The other ligand field para- meters for the complex are : /3=0.792, P0=20. 78%, LFSE-20.78 kcal/mole and A'= 114 cm-l. The value of the Racah parameter B' for the complex show a considerable amount of convalency in the metal-ligand bond which is also supported by the value of the effective spin-orbit coupling c~nstaht,  At (=63.3% of the free metal ion value). The two weakintensity bands occurring in the ranges 9400-10350 and 15400-16800 cm-1 in the spec- tra of nickel (11) complexes may be assigned to 3A2g+3T2q (F) ,  v1 and 3Tlq (F) ,  ve transitions respectively in Oh symmetry Is. The ratio of v2 and v l  for the complexes lie in the range 1.62-1.64, usually accepted for octahedral nickel (11) complexes20. The splitting of vl band in [Ni(BH& (H,O),] ( P i ~ r a l e ) ~ :  indi- cates a trans-octahedral geometry for the complex21. The values of the ligand field parameters calculated from and v2 values are given in Table 4. Aaaaawar, & SINGE : Complexes of First Row Transition Medetel Picrates TABLE 4 - LIUAND ?XI&LD P A W E T E R S  10B BH AND SH COMPLEXES OB NIOEEL (11) PIORATE - 10 Dq B' A' LFSE Complex ( ~ m - l )  (om-1) fi 8" va\vl (om-I) (kcall (%I , mole) - - [Ni(BH), (H,O),] (Picrate), 9400 900 0.852 14-77 1- 63 196 32-00 [Ni(BH) J (Picrate), flaO 9760 934 0-884 11.66 1-84 I 152 33-37 [Ni(SH)J (Picrate), 10360 912 0.863 13.63 1- 62 143 36-00 - . According to the average environment rule, the Dq value of [Ni(BH), (Haof,] (Picrate), should be 934 om-1 which is in excellant agreement with the observed value of 940 cm-I. The value of Dq and B' (Table 4) suggest a place between water and ammonia for the ligands with the following order of the ~~ectrochemical series : The electronic spectra of fCu(BH),] (Picrate), and [CU(SH)~] (Picrate)? show one band a t  16950 and 18350 cm-1 respectively which may be assigned to the envelope of 2Blp2Al, and 2Bl#BB transitions as reported for a number of square planar complexes19 of copper (11). r- Infrared Spectral Stzcdies The bands occurring in the ranges 3650-3350 and 3530-3465 cm-I in the spectra of the hydrated corn- p l e x ~  of BH and SH respectively which are absent in the anhydrous complexes may be assigned to ,,(OH) of the water molecules. The v(0H) oscurring at 3620-3540 cmil in SH in the acetonitfile mlution is shifted to 3600-3550 cm-1 in the spectra of its anhydrous metal complexes indicating that this group is not involvgd in bonding. The small negative shift appears to be due to intermolecular hydrogen bonding between phenolic glol~p of the ligand and the nitro group of the picrate ion and this seems to be the reason for-OH group not involving in coordination. The spectra of benzoyl hydrazine in KBr and acetonitrile solution have been discussed by Mashima22. BH shows only one band at 3350 om-l while SH shows two bands a t  333OS and 3 2 3 0 ~  cm-1 in the acetonitrile solution spectra assigned to v(NH) and these bands shift to 3320-3140 and 3310-3060 cm-1 in their respective complexes. A negative shift in v(NH) of 30-210 cm-1 in the BH com- plexes and 10.110 om-1 in the SH complexes indicate that -NH- and/or -NHa groups are involved in coordi- mtion. The spectrum of BH shows a band at 1672 cm-l assigned2a to v(C=O). Salicylyl hydrazine shows two bands at 1642 and 1630 cmyl in solid st& while in solution it gives only one band a t  1650 em-1. The bands at 1642 and 1630 cm-l may be assigned to v(C=O) and b(NHa) respectively. Because of the breakdown of the hydrogen bonding in solution, p(NH2) and v(C= 0 )  are expected to occur a t  higher fre- quency than in the solid state. The existence of broad band a t  1650 cm--1 in the solution spectrum of .SB may be due to the coupling of v(C=O) and p(NH2) modes. A strong band occurring at 1642-1625 and 1628-. 1616 cm-1 in the spectra of the metal complexes of BH and 4SH respectively may be assigned to P(C=O). A negative shift of 30-47 and 20-32 cm-1 in v(C=O) indicates coordination through the carbony1 0xyg;en. The bands occurring in the ranges 1600-1610 and 1600-1612 om-l in the BH and SH complexes respectively may be assigned to fl(NB,). A negative shift of 24-34 add 38-50 cm-I in this mode' indicates coordina- tion taking place through the primary amine nitrogen of the ligand. The v(N-N) band occurring a t  885 and 880 cm-1 in BH and .SH are shifted in 910-918 and 908-916 cm-l ranges respectively in their complexes. Thus the v(N-N) falls in the range reported for the complexes in which only one of the nitrogens of acyl hydrazines is involved in b0nding~s32~. The bands observed in the range 792-756 cm-l in [ML8(HaO)d(P&ate)a type of complexes which are absent in the anhydrous complexes may be assigned to pr(HzO) mode of the coordinated water molecule25. The non-ligand bands occurring in the ranges 492-425 and 366-312 om-1 re6iol)s may be assigned to ( M t O )  and (JfcN) vibrations DEF. SOI. J., VOL. 26, OOMBBR 1976 1. BOYE, W.0. & Dm-, R. N., J.  Am. pharm. Ass., Bci. Edn., W (1958), 286. 2. A m m w a ~ ,  R.C. & BAEADUR, A., Ind. J .  Chem., 7 (1969), 1038. 3. I s s ~ ,  R.M., SWY, E.L. & ISIUNPER, M.F., 2. Anorg. Allg. Chem., 354 (1967). 90. 4. I(aali~wAHA, M.8. & BHATTA~HARYA, A. K., J .  Znorg. Nuc~ .  Chem., 25 (1963), 361. c 6. D ~ T A  & D, A. & RAY CH~UDBBRY, N.  J.  Inorg. Nucl. Chem., 83 (i971). 189. 6. A L ~ o ~ K ,  J.F., BAKER, R. J. & DIAMANTIS, A. A., Awt. J .  Chem., 2 3 (1972), 289. 7. I s x m ~ m ,  M.F., ZAYAX, S.E., KHALIFA, M.A. & EL-SAYED, L., J .  Inorg. Nucl. Chem., 86 (1974), 36. 8. AWARWAL, R.C. & SINOH, N.K., Def. #So J., 25 (1976), 163. 9. CURTIUS, T. & S T R ~ ,  C. T., J .  Prakt. Ohem. (2), 50 (1894), 285. 10. BONDI, S., 2. Phyeiol Chem., 52 (1907), 170. 11. VOUEL, A.I., <A Text Book of Quantitative Inorganic Analysis' (Longmen Green & Co., London 3rd Ed.), 1961, p. 380. 12. LEVER, A.B.P., J .  Chem. Ed., 45 (1968), 711. 13. BIUUI~, B.N. & LEWIS, J., 'Modern Coordination Chemistry', Edited by Lewis, J. $ Wilkins, R.G. (Interscience Publiehers Ino., New York), 1960, p. 403. 14. Saooom, L. & C ~ ~ P O L I N I ,  M., J .  Chem. Soc., ( A )  (1964), 276. 15. Szitius~ov~oz, J. & GRIEU, M.E., J .  Xed. Pham. @hem., 4 (1961), 269. 16. J A E ~ ,  H.H. & O R O K ~ ,  M., 'Theory and AppIication of Ultaviolet Spectroscopy (John Wiley & Sons, New York), 1966, p. 265, 267. 17. 'YADA, H., TAN-, J. & NAGAKURA, S., Bull. Chem. Soc., Japan, 38 (1960), 1660. > 18. Durn, T.M., 'Modern Coordination Chemistry' Principles and Methods, Edited by Lewis, J. & Wilkins, -It.&t(1nbraeienoe Publishers, N.Y.) 1960, p. 291. 19. MANOH, W. & ~ERNIELIUS, W.C., J. Chem. Edn., 38 (1961), 192. 20. SAOOONI, L., Transition ,Metal Chem., 4 (l969), 199. 21. UHLIU, E., Coord. Chem. Rev., 10 (1973), 246. 22. m s ~ n u ,  M., Bull. Chem. Boc., Japrc. 85 (1962), 332. 23. &IOHOLIB, D., R O ~ E Y , ' M .  & SW&DE&S, R., J. Chem. Soc., A (1966), 960. 24. BRAIBA~I, A., ~ALLAVALLE,  F., PELLRPUHELLI, M.A. & LEOPOILBTI, E., Inorg. Chem., 7 (1968). 1430. 26. G a o ,  I., Bull. Chem. Soc., Japan, 84 (1961), 760, 765 & 1430. 26. N u o l r o ,  K., 'Infrared Spectra of Inorganic and Coordination Compounds' (Wiley-Inbrscienoe, N.Y.), 1970, p. 152, 187. 

Acyl Hydrazine Complexes of Some First Row Transition Metal II Picrates

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Acyl Hydrazine Complexes of Some First Row Transition Metal II Picrates

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