Indian Journal of Chemistry

Vol. 38A, March 1999, pp. 262-266

Preferential hexacoordination of cobalt(II) complexes with

heteroaroyl-hydrazones
M Sayaji Rao & K Hussain Reddy'

Department of Chemistry, Sri Kri shnadevaraya University, Anantapu r 515003, Indi a

Received 17 February 1998; revised /I December 1998

Coball(l!) complexes of benzoic acid [(furan-2-yl) methyl enejh ydrazide, benzoic acid [1-(furan-2-yl ) eth ylidenel hyd razide, ben-
zoic acid {(thiophen-2- yl)methylene hyd razide and benzoic acid [1-(thiophen-2-yl)-ethylidene] hydrazide have been synthesized and
characteri zed by elemental analysis, conductivi ty, mag netic susceptibility measurements, IR and electronic spectral data. Vari ous
liga nd field parameters have been calcu lated . Electronic spectral data and the magnetic moment values suggest an octahedral structure
fo r all cobalt(lI ) compl exes. This observation suggests liga nd independent structural features of cobalt complexes of aroylhydrazones.
The cyclic voltammetri c results suggest that BFEH has greater ability to stab ili ze cobalt(l ) oxidation state.

Metal complexes of aroylhydrazones have broad appli- Preparation of the ligands (BFMH, BFEH, BTMH and
cations ill biological processes such as ill th e treatment BTEH)
of tumourl.2, tuberculosis J , leprosl and mental di sor-
Hot aqueous solution of benzh ydraz ide (6.8 g, 0.05
ders. These are also known to act as herb icides\ insec-
. mol ) was added to a boiling so lution of carbon yl com-
ti cides 6 and acaricides 6 . The biological activity has been
pound (0 .05 mol ) in methano l (200 ml). The react ion
attributed 7 to the co mpl ex formin g abilities of ligands
mixture was boiled under reflux for I h. A pale ye ll ow
with th e metal ions present in th e cell s. The prese nt
co loured crystalline product was formed on cooling the
interest in the coordination chemi stry of aroylhydrazones
reaction mixture. This was coll ected by filtration,
stems from their li gational behaviourR. These li ga nds
washed several times with hot water and dried ill vaclfo.
can act both as neutral and mononegative ligands and
These li gands were recrystallized from methan ol.
favour certain geo metri es 9 to the co mplexes .
Preparation of complexes
In view of th e grow ing importance of aroylhydrazone
and in co ntinu ati on of our studi es on cobalt co m- The complexes were prepared by reactin g hot aq ue-
plexes lO . 12 to mimi c th e chemical , structural and elec- ous soluti on of CoC I2 .6H 20 and liga nds in th e mol ar
troc hemi cal properti es of vitami n B 12 and its deri vat ives, ratio of I :2. To th e boiling so luti on of li ga nd s (0.01
we have investi gated co balt comp lexes of heterocyclic mol) in methan ol ( 100 ml ), was added CoC I ~. 6H, 0 (0.05
ar oy lh ydrazones viz., ben zo ic ac id [(furan -2- mol ) disso lved in minimum quantity of water and heated
yl)methylene-hydrazide (I, BFMH), benzoi c acid [I -(fu- under reflu x for 2-6 h. Crystal Iine co mplexes whi ch sepa-
ran-2-y l)ethylidene] hydrazide (II, BFEH), benzo ic acid rated out were collected by filtrati on, washed with hot
[(thi op hen-2-yl)methylene hyd raz ide (III, BFMH) and water, small quantity of methanol and hexane an d dried
benzo ic acid ( l-thi ophen-2-y l)eth ylidene]hydraz icl e (IV. ill vacuo . The analy ti cal data of the ligands and their
BTH-l). co mpl exes are presented in Tab le I.
Materials and Methods The element al analyses were perfo rmed at RSIC,
Reagent grad e furfurald ehyde, 2-furylllleth ylketo ne, CDR I, Luckn ow. Magneti c measurements were carri ed
ou t in the polycrystallin e state on a PAR model ISS vi-
thi ophene-2-carboxaldehy de, 2-acety l-thiophene and
brating sample magnetometer ope rat ing at a fi eld strength
benzh ydraz ide were purchased from M is Fluka '.IIld were
of 2 KG to 8 KG. The molar co nductance of the com-
used as received. The so lvents used for the synt hes is of
plexes in DMF ( I O-J M ) soluti on were meas ured at 27 ±
li ga nd s and th eir cobal t(l l) compl exes we re di still ed
2"C with Systroni c Model 3m direc t readin g condu cti v-
before use. All oth er chemicals were of reage nt grade
ity bridge. The electroni c spectra in nuj ol were reco rd ed
qu ality and were used without furth er purification.
 RAO el af.: HEXACOORDINATION OF COBALT(II) COMPLEXES 263

Table I - Analytical data and selected IR spectral bands of ligands and their cobalt complexes

Compound Colour Found (Caled) % IR spectral bands (em·')

M.P. (0C)' C H N v(N-H) v(C=O) v(C=N) v(N-N)

BFMH Light Yellow 67.4 4.6 13.2 3246(m) I 665(m) I 642(m) 1013(m)

151-152 (67.3) (4.6) (13.1 )

[Co(BFMH)2CI 21 Reddish brown 50.0 4.3 10.8 3251(m) I 643(s) 1622(s) 1029(m)
>250 (60.8) (4.3) (10.9)

BFEH Dark brown 67.8 5.4 12.5 3229(m) 1660(s) 1630(m) 1020(5)
143-145 (68.4) (5.3) (12 .3)

[Co(BFEhl Red 59.9 4.5 10.8 1625(5) 1029(m)

171-173 (60.8) (4.3) (10.9)

BTMH Dark yellow 63 .3 4.1 12.2 3254(m) 1660(5) 1638(5) 998(m)

192-194 (62.6) (4.3) (12.2)

[Co(BTMH)2CI21 Red 49.4 4.3 9.8 3256(m) 1640(5) 1616(s) 1015(m)

>250 (48.8) (4.4) (10.3)

BTEH Yellow 64.5 4.8 11.5 3329(m) 1650(5) 1638(5) 1023(m)

197-199 (63.9) (4.9) (11.4)

[Co(BTEhl Reddish brown 56.7 4.3 9.8 1629(s) 1028(m)

179- 181 (57.2) (4.4) (10.2)

*Comp1exe5 decompose in the range indicated

with Cary Model 2390 spectrophotometer. The infrared BTEH in CDCI 3 show low field signals respectively at
spectra were recorded in the range 4000- I 80 cm·' with a 11 .23,11.35,9.07,8 .91 ppm forthe imino proton present
Perkin-Elmer 983 G spectrophotometer. The' H NMR in ligands. In the spectra of BFMH and BTMH, CH=N
spectra were recorded on a Varian XL-300 MHz high peak is observed respectively at 8.60 and 8.80 ppm. Sig-
resolution instrument in CDCI) so lvent. The mass spec- nals due to aromatic protons occurs as multiplets be-
tra were recorded using Fan ning Mat 8230 mass spec- tween 86.4 - 7.4 ppm. The resonance signal due to -
trophotometer. The cyclic vo ltammetry was performed CH 3 protons present in BFEH and BTEH occur at 2.38
with a BAS model CV-27 controller and a conventional and 2.30 ppm respectively.
three electrode configuration with glassy carbon work-
ing electrode, silver/si lver chloride reference e lectrode The mass spectra of BFMH, BFEH, BTMH and
and platinum counter electrode. Nitrogen was used as a BTEH show molecular ion peaks. The important peaks
purge gas and all solutions were prepared using 0. 1 M observed in the mass spectra of these li gands are m/e 67,
tetrabutylammonium perchlorate (TBAP) supporting 77, 105, 125, 139 and 161 respectively corresponding to
electrolyte. C 4 H )O, C 6 H s ' C 6 H s CO, C 4 H 3 0(CH 3 )C : N-NH 2'
(BFEH), C4 H)S(CH))-C : N-NH2 (BTEH); C 6HsCONH ;
Results and Discussion N-C-CH) (BTEH).
The analytical and IR data for all the ligands and All the complexes are crystalline solids, stable at room
their cobalt(II) complexes are summarized in Table 1. temperature, non-hygroscopic, soluble in chloroform,
The 'H NMR spectra of BFMH, BFFH, BTMH and DMF and DMSO, but insoluble in water, methanol and
264 iNDIAN J CHEM, SEC. A, MARCH 1999

Table 2 - Elec'ronic spectral data and ligand field parameters of cobalt complexes

Complex Method of v1 v2 v3 8 ova 8 35 b 10Dq v2 -v 1 v!v 1 LFSE

evaluation K-cal.
mole-I
[Co(BFMH)2 Ci 2J Observed 14705 18180
A 6692 143 52 17487 785 - 693 0.8 1 7668 7660 2.144 21.88
B Fitted! 14361 17488 815 ±692 0.84 7429 7669 2.146
C Fitted 14632 18045 854 - 135 0.88 8013 7940 2.186

[Co(BFE)2J Observed 15040 17543

A 6924 1483 1 17127 745 - 416 0.77 7904 7907 2.142 22.60
B Fitted 14002 17174 774 -1038 0.797 7480 7078 2.022
C Fitted 15218 17894 787 ± 351 0.8 10 81 16 8294 2. 197

[Co(BTMH)2 Ci 2J Observed 15387 17390

A 7185 15382 17384 746 - 16 0.768 8189 8197 2.140 23.42
B Fitted 15344 17355 745 - 45 0.767 8170 8159 2.135
C Fitted 15402 17424 748 ± 45 0.770 8202 8217 2. 143

[Co[BTE)2J Observed 15625 17240

A 7249 15480 16950 712 - 290 0.733 8230 8231 2. 130 23.51
B Fitted 14892 16975 732 - 733 0.753 7938 7643 2.054
C Fitted 14295 17476 241 ±1330 0.763 8376 7046 1.971

a Difference between observed and calculated value

b Ratio of free ion and the complex

~C /R fIl
~S~C
/ R

N
II IIN
""--NH ~NH

I I
50)J A
O=C'@ \
O=C

1_ R = H BFM H
"©
111_ R= H BTMH
II. R=CH3BFEH =
. IV _ R CH 3 BTEH

ethanol. The molar conductivities of -10- 3 M solution

of the complex in DMF were found in the range
n-
8-15 I cm- 2 mol -I indicating their non -e lectrolytic na-
ture l3 . The analytical data support the 1:2 (metal :ligand)
composition of the comp lexes . The magnetic moments
of cobalt(II) complexes of BFMH, BFEH, BTMH and
BTEH are respectively found to be 4.5, 4.0,4.3 and 4.5
BM suggesting a high spin octahedral geometry with a
0-7 0·9 1.1 1.3 1-5 1.7
very high orbital contribution attributable to the three-
- E/V
fold degeneracy of the 4T? (F) ground state term I4.15 .
-g
The electronic spectra of complexes were recorde d in
Fig. I - Cycli c voltammogram of [Co(BFMH)zJ in DMF in 0.1
M [TBAP] vs Ag/AgCl reference eleclfode (Scan rate DMF. Two distinct bands in the range 14705-15625 and
100 mY s-I ) , " 17242-18180 cm- I were observed in the electronic spec-
 RAO e/ al. : HEXACOORDIN ATION OF COBALT(II ) CO MPLEXES 265

Tab le 3 - Cyclic voltammetric data of cobalt co mpl exes in DMF co nt ainin g 0.1 M TB A I at glassy carbon electrode, temp. 25°C

Complex Cobalt 6.E (mY )

redox
co uple
Co(II )- BFMH 111/1/ -0.65
JIll -1 .435 -1.350 -1.39 85
Co(II)-BFEH 11//1/ -0.54
JIll -1 .54 - 1.47 -1.50 70
Co(II)-BTMH 111111 -0.73
JIll -1. 24
Co(lI)-BTEH I11111 -0 .62

1/11 -1 .36

Cobalt complexes of BFMH and BTMH

tra of cobalt complexes (Table 2) attributable to th e
4T lg(F) ~ 4A 2g(F) (V 2 ) and 4T l g(F) .~ 4A Ig (P)(v 3 ) The presence of v(N-H) in the spectra of these co m-
tran sition respectively in an octahedral fi eld . Important plexes suggest that FABH and TABH re main protonated
li gand field parameters are presented in Tabl e 2. The in chelation. The amide I and amide II bands shi ft to
calculated values for Dq. B and B,,; li e in the same range lower frequencies in the spectra of these complexes. A
as that reported for octahedral cobalt(II) complexes. The strong band observed in the spectra o f these li ga nds at
va lue of v I is calculated theoretica Il y l5,16 by u sin g th e 1640 cm, l is shifted to lower wave numbe r suggest ing
equation, VI = 5 Dq - 7.5 B + 1/2 (225 B2 + 100 Dq2 the participation of azomethine nitrogen in coOt'dina-
+ 180 Dq) I/2 . tion 21 On the other hand v (M-N) band is shifted to
The values of 10 Dq and Racah paramete rs of the higher frequ e nc ies 22 in the spec tra of both comp lex es
complexes were calculated u sing the observed v 2 and V3 supporting th e coordination of azo methin e nitroge n
values. The rati o of v? observed to v I calculated is found atom. Simila rl y, the hi g hest frequency ba nd observed
to be in the range 1.97-2.19 as required for octahedral due to v(C=O) is shifted to lowe r wave numbe r sug-
coba lt(IT) co mpl exes l7. C o balt complexes with BFEH gest in g the parti c ipation of carbo ny l oxygen in coordi-
and BTEH have hi g h 10 Dq valu es presumably due to nation. Th e non-li gand bands occurrin g in the region
the high stability fac ilitated by hi g h denticity of these 500-585 ; 475-490 and 260-295 cm,l are tentati ve ly as-
li gand s. s ig ned to v(M -O ), v (M-N) and v (M-CI ) vibrat io na l
Some important bands observed (Tabl e I) in the in- modes respective ly23,
frared spectra of BFMH, BFEH and BTE H , and the ir
co mplex es are considered for the ide ntifi cation o f don or Cobalt complexes of BFEH and BTEH
sites of the li gand s. The IR spectra of free li gand s ex-
hibit v(N-H) absorbance band s at c([.3250 and v (C=N) B and s due to v (N-H ) and v(C=O) stretc hin g vibra-
band s ca. 1640 c m- I indicating th at the li gands ex ist in tion s are no t observed in the IR spectra of these co m-
keto form in the so lid state. However, in so luti on, the plexes. In stead, they show new bands charac teri st ic 24
li gands probably ex ist in equilibrium with tauto meric o f v (NCO) in the spec tra o f these complexes. Th e ap-
enol form . By the loss of proton, the enoli c form may pea rance of ~ (NCO) stre tc hing vibrat ion in the spect ra
act as a unin egat ive li gand . The band s appearin g in th e of these cobalt co mpl exes suggests th e presence of
spectra of li gand s - 1660, 1640, 1535, 1015 cm, l are >C=N-N=C< res idues of the stoic hi ometry and th e de-
attributed 18 to amide I [v(C=O)] , v(C=N), amide U [~ ( N­ structi on of keto group presumabl y via enoli sati o n and
H ) + (C-N)] modes respecti ve ly. Th e two strong band s bondin g of the li gand throug h the res ultin g e nolate oxy-
o bserved at 7 10-690 and 610-605 cm,l reg ions 19.20 are gen. The red s hift of the rin g de formation vibrations in
due to furan/thi oph e ne rin g de formation modes. the IR spectra of these comp lexes suggest th e parti c ipa-
 266 INDIAN J CHEM , SEC. A, MARCH 1999

Based on molar conductance, magnetic and spectral

data, octahedral structure (V, VI) is suggested for the
complexes. Our results suggest th at cobalt(lI) complexes
prefers to exist as octahedral structure irrespecti ve of
substitution and denticity of aroylhydrazones probabl y
to mimic the naturally occurring biomo lecul e viz. vita-
min B 12 •

Acknowledgement

We are thankful to the DST, New Delhi (Grant NO.SPI

S I IF-07/92), for financial support.
v References
I Mesubi M, Adediran D & Ugo B, Synth React inorg IIwt -org
Cltem, 23 (1993) 435.
2 Mohan M, Kumar A, Kumar M & Jha N K, II/org chilli acta.
136 ( 1987) 65.
3 Ma T S & Tei n T M, Antibodies GI/d Chelll othemp.". 3 ( 1953)
491.
4 Bau-Hri . N P, Xuong M D, Binon F & Roger F, J chell/ Soc
( 1953) 1358.
5 Moon M W, Friedman A R & Sieinhard A, J Agr Food ClWIII ,
20 ( 1972) 11 87 and Cltem Abstr 105 ( 1986) 78839 .
6 Moon M W, Geomrich E G & Kauga rs G, J Ag r Food Chem,
20 ( 1972) 888.
7 Srivaslava R S, II/ org Chilll Acta , 56 (198 1) 65 and references
Iherein .
8 Dulla K L & Hussa in M M,.I sciel/tll/d Res, 44 ( 1985 ) 635.
9 Say,~ i Rao & Hussain Reddy, II/ dial/ J ChcIII , 35A ( 1996) 68 1.
X=O or S 10 Radhakrishna Reddy M, Mohana R ,~u K & Hu ssain Reddy K,
VI Indial/ J Chelll , 35A ( 1996) 677.
II Hussain Redd y K, Radhakrishna Reddy M & Mohan3 Raju K,
ti on of furan oxygen and thi ophene sulphur in complex Polyhedrol/ , 16 ( 1997) 2679.
formation. The bands observed in the 500-585 and 475- 12 Radhakrishna Reddy M, Hu ssai n Rcdd y K & Mohan 3 Rajll K,
490 e m-I reg ions which are absent in th e spect ra of Polyhedrol/ , 17 ( 1998) 1355. _
13 Geary M J, Coo rd chem Rev, 7 (1971 ) XI.
li gands may tentatively be assigned to v(M-O) and v(M- 14 COllon F A & Wilkinson G, Adl'al/ ced iI/organic cile//lis/l)'
N) modes respectively. (Jo hn Wiley, New York) 1988.
15 Singh M, Syl/tfl React inO/'R met org Chem, 16 ( 1986) 915.
The cyclic voltammetri cs result s of compl exes are 16 Figgis B M, IlIIrodllction to ligal/d fields (Intersciencc, ew
summari zed in Table 3. Typica l cyc li c vo ltam mog ram York) 1960.
17 Lever A B P & Odgen P, J chelll Soc A, ( 1967) 204.
of coba lt complex of BFMH IS g iv e n In
18 Rastogi D K & Sharma K C, J il/org lWei Cho l/ , 36 ( 1974)
F ig. I. The reduction of cobalt(H) to cobalt(l) depend s 2222.
on the ab ility of equatorial ligand to stabilize the cobalt(l) 19 Co lthup N B, Dal y L H & Wiberly S B, II/ frod llctiol/ to iI/Fa-
ox idation state 25 . The cobalt complexes o f BFMH and red and Ra//lal/ spectroscol')' (A cademic Press, New York )
1964, p. 237.
BFEH are reduced from cobalt(II) to coba lt(l) at EII2
20 Ibrahim K M, Bill! Soc chilli F,:, 28 ( 1991) 327.
va lues of -1 .39 and 1.50 V vs Ag-AgCI. These results 21 Agarwal K C & Nagang K K.II/ org chilli ACla, I (1973) 65 .
indi cate that the B FEH has greater ability to stabili ze 22 Roastzur M, Specfmchim Acta , 19 ( 1963) 1107 .
Co(!) oxidati on state. The EII2 va lues of present com- 23 Nakamoto K, II/Fared al/d Ra//lal/ speClra 0/ inorgclllic and
plexes for Co(lII) ~ Co(II) and Co (II) ~ Co(!) are com- coordination cOIllPounds. 3rd Edn (Wiley, New York). 1978.
24 Singh N K & Tripathi R. Trans Met Che//l . i 3 ( 1988) 346.
parable to those cobinamides 26 . The absence of counter
2S Costa G. PlIxeddu A & Tauzer G, In olS nucl che//l Le/{, 4,
oxidati on wave for Co(II) ~ Co(IlI) may be understood (1968) 319.
in term s of increas in g difficulty to oxidize Co(H) in th e 26 Lippard S J (ed), Current research topics in iJlOillorganic che//l -
form of co mplex and in non-aqu eous conditions. istl )' (John Wiley. New York ) 1973 , p 196.