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PREPARATION AND CHARACTERISATION OF SOME
TRANSITION METAL COMPLEXES OF NEW 4-[(5-ETHYL-1,3,4-OXADIAZOL-2-YL)SULFANYL]ANILINE
Bassam Abdulhussein Hasan Alsafee *
*Department of Pharmaceutical Chemistry, College of pharmacy, Thi-qar University
1. I NTRODUCTION
1,3,4-Oxadiazole is a heterocyclic olec!le with oxy"e# ato at 1 a#d two #itro"e# atos at 3 a#d 4 $ositio#. They ha%e
&ee# '#ow# (or a&o!t )* years, it is o#ly i# the last decade that i#%esti"atio#s i# this (ield ha%e &ee# i#te#si(ied. This is
&eca!se o( lar"e #!&er o( a$$licatio#s o( 1,3,4-oxadiazoles i# the ost di%erse areas.
It also co#tai#s &road ra#"e o( thera$e!tic acti%ity Oxadiazoles &elo#" to a# i$orta#t "ro!$ o( heterocyclic co$o!#ds
ha%i#" +NC-O- li#'a"e 1. 1,3,4-Oxadiazole /10 is therally sta&le aroatic heterocyclic a#d exists i# two $artially red!ced
(or /02,3,-dihydro 1,3,4-Oxadiazole a#d/30 ,-dihydro-1,3,4-Oxadiazole de$e#di#" o# the $ositio# o( the do!&le &o#d
.the co$letely red!ced (ro o( 1,3,4-Oxadiazole is desi"#ated as ,3,,4,-tetrahydro-1,3,4-Oxadiazole/40 .
D!e to the i#teresti#" acti%ity o( , -dis!&stit!ted 1,3, 4-oxadiazole as &iolo"ical a"e#ts co#sidera&le atte#tio# has &ee#
(oc!sed o# this class. The $harace!tical i$orta#ce o( these co$o!#ds lies i# the (act that they ca# &e e((ecti%ely !tilizi#"
as a#ti&acterial, a#ti- t!&erc!lar a#d i#secticidal a"e#ts .5oe o( these co$o!#ds ha%e also a#al"esic, a#ti-i#(laatory,
a#tica#cer, a#ti-6I7 a"e#t , a#ti- 8ar'i#so#is a#d a#ti-$roli(erati%e a"e#t. I# additio#, 1,3,4-oxadiazole ha%e $layed a cr!-
cial $art i# the de%elo$e#t o( theory i# heterocyclic cheistry a#d also !sed exte#si%ely i# or"a#ic sy#thesis 3 .
Abstract
1,3,4-oxadiazoles are i$orta#t &eca!se o( its %ersatile &iolo"ical actio#s s!ch as a#tiicro&ial , a#ti-
alarial , a#tico#%!lsa#t , hy$o"lyceic, also a#al"esic, a#ti-i#(laatory, a#tica#cer, a#ti-6I7 a"e#t
.I# the $rese#t st!dy The solid co$lexes o( 9e/II0, Cr/III0, Co/II0, Ni/II0, a#d C!/II00 with 5y#thesis o( 4-/-
ethyl-1,3,4-oxadiazol--yl0s!l(a#yla#ili#e ha%e &ee# sy#thesized a#d characterized &y !si#" the s$ec-trosco$ic IR,16N:R, :ass as well as &y elee#tal a#alyses C,6,N a#d :olar co#d!cta#cethey were
st!died . It ay &e co#cl!ded that the li"a#ds coordi#ate thro!"h Nitro"e# a#d 5!l(!r as atos show#
i# 5chee /0. 9or all the co$lexes. The li"a#d acts as a dide#tate li"a#d coordi#ati#" thro!"h the
oxadiazole #itro"e# a#d the 5!l(!r ato o( -s!l(a#yl. This %iew is (!rther s!$$orted &y the a$$eara#ce
o( a &a#d corres$o#di#" to the etal+#itro"e# a#d the etal+5!l(!r stretchi#" %i&ratio# at *3+3
c+1 a#d 4;4-4)4 c+1 i# the co$lexes. The $hysicocheical data s!""est the octahedral "eoetry
(or all co$lexes exce$t (or Ni a#d Ca co$lexes which where tetrahedral res$ecti%ely.
KEYWORDS: PREPARATO!" #HARA#TERSATO!" TRA!STO!" $ETA%" S&%'A!Y%"
O
N N
O
N N
H
O
N N
O
N
H
N
H
1 2 3 4
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ass is th!s se$arated o!t was dried a#d recrystallized (ro etha#ol.The $!rity o( the co$o!#d was (ollowed &y T=C
.Hield ;4.) J, . $. 13;-13KC .K
4. 8R8>R>TION O9 CO:8=E5
The hydrated etal chloridesalts o( The 9e/III0, Cr/III0, Co/III0, Ni/II0 a#d C!/II0/*.*1 ol0 was added to sol!tio# o( the li"a#d
.1" /*.*1ol0 i# hot a&sol!te etha#ol /4* =0 a#d the ixt!re was re(l!xed o# a water &ath (or ho!rs a#d the sol%e#t
was e%a$orated i# %ac!! to hal( o( the ori"i#al %ol!e a#d the# cooled . The isolated co$lexes were (iltered o(( , washed
se%eral ties with etha#ol a#d (i#allydried i# air 1* .
. 8RCNT FORB
.1 8R8>R>TION O9 =IND
. 8R8>R>TION O9 CO:8=E5
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. R5U=T5 >ND DI5CU55ION
The $!rity o( the li"a#d a#d its co$lexes were chec'ed &y T=C. :olec!lar (or!la, $hysical $ro$erties a#d :olec!larwei"ht a#d olar co#d!cta#ce data o( the li"a#d a#d its co$lexes ta&!lated i# ta&le /10 a#d /0 .
elee#tal a#alysis ,I#(ra-Red 5$ectrosco$y as show# i# a (i"!re /1,,30 ta&!lated i# ta&le /30 a#d /40.The s$ectral data o( 16-
N:R 5$ectra (or the (ree li"a#d re$orted i# (i"!re /40 whileThe :ass 5$ectra show# i# a (i"!re /,,;,),K,1*0 a#d ta&!lated
i# Ta&le/0. The calc!lated %al!es were i# a "ood a"reee#t with the ex$erie#tal %al!es.
Ta&le 1. :olec!lar (or!la, $hysical $ro$erties a#d :olec!lar wei"ht data o( the li"a#d a#d its co$lexes.
NO 9or!la :.Ft Color :.8 C Hield J
= C1*611N3O5 1 @row#ish yellow 13;-13K ;4.)
1 9e/=0ClCl *4 @row# 1;*-1) )3.3
Cr/=0ClCl ** 8ale @row# 13-1 )K.1
3 Co/=0ClCl *;
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.1 IN9R>-RD 58CTRO5CO8H
The 9TIR s$ectr! (or = shows a characteristic stretchi#" a&sor$tio# &a#ds . 33**c-1, 3*c-1, K43 c-1, 1)1 c-1,141K c-1, 131 c-1 assi"#ed to M N-6 "ro!$ ,M C-6 >roatic C-6 >li$hatic ,CN o( the oxadiazole ri#", syetrical C-O-
C, asyetrical C-O-C stretchi#" res$ecti%ely. The CN stretchi#" %i&ratio#s are i$orta#t to $redict the &o#di#" ode o(
the li"a#d ,these &a#ds shi(t lower wa%ele#"th i# the s$ectra o( co$lexes co$are with li"a#d, o&ser%ed cha#"es are the
e%ide#ces o( co$lexio# had ha$$e#ed 11. The IR data o( the co$lexes are show# i# Ta&le /40 a#d (i"!res /1,,30. The
Ta&le lists the stretchi#" (reG!e#cy /M0 (or soe o( the characteristics "ro!$s exhi&ited &y the li"a#d a#d co$lexes.
. 16-N:R 58CTR>
The s$ectral data (or the (ree li"a#d i# D:5O-sol!tio# was re$orted alo#" with the $ossi&le assi"#e#ts i# ex$erie#tal.
The $roto# #!clear a"#etic reso#a#ce s$ectral data "a%e additio#al s!$$ort (or the co$ositio# o( the li"a#d, >ll the
$roto#s are at their ex$ected re"io#. The >r-6, N6a#d C63, C6-CN $roto# si"#als, are show# i# the re"io#s o( ;.-).*,.3,
1.3,.) a#d $$, res$ecti%ely, The #!&er o( $roto#s calc!lated (ro i#te"ratio# c!r%es a#d the recorded cheical shi(ts
i# (i"!re /401 .
.3 :>55 58CTR>
The ass s$ectr! o( the li"a#d shows a olec!lar io# $ea' :e at 1,the li"a#d s$ectra shows (ra"e#t io# $ea' at
e /*,1K,1,14,K;,K,;; a#d d!e to C1*6KNO5A.
C)6N3O5A./C;6NO5
A./C6N5A./C46NO
A./C6NA./C6
A./C6A. / res$ecti%ely as show# i# 9i"!re/0 . The ass
s$ectr! o( the co$lex 9e/=0.ClCl shows a olec!lar io# $ea' at z *4 which is eG!i%ale#t to olec!lar ass o( the
co$lex. This co$lex shows a#other a (ra"e#t io# $ea' with loss o( chlori#e ato at z K. the l i"a#d s$ectra shows
(ra"e#t io# $ea' with loss two chlori#e ato at e /33,4K)0 d!e to 9e/=0ClA.a#d9e/=0
A.Res$ecti%ely as show# i#
9i"!re/0.
The ass s$ectr! o( the co$lex Cr/=0.ClCl shows a olec!lar io# $ea' at z ** which is eG!i%ale#t to olec!lar
ass o( the co$lex. This co$lex shows a#other a (ra"e#t io# $ea' with loss o( chlori#e ato at z . The li"a#ds$ectra shows (ra"e#t io# $ea' with loss two chlori#e ato at z /3*,4K40 d!e toCr/=0 ClA.>#d Cr/=0
A.Res$ecti%ely
as show# i# 9i"!re /;0.The ass s$ectr! o( the co$lex Co/=0.ClCl shows a olec!lar io# $ea' at z *; which is
eG!i%ale#t to olec!lar ass o( the co$lex. This co$lex shows a#other a (ra"e#t io# $ea' with loss o( chlori#e ato
at z ;. the li"a#d s$ectra shows (ra"e#t io# $ea' with loss two chlori#e ato at z /3,*10 d!e toCo/=0ClA.a#d
Co/=0A.Res$ecti%ely as show# i# 9i"!re/)0. The ass s$ectr! o( the co$lex Ni/=0Cl
A.shows a olec!lar io# $ea' at
z 3* , This co$lex shows a#other a (ra"e#t io# $ea' with loss two chlori#e ato at z 31,;K d!e to Ni/=0ClA. ,
Ni/=0A. Res$ecti%ely as show# i# 9i"!re /K0.
The ass s$ectr! o( the co$lex C!/=0ClA.shows a olec!lar io# $ea' at z 3 , This co$lex shows a#other a (ra"-
e#t io# $ea' with loss two chlori#e ato at z 3*,)4 d!e to C!/=0ClA., C!/=0A.res$ecti%ely as show# i# 9i"!re /1*0.
;. CONC=U5ION5
I# the $rese#t wor', a series o( 9e/III0, Cr/III0, Co/III0, Ni/II0, C!/II0 co$lexes with #ew li"a#d /=0,ha%e &ee# $re$ared a#dcharacterized o# the &asis o(IR,16N:R, :ass s$ectrosco$icas well as &y elee#tal a#alyses C,6,N a#d :olar co#d!cta#ce.
>ccordi#" to all the a#d $hysiocheical eas!ree#ts as the $re$ared co$lexes, we ca# s!""ested the cheical co#(i"-
!ratio# (or the co$lexes. The li"a#d /4-/-ethyl-1,3,4-oxadiazol--yl0s!l(a#yla#ili#e0 was s!ccess(!lly sy#thesized as
show# i# the schee /10. The li"a#d was treated to di((ere#t tra#sitio# etal salt to (or the corres$o#di#" co$lexes as
show# i# the schee /0. It ay &e co#cl!ded that the li"a#d coordi#ate thro!"h Nitro"e# a#d 5!l(!r atos .This %iew is
(!rther s!$$orted &y the a$$eara#ce o( a &a#d corres$o#di#" to the etal+#itro"e# a#d the etal+5!l(!r stretchi#" 7i-
&ratio# at *3+3 c+1,4;4-4)4 c+1 res$ecti%ely i# the co$lexes . /Cr/III0,9e/III0a#d Co/III0 leadi#" to the (oratio#
Octahedral "eoetry co$lexes .while the C! a#d Ni atos leadi#" to the (oratio# tetrahedral "eoetry co$lexes.
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R9RNC5
1. DR. ?IRIH> , DR. D6>IRH> @6>7>5>R 2 Oxadiazole Core as a lo' 8a#dey, T.5i%a'!ar, R.Raja%el, Ra%i#dra Dhar D!&ey 2 5y#thesis o( soe No%el , -
Dis!&stit!ted 1, 3, 4-Oxadiazole a#d its >#al"esic, >#ti-I#(laatory, >#ti-@acterial a#d >#ti-T!&erc!lar >cti%ity 2
I#ter#atio#al ?o!r#al o( CheTech Research 2 7ol., No.3, $$ 13K;-1412 ?!ly-5e$t *1*.
4. cti%e 6eterocycles 5y#thesis, Characterizatio# a#d >#tiicro&ial >cti%ity
o( 5oe ,-Dis!&stit!ted-1,3,4-Oxadiazoles2 Dha'a U#i%. ?. 8har. 5ci2 /0$$ K2 **; /Dece&er0.
. :aho!d Naji >l-?i&ori2 5i#a# :idhat>l-@ayatia#d >#aa :ajeed Rasheed2 Coordi#atio# :odes o( a New =i"-
a#d Deri%ed (ro 8yrazoli#e with Cr/III0, :#/II0, Co/II0, Ni/II0, C!/II0 a#d #/II0 :etal Io#s25y#thesis, Ide#ti(icatio#
a#d @iolo"ical 5t!dies2 Cheistry a#d :aterials Research2 7ol.3 No.1, $$ 12 *13.
. 5.B. I&rahe, 9.:. a&d!l+6aeed a#d :.9. >lias2 8R8>R>TION, C6>R>CTRI5>TION >ND @IO=O= >CTI7I-
TI5 O9 5O: :T>= CO:8=E5 O9 NF N 4-@I/-T6ION-1,3,4-OE>DI>O=-H=0:T6>N0:TH= DI@UTH=
>:IN >ND T6ORTIC>= 5TUDH 2 ?o!r#al o( >l-Nahrai# U#i%ersity 2 7ol.11/02$ 4-32 >!"!st, **).
;. B.:. Dao!d, >.F. >l-O&aydi, :.?. :ohaed2 5y#thesis a#d >#ti&acterial >cti%ity o( soe 6drazides, 5!&stit!ted
Thioseicar&azide, 1,3,4-Oxadiazoles, Thiadiazoles a#d 1,,4-Triazoles 2 Natio#al ?o!r#al o( Cheistry2 7ol!e
31,$$ 312**) .
). 5hashi'a#t R 8atta# , 8 > Ra&ara , ?ayashri 5 8atta#2 25y#thesis a#d e%al!atio# a#d e%al!atio# o( soe #o%el s!&-
stit!ted 1,3,4 Oxadiazole a#d $yrazole deri%ati%es (or a#tit!&erc!lar acti%ity 2 I#dia# ?o!r#al o( cheistry . 7ol. 13
No./10 2 $$ 143 2 Octo&er **K.
K. 8ala' B. 8ari'hP, 6ire# :. :ar%a#iya a#d 8ro(. Dr. Dhr!&o?yoti5e# 5HNT65I5 >ND @IO=O= 7>=U>TION O9
1,3,4-OE>DI>O= DRI7>TI75 >5 8OTNTI>= >NTI@>CTRI>= >ND >NTI9UN= >
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>88ND>
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9i"!re /0 IR s$ectr! o( the 9e/=0ClCl c-1
9i"!re /30 IR s$ectr! o( the C!/=0Cl c-1
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9i"!re /4 0 N:R s$ectra o( the li"a#d
Table ," The mass s(ectrum f li8and and its cm(le2es
n 5tr!ct!re :olec!lar Io#
% 1
4#.H;!3OS7H9!3OS7
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4#9H,7
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4#5%63#l37#l *;
4#5%63#l37
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9i"!re /0 ass s$ectra o( li"a#d
9i"!re /0 ass s$ectra o( 9e /=0Cl Cl c-1
9i"!re /;0 ass s$ectra o( Cr /=0ClCl c-1
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9i"!re /)0 ass s$ectra o( Co/=0ClCl c-1
9i"!re /K0 ass s$ectra o( Ni/=0Cl c-1
9i"!re /1*0 ass s$ectra o( C!/=0Cl c-1
Address fr crres(ndence:
Authors: Bassam Abdulhussein Hasan Alsafee, Department of Pharmaceutical Chemistry /
College of Pharmacy, Thi-qar University.
E-mail : &assaVor"Wyahoo.co