OLAR et al.
three exothermal steps beginning with the
(3) Analysis, found: Ni, 10.82; C, 26.81;
Cl, 13.22; H, 6.03; N, 31.36%; NiC12Cl2H32N12O4
requires: Ni, 10.91; C, 26.79; Cl, 13.18; H, 5.99;
1,2,4-triazole moiety elimination. The metallic oxides
are the final products as powder XRD indicates.
The biological assays indicated that complexes
do not behave as HIV inhibitors but exhibited a good
antimicrobial activity. It is to be mentioned that in the
most cases Cu(II) complexes present a higher activity
by comparison with Ni(II) compounds.
N, 31.24%; IR (KBr pellet), cm–1: nOH, 3420s, nNH
,
3300m; nas(CH ) , 2950m; ns(CH , 2880m; nC=N, 1620vs,
)
2
2
1590s; dNH, 1535m, 1465m; dCH, 1400m; n
1320m, 1295m, 1220m; nC –N , 1180m, 1160m,
,
Cheterocyclic –N
aliphatic
1140m; nN–N, 980w; r , 760m; nNi–N, 480w;
CH 2
UV-Vis (MgO pellet), cm–1: 3A2®3T2: 24390;
3A2®3T1(F):
14490;
B=865 cm–1; b=0.83; meff, mB: 3.16.
3A2®3T1(P):
12990;
Experimental
(4) Analysis, found: Cu, 11.67; C, 26.46;
Cl, 13.07; H, 5.88; N, 30.80%; CuC12Cl2H32N12O4
requires: Cu, 11.70; C, 26.55; Cl, 13.06; H, 5.94;
Synthesis of the complexes
Compounds ML(1)Cl2·6H2O
N, 30.96%; IR (KBr pellet), cm–1: nOH, 3500s, sh; nNH
,
To a suspension of hydrated metal(II) chloride
(5 mmol), 3-amino-4H-1,2,4-triazole (T) (5 mmol,
0.42 g) and 3,6-diazaoctane-1,8-diamine (5 mmol,
0.82 mL) in 100 mL ethanol was added dropwise
1 mL triethylamine and 2 mL formaldehyde (37%).
The reaction mixture was refluxed 24 h until a
sparingly soluble compound was formed. The
microcrystalline product was filtered off, washed
with EtOH, Et2O and air-dried.
3300vs; nas(CH ) , 2940m; ns(CH , 2860m; nC=N, 1620s,
)
2
2
1600vs; dNH, 1440m; dCH, 1360s; n
–N , 1230m;
Cheterocyclic
nC –N , 1140m; nC–C, 1045m; nN–N, 980s; r
,
CH 2
aliphatic
770m; nCu–N, 410w; UV-Vis (MgO pellet), cm–1: CT:
25316; dxz,dyz®dx2–y2: 16800; dxy®dx2–y2: 14140; meff,
mB: 1.16.
Methods
(1) Analysis, found: Ni, 11.52; C, 24.77; Cl, 14.52;
H, 6.89; N, 22.82%; NiC10Cl2H34N8O6 requires:
Ni, 11.93; C, 24.41; Cl, 14.41; H, 6.96; N, 22.77%; IR
(KBr pellet), cm–1: nOH, 3410s, sh; nNH, 3200–3300m,
All reagents were of commercial analytical quality and
have been used without further purification. Chemical
analysis of carbon, nitrogen, sulphur and hydrogen has
been performed using a Perkin Elmer PE 2400
analyzer. Nickel and chloride were determined gravi-
metrically using dimethylglyoxyme and silver nitrate
respectively while copper was determined volu-
metrically using thiosulfate method in the laboratories
of Inorganic Chemistry Department.
IR spectra were recorded in KBr pellets with a
BIO-RAD FTIR 135 spectrometer in the range
400–4000 cm–1. Electronic spectra by diffuse
reflectance technique, with MgO as standard, were re-
corded in the range 300–2000 nm, on a Jasco V 670
spectrophotometer. Magnetic measurements were
done by Faraday’s method, at room temperature, us-
ing Hg[Co(NCS)4] as standard. The molar magnetic
susceptibilities were calculated and corrected for the
atomic diamagnetism. EPR spectra were recorded on
microcrystalline samples at room temperature with a
Varian E-9 spectrometer. The field was calibrated us-
ing crystalline diphenyylpicrylhydrazyl (g=2.0036).
The qualitative screening of the susceptibility
spectra of different microbial strains to the complexes
was performed by adapted diffusion techniques,
while the quantitative assay of minimal inhibitory
concentration (M.I.C., mg cm–3) value was based on
liquid medium serial microdilutions [16]. The com-
pounds were solubilised in DMF to a final concentra-
tion of 1 mg mL–1. The in vitro biological screening
effects were tested against a microbial inoculum of
br;
1630vs,1590vs; dNH, 1460m, 1430m; dCH, 1370s,
1350m; n –N , 1290s, 1280m, 1220m; n
n
,
2920m;
n
,
2865m; nC=N,
as(CH 2
)
s(CH 2 )
,
Caliphatic –N
Cheterocyclic
1180m, 1175m, 1160m; nC–C, 1075s, 1050s; nN–N
,
920w, 900w; r , 790w; nNi–N, 405w; UV-Vis (MgO
CH 2
3
3
pellet), cm–1: A2®3T2: 25640; A2®3T1(F): 16035;
3A2®3T1(P): 10150; B= 749 cm–1; b=0.72; meff, mB: 3.08.
(2) Analysis, found: Cu, 12.69; C, 24.28;
Cl, 14.35; H, 6.78; N, 22.62%; CuC10Cl2H34N8O6
requires: Cu, 12.79; C, 24.17; Cl, 14.27; H, 6.86;
N, 22.55%; IR (KBr pellet), cm–1: nOH, 3557s, sh; nNH
3428vs; n ) , 2940m; n ) , 2830m; nC=N, 1636m,
,
as(CH 2
s(CH 2
1618m; dNH, 1457m; dCH, 1384m; n
–N , 1287m;
, 1140m; nC–C, 1110s, 1090s; nN–N, 910w;
Cheterocyclic
n
r
Caliphatic –N
, 746w; nCu–N, 415w; UV-Vis (MgO pellet), cm–1:
CH 2
CT: 25445; dxz,dyz®dx2–y2: 16670; dxy®dx2–y2: 13530;
meff, mB: 1.52.
Compounds ML(2)Cl2·4H2O
To a suspension of hydrated metal(II) chloride
(5 mmol),
T (10 mmol, 0.84 g) and 1,2-
diaminoethane (10 mmol, 0.67 mL) in 100 mL
ethanol was added dropwise 1 mL triethylamine and
2 mL formaldehyde (37%). The reaction mixture was
refluxed 24 h until a sparingly soluble compound was
formed. The microcrystalline product was filtered off,
washed with EtOH, Et2O and air-dried.
J. Therm. Anal. Cal., 97, 2009
316