Sulfanilamide-containing coordination compounds of Cu(II) with isatin and N-methylisatin thiosemicarbazones

Article abstract of DOI:10.1134/S1070363206090179

Isatin (L¹) and N-methylisatin (L²) β-thiosemicarbazones react in ethanol with Cu(II) chloride and bromide in the presence of sulfanilamide (Streptocid, Sf¹), N′- acetylsulfanilamide (Sulfacyl, Sf²), Norsulfazole (Sf³), Aethazolum (Sf⁴), and Sulfadimesine (Sf⁵) to form coordination compounds Cu(Sf^1-5)L^1-2X₂· nH₂O (X = Cl, Br; n = 2-5). All the complexes have a monomeric structure. Thiosemicarbazones L¹ and L² in these complexes are tridentate O,N,S ligands, and sulfanilamides Sf^1-5 are monodentate ligands. Thermolysis of the substances involves the steps of dehydration (70-95°C) and complete decomposition (410-530°C).

Full text of DOI:10.1134/S1070363206090179

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 9, pp. 1458 1463.
Pleiades Publishing, Inc., 2006.
Original Russian Text
pp. 1521 1526.
A.P. Gulea, S.N. Spynu, V.I. Tsapkov, D. Poirier, J. Roy, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 9,
Sulfanilamide-containing Coordination Compounds of Cu(II)
with Isatin and N-Methylisatin Thiosemicarbazones
A. P. Guleaa, S. N. Spynua, V. I. Tsapkova, D. Poirierb, and J. Royb
a Moldavian State University, ul. A. Mateevicha 60, Chisinau, 2009 Moldova
b Laval University, CHUQ, G1V4G2, Quebec, Canada
Received February 10, 2006
Abstract Isatin (L1) and N-methylisatin (L2) -thiosemicarbazones react in ethanol with Cu(II) chloride
and bromide in the presence of sulfanilamide (Streptocid, Sf1), N-acetylsulfanilamide (Sulfacyl, Sf2), Nor-
sulfazole (Sf3), Aethazolum (Sf4), and Sulfadimesine (Sf5) to form coordination compounds Cu(Sf1 5)L1 2X2
nH2O (X = Cl, Br; n = 2 5). All the complexes have a monomeric structure. Thiosemicarbazones L1 and L2
in these complexes are tridentate O,N,S ligands, and sulfanilamides Sf1 5 are monodentate ligands. Thermo-
lysis of the substances involves the steps of dehydration (70 95 C) and complete decomposition (410 530 C).
DOI: 10.1134/S1070363206090179
Isatin -thiosemicarbazide and its derivatives form
with transition metal ions coordination compounds of
diverse compositions and structures [1 4]. Some of
these substances are biologically active [5, 6], which
allows their use as a base for the development of
selective microbiological media and potential disin-
fectants and antiseptics. It was found that the physio-
logical activity of these compounds is determined by
the simultaneous presence of complexing metal ions
and their inner-sphere surrounding. In this connection,
synthesis and study of new coordination compounds
of biometals with such ligands is of both scientific
and practical interest.
The goal of this study is synthesis and determina-
tion of the composition, probable structure, and phys-
icochemical properties of mixed-ligand complexes
of copper(II) chloride and bromide with isatin and
N-methylisatin -thiosemicarbazones (L1 and L2,
respectively) and selected sulfanilamides: sulfanil-
amide (Streptocid, Sf1), N-acetylsulfanilamide (Sulfa-
cyl, Sf2), Norsulfazole (Sf3), Aethazolum (Sf4), and
Sulfadimesine (Sf5).
H
CH3
N
O
N
O
S
S
NH
NH
N
N
NH2
NH2
L1
L2
O
S NH R
H2N
O
Sf1 5
(Sf3),
CH3
S
S
C2H5 (Sf4),
(Sf5).
N
N
R = H (Sf1), C(O)CH3 (Sf2),
N
N
N
CH3
It was found that the reaction of hot (50 55 C)
ethanol solutions of the above copper(II) halides with
thiosemicarbazones L1 2 and sulfanilamides Sf1 5
taken in a 1 : 1 : 1 molar ratio yields finely crystalline
substances I XV; according to elemental analysis
(Table 1), they have the composition Cu(Sf1 5).
1458

SULFANILAMIDE-CONTAINING COORDINATION COMPOUNDS OF Cu(II)
1459
Table 1. Physicochemical characteristics of sulfanilamide-containing coordination compounds of Cu(II) with isatin and
N-methylisatin -thiosemicarbazones
Found, %
Calculated, %
Cl (Br) Cu
Comp. Yield,
ef, BM
(294 K)
Formula
no.
%
C
H
Cl (Br) Cu
N
C
H
N
I
II
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
XV
62
68
60
65
69
73
72
77
73
75
66
67
72
75
74
2.09
1.79
1.75
1.84
1.92
2.06
2.18
1.94
1.88
1.93
2.11
1.79
1.89
1.75
1.78
30.00 3.81 11.64 10.45 13.88 C15H24Cl2CuN6O7S2 30.05 4.01 11.85 10.68 14.02
25.38 3.50 22.45 8.88 11.65 C15H26Br2CuN6O8S2 25.50 3.68 22.66 9.07 11.90
33.54 3.50 11.50 10.33 13.59 C17H22Cl2CuN6O6S2 33.72 3.64 11.74 10.58 13.88
27.70 3.44 21.70
32.33 3.40 10.41
28.84 2.87 21.01
33.31 3.26 10.75
27.90 3.14 20.55
35.01 4.31 9.61
30.90 4.12 19.33
8.53 11.67 C17H26Br2CuN6O8S2 27.95 3.56 21.92 8.77 11.51
9.48 14.50 C18H23Cl2CuN7O6S3 32.53 3.46 10.70 9.64 14.76
8.32 12.84 C18H23Br2CuN7O6S3 28.69 3.05 21.25 8.50 13.01
9.79 16.30 C18H22Cl2CuN8O4S3 33.49 3.41 11.01 9.92 17.36
8.18 14.44 C18H26Br2CuN8O6S3 28.05 3.38 20.78 8.31 14.54
8.97 15.20 C21H32Cl2CuN8O8S2 34.85 4.43
9.82 8.85 15.49
7.99 13.50 C21H32Br2CuN8O8S2 31.03 3.94 19.70 7.88 13.79
33.09 3.65 12.09 12.85 14.30 C16H22Cl2CuN6O5S2 33.28 3.81 12.31 11.09 14.56
32.05 3.94 10.90
33.47 3.48 10.18
35.18 4.59 10.21
37.54 4.04 9.88
9.86 12.90 C18H26Cl2CuN6O7S2 33.91 4.08 11.15 10.05 13.19
9.25 14.29 C19H25Cl2CuN7O6S3 33.63 3.69 10.47 9.44 14.45
9.32 16.79 C20H32Cl2CuN8O6S2 35.35 4.71 10.46 9.43 16.49
8.90 16.11 C22H30Cl2CuN8O6S2 37.66 4.28 10.13 9.13 15.98
(L1 2)X2 nH2O [Sf1 5 = Sf1 (I, II, XI), Sf2 (III, IV,
XII), Sf3 (V, VI, XIII), Sf4 (VII, VIII, XIV), Sf5 (IX,
X, XV); L1 2 = L1 (I X), L2 (XI XV); X = Cl (I, III,
V, VII, IX, XI XV), Br (II, IV, VI, VIII, X); n = 1
(VII), 2 (III, XI), 3 (V, VI, VIII, XII, XIII, XV), 4 (I,
IV), 5 (II, IX, X, XIV)].
curves of all the complexes exhibit an endothermic
effect at 70 95 C corresponding to dehydration.
The subsequent thermal effect in the DTA curves,
observed in the range 410 530 C, is exothermic and
is associated with thermal oxidative degradation of
the coordinated sulfanilamides (Sf1 5) and thiosemi-
carbazones (L1, L2). The temperature (Tdec) of
complete decomposition of the substances depends on
the nature of the inner-sphere ligands and increases on
replacement of the isatin moiety in L1 by N-methyl-
isatin moiety and of bromide ion by chloride ion; with
the same halide ion and thiosemicarbazone, Tdec de-
Coordination compounds I XV are insoluble in
ether, poorly soluble in water and alcohols, and readi-
ly soluble in dimethylformamide (DMF) and dimethyl
sulfoxide. Their yields and physicochemical character-
istics are given in Tables 1 3.
creases in the order Sf4
Sf5 > Sf3 > Sf2 > Sf1.
Visual microscopic examination of complexes
I XV showed that their powders exhibited phase uni-
formity and consisted of crystals of various shapes.
We failed to prepare single crystals of X-ray quality;
we identified the compounds and examined their
structures by elemental and thermal analyses, molar
electrolytic conductivity measurements, IR spectros-
copy, and magnetic measurements.
Using the Horowitz Metzger’s method [7] with
Topor’s modifications [8], we estimated the kinetic
parameters of the dehydration of complexes I XV:
activation energy Ea and preexponential factor Z. As
seen from Table 2, they are close to the parameters of
related reactions described in the literatrue [9 11].
With the aim to determine the mode of ligand
coordination with the central ion, we compared the IR
spectra of complexes I XV and of the starting thio-
semicarbazones L1, 2 and sulfanilamides Sf1 5, taking
into account the published data [1 6] for coordination
compounds of transition metals with related Schiff
bases. We found (Table 3) that azomethines L1 and L2
in I XV behave as tridentate O,N,S ligands and coor-
dinate with the metal via the carbonyl oxygen atom
of the isatin moiety, C=N nitrogen atom, and sulfur
atom, forming two five-membered chelate rings. This
All the compounds prepared are nonelectrolytes in
DMF ( = 2 4
1
1 cm2 mol ).
A magnetochemical study of complexes I XV at
room temperature (Table 1) showed that their effective
magnetic moments correspond to the spin values for
one unpaired electron. This fact suggests for them a
monomeric structure.
Thermal analysis of I XV showed (Table 2) that
these compounds decompose in two steps. The DTA
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 9 2006

1460
GULEA et al.
Table 2. Results of thermal analysis of sulfanilamide-containing coordination compounds of Cu(II) with isatin and
N-methylisatin -thiosemicarbazones
Weight loss, %
Kinetic parameters
Temperature of
complete
Comp.
no.
Dehydration
temperature, C
1
found, % calculated, % elimination of
Ea, kJmol
logZ decomposition, C
I
II
70
85
80
75
95
80
75
85
70
80
90
75
85
80
75
11.7
12.5
6.2
10.0
8.5
7.0
3.0
7.0
12.1
11.0
6.0
8.2
8.3
12.0
12.7
6.0
9.9
8.1
7.2
2.7
6.9
12.4
11.1
6.2
8.5
8.0
4H2O
5H2O
2H2O
4H2O
3H3O
3H2O
H2O
3H2O
5H2O
5H2O
2H2O
3H2O
3H2O
5H2O
3H2O
35.1
42.6
30.9
32.1
40.3
26.9
30.1
38.5
35.6
37.4
45.1
43.2
28.8
31.3
40.1
4.1
4.7
3.8
3.9
4.5
2.9
3.7
4.4
4.2
4.3
5.1
4.8
3.1
3.8
4.5
430
410
440
430
460
440
510
500
500
480
450
460
480
530
520
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
XV
12.0
7.5
12.1
7.7
1
Table 3. Frequencies (cm ) of absorption bands in the IR spectra of sulfanilamide-containing coordination compounds of
Cu(II) with isatin and N-methylisatin -thiosemicarbazones
(NH)
of
isatin
(M N),
(M O),
(M S)
Comp.
no. a
(NH2),
(NH)
as(SO2),
2(SO2)
(C=O) (C=N)
(C N) (C=S) (C N) (S N) (C S) (SO2)
L
3320, 3430, 3315, 1710
1620
1185, 1120
1110
980,
945
3300
3180, 1540
Sf1
I
3440, 3330
3210, 1530
1320,
1145
1330
1115
975,
930
860
855
745
740
560
555
3322, 3425, 3415, 1685
1600
1605
1325,
1140
1325, 1100
1180,
1115
975,
940,
930
530, 490,
475, 415
3300
3310, 3305,
3190, 1525
II
3325, 3425, 3415, 1680
1320,
1140
1325, 1100
1185,
1110
975,
945,
935
855
745
560
520, 485,
470, 435
3305
3310, 3305,
3190, 1520
Sf2
3440, 3320
3210, 1540
1675
1325,
1140
1330,
1115
985,
935
865
860
740
740
560
555
III
3320, 3420, 3415, 1685, 1605
1320,
1130
1335, 1105
1180,
1115
980,
935,
930
525, 480,
465, 410
3305
3310, 3305, 1670
3190, 1525
IV
3323, 3425, 3415, 1690, 1600
1325,
1135
1330, 1105
1185,
1120
985,
940,
935
860
870
745
745
555
560
530, 475,
470, 430
3305
3310, 3305, 1670
3190, 1525
Sf3
3435, 3335
3200, 1530
1625
1315,
1130
1320,
1110
980,
925
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 9 2006

SULFANILAMIDE-CONTAINING COORDINATION COMPOUNDS OF Cu(II)
Table 3. (Contd.)
1461
(NH)
of
isatin
(M N),
(M O),
(M S)
Comp.
no. a
(NH2),
(NH)
as(SO2),
2(SO2)
(C=O) (C=N)
(C N) (C=S) (C N) (S N) (C S) (SO2)
V
3321, 3430, 3330, 1695
1605,
1600
1310,
1125
1325, 1100
1180,
1105
1325, 1105
1185,
1110
1330
1120
1325, 1100
1180,
1115
1330, 1100
1185,
1125
1335
1110
1330, 1100
1180,
1115
1335, 1100
1185,
1110
985,
945,
930
985,
940,
930
985,
930
980,
940,
925
985,
935,
930
980,
940
985,
940,
930
980,
945,
930
870
865
745
745
555
560
520, 480,
465, 415
3305
3320, 3205,
3185, 1535
VI
3320, 3435, 3330, 1690
1600,
1595
1315,
1125
525, 485,
465, 425
3305
3325, 3200,
3190, 1530
3435, 3330
3200, 1535
Sf4
1620
1320
1135
1315,
1130
870
865
750
745
560
560
VII
3322, 3430, 3335, 1695
1615,
1605,
1600
1610,
1600,
1595
1630
530, 480,
470, 420
3300
3315, 3205,
3195, 1535
VIII
3320, 3435, 3330, 1690
1315,
1135
870
745
555
525, 490,
475, 410
3297
3320, 3200,
3190, 1530
3460, 3350
3245, 1535
Sf5
1320
1145
1315,
1140
870
865
755
750
570
560
IX
3323, 3455, 3350, 1695
1625,
1605,
1600
1620,
1600,
1595
1615
530, 480,
460, 415
3298
3320, 3245,
3190, 1535
X
3320, 3460, 3355, 1690
1320,
1145
870
750
565
510, 490,
480, 435
3299
3325, 3240,
3195, 1530
3435, 3325
3190, 1545
L1
1700
1190
1120
1115
980,
935
XI
3420, 3410, 1680
3315, 3310,
3195, 1535
3425, 3415, 1695, 1600
3315, 3300, 1675
3195, 1530
3430, 3320, 1685
3315, 3200,
3195, 1540
3435, 3330, 1690
3320, 3200,
3195, 1530
3445, 3355, 1690
3320, 3240,
1595
1320
1140
1320, 1100
1185,
1110
1330, 1100
1185,
1115
1330, 1100
1185,
1105
1320, 1095
1185,
1115
975,
935,
930
980,
940,
935
980,
940,
930
985,
945,
930
850
860
865
860
860
745
745
750
745
750
565
565
560
560
560
510, 485,
470, 435
XII
1325,
1135
515, 490,
475, 430
XIII
XIV
XV
1600,
1595
1315,
1120
530, 495,
485, 435
1610,
1600,
1595
1610,
1600,
1585
1310,
1125
515, 475,
470, 410
1315,
1135
1335, 1100
1185,
1110
980,
945,
935
510, 485,
475, 435
3200, 1530
a
Complexes were preliminarily kept in an oven at 105 C to constant weight.
is indicated by a 30 15 cm 1 low-frequency shift of the
(C=O) and (C=N) bands compared to the related
absorption bands of the starting thiosemicarbazones
(in L1 and L2 they are manifested at 1710 1700 and
spectra of all the complexes: (Cu N) at 525 505 and
1
1
430 405 cm , (Cu O) at 490 460 cm , and
1
(Cu S) at 460 445 cm . Participation of other
functional groups of L1 and L2 in the coordination is
unlikely, because the characteristic absorption bands
are not noticeably shifted relative to the starting thio-
semicarbazones. As for sulfanilamides, their presence
1
1620 1610 cm , respectively). The suggested coor-
dination mode of L1 and L2 is also supported by the
1
appearance of new bands at 530 405 cm in the IR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 9 2006

1462
GULEA et al.
in the complexes is confirmed by the corresponding
absorption bands (Table 3). The spectra suggest that
Streptocid and Sulfacyl are coordinated via the amine
nitrogen atom; Norsulfazole and Aethazolum, via the
thiazole and thiadiazole nitrogen atoms; and Sulfadi-
mesine and Sulfapyridazine, via one of pyrimidine and
pyridazine nitrogen atoms. In the case of I IV, XI,
ylisatin -thiosemicarbazones (mp 251 253 and 242
244 C, respectively) were prepared by the procedure
described in [1].
Dichloro(1H-indole-2,3-dione 3-thiosemicarba-
zone)(4-aminobenzenesulfamide)copper tetrahyd-
rate (I). Hot (50 55 C) ethanolic solutions of
10 mmol of copper(II) chloride dihydrate and 10 mmol
of isatin -thiosemicarbazone (L1) were mixed with
an alcoholic solution of 10 mmol of Streptocid (4-
aminobenzenesulfamide). The mixture was refluxed
on a water bath for 40 45 min with continuous stir-
ring. A dark green finely crystalline product precipi-
tated on cooling; it was filtered off, washed with etha-
nol and ether, and dried in air.
1
and XII, this follows from the 25 15 cm long-wave
shift of the (NH2) and (NH) absorption bands, and
in the case of V X and XIII XV, from the splitting
1
and 25 20 cm long-wave shift of the (C=N) band
(Table 3).
Thus, we have determined the composition and
struture of the synthesized compounds by elemental
analysis and physicochemical methods.
The following structure can be suggested for I XV:
Compounds II XV were prepared similarly start-
ing from copper(II) chloride and bromide, thiosemi-
carbazones L1, 2, and sulfanilamides Sf1 5 (molar ratio
1 : 1 : 1). Their yields and physicochemical character-
istics are given in Tables 1 3.
NH2
N
X Cu
O
X
S
Sf1 5
nH2O
N
R
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