Synthesis, structural and spectral characterization of Zn(II) complexes, derived from thiourea and thiosemicarbazide

Article abstract of DOI:10.1016/j.ica.2011.10.027

Novel mono- and binuclear complexes of Zn(II) with thiourea derivatives (H₂L) (N-2-propenyl-N′-2-pyridinylthiourea) and thiosemicarbazide, H₃L (2-[(2-hydroxyphenyl)methylene]hydrazine-N-(2- propenyl)carbothioamide, (2-[(2-hydroxyphen

Full text of DOI:10.1016/j.ica.2011.10.027

Inorganica Chimica Acta 382 (2012) 127–138
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Inorganica Chimica Acta
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Synthesis, structural and spectral characterization of Zn(II) complexes, derived
from thiourea and thiosemicarbazide
a
a
b
b
a
S.I. Orysyk a, , V.V. Bon , O.O. Obolentseva , Yu. L. Zborovskii , V.V. Orysyk , V.I. Pekhnyo ,
⇑
V.I. Staninets b, V.M. Vovk b
a V.I. Vernadskii Institute of General and Inorganic Chemistry NAS of Ukraine, Palladin Av. 32/34, 03680 Kyiv, Ukraine
b Institute of Organic Chemistry NAS of Ukraine, Murmanska Str. 5, 02660 Kyiv, Ukraine
a r t i c l e i n f o
a b s t r a c t
Novel mono- and binuclear complexes of Zn(II) with thiourea derivatives (H2L) (N-2-propenyl-N0-2-
pyridinylthiourea) and thiosemicarbazide, H3L (2-[(2-hydroxyphenyl)methylene]hydrazine-N-(2-prope-
nyl)carbothioamide, (2-[(2-hydroxyphenyl)methylene]hydrazine-N-phenylcarbothioamide) have been
synthesized. The possibility of mono- or tridentate coordination to the central metal ion of these ligands
both in neutral and in monodeprotonated thionic tautomeric form with the stoichiometric ratios
Zn:L = 1:1 and 1:2 has been shown. The synthesized complexes Zn(CH3COO)2(H2L)2 (I), Zn2(CH3COO)2
(H2L)2ꢀZn2(CH3COO)(H2O)(H2L)2 (II), Zn(H2L)2 (III), Zn2(CH3COO)2(H2L)2 (IV) have been studied by IR,
UV–Vis, 1H, 13C NMR spectroscopy and single crystal X-ray diffraction (I, II, IV). It has been established that
in compound (I) the central Zn atom forms a strongly distorted tetrahedral ZnS2O2 coordination, while in
(II) and (IV) it forms a square-pyramidal ZnSNO3 environment. In the case of complex (II) the asymmetric
unit contains two molecules of binuclear complex compounds, which are slightly differ by coordination in
vertex direction of Zn polyhedron. The square-pyramidal geometry of Zn(II) ions from the first molecule
completed by two acetate anions, which is similar to compound (IV). In the second molecule, the Zn(II) coor-
dination polyhedrons are completed by one acetate anion and one water molecule.
Article history:
Received 9 April 2011
Received in revised form 18 August 2011
Accepted 6 October 2011
Available online 20 October 2011
Keywords:
Thiourea derivatives
Carbothioamide
Zn(II) complexes
NMR spectroscopy
X-ray diffraction study
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
complexes Zn(II) ions, located in the active site of enzymes can
serve as such inhibitors [3–7,11,14,15]. It is logical to assume that
Zinc is a biologically essential element [1]. Zn(II) ions as a cofac-
tor are part of over 300 enzymes (carbonic anhydrases, zinc pro-
teinases, histone deacetylases, alkaline phosphatases, alcohol
dehydrogenases, aminopeptidases, etc.), which involved in meta-
bolic processes of living organisms: viruses, bacteria, plants and
animals [1–8]. Many of the above mentioned enzymes can also
participate in processes giving rise to pathological states. For
example, zinc-containing proteinases, which are produced by
viruses, split the host’s protein into small fragments, from which
new copies of viruses are then created [9,10]. Zinc proteinases
are included in the life cycle of different kind of bacteria sometimes
also pathogenic ones [8]. The activity of zinc proteinases and his-
tone deacetylases increases greatly when cancer diseases or a
number of other diseases arise [3,5–7,11–14]. Therefore, the efforts
of many laboratories are directed at search for effective inhibitors
of zinc-containing enzymes, which are of interest as potential
pharmaceuticals. The compounds that are able to bind into stable
the functional derivatives of thiocarbamic acid, in particular thio-
urea and thiosemicarbazone, which are known in literature as sen-
sitive reagents for the extraction–photometric determination of
Zn(II) [16], will possess such an activity. Moreover, complexes of
thiosemicarbazones with a number of transition metal ions show
a high bioactivity and are of interest as potential anticancer, anti-
viral, antibacterial and anti-inflammatory drugs [17–21].
In the synthetic aspect, thiourea and thiosemicarbazide deriva-
tives are of interest as effective complexing agents for transition
metal ions. In particular, it has been shown that N-2-propenyl-
N0-2-pyridinylthiourea forms stable complexes with Bi(III) ions
[22], while 2-[(2-hydroxyphenyl)methylene]hydrazincarbothioa-
mide derivatives form ones with Zn(II) ions [23–25].
Thiourea and its derivatives are part of the complexes as poly-
dentate ligands since their molecule contains several nucleophilic
electron-donor centers, the geometry of whose arrangement and
the electronic configuration of complexing metal determine the
possibility of forming various structure complexes [26–30]. Like
other ambidentate ligand systems, they are characterized by com-
petitive coordination; which defines the scientific interest in study
⇑
Corresponding author.
E-mail address: orysyk@ionc.kiev.ua (S.I. Orysyk).
0020-1693/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2011.10.027

128
S.I. Orysyk et al. / Inorganica Chimica Acta 382 (2012) 127–138
their interaction with metal ions, in particular with Zn(II), which is
able to form both a tetrahedral and an octahedral coordination
unit.
located objectively from a difference map of electron density and
0
refined using the distance restraints d(O–H0 ) = 0.82 0.04 ÅA, Uiso
(H) = 1.5 Ueq(O) and d(N–H) = 0.87 0.04 ÅA, Uiso(H) = 1.2 Ueq(N).
The H atoms bonded to C atoms were placed in turn in geometri-
cally idealized positions in accordance with hybridization of the
accompanying atom and refined using a riding model with Uiso
(H) = 1.5 Ueq(C) in the case of CH3 group and Uiso(H) = 1.2 Ueq(C)
in all other cases. When refining the structure of I, disorder of
the allyl groups C7–C9 and C16–C18 over two positions was estab-
lished. As a result, the mentioned groups were refined with occu-
pancies of 0.348/0.652 and 0.563/0.437, respectively. During
refining the structure II, a highly disordered lattice water molecule
was observed, all positions of which could not be refined. There-
In the present work, the ability of a number of chelating thiourea
derivatives: N-2-propenyl-N0-2-pyridinylthiourea (A), 2-[(2-hydroxy-
phenyl)methylene]hydrazine-N-(2-propenyl)carbothioami de(B) and
2-[(2-hydroxyphenyl)methylene]hydrazine-N-phenylcarboth ioami
de (C) (Scheme 1) for complex formation with zinc ions has been
shown. The procedures for the synthesis of coordination compounds
in the crystalline form has been developed, their spectral character-
istics, composition and structure have been studied.
2. Materials and methods
fore, SQUEEZE
intensities with subtraction of the electron density of the disor-
dered molecule [32]. Besides, disorder of the allyl fragment C13
/PLATON routine was employed to correct reflection
2.1. Material sources
–
C15 over two positions with occupancies of 0.374/0.626 was estab-
lished in the course of refinement. CCDC 817648–817650 contain
the complete set of data on the compounds I, II and IV and can
be request free of charge from Cambridge Crystallographic Data,
12 Union Road, Cambridge, CB2 1EZ, UK (http://www.ccdc.cam.
ac.uk/products/csd/request/).
Chemically pure Zn(CH3COO)2ꢀ2H2O was used as a source of
zinc salts for the synthesis of complexes I, II, IV, and chemically
pure Zn(NO3)2ꢀ6H2O was used for synthesize the product III.
2.2. Physical measurements
The UV–Vis spectra of compounds in 10ꢁ4 M DMF solutions
were recorded on Specord M 40 spectrophotometer in the range
of 50000–11000 cmꢁ1 (lquartz cells = 0.1 cm). The IR spectra were
obtained on Specord M 80 spectrophotometer in the range 4000–
200 cmꢁ1 using pellets with KBr. The 1H and 13C NMR spectra were
measured on Bruker Advance DRX-500 spectrometer (500.13 and
125.75 MHz, respectively), in DMSO-d6 solution using TMS as
internal standard.
3. Experimental
3.1. N-2-Propenyl-N0-2-pyridinylthiourea, H2L (A)
4
S
3
2
5
7
9
2.3. X-ray crystallography
3'
1'
6
N
N
2'
N
1
8
H
H
The unit cell parameters and three-dimensional set of reflection
intensities for single crystals ofI, II and IV were measured on a Bru-
0
ker Smart Apex II diffractometer (Mo K radiation, k = 0.71073 ÅA,
a
graphite monochromator) at room temperature. The experimental
data from X-ray structural experiment are listed in Table 1. The
structures were solved by direct methods and refined by the full-
matrix least-squares on F2 in anisotropic approximation for non
hydrogen atoms using the SHELXTL program package [31]. The
hydrogen atoms bonded to nitrogen and oxygen atoms were
It has been synthesized by the method reported in [33], m.p.
100–101 °C. Yield: 88%; Anal. Calc. for C9H11N3S: C, 55.93; H,
5.74; N, 21.74; S, 16.59. Found: C, 55.61; H, 5.59; N, 21.42; S,
16.29%. UV–Vis date,
(1930) and 34050 (1960). IR data,
m,
cmꢁ1 (DMF): 40560 (1710); 37400
m
, cmꢁ1: 3243,
m(NH); 3117,
Scheme 1. Tautomeric forms of the ligands.

S.I. Orysyk et al. / Inorganica Chimica Acta 382 (2012) 127–138
129
Table 1
Crystal data and structure refinement for I, II and IV.
Complexes
I
II
IV
Molecular formula
Crystal size (mm)
Crystal system
C
22H28N6O4S2Zn
C52H62N12O13S4Zn4
0.20 ꢂ 0.15 ꢂ 0.03
Monoclinic
P21/c
8.1414 (12)
C32H30N6O6S2Zn2
0.35 ꢂ 0.25 ꢂ 0.05
Monoclinic
P21/c
14.751 (10)
0.35 ꢂ 0.25 ꢂ 0.15
Monoclinic
P21/c
Space group
0
10.0669 (12)
a (AÅ)
0
16.2275 (16)
16.6857 (17)
28.470 (4)
27.907 (4)
29.57 (2)
7.820 (4)
b (AÅ)
0
c (AÅ)
b (°)
V (ÅA3)
92.818 (5)
2722.5 (5)
95.858 (2)
6434.7 (16)
100.51 (4)
3354 (4)
0
Z
4
4
4
Dcalc (g cmꢁ3
)
1.391
1.0 93
1184
1.500
1.670
2984
1.564
1.608
1616
l
(mmꢁ1
F(000)
h Range (°)
)
1.75 6 h 6 26.48
ꢁ9 6 h 6 2
ꢁ19 6 k 6 20
ꢁ20 6 1 6 20
19269/5591 [R(int) = 0.0249]
4261
1.02 6 h 6 26.34
ꢁ10 6 h 6 10
ꢁ35 6 k 6 28
ꢁ34 6 1 6 34
43211/13045 [R(int) = 0.0731]
6997
1.56 6 h 6 26.63
ꢁ18 6 h 6 18
ꢁ36 6 k 6 36
ꢁ9 6 1 6 9
Range of indices
Total/independent reflections
Number of reflections with I > 4
29441/6802 [R(int) = 0.0978]
r(I)
3680
Number of parameters to be refined
348
1.054
809
0.931
447
1.005
GOOF (F2)
R1, wR2 (I P 4
R1, wR2 (all reflections)
r
(I))
0.0371, 0.0955
0.0570, 0.1098
0.564/ꢁ0.234
0.0556, 0.1074
0.1254, 0.1271
0.687/ꢁ0.379
0.0538, 0.1092
0.1267, 0.1370
0.553/ꢁ0.444
0
D
q
/
max Dqmin (e ÅAꢁ3
)
m
(@CH); 3057,
2859, (C–H); 1600, 1556, 1536 in-plane deformation vibrations
d(NH–CS–NH); 1478, 1450, 1422, pyridine ring vibrations (PyH);
1330, 1302, 1275, 1260; 1242; 1194; 1143 (NH–CS–NH); 1103;
m
(CHPy); 2960, asymmetric vibrations
m
(CH2)allyl
;
J = 6.0 Hz, C3HPy); 7.19 (d, 1H, J = 8.5 Hz, C5HPy); 7.78 (t, 1H,
J = 8.5 Hz, C4HPy); 8.23 (d, 1H, J = 5.0 Hz, C2HPy); 10.66 (s, 1H,
m
0
0
m
N3 H); 11.79 (s, 1H, N1 H). 13C NMR data, d, ppm (DMSO-d6):
m
22.47 C(Ac); 46.72 C(7); 112.42 C(5); 115.78 C(9); 117.63 C(3)
133.78 C(8); 138.65 C(4); 145.37 C(2); 153.81 C(1); 176.63 C(C@O)
;
;
998, 953, 935; 915, 897 in-plane deformation vibrations d(CH);
849; 811; 760; 707, 687 out-of-plane deformation vibrations
d(CH); 626; 538, 525, 512 deformation vibrations d(CHallyl). 1H
NMR data, d, ppm (DMSO-d6): 4.31 (m, 2H, C7H2); 5.16–5.26 (dd,
J = 10.5, 17.0 Hz, 2H, @C9H2); 5.93–6.06 (m, 1H, @C8H); 7.04 (t,
J = 6.0 Hz, 1H, C3HPy); 7.18 (d, J = 8.5 Hz, 1H, C5HPy); 7.78 (t,
J = 8.5 Hz, 1H, C4HPy);8.23 (d, J = 5.0 Hz, 1H, C2HPy); 10.65 (s, 1H,
179.75 C(6)
.
3.3. 2-[(2-Hydroxyphenyl)methylene]hydrazine-N-(2-propenyl)-
carbothioamide, H3L (B)
0
0
N3 H); 11.80 (s, 1H, N1 H). 13C NMR data, d, ppm (DMSO-d6):
46.68 C(7); 112.71 C(5); 115.75 C(9); 117.58 C(3); 134.19 C(8)
138.78 C(4); 145.12 C(2); 153.75 C(1); 179.77 C(6)
;
3
.
2
1
S
8
OH
4
5
1'
N
9
11
3'
3.2. Bis[(N-2-propenyl-N0-2-pyridinylthiourea-
-O)]zinc(II), Zn(CH3COO)2(H2L)2 (I)
j-S)(acetate
2'
7
N
N
10
6
-
j
H
H
Twenty milliliter of ethanolic solution of Zn(CH3COO)2ꢀ2H2O
(0.2194 g, 0.1 mmol) acidified with 3 ml of concentrate acetic acid
was mixed with 20 ml of hot ethanolic solution of ligand (A)
(0.3866 g, 0.2 mmol). The mixture was stirred for 25 min at 65 °C
until evaporation of more than half of its volume. The resulting col-
orless solution was corked and left for crystallization for 3 weeks. I
result, the needle-shaped transparent crystals of the complex I
formed. m.p. 124–125 °C. Yield 0.39 g (65%). Anal. Calc. for
It has been synthesized by the method reported in [34]. m.p.
153–154 °C. Yield 79%. Anal. Calc. for C11H13N3SO: C, 56.17; H,
5.53; N, 17.87; S, 13.62. Found: C, 56.20; H, 5.60; N, 17.81; S,
13.66%. UV–Vis date,
32650 (710); 30055 (695). IR data,
(OH); 3099, (@CH); 2943, asymmetric vibrations
3005, (CH); 1624, d, (C@N); 1604, 1550, 1528, in-plane deforma-
tion vibrations d(NH–CS–NH); 1489, 1472, 1438, 1414, phenolic
ring vibrations (PhH); 1357, 1330, (CS); 1294, 1228 (C–OPh);
1154, 1127, 1090, (NH–CS–NH); 1042, 1010, (N–N); 978, 948
m
, cmꢁ1 (DMF): 34200 shoulder (670);
m
, cmꢁ1: 3291,
m
(NH); 3168,
C
22H28N6O4S2Zn: C, 46.32; H, 4.91; N, 14.74; S, 11.23. Found: C,
46.35; H, 4.95; N, 14.79; S, 11.25%. UV–Vis date,
, cmꢁ1 (DMF):
40330 (2830); 36645 (1452) and 33635 (1555). IR data,
, cmꢁ1
(CHPy); 2977
(CH3Ac); 2859, 2783,
m
m
m
(CH2)allyl
;
m
m
m
m
:
3239 (shoulder), 3185,
asymmetric vibrations,
m
m
(NH); 3071,
(CH2)allyl; 2935,
m
(@CH); 3011,
m
m
m
m
m
m
m
m
(CH); 1630,
tions d(NH–CS–NH); 1478, 1437, 1400 pyridine ring vibrations
(PyH); 1330; low intensity 968, 943, 917; 898, 878 in-plane defor-
m
(C@OAc); 1577,1544 d, in-plane deformation vibra-
d, 936, 905, in-plane deformation vibrations d(CH); 800, 738,
650, out-of-plane deformation vibrations d(CH); broadened 619,
577, 548, 525, 481, 464, deformation vibrations d(CHallyl). 1H
NMR data, d, ppm (DMSO-d6): 4.23 (m, 2H, C9H2); 5.09–5.18 (dd,
2H, J = 10.0, 17.0 Hz, C11H2); 5.90–5.95 (m, 1H, @C10H); 6.84 (t,
1H, J = 7.5 Hz, C5HAr); 6.89 (d, 1H, J = 8.5 Hz, C3HAr); 7.23 (t, 1H,
m
mation vibrations d(CH); 839; intense 773, 722, 660, out of-plane
deformation vibrations d(CH); 629, 616, 550, 514 deformation
vibrations d(CHallyl); 284, m(Zn–S). 1H NMR data, d, ppm (DMSO-
d6): 1.83 (s, 3H, CH3CO); 4.31 (m, 2H, C7H2); 5.15–5.26 (dd, 2H,
J = 10.5, 17.0 Hz, @C9H2); 5.93–6.06 (m, 1H@C8H); 7.04 (t, 1H,
J = 8.0 Hz, C4HAr); 7.96 (d, 1H, J = 7.5 Hz, C6HAr); 8.40 (s, 1H,
0
@C7H); 8.60 (t, 1H, J = 5.5 Hz, N3 H); 9.90 (s, 1H, OH); 11.46 (s,

130
S.I. Orysyk et al. / Inorganica Chimica Acta 382 (2012) 127–138
0
1H, N2 H). 13C NMR data, d, ppm (DMSO-d6): 45.71 C(9); 115.40
C(11); 115.95C(3); 118.92 C(5); 120.35 C(1); 126.43 C(6); 130.77 C(4)
134.73 C(10); 139.12 C(7); 156.32 C(2); 177.00 C(8)
3.6. 2-[(2-Hydroxyphenyl)methylene]hydrazine-N-phenyl)carbothioa
mide, H3L (C)
;
.
3.4. Bis{
propenyl)carbothioamide–
Zn2(CH3COO)2(H2L)2ꢀZn2(CH3COO)(H2O)(H2L)2 (II)
l
2-O[(E)-2-[(2-hydroxyphenyl)methylene]hydrazine-N-(2-
3-O,N,S][acetate–
-O]zinc(II)},
7
6
3
H
N
1
j
j
S
5
4
N
1'
2'
8
2
10
13
OH
HN
3'
9
Twenty milliliter of ethanolic solution of Zn (CH3COO)2ꢀ2H2O
(0.47 g, 0.1 mmol) (acidified with 3 ml of concentrate acetic acid)
was mixed with 20 ml of hot ethanol solution of ligand (B)
(0.44 g, 0.1 mmol). The mixture was refluxed for 45 min. The color
of reaction mixture solution changed to yellow immediately after
adding the first drops of ligand solution. The mixture was left for
crystallization in dark place. After 4 days, needle-shaped light
green-yellow crystals grown. Decomposition temperature 265–
270 °C. Yield 0.86 g (95%). Anal. Calc. for C52H62N12O13S4Zn4: C,
42.94; H, 4.27; N, 11.56; S, 8.81. Found: C, 42.92; H, 4.29; N,
11
12
14
It was obtained by the modified method [35] the interaction of
4-phenylthiosemicarbazide with 2-hydroxybenzaldehyde in
refluxing ethanol. m.p. 186–187 °C (with decomposition). Yield
77%. Anal. Calc. for C14H13N3OS: C, 61.97; H, 4.83; N, 15.49; S,
11.82. Found: C, 61.85; H, 4.78; N, 15.35; S, 11.38%. UV–Vis date,
11.75; S, 8.88%. UV–Vis date,
(290); 31000 (275); 26650 (342). IR data,
3076, (@CH); 3017, (CH); 2975, asymmetric vibrations
lyl; 2917, (C@N) and
(CH3Ac); 1631, (C@OAc); 1608, 1592, 1550,
in-plane deformation vibrations d(NH–CS–NH); 1474, 1438, 1409,
phenolic ring vibrations (PhH); 1345, 1321, (CS); 1279, 1257,
1205, (C–OPh); 1152, 1125, 1088, (NH–CS–NH); 1039 d, 1017,
(N–N); 993, 973, 944, 905, in-plane deformation vibrations
d(CH); 800, 743, 653, out-of-plane deformation vibrations d(CH);
613, 575, 557, 464, deformation vibrations d(CHallyl); 438, (Zn–
m
, cmꢁ1 (DMF): 32190 shoulder
, cmꢁ1: 3242,
(NH);
(CH2)al-
m
m
m
m
m
m
, cmꢁ1 (DMF): 33450, shoulder (490); 32470 (510); 29360
m
m
m
(670). IR data,
m
m
, cmꢁ1: 3340, w,
(C–H); 1623, 1602, 1595, d, 1539, 1515
m
(NH); 3156
m
(OH); 3056, 2999
m(CHAr); 2856
m
(C@N)
m
m
and in-plane deformation vibrations d(NH–CS–NH); 1472, 1447,
1403, phenolic ring vibrations (PhH); 1342, 1320, d, (CS); 1279,
d, 1267, 1218 (C–OPh); 1159, 1088, (NH–CS–NH); 1044, d, 1013
(N–N); 960, 930, d, 914 in-plane deformation vibrations d(CH);
m
m
m
m
m
m
m
m
m
880, 781, 744 d, 731, 681, 648, out-of-plane deformation vibrations
d(CH); 601, 567, out-of-plane deformation vibrations of aromatic
ring d(CHAr). 1H NMR data, d, ppm (DMSO-d6): 6.86 (t, 1H,
J = 7.5 Hz, C5HAr); 6.90 (d, 1H, J = 8.5 Hz, C3HAr); 7.21 (t, 1H,
J = 7.0 Hz, C12HAr); 7.25 (t, 1H, J = 8.0 Hz, C4HAr); 7.38 (t, 2H,
J = 8.0 Hz, C11,13HAr); 7.61 (d, 2H, J = 8.5 Hz, C10,14HAr); 8.10 (d,
1H, J = 7.0 Hz, C6HAr); 8.52 (s, 1H, @C7H); 9.98 (s, 1H, OH); 10.06
N); 285 m
(Zn–S). 1H NMR data, d, ppm (DMSO-d6): 1H NMR, d,
ppm (DMSO-d6): 1.91 (s, 3H, CH3CO); 3.91 (m, 2H, C9H2); 5.01–
5.15 (dd, 2H, J = 10.0, 17.5 Hz, @C11H2); 5.86–5.92 (m, 1H,
@C10H); 6.65 (m, 1H, C5HAr); 6.78 (m, 1H, C3HAr); 6.89 (m, 1H,
0
C4HAr); 7.10 (m, 1H, N3 H); 7.25 (m, 1H, C6HAr); 8.38 (s, 1H,
0
@C7H); 11.80 (s, 1H, N2 H). 13C NMR data, d, ppm (DMSO-d6):
21.19 C(Ac)
;
44.25C(9)
;
114.71 C(11)
;
116.06 C(3)
;
120.74C(1)
;
;
0
0
(s, 1H, N3 H); 11.78 (s, 1H, N2 H). 13C NMR,d, ppm (DMSO-d6):
121.06 C(5); 130.28 C(6); 132.95 C(4); 136.29 C(10); 152.23 C(7)
163.15 C(2); 172.42 C(8); 173.29 C(C@O)
116.05C(3); 119.14 C(5); 120.20 C(1); 125.05 C(12); 125.49 C(10,14)
127.12 C(6); 128.00 C(11,13); 131.20 C(4); 139.10 C(9); 140.15 C(7)
;
;
.
156.54 C(2); 175.70 C(8)
.
3.5. Bis[
propenyl)carbothioamide–
O]zinc(II)acetate, Zn(H2L)2 (III)
l
2-O(E)-2-[(2-hydroxyphenyl)methylene]hydrazine-N-(2-
3-O,N,S][acetate–
-O][aqua-
j
j
j-
3.7. Bis{
phenylcarbothioamide–
Zn2(CH3COO)2(H2L)2 (IV)
l
2-O[(E)-2-(2-[(hydroxyphenyl)methylene]hydrazine-N-
3-O,N,S][acetate–
-O]zinc(II)},
j
j
The synthesis was carried out analogously to complex II using
molar ratio M:L = 1:2 and Zn(NO3)2ꢀ6H2O as initial Zn salt. Decom-
position temperature >260 °C. Yield 73%. Anal. Calc. for
The synthesis was carried out analogously to complex II using
molar ratio Zn:H2L = 1:1. Decomposition temperature >260 °C.
Yield 89%. Anal. Calc. for C32H30N6O6S2Zn2: C 48.63; H 3.80; N
10.64; S 8.11. Found: C 48.73; H 3.75; N 10.75; S 8.15%. UV–Vis
C
22H24N6O2S2Zn: C, 49.44; H, 4.49; N, 15.73; S, 11.99. Found: C,
49.48; H, 4.52; N, 15.68; S, 12.02%. UV–Vis date,
, cmꢁ1 (DMF):
32360, shoulder (165); 30900 (157); 26650 (170). IR data,
cmꢁ1: 3230,
(NH); 3063, (@CH); 3015 (CH); 2985, asymmetric
vibrations (CH2)allyl; 1604, 1594, d, 1568, 1547, (C@N) and in-
plane deformation vibrations d(NH–CS–NH); 1470, 1438, 1412,
phenolic ring vibrations (PhH); 1348, 1312 (CS); 1275, 1254,
1203, (C–OPh); 1157, 1125, 1095, (NH–CS–NH); 1042, 1019,
(N–N); 993, 972, 940, 901, in-plane deformation vibrations
m
m
,
date,
(550). IR data,
(CH3Ac); 2818; 1632 (C@OAc); 1598, 1549, 1493
plane deformation vibrations d(NH–CS–NH); 1475, 1434, 1412,
1384, phenolic ring vibrations (PhH); 1326, 1301 (CS); 1202
(C–OPh); 1159, 1118 (NH–CS–NH); 1044, d, 1025 (N–N); 942,
m
, cmꢁ1 (DMF): 33760, shoulder (417); 31840 (423); 25960
m
m
m
m
, cmꢁ1: 3217, w,
m(NH); 3014
m(CHAr); 2918
m
m
m
m(C@N) and in-
m
m
m
m
m
m
m
m
m
m
907, 914 in-plane deformation vibrations d(CN); 852, 790, 740,
697, d, 682, 645, out-of-plane deformation vibrations d(CH); 564,
out-of-plane deformation vibrations of aromatic ring d(CHAr);
d(CH); 840, 801, 749, 655, out-of-plane deformation vibrations
d(CH); 613, 575, 557, 464, deformation vibrations d(CHallyl); 438,
m
(Zn–N); 285
m
(Zn–S). 1H NMR data, d, ppm (DMSO-d6): 3.90 (m,
418 m(Zn–N); 301 m(Zn–S). 1H NMR data, d, ppm (DMSO-d6): 1.92
2H, C9H2); 5.01–5.15 (dd, 2H, J = 10.0, 17.5 Hz, @C11H2); 5.86–
(s, 3H, CH3CO); 6.70 (m, 1H, C5HAr); 6.88 (t, 1H, J = 7.0 Hz, C4HAr);
6.97 (m, 1H, C3HAr); 7.22 (m, 3H, C11,12,13HAr); 7.36 (m, 1H,
C6HAr); 7.82 (d, 2H, J = 8.0 Hz, C10,14HAr); 8.61 (s, 1H, @C7H); 8.92
5.92 (m, 1H, @C10H); 6.64 (m, 1H, C5HAr); 6.78 (m, 1H, C3HAr);
0
6.89 (m, 1H, C4HAr); 7.11 (m, 1H, N3 H); 7.25 (m, 1H, C6HAr); 8.39
0
0
0
(s, 1H, @C7H); 11.80 (s, 1H, N2 H). 13C NMR data, d, ppm (DMSO-
(s, 1H, N3 H); 11.97 (s, 1H, N2 H). 13C NMR, d, ppm (DMSO-d6):
d6): 13C NMR, d, ppm (DMSO-d6): 44.25C(9); 114.70 C(11); 117.06
21.11C(Ac); 119.52C(10,14); 120.26 C(1); 120.79 C(3); 121.15C(5)
128.09 C(11,13); 131.08 C(6,12); 133.45 C(4); 141.51 C(9); 155.21
C(7); 168.40 C(2); 171.99 C(8); 173.31 C(C@O)
;
C(3); 120.68C(1); 121.09 C(5); 130.20 C(6); 132.86 C(4); 136.33 C(10)
;
152.16 C(7); 163.00C(2); 172.39 C(8)
.
.

S.I. Orysyk et al. / Inorganica Chimica Acta 382 (2012) 127–138
131
X-ray diffraction study, most likely due to formation of the hydro-
gen bonds N(3)–H(3N). . .N(2) and N(1)–H(1N)...O(2)(C@OAc) (Table 3,
Fig. 4). In the IR spectra of thiosemicarbazones B and C, the broad-
4. Results and discussion
4.1. Spectroscopic characterization
ened bands of stretching vibrations of m(OH) from phenyl rings at
3168 and 3156 cmꢁ1 are found. It may indicates the presence of
the intramolecular hydrogen bond between OH and C@N groups,
the existence of which has been confirmed by X-ray diffraction
(Tables 5 and 7).
The ligands A–C are characterized by the presence of thione–
thiol (H2L) and/or benzoid–quinoid (H3L) tautomerism (Scheme
1), which allows them to act both as monobasic, dibasic and as pol-
ybasic acid with ensuring of N-, S- and/or O-, N-, S-donor interac-
tion. In this case, the composition and structure of the complexes
formed depend on reaction conditions: pH, heating temperature
and time, ratio and concentration of the initial substances.
It has been found that reaction of thiourea derivatives A and
thiosemicarbazides B, C with Zn(II) ions in the acid media, where
ligands exist in thionic form and behave as monobasic acids with
coordination to the central metal ion in mono- or tridentate man-
ner, led to formation of complexes I–IV (Scheme 2). The location of
coordination bonds and the structure of the complexes were deter-
mined by comparing of IR, UV–Vis and 1H, 13C NMR spectra of the
ligands A–C and corresponding complexes I–IV.
IR-spectra of the complexes II–IV contain no
band due to the deprotonation of hydroxyl group, while the vibra-
tion frequency
(NH) is lower by 58, 49 or 123 cmꢁ1 in comparison
m(OH) absorption
m
with the spectra of uncoordinated ligands, which may be due to the
coordination to the metal ion via thioureide group and/or formation
of an intramolecular hydrogen bond. In according with the results of
X-ray diffraction study of the complexes I–IV, the decreasing of
m
(NH) frequencies can be explain by formation of the hydrogen
bonds N(6)H. . .N(5), N(3)H. . .N(2) b N(4)H. . .O(4), N(1)H. . .O(2) in the
complex I, N(9)H. . .O(4), N(11)H. . .O(3), N(3)H. . .O(13), N(5)H. . .O(12) in
the complex II, N(1)H. . .O(5), N(3)H. . .O(3), N(4)H. . .O(4), N(6)H. . .O(6)
in the complex IV. Besides, the IR spectra of the complexes contain
a set of low-intensity absorption bands of stretching vibrations
4.1.1. IR spectra
m
(@CH),
acetic acid molecules. The absence of absorption bands of stretching
vibrations
(S–H) in the range 2550–2590 cmꢁ1 indicates coordina-
m(CH)Py, m(CHz)allyl and symmetrical vibrations m(C–H) of
The high-frequency region of infrared spectra of thiourea (A)
and thiosemicarbazones (B, C) characterized by the presence of
absorption bands at 3243, 3291, 3340 cmꢁ1, related to stretching
m
tion of the ligands A–C in thionic tautomeric form.
vibrations
m
(NH) of thioureide group. The frequency of the second
It should be noted that coordination of acetic acid molecules to
the metal ion complicates the interpretation of the IR spectra of the
complexes I, II and IV in the frequency range 1630–1500 cmꢁ1
since the vibrations of carbonyl group (C@O), partially overlapped
peak is lower by 58 cmꢁ1 in comparison with the original ligand,
which may be due to the coordination of thiourea (A) to the metal
ion vis sulfur atom of the thioureide group and/or, as shown by
Scheme 2. Scheme of synthesis of the complex compounds.

132
S.I. Orysyk et al. / Inorganica Chimica Acta 382 (2012) 127–138
Fig. 1. IR spectra of the thiourea (A), thiosemicarbazones (B, C) and there complexes I–IV.
Fig. 2. UV–Vis spectrum of the thiosemicarbazones (B, C) and the complexes II–IV.

S.I. Orysyk et al. / Inorganica Chimica Acta 382 (2012) 127–138
133
Fig. 3. NMR 13C spectrum of the ligand C (a) and complex IV (b).
Table 2
Bond lengths and valence angles of the complex I.
0
0
Parameter
Parameter
O(3)–Zn(1)–O(1)
Value (AÅ, °)
Value (AÅ, °)
Zn(1)–O(3)
Zn(1)–O(1)
Zn(1)–S(2)
Zn(1)–S(1)
S(1)–C(1)
1.9437(19)
1.9516(18)
2.3451(8)
2.3588(8)
1.719(3)
1.725(3)
1.343(3)
1.313(3)
1.343(3)
1.310(3)
121.3(2)
96.63(8)
117.81(7)
105.80(6)
104.55(8)
117.91(6)
113.51(3)
119.6(2)
121.7(2)
118.67(19)
120.2(2)
118.5(2)
O(3)–Zn(1)–S(2)
O(1)–Zn(1)–S(2)
O(3)–Zn(1)–S(1)
O(1)–Zn(1)–S(1)
S(2)–Zn(1)–S(1)
N(3)–C(1)–N(1)
N(3)–C(1)–S(1)
N(1)–C(1)–S(1)
N(6)–C(10)–N(4)
N(4)–C(10)–S(2)
S(2)–C(10)
N(1)–C(1)
N(3)–C(1)
N(4)–C(10)
N(6)–C(10)
N(6)–C(10)–S(2)
with vibrations of d(NH–CS–NH) and
m(C@N) groups. By analyzing
the positions of mentioned absorption bands in the spectra of com-
plexes with uncoordinated ligands one can identify the absorption
bands of stretching vibrations
coordinated acetic acid molecules at 1630–1632 cmꢁ1. The lower
vibration frequency (C@O)Ac indicates the formation of the intra-
molecular hydrogen bond C@O. . .HN, which was confirmed later
by X-ray diffraction (Fig. 4).
m(C@OAc) of the carbonyl group of
m
Fig. 4. General view of the complex I molecule. The thermal ellipsoids are shown
with 30% probability. The dashed lines denote intramolecular hydrogen bonds.
In the IR spectrum of the complex I, some frequencies corre-
sponding to stretching vibrations of pyridine ring are lowered by
13–22 cmꢁ1 due to the participation of pyridine nitrogen atom in
the formation of six-membered pseudoheterocycles through the
hydrogen bonds N(3)–H(3N). . .N(2) and N(6)–H(6N). . .N(5) (Fig. 4).
of pyridine ring at 897–687 cmꢁ1 appear in the same region as
well. However, the absorption bands in the range 1143–
1194 cmꢁ1 also correspond to the stretching vibration
m(C@S) of
the thioureide group (–N–CS–N–) [29,30,36]. The value of these
frequencies in the spectra of the complexes increased by 17 cmꢁ1
(Fig. 1), indicating participation of the sulfur atom in coordination
to the central metal ion.
The low-frequency region of the IR spectrum of the complex I
contains intense absorption bands of the stretching vibrations
The identification of the m(C@S) absorption bands involves cer-
tain difficulties because of its partially overlapping with absorption
bands from another groups in the low-frequency region. The
absorption bands of other molecule fragments, e.g. out-of-plane
deformation vibrations d(–CH@CH2) of allyl fragment and d(CH)

134
S.I. Orysyk et al. / Inorganica Chimica Acta 382 (2012) 127–138
transfer transitions
p ?
p⁄Py and n ? p⁄, (C@NPy)/(C@S). When the
complex is formed, a 685–365 cmꢁ1 shift of these bands to the
low-frequency region is observed, which confirm the coordination
of the ligand A to the central metal ion.
The UV–Vis spectra of the thiosemicarbazones B and C are of the
same type and consist of absorption bands at 34200–33450,
32650–32470 and 30055–29360 cmꢁ1
, corresponding to the
intraligand n ? p⁄ transitions of the azomethine fragment (C@N)
and (C@S) of thioureide group (Fig. 2). The first band has a shoul-
der-like form. When the complexes are formed, a valuable shift
of these bands to the low-frequency region is observed, which indi-
cates participation of the above functional groups in coordination
to the central metal ion. It should be noted that the broad absorp-
tion bands at 28000, 26650 cmꢁ1 (II, III) and 25960–25100 cmꢁ1
(IV) correspond to charge transfers from ligand to metal
[S ? Zn], which is associated with the participation of the ligand
(C@S) group in coordination to the central metal ion with the for-
mation of a chelate metallocycle. In contrast to the complexes II–
IV, there is no charge transfer band [S?Zn] in the spectrum of
complex I, which is, most likely, due to the monodentate coordina-
tion of thiourea (A) in a non-chelate manner.
4.1.3. 1H and 13C NMR spectra
The comparative analysis of 1H NMR spectra of the complex I and
uncoordinated thiourea (A) showed the slight shift of all protons sig-
nals, mainly to the strong field direction by
D
d = ꢁ0.01 ppm (with
0
the exception of @C9H2,
D Dd = +0.01), in the
d = +0.02 and N1 H,
Fig. 5. Asymmetric unit of the complex II. The thermal ellipsoids for all nonhydro-
gen atoms are shown with 30% probability. The hydrogen atoms bonded to carbon
atoms were omitted for clarity.
spectrum I. In the 13C NMR spectrum of the complex I, the signals
of carbon atoms shift slightly in comparison with spectrum of unco-
ordinated thiourea both to the upfield and downfield (
D
d = ꢁ0.02
(C6), ꢁ0.13 (C4), ꢁ0.41 (C8), ꢁ0.29 ppm (C5);
D
d = +0.06 (C1), 0.25
(C2), +0.05 (C3), +0.03 (C9), +0.04 ppm (C7)). This indicates the pres-
ence of N–H. . .NPy hydrogen bonds both in thiourea and in the com-
plex I. In this case, the coordination of ligand only via the sulfur atom
of thioureide group does not affect the chemical shift of signals in 1H
and 13C NMR spectra. The presence of coordinated acetate anions in
the compound I is confirmed by appearance of intense singlet signal
in the upfield at 1.83 ppm (1H NMR) and signals of carbon atoms at
176.63 ppm (C@O) and 22.47 ppm (CH3) (13C NMR).
Table 3
Geometric parameters of the hydrogen bonds in the crystal structure of complex I.
D–H. . .A
d(D–H)
d(H. . .A)
d(D. . .A)
<(DHA)
N(1)–H(1N). . .O(2)
N(3)–H(3N). . .N(2)
N(4)–H(4N). . .O(4)
N(6)–H(6N). . .N(5)
0.83(3)
0.77(3)
0.83(3)
0.80(3)
1.93(3)
2.01(3)
1.94(3)
2.09(3)
2.757(3)
2.666(3)
2.747(3)
2.685(3)
171(3)
143(3)
165(3)
132(3)
In the complex compounds II and III, all proton signals (with the
m
(Zn–OAc) and m
(Zn–S) at 550 and 284 cmꢁ1, which confirms the
0
exception of N(2 )H,
Dd = +0.34 ppm) shift to the upfield, which is
typical for five- and six-membered chelate metallocycles. The pro-
tons signals from benzene rings in the positions 6, 4 and 5
coordination of ligand to metal.
The valuable changes are observed in the range 1350–1200 cmꢁ1
(Fig. 1), there the vibrations bands m(CS) and m(C–OPh) are located. In
(D
d = ꢁ0.71, ꢁ0.34, ꢁ0.19 ppm), as well as NH of thioureide group
the spectra of the complexes II–IV, the stretching vibration fre-
quency of mentioned bonds is lowered by 12–23 cmꢁ1, which indi-
cates their coordination to the metal ion. In contrast to I, besides
0
0
(N(3 )H,
D
d = ꢁ1.49; N(2 ) H,
Dd = +0.34 ppm) are most sensitive to
complex formation. In the 13C NMR spectra of the complexes II
and III, the strongest shift to the upfield corresponds to signals of
stretching vibrations
region of the IR spectra of II–IV are characterized by appearance of
stretching vibrations
(Zn–N) at 438/418 cmꢁ1. The bond vibrations
(Zn–O) in the IR spectra of II–IV cannot be identified because of
m
(Zn–S) at 285/301 cmꢁ1, the low-frequency
carbon atoms (C8,
D
d = ꢁ4.61; C2,
D
d = ꢁ3.91 (ꢁ4.16); C7,
D
d = ꢁ2.83), which are directly bonded to sulfur, oxygen and nitro-
m
gen, involved in the formation of the bonds Zn S, Zn–O and Zn N.
m
The downfield shift observed for the signals of carbon atoms C4
overlappingwith d(CH)allyl in thecase ofcompounds II and III or with
out-of-plane deformation vibrations d(CH)Ar of aromatic ring in the
case of IV.
(D Dd = +3.85 (+3.77)), located in the ortho-
d = +2.18 (+2.09))and C6 (
and para- positions referring to thiosemicarbazone substituent.
In the 1H NMR spectrum of complex IV, the most sensitive for
complex formation are protons signals of benzene ring at the posi-
Thus, comparison of the characteristic absorption bands of the
IR spectra of complexes and uncoordinated thiosemicarbazones
(B, C) allows one to conclude that in the complexes II–IV, the
ligand molecules are bonded to the central metal atom in a triden-
tate manner via oxygen atoms of the deprotonated OH group of
benzene ring, azomethine nitrogen atom (C@N) and sulfur of thio-
ureide group with the formation of five- and six-membered
metallocycles.
tions 6, 4 and 5 (
D
d = ꢁ0.75, ꢁ0.32, ꢁ0.16 ppm) as well as NH of
0
0
thioureide group (N(3 )H,
D
d = ꢁ1.14; N(2 )H,
Dd = +0.19 ppm). The
signals of benzene ring protons in the positions 10 and 14
(D
d = +0.218 ppm) are shifted to the downfield significantly. In
contrast, another pair of protons at the positions 11 and 13 are
shifted to the upfield (
d = ꢁ0.15 ppm). Signals, corresponding to
protons at carbon atoms 3, 7 and 12 are shifted slightly by
D
D
d = +0.05, +0.09 and ꢁ0.03 ppm, respectively.
4.1.2. UV–Vis spectra
In the 13C NMR spectrum of the complex IV (Fig. 3), most signals
The UV–Vis spectrum of thiourea (A) includes three absorption
of carbon atoms are shifted to the downfield (with the exception of
bands at 40560, 37400 and 34050 cmꢁ1 of the intraligand charge-
C8,
D
d = ꢁ3.71; C10 and C14
,
D
d = ꢁ5.97). In this case, a considerable

S.I. Orysyk et al. / Inorganica Chimica Acta 382 (2012) 127–138
135
shift to the downfield is observed for the signals of the atoms C2
d = +11.86) and C7
d = +15.06), which is typical for the
Table 4
Geometric parameters of the complex II.
(D
(D
0
0
formation of a covalent (Zn–O) and a donor-acceptor (Zn N) bond
Parameter
Parameter
Value (ÅA, °)
Value (AÅ, °)
[37].
Zn(1)–Zn(2)
Zn(3)–Zn(4)
Zn(1)–O(5)
3.1813(9)
3.1566(9)
1.991(3)
2.000(3)
2.069(3)
2.102(4)
2.4012(16)
1.990(3)
2.030(3)
2.051(3)
2.097(4)
O(5)–Zn(1)–O(2)
O(5)–Zn(1)–O(1)
O(2)–Zn(1)–O(1)
O(5)–Zn(1)–N(2)
O(2)–Zn(1)–N(2)
O(1)–Zn(1)–N(2)
O(5)–Zn(1)–S(1)
O(2)–Zn(1)–S(1)
O(1)–Zn(1)–S(1)
N(2)–Zn(1)–S(1)
O(3)–Zn(2)–O(1)
O(3)–Zn(2)–O(2)
O(1)–Zn(2)–O(2)
O(3)–Zn(2)–N(4)
O(1)–Zn(2)–N(4)
O(2)–Zn(2)–N(4)
O(3)–Zn(2)–S(2)
O(1)–Zn(2)–S(2)
O(2)–Zn(2)–S(2)
N(4)–Zn(2)–S(2)
O(10)–Zn(3)–O(8)
O(10)–Zn(3)–O(7)
O(8)–Zn(3)–O(7)
O(10)–Zn(3)–N(8)
O(8)–Zn(3)–N(8)
115.41(13)
100.05(14)
76.88(12)
102.80(13)
139.65(13)
84.45(14)
104.11(11)
99.44(10)
154.57(10)
82.59(12)
117.25(14)
98.37(14)
76.62(12)
95.81(14)
143.70(15)
84.52(14)
105.91(12)
100.25(10)
153.78(10)
83.34(12)
108.17(13)
103.83(15)
77.40(13)
101.68(13)
147.33(13)
82.92(15)
100.48(10)
82.19(13)
103.39(17)
98.03(18)
155.75(16)
146.26(11)
82.67(12)
4.2. X-ray diffraction study
Zn(1)–O(2)
Zn(1)–O(1)
4.2.1. Structure of complex I
Zn(1)–N(2)
Zn(1)–S(1)
The complex I crystallize in the monoclinic crystal system
(space group P21/c) with one molecule per asymmetric unit. The
central Zn(1) atom forms a strongly distorted tetrahedral ZnS2O2
environment with a valence angle range 96.63(8)–117.91(6)°.
The Zn–S and Zn–O bond lengths correlate well with the previously
published for the complexes with similar coordination of ligands
[38–40]. Both molecules of organic ligand coordinate in monoden-
tant manner via the sulfur atom of thioureide fragment. The
lengths of the C–S and C–N bonds do not allow determining the
tautomeric form of the ligand unambiguously (Table 2). However,
the sum of the adjacent valence angles around the atoms C(1)
(359.97(20)°) and C(10) (360.0(2)°) indicates their sp2 hybridiza-
tion, which together with the presence of objectively identified
hydrogen atoms on the nitrogen atoms of thiourea fragment makes
it possible to formally determine the form of coordinated ligands to
be thionic one. The pyridine and thiourea fragments are coplanar,
which is accounted for the presence of strong intramolecular
hydrogen bonds N(6)–H(6N). . .N(5) and N(3)–H(3N). . .N(2), producing
six-membered pseudoheterocycles (Fig. 4, Table 2). The mean devi-
ation from planes S(1)/C(1)/N(3)/N(1)/C(2)/N(2)/C(3)/C(4)/C(5)/C(6) and
S(2)/C(10)0/N(6)/N(4)/C(11)/N(5)/C(12)/C(13)/C(14)/C(15) is 0.0364 and
0.0720 ÅA, respectively. The solid angle between the above planes
is 5.00(10)°, which indicates coplanarity of the mentioned
fragments.
Zn(2)–O(3)
Zn(2)–O(1)
Zn(2)–O(2)
Zn(2)–N(4)
Zn(2)–S(2)
2.3669(15)
1.995(3)
2.035(3)
Zn(3)–O(10)
Zn(3)–O(8)
Zn(3)–O(7)
2.045(3)
Zn(3)–N(8)
Zn(3)–S(3)
2.124(4)
2.3741(16)
2.014(5)
2.024(3)
2.025(3)
Zn(4)–O(9)
Zn(4)–O(8)
Zn(4)–O(7)
Zn(4)–N(10)
Zn(4)–S(4)
2.079(4)
2.3780(16)
1.695(5)
1.692(5)
1.707(5)
1.696(5)
108.08(12)
146.88(11)
107.19(17)
78.09(13)
84.88(14)
105.53(14)
102.11(10)
S(1)–C(1)
S(2)–C(5)
S(3)–C(27)
S(4)–C(31)
O(7)–Zn(3)–N(8
)
O(10)–Zn(3)–S(3)
O(7)–Zn(3)–S(3)
O(9)–Zn(4)–O(8)
O(8)–Zn(4)–O(7)
O(8)–Zn(4)–N(10)
O(9)–Zn(4)–S(4)
O(7)–Zn(4)–S(4)
O(8)–Zn(3)–S(3)
N(8)–Zn(3)–S(3)
O(9)–Zn(4)–O(7)
O(9)–Zn(4)–N(10)
O(7)–Zn(4)–N(10)
O(8)–Zn(4)–S(4)
N(10)–Zn(4)–S(4)
Two acetic acid molecules are monodentate-coordinated to the
central zinc ion. In this case, the uncoordinated oxygen atom of
each of the carboxyl groups participates in the formation of the
Table 5
Geometric parameters of the hydrogen bonds for the complex II.
strong intramolecular hydrogen bonds N(1)–H(1N). . .O(2) and N(4)
–
H(4N). . .O(4) (Fig. 4, Table 3). The molecules of the complex I interact
to each other in the crystal structure mainly by weak Van der
Waals interactions.
D–H. . .A
d(D–H)
d(H. . .A)
d(D. . .A)
<(DHA)
N(1)–H(1N). . .O(10)#1
N(3)–H(3N). . .O(13)
N(5)–H(5N). . .O(12)
N(6)–H(6N). . .O(11)#1
N(7)–H(7N). . .O(5)#2
N(9)–H(9N). . .O(4)
0.89(3)
0.88(3)
0.87(3)
0.90(3)
0.85(3)
0.86(3)
0.83(3)
0.85(3)
0.79(4)
1.99(3)
1.88(3)
1.90(3)
1.90(3)
1.97(3)
1.81(3)
2.23(4)
2.00(3)
1.82(4)
2.843(5)
2.748(5)
2.762(6)
2.800(6)
2.790(5)
2.664(5)
3.013(5)
2.843(5)
2.571(5)
160(4)
169(4)
177(6)
173(5)
162(4)
172(5)
157(5)
170(5)
160(7)
As had been shown earlier [36], in contrast to Zn(II) ion, the li-
gand A coordinates to Pd(II) under similar conditions in a bidentate
manner with the formation of a six-membered metalla rings. It is
probable that utilizing another synthesis conditions (heating time,
initial zinc salts) can lead to formation of the complex with biden-
tate coordination of A as well.
N(11)–H(11N). . .O(3)
N(12)–H(12N). . .O(6)#2
O(9)–H(92O). . .O(13)#3
Symmetry elements used for the generation of symmetrically dependent atoms: #1
ꢁ x + 1, y + ½, ꢁz + ½; #2 ꢁ x + 1, y ꢁ ½, ꢁz + ½; #3 x ꢁ 1, y, z.
4.2.2. Structure of complex II
The asymmetric unit of the compound II contains two
molecules of binuclear complex compounds with the ratio metal:-
ligand = 1:1, in which the base of the distorted square-pyramidal
coordination environment of zinc ion is formed in all cases by
The values of the valence angles between the atom from the vertex
and the atoms from the base of the square-pyramidal environment
of zinc atoms are 98.03(18)–115.41(13)°, indicating a considerable
tetrahedral distortion of the coordination polyhedron.
the thioureide sulfur atom, imine nitrogen atom and two l
2-bridg-
ing phenyl oxygen atoms (Fig. 5). The vertices of the coordination
polyhedra of the zinc ions Zn(1), Zn(2) and Zn(3) are occupied by
monodentate-coordinated acetic acid molecules. In the case of
Zn(4) atom, the vertex of square pyramid is completed by the
coordination of water molecule. The lengths of the Zn–S, Zn–N
and Zn–O bonds in the molecule of the complex correspond to
published data for such compounds (Table 4) [25,41].
The S–Zn–N valence angles deviate from the ideal values and
are in range 82.19(13)–83.34(12)°, which is caused by the steric
influence of five-membered metallocycles (Table 4). The values of
In both molecules of the complex from the asymmetric unit, the
molecules of organic ligand are coordinated in the tridentate man-
ner in thionic form with conjugation of five- and six-membered che-
late metallocycles. The thionic form of coordinated ligand molecules
0
is confirmed by the values of C–S bond length (1.692(5)–1.707(5) ÅA)
on the one hand and by the presence of objectively identified hydro-
gen atoms on the nitrogen atoms of thiourea group on the other
hand. The five-membered metallocycles Zn(1)/S(1)/C(1)/N(1)/N(2)
,
Zn(2)/S(2)/C(5)/N(3)/N(4), Zn(3)/S(3)/C(27)/N(7)/N(8) and Zn(4)/S(4)/C(31)
/
N(9)/N(10) are planar with a mean deviation from planes of 0.0488,
0
l
O–Zn–
l
O angles are in turn 76.62(12)–78.09(13)°, which is due
0.0625, 0.0747 and 0.0975 ÅA, respectively. The six-membered
to the mutual repulsion of zinc ions. The Zn(1)–Zn(2) and Zn(3)
–
metallocycles Zn(1)/O(1)/C(4)/C(3)/C(2)/N(2)
,
Zn(2)/O(2)/C(8)/C(7)/C(6)
/
/
0
Zn(4) distances in molecules are 3.1813(9) and 3.1569(9) ÅA, which
are much smaller than the sum of Van der Waals radii (ꢃ4.5 ÅA).
N(4) Zn(3)/O(7)/C(30)/C(29)/C(28)/N(8) and Zn(4)/O(8)/C(34)/C(33)/C(32)
,
0
N(10) have an envelope conformation with dihedral angles of

136
S.I. Orysyk et al. / Inorganica Chimica Acta 382 (2012) 127–138
4.2.3. Structure of complex IV
In contrast to the compound II, crystal structure of the indepen-
dent IV contains one molecule of binuclear zinc complex. The zinc
atoms Zn(1) and Zn(2), as in the case of the compound II, form a dis-
torted square-pyramidal coordination environment of ZnO3NS,
whose base contains a thioureide sulfur atom, and imine nitrogen
atom and two
l
2-bridging phenyl oxygen atoms. The monoden-
tate-coordinated acetic acid molecules are in both cases (Zn(1)
and Zn(2)) at the vertices of the pyramid (Fig. 6). It has to be men-
tioned that similar binuclear Zn complex with 2,4-dihydroxybenz-
aldehyde 4-phenyl thiosemicarbazone was synthesized by Tan
et al. [25] using zinc chloride as a starting metal salt. The main
structural difference between complex IV and mentioned com-
pound is coordination environment of Zn in vertical direction. In
the case of complex, reported by Tan et al. vertical positions in
the square-pyramidal coordination environment of Zn occupied
by chlorine anions, which cause a slight influence on molecular
structure. The dihedral angles between pyramidal bases increasing
from 43.3° in the case of IV to 49.8° for earlier reported compound.
This effect can be explained by repulsion effect between two chlo-
rine anions.
The atoms Zn(1) and Zn(2) are at distances of 0.5668(6) and
0
0.5288(6) ÅA from the planes of the bases of their coordination
polyhedra O(1)/O(2)/N(2)/S(1) and O(1)/O(2)/N(4)/S(2). The solid angle
between the above planes is 43.22(14)°. The distance Zn(1)
–
0
Zn(2) = 3.174(2) ÅA as well as other linear and angular characteristics
of the coordination environment of zinc ions are in agreement with
the analogous parameters of the compound II (Table 6). The mole-
cules of the ligands are coordinated, as in the case of the compound
II, in a tridentate cyclic manner with the formation of conjugate
five- and six-membered metallocycles. Formally, the molecules of
the ligands are coordinated in a thionic tautomeric form, as evi-
denced by the presence of objectively identified hydrogen atoms
on the nitrogen atoms bonded to the (CS) group. At the same time,
the C(1)–S(1) and C(5)–S(2) bonds are somewhat slightly longer than
those in the complex II (Tables 4 and 6), indicating a delocalization
of electron density between the C–S and C–N bonds. The five-
Fig. 6. General view of the complex IV molecule. The thermal ellipsoids are shown
with 30% probability.
Table 6
Geometric parameters of the molecule of IV.
0
0
Parameter
Parameter
Value (AÅ, °)
Value (AÅ, °)
Zn(1)–Zn(2)
Zn(1)–O(5)
3.174(2)
2.006(4)
2.034(3)
2.053(4)
2.115(4)
2.398(2)
2.000(5)
2.008(4)
2.085(3)
2.164(4)
2.333(2)
1.716(5)
1.735(6)
109.78(14)
101.90(15)
78.23(13)
99.93(15)
O(2)–Zn(1)–N(2)
O(1)–Zn(1)–N(2)
O(5)–Zn(1)–S(1)
O(2)–Zn(1)–S(1)
O(1)–Zn(1)–S(1)
N(2)–Zn(1)–S(1)
O(3)–Zn(2)–O(2)
O(3)–Zn(2)–O(1)
O(2)–Zn(2)–O(1)
O(3)–Zn(2)–N(4)
O(2)–Zn(2)–N(4)
O(1)–Zn(2)–N(4)
O(3)–Zn(2)–S(2)
O(2)–Zn(2)–S(2)
O(1)–Zn(2)–S(2)
N(4)–Zn(2)–S(2)
147.88(15)
84.09(15)
108.16(12)
98.87(11)
148.79(12)
82.70(12)
100.05(17)
108.10(17)
78.07(13)
99.97(17)
83.95(14)
148.79(15)
107.32(15)
151.12(12)
101.46(11)
82.44(12)
Zn(1)–O(2)
Zn(1)–O(1)
Zn(1)–N(2)
Zn(1)–S(1)
membered metallocycles Zn(1)/N(2)/N(1)/C(1)/S(1) and Zn(2)/N(4)
/
Zn(2)–O(3)
N(3)/C(5)/S(2) are planar with a mean deviation from planes of
Zn(2)–O(2)
0
Zn(2)–O(1)
0.0654 and 0.0494 ÅA, respectively.
Zn(2)–N(4)
Zn(2)–S(2)
The six-membered metallocycles Zn(1)/O(1)/C(4)/C(3)/C(2)/N(2)
and Zn(2)/O(2)/C(8)/C(7)/C(6)/N(4) have an envelope conformation
with dihedral angles of 17.9(2)° and 26.8(2)°, respectively. The
S(1)–C(1)
S(2)–C(5)
dihedral angle between the planes containing the atoms S(1)/C(1)
N(1)/N(2)/C(2)/C(3)/C(4)/O(1)/C(21)/C(22)/C(23)/C(24) and S(2)/C(5)/N(3)
/
/
O(5)–Zn(1)–O(2)
O(5)–Zn(1)–O(1)
O(2)–Zn(1)–O(1)
O(5)–Zn(1)–N(2)
N(4)/C(6)/C(7)/C(8)/O(2)/C(9)/C(10)/C(11)/C(12) is 48.06(12)°, which cor-
responds to the conformation of one of the molecules of the com-
pound II. The molecules of the complex in the crystal structure of
IV form a branched network of N–H. . .O hydrogen bonds, which
stabilize the structure (Fig. 7, Table 7).
20.1(2)°, 22.2(2)°, 20.8(2)° and 20.2(2)°, respectively. Besides, the
molecules of complexes contain several almost planar fragments:
S(1)/C(1)/N(1)/N(2)/C(2)/C(3)/C(4)/O(1)/C(18)0/C(19)/C(20)/C(21) (plane A,
The formation of zinc complexes such as II and IV is fairly typ-
ical for the ligands containing a ‘‘rigid’’ donor center (in these cases
oxygen atoms of phenoxyl group and acetic acid hydroxyl). As is
known, the appearance of ‘‘rigid’’ oxygen donor atoms in the coor-
dination sphere of the central ion makes it coordinatively unsatu-
rated, which may result in the formation of heteroligand and
polynuclear complexes, in which the central ion has the coordina-
tion number 5 or 6, as occurred in this particular case.
mean deviation from plane: 0.0552 ÅA), S(2)/C(5)/N(3)/N(4)/C(6)/C(7)
/
C(8)/O(2)/C(9)/C(10)/C(11)/C(12) (plane B, mean deviation from plane:
0
0.0590 ÅA),
S(3)/C(27)/N(7)/N(8)/C(28)/C(29)/C(30)/O(7)/C(42)/C(43)/C(44)
/
/
0
C(45) (plane C, mean deviation from plane: 0.0471 ÅA), S(4)/C(31)/N(9)
N(10)/C(32)/C(33)/C(34)/O(8)/C(35)/C(36)/C(37)/C(38) (plane D, mean devia-
0
tion from plane: 0.0330 ÅA). The dihedral angles between the planes
A/B and C/D are 64.95(10)° and 46.12(12)°, respectively, which may
be due to the different mode of intermolecular interactions of
fragments.
The asymmetric unit of the compound II contains an acetate an-
ion, which compensates the charge of one of the molecules and is
strongly bonded to one of the molecules of complexes by N–H. . .O
hydrogen bonds, forming a six-membered ring (Fig. 5, Table 5). In
the crystal structure, the molecules of the complex are bonded to a
network by strong; mainly N–H. . .O hydrogen bonds (Table 5).
5. Conclusions
Thus, we have reported the synthesis and structure investiga-
tion of novel Zn(II) complexes with different coordination mode
of thiourea and thiosemicarbazide derivatives. It has been shown
that in above synthesis conditions two molecules of ligand (A)

S.I. Orysyk et al. / Inorganica Chimica Acta 382 (2012) 127–138
137
Fig. 7. Packings of the compound IV. Projection along the z axis. The hydrogen bonds are denoted by dashed lines.
Table 7
in which two metal ions are bonded by the bridging oxygen of phe-
noxyl group (Figs. 5 and 6).
Geometric parameters of the hydrogen bonds for the complex IV.
X-ray diffraction study of II and IV showed that the central zinc
atom forms a square pyramid coordination geometry, whose verti-
ces are formed by three oxygen atoms, azomethine group nitrogen
and thioureide sulfur. The two oxygen atoms belonging to the
deprotonated phenoxyl group, as well as nitrogen and sulfur make
up the base of the pyramid, and acetic acid oxygen is at the vertex
of the formed pyramid.
At the component ratio M:L = 1:1, we have obtained a mononu-
clear zinc complex III, in which two ligand molecules form a dis-
torted octahedron, whose base consists of thioureide sulfur
atoms and deprotonated phenoxyl group oxygen, and at the verti-
ces are azomethine group nitrogen atoms (Scheme 2).
D–H. . .A
d(D–H)
d(H. . .A)
d(D. . .A)
<(DHA)
N(1)–H(1N). . .O(5)#1
N(3)–H(3N). . .O(3)#2
N(3)–H(3N). . .O(4)#2
N(5)–H(5N). . .O(4)#2
N(6)–H(6N). . .O(6)#1
0.79(5)
0.84(5)
0.84(5)
0.88(6)
0.82(3)
2.10(5)
2.17(5)
2.47(6)
2.08(6)
1.92(3)
2.873(6)
2.950(7)
3.174(10)
2.956(9)
2.743(6)
165(6)
153(5)
142(5)
169(6)
175(6)
Symmetry elements used for the generation of symmetrically dependent atoms: #1
ꢁx, ꢁy, ꢁz + 1, #2 x, ꢁy + ½, z ꢁ ½.
coordinates to the zinc ion in monodentate manner via the sulfur
atom of thioureide group. The zinc ion forms distorted tetrahedral
coordination geometry, consist of two sulfur atoms of thioureide
group and two oxygen atoms of acetate ions (Fig. 4). It has been
shown that the heating of reaction mixture and oxygen affinity
of zinc ions did not allow the potentially bidentate ligand A to be
coordinated additionally by the nitrogen atom of pyridine ring.
In contrast to thiourea A, the thiosemicarbazones B and C be-
have as monobasic acids with coordination to the metal ion in a tri-
dentate manner via the oxygen atom of the deprotonated phenoxyl
group, thioureide sulfur and azomethine nitrogen. We have syn-
thesized two types of complexes (II, IV). At the component ratio
M:L = 1:1, binuclear zinc complexes (II and IV) have been obtained,
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.ica.2011.10.027.
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