Unusual template condensation of benzophenone thiosemicarbazones and salicylaldehydes with nickel(II)

Article abstract of DOI:10.1080/00958971003628868

Reactions of 5-R-2-hydroxybenzophenone S-methylthiosemicarbazones (R: H, Br, Cl) and 2-hydroxy-benzaldehydes in the presence of NiCl₂ yielded template complexes by chelating with two of the ligands in the monoanionic form. The N₄O

Full text of DOI:10.1080/00958971003628868

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Unusual template condensation of
benzophenone thiosemicarbazones and
salicylaldehydes with nickel(II)
Yasemın Daşdemır Kurt a & Bahrı Ülküseven a
a Department of Chemistry, Istanbul University, 34320 Avcılar,
Istanbul, Turkey
Version of record first published: 16 Feb 2010.
To cite this article: Yasemın Daşdemır Kurt & Bahrı Ülküseven (2010): Unusual template
condensation of benzophenone thiosemicarbazones and salicylaldehydes with nickel(II), Journal of
Coordination Chemistry, 63:5, 828-836
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Journal of Coordination Chemistry
Vol. 63, No. 5, 10 March 2010, 828–836
Unusual template condensation of benzophenone
thiosemicarbazones and salicylaldehydes with nickel(II)
_
_
¨
YASEMIN DASꢀ DEMIR KURT* and BAHRI ULKUSEVEN
_
¨
Department of Chemistry, Istanbul University, 34320 Avc|lar, Istanbul, Turkey
(Received 4 September 2009; in final form 12 October 2009)
Reactions of 5-R-2-hydroxybenzophenone S-methylthiosemicarbazones (R: H, Br, Cl) and
2-hydroxy-benzaldehydes in the presence of NiCl2 yielded template complexes by chelating with
two of the ligands in the monoanionic form. The N4O2 complexes of the thiosemicarbazones
show distorted-octahedral geometry around nickel(II). The compounds were characterized
by elemental analysis, conductivity and magnetic measurements, UV-Vis, IR, 1H-NMR, and
mass spectra. Crystal structure of bis-N1-(2-hydroxy-5-bromo-phenyl)(phenyl)methylene-N4-
(2-hydroxy-phenyl)methylene-S-methyl-thiosemicarbazidato-Ni(II)
single-crystal X-ray diffraction.
was
determined
by
Keywords: Thiosemicarbazone; Benzophenone; Template condensation; N4O2 complex;
X-ray crystal structure
1. Introduction
Thiosemicarbazones and their metal complexes have a variety of biological activities
ranging from antitumor, anticonvulsant, antifungal, antibacterial, antimicrobial, and
antiviral activities [1–3]. Thiosemicarbazones are also used in the determination of trace
metals in biological and pharmaceutical samples [4]. Because of these properties,
transition metal complexes of thiosemicarbazone derivatives have been intensively
studied in view of their structural chemistry and biological potential.
Thiosemicarbazones can be mono-, bi-, or tridentate ligands coordinating the metal
through sulfur, azomethine nitrogen, and heteroatom of the condensed aldehyde
or ketone [5–7]; bis-thiosemicarbazone derivatives can be tetradentate [4, 8]. Some
tetradentate thiosemicarbazones have been synthesized by metal-directed condensation
of thiosemicarbazones with carbonyl compounds. The template reaction
of S-alkylthiosemicarbazones involve condensation of the thioamide (N4H2) of
S-alkylthiosemicarbazone and carbonyl of an aldehyde or ketone in the presence
of metal ion; the template complexes can have N4, N3O, or N2O2 binding systems
[9–11]. To synthesize N2O2-type template complexes, Fe(III) [12, 13], Co(II) [14, 15],
*Corresponding author. Email: dasdemir@istanbul.edu.tr
Journal of Coordination Chemistry
ISSN 0095-8972 print/ISSN 1029-0389 online ꢁ 2010 Taylor & Francis
DOI: 10.1080/00958971003628868

Nickel(II) thiosemicarbazones and salicylaldehydes
829
S
2
H3C
N
R1
1
b
4
1
c
N
N
R3
2
R1
a
R
R2
O
d
g
3
R
1
O
R2
HO
O
e
4
Ni
2
N
2
+
2
+
N H
NiCl2
2
f
2
R3
N
–2HCl, –2H2O
R1
4
j
N
S
CH3
N
h
i
N
CH3
S
Figure 1. Template reaction scheme. Thiosemicarbazones, R1/R2: H/H (L1); Br/OH (L2); Cl/OH (L3), and
complexes, R1/R2/R3: H/H/H (1); H/H/Br (2); Br/OH/H (3); Br/OH/Br (4); Cl/OH/H (5); and Cl/OH/Br (6).
Ni(II) [16, 17], Cu(II) [18, 19], Zn [20, 21], Pd(II) [22], UO2(II) [23], and VO(II) [24, 25]
were used.
Herein, we report the first N4O2-type template complexes of nickel(II) in octahedral
geometry synthesized by chelating with two monoanionic benzophenone thiosemicar-
bazones having ONN donor sets and 2-hydroxy-benzaldehydes. The ligands and 1 : 2
template compounds (figure 1) were characterized by elemental analysis, conductivity
1
and magnetic measurements, UV-Vis, IR, H-NMR, and mass spectra. The crystal
structure of 3 was determined by single-crystal X-ray diffraction.
2. Experimental
2.1. Chemicals and apparatus
All chemicals were reagent grade and used as purchased. Analytical data were obtained
with a Thermo Finnigan Flash EA 1112 analyzer and Unicam Solar 929 atomic
absorption spectrometer. IR spectra of the compounds were recorded on KBr pellets
with a Mattson 1000 FT-IR spectrometer. UV-Vis spectra were performed on an
1
ATI-Unicam UV-Vis spectrometer UV2 Series. H-NMR spectra were recorded on
a Varian UNITY INOVA-500 MHz spectrometer relative to SiMe4 using deuterated
DMSO-d6 as solvent. The APCI-MS analyses were carried out in positive and negative
ion modes using a Thermo Finnigan LCQ Advantage MAX LC/MS/MS. Molar
conductivities were measured using a digital CMD 750 conductivity meter. Magnetic
measurements were carried out at room temperature by the Gouy technique with an
MK I model device obtained from Sherwood Scientific.
2.2. Crystallographic analyses
A red, platelet crystal of C44H34Br2N6NiO4S2 having dimensions 0.40 ꢀ 0.20 ꢀ 0.10 mm
was mounted on a glass fiber. The diffraction data was collected on a Rigaku RAXIS
˚
RAPID imaging plate area detector with graphite-monochromated Mo-Ka (0.7107 A)
radiation at 294 K. The data were corrected for Lorentz and polarization effects.
An empirical absorption correction was applied, which resulted in transmission factors
ranging from 0.63 to 1.00. The molecular and crystal structures were solved by direct
methods using SIR92 [26, 27]. Hydrogens were refined using the riding model and

¨
Y.D. Kurt and B. Ulkuseven
¨
830
non-hydrogen atoms were refined anisotropically. All calculations were performed
using the Crystal Structure crystallographic software package [28, 29].
2.3. Synthesis of benzophenone thiosemicarbazones
The S-methylthiosemicarbazones, L1, L2, and L3, were prepared with small
modifications of general methods [30, 31].
Benzophenone S-methylthiosemicarbazone (L1): benzophenone thiosemicarbazone
(0.76 g, 3 mmol) was dissolved in THF (8 mL) at 60ꢁC on a water bath. To the
solution, methyl iodide (0.23 mL, 3.6 mmol) was added and the mixture was allowed to
stand at room temperature for 24 h. The precipitated hydroiodide salt was filtered off
and washed with cold diethyl ether (5 mL). The colorless product was dissolved in 5 mL
alcohol by heating and neutralized with a sufficient amount of aqueous NaHCO3
solution (10%, w/w). The precipitate was collected by filtration and washed with 10 mL
portions of water and diethylether, respectively. The final product was recrystallized
from ethanol. Yield 0.48 g (60%).
L2 and L3 were synthesized by a similar procedure. The analytical, physical, UV-Vis
[ꢀmax, nm (log ꢁ), in DMF], FT-IR (KBr, cmꢂ1), 1H-NMR (DMSO-d6, 500 MHz, 25ꢁC,
ꢂ ppm), and (þc APCI)-MS (m/z, %) data of the ligands were given as follows.
L1: yield 0.48 g (60%), m.p. 134.5ꢁC. Anal. Calcd for C15H15N3S (%): C, 66.88; H, 5.61;
N, 15.60; S, 11.90. Found (%): C, 66.75; H, 5.52; N, 15.49; S, 11.83. UV-Vis: 240 (4.38),
309 (4.39). FT-IR: ꢃ(NH2) 3472, 3287, ꢂ(NH2) 1639, ꢃ(C¼N1) 1602, ꢃ(N2 ¼C) 1589.
1H-NMR: 7.63 (dd, 1H, e), 7.46–7.30 (m, 7H, c–j), 7.24 (dd, 1H, b), 7.18 (dd, 1H, a),
6.88, 6.64 (cis/trans ratio: 3/2, s, 2H, NH2), 2.31, 2.08 (cis/trans ratio: 2/3, s, 3H,
S-CH3). MS m/z (%): [M]þ, 270.09 (100); [M þ H]þ, 271.11 (18.77); [M þ 2H]þ, 272.10
(5.07); [Mꢂ(ꢂN¼C(SCH3)ꢂNH2)]þ, 180.19 (4.74).
L2: yield 0.58 g (75%), m.p. 137ꢁC. Anal. Calcd for C15H14BrN3OS (%): C, 49.46; H,
3.87; N, 11.54; S, 8.80. Found (%): C, 49.38; H, 3.94; N, 11.48; S, 8.71. UV-Vis: 242
(4.34), 306 (4.26). IR: ꢃ(OH) 3312, ꢃ(NH2) 3466, 3442, ꢂ(NH2) 1634, ꢃ(C¼N1) 1601,
1
ꢃ(N2 ¼ C) 1592. H-NMR: 10.28, 9.93 (cis/trans ratio: 2/1, s, 1H, 2-OH), 7.63 (dd, 1H,
e), 7.47–7.30 (m, 5H, f–j), 7.00 (s, 2H, NH2), 7.03 (dd, 1H, c), 6.87 (t, 1H, b), 2.34, 2.21
(cis/trans ratio: 3/2, s, 3H, S-CH3). MS m/z (%): [M]þ, 364.01 (99.09); [M þ H]þ, 365.05
(18.66); [M þ 2H]þ, 365.98 (100); [Mꢂ(ꢂN¼C(SCH3)ꢂNH2)]þ, 274.17 (1.41).
L3: yield 0.53 g (55%), m.p. 169ꢁC. Anal. Calcd for C15H14ClN3OS (%): C, 56.33; H,
4.41; N, 13.14; S, 10.03. Found (%): C, 56.26; H, 4.26; N, 12.94; S, 9.82. UV-Vis: 242
(4.47), 306 (4.45). IR: ꢃ(OH) 3317, ꢃ(NH2) 3463, 3441, ꢂ(NH2) 1635, ꢃ(C¼N1) 1604,
1
ꢃ(N2¼C) 1594. H-NMR: 10.26, 9.91 (cis/trans ratio: 2/1, s, 1H, 2-OH), 7.63 (dd, 1H,
e), 7.45-7.28 (m, 5H, f–j), 7.00 (s, 2H, NH2), 6.93 (d, 1H, c), 6.90 (t, 1H, b), 2.34, 2.21
(cis/trans ratio: 3/2, s, 3H, S-CH3). MS m/z (%): [M]þ, 320.06 (100); [M þ H]þ, 321.08
(18.32); [M þ 2H]þ, 322.05 (38.72); [Mꢂ(ꢂN¼C(SCH3)ꢂNH2)]þ, 230.23 (1.20).
2.4. Synthesis of complexes
Complex 1: NiCl2 ꢃ 6H2O (0.24 g, 1 mmol) was dissolved in absolute ethanol (10 mL)
and then 1.5 mL of ortho-formic ester was added to the solution. The solution was

Nickel(II) thiosemicarbazones and salicylaldehydes
831
allowed to stand at room temperature for 24 h, after which a mixture of L1 (0.27 g,
1 mmol) and salicylaldehyde (0.11 mL, 1 mmol) in absolute ethanol (10 mL) was added
dropwise. The reaction mixture was stirred vigorously for 1 h, and then the solvent was
reduced to half of its volume under vacuum. After standing at room temperature for 1
week, the resulting blackish-green precipitates were filtered off, washed with a mixture
of ethanol/ether (1 : 1, 10 mL), and dried in vacuo over P2O5. Yield: 0.20 g (25%).
The nickel(II) templates (2–6) were prepared by the same synthesis. The colors, yield
(%), m.p. (ꢁC), ꢄeff value (BM), molar conductivity (ohmꢂ1 cm2 molꢂ1, in 10ꢂ3 M DMF),
elemental analysis and spectroscopic data of the complexes were given as follows.
Compound 1: Blackish-green, 25, 251, 2.87, 0.04. Anal. Calcd for C44H36N6NiO2S2
(%): C, 65.76; H, 4.52; N, 10.46; S, 7.98; Ni, 7.30. Found (%): C, 65.61; H, 4.52; N,
10.32; S, 7.78; Ni, 7.21. UV-Vis: 241 (4.77), 313 (4.51), 355 (4.56), 488 (4.36), 762
(2.78). IR: ꢃ(C¼N1, N2¼C, N4¼C) 1616, 1585, 1555. MS m/z (%): [M]þ, 803.81 (61.40);
[M ꢂ H]þ,
802.80
(100);
[M þ H]þ,
804.82
(10.07);
(59.66);
[M þ 2]þ,
805.71
(24.30);
[Mꢂ(CH3SH2)]þ,
754.65
{Mꢂ[HOC6H4CH¼NꢂC(SCH3)
¼NꢂN¼C(C6H5)2]}þ,
430.08
(26.85),
{Mꢂ[HOC6H4ꢂCH¼NꢂC(SCH3)
¼NꢂN¼C(C6H5)2] þ Ni}þ, 373.90 (16.89).
Compound 2: Dark red, 15, 249, 3.07, 0.01. Anal. Calcd for C44H34Br2N6NiO2S2 (%):
C, 54.97; H, 3.56; N, 8.74; S, 6.67; Ni, 6.10. Found (%): C, 54.81; H, 3.61; N, 8.64; S,
6.53; Ni, 6.16. UV-Vis: 239 (5.12), 307 (4.89), 355 (4.91), 498 (4.78), 762 (2.84). IR:
ꢃ(C¼N1, N2¼C, N4¼C) 1612, 1582, 1564. MS m/z (%): [M]þ, 961.66 (52.97); [M ꢂ H]þ,
960.63 (100); [M þ H]þ, 962.63 (76.04); [M þ 2H]þ, 963.62 (34.74); [Mꢂ(CH3SH2)]þ,
912.64 (2.06); {Mꢂ[BrC6H3(O)ꢂCH¼NꢂC(SCH3)¼NꢂN¼C(C6H5)2]}þ, 510.09
(47.31); {Mꢂ[BrC6H3(O)ꢂCH¼NꢂC(SCH3)¼NꢂN¼C(C6H5)2]
þ
Ni}þ, 451.99
(30.77).
Compound 3: Brick red, 42, 254, 2.86, 0.01. Anal. Calcd for C44H34Br2N6NiO4S2 (%):
C, 53.20; H, 3.45; N, 8.46; S, 6.46; Ni, 5.91. Found (%): C, 53.09; H, 3.38; N, 8.23; S,
6.34; Ni, 5.75. UV-Vis: 241 (5.09), 312 (4.83), 330 (4.84), 466 (4.60), 762 (3.07). IR:
ꢃ(OH) 3435, ꢃ(C¼N1, N2¼C, N4¼C) 1609, 1578, 1559. MS m/z (%): [M]þ, 993.72
(13.41); [M ꢂ H]þ, 992.70 (22.85); [M þ H]þ, 994.63 (19.81); [Mꢂ(CH3SH2)]þ, 946.62
(9.02); {Mꢂ[ꢂOC6H4ꢂCH¼NꢂC(SCH3)¼NꢂN¼C(C6H5)(HOC6H3Br)]}þ, 526.11
(31.98);
{Mꢂ[HOC6H4ꢂCH¼NꢂC(SCH3)¼NꢂN¼C(C6H5)(HOC6H3Br)] þ Ni
þ Hþ}þ, 470.00 (100).
Compound 4: Brick red, 17, 4350, 2.93, 0.01. Anal. Calcd for C44H32Br4N6NiO4S2
(%): C, 45.91; H, 2.80; N, 7.30; S, 5.57; Ni, 5.10. Found (%): C, 45.74; H, 2.70; N, 7.13;
S, 5.46; Ni, 5.03. UV-Vis: 241 (5.01), 308 (4.67), 334 (4.68), 480 (4.48), 762 (2.85).
IR: ꢃ(OH) 3435, ꢃ(C¼N1, N2¼C, N4¼C) 1610, 1583, 1557. MS m/z (%): [M]þ,
1151.44 (15.81); [M ꢂ H]þ, 1150.45 (29.04); [M þ H]þ, 1152.38 (25.64);
[Mꢂ(CH3SH2)]þ, 1102.39 (2.04); {Mꢂ[HOC6H3(Br)ꢂCH¼NꢂC(SCH3)¼NꢂN
¼C(C6H5)(HOC6H3Br)]}þ, 603.96 (40.62); {Mꢂ[HOC6H3(Br)ꢂCH¼NꢂC(SCH3)
¼NꢂN¼C(C6H5)(HOC6H3Br)]þNi þ Hþ}þ, 547.90 (100).
Compound 5: Brick red, 35, 258.5, 2.83, 0.02. Anal. Calcd for C44H34Cl2N6NiO4S2 (%):
C, 58.43; H, 3.79; N, 9.29; S, 7.09; Ni, 6.49. Found (%): C, 58.32; H, 3.63; N, 9.11; S,
6.90; Ni, 6.39. UV-Vis: 242 (5.02), 311 (4.78), 333 (4.80), 468 (4.57), 763 (2.78). IR:
ꢃ(OH) 3441, ꢃ(C¼N1, N2¼C, N4¼C) 1616, 1578, 1558. MS m/z (%): [M]þ, 904.75 (100);

¨
Y.D. Kurt and B. Ulkuseven
¨
832
[M ꢂ H]þ, 903.80 (45.74); [M ꢂ 2H]þ, 902.76 (84.24); [M þ H]þ, 905.76 (50.51);
[M þ 2H]þ, 906.73 (50.88); [Mꢂ(CH3SH2)]þ, 854.86 (2.14); {Mꢂ[HOC6H4ꢂCH¼N
ꢂC(SCH3)¼NꢂN¼C(C6H5)(HOC6H3Cl)]}þ, 480.11 (59.76); {Mꢂ[ꢂOC6H4ꢂCH¼N
ꢂC(SCH3)¼NꢂN¼C(C6H5)(HOC6H3Cl)]þNi}þ, 423.25 (46.61).
Compound 6: Bright black, 25, 307, 2.95, 0.01. Anal. Calcd for C44H32Br2Cl2N6NiO4S2
(%): C, 49.75; H, 3.04; N, 7.91; S, 6.04; Ni, 5.53. Found (%): C, 49.72; H, 2.98; N, 7.82;
S, 5.87; Ni, 5.46. UV-Vis: 240 (4.90), 308 (4.62), 331 (4.63), 480 (4.43), 762 (2.81). IR:
ꢃ(OH) 3426, ꢃ(C¼N1, N2¼C, N4¼C) 1608, 1582, 1562. MS m/z (%): [M]þ, 1062.42
(100); [M ꢂ 1]þ, 1061.41 (42.81); [M þ 1]þ, 1063.43 (53.51); [Mꢂ(CH3SH2)]þ, 1013.37
(4.75); {Mꢂ[HOC6H3(Br)ꢂCH¼NꢂC(SCH3)¼NꢂN¼C(C6H5)(HOC6H3Cl]}þ, 501.94
(67.50); {Mꢂ[ꢂOC6H3(Br)ꢂCH¼NꢂC(SCH3)¼N(C6H5)(HOC6H3Cl)]þNi}þ, 560.32
(72.24).
3. Results and discussion
3.1. Physical properties
5-(H/Br/Cl)-2-hydroxybenzophenone S-methylthiosemicarbazones are in the form
of powder crystals and soluble in methanol, ethanol, and chlorinated hydrocarbons.
Metal-directed condensation of the thiosemicarbazones with aldehydes gave stable
compounds in a few minutes, but crystals of the products were obtained from the
mother liquor after 1 week at room temperature.
The thiosemicarbazones, L1, L2, and L3, gave asymmetrical 1 : 2 template complexes
through N2O donor sets of two thiosemicarbazones in the monoanionic form
even when a 1 : 1 : 1 mole ratio of the reactants (L1-3, NiCl2, and aldehydes) was used
(figure 1).
Template complexes (1–6) form as very fine crystal materials, very soluble in common
organic solvents. The low molar conductances of the complexes indicate non-ionic
structures. All of the complexes are stable in air and the magnetic susceptibility values
(2.83–3.07 BM) are compatible with high-spin d8 nickel(II) in an octahedral
environment.
3.2. Spectroscopic data
The electronic absorption bands of the thiosemicarbazones and complexes were
obtained in 3 ꢀ 10ꢂ5 M DMF solution between 200 and 800 nm. The spectra of the
thiosemicarbazones revealed bands at 240 and 309 nm for L1 and at 242 and 306 nm for
L2 and L3, which can be assigned to ꢅ ! ꢅ* and n ! ꢅ* transitions associated with the
thiosemicarbazone moiety and aromatic ring. In spectra of the nickel complexes,
ꢅ ! ꢅ* transitions of the aromatic rings were recorded at 239–242 nm and n ! ꢅ*
transitions of the azomethine and thioamide groups were observed at 307–313 nm and
330–355 nm region, respectively [32]. The spectra have two spin-allowed transitions
predicted for an octahedral nickel(II) complex. The bands at 466–498 and 762–763 nm
3
3
3
3
can be attributed to A2g(F) ! T1g(P) and A2g(F) ! T1g(F) transitions [33, 34].
IR spectra of the thiosemicarbazones displayed typical OH, N4H2, C¼N1, N2¼C
vibrations and the expected proton signals in the NMR spectra also confirmed the
structures of L1, L2, and L3 [35, 36].

Nickel(II) thiosemicarbazones and salicylaldehydes
833
The template reaction of S-methylthiosemicarbazones with aldehydes can be easily
monitored by IR spectra. The ꢃ(N4H2) bands of L1, L2, L3, and ꢃ(OH) band of the
condensed aldehydes are absent in the complex spectra due to coordination of aldehyde
hydroxyl by losing proton and the formation of a new C¼N band between thioamide
and the aldehyde. The ꢃ(C¼N1) bands of 1–6 shifted to lower energies ca 19–27 cmꢂ1
compared with free ligands, while ꢃ(N2¼C) bands shifted ca 4–16 cmꢂ1
.
Medium-intensity bands of new azomethine groups, (N4¼C), arising by condensation
of the thioamide nitrogen and aldehyde, are observed at 1555–1564 cmꢂ1
.
Mass specta of the ligands contain [Mꢂ(ꢂN¼C(SCH3)ꢂNH2)]þ. All the complex
spectra show peaks attributable to [MꢂCH3SH2]þ, [M ꢂ L]þ, and [M ꢂ NiL]þ. The Mþ
and MHþ fragments indicate expected molecular weight proving compositions [Ni(L)2].
3.3. Crystal structure of 3
Single crystals of 3 suitable for X-ray diffraction were grown by slow evaporation from
a mixed solution of ethanol and chloroform (2 : 1, v/v) at room temperature.
It crystallizes in a monoclinic crystal system with space group P21/c (#14). The
relevant details of the crystal, data collection and structure refinement are found
in table 1. Selected bond distances and angles are presented in tables 2 and 3. The
complete list of bond distances, bond angles, atomic coordinates and anisotropic
thermal parameters are presented in supporting information.
The six-coordinate nickel(II) (figure 2) bonds to two ligands, two nitrogens from
thiosemicarbazone moiety, and one oxygen from salicyl in the NNO mode, forming
N4O2 donor-set around nickel. The structure includes two five-membered NiN2C2 and
two six-membered NiONC3 chelate rings.
The molecular geometry of the complex is distorted octahedron with asymmetric
thiosemicarbazone. The N6–Ni1–N3 with 173.0(3)ꢁ angle can be designated as the z axis.
Table 1. Crystallographic data and processing parameters for 3.
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
C44H34N6O4S2NiBr2
993.42
294
Monoclinic
P21/c (#14)
ꢁ
˚
Unit cell dimensions (A,
)
a
b
c
ꢆ
ꢇ
ꢈ
19.4005(3)
9.7276(2)
24.1438(4)
90
90.8241(11)
90
4556.0(1), 4
1.448
3
˚
Volume (A ), Z
Calculated density (g cmꢂ3
)
Absorption coefficient (Mo-Ka) (cmꢂ1
F(000)
Limiting indices
)
23.24
2008.00
h ¼ 23; k ¼ 11; lmax ¼ 28
Reflections collected
Independent reflection
Observed reflection
Goodness-of-fit on F2
176,302
8248 [R(int) ¼ 0.095]
7478
1.157
Final R indices [I 4 3ꢉ(I )], Rw [I 4 3ꢉ(I )]
R1 ¼ 0.1455, wR2 ¼ 0.1600

¨
Y.D. Kurt and B. Ulkuseven
¨
834
The other axes in the horizontal plane, O1–Ni1–N2 and O2–Ni1–N4, are bent with
162.5(3)ꢁ and 167.0(3)ꢁ angles. Lengths of coordination bonds are not equal and so the
five-membered NiN2C2 and six-membered NiONC3 chelate rings are bent (table 2).
In crystal form, the molecular conformation of 3 is stabilized by C–X ꢃ ꢃ ꢃ Y (where X:
Br, H, and O; Y: O and H), type intermolecular interactions. Four of them, H32 ꢃ ꢃ ꢃ O3,
Table 2. Coordination bond lengths and angles of 3.
Angles (ꢁ)
˚
Bond lengths (A)
Ni1–O1
Ni1–N2
Ni1–N4
Ni1–O2
Ni1–N6
Ni1–N3
2.071(6)
N6–Ni1–N3
O1–Ni1–N2
O2–Ni1–N4
O1–Ni1–N6
O2–Ni1–N3
173.0(3)
N6–Ni1–N4
N2–Ni1–N3
O1ꢂNi1ꢂN3
O2–Ni1–N6
O1–Ni1–O2
N2–Ni1–N4
77.7(3)
76.7(3)
86.9(3)
89.3(3)
94.8(3)
103.4(3)
2.203(9)
2.216(7)
2.130(7)
2.038(9)
1.991(6)
162.5(3)
167.0(3)
87.5(3)
95.3(3)
Table 3. Interaction parameters related to oxygen (A and ꢁ) in 3.
˚
C–X ꢃ ꢃ ꢃ O
d(D–X)
d(X ꢃ ꢃ ꢃ O)
d(D ꢃ ꢃ ꢃ O)
ff(DXO)
C5–H15 ꢃ ꢃ ꢃ O1i
C5–H15 ꢃ ꢃ ꢃ O2i
C38–H32 ꢃ ꢃ ꢃ O3ii
C6–O3 ꢃ ꢃ ꢃ O2i
0.95
0.95
0.95
1.356
1.276
2.578
2.653
2.608
2.263
2.263
3.486
3.307
3.301
3.326
3.407
159.74
126.35
129.98
107.21
115.19
C37–O2 ꢃ ꢃ ꢃ O3ii
ix, 1þy, z.
iix, ꢂ1þy, z.
Figure 2. Molecular structure and atom-numbering scheme for 3. The H atoms (except H27 and H29) have
been omitted for clarity.

Nickel(II) thiosemicarbazones and salicylaldehydes
835
H15 ꢃ ꢃ ꢃ O1, H15 ꢃ ꢃ ꢃ O2, and O3 ꢃ ꢃ ꢃ O2, connect two molecules giving zig zag bonding
(table 3). Propagation of this interaction motif generates a molecular chain and this
chain structure repeats through other short contacts in the form of a parallel chain
˚
arrangement. Contacts with distances less than 3 A are H5–Br1 2.988, H26–C17 2.857,
H30–C25 2.890, H2–C38 2.727, H13–H31 2.157, and C14–H15 2.897.
4. Conclusion
The tendency of nickel(II) to form a square-planar complex has been reported for many
common complexes of thiosemicarbazones and their template compounds [1, 4, 5, 37,
38]. In our previous study, 4-substituted 2-hydroxybenzophenone thiosemicarbazone
gave expected square-planar complexes in N2O2 coordination mode [39].
In this study, the phenyl ring of the benzophenone thiosemicarbazone L1 has no
2-OH substituent and can generate a tridentate donor set (N2O). To complete the
coordination sites of nickel(II), two tridentate ligands coordinate (1 and 2). In contrast,
the 5-(Br/Cl)-2-hydroxy benzophenone thiosemicarbazones, L2 and L3, gave tetra-
dentate (N2O2) ligand systems and an octahedral structure involving N4O2 donors
formed instead of the expected square-planar structure.
This unusual half-template condensation occurs by using the 5-substituted
benzophenone thiosemicarbazone. 5-Bromo- and chloro-substituted phenol rings with
relatively high acidity compared to 4-substituted phenol, and the hydroxyl protons
of L2 and L3 are more dissociated. So, the deprotonated 2-OH of the benzophenone
thiosemicarbazone cannot react with NiCl2 and the template condensation is completed
over only hydroxyl group of salicylaldehyde as second arylidene moiety.
The nickel in the template condensation of L1, L2, and L3 showed a tendency
to compose the maximum number of chelate rings due to the symbiosis effect and the
coordination sites of nickel are occupied by N2O donor set of two monoanionic
thiosemicarbazones.
Supplementary material
Crystallographic data for [Ni(L)2] (C44H34Br2N6NiO4S2 (3)) has been deposited at the
Cambridge Crystallographic Data Centre as supplementary publication (CCDC
711558). These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html or from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK [Fax: þ44-1223-336033; Email: deposit@ccdc.cam.ac.uk].
Acknowledgment
This work was supported by the Research Fund of Istanbul University, Project
No. 256/23082004.

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Y.D. Kurt and B. Ulkuseven
¨
836
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