Polyhedron 96 (2015) 6670

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Polyhedron
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Syntheses, structures and biological evaluation of some transition metal

complexes with a tetradentate benzamidine/thiosemicarbazone ligand
Thi Bao Yen Nguyen a, Chien Thang Pham a,b, Thi Nguyet Trieu a, Ulrich Abram b,, Hung Huy Nguyen a,
a
b

Department of Chemistry, Hanoi University of Science, 19 Le Thanh Tong, Hanoi, Viet Nam
Freie Universitt Berlin, Institute of Chemistry and Biochemistry, Fabeckstr. 34-36, D-14195 Berlin, Germany

a r t i c l e

i n f o

Article history:
Received 5 March 2015
Accepted 21 April 2015
Available online 27 April 2015
Keywords:
Transition metals
Benzamidines
Thiosemicarbazones
X-ray structure
Cytotoxicity

a b s t r a c t
The potentially tetradentate benzamidine/thiosemicarbazone ligand, Et2N(C@S)NH-C(Ph) = N(oC4H6)C(Me) = NNH(C@S)NHMe (H2L) readily reacts with Ni(CH3COO)2, [PdCl2(CH3CN)2],
[PtCl2(PPh3)2] and (NBu4)[ReOCl4] under formation of complexes of the compositions [M(L)] (M = Ni
(1), Pd (2), Pt (3)) and [ReO(L)(OMe)] (4). In all complexes, H2L is doubly deprotonated and bonded to
the central metal ion via its N2S2 donor set. Complexes 1, 2 and 3 have distorted square-planar coordination spheres, while the rhenium compound 4 is an octahedral trans oxido/methoxido complex. The H2L
proligand shows a medium cytotoxicity with an IC50 value of 21.1 lM. While the rhenium complex 4
exhibits a stronger antiproliferative effect (IC50 = 5.52 lM), the nickel, palladium and platinum complexes
are almost inactive.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Thiosemicarbazones, which form stable complexes with many
main group and transition metals [1,2], constantly attract the
interest of chemists and pharmacists due to their remarkable biological and pharmacological properties such as antibacterial,
antiviral, antineoplastic, or antimalarial activity [35].
Modications of the thiosemicarbazone framework, in order to nd
new compounds with higher activity and/or to tune their biological
activity, have been extensively studied, and relationships between
the biological activity and chelate formation are evident in a number of cases [68].

Recently we reported the synthesis and structural characterization of a series of tridentate benzamidine/thiosemicarbazide
ligands (H2L0 ), which were prepared by reactions of N-[N0 ,N0 -dialkylamino(thiocarbonyl)]benzimidoyl chlorides (Bzm-Cl) and
thiosemicarbazides [9,10]. They form stable complexes with various transition metals [912]. Additionally, the organic ligands as
well as their oxorhenium(V) and gold(III) complexes show a
promising cytotoxicity on breast cancer cell lines [1012]. The
reaction
of
2-aminoacetophenone-N-(4-methylthiosemicarbazone) with Bzm-Cl results in the formation of a tetradentate
hybrid thiosemicarbazone/benzamidine ligand, H2L [13]. This
ligand has hitherto only been used for reactions with

Corresponding authors.
E-mail addresses: ulrich.abram@fu-berlin.de (U. Abram), nguyenhunghuy@hus.edu.vn (H.H. Nguyen).
http://dx.doi.org/10.1016/j.poly.2015.04.026
0277-5387/ 2015 Elsevier Ltd. All rights reserved.

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T.B.Y. Nguyen et al. / Polyhedron 96 (2015) 6670

nitridotechnetium and rhenium complexes, which resulted in

stable, neutral TcVN and ReVN complexes [13].
With respect to the stability of these products, H2L should also
be suitable for the coordination of other metal ions and the
obtained products may possibly show interesting biological properties. Here, we report about reactions of H2L with Ni(CH3COO)2,
[PdCl2(CH3CN)2], [PtCl2(PPh3)2] and (NBu4)[ReOCl4], the structures
of the obtained products as well as their cytotoxicity against
human MCF-7 breast cancer cells.

2. Results and discussion

2.1. Syntheses and structures of the nickel, palladium and platinum
complexes
H2L readily reacts with Ni(CH3COO)2, [PdCl2(CH3CN)2] or
[PtCl2(PPh3)2] under formation of complexes of the composition
[M(L)] (Scheme 1). Depending on the solubility of the starting
materials, the reactions were carried out in MeOH for
Ni(CH3COO)2 or in a MeOH/CH2Cl2 mixture (v/v: 1/1) for
[PdCl2(CH3CN)2] and [PtCl2(PPh3)2]. While the rst reaction proceeds very quickly, the two latter reactions require more time.
The addition of a supporting base such as Et3N accelerates the formation of the complexes and allows the syntheses to be carried out
at ambient temperature with good yields. The products are only
sparingly soluble in alcohols, but well soluble in CH2Cl2 or CHCl3
and can be recrystallized from CH2Cl2/MeOH mixtures.
The IR spectra of all three compounds show a moderate absorption at about 3400 cm1, which is assigned to the mNH stretch of
the MeNH-CS group. The absorption band of the mC@N vibration is
observed as a very intense band around 1550 cm1. This corresponds to a strong bathochromic shift of the corresponding band
in H2L by about 170 cm1. Such shifts are commonly explained
by a chelate formation with a large degree of p-electron delocalization within the benzamidine chelate rings [912]. Expectedly, the
1
H NMR spectra of the complexes no longer show resonances at
12.62 ppm and 8.41 ppm, which are assigned to the NH protons
of the benzamidine and thiocarbazone moieties in the proligand.
Additionally, a high eld shift of the signal of the NH proton of
the CS-NHMe residue from 7.64 ppm in the proligand [13] to the
region around 5.0 ppm in the spectra of the complexes 1, 2 and 3
is observed, which conrms that the organic ligand is doubly
deprotonated and chelated to the central metal ions. A hindered
rotation around the CNEt2 bond is observed and results in two
magnetically non-equivalent ethyl groups. Thus, two triplet signals
of the methyl groups of the NEt2 residues are observed in the 1H
NMR spectra of the complexes. The signals of the two methylene
groups appear as four well separated multiplet resonances. This
pattern has previously been rationalized by the rigid structure of
the tertiary amine group, which makes ethylene protons

Ni(CH 3COO) 2

H 2L

[Pd(MeCN) 2Cl 2]

[Pt(PPh 3) 2Cl2]

Fig. 1. Ellipsoid representation of the molecular structure of [Ni(L)] [19]. Thermal

ellipsoids represent 60% probability. Hydrogen atoms bonded on carbon atoms have
been omitted for clarity.

Table 1
Selected bond lengths () and angles () in 1 and 2.
1

MS1
MS11
MN5
MN8
S1C2
C2N3

2.154(1)
2.157(1)
1.878(1)
1.909(1)
1.723(1)
1.355(2)

2.252(1)
2.270(1)
2.017(1)
2.033(1)
1.729(2)
1.348(2)

S1MN5
S1MN8
S1MS11

95.56(4)
166.46(4)
85.49(1)

94.85(4)
173.03(4)
88.64(2)

N3C4
C4N5
S11C10
C10N9
N9N8
N8C6

1.316(2)
1.357(2)
1.739(1)
1.300(2)
1.404(2)
1.313(2)

1.318(2)
1.348(2)
1.748(2)
1.296(2)
1.397(2)
1.308(2)

N5MN8
N5MS11
N8MS11

93.49(5)
167.64(4)
87.83(4)

91.70(6)
172.40(4)
85.14(4)

magnetically nonequivalent with respect to their axial and equatorial positions [9,10].
Single crystals suitable for X-ray studies were obtained by slow
evaporation of CH2Cl2/MeOH mixtures for the nickel and palladium
compounds. Fig. 1 illustrates the molecular structure of 1 as a
representative for this class of compounds. The structure of the
analogous palladium compound 2 is virtually identical and, thus,
no extra gure is shown. Selected bond lengths and angles of 1
and 2 are compared in Table 1. The atomic labeling scheme of
the palladium complex has been adopted from that of the nickel
complex. Both metal ions are coordinated by the S2N2 donor set
of the organic ligand in a distorted square-planar coordination
environment. The molecular planes dened by the metal atoms

MeOH, Et 3N
N

- 2 Et 3NHCH 3COO
CH 2Cl 2 / MeOH, Et 3N

S
M

- 2 Et 3NHCl, - 2 MeCN
CH 2Cl 2 / MeOH, Et 3N

S
N

- 2 Et 3NHCl, - 2 PPh 3

HN

1: M = Ni, 2: M = Pd; 3: M = Pt
Scheme 1. Synthesis of the [M(L)] complexes.

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T.B.Y. Nguyen et al. / Polyhedron 96 (2015) 6670

N
NH
(NBu 4)[ReOCl 4]

+
N

N
S
S

MeOH, Et 3N
- NBu 4Cl, HNEt 3Cl

N
S

Re
N

HN
HN

H 2L

OMe S
N
HN

4
Scheme 2. Synthesis of [ReO(OMe)(L)].

Table 2
Selected bond lengths () and angles () in 4.
ReS1
ReS11
ReN5
ReN8
ReO10
O10ReS1
O10ReN5
O10ReN8
O10ReS11
O10ReO20
S1ReN5
S1ReN8
S1ReS11

2.358(1)
2.379(1)
2.095(4)
2.127(4)
1.707(4)

ReO20
S1C2
C2N3
N3C4
C4N5
97.2(1)
91.2(2)
90.8(2)
96.0(1)
172.1(2)
93.7(1)
171.2(1)
93.5(4)

1.917(4)
1.753(5)
1.336(7)
1.311(7)
1.347(6)

S11C10
C10N9
N9N8
N8C6

S1ReO20
N5ReN8
N5ReS11
N5ReO20
N8ReS11
N8ReO20
S11ReO20

1.753(5)
1.309(7)
1.393(6)
1.311(7)
89.5(1)
89.8(2)
169.1(1)
84.2(2)
82.0(1)
82.8(2)
87.7(1)

and the four donor atoms S1, N5, N8 and S11 are slightly distorted
with maximum deviations from the mean least-squares planes of
0.215(1) for N8 (in 1) and of 0.098(1) for N5 (in 2).
2.2. Synthesis and structures of the oxidorhenium(V) complex
H2L reacts with (NBu4)[ReOCl4] in MeOH in the presence of the
supporting base Et3N under formation of a red crystalline solid of
the composition [ReO(OMe)(L)] (4) in high yields (Scheme 2). The
reaction can be carried out at room temperature or under reux
without signicant change in the yield.
The IR spectrum of 4 is similar to those discussed for the complexes 13 with a sharp medium absorption band of the NH
stretch at 3387 cm1 and a strong bathochromic shift of the mC@N
band with respect to the corresponding vibration in the spectrum
of H2L. The strong absorption at 941 cm1 is assigned to the
mRe@O vibration. This wavenumber is slightly lower than those,
which are normally reported for common six-coordinate
oxidorhenium(V) complexes [14], but within the typical range for
octahedral trans oxido/alkoxido rhenium(V) complexes [15,16].
The 1H NMR spectrum of 4 shows the same features as those of
the nickel, palladium and platinum compounds: the absence of
two NH resonances and a high eld shift of the NH signal of
the CSNHMe moiety to 5.26 ppm. The chelate formation also
leads to a strong downeld shift of about 1.1 ppm of the Me
C@N signal. The presence of a methoxy group in 4 is clearly indicated by an additional singlet at 3.04 ppm. The +ESI mass spectrum
of 4 shows no molecular ion peak, but an intense peak at
m/z = 641.11, which can be assigned to the fragment [MOMe]+.
The X-ray diffraction data of 4 are in a good agreement with the
spectroscopic results. Fig. 2 shows the molecular structure of the
complex. Selected bond lengths and angles are given in (Table 2).
The environment of the rhenium atom is best described as a distorted octahedron with an oxido and a methoxido ligand arranged
in trans positions to each other. The L2 ligand is expectedly coordinated to the metal via its N2S2 donor set. The Re atom is located
only 0.151(2) above the mean least-square plane formed by the
four donor atoms of L2 towards the oxido ligand. The ReO20

Fig. 2. Ellipsoid representation of the molecular structure of [ReO(OMe)(L)] [19].

Thermal ellipsoids represent 50% probability. Hydrogen atoms bonded on carbon
atoms have been omitted for clarity.

bond length of 1.917(4) is shorter than a typical rheniumoxygen single bond and reects some double bond character. The
required electron density is transferred from the double bond of
the oxido ligand. Consequently, the ReO10 bond length of
1.707(4) is slightly longer than those in ve-coordinate or other
octahedral oxidorhenium(V) complexes. This is in a good agreement with the relatively low wavenumber of the mRe@O absorption
in the IR spectrum of 4.
2.3. In vitro cell tests
We investigated the antiproliferative effects of the ligand H2L
and its complexes on human MCF-7 breast cancer cells in a concentration response assay. This allows the determination of their IC50
values. The uncoordinated H2L shows an IC50 value of 21.1(9) lM
reecting a medium antiproliferative effect. The complexation of
H2L with Ni2+, Pd2+ and Pt2+ ions dramatically decreases the cytotoxicity of the compound. Thus, complex 1 only causes a very weak
reduction of the growth of human MCF-7 breast cancer cells
(IC50 = 258(10) lM), while complexes 2 and 3 show almost no
antiproliferative effect. The low cytotoxicity of the square-planar
complexes reects their limited dissociation inside the cell and
the stable metal chelates themselves exhibit no antiproliferative
effects. This can be understood by the rigid tetradentate N2S2 coordination of the ligand, which is expected to form stable complexes
with Ni2+, Pd2+ and Pt2+. Additionally, no labile coordination site is
available, as they are present in all metal complexes of the previously studied tridentate thiosemicarbazone/benzamidine hybrid
ligands, for which promising antiproliferative effects have been
found [1012]. Such a potentially labile ligand is present in the

T.B.Y. Nguyen et al. / Polyhedron 96 (2015) 6670

rhenium complex 4, where the methoxo ligand can readily be

hydrolyzed, which enables the resulting complex fragment for
interactions with biological targets. In fact, compound 4 exhibits
an IC50 value of 5.52(14) mM, which is markedly lower than that
of H2L. The cytotoxicity of 4 is in the magnitude of those reported
for oxidorhenium(V) and gold(III) complexes with tridentate H2L
ligands [10,12], which also possess a labile (chlorido) ligand in
their coordination spheres, and it is almost equal to that of cisplatin (IC50 = 7.10) determined under the same experimental conditions [17].
3. Conclusions
In the present communication, we could show that the
benzamidine/thiosemicarbazone hybrid ligand H2L forms stable
complexes with Ni2+, Pd2+ and Pt2+ and ReO3+ metal centers. The
proligand H2L and its oxidorhenium(V) complex show some
antiproliferative effects on human MCF-7 breast cancer cells.
Since H2L is the hitherto only representative of this new class of
potentially bioactive hybrid ligands, studies with other derivatives
of this class are recommended and are in preparation in our
laboratories.
4. Experimental
4.1. Materials
All reagents used in this study were reagent grade and used
without further purication. H2L was prepared as reported previously [13].
4.2. Physical measurements
Infrared spectra were measured from KBr pellets on a Shimadzu
IRAfnity-1S FTIR spectrometer between 400 and 4000 cm1. ESI
mass spectra were measured with an Agilent 6210 ESI-TOF
(Agilent Technologies). All MS results are given in the form: m/z,
assignment. Elemental analysis of carbon, hydrogen, nitrogen,
and sulfur were determined using a Heraeus Vario EL elemental
analyzer. NMR-spectra were taken with a JEOL 400 MHz
spectrometer or a BRUKER 500 MHz spectrometer.
4.3. Syntheses
4.3.1. Synthesis of [Ni(L)], 1
Ni(CH3COO)24H2O (25 mg, 0.1 mmol) was added to a solution
of H2L (44 mg, 0.1 mmol) in 5 mL of MeOH. A deep red solution
was obtained after the addition of three drops of Et3N, and a dark
red solid deposited within a few minutes. The mixture was stirred
for additional 2 h at room temperature and then the precipitate
was ltered off, washed with MeOH and dried in vacuum. Single
crystals of 1 were obtained by slow evaporation of a
CH2Cl2/MeOH (v/v: 1/1) solution. Yield 84% (42 mg). Elemental
analysis: Anal. Calc. for C22H26N6S2Ni: C, 53.13; H, 5.27; N, 16.90;
S, 12.90. Found: C, 53.01; H, 5.14; N, 16.95; S, 12.63%. IR (KBr,
cm1): 3407 (m), 3086 (w), 2923 (m), 1547 (vs), 1502 (vs), 1486
(s), 1424 (s), 1361 (s), 1230 (m), 1022 (m), 810 (w), 702 (m), 630
(m). 1H NMR (500 MHz, CDCl3, ppm): 1.30 (t, J = 7.0 Hz, 3H, CH3),
1.31 (t, J = 7.0 Hz, 3H, CH3), 2.70 (s, 3H, N@CCH3), 2.97 (d,
J = 5.0, 3H, NCH3), 3.69 (m, 1H, NCH2), 3.74 (m, 1H, NCH2), 3.86
(m, 1H, NCH2), 4.09 (m, 1H, NCH2), 4.84 (s, br, NH), 6.41 (d,
J = 8.0 Hz, 1H, C6H4), 6.78 (t, J = 7.7 Hz, 1H, C6H4), 6.86 (t,
J = 7.7 Hz, 1H, C6H4), 7.12 (t, J = 7.5 Hz, 2H, Ph), 7.20 (t, J = 7.3 Hz,
1H, Ph), 7.32 (d, J = 7.0 Hz, 2H, Ph), 7.52 (d, J = 8.0 Hz, 1H, C6H4).
+ESI MS (m/z): 497.09, 100%, [M+H]+.

69

4.3.2. Synthesis of [Pd(L)], 2

[PdCl2(CH3CN)2] (26 mg, 0.1 mmol) was added to a solution of
H2L (44 mg, 0.1 mmol) in 5 mL of a CH2Cl2/MeOH (v/v 1/1) mixture, and then three drops of Et3N were added. The mixture was
stirred for 3 h at room temperature to obtain a clear yellow solution. Slow evaporation of the solvents gave light yellow crystals
of 2. The product was ltered off, washed with MeOH and dried
in vacuum. Yield 65% (35 mg). Elemental analysis: Anal. Calc. for
C22H26N6S2Pd: C, 48.48; H, 4.81; N, 15.42; S, 11.77. Found: C,
48.21; H, 4.85; N, 15.35; S, 11.60%. IR (KBr, cm1): 3434 (m),
3052 (w), 2967 (m), 1547 (vs), 1503 (vs), 1467 (s), 1420 (s), 1379
(s), 1223 (m), 1089 (m), 749 (m), 618 (m). 1H NMR (500 MHz,
CDCl3, ppm): 1.33 (t, J = 7.0 Hz, 3H, CH3), 1.36 (t, J = 7.0 Hz, 3H,
CH3), 2.78 (s, 3H, N@CCH3), 3.03 (d, J = 5.0, 3H, NCH3), 3.65 (m,
1H, NCH2), 3.74 (m, 1H, NCH2), 4.04 (m, 1H, NCH2), 4.24 (m, 1H,
NCH2), 4.95 (s, br, NH), 6.53 (d, J = 8.0 Hz, 1H, C6H4), 6.83 (t,
J = 7.7 Hz, 1H, C6H4), 6.86 (t, J = 7.6 Hz, 1H, C6H4), 7.15 (t,
J = 7.5 Hz, 2H, Ph), 7.21 (t, J = 7.2 Hz, 1H, Ph), 7.37 (d, J = 7.4 Hz,
2H, Ph), 7.59 (d, J = 8.0 Hz, 1H, C6H4). +ESI MS (m/z): 544.98,
100%, [M+H]+.
4.3.3. Synthesis of [Pt(L)], 3
The compound was prepared as described for complex 2, but
starting from [PtCl2(PPh3)2] (79 mg, 0.1 mmol) to obtain yellow
crystals. Yield 62% (39 mg). Elemental analysis: Anal. Calcd. for
C22H26N6S2Pt: C, 41.70; H, 4.14; N, 13.26; S, 10.12. Found: C,
41.63; H, 4.05; N, 13.32; S, 10.10%. IR (KBr, cm1): 3415 (m),
3058 (w), 2966 (m), 1548 (vs), 1502 (vs), 1467 (s), 1421 (s), 1375
(s), 1230 (m), 1081 (m), 747 (m), 623 (m). 1H NMR (500 MHz,
CDCl3, ppm): 1.32 (t, J = 7.0 Hz, 3H, CH3), 1.36 (t, J = 7.0 Hz, 3H,
CH3), 2.80 (s, 3H, N@CCH3), 3.01 (d, J = 5.0, 3H, NCH3), 3.63 (m,
1H, NCH2), 3.72 (m, 1H, NCH2), 4.03 (m, 1H, NCH2), 4.25 (m, 1H,
NCH2), 4.96 (s, br, NH), 6.50 (d, J = 8.0 Hz, 1H, C6H4), 6.81 (t,
J = 7.7 Hz, 1H, C6H4), 6.86 (t, J = 7.7 Hz, 1H, C6H4), 7.14 (t,
J = 7.5 Hz, 2H, Ph), 7.20 (t, J = 7.3 Hz, 1H, Ph), 7.35 (d, J = 7.5 Hz,
2H, Ph), 7.60 (d, J = 8.0 Hz, 1H, C6H4). +ESI MS (m/z): 634.08,
100%, [M+H]+.
4.3.4. Synthesis of [ReO(OCH3)(L), 4
H2L (44 mg, 0.1 mmol) was dissolved in 3 mL of CH2Cl2 and
added to a stirred solution of (NBu4)[ReOCl4] (58 mg, 0.1 mmol)
in 2 mL MeOH. After the addition of 3 drops of Et3N, the reaction
mixture was heated to 40 C for 30 min. The solvent of the resulting clear red solution was slowly evaporated to give red crystals of
4. Yield 60% (40 mg). Elemental analysis: Anal. Calc. for
C23H29N6O2S2Re: C, 41.12; H, 4.35; N, 12.51; S, 9.55. Found: C,
40.71; H, 4.09; N, 12.56; S, 9.21%. IR (KBr, cm1): 3387 (m), 3070
(w), 2970 (m), 2924 (m), 2800 (w), 1558 (s), 1512 (s), 1425 (m),
1359 (m), 1288 (m), 1250 (m), 1227 (m), 1172 (w), 1110 (m),
942 (s), 810 (w), 771 (w). 1H NMR (400 MHz, CDCl3, ppm): 1.36
(t, J = 7.1 Hz, 3H, CH3), 1.41 (t, J = 7.2 Hz, 3H, CH3), 2.92 (s, 3H,
N@CCH3), 3.04 (s, 3H, OCH3), 3.14 (d, J = 5.0, 3H, NCH3), 3.74
(m, 2H, NCH2), 4.33 (m, 1H, NCH2), 4.53 (m, 1H, NCH2), 5.26 (s,
br, NH), 6.56 (d, J = 7.9 Hz, 1H, C6H4), 6.82 (t, J = 7.9 Hz, 1H, C6H4),
6.91 (t, J = 8.0 Hz, 1H, C6H4), 7.15 (m, 3H, Ph), 7.52 (d, J = 7.8, 2H,
Ph), 7.66 (d, J = 7.8, 1H, C6H4). +ESI MS (m/z): 641.11, 100%,
[MOMe]+.
4.4. X-ray crystallography
The intensities for the X-ray determinations were collected on a
Bruker D8-QUEST (1 and 2) and a STOE IPDS 2T instrument (4) with
Mo Ka radiation (k = 0.71073 ). Standard procedures were applied
for data reduction and absorption correction. Structure solution
and renement were performed with SHELXS and SHELXL [18].

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T.B.Y. Nguyen et al. / Polyhedron 96 (2015) 6670

Table 3
X-ray structure data collection and renement parameter.

Formula
Mw
Crystal system
a ()
b ()
c ()
a ()
b ()
c ()
V (3)
Space group
Z
Dcalc (g cm3)
l (mm1)
Tmin
Tmax
Abs. Corr.
No. of reections
No. of indep.
No. parameters
R1/wR2
Goodness-of-t (GOF) on F2

C22H26N6S2Ni
497.32
orthorhombic
13.0699(3)
17.3185(5)
20.1027(5)
90
90
90
4550.3(2)
Pbca
8
1.452
1.059
0.5457
0.7457
multiscan
85,358
5422
284
0.0266/0.0638
1.056

C22H26N6S2Pd
545.01
orthorhombic
13.3416(3)
16.8770(5)
20.6174(5)
90
90
90
4642.3(2)
Pbca
8
1.560
1.001
0.6958
0.7457
multiscan
76,416
5774
284
0.0239/0.0539
1.081

C23H29N6O2S2Re
671.84
triclinic
9.927(1)
10.623(1)
13.863(1)
79.89(1)
79.07(1)
64.31(1)
1286.3(2)

P1
2
1.735
4.918
0.3537
0.7682
integration
23,666
6895
323
0.0377/0.0790
1.047

Hydrogen atom positions were calculated for idealized positions

and treated with the riding model option of SHELXL. More details
on data collections and structure calculations are contained in
Table 3.
4.5. In vitro cell tests
The cytotoxic activity of the compounds was determined using
a MTT assay. Human cancer cells of the cell line MCF-7 were
obtained from the American Type Culture Collection (Manassas,
VA) ATCC. Cells were cultured in medium RPMI 1640 supplemented with 10% FBS (Fetal bovine serum) under a humidied
atmosphere of 5% CO2 at 37 C. The testing substances were initially dissolved in DMSO, then diluted to the desired concentration
by adding cell culture medium. The samples (100 lL) of the complexes with different concentrations were added to the wells on
96-well plates. Cells were detached with trypsin and EDTA and
seeded in each well with 3  104 cells per well. After incubation
for 48 h, a MTT solution (20 lL, 4 mg mL1) of phosphate buffer
saline (8 g NaCl, 0.2 g KCl, 1.44 g Na2HPO4 and 0.24 g KH2PO4/L)
was added into each well. The cells were further incubated for
4 h and a purple formazan precipitate was formed, which was separated by centrifugation. DMSO (100 lL) was added to each well to

dissolve the precipitate. The optical density of the solution was

determined by a plate reader (TECAN) at 540 nm. The inhibition
ratio was calculated on the basis of the optical densities obtained
from three replicate tests.
Acknowledgments
We gratefully acknowledge nancial support from NAFOSTED
(Vietnams National Foundation for Science and Technology
Development) through project 104.02-2012.76. and Ph.D grants
from DAAD (Deutscher Akademischer Austauschdienst, Germany).
Appendix A. Supplementary data
CCDC 10522131052215; contains the supplementary crystallographic data for 1, 2 and 4. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; or e-mail:
deposit@ccdc.cam.ac.uk.
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