M.-X. Li et al. / Inorganic Chemistry Communications 13 (2010) 1572–1575
1575
[
[
[
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of Göttingen, Göttingen, 1997.
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[24] Crystal data for complex 1: C28H38MnN8S2 (605.72), Crystal dimensions
0.22×0.19×0.18 mm3, triclinic, space group P−1, a=10.515(4) Å, b=12.533
(2) Å, c = 13.177(2) Å, α = 115.923(2)° β = 98.045(3)° γ = 99.434(3)°
V=1496.2(6) Å 3, Z=2, ρcalcd=1.344 Mg⋅m−3, 5238 reflections collected,
4283 unique (Rint=0.0177), R1=0.0375 [IN2σ (I)], and wR2=0.1084 (all
data). The data were collected on a Bruker APEX-II CCD diffractometer (MoKa,
λ=0.71073 Å) at 296(2) K. All structures were solved by the direct method and
refined by the full-matrix least-squares on F2 using the SHELXL-97. All of the non-
hydrogen atoms were refined anisotropically.
5
5] S. Padhye, Z. Afrasiabi, E. Sinn, J. Fok, K. Mehta, N. Rath, Inorg. Chem. 44 (2005)
1154.
6] C.R. Kowol, R. Trondl, P. Heffeter, V.B. Arion, M.A. Jakupec, A. Roller, M. Galanski,
W. Berger, B.K. Keppler, J. Med. Chem. 52 (2009) 5032.
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Inorg. Chim. Acta 249 (1996) 207.
[
[
[
9] H. Beraldo, D. Gambino, Mini Rev. Med. Chem. 4 (2004) 159.
[
[
10] Z. Afrasiabi, E. Sinn, J. Chen, Y. Ma, S. Padhye, Toxicol. Appl. Pharmacol. 197 (2004)
0.
11] D. Kovala-Demertzi, A. Domopoulou, M.A. Demertzis, G. Valle, A. Papageorgiou, J.
Inorg. Biochem. 68 (1997) 147.
4
[
[
[
12] A.G. Quiroga, C.N. Ranninger, Coord. Chem. Rev. 248 (2004) 119.
13] S. Singh, N. Bharti, P.P. Mohapatra, Chem. Rev. 109 (2009) 1900.
14] (a) M.X. Li, C.L. Chen, C.S. Ling, J. Zhou, B.S. Ji, Y.J. Wu, J.Y. Niu, Bioorg. Med. Chem.
Lett. 19 (2009) 2704;
[25] Crystal data for complex 2: C28H38NiN8S2 (609.49), Crystal dimensions
0.30× 0.27× 0.22 mm3, monoclinic, space group P21/c, a =11.697(1) Å,
b=20.844(1) Å, c=12.129(1) Å, β=92.946(1)° V=2953.3(3)
Å 3, Z=4,
ρcalcd = 1.371 Mg⋅m−3, 5140 reflections collected, 4179 unique
(Rint=0.0417), R1=0.0737 [IN2σ (I)], and wR2=0.2411 (all data). The data
were collected on a Bruker APEX-II CCD diffractometer (MoKa, λ=0.71073 Å) at
296(2) K. All structures were solved by the direct method and refined by the full-
matrix least-squares on F2 using the SHELXL-97. All of the non-hydrogen atoms
were refined anisotropically.
(
b) M.X. Li, Y. Bai, B.G. Zhang, C.Y. Duan, J. Xu, Q.J. Meng, Inorg. Chem. 44 (2005)
459;
c) M.X. Li, Q.Z. Sun, Y. Bai, C.Y. Duan, B.G. Zhang, Q.J. Meng, Dalton Trans. (2006)
572;
5
(
2
(
(
(
d) M.X. Li, J. Zhou, C.L. Chen, J.P. Wang, Z. Naturforsch. 63b (2008) 280;
e) D. Zhang, Q. Li, M.X. Li, D.Y. Chen, J.Y. Niu, J. Coord. Chem. 63 (2010) 1063;
f) D.Y. Chen, C.L. Chen, M.X. Li, J.Y. Niu, X.F. Zhu, H.M. Guo, J. Coord. Chem. 63
[26] K.V. Katti, P.R. Singh, C.L. Barnes, J. Chem. Soc., Dalton Trans. (1993) 2153.
[27] F.A. Beckford, G. Leblanc, J. Thessing, M. Shaloski, B.J. Frost, L. Li, N.P. Seeram, Inorg.
Chem. Commun. 12 (2009) 1094.
(
2010) 1546;
(
g) M.X. Li, C.L. Chen, D. Zhang, J.Y. Niu, B.S. Ji, Eur. J. Med. Chem. 45 (2010) 3169.
[28] T.S. Lobana, P. Kumari, R.J. Butcher, Inorg. Chem. Commun. 11 (2008) 11.
[29] M. Joseph, M. Kuriakose, M.R.P. Kurup, E. Suresh, A. Kishore, S.G. Bhat, Polyhedron
25 (2006) 61.
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[31] M. Joseph, M. Kuriakose, M.R.P. Kurup, E. Suresh, A. Kishore, S.G. Bhat, Polyhedron
25 (2006) 61.
[32] The minimal inhibitory concentrations (MIC, μg/mL) were estimated by the disk
diffusion method. The final concentration of all cultures in Mueller-Hinon agar
(MHA) for bacteria was adjusted to 106 CFU/mL and used for inoculation in the
MIC test. Serial dilutions of the test compounds (dissolved in DMSO) were
prepared at concentrations of 0–2000 μg/mL. Each plate was inoculated with
0.1 mL of the prepared bacterial cultures. Similarly, each plate carried a blank disc,
with solvent DMSO only in the center to serve as negative control. The inoculated
plates were then incubated at 37 °C for 18–20 h. The minimal inhibitory
concentration (MIC) was detected as the lowest concentration of drug in plate
for which no visible growth took place by macroscopic evaluation. All
determinations were performed in triplicate and confirmed by three separate
experiments.
[
[
15] M. Joseph, V. Suni, C.R. Nayar, M.R.P. Kurup, H.-K. Fun, J. Mol. Struct. 705 (2004)
3.
6
16] Synthesis of HL: Cyclohexyl isothiocyanate (1.41 g, 10 mmol) and hydrazine
hydrate (0.50 g, 10 mmol), each dissolved in 20 ml methanol were mixed with
constant stirring. The stirring was continued for 1 h and the white product, N(4)-
cyclohexyl thiosemicarbazide formed was filtered, washed, dried and recrystal-
lized from methanol. A methanolic solution of 2-acetylpyridine (0.36 g, 3 mmol)
was added dropwise to
a methanolic solution (30 mL) of N(4)-cyclohexyl
thiosemicarbazide (0.52 g, 3 mmol) with five drops of acetic acid as catalyst.
After refluxed for 4 h with stirring, the resultant solution was filtered. Colorless
crystals suitable for X-ray studies were obtained by slow evaporation of its
methanol solution. Anal. Calcd. for C14H20N4S: C 60.78, H 7.24, N 20.26; found C
6
+
0.53, H 7.06, N 20.74; ESI-MS (m/z): 277.2 [HL+H ].
[
17] Synthesis of complex 1: An ethanol solution containing Mn(ClO
.5 mmol) was added dropwise to an ethanol solution (30 mL) of 2-acetylpyr-
idine N(4)-cyclohexylthiosemicarbazone (0.28 g, 1.0 mmol) and NaOAc (0.08 g,
.0 mmol). After refluxed for 2 h with stirring, the resultant solution was filtered.
Dark-red Crystals suitable for X-ray studies were obtained by slow evaporation of
its ethanol solution. Anal. Calcd. for C28 38MnN : C 55.47, H 6.27, N 18.49;
found C 54.98, H 6.04, N 18.11; ESI-MS (m/z): 606.6 [Mn(L)
was prepared by a similar procedure to that of complex 1 using Ni(ClO
place of Mn(ClO ∙6H O. By evaporation of the solvent, violet–red crystals
suitable for X-ray work are separated. Anal. Calcd. for C28 38NiN : C 55.13, H
.23, N 18.37; found C 55.92, H 6.34, N 18.03; ESI-MS (m/z): 610.3 [Ni(L)
18] Crystal data for HL: C14H20N4S (276.40), Crystal dimensions
4 2
) ∙6H
2
O (0.18 g,
0
1
[33] J.G. Tojal, A.G. Orad, J.L. Serra, J.L. Pizarro, L. Lezama, M.I. Arriortua, T. Rojo, J. Inorg.
Biochem. 75 (1999) 45.
H
8 2
S
+
2
+H ]. Complex 2
∙6H O in
[34] K562 leukaemia cell line, (purchased from the Institute of Biochemistry and Cell
Biology, SIBS, CAS) was cultured in RPMI-1640 medium supplemented with 10%
FBS, 100 UmL− of penicillin, 100 μg (200 μL per well) of streptomycin at 37 °C in
4
)
2
2
1
4
)
2
2
H
8
S
2
2
humid air atmosphere of 5% CO . Cell cytotoxicity was assessed by the MTT assay.
Briefly, cells were placed into a 96-well-plate (5×103 cells per well). The next day
+
6
2
+H ].
[
the compound diluted in culture medium at various concentrations was added
3
−1
0
.37×0.19×0.17 mm , triclinic, space group P−1, a=5.889(1) Å, b=10.236
1) Å, c = 12.383(1) Å, α = 94.628(2)° β = 90.468(2)° γ = 90.987(2)°
V=743.86(13) Å 3, Z=2, ρcalcd=1.234 Mg·m−3, 2595 reflections collected,
099 unique (Rint=0.0454), R1=0.0608 [IN2σ (I)], and wR2=0.1850 (all
(200 μL per well) to the wells. 48 h later 20 μL of MTT (0.5 mg mL MTT in PBS)
(
was added and cells were incubated for a further 4 h. 200 μL of DMSO were added
to each culture to dissolve the MTT crystals. The MTT-formazan product dissolved
in DMSO was estimated by measuring absorbance at 570 nm with a micro plate
reader. Then the inhibitory percentage of each compound at various concentra-
tions was calculated, and the IC50 value was determined.
2
data). The data were collected on a Bruker APEX-II CCD diffractometer (MoKa,
λ=0.71073 Å) at 296(2) K. All structures were solved by the direct method and
refined by the full-matrix least-squares on F2 using the SHELXL-97 [19,20]. All of
the non-hydrogen atoms were refined anisotropically.
[35] H.G. Petering, G.J. Van Giessen, Biochem. Copper, Proc. Symp. (1966) 197.
[36] H. Beraldo, D. Gambino, Mini-Rev. Med. Chem. 4 (2004) 31.
[19] G.M. Sheldrick, SHELXS 97, Program for Crystal Structure Solution, University of
Göttingen, Göttingen, 1997.