close

Вход

Забыли?

вход по аккаунту

?

S N-Chelated organotin(IV) compounds containing 6-phenylpyridazine-3-thiolate ligandЧstructural antibacterial and antifungal study.

код для вставкиСкачать
Full Paper
Received: 21 March 2011
Revised: 24 May 2011
Accepted: 8 June 2011
Published online in Wiley Online Library: 7 September 2011
(wileyonlinelibrary.com) DOI 10.1002/aoc.1823
S,N-Chelated organotin(IV) compounds
containing 6-phenylpyridazine-3-thiolate
ligand – structural, antibacterial and antifungal
study
Andrii Ozerianskyia , Petr Šveca , Hana Vaňkátováa , Marcela Vejsováb ,
Lenka Česlovác , Zdeňka Padělkováa, Aleš Růžičkaa∗ and Jaroslav Holečeka
A series of tri- and diorganotin(IV) compounds containing potentially chelating S,N-ligand(s) (LSN , where LSN is 6phenylpyridazine-3-thiolate) were prepared and structurally characterized by multinuclear NMR spectroscopy. X-ray diffraction
techniques were used for determination of the structure of compounds containing one [(LSN )Ph2 SnCl], two [(n-Bu)2 Sn(LSN )2 ] and
the combination of two LSN and one LCN [(LCN )(n-Bu)Sn(LSN )2 ] (where LCN is {2-[(CH3 )2 NCH2 ]C6 H4 }-) ligands. The coordination
number of the tin atom varies from five to seven and is dependent on the number of chelating ligands present. The formation
of the five-membered azastanna heterocycle is favored over the formation of four-membered azastannathia heterocycle in
compounds containing both types of ligands. The di-n-butyl-substituted compounds are the most efficient ones in inhibition of
c 2011 John Wiley & Sons, Ltd.
growth of yeasts, molds and G+ bacteria strains. Copyright Supporting information may be found in the online version of this article.
Keywords: organotin(IV) compounds; NMR spectroscopy; X-ray diffraction analyses; antibacterial and fungicidal study
Introduction
Appl. Organometal. Chem. 2011, 25, 725–734
∗
Correspondence to: Aleš Růžička, Department of General and Inorganic
Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská
95, CZ-532 10, Pardubice, Czech Republic. E-mail: ales.ruzicka@upce.cz
a Department of General and Inorganic Chemistry, Faculty of Chemical
Technology, University of Pardubice, Studentská 95, CZ-53210, Pardubice,
Czech Republic
b Department of Biological and Medicinal Sciences, Faculty of Pharmacy, Charles
University in Prague, Heyrovského 1203, CZ-50005, Hradec Králové, Czech
Republic
c DepartmentofAnalyticalChemistry,FacultyofChemicalTechnology,University
of Pardubice, Studentská 95, CZ-53210, Pardubice, Czech Republic
c 2011 John Wiley & Sons, Ltd.
Copyright 725
Organotin compounds have numerous applications.[1] Among
others, they are commercially used as agricultural biocides owing
to their antifungal properties.[1,2] Biological aspects of organotin
compounds have been thoroughly discussed in the literature.[3]
Diorganotin compounds have been evaluated for their antitumor
activity as well.[4]
The coordination chemistry of tin is extensive with various
geometries and coordination numbers well known for both
organometallic and inorganic compounds.[1] The tin atom can
increase its coordination number by inter- and/or intra-molecular
interactions with electronegative atoms, namely nitrogen, oxygen
and sulfur. Whereas tin is considered to be a hard acid,
many compounds containing the tin–sulfur bond(s) are known.
Simple tri- and diorganotin(IV) thiolates of general formula
R3 SnSR and R2 Sn(SR )2 , where the R groups contain no donor
centers, are strictly four-coordinate species with nearly tetrahedral
geometry.[5] On the other hand, the situation dramatically changes
if the R groups contain a potentially donor atom (N, O, S). If donor
atoms are available, the coordination number of the tin atom may
increase from four to five and even to six. Such compounds have
been reported.[6] The vicinity of the tin atom in five-coordinated
compounds usually reveals a distorted trigonal bipyramidal
geometry.[6] Compounds having six-coordinated tin atom have
been described as both monocapped trigonal bipyramidal[7]
and heavily distorted octahedral structures.[6] The five-membered
chelate rings seem to be much more stable than four-membered
chelate rings, which usually do not persist in solution.[8] SousaPedrares et al. reported on compounds where the tin atom is
even eight-coordinated, bearing four S,N-chelating ligands.[9] In
all these cases sulfur is covalently bonded to the tin atom whereas
nitrogen atom coordinates to the same tin atom. To the best of
our knowledge no compounds containing S,N-chelating ligands,
where covalent Sn–N bond(s) and S → Sn interaction(s) could be
identified, are known.
Our interest is mainly focused on the family of organotin(IV)
compounds containing a [2-(N,N-dimethylamino)methyl]phenylgroup (LCN ) or related ligands that reveal interesting structural
properties[10,11] and potential use as transesterification catalysts,
antimycotical or fluorinating agents.[12]
In our recent paper, we described the preparation, structure and reactivity of triorganotin(IV) cyclopentadienides, hydrides and distannanes bearing the LCN ligand.[13] We have
also published the preparation and structural determination
of zwitterionic tri- and diorganostannates bearing protonated
A. Ozerianskyi et al.
Scheme 1. List of compounds prepared and their general NMR numbering.
[2-(N,N-dimethylamino)methyl]phenyl moiety.[14] Novel zwitterionic triorganostannate bearing two trifluoroacetate substituents
was also prepared during this work. Based on the latter results one
paper concerning the synthesis, structural characterization and
potential use of some C,N-chelated organotin(IV) trifluoroacetates
followed.[15]
In this paper we report on the preparation of some new
organotin(IV) compounds bearing potentially chelating S,Nligand(s) (LSN = 6-phenylpyridazine-3-thiolate) with the different
coordination modes by two possible tautomeric forms. Structural
investigation of prepared compounds in solution as well as in the
solid state, and the results of in vitro antimycotical and antibacterial
screening, are also discussed in this paper (for general NMR
numbering of compounds see Scheme 1).
Experimental Section
General Remarks
All experiments were carried out under an argon atmosphere
using standard Schlenk technique except for the 6-phenyl-3(2H)pyridazinethione, which was synthesized in air. All reactants
and solvents were obtained from commercial sources (SigmaAldrich). Dichloromethane was dried over and distilled from
calcium hydride, degassed and stored under argon. Other solvents
were used as received. LCN (n-Bu)2 SnCl,[16] LCN (n-Bu)SnCl2 [16] and
6-phenyl-3(2H)-pyridazinone[17] were synthesized according to
published procedures.
NMR Spectroscopy
726
The solution NMR spectra were recorded in CDCl3 , benzened6 and dimethyl sulfoxide (DMSO)-d6 on a Bruker Avance
500 spectrometer (equipped with a Z-gradient 5 mm probe) at
frequencies 1 H (500.13 MHz), 13 C{1 H} (125.76 MHz) and 119 Sn{1 H}
(186.50 MHz) at 295 K. The solutions were obtained by dissolving
approximately 30 mg of each compound in 0.6 ml of deuterated
solvent. The values of 1 H chemical shifts were calibrated to
residual signals of CDCl3 [δ(1 H) = 7.27 ppm], benzene-d6 [δ(1 H) =
7.1 ppm] or DMSO-d6 [δ(1 H) = 2.50 ppm]. The 13 C chemical shift
values were calibrated to signals of CDCl3 [δ(13 C) = 77.2 ppm].
The 119 Sn chemical shift values are referred to external neat
tetramethylstannane [δ(119 Sn) = 0.0 ppm]. Positive chemical shift
values denote shifts to the higher frequencies relative to the
standards. 119 Sn NMR spectra were measured using the inverse
gated-decoupling mode.
wileyonlinelibrary.com/journal/aoc
X-Ray Crystallography
The X-ray data (Table 1) for single crystals of (LSN )2 CH2 , 2, 3,
and 6 were obtained at 150 K using an Oxford Cryostream lowtemperature device on a Nonius KappaCCD diffractometer with
MoKα radiation (λ = 0.71073 Å), a graphite monochromator, and
the φ and χ scan mode. Data reductions were performed with
DENZO-SMN.[18] Absorption effects were corrected by integration
methods.[19] Structures were solved by direct methods (Sir92)[20]
and refined by full matrix least-square based on F2 (SHELXL-97).[21]
Hydrogen atoms were mostly localized on a difference Fourier map;
however to ensure uniformity of the treatment of the crystal, all
hydrogen atoms were recalculated into idealized positions (riding
model) and assigned temperature factors Hiso (H) = 1.2 Ueq (pivot
atom) or of 1.5Ueq for the methyl moiety with C–H = 0.96, 0.97,
and 0.93 Å for methyl, methylene and hydrogen atoms in aromatic
rings, respectively.
Crystallographic data for structural analysis have been deposited with the Cambridge Crystallographic Data Centre. Copies
of this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge CB2 1EY, UK
(fax: +44-1223-336033; email: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
Mass Spectrometry
Positive-ion electrospray ionization (ESI) mass spectra (MS) were
measured on the LCQ ion trap analyzer (Thermo Fisher Scientific,
Waltham, MA, USA) in the range m/z 100–1200. The samples were
dissolved in acetonitrile and analyzed by direct infusion at the flow
rate 3 µL/min. The ESI ion source spray voltage was set to 4.0 kV.
The capillary temperature was set to 250 ◦ C, capillary voltage to
5 V and tube lens offset voltage to 15 V.
In Vitro Antifungal Screening
The in vitro testing was carried out by the modified microdilution
broth method according to the M27-A guideline (NCCLS 1997).
Quality control strains (Candida albicans ATCC 90 028, C. parapsilosis ATCC 22 019, C. krusei ATCC 6258) and amphotericin B (Sigma),
fluconazole (Pfizer) and ketoconazole (Janssen-Cilag, Beerse) as
reference drugs were studied. All fungal strains were added on
Sabouraud dextrose agar at 35 ◦ C prior to being tested.
The minimum inhibitory concentration (MIC) and the minimum
fungicidal concentration (MFC) were determined by the following method.[22] Dimethyl sulfoxide served as a co-solvent for all
compounds tested. DMSO did not exceed the final concentration
of 2%. RPMI 1640 (Sevapharma, Prague) medium supplemented
c 2011 John Wiley & Sons, Ltd.
Copyright Appl. Organometal. Chem. 2011, 25, 725–734
S,N-Chelated organotin(IV) compounds
Table 1. Selected crystallographic parameters of prepared compounds
Compound
Formula
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
Z
V (Å 3 )
Dc (g cm−3 )
Crystal size (mm)
Crystal shape
µ (mm−1 )
F(000)
h; k; l range
θ range (deg)
Reflections measured
independent (Rint )a
observed [I > 2σ (I)]
Parameters
Max/min ρ (e Å −3 )
GOFb
R/wRc
CCDC no.
(LSN )2 CH2
2
3
6
C21 H16 N4 S2
Monoclinic
C2/c
21.8238(8)
8.0020(6)
11.2381(8)
90
113.231(6)
90
4
1803.5(3)
1.431
0.31 × 0.19 × 0.15
Block
0.309
808
−28, 24; −9, 10; −14, 14
2.7–27.5
8165
2043
1347
123
0.518/−1.264
1.165
0.082/0.126
804 248
C22 H17 ClN2 SSn
Triclinic
P-1
9.5788(8)
9.6831(12)
11.8803(19)
76.268(11)
78.210(14)
77.178(15)
2
1030.3(3)
1.598
0.71 × 0.25 × 0.23
Block
1.480
492
−12, 12; −12, 12; −15, 15
1.8–27.5
18 952
4715
3875
244
0.534/−0.541
1.121
0.031/0.064
804 249
C28 H32 N4 S2 Sn
Monoclinic
C2/c
33.5992(10)
10.4548(8)
16.6152(9)
90
102.12(5)
90
8
5706.8(2)
1.414
0.47 × 0.29 × 0.16
Block
1.065
2480
−42, 43; −13, 13; −21, 21
2.0–27.5
58 377
6534
4396
316
0.779/−0.572
1.121
0.040/0.079
804 250
C25 H15 N5 S2 Sn 2(C4 H10 O)
Orthorhombic
Pba2
16.8620(8)
23.5551(7)
8.9360(15)
90
90
90
4
3549.2(6)
1.341
0.22 × 0.21 × 0.15
Block
0.872
1464
−21, 20; −30, 30; −10, 11
1.5–27.5
27 006
7051
5659
370
0.465/−0.653
1.021
0.041/0.072
804 251
Rint = |F o 2 − F o,mean 2 |/F o 2 ;
S = {[w(F o 2 − F c 2 )2 ]/(Ndiffrs − Nparams )}1/2 ;
c weighting scheme: w = [σ 2 (F 2 ) + (w P)2 + w P]−1 , where P = [max(F 2 ) + 2F 2 ], R(F) = | |F | − |F | |/|F |, wR(F 2 ) = {[w(F 2 −
o
1
2
o
c
o
c
o
o
F c 2 )2 ]/[w(F o 2 )2 ]}1/2 .
a
b
with L-glutamine and buffered with 0.165 M morpholinepropanesulfonic acid (Serva) to pH 7.0 using 10 M NaOH was used as a test
medium. Each well of the microdilution tray was filled with 200 µl
of the RPMI 1640 medium with a diluted compound tested and
then inoculated with 10 L of suspension of a given fungal strain in
sterile water. Fungal inoculum was prepared to give a final size of
5 × 103 ± 0.2 CFU ml−1 . The trays were incubated at 35 ◦ C and the
MICs read after 24 and 48 h. Owing to slow growth, Trichophyton
mentagrophytes strain was read at 72 and 120 h. The MICs were
determined visually and defined as 80% inhibition of the growth
of control.
In Vitro Antibacterial Screening
Appl. Organometal. Chem. 2011, 25, 725–734
Synthesis
Preparation of 6-phenyl-3(2H)-pyridazinethione (LSN H)
6-Phenyl-3(2H)-pyridazinone (21.3 g, 0.124 mol) and Lawesson’s
reagent (27.52 g, 0.068 mol) were dissolved in 1,4-dioxane (300 ml).
The reaction mixture was heated to reflux for 3 h. Afterwards
the dioxane was removed in vacuo and the reaction residue
was suspended in sodium hydroxide solution (0.15 mol NaOH in
50 ml of water). The suspension was filtered and the filtrate was
acidified by dropwise addition of aqueous HCl (36%, ca. 15 ml) to
obtain a neutral pH. Resulting precipitate was filtered and washed
with 20 ml of cold water. Desired yellow solid 1 was dried in
vacuo. Isolated yield was 17.5 g (75%). The compound exhibits a
characteristic unpleasant odor. M.p. 155–157 ◦ C. 1 H NMR (DMSOd6, 295 K, ppm): 14.89 (s, 1H, NH); 7.89 [m, 3H, H(3×) and H(4×)];
7.71 {d, 1H, H(4), 3 J[1 H(5), 1 H(4)] = 8.1 Hz}; 7.51 [m, 3H, H(2×) and
H(5)]. ESI-MS, positive-ion mode: m/z 375, [(LSN )2 + H]+ , 100%;
m/z 189, [M + H]+ , 91%. Elemental analysis (%): found C, 63.3;
H, 4.8; N, 14.4. Calcd for C10 H8 N2 S (188.25): C, 63.80; H, 4.28; N,
14.88.
c 2011 John Wiley & Sons, Ltd.
Copyright wileyonlinelibrary.com/journal/aoc
727
All strains were subcultured on nutrient agar (HiMedia) and
maintained on the same medium at 4 ◦ C. Prior to testing, each
strain was added onto nutrient agar and bacterial inocula were
prepared by suspending small portion of bacterial colony in sterile
0.85% saline. The cell density was adjusted to 105 CFU ml−1 using
densitometer (Densi-La-Meter, PLIVA Lachema Diagnostika). The
final inoculum was made by 1 : 20 dilution of the suspension with
the test medium (Mueller-Hinton broth). The compounds were
dissolved in DMSO and antibacterial activity was determined in
Mueller–Hinton broth (MH broth, HiMedia, pH 7.0 ± 0.2). Controls
consisted of MH broth and DMSO alone. The final concentration of
DMSO in the MH broth did not exceed 1% (v/v) of the total
solution composition. The MIC, defined as 80% inhibition of
bacterial growth compared with control, was determined after
24 and 48 h of static incubation at 37 ◦ C.
A. Ozerianskyi et al.
Preparation of (6-phenylpyridazine-3-thiolate)-di-n-butyltin(IV) chloride LSN (n-Bu)2 SnCl (1)
(LSN H) (0.700 g, 3.72 mmol) reacted with slight excess of t-BuOK
(97%, 0.473 g, 4.09 mmol) in anhydrous dichloromethane (25 ml)
for 30 min to give LSN K quantitatively. Afterwards the solution of
(n-Bu)2 SnCl2 (1.130 g, 3.72 mmol) in anhydrous dichloromethane
(15 ml) was added. The reaction mixture was heated to reflux for
1 h and filtered to remove the potassium chloride. The filtrate was
reduced in vacuo and the crude product was washed with hexane
(2 × 10 ml), giving an yellow oily product. Yield was 1.615 g (95%).
1 H NMR (CDCl , 295 K, ppm): 7.91 {d, 2H, H(2×), 3 J[1 H(3×), 1 H(2×)]
3
= 9.0 Hz}; 7.65 [m, 2H, H(4) and H(5)]; 7.50–7.46 [m, 3H, H(3×) and
H(4×)]; 1.79 [m, 4H, H(1)]; 1.59 [m, 4H, H(2)]; 1.39 [m, 4H, H(3)];
0.88 [t, 6H, H(4)]. 119 Sn NMR (CDCl3 , 295 K, ppm): −43.1. ESI-MS,
positive-ion mode: m/z 921, [M − Cl + 2 × Me(n-Bu)2 SnH]+ , 23%;
m/z 671, [M − Cl + Me(n-Bu)2 SnH]+ , 88%; m/z 421, [M − Cl]+ ,
100%. Elemental analysis (%): found C, 48.0; H, 5.8; N, 6.0. Calcd for
C18 H25 ClN2 SSn (455.62): C, 47.45; H, 5.53; N, 6.15.
Preparation of (6-phenylpyridazine-3-thiolate)diphenyltin(IV) chloride (LSN )Ph2 SnCl (2)
The synthesis was similar to the preparation of 1, but the
temperature was maintained at 0 ◦ C. Reactants used were LSN H
(0.700 g, 3.72 mmol), t-BuOK (97%, 0.473 g, 4.09 mmol) and
Ph2 SnCl2 (1.278 g, 3.72 mmol). Pale-yellow crystalline product
resulted. Yield was 1.732 g (94%). Single crystals were obtained by
slow vapour diffusion of n-hexane to a chloroform solution of 2.
M.p. 172–174 ◦ C. 1 H NMR (CDCl3 , 295 K, ppm): 8.06 {d, 4H, H(2 ),
3 1
J[ H(3 ), 1 H(2 )] = 6.2 Hz, 3 J(119 Sn, 1 H) = 84.0 Hz}; 7.92 [broad d,
2H, H(2×)]; 7.68 and 7.62 {AB pattern, 2H, H(4, 5), 3 J[1 H(5), 1 H(4)]
= 9.0 Hz}; 7.55–7.49 (m, 3H, Ph and LSN ); 7.45–7.38 (m, 6H, Ph
and LSN ). 13 C NMR (CDCl3 , 295 K, ppm): 168.2 [C(3)]; 156.2 [C(6)];
140.7 [C(1 ),117/119 Sn satellites were not found]; 137.2 [C(1×)];
136.0 [C(2 ), 2 J(119 Sn, 13 C) = 59.2 Hz]; 135.0 [C(4×)]; 130.7 [C(5)];
130.6 [C(4 )]; 129.4 [C(3×)]; 129.2 [C(3 ), 3 J(119 Sn, 13 C) = 78.3 Hz];
127.1 [C(4)]; 126.8 [C(2×)]. 119 Sn NMR (CDCl3 , 295 K, ppm): −187.3.
ESI-MS, positive-ion mode: m/z 687, [Ph2 Sn(LSN )2 + K]+ , 30%; m/z
671, [Ph2 Sn(LSN )2 + Na]+ , 85%; m/z 519, [M + Na]+ , 6%; m/z 461,
[M − Cl]+ , 100%. Elemental analysis (%): found C, 53.8; H, 3.6; N,
5.4. Calcd for C22 H17 ClN2 SSn (495.60): C, 53.32; H, 3.46; N, 5.65.
Preparation of di-n-butyltin(IV) bis(6-phenylpyridazine-3-thiolate) (nBu)2 Sn(LSN )2 (3)
728
The synthesis was similar to the preparation of 1. Reactants used
were LSN H (1.000 g, 5.31 mmol), t-BuOK (97%, 0.676 g, 5.84 mmol)
and (n-Bu)2 SnCl2 (0.807 g, 2.66 mmol). Yield was 1.548 g (96%).
Light ochre single crystals were obtained by slow vapour diffusion
of n-hexane to a chloroform solution of 3. M.p. 143–145 ◦ C. 1 H
NMR (CDCl3 , 295 K, ppm): 7.95 {d, 4H, H(2×), 3 J[1 H(3×), 1 H(2×)]
= 7.3 Hz}; 7.62 and 7.57 {AB pattern, 4H, H(4, 5), 3 J[1 H(5), 1 H(4)] =
9.0 Hz}; 7.51–7.45 [m, 6H, H(3×) and H(4×)]; 1.87 [t, 4H, H(1)]; 1.69
[m, 4H, H(2)]; 1.34 [m, 4H, H(3)]; 0.78 [t, 6H, H(4)]. 13 C NMR (CDCl3 ,
295 K, ppm): 168.2 [br, C(3)]; 154.8 [C(6)]; 136.3 [C(4×)]; 129.9 [C(5)];
129.2 [C(3×)]; 126.7 [C(2×)]; 124.9 [C(4)]; 28.3 [C(2), 2 J(119 Sn, 13 C) =
38.6 Hz]; 27.3 [C(1), 1 J(119 Sn, 13 C) = 552.0 Hz]; 26.4 [C(3), 3 J(119 Sn,
13
C) = 110.4 Hz]; 13.9 [C(4)]; the resonance of the C(1×) atom
was not found. 119 Sn NMR (CDCl3 , 295 K, ppm): −108.2. ESI-MS,
positive-ion mode: m/z 921, [M − LSN + 2 × Me(n-Bu)2 SnH]+ , 25%;
m/z 671, [M − LSN + Me(n-Bu)2 SnH]+ , 48%; m/z 631, [M + Na]+ ,
7%; m/z 421, [M − LSN ]+ , 100%. Elemental analysis (%): found C,
wileyonlinelibrary.com/journal/aoc
55.8; H, 5.6; N, 8.9. Calcd for C28 H32 N4 S2 Sn (607.41): C, 55.37; H,
5.31; N, 9.22.
Preparation of diphenyltin(IV) bis(6-phenylpyridazine-3-thiolate)
Ph2 Sn(LSN )2 (4)
The synthesis was similar to the preparation of 1. Reactants used
were LSN H (0.700 g, 3.72 mmol), t-BuOK (97%, 0.473 g, 4.09 mmol)
and Ph2 SnCl2 (0.639 g, 1.86 mmol). Light ochre crystalline product
resulted. Yield was 1.120 g (93%). M.p. 173–176 ◦ C. 1 H NMR (CDCl3 ,
295 K, ppm): 8.06 {d, 4H, H(2 ), 3 J[1 H(3 ), 1 H(2 )] = 6.8 Hz, 3 J(119 Sn,
1 H) = 83.0 Hz}; 7.80 {d, 4H, H(2×), 3 J[1 H(3×), 1 H(2×)] = 6.4 Hz};
7.53 and 7.50 {AB pattern, 4H, H(4, 5), 3 J[1 H(5), 1 H(4)] = 9.0 Hz};
7.41–7.36 (m, 6H, Ph and LSN ); 7.33–7.24 (m, 6H, Ph and LSN ). 119 Sn
NMR (CDCl3 , 295 K, ppm): −233.1. ESI-MS, positive-ion mode: m/z
687, [M + K]+ , 96%; m/z 671, [M + Na]+ , 22%; m/z 461, [M − LSN ]+ ,
100%. Elemental analysis (%): found C, 59.8; H, 3.6; N, 8.8. Calcd for
C32 H24 N4 S2 Sn (647.39): C, 59.37; H, 3.74; N, 8.65.
Preparation of {2-[(N,N-dimethylaminomethyl)phenyl]}-di-n-butyltin(IV) (6-phenylpyridazine-3-thiolate) LCN (n-Bu)2 SnLSN (5)
The synthesis was similar to the preparation of 1. Reactants used
were LSN H (0.700 g, 3.72 mmol), t-BuOK (97%, 0.473 g, 4.09 mmol)
and LCN (n-Bu)2 SnCl (1.497 g, 3.72 mmol). Yellowish oily product
resulted. Isolated yield was 1.752 g (85%). 1 H NMR (CDCl3 , 295 K,
ppm): 7.90 {d, 2H, H(2×), 3 J[1 H(3×), 1 H(2×)] = 7.0 Hz}; 7.86 {d, 1H,
H(6 ), 3 J[1 H(5 ), 1 H(6 )] = 7.3 Hz,3 J(119 Sn, 1 H) = 58.9 Hz}; 7.55 and
7.48 {AB pattern, 2H, H(4, 5), 3 J[1 H(5), 1 H(4)] = 8.8 Hz}; 7.45–7.40
(m, 3H, LCN and LSN ); 7.19 (m, 2H, LCN and LSN ); 7.06 {d, 1H, H(3 ),
3 J[1 H(4 ), 1 H(3 )] = 6.7 Hz}; 3.54 (s, 2H, CH N); 2.27 [s, 6H, N(CH ) ];
2
3 2
1.56 [m, 4H, H(1)]; 1.43 [m, 4H, H(2)]; 1.26 [m, 4H, H(3)]; 0.78 [t, 6H,
H(4)]. 119 Sn NMR (CDCl3 , 295 K, ppm): −53.8. ESI-MS, positive-ion
mode: m/z 368, [M − LSN ]+ , 100%. Elemental analysis (%): found
C, 58.3; H, 6.3; N, 7.7. Calcd for C27 H37 N3 SSn (554.37): C, 58.50; H,
6.73; N, 7.58.
Preparation of {2-[(N,N-dimethylaminomethyl)phenyl]}-n-butyltin(IV) bis(6-phenylpyridazine-3-thiolate) (LCN )(n-Bu)Sn(LSN )2 (6)
The synthesis was similar to the preparation of 1. Reactants used
were LSN H (0.516 g, 2.74 mmol), t-BuOK (97%, 0.349 g, 3.01 mmol)
and LCN (n-Bu)SnCl2 (0.522 g, 1.37 mmol). Pale-yellow crystalline
product resulted. Crystallization of the crude product from diethyl
ether gave single crystals of the desired product. Isolated yield
was 0.647 g (69%). M.p. 102–104 ◦ C. 1 H NMR (C6 D6 , 295 K, ppm):
7.90 {d, 4H, H(2×), 3 J[1 H(3×), 1 H(2×)] = 7.1 Hz}; 7.85 {d, 1H, H(6 ),
3 J[1 H(5 ), 1 H(6 )] = 7.0 Hz,3 J(119 Sn, 1 H) = 93.0 Hz}; 7.53–7.40 (m,
8H, LCN and LSN ); 7.10 (m, 4H, LCN and LSN ); 6.99 {d, 1H, H(3 ),
3 J[1 H(4 ), 1 H(3 )] = 6.6 Hz}; 3.99 (s, 2H, CH N); 2.76 [s, 6H, N(CH ) ];
2
3 2
1.61 [m, 2H, H(1)]; 1.32 [m, 2H, H(2)]; 1.15 [m, 2H, H(3)]; 0.73 [t, 3H,
H(4)]. 119 Sn NMR (C6 D6 , 295 K, ppm): −284.1. ESI-MS, positive-ion
mode: m/z 498, [M − LSN ]+ , 94%; m/z 328, [LCN (n-Bu)SnOH]+ ,
100%. Elemental analysis (%): found C, 58.3; H, 5.3; N, 10.0. Calcd
for C33 H35 N5 S2 Sn (684.50): C, 57.91; H, 5.15; N, 10.23.
Results and Discussion
Synthesis
The studied organotin(IV) compounds bearing the LSN ligand(s)
were prepared by the reaction of the respective organotin(IV) chloride with appropriate amount of 6-phenyl-3(2H)-pyridazinethione
c 2011 John Wiley & Sons, Ltd.
Copyright Appl. Organometal. Chem. 2011, 25, 725–734
S,N-Chelated organotin(IV) compounds
Figure 1. Molecular structure of (LSN )2 CH2 (ORTEP view, 50% probability level). Hydrogen atoms are omitted for clarity. Selected interatomic distances
(Å) and angles (deg): S1–Cl 1.800(3), S1a–C1 1.800(3), S1–C2 1.764(4), S1a–C2a 1.764(4), S1–C1–S1a 115.9(3), C1–S1–C2 101.94(14), C1–S1a–C2a
101.94(14), S1–C2–N1 117.9(3), S1a–C2a–N1a 117.9(3).
and potassium tert-butoxide in boiling dichloromethane (except
for 2, see Experimental). All reactions gave satisfactory (85% for 5)
to nearly quantitative yields (96% for 3) of desired products except
for 6, which had to be purified by crystallization, thus decreasing
the yield to 69%. All prepared compounds are stable in the air and
do not react with moisture.
Only several yellow single crystals of (LSN )2 CH2 were isolated
from the flask containing the reaction mixture of LSN H, potassium
tert-butoxide and Ph2 SnCl2 in dichloromethane when preparing
4. This compound was formed in a negligible yield as a by-product.
The presumably formed LSN K reacted apparently with the boiling
dichloromethane used as a solvent to give (LSN )2 CH2 , which is very
unusual reaction. Unfortunately when we tried to reproduce the
reaction without the presence of Ph2 SnCl2 , we did not observed
any formation of mentioned product and thus no NMR spectra
are available for this compound. Despite this fact, isolated single
crystals were fortunately suitable for the X-ray diffraction analysis.
The molecule of (LSN )2 CH2 crystallizes in the monoclinic system
and reveals a two-fold C2/c symmetry (Fig. 1). The interatomic
distances S1–C1 [1.800(3) Å] and S1–C2 [1.764(4) Å] are very close
to the sum of covalent radii of carbon and sulfur (1.82 and 1.78 Å,
respectively).[23] Other selected interatomic distances and angles
are given in the caption for Fig. 1.
ESI-MS
The ESI-MS spectra can be taken as an indirect proof for the
compounds’ identities. The results of ESI-MS measurements are
given in the Experimental section. Owing to the characteristic
isotopic distribution of the tin element, the presence or absence of
the tin atom in individual fragment can be easily recognized.[11b]
There are two main mechanisms of the ion formation: (1) the
cleavage of the most labile Sn–S bond in compounds having no
Sn–Cl bond results in formation of [M − LSN ]+ ion (3–6) and
(2) the cleavage of the Sn–Cl bond in compounds where chloride
is bonded directly to the tin atom gives the [M − Cl]+ ion (1 and
2). In addition to these ions, the spectra also reveal the existence
of [M + H]+ (LSN H) and/or [M + Na]+ ions (2– 4).
Solution-state Study
Appl. Organometal. Chem. 2011, 25, 725–734
c 2011 John Wiley & Sons, Ltd.
Copyright wileyonlinelibrary.com/journal/aoc
729
The 1 H and 119 Sn NMR spectra of all prepared compounds were
measured in CDCl3 (except for 6, which was measured in benzene-
d6) at 295 K. Owing to the limited solubility of compounds in
noncoordinating solvents, not all 13 C NMR spectra were measured
and low-temperature measurements were not performed. All
recorded 1 H NMR spectra are in good conformity with the
proposed composition of each compound with respect to the
nature and number of each substituent. The 1 H NMR spectra of all
compounds reveal only one sharp and resolved set of signals at
room temperature. The only exception is compound 6, where the
resonances are somewhat broadened owing to the proposed fast
equilibrium (at least on the NMR time scale) between mono- and
bidentately bonded LSN ligands (see below). The 13 C NMR spectra
of 2 and 3 were recorded (see Experimental section) giving no
additional information to the uniformity and structure of these
compounds.
The solution structures of diorganotin(IV) compounds studied
can be described on the basis of several NMR spectra parameters.
The most important parameters for the direct evaluation of the
structure arise from nuclei involved directly in the coordination
polyhedra of the central tin atom.[16,24] On the basis of this
approach, we consider structures of 1 and 2 to have a distorted
trigonal bipyramid geometry since the 119 Sn NMR chemical
shift values (summarized in Table 2) are in accordance with
the values found for five-coordinated tin species in a solution
of a noncoordinating solvent.[6,16,24,25] The more electronegative
nitrogen and chlorine atoms occupy axial positions while two
carbon atoms and sulfur atom originating from the LSN moiety are
situated in the equatorial plane.
The triorganotin(IV) compound 5 has been prepared in
order to compare the coordination behavior with tin atoms
in diorganotin(IV) compounds 1 and 2. In 5 where the tin
is presumably five-coordinated, there are also three carbon
atoms situated in the equatorial plane since the sulfur atom
already occupies the axial position, and the second axial
position is occupied by coordinated pendant NMe2 group.
In all these cases (for compounds 1, 2 and 5), we assume
relatively strong intramolecular N → Sn interactions. The N →
Sn interaction persists even in the solution. In the case of 5,
where both LCN and LSN ligands are present, we believe the
formation of five-membered azastannaheterocycle (e.g. LCN → Sn
interaction) is favored instead of formation of only four-membered
azastannathioheterocycle, which is presumably less stable owing
to its strained geometry. The indirect proof of this coordination is
A. Ozerianskyi et al.
Table 2. Tin coordination number and δ(119 Sn) of 1–6
Sn coordination number
Compound
1
2
3
4
5
6
Solid state
Solution
δ(119 Sn) (CDCl3 , ppm)
–
5a
6b
–
–
7d
5a
5a
5–6c
5–6c
5a
6
−43.1
−187.3
−108.2
−233.1
−53.8
−284.1e
a
Distorted trigonal bipyramid;
distorted octahedron;
c
fast equilibrium on the NMR time scale;
d distorted pentagonal bipyramid;
e in C D .
6 6
Solid-state Study
b
730
the similarities in values of chemical shifts of CH2 N(CH3 )2 group
in 1 H NMR spectra of 5 (and also 6 – see below) to the known
compounds with rather strong coordination.[10,16,25]
In addition, the 119 Sn NMR chemical shift values of 1
(−43.1 ppm) and 5 (−53.8 ppm) are relatively close to the
−47.5 ppm found for LCN (n-Bu)2 SnCl, where the tin is fivecoordinated too.[16] Similarly, the δ(119 Sn) of 2 (−187.3 ppm)
is comparable to the δ(119 Sn) of LCN Ph2 SnCl (−177.1 ppm)
which reveals a distorted trigonal bipyramidal geometry around
the central tin atom.[24] Furthermore, all discussed δ(119 Sn) of
compounds 1, 2 and 5 are in very good agreement with 119 Sn
NMR chemical shift values found for related five-coordinated
S,N-chelated organotin(IV) compounds.[6]
On the other hand, compounds 3 and 4 contain two potentially
bidentate LSN ligands and therefore the coordination number
of the tin atom might be presumably five or six in the chloroform solution. We deduce this conclusion from the differences
between the 119 Sn NMR chemical shift values of starting fourcoordinated diorganotin(IV) dichloride (124 ppm for (n-Bu)2 SnCl2
[26] and −27 ppm for Ph SnCl ,[27] respectively) and the corre2
2
sponding product (−108.2 ppm for 3 and −233.1 ppm for 4,
respectively). According to the differences of δ(119 Sn), we infer
the increase of the coordination number from four to five/six and
therefore fast alternation between the trigonal bipyramidal and
deformed pseudo-octahedral vicinity of the central tin atom in
these compounds in solution (e.g. fast equilibrium between one
monodentately and one bidentately bonded LSN ligands on the
NMR time scale), contrary to other authors who consider diorganotin(IV) compounds bearing two S,N-chelating ligands to be strictly
six-coordinated in the solution.[6i,k,l,28] This hypothesis is not incompatible with the X-ray structure of 3, where the tin atom is unambiguously six-coordinated (see Fig. 4), and its NMR spectra, as it is
known that the N → Sn interaction may not persist in solution.[6ik,l,8]
The compound 6 has been prepared in order to increase the coordination number of the tin atom and thus change some spectral
as well as biological properties. The tin atom in the solid 6 is [6 + 1]
coordinated with distorted pentagonal bipyramidal vicinity (see
below). According to recorded 119 Sn NMR spectrum of 6 [δ(119 Sn) =
−284.1 ppm], we suggest the presence of six-coordinated tin(IV)
species in the benzene solution. This deduction is based on the
known 119 Sn NMR chemical shift values of similar diorganotin(IV)
compounds [for example LCN (n-Bu)Sn(OCOCF3 )2 , δ(119 Sn) =
−282.8 ppm;[29] (LCN )2 SnCl2 , δ(119 Sn) = −252.8 ppm; (LCN )2 SnBr2 ,
δ(119 Sn) = −271.2 ppm], prepared by us where the tin atom is
wileyonlinelibrary.com/journal/aoc
actually six-coordinated too.[30] Based on this fact we presume the
dynamic bonding fashion of both LSN moieties (e.g. fast equilibrium
between monodentately and bidentately bonded LSN ligands),
which is undetectable on the relatively slow NMR time scale.
Compounds bearing the LCN ligand can be also characterized
by the value of the coupling constant 3 J[119 Sn, 1 H(6 )]. Compound
6 exhibits 3 J(119 Sn, 1 H) of 93.0 Hz, which is within the range
found for hypercoordinated diorganotin(IV) species, and also
compound 5 reveals 3 J(119 Sn, 1 H) to be 58.9 Hz, which is typical
for hypercoordinated triorganotin(IV) compounds.[16]
Yellow single crystals of 2 were grown from its chloroform solution
into which n-hexane was charged via slow vapour diffusion.
According to the X-ray diffraction analysis, we found that the
central tin atom is five-coordinated and reveals distorted trigonal
bipyramidal geometry (Fig. 2), as we expected from the 119 Sn
NMR spectrum. In accordance with Bent’s rule,[31] the more
electronegative atoms X (X N and Cl) occupy axial positions, and
a slightly more electropositive sulfur atom and two carbon atoms
are situated in equatorial positions. The interatomic distances
Sn1–S1 [2.4520(11) Å] and Sn1–N1 [2.420(3) Å] differ (0.05 Å) from
distances in compounds containing covalent Sn–S bond(s)[32,33]
and are significantly shorter than the sum of the van der Waals radii
for Sn and N atoms (3.97 Å).[34] This is evidently a consequence
of the presence of only one S,N-chelating ligand bonded to
the tin atom. The Sn1–Cl1 interatomic distance [2.4162(10) Å]
is about 0.08 Å shorter in comparison to previously reported
Sn–Cl distances in C,N-chelated organotin(IV) chlorides where the
tin atom is five-coordinated too.[35] The N1–Sn1–Cl1 interatomic
angle [153.29(7)◦ ] differs roughly from the ideal angle (180◦ ) owing
to the sterical hindrance of the two phenyl substituents as well as
the presence of the strained four-membered tin-containing ring.
In 2, the sum of all equatorial interatomic angles is 355.4◦ . The
molecular structure as well as relevant interatomic distances and
angles in 2 are comparable to those found in similar S,N-chelated
diphenyltin(IV) chlorides described in the literature.[6,36]
Colorless single crystals of 3 were obtained similarly as in
the case of 2. The tin atom in 3 is six-coordinated with
heavily distorted octahedral geometry having both carbon atoms
originating from n-Bu substituents mutually in trans positions
(Fig. 3). The S1 atom is in the cis position to the S2 atom
as well as the N1 atom is in the cis position to the N3
atom. Both Sn–S interatomic distances [Sn1–S1 2.5170(12)
and Sn1–S2 2.5039(14) Å, respectively] are about 0.05–0.1 Å
longer when compared with corresponding distances in 2 and
published compounds containing covalent Sn–S bond(s),[32,33]
which is apparently caused by the intramolecular N → Sn
interaction. Also the interatomic distances Sn1–N1 2.581(3) Å and
Sn1–N3 2.637(3) Å are longer than the corresponding distances
in 2 [Sn1–N1 2.420(3) Å] discussed above. The interatomic
distances Sn1–N1 [2.581(3) Å] and Sn1–N3 [2.637(3) Å] are
mutually slightly different but still represent the intramolecular
interaction N → Sn, forming thus highly strained four-membered
azastannathioheterocycles in the solid state, which is a common
attribute of all prepared organotin(IV) compounds bearing the
LSN ligand(s). The strength of this intramolecular interaction in
3 is within the range of N → Sn donor–acceptor interactions
found in previously published organotin(IV) species bearing
various S,N-chelating ligand(s).[6,7,37] The heavy distortion of the
octahedral vicinity of the central tin atom is demonstrated by the
c 2011 John Wiley & Sons, Ltd.
Copyright Appl. Organometal. Chem. 2011, 25, 725–734
S,N-Chelated organotin(IV) compounds
Figure 2. Molecular structure of 2 (ORTEP view, 30% probability level). Hydrogen atoms are omitted for clarity. Selected interatomic distances (Å)
and angles (deg): Sn1–Cl1 2.4162(10), Sn1–S1 2.4520(11), Sn1–N1 2.420(3), Sn1–C11 2.120(3), Sn1–C17 2.126(3), Cl1–Sn1–N1 153.29(7), Cl1–Sn1–S1
89.60(4), S1–Sn1–N1 63.89(7), S1–Sn1–C11 113.59(9), S1–Sn1–C17 121.41(7), C11–Sn1–C17 120.40(11), Sn1–S1–C1 85.79(12), Sn1–N1–C1 96.6(2),
S1–C1–N1 113.4(2).
Figure 3. Molecular structure of 3 (ORTEP view, 50% probability level). Hydrogen atoms are omitted for clarity. Selected interatomic distances (Å) and
angles (deg): Sn1–S1 2.5170(12), Sn1–S2 2.5039(14), Sn1–N1 2.581(3), Sn1–N3 2.637(3), Sn1–C21 2.133(5), Sn1–C25 2.145(5), S1–Sn1–S2 88.23(6),
N1–Sn1–N3 150.17(11), S1–Sn1–N1 61.03(9), S2–Sn1–N3 60.61(9), C21–Sn1–C25 131.0(2), Sn1–S1–C1 88.40(15), Sn1–S2–C11 89.84(14), Sn1–N1–C1
95.9(2).
Appl. Organometal. Chem. 2011, 25, 725–734
geometry (Fig. 4). Two LSN ligands [Sn1–S1 2.5787(12) Å and
Sn1–N2 2.596(3) Å; Sn1–S2 2.5876(13) Å and Sn1–N4 2.750(3) Å]
are situated in the equatorial plane of the distorted pentagonal
bipyramid as well as the nitrogen atom of the C,N-chelating
ligand. The interatomic distances Sn–S are evidently longer
(by ca. 0.12 and 0.06 Å, respectively) when compared with
corresponding distances found in 2 and 3. The molecule reveals
relatively weak donor–acceptor interaction N1 → Sn1 (N1–Sn1
2.691(4) Å) originating from the presence of the LCN moiety. The
intramolecular interaction N4 → Sn1 is even weaker [Sn1–N4
c 2011 John Wiley & Sons, Ltd.
Copyright wileyonlinelibrary.com/journal/aoc
731
C21–Sn1–C25 interatomic angle value being only 131.0(2)◦ . From
this point of view the coordination geometry of the tin atom can
be thus also described as skewed-trapezoidal bipyramidal. The
molecular structure together with relevant interatomic distances
and angles in 3 are comparable to those found in doubly S,Nchelated diorganotin(IV) species that have been already described
in the same literature.[6,36]
Colorless single crystals of 6 were grown from the diethyl ether
solution of crude 6. The central tin atom in 6 is seven-coordinated
in the solid state and reveals distorted pentagonal bipyramidal
A. Ozerianskyi et al.
Figure 4. Molecular structure of 6 (ORTEP view, 50% probability level). Hydrogen atoms are omitted for clarity. Selected interatomic distances (Å)
and angles (deg): Sn1–S1 2.5787(12), Sn1–S2 2.5876(13), Sn1–N1 2.691(4), Sn1–N2 2.596(3), Sn1–N4 2.750(3), Sn1–C1 2.132(4), Sn1–C10 2.147(5),
S1–Sn1–S2 82.67(4), S1–Sn1–N2 60.47(8), S2–Sn1–N4 58.65(8), N1–Sn1–N2 77.51(10), N1–Sn1–N4 82.00(11), N2–Sn1–N4 158.01(11), C1–Sn1–C10
156.64(16), Sn1–S1–C14 88.12(13), Sn1–S2–C24 91.48(15), S1–C14–N2 115.0(3), S2–C24–N4 115.5(3).
2.750(3) Å]. From this point of view, the coordination number
of the tin atom can be better described as [6 + 1] instead
of seven. Both carbon atoms C1 (of the C,N-chelating ligand)
and C10 (originating from the n-butyl substituent) occupy
axial positions and form an interatomic angle C1–Sn1–C10 of
156.64(16)◦ . Other selected interatomic distances and angles are
given in the caption to Fig. 4. The vicinity of the central tin
atoms exhibits analogous geometry as in the case of LCN (nBu)Sn[OC(O)Fc]2 discussed elsewhere,[29] where the tin atom is
seven-coordinated too.
bacteria was almost zero (for tested concentrations). A marked
decrease in inhibition (let us say an MIC increase) could be seen
after 48 h incubation in some yeasts. Compound 6 took effect
mainly on yeasts and weakly on G+ bacteria. Compound 2 took
effect on bacteria (except PA) and mainly on G+ . Compound 4
took effect mainly on staphylococci and yeasts but the effect
became almost zero, in all tested microbes, after 48 h incubation
(Table 3).
Conclusion
In Vitro Antifungal and Antibacterial Activity
732
Yeast, bacteria and mold strains were chosen so the basic spectrum
of the most common pathogens was covered. Substances causing
nosocomial infection were also included because we assume
higher resistance. One of them is Pseudomonas aeruginosa
(PA), which was resistant to all tested substances (in given
concentrations). Resistant strains MRSA and Klebsiella pneumoniae
(KP)-E embodied the same sensitivity to the tested substances
as well as their sensitive equivalents Staphylococcus aureus (SA)
and KP. Yeasts, molds and G+ bacteria (SA, MRSA, Staphylococcus
epidermidis, Enterococcus sp.) were the most sensitive ones in the
whole point of view. On the other hand, only compound 3 and
partially substance 2 took effect on G− bacteria. This could be
caused by different cell-wall structures or transport mechanisms,
but also by other factors.
The efficiency of tested compounds depended on the type
of the compound – each compound influences a different group
(or better group combination) of microbes. The most efficient
was compound 3, which proved to have a very good inhibitory
effect on all tested microbes except PA. Compound 1 was also
very efficient on yeasts, molds and G+ bacteria. The effect on G−
wileyonlinelibrary.com/journal/aoc
In conclusion, we have prepared novel organotin(IV) compounds
containing a new S,N-chelating ligand. The ability of this ligand to
act as a bidentate one, via the covalent Sn–S bond and a medium
strong N → Sn intramolecular coordination, was investigated.
We also introduced the structure of prepared compounds in
both solution and the solid state by NMR spectroscopy and
X-ray diffraction techniques. The coordination number of the tin
atom varies from five to seven and is dependent on the number
of chelating ligands present. Two compounds with both S,Nand C,N-chelating ligands were prepared in order to distinguish
between the possible formation of four-membered azastannathio
heterocycle or the five-membered azastanna heterocycle, while
the five-membered heterocycle seems to be slightly favored. The
di-n-butyl substituted compounds are the most efficient ones in
inhibition of growth of yeasts, molds and G+ bacteria strains.
Acknowledgments
The authors would like to thank the Science Foundation of the
Czech Republic (grant no. P207/10/0215) for financial support.
c 2011 John Wiley & Sons, Ltd.
Copyright Appl. Organometal. Chem. 2011, 25, 725–734
S,N-Chelated organotin(IV) compounds
Table 3. The results of antifungal and antibacterial screening of 1–5
MIC/IC80 (µmol l−1 )
Strain (code)a
CA
CT
CK
CG
TB
AF
AC
TM
SA
MRSA
SE
EF
EC
KP
KP-E
PA
24 h
48 h
24 h
48 h
24 h
48 h
24 h
48 h
24 h
48 h
24 h
48 h
24 h
48 h
72 h
120 h
24 h
48 h
24 h
48 h
24 h
48 h
24 h
48 h
24 h
48 h
24 h
48 h
24 h
48 h
24 h
48 h
1
2
3
7.8
62.5
7.8
62.5
7.8
31.3
7.8
15.6
7.8
15.6
15.6
125
7.8
15.6
7.8
15.6
7.8
15.6
7.8
15.6
7.8
7.8
7.8
31.3
125
125
125
>125
125
125
>125
>125
>125
>125
>125
>125
>125
>125
>125
>125
>125
>125
>125
>125
>125
>125
125
125
7.8
31.3
7.8
31.3
7.8
31.3
7.8
31.3
15.6
62.5
62.5
125
62.5
62.5
>125
>125
7.8
15.6
7.8
15.6
7.8
15.6
7.8
15.6
15.6
15.6
15.6
15.6
7.8
15.6
7.8
15.6
7.8
62.5
7.8
31.3
7.8
62.5
7.8
31.3
31.3
31.3
31.3
31.3
31.3
31.3
>125
>125
4
6
31.3
7.8
125
62.5
62.5
15.6
125
62.5
62.5
15.6
125
31.3
31.3
15.6
62.5
62.5
31.25
7.8
62.5
31.3
125
62.5
>125
125
62.5
7.8
125
31.3
62.5
7.8
62.5
15.6
31.3
31.3
31.3
62.5
7.8
31.3
>125
62.5
7.8
31.3
>125
62.5
31.3
31.3
>125
31.3
125
125
>125
125
>125
125
>125
>125
125
125
>125
>125
>125
125
>125
>125
a CA, Candida albicans ATCC 44 859; CT, Candida tropicalis 159; CK,
Candida krusei E28; CG, Candida glabrata 20/I; TB, Trichosporon beigelii
1188; AF, Aspergillus fumigatus 231; AC, Absidia corymbifera 272; TM,
Trichophyton mentagrophytes 445; SA, Staphylococcus aureus CCM
4516/8; MRSA, Staphylococcus aureus H 5996/08 (methilin resistance);
SE, Staphylococcus epidermidis H 6966/08; EF, Enterococcus sp. J
14 365/08; EC, Escherichia coli CCM4517; KP, Klebsiella pneumoniae
D 11 750/08; KP-E, Klebsiella pneumoniae J 14 368/08 (ESBL positive);
PA, Pseudomonas aeruginosa CCM 1961.
Supporting information
Supporting information may be found in the online version of this
article.
References
Appl. Organometal. Chem. 2011, 25, 725–734
c 2011 John Wiley & Sons, Ltd.
Copyright 733
[1] a) A. G. Davies, Organotin Chemistry, 2nd edn, VCH: Weinheim, 2004;
b) P. J. Smith, Chemistry of Tin, 2nd edn, Blackie: London, 1997.
[2] a) W. T. Piver, Environ. Health Perspect. 1973, 4, 61; b) G. J. M. van
de Kerk, in Organotin Compounds (Ed.: J. J. Zuckerman), American
Chemical Society: Washington, DC, 1976.
[3] M. Gielen, A. G. Davies, K. H. Pannell, E. R. T. Tiekink (Eds.), Tin
Chemistry: Fundamentals, Frontiers, and Applications, Chapter 4,
John Wiley & Sons: Chichester, 2008.
[4] a) V. Narayanan, M. Nasr, K. D. Paull, in Tin-Based Anti-Tumor Drugs
(Ed.: M. Gielen), Springer: Berlin, 1990, p. 201; b) P. Yang, M. Guo,
Coord. Chem. Rev. 1999, 185/186, 189; c) M. Gielen, Coord. Chem. Rev.
1996, 151, 41; d) M. Gielen, Appl. Organometal. Chem. 2002, 16, 481;
e) A. J. Crowe, in Metal-Based Drugs (Ed.: M. Gielen), Freund: London,
Vol. 1, 1989; f) M. Gielen, E. R. T. Tiekink, in Metallotherapeutic Drugs
and Metal-based Diagnostic Agents (Ed.: M. Gielen), John Wiley &
Sons: Chichester, 2005, pp. 421–439.
[5] a) G. D. Andreeti, G. Bocelli, G. Calestani, P. Sgarabotto,
J. Organometal. Chem. 1984, 273, 31; b) N. L. Speziali,
B. G. Guimaraes, R. M. Silva, P. H. Duarte, S. R. Aguiar, Acta
Crystallogr., Sect. C 1994, 50, 1059.
[6] a) N. G. Furmanova, Y. T. Struchkov, E. M. Rokhlina, D. N. Kravtsov,
J. Struct. Chem. 1980, 21, 766; b) C.-W. Ng, S. W. Wei, V. G. Kumar
Das, T. C. W. Mak, J. Organometal. Chem. 1987, 334, 283; c)
N. G. Furmanova, Y. T. Struchkov, E. M. Rokhlina, D. N. Kravtsov, J.
Struct. Chem. 1981, 22, 569; d) M. N. Xanthopoulou, S. K. Hadjikakou,
N. Hadjiliadis, M. Kubicki, S. Karkabounas, K. Charalabopoulos,
N. Kourkoumelis, T. Bakas, J. Organometal. Chem. 2006, 691,
1780; e) J. Martincová, L. Dostál, J. Taraba, A. Růžička, R. Jambor,
J. Organometal. Chem. 2007, 692, 3415; f) T. Munguia, M. LopezCardoso, F. Cervantes-Lee, K. H. Pannell, Inorg. Chem. 2007, 46,
1305; g) T. Munguia, F. Cervantes-Lee, L. Párkányi, K. H. Pannell, ACS
Symp. Ser. 2006, 917, 422; h) T. Munguia, I. S. Pavel, R. N. Kapoor,
F. Cervantes-Lee, L. Párkányi, K. H. Pannell, Can. J. Chem. 2003, 81,
1388; i) C. Ma, J. Zhang, G. Tian, R. Zhang, J. Organometal. Chem.
2005, 690, 519; j) R. Schmiedgen, F. Huber, A. Silvestri, G. Ruisi,
M. Rossi, R. Barbieri, Appl. Organometal. Chem. 1998, 12, 861; k)
A. Rodríguez, A. Sousa-Pedrares, J. A García-Vázquez, J. Romero,
A. Sousa, U. Russo, Eur. J. Inorg. Chem. 2007, 1444; l) E. LópezTorres, M. A. Mendiola, C. J. Pastor, J. R. Procopio, Eur. J. Inorg. Chem.
2003, 2711.
[7] R. Cea-Olivares, O. Jimenez-Sandoval, G. Espinosa-Perez, C. Silvestru,
J. Organometal. Chem. 1994, 484, 33.
[8] A. Lyčka, J. Holeček, B. Schneider, J. Straka, J. Organometal. Chem.
1990, 389, 29.
[9] A. Sousa-Pedrares, M. I. Casanova, J. A. García-Vázquez, M. L. Durán,
J. Romero, A. Sousa, J. Silver, P. J. Titler, Eur. J. Inorg. Chem. 2003, 678.
[10] J. T. B. H. Jastrzebski, G. van Koten, Adv. Organometal. Chem. 1993,
35, 241.
[11] a) J. Bareš, P. Novák, M. Nádvorník, R. Jambor, T. Lébl, I. Císařová,
A. Růžička, J. Holeček, Organometallics 2004, 23, 2967; b) A. Růžička,
L. Dostál, R. Jambor, V. Buchta, J. Brus, I. Císařová, M. Holčapek,
J. Holeček, Appl. Organometal. Chem. 2002, 16, 315; c) P. Novák,
A. Lyčka, I. Císařová, V. Buchta, L. Silva, L. Kolářová, A. Růžička,
J. Holeček, J. Appl. Organometal. Chem. 2005, 19, 500; d) A. Růžička,
A. Lyčka, R. Jambor, P. Novák, I. Císařová, M. Holčapek, M. Erben,
J. Holeček, J. Appl. Organometal. Chem. 2003, 17, 168.
[12] a) Z. Padělková, M. S. Nechaev, Z. Černošek, J. Brus, A. Růžička,
Organometallics 2008, 27, 5303; b) Z. Padělková, H. Vaňkátová,
I. Císařová, M. S. Nechaev, T. A. Zevaco, O. Walter, A. Růžička,
Organometallics 2009, 28, 2629; c) J. Bareš, P. Richard, P. Meunier,
N. Pirio, Z. Padělková, Z. Černošek, I. Císařová, A. Růžička,
Organometallics 2009, 28, 3105; d) P. Švec, A. Eisner, L. Kolářová,
T. Weidlich, V. Pejchal, A. Růžička, TetrahedronLett. 2008, 49, 6320; e)
P. Švec, P. Novák, M. Nádvorník, Z. Padělková, I. Císařová, A. Růžička,
J. Holeček, J. Fluorine Chem. 2007, 128, 1390; f) P. Švec, Z. Padělková,
Z. Černošek, F. De Proft, A. Růžička, J.Organometal.Chem. 2008, 693,
2937.
[13] J. Turek, Z. Padělková, Z. Černošek, M. Erben, A. Lyčka, M. S. Nechaev,
I. Císařová, A. Růžička, J. Organometal. Chem. 2009, 694, 3000.
[14] P. Švec, E. Černošková, Z. Padělková, A. Růžička, J. Holeček,
J. Organometal. Chem. 2010, 695, 2475.
[15] P. Švec, Z. Padělková, A. Růžička, T. Weidlich, L. Dušek, L. Plasseraud,
J. Organometal. Chem. 2011, 696, 676.
[16] A. Růžička, V. Pejchal, J. Holeček, A. Lyčka, K. Jacob, Collect. Czech.
Chem. Commun. 1998, 63, 977.
[17] W. J. Coates, A. McKillop, Synthesis 1993, 334.
[18] Z. Otwinowski, W. Minor, Meth. Enzymol. 1997, 276, 307.
[19] P. Coppens, in Crystallographic Computing (Eds.: F. R. Ahmed,
S. R. Hall, C. P. Huber), Munksgaard: Copenhagen, 1970,
pp. 255–270.
[20] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, J. Appl.
Crystallogr. 1993, 26, 343.
wileyonlinelibrary.com/journal/aoc
A. Ozerianskyi et al.
[21] G. M. Sheldrick, SHELXL-97, University of Göttingen, Göttingen,
1997.
[22] National Committee for Clinical Laboratory Standards. Reference
method for broth dilution antifungal susceptibility testing of
yeasts. Approved standard. Document M27-A, Wayne, PA, National
Committee for Clinical Laboratory Standards, 1997.
[23] B. Cordero, V. Gómez, A. E. Platero-Prats, M. Revés, J. Echeverría,
E. Cremades, F. Barragán, S. Alvarez, Dalton Trans. 2008, 2832.
[24] A. Růžička, R. Jambor, J. Brus, I. Císařová, J. Holeček, Inorg. Chim.
Acta 2001, 323, 163.
[25] a) M. Biesemans, J. C. Martins, R. Willem, A. Lyčka, A. Růžička,
J. Holeček, Magn. Reson. Chem. 2002, 40, 65; b) P. J. Smith, L. Smith,
Inorg. Chim. Acta Rev. 1973, 7, 11; c) M. Nádvorník, J. Holeček,
K. Handlíř, A. Lyčka, J. Organometal. Chem. 1984, 275, 43; d) A. Lyčka,
J. Jirman, A. Koloničný, J. Holeček, J. Organometal. Chem. 1987, 333,
305.
[26] J. Holeček, M. Nádvorník, K. Handlíř, A. Lyčka, J. Organomet Chem.
1986, 315, 299.
[27] J. Holeček, A. Lyčka, M. Nádvorník, K. Handlíř, Collect. Czech. Chem.
Commun. 1983, 241, 177.
[28] R. Schmiedgen, F. Huber, H. Preut, G. Ruisi, R. Barbieri, Appl.
Organometal. Chem. 1994, 8, 397.
[29] P. Švec, Z. Padělková, P. Štěpnička, A. Růžička, J. Holeček,
J. Organometal. Chem. 2011, 696, 1809 in press; doi: 10. 1016/j.
jorganchem. 2011.02.005
[30] P. Novák, Z. Padělková, L. Kolářová, I. Císařová, A. Růžička,
J. Holeček, Appl. Organometal. Chem. 2005, 19, 1101.
[31] H. A. Bent, J. Chem. Phys. 1959, 33, 1258.
[32] a) O. A. Dyachenko, A. B. Zolotoi, L. O. Atovmyan, R. G. Mirskov,
M. G. Voronkov, Dokl. Akad. Nauk SSSR 1977, 237, 863;
b) R. R. Holmes, S. Shafieezad, V. Chandrasekhar, J. M. Holmes,
R. O. Day, J. Am. Chem. Soc. 1988, 110, 1174.
[33] J. Turek, Z. Padělková, M. S. Nechaev, A. Růžička, J. Organometal.
Chem. 2010, 695, 1843.
[34] A. Bondi, J. Phys. Chem. 1964, 68, 441.
[35] a) R. A. Varga, A. Rotar, M. Schürmann, K. Jurkschat, C. Silvestru, Eur.
J. Inorg. Chem. 2006, 1475; b) P. Švec, Z. Padělková, I. Císařová,
A. Růžička, J. Holeček, Main Group Met. Chem. 2008, 31, 305.
[36] a)
M. N. Xanthopoulou,
S. K. Hadjikakou,
N. Hadjiliadis,
M. Schürmann, K. Jurkschat, A. Michaelides, S. Skoulika, T. Bakas,
J. J. Binolis, S. Karkabounas, C. Haralampopoulos, J. Inorg. Biochem.
2003, 96, 425; b) M. D. Couse, G. Faraglia, U. Russo, L. Sindellari,
G. Valle, J. Organometal. Chem. 1996, 513, 77; c) A. Paula, G. de
Sousa, R. M. Silva, A. Cesar, J. L. Wardell, J. C. Huffman, A. Abras,
J. Organometal. Chem. 2000, 605, 82.
734
wileyonlinelibrary.com/journal/aoc
c 2011 John Wiley & Sons, Ltd.
Copyright Appl. Organometal. Chem. 2011, 25, 725–734
Документ
Категория
Без категории
Просмотров
0
Размер файла
322 Кб
Теги
antibacterial, containing, compounds, stud, thiolate, organotin, antifungal, chelate, ligandчstructural, phenylpyridazine
1/--страниц
Пожаловаться на содержимое документа