Synthesis, structural characterization, and antibacterial activity of tricyclohexyltin aryloxyacetates

Article abstract of DOI:10.1515/mgmc-2015-0025

Three tricyclohexyltin aryloxyacetates, p-YC₆H₄OCH₂COOSn(C₆H₁₁-c)₃ (where Y=H, 1; CHO, 2; CH₂OH, 3), have been synthesized and characterized by means of elemental analysis, IR, and NMR (¹H, ¹³C, and ¹¹⁹Sn) spectroscopy. The crystal structures of complexes 1 and 3 are determined by X-ray single-crystal diffraction. The carboxylate in the compounds is monodentate. The tin atom of compound 1 adopts distorted tetrahedral coordination geometry. In the crystal lattice of compound 3, there is a four-coordinated tin and a five-coordinated tin in which the fifth coordination site is occupied by a water molecule, and the molecules are linked by R₃³(30) and R₅⁵(28) hydrogen bonds into a two-dimensional supramolecular network. Bioassay results have shown that the compounds have good in vitro antibacterial activity against Escherichia coli.

Full text of DOI:10.1515/mgmc-2015-0025

Main Group Met. Chem. 2015; 38(5-6): 157–164
Hao Zhang, Haixia Yu, Xijie Liu and Laijin Tian*
Synthesis, structural characterization,
and antibacterial activity of tricyclohexyltin
aryloxyacetates
DOI 10.1515/mgmc-2015-0025
Received August 16, 2015; accepted October 6, 2015; previously
published online November 5, 2015
2009; Shang et al., 2011; Amir et al., 2014; Carraher and
Roner, 2014; Wang et al., 2014; Mao et al., 2015). The
organotin moiety and ligands appear to play an impor-
tant role in determining their biological activity (Davies
et al., 2008; Hadjikakou and Hadjiliadis, 2009; Amir et al.,
Abstract: Three tricyclohexyltin aryloxyacetates, p-YC H
6
4
OCH COOSn(C H -c) (where Yꢀ=ꢀH, 1; CHO, 2; CH OH, 3),
2
6
11
3
2
2
014). In general, the toxicity of organotin compounds
have been synthesized and characterized by means of
seems to increase with the chain length of the organic
alkyl groups, which are often more active than aryl ones.
To design new active tin compounds, it is necessary to
balance some factors such as solubility and lipophilicity
to achieve efficacy (Hadjikakou and Hadjiliadis, 2009;
Arjmand et al., 2014).
1
13
119
elemental analysis, IR, and NMR ( H, C, and Sn) spec-
troscopy. The crystal structures of complexes 1 and 3 are
determined by X-ray single-crystal diffraction. The car-
boxylate in the compounds is monodentate. The tin atom
of compound 1 adopts distorted tetrahedral coordination
geometry. In the crystal lattice of compound 3, there is a
four-coordinated tin and a five-coordinated tin in which
the fifth coordination site is occupied by a water mol-
Aryloxyacetic acid derivatives possess a wide array
of diverse bioactivities such as antimicrobacterial, anti-
inflammatory, antibacterial, analgesic, antisickling,
antipaemic, antiplatelet, non-prostanoid prostacyclin
mimetic, diuretic, and growth regulators (Fracchiolla
et al., 2007; Bala et al., 2010; Kumar et al., 2013). The syn-
thesis, structure, and property of some organotin com-
plexes with ligands have been reported, such as dibutyltin
3
5
ecule, and the molecules are linked by R (30) and R (28)
3
5
hydrogen bonds into a two-dimensional supramolecu-
lar network. Bioassay results have shown that the com-
pounds have good in vitro antibacterial activity against
Escherichia coli.
Keywords: antibacterial activity; aryloxyacetic acid; crystal bis(2-naphthoxyacetate) (Ma et al., 2004), tris(2-methyl-
structure; organotin; organotin carboxylate.
2-phenylpropyl)tin phenoxyacetate (Bao et al., 1998),
tributyltin 2,4-dichlorophenoxyacetate (Yu et al., 2010),
and triphenyltin 8-quinolyloxyacetate (Das et al., 1987). To
continue to increase the chemistry and therapeutic poten-
tial of the organotin complexes of aryloxyacetic acids, we
select phenoxyacetic acid with polar substituent groups as
ligands (Scheme 1) and synthesized three new tricyclohex-
yltin complexes, p-YC H OCH COOSn(C H -c) (where
Introduction
Organotin carboxylates have been widely researched
because of their novel structures and various applications
in the last few decades (Tiekink, 1991, 1994; Davies et al.,
6
4
2
6
11
3
Yꢀ=ꢀH, CHO, and CH OH), and determined their in vitro
2
2
008). Many organotin carboxylates display good activi-
antibacterial activity.
ties against tumors, fungi, bacteria, and other microor-
ganisms (Davies et al., 2008; Hadjikakou and Hadjiliadis,
*
Corresponding author: Laijin Tian, Key Laboratory of Natural
Results and discussion
Products and Pharmaceutical Intermediates, Qufu Normal
University, Qufu 273165, China, e-mail: laijintian@163.com
Hao Zhang: Key Laboratory of Natural Products and Pharmaceutical
Intermediates, Qufu Normal University, Qufu 273165, China
Haixia Yu: Key Laboratory of Natural Products and Pharmaceutical
Intermediates, Qufu Normal University, Qufu 273165, China; and
Affiliated School of Qufu Normal University, Qufu 273165, China
Xijie Liu: Beijing Centaurus BioPharma Technology, Beijing
Synthesis
The reaction of tricyclohexyltin hydroxide with phenoxy-
acetic acid or p-substituted phenoxyacetic acid in a 1:1
molar ratio in anhydrous benzene afforded products 1–3,
with a yield of 65–81% (Scheme 2).
100089, China
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58ꢀꢀꢀꢀꢁꢀH. Zhang et al.: Tricyclohexyltin aryloxyacetates
1
119
coupling constants (Nadvornik et al., 1984). The J( Sn-
1
3
C) coupling of the compounds is close to that of other
four-coordinate tricyclohexyltin carboxylates, such as
Scheme 1:ꢀThe structure of the ligand.
2-HOC H Nꢀ=ꢀNC H COOSn(C H -c) (335 Hz) (Willem et al.,
6
4
6
4
6
11
3
1
998), C H SCOOSn(C H -c) (333 Hz) (Abbas et al., 2013),
4 3 6 11 3
(
c-C H ) SnO CCH CH COCH CH CO Sn(C H -c) (325 Hz)
6 11 3 2 2 2 2 2 2 6 11 3
(
Chalupa et al., 2006), and (2-C H C HN )COOSn(C H -c)
6 5 2 3 6 11 3
(
330 Hz) (Tian et al., 2015). Data suggest that the tin atom
in these compounds is four-coordinated in CDCl solution.
3
1
19
The Sn chemical shifts primarily depend on the
coordination number and the nature of the donor atom
directly bonded to the central tin atom (Davis, 2004). The
Scheme 2:ꢀSynthesis of compounds 1–3.
1
19
Sn chemical shifts of 1–3 (30.0–33.0 ppm) are in accord
These compounds are white crystals, air stable, and with the values of the four-coordinated tricyclohexyltin
soluble in benzene and in common polar organic solvents carboxyl ester in the solution of the non-coordinating
such as methanol, ethanol, dichloromethane, chloroform, solvent (Tian et al., 2005, 2015; Chalupa et al., 2006).
acetone, and N,N-dimethylformamide, but insoluble in
water and saturated hydrocarbons such as hexane and
petroleum ether.
Structure analysis of 1 and 3
The structures of complexes 1 and 3 are shown in
Figures 1–3, and the selected geometric parameters are
given in Table 1. Compound 1 crystallizes with two inde-
Spectroscopic analysis
In the IR spectra of compounds 1–3, the bands at ~3450 and pendent molecules in the crystallographic asymmetric
-1
~
1760 cm assigned to ν (O-H) and ν (Cꢀ=ꢀO), respectively, unit that do not differ from each other significantly. The
of free aryloxyacetic acid do not appear, and new strong coordination geometry of the tin atom is a distorted tetra-
-1
bands at ~1660 and ~1350 cm are assigned to the asym- hedron shaped by three carbon atoms from the cyclohexyl
-
metrical, ν (CO ), and symmetrical stretching vibrations, groups and one carboxyl O atom [O(1) and O(4)] from the
as
2
-
ν (CO ), of the aryloxyacetate, respectively. The difference carboxylate ligand. The separation between the other O
s
2
-
-
-
between the ν (CO ) and the ν (CO ) bands, Δν(CO ), is atom of the carboxylate ligand and Sn atom is Sn(1)···O(2)
as
2
s
2
2
-1
-1
-1
3
13 cm for 1, 272 cm for 2, and 331 cm for 3, which is 3.017(4) Å and Sn(2)···O(5) 2.994(4) Å. The weak interac-
-1
larger than 200 cm , suggesting that the carboxylate group tion distorts the tetrahedral geometry by opening up the
is coordinated to tin in the monodentate mode in the solid
state (Deacon and Phillips, 1980; Li et al., 2010).
1
In H NMR spectra of 1–3, the single resonances of
COOH in the spectra of the free ligands are not observed
at ~12 ppm, which further confirms the replacement of
the carboxylic acid protons by the tricyclohexyltin moiety
on complex formation. The complexes show multiplets in
the range of 1.17–1.97 ppm due to the cyclohexyl protons
and singlets at 4.43–4.71 ppm assigned to the OCH2
protons. The resonances in the range between 6.76 and
7
.82 ppm are assigned to the aryl protons.
The 13C chemical shifts of the carboxyl and meth-
ylene carbon atoms in 1–3 appear at 172.21–173.36
and 65.56–66.41 ppm, respectively. The signals of the
cyclohexyl carbon atoms are in the range of 26.97–36.49
1
119
13
2
119
13
3
119
13
ppm, and the J( Sn- C), J( Sn- C), and J( Sn- C)
coupling constants are ~330, 20, and 60 Hz, respec-
tively. The coordination number of the tin atom in the
Figure 1:ꢀThe molecular structure of 1.
1
119
13
organotin compounds has been related to the J( Sn- C) Hydrogen atoms are omitted for clarity.
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H. Zhang et al.: Tricyclohexyltin aryloxyacetatesꢂꢁꢀꢀꢀꢂ159
Figure 2:ꢀThe molecular structure of 3.
Hydrogen atoms are omitted for clarity.
Figure 3:ꢀThe 2D supramolecular network of 3 formed by the intermolecular O-H···O hydrogen bonds.
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60ꢀꢀꢀꢀꢁꢀH. Zhang et al.: Tricyclohexyltin aryloxyacetates
Table 1:ꢀSelected bond lengths (Å) and angles (°) for compound 1 and 3.
ꢁ
Sn(ꢃ)-O(ꢃ)
Sn(ꢃ)-C(ꢃ)
Sn(ꢃ)-C(ꢌ)
Sn(ꢃ)-C(ꢃꢈ)
ꢄ
ꢄ
ꢄ
ꢄ
ꢅ.ꢆꢇꢅ(ꢈ)ꢄ
ꢅ.ꢃꢅꢅ(ꢊ)ꢄ
ꢅ.ꢃꢈꢌ(ꢌ)ꢄ
ꢅ.ꢃꢉꢈ(ꢌ)ꢄ
ꢃꢆꢌ.ꢍ(ꢅ)ꢄ
ꢋꢉ.ꢆ(ꢅ)ꢄ
Sn(ꢅ)-O(ꢉ)
Sn(ꢃ)-C(ꢅꢌ)
Sn(ꢃ)-C(ꢈꢈ)
Sn(ꢃ)-C(ꢈꢋ)
C(ꢃ)-Sn(ꢃ)-C(ꢃꢈ)ꢄ
C(ꢌ)-Sn(ꢃ)-C(ꢃꢈ)ꢄ
O(ꢉ)-Sn(ꢅ)-C(ꢈꢋ)ꢄ
O(ꢉ)-Sn(ꢅ)-C(ꢅꢌ)ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢅ.ꢆꢊꢅ(ꢈ)ꢄ
ꢅ.ꢃꢇꢃ(ꢇ)ꢄ
ꢅ.ꢃꢊꢆ(ꢇ)ꢄ
ꢅ.ꢃꢈꢋ(ꢊ)ꢄ
ꢃꢃꢌ.ꢅ(ꢉ)ꢄ
ꢃꢃꢊ.ꢌ(ꢈ)ꢄ
ꢃꢆꢌ.ꢆ(ꢅ)ꢄ
ꢋꢇ.ꢊꢇ(ꢃꢌ)ꢄ
C(ꢃꢋ)-O(ꢅ)
C(ꢃꢋ)-O(ꢃ)
C(ꢉꢇ)-O(ꢇ)
C(ꢉꢇ)-O(ꢉ)
O(ꢉ)-Sn(ꢅ)-C(ꢈꢈ) ꢄ
C(ꢈꢋ)-Sn(ꢅ)-C(ꢅꢌ)ꢄ
C(ꢈꢋ)-Sn(ꢅ)-C(ꢈꢈ)ꢄ
C(ꢅꢌ)-Sn(ꢅ)-C(ꢈꢈ)ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢃ.ꢅꢆꢊ(ꢊ)
ꢃ.ꢅꢋꢉ(ꢊ)
ꢃ.ꢅꢃꢆ(ꢌ)
ꢃ.ꢅꢍꢅ(ꢊ)
ꢃꢆꢊ.ꢉꢈ(ꢃꢋ)
ꢃꢃꢆ.ꢃ(ꢈ)
ꢃꢅꢃ.ꢃ(ꢈ)
ꢃꢃꢈ.ꢅ(ꢅ)
O(ꢃ)-Sn(ꢃ)-C(ꢃ) ꢄ
O(ꢃ)-Sn(ꢃ)-C(ꢌ) ꢄ
O(ꢃ)-Sn(ꢃ)-C(ꢃꢈ)ꢄ
ꢃꢆꢌ.ꢆ(ꢅ)ꢄ
ꢃꢃꢃ.ꢃ(ꢈ)ꢄ
C(ꢃ)-Sn(ꢃ)-C(ꢌ)
ꢄ
ꢂ
Sn(ꢃ)-O(ꢃ)
Sn(ꢃ)-O(ꢅ)
Sn(ꢃ)-C(ꢃ)
Sn(ꢃ)-C(ꢌ)
Sn(ꢃ)-C(ꢃꢈ)
C(ꢌ)-Sn(ꢃ)-C(ꢃꢈ) ꢄ
C(ꢌ)-Sn(ꢃ)-C(ꢃ)
C(ꢃꢈ)-Sn(ꢃ)-C(ꢃ) ꢄ
C(ꢌ)-Sn(ꢃ)-O(ꢅ) ꢄ
C(ꢃꢈ)-Sn(ꢃ)-O(ꢅ)ꢄ
C(ꢃ)-Sn(ꢃ)-O(ꢅ) ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢅ.ꢉꢈꢅ(ꢉ)ꢄ
ꢅ.ꢃꢌꢇ(ꢉ)ꢄ
ꢅ.ꢃꢇꢋ(ꢊ)ꢄ
ꢅ.ꢃꢈꢅ(ꢇ)ꢄ
ꢅ.ꢃꢉꢈ(ꢇ)ꢄ
ꢃꢃꢋ.ꢅ(ꢅ)ꢄ
ꢃꢅꢈ.ꢆ(ꢈ)ꢄ
ꢃꢃꢊ.ꢅ(ꢅ)ꢄ
ꢍꢌ.ꢉ(ꢅ)ꢄ
Sn(ꢅ)-O(ꢊ)
Sn(ꢅ)-C(ꢅꢍ)
Sn(ꢅ)-C(ꢈꢉ)
Sn(ꢅ)-C(ꢉꢆ)
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢅ.ꢆꢍꢃ(ꢇ)ꢄ
ꢅ.ꢃꢉꢍ(ꢊ)ꢄ
ꢅ.ꢃꢅꢌ(ꢊ)ꢄ
ꢅ.ꢃꢅꢊ(ꢌ)ꢄ
ꢄ
ꢍꢌ.ꢉ(ꢅ)ꢄ
ꢍꢇ.ꢍꢃ(ꢃꢍ)ꢄ
ꢍꢉ.ꢈ(ꢅ)ꢄ
ꢃꢌꢉ.ꢇꢅ(ꢃꢇ)ꢄ
ꢃꢆꢅ.ꢃ(ꢈ)ꢄ
ꢄ
C(ꢃꢋ)-O(ꢅ)
C(ꢃꢋ)-O(ꢈ)
C(ꢉꢊ)-O(ꢊ)
C(ꢉꢊ)-O(ꢌ)
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢃ.ꢅꢍꢌ(ꢌ)
ꢃ.ꢅꢅꢅ(ꢌ)
ꢃ.ꢅꢍꢅ(ꢌ)
ꢃ.ꢅꢅꢃ(ꢌ)
C(ꢌ)-Sn(ꢃ)-O(ꢃ) ꢄ
C(ꢃꢈ)-Sn(ꢃ)-O(ꢃ)ꢄ
C(ꢃ)-Sn(ꢃ)-O(ꢃ) ꢄ
O(ꢅ)-Sn(ꢃ)-O(ꢃ) ꢄ
O(ꢊ)-Sn(ꢅ)-C(ꢉꢆ)ꢄ
ꢄ
O(ꢊ)-Sn(ꢅ)-C(ꢈꢉ) ꢄ
C(ꢉꢆ)-Sn(ꢅ)-C(ꢈꢉ)ꢄ
O(ꢊ)-Sn(ꢅ)-C(ꢅꢍ) ꢄ
C(ꢉꢆ)-Sn(ꢅ)-C(ꢅꢍ)ꢄ
C(ꢈꢉ)-Sn(ꢅ)-C(ꢅꢍ)ꢄ
ꢄ
ꢋꢌ.ꢈ(ꢅ)
ꢃꢃꢉ.ꢇ(ꢈ)
ꢃꢆꢌ.ꢍ(ꢅ)
ꢃꢃꢊ.ꢋ(ꢈ)
ꢃꢃꢇ.ꢆ(ꢈ)
ꢄ
ꢋꢍ.ꢈꢉ(ꢃꢋ)ꢄ
ꢋꢊ.ꢋ(ꢅ)ꢄ
C(1)-Sn(1)-C(13) and C(33)-Sn(2)-C(39) to 117.2(4)° and (Yu et al., 2012). The bond length of Sn(1)-O(1) [2.432(4) Å]
1
21.1(3)°, respectively, and reducing the O(1)-Sn(1)-C(7) is significantly longer than that of Sn(1)-O(2) [2.175(4)Å],
and O(5)-Sn(2)-C(27) to 94.0(2)° and 95.65(17)°, respec- so that the Sn(1) atom is displaced out of the C trigonal
3
tively. The monodentate mode of the carboxylate coordi- plane of the trans-C SnO trigonal bipyramidal polyhe-
3
2
nation is expressed in two disparate C-O bond distances dron in the direction of O(2) by 0.155(2) Å.
(Table 1). The four bond distances around Sn are similar
The structure of molecule B is similar to compound 1,
to those found in other reported tricyclohexyltin carboxy- and Sn(2) has also a distorted tetrahedral geometry with the
lates, such as tricyclohexyltin indole-3-acetate (Molloy angles range of 97.3(2)–116.9(3)°. As expected, the C-O bond
et al., 1986), 2-(4-chlorophenyl)-3-methylbutyrate (Song distances [C(19)-O(3) 1.222(7) Å and C(46)-O(7) 1.221(7) Å]
et al., 2003), and ferrocene carboxylate (Dong et al., 2014). associated with the non-coordinating carbonyl O atoms are
Compound 3 crystallizes in the monoclinic space shorter than the coordinating C-O bond distances [C(19)-O(2)
group P2 , and the crystal structure reveals that there are 1.287(7) Å and C(46)-O(6) 1.282(7) Å]. Although not involved
1
two crystallographically non-equivalent molecules in the in coordination to tin, the O(3) and O(7) atoms form signifi-
crystallographic asymmetric unit. The tin atom Sn(1) of cant intermolecular contacts in the crystal lattice. Through
one molecule (A) is five-coordinated, and the tin atom the coordinated water molecules and the hydroxyl groups of
Sn(2) of the other molecule (B) is four-coordinated. In A, ligands, the monomeric structures (A and B) get into contact
the coordination geometry of the tin center displays a dis- with each other via hydrogen bonds (Table 2), and a two-
3
5
torted trans-O SnC trigonal bipyramid with three carbon dimensional (2D) network containing R (30) and R (28)
2
3
3
5
atoms [C(1), C(7), and C(13)] of cyclohexyl groups defin- hydrogen bonding patterns is formed (Figure 3).
ing the trigonal plane and a unidentate carboxylate O(2)
and a O(1) atom from the water molecule occupying the
axial positions. The C-Sn-C angles were in the range of Antibacterial activity
1
16.2(2)–123.0(3)°. The O(1)-Sn(1)-O(2) angle is 174.52(15)°,
which is similar to that observed in related tricyclohex- The antibacterial activities of the compounds and
yltin analogues, such as 3-C H NCO Sn(C H -c) (H O) the reference drug (penicillin sodium and cefazolin
5
4
2
6
11
3
2
[
176.11(11)°] (Teoh et al., 1999), (4-MeC H ) GeCH(C H
4
sodium) are listed in Table 3. Results show that com-
6
4
3
6
OMe-4)CH CO Sn(C H -c) (H O) [170.35(6)°] (Din et al., plexes 1–3 is active against Escherichia coli, which
2
2
6
11
3
2
2
003), and 2-Cl-3-C H NCO Sn(C H -c) (H O) [176.40(11)°] is comparable with the reported tricyclohexyltin
5 4 2 6 11 3 2
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H. Zhang et al.: Tricyclohexyltin aryloxyacetatesꢂꢁꢀꢀꢀꢂ161
Table 2:ꢀHydrogen bonds in compound 3.
D-H···A
ꢃ
D-H (Å)ꢃ
H···A (Å)ꢃ
D···A (Å)ꢃ
D-H···A (°)ꢃ
Symmetry code
O(ꢃ)-H(ꢃA)···O(ꢌ)
ꢄ
ꢄ
ꢄ
ꢄ
ꢆ.ꢍꢇꢄ
ꢆ.ꢍꢅꢄ
ꢆ.ꢍꢇꢄ
ꢆ.ꢍꢅꢄ
ꢃ.ꢋꢍꢌꢄ
ꢃ.ꢍꢌꢉꢄ
ꢃ.ꢍꢃꢌꢄ
ꢃ.ꢋꢊꢈꢄ
ꢅ.ꢌꢉꢉ(ꢊ)ꢄ
ꢅ.ꢊꢇꢇ(ꢌ)ꢄ
ꢅ.ꢊꢇꢊ(ꢌ)ꢄ
ꢅ.ꢌꢆꢍ(ꢌ)ꢄ
ꢃꢉꢌ.ꢍꢄ
ꢃꢇꢍ.ꢌꢄ
ꢃꢊꢋ.ꢆꢄ
ꢃꢇꢆ.ꢍꢄ
#
ꢃ
O(ꢇ)-H(ꢇ)···O(ꢈ)
#ꢃ: x-ꢃ, y, z
#ꢅ: x+ꢃ, y, z
#ꢈ: -x, y-ꢃ/ꢅ, -z+ꢅ
#
ꢅ
O(ꢃ)-H(ꢃB)···O(ꢋ)
#
ꢈ
O(ꢋ)-H(ꢋ)···O(ꢇ)
Table 3:ꢀAntibacterial activity (MIC, μg/mL) of the synthesized
elemental analyzer (Perkin Elmer, Waltham, MA, USA). The IR spectra
were recorded on a Nicolet Nexus 470 FT-IR spectrophotometer using
compounds.
-1
KBr discs in the range of 4000–400 cm (Thermo Nicolet, Madison,
1
13
WI, USA). H and C NMR spectral data were collected using a Bruker
Avance DPX300 NMR spectrometer (Bruker, Fallanden, Switzerland)
ꢃ
ꢃ
Compoundꢃ Penicillin sodiumꢃ Cefazolin sodium
ꢃ
ꢃ
ꢁꢃ
ꢄꢃ
ꢂ
119
with CD SOCD or CDCl as solvent and TMS as internal standard. Sn
3
3
3
NMR spectra were recorded in CDCl on a Varian Mercury Vx300 spec-
trometer. Me Sn was used as external reference (Varian, Palo Alto, USA).
E. coliꢄ ꢅꢇ.ꢅꢅꢄ ꢃꢊ.ꢇꢆꢄ ꢃꢉ.ꢌꢍꢄ
ꢍ.ꢆꢈꢄ
ꢅ.ꢆꢃ
3
4
2
-phenyl-1,2,3-triazole-4-carboxylate (MICꢀ=ꢀ13.50 μg/mL)
Synthesis of ligands
(
Tian et al., 2005) and ferrocenecarboxylate (MICꢀ=ꢀ23.98
μg/mL) (Dong et al., 2014). The activity of the three com-
pounds against E. coli decreased in the order 3ꢀ>ꢀ2ꢀ>ꢀ1 under
Synthesis of p-formylphenoxyacetic acid:ꢁThe ligand was prepared
by a modified literature procedure (Liu et al., 2005). To a stirred solu-
experimental conditions. However, the activity is lower tion of p-hydroxybenzaldehyde (1.22 g, 10 mmol) and bromoacetic
acid (1.67 g, 12 mmol) in water (20 mL) was dropwise added 20 mL
than that of the reference drugs.
water solution of sodium hydroxide (0.96 g, 24 mmol) within 30 min
at room temperature. Stirring of the reaction mixture continued for
1
.5 h under reflux and then cooled to room temperature. The solu-
Conclusion
tion was acidified with concentrated hydrochloric acid to pH 1–2, and
the resulting solid was filtered and recrystallized from 95% alcohol to
Three tricyclohexyltin aryloxyacetates have been synthe- give p-formylphenoxyacetyl acid as a white solid (1.40 g, 78%); m.p.
2
5
00–201°C. Anal. calcd. for C H O (%): C, 60.00; H, 4.48. Found: C,
9 8 4
sized from triorganotin hydroxide and aryloxyacetic acid
and characterized. In both the solid state and the CDCl3
solution, the carboxylate moiety coordinates the tin center
in a monodentate fashion. The tin atom of compound 1
possesses a distorted tetrahedral geometry. In the crystal
9.94; H, 4.42. IR (KBr): 3460 (br, OH), 1755 (COOH), 1718 (CHO), 1226
-1
1
(
Ar-O) cm . H NMR (CD SOCD ) δ 12.46 (s, 1H, COOH), 9.85 (s, 1H,
3 3
CHO), 7.80 (d, Jꢀ=ꢀ8.4 Hz, 2H, m-H-C H ), 7.08 (d, Jꢀ=ꢀ8.4 Hz, 2H, o-H-
C H ), 4.81 (s, 2H, OCH ) ppm.
6
4
6
4
2
lattice of compound 3, there is a four-coordinated tin and Synthesis of p-(hydroxymethyl)phenoxyacetic acid:ꢁTo a solution
of p-formylphenoxyacetic acid (1.80 g, 10 mmol) in water (15 mL)
a five-coordinated tin possessing a trigonal bipyramidal
containing KOH (0.56 g, 10 mmol) was slowly added an excess of
environment with the axial positions occupied by a car-
sodium borohydride (0.46 g, 12 mmol) in water (10 mL) containing
boxylate oxygen atom and an oxygen atom of a water mol-
a few drops of sodium hydroxide solution within 15 min in an ice
ecule and the 2D supramolecular network is formed by
bath. The reactive mixture was stirred for 1 h at room temperature
3
5
R (30) and R (28) hydrogen bonds. In the CDCl solution, and then acidified with concentrated HCl to a pH of 2–3. The result-
3
5
3
the tin atoms of the compounds are all four-coordinated. ing white solid was filtered off, washed with cold water, dried, and
The compounds have activity against E. coli and can be
considered as antibacterial compounds to further study.
was recrystallized from ethyl acetate/n-hexane (1:1, v/v). Yield 1.56 g
(
86%); m.p. 116–117°C. Anal. calcd. for C H O (%): C, 59.34; H, 5.53.
9 10 4
Found: C, 59.36; H, 5.56. IR (KBr): 3500 (br, OH), 1761 (COOH), 1235
-1 1
(
Ar-O) cm . H NMR (CD SOCD ) δ 12.31 ((s, 1H, COOH), 7.22 (d, Jꢀ=ꢀ8.0
3 3
Hz, 2H, m-H-C H ), 6.82 (d, Jꢀ=ꢀ8.0 Hz, 2H, o-H-C H ), 4.85 (s, 1H, OH),
6
4
6
4
Experimental
4.50 (s, 2H, OCH ), 4.42 (s, 2H, OCH Ar) ppm.
2
2
General
Synthesis of the complexes
All chemicals used in the syntheses were of analytical grade and were
purchased from commercial sources (Sinopharm Chemical Reagent Tricyclohexyltin phenoxyacetate (1):ꢁTo a suspension of tricy-
Company, Shanghai, China) and used as received. Carbon and hydro- clohexyltin hydroxide (0.77 g, 2 mmol) in 50 mL of benzene was added
gen analyses were determined using a Perkin Elmer 2400 Series II phenoxyacetic acid (0.30 g, 2 mmol). Under magnetic stirring, the
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62ꢀꢀꢀꢀꢁꢀH. Zhang et al.: Tricyclohexyltin aryloxyacetates
reaction mixture heated at reflux for 5 h with a Dean-Stark separa- complex 3, the site occupancies of the cyclohexyls were refined to
tor and then allowed to cool to room temperature. The solution was 0.802(10):0.198(10) for C(7)-C(12) and 0.65(2):0.35(2) for C(40)-C(45),
filtered, and the solvent was removed under reduced pressure by a respectively. In refinements, the C-C bonds and 1,3-distances of the
rotary evaporator. The resulting white solid was recrystallized from disorderly cyclohexyl groups were restrained to 1.52(1) and 2.50(2)
methanol and dried in a vacuum dryer for 24 h to afford colorless crys- Å, respectively. Crystal data, collection procedures, and refinement
tal of 1 (0.81 g, 78%); m.p. 70–71°C. Anal. calcd. for C H O Sn (%): results are shown in Table 4. The crystallographic data of compounds
2
6
40
3
-
C, 60.13; H, 7.76. Found: C, 59.94; H, 7.52. IR (KBr): 1665 [ν(COO ) ], 1 and 3 were deposited at the Cambridge Crystallographic Data Centre
as
-
-1 1
1
352 [ν(COO ) ] cm . H NMR (CDCl ) δ 7.27 (t, 2H, m-H-C H ), 7.10–6.89 as supplementary publication numbers CCDC 1014268 and 1043087.
s
3
6
5
(
m, 3H, o-H-, p-H-C H ), 4.56 (s, 2H, OCH ), 1.21–1.90 (m, 33H, c-C H )
6
5
2
6
1
1
1
3
ppm. C NMR (CDCl ) δ 173.36 (COOSn), 158.17 (i-C-C H ), 129.26 (m-C-
3
6
5
1
119
C H ), 121.04 (p-C-C H ), 114.56 (o-C-C H ), 65.56 (OCH ), 34.04 [ J( Sn-
6
5
6
5
6
5
2
Antibacterial activity
13
2
119
13
3
119
13
C)ꢀ=ꢀ332 Hz, C-α], 31.01 [ J( Sn- C)ꢀ=ꢀ20 Hz, C-β], 28.86 [ J( Sn- C)ꢀ=ꢀ62
Hz, C-γ], 26.97 (C-δ) ppm. 1 Sn NMR (CDCl ) δ 30.0 ppm.
19
3
The antibacterial activity of compounds 1–3 against E. coli was deter-
mined by the microcalorimetric method according to the literature
Tricyclohexyltin p-formylphenoxyacetate (2):ꢁThis compound was
prepared in the same way as 1 by the reaction of tricyclohexyltin
hydroxide (0.77 g, 2 mmol) with p-formylphenoxyacetic acid (0.36 g,
(
Zhang et al., 2004). A 2277 Thermal Activity Monitor (Thermometric
AB, Jarfalla, Sweden) was used to determine the power-time curves
of bacterial growth at 310 K. Af er a stable baseline was obtained,
the bacterial sample, a beef-extract-soluble medium (pHꢀ=ꢀ7.2–7.4)
containing NaCl (1 g), peptone (2 g), beef extract (1 g), and different
concentrations of organotin medicine in each 200 mL were pumped
into the flow cell system and the monitor began to record the power-
time curves of continuous growth for bacteria. When the recording
pen returned to the baseline, the process of bacterial growth was
completed. Based on the data of power-time curves and theoreti-
cal model, the growth rate constants were calculated (Zhang et al.,
2
mmol). Yield 0.71 g (65%); m.p. 88–89°C. Anal. calcd for C H O Sn:
27 40 4
C, 59.25; H, 7.37. Found: C, 59.19; H, 7.25. IR (KBr): 1720 (CHO), 1668
-
-
-1
1
[
ν(COO ) ], 1396 [ν(COO ) ] cm , H NMR (CDCl ) δ 9.86 (1H, s, CHO),
a
s
s
3
7
.82 (d, Jꢀ=ꢀ8.2 Hz, 2H, m-H-C H ), 7.01 (d, Jꢀ=ꢀ8.2 Hz, 2H, o-H-C H ), 4.71
6
4
6
4
13
(
s, 2H, OCH ), 1.30–1.97 (m, 33H, c-C H ). C NMR (CDCl ) δ 191.76
2
6
1
1
3
(
CHꢀ=ꢀO), 172.21 (COOSn), 164.87 (i-C-C H ), 131.92 (m-C-C H ), 129.93
6
4
6
4
1
119
13
(
p-C-C H ), 114.48 (o-C-C H ), 65.76 (OCH ), 34.12 [ J( Sn- C)ꢀ=ꢀ320 Hz,
6
4
6
4
2
2
119
13
3
119
13
C-α], 30.92 [ J( Sn- C)ꢀ=ꢀ20 Hz, C-β], 28.83 [ J( Sn- C)ꢀ=ꢀ62 Hz, C-γ],
1
19
2
7.54 (C-δ) ppm. Sn NMR (CDCl ) δ 33.0 ppm.
3
2
004). The relationship between the growth rate constants (μ) and
the concentration (C) of the organotin medicine was fitted using a
computer (μꢀ=ꢀaC+b). When the growth rate constant is 0, the mini-
mum inhibitory concentration (MIC) was confirmed.
Tricyclohexyltin p-(hydroxymethyl)phenoxyacetate (3):ꢁComplex
was prepared by the same procedure as 1 by the reaction of tricy-
3
clohexyltin hydroxide (0.77 g, 2 mmol) with p-(hydroxymethyl)phe-
noxyacetic acid (0.36 g, 2 mmol). Yield 0.89 g (81%); m.p. 91–92°C.
Anal. calcd. for C H O Sn (%): C, 59.03; H, 7.71. Found: C, 58.77; H,
2
7
42
4
Table 4:ꢀCrystallographic data and structure refinement for 1 and 3.
-
-
-1 1
7
.64. IR (KBr): 3452 (br, OH), 1656 [ν(COO ) ], 1325 [ν(COO ) ] cm . H
a
s
s
NMR (CDCl ) δ 7.14 (d, Jꢀ=ꢀ8.0 Hz, 2H, m-H-C H ), 6.76 (d, Jꢀ=ꢀ8.0 Hz,
3
6
4
ꢃ
ꢃ
Compound
ꢁ
2
H, o-H-C H ), 5.01 (s, 1H, OH), 4.43 (s, 2H, OCH COO), 4.36 (s, 2H,
6
4
2
13
OCH Ar), 1.17–1.83 (m, 33H, c-C H ). C NMR (CDCl ) δ 172.37 (COOSn),
2
6
11
3
ꢃ
ꢂ
1
57.57 (i-C-C H ), 134.78 (m-C-C H ), 127.90 (p-C-C H ), 114.41 (o-C-
6 4 6 4 6 4
1
119
13
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
C H O Sn
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
ꢄ
C H O Sn
ꢇꢉ ꢍꢊ ꢋ ꢅ
C H ), 66.14 (OCH ), 62.98 (HOCH ), 36.49 [ J( Sn- C)ꢀ=ꢀ332 Hz, C-α],
ꢅꢊ ꢉꢆ
ꢇꢃꢋ.ꢅꢌ
ꢈ
6
4
2
2
2
119
13
3
119
13
ꢃꢃꢃꢊ.ꢊꢃ
3
(
0.88 [ J( Sn- C)ꢀ=ꢀ20 Hz, C-β], 29.17 [ J( Sn- C)ꢀ=ꢀ64 Hz, C-γ], 27.07
1
19
Monoclinic
Monoclinic
Pꢅꢃ
ꢃꢆ.ꢊꢊꢆꢋ(ꢃꢉ)
ꢃꢍ.ꢅꢌꢉ(ꢅ)
ꢃꢉ.ꢃꢃꢆꢌ(ꢃꢍ)
ꢋꢆ
C-δ) ppm. Sn NMR (CDCl ) δ 30.8 ppm.
3
Pꢅ /c
ꢃ
ꢋ.ꢌꢊꢋꢌ(ꢃꢅ)
ꢅꢍ.ꢇꢉꢊ(ꢉ)
ꢃꢍ.ꢉꢅꢌ(ꢅ)
ꢋꢆ
b (Å)
c (Å)
X-ray crystallography
α (°)
β (°)
ꢋꢅ.ꢆꢅꢍ(ꢅ)
ꢋꢆ
ꢋꢆ.ꢆꢃꢊ(ꢅ)
ꢋꢆ
The colorless single crystals of 1 and 3 were obtained from metha-
nol by slow evaporation at room temperature. Diffractions measure-
ments were performed on a Bruker Smart Apex imaging plate area
detector fitted with graphite monochromatized Mo-Kα radiation
γ (°)
ꢈ
Volume (Å )
ꢇꢃꢈꢇ.ꢋ(ꢃꢃ)
ꢍ
ꢅꢌꢉꢋ.ꢃ(ꢊ)
ꢅ
Z
ꢈ
D (g/cm )
c
ꢃ.ꢈꢉꢈ
ꢃ.ꢈꢉꢋ
(
0.71073 Å) using the ϕ and ω scan technique at 295(2) K. The struc-
-
ꢃ
μ (mm )
ꢃ.ꢆꢃꢌ
ꢆ.ꢋꢇꢋ
tures were solved by direct methods and refined by a full-matrix
F(ꢆꢆꢆ)
ꢅꢃꢊꢆ
ꢃꢃꢊꢉ
2
least-squares procedure based on F using SHELXL-97 (Sheldrick,
2
θ range
ꢃ.ꢈꢅ–ꢅꢊ.ꢆꢆ
ꢆ.ꢅꢆꢄ×ꢄꢆ.ꢆꢌꢄ×ꢄꢆ.ꢆꢇ
ꢃ.ꢉꢉ–ꢅꢇ.ꢇꢆ
ꢆ.ꢅꢆꢄ×ꢄꢆ.ꢃꢍꢄ×ꢄꢆ.ꢃꢆ
008). The non-hydrogen atoms were refined anisotropically, and
Crystal size (mm)
Unique reflections
Reflections [Iꢄ>ꢄꢅσ(I)] ꢄ ꢊꢉꢅꢅ
Goodness of fit on F ꢄ ꢃ.ꢆꢅꢉ
the hydrogen atoms were placed at calculated positions in the rid-
ing model approximation, with C-Hꢀ=ꢀ0.93 Å for aromatic and for-
myl H atoms, C-Hꢀ=ꢀ0.97 Å for methylene H atoms, C-Hꢀ=ꢀ0.98 Å for
methine H atoms, O-Hꢀ=ꢀ0.82 Å for hydroxy H atoms, and O-Hꢀ=ꢀ0.85(1)
Å for water H atoms. In complex 1, two cyclohexyl groups are disor-
dered over two positions, and their site occupancies were refined to
ꢃꢆ,ꢆꢅꢆ (R ꢄ=ꢄꢆ.ꢆꢉꢇ) ꢄ ꢃꢆ,ꢃꢍꢊ (R ꢄ=ꢄꢆ.ꢆꢈꢃ)
int
int
ꢄ
ꢄ
ꢍꢋꢍꢊ
ꢃ.ꢆꢅꢍ
ꢅ
R indices [Iꢄ>ꢄꢅσ(I)]
R indices (all data)
ꢄ
ꢄ
ꢄ
Rꢄ=ꢄꢆ.ꢆꢇꢆ, wRꢄ=ꢄꢆ.ꢃꢅꢊꢄ Rꢄ=ꢄꢆ.ꢆꢉꢉ, wRꢄ=ꢄꢆ.ꢆꢋꢍ
Rꢄ=ꢄꢆ.ꢆꢍꢌ, wRꢄ=ꢄꢆ.ꢃꢉꢌꢄ Rꢄ=ꢄꢆ.ꢆꢇꢅ, wRꢄ=ꢄꢆ.ꢃꢆꢅ
-
ꢈ
Δρmax, Δρmin (e/Å )
ꢆ.ꢌꢃꢆ, -ꢆ.ꢉꢃꢉ
ꢄ
ꢆ.ꢍꢆꢈ, -ꢆ.ꢈꢋꢅ
0.54(6):0.46(6) for C(13)-C(18) and 0.70(2):0.30(2) for C(39)-C(44). In
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H. Zhang et al.: Tricyclohexyltin aryloxyacetatesꢂꢁꢀꢀꢀꢂ163
Acknowledgments: This work was supported by Shan- Kumar G. S. S.; Seethalakshmi P. G.; Bhuvanesh N.; Kumaresan, S.
Cocrystals of caffeine with formylphenoxyaliphatic acids:
dong Provincial Natural Science Foundation, China
syntheses, structural characterization, and biological activity. J.
(ZR2013BM007), and the National Natural Science Foun-
Mol. Struct. 2013, 1034, 302–309.
dation of China (21302110).
Li, W.; Du, D.; Liu, S.; Zhu, C.; Sakho, A. M.; Zhu, D.; Xu, L.
Self-assembly of a novel 2D network polymer: syntheses,
characterization, crystal structure and properties of a four-tin-
nuclear 36-membered diorganotin(IV) macrocyclic carboxylate.
J. Organomet. Chem. 2010, 695, 2153–2159.
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diffraction structural data of triorganotin 2-[(E)-2-(2-hydroxy-
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