Structural diversity of organotin(IV) complexes self-assembled from hydroxamic acid and mono- or dialkyltin salts

Article abstract of DOI:10.1016/j.jorganchem.2011.02.017

Three hydroxamic acid ligands (HL₁ = acetohydroxamic acid; HL₂ = benzohydroxamic acid; HL₃ = N-phenylbenzohydroxamic acid), have been used to synthesize series of mono- or dialkyltin(IV) complexes, which include (i) the ca

Full text of DOI:10.1016/j.jorganchem.2011.02.017

Journal of Organometallic Chemistry 696 (2011) 1824e1833
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Structural diversity of organotin(IV) complexes self-assembled from hydroxamic
acid and mono- or dialkyltin salts
*
Handong Yin , Lei Dong, Min Hong, Jichun Cui
Department of Chemistry, Liaocheng University, Liaocheng 252059, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Three hydroxamic acid ligands (HL1 ¼ acetohydroxamic acid; HL2 ¼ benzohydroxamic acid; HL3 ¼ N
ephenylbenzohydroxamic acid), have been used to synthesize series of mono- or dialkyltin(IV)
complexes, which include (i) the carboxyl acid hybrid five-coordinated dialkyltin complexes
(C4H9)2SnL1L4 (1), [(CH3)2SnL2L5]·0.5C6H6 (2), (HL4 ¼ acetic acid; HL5 ¼ benzoic acid); (ii) the six-coor-
dinated mono-n-butyltin complexes (C4H9)SnL1$Cl2$H2O (3), (C4H9)SnL2$Cl2$H2O (4), [(C4H9)
SnL3$Cl2$H2O]$H2O (5), [(C4H9Sn)2(L3)2$Cl2$(OCH3)2] (6); and (iii) the alkali metal-mingled seven-coor-
dinated mono-n-butyltin complexes [(C4H9Sn)3L2Na]þ$Clꢀ$(CH3CH2)2O (7), [(C4H9Sn)3L2K]þ$Clꢀ$CH2Cl2
(8). All complexes were characterized by elemental analyses, IR, 1H, 13C, 119Sn NMR and X-ray single
crystal diffraction. In these complexes, hydroxamic acids present bidentate coordination modes with the
carbonyl O atom and the hydroxyl O atom binding to tin center. In complexes 1e6, each tin atom is
coordinated by one hydroxamic acid ligand. However, in complexes 7 and 8, tin atom is surrounded by
three hydroxamic acid ligands, and all hydroxyl O atoms of the ligands also bind to the alkali metal center
(Na or K). This kind of organotin(IV) framework containing one alkali metal is found for the first time.
Furthermore, the supramolecular structures of 1, 3, 4 and 6 have been found to consist of 1D linear
molecular chains formed by intermolecular NeH$$$X or CeH$$$X (X ¼ O, N or Cl) hydrogen bonds. For
complex 2, an interesting macrocyclic tetramer has been built by the intermolecular NeH$$$O hydrogen
bonds. Fascinatingly, two unique symmetric dimeric structures are recognized in complexes 7 and 8,
which is individually bridged by intermolecular NeH$$$Cl and NeH$$$O hydrogen bonds. In addition, for
8, the dimeric cycles have been further connected into a 1D supramolecular chain.
Received 23 December 2010
Received in revised form
5 February 2011
Accepted 14 February 2011
Keywords:
Mono- or diorganotin(IV) complex
Hydroxamic acid
Structure analysis
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
example, Li and coworkers have reported a series of diorganotin(IV)
complexes with substituted benzohydroxamic acids and studied
The studies of organotin(IV) complexes are of current interest
owing to their biomedical and commercial application [1e4].
Recently, there have been a mass of reports on the synthesis, anti-
tumor activities and structural elucidations of various organotin(IV)
derivatives of carboxylic acid [5e11]. Hydroxamic acids are usually
used as supporting ligands in organometallic chemistry and biology
because of their tautomerization and potential as therapeutics
agents [12e19]. In the last decades, organotin(IV) derivatives of
hydroxamic acids are attracting more and more attention due to
their biological properties such as antifungicidal and the promising
antitumor activity [20,21].
their antitumor activity [12,20e22]. It is well-known that the
biochemical activity of organotin(IV) complexes is influenced
greatly by the structure of the molecule, the coordination number
of the tin atoms and the type of alkyl groups attached to the tin
atom. The structural characterization of such organotin(IV)
complexes may provide important clues to the structureeactivity
relationship of the ligand and alkyl species and provide an
invaluable insight to the reaction mechanism that may, in turn,
allow synthetic chemists to further optimize reaction conditions.
Thus it is required to construct a variety of types of organotins
through new rational strategies.
However, from the viewpoint of coordination architecture, their
investigation is still very limited, and only a few simple organotin
complexes with hydroxamato ligands have been studied. For
As an extension of this field, herein we choose three different
hydroxamic acids as building blocks to construct various organotin
complexes, particularly systematic investigations on the topology
about the effect of alkyltin salts.
We began to treat carboxylic acid and hydroxamic acid reacting
with dialkyltin salts with the hope of obtaining interesting
* Corresponding author. Tel.: þ86 635 8239121; fax: þ86 635 8238121.
E-mail address: handongyin@163.com (H. Yin).
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.02.017

H. Yin et al. / Journal of Organometallic Chemistry 696 (2011) 1824e1833
1825
Scheme 1. The syntheses procedures of complexes 1e8.

1826
H. Yin et al. / Journal of Organometallic Chemistry 696 (2011) 1824e1833
Table 1
coordination structures. As a result, complexes 1 and 2 were
obtained, in which both monodentate carboxyl group and biden-
tate O-donors hydroxamic acid coordinate to tin center as sup-
porting ligands and both tin atoms are in the five-coordinated
trigonal-bipyramid environment. As part of our continuing interest
of organotin(IV) complexes with hydroxamato ligands, we have
synthesized and characterized four monoorganotin(IV) complexes
3e6 by the reaction of hydroxamic acid with mono-n-butyltin
chlorides. In these four complexes, 3e5 are simple monomer, but 6
presents as a methoxy-bridged dimmer. To the best of our knowl-
edge, there are no monoorganotin complexes with hydroxamic acid
ligand being reported until now. Unprecedentedly, we have also
obtained two novel alkali metal-mingled three tin nuclei mono-
organotin(IV) complexes 7 and 8, which consist of three C4H9SnL3
moieties and one half KCl or NaCl, and the alkali metal cation lies in
the center of the complex presenting an crown ether-like coordi-
nation geometry with nine hydroxylO atoms fromthe hydroxamato.
Selected bond lengths (Å) and angles (ꢁ) for complexes 1 and 2
Complex 1
Sn(1)eO(1)
Sn(1)eC(5)
Sn(1)eC(9)
Sn(1)eO(3)
2.086(5)
2.107(7)
2.109(8)
2.200(5)
2.269(5)
104.9(2)
104.4(3)
150.3(3)
O(1)-Sn(1)-O(3)
C(5)-Sn(1)-O(3)
C(9)-Sn(1)-O(3)
O(1)-Sn(1)-O(2)
C(5)-Sn(1)-O(2)
C(9)-Sn(1)-O(2)
O(3)-Sn(1)-O(2)
78.60(18)
94.5(2)
96.0(3)
74.63(18)
91.5(3)
91.5(3)
Sn(1)eO(2)
O(1)eSn(1)eC(5)
O(1)eSn(1)eC(9)
C(5)eSn(1)eC(9)
153.21(17)
Complex 2
Sn(1)eO(1)
Sn(1)eC(16)
Sn(1)eC(15)
Sn(1)eO(3)
Sn(1)eO(2)
O(1)eSn(1)eC(16)
O(1)eSn(1)eC(15)
C(16)eSn(1)eC(15)
2.102(17)
2.11(3)
2.13(3)
2.178(18)
2.284(17)
110.3(10)
109.5(10)
138.6(12)
O(1)-Sn(1)-O(3)
C(16)-Sn(1)-O(3)
C(15)-Sn(1)-O(3)
O(1)-Sn(1)-O(2)
C(16)-Sn(1)-O(2)
C(15)-Sn(1)-O(2)
O(3)-Sn(1)-O(2)
76.2(7)
100.6(9)
99.3(10)
73.2(7)
91.7(9)
89.3(10)
149.4(8)
2. Results and discussion
2.1. Syntheses
The syntheses procedures of complexes 1e8 are given in
Scheme 1.
2.2. IR spectra
By comparing the IR spectra of the free ligands with those of the
complexes, a remarkable difference is the complete disappearance
of the stretching vibration bands of OeH. The peak appearing at
400e555 cmꢀ1 can be assigned to the stretching mode of the SneO
linkage. The absorption about 3200 cmꢀ1 region for the complexes
1e4 and 7e8 can be assigned to the NeH stretching mode of the
vibration. Therefore, the IR spectra suggest the coordination of
carbonyl and hydroxyl O atoms to the organotin(IV) ions. For
complexes 1 and 2, it is worthy to note that there are more than one
SneO bands, which is more obvious for the mixed-ligand
complexes. Above these are also confirmed by X-ray structure
analyses.
2.3. NMR spectra
Fig. 1. The molecular structure of complex 1 (Butyl atoms is somewhat disordered).
The 1H NMR spectrum of the complex shows that the signal for
the eOH proton in the spectrum of the ligand is absent, thus
indicating the removal of the eOH proton and the formation of
SneO bonds in all the complexes. This is consistent with the IR data.
The 13C NMR spectral pattern is consistent with the formulation of
the complexes. In the 13C NMR spectra in CDCl3 for complex 6, the
data of 50.81 ppm gives evidence for the existence of methanol
molecule. The single resonances at 160e166 ppm are attributed to
the CON groups in complexes 1e8. Especially, there are two signal
Fig. 2. One-dimension zigzag chain of complex 1, formed by intermolecular CeH$$$O and NeH$$$O hydrogen-bonding interactions.

H. Yin et al. / Journal of Organometallic Chemistry 696 (2011) 1824e1833
1827
Table 2
Hydrogen-bonding geometries for complexes 1-8.
D-H A
H$$$A
D$$$A
D-H$$$A
Complex 1
C(2)eH(2B).O(1)#1
C(5)eH(5B).O(4)#2
N(1)eH(1).O(3)#1
2.66
2.60
1.96
3.511(9)
3.499(10)
2.796(7)
148.3
154.5
163.0
Complex 2
N(1)eH(1).O(1)#3
Fig. 3. The molecular structure of complex
molecules are omitted).
2
(For clarity, uncoordinated solvent
2.01
2.82(3)
158.2
Complex 3
C(1)eH(1A).O(6)#1
N(1)eH(1).Cl(1)#2
2.71
2.32
3.659(7)
3.176(4)
168.7
171.4
compound 3e6 (
d
¼ ꢀ380 ppm for 3; ꢀ377 ppm for 4; ꢀ367 ppm
for 5; ꢀ353 ppm for 6) show signals in the normal range for six-
coordinate mono-n-butyltin(IV) derivatives, which are similar to
that found in the compounds reported previously [25,26]. For
compounds 7 and 8, the 119Sn NMR spectroscopic data show one
resonance signal at
respectively, which fall in the range corresponding to a type of
seven-coordinated tin compounds [27].
Complex 4
C(17)eH(17).Cl(4)#1
C(5)eH(5).Cl(2)#2
C(14)eH(14).Cl(3)#3
N(1)eH(1).Cl(4)#4
N(2)eH(2).Cl(1)#4
2.92
2.86
2.92
2.49
2.50
3.77(2)
3.78(3)
3.78(2)
3.323(17)
3.310(16)
153.2
170.4
154.8
164.9
157.2
d
¼ ꢀ482 ppm for 7 and ꢀ480 ppm for 8,
Complex 6
C(10)eH(10).O(2)#2
2.61
3.402(10)
143.8
2.4. Description of crystal structures
Complex 7
2.4.1. X-ray crystallography of complexes 1 and 2
N(18)eH(18).O(13)
N(8)eH(8).Cl(1)
N(1)eH(1).Cl(1)
N(4)eH(4).Cl(1)
N(14)eH(14).Cl(2)
N(17)eH(17).Cl(2)
N(11)eH(11).Cl(2)
N(15)eH(15).O(9)
N(6)eH(6).O(25)
N(12)eH(12).O(3)
N(3)eH(3).O(19)
N(9)eH(9).O(31)
2.13
2.34
2.33
2.36
2.36
2.30
2.32
2.11
2.10
2.06
2.16
2.13
2.938(11)
3.159(10)
3.157(9)
3.155(9)
3.168(8)
3.119(9)
3.127(9)
2.944(10)
2.910(10)
2.877(10)
2.964(10)
2.936(10)
155.5
160.4
160.4
154.6
157.0
159.6
156.2
162.5
157.7
158.5
156.4
156.4
Selected bond lengths and angles of complexes 1 and 2 are listed
in Table 1. The molecular structure of complex 1 is shown in Fig. 1. It
can be seen that the tin atom has a coordination number of five.
Central Sn atom is coordinated by one carboxyl O atom from acetic
acid, one carbonyl O atom and one hydroxyl O atom from aceto-
hydroxamic acid, and two C atoms of trans n-butyl groups. The
bond length of Sn(1)eO(1), Sn(1)eO(2) and Sn(1)eO(3) are 2.086
(5) Å, 2.269(5) Å and 2.200(5) Å, which are close to the corre-
sponding bond length in the literature [22]. The angle of C(5)eSn
(1)eC(9), 150.3(3)ꢁ, which deviates from the linear angle of 180ꢁ.
Thus, the coordination geometry of the tin center is best described
as distorted trigonal bipyramid. As can be seen in Fig. 2 that
molecules of 1 have been connected by intermolecular CeH$$$O
and NeH$$$O hydrogen-bonding interactions (shown in Table 2)
Complex 8
C(59)eH(59).Cl(1)
C(17)eH(17).Cl(1)
C(38)eH(38).Cl(1)
C(35)eH(35).O(1)#1
C(52)eH(52).O(13)#1
C(52)eH(52).N(7)#1
C(14)eH(14).O(7)#1
C(14)eH(14).N(4)#1
C(35)eH(35).N(1)#1
N(6)eH(6).Cl(1)
N(9)eH(9).Cl(1)
N(3)eH(3).Cl(1)
N(2)eH(2).O(7)#1
N(8)eH(8).O(13)#1
N(5)eH(5).O(1)#1
2.83
2.78
2.74
2.53
2.61
2.72
2.57
2.69
2.70
2.33
2.29
2.33
2.10
2.16
2.14
3.727(16)
3.640(13)
3.563(15)
3.435(17)
3.497(18)
3.621(19)
3.454(19)
3.59(2)
163.2
154.9
148.3
164.6
160.3
163.0
158.9
162.2
164.9
158.9
159.5
155.8
157.6
154.0
159.0
3.610(17)
3.151(9)
3.113(10)
3.132(10)
2.911(11)
2.952(12)
2.961(12)
Symmetry code: (#1 for 1) ꢀxþ1/2,yꢀ1/2,ꢀzþ1/2; (#2 for 1) ꢀxþ1/2,ꢀyþ3/2,-z;
(#3 for 2) #3 ꢀyþ1,x,ꢀz; (#1 for 3) ꢀxþ1,ꢀy,ꢀzþ1; (#2 for 3) ꢀxþ1,ꢀyþ1,ꢀzþ1;
(#1 for 4) ꢀxþ1,ꢀyþ1,ꢀz; (#2 for 4) x,yþ1,z; (#3 for 4) -xþ1,ꢀyþ2,ꢀz; (#4 for
4) ꢀx, ꢀyþ1,-z; (#3 for 6) ꢀxþ1,yþ1/2,ꢀzþ1/2; (#1 for 5) ꢀx, ꢀy, 2ꢀz; (#1 for 6)
1 þ x, y, z; (#1 for 8) ꢀxþ1,y,ꢀzþ1/2.
resonances in the region 170e180 ppm, indicating the presence of
the COO groups in complexes 1 and 2.
The 119Sn NMR chemical shifts of organotin(IV) complexes
appear to depend not only on the coordination number, but also on
the types of donor atoms and alkyl groups bound to the metal ion
[23]. Although bonding with different alkyl groups, n-butyl group
for 1 and methyl group for 2, the 119Sn NMR spectroscopy data of
compounds 1 and 2 show similar resonance signals at
d
¼ ꢀ70 ppm
for 1 and -76 ppm for 2, respectively, which are different from the
values (ꢀ90 to ꢀ190 ppm) reported for the di-n-butyltin
compounds mentioned in the reference [24]. It may be due to the
effect of different ligands. The 119Sn NMR spectroscopy data of
Fig. 4. The macrocyclic polymer structure of complex 2, formed by intermolecular
NeH$$$O hydrogen-bonding interactions.

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H. Yin et al. / Journal of Organometallic Chemistry 696 (2011) 1824e1833
Table 3
Selected bond lengths (Å) and angles (ꢁ) for complexes 3e6
Complex 3
Sn(1)eO(5)
Sn(1)eC(6)
Sn(1)eO(6)
2.087(3)
2.128(5)
2.212(3)
165.48(19)
74.93(12)
92.44(18)
83.38(14)
88.1(2)
Sn(1)eO(7)
Sn(1)eCl(2)
Sn(1)eCl(1)
O(6)eSn(1)eCl(2)
O(7)eSn(1)eCl(2)
O(5)eSn(1)eCl(1)
C(6)eSn(1)eCl(1)
O(6)eSn(1)eCl(1)
O(7)eSn(1)eCl(1)
Cl(2)eSn(1)eCl(1)
2.255(4)
2.3783(13)
2.4517(15)
156.82(9)
87.91(10)
88.90(9)
98.12(17)
88.79(10)
170.07(12)
97.34(6)
O(5)eSn(1)eC(6)
O(5)eSn(1)eO(6)
C(6)eSn(1)eO(6)
O(5)eSn(1)eO(7)
C(6)eSn(1)eO(7)
O(6)eSn(1)eO(7)
O(5)eSn(1)eCl(2)
C(6)-Sn(1)eCl(2)
83.19(14)
82.83(9)
108.66(16)
Fig. 5. The molecular structure of complex 3.
Complex 4
Sn(1)eO(1)
Sn(1)eC(8)
Sn(1)eO(2)
Sn(1)eCl(2)
Sn(1)eCl(1)
Sn(1)eO(3)
2.084(12)
2.13(2)
Sn(2)eO(4)
Sn(2)eC(19)
Sn(2)eO(5)
Sn(2)eO(6)
Sn(2)eCl(3)
Sn(2)eCl(4)
2.094(12)
2.108(18)
2.158(13)
2.276(13)
2.426(5)
2.448(5)
166.6(8)
76.8(5)
92.5(7)
78.3(5)
92.6(8)
83.9(5)
2.155(13)
2.435(5)
2.457(5)
2.260(12)
171.0(9)
77.2(5)
97.9(8)
80.1(5)
91.9(9)
83.0(5)
O(1)eSn(1)eC(8)
O(1)eSn(1)eO(2)
C(8)eSn(1)eO(2)
O(1)eSn(1)eO(3)
C(8)eSn(1)eO(3)
O(2)eSn(1)eO(3)
O(1)eSn(1)eCl(2)
C(8)eSn(1)eCl(2)
O(2)eSn(1)eCl(2)
O(3)eSn(1)eCl(2)
O(1)eSn(1)eCl(1)
C(8)eSn(1)eCl(1)
O(2)eSn(1)eCl(1)
O(3)eSn(1)eCl(1)
Cl(2)eSn(1)eCl(1)
O(4)eSn(2)eC(19)
O(4)eSn(2)eO(5)
C(19)eSn(2)eO(5)
O(4)eSn(2)eO(6)
C(19)eSn(2)eO(6)
O(5)eSn(2)eO(6)
O(4)eSn(2)eCl(3)
C(19)eSn(2)eCl(3)
O(5)-Sn(2)-Cl(3)
O(6)eSn(2)eCl(3)
O(4)eSn(2)eCl(4)
C(19)eSn(2)eCl(4)
O(5)eSn(2)eCl(4)
O(6)eSn(2)eCl(4)
Cl(3)eSn(2)eCl(4)
83.0(3)
83.9(3)
100.9(7)
159.1(4)
87.3(3)
87.4(4)
100.3(9)
90.9(4)
105.6(6)
160.0(4)
86.8(4)
88.4(4)
100.3(7)
91.8(4)
Fig. 6. The molecular structure of complex 4.
167.0(3)
94.76(19)
166.6(4)
93.19(19)
Complex 5
Sn(1)eO(1)
Sn(1)eO(2)
Sn(1)eCl(2)
O(1)eSn(1)eC(14)
O(1)eSn(1)eO(2)
C(14)eSn(1)eO(2)
O(1)eSn(1)eO(3)
C(14)eSn(1)eO(3)
O(2)eSn(1)eO(3)
O(1)eSn(1)eCl(2)
Cl(2)eSn(1)eCl(1)
2.4.2. X-ray crystallography of complexes 3, 4, 5 and 6
2.089(3)
2.172(3)
2.4072(13)
169.89(19)
74.60(11)
97.4(2)
83.49(13)
89.27(19)
81.31(14)
83.14(9)
Sn(1)eC(14)
Sn(1)eO(3)
Sn(1)eCl(1)
C(14)eSn(1)eCl(2)
O(2)eSn(1)eCl(2)
O(3)eSn(1)eCl(2)
O(1)eSn(1)eCl(1)
C(14)eSn(1)eCl(1)
O(2)eSn(1)eCl(1)
O(3)eSn(1)eCl(1)
2.135(5)
2.210(3)
Selected bond lengths and angles of complexes 3e6 are listed in
Table 3. As can be seen from Figs. 5, 6 and 7, complexes 3e5 have
the similar structure features. The center tin atoms are six-coor-
dinated with one O atom and one Cl atom occupying the axial sites
[axial angles: O(7)eSn(1)eCl(1) ¼ 170.07ꢁ, for complex 3; O(6)eSn
(2)eCl(4) ¼ 166.6(4)ꢁ, for complex 4; O(3)eSn(1)eCl(1) ¼ 167.64
(11)ꢁ, for complex 5], and one Cl atom, one C atom and two O atoms
define the equatorial plane. All of the center tin atoms have six-
coordinate geometry in a distorted octahedral arrangement. The
sum of the angles subtended at the tin center in the equatorial
plane is 357.9ꢁ, 358.9ꢁ and 358.78ꢁ for complexes 3, 4 and 5,
respectively. So the central tin atom and the corresponding two
oxygen atoms, one chlorine atom and one n-butyl carbon atom
bonding with tin center are almost coplanar. For complex 6, to our
2.4505(13)
103.64(18)
156.00(10)
87.46(11)
85.96(9)
100.34(17)
89.71(10)
167.64(11)
97.67(5)
Complex 6
Sn(1)eO(3)#1
Sn(1)eC(14)
Sn(1)eO(1)
O(3)#1eSn(1)eC(14)
O(3)#1eSn(1)eO(1)
C(14)eSn(1)eO(1)
O(3)#1eSn(1)eO(2)
C(14)eSn(1)eO(2)
O(1)eSn(1)eO(2)
O(3)#1eSn(1)eO(3)
C(14)eSn(1)eO(3)
2.081(4)
2.113(7)
2.114(5)
105.3(3)
155.26(19)
94.4(3)
84.57(18)
169.3(3)
75.00(18)
73.0(2)
Sn(1)eO(2)
Sn(1)eO(3)
Sn(1)eCl(1)
O(1)vSn(1)eO(3)
O(2)eSn(1)eO(3)
O(3)#1eSn(1)eCl(1)
C(14)eSn(1)eCl(1)
O(1)eSn(1)eCl(1)
O(2)eSn(1)eCl(1)
O(3)eSn(1)eCl(1)
2.127(5)
2.173(4)
2.428(2)
90.5(2)
82.96(19)
93.57(14)
97.6(2)
98.61(17)
85.80(17)
163.21(13)
95.7(3)
Symmetry code for complex 6: #1 ꢀxþ1, ꢀy, ꢀzþ1.
into an interesting 1D zigzag chain structure, and the crystal
structure is stabilized by the intramolecular hydrogen bonds.
For complex 2, the overall structure (Fig. 3) is similar to that of
complex 1. The coordination number of the Sn atom is five. The
Sn4þ ion is bonded with two CH3 groups, one benzoic acid and one
benzohydroximic ligand. It is worthwhile to note that four mole-
cules of complex 2 form a fascinating macrocyclic tetramer (see
Fig. 4), which is linked by intermolecular NeH$$$O hydrogen-
bonding interactions (shown in Table 2).
Fig. 7. The molecular structure of complex 5.

H. Yin et al. / Journal of Organometallic Chemistry 696 (2011) 1824e1833
1829
Fig. 8. The 1D chain structure of complex 3, formed by intermolecular CeH$$$O and NeH$$$Cl hydrogen-bonding interactions.
Fig. 9. The 1D chain structure of complex 4, formed by intermolecular CeH$$$Cl and NeH$$$Cl hydrogen-bonding interactions.
surprise, the Sn atoms are six-coordinate with a octahedral struc-
ture by coordinating two additional methoxy groups [Sn(1)eO(3)
#1 (ꢀxþ1,ꢀy,ꢀzþ1) ¼ 2.081 Å, Sn(1)eO(3) ¼ 2.173 Å]. Each of the
tin atoms bounds to one butyl group, two methoxy oxygen atoms,
two hydroxamic oxygen atoms and a chlorine atom.
Fascinating supramolecular structures have been found for
complexes 3 and 4, which are built up by intermolecular hydrogen
bonds. As can be seen from Fig. 8 that molecules of 3 are connected
by intermolecular CeH$$$O and NeH$$$Cl hydrogen-bonding
interactions forming a 1D extended chain structure (shown in
Table 2). For complex 4, the asymmetric unit contains two mono-
mers, which are different from a crystallographic point of view. The
conformations of the two independent molecules are almost the
same, with only small differences in bond lengths and bond angles.
The molecules are connected by intermolecular CeH$$$Cl and
NeH$$$Cl hydrogen-bonding interactions (shown in Table 2)
forming a 1D supramolcular chain (see Fig. 9). It is worthwhile to
note that there were no intermolecular interactions in the complex
5. As shown in Fig. 10, the complex 6 presents a centrosymmetric
dinuclear complex. In the crystal structure, which is shown in
Fig. 11, molecules are also connected by intermolecular CeH$$$O
hydrogen-bonding interactions forming a 1D linear chain structure
(shown in Table 2).
2.4.3. X-ray crystallography of complexes 7 and 8
Selected bond lengths and angles of complexes 7 and 8 are listed
in Table 4, and their molecular structures are shown in Figs. 12 and
13, respectively. To obtain a deeper insight into the coordination of
hydroxamic acid to the tin center, the reaction of dialkyltin
dichloride with benzohydroxamic acid in the different molar ratio
was also studied as a part of experimental design. Unexpectedly, we
got two novel alkali metal-mingled three tin nuclei monoorganotin
(IV) complexes, which are obviously different from the well-known
Fig. 10. The molecular structure of complex 6.

1830
H. Yin et al. / Journal of Organometallic Chemistry 696 (2011) 1824e1833
Fig. 11. The 1D chain structure of complex 6, formed by intermolecular CeH$$$O hydrogen-bonding interactions.
Table 4
Selected bond lengths (Å) and angles (ꢁ) for complexes 7 and 8
Complex 7
Sn(1)eO(1)
Sn(1)eO(5)
Sn(1)eO(2)
Sn(1)eC(127)
Sn(1)eO(3)
Sn(1)eO(4)
Sn(1)eO(6)
Sn(1)eK(1)
2.082(7)
2.158(7)
2.206(6)
2.121(11)
2.189(6)
2.276(7)
2.316(7)
3.863(2)
O(1)eSn(1)eO(2)
O(3)eSn(1)eO(4)
O(5)eSn(1)eO(6)
O(2)eSn(1)eO(4)
O(1)eSn(1)eO(5)
O(1)eSn(1)eO(3)
O(5)eSn(1)eO(3)
74.3(2)
71.6(2)
70.0(2)
73.0(2)
81.4(3)
85.7(3)
69.4(3)
Complex 8
Sn(1)eO(5)
Sn(1)eO(3)
Sn(1)eO(1)
Sn(1)eO(6)
Sn(1)eO(2)
Sn(1)eO(4)
Sn(1)eC(64)
2.057(7)
2.128(7)
2.169(7)
2.220(7)
2.266(8)
2.326(8)
2.087(12)
O(1)eSn(1)-O(2)
O(3)eSn(1)-O(4)
O(5)eSn(1)-O(6)
O(5)eSn(1)eO(1)
O(6)eSn(1)-O(2)
O(3)eSn(1)eO(1)
70.9(3)
69.8(3)
75.4(3)
83.0(3)
74.2(3)
70.6(3)
organotin hydroxamates [20e22,28,29]. Figs. 14 and 15 show the
dimeric structure of 7 and the 1D supramolecular chain of 8, which
are both formed through intermolecular hydrogen bonds.
As can be seen from Figs. 12 and 13, complexes 7 and 8 have the
similar topology architectures, which both consist of three
C4H9SnL3 moieties and one half KCl or NaCl, and the alkali metal
cation lies in the center of the complex presenting a crown ether-
Fig. 13. The molecular structure of complex 8 (For clarity, solvent molecules are
omitted).
like coordination geometry with nine hydroxyl O atoms from the
hydroxamato. All the tin atoms possess the same ligand environ-
ments, with only minor differences in bond lengths and bond
angles. For the coordination environment analysis of tin atoms of
Fig. 12. The molecular structure of complex 7 (For clarity, solvent molecules are
omitted).
Fig. 14. The symmetric dimeric structure of complex 7, formed by intramolecular
NeH$$$Cl and NeH$$$O weak interactions hydrogen-bonding interactions.

H. Yin et al. / Journal of Organometallic Chemistry 696 (2011) 1824e1833
1831
Fig. 15. The 1D chain structure of complex 8, formed by CeH$$$O, CeH$$$Cl and CeH$$$N hydrogen-bonding interactions.
Table 5
Crystal data and structure refinement parameters for complexes 1e4
Complex
1
2
3
4
Empirical formula
Formula weight
Wavelength (Å)
Crystal system
Space group
a (Å)
C12H25NO4Sn
366.02
0.71073
Monoclinic
C2/c
25.429(3)
8.9786(11)
17.7388(18)
C19H20NO4Sn
445.05
0.71073
Triclinic
C6H15Cl2NO3Sn
338.78
0.71073
Monoclinic
P2(1)/n
12.8174(13)
7.3990(8)
14.6512(15)
C11H17Cl2NO3Sn
400.85
0.71073
Triclinic
P-1
10.5637(12)
12.9306(13)
13.1131(14)
63.4760(10)
89.309(2)
84.0920(10)
1593.0(3)
4
P1
14.1691(15)
14.1691(15)
41.350(4)
90
90
90
8301.6(14)
16
1.424
1.251
b (Å)
c (Å)
a
b
g
(ꢁ)
(ꢁ)
(ꢁ)
90
90
125.543(2)
90
3295.5(6)
8
1.475
1.557
114.273(2)
90
1266.6(2)
4
1.777
2.419
V (Å3)
Z
Dcalc (Mg/m3)
1.671
1.939
m
(mmꢀ1
)
F(000)
1488
3568
664
792
Crystal size (mm)
Reflections collected
Unique reflections [Rint
0.21 ꢂ 0.17 ꢂ 0.16
0.22 ꢂ 0.17 ꢂ 0.15
0.40 ꢂ 0.28 ꢂ 0.10
0.48 ꢂ 0.37 ꢂ 0.36
8009
18158
6077
8011
]
2894 [R(int) ¼ 0.0485]
2894/0/196
1.118
3674 [R(int) ¼ 0.2211]
3674/0/256
1.009
2240 [R(int) ¼ 0.0321]
2240/2/128
1.066
5432 [R(int) ¼ 0.0294]
5432/652/327
1.146
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2
R indices (all data)
s
(I)]
R1 ¼ 0.0437 wR2 ¼ 0.0932
R1 ¼ 0.1040 wR2 ¼ 0.2830
R1 ¼ 0.0328 wR2 ¼ 0.0771
R1 ¼ 0.0946 wR2 ¼ 0.2580
R1 ¼ 0.0854 wR2 ¼ 0.1212
R1 ¼ 0.1884 wR2 ¼ 0.3490
R1 ¼ 0.0505 wR2 ¼ 0.0918
R1 ¼ 0.1166 wR2 ¼ 0.2709
Table 6
Crystal data and structure refinement parameters for complexes 5e8
Complex
5
6
7
8
Empirical formula
Formula weight
Wavelength (Å)
Crystal system
Space group
a (Å)
C17H23Cl2NO4Sn
494.95
0.71073
Triclinic
P-1
C18H22ClNO3Sn
454.51
0.71073
Monoclinic
P2(1)/c
8.3699(8)
C9.63H10.75Cl0.13K0.13N1.13O2.31 Sn0.38
233.02
0.71073
Monoclinic
C25.33H27.67ClN3Na0.33O6Sn
631.97
0.71073
Monoclinic
C2/c
29.699(3)
Cc
8.1542(7)
29.957(3)
b (Å)
c (Å)
10.6201(11)
14.1153(12)
109.726(2)
92.1470(10)
110.205(2)
1063.28(17)
2
16.0246(16)
14.9992(13)
90
97.9110(10)
90
1992.6(3)
4
25.681(2)
22.521(2)
90
101.8590(10)
90
16956(3)
64
26.219(2)
22.220(2)
90
102.933(2)
90
16863(3)
24
a
b
g
(ꢁ)
(ꢁ)
(ꢁ)
V (Å3)
Z
Dcalc (Mg/m3)
1.546
1.472
1.515
1.430
1.460
1.027
1.494
1.052
m
(mmꢀ1
)
F(000)
496
912
7560
7664
Crystal size (mm)
Reflections collected
Unique reflections [Rint
0.47 ꢂ 0.46 ꢂ 0.35
0.44 ꢂ 0.43 ꢂ 0.36
0.19 ꢂ 0.18 ꢂ 0.13
0.45 ꢂ 0.38 ꢂ 0.33
5501
9812
43846
43372
]
3688 [R(int) ¼ 0.0210]
3688/0/227
0.625
3511 [R(int) ¼ 0.0332]
3511/0/219
1.162
26087 [R(int) ¼ 0.0423]
26087/2/1980
0.936
14887 [R(int) ¼ 0.0632]
14887/2807/994
1.134
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2
R indices (all data)
s
(I)]
R1 ¼ 0.0342 wR2 ¼ 0.0862
R1 ¼ 0.0462 wR2 ¼ 0.0946
R1 ¼ 0.0514 wR2 ¼ 0.1076
R1 ¼ 0.0640 wR2 ¼ 0.1613
R1 ¼ 0.0450 wR2 ¼ 0.1021
R1 ¼ 0.0747 wR2 ¼ 0.1091
R1 ¼ 0.1080 wR2 ¼ 0.1305
R1 ¼ 0.1757 wR2 ¼ 0.2579

1832
H. Yin et al. / Journal of Organometallic Chemistry 696 (2011) 1824e1833
complex 7, Sn(1) is taken for example, which has a coordination
number of seven. The Sn atom is coordinated by three carbonyl O
atoms and three hydroxyl O atoms from benzohydroxamic acid, one
C atom from n-butyl. The bond length of Sn(1)eO(1), Sn(1)eO(2),
Sn(1)eO(3), Sn(1)eO(4), Sn(1)eO(5) and Sn(1)eO(6) are 2.082(7)
Å, 2.206(6) Å, 2.189(6) Å, 2.276(7) Å, 2.158(7) Å and 2.316(7) Å,
which are close to the bond length in the complexes 3e6. The
potassium ions in the compound are nine-coordinated, composed
of nine hydroxyl oxygens from hydroxamic acid. The KeO bond
distances are in the range of [2.761(7) Å-3.025(7) Å]. As can be seen
from Fig. 14, the conformations of the two independent molecules
are connected by a series of intramolecular NeH$$$Cl and NeH$$$O
weak interactions forming a symmetric dimer, and the crystal
structure is stabilized by the intramolecular hydrogen bonds
(shown in Table 2).
The structure of complex 8 is presented in Fig. 13. The tin atoms
of complex 8 are seven-coordinated with six oxygens benzohy-
droxamic acid and one C atom from butyl. The central sodium atom
has a coordination number of nine, and is bonded with nine
hydroxyl oxygens. The NaeO bond distances are in the range of
[2.780(8) Å ꢀ3.006(8) Å]. For complex 8, hydrogen bridged dimmer
has also been found. In addition, due to the existing of the unco-
ordinated dichloromethane solvate molecules, these dimeric
structures are connected by intermolecular CeH$$$O, CeH$$$Cl
and CeH$$$N hydrogen-bonding interactions (shown in Table 2)
forming an interesting 1D extended chain structure, which is
shown in Fig. 15.
4.2. Syntheses of the complexes 1e8
4.2.1. [(C4H9)2Sn(CH3CONHO)(CH3COO)] (1)
The reaction was carried out under nitrogen atmosphere. Ace-
tohydroxamic acid (0.06 g, 0.8 mmol), acetic acid (0.048 g, 0.8 mmol)
and KOH (0.0896 g, 1.6 mmol) were added to a stirred solution of
methanol (30 ml) in a Schlenk flask and stirred for 0.5 h. Dibutyltin
dichloride (0.243 g, 0.8 mmol) was then added to the reactor. The
reaction mixture was stirred for 8 h at room temperature and then
filtrated. The filtrate was evaporated in vacuo. The obtained solid was
recrystallized from ethylether/petroleum (1:1). yield: 75%, m.p.
65e67 ꢁC. Anal. Calc. for C12H25NO4Sn: C, 39.37; H, 6.88; N, 3.83%.
Found: C, 39.28; H, 6.96; N, 3.92%. IR (KBr, cmꢀ1): 3180s (NeH),
1621s, 1539m (CO/NC); 918s (NeO); 520s (SneC); 448s (SneO);
1380s (COO). 1H NMR (CDCl3, ppm):
¼ 0.90 (s, 3H, NeCeCH3); ¼ 1.25e1.63 (m,18H,eCH2CH2CH2CH3).
13C NMR (CDCl3, ppm):
¼ 13.60, 22.10, 25.24, 26.10 (ꢀCH2CH2CH2CH3,);
(CH3eC]O, CH3eCONH). 119Sn NMR (CDCl3, ppm):
d
¼ 1.99 (s, 3H, O]CeCH3);
d
d
d
¼ 178.98 (COO);
d
¼ 165.26 (CON);
d
d
¼ 27.21, 29.67
¼ ꢀ70.
d
4.2.2. [(CH3)2Sn(CONHOC6H5)(COOC6H5)]$0.5C6H6 (2)
Complex 2 was prepared in the same way as 1. The colourless
solid was recrystallized from benzene/hexane (1:1) to give col-
ourless powder, yield: 77%, m.p.127e130 ꢁC. Anal. Calc. for
C19H20NO4Sn: C, 51.27; H, 4.53; N, 3.15%. Found: C, 51.18; H, 4.59; N,
3.21%. IR (KBr, cmꢀ1): 3200 w (NeH); 1598w, 1563w (CO/NC);
1380m (COO); 918s (NeO); 434s, 523m (SneO); 548 m and 570w
(SneC). 1H NMR (CDCl3, ppm):
d
d
¼ 7.40e7.81 (m,13H, PheH);
¼ 0.10 (s, 6H, ꢀCH3). 13C NMR (CDCl3, ppm):
d
¼ 172.10 (COO);
3. Conclusion
d
¼ 164.22 (CON); ¼ 126.61, 127.32, 128.21, 128.41, 128.93, 129.26,
d
130.08, 130.43, 132.80 (PheC). 119Sn NMR (CDCl3, ppm):
d
¼ ꢀ76.
Eight organotin(IV) complexes with hydroxamic acids, the
carboxyl acid hybrid five-coordinated dialkyltin complexes, 1
and 2, the six-coordinated mono-n-butyltin complexes, 3e6, and
the alkali metal-mingled seven-coordinated mono-n-butyltin
complexes, 7 and 8, are reported in this paper. These complexes
are obtained by selecting mono- or dialkyltin chlorides and three
ligands with different molar ratios. The results demonstrate that
the changing of reaction ratio of between the hydroxamic acid
ligand and alkyltin salt have a significant influence on the
structures from 1 : 1 for complexes 3e6 to 2 : 1 for complexes 7
and 8, and, therefore, the properties of the corresponding
organotin complexes. With the aim to finally design and
synthesize organotin complexes with desired structures and
high anti-tumor activities, more work is required to explore new
complexes using hydroxamic acid ligands attached with
different tin salts.
4.2.3. [(C4H9)Sn(CH3CONHO)$Cl2$H2O] (3)
The reaction was carried out under nitrogen atmosphere. Ace-
tohydroxamic acid (0.06 g, 0.8 mmol) and KOH (0.0449 g, 0.8 mmol)
were added to a stirred solution of methanol (30 ml) in a Schlenk
flask and stirred for 0.5 h. Butyltin trichloride (0.2256 g, 0.8 mmol)
was then added to the reactor. The reaction mixture was stirred for
8 h at room temperature and then filtrated. The filtrate was evapo-
rated in vacuo. The obtained solid was recrystallized from ethyl-
ether/petroleum (1:1), yield: 80%，m.p.107e108 ꢁC. Anal. Calc. for
C6H15Cl2NO3Sn: C, 21.27; H, 4.46; N, 4.13%. Found: C, 21.19; H, 4.51; N,
4.18%. IR (KBr, cmꢀ1): 3154w (NeH); 1613s, 1559m (CO/NC); 920s
(NeO); 590s (SneC); 434s (SneO). 1H NMR (CDCl3, ppm):
d
¼ 11.60
(s, 1H, NeH);
d
¼ 0.94 (t, 3H, eCH3);
d
¼ 2.20 (s, 3H, NeCeCH3);
d
¼ 1.20e1.82 (m, 6H, eCH2CH2CH2-);
d
¼ 2.06 (s, 2H, H2O). 13C NMR
(CDCl3, ppm):
d
¼ 164.96(CON);
d
¼ 13.32, 17.39, 25.26, 27.40, 29.68
(eCH2CH2CH2CH3, eCH3). 119Sn NMR (CDCl3, ppm):
d
¼ ꢀ380.
4. Experimental details
4.2.4. [(C4H9)Sn(CONHOC6H5)$Cl2$H2O] (4)
4.1. Materials and measurements
Complex 4 was prepared in the same way as 3 The colourless
solid was recrystallized from ethylether/petroleum (1:1) to give
colourless powder, yield: 83%, m.p. 76e78 ꢁC. Anal. Calc. for
C11H17Cl2NO3Sn: C, 32.96; H, 4.27; N, 3.49%. Found: C, 32.91; H, 4.33;
N, 3.52%. IR (KBr, cmꢀ1): 3235w (NeH); 1617s, 1600m (CO/NC); 920s
(NeO); 439s, 518s (SneO); 573s (SneC). 1H NMR [(CD3)2SO, ppm]:
Dibutyltin dichloride, dimethyltin dichloride, butyltin tri-
chloride, acetic acid, Acetohydroxamic acid and benzoic acid
were commercially available, and they were used without
further purification. Benzohydroxamic acid was prepared by the
reported method [23]. The elemental analyses were performed
on a PE-2400eII elemental analyzer. IR spectra were recorded on
d
¼ 13.90 (s, 1H, NeH);
d
¼ 7.48e7.88 (m, 5H, PheH);
d
¼ 3.36 (s, 2H,
H2O);
d
¼ 1.37e1.78 (m, 6H, eCH2CH2CH2-);
d
d
¼ 0.93 (t, 3H, eCH3).
¼ 13.44, 25.06, 27.07,
a
Nicolet-5700 spectrophotometer using KBr discs. X-ray
13C NMR [(CD3)2SO, ppm]:
d
d
¼ 161.14 (CON);
measurements were made on Bruker Smart-1000 CCD
a
34.99, (eCH2CH2CH2CH3);
¼ 126.12, 127.60, 128.44, 131.82 (PheC).
diffractometer with graphite monochromated Mo-K
a
radiation
119Sn NMR [DMSO-d6, ppm]:
d
¼ ꢀ377.
(
l
¼ 0.71073 Å). 1H, 13C and 119Sn NMR spectra were recorded on
a Varian Mercury Plus-400 NMR spectrometer. Chemical shifts
were given in ppm relative to Me4Si and Me4Sn in CDCl3 or
DMSO-d6 solvent.
4.2.5. [(C4H9)SnONCO(C6H5)2$Cl2$H2O]$H2O (5)
Complex 5 was prepared in the same way as 3. The brown solid
was recrystallized from ethylether/petroleum (1:1) to give

H. Yin et al. / Journal of Organometallic Chemistry 696 (2011) 1824e1833
1833
colourless powder, yield: 80%, m.p. 96e97 ꢁC. Anal. Calc. for
4.3. X-ray crystallographic studies
C17H23Cl2NO4Sn: C, 41.25; H, 4.68; N, 2.83%. Found: C, 41.20; H,
4.72; N, 2.88%. IR (KBr, cmꢀ1): 1614w, 1587w (CO/NC); 923s (NeO);
439s, 518w (SneO); 580w, (SneC). 1H NMR (CDCl3, ppm):
Diffraction data were collected on a Smart CCD area-detector
with graphite monochromated Mo K radiation (
a
l
¼ 0.71073 Å). A
d
¼
7.27e7.44 (m, 10H, PheH);
d
¼
0.93e1.94 (m, 9H,
semiempirical absorption correction was applied to the data. The
structure was solved by direct methods using SHELXS-97 and
refined against F2 by full-matrix least squares using SHELXL-97.
Hydrogen atoms were placed in calculated positions. Crystal data
and experimental details of the structure determinations are listed
in Table 5 and Table 6
eCH2CH2CH2CH3)
d
d
¼ 2.19 (s, 4H, H2O). 13C NMR (CDCl3, ppm):
¼ 163.93 (CON); ¼ 13.24, 25.48, 26.79, 33.01 (ꢀCH2CH2CH2CH3);
d
d
¼ 126.44, 128.17, 129.15, 129.22, 129.28, 129.73, 131.75, 138.62
¼ ꢀ367.
(PheC). 119Sn NMR (CDCl3, ppm):
d
4.2.6. [(C4H9Sn)2(ONCO(C6H5)2)2$Cl2$(OCH3)2] (6)
Complex 6 was prepared in the same way as 3. The brown solid
was recrystallized from methanol/petroleum (2:1) to give colour-
less powder, yield: 63%, m.p. 93e95 ꢁC. Anal. Calc. for
C18H22ClNO3Sn: C, 47.56; H, 4.88; N, 3.08%. Found: C, 47.48; H, 4.95;
N,3.12%. IR (KBr, cmꢀ1): 1604w, 1538w (CO/NC); 925s (NeO);
481s and 545s (SneO); 569w(SneC). 1H NMR (CDCl3, ppm):
Acknowledgments
We acknowledge the National Natural Foundation of China
(20771053), the National Basic Research Program (No. 2010CB
234601), the Natural Science Foundation of Shandong Province
(Y2008B48) for financial support. And this work was supported by
Shandong “TaieShan Scholar Research Fund”.
d
¼
7.23e7.40 (m, 10H, PheH);
d
¼
0.93e1.89 (m,
9H, ꢀCH2CH2CH2CH3);
ppm):
(ꢀCH2CH2CH2CH3);
129.32, 129.39, 129.80, 131.82, 139.06 (PheC). 119Sn NMR (CDCl3,
ppm):
¼ ꢀ353.
d
¼ 3.47 (s, 3H, ꢀOCH3). 13C NMR (CDCl3,
d
¼
164.13 (CON);
d
¼
13.45, 25.57, 27.07, 33.84
Appendix. Supplementary material
d
¼ 50.81(ꢀOCH3);
d
¼ 126.80, 128.29, 129.03,
Supplementary data related to this article can be found online at
doi:10.1016/j.jorganchem.2011.02.017.
d
4.2.7. [(C4H9Sn)3(NHOCOC6H5)9K]þ$Clꢀ$(CH3CH2)2O (7)
The reaction was carried out under nitrogen atmosphere. ben-
zohydroxamic acid (0.1097 g, 0.8 mmol) and KOH (0.0449 g,
0.8 mmol) were added to a stirred solution of methanol (30 ml) in
a Schlenk flask and stirred for 0.5 h. Dibutyltin dichloride(0.1215 g,
0.4 mmol) was then added to the reactor. The reaction mixture was
stirred for 8 h at room temperature and then filtrated. The filtrate
was evaporated in vacuo. The obtained solid was recrystallized from
ethylether/petroleum (1:1) to give colourless blocks of crystals,
References
[1] L. Pellerit, L. Nagy, Coord. Chem. Rev. 224 (2002) 111e150.
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Frontiers, and Applications. Wiley, 2008.
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tallics 5 (1986) 85e89.
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68e72.
yield: 78%, m.p.124e126 ꢁC. Anal. Calc. for C9.63H10.75Cl0.13
-
K0.13N1.13O2.31Sn0.38: C, 49.41; H, 4.63; N, 6.76%. Found: C, 49.35; H,
4.69; N, 6.82%. IR (KBr, cmꢀ1): 3191w (NeH); 1600s, 1569s (CO/NC);
917s (NeO); 449m and 509m (SneO); 554s, (SneC). 1H NMR(CDCl3,
[10] H.D. Yin, C.H. Wang, C.L. Ma, D.Q. Wang, J. Organomet, Chem 689 (2004)
246e251.
ppm):
d
¼ 7.02e7.93 (m, 45H, PheH); ¼ 4.02 (m, 4H, eCH2OCH2-);
d
¼ 0.85e1.70 (m, 33H, ꢀCH2CH2CH2-, eCH3). 13C NMR (CDCl3, ppm):
[11] C.L. Ma, J.S. Sun, R.F. Zhang, J. Organomet. Chem. 691 (2006) 5873e5886.
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T.R. Deam, D.W. Christianson, J. Am. Chem. Soc. 119 (1997) 850e851.
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d
d
d
d
¼ 162.23 (CON);
d
¼ 126.55, 128.24, 130.12, 131.26 (PheC);
¼ 15.14, 15.77, 18.75, 25.27, 29.65 (ꢀCH2CH2CH2CH3, eCH3).
¼ 63.90 (ꢀCH2OCH2). 119Sn NMR (CDCl3, ppm):
d
¼ ꢀ482.
4.2.8. [(C4H9Sn)3(NHOCOC6H5)9Na]þ$Clꢀ$CH2Cl2 (8)
The reaction was carried out under nitrogen atmosphere. Ben-
zohydroxamic acid (0.1097 g, 0.8 mmol) and NaOH (0.032 g,
0.8 mmol) were added to a stirred solution of methanol (30 ml) in
a Schlenk flask and stirred for 0.5 h. Dibutyltin dichloride(0.1215 g,
0.4 mmol) was then added to the reactor. The reaction mixture was
stirred for 8 h at room temperature and then filtrated. The filtrate
was evaporated in vacuo. The obtained solid was recrystallized
from dichloromethane/petroleum (1:1) to give colourless blocks of
crystals, yield: 78%, m.p.122e124 ꢁC. Anal. Calc. for C25.33H27.67
-
ClN3Na0.33O6Sn: C, 48.15; H, 4.41; N, 6.65%. Found: C, 48.10; H, 4.35;
N, 6.71%. IR (KBr cmꢀ1): 3200m (NeH); 1600s, 1569s (CO/NC); 917s
(NeO); 449m and 509m (SneO); 554s, (SneC); 1H NMR (CDCl3,
ppm):
27H, ꢀCH2CH2CH2CH3).
ppm):
¼ 162.45 (CON);
d
¼
7.06e7.62 (m, 45H, PheH);
d
¼
0.85e1.70 (m,
d
¼ 5.25 (s, 2H, CH2Cl2). 13C NMR (CDCl3,
¼ 128.01, 128.23, 129.75, 130.59 (PheC);
d
d
d
¼ 13.53, 19.19, 26.16, 29.78 (ꢀCH2CH2CH2CH3); ¼ 53.33 (CH2Cl2).
d
119Sn NMR (CDCl3, ppm):
d
¼ ꢀ480.