Structural study of di- and triorganotin(IV) dicarboxylates containing one double bond

Article abstract of DOI:10.1016/j.jorganchem.2010.07.032

Tri- and diorganotin(IV) dicarboxylates derived from trans-glutaconic acid and acetone 1,3-dicarboxylic acid were prepared. Their structure was studied using NMR, IR, and MS data. All of these compounds (except for compound 2a) are polymeric in the solid state and depolymerise upon dissolving in deuteriochloroform to give monomeric particles with four-coordinated central tin atoms. X-ray crystallography was used to characterize (E)-bis(tributylstannyl) pent-2-enedioate (1a). This compound crystallizes in a monoclinic space group system. The supramolecular organization of 1a can be described as layered polymeric sheets constructed of forty-membered rings that are interconnected on four different sites to the third dimension. Each layer assembled of the forty-membered rings, is made up of six triorganotin fragments and six trans-glutaconic acids, where four of them are incorporated in the core of the ring and other two are bidentate bridging and participating in the ring system by three atoms of CO₂ group only.

Full text of DOI:10.1016/j.jorganchem.2010.07.032

Journal of Organometallic Chemistry 695 (2010) 2493e2498
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Structural study of di- and triorganotin(IV) dicarboxylates containing
one double bond
a
,
b
a
c
ꢀ
*
ꢀ
ꢀ ꢁꢀ ꢀ
ꢀꢀ
Antonín Lycka , Ales Ruzicka , Jan Vanecek , Lenka Ceslová
a Research Institute for Syntheses (VUOS), Rybitví 296, CZ-533 54 Pardubice 20, Czech Republic
b Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, CZ-532 10 Pardubice, Czech Republic
c Department of Analytical Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, CZ-532 10 Pardubice, Czech Republic
a r t i c l e i n f o
a b s t r a c t
Article history:
Tri- and diorganotin(IV) dicarboxylates derived from trans-glutaconic acid and acetone 1,3-dicarboxylic
acid were prepared. Their structure was studied using NMR, IR, and MS data. All of these compounds
(except for compound 2a) are polymeric in the solid state and depolymerise upon dissolving in deu-
teriochloroform to give monomeric particles with four-coordinated central tin atoms. X-ray crystallog-
raphy was used to characterize (E)-bis(tributylstannyl) pent-2-enedioate (1a). This compound
crystallizes in a monoclinic space group system. The supramolecular organization of 1a can be described
as layered polymeric sheets constructed of forty-membered rings that are interconnected on four
different sites to the third dimension. Each layer assembled of the forty-membered rings, is made up of
six triorganotin fragments and six trans-glutaconic acids, where four of them are incorporated in the core
of the ring and other two are bidentate bridging and participating in the ring system by three atoms of
CO2 group only.
Received 3 February 2010
Received in revised form
13 July 2010
Accepted 30 July 2010
Available online 7 August 2010
Keywords:
Organotin(IV) dicarboxylates
Acetone 1,3-dicarboxylic acid
trans-Glutaconic acid
NMR
X-ray
Ó 2010 Published by Elsevier B.V.
1. Introduction
dicarboxylic acid and trans-glutaconic acid. Acetone 1,3-dicarbox-
ylic acid (3-oxopentanedioic acid, HOOCCH2C(]O)CH2COOH) is
Organotin(IV) carboxylates have been studied very frequently
up to now because of their well known catalytic and medical
activity [1,2]. The structural motifs of these compounds are well
established and studied by X-ray diffraction [3], Moessbauer and CP
MAS NMR techniques in the solid state and, mainly, multinuclear
NMR techniques in solution [3,4]. The tin atom in these compounds
can be four-coordinated or five-coordinated (with major occur-
rence in the solid state). In the second case, the tin atom is sur-
rounded by three carbon atoms originated from organic groups and
two oxygen atoms from one asymmetrically bidentate carboxylate
(intramoleculary chelated or two different carboxylate groups
(intermolecularly bridging)).
a “shorter” analogue of 4-ketopimelic acid [6,7] studied recently. In
contrast to 4-ketopimelic acid, acetone 1,3-dicarboxylic acid exists
partially in its enol form e HOOCCH]C(eOH)CH2COOH. Trans-
glutaconic acid ((E)-pent-2-enedioic acid, HOOCCH]CHCH2COOH)
is a suitable model compound for the enol form of acetone 1,3-
dicarboxylic acid, having also two different carboxylic groups, one
double bond and hydrogen instead of hydroxy group.
2. Results and discussion
2.1. Synthesis and NMR spectra
Such compounds that are polymeric in the solid state usually
depolymerise to give oligomeric or even monomeric structural
units in solutions of various solvents [4].
Only relatively little is known about structure of bis(organotin
(IV)) dicarboxylates (Refs. [5e7] and references therein).
In this contribution, we would like to present our results con-
cerning the structure of organotin(IV) derivatives of acetone 1,3-
Bis(triorganostannyl) trans-glutaconates (1a,b) were prepared
by the reaction of bis(tributyltin(IV)) oxide with trans-glutaconic
acid in refluxing toluene and, analogously, 1b by the reaction of
trans-glutaconic acid with triphenyltin(IV) hydroxide. Both reac-
tions gave good yields of products the purity of which was checked
using 1H and 119Sn NMR spectra.
We observed 3J(1H, 1H) coupling constant in the 1H NMR spectra
belonging to protons on the double bond being 15.6 Hz for 1a and
15.7 Hz for lb, respectively. Their values mean that trans arrange-
ment of double bond protons from starting acid was retained in
both compounds. In line with the structure, two different 119Sn
* Corresponding author. Fax: þ420 46 6823900.
ꢀ
E-mail address: antonin.lycka@vuos.com (A. Lycka).
0022-328X/$ e see front matter Ó 2010 Published by Elsevier B.V.
doi:10.1016/j.jorganchem.2010.07.032

ꢀ
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A. Lycka et al. / Journal of Organometallic Chemistry 695 (2010) 2493e2498
Table 1
119Sn, 13C and 1H chemical shifts and nJ(119Sn, 13C) and 3J(1HC]C1H) coupling
constants (Hz, ꢀ0.3 Hz) in compounds 1a,b and 2a measured in deuteriochlorofom.
1a
1b
2a
d(
119Sn)
CH2COOSn
]CHCOOSn
117.3
107.8
ꢁ100.5
ꢁ111.8
ꢁ139.1
ꢁ139.1
d(
13C)
]CHCOO
]CHCOO
CH]CHeCH2
CH2COO
171.2
125.2
140.5
38.2
172.2
124.2
141.9
37.5
175.2
123.7
142.4
37.6
CH2COO
175.3
176.1
179.2
10
16.4 (358.8a)
25.3 (574.8a)
27.6 (20.2a)
26.9 (66.1a)
13.6
138.3 (635.7a)
137.8 (632.3a)
20
30
40
136.8 (48.2a)
128.9 (63.3a)
130.1
26.5 (35.4a)
26.3 (99.1a)
13.5
d
(1H)
]CHCOO
]CH-
CH2COO
10
20
30
40
5.86 (15.6b)
6.90 (15.6b)
3.14c
5.99 (15.7b)
7.12 (15.7b)
3.30
5.93 (15.7b)
7.16 (15.7b)
3.29c
Fig. 1. 119Sn NMR spectra of compounds 1a (upper trace) and 3a (bottom trace).
1.20c
ec
1.62c
1.55c
7.71c
1.62c
1.28c
7.42c
1.34c
chemical shifts were detected in the 119Sn NMR spectra of
compounds 1a (Fig. 1) and 1b.
0.86c
7.42c
0.87c
nJ(119Sn, 13C).
a
b
3J(1HeC]Ce1H).
We tried to assign them experimentally using two-dimensional
1H e 119Sn HMQC spectra [8] based on nJ(119Sn, 1H) coupling
constants of tin atoms with protons of glutaconic acid. No tin
satellites were observable in the standard 1H NMR spectra for
protons of glutaconic acid, contrary to those in R3Sn. Two-
dimensional 1He119Sn HMQC experiments were thus optimized for
nJ (119Sn, 1H) coupling constants being very small (from 3 to 15 Hz).
Unfortunately, only correlations of tin resonances with tributyl and
triphenyl moieties were observable. We can conclude that nJ(119Sn,
1H) coupling constants of tin atoms with protons of glutaconic acid
must be (if any) very close to zero.
c
The numbering of the butyl or phenyl atoms is indicated as 10- 400in the
following scheme:
2´ 3´
4´
2´
1´
4´
Sn
Sn
1´
3´
.
The 13C resonances of COO groups are well separated and were
a reactive agent. An attempt to react acetone 1,3-dicarboxylic acid
with Bu3SnOCH3 in a NMR tube afforded successfully compound
3a. This compound is stable in the solution, however, it decom-
poses during separation. The compound 3b was prepared using
sodium methylate in methanol and Ph3SnCl. The 119Sn, 13C and 1H
NMR data are given in Table 2. There were two sets of NMR signals
in the NMR spectra of compounds 3a,b (Scheme 1) corresponding
to a mixture of keto and enol forms (keto to enol ratio being ca 8:1
for 3a and ca 15:1 for 3b). The keto forms are more abundant and
symmetric and, thus, the assignment of all NMR resonances was
straightforward. Two tin resonances were detected in enol forms
in 3a (Fig. 1) and 3b, similarly to compounds 1a,b. A comparison of
119Sn chemical shifts allowed a tentative assignment of 119Sn
resonances in enol forms and compounds 1a,b. Signals being
closer to the 119Sn chemical shift in keto form in compound 3a,b
were assigned to CH2COOSn. The 119Sn resonances in 3a (Fig. 1)
and 3b were slightly more broadened than those in compounds 1a
(Fig. 1) and 1b. This is very likely due to the existence of the
dynamic ketoeenol equilibrium involving an enol proton transfer
in between the enol and keto tautomers of the organotin dicar-
boxylate compounds 3a,b.
differentiated using proton-coupled 13C NMR spectra: the signal
with less complicated multiplet was assigned to ]CHCOO
2
(
d
¼ 171.2, the coupling with one proton via J(13C, 1H)) while the
more complicated one to CH2COO carbon (
d
¼ 175.3, the coupling
with two protons via J(13C, 1H)). On the contrary, the 13C reso-
nances of butyl and phenyl groups in COOSnR3 fragments in
compounds 1a,b were only slightly broadened and, except for ipso
carbons of phenyl groups, were not resolved. 2D 1He13C HMQC
experiments were used for the assignment of proton resonances in
butyl and phenyl groups since the unambiguous assignment of the
13C resonances was straightforward using nJ(119Sn, 13C) coupling
constants.
2
We performed the reaction of trans-glutaconic acid with dibu-
tyltin oxide and with diphenyldichlorodistannane and obtained
compounds 2a and 2b, respectively. The 119Sn, 13C and 1H chemical
shifts were determined for compound 2a (Table 1) (compound 2b is
insoluble both in deuteriochloroform and hexadeuteriodimethyl
sulfoxide). We obtained one set of sharp and resolved signals in 13C
and 1H NMR spectra and only one signal in 119Sn, NMR spectrum.
The problem in application of acetone 1,3-dicarboxylic acid
consists in its rather low thermal stability. We performed the
reaction of bis(tributyltin(IV)) oxide with acetone 1,3-dicarboxylic
acid in refluxing benzene or toluene, however, under these
experimental conditions 1,3-dicarboxylic acid undergoes decar-
boxylation to give CH3COCH2COOH first and, finally, acetone which
is removed from the reaction mixture leaving, after removal of
benzene or toluene, only traces of compounds having appropriate
protons and carbons belonging to acetone 1,3-dicarboxylic acid. It
was thus necessary to perform the reaction at 300 K and to use
In the 13C NMR spectra of the keto forms of compounds 3a,b,
two resonances are observed in relative intensity ratio 1:2
belonging to C]O and two equivalent COO while there are three
resonances corresponding to two different COO groups and ]C
(OH)e in enol form of compounds 3a,b. Proton-coupled spectrum
was used for their assignment where a broadened signal was
assigned to ]CHCOO, quartet-like signal due to the interaction of
carbon with CH2 and OH protons to ]C(OH)e and triplet due to the
interaction of carbon with CH2 protons to C(OH)CH2COO.

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A. Lycka et al. / Journal of Organometallic Chemistry 695 (2010) 2493e2498
2495
Table 2
Table 3
119Sn, 13C and 1H chemical shifts and nJ(119Sn, 13C) coupling constants (Hz, ꢀ0.3 Hz)
in compounds 3a,b measured in deuteriochlorofom.
Selected parameters of IR spectra for compounds 1e3 [cmꢁ1].
Medium
n(C]O)
nas(CO2)
ns(CO2)
3a (Keto)
3a (Enol)
3b (Keto)
3b (Enol)
1a
1b
2a
2b
CH2Cl2
KBr
e
e
e
1651, 1617
1587, 1551
1584, 1549
1336
1378
1377
d(
119Sn)
CH2COOSn
]CHCOOSn
118.2
e
115.9
111.5
ꢁ82.3
ꢁ84.0
ꢁ99.2
ATRa
e
CH2Cl2
KBr
e
e
e
1652, 1620
1574, 1547
1574, 1545
1335
1350
1347
d(
13C)
CH2COO
CH2COO
CO
]CHCOO
]CHCOO
]C(OH)-
C(OH)CH2COO
171.8
49.6
198.2
e
e
173.2
50.2
201.4
e
e
ATRa
e
e
CH2Cl2
KBr
e
e
e
1606, 1583
1602, 1572
1600, 1565
1370
1378
1378
e
e
176.4
92.5
170.3
41.6
177.0
89.8
172.2
50.2
ATRa
e
e
KBr
e
e
1560b
1557b
1389
1390
e
e
ATRa
e
e
C(OH)CH2COO
e
173.4
e
173.2
b
b
3a
3b
CDCl3
1724
1652
1340
1
2
3
4
16.5 (358.4a)
27.6 (20.6a)
26.8 (66.0a)
13.4
138.3 (639.7a)
136.2 (43.7a)
128.3 (58.2a)
129.3
b
b
b
b
b
b
KBr
1722
1722
1579
1579
1380
1381
ATRa
a
Attenuated total reflection IR.
Broad signal.
d
(1H)
b
CH2COO
]CHCOO
]C(OH)COO
C(OH)CH2COO
1
2
3
4
2.28
e
e
2.23
e
e
5.03
12.67
5.12
12.36
3.47
e
b
e
e
The reactions of acetone 1,3-dicarboxylic acid with dibutyldi-
e
3.14
e
b
chlorodistannane and with diphenyldichlorodistannane gave white
solid material completely insoluble both in deuteriochloroform and
hexadeuteriodimethyl sulfoxide having high melting points. The
reason might be that oxygen from enol form of acetone 1,3-
dicarboxylic acid can participate as tridentate ligand and form
a complicated structure of these insoluble materials.
1.20
1.54
1.27
0.84
e
b
b
b
7.56
7.38
7.38
b
b
nJ(119Sn, 13C).
a
b
Not resolved from signals of the prevailing keto form.
2.2. Mass spectra
The results of electrospray ionization (ESI) mass spectrometry
measurements in positive-ion mode are summarized in the
Experimental Section. The typical feature of ESI mass spectra of
organotin carboxylates is the cleavage of the most labile bond SneO
in the molecules yielding two complementary ions where the
cationic part of the molecule is measured in the positive-ion mode.
The cationic part [SnR3]þ and subsequent fragment ions [HSnR2]þ
and [H2SnR]þ are observed in the first-order positive ESI mass
spectra.
R
Sn
R
R
O
O
R
R
Sn
R
O
O
1a,b
R
Sn
R
O
O
2.3. Infrared spectra
O
O
The significant tool for evaluation of organotin carboxylate
structures is IR spectroscopy, especially the values of nas and nS for
carbonyl vibration in the CO2 group [2].
2a,b
n
R
Sn
R
R
Sn
R
These values and n(C]O) for 1a,be3a,b in methylenedichloride
O
O
solution (3a in deuteriochloroform), KBr pellets and using ATR
(Attenuated Total Reflection) spectra, respectively, are collected
R
R
in Table 3. The nas(CO2) (1540e1590 cmꢁ1
)
and ns(CO2)
O
O
O
(1330e1390 cmꢁ1) values found for all compounds in solid state
spectra except for 2a, are in agreement with those reported earlier
for a polymeric structure with bridging bidentate carboxylic
groups. The increase of nas(CO2) values in methylenedichloride (in
deuteriochroform for 3a) solution compared to the same parameter
in KBr pellets and ATR corresponds to breaking up solid state
polymeric structure into the monomers upon dissolving of these
compounds. Only one absorption was obtained for the “symmetric”
keto forms of compounds 3a,b while in other compounds two
absorptions were detected in line with the existence of two
different eC(]O)OSn moieties. In other cases (Table 3), there are
always two C]O frequencies, which are different in CH2Cl2 solution
and the solid state IR while there are two C]O frequencies in 2a
which are the same in solution and the solid state IR. Two C]O
frequencies mean two different structural motifs [6].
R
Sn
R
R
Sn
R
O
O
R
R
O
OH
O
3a,b
2´
3´
1´ 2´
3´
4´
1´
4´
b:
a: -CH2CH2CH2CH3
Scheme 1.

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A. Lycka et al. / Journal of Organometallic Chemistry 695 (2010) 2493e2498
2496
within each carboxylic group differ by 0.02 Å. The shorter distance
CeO is associated with the closer contact to the tin atom (C1, O1,
Sn1 and C5, O3, Sn2) and the parallel orientation of the contact to
the carboxylic acid chain. The second type of SneO bond, for
example Sn2eO2, which is oriented almost perpendicularly to the
acid chain, is significantly elongated (difference about 0.3 Å, Fig. 3).
Both types of the tin atom have almost perfect trigonal bipyramidal
geometry with oxygen atoms in axial positions and O1eSn1eO4,
and O3eSn2eO2 angles approaching the ideal value (172.34(14)
and 173.68(15)ꢃ). The equatorial girdles have also nearly perfect
planar fashion with the values of sums of interatomic angles being
around 357ꢃ. The significant differences between the CeC distances
in the trans-glutaconic acid chain determine the C]C double bond
position.
3. Experimental part
The syntheses were performed without protection from air.
Trans-glutaconic acid ((E)-pent-2-enedioic acid), di- and tri-
organotin chlorides, oxides or methoxide, methanol, toluene and
deuteriochloform were obtained from Sigma-Aldrich and acetone
1,3-dicarboxylic acid (3-oxopentanedioic acid) from the Research
Institute for Organic Syntheses, Pardubice.
Fig. 2. Molecular structure of 1a, ORTEP diagram, 30% probability level, hydrogen
atoms as well as disordered groups are omitted for clarity. Selected interatomic
distances and angles [Å, ꢃ]: Sn1C22 2.130(8), Sn1C18 2.137(6), Sn1C26 2.143(8), Sn1 O1
2.170(4), Sn1 O4 2.462(4), Sn2C6 2.122(6), Sn2 C10X 2.133(7), Sn2 C14X 2.138(9), Sn2
O3 2.177(4), Sn2 O2 2.434(4), O1C1 1.270(7), O2C1 1.248(6), O3C5 1.262(8), O4C5 1.243
(8), C1 C2X 1.489(15), C2X C3X 1.20(2), C3X C4X 1.569(19), C4X C5 1.586(14), C22
Sn1C18 119.9(3), C22 Sn1C26 120.8(3), C18 Sn1C26 116.0(3), C22 Sn1 O1 100.2(3), C18
Sn1 O1 90.0(2), C26 Sn1 O1 97.6(2), C22 Sn1 O4 82.9(3), C18 Sn1 O4 82.4(2), C26 Sn1
O4 86.7(2), O1 Sn1 O4 172.34(14), C6 Sn2 C10X 116.7(3), C6 Sn2 C14X 118.2(3), C10X
Sn2 C14X 123.3(3), C6 Sn2 O3 90.0(2), C10X Sn2 O3 96.6(2), C14X Sn2 O3 96.5(3), C6
Sn2 O2 83.69(18), C10X Sn2 O2 86.8(2), C14X Sn2 O2 85.9(2), O3 Sn2 O2 173.68(15), O2
C1 O1 122.9(5), O4C5 O3 123.8(6).
3.1. NMR spectroscopy
The solution state 1H (500.13 MHz), 119Sn (186.50 MHz) and 13
C
NMR (125.76 MHz) spectra of the studied compounds were
measured on a Bruker Avance 500 spectrometer equipped with
5 mm tuneable probe with z-gradient at laboratory temperature.
The samples were dissolved in deuteriochloroform. The 1H NMR
spectra were obtained using standard procedure; proton-decou-
pled and proton-coupled 13C NMR as well as two-dimensional
1He13C HMQC and 1He13C HMBC spectra were measured. The 1H
and 13C chemical shifts were referred to the signal of internal tet-
The values of
n
(C]O) in carbonyl group in compounds 3a,b are
very similar (1722e4 cmꢁ1). Though
n
(C]O) of the CO2 groups in
the minor enol forms in 3a,b are very likely overlapped by stronger
absorptions of the keto forms, the sharp signal of the enolic OH was
detected at 3631 cmꢁ1 (chloroform), 3616 cmꢁ1 (KBr) and 3617
cmꢁ1(ATR).
ramethylsilane (
d
¼ 0.0). One-dimensional 119Sn NMR spectra were
measured using the inverse gated-decoupling mode. Two-
dimensional 1He119Sn HMQC experiments were optimized for nJ
2.4. X-ray crystallography
(
119Sn, 1H) coupling constants from 3 to 15 Hz. The 119Sn chemical
shifts are referred to external neat tetramethylstannane (
The numbering system for the NMR spectral data is shown in
Scheme 1.
d
¼ 0.0).
The solid state structure of 1a was determined by diffraction
techniques. Compound 1a crystallizes in a monoclinic space group
system. The supramolecular organization of 1a can be described as
layered polymeric sheets (Fig. 2) constructed of forty-membered
rings which are interconnected on four different sites to the third
dimension. Each layer assembled of the forty-membered rings, is
made up of six triorganotin fragments and six trans-glutaconic
acids (Fig. 3), where four of them are incorporated in the core of the
ring and two other are bidentate bridging and participating in the
ring system by three atoms of CO2 group only. Each ring is
3.2. Mass spectrometry
Positive-ion electrospray ionization (ESI) mass spectra (MS)
were measured on the LCQ ion trap analyser (Thermo Fisher
Scientific, Waltham, MA, USA) in the range m/z 100e2000. The
samples were dissolved in methanol and analysed by direct infu-
sion at the flow rate 3 ml/min. The ESI ion source spray voltage was
composed
of
(eSneAeSneAeSneBeSneAeSneAeSneBe)
set to 3.5 kV, capillary temperature was 250 ꢃC, capillary voltage
sequence; where A is the core acid, B is the bridging one and Sn is
SnBu3 moiety. This is in strong contrast with the supramolecular
arrangement of triorganotin(IV) carboxylates with a longer chain-
ketopimelic acid [6,7] where only twenty eight-, twenty-
membered rings or monomeric structures were found. The ring
sequence consisted of four alternating terminal and bridging acids
between four organotin moieties for the unit with the largest ring.
This is probably caused by the non-symmetric structure of trans-
glutaconic acid and the restricted rotation around the double bond.
The n-butyl chains are located within the cavities
(17.8 ꢂ 17.8 ꢂ 10.5 Å) determined by the rings in the crystal lattice.
The trans-glutaconic acid is interconnecting two geometrically
different tin atoms as a bridge in a non-symmetrical bidentate
bridging mode (Fig. 2). The mutual separations of C and O atoms
27 V and tube lens offset ꢁ5 V.
3.3. IR spectroscopy
IR spectra were recorded on a Thermo Scientific Nicolet 6700
FT-IR spectrometer in dichloromethane solution (in deuterio-
chloroform for 3a), in KBr pellet or by ATR (Attenuated Total
Reflection) equipment (Diamond/ZnSe, range 4000e640 cmꢁ1) at
laboratory conditions.
3.4. X-ray crystallography
The X-ray data for colorless crystals of 1a were obtained at 150 K
using Oxford Cryostream low-temperature device on a Nonius

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A. Lycka et al. / Journal of Organometallic Chemistry 695 (2010) 2493e2498
2497
Fig. 3. Supramolecular architecture of 1a, PLUTON view, hydrogen atoms as well as disordered groups are omitted for clarity.
KappaCCD diffractometer with Mo K
a graphite monochromator, and the
a
f
radiation (
l
¼ 0.71073 Å),
a positional disorder maybe due to the low mechanical stability
of crystals when removed from mother liqueur. When the
disordered atoms are split into two positions, these disorders
have no influence to the quality of the data and molecular nor
supramolecular structure of 1a. These disorders were treated by
different methods while the best result has been obtained by
using SADI and EADP instructions in SHELXL software package
and data refinements.
and scan mode. Data
c
reductions were performed with DENZO-SMN [9]. The absorption
was corrected by integration methods.[10] Structures were solved
by direct methods (Sir92) [11] and refined by full matrix least-
square based on F2 (SHELXL97) [12]. Hydrogen atoms were mostly
localized on a difference Fourier map, however to ensure unifor-
mity of treatment of crystal, all hydrogen were recalculated into
idealized positions (riding model) and assigned temperature
factors Hiso(H) ¼ 1.2 Ueq(pivot atom) or of 1.5 Ueq for the methyl
moiety with CeH ¼ 0.96 Å, 0.97, and 0.93 Å for methyl, methylene
and the vinyl hydrogen atoms, respectively.
3.5. Synthesis
Crystallographic data for 1a: C29H58O4Sn2, M ¼ 708.13, mono-
3.5.1. (E)-Bis(tributylstannyl) pent-2-enedioate (1a)
clinic, Cc, a ¼ 13.8651(10), b ¼ 15.8783(9), c ¼ 16.4918(6)Å,
The mixture of (E)-pent-2-enedioic acid (130 mg; 1 mmol) and
(Bu3Sn)2O (598 mg; 1 mmol) was refluxed in toluene (25 ml) and
water was removed azeotropically. The residual toluene was
evaporated to give 1a as white crystalline product (646 mg; 91%),
mp: 88e91 ꢃC. The 119Sn, 13C and 1H, NMR data are given in Table 1.
Molecular weight ¼ 708.15. MS: m/z 1443, [2M þ Na]þ, 38%; m/z
1001, [M þ SnBu3]þ, 100%; m/z 733, [M þ Na]þ, 25%; m/z 711,
[M þ H]þ, 4%; m/z 653, [M þ H-butane]þ, 6%; m/z 609,
[M þ H ꢁ butane ꢁ CO2]þ, 5%. IR analysis (nmax, cmꢁ1): CH2Cl2
solution: 2959, 2925, 2872, 2855, 1651, 1617, 1465, 1336, 1076, KBr
pellet: 2957, 2923, 2871, 2856, 1657, 1587, 1551, 1464, 1378, 1078,
976, 742, 673.
b
¼ 107.56(8)ꢃ, Z ¼ 4, V ¼ 3461.4(2) Å3, Dc ¼ 1.359 g cmꢁ3
,
m
¼ 1.470
mm‑1, Tmin ¼ 0.621, Tmax ¼ 0.827; 14,942 reflections measured
(
qmax ¼ 27.5ꢃ), 7056 independent (Rint ¼ 0.0467), 6213 with I > 2
s
(I), 356 parameters, S ¼ 1.116, R1(obs. data) ¼ 0.0378, wR2(all
data) ¼ 0.0788; max, min residual electron density ¼ 0.764,
ꢁ0.524 eÅꢁ3
.
Rint ¼ SjFo2 ꢁ Fo2,meanj/SFo2,
GOF ¼ [S(w(Fo2 ꢁ Fc2)2)/(Ndiffrs ꢁ Npar-
½
ams)] for all data, R(F) ¼ SkFoj ꢁ jFck/SjFoj for observed data, wR
(F2) ¼ [S(w(Fo2 ꢁ F2c)2)/(Sw(Fo2)2)] for all data.
½
In the crystal of 1a there are a couple of disordered atoms
mainly in n-butyl moieties; the dicarboxylic acid chain reveals

ꢀ
A. Lycka et al. / Journal of Organometallic Chemistry 695 (2010) 2493e2498
2498
ATR: 2956, 2922, 2871, 2855, 1657, 1584, 1549, 1463, 1377, 1077,
976, 742, 670. Elemental analysis found: C, 49.5%; H, 8.1%. Calcu-
lated: C, 49.19%; H, 8.26%.
2 mmol) was added and the mixture was stirred at laboratory
temperature for 1 h. Methanol was removed by evaporation in vacuo
at laboratory temperature and sodium chloride was extracted twice
with water to give 3b as yellowish solid (660 mg; 78%), mp: >300 ꢃC.
The 119Sn, 13C and 1H, NMR data are given in Table 1. Molecular
weight ¼ 844.09. MS: m/z 747, [SnPh3OCHO þ SnPh3]þ, 47%; m/z 383,
3.5.2. (E)-Bis(triphenylstannyl) pent-2-enedioate (1b)
The mixture of (E)-pent-2-enedioic acid (130 mg; 1 mmol) and
Ph3SnOH (736 mg; 2 mmol) was refluxed in toluene (25 ml) and
water was removed azeotropically. The residual toluene was evapo-
rated to give 1b as a white crystalline product (714 mg; 86%), mp:
156e9 ꢃC. The 119Sn, 13C and 1H, NMR data are given in Table 1.
Molecular weight ¼ 828.09. MS: m/z 1683, [2M þ Na]þ,11%; m/z 1181,
[M þ SnPh3]þ, 12%; m/z 853, [M þ Na]þ, 16%; m/z 831, [M þ H]þ, 4%;
m/z 747, [SnPh3OCHO þ SnPh3]þ, 50%; m/z 383, [SnPh3OCH3 þ H]þ,
100% m/z 351, [SnPh3]þ, 43%. IR analysis (nmax, cmꢁ1): CH2Cl2 solu-
tion: 1652, 1482, 1335, 1077, 1023, 997, 985, 449, KBr pellet: 3066,
3047,1658,1574,1547,1481,1430,1350,1076,1023, 997, 984, 729, 697,
452, ATR: 3066, 3047, 1660, 1574, 1545, 1481, 1429, 1347, 1076, 1023,
997, 983, 729, 696. Elemental analysis found: C, 59.2%; H, 4.4%.
Calculated: C, 59.47%; H, 4.14%.
[SnPh3OCH3 þ H]þ, 100%; m/z 351, [SnPh3]þ, 49%. IR analysis (nmax
,
cmꢁ1): KBr pellet: 3616, 3064, 3045, 1722, 1636, 1579, 1480, 1428,
1380,1078, 1022, 997, 896, 775, 723, 694, 447, ATR: 3617, 3064, 3045,
1722, 1579, 1480, 1428, 1381, 1078, 1022, 997, 895, 774, 723, 694.
Elemental analysis found: C, 57.9%; H, 3.7%. Calculated: C, 58.34%; H,
4.06%.
Acknowledgement
The authors thank the Czech Science Foundation (grant No. 203/
07/0469) for financial support.
Appendix A. Supplementary material
3.5.3. Reaction of dibutyltin oxide with (E)-pent-2-enedioic acid
(2a)
CCDC 765425 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
The mixture of (E)-pent-2-enedioic acid (260 mg; 2 mmol) and
dibutyltin oxide (500 mg; 2 mmol) was refluxed in toluene (25 ml)
and water was removed azeotropically. The residual toluene was
evaporated to give 2a as white solid product (650 mg; 90%), mp:
216e9 ꢃC. The 119Sn, 13C and 1H, NMR data are given in Table 1. IR
analysis (nmax, cmꢁ1): CH2Cl2 solution: 2961, 2929, 2873, 2860,
1660, 1606, 1583, 1465, 1370, KBr pellet: 2958, 2927, 2872, 2858,
1657, 1602, 1572, 1464, 1378, 1287, 1211, 1083, 779, 687, 613, ATR:
2955, 2923, 2871, 2858, 1657, 1600, 1565, 1462, 1378, 1286, 1209,
1089, 780, 688. Elemental analysis found: C, 45.1%; H, 6.7%. Calcu-
lated: C, 44.84%; H, 6.45%.
References
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To the mixture of (E)-pent-2-enedioic acid (260 mg; 2 mmol),
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(688 mg; 2 mmol) was added and heated for 20 min. The solvent
was evaporated and sodium chloride was extracted twice with
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1076, 1023, 998, 985, 730, 695, 449, ATR: 3049, 1653, 1557, 1481,
1431, 1390, 1076, 1023, 998, 984, 730, 695. Elemental analysis
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119Sn, 13C and 1H, NMR data are given in Table 2. IR analysis (nmax
,
cmꢁ1): CDCl3 solution: 3631, 2960, 2925, 2873, 2855, 1724, 1652,
1465, 1340, 1292, 1076, 1017, 606, 524.
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3.5.6. Bis(triphenyltin) 3-oxopentanedioate (3b)
The mixture of 3-oxopentanedioic acid (146 mg; 1 mmol) 1 M
sodium methylate (2 mmol) and methanol (20 ml), Ph3SnCl (722 mg;
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