Ambient temperature Sn-C bond cleavage reaction involving the Sn-n-butyl group. weak f···f interactions in the solid state structure of [{nBu2SnO2C-C6H4-4-CF 3}2O]2

Article abstract of DOI:10.1002/zaac.201300620

The reaction of bis(tri-n-butyltin)oxide, [nBu₃Sn]₂O, with HO₂C-C₆H₄-4-CF₃ (R _fTol-CO₂H) affords a coordination polymer [nBu ₃SnO₂C-R_fTol]_n (1). 1 undergoes hydrolysis in the presence of atmospheric moisture, at room temperature, resulting in the formation of the diorgano stannoxane [{nBu₂SnO ₂C-R_fTol}₂O]₂ (2). The transformation of 1 to 2 is accompanied by a Sn-C bond cleavage reaction. Formation of 2 also occurs in a direct reaction, involving [nBu ₃Sn]₂O and R_fTol-CO₂H in the presence of water. 2 can also be prepared in a 1:1 reaction of di-n-butyltin oxide, [nBu₂SnO]_n with R_fTol-CO₂H. The conversion of 2 from 1 was monitored by ¹¹⁹Sn NMR spectroscopy over a period of eight days. The molecular structure of 2 reveals a tetranuclear assembly consisting of two pairs of structurally distinct six-coordinate tin atoms. Extensive hydrogen-bonding interactions (C-H···O, C-H···F) and weak F···F interactions involving organo-fluorine atoms in the crystal structure result in the formation of a three-dimensional supramolecular architecture for 2. Copyright

Full text of DOI:10.1002/zaac.201300620

Job/Unit: Z13620
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Date: 11-02-14 14:51:38
Pages: 6
ARTICLE
DOI: 10.1002/zaac.201300620
Ambient Temperature Sn–C Bond Cleavage Reaction Involving the Sn-n-
butyl Group. Weak F···F Interactions in the Solid State Structure of
[{nBu2SnO2C–C6H4-4-CF3}2O]2
Kandasamy Gopal,[a] Subrata Kundu,[b] Ramesh K. Metre,[b] and
Vadapalli Chandrasekhar*[b,c]
Dedicated to Professor C. N. R. Rao on the Occasion of His 80th Birthday
Keywords: F···F Interactions; Tin; Cleavage reaction; Organostannoxanes
Abstract. The reaction of bis(tri-n-butyltin)oxide, [nBu3Sn]2O, with 1:1 reaction of di-n-butyltin oxide, [nBu2SnO]n with RfTol–CO2H. The
HO2C–C6H4–4-CF3 (RfTol-CO2H) affords a coordination polymer
[nBu3SnO2C–RfTol]n (1). 1 undergoes hydrolysis in the presence of
conversion of 2 from 1 was monitored by 119Sn NMR spectroscopy
over a period of eight days. The molecular structure of 2 reveals a
atmospheric moisture, at room temperature, resulting in the formation tetranuclear assembly consisting of two pairs of structurally distinct
of the diorgano stannoxane [{nBu2SnO2C–RfTol}2O]2 (2). The trans-
formation of 1 to 2 is accompanied by a Sn–C bond cleavage reaction.
Formation of 2 also occurs in a direct reaction, involving [nBu3Sn]2O
six-coordinate tin atoms. Extensive hydrogen-bonding interactions
(C-H···O, C-H···F) and weak F···F interactions involving organo-fluor-
ine atoms in the crystal structure result in the formation of a three-
and RfTol–CO2H in the presence of water. 2 can also be prepared in a dimensional supramolecular architecture for 2.
Sn-benzyl[6b] or Sn-allyl[6c] motifs, there have been reports,
Introduction
admittedly sparse, on such reactions in compounds containing
Sn–Ph[6d] and even Sn–butyl[6e] motifs. Thus, recently, we
have utilized such Sn–C bond cleavage reactions for the syn-
thesis of novel organostannoxanes. These include a tetranu-
clear cage,[7] [Sn2(μ-OH)2] cored diorganotin derivative,[6e]
and a hydrated organotin cation.[8] One interesting example
involves a Sn–Ph scission in the reaction of [Ph3Sn]2O with
perfluoromesityl carboxylic acid, HO2C–C6H2-2,4,6-(CF3)3
(RfMes–CO2H) leading to the formation of a distannoxane,
[Ph2Sn(μ-OH)O2C–RfMes]2 instead of the expected product
Ph3SnO2C–RfMes.[6c] The reason for the facile Sn–C bond
cleavage in the above reaction has been suggested as due to
the steric and electronic withdrawing character of the perfluo-
romesityl carboxylate group.
In order to test the generality of this approach (Sn–C bond
cleavage approach), we have utilized perfluoro-p-tolyl carbox-
ylic acid, HO2C–C6H4-4-CF3 (RfTol–CO2H) which is steri-
cally less encumbered than RfMes–CO2H and contains only
one strong electron withdrawing group (–CF3). Accordingly,
herein we report the reaction of bis(tri-n-butyltin)oxide,
(nBu3Sn)2O with HO2C–C6H4-4-CF3 (RfTol–CO2H) which af-
fords the expected tri-n-butyltin carboxylate coordination poly-
mer [nBu3SnO2C–RfTol]n (1). The influence of the –CF3
group, however, is manifested in a facile ambient temperature
hydrolysis of 1, involving the Sn–C bond cleavage of the Sn-
n-butyl substituent, leading to the formation of [{nBu2SnO2C–
RfTol}2O]2 (2). We could prepare 2, in a direct Sn–C bond
cleavage reaction from [nBu3Sn]2O as well as in a normal re-
Organostannoxanes are a family of structurally interesting
organometallic compounds.[1] The remarkable structural vari-
ability of these compounds has been manifested in several
structural forms: ladder, cube, drum, butterfly cluster, O-
capped cluster, double O-capped cluster, trigonal prism, foot-
ball cage.[2] Also, organostannoxanes are known in both mo-
lecular forms and coordination polymers.[3] Further, the nu-
clearity of tin can traverse from one to twelve in these various
compounds.[4] The synthesis of organostannoxanes, usually
involves the reactions of organotin halides, organotin oxides,
-hydroxides, or -oxide-hydroxides with protic acids.[5] In ad-
dition to these well-established synthetic procedures, the la-
bility of the Sn–C bond, in certain situations, has also been
utilized for preparing new organostannoxanes.[6] Although,
Sn–C bond cleavage is most facile in compounds containing
* Dr. V. Chandrasekhar
E-Mail: vc@iitk.ac.in
[a] Department of Chemistry
Central University of Rajasthan
Kishangarh, Rajasthan – 305802, India
[b] Department of Chemistry
Indian Institute of Technology Kanpur
Kanpur – 208016, India
[c] Tata Institute of Fundamental Research
Centre for Interdisciplinary Sciences
21, Brundavan Colony
Narsingi, Hyderabad – 500075, India
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201300620 or from the au-
thor.
Z. Anorg. Allg. Chem. 0000, ᭿,(᭿), 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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K. Gopal, S. Kundu, R. K. Metre, V. Chandrasekhar
ARTICLE
action involving [nBu2SnO]n. On the other hand, from several perimental Section). We also performed a 1:1 reaction of the
diorganotin oxide, (nBu2SnO)n with RfTol–CO2H. This reac-
tion also affords 2 in nearly quantitative yields (see Experi-
mental Section). Compound 2 shows two resonances at δ =
–254 and –272 ppm in its 119Sn NMR spectrum indicating the
presence of two types of tin atoms in its molecular structure.
These values are comparable to the literature precedents.[4c]
The 19F NMR spectrum of both 1 and 2 show singlets that
resonate at δ = –69 and –67 ppm, respectively.
interactions involving halogen atoms, those containing fluor-
ine, the F···F and C–H···F interactions, are attracting attention
recently due to several reasons including their role in the me-
dicinal chemistry.[6d,9]
The crystal structure of 2 reveals, that due to rich intermo-
lecular C–H···O, C–H···F and weak F···F interactions, a 3D-
supramolecular architecture is realized in the solid-state. These
results are discussed herein.
The hydrolysis of 1 was monitored by using 119Sn NMR
spectroscopy at various time intervals. Thus, compound 1
shows a single resonance at δ = 63 ppm (Figure 1a). After two
days, a new signal appears at δ = –271 ppm indicating the
onset of hydrolysis and increase of the coordination number
around tin (Figure 1b). After five days, three new signals (δ =
–201, –262, and –269 ppm) appeared along with the one at δ =
–271 ppm observed previously, (Figure 1c). Finally, after eight
days two signals, corresponding to 2 were observed at δ =
–254 and δ = –272 ppm indicating the complete conversion of
1 to 2 (Figure 1d). At this point we are unable to offer a de-
tailed mechanism regarding this conversion except to note that
the reaction appears to be more facile in an open atmosphere,
in light. In dark, the reaction appears to be very sluggish.
Results and Discussion
Synthetic Aspects
The reaction of [nBu3Sn]2O with two equivalents of RfTol–
CO2H in toluene leads to the formation of mononuclear trior-
ganotin carboxylate 1 (Scheme 1) which is a viscous oil. Based
on the molecular structures of this family of compounds[3b] we
presume that it should possess a polymeric structure. However,
this could not be confirmed since attempts to crystallize it af-
forded, through a Sn–C bond cleavage reaction, 2 (see below).
The 119Sn NMR spectrum of 1 shows a single resonance at δ
= 63 ppm. It is known that triorganotin carboxylates that are
coordination polymers in the solid-state break down in solu-
tion, typically into their monomeric form.
Scheme 1. Synthesis of the organostannoxanes 1 and 2.
Efforts to crystallize 1 resulted in the formation of 2. The
conditions for this were optimized and block shaped crystals
of 2 were isolated when neat 1 in the form of a viscous oil was
kept undisturbed in open air for 8 days. Since the formation of
2 involves a Sn–C bond cleavage and hydrolysis, we reacted
[nBu3Sn]2O and RfTol–CO2H in the presence of water in a
mixture of solvents (1:2 toluene and acetonitrile) at room tem-
perature for 3 days (Scheme 1). Interestingly, this direct reac-
tion, which involves a facile ambient temperature Sn–butyl
Figure 1. Monitoring the conversion of 1 to 2 by 119Sn NMR spec-
troscopy. (a) Compound 1. (b) After 2 days. (c) After 5 days. (d) After
8 days. Note that the chemical shifts at this stage exactly match that
of 2.
Molecular and Supramolecular Structures
The molecular structure of compound 2 is shown in Figure 2
bond cleavage reaction, afforded 2 in very good yield (see Ex- and its selected bond parameters are summarized in the caption
2
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F···F Interactions in [{nBu2SnO2C–C6H4-4-CF3}2O]2
Figure 2. Molecular structure of 2. The unlabeled atoms are symmetry
related to the labeled atoms. Selected bond parameters are as follows:
Sn1–O1 2.051(2), Sn1–O1* 2.142(2), Sn1–O2 2.290(2), Sn1–O4*
2.815(3), Sn1–C25 2.122(4), Sn1–C29 2.126(4), Sn2–O1 2.048(2),
Sn2–O3 2.312(3), Sn2–O4 2.196(2), Sn2–O5 2.818(7), Sn2–C21
2.123(4), Sn2–C17 2.130(4) Å; C25–Sn1–C29 143.55(15), O2–Sn1–
O1* 162.91(9), O1–Sn1–O4* 140.38(8), C21–Sn2–C17 139.31(14),
O3–Sn2–O4 166.15(9), O1–Sn2–O5 129.35(3)°.
of this figure. The molecular structure of 2 shows that four
carboxylate ligands present in this compound are supported by
a planar [Sn4O2] core and adopt the familiar ladder framework
with two central (Sn1 and Sn1*) and two terminal tin atoms
(Sn2 and Sn2*). The Sn–O distances in the central [Sn2O2]
core [Sn1–O1 2.051(2) and Sn1–O1* 2.142(2) Å] are compar-
able with literature precedents.[2b,3d] All the tin atoms are pres-
ent in a distorted trigonal bipyramidal arrangement (2C, 3O).
Also, an additional carboxylate oxygen (O5 with terminal tin
atom Sn2 and O4* with central tin atom Sn1) is involved in a
sixth weaker bonding interaction [Sn2–O5 2.818(7) Å and
Figure 3. (a) View showing the two-dimensional staircase like net-
work. One fluorine atom of the CF3 group is omitted for clarity. (b)
Three-dimensional supramolecular network formed by C–H···O, C–
H···F, and weak F···F interactions in 2.
Sn1–O4* 2.815(3) Å] with a tin atom along its trigonal bipy- two-proton donor type of C–H···O bonding interactions along
ramidal face (Figure 2). Considering that the sum of the van with two types of F···F interactions to form a linear one-dimen-
der Waals radii of tin and oxygen is 3.7 Å[10] the coordination sional tape (Figure 3a). In this interaction, a proton (H15) on
arrangement around the tin atoms (Sn1 and Sn2) can be as- the RfTol–CO2 moiety is intermolecularly hydrogen-bonded
sumed to be distorted octahedral. The carboxylate ligands are with the carboxylate oxygen (O3) of the central RfTol–CO2
involved in both anisobidentate chelating (Sn2–O4 and Sn2– ligand [H15···O3 2.683(7) Å, 167.73(22)°, symmetry code: 2–
O5) as well as isobidentate bridging (Sn1–O2 and Sn2–O3) x, 1–y, 1–z]. Similarly, two of the fluorine atoms (F2 and F3)
coordination modes. The carboxylate groups in 2 are nearly in present in the terminal RfTol–CO2 ligands interact very weakly
the same plane as that of the aromatic ring (with a deviation with two other fluorine atoms (F6 and F5) present in the cen-
of 9.7° for terminal chelating RfTol–CO2 and 29.2° for central tral RfTol–CO2 ligands in the form of CF2 dimer [F2···F6
bridging RfTol–CO2) and are comparable with our previous 3.016(11) Å, symmetry code: 2–x, 1–y, 1–z; F3···F5
observations.[3d]
3.277(11) Å, symmetry code. 2–x, 1–y, 1–z]. At the second-
There is a great interest in the assembly of ordered supra- level, two such one-dimensional networks are interconnected
molecular structures through crystal engineering because of the by means of H···F interactions to form a staircase like two-
potential for realizing new types of functional solids.[11] Many dimensional supramolecular network (Figure 3a). Here, one of
types of secondary interactions are known to mediate supra- the protons (H7) on the central RfTol–CO2 ligand is hydrogen
molecular assembly formation in organic and inorganic com- bonded with two fluorine atoms (F2 and F6) of two different
pounds. These include O–H···O, N–H···O, and N–H···N (strong ladder molecules in a bifurcated manner [H7···F2 2.822(8) Å,
interactions); C–H···O, C–H···π, π···π, C–H···X and X···X (X = 134.14(29)°, symmetry code: x, y, –1+z; H7···F6 2.797(6) Å,
halogen) interactions (weak interactions) etc.[11] Since 2 con- 132.19(27)°, symmetry code: 2–x, 1–y, z]. Finally, these stair-
tain many fluorine atoms in the periphery we examined its case like two-dimensional networks are interconnected by
solid-state crystal structure in greater detail. The supramolec- other F···F interactions to afford a three-dimensional supra-
ular organization in this compound may be considered in a molecular assembly (Figure 3b). The bonding parameter for
step-wise manner. At the first-level, each molecule interacts this interaction is: F1···F1 3.065(9) and its symmetry code is
with two other neighbors by means of two-proton acceptor and 3–x, –y, 2–z.
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K. Gopal, S. Kundu, R. K. Metre, V. Chandrasekhar
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Dean-Stark apparatus. The reaction mixture was filtered, the filtrate
stripped of the solvent and the residue obtained was identified and
characterized as 2. Yield: 0.80 g (93.1%).
Summary
We have observed an interesting and rare ambient tempera-
ture Sn–C bond cleavage involving the crystallization of the
triorganotin carboxylate, [nBu3SnO2C–RfTol]n (1) affording
[{nBu2SnO2C–RfTol}2O]2 (2). 2 could also be prepared in two
direct reactions: one, involving the reaction of (nBu3Sn)2O
with RfTol–CO2H in presence of water and another involving
the reaction of (nBu2SnO)n with RfTol–CO2H. The conversion
of 1 into 2 could be monitored by 119Sn NMR; the conversion
M.p.: 155 °C. C64H88O10F12Sn4: calcd. C 44.69; H 5.16%; found: C,
1
44.41; H, 5.30%. H NMR (ppm): δ = 0.81 (t, J = 7.31 Hz, 24 H, n-
butyl CH3), 1.35–1.66 (m, 48 H, n-butyl CH2’s), 7.81 (m, 16 H, aro-
matic CH). 19F NMR (ppm): δ = –67 (s). 119Sn NMR (ppm): δ = –254
(s), –272 (s). Colorless crystals were obtained from slow diffusion of
diethyl ether into the dichloromethane solution of 2.
is slow, takes 8 days, but is quantitative. The crystal structure X-ray Crystallography: Suitable crystals for single-crystal X-ray dif-
fractions were loaded with a Bruker AXS Smart Apex CCD dif-
fractometer. SMART software package (version 5.628) was used for
collecting data frames, SAINT software package (version 6.45) for
integration of the intensity and scaling and SADABS was used for
absorption correction. The structure was solved and refined by full-
matrix least-squares on F2 using SHELXTL software package.[12]
Non-hydrogen atoms were refined with anisotropic displacement pa-
rameters. All the hydrogen atoms with occupancy Ͼ 0.5 were included
in idealized positions and their positions were refined isotropically by
a riding model. Figure 2 and Figure 3 and its bonding parameters were
obtained from DIAMOND 3.1 software package.[13]
of 2 reveals the presence of an interesting 3D supramolecular
structure formed as a result of intermolecular C–H···O, C–
H···F, and weak F···F interactions.
Experimental Section
Reagents and General Procedures: Solvents and other general rea-
gents used in this work were purified according to standard procedures.
The following chemicals were purchased and used as such without
further purification: (nBu3Sn)2O, [nBu2SnO]n, RfTol–CO2H (all from
Aldrich, USA).
Crystallographic data (excluding structure factors) for the structure in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.
Copies of the data can be obtained free of charge on quoting the de-
pository number CCDC-974962 (Fax: +44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
Instrumentation: Melting points were recorded using a JSGW melt-
ing point apparatus and are uncorrected. Elemental analyses were car-
ried out with a Thermoquest CE instruments model EA/110 CHNS-O
1
elemental analyzer. H, 19F and 119Sn NMR spectra were recorded in
CDCl3 solutions with a JEOL JNM Lambda spectrometer operating
at 400.0, 376.0, and 150.0 MHz respectively. The chemical shifts are
1
referenced with respect to tetramethylsilane (for H), CFCl3 (for 19F)
Crystallographic Data for 2 : Empirical formula C64H88O10F12Sn4;
Size 0.2ϫ0.2ϫ0.1 mm3; Mw
¯
= 1720.10 g; triclinic; P1; a =
and tetramethyltin (for 119Sn). All the 119Sn NMR spectra were re-
corded under broadband decoupled conditions.
11.083(5) Å; b = 11.871(5) Å; c = 14.229(5) Å; α = 84.706(5)°; β =
80.842(5)°; γ = 69.376(5)°; V = 1728.4(12) Å3; Z = 2; T = 153(2) K;
θ range: 4.13 to 25.02°; 9119 reflections collected, 5997 independent
reflections (Rint = 0.0193); R1 = 0.0332, wR2 = 0.0751 [for I Ͼ 2σ(I)];
R1 = 0.0395, wR2 = 0.0779 (for all data); GOF = 1.030; maximum and
minimum electron densities = 1.191 and –0.662 e·Å–3 respectively.
[nBu3SnO2C–RfTol]n (1):
A mixture of [nBu3Sn]2O (0.36 g,
0.60 mmol) and RfTol–CO2H (0.23 g, 1.20 mmol) in toluene (60 mL)
was heated under reflux for 6 h. The water formed in the reaction was
removed by using a Dean-Stark apparatus. The reaction mixture was
filtered and evaporated to afford the corresponding product as viscous
oil. Yield: 0.56 g (96.6%). C20H31O2F3Sn: calcd. C 50.13, H 6.52%;
Supporting Information (see footnote on the first page of this article):
Crystallographic Information File (CIF) and bond lengths, bond angles
table for compound 2. This materials are available free of charge via
the Internet at http://pubs.acs.org.
1
found: C 49.79, H 6.18%. H NMR (ppm): δ = 0.75 (t, J = 7.21 Hz,
9 H, n-butyl CH3), 1.21–1.69 (m, 18 H, n-butyl CH2), 7.65 (br., 2 H,
aromatic CH), 8.09 (br., 2 H, aromatic CH). 19F NMR (ppm): δ = –69
(s). 119Sn NMR (ppm): δ = +63 (s).
Acknowledgements
[{nBu2SnO2C–RfTol}2O]2 (2): Three synthetic procedures were uti-
lized for the preparation of 2.
We thank the Department of Science and Technology, India and the
Council of Scientific and Industrial Research, India for financial sup-
port. V. C. is thankful to the Department of Science and Technology
for a J. C. Bose fellowship. S. K. thanks CSIR, India, and R. K. M
thanks UGC, India for a Senior Research Fellowship.
Method A: Colorless block shaped crystals were obtained from 1
(0.56 g, 1.17 mmol) (viscous oil) when kept undisturbed in open air
for a period of 8 d and are identified as 2 by single-crystal X-ray
analysis. Yield: 0.21 g (40.7%, isolated crystals).
Method B: A mixture of [nBu3Sn]2O (0.72 g, 1.2 mmol) and RfTol–
CO2H (0.46 g, 2.4 mmol) was taken in a mixture of solvents toluene References
(20 mL) and acetonitrile (40 mL). To the mixture was added H2O
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CO2H (0.38 g, 2.0 mmol) in toluene (60 mL) was heated under reflux
for 6 h. The water formed in the reaction was removed by using a
4
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F···F Interactions in [{nBu2SnO2C–C6H4-4-CF3}2O]2
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Received: December 5, 2013
Published Online: ᭿
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Job/Unit: Z13620
/KAP1
Date: 11-02-14 14:51:38
Pages: 6
K. Gopal, S. Kundu, R. K. Metre, V. Chandrasekhar
ARTICLE
K. Gopal, S. Kundu, R. K. Metre, V. Chandrasekhar* .... 1–6
Ambient Temperature Sn–C Bond Cleavage Reaction Involv-
ing the Sn-n-butyl Group. Weak F···F Interactions in the Solid
State Structure of [{nBu2SnO2C–C6H4-4-CF3}2O]2
6
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Z. Anorg. Allg. Chem. 0000, 0–0