Upload
ramesh-k
View
216
Download
3
Embed Size (px)
Citation preview
Subscriber access provided by HAIFA UNIV
Crystal Growth & Design is published by the American Chemical Society. 1155Sixteenth Street N.W., Washington, DC 20036Published by American Chemical Society. Copyright © American Chemical Society.However, no copyright claim is made to original U.S. Government works, or worksproduced by employees of any Commonwealth realm Crown government in the courseof their duties.
Article
Reactions of (E)-5-(pyridin-4-yl-methyleneamino)isophthalicacid (LH2) with Triorganotin Oxides and –Chloride.
Formation of 1D- and 2D-Coordination PolymersVadapalli Chandrasekhar, Chandrajeet Mohapatra, and Ramesh Metre
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg401201w • Publication Date (Web): 29 Aug 2013
Downloaded from http://pubs.acs.org on September 2, 2013
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are postedonline prior to technical editing, formatting for publication and author proofing. The American ChemicalSociety provides “Just Accepted” as a free service to the research community to expedite thedissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscriptsappear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have beenfully peer reviewed, but should not be considered the official version of record. They are accessible to allreaders and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offeredto authors. Therefore, the “Just Accepted” Web site may not include all articles that will be publishedin the journal. After a manuscript is technically edited and formatted, it will be removed from the “JustAccepted” Web site and published as an ASAP article. Note that technical editing may introduce minorchanges to the manuscript text and/or graphics which could affect content, and all legal disclaimersand ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errorsor consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Reactions of (E)-5-(pyridin-4-yl-methyleneamino)isophthalic
acid (LH2) with Triorganotin Oxides and –Chloride.
Formation of 1D- and 2D-Coordination Polymers
Vadapalli Chandrasekhar,*a,b Chandrajeet Mohapatraa and Ramesh K. Metrea aDepartment of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India
bTata Institute of Fundamental Research, Centre for Interdisciplinary Sciences, 21, Brundavan
Colony, Narsingi, Hyderabad- 500075,India
*E-mail: [email protected];[email protected]; Phone: (+91) 512-259-7259. Fax: (+91) 521-259-0007/7436.
Page 1 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
Abstract: The reaction of (n-Bu3Sn)2O with (E)-5-(pyridin-4-yl-methyleneamino)isophthalic
acid (LH2) in a stoichiometric ratio of 1:1 resulted in the formation of a 2D coordination polymer
[(n-Bu3Sn)2(µ-L)]n (1). The structure of 1 contains a 36-membered macrocycle as its repeating
building block. The reactions of Me3SnCl or (Ph3Sn)2O with LH2, on the other hand, result in the
generation of [(Me3Sn)2(µ-L)(H2O)]n (a neutral 1D coordination polymer) (2) and [(Ph3Sn)(µ-
L)(Et3NH)]n (an anionic 1D coordination polymer) (3) respectively. Compounds 1-3 show a rich
supramolecular architecture in their solid-state as a result of multiple secondary interactions.
Introduction
Apart from their utility in various areas including catalysis, organotin compounds, in general,
and organooxotin compounds in particular are of considerable interest because they display a
rich structural diversity.1 Many interesting types of organoxotin compounds, possessing novel
structural features, have been discovered in the reactions of organotin oxides, -hydroxides and
oxide-hydroxides with protic acids (carboxylic acids, phosphinic acids, phosphonic acids and
sulfonic acids).2-4 Another reason of interest among this family of compounds is the realization
that the organostannoxane core can be used as an inert scaffold to support a functional
periphery.5 In light of the recent surge of research activity in metal-organic frameworks6 there
have also been attempts to delineate the reaction products involving appropriate organotin
substrates and dicarboxylic acids.7 However, this field is still sparsely investigated. Recent work
from some research groups7(a)-(f) and ours7(g)-(n) have thrown open the exciting possibilities that
exist in these systems. Thus, for example, Höpfl and co-workers have reported the isolation of
novel macrocycles and coordination polymers in the reactions of diorganotin compounds with
aromatic dicarboxylic acids.7(c) From our research group we have explored the reactions of
organotin compounds with pyrazole dicarboxylic acids as well as pyridine dicarboxylic acids and
Page 2 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
have shown the formation of novel macrocycles and coordination polymers (Chart 1). More
recently we have also reported selective gas adsorption (H2 and CO2 over N2) property of a 4-
connected 3-fold interpenetrated triorganotin coordination polymer with a sqc-topology. This
coordination polymer involved the use of an imidazole-4,5-dicarboxylic acid as the reactant.7(m)
Many of the above studies involved diorganotin precursors and dicarboxylic acids. We have felt
that a better understanding can be achieved if the reactions involving triorganotin compounds
with dicarboxylic acids are studied, since the complexities would be much less in this system.
Accordingly, we have investigated the reactions of (n-Bu3Sn)2O, Me3SnCl and (Ph3Sn)2O with
(E)-5-(pyridin-4-yl-methyleneamino)isophthalic acid (LH2) and the products obtained viz., [(n-
Bu3Sn)2(µ-L)]n (1), [(Me3Sn)2(µ-L)(H2O)]n (2) and [(Ph3Sn)(µ-L)(Et3NH)]n (3) were
characterized as coordination polymers.
Chart 1. (a) The repeating unit of [(Bz2Sn)6(L)4(µ-OH)2(Bz2SnCl)2]n 7(k) (b) Schematic figure of
[{n-Bu2Sn(2,5-pdc)(H2O)}3] 7(c) (c) Macrocyclic repeating unit of [(n-Bu3Sn)2(n-Bu2Sn)2(µ-
L1)2(µ-OH)2]n 7(l) (d), (e) and (f) Macrocyclic repeating units of [(n-Bu3Sn)4(µ-L3)2]n
7(l).
Page 3 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
Results and Discussion
The reaction of LH2 with various triorganotin precursors (n-Bu3Sn)2O, Me3SnCl and (Ph3Sn)2O
afforded compounds 1-3 (Scheme 1; see also experimental section). 1 is a 2D-coordination
polymer built by the fusion of 36-membered macrocycle repeat units. 2 and 3 are 1D-
coordination polymers. While 2 is a neutral coordination polymer, 3 is anionic and contains
triethylammonium counter cations. Compounds 1−3 do not retain their structural integrity in
solution as evidenced by electrospray ionization mass spectrometry (ESI-MS) (see experimental
Section).
Scheme 1
N
N
OH
O
HO
O
LH2
Me3SnCl
Et3N
(Ph3Sn)2O
Et3N
(n-Bu3Sn)2O
N
N
OO
O
O
Sn
Sn
Sn
Sn
nBu
nBunBu
nBu
nBunBu
N
O
n1
N
N
OO
O
O
Sn
Sn
Me
Me
Me
Me
Me
Me
OH2
N Snn
2
N
N
O
O
O
O
Sn
Ph
NH
Ph
Ph
Sn Sn
n
3
Page 4 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
X-ray Crystal Structure of 1
The X-ray crystal structure of 1 is depicted in Figure 1a. Selected metric parameters of 1
are summarized in Table 2. Compound 1 is a 2D coordination polymer owing to the 4.11101
coordination mode of the ligand (Chart 2a). Each ligand binds to four tin atoms which includes a
bidentate coordination of one carboxylate group and a monodentate coordination of another
carboxylate group along with coordination from the pyridine nitrogen (Figure 1b). Two
different types of tin centers are present in 1. Both of these (Sn1 and Sn2) are 5-coordinated in a
distorted trigonal bipyramidal geometry. In Sn1 both the axial positions are occupied by oxygen
atoms [O1 and O3; Sn1-O1, 2.099(5)Å; Sn1-O3, 2.474(4)Å] (see Supporting Information). On
the other hand the axial positions around Sn2 are occupied by an oxygen and a nitrogen atom
[O4 and N2; Sn2-O4, 2.181(4); Sn2-N2, 2.509(5) Å] (see Supporting Information). The 2D
coordination polymer of 1 contains inter-connected 36-membered tetranuclear macrocyclic rings
(Figure 1c). In spite of its large size, the 36-membered macrocylic ring is nearly planar. The
mean plane information for the macrocylic ring is summarized in Supporting Information. The
packing organization reveals that the 2D sheets are arranged parallel to each other with a slight
offset in an AB type arrangement (Figure 1d). Intermolecular C-H--π interactions serve as the
glue between the stacked sheets. The inter layer distance is approximately ~15 Å [A--A
distance]. It is interesting to compare the structure of 1 with some literature precedents. Thus, we
have reported previously a 2D-coordination polymer consisting of a tetranuclear macrocycle
(Sn4O6C2) (Chart 1a).7(k) A coordination polymer containing a trinuclear macrocycle
(Sn3O3N3C9) was reported by Höpfl and co-workers in the reactions of diorganotin compounds
with pyridine-2,5-dicarboxylic acid (Chart 1b).7(c) The orientation of the coordination sites of the
ligand LH2, used in the present study, are comparable with pyridine-3,5-dicarboxylic acid (Chart
Page 5 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
2b). We have also reported, recently an organotin-based 2D coordination polymer, by using
pyridine-3,5-dicarboxylic acid. This compound was shown to contain three types of organotin
macrocycles [28-membered (Sn4O6C16N2)], [20-membered (Sn4O6C8N2)] and [24-membered
(Sn4O6N2C12)] (Charts 1d-1f). 7(l) However, in spite of the fact that in the latter as well in the
present instance the ligand is involved in a 4.11101 coordination (Chart 2a) compound 1 contains
only one type of organotin macrocycle (Sn4O6N4C22) as discussed above.
(a) (b)
Chart 2. (a) Coordination modes of ligand LH2 in compounds 1-3 (Harris notation used as per
reference 8) (b) Schematic representation showing the similarity between pyridine-3,5-
dicarboxylic acid and LH2.
N
N
O
O
O
O
N
N
O
O
O
O
N
N
O
O
O
O
M
MM
M M
MM
4.11101 3.10101 2.01010
1 2 3
MM
N
OHHO
O O
N
OHHO
O O
N
Page 6 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
(a)
(b) (c)
(d)
Page 7 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
Figure 1. (a) 2D polymeric structure of compound 1 (b) Coordination mode of ligand (c) An
isolated 36-membered macrocycle (d) AB packing of 2D parallel sheets (butyl groups have been
omiited from Figures 1c and 1d)
X-ray Crystal structure of 2
The X-ray crystal structure of 2 is shown in Figure 2a. Selected metric parameters of this
compound are summarized in Table 2. Compound 2 is a 1D coordination polymer formed as a
result of the 3.10101 coordination mode of the ligand LH2 (Chart 2a). In 2, the ligand binds to
three tin centers; both the carboxylate groups are monodentate along with the pyridine nitrogen
atom (Figure 2b). The growth of the coordination polymer is arrested at the Sn2 centre as a result
of coordination by a terminal water molecule. Consequently, 2 forms a 1D coordination polymer.
Similar to 1, in this instance also the two tin centers (Sn1 and Sn2) are five-coordinate in a
distorted tbp coordination geometry (Supporting Information). While the Sn1 centre contains an
oxygen (O1) and a nitrogen (N1) in its axial sites [Sn1-O1, 2.165(4)Å; Sn1-N1, 2.532 (4)Å; O1-
Sn1-N1 175.22(15)°] the Sn2 centre contains two oxygen atoms (O3 and O5) in its axial sites
[Sn2-O3, 2.175(4) Å; Sn2-O5, 2.434(5) Å; O3-Sn2-O5, 171.7 (2)°]. The terminal H2O (O5) is
involved in O-H--O hydrogen bonding with a carboxylate oxygen atom [O5-H1W--O4, 2.020 (5)
Å; D-H-A angle, 172.2 (6)°; O5-H2W--O2, 2.005 (7); D-H-A angle, 165.2 (8)°] (Figure 2c). In
addition a C-H---N interaction between a methyl proton of the trimethyl tin motifs of one 1D
chain with the nitrogen atom N2 of another 1D chain [C18-H18---N2, 3.362(5)Å; D-H-A angle,
155.75(38)°] is also seen (Supporting Information). These two kinds of secondary interactions
collectively afford a 3D supramolecular architecture (Figure 2c).
Page 8 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
(a)
(b) (c)
Figure 2. (a) 1D polymeric structure of 2 (b) Coordination mode of the ligand (c) 3D
supramolecular architecture of 2. (Methyl groups are omitted from Figure 2c)
X-ray Crystal structure of 3
In contrast to the structures of 1 and 2 where all the coordinating atoms take part in binding with
the tin centers, in 3, only the two carboxylate groups participate, both in a monodentate manner;
the pyridine nitrogen atom is not involved in coordination (Chart 2a). Such a 2.01010 mode of
coordination leads to the formation a 1D coordination polymer (Figure 3a). Another point of
Page 9 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
difference is that 3 is an anionic coordination polymer; the asymmetric unit contains two
triphenyl tin units bound to two different, fully deprotonated ligands. The charge is balanced by
the presence of triethylammonium cations (Figure 3b). Selected metric parameters of 3 are
summarized in Table 2. The crystal packing reveals that two 1D chains of 3 are stacked together
by means of three different π-π interactions (Figure 3c).
(a)
(b) (c)
Figure 3. (a) 1D polymeric structure of 3 (b) asymmetric unit of 3 (c) π-π stacking between 1D
anionic chains of 3 [A (pink), 3.771(7)Å; B (blue), 3.730(7)Å and C (green), 3.934(6)Å] .
Page 10 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
Conclusion
The reactions of triorganotin compounds with (E)-5-(pyridin-4-ylmethyleneamino)isophthalic
acid (LH2) afforded 2D and 1D coordination polymers. Reaction of (n-Bu3Sn)2O with LH2
produces a 2D coordination polymer 1 containing 36-membered macrocycles as repeating
blocks. In contrast, the reaction of Me3SnCl with the ligand LH2 afforded a 1D coordination
polymer 2 which shows extended supramolecular assembly in the solid-state. Unlike 1 and 2
which are neutral coordination polymers, the reaction of (Ph3Sn)2O with LH2 results in the
generation of an anionic 1D coordination polymer 3.
Experimental Section
Solvents were distilled and dried prior to use according to standard procedures. (n-Bu3Sn)2O,
Me3SnCl, (Ph3Sn)2O, isonicotinaldehyde and 5-aminoisophthalic acid (all from Aldrich) were
used as received. Melting points were measured using a JSGW melting point apparatus and are
uncorrected. Elemental analyses were carried out using a Thermoquest CE instruments model
EA/110 CHNS-O elemental analyzer. Infrared spectra were recorded as KBr pellets on a FT-IR
Bruker-Vector Model. 1H and 119Sn NMR spectra were obtained on a JEOL-DELTA2 500 model
spectrometer using CDCl3 as the solvent. Chemical shifts were referenced with respect to
tetramethylsilane (for 1H NMR) and tetramethyltin (for 119Sn NMR) respectively. 119Sn NMR
spectra were recorded under broad-band decoupled conditions. Thermogravimetric Analysis was
carried out on a Perkin Elmer Pyris 6 Thermogravimetric analyzer. UV−Vis spectra were
recorded on a Perkin-Elmer Lambda 20 UV−Vis spectrometer in a 1 × 10−5 M methanol solution.
The steady-state emission spectra were measured using a Perkin-Elmer LS-55 model
spectrophotometer in a 1 × 10−5 M methanol solution.
Page 11 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
Synthesis
(E)-5-(Pyridin-4-ylmethyleneamino)isophthalic acid (LH2)
The synthesis of LH2 is depicted in Scheme 2. To a solution of isonicotinaldehyde (0.107 g, 1
mmol) in 20 mL EtOH, 5-aminoisophthalic acid (0.181g, 1 mmol) was added. The mixture was
stirred for 2 h at room temperature to afford a pale-yellow precipitate of LH2 (Scheme 2). This
was washed with methanol several times and dried. Yield: 0.26 g (96 %). Mp: >230 °C. Anal.
Calcd for C14H10N2O4 (270.06 g) (%): C, 62.22, H, 3.73, N, 10.37; Found: C 62.17, H 3.71, N,
10.42. IR(KBr, cm-1): 3387.33 (b), 3070.46 (m), 2448 (w), 1717.42 (s), 1614.93 (s), 1414.36 (m),
1228.50 (s), 1193.99 (s), 823.11 (s), 760.68 (s), 677.94 (s), 505.17 (m), 473.33 (w). 1H NMR
(500 MHz, ppm): δ = 8.75-8.76 (d, 1H); 8.71-8.72 (d, 1H); 8.55 (s, 1H); 8.06 (s, 2H); 7.82-7.83
(d, 1H); 7.74-7.75 (d, 1H). ESI-MS: m/z (%) 269.0537 [M-H]- (100) .
Scheme 2. Synthesis of ligand (LH2).
[(n-Bu3Sn)2(µ-L)]n (1)
(n-Bu3Sn)2O (0.23 mL, 0.5 mmol) was added to a mixture of LH2 (0.135g, 0.5 mmol) in 40 mL
of toluene. The mixture of was heated under reflux for 9 h. The reaction mixture was cooled to
room temperature and evaporated to yield 1 as a powder. This was dissolved in n-hexane and left
NH2
OH
O
HO
O
CHO
N
+EtOH
RT
N
N
OH
O
HO
O
LH2
Page 12 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
for crystallization to afford crystals of 1. Yield: 0.34 g (80 %). Mp: >230 °C. Anal. Calcd for
C38H62N2O4Sn2 (848.33 g) (%): C 53.80; H 7.37; N 3.30; Found: C 53.67, H 7.42, N, 3.46. IR
(KBr, cm-1): 3419.87 (b), 2954 (s), 2922.55 (s), 2854 (m), 2869.78 (m), 1647.26 (s), 1605.25 (s),
1569.06 (s), 1385.23 (s), 1320.13 (s), 773.39 (m), 724.31 (m), 672.84 (m). 1H NMR (500 MHz,
ppm): δ = 8.75-8.76 (d, 1H, LH2); 8.71-8.72 (d, 1H, LH2); 8.55 (s, 1H, LH2); 8.06 (s, 2H, LH2);
7.82-7.83 (d, 1H, LH2); 7.74-7.75 (d, 1H, LH2); 0.89-0.92 (t, 15H, butyl CH3); 1.30-1.41 (m,
10H, butyl -CH2-); 1.63-1.72 (b, 20H, butyl Sn-CH2-CH2-).119Sn NMR (500 MHz, ppm): δ =
121.81; 130.66. ESI-MS: m/z (%) 291.1146 [n-Bu3Sn]+ (52); 364.1635 [(n-
Bu3SnH)(Na)(H2O)MeOH]+ (42); 625.2206 [(Bu3Sn)2(CHOO)]+ (100).
[(Me3Sn)2(µ-L)(H2O)]n (2)
A mixture of Me3SnCl (0.099g, 0.5 mmol), LH2 (0.135g, 0.5 mmol) and triethyl amine (0.21 mL,
1.5 mmol) in 30 mL EtOH was stirred for 1 day to afford a clear yellow solution. The mixture
was filtered and kept for slow evaporation to get single crystals of 2. Yield: 0.21 g (68 %). Mp:
>230 °C. Anal. Calcd for C20H28N2O5Sn2 (613.87 g) (%): C 39.13; H 4.60; N 4.56; Found: C
39.09, H 4.69, N, 4.67. IR (KBr, cm-1): 3417.16 (b), 2990.39 (m), 2921.41 (m), 1673.94 (s),
1608.84 (s), 1562.96 (s), 1413.99 (s), 1375.19 (s), 1249.92 (s), 1232.50 (s), 772.48 (s), 685.78
(m), 596.68 (m), 549.89 (m). 1H NMR (500 MHz, ppm): δ = 8.75-8.76 (d, 1H, LH2); 8.71-8.72
(d, 1H, LH2); 8.55 (s, 1H, LH2); 8.06 (s, 2H, LH2); 7.82-7.83 (d, 1H, LH2); 7.74-7.75 (d, 1H,
LH2); 0.51 (s, 9H, Sn-CH3).119Sn NMR (500 MHz, ppm): δ = 24.46 . ESI-MS: m/z (%) 197.0046
[(Me3Sn)(MeOH)]+ (38); 206.0056 [[(Me3Sn)(Na)(H2O)]+ (27); 372.9478 [(Me3Sn)2(HCOO]+
(12).
Page 13 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
[(Ph3Sn)(µ-L)(Et3NH)]n (3)
A mixture of (Ph3Sn)2O (0.179g, 0.25 mmol), LH2 (0.135g, 0.5 mmol) and triethyl amine (0.21
mL, 1.5 mmol) in 30 mL EtOH was stirred for 1 day to afford a clear yellow solution. The
mixture was filtered and kept for slow evaporation to get single crystals of 3. Yield: 0.27 g (75
%). Mp: charred at 210 °C. Anal. Calcd for C38H39N3O4Sn (720.44 g) (%): C 63.35; H 5.46; N
5.83; Found: C 63.29, H 5.53, N, 5.92. IR (KBr, cm-1): 3343.72 (b), 3043.35 (m), 2989.14 (m),
2698.52 (b), 1718.30 (m), 1625.16 (s), 1601.07 (s), 1573.82 (s), 1480.48 (m), 1429.47 (s),
777.05 (m), 732.83 (m), 699.33 (s), 553.98 (s), 456.10 (s). 1H NMR (500 MHz, ppm): δ = 8.75-
8.76 (d, 1H, LH2); 8.71-8.72 (d, 1H, LH2); 8.55 (s, 1H, LH2); 8.06 (s, 2H, LH2); 7.82-7.83 (d,
1H, LH2); 7.74-7.75 (d, 1H, LH2); 7.35-7.44 (m, 15H, Sn-Ph); 3.07-3.11 (q, 6H, -CH2- Et3NH);
1.21-1.23 (t, 9H, -CH3 Et3NH). ESI-MS: m/z (%) 351.0209 [Ph3Sn]+ (30); 745.0406
[(Ph3Sn)2(HCOO)]+ (10).
X-ray Crystallography
The crystal data for 1-3 were collected on a Bruker SMART APEX CCD Diffractrometer.
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 structures were solved and refined by full-matrix least squares on F2
using SHELXTL software package.9 Non-hydrogen atoms were refined with anisotropic
displacement parameters. Figures (1-3) and their bonding parameters were obtained from
DIAMOND 3.1f software package.10 CCDC reference numbers for 1, 2 and 3 are 935287,
935288 and 935289 respectively.
Page 14 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
Acknowledgments
We thank the Department of Science and Technology (DST), India, and Council of Scientific
and Industrial Research (CSIR), India, for financial support. V.C. is thankful to the Department
of Science and Technology for a J. C. Bose fellowship. C.M. and R. K.M. thanks UGC, India,
for a Senior Research Fellowship.
Supporting Information
Crystallographic information files (CIFs) for 1-3, Details of photophysical studies, TGA,
Additional DIAMOND figures for 1-3. This information is available free of charge via the
Internet at http://pubs.acs.org/.
Table 1. Crystal data and structure refinement parameters of 1-3
Parameters 1 2 3
Empirical formula C38 H62 N2 O4 Sn2 C20 H28 N2 O5 Sn2 C38 H39 N3 O4 Sn
Formula weight 848.28 613.82 720.43
Temperature 293(2) K 293(2)K 293(2)K
Wavelength 0.71069Å 0.71069 Å 0.71069Å
Crystal system, space group Monoclinic, P21/n Monoclinic, P21/n Monoclinic, P21/n
Unit cell dimensions a = 10.335(5)Å a = 6.915(5)Å a = 18.736(5)Å
b = 27.054(5)Å b = 12.362(5)Å b = 11.368(5)Å
c = 15.012(5)Å c = 27.938(5)Å c = 31.720(5)Å
α = 90° α = 90 ° α = 90°
β = 99.885(5)° β = 96.110(5)° β = 97.254(5)°
γ = 90° γ = 90 ° γ = 90°
Volume 4135(3)Å3 2375(2)Å3 6702(4)Å3
Z, Calculated density 4,1.363 Mg/m3 4,1.717 Mg/m3 8, 1.428 Mg/m3
Absorption coefficient 1.244mm-1 2.134mm-1 0.807mm-1
F(000) 1744 1208 2960
Crystal size 0.21x 0.15x 0.11mm3 0.19 x 0.13 x 0.09 mm3 0.23 x 0.16 x 0.12mm3
θ range for data collection 2.04 to 25.50°. 2.21 to 26.00 °. 1.20 to 25.50°.
Page 15 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
Limiting indices -12<=h<=11,
-32<=k<=24,
-17<=l<=18
-6<=h<=8,
-15<=k<=14,
-34<=l<=31
-22<=h<=16,
-13<=k<=13,
-36<=l<=38
Reflections collected / unique 22181 / 7669
[R(int) = 0.0487]
13104 / 4668
[R(int) = 0.0517]
35825 / 12437
[R(int) = 0.0895]
Completeness to theta 99.5 % 99.6% 99.6 %
Data / restraints / parameters 7669 / 58 / 403 4668 / 0 / 276 12437 / 0 / 843
Goodness-of-fit on F2 1.050 1.007 1.024
Final R indices [I >2σ(I)] R1 = 0.0604,
wR2 = 0.1576
R1 = 0.0421,
wR2 = 0.0901
R1 = 0.0547,
wR2 = 0.1141
R indices (all data) R1 = 0.0745,
wR2 = 0.1740
R1 = 0.0639,
wR2 = 0.1012
R1 = 0.1001,
wR2 = 0.1506
Largest diff. peak and hole 3.358 and -1.443 e.Å-3 1.083 and -0.546 e.Å-3 1.063 and -0.558 e.Å-3
Table 2. Selected bond distances (Å) and angles (°) of 1-3
1 2 3
Bond distances
(Å)
Bond angles (°) Bond distances
(Å)
Bond angles (°) Bond distances
(Å)
Bond angles (°)
Sn1-O1
2.099(5)
O1-Sn1-O3
173.80(18)
Sn1-O1
2.165(3)
O1-Sn1-N1
175.23(14)
Sn1-O1
2.215(5)
O1-Sn1-O4
171.63(15)
Sn1-O3
2.474(4)
O4-Sn2-N2
177.16(15)
Sn1-N1
2.532(4)
O3-Sn2-O5
171.67(16)
Sn1-O4
2.198(4)
Sn2-O4
2.181(4)
Sn2-O3
2.175(4)
Sn2-N2
2.509(5)
Sn2-O5
2.434(5)
Page 16 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
References:
[1] (a) Chandrasekhar, V.; Singh, P.; Gopal, K. In Tin Chemistry: Fundamental, Frontiers and
Applications; Davies, Gielen, A. G.; Pannell, M.; Tiekink, K. H.; Eds, E. R. T. Wiley-VCH:
Weinheim., 2008, 93. (b) Davies, A. G. Organotin Chemistry; Wiley-VCH, Verlag, GmbH and
Co. KGaA: Weinheim., 2004. (c) Beckmann J.; Jurkschat, K. Coord. Chem. Rev. 2001, 215, 267.
[2] (a) Chandrasekhar, V.; Gopal, K.; Nagendran, S.; Singh, P.; Steiner, A.; Zacchini, S.;
Bickley, J. F. Chem. -Eur. J. 2005, 11, 5437. (c) Chandrasekhar, V.; Thilagar, P.; Bickley, J. F.;
Steiner, A. J. Am. Chem. Soc. 2005, 127, 11556. (d) Chandrasekhar, V.; Nagendran, S.; Baskar,
V. Coord. Chem. Rev. 2002, 235, 1. (b) Chandrasekhar, V.; Gopal, K.; Nagendran, S.; Singh, P.;
Steiner, A.; Zacchini, S.; Azhakar, R.; Kumar, M. R.; Srinivasan, A.; Ray, K.; Chandrashekar, T.
K.; Madhavaiah, C.; Verma, S.; Priyakumar, U. D.; Sastry, G. N. J. Am. Chem. Soc. 2005, 127,
2410. (e) Zheng, G. L.; Ma, J. F.; Su, Z. M.; Yan, L. K.; Yang, J.; Li Y. Y.; Liu, J. F. Angew.
Chem., Int. Ed. 2004, 43, 2409. (f) Zheng, G.-L.; Ma, J.-F.; Yang, J.; Li, Y.-Y.; Hao, X.-R.
Chem. -Eur. J., 2004, 10, 3761.
[3] (a) Chandrasekhar, V.; Baskar, V.; Steiner, A.; Zacchini, S. Organometallics 2004, 23, 1390.
(b) Chandrasekhar, V.; Baskar, V.; Steiner, A.; Zacchini, S. Organometallics 2002, 21, 4528. (c)
Beckmann, J.; Dakternieks, D.; Duthie, A.; Mitchell, C. Organometallics 2003, 22, 2161. (d)
Ribot, F.; Sanchez, C. Organometallics 2001, 20, 2593. (e) Xie, Y. P.; Ma, J. F.; Yang, J.; Su,
M. Z. Dalton Trans. 2010, 39, 1568. (f) Song, S. Y.; Ma, J. F.; Yang, J.; Gao, L. L.; Su, Z. M.
Organometallics 2007, 26, 2125.
[4] (a) Chandrasekhar, V.; Boomishankar, R.; Singh, S.; Steiner, A.; Zacchini, S.
Organometallics 2002, 21, 4575. (b) Chandrasekhar, V.; Boomishankar, R.; Gopal, K.;
Sasikumar, P.; Singh, P.; Steiner, A.; Zacchini, S. Eur. J. Inorg. Chem. 2006, 4129. (c) Baron,
Page 17 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
C. E.; Ribot, F.; Steunou, N.; Sanchez, C.; Fayon, F.; Biesemans, M.; Martins, J. C.; Willem, R.
Organometallics 2000, 19, 1940. (d) Prabusankar, G.; Jousseaume, B.; Toupance, T.; Allouchi,
H. Dalton Trans. 2007, 3121. (e) Shankar, R.; Jain, A.; Kociok-Köhn, G.; Mahon, M. F.;
Molloy, K. C. Inorg. Chem. 2010, 49, 4708.
[5] (a) Chandrasekhar, V.; Nagendran, S.; Bansal, S.; Kozee, M. A.; Powell, D. R. Angew.
Chem., Int. Ed. 2000, 39, 1833. (b) Hahn, U.; Gégout, A.; Duhayon, C.; Coppel, Y.; Saquet, A.;
Nierengarten, J. F. Chem. Commun. 2007, 516. (c) Li, S. L.; Zhang, Y. M.; Ma, J. F.; Lan, Y.
Q.; Yang, J. Dalton Trans. 2008, 1000.
[6] (a) Gianneschi, N. C.; Masar, M. S.; Mirkin, C. A. Acc. Chem. Res. 2005, 38, 825. (b)
Hosseini, M. W. Acc. Chem. Res. 2005, 38, 313. (c) Nitschke, J. R. Acc. Chem. Res. 2007, 40,
103. (d) MacGillivray, L. R.; Papaefstathiou, G. S.; Friščić, T.; Hamilton, T. D.; Dejan-Krešimir,
B.; Chu, Q.; Varshney, D. B.; Georgiev, I. G. Acc. Chem. Res. 2008, 41, 280. (e) Chae, H. K.;
Siberio-Perez, D. Y.; Kim, J.; Go, Y.; Eddaoudi, M.; Matzger, A. J.; O’Keeffe, M.; Yaghi, O. M.
Nature. 2004, 427, 523. (f) Zhao, X.; Xiao, B.; Fletcher, J. A.; Thomas, K. M.; Bradshaw, D.;
Rosseinsky, M. J. Science. 2004, 306, 1012. (g) Ferey, G.; Mellot- Draznieks, C.; Serre, C.;
Millange, F.; Dutour, J.; Surble, S.; Margiolaki, I. Science. 2005, 309, 2040. (h) Chandler, B. D.;
Enright, G. D.; Udachin, K. A.; Pawsey, S.; Ripmeester, J. A.; Cramb, D. T.; Shimizu, G. K. H.;
Nat. Mater. 2008, 7, 229. (i) Lee, J. Y.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.;
Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450. (j) Seo, J. S.; Whang, D.; Lee, H.; Jun, S. I.; Oh, J.;
Jeon, Y. J.; Kim, K. Nature. 2000, 404, 982. (k) Zou, R.-Q.; Sakurai, H.; Xu, Q. Angew. Chem.,
Int. Ed. 2006, 45, 2542. (l) Kurmoo, M. Chem. Soc. Rev. 2009, 38, 1353. (m) Ohba, M.; Okawa,
H. Coord. Chem. Rev. 2000, 198, 313. (n) Shiga, T.; Okawa, H.; Kitagawa, S.; Ohba, M.; J. Am.
Chem. Soc. 2006, 128, 16426.
Page 18 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
[7] (a) Garcia-Zarracino, R.; Ramos-Quińones, J.; Höpfl, H. Inorg. Chem. 2003, 42, 3835. (b)
Garcia-Zarracino, R.; Höpfl, H.; Angew. Chem., Int. Ed. 2004, 43, 1507. (c) Garcia-Zarracino,
R.; Höpfl , H. J. Am. Chem. Soc. 2005, 127, 3120. (d) Garcia-Zarracino, R.; Höpfl , H. Appl.
Organomet. Chem. 2005, 19, 451. (e) Ma, C.; Wang, Q.; Zhang, R. Inorg. Chem. 2008, 47, 7060.
(f) Zhang, R.; Ren, Y.; Wang, Q.; Ma, C. J Inorg Organomet Polym. 2010, 20, 399. (g)
Chandrasekhar, V.; Nagendran, S.; Bansal, S.; Cordes, A. W.; Vij, A. Organometallics 2002,
21, 3297. (h) Chandrasekhar, V.; Boomishankar, R.; Steiner, A.; Bickley, J. F. Organometallics
2003, 22, 3342. (i) Chandrasekhar, V.; Singh, P. Cryst. Growth Des. 2010, 10, 3077. (j)
Chandrasekhar, V.; Thilagar, P.; Steiner, A. Cryst. Growth Des. 2011, 11, 1446. (k)
Chandrasekhar, V.; Thirumoorthi, R.; Azhakar, R. Organometallics 2007, 26, 26. (l)
Chandrasekhar, V.; Mohapatra, C.; Butcher, R. J. Cryst. Growth Des. 2012, 12, 3285. (m)
Chandrasekhar, V.; Mohapatra, C.; Banerjee, R.; Mallick. A. Inorg. Chem. 2013, 52, 3579. (n)
Chandrasekhar, V.; Kundu, S.; Kumar, J.; Verma, S.; Gopal, K.; Chaturbedi, A.; Subramaniam,
K. Cryst. Growth Des. 2013, 13, 1665. (o) Zarracino, R. G-.; Höpfl, H.; Rodríguez, M. G-. Cryst.
Growth Des. 2009, 9, 1651. (p) Ahuactzi, I. F. H-.; Huerta, J. C-.; Barba, V.; Höpfl, H.; Rivera,
L. S. Z-.; Beltrán, H. I. Eur. J. Inorg. Chem. 2008, 9, 1200. (q) Ma, C.; Li, J.; Zhang, R.; Wang,
D. J. Organomet. Chem. 2006, 691, 1713. (r) Zhang, R-.F.; Wang, Q-.F.; Yang, M-.Q.; Wang,
Y-. R.; Ma, C. Polyhedron. 2008, 27, 3123.
[8] Coxall, R. A.; Harris, S. G.; Henderson, D. K.; Parsons, S.; Tasker, P. A.; Winpenny, R. E. P.
J. Chem. Soc., Dalton Trans. 2000, 2349.
[9] Sheldrick, G. M. SHELXTL version 6.14, Bruker AXS Inc., Madison, WI, 2003.
[10] DIAMOND version 3.1f, Crystal Impact GbR, Bonn, Germany, 2004.
Page 19 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960
Graphical Absract
Reactions of (E)-5-(pyridin-4-yl-methyleneamino)isophthalic acid
(LH2) with Triorganotin Oxides and –Chloride. Formation of 1D-
and 2D-Coordination Polymers
Vadapalli Chandrasekhar,*a,b Chandrajeet Mohapatraa and Ramesh K. Metre a
aDepartment of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India
bTata Institute of Fundamental Research, Centre for Interdisciplinary Sciences, 21, Brindavan
Colony, Narsingi, Hyderabad- 500075, India
Three coordination polymers containing tri-n-butyl,-methyl and -phenyl tin units as nodes and a
Schiff base-containing dicarboxylate ligand as the linker have been synthesized and structurally
characterized.
Page 20 of 20
ACS Paragon Plus Environment
Crystal Growth & Design
123456789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960