Synthesis, crystal structure and theoretical calculation of triphenyltin (IV) polymer based on 2,4-dichlorophenylacrylic acid

Article abstract of DOI:10.1080/24701556.2019.1703747

Reaction between 2,4-dichlorophenylacrylic acid (HL) and triphenyltin (IV) hydroxide to yield the complex [(Ph₃Sn)L]_n (1). The complex has been characterized by elemental analysis, infrared spectrum and single crystal X-ray diffracti

Full text of DOI:10.1080/24701556.2019.1703747

Inorganic and Nano-Metal Chemistry
ISSN: 2470-1556 (Print) 2470-1564 (Online) Journal homepage: https://www.tandfonline.com/loi/lsrt21
Synthesis, crystal structure and theoretical
calculation of triphenyltin (IV) polymer based on
2,4-dichlorophenylacrylic acid
Shuang Han, He Wang, Jiajun Wang, Linan Dun, Chuanbi Li & Chunling Liu
To cite this article: Shuang Han, He Wang, Jiajun Wang, Linan Dun, Chuanbi Li & Chunling
Liu (2019): Synthesis, crystal structure and theoretical calculation of triphenyltin (IV) polymer
based on 2,4-dichlorophenylacrylic acid, Inorganic and Nano-Metal Chemistry, DOI:
10.1080/24701556.2019.1703747
To link to this article: https://doi.org/10.1080/24701556.2019.1703747
Published online: 23 Dec 2019.
Submit your article to this journal
Article views: 9
View related articles
View Crossmark data
Full Terms & Conditions of access and use can be found at
https://www.tandfonline.com/action/journalInformation?journalCode=lsrt21

INORGANIC AND NANO-METAL CHEMISTRY
https://doi.org/10.1080/24701556.2019.1703747
SHORT COMMUNICATION
Synthesis, crystal structure and theoretical calculation of triphenyltin (IV)
polymer based on 2,4-dichlorophenylacrylic acid
Shuang Hana,b, He Wanga,b, Jiajun Wanga,b, Linan Duna,b, Chuanbi Lia,b, and Chunling Liua,b
b
aDepartment of Chemistry, Jilin Normal University, Siping, PR China; Key Laboratory of Preparation and Application of Environmental
Friendly Materials, Ministry of Education, Jilin Normal University, Changchun, China
ABSTRACT
ARTICLE HISTORY
Received 29 October 2019
Accepted 9 December 2019
Reaction between 2,4-dichlorophenylacrylic acid (HL) and triphenyltin (IV) hydroxide to yield
the complex [(Ph3Sn)L]n (1). The complex has been characterized by elemental analysis, infrared
spectrum and single crystal X-ray diffraction. The structural analysis shows that complex 1
possesses 1 D chain structure in which every tin atom is five coordinated. The 1 D chains linked by
C(66)-H(66)ꢀCl(2) hydrogen bonds to aggregate in 2 D framework. Additionally, the PXRD, TG, and
luminescent property were also investigated. The quantum chemistry calculations was performed
with the Gaussian09 program.
KEYWORDS
2,4-dichlorophenylacrylic
acid; triphenyltin (IV)
polymer; crystal structure;
theoretical calculations
Introduction
Experimental
Coordination polymers[1] and metal–organic frame- Synthesis of 2,4-dichlorophenyl acrylic acid
works,[2–4] colloquially known as MOFs, have attracted
b-substituted phenylacrylic acid has many physiological
increasing attention, due to their potential broad applica-
functions and it can be prepared by Knoevenagel-Doebner
tions in catalysis,[5,6] batteries,[7] gas storage/separation,[8]
synthesis method.[25] 2,4-dichlorophenylacrylic acid (HL)
sensor,[9] and drug delivery.[10] Organotin chemistry is an
was synthesized from 2,4-dichlorobenzaldehyde and malonic
important part of organometallic chemistry. The environ-
acid with pyridine as basic solvent and toluene as dispersant
mental and biological chemisty of Organotin complexes
under the condition of aniline as the catalyst (Route 1). The
have been the subjects of interest for some time due to their
detail steps are as follows:
increasingly widespread use.[11,12] Organotin complexes
In a round-bottom flask, 7.5 g malonic acid (0.07 mol)
are widely used in industry, agriculture and medicine,[13,14]
and 8 mL pyridine were added to dissolve malonic acid.
for example as homogeneous catalysts (function as supports
After the malonic acid dissolved, toluene 15 mL, 2,4-
for anchoring electroactive, photoactive, coordination
Dichlorobenzaldehyde 11.37 g (0.065 mol) and with catalytic
platforms),[15,16] special anti-tumour materials,[17,19] wood
amount 0.7 mL aniline were added. A reflux equipment was
preservatives and fungicides for plant protection.[20] From
assembled and heated for 2 hours under electromagnetic stir-
all the studied organotin compounds, the tin coordination
polymers[21] are no doubt the most intensively investi-
gated.[22] The tin complexes have a rich variety of coordin-
ation modes so that it makes the property diversified,[23]
among these coordination modes the carboxylate ligands
have monodentate and bidentate coordination forms.
Through changing the types of carboxylate ligands and
the hydrocarbon groups in organotin compounds, a large
ring. After the reaction, the mixture cooled to room tempera-
ture, K2CO3 solution added to the reaction solution, stirred for
10 minutes (if the solid precipitated, then heated dissolved
completely in water bath), separated the solution while hot, the
water layer is adjusted to pH 2-3 using concentrated HCl. The
precipitated solids are filtered, washed and dried. Colorless
crystals were obtained by recrystallizing in anhydrous ethanol-
water. Productivity: 63.2%, melting point: 158.7–159.4 ꢁC.
number of organotin carboxylates compounds with novel and Elemental analysis: calcd. (%) for C9H6O2Cl2: C, 49.80; H,
2.79; found (%): C, 47.54; H, 2.62. IR (cm-1): 2823ꢂ2567
diverse structures can be obtained. Mazhar et al. summarized
ꢀ(COOH), 1690 ꢀ(C ¼ O), 1619 ꢀ(C ¼ C).
the synthetic methods, physical properties and chemical
properties of more than 300 organotin carboxylates.[24]
In order to further exploring the structural types of
organotin carboxylates and the coordination mode of central
Synthesis of [(Ph3Sn)L]n (1)
tin atoms, an organotin carboxylate was designed and
synthesized from the reaction of 2,4-dichlorophenylacrylic
acid (HL) with triphenyltin hydroxide.
HL (0.43 g, 2.0 mmol) and triphenyltin hydroxide (0.77 g,
2.0 mmol) were added to 40 mL anhydrous toluene solution,
heated and refluxed under stirring for 8 hours, cooled to
CONTACT Chunling Liu
liu_chunling@126.com
Department of Chemistry, Jilin Normal University, Siping, PR China.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsrt.
ß 2019 Taylor & Francis Group, LLC

2
S. HAN ET AL.
room temperature, filtered, and the filtrate was evaporated triphenyltin groups and forms a one-dimensional chain
to obtain white solid (Route 2). The solid was dissolved
in ethanol and stayed at room temperature. The colorless
transparent crystal was obtained by slowly volatilizing the
solvent. Productivity: 52.6%, melting point: 261.1–262.7 ꢁC.
Elemental analysis: calcd.(%) for C54H40Cl4O4Sn2: C, 57.29;
H,3.56; found (%): C, 57.44; H, 3.36. IR data (cmꢃ1): 1638
vas(COO), 1582ꢀ(-C ¼ C-), 1469ꢀs(COO), 1514, 1428,
1398ꢀ(C-C of benzene ring), 569ꢀ(Sn-C), 453ꢀ(Sn-O).
structure. Each tin atom is five coordinated, forming a
twisted trigonal bipyramidal configuration.[29] The positions
on the equatorial plane are occupied by carbon atoms
from three benzene rings, and oxygen atoms from two
different carboxyl groups occupy the axial positions. In
Table 2, Sn(1)-O(1) ¼ 2.2704(1) Å, Sn(1)-O(3) ¼ 2.2101(2)
Å, Sn(2)-O(2) ¼ 2.1944(2) Å, Sn(2)-O(4) ¼ 2.2941(2) Å,
these distances are in accordance with the simillar complex
in literature.[30] The sum of angles between carbon atoms
and Sn (1) atoms on the equatorial plane is 359.8 degrees,
and that between Sn (2) atoms is 360 degrees, indicating
that Sn (1), C (31), C (41) and C (51) are almost coplanar,
Sn (2), C (61), C (71) and C (81) are on the same plane.
At the same time, there are interesting intermolecular
interactions in complex 1 which help in the construction of
the supramolecule. As shown in Figure 3, every pair of
chain structure of the molecule is linked by intermolecular
X-ray crystallography
Crystal structure measurement was performed on a Bruker
SMART APEX II CCD diffractometer equipped with a graph-
ite-monochromatic Mo Ka (k ¼ 0.071073 nm) radiation by
using the 2h and x scan mode at 296(2) K.[26,27] The
structure was determined by direct method and refined by
full-matrix least-squares procedure using the SHELXL-
2013.[28] A total of 27332 independent diffraction intensity
data were collected in the range of 3.42ꢁ ꢄ 2h ꢄ 52.18ꢁ, of
which 9938 were observed reflections [I> 2r (I)] . The final
deviation factor is R1¼0.0233, wR2 ¼ 0.0522. Crystallographic
parameters and the data collection statistics are given in
Table 1. Selected bond lengths and bond angles are listed
in Table 2. The Crystallographic data have been deposited
Table 1. Crystallographic data and structure refinement parameters for the
complex 1.
Empirical formula
Formula weight
Temperature
C54H40Cl4O4Sn2
1132.04
296(2) K
Wavelength (Å)
Crystal system
0.71073
Monoclinic
with the Cambridge Crystallographic Data Center: deposition Space group
P21/n
10.0635(13)
23.887(3)
21.551(3)
a (Å)
numbers CCDC 1922167. These data may be obtained free of
charge from the Cambridge Crystallographic Data Center
through http://www.ccdc.cam.ac.uk/data_request/cif.
b (Å)
c (Å)
a (ꢁ)
90
b (ꢁ)
102.636(2)
90
5055.0(11)
4
1.487
1.243
2256
c (ꢁ)
Volume (Å3)
Results and discussion
Z
Density (Mg/m3) calculated
Absorption coefficient (mmꢃ1
F(000)
Description of crystal structure
)
The structure of complex 1 is shown in Figures 1 and 2.
The carboxylate as bridging ligand connects two adjacent
Crystal size (mm3)
Theta range (ꢁ)
Limiting indices
0.28 ꢅ 0.26 ꢅ 0.22
1.71–26.09
ꢃ12 ꢄ h ꢄ 12, ꢃ29 ꢄ k ꢄ 17,
ꢃ26 ꢄ l ꢄ 26
CHO
CH=CHCOOH
Cl
Reflections collected/unique
Refinement method
27332/9938 [Rint ¼ 0.0168]
Full-matrix least-squares on F2
9938/0/577
COOH
CH2
COOH
Cl
+
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r (I)]
R indices (all data)
1.027
R1 ¼ 0.0233, wR2 ¼ 0.0522
R1 ¼ 0.0312, wR2 ¼ 0.0562
0.436 and ꢃ0.454
Cl
Cl
Largest diff. peak and hole (e Åꢃ3
)
Route 1.
Cl
O
Cl
COOH
Ph
Sn
Ph
Ph
Sn
Ph
Ph
O
+
Ph3SnOH
O
O
Cl
Cl
Ph
n
Cl
Cl
Route 2.

INORGANIC AND NANO-METAL CHEMISTRY
3
Table 2. Selected bond length and angles for complex 1.
C(66)-H(66)ꢀꢀꢀCl(2) hydrogen bonding [H(66)ꢀꢀꢀCl(2)] ¼
2.941 Å, C(66)ꢀꢀꢀCl(2)] ¼ 3.446 Å, and the angle of the C(66)-
H(66)ꢀꢀꢀCl(2) ¼ 115.56o]. The complex is further inter-
connected and assembled into two-dimensional network
structure.
O(1)-Sn(1)
O(3)-Sn(1)
C(1)-O(1)
C(10)-O(3)
C(31)-Sn(1)
C(51)-Sn(1)
C(71)-Sn(2)
C(51)-Sn(1)-C(41)
C(41)-Sn(1)-C(31)
C(41)-Sn(1)-O(3)
C(51)-Sn(1)-O(1)
C(31)-Sn(1)-O(1)
C(61)-Sn(2)-C(71)
C(71)-Sn(2)-C(81)
C(71)-Sn(2)-O(2)
C(61)-Sn(2)-O(4)
C(81)-Sn(2)-O(4)
2.2704(1)
2.2101(2)
1.249(2)
1.255(2)
2.130(2)
2.121(2)
2.125(2)
120.09(9)
121.27(9)
96.88(8)
90.72(8)
85.38(7)
123.51(9)
116.07(9)
83.92(7)
92.63(7)
87.36(7)
O(2)-Sn(2)
O(4)-Sn(2)
C(1)-O(2)
C(10)-O(4)#1
C(41)-Sn(1)
C(61)-Sn(2)
C(81)-Sn(2)
C(51)-Sn(1)-C(3)
C(51)-Sn(1)-O(3)
C(31)-Sn(1)-O(3)
C(41)-Sn(1)-O(1)
O(3)-Sn(1)-O(1)
C(61)-Sn(2)-C(8)
C(61)-Sn(2)-O(2)
C(81)-Sn(2)-O(2)
C(71)-Sn(2)-O(4)
O(2)-Sn(2)-O(4)
2.1944(2)
2.2941(2)
1.264(2)
1.260(3)
2.129(2)
2.118(2)
2.128(2)
118.44(9)
88.77(8)
88.76(7)
89.38(7)
173.04(6)
120.42(9)
92.57(7)
93.11(7)
90.21(7)
173.68(6)
IR spectra
The infrared spectra of complex 1 is consistent with those
of organotin carboxylates with similar structures.[31,32]
The bands at 2823–2567 cmꢃ1 which appear in the free
ligand as the ꢀ(OH) stretching vibrations, are not
observed in complex 1, thus indicating metale-ligand
bond formation. The difference between the asymmetric
Symmetry transformations used to generate equivalent atoms: #1 x þ 1/2,
ꢃy þ 1/2,z þ 1/2.
[ꢀas(COO)]
and
symmetric[ꢀs(COO)]
stretching
vibrations frequencies of carboxyl groups is a reflection
of coordination mode between carboxyl oxygen atoms
and Sn atoms.[33,34] The asymmetric stretching vibration
[ꢀas (COO)] and the symmetric stretching vibration [ꢀs
(COO)] of the carboxyl groups of the complex 1 appear
at 1638 cmꢃ1 and 1469 cmꢃ1, respectively, the Dꢀ [ꢀas
(COO) ꢃꢀs(COO)] is 169 cmꢃ1, which indicates that the
carboxyl group in complex 1 coordinated with tin atoms
in the bidentate form. In addition, the absorption peaks
at 569 and 453 cmꢃ1 indicate that Sn-C and Sn-O bonds
are present in the product.[35]
Luminescent spectra
The luminescent properties of complex 1 and ligand HL
have been tested with a 150 W xenon lamp as the excitation
source at room temperature and the fluorescence emission
spectra of them are illustrated in Figure 4. The emission
peak of the ligand HL is located at 410 nm (excitation
at 287 nm) and the maximum emission wavelength of the
complex 1 shows at 428 nm (excitation at 325 nm). The
results indicate that optical transitions of complex is
centered on the 2,4-dichlorophenylacrylic acid ligand and
ꢆ
the emission peaks are attributed to intra-ligand p !p
transitions. Compared to the ligand HL, complex1 exhibits
a significant red shift and lower intensity, which can be
assigned to the formation of the complex.
Figure 1. Molecular Structure of Complex 1. (The Symmetry Code A: 0.5 þ x,
0.5ꢃy, 0.5 þ z, Ellipsoid Probability 30%).
Figure 2. One-dimensional Chain Molecular Structure of Complex 1.

4
S. HAN ET AL.
Figure 3. 2 D network structure assembled by intermolecular hydrogen bonds.
Figure 4. Solid-state emission spectra of HL and complex 1.
PXRD and thermal analyses
Figure 5. PXRD patterns of complex 1.
PXRD analyses of complex 1 was carried out at room
temperature in order to confirm the phase purity (Figure 5).
The experimental PXRD pattern is closely matched with
those in the simulated pattern from single-crystal structure,
revealing the good phase purity of the bulk crystalline
material.
the whole structure. The final residue was SnO2 (found
22.4%, calc. 13.31%). In general, complex 1 exhibited good
thermal stability.[36–38]
To study the thermal stability of complex 1, the thermo-
gravimetric analyses were performed in the temperature
range 30–800 ꢁC (Figure 6). Complex 1 was stable up to
Theoretical calculation
The quantum chemistry calculation of complex 1 was
214 ꢁC. The obvious weight loss process occurred in the performed with the Gaussian09 program[39] at the B3LYP/
range of 214–603 ꢁC, which indicated the decomposition of GenECP level (the 6–31 þ G(d) basis set for C, H, O, Cl and

INORGANIC AND NANO-METAL CHEMISTRY
5
LANL2DZ basis set for Sn). The initial structure of the title deprotonated 2,4-dichlorophenyl acrylic acid (left L in
complex 1 was obtained from the X-ray refinement data
(cif). On the base of the crystal fragments, the single point
energy calculations were performed. For keeping the charge
balance in the model, we used a neutral 2,4-dichlorophenyl
acrylic acid (containing a proton) and used two deproto-
Figure 7) and the LUMO electron cloud at the 2,4-dichloro-
phenyl acrylic acid which contains proton (right HL
in Figure 7). The electron cloud of the LUMO þ 2 is mainly
located at the benzene ring of HL. The LUMO þ 1 and
HOMO-1 is mainly located at deprotonated L (middle L in
Figure 7 for LUMO þ 1 and the left L in Figure 7 for
HOMO-1). While the electron cloud of HOMO-2 is mainly
sited at phenyl (the benzene ring which bonds the Sn2A
in the left in Figure 7). Selected atom net charges and
electronic configuration of the title complex at the B3LYP/
(6-31 þ G(d) (for C, H, O and Cl) and LANL2DZ (for Sn)
levels are listed in Table 3. The calculation results show
that electronic configurations of the central Sn atoms are
nated 2,4-dichlorophenyl acrylic anion in complex
1
for simplifying the polymeric complexes 1 to a ‘monomer’.
The calculation covered 123 atoms, 1482 basis functions,
2752 primitive gaussians, 291 a electrons and 291 b
electrons for the model of complex 1. The total molecular
energy is -5646.718 a.u., the energies of HOMO and LUMO
are ꢃ0.211 and ꢃ0.129 a.u., respectively, with the DE
(ELUMO ꢃEHOMO) value to be ꢃ0.082 a.u., which shows
the complex is stable in the ground state. The HOMO
and LUMO are presented in Figure 7, from which we
can see the HOMO electron cloud is mainly located at the
5 s0.80ꢂ0.825p0.94
2 s1.61ꢂ1.722p4.94ꢂ5.163p0.013d0.01 and 2 s0.76 2p2.423d0.014p0.03
, and those of O and Cl atoms are
.
The net charge of Sn is above 2. It indicated the Sn partially
obtains electrons from the 2, 4-dichlorophenyl acrylic acid
and the benzene ring.
Table 3. Selected atom net charges and electronic configuration of complex 1
at the B3LYP/(6-31 þG(d) (for C, H, Cl and O) and Lanl2dz (for Sn) levels.
Atom
Charge
Electron configuration
Sn1
Sn2A
O1
O2A
O2
O1A
O3
O4A
C1
C10
C31
C41
C51
C61
C71
C81
2.22818
2.25424
[core]5s(0.82)5p(0.94)
[core]5s(0.80)5p(0.94)
ꢃ0.68892
ꢃ0.85803
ꢃ0.71275
ꢃ0.67983
ꢃ0.80622
ꢃ0.77941
0.77461
[core]2s(1.68)2p(4.99)3p(0.01)
[core]2s(1.68)2p(5.16)3p(0.01)
[core]2s(1.61)2p(5.08)3p(0.01)3d(0.01)
[core]2s(1.72)2p(4.94)3d(0.01)
[core]2s(1.66)2p(5.12)3p(0.01)
[core]2s(1.68)2p(5.08)3p(0.01)
[core]2s(0.76)2p(2.42)3d(0.01)4p(0.03)
[core]2s(0.75)2p(2.36)4S(0.01)3d(0.01)4p(0.02)
[core]2s(1.04)2p(3.47)4p(0.02)
[core]2s(1.04)2p(3.49)4p(0.02)
[core]2s(1.05)2p(3.48)4p(0.02)
[core]2s(1.05)2p(3.46)4p(0.02)
[core]2s(1.05)2p(3.46)4p(0.02)
[core]2s(1.05)2p(3.45)4p(0.02)
0.84063
ꢃ0.54139
ꢃ0.55369
ꢃ0.55549
ꢃ0.53603
ꢃ0.54846
ꢃ0.53818
Figure 6. TG curves of complex 1.
Figure 7. The molecular orbitals of the complex 1.

6
S. HAN ET AL.
4-methyl-5-thiazoleacetic acid: X-ray crystal structures of poly-
meric Me3Sn[O2CCH2(C4H3NS)S]SnMe3 and Ph3Sn[O2CCH2
(C4H3NS)S]SnPh3. J. Inorg. Organomet. Polym. Mater 2005, 15,
341–343. DOI: 10.1007/s10904-005-7875-4.
Conclusion
This contribution has shown that the combination of
triphenyltin (IV) moiety with the 2,4-dichlorophenyl acrylic
acid result in the formation of a chain polymer. The inter-
molecular hydrogen bonds of C-HꢀꢀꢀCl play an important
role in the 2 D network structure. The calculation results
show reasonable electronic configurations of the central
Sn atoms. In addition, complex1 has good thermal stability
and exhibit the red shifts in solid state. These properties
are expected to have further applications in the future.
[12] Chandrasekhar, V.; Gopal, K.; Sasikumar, P.; Thirumoorthi, R.
ꢆ
Organooxotin assemblies from snc bond cleavage reactions .
Coord. Chem. Rev 2005, 249, 1745–1765. DOI: 10.1016/j.ccr.
2005.03.028.
[13] Hadi, A. G.; Jawad, K.; Ahmed, D. S.; Yousif, E. Srp. 2019, 10,
26–31. DOI: 10.5530/srp.2019.1.5.
[14] Chandrasekhar, V.; Nagendran, S.; Baskar, V. Organotin assem-
blies containing SnAO bonds. Coord. Chem. Rev 2002, 235,
1–52. DOI: 10.1016/S0010-8545(02)00178-9.
[15] Chandrasekhar, V.; Thirumoorthi, R. Reactions of 3,5-pyrazoledi-
carboxylic acid with organotin chlorides and oxides.
Coordination polymers containing organotin macrocycles.
Organometallics 2009, 28, 2096–2106. DOI: 10.1021/om900113q.
[16] Yin, H. D.; Chen, S. W.; Li, L. W.; Wang, D. Q. Synthesis,
characterization and crystal structures of the organotin(IV)
compounds with the schiff base ligands of pyruvic acid
thiophene-2-carboxylic hydrazone and salicylaldehyde thiophene-
2-carboxylic hydrazone. Inorganica Chimica Acta 2007, 360,
2215–2223. DOI: 10.1016/j.ica.2006.10.038.
[17] Hadjikakou, S. K.; Hadjiliadis, N. Antiproliferative and anti-
tumor activity of organotin compounds. Coord. Chem. Rev 2009,
253, 235–249. DOI: 10.1016/j.ccr.2007.12.026.
[18] Wang, H.; Hu, L.; Du, W.; Tian, X. H.; Zhang, Q.; Hu, Z. J.;
Luo, L.; Zhou, H. P.; Wu, J. Y.; Tian, Y. P. Two-photon active
organotin(IV) carboxylate complexes for visualization of anti-
cancer action. ACS Biomater. Sci. Eng. 2017, 3, 836–842. DOI:
10.1021/acsbiomaterials.6b00786.
Acknowledgments
We thank the National Natural Science Foundation of China (No.
21805110) for financial support.
References
[1] Sun, Y. X.; Sun, W. Y. Zinc( ii )– and cadmium( ii )–organic
frameworks with 1-imidazole-containing and 1-imidazole-
carboxylate ligands. Cryst. Eng. Comm 2015, 17, 4045–4063.
DOI: 10.1039/C5CE00372E.
[2] Rowsell Rowsell, J. L. C.; Yaghi, O. M. Metal–organic frame-
works:
a
new class of porous materials. Microporous
Mesoporous Mater. 2004, 73, 3–14. DOI: 10.1016/j.micromeso.
2004.03.034.
[3] Long, J. R.; Yaghi, O. M. The pervasive chemistry of metal–or-
ganic frameworks. Chem. Soc. Rev. 2009, 38, 1213–1214. DOI:
10.1039/b903811f.
[19] Rosenberg, E. Persistent organic pollutants and toxic metals in
foods 2013, 430–475.
[4] Batten, S. R.; Champness, N. R.; Chen, X. M.; et al. Cryst. Eng.
Comm 2012, 9, 3001–3004. DOI: 10.1039/c2ce06488j.
[5] Zou, R. Q.; Sakurai, H.; Xu, Q. Preparation, adsorption
properties, and catalytic activity of 3D porous metal–organic
frameworks composed of cubic building blocks and alkali-metal
ions. Angew. Chem. Int. Ed. 2006, 45, 2542–2546. DOI:
10.1002/anie.200503923.
[7] Nasalevich, M. A.; Becker, R.; Ramos Fernandez, E. V.;
Castellanos, S.; Veber, S. L.; Fedin, M. V.; Kapteijn, F.; Reek,
J. N. H.; van der Vlugt, J. I.; Gascon, J. Co@NH 2-MIL-125(Ti):
Cobaloxime-Derived Metal–Organic Framework-Based Composite
for Light-Driven H 2 Production. Energy Environ. Sci. 2015,
8, 364–375. DOI: 10.1039/C4EE02853H.
[6] Ning, G. H.; Tian, B.; Tan, L. M.; Ding, Z.; Herng, T. S.;
Ding, J.; Loh, K. P. Networked spin cages: tunable magnetism
and lithium ion storage via modulation of spin-electron
interactions. Inorg. Chem. 2016, 55, 9892–9897. DOI: 10.1021/
acs.inorgchem.6b01740.
[7] Banerjee, R.; Furukawa, H.; Knobler, D.; Britt, C.; Keeffe,
M. O.; Yaghi, O. M. Control of pore size and functionality in
isoreticular zeolitic imidazolate frameworks and their carbon
dioxide selective capture properties. J. Am. Chem. Soc. 2009,
131, 3875–3877. DOI: 10.1021/ja809459e.
[20] Kovala-Demertzi, D.; Dokorou, V. N.; Jasinski, J. P.; Opolski,
A.; Wiecek, J.; Zervou, M.; Demertzis, M. A. Organotin flufena-
mates: Synthesis, characterization and antiproliferative activity
of organotin flufenamates. J. Organomet. Chem 2005, 690,
1800–1806. DOI: 10.1016/j.jorganchem.2005.02.004.
[21] Guan, R.; Zhou, Z.; Zhang, M.; Liu, H.; Du, W.; Tian, X.;
Zhang, Q.; Zhou, H.; Wu, J.; Tian, Y. Organotin(IV) carboxyl-
ate complexes containing polyether oxygen chains with two-photon
absorption in the near infrared region and their anticancer activity.
Dyes and Pigments 2018, 158, 428–437. DOI: 10.1016/j.dyepig.2018.
05.072.
[22] Chandrasekhar, V.; Gopal, K.; Thilagar, P. Nanodimensional
organostannoxane molecular assemblies. Acc. Chem. Res. 2007,
40, 420–434. DOI: 10.1021/ar600061f.
[23] Zhang, Z. J.; Zeng, H. T.; Liu, Y.; Kuang, D. Z.; Zhang, F. X.;
Tan, Y. X.; Jiang, W. J. Synthesis, crystal structure and anti-
cancer activity of the dibutyltin(IV)oxide complexes containing
substituted salicylaldehyde- o -Aminophenol Schiff base with
appended donor functionality. Inorg. Nano-Met. Chem 2018,
48, 486–494. DOI: 10.1080/24701556.2019.1571513.
[24] Mazhar, M.; Choudhary, M. A.; Ali, S.; Xie, Q. L.; Song, X. Q.
Chem. Soc. Pak 2001, 23, 103–131.
[25] Augustine, J. K.; Naik, Y. A.; Mandal, A. B.; Chowdappa, N.;
Praveen, V. B. gem-Dibromomethylarenes: A convenient substi-
tute for noncommercial aldehydes in the Knoevenagel-Doebner
reaction for the synthesis of alpha,beta-unsaturated carboxylic
acids. J. Org. Chem. 2007, 72, 9854–9856. DOI: 10.1021/
jo701888m.
[8] Zhang, T.; Lin, W. Metal-organic frameworks for artificial
photosynthesis and photocatalysis. Chem. Soc. Rev. 2014, 43,
5982–5993. DOI: 10.1039/c4cs00103f.
[9] Sun, H. Y.; Li, X.; Wang, Z. R.; Sun, S. Q.; Li, C. B.; Wang, J. J.
Synthesis, crystal structure and theoretical calculations of two
Zn (II) coordination polymers based on 2,5-dihydroxytereph-
thalic acid. J. Clust. Sci. 2018, 29, 1275–1283. DOI: 10.1007/
s10876-018-1444-9.
[10] Gao, Z. J.; Yin, H.; Sun, L. Synthesis of diorganotin esters of
5-bromonicotinic acid: X-ray crystal structure of polymeric
5-bromonicotinatodiorganotin. J. Inorg. Organomet. Polym.
Mater 2006, 16, 83–89. DOI: 10.1007/s10904-006-9026-y.
[11] Ma, C. L.; Sun, J. F.; Qiu, L. L.; Cui, J. C. The synthesis and
characterization of triorganotin carboxylates of 2-mercapto-
[26] Bai, Y. P.; Li, Y. G.; Wang, E. B.; Wang, X. L.; Lu, Y.; Xu, L. A
novel reduced a-Keggin type polyoxometalate coordinated to
two and
a
half copper complex moieties: [Cu(2,20-
bipy)2][PMoVI8MoV4O40fCu(2,20-bipy)g2.5]ꢀH2O. J. Mol.
Struct 2005, 752, 54–59. DOI: 10.1016/j.molstruc.2005.04.013.
[27] Spek, A. L. Structure validation in chemical crystallography.
Acta Crystallogr. D Biol. Crystallogr. 2009, 65, 148–155. DOI:
10.1107/S090744490804362X.

INORGANIC AND NANO-METAL CHEMISTRY
7
[28] Sheldrick, G. M. Crystal structure refinement with SHELXL.
Acta Crystallogr. C Struct. Chem. 2015, 71, 3–8. DOI: 10.1107/
S2053229614024218.
Amino]benzoato-O-1,2,4:2,3,4-di-l3-Oxo-Tetrakis[di-n-Butyltin(IV)].
J. Organomet. Chem 2001, 620, 194–201. DOI: 10.1016/S0022-
328X(00)00819-6.
[29] Tiekink, E. R. T. Structural chemistry of organotin carboxylates:
a review of the crystallographic literature. Appl. Organometal.
Chem. 1991, 5, 1–23. DOI: 10.1002/aoc.590080108.
[30] Liu, C. L.; Liu, S. S.; Du, D. F.; Zhu, D. S.; Xu, L.
Organotin(IV) carboxylates of (E)-3-(2-Nitrophenyl) propenoic
acid: synthesis, spectroscopic characterization, crystal structure
and antitumor activity. J. Mol. Struct. 2011, 1003, 134–140.
DOI: 10.1016/j.molstruc.2011.07.052.
[31] Yousif, E. Synthesis, spectroscopic studies and fungicidal activity
of some diorganotin(IV) with 2-[(Phenylcarbonyl)Amino]propa-
noato. J. King Saud Univ. Sci 2012, 24, 167–170. DOI: 10.1016/
j.jksus.2010.12.002.
[32] Li, F. L.; Dai, B.; Song, H. B.; Mi, N.; Tang, L. F. Heteroat.
Chem 2010, 20, 411–417.
[33] You, Z. L.; Zhu, H. L. Syntheses, crystal structures, and antibac-
terial activities of four Schiff Base complexes of copper and
zinc. Z Anorg. Allg. Chem. 2004, 630, 2754–2760. DOI: 10.
1002/zaac.200400270.
[34] Kovala-Demertzi, D.; Kourkoumelis, N.; Koutsodimou, A.;
Moukarika, A.; Horn, E.; Tiekink, E. R. T. Synthesis and spec-
troscopic studies of diorganotin derivatives with tolfenamic
acid. crystal and molecular structure of the first complex of tol-
[35] Nakamoto, K. The handbook of infrared and raman spectra of
inorganic compounds and organic salts. Vibrational Spectroscopy
1997, 14, 303–304. DOI: 10.1016/S0924-2031(97)00012-X.
[36] Menezes, D. C.; Lima, G. M.; Porto, A. O.; Donnici, C. L.;
Ardisson, J. D.; Doriguetto, A. C.; Ellena, J. Synthesis, characterisa-
tion and thermal decomposition of Tin(IV) dithiocarbamate deriv-
atives
– single source precursors for tin sulfide powders.
Polyhedron 2004, 23, 2103–2109. DOI: 10.1016/j.poly.2004.06.007.
[37] Ma, C. L.; Tian, G. R.; Zhang, R. F. Solvothermal synthesis and
structural characterization of a novel one-dimensional organo-
tin polymer involving high centrosymmetric units containing
polyfunctional ligand 4-hydroxy-2-mercapto-6-methylpyrimi-
dine. Inorg. Chem. Commun 2006, 9, 882–886. DOI: 10.1016/j.
inoche.2006.05.029.
[38] Liu, C. L.; Li, W. J.; Du, D. F.; Prof. Dr. Zhu, D. S.; Xu, L.
Synthesis and characterization of triphenyltin(IV) carboxylates
with isophthalic acid and benzoic acid derivatives: X-ray crystal
structures of 1D supramolecular chains. Z Anorg. Allg. Chem.
2011, 637, 1253–1257. DOI: 10.1002/zaac.201100048.
[39] Frisch, G. W. T. M. J.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Men_Nucci,
B.; Petersson, G. A.; Nakatsuji, H.; Caricato.; et al. Gaussian 09;
Gaussian, Inc.: Wallingford CT, 2009.
fenamic
acid,
1,2:3,4-di-l2-2-[(3-Chloro-2-Methylphenyl)
Amino]-benzoato-O,O-1,3-Bis-2-[(3-Chloro-2-Methylphenyl)