Synthesis and structural characterization of phosphinate coordination polymers with tin(IV) and copper(II)

Article abstract of DOI:10.1016/j.molstruc.2019.127369

In this work, we report the synthesis and X–ray characterization of diphenylphosphinic acid (L) (redetermination at 100 K), and its two polymeric phosphinate complexes; [(C₆H₅)₂P(O)OSn(C₆H₅)₃]_n (C1) and [Cu(O₂PPh₂)₂]_n (C2), resulted from the bidentate coordinatioan of L. Sn(IV) centers in C1 are five-coordinate in a distorted trigonal bipyramidal geometry. One dimensional coordination chains of C2 are made by double-bridging ligands between the copper atoms, surrounded with four P–O in a square planar polyhedron. Structural characterization of the complexes revealed that M ? O bonds are responsible for the assembly of the primary structural motifs in both the complexes while C–H … π and H?H interactions are effective in organizing these molecules into extended 3D architectures. The quantitative mapping of interactions was also analyzed using Hirshfeld surface analysis. With respect to the ³¹PNMR spectra, there are probably fast transformations in the solution and different types of coordinated and dissociated species are in balance, consistent with the optimized structures in the solvent and gas phases.

Full text of DOI:10.1016/j.molstruc.2019.127369

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Synthesis and structural characterization of phosphinate coordination polymers with
tin(IV) and copper(II)
Khodayar Gholivand, Nasrin Fallah, Ali Asghar Ebrahimi Valmoozi, Akram Gholami,
Michal Dusek, Vaclav Eigner, Mahsa Pooyan, Fahimeh Mohammadpanah
PII:
S0022-2860(19)31478-4
DOI:
https://doi.org/10.1016/j.molstruc.2019.127369
MOLSTR 127369
Reference:
To appear in: Journal of Molecular Structure
Received Date: 13 April 2019
Revised Date: 16 October 2019
Accepted Date: 5 November 2019
Please cite this article as: K. Gholivand, N. Fallah, A.A. Ebrahimi Valmoozi, A. Gholami, M. Dusek,
V. Eigner, M. Pooyan, F. Mohammadpanah, Synthesis and structural characterization of phosphinate
coordination polymers with tin(IV) and copper(II), Journal of Molecular Structure (2019), doi: https://
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Synthesis and structural characterization of phosphinate coordination polymers with
tin(IV) and copper(II)
Khodayar Gholivanda, *, Nasrin Fallahb, Ali Asghar Ebrahimi Valmoozia, Akram Gholamia, Michal Dusekc,
Vaclav Eignerc, Mahsa Pooyana Fahimeh Mohammadpanaha
,
aDepartment of Chemistry, Faculty of Basic Sciences, TarbiatModares University, Tehran, Iran.
bDepartment of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran.
cInstitute of Physics ASCR, Na Slovance 2, 182 21 Prague 8, Czech Republic.
Abstract
In this work, we report the synthesis and X–ray characterization of diphenylphosphinic acid (L)
(redetermination at 100 K), and its two polymeric phosphinate complexes; [(C6H5)2P(O)OSn(C6H5)3]n (C1) and
[Cu(O2PPh2)2]n (C2), resulted from the bidentate coordinatioan of L. Sn(IV) centers in C1 are five-coordinate in
a distorted trigonal bipyramidal geometry. One dimensional coordination chains of C2 are made by double-
bridging ligands between the copper atoms, surrounded with four P-O in a square planar polyhedron. Structural
characterization of the complexes revealed that M-O bonds are responsible for the assembly of the primary
structural motifs in both the complexes while C–H…π and H…H interactions are effective in organizing these
molecules into extended 3D architectures. The quantitative mapping of interactions was also analyzed using
Hirshfeld surface analysis. With respect to the 31PNMR spectra, there are probably fast transformations in the
solution and different types of coordinated and dissociated species are in balance, consistent with the optimized
structures in the solvent and gas phases.
Keywords: Coordination polymer; Phosphinate; Tin(IV); Copper(II); Intermolecular interactions; Hirshfeld
surface analysis.
1. Introduction
In the last decades, the structural diversity of coordination polymers, as this type of materials
makes them attractive for a variety of potential applications that contain optics, small-
molecule storage, and separation science [1-3]. The apparently limitless combination of metal
ions and organic molecules have created a massive array of structural topologies. In order to
identify the full potential of this exciting field, extensions to a variety of organic molecules
have been explored. Phosphonates are one of the things that have attracted a lot of attention.
1

phosphonates have been used for vigorous crystalline materials that are capable of being
characterized by single-crystal X-ray diffraction. Challenges with phosphonates, as a class of
organic molecules, historically have included quick precipitation due to the formation of
densely layered phases which frequently form intractable solids that are problematic to
characterize [4]. Additionally, compared to other organic compounds such as carboxylates,
phosphonates offer much more bridging modes to metals, making the formation of structural
motifs for the design of specific materials less predictable. Our interest lies in exploring
−
phosphinates (Ar2PO2 ) as less conventional organic linker molecules that could be useful in
the synthesis of coordination polymers.
In this research, diphenylphosphinic acid (L) has been used in the reaction with SnPh3Cl and
Cu(NO3)2, 3H2O. This ligand bears the close resemblance to Benzoic acid, and it seems
interesting to compare the pattern and strength of hydrogen bonding and to study the packing
in these two structures. Crystal structures of many complexes of carboxylate ligands with tin
and copper compounds have been reported, and in some cases, their anticancer and
antibacterial properties have been investigated [5-9]. It is expected that by replacing these
ligands with phosphates, new and different structures are obtained which can affect the
properties and activities of the complex
.
In this regard, structural studies of ligand L and two new coordination polymers with the
formula [(C6H5)2P(O)OSn(C6H5)3]n (C1) and [Cu(O2PPh2)2]n (C2) in the solid form were
carried out using crystallography and the main noncovalent intermolecular interactions were
elucidated by Hirshfeld surface analysis. The chemical behavior and stability of C1 and C2,
in comparison with other synthetized complexes, were investigated.
2. Experimental
2.1. Chemicals and Characterizations
2

Triphenyltin chloride and copper (II) nitrate trihydrate used in this study were purchased
from Merck, and diphenylphosphinic chloride (98%) from Acros Organics chemical
company and used without further purification. Solvents were purified and dried following
the standard procedures. Melting point was obtained with an Electrothermal instrument.
Infrared spectra were recorded in KBr discs in the region 4000–400 cm−1 on a Thermo
Nicolet NEXUS 870 FT-IR spectrometer. The FT-Raman spectrum (in the range 3600-100
cm-1) was measured on a NICOLET 960-ESP FT-RAMAN spectrometer equipped with a
liquid nitrogen cooled germanium detector and a Diode-pumped solid state laser (emitting
radiation at a wavelength of 1064 nm). The spectrum was recorded at a resolution of 2 cm-1.
1
NMR spectra were recorded on a Bruker Avance DRX500 spectrometer. H chemical shifts
was measured relative to internal TMS. 31P and 119Sn chemical shifts were determined
relative to 85% H3PO4 and Sn(CH3)4 as external standards, respectively.
X-ray data were collected on a Bruker APEX II CCD area detector [10] with graphite
monochromated Mo Ka radiation (λ = 0.71073 Å). The structure was refined with SHELXL
97 [11] by full-matrix leastsquares on F2. The positions of hydrogen atoms were obtained
from the difference Fourier map. The CIF files have been deposited with the CCDC and have
been given the deposition numbers 1861944, 1846819 and 1835509 for L, C1 and C2,
respectively. Crystal data and experimental details of the structure determination for
compound L, C1 and C2 are listed in Table 1 of Supporting Information
2.2. Synthesis of ligand
(C6H5)2P(O)OH (L)
Diphenylphosphinic acid was synthesized by the reaction of 2 mmol (0.473g) of
(C6H5)2P(O)Cl and 2 mmol (0.04g) of H2O in CH2Cl2 at room temperature. After stirring for
4 h, the solvent was evaporated, and the residue was washed with cold water and dried. A
white solid resulted in a yield of 90%. Suitable single crystals of L were obtained by a slow
3

evaporation method using methanol/ dichloromethane solvents mixture. Physical and
spectroscopic data of L are presented below. (C6H5)2P(O)OH (L). Yield: 90%; m.p. 194-
196 C, Selected IR data (KBr, cm-1):3429 s (υO-H), 1639 s (υC=C), 1433 s (υP-C), 1184 s
(υP=O), 1120 s, 968 s. Selected Raman data: 3352, 1593, 1307, 1273, 202. 31P NMR (CDCl3,
1
31
ppm): δ= 24.2. H NMR (DMSO-d6, ppm): δ= 7.47 (m, 6H, 2Ph), 7.71 (m, 4H, 2Ph). P
NMR (DMSO-d6, ppm): δ= 23.4.
2.3. Synthesis of complexes
[(C6H5)2P(O)OSn(C6H5)3]n (C1)
A solution of triphenyl tin chloride (0.038 g, 0.01 mmol) in 10 ml chloroform was added to
the 10 ml solution of L (0.022 g, 0.01 mmol) in chloroform. The resulting mixture was stirred
at room temperature for 2 days. Single crystals of C1 were obtained by slow evaporation of
the solvents. Yield: 86%; m.p. 225-227°C, Selected IR data (KBr, cm-1): 3058 m,1652 m
(υC=C), 1427 m (υP-C), 1128 s (υP=O), Selected Raman data: 3357, 1593, 1342, 1290, 123,
1H NMR (CDCl3, ppm): δ= 7.45 (m, 12H, 2Ph+Ph3Sn), 7.70 (m, 6H, O-Ph3Sn), 7.80 (m, 4H,
2Ph). 31P NMR (CDCl3, ppm): δ=24.4, 33.4.
[Cu(O2PPh2)2]n, (C2)
To a methanolic solution of Cu(NO3)3 .3H2O (1.0 mmol in 10 ml methanol), a solution of L
(1.0 mmol in 10 ml acetonitrile) was added under stirring. The stirring was continued for 2
days. Single crystals of C2 were obtained by slow evaporation of the solvents. Single crystals
were filtered, washed with n-hexane and dried. Yield: 78%; m.p. 308-310°C, Selected IR
data (KBr, cm-1): 1437 m (υP-C), 1128 s (υP=O), 1051 s, 692, Selected Raman data: 3097,
1
31
1595, 1383, 1383, 1298, 1219, 166. H NMR (DMSO-d6, ppm): δ= 7.35-7.64 (m, 2Ph). P
NMR (DMSO-d6, ppm): δ= 23.2, 34.6.
4

Changing the stoichiometric ratio to 1: 0.5 (ligand: metal) also leads to the formation of the
same complexes. The synthesis pathway of compounds L, C1 and C2 was represented in
Scheme 1
Ph
Sn
Ph
P
O
O
O
n
3
Ph
Ph
Ph
O
P
H2O
O
P
OH
CH2Cl2
Ph
Ph
Ph
Ph
Cl
Ph
Ph
P
O
O
O
Cu
Cu
O
O
O
n
P
Ph
Ph
Scheme 1. Synthesis pathway of L, C1 and C2.
Table 1 Single crystal data collection and refinement for L, C1 and C2
.
Parameters
L
C1
C2
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
space group
C12H11O2P
218.18
C30H25O2PSn
567.16
C24H20Cu1O4P2
497.9
100(2)
100(2)
120
0.71073
Monoclinic
P21/c
0.71073
Monoclinic
P21/n
0.71073
Monoclinic
C12/c1
a (Å)
b (Å)
c (Å)
α (°)
β (°)
γ (°)
11.4612(10)
5.9559(5)
15.6442(13)
90
100.2093(16)
90
13.7991(4)
12.3203(4)
14.7297(5)
90
96.8640(10)
90
16.5181(8)
5.0529(3)
25.4454(13)
90
96.231(4)
90
V (Å3)
1050.99(15)
4, 1.379
2486.23(14)
4, 1.515
2111.2(2)
4, 1.566
Z, Calculated density (Mg.m-3)
Absorption coefficient (mm-1)
F(000)
0.236
1.117
1.219
456
1144
1020.0
Crystal size (mm)
0.21×0.18×0.17
1.81-29.00
0.30×0.22×0.20
1.91-30.00
0.339×0.131×0.051
3.85-29.47
θ range for data collection (°)
Limiting indices
-15<=h<=15
-8<=k<=8
-21<=l<=21
-19<=h<=19
-17<=k<=17
-20<=l<=2
-20<=h<=21
-6<=k<=6
-30<=l<=33
Reflections collected / unique
Completeness to theta
12304./.2793 [R(int)=0.0335]
100.0 %
31919./.7243 [R(int) =0.0283]
100.0 %
12362./.2640 [R(int) =0.0265]
98%
Absorption correction
Semi-empirical
equivalents
from Semi-empirical
from analytical
equivalents
Max.andmin.transmission
Refinement method
0.961 and 0.952
0.807.and.0.730
0.942 and 0.804
Full-matrix least-squares on F2
Full-matrix least-squares on F2
Full-matrix least-squares on F2
5

Data/restraints/parameters
Goodness-of-fit on F2
Final R indices
2793 / 0 / 140
7243 / 0 / 307
2640 / 0 / 108
1.041
1.001
2.02
R1=0.0338, wR2 = 0.0924
R1=.0.0438, wR2= 0.1000
0.504 and -0.344
R1=0.0201, wR2 = 0.0470
R1= 0.0258, wR2= 0.0493
0.419 and -0.315
R1= 0.0432, wR2 = 0.1270
R1= 0.0530, wR2= 0.1314
0.56 and -0.58
R indices (all data)
Largest diff. peak and hole
(e.Å-3)
2.4.Computational details
The computations were performed with the Gaussian 09 set of programs [12]. Full
optimization of the molecular geometry of L, C1 and C2 has been made .The theoretical
studies have been performed by density functional methods: B3LYP, which is the widely
used three parameter hybrid functional [13]. We employed the LanL2DZ effective core
potential and basis set for tin and copper [14] and the 6-311G(d) basis set for the remaining
atoms(C, H, O and P) of C1 and C2
3 Results and discussion
3.1 Spectroscopic studies
The spectrum of L shows a broad band centered around 3429 cm–1 assignable to υ−str(O–H)
vibration, whereas in C1 and C2, this signal is completely removed, indicating the connection
of oxygen to the metal. The P=O stretching vibrations were observed at 1184 and 1120 cm-1
in L which shift to 1128 and 1062 cm-1in C1 and 1128 and 1051cm-1 in C2.
FT-Raman vibrational patterns have very slight variations compared to FT-IR. The P=O
stretching vibrations were observed at 1307 and 1273 cm-1 in L while shift to 1342 and 1290
cm-1 in C1 and 1298 and 1219 cm-1 in C2. FT-IR and FT-Raman vibrational patterns of L, C1
and C2 are presented in Figure S1 and S2 of Supporting Information.
According to experimental section, the integrated intensities of 1H NMR signals of the ligand
L correspond to its structural formula; 6H in 7.47 ppm refers to ortho and para position, and
31
4H in 7.71 ppm refers to meta position. In P NMR, the chemical shift is affected by the
solvent, giving δ = 24.2 ppm in CDCl3 and δ = 23.4 ppm in DMSO.
6

1
The integrated intensities of H NMR signals of the complex C1 correspond to its structural
formula (1:1, mole ratio of ligand to tin reactant compound). The peak of 119Sn NMR is
appeared at -61 ppm, falling in the range of four-coordinate tin(IV) compounds. It seems that
the binding of ligand is apparently different in the solution and in the crystal state and the
ligand functions as monodentate. Similar to what was mentioned earlier about that
phosphorus-based tin complexes [15-18], there are probably fast transactions in the solution
and different types of five-coordinate and four-coordinate tin are in balance. In comparison
with the ligand, 31PNMR spectrum of the complex C1 shows two peaks: one with the
chemical displacement similar to the free ligand (24.4 ppm) and the other with an
approximate difference of 9 ppm (33.4 ppm). Obtaining more information about these types
31
requires the study of P NMR at various temperatures, which, unfortunately, was not easily
possible.
31P NMR spectrum of the complex C2 shows also two peaks: one with the chemical
displacement similar to the free ligand (23.2 ppm) and the other with an approximate
difference of 11 ppm (34.6 ppm).
For more accurate studies, computational methods were used to interpret the data. A fragment
of crystal structure C1 and C2 complexes, including two metal centers and three bridging
ligands was extracted from X-ray atomic coordinates and fully optimized in the solvent and
gas phases using the relativistic effective core potential standard basis set LANL2DZ for
metal atoms (Sn and Cu) and 6-311G(d) for the other atoms. The solvents used in the
calculations include chloroform solvent for C1 and DMSO solvent for C2 (exactly the same
conditions used in NMR spectra).
Interestingly, the optimized structure of the C1 complex confirms the proposed four-
coordinate type in solution (Ph2P(O)O-SnPh3), and it shows two different Sn-O interactions:
2.142 and 2.112 Å (in covalent range) and 2.269 and 2.325 Å (in coordination range) in the
7

chloroform solvent and gas phases respectively (Figures 1 and S3 of Supporting
Information).
Similarly for C2, two different Cu-O interactions are observed (Figures 1 and S3 of
Supporting Information). Interactions in covalent range (1.939 and 1.914Å) and two
interactions within the coordinated range (2.067 and 1.976Å), in the DMSO solvent and gas
phases respectively.
C1
C2
Fig. 1. Optimized structure of a fragment of coordination polymer C1 and C2 in solvent phase.
3.2 Description of Crystal Structures
All three compounds L, C1 and C2 crystallized in a monoclinic crystal system with P21/c,
P21/n and C2/c space group, respectively (Table 1). Selected bond lengths and angles are
listed in Table 2 and hydrogen bonding data in Table 3.
Table 2. Selected bond distances (Å) and angles (°) for L, C1, and C2
Compound Bond length (Å) Bond angles(°)
.
8

P(1)-O(1)
P(1)-O(2)
P(1)-C(1)
P(1)-C(7)
1.505(10)
1.550(10)
1.794(13)
1.798(13)
O(1)-P(1)-O(2)
O(1)-P(1)-C(1)
O(2)-P(1)-C(1)
O(1)-P(1)-C(7)
O(2)-P(1)-C(7)
C(1)-P(1)-C(7)
116.54(6)
110.43(6)
102.92(6)
111.01(6)
107.33(6)
108.05(6)
L
Sn(1)-C(1)
Sn(1)-C(7)
Sn(1)-C(13)
Sn(1)-O(2)#1
Sn(1)-O(1)
P(1)-O(2)
P(1)-O(1)
P(1)-C(19)
P(1)-C(25)
2.122(14)
2.122(14)
2.135(14)
2.225(10)
2.238(10)
1.514(10)
1.516(10)
1.803(14)
1.810(15)
O(2)#1-Sn(1)-O(1)
C(1)-Sn(1)-C(7)
C(1)-Sn(1)-C(13)
C(7)-Sn(1)-C(13)
C(1)-Sn(1)-O(2)#1
C(7)-Sn(1)-O(2)#1
C(13)-Sn(1)-O(2)#1
C(1)-Sn(1)-O(1)
C(7)-Sn(1)-O(1)
C(13)-Sn(1)-O(1)
174.57(4)
124.31(6)
119.38(6)
116.25(5)
83.52(5)
92.32(5)
92.22(5)
91.09(5)
91.32(5)
89.79(5)
C1
Cu(1)-O(1)
Cu(1)-O(1)
Cu(1)-O(2)
Cu(1)-O(2)
P(1)-O(1)
P(1)-O(2)
P(1)-C(1)a
P(1)-C(1)
1.925(16)
1.925(16)
1.919(16)
1.919(16)
1.505(18)
1.515(16)
1.827(5)
1.783(5)
1.829(3)
1.781(3)
O(1)-Cu(1)-O(1)
O(1)-Cu(1)-O(2)
O(1)-Cu(1)-O(2)
O(1)-Cu(1)-O(2)
O(1)-Cu(1)-O(2)
O(2)-Cu(1)-O(2)
180.0(5)
88.83(7)
91.17(7)
91.17(7)
88.83(7)
180.0(5)
C2
P(1)-C(1)c
P(1)-C(1)d
3.2.1 Crystal structure of ligand L
Previously, the crystal structure of diphenylphosphinic acid (L) reported at different
temperatures [19-22], and in this study, the crystal structure of L has been determined at 100
°K. Crystal data for the diphenylphosphonic acid in different temperature are listed in Table
S1 of Supporting Information. The important point is that temperature variations do not have
much effect on the structure, and in all literature diphenylphosphonic acid crystallized in a
monoclinic crystal system with P21/c space group (Table S1).
In this study, the structure of diphenylphosphonic acid was investigated in a different
interpretation. The geometry of phosphorus is tetrahedral and the lengths of P-O bonds are
1.505(10) and 1.550(10) Å respectively. O-H groups engage in intermolecular hydrogen bond
with the adjacent P=O unit and create a chain along b-axis. Moreover, the phosphoryl
oxygen, in another hydrogen interaction, is involved with phenyl ring, resulting in the 2D
aggregation of molecules. Finally, weak bonds C5…C5 (3.337(3) Å) develop a crystal
network in the third dimension (a-axis) (The structures of L are shown in Figures 2 and 3). In
9

comparison with hydrogen bonding pattern of L, benzoic acid and its derivatives are present
as binary accumulations and intermolecular hydrogen bonds result in the formation of six
membered rings. (Figure 4).
Table 3. Hydrogen bond data for compound L (distances in Å and angles in °).
D-H...A
d(D-H)
0.95
d(H...A)
1.53
d(D...A)
<(DHA)
174
Symm. code
O(2)-H(2O)...O(1)#1
C(10)-H(10A)…O(1)
2.478(14)
3.395(19)
#1 -x+1,y-1/2,-z+1/2
x+1,y-3/2,-z+2
0.95
2.61
140
Fig. 2. Molecule of L with displacement ellipsoids at 50% probability.
(a)
10

(b)
Fig. 3 1D polymeric chains along c-axis, showing intermolecular hydrogen bonds (a), and crystal packing
fragment of L (b).
O
H
O
O
H
O
Fig. 4 Hydrogen bonding pattern in the structure of benzoic acid and its derivatives.
3.2.2 Crystal structure of complex C1
In crystal structure of C1, tin centers are connected by bidentate ligand L, creating chains
along the b-axis. The distance between the two centers of Sn is 6.341(19) Å. Sn(IV) centers
have distorted trigonal bipyramidal coordination geometry with oxygen atoms at the axial
positions and phenyl groups on equatorial planes. The trans angle around the tin atom is
174.57(4) º and the angles of C—Sn—C in belt position are 116.25(5)-124.31(6) º. The
different bond lengths of Sn—O [2.225(10) and 2.238(10) Å] and also different angles of P—
O—Sn (145.79(6) and 141.98(6) º, respectively) show that the bridging ligand is
asymmetrically coordinated to metal centers. It seems that a more suitable interaction angle
11

has resulted in a better orbital overlap and a shorter bond. Beside, elongation of P—O bond in
C1 is simply attributed to the polarization of phosphoryl in the electrostatic field of Sn(IV).
(a)
(b)
Fig. 5 Molecule of C1 with displacement ellipsoids drawn at 50% probability level (a), A chain of molecules of
C1 bridged by tin. Phenyl groups on the ligand have been omitted for clarity (b).
Fig. 6 A two-dimensional zigzag polymeric network of C1 formed by CH–π intermolecular interactions.
12

As mentioned earlier, coordination interactions of Sn—O play an essential role in the
formation and stability of supramolecular C1. Adjacent coordination polymers are connected
to two-dimensional networks (Figures 5-6) through CH…π interactions between the phenyl
rings of ligands [C10–H10…Cg (Cg: the center of gravity of ligand phenyl ring): θ=161.36°,
d(C23…Cg)=3.469(7) Å, d(H23…Cg)=2.535 Å]. These layers are also stabilized by weaker
interactions H…H.
3.2.3 Crystal structure of complex C2
The structure of C2 comprises [010] chain motifs in which Cu atoms separated 5.053 Å are
linked by two bridging phosphinate ligands. Copper has a square planar coordination with
four O atoms each from four different phosphinates. The Cu—O bond lengths are in the
range 1.919(16) – 1.925(16) Å, showing that the bridging ligand is asymmetrically
coordinated to metal centers. The trans-O—Cu—O bond angles are 180.0(5), while the cis-
O—Cu—O angles range from 88.83(7) to 91.17(7). Selected list of bond lengths and angles
involving the Cu(II) centers is given in Table 2.
Adjacent 1D coordination polymers are connected through the CH…π interaction between
the phenyl rings of ligands [C3d–H1…Cg and C4d–H1…Cg (Cg: the center of gravity of
ligand phenyl ring): d(C3d–H1…Cg)=3.328 Å, d(C4d–H1…Cg)=3.626 Å]. As a result of
these interactions, two-dimensional networks are formed in the structure. Weaker interactions
of H…H stabilize the structure by connecting the two-dimensional layers into a 3D network.
(The structures of C2 are presented in Figures 7 and 8).
13

(a)
(b)
Fig. 7 (a) A molecule of C2 with displacement ellipsoids drawn at the 50% probability level, (b) The
coordination chain of C2 extended along b.
Fig. 8 CH–π interactions in C2, connecting the coordination chains in a 2D network.
3.3 Hirsfeld surface analysis
The Hirshfeld surfaces and associated fingerprint plots were performed using Crystal
Explorer 3.1 [23]. The derivation of Hirshfeld surfaces and their breakdown of the
corresponding 2D fingerprint plots [24] provide a convenient mean of quantifying the
interactions within the crystal structures, revealing significant similarities and differences
14

between related structures. The sharp spikes of the fingerprint plots represent their
importance in the formation of a given crystal structure and also provide a platform for the
evaluation of the contribution of different atom....atom contacts which contribute to the
packing. It should be noted that after reading CIF into the Crystal Explorer program, all bond
lengths to hydrogen are automatically modified to typical standard neutron values (C-H =
1.083 Å, N-H = 1.009 Å and O-H = 0.983 Å) [25]. Figure 9 shows the Hirshfeld surfaces and
fingerprint plots of the three title compounds L, C1 and C2. Hirshfeld surfaces were
generated using a high (standard) surface resolution. The 3-D dnorm surfaces were mapped by
using a fixed color scale of 0.76 (red) to 2.4 (blue) over dnorm ranges –0.864 to 1.217Å for L,
range –0.777 to 1.392Å for C1, and –0.682 to 1.239Å for C2, respectively. The 2-D
fingerprint plots were displayed by using the standard 0.6-2.8 Å view with the de and di
distance scales displayed on the graph axes. Two sharp spikes in L imply to O⋯H hydrogen
bond, and in C1 and C2 sharp spikes represent Sn...O and Cu...O contacts. According to
Figure 9, the Hirshfeld surfaces of L, C1 and C2 contain relatively large red circles (label
“a”) corresponding H…O=P hydrogen bonds between the hydroxyl and phosphoryl groups
from two adjacent molecules of L, or. Sn...O and Cu...O bonds in C1 and C2. Lighter and
smaller red circles (label “b”) in C2 belong to either CH⋯π contacts.
The Quantitative measures of the Hirshfeld surface for molecules L, C1, and C2 are presented
in Table 4. The lowest Hirshfeld volume and surface area of L indicates that this molecule
has a more crowded environment than the other molecules, and this feature is also apparent in
the fingerprint plot by the compact pattern of this molecule.
The globularity is a quantity measuring the extent the surface area varies from that of a
sphere, being 1.0 for a sphere, the molecule of L has a maximum amount of globularity as a
result of the most convex character of its surface. Also, asphericity is highest for L, which
shows more ablations of these surfaces. According to the Table 4, the largest volume and
15

surface area and the lowest of globularity and asphericity are shown for C1, caused by three
phenyl groups bound to tin.
Table 4. Quantitative measures of Hirshfeld surface for L, C1 and C2.
Compound
Molecular volume (Å3)
surface area (Å2)
Globularity of the surface
Asphericity
0.125
255.17
245.44
0.793
0.718
0.776
L
612.41
485.46
0.022
C1
C2
266.53
258.27
0.113
16

L
C1
C2
Fig. 9 Hirshfeld surfaces mapped with dnorm function and fingerprint plots for L, C1 and C2
The relative contributions of particular intermolecular interactions are presented as a chart in
Figure10. The H⋯H interaction dominates in crystal packing, followed by C⋯H contacts of
CH⋯π interactions. The O⋯H interaction is largest for the L molecule.
17

48.10%
30.40%
17.40% 4.10%
L
C1
C2
63.20%
27%
5.60% 1.90%
2.30%
46.10%
25.40%
9.70% 9.40% 9.40%
0%
20%
H…H
40%
C...H
60%
80%
Sn…O Cu…O
100%
other
O…H
Fig. 10 Relative contribution of various atom…atom contacts contributing towards the crystal packing of the L,
C1 and C2.
4 Conclusions
In summary, we reported the crystal structure of ligand (L) and its coordination polymers
with tin and copper (C1 and C2). The X-ray results reveal that the crystal structure of L is
mainly governed by chains of O-H…O=P hydrogen bonds, which is a different pattern
compared to the similar compound of benzoic acid with H-bonded ring motifs. The
deprotonated ligand functions in a bridging mode in both complexes, generating coordination
chain motifs. In C1 structure, Sn(IV) centers are five-coordinate and have distorted trigonal
bipyramidal geometry while in the case of C2, adjacent copper atoms are double-bridged by
two ligands and the geometry of the copper atom has a square planar configuration. The
metal-contributed chains in C1 and C2 are connected by C–H…π and H…H interactions to
construct the crystal packing networks. The molecular Hirshfeld surface and 2D fingerprint
plots were used for quantitative mapping of these interactions. The chemical behavior of the
complexes in the solution is different from the solid state structures, confirmed by the
calculated in the solvent and gas phase structures. It seems that the binding of the ligand is
different in the soluble state than in the crystal structure; monodentate in the solvent and
18

bidentate in solid-state. Sn NMR spectrum in solution suggests an exchange between
coordination compounds and dissociated species, at ambient temperature.
Acknowledgement
The financial supports of this work was provided by Tarbiat Modares University, Iran
National Science Foundation (INSF) Tehran, Iran and by the Research Branch, Islamic Azad
University, Tehran, Iran. The crystallographic part was supported by the project 18-10438S
of the Czech Science Foundation using instruments of the ASTRA lab established within the
Operation program Prague Competitiveness - project CZ.2.16/3.1.00/24510.
References
[1] A. U. Czaja, N. Trukhan, U. Muller, Industrial applications of metal–organic frameworks,
Chem. Soc. Rev. 38 (2009) 1284– 1293.
[2] H. Furukawa, K. E. Cordova, M. O’Keeffe, O. M. Yaghi, The chemistry and applications
of metal-organic frameworks. Science, 341 (2013). 974.
[3] M. Dincˇa, J. R. Long, Hydrogen Storage in Microporous Metal–Organic Frameworks
with Exposed Metal Sites. Angew. Chem. Int. Ed. 47 (2008) 6766–6779.
[4] G. K. H. Shimizu, R. Vaidhyanathan, J. M. Taylor, Phosphonate and sulfonate metal
organic frameworks, Chem. Soc. Rev. 38 (2009) 1430–1449.
[5] T. S. Basu Baul, D. Dutta, A. Duthie, N. Guchhait, B. G. M. Rocha, M. F. C. Guedes da
Silva, R. B Mokhamatam,.N. Raviprakash, S. K. Manna, New dibutyltin(IV) ladders:
Syntheses, structures and, optimization and evaluation of cytotoxic potential employing
A375 (melanoma) and HCT116 (colon carcinoma) cell lines in vitro, J. Inorg. Biochem.,
166 (2017) 34-48
[6] S. Shahzadi, S. Ali, K. Shahid, M. Yousaf , S. K. Sharma, K. Qanungo, Interaction of Di‐
and Triorganotin(IV) Compounds with Carboxylate Ligand: Synthesis, Spectral
19

Characterization, Semi‐Empirical Study and In Vitro Antimicrobial Activities, J. Chin.
Chem. Soc., 57 (2010) 659-670
[7] D.L. Reger, A. Debreczeni, M.D. Smith, J. Jezierska, A. Ozarowski, Copper(II)
Carboxylate Dimers Prepared from Ligands Designed to Form a Robust π···π Stacking
Synthon: Supramolecular Structures and Molecular Properties, Inorg. Chem., 51 (2012)
1068–1083
[8] A.N. Wein, R. Cordeiro, N. Owens, H. Olivier, K. I. Hardcastle, J. F. Eichler, Synthesis
and characterization of Cu(II) paddlewheel complexes possessing fluorinated carboxylate
ligands, Journal of Fluorine Chemistry, 130(2009) 197-203
[9] T. Aiyelabol, E. Akinkunmi, E. Obuotor, I. Olawuni, D. Isabirye, J. Jordaan, Synthesis
Characterization and Biological Activities of Coordination Compounds of 4-Hydroxy-3-
nitro-2 H -chromen-2-one and Its Aminoethanoic Acid and Pyrrolidine-2-carboxylic Acid
Mixed
Ligand
Complexes,
Bioinorg
Chem
Appl.,
9
(2017)1-9.DOI:
10.1155/2017/6426747
[10] For C1: Bruker, Programs APEX II, version 2.0-1; SAINT, version 7.23A, For C2:
Bruker (2005). APEX2 software package, Bruker AXS Inc., 5465, East Cheryl Parkway,
Madison, WI 5317.
[11] A.D. Becke, Density‐functional thermochemistry. III. The role of exact exchange, J.
Chem. Phys. 98 (1993) 5648-5652.
[12] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G.
Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P.
Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K.
Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai,
T. Vreven, J.A. Montgomery Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E.
20

Brothers, K.N. Kudin, V.N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K.
Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M.
Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R.
Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W.
Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J.
Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman, J.V. Ortiz, J.
Cioslowski, D.J. Fox, Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford CT, 2013.
[13] C.T. Lee, W.T. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785-789.
[14] P.J. Hay, W.R. Wadt, J. Chem. Phys. 82 (1985) 299-310.
[15] K. Gholivand, A. Gholami, S. K. Tizhoush, K. J. Schenk, F. Fadaei, A. Bahrami, Steric
and electronic control over the structural diversity of N-(n-pyridinyl)
diphenylphosphinicamides (n ¼ 2 and 4) as difunctional ligands in triphenyltin(IV)
adducts, RSC Adv, 4.(2014) 44509 44516.
-
[16] K. Gholivand, A. Gholami, A. A. V. Ebrahimi, S. T. Abolghasemi, M. D. Esrafili, F. T.
Fadaei, K. J. Schenk, Triphenyltin(IV) adducts of diphosphoryl ligands: structural,
electronic and energy aspects from X-ray crystallography and theoretical calculations,
RSC Adv., 5 (2015) 17482-17492.
[17] K. Gholivand, A. Gholami, K. J. Schenk, M. D. Esrafili, K. Farshadfar, Supramolecular
assemblies of organotin(IV)diphosphoryl adducts: Insights from X-rays and DFT. RSC
Adv., 5 (2015), 98610-98617.
[18] K. Gholivand, A. A. EbrahimiValmoozi, A. Gholami, M. Dusek, V. Eigner, S.
Abolghasemi, Synthesis, characterization, crystal structures, QSAR study and antibacterial
activities of organotin bisphosphoramidates. J. Organomet. Chem., 806, 15 (2016) 33-44.
[19] D. Fenske, R Mattes, J. Löns, K. F. Tebbe, Die Kristallstruktur von
Diphenylphosphinsaure, Chem. Ber. 106 (1973) 1139-1144
21

[20] G. Siasios and E. R. T. Tiekink, Crystal structure of diphenylphosphinic acid
(redetermination at 173 K), C12H11O2P, Zeitschrift für Kristallographie 209 (1994) 547.
[21] K. A. Lyssenko, G. V. Grintselev-Knyazev, M. Yu. Antipin, Nature of the P–O bond in
diphenylphosphonic acid: experimental charge density and electron localization function
analysis, Mendeleev Commun., 12(4) (2002) 128–130.
[22] W. Gao, B. Shi, Crystal Structure of Diphenylphosphinic Acid, Mol. Cryst. Liq. Cryst.,
623(2015)305–309.
[23] S. K. Wolff, D. J. Grimwood, J. J. McKinnon, M. J. Turner, D. Jayatilaka and M. A.
Spackman, CrystalExplorer, version 3.0; University of Western Australia: Crawley,
Australia, 2012.
[24] M. A. Spackman and J. J. McKinnon, CrystEngComm, 2002, 4, 378
[25] F. H. Allen, O. Kennard, D. G Watson, L. Brammer, A. G. Orpen, R. Taylor, Tables of
Bond Lengths determined by X-Ray and Neutron Diffraction. Part 1. Bond Lengths in
Organic Compounds. Journal of the Chemical Society, Perkin Transactions, 2 (1987) S1-
S19. http://dx.doi.org/10.1039/p298700000s1
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Highlights
ꢀ Synthesis and characterization of a phosphinic acid ligand and its two polymeric
complexes.
ꢀ The structural motifs in the complexes are linked by M—O—P—O—M bonds."
ꢀ The chemical behavior of the complexes in the solution is different from the solid
state structures.

Editor-in-Chief of Journal of Molecular Structure
Dear Prof. Rui Fausto
Wishing you a pleasant time, it is a great honor for me to have the opportunity of writing to you. My co-
authors and I are submitting a revised manuscript entitled: "Synthesis and structural characterization
of phosphinate coordination polymers with tin(IV) and copper(II)", by Khodayar Gholivand, Nasrin
Fallah, Ali Asghar Ebrahimi, Akram Gholami, Michal Dusek, Vaclav Eigner, Mahsa Pooyan, Fahimeh
Mohammadpanah for possible publication in one of the forthcoming volumes of J. Mol. Stru. The
article is original and unpublished and is not being considered for publication elsewhere. I also
confirm that all co-authors are aware of its content, approve its submission, and certify that the
article has not been published previously and is not under consideration for publication
elsewhere. Also, no conflict of interest exists and the authors declare no competing financial interest.
Yours sincerely,
Khodayar Gholivand, Ph.D.
Research Officer
Department of Chemistry-Faculty of Sciences
Tarbiat Modares University, P.O.Box: 14115-175
Phone: +98-21-82884422