Symmetric quaternary phosphonium cation and perchlorate/chlorate anions: Crystal structure, Database study and Hirshfeld surface analysis

Article abstract of DOI:10.1016/j.molstruc.2018.11.037

Two new quaternary phosphonium salts of 1,2-ethandiylbis (triphenylphosphonium) Diperchlorate (I), 1,2-ethandiylbis (triphenylphosphonium) Dichlorate (II) were prepared and used for oxidation of different benzylic alcohols to afford their corresponding ca

Full text of DOI:10.1016/j.molstruc.2018.11.037

Accepted Manuscript
Symmetric quaternary phosphonium cation and perchlorate/chlorate anions: Crystal
structure, database study and Hirshfeld surface analysis
R. Salmasi, A. Salimi, M. Gholizadeh, M. Rahmani, J.C. Garrison
PII:
S0022-2860(18)31347-4
DOI:
https://doi.org/10.1016/j.molstruc.2018.11.037
MOLSTR 25866
Reference:
To appear in: Journal of Molecular Structure
Received Date: 24 August 2018
Revised Date: 9 November 2018
Accepted Date: 10 November 2018
Please cite this article as: R. Salmasi, A. Salimi, M. Gholizadeh, M. Rahmani, J.C. Garrison, Symmetric
quaternary phosphonium cation and perchlorate/chlorate anions: Crystal structure, database study
and Hirshfeld surface analysis, Journal of Molecular Structure (2018), doi: https://doi.org/10.1016/
j.molstruc.2018.11.037.
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ACCEPTED MANUSCRIPT
Symmetric Quaternary Phosphonium Cation and Perchlorate/Chlorate Anions:
Crystal Structure, Database Study and Hirshfeld Surface Analysis
1
1,*
1
1
2
R. Salmasi , A. Salimi , M. Gholizadeh , M. Rahmani , J. C. Garrison
1
Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad 91775-1436, I.R. IRAN
Department of Pharmaceutical Sciences, University of Nebraska Medical Center, 985830. USA
2
Corresponding author e-mail: salimi-a@um.ac.ir
Hirshfeld Surface analysis
Compound I
Compound II

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Symmetric Quaternary Phosphonium Cation and Perchlorate/Chlorate Anions:
Crystal Structure, Database Study and Hirshfeld Surface Analysis
1
1,*
1
1
2
R. Salmasi , A. Salimi , M. Gholizadeh , M. Rahmani , J. C. Garrison
1
Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad 91775-1436, I.R. IRAN
2
Department of Pharmaceutical Sciences, University of Nebraska Medical Center, 985830. USA
Abstract
Two new quaternary phosphonium salts of 1,2-ethandiylbis(triphenylphosphonium)
Diperchlorate (I), 1,2-ethandiylbis(triphenylphosphonium) Dichlorate (II) were prepared and
used for oxidation of different benzylic alcohols to afford their corresponding carbonyl
compounds. These new compounds were characterized by IR, NMR spectroscopy and single
crystal X-ray analysis. The crystal structure and Hirshfield surface analysis of titled
compounds revealed that the change of accompanying anionic moiety can affect the
directional interactions of CHꢀꢀꢀO hydrogen bonds between anionic and cationic units which
lead to various supramolecular aggregations on the crystal packing. In order to exploring the
influence of crystal environment of anionic moieties on the geometry of main symmetric
cationic unit, the relative contribution of various close contacts and 2D fingerprint plots of
title compounds and twenty three analogous structures retrieved from Cambridge Structural
Database (CSD) were investigated through the distortion of tetrahedral coordination
geometry of P center of main cationic unit based on τ indices.
4
Keywords: Quaternary phosphonium salt; Accompaning anions; Crystal structure analysis;
Oxidation agent; Hirshfeld surface analysis.
1

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Introduction
The quaternary phosphonium cations which can be able to transfer the anionic reactants from
aqueous media into organic media (as phase transfer catalysis) have received great interest
1
-3
with their structures and properties as room-temperature ionic liquids. The results of studies
have shown to increase the rate of the organic reaction by enhancing the reactivity of the
ionic species and increasing the encounter rate with the organic substrate. The chlorate and
perchlorate species are strong oxidant, and their salts such as some phosphonium chlorates
4
-10
and perchlorates compounds are frequently used to oxidize a variety of functional groups;
so, the application of chlorate and perchlorate-based compounds in organic synthesis has
1
1-13
been extensively reviewed.
reactions in organic chemistry and up to the present moment a variety of reagents has been
introduced for this subject such as ionic liquids in terms of
methoxymethyltriphenylphosphonium halochromates, triphenylphosphine surface-modified
Oxidation of benzylic alcohols is one of the significant
1
4
1
5
16
iron oxide nanoparticles, benzyltriphenylphosphonium chlorate. Although a wide variety
of methods have been reported for oxidation of benzylic alcohols to the corresponding
carbonyl compounds, some of them encounter disadvantages such as use of expensive
oxidizing agents, low yields of the oxidized species and causing side products and harsh
condition reaction. Eventually of these characteristics, introduce of methods and oxidizing
agents for such functional group transformations is still in demand.
As part of our current study concerning the structural characteristics of bis
triphenylphosphonium moiety, we have synthesized and characterized two new oxidation
agents as 1,1'-(1,2-ethanediyl)bis[1,1,1-triphenyl]phosphonium diperchlorate (I) and 1,1'-
(1,2-ethanediyl)bis[1,1,1-triphenyl]phosphonium dichlorate (II). The results of oxidation
reactions by title compounds are very satisfactory and showed that these new reagents have
valuable additions in comparison to existing oxidizing agents. We described the crystal
2

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structure of titled compounds as well as the intermolecular interactions between
bistriphenylphosphonium cationic and perchlorate and chlorate anionic moieties by Hirshfeld
surface analysis. In fact, Hirshfeld surface analysis represents unique quantitative and
qualitative tools to decode intermolecular interactions and offer a facile way of obtaining
1
7-24
information from comparable structures.
In order to evaluate the role of various anionic
moieties on the packing of cationic unit, the CSD search was performed for the analogous
structures. The relative contribution of different intermolecular contacts of the main unit in
these structures was investigated by Hirshfeld surfaces over a dnorm and the 2D fingerprint
plots.
Results and Discussion
Crystal structure description
-
The asymmetric unit of compound I contains the 1:2 ratio of cationic unit and discrete ClO4
anionic unit. One of perchlorate anions was disordered over two positions with the occupancy
ratio of 0.9 to 0.1 in which the moiety with major site occupation factor was considered in the
structural investigations. The asymmetric unit of II contains half of cationic unit and one
-
ClO anionic unit. The bond angles around the P atoms are in the range of 107.8(2)˚ to
3
1
12.1(3)˚ in compound I and 107.6(2)˚ to 111.3(2)˚ in compound II. The torsion angles of P-
C-C-P for dications is -134.35(13)˚ and 131.78(12). The geometry of dications (bond lengths
2
5, 26
and angles) are general and comparable with our previously reported periodate salt.
The
arrangement of the phenyl rings in the –PPh moieties diverged from planarity with the mean
3
deviations of 0.184 and 0.122 Å for the phenyl rings around P and 0.070 and 0.122 Å for the
1
phenyl rings attached to P of compounds I and II, respectively.
2
The 3D supramolecular networks of these compounds are dominated by the variety of C-
HꢀꢀꢀO and C-Hꢀꢀꢀπ hydrogen bonds. According to the supramolecular aggregations of these
structures, the π-system of benzene rings of cationic unit and also oxygen atoms of anionic
3

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units play key role in packing them in all directions. Changing accompanying anionic moiety
effects directional interactions between anionic and cationic units and therefore different
supramolecular aggregation can be observed for these structures, including weak hydrogen
bonding C−HꢀꢀꢀO and C−HꢀꢀꢀCl which their structural parameters were listed in Table 1.
Obviously, one of the main interactions in these compounds, which can play the important
role in the crystal packing of title structures, is C−HꢀꢀꢀO interaction which is illustrated in c
and d parts of Figures 1 and 2.
The results showed that the special direction of aromatic rings around the P centers in I and II
prepare the suitable arrangement of cationic units alongside each other through the formation
of C-Hꢀꢀꢀπ interactions of benzene rings which illustrated in b part of Figures 1 and 2,
respectively. Geometrical parameters of these interactions were presented in Table 2. One of
three phenyl rings around the P-center interestingly engaged in πꢀꢀꢀπ intramolecular
interactions while the other phenyl rings contribute in formation of effective C−Hꢀꢀꢀπ
2
7-32
interactions. Regarding to the recent studies of πꢀꢀꢀπ stacking interactions
, the
geometrical parameters of aromatic phenyl interactions were distance of ring centroids as C-
C distances of 3.795 Å and 4.246 Å and the angles between two ring planes 13.90° and
1
7.31° and also normal distance of centroid to ring planes as P–CC distances of 3.535 Å and
.573 Å for compounds I and II, respectively.
3
Hirshfeld surface analysis
2+
Intermolecular interactions of the main unit functionality of the [EDBTPP] cation in the
different crystalline environments of title compounds were mapped by the Hirshfeld surface
analysis which is an extremely useful method for visualizing molecular contacts. The
3
3
Hirshfeld surfaces were generated using Crystal Explorer 3.1
based upon the X-ray
structure analysis. Since, the internal consistency is important for comparison of
4

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intermolecular contacts in different structures, the bond lengths of C−H, O−H and N−H have
been normalized to standard neutron diffraction values which equals to 1.083, 0.983 and
1
.009 Å, respectively. The red and blue colors in the Hirshfeld surface, mapped with dnorm,
are associated with distances that are shorter and longer than van der Waals intermolecular
contacts, respectively. Similarities and differences in behavior of hydrogen bond donor and
acceptor was compared based on careful evaluation of the normalized contact distance (dnorm
-0.283–1.367 Å) , and the decomposed fingerprint plots for close contacts of each unit have
been prepared from compounds I, and II (Figures 3 and 4).
)
(
The comparison of these surfaces, despite differences in anionic fragments and different
crystal structures, reveals that there is similarity between the treatment of the hydrogen bond
acceptor and donor groups of these compounds. Figure 3 shows the percentage of
participation of close contact between different atoms of the main unit, with the decomposed
2
D fingerprint plots. Brief overview at the decomposed 2D fingerprint plots of title
compounds, shows a considerable contribution of OꢀꢀꢀH/HꢀꢀꢀO, CꢀꢀꢀH/HꢀꢀꢀC, and HꢀꢀꢀH
contacts in these compounds. Considering species of cationic moiety, investigated, the less
contribution of other contacts such as CꢀꢀꢀO, CꢀꢀꢀC, CꢀꢀꢀCl, and ClꢀꢀꢀH. One of the main
interactions in these compounds, which play an important role in their stacked structures, is
C−HꢀꢀꢀO interactions, which are shown as OꢀꢀꢀH/HꢀꢀꢀO contacts in the decomposed 2D
fingerprint plots. Most parts of red circular depressions with a range of different intensity, on
these dnorm surfaces, are due to the C−HꢀꢀꢀO interactions, which created between oxygen
atoms of anionic moiety and hydrogen atoms of main unit. These contacts, with a range of
different energies, appear as a sharp spike in the 2D fingerprint plots with points with
minimum di + de values equals to 2.2 and 2.1 Å, respectively. The percentage of contribution
of OꢀꢀꢀH/HꢀꢀꢀO contacts is 28.2% for compound I, and 21.3% for compound II of the total
surfaces, which the more the proportion of OꢀꢀꢀH contacts in compound I revealed because of
5

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-
the presence of more oxygen atoms in the anionic moiety ClO .
4
On the other hand, the C−Hꢀꢀꢀπ interactions can be mentioned as one of the dominant
interactions of these structures that are shown as CꢀꢀꢀH/HꢀꢀꢀC contacts and includes 25%, and
3
0.4% of the Hirshfeld surfaces for compounds I and II, respectively. The significant
contribution of these surfaces is related to HꢀꢀꢀH interactions, which covers a vast range of
surfaces in the center of the plots with proportions of 41.3% and 43.6% for compounds I and
II, respectively. These contacts illustrated as sharp peaks with minimum di + de values in the
2
D fingerprint plots (Figure 4). As it was previously mentioned about πꢀꢀꢀπ stacking
interactions in titled compounds, the low contribution of CꢀꢀꢀC contact was expected with
proportions of 2.7% and 0.8% for I and II, in which minimum di + de values equals to 3.6
and 3.5 Å, respectively.
Shape index and curvedness surfaces of cationic units as an interesting features of Hirshfeld
2+
surface analysis were prepared to compare the arrangement of [EDBTPP] moiety against
-
-
ClO and ClO anionic units in compounds I and II, respectively (Fig. S1). Features on these
4
3
surfaces indicate to the intermolecular contact areas by identical pattern with various colors
which show the complementarity between constituent moieties in the title molecules. This
complementarity helps to better understand the packing arrangement of ionic moieties in the
crystal structures.
Database study
In order to evaluate the performance of the main unit on the relative contribution of different
intermolecular contacts to the Hirshfeld surfaces and its impact on the packing of the similar
3
4
structures, the Cambridge Structural Database (CSD)
search was performed on the
2
+
compounds including the [EDBTPP] cationic unit, which led to 23 cases. In this regard, the
6

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Hirshfeld surfaces of the main unit over a dnorm and the 2D fingerprint plots have been also
studied, that represented in Figure 5 and Table 3.
The comparison of the relative contribution of various contacts shows that CꢀꢀꢀC, CꢀꢀꢀH/HꢀꢀꢀC,
and HꢀꢀꢀH contacts exist in all of them, so that the contribution of CꢀꢀꢀH/HꢀꢀꢀC, and HꢀꢀꢀH
contacts, apart from the role of anionic moiety, are significant. Furthermore, the highest
contribution in all of the structures is relevant to the HꢀꢀꢀH contacts, which is changed from
1
8.9 to 78.3 Å. Indeed, CꢀꢀꢀH/HꢀꢀꢀC contacts which assigned to C-Hꢀꢀꢀπ interaction have
variety of contributions to the Hirshfeld surface from 11.2% to 30.7% in DUGKOG and
AZUZIG refcodes, respectively. In these cases, the smallest contribution of CꢀꢀꢀC contacts
demonstrating little effect of πꢀꢀꢀπ interactions in crystal packing of these structures.
Analysis of the crystalline environment of these structures demonstrates little effect of πꢀꢀꢀπ
interactions in their crystal packing because of special direction of aromatic rings around the
phosphor centers which confirmed by the little contribution of CꢀꢀꢀC contacts in the
decomposed Hirshfeld surfaces. In this regard, relationship between the relative contribution
of various close contacts in the crystal packing and the amounts of τ parameter for P centers
4
of main unit were investigated and also their decomposed 2D fingerprint plots analyzed
separately. The geometry index for four-coordinated complex as τ parameter was developed
4
by Yang et al. to distinguish whether the geometry of the coordination center is square planar
or tetrahedral. In this equation, α and β are the two largest θ angles in the four-coordinate
3
5
species.
The results indicated to the special direction of aromatic rings around the P centers, which
can decrease the possibility of formation the effective πꢀꢀꢀπ interactions between the aromatic
moieties. However, C−Hꢀꢀꢀπ interactions based on π-system of benzene rings as well as the
7

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2
+
other interaction, such as HꢀꢀꢀH and ClꢀꢀꢀH become dominant in the stability of [EDBTPP]
cationic unit in their crystal structures.
Oxidation reagent activity
The reagent of I as a white powder which is prepared by addition of an aqueous solution of
8
NaClO to an aqueous solution of 1,2-Ethandiylbis(triphenylphosphonium) dibromide at
4
room temperature. The white precipitate of I was filtered and dried in vacuum (95% yield,
m.p:258-260°C). This powder recrystallized in chloroform to obtain suitable single crystals
which are shown in Figure S2 and it could be stored for several months without losing its
oxidation ability and so it has high efficiency. Similarly, the reagent of II is a white powder
which is prepared by addition of an aqueous solution of NaClO to an aqueous solution of
3
8
1
,2-Ethandiylbis(triphenylphosphonium) dibromide
at room temperature. (96% yield,
m.p:184-186°C). After one week from the suspension formation, the salt crystals of 1,2-
ethandiylbis(triphenylphosphonium) Dichlorate (II) are obtained and separated through
filtration (Fig. S3). This compound was stable for several months at room temperature
without loss of its activity (as bench top reagent). More ever the similar combinations, such
1
6
as benzyltriphenylphosphonium chlorate , which has already been reported show the
stability of this compound. Benzylic alcohols were converted to their corresponding carbonyl
compounds with I and II in good to high yields (scheme 1).
Sodium perchlorate and sodium chlorate are cheap and stable oxidizing agents. These are
insoluble in non-aqueous solutions. Title reagents are quite soluble in DMF, DMSO and
insoluble in nonpolar solvents such as carbon tetrachloride, n-hexane and diethyl ether. The
effect of various solvents such as DMF, DCM, acetonitrile on the oxidation of 4-chlorobenzyl
alcohol with I and II was examined (Table 4). DMF for I and II were found to be the best
solvent. The oxidation of benzylic alcohols to their corresponding carbonyl compounds in
8

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presence of different oxidants (I and II) were performed in good to excellent yields at the
reflux condition (Table S1). All of the products were identified by the comparison of their
5
, 7
physical and spectral data with those of authentic sample (melting and boiling point).
Different benzyl alcohols were subjected to oxidations with I and II in DMF. This oxidation
takes place under mild and quantitative conditions giving in good to excellent yields.
The results showed that the reactivity of oxidant I is more than II. On the other hand the
oxidation reactions in the presence of reagent I have high rates and accompany excellent
yields under reflux conditions.
Conclusion
In this study, the syntheses, characterization and X-ray crystal structures of two new
quaternary phosphonium salts of 1, 2-ethandiylbis(triphenylphosphonium) diperchlorate (I)
and 1,2-ethandiylbis(triphenylphosphonium) dichlorate (II) have been reported with certain
advantages over similar oxidizing agents in terms of stability, easy storage, short reaction
time, easy preparation and high yields of the products. These reagents are stable for several
months at room temperature without loss of their activities (Bench top reagents). The
Hirshfeld surface analysis of crystal structures of titled compounds as well as analogous
2+
structures containing [EDBTPP] cationic unit obtained from CSD survey, revealed that the
arrangement of aromatic rings around the P centers of cationic unit and tetrahedral geometry
of phosphorous atom by τ indices are related to the various intermolecular interactions of
4
neighboring anionic moieties.
Experimental and methods
Materials and methods
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Alcohols, 1,2-dibromo ethane, triphenylphosphine, sodium perchlorate, sodium chlorate,
chromium trioxide were purchased from Fluka and Merck Co and used without further
purification. Solvents were purified by standard methods. Infrared spectra were recorded as
1
13
KBr disk on a Shimadzu FT-IR 8440S spectrophotometer. H NMR and C NMR (for
products) were carried out on a Bruker AC, 300 MHZ spectrometer with tetra methyl silane
as an internal reference and DMSO-d and also CDCl as solvents. GC spectra were recorded
6
3
by a Shimadzu 17a-GC spectrometer. Elemental analysis was performed on a LECO 250
instrument. The reactions were monitored by TLC using Silica gel plates. The products were
1
13
identified by comparison of their H NMR, C NMR, IR and GC spectra and physical data
with those of authentic samples.
Preparation of 1, 2-Ethandiylbis(triphenylphosphonium) Diperchlorate(C H Cl O ) (I)
38
34
2
8
8
1
, 1´-(Ethane, 1, 2-Diyl)Ditriphenylphosphonium Dibromide (C H Br ) (5 mmol, 3.56 g)
38 34 2
in H O (20 ml) was prepared in a 50 ml round bottomed flask with a magnetic stirrer. Then
2
NaClO (10 mmol, 1.225 g) in H O (10 ml) was added to this solution, and the reaction was
4
2
stirred at ambient temperature for 30 minute. The resulting white precipitate was filtered,
washed with distilled water (2×10 ml) and dried in vacuum. (95% yields, 3.57g). m.p: 258-
2
60 ˚C.
1
H NMR (100 MHz, DMSO) :
δ
δ
(ppm) = 4 (d, CH ), 7.8, 7.98 (m, aromatic hydrogens)
2
1
3
C NMR (100 MHz, DMSO):
(ppm)135.8, 134.5, 129.8, 117, 15.6.
-1
IR(KBr):
(cm )= 689(s), 738(s), 1099(s), 1439(s), 1486,1589(m), 2917(w), 3064(w).
Preparation of 1, 2-Ethandiylbis(triphenylphosphonium) Dichlorate(C H Cl O ) (II)
3
8
34
2
6
8
1
, 1´-(Ethane, 1, 2-Diyl)Ditriphenylphosphonium Dibromide (C H Br ) (5 mmol, 3.56 g)
3
8
34
2
in H O (20 ml) was prepared in a 50 ml round bottomed flask with a magnetic stirrer. Then
2
1
0

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NaClO (10 mmol, 1.06 g) in H O (10 ml) was added to this solution, and the reaction was
3
2
stirred at ambient temperature for 1 h. The resulting white suspension was allowed to stand at
room temperature for 1 week. Then the solution was filtered and dried in vacuum. (96%
yields, 3.45g). m. p : 184-186 ˚C.
1
H NMR (100 MHz, DMSO) :
δ
δ
(ppm) = 4 (d, CH ), 7.8, 7.95 (m, aromatic hydrogens).
2
1
3
C NMR (100 MHz, DMSO):
(ppm) = 135,9, 134.5, 130.8, 117.8, 15,6.
-1
IR(KBr):
064(w).
(cm )= 689(s), 741(s), 1110(s), 1436(s), 1482,1589(m), 2900(w), 2940 (m),
3
Single crystal X-ray diffraction analysis
The suitable single crystals for X-ray diffraction analysis were obtained by slow evaporation
at room temperature. Diffraction data for I and II crystals were collected at 100(2) K on
Oxford Diffraction Excalibur PX Ultra diffractometer equipped with enhance ultra (Cu) X-
ray source and Onyx CCD detector. Data reduction and analysis for those structures were
3
6
carried out with CrysAlisPro program v. 1.171.37.35. X-ray The structures were solved by
37
2
direct methods and subsequent different Fourier maps were used for refinement on F by a
full-matrix least-square procedure using anisotropic displacement parameters. The structures
3
8
were checked for higher symmetry with the help of the program PLATON. For title
compounds, the non-H atoms were refined anisotropically and H-atoms were placed in the
ideal positions. The structural resolution procedure was performed using WinGX
3
9
crystallographic software package. Summary of crystallographic data and structural
refinement of titled compounds is presented in Table 5. CCDC 1577312-1577313 contains
the supplementary crystallographic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/retrieving.html (or from the Cambridge Crystallographic
Data Centre, 12, Union Road, Cambridge, B2 1EZ, UK; fax +44 1223 336033; or
deposit@ccdc.cam.ac.uk).
1
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Acknowledgements The authors are grateful to the Ferdowsi University of Mashhad
Research Council for the financial support of the project Code Number3/36987. A. Salimi
also gratefully thanks the Cambridge Crystallographic Data Centre for access to the CSD
Enterprise.
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3. Seth, S. K.; Sarkar, D.; Jana, A.D.; Kar, T., Cryst. Growth Des. 2011, 11, 4837-4849.
4. Seth, S. K, J. Mol. Struct. 2014, 1070, 65-74
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5. Salmasi, R.; Gholizadeh, M.; Salimi, A.; Garrison, J.C. J. Iran. Chem. Soc. 2016, 13,
2019-2028.
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6. Salmasi, R.; Salimi, A.; Gholizadeh, M.; Abolghasempour, A.; Garrison, J.C.
Phosphorus, Sulfur Silicon Relat. Elem. 2016, 191, 1380-1387.
2
2
7. Seth, S. K.; Sarkar, D.; Kar, T., CrystEngComm, 2011, 13, 4528-4535.
8. Seth, S. K.; Manna, P.; Singh, N. J.; Mitra, M.; Jana, A. D.; Das, A.; Choudhury, S. R.;
Kar, T.; Mukhopadhyay, S.; Kim, K. S., CrystEngComm, 2013, 15, 1285-1288.
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9. Manna, P.; Seth, S. K.; Mitra, M.; Das, A.; Singh, N. J.; Choudhury, S. R.; Kar, T.;
Mukhopadhyay, S., CrystEngComm, 2013, 15, 7879-7886.
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0. Manna, P.; Seth, S. K.; Bauzá, A.; Mitra, M.; Ray Choudhury, S.; Frontera, A.;
Mukhopadhyay, S., Cryst. Growth Des. 2014, 14, 747-755.
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1. Manna, P.; Seth, S. K.; Mitra, M.; Choudhury, S. R.; Bauzá, A.; Frontera, A.;
Mukhopadhyay, S., Cryst. Growth Des. 2014, 14, 5812-5821.
2. Rahmani, M.; Salimi, A.; Mohammadzadeh, S.; Sparkes, H. A., CrystEngComm, 2016,
18, 8953-8960.
3. Wolff, S. K.; Grimwood, D.J.; McKinnon, J. J.; Turner, M. J.; Jayatilaka, D.; Spackman,
M. A., Crystal explorer ver. 3.1. University of Western Australia, Perth, Australia, 2013.
4. Groom, C. R.; Bruno, I. J.; Lightfoot, M. P.; Ward, S. C. The Cambridge Structural
Database, Acta Cryst. 2016, B72, 171-179.
3
3
5. Yang, L.; Powell, D. R.; Houser, R. P. Dalton Trans., 2007, 955-964.
6. Agilent, CrysAlisPro Version 1.171.37.35, Agilent Technologies UK Ltd, Yarnton,
England, 2014.
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7. Sheldrick, G. M. Acta Crystallogr. Sect. C: Struct. Chem., 2015, 71, 3-8.
8. Spek, A. L. J. ActaCryst., 2009, 65, 148-155.
9. Farrugia, L. J. J. Appl.Cryst., 2012, 45, 849-854.
1
3

ACCEPTED MANUSCRIPT
4
0. Hayward, C.M.T.; Shapley, J.R.; Churchill, M.R.; Bueno, C.; Rheingold, A.L., J. Am.
Chem. Soc., 1982, 104, 7347–7349.
4
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4
1. Hołyńska, M.; Lis, T., Dalton Trans., 2009, 19, 3840-3846.
2. Hołyńska, M.; Lis, T., Inorg. Chim. Acta, 2014, 419, 96-104.
3. Plesek, J.; Backovsky, J.; Cisarova, I. CCDC 158086, CSD Communication, 2003.
4. Lee, K.; Shapley, J.R., Organometallics, 1998, 17, 4030–4036.
5. Tanaka, K.; Nakashima, A.; Shimada, Y.; Scott, J. L., Eur. J. Org. Chem., 2006, 10,
2
423-2428.
6. Smith, E.J.; Pridmore, N.E.; Whitwood, A.C; Lynam, J.M., Organometallics, 2014, 33,
260-7269.
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7. Lau, S.S.; Wu, W.; Fanwick, P.E.; Walton, R.A., Polyhedron, 1997, 16, 3649-3654.
8. Ma, L.; Rodgers, D.P.S.; Wilson, S.R.; Shapley, J.R., Inorg. Chem., 1991, 30, 3591-3595.
9. Gholizadeh, M.; Zonoz, F.M.; Pourayoubi, M. Ebrahimpour, M.; Salehabadi, M. Acta
Crystallogr., Sect. E: Struct. Rep., 2011, 67, o863-o865.
5
5
5
5
5
5
5
0. Sharutin,V.; Sharutina, O.; Somov N. CCDC 823545, CSD Communication, 2016.
1. Sharutin V. CCDC 824491, CSD Communication, 2016.
2. Sharutin V. CCDC 828022, CSD Communication, 2016.
3. Sharutin V. CCDC 821580, CSD Communication, 2016.
4. Sharutin V. CCDC 828023, CSD Communication, 2016.
5. Sharutin V. CCDC 1061290, CSD Communication, 2016.
6. Churchill, M.R.; Bueno, C.; Rheingold A.L.; J. Organomet. Chem. 1990, 395, 85-103.
Figure Captions:
Figure 1 (a) ORTEP diagram and partial atom-numbering scheme represent asymmetric unit
of I. The perchlorate anion (Cl1) with major occupation factor of 0.9 was only represented for
more clarity. Displacement ellipsoids are given at 40% probability level. (b) C-H…π
interactions involving cation molecules of Ialong b direction. The intermolecular interactions
are represented by dashed lines. (c) and (d) representations of selected intermolecular
hydrogen bonds present in one dimensional hydrogen bonded chains in I. The hydrogen
bonds are represented by dashed lines. The centroid of phenyl rings are called as Cg (No).
1
4

ACCEPTED MANUSCRIPT
Figure 2 (a) ORTEP diagram and partial atom-numbering scheme represent asymmetric unit
of II. Displacement ellipsoids are given at 40% probability level. (b) C-H…π interactions
involving cation molecules of II in side view. The intermolecular interactions are represented
by dashed lines. (c) and (d) representations of selected intermolecular hydrogen bonds
present in one dimensional hydrogen bonded chains in compound II along a and c directions,
respectively. The hydrogen bonds are represented by dashed lines. The centroid of phenyl
rings are called as Cg (No).
Figure 3 Schematic illustrations of decomposed fingerprint plots of compounds I and II.
Figure 4 Representation of the Hirshfeld surfaces of compounds I and II, which mapped over
dnorm and their related the 2D fingerprint plots. The CH···O interactions were presented by
red spot in the upper section.
Figure 5 Fingerprint plots of twenty three structures obtained from the CSD analysis.
Scheme 1
Br
ClO4
PPh3
Ph P
3
NaClO4
Ph P
3
PPh3
r. t.
ClO4
Br
OH
O
Reagent I or II or III
CH CN or DMF
3
R
R
1
5

ACCEPTED MANUSCRIPT
Figure 1
1
6

ACCEPTED MANUSCRIPT
Figure 2
1
7

ACCEPTED MANUSCRIPT
I
Figure 3
1
8

ACCEPTED MANUSCRIPT
CH···O Interaction
Compound II
Compound I
Figure 4
1
9

ACCEPTED MANUSCRIPT
Figure 5
2
0

ACCEPTED MANUSCRIPT
Table 1. Selected hydrogen-bond parameters of compounds I and II
D–H…A
d(D–H)/Å
d(H…A)/Å
d(D…A)/Å
∠D–H…A/°
Compound I
C4-H4…O2(i)
C8-H8….O4
0.95
0.95
0.99
0.99
0.99
0.95
0.95
0.95
0.95
0.95
0.95
0.95
2.65
2.57
2.34
2.58
2.42
2.52
2.67
2.60
2.64
2.43
2.67
2.91
3.572 (3)
3.436 (2)
3.188 (2)
3.548 (3)
3.396 (3)
3.463 (3)
3.325 (2)
3.534 (2)
3.176 (2)
3.380 (2)
3.619 (3)
3.714 (3)
163.6
151.3
143.4
167.4
169.6
170.7
126.5
167.1
116.3
174.9
175.6
143.2
C19-H19A…O7
C19-H19B…O4
C20-H20B…O5(ii)
C22-H22….O3 (iii)
C24-H24…O6 (ii)
C30-H30…O3 (ii)
C32-H32…O7
C36-H36….O6 (iv)
C38-H38…O3 (iii)
C24-H24…Cl2(ii)
Compound II
C3-H3…O1(i)
C8-H8…O2
C10-H10….O1(ii)
C11-H11…O3(ii)
C12-H12…O3
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.99
2.47
2.55
2.59
2.60
2.46
2.49
2.62
2.65
2.52
2.27
3.294 (2)
3.314 (3)
3.281 (2)
3.547 (3)
3.339 (3)
3.389 (4)
3.290 (2)
3.555 (3)
2.280 (3)
3.250 (2)
144.9
137.5
129.8
171.4
154.1
158.2
127.9
158.4
137.6
171.0
C14-H14…O1
C16-H16…O3(iii)
C17-H17….O2 (iv)
C18-H18…O2 (iii)
C19-H19A…O2
Symmetry codes, compound I: (i) -1+x, y, z ; (ii) 1/2-x,1/2+y,1/2-z; (iii) 1/2+x,1/2-y,1/2+z; (iv) -
/2+x,1/2-y,1/2+z, compound II: (i) 1-x, -y, 2-z; (ii) -1/2+x,1/2-y,-1/2+z; (iii) 1/2-x,1/2+y,1/2-z; (iv) -1/2+x,-
/2+y, z.
1
1
Table 2. CHꢀꢀꢀπ interaction geometries of I and II
CH…π Interaction
Compound I
HꢀꢀꢀCg/Å
CꢀꢀꢀCg/Å
CHꢀꢀꢀCg /°
C-H10ꢀꢀꢀπ(Cg2)*
C-H14ꢀꢀꢀπ(Cg4)
C-H23ꢀꢀꢀπ(Cg6)
C-H37ꢀꢀꢀπ(Cg1)
Compound II
2.720
3.316
3.694
2.760
3.427
131.77
164.87
153.67
127.67
4.241
4.565
3.443
C-H6ꢀꢀꢀπ(Cg2)
C-H9ꢀꢀꢀπ(Cg3)
3.435
2.779
4.121
3.679
130.94
158.51
*
The centroid of phenyl rings are called as Cg (No).
2
1

ACCEPTED MANUSCRIPT
Table 3. Relative contribution of various atom pair contacts to the Hirshfeld surface area
2
+
compounds I and II and twenty three structures including the [EDBTPP] cationic unit
obtained from the CSD analysis
[
Counter anion]
τ
τ
C
H
ꢀꢀꢀ
ꢀꢀꢀ
H
C
C
O
ꢀꢀꢀ
ꢀꢀꢀ
O
C
O
ꢀꢀꢀ
H
O
X
C
ꢀꢀꢀ
ꢀꢀꢀ
C
X
X
H
ꢀꢀꢀ
ꢀꢀꢀ
H
X
M
ꢀꢀꢀ
M
C
M
ꢀꢀꢀ
M
H
SꢀꢀꢀC
CꢀꢀꢀS
SꢀꢀꢀH
HꢀꢀꢀS
1
2
CꢀꢀꢀC
No.
Refcode
ꢁτ
HꢀꢀꢀH
Ref
Hꢀꢀꢀ
C
ꢀꢀꢀ
Hꢀꢀꢀ
(
solvent)
(P1)
(P2)
-
-
This
study
I
II
1
Compound I
CompoundII
BORJEX
2[ClO4]
0.971 0.974
41.3
43.6
26.0
2.7
0.8
1.3
25.0
30.4
12.4
2.8 28.2
1.0 21.3
8.4 51.9
-
-
-
-
-
-
-
-
-
-
-
-
-
-
0
.003
2
-
This
study
[ClO3]
0.977 0.977 0.000
1.6
-
1.3
-
2
-
-
[
C O Ru ]
-
0.975 0.984
0.008
26
24
10
40
41
2
(C H O)
3
6
2
[
Cl O Re ]
8 3 2
2
DUGKOG
0.992 0.992 0.000
18.9
0.1
11.2
1.2
5.2
12.2 51.1
-
-
-
-
4
(CHCl3)
2
-
3
4
DUGLEX
EGAVAL
[Cl O Re ]
0.985 0.985 0.000
0.965 0.965 0.000
38.9
45.2
3.1
1.3
18.9
19.4
1.2
1.1
4.9
7.1
4.8
3.5
28.2
22.4
-
-
-
-
-
-
-
-
41
42
8
3
2
-
2[CH Cl O Re]
4
4
2
-
-
5
6
7
HADWIT
HISPOO
HISPUU
2[C H B Co]
0.979 0.992
78.3
32.1
33.8
0.2
1.3
1.3
21.5
15.0
15.4
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
43
44
44
4
22 18
0
.013
2
-
-
[
[
C H O Ru ]
27 4 22 10
0.970 0.970 0.000
0.967 0.935 0.032
6.3 45.3
6.4 43.1
2
(C H O)
3 6
2
C H O Ru ]
28
8
20
10
2
(C H O)
3 6
-
2[Br]
8
JEGZEB*
1.33(C H O )
-
-
-
-
-
-
47.8
5.8
24.9
1.2 13.4
-
6.8
-
-
-
-
45
6
12
2
2
(C H O)
2 6
-
2[Br] ,
9
JEGZIF*
MOZQAV*
NIPTUB
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
45
46
47
2
(C H O )
6
12
3
-
1
1
0
1
2[BF4]
0.986 0.981 0.005
46.2
41.6
0.1
2.1
22.4
24.5
3.1
2.8
28.2
2.7
2-
-
[Cl Re ]
0.985 0.986
0.4
0.3
1.5
-
8
2
0
0
.001
-
.016
-
0.001
2-
1
2
NIPVAJ
[Cl Os ]
0.946 0.962
0.983 0.984
44.8
2.1
19.4
-
-
4.2
29.2
-
-
47
8
2
2
-
[
C H O Ru ]
38 10 22 10
1
1
1
1
1
3
4
5
6
7
SONKAH
UNUREB
IWUWAA
UWOVOT
SALKAU
23.7
39.8
48.9
41.7
52.1
5.0
2.3
3.1
1.6
0.4
15.1
22.5
25.4
25.9
18.1
9.5 46.8
3.8 31.4
1.8 20.8
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
48
49
26
25
50
2
(C H O)
3
6
-
2[IO4]
0.988 0.975 0.013
0.994 0.986 0.008
0.982 0.982 0.000
0.1
-
2
-
[
O S ]
8 2
-
-
-
2
(H O)
2
-
2[Br3]
-
-
-
-
4.2
3.8
26.7
17.2
-
-
-
-
-
2[AuCl2]
2[AuCl4]
0.968 0.999
3.0
5.3
0
0
.031
-
.001
1
1
2
8
9
0
AZUZOM
AZUZIG
AZUXUQ
0.991 0.992
39.7
47.7
47.2
2.2
1.4
0.5
19.0
30.7
21.1
-
-
4.3
0.2
3.0
31.6
13.4
23.8
2.7
0.4
-
0.6
0.7
-
-
-
-
-
51
52
53
-
2[C H Cl OPdS]
0.964 0.964 0.000
0.994 0.982 0.012
1.4
0.7
4.1
3.2
2
6
3
(
C H OS)
2
6
-
0.2
0.2
2
[I ]
3
4
(C H OS)
-
0.965 0.977
0.012
2
6
2
2
2
1
2
3
AZUSEV
AZOYEV
BORJEX10
30.7
46.7
26.0
3.3
-
29.1
28.4
12.4
2.4 11.6
-
1.4
-
14.9
18.2
-
1.0
1.4
-
-
3.8
-
2.5
4.6
54
55
56
2-
[
Cl Pt]
6
2-
[Ag Cl ]
0.969 0.969 0.000
-
-
-
-
-
-
2
4
2
-
[
C O Ru ]
-
0.975 0.984
0.008
2
6
24
10
1.3
8.4 51.9
2
(C H O)
3 6
*
disorder structure- M= Metal - X= Halogen
2
2

ACCEPTED MANUSCRIPT
Table 4 . The optimized oxidation conditions of 4-chlorobenzyl alcohol by using the various
oxidants in different solvents.
Entries
Type of Oxidant
Solvent
Yield (%)(Time)
II
I
1
2
DMF
98 (5min)
95 (5min)
CH Cl2
65 (70min)
10 (<5min)
2
3
4
CHCl3
N. R.
N. R.
CH CN
90 (15min)
30 (25min)
3
5
6
THF
N. R.
N. R.
N. R.
N. R.
n-Hexane
1
:1 Molar ratio of substrate to oxidant at the reflux condition
2
3

ACCEPTED MANUSCRIPT
Table 5. Structural data and refinement for title compounds
compound
I
II
chemical formula
(C H P )
·
2(ClO4)
(C H P )·2(ClO3)
2
3
8
34
2
38 34
Mr
751.49
719.49
Crystal system, space group
Monoclinic, P2 /n
Monoclinic, C2/c
100(2)
1
Temperature (K)
a (Å)
100(2)
8.9446(1)
17.6952(1)
21.8856(2)
94.301(1)
3454.22(5)
4
13.10880(10)
14.47530(10)
18.3261(2)
98.0420(10)
3443.25(5)
4
b (Å)
c (Å)
β (˚)
3
V (Å )
Z
Radiation type
CuKα
CuKα
-1
ꢂ (mm )
3.024
2.963
Crystal size (mm)
Diffractometer
Absorption correction
No. of measured, unique
GOOF
0.2 × 0. 5 × 0. 5
Xcalibur, Onyx, Ultra
Multi-scan
24228, 6332
1.040
0.2 × 0. 3 × 0. 6
Xcalibur, Onyx, Ultra
Multi-scan
47119, 3180
1.057
R1(I>2σ(I))
0.0487
0.0383
wR (I>2σ(I))
0.1252
0.1023
2
3
Largest diff. peak and hole [e/Å ]
1.640 and -0.530
0.370 and -0.460
2
4

ACCEPTED MANUSCRIPT
•
•
Two new quaternary phosphonium salts of perchlorate (I) and chlorate (II) have been synthesized
and characterized.
The Hirshfeld surface analysis of crystal structures of titled compounds as well as analogous
structures obtained from CSD revealed that the arrangement of phenyl rings around the P centers
and
4
τ tetrahedral geometry indices are related to the various intermolecular interactions of
neighboring moieties.
•
Crystal packing in both compounds is mostly governed by hydrogen bond which assisted by
based interactions.
π–