Crystal structure, quantum mechanical study and spectroscopic studies of nitrate and perchlorate salts of 3-chloroaniline, [C6H7ClN]NO3 (I) and [C6H7ClN]ClO4 (II)

Article abstract of DOI:10.1016/j.molstruc.2017.02.042

Two new organic-inorganic hybrid compounds, 3-chloroanilinium nitrate (I) and 3-chloanilinium perchlorate (II), have been synthesized by an acid/base reaction at room temperature in the presence of 3-chloroaniline as an organic-structure directing agent and their structures were determined by single crystal X-ray diffraction. Compound I, [C₆H₇ClN]NO₃, crystallizes in the orthorhombic space group Pbca with a?=?10.4137(16), b?=?9.6232(11), c?=?16.059(2) ?, V?=?1609.3(4) and z?=?8. Full-matrix least-squares refinement converged at R?=?0.041 and Rw?=?0.121. Compound II, [C₆H₇ClN]ClO₄, belongs to the monoclinic system, space group P21/n with the following parameters: a?=?10.684(2), b?=?7.2667(12), c?=?12.229(2) ?, β?=?104.27(2)°, V?=?920.1(3) and z?=?4. The structure was refined to R?=?0.054 and Rw?=?0.102. Both salts form anionic parallel layers alternating with thick slabs of [C₆H₇NCl]⁺ organic molecules. Charge balance is achieved by the protonated amine which interacts with the inorganic framework through hydrogen bonding. Solid-state ¹³C CP-MAS NMR spectroscopy is in agreement with the X-ray structures. Ab initio calculations allow the partial attribution of carbon signals to the various atoms of the organic groups. Electronic properties such as HOMO and LUMO energies were studied by Quantum mechanical evaluation by using the B3LYP/6-31+G* method.

Full text of DOI:10.1016/j.molstruc.2017.02.042

Accepted Manuscript
Crystal structure, quantum mechanical study and spectroscopic studies of nitrate and
perchlorate salts of 3-chloroaniline, [C H ClN]NO (I) and [C H ClN]ClO (II)
6 7
3
6 7
4
I. Bayar, L. Khedhiri, E. Jeanneau, F. Lefebvre, C. Ben Nasr
PII:
S0022-2860(17)30188-6
10.1016/j.molstruc.2017.02.042
MOLSTR 23436
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 2 November 2016
Revised Date: 9 February 2017
Accepted Date: 10 February 2017
Please cite this article as: I. Bayar, L. Khedhiri, E. Jeanneau, F. Lefebvre, C. Ben Nasr, Crystal structure,
quantum mechanical study and spectroscopic studies of nitrate and perchlorate salts of 3-chloroaniline,
[C H ClN]NO (I) and [C H ClN]ClO (II), Journal of Molecular Structure (2017), doi: 10.1016/
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j.molstruc.2017.02.042.
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ACCEPTED MANUSCRIPT
Crystal structure, quantum mechanical study and
spectroscopic studies of nitrate and perchlorate salts of 3-
chloroaniline, [C6H7ClN]NO3 (I) and [C6H7ClN]ClO4 (II)
I. Bayara, L. Khedhiria, E. Jeanneaub, F. Lefebvrec, C. Ben Nasra
aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna,
Université de Carthage, Tunisie.
bLaboratoire de Chimie Organométallique de Surface (LCOMS), Ecole Supérieure de Chimie
Physique Electronique, 69622 Villeurbanne Cedex, France.
cLaboratoire de Chimie Organométallique de Surface (LCOMS), Ecole Supérieure de Chimie
Physique Electronique, 69626Villeurbanne Cedex, France.
Corresponding e-mail: Lamia.Khedhiri@gmail.com
Abstract
Two new organic-inorganic hybrid compounds, 3-chloroanilinium nitrate (I) and 3-
chloanilinium perchlorate (II) have been synthesized by an acide/base reaction at room
temperature in the presence of 3-chloroaniline as an organic-structure directing agent and
their structures were determined by single crystal X-ray diffraction. Compound I,
[C6H7ClN]NO3, crystallizes in the orthorhombic space group Pbca with a = 10.4137(16), b =
9.6232(11), c = 16.059(2) Å, V = 1609.3(4) and z = 8. Full-matrix least-squares refinement
converged at R = 0.041 and Rw = 0.121. Compound II, [C6H7ClN]ClO4, belongs to the
monoclinic system, space group P21/n with the following parameters: a = 10.684(2), b =
7.2667(12), c = 12.229(2) Å, β = 104.27(2) °, V = 920.1(3) and z = 4. The structure was
refined to R = 0.054 and Rw = 0.102.
Both salts form anionic parallel layers alternating with thick slabs of [C6H7NCl]+
organic molecules. Charge balance is achieved by the protonated amine which interacts with
the inorganic framework through hydrogen bonding. Solid-state 13C CP-MAS NMR
spectroscopy is in agreement with the X-ray structures. Ab initio calculations allow the partial
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attribution of carbon signals to the various atoms of the organic groups. Electronic properties
such as HOMO and LUMO energies were studied by Quantum mechanical evaluation by
using the B3LYP/6-31+G* method.
Keywords: Organic-inorganic hybrid materials; X-ray structure; IR absorption; Quantum
calculations; DFT calculations
1. Introduction
Hybrid compounds are materials that involve both organic and inorganic components
blended in the solid state on the molecular scale.
Research in organic-inorganic materials has experienced considerable growth in recent
years for the purpose of generating materials with desirable properties and functionalities. An
important strategy employed in studying such systems has been to take advantage of
hydrogen-bond interactions between organic cations and inorganic anions, since they have
been recognized as the most powerful force to generate supramolecular networks in one, two
and three dimensions [1, 2]. In this context, our aims have been focused on the organic salts
of oxoanions systems.
Coordination chemistry of oxanions does not cease developing and being the subject
of main research topic in several laboratories. Oxanions the most studied are of tetrahedral
and pyramidal geometries such as sulfates, phosphates, molybdates, nitrate, perchlorate,
selenite, iodate, etc. These anions are Lewis bases used as ligands for elaborate interesting
metal complexes having applications in various fields: stabilization of PVC, protection of
wood, catalyses, pesticides, fungicides, pharmacology etc. [3–7]. Several organic cations
(protonated amines) can be used as stabilizing of these anions especially those that are acidic
[8–10]. We report in this work synthesis and physico-chemical and structural study of the
nitrate and perchlorate salts of 3-chloroaniline, [C6H7ClN]NO3(I) and [C6H7ClN]ClO4(II)
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3-Chloroaniline is used as an intermediate in the production of several urea herbicides
and insecticides (monuron, diflubenzuron), azo dyes, pigments, pharmaceutical and cosmetic
products. It is a precursor to the widely used antimicrobial and bactericide chlorhexidine and
is used in the manufacture of pesticides, including pyraclostrobin, anilofos, monolinuron and
chlorphthalim [11].
2. Experimental
2.1. Chemical preparation
The salts (I) and (II) were synthesized from an aqueous mixture of 3-chloroaniline and
the corresponding concentrated acids (cold 65% HNO3 and cold 70% ClO4) with a
stoichiometric ratio of 1:1 at room temperature followed by slow evaporation in accordance
with the reaction (Scheme 1). After a week period, block type red crystals of both compounds
were obtained. The quality of the crystals was improved by recrystallization in a minimum
amount of ethanol (10 mL) at room temperature.
+
NH3
Cold 65% HNO3
-
.
NO3
(I)
NH2
Cl
+
NH3
Cl
-
.
(II)
ClO4
Cold 70% HClO4
Cl
Scheme 1
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2.2. Investigation techniques
2.2.1. X-ray single crystal structural analysis
Suitable crystals of (I) and (II) were selected and mounted on a Gemini kappa-
geometry diffractometer (Agilent Technologies UK Ltd) equipped with an Atlas CCD
detector and using Mo radiation ( λ= 0.71073 Å). Intensities were collected at 150 K by
means of the CrysalisPro software [12]. Reflection indexing, unit-cell parameters refinement,
Lorentz-polarization correction, peak integration and background determination were carried
out with the CrysalisPro software [12]. An analytical absorption correction was applied using
the modeled faces of the crystal [13]. The resulting set of hkl was used for structure solution
and refinement. Both structures were solved by direct methods with SIR97 [14] and the least-
square refinement on F2 was achieved with the CRYSTALS software [15].
All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were
located in a difference map, but those attached to carbon atoms were repositioned
geometrically. The H atoms were initially refined with soft restraints on the bond lengths and
angles to regularize their geometry (C-H in the range 0.93-0.98 and N-H in the range 0.86-
0.89 Å) and Uiso(H) (in the range 1.2-1.5 times Ueq of the parent atom), after which the
positions were refined with riding constraints.
The drawings were made with Diamond [16]. The details of data collection,
refinement and crystallographic data are summarized in Table S1.
Crystallographic data for the structural analysis have been deposited at the Cambridge
Crystallographic Data Centre, CCDC No 1478905 for (I) and CCDC No 1478906 for (II).
These
data
can
be
obtained
free
of
charge
via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK: fax: (+44) 01223-336-033; e-mail: deposit@ccdc.cam.ac.
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2.2.2. NMR and IR measurements
The 13C NMR spectra were recorded on a solid-state high-resolution Bruker DSX-500
spectrometer operating at 125.78 MHz with a classical 4 mm probehead allowing spinning
rates up to 10 kHz. 13C NMR chemical shifts are given relative to tetramethylsilane (precision
0.5 ppm). The spectra were recorded by use of cross polarization (CP) from protons (contact
time 2 ms) and magic angle spinning (MAS). Before recording each spectrum it was checked
that there was a sufficient delay between the scans allowing a full relaxation of the protons
(typically 10 s). The IR spectra were recorded in the range 4000-400 cm-1 with a ‘‘Perkin–
Elmer FTIR’’ spectrophotometer1000 using samples dispersed in spectroscopically pure KBr
pressed into a pellet.
3. Results and discussion
3.1. X-ray diffraction study
The solid state molecular and crystal structures of nitrate and perchlorate salts of 3-
chloroaniline: [C6H7ClN]NO3(I) and [C6H7ClN]ClO4(II) are illustrated from the single crystal
XRD studies. All data concerning the experimental parameters used for the structures
determination as well as their final results are gathered in Table S1. Selected bond distances
and bond angles are presented in Tables S2 and S3. The asymmetric part of each unit cell
-
-
contains a 3-chloroanilinium cation and the corresponding anion (NO3 /ClO4 ) as shown in
Fig. 1-I and Fig. 1-II. Protonation on the N site of the cation is confirmed from the elongated
C-N bond distance [1.464(4)/1.467(4) Å respectively] and deprotonation from the anion is
confirmed from the N-O/Cl-O bond distances and O-N-O/O-Cl-O angles as listed in Tables
S2 and S3. The molecular structure of 3-chloroanilinium nitrate (I) is shown in Fig. 1-I. This
compound crystallizes in the orthorhombic space group Pbca (Z = 8). The atomic arrangement
can be described by corrugated layers of inorganic entities, made up from NO3 anions and
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NH3 groups, developed parallel to the (a, b) planes at z = 1/4 and 3/4 (Fig. 2-I). The organic
cations are anchored between these layers and connect them via hydrogen bonds to form an
infinite three-dimensional network. The complete atomic arrangement, projected along the a-
axis direction is shown in Fig. 3-I, whereas Fig. S4-I exhibits how the nitrate molecule, binds
the three molecules of 3-chloroaniline generating a supramolecule with different types of H-
bonds. N-H…O interactions are in the range of 2.837(3)-3.128(3) Å while N-H…N
interactions range between 3.339(3) and 3.425(3) Å (Table S4). It should be noticed that all
the amino hydrogen atoms are involved in N-H···O and N-H…N hydrogen bonding, with H1,
H3 trifurcated and H2 bifurcated (Fig. S4-I).
A comparison of the title compound (I) to aniliniumnitrate (III) [17] shows that the
two compounds differ only by the nature of the substituent of the organic cation at the C3
position. This situation does not affect the space group, unit cell parameters, atomic
arrangement and hydrogen bond network. In fact both compounds crystallize in the same
Pbca space group of the orthorhombic system (Z = 8). Furthermore, both structures have a
similarly typical layered organization and the same arrangement in opposite direction of
organic cations. In addition the inorganic anions are connected to the organic cations via
medium H-bonds involving the three atoms of the NH3 groups.
3-chloroanilinium perchlorate [C6H7ClN]ClO4 (II) crystallizes in monoclinic space
group P21/n (Z = 4). Configurations of the different organic and inorganic species including
the vibrational ellipsoids at 50% probability are depicted in Fig. 1-II. In the present crystal
structure, the molecular components are stabilized through intricate three dimensional
hydrogen bonding network as listed in Table S5. In this compound one perchlorate ion links
the five molecules of amine through N-H…O and C-H…O type of H-bonds (Fig. S4-II). The
N-H…O interactions are in the range of 2.864(5)-2.911(5)Å, while the C-H…O
interactionis3.283(5)Å. These interactions lead to the formation of two-dimensional infinite
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inorganic layers parallel to the (b, c) plane (Fig. 2-II). The bodies of the organic entities are
located between these layers and connect each other via C-H…O hydrogen bonds to perform
an infinite three-dimensional network (Fig. 3-II).
The calculated average values of the distortion indices [18] corresponding to the
different angles and distances in the ClO4 tetrahedra, DI(ClO) = 0.010, DI(OClO) = 0.008
and DI(OO) = 0.007 show an above distortion of the Cl-O distances compared to O-O ones.
The ClO4 tetrahedron is then described by regular oxygen atoms arrangement with the
chlorine atom slightly shifted from the centre of gravity (δCl1 = 0.026).
A comparison of the title compound, 3-chloroanilinium perchlorate (II), to 4-
chloroanilinium perchlorate [19] and to 2-chloroanilinium perchlorate [20] shows that they
differ essentially by the position of the chlorine at the para and ortho-positions on the phenyl
ring respectively. This simple difference affects only the unit-cell parameters and some
similarities can be observed between these structures. In each isomer, the structure has a layer
organization, which contains centrosymmetric ClO4 anions encapsulating the organic cations.
3.2. Quantum mechanical study
The HOMO and LUMO orbitals were determined on the cation/anion system
corresponding to the atoms of the asymmetric unit. The calculations were made with the
Gaussian A-09 software by using the B3LYP/6-31+G* method. The positions of the atoms
were those determined by the X-ray study.
Even if it is difficult to determine discrete orbitals for a crystal (a better choice would
be to perform periodic calculations which are highly time consuming) a good approximation
of the gap between the occupied and unoccupied orbitals can be obtained by this way. Figs. 4
and 5 show the HOMOs and LUMOs for the two title compounds calculated at the B3LYP/6-
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31+G* level. Clearly, for both materials, the highest occupied orbitals are localized on the
chlorine and a part of the aromatic ring, while the lowest unoccupied orbitals are located
primarily on the NH3 group. The large HOMO-LUMO gaps of 5.61 eV and 5.66 eV for (I)
and (II), respectively, imply high kinetic stability and low chemical reactivity [21, 22],
because it is energetically unfavorable to add electron to a high-lying LUMO or to extract
electrons from a low-lying HOMO [23].
3.3. NMR results
The 13C CP–MAS NMR spectrum of (I) is shown in Fig. 6. It exhibits four resonances
corresponding to the six crystallographically independent carbon atoms, with two of the
peaks, at 120 and 137 ppm being asymmetric (having a shoulder). The spectrum can thus be
interpreted as featuring six resonances. This is in agreement with one organic molecule being
present in the asymmetric unit cell as revealed by X-ray structure determination.
The 13C CP–MAS NMR spectrum of (II) is shown in Fig. 7. It exhibits five resonances
corresponding to the six crystallographically independent carbon atoms, with one of the
peaks, at 120.3 ppm being asymmetric (having a shoulder). This is in agreement with one
organic molecule being present in the asymmetric unit cell as revealed by X-ray structure
determination. The peak related to the C2 carbon atom is not observed since this atom is not
directly bonded to a hydrogen atom.
In order to assign the NMR resonances to the different crystallographically
inequivalent carbon atoms of the unit cell, Density Functional Theory calculations were
undertaken. The chemical shifts calculations were made on the organic molecules after
optimization of the positions of the protons and the calculated values were calibrated relative
to tetramethylsilane with δexp = 0 ppm. The atoms are labeled as depicted below:
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The obtained results, gathered in Table 1, indicate a good agreement between the
experimental the theoretical values. The discrepancy between the calculated and experimental
values is mainly due to the fact that an isolated molecule was taken into account.
It is worth noticing that the discrepancy between the calculated and experimental
values is mainly due to the fact that an isolated molecule was taken into account. A better
agreement should be obtained by using periodic calculations but such studies are too time
consuming and could not be done on this system. However such calculations allow to see
where the effect of the surrounding molecules is the most important and so can be correlated
indirectly to the X-ray data.
3.4. IR spectroscopy
To gain information on the crystal structure, we have carried out a vibrational study
using infrared absorption. The infrared spectra of both compounds recorded at room
temperature are shown in Fig. S2 and Fig. S3. Based on some studies carried out for previous
works and reported on similar nitrate and perchlorate compounds [24], we propose an attempt
of assignment of the observed bands.
The molecular structures of both compounds have various functional groups such as
+
NH3 , C-H, C-N, C=C and disubstituted benzene ring. These groups are expected to undergo
changes in their intensity and position according to their environments [25].
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Hydrogen bonding interactions are able to affect the frequency as well as the intensity
and width of these vibrations. As these structures feature N-H…O hydrogen bonds, the N-H
stretching modes are altered largely. In the high-frequency region, between 3600 and 2300
cm-1, the observed bands correspond to the stretching vibrations of the N-H, C-H and C-N
groups [26]. The low wavenumber region around 1500-450 cm-1 contains bands due to
deformation vibrations of the various groups. The lattice vibration modes occur below 450
cm-1.
-
For the NO3 anion, Fig. S2 shows different groups of bands between 1400 and 700
cm-1. In this case, the intense peak appears at 1328 cm-1 shows the presence of antisymmetric
-
stretching vibration of NO3 (ν3). The bands between 1140 - 918 cm-1 are related to the
symmetric stretching modes ν(NO3). Then we attribute the observed shoulder at 871 cm-1
and the weak band at 724 cm-1 respectively to the γ(NO3) in the plane bending and δ(NO3)
out of the plane bending modes.
Whereas Fig. S3 shows that the asymmetric stretching vibration of the ClO4 anion is
observed as intense peaks at 1047 and 1099 cm-1. The band at 673 cm-1 is assigned for
wagging vibration and the peak at 626 cm-1 is assigned for twisting vibration of the anion.
DFT calculations of the frequencies were made on the geometry obtained after optimization
of the protons. An additional calculation was also made on the anion and the contributions of
the two components were summed to lead the full spectrum. The resulting IR spectra between
500 and 4000 cm-1 are shown on Figs. S4 and S5 for (I) and (II), respectively, and are very
similar to the experimental ones. A close agreement between the experimental and theoretical
wave numbers is mostly achieved in the finger print region as shown in Figs. S6 and S7, for
(I) and (II). Thus, the precision is well-sufficient to assign the experimental frequencies and to
confirm the attributions proposed above.
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Conclusion
Two new salts containing the 3-chloroaniline cation with nitrate and perchlorate have been
prepared at room temperature and characterized by physicochemical methods. Both structures
involve a network of inorganic parallel layers built up by the corresponding anion and NH3
groups. Charge balance is achieved by the protonated amine which is trapped in the interlayer
space and interacts with the organic framework through N-H…O, C-H…O, O-H…O
hydrogen bonding to form an infinite three-dimensional network. The band gap energy
indicates that the title compound is kinetically stable. NMR signals are in full agreement with
the crystallographic data. DFT calculations allow the attribution of the experimental NMR
lines and of IR bands at low frequencies.
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References
[1]
G. A. Ozin, Nanochemistry: Synthesis in diminishing dimensions, Adv. Mater.
4 (1992) 612-649.
[2]
O. Terasaki, K. Yamazaki, J. M. Thomas, T. Ohsuna, D. Watanabe, J. V. Sanders, J.
C. Barry, Isolating individual chains of selenium by incorporation into the channels of
a zeolite, Nature (London). 330 (1987) 58-60.
[3]
J. F. Vollano, R. O. Day, D. N. Rau, V. Chadrasekhar, R. R. Holmes,
Pentacoordinated molecules. 55. Intramolecularly formed pentacoordinated structures
of triphenyltin esters of salicylic acid, o-anisic acid, and p-methylthiobenzoic acid,
Inorg. Chem. 23 (1984) 3153-3160.
[4]
[5]
K. C. Molloy, Solid state 119Sn NMR study of organotin carboxylates and
thiophosphates, Inorg. Chem. Acta. 141 (1988) 151-152.
C. Peltinari, F. Marchetti, M. Pelli, A. Cingolani, L. Barba, A. Cassetta, Tin(IV)
and organotin(IV) complexes containing mono or bidentate N-donor ligands II. 14-
Phenylimidazole derivatives. Crystal and molecular structure of [bis(4-
phenylimidazole) trimethyltin(IV) ] chloride, J. Organomet. Chem. 515 (1996)
119-130.
[6]
S. K. Vasisht, T. P. Kaur, J. Kaushal, S. Dixit, Synthesis and characterization of
sodium bis(trimethylstannyl) amide and bis(trimethylsilyl) bis(trimethylstannyl) -
phospha-tetrazene, J. Organomet. Chem. 540 (1997) 51-54.
[7]
[8]
M. Gielen, Tin-based antitumour drugs, Coord. Chem. Rev. 151 (1996) 41-51.
A. Rayes, C. Ben Nasr, M. Rzaigui, Synthesis and crystal structures of a new (2,3-
(CH3)2C6H3NH3)H2XO4 (X=P, As), Mater. Res. Bull. 39 (2004) 1113-1121.
12

ACCEPTED MANUSCRIPT
[9]
K. Kaabi, C. Ben Nasr, M. Rzaigui, Synthesis and characterization of a new
monophosphate [2,5-(CH3)2C6H3NH3]H2PO4, J. Phys. Chem. Solids. 65 (2004) 1759-
1764.
[10] H. Rahmouni, W. Smirani, M. Rzaigui, S. S. Al-Deyab, 4-Chloro-anilinium hydrogen
oxalate hemihydrate, Acta Cryst. E66 (2010) 993.
[11] R. D. Ashford, Ashford’s Dictionary of Industrial Chemistry, third ed.,Wavelength
Publications, Botus Fleming, England, 2011.
[12] CrysAlisPro, Agilent Technologies, Version 1.171.34.49 (release 20-01-
2011CrysAlis171.NET) (compiled Jan 20 2011, 15: 58: 25).
[13] R. C. Clark, J. S. Reid, The analytical calculation of absorption in multifaceted
crystals, Acta Cryst. A51 (1995) 887-897.
[14] A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C. Giacovazzo,A.
Guagliardi, A. Grazia, G. Moliterni, G. Polidori, R. J. Spagna, SIR97: a new tool for
crystal structure determination and refinement, J. Appl. Cryst. 32 (1999) 115-119.
[15] P. W. Betteridge, J. R. Carruthers, R. I. Cooper, K. Prout, D. J. Watkin,
CRYSTALS version 12: software for guided crystal structure analysis, J. Appl. Cryst.
36 (2003) 1487.
[16] K. Brandenburg, Diamond Version 2.0, Impact GbR, Bonn, Germany, 1998.
[17] M. K. Marchewka, A. Pietraszko, Structural and vibrational studies of anilinium
nitrate , J. Phys. Chem. Solids. 66 (2005) 1039-1048.
[18] W. H. Baur, The geometry of polyhedral distortions. Predictive relationships for the
phosphate group, Acta Cryst. B30 (1974) 1191-1195.
[19] R. Anitha, S. Athimoolam, M. Gunasekaran, K. Anitha, X-ray, vibrational spectra and
quantum chemical studies on a new semiorganic crystal: 4-Chloroanilinium
perchlorate, J. Mol. Struct. 1076 (2014) 115-125.
13

ACCEPTED MANUSCRIPT
[20] B. Zhou, J. Cai, 2-Chloroanilinium perchlorate, Acta Cryst. E68 (2012) o2113.
[21] S. K. Seth, S. Banerjee, T. Kar, Crystal structure and DFT calculations of
andrographiside, J. Mol. Struct. 965 (2010) 45-49.
[22] S. K. Seth, N. C. Saha, S. Ghosh, T. Kar, Structural elucidation and electronic
properties of two pyrazole derivatives: A combined X-ray, Hirshfeld surface analyses
and quantum mechanical study, Chem. Phys. Lett. 506 (2011) 309-314.
[23] Z. L. Wang, L. H. Wei, L. Y. Jin, J. P. Wang, Synthesis, Structure and Theoretical
Calculation of Imidazolium 3,5-Dinitrobenzoate, Chin. J. Struct. Chem. 26 (2007)
1423-1428.
[24] T. M. Klapötke, C. Miró Sabaté, The preparation and characterization of guanylurea
nitrate and perchlorate salts, Heteroatom Chem.19 (2008) 301-306.
[25] S. Soudani, J.-X. Mi, F. Lefebvre, C. Jelsch, C. Ben Nasr, Synthesis and physico-
chemical studies of a novel layered structure with a heptanuclear Cd complex:
(C9N4H28)Cd7(H2O)2Cl18·nH2O(n = 5.89), J. Mol. Struct. 1084 (2015) 46-54.
[26] A. Lemmerer, D. G. Billing, 2,4,6-Trimethylanilinium iodide, Acta Cryst. E63 (2007)
929-931.
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Figure captions
Fig. 1
ORTEP view of (I) and (II) with the atom-labeling. Displacement ellipsoids are drawn at 50%
probability. H-atoms are represented as small arbitrary radii.
Fig. 2
Projection, along the c-axis and a-axis of one inorganic layer of (I) and (II) respectively.
-
+
The voids between the ClO4 anions are filled with NH3 units for (II)
Fig. 3
Three dimensional network of (I) and (II), projected along the a-axis and b-axis, respectively
(For clarity, the H atoms of Carbon are omitted; H-bonds are represented by dashed lines).
Fig. 4
Frontier molecular orbitals (HOMO and LUMO) of (I).
Fig. 5
Frontier molecular orbitals (HOMO and LUMO) of (II).
Fig. 6
13C CP-MAS NMR spectrum of (I). The simulated spectrum is shown in the insert.
Fig. 7
13C CP-MAS NMR spectrum of (II). The simulated spectrum is shown in the insert.
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(I)
(II)
Fig. 1
16

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(I)
(II)
Fig. 2
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Fig. 2
(I)
(II)
Fig. 3
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Fig .4
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Fig. 5
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ppm
Fig. 6
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ppm
Fig. 7
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Table 1. Comparison of calculated and experimental chemical shift values of the
carbon atoms in (I) and (II).
Compounds
(I)
(II)
Atoms
C1
Experimental Calculated Experimental Calculated
121.7 (6.4)
139.4 (6.4)
137.7 (6.4)
130.8 (6.4)
119.9 (6.4)
127.5 (6.4)
123.9 (6.4)
155.7 (6.4)
142.6 (6.4)
139.0 (6.4)
121.0 (6.4)
125.3 (6.4)
121.7 (6.4)
-
123.1 (6.4)
154.5 (6.4)
141.4 (6.4)
138.6 (6.4)
120.6 (6.4)
124.8 (6.4)
C2
C3
138.5 (6.4)
130.2 (6.4)
120.3 (6.4)
127.6 (6.4)
C4
C5
C6
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Highlights
•
Two new nitrate and perchlorate salts of 3-chloroaniline, were synthesized.
•
•
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Vibrational properties were studied by IR spectroscopy.
Solid-state 13C CP-MAS NMR spectroscopy is in agreement with the X-ray structure.
NMR peaks were attributed with the help of DFT calculations.
The electronic properties such as HOMO and LUMO energies were studied.