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j.molstruc.2017.10.063

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Accepted Manuscript
Synthesis, crystal structure and dielectric properties of the new organic -inorganic
hybrid compound [C6H10N2]7[Bi2Cl11]2.4[Cl]
Mohamed Hamdi, Sahel Karoui, Abderrazek Oueslati, Slaheddine Kamoun,
Faouzi Hlel
PII:
S0022-2860(17)31410-2
DOI:
10.1016/j.molstruc.2017.10.063
Reference:
MOLSTR 24434
To appear in:
Journal of Molecular Structure
Received Date:
27 April 2017
Revised Date:
16 October 2017
Accepted Date:
17 October 2017
Please cite this article as: Mohamed Hamdi, Sahel Karoui, Abderrazek Oueslati, Slaheddine
Kamoun, Faouzi Hlel, Synthesis, crystal structure and dielectric properties of the new organic inorganic hybrid compound [C6H10N2]7[Bi2Cl11]2.4[Cl], Journal of Molecular Structure (2017), doi:
10.1016/j.molstruc.2017.10.063
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ACCEPTED MANUSCRIPT
- A new organic–inorganic hybrid compound, [C6H10N2]7[Bi2Cl11]2.4[Cl], has been
successfully synthesized
- The AC conductivity is well described by Jonscher’s universal power law
- The DC conductivity variation suggests Arrhenius type of electrical conductivity
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Fig: ORTEP view of [C6H10N2]7[Bi2Cl11]2.4[Cl]
ACCEPTED MANUSCRIPT
Synthesis, crystal structure and dielectric properties of the new
organic -inorganic hybrid compound [C6H10N2]7[Bi2Cl11]2.4[Cl]
Mohamed Hamdi (a)*, Sahel Karoui(b), Abderrazek Oueslati(a), Slaheddine
Kamoun(b) and Faouzi Hlel(a)
*Corresponding author: hamdymed@gmail.com
(Tel: + 216 22 47 46 48)
(a): University of Sfax, Laboratory of Spectroscopic Characterisation and Optics of Materials, Faculty
of Sciences BP. 1171, 3000 Sfax, Tunisia
(b): University of Sfax, Laboratory of Material Engineering and Environment, National School of
Engineering, Box 1173, 3038, Sfax, Tunisia
ABSTRACT: A new organic-inorganic hybrid compound, [C6H10N2]7[Bi2Cl11]2.4[Cl], was
synthesized, the crystal was grown by slow evaporation solution technique at room
temperature and its structure determined by means of single crystal X-ray diffraction studies.
The molecule crystallizes in the tetragonal P4/n space group with cell parameters a = b =
12.9758(14) Å, c = 14.2611(17) Å, V = 2401.2(5) Å3 and Z=1. Crystal structure was solved
with a final R = 0.033 for 2185 independent reflections. The structure consists of alternate
organic and inorganic layers stacked in the a-direction. The anionic layers are made up of
discrete [Bi2Cl11]5- tetrahedrons, while the cationic layers are formed by [C6H10N2]2+ cations.
Hirschfeld surface analyses of the studied salt have also been carried out. Furthermore, the
complex impedance of the compound has been investigated in the temperature range of 293–
423 K and in the frequency range of 209 Hz–5 MHz. The frequency-dependent AC
conductivity is well described by Jonscher’s universal power law. The nature of DC
conductivity variation suggests Arrhenius type of electrical conductivity. Besides, ananalys is
of the dielectric constants ε’, ε’’ versus temperature, at several frequencies, shows a
distribution of relaxation times. Which is probably related to the change in the dynamical state
of the [C6H10N2]2+ cations and the [Bi2Cl11]5- anions.
Keywords: Organic–inorganic hybrid material. Crystal structure. AC conductivity. DC
conductivity. Dielectric properties.
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1. Introduction
Organic–inorganic hybrid compounds have attracted much attention in recent research due not
only to their fascinating architectures, but also because of their ability to combine the specific
properties of inorganic frameworks and the features of organic molecules [1, 2, 3, 4, 5, 6].
Indeed, the synthesis of low-dimensional mixed inorganic–organic materials enables both
inorganic and organic components at the molecular level to exhibit specific properties such as
dielectrics [7,8], metallic conductivity [9,10], magnetic [11], luminescence, nonlinear optics
[12,13] and photochemical properties [14]. In the literature, the investigation of hybrid
compounds with the general formula A4M2Xn (where A is an organic cation, M is a divalent
metal (Sn, Zn, Cu, Cd, Hg, Bi, Sb…), and X is a halogen (Cl, Br and I)) has aroused
considerable attention in the recent years due to the remarkable chemical and physical
properties [15, 16, 17, 18].
Currently, the results on the field of hybrid materials are very courageous. In view of the wide
range of functionality of these materials, they have improved inhabited characteristics
allowing the development of innovative industrial applications such as transport, medical
biology, fuel cells and photovoltaic cells [16 - 18]
Impedance spectroscopy is one of the significant experimental techniques to analyze the
dynamics of the ionic mobility in solids. Moreover, it gives valuable information about
conduction mechanism and to understand the nature and the origin of dielectric losses [19,20,
21, 22]. Besides, measurement of ac conductivity and dc conductivity are extensively used to
characterize electrical properties of various compounds.
The structure of this hybrid compound consists of alternating organic and inorganic layers.
The bond between the two components was achieved by an aromatic ring which makes a
hydrogen/ion bond with the halogen atoms (chloride) and makes this type of material a good
candidate for conduction of the proton.
In the present investigation, the synthesis, structural characterization at room temperature, the
dielectric relaxation and the conduction mechanism in [C6H10N2]7[Bi2Cl11]2.4[Cl] is examined
by ac and dc conductivity in the frequency range of 209 Hz–5 MHz and the temperature range
of 293–423 K. The results were presented and discussed.
2. Experimental details
2.1. Synthesis of single crystals
1,2-Diaminocyclohexane (purity 98%; Sigma Aldrich) and bismuth(III) oxide Bi2O3 (purity
98%; FLUKA) were dissolved in a 1 M HCl (37%; Fluka) aqueous solution and stirred for a
few minutes. The obtained solution was slowly evaporated at room temperature. After four
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days, plate [C6H10N2]7[Bi2Cl11]2.4[Cl] colorless crystals appeared. The single crystal was
selected by using the microscope.
Schematically the reaction is shown in the following equation:
7[C6H8N2] + 2Bi2O3 + 26HCl → [C6H10N2]7[Bi2Cl11]2.4[Cl]+ 6H2 + 3O2
2.2. Investigation techniques
2.2.1. X-ray diffraction
The single-crystal X-ray data collection was performed on plate single crystal with
dimensions (0.43×0.36×0.43 mm3) chosen by optical microscope. Data were obtained using a
Bruker APEXII diffractometer with monochromated graphite MoKα radiation (λ=0.71073 Å).
The absorption corrections were based on multiple and symmetry-equivalent reflections in the
data set using the SADABS program [23]. The compound crystallizes, at room temperature,
in the tetragonal system with the non-centro-symetric space group, P4/n. The structure was
solved by the Patterson methods, using the SHELXS-97 [24] and refined with SHELXL-97 [
25] programs. All reflections were executed from the WINGX program [26], which readily
established the heavy atoms positions and facilitated the identification of the light atoms from
different Fourier maps. The molecular drawings were generated utilizing DIAMOND
program [27]. Pertinent details of the crystal structure of [C6H10N2]7[Bi2Cl11]2.4[Cl] are listed
in Table 1.
Atomic coordinates anisotropic displacement parameters, tables for all bond distances, and
angles have been deposited at the Cambridge Crystallographic Data Centre (deposition
number: CCDC1472595). Copies of the data can be obtained, free of charge, on application to
the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: (44) 1223 336-033; email: deposit@ccdc.cam.ac.uk).
2.2.2. Hirshfeld surface analysis
The percentage contributions for various intermolecular contacts in the crystals of Bismuth
salt were obtained from Hirschfield surface analyses, and 2D fingerprint plots were recorded
on Crystal-Explorer .2.1 [28]. Both de and di are responsible for the normalized contact
distance (dnorm).
2.2.3. Dielectric measurements
The electrical measurements were performed on polycrystalline sample pressed into pellets of
8 mm in diameter and 1.2 mm in thickness using 3 t/cm2 uniaxial pressures. The pellet was
sandwiched between two silver electrodes of the configuration Ag/electrolyte/Ag. The
complex electric permittivity ε* = ε’ + j ε’’ were measured in the frequency range 209 Hz – 5
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MHz with a TEGAM 3550 automatic bridge monitored by a microcomputer. Measurements
were made over the temperature range 293 – 423 K. Temperature was measured using a
thermocouple with 2° precision.
3. Results and discussions
3.1. Crystal structure description
The single crystal X-ray diffraction measurements revealed that [C6H10N2]7[Bi2Cl11]2.4[Cl]
crystallized into the Tetragonal crystal system with the space groups P4/n, the unit cell
parameters a=12.9758(14) Å, b=12.9758(14) Å, c=14.2611(17) Å, V=2401.2(5)Å3 with Z=1
at 293 K (Table 1).
The final atomic coordinates and Ueq or Uiso are given in Table 2. Interatomic distances,
bond angles, and the hydrogen bonds schemes are listed in Table 3, respectively. In the title
compound, [C6H10N2]7[Bi2Cl11]2.4[Cl], the asymmetric unit contains seven kinds of
nonequivalent 1-2 diamonium cyclohexane cations, two of discrete [Bi2Cl11]5− and four
chloride anion (Fig.1). A perspective view of the arrangement of these constituent entities is
shown in Fig. 2 together with the atom numbering scheme. The [Bi2Cl11]5− anion forms a
bioctahedron with a common Cl atom [Cl(3)]. Each Bi atom is surrounded by six Cl atoms
forming a distorted octahedral configuration with Bi-C1 bond lengths ranging from 2.522(3)
to 2.923(3)Å. These values are much shorter than the sum of Van der Waal's radii of Bi and
Cl (4.7Å, according to Pauling) [29]. The average Cl-Bi-Cl angle is 96.04(5)°. The terminal
bond lengths of the [Bi2Cl11]5- anion range from 2.522(3) to 2.923(3)Å. The long distances
Bi(1)-C1(2) = 2.719(2)Å and Bi(2)-Cl(4)= 2.702(2)Å are due to the presence of intermediate
strength hydrogen bonds between Cl atoms and H atoms belonging to the N atoms of the
organic groups: [N(1)···Cl(2) = 3.275(7), N(1) ···Cl(4) = 3.350(7) and N(2)...Cl(4) =
3.554(7)Å], the sum of the Van der Waal's radii of N and Cl is 3.3Å. The bridging Bi-Cl(3)
bonds [2.923(3) and 2.790(3)Å] are elongated and the trans Bi-C1 terminal bonds [Bi(1)Cl(1) = 2.522(3), Bi(1)-Cl(2) = 2.719(2) and Bi(2)-Cl(4) =2.702(2)Å,] are shortened
compared with the remaining average Bi-C1 bond lengths [2.719(2)Å and 2.655(2 )Å,
respectively, for the Bi(1)Cl6 and Bi(2)Cl6 octahedral]. The bond angles within the [Bi2Cl11]5anion of the title compound, listed in Table 3, do not indicate stereochemical activity of the Bi
lone electron pair, which, however, has not been observed, in other halogenobismuthates (III)
either [ 30, 31].
The [Bi2Cl11]5- bioctahedra are connected through N–H···Cl hydrogen bonds, so that infinite
two dimensional chains parallel to the [001] plan (Fig.3) are formed in the structure. Table 4
reports the principal geometrical features of the organic group. The C–N and C–C bond
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lengths vary from1.497 (9) to1.532 (10) and 1.487(13) to 1.515(12), respectively. The phenyl
ring is practically planar with the greatest deviation from the six-atoms least squares plane
being 0.2210Å. The torsion angle N1–C1–C2–N2 is 63.0(8)° indicating that the N1–C1 and
C2–N2 groups deviate from the phenyl ring plane. The phenyl ring is regular with C≈C≈C
angles in agreement with the expected sp2 hybridation. The intermolecular hydrogen bonding
contacts N–H···Cl provide a linkage between the [C6H10N2]2+ entities, the chloride and the
[Bi2Cl11]5- anions (Fig. 3). All these hydrogen bonds (Table 5) give rise to a bi-dimensional
network and add stability to this compound (Figs. 2 and 3).
3.2. Hirshfeld surface analysis
The intermolecular interactions of this new compound and of the previously reported [32]
were analyzed using the two dimensional fingerprint plots [33] derived from Hirshfeld
surfaces [34], using the software Crystal Explorer, version 2.1 [28]. 2D-fingerprint plots were
generated by using the di and de pairs measured on each individual spot of the calculated
Hirshfeld surface. Here, we estimate the intermolecular contacts, which are shown in Fig. 4.
86.1% contribution with pair of sharp spikes towards Hirshfeld surfaces were noticed from
H⋯Cl, hydrogen bond contacts. However, 9.1% contributions arise from H⋯H contact
appearing as a sharp spike between two peaks of hydrogen bond over Hirshfeld surface of the
studied salt. However, Cl⋯Cl, and Bi⋯H contacts have little contributions of 4.7 and 0.1%,
respectively.
3.3. Complex impedance spectroscopy
3.3.1. Dielectric studies
The study of complex permittivity formalism is an important source for valuable information
about the mechanisms of conduction in the materials and the origin of the dielectric
relaxation. The complex dielectric function is expressed as [35]:
ε*() = ε’ () + jε’’ ()
Where ’() and
(I)
’’() are the real and imaginary parts of the dielectric constant,
respectively.
The temperature dependences of the real ε’ and imaginary ε’’ parts of the dielectric
permittivity for the [C6H10N2]7[Bi2Cl11]2.4[Cl] compound at different frequencies are shown
in Figs. 5 and 6 respectively. At low temperature (up to 373 K), the variations of ε' and ε''
with temperature are almost constants. This behavior may be explained by the restricted
reorientational motions of the cation which cannot orient itself with respect to the direction of
applied electric field [36]. Beyond T=373K, the variations of the dielectric constants (ε′ and
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ε″) starts to increase quickly with the temperature and its value strongly depends on the
frequency, which may be related to the increase of disorder in the sample. The corresponding
disorder induced weakens forces of Van Der Waals, as well as electrostatic interaction.
However, charge carriers can orient themselves with respect to the direction of applied
electric field [37]. As the temperature increases, the bound charge carriers get gradually an
amount of thermal excitation energy to be able to respond to the change in the external field
more easily. This phenomenon could be due to the accumulation of several mechanisms, such
as the reorientation of the organic groups and the increase of the mobility of charge carriers.
The variation of the real part of the permittivity with angular frequency is presented in Fig. 7.
This figure shows that at low frequencies the dispersions are very strong and they are
proportional to -(1-n) [38, 39]. Such behavior is characteristic of interaction between mobile
ions when they are in motion.
The dielectric loss can be plotted as log (ε'') versus angular frequency () as it is represented
in Fig. 8. From this figure, the obtained curves are straight lines at various temperatures with
different slopes separated by the frequency region are present in the frequency dependence of
ε′'. The imaginary ( ε′') part of the dielectric constant, decreases as the frequency increases
and it increases as the temperature increases and show a (-1) slope, that because they are
dominated by the dc conduction mechanism [40, 41].
3.3.2. Modulus studies
The electrical modulus formalism is an important theory formulated by Macedo et al. [42].
This formalism permits to study charge transport processes such as mechanism of electrical
transport, conductivity relaxation, and ion dynamics. It allows eliminating the problems
related to the polarization of electrodes or other interfacial effect in the solid electrode [43].
The electric modulus (M*) is calculated from the following equation:
M* = jC0Z* = M’ + j M’’
(II)
Where M’ and M’’ are real and imaginary part of electric modulus, and C0 is the vacuum
capacitance of the measuring cell.
Together with: M’= jC0Z’’ and M’’ = jC0Z’
Where C0 = 0S / e, 0 is the permittivity of vacuum, S is the surface of the sample, e is the
sample thickness and  is the angular frequency ( = 2f (f being the frequency in Hz)).
The graph of the imaginary part of the dielectric modulus, as a function of frequency at
different temperatures, for [C6H10N2]7[Bi2Cl11]2.4[Cl] compound, is shown in Fig. 9 The plot
of imaginary part of M shows a slightly asymmetric peak at each temperature. The peak shifts
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toward higher angular frequencies (107) with the increase in temperature. This behavior
suggests that the dielectric relaxation is thermally activated, where a hopping mechanism of
charge carriers dominates intrinsically [44, 45]. The asymmetry in peak broadening shows the
spread of relaxation times with different time constants. The frequency of the modulus
maximum shifts to higher frequency side with the increase in temperature [46, 47].
The angular frequency, ωmax = 2πfmax, which corresponds to peak M’’max, gives the relaxation
time τ, from the condition ωmax. τ=1. The plot of Ln(τ) versus 103/T for relaxation from M’’ at
different temperatures is shown in Fig. 10. The relaxation time τ obeys the Arrhenius relation
[48, 49]:
τ
=
τ0
exp
(
Ea
)
k BT
(III)
Where τ0 is the characteristic relaxation time, Ea is the activation energy and kB the
Boltzmann’s constant.
The values of these parameters calculated from a linear fit are Ea(I)=0.47 eV and Ea(II)=1.12
eV for both phases I and II, respectively. The activation energy calculated from the modulus
spectrum is also comparable to the values obtained from the conductivity, for the same
temperature range,
which confirms that the transport is made through an ion hopping
mechanism [50].
3.3.3. Conductivity study
** DC conductivity
The values of bulk resistance (R) at different temperatures have been obtained from the
intercept of the semicircular arcs on the real axis (Z’). It is observed that (R) decreases with
rise in the temperature. The values of resistance R, the area of the sample S and the material
thickness e are used to determine the dc conductivity, which is given by means of the relation
[51]:
σdc =
1 e
×
R S
(IV)
The temperature dependence of the dc conductivity is presented in Fig. 11, indicating an
Arrhenius-type behavior [52].
 = σ0 exp [-(Ea / KBT)]
(V)
Where σ0 is a constant, KB is the Boltzmann's constant and Ea is the apparent activation
energy for the ion migration.
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A change in the slope is noted around the temperature 273 K, where two regions of
conductivity may be identified as (I) and (II) are observed. This change is probably due to the
traces of moisture in the compound. However, the values of activation energies determined
from (Fig. 11) in regions (I) and (II) are 1.41 and 0.62 eV, respectively.
** AC conductivity
AC measurements are very important for any dielectric material as it gives a lot of
information about dynamic properties. AC measurements are also helpful in identifying the
nature of conduction mechanism.
The AC conductivity has been calculated from the real (Z’) and imaginary (Z’’) parts of the
impedance data measured over a study range of temperatures using the relation:
σAC = (e/s)[Z’/(Z’2 + Z’’2)]
(VI)
Where e and s are the thickness and the area of the pellets.
The frequency dependence of alternating current AC conductivity for the studied materials at
various temperatures is depicted in Fig. 12. The phenomenon of the conductivity dispersion is
generally analyzed using Jonscher’s law [53]:
σac(ω) = σdc + Aωn
(VII)
Where σdc is the direct current conductivity, A is a constant which determines the strength of
polarizability, ω = 2πf is the angular frequency and n is an exponent less than or equal to
unity which represent the degree of interaction between mobile ions and its surrounding
lattices.
In fact, the conductivity curves reveal two distinct regions the low frequency regions and high
frequency regions. The appearance of plateau at low frequency region which increases with
temperature reflecting the direct current conductivity σdc due to the uncorrelated hopping
motions of charges carriers [54]. At fixed angular frequency, the conductivity increases with
increasing temperature. While at high frequencies the conductivity increases gradually with
the increase in frequency. The observed behavior is in general agreement with the prediction
of the jump relaxation model [55, 56].
4. Conclusions
In summary, a novel organic–inorganic hybrid compound, [C6H10N2]7[Bi2Cl11]2.4[Cl], has
been successfully synthesized at room temperature by slow evaporation. This compound
belongs to the tetragonal system with the P4/n space group. The atomic arrangement can be
described as an alternation of organic/inorganic layers along the a direction. The asymmetric
unit contains seven kinds of nonequivalent 1-2 diamonium cyclohexane cations, two of
discrete [Bi2Cl11]5− and four chloride anion. The intermolecular hydrogen bonding contacts
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N–H···Cl provide a linkage between the [C6H10N2]2+ entities, the chloride and the [Bi2Cl11]5anions. The [Bi2Cl11]5- bioctahedra are connected through N–H···Cl hydrogen bonds.
The electrical and dielectric properties of [C6H10N2]7[Bi2Cl11]2.4[Cl] single crystals, in the
frequency interval of 209 Hz – 5 MHz and temperature interval of 293–423 K , were reported
by the first time in the present work. The imaginary (ε′') part of the dielectric constant,
decreases as the frequency increases and it increases as the temperature increases. The plot of
imaginary part of M shows a slightly asymmetric peak at each temperature. The peak shifts
toward higher angular frequencies (107) with the increase in temperature. The AC
conductivity curves reveal two distinct regions the low frequency regions and high frequency
regions. The appearance of plateau at low frequency region which increases with temperature
reflecting the direct current conductivity σdc due to the uncorrelated hopping motions of
charges carriers. The temperature dependence of the DC conductivity was analyzed using the
Arrhenius approach and showed the appearance of two regions. However, the values of
activation energies determined from in regions (I) and (II) are 1.41 and 0.62 eV, respectively.
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Fig.1
Fig. 2
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Fig. 3
Fig. 4
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Fig.5
Fig.6
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Fig.7
Fig.8
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Fig.9
Fig.10
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Fig.11
Fig.12
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Table 1
Compound
[C6H10N2]7[Bi2Cl11]2. 4[Cl]
Molecular weight
2528.74
Crystal color/form
Colorless / plate
System/ Space group
Tetragonal/ P4/n
Temperature (K)
293(2)
Cell dimensions
a, (Å)
12.9758(14)
b, (Å)
12.9758(14)
c, (Å)
14.2611(17)
Cell volume, (Å3)/ Z
2401.2(5) /1
Diffractometer/scan
SADABS; Bruker, 2006
Radiation, k (Å), monochromator
MoKα, 0.71069, graphite
Dimension du cristal, (mm)
0.43 x 0.36 x 0.43
Scan angle (°)
θ–2θ
θ Range (°)
1.43- 25.29
Unique reflections
2185
Reflections with I > 2σ(I)
1906
Range of h, k, l
−15→14, −12→15, −13→16
Tmin, Tmax
0.042, 0.062
Structure solution:
Patterson methods: SHELXS-86
Structure refinement with
SHELXL-97
Refinement
F2 full matrix
F(000)
1322
Goodness-of-fit (GOF)
1.057
Refined parameters
115
Final R and Rw
0.0336, 0.0811
Final R and Rw (for all data)
0.0424, 0.0856
w=1/[σ2 (Fo)2 + (0.0437 P)2 + 7.0405 P]
where P=(Fo2+2Fc2)/3
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Table 2
Atomes
Bi(1)
x
1/4
y
1/4
z
0.11021(3)
Ueq. and U*iso
0.02510(15)
Bi(2)
1/4
1/4
0.51081(3)
0.02342(15)
Cl(5)
1/4
1/4
-0.3079(2)
0.0538(10)
Cl(3)
1/4
1/4
0.3152(2)
0.0508(10)
Cl(1)
1/4
1/4
-0.0666(2)
0.0555(10)
Cl(4)
0.42488(16)
0.36305(18)
0.50996(15)
0.0611(6)
Cl(2)
0.28205(14)
0.45593(15)
0.13027(16)
0.0535(5)
Cl(6)
0.31478(17)
0.59112(18)
0.37967(15)
0.0622(6)
C(1)
C(2)
C(3)
C(4)
C(5)
0.5513(5)
0.6612(5)
0.6991(6)
0.6893(7)
0.5824(7)
0.4949(6)
0.4585(5)
0.3895(6)
0.4441(8)
0.4851(8)
0.2809(5)
0.2941(5)
0.2158(5)
0.1224(6)
0.1068(6)
0.0453(18)
0.0407(17)
0.0506(19)
0.067(3)
0.067(3)
C(6)
N(1)
N(2)
H(3)
H(4)
H(5)
H(6)
H(1A)
H(1B)
H(1C)
H(2A)
H(2B)
H(2C)
0.5441(7)
0.4735(5)
0.6773(5)
0.7247
0.743
0.5442
0.518
0.4102
0.4768
0.4882
0.7428
0.6365
0.6622
0.5482(7)
0.4061(5)
0.4090(5)
0.3232
0.4513
0.4725
0.6144
0.4309
0.374
0.3618
0.3895
0.3542
0.454
0.1866(7)
0.2826(4)
0.3878(4)
0.2238
0.0797
0.0529
0.1793
0.2742
0.3376
0.2369
0.3933
0.393
0.4329
0.064(3)
0.0525(17)
0.0535(17)
0.061*
0.08*
0.08*
0.077*
0.079*
0.079*
0.079*
0.08*
0.08*
0.08*
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Table 3
[Bi2Cl11]5Atoms
Distances (Å) Atoms
Angles(°)
Atoms
Angles(°)
Bi(1)-Cl(1)
2.522(3)
Cl(1)-Bi(1)-Cl(2)i
96.04(5)
Cl(5)iv-Bi(2)-C(l4)i
90.26(5)
Bi(1)-Cl(2)i
2.719(2)
Cl(1)-Bi(1)-Cl(2)
96.04(5)
Cl(5)iv-Bi(2)-Cl(4)
90.26(5)
Bi(1)-Cl(2)
2.719(2)
Cl(2)i-Bi(1)-Cl(2)
167.92(6
Cl(4)i-Bi(2)-Cl(4)
179.49(6)
Bi(1)-Cl(2)ii 2.719(2)
Cl(1)-Bi(1)-Cl(2)ii 96.04(5)
Cl(5)iv-Bi(2)-Cl(4)iii
90.26(5)
Bi(1)-Cl(2)iii 2.719(2)
Cl(2)i-Bi(1)-Cl(2)ii 89.37(5)
Cl(4)i-Bi(2)-Cl(4)iii
90.00(7)
Bi(1)-Cl(3)
2.923(3)
Cl(2)-Bi(1)-Cl(2)ii 89.37(5)
Cl(4)-Bi(2)-Cl(4)iii
90.00(7)
Bi(2)-Cl(5)iv 2.585(3)
Cl(1)-Bi(1)-Cl(2)iii 96.04(5)
Cl(5)iv-Bi(2)-Cl(4)ii
90.26(5)
Bi(2)-Cl(4)i
2.702(2)
Cl(2)i-Bi(1)-Cl(2)iii 89.37(5)
Cl(4)i-Bi(2)-Cl(4)ii
90.00(7)
Bi(2)-Cl(4)
2.702(2)
Cl(2)-Bi(1)-Cl(2)iii 89.37(5)
Cl(4)-Bi(2)-Cl(4)ii
90.00(7)
Bi(2)-Cl(4)iii 2.702(2)
Cl(2)ii-Bi(1)-Cl(2)iii 167.92(6)
Cl(4)iii-Bi(2)-Cl(4)ii
179.49(6)
Bi(2)-Cl(4)ii 2.702(2)
Cl(1)-Bi(1)-Cl(3)
180.00(5
Cl(5)iv-Bi(2)-Cl(3)
179.99(5)
Bi(2)-Cl(3)
2.790(3)
Cl(2)i-Bi(1)-Cl(3)
83.96(5)
Cl(4)i-Bi(2)-Cl(3)
89.74(5)
Bi(2) - Cl(5)iv 2.585(3)
Cl(2)-Bi(1)-Cl(3)
83.96(5)
Cl(4)-Bi(2)-Cl(3)
89.74(5)
Cl(2)ii-Bi(1)-Cl(3)
83.96(5)
Cl(4)iii-Bi(2)-Cl(3)
89.74(5)
Cl(2)iii-Bi(1)-CL(3) 83.96(5)
Cl(4)ii-Bi(2)-Cl(3)
89.74(5)
Bi(2)-Cl(3)-Bi(1)
180.00(7)
Symmetry codes: (i) 0.5-x, 0.5-y, z; (ii) 0.5-y, x, z; (iii) y, 0.5-x, z; (iv) x, y, 1+z; (v) x, y, -1+z.
ACCEPTED MANUSCRIPT
Table 4
[C6H10N2]2+
Atoms
Distances/Å
Atoms
Angles(°)
C(2)-N(2)
1.497(9)
N(2)-C(2)-C(3)
111.06(57)
C(2)-C(3)
1.513(10)
N(2)-C(2)-C(1)
112.10(56)
C(2)-C(1)
1.514(9)
C(3)-C(2)-C(1)
113.51(58)
C(1)-C(6)
1.515(12)
C(2)-C(1)-C(6)
108.11(61)
C(1)-N(1)
1.532(10)
C(2)-C(1)-N(1)
112.58(54)
C(5)-C(6)
1.487(13)
C(6)-C(1)-N(1)
108.46(61)
C(5)-C(4)
1.502(13)
C(6)-C(5)-C(4)
112.96(78)
C(3)-C(4)
1.514(12)
C(4)-C(3)-C(2)
110.18(62)
C(5)-C(6)-C(1)
114.03(77)
C(5)-C(4)-C(3)
111.94(73)
C(3)-C(2)-C(1)
113.51(58)
C(2)-C(1)-C(6)
108.11(61)
C(2)-C(1)-N(1)
112.58(54)
Table 5
D-H···A
N···H
H···Cl
N···Cl
N–H···Cl
N(1) –H(1A) –Cl(2)
0.89
2.66
3.362(7)
136.4
N(1) –H(1A) –Cl(6)
0.89
2.85
3.453(8)
126.4
N(1) –H(1B) –Cl(4)
0.89
2.55
3.350(7)
149.6
N(1) –H(1B) –Cl(6)
0.89
2.93
3.530(7)
126.7
N(1) –H(1C) –Cl(2)
0.89
2.44
3.275(7)
155.8
N(2) –H(2A) –Cl(6)
0.89
2.37
3.246(7)
167.7
N(2) –H(2B) –Cl(6)
0.89
2.28
3.114(7)
156.4
N(2) –H(2C) –Cl(6)
0.89
2.75
3.317(6)
122.6
N(2) –H(2C) –Cl(4)
0.89
2.75
3.554(7)
150.4
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