Journal of Molecular Structure 1031 (2013) 152–159

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Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstruc

New molybdate Li2Co2x Nix (MoO4)3 (0 6 x 6 2) materials with a lyonsite

structure: X-ray diffraction and Raman spectroscopy studies
H. Bensaid a, A. El Bouari a,⇑, S. Benmokhtar b, B. Manoun c, L. Bih c, P. Lazor d
a
LCMS, Laboratory of Chemistry of Solid Materials, Department of Chemistry, Faculty of Sciences, Ben M’Sik-Casablanca, Morocco
b
LRCPGM, Research Laboratory of General Chemistry–Physics of Materials, Department of Chemistry, Faculty of Sciences, Ben M’Sik-Casablanca, Morocco
c
LPCM, Laboratory of Physico-Chemistry of Materials, Department of Chemistry, FST Errachidia, Morocco
d
Department of Earth Sciences, Uppsala University, S-752 36 Uppsala, Sweden

h i g h l i g h t s

" New series of Lyonsite Li2Co2xNix(MoO4)3 (0 6 x 6 2) were prepared by soft-combustion method.

" Raman vibrational spectroscopy and their structures was discussed based on structural analysis.
" We studied the soft-combution reactions of the compositions Li2Co2xNix(MoO4)3 (0 6 x 62).
" Structural characterization of a compounds via Rietveld Method.
" We analyzed the obtained lyonsite via Raman spectroscopy.

a r t i c l e i n f o a b s t r a c t

Article history: A solid solution was found to exist in the quaternary Li2O–CoO–NiO–MoO3 system between the two
Received 5 April 2012 phases Li2Co2(MoO4)3 and Li2Ni2(MoO4)3. Both Li2Co2(MoO4)3 and Li2Ni2(MoO4)3 are isostructural with
Received in revised form 25 June 2012 the mineral lyonsite, and substitution according to the formula Li2Co2xNix(MoO4)3 (0 6 x 6 2) demon-
Accepted 27 June 2012
strates that a complete solid solution exits. Rietveld analysis revealed that solid solution crystallizes at
Available online 25 July 2012
room temperature in orthorhombic space group Pnma (D2h). The structure shows that if the corners
and edges octahedra share in the leaves, they share faces columns. Nickel and cobalt are shared statically
Keywords:
in the trigonal prism and octahedral sites. The results of these compositions are consistent with studies
X-ray diffraction
Raman spectroscopy
where the Raman spectra. Therefore, all compositions are similar and show linear changes frequencies
Lyonsite Li2Co2xNix(MoO4)3 depending on the composition due to the substitution of Co2+ by Ni2+ with a larger radius.
Solid state Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction to the orthorhombic NaCo2.31(MoO4)3 [20], contain open frame-

Triple molybdates MM0 xM00 y(MoO4)Z (M: univalent cation, M0
and M00 : di-, tri or tetravalent cations) are well-known and promis-
ing as ferroelectrics, solid electrolytes, laser, acousto-optical, lumi-
nescent and other inorganic materials [1–5]. The range of complex
Mo(VI) oxide phases has been expanding over the past two dec-
ades, mainly, for account of triple molybdates revealed in the
course of exploring ternary salt systems [5–10]. In our laboratory
we have already reported in [11] about a synthesis and structural
characterization by X-ray diffraction and vibrational Raman spec-
tra of the Li2xNaxCo2(MoO4)3 (0 6 x 6 1.4) solid solution.
The structures of molybdates Li2M2II(MoO4)3 (M = Mg, Mn, Co,
Ni, Cu, Zn), [12–16], Li3MIII(MoO4)3 (M = Al, Cr, Ga, Sc, In, Co),
[17–19] and Li2MIV(MoO4)3 (M = Ti, Zr, Hf) [27–2] closely related
⇑ Corresponding author.
E-mail address: elbouari@yahoo.fr (A. El Bouari).
works formed by MoO4 tetrahedra, NaO6 and CoO6 octahedra.
Since then, both powder and single-crystal X-ray and neutron dif-
fraction studies have been performed to establish the structure of
others triple molybdates. Li2M3R(MoO4)4 (MR = TlAl, RbAl, RbGa,
CsAl, CsGa, CsFe) closely related to the cubic Cs6Zn5(MoO4)8 type

[21,22], contain open frameworks formed by MoO 4 ; LiO4 and
RO4 tetrahedra with 12-coordinate M +
ions located in their large
cavities. A triple molybdates LiMR2(MoO4)4 (M = K, Rb, Tl; R = Ln,
Bi) comprising 26 members has a structure being a stuffed deriva-
tive of the monoclinic BaNd2(MoO4)4 structure type (space group
C2/c, Z = 4) [23,24]. In LiMR2(MoO4)4 structures, RO8 polyhedra
sharing vertices with MoO4 tetrahedra form open layers linked
via MO10 polyhedra and LiO6 octahedra.
Among lithium transition metal oxides with lyonsite structures,
Li2M2(MoO4)3 and Li3M(MoO4)3 (M = Fe, Co, Ni) can perform very
well. Recently, Prabaharan and all [25,26] have discovered the
high-voltage redox behavior of the lithiated phase of Li2Ni2(MoO4)3

0022-2860/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2012.06.060
 H. Bensaid et al. / Journal of Molecular Structure 1031 (2013) 152–159
with a discharge capacity of 115 mA h g1. Thus, it is revealed
now that the open framework-type polyanion family of com-
pounds with the general formula Li2M2(MoO4)3 (M = transition
metal) indeed exemplifies the topotactic extraction/insertion of
Li+ within the framework [27]. The compounds Li2M2(MoO4)3
and Li3M(MoO4)3 (M = Fe, Co, Ni) are isostructural and attracted re-
cently attention, because of their ability for reversible Li insertion
[26–28]. They crystallize in a lyonsite-type structure, which was
first described for the Na, Co-containing molybdate with NaCo2.31(-
MoO4)3 stoichiometry [29]. The nominal lyonsite structure is
orthorhombic (space group Pnma) and high-oxidation state cation
(Mo6+) occupy the two unique tetrahedrally coordinated sites. The
structural connectivity of lyonsite type oxides is based on an array
of pseudo-hexagonal oxygen atoms, and built up of isolated MoO4
tetrahedra linked by MO6 chains, which can be seen. The most un-
ique features of the structure are the hexagonal tunnels that con-
sist of MO6 polyhedra. Two sides of the hexagonal tunnel are
created by zigzag sheets of edge-sharing M-centered trigonal
prisms, while the remaining four sides are composed of columns
of edge-sharing M-centered octahedra. Isolated MoO4 tetrahedra
are joined to the inside of the tunnel, and infinite chains of face
shared MO6 octahedra pass through the center of these tunnels.
There are large channels along one crystallographic axis in the
structure, which are occupied by either only Li atoms as in the case
of Li3M(MoO4)3 or by Li and M atoms as for Li2M2(MoO4)3. The
structural similarity of Li2M2(MoO4)3 and Li3M(MoO4)3 can be de-
scribed as a heterovalent replacement Li2M2(MoO4)3 ? Li2(Li,
M)(MoO4)3 ? Li3M(MoO4)3.
The number of different cations known to occupy the six coordi-
nate M position is extensive [30]. The identity of the M-site cation
seems to depend almost exclusively on size (0.46 6 r(Å) 6 1.02).
Fig. 1. Powder diffraction patterns of Li2Co2x Nix(MoO4)3 (0 6 x 6 2).
153
The cation charge has almost no effect on the identity of M, with
cations of oxidation state +1 through +4 shown to occupy the
six-coordinate positions. A close examination of the literature data
dedicated to the lyonsite shows that among the large number of re-
ported structures, the phases Li3M(MoO4)3 (M = Fe, Al, Ga, Cr, Sc, In)
[16–19–31], Li2M2(MoO4)3 (M = Fe, Co, Ni, Mg, Mn, Zn) [32–13],
Li2Zr(MoO4)3 [33] are the lithium containing ones. To overcome
these bibliographic shortcomings, we recently started a systematic
investigation of the quaternary Li2O–CoO–NiO–MoO4 system
leading to the preparation of Li2Co2xNix(MoO4)3 solid solution
(0 6 x 6 2). As a result of further investigation of other quaternary
Li2O–CoO–NiO–MoO4 systems, we report herein on the synthesis
and characterization by X-ray diffraction and Raman spectroscopy
of Li2Co2xNix(MoO4)3 (0 6 x 6 2) solid solution which exhibits an
original tridimensional structure.
2. Experimental details
2.1. Synthesis of Li2Co2xNix(MoO4)3
Compounds of Li2Co2xNix(MoO4)3 solid solution were prepared
by precipitation wet method at 25 °C in glycine-nitrate aqueous
solutions containing (NH4)6Mo7O244H2O, Li(NO3) and M(NO3)2
(where M = Co, Ni) in an appropriate molar ratio (Li/Co/Ni/Mo stoi-
chiometry) and then mixed that acted as a mild combustion and
(fuel). Different compositions were prepared by changing the nick-
el content x in the Li2Co2xNix(MoO4)3. The mixture is then heated
under agitation at 85 °C during 2 h of precipitation, resulting in a
dark blue color paste-like substance upon evaporating the water.
The paste-like substance was allowed to decompose at 250 °C.
The heat disintegration reaction duly ignited by glycine due to
154 H. Bensaid et al. / Journal of Molecular Structure 1031 (2013) 152–159

spontaneous decomposition gave rise to semi-solid precursors be-

fore being finally decomposed to get dry powders of the product.
The powders of Li2Co2x Nix (MoO4)3 were obtained upon anneal-
ing the as-prepared dry powders at 600 and 700 °C in ambient
air during 24 h before different physicochemical characterizations.
The lyonsite structure has been confirmed by X-ray powder diffrac-
tion, Raman spectroscopy.

2.2. Data acquisition and processing

The X-ray powder diffraction data (XRPD) were collected at

room temperature using a Siemens D5000 diffractometer using a
graphite-monochromated (Cu Ka radiation, k = 1.5406 Å). The
structure of the lyonsite compound was derived from the step-
scanned X-ray intensity data, in the range 5–120 (2h) with a step
size of 0.017° and counting time of 12 s for each step. The struc-
tural parameters were refined by the Rietveld method [34] using
the computer program FULLPROF [35]. The values (a, b and c cell Fig. 2. (a) Cell parameter variation as a function of x for Li2Co2x Nix(MoO4)3
parameters, atomic positions, site occupancies, thermal parame- (0 6 x 6 2).
ters) of the Li2xNaxCo2(MoO4)3 were used as a starting model.
Pseudo-Voigt function was used to fit the individual reflection pro-
files. In the final step of refinement, all atomic positions and site
occupancies were refined simultaneously with thermal factor.
Unpolarized Raman spectra were collected in the back-scatter-
ing geometry, in the range 180–2280 cm1, at a resolution of about
3 cm1. Accuracy of spectral measurements, resulting from the
wavelength calibration procedure and experimental conditions, is
estimated to be about 1.5 cm1. Precision of the reported peak
positions, as represented by standard errors obtained in peak fits
is 0.04 cm1. The acquisition time varied from 2 to 5 s.

2.3. X-ray diffraction study

A continuous solid solution exists between Li2Co2(MoO4)3 and

Li2Ni2(MoO4)3 with (0 6 x 6 2). Fig. 1 shows the room temperature
XRD patterns of Li2Co2xNix(MoO4)3 (0 6 x 6 2). The patterns of all
compositions were indexed by DICVOL program [36]. Thus, the
powders are pure and they have crystallized in a lyonsite-type
structure without secondary phases being present within the
detection limits of ours instrument. In the orthorhombic system
with the space group Pnma and all samples with the compositions
(0 6 x 6 2) are pure phases. The experimental XRD data for all sam- Fig. 3. (b) Cell parameter variation as a function of x for Li2Co2x Nix(MoO4)3
ples were successfully indexed by DICVOL04 software is listed in (0 6 x 6 2).

Table 1. The lattice parameters were refined using the complete

powder diffraction. Table 1. depicted the cell parameter variations
as a function of the nickel content (x) for Li2Co2xNix(MoO4)3
(0 6 x 6 2). The replacement of Co2+ by Ni2+ in the framework re-
sults in a shift of the X-ray peak positions due to unit cell changes
by considering the respective ionic radius and coordination of
these elements [37], the substitution of Co2+ (ri = 0.745 Å) for
Ni2+ ion (ri = 0.69 Å)) are possible. Such a proximity in size agrees

Table 1
Crystallographic data for solid solutions Li2Co2x Nix (MoO4)3 (0 6 x 6 2).

Parameters a (Å) b(Å) c(Å) V(Å3)

0 5.142(2) 10.551(3) 17.618(7) 955.834(5)
0.2 5.138(2) 10.542(3) 17.603(6) 953.463(5)
0.4 5.130(2) 10.483(2) 17.592(6) 946.059(6)
0.6 5.109(2) 10.472(2) 17.553(5) 939.111(6)
0.8 5.106(2) 10.463(3) 17.496(5) 934.708(4)
1 5.103(2) 10.446(3) 17.476(5) 931.575(4)
1.2 5.098(1) 10.437(2) 17.462(4) 929.115(4)
1.4 5.090(1) 10.418(2) 17.457(4) 925.703(4)
1.6 5.089(1) 10.381(1) 17.449(4) 921.811(3)
1.8 5.067(1) 10.374(1) 17.432(4) 916.314(3)
2 5.065(1) 10.362(1) 17.421(4) 914.316(3) Fig. 4. (c) Cell parameter variation as a function of x for Li2Co2x Nix(MoO4)3
(0 6 x 6 2).
 H. Bensaid et al. / Journal of Molecular Structure 1031 (2013) 152–159
Fig. 5. (V) Cell parameter variation as a function of x for Li2Co2xNix(MoO4)3
(0 6 x 6 2).
well with the fact that one Co can be replaced by Ni. In this case,
due to the slightly larger ionic radius sum of Co2+ compared to that
of Ni2+, the lattice parameters decreases when increasing nickel
content, i.e., the a-, b- and the c-axis decreases (Figs. 2–4). Both lat-
tice parameters vary linearly with the degree of substitution for
compositions relative to (0 6 x 6 2), thus, the Vegard’s law is
verified, as already observed when replacing Co by Ni in other
Co-containing lyonsite [29–38]. This confirms a homogeneous
distribution of both cations in the crystalline network. Concerning
Fig. 6. Final Rietveld plot of Li2Co2x Nix(MoO4)3 for (x = 1; x = 1.4).
155
the unit cell volume (Fig. 5), as the replacement of Co by Ni leads to
the contraction of both the a-, b- and c-axis, the decrease of the
unit cell volume is easy to predict and is in good agreement with
the fact that Co ion is smaller larger than the Ni ion. The observed,
calculated and the difference of the X-ray diffraction patterns for
compositions Li2Co2xNix(MoO4)3 (x = 1 and x = 1.4) are depicted
in Fig. 6 as examples.
2.4. Structural description
The structure solutions of these three crystal samples were per-
formed proceeding from their isostructurality to Li2xNaxCo2(-
MoO4)3 [11]. Correspond to space group (Pnma) and the atomic
positions was used as starting sets in the refinement procedure
for the Li2Co2xNix(MoO4)3 (0 6 x 6 2) samples (Fig. 7). A third-or-
der polynomial was employed to assimilate the background while
the peaks were fitted by using a pseudo-voigt function. The half-
width of the diffraction peaks as a function of 2h was evaluated
by the Caglioti equation [39]. In the first cycles, the scale factor
and the background coefficients were refined. Successively, the
profile parameters and the lattice parameters were allowed to vary
too. Finally, the occupancy factors were refined and the cation sub-
stitution was tested. No constraint was imposed. Details of exper-
iment and anisotropic refinement the samples Li2Co1Ni1(MoO4)3
and Li2Co0.6Ni1.4(MoO4)3 are listed in (Table 2.) The final positional
and thermal parameters of atoms are given in (Table 3); selected
interatomic distances are presented in (Table 4).
The structures Li2Co2xNix(MoO4)3 (x = 1, x = 1.4) are isostructur-
al to Li2M2(MoO4)3 with M = Co, Ni [25,26]. This structure type
was first described for the Na, Co-containing molybdate with
156 H. Bensaid et al. / Journal of Molecular Structure 1031 (2013) 152–159

Fig. 7. Schematic projection of the Li2Co2xNix(MoO4)3 (x = 1).

Table 2 NaCo2.31(MoO4)3 stoichiometry [29]. In the structure, there are two

Crystal data and structure refinement details for Li2Co2xNix(MoO4)3 (x = 1; x = 1.4). types of (Li/Co/Ni)-octahedra: infinite chains of face-sharing Li(1)/
Co(1)/Ni(1)–O(6) along (1 0 0) and networks of corner and edge-
Formula Li2Co1Ni1(MoO4)3 Li2Co0.6Ni1.4(MoO4)3
sharing Li(2)/Co(2)/Ni(2)–O(6) parallel to (0 0 1). The isolated
Crystal system Orthorhombique Orthorhombique
MoO4-tetrahedra connect networks and chains via corner into a
Espace group Pnma Pnma
Z 4 4 pseudohexagonal framework with channels parallel to [1 0 0], which
Unit cell dimension (Å) a = 5.103(2) a = 5.090(1) are occupied by Li/Co/Ni-atoms. The average Li(1)/Co(1)/Ni(1)–O
b = 10.446(3) b = 10.418(2) distances are of 2.139–2.152 Å, the Li(2)/Co(2)/Ni(2)–O distances
c = 17.476(5) c = 17.457(4) are between 2.088–2.079 Å and for Li(3)/Co(3)/Ni(3)–O distances
Volume (Å3) 931.575 (4) 925.703 (4)
Wavelength (Å) k1 = 1.5406 k1 = 1.5406
are of 2.161–2.229 Å. Also, two kinds of crystallographically inde-
2h range (°) 5.005–119.989 10.014–119.987 pendent MoO4 tetrahedra have a normal geometry with close
Step scan increment (2h) 0.017 0.017 dimensions and average Mo–O distances of 1.704–1.715 Å (Table 4).
Program FULLPROF FULLPROF Different synthesis temperatures (up to 650 °C) do not influence sig-
No. of reflections 767 760
nificantly the degree of the cation disorder (Li, Co and Ni) on the 4c
No. of refined Parameters 170 108
Caglioti law parameters U = 0.0211(2) U = 0.0125(2) and 8d sites. In order to confirm these XRPD experimental results we
V = 0.0223(1) V = 0.0096(1) discuss in the next section the Raman spectroscopic analysis.
W = 0.0132(2) W = 0.0083(1)
RF 7.56 4.38
RBragg 6.18 4.61 3. Raman spectroscopy
Rp 2.27 3.60
Rwp 3.33 4.67
Raman spectroscopy has been successfully used as a tool for
Rexp 1.40 3.77
studying the structure of lyonsite for the detection symmetry
 H. Bensaid et al. / Journal of Molecular Structure 1031 (2013) 152–159 157

Table 3
Positional and equivalent isotropic displacement parameters for Li2Co2xNix(MoO4)3 (x = 1; x = 1.4).

Atom wyckoff position x y z Biso Occ

Li2Co1Ni1(MoO4)3
Mo(1) 4c 0.2179(3) 0.25 0.0567(7) 2.76 (4) 1.00
Mo(2) 8d 0.2810 (2) 0.0270(7) 0.8435(5) 2.76(4) 2.00
Li(1) 8d 0.7504(6) 0.0729(19) 0.9736(13) 4.18(8) 0.44
Ni(1) 8d 0.7504(6) 0.0729(19) 0.9736(13) 4.18(8) 0.96
Co(1) 8d 0.7504(6) 0.0729(19) 0.9736(13) 4.18(8) 0.50
Li(2) 4c 0.3931(8) 0.25 0.2485(2) 3.71(15) 0.29
Ni(2) 4c 0.3931(8) 0.25 0.2485(2) 3.71(15) 0.34
Co(2) 4c 0.3931(8) 0.25 0.2485(2) 3.71(15) 0.25
Li(3) 4c 0.764(3) 0.25 0.8053(5) 4.0 (3) 0.40
Ni(3) 4c 0.764(3) 0.25 0.8053(5) 4.0 (3) 0.25
Co(3) 4c 0.764(3) 0.25 0.8053(5) 4.0 (3) 0.15
O(1) 8d 0.5704(12) 0.1008(7) 0.8662(4) 4.74(9) 2.00
O(2) 4c 0.1444(17) 0.25 0.1486(5) 4.74(9) 1.00
O(3) 8d 0.4301(12) 0.1272 (6) 0.0328(4) 4.74(9) 2.00
O(4) 4c 0.9315(17) 0.25 0.0028(6) 4.74(9) 1.00
O(5) 8d 0.3686(13) 0.1142 (6) 0.7915 (4) 4.74(9) 2.00
O(6) 8d 0.0884(11) 0.0014(6) 0.9195(4) 4.74(9) 2.00
O(7) 8d 0.0793(14) 0.1131(6) 0.7897(4) 4.74(9) 2.00
Li2Co0.6Ni1.4(MoO4)3
Mo(1) 4c 0.2167(4) 0.25 0.0567(10) 1.78(6) 1.00
Mo(2) 8d 0.2781(3) 0.02660(10) 0.8432(7) 1.78(6) 2.00
Li(1) 8d 0.7521(8) 0.0733(3) 0.9740(18) 3.09(10) 0.32
Ni(1) 8d 0.7521(8) 0.0733(3) 0.9740(18) 3.09(10) 1.20
Co(1) 8d 0.7521(8) 0.0733(3) 0.9740(18) 3.09(10) 0.30
Li(2) 4c 0.39(12) 0.25 0.2485(4) 4.2 (2) 0.41
Ni(2) 4c 0.39(12) 0.25 0.2485(4) 4.2 (2) 0.47
Co(2) 4c 0.39(12) 0.25 0.2485(4) 4.2 (2) 0.15
Li(3) 4c 0.752(4) 0.25 0.8031(8) 1.7(4) 0.40
Ni(3) 4c 0.752(4) 0.25 0.8031(8) 1.7(4) 0.45
Co(3) 4c 0.752(4) 0.25 0.8031(8) 1.7(4) 0.15
O(1) 8d 0.5530(17) 0.1097(9) 0.8687 (5) 3.51(12) 2.00
O(2) 4c 0.147(2) 0.25 0.1522 (7) 3.51(12) 1.00
O(3) 8d 0.4133(17) 0.1254(8) 0.0384(6) 3.51(12) 2.00
O(4) 4c 0.932 (2) 0.25 0.9987 (8) 3.51(12) 1.00
O(5) 8d 0.3544(18) 0.1141(8) 0.7939 (6) 3.51(12) 2.00
O(6) 8d 0.0891(16) 0.0086(9) 0.9186 (5) 3.51(12) 2.00
O(7) 8d 0.0837(19) 0.1243(8) 0.7859 (5) 3.51(12) 2.00

Table 4
Selected interatomic distances (Å) for Li2Co2xNix(MoO4)3 (x = 1; x = 1.4).

x=1 x = 1.4
Bond Length Bond Length
Mo(1)AO(3) 1.654(8) Mo(1)AO(2) 1.710(12)
Mo(1)AO(3)  2 1.729(6) Mo(1)AO(3)  2 1.670(8)
Mo(1)AO(4) 1.738(9) Mo(1)AO(4) 1.769(11)
<Mo(1)AO> 1.712 <Mo(1)-O> 1.704
Mo(2)AO(1) 1.709(6) Mo(2)AO(1) 1.703(9)
Mo(2)AO(5) 1.791(6) Mo(2)AO(5) 1.747(9)
Mo(2)AO(6) 1.677(6) Mo(2)AO(6) 1.673(8)
Mo(2)AO(7) 1.659(6) Mo(2)AO(7) 1.739(9)
<Mo(2)AO> 1.709 <Mo(2)AO> 1.715
Li(1)/Co(1)/Ni(1)AO(1) 2.116(7) Li(1)/Co(1)/Ni(1)AO(1) 2.138(9)
Li(1)/Co(1)/Ni(1)AO(3) 2.014(7) Li(1)/Co(1)/Ni(1)AO(3) 2.129(9)
Li(1)/Co(1)/Ni(1)AO(3) 2.286(6) Li(1)/Co(1)/Ni(1)AO(3) 2.246(9)
Li(1)/Co(1)/Ni(1)AO(4) 2.129(5) Li(1)/Co(1)/Ni(1)AO(4) 2.102(6)
Li(1)/Co(1)/Ni(1)AO(6) 2.103(6) Li(1)/Co(1)/Ni(1)AO(6) 2.146(9)
Li(1)/Co(1)/Ni(1)AO(6) 2.189(7) Li(1)/Co(1)/Ni(1)AO(6) 2.155(9)
Li(1)/Co(1)/Ni(1)AO 2.139 Li(1)/Co(1)/Ni(1)AO 2.152
Li(2)/Co(2)/Ni(2)AO(2) 2.162(9) Li(2)/Co(2)/Ni(2)AO(2) 2.089(13)
Li(2)/Co(2)/Ni(2)AO(2) 2.213(9) Li(2)/Co(2)/Ni(2)AO(2) 2.174(13)
Li(2)/Co(2)/Ni(2)AO(5)  2 2.087(7) Li(2)/Co(2)/Ni(2)AO(5)  2 2.061(10)
Li(2)/Co(2)/Ni(2)AO(5)  2 1.994(7) Li(2)/Co(2)/Ni(2)AO(5)  2 2.045(10)
Li(2)/Co(2)/Ni(2)AO 2.088 <Li(2)/Co(2)/Ni(2)AO> 2.079
Li(3)/Co(3)/Ni(3)AO(1)  2 2.131(10) Li(3)/Co(3)/Ni(3)AO(1)  2 2.117(15)
Li(3)/Co(3)/Ni(3)AO(7)  2 2.167(10) Li(3)/Co(3)/Ni(3)AO(7)  2 2.209(15)
Li(3)/Co(3)/Ni(3)AO(7)  2 2.389(10) Li(3)/Co(3)/Ni(3)AO(7)  2 2.157(18)
<Li(3)/Co(3)/Ni(3)AO> 2.229 <Li(3)/Co(3)/Ni(3)AO> 2.161
158 H. Bensaid et al. / Journal of Molecular Structure 1031 (2013) 152–159
Fig. 8. Raman spectra of Li2Co2x Nix (MoO4)3 (0 6 x 6 2).
changes for Li2Co2xNix(MoO4)3 (0 6 x 6 2) as a function of x. The
sites of the various ions, within the conventional labeling, are as
follows: Mo(1):4c, Mo(2):8d, Li(1)/Co(1)/Ni(1): 8d, Li(2)/Co(2)/
Ni(2): 4c, Li(3)/Co(3)/Ni(3): 4c, O: 8d, 4c.
Fig 8 shows the Raman spectra of Li2Co2xNix(MoO4)3.
Vibrational analysis can be performed by site group analysis, factor
group analysis, and the correlation method. The Pnma space group
of the orthorhombic crystals has the D2 h factor group. The
internal vibrational modes of the D2h factor group consist of Ag,
Bg, Au, and Bu [40]. The in-phase vibrations (Ag and Bg) are Raman
active and the out-of phase modes (Au and Bu) are IR active, since
the mutual exclusion principle holds within the crystal. A simpli-
fied structural model of Li2Co2xNix(MoO4)3 which is composed
of (Li/Co/Ni)O(6) and tetrahedral MoO4 sublattices occupying the
D2h symmetry sites can be considered. The internal vibrational
modes of the free tetrahedral molecule/ion with Td symmetry are
classified as m1 (the symmetric stretching mode of A1 symmetry),
m2 (the bending mode of E symmetry), m3 (the antisymmetric
stretching mode of T2 symmetry), and m4 (the bending mode of T2
symmetry), all four vibrations are Raman active. The m1(A1), m2(E),
m3(T2), and m4(T2) modes of the orthorhombic phase with the D2h
symmetry split into Ag, 2Ag, B1g + B2g + B3g, and B1g + B2g + B3g,
respectively [41].
On the basis of known trends of positions and relative intensi-
ties of the m1(A1) Raman bands for MoO4 tetrahedra and by com-
paring Raman spectral features for Mg2.5VMoO8 in a companion
paper [42], the bands centered at 915 and 895 cm1 in the Raman
spectrum of Li2Co2xNix(MoO4)3 are assigned to the symmetric
stretching m1 mode of MoO4 tetrahedra, respectively. The bands
at 370 cm1 are assigned to the bending (m2(E) or m4(T2)) vibration
of MoO4 tetrahedra, respectively. Also, bands at 895 and 842 cm1
are assigned to m3(T2) asymmetric stretching vibration of MoO4 tet-
rahedra, respectively. The m2 band positions of the aqueous MoO2 4
tetrahedra have been observed at 320 cm1, respectively, and are
estimated to overlap with m4 band positions [43]. A relatively weak,
but distinct band at 326 cm1 is likely due to m2(E) or m4(T2)
bending vibration of MoO4 tetrahedra because it is stronger when
the Mo concentration is relatively higher. Therefore, the highest
Mo–O Raman stretching frequency for (Co/Ni)2Li2(MoO4)3 is ex-
pected to appear at a higher frequency than the highest observed
Mo–O stretching band at 903 cm1 for the Li2MoO4 [44].
4. Conclusion
Nominal Li2Co2xNix(MoO4)3 (0 6 x 6 2) series has been pre-
pared with soft-combustion and structurally characterized by the
Rietveld analysis of LXRPD patterns. In all samples, crystallizes at
room temperature in orthorhombic systems with space group
Pnma (D2 h). The lattice constants of the solid solutions varied lin-
early as a function of the nickel content x in the range (0 6 x 6 2).
The results of Raman vibrational spectroscopy present the assign-
ments of internal modes of (MoO4) tetrahedral have been made.
Raman spectra of all the compositions as a function of the compo-
sition in range (0 6 x 6 2).
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