Solid State Communications 201 (2015) 102–106

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Solid State Communications

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Crystal structure and characterization of mixed anion compounds

Rb2Bi(PO4)(MO4) (M ¼Mo, W)
M.J. Xia a,b, R.K. Li a,n
a
Beijing Center for Crystal Research and Development, Key Laboratory of Functional Crystals and Laser Technology, Technical Institute of Physics
and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
b
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, Shandong, China

art ic l e i nf o a b s t r a c t

Article history: Two new phosphates Rb2Bi(PO4)(MO4) (M ¼Mo, W) were grown from congruent melt, and their crystal
Received 4 June 2014 structures were determined by a single crystal X-ray diffraction technique. In the structure, BiO8
Received in revised form dodecahedra share an edge to form zig-zag chains which are linked by edge sharing with the PO4
22 September 2014 8
tetrahedra to build two dimensional 21 ðBi2 P2 O12 Þ planes. The MO4 tetrahedra are attached to the
Accepted 26 September 2014
plane in both sides by corner sharing with the apical O atoms of the BiO8 dodecahedra. The expansion
by T.T.M. Palstra
Available online 7 October 2014 coefficients of αa ¼ 9.15  10  5 Å 1C  1, αb ¼2.57  10  4 Å 1C  1 and αc ¼3.83  10-4 Å 1C  1 for Rb2Bi(PO4)
(MoO4), and αa ¼8.53  10  5 Å 1C  1, αb ¼2.54  10-4 Å 1C  1 and αc ¼3.41  10-4 Å 1C  1 for Rb2Bi(PO4)
Keywords: (WO4) were obtained by variable temperature X-ray diffraction measurement. They are both transparent
A. Mixed anion compound
in the range of 400–2500 nm with a UV absorption edge of 290 nm for Rb2Bi(PO4)(MoO4) and 311 nm for
C. Congruent melt
Rb2Bi(PO4)(WO4) according to the reflection spectra. Similar to the sheelite crystals, Rb2Bi (PO4)(MO4)
D. Expansion coefficient
D. Stimulated Raman scattering crystal may be promising stimulated Raman scattering crystals with narrow linewidths due to isolated MO4
groups.
& 2014 Elsevier Ltd. All rights reserved.

1. Introduction 2. Experimental section

Molybdate and tungstate compounds as multifunctional mate- 2.1. Materials and methods
rials were investigated extensively in the past decades. A typical
example is the commercial scintillating crystal PbWO4 which was All chemical reagents were analytically pure from commercial
widely applied in high energy detector due to its low cost, high source and used as without further purification. The differential
density and fast decay time [1]. PbWO4 and Bi2MoO6 can be served scanning calorimetric (DSC) and thermo-gravimetric (TG) analyses
as photocatalytic material for water splitting into O2 and H2 [2,3]. were performed on a Q600SDT thermo-gravimetric apparatus. Both
There are reports of strong second harmonic generation (SHG ) samples of Rb2Bi(PO4)(MoO4) were heated in air at a rate of 15 1C per
response resulting from second order Jahn–Teller (SOJT) effect minute from room temperature to 900 1C. The in-situ temperature
in the systems of BaTeM2O9 (M¼ Mo, W) [4] and Na2TeW2O9 [5]. dependent powder X-ray diffraction data of Rb2Bi(PO4)(MoO4) sam-
Besides, several molybdate and tungstate compounds interestingly ples were recorded on a Bruker D8 Advance diffractometer with Cu Kα
exhibit zero-thermal expansion (ZTE) or negative-thermal expansion radiation (λ ¼1.54178 Å) in the 2θ range 5–401 with scanning speed of
(NTE) behavior [6]. Recently, molybdate and tungstate crystals are 11 per minute from 50 1C to 600 1C. The UV–vis diffuse reflectance
also proposed as efficient stimulated Raman scattering (SRC) mat- spectra were collected on a Varian Cary 5000 spectrophotometer fitted
erials because of its large peak Raman scattering cross-section from with an integrating sphere. The spectra ranged from 200 nm to
symmetrical vibrations of (MoO4)2 and (WO4)2 anionic groups 2500 nm with BaSO4 used as a reference material. Single crystals of
[7,8]. Following those leads, we have explored Rb2O–Bi2O3–MoO3/ Rb2Bi(PO4)(MoO4) were chosen to perform Raman spectra on a
WO3–P2O5 systems in an attempt to find novel functional materials, Renishaw inVia-Reflex micro-zone Raman spectrometer. Raman spec-
and as a result two new compounds, Rb2Bi(PO4)(MoO4) and Rb2Bi tra of the two crystals are collected under a 532 nm laser excitation at
(PO4)(WO4) were obtained. room temperature.

2.2. Synthesis and crystal growth

n
Corresponding author. Tel./fax: þ 86 10 82543711. All analytical pure reagents Rb2CO3, Bi2O3, MoO3, WO3 and
E-mail address: [email protected] (R.K. Li). NH4H2PO4 were used as received. Stoichiometric mixtures were

http://dx.doi.org/10.1016/j.ssc.2014.09.023
0038-1098/& 2014 Elsevier Ltd. All rights reserved.
 M.J. Xia, R.K. Li / Solid State Communications 201 (2015) 102–106 103

firstly preheated at 450 1C for 12 h and then calcined at 600 1C for than that of Mo6 þ , the cell parameters of Rb2Bi(PO4)(WO4) (a¼
Rb2Bi(PO4)(MoO4) and 700 1C for Rb2Bi(PO4)(WO4) for 14 h with 7.0696(9) Å, b¼ 12.5195(15) Å, c¼20.458(3) Å) are slight larger
intermediate grindings. The polycrystalline samples were melted than those of Rb2Bi(PO4)(MoO4) (a¼ 7.0671(11) Å, b¼12.5150(19) Å,
at 750 1C for Rb2Bi(PO4)(MoO4) and 800 1C for Rb2Bi(PO4)(WO4) in c¼20.441(3) Å). Since the two structures are isotypic, only the crystal
a resistant furnace. And then the melts were slowly cooled down to structure of Rb2Bi(PO4)(WO4) will be described in detail hereafter
700 1C at a rate of 0.5 1C per hour. Colorless crystals with plate habit (Fig. 1a). As shown in Fig. S1, P and W atoms both coordinate to four O
for Rb2Bi(PO4)(MoO4) and needle habit for Rb2Bi(PO4)(WO4) were atoms to form PO4 (d(P–O): 1.540(5)–1.544(6) Å) and WO4 (d(W–O):
obtained by mechanically separation from the surface of the melt. 1.758(6)–1.794(6) Å) tetrahedra. Bi atoms are surrounded by eight O
atoms forming BiO8 dodecahedra with the bond lengths of 2.361(5)–
2.3. Single crystal X-ray diffraction 2.603(5) Å. The BiO8 dodecahedra are connected by edge-sharing
with the other BiO8 to form (BiO4O4/2)3 chains along a direction.
Single crystals of Rb2Bi(PO4)(MoO4) and Rb2Bi(PO4)(WO4) with Then the chains are also linked by edge-sharing with PO4 tetrahedra
8
about the same size of 0.04  0.04  0.05 mm3 were chosen for the to build two dimensional 21 ðBi2 P2 O12 Þ layers at ab plane (Fig. 1b).
single crystal X-ray diffraction on a Bruker Smart APEX II diffract- Finally, the WO4 tetrahedra attach to the plane in both sides along
ometer equipped with Mo Kα radiation (λ ¼0.71073 Å). Their crystal
structures were solved using a Patterson method by SHELXS-97 and
Table 2
refined by full matrix least squares on F2 using SHELXL-97 programs Atomic coordinates, equivalent displacement parameters (Å2) and bond valence
[9]. All atoms were refined with anisotropic displacement parameters. sums (BVS) for Rb2Bi(PO4)(MO4) (M¼ Mo, W).
The detailed crystallographic data and refinements for Rb2Bi(PO4)
(MO4) are summarized in Table 1. The positional, equivalent para- Atom Wyckoff site x y z Ueq BVS

meters and bond valence sums (BVS) are listed in Table 2. The selected Rb2Bi(PO4)(MoO4)
bond lengths and angles are presented in Table S1. Further details of
Rb1 16f 0.46513(8) 0.58274(6) 0.34255(3) 0.0248(2) 1.088
the crystal structure data can be obtained from Fachinformationszen- Bi1 8d 0.75 0.66716(2) 0.5 0.01131(9) 3.086
trum Karlsruhe, D-76344 Eggenstein-Leopoldshafen, Germany (fax: Mo1 8e 0.5 0.75 0.66352(4) 0.0154(2) 5.902
(þ49) 7247-808-666; e-mail: crysdata@fiz-karlsruhe.de) on quoting P1 8d 0.75 0.4269(2) 0.5 0.0107(4) 4.938
the depository numbers CSD-426593 for Rb2Bi(PO4)(MoO4) and O1 16f 0.7768(6) 0.5008(3) 0.5593(2) 0.0167(9) 2.053
O2 16f 0.7001(6) 0.7165(4) 0.6147(2) 0.0226(10) 1.985
CSD-426594 for Rb2Bi(PO4)(WO4). O3 16f 0.5814(5) 0.8506(3) 0.4899(2) 0.0160(10) 2.065
O4 16f 0.4378(7) 0.6406(4) 0.7121(2) 0.0309(12) 1.949

Rb2Bi(PO4)(WO4)
3. Results and discussion
Rb1 16f 0.46598(11) 0.58202(7) 0.34228(4) 0.0229(2) 1.092
Bi1 8d 0.75 0.66649(3) 0.5 0.01008(12) 3.102
3.1. Crystal structures W1 8e 0.5 0.75 0.66359(2) 0.01376(13) 5.862
P1 8d 0.75 0.4264 (2) 0.5 0.0105(6) 4.898
The title compounds are found isostructural to the Na2Y(PO4) O1 16f 0.7750(7) 0.5011(4) 0.5594(3) 0.0149(12) 2.04
O2 16f 0.7014(8) 0.7150(5) 0.6148(3) 0.0211(14) 1.976
(MoO4) which represents a family of several isomorphous compounds
O3 16f 0.5812(7) 0.8505(4) 0.4897(3) 0.0145(13) 2.061
[10]. They crystallize in centrosymmetric space group Ibca with eight O4 16f 0.4354(9) 0.6398(5) 0.7120(3) 0.027(2) 1.951
formulas per unit cell. Because the ionic radius of W6þ is a little larger

Table 1
Detailed data and structure refinement for Rb2Bi(PO4)(MO4) (M ¼Mo, W).

Empirical formula Rb2Bi(PO4)(MoO4) Rb2Bi(PO4)(WO4)

Formula weight 634.83 722.74

Crystal system, space group Orthorhombic, Ibca Orthorhombic, Ibca
a (Å) a¼ 7.0671(11) a¼ 7.0696(9)
b (Å) b¼ 12.5150(19) b¼ 12.5195(15)
c (Å) c¼ 20.441(3) A c¼ 20.458(3)
Z 8 8
Volume (Å3) 1807.9(5) 1810.7(4)
Temperature (K) 296(2) 296(2)
Wavelength (Å) 0.71073 0.71073
Calculated density (g/cm3) 4.665 5.302
Absorption coefficient (mm  1) 31.714 42.975
F(000) 2224 2480
Crystal size (mm3) 0.05  0.04  0.04 0.05  0.04  0.04
Theta range for data collection 1.99 to 27.51 1.99 to 27.52
Limiting indices  9 rh r 9,  16r k r16,  26r l r 26  9 rh r8,  16r k r 12,  25r l r26
Reflections collected/unique 9691/1042 5165/1041
Rint 0.0534 0.0468
Completeness 99.9 % 99.6 %
Absorption correction Numerical Numerical
Max. and min. transmission 0.7456 and 0.5095 0.7456 and 0.4757
Data/restraints/parameters 1042/0/61 1041/0/61
Goodness-of-fit on F2 1.031 1.028
Final R indices [I 42sigma(I)]a R1 ¼ 0.0218, wR2 ¼ 0.0417 R1 ¼ 0.0244, wR2 ¼ 0.0508
R indices (all data)a R1 ¼ 0.0344, wR2 ¼ 0.0453 R1 ¼ 0.0388, wR2 ¼0.0551
Largest diff. peak and hole (eÅ  3) 0.917 and  0.910 1.540 and  1.502

a
R1 ¼ ∑jjF o j  jF c jj=∑jF O j: wR2 ¼ ½∑wðF 2o  F 2c Þ2 =∑wðF 2o Þ2 1=2 :
104 M.J. Xia, R.K. Li / Solid State Communications 201 (2015) 102–106

Fig. 1. (a) The crystal structure of Rb2Bi(PO4)(MO4) (M ¼Mo, W) viewed along a axis. Blue balls are Rb atoms, green tetrahedra are PO4, gray tetrahedra are MO4 and orange
8
polyhedra are BiO8. (b) Two dimensional 21 ðBi2 P2 O12 Þ layer at ab plane.

Fig. 2. Unit cell parameters versus temperature for (a) Rb2Bi(PO4)(MoO4) and (b) Rb2Bi(PO4)(WO4).

2
c direction to form 21 ðBi2 P2 W2 O16 Þ sheets. Rb atoms, which are parameters of a, b and c as a function of temperature. It shows that
surrounded by eight O atoms, reside among the voids between the both Rb2Bi(PO4)(MoO4) and Rb2Bi(PO4)(WO4) are positive-thermal
neighboring sheets. expansion materials as majority of known compounds. Significantly
lower linear expansion along the a direction was observed in compar-
3.2. Thermal analysis ison with those along b and c directions with αa ¼9.15  10  5 Å 1C  1,
αb ¼2.57  10  4 Å 1C  1 and αc ¼ 3.83  10-4 Å 1C  1 for Rb2Bi(PO4)
Both Rb2Bi(PO4)(MoO4) and Rb2Bi(PO4)(WO4) show sharp (MoO4), and αa ¼8.53  10  5 Å 1C  1, αb ¼2.54  10  4 Å 1C  1 and
endothermic peaks at 712 1C and 747 1C, respectively and obvious αc ¼3.41  10-4 Å 1C  1 for Rb2Bi(PO4)(WO4).
weight losses from the TG curves were not observed until the
melting points were reached during the heating process, indicat- 3.4. Optical properties
ing congruent melting for both of the compounds. (Figs. S2 and S3)
The absorption spectra were obtained from reflectance spectra
3.3. Variable temperature XRD according to the Kubelka–Munk function [11]: α/S ¼(1  R)2/2R,
where α, S and R is the absorption, scattering and reflectance
The powder XRD data, which were collected from 50 1C to 600 1C, coefficient, respectively. As presented in Fig. 3, both compounds
were profile refined by the least square to obtain the unit cell are transparent in the range of 400–2500 nm and start to show
parameters. Fig. 2 presents the temperature dependence of cell absorption around 300 nm.
 M.J. Xia, R.K. Li / Solid State Communications 201 (2015) 102–106 105

Their structures were found isostructural to that of Na2Y(PO4)

(MoO4). In the structure, BiO8 dodecahedra are interconnected to
form zig-zag chains by edge sharing and those chains are linked by
edge sharing with the PO4 tetrahedra to form two dimensional
2
1 ðBi2 P2 O12 Þ8  planes. The MoO4 or WO4 tetrahedra attached to
the plane in both sides by corner sharing with the apical O atoms
of the BiO8 dodecahedra. Narrow linewidths of ν1(MO4) in Raman
spectra were observed for both of the compounds, which may
provide high value of SRC gain coefficient as other Raman crystal
with isolated MO4 groups.

Appendix A. Supporting information

Crystal data in cif for Rb2Bi(PO4)(MO4) (M ¼Mo, W); coordina-

tion environments of the cations; DSC and TG curves for Rb2Bi
(PO4)(MO4) (M ¼Mo, W); selected bond lengths (Å) and angles (1)
for Rb2Bi(PO4)(MO4) (M ¼Mo, W).

Fig. 3. UV–vis diffuse reflectance spectrum for Rb2Bi(PO4)(MO4) (M ¼Mo, W) (Inset

is in the range of 200–400 nm). Acknowledgments

This work was supported by the National Natural Science

Foundation of China (Grant nos. 90922036 and 51032004/E0201)
and the Open Project from the State Key Laboratory of Crystal
Materials (Shandong University). We also thank Dr. Yonggang
Wang from Peking University and Miss. Jie Liu from Shandong
University for their helps with thermal measurement and single
crystal data collection, respectively.

Appendix A. Supporting information

Supplementary data associated with this article can be found in

the online version at http://dx.doi.org/10.1016/j.ssc.2014.09.023.

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