Crystal Structure of Mixed-metal Phosphite,
Pb2Ga(HPIIIO3)3(PVO3)

Jun-Ling Song1; Xi-Jia Wang2

Crystal Structure of Mixed-metal Phosphite, Pb2Ga(HPIIIO3)3(PVO3)

Jun-Ling Song1 and Xi-Jia Wang2

Published Date: 2016-01-12

Jun-Ling Song^1* and Xi-Jia Wang²

¹China-Australia Joint Research Centre for Functional Molecular Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China

²State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, People's Republic of China

*Corresponding Author:: Song JL
China-Australia Joint Research Centre for Functional Molecular Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China
Tel: +8659183736672
E-mail: s070054@e.ntu.edu.sg

Received Date: December 18, 2015 Accepted Date: January 07, 2016 Published Date:J anauary 12,2016

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Abstract

One mixed-metal phosphite namely, Pb2Ga(HPO3)3(PO3) (Compound 1) was obtained by a facile hydrothermal method and structurally characterized. Single crystal X-ray diffraction analysis reveals that crystallizes in the orthorhombic, space group Cmcm with unit cell dimensions, a=5.2572(12) Å, b=18.505(5) Å, c=12.544(3) Å and α=β=γ=90°. The crystal structure of Pb2Ga(HPO3)3(PO3) exhibits a complicated 3D framework based on PbO6 and GaO6 octahedral connected by HPO3 and H2PO3 anions via corner- or edge-sharing

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Keywords

Crystal structure; Hydrothermal reactions; Mixed-metal phosphites; 3D framework; Single-crystal X-ray diffraction

Introduction

Metal phosphites have been paid more and more attention because of their abundant structures and potential applications in sorption, magnetism, photocatalyst and nonlinear optics [1-10]. Especially, pure inorganic metal phosphites with good thermostability and chemical stability have been exploited their application in various fields [9-13]. For example, two maingroup metal phosphites, namely, RbIn(HPO₃)₂ [9] and SnHPO3 [10], exhibit second harmonic generation (SHG) responses. Two alkali transition metal phosphites, namely, Li₃Fe₂(HPO₃)₃Cl and Li_1.43[Fe^II _4.43Fe^III 0.57(HPO₃)₆]1.5H₂O, are good candidates of cathode materials [11,12]. In addition, a series of transition-metal (TM) phosphites exhibit different magnetic properties, such as Na₂M(HPO₃)₂ (M=Ni, Fe, Co) and A [M(HPO₃)₂] (A=NH₄, K, Rb and M=V, Fe) [13,14]. The above-mentioned compounds display different properties with amazing structures due to the different connectivity modes between metal ions and phosphite anions. Thus, it is of vital importance and urgent to explore the structure of phosphite compounds to understand the relationship in the above mentioned properties. In view of the above mentioned discussion, new mixed-metal phosphite should been prepared and study the relationship between the crystal structural and the properties. Thus, here, we prepared the synthesis and crystal structure one new mixed-metal phosphite, namely, Pb₂Ga(HPO₃)₃(PO₃).

Experimental

The starting materials were purchased from the Shanghai Reagent Factory (AR, 99.0%) without further purification.

Synthesis of Pb₂Ga(HPO₃)₃(PO₃)

A mixture of PbO (1 mmol), Ga₂O₃ (0.3 mmol), H₃PO₃ (2.5 mmol) and H₂O (5 mL) was sealed in an autoclave equipped with a Teflon liner (25 mL) and heated at 180°C for three days followed by being slowly cooled to room temperature at a rate of 5°C/h. The initial and final pH values of the solution were about 0.5 and 1, respectively. Single crystals suitable for X-ray diffraction studies were obtained and the product was colorless prism-shaped crystals.

Data collection

X-ray diffraction data collection for Pb₂Ga(HPO₃)₃(PO₃) was performed on a Rigaku Mercury CCD diffractometer with Mo-Kα radiation (λ=0.71073 Å) at 293(2) K. The data sets were corrected for Lorentz and polarization factors as well as absorption by the multi-scan method [15-17]. The structure was solved by the direct method and refined by full-matrix least-squares fitting on F²by SHELX-97 [18,19]. All non-hydrogen atoms were refined with anisotropic thermal parameters. According to the charge balance and bond valence calculations, all the H atoms in Pb₂Ga(HPO₃)₃(PO₃) were needed and assigned to P-H bonds, but they were not refined due to the difficulty in the determination of their precise locations. All atoms were refined with anisotropic thermal parameters except for O(1) and O(2) in Pb₂Ga(HPO₃)₃(PO₃), which was refined with ‘isor’ instruction. If this constraint is not applied, the displacement parameters for O(1) and O(2) will be abnormally small. The P(2) atoms in this compound is disordered with the P(2)-P(2)’ distance of 0.889(12) Å. And the structure was also checked for possible missing symmetry with PLATON. Crystallographic data and structural refinements are summarized in Table 1. Atomic coordinates (× 10⁴) and equivalent isotropic displacement parameters, important bond distances and angles are listed in Tables 2 and 3, respectively.

Compound	1
Empirical formula	Pb₂Ga(HPO₃)₃(PO₃)
Formula weight	833.97
Temperature	293(2) K
Crystal system	Orthorhombic
Space group	Cmcm
a/Å	5.2572(12)
b/Å	18.505(5)
c/Å	12.544(3).
V/Å³	1220.3(5)
Z	4
D_c/g.cm^-3	4.539
m(Mo Kα)/mm^-1	30.432
F(000)	1484
Reflections collected/unique	5010/809 [R(int)=0.0602]
Completeness to theta=27.46	99.4 %
Data/restraints/parameters	809/6/65
Goodness-of-fit on F^2	1.183
Final R indices [I>2sigma(I)]^a	R₁=0.0333, wR₂=0.0686
R indices (all data)	R₁=0.0355, wR₂=0.0696
Extinction coefficient	0.00091(9)
Largest diff. peak and hole	1.813 and -1.714 e. Å-3

^aR₁=Σ||F_o|-|F_c||/Σ|F_o|; ωR₂={Σω[(F_o)² (F_c)²]²/Σω[(F_o)²]²}^1/2

Table 1: Crystal data and structural refinement for Pb₂Ga₂(HPO₃)₃(H₂PO₃).

Atoms	x	y	z	U(eq)
Pb(1)	5000	1900(1)	1004(1)	15(1)
Ga(1)	5000	0	5000	8(1)
P(1)	0	2841(2)	2500	12(1)
P(2)	4155(11)	200(3)	2500	12(1)
P(3)	5000	3924(1)	190(2)	9(1)
O(1)	0	3338(8)	3470(11)	11(3)
O(2)	2370(19)	2403(5)	2500	33(2)
O(3)	5000	987(6)	2500	18(2)
O(4)	5000	-231(4)	3470(6)	16(2)
O(5)	2581(10)	4260(3)	-269(4)	14(1)
O(6)	5000	3119(4)	-65(7)	19(2)

Table 2: Table 2 Atomic coordinates (× 10⁴) and equivalent isotropic displacement parameters (Å² × 10³) for the non-hydrogen atoms of Pb₂Ga(HPO₃)₃(H₂PO₃).

Pb(1)-O(2)#1	2.510(6)	Ga(1)-O(5)#5	1.957(5)
Pb(1)-O(2)	2.510(6)	Ga(1)-O(5)#6	1.957(5)
Pb(1)-O(3)	2.525(7)	Ga(1)-O(5)#7	1.957(5)
Pb(1)-O(6)	2.624(7)	Ga(1)-O(4)	1.966(7)
Pb(1)-O(5)#2	2.702(5)	Ga(1)-O(4)#8	1.966(7)
Pb(1)-O(5)#3	2.702(5)	P(1)-O(2)#9	1.486(9)
Ga(1)-O(5)#4	1.957(5)	P(1)-O(2)	1.486(9)
P(1)-O(1)	1.525(14)	P(3)-O(5)#1	1.528(5)
P(1)-O(1)#10	1.525(14)	P(2)-O(4)#10	1.521(8)
P(3)-O(6)	1.525(7)	P(2)-O(4)	1.521(8)
P(3)-O(5)	1.528(5)	P(2)-O(3)	1.522(12)
O(2)#1-Pb(1)-O(2)	66.9(4)	O(5)#4-Ga(1)-O(5)#5	87.8(3)
O(2)#1-Pb(1)-O(3)	72.1(2)	O(5)#4-Ga(1)-O(5)#6	180.0(2)
O(2)-Pb(1)-O(3)	72.1(2)	O(5)#5-Ga(1)-O(5)#6	92.2(3)
O(2)#1-Pb(1)-O(6)	93.6(2)	O(5)#4-Ga(1)-O(5)#7	92.2(3)
O(2)-Pb(1)-O(6)	93.6(2)	O(5)#5-Ga(1)-O(5)#7	180.000(1)
O(3)-Pb(1)-O(6)	162.8(3)	O(5)#6-Ga(1)-O(5)#7	87.8(3)
O(2)#1-Pb(1)-O(5)#2	145.7(2)	O(5)#4-Ga(1)-O(4)	90.9(2)
O(2)-Pb(1)-O(5)#2	105.9(3)	O(5)#5-Ga(1)-O(4)	90.9(2)
O(3)-Pb(1)-O(5)#2	73.85(19)	O(5)#6-Ga(1)-O(4)	89.1(2)
O(6)-Pb(1)-O(5)#2	120.56(19)	O(5)#7-Ga(1)-O(4)	89.1(2)
O(2)#1-Pb(1)-O(5)#3	105.9(3)	O(5)#4-Ga(1)-O(4)#8	89.1(2)
O(2)-Pb(1)-O(5)#3	145.7(2)	O(5)#5-Ga(1)-O(4)#8	89.1(2)
O(3)-Pb(1)-O(5)#3	73.85(19)	O(5)#6-Ga(1)-O(4)#8	90.9(2)
O(6)-Pb(1)-O(5)#3	120.56(19)	O(5)#7-Ga(1)-O(4)#8	90.9(2)
O(5)#2-Pb(1)-O(5)#3	60.3(2)	O(4)-Ga(1)-O(4)#8	180.000(1)
P(2)#1-P(2)-O(4)#10	73.0(2)	O(2)#9-P(1)-O(2)	113.9(9)
P(2)#1-P(2)-O(4)	73.0(2)	O(2)#9-P(1)-O(1)	109.2(3)
O(4)#10-P(2)-O(4)	106.2(6)	O(2)-P(1)-O(1)	109.2(3)
P(2)#1-P(2)-O(3)	73.0(2)	O(2)#9-P(1)-O(1)#10	109.2(3)
O(4)#10-P(2)-O(3)	114.6(4)	O(2)-P(1)-O(1)#10	109.2(3)
O(4)-P(2)-O(3)	114.6(4)	O(1)-P(1)-O(1)#10	105.9(11)
O(6)-P(3)-O(5)	108.6(3)	O(6)-P(3)-O(5)#1	108.6(3)
		O(5)-P(3)-O(5)#1	112.7(4)

Table 3: Bond distances (Å) and angles [o] for Pb₂Ga(HPO₃)₃(PO₃).

Results and Discussion

Structure solving and refinement

Compound 1, namely, Pb₂Ga(HPO₃)₃(PO₃), crystallizes in the orthorhombic space group Cmcm (no. 63) and features a 3D framework formed by the interconnection of 2D layer of lead phosphites and gallium phosphites (Figure 1). The asymmetric unit of Pb₂Ga(HPO₃)₃(PO₃) includes 11 independent non-H atoms, including one Pb, one Ga, three P and six O atoms, in addition, all atoms except O(5) lie in special positions. Pb(1) is six coordinated by six oxygens from five HPO₃ anions and one P(1)O₄ anion in a distorted pentagonal pyramid geometry, Ga(1) is also six coordinated by six oxygens from six HPO3 anions in a octahedral geometry. And the Pb2+ ions shows stereochemically active lone pairs. The Pb−O and Ga-O distances range from 2.510(6) to 2.702(5) Å, 1.957 (5) to 1.966 (7) Å, respectively. All of these bond distances are comparable to those reported for other lead(II) phosphites [20] and gallium phosphites [9,21]. The calculated total bond valences for Pb(1), Ga(1) and P(1) atoms are 1.671 3.025 and 5.430, respectively, indicating that Pb, Ga and P(1) are in oxidation states of +2, +3 and +5, respectively, in accordance with the crystal structure results. P(1) atom is coordinated with two O(1) and two O(2) atoms to form [PO₄]³⁻ tetrahedral units, and the occupancy of P(1), O(1) and O(2) is 25%, 25% and 50%, respectively, while P(2) and P(3) atoms bond to three oxygen atoms and one hydrogen atom, forming the pseudo-tetrahedral coordination geometry. The presence of P(1)O₄ phosphates might be due to the H₃PO₃ is oxidized in the reaction progress. The P−O bond distances range from 1.486 (9) to 1.528(5) (Table 2). The phosphates and phosphites anions adopt different coordination modes. P(1)O₄ phosphates shows a μ₄-η²η²-coordination mode that bridges 4Pb atoms with two O atoms, HP(2)O₃ anion displays 4.211 coordination mode that bridges 4Pb atoms, and HP(3)O₃ anion adopts 5.221 coordination mode that bridges 5Pb atoms. The PbO₆ octahedra and HPO3 and PO₄ anions are interconnected via edge-sharing into a novel 2D anionic network in the ac palne with the 6-member rings tunnels along b-axis (Figure 2). While, the GaO₆ octahedra and HPO3 pseudo-tetrahedra are interconnected via vertex-sharing resulting in a 2D anionic network in the ac palne with the 4-Member Rings tunnels along b-axis (Figure 3). Such two type of 2D layers further bridges by corner-sharing oxygen atom to yield a 3D framework in the ab plane (Figure 1).

structural-crystallography-blue-polyhedra

Figure 1: View of structure of compound 1 perpendicular to the a axis, the green and blue polyhedra represent the PbO6 and GaO6 octahedra, respectively.

structural-crystallography-layer-constructed

Figure 2: 2D layer constructed from lead(II) phosphites perpendicular to the b axis.

Figure 3: 2D layer constructed from gallium (II) phosphites in the ac plane.

Conclusions

In summary, we reported one new mixed-metal phosphites, namely, Pb₂Ga(HPO₃)₃(PO₃) using a facile hydrothermal method and it crystallizes in the orthorhombic space group Cmcm, which features 3D framework formed by the interconnection of 2D layer of lead(II) phosphites and 2D layer of gallium(III) phosphites. Our future research efforts will be devoted to the design and preparation of different mixed-metal phosphites with d⁰-transition metals such as Ti⁴⁺, V⁵⁺ and Mo⁶⁺ to exploit this related systems and study the relationship between the crystal structures and properties of this related materials.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 21403232) and the Fundamental Research Funds for the Central Universities (No. JUSRP11518).

Additional Information

Crystallographic data for the structures reported here can be obtained from the FIZ Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany, Fax: +497247808666; E-mail: crysdata@fiz-karlsruhe. de on quoting the depository numbers CSD 430503.

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