Synthesis and Characterization of a New Open-framework Iron Phosphate†

doi:10.7503/cjcu20131247

Abstract

Abstract:

Synthesis of novel iron phosphates has gained much attention due to their structure diversity and unique magnetic property. In this work, a new iron phosphate JU94( $2 H 3 O$ [Fe₂P₂O₈(OH)₂]) with novel three-dimensional open framework has been hydrothermally synthesized using dipropylenetriamine as the structure-directing agent(SDA). Its structure was determined by single-crystal X-ray diffraction. It crystallizes in monoclinics pace group, P2₁/c, with a=0.97566(5) nm, b=0.98560(5) nm, c=1.24514(5) nm, β=129.651(3)°, V=0.92189(8) nm³. The framework structure is made of tetranuclear iron-oxygen clusters as building unit formed by connection of FeO₆ and PO₄ polyhedra, which contains intersecting 8-ring channels along the [101], [ $1 ¯$ 01], [010] and [111] directions. Water molecules are occluded in the free space of channels. Mössbauer analysis shows that there are two types of Fe atoms in the framework, and they are both trivalent. Magnetic measurement shows anti-ferromagnetic ordering of JU94 at room temperature.

Key words: Iron phosphate, Open-framework, Hydrothermal synthesis, Anti-ferromagnetic property

CLC Number:

O614

TrendMD:

WANG Yanyan, ZHANG Zheng, SUN Yanjun, LI Jiyang. Synthesis and Characterization of a New Open-framework Iron Phosphate^†[J]. Chem. J. Chinese Universities, 2014, 35(3): 449.

Figures/Tables 9

Table 1 Crystal data and structure refinement for JU94*

Empirical formula	Fe₂P₂ $O 1 2$ H₈
Formula weight	373.70
Temperature/K	293(2)
Wavelength/nm	0.071073
Crystal system, space group	Monoclinic, P2₁/c
a/nm	0.97566(5)
b/nm	0.98560(5)
c/nm	1.24514(5)
β/(°)	129.651(3)
V/nm³	0.92189(8)
Z, calculated density/(Mg·m^-3)	4, 2.693
Absorption coefficient/mm^-1	3.556
F(000)	744
Crystal size	0.15 mm×0.12 mm×0.10 mm
θ range for data collection/(°)	2.71—28.31
Limiting indices	-10≤h≤3
	-13≤k≤11
	-16≤l≤16
Reflections collected/unique	6615/2283(R_int=0.0606)
Completeness to θ=28.31	100.0%
Max. and min. transmission	0.7175 and 0.6176
Refinement method	Full-matrix least-squares on F²
Data/restraints/parameters	2283/0/151
Goodness-of-fit on F²	1.068
Final R indices[I>2σ(I)]	R₁=0.0338, wR₂=0.0965
R indices(all data)	R₁=0.0372, wR₂=0.0987
Largest diff. peak and hole/(e·nm^-3)	1204, -721

Table 1 Crystal data and structure refinement for JU94*

Empirical formula	Fe₂P₂ $O 1 2$ H₈
Formula weight	373.70
Temperature/K	293(2)
Wavelength/nm	0.071073
Crystal system, space group	Monoclinic, P2₁/c
a/nm	0.97566(5)
b/nm	0.98560(5)
c/nm	1.24514(5)
β/(°)	129.651(3)
V/nm³	0.92189(8)
Z, calculated density/(Mg·m^-3)	4, 2.693
Absorption coefficient/mm^-1	3.556
F(000)	744
Crystal size	0.15 mm×0.12 mm×0.10 mm
θ range for data collection/(°)	2.71—28.31
Limiting indices	-10≤h≤3
	-13≤k≤11
	-16≤l≤16
Reflections collected/unique	6615/2283(R_int=0.0606)
Completeness to θ=28.31	100.0%
Max. and min. transmission	0.7175 and 0.6176
Refinement method	Full-matrix least-squares on F²
Data/restraints/parameters	2283/0/151
Goodness-of-fit on F²	1.068
Final R indices[I>2σ(I)]	R₁=0.0338, wR₂=0.0965
R indices(all data)	R₁=0.0372, wR₂=0.0987
Largest diff. peak and hole/(e·nm^-3)	1204, -721

Fig.1 Experimental(a) and simulated(b) XRD patterns of JU94

Fig.2 Thermal ellipsoids of JU94 given at 30% probabilitySymmetry codes: #1. -x+2, y-1/2, -z+3/2; #2. -x+2, y+1/2, -z+3/2; #3. x+1, y, z+1; #4. -x+3, -y+2, -z+2; #5. x+1, -y+3/2, z+1/2; #6. x, -y+3/2, z-1/2.

Fig.3 Tetranuclear iron cluster(Fe4P6O30H4) in JU94(A), the layer formed by clusters through sharing PO4 tetrahedra(B) and 3D framework constructed by the layers linked through O atoms(C)

Fig.4 Framework of JU94 viewed along [101](A) and [1ˉ01](B) directions and the channel along [[101]] or [1ˉ01] direction(C)

Fig.5 Framework of JU94 viewed along [010](A) and [111](B) directions

Fig.6 57Fe Mössbauer spectra of JU94

Table 2 Parameters obtained in Mössbauer analysis*

Absorption peak	IS/(mm·s^-1)	QS/(mm·s^-1)	HWHM/(mm·s^-1)	Area fraction(%)
1	0.40±0	0.36±0	0.19±0	51.4
2	0.42±0	0.67±0	0.18±0	48.6

Fig.7 Variable-temperature magnetic susceptibilities of JU94

References 29

[1]	Wilson S. T., Lok B. M., Messina C. A., Marcus B. K., Patton R. L., Flanigen E. M., J. Am. Chem. Soc., 1982, 104, 1146—1147
[2]	Lu H. Y., Tong X. Q., Yan Y., Yan W. F., Yu J. H., Xu R. R., Chem. J. Chinese Universities,2013, 34(7), 1571—1575
	(卢慧英, 仝晓强, 颜岩, 闫文付, 于吉红, 徐如人. 高等学校化学学报, 2013, 34(7), 1571—1575)
[3]	Yu J. H., Xu R. R., Acc. Chem. Res., 2010, 43, 1195—1204
[4]	Li Y., Yu J. H., Xu R. R., Baerlocher C., McCusker L. B., Angew. Chem. Int. Ed., 2008, 47, 4401—4405
[5]	Li Y., Yu J. H., Xu R. R., Angew. Chem. Int. Ed., 2013, 52, 1673—1677
[6]	Yu J. H., Xu R. R., Chem. Soc. Rev., 2006, 35, 593—604
[7]	Song X., Li Y., Gan L., Wang Z., Yu J., Xu R., Angew. Chem. Int. Ed., 2008, 48, 314—317
[8]	Rao C. N. R., Natarajan S., Choudhury A., Neeraj S., Ayi A. A., Acc. Chem. Res., 2001, 34, 80—87
[9]	Yang G. Y., Sevov S. C., J. Am. Chem. Soc., 1999, 121, 8389—8390
[10]	Thirumurugan A., Natarajan S., Dalton Trans., 2003, 17, 3387—3391
[11]	Du Y., Yu J. H., Wang Y., Pan Q. H., Zou Y. C., Xu R. R., J. Solid State Chem., 2004, 177, 3032—3037
[12]	Sassoye C., Marrot J., Loiseau T., Loiseau T., Férey G., Chem. Mater., 2002, 14, 1340—1347
[13]	Beitone L., Marrot J., Loiseau T., Férey G., Henry M., Huguenard C., Gansmuller A., Taulelle F., J. Am. Chem. Soc., 2003, 125, 1912—1922
[14]	Lin C. H., Wang S. N., Lii K. H., J. Am. Chem. Soc., 2001, 123, 4649—4650
[15]	Soghomonian V., Chen Q., Haushalter R.C., Zubieta J., Charles J. O., Science, 199,259, 1596—1599
[16]	Khan M. I., Meyer L. M., Haushalter R. C., Schweitzer A. L., Zubieta J., Dye J. L., Chem. Mater., 1996, 8, 43—53
[17]	Murugavel R., Choudhury A., Walawalkar M. G., Pothiraja R., Rao C. N. R., Chem. Rev., 2008, 108, 3549—3655
[18]	Choudhury A., Rao C. N. R., J. Struct. Chem., 2002, 43, 632—642
[19]	Cavellec M., Grenèche J. M., Riou D., Férey G., Chem. Mater., 1998, 10, 2434—2439
[20]	Cavellec M., Riou D., Férey G., Acta Crystallogr., 1994, C50, 1379—1381
[21]	Choudhury A., Natarajan S., Rao C. N. R., Chem. Commun., 1999, 14, 1305—1306
[22]	Armas S. F., Mesa J. L., Pizarro J. L., Garitaonandia J. S., Arriortua M. I., Rojo T., Angew. Chem. Int. Ed., 2004, 43, 977—980
[23]	Rhule J. T., Hill C. L. , Jadd C. L., Schinazi R. F., Chem. Rev., 1998, 98, 327—358
[24]	Rowan E., Nolte R. J. M., Angew. Chem. Int. Ed. Engl., 1998, 37, 63—68
[25]	Kagan R., Mitzi D. B., Dimitrakopoulos C. D., Science,1999, 286, 945—947
[26]	Knof U., Zelewsky A. V., Angew. Chem. Int. Ed. Engl., 1999, 38, 302—322
[27]	Bruker AXS Inc., SAINT, Madison, WI, 2000
[28]	Bruker AXS Inc., SHELXTL, Madison, WI, 2000
[29]	Zima V., Lii K., J. Chem. Soc.,Dalton Trans., 1998, (24), 4109—4112