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Volume 68 
Part 1 
Pages i5-i6  
January 2012  

Received 4 November 2011
Accepted 6 December 2011
Online 10 December 2011

Key indicators
Single-crystal X-ray study
T = 173 K
Mean [sigma](Fe-O) = 0.003 Å
R = 0.040
wR = 0.085
Data-to-parameter ratio = 12.2
Details
Open access

An ammonium iron(II) pyrophosphate, (NH4)2[Fe3(P2O7)2(H2O)2], with a layered structure

aDepartment of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005, Fujian Province, People's Republic of China
Correspondence e-mail: yaxihuang@xmu.edu.cn

Diammonium diaquabis(phosphato)triferrate(II), (NH4)2[Fe3(P2O7)2(H2O)2], was synthesized under solvothermal conditions at 463 K. The crystal structure, isotypic to its Mn and Ni analogues, is built from iron pyrophosphate layers parallel to (100), which are linked by ammonium ions sitting in the interlayer space via O-H...O and N-H...O hydrogen bonds. There are two crystallographic Fe sites in the crystal structure, one at a special position (2a, -1), the other at a general position (4e, 1). The former Fe atom on the inversion centre is coordinated by six O atoms, forming an FeO6 octahedron, while the latter is coordinated by five phosphate O atoms and one water molecule, forming an FeO5(H2O) octahedron. Each FeO6 octahedron shares trans edges with two FeO5(H2O) octahedra, forming a linear trimeric unit. These trimers share the lateral edges of FeO5(H2O) with other trimers, forming a zigzag chain running along [010]. The zigzag chains are further linked by P2O7 groups into a layered structure parallel to (100).

Related literature

For background to this compound, see: Moore & Shen (1983[Moore, P. B. & Shen, J. (1983). Nature (London), 306, 356-358.]); Lii et al. (1998[Lii, K.-H., Huang, Y.-F., Zima, V., Huang, C.-Y., Lin, H.-M., Jiang, Y.-C., Liao, F.-L. & Wang, S.-L. (1998). Chem. Mater. 10, 2599-2609.]); Alfonso et al. (2010[Alfonso, B. F., Blanco, J. A., Fernández-Díaz, M. T., Trobajo, C., Khainakov, S. A. & García, J. R. (2010). Dalton Trans. 39, 1791-1796.]); Mi et al. (2010[Mi, J.-X., Wang, C.-X., Chen, N., Li, R. & Pan, Y.-M. (2010). J. Solid State Chem. 183, 2763-2769.]). For background to the bond-valence method, see: Brown & Altermatt (1985[Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244-247.]). For related structures, see: Chippindale et al. (2003[Chippindale, A. M., Gaslain, F. O. M., Bond, A. D. & Powell, A. V. (2003). J. Mater. Chem. 13, 1950-1955.]) for (NH4)2[Mn3(P2O7)2(H2O)2]; Lightfoot et al. (1990[Lightfoot, P., Cheetham, A. K. & Sleight, A. W. (1990). J. Solid State Chem. 85, 275-282.]) for K2Co3(P2O7)2·2H2O; Liu et al. (2004[Liu, W., Yang, X.-X., Chen, H.-H., Huang, Y.-X., Schnelle, W. & Zhao, J.-T. (2004). Solid State Sci. 6, 1375-1380.]) for Na(NH4)[Ni3(P2O7)2(H2O)2]; Wei et al. (2010[Wei, Y., Gies, H., Tian, Z., Marler, B., Xu, Y., Wang, L., Ma, H., Pei, R., Li, K. & Wang, B. (2010). Inorg. Chem. Commun. 13, 1357-1360.]) for (NH4)2[Ni3(P2O7)2(H2O)2].

Experimental

Crystal data
  • (NH4)2[Fe3(P2O7)2(H2O)2]

  • Mr = 587.55

  • Monoclinic, P 21 /c

  • a = 9.4131 (17) Å

  • b = 8.1940 (15) Å

  • c = 9.3987 (17) Å

  • [beta] = 99.651 (3)°

  • V = 714.7 (2) Å3

  • Z = 2

  • Mo K[alpha] radiation

  • [mu] = 3.55 mm-1

  • T = 173 K

  • 0.08 × 0.06 × 0.06 mm

Data collection
  • Bruker Smart APEXI diffractometer equipped with CCD area-detector

  • Absorption correction: numerical (SMART; Bruker, 2001[Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.775, Tmax = 0.808

  • 4127 measured reflections

  • 1652 independent reflections

  • 1417 reflections with I > 2[sigma](I)

  • Rint = 0.035

Refinement
  • R[F2 > 2[sigma](F2)] = 0.040

  • wR(F2) = 0.085

  • S = 1.05

  • 1652 reflections

  • 135 parameters

  • All H-atom parameters refined

  • [Delta][rho]max = 0.55 e Å-3

  • [Delta][rho]min = -0.55 e Å-3

Table 1
Selected geometric parameters (Å, °)

Fe1-O1i 2.055 (3)
Fe1-O4ii 2.092 (3)
Fe1-O6iii 2.108 (3)
Fe1-O8 2.134 (3)
Fe1-O6i 2.185 (3)
Fe1-O5 2.261 (3)
Fe2-O5 2.127 (3)
Fe2-O4 2.135 (3)
Fe2-O3iv 2.201 (3)
P1-O3 1.514 (3)
P1-O6 1.517 (3)
P1-O4 1.523 (3)
P1-O2 1.620 (3)
P2-O7 1.510 (3)
P2-O1 1.516 (3)
P2-O5 1.518 (3)
P2-O2 1.631 (3)
P1-O2-P2 128.83 (18)
Symmetry codes: (i) [x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]; (ii) -x+2, -y+1, -z+1; (iii) [-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) [x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].

Table 2
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
O8-H1...O3v 0.89 (6) 1.87 (6) 2.734 (4) 162 (5)
O8-H2...O7vi 0.82 (6) 2.00 (6) 2.785 (4) 159 (5)
N1-H3...O1vii 0.91 (7) 1.86 (7) 2.717 (5) 156 (6)
N1-H4...O8viii 0.89 (6) 2.56 (7) 3.310 (6) 142 (5)
N1-H5...O7ix 0.96 (7) 1.99 (7) 2.859 (5) 150 (5)
N1-H6...O7 0.88 (7) 1.91 (7) 2.791 (5) 174 (6)
Symmetry codes: (v) x, y+1, z; (vi) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (vii) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (viii) x, y-1, z; (ix) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2001[Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2005[Brandenburg, K. (2005). DIAMOND Crystal Impact GbR, Bonn, Germany.]) and ATOMS (Dowty, 2004[Dowty, E. (2004). ATOMS. Shape Software, Kingsport, Tennessee, USA.]); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FI2119 ).


Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 40972035), the Natural Science Foundation of Fujian Province of China (No. 2010 J01308) and the Scientific and Technical Project of Fujian Province of China (No. 2009 J1009).

References

Alfonso, B. F., Blanco, J. A., Fernández-Díaz, M. T., Trobajo, C., Khainakov, S. A. & García, J. R. (2010). Dalton Trans. 39, 1791-1796.  [CSD] [CrossRef] [ChemPort] [PubMed]
Brandenburg, K. (2005). DIAMOND Crystal Impact GbR, Bonn, Germany.
Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244-247.  [CrossRef] [ISI] [details]
Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.
Chippindale, A. M., Gaslain, F. O. M., Bond, A. D. & Powell, A. V. (2003). J. Mater. Chem. 13, 1950-1955.  [ISI] [CrossRef] [ChemPort]
Dowty, E. (2004). ATOMS. Shape Software, Kingsport, Tennessee, USA.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.  [CrossRef] [ChemPort] [details]
Lightfoot, P., Cheetham, A. K. & Sleight, A. W. (1990). J. Solid State Chem. 85, 275-282.  [CrossRef] [ChemPort] [ISI]
Lii, K.-H., Huang, Y.-F., Zima, V., Huang, C.-Y., Lin, H.-M., Jiang, Y.-C., Liao, F.-L. & Wang, S.-L. (1998). Chem. Mater. 10, 2599-2609.  [ISI] [CrossRef] [ChemPort]
Liu, W., Yang, X.-X., Chen, H.-H., Huang, Y.-X., Schnelle, W. & Zhao, J.-T. (2004). Solid State Sci. 6, 1375-1380.  [ISI] [CrossRef] [ChemPort]
Mi, J.-X., Wang, C.-X., Chen, N., Li, R. & Pan, Y.-M. (2010). J. Solid State Chem. 183, 2763-2769.  [ISI] [CrossRef] [ChemPort]
Moore, P. B. & Shen, J. (1983). Nature (London), 306, 356-358.  [CrossRef] [ChemPort] [ISI]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Wei, Y., Gies, H., Tian, Z., Marler, B., Xu, Y., Wang, L., Ma, H., Pei, R., Li, K. & Wang, B. (2010). Inorg. Chem. Commun. 13, 1357-1360.  [ISI] [CrossRef] [ChemPort]


Acta Cryst (2012). E68, i5-i6   [ doi:10.1107/S1600536811052482 ]

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