research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 11| November 2014| Pages 309-311
doi:10.1107/S1600536814021783

Crystal structure of (NH4)2[FeII5(HPO3)6], a new open-framework phosphite

Teresa Berrocal,a Jose Luis Mesa,a Edurne Larreab* and Juan Manuel Arrietaa

aDpto. de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco, UPV/EHU, 48080 Leioa, Spain, and bDpto. Mineralogía y Petrología, Facultad Ciencia y Tecnología, Universidad del País Vasco, UPV/EHU, 48080 Leioa, Spain
*Correspondence e-mail: edurne.serrano@ehu.es

Edited by M. Weil, Vienna University of Technology, Austria (Received 11 July 2014; accepted 2 October 2014; online 8 October 2014)

Di­ammonium hexa­phosphito­penta­ferrate(II), (NH4)2[Fe5(HPO3)6], was synthesized under mild hydro­thermal conditions and autogeneous pressure, yielding twinned crystals. The crystal structure exhibits an [FeII5(HPO3)6]2− open framework with NH4+ groups as counter-cations. The anionic skeleton is based on (001) sheets of [FeO6] octa­hedra (one with point-group symmetry 3.. and one with .2.) linked along [001] through [HPO3]2− oxoanions. Each sheet is constructed from 12-membered rings of edge-sharing [FeO6] octa­hedra, giving rise to channels with a radius of ca 3.1 Å in which the disordered NH4+ cations are located. The IR spectrum shows vibrational bands typical for phosphite and ammonium groups.

CCDC reference: 1027279

1. Chemical context

Research in the area of solids exhibiting open-framework structures continues to be exciting because of their numerous potential applications (Barrer, 1982[Barrer, R. M. (1982). In Hydrothermal Chemistry of Zeolites. London: Academic Press.]; Hagrman et al., 1999[Hagrman, P. J., Hagrman, D. & Zubieta, J. (1999). Angew. Chem. Int. Ed. 38, 2638-2684.]). Prior to the early 1980s when nanoporous aluminium phosphates were first reported by Flanigen and co-workers, aluminosilicate-based zeolites (Wilson et al., 1982[Wilson, S. T., Lok, B. M., Messina, C. A., Cannan, T. R. & Flanigen, E. D. (1982). J. Am. Chem. Soc. 104, 1146-1147.]) and closely related systems represented the predominant class of mat­erials with open-framework structures. In the me­antime, a plethora of activities and efforts have been undertaken for the synthesis of numerous other compounds with open-framework structures of different dimensionalities (Yu & Xu, 2006[Yu, J. & Xu, R. (2006). Chem. Soc. Rev. 35, 593-604.]).

Recently a new ammonium iron phosphite, (NH4)[Fe(HPO3)2], has been reported (Hamchaoui et al., 2013[Hamchaoui, F., Alonzo, V., Venegas-Yazigi, D., Rebbah, H. & Le Fur, E. (2013). J. Solid State Chem. 198, 295-302.]) that consists of [FeIII(HPO3)2]− layers formed by [FeO6] octa­hedra inter­connected by [HPO3]2− oxoanions. The ammonium counter-cations are located in the inter­layer space. Here we report on synthesis and the crystal structure of another ammonium iron phosphite, (NH4)2[Fe5(HPO3)6], in which iron exhibits oxidation state +II.

2. Structural commentary

Tha asymmetric unit of (NH4)2[Fe5(HPO3)6] is displayed in Fig. 1[link]. The crystal structure of the title compound contains [FeO6] octa­hedra linked via edge-sharing into sheets parallel to (001). These sheets consist of 12-membered rings whereby each ring is formed by six [Fe(1)O6] octa­hedra and six [Fe(2)O6] octa­hedra. The iron(II) ions occupy two different special positions (6f and 4d) with site symmetries of .2. and 3.., respectively. In one of the FeO6 octa­hedra (Fe1), the Fe—O bond lengths range from 2.030 (2) to 2.217 (3) Å while in the [Fe(2)O6] octa­hedron a more uniform bond-length distribution from 2.138 (3) to 2.140 (3) Å is observed. The bond angles of the two [FeO6] octa­hedra range between 76.48 (10) and 103.18 (9)° for the cis- and between 163.65 (12) and 178.24 (17)° for the trans-angles.

[Figure 1]
Figure 1
The asymmetric unit of (NH4)2[FeII5(HPO3)6], with displacement parameters drawn at the 50% probability level.

The iron oxide sheets are linked through phosphite groups in which six anions share the most inter­ior oxygen atoms of each ring (Fig. 2[link]), forming 12-membered channels along [001] with a radius of about 3.1 Å. The phospho­rus(III) atom of the complex oxoanion is located on a general position of this space group. The P—O bond lengths of the anion range from 1.514 (3) to 1.538 (3) Å, and the P—H distance is 1.28 (5) Å, with O—P—O bond angles from 110.28 (17) to 114.29 (17)°.

[Figure 2]
Figure 2
The crystal structure of (NH4)2[FeII5(HPO3)6] in polyhedral representation, in a projection along [001]. Displacement parameters are drawn at the 50% probability level.

3. Supra­molecular features

The ammonium cations are located in the 12-membered channels of the framework structure. Although no hydrogen atoms of the cations could be located due to the positional disorder, N⋯O contacts of 2.67 (6), 2.85 (7), 2.87 (8) and 2.98 (6) Å between the cations and the O atoms of the anions suggest hydrogen-bonding inter­actions of medium strength. The H atom of the [HPO3]2− anion shows a distance of 2.51 (3) Å to atom O1 [P—H⋯O angle 116.8 (14)°] and seems not to be part of relevant hydrogen-bonding inter­actions.

4. Synthesis and characterization

(NH4)2[FeII5(HPO3)6] was synthesized under mild hydro­thermal conditions and autogeneous pressure (10–20 bar at 343 K). The reaction mixture was prepared from 30 ml water, 2 ml of phospho­rous acid, 0.17 mmol of NH4OH and 0.37 mmol of FeCl3. The mixture had a pH value of ≃ 6.0. The reaction mixture was sealed in a polytetra­fluoro­ethyl­ene (PTFE)-lined steel pressure vessel, which was maintained at 343 K for five days. This procedure apparently caused reduction of iron(III) to iron(II) and led to the formation of single crystals of the title compound with a dark-green colour. All crystals appeared to be twinned. The presence of ammonium cations in the title compound was confirmed by infra-red spectroscopy, showing bands at 3190 and 1450 cm−1. Characteristic bands of the phosphite P—H group were also observed at 2510 and 1050 cm−1 (Nakamoto, 1997[Nakamoto, K. (1997). In Infrared and Raman Spectroscopy of Inorganic and Coordination Compounds. New York: John Wiley & Sons.]).[link]

[Figure 3]
Figure 3
The IR spectrum of (NH4)2[FeII5(HPO3)6], with partial band assignments.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1[link]. The title crystal was confirmed to be twinned by merohedry using the TwinRotMap option in PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]). The twin element is a 180°-rotation around the <1[\overline{1}]0> direction, or any other equivalent representations of the coset decomposition of the 6/mmm holohedry under crystal class [\overline{3}]m1. The twin law (0[\overline{1}]0/[\overline{1}]00/00[\overline{1}]) was used during the refinements, and the twin volume of the second component refined to a value of 0.079 (1)%.

Table 1
Experimental details

Crystal data
Chemical formula (NH4)2[Fe5(HPO3)6]
Mr 795.20
Crystal system, space group Trigonal, P[\overline{3}]c1
Temperature (K) 100
a, c (Å) 10.3862 (15), 9.2089 (14)
V (Å3) 860.3 (3)
Z 2
Radiation type Mo Kα
μ (mm−1) 4.78
Crystal size (mm) 0.18 × 0.05 × 0.02
 
Data collection
Diffractometer Agilent SuperNova (single source at offset)
Absorption correction Gaussian (CrysAlis PRO; Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, England])
Tmin, Tmax 0.566, 0.893
No. of measured, independent and observed [I > 2σ(I)] reflections 6343, 659, 618
Rint 0.073
(sin θ/λ)max (Å−1) 0.649
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.065, 1.17
No. of reflections 659
No. of parameters 68
No. of restraints 15
H-atom treatment Only H-atom coordinates refined
Δρmax, Δρmin (e Å−3) 0.53, −0.76
Computer programs: CrysAlis PRO (Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, England]), SUPERFLIP (Palatinus & Chapuis, 2007[Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786-790.]), SHELXL2014 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), DIAMOND (Brandenburg, 2010[Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany]) and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

The hydrogen atom of the phosphite group was located in a difference map and restrained to be equidistant to the three oxygen atoms of the group, and a fixed isotropic displacement parameter with a value equal to 1.2Ueq of the parent P atom was assigned.

The ammonium cation is equally disordered around a threefold rotation axis along (00z) and was refined with two positions, N1 and N2. The occupancy factors of N1 and N2 were initially freely refined, but since they refined close to the expected value of 1/6, this value was fixed during the last cycles. Because the ellipsoids of these atoms were very elongated, ISOR commands of SHELXL2014 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) were used to achieve more regular displacements. This command restrains the Uij components of anisotropically refined atoms to behave approximately isotropically within a standard uncertainty. H atoms belonging to the disordered ammonium atoms were not considered in the final model.

Supporting information

CCDC reference: 1027279

Crystal structure: contains datablocks global, I, New_Global_Publ_Block. DOI: 10.1107/S1600536814021783/wm5036sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814021783/wm5036Isup2.hkl

checkCIF report


Chemical context top

Research in the area of solids exhibiting open-framework structures continues to be exciting because of their numerous potential applications (Barrer, 1982; Hagrman et al., 1999). Prior to the early 1980s when nanoporous aluminium phosphates were first reported by Flanigen and co-workers, aluminosilicate-based zeolites (Wilson et al., 1982) and closely related systems represented the predominant class of materials with open-framework structures. In the me­antime, a plethora of activities and efforts have been undertaken for the synthesis of numerous other compounds with open-framework structures of different dimensionalities (Yu & Xu, 2006).

Recently a new ammonium iron phosphite, (NH4)[Fe(HPO3)2], has been reported (Hamchaoui et al., 2013) that consists of [FeIII(HPO3)2]- layers formed by [FeO6] o­cta­hedra inter­connected by [HPO3]2- oxoanions. The ammonium counter-cations are located in the inter­layer space. Here we report on synthesis and the crystal structure of another ammonium iron phosphite, (NH4)2[Fe5(HPO3)6], in which iron exhibits oxidation state +II.

Structural commentary top

Tha asymmetric unit of (NH4)2[Fe5(HPO3)6] is displayed in Fig. 1. The crystal structure of the title compound contains [FeO6] o­cta­hedra linked via edge-sharing into sheets parallel to (001). These sheets consist of 12-membered rings whereby each ring is formed by six [Fe(1)O6] o­cta­hedra and six [Fe(2)O6] o­cta­hedra. The iron(II) ions occupy two different special positions (6f and 4d) with site symmetries of .2. and 3.., respectively. In one of the FeO6 o­cta­hedra (Fe1), the Fe—O bond lengths range from 2.030 (2) to 2.217 (3) Å while in the [Fe(2)O6] o­cta­hedron a more uniform bond-length distribution from 2.138 (3) to 2.140 (3) is observed. The bond angles of the two [FeO6] o­cta­hedra range between 76.48 (10) and 103.18 (9)° for the cis- and between 163.65 (12) and 178.24 (17)° for the trans-angles.

The iron oxide sheets are linked through phosphite groups in which six anions share the most inter­ior oxygen atoms of each ring (Fig. 2), forming 12-membered channels along [001] with a radius of about 3.1 Å. The phospho­rus(III) atom of the complex oxoanion is located on a general position of this space group. The P—O bond lengths of the anion range from 1.514 (3) to 1.538 (3) Å, and the P—H distance is 1.28 (5) Å, with O—P—O bond angles from 110.28 (17) to 114.29 (17) °.

Supra­molecular features top

The ammonium cations are located in the 12-membered channels of the framework structure. Although no hydrogen atoms of the cations could be located due to the positional disorder, N···O contacts of 2.67 (6), 2.85 (7), 2.87 (8) and 2.98 (6) Å between the cations and the O atoms of the anions suggest hydrogen-bonding inter­actions of medium strength. The H atom of the [HPO3]2- anion shows a distance of 2.51 (3) Å to atom O1 [P—H···O angle 116.8 (14)°] and seems not to be part of relevant hydrogen-bonding inter­actions.

Synthesis and characterization top

(NH4)2[FeII5(HPO3)6] was synthesized under mild hydro­thermal conditions and autogeneous pressure (10–20 bar at 343 K). The reaction mixture was prepared from 30 ml water, 2 ml of phospho­rous acid, 0.17 mmol of NH4OH and 0.37 mmol of FeCl3. The mixture had a pH value of ≈ 6.0. The reaction mixture was sealed in a polytetra­fluoro­ethyl­ene (PTFE)-lined steel pressure vessel, which was maintained at 343 K for five days. This procedure apparently caused reduction of iron(III) to iron(II) and led to the formation of single crystals of the title compound with a dark-green colour. All crystals appeared to be twinned. The presence of ammonium cations in the title compound was confirmed by infra-red spectroscopy, showing bands at 3190 and 1450 cm-1. Characteristic bands of the phosphite P—H group were also observed at 2510 and 1050 cm-1 (Nakamoto, 1997).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The title crystal was confirmed to be twinned by merohedry using the TwinRotMap option in PLATON (Spek, 2009). The twin element is a 180°-rotation around the <110> direction, or any other equivalent representations of the coset decomposition of the 6/mmm holohedry under crystal class 3m1. The twin law (010/100/001) was used during the refinements, and the twin volume of the second component refined to a value of 0.079 (1)%.

The hydrogen atom of the phosphite group was located in a difference map and restrained to be equidistant to the three oxygen atoms of the group, and a fixed isotropic displacement parameter with a value equal to 1.2Ueq of the parent P atom was assigned.

The ammonium cation is equally disordered around a threefold rotation axis along (00z) and was refined with two positions, N1 and N2. The occupancy factors of N1 and N2 were initially freely refined, but since they refined close to the expected value of 1/6, this value was fixed during the last cycles. Because the ellipsoids of these atoms were very elongated, ISOR commands of SHELXL2014 (Sheldrick, 2008) were used to achieve more regular displacements. This command restrains the Uij components of anisotropically refined atoms to behave approximately isotropically within a standard uncertainty. H atoms belonging to the disordered ammonium atoms were not considered in the final model.

Related literature top

For related literature, see: Barrer (1982); Hagrman et al. (1999); Hamchaoui et al. (2013); Nakamoto (1997); Sheldrick (2008); Spek (2009); Wilson et al. (1982); Yu & Xu (2006).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top
The asymmetric unit of (NH4)2[FeII5(HPO3)6], with displacement parameters drawn at the 50% probability level.

The crystal structure of (NH4)2[FeII5(HPO3)6] in polyhedral representation, in a projection along [001]. Displacement parameters are drawn at the 50% probability level.

The IR spectrum of (NH4)2[FeII5(HPO3)6], with partial band assignment.
Diammonium hexaphosphitopentaferrate(II) top
Crystal data top
(NH4)2[Fe5(HPO3)6]Dx = 3.070 Mg m−3
Mr = 795.20Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3c1Cell parameters from 2414 reflections
a = 10.3862 (15) Åθ = 2.3–28.3°
c = 9.2089 (14) ŵ = 4.78 mm−1
V = 860.3 (3) Å3T = 100 K
Z = 2Acicular, dark green
F(000) = 7840.18 × 0.05 × 0.02 mm
Data collection top
Agilent SuperNova (single source at offset)
diffractometer		659 independent reflections
Radiation source: SuperNova (Mo) X-ray Source618 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.073
Detector resolution: 16.2439 pixels mm-1θmax = 27.5°, θmin = 2.2°
ω scansh = −13→11
Absorption correction: gaussian
(CrysAlis PRO; Agilent, 2014)		k = −10→13
Tmin = 0.566, Tmax = 0.893l = −11→11
6343 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: difference Fourier map
wR(F2) = 0.065Only H-atom coordinates refined
S = 1.17 w = 1/[σ2(Fo2) + (0.0126P)2 + 2.2823P]
where P = (Fo2 + 2Fc2)/3
659 reflections(Δ/σ)max < 0.001
68 parametersΔρmax = 0.53 e Å−3
15 restraintsΔρmin = −0.76 e Å−3
Crystal data top
(NH4)2[Fe5(HPO3)6]Z = 2
Mr = 795.20Mo Kα radiation
Trigonal, P3c1µ = 4.78 mm−1
a = 10.3862 (15) ÅT = 100 K
c = 9.2089 (14) Å0.18 × 0.05 × 0.02 mm
V = 860.3 (3) Å3
Data collection top
Agilent SuperNova (single source at offset)
diffractometer		659 independent reflections
Absorption correction: gaussian
(CrysAlis PRO; Agilent, 2014)		618 reflections with I > 2σ(I)
Tmin = 0.566, Tmax = 0.893Rint = 0.073
6343 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03315 restraints
wR(F2) = 0.065Only H-atom coordinates refined
S = 1.17Δρmax = 0.53 e Å−3
659 reflectionsΔρmin = −0.76 e Å−3
68 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Fe10.61330 (9)0.00000.25000.0209 (2)
Fe20.66670.33330.33453 (10)0.0202 (3)
P10.88002 (13)0.29352 (13)0.09044 (10)0.0224 (3)
H1P1.020 (5)0.343 (3)0.091 (2)0.027*
O20.8512 (3)0.3935 (3)0.1927 (3)0.0234 (7)
O30.8404 (3)0.3102 (4)−0.0665 (3)0.0243 (7)
O10.8063 (4)0.1345 (4)0.1440 (3)0.0284 (8)
N20.970 (5)−0.047 (3)0.059 (2)0.045 (9)0.1667
N11.024 (5)−0.015 (6)0.2033 (17)0.020 (7)0.1667
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0286 (4)0.0250 (5)0.0080 (4)0.0125 (2)0.00013 (16)0.0003 (3)
Fe20.0264 (4)0.0264 (4)0.0077 (4)0.01319 (19)0.0000.000
P10.0278 (6)0.0323 (7)0.0066 (4)0.0148 (5)−0.0011 (4)−0.0018 (4)
O20.0265 (17)0.0314 (17)0.0088 (12)0.0119 (14)−0.0013 (11)−0.0049 (12)
O30.0330 (18)0.0366 (18)0.0062 (11)0.0195 (15)−0.0043 (11)−0.0037 (12)
O10.041 (2)0.0311 (18)0.0123 (13)0.0176 (16)−0.0007 (13)−0.0011 (13)
N20.036 (17)0.040 (17)0.051 (11)0.014 (13)−0.015 (15)0.004 (10)
N10.012 (17)0.011 (15)0.030 (8)0.002 (7)0.002 (9)−0.002 (10)
Geometric parameters (Å, º) top
Fe1—O2i2.086 (3)Fe2—O3vii2.140 (3)
Fe1—O2ii2.086 (3)Fe2—O3viii2.140 (3)
Fe1—O3iii2.217 (3)P1—O21.538 (3)
Fe1—O3iv2.217 (3)P1—O31.536 (3)
Fe1—O12.030 (3)P1—O11.514 (3)
Fe1—O1v2.030 (3)O2—Fe1vi2.086 (3)
Fe2—O22.138 (3)O3—Fe1ix2.217 (3)
Fe2—O2ii2.138 (3)O3—Fe2x2.140 (3)
Fe2—O2vi2.138 (3)P1—H1P1.28 (5)
Fe2—O3iii2.140 (3)
O2i—Fe1—O2ii87.23 (17)O2—Fe2—O3vii163.65 (11)
O2ii—Fe1—O3iv102.21 (11)O2—Fe2—O3viii77.08 (11)
O2ii—Fe1—O3iii76.48 (10)O2vi—Fe2—O3vii77.08 (11)
O2i—Fe1—O3iv76.48 (10)O2ii—Fe2—O3viii163.65 (11)
O2i—Fe1—O3iii102.21 (11)O2ii—Fe2—O3iii77.08 (11)
O3iv—Fe1—O3iii178.24 (17)O3iii—Fe2—O3vii103.18 (9)
O1v—Fe1—O2ii165.86 (10)O3iii—Fe2—O3viii103.18 (9)
O1v—Fe1—O2i87.80 (12)O3viii—Fe2—O3vii103.18 (9)
O1—Fe1—O2ii87.80 (12)O3—P1—O2110.28 (17)
O1—Fe1—O2i165.86 (10)O1—P1—O2111.96 (17)
O1v—Fe1—O3iv89.46 (11)O1—P1—O3114.29 (17)
O1—Fe1—O3iii89.46 (11)Fe1vi—O2—Fe2103.34 (12)
O1—Fe1—O3iv91.67 (11)P1—O2—Fe1vi127.30 (17)
O1v—Fe1—O3iii91.67 (11)P1—O2—Fe2128.71 (18)
O1v—Fe1—O199.93 (18)Fe2x—O3—Fe1ix99.01 (10)
O2ii—Fe2—O2vi86.57 (11)P1—O3—Fe1ix124.27 (18)
O2—Fe2—O2vi86.57 (11)P1—O3—Fe2x134.56 (18)
O2—Fe2—O2ii86.57 (11)P1—O1—Fe1133.9 (2)
O2—Fe2—O3iii92.54 (11)O1—P1—H1P106.9 (14)
O2vi—Fe2—O3viii92.54 (11)O2—P1—H1P107.0 (12)
O2ii—Fe2—O3vii92.54 (11)O3—P1—H1P105.9 (12)
O2vi—Fe2—O3iii163.65 (12)
O2—P1—O3—Fe1ix120.4 (2)O3—P1—O1—Fe1−91.5 (3)
O2—P1—O3—Fe2x−39.2 (3)O1—P1—O2—Fe1vi141.7 (2)
O2—P1—O1—Fe134.8 (3)O1—P1—O2—Fe2−27.5 (3)
O3—P1—O2—Fe1vi−89.9 (2)O1—P1—O3—Fe1ix−112.4 (2)
O3—P1—O2—Fe2101.0 (2)O1—P1—O3—Fe2x88.0 (3)
Symmetry codes: (i) y, x−1, −z+1/2; (ii) −x+y+1, −x+1, z; (iii) −y+1, −x+1, z+1/2; (iv) x−y, x−1, −z; (v) x−y, −y, −z+1/2; (vi) −y+1, x−y, z; (vii) −x+y+1, y, z+1/2; (viii) x, x−y, z+1/2; (ix) y+1, −x+y+1, −z; (x) −y+1, −x+1, z−1/2.

Experimental details

Crystal data
Chemical formula(NH4)2[Fe5(HPO3)6]
Mr795.20
Crystal system, space groupTrigonal, P3c1
Temperature (K)100
a, c (Å)10.3862 (15), 9.2089 (14)
V (Å3)860.3 (3)
Z2
Radiation typeMo Kα
µ (mm−1)4.78
Crystal size (mm)0.18 × 0.05 × 0.02
Data collection
DiffractometerAgilent SuperNova (single source at offset)
diffractometer
Absorption correctionGaussian
(CrysAlis PRO; Agilent, 2014)
Tmin, Tmax0.566, 0.893
No. of measured, independent and
observed [I > 2σ(I)] reflections		6343, 659, 618
Rint0.073
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.065, 1.17
No. of reflections659
No. of parameters68
No. of restraints15
H-atom treatmentOnly H-atom coordinates refined
Δρmax, Δρmin (e Å−3)0.53, −0.76

Computer programs: CrysAlis PRO (Agilent, 2014), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL2014 (Sheldrick, 2008), DIAMOND (Brandenburg, 2010), OLEX2 (Dolomanov et al., 2009).

 

Acknowledgements

We gratefully acknowledge financial support of this work by te Gobierno Vasco (SAI12/82). The authors also thank the technicians of SGIkers, Dr J. Sangüesa, Dr Leire San Felices and Dr A. Larrañaga, financed by the National Program for the Promotion of Human Resources within the National Plan of Scientific Research, Development and Innovation, and the Ministerio de Ciencia y Tecnologia and Fondo Social Europeo (FSE), for the X-ray diffraction measurements. ESL thanks the Basque Government for her postdoctoral contract.

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ISSN: 2056-9890
Volume 70| Part 11| November 2014| Pages 309-311
doi:10.1107/S1600536814021783
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