supporting information


Acta Cryst. (2007). E63, m2350    [ doi:10.1107/S1600536807036598 ]

Poly[sodium [[mu]4-2-hydroxy­phosphono­acetato(3-)]iron(II)]

J. Li, Y.-Y. Zhu, C.-Y. Huang, Z.-G. Sun and D.-P. Dong

Abstract top

The title compound, NaFe[(O3PCH(OH)CO2)] or {Na[Fe(C2H2O6P)]}n, was synthesized under mild hydro­thermal conditions. The FeII ion is octa­hedrally coordinated; all O atoms from the 2-hydroxy­phosphono­acetate­(3-) are involved in metal coordination. The overall structure can be described as a three-dimensional open framework with channels running along the a axis and with the charge?compensating Na+ cations located inside these channels. This architecture is further stabilized by a number of O-H...O hydrogen bonds involving the protonated hydroxyl O atoms and carboxylate O atoms.

Comment top

Metal phosphonates with rich composition and structural diversity have attracted considerable attention during the past few years due to their potential applications in catalysis (Clearfield, 1996), ion exchange (Alberti et al., 1999), proton conductivity (Odobel et al., 2001) and gas and liquid separations (Riou et al., 1998,2000). The strategy of attaching additional functional groups such as amine, hydroxyl and carboxylate groups to the phosphonic acid has proven to be effective for the synthesis of metal phosphonates with open-framework and microporous structures. For example, 2-hydroxyphosphonoacetic acid (H3L) with functional hydroxyl and carboxylate groups is an interesting ligand for the synthesis of metal phosphonates with open-framework structures, since it can adopt various kinds of coordination modes under different reaction conditions which may result in various interesting structures.

The title compound, (I), has been synthesized by hydrothermal technique, using 2-hydroxyphosphonoacetic acid as ligand. Analysis of the single-crystal data reveals that there are one iron(II) ion, one L3- [L = O3PCH(OH)CO2] ligand, and one Na+ ion in the asymmetric unit of (I). Each iron(II) ion is octahedrally coordinated by three phosphonate O atoms from three separate L3- ligands (Fig 1) [the Fe—O distance range from 2.032 (1) to 2.196 (1) Å], two carboxylate O atoms from two separate L3- ligands [the Fe—O bond lengths are 2.143 (1) and 2.185 (1) Å] and one hydroxyl O atom [the Fe—O bond length is 2.272 (1) Å]. These values are close to those reported for other analogous six-coordinated iron(II) phosphonates (Fu et al., 2005). As a result, all the O atoms from the L3- ligand are involved in metal coordination, and act as a monodentate connecting one iron(II) ion. The values of the O—Fe—O angles are in the range 69.39 (5)–171.49 (5)°. The overall structure can be described as a three-dimensional open-framework type with channels running along the a axis (Fig 2).

Related literature top

For related literature, see: Alberti et al. (1999); Clearfield (1996); Fu et al. (2005); Odobel et al. (2001); Riou et al. (1998, 2000).

Experimental top

A mixture of 0.16 g (0.6 mmol) FeSO4.7H2O, 0.5 ml (2.0 mmol) 2-hydroxyphosphonoacetic acid (48.0 wt %) and 0.17 g (4.0 mmol) NaF (as a mineralizer) were dissolved in 10 ml of deionized water, and then 2 mol/L NaOH (aq) was added with stirring to adjust the pH of the mixture. The mixture (pH = 4) was sealed in a 20 ml Teflon-lined stainless steel autoclave, and then heated at 433 K for 72 h. Colorless block crystals were obtained, washed with distilled water, and dried in air at room temperature.

Refinement top

H atoms were placed in calculated positions and allaowed to ride, with C—H = 0.93 Å or O—H = and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. View showing the octahedral coordination of the iron with the atom-labelling scheme. Ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.[Symmetry codes: (i) 1/2 - x, 3/2 - y, 1/2 + z; (ii) -x - 1/2, 3/2 - y, 1 - z; (iii) -x, 1 - y, 1 - z; (iv) x - 1/2, y, 1/2 - z; (v) 1/2 - x, y - 1/2, z].
[Figure 2] Fig. 2. View of the packing of (I) with the unit cell outlined along the a axis, showing the stacking of compound (I). H and Na atoms have been omitted for clarity.
Poly[sodium [µ4-2-hydroxyphosphonoacetato(3-)]iron(II)] top
Crystal data top
Na[Fe(C2H2O6P)]F(000) = 912
Mr = 231.85Dx = 2.837 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3081 reflections
a = 10.2676 (8) Åθ = 3.4–28.9°
b = 9.7330 (8) ŵ = 3.12 mm1
c = 10.8624 (9) ÅT = 295 K
V = 1085.53 (15) Å3Block, colourless
Z = 80.23 × 0.17 × 0.08 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer
1309 independent reflections
Radiation source: fine-focus sealed tube1213 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 28.0°, θmin = 3.4°
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 2005)
h = 1313
Tmin = 0.531, Tmax = 0.795k = 912
6143 measured reflectionsl = 1411
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)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0281P)2 + 1.0108P]
where P = (Fo2 + 2Fc2)/3
1309 reflections(Δ/σ)max = 0.001
100 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
Na[Fe(C2H2O6P)]V = 1085.53 (15) Å3
Mr = 231.85Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 10.2676 (8) ŵ = 3.12 mm1
b = 9.7330 (8) ÅT = 295 K
c = 10.8624 (9) Å0.23 × 0.17 × 0.08 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer
1309 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 2005)
1213 reflections with I > 2σ(I)
Tmin = 0.531, Tmax = 0.795Rint = 0.022
6143 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.056H-atom parameters constrained
S = 1.07Δρmax = 0.50 e Å3
1309 reflectionsΔρmin = 0.36 e Å3
100 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 > σ(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*/Ueq
Fe10.17708 (3)0.41645 (3)0.60678 (3)0.01090 (10)
P10.09669 (4)0.72190 (5)0.45975 (5)0.01002 (12)
Na10.37599 (8)0.58426 (8)0.42567 (8)0.01915 (19)
O10.17072 (14)0.60193 (14)0.51501 (14)0.0155 (3)
O20.05078 (13)0.71517 (14)0.47584 (13)0.0156 (3)
O30.14845 (13)0.86102 (14)0.50091 (13)0.0151 (3)
O40.26320 (13)0.72206 (14)0.26531 (13)0.0138 (3)
H40.27600.81090.25650.017*
O50.18556 (13)0.48131 (14)0.22376 (14)0.0162 (3)
O60.02360 (13)0.51846 (14)0.26669 (13)0.0156 (3)
C10.12691 (18)0.70391 (19)0.29329 (18)0.0108 (4)
H10.07370.76930.24660.013*
C20.09253 (18)0.5568 (2)0.25833 (18)0.0120 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.00952 (15)0.01086 (15)0.01232 (15)0.00084 (9)0.00043 (10)0.00006 (10)
P10.0097 (2)0.0090 (2)0.0113 (2)0.00012 (16)0.00040 (17)0.00060 (17)
Na10.0176 (4)0.0158 (4)0.0241 (5)0.0005 (3)0.0032 (4)0.0014 (3)
O10.0161 (7)0.0137 (7)0.0168 (7)0.0025 (5)0.0003 (6)0.0041 (5)
O20.0102 (6)0.0180 (7)0.0187 (7)0.0002 (5)0.0005 (5)0.0056 (5)
O30.0168 (7)0.0114 (7)0.0170 (7)0.0017 (5)0.0040 (6)0.0014 (5)
O40.0126 (6)0.0097 (6)0.0189 (7)0.0017 (5)0.0034 (6)0.0008 (5)
O50.0155 (7)0.0100 (6)0.0230 (8)0.0017 (5)0.0065 (6)0.0006 (5)
O60.0117 (6)0.0155 (7)0.0196 (7)0.0020 (5)0.0006 (5)0.0042 (6)
C10.0095 (8)0.0104 (8)0.0126 (9)0.0011 (7)0.0002 (7)0.0005 (7)
C20.0138 (9)0.0111 (9)0.0110 (9)0.0007 (7)0.0003 (7)0.0001 (7)
Geometric parameters (Å, º) top
Fe1—O2i2.0318 (14)Na1—C2vi3.002 (2)
Fe1—O12.0633 (14)Na1—P1v3.2006 (10)
Fe1—O5ii2.1434 (14)Na1—Na1vii3.4326 (18)
Fe1—O6i2.1849 (14)Na1—Fe1viii3.5065 (10)
Fe1—O3iii2.1960 (14)O2—Fe1i2.0318 (14)
Fe1—O4ii2.2713 (14)O2—Na1iv2.3497 (16)
Fe1—Na13.2725 (9)O3—Fe1ix2.1960 (14)
Fe1—Na1ii3.5065 (10)O3—Na1ix2.3349 (16)
P1—O11.5171 (14)O3—Na1iv2.9574 (17)
P1—O31.5218 (14)O4—C11.443 (2)
P1—O21.5256 (14)O4—Fe1viii2.2713 (14)
P1—C11.843 (2)O4—H40.8797
P1—Na13.1868 (10)O5—C21.262 (2)
P1—Na1iv3.2006 (10)O5—Fe1viii2.1434 (14)
Na1—O12.3267 (17)O6—C21.253 (2)
Na1—O3iii2.3349 (16)O6—Fe1i2.1849 (14)
Na1—O2v2.3497 (16)O6—Na1x2.4164 (17)
Na1—O6vi2.4164 (17)C1—C21.523 (3)
Na1—O42.4848 (16)C1—H10.9800
Na1—O3v2.9574 (17)C2—Na1x3.002 (2)
O2i—Fe1—O1108.55 (6)O3iii—Na1—P1v119.24 (5)
O2i—Fe1—O5ii167.05 (6)O2v—Na1—P1v26.70 (3)
O1—Fe1—O5ii84.32 (6)O6vi—Na1—P1v100.98 (4)
O2i—Fe1—O6i90.02 (5)O4—Na1—P1v106.52 (4)
O1—Fe1—O6i91.57 (6)O3v—Na1—P1v28.26 (3)
O5ii—Fe1—O6i88.11 (5)C2vi—Na1—P1v77.70 (4)
O2i—Fe1—O3iii97.73 (5)P1—Na1—P1v110.13 (2)
O1—Fe1—O3iii89.30 (5)O1—Na1—Fe138.81 (4)
O5ii—Fe1—O3iii83.55 (5)O3iii—Na1—Fe142.10 (4)
O6i—Fe1—O3iii171.49 (5)O2v—Na1—Fe1109.92 (5)
O2i—Fe1—O4ii97.64 (5)O6vi—Na1—Fe1130.83 (5)
O1—Fe1—O4ii153.40 (6)O4—Na1—Fe1113.58 (4)
O5ii—Fe1—O4ii69.42 (5)O3v—Na1—Fe1121.21 (4)
O6i—Fe1—O4ii83.68 (5)C2vi—Na1—Fe1144.90 (5)
O3iii—Fe1—O4ii91.78 (5)P1—Na1—Fe165.06 (2)
O2i—Fe1—Na1116.58 (5)P1v—Na1—Fe1120.15 (3)
O1—Fe1—Na144.98 (4)O1—Na1—Na1vii120.74 (6)
O5ii—Fe1—Na173.38 (4)O3iii—Na1—Na1vii58.02 (4)
O6i—Fe1—Na1133.12 (4)O2v—Na1—Na1vii86.87 (5)
O3iii—Fe1—Na145.47 (4)O6vi—Na1—Na1vii87.91 (5)
O4ii—Fe1—Na1125.70 (4)O4—Na1—Na1vii158.98 (6)
O2i—Fe1—Na1ii109.63 (4)O3v—Na1—Na1vii42.05 (3)
O1—Fe1—Na1ii118.30 (5)C2vi—Na1—Na1vii73.81 (5)
O5ii—Fe1—Na1ii61.15 (4)P1—Na1—Na1vii144.47 (5)
O6i—Fe1—Na1ii42.87 (4)P1v—Na1—Na1vii64.75 (3)
O3iii—Fe1—Na1ii130.06 (4)Fe1—Na1—Na1vii86.66 (3)
O4ii—Fe1—Na1ii44.91 (4)O1—Na1—Fe1viii105.75 (5)
Na1—Fe1—Na1ii133.773 (18)O3iii—Na1—Fe1viii109.10 (5)
O1—P1—O3113.18 (8)O2v—Na1—Fe1viii120.07 (5)
O1—P1—O2114.76 (8)O6vi—Na1—Fe1viii37.96 (3)
O3—P1—O2110.56 (8)O4—Na1—Fe1viii40.19 (3)
O1—P1—C1103.34 (8)O3v—Na1—Fe1viii114.44 (4)
O3—P1—C1108.30 (8)C2vi—Na1—Fe1viii57.12 (4)
O2—P1—C1105.99 (8)P1—Na1—Fe1viii88.61 (2)
O1—P1—Na143.24 (6)P1v—Na1—Fe1viii119.69 (3)
O3—P1—Na195.39 (6)Fe1—Na1—Fe1viii119.73 (3)
O2—P1—Na1152.67 (6)Na1vii—Na1—Fe1viii125.38 (4)
C1—P1—Na172.21 (6)P1—O1—Fe1151.70 (9)
O1—P1—Na1iv130.89 (6)P1—O1—Na1110.23 (8)
O3—P1—Na1iv66.95 (6)Fe1—O1—Na196.21 (6)
O2—P1—Na1iv43.78 (6)P1—O2—Fe1i127.58 (8)
C1—P1—Na1iv123.83 (6)P1—O2—Na1iv109.52 (7)
Na1—P1—Na1iv158.45 (2)Fe1i—O2—Na1iv121.38 (7)
O1—Na1—O3iii79.95 (5)P1—O3—Fe1ix131.10 (8)
O1—Na1—O2v92.21 (6)P1—O3—Na1ix133.44 (8)
O3iii—Na1—O2v130.40 (7)Fe1ix—O3—Na1ix92.43 (6)
O1—Na1—O6vi140.06 (6)P1—O3—Na1iv84.78 (6)
O3iii—Na1—O6vi95.85 (6)Fe1ix—O3—Na1iv125.89 (6)
O2v—Na1—O6vi118.51 (6)Na1ix—O3—Na1iv79.93 (5)
O1—Na1—O480.23 (5)C1—O4—Fe1viii110.42 (10)
O3iii—Na1—O4134.23 (6)C1—O4—Na1103.78 (10)
O2v—Na1—O491.14 (5)Fe1viii—O4—Na194.89 (5)
O6vi—Na1—O474.68 (5)C1—O4—H4106.7
O1—Na1—O3v136.98 (6)Fe1viii—O4—H4117.4
O3iii—Na1—O3v100.07 (5)Na1—O4—H4122.5
O2v—Na1—O3v54.89 (5)C2—O5—Fe1viii113.84 (12)
O6vi—Na1—O3v82.95 (5)C2—O6—Fe1i130.23 (13)
O4—Na1—O3v122.19 (5)C2—O6—Na1x105.34 (12)
O1—Na1—C2vi162.81 (7)Fe1i—O6—Na1x99.17 (6)
O3iii—Na1—C2vi103.28 (6)O4—C1—C2106.71 (14)
O2v—Na1—C2vi98.06 (6)O4—C1—P1111.00 (12)
O6vi—Na1—C2vi23.73 (5)C2—C1—P1107.16 (13)
O4—Na1—C2vi85.79 (5)O4—C1—H1110.6
O3v—Na1—C2vi59.66 (5)C2—C1—H1110.6
O1—Na1—P126.53 (4)P1—C1—H1110.6
O3iii—Na1—P1104.70 (5)O6—C2—O5124.66 (18)
O2v—Na1—P183.44 (4)O6—C2—C1118.85 (17)
O6vi—Na1—P1126.57 (5)O5—C2—C1116.49 (16)
O4—Na1—P155.61 (4)O6—C2—Na1x50.93 (10)
O3v—Na1—P1138.09 (4)O5—C2—Na1x114.47 (13)
C2vi—Na1—P1141.39 (5)C1—C2—Na1x104.71 (11)
O1—Na1—P1v115.82 (5)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1/2, y+1, z+1/2; (iii) x+1/2, y1/2, z; (iv) x1/2, y+3/2, z+1; (v) x+1/2, y+3/2, z+1; (vi) x+1/2, y, z+1/2; (vii) x+1, y+1, z+1; (viii) x+1/2, y+1, z1/2; (ix) x+1/2, y+1/2, z; (x) x1/2, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O5ix0.881.742.6168 (19)173
Symmetry code: (ix) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaNa[Fe(C2H2O6P)]
Mr231.85
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)295
a, b, c (Å)10.2676 (8), 9.7330 (8), 10.8624 (9)
V3)1085.53 (15)
Z8
Radiation typeMo Kα
µ (mm1)3.12
Crystal size (mm)0.23 × 0.17 × 0.08
Data collection
DiffractometerBruker SMART APEXII CCD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Bruker, 2005)
Tmin, Tmax0.531, 0.795
No. of measured, independent and
observed [I > 2σ(I)] reflections
6143, 1309, 1213
Rint0.022
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.056, 1.07
No. of reflections1309
No. of parameters100
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.36

Computer programs: APEX2 (Bruker, 2005), APEX2, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997) and PLATON (Spek, 2003), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O5i0.881.742.6168 (19)172.7
Symmetry code: (i) x+1/2, y+1/2, z.
 
Acknowledgements top

This research was supported by grants from the Natural Science Foundation of Liaoning Province of China (20062140) and the Education Department of Liaoning Province of China (05 L214).