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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): i10.
Published online 2008 January 9. doi:  10.1107/S1600536808000214
PMCID: PMC2960384

Disodium tetra­aqua­bis(sulfato)iron(II)

Abstract

In the title compound, [FeNa2(SO4)2(H2O)4], the Fe2+ cation is situated on a centre of inversion and is hexa­coordinated by four O atoms from water mol­ecules and two O atoms from two sulfate anions in an octa­hedral geometry. The coordination environment of Na+ comprises six O atoms in a more distorted octa­hedral arrangement, with Na—O distances between 2.368 (1) and 2.612 (1) Å. The structure contains an extensive three-dimensional network of O—H(...)O hydrogen bonds.

Related literature

For related structures, see: Held (2003 [triangle]); Barton et al. (2002 [triangle]).

Experimental

Crystal data

  • [FeNa2(SO4)2(H2O)4]
  • M r = 366.01
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00i10-efi1.jpg
  • a = 5.551 (1) Å
  • b = 8.252 (1) Å
  • c = 11.162 (1) Å
  • β = 100.20 (1)°
  • V = 503.1 (1) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.06 mm−1
  • T = 301 (2) K
  • 0.55 × 0.44 × 0.17 mm

Data collection

  • Oxford Diffraction Gemini R CCD diffractometer
  • Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2007 [triangle]), based on Clark & Reid (1995 [triangle])] T min = 0.398, T max = 0.720
  • 19525 measured reflections
  • 1343 independent reflections
  • 1288 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.018
  • wR(F 2) = 0.047
  • S = 1.07
  • 1343 reflections
  • 96 parameters
  • All H-atom parameters refined
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.40 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 1998 [triangle]); software used to prepare material for publication: enCIFer (Allen et al., 2004 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808000214/bi2271sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808000214/bi2271Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Grant Agency of the Slovak Republic (grant Nos. VEGA 1/2449/05 and COSNET 545.03-P) and Structural Funds, Interreg IIIA, for financial support in purchasing the diffractometer.

supplementary crystallographic information

Comment

In order to find convenient crystals as model compounds for investigation of the electronic structure of FeII complexes, the title compound was prepared. The unit cell contains two FeII cations situated on centres of inversion, four Na+ cations, four SO42- anions and eight water molecules. The structure contains a three-dimensional network of O—H···O hydrogen bonds.

In the title compound (Fig. 1), the Fe1—O8 [2.115 (1) Å] and Fe1—O9 [2.170 (1) Å] bond lengths are in reasonable agreement with a similar compounds in the Cambridge Structural Database (CSD; Version 5.27, 2006 release). For example, in ethylenediammonium tetra-aqua-bis(sulfato-O)-iron(II) (Held, 2003; CSD refcode WABHIR), the Fe—O(water) distances are 2.111 and 2.143 Å, respectively. The Fe1—O2 distance to the sulfate anion [2.095 (1) Å] compares to 2.126 Å in WABHIR. In the crystal structure of pentaaqua-(3-(diphenylphosphino)phenylsulfonato)-iron(II) (diphenyl(3-sulfonatophenyl)phosphine) (Barton et al., 2002; CSD refcode XOHHOR), there are two symmetrically independent units with corresponding distances for Fe—O(water) in the range 2.085 to 2.125 Å and for Fe—O of the sulfonato anion between 2.10 and 2.126 Å.

Experimental

A solution of 1.0 mmol of Fe(SO4)2 in 2 ml water with one drop of diluted H2SO4(aq) and a piece of Fe metal was mixed with a solution of 2.0 mmol NaNO2NCN in 10 ml water and a solution of 2.0 mmol of imidazole in 10 ml me thanol. From this system, pale yellow crystals were isolated after a few days standing.

Refinement

H atoms were located in difference Fourier maps and refined freely with isotropic displacement parameters.

Figures

Fig. 1.
The asymmetric unit of the title compound with displacement ellipsoids shown at the 30% probability level for non-H atoms.
Fig. 2.
Packing diagram viewed along the a axis. Hydrogen-bond interactions are indicated by dashed lines.

Crystal data

[FeNa2(SO4)2(H2O)4]F000 = 368
Mr = 366.01Dx = 2.416 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 17533 reflections
a = 5.551 (1) Åθ = 3.0–31.4º
b = 8.252 (1) ŵ = 2.06 mm1
c = 11.162 (1) ÅT = 301 (2) K
β = 100.20 (1)ºBlock, pale yellow
V = 503.1 (1) Å30.55 × 0.44 × 0.17 mm
Z = 2

Data collection

Oxford Diffraction Gemini R CCD diffractometer1343 independent reflections
Radiation source: fine-focus sealed tube1288 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.022
T = 301(2) Kθmax = 29.5º
ω and [var phi] scansθmin = 6.6º
Absorption correction: analytical[CrysAlis RED (Oxford Diffraction, 2007), based on Clark & Reid (1995)]h = −7→7
Tmin = 0.398, Tmax = 0.720k = −11→11
19525 measured reflectionsl = −15→15

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.018  w = 1/[σ2(Fo2) + (0.0245P)2 + 0.3061P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.047(Δ/σ)max = 0.001
S = 1.08Δρmax = 0.31 e Å3
1343 reflectionsΔρmin = −0.40 e Å3
96 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.062 (3)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/Ueq
O20.81620 (17)0.63212 (12)0.56957 (10)0.0228 (2)
O40.70650 (19)0.91424 (13)0.57758 (9)0.0234 (2)
O51.12799 (17)0.82849 (12)0.63063 (10)0.0234 (2)
O60.84525 (19)0.76778 (12)0.76330 (9)0.0224 (2)
O80.37101 (18)0.53699 (14)0.66515 (9)0.01827 (19)
H8A0.294 (4)0.617 (3)0.660 (2)0.039 (6)*
H8B0.290 (4)0.472 (3)0.679 (2)0.031 (6)*
O90.31917 (19)0.71528 (13)0.41612 (10)0.0201 (2)
H9A0.211 (5)0.707 (3)0.368 (2)0.039 (6)*
H9B0.272 (5)0.771 (3)0.453 (2)0.040 (7)*
S30.86989 (5)0.78740 (3)0.63455 (3)0.01276 (9)
Na70.62761 (10)0.56900 (7)0.86236 (5)0.02189 (13)
Fe10.50000.50000.50000.01297 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O20.0175 (4)0.0203 (5)0.0302 (5)−0.0039 (3)0.0031 (4)−0.0113 (4)
O40.0263 (5)0.0248 (5)0.0183 (4)0.0113 (4)0.0017 (4)0.0034 (4)
O50.0148 (4)0.0218 (5)0.0342 (5)−0.0049 (4)0.0058 (4)−0.0040 (4)
O60.0292 (5)0.0243 (5)0.0142 (4)0.0024 (4)0.0054 (4)0.0024 (4)
O80.0190 (4)0.0188 (5)0.0182 (4)0.0011 (4)0.0068 (3)0.0005 (4)
O90.0203 (5)0.0178 (5)0.0198 (5)0.0025 (4)−0.0030 (4)−0.0015 (4)
S30.01181 (14)0.01334 (15)0.01272 (15)0.00036 (9)0.00107 (10)−0.00092 (10)
Na70.0242 (3)0.0222 (3)0.0185 (3)−0.0010 (2)0.0018 (2)0.0011 (2)
Fe10.01386 (13)0.01298 (13)0.01206 (13)−0.00055 (8)0.00225 (8)−0.00057 (8)

Geometric parameters (Å, °)

O2—S31.4765 (10)O9—Na7i2.6122 (12)
O2—Fe12.0951 (9)O9—H9A0.74 (3)
O4—S31.4553 (10)O9—H9B0.70 (3)
O4—Na7i2.3683 (11)S3—Na7i3.3160 (6)
O4—Na7ii2.4413 (11)Na7—O4iv2.3684 (11)
O5—S31.4805 (9)Na7—O5v2.3974 (11)
O5—Na7iii2.3975 (11)Na7—O4vi2.4413 (11)
O6—S31.4764 (10)Na7—O9iv2.6123 (12)
O6—Na72.4178 (11)Na7—S3iv3.3160 (6)
O8—Fe12.1146 (9)Na7—Na7vii3.7798 (11)
O8—Na72.4153 (11)Na7—H8B2.64 (2)
O8—H8A0.78 (3)Fe1—O2viii2.0951 (9)
O8—H8B0.73 (3)Fe1—O8viii2.1146 (9)
O9—Fe12.1695 (10)Fe1—O9viii2.1695 (10)
S3—O2—Fe1135.77 (6)O8—Na7—O9iv88.81 (4)
S3—O4—Na7i118.30 (6)O6—Na7—O9iv92.51 (4)
S3—O4—Na7ii134.52 (6)O4vi—Na7—O9iv74.50 (4)
Na7i—O4—Na7ii103.59 (4)O4iv—Na7—S3iv22.73 (2)
S3—O5—Na7iii137.19 (6)O5v—Na7—S3iv97.50 (3)
S3—O6—Na7131.26 (6)O8—Na7—S3iv162.20 (3)
Fe1—O8—Na7125.04 (5)O6—Na7—S3iv91.27 (3)
Fe1—O8—H8A108.5 (17)O4vi—Na7—S3iv98.04 (3)
Na7—O8—H8A102.0 (17)O9iv—Na7—S3iv73.86 (3)
Fe1—O8—H8B113.3 (17)O4iv—Na7—Na7vii38.89 (3)
Na7—O8—H8B99.8 (17)O5v—Na7—Na7vii90.89 (3)
H8A—O8—H8B106 (2)O8—Na7—Na7vii117.55 (3)
Fe1—O9—Na7i112.65 (4)O6—Na7—Na7vii149.97 (4)
Fe1—O9—H9A120.0 (19)O4vi—Na7—Na7vii37.52 (2)
Na7i—O9—H9A111.8 (19)O9iv—Na7—Na7vii70.32 (3)
Fe1—O9—H9B118 (2)S3iv—Na7—Na7vii60.819 (15)
Na7i—O9—H9B91 (2)O4iv—Na7—H8B141.4 (5)
H9A—O9—H9B99 (3)O5v—Na7—H8B95.4 (5)
O4—S3—O6110.26 (6)O8—Na7—H8B15.9 (5)
O4—S3—O2110.70 (6)O6—Na7—H8B101.2 (5)
O6—S3—O2109.73 (6)O4vi—Na7—H8B65.5 (5)
O4—S3—O5110.72 (6)O9iv—Na7—H8B88.8 (5)
O6—S3—O5108.11 (6)S3iv—Na7—H8B159.2 (5)
O2—S3—O5107.24 (6)Na7vii—Na7—H8B102.8 (5)
O6—S3—Na7i146.99 (4)O2viii—Fe1—O2180.0
O2—S3—Na7i81.15 (5)O2viii—Fe1—O890.43 (4)
O5—S3—Na7i97.39 (5)O2—Fe1—O889.57 (4)
O4iv—Na7—O5v90.76 (4)O2viii—Fe1—O8viii89.57 (4)
O4iv—Na7—O8154.70 (4)O2—Fe1—O8viii90.43 (4)
O5v—Na7—O8100.26 (4)O8—Fe1—O8viii180.0
O4iv—Na7—O6114.00 (4)O2viii—Fe1—O9viii91.55 (4)
O5v—Na7—O6104.53 (4)O2—Fe1—O9viii88.45 (4)
O8—Na7—O685.36 (4)O8—Fe1—O9viii86.80 (4)
O4iv—Na7—O4vi76.41 (4)O8viii—Fe1—O9viii93.20 (4)
O5v—Na7—O4vi90.63 (4)O2viii—Fe1—O988.45 (4)
O8—Na7—O4vi80.73 (4)O2—Fe1—O991.55 (4)
O6—Na7—O4vi161.06 (4)O8—Fe1—O993.20 (4)
O4iv—Na7—O9iv74.82 (4)O8viii—Fe1—O986.80 (4)
O5v—Na7—O9iv161.21 (4)O9viii—Fe1—O9179.999 (1)
Na7i—O4—S3—O6−164.83 (6)Fe1—O8—Na7—O9iv142.28 (6)
Na7ii—O4—S3—O6−10.15 (11)Fe1—O8—Na7—S3iv129.32 (9)
Na7i—O4—S3—O2−43.22 (8)Fe1—O8—Na7—Na7vii−150.72 (5)
Na7ii—O4—S3—O2111.45 (9)S3—O6—Na7—O4iv172.17 (7)
Na7i—O4—S3—O575.58 (8)S3—O6—Na7—O5v74.68 (8)
Na7ii—O4—S3—O5−129.75 (9)S3—O6—Na7—O8−24.74 (8)
Na7ii—O4—S3—Na7i154.67 (13)S3—O6—Na7—O4vi−67.51 (16)
Na7—O6—S3—O4101.13 (8)S3—O6—Na7—O9iv−113.34 (8)
Na7—O6—S3—O2−21.05 (9)S3—O6—Na7—S3iv172.76 (7)
Na7—O6—S3—O5−137.70 (7)S3—O6—Na7—Na7vii−166.63 (6)
Na7—O6—S3—Na7i83.55 (10)S3—O2—Fe1—O8−46.73 (10)
Fe1—O2—S3—O4−45.49 (11)S3—O2—Fe1—O8viii133.27 (10)
Fe1—O2—S3—O676.42 (10)S3—O2—Fe1—O9viii−133.54 (10)
Fe1—O2—S3—O5−166.38 (9)S3—O2—Fe1—O946.46 (10)
Fe1—O2—S3—Na7i−71.33 (9)Na7—O8—Fe1—O2viii150.22 (6)
Na7iii—O5—S3—O432.62 (11)Na7—O8—Fe1—O2−29.78 (6)
Na7iii—O5—S3—O6−88.26 (10)Na7—O8—Fe1—O9viii58.69 (6)
Na7iii—O5—S3—O2153.49 (9)Na7—O8—Fe1—O9−121.31 (6)
Na7iii—O5—S3—Na7i70.50 (9)Na7i—O9—Fe1—O2viii−152.73 (5)
Fe1—O8—Na7—O4iv−168.78 (8)Na7i—O9—Fe1—O227.27 (5)
Fe1—O8—Na7—O5v−54.28 (7)Na7i—O9—Fe1—O8116.93 (5)
Fe1—O8—Na7—O649.67 (6)Na7i—O9—Fe1—O8viii−63.07 (5)
Fe1—O8—Na7—O4vi−143.24 (7)

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+2, y+1/2, −z+3/2; (iv) x, −y+3/2, z+1/2; (v) −x+2, y−1/2, −z+3/2; (vi) −x+1, y−1/2, −z+3/2; (vii) −x+1, −y+1, −z+2; (viii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O8—H8A···O5ix0.78 (3)1.97 (3)2.7513 (15)172 (2)
O8—H8B···O6vi0.73 (3)2.00 (3)2.7116 (15)165 (2)
O9—H9A···O6x0.74 (3)2.16 (3)2.8741 (14)162 (2)
O9—H9B···O5ix0.70 (3)2.32 (3)2.9379 (15)150 (3)

Symmetry codes: (ix) x−1, y, z; (vi) −x+1, y−1/2, −z+3/2; (x) x−1, −y+3/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2271).

References

  • Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst.37, 335–338.
  • Barton, M. R., Zhang, Y. G. & Atwood, J. D. (2002). J. Coord. Chem.55, 969–983.
  • Brandenburg, K. (1998). DIAMOND University of Bonn, Germany.
  • Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.
  • Held, P. (2003). Acta Cryst. E59, m197–m198.
  • Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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