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Acta Cryst. (2008). E64, i10    [ doi:10.1107/S1600536808000214 ]

Disodium tetraaquabis(sulfato)iron(II)

M. Hudák, J. G. Díaz and J. Kozísek

Abstract top

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.

Comment top

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.

Related literature top

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

Experimental top

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 top

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

Computing details top

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

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids shown at the 30% probability level for non-H atoms.
[Figure 2] Fig. 2. Packing diagram viewed along the a axis. Hydrogen-bond interactions are indicated by dashed lines.
Disodium tetraaquabis(sulfonato)iron(II) top
Crystal data top
[FeNa2(SO4)2(H2O)4]F000 = 368
Mr = 366.01Dx = 2.416 Mg m−3
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 mm−1
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 top
Oxford Diffraction Gemini R CCD
diffractometer		1343 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 φ 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 top
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 Å−3
1343 reflectionsΔρmin = −0.40 e Å−3
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
Crystal data top
[FeNa2(SO4)2(H2O)4]V = 503.1 (1) Å3
Mr = 366.01Z = 2
Monoclinic, P21/cMo Kα
a = 5.551 (1) ŵ = 2.06 mm−1
b = 8.252 (1) ÅT = 301 (2) K
c = 11.162 (1) Å0.55 × 0.44 × 0.17 mm
β = 100.20 (1)º
Data collection top
Oxford Diffraction Gemini R CCD
diffractometer		1343 independent reflections
Absorption correction: analytical
[CrysAlis RED (Oxford Diffraction, 2007), based on Clark & Reid (1995)]		1288 reflections with I > 2σ(I)
Tmin = 0.398, Tmax = 0.720Rint = 0.022
19525 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.01896 parameters
wR(F2) = 0.047All H-atom parameters refined
S = 1.08Δρmax = 0.31 e Å−3
1343 reflectionsΔρmin = −0.40 e Å−3
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
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O8—H8A···O5i0.78 (3)1.97 (3)2.7513 (15)172 (2)
O8—H8B···O6ii0.73 (3)2.00 (3)2.7116 (15)165 (2)
O9—H9A···O6iii0.74 (3)2.16 (3)2.8741 (14)162 (2)
O9—H9B···O5i0.70 (3)2.32 (3)2.9379 (15)150 (3)
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y−1/2, −z+3/2; (iii) x−1, −y+3/2, z−1/2.
Acknowledgements top

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.

references
References top

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Held, P. (2003). Acta Cryst. E59, m197–m198.

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.