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Acta Cryst. (2007). E63, m2315    [ doi:10.1107/S1600536807038743 ]

Poly[diaqua-[mu]3-malonato-[mu]-pyrazine-diiron(II)]

Z.-F. Li, Y. Liu, Q. Zhang and X.-J. Yu

Abstract top

The title compound, [Fe2(C3H2O4)2(C4H4N2)(H2O)2]n, prepared by hydrothermal synthesis, is isostructural with its CoII, NiII, ZnII and CdII analogues. The FeII atoms are linked via coordinated malonates into two-dimensional sheets containing cavities. The sheets are connected by bridging pyrazine ligands which lie on centres of inversion. The coordination geometry around FeII is a tetragonally elongated octahedron, in which pyrazine N and aqua O atoms occupy the axial positions. The coordinated water molecules form O-H...O hydrogen bonds to the malonate ligands.

Comment top

The title compound is isostructural with its CoII (Delgado et al., 2003), NiII (Liu et al., 2005), ZnII (Zhang et al., 2003; Delgado et al., 2003) and CdII (Mao et al., 2004) analogues. The FeII atom exhibits sixfold coordination, chelated by two O atoms from one malonate ligand to form a six-membered boat-type ring, and by two O atoms from two neighbouring malonates, one water molecule and one N atom from the bridging pyrazine ligand (Fig. 1). The Fe—O(carboxylate) and Fe—N bond lengths are in the range 2.064 (4)–2.202 (4) and 2.272 (4) Å, respectively.

The [Fe(malonate)(H2O)] units form two-dimensional networks parallel to the (010) planes. These are linked by the bridging pyrazine ligands into a three-dimensional structure. O—H···O hydrogen bonds (Table 1) are formed between the coordinated water molecules and the malonate ligands.

Related literature top

For the isostructural analogues, see: CoII (Delgado et al., 2003); NiII (Liu et al., 2005); ZnII (Zhang et al., 2003; Delgado et al., 2003); CdII (Mao et al., 2004).

Experimental top

A mixture of FeSO4 (0.5 mmol), malonic acid (0.5 mmol), NaOH (1 mmol), pyrazine (1 mmol) and H2O (8 ml) in a 25 ml Teflon-lined stainless steel autoclave was heated at 443 K for two days, and then cooled to room temperature. Light green block crystals of the title compound were obtained with a yield of 22%. Elemental analysis: calculated C 27.91, H 2.79, N 6.51%; found: C 27.88, H 2.75, N 6.47%.

Refinement top

All H atoms on C atoms were generated geometrically and refined as riding atoms with C—H = 0.93 or 0.97 Å and with Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule were located from difference Fourier maps and were refined with distance restraints of d(H—H) = 1.38 (2) Å, d(O—H) = 0.82 (1) Å.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Part of the polymeric structure of the title complex showing displacement ellipsoids at 30% probability for non-H atoms. Atoms labeled with the suffix I are generated by the symmetry operator (−x + 1, y + 1/2,-z + 3/2).
[Figure 2] Fig. 2. Packing diagram for the title complex viewed along the c-axis.
Poly[diaqua-µ3-malonato-µ-pyrazine-diiron(II)] top
Crystal data top
[Fe2(C3H2O4)2(C4H4N2)(H2O)2]F000 = 436
Mr = 431.92Dx = 1.930 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1293 reflections
a = 6.9652 (10) Åθ = 2.8–25.0º
b = 14.589 (2) ŵ = 2.01 mm−1
c = 7.3212 (10) ÅT = 293 (2) K
β = 92.179 (1)ºBlock, green
V = 743.39 (18) Å30.36 × 0.28 × 0.24 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer		1293 independent reflections
Radiation source: fine-focus sealed tube1100 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
T = 293(2) Kθmax = 25.0º
φ and ω scansθmin = 2.8º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −8→3
Tmin = 0.532, Tmax = 0.644k = −13→16
2391 measured reflectionsl = −8→8
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.106  w = 1/[σ2(Fo2) + (0.0653P)2 + 1.1979P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.010
1293 reflectionsΔρmax = 0.65 e Å−3
116 parametersΔρmin = −0.40 e Å−3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.039 (4)
Crystal data top
[Fe2(C3H2O4)2(C4H4N2)(H2O)2]V = 743.39 (18) Å3
Mr = 431.92Z = 2
Monoclinic, P21/nMo Kα
a = 6.9652 (10) ŵ = 2.01 mm−1
b = 14.589 (2) ÅT = 293 (2) K
c = 7.3212 (10) Å0.36 × 0.28 × 0.24 mm
β = 92.179 (1)º
Data collection top
Bruker APEXII CCD
diffractometer		1293 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		1100 reflections with I > 2σ(I)
Tmin = 0.532, Tmax = 0.644Rint = 0.023
2391 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0403 restraints
wR(F2) = 0.106H atoms treated by a mixture of
independent and constrained refinement
S = 1.00Δρmax = 0.65 e Å−3
1293 reflectionsΔρmin = −0.40 e Å−3
116 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
C10.5845 (6)0.3316 (3)0.7563 (6)0.0316 (9)
C20.6129 (7)0.3912 (3)0.5893 (6)0.0397 (10)
H2A0.52380.44230.59120.048*
H2B0.74220.41600.59550.048*
C30.5827 (6)0.3401 (3)0.4125 (6)0.0317 (9)
C40.4533 (7)0.0742 (3)0.5913 (7)0.0473 (12)
H40.41380.12510.65650.057*
C50.6788 (6)−0.0045 (3)0.4450 (7)0.0437 (11)
H50.8030−0.01070.40420.052*
Fe10.83758 (7)0.19136 (3)0.58103 (6)0.0177 (3)
N10.6323 (5)0.0716 (2)0.5376 (5)0.0357 (8)
O10.6634 (4)0.2528 (2)0.7697 (4)0.0397 (8)
O20.4864 (4)0.3672 (2)0.8748 (4)0.0403 (8)
O30.6700 (5)0.2644 (2)0.3900 (4)0.0429 (8)
O40.4752 (4)0.3774 (2)0.2946 (4)0.0393 (7)
O51.0315 (5)0.3106 (2)0.5861 (4)0.0439 (8)
H2W1.090 (8)0.308 (4)0.490 (4)0.080*
H1W1.101 (7)0.298 (4)0.677 (5)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.034 (2)0.029 (2)0.032 (2)0.0001 (18)0.0005 (16)−0.0053 (18)
C20.056 (3)0.034 (2)0.029 (2)0.005 (2)0.0022 (19)0.0010 (19)
C30.036 (2)0.028 (2)0.032 (2)0.0035 (18)0.0042 (17)0.0045 (18)
C40.044 (3)0.039 (3)0.060 (3)−0.005 (2)0.018 (2)−0.014 (2)
C50.038 (2)0.034 (3)0.060 (3)−0.002 (2)0.012 (2)−0.009 (2)
Fe10.0219 (3)0.0169 (4)0.0145 (3)0.00068 (19)0.0018 (2)−0.00062 (19)
N10.0357 (18)0.033 (2)0.038 (2)−0.0020 (16)0.0017 (15)−0.0011 (16)
O10.0516 (18)0.0358 (18)0.0325 (16)0.0069 (14)0.0116 (13)0.0027 (13)
O20.0454 (17)0.0379 (18)0.0387 (17)0.0043 (14)0.0168 (13)0.0000 (14)
O30.054 (2)0.042 (2)0.0325 (16)0.0114 (15)−0.0052 (14)−0.0031 (14)
O40.0476 (17)0.0335 (17)0.0363 (16)0.0027 (14)−0.0060 (13)0.0027 (14)
O50.0467 (19)0.053 (2)0.0325 (17)−0.0013 (15)0.0019 (14)0.0000 (15)
Geometric parameters (Å, °) top
C1—O21.239 (5)C5—C4i1.390 (7)
C1—O11.276 (5)C5—H50.930
C1—C21.519 (6)Fe1—O2ii2.050 (3)
C2—C31.501 (6)Fe1—O4iii2.064 (3)
C2—H2A0.970Fe1—O12.076 (3)
C2—H2B0.970Fe1—O32.081 (3)
C3—O41.246 (5)Fe1—O52.202 (4)
C3—O31.275 (6)Fe1—N12.272 (4)
C4—N11.322 (6)O2—Fe1iv2.050 (3)
C4—C5i1.390 (7)O4—Fe1v2.064 (3)
C4—H40.930O5—H2W0.83 (4)
C5—N11.347 (6)O5—H1W0.83 (4)
O2—C1—O1124.8 (4)O4iii—Fe1—O3172.32 (12)
O2—C1—C2114.6 (4)O1—Fe1—O384.20 (12)
O1—C1—C2120.6 (4)O2ii—Fe1—O590.84 (12)
C3—C2—C1113.1 (4)O4iii—Fe1—O595.99 (12)
C3—C2—H2A109.0O1—Fe1—O591.21 (12)
C1—C2—H2A109.0O3—Fe1—O586.27 (14)
C3—C2—H2B109.0O2ii—Fe1—N184.81 (12)
C1—C2—H2B109.0O4iii—Fe1—N190.23 (13)
H2A—C2—H2B107.8O1—Fe1—N192.56 (13)
O4—C3—O3124.5 (4)O3—Fe1—N188.03 (13)
O4—C3—C2116.2 (4)O5—Fe1—N1172.81 (13)
O3—C3—C2119.3 (4)C4—N1—C5114.9 (4)
N1—C4—C5i123.2 (4)C4—N1—Fe1122.1 (3)
N1—C4—H4118.4C5—N1—Fe1122.9 (3)
C5i—C4—H4118.4C1—O1—Fe1126.8 (3)
N1—C5—C4i122.0 (4)C1—O2—Fe1iv130.5 (3)
N1—C5—H5119.0C3—O3—Fe1128.0 (3)
C4i—C5—H5119.0C3—O4—Fe1v124.2 (3)
O2ii—Fe1—O4iii97.03 (13)Fe1—O5—H2W106 (4)
O2ii—Fe1—O1173.95 (12)Fe1—O5—H1W100 (5)
O4iii—Fe1—O188.42 (13)H2W—O5—H1W113 (3)
O2ii—Fe1—O390.26 (13)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) x−1/2, −y+1/2, z+1/2; (v) x−1/2, −y+1/2, z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H2W···O1ii0.83 (4)1.93 (3)2.689 (4)152 (6)
O5—H2W···O2ii0.83 (4)2.78 (6)3.031 (5)99 (5)
Symmetry codes: (ii) x+1/2, −y+1/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H2W···O1i0.83 (4)1.93 (3)2.689 (4)152 (6)
O5—H2W···O2i0.83 (4)2.78 (6)3.031 (5)99 (5)
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2.
Acknowledgements top

The authors thank Shandong University of Technology for financial support.

references
References top

Bruker (2001). SAINT-Plus and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

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Liu, Y., Dou, J., Wang, D., Ma, G. & Li, D. (2005). Acta Cryst. E61, m1834–m1836.

Mao, H. Y., Zhang, C. Z., Li, G., Zhang, H. Y., Hou, H. W., Li, L. J., Wu, Q. G., Zhu, Y. & Wang, E. B. (2004). Discuss. Faraday Soc. pp. 3918–3919.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Zhang, X. T., Lu, C. Z., Zhang, Q. Z., Lu, S. F., Yang, W. B., Liu, J. C. & Zhuang, H. H. (2003). Eur. J. Inorg. Chem. pp. 1181–11816.