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The title complex, {[Fe(C4H4O4)(H2O)4]}n, is an infinite poly­meric compound bridged by the succinate dianion. Two carboxyl­ate groups coordinate in a monodentate manner to the FeII atom, in a trans fashion, with an O—Fe—O bond angle of 175.72 (6)° and Fe—O distances of 2.0886 (14) and 2.1008 (15) Å. One of the uncoordinated carboxyl­ate O atom forms an intramolecular hydrogen bond with a coordinated water mol­ecule. Extensive hydrogen bonding between parallel poly­meric complex chains results in a three-dimensional supramolecular structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102020693/fr1400sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102020693/fr1400Isup2.hkl
Contains datablock I

CCDC reference: 201268

Comment top

The succinate dianion has been used as a bridging ligand in the preparation of multinuclear metal complexes. A variety of bridging modes, including µ2–, µ3– and µ4, has been found (Ng, 1998; Rastsvetaeva et al., 1996; Ng & Kumar Das, 1993). Some recent structure determinations have shown that the coordination mode of the succinate dianion is affected by hydrogen bonding between water and one of the carboxylate group (Liu et al., 2002).

A section of the structure of the title compound, (I), is shown in Fig. 1. Two succinate O atoms, related by the translation symmetry, and four water molecules coordinate to the FeII center with normal octahedral coordination geometry. The succinate carbon skeleton assumes a trans-planar conformation, with a C1—C2—C3—C4 torsion angle of -173.67 (18)°. This skeleton is approximately coplanar with the coordination plane formed by atoms O1, O3i, O6 and O8 [symmetry code: (i) 1 + x, y, 1 + z] and perpendicular to the coordination plane formed by atoms O1, O3i, O5 and O7; the dihedral angles between the succinate carbon skeleton and the two coordination planes are 6.08 (11) and 89.84 (19)°, respectively. The two carboxylate groups of the same succinate dianion are nearly perpendicular to one another [dihedral angle 75.98 (17)°]. One of the carboxylate groups is nearly coplanar with the carbon skeleton [dihedral angle 4.5 (3)°], while the other is nearly perpendicular to it [dihedral angle 79.5 (2)°]. A search in Cambridge Structural Database (Allen, 2002) showed that this perpendicular geometry of the two carboxylate groups is different from the situation in µ2-succinate–metal complexes, including the similar NiII complex tetraaqua(µ2-succinato)nickel(II) (Gupta et al., 1983). Two separate intramolecular hydrogen bonds are observed between the carboxylate groups and coordinated water molecules (Fig. 1), which may be responsible for the nearly perpendicular arrangement of the carboxylate groups.

The succinate dianions act as bridging ligands in the structure, linking neighboring FeII atoms related by translational symmetry to form infinite polymeric complex chains spreading along the [101] direction. Each carboxylate group of the succinate dianion acts is monodentate, perhaps owing to the intramolecular hydrogen bonding between the coordinated carboxylate groups and coordinated water molecules.

An extensive hydrogen-bonding network exists in the crystal structure of (I), involving all carboxylate O atoms. The uncoordinated carboxylate atoms O2 and O4 are involved in the hydrogen bonding, intramolecularly to a neighboring coordinated water molecules, as mentioned above, and intermolecularly to adjacent polymeric chains. The water atoms O5 and O7 act as both donors and acceptors in the hydrogen bonding. The polymeric chains are interlinked via hydrogen bonding, resulting in a three-dimensional supramolecular structure.

Experimental top

An acetonitrile solution (20 ml) containing succinic acid (0.12 g, 1 mmol), FeCl3·6H2O (0.27 g, 1 mmol) and NaOH (0.08 g, 2 mmol) was refluxed for 1 h. The resulting dark-yellow solution was cooled to room temperature and filtered. Orange crystals were obtained from the filtrate after one week.

Refinement top

The methylene H atoms were placed in calculated positions (C—H = 0.97 Å) and included in the final cycles of refinement as riding, with Uiso(H) = 1.2Ueq of the carrier atom. The H atoms of the coordinated water molecules were located in a difference Fourier map and were refined with fixed positional parameters and Uiso(H) values of 0.08 Å2.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994).

Figures top
[Figure 1] Fig. 1. A section of the structure of the title polymeric compound shown with 50% probability displacement ellipsoids. [Symmetry code: (i) 1 + x, y, 1 + z.]
[Figure 2] Fig. 2. A packing diagram, showing the intermolecular hydrogen bonding between neighboring polymeric chains.
(I) top
Crystal data top
[Fe(C4H4O4)(H2O)4]F(000) = 504
Mr = 243.99Dx = 1.929 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 20 reflections
a = 7.4046 (10) Åθ = 4.5–10.0°
b = 14.7960 (13) ŵ = 1.81 mm1
c = 7.7788 (11) ÅT = 298 K
β = 99.727 (12)°Prism, orange
V = 839.98 (18) Å30.45 × 0.40 × 0.35 mm
Z = 4
Data collection top
Rigaku AFC-7S
diffractometer
1496 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.018
Graphite monochromatorθmax = 26.0°, θmin = 2.8°
ω/2θ scansh = 09
Absorption correction: ψ scan
(North et al., 1968)
k = 018
Tmin = 0.443, Tmax = 0.509l = 99
1778 measured reflections3 standard reflections every 150 reflections
1651 independent reflections intensity decay: 0.1%
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)] = 0.027H-atom parameters constrained
wR(F2) = 0.076 w = 1/[σ2(Fo2) + 0.3528P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
1651 reflectionsΔρmax = 0.42 e Å3
119 parametersΔρmin = 0.79 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.025 (2)
Crystal data top
[Fe(C4H4O4)(H2O)4]V = 839.98 (18) Å3
Mr = 243.99Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.4046 (10) ŵ = 1.81 mm1
b = 14.7960 (13) ÅT = 298 K
c = 7.7788 (11) Å0.45 × 0.40 × 0.35 mm
β = 99.727 (12)°
Data collection top
Rigaku AFC-7S
diffractometer
1496 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.018
Tmin = 0.443, Tmax = 0.5093 standard reflections every 150 reflections
1778 measured reflections intensity decay: 0.1%
1651 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.076H-atom parameters constrained
S = 1.04Δρmax = 0.42 e Å3
1651 reflectionsΔρmin = 0.79 e Å3
119 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
Fe0.57091 (4)0.644517 (17)0.81242 (3)0.01580 (14)
O10.3698 (2)0.66723 (11)0.59398 (18)0.0259 (3)
O20.2599 (2)0.52946 (10)0.53014 (19)0.0332 (4)
O30.2376 (2)0.62833 (11)0.04247 (19)0.0276 (3)
O40.0191 (2)0.63257 (11)0.0694 (2)0.0298 (4)
O50.38358 (19)0.66013 (10)0.98199 (19)0.0248 (3)
O60.5205 (2)0.50515 (11)0.79900 (19)0.0332 (4)
O70.7687 (2)0.62922 (10)0.64283 (19)0.0245 (3)
O80.6345 (2)0.78344 (10)0.82042 (18)0.0290 (3)
C10.2663 (3)0.61177 (14)0.4984 (2)0.0215 (4)
C20.1461 (3)0.65115 (14)0.3387 (3)0.0268 (5)
H2A0.22260.68420.27070.032*
H2B0.06100.69370.37610.032*
C30.0386 (3)0.58003 (14)0.2235 (3)0.0261 (4)
H3A0.12270.53380.19720.031*
H3B0.04750.55160.28780.031*
C40.0660 (3)0.61693 (13)0.0537 (2)0.0208 (4)
H510.36840.71671.02310.080*
H520.26890.64420.94770.080*
H610.42860.50310.70720.080*
H620.52280.46410.87560.080*
H710.77550.57720.59200.080*
H720.86930.63690.72620.080*
H810.68470.80770.92450.080*
H820.67870.81890.73870.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe0.01218 (19)0.02061 (19)0.01357 (19)0.00070 (9)0.00082 (12)0.00106 (9)
O10.0239 (8)0.0285 (7)0.0216 (7)0.0030 (6)0.0067 (6)0.0010 (6)
O20.0394 (9)0.0270 (8)0.0276 (8)0.0027 (7)0.0102 (7)0.0010 (6)
O30.0176 (8)0.0446 (9)0.0191 (7)0.0044 (6)0.0008 (6)0.0017 (6)
O40.0164 (7)0.0463 (9)0.0258 (8)0.0037 (6)0.0008 (6)0.0029 (6)
O50.0152 (7)0.0320 (7)0.0268 (8)0.0004 (6)0.0030 (6)0.0036 (6)
O60.0371 (9)0.0261 (8)0.0322 (8)0.0030 (7)0.0062 (7)0.0055 (6)
O70.0230 (8)0.0276 (7)0.0220 (7)0.0007 (6)0.0013 (6)0.0010 (5)
O80.0372 (9)0.0264 (7)0.0225 (7)0.0084 (7)0.0021 (6)0.0005 (5)
C10.0162 (9)0.0288 (10)0.0185 (9)0.0000 (8)0.0005 (7)0.0010 (8)
C20.0271 (12)0.0279 (10)0.0221 (10)0.0000 (8)0.0054 (9)0.0008 (7)
C30.0212 (10)0.0278 (10)0.0257 (10)0.0016 (8)0.0060 (8)0.0035 (8)
C40.0167 (9)0.0222 (9)0.0218 (9)0.0022 (8)0.0013 (7)0.0021 (7)
Geometric parameters (Å, º) top
Fe—O52.0821 (15)O6—H620.85
Fe—O12.0886 (14)O7—H710.87
Fe—O62.0951 (16)O7—H720.91
Fe—O3i2.1008 (15)O8—H810.91
Fe—O82.1074 (15)O8—H820.93
Fe—O72.1424 (16)C1—C21.517 (3)
O1—C11.273 (3)C2—C31.518 (3)
O2—C11.245 (3)C2—H2A0.970
O3—C41.269 (3)C2—H2B0.970
O4—C41.254 (2)C3—C41.516 (3)
O5—H510.91C3—H3A0.97
O5—H520.88C3—H3B0.97
O6—H610.90
O5—Fe—O192.17 (6)Fe—O7—H7296.4
O5—Fe—O690.50 (6)H71—O7—H72109.4
O1—Fe—O691.22 (6)Fe—O8—H81118.0
O5—Fe—O3i84.21 (6)Fe—O8—H82129.5
O1—Fe—O3i175.72 (6)H81—O8—H82104.5
O6—Fe—O3i91.10 (6)O2—C1—O1123.63 (18)
O5—Fe—O892.44 (6)O2—C1—C2120.09 (18)
O1—Fe—O889.55 (6)O1—C1—C2116.28 (18)
O6—Fe—O8176.94 (6)C1—C2—C3113.19 (17)
O3i—Fe—O888.32 (6)C1—C2—H2A108.9
O5—Fe—O7178.66 (5)C3—C2—H2A108.9
O1—Fe—O789.06 (6)C1—C2—H2B108.9
O6—Fe—O789.99 (6)C3—C2—H2B108.9
O3i—Fe—O794.54 (6)H2A—C2—H2B107.8
O8—Fe—O787.05 (6)C4—C3—C2113.86 (17)
C1—O1—Fe130.35 (14)C4—C3—H3A108.8
C4—O3—Feii126.69 (14)C2—C3—H3A108.8
Fe—O5—H51117.4C4—C3—H3B108.8
Fe—O5—H52119.4C2—C3—H3B108.8
H51—O5—H52100.6H3A—C3—H3B107.7
Fe—O6—H61100.2O4—C4—O3123.30 (18)
Fe—O6—H62133.4O4—C4—C3118.90 (18)
H61—O6—H62117.1O3—C4—C3117.78 (18)
Fe—O7—H71118.1
O5—Fe—O1—C191.29 (18)O1—C1—C2—C3175.25 (19)
O6—Fe—O1—C10.75 (18)C1—C2—C3—C4173.67 (18)
O8—Fe—O1—C1176.29 (18)Feii—O3—C4—O415.6 (3)
O7—Fe—O1—C189.22 (18)Feii—O3—C4—C3162.60 (13)
Fe—O1—C1—O25.5 (3)C2—C3—C4—O478.9 (3)
Fe—O1—C1—C2174.65 (14)C2—C3—C4—O3102.8 (2)
O2—C1—C2—C34.9 (3)
Symmetry codes: (i) x+1, y, z+1; (ii) x1, y, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H51···O1iii0.911.802.706 (2)172
O5—H52···O4iv0.881.842.692 (2)163
O6—H61···O20.901.742.620 (2)165
O6—H62···O5v0.852.202.996 (2)157
O7—H71···O2vi0.871.842.697 (2)169
O7—H72···O4i0.911.782.655 (2)161
O8—H81···O7iii0.911.952.847 (2)173
O8—H82···O3vii0.931.912.823 (2)169
Symmetry codes: (i) x+1, y, z+1; (iii) x, y+3/2, z+1/2; (iv) x, y, z+1; (v) x+1, y+1, z+2; (vi) x+1, y+1, z+1; (vii) x+1, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Fe(C4H4O4)(H2O)4]
Mr243.99
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)7.4046 (10), 14.7960 (13), 7.7788 (11)
β (°) 99.727 (12)
V3)839.98 (18)
Z4
Radiation typeMo Kα
µ (mm1)1.81
Crystal size (mm)0.45 × 0.40 × 0.35
Data collection
DiffractometerRigaku AFC-7S
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.443, 0.509
No. of measured, independent and
observed [I > 2σ(I)] reflections
1778, 1651, 1496
Rint0.018
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.076, 1.04
No. of reflections1651
No. of parameters119
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.42, 0.79

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1985), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994).

Selected geometric parameters (Å, º) top
Fe—O52.0821 (15)Fe—O72.1424 (16)
Fe—O12.0886 (14)O1—C11.273 (3)
Fe—O62.0951 (16)O2—C11.245 (3)
Fe—O3i2.1008 (15)O3—C41.269 (3)
Fe—O82.1074 (15)O4—C41.254 (2)
O5—Fe—O192.17 (6)O1—Fe—O889.55 (6)
O1—Fe—O691.22 (6)O3i—Fe—O888.32 (6)
O5—Fe—O3i84.21 (6)O1—Fe—O789.06 (6)
O1—Fe—O3i175.72 (6)O3i—Fe—O794.54 (6)
O6—Fe—O3i91.10 (6)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H51···O1ii0.911.802.706 (2)172
O5—H52···O4iii0.881.842.692 (2)163
O6—H61···O20.901.742.620 (2)165
O6—H62···O5iv0.852.202.996 (2)157
O7—H71···O2v0.871.842.697 (2)169
O7—H72···O4i0.911.782.655 (2)161
O8—H81···O7ii0.911.952.847 (2)173
O8—H82···O3vi0.931.912.823 (2)169
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+3/2, z+1/2; (iii) x, y, z+1; (iv) x+1, y+1, z+2; (v) x+1, y+1, z+1; (vi) x+1, y+3/2, z+1/2.
 

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