Acta Cryst. (2007). E63, m2966 [ doi:10.1107/S1600536807055377 ]
![[mu]](/logos/entities/mu_rmgif.gif)
3-malonato-iron(II)] monohydrate]The title coordination polymer, [[Fe(C4H4O5)(H2O)2]·H2O]n, was obtained by the hydrothermal reaction of FeSO4 with malic acid in alkaline aqueous solution. Each FeII atom is coordinated by four O atoms from three malate ligands and two water molecules, and displays a distorted octahedral geometry. The polychelated malate ligands bridge Fe ions to form corrugated layers; these layers are further assembled by intermolecular O-H
O hydrogen-bonding interactions to form a three-dimensional supramolecular network, with channels running along the b axis in which the uncoordinated water molecules are located. The solvent water molecule is disordered over two positions, with occupancy ratios of 0.78/0.22.
A mixture of FeSO4 (0.5 mmol), malic acid (0.5 mmol), NaOH(1 mmol) and H2O (10 ml) was placed in a 23 ml Teflon reactor, which was heated at 433 K for three days and then cooled to room temperature at a rate of 5 K h−1. Single crystals were obtained after washing with water and drying in air.
The solvate water molecule is disordered over two positions with occupancy ratios of 0.78/0.22. Water and hydroxyl H atoms were located in difference density Fourier maps and were refined using restraints (O—H= 0.82 (1) Å and H···H= 1.33 (2) Å) with Uiso(H) = 1.5 Ueq(O). The hydrogen atoms of the disordered water molecule were set to have each the same coordinates for both disordered H2O molecules. H atoms attached to carbon were placed at calculated positions and were treated as riding on their parent C atoms with C—H = 0.97 Å (methylene) or 0.98 Å (methine), and with Uiso(H) = 1.2 Ueq(C).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
![[Figure 1]](./dn2256fig1thm.gif)
| Fig. 1. The structure of (I), showing the atom-numbering scheme and the formation of the polymetric structure. displacement ellipsoids are drawn at the 30% probability level. The solvate water molecule and H atoms have been omitted for clarity. [Symmetry codes: (i) −x, −y + 2, −z; (ii) x, −y + 3/2, z + 1/2; (iii) −x, y − 1/2, −z + 1/2] |
![[Figure 2]](./dn2256fig2thm.gif)
| Fig. 2. View of the supramolecular network along the b axis. The minor moiety of the disordered water molecules were omitted for clarity. |
| [Fe(C4H4O5)(H2O)2]·H2O | F000 = 992 |
| Mr = 241.97 | Dx = 1.857 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 1506 reflections |
| a = 14.2225 (8) Å | θ = 1.4–28.0º |
| b = 8.2788 (5) Å | µ = 1.76 mm−1 |
| c = 14.7043 (8) Å | T = 293 (2) K |
| V = 1731.36 (17) Å3 | Blocky, red |
| Z = 8 | 0.32 × 0.26 × 0.23 mm |
| Bruker APEXII area-detector diffractometer | 1603 independent reflections |
| Radiation source: fine-focus sealed tube | 1420 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.026 |
| T = 293(2) K | θmax = 25.5º |
| φ and ω scan | θmin = 2.8º |
| Absorption correction: multi-scan SADABS (Sheldrick, 1996) | h = −17→14 |
| Tmin = 0.587, Tmax = 0.670 | k = −10→7 |
| 8229 measured reflections | l = −17→17 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.040P)2 + 1.9411P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.10 | (Δ/σ)max = 0.003 |
| 1603 reflections | Δρmax = 0.38 e Å−3 |
| 142 parameters | Δρmin = −0.38 e Å−3 |
| 7 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| [Fe(C4H4O5)(H2O)2]·H2O | V = 1731.36 (17) Å3 |
| Mr = 241.97 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα |
| a = 14.2225 (8) Å | µ = 1.76 mm−1 |
| b = 8.2788 (5) Å | T = 293 (2) K |
| c = 14.7043 (8) Å | 0.32 × 0.26 × 0.23 mm |
| Bruker APEXII area-detector diffractometer | 1603 independent reflections |
| Absorption correction: multi-scan SADABS (Sheldrick, 1996) | 1420 reflections with I > 2σ(I) |
| Tmin = 0.587, Tmax = 0.670 | Rint = 0.026 |
| 8229 measured reflections |
| R[F2 > 2σ(F2)] = 0.028 | 7 restraints |
| wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.10 | Δρmax = 0.38 e Å−3 |
| 1603 reflections | Δρmin = −0.38 e Å−3 |
| 142 parameters |
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. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| C1 | 0.20311 (17) | 0.8001 (3) | 0.04422 (16) | 0.0237 (5) | |
| C2 | 0.13407 (16) | 0.7905 (3) | −0.03528 (15) | 0.0219 (5) | |
| H2 | 0.1599 | 0.7192 | −0.0822 | 0.026* | |
| C3 | 0.11770 (18) | 0.9566 (3) | −0.07561 (16) | 0.0252 (5) | |
| H3A | 0.1781 | 1.0064 | −0.0880 | 0.030* | |
| H3B | 0.0855 | 1.0230 | −0.0311 | 0.030* | |
| C4 | 0.06047 (18) | 0.9543 (3) | −0.16261 (16) | 0.0240 (5) | |
| Fe1 | 0.02997 (3) | 0.68818 (4) | 0.14709 (2) | 0.02428 (15) | |
| O1 | 0.17406 (12) | 0.7638 (2) | 0.12267 (11) | 0.0272 (4) | |
| O2 | 0.28461 (13) | 0.8461 (3) | 0.02750 (12) | 0.0414 (5) | |
| O3 | 0.04782 (12) | 0.7240 (2) | −0.00225 (12) | 0.0281 (4) | |
| H3 | 0.018 (2) | 0.677 (3) | −0.0408 (17) | 0.042* | |
| O4 | 0.06326 (15) | 0.8301 (2) | −0.21102 (12) | 0.0317 (4) | |
| O5 | 0.01587 (17) | 1.0778 (3) | −0.18482 (14) | 0.0469 (6) | |
| O1W | 0.06641 (13) | 0.4258 (2) | 0.12724 (12) | 0.0263 (4) | |
| H11 | 0.1195 (11) | 0.402 (4) | 0.1098 (18) | 0.039* | |
| H12 | 0.0556 (19) | 0.378 (4) | 0.1741 (13) | 0.039* | |
| O2W | −0.11083 (13) | 0.6067 (3) | 0.12508 (14) | 0.0416 (5) | |
| H21 | −0.144 (2) | 0.595 (5) | 0.1692 (14) | 0.062* | |
| H22 | −0.143 (2) | 0.630 (5) | 0.0812 (14) | 0.062* | |
| O30A | −0.2284 (3) | 0.5249 (6) | 0.2582 (3) | 0.0559 (11) | 0.77 |
| H31A | −0.2472 | 0.6044 | 0.2892 | 0.084* | 0.77 |
| H32A | −0.2001 | 0.4884 | 0.3040 | 0.084* | 0.77 |
| O30B | −0.1891 (9) | 0.5849 (17) | 0.2825 (10) | 0.055 (4) | 0.23 |
| H31B | −0.2473 | 0.6043 | 0.2888 | 0.083* | 0.23 |
| H32B | −0.2002 | 0.4883 | 0.3036 | 0.083* | 0.23 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0222 (13) | 0.0283 (13) | 0.0207 (12) | 0.0000 (10) | −0.0009 (10) | 0.0008 (9) |
| C2 | 0.0206 (12) | 0.0278 (13) | 0.0173 (11) | −0.0018 (10) | −0.0014 (9) | −0.0005 (9) |
| C3 | 0.0288 (13) | 0.0256 (13) | 0.0211 (12) | −0.0023 (10) | −0.0020 (10) | −0.0018 (9) |
| C4 | 0.0286 (13) | 0.0251 (13) | 0.0183 (11) | 0.0003 (10) | 0.0005 (10) | 0.0010 (10) |
| Fe1 | 0.0240 (2) | 0.0278 (2) | 0.0211 (2) | −0.00038 (14) | −0.00096 (13) | −0.00105 (13) |
| O1 | 0.0233 (9) | 0.0404 (10) | 0.0180 (8) | −0.0054 (8) | −0.0034 (7) | 0.0032 (7) |
| O2 | 0.0217 (10) | 0.0778 (15) | 0.0247 (9) | −0.0132 (10) | −0.0012 (7) | 0.0072 (10) |
| O3 | 0.0265 (9) | 0.0387 (11) | 0.0190 (9) | −0.0141 (8) | −0.0037 (7) | 0.0006 (7) |
| O4 | 0.0504 (12) | 0.0260 (9) | 0.0187 (9) | 0.0045 (8) | −0.0066 (8) | −0.0028 (7) |
| O5 | 0.0678 (15) | 0.0368 (11) | 0.0362 (11) | 0.0268 (11) | −0.0182 (10) | −0.0093 (9) |
| O1W | 0.0281 (9) | 0.0277 (9) | 0.0232 (9) | −0.0001 (8) | 0.0050 (7) | 0.0010 (7) |
| O2W | 0.0231 (10) | 0.0722 (15) | 0.0293 (10) | −0.0078 (10) | −0.0031 (8) | 0.0100 (10) |
| O30A | 0.048 (3) | 0.076 (3) | 0.043 (2) | 0.0182 (19) | 0.0119 (17) | 0.024 (2) |
| O30B | 0.050 (9) | 0.061 (9) | 0.054 (9) | 0.035 (7) | 0.029 (7) | 0.025 (7) |
| C1—O2 | 1.245 (3) | Fe1—O1W | 2.2522 (18) |
| C1—O1 | 1.262 (3) | O3—H3 | 0.81 (3) |
| C1—C2 | 1.529 (3) | O1W—H11 | 0.820 (10) |
| C2—O3 | 1.430 (3) | O1W—H12 | 0.809 (10) |
| C2—C3 | 1.515 (3) | O2W—H21 | 0.811 (10) |
| C2—H2 | 0.9800 | O2W—H22 | 0.81 (3) |
| C3—C4 | 1.516 (3) | O30A—O30B | 0.828 (14) |
| C3—H3A | 0.9700 | O30A—H31A | 0.8441 |
| C3—H3B | 0.9700 | O30A—H32A | 0.8407 |
| C4—O5 | 1.247 (3) | O30A—H31B | 0.8404 |
| C4—O4 | 1.251 (3) | O30A—H32B | 0.8348 |
| Fe1—O5i | 2.118 (2) | O30B—H31A | 0.8472 |
| Fe1—O2W | 2.1376 (19) | O30B—H32A | 0.8736 |
| Fe1—O4ii | 2.1448 (17) | O30B—H31B | 0.8482 |
| Fe1—O1 | 2.1728 (18) | O30B—H32B | 0.8724 |
| Fe1—O3 | 2.2304 (18) | ||
| O2—C1—O1 | 123.9 (2) | C1—O1—Fe1 | 121.91 (15) |
| O2—C1—C2 | 117.6 (2) | C2—O3—Fe1 | 118.91 (13) |
| O1—C1—C2 | 118.5 (2) | C2—O3—H3 | 114 (2) |
| O3—C2—C3 | 110.5 (2) | Fe1—O3—H3 | 124 (2) |
| O3—C2—C1 | 108.14 (18) | C4—O4—Fe1iii | 127.20 (16) |
| C3—C2—C1 | 110.55 (19) | C4—O5—Fe1i | 146.95 (17) |
| O3—C2—H2 | 109.2 | Fe1—O1W—H11 | 119 (2) |
| C3—C2—H2 | 109.2 | Fe1—O1W—H12 | 109 (2) |
| C1—C2—H2 | 109.2 | H11—O1W—H12 | 109 (2) |
| C2—C3—C4 | 113.64 (19) | Fe1—O2W—H21 | 118 (3) |
| C2—C3—H3A | 108.8 | Fe1—O2W—H22 | 124 (3) |
| C4—C3—H3A | 108.8 | H21—O2W—H22 | 110 (2) |
| C2—C3—H3B | 108.8 | O30B—O30A—H31A | 60.9 |
| C4—C3—H3B | 108.8 | O30B—O30A—H32A | 63.1 |
| H3A—C3—H3B | 107.7 | H31A—O30A—H32A | 90.0 |
| O5—C4—O4 | 122.8 (2) | O30B—O30A—H31B | 61.1 |
| O5—C4—C3 | 118.9 (2) | H31A—O30A—H31B | 0.4 |
| O4—C4—C3 | 118.3 (2) | H32A—O30A—H31B | 90.4 |
| O5i—Fe1—O2W | 92.28 (10) | O30B—O30A—H32B | 63.3 |
| O5i—Fe1—O4ii | 82.98 (7) | H31A—O30A—H32B | 90.2 |
| O2W—Fe1—O4ii | 109.38 (8) | H32A—O30A—H32B | 0.3 |
| O5i—Fe1—O1 | 94.01 (9) | H31B—O30A—H32B | 90.6 |
| O2W—Fe1—O1 | 161.71 (7) | O30A—O30B—H31A | 60.5 |
| O4ii—Fe1—O1 | 88.44 (7) | O30A—O30B—H32A | 59.1 |
| O5i—Fe1—O3 | 99.86 (8) | H31A—O30B—H32A | 87.6 |
| O2W—Fe1—O3 | 89.97 (7) | O30A—O30B—H31B | 60.2 |
| O4ii—Fe1—O3 | 160.39 (8) | H31A—O30B—H31B | 0.5 |
| O1—Fe1—O3 | 72.04 (6) | H32A—O30B—H31B | 87.7 |
| O5i—Fe1—O1W | 170.75 (8) | O30A—O30B—H32B | 58.7 |
| O2W—Fe1—O1W | 83.78 (8) | H31A—O30B—H32B | 87.5 |
| O4ii—Fe1—O1W | 90.41 (7) | H32A—O30B—H32B | 0.5 |
| O1—Fe1—O1W | 92.26 (7) | H31B—O30B—H32B | 87.6 |
| O3—Fe1—O1W | 88.54 (7) |
| Symmetry codes: (i) −x, −y+2, −z; (ii) x, −y+3/2, z+1/2; (iii) x, −y+3/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3···O1Wiv | 0.81 (3) | 1.95 (3) | 2.749 (2) | 174 (3) |
| O1W—H11···O2v | 0.820 (10) | 1.882 (14) | 2.660 (3) | 158 (3) |
| O1W—H12···O5ii | 0.809 (10) | 2.18 (2) | 2.856 (3) | 141 (3) |
| O1W—H12···O4iv | 0.809 (10) | 2.47 (3) | 3.067 (3) | 131 (3) |
| O2W—H21···O30A | 0.811 (10) | 1.866 (14) | 2.662 (4) | 167 (4) |
| O2W—H21···O30B | 0.811 (10) | 1.785 (18) | 2.575 (13) | 164 (4) |
| O2W—H22···O2vi | 0.81 (3) | 1.915 (11) | 2.720 (3) | 172 (4) |
| O30A—H31B···O1vii | 0.84 | 2.17 | 2.984 (5) | 165 |
| O30A—H32B···O1viii | 0.83 | 2.18 | 2.887 (5) | 142 |
| Symmetry codes: (iv) −x, −y+1, −z; (v) −x+1/2, y−1/2, z; (ii) x, −y+3/2, z+1/2; (vi) x−1/2, −y+3/2, −z; (vii) x−1/2, y, −z+1/2; (viii) −x, y−1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3···O1Wi | 0.81 (3) | 1.95 (3) | 2.749 (2) | 174 (3) |
| O1W—H11···O2ii | 0.820 (10) | 1.882 (14) | 2.660 (3) | 158 (3) |
| O1W—H12···O5iii | 0.809 (10) | 2.18 (2) | 2.856 (3) | 141 (3) |
| O1W—H12···O4i | 0.809 (10) | 2.47 (3) | 3.067 (3) | 131 (3) |
| O2W—H21···O30A | 0.811 (10) | 1.866 (14) | 2.662 (4) | 167 (4) |
| O2W—H21···O30B | 0.811 (10) | 1.785 (18) | 2.575 (13) | 164 (4) |
| O2W—H22···O2iv | 0.81 (3) | 1.915 (11) | 2.720 (3) | 172 (4) |
| O30A—H31B···O1v | 0.84 | 2.17 | 2.984 (5) | 165 |
| O30A—H32B···O1vi | 0.83 | 2.18 | 2.887 (5) | 142 |
| Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1/2, y−1/2, z; (iii) x, −y+3/2, z+1/2; (iv) x−1/2, −y+3/2, −z; (v) x−1/2, y, −z+1/2; (vi) −x, y−1/2, −z+1/2. |
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Molecular self-assembly of supramolecular architectures has received much attention during recent decades (Iglesias et al., 2003; Moulton & Zaworotko, 2001; Karipides & Reed, 1976). The structures and properties of such systems depend on the coordination and geometric preferences of both the central metals ions and bridging building blocks as well as the influence of weaker non-covalent interactions, such as hydrogen bonds and π-π stacking interactions.
In the structure of (I), each FeII atom is coordinated by four O atoms from three malate ligands and two water molecules, and displayed a distorted octahedral geometry (Fig. 1). Pairs of Fe···Fe ions are bridged by the malate ligands at a distance of 6.789 (3) Å to form corrugated layers which are further assembled into a three-dimensional supramolecular network through intermolecular hydrogen bonding interactions (Table 1) with channels running along the b axis hosting the uncoordinated water molecules (Fig 2).