supplementary materials
Poly[diaquabis[![[mu]](/logos/entities/mu_rmgif.gif)
2-2,4-(dichlorophenoxy)acetato-![[kappa]](/logos/entities/kappa_rmgif.gif)
2O:O']iron(II)]
In the title compound, [Fe(C8H5Cl2O3)2(H2O)2]n, the FeII atom is located on an inversion center. It is coordinated by four O atoms from four 2,4-dichlorophenoxyacetate ligands and two water molecules, displaying a distorted octahedral geometry. The carboxylate groups of the 2,4-dichlorophenoxyacetate ligands link the Fe atoms, forming a polymeric layered network in the bc plane. Intralayer O-H
O hydrogen bonds enhance the stability of the two-dimensional network.
A mixture of FeCl2 (0.127 g, 1 mmol), 2,4-dichlorophenoxyacetic acid
(0.221 g, 1 mmol), NaOH (0.04 g, 1 mmol) and water (10 ml) was stirred
vigorously for 20 min, and then sealed in a 20 ml Teflon-lined stainless steel
autoclave. The autoclave was heated to and maintained at 433 K for 2 d, and
then cooled to room temperature at 5 K h-1 to afford red block crystals.
H atoms of water molecule were located in difference Fourier maps and fixed
with Uiso(H) = 1.5Ueq(O). C-bound H atoms were positioned
geometrically and refined as riding atoms, with C—H = 0.97 (CH2) and 0.93
(CH) Å and with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
Poly[diaquabis[µ
2-(2,4-dichlorophenoxy)acetato-
κ2O:O']iron(II)]
top
Crystal data top
| [Fe(C8H5Cl2O3)2(H2O)2] | F(000) = 536 |
| Mr = 531.92 | Dx = 1.714 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 6377 reflections |
| a = 17.604 (2) Å | θ = 1.7–28.0° |
| b = 7.3122 (8) Å | µ = 1.29 mm−1 |
| c = 8.0312 (9) Å | T = 296 K |
| β = 94.258 (2)° | Block, colourless |
| V = 1031.0 (2) Å3 | 0.23 × 0.21 × 0.20 mm |
| Z = 2 | |
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer | 1849 independent reflections |
| Radiation source: fine-focus sealed tube | 1675 reflections with I > 2σ(I) |
| graphite | Rint = 0.021 |
| φ and ω scan | θmax = 25.2°, θmin = 2.3° |
Absorption correction: multi-scan
(SADABS; Bruker, 2001) | h = −21→17 |
| Tmin = 0.756, Tmax = 0.782 | k = −8→8 |
| 5059 measured reflections | l = −9→9 |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.097 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0473P)2 + 1.0193P]
where P = (Fo2 + 2Fc2)/3 |
| 1849 reflections | (Δ/σ)max < 0.001 |
| 137 parameters | Δρmax = 0.49 e Å−3 |
| 0 restraints | Δρmin = −0.48 e Å−3 |
Crystal data top
| [Fe(C8H5Cl2O3)2(H2O)2] | V = 1031.0 (2) Å3 |
| Mr = 531.92 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 17.604 (2) Å | µ = 1.29 mm−1 |
| b = 7.3122 (8) Å | T = 296 K |
| c = 8.0312 (9) Å | 0.23 × 0.21 × 0.20 mm |
| β = 94.258 (2)° | |
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer | 1849 independent reflections |
Absorption correction: multi-scan
(SADABS; Bruker, 2001) | 1675 reflections with I > 2σ(I) |
| Tmin = 0.756, Tmax = 0.782 | Rint = 0.021 |
| 5059 measured reflections | θmax = 25.2° |
Refinement top
| R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
| wR(F2) = 0.097 | Δρmax = 0.49 e Å−3 |
| S = 1.05 | Δρmin = −0.48 e Å−3 |
| 1849 reflections | Absolute structure: ? |
| 137 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| Fe1 | 0.0000 | 0.5000 | 0.5000 | 0.03073 (17) | |
| Cl1 | 0.30460 (6) | 0.78166 (12) | 0.11801 (14) | 0.0735 (3) | |
| Cl2 | 0.46770 (6) | 0.2467 (2) | 0.43433 (14) | 0.0928 (4) | |
| C5 | 0.24797 (14) | 0.4477 (4) | 0.1746 (3) | 0.0356 (6) | |
| C4 | 0.31062 (16) | 0.5621 (4) | 0.1975 (4) | 0.0431 (6) | |
| C1 | 0.32151 (18) | 0.2103 (5) | 0.3170 (4) | 0.0530 (8) | |
| H1 | 0.3253 | 0.0913 | 0.3575 | 0.064* | |
| C6 | 0.25386 (16) | 0.2715 (4) | 0.2358 (4) | 0.0435 (6) | |
| H6 | 0.2122 | 0.1932 | 0.2226 | 0.052* | |
| C2 | 0.38251 (18) | 0.3256 (5) | 0.3371 (4) | 0.0565 (8) | |
| C3 | 0.37794 (18) | 0.5028 (5) | 0.2792 (4) | 0.0553 (8) | |
| H3 | 0.4195 | 0.5812 | 0.2948 | 0.066* | |
| O1 | 0.18551 (10) | 0.5189 (2) | 0.0859 (2) | 0.0385 (4) | |
| O2 | 0.07809 (9) | 0.4569 (2) | 0.3070 (2) | 0.0323 (4) | |
| C7 | 0.07058 (13) | 0.3655 (3) | 0.1753 (3) | 0.0277 (5) | |
| C8 | 0.12459 (15) | 0.3979 (4) | 0.0403 (3) | 0.0367 (6) | |
| H8A | 0.1456 | 0.2812 | 0.0092 | 0.044* | |
| H8B | 0.0958 | 0.4467 | −0.0575 | 0.044* | |
| O3 | 0.01927 (10) | 0.2497 (2) | 0.1419 (2) | 0.0407 (4) | |
| O1W | 0.09385 (11) | 0.6384 (3) | 0.6535 (2) | 0.0416 (4) | |
| H1W | 0.1227 | 0.6879 | 0.5917 | 0.062* | |
| H2W | 0.0708 | 0.7130 | 0.7070 | 0.062* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Fe1 | 0.0341 (3) | 0.0280 (3) | 0.0304 (3) | 0.00233 (19) | 0.0045 (2) | 0.00195 (19) |
| Cl1 | 0.0771 (6) | 0.0489 (5) | 0.0935 (7) | −0.0269 (4) | −0.0007 (5) | 0.0116 (4) |
| Cl2 | 0.0567 (6) | 0.1397 (11) | 0.0803 (7) | 0.0293 (6) | −0.0068 (5) | 0.0080 (7) |
| C5 | 0.0338 (13) | 0.0400 (13) | 0.0344 (13) | −0.0029 (11) | 0.0113 (10) | −0.0048 (11) |
| C4 | 0.0430 (15) | 0.0433 (15) | 0.0439 (15) | −0.0095 (12) | 0.0089 (12) | −0.0045 (12) |
| C1 | 0.0574 (19) | 0.0538 (18) | 0.0493 (17) | 0.0108 (15) | 0.0136 (14) | 0.0055 (14) |
| C6 | 0.0434 (15) | 0.0410 (15) | 0.0474 (16) | −0.0046 (12) | 0.0119 (12) | 0.0001 (12) |
| C2 | 0.0435 (17) | 0.081 (2) | 0.0451 (17) | 0.0115 (16) | 0.0060 (13) | −0.0031 (16) |
| C3 | 0.0384 (16) | 0.073 (2) | 0.0546 (18) | −0.0126 (15) | 0.0041 (13) | −0.0088 (16) |
| O1 | 0.0344 (10) | 0.0370 (10) | 0.0444 (10) | −0.0064 (7) | 0.0052 (8) | 0.0011 (8) |
| O2 | 0.0327 (9) | 0.0342 (9) | 0.0305 (9) | −0.0017 (7) | 0.0056 (7) | −0.0074 (7) |
| C7 | 0.0291 (12) | 0.0234 (11) | 0.0305 (12) | 0.0049 (9) | 0.0025 (9) | 0.0012 (9) |
| C8 | 0.0369 (13) | 0.0429 (15) | 0.0306 (12) | −0.0072 (11) | 0.0052 (10) | −0.0047 (11) |
| O3 | 0.0423 (10) | 0.0358 (10) | 0.0456 (11) | −0.0128 (8) | 0.0140 (8) | −0.0149 (8) |
| O1W | 0.0415 (11) | 0.0412 (10) | 0.0419 (10) | −0.0042 (9) | 0.0030 (8) | −0.0053 (9) |
Geometric parameters (Å, °) top
| Fe1—O3i | 2.1654 (17) | C1—H1 | 0.9300 |
| Fe1—O3ii | 2.1654 (17) | C6—H6 | 0.9300 |
| Fe1—O2iii | 2.1697 (16) | C2—C3 | 1.377 (5) |
| Fe1—O2 | 2.1697 (16) | C3—H3 | 0.9300 |
| Fe1—O1W | 2.2297 (18) | O1—C8 | 1.417 (3) |
| Fe1—O1Wiii | 2.2297 (18) | O2—C7 | 1.250 (3) |
| Cl1—C4 | 1.728 (3) | C7—O3 | 1.253 (3) |
| Cl2—C2 | 1.737 (3) | C7—C8 | 1.513 (3) |
| C5—O1 | 1.368 (3) | C8—H8A | 0.9700 |
| C5—C6 | 1.380 (4) | C8—H8B | 0.9700 |
| C5—C4 | 1.386 (4) | O3—Fe1iv | 2.1654 (17) |
| C4—C3 | 1.381 (4) | O1W—H1W | 0.8200 |
| C1—C2 | 1.365 (5) | O1W—H2W | 0.8200 |
| C1—C6 | 1.389 (4) | | |
| | | |
| O3i—Fe1—O3ii | 180.0 | C6—C1—H1 | 120.1 |
| O3i—Fe1—O2iii | 99.82 (6) | C5—C6—C1 | 120.5 (3) |
| O3ii—Fe1—O2iii | 80.18 (6) | C5—C6—H6 | 119.8 |
| O3i—Fe1—O2 | 80.18 (6) | C1—C6—H6 | 119.8 |
| O3ii—Fe1—O2 | 99.82 (6) | C1—C2—C3 | 121.0 (3) |
| O2iii—Fe1—O2 | 180.0 | C1—C2—Cl2 | 119.5 (3) |
| O3i—Fe1—O1W | 89.36 (7) | C3—C2—Cl2 | 119.4 (3) |
| O3ii—Fe1—O1W | 90.64 (7) | C2—C3—C4 | 118.8 (3) |
| O2iii—Fe1—O1W | 91.25 (7) | C2—C3—H3 | 120.6 |
| O2—Fe1—O1W | 88.75 (7) | C4—C3—H3 | 120.6 |
| O3i—Fe1—O1Wiii | 90.64 (7) | C5—O1—C8 | 117.4 (2) |
| O3ii—Fe1—O1Wiii | 89.36 (7) | C7—O2—Fe1 | 130.51 (15) |
| O2iii—Fe1—O1Wiii | 88.75 (7) | O2—C7—O3 | 124.9 (2) |
| O2—Fe1—O1Wiii | 91.25 (7) | O2—C7—C8 | 119.4 (2) |
| O1W—Fe1—O1Wiii | 180.00 (7) | O3—C7—C8 | 115.7 (2) |
| O1—C5—C6 | 125.3 (2) | O1—C8—C7 | 114.6 (2) |
| O1—C5—C4 | 116.1 (2) | O1—C8—H8A | 108.6 |
| C6—C5—C4 | 118.6 (3) | C7—C8—H8A | 108.6 |
| C3—C4—C5 | 121.3 (3) | O1—C8—H8B | 108.6 |
| C3—C4—Cl1 | 119.6 (2) | C7—C8—H8B | 108.6 |
| C5—C4—Cl1 | 119.0 (2) | H8A—C8—H8B | 107.6 |
| C2—C1—C6 | 119.7 (3) | C7—O3—Fe1iv | 139.91 (16) |
| C2—C1—H1 | 120.1 | H1W—O1W—H2W | 112 |
| Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y+1, −z+1; (iv) −x, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1W···O1v | 0.82 | 2.41 | 3.051 (3) | 135 |
| O1W—H2W···O3iii | 0.82 | 2.08 | 2.797 (3) | 145 |
| Symmetry codes: (v) x, −y+3/2, z+1/2; (iii) −x, −y+1, −z+1. |
Table 1
Selected geometric parameters (Å, °) top| Fe1—O3i | 2.1654 (17) | Fe1—O1W | 2.2297 (18) |
| Fe1—O2 | 2.1697 (16) | | |
| | | |
| O3i—Fe1—O2 | 80.18 (6) | O3ii—Fe1—O1W | 90.64 (7) |
| O3ii—Fe1—O2 | 99.82 (6) | O2iii—Fe1—O1W | 91.25 (7) |
| O3i—Fe1—O1W | 89.36 (7) | O2—Fe1—O1W | 88.75 (7) |
| Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y+1, −z+1. |
Table 2
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1W···O1iv | 0.82 | 2.41 | 3.051 (3) | 135 |
| O1W—H2W···O3iii | 0.82 | 2.08 | 2.797 (3) | 145 |
| Symmetry codes: (iv) x, −y+3/2, z+1/2; (iii) −x, −y+1, −z+1. |
The authors acknowledge South China Normal University for supporting this work.
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc, Madison, Wisconsin, USA.
Eddaoudi, M., Moler, D. B., Li, H., Chen, B., Reineke, T. M., O'Keeffe, M. & Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319–330.
Rizk, A. T., Kilner, C. A. & Halcrow, M. A. (2005). CrystEngComm, 7, 359–362.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./hy2149fig1thm.gif)
![[Figure 2]](./hy2149fig2thm.gif)
The design, synthesis, characterization and properties of supramolecular networks formed by using functionalized organic molecules as bridges between metal centers are of great interest (Eddaoudi et al., 2001; Rizk et al., 2005). As a building block, 2,4-dichlorophenoxyacetate is an excellent candidate for the construction of supramolecular complexes. Recently, we obtained the title compound, a new coordination polymer.
In the title compound, the FeII atom is located on an inversion center and coordinated by four O atoms from four 2,4-dichlorophenoxyacetate ligands and two water molecules in an octahedral geometry (Fig. 1; Table 1). The FeII atoms are linked by 2,4-dichlorophenoxyacetate ligands to form a polymeric layered network in the bc-plane (Fig. 2). The two-dimensional network is further stabilized by intralayer O—H···O hydrogen bonds involving the coordinated water molecules and the O atoms from the ligands (Table 2). The adjacent Fe···Fe separation is 5.431 (4) Å.