metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Poly[di­aqua­bis­[μ2-2,4-(di­chloro­phen­oxy)­acetato-κ2O:O′]iron(II)]

aSchool of Chemistry and the Environment, South China Normal University, Guangzhou 510006, People's Republic of China, and bKey Laboratory of Electrochemical Technology, of Energy Storage and Power Generation in Guangdong Universities, Guangzhou 510631, People's Republic of China
*Correspondence e-mail: zrh321@yahoo.com.cn

(Received 15 August 2008; accepted 12 September 2008; online 20 September 2008)

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.

Related literature

For background on supra­molecular networks, see: Eddaoudi et al. (2001[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 et al. (2005[Rizk, A. T., Kilner, C. A. & Halcrow, M. A. (2005). CrystEngComm, 7, 359-362.]).

[Scheme 1]

Experimental

Crystal data
  • [Fe(C8H5Cl2O3)2(H2O)2]

  • Mr = 531.92

  • Monoclinic, P 21 /c

  • a = 17.604 (2) Å

  • b = 7.3122 (8) Å

  • c = 8.0312 (9) Å

  • β = 94.258 (2)°

  • V = 1031.0 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 1.29 mm−1

  • T = 296 (2) K

  • 0.23 × 0.21 × 0.20 mm

Data collection
  • Bruker SMART APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.756, Tmax = 0.782

  • 5059 measured reflections

  • 1849 independent reflections

  • 1675 reflections with I > 2σ(I)

  • Rint = 0.021

Refinement
  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 0.097

  • S = 1.05

  • 1849 reflections

  • 137 parameters

  • H-atom parameters constrained

  • Δρmax = 0.48 e Å−3

  • Δρmin = −0.48 e Å−3

Table 1
Selected geometric parameters (Å, °)

Fe1—O3i 2.1654 (17)
Fe1—O2 2.1697 (16)
Fe1—O1W 2.2297 (18)
O3i—Fe1—O2 80.18 (6)
O3ii—Fe1—O2 99.82 (6)
O3i—Fe1—O1W 89.36 (7)
O3ii—Fe1—O1W 90.64 (7)
O2iii—Fe1—O1W 91.25 (7)
O2—Fe1—O1W 88.75 (7)
Symmetry codes: (i) [-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]; (iii) -x, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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: (iii) -x, -y+1, -z+1; (iv) [x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc, Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc, Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

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.

Related literature top

For background on supramolecular networks, see: Eddaoudi et al. (2001); Rizk et al. (2005).

Experimental top

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.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, together with symmetry-related atoms to complete the coordination units. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i)-x, 1-y, 1-z; (ii) x, 1/2-y, 1/2+z; (iii) -x, 1/2+y, 1/2-z.]
[Figure 2] Fig. 2. View of the two-dimensional network in the title compound.
Poly[diaquabis[µ2-(2,4-dichlorophenoxy)acetato-κ2O:O']iron(II)] top
Crystal data top
[Fe(C8H5Cl2O3)2(H2O)2]F(000) = 536
Mr = 531.92Dx = 1.714 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6377 reflections
a = 17.604 (2) Åθ = 1.7–28.0°
b = 7.3122 (8) ŵ = 1.29 mm1
c = 8.0312 (9) ÅT = 296 K
β = 94.258 (2)°Block, colourless
V = 1031.0 (2) Å30.23 × 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 tube1675 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
ϕ and ω scanθmax = 25.2°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 2117
Tmin = 0.756, Tmax = 0.782k = 88
5059 measured reflectionsl = 99
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-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 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
[Fe(C8H5Cl2O3)2(H2O)2]V = 1031.0 (2) Å3
Mr = 531.92Z = 2
Monoclinic, P21/cMo Kα radiation
a = 17.604 (2) ŵ = 1.29 mm1
b = 7.3122 (8) ÅT = 296 K
c = 8.0312 (9) Å0.23 × 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 = 0.782Rint = 0.021
5059 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 1.05Δρmax = 0.49 e Å3
1849 reflectionsΔρmin = 0.48 e Å3
137 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.00000.50000.50000.03073 (17)
Cl10.30460 (6)0.78166 (12)0.11801 (14)0.0735 (3)
Cl20.46770 (6)0.2467 (2)0.43433 (14)0.0928 (4)
C50.24797 (14)0.4477 (4)0.1746 (3)0.0356 (6)
C40.31062 (16)0.5621 (4)0.1975 (4)0.0431 (6)
C10.32151 (18)0.2103 (5)0.3170 (4)0.0530 (8)
H10.32530.09130.35750.064*
C60.25386 (16)0.2715 (4)0.2358 (4)0.0435 (6)
H60.21220.19320.22260.052*
C20.38251 (18)0.3256 (5)0.3371 (4)0.0565 (8)
C30.37794 (18)0.5028 (5)0.2792 (4)0.0553 (8)
H30.41950.58120.29480.066*
O10.18551 (10)0.5189 (2)0.0859 (2)0.0385 (4)
O20.07809 (9)0.4569 (2)0.3070 (2)0.0323 (4)
C70.07058 (13)0.3655 (3)0.1753 (3)0.0277 (5)
C80.12459 (15)0.3979 (4)0.0403 (3)0.0367 (6)
H8A0.14560.28120.00920.044*
H8B0.09580.44670.05750.044*
O30.01927 (10)0.2497 (2)0.1419 (2)0.0407 (4)
O1W0.09385 (11)0.6384 (3)0.6535 (2)0.0416 (4)
H1W0.12270.68790.59170.062*
H2W0.07080.71300.70700.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0341 (3)0.0280 (3)0.0304 (3)0.00233 (19)0.0045 (2)0.00195 (19)
Cl10.0771 (6)0.0489 (5)0.0935 (7)0.0269 (4)0.0007 (5)0.0116 (4)
Cl20.0567 (6)0.1397 (11)0.0803 (7)0.0293 (6)0.0068 (5)0.0080 (7)
C50.0338 (13)0.0400 (13)0.0344 (13)0.0029 (11)0.0113 (10)0.0048 (11)
C40.0430 (15)0.0433 (15)0.0439 (15)0.0095 (12)0.0089 (12)0.0045 (12)
C10.0574 (19)0.0538 (18)0.0493 (17)0.0108 (15)0.0136 (14)0.0055 (14)
C60.0434 (15)0.0410 (15)0.0474 (16)0.0046 (12)0.0119 (12)0.0001 (12)
C20.0435 (17)0.081 (2)0.0451 (17)0.0115 (16)0.0060 (13)0.0031 (16)
C30.0384 (16)0.073 (2)0.0546 (18)0.0126 (15)0.0041 (13)0.0088 (16)
O10.0344 (10)0.0370 (10)0.0444 (10)0.0064 (7)0.0052 (8)0.0011 (8)
O20.0327 (9)0.0342 (9)0.0305 (9)0.0017 (7)0.0056 (7)0.0074 (7)
C70.0291 (12)0.0234 (11)0.0305 (12)0.0049 (9)0.0025 (9)0.0012 (9)
C80.0369 (13)0.0429 (15)0.0306 (12)0.0072 (11)0.0052 (10)0.0047 (11)
O30.0423 (10)0.0358 (10)0.0456 (11)0.0128 (8)0.0140 (8)0.0149 (8)
O1W0.0415 (11)0.0412 (10)0.0419 (10)0.0042 (9)0.0030 (8)0.0053 (9)
Geometric parameters (Å, º) top
Fe1—O3i2.1654 (17)C1—H10.9300
Fe1—O3ii2.1654 (17)C6—H60.9300
Fe1—O2iii2.1697 (16)C2—C31.377 (5)
Fe1—O22.1697 (16)C3—H30.9300
Fe1—O1W2.2297 (18)O1—C81.417 (3)
Fe1—O1Wiii2.2297 (18)O2—C71.250 (3)
Cl1—C41.728 (3)C7—O31.253 (3)
Cl2—C21.737 (3)C7—C81.513 (3)
C5—O11.368 (3)C8—H8A0.9700
C5—C61.380 (4)C8—H8B0.9700
C5—C41.386 (4)O3—Fe1iv2.1654 (17)
C4—C31.381 (4)O1W—H1W0.8200
C1—C21.365 (5)O1W—H2W0.8200
C1—C61.389 (4)
O3i—Fe1—O3ii180.0C6—C1—H1120.1
O3i—Fe1—O2iii99.82 (6)C5—C6—C1120.5 (3)
O3ii—Fe1—O2iii80.18 (6)C5—C6—H6119.8
O3i—Fe1—O280.18 (6)C1—C6—H6119.8
O3ii—Fe1—O299.82 (6)C1—C2—C3121.0 (3)
O2iii—Fe1—O2180.0C1—C2—Cl2119.5 (3)
O3i—Fe1—O1W89.36 (7)C3—C2—Cl2119.4 (3)
O3ii—Fe1—O1W90.64 (7)C2—C3—C4118.8 (3)
O2iii—Fe1—O1W91.25 (7)C2—C3—H3120.6
O2—Fe1—O1W88.75 (7)C4—C3—H3120.6
O3i—Fe1—O1Wiii90.64 (7)C5—O1—C8117.4 (2)
O3ii—Fe1—O1Wiii89.36 (7)C7—O2—Fe1130.51 (15)
O2iii—Fe1—O1Wiii88.75 (7)O2—C7—O3124.9 (2)
O2—Fe1—O1Wiii91.25 (7)O2—C7—C8119.4 (2)
O1W—Fe1—O1Wiii180.00 (7)O3—C7—C8115.7 (2)
O1—C5—C6125.3 (2)O1—C8—C7114.6 (2)
O1—C5—C4116.1 (2)O1—C8—H8A108.6
C6—C5—C4118.6 (3)C7—C8—H8A108.6
C3—C4—C5121.3 (3)O1—C8—H8B108.6
C3—C4—Cl1119.6 (2)C7—C8—H8B108.6
C5—C4—Cl1119.0 (2)H8A—C8—H8B107.6
C2—C1—C6119.7 (3)C7—O3—Fe1iv139.91 (16)
C2—C1—H1120.1H1W—O1W—H2W112
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, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O1v0.822.413.051 (3)135
O1W—H2W···O3iii0.822.082.797 (3)145
Symmetry codes: (iii) x, y+1, z+1; (v) x, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Fe(C8H5Cl2O3)2(H2O)2]
Mr531.92
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)17.604 (2), 7.3122 (8), 8.0312 (9)
β (°) 94.258 (2)
V3)1031.0 (2)
Z2
Radiation typeMo Kα
µ (mm1)1.29
Crystal size (mm)0.23 × 0.21 × 0.20
Data collection
DiffractometerBruker SMART APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.756, 0.782
No. of measured, independent and
observed [I > 2σ(I)] reflections
5059, 1849, 1675
Rint0.021
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.097, 1.05
No. of reflections1849
No. of parameters137
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.49, 0.48

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Fe1—O3i2.1654 (17)Fe1—O1W2.2297 (18)
Fe1—O22.1697 (16)
O3i—Fe1—O280.18 (6)O3ii—Fe1—O1W90.64 (7)
O3ii—Fe1—O299.82 (6)O2iii—Fe1—O1W91.25 (7)
O3i—Fe1—O1W89.36 (7)O2—Fe1—O1W88.75 (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.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O1iv0.822.413.051 (3)135
O1W—H2W···O3iii0.822.082.797 (3)145
Symmetry codes: (iii) x, y+1, z+1; (iv) x, y+3/2, z+1/2.
 

Acknowledgements

The authors acknowledge South China Normal University for supporting this work.

References

First citationBruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc, Madison, Wisconsin, USA.  Google Scholar
First citationEddaoudi, M., Moler, D. B., Li, H., Chen, B., Reineke, T. M., O'Keeffe, M. & Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319–330.  Web of Science CrossRef PubMed CAS Google Scholar
First citationRizk, A. T., Kilner, C. A. & Halcrow, M. A. (2005). CrystEngComm, 7, 359–362.  Web of Science CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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