Poly[diaqua­bis[μ₂-2,4-(dichloro­phenoxy)­acetato-κ² O:O′]iron(II)]

Abstract

In the title compound, [Fe(C₈H₅Cl₂O₃)₂(H₂O)₂]_n, the Fe^II 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 ▶); Rizk et al. (2005 ▶).

Experimental

Crystal data

• [Fe(C₈H₅Cl₂O₃)₂(H₂O)₂]

• M _r = 531.92

• Monoclinic,

• a = 17.604 (2) Å

• b = 7.3122 (8) Å

• c = 8.0312 (9) Å

• β = 94.258 (2)°

• V = 1031.0 (2) ų

• 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 ▶) T _min = 0.756, T _max = 0.782

• 5059 measured reflections

• 1849 independent reflections

• 1675 reflections with I > 2σ(I)

• R _int = 0.021

Refinement

• R[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 0.097

• S = 1.05

• 1849 reflections

• 137 parameters

• H-atom parameters constrained

• Δρ_max = 0.48 e Å⁻³

• Δρ_min = −0.48 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) ; (iii) .

Table 2. Hydrogen-bond geometry (Å, °).

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: (iii) ; (iv) .

supplementary crystallographic information

Comment

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 Fe^II 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 Fe^II 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.

Experimental

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

H atoms of water molecule were located in difference Fourier maps and fixed with U_iso(H) = 1.5U_eq(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 U_iso(H) = 1.2U_eq(C).

Figures

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.]

Fig. 2.

View of the two-dimensional network in the title compound.

Crystal data

[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

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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 (Ų)

	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, °)

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, °)

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.