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The crystal structure of the title compound, [FeCl2(C4H8O2)(H2O)2]n, contains six-coordinate FeII atoms in approximately octahedral environments. The FeII atoms have \overline 1 symmetry, i.e. all pairs of identical ligands are trans. The structure consists of polymeric chains made up of dioxane mol­ecules, in the chair conformation with \overline 1 symmetry, linking the FeII centers. The chains are crosslinked by O—H...Cl hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102010508/fr1377sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102010508/fr1377Isup2.hkl
Contains datablock I

CCDC reference: 193402

Comment top

For many years, crystal engineering has utilized the hydrogen bond for the formation of extended networks, thus creating structures with a variety of pore shapes and sizes able to accommodate various guest molecules. Many of the networks that have been reported are neutral. An obvious alternative to neutral frameworks are ionic ones, in particular, cationic frameworks. These could then play host to a variety of negatively charged species of various sizes. It has been suggested that a metal-cation–dioxane network could achieve this (Hasch et al., 2000). A number of structures have been reported involving alkali-metal–dioxane networks (Taube et al., 1993; Eaborn et al., 1997; Kühl et al., 1999, 2000; Hasche et al., 2000). These structures indicate the variety of structures obtainable as a result of variations in the coordination at the metal center; thus, one-dimensional chains, two-dimensional sheets, and three-dimensional networks have all been observed. The only other known extended dioxane–metal structures are chains with hard metal centers, for example, AlIII (Boardman et al., 1983), GaIII (Boardman et al., 1984), MgII (Parvez et al., 1988), CdII (Almond et al., 1991), TlIII (Jeffs et al., 1983), NdIII (Taube et al., 1996), and FeII (Müller et al., 1997). Recently, another type of chain structure has been reported where 1,4-dioxane links 1,2-diiodotetrafluoroethane molecules by coordination to the two I atoms (Chu et al., 2001).

While attempting to extend our work on lithium-containing cationic networks to include iron(II)-containing anions by the reaction of LiCl and FeCl2 in dioxane, only the lithium-free title compound, (I), a one-dimensional polymeric structure, was obtained. This compound contains a pseudo-octahedral six-coordinate FeII cation with 1 symmetry, coordinated by two trans Cl- ions and two trans water molecules. The final two coordination sites are occupied by 1,4-dioxane rings bound through O atoms, as shown in Fig. 1. The O atoms of the dioxane ring, which adopts a chair conformation, bind to two FeII atoms on either side, with a bond distance of 2.1830 (17) Å. This coordination results in the formation of chains parallel to a and these chains build the backbone of the crystal structure, similar to the case in catena-[[bis(2,2,6,6-tetramethylheptane-3,5-dionato)iron(II)]-µ-1,4-dioxane] (Müller et al., 1997). In the present case, the iron–dioxane chains are crosslinked by Owater···Cl hydrogen bonding (Fig. 2). The hydrogen bonding involves the H atoms located on the coordinated water molecules and the coordinated Cl- ions on the FeII atoms of two adjacent chains. Each water molecule hydrogen bonds to two Cl- ions from two adjacent FeII centers, and each chloride ion accepts two hydrogen bonds from two adjacent FeII centers, i.e. an approximately square arrangement with the two Cl and two O atoms at opposite corners, each side representing a hydrogen bond, and each corner bound to a different FeII atom; an approximately planar FeOClH layer is thus formed perpendicular to the Fe—Odioxane vector within the polymer chain.

Experimental top

Anhydrous iron(II) chloride (0.50 g) and lithium chloride (0.50 g) were placed in a 100 ml beaker. 1,4-Dioxane (50 ml) was added and the solution was heated and stirred for 2 h. After filtering off unreacted starting material, the resulting solution was separated in 5 ml vials for evaporation and crystallization.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. One polymeric chain in (I) parallel to a.
[Figure 2] Fig. 2. The hydrogen-bonded layer perpendicular to the Fe—Odioxane vector in the polymer chains of (I).
catena-diaqua-dichloro-(µ-1,4-dioxane-O,O')-iron(II) top
Crystal data top
[FeCl2(C4H8O2)(H2O)2]F(000) = 256
Mr = 250.89Dx = 1.811 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.8590 (18) ÅCell parameters from 1309 reflections
b = 9.273 (2) Åθ = 3.3–29.2°
c = 7.925 (2) ŵ = 2.19 mm1
β = 114.082 (5)°T = 100 K
V = 460.2 (2) Å3Irregular, red–brown
Z = 20.20 × 0.20 × 0.15 mm
Data collection top
Bruker SMART CCD
diffractometer
1058 independent reflections
Radiation source: fine-focus sealed tube965 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
ω scansθmax = 29.2°, θmin = 3.3°
Absorption correction: empirical (using intensity measurements)
multipole expansion (Blessing, 1995; Sheldrick, 1996)
h = 97
Tmin = 0.364, Tmax = 0.659k = 512
1799 measured reflectionsl = 109
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094All H-atom parameters refined
S = 1.05 w = 1/[σ2(Fo2) + (0.0666P)2 + 0.1903P]
where P = (Fo2 + 2Fc2)/3
1058 reflections(Δ/σ)max < 0.001
76 parametersΔρmax = 0.92 e Å3
0 restraintsΔρmin = 0.67 e Å3
Crystal data top
[FeCl2(C4H8O2)(H2O)2]V = 460.2 (2) Å3
Mr = 250.89Z = 2
Monoclinic, P21/nMo Kα radiation
a = 6.8590 (18) ŵ = 2.19 mm1
b = 9.273 (2) ÅT = 100 K
c = 7.925 (2) Å0.20 × 0.20 × 0.15 mm
β = 114.082 (5)°
Data collection top
Bruker SMART CCD
diffractometer
1058 independent reflections
Absorption correction: empirical (using intensity measurements)
multipole expansion (Blessing, 1995; Sheldrick, 1996)
965 reflections with I > 2σ(I)
Tmin = 0.364, Tmax = 0.659Rint = 0.021
1799 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.094All H-atom parameters refined
S = 1.05Δρmax = 0.92 e Å3
1058 reflectionsΔρmin = 0.67 e Å3
76 parameters
Special details top

Experimental. The decay correction was applied simultaneously with the absorption correction in SADABS. No formal measure of the extent of decay is printed out by this program. The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 15 σ(I).

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
Fe10.00000.50000.00000.01226 (17)
Cl10.03854 (8)0.23836 (5)0.02603 (7)0.01541 (18)
O20.1774 (3)0.48894 (17)0.2862 (3)0.0173 (4)
H1A0.240 (6)0.561 (4)0.343 (5)0.031 (9)*
H1B0.268 (7)0.425 (4)0.327 (5)0.033 (9)*
O10.2847 (3)0.54151 (18)0.0509 (2)0.0168 (4)
C10.3476 (4)0.4532 (2)0.1708 (3)0.0172 (4)
H2A0.225 (5)0.388 (3)0.237 (4)0.016 (7)*
H2B0.379 (6)0.518 (3)0.254 (5)0.026 (9)*
C20.4591 (4)0.6350 (2)0.0583 (4)0.0178 (5)
H3A0.492 (5)0.697 (4)0.028 (4)0.022 (8)*
H3B0.406 (5)0.690 (3)0.140 (4)0.022 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0110 (3)0.0113 (3)0.0139 (3)0.00039 (15)0.00445 (19)0.00011 (14)
Cl10.0147 (3)0.0115 (3)0.0183 (3)0.00052 (17)0.0050 (2)0.00036 (17)
O20.0167 (9)0.0136 (7)0.0181 (9)0.0005 (6)0.0034 (7)0.0013 (6)
O10.0125 (8)0.0181 (7)0.0211 (8)0.0019 (6)0.0082 (6)0.0052 (6)
C10.0164 (11)0.0201 (10)0.0167 (10)0.0007 (9)0.0084 (9)0.0028 (9)
C20.0149 (11)0.0166 (11)0.0230 (11)0.0030 (8)0.0090 (9)0.0026 (8)
Geometric parameters (Å, º) top
Fe1—O12.1830 (17)O1—C21.444 (3)
Fe1—O1i2.1830 (17)O1—C11.448 (3)
Fe1—O2i2.0934 (19)C1—C2ii1.502 (3)
Fe1—O22.0934 (19)C1—H2A0.99 (3)
Fe1—Cl1i2.4583 (8)C1—H2B0.98 (3)
Fe1—Cl12.4583 (8)C2—C1ii1.502 (3)
O2—H1A0.82 (4)C2—H3A0.99 (3)
O2—H1B0.83 (4)C2—H3B1.00 (3)
O1—Fe1—O1i180.0H1A—O2—H1B103 (4)
O1—Fe1—Cl1i88.65 (5)C2—O1—C1109.67 (18)
O1i—Fe1—Cl1i91.35 (5)C2—O1—Fe1125.44 (13)
O1—Fe1—Cl191.35 (5)C1—O1—Fe1123.40 (14)
O1i—Fe1—Cl188.65 (5)O1—C1—C2ii110.2 (2)
O2i—Fe1—O2180.0O1—C1—H2A105.9 (17)
O2i—Fe1—O187.69 (7)C2ii—C1—H2A109.5 (16)
O2—Fe1—O192.31 (7)O1—C1—H2B107.4 (19)
O2i—Fe1—O1i92.31 (7)C2ii—C1—H2B110 (2)
O2—Fe1—O1i87.69 (7)H2A—C1—H2B113 (3)
O2i—Fe1—Cl1i90.44 (4)O1—C2—C1ii110.13 (18)
O2—Fe1—Cl1i89.56 (4)O1—C2—H3A107.6 (18)
O2i—Fe1—Cl189.56 (4)C1ii—C2—H3A109.5 (18)
O2—Fe1—Cl190.44 (4)O1—C2—H3B105.1 (19)
Cl1i—Fe1—Cl1180.0C1ii—C2—H3B111.1 (18)
Fe1—O2—H1A120 (3)H3A—C2—H3B113 (3)
Fe1—O2—H1B118 (3)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1A···Cl1iii0.82 (4)2.31 (4)3.1202 (19)171 (4)
O2—H1B···Cl1iv0.83 (4)2.31 (4)3.1280 (19)173 (3)
Symmetry codes: (iii) x+1/2, y+1/2, z+1/2; (iv) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[FeCl2(C4H8O2)(H2O)2]
Mr250.89
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)6.8590 (18), 9.273 (2), 7.925 (2)
β (°) 114.082 (5)
V3)460.2 (2)
Z2
Radiation typeMo Kα
µ (mm1)2.19
Crystal size (mm)0.20 × 0.20 × 0.15
Data collection
DiffractometerBruker SMART CCD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
multipole expansion (Blessing, 1995; Sheldrick, 1996)
Tmin, Tmax0.364, 0.659
No. of measured, independent and
observed [I > 2σ(I)] reflections
1799, 1058, 965
Rint0.021
(sin θ/λ)max1)0.686
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.094, 1.05
No. of reflections1058
No. of parameters76
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.92, 0.67

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
Fe1—O12.1830 (17)Fe1—Cl12.4583 (8)
Fe1—O22.0934 (19)
O1—Fe1—O1i180.0O2—Fe1—O192.31 (7)
O1—Fe1—Cl1i88.65 (5)O2—Fe1—Cl1i89.56 (4)
O1—Fe1—Cl191.35 (5)O2—Fe1—Cl190.44 (4)
O2i—Fe1—O2180.0Cl1i—Fe1—Cl1180.0
O2i—Fe1—O187.69 (7)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1A···Cl1ii0.82 (4)2.31 (4)3.1202 (19)171 (4)
O2—H1B···Cl1iii0.83 (4)2.31 (4)3.1280 (19)173 (3)
Symmetry codes: (ii) x+1/2, y+1/2, z+1/2; (iii) x+1/2, y+1/2, z+1/2.
 

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