supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2009). E65, m102    [ doi:10.1107/S1600536808042669 ]

Poly[([mu]6-naphthalene-1,4-dicarboxylato-[kappa]6O1:O1':O1':O4:O4':O4')iron(II)]

J. Boeckmann, I. Jess and C. Näther

Abstract top

In the title compound, [Fe(C12H6O4)]n, the FeII atom is coordinated by six O atoms from six symmetrically equivalent naphthalene-1,4-dicarboxylate ligands in a strongly distorted octahedral geometry. These octahedra are connected via common edges into chains that elongate along the a axis, with Fe...Fe distances of 2.9712 (4) and 2.9724 (4) Å. The chains are linked via the naphthalene-1,4-dicarboxylate ligands into a three-dimensional coordination network.

Comment top

The structure determination of the title compound was performed as a part of a project on the synthesis of new metal–organic frameworks. In this project we have reacted iron(II) sulfate with naphthalene-1,4-dicarboxylic acid in potassium hydroxide and water, which leads to the formation of a naphthalene-1,4-dicarboxylate iron(II) coordination polymer.

The title compound is isostructural to the manganese(II) and cobalt(II) complexes of naphthalene-1,4-dicarboxylate (Maji et al., 2005). In the title compound, the FeII atom is surrounded by six O atoms from six crystallographically equivalent naphthalene-1,4-dicarboxylate ligands in a distorted octahedral coordination environment (Fig. 1 and Table 1). The Fe atoms are linked by O atoms of the carboxylate groups in a µ3-O:O':O' mode into chains, which elongate along the a axis (Fig. 2). Within these chains the Fe coordination octahedra are connected via common edges. These chains are connected by the naphthalene-1,4-dicarboxylate ligands into a three-dimensional network.

Related literature top

For isotypical structures with MnII and CoII, see: Maji et al. (2005).

Experimental top

A mixture of FeSO4.7H2O (0.139 g, 0.5 mmol), naphthalene-1,4-dicarboxylic acid (0.108 g, 0.5 mmol), KOH (0.112 g, 1 mmol) and water (5 ml) was transfered into a glass tube and heated to 423 K for 4 d. On cooling, yellow needle crystals of the title compound were obtained.

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.95 Å and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: IPDS (Stoe & Cie, 1998); cell refinement: IPDS (Stoe & Cie, 1998); data reduction: IPDS (Stoe & Cie, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound, together with symmetry-related atoms to complete the Fe coordination. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x+1/2, -y+1/2, z-1/2; (ii) x-1, y, z; (iii) x-1/2, -y+1/2, z-1/2; (iv) -x+1/2, y+1/2, -z+3/2; (v) -x+1, -y+1, -z+1.]
[Figure 2] Fig. 2. A view of the chains formed by the Fe coordination octahedra.
[Figure 3] Fig. 3. Three-dimensional structure of the title compound viewed along the a axis.
Poly[(µ6-naphthalene-1,4-dicarboxylato- κ6O1:O1':O1':O4:O4':O4')iron(II)] top
Crystal data top
[Fe(C12H6O4)]F(000) = 544
Mr = 270.02Dx = 1.868 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 8000 reflections
a = 4.7863 (4) Åθ = 9–26°
b = 14.8940 (9) ŵ = 1.57 mm−1
c = 13.4705 (10) ÅT = 170 K
β = 91.098 (9)°Needle, yellow
V = 960.10 (12) Å30.30 × 0.04 × 0.04 mm
Z = 4
Data collection top
Stoe IPDS-1
diffractometer		1816 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.026
graphiteθmax = 28.0°, θmin = 2.7°
φ scansh = −6→6
13722 measured reflectionsk = −19→19
2256 independent reflectionsl = −17→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.087 w = 1/[σ2(Fo2) + (0.0535P)2 + 0.4222P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.002
2256 reflectionsΔρmax = 0.40 e Å−3
155 parametersΔρmin = −0.46 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.012 (3)
Crystal data top
[Fe(C12H6O4)]V = 960.10 (12) Å3
Mr = 270.02Z = 4
Monoclinic, P21/nMo Kα radiation
a = 4.7863 (4) ŵ = 1.57 mm−1
b = 14.8940 (9) ÅT = 170 K
c = 13.4705 (10) Å0.30 × 0.04 × 0.04 mm
β = 91.098 (9)°
Data collection top
Stoe IPDS-1
diffractometer		1816 reflections with I > 2σ(I)
13722 measured reflectionsRint = 0.026
2256 independent reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.087Δρmax = 0.40 e Å−3
S = 1.06Δρmin = −0.46 e Å−3
2256 reflectionsAbsolute structure: ?
155 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.24998 (4)0.440859 (14)0.501167 (14)0.00529 (13)
O10.6268 (3)0.44515 (7)0.59098 (9)0.0071 (2)
O21.0178 (2)0.36165 (8)0.59405 (9)0.0095 (2)
O3−0.0120 (2)0.13335 (8)0.90581 (9)0.0099 (2)
O40.3838 (3)0.05263 (7)0.90583 (9)0.0067 (2)
C10.6451 (3)0.31639 (10)0.69582 (11)0.0077 (3)
C20.6838 (4)0.22537 (11)0.68337 (12)0.0097 (3)
H20.80260.20440.63260.012*
C30.5492 (4)0.16326 (11)0.74501 (12)0.0097 (3)
H30.57820.10080.73530.012*
C40.3761 (3)0.19163 (10)0.81920 (11)0.0074 (3)
C50.1863 (4)0.31859 (12)0.91907 (13)0.0165 (4)
H50.08690.27760.95930.020*
C60.1788 (5)0.40864 (12)0.94029 (14)0.0233 (5)
H60.07770.42920.99590.028*
C70.3198 (5)0.47108 (12)0.88038 (13)0.0199 (4)
H70.31550.53320.89630.024*
C80.4628 (4)0.44215 (10)0.79915 (13)0.0135 (4)
H80.55190.48480.75790.016*
C90.4798 (3)0.34898 (10)0.77570 (11)0.0081 (3)
C100.3413 (3)0.28589 (11)0.83760 (11)0.0084 (3)
C110.7751 (3)0.37880 (10)0.62232 (11)0.0067 (3)
C120.2371 (3)0.12168 (10)0.88160 (11)0.0067 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.00470 (18)0.00449 (16)0.00679 (17)0.00009 (8)0.00311 (10)0.00003 (7)
O10.0072 (6)0.0065 (5)0.0076 (5)0.0000 (4)0.0012 (4)0.0020 (4)
O20.0071 (6)0.0088 (5)0.0129 (5)0.0000 (4)0.0048 (4)0.0036 (4)
O30.0063 (6)0.0095 (5)0.0139 (5)−0.0002 (4)0.0036 (4)0.0044 (4)
O40.0071 (6)0.0056 (5)0.0074 (5)−0.0002 (4)0.0009 (4)0.0023 (4)
C10.0069 (7)0.0085 (7)0.0078 (7)−0.0012 (6)0.0011 (6)0.0027 (5)
C20.0103 (8)0.0096 (7)0.0094 (7)0.0010 (6)0.0048 (6)0.0017 (5)
C30.0116 (8)0.0071 (7)0.0104 (7)0.0008 (5)0.0032 (6)0.0020 (6)
C40.0068 (8)0.0071 (7)0.0082 (6)−0.0004 (5)0.0009 (5)0.0029 (5)
C50.0230 (10)0.0120 (8)0.0150 (8)0.0004 (7)0.0117 (7)0.0020 (6)
C60.0367 (12)0.0128 (9)0.0210 (9)0.0038 (8)0.0183 (8)−0.0011 (7)
C70.0338 (11)0.0089 (8)0.0173 (8)0.0011 (7)0.0100 (8)−0.0005 (6)
C80.0207 (10)0.0077 (8)0.0122 (7)−0.0020 (6)0.0050 (7)0.0011 (6)
C90.0084 (8)0.0075 (7)0.0083 (7)−0.0003 (5)0.0017 (6)0.0017 (5)
C100.0091 (8)0.0081 (7)0.0080 (7)0.0004 (5)0.0025 (6)0.0016 (5)
C110.0074 (8)0.0066 (7)0.0061 (6)−0.0018 (5)0.0012 (5)0.0000 (5)
C120.0076 (8)0.0070 (7)0.0056 (6)−0.0011 (5)0.0015 (5)0.0004 (5)
Geometric parameters (Å, °) top
Fe1—O3i2.0557 (11)C2—H20.9500
Fe1—O2ii2.0604 (11)C3—C41.377 (2)
Fe1—O12.1533 (13)C3—H30.9500
Fe1—O4iii2.1550 (13)C4—C101.436 (2)
Fe1—O4iv2.1867 (11)C4—C121.502 (2)
Fe1—O1v2.1908 (11)C5—C61.372 (3)
Fe1—Fe1vi2.9712 (4)C5—C101.422 (2)
Fe1—Fe1v2.9724 (4)C5—H50.9500
O1—C111.2835 (19)C6—C71.411 (3)
O2—C111.256 (2)C6—H60.9500
O3—C121.254 (2)C7—C81.371 (2)
O4—C121.2839 (19)C7—H70.9500
C1—C21.379 (2)C8—C91.426 (2)
C1—C91.433 (2)C8—H80.9500
C1—C111.502 (2)C9—C101.428 (2)
C2—C31.407 (2)
O3i—Fe1—O2ii112.54 (5)C2—C1—C9120.12 (14)
O3i—Fe1—O184.19 (5)C2—C1—C11118.04 (13)
O2ii—Fe1—O197.55 (5)C9—C1—C11121.82 (14)
O3i—Fe1—O4iii96.08 (5)C1—C2—C3120.69 (15)
O2ii—Fe1—O4iii86.89 (5)C1—C2—H2119.7
O1—Fe1—O4iii175.08 (4)C3—C2—H2119.7
O3i—Fe1—O4iv159.92 (5)C4—C3—C2121.01 (15)
O2ii—Fe1—O4iv85.45 (4)C4—C3—H3119.5
O1—Fe1—O4iv84.65 (4)C2—C3—H3119.5
O4iii—Fe1—O4iv93.64 (4)C3—C4—C10119.93 (14)
O3i—Fe1—O1v84.50 (4)C3—C4—C12118.20 (14)
O2ii—Fe1—O1v160.39 (5)C10—C4—C12121.83 (13)
O1—Fe1—O1v93.65 (4)C6—C5—C10120.77 (16)
O4iii—Fe1—O1v81.50 (4)C6—C5—H5119.6
O4iv—Fe1—O1v79.61 (5)C10—C5—H5119.6
O3i—Fe1—Fe1vi140.19 (4)C5—C6—C7120.69 (16)
O2ii—Fe1—Fe1vi84.39 (3)C5—C6—H6119.7
O1—Fe1—Fe1vi130.85 (3)C7—C6—H6119.7
O4iii—Fe1—Fe1vi47.26 (3)C8—C7—C6120.04 (16)
O4iv—Fe1—Fe1vi46.37 (3)C8—C7—H7120.0
O1v—Fe1—Fe1vi76.12 (3)C6—C7—H7120.0
O3i—Fe1—Fe1v81.72 (3)C7—C8—C9120.93 (15)
O2ii—Fe1—Fe1v142.14 (4)C7—C8—H8119.5
O1—Fe1—Fe1v47.35 (3)C9—C8—H8119.5
O4iii—Fe1—Fe1v127.79 (3)C8—C9—C10118.82 (14)
O4iv—Fe1—Fe1v78.44 (3)C8—C9—C1122.06 (14)
O1v—Fe1—Fe1v46.30 (3)C10—C9—C1119.01 (14)
Fe1vi—Fe1—Fe1v107.275 (14)C5—C10—C9118.68 (14)
C11—O1—Fe1127.88 (10)C5—C10—C4122.14 (14)
C11—O1—Fe1v129.03 (11)C9—C10—C4119.07 (13)
Fe1—O1—Fe1v86.35 (4)O2—C11—O1124.47 (14)
C11—O2—Fe1vii125.49 (10)O2—C11—C1118.13 (14)
C12—O3—Fe1viii128.98 (10)O1—C11—C1117.38 (14)
C12—O4—Fe1ix123.36 (10)O3—C12—O4124.25 (14)
C12—O4—Fe1x126.21 (10)O3—C12—C4118.88 (14)
Fe1ix—O4—Fe1x86.36 (4)O4—C12—C4116.87 (14)
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x−1, y, z; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1/2, y+1/2, −z+3/2; (v) −x+1, −y+1, −z+1; (vi) −x, −y+1, −z+1; (vii) x+1, y, z; (viii) x−1/2, −y+1/2, z+1/2; (ix) x+1/2, −y+1/2, z+1/2; (x) −x+1/2, y−1/2, −z+3/2.
Table 1
Selected geometric parameters (Å) top
Fe1—O3i2.0557 (11)Fe1—O4iv2.1867 (11)
Fe1—O2ii2.0604 (11)Fe1—O1v2.1908 (11)
Fe1—O12.1533 (13)Fe1—Fe1vi2.9712 (4)
Fe1—O4iii2.1550 (13)Fe1—Fe1v2.9724 (4)
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x−1, y, z; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1/2, y+1/2, −z+3/2; (v) −x+1, −y+1, −z+1; (vi) −x, −y+1, −z+1.
Acknowledgements top

This work was supported by the State of Schleswig-Holstein. We thank Professor Dr Wolfgang Bensch for the facility to use his equipment.

references
References top

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Maji, T. K., Kaneko, W., Ohba, M. & Kitagawa, S. (2005). Chem. Commun. pp. 4613–4615.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Stoe & Cie (1998). IPDS. Stoe & Cie, Darmstadt, Germany.