supplementary materials


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

Acta Cryst. (2009). E65, m315-m316    [ doi:10.1107/S1600536809005765 ]

Diaquabis(pyridine-2-carboxylato-[kappa]2N,O)iron(II)

G. Xia and Z. Sun

Abstract top

The FeII atom in the title complex, [Fe(C6H4NO2)2(H2O)2], exists in a distorted octahedral coordination geometry defined by two O and two N atoms from two pyridine-2-carboxylate ligands and two O atoms of two water molecules. In the crystal structure, molecules are linked into a three-dimensional framework by O-H...O hydrogen bonds.

Comment top

In the synthesis of crystal structures by design, the assembly of molecular units in predefined arrangements is a key goal (Desiraju, 1997; Braga et al., 1998). Due to carboxyl groups are one of the most important classes of biological ligands, the coordination of metal-carboxyl groups complexes are of critical importance in biological systems, organic materials and coordination chemistry. Recently, carboxyl groups with variable coordination modes have been used to construct metal-organic supramolecular structures (Mccann et al., 1996; Wai et al., 1990; Yaghi et al., 1996; Min & Lee 2002; Maira et al., 2001). We report here in the crystal structure of the title compound, (I).

In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). In the title complex, each FeII atom is axially coordinated by water molecules and consists of an equatorial plane of two oxygen donors and two nitrogen donors from two pyridine-2-carboxylato ligands with a distorted octahedral coordination geometry. The Fe—O bonds [average 2.152 (4) Å] are somewhat shorter than the Fe—N distances [average 2.270 (8) Å].

In the crystal structure, O—H···O hydrogen bonds (Fig. 2 and Table 2) seem to be effective in the stabilization of the structure, resulting in the formation of a supramolecular network structure.

Related literature top

For general backgroud, see: Desiraju (1997); Braga et al. (1998); Mccann et al. (1996); Wai et al. (1990); Yaghi et al. (1996); Min & Lee (2002); Maira et al. (2001). For bond length data, see: Allen et al. (1987).

Experimental top

Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb, which was then sealed. Iron(II) chloride tetrahydrate (198.71 mg, 1 mmol), pyridine-2-carboxylic acid (246 mg, 2 mmol) and distilled water (10 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 433 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colourless solution was decanted from small purple crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.

Refinement top

H1B and H2B (for two water molecules) were located in difference syntheses and refined isotropically [O—H = 0.805 (18) and 0.82 (5) Å, Uiso(H) = 0.093 (15) and 0.18 (3) Å2]. The remaining H atoms were positioned geometrically, with O—H = 0.82 Å (for H2O) and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,O), where x = 1.2 for aromatic H atoms and x = 1.5 for all other H atoms.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.
Diaquabis(pyridine-2-carboxylato-κ2N,O)iron(II) top
Crystal data top
[Fe(C6H4NO2)2(H2O)2]F(000) = 688
Mr = 336.09Dx = 1.475 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2834 reflections
a = 11.6255 (3) Åθ = 2.4–24.8°
b = 9.0247 (4) ŵ = 1.02 mm−1
c = 14.9724 (2) ÅT = 293 K
β = 105.568 (2)°Plane, purple
V = 1513.22 (8) Å30.23 × 0.19 × 0.07 mm
Z = 4
Data collection top
Bruker SMART APEX area-detector
diffractometer		3283 independent reflections
Radiation source: fine-focus sealed tube2158 reflections with I > 2σ(I)
graphiteRint = 0.043
φ and ω scansθmax = 27.3°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→14
Tmin = 0.796, Tmax = 0.928k = −11→11
10191 measured reflectionsl = −19→18
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)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.166 w = 1/[σ2(Fo2) + (0.089P)2 + 0.0485P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
3283 reflectionsΔρmax = 0.72 e Å−3
201 parametersΔρmin = −0.47 e Å−3
6 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0048 (16)
Crystal data top
[Fe(C6H4NO2)2(H2O)2]V = 1513.22 (8) Å3
Mr = 336.09Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.6255 (3) ŵ = 1.02 mm−1
b = 9.0247 (4) ÅT = 293 K
c = 14.9724 (2) Å0.23 × 0.19 × 0.07 mm
β = 105.568 (2)°
Data collection top
Bruker SMART APEX area-detector
diffractometer		3283 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2158 reflections with I > 2σ(I)
Tmin = 0.796, Tmax = 0.928Rint = 0.043
10191 measured reflectionsθmax = 27.3°
Refinement top
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.166Δρmax = 0.72 e Å−3
S = 1.08Δρmin = −0.47 e Å−3
3283 reflectionsAbsolute structure: ?
201 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
Special details top

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
Fe10.74557 (4)0.85895 (5)0.62770 (3)0.0492 (2)
O10.8189 (2)0.7456 (3)0.75783 (16)0.0565 (6)
H1A0.76460.70750.77520.085*
O20.5913 (2)0.8895 (3)0.6788 (2)0.0606 (7)
H2A0.59610.83510.72350.091*
O30.65069 (19)0.9271 (3)0.48892 (15)0.0527 (6)
O40.5389 (2)0.8582 (3)0.35014 (17)0.0592 (7)
O50.8181 (2)1.0762 (3)0.66750 (16)0.0540 (6)
O60.9719 (3)1.2298 (3)0.6897 (2)0.0772 (8)
N10.9337 (3)0.8594 (3)0.6119 (2)0.0534 (7)
N20.6907 (2)0.6454 (3)0.54619 (18)0.0435 (6)
C10.6030 (3)0.8306 (4)0.4297 (2)0.0454 (7)
C20.6264 (3)0.6693 (3)0.4578 (2)0.0418 (7)
C30.5833 (3)0.5536 (4)0.3976 (2)0.0561 (9)
H30.54070.57240.33670.067*
C40.6042 (3)0.4112 (4)0.4288 (3)0.0587 (9)
H40.57420.33200.38970.070*
C50.6703 (3)0.3863 (4)0.5188 (3)0.0580 (9)
H50.68640.29000.54070.070*
C60.7123 (3)0.5052 (4)0.5758 (2)0.0530 (8)
H60.75680.48800.63650.064*
C70.9225 (3)1.1079 (4)0.6662 (2)0.0538 (8)
C80.9906 (3)0.9877 (4)0.6345 (2)0.0514 (8)
C91.1059 (3)1.0068 (5)0.6312 (3)0.0731 (11)
H91.14481.09670.64810.088*
C101.1632 (4)0.8908 (6)0.6027 (4)0.0974 (17)
H101.24060.90230.59740.117*
C111.1060 (4)0.7585 (6)0.5820 (4)0.108 (2)
H111.14520.67710.56590.130*
C120.9911 (4)0.7474 (5)0.5854 (3)0.0813 (13)
H120.95100.65830.56860.098*
H1B0.8859 (15)0.715 (5)0.778 (3)0.093 (15)*
H2B0.539 (5)0.953 (5)0.673 (4)0.18 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0490 (3)0.0448 (4)0.0474 (3)−0.0005 (2)0.0020 (2)−0.00062 (19)
O10.0430 (12)0.0648 (16)0.0542 (14)0.0009 (12)0.0002 (10)0.0158 (11)
O20.0602 (15)0.0518 (15)0.0723 (18)0.0102 (12)0.0223 (13)0.0148 (12)
O30.0536 (13)0.0450 (14)0.0507 (13)−0.0018 (10)−0.0013 (10)0.0043 (10)
O40.0566 (14)0.0563 (16)0.0512 (14)0.0076 (11)−0.0091 (10)0.0080 (10)
O50.0489 (13)0.0466 (13)0.0659 (15)−0.0013 (10)0.0144 (10)−0.0088 (11)
O60.0798 (18)0.0646 (18)0.096 (2)−0.0277 (15)0.0388 (15)−0.0312 (15)
N10.0535 (16)0.0470 (18)0.0624 (18)−0.0004 (13)0.0205 (13)−0.0032 (13)
N20.0437 (13)0.0411 (15)0.0403 (14)0.0004 (11)0.0018 (10)0.0027 (10)
C10.0345 (14)0.054 (2)0.0428 (17)0.0025 (13)0.0016 (12)0.0015 (14)
C20.0361 (14)0.0442 (18)0.0418 (16)−0.0003 (12)0.0045 (11)−0.0028 (13)
C30.0540 (19)0.057 (2)0.0473 (18)0.0048 (16)−0.0028 (14)−0.0067 (16)
C40.059 (2)0.047 (2)0.065 (2)0.0017 (17)0.0074 (17)−0.0142 (17)
C50.064 (2)0.043 (2)0.070 (2)0.0023 (16)0.0226 (18)−0.0010 (16)
C60.0591 (18)0.047 (2)0.0489 (18)0.0017 (16)0.0080 (14)0.0045 (15)
C70.059 (2)0.057 (2)0.0445 (18)−0.0115 (16)0.0121 (15)−0.0065 (15)
C80.0509 (17)0.058 (2)0.0456 (17)0.0039 (16)0.0140 (13)0.0021 (15)
C90.061 (2)0.075 (3)0.088 (3)−0.008 (2)0.029 (2)−0.001 (2)
C100.070 (3)0.095 (4)0.143 (5)0.002 (3)0.055 (3)0.007 (3)
C110.090 (3)0.077 (3)0.183 (6)0.013 (3)0.081 (4)−0.007 (3)
C120.076 (3)0.056 (3)0.124 (4)0.003 (2)0.047 (3)−0.007 (2)
Geometric parameters (Å, °) top
Fe1—O12.163 (2)C1—C21.520 (4)
Fe1—O22.148 (3)C2—C31.382 (4)
Fe1—O32.164 (2)C3—C41.366 (5)
Fe1—O52.154 (2)C3—H30.9300
Fe1—N12.262 (3)C4—C51.379 (5)
Fe1—N22.279 (2)C4—H40.9300
O1—H1A0.8200C5—C61.377 (5)
O1—H1B0.805 (18)C5—H50.9300
O2—H2A0.8200C6—H60.9300
O2—H2B0.82 (5)C7—C81.494 (5)
O3—C11.260 (4)C8—C91.365 (5)
O4—C11.249 (4)C9—C101.369 (6)
O5—C71.251 (4)C9—H90.9300
O6—C71.247 (4)C10—C111.361 (7)
N1—C121.329 (5)C10—H100.9300
N1—C81.332 (4)C11—C121.353 (6)
N2—C61.342 (4)C11—H110.9300
N2—C21.351 (4)C12—H120.9300
O1—Fe1—O284.52 (10)N2—C2—C1115.8 (3)
O1—Fe1—O3167.30 (9)C3—C2—C1122.4 (3)
O1—Fe1—O598.68 (10)C4—C3—C2119.2 (3)
O2—Fe1—O392.66 (10)C4—C3—H3120.4
O2—Fe1—O595.00 (10)C2—C3—H3120.4
O3—Fe1—O593.89 (9)C3—C4—C5119.2 (3)
O1—Fe1—N186.39 (10)C3—C4—H4120.4
O2—Fe1—N1163.77 (12)C5—C4—H4120.4
O3—Fe1—N199.03 (10)C6—C5—C4119.4 (3)
O5—Fe1—N173.12 (9)C6—C5—H5120.3
O1—Fe1—N293.92 (9)C4—C5—H5120.3
O2—Fe1—N299.14 (10)N2—C6—C5121.7 (3)
O3—Fe1—N274.26 (9)N2—C6—H6119.1
O5—Fe1—N2161.88 (9)C5—C6—H6119.1
N1—Fe1—N294.86 (10)O6—C7—O5124.9 (3)
Fe1—O1—H1A109.5O6—C7—C8119.1 (3)
Fe1—O1—H1B128 (3)O5—C7—C8116.0 (3)
H1A—O1—H1B119.0N1—C8—C9121.7 (3)
Fe1—O2—H2A109.5N1—C8—C7116.3 (3)
Fe1—O2—H2B136 (3)C9—C8—C7122.0 (3)
H2A—O2—H2B112.5C8—C9—C10118.6 (4)
C1—O3—Fe1119.6 (2)C8—C9—H9120.7
C7—O5—Fe1120.9 (2)C10—C9—H9120.7
C12—N1—C8118.8 (3)C11—C10—C9119.5 (4)
C12—N1—Fe1127.4 (3)C11—C10—H10120.2
C8—N1—Fe1113.8 (2)C9—C10—H10120.2
C6—N2—C2118.7 (3)C12—C11—C10118.9 (4)
C6—N2—Fe1128.3 (2)C12—C11—H11120.5
C2—N2—Fe1113.04 (19)C10—C11—H11120.5
O4—C1—O3124.8 (3)N1—C12—C11122.3 (4)
O4—C1—C2118.1 (3)N1—C12—H12118.8
O3—C1—C2117.0 (3)C11—C12—H12118.8
N2—C2—C3121.8 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O4i0.81 (2)1.93 (2)2.726 (3)169 (4)
O1—H1A···O5ii0.821.872.661 (3)161
O2—H2B···O4iii0.82 (5)1.92 (5)2.704 (3)159 (6)
O2—H2A···O6ii0.821.942.697 (4)153
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+1, −y+2, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Fe1—O12.163 (2)Fe1—O52.154 (2)
Fe1—O22.148 (3)Fe1—N12.262 (3)
Fe1—O32.164 (2)Fe1—N22.279 (2)
O1—Fe1—O284.52 (10)O3—Fe1—N199.03 (10)
O1—Fe1—O3167.30 (9)O5—Fe1—N173.12 (9)
O1—Fe1—O598.68 (10)O1—Fe1—N293.92 (9)
O2—Fe1—O392.66 (10)O2—Fe1—N299.14 (10)
O2—Fe1—O595.00 (10)O3—Fe1—N274.26 (9)
O3—Fe1—O593.89 (9)O5—Fe1—N2161.88 (9)
O1—Fe1—N186.39 (10)N1—Fe1—N294.86 (10)
O2—Fe1—N1163.77 (12)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O4i0.81 (2)1.93 (2)2.726 (3)169 (4)
O1—H1A···O5ii0.821.872.661 (3)161
O2—H2B···O4iii0.82 (5)1.92 (5)2.704 (3)159 (6)
O2—H2A···O6ii0.821.942.697 (4)153
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+1, −y+2, −z+1.
Acknowledgements top

We thank the Youth Program of Jiangxi University of Finance and Economics for financial support of this work.

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Braga, D., Grepioni, F. & Desiraju, G. R. (1998). Chem. Rev. 98, 1375–1386.

Desiraju, G. R. (1997). J. Chem. Soc. Chem. Commun. pp. 1475–1476.

Maira, S. M., Galetic, I., Brazil, D. P., Decech, S., Ingley, E., thelen, M. & Hemmings, B. A. (2001). Science, 294(5341), 374–380.

Mccann, M., Casey, M. T., Devereux, M., Curran, M. & Cardin, C. (1996). Polyhedron, 15, 2117–2120.

Min, D. & Lee, S. M. (2002). Inorg. Chem. Commun. 5, 978–983.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

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

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Wai, H. Y., Ru, J. W. & Mark, T. C. W. (1990). J. Crystallogr. Spectrosc. Res. 20, 307–312.

Yaghi, O. M., Li, H. & Groy, T. L. (1996). J. Am. Chem. Soc. 118, 9096–9101.