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Acta Cryst. (2008). E64, m1343    [ doi:10.1107/S1600536808030663 ]

Aqua(picolinato N-oxide-[kappa]2O1,O2)(pyridine-2,6-dicarboxylato-[kappa]3O,N,O')iron(III) monohydrate

D. Han and D. Wang

Abstract top

In the title compound, [Fe(C6H4NO3)(C7H3NO4)(H2O)]·H2O, the FeIII ion is coordinated by two O and one N atoms from a pyridine-2,6-dicarboxylate ligand, by two O atoms from a picolinate N-oxide ligand and by one water O atom in a distorted octahedral geometry [Fe-O = 1.940 (3)-2.033 (3) Å and Fe-N = 2.057 (4) Å]. In the crystal structure, the coordinated and solvent water molecules contribute to the formation of O-H...O hydrogen bonds, which link the molecules into layers parallel to the ab plane.

Comment top

Recently, the 2D zinc(II) and 1D copper(II) complexes with pyridine-2,6-dicarboxylic acid N-oxide and dicarboxylato ligands were reported by Wu et al. (2007). As a contribution to this area, we report the crystal structure of the title compound, (I).

In (I) (Fig. 1), the FeIII ion is coordinated by two O and one N atoms from pyridine-2,6-dicarboxylato ligand, two O atoms from picolinato-N-oxide ligand, and one water molecule in a distorted octahedral geometry. Atoms O1, O4, O7 and N1 lie in equatorial plane, with the O1—N1—O4—O7 torsion angle of 1.94 (15)°, while Fe1 deviates from the equatorial plane at 0.057 Å. Atoms O5 and O8 occupy the axial sites with the angle O5—Fe1—O8 of 167.93 (14)°. The bond lengths and angles in (I) are similar to those in the related FeIII complex (Lainé et al.,1995).

In the crystal, the coordinated and crystalline water molecules contribute to the formation of O—H···O hydrogen bonds (Table 1, Fig. 2), which link the molecules into the layers parallel to ab plane.

Related literature top

For related crystal structures, see: Lainé et al. (1995); Wu et al. (2007).

Experimental top

A mixture of Fe2(SO4)3(0.5 mmol), pyco (0.5 mmol), pydc (0.50 mmol), and H2O (3.00 ml), was placed in a Parr Teflon-lined stainless steel vessel (10 ml), and then the vessel was sealed and heated at 393 K for 3 d. After the mixture was slowly cooled to room temperature, several red crystals of (I) were obtained.

Refinement top

C-bound H atoms were introduced at calculated positions (C—H 0.93 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C). H atoms of water molecules were located in a difference Fourier map and refined with O—H and H···H distance restraints of 0.85 (3) and 1.39 (3) Å, respectively, and Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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. The molecular structure of (I) showing the atomic numbering and 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. A portion of the crystal packing showing H-bonds as dashed lines.
Aqua(picolinato N-oxide-κ2O1,O2)(pyridine-2,6- dicarboxylato-κ3O,N,O')iron(III) monohydrate top
Crystal data top
[Fe(C6H4NO3)(C7H3NO4)(H2O)]·H2OZ = 2
Mr = 395.09F(000) = 402
Triclinic, P1Dx = 1.791 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.6023 (13) ÅCell parameters from 544 reflections
b = 7.7256 (16) Åθ = 2.7–20.0°
c = 15.520 (3) ŵ = 1.09 mm−1
α = 102.585 (4)°T = 293 K
β = 95.801 (4)°Block, red
γ = 105.743 (4)°0.16 × 0.14 × 0.12 mm
V = 732.7 (3) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		2749 independent reflections
Radiation source: fine-focus sealed tube1667 reflections with I > 2σ(I)
graphiteRint = 0.047
φ and ω scansθmax = 25.8°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		h = −8→7
Tmin = 0.84, Tmax = 0.87k = −9→9
3915 measured reflectionsl = −18→17
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)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096H atoms treated by a mixture of independent and constrained refinement
S = 0.85 w = 1/[σ2(Fo2) + (0.0145P)2]
where P = (Fo2 + 2Fc2)/3
2749 reflections(Δ/σ)max = 0.001
238 parametersΔρmax = 0.49 e Å−3
4 restraintsΔρmin = −0.36 e Å−3
Crystal data top
[Fe(C6H4NO3)(C7H3NO4)(H2O)]·H2Oγ = 105.743 (4)°
Mr = 395.09V = 732.7 (3) Å3
Triclinic, P1Z = 2
a = 6.6023 (13) ÅMo Kα radiation
b = 7.7256 (16) ŵ = 1.09 mm−1
c = 15.520 (3) ÅT = 293 K
α = 102.585 (4)°0.16 × 0.14 × 0.12 mm
β = 95.801 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2749 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		1667 reflections with I > 2σ(I)
Tmin = 0.84, Tmax = 0.87Rint = 0.047
3915 measured reflectionsθmax = 25.8°
Refinement top
R[F2 > 2σ(F2)] = 0.060H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096Δρmax = 0.49 e Å−3
S = 0.85Δρmin = −0.36 e Å−3
2749 reflectionsAbsolute structure: ?
238 parametersFlack parameter: ?
4 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
Fe10.47020 (11)0.38418 (9)0.22899 (5)0.0363 (2)
N10.4982 (6)0.5619 (5)0.3522 (2)0.0317 (10)
N20.3098 (6)0.1709 (5)0.0392 (3)0.0358 (10)
O10.1839 (4)0.2941 (4)0.2682 (2)0.0404 (9)
O40.7711 (5)0.5595 (4)0.2520 (2)0.0439 (9)
O50.3665 (5)0.5275 (4)0.1559 (2)0.0497 (10)
O80.5897 (5)0.2107 (4)0.2796 (2)0.0450 (10)
H8A0.722 (5)0.241 (7)0.300 (3)0.067*
H8B0.553 (8)0.098 (4)0.276 (4)0.067*
C10.1473 (7)0.3772 (6)0.3417 (3)0.0344 (12)
C20.3323 (7)0.5401 (6)0.3952 (3)0.0293 (11)
C30.3435 (7)0.6559 (6)0.4769 (3)0.0408 (13)
H30.22690.64220.50660.049*
C40.5325 (8)0.7933 (6)0.5138 (3)0.0467 (14)
H40.54540.87340.56960.056*
C50.7012 (7)0.8134 (6)0.4693 (3)0.0448 (14)
H50.82940.90620.49450.054*
C60.6799 (7)0.6952 (6)0.3869 (3)0.0390 (13)
C70.8408 (8)0.6911 (7)0.3244 (4)0.0444 (14)
C80.3104 (8)0.5009 (7)0.0716 (4)0.0415 (13)
C90.2594 (7)0.3099 (6)0.0109 (3)0.0322 (12)
C100.1569 (7)0.2692 (7)−0.0765 (3)0.0444 (14)
H100.12150.3625−0.09790.053*
C110.1064 (8)0.0935 (7)−0.1323 (4)0.0501 (15)
H110.03910.0679−0.19130.060*
C120.1560 (8)−0.0406 (7)−0.1002 (4)0.0462 (14)
H120.1214−0.1602−0.13730.055*
C130.2553 (7)−0.0048 (6)−0.0149 (3)0.0377 (13)
H130.2863−0.09960.00680.045*
O2−0.0192 (5)0.3380 (4)0.3721 (2)0.0479 (10)
O31.0189 (5)0.8053 (5)0.3461 (2)0.0594 (11)
O60.2880 (6)0.6231 (5)0.0361 (3)0.0600 (11)
O70.4227 (5)0.1917 (4)0.1189 (2)0.0463 (9)
O90.3706 (6)0.8722 (5)0.2653 (3)0.0608 (12)
H9A0.249 (6)0.839 (7)0.283 (4)0.091*
H9B0.366 (9)0.771 (5)0.228 (3)0.091*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0375 (4)0.0354 (4)0.0324 (4)0.0069 (3)0.0085 (3)0.0053 (3)
N10.027 (2)0.031 (2)0.036 (3)0.0067 (18)0.0058 (19)0.0084 (19)
N20.031 (2)0.046 (3)0.028 (3)0.007 (2)0.0038 (19)0.011 (2)
O10.0294 (19)0.040 (2)0.035 (2)−0.0034 (15)0.0042 (16)−0.0056 (16)
O40.033 (2)0.049 (2)0.046 (2)0.0054 (16)0.0136 (17)0.0112 (18)
O50.069 (3)0.042 (2)0.039 (2)0.0211 (18)0.004 (2)0.0075 (18)
O80.042 (2)0.035 (2)0.051 (3)0.0033 (19)−0.0009 (19)0.0104 (19)
C10.029 (3)0.040 (3)0.033 (3)0.009 (2)−0.001 (2)0.012 (2)
C20.022 (3)0.032 (3)0.032 (3)0.008 (2)0.000 (2)0.008 (2)
C30.037 (3)0.047 (3)0.035 (3)0.010 (2)0.009 (2)0.004 (3)
C40.057 (4)0.041 (3)0.032 (3)0.006 (3)0.003 (3)0.000 (3)
C50.038 (3)0.037 (3)0.043 (4)−0.008 (2)−0.001 (3)0.005 (3)
C60.036 (3)0.031 (3)0.045 (4)0.002 (2)0.005 (3)0.010 (3)
C70.040 (3)0.049 (3)0.043 (4)0.007 (3)0.004 (3)0.019 (3)
C80.033 (3)0.044 (3)0.049 (4)0.010 (3)0.011 (3)0.015 (3)
C90.031 (3)0.032 (3)0.033 (3)0.005 (2)0.011 (2)0.010 (2)
C100.035 (3)0.054 (4)0.048 (4)0.011 (3)0.008 (3)0.023 (3)
C110.050 (4)0.053 (4)0.040 (4)0.010 (3)0.002 (3)0.009 (3)
C120.036 (3)0.049 (3)0.042 (4)0.007 (3)0.006 (3)−0.004 (3)
C130.032 (3)0.033 (3)0.045 (4)0.007 (2)0.013 (3)0.005 (3)
O20.027 (2)0.061 (2)0.044 (2)0.0007 (16)0.0073 (17)0.0029 (18)
O30.034 (2)0.063 (2)0.065 (3)−0.0095 (18)0.0098 (19)0.013 (2)
O60.071 (3)0.051 (2)0.065 (3)0.021 (2)0.007 (2)0.028 (2)
O70.054 (2)0.055 (2)0.026 (2)0.0208 (18)−0.0004 (18)0.0015 (17)
O90.060 (3)0.034 (2)0.079 (3)0.005 (2)0.027 (2)0.000 (2)
Geometric parameters (Å, °) top
Fe1—O71.939 (3)C3—H30.9300
Fe1—O51.945 (4)C4—C51.360 (6)
Fe1—O81.986 (4)C4—H40.9300
Fe1—O42.023 (3)C5—C61.369 (6)
Fe1—O12.032 (3)C5—H50.9300
Fe1—N12.055 (4)C6—C71.511 (6)
N1—C61.321 (5)C7—O31.226 (5)
N1—C21.331 (5)C8—O61.226 (6)
N2—O71.332 (5)C8—C91.496 (6)
N2—C91.352 (5)C9—C101.382 (6)
N2—C131.362 (5)C10—C111.374 (6)
O1—C11.262 (5)C10—H100.9300
O4—C71.285 (5)C11—C121.344 (7)
O5—C81.279 (6)C11—H110.9300
O8—H8A0.85 (3)C12—C131.351 (7)
O8—H8B0.83 (3)C12—H120.9300
C1—O21.228 (5)C13—H130.9300
C1—C21.507 (6)O9—H9A0.87 (3)
C2—C31.365 (6)O9—H9B0.86 (3)
C3—C41.372 (6)
O7—Fe1—O586.72 (14)C2—C3—H3121.1
O7—Fe1—O882.18 (14)C4—C3—H3121.1
O5—Fe1—O8167.93 (15)C5—C4—C3120.6 (4)
O7—Fe1—O4110.22 (14)C5—C4—H4119.7
O5—Fe1—O491.59 (14)C3—C4—H4119.7
O8—Fe1—O487.85 (14)C4—C5—C6119.1 (4)
O7—Fe1—O198.80 (13)C4—C5—H5120.4
O5—Fe1—O193.23 (14)C6—C5—H5120.4
O8—Fe1—O193.13 (14)N1—C6—C5120.0 (4)
O4—Fe1—O1150.80 (13)N1—C6—C7111.0 (4)
O7—Fe1—N1172.69 (15)C5—C6—C7129.1 (4)
O5—Fe1—N197.84 (14)O3—C7—O4126.8 (5)
O8—Fe1—N193.69 (15)O3—C7—C6119.7 (5)
O4—Fe1—N175.50 (13)O4—C7—C6113.5 (4)
O1—Fe1—N175.31 (13)O6—C8—O5123.9 (5)
C6—N1—C2121.5 (4)O6—C8—C9116.3 (5)
C6—N1—Fe1119.4 (3)O5—C8—C9119.8 (5)
C2—N1—Fe1119.1 (3)N2—C9—C10117.5 (4)
O7—N2—C9124.5 (4)N2—C9—C8121.7 (5)
O7—N2—C13113.8 (4)C10—C9—C8120.8 (5)
C9—N2—C13121.6 (4)C11—C10—C9121.3 (5)
C1—O1—Fe1120.7 (3)C11—C10—H10119.4
C7—O4—Fe1120.6 (3)C9—C10—H10119.4
C8—O5—Fe1133.6 (3)C12—C11—C10118.8 (5)
Fe1—O8—H8A121 (3)C12—C11—H11120.6
Fe1—O8—H8B136 (4)C10—C11—H11120.6
H8A—O8—H8B101 (5)C11—C12—C13121.2 (5)
O2—C1—O1126.8 (4)C11—C12—H12119.4
O2—C1—C2118.9 (4)C13—C12—H12119.4
O1—C1—C2114.3 (4)C12—C13—N2119.5 (5)
N1—C2—C3121.0 (4)C12—C13—H13120.2
N1—C2—C1110.7 (4)N2—C13—H13120.2
C3—C2—C1128.3 (4)N2—O7—Fe1129.5 (3)
C2—C3—C4117.8 (4)H9A—O9—H9B101 (5)
O7—Fe1—N1—C6142.0 (11)C3—C4—C5—C60.3 (8)
O5—Fe1—N1—C6−89.7 (4)C2—N1—C6—C50.7 (8)
O8—Fe1—N1—C686.7 (4)Fe1—N1—C6—C5−179.4 (4)
O4—Fe1—N1—C6−0.1 (4)C2—N1—C6—C7−179.3 (4)
O1—Fe1—N1—C6179.0 (4)Fe1—N1—C6—C70.6 (5)
O7—Fe1—N1—C2−38.1 (14)C4—C5—C6—N1−1.0 (8)
O5—Fe1—N1—C290.2 (4)C4—C5—C6—C7179.0 (5)
O8—Fe1—N1—C2−93.4 (4)Fe1—O4—C7—O3179.8 (4)
O4—Fe1—N1—C2179.8 (4)Fe1—O4—C7—C61.0 (6)
O1—Fe1—N1—C2−1.1 (3)N1—C6—C7—O3−179.9 (5)
O7—Fe1—O1—C1176.8 (4)C5—C6—C7—O30.1 (9)
O5—Fe1—O1—C1−96.0 (4)N1—C6—C7—O4−1.0 (6)
O8—Fe1—O1—C194.3 (4)C5—C6—C7—O4179.0 (5)
O4—Fe1—O1—C13.1 (5)Fe1—O5—C8—O6−165.3 (3)
N1—Fe1—O1—C11.3 (4)Fe1—O5—C8—C917.2 (7)
O7—Fe1—O4—C7−175.7 (4)O7—N2—C9—C10174.6 (4)
O5—Fe1—O4—C797.2 (4)C13—N2—C9—C10−2.3 (6)
O8—Fe1—O4—C7−94.9 (4)O7—N2—C9—C8−5.9 (7)
O1—Fe1—O4—C7−2.3 (5)C13—N2—C9—C8177.2 (4)
N1—Fe1—O4—C7−0.5 (4)O6—C8—C9—N2169.3 (4)
O7—Fe1—O5—C8−4.4 (5)O5—C8—C9—N2−13.0 (7)
O8—Fe1—O5—C818.6 (10)O6—C8—C9—C10−11.3 (7)
O4—Fe1—O5—C8105.7 (5)O5—C8—C9—C10166.5 (5)
O1—Fe1—O5—C8−103.1 (5)N2—C9—C10—C110.6 (7)
N1—Fe1—O5—C8−178.7 (5)C8—C9—C10—C11−178.9 (4)
Fe1—O1—C1—O2179.0 (4)C9—C10—C11—C120.8 (8)
Fe1—O1—C1—C2−1.2 (5)C10—C11—C12—C13−0.5 (8)
C6—N1—C2—C30.4 (7)C11—C12—C13—N2−1.2 (8)
Fe1—N1—C2—C3−179.5 (3)O7—N2—C13—C12−174.5 (4)
C6—N1—C2—C1−179.2 (4)C9—N2—C13—C122.7 (7)
Fe1—N1—C2—C10.8 (5)C9—N2—O7—Fe122.0 (6)
O2—C1—C2—N1−180.0 (4)C13—N2—O7—Fe1−160.9 (3)
O1—C1—C2—N10.2 (6)O5—Fe1—O7—N2−15.4 (4)
O2—C1—C2—C30.4 (8)O8—Fe1—O7—N2169.3 (4)
O1—C1—C2—C3−179.4 (5)O4—Fe1—O7—N2−105.9 (4)
N1—C2—C3—C4−1.1 (7)O1—Fe1—O7—N277.3 (4)
C1—C2—C3—C4178.5 (5)N1—Fe1—O7—N2113.4 (12)
C2—C3—C4—C50.7 (8)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O8—H8A···O2i0.85 (4)1.81 (4)2.637 (5)164 (4)
O8—H8B···O9ii0.83 (3)1.79 (4)2.571 (5)157 (5)
O9—H9A···O3iii0.87 (5)1.88 (5)2.730 (5)167 (5)
O9—H9B···O50.86 (5)1.97 (6)2.821 (5)173 (4)
Symmetry codes: (i) x+1, y, z; (ii) x, y−1, z; (iii) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O8—H8A···O2i0.85 (4)1.81 (4)2.637 (5)164 (4)
O8—H8B···O9ii0.83 (3)1.79 (4)2.571 (5)157 (5)
O9—H9A···O3iii0.87 (5)1.88 (5)2.730 (5)167 (5)
O9—H9B···O50.86 (5)1.97 (6)2.821 (5)173 (4)
Symmetry codes: (i) x+1, y, z; (ii) x, y−1, z; (iii) x−1, y, z.
references
References top

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Lainé, P., Gourdon, A. & Launay, J. P. (1995). Inorg. Chem. 34, 5129–5137.

Sheldrick, G. M. (2000). SADABS. University of Göttingen, Germany.

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

Wu, W. P., Wang, Y. Y., Wu, Y. P., Liu, J. Q., Zeng, X. R., Shi, Q. Z. & Peng, S. M. (2007). CrystEngComm, 9, 753–757.