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Acta Cryst. (2007). E63, m1926    [ doi:10.1107/S160053680702867X ]

Poly[[[aqua(2,2-bipyridine)iron(II)]-[mu]3-pyridine-3,4-dicarboxylato] monohydrate]

L.-J. Hao and T.-L. Yu

Abstract top

In the title complex, {[Fe(C7H3NO4)(C10H8N2)(H2O)]·H2O}n, the divalent iron cation is in the centre of a distorted octahedron formed by three N and three O atoms. Two N atoms belong to the chelating 2,2-bipyridine ligand and the third to the pyridine-3,4-dicarboxylate ligand, while the O atoms belong to monodentate carboxylate groups of two different pyridine-3,4-dicarboxylate ligands and to one water molecule. The connectivity between the FeII cations and the pyridine-3,4-dicarboxylate units gives rise to corrugated layers parallel to the ab plane. The water molecules of crystallization are located between the layers. Medium-strong O-H...O hydrogen bonds between the water molecules and the layers stabilize the structure.

Comment top

The molecular structure of the title compound is shown in Fig. 1. The FeII cation is in a distorted octahedral coordination by three O and three N atoms. The 2,2-bipyridine ligand provides two N atoms and the third N atom comes from the pyridine ring of the pyridine-3,4-dicarboxylate ligand. Two O atoms belong to the carboxylate groups of two different pyridine-3,4-dicarboxylate ligands and the third O atom is an aqua ligand. The Fe—O and Fe—N bond distances range from 2.1192 (19) to 2.194 (2) and from 2.224 (2) to 2.361 (2) Å, respectively. The connectivity between the FeII cations to three different pyridine-3,4-dicarboxylate ligands leads to the formation of corrugated layers parallel to the ab plane, as shown in Fig. 2. An additional sheet of water molecules is located between the polymeric layers. The structure is stabilized by medium-strong hydrogen bonds of the type O—H···O between the water molecules and the layers (Table 2).

Experimental top

All chemicals were purchased from Acros without further purification. A mixture of FeCl2 (98%, 0.5 mmol, 0.149 g), pyridine-3,4,-dicarboxylic acid (98%, 0.5 mmol, 0.162 g), and 2,2-bipyridine (98%, 0.5 mmol, 0.10 g) in a 20 ml mixture of water and ethanol (1:1) was sealed in an 30 ml Teflon-lined stainless autoclave, and kept at 423 K for 2 d. Colourless, block-shaped crystals of the title compound were obtained with an approximate yield of 20% after slowly cooling to room temperature. Anal. Calc. for C17H15FeN3O6: C 49.39, H 3.63, N 10.17, Fe 13.56%; Found: C 49.36, H 3.67, N 10.15, Fe 13.52%.

Refinement top

The H atoms of the water molecules (except for HW2) were located from difference Fourier maps and were refined with distance restraints of d(H–H) = 1.38 (2) Å and d(O–H) = 0.83 (2) Å. All other H atoms were placed in calculated positions with a C–H bond distance of 0.93 Å (O–HW2 distance of 0.82 Å) and Uiso(H) = 1.2Ueq of the respective carrier atom.

Computing details top

Data collection: SMART (Bruker, 1998); 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: XP in SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the coordination of the FeII cation in the structure of compound (I). Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: I) -x + 1,-y,-z + 2.]
[Figure 2] Fig. 2. two-dimensional wave-like layer of (I).
Poly[[[aqua(2,2-bipyridine)iron(II)]-µ3-pyridine-3,4-dicarboxylato] monohydrate] top
Crystal data top
[Fe(C7H3NO4)(C10H8N2)(H2O)]·H2OF(000) = 1696
Mr = 413.17Dx = 1.673 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2870 reflections
a = 15.7231 (13) Åθ = 2.4–25.0°
b = 12.630 (2) ŵ = 0.96 mm−1
c = 16.522 (2) ÅT = 293 K
V = 3281.1 (7) Å3Cube, colourless
Z = 80.10 × 0.10 × 0.10 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2870 independent reflections
Radiation source: fine-focus sealed tube2330 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.071
φ and ω scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)		h = −18→18
Tmin = 0.910, Tmax = 0.910k = −15→15
24153 measured reflectionsl = −19→19
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.073P)2 + 0.2586P]
where P = (Fo2 + 2Fc2)/3
2870 reflections(Δ/σ)max = 0.001
257 parametersΔρmax = 0.46 e Å−3
6 restraintsΔρmin = −0.68 e Å−3
Crystal data top
[Fe(C7H3NO4)(C10H8N2)(H2O)]·H2OV = 3281.1 (7) Å3
Mr = 413.17Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 15.7231 (13) ŵ = 0.96 mm−1
b = 12.630 (2) ÅT = 293 K
c = 16.522 (2) Å0.10 × 0.10 × 0.10 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2870 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)		2330 reflections with I > 2σ(I)
Tmin = 0.910, Tmax = 0.910Rint = 0.071
24153 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109Δρmax = 0.46 e Å−3
S = 1.00Δρmin = −0.68 e Å−3
2870 reflectionsAbsolute structure: ?
257 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
Fe10.43846 (2)0.18949 (3)0.93122 (2)0.02606 (16)
C10.33340 (16)−0.0122 (2)0.94563 (16)0.0223 (6)
C20.29361 (15)−0.10090 (19)0.99332 (15)0.0202 (5)
C30.31859 (16)−0.1280 (2)1.07044 (15)0.0227 (6)
C40.38443 (16)−0.0688 (2)1.11962 (15)0.0246 (6)
C50.27582 (17)−0.2132 (2)1.10595 (17)0.0299 (6)
H50.2920−0.23571.15730.036*
C60.20945 (18)−0.2652 (2)1.06631 (17)0.0306 (7)
H60.1829−0.32171.09220.037*
C70.22564 (16)−0.1578 (2)0.95950 (16)0.0237 (6)
H70.2085−0.13810.90780.028*
C80.47919 (18)0.4002 (2)0.82369 (17)0.0318 (6)
H80.43570.37500.79070.038*
C90.52747 (19)0.4850 (2)0.79578 (18)0.0346 (7)
H90.51580.51590.74590.042*
C100.5923 (2)0.5219 (3)0.84312 (19)0.0435 (8)
H100.62610.57800.82600.052*
C110.6062 (2)0.4748 (3)0.91530 (19)0.0414 (8)
H110.65060.49790.94810.050*
C120.55395 (16)0.3913 (2)0.94102 (16)0.0244 (6)
C130.56429 (15)0.3397 (2)1.01905 (16)0.0234 (6)
C140.61829 (18)0.3804 (2)1.07782 (17)0.0325 (7)
H140.65000.44121.06800.039*
C150.6237 (2)0.3293 (3)1.14976 (19)0.0402 (8)
H150.65880.35531.19050.048*
C160.5766 (2)0.2386 (3)1.16216 (18)0.0404 (8)
H160.58050.20281.21120.049*
C170.52435 (18)0.2010 (2)1.10260 (18)0.0316 (7)
H170.49290.13981.11170.038*
N10.18306 (13)−0.23758 (17)0.99403 (13)0.0272 (5)
N20.51787 (13)0.24994 (17)1.03256 (13)0.0240 (5)
N30.49137 (13)0.35332 (17)0.89404 (13)0.0246 (5)
O10.45895 (11)−0.10617 (16)1.12228 (12)0.0349 (5)
O20.35844 (13)0.00840 (16)1.15898 (12)0.0387 (5)
O30.38972 (11)0.04329 (13)0.97871 (11)0.0269 (4)
O40.30668 (14)0.00132 (15)0.87610 (11)0.0356 (5)
O50.26467 (14)0.13856 (16)0.26104 (13)0.0363 (5)
O60.36334 (13)0.18725 (15)0.81936 (12)0.0311 (5)
H2W0.33540.13250.81730.047*
H4W0.2378 (19)0.104 (2)0.2948 (16)0.055 (11)*
H3W0.2908 (19)0.097 (2)0.2303 (16)0.048 (10)*
H1W0.3316 (19)0.2383 (15)0.808 (2)0.053 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0263 (3)0.0223 (3)0.0296 (3)−0.00241 (15)−0.00159 (16)0.00010 (15)
C10.0208 (13)0.0166 (13)0.0296 (15)0.0019 (10)0.0021 (11)−0.0009 (11)
C20.0206 (12)0.0165 (13)0.0236 (13)0.0008 (10)0.0036 (10)−0.0017 (10)
C30.0200 (13)0.0213 (14)0.0268 (14)0.0055 (10)0.0052 (11)−0.0015 (10)
C40.0291 (15)0.0265 (14)0.0183 (14)0.0011 (12)0.0033 (11)0.0035 (11)
C50.0327 (15)0.0307 (15)0.0263 (15)0.0007 (12)−0.0020 (12)0.0066 (12)
C60.0307 (15)0.0261 (15)0.0349 (17)−0.0076 (12)0.0011 (12)0.0069 (12)
C70.0276 (14)0.0230 (13)0.0205 (13)−0.0002 (11)0.0004 (11)0.0006 (11)
C80.0327 (15)0.0342 (16)0.0284 (15)−0.0051 (12)−0.0047 (12)0.0009 (12)
C90.0442 (17)0.0329 (16)0.0269 (16)−0.0037 (13)0.0011 (13)0.0070 (12)
C100.0533 (19)0.0393 (19)0.0379 (19)−0.0221 (15)0.0009 (16)0.0075 (14)
C110.0441 (18)0.0443 (19)0.0359 (18)−0.0251 (15)−0.0066 (14)0.0037 (14)
C120.0241 (13)0.0203 (14)0.0288 (15)−0.0020 (11)0.0012 (11)−0.0037 (11)
C130.0208 (13)0.0241 (14)0.0251 (14)0.0009 (11)0.0012 (11)−0.0027 (11)
C140.0327 (16)0.0292 (15)0.0356 (17)−0.0083 (12)−0.0054 (13)−0.0012 (12)
C150.0382 (17)0.048 (2)0.0342 (17)−0.0031 (15)−0.0108 (14)−0.0014 (14)
C160.0422 (18)0.050 (2)0.0290 (16)0.0025 (15)−0.0029 (14)0.0112 (14)
C170.0298 (15)0.0318 (16)0.0333 (16)−0.0024 (12)0.0021 (13)0.0077 (12)
N10.0258 (12)0.0261 (13)0.0298 (13)−0.0037 (10)−0.0015 (10)0.0004 (10)
N20.0230 (11)0.0234 (12)0.0255 (12)−0.0004 (9)0.0011 (9)−0.0001 (9)
N30.0241 (12)0.0252 (12)0.0246 (12)−0.0033 (9)−0.0002 (9)0.0025 (10)
O10.0242 (10)0.0425 (12)0.0380 (12)0.0104 (9)−0.0030 (9)−0.0105 (9)
O20.0437 (12)0.0366 (12)0.0359 (12)0.0109 (10)−0.0016 (10)−0.0147 (9)
O30.0289 (10)0.0221 (10)0.0298 (10)−0.0060 (8)−0.0018 (8)0.0018 (8)
O40.0497 (12)0.0317 (11)0.0255 (11)−0.0131 (9)−0.0087 (9)0.0063 (8)
O50.0472 (13)0.0332 (12)0.0285 (11)0.0011 (10)0.0065 (10)0.0000 (10)
O60.0346 (11)0.0268 (11)0.0317 (11)−0.0041 (9)−0.0044 (9)−0.0007 (8)
Geometric parameters (Å, º) top
Fe1—O1i2.1192 (19)C9—C101.367 (4)
Fe1—O32.1478 (18)C9—H90.9300
Fe1—O62.194 (2)C10—C111.350 (4)
Fe1—N22.224 (2)C10—H100.9300
Fe1—N32.313 (2)C11—C121.404 (4)
Fe1—N1ii2.361 (2)C11—H110.9300
C1—O41.235 (3)C12—N31.342 (3)
C1—O31.255 (3)C12—C131.454 (4)
C1—C21.505 (4)C13—N21.367 (3)
C2—C31.377 (4)C13—C141.388 (4)
C2—C71.404 (4)C14—C151.355 (4)
C3—C51.397 (4)C14—H140.9300
C3—C41.514 (4)C15—C161.380 (5)
C4—O21.241 (3)C15—H150.9300
C4—O11.264 (3)C16—C171.367 (4)
C5—C61.397 (4)C16—H160.9300
C5—H50.9300C17—N21.316 (4)
C6—N11.312 (3)C17—H170.9300
C6—H60.9300N1—Fe1iii2.361 (2)
C7—N11.337 (3)O1—Fe1i2.1192 (18)
C7—H70.9300O5—H4W0.824 (17)
C8—N31.318 (4)O5—H3W0.838 (17)
C8—C91.391 (4)O6—H2W0.8200
C8—H80.9300O6—H1W0.837 (17)
O1i—Fe1—O389.83 (8)C8—C9—H9120.7
O1i—Fe1—O692.98 (8)C11—C10—C9118.4 (3)
O3—Fe1—O696.01 (7)C11—C10—H10120.8
O1i—Fe1—N293.28 (8)C9—C10—H10120.8
O3—Fe1—N2102.73 (8)C10—C11—C12120.2 (3)
O6—Fe1—N2160.24 (8)C10—C11—H11119.9
O1i—Fe1—N393.42 (8)C12—C11—H11119.9
O3—Fe1—N3173.94 (8)N3—C12—C11121.5 (3)
O6—Fe1—N388.94 (7)N3—C12—C13115.8 (2)
N2—Fe1—N372.00 (8)C11—C12—C13122.7 (2)
O1i—Fe1—N1ii173.18 (8)N2—C13—C14121.3 (2)
O3—Fe1—N1ii83.46 (7)N2—C13—C12117.2 (2)
O6—Fe1—N1ii86.54 (8)C14—C13—C12121.5 (3)
N2—Fe1—N1ii89.40 (8)C15—C14—C13118.4 (3)
N3—Fe1—N1ii93.37 (8)C15—C14—H14120.8
O4—C1—O3124.6 (2)C13—C14—H14120.8
O4—C1—C2116.7 (2)C14—C15—C16119.5 (3)
O3—C1—C2118.8 (2)C14—C15—H15120.3
C3—C2—C7117.3 (2)C16—C15—H15120.3
C3—C2—C1123.4 (2)C17—C16—C15120.3 (3)
C7—C2—C1119.3 (2)C17—C16—H16119.9
C2—C3—C5116.3 (2)C15—C16—H16119.9
C2—C3—C4124.7 (2)N2—C17—C16121.1 (3)
C5—C3—C4118.9 (2)N2—C17—H17119.5
O2—C4—O1125.5 (3)C16—C17—H17119.5
O2—C4—C3116.4 (2)C6—N1—C7115.5 (2)
O1—C4—C3117.9 (2)C6—N1—Fe1iii123.53 (18)
C6—C5—C3121.7 (3)C7—N1—Fe1iii120.76 (17)
C6—C5—H5119.2C17—N2—C13119.5 (2)
C3—C5—H5119.2C17—N2—Fe1122.96 (19)
N1—C6—C5122.5 (3)C13—N2—Fe1117.49 (17)
N1—C6—H6118.7C8—N3—C12117.1 (2)
C5—C6—H6118.7C8—N3—Fe1125.69 (18)
N1—C7—C2126.7 (2)C12—N3—Fe1115.46 (17)
N1—C7—H7116.7C4—O1—Fe1i151.22 (18)
C2—C7—H7116.7C1—O3—Fe1124.97 (17)
N3—C8—C9124.0 (3)H4W—O5—H3W109 (2)
N3—C8—H8118.0Fe1—O6—H2W109.5
C9—C8—H8118.0Fe1—O6—H1W120 (2)
C10—C9—C8118.7 (3)H2W—O6—H1W108.7
C10—C9—H9120.7
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1/2, y+1/2, z; (iii) −x+1/2, y−1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H4W···O4iv0.82 (2)2.02 (2)2.827 (3)168 (3)
O5—H3W···O2v0.84 (2)1.94 (2)2.779 (3)176 (3)
O6—H1W···O5vi0.84 (2)2.03 (2)2.859 (3)170 (4)
Symmetry codes: (iv) −x+1/2, −y, z−1/2; (v) x, y, z−1; (vi) x, −y+1/2, z+1/2.
Selected bond lengths (Å) top
Fe1—O1i2.1192 (19)Fe1—N22.224 (2)
Fe1—O32.1478 (18)Fe1—N32.313 (2)
Fe1—O62.194 (2)Fe1—N1ii2.361 (2)
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H4W···O4iii0.824 (17)2.02 (2)2.827 (3)168 (3)
O5—H3W···O2iv0.838 (17)1.942 (17)2.779 (3)176 (3)
O6—H1W···O5v0.837 (17)2.031 (18)2.859 (3)170 (4)
Symmetry codes: (iii) −x+1/2, −y, z−1/2; (iv) x, y, z−1; (v) x, −y+1/2, z+1/2.
references
References top

Bruker (1998). SMART (Version 5.0). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (1999). SAINT (Version 5.10), SHELXTL (Version 5.10) and SADABS (Version ???). Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.