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The title compound, [Co(C6H9O4)2(C12H12N2)(H2O)2]n, crystallizes in the space group P\overline{1}. The Co atom is on a center of symmetry and the 1,2-di-4-pyridylethane (bpe) ligand also sits across a crystallographic inversion center. The Co atom is octa­hedrally coordinated by two aqua ligands, two carboxyl­ate O atoms and two pyridyl N atoms, and is bridged by the anti-bpe ligands to generate one-dimensional ^1_{\infty}{[Co(Hadip)2(H2O)2](bpe)2/2} chains (Hadip is 5-carboxypentanoate), which are further inter­linked by O—H...O and C—H...O hydrogen bonds into two-dimensional layers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105022882/fa1144sup1.cif
Contains datablocks global, emp97

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105022882/fa1144Isup2.hkl
Contains datablock I

CCDC reference: 285644

Comment top

Investigation of coordination polymers has been expanded over the past decade (Moulton & Zaworotko, 2001) because of their intriguing structural motifs and their potential applications in catalysis, host–guest chemistry and magnetism (Leininger et al., 2000; Hagrman et al., 1999; Zhang et al., 2002; Feng & Xu, 2001; Yuan et al., 2002), and the rational design and syntheses of coordination polymers have been focused on the use of benzene di- and polycarboxylates as rigid bridging spacers (Li et al., 1999; Chui et al., 1999). On the other hand, utilization of aliphatic α,ω-dicarboxylates to construct supramolecular aggregates is of growing interest (Rao et al., 2004; Kitagawa et al., 2004). Our recent research effort has been intensively concentrated on construction of coordination polymers with specific topologies based on co-bridging of rigid 4,4'-bipyridine and α,ω-dicarboxylates (Zheng et al., 2004; Zheng & Ying, 2005). However, investigation of coordination polymers using 1,2-di-4-pyridylethane (bpe) and dicarboxylate anions to co-bridge metal ions has been very limited (Mukherjee et al., 2003). We report here a novel coordination polymer, [Co(C6H9O4)2(H2O)2(anti-bpe)], (I), which was obtained by reaction of bpe, adipic acid and CoCl2·6H2O in CH3OH/H2O (1:1, v:v).

In (I), the Co atoms sit on crystallographic inversion centers, and each Co atom is octahedrally coordinated by two N atoms of different anti-bpe ligands, four O atoms of two carboxypentanoate ligands and two aqua ligands. The Co—O bond distances are 2.1102 (14) and 2.1223 (14) Å, and the Co—N distance is 2.1576 (13) Å, with the cis bond angles in the range 88.51 (6)–91.49 (6)°. The anti-bpe ligands bridge the Co atoms along the [110] direction to generate one-dimensional 1{Co(Hadipa)2(H2O)2](bpe)2/2} chains, as shown in Fig. 1, which exhibit a relatively strong intrachain hydrogen bond between the aqua O atom and uncoordinated carboxylate atom O1 [O···O = 2.624 (2) Å and O—H···O = 163 (3)°]. Additionally (Table 1), aqua ligand O5 and carboxylic acid group O3 donate H atoms, respectively, to carboxylate atom O4i [symmetry code: (i) −x, 1 − y, 2 − z] and the coordinating carboxylate atom O2ii [symmetry code: (ii) x, y, z + 1] of neighboring chains, to form interchain hydrogen bonds [O···O = 2.753 (2) and 2.658 (2) Å, and O—H···O = 179 (3) and 161 (3)°]. The polymeric chains are linked through these bonds to form two-dimensional layers parallel to (100). The resulting layers are further stabilized by weak interchain hydrogen bonds between atom C12 of one anti-bpe ligand and uncoordinated carboxylate atom O1iii [symmetry code: (iii) x, y + 1, z]. The twisted carboxypentanoate ligands of one layer protrude into the grooves of the neighboring layers, as shown in Fig. 2. The carboxypentanoate ligands exhibit normal geometry (Ying et al., 2004), and the C6—O4 distance [1.205 (2) Å] is distinctly shorter than the C6—O3 distance [1.320 (2) Å], indicating C6O4 double-bond character.

Experimental top

In a typical synthesis, bpe (0.0921 g) and adipic acid (0.0731 g) were dissolved in CH3OH/H2O (1:1, v/v, 50 ml), and to the resulting solution, CoCl2·6H2O (0.1190 g) was added with stirring. The mixture was stirred for a further ca 30 min, yielding a red-colored solution, which was then maintained at room temperature; red crystals suitable for X-ray analysis were obtained after two weeks.

Refinement top

Compound (I) is triclinic; space group P1 was assumed and comfirmed by the analysis. H atoms associated with C atoms were positioned geometrically and refined using a riding model [C—H = 0.93 and 0.97 Å, and Uiso(H) = 1.2Ueq(C)], while H atoms of the aqua ligands and carboxyl group O3 were located from the difference Fourier syntheses with O—H distances refined.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of a fragment of the one-dimensional 1{Co(Hadipa)2(H2O)2](bpe)2/2} polymeric chains in (I). Displacement ellipsoids are drawn at the 45% probability level. Dashed lines indicate hydrogen bonds.
[Figure 2] Fig. 2. The crystal stucture of (I) (dashed lines indicate hydrogen bonds).
catena-Poly[[diaquabis(5-carboxypentanoato-κO)cobalt(II)]-µ- 1,2-di-4-pyridylethane-K2N:N'] top
Crystal data top
[Co(C6H9O4)2(C12H12N2)(H2O)2]Z = 1
Mr = 569.46F(000) = 299
Triclinic, P1Dx = 1.466 Mg m3
Hall symbol: -P1Mo Kα radiation, λ = 0.71073 Å
a = 8.6928 (17) ÅCell parameters from 25 reflections
b = 8.8579 (18) Åθ = 10–25°
c = 9.6059 (19) ŵ = 0.72 mm1
α = 85.17 (3)°T = 296 K
β = 65.14 (3)°Prism, red
γ = 74.03 (3)°0.39 × 0.31 × 0.22 mm
V = 644.8 (2) Å3
Data collection top
Bruker P4
diffractometer
2670 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.024
Graphite monochromatorθmax = 27.5°, θmin = 2.3°
θ/2θ scansh = 111
Absorption correction: ψ scan
(XSCANS; Siemens, 1996)
k = 1111
Tmin = 0.818, Tmax = 0.853l = 1112
3546 measured reflections3 standard reflections every 97 reflections
2959 independent reflections intensity decay: no
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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0298P)2 + 0.2282P]
where P = (Fo2 + 2Fc2)/3
2959 reflections(Δ/σ)max < 0.001
182 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
[Co(C6H9O4)2(C12H12N2)(H2O)2]γ = 74.03 (3)°
Mr = 569.46V = 644.8 (2) Å3
Triclinic, P1Z = 1
a = 8.6928 (17) ÅMo Kα radiation
b = 8.8579 (18) ŵ = 0.72 mm1
c = 9.6059 (19) ÅT = 296 K
α = 85.17 (3)°0.39 × 0.31 × 0.22 mm
β = 65.14 (3)°
Data collection top
Bruker P4
diffractometer
2670 reflections with I > 2σ(I)
Absorption correction: ψ scan
(XSCANS; Siemens, 1996)
Rint = 0.024
Tmin = 0.818, Tmax = 0.8533 standard reflections every 97 reflections
3546 measured reflections intensity decay: no
2959 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.25 e Å3
2959 reflectionsΔρmin = 0.24 e Å3
182 parameters
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
Co0.00000.50000.50000.02339 (9)
N10.01189 (18)0.65316 (15)0.65628 (14)0.0277 (3)
O10.21630 (17)0.20575 (15)0.64748 (15)0.0402 (3)
O20.26087 (15)0.36416 (14)0.45035 (12)0.0311 (2)
O30.4607 (2)0.25849 (19)1.16196 (15)0.0521 (4)
O40.31661 (18)0.45166 (16)1.06256 (14)0.0432 (3)
O50.10399 (17)0.35414 (14)0.68103 (14)0.0318 (2)
C10.3139 (2)0.26778 (18)0.53829 (17)0.0279 (3)
C20.5074 (2)0.2315 (2)0.50342 (19)0.0378 (4)
H2A0.54600.32630.46960.045*
H2B0.57280.15410.41910.045*
C30.5527 (2)0.1696 (2)0.63869 (19)0.0377 (4)
H3A0.51220.07590.67430.045*
H3B0.67950.14000.60380.045*
C40.4715 (2)0.2885 (2)0.77236 (19)0.0373 (4)
H4A0.51500.38090.73820.045*
H4B0.34490.32070.80590.045*
C50.5139 (3)0.2225 (2)0.90591 (19)0.0404 (4)
H5A0.48610.12190.92910.048*
H5B0.63940.20330.87480.048*
C60.4190 (2)0.3247 (2)1.04974 (18)0.0336 (3)
C70.0758 (2)0.59803 (19)0.76044 (19)0.0333 (3)
H7A0.10470.49000.77200.040*
C80.1013 (2)0.6920 (2)0.8517 (2)0.0356 (4)
H8A0.14640.64730.92240.043*
C90.0594 (2)0.85315 (19)0.83761 (18)0.0306 (3)
C100.0109 (2)0.91147 (19)0.73211 (19)0.0345 (4)
H10A0.04371.01930.72040.041*
C110.0320 (2)0.80941 (19)0.64446 (18)0.0321 (3)
H11A0.07890.85110.57410.038*
C120.0860 (2)0.9603 (2)0.9345 (2)0.0369 (4)
H12A0.13721.03980.87060.044*
H12B0.16760.89990.97590.044*
H3C0.405 (4)0.310 (3)1.243 (3)0.062 (8)*
H5D0.014 (4)0.300 (3)0.688 (3)0.054 (7)*
H5C0.170 (3)0.414 (3)0.762 (3)0.055 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.03023 (16)0.02187 (14)0.02134 (14)0.00585 (11)0.01357 (11)0.00389 (10)
N10.0349 (7)0.0258 (6)0.0260 (6)0.0060 (5)0.0158 (5)0.0066 (5)
O10.0386 (7)0.0409 (7)0.0424 (7)0.0108 (5)0.0196 (6)0.0122 (5)
O20.0329 (6)0.0363 (6)0.0230 (5)0.0029 (5)0.0141 (5)0.0014 (4)
O30.0564 (9)0.0617 (9)0.0250 (6)0.0115 (7)0.0200 (6)0.0056 (6)
O40.0451 (7)0.0450 (7)0.0300 (6)0.0031 (6)0.0148 (5)0.0046 (5)
O50.0350 (6)0.0312 (6)0.0290 (6)0.0088 (5)0.0127 (5)0.0015 (5)
C10.0326 (8)0.0286 (7)0.0231 (7)0.0027 (6)0.0143 (6)0.0056 (6)
C20.0321 (8)0.0535 (10)0.0241 (7)0.0026 (7)0.0126 (7)0.0033 (7)
C30.0333 (9)0.0465 (10)0.0291 (8)0.0038 (7)0.0165 (7)0.0058 (7)
C40.0426 (9)0.0401 (9)0.0313 (8)0.0020 (7)0.0222 (7)0.0027 (7)
C50.0435 (10)0.0429 (10)0.0287 (8)0.0036 (8)0.0177 (7)0.0031 (7)
C60.0317 (8)0.0438 (9)0.0245 (7)0.0074 (7)0.0123 (6)0.0007 (6)
C70.0456 (9)0.0246 (7)0.0352 (8)0.0042 (7)0.0240 (7)0.0042 (6)
C80.0460 (10)0.0343 (8)0.0340 (8)0.0052 (7)0.0258 (8)0.0060 (7)
C90.0325 (8)0.0337 (8)0.0271 (7)0.0090 (6)0.0114 (6)0.0109 (6)
C100.0486 (10)0.0240 (7)0.0342 (8)0.0090 (7)0.0197 (8)0.0048 (6)
C110.0453 (9)0.0276 (7)0.0289 (7)0.0079 (7)0.0212 (7)0.0025 (6)
C120.0404 (9)0.0403 (9)0.0351 (9)0.0124 (7)0.0168 (8)0.0134 (7)
Geometric parameters (Å, º) top
Co—O5i2.1102 (14)C3—H3A0.9700
Co—O52.1102 (14)C3—H3B0.9700
Co—O22.1223 (14)C4—C51.509 (2)
Co—O2i2.1223 (14)C4—H4A0.9700
Co—N12.1576 (13)C4—H4B0.9700
Co—N1i2.1576 (13)C5—C61.500 (2)
N1—C71.336 (2)C5—H5A0.9700
N1—C111.339 (2)C5—H5B0.9700
O1—C11.238 (2)C7—C81.378 (2)
O2—C11.2825 (19)C7—H7A0.9300
O3—C61.320 (2)C8—C91.383 (2)
O3—H3C0.82 (3)C8—H8A0.9300
O4—C61.205 (2)C9—C101.388 (2)
O5—H5D0.82 (3)C9—C121.506 (2)
O5—H5C0.86 (3)C10—C111.382 (2)
C1—C21.514 (2)C10—H10A0.9300
C2—C31.528 (2)C11—H11A0.9300
C2—H2A0.9700C12—C12ii1.517 (3)
C2—H2B0.9700C12—H12A0.9700
C3—C41.521 (2)C12—H12B0.9700
O5i—Co—O5180.00 (5)H3A—C3—H3B107.7
O5i—Co—O288.51 (6)C5—C4—C3112.01 (15)
O5—Co—O291.49 (6)C5—C4—H4A109.2
O5i—Co—O2i91.49 (6)C3—C4—H4A109.2
O5—Co—O2i88.51 (6)C5—C4—H4B109.2
O2—Co—O2i180.0C3—C4—H4B109.2
O5i—Co—N189.13 (5)H4A—C4—H4B107.9
O5—Co—N190.87 (5)C6—C5—C4115.16 (15)
O2—Co—N191.23 (6)C6—C5—H5A108.5
O2i—Co—N188.77 (6)C4—C5—H5A108.5
O5i—Co—N1i90.87 (5)C6—C5—H5B108.5
O5—Co—N1i89.13 (5)C4—C5—H5B108.5
O2—Co—N1i88.77 (6)H5A—C5—H5B107.5
O2i—Co—N1i91.23 (6)O4—C6—O3123.68 (16)
N1—Co—N1i180.000 (1)O4—C6—C5124.58 (15)
C7—N1—C11116.74 (13)O3—C6—C5111.74 (15)
C7—N1—Co122.23 (10)N1—C7—C8123.78 (15)
C11—N1—Co120.83 (10)N1—C7—H7A118.1
C1—O2—Co127.23 (10)C8—C7—H7A118.1
C6—O3—H3C113.2 (19)C7—C8—C9119.63 (15)
Co—O5—H5D101.5 (18)C7—C8—H8A120.2
Co—O5—H5C107.4 (17)C9—C8—H8A120.2
H5D—O5—H5C110 (2)C8—C9—C10116.88 (14)
O1—C1—O2123.68 (15)C8—C9—C12121.43 (15)
O1—C1—C2119.85 (15)C10—C9—C12121.69 (15)
O2—C1—C2116.47 (15)C11—C10—C9120.02 (15)
C1—C2—C3114.48 (14)C11—C10—H10A120.0
C1—C2—H2A108.6C9—C10—H10A120.0
C3—C2—H2A108.6N1—C11—C10122.93 (15)
C1—C2—H2B108.6N1—C11—H11A118.5
C3—C2—H2B108.6C10—C11—H11A118.5
H2A—C2—H2B107.6C9—C12—C12ii111.61 (18)
C4—C3—C2113.23 (15)C9—C12—H12A109.3
C4—C3—H3A108.9C12ii—C12—H12A109.3
C2—C3—H3A108.9C9—C12—H12B109.3
C4—C3—H3B108.9C12ii—C12—H12B109.3
C2—C3—H3B108.9H12A—C12—H12B108.0
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+2, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5D···O10.82 (3)1.83 (4)2.624 (2)163 (3)
O5—H5C···O4iii0.86 (3)1.89 (3)2.753 (2)179 (3)
O3—H3C···O2iv0.82 (3)1.87 (3)2.658 (2)161 (3)
Symmetry codes: (iii) x, y+1, z+2; (iv) x, y, z+1.

Experimental details

Crystal data
Chemical formula[Co(C6H9O4)2(C12H12N2)(H2O)2]
Mr569.46
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)8.6928 (17), 8.8579 (18), 9.6059 (19)
α, β, γ (°)85.17 (3), 65.14 (3), 74.03 (3)
V3)644.8 (2)
Z1
Radiation typeMo Kα
µ (mm1)0.72
Crystal size (mm)0.39 × 0.31 × 0.22
Data collection
DiffractometerBruker P4
diffractometer
Absorption correctionψ scan
(XSCANS; Siemens, 1996)
Tmin, Tmax0.818, 0.853
No. of measured, independent and
observed [I > 2σ(I)] reflections
3546, 2959, 2670
Rint0.024
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.078, 1.05
No. of reflections2959
No. of parameters182
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.25, 0.24

Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5D···O10.82 (3)1.83 (4)2.624 (2)163 (3)
O5—H5C···O4i0.86 (3)1.89 (3)2.753 (2)179 (3)
O3—H3C···O2ii0.82 (3)1.87 (3)2.658 (2)161 (3)
Symmetry codes: (i) x, y+1, z+2; (ii) x, y, z+1.
 

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