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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): m1498.
Published online 2010 October 31. doi:  10.1107/S1600536810043540
PMCID: PMC3009297

catena-Poly[[cobalt(II)-μ-aqua-μ-propano­ato-κ2 O:O′-μ-propano­ato-κ2 O:O] monohydrate]

Abstract

The title compound, {[Co(C2H5COO)2(H2O)]·H2O}n, was synthesized by the reaction of cobalt(II) carbonate hydrate with aqueous propionic acid. The structure consists of polymeric infinite linear chains with composition [Co(C2H5COO)4/2(H2O)2/2] running along [010]. The chains are formed by Co2+ ions linked with bridging propionate groups and water mol­ecules, with a Co(...)Co distance along the chains of 3.2587 (9) Å. The Co2+ ion is six-coordinated in a strongly distorted octa­hedral geometry. The chains are connected to each other by a network of O—H(...)O hydrogen bonds involving solvent water mol­ecules.

Related literature

For the related cobalt(II) acetate dihydrate, see: Jiao et al. (2000 [triangle]). For the structure of a hydrated cobalt(II) acetate which has been isolated in similar conditions, see: Sobolev et al. (2003 [triangle]). For properties and applications of cobalt carboxyl­ates, see: Eremenko et al. (2009 [triangle]); Gates (1992 [triangle]); Parshall & Ittel (1992 [triangle]); Partenheimer (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1498-scheme1.jpg

Experimental

Crystal data

  • [Co(C3H5O2)2(H2O)]·H2O
  • M r = 241.10
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1498-efi6.jpg
  • a = 13.997 (4) Å
  • b = 6.4987 (18) Å
  • c = 21.440 (6) Å
  • β = 103.216 (5)°
  • V = 1898.6 (9) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 1.81 mm−1
  • T = 170 K
  • 0.5 × 0.3 × 0.2 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2007 [triangle]) T min = 0.276, T max = 0.332
  • 11986 measured reflections
  • 2762 independent reflections
  • 2542 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.067
  • S = 1.09
  • 2762 reflections
  • 130 parameters
  • 5 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.41 e Å−3
  • Δρmin = −0.57 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2008 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810043540/fj2358sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043540/fj2358Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Cobalt carboxylates are of great importance because of their application in homogeneous oxidation catalysis (Gates, 1992; Parshall & Ittel, 1992; Partenheimer, 1995), and their interesting magnetic properties (Eremenko et al., 2009). Carboxylate ligands coordinated to transition metal ions can adopt different binding modes and form a great number of various cage complexes and a variety of different one-dimensional, two-dimensional and three-dimensional structures.

The title compound, [Co(C2H5COO)2(H2O)]n.nH2O (I), actually named as cobalt(II) propionate dihydrate, is attracting our attention as the starting substance for the synthesis of mixed-valence cobalt carboxylates. This salt was synthesized and its crystal structure is reported herein.

The crystal structure of (I) contains one symmetrically independent Co2+ cation coordinated to four O atoms of four bridging propionates and two O atoms of bridging water molecules in a strongly distorted octahedral coordination (Fig. 1). The cis-angles about the Co atom range from 77.35 (4) to 109.40 (5)°, the Co—O bond length ranges from 2.0406 (12) to 2.2460 (12) Å; this is in agreement with the angles and the distances in isostructural cobalt(II) acetate dihydrate (Jiao et al., 2000). The structure of (I) consists of polymeric infinite linear chains with composition [Co(C2H5COO)4/2(H2O)2/2] running along [010]. The Co···Co separation is 3.2587 (9) Å. The bridging carboxylate groups adopt two coordination modes, monodentate and syn-syn bidentate. The bidentate carboxylate group has C—O bonds of equal length, 1.267 (2) Å, whereas monodentate carboxylate group has different C—O bond lengths, 1.235 (2) and 1.305 (2) Å. The chains are connected to each other by a network of hydrogen bonds to solvate water molecules (Fig. 2).

It is rather interesting that the use of acetic acid instead of propionic acid in the synthesis of (I) result in the formation of monomeric cobalt(II) acetate tetrahydrate (Sobolev et al., 2003), and the polymeric cobalt(II) acetate dihydrate is formed by recrystallization of cobalt(II) acetate tetrahydrate from acetic acid (Jiao et al., 2000).

Experimental

To a solution of propionic acid (7.4 g, 100 mmol) in water (15 ml), an excess of fresh cobalt(II) carbonate hydrate, CoCO3.xH2O, (8.0 g, approximately 60 mmol) was added. The reaction mixture was stirred for 8 h at room temperature, followed by filtrating the unreacted CoCO3.xH2O out. The filtrate was allowed to stand at room temperature for slow evaporation. The red single crystals of (I) suitable for X-ray diffraction studies were obtained after several days. Yield 85%.

Refinement

For a single-crystal X-ray diffraction experiment, a red transparent crystal of (I) was mounted on the Bruker Smart APEX II diffractometer. The experiment was performed at 170 K. The structure was solved by the direct method and refined using SHELXL-97 program (Sheldrick, 2008). The positions of hydrogen atoms of water molecules were localized from the differential Fourier synthesis and H atoms of the CH2 and CH3 groups were calculated by the algorithm incorporated in the SHELXL program complex. Hydrogen atoms kept fixed with Uiso(H) = 1.5Ueq(C).

Figures

Fig. 1.
[Figure 1. The coordinated mode and linkage of the complex (I). Displacement ellipsoids of non-H atoms are drawn at the 40% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. Symmetry codes: i = –x + 1/2, y + 1/2,–z ...
Fig. 2.
[Figure 2. Sticks representation of the crystal structure of (I) showing hydrogen bonds as green dashed lines. Only the H atoms involved in hydrogen bonds are shown. Co atoms are blue, O atoms are red, C atoms are grey, and selected H atoms are green ...

Crystal data

[Co(C3H5O2)2(H2O)]·H2OF(000) = 1000
Mr = 241.10Dx = 1.687 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 7703 reflections
a = 13.997 (4) Åθ = 2.9–35.9°
b = 6.4987 (18) ŵ = 1.81 mm1
c = 21.440 (6) ÅT = 170 K
β = 103.216 (5)°Prism, red
V = 1898.6 (9) Å30.5 × 0.3 × 0.2 mm
Z = 8

Data collection

Bruker APEXII CCD diffractometer2762 independent reflections
Radiation source: fine-focus sealed tube2542 reflections with I > 2σ(I)
graphiteRint = 0.032
[var phi] and ω scansθmax = 30.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)h = −19→19
Tmin = 0.276, Tmax = 0.332k = −9→9
11986 measured reflectionsl = −30→30

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067H atoms treated by a mixture of independent and constrained refinement
S = 1.09w = 1/[σ2(Fo2) + (0.0329P)2 + 1.4667P] where P = (Fo2 + 2Fc2)/3
2762 reflections(Δ/σ)max < 0.001
130 parametersΔρmax = 0.41 e Å3
5 restraintsΔρmin = −0.57 e Å3

Special details

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 > 2σ(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)

xyzUiso*/Ueq
Co10.248706 (13)0.18331 (3)0.244111 (9)0.01830 (7)
O10.29927 (8)0.44228 (16)0.19444 (5)0.0231 (2)
H110.267 (2)0.511 (5)0.1580 (14)0.080*
H120.362 (2)0.441 (5)0.1918 (16)0.080*
O20.39246 (8)−0.23440 (17)0.29662 (6)0.0262 (2)
O30.23831 (8)−0.08151 (15)0.18689 (5)0.0217 (2)
O40.39309 (8)0.10838 (17)0.28586 (5)0.0246 (2)
O50.47910 (10)0.4367 (2)0.17307 (8)0.0391 (3)
H510.516 (2)0.328 (5)0.1935 (15)0.080*
H520.517 (2)0.543 (4)0.1846 (16)0.080*
O60.21765 (10)−0.29849 (19)0.10436 (6)0.0338 (3)
C10.53359 (12)−0.0526 (3)0.35261 (9)0.0304 (3)
H1A0.57320.05980.33900.046*
H1B0.5683−0.18600.35050.046*
C20.21658 (11)−0.1222 (2)0.12565 (7)0.0229 (3)
C30.1606 (2)0.0073 (4)0.01094 (10)0.0580 (7)
H3A0.14500.1368−0.01460.087*
H3B0.1013−0.08340.00290.087*
H3C0.2157−0.0660−0.00210.087*
C40.52401 (19)−0.0140 (5)0.42103 (11)0.0600 (7)
H4A0.5908−0.01010.45030.090*
H4B0.4847−0.12720.43460.090*
H4C0.49020.12060.42310.090*
C50.43274 (11)−0.0596 (2)0.30805 (7)0.0208 (3)
C60.19027 (18)0.0594 (3)0.08116 (9)0.0418 (5)
H6A0.13510.13580.09320.063*
H6B0.24800.15440.08810.063*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Co10.01681 (10)0.01335 (10)0.02365 (11)0.00019 (7)0.00237 (7)0.00019 (7)
O10.0216 (5)0.0199 (5)0.0281 (5)0.0003 (4)0.0061 (4)0.0025 (4)
O20.0192 (5)0.0173 (5)0.0387 (6)−0.0008 (4)−0.0006 (4)0.0004 (4)
O30.0247 (5)0.0170 (5)0.0221 (5)0.0004 (4)0.0026 (4)0.0003 (4)
O40.0185 (5)0.0181 (5)0.0347 (6)0.0001 (4)0.0010 (4)0.0004 (4)
O50.0241 (6)0.0228 (6)0.0687 (10)0.0001 (5)0.0068 (6)0.0011 (6)
O60.0486 (8)0.0254 (6)0.0255 (5)0.0056 (5)0.0044 (5)−0.0032 (4)
C10.0188 (7)0.0231 (8)0.0443 (9)0.0001 (6)−0.0034 (6)0.0012 (6)
C20.0225 (7)0.0225 (7)0.0234 (6)0.0027 (6)0.0043 (5)0.0012 (5)
C30.089 (2)0.0507 (13)0.0271 (9)0.0158 (13)−0.0012 (10)0.0075 (9)
C40.0477 (13)0.0883 (19)0.0351 (10)−0.0161 (13)−0.0093 (9)0.0042 (12)
C50.0170 (6)0.0199 (7)0.0253 (6)0.0002 (5)0.0044 (5)−0.0005 (5)
C60.0667 (14)0.0300 (9)0.0270 (8)0.0139 (9)0.0069 (8)0.0065 (7)

Geometric parameters (Å, °)

Co1—O2i2.0406 (12)C1—C51.514 (2)
Co1—O42.0726 (12)C1—C41.524 (3)
Co1—O32.0991 (11)C1—H1A1.0000
Co1—O3i2.1058 (11)C1—H1B1.0000
Co1—O12.1936 (12)C2—C61.509 (2)
Co1—O1ii2.2460 (12)C3—C61.506 (3)
O1—H110.92 (3)C3—H3A1.0000
O1—H120.89 (3)C3—H3B1.0000
O2—C51.2669 (18)C3—H3C1.0000
O3—C21.3053 (18)C4—H4A1.0000
O4—C51.2670 (18)C4—H4B1.0000
O5—H510.92 (3)C4—H4C1.0000
O5—H520.87 (3)C6—H6A1.0000
O6—C21.2346 (19)C6—H6B1.0000
O2i—Co1—O4178.40 (4)C4—C1—H1A109.7
O2i—Co1—O391.94 (5)C5—C1—H1B109.7
O4—Co1—O389.44 (4)C4—C1—H1B109.7
O2i—Co1—O3i91.72 (5)H1A—C1—H1B108.2
O4—Co1—O3i87.03 (4)O6—C2—O3122.70 (14)
O3—Co1—O3i171.46 (4)O6—C2—C6120.92 (14)
O2i—Co1—O188.83 (5)O3—C2—C6116.38 (14)
O4—Co1—O189.94 (5)C6—C3—H3A109.5
O3—Co1—O1109.40 (5)C6—C3—H3B109.5
O3i—Co1—O178.38 (5)H3A—C3—H3B109.5
O2i—Co1—O1ii92.50 (5)C6—C3—H3C109.5
O4—Co1—O1ii88.60 (5)H3A—C3—H3C109.5
O3—Co1—O1ii77.35 (4)H3B—C3—H3C109.5
O3i—Co1—O1ii94.79 (5)C1—C4—H4A109.5
O1—Co1—O1ii173.08 (3)C1—C4—H4B109.5
Co1—O1—Co1i94.44 (5)H4A—C4—H4B109.5
Co1—O1—H11129 (2)C1—C4—H4C109.5
Co1i—O1—H1190 (2)H4A—C4—H4C109.5
Co1—O1—H12117 (2)H4B—C4—H4C109.5
Co1i—O1—H12118 (2)O2—C5—O4124.23 (14)
H11—O1—H12104 (3)O2—C5—C1117.31 (13)
C5—O2—Co1ii131.47 (10)O4—C5—C1118.44 (13)
C2—O3—Co1136.31 (10)C3—C6—C2115.31 (17)
C2—O3—Co1ii121.50 (10)C3—C6—H6A108.4
Co1—O3—Co1ii101.60 (5)C2—C6—H6A108.4
C5—O4—Co1131.66 (10)C3—C6—H6B108.4
H51—O5—H52104 (3)C2—C6—H6B108.4
C5—C1—C4109.75 (16)H6A—C6—H6B107.5
C5—C1—H1A109.7

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H11···O6iii0.92 (3)1.72 (3)2.620 (2)163 (3)
O1—H12···O50.89 (3)1.78 (3)2.660 (2)171 (3)
O5—H51···O4iv0.92 (3)1.90 (3)2.794 (2)163 (3)
O5—H52···O2v0.87 (3)1.91 (3)2.773 (2)174 (3)

Symmetry codes: (iii) x, y+1, z; (iv) −x+1, y, −z+1/2; (v) −x+1, y+1, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2358).

References

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