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A mononuclear cobalt(II) coordination complex, [Co(Hpydc)2(H2O)2] (pydc = 2,5-pyridine­di­carboxyl­ate, C7H4NO4), has been prepared from the hydro­thermal reaction of Co(CH3COO)2·4H2O and H2pydc in water. Cobalt(II) is coordinated by four O atoms, two from pydc ligand, two from water mol­ecules, and two N atoms from the pydc ligands, to form a slightly distorted octahedral geometry. The Co-O and Co-N distances range from 2.055 (2) to 2.169 (2) Å. The discrete structure is further extended to form a three-dimensional structure involving weak hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011436/wn6024sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011436/wn6024Isup2.hkl
Contains datablock I

CCDC reference: 170881

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.029
  • wR factor = 0.078
  • Data-to-parameter ratio = 10.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Research into transition metal complexes has been rapidly expanding because of their fascinating structural diversity and potential applications as functional materials and enzymes (Li et al., 1998, 1999). The selection of a suitable ligand is essential in the design of transition metal complexes. Although some complexes containing the pyridine-2,5-dicarboxylic acid ligand have been reported (Plater et al., 1998), we still chose it as the ligand. It reacts with transition metals or rare earths; a series of novel complexes having infinite or discrete structures has been obtained and reported (Liang et al., 2000a,b, 2001). We report here the synthesis and crystal structure of the mononuclear cobalt(II) compound [Co(Hpydc)2(H2O)2] (pydc = pyridine-2,5-dicarboxylate), (I).

The coordination complex (I) was prepared by the hydrothermal reaction of Co(CH3COO)2.4(H2O) and H2pydc in H2O. The crystallographic analysis reveals that the compound is a discrete molecule [Co(Hpydc)2(H2O)2], in which each CoII atom is coordinated by two N and two O atoms of the two Hpydc ligands to form two five-membered chelating rings, and further coordinated by two water molecules to produce a slightly distorted octahedral geometry, as shown in Fig. 1. The distances and angles around Co are listed in Table 1. The hydrogen bond interactions, having an average O···O distance of 2.749 (3) Å, lead to the formation of a three-dimensional network structure, as shown in Fig. 2.

Experimental top

A mixture of Co(CH3COO)2.4(H2O) (0.225 g), [H2pydc].H2O (0.237 g) and H2O (15 ml) was sealed in a 25 ml stainless-steel reactor with Teflon liner. The reaction system was heated at 443 K for 72 h. Slow cooling of the system to room temperature yielded orange block-shaped crystals of the complex, which were collected by filtration.

Refinement top

The organic H atoms were positioned geometrically (C—H bond fixed at 0.96 Å), and allowed to ride on their parent C atoms before the final cycle of refinement. The aqua H atoms were located from difference maps, the O—H distance fixed at 0.94 Å and refined using isotropic displacement parameters.

Computing details top

Data collection: SMART (Siemens, 1994); cell refinement: SMART; data reduction: XPREP (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of [Co(Hpydc)2(H2O)2]. Displacement ellipsoids are plotted at the 50% probability level.
[Figure 2] Fig. 2. Packing diagram of [Co(Hpydc)2(H2O)2]. Dashed lines indicate the hydrogen bonds.
Diaquabis(pyridine-2,5-dicarboxylato)cobalt(II) top
Crystal data top
C14H12CoN2O10F(000) = 868
Mr = 427.19Dx = 1.794 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 8.623 (5) ÅCell parameters from 40 reflections
b = 12.091 (4) Åθ = 4.3–20.6°
c = 15.436 (7) ŵ = 1.15 mm1
β = 100.59 (4)°T = 293 K
V = 1582.0 (12) Å3Block, orange
Z = 40.28 × 0.06 × 0.06 mm
Data collection top
SMART CCD
diffractometer
1386 independent reflections
Radiation source: fine-focus sealed tube1243 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ω scansθmax = 25.0°, θmin = 2.7°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 810
Tmin = 0.723, Tmax = 0.933k = 1412
4031 measured reflectionsl = 1818
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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0351P)2 + 1.4634P]
where P = (Fo2 + 2Fc2)/3
1386 reflections(Δ/σ)max < 0.001
130 parametersΔρmax = 0.34 e Å3
2 restraintsΔρmin = 0.36 e Å3
Crystal data top
C14H12CoN2O10V = 1582.0 (12) Å3
Mr = 427.19Z = 4
Monoclinic, C2/cMo Kα radiation
a = 8.623 (5) ŵ = 1.15 mm1
b = 12.091 (4) ÅT = 293 K
c = 15.436 (7) Å0.28 × 0.06 × 0.06 mm
β = 100.59 (4)°
Data collection top
SMART CCD
diffractometer
1386 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
1243 reflections with I > 2σ(I)
Tmin = 0.723, Tmax = 0.933Rint = 0.031
4031 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0292 restraints
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.34 e Å3
1386 reflectionsΔρmin = 0.36 e Å3
130 parameters
Special details top

Experimental. Empirical; from equivalent reflections(XEMP in SHELXTL; Siemens,1994

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
Co0.00000.69456 (3)0.25000.02342 (16)
N0.0211 (2)0.72524 (15)0.39011 (12)0.0234 (4)
O10.2483 (3)0.96069 (16)0.36084 (12)0.0543 (6)
O20.16817 (19)0.82089 (13)0.27067 (10)0.0291 (4)
O30.1700 (2)0.56798 (15)0.58909 (11)0.0441 (5)
O40.1320 (2)0.72348 (14)0.66777 (11)0.0397 (5)
H4A0.20010.69820.69290.059*
O50.1760 (2)0.57771 (14)0.27037 (12)0.0378 (4)
H5A0.198 (4)0.538 (2)0.2247 (16)0.057*
H5B0.173 (4)0.529 (2)0.3146 (18)0.077 (12)*
C10.1781 (3)0.87315 (19)0.34284 (15)0.0285 (5)
C20.0975 (3)0.82152 (17)0.41216 (15)0.0236 (5)
C30.1063 (3)0.87124 (19)0.49306 (15)0.0304 (6)
H30.15980.93780.50550.036*
C40.0345 (3)0.82071 (19)0.55555 (15)0.0307 (6)
H40.03650.85340.61030.037*
C50.0408 (3)0.72025 (18)0.53497 (14)0.0241 (5)
C60.0446 (3)0.67516 (18)0.45192 (15)0.0246 (5)
H60.09460.60750.43860.029*
C70.1205 (3)0.6617 (2)0.59983 (15)0.0265 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0338 (3)0.0175 (2)0.0215 (3)0.0000.01177 (18)0.000
N0.0294 (10)0.0207 (10)0.0214 (10)0.0014 (8)0.0083 (8)0.0009 (7)
O10.0882 (16)0.0464 (12)0.0336 (10)0.0420 (11)0.0251 (10)0.0094 (9)
O20.0383 (10)0.0270 (9)0.0265 (9)0.0068 (7)0.0178 (7)0.0039 (7)
O30.0691 (13)0.0355 (11)0.0324 (10)0.0183 (9)0.0213 (9)0.0021 (8)
O40.0532 (12)0.0418 (10)0.0307 (10)0.0118 (9)0.0252 (8)0.0064 (8)
O50.0581 (12)0.0291 (10)0.0305 (10)0.0153 (8)0.0197 (9)0.0050 (8)
C10.0340 (13)0.0244 (12)0.0283 (13)0.0055 (10)0.0090 (10)0.0009 (10)
C20.0291 (12)0.0187 (11)0.0243 (12)0.0007 (9)0.0081 (9)0.0008 (9)
C30.0408 (14)0.0233 (13)0.0288 (13)0.0101 (10)0.0111 (11)0.0040 (10)
C40.0407 (14)0.0316 (13)0.0222 (12)0.0076 (11)0.0118 (10)0.0072 (10)
C50.0265 (12)0.0244 (12)0.0225 (12)0.0003 (9)0.0070 (9)0.0021 (9)
C60.0321 (12)0.0186 (11)0.0245 (12)0.0037 (9)0.0091 (9)0.0002 (9)
C70.0278 (12)0.0306 (13)0.0215 (12)0.0013 (10)0.0056 (9)0.0016 (9)
Geometric parameters (Å, º) top
Co—O5i2.0547 (18)O3—O5iv2.802 (3)
Co—O52.0547 (18)O4—C71.306 (3)
Co—O22.0899 (17)O4—H4A0.8200
Co—O2i2.0899 (17)O5—H5A0.903 (18)
Co—N2.169 (2)O5—H5B0.905 (18)
Co—Ni2.169 (2)C1—C21.514 (3)
N—C61.340 (3)C2—C31.376 (3)
N—C21.350 (3)C3—C41.381 (3)
O1—C11.226 (3)C3—H30.9300
O1—O5ii2.649 (2)C4—C51.386 (3)
O2—C11.270 (3)C4—H40.9300
O2—O4iii2.605 (3)C5—C61.388 (3)
O2—O52.941 (2)C5—C71.493 (3)
O3—C71.211 (3)C6—H60.9300
O5i—Co—O593.12 (12)Co—O5—O245.28 (5)
O5i—Co—O2176.44 (7)Co—O5—H5A120 (2)
O5—Co—O290.41 (8)O2—O5—H5A122.8 (19)
O5i—Co—O2i90.41 (8)Co—O5—H5B116 (2)
O5—Co—O2i176.44 (7)O2—O5—H5B130 (2)
O2—Co—O2i86.08 (10)H5A—O5—H5B106 (3)
O5i—Co—N101.21 (7)O1—C1—O2125.4 (2)
O5—Co—N92.35 (7)O1—C1—C2117.9 (2)
O2—Co—N78.12 (7)O2—C1—C2116.7 (2)
O2i—Co—N87.46 (7)N—C2—C3123.3 (2)
O5i—Co—Ni92.35 (8)N—C2—C1116.34 (19)
O5—Co—Ni101.21 (7)C3—C2—C1120.4 (2)
O2—Co—Ni87.46 (7)C2—C3—C4118.9 (2)
O2i—Co—Ni78.12 (7)C2—C3—H3120.5
N—Co—Ni160.30 (10)C4—C3—H3120.5
C6—N—C2117.42 (19)C3—C4—C5118.6 (2)
C6—N—Co131.59 (15)C3—C4—H4120.7
C2—N—Co110.27 (14)C5—C4—H4120.7
C1—O1—O5ii117.97 (16)C4—C5—C6119.1 (2)
C1—O2—Co115.50 (14)C4—C5—C7121.0 (2)
C1—O2—O4iii133.79 (16)C6—C5—C7119.8 (2)
Co—O2—O4iii105.94 (8)N—C6—C5122.6 (2)
C1—O2—O5120.06 (14)N—C6—H6118.7
Co—O2—O544.31 (5)C5—C6—H6118.7
O4iii—O2—O577.01 (7)O3—C7—O4124.6 (2)
C7—O3—O5iv122.56 (16)O3—C7—C5123.1 (2)
C7—O4—H4A109.5O4—C7—C5112.3 (2)
Symmetry codes: (i) x, y, z+1/2; (ii) x+1/2, y+1/2, z+1/2; (iii) x+1/2, y+3/2, z1/2; (iv) x, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC14H12CoN2O10
Mr427.19
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)8.623 (5), 12.091 (4), 15.436 (7)
β (°) 100.59 (4)
V3)1582.0 (12)
Z4
Radiation typeMo Kα
µ (mm1)1.15
Crystal size (mm)0.28 × 0.06 × 0.06
Data collection
DiffractometerSMART CCD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.723, 0.933
No. of measured, independent and
observed [I > 2σ(I)] reflections
4031, 1386, 1243
Rint0.031
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.078, 1.09
No. of reflections1386
No. of parameters130
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.34, 0.36

Computer programs: SMART (Siemens, 1994), SMART, XPREP (Siemens, 1994), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
Co—O52.0547 (18)O2—O4ii2.605 (3)
Co—O22.0899 (17)O2—O52.941 (2)
Co—N2.169 (2)O3—O5iii2.802 (3)
O1—O5i2.649 (2)
O5iv—Co—O593.12 (12)O2iv—Co—N87.46 (7)
O5iv—Co—O2176.44 (7)O5iv—Co—Niv92.35 (8)
O5—Co—O290.41 (8)N—Co—Niv160.30 (10)
O2—Co—O2iv86.08 (10)C6—N—Co131.59 (15)
O5iv—Co—N101.21 (7)C2—N—Co110.27 (14)
O5—Co—N92.35 (7)C1—O2—Co115.50 (14)
O2—Co—N78.12 (7)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1/2, y+3/2, z1/2; (iii) x, y+1, z+1; (iv) x, y, z+1/2.
 

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