Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011436/wn6024sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011436/wn6024Isup2.hkl |
CCDC reference: 170881
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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.
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.
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.
Fig. 1. The structure of [Co(Hpydc)2(H2O)2]. Displacement ellipsoids are plotted at the 50% probability level. | |
Fig. 2. Packing diagram of [Co(Hpydc)2(H2O)2]. Dashed lines indicate the hydrogen bonds. |
C14H12CoN2O10 | F(000) = 868 |
Mr = 427.19 | Dx = 1.794 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.623 (5) Å | Cell parameters from 40 reflections |
b = 12.091 (4) Å | θ = 4.3–20.6° |
c = 15.436 (7) Å | µ = 1.15 mm−1 |
β = 100.59 (4)° | T = 293 K |
V = 1582.0 (12) Å3 | Block, orange |
Z = 4 | 0.28 × 0.06 × 0.06 mm |
SMART CCD diffractometer | 1386 independent reflections |
Radiation source: fine-focus sealed tube | 1243 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω scans | θmax = 25.0°, θmin = 2.7° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −8→10 |
Tmin = 0.723, Tmax = 0.933 | k = −14→12 |
4031 measured reflections | l = −18→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H 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 parameters | Δρmax = 0.34 e Å−3 |
2 restraints | Δρmin = −0.36 e Å−3 |
C14H12CoN2O10 | V = 1582.0 (12) Å3 |
Mr = 427.19 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 8.623 (5) Å | µ = 1.15 mm−1 |
b = 12.091 (4) Å | T = 293 K |
c = 15.436 (7) Å | 0.28 × 0.06 × 0.06 mm |
β = 100.59 (4)° |
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 = 0.933 | Rint = 0.031 |
4031 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 2 restraints |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.34 e Å−3 |
1386 reflections | Δρmin = −0.36 e Å−3 |
130 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Co | 0.0000 | 0.69456 (3) | 0.2500 | 0.02342 (16) | |
N | 0.0211 (2) | 0.72524 (15) | 0.39011 (12) | 0.0234 (4) | |
O1 | 0.2483 (3) | 0.96069 (16) | 0.36084 (12) | 0.0543 (6) | |
O2 | 0.16817 (19) | 0.82089 (13) | 0.27067 (10) | 0.0291 (4) | |
O3 | −0.1700 (2) | 0.56798 (15) | 0.58909 (11) | 0.0441 (5) | |
O4 | −0.1320 (2) | 0.72348 (14) | 0.66777 (11) | 0.0397 (5) | |
H4A | −0.2001 | 0.6982 | 0.6929 | 0.059* | |
O5 | 0.1760 (2) | 0.57771 (14) | 0.27037 (12) | 0.0378 (4) | |
H5A | 0.198 (4) | 0.538 (2) | 0.2247 (16) | 0.057* | |
H5B | 0.173 (4) | 0.529 (2) | 0.3146 (18) | 0.077 (12)* | |
C1 | 0.1781 (3) | 0.87315 (19) | 0.34284 (15) | 0.0285 (5) | |
C2 | 0.0975 (3) | 0.82152 (17) | 0.41216 (15) | 0.0236 (5) | |
C3 | 0.1063 (3) | 0.87124 (19) | 0.49306 (15) | 0.0304 (6) | |
H3 | 0.1598 | 0.9378 | 0.5055 | 0.036* | |
C4 | 0.0345 (3) | 0.82071 (19) | 0.55555 (15) | 0.0307 (6) | |
H4 | 0.0365 | 0.8534 | 0.6103 | 0.037* | |
C5 | −0.0408 (3) | 0.72025 (18) | 0.53497 (14) | 0.0241 (5) | |
C6 | −0.0446 (3) | 0.67516 (18) | 0.45192 (15) | 0.0246 (5) | |
H6 | −0.0946 | 0.6075 | 0.4386 | 0.029* | |
C7 | −0.1205 (3) | 0.6617 (2) | 0.59983 (15) | 0.0265 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.0338 (3) | 0.0175 (2) | 0.0215 (3) | 0.000 | 0.01177 (18) | 0.000 |
N | 0.0294 (10) | 0.0207 (10) | 0.0214 (10) | −0.0014 (8) | 0.0083 (8) | −0.0009 (7) |
O1 | 0.0882 (16) | 0.0464 (12) | 0.0336 (10) | −0.0420 (11) | 0.0251 (10) | −0.0094 (9) |
O2 | 0.0383 (10) | 0.0270 (9) | 0.0265 (9) | −0.0068 (7) | 0.0178 (7) | −0.0039 (7) |
O3 | 0.0691 (13) | 0.0355 (11) | 0.0324 (10) | −0.0183 (9) | 0.0213 (9) | −0.0021 (8) |
O4 | 0.0532 (12) | 0.0418 (10) | 0.0307 (10) | −0.0118 (9) | 0.0252 (8) | −0.0064 (8) |
O5 | 0.0581 (12) | 0.0291 (10) | 0.0305 (10) | 0.0153 (8) | 0.0197 (9) | 0.0050 (8) |
C1 | 0.0340 (13) | 0.0244 (12) | 0.0283 (13) | −0.0055 (10) | 0.0090 (10) | 0.0009 (10) |
C2 | 0.0291 (12) | 0.0187 (11) | 0.0243 (12) | −0.0007 (9) | 0.0081 (9) | −0.0008 (9) |
C3 | 0.0408 (14) | 0.0233 (13) | 0.0288 (13) | −0.0101 (10) | 0.0111 (11) | −0.0040 (10) |
C4 | 0.0407 (14) | 0.0316 (13) | 0.0222 (12) | −0.0076 (11) | 0.0118 (10) | −0.0072 (10) |
C5 | 0.0265 (12) | 0.0244 (12) | 0.0225 (12) | −0.0003 (9) | 0.0070 (9) | 0.0021 (9) |
C6 | 0.0321 (12) | 0.0186 (11) | 0.0245 (12) | −0.0037 (9) | 0.0091 (9) | 0.0002 (9) |
C7 | 0.0278 (12) | 0.0306 (13) | 0.0215 (12) | −0.0013 (10) | 0.0056 (9) | 0.0016 (9) |
Co—O5i | 2.0547 (18) | O3—O5iv | 2.802 (3) |
Co—O5 | 2.0547 (18) | O4—C7 | 1.306 (3) |
Co—O2 | 2.0899 (17) | O4—H4A | 0.8200 |
Co—O2i | 2.0899 (17) | O5—H5A | 0.903 (18) |
Co—N | 2.169 (2) | O5—H5B | 0.905 (18) |
Co—Ni | 2.169 (2) | C1—C2 | 1.514 (3) |
N—C6 | 1.340 (3) | C2—C3 | 1.376 (3) |
N—C2 | 1.350 (3) | C3—C4 | 1.381 (3) |
O1—C1 | 1.226 (3) | C3—H3 | 0.9300 |
O1—O5ii | 2.649 (2) | C4—C5 | 1.386 (3) |
O2—C1 | 1.270 (3) | C4—H4 | 0.9300 |
O2—O4iii | 2.605 (3) | C5—C6 | 1.388 (3) |
O2—O5 | 2.941 (2) | C5—C7 | 1.493 (3) |
O3—C7 | 1.211 (3) | C6—H6 | 0.9300 |
O5i—Co—O5 | 93.12 (12) | Co—O5—O2 | 45.28 (5) |
O5i—Co—O2 | 176.44 (7) | Co—O5—H5A | 120 (2) |
O5—Co—O2 | 90.41 (8) | O2—O5—H5A | 122.8 (19) |
O5i—Co—O2i | 90.41 (8) | Co—O5—H5B | 116 (2) |
O5—Co—O2i | 176.44 (7) | O2—O5—H5B | 130 (2) |
O2—Co—O2i | 86.08 (10) | H5A—O5—H5B | 106 (3) |
O5i—Co—N | 101.21 (7) | O1—C1—O2 | 125.4 (2) |
O5—Co—N | 92.35 (7) | O1—C1—C2 | 117.9 (2) |
O2—Co—N | 78.12 (7) | O2—C1—C2 | 116.7 (2) |
O2i—Co—N | 87.46 (7) | N—C2—C3 | 123.3 (2) |
O5i—Co—Ni | 92.35 (8) | N—C2—C1 | 116.34 (19) |
O5—Co—Ni | 101.21 (7) | C3—C2—C1 | 120.4 (2) |
O2—Co—Ni | 87.46 (7) | C2—C3—C4 | 118.9 (2) |
O2i—Co—Ni | 78.12 (7) | C2—C3—H3 | 120.5 |
N—Co—Ni | 160.30 (10) | C4—C3—H3 | 120.5 |
C6—N—C2 | 117.42 (19) | C3—C4—C5 | 118.6 (2) |
C6—N—Co | 131.59 (15) | C3—C4—H4 | 120.7 |
C2—N—Co | 110.27 (14) | C5—C4—H4 | 120.7 |
C1—O1—O5ii | 117.97 (16) | C4—C5—C6 | 119.1 (2) |
C1—O2—Co | 115.50 (14) | C4—C5—C7 | 121.0 (2) |
C1—O2—O4iii | 133.79 (16) | C6—C5—C7 | 119.8 (2) |
Co—O2—O4iii | 105.94 (8) | N—C6—C5 | 122.6 (2) |
C1—O2—O5 | 120.06 (14) | N—C6—H6 | 118.7 |
Co—O2—O5 | 44.31 (5) | C5—C6—H6 | 118.7 |
O4iii—O2—O5 | 77.01 (7) | O3—C7—O4 | 124.6 (2) |
C7—O3—O5iv | 122.56 (16) | O3—C7—C5 | 123.1 (2) |
C7—O4—H4A | 109.5 | O4—C7—C5 | 112.3 (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, z−1/2; (iv) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H12CoN2O10 |
Mr | 427.19 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.623 (5), 12.091 (4), 15.436 (7) |
β (°) | 100.59 (4) |
V (Å3) | 1582.0 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.15 |
Crystal size (mm) | 0.28 × 0.06 × 0.06 |
Data collection | |
Diffractometer | SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.723, 0.933 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4031, 1386, 1243 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.078, 1.09 |
No. of reflections | 1386 |
No. of parameters | 130 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.36 |
Computer programs: SMART (Siemens, 1994), SMART, XPREP (Siemens, 1994), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Co—O5 | 2.0547 (18) | O2—O4ii | 2.605 (3) |
Co—O2 | 2.0899 (17) | O2—O5 | 2.941 (2) |
Co—N | 2.169 (2) | O3—O5iii | 2.802 (3) |
O1—O5i | 2.649 (2) | ||
O5iv—Co—O5 | 93.12 (12) | O2iv—Co—N | 87.46 (7) |
O5iv—Co—O2 | 176.44 (7) | O5iv—Co—Niv | 92.35 (8) |
O5—Co—O2 | 90.41 (8) | N—Co—Niv | 160.30 (10) |
O2—Co—O2iv | 86.08 (10) | C6—N—Co | 131.59 (15) |
O5iv—Co—N | 101.21 (7) | C2—N—Co | 110.27 (14) |
O5—Co—N | 92.35 (7) | C1—O2—Co | 115.50 (14) |
O2—Co—N | 78.12 (7) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x+1/2, −y+3/2, z−1/2; (iii) −x, −y+1, −z+1; (iv) −x, y, −z+1/2. |
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.