Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049161/ng2335sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049161/ng2335Isup2.hkl |
CCDC reference: 667151
2,6-Dimethylpyridine-3,5-dicarboxylic acid was prepared by basic hydrolysis of diethyl 2,6-dimethylpyridine-3,5-dicarboxylate (Checchi, 1959). Diethyl 2,6-dimethylpyridine-3,5-dicarboxylate (25.1 g, 0.1 mol) and potassium hydroxide (13.44 g, 0.24 mol) were dissolved in 150 ml e thanol and 150 ml water. The solution was stirred for three hours under reflux conditions. 2,6-Dimethylpyridine-3,5-dicarboxylic acid (10.5 g), a white precipitate, was formed by adjusting the pH of the solution to 3 with 0.1 M HCl after ethanol was removed by evaporation.
The complex was synthesized with cobalt(II) dinitrate hexahydrate (0.582 g, 2 mmol) and 2,6-dimethylpyridine-3,5-dicarboxylic acid (0.390 g, 2 mmol) in water; the pH was adjusted to 6 with 0.01 M sodium hydroxide. Pink crystals separated from the filtered solution after several days.
H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å, 0.97 Å for aromatic and methyl H atoms respectively; Uiso(H) was set to = 1.2Ueq of the carrier atom (1.5 Ueq for methyl H atoms). Water H atoms were initially located in a difference Fourier map; they were treated as riding on their parent atoms. The H4 atom bond to N1 atoms was located in a difference Fourier map and refined isotropically.
Recently, we reported the crystal structure of trans-tetraaqua-bis(2,6-dimethylpyridinium-3,5-dicarboxylato) copper(II) tetrahydrate (Shi et al. 2007). The title cobalt analog (Fig. 1) is centrosymmetric, and the metal exists in an octahedral coordination geometry. Molecules are linked by O—H···O and N—H···O hydrogen bonds involving allpotential donors to generate infinite three-dimensional network. (Table 1; Fig. 2). The two compounds are not isostructural although both have the same formula.
For the synthesis of the ligand, see: Checchi (1959). For the crystal structure of the copper compound (which is not isostructural), see: Shi et al. (2007)
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997a).
[Co(C9H8NO4)2(H2O)4]·4H2O | Z = 1 |
Mr = 591.39 | F(000) = 309 |
Triclinic, P1 | Dx = 1.583 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.597 (5) Å | Cell parameters from 5838 reflections |
b = 8.651 (7) Å | θ = 3.4–27.5° |
c = 10.715 (7) Å | µ = 0.77 mm−1 |
α = 69.90 (3)° | T = 295 K |
β = 69.75 (2)° | Block, pink |
γ = 83.58 (2)° | 0.48 × 0.39 × 0.31 mm |
V = 620.4 (8) Å3 |
Rigaku R-AXIS RAPID diffractometer | 2803 independent reflections |
Radiation source: fine-focus sealed tube | 2631 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ω scans | θmax = 27.5°, θmin = 3.4° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −9→8 |
Tmin = 0.706, Tmax = 0.794 | k = −11→11 |
6106 measured reflections | l = −13→13 |
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) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.21 | w = 1/[σ2(Fo2) + (0.0531P)2 + 0.2698P] where P = (Fo2 + 2Fc2)/3 |
2803 reflections | (Δ/σ)max = 0.004 |
175 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
[Co(C9H8NO4)2(H2O)4]·4H2O | γ = 83.58 (2)° |
Mr = 591.39 | V = 620.4 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.597 (5) Å | Mo Kα radiation |
b = 8.651 (7) Å | µ = 0.77 mm−1 |
c = 10.715 (7) Å | T = 295 K |
α = 69.90 (3)° | 0.48 × 0.39 × 0.31 mm |
β = 69.75 (2)° |
Rigaku R-AXIS RAPID diffractometer | 2803 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2631 reflections with I > 2σ(I) |
Tmin = 0.706, Tmax = 0.794 | Rint = 0.015 |
6106 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.21 | Δρmax = 0.46 e Å−3 |
2803 reflections | Δρmin = −0.30 e Å−3 |
175 parameters |
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 | ||
O7 | 0.6205 (2) | 0.66640 (19) | 0.29668 (15) | 0.0360 (3) | |
Co1 | 1.0000 | 0.5000 | 0.0000 | 0.01986 (12) | |
O1 | 0.9067 (2) | 0.33848 (17) | 0.20120 (14) | 0.0325 (3) | |
O2 | 0.9725 (3) | 0.08988 (19) | 0.17835 (15) | 0.0469 (4) | |
O3 | 0.5899 (2) | −0.39084 (16) | 0.78211 (14) | 0.0282 (3) | |
O4 | 0.5555 (2) | −0.34851 (18) | 0.57558 (15) | 0.0348 (3) | |
O6 | 0.7258 (2) | 0.5352 (2) | 0.00197 (15) | 0.0364 (4) | |
H11 | 0.6395 | 0.4893 | 0.0785 | 0.055* | |
H10 | 0.6940 | 0.5771 | −0.0713 | 0.055* | |
O5 | 1.0344 (2) | 0.30316 (17) | −0.08666 (14) | 0.0291 (3) | |
H8 | 1.0355 | 0.2192 | −0.0163 | 0.044* | |
H9 | 1.1412 | 0.3114 | −0.1501 | 0.044* | |
N1 | 0.7321 (2) | 0.11394 (18) | 0.63709 (16) | 0.0228 (3) | |
H4 | 0.728 (4) | 0.167 (3) | 0.691 (3) | 0.029 (6)* | |
C1 | 0.9123 (3) | 0.1843 (2) | 0.24754 (18) | 0.0239 (4) | |
C2 | 0.8308 (2) | 0.1072 (2) | 0.40626 (17) | 0.0205 (3) | |
C3 | 0.8208 (2) | 0.1904 (2) | 0.49864 (18) | 0.0212 (3) | |
C4 | 0.9000 (3) | 0.3567 (2) | 0.4621 (2) | 0.0319 (4) | |
H2 | 0.8069 | 0.4388 | 0.4462 | 0.048* | |
H1 | 1.0078 | 0.3772 | 0.3783 | 0.048* | |
H3 | 0.9364 | 0.3610 | 0.5382 | 0.048* | |
C5 | 0.6508 (3) | −0.0367 (2) | 0.69532 (18) | 0.0221 (3) | |
C6 | 0.5440 (3) | −0.0842 (3) | 0.8498 (2) | 0.0356 (5) | |
H6 | 0.6258 | −0.1405 | 0.9019 | 0.053* | |
H7 | 0.4413 | −0.1555 | 0.8723 | 0.053* | |
H5 | 0.4963 | 0.0129 | 0.8740 | 0.053* | |
C7 | 0.6681 (2) | −0.1265 (2) | 0.60701 (17) | 0.0197 (3) | |
C8 | 0.5976 (2) | −0.3021 (2) | 0.65888 (18) | 0.0213 (3) | |
C9 | 0.7573 (2) | −0.0511 (2) | 0.46273 (17) | 0.0211 (3) | |
H16 | 0.7677 | −0.1096 | 0.4021 | 0.025* | |
O8 | 0.7410 (3) | 0.2787 (2) | 0.81069 (18) | 0.0437 (4) | |
H14 | 0.6800 | 0.3662 | 0.8155 | 0.066* | |
H15 | 0.8350 | 0.2779 | 0.8367 | 0.066* | |
H13 | 0.5924 | 0.6709 | 0.3793 | 0.066* | |
H12 | 0.5774 | 0.5721 | 0.3141 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O7 | 0.0431 (8) | 0.0336 (8) | 0.0282 (7) | −0.0047 (6) | −0.0064 (6) | −0.0101 (6) |
Co1 | 0.02236 (19) | 0.01968 (18) | 0.01346 (17) | −0.00420 (12) | −0.00471 (12) | −0.00036 (12) |
O1 | 0.0482 (9) | 0.0219 (7) | 0.0171 (6) | −0.0023 (6) | −0.0052 (6) | 0.0013 (5) |
O2 | 0.0793 (13) | 0.0293 (8) | 0.0188 (7) | −0.0015 (8) | −0.0021 (7) | −0.0054 (6) |
O3 | 0.0373 (7) | 0.0235 (6) | 0.0198 (6) | −0.0074 (5) | −0.0110 (6) | 0.0015 (5) |
O4 | 0.0510 (9) | 0.0302 (7) | 0.0246 (7) | −0.0152 (6) | −0.0114 (6) | −0.0070 (6) |
O6 | 0.0247 (7) | 0.0553 (10) | 0.0211 (6) | −0.0045 (6) | −0.0080 (5) | −0.0007 (6) |
O5 | 0.0333 (7) | 0.0284 (7) | 0.0221 (6) | −0.0036 (5) | −0.0051 (6) | −0.0067 (5) |
N1 | 0.0297 (8) | 0.0188 (7) | 0.0193 (7) | −0.0003 (6) | −0.0066 (6) | −0.0069 (6) |
C1 | 0.0259 (9) | 0.0239 (8) | 0.0165 (8) | −0.0053 (7) | −0.0050 (7) | −0.0003 (6) |
C2 | 0.0241 (8) | 0.0188 (8) | 0.0157 (7) | 0.0002 (6) | −0.0069 (6) | −0.0016 (6) |
C3 | 0.0230 (8) | 0.0168 (8) | 0.0210 (8) | −0.0002 (6) | −0.0073 (7) | −0.0026 (6) |
C4 | 0.0420 (11) | 0.0203 (9) | 0.0313 (10) | −0.0068 (8) | −0.0102 (9) | −0.0059 (7) |
C5 | 0.0261 (8) | 0.0192 (8) | 0.0179 (8) | −0.0001 (6) | −0.0055 (7) | −0.0040 (6) |
C6 | 0.0512 (13) | 0.0297 (10) | 0.0173 (8) | −0.0049 (9) | 0.0006 (8) | −0.0077 (7) |
C7 | 0.0225 (8) | 0.0174 (7) | 0.0166 (7) | −0.0017 (6) | −0.0052 (6) | −0.0031 (6) |
C8 | 0.0231 (8) | 0.0182 (8) | 0.0190 (8) | −0.0026 (6) | −0.0038 (6) | −0.0040 (6) |
C9 | 0.0259 (8) | 0.0196 (8) | 0.0159 (7) | −0.0012 (6) | −0.0061 (6) | −0.0039 (6) |
O8 | 0.0581 (10) | 0.0410 (9) | 0.0516 (10) | 0.0106 (7) | −0.0325 (9) | −0.0276 (8) |
O7—H13 | 0.8497 | N1—H4 | 0.84 (3) |
O7—H12 | 0.8491 | C1—C2 | 1.518 (2) |
Co1—O1 | 2.0483 (18) | C2—C9 | 1.386 (3) |
Co1—O1i | 2.0483 (18) | C2—C3 | 1.389 (2) |
Co1—O6i | 2.0652 (19) | C3—C4 | 1.492 (3) |
Co1—O6 | 2.0652 (19) | C4—H2 | 0.9600 |
Co1—O5 | 2.1562 (19) | C4—H1 | 0.9600 |
Co1—O5i | 2.1562 (19) | C4—H3 | 0.9600 |
O1—C1 | 1.254 (2) | C5—C7 | 1.384 (2) |
O2—C1 | 1.235 (3) | C5—C6 | 1.498 (3) |
O3—C8 | 1.263 (2) | C6—H6 | 0.9600 |
O4—C8 | 1.238 (2) | C6—H7 | 0.9600 |
O6—H11 | 0.8500 | C6—H5 | 0.9600 |
O6—H10 | 0.8500 | C7—C9 | 1.398 (2) |
O5—H8 | 0.8499 | C7—C8 | 1.516 (3) |
O5—H9 | 0.8500 | C9—H16 | 0.9300 |
N1—C5 | 1.350 (2) | O8—H14 | 0.8499 |
N1—C3 | 1.351 (2) | O8—H15 | 0.8501 |
H13—O7—H12 | 101.1 | C9—C2—C1 | 119.22 (15) |
O1—Co1—O1i | 180.00 (8) | C3—C2—C1 | 122.83 (16) |
O1—Co1—O6i | 90.73 (7) | N1—C3—C2 | 117.51 (16) |
O1i—Co1—O6i | 89.28 (7) | N1—C3—C4 | 115.52 (16) |
O1—Co1—O6 | 89.27 (7) | C2—C3—C4 | 126.97 (17) |
O1i—Co1—O6 | 90.73 (7) | C3—C4—H2 | 109.5 |
O6i—Co1—O6 | 180.00 (8) | C3—C4—H1 | 109.5 |
O1—Co1—O5 | 91.39 (8) | H2—C4—H1 | 109.5 |
O1i—Co1—O5 | 88.61 (8) | C3—C4—H3 | 109.5 |
O6i—Co1—O5 | 88.52 (7) | H2—C4—H3 | 109.5 |
O6—Co1—O5 | 91.48 (7) | H1—C4—H3 | 109.5 |
O1—Co1—O5i | 88.61 (8) | N1—C5—C7 | 117.54 (16) |
O1i—Co1—O5i | 91.39 (8) | N1—C5—C6 | 115.12 (16) |
O6i—Co1—O5i | 91.48 (7) | C7—C5—C6 | 127.28 (17) |
O6—Co1—O5i | 88.52 (7) | C5—C6—H6 | 109.5 |
O5—Co1—O5i | 180.0 | C5—C6—H7 | 109.5 |
C1—O1—Co1 | 131.02 (13) | H6—C6—H7 | 109.5 |
Co1—O6—H11 | 117.8 | C5—C6—H5 | 109.5 |
Co1—O6—H10 | 124.3 | H6—C6—H5 | 109.5 |
H11—O6—H10 | 116.9 | H7—C6—H5 | 109.5 |
Co1—O5—H8 | 101.7 | C5—C7—C9 | 117.86 (16) |
Co1—O5—H9 | 109.8 | C5—C7—C8 | 123.42 (15) |
H8—O5—H9 | 108.2 | C9—C7—C8 | 118.72 (15) |
C5—N1—C3 | 126.27 (16) | O4—C8—O3 | 124.96 (17) |
C5—N1—H4 | 118.0 (17) | O4—C8—C7 | 117.14 (16) |
C3—N1—H4 | 115.7 (17) | O3—C8—C7 | 117.87 (16) |
O2—C1—O1 | 127.22 (17) | C2—C9—C7 | 122.72 (16) |
O2—C1—C2 | 117.17 (17) | C2—C9—H16 | 118.6 |
O1—C1—C2 | 115.59 (16) | C7—C9—H16 | 118.6 |
C9—C2—C3 | 117.92 (16) | H14—O8—H15 | 107.8 |
Symmetry code: (i) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O8 | 0.84 (3) | 1.89 (3) | 2.726 (3) | 175 (2) |
O5—H8···O2 | 0.85 | 1.91 | 2.712 (3) | 156 |
O5—H9···O7i | 0.85 | 1.92 | 2.769 (3) | 179 |
O6—H11···O3ii | 0.85 | 1.91 | 2.740 (2) | 165 |
O6—H10···O3iii | 0.85 | 1.92 | 2.743 (2) | 163 |
O7—H13···O4iv | 0.85 | 1.97 | 2.814 (3) | 171 |
O7—H12···O4ii | 0.85 | 2.05 | 2.862 (3) | 160 |
O8—H14···O3iv | 0.85 | 2.08 | 2.914 (3) | 165 |
O8—H15···O5v | 0.85 | 2.02 | 2.861 (3) | 171 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y, −z+1; (iii) x, y+1, z−1; (iv) x, y+1, z; (v) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co(C9H8NO4)2(H2O)4]·4H2O |
Mr | 591.39 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 7.597 (5), 8.651 (7), 10.715 (7) |
α, β, γ (°) | 69.90 (3), 69.75 (2), 83.58 (2) |
V (Å3) | 620.4 (8) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.77 |
Crystal size (mm) | 0.48 × 0.39 × 0.31 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.706, 0.794 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6106, 2803, 2631 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.100, 1.21 |
No. of reflections | 2803 |
No. of parameters | 175 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.46, −0.30 |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O8 | 0.84 (3) | 1.89 (3) | 2.726 (3) | 175 (2) |
O5—H8···O2 | 0.85 | 1.91 | 2.712 (3) | 156.4 |
O5—H9···O7i | 0.85 | 1.92 | 2.769 (3) | 178.6 |
O6—H11···O3ii | 0.85 | 1.91 | 2.740 (2) | 165.0 |
O6—H10···O3iii | 0.85 | 1.92 | 2.743 (2) | 163.2 |
O7—H13···O4iv | 0.85 | 1.97 | 2.814 (3) | 170.7 |
O7—H12···O4ii | 0.85 | 2.05 | 2.862 (3) | 160.3 |
O8—H14···O3iv | 0.85 | 2.08 | 2.914 (3) | 165.1 |
O8—H15···O5v | 0.85 | 2.02 | 2.861 (3) | 170.6 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y, −z+1; (iii) x, y+1, z−1; (iv) x, y+1, z; (v) x, y, z+1. |
Recently, we reported the crystal structure of trans-tetraaqua-bis(2,6-dimethylpyridinium-3,5-dicarboxylato) copper(II) tetrahydrate (Shi et al. 2007). The title cobalt analog (Fig. 1) is centrosymmetric, and the metal exists in an octahedral coordination geometry. Molecules are linked by O—H···O and N—H···O hydrogen bonds involving allpotential donors to generate infinite three-dimensional network. (Table 1; Fig. 2). The two compounds are not isostructural although both have the same formula.