Acta Cryst. (2007). E63, m2605 [ doi:10.1107/S1600536807046314 ]
![[mu]](/logos/entities/mu_rmgif.gif)
2-4-pyridinecarboxylato-![[kappa]](/logos/entities/kappa_rmgif.gif)
3N:O,O')cobalt(II)]: a triply interpenetrated structure with diamonoid topologyThe binary title complex, [Co(C6H4NO2)2]n, is a three-dimensional coordination polymer that is triply interpenetrated with diamonoid topology. The asymmetric unit comprises half a Co atom, which lies on a twofold axis, and a 4-pyridinecarboxylate anion, in a general position. The Co atom is in a distorted cis-N2O4 octahedral geometry defined by two chelating carboxylate groups and two pyridyl N atoms.
To a ethanol-water solution (2:1 v:v, 10 ml) of Co(NO3)2·6H2O (0.146 g, 0.5 mmol) and Gd(NO3)3·6H2O (0.226 g, 0.5 mmol), a solution of 4-pyridinecarboxylic acid (0.123 g, 1.0 mmol) in EtOH (5 ml) was added slowly with stirring over 30 min at 333 K. This solution was transferred into a sealed 23-ml Teflon-lined stainless container and heated to 160 °C for 3 days. After slow cooling to room temperature over 8 h, red crystals of (I) separated from the solution (yield 75%).
All the H atoms were included in the riding-model approximation, with C–H = 0.93 Å, and with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXTL (Bruker, 1998).
![[Figure 1]](./tk2191fig1thm.gif)
| Fig. 1. Molecular structure of (I) extended to show the octahedral coordination geometry for the Co atom and the atom-labeling scheme. Displacement ellipsoids are shown at the 50% probability level. [Symmetry codes: (a) x − 1/2, −y + 1/2, −z − 3/4; (b) −y + 1/2, x − 1/2, z + 3/4; (c) y, x, −z; (d) y + 1/2, −x + 1/2, z − 3/4.] |
![[Figure 2]](./tk2191fig2thm.gif)
| Fig. 2. Plot of a single diamonoid network in (I) viewed along the a axis. |
| [Co(C6H4NO2)2] | Z = 4 |
| Mr = 303.13 | F000 = 612 |
| Tetragonal, P43212 | Dx = 1.698 Mg m−3 |
| Hall symbol: P 4nw 2abw | Mo Kα radiation λ = 0.71073 Å |
| a = 11.6304 (7) Å | Cell parameters from 1288 reflections |
| b = 11.6304 (7) Å | θ = 2.5–27.5º |
| c = 8.7665 (10) Å | µ = 1.46 mm−1 |
| α = 90º | T = 293 (2) K |
| β = 90º | Block, red |
| γ = 90º | 0.21 × 0.15 × 0.07 mm |
| V = 1185.81 (17) Å3 |
| Bruker SMART CCD area-detector diffractometer | 1288 independent reflections |
| Radiation source: fine-focus sealed tube | 1219 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.027 |
| T = 293(2) K | θmax = 27.5º |
| φ and ω scans | θmin = 2.5º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −10→14 |
| Tmin = 0.749, Tmax = 0.905 | k = −14→14 |
| 4769 measured reflections | l = −11→4 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.027 | w = 1/[σ2(Fo2) + (0.033P)2 + 0.0513P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.063 | (Δ/σ)max < 0.001 |
| S = 1.11 | Δρmax = 0.39 e Å−3 |
| 1288 reflections | Δρmin = −0.24 e Å−3 |
| 87 parameters | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods | Absolute structure: (Flack, 1983) |
| Secondary atom site location: difference Fourier map | Flack parameter: −0.03 (2) |
| [Co(C6H4NO2)2] | γ = 90º |
| Mr = 303.13 | V = 1185.81 (17) Å3 |
| Tetragonal, P43212 | Z = 4 |
| a = 11.6304 (7) Å | Mo Kα |
| b = 11.6304 (7) Å | µ = 1.46 mm−1 |
| c = 8.7665 (10) Å | T = 293 (2) K |
| α = 90º | 0.21 × 0.15 × 0.07 mm |
| β = 90º |
| Bruker SMART CCD area-detector diffractometer | 1288 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 1219 reflections with I > 2σ(I) |
| Tmin = 0.749, Tmax = 0.905 | Rint = 0.027 |
| 4769 measured reflections |
| R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
| wR(F2) = 0.063 | Δρmax = 0.39 e Å−3 |
| S = 1.11 | Δρmin = −0.24 e Å−3 |
| 1288 reflections | Absolute structure: (Flack, 1983) |
| 87 parameters | Flack parameter: −0.03 (2) |
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 | ||
| Co1 | 0.27729 (2) | 0.27729 (2) | 0.0000 | 0.02511 (13) | |
| O1 | 0.39522 (15) | 0.18731 (17) | −0.13866 (18) | 0.0475 (5) | |
| O2 | 0.37226 (15) | 0.37088 (16) | −0.18249 (19) | 0.0457 (4) | |
| N1 | 0.64350 (14) | 0.24467 (16) | −0.59662 (19) | 0.0299 (4) | |
| C1 | 0.5913 (2) | 0.15229 (19) | −0.5376 (2) | 0.0369 (5) | |
| H1 | 0.6066 | 0.0806 | −0.5799 | 0.044* | |
| C2 | 0.5157 (2) | 0.1592 (2) | −0.4165 (3) | 0.0370 (5) | |
| H2 | 0.4812 | 0.0932 | −0.3779 | 0.044* | |
| C3 | 0.49211 (18) | 0.2652 (2) | −0.3537 (2) | 0.0315 (5) | |
| C4 | 0.5420 (2) | 0.36043 (19) | −0.4179 (3) | 0.0354 (5) | |
| H4 | 0.5257 | 0.4334 | −0.3802 | 0.042* | |
| C5 | 0.61669 (19) | 0.34707 (18) | −0.5389 (2) | 0.0331 (5) | |
| H5 | 0.6497 | 0.4123 | −0.5819 | 0.040* | |
| C6 | 0.41504 (18) | 0.2756 (2) | −0.2161 (2) | 0.0352 (5) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co1 | 0.02932 (16) | 0.02932 (16) | 0.01668 (18) | −0.00108 (16) | 0.00053 (11) | −0.00053 (11) |
| O1 | 0.0495 (10) | 0.0624 (12) | 0.0305 (8) | 0.0157 (9) | 0.0138 (8) | 0.0114 (9) |
| O2 | 0.0435 (11) | 0.0472 (11) | 0.0464 (9) | −0.0054 (7) | 0.0189 (8) | −0.0158 (9) |
| N1 | 0.0315 (9) | 0.0357 (10) | 0.0225 (8) | −0.0011 (7) | 0.0037 (7) | 0.0011 (7) |
| C1 | 0.0467 (14) | 0.0288 (12) | 0.0352 (12) | 0.0008 (10) | 0.0074 (11) | −0.0039 (10) |
| C2 | 0.0431 (13) | 0.0349 (13) | 0.0330 (11) | −0.0033 (11) | 0.0104 (11) | 0.0013 (10) |
| C3 | 0.0298 (11) | 0.0408 (13) | 0.0238 (9) | 0.0012 (10) | 0.0026 (9) | 0.0011 (10) |
| C4 | 0.0412 (13) | 0.0354 (13) | 0.0294 (11) | 0.0055 (10) | 0.0035 (10) | −0.0063 (10) |
| C5 | 0.0414 (13) | 0.0292 (11) | 0.0288 (11) | −0.0013 (9) | 0.0057 (9) | 0.0034 (9) |
| C6 | 0.0291 (11) | 0.0529 (14) | 0.0235 (10) | −0.0028 (11) | 0.0005 (8) | −0.0043 (11) |
| Co1—N1i | 2.0723 (16) | N1—Co1iv | 2.0723 (16) |
| Co1—N1ii | 2.0723 (16) | C1—C2 | 1.381 (3) |
| Co1—O1iii | 2.1104 (16) | C1—H1 | 0.9300 |
| Co1—O1 | 2.1104 (16) | C2—C3 | 1.377 (3) |
| Co1—O2iii | 2.2279 (16) | C2—H2 | 0.9300 |
| Co1—O2 | 2.2279 (16) | C3—C4 | 1.372 (3) |
| O1—C6 | 1.253 (3) | C3—C6 | 1.508 (3) |
| O2—C6 | 1.250 (3) | C4—C5 | 1.379 (3) |
| N1—C5 | 1.331 (3) | C4—H4 | 0.9300 |
| N1—C1 | 1.338 (3) | C5—H5 | 0.9300 |
| N1i—Co1—N1ii | 103.65 (10) | C1—N1—Co1iv | 119.51 (15) |
| N1i—Co1—O1iii | 94.67 (7) | N1—C1—C2 | 122.6 (2) |
| N1ii—Co1—O1iii | 93.05 (7) | N1—C1—H1 | 118.7 |
| N1i—Co1—O1 | 93.05 (7) | C2—C1—H1 | 118.7 |
| N1ii—Co1—O1 | 94.67 (7) | C3—C2—C1 | 119.1 (2) |
| O1iii—Co1—O1 | 167.50 (11) | C3—C2—H2 | 120.5 |
| N1i—Co1—O2iii | 153.36 (7) | C1—C2—H2 | 120.5 |
| N1ii—Co1—O2iii | 88.08 (6) | C4—C3—C2 | 118.33 (19) |
| O1iii—Co1—O2iii | 60.43 (7) | C4—C3—C6 | 121.0 (2) |
| O1—Co1—O2iii | 109.99 (7) | C2—C3—C6 | 120.7 (2) |
| N1i—Co1—O2 | 88.08 (6) | C3—C4—C5 | 119.4 (2) |
| N1ii—Co1—O2 | 153.36 (7) | C3—C4—H4 | 120.3 |
| O1iii—Co1—O2 | 109.99 (7) | C5—C4—H4 | 120.3 |
| O1—Co1—O2 | 60.43 (7) | N1—C5—C4 | 122.7 (2) |
| O2iii—Co1—O2 | 91.79 (8) | N1—C5—H5 | 118.6 |
| C6—O1—Co1 | 91.44 (14) | C4—C5—H5 | 118.6 |
| C6—O2—Co1 | 86.20 (13) | O2—C6—O1 | 121.71 (19) |
| C5—N1—C1 | 117.73 (18) | O2—C6—C3 | 119.8 (2) |
| C5—N1—Co1iv | 122.20 (14) | O1—C6—C3 | 118.5 (2) |
| Symmetry codes: (i) x−1/2, −y+1/2, −z−3/4; (ii) −y+1/2, x−1/2, z+3/4; (iii) y, x, −z; (iv) y+1/2, −x+1/2, z−3/4. |
Bruker (1998). SMART (Version 5.0) and SHELXTL (Version 5.1). Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (1999). SAINT. Version 6.0. Bruker AXS Inc., Madison, Wisconsin, USA.
Evans, O. R., Xiong, R.-G., Wang, Z., Wong, G. K. & Lin, W. (1999). Angew. Chem. Int. Ed. 38, 536–538.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
Lu, J. Y. (2003). Coord. Chem. Rev. 246, 327–347.
MacGillivray, L. R., Groeneman, R. H. & Atwood, J. L. (1998). J. Am. Chem. Soc. 120, 2676–2677.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.
Sheldrick, G. M. (2002). SADABS. University of Göttingen, Germany.
Tong, M.-L., Chen, X.-M. & Batten, S. R. (2003). J. Am. Chem. Soc. 125, 16170–16171.
Tong, M.-L., Li, L.-J., Mochizuki, K., Chang, H.-C., Chen, X.-M., Li, Y. & Kitagawa, S. (2003). Chem. Commun. pp. 428–429.
Wang, R., Hong, M., Luo, J., Cao, R. & Weng, J. (2003). Chem. Commun. pp. 1018–1019.
Wei, Q., Nieuwenhuyzen, M., Meunier, F., Hardacre, C. & James, S. L. (2004). Dalton Trans. pp. 1807–1811.
Pyridinecarboxylates and their derivatives are good bridging ligands in the construction of 2- and 3-D functional metal-organic frameworks (Evans et al., 1999; Lu, 2003; Tong, Chen & Batten, 2003; Tong, Li et al., 2003; Wang et al., 2003). The title complex, (I), was obtained unexpectedly in an attempt to prepare a bimetallic coordination network (see Experimental) with 4-pyridinecarboxylate (4-pya).
The structure of (I) is a three-dimensional coordination network. The Co(II) atom, which is located on a 2-fold axis (Fig. 1), is coordinated by four O atoms derived from two chelating carboxylate ligands and two pyridine-N atoms that define a distorted octahedral geometry within a cis-N2O4 donor set. The major distortion from the ideal octahedral geometry is caused by the acute chelate angle of 60.43 (7)° for O1—Co—O2.
The Co—N bond length [2.0723 (16) Å] is slightly shorter than those of 2.133 (3) Å, found in [Co(4-pya)2]·0.5EtOH (Wei et al., 2004), and 2.166 (4) Å, found in [Co(4,4-bipyridine)(4-pya)(H2O)]NO3.4,4'-bipyridine·1.5H2O (MacGillivray et al., 1998). By contrast, the Co—O bond distances of 2.1104 (16) and 2.2279 (16) Å are longer than those of 2.082 (4)–2.098 (4) Å formed by the 4-pya ligands in poly[tetrakis(µ3-4-pya)dicobalt(II)] (Wei et al., 2004).
In the crystal structure, the polymeric chains are triply interpenetrated with a diamonoid topology (Fig. 2). This resembles the situation in [Zn(4-pya)2]n (Evans et al., 1999) but, the structures are not isomorphous.