Acta Cryst. (2008). E64, m77 [ doi:10.1107/S1600536807063258 ]
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2N,O)cobalt(II) dichlorideIn the title salt, [Co(C5H4N2O2)2(H2O)2]Cl2, the CoII ion is located on an inversion center. It is chelated by two neutral pyrimidine-2-carboxylic acid molecules and is coordinated by two water molecules in an octahedral coordination geometry. The cations and anions are linked via O-H
Cl hydrogen bonds into a layer structure; an intramolecular O-HN hydrogen bond connects the carboxylic acid group to the pyrimidine N atom.
2-Cyanopyrimidine (0.19 g, 1.8 mmol), CoCl2.6(H2O) (0.24 g, 1 mmol) were dissolved in a mixture solution of water (15 ml) and ethanol (5 ml), then hydrochloric acid solution (3 ml, 37%) was added into the solution. The solution was refluxed for 5 h. Single crystals of the title compound were obtained after about one month.
Hydroxy and water H atoms were located in a difference Fourier map and refined as riding in as-found relative positions, with Uiso(H) = 1.5Ueq(O). Other H atoms were placed in calculated positions with C—H = 0.93 Å and refined in riding mode with Uiso(H) = 1.2Ueq(C).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./ng2402fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with 30% probability displacement (arbitrary spheres for H atoms), dashed lines indicate hydrogen bonding [symmetry codes: (i) 1 - x,1 - y,1 - z]. |
| [Co(C5H4N2O2)2(H2O)2]Cl2 | F000 = 418 |
| Mr = 414.07 | Dx = 1.782 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 2668 reflections |
| a = 6.2803 (8) Å | θ = 3.5–24.5º |
| b = 10.361 (2) Å | µ = 1.49 mm−1 |
| c = 11.906 (2) Å | T = 293 (2) K |
| β = 95.254 (15)º | Prism, pink |
| V = 771.5 (2) Å3 | 0.25 × 0.12 × 0.10 mm |
| Z = 2 |
| Rigaku R-AXIS RAPID IP diffractometer | 1763 independent reflections |
| Radiation source: fine-focus sealed tube | 1178 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.052 |
| Detector resolution: 10.0 pixels mm-1 | θmax = 27.4º |
| T = 291(2) K | θmin = 3.4º |
| ω scans | h = −8→8 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −12→13 |
| Tmin = 0.726, Tmax = 0.862 | l = −15→15 |
| 7413 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
| wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0359P)2 + 1.9784P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.12 | (Δ/σ)max < 0.001 |
| 1763 reflections | Δρmax = 0.70 e Å−3 |
| 107 parameters | Δρmin = −0.72 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Co(C5H4N2O2)2(H2O)2]Cl2 | V = 771.5 (2) Å3 |
| Mr = 414.07 | Z = 2 |
| Monoclinic, P21/n | Mo Kα |
| a = 6.2803 (8) Å | µ = 1.49 mm−1 |
| b = 10.361 (2) Å | T = 293 (2) K |
| c = 11.906 (2) Å | 0.25 × 0.12 × 0.10 mm |
| β = 95.254 (15)º |
| Rigaku R-AXIS RAPID IP diffractometer | 1763 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1178 reflections with I > 2σ(I) |
| Tmin = 0.726, Tmax = 0.862 | Rint = 0.052 |
| 7413 measured reflections |
| R[F2 > 2σ(F2)] = 0.040 | 107 parameters |
| wR(F2) = 0.119 | H-atom parameters constrained |
| S = 1.12 | Δρmax = 0.70 e Å−3 |
| 1763 reflections | Δρmin = −0.72 e Å−3 |
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 | 0.5000 | 0.5000 | 0.5000 | 0.0257 (2) | |
| Cl1 | 0.83609 (17) | 0.85016 (10) | 0.65401 (9) | 0.0367 (3) | |
| N1 | 0.6455 (5) | 0.6498 (3) | 0.4186 (3) | 0.0250 (7) | |
| N2 | 0.5891 (6) | 0.8696 (3) | 0.3695 (3) | 0.0340 (8) | |
| O1 | 0.3012 (4) | 0.6537 (3) | 0.5310 (2) | 0.0329 (7) | |
| O2 | 0.2425 (6) | 0.8657 (3) | 0.4995 (3) | 0.0541 (9) | |
| H2 | 0.2993 | 0.9247 | 0.4674 | 0.081* | |
| O3 | 0.7051 (5) | 0.5443 (3) | 0.6466 (3) | 0.0397 (7) | |
| H3A | 0.7018 | 0.4951 | 0.7142 | 0.060* | |
| H3B | 0.7642 | 0.6288 | 0.6649 | 0.060* | |
| C1 | 0.3501 (6) | 0.7589 (3) | 0.4885 (3) | 0.0268 (8) | |
| C2 | 0.5395 (6) | 0.7618 (4) | 0.4203 (3) | 0.0258 (8) | |
| C3 | 0.7628 (8) | 0.8641 (5) | 0.3124 (4) | 0.0415 (11) | |
| H3 | 0.8027 | 0.9374 | 0.2746 | 0.050* | |
| C4 | 0.8852 (7) | 0.7540 (4) | 0.3075 (4) | 0.0381 (10) | |
| H4 | 1.0058 | 0.7524 | 0.2677 | 0.046* | |
| C5 | 0.8217 (6) | 0.6467 (4) | 0.3637 (3) | 0.0323 (9) | |
| H5 | 0.9021 | 0.5713 | 0.3635 | 0.039* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co | 0.0300 (4) | 0.0184 (4) | 0.0294 (4) | 0.0009 (3) | 0.0068 (3) | 0.0022 (3) |
| Cl1 | 0.0399 (6) | 0.0365 (6) | 0.0339 (6) | −0.0014 (5) | 0.0045 (4) | −0.0036 (4) |
| N1 | 0.0274 (16) | 0.0192 (15) | 0.0289 (17) | −0.0015 (14) | 0.0056 (13) | −0.0003 (13) |
| N2 | 0.0376 (19) | 0.0261 (18) | 0.039 (2) | −0.0039 (16) | 0.0045 (16) | 0.0076 (15) |
| O1 | 0.0352 (15) | 0.0248 (14) | 0.0410 (17) | 0.0033 (13) | 0.0157 (13) | 0.0007 (13) |
| O2 | 0.058 (2) | 0.0387 (19) | 0.067 (3) | 0.0051 (18) | 0.0102 (19) | −0.0011 (18) |
| O3 | 0.0529 (19) | 0.0332 (16) | 0.0317 (16) | −0.0045 (15) | −0.0028 (14) | 0.0010 (13) |
| C1 | 0.030 (2) | 0.0167 (17) | 0.034 (2) | 0.0004 (16) | 0.0038 (17) | −0.0033 (16) |
| C2 | 0.031 (2) | 0.0210 (18) | 0.025 (2) | −0.0024 (17) | 0.0017 (16) | 0.0000 (15) |
| C3 | 0.047 (3) | 0.037 (2) | 0.041 (3) | −0.010 (2) | 0.007 (2) | 0.014 (2) |
| C4 | 0.037 (2) | 0.042 (3) | 0.037 (2) | −0.007 (2) | 0.0124 (19) | 0.005 (2) |
| C5 | 0.028 (2) | 0.036 (2) | 0.033 (2) | 0.0004 (19) | 0.0047 (17) | −0.0040 (18) |
| Co—O1 | 2.077 (3) | O2—C1 | 1.309 (5) |
| Co—O1i | 2.077 (3) | O2—H2 | 0.8200 |
| Co—O3i | 2.123 (3) | O3—H3A | 0.9545 |
| Co—O3 | 2.123 (3) | O3—H3B | 0.9674 |
| Co—N1i | 2.085 (3) | C1—C2 | 1.501 (5) |
| Co—N1 | 2.085 (3) | C3—C4 | 1.379 (7) |
| N1—C5 | 1.337 (5) | C3—H3 | 0.9300 |
| N1—C2 | 1.338 (5) | C4—C5 | 1.375 (6) |
| N2—C2 | 1.321 (5) | C4—H4 | 0.9300 |
| N2—C3 | 1.338 (6) | C5—H5 | 0.9300 |
| O1—C1 | 1.252 (5) | ||
| O1—Co—O1i | 180.00 (16) | C1—O2—H2 | 109.5 |
| O1—Co—N1i | 101.08 (11) | Co—O3—H3A | 121.3 |
| O1i—Co—N1i | 78.92 (11) | Co—O3—H3B | 124.9 |
| O1—Co—N1 | 78.92 (11) | H3A—O3—H3B | 109.3 |
| O1i—Co—N1 | 101.08 (11) | O1—C1—O2 | 123.2 (4) |
| N1i—Co—N1 | 180.00 (11) | O1—C1—C2 | 118.2 (3) |
| O1—Co—O3i | 88.99 (12) | O2—C1—C2 | 118.6 (3) |
| O1i—Co—O3i | 91.01 (12) | N2—C2—N1 | 126.0 (4) |
| N1i—Co—O3i | 87.84 (12) | N2—C2—C1 | 119.7 (3) |
| N1—Co—O3i | 92.16 (12) | N1—C2—C1 | 114.3 (3) |
| O1—Co—O3 | 91.01 (12) | N2—C3—C4 | 122.7 (4) |
| O1i—Co—O3 | 88.99 (12) | N2—C3—H3 | 118.6 |
| N1i—Co—O3 | 92.16 (12) | C4—C3—H3 | 118.6 |
| N1—Co—O3 | 87.84 (12) | C5—C4—C3 | 117.4 (4) |
| O3i—Co—O3 | 180.000 (1) | C5—C4—H4 | 121.3 |
| C5—N1—C2 | 117.6 (3) | C3—C4—H4 | 121.3 |
| C5—N1—Co | 128.8 (3) | N1—C5—C4 | 120.5 (4) |
| C2—N1—Co | 113.5 (2) | N1—C5—H5 | 119.7 |
| C2—N2—C3 | 115.7 (4) | C4—C5—H5 | 119.7 |
| C1—O1—Co | 115.0 (2) |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···N2 | 0.82 | 2.32 | 2.784 (5) | 116 |
| O3—H3A···Cl1ii | 0.95 | 2.20 | 3.140 (4) | 168 |
| O3—H3B···Cl1 | 0.97 | 2.34 | 3.273 (3) | 161 |
| C4—H4···Cl1iii | 0.93 | 2.79 | 3.670 (5) | 159 |
| Symmetry codes: (ii) −x+3/2, y−1/2, −z+3/2; (iii) x+1/2, −y+3/2, z−1/2. |
| Co—O1 | 2.077 (3) | O1—C1 | 1.252 (5) |
| Co—O3 | 2.123 (3) | O2—C1 | 1.309 (5) |
| Co—N1 | 2.085 (3) | ||
| O1—Co—N1 | 78.92 (11) | N1—Co—O3 | 87.84 (12) |
| O1—Co—O3 | 91.01 (12) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···N2 | 0.82 | 2.32 | 2.784 (5) | 116 |
| O3—H3A···Cl1i | 0.95 | 2.20 | 3.140 (4) | 168 |
| O3—H3B···Cl1 | 0.97 | 2.34 | 3.273 (3) | 161 |
| Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2. |
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As part of our ongoing investigation on the nature of aromatic stacking (Cheng et al., 2000; Wu et al., 2003), the title CoII compound has recently been prepared and its crystal structure is presented here.
The molecular structure of the title compound is shown in Fig. 1. The crystal of the title compound consists of complex cations and Cl- anions. The CoII located on an inversion center is coordinated by two neutral pyrimidine-2-carboxylic acid and two water molecules with an octahedral geometry (Table 1). The Cl- anions link with the complex cations via O—H···Cl hydrogen bonding (Table 2 and Fig. 1). The charge balance indicates that the pyrimidine-2-carboxylic acid is a neutral ligand but not an anion; and the significant difference in C—O bond distances (Table 1) also suggests that the carboxyl group is not deprotonated. This is obviously owing to the acidified solution environment in the preparation of the compound (see _publ_section_exptl_prep). The intra-molecular O—H···N hydrogen bonding exsits between the carboxyl group and adjacent pyrimidine-N atom (Fig. 1). Thus the pyrimidine-2-carboxylic acid can not play a role of bridge ligand in this structure, contrast to that found in pyrimidine-2-carboxylate complex of Co(II) reported previously (Rodriquez-Dieguez et al., 2007).
π-π stacking is not observed in this crystal structure, which is different from the situation in a related CuII complex with pyrimidine-2-carboxylate (Zhang et al., 2008). It may be due to extensive hydrogen bonding network involving coordinated water molecules and counter Cl- anions.