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accessDichloridobis[2-methylsulfanyl-4-(pyridin-2-yl)pyrimidine-κ2N3,N4]cobalt(II)
aSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
*Correspondence e-mail: yjs_seu@163.com
The of the title compound, [CoCl2(C10H9N3S)2], contains one half-molecule with the CoII atom situtated on a twofold rotational axis. The CoII atom, in an octahedral enviroment, is coordinated by four N atoms from two 2-methylsulfanyl-4-(pyridin-2-yl)pyrimidine ligands and two Cl atoms.
Related literature
For coordination compounds derived from the prototypical ligands 4-(pyridin-n-yl)pyrimidine-2-thiol (n = 2, 3, 4) and their S-modified derivatives reported by our group, see: Huang et al. (2007![[Huang, C. H., Gou, S. H., Zhu, H. B. & Huang, W. (2007). Inorg. Chem. 46, 5537-5543.]](../../../../../../logos/arrows/e_arr.gif "Huang, C. H., Gou, S. H., Zhu, H. B. & Huang, W. (2007). Inorg. Chem. 46, 5537-5543.")
); Dong et al. (2009); Zhu et al. (2009).
![[Scheme 1]](vm2113scheme1.gif)
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2007); cell SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536811030881/vm2113sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536811030881/vm2113Isup2.hkl
The mixture of CoCl2 (0.1 mmol) and L (0.2 mmol) in 10 ml of ethanol was stirred for 20 min at room temperature. After filtration, the mother solution was allowed to stand for one week to give blue crystals suitable for X-ray diffraction analysis.
All H atoms bounded to C atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93Å (CH) and Uiso(H) = 1.2Ueq(C), C—H = 0.97Å (CH3) and Uiso(H) = 1.5Ueq(C).
Data collection: APEX2 (Bruker, 2007); cell SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./vm2113fig1thm.gif) | Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level; Atoms labeled with flag A are generated by symmetry operation -x + 1, y, -z + 1/2. |
| [CoCl2(C10H9N3S)2] | F(000) = 1092 |
| Mr = 536.37 | Dx = 1.598 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2588 reflections |
| a = 8.709 (11) Å | θ = 2.3–25.5° |
| b = 17.10 (2) Å | µ = 1.22 mm−1 |
| c = 15.328 (19) Å | T = 298 K |
| β = 102.34 (3)° | Block, blue |
| V = 2230 (5) Å3 | 0.35 × 0.28 × 0.24 mm |
| Z = 4 |
| Bruker APEXII CCD area-detector diffractometer | 2586 independent reflections |
| Radiation source: fine-focus sealed tube | 1636 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.052 |
| ϕ and ω scans | θmax = 28.4°, θmin = 2.7° |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −11→9 |
| Tmin = 0.671, Tmax = 0.747 | k = −21→17 |
| 6138 measured reflections | l = −14→20 |
| 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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.060 | H-atom parameters constrained |
| S = 0.93 | w = 1/[σ2(Fo2) + (0.0104P)2] where P = (Fo2 + 2Fc2)/3 |
| 2586 reflections | (Δ/σ)max < 0.001 |
| 141 parameters | Δρmax = 0.33 e Å−3 |
| 0 restraints | Δρmin = −0.50 e Å−3 |
| [CoCl2(C10H9N3S)2] | V = 2230 (5) Å3 |
| Mr = 536.37 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 8.709 (11) Å | µ = 1.22 mm−1 |
| b = 17.10 (2) Å | T = 298 K |
| c = 15.328 (19) Å | 0.35 × 0.28 × 0.24 mm |
| β = 102.34 (3)° |
| Bruker APEXII CCD area-detector diffractometer | 2586 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1636 reflections with I > 2σ(I) |
| Tmin = 0.671, Tmax = 0.747 | Rint = 0.052 |
| 6138 measured reflections |
| R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
| wR(F2) = 0.060 | H-atom parameters constrained |
| S = 0.93 | Δρmax = 0.33 e Å−3 |
| 2586 reflections | Δρmin = −0.50 e Å−3 |
| 141 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 | ||
| Co1 | 0.5000 | 0.29835 (3) | 0.2500 | 0.02888 (15) | |
| Cl1 | 0.56198 (8) | 0.38235 (4) | 0.13403 (4) | 0.0435 (2) | |
| S1 | 0.76922 (8) | 0.15867 (5) | 0.18274 (4) | 0.0419 (2) | |
| N2 | 0.4663 (2) | 0.19418 (12) | 0.15296 (11) | 0.0274 (5) | |
| N1 | 0.2595 (2) | 0.30314 (13) | 0.17840 (12) | 0.0309 (5) | |
| C6 | 0.3142 (3) | 0.18317 (15) | 0.10981 (14) | 0.0279 (6) | |
| C9 | 0.5705 (3) | 0.13805 (16) | 0.13928 (15) | 0.0314 (7) | |
| C5 | 0.2020 (3) | 0.24704 (16) | 0.11833 (14) | 0.0288 (6) | |
| C7 | 0.2671 (3) | 0.11737 (17) | 0.05868 (16) | 0.0389 (7) | |
| H7A | 0.1634 | 0.1105 | 0.0285 | 0.047* | |
| C1 | 0.1648 (3) | 0.36330 (17) | 0.18607 (16) | 0.0381 (7) | |
| H1A | 0.2041 | 0.4035 | 0.2255 | 0.046* | |
| N3 | 0.5331 (3) | 0.07212 (14) | 0.09342 (13) | 0.0402 (6) | |
| C2 | 0.0109 (3) | 0.36861 (17) | 0.13814 (17) | 0.0422 (8) | |
| H2A | −0.0516 | 0.4109 | 0.1463 | 0.051* | |
| C8 | 0.3816 (3) | 0.06227 (17) | 0.05450 (17) | 0.0440 (8) | |
| H8A | 0.3519 | 0.0162 | 0.0232 | 0.053* | |
| C4 | 0.0501 (3) | 0.24955 (17) | 0.06704 (15) | 0.0364 (7) | |
| H4A | 0.0145 | 0.2105 | 0.0254 | 0.044* | |
| C10 | 0.8661 (3) | 0.07695 (18) | 0.14226 (19) | 0.0572 (9) | |
| H10A | 0.9779 | 0.0822 | 0.1622 | 0.086* | |
| H10B | 0.8396 | 0.0762 | 0.0782 | 0.086* | |
| H10C | 0.8323 | 0.0291 | 0.1649 | 0.086* | |
| C3 | −0.0481 (3) | 0.31061 (18) | 0.07843 (17) | 0.0424 (8) | |
| H3B | −0.1516 | 0.3123 | 0.0464 | 0.051* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co1 | 0.0301 (3) | 0.0267 (3) | 0.0278 (2) | 0.000 | 0.0016 (2) | 0.000 |
| Cl1 | 0.0447 (5) | 0.0451 (5) | 0.0379 (4) | −0.0040 (4) | 0.0027 (3) | 0.0098 (3) |
| S1 | 0.0323 (4) | 0.0441 (6) | 0.0470 (4) | 0.0022 (4) | 0.0030 (4) | −0.0135 (3) |
| N2 | 0.0295 (13) | 0.0292 (14) | 0.0223 (9) | 0.0010 (11) | 0.0029 (10) | 0.0001 (9) |
| N1 | 0.0313 (13) | 0.0318 (15) | 0.0296 (10) | 0.0039 (12) | 0.0069 (10) | 0.0007 (10) |
| C6 | 0.0299 (16) | 0.0316 (18) | 0.0211 (11) | −0.0022 (13) | 0.0029 (12) | −0.0015 (11) |
| C9 | 0.0344 (16) | 0.0310 (19) | 0.0278 (12) | 0.0009 (14) | 0.0046 (12) | 0.0004 (11) |
| C5 | 0.0316 (16) | 0.0309 (17) | 0.0233 (12) | −0.0039 (14) | 0.0044 (12) | 0.0029 (11) |
| C7 | 0.0306 (16) | 0.045 (2) | 0.0376 (15) | −0.0031 (16) | −0.0006 (13) | −0.0075 (13) |
| C1 | 0.0410 (18) | 0.037 (2) | 0.0349 (14) | 0.0062 (16) | 0.0057 (14) | −0.0009 (12) |
| N3 | 0.0412 (16) | 0.0333 (17) | 0.0426 (13) | 0.0021 (13) | 0.0015 (12) | −0.0111 (11) |
| C2 | 0.0423 (19) | 0.047 (2) | 0.0384 (15) | 0.0148 (17) | 0.0102 (15) | 0.0071 (14) |
| C8 | 0.047 (2) | 0.033 (2) | 0.0492 (17) | −0.0070 (17) | 0.0031 (16) | −0.0157 (14) |
| C4 | 0.0339 (17) | 0.041 (2) | 0.0322 (14) | −0.0013 (15) | 0.0022 (13) | 0.0014 (13) |
| C10 | 0.0378 (19) | 0.059 (2) | 0.072 (2) | 0.0117 (18) | 0.0058 (16) | −0.0197 (17) |
| C3 | 0.0294 (16) | 0.055 (2) | 0.0398 (15) | 0.0046 (16) | 0.0017 (14) | 0.0122 (15) |
| Co1—N1i | 2.148 (3) | C5—C4 | 1.388 (4) |
| Co1—N1 | 2.148 (3) | C7—C8 | 1.383 (4) |
| Co1—N2 | 2.299 (3) | C7—H7A | 0.9300 |
| Co1—N2i | 2.299 (3) | C1—C2 | 1.387 (4) |
| Co1—Cl1i | 2.434 (2) | C1—H1A | 0.9300 |
| Co1—Cl1 | 2.434 (2) | N3—C8 | 1.337 (3) |
| S1—C9 | 1.752 (3) | C2—C3 | 1.373 (4) |
| S1—C10 | 1.810 (3) | C2—H2A | 0.9300 |
| N2—C6 | 1.361 (3) | C8—H8A | 0.9300 |
| N2—C9 | 1.368 (3) | C4—C3 | 1.384 (4) |
| N1—C5 | 1.350 (3) | C4—H4A | 0.9300 |
| N1—C1 | 1.340 (3) | C10—H10A | 0.9600 |
| C6—C7 | 1.382 (4) | C10—H10B | 0.9600 |
| C6—C5 | 1.490 (4) | C10—H10C | 0.9600 |
| C9—N3 | 1.332 (3) | C3—H3B | 0.9300 |
| N1i—Co1—N1 | 175.62 (12) | N1—C5—C4 | 122.3 (2) |
| N1i—Co1—N2 | 109.62 (8) | N1—C5—C6 | 115.2 (2) |
| N1—Co1—N2 | 73.94 (8) | C4—C5—C6 | 122.5 (2) |
| N1i—Co1—N2i | 73.94 (8) | C8—C7—C6 | 116.8 (3) |
| N1—Co1—N2i | 109.62 (8) | C8—C7—H7A | 121.6 |
| N2—Co1—N2i | 78.41 (14) | C6—C7—H7A | 121.6 |
| N1i—Co1—Cl1i | 87.05 (8) | N1—C1—C2 | 123.2 (3) |
| N1—Co1—Cl1i | 90.36 (8) | N1—C1—H1A | 118.4 |
| N2—Co1—Cl1i | 155.81 (5) | C2—C1—H1A | 118.4 |
| N2i—Co1—Cl1i | 90.14 (11) | C9—N3—C8 | 116.7 (2) |
| N1i—Co1—Cl1 | 90.36 (8) | C3—C2—C1 | 119.2 (3) |
| N1—Co1—Cl1 | 87.05 (8) | C3—C2—H2A | 120.4 |
| N2—Co1—Cl1 | 90.14 (11) | C1—C2—H2A | 120.4 |
| N2i—Co1—Cl1 | 155.81 (5) | N3—C8—C7 | 123.1 (3) |
| Cl1i—Co1—Cl1 | 107.66 (10) | N3—C8—H8A | 118.5 |
| C9—S1—C10 | 102.08 (15) | C7—C8—H8A | 118.5 |
| C6—N2—C9 | 115.9 (2) | C5—C4—C3 | 119.4 (3) |
| C6—N2—Co1 | 113.46 (15) | C5—C4—H4A | 120.3 |
| C9—N2—Co1 | 130.23 (17) | C3—C4—H4A | 120.3 |
| C5—N1—C1 | 117.4 (2) | S1—C10—H10A | 109.5 |
| C5—N1—Co1 | 120.02 (17) | S1—C10—H10B | 109.5 |
| C1—N1—Co1 | 122.42 (19) | H10A—C10—H10B | 109.5 |
| N2—C6—C7 | 121.9 (2) | S1—C10—H10C | 109.5 |
| N2—C6—C5 | 116.4 (2) | H10A—C10—H10C | 109.5 |
| C7—C6—C5 | 121.7 (3) | H10B—C10—H10C | 109.5 |
| N3—C9—N2 | 125.4 (2) | C4—C3—C2 | 118.4 (3) |
| N3—C9—S1 | 118.8 (2) | C4—C3—H3B | 120.8 |
| N2—C9—S1 | 115.7 (2) | C2—C3—H3B | 120.8 |
| Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
| Crystal data | |
| Chemical formula | [CoCl2(C10H9N3S)2] |
| Mr | 536.37 |
| Crystal system, space group | Monoclinic, C2/c |
| Temperature (K) | 298 |
| a, b, c (Å) | 8.709 (11), 17.10 (2), 15.328 (19) |
| β (°) | 102.34 (3) |
| V (Å3) | 2230 (5) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 1.22 |
| Crystal size (mm) | 0.35 × 0.28 × 0.24 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD area-detector diffractometer |
| Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
| Tmin, Tmax | 0.671, 0.747 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6138, 2586, 1636 |
| Rint | 0.052 |
| (sin θ/λ)max (Å−1) | 0.668 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.060, 0.93 |
| No. of reflections | 2586 |
| No. of parameters | 141 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.33, −0.50 |
Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by the Teaching and Research Program for Excellent Young Teachers of Southeast University (No. 3207041202).
References
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA Google Scholar
Dong, H. Z., Zhao, J., Gou, S. H. & Zhu, H. B. (2009). Polyhedron, 28, 1040–1048. Web of Science CSD CrossRef CAS Google Scholar
Huang, C. H., Gou, S. H., Zhu, H. B. & Huang, W. (2007). Inorg. Chem. 46, 5537–5543. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhu, H. B., Zhao, J., Kong, F., Gou, S. H. & Sun, Y. M. (2009). J. Mol. Struct. 928, 95–98. Web of Science CrossRef CAS Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Over the past few years, a number of coordination compounds derived from the prototypical ligands of 4-(pyridin-n-yl)pyrimidine-2-thiol (n = 2, 3, 4) and their S-modified derivatives have been reported by our group (Huang et al., 2007; Dong et al., 2009; Zhu et al., 2009). In light of our previous study, it is apparent that the coordination chemistry of such type of ligands is profoundly effected by the nature of the S atom. As part of our research program, we present here a discrete CoII coordination compound with ligand L (L = 2-(methylthio)-4-(pyridin-2-yl)pyrimidine) bearing a methylthio group.
The asymmetric unit of the title compound owns half of one molecule. A twofold rotational axis passes through the CoII atom. As depicted in Fig. 1, the CoII atom in the title compound is surrounded by two L ligands and two Cl atoms, adopting an octahedral coordination geometry. Like 2,2'-bipyridine, the ligand L serves as a chelating ligand through two N atoms with Co—N bond distances being 2.148 (3)Å and 2.299 (3) Å, whilst two Cl atoms are bound to the CoII atom in cis positions with equal Co—Cl bond distance (2.434 Å). In L, the pyridyl and pyrimidinyl rings are twisted by a dihedral angle of 9.9 (1)°, and the methylthio group is not involved into the metal coordination as a result of the weak affinity of the S atom for Co.