supplementary materials
{Bis[4-(2-pyridyl)pyrimidin-2-yl]sulfane}dichloridocobalt(II)
The asymmetric unit of the title compound, [CoCl2(C18H12N6S)], contains one half-molecule situated on a twofold rotation axis which passes through the Co and S atoms. The metal centre is in a distorted octahedral CoCl2N4 coordination with the Cl atoms in the axial positions. In the crystal structure, intermolecular C-H
Cl interactions help to establish the packing.
To a solution of CoCl2 (0.1 mmol) in MeOH (10 ml) was added a solution of
bis(4-(pyridin-2-yl)pyrimidin-2-yl)sulfane (0.1 mmol) in CH2Cl2 (5 ml).
The mixture was stirred for 30 min, then filtered. The mother liquid was stood
at ambient temperature for two days to give the orange crystals.
All H atoms were positioned geometrically and allowed to ride on their parent
atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for
aromatic H atoms.
Data collection: APEX2 (Bruker, 2007); cell refinement: 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).
{Bis[4-(2-pyridyl)pyrimidin-2-yl]sulfane}dichloridocobalt(II)
top
Crystal data top
| [CoCl2(C18H12N6S)] | F(000) = 956 |
| Mr = 474.24 | Dx = 1.679 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2302 reflections |
| a = 14.685 (3) Å | θ = 2.3–25.5° |
| b = 10.325 (2) Å | µ = 1.33 mm−1 |
| c = 13.376 (3) Å | T = 298 K |
| β = 112.339 (3)° | Block, orange |
| V = 1875.9 (7) Å3 | 0.20 × 0.18 × 0.12 mm |
| Z = 4 | |
Data collection top
Bruker APEXII CCD area-detector
diffractometer | 2302 independent reflections |
| Radiation source: fine-focus sealed tube | 1526 reflections with I > 2σ(I) |
| graphite | Rint = 0.141 |
| φ and ω scans | θmax = 28.4°, θmin = 2.5° |
Absorption correction: multi-scan
(SADABS; Bruker, 2001) | h = −17→19 |
| Tmin = 0.884, Tmax = 0.920 | k = −6→13 |
| 6015 measured reflections | l = −17→17 |
Refinement top
| 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.077 | H-atom parameters constrained |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.01P)2]
where P = (Fo2 + 2Fc2)/3 |
| 2302 reflections | (Δ/σ)max = 0.001 |
| 128 parameters | Δρmax = 0.51 e Å−3 |
| 0 restraints | Δρmin = −0.67 e Å−3 |
Crystal data top
| [CoCl2(C18H12N6S)] | V = 1875.9 (7) Å3 |
| Mr = 474.24 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 14.685 (3) Å | µ = 1.33 mm−1 |
| b = 10.325 (2) Å | T = 298 K |
| c = 13.376 (3) Å | 0.20 × 0.18 × 0.12 mm |
| β = 112.339 (3)° | |
Data collection top
Bruker APEXII CCD area-detector
diffractometer | 2302 independent reflections |
Absorption correction: multi-scan
(SADABS; Bruker, 2001) | 1526 reflections with I > 2σ(I) |
| Tmin = 0.884, Tmax = 0.920 | Rint = 0.141 |
| 6015 measured reflections | θmax = 28.4° |
Refinement top
| R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
| wR(F2) = 0.077 | Δρmax = 0.51 e Å−3 |
| S = 1.00 | Δρmin = −0.67 e Å−3 |
| 2302 reflections | Absolute structure: ? |
| 128 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| Co1 | 0.5000 | 0.21623 (4) | 0.2500 | 0.03357 (15) | |
| Cl1 | 0.52209 (5) | 0.21891 (6) | 0.07848 (5) | 0.04298 (19) | |
| S1 | 0.5000 | 0.57242 (8) | 0.2500 | 0.0646 (4) | |
| N3 | 0.37405 (17) | 0.09651 (17) | 0.17599 (17) | 0.0358 (5) | |
| N2 | 0.38470 (16) | 0.35147 (16) | 0.19288 (16) | 0.0327 (5) | |
| C4 | 0.2933 (2) | 0.3022 (2) | 0.15111 (19) | 0.0353 (6) | |
| C1 | 0.3909 (2) | 0.4812 (2) | 0.2002 (2) | 0.0382 (7) | |
| N1 | 0.3163 (2) | 0.56366 (19) | 0.16953 (19) | 0.0473 (6) | |
| C5 | 0.2875 (2) | 0.1579 (2) | 0.14019 (19) | 0.0350 (6) | |
| C3 | 0.2114 (2) | 0.3803 (3) | 0.1175 (2) | 0.0456 (7) | |
| H3A | 0.1482 | 0.3460 | 0.0884 | 0.055* | |
| C2 | 0.2275 (2) | 0.5119 (3) | 0.1289 (2) | 0.0500 (8) | |
| H2A | 0.1733 | 0.5669 | 0.1070 | 0.060* | |
| C6 | 0.1984 (2) | 0.0954 (2) | 0.0938 (2) | 0.0472 (7) | |
| H6A | 0.1398 | 0.1419 | 0.0695 | 0.057* | |
| C8 | 0.2854 (3) | −0.1011 (3) | 0.1176 (2) | 0.0586 (9) | |
| H8A | 0.2869 | −0.1906 | 0.1108 | 0.070* | |
| C9 | 0.3722 (2) | −0.0329 (2) | 0.1618 (2) | 0.0523 (9) | |
| H9A | 0.4315 | −0.0777 | 0.1825 | 0.063* | |
| C7 | 0.1980 (3) | −0.0383 (3) | 0.0841 (2) | 0.0566 (9) | |
| H7A | 0.1390 | −0.0837 | 0.0552 | 0.068* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Co1 | 0.0269 (3) | 0.0223 (2) | 0.0436 (3) | 0.000 | 0.0045 (2) | 0.000 |
| Cl1 | 0.0342 (4) | 0.0443 (4) | 0.0449 (4) | 0.0018 (3) | 0.0089 (3) | 0.0000 (3) |
| S1 | 0.0532 (8) | 0.0242 (5) | 0.0984 (10) | 0.000 | 0.0086 (7) | 0.000 |
| N3 | 0.0360 (14) | 0.0272 (10) | 0.0381 (12) | −0.0012 (10) | 0.0072 (10) | 0.0015 (9) |
| N2 | 0.0333 (13) | 0.0253 (10) | 0.0349 (12) | 0.0029 (10) | 0.0077 (10) | 0.0012 (8) |
| C4 | 0.0382 (17) | 0.0384 (14) | 0.0244 (13) | 0.0011 (13) | 0.0064 (12) | 0.0006 (10) |
| C1 | 0.0434 (18) | 0.0290 (12) | 0.0390 (15) | 0.0063 (12) | 0.0121 (14) | 0.0017 (11) |
| N1 | 0.0512 (18) | 0.0374 (12) | 0.0472 (15) | 0.0170 (12) | 0.0117 (13) | 0.0037 (10) |
| C5 | 0.0354 (16) | 0.0382 (13) | 0.0280 (13) | −0.0061 (13) | 0.0083 (13) | 0.0016 (11) |
| C3 | 0.0343 (17) | 0.0556 (17) | 0.0403 (16) | 0.0079 (15) | 0.0067 (14) | 0.0014 (13) |
| C2 | 0.047 (2) | 0.0529 (17) | 0.0445 (18) | 0.0276 (16) | 0.0118 (16) | 0.0072 (13) |
| C6 | 0.0395 (18) | 0.0564 (17) | 0.0403 (16) | −0.0103 (15) | 0.0092 (14) | 0.0023 (13) |
| C8 | 0.076 (3) | 0.0356 (14) | 0.0502 (19) | −0.0182 (17) | 0.0082 (19) | −0.0005 (13) |
| C9 | 0.058 (2) | 0.0286 (13) | 0.0580 (19) | −0.0056 (14) | 0.0079 (17) | −0.0030 (12) |
| C7 | 0.059 (2) | 0.0570 (18) | 0.0466 (18) | −0.0322 (17) | 0.0116 (17) | −0.0023 (14) |
Geometric parameters (Å, °) top
| Co1—N2i | 2.102 (2) | C1—N1 | 1.323 (3) |
| Co1—N2 | 2.1017 (19) | N1—C2 | 1.320 (4) |
| Co1—N3 | 2.130 (2) | C5—C6 | 1.377 (4) |
| Co1—N3i | 2.130 (2) | C3—C2 | 1.378 (3) |
| Co1—Cl1i | 2.4363 (9) | C3—H3A | 0.9300 |
| Co1—Cl1 | 2.4363 (9) | C2—H2A | 0.9300 |
| S1—C1 | 1.757 (3) | C6—C7 | 1.386 (3) |
| S1—C1i | 1.757 (3) | C6—H6A | 0.9300 |
| N3—C5 | 1.335 (3) | C8—C7 | 1.354 (5) |
| N3—C9 | 1.349 (3) | C8—C9 | 1.377 (4) |
| N2—C4 | 1.343 (3) | C8—H8A | 0.9300 |
| N2—C1 | 1.343 (3) | C9—H9A | 0.9300 |
| C4—C3 | 1.374 (4) | C7—H7A | 0.9300 |
| C4—C5 | 1.497 (3) | | |
| | | |
| N2i—Co1—N2 | 96.73 (11) | N1—C1—N2 | 126.5 (3) |
| N2i—Co1—N3 | 172.65 (7) | N1—C1—S1 | 107.47 (18) |
| N2—Co1—N3 | 77.25 (8) | N2—C1—S1 | 126.1 (2) |
| N2i—Co1—N3i | 77.25 (8) | C2—N1—C1 | 116.0 (2) |
| N2—Co1—N3i | 172.65 (7) | N3—C5—C6 | 123.5 (2) |
| N3—Co1—N3i | 109.05 (11) | N3—C5—C4 | 115.3 (2) |
| N2i—Co1—Cl1i | 91.57 (6) | C6—C5—C4 | 121.3 (3) |
| N2—Co1—Cl1i | 87.57 (6) | C4—C3—C2 | 116.8 (3) |
| N3—Co1—Cl1i | 92.37 (6) | C4—C3—H3A | 121.6 |
| N3i—Co1—Cl1i | 88.39 (6) | C2—C3—H3A | 121.6 |
| N2i—Co1—Cl1 | 87.57 (6) | N1—C2—C3 | 123.1 (3) |
| N2—Co1—Cl1 | 91.57 (6) | N1—C2—H2A | 118.5 |
| N3—Co1—Cl1 | 88.39 (6) | C3—C2—H2A | 118.5 |
| N3i—Co1—Cl1 | 92.37 (6) | C5—C6—C7 | 118.6 (3) |
| Cl1i—Co1—Cl1 | 178.70 (3) | C5—C6—H6A | 120.7 |
| C1—S1—C1i | 115.15 (17) | C7—C6—H6A | 120.7 |
| C5—N3—C9 | 117.0 (2) | C7—C8—C9 | 120.3 (3) |
| C5—N3—Co1 | 115.55 (15) | C7—C8—H8A | 119.9 |
| C9—N3—Co1 | 127.4 (2) | C9—C8—H8A | 119.9 |
| C4—N2—C1 | 115.9 (2) | N3—C9—C8 | 122.1 (3) |
| C4—N2—Co1 | 116.07 (15) | N3—C9—H9A | 118.9 |
| C1—N2—Co1 | 127.82 (19) | C8—C9—H9A | 118.9 |
| N2—C4—C3 | 121.7 (2) | C8—C7—C6 | 118.4 (3) |
| N2—C4—C5 | 115.4 (2) | C8—C7—H7A | 120.8 |
| C3—C4—C5 | 122.9 (3) | C6—C7—H7A | 120.8 |
| | | |
| N2—Co1—N3—C5 | −5.56 (17) | C1i—S1—C1—N1 | 177.9 (2) |
| N3i—Co1—N3—C5 | 170.5 (2) | C1i—S1—C1—N2 | −3.15 (18) |
| Cl1i—Co1—N3—C5 | 81.40 (18) | N2—C1—N1—C2 | 0.7 (4) |
| Cl1—Co1—N3—C5 | −97.53 (18) | S1—C1—N1—C2 | 179.6 (2) |
| N2—Co1—N3—C9 | 174.6 (2) | C9—N3—C5—C6 | 2.2 (4) |
| N3i—Co1—N3—C9 | −9.30 (19) | Co1—N3—C5—C6 | −177.6 (2) |
| Cl1i—Co1—N3—C9 | −98.4 (2) | C9—N3—C5—C4 | −176.2 (2) |
| Cl1—Co1—N3—C9 | 82.7 (2) | Co1—N3—C5—C4 | 3.9 (3) |
| N2i—Co1—N2—C4 | −177.8 (2) | N2—C4—C5—N3 | 1.7 (3) |
| N3—Co1—N2—C4 | 6.51 (17) | C3—C4—C5—N3 | 179.4 (2) |
| Cl1i—Co1—N2—C4 | −86.47 (17) | N2—C4—C5—C6 | −176.9 (2) |
| Cl1—Co1—N2—C4 | 94.50 (17) | C3—C4—C5—C6 | 0.9 (4) |
| N2i—Co1—N2—C1 | −3.04 (17) | N2—C4—C3—C2 | −0.2 (4) |
| N3—Co1—N2—C1 | −178.8 (2) | C5—C4—C3—C2 | −177.8 (2) |
| Cl1i—Co1—N2—C1 | 88.2 (2) | C1—N1—C2—C3 | −0.5 (4) |
| Cl1—Co1—N2—C1 | −90.8 (2) | C4—C3—C2—N1 | 0.2 (4) |
| C1—N2—C4—C3 | 0.3 (4) | N3—C5—C6—C7 | 0.4 (4) |
| Co1—N2—C4—C3 | 175.7 (2) | C4—C5—C6—C7 | 178.8 (2) |
| C1—N2—C4—C5 | 178.1 (2) | C5—N3—C9—C8 | −3.3 (4) |
| Co1—N2—C4—C5 | −6.5 (3) | Co1—N3—C9—C8 | 176.5 (2) |
| C4—N2—C1—N1 | −0.6 (4) | C7—C8—C9—N3 | 1.7 (5) |
| Co1—N2—C1—N1 | −175.4 (2) | C9—C8—C7—C6 | 1.0 (5) |
| C4—N2—C1—S1 | −179.38 (19) | C5—C6—C7—C8 | −2.0 (4) |
| Co1—N2—C1—S1 | 5.9 (3) | | |
| Symmetry codes: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2A···Cl1ii | 0.93 | 2.63 | 3.546 (3) | 170 |
| C3—H3A···Cl1iii | 0.93 | 2.73 | 3.584 (3) | 154 |
| C7—H7A···Cl1iv | 0.93 | 2.76 | 3.580 (4) | 148 |
| Symmetry codes: (ii) x−1/2, y+1/2, z; (iii) −x+1/2, −y+1/2, −z; (iv) x−1/2, y−1/2, z. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2A···Cl1i | 0.93 | 2.63 | 3.546 (3) | 170 |
| C3—H3A···Cl1ii | 0.93 | 2.73 | 3.584 (3) | 154 |
| C7—H7A···Cl1iii | 0.93 | 2.76 | 3.580 (4) | 148 |
| Symmetry codes: (i) x−1/2, y+1/2, z; (ii) −x+1/2, −y+1/2, −z; (iii) x−1/2, y−1/2, z. |
The authors acknowledge the finanical support of the Young Teachers' Starting
Fund of Southeast University.
Bruker (2001). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2007). APEX2 and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.
Jung, O. S., Park, S. H., Kim, D. C. & Kim, K. M. (1998). Inorg. Chem. 37, 610-611.
Ni, Z. & Vittal, J. J. (2001). Cryst. Growth Des. 1, 195-197.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./at2809fig1thm.gif)
Organic ligand of bis(4-pyridinyl)sulfane has been employed to construct some intriguing metal–orgainc frameworks (MOFs) (Jung et al.,1998; Ni & Vittal, 2001). Herein, we report the molecular structure of a mononuclear CoII coordination complex (I) with bis(4-(pyridin-2-yl)pyrimidin-2-yl)sulfane.
In compound (I), the cobalt(II) ion is six-coordinated by four N atoms in equatorial position and two Cl atoms in apical position (Fig. 1). The Co—N bond lengths are 2.102 (2) Å and 2.130 (2) Å and the Co—Cl bond distance is 2.4363 (9) Å. In the crystal, intermolecular C—H···Cl interactions help to establish the packing.