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The asymmetric unit 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811030881/vm2113sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536811030881/vm2113Isup2.hkl
Contains datablock I

CCDC reference: 845209

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.045
  • wR factor = 0.060
  • Data-to-parameter ratio = 18.3

checkCIF/PLATON results

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Alert level C PLAT148_ALERT_3_C su on the a - Axis is (Too) Large ........ 0.011 Ang. PLAT148_ALERT_3_C su on the b - Axis is (Too) Large ........ 0.0200 Ang. PLAT148_ALERT_3_C su on the c - Axis is (Too) Large ........ 0.019 Ang. PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 1 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 7 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 193
Alert level G PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ? PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Co1 -- Cl1 .. 6.6 su
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 6 ALERT level C = Check. Ensure it is not caused by an omission or oversight 2 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

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.

Related literature top

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); Dong et al. (2009); Zhu et al. (2009)

Experimental top

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.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] 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.
Dichloridobis[2-methylsulfanyl-4-(pyridin-2-yl)pyrimidine- κ2N3,N4)cobalt(II) top
Crystal data top
[CoCl2(C10H9N3S)2]F(000) = 1092
Mr = 536.37Dx = 1.598 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2588 reflections
a = 8.709 (11) Åθ = 2.3–25.5°
b = 17.10 (2) ŵ = 1.22 mm1
c = 15.328 (19) ÅT = 298 K
β = 102.34 (3)°Block, blue
V = 2230 (5) Å30.35 × 0.28 × 0.24 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2586 independent reflections
Radiation source: fine-focus sealed tube1636 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
ϕ and ω scansθmax = 28.4°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 119
Tmin = 0.671, Tmax = 0.747k = 2117
6138 measured reflectionsl = 1420
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.060H-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 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.50 e Å3
Crystal data top
[CoCl2(C10H9N3S)2]V = 2230 (5) Å3
Mr = 536.37Z = 4
Monoclinic, C2/cMo Kα radiation
a = 8.709 (11) ŵ = 1.22 mm1
b = 17.10 (2) ÅT = 298 K
c = 15.328 (19) Å0.35 × 0.28 × 0.24 mm
β = 102.34 (3)°
Data collection top
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 = 0.747Rint = 0.052
6138 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.060H-atom parameters constrained
S = 0.93Δρmax = 0.33 e Å3
2586 reflectionsΔρmin = 0.50 e Å3
141 parameters
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
xyzUiso*/Ueq
Co10.50000.29835 (3)0.25000.02888 (15)
Cl10.56198 (8)0.38235 (4)0.13403 (4)0.0435 (2)
S10.76922 (8)0.15867 (5)0.18274 (4)0.0419 (2)
N20.4663 (2)0.19418 (12)0.15296 (11)0.0274 (5)
N10.2595 (2)0.30314 (13)0.17840 (12)0.0309 (5)
C60.3142 (3)0.18317 (15)0.10981 (14)0.0279 (6)
C90.5705 (3)0.13805 (16)0.13928 (15)0.0314 (7)
C50.2020 (3)0.24704 (16)0.11833 (14)0.0288 (6)
C70.2671 (3)0.11737 (17)0.05868 (16)0.0389 (7)
H7A0.16340.11050.02850.047*
C10.1648 (3)0.36330 (17)0.18607 (16)0.0381 (7)
H1A0.20410.40350.22550.046*
N30.5331 (3)0.07212 (14)0.09342 (13)0.0402 (6)
C20.0109 (3)0.36861 (17)0.13814 (17)0.0422 (8)
H2A0.05160.41090.14630.051*
C80.3816 (3)0.06227 (17)0.05450 (17)0.0440 (8)
H8A0.35190.01620.02320.053*
C40.0501 (3)0.24955 (17)0.06704 (15)0.0364 (7)
H4A0.01450.21050.02540.044*
C100.8661 (3)0.07695 (18)0.14226 (19)0.0572 (9)
H10A0.97790.08220.16220.086*
H10B0.83960.07620.07820.086*
H10C0.83230.02910.16490.086*
C30.0481 (3)0.31061 (18)0.07843 (17)0.0424 (8)
H3B0.15160.31230.04640.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0301 (3)0.0267 (3)0.0278 (2)0.0000.0016 (2)0.000
Cl10.0447 (5)0.0451 (5)0.0379 (4)0.0040 (4)0.0027 (3)0.0098 (3)
S10.0323 (4)0.0441 (6)0.0470 (4)0.0022 (4)0.0030 (4)0.0135 (3)
N20.0295 (13)0.0292 (14)0.0223 (9)0.0010 (11)0.0029 (10)0.0001 (9)
N10.0313 (13)0.0318 (15)0.0296 (10)0.0039 (12)0.0069 (10)0.0007 (10)
C60.0299 (16)0.0316 (18)0.0211 (11)0.0022 (13)0.0029 (12)0.0015 (11)
C90.0344 (16)0.0310 (19)0.0278 (12)0.0009 (14)0.0046 (12)0.0004 (11)
C50.0316 (16)0.0309 (17)0.0233 (12)0.0039 (14)0.0044 (12)0.0029 (11)
C70.0306 (16)0.045 (2)0.0376 (15)0.0031 (16)0.0006 (13)0.0075 (13)
C10.0410 (18)0.037 (2)0.0349 (14)0.0062 (16)0.0057 (14)0.0009 (12)
N30.0412 (16)0.0333 (17)0.0426 (13)0.0021 (13)0.0015 (12)0.0111 (11)
C20.0423 (19)0.047 (2)0.0384 (15)0.0148 (17)0.0102 (15)0.0071 (14)
C80.047 (2)0.033 (2)0.0492 (17)0.0070 (17)0.0031 (16)0.0157 (14)
C40.0339 (17)0.041 (2)0.0322 (14)0.0013 (15)0.0022 (13)0.0014 (13)
C100.0378 (19)0.059 (2)0.072 (2)0.0117 (18)0.0058 (16)0.0197 (17)
C30.0294 (16)0.055 (2)0.0398 (15)0.0046 (16)0.0017 (14)0.0122 (15)
Geometric parameters (Å, º) top
Co1—N1i2.148 (3)C5—C41.388 (4)
Co1—N12.148 (3)C7—C81.383 (4)
Co1—N22.299 (3)C7—H7A0.9300
Co1—N2i2.299 (3)C1—C21.387 (4)
Co1—Cl1i2.434 (2)C1—H1A0.9300
Co1—Cl12.434 (2)N3—C81.337 (3)
S1—C91.752 (3)C2—C31.373 (4)
S1—C101.810 (3)C2—H2A0.9300
N2—C61.361 (3)C8—H8A0.9300
N2—C91.368 (3)C4—C31.384 (4)
N1—C51.350 (3)C4—H4A0.9300
N1—C11.340 (3)C10—H10A0.9600
C6—C71.382 (4)C10—H10B0.9600
C6—C51.490 (4)C10—H10C0.9600
C9—N31.332 (3)C3—H3B0.9300
N1i—Co1—N1175.62 (12)N1—C5—C4122.3 (2)
N1i—Co1—N2109.62 (8)N1—C5—C6115.2 (2)
N1—Co1—N273.94 (8)C4—C5—C6122.5 (2)
N1i—Co1—N2i73.94 (8)C8—C7—C6116.8 (3)
N1—Co1—N2i109.62 (8)C8—C7—H7A121.6
N2—Co1—N2i78.41 (14)C6—C7—H7A121.6
N1i—Co1—Cl1i87.05 (8)N1—C1—C2123.2 (3)
N1—Co1—Cl1i90.36 (8)N1—C1—H1A118.4
N2—Co1—Cl1i155.81 (5)C2—C1—H1A118.4
N2i—Co1—Cl1i90.14 (11)C9—N3—C8116.7 (2)
N1i—Co1—Cl190.36 (8)C3—C2—C1119.2 (3)
N1—Co1—Cl187.05 (8)C3—C2—H2A120.4
N2—Co1—Cl190.14 (11)C1—C2—H2A120.4
N2i—Co1—Cl1155.81 (5)N3—C8—C7123.1 (3)
Cl1i—Co1—Cl1107.66 (10)N3—C8—H8A118.5
C9—S1—C10102.08 (15)C7—C8—H8A118.5
C6—N2—C9115.9 (2)C5—C4—C3119.4 (3)
C6—N2—Co1113.46 (15)C5—C4—H4A120.3
C9—N2—Co1130.23 (17)C3—C4—H4A120.3
C5—N1—C1117.4 (2)S1—C10—H10A109.5
C5—N1—Co1120.02 (17)S1—C10—H10B109.5
C1—N1—Co1122.42 (19)H10A—C10—H10B109.5
N2—C6—C7121.9 (2)S1—C10—H10C109.5
N2—C6—C5116.4 (2)H10A—C10—H10C109.5
C7—C6—C5121.7 (3)H10B—C10—H10C109.5
N3—C9—N2125.4 (2)C4—C3—C2118.4 (3)
N3—C9—S1118.8 (2)C4—C3—H3B120.8
N2—C9—S1115.7 (2)C2—C3—H3B120.8
Symmetry code: (i) x+1, y, z+1/2.

Experimental details

Crystal data
Chemical formula[CoCl2(C10H9N3S)2]
Mr536.37
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)8.709 (11), 17.10 (2), 15.328 (19)
β (°) 102.34 (3)
V3)2230 (5)
Z4
Radiation typeMo Kα
µ (mm1)1.22
Crystal size (mm)0.35 × 0.28 × 0.24
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.671, 0.747
No. of measured, independent and
observed [I > 2σ(I)] reflections
6138, 2586, 1636
Rint0.052
(sin θ/λ)max1)0.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.060, 0.93
No. of reflections2586
No. of parameters141
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.50

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

 

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