{Bis[4-(2-pyrid­yl)pyrimidin-2-yl]sulfane}dichloridocobalt(II)

Zhu, H.-B.; Li, L.; Ji, J.-F.

doi:10.1107/S1600536809022636

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page m784

doi:10.1107/S1600536809022636

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{Bis[4-(2-pyridyl)pyrimidin-2-yl]sulfane}dichloridocobalt(II)

Hai-Bin Zhu,^a ^* Lei Li ^a and Jun-Feng Ji ^a

^aSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: zhuhaibin@seu.edu.cn

(Received 10 June 2009; accepted 12 June 2009; online 17 June 2009)

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.

Related literature

For coordination compounds with bis(4-pyridinyl)sulfane, see: Jung et al. (1998 ); Ni & Vittal (2001 ).

Experimental

Crystal data

[CoCl₂(C₁₈H₁₂N₆S)]
M_r = 474.24
Monoclinic, C 2/c
a = 14.685 (3) Å
b = 10.325 (2) Å
c = 13.376 (3) Å
β = 112.339 (3)°
V = 1875.9 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.33 mm⁻¹
T = 298 K
0.20 × 0.18 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.884, T_max = 0.920 (expected range = 0.819–0.853)
6015 measured reflections
2302 independent reflections
1526 reflections with I > 2σ(I)
R_int = 0.141

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.077
S = 1.00
2302 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022636/at2809sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022636/at2809Isup2.hkl

checkCIF report

Comment top

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 Co^II 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.

Related literature top

For coordination compounds with bis(4-pyridinyl)sulfane, see: Jung et al. (1998); Ni & Vittal (2001).

Experimental top

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.

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

Fig. 1. The molecular structure of the title compound showing the atomic numbering and 40% probability displacement ellipsoids [symmetry code: (A) -x, y, 1/2 - z.]

{Bis[4-(2-pyridyl)pyrimidin-2-yl]sulfane}dichloridocobalt(II) top

Crystal data top

[CoCl₂(C₁₈H₁₂N₆S)]	F(000) = 956
M_r = 474.24	D_x = 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 monochromator	R_int = 0.141
ϕ and ω scans	θ_max = 28.4°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −17→19
T_min = 0.884, T_max = 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(F_o²) + (0.01P)²] where P = (F_o² + 2F_c²)/3
2302 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

[CoCl₂(C₁₈H₁₂N₆S)]	V = 1875.9 (7) Å³
M_r = 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)
T_min = 0.884, T_max = 0.920	R_int = 0.141
6015 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.00	Δρ_max = 0.51 e Å⁻³
2302 reflections	Δρ_min = −0.68 e Å⁻³
128 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

	x	y	z	U_iso*/U_eq
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, º) 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 code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) 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···Cl1^iv	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.

Experimental details

Crystal data
Chemical formula	[CoCl₂(C₁₈H₁₂N₆S)]
M_r	474.24
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	14.685 (3), 10.325 (2), 13.376 (3)
β (°)	112.339 (3)
V (Å³)	1875.9 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.33
Crystal size (mm)	0.20 × 0.18 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.884, 0.920
No. of measured, independent and observed [I > 2σ(I)] reflections	6015, 2302, 1526
R_int	0.141
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.077, 1.00
No. of reflections	2302
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.68

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

Hydrogen-bond geometry (Å, º) 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.

Acknowledgements

The authors acknowledge the finanical support of the Young Teachers' Starting Fund of Southeast University.

References

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