{Bis[4-(2-pyrid­yl)pyrimidin-2-yl] sulfide}dibromidocobalt(II)

Li, C.-Y.; Tong, X.-L.; Hu, T.-L.

doi:10.1107/S1600536808015821

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m856

doi:10.1107/S1600536808015821

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{Bis[4-(2-pyridyl)pyrimidin-2-yl] sulfide}dibromidocobalt(II)

Cai-Yun Li,^a Xiao-Lan Tong ^b and Tong-Liang Hu ^b ^*

^aDepartment of Pharmaceutical Science, Tianjin Medical College, Tianjin 300222, People's Republic of China, and ^bDepartment of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
^*Correspondence e-mail: tlhu@nankai.edu.cn

(Received 15 May 2008; accepted 26 May 2008; online 7 June 2008)

The title compound, [CoBr₂(C₁₈H₁₂N₆S)], is a mononuclear complex in which a twofold rotation axis passes through the Co and S atoms. The Co^II center is six-coordinated by four N atoms from one bis[4-(2-pyridyl)pyrimidin-2-yl] sulfide (L) ligand and two bromide anions, forming an octahedral coordination geometry, where the four donor N atoms are located in the equatorial plane and the Br atoms occupy the axial positions. The sum of the bond angles around the Co atom in the equatorial plane is 360.5°, with the four N atoms and the central Co atom almost coplanar. In the crystal structure, the mononuclear units are linked by π–π stacking interactions (the interplanar distances are 3.469 and 3.533 Å, and the corresponding centroid–centroid distances are 3.791 and 3.896 Å) into a three-dimensional supramolecular network.

Related literature

For related literature, see: de Faria et al. (2007 ); Teles et al. (2006 ); Li & Bu (2008 ); Bridson & Walker (1970 ).

Experimental

Crystal data

[CoBr₂(C₁₈H₁₂N₆S)]
M_r = 563.15
Monoclinic, C 2/c
a = 15.191 (5) Å
b = 10.350 (4) Å
c = 13.338 (5) Å
β = 112.312 (5)°
V = 1940.0 (12) Å³
Z = 4
Mo Kα radiation
μ = 5.13 mm⁻¹
T = 294 (2) K
0.20 × 0.18 × 0.14 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.375, T_max = 0.489
5288 measured reflections
1970 independent reflections
1456 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.061
S = 1.04
1970 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Br1—Co1	2.6178 (10)
Co1—N2	2.099 (2)
Co1—N1	2.125 (2)

N2ⁱ—Co1—N2	96.18 (13)
N2—Co1—N1	78.04 (9)
N1—Co1—N1ⁱ	108.24 (13)
N2—Co1—Br1	86.87 (7)
N1—Co1—Br1	92.90 (7)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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 global, I. DOI: 10.1107/S1600536808015821/bq2083sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015821/bq2083Isup2.hkl

checkCIF report

Comment top

Semirigid thioether ligands containing heterocycle with N-donors are gradually used in constructing coordination architectures with novel topologies and useful functions in recent years (de Faria et al., 2007; Teles et al., 2006). The pyridine and pyrimidine groups as normal heterocycle were used to incorporate with different mercapto units to form a series of bi- and multi-dentate ligands, which can adopt different conformations according to the different geometric requirements of metal centers when forming metal complexes (Li & Bu, 2008). Herein, we synthesized a semirigid thioether ligand bis[4-(pyridin-2-yl)pyrimidin-2-yl]sulfide (L) as well as its Co^II complex, [Co(C₁₈H₁₂N₆S)Br₂] (I), and report the crystal structure of this complex.

In the molecule of (I), (Fig. 1), the bond lengths and angles are generally within normal ranges (Bridson & Walker, 1970). The Co^II center is six-coordinated by four N atoms from one L ligand and two bromine ions, forming an octahedral coordination geometry. The bond angles N1—Co1—N2, N2—Co1—N2A, N2A—Co1—N1A and N1A—Co1—N1 are 78.04 (9), 96.18 (1), 78.04 (9) and 108.24 (1)°, respectively. The sum of these angles is 360.5 (2)°, suggesting that N1, N2, N1A, N2A and Co1 are almost in a plane. In the crystal structure of (I), the mononuclear units are interconnected by two π···π stacking interactions between the rings (N1/C1-C5) and (N2/N3/C6-C9) forming a three-dimensional supramolecular network.

Related literature top

For related literatures, see: de Faria et al. (2007); Teles et al. (2006); Li & Bu (2008); Bridson & Walker (1970).

Experimental top

The ligand bis[4-(pyridin-2-yl)pyrimidin-2-yl]sulfide (L) was synthesized according to the following method. Some amount of potassium 4-(pyridin-2-yl)pyrimine-2-thiolate was dissolved in the distilled water, and the dense hydrochloric acid was added drop by drop with slowly stirring. A lot of yellow precipitate appeared and then gradually disappear when the dense hydrochloric acid was continuously added. After complete disappearance of the yellow precipitate, the potassium hydroxide solution was added to the mixture until another kind of precipitate was obtained largely. The crude product was filtered and washed with the distilled water three times, and recrystallized with the mixture of chloroform and hexane (v/v=1:1), yield: 60%. The title coordination complex, (I), was synthesized according to the following method. A buffer layer of chloroform/methanol (v/v=2:1, 5 ml) was carefully layered over a chloroform solution (4 mL) of L (6.8 mg, 0.02 mmol). Then a solution of CoBr₂ (4.4 mg, 0.02 mmol) in methanol (4 ml) was layered on the buffer layer. Red block crystals suitable for X-ray analysis were collected after five weeks, yield: 30%.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radius [symmetry code: (i) -x + 1, y, -z + 1/2].

{Bis[4-(2-pyridyl)pyrimidin-2-yl] sulfide}dibromidocobalt(II) top

Crystal data top

[CoBr₂(C₁₈H₁₂N₆S)]	F(000) = 1100
M_r = 563.15	D_x = 1.928 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -c 2yc	Cell parameters from 2104 reflections
a = 15.191 (5) Å	θ = 2.6–26.1°
b = 10.350 (4) Å	µ = 5.13 mm⁻¹
c = 13.338 (5) Å	T = 294 K
β = 112.312 (5)°	Block, red
V = 1940.0 (12) Å³	0.20 × 0.18 × 0.14 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	1970 independent reflections
Radiation source: fine-focus sealed tube	1456 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scans	θ_max = 26.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −18→16
T_min = 0.375, T_max = 0.489	k = −12→8
5288 measured reflections	l = −16→16

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0192P)² + 2.0266P] where P = (F_o² + 2F_c²)/3
1970 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[CoBr₂(C₁₈H₁₂N₆S)]	V = 1940.0 (12) Å³
M_r = 563.15	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.191 (5) Å	µ = 5.13 mm⁻¹
b = 10.350 (4) Å	T = 294 K
c = 13.338 (5) Å	0.20 × 0.18 × 0.14 mm
β = 112.312 (5)°

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	1970 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1456 reflections with I > 2σ(I)
T_min = 0.375, T_max = 0.489	R_int = 0.037
5288 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.04	Δρ_max = 0.39 e Å⁻³
1970 reflections	Δρ_min = −0.36 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
Br1	0.47796 (2)	0.71842 (3)	0.43535 (3)	0.04031 (12)
C1	0.3781 (2)	0.4680 (3)	0.1581 (3)	0.0462 (9)
H1	0.4358	0.4248	0.1763	0.055*
C2	0.2944 (3)	0.3973 (3)	0.1140 (3)	0.0540 (10)
H2	0.2962	0.3085	0.1046	0.065*
C3	0.2092 (3)	0.4609 (4)	0.0846 (3)	0.0515 (10)
H3	0.1522	0.4153	0.0562	0.062*
C4	0.2086 (2)	0.5924 (3)	0.0976 (3)	0.0425 (9)
H4	0.1514	0.6372	0.0765	0.051*
C5	0.29483 (19)	0.6578 (3)	0.1429 (2)	0.0297 (7)
C6	0.30020 (19)	0.7994 (3)	0.1562 (2)	0.0302 (7)
C7	0.2209 (2)	0.8785 (3)	0.1266 (3)	0.0415 (8)
H7	0.1598	0.8441	0.1002	0.050*
C8	0.2354 (2)	1.0094 (4)	0.1374 (3)	0.0457 (9)
H8	0.1827	1.0636	0.1177	0.055*
C9	0.3946 (2)	0.9792 (3)	0.2033 (2)	0.0353 (7)
Co1	0.5000	0.71573 (5)	0.2500	0.02984 (15)
N1	0.37930 (17)	0.5954 (2)	0.1755 (2)	0.0332 (6)
N2	0.38904 (15)	0.8512 (2)	0.1956 (2)	0.0294 (6)
N3	0.3215 (2)	1.0622 (3)	0.1749 (2)	0.0429 (7)
S1	0.5000	1.07169 (11)	0.2500	0.0597 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02302 (16)	0.0472 (2)	0.0458 (2)	−0.00028 (14)	0.00748 (13)	0.00055 (16)
C1	0.044 (2)	0.0312 (19)	0.052 (2)	−0.0043 (15)	0.0054 (17)	−0.0006 (15)
C2	0.067 (3)	0.041 (2)	0.045 (2)	−0.0245 (19)	0.011 (2)	−0.0037 (17)
C3	0.042 (2)	0.060 (3)	0.045 (2)	−0.0292 (19)	0.0083 (18)	0.0007 (18)
C4	0.0269 (17)	0.060 (2)	0.038 (2)	−0.0124 (15)	0.0093 (15)	0.0018 (16)
C5	0.0214 (15)	0.0413 (18)	0.0251 (17)	−0.0055 (13)	0.0072 (13)	0.0007 (13)
C6	0.0209 (14)	0.043 (2)	0.0235 (16)	0.0028 (13)	0.0047 (12)	0.0025 (13)
C7	0.0206 (16)	0.061 (2)	0.040 (2)	0.0065 (15)	0.0089 (14)	0.0005 (17)
C8	0.0348 (19)	0.058 (2)	0.041 (2)	0.0238 (17)	0.0110 (16)	0.0041 (17)
C9	0.0355 (18)	0.0325 (17)	0.0349 (19)	0.0081 (14)	0.0100 (15)	0.0010 (14)
Co1	0.0159 (3)	0.0224 (3)	0.0438 (4)	0.000	0.0030 (2)	0.000
N1	0.0245 (13)	0.0318 (15)	0.0373 (16)	−0.0042 (10)	0.0051 (12)	0.0002 (11)
N2	0.0203 (12)	0.0295 (14)	0.0343 (15)	0.0032 (10)	0.0060 (11)	0.0024 (11)
N3	0.0433 (17)	0.0387 (16)	0.0437 (18)	0.0201 (13)	0.0130 (14)	0.0052 (13)
S1	0.0424 (7)	0.0221 (6)	0.0980 (12)	0.000	0.0079 (7)	0.000

Geometric parameters (Å, º) top

Br1—Co1	2.6178 (10)	C7—C8	1.371 (5)
C1—N1	1.338 (4)	C7—H7	0.9300
C1—C2	1.388 (5)	C8—N3	1.328 (4)
C1—H1	0.9300	C8—H8	0.9300
C2—C3	1.371 (5)	C9—N2	1.329 (4)
C2—H2	0.9300	C9—N3	1.339 (4)
C3—C4	1.373 (5)	C9—S1	1.764 (3)
C3—H3	0.9300	Co1—N2ⁱ	2.099 (2)
C4—C5	1.392 (4)	Co1—N2	2.099 (2)
C4—H4	0.9300	Co1—N1	2.125 (2)
C5—N1	1.353 (4)	Co1—N1ⁱ	2.125 (2)
C5—C6	1.475 (4)	Co1—Br1ⁱ	2.6178 (10)
C6—N2	1.359 (3)	S1—C9ⁱ	1.764 (3)
C6—C7	1.385 (4)

N1—C1—C2	122.9 (3)	N2—C9—S1	126.2 (2)
N1—C1—H1	118.6	N3—C9—S1	107.2 (2)
C2—C1—H1	118.6	N2ⁱ—Co1—N2	96.18 (13)
C3—C2—C1	118.8 (3)	N2ⁱ—Co1—N1	171.98 (9)
C3—C2—H2	120.6	N2—Co1—N1	78.04 (9)
C1—C2—H2	120.6	N2ⁱ—Co1—N1ⁱ	78.04 (9)
C2—C3—C4	119.4 (3)	N2—Co1—N1ⁱ	171.98 (9)
C2—C3—H3	120.3	N1—Co1—N1ⁱ	108.24 (13)
C4—C3—H3	120.3	N2ⁱ—Co1—Br1	92.32 (7)
C3—C4—C5	119.1 (3)	N2—Co1—Br1	86.87 (7)
C3—C4—H4	120.4	N1—Co1—Br1	92.90 (7)
C5—C4—H4	120.4	N1ⁱ—Co1—Br1	87.82 (7)
N1—C5—C4	121.9 (3)	N2ⁱ—Co1—Br1ⁱ	86.87 (7)
N1—C5—C6	115.7 (2)	N2—Co1—Br1ⁱ	92.32 (7)
C4—C5—C6	122.4 (3)	N1—Co1—Br1ⁱ	87.82 (7)
N2—C6—C7	120.4 (3)	N1ⁱ—Co1—Br1ⁱ	92.90 (7)
N2—C6—C5	116.1 (2)	Br1—Co1—Br1ⁱ	178.78 (3)
C7—C6—C5	123.5 (3)	C1—N1—C5	117.8 (3)
C8—C7—C6	117.8 (3)	C1—N1—Co1	127.7 (2)
C8—C7—H7	121.1	C5—N1—Co1	114.53 (19)
C6—C7—H7	121.1	C9—N2—C6	116.6 (2)
N3—C8—C7	122.8 (3)	C9—N2—Co1	128.34 (19)
N3—C8—H8	118.6	C6—N2—Co1	114.81 (19)
C7—C8—H8	118.6	C8—N3—C9	115.7 (3)
N2—C9—N3	126.6 (3)	C9—S1—C9ⁱ	114.3 (2)

N1—C1—C2—C3	1.5 (6)	Br1—Co1—N1—C5	79.4 (2)
C1—C2—C3—C4	1.2 (6)	Br1ⁱ—Co1—N1—C5	−99.7 (2)
C2—C3—C4—C5	−1.6 (5)	N3—C9—N2—C6	−0.9 (4)
C3—C4—C5—N1	−0.7 (5)	S1—C9—N2—C6	−179.2 (2)
C3—C4—C5—C6	178.0 (3)	N3—C9—N2—Co1	−174.6 (2)
N1—C5—C6—N2	2.5 (4)	S1—C9—N2—Co1	7.1 (4)
C4—C5—C6—N2	−176.2 (3)	C7—C6—N2—C9	−0.2 (4)
N1—C5—C6—C7	179.6 (3)	C5—C6—N2—C9	177.1 (3)
C4—C5—C6—C7	0.9 (5)	C7—C6—N2—Co1	174.4 (2)
N2—C6—C7—C8	0.7 (5)	C5—C6—N2—Co1	−8.4 (3)
C5—C6—C7—C8	−176.4 (3)	N2ⁱ—Co1—N2—C9	−3.7 (2)
C6—C7—C8—N3	−0.1 (5)	N1—Co1—N2—C9	−178.0 (3)
C2—C1—N1—C5	−3.7 (5)	Br1—Co1—N2—C9	88.3 (2)
C2—C1—N1—Co1	176.2 (3)	Br1ⁱ—Co1—N2—C9	−90.8 (2)
C4—C5—N1—C1	3.3 (4)	N2ⁱ—Co1—N2—C6	−177.5 (2)
C6—C5—N1—C1	−175.5 (3)	N1—Co1—N2—C6	8.2 (2)
C4—C5—N1—Co1	−176.7 (2)	Br1—Co1—N2—C6	−85.46 (19)
C6—C5—N1—Co1	4.6 (3)	Br1ⁱ—Co1—N2—C6	95.45 (19)
N2—Co1—N1—C1	173.2 (3)	C7—C8—N3—C9	−0.9 (5)
N1ⁱ—Co1—N1—C1	−12.0 (2)	N2—C9—N3—C8	1.5 (5)
Br1—Co1—N1—C1	−100.6 (3)	S1—C9—N3—C8	−180.0 (2)
Br1ⁱ—Co1—N1—C1	80.4 (3)	N2—C9—S1—C9ⁱ	−3.8 (2)
N2—Co1—N1—C5	−6.8 (2)	N3—C9—S1—C9ⁱ	177.7 (3)
N1ⁱ—Co1—N1—C5	168.0 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[CoBr₂(C₁₈H₁₂N₆S)]
M_r	563.15
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	15.191 (5), 10.350 (4), 13.338 (5)
β (°)	112.312 (5)
V (Å³)	1940.0 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.13
Crystal size (mm)	0.20 × 0.18 × 0.14

Data collection
Diffractometer	Rigaku R-AXIS RAPID-S diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.375, 0.489
No. of measured, independent and observed [I > 2σ(I)] reflections	5288, 1970, 1456
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.061, 1.04
No. of reflections	1970
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.36

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Br1—Co1	2.6178 (10)	Co1—N1	2.125 (2)
Co1—N2	2.099 (2)

N2ⁱ—Co1—N2	96.18 (13)	N1—Co1—N1ⁱ	108.24 (13)
N2—Co1—N1	78.04 (9)	N2—Co1—Br1	86.87 (7)
N2ⁱ—Co1—N1ⁱ	78.04 (9)	N1—Co1—Br1	92.90 (7)

Symmetry code: (i) −x+1, y, −z+1/2.

Acknowledgements

The authors thank Nankai University for supporting this work.

References

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