Poly[dichloridobis(μ2-di-4-pyridyl sulfide-κ2N,N′)cobalt(II)]

Wang, J.-G.; Qin, J.-H.; Zhang, G.-Y.

doi:10.1107/S1600536809001676

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page m247

doi:10.1107/S1600536809001676

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Poly[dichloridobis(μ₂-di-4-pyridyl sulfide-κ²N,N′)cobalt(II)]

Jian-Ge Wang,^a Jian-Hua Qin ^a ^* and Gui-Ying Zhang ^a

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China
^*Correspondence e-mail: jh_q128105@126.com

(Received 5 January 2009; accepted 14 January 2009; online 4 February 2009)

In the title compound, [CoCl₂(C₁₀H₈N₂S)₂]_n, the Co^II atom is located on an inversion centre and is six-coordinated by four N atoms of four symmetry-related di-4-pyridyl sulfide ligands, and two Cl atoms in trans positions, in a distorted octahedral geometry. The bridging bidentate di-4-pyridyl sulfide ligands link the Co^II centres into a three-dimensional network. The four coordinating pyridine groups are donors and acceptors (N atoms) for intramolecular C—H⋯N and C—H⋯Cl hydrogen bonds.

Related literature

For di-4-pyridyl sulfide metal complexes, see: Jung et al. (1998 , 1999 ); Kondo et al. (2004 ); Muthu et al. (2005 ).

Experimental

Crystal data

[CoCl₂(C₁₀H₈N₂S)₂]
M_r = 506.32
Monoclinic, P 2₁ /c
a = 7.4940 (11) Å
b = 15.355 (2) Å
c = 9.4009 (14) Å
β = 98.413 (2)°
V = 1070.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.26 mm⁻¹
T = 296 (2) K
0.44 × 0.34 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.608, T_max = 0.747
5174 measured reflections
1969 independent reflections
1720 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.070
S = 1.05
1969 reflections
133 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co1—N1	2.2185 (18)
Co1—N2ⁱ	2.2822 (17)
Co1—Cl1	2.4221 (5)

N1—Co1—N2ⁱ	94.00 (6)
N1—Co1—Cl1	90.50 (5)
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯N2ⁱⁱ	0.93	2.62	3.119 (3)	114
C6—H6⋯Cl1ⁱⁱⁱ	0.93	2.66	3.292 (2)	126
C10—H10⋯Cl1^iv	0.93	2.64	3.292 (2)	128
Symmetry codes: (ii) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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 I, global. DOI: 10.1107/S1600536809001676/si2149sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001676/si2149Isup2.hkl

checkCIF report

Comment top

As well known, di-4-pyridyl sulfide possesses a magic angle (C-S-C, ~100°) and conformational nonrigidity so it has some flexibility compared with other linear rigid ligands such as simple 4, 4'-bipyridine analogues. A number of metal complexes derived from di-4-pyridyl sulfide have been reported previously, such as the silver(I) complexes (Jung et al., 1999), copper(II) complexes (Muthu et al., 2005), nickel(II) complex (Kondo et al., 2004), as well as the cobalt(II) complex that showing 2-fold interpenetrating structures (Jung et al., 1998).

As shown in Fig. 1, the local geometry of the cobalt atoms is a distorted octahedral arrangement with two chlorine atoms in trans positions and four pyridine units in a propeller arrangement (Tab. 1). Each di-4-pyridyl sulfide ligand connects two cobalt(II) ions defining the edges of a 40-membered [Co(II)]₄ sheet (Fig. 2). The bent angle of the sulfur atom [C-S-C = 102.90 (10) °]. The Co-Co separation through a di-4-pyridyl sulfide ligand is 11.2646 (10) Å, and through the diagonal of the rhombus is 15.355 (2) Å. There are six intramolecular C—H···N and C—H···Cl hydrogen bonding contacts around the coordination sphere of the cobalt atom (Tab. 2). The packing of the layered structure is shown in Fig.3.

Related literature top

For di-4-pyridyl sulfide metal complexes, see: Jung et al. (1998, 1999); Kondo et al. (2004); Muthu et al. (2005).

Experimental top

To a stirred solution of di-4-pyridyl sulfide (0.5 mmol) in ethanol-H₂O 20 ml (v/v, 1:1) was added solid CoCl₂(0.5 mmol). Then the obtained mixture was basified with NaOH (0.5 mol/l) to a pH of 6.0 and stirred at 343K for 4h, filtrated. One week later, red crystals appeared.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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. A view of the local coordination of the Co(II) cation in the title compound. Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes: (A) (-x, 1 - y, 1 - z); (B) (-1 + x, 3/2 - y, -1/2 + z); (C) (1 - x, -1/2 + y, 3/2 - z).
	Fig. 2. A view of the two-dimensional network.
	Fig. 3. A view of the compound packing down the a axis.

Poly[dichloridobis(µ₂-di-4-pyridyl sulfide-κ²N,N')cobalt(II)] top

Crystal data top

[CoCl₂(C₁₀H₈N₂S)₂]	F(000) = 514
M_r = 506.32	D_x = 1.571 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2498 reflections
a = 7.4940 (11) Å	θ = 2.6–29.0°
b = 15.355 (2) Å	µ = 1.26 mm⁻¹
c = 9.4009 (14) Å	T = 296 K
β = 98.413 (2)°	Block, red
V = 1070.1 (3) Å³	0.44 × 0.34 × 0.24 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	1969 independent reflections
Radiation source: fine-focus sealed tube	1720 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→8
T_min = 0.608, T_max = 0.747	k = −14→18
5174 measured reflections	l = −11→11

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0329P)² + 0.5314P] where P = (F_o² + 2F_c²)/3
1969 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

[CoCl₂(C₁₀H₈N₂S)₂]	V = 1070.1 (3) Å³
M_r = 506.32	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4940 (11) Å	µ = 1.26 mm⁻¹
b = 15.355 (2) Å	T = 296 K
c = 9.4009 (14) Å	0.44 × 0.34 × 0.24 mm
β = 98.413 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1969 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1720 reflections with I > 2σ(I)
T_min = 0.608, T_max = 0.747	R_int = 0.017
5174 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 1.05	Δρ_max = 0.38 e Å⁻³
1969 reflections	Δρ_min = −0.26 e Å⁻³
133 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.0000	0.5000	0.5000	0.02605 (13)
Cl1	0.20061 (7)	0.43179 (4)	0.35327 (6)	0.04042 (16)
S1	0.46119 (10)	0.86590 (4)	0.38777 (6)	0.0496 (2)
N1	0.1375 (2)	0.62685 (11)	0.48432 (19)	0.0336 (4)
N2	0.8140 (2)	0.95816 (11)	0.79735 (18)	0.0295 (4)
C1	0.3135 (3)	0.63405 (14)	0.5315 (2)	0.0319 (5)
H1	0.3717	0.5866	0.5793	0.038*
C2	0.4148 (3)	0.70682 (14)	0.5143 (2)	0.0335 (5)
H2	0.5363	0.7088	0.5527	0.040*
C3	0.3335 (3)	0.77696 (14)	0.4393 (2)	0.0336 (5)
C4	0.1498 (3)	0.77243 (16)	0.3907 (3)	0.0485 (6)
H4	0.0894	0.8187	0.3410	0.058*
C5	0.0589 (3)	0.69710 (16)	0.4181 (3)	0.0492 (6)
H5	−0.0651	0.6952	0.3886	0.059*
C6	0.6455 (3)	0.92970 (14)	0.8003 (2)	0.0316 (5)
H6	0.6015	0.9310	0.8877	0.038*
C7	0.5337 (3)	0.89872 (14)	0.6820 (2)	0.0349 (5)
H7	0.4174	0.8803	0.6902	0.042*
C8	0.5962 (3)	0.89534 (14)	0.5507 (2)	0.0335 (5)
C9	0.7705 (3)	0.92370 (16)	0.5454 (2)	0.0433 (6)
H9	0.8182	0.9221	0.4595	0.052*
C10	0.8725 (3)	0.95443 (16)	0.6695 (2)	0.0411 (6)
H10	0.9889	0.9737	0.6640	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0256 (2)	0.0273 (2)	0.0247 (2)	0.00031 (16)	0.00196 (15)	0.00041 (15)
Cl1	0.0376 (3)	0.0546 (4)	0.0284 (3)	0.0153 (3)	0.0027 (2)	−0.0004 (2)
S1	0.0709 (4)	0.0438 (4)	0.0278 (3)	−0.0271 (3)	−0.0134 (3)	0.0079 (3)
N1	0.0322 (10)	0.0303 (10)	0.0371 (10)	−0.0001 (8)	0.0009 (8)	0.0009 (8)
N2	0.0310 (9)	0.0302 (10)	0.0261 (9)	−0.0020 (8)	0.0000 (7)	−0.0012 (7)
C1	0.0358 (12)	0.0290 (11)	0.0287 (11)	0.0006 (9)	−0.0023 (9)	0.0031 (9)
C2	0.0326 (11)	0.0336 (12)	0.0310 (11)	−0.0032 (9)	−0.0064 (9)	−0.0002 (9)
C3	0.0436 (13)	0.0287 (11)	0.0259 (10)	−0.0068 (9)	−0.0037 (9)	−0.0022 (9)
C4	0.0454 (14)	0.0302 (13)	0.0637 (17)	0.0008 (11)	−0.0125 (12)	0.0064 (12)
C5	0.0309 (12)	0.0374 (13)	0.0743 (18)	−0.0003 (10)	−0.0086 (12)	0.0023 (13)
C6	0.0339 (11)	0.0340 (11)	0.0265 (10)	−0.0025 (9)	0.0031 (9)	0.0002 (9)
C7	0.0345 (11)	0.0352 (12)	0.0333 (12)	−0.0093 (10)	−0.0004 (9)	0.0005 (10)
C8	0.0437 (13)	0.0265 (11)	0.0269 (11)	−0.0063 (9)	−0.0058 (9)	0.0022 (9)
C9	0.0495 (14)	0.0531 (15)	0.0280 (12)	−0.0121 (12)	0.0079 (10)	−0.0043 (11)
C10	0.0346 (12)	0.0550 (15)	0.0340 (12)	−0.0127 (11)	0.0061 (10)	−0.0060 (11)

Geometric parameters (Å, º) top

Co1—N1ⁱ	2.2184 (18)	C2—C3	1.379 (3)
Co1—N1	2.2185 (18)	C2—H2	0.9300
Co1—N2ⁱⁱ	2.2822 (17)	C3—C4	1.388 (3)
Co1—N2ⁱⁱⁱ	2.2822 (17)	C4—C5	1.386 (3)
Co1—Cl1	2.4221 (5)	C4—H4	0.9300
Co1—Cl1ⁱ	2.4222 (5)	C5—H5	0.9300
S1—C8	1.766 (2)	C6—C7	1.376 (3)
S1—C3	1.775 (2)	C6—H6	0.9300
N1—C1	1.334 (3)	C7—C8	1.384 (3)
N1—C5	1.338 (3)	C7—H7	0.9300
N2—C10	1.340 (3)	C8—C9	1.385 (3)
N2—C6	1.340 (3)	C9—C10	1.381 (3)
N2—Co1^iv	2.2822 (17)	C9—H9	0.9300
C1—C2	1.373 (3)	C10—H10	0.9300
C1—H1	0.9300

N1ⁱ—Co1—N1	180.0	C1—C2—H2	120.5
N1ⁱ—Co1—N2ⁱⁱ	94.00 (6)	C3—C2—H2	120.5
N1—Co1—N2ⁱⁱ	86.00 (6)	C2—C3—C4	118.2 (2)
N1ⁱ—Co1—N2ⁱⁱⁱ	86.00 (6)	C2—C3—S1	121.68 (17)
N1—Co1—N2ⁱⁱⁱ	94.00 (6)	C4—C3—S1	119.80 (17)
N2ⁱⁱ—Co1—N2ⁱⁱⁱ	180.00 (8)	C5—C4—C3	118.1 (2)
N1ⁱ—Co1—Cl1	89.50 (5)	C5—C4—H4	120.9
N1—Co1—Cl1	90.50 (5)	C3—C4—H4	120.9
N2ⁱⁱ—Co1—Cl1	90.03 (4)	N1—C5—C4	124.4 (2)
N2ⁱⁱⁱ—Co1—Cl1	89.97 (4)	N1—C5—H5	117.8
N1ⁱ—Co1—Cl1ⁱ	90.50 (5)	C4—C5—H5	117.8
N1—Co1—Cl1ⁱ	89.50 (5)	N2—C6—C7	124.10 (19)
N2ⁱⁱ—Co1—Cl1ⁱ	89.97 (4)	N2—C6—H6	118.0
N2ⁱⁱⁱ—Co1—Cl1ⁱ	90.03 (4)	C7—C6—H6	118.0
Cl1—Co1—Cl1ⁱ	179.999 (1)	C6—C7—C8	119.2 (2)
C8—S1—C3	102.90 (10)	C6—C7—H7	120.4
C1—N1—C5	115.77 (19)	C8—C7—H7	120.4
C1—N1—Co1	119.81 (14)	C7—C8—C9	117.7 (2)
C5—N1—Co1	124.16 (15)	C7—C8—S1	123.87 (17)
C10—N2—C6	115.96 (18)	C9—C8—S1	118.24 (16)
C10—N2—Co1^iv	121.39 (14)	C10—C9—C8	119.1 (2)
C6—N2—Co1^iv	122.47 (13)	C10—C9—H9	120.5
N1—C1—C2	124.4 (2)	C8—C9—H9	120.5
N1—C1—H1	117.8	N2—C10—C9	124.0 (2)
C2—C1—H1	117.8	N2—C10—H10	118.0
C1—C2—C3	119.0 (2)	C9—C10—H10	118.0

N2ⁱⁱ—Co1—N1—C1	−149.12 (16)	S1—C3—C4—C5	172.1 (2)
N2ⁱⁱⁱ—Co1—N1—C1	30.88 (16)	C1—N1—C5—C4	3.4 (4)
Cl1—Co1—N1—C1	−59.12 (16)	Co1—N1—C5—C4	−170.7 (2)
Cl1ⁱ—Co1—N1—C1	120.88 (16)	C3—C4—C5—N1	−2.4 (4)
N2ⁱⁱ—Co1—N1—C5	24.8 (2)	C10—N2—C6—C7	−0.6 (3)
N2ⁱⁱⁱ—Co1—N1—C5	−155.2 (2)	Co1^iv—N2—C6—C7	−175.65 (16)
Cl1—Co1—N1—C5	114.8 (2)	N2—C6—C7—C8	0.6 (3)
Cl1ⁱ—Co1—N1—C5	−65.2 (2)	C6—C7—C8—C9	0.0 (3)
C5—N1—C1—C2	−1.0 (3)	C6—C7—C8—S1	−174.41 (17)
Co1—N1—C1—C2	173.43 (16)	C3—S1—C8—C7	−41.6 (2)
N1—C1—C2—C3	−2.4 (3)	C3—S1—C8—C9	144.02 (19)
C1—C2—C3—C4	3.3 (3)	C7—C8—C9—C10	−0.6 (4)
C1—C2—C3—S1	−169.79 (17)	S1—C8—C9—C10	174.20 (19)
C8—S1—C3—C2	−51.6 (2)	C6—N2—C10—C9	0.0 (4)
C8—S1—C3—C4	135.4 (2)	Co1^iv—N2—C10—C9	175.13 (19)
C2—C3—C4—C5	−1.0 (4)	C8—C9—C10—N2	0.6 (4)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, −y+3/2, z−1/2; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N2ⁱⁱ	0.93	2.62	3.119 (3)	114
C6—H6···Cl1^iv	0.93	2.66	3.292 (2)	126
C10—H10···Cl1^v	0.93	2.64	3.292 (2)	128

Symmetry codes: (ii) x−1, −y+3/2, z−1/2; (iv) −x+1, y+1/2, −z+3/2; (v) x+1, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[CoCl₂(C₁₀H₈N₂S)₂]
M_r	506.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.4940 (11), 15.355 (2), 9.4009 (14)
β (°)	98.413 (2)
V (Å³)	1070.1 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.26
Crystal size (mm)	0.44 × 0.34 × 0.24

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.608, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	5174, 1969, 1720
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.070, 1.05
No. of reflections	1969
No. of parameters	133
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.26

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Co1—N1	2.2185 (18)	Co1—Cl1	2.4221 (5)
Co1—N2ⁱ	2.2822 (17)

N1—Co1—N2ⁱ	94.00 (6)	N1—Co1—Cl1	90.50 (5)

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N2ⁱⁱ	0.93	2.62	3.119 (3)	114.0
C6—H6···Cl1ⁱⁱⁱ	0.93	2.66	3.292 (2)	125.9
C10—H10···Cl1^iv	0.93	2.64	3.292 (2)	127.9

Symmetry codes: (ii) x−1, −y+3/2, z−1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) x+1, −y+3/2, z+1/2.

Acknowledgements

The authors thank Luo Yang Normal University for supporting this work.

References

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