Poly[dichloridobis(μ₂-di-4-pyridyl sulfide-κ² N,N′)cobalt(II)]

Abstract

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,

• a = 7.4940 (11) Å

• b = 15.355 (2) Å

• c = 9.4009 (14) Å

• β = 98.413 (2)°

• V = 1070.1 (3) ų

• 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[F ² > 2σ(F ²)] = 0.027

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

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⋯Cl1iv	0.93	2.64	3.292 (2)	128

Symmetry codes: (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

The H atoms were positioned geometrically and treated as riding, with C—H = 0.93 Å (CH) and Uĩso~(H) = 1.2Ueq(C).

Figures

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.

Crystal data

[CoCl2(C10H8N2S)2]	F(000) = 514
Mr = 506.32	Dx = 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

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

Refinement

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(Fo2) + (0.0329P)2 + 0.5314P] where P = (Fo2 + 2Fc2)/3
1969 reflections	(Δ/σ)max < 0.001
133 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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—Co1iv	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—Co1iv	121.39 (14)	C10—C9—C8	119.1 (2)
C6—N2—Co1iv	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)	Co1iv—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)	Co1iv—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, °)

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···Cl1iv	0.93	2.66	3.292 (2)	126
C10—H10···Cl1v	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.