catena-Poly[[dichloridocobalt(II)]-μ-1,2-di-4-pyridylethane-κ2N:N′]

Wang, Z.-M.

doi:10.1107/S1600536808006685

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page m544

doi:10.1107/S1600536808006685

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catena-Poly[[dichloridocobalt(II)]-μ-1,2-di-4-pyridylethane-κ²N:N′]

Zhi-Min Wang ^a ^*

^aCollege of Biology and Environmental Engineering, Shuren University, Hangzhou 310015, Zhejiang, People's Republic of China
^*Correspondence e-mail: hslj2004@126.com

(Received 7 March 2008; accepted 10 March 2008; online 14 March 2008)

In the title compound, [CoCl₂(C₁₂H₁₂N₂)], the Co^II atom is coordinated in a tetrahedral geometry by the N atoms of two different 1,3-di-4-pyridylpropane ligands. The compound adopts a linear chain structure.

Related literature

For related literature, see: Carlucci et al. (2003 ); Fujita et al. (1998 ).

Experimental

Crystal data

[CoCl₂(C₁₂H₁₂N₂)]
M_r = 314.07
Triclinic, $[P \overline 1]$
a = 5.3979 (17) Å
b = 8.806 (3) Å
c = 14.018 (4) Å
α = 87.988 (5)°
β = 84.165 (5)°
γ = 84.475 (5)°
V = 659.6 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.68 mm⁻¹
T = 298 (2) K
0.27 × 0.21 × 0.18 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.659, T_max = 0.751
3306 measured reflections
2297 independent reflections
1942 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.134
S = 1.02
2297 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −1.01 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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/S1600536808006685/ng2432sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808006685/ng2432Isup2.hkl

checkCIF report

Comment top

In recent years, a wide range of 1-D infinite frameworks have been generated by using simple linear bifunctional ligands (Fujita et al., 1998), such as 4,4'-bipyridine (bpy). 1,3-bis(4-pyridyl)propane (bpp) ligand is typical building element for the assembly of infinite architectures. A double-helical chain was synthesized based on transition metal salts and bpp ligand (Carlucci et al., 2003). In this paper, we report the synthesis and crystal structure of the title complex,(I).

As shown in Fig. 1, the complex I is connected to two bpp ligands. The Co^II atom in compound I is tetrahedrally coordinatted by two N atoms of two different pyridyl groups and two chloride anions. This coordination mode of cobalt atom is very rare so far. The Co^II ions are linked by bpp liagnds and form a zigzag chain. The Co—N bond lengths range from 2.036 (3) to 2.038 (3)Å (Table1). While the Co—Cl bond lengths range from 2.2399 (10) to 2.2484 (11) Å.

Related literature top

For related literature, see: Carlucci et al. (2003); Fujita et al. (1998).

Experimental top

CoCl₂(0.023 g, 0.012 mmol), bpp(0.021 g, 0.013 mmol) were added in a mixed solvent of methanol and benzene, the mixture was heated for ten hours under reflux. During the process stirring and influx were required. The resultant was then filtered to give a pure solution which was infiltrated by diethyl ether freely in a closed vessel, Six weeks later some single crystals was obtained.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 asymmetric unit of (I), showing 30% probability displacement ellipsoids. (symmetrical code: (i) 1 - x, -y, 1 - z).

catena-Poly[[dichloridocobalt(II)]-µ-1,2-di-4-pyridylethane- κ²N:N'] top

Crystal data top

[CoCl₂(C₁₂H₁₂N₂)]	Z = 2
M_r = 314.07	F(000) = 318
Triclinic, P1	D_x = 1.581 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.3979 (17) Å	Cell parameters from 2297 reflections
b = 8.806 (3) Å	θ = 1.5–25.1°
c = 14.018 (4) Å	µ = 1.68 mm⁻¹
α = 87.988 (5)°	T = 298 K
β = 84.165 (5)°	Block, pink
γ = 84.475 (5)°	0.27 × 0.21 × 0.18 mm
V = 659.6 (4) Å³

Data collection top

Bruker APEXII area-detector diffractometer	2297 independent reflections
Radiation source: fine-focus sealed tube	1942 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→6
T_min = 0.659, T_max = 0.752	k = −9→10
3306 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.1008P)²] where P = (F_o² + 2F_c²)/3
2297 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.98 e Å⁻³
0 restraints	Δρ_min = −1.01 e Å⁻³

Crystal data top

[CoCl₂(C₁₂H₁₂N₂)]	γ = 84.475 (5)°
M_r = 314.07	V = 659.6 (4) Å³
Triclinic, P1	Z = 2
a = 5.3979 (17) Å	Mo Kα radiation
b = 8.806 (3) Å	µ = 1.68 mm⁻¹
c = 14.018 (4) Å	T = 298 K
α = 87.988 (5)°	0.27 × 0.21 × 0.18 mm
β = 84.165 (5)°

Data collection top

Bruker APEXII area-detector diffractometer	2297 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1942 reflections with I > 2σ(I)
T_min = 0.659, T_max = 0.752	R_int = 0.022
3306 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.03	Δρ_max = 0.98 e Å⁻³
2297 reflections	Δρ_min = −1.01 e Å⁻³
154 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	0.88487 (8)	0.54658 (4)	0.74750 (3)	0.0386 (2)
Cl1	1.00798 (18)	0.70640 (10)	0.62711 (6)	0.0535 (3)
Cl2	1.14897 (18)	0.42183 (11)	0.84306 (6)	0.0533 (3)
N1	0.7275 (5)	0.3806 (3)	0.68363 (19)	0.0403 (6)
N2	0.6308 (5)	0.6763 (3)	0.8353 (2)	0.0421 (7)
C1	0.5435 (7)	0.4131 (4)	0.6281 (3)	0.0456 (8)
H1	0.4851	0.5151	0.6200	0.055*
C2	0.4336 (7)	0.3066 (4)	0.5819 (3)	0.0489 (9)
H2	0.3053	0.3362	0.5438	0.059*
C3	0.5184 (7)	0.1528 (4)	0.5933 (2)	0.0466 (8)
C4	0.7079 (8)	0.1187 (4)	0.6500 (3)	0.0564 (10)
H4	0.7711	0.0176	0.6585	0.068*
C5	0.8076 (7)	0.2329 (4)	0.6950 (3)	0.0518 (9)
H5	0.9343	0.2062	0.7344	0.062*
C6	0.4098 (7)	0.0307 (4)	0.5416 (3)	0.0536 (9)
H6A	0.2547	0.0730	0.5176	0.064*
H6B	0.3720	−0.0523	0.5864	0.064*
C7	0.4596 (8)	0.7756 (4)	0.7979 (3)	0.0561 (10)
H7	0.4611	0.7858	0.7316	0.067*
C8	0.2815 (8)	0.8629 (5)	0.8552 (3)	0.0628 (11)
H8	0.1652	0.9304	0.8270	0.075*
C9	0.2745 (7)	0.8507 (4)	0.9545 (3)	0.0508 (9)
C10	0.4501 (8)	0.7480 (5)	0.9904 (3)	0.0582 (10)
H10	0.4527	0.7354	1.0565	0.070*
C11	0.6216 (7)	0.6636 (4)	0.9308 (3)	0.0532 (9)
H11	0.7372	0.5942	0.9578	0.064*
C12	0.0852 (8)	0.9406 (4)	1.0232 (3)	0.0610 (11)
H12A	−0.0164	0.8697	1.0598	0.073*
H12B	0.1746	0.9903	1.0680	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0492 (3)	0.0344 (3)	0.0329 (3)	−0.0032 (2)	−0.0083 (2)	−0.00010 (19)
Cl1	0.0644 (6)	0.0466 (5)	0.0484 (5)	−0.0056 (4)	−0.0054 (4)	0.0137 (4)
Cl2	0.0599 (6)	0.0565 (6)	0.0444 (5)	−0.0006 (4)	−0.0178 (4)	0.0065 (4)
N1	0.0491 (16)	0.0361 (15)	0.0366 (15)	−0.0040 (12)	−0.0079 (12)	−0.0013 (11)
N2	0.0495 (16)	0.0389 (15)	0.0389 (15)	−0.0014 (12)	−0.0116 (12)	−0.0018 (12)
C1	0.055 (2)	0.0361 (18)	0.046 (2)	−0.0001 (15)	−0.0103 (16)	−0.0003 (15)
C2	0.055 (2)	0.049 (2)	0.045 (2)	−0.0050 (16)	−0.0140 (16)	−0.0012 (16)
C3	0.057 (2)	0.044 (2)	0.0397 (19)	−0.0111 (16)	−0.0043 (16)	−0.0026 (15)
C4	0.076 (3)	0.0332 (19)	0.063 (3)	−0.0038 (17)	−0.020 (2)	−0.0002 (17)
C5	0.064 (2)	0.039 (2)	0.055 (2)	−0.0021 (16)	−0.0222 (18)	−0.0003 (16)
C6	0.066 (2)	0.049 (2)	0.049 (2)	−0.0170 (18)	−0.0087 (18)	−0.0057 (17)
C7	0.070 (2)	0.060 (2)	0.0354 (19)	0.0119 (19)	−0.0096 (17)	0.0024 (17)
C8	0.068 (3)	0.065 (3)	0.050 (2)	0.023 (2)	−0.0088 (19)	0.0051 (19)
C9	0.060 (2)	0.047 (2)	0.043 (2)	0.0028 (17)	−0.0025 (16)	−0.0014 (16)
C10	0.070 (3)	0.065 (3)	0.0367 (19)	0.012 (2)	−0.0080 (17)	−0.0022 (17)
C11	0.061 (2)	0.053 (2)	0.045 (2)	0.0080 (17)	−0.0085 (17)	−0.0017 (17)
C12	0.070 (3)	0.061 (3)	0.047 (2)	0.012 (2)	−0.0005 (19)	0.0018 (18)

Geometric parameters (Å, º) top

Co1—N1	2.036 (3)	C5—H5	0.9300
Co1—N2	2.038 (3)	C6—C6ⁱ	1.521 (7)
Co1—Cl2	2.2399 (10)	C6—H6A	0.9700
Co1—Cl1	2.2484 (11)	C6—H6B	0.9700
N1—C1	1.327 (4)	C7—C8	1.379 (5)
N1—C5	1.340 (4)	C7—H7	0.9300
N2—C11	1.335 (5)	C8—C9	1.390 (5)
N2—C7	1.343 (5)	C8—H8	0.9300
C1—C2	1.370 (5)	C9—C10	1.368 (5)
C1—H1	0.9300	C9—C12	1.514 (5)
C2—C3	1.397 (5)	C10—C11	1.364 (5)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.362 (5)	C11—H11	0.9300
C3—C6	1.512 (5)	C12—C12ⁱⁱ	1.500 (8)
C4—C5	1.385 (5)	C12—H12A	0.9700
C4—H4	0.9300	C12—H12B	0.9700

N1—Co1—N2	112.50 (11)	C3—C6—C6ⁱ	111.5 (4)
N1—Co1—Cl2	105.20 (8)	C3—C6—H6A	109.3
N2—Co1—Cl2	106.04 (8)	C6ⁱ—C6—H6A	109.3
N1—Co1—Cl1	105.09 (9)	C3—C6—H6B	109.3
N2—Co1—Cl1	104.94 (9)	C6ⁱ—C6—H6B	109.3
Cl2—Co1—Cl1	123.22 (4)	H6A—C6—H6B	108.0
C1—N1—C5	116.8 (3)	N2—C7—C8	121.8 (3)
C1—N1—Co1	121.9 (2)	N2—C7—H7	119.1
C5—N1—Co1	121.3 (2)	C8—C7—H7	119.1
C11—N2—C7	117.5 (3)	C7—C8—C9	120.5 (4)
C11—N2—Co1	122.3 (2)	C7—C8—H8	119.7
C7—N2—Co1	120.2 (2)	C9—C8—H8	119.7
N1—C1—C2	124.5 (3)	C10—C9—C8	116.2 (3)
N1—C1—H1	117.8	C10—C9—C12	119.4 (3)
C2—C1—H1	117.8	C8—C9—C12	124.4 (4)
C1—C2—C3	118.7 (3)	C11—C10—C9	121.0 (4)
C1—C2—H2	120.7	C11—C10—H10	119.5
C3—C2—H2	120.7	C9—C10—H10	119.5
C4—C3—C2	117.2 (3)	N2—C11—C10	122.9 (3)
C4—C3—C6	121.9 (3)	N2—C11—H11	118.5
C2—C3—C6	120.9 (3)	C10—C11—H11	118.5
C3—C4—C5	120.7 (3)	C12ⁱⁱ—C12—C9	115.1 (4)
C3—C4—H4	119.6	C12ⁱⁱ—C12—H12A	108.5
C5—C4—H4	119.6	C9—C12—H12A	108.5
N1—C5—C4	122.1 (3)	C12ⁱⁱ—C12—H12B	108.5
N1—C5—H5	118.9	C9—C12—H12B	108.5
C4—C5—H5	118.9	H12A—C12—H12B	107.5

N2—Co1—N1—C1	58.9 (3)	C6—C3—C4—C5	178.7 (4)
Cl2—Co1—N1—C1	173.9 (3)	C1—N1—C5—C4	1.1 (6)
Cl1—Co1—N1—C1	−54.7 (3)	Co1—N1—C5—C4	−178.1 (3)
N2—Co1—N1—C5	−121.9 (3)	C3—C4—C5—N1	−1.4 (7)
Cl2—Co1—N1—C5	−6.9 (3)	C4—C3—C6—C6ⁱ	−72.0 (6)
Cl1—Co1—N1—C5	124.5 (3)	C2—C3—C6—C6ⁱ	105.6 (5)
N1—Co1—N2—C11	106.3 (3)	C11—N2—C7—C8	0.6 (6)
Cl2—Co1—N2—C11	−8.2 (3)	Co1—N2—C7—C8	178.6 (3)
Cl1—Co1—N2—C11	−140.0 (3)	N2—C7—C8—C9	0.2 (7)
N1—Co1—N2—C7	−71.5 (3)	C7—C8—C9—C10	−0.6 (7)
Cl2—Co1—N2—C7	174.0 (3)	C7—C8—C9—C12	−179.5 (4)
Cl1—Co1—N2—C7	42.2 (3)	C8—C9—C10—C11	0.3 (6)
C5—N1—C1—C2	−0.5 (6)	C12—C9—C10—C11	179.2 (4)
Co1—N1—C1—C2	178.8 (3)	C7—N2—C11—C10	−1.0 (6)
N1—C1—C2—C3	0.1 (6)	Co1—N2—C11—C10	−178.9 (3)
C1—C2—C3—C4	−0.3 (6)	C9—C10—C11—N2	0.6 (7)
C1—C2—C3—C6	−178.0 (3)	C10—C9—C12—C12ⁱⁱ	175.1 (5)
C2—C3—C4—C5	1.0 (6)	C8—C9—C12—C12ⁱⁱ	−6.1 (8)

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

Experimental details

Crystal data
Chemical formula	[CoCl₂(C₁₂H₁₂N₂)]
M_r	314.07
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.3979 (17), 8.806 (3), 14.018 (4)
α, β, γ (°)	87.988 (5), 84.165 (5), 84.475 (5)
V (Å³)	659.6 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.68
Crystal size (mm)	0.27 × 0.21 × 0.18

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.659, 0.752
No. of measured, independent and observed [I > 2σ(I)] reflections	3306, 2297, 1942
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.134, 1.03
No. of reflections	2297
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.98, −1.01

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The author is grateful to Shuren University for financial support.

References

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc, Madison, Wisconsin, USA. Google Scholar
Carlucci, L., Ciani, G., Proserpio, D. M. & Rizzato, S. (2003). CrystEngComm, 5, 190–199. Web of Science CSD CrossRef CAS Google Scholar
Fujita, M., Sasaki, O., Watanabe, K., Ogura, K. & Yamaguchi, K. (1998). New J. Chem. pp. 189–191. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar