Bis(2,4-dichloro­phen­oxy­acetato-κ2O1,O1′)(5,5′-dimethyl-2,2′-bipyridine-κ2N,N′)cobalt(II)

Ji, L.-L.; Liu, J.-S.; Song, W.-D.

doi:10.1107/S1600536811010579

metal-organic compounds

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Volume 67| Part 4| April 2011| Page m493

doi:10.1107/S1600536811010579

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Bis(2,4-dichlorophenoxyacetato-κ²O¹,O^1′)(5,5′-dimethyl-2,2′-bipyridine-κ²N,N′)cobalt(II)

Li-Li Ji,^a Jian-She Liu ^a ^* and Wen-Dong Song ^b

^aEnvironment Science and Engineering, Dong Hua University, Shanghai 200051, People's Republic of China, and ^bCollege of Science, Guangdong Ocean University, Zhanjiang 524088, People's Republic of China
^*Correspondence e-mail: liujianshe@dhu.edu.cn

(Received 18 March 2011; accepted 22 March 2011; online 26 March 2011)

In the title compound, [Co(C₈H₅Cl₂O₃)(C₁₂H₁₂N₂)], the Co^II atom, lying on a twofold rotation axis, is coordinated by four O atoms from two chelating 2,4-dichlorophenoxyacetate ligands and two N atoms from a 5,5′-dimethyl-2,2′-bipyridine ligand, displaying a distorted octahedral geometry. A three-dimensional supramolecular structure is formed through intermolecular C—H⋯O hydrogen bonds and π–π stacking interactions between the pyridine and benzene rings [centroid–centroid distance = 3.779 (2) Å].

Related literature

For related structures with 2,4-dichlorophenoxyacetate ligands, see: Liu (2010 ); Song & Xi (2006 ).

Experimental

Crystal data

[Co(C₈H₅Cl₂O₃)(C₁₂H₁₂N₂)]
M_r = 683.21
Monoclinic, P 2/c
a = 13.397 (2) Å
b = 8.4152 (14) Å
c = 13.752 (2) Å
β = 112.570 (3)°
V = 1431.7 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.02 mm⁻¹
T = 296 K
0.30 × 0.28 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.756, T_max = 0.819
10343 measured reflections
2567 independent reflections
2229 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.106
S = 1.14
2567 reflections
187 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O3ⁱ	0.97	2.49	3.391 (3)	154
C12—H12⋯O2ⁱⁱ	0.93	2.40	3.157 (4)	139
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x+1, y+1, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811010579/hy2417sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811010579/hy2417Isup2.hkl

checkCIF report

Comment top

In the structural investigation of 2,4-dichlorophenoxyacetate complexes, it has been found that 2,4-dichlorophenoxyacetic acid functions as a multidentate ligand (Liu, 2010; Song & Xi, 2006), with versatile binding and coordination modes. In this paper, we report the crystal structure of the title compound, a new Co(II) complex obtained by the reaction of 2,4-dichlorophenoxyacetic acid, 5,5'-dimethyl-2,2'-bipyridine and cobalt nitrate hexahydrate in an alkaline aqueous solution.

As illustrated in Fig. 1, the Co^II atom, lying on a twofold rotation axis, exists in an distorted octahedral environment defined by four carboxylate O atoms from two different bidentate 2,4-dichlorophenoxyacetate ligands and two N atoms from one 5,5'-dimethyl-2,2'-bipyridine ligand. Intermolecular C—H···O hydrogen bonds (Table 1) and π–π stacking interactions are observed (Fig. 2). The centroid–centroid distance between a pyridine ring and a benzene ring at (1-x, 1-y, -z) is 3.779 (2) Å, thus indicating a weak π–π stacking interaction.

Related literature top

For related structures with 2,4-dichlorophenoxyacetate ligands, see: Liu (2010); Song & Xi (2006).

Experimental top

A mixture of 2,4-dichlorophenoxyacetic acid (0.110 g, 0.5 mmol), 5,5'-dimethyl-2,2'-bipyridine (0.092 g, 0.5 mmol), cobalt nitrate hexahydrate (0.145 g, 0.5 mmol), NaOH (0.08 g, 0.2 mmol) and H₂O (10 ml) was placed in a 23 ml Teflon-lined reactor, which was heated to 423 K for 3 days, and then cooled to room temperature at a rate of 10 K h^-1. The block purple crystals obtained were washed with water and dried in air (yield: 45% based on Co).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (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) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids. [Symmetry code: (i) 1-x, y, 1/2-z.]
	Fig. 2. Packing diagram of the title compound. C—H···O hydrogen bonds and π–π interactions are shown as dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity.

Bis(2,4-dichlorophenoxyacetato-κ²O¹,O^1')(5,5'- dimethyl-2,2'-bipyridine-κ²N,N')cobalt(II) top

Crystal data top

[Co(C₈H₅Cl₂O₃)(C₁₂H₁₂N₂)]	F(000) = 694
M_r = 683.21	D_x = 1.585 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 5837 reflections
a = 13.397 (2) Å	θ = 2.8–27.9°
b = 8.4152 (14) Å	µ = 1.02 mm⁻¹
c = 13.752 (2) Å	T = 296 K
β = 112.570 (3)°	Block, purple
V = 1431.7 (4) Å³	0.30 × 0.28 × 0.21 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	2567 independent reflections
Radiation source: fine-focus sealed tube	2229 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 25.2°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
T_min = 0.756, T_max = 0.819	k = −10→9
10343 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0443P)² + 1.0781P] where P = (F_o² + 2F_c²)/3
2567 reflections	(Δ/σ)_max = 0.001
187 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Co(C₈H₅Cl₂O₃)(C₁₂H₁₂N₂)]	V = 1431.7 (4) Å³
M_r = 683.21	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 13.397 (2) Å	µ = 1.02 mm⁻¹
b = 8.4152 (14) Å	T = 296 K
c = 13.752 (2) Å	0.30 × 0.28 × 0.21 mm
β = 112.570 (3)°

Data collection top

Bruker APEXII CCD diffractometer	2567 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2229 reflections with I > 2σ(I)
T_min = 0.756, T_max = 0.819	R_int = 0.028
10343 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.14	Δρ_max = 0.28 e Å⁻³
2567 reflections	Δρ_min = −0.37 e Å⁻³
187 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.7163 (2)	0.1694 (3)	0.0470 (2)	0.0440 (7)
C2	0.7908 (3)	0.0498 (4)	0.0494 (2)	0.0514 (7)
C3	0.8966 (3)	0.0881 (5)	0.0701 (3)	0.0670 (10)
H3	0.9462	0.0089	0.0732	0.080*
C4	0.9289 (3)	0.2447 (5)	0.0861 (3)	0.0689 (10)
C5	0.8566 (3)	0.3634 (5)	0.0807 (3)	0.0693 (10)
H5	0.8790	0.4689	0.0900	0.083*
C6	0.7503 (3)	0.3250 (4)	0.0612 (3)	0.0563 (8)
H6	0.7013	0.4052	0.0577	0.068*
C7	0.5307 (2)	0.2314 (3)	0.0072 (2)	0.0426 (6)
H7A	0.4623	0.1799	−0.0321	0.051*
H7B	0.5408	0.3142	−0.0373	0.051*
C8	0.5240 (2)	0.3081 (3)	0.1036 (2)	0.0363 (6)
C9	0.2940 (3)	0.6310 (4)	0.2236 (2)	0.0543 (8)
H9	0.2643	0.5303	0.2203	0.065*
C10	0.2281 (3)	0.7617 (5)	0.2140 (3)	0.0638 (9)
C11	0.2754 (4)	0.9083 (5)	0.2190 (3)	0.0766 (12)
H11	0.2344	0.9995	0.2134	0.092*
C12	0.3815 (4)	0.9229 (4)	0.2320 (2)	0.0644 (10)
H12	0.4123	1.0226	0.2343	0.077*
C13	0.4424 (3)	0.7856 (3)	0.2417 (2)	0.0446 (7)
C14	0.1122 (3)	0.7418 (6)	0.2007 (4)	0.0932 (14)
H14A	0.0665	0.7517	0.1276	0.140*
H14B	0.0937	0.8222	0.2404	0.140*
H14C	0.1025	0.6387	0.2257	0.140*
Cl1	0.74751 (8)	−0.14382 (10)	0.02104 (8)	0.0675 (3)
Cl2	1.06334 (9)	0.28906 (19)	0.11140 (13)	0.1133 (5)
Co1	0.5000	0.45028 (5)	0.2500	0.03575 (17)
N1	0.3975 (2)	0.6418 (3)	0.23719 (18)	0.0429 (6)
O1	0.61468 (16)	0.1179 (2)	0.02776 (17)	0.0482 (5)
O2	0.59131 (17)	0.2812 (2)	0.19438 (15)	0.0471 (5)
O3	0.44679 (16)	0.4039 (2)	0.08733 (15)	0.0460 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0543 (17)	0.0405 (15)	0.0426 (15)	0.0081 (13)	0.0248 (13)	−0.0017 (12)
C2	0.0608 (19)	0.0482 (17)	0.0496 (17)	0.0134 (15)	0.0261 (15)	0.0016 (14)
C3	0.055 (2)	0.081 (3)	0.067 (2)	0.0212 (18)	0.0251 (17)	0.0001 (19)
C4	0.0500 (19)	0.084 (3)	0.074 (2)	−0.0019 (18)	0.0245 (17)	−0.013 (2)
C5	0.064 (2)	0.071 (2)	0.080 (3)	−0.0110 (19)	0.0352 (19)	−0.019 (2)
C6	0.061 (2)	0.0475 (18)	0.069 (2)	0.0053 (15)	0.0347 (17)	−0.0076 (16)
C7	0.0504 (16)	0.0378 (14)	0.0447 (15)	0.0063 (12)	0.0239 (13)	−0.0020 (12)
C8	0.0499 (15)	0.0237 (12)	0.0429 (15)	−0.0003 (11)	0.0262 (13)	0.0016 (11)
C9	0.0608 (19)	0.0546 (19)	0.0493 (17)	0.0114 (15)	0.0232 (15)	−0.0006 (14)
C10	0.079 (2)	0.067 (2)	0.0501 (19)	0.0319 (19)	0.0292 (17)	0.0086 (16)
C11	0.110 (3)	0.068 (3)	0.057 (2)	0.049 (2)	0.038 (2)	0.0093 (18)
C12	0.110 (3)	0.0374 (17)	0.0464 (18)	0.0194 (18)	0.0307 (19)	0.0019 (13)
C13	0.0789 (19)	0.0252 (13)	0.0302 (13)	0.0057 (12)	0.0217 (14)	−0.0008 (10)
C14	0.079 (3)	0.116 (4)	0.087 (3)	0.045 (3)	0.035 (2)	0.009 (3)
Cl1	0.0849 (6)	0.0432 (5)	0.0889 (7)	0.0162 (4)	0.0495 (5)	0.0002 (4)
Cl2	0.0555 (6)	0.1306 (11)	0.1526 (12)	−0.0124 (6)	0.0388 (7)	−0.0322 (9)
Co1	0.0512 (3)	0.0227 (3)	0.0400 (3)	0.000	0.0248 (2)	0.000
N1	0.0590 (15)	0.0341 (13)	0.0390 (13)	0.0066 (11)	0.0225 (11)	−0.0005 (10)
O1	0.0547 (12)	0.0372 (10)	0.0628 (13)	0.0063 (9)	0.0338 (10)	−0.0038 (9)
O2	0.0657 (13)	0.0352 (10)	0.0421 (11)	0.0102 (9)	0.0227 (10)	0.0026 (8)
O3	0.0540 (11)	0.0430 (11)	0.0456 (11)	0.0099 (9)	0.0242 (9)	−0.0030 (9)

Geometric parameters (Å, º) top

C1—O1	1.355 (4)	C9—H9	0.9300
C1—C6	1.375 (4)	C10—C11	1.377 (6)
C1—C2	1.408 (4)	C10—C14	1.500 (6)
C2—C3	1.374 (5)	C11—C12	1.368 (6)
C2—Cl1	1.723 (3)	C11—H11	0.9300
C3—C4	1.378 (6)	C12—C13	1.391 (4)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.372 (5)	C13—N1	1.342 (4)
C4—Cl2	1.739 (4)	C13—C13ⁱ	1.470 (6)
C5—C6	1.383 (5)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—H6	0.9300	C14—H14C	0.9600
C7—O1	1.419 (3)	Co1—N1ⁱ	2.080 (2)
C7—C8	1.508 (4)	Co1—N1	2.080 (2)
C7—H7A	0.9700	Co1—O3	2.1073 (19)
C7—H7B	0.9700	Co1—O3ⁱ	2.1074 (19)
C8—O2	1.249 (3)	Co1—O2	2.1963 (19)
C8—O3	1.262 (3)	Co1—O2ⁱ	2.1963 (19)
C9—N1	1.329 (4)	Co1—C8ⁱ	2.467 (3)
C9—C10	1.385 (4)

O1—C1—C6	125.8 (3)	C13—C12—H12	120.7
O1—C1—C2	115.2 (3)	N1—C13—C12	120.5 (3)
C6—C1—C2	119.0 (3)	N1—C13—C13ⁱ	115.62 (16)
C3—C2—C1	120.2 (3)	C12—C13—C13ⁱ	123.9 (2)
C3—C2—Cl1	120.0 (3)	C10—C14—H14A	109.5
C1—C2—Cl1	119.8 (2)	C10—C14—H14B	109.5
C2—C3—C4	119.5 (3)	H14A—C14—H14B	109.5
C2—C3—H3	120.3	C10—C14—H14C	109.5
C4—C3—H3	120.3	H14A—C14—H14C	109.5
C5—C4—C3	121.1 (3)	H14B—C14—H14C	109.5
C5—C4—Cl2	120.6 (3)	N1ⁱ—Co1—N1	78.44 (14)
C3—C4—Cl2	118.3 (3)	N1ⁱ—Co1—O3	100.17 (8)
C4—C5—C6	119.5 (4)	N1—Co1—O3	96.32 (8)
C4—C5—H5	120.2	N1ⁱ—Co1—O3ⁱ	96.32 (8)
C6—C5—H5	120.2	N1—Co1—O3ⁱ	100.17 (8)
C1—C6—C5	120.7 (3)	O3—Co1—O3ⁱ	158.67 (11)
C1—C6—H6	119.7	N1ⁱ—Co1—O2	95.37 (9)
C5—C6—H6	119.7	N1—Co1—O2	155.51 (8)
O1—C7—C8	115.0 (2)	O3—Co1—O2	61.12 (7)
O1—C7—H7A	108.5	O3ⁱ—Co1—O2	104.07 (8)
C8—C7—H7A	108.5	N1ⁱ—Co1—O2ⁱ	155.51 (8)
O1—C7—H7B	108.5	N1—Co1—O2ⁱ	95.37 (9)
C8—C7—H7B	108.5	O3—Co1—O2ⁱ	104.07 (8)
H7A—C7—H7B	107.5	O3ⁱ—Co1—O2ⁱ	61.12 (7)
O2—C8—O3	121.4 (2)	O2—Co1—O2ⁱ	99.27 (11)
O2—C8—C7	122.5 (2)	N1ⁱ—Co1—C8ⁱ	126.52 (9)
O3—C8—C7	116.1 (2)	N1—Co1—C8ⁱ	98.99 (9)
N1—C9—C10	123.5 (3)	O3—Co1—C8ⁱ	132.83 (9)
N1—C9—H9	118.2	O3ⁱ—Co1—C8ⁱ	30.76 (8)
C10—C9—H9	118.2	O2—Co1—C8ⁱ	103.57 (8)
C11—C10—C9	116.2 (4)	O2ⁱ—Co1—C8ⁱ	30.36 (8)
C11—C10—C14	122.8 (3)	C9—N1—C13	119.5 (3)
C9—C10—C14	121.0 (4)	C9—N1—Co1	125.3 (2)
C12—C11—C10	121.5 (3)	C13—N1—Co1	115.1 (2)
C12—C11—H11	119.2	C1—O1—C7	118.9 (2)
C10—C11—H11	119.2	C8—O2—Co1	86.89 (15)
C11—C12—C13	118.7 (3)	C8—O3—Co1	90.57 (16)
C11—C12—H12	120.7

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
C7—H7B···O3ⁱⁱ	0.97	2.49	3.391 (3)	154
C12—H12···O2ⁱⁱⁱ	0.93	2.40	3.157 (4)	139

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

Experimental details

Crystal data
Chemical formula	[Co(C₈H₅Cl₂O₃)(C₁₂H₁₂N₂)]
M_r	683.21
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	296
a, b, c (Å)	13.397 (2), 8.4152 (14), 13.752 (2)
β (°)	112.570 (3)
V (Å³)	1431.7 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.30 × 0.28 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.756, 0.819
No. of measured, independent and observed [I > 2σ(I)] reflections	10343, 2567, 2229
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.106, 1.14
No. of reflections	2567
No. of parameters	187
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.37

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O3ⁱ	0.97	2.49	3.391 (3)	154
C12—H12···O2ⁱⁱ	0.93	2.40	3.157 (4)	139

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

Acknowledgements

The authors acknowledge Donghua University for supporting this work.

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, S.-Z. (2010). Acta Cryst. E66, m199. Web of Science CSD CrossRef IUCr Journals 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
Song, W.-D. & Xi, D.-L. (2006). Acta Cryst. E62, m2594–m2596. Web of Science CSD CrossRef IUCr Journals Google Scholar

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