Bis{2-[(E)-benzyl­imino­meth­yl]-4,6-dibromo­phenolato-κ2N,O}cobalt(II)

Jiang, W.; Mo, G.-D.; Jin, L.

doi:10.1107/S1600536808032303

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1394

doi:10.1107/S1600536808032303

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Bis{2-[(E)-benzyliminomethyl]-4,6-dibromophenolato-κ²N,O}cobalt(II)

Wei Jiang,^a ^* Gui-Di Mo ^a and Lie Jin ^a

^aSchool of Chemistry and Life Sciences, Maoming University, Guandu Second Road 139, Maoming 525000, Guangdong, People's Republic of China
^*Correspondence e-mail: gdmmjw@yahoo.cn

(Received 2 October 2008; accepted 7 October 2008; online 15 October 2008)

In the title compound, [Co(C₁₄H₁₀Br₂NO)₂], the Co^II ion is coordinated by an O and an N atom from two equivalent 2-[(E)-benzyliminomethyl]-4,6-dibromophenolate ligands, displaying a distorted tetrahedral geometry. The Co^II ion occupies a special position on a twofold rotation axis and thus the molecular symmetry of the complex is C₂. The two phenolate rings are perpendicular [89.8 (3)°].

Related literature

For general background on the applications of Schiff bases, see: Vigato et al. (2007 ).

Experimental

Crystal data

[Co(C₁₄H₁₀Br₂NO)₂]
M_r = 795.03
Monoclinic, C 2/c
a = 23.875 (3) Å
b = 4.8190 (6) Å
c = 24.209 (3) Å
β = 105.8730 (1)°
V = 2679.1 (6) Å³
Z = 4
Mo Kα radiation
μ = 6.64 mm⁻¹
T = 296 (2) K
0.30 × 0.26 × 0.22 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ) T_min = 0.165, T_max = 0.232
11046 measured reflections
3094 independent reflections
2627 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.172
S = 1.07
3094 reflections
168 parameters
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −1.46 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co1—O1	1.935 (4)
Co1—N1	2.005 (4)

O1ⁱ—Co1—O1	126.8 (2)
O1ⁱ—Co1—N1	94.16 (17)
O1—Co1—N1	113.29 (17)
N1—Co1—N1ⁱ	117.1 (3)
Symmetry code: (i) $[-x, y, -z+{\script{1\over 2}}]$ .

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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: XP in SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808032303/kp2194sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808032303/kp2194Isup2.hkl

checkCIF report

Comment top

The Schiff bases are widely employed as ligands in coordination chemistry. The advantages of Schiff bases enable their use in the synthesis of metal complexes of interest in bioinorganic chemistry, catalysis, encapsulation, transport and separation processes, and magnetochemistry (Choi & Jeon, 2003). Salicylaldehyde and its derivatives are useful carbonyl precursors for the synthesis of a large variety of Schiff bases. In this paper we report on a new cobalt(II) complex (I).

In the title complex Co^II atom is tetrahedrally coordinated by two O atoms and two N atoms from two 2-((E)-(benzylimino)methyl)-4,6-dibromophenol bidentate chelating ligand. The Co1—O1 distance of 1.935 (4) Å is shorter than the distance of Co1—N1 (2.005 (4) Å) (Table 1). The dihedral angle between two phenol rings is 89.8 (3)°.

Related literature top

For general background on the applications of Schiff bases, see: Choi & Jeon (2003). [Please check rephrasing]

Experimental top

To a solution containing 2 mmol (0.738 g) 2-((E)-(benzylimino)methyl)-4,6-dibromophenol dissolved in 20 mL ethanol, 1 mmol of CoCl₂.6H₂O (0.238 g) were added, and the resulting mixture was stirred for about 1 h. The slow evaporisation of the solvent after about 3 d yielded dark brown single crystals. Yield: 51.4%. Calcd. for C₂₈H₂₀Br₄CoN₂O₂: C, 42.30; H, 2.54; N, 3.52; Found: C, 42.24; H, 3.41; N,3.46%.

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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: XP in SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of (I), showing displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) -x, y, -z+0.5]

Bis{2-[(E)-benzyliminomethyl]-4,6-dibromophenolato-κ²N,O}cobalt(II) top

Crystal data top

[Co(C₁₄H₁₀Br₂NO)₂]	F(000) = 1540
M_r = 795.03	D_x = 1.971 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2269 reflections
a = 23.875 (3) Å	θ = 1.0–27.7°
b = 4.8190 (6) Å	µ = 6.64 mm⁻¹
c = 24.209 (3) Å	T = 296 K
β = 105.873 (1)°	Block, brown
V = 2679.1 (6) Å³	0.30 × 0.26 × 0.22 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	3094 independent reflections
Radiation source: fine-focus sealed tube	2627 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 27.7°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −30→30
T_min = 0.165, T_max = 0.232	k = −6→6
11046 measured reflections	l = −30→31

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1045P)² + 20.5054P] where P = (F_o² + 2F_c²)/3
3094 reflections	(Δ/σ)_max < 0.001
168 parameters	Δρ_max = 0.98 e Å⁻³
0 restraints	Δρ_min = −1.46 e Å⁻³

Crystal data top

[Co(C₁₄H₁₀Br₂NO)₂]	V = 2679.1 (6) Å³
M_r = 795.03	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 23.875 (3) Å	µ = 6.64 mm⁻¹
b = 4.8190 (6) Å	T = 296 K
c = 24.209 (3) Å	0.30 × 0.26 × 0.22 mm
β = 105.873 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3094 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	2627 reflections with I > 2σ(I)
T_min = 0.165, T_max = 0.232	R_int = 0.027
11046 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1045P)² + 20.5054P] where P = (F_o² + 2F_c²)/3
3094 reflections	Δρ_max = 0.98 e Å⁻³
168 parameters	Δρ_min = −1.46 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.0000	0.9824 (2)	0.2500	0.0481 (3)
Br1	0.25733 (3)	0.73207 (15)	0.14570 (3)	0.0446 (2)
Br2	0.06423 (3)	1.45190 (13)	0.09822 (2)	0.0389 (2)
O1	0.04168 (16)	1.1622 (8)	0.20173 (16)	0.0316 (8)
N1	−0.06936 (19)	0.7651 (9)	0.20554 (18)	0.0269 (9)
C1	0.0898 (2)	1.0738 (10)	0.1927 (2)	0.0260 (10)
C2	0.1095 (2)	1.1793 (11)	0.1464 (2)	0.0285 (10)
C3	0.1595 (2)	1.0865 (12)	0.1339 (2)	0.0313 (11)
H3A	0.1707	1.1621	0.1032	0.038*
C4	0.1925 (2)	0.8813 (13)	0.1672 (2)	0.0321 (11)
C5	0.1772 (2)	0.7738 (12)	0.2136 (2)	0.0336 (11)
H5A	0.2005	0.6395	0.2364	0.040*
C6	0.1268 (2)	0.8649 (12)	0.2269 (2)	0.0281 (10)
C7	−0.1144 (2)	0.7334 (12)	0.2242 (2)	0.0309 (11)
H7A	−0.1425	0.6106	0.2037	0.037*
C8	−0.0702 (3)	0.6166 (12)	0.1512 (2)	0.0327 (11)
H8A	−0.0934	0.4492	0.1482	0.039*
H8B	−0.0309	0.5631	0.1517	0.039*
C9	−0.0954 (3)	0.7997 (11)	0.1000 (2)	0.0320 (11)
C10	−0.1555 (3)	0.8139 (16)	0.0759 (3)	0.0483 (16)
H10A	−0.1807	0.7055	0.0901	0.058*
C11	−0.1773 (4)	0.9955 (19)	0.0296 (3)	0.059 (2)
H11A	−0.2174	1.0061	0.0137	0.071*
C12	−0.1433 (4)	1.1523 (16)	0.0075 (3)	0.0555 (19)
H12A	−0.1593	1.2715	−0.0229	0.067*
C13	−0.0827 (4)	1.1356 (17)	0.0309 (3)	0.0533 (17)
H13A	−0.0581	1.2426	0.0157	0.064*
C14	−0.0597 (3)	0.9608 (14)	0.0764 (3)	0.0420 (14)
H14A	−0.0195	0.9504	0.0915	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0443 (5)	0.0596 (6)	0.0428 (5)	0.000	0.0163 (4)	0.000
Br1	0.0289 (3)	0.0637 (4)	0.0467 (4)	0.0012 (2)	0.0197 (3)	−0.0043 (3)
Br2	0.0460 (4)	0.0389 (3)	0.0348 (3)	0.0015 (2)	0.0160 (3)	0.0099 (2)
O1	0.0320 (19)	0.039 (2)	0.0299 (19)	0.0049 (16)	0.0186 (16)	0.0067 (16)
N1	0.027 (2)	0.033 (2)	0.021 (2)	0.0010 (16)	0.0071 (17)	0.0003 (16)
C1	0.028 (2)	0.030 (2)	0.022 (2)	−0.0039 (19)	0.0092 (19)	−0.0012 (18)
C2	0.033 (3)	0.031 (3)	0.024 (2)	−0.006 (2)	0.011 (2)	−0.0022 (19)
C3	0.032 (3)	0.038 (3)	0.028 (3)	−0.010 (2)	0.014 (2)	−0.005 (2)
C4	0.026 (2)	0.042 (3)	0.032 (3)	−0.004 (2)	0.012 (2)	−0.006 (2)
C5	0.027 (3)	0.044 (3)	0.029 (3)	0.001 (2)	0.006 (2)	0.000 (2)
C6	0.026 (2)	0.038 (3)	0.022 (2)	−0.002 (2)	0.0078 (19)	−0.001 (2)
C7	0.027 (3)	0.042 (3)	0.023 (2)	−0.004 (2)	0.006 (2)	−0.003 (2)
C8	0.041 (3)	0.034 (3)	0.025 (2)	0.006 (2)	0.013 (2)	−0.002 (2)
C9	0.045 (3)	0.031 (3)	0.023 (2)	0.001 (2)	0.013 (2)	−0.0074 (19)
C10	0.043 (4)	0.061 (4)	0.042 (4)	0.007 (3)	0.014 (3)	0.004 (3)
C11	0.048 (4)	0.076 (5)	0.046 (4)	0.016 (4)	0.000 (3)	0.003 (4)
C12	0.084 (6)	0.051 (4)	0.025 (3)	0.005 (4)	0.005 (3)	0.001 (3)
C13	0.065 (5)	0.056 (4)	0.036 (3)	−0.011 (4)	0.010 (3)	0.006 (3)
C14	0.044 (3)	0.052 (4)	0.029 (3)	−0.007 (3)	0.008 (3)	0.000 (2)

Geometric parameters (Å, º) top

Co1—O1ⁱ	1.935 (4)	C6—C7ⁱ	1.441 (7)
Co1—O1	1.935 (4)	C7—C6ⁱ	1.441 (7)
Co1—N1	2.005 (4)	C7—H7A	0.9300
Co1—N1ⁱ	2.005 (4)	C8—C9	1.505 (8)
Br1—C4	1.902 (5)	C8—H8A	0.9700
Br2—C2	1.888 (6)	C8—H8B	0.9700
O1—C1	1.298 (6)	C9—C14	1.388 (8)
N1—C7	1.285 (7)	C9—C10	1.396 (9)
N1—C8	1.493 (7)	C10—C11	1.404 (11)
C1—C2	1.424 (7)	C10—H10A	0.9300
C1—C6	1.442 (7)	C11—C12	1.323 (12)
C2—C3	1.383 (7)	C11—H11A	0.9300
C3—C4	1.379 (8)	C12—C13	1.405 (11)
C3—H3A	0.9300	C12—H12A	0.9300
C4—C5	1.376 (8)	C13—C14	1.375 (10)
C5—C6	1.399 (8)	C13—H13A	0.9300
C5—H5A	0.9300	C14—H14A	0.9300

O1ⁱ—Co1—O1	126.8 (2)	N1—C7—C6ⁱ	127.9 (5)
O1ⁱ—Co1—N1	94.16 (17)	N1—C7—H7A	116.0
O1—Co1—N1	113.29 (17)	C6ⁱ—C7—H7A	116.0
O1ⁱ—Co1—N1ⁱ	113.29 (17)	N1—C8—C9	110.5 (4)
O1—Co1—N1ⁱ	94.16 (17)	N1—C8—H8A	109.6
N1—Co1—N1ⁱ	117.1 (3)	C9—C8—H8A	109.6
C1—O1—Co1	125.4 (3)	N1—C8—H8B	109.6
C7—N1—C8	116.2 (5)	C9—C8—H8B	109.6
C7—N1—Co1	121.4 (4)	H8A—C8—H8B	108.1
C8—N1—Co1	122.3 (4)	C14—C9—C10	118.5 (6)
O1—C1—C2	120.9 (5)	C14—C9—C8	121.1 (6)
O1—C1—C6	124.4 (4)	C10—C9—C8	120.5 (6)
C2—C1—C6	114.7 (4)	C9—C10—C11	118.6 (7)
C3—C2—C1	123.3 (5)	C9—C10—H10A	120.7
C3—C2—Br2	118.2 (4)	C11—C10—H10A	120.7
C1—C2—Br2	118.6 (4)	C12—C11—C10	123.0 (7)
C4—C3—C2	119.6 (5)	C12—C11—H11A	118.5
C4—C3—H3A	120.2	C10—C11—H11A	118.5
C2—C3—H3A	120.2	C11—C12—C13	118.8 (7)
C5—C4—C3	120.6 (5)	C11—C12—H12A	120.6
C5—C4—Br1	120.0 (5)	C13—C12—H12A	120.6
C3—C4—Br1	119.3 (4)	C14—C13—C12	120.0 (7)
C4—C5—C6	120.6 (5)	C14—C13—H13A	120.0
C4—C5—H5A	119.7	C12—C13—H13A	120.0
C6—C5—H5A	119.7	C13—C14—C9	121.2 (7)
C5—C6—C7ⁱ	115.6 (5)	C13—C14—H14A	119.4
C5—C6—C1	121.2 (5)	C9—C14—H14A	119.4
C7ⁱ—C6—C1	123.2 (5)

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Co(C₁₄H₁₀Br₂NO)₂]
M_r	795.03
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	23.875 (3), 4.8190 (6), 24.209 (3)
β (°)	105.873 (1)
V (Å³)	2679.1 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.64
Crystal size (mm)	0.30 × 0.26 × 0.22

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2000)
T_min, T_max	0.165, 0.232
No. of measured, independent and observed [I > 2σ(I)] reflections	11046, 3094, 2627
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.172, 1.07
No. of reflections	3094
No. of parameters	168
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.1045P)² + 20.5054P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.98, −1.46

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

Selected geometric parameters (Å, º) top

Co1—O1	1.935 (4)	Co1—N1	2.005 (4)

O1ⁱ—Co1—O1	126.8 (2)	O1—Co1—N1	113.29 (17)
O1ⁱ—Co1—N1	94.16 (17)	N1—Co1—N1ⁱ	117.1 (3)

Symmetry code: (i) −x, y, −z+1/2.

Acknowledgements

We are grateful to the Starting Fund for the Doctoral Program of Maoming University for financial support.

References

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2000). 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
Vigato, P.A., Tamburini, S. & Bertolo, L. (2007). Coord. Chem. Rev. 251, 1311–1316. Web of Science CrossRef CAS Google Scholar