Bis{2,4-dibromo-6-[(E)-(4-fluoro­benz­yl)imino­meth­yl]phenolato-κ2N,O}cobalt(II)

Yu, H.; Chen, Z.-J.; Jin, Y.-B.; Chang, Y.-K.; Lei, K.-W.

doi:10.1107/S1600536812043929

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page m1423

doi:10.1107/S1600536812043929

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Bis{2,4-dibromo-6-[(E)-(4-fluorobenzyl)iminomethyl]phenolato-κ²N,O}cobalt(II)

Hong Yu,^a Zhu-Jun Chen,^b Yue-Bao Jin,^a Yong-Kang Chang ^a and Ke-Wei Lei ^a ^*

^aState Key Lab. Base of Novel Functional Materials and Preparation Science, Institute of Solid Materials Chemistry, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China, and ^bZhejiang Textile and Fashion College, Ningbo 315211, People's Republic of China
^*Correspondence e-mail: leikeweipublic@hotmail.com

(Received 17 August 2012; accepted 23 October 2012; online 31 October 2012)

The complete molecule of the title complex, [Co(C₁₄H₉Br₂FNO)₂], is generated by crystallographic twofold symmetry, with the Co^II atom lying on the rotation axis. The coordination of the metal atom by the two N,O-bidentate ligands results in a squashed CoN₂O₂ tetrahedron. The six-membered chelate ring is an envelope, with the metal atom as the flap. The dihedral angle between the planes of the aromatic rings within each ligand is 84.1 (6)°.

Related literature

For a related structure, see: Jadeja & Shah (2007 ).

Experimental

Crystal data

[Co(C₁₄H₉Br₂FNO)₂]
M_r = 830.97
Monoclinic, C 2
a = 14.6921 (14) Å
b = 9.7598 (3) Å
c = 13.1195 (13) Å
β = 133.608 (17)°
V = 1362.2 (4) Å³
Z = 2
Mo Kα radiation
μ = 6.54 mm⁻¹
T = 293 K
0.33 × 0.21 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID CCD diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.210, T_max = 0.456
5582 measured reflections
2437 independent reflections
2161 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.079
S = 1.02
2437 reflections
177 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.46 e Å⁻³
Absolute structure: Flack (1983 ), 961 Friedel pairs
Flack parameter: −0.012 (14)

Table 1
Selected geometric parameters (Å, °)

Co1—O1	1.933 (4)
Co1—N1	2.023 (5)

O1—Co1—O1ⁱ	143.6 (2)
O1—Co1—N1	92.90 (17)
O1ⁱ—Co1—N1	104.12 (18)
N1—Co1—N1ⁱ	123.7 (3)
Symmetry code: (i) -x+2, y, -z+2.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812043929/hb6941sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043929/hb6941Isup2.hkl

checkCIF report

Related literature top

For a related structure, see: Jadeja & Shah (2007).

Experimental top

Synthesis of the ligand 2-((E)-(4-fluorobenzylimino) methyl)-4,6-dibromophenol: 3,5-dibromo-2-hydroxybenzal dehyde and (4-fluorophenyl)methanamine (1:1) were dissolved in ethanol and the solution was refluxed for 2 h. After evaporation, a crude product was recrystallized twice from ethanol solution to give a yellow product.

1 mmol (0.77 g) of the ligand and 0.5 mmol (0.145 g) Co(NO₃)₂ were dissolved in ethanol and the solutions mixed and stirred for about 10 minutes. The slow vaporization of the solvent yielded after about 3 d dark red single blocks. Yield: 72.3%. Calcd. for C₂₈H₁₈Br₄CoF₂N₂O₂: C 40.37; H 2.42; O 3.84; N 3.36; Found: C 40.26; H 2.40; O 3.83; N 3.35%.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 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: SHELXL97 (Sheldrick, 2008.

Figures top

Fig. 1. The molecular structure of the title complex, showing 30% probability displacement ellipsoids. Atoms with label suffix A are generated by (2–x, –y, 2–z).

Bis{2,4-dibromo-6-[(E)-(4-fluorobenzyl)iminomethyl]phenolato- κ²N,O}cobalt(II) top

Crystal data top

[Co(C₁₄H₉Br₂FNO)₂]	Z = 2
M_r = 830.97	F(000) = 802
Monoclinic, C2	D_x = 2.026 Mg m⁻³
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 14.6921 (14) Å	θ = 2.8–26.4°
b = 9.7598 (3) Å	µ = 6.54 mm⁻¹
c = 13.1195 (13) Å	T = 293 K
β = 133.608 (17)°	Block, red
V = 1362.2 (4) Å³	0.33 × 0.21 × 0.12 mm

Data collection top

Rigaku R-AXIS RAPID CCD diffractometer	2437 independent reflections
Radiation source: fine-focus sealed tube	2161 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 26.4°, θ_min = 2.8°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −16→18
T_min = 0.210, T_max = 0.456	k = −12→11
5582 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.079	w = 1/[σ²(F_o²) + (0.0352P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
2437 reflections	Δρ_max = 0.44 e Å⁻³
177 parameters	Δρ_min = −0.46 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 961 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.012 (14)

Crystal data top

[Co(C₁₄H₉Br₂FNO)₂]	V = 1362.2 (4) Å³
M_r = 830.97	Z = 2
Monoclinic, C2	Mo Kα radiation
a = 14.6921 (14) Å	µ = 6.54 mm⁻¹
b = 9.7598 (3) Å	T = 293 K
c = 13.1195 (13) Å	0.33 × 0.21 × 0.12 mm
β = 133.608 (17)°

Data collection top

Rigaku R-AXIS RAPID CCD diffractometer	2437 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2161 reflections with I > 2σ(I)
T_min = 0.210, T_max = 0.456	R_int = 0.035
5582 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.079	Δρ_max = 0.44 e Å⁻³
S = 1.02	Δρ_min = −0.46 e Å⁻³
2437 reflections	Absolute structure: Flack (1983), 961 Friedel pairs
177 parameters	Absolute structure parameter: −0.012 (14)
1 restraint

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
Br1	1.04553 (6)	0.62756 (5)	1.37969 (7)	0.04722 (19)
Br2	0.66469 (6)	0.25233 (7)	1.20378 (7)	0.0518 (2)
Co1	1.0000	0.46517 (11)	1.0000	0.0378 (3)
F1	1.0441 (5)	0.0042 (6)	0.6661 (7)	0.108 (2)
O1	0.9762 (3)	0.5270 (4)	1.1203 (4)	0.0377 (9)
N1	0.8324 (4)	0.3673 (5)	0.8675 (5)	0.0380 (11)
C1	0.9177 (5)	0.5015 (5)	1.2457 (6)	0.0317 (12)
C2	0.8477 (5)	0.4400 (6)	1.2682 (6)	0.0354 (13)
H2	0.8609	0.4636	1.3462	0.043*
C3	0.7584 (5)	0.3434 (6)	1.1736 (6)	0.0372 (14)
C4	0.7374 (5)	0.3097 (6)	1.0577 (6)	0.0358 (13)
H4	0.6756	0.2459	0.9939	0.043*
C5	0.8088 (5)	0.3712 (6)	1.0336 (6)	0.0323 (12)
C6	0.9041 (5)	0.4673 (5)	1.1321 (6)	0.0294 (12)
C7	0.7747 (5)	0.3358 (6)	0.9051 (6)	0.0395 (14)
H7	0.7020	0.2837	0.8416	0.047*
C8	0.7686 (5)	0.3365 (7)	0.7212 (6)	0.0437 (15)
H8A	0.7490	0.4220	0.6718	0.052*
H8B	0.6898	0.2904	0.6748	0.052*
C9	0.8460 (5)	0.2477 (7)	0.7099 (6)	0.0373 (13)
C10	0.9141 (7)	0.1382 (8)	0.7983 (8)	0.0622 (19)
H10	0.9152	0.1193	0.8686	0.075*
C11	0.9810 (8)	0.0557 (8)	0.7835 (11)	0.076 (3)
H11	1.0272	−0.0183	0.8435	0.092*
C12	0.9781 (7)	0.0843 (8)	0.6809 (9)	0.063 (2)
C13	0.9111 (6)	0.1905 (8)	0.5902 (8)	0.0566 (18)
H13	0.9091	0.2069	0.5189	0.068*
C14	0.8456 (5)	0.2737 (7)	0.6069 (7)	0.0431 (15)
H14	0.8008	0.3483	0.5474	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0476 (3)	0.0584 (4)	0.0421 (4)	−0.0195 (3)	0.0334 (3)	−0.0154 (3)
Br2	0.0528 (4)	0.0658 (4)	0.0576 (5)	−0.0160 (3)	0.0460 (4)	−0.0025 (3)
Co1	0.0322 (6)	0.0575 (7)	0.0337 (6)	0.000	0.0265 (5)	0.000
F1	0.113 (4)	0.110 (4)	0.138 (5)	0.045 (4)	0.101 (4)	0.006 (4)
O1	0.035 (2)	0.049 (2)	0.041 (2)	−0.0131 (18)	0.031 (2)	−0.0094 (18)
N1	0.031 (2)	0.056 (3)	0.030 (3)	0.002 (2)	0.022 (2)	−0.001 (2)
C1	0.031 (3)	0.034 (3)	0.035 (3)	−0.008 (2)	0.025 (3)	−0.005 (2)
C2	0.043 (3)	0.040 (3)	0.041 (4)	−0.003 (3)	0.035 (3)	−0.001 (3)
C3	0.036 (3)	0.045 (3)	0.042 (4)	−0.008 (3)	0.032 (3)	−0.002 (3)
C4	0.033 (3)	0.039 (3)	0.033 (3)	−0.005 (3)	0.022 (3)	−0.003 (3)
C5	0.032 (3)	0.038 (3)	0.031 (3)	−0.001 (3)	0.023 (3)	0.002 (2)
C6	0.028 (3)	0.033 (3)	0.032 (3)	0.004 (2)	0.022 (3)	0.006 (2)
C7	0.034 (3)	0.048 (3)	0.036 (4)	−0.009 (3)	0.024 (3)	−0.009 (3)
C8	0.034 (3)	0.063 (4)	0.026 (3)	0.002 (3)	0.018 (3)	−0.003 (3)
C9	0.033 (3)	0.046 (3)	0.033 (3)	−0.010 (3)	0.023 (3)	−0.011 (3)
C10	0.071 (5)	0.066 (5)	0.067 (5)	0.008 (4)	0.055 (4)	0.015 (4)
C11	0.079 (5)	0.059 (5)	0.099 (8)	0.029 (4)	0.065 (6)	0.024 (5)
C12	0.061 (5)	0.069 (5)	0.072 (6)	0.005 (4)	0.051 (5)	−0.011 (4)
C13	0.053 (4)	0.076 (5)	0.050 (4)	−0.002 (4)	0.039 (4)	−0.008 (4)
C14	0.043 (3)	0.049 (4)	0.040 (4)	0.001 (3)	0.030 (3)	−0.002 (3)

Geometric parameters (Å, º) top

Br1—C1	1.891 (5)	C5—C6	1.419 (7)
Br2—C3	1.896 (5)	C5—C7	1.430 (8)
Co1—O1	1.933 (4)	C7—H7	0.9300
Co1—O1ⁱ	1.933 (4)	C8—C9	1.515 (8)
Co1—N1	2.023 (5)	C8—H8A	0.9700
Co1—N1ⁱ	2.023 (5)	C8—H8B	0.9700
F1—C12	1.359 (8)	C9—C14	1.371 (8)
O1—C6	1.308 (6)	C9—C10	1.374 (10)
N1—C7	1.279 (7)	C10—C11	1.383 (11)
N1—C8	1.474 (8)	C10—H10	0.9300
C1—C2	1.387 (8)	C11—C12	1.346 (12)
C1—C6	1.400 (7)	C11—H11	0.9300
C2—C3	1.380 (8)	C12—C13	1.358 (10)
C2—H2	0.9300	C13—C14	1.388 (8)
C3—C4	1.367 (8)	C13—H13	0.9300
C4—C5	1.420 (7)	C14—H14	0.9300
C4—H4	0.9300

O1—Co1—O1ⁱ	143.6 (2)	N1—C7—C5	127.6 (5)
O1—Co1—N1	92.90 (17)	N1—C7—H7	116.2
O1ⁱ—Co1—N1	104.12 (18)	C5—C7—H7	116.2
O1—Co1—N1ⁱ	104.12 (18)	N1—C8—C9	113.4 (5)
O1ⁱ—Co1—N1ⁱ	92.90 (17)	N1—C8—H8A	108.9
N1—Co1—N1ⁱ	123.7 (3)	C9—C8—H8A	108.9
C6—O1—Co1	125.1 (3)	N1—C8—H8B	108.9
C7—N1—C8	117.3 (5)	C9—C8—H8B	108.9
C7—N1—Co1	121.3 (4)	H8A—C8—H8B	107.7
C8—N1—Co1	121.3 (4)	C14—C9—C10	118.7 (6)
C2—C1—C6	122.7 (5)	C14—C9—C8	119.8 (6)
C2—C1—Br1	119.3 (4)	C10—C9—C8	121.5 (6)
C6—C1—Br1	117.8 (4)	C9—C10—C11	120.6 (7)
C3—C2—C1	119.3 (5)	C9—C10—H10	119.7
C3—C2—H2	120.4	C11—C10—H10	119.7
C1—C2—H2	120.4	C12—C11—C10	119.0 (7)
C4—C3—C2	120.6 (5)	C12—C11—H11	120.5
C4—C3—Br2	118.7 (4)	C10—C11—H11	120.5
C2—C3—Br2	120.6 (4)	C11—C12—C13	122.6 (7)
C3—C4—C5	120.8 (5)	C11—C12—F1	119.4 (8)
C3—C4—H4	119.6	C13—C12—F1	118.1 (8)
C5—C4—H4	119.6	C12—C13—C14	118.1 (7)
C6—C5—C4	119.5 (5)	C12—C13—H13	121.0
C6—C5—C7	123.8 (5)	C14—C13—H13	121.0
C4—C5—C7	116.6 (5)	C9—C14—C13	121.1 (6)
O1—C6—C1	119.1 (5)	C9—C14—H14	119.5
O1—C6—C5	123.9 (5)	C13—C14—H14	119.5
C1—C6—C5	117.0 (5)

O1ⁱ—Co1—O1—C6	143.4 (4)	C4—C5—C6—O1	178.6 (5)
N1—Co1—O1—C6	24.7 (4)	C7—C5—C6—O1	−4.6 (8)
N1ⁱ—Co1—O1—C6	−101.1 (4)	C4—C5—C6—C1	−3.2 (7)
O1—Co1—N1—C7	−18.8 (5)	C7—C5—C6—C1	173.6 (5)
O1ⁱ—Co1—N1—C7	−166.3 (5)	C8—N1—C7—C5	−171.0 (6)
N1ⁱ—Co1—N1—C7	90.3 (5)	Co1—N1—C7—C5	5.6 (9)
O1—Co1—N1—C8	157.8 (4)	C6—C5—C7—N1	10.5 (10)
O1ⁱ—Co1—N1—C8	10.2 (5)	C4—C5—C7—N1	−172.7 (6)
N1ⁱ—Co1—N1—C8	−93.1 (4)	C7—N1—C8—C9	−124.3 (6)
C6—C1—C2—C3	−1.7 (9)	Co1—N1—C8—C9	59.1 (7)
Br1—C1—C2—C3	−177.1 (4)	N1—C8—C9—C14	−140.6 (6)
C1—C2—C3—C4	−0.9 (9)	N1—C8—C9—C10	41.5 (8)
C1—C2—C3—Br2	177.8 (4)	C14—C9—C10—C11	0.0 (10)
C2—C3—C4—C5	1.3 (9)	C8—C9—C10—C11	178.0 (7)
Br2—C3—C4—C5	−177.4 (4)	C9—C10—C11—C12	−0.2 (13)
C3—C4—C5—C6	0.8 (8)	C10—C11—C12—C13	−0.6 (13)
C3—C4—C5—C7	−176.2 (5)	C10—C11—C12—F1	179.6 (7)
Co1—O1—C6—C1	164.8 (4)	C11—C12—C13—C14	1.4 (11)
Co1—O1—C6—C5	−17.0 (7)	F1—C12—C13—C14	−178.8 (6)
C2—C1—C6—O1	−178.0 (5)	C10—C9—C14—C13	0.9 (9)
Br1—C1—C6—O1	−2.5 (7)	C8—C9—C14—C13	−177.1 (6)
C2—C1—C6—C5	3.7 (8)	C12—C13—C14—C9	−1.5 (9)
Br1—C1—C6—C5	179.2 (4)

Symmetry code: (i) −x+2, y, −z+2.

Experimental details

Crystal data
Chemical formula	[Co(C₁₄H₉Br₂FNO)₂]
M_r	830.97
Crystal system, space group	Monoclinic, C2
Temperature (K)	293
a, b, c (Å)	14.6921 (14), 9.7598 (3), 13.1195 (13)
β (°)	133.608 (17)
V (Å³)	1362.2 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.54
Crystal size (mm)	0.33 × 0.21 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS RAPID CCD diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.210, 0.456
No. of measured, independent and observed [I > 2σ(I)] reflections	5582, 2437, 2161
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.079, 1.02
No. of reflections	2437
No. of parameters	177
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.46
Absolute structure	Flack (1983), 961 Friedel pairs
Absolute structure parameter	−0.012 (14)

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008.

Selected geometric parameters (Å, º) top

Co1—O1	1.933 (4)	Co1—N1	2.023 (5)

O1—Co1—O1ⁱ	143.6 (2)	O1ⁱ—Co1—N1	104.12 (18)
O1—Co1—N1	92.90 (17)	N1—Co1—N1ⁱ	123.7 (3)

Symmetry code: (i) −x+2, y, −z+2.

Acknowledgements

This project was sponsored by K. C. Wong Magna Fund in Ningbo University, the Talent Fund of Ningbo Municipal Natural Science Foundation (No. 2010 A610187) and the Talent Fund of Ningbo University (No. Xkl09070).

References

Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Jadeja, R. T. & Shah, J. R. (2007). Polyhedron, 26, 1677–1685. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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