supplementary materials


hb6941 scheme

Acta Cryst. (2012). E68, m1423    [ doi:10.1107/S1600536812043929 ]

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

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

Abstract top

The complete molecule of the title complex, [Co(C14H9Br2FNO)2], is generated by crystallographic twofold symmetry, with the CoII 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 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%.

Refinement top

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms (C—H = 0.93%A) and Uiso(H) values equal to 1.2 Ueq(C).

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
[Figure 1] 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
Mr = 830.97F(000) = 802
Monoclinic, C2Dx = 2.026 Mg m3
Hall symbol: C 2yMo Kα radiation, λ = 0.71073 Å
a = 14.6921 (14) Åθ = 2.8–26.4°
b = 9.7598 (3) ŵ = 6.54 mm1
c = 13.1195 (13) ÅT = 293 K
β = 133.608 (17)°Block, red
V = 1362.2 (4) Å30.33 × 0.21 × 0.12 mm
Data collection top
Rigaku R-AXIS RAPID CCD
diffractometer
2437 independent reflections
Radiation source: fine-focus sealed tube2161 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ω scansθmax = 26.4°, θmin = 2.8°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 1618
Tmin = 0.210, Tmax = 0.456k = 1211
5582 measured reflectionsl = 1616
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.079 w = 1/[σ2(Fo2) + (0.0352P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
2437 reflectionsΔρmax = 0.44 e Å3
177 parametersΔρmin = 0.46 e Å3
1 restraintAbsolute structure: Flack (1983), 961 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.012 (14)
Crystal data top
[Co(C14H9Br2FNO)2]V = 1362.2 (4) Å3
Mr = 830.97Z = 2
Monoclinic, C2Mo Kα radiation
a = 14.6921 (14) ŵ = 6.54 mm1
b = 9.7598 (3) ÅT = 293 K
c = 13.1195 (13) Å0.33 × 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)
Tmin = 0.210, Tmax = 0.456Rint = 0.035
5582 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.079Δρmax = 0.44 e Å3
S = 1.02Δρmin = 0.46 e Å3
2437 reflectionsAbsolute structure: Flack (1983), 961 Friedel pairs
177 parametersFlack 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
xyzUiso*/Ueq
Br11.04553 (6)0.62756 (5)1.37969 (7)0.04722 (19)
Br20.66469 (6)0.25233 (7)1.20378 (7)0.0518 (2)
Co11.00000.46517 (11)1.00000.0378 (3)
F11.0441 (5)0.0042 (6)0.6661 (7)0.108 (2)
O10.9762 (3)0.5270 (4)1.1203 (4)0.0377 (9)
N10.8324 (4)0.3673 (5)0.8675 (5)0.0380 (11)
C10.9177 (5)0.5015 (5)1.2457 (6)0.0317 (12)
C20.8477 (5)0.4400 (6)1.2682 (6)0.0354 (13)
H20.86090.46361.34620.043*
C30.7584 (5)0.3434 (6)1.1736 (6)0.0372 (14)
C40.7374 (5)0.3097 (6)1.0577 (6)0.0358 (13)
H40.67560.24590.99390.043*
C50.8088 (5)0.3712 (6)1.0336 (6)0.0323 (12)
C60.9041 (5)0.4673 (5)1.1321 (6)0.0294 (12)
C70.7747 (5)0.3358 (6)0.9051 (6)0.0395 (14)
H70.70200.28370.84160.047*
C80.7686 (5)0.3365 (7)0.7212 (6)0.0437 (15)
H8A0.74900.42200.67180.052*
H8B0.68980.29040.67480.052*
C90.8460 (5)0.2477 (7)0.7099 (6)0.0373 (13)
C100.9141 (7)0.1382 (8)0.7983 (8)0.0622 (19)
H100.91520.11930.86860.075*
C110.9810 (8)0.0557 (8)0.7835 (11)0.076 (3)
H111.02720.01830.84350.092*
C120.9781 (7)0.0843 (8)0.6809 (9)0.063 (2)
C130.9111 (6)0.1905 (8)0.5902 (8)0.0566 (18)
H130.90910.20690.51890.068*
C140.8456 (5)0.2737 (7)0.6069 (7)0.0431 (15)
H140.80080.34830.54740.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0476 (3)0.0584 (4)0.0421 (4)0.0195 (3)0.0334 (3)0.0154 (3)
Br20.0528 (4)0.0658 (4)0.0576 (5)0.0160 (3)0.0460 (4)0.0025 (3)
Co10.0322 (6)0.0575 (7)0.0337 (6)0.0000.0265 (5)0.000
F10.113 (4)0.110 (4)0.138 (5)0.045 (4)0.101 (4)0.006 (4)
O10.035 (2)0.049 (2)0.041 (2)0.0131 (18)0.031 (2)0.0094 (18)
N10.031 (2)0.056 (3)0.030 (3)0.002 (2)0.022 (2)0.001 (2)
C10.031 (3)0.034 (3)0.035 (3)0.008 (2)0.025 (3)0.005 (2)
C20.043 (3)0.040 (3)0.041 (4)0.003 (3)0.035 (3)0.001 (3)
C30.036 (3)0.045 (3)0.042 (4)0.008 (3)0.032 (3)0.002 (3)
C40.033 (3)0.039 (3)0.033 (3)0.005 (3)0.022 (3)0.003 (3)
C50.032 (3)0.038 (3)0.031 (3)0.001 (3)0.023 (3)0.002 (2)
C60.028 (3)0.033 (3)0.032 (3)0.004 (2)0.022 (3)0.006 (2)
C70.034 (3)0.048 (3)0.036 (4)0.009 (3)0.024 (3)0.009 (3)
C80.034 (3)0.063 (4)0.026 (3)0.002 (3)0.018 (3)0.003 (3)
C90.033 (3)0.046 (3)0.033 (3)0.010 (3)0.023 (3)0.011 (3)
C100.071 (5)0.066 (5)0.067 (5)0.008 (4)0.055 (4)0.015 (4)
C110.079 (5)0.059 (5)0.099 (8)0.029 (4)0.065 (6)0.024 (5)
C120.061 (5)0.069 (5)0.072 (6)0.005 (4)0.051 (5)0.011 (4)
C130.053 (4)0.076 (5)0.050 (4)0.002 (4)0.039 (4)0.008 (4)
C140.043 (3)0.049 (4)0.040 (4)0.001 (3)0.030 (3)0.002 (3)
Geometric parameters (Å, º) top
Br1—C11.891 (5)C5—C61.419 (7)
Br2—C31.896 (5)C5—C71.430 (8)
Co1—O11.933 (4)C7—H70.9300
Co1—O1i1.933 (4)C8—C91.515 (8)
Co1—N12.023 (5)C8—H8A0.9700
Co1—N1i2.023 (5)C8—H8B0.9700
F1—C121.359 (8)C9—C141.371 (8)
O1—C61.308 (6)C9—C101.374 (10)
N1—C71.279 (7)C10—C111.383 (11)
N1—C81.474 (8)C10—H100.9300
C1—C21.387 (8)C11—C121.346 (12)
C1—C61.400 (7)C11—H110.9300
C2—C31.380 (8)C12—C131.358 (10)
C2—H20.9300C13—C141.388 (8)
C3—C41.367 (8)C13—H130.9300
C4—C51.420 (7)C14—H140.9300
C4—H40.9300
O1—Co1—O1i143.6 (2)N1—C7—C5127.6 (5)
O1—Co1—N192.90 (17)N1—C7—H7116.2
O1i—Co1—N1104.12 (18)C5—C7—H7116.2
O1—Co1—N1i104.12 (18)N1—C8—C9113.4 (5)
O1i—Co1—N1i92.90 (17)N1—C8—H8A108.9
N1—Co1—N1i123.7 (3)C9—C8—H8A108.9
C6—O1—Co1125.1 (3)N1—C8—H8B108.9
C7—N1—C8117.3 (5)C9—C8—H8B108.9
C7—N1—Co1121.3 (4)H8A—C8—H8B107.7
C8—N1—Co1121.3 (4)C14—C9—C10118.7 (6)
C2—C1—C6122.7 (5)C14—C9—C8119.8 (6)
C2—C1—Br1119.3 (4)C10—C9—C8121.5 (6)
C6—C1—Br1117.8 (4)C9—C10—C11120.6 (7)
C3—C2—C1119.3 (5)C9—C10—H10119.7
C3—C2—H2120.4C11—C10—H10119.7
C1—C2—H2120.4C12—C11—C10119.0 (7)
C4—C3—C2120.6 (5)C12—C11—H11120.5
C4—C3—Br2118.7 (4)C10—C11—H11120.5
C2—C3—Br2120.6 (4)C11—C12—C13122.6 (7)
C3—C4—C5120.8 (5)C11—C12—F1119.4 (8)
C3—C4—H4119.6C13—C12—F1118.1 (8)
C5—C4—H4119.6C12—C13—C14118.1 (7)
C6—C5—C4119.5 (5)C12—C13—H13121.0
C6—C5—C7123.8 (5)C14—C13—H13121.0
C4—C5—C7116.6 (5)C9—C14—C13121.1 (6)
O1—C6—C1119.1 (5)C9—C14—H14119.5
O1—C6—C5123.9 (5)C13—C14—H14119.5
C1—C6—C5117.0 (5)
O1i—Co1—O1—C6143.4 (4)C4—C5—C6—O1178.6 (5)
N1—Co1—O1—C624.7 (4)C7—C5—C6—O14.6 (8)
N1i—Co1—O1—C6101.1 (4)C4—C5—C6—C13.2 (7)
O1—Co1—N1—C718.8 (5)C7—C5—C6—C1173.6 (5)
O1i—Co1—N1—C7166.3 (5)C8—N1—C7—C5171.0 (6)
N1i—Co1—N1—C790.3 (5)Co1—N1—C7—C55.6 (9)
O1—Co1—N1—C8157.8 (4)C6—C5—C7—N110.5 (10)
O1i—Co1—N1—C810.2 (5)C4—C5—C7—N1172.7 (6)
N1i—Co1—N1—C893.1 (4)C7—N1—C8—C9124.3 (6)
C6—C1—C2—C31.7 (9)Co1—N1—C8—C959.1 (7)
Br1—C1—C2—C3177.1 (4)N1—C8—C9—C14140.6 (6)
C1—C2—C3—C40.9 (9)N1—C8—C9—C1041.5 (8)
C1—C2—C3—Br2177.8 (4)C14—C9—C10—C110.0 (10)
C2—C3—C4—C51.3 (9)C8—C9—C10—C11178.0 (7)
Br2—C3—C4—C5177.4 (4)C9—C10—C11—C120.2 (13)
C3—C4—C5—C60.8 (8)C10—C11—C12—C130.6 (13)
C3—C4—C5—C7176.2 (5)C10—C11—C12—F1179.6 (7)
Co1—O1—C6—C1164.8 (4)C11—C12—C13—C141.4 (11)
Co1—O1—C6—C517.0 (7)F1—C12—C13—C14178.8 (6)
C2—C1—C6—O1178.0 (5)C10—C9—C14—C130.9 (9)
Br1—C1—C6—O12.5 (7)C8—C9—C14—C13177.1 (6)
C2—C1—C6—C53.7 (8)C12—C13—C14—C91.5 (9)
Br1—C1—C6—C5179.2 (4)
Symmetry code: (i) x+2, y, z+2.
Selected geometric parameters (Å, º) top
Co1—O11.933 (4)Co1—N12.023 (5)
O1—Co1—O1i143.6 (2)O1i—Co1—N1104.12 (18)
O1—Co1—N192.90 (17)N1—Co1—N1i123.7 (3)
Symmetry code: (i) x+2, y, z+2.
Acknowledgements top

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
References top

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Jadeja, R. T. & Shah, J. R. (2007). Polyhedron, 26, 1677–1685.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.