metal-organic compounds
Bis{2,4-dibromo-6-[(E)-(4-fluorobenzyl)iminomethyl]phenolato-κ2N,O}cobalt(II)
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
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)°.
Experimental
Crystal data
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Data collection: RAPID-AUTO (Rigaku, 1998); cell 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
10.1107/S1600536812043929/hb6941sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812043929/hb6941Isup2.hkl
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%.
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).
Data collection: RAPID-AUTO (Rigaku, 1998); cell
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.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). |
[Co(C14H9Br2FNO)2] | Z = 2 |
Mr = 830.97 | F(000) = 802 |
Monoclinic, C2 | Dx = 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 |
Rigaku R-AXIS RAPID CCD diffractometer | 2437 independent reflections |
Radiation source: fine-focus sealed tube | 2161 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ω scans | θmax = 26.4°, θmin = 2.8° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −16→18 |
Tmin = 0.210, Tmax = 0.456 | k = −12→11 |
5582 measured reflections | l = −16→16 |
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(Fo2) + (0.0352P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
2437 reflections | Δρmax = 0.44 e Å−3 |
177 parameters | Δρmin = −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) |
[Co(C14H9Br2FNO)2] | V = 1362.2 (4) Å3 |
Mr = 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)° |
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 = 0.456 | Rint = 0.035 |
5582 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.079 | Δρmax = 0.44 e Å−3 |
S = 1.02 | Δρmin = −0.46 e Å−3 |
2437 reflections | Absolute structure: Flack (1983), 961 Friedel pairs |
177 parameters | Absolute structure parameter: −0.012 (14) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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] |
Mr | 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) |
Tmin, Tmax | 0.210, 0.456 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5582, 2437, 2161 |
Rint | 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 |
Δρmax, Δρmin (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.
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
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