metal-organic compounds
Bis{2,4-dibromo-6-[(E)-(4-fluorobenzyl)iminomethyl]phenolato-κ2N,O}zinc
aLanzhou University of Technology, State Key Laboratory of Gansu Advanced Non-ferrous Metal Materials, Lanzhou 730000, Gansu Province, People's Republic of China, and bState 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
*Correspondence e-mail: leikeweipublic@hotmail.com
In the title Schiff base complex, [Zn(C14H9Br2FNO)2], the ZnII atom is located on a twofold rotation axis and is coordinated by two O and two N atoms from two symmetry-related bidentate Schiff base ligands in a compressed tetrahedral geometry. The bond lengths and bond angles are within normal ranges. The dihedral angle between the least-squares planes of the aromatic rings within each ligand is 82.76 (17)°.
Related literature
For the coordination ability of et al. (1994). For and thermochromism in see: Cohen (1964).
ligands, see: Rodriguez BarbarinExperimental
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/S1600536812043930/ds2215sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812043930/ds2215Isup2.hkl
1 mmol(0.29g) of Zn(NO3)2 were added to 20 ml ethanol solution containing 2 mmol(0.77g) 2-((E)-(4-fluorobenzylimino) methyl)-4,6-dibromophenol.The resulting mixture was stirred for about 10 minute.The slow vaporisation of the solvent yielded after about 2 d yellow product.Yield:87.1%. Calcd.for C28 H18 Br4 F2 N2 O2 Zn: C,43.44;H,2.60;O,4.13;N,3.62; Found:C,43.50;H,2.61;O,14.15;N,3.61%
3,5-dibromo-2-hydroxybenzal dehyde(10mmol,2.80g) and (4-fluorophenyl)methanamine (10mmol,1.25g) dissolved in ethanol respectively. Then put them together and the solution was refluxed for 0.5h. After evaporation,a crude product was recrystallized twice from ethanol to give a pure yellow product.
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 structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme. |
[Zn(C14H9Br2FNO)2] | Z = 2 |
Mr = 837.43 | F(000) = 808 |
Monoclinic, C2 | Dx = 2.038 Mg m−3 |
Hall symbol: C 2Y | Mo Kα radiation, λ = 0.71073 Å |
a = 14.6277 (11) Å | θ = 2.8–26.4° |
b = 9.8273 (3) Å | µ = 6.80 mm−1 |
c = 13.0879 (10) Å | T = 293 K |
β = 133.490 (13)° | Block, yellow |
V = 1364.9 (3) Å3 | 0.33 × 0.21 × 0.12 mm |
Rigaku R-AXIS RAPID diffractometer | 2785 independent reflections |
Radiation source: fine-focus sealed tube | 2733 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 26.4°, θmin = 2.8° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −18→18 |
Tmin = 0.197, Tmax = 0.442 | k = −12→12 |
16865 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)] = 0.017 | H-atom parameters constrained |
wR(F2) = 0.041 | w = 1/[σ2(Fo2) + (0.0207P)2 + 0.6898P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
2785 reflections | Δρmax = 0.22 e Å−3 |
177 parameters | Δρmin = −0.24 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1307 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.009 (7) |
[Zn(C14H9Br2FNO)2] | V = 1364.9 (3) Å3 |
Mr = 837.43 | Z = 2 |
Monoclinic, C2 | Mo Kα radiation |
a = 14.6277 (11) Å | µ = 6.80 mm−1 |
b = 9.8273 (3) Å | T = 293 K |
c = 13.0879 (10) Å | 0.33 × 0.21 × 0.12 mm |
β = 133.490 (13)° |
Rigaku R-AXIS RAPID diffractometer | 2785 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2733 reflections with I > 2σ(I) |
Tmin = 0.197, Tmax = 0.442 | Rint = 0.025 |
16865 measured reflections |
R[F2 > 2σ(F2)] = 0.017 | H-atom parameters constrained |
wR(F2) = 0.041 | Δρmax = 0.22 e Å−3 |
S = 1.05 | Δρmin = −0.24 e Å−3 |
2785 reflections | Absolute structure: Flack (1983), 1307 Friedel pairs |
177 parameters | Absolute structure parameter: −0.009 (7) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 1.04547 (2) | 0.46777 (3) | 1.37836 (3) | 0.04434 (8) | |
Br2 | 0.66508 (3) | 0.09397 (3) | 1.20503 (3) | 0.05004 (8) | |
Zn1 | 1.0000 | 0.30224 (4) | 1.0000 | 0.03419 (10) | |
F1 | 1.0457 (3) | −0.1547 (3) | 0.6672 (3) | 0.1080 (9) | |
O1 | 0.97414 (16) | 0.36983 (17) | 1.11706 (18) | 0.0347 (4) | |
N1 | 0.83087 (19) | 0.2066 (2) | 0.8654 (2) | 0.0366 (5) | |
C1 | 0.9037 (2) | 0.3095 (2) | 1.1302 (2) | 0.0281 (4) | |
C2 | 0.9183 (2) | 0.3416 (2) | 1.2459 (3) | 0.0310 (5) | |
C3 | 0.8483 (2) | 0.2810 (3) | 1.2690 (3) | 0.0346 (5) | |
H3 | 0.8609 | 0.3047 | 1.3467 | 0.042* | |
C4 | 0.7589 (2) | 0.1838 (3) | 1.1733 (3) | 0.0360 (5) | |
C5 | 0.7374 (2) | 0.1507 (3) | 1.0573 (3) | 0.0356 (5) | |
H5 | 0.6754 | 0.0874 | 0.9933 | 0.043* | |
C6 | 0.8086 (2) | 0.2117 (2) | 1.0336 (3) | 0.0314 (5) | |
C7 | 0.7726 (2) | 0.1769 (3) | 0.9027 (3) | 0.0364 (5) | |
H7 | 0.6986 | 0.1271 | 0.8384 | 0.044* | |
C8 | 0.7676 (2) | 0.1760 (3) | 0.7192 (3) | 0.0445 (6) | |
H8A | 0.7485 | 0.2608 | 0.6700 | 0.053* | |
H8B | 0.6883 | 0.1305 | 0.6725 | 0.053* | |
C9 | 0.8450 (2) | 0.0878 (3) | 0.7088 (3) | 0.0373 (5) | |
C10 | 0.9129 (3) | −0.0210 (4) | 0.7977 (3) | 0.0583 (8) | |
H10 | 0.9133 | −0.0392 | 0.8677 | 0.070* | |
C11 | 0.9809 (4) | −0.1039 (4) | 0.7839 (5) | 0.0726 (11) | |
H11 | 1.0268 | −0.1776 | 0.8438 | 0.087* | |
C12 | 0.9785 (3) | −0.0746 (4) | 0.6806 (4) | 0.0613 (9) | |
C13 | 0.9123 (3) | 0.0310 (4) | 0.5906 (3) | 0.0547 (8) | |
H13 | 0.9120 | 0.0479 | 0.5205 | 0.066* | |
C14 | 0.8450 (2) | 0.1132 (3) | 0.6051 (3) | 0.0419 (6) | |
H14 | 0.7993 | 0.1863 | 0.5443 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.04587 (15) | 0.05435 (16) | 0.03650 (13) | −0.01934 (12) | 0.02976 (12) | −0.01577 (12) |
Br2 | 0.05293 (16) | 0.06223 (18) | 0.05420 (17) | −0.01660 (14) | 0.04423 (15) | −0.00359 (13) |
Zn1 | 0.0318 (2) | 0.0480 (2) | 0.0308 (2) | 0.000 | 0.02466 (19) | 0.000 |
F1 | 0.117 (2) | 0.1067 (19) | 0.136 (2) | 0.0427 (17) | 0.101 (2) | 0.0050 (17) |
O1 | 0.0378 (9) | 0.0428 (9) | 0.0360 (9) | −0.0102 (7) | 0.0302 (8) | −0.0072 (7) |
N1 | 0.0344 (11) | 0.0514 (12) | 0.0280 (11) | −0.0005 (9) | 0.0230 (10) | −0.0038 (9) |
C1 | 0.0265 (11) | 0.0328 (11) | 0.0279 (11) | 0.0017 (9) | 0.0198 (10) | 0.0031 (9) |
C2 | 0.0289 (12) | 0.0357 (12) | 0.0282 (12) | −0.0034 (9) | 0.0196 (11) | −0.0021 (9) |
C3 | 0.0388 (13) | 0.0420 (12) | 0.0345 (13) | −0.0029 (10) | 0.0296 (12) | −0.0015 (10) |
C4 | 0.0349 (12) | 0.0438 (13) | 0.0406 (14) | −0.0041 (11) | 0.0303 (12) | 0.0030 (11) |
C5 | 0.0342 (13) | 0.0404 (12) | 0.0356 (13) | −0.0066 (10) | 0.0253 (12) | −0.0041 (10) |
C6 | 0.0300 (11) | 0.0383 (12) | 0.0300 (12) | −0.0030 (9) | 0.0222 (11) | −0.0023 (9) |
C7 | 0.0304 (12) | 0.0444 (14) | 0.0329 (13) | −0.0078 (11) | 0.0212 (11) | −0.0106 (11) |
C8 | 0.0353 (14) | 0.0686 (17) | 0.0274 (13) | 0.0040 (13) | 0.0207 (12) | −0.0035 (12) |
C9 | 0.0359 (12) | 0.0437 (13) | 0.0307 (12) | −0.0058 (11) | 0.0222 (11) | −0.0080 (11) |
C10 | 0.0658 (19) | 0.0631 (18) | 0.0575 (18) | 0.0062 (17) | 0.0469 (17) | 0.0110 (16) |
C11 | 0.074 (2) | 0.060 (2) | 0.083 (3) | 0.0224 (18) | 0.054 (2) | 0.019 (2) |
C12 | 0.061 (2) | 0.063 (2) | 0.068 (2) | 0.0075 (17) | 0.0479 (18) | −0.0103 (18) |
C13 | 0.0561 (18) | 0.073 (2) | 0.0455 (16) | −0.0029 (16) | 0.0389 (15) | −0.0098 (16) |
C14 | 0.0401 (14) | 0.0511 (15) | 0.0349 (13) | 0.0004 (12) | 0.0260 (12) | −0.0039 (11) |
Br1—C2 | 1.888 (2) | C5—H5 | 0.9300 |
Br2—C4 | 1.902 (2) | C6—C7 | 1.446 (3) |
Zn1—O1 | 1.9311 (16) | C7—H7 | 0.9300 |
Zn1—O1i | 1.9311 (17) | C8—C9 | 1.505 (4) |
Zn1—N1 | 2.027 (2) | C8—H8A | 0.9700 |
Zn1—N1i | 2.027 (2) | C8—H8B | 0.9700 |
F1—C12 | 1.361 (4) | C9—C10 | 1.375 (4) |
O1—C1 | 1.299 (3) | C9—C14 | 1.380 (4) |
N1—C7 | 1.274 (3) | C10—C11 | 1.390 (5) |
N1—C8 | 1.473 (3) | C10—H10 | 0.9300 |
C1—C2 | 1.412 (3) | C11—C12 | 1.360 (5) |
C1—C6 | 1.427 (3) | C11—H11 | 0.9300 |
C2—C3 | 1.384 (3) | C12—C13 | 1.353 (5) |
C3—C4 | 1.392 (4) | C13—C14 | 1.384 (4) |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.362 (3) | C14—H14 | 0.9300 |
C5—C6 | 1.408 (3) | ||
O1—Zn1—O1i | 139.77 (10) | N1—C7—C6 | 127.3 (2) |
O1—Zn1—N1 | 93.47 (7) | N1—C7—H7 | 116.3 |
O1i—Zn1—N1 | 104.97 (8) | C6—C7—H7 | 116.3 |
O1—Zn1—N1i | 104.97 (8) | N1—C8—C9 | 113.3 (2) |
O1i—Zn1—N1i | 93.47 (7) | N1—C8—H8A | 108.9 |
N1—Zn1—N1i | 124.76 (13) | C9—C8—H8A | 108.9 |
C1—O1—Zn1 | 123.68 (15) | N1—C8—H8B | 108.9 |
C7—N1—C8 | 117.5 (2) | C9—C8—H8B | 108.9 |
C7—N1—Zn1 | 120.79 (17) | H8A—C8—H8B | 107.7 |
C8—N1—Zn1 | 121.59 (16) | C10—C9—C14 | 118.9 (3) |
O1—C1—C2 | 119.5 (2) | C10—C9—C8 | 121.4 (2) |
O1—C1—C6 | 124.7 (2) | C14—C9—C8 | 119.7 (2) |
C2—C1—C6 | 115.9 (2) | C9—C10—C11 | 120.7 (3) |
C3—C2—C1 | 123.3 (2) | C9—C10—H10 | 119.6 |
C3—C2—Br1 | 119.44 (18) | C11—C10—H10 | 119.6 |
C1—C2—Br1 | 117.22 (16) | C12—C11—C10 | 118.3 (3) |
C2—C3—C4 | 118.5 (2) | C12—C11—H11 | 120.9 |
C2—C3—H3 | 120.7 | C10—C11—H11 | 120.9 |
C4—C3—H3 | 120.7 | C13—C12—C11 | 122.7 (3) |
C5—C4—C3 | 121.3 (2) | C13—C12—F1 | 118.6 (3) |
C5—C4—Br2 | 119.04 (19) | C11—C12—F1 | 118.7 (3) |
C3—C4—Br2 | 119.68 (18) | C12—C13—C14 | 118.6 (3) |
C4—C5—C6 | 120.4 (2) | C12—C13—H13 | 120.7 |
C4—C5—H5 | 119.8 | C14—C13—H13 | 120.7 |
C6—C5—H5 | 119.8 | C9—C14—C13 | 120.8 (3) |
C5—C6—C1 | 120.6 (2) | C9—C14—H14 | 119.6 |
C5—C6—C7 | 116.0 (2) | C13—C14—H14 | 119.6 |
C1—C6—C7 | 123.2 (2) | ||
O1i—Zn1—O1—C1 | 145.92 (19) | O1—C1—C6—C5 | 179.5 (2) |
N1—Zn1—O1—C1 | 27.73 (19) | C2—C1—C6—C5 | −1.4 (3) |
N1i—Zn1—O1—C1 | −99.68 (19) | O1—C1—C6—C7 | −5.3 (4) |
O1—Zn1—N1—C7 | −20.3 (2) | C2—C1—C6—C7 | 173.8 (2) |
O1i—Zn1—N1—C7 | −164.2 (2) | C8—N1—C7—C6 | −172.0 (3) |
N1i—Zn1—N1—C7 | 90.6 (2) | Zn1—N1—C7—C6 | 4.6 (4) |
O1—Zn1—N1—C8 | 156.2 (2) | C5—C6—C7—N1 | −171.5 (3) |
O1i—Zn1—N1—C8 | 12.3 (2) | C1—C6—C7—N1 | 13.1 (4) |
N1i—Zn1—N1—C8 | −92.9 (2) | C7—N1—C8—C9 | −124.7 (3) |
Zn1—O1—C1—C2 | 161.59 (16) | Zn1—N1—C8—C9 | 58.7 (3) |
Zn1—O1—C1—C6 | −19.3 (3) | N1—C8—C9—C10 | 41.3 (4) |
O1—C1—C2—C3 | −179.2 (2) | N1—C8—C9—C14 | −140.9 (3) |
C6—C1—C2—C3 | 1.7 (3) | C14—C9—C10—C11 | 0.2 (5) |
O1—C1—C2—Br1 | −2.1 (3) | C8—C9—C10—C11 | 178.0 (3) |
C6—C1—C2—Br1 | 178.73 (17) | C9—C10—C11—C12 | 0.1 (6) |
C1—C2—C3—C4 | −0.2 (4) | C10—C11—C12—C13 | −0.4 (6) |
Br1—C2—C3—C4 | −177.20 (19) | C10—C11—C12—F1 | 179.5 (3) |
C2—C3—C4—C5 | −1.7 (4) | C11—C12—C13—C14 | 0.5 (5) |
C2—C3—C4—Br2 | 177.87 (19) | F1—C12—C13—C14 | −179.4 (3) |
C3—C4—C5—C6 | 1.9 (4) | C10—C9—C14—C13 | −0.1 (4) |
Br2—C4—C5—C6 | −177.63 (19) | C8—C9—C14—C13 | −178.0 (3) |
C4—C5—C6—C1 | −0.3 (4) | C12—C13—C14—C9 | −0.2 (4) |
C4—C5—C6—C7 | −175.8 (2) |
Symmetry code: (i) −x+2, y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C14H9Br2FNO)2] |
Mr | 837.43 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 293 |
a, b, c (Å) | 14.6277 (11), 9.8273 (3), 13.0879 (10) |
β (°) | 133.490 (13) |
V (Å3) | 1364.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 6.80 |
Crystal size (mm) | 0.33 × 0.21 × 0.12 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.197, 0.442 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16865, 2785, 2733 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.017, 0.041, 1.05 |
No. of reflections | 2785 |
No. of parameters | 177 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.24 |
Absolute structure | Flack (1983), 1307 Friedel pairs |
Absolute structure parameter | −0.009 (7) |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This project was sponsored by the 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
Cohen, M. D., Schmidt, G. M. J. & Flavian, S. (1964). J. Chem. Soc. pp. 2041–2043. CrossRef Web of Science Google Scholar
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
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Rodriguez Barbarin, C. O., Bailey, N. A., Fenton, D. E. & He, Q. (1994). Inorg. Chim. Acta, 219, 205–207. CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Schiff bases ligands have been used with remarkable success in the field of coordination chemistry over past decades (Rodriguez Barbarin et al., 1994). Schiff bases complexs show photochromism and thermochromism in the solid state by proton transfer from the hydroxyl O atom to the imine N atom (Cohen et al.,1964). Here we report on a new Schiff bases complex.
The molecular structure of title complex as illustrated in Fig.1. The dihedral angle between two benzenes rings is 83.281 (4)°. The Zn2+ atom is located on a twofold rotation axis in a compressed tetrahedral geometry and is is coordinated by two O atoms and two N atoms. The Zn1-O1 distance of 1.9311 (1)Å is shorter than the distance of Zn1-N1[2.0268 (4)Å](table 1) The bond lengths and bond angles in title complex are within normal ranges.