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

Zhang, D.; Yu, H.; Jin, Y.-B.; Lei, K.-W.

doi:10.1107/S1600536812043930

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page m1424

doi:10.1107/S1600536812043930

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

Dingjun Zhang,^a Hong Yu,^b Yue-Bao Jin ^b and Ke-Wei Lei ^b ^*

^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

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

In the title Schiff base complex, [Zn(C₁₄H₉Br₂FNO)₂], the Zn^II 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 Schiff bases ligands, see: Rodriguez Barbarin et al. (1994 ). For photochromism and thermochromism in Schiff bases, see: Cohen (1964 ).

Experimental

Crystal data

[Zn(C₁₄H₉Br₂FNO)₂]
M_r = 837.43
Monoclinic, C 2
a = 14.6277 (11) Å
b = 9.8273 (3) Å
c = 13.0879 (10) Å
β = 133.490 (13)°
V = 1364.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 6.80 mm⁻¹
T = 293 K
0.33 × 0.21 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.197, T_max = 0.442
16865 measured reflections
2785 independent reflections
2733 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.041
S = 1.05
2785 reflections
177 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 1307 Friedel pairs
Flack parameter: −0.009 (7)

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/S1600536812043930/ds2215sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043930/ds2215Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For the coordination ability of Schiff bases ligands, see: Rodriguez Barbarin et al. (1994). For photochromism and thermochromism in Schiff bases, see: Cohen (1964).

Experimental top

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.

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 structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme.

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

Crystal data top

[Zn(C₁₄H₉Br₂FNO)₂]	Z = 2
M_r = 837.43	F(000) = 808
Monoclinic, C2	D_x = 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

Data collection top

Rigaku R-AXIS RAPID diffractometer	2785 independent reflections
Radiation source: fine-focus sealed tube	2733 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 26.4°, θ_min = 2.8°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −18→18
T_min = 0.197, T_max = 0.442	k = −12→12
16865 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)] = 0.017	H-atom parameters constrained
wR(F²) = 0.041	w = 1/[σ²(F_o²) + (0.0207P)² + 0.6898P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.002
2785 reflections	Δρ_max = 0.22 e Å⁻³
177 parameters	Δρ_min = −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)

Crystal data top

[Zn(C₁₄H₉Br₂FNO)₂]	V = 1364.9 (3) Å³
M_r = 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)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2785 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2733 reflections with I > 2σ(I)
T_min = 0.197, T_max = 0.442	R_int = 0.025
16865 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	H-atom parameters constrained
wR(F²) = 0.041	Δρ_max = 0.22 e Å⁻³
S = 1.05	Δρ_min = −0.24 e Å⁻³
2785 reflections	Absolute structure: Flack (1983), 1307 Friedel pairs
177 parameters	Absolute structure parameter: −0.009 (7)
1 restraint

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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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]
M_r	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)
T_min, T_max	0.197, 0.442
No. of measured, independent and observed [I > 2σ(I)] reflections	16865, 2785, 2733
R_int	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
Δρ_max, Δρ_min (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