Bis{(E)-2-meth­oxy-6-[(4-methyl­phen­yl)­imino­meth­yl]phenolato}zinc(II)

Xian, H.-D.; Liu, J.-F.; Li, H.-Q.; Zhao, G.-L.

doi:10.1107/S1600536808033102

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1422

doi:10.1107/S1600536808033102

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Bis{(E)-2-methoxy-6-[(4-methylphenyl)iminomethyl]phenolato}zinc(II)

Hui-Duo Xian,^a Jian-Feng Liu,^a Hua-Qiong Li ^a and Guo-Liang Zhao ^a ^*

^aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China, and, College of Chemistry and Life Science, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China
^*Correspondence e-mail: sky53@zjnu.cn

(Received 19 September 2008; accepted 13 October 2008; online 18 October 2008)

The title compound, [Zn(C₁₅H₁₄NO₂)₂], contains a four-coordinate Zn atom located on a twofold rotation axis that exhibits a distorted tetrahedral geometry by two phenolate O atoms and two azomethine N atoms of the Schiff base 2-methoxy-6-[(4-methylphenyl)iminomethyl]phenolate ligands.

Related literature

For related literature, see: Bhattacharyya et al. (2002 ); Iyere et al. (2004 ); Müller et al. (2001 ); Yu et al. (2007 ); Zhou & Zhao (2007 ).

Experimental

Crystal data

[Zn(C₁₅H₁₄NO₂)₂]
M_r = 545.93
Monoclinic, C 2/c
a = 14.0698 (4) Å
b = 16.3828 (5) Å
c = 12.0532 (3) Å
β = 107.5880 (10)°
V = 2648.42 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 296 (2) K
0.52 × 0.08 × 0.08 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.914, T_max = 0.930
10967 measured reflections
3013 independent reflections
2523 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.096
S = 1.03
3013 reflections
168 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; 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 I, global. DOI: 10.1107/S1600536808033102/at2636sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808033102/at2636Isup2.hkl

checkCIF report

Comment top

Schiff base ligands derived from substituted salicylaldehyde and aniline and their metal complexes have been widely investigated because of their novel structural features (Müller et al., 2001; Bhattacharyya et al., 2002). They include complexes with a methoxy group in the ortho position as the methoxy group can also bind to the metal. Such Schiff bases behave as bidentate ligands to divalent first-row transition metals (Zhou & Zhao, 2007). Similar cobalt (II) complexes have been reported by Iyere et al. (2004). Here, we describe the synthesis and crystal structure of a zinc complex, (I), of a Schiff base derived from o-vanillin and p-toluidine.

The structural features of the (I) dimer shown in Fig.ure 1. The Zn atom sits on a twofold axis. The tridentate ligands coordinate to the Zinc ion through the phenolic hydroxy O atom and the azomethine N atom, forming a distorted tetrahedral geometry around the metal ion. It is different from the complex [ZnL₂(NO₃)₂] (Yu et al., 2007) in which Zn is coordinated by the methoxy O atom and the azomethine N atom.

Related literature top

For related literature, see: Bhattacharyya et al. (2002); Iyere et al. (2004); Müller et al. (2001); Yu et al. (2007); Zhou & Zhao (2007). It would be much more useful to readers if the "Related literature" section had some kind of simple sub-division, so that, instead of just "For related literature, see···;" it said, for example, "For general background, see··· For related structures, see···; etc. Please revise this section as indicated.

Experimental top

The ligand was prepared by the direct solid-phase reaction of o-vanillin (10 mmol, 1.5251 g) and p-toluidine (10 mmol, 1.0700 g). The reactants were ground in an agate mortar. The colour of the mixture changed from light yellow to orange. A solution of Zn(C₂O₄) (1 mmol, 0.153 g) in methanol (10 ml) was added to a methanol solution of the Schiff base ligand (2 mmol, 0.48 g). orange crystals were isolated after two weeks.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 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 (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Bis{(E)-2-methoxy-6-[(4-methylphenyl)iminomethyl]phenolato}zinc(II) top

Crystal data top

[Zn(C₁₅H₁₄NO₂)₂]	F(000) = 1136
M_r = 545.93	D_x = 1.369 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4200 reflections
a = 14.0698 (4) Å	θ = 2.0–27.5°
b = 16.3828 (5) Å	µ = 0.97 mm⁻¹
c = 12.0532 (3) Å	T = 296 K
β = 107.588 (1)°	Prism, orange
V = 2648.42 (13) Å³	0.52 × 0.08 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	3013 independent reflections
Radiation source: fine-focus sealed tube	2523 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
T_min = 0.914, T_max = 0.930	k = −16→21
10967 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0548P)² + 1.3911P] where P = (F_o² + 2F_c²)/3
3013 reflections	(Δ/σ)_max < 0.001
168 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Zn(C₁₅H₁₄NO₂)₂]	V = 2648.42 (13) Å³
M_r = 545.93	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.0698 (4) Å	µ = 0.97 mm⁻¹
b = 16.3828 (5) Å	T = 296 K
c = 12.0532 (3) Å	0.52 × 0.08 × 0.08 mm
β = 107.588 (1)°

Data collection top

Bruker APEXII diffractometer	3013 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2523 reflections with I > 2σ(I)
T_min = 0.914, T_max = 0.930	R_int = 0.025
10967 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.03	Δρ_max = 0.35 e Å⁻³
3013 reflections	Δρ_min = −0.27 e Å⁻³
168 parameters

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
Zn1	0.0000	0.029267 (18)	0.2500	0.03242 (12)
N1	0.04480 (11)	0.08214 (9)	0.12438 (13)	0.0314 (3)
O1	0.26186 (12)	−0.13463 (10)	0.42256 (14)	0.0539 (4)
O2	0.11926 (10)	−0.03384 (8)	0.31639 (12)	0.0386 (3)
C1	−0.1868 (3)	0.3361 (2)	−0.1614 (3)	0.0881 (10)
H1A	−0.1785	0.3347	−0.2376	0.132*
H1B	−0.1641	0.3876	−0.1253	0.132*
H1C	−0.2561	0.3291	−0.1680	0.132*
C2	−0.12681 (17)	0.26797 (15)	−0.0881 (2)	0.0526 (6)
C3	−0.07130 (16)	0.21486 (15)	−0.13218 (19)	0.0479 (5)
H3A	−0.0719	0.2207	−0.2091	0.058*
C4	−0.01499 (15)	0.15341 (13)	−0.06598 (17)	0.0393 (5)
H4A	0.0220	0.1188	−0.0982	0.047*
C5	−0.01341 (13)	0.14317 (11)	0.04915 (16)	0.0326 (4)
C6	−0.07168 (16)	0.19465 (15)	0.09294 (19)	0.0481 (5)
H6A	−0.0740	0.1874	0.1686	0.058*
C7	−0.12619 (19)	0.25644 (17)	0.0254 (2)	0.0587 (6)
H7A	−0.1634	0.2912	0.0571	0.070*
C8	0.12692 (13)	0.05742 (13)	0.10587 (17)	0.0344 (4)
H8A	0.1411	0.0807	0.0423	0.041*
C9	0.19768 (14)	−0.00060 (13)	0.17051 (17)	0.0340 (4)
C10	0.28175 (17)	−0.01304 (15)	0.1298 (2)	0.0492 (6)
H10A	0.2847	0.0137	0.0629	0.059*
C11	0.35710 (17)	−0.06289 (18)	0.1865 (2)	0.0611 (7)
H11A	0.4118	−0.0695	0.1593	0.073*
C12	0.35297 (16)	−0.10458 (16)	0.2861 (2)	0.0541 (6)
H12A	0.4050	−0.1390	0.3248	0.065*
C13	0.27268 (15)	−0.09502 (13)	0.32723 (18)	0.0411 (5)
C14	0.19242 (13)	−0.04184 (11)	0.27139 (17)	0.0321 (4)
C15	0.3448 (2)	−0.1804 (2)	0.4906 (3)	0.0850 (10)
H15A	0.3283	−0.2056	0.5543	0.128*
H15B	0.4009	−0.1448	0.5202	0.128*
H15C	0.3612	−0.2219	0.4431	0.128*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02977 (17)	0.0356 (2)	0.0350 (2)	0.000	0.01448 (13)	0.000
N1	0.0318 (7)	0.0305 (8)	0.0330 (8)	−0.0016 (6)	0.0113 (6)	−0.0010 (6)
O1	0.0533 (9)	0.0591 (10)	0.0499 (10)	0.0229 (8)	0.0166 (8)	0.0156 (8)
O2	0.0340 (7)	0.0464 (9)	0.0391 (8)	0.0076 (6)	0.0167 (6)	0.0083 (6)
C1	0.094 (2)	0.087 (2)	0.086 (2)	0.0422 (19)	0.0316 (19)	0.0423 (19)
C2	0.0495 (12)	0.0524 (14)	0.0538 (14)	0.0119 (11)	0.0124 (11)	0.0160 (11)
C3	0.0497 (12)	0.0564 (14)	0.0368 (12)	0.0018 (10)	0.0118 (10)	0.0095 (10)
C4	0.0425 (10)	0.0401 (12)	0.0357 (11)	0.0003 (9)	0.0123 (9)	−0.0037 (9)
C5	0.0322 (9)	0.0305 (10)	0.0356 (10)	−0.0026 (7)	0.0110 (8)	0.0003 (8)
C6	0.0486 (12)	0.0614 (15)	0.0368 (12)	0.0157 (11)	0.0166 (10)	0.0043 (10)
C7	0.0610 (14)	0.0629 (16)	0.0547 (14)	0.0272 (13)	0.0213 (12)	0.0037 (12)
C8	0.0344 (9)	0.0373 (10)	0.0344 (10)	−0.0048 (8)	0.0148 (8)	0.0001 (8)
C9	0.0308 (9)	0.0358 (10)	0.0378 (11)	−0.0009 (8)	0.0143 (8)	−0.0030 (9)
C10	0.0444 (12)	0.0583 (15)	0.0539 (14)	0.0054 (10)	0.0283 (11)	0.0048 (11)
C11	0.0429 (12)	0.0791 (18)	0.0708 (17)	0.0175 (13)	0.0312 (12)	0.0049 (15)
C12	0.0404 (11)	0.0606 (15)	0.0620 (15)	0.0184 (11)	0.0167 (11)	0.0040 (12)
C13	0.0399 (10)	0.0424 (12)	0.0400 (11)	0.0060 (9)	0.0106 (9)	−0.0013 (9)
C14	0.0291 (9)	0.0324 (10)	0.0349 (10)	−0.0012 (7)	0.0096 (8)	−0.0057 (8)
C15	0.078 (2)	0.098 (2)	0.077 (2)	0.0455 (18)	0.0210 (16)	0.0416 (19)

Geometric parameters (Å, º) top

Zn1—O2ⁱ	1.9270 (13)	C5—C6	1.387 (3)
Zn1—O2	1.9270 (13)	C6—C7	1.378 (3)
Zn1—N1	2.0043 (15)	C6—H6A	0.9300
Zn1—N1ⁱ	2.0043 (15)	C7—H7A	0.9300
N1—C8	1.306 (2)	C8—C9	1.426 (3)
N1—C5	1.430 (2)	C8—H8A	0.9300
O1—C13	1.368 (2)	C9—C14	1.412 (3)
O1—C15	1.421 (3)	C9—C10	1.426 (2)
O2—C14	1.307 (2)	C10—C11	1.349 (3)
C1—C2	1.512 (3)	C10—H10A	0.9300
C1—H1A	0.9600	C11—C12	1.398 (3)
C1—H1B	0.9600	C11—H11A	0.9300
C1—H1C	0.9600	C12—C13	1.373 (3)
C2—C3	1.378 (3)	C12—H12A	0.9300
C2—C7	1.379 (3)	C13—C14	1.424 (3)
C3—C4	1.377 (3)	C15—H15A	0.9600
C3—H3A	0.9300	C15—H15B	0.9600
C4—C5	1.391 (3)	C15—H15C	0.9600
C4—H4A	0.9300

O2ⁱ—Zn1—O2	115.11 (9)	C5—C6—H6A	119.7
O2ⁱ—Zn1—N1	110.57 (6)	C6—C7—C2	121.5 (2)
O2—Zn1—N1	96.45 (6)	C6—C7—H7A	119.3
O2ⁱ—Zn1—N1ⁱ	96.45 (6)	C2—C7—H7A	119.3
O2—Zn1—N1ⁱ	110.57 (6)	N1—C8—C9	128.41 (17)
N1—Zn1—N1ⁱ	128.79 (9)	N1—C8—H8A	115.8
C8—N1—C5	118.39 (15)	C9—C8—H8A	115.8
C8—N1—Zn1	119.45 (13)	C14—C9—C10	119.53 (19)
C5—N1—Zn1	122.05 (11)	C14—C9—C8	125.43 (16)
C13—O1—C15	117.05 (19)	C10—C9—C8	114.97 (18)
C14—O2—Zn1	125.29 (12)	C11—C10—C9	121.3 (2)
C2—C1—H1A	109.5	C11—C10—H10A	119.4
C2—C1—H1B	109.5	C9—C10—H10A	119.4
H1A—C1—H1B	109.5	C10—C11—C12	120.0 (2)
C2—C1—H1C	109.5	C10—C11—H11A	120.0
H1A—C1—H1C	109.5	C12—C11—H11A	120.0
H1B—C1—H1C	109.5	C13—C12—C11	120.4 (2)
C3—C2—C7	117.5 (2)	C13—C12—H12A	119.8
C3—C2—C1	121.5 (2)	C11—C12—H12A	119.8
C7—C2—C1	121.0 (2)	O1—C13—C12	124.2 (2)
C4—C3—C2	122.1 (2)	O1—C13—C14	114.43 (16)
C4—C3—H3A	118.9	C12—C13—C14	121.4 (2)
C2—C3—H3A	118.9	O2—C14—C9	124.19 (17)
C3—C4—C5	119.94 (19)	O2—C14—C13	118.47 (17)
C3—C4—H4A	120.0	C9—C14—C13	117.33 (16)
C5—C4—H4A	120.0	O1—C15—H15A	109.5
C6—C5—C4	118.24 (19)	O1—C15—H15B	109.5
C6—C5—N1	118.37 (17)	H15A—C15—H15B	109.5
C4—C5—N1	123.39 (17)	O1—C15—H15C	109.5
C7—C6—C5	120.6 (2)	H15A—C15—H15C	109.5
C7—C6—H6A	119.7	H15B—C15—H15C	109.5

O2ⁱ—Zn1—N1—C8	−111.17 (15)	C5—N1—C8—C9	178.22 (19)
O2—Zn1—N1—C8	8.73 (15)	Zn1—N1—C8—C9	−5.4 (3)
N1ⁱ—Zn1—N1—C8	131.72 (15)	N1—C8—C9—C14	−1.6 (3)
O2ⁱ—Zn1—N1—C5	65.06 (15)	N1—C8—C9—C10	−178.4 (2)
O2—Zn1—N1—C5	−175.04 (14)	C14—C9—C10—C11	−0.7 (4)
N1ⁱ—Zn1—N1—C5	−52.05 (13)	C8—C9—C10—C11	176.4 (2)
O2ⁱ—Zn1—O2—C14	107.71 (16)	C9—C10—C11—C12	1.0 (4)
N1—Zn1—O2—C14	−8.61 (16)	C10—C11—C12—C13	−0.2 (4)
N1ⁱ—Zn1—O2—C14	−144.32 (15)	C15—O1—C13—C12	8.0 (4)
C7—C2—C3—C4	−1.5 (4)	C15—O1—C13—C14	−172.3 (2)
C1—C2—C3—C4	178.9 (2)	C11—C12—C13—O1	178.7 (2)
C2—C3—C4—C5	0.4 (3)	C11—C12—C13—C14	−1.0 (4)
C3—C4—C5—C6	1.7 (3)	Zn1—O2—C14—C9	4.4 (3)
C3—C4—C5—N1	−178.54 (18)	Zn1—O2—C14—C13	−175.95 (14)
C8—N1—C5—C6	−151.95 (19)	C10—C9—C14—O2	179.16 (19)
Zn1—N1—C5—C6	31.8 (2)	C8—C9—C14—O2	2.4 (3)
C8—N1—C5—C4	28.3 (3)	C10—C9—C14—C13	−0.5 (3)
Zn1—N1—C5—C4	−147.93 (15)	C8—C9—C14—C13	−177.21 (19)
C4—C5—C6—C7	−2.8 (3)	O1—C13—C14—O2	1.9 (3)
N1—C5—C6—C7	177.5 (2)	C12—C13—C14—O2	−178.3 (2)
C5—C6—C7—C2	1.7 (4)	O1—C13—C14—C9	−178.41 (18)
C3—C2—C7—C6	0.5 (4)	C12—C13—C14—C9	1.3 (3)
C1—C2—C7—C6	−179.9 (3)

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(C₁₅H₁₄NO₂)₂]
M_r	545.93
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	14.0698 (4), 16.3828 (5), 12.0532 (3)
β (°)	107.588 (1)
V (Å³)	2648.42 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.52 × 0.08 × 0.08

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.914, 0.930
No. of measured, independent and observed [I > 2σ(I)] reflections	10967, 3013, 2523
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.096, 1.03
No. of reflections	3013
No. of parameters	168
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.27

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

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