metal-organic compounds
{4-Bromo-2-[2-(piperidin-1-ium-1yl)ethyliminomethyl]phenolato}diiodidozinc(II)
aKey Laboratory of Surface and Interface Science of Henan, School of Materials and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, People's Republic of China
*Correspondence e-mail: xuewen-zhu@163.com
In the title complex, [ZnI2(C14H19BrN2O)], the ZnII atom is four-coordinated by the imine N and phenolate O atoms of the Schiff base ligand and by two iodide ions in a distorted tetrahedral coordination. In the molecules are linked through intermolecular N—H⋯O hydrogen bonds, forming chains running along the b axis.
Related literature
For background to the chemistry of Schiff base complexes, see: Ali et al. (2008); Biswas et al. (2008); Chen et al. (2008); Darensbourg & Frantz (2007); Habibi et al. (2007); Kawamoto et al. (2008); Lipscomb & Sträter (1996); Tomat et al. (2007); Wu et al. (2008); Yuan et al. (2007). For related structures, see: Zhu (2008); Zhu & Yang (2008a,b,c); Qiu (2006a,b); Wei et al. (2007); Zhu et al. (2007).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); 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
10.1107/S1600536809037210/om2276sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809037210/om2276Isup2.hkl
The Schiff base compound was prepared by the condensation of equimolar amounts of 5-bromosalicylaldehyde with 2-piperidin-1-ylethylamine in a methanol solution. The complex was prepared by the following method. To an anhydrous methanol solution (5 ml) of ZnI2 (31.9 mg, 0.1 mmol) was added a methanol solution (10 ml) of the Schiff base compound (31.1 mg, 0.1 mmol) with stirring. The mixture was stirred for 30 min at room temperature and filtered. Upon keeping the filtrate in air for a few days, colorless block-shaped crystals were formed.
H2 was located from a difference Fourier map and refined isotropically, with N—H distance restrained to 0.90 (1) Å. Other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2004); cell
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).Fig. 1. The molecular structure of the title complex, with ellipsoids drawn at the 30% probability level. | |
Fig. 2. The crystal packing of the title complex. |
[ZnI2(C14H19BrN2O)] | F(000) = 1184 |
Mr = 630.39 | Dx = 2.149 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2365 reflections |
a = 10.470 (3) Å | θ = 2.5–25.1° |
b = 12.351 (3) Å | µ = 6.48 mm−1 |
c = 15.426 (4) Å | T = 298 K |
β = 102.326 (3)° | Block, colorless |
V = 1948.8 (9) Å3 | 0.17 × 0.15 × 0.15 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 4193 independent reflections |
Radiation source: fine-focus sealed tube | 2953 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ω scans | θmax = 27.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −13→12 |
Tmin = 0.406, Tmax = 0.443 | k = −15→15 |
14478 measured reflections | l = −19→19 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0326P)2 + 0.0119P] where P = (Fo2 + 2Fc2)/3 |
4193 reflections | (Δ/σ)max = 0.001 |
193 parameters | Δρmax = 0.68 e Å−3 |
1 restraint | Δρmin = −1.09 e Å−3 |
[ZnI2(C14H19BrN2O)] | V = 1948.8 (9) Å3 |
Mr = 630.39 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.470 (3) Å | µ = 6.48 mm−1 |
b = 12.351 (3) Å | T = 298 K |
c = 15.426 (4) Å | 0.17 × 0.15 × 0.15 mm |
β = 102.326 (3)° |
Bruker APEXII CCD area-detector diffractometer | 4193 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2953 reflections with I > 2σ(I) |
Tmin = 0.406, Tmax = 0.443 | Rint = 0.053 |
14478 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 1 restraint |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.68 e Å−3 |
4193 reflections | Δρmin = −1.09 e Å−3 |
193 parameters |
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 | ||
Zn1 | 0.16997 (7) | 0.57708 (5) | 0.70705 (4) | 0.03725 (18) | |
I1 | −0.02704 (5) | 0.68332 (4) | 0.61843 (3) | 0.05599 (16) | |
I2 | 0.16625 (5) | 0.53139 (4) | 0.86722 (3) | 0.05989 (16) | |
Br1 | 0.46329 (7) | 0.66143 (6) | 0.32863 (4) | 0.04966 (19) | |
O1 | 0.3336 (4) | 0.6472 (3) | 0.6911 (2) | 0.0409 (10) | |
N1 | 0.2025 (4) | 0.4456 (3) | 0.6339 (3) | 0.0316 (10) | |
N2 | −0.0218 (5) | 0.2189 (4) | 0.6686 (3) | 0.0329 (10) | |
C1 | 0.3224 (5) | 0.5601 (4) | 0.5493 (3) | 0.0331 (13) | |
C2 | 0.3580 (6) | 0.6466 (4) | 0.6099 (3) | 0.0354 (13) | |
C3 | 0.4260 (6) | 0.7331 (5) | 0.5832 (4) | 0.0463 (16) | |
H3 | 0.4494 | 0.7909 | 0.6221 | 0.056* | |
C4 | 0.4595 (6) | 0.7367 (5) | 0.5032 (4) | 0.0464 (15) | |
H4 | 0.5063 | 0.7953 | 0.4883 | 0.056* | |
C5 | 0.4238 (6) | 0.6527 (5) | 0.4440 (3) | 0.0356 (14) | |
C6 | 0.3578 (6) | 0.5660 (4) | 0.4664 (3) | 0.0365 (14) | |
H6 | 0.3356 | 0.5095 | 0.4261 | 0.044* | |
C7 | 0.2634 (5) | 0.4608 (4) | 0.5703 (3) | 0.0321 (13) | |
H7 | 0.2697 | 0.4014 | 0.5343 | 0.039* | |
C8 | 0.1621 (6) | 0.3353 (4) | 0.6490 (4) | 0.0382 (14) | |
H8A | 0.2113 | 0.3096 | 0.7059 | 0.046* | |
H8B | 0.1814 | 0.2880 | 0.6032 | 0.046* | |
C9 | 0.0187 (6) | 0.3307 (4) | 0.6481 (4) | 0.0405 (14) | |
H9A | −0.0013 | 0.3811 | 0.6916 | 0.049* | |
H9B | −0.0305 | 0.3525 | 0.5901 | 0.049* | |
C10 | −0.1500 (6) | 0.2221 (5) | 0.6981 (4) | 0.0511 (17) | |
H10A | −0.2166 | 0.2535 | 0.6514 | 0.061* | |
H10B | −0.1411 | 0.2680 | 0.7501 | 0.061* | |
C11 | −0.1929 (7) | 0.1106 (6) | 0.7199 (5) | 0.0611 (19) | |
H11A | −0.1316 | 0.0830 | 0.7714 | 0.073* | |
H11B | −0.2780 | 0.1158 | 0.7352 | 0.073* | |
C12 | −0.2011 (7) | 0.0321 (6) | 0.6442 (5) | 0.068 (2) | |
H12A | −0.2200 | −0.0400 | 0.6630 | 0.082* | |
H12B | −0.2711 | 0.0533 | 0.5951 | 0.082* | |
C13 | −0.0735 (8) | 0.0318 (5) | 0.6150 (4) | 0.0585 (19) | |
H13A | −0.0804 | −0.0155 | 0.5641 | 0.070* | |
H13B | −0.0060 | 0.0030 | 0.6625 | 0.070* | |
C14 | −0.0340 (7) | 0.1429 (5) | 0.5910 (4) | 0.0466 (16) | |
H14A | −0.0989 | 0.1706 | 0.5414 | 0.056* | |
H14B | 0.0490 | 0.1388 | 0.5728 | 0.056* | |
H2 | 0.038 (5) | 0.197 (5) | 0.716 (3) | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0429 (4) | 0.0396 (4) | 0.0303 (3) | −0.0049 (3) | 0.0101 (3) | −0.0033 (3) |
I1 | 0.0597 (3) | 0.0710 (3) | 0.0357 (2) | 0.0164 (2) | 0.0068 (2) | 0.0024 (2) |
I2 | 0.0858 (4) | 0.0614 (3) | 0.0341 (2) | −0.0066 (3) | 0.0165 (2) | 0.0058 (2) |
Br1 | 0.0485 (4) | 0.0681 (5) | 0.0363 (3) | 0.0073 (3) | 0.0178 (3) | 0.0093 (3) |
O1 | 0.046 (3) | 0.049 (2) | 0.0271 (19) | −0.013 (2) | 0.0072 (17) | −0.0100 (17) |
N1 | 0.031 (3) | 0.028 (2) | 0.036 (2) | −0.003 (2) | 0.008 (2) | 0.0024 (19) |
N2 | 0.034 (3) | 0.034 (3) | 0.030 (2) | −0.001 (2) | 0.008 (2) | 0.004 (2) |
C1 | 0.030 (3) | 0.034 (3) | 0.032 (3) | 0.002 (3) | 0.000 (2) | −0.004 (2) |
C2 | 0.036 (4) | 0.040 (3) | 0.029 (3) | −0.002 (3) | 0.004 (2) | 0.002 (2) |
C3 | 0.062 (5) | 0.047 (4) | 0.029 (3) | −0.011 (3) | 0.009 (3) | −0.007 (3) |
C4 | 0.049 (4) | 0.042 (4) | 0.050 (4) | −0.009 (3) | 0.015 (3) | 0.005 (3) |
C5 | 0.037 (4) | 0.047 (4) | 0.025 (3) | 0.010 (3) | 0.012 (2) | 0.012 (2) |
C6 | 0.043 (4) | 0.040 (3) | 0.026 (3) | 0.006 (3) | 0.006 (2) | −0.003 (2) |
C7 | 0.037 (4) | 0.028 (3) | 0.030 (3) | 0.001 (2) | 0.004 (2) | −0.008 (2) |
C8 | 0.038 (4) | 0.037 (3) | 0.039 (3) | −0.001 (3) | 0.007 (3) | 0.003 (3) |
C9 | 0.040 (4) | 0.036 (3) | 0.045 (3) | 0.004 (3) | 0.009 (3) | 0.007 (3) |
C10 | 0.040 (4) | 0.061 (4) | 0.054 (4) | 0.010 (3) | 0.015 (3) | 0.013 (3) |
C11 | 0.047 (4) | 0.066 (5) | 0.075 (5) | −0.003 (4) | 0.022 (4) | 0.021 (4) |
C12 | 0.061 (5) | 0.061 (5) | 0.078 (5) | −0.018 (4) | 0.006 (4) | 0.019 (4) |
C13 | 0.075 (5) | 0.050 (4) | 0.053 (4) | −0.018 (4) | 0.017 (4) | −0.010 (3) |
C14 | 0.053 (4) | 0.052 (4) | 0.036 (3) | −0.014 (3) | 0.014 (3) | −0.002 (3) |
Zn1—O1 | 1.981 (4) | C6—H6 | 0.9300 |
Zn1—N1 | 2.047 (4) | C7—H7 | 0.9300 |
Zn1—I2 | 2.5428 (9) | C8—C9 | 1.500 (8) |
Zn1—I1 | 2.5771 (9) | C8—H8A | 0.9700 |
Br1—C5 | 1.914 (5) | C8—H8B | 0.9700 |
O1—C2 | 1.329 (6) | C9—H9A | 0.9700 |
N1—C7 | 1.293 (7) | C9—H9B | 0.9700 |
N1—C8 | 1.460 (6) | C10—C11 | 1.509 (9) |
N2—C9 | 1.498 (7) | C10—H10A | 0.9700 |
N2—C14 | 1.505 (7) | C10—H10B | 0.9700 |
N2—C10 | 1.508 (7) | C11—C12 | 1.507 (10) |
N2—H2 | 0.90 (5) | C11—H11A | 0.9700 |
C1—C6 | 1.407 (7) | C11—H11B | 0.9700 |
C1—C2 | 1.417 (7) | C12—C13 | 1.498 (10) |
C1—C7 | 1.441 (7) | C12—H12A | 0.9700 |
C2—C3 | 1.395 (8) | C12—H12B | 0.9700 |
C3—C4 | 1.354 (8) | C13—C14 | 1.502 (8) |
C3—H3 | 0.9300 | C13—H13A | 0.9700 |
C4—C5 | 1.380 (8) | C13—H13B | 0.9700 |
C4—H4 | 0.9300 | C14—H14A | 0.9700 |
C5—C6 | 1.359 (8) | C14—H14B | 0.9700 |
O1—Zn1—N1 | 91.61 (16) | N1—C8—H8B | 109.5 |
O1—Zn1—I2 | 114.27 (10) | C9—C8—H8B | 109.5 |
N1—Zn1—I2 | 113.47 (12) | H8A—C8—H8B | 108.0 |
O1—Zn1—I1 | 109.08 (12) | N2—C9—C8 | 111.1 (4) |
N1—Zn1—I1 | 108.67 (12) | N2—C9—H9A | 109.4 |
I2—Zn1—I1 | 116.86 (3) | C8—C9—H9A | 109.4 |
C2—O1—Zn1 | 117.4 (3) | N2—C9—H9B | 109.4 |
C7—N1—C8 | 117.6 (4) | C8—C9—H9B | 109.4 |
C7—N1—Zn1 | 118.0 (3) | H9A—C9—H9B | 108.0 |
C8—N1—Zn1 | 124.4 (3) | N2—C10—C11 | 111.7 (5) |
C9—N2—C14 | 112.8 (4) | N2—C10—H10A | 109.3 |
C9—N2—C10 | 110.5 (4) | C11—C10—H10A | 109.3 |
C14—N2—C10 | 109.1 (5) | N2—C10—H10B | 109.3 |
C9—N2—H2 | 106 (5) | C11—C10—H10B | 109.3 |
C14—N2—H2 | 113 (4) | H10A—C10—H10B | 107.9 |
C10—N2—H2 | 106 (5) | C12—C11—C10 | 112.6 (6) |
C6—C1—C2 | 118.6 (5) | C12—C11—H11A | 109.1 |
C6—C1—C7 | 117.2 (5) | C10—C11—H11A | 109.1 |
C2—C1—C7 | 123.9 (5) | C12—C11—H11B | 109.1 |
O1—C2—C3 | 119.1 (5) | C10—C11—H11B | 109.1 |
O1—C2—C1 | 123.3 (5) | H11A—C11—H11B | 107.8 |
C3—C2—C1 | 117.5 (5) | C13—C12—C11 | 109.1 (6) |
C4—C3—C2 | 122.8 (6) | C13—C12—H12A | 109.9 |
C4—C3—H3 | 118.6 | C11—C12—H12A | 109.9 |
C2—C3—H3 | 118.6 | C13—C12—H12B | 109.9 |
C3—C4—C5 | 119.5 (6) | C11—C12—H12B | 109.9 |
C3—C4—H4 | 120.2 | H12A—C12—H12B | 108.3 |
C5—C4—H4 | 120.2 | C12—C13—C14 | 112.5 (6) |
C6—C5—C4 | 120.3 (5) | C12—C13—H13A | 109.1 |
C6—C5—Br1 | 120.2 (4) | C14—C13—H13A | 109.1 |
C4—C5—Br1 | 119.4 (4) | C12—C13—H13B | 109.1 |
C5—C6—C1 | 121.3 (5) | C14—C13—H13B | 109.1 |
C5—C6—H6 | 119.4 | H13A—C13—H13B | 107.8 |
C1—C6—H6 | 119.4 | C13—C14—N2 | 110.8 (5) |
N1—C7—C1 | 126.8 (5) | C13—C14—H14A | 109.5 |
N1—C7—H7 | 116.6 | N2—C14—H14A | 109.5 |
C1—C7—H7 | 116.6 | C13—C14—H14B | 109.5 |
N1—C8—C9 | 110.9 (4) | N2—C14—H14B | 109.5 |
N1—C8—H8A | 109.5 | H14A—C14—H14B | 108.1 |
C9—C8—H8A | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.90 (5) | 1.85 (5) | 2.745 (6) | 176 (7) |
Symmetry code: (i) −x+1/2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [ZnI2(C14H19BrN2O)] |
Mr | 630.39 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 10.470 (3), 12.351 (3), 15.426 (4) |
β (°) | 102.326 (3) |
V (Å3) | 1948.8 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 6.48 |
Crystal size (mm) | 0.17 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.406, 0.443 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14478, 4193, 2953 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.093, 1.03 |
No. of reflections | 4193 |
No. of parameters | 193 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.68, −1.09 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Zn1—O1 | 1.981 (4) | Zn1—I2 | 2.5428 (9) |
Zn1—N1 | 2.047 (4) | Zn1—I1 | 2.5771 (9) |
O1—Zn1—N1 | 91.61 (16) | O1—Zn1—I1 | 109.08 (12) |
O1—Zn1—I2 | 114.27 (10) | N1—Zn1—I1 | 108.67 (12) |
N1—Zn1—I2 | 113.47 (12) | I2—Zn1—I1 | 116.86 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.90 (5) | 1.85 (5) | 2.745 (6) | 176 (7) |
Symmetry code: (i) −x+1/2, y−1/2, −z+3/2. |
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Schiff bases have widely been used as versatile ligands in coordination chemistry (Biswas et al., 2008; Wu et al., 2008; Kawamoto et al., 2008; Ali et al., 2008; Habibi et al., 2007), and their metal complexes are of great interest in many fields (Chen et al., 2008; Yuan et al., 2007; Tomat et al., 2007; Darensbourg & Frantz, 2007). Zinc(II) is an important element in biological systems and functions as the active site of hydrolytic enzymes, such as carboxypeptidase and carbonic anhydrase where it is in a hard-donor coordination environment of nitrogen and oxygen ligands (Lipscomb & Sträter, 1996). Recently, we have reported a few Schiff base zinc complexes (Zhu, 2008; Zhu & Yang, 2008a,b,c). In this paper, the title new zinc(II) complex, Fig. 1, is reported.
In the title complex, the ZnII atom is four-coordinated by the imine N and phenolate O atoms of the Schiff base ligand, and by two iodide ions in a tetrahedral coordination. The coordinate bond lengths (Table 1) are typical and comparable to the corresponding values observed in the Schiff base zinc complexes we reported previously and other similar Schiff base zinc complexes (Zhu et al., 2007; Wei et al., 2007; Qiu, 2006a,b).
In the crystal structure, molecules are linked through intermolecular N—H···O hydrogen bonds, forming chains running along the b axis (Table 2, Fig. 2).