PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m1090–m1091.
Published online 2008 July 31. doi:  10.1107/S1600536808023659
PMCID: PMC2961998

{(E)-2-[3-(Dimethyl­ammonio)propyl­iminometh­yl]phenolato}diiodidozinc(II)

Abstract

The title complex, [ZnI2(C12H18N2O)], is a mononuclear zinc(II) compound derived from the zwitterionic form of the Schiff base (E)-2-[(3-dimethyl­amino­propyl­imino)meth­yl]phenol. 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 geometry. In the crystal structure, 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 [triangle]); Biswas et al. (2008 [triangle]); Chen et al. (2008 [triangle]); Darensbourg & Frantz (2007 [triangle]); Habibi et al. (2007 [triangle]); Kawamoto et al. (2008 [triangle]); Lipscomb & Sträter (1996 [triangle]); Tomat et al. (2007 [triangle]); Wu et al. (2008 [triangle]); Yuan et al. (2007 [triangle]). For related structures, see: Qiu (2006a [triangle],b [triangle]); Wei et al. (2007 [triangle]); Zhu et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1090-scheme1.jpg

Experimental

Crystal data

  • [ZnI2(C12H18N2O)]
  • M r = 525.45
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1090-efi1.jpg
  • a = 13.892 (3) Å
  • b = 16.640 (2) Å
  • c = 7.372 (3) Å
  • V = 1704.1 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 5.06 mm−1
  • T = 298 (2) K
  • 0.20 × 0.20 × 0.18 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004 [triangle]) T min = 0.431, T max = 0.463 (expected range = 0.375–0.402)
  • 12154 measured reflections
  • 3669 independent reflections
  • 3271 reflections with I > 2σ(I)
  • R int = 0.048

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.100
  • S = 1.04
  • 3669 reflections
  • 165 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 1.82 e Å−3
  • Δρmin = −0.47 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1660 Friedel pairs
  • Flack parameter: 0.00 (4)

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808023659/sj2522sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808023659/sj2522Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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). In this paper, a new zinc(II) complex, (I), Fig. 1, of the Schiff base ligand (E)-2-[(3-dimethylaminopropylimino)methyl]phenol has been synthesized and structurally characterized.

The ZnII atom in (I) is four-coordinated by the imine N and phenolate O atoms of the zwitterionic form of the Schiff base ligand, and by two I- ions, in a tetrahedral coordination geometry. The coordinate bond lengths (Table 1) are typical and comparable to the corresponding values observed in other similar zinc(II) Schiff base 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 (Table 2), forming chains running along the b axis (Fig. 2).

Experimental

The Schiff base compound was prepared by the condensation of equimolar amounts of salicylaldehyde with N,N-dimethylpropane-1,3-diamine 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 (20.6 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 at the bottom of the vessel on slow evaporation of the solvent.

Refinement

All 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, N–H distances of 0.91 Å, and with Uiso(H) = 1.2Ueq(C,N) and 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I) with ellipsoids drawn at the 30% probability level.
Fig. 2.
The crystal packing of (I), viewed along the c axis.

Crystal data

[ZnI2(C12H18N2O)]F000 = 992
Mr = 525.45Dx = 2.048 Mg m3
Orthorhombic, Pna21Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 4125 reflections
a = 13.892 (3) Åθ = 2.4–25.0º
b = 16.640 (2) ŵ = 5.06 mm1
c = 7.372 (3) ÅT = 298 (2) K
V = 1704.1 (8) Å3Block, colorless
Z = 40.20 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD area-detector diffractometer3669 independent reflections
Radiation source: fine-focus sealed tube3271 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.048
T = 298(2) Kθmax = 27.0º
ω scansθmin = 1.9º
Absorption correction: multi-scan(SADABS; Sheldrick, 2004)h = −17→17
Tmin = 0.431, Tmax = 0.463k = −20→21
12154 measured reflectionsl = −9→9

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.043  w = 1/[σ2(Fo2) + (0.0426P)2 + 0.9395P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.100(Δ/σ)max = 0.001
S = 1.04Δρmax = 1.82 e Å3
3669 reflectionsΔρmin = −0.46 e Å3
165 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 1660 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.00 (4)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/Ueq
Zn10.75194 (6)0.90239 (4)0.72869 (14)0.03631 (19)
I10.58993 (3)0.92236 (3)0.88834 (9)0.04992 (15)
I20.89258 (4)0.98333 (3)0.85716 (9)0.05741 (18)
N10.7294 (4)0.9228 (3)0.4634 (8)0.0379 (13)
N20.8361 (5)1.1716 (3)0.3321 (11)0.0544 (19)
H2A0.78571.20520.31060.065*
O10.7847 (4)0.7893 (3)0.6946 (7)0.0429 (12)
C10.8309 (5)0.7664 (4)0.5451 (11)0.0385 (16)
C20.8869 (6)0.6960 (5)0.5496 (14)0.053 (2)
H20.89230.66720.65730.063*
C30.9338 (6)0.6691 (5)0.396 (2)0.070 (3)
H30.97220.62340.40300.084*
C40.9256 (7)0.7066 (5)0.2392 (16)0.063 (3)
H40.95750.68650.13800.075*
C50.8701 (7)0.7758 (5)0.2225 (15)0.063 (2)
H50.86530.80190.11130.075*
C60.8209 (5)0.8061 (4)0.3760 (13)0.0422 (15)
C70.7648 (5)0.8782 (4)0.3445 (10)0.0389 (16)
H70.75420.89260.22430.047*
C80.6691 (5)0.9919 (4)0.4056 (12)0.0456 (19)
H8A0.60740.98890.46670.055*
H8B0.65740.98800.27610.055*
C90.7143 (6)1.0712 (4)0.4458 (11)0.0459 (19)
H9A0.73581.07210.57100.055*
H9B0.66681.11340.43050.055*
C100.7992 (6)1.0871 (4)0.3217 (13)0.049 (2)
H10A0.85101.05050.35310.059*
H10B0.78021.07580.19770.059*
C110.8730 (10)1.1894 (6)0.5117 (19)0.100 (5)
H11A0.91641.14760.54880.150*
H11B0.82051.19260.59600.150*
H11C0.90661.23980.50920.150*
C120.9089 (8)1.1848 (6)0.186 (2)0.101 (5)
H12A0.92691.24050.18340.151*
H12B0.88191.16990.07110.151*
H12C0.96481.15250.20990.151*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0426 (5)0.0328 (3)0.0335 (4)0.0041 (3)0.0026 (4)0.0028 (3)
I10.0415 (3)0.0491 (2)0.0591 (3)0.00396 (18)0.0126 (3)−0.0002 (3)
I20.0486 (3)0.0603 (3)0.0633 (4)−0.0039 (2)−0.0084 (3)−0.0062 (3)
N10.037 (3)0.042 (3)0.035 (3)−0.012 (2)−0.001 (3)−0.004 (3)
N20.048 (4)0.029 (3)0.086 (6)0.005 (3)−0.002 (4)0.007 (3)
O10.052 (3)0.032 (2)0.045 (3)0.008 (2)0.007 (3)0.006 (2)
C10.034 (4)0.033 (3)0.048 (5)−0.008 (3)0.005 (3)−0.002 (3)
C20.055 (5)0.040 (4)0.063 (6)0.008 (4)0.016 (4)0.005 (4)
C30.059 (5)0.040 (4)0.111 (9)0.008 (4)0.019 (7)−0.003 (6)
C40.063 (6)0.052 (5)0.073 (7)0.010 (4)0.028 (5)−0.016 (5)
C50.070 (6)0.063 (5)0.055 (6)0.001 (4)0.014 (5)−0.012 (5)
C60.040 (4)0.040 (3)0.046 (4)0.003 (3)0.008 (4)−0.004 (4)
C70.049 (4)0.044 (3)0.024 (4)0.001 (3)0.003 (3)0.001 (3)
C80.041 (4)0.045 (3)0.051 (5)0.001 (3)−0.004 (4)0.017 (4)
C90.051 (5)0.039 (4)0.047 (5)0.016 (3)−0.006 (4)0.005 (3)
C100.051 (5)0.027 (3)0.070 (6)0.005 (3)0.005 (4)0.006 (3)
C110.111 (10)0.054 (6)0.135 (11)−0.023 (6)−0.078 (9)0.026 (6)
C120.074 (7)0.052 (5)0.177 (15)0.007 (5)0.051 (8)0.028 (8)

Geometric parameters (Å, °)

Zn1—O11.952 (4)C5—C61.415 (12)
Zn1—N12.010 (6)C5—H50.9300
Zn1—I22.5550 (11)C6—C71.449 (9)
Zn1—I12.5615 (11)C7—H70.9300
N1—C71.250 (9)C8—C91.491 (10)
N1—C81.485 (9)C8—H8A0.9700
N2—C111.451 (14)C8—H8B0.9700
N2—C121.493 (15)C9—C101.516 (12)
N2—C101.498 (8)C9—H9A0.9700
N2—H2A0.9100C9—H9B0.9700
O1—C11.331 (9)C10—H10A0.9700
C1—C21.406 (10)C10—H10B0.9700
C1—C61.417 (12)C11—H11A0.9600
C2—C31.384 (15)C11—H11B0.9600
C2—H20.9300C11—H11C0.9600
C3—C41.317 (17)C12—H12A0.9600
C3—H30.9300C12—H12B0.9600
C4—C51.392 (12)C12—H12C0.9600
C4—H40.9300
O1—Zn1—N194.3 (2)N1—C7—C6126.2 (7)
O1—Zn1—I2112.17 (16)N1—C7—H7116.9
N1—Zn1—I2113.02 (16)C6—C7—H7116.9
O1—Zn1—I1112.90 (16)N1—C8—C9113.0 (6)
N1—Zn1—I1106.74 (18)N1—C8—H8A109.0
I2—Zn1—I1115.67 (4)C9—C8—H8A109.0
C7—N1—C8118.8 (7)N1—C8—H8B109.0
C7—N1—Zn1121.4 (5)C9—C8—H8B109.0
C8—N1—Zn1119.9 (5)H8A—C8—H8B107.8
C11—N2—C12112.8 (9)C8—C9—C10111.2 (6)
C11—N2—C10111.1 (7)C8—C9—H9A109.4
C12—N2—C10109.5 (8)C10—C9—H9A109.4
C11—N2—H2A107.8C8—C9—H9B109.4
C12—N2—H2A107.8C10—C9—H9B109.4
C10—N2—H2A107.8H9A—C9—H9B108.0
C1—O1—Zn1119.6 (4)N2—C10—C9113.5 (6)
O1—C1—C2119.0 (7)N2—C10—H10A108.9
O1—C1—C6123.2 (6)C9—C10—H10A108.9
C2—C1—C6117.6 (7)N2—C10—H10B108.9
C3—C2—C1120.7 (9)C9—C10—H10B108.9
C3—C2—H2119.6H10A—C10—H10B107.7
C1—C2—H2119.6N2—C11—H11A109.5
C4—C3—C2121.6 (8)N2—C11—H11B109.5
C4—C3—H3119.2H11A—C11—H11B109.5
C2—C3—H3119.2N2—C11—H11C109.5
C3—C4—C5121.2 (9)H11A—C11—H11C109.5
C3—C4—H4119.4H11B—C11—H11C109.5
C5—C4—H4119.4N2—C12—H12A109.5
C4—C5—C6119.5 (10)N2—C12—H12B109.5
C4—C5—H5120.3H12A—C12—H12B109.5
C6—C5—H5120.3N2—C12—H12C109.5
C5—C6—C1119.3 (7)H12A—C12—H12C109.5
C5—C6—C7115.2 (8)H12B—C12—H12C109.5
C1—C6—C7125.4 (7)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.911.912.772 (8)157

Symmetry codes: (i) −x+3/2, y+1/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2522).

References

  • Ali, H. M., Mohamed Mustafa, M. I., Rizal, M. R. & Ng, S. W. (2008). Acta Cryst. E64, m718–m719. [PMC free article] [PubMed]
  • Biswas, C., Drew, M. G. B. & Ghosh, A. (2008). Inorg. Chem.47, 4513–4519. [PubMed]
  • Bruker (2004). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, Z., Morimoto, H., Matsunaga, S. & Shibasaki, M. (2008). J. Am. Chem. Soc.130, 2170–2171. [PubMed]
  • Darensbourg, D. J. & Frantz, E. B. (2007). Inorg. Chem.46, 5967–5978. [PubMed]
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Habibi, M. H., Askari, E., Chantrapromma, S. & Fun, H.-K. (2007). Acta Cryst. E63, m2905–m2906.
  • Kawamoto, T., Nishiwaki, M., Tsunekawa, Y., Nozaki, K. & Konno, T. (2008). Inorg. Chem.47, 3095–3104. [PubMed]
  • Lipscomb, W. N. & Sträter, N. (1996). Chem. Rev.96, 2375–2434. [PubMed]
  • Qiu, X.-Y. (2006a). Acta Cryst. E62, m717–m718.
  • Qiu, X.-Y. (2006b). Acta Cryst. E62, m2173–m2174.
  • Sheldrick, G. M. (2004). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tomat, E., Cuesta, L., Lynch, V. M. & Sessler, J. L. (2007). Inorg. Chem.46, 6224–6226. [PubMed]
  • Wei, Y.-J., Wang, F.-W. & Zhu, Q.-Y. (2007). Acta Cryst. E63, m654–m655.
  • Wu, J.-C., Liu, S.-X., Keene, T. D., Neels, A., Mereacre, V., Powell, A. K. & Decurtins, S. (2008). Inorg. Chem.47, 3452–3459. [PubMed]
  • Yuan, M., Zhao, F., Zhang, W., WAng, Z.-M. & Gao, S. (2007). Inorg. Chem.46, 11235–11242. [PubMed]
  • Zhu, Q.-Y., Wei, Y.-J. & Wang, F.-W. (2007). Acta Cryst. E63, m1431–m1432.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography