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Acta Cryst. (2008). E64, m1456-m1457    [ doi:10.1107/S1600536808033977 ]

Dichlorido{2-[3-(dimethylammonio)propyliminomethyl]phenolato}zinc(II) hemihydrate

X.-W. Zhu

Abstract top

The title complex, [ZnCl2(C12H18N2O)]·0.5H2O, is a mononuclear zinc(II) compound derived from the zwitterionic form of the Schiff base 2-[3-(dimethylamino)propyliminomethyl]phenol. The ZnII atom is four-coordinated by the imine N and the phenolate O atoms of the Schiff base ligand, and by two chloride ions, in a distorted tetrahedral coordination geometry. The dimethylammonio group is disordered over two positions with site occupancies of 0.51 (3) and 0.49 (3). In the asymmetric unit, there is also a disordered water molecule with a partial occupancy of 0.5. In the crystal structure, the water molecules are linked to the Schiff base complex molecules through intermolecular N-H...O hydrogen bonds. Molecules are further linked through additional intermolecular N-H...O hydrogen bonds, forming chains running along the b axis.

Comment top

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 an 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 some Schiff base complexes (Zhu & Yang, 2008a,b,c,d). In this paper, the synthesis and structural characterization of a new zinc(II) complex (Fig. 1) of the Schiff base ligand 2-[(3-dimethylaminopropylimino)methyl]phenol is reported.

The zinc(II) atom in the title compound is four-coordinated by the imine N and phenolate O atoms of the zwitterionic form of the Schiff base ligand, and by two Cl- 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, the water molecules are linked to the Schiff base complex molecules through intermolecular N–H···O hydrogen bonds (Table 2). The molecules are further linked through intermolecular N–H···O hydrogen bonds (Table 2), forming chains running along the b axis (Fig. 2).

Related literature top

For a general background on 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 & Yang (2008a,b,c,d); Qiu (2006a,b); Wei et al. (2007); Zhu et al. (2007).

Experimental top

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 ZnCl2 (13.7 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, colourless block-shaped crystals were formed at the bottom of the vessel on slow evaporation of the solvent.

Refinement top

H atoms bound to C and N 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). The dimethylammmonium group is disordered over two distinct sites, with occupancies of 0.51 (3) and 0.49 (3), respectively. The lattice water molecule is also disordered, with an occupancy restrained to 0.50. The water H atoms were placed at calculated positions and refined with the O—H and H···H lengths constrained to 0.85 (1) and 1.37 (2) Å, respectively, and with the isotropic thermal parameter fixed at 0.08 Å2.

Computing details top

Data collection: APEX2 (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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with ellipsoids drawn at the 30% probability level. Only the major component of disorder is shown.
[Figure 2] Fig. 2. The crystal packing of the title compound viewed along the c axis. Hydrogen atoms not involved in hydrogen bonding interactions (dashed lines) are omitted for clarity. Only the major component of disorder is shown.
Dichlorido{2-[3-(dimethylammonio)propyliminomethyl]phenolato}zinc(II) hemihydrate top
Crystal data top
[ZnCl2(C12H18N2O)]·0.5H2OF(000) = 724
Mr = 351.58Dx = 1.482 Mg m−3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 3872 reflections
a = 13.335 (2) Åθ = 2.4–25.3°
b = 16.384 (2) ŵ = 1.89 mm−1
c = 7.212 (1) ÅT = 298 K
V = 1575.7 (4) Å3Block, colorless
Z = 40.23 × 0.23 × 0.22 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3426 independent reflections
Radiation source: fine-focus sealed tube2915 reflections with I > 2σ(I)
graphiteRint = 0.035
ω scansθmax = 27.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −17→17
Tmin = 0.650, Tmax = 0.661k = −20→20
12635 measured reflectionsl = −9→9
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.103 w = 1/[σ2(Fo2) + (0.0381P)2 + 0.643P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
3426 reflectionsΔρmax = 0.42 e Å−3
206 parametersΔρmin = −0.40 e Å−3
4 restraintsAbsolute structure: Flack (1983), 1569 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.03 (2)
Crystal data top
[ZnCl2(C12H18N2O)]·0.5H2OV = 1575.7 (4) Å3
Mr = 351.58Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 13.335 (2) ŵ = 1.89 mm−1
b = 16.384 (2) ÅT = 298 K
c = 7.212 (1) Å0.23 × 0.23 × 0.22 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3426 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		2915 reflections with I > 2σ(I)
Tmin = 0.650, Tmax = 0.661Rint = 0.035
12635 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.103Δρmax = 0.42 e Å−3
S = 1.08Δρmin = −0.40 e Å−3
3426 reflectionsAbsolute structure: Flack (1983), 1569 Friedel pairs
206 parametersFlack parameter: 0.03 (2)
4 restraints
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
xyzUiso*/UeqOcc. (<1)
Zn10.73458 (3)1.10664 (2)1.00222 (10)0.04900 (15)
Cl10.59091 (11)1.09513 (7)1.1550 (2)0.0746 (4)
Cl20.86270 (14)1.03257 (11)1.1229 (3)0.1022 (5)
N10.7159 (3)1.0824 (2)0.7323 (5)0.0449 (7)
O10.7749 (2)1.21988 (16)0.9610 (4)0.0563 (8)
O20.9856 (5)0.9368 (4)0.1435 (12)0.0704 (18)0.50
C10.8128 (3)1.2011 (2)0.6371 (6)0.0488 (9)
C20.8218 (3)1.2425 (2)0.8055 (6)0.0464 (9)
C30.8817 (4)1.3118 (3)0.8081 (9)0.0656 (13)
H30.88971.34010.91890.079*
C40.9288 (4)1.3393 (3)0.6546 (10)0.0783 (16)
H40.96681.38680.66150.094*
C50.9217 (4)1.2989 (3)0.4892 (11)0.0835 (17)
H50.95641.31720.38530.100*
C60.8631 (4)1.2317 (3)0.4807 (8)0.0736 (14)
H60.85581.20490.36780.088*
C70.7537 (3)1.1280 (3)0.6068 (6)0.0506 (10)
H70.74231.11290.48430.061*
C80.6601 (3)1.0080 (2)0.6728 (7)0.0575 (11)
H8A0.59681.00530.73890.069*
H8B0.64551.01170.54130.069*
C90.7184 (4)0.9327 (3)0.7093 (7)0.0674 (13)
H9A0.67480.88580.69470.081*
H9B0.74190.93350.83650.081*
N20.8576 (13)0.8452 (7)0.543 (2)0.055 (4)0.51 (3)
H2C0.80900.80710.52470.066*0.51 (3)
C100.8059 (4)0.9240 (3)0.5831 (9)0.0800 (18)0.51 (3)
H10A0.85700.96080.62960.096*0.51 (3)
H10B0.78490.94560.46410.096*0.51 (3)
C110.9122 (17)0.8214 (9)0.713 (4)0.091 (8)0.51 (3)
H11A0.86830.82570.81760.137*0.51 (3)
H11B0.96870.85690.72960.137*0.51 (3)
H11C0.93510.76610.70080.137*0.51 (3)
C120.9244 (10)0.8403 (9)0.389 (3)0.082 (6)0.51 (3)
H12A0.95230.78640.38160.123*0.51 (3)
H12B0.97750.87930.40360.123*0.51 (3)
H12C0.88830.85190.27650.123*0.51 (3)
N2'0.8443 (12)0.8327 (9)0.641 (4)0.071 (5)0.49 (3)
H2'A0.79700.79700.59980.085*0.49 (3)
C10'0.8059 (4)0.9240 (3)0.5831 (9)0.0800 (18)0.49 (3)
H10C0.85660.96500.60720.096*0.49 (3)
H10D0.78600.92650.45380.096*0.49 (3)
C11'0.8661 (16)0.8106 (11)0.824 (4)0.101 (8)0.49 (3)
H11D0.88120.75340.82880.152*0.49 (3)
H11E0.80910.82200.90100.152*0.49 (3)
H11F0.92280.84130.86680.152*0.49 (3)
C12'0.9351 (17)0.8164 (14)0.534 (6)0.139 (12)0.49 (3)
H12D0.95920.76260.56290.209*0.49 (3)
H12E0.98550.85590.56580.209*0.49 (3)
H12F0.92030.81990.40440.209*0.49 (3)
H2A0.984 (7)0.973 (5)0.228 (11)0.080*0.50
H2B0.930 (4)0.911 (5)0.146 (15)0.080*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0640 (3)0.0390 (2)0.0440 (2)−0.00734 (18)0.0112 (3)−0.0061 (3)
Cl10.0750 (8)0.0720 (8)0.0768 (8)−0.0113 (6)0.0324 (7)−0.0094 (6)
Cl20.1140 (13)0.1004 (11)0.0921 (11)−0.0145 (9)−0.0136 (10)0.0143 (9)
N10.0476 (18)0.0393 (16)0.0478 (18)0.0030 (14)0.0062 (15)−0.0058 (14)
O10.0774 (18)0.0361 (12)0.055 (2)−0.0102 (12)0.0190 (14)−0.0142 (12)
O20.056 (4)0.054 (4)0.102 (6)0.011 (3)0.005 (4)0.015 (4)
C10.052 (2)0.0417 (19)0.053 (2)0.0019 (17)0.0052 (18)0.0038 (18)
C20.051 (2)0.0308 (17)0.058 (2)−0.0004 (16)0.0125 (19)0.0006 (16)
C30.067 (3)0.042 (2)0.088 (4)−0.008 (2)0.011 (3)−0.014 (2)
C40.064 (3)0.048 (2)0.123 (5)−0.009 (2)0.031 (3)0.009 (3)
C50.079 (3)0.072 (3)0.100 (4)0.002 (2)0.041 (4)0.019 (4)
C60.088 (3)0.070 (3)0.063 (3)0.001 (2)0.030 (3)0.010 (3)
C70.062 (3)0.049 (2)0.041 (2)−0.0007 (18)0.0022 (19)−0.0092 (19)
C80.059 (3)0.046 (2)0.068 (3)−0.0111 (19)0.001 (2)−0.018 (2)
C90.098 (4)0.043 (2)0.061 (3)−0.021 (2)−0.006 (3)−0.010 (2)
N20.070 (7)0.026 (3)0.069 (9)−0.004 (3)−0.020 (7)−0.001 (5)
C100.078 (3)0.037 (2)0.124 (5)−0.002 (2)−0.008 (3)−0.020 (3)
C110.085 (14)0.052 (7)0.136 (19)0.000 (7)−0.051 (14)0.024 (9)
C120.072 (8)0.049 (7)0.125 (14)0.020 (5)0.017 (9)−0.028 (7)
N2'0.067 (8)0.044 (7)0.101 (14)0.004 (5)−0.006 (9)−0.029 (8)
C10'0.078 (3)0.037 (2)0.124 (5)−0.002 (2)−0.008 (3)−0.020 (3)
C11'0.094 (12)0.051 (8)0.16 (2)0.014 (8)−0.054 (13)−0.027 (10)
C12'0.094 (12)0.127 (16)0.20 (4)0.010 (12)0.068 (19)−0.002 (19)
Geometric parameters (Å, °) top
Zn1—O11.954 (3)C9—C101.487 (8)
Zn1—N12.003 (4)C9—H9A0.9700
Zn1—Cl12.2182 (13)C9—H9B0.9700
Zn1—Cl22.2692 (18)N2—C121.430 (19)
N1—C71.277 (6)N2—C111.47 (2)
N1—C81.491 (5)N2—C101.491 (15)
O1—C21.336 (5)N2—H2C0.9100
O2—H2A0.852 (10)C10—H10A0.9700
O2—H2B0.848 (10)C10—H10B0.9700
C1—C21.396 (6)C11—H11A0.9600
C1—C61.405 (6)C11—H11B0.9600
C1—C71.451 (6)C11—H11C0.9600
C2—C31.389 (6)C12—H12A0.9600
C3—C41.350 (8)C12—H12B0.9600
C3—H30.9300C12—H12C0.9600
C4—C51.368 (9)N2'—C11'1.40 (3)
C4—H40.9300N2'—C12'1.46 (2)
C5—C61.352 (7)N2'—H2'A0.9100
C5—H50.9300C11'—H11D0.9600
C6—H60.9300C11'—H11E0.9600
C7—H70.9300C11'—H11F0.9600
C8—C91.481 (7)C12'—H12D0.9600
C8—H8A0.9700C12'—H12E0.9600
C8—H8B0.9700C12'—H12F0.9600
O1—Zn1—N194.29 (13)C10—C9—H9B109.1
O1—Zn1—Cl1113.19 (9)H9A—C9—H9B107.8
N1—Zn1—Cl1111.04 (11)C12—N2—C11108.9 (14)
O1—Zn1—Cl2111.03 (11)C12—N2—C10119.2 (9)
N1—Zn1—Cl2111.10 (11)C11—N2—C10107.3 (12)
Cl1—Zn1—Cl2114.48 (7)C12—N2—H2C106.9
C7—N1—C8118.1 (4)C11—N2—H2C106.9
C7—N1—Zn1121.6 (3)C10—N2—H2C106.9
C8—N1—Zn1120.3 (3)C9—C10—N2124.4 (8)
C2—O1—Zn1121.3 (2)C9—C10—H10A106.2
H2A—O2—H2B108 (3)N2—C10—H10A106.2
C2—C1—C6119.0 (4)C9—C10—H10B106.2
C2—C1—C7125.4 (4)N2—C10—H10B106.2
C6—C1—C7115.6 (4)H10A—C10—H10B106.4
O1—C2—C3119.0 (4)N2—C11—H11A109.5
O1—C2—C1123.7 (3)N2—C11—H11B109.5
C3—C2—C1117.2 (4)H11A—C11—H11B109.5
C4—C3—C2122.0 (5)N2—C11—H11C109.5
C4—C3—H3119.0H11A—C11—H11C109.5
C2—C3—H3119.0H11B—C11—H11C109.5
C3—C4—C5121.4 (5)N2—C12—H12A109.5
C3—C4—H4119.3N2—C12—H12B109.5
C5—C4—H4119.3H12A—C12—H12B109.5
C6—C5—C4118.3 (5)N2—C12—H12C109.5
C6—C5—H5120.8H12A—C12—H12C109.5
C4—C5—H5120.8H12B—C12—H12C109.5
C5—C6—C1122.0 (6)C11'—N2'—C12'106.1 (19)
C5—C6—H6119.0C11'—N2'—H2'A106.6
C1—C6—H6119.0C12'—N2'—H2'A106.6
N1—C7—C1126.2 (4)N2'—C11'—H11D109.5
N1—C7—H7116.9N2'—C11'—H11E109.5
C1—C7—H7116.9H11D—C11'—H11E109.5
C9—C8—N1111.5 (4)N2'—C11'—H11F109.5
C9—C8—H8A109.3H11D—C11'—H11F109.5
N1—C8—H8A109.3H11E—C11'—H11F109.5
C9—C8—H8B109.3N2'—C12'—H12D109.5
N1—C8—H8B109.3N2'—C12'—H12E109.5
H8A—C8—H8B108.0H12D—C12'—H12E109.5
C8—C9—C10112.6 (4)N2'—C12'—H12F109.5
C8—C9—H9A109.1H12D—C12'—H12F109.5
C10—C9—H9A109.1H12E—C12'—H12F109.5
C8—C9—H9B109.1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2'—H2'A···O1i0.911.882.762 (14)164
N2—H2C···O1i0.911.872.773 (12)170
Symmetry codes: (i) −x+3/2, y−1/2, z−1/2.
Table 1
Selected geometric parameters (Å) top
Zn1—O11.954 (3)Zn1—Cl12.2182 (13)
Zn1—N12.003 (4)Zn1—Cl22.2692 (18)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2'—H2'A···O1i0.911.882.762 (14)164
N2—H2C···O1i0.911.872.773 (12)170
Symmetry codes: (i) −x+3/2, y−1/2, z−1/2.
Acknowledgements top

No acknowledgements

references
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