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Acta Cryst. (2010). E66, m469    [ doi:10.1107/S160053681001127X ]

Dichlorido{2-[(2-isopropylammonioethyl)iminomethyl]-5-methoxyphenolato}zinc(II)

Z.-Q. Han, Y. Wang and S. Han

Abstract top

The ZnII atom in the title compound, [ZnCl2(C13H20N2O2)], is four-coordinated by the imine N and phenolate O atoms of the zwitterionic Schiff base ligand, and by two choride ions in a distorted tetrahedral coordination. In the crystal structure, molecules are linked through intermolecular N-H...O and N-H...Cl hydrogen bonds along [010].

Comment top

Recently, we have reported a nickel(II) complex with the ligand 3-ethoxysalicylaldehyde (Han, 2008). We report here a new zinc(II) complex derived from the Schiff base ligand 2-[(2-isopropylammonioethylimino)methyl]-5-methoxyphenol, which was formed by the condensation reaction of 4-methoxysalicylaldehyde with N-isopropylethane-1,2-diamine in a methanol solution.The ZnII atom is four-coordinated by the imine N and phenolate O atoms of the Schiff base ligand, and by two choride ions in a distorted tetrahedral coordination. In the crystal structure, molecules are linked through intermolecular N—H··· O and N—H ···O and hydrogen bonds along [010], (Fig. 2). The geometric parameters are comparable to those in similar zinc(II) complexes with Schiff bases (Wang, 2007; Ali et al., 2008; Zhang et al., 2008; Zhu et al., 2009) as representative examples.

Related literature top

For a nickel(II) complex with the 3-ethoxysalicylaldehyde ligand, see: Han (2008). For similar zinc(II) complexes with Schiff bases, see: Ali et al. (2008); Wang (2007); Zhang et al. (2008); Zhu et al. (2009).

Experimental top

All the chemicals were of AR grade. 4-Methoxysalicylaldehyde (30.4 mg, 0.2 mmol) and N-isopropylethane-1,2-diamine (20.4 mg, 0.2 mmol) were stirred in a methanol solution for 2 h at reflux. Then the zinc(II) chloride (27.5 mg, 0.2 mmol) was added to the mixture. The mixture was further stirred at reflux for 1 h. The mixture was cooled to room temperature and filtered. After keeping the filtrate in air for a week, yielding colorless block crystals suitable for X-ray analysis.

Refinement top

H atoms were placed in 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 0.90 Å, and with Uiso(H) set at 1.2Ueq(C,N) and 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. Molecular packing of the title complex.
Dichlorido{2-[(2-isopropylammonioethyl)iminomethyl]-5-methoxyphenolato}zinc(II) top
Crystal data top
[ZnCl2(C13H20N2O2)]F(000) = 768
Mr = 372.58Dx = 1.504 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.2915 (9) ÅCell parameters from 1935 reflections
b = 11.8990 (18) Åθ = 2.5–24.5°
c = 22.115 (4) ŵ = 1.82 mm−1
β = 96.518 (4)°T = 298 K
V = 1644.9 (4) Å3Block, colourless
Z = 40.18 × 0.18 × 0.18 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3557 independent reflections
Radiation source: fine-focus sealed tube2515 reflections with I > 2σ(I)
graphiteRint = 0.042
ω scansθmax = 27.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −7→8
Tmin = 0.735, Tmax = 0.735k = −13→15
9437 measured reflectionsl = −27→28
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0339P)2 + 0.3384P]
where P = (Fo2 + 2Fc2)/3
3557 reflections(Δ/σ)max = 0.001
184 parametersΔρmax = 0.46 e Å−3
0 restraintsΔρmin = −0.31 e Å−3
Crystal data top
[ZnCl2(C13H20N2O2)]V = 1644.9 (4) Å3
Mr = 372.58Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.2915 (9) ŵ = 1.82 mm−1
b = 11.8990 (18) ÅT = 298 K
c = 22.115 (4) Å0.18 × 0.18 × 0.18 mm
β = 96.518 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3557 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2515 reflections with I > 2σ(I)
Tmin = 0.735, Tmax = 0.735Rint = 0.042
9437 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.086Δρmax = 0.46 e Å−3
S = 1.01Δρmin = −0.31 e Å−3
3557 reflectionsAbsolute structure: ?
184 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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 > 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
xyzUiso*/Ueq
Zn10.75702 (6)0.83340 (3)0.763592 (16)0.03646 (12)
Cl10.56343 (14)0.81826 (7)0.67166 (4)0.0519 (2)
Cl21.00002 (12)0.97048 (6)0.77248 (4)0.0497 (2)
N10.8725 (4)0.68364 (18)0.79167 (11)0.0336 (6)
N20.9034 (4)0.58914 (18)0.66336 (10)0.0329 (6)
H2A0.77880.59590.67940.039*
H2B0.94120.51620.66580.039*
O10.5732 (3)0.85623 (15)0.82740 (9)0.0399 (5)
O20.0900 (4)0.7411 (2)0.95938 (11)0.0652 (7)
C10.6016 (5)0.6635 (2)0.86232 (13)0.0360 (7)
C20.5081 (5)0.7727 (2)0.85973 (13)0.0336 (7)
C30.3364 (5)0.7916 (2)0.89406 (14)0.0397 (7)
H30.27350.86250.89310.048*
C40.2582 (5)0.7086 (3)0.92900 (14)0.0449 (8)
C50.3475 (6)0.6021 (3)0.93171 (16)0.0524 (9)
H50.29560.54600.95540.063*
C60.5158 (5)0.5815 (3)0.89822 (15)0.0483 (8)
H60.57520.50990.89950.058*
C70.7806 (5)0.6282 (2)0.83109 (13)0.0367 (7)
H70.83530.55710.84080.044*
C81.0626 (5)0.6333 (3)0.76875 (14)0.0417 (8)
H8A1.06220.55280.77580.050*
H8B1.19070.66400.79130.050*
C91.0685 (5)0.6552 (2)0.70159 (14)0.0374 (7)
H9A1.04540.73460.69350.045*
H9B1.20890.63580.69060.045*
C100.8660 (6)0.6211 (3)0.59723 (15)0.0513 (9)
H100.81150.69830.59520.062*
C110.6940 (6)0.5472 (3)0.56592 (17)0.0732 (12)
H11A0.74280.47070.56690.110*
H11B0.66130.57090.52440.110*
H11C0.56790.55260.58640.110*
C121.0658 (7)0.6201 (4)0.56802 (18)0.0780 (13)
H12A1.12820.54650.57150.117*
H12B1.16430.67380.58780.117*
H12C1.03460.63940.52580.117*
C130.0014 (7)0.6613 (3)0.99717 (18)0.0725 (12)
H13A−0.04950.59740.97320.109*
H13B−0.11550.69491.01500.109*
H13C0.10920.63761.02880.109*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0419 (2)0.02734 (18)0.0413 (2)0.00185 (15)0.00994 (15)−0.00074 (15)
Cl10.0564 (5)0.0489 (5)0.0486 (5)0.0057 (4)−0.0021 (4)−0.0049 (4)
Cl20.0413 (5)0.0393 (4)0.0687 (6)−0.0057 (4)0.0072 (4)0.0064 (4)
N10.0342 (14)0.0289 (13)0.0369 (14)0.0010 (10)0.0005 (11)−0.0047 (10)
N20.0353 (14)0.0291 (12)0.0351 (14)0.0002 (10)0.0076 (11)−0.0013 (10)
O10.0491 (13)0.0260 (10)0.0477 (13)0.0021 (9)0.0186 (11)0.0011 (9)
O20.0748 (18)0.0618 (15)0.0661 (17)−0.0106 (13)0.0389 (15)−0.0050 (13)
C10.0391 (17)0.0321 (15)0.0365 (17)−0.0011 (13)0.0028 (13)−0.0009 (13)
C20.0367 (17)0.0316 (16)0.0320 (17)−0.0050 (13)0.0018 (13)−0.0046 (13)
C30.0457 (19)0.0347 (16)0.0399 (18)−0.0030 (14)0.0095 (15)−0.0069 (14)
C40.047 (2)0.051 (2)0.0370 (18)−0.0116 (16)0.0082 (15)−0.0074 (15)
C50.061 (2)0.048 (2)0.050 (2)−0.0107 (17)0.0151 (18)0.0073 (16)
C60.055 (2)0.0361 (17)0.054 (2)−0.0002 (15)0.0057 (18)0.0081 (15)
C70.0444 (18)0.0255 (14)0.0384 (18)0.0035 (13)−0.0035 (15)−0.0021 (13)
C80.0338 (17)0.0439 (18)0.046 (2)0.0068 (14)0.0002 (14)−0.0072 (14)
C90.0297 (15)0.0320 (16)0.051 (2)−0.0015 (13)0.0076 (14)−0.0029 (14)
C100.069 (2)0.0459 (19)0.039 (2)0.0039 (18)0.0056 (18)0.0044 (15)
C110.085 (3)0.084 (3)0.046 (2)−0.011 (2)−0.014 (2)−0.005 (2)
C120.085 (3)0.095 (3)0.058 (3)0.002 (3)0.025 (2)0.011 (2)
C130.082 (3)0.080 (3)0.062 (3)−0.020 (2)0.035 (2)0.000 (2)
Geometric parameters (Å, °) top
Zn1—O11.9425 (19)C5—H50.9300
Zn1—N11.997 (2)C6—H60.9300
Zn1—Cl22.2290 (9)C7—H70.9300
Zn1—Cl12.2554 (10)C8—C91.513 (4)
N1—C71.282 (3)C8—H8A0.9700
N1—C81.478 (3)C8—H8B0.9700
N2—C91.487 (4)C9—H9A0.9700
N2—C101.504 (4)C9—H9B0.9700
N2—H2A0.9000C10—C121.477 (5)
N2—H2B0.9000C10—C111.502 (5)
O1—C21.317 (3)C10—H100.9800
O2—C41.372 (4)C11—H11A0.9600
O2—C131.420 (4)C11—H11B0.9600
C1—C61.404 (4)C11—H11C0.9600
C1—C21.425 (4)C12—H12A0.9600
C1—C71.448 (4)C12—H12B0.9600
C2—C31.408 (4)C12—H12C0.9600
C3—C41.379 (4)C13—H13A0.9600
C3—H30.9300C13—H13B0.9600
C4—C51.385 (4)C13—H13C0.9600
C5—C61.381 (4)
O1—Zn1—N197.16 (9)C1—C7—H7116.2
O1—Zn1—Cl2107.02 (6)N1—C8—C9112.2 (2)
N1—Zn1—Cl2113.82 (7)N1—C8—H8A109.2
O1—Zn1—Cl1111.15 (7)C9—C8—H8A109.2
N1—Zn1—Cl1110.44 (7)N1—C8—H8B109.2
Cl2—Zn1—Cl1115.64 (3)C9—C8—H8B109.2
C7—N1—C8118.0 (2)H8A—C8—H8B107.9
C7—N1—Zn1119.60 (19)N2—C9—C8111.9 (2)
C8—N1—Zn1122.37 (19)N2—C9—H9A109.2
C9—N2—C10116.2 (2)C8—C9—H9A109.2
C9—N2—H2A108.2N2—C9—H9B109.2
C10—N2—H2A108.2C8—C9—H9B109.2
C9—N2—H2B108.2H9A—C9—H9B107.9
C10—N2—H2B108.2C12—C10—C11113.4 (3)
H2A—N2—H2B107.4C12—C10—N2112.1 (3)
C2—O1—Zn1122.43 (17)C11—C10—N2109.0 (3)
C4—O2—C13118.4 (3)C12—C10—H10107.3
C6—C1—C2118.2 (3)C11—C10—H10107.3
C6—C1—C7116.0 (3)N2—C10—H10107.3
C2—C1—C7125.8 (3)C10—C11—H11A109.5
O1—C2—C3118.5 (2)C10—C11—H11B109.5
O1—C2—C1123.9 (2)H11A—C11—H11B109.5
C3—C2—C1117.6 (3)C10—C11—H11C109.5
C4—C3—C2122.1 (3)H11A—C11—H11C109.5
C4—C3—H3118.9H11B—C11—H11C109.5
C2—C3—H3118.9C10—C12—H12A109.5
O2—C4—C3114.6 (3)C10—C12—H12B109.5
O2—C4—C5124.6 (3)H12A—C12—H12B109.5
C3—C4—C5120.8 (3)C10—C12—H12C109.5
C6—C5—C4118.1 (3)H12A—C12—H12C109.5
C6—C5—H5121.0H12B—C12—H12C109.5
C4—C5—H5121.0O2—C13—H13A109.5
C5—C6—C1123.2 (3)O2—C13—H13B109.5
C5—C6—H6118.4H13A—C13—H13B109.5
C1—C6—H6118.4O2—C13—H13C109.5
N1—C7—C1127.6 (3)H13A—C13—H13C109.5
N1—C7—H7116.2H13B—C13—H13C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Cl2i0.902.623.357 (2)140
N2—H2B···O1i0.901.912.782 (3)162
N2—H2A···Cl10.902.973.483 (2)118
Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2.
Table 1
Selected geometric parameters (Å, °) top
Zn1—O11.9425 (19)Zn1—Cl22.2290 (9)
Zn1—N11.997 (2)Zn1—Cl12.2554 (10)
O1—Zn1—N197.16 (9)O1—Zn1—Cl1111.15 (7)
O1—Zn1—Cl2107.02 (6)N1—Zn1—Cl1110.44 (7)
N1—Zn1—Cl2113.82 (7)Cl2—Zn1—Cl1115.64 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Cl2i0.902.623.357 (2)140
N2—H2B···O1i0.901.912.782 (3)162
N2—H2A···Cl10.902.973.483 (2)118
Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2.
Acknowledgements top

The authors acknowledge Qiqihar University for a research grant.

references
References top

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