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Acta Cryst. (2008). E64, m1597    [ doi:10.1107/S1600536808037860 ]

{N,N'-Bis[(E)-3-phenylallylidene]ethane-1,2-diamine}dichloridozinc(II)

H.-L. Cai, B. Liu and Z.-D. Lin

Abstract top

In the title compound, [ZnCl2(C20H20N2)], the ZnII atom is four coordinated in a distorted tetrahedral geometry by two N atoms of the Schiff base ligand and by two Cl atoms. Edge-to-face C-H...[pi] interactions exist between molecules, with a dihedral angle of 37.8 (1)° between the benzene ring planes and a shortest H...centroid distance of 3.62 (5) Å.

Comment top

Transition-metal compounds containing Schiff-base ligands play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions, magnetism and molecular architectures (Costamagna et al., 1992; Bhatia et al., 1981). In the title compound (Fig. 1), the ZnII atom is coordinated by a bidentate Schiff-base ligand and two Cl atoms in a slightly distorted tetrahedral geometry. The Zn—Cl bond distances are comparable to those observed in the related compounds [ZnCl2(C12H16BrClN2O)] (Wang et al., 2007) and [ZnCl2(C16H18N4O)] (Tolman et al., 1991).

Related literature top

For related literature on transition metal complexes of Schiff base ligands, see: Bhatia et al. (1981); Costamagna et al. (1992). For related complexes of ZnCl2 with bidentate ligands, see: Tolman et al. (1991); Wang et al. (2007).

Experimental top

Cinnamaldehyde (0.2 mmol, 26.4 mg), ZnCl2.6H2O (0.1 mmol, 24 mg) and ethylenediamine (0.1 mmol, 6.4 mg) were dissolved in methanol (10 ml). The mixture was stirred for 30 min at room temperature to give a clear yellow solution, which was left in air for a few days to give yellow crystals of the title compound (yield 79%). Elemental analysis calculated: C 56.56, H 4.75, N 6.60%; found: C 56.79, H 4.49, N 6.31%.

Refinement top

H atoms were positioned geometrically, with C—H = 0.93 or 0.97 Å for aromatic and ethyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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. Molecular structure with displacement ellipsoids drawn at 50% probability for non-H atoms.
[Figure 2] Fig. 2. Packing diagram viewed along the a axis.
{N,N'-Bis[(E)-3-phenylallylidene]ethane-1,2-diamine} dichloridozinc(II) top
Crystal data top
[ZnCl2(C20H20N2)]F(000) = 872
Mr = 424.65Dx = 1.374 Mg m−3
Monoclinic, P21/cMelting point: 553 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.2140 (8) ÅCell parameters from 2760 reflections
b = 20.265 (2) Åθ = 2.1–28.1°
c = 14.0906 (16) ŵ = 1.46 mm−1
β = 94.913 (2)°T = 300 K
V = 2052.4 (4) Å3Block, yellow
Z = 40.23 × 0.20 × 0.10 mm
Data collection top
Bruker SMART CCD
diffractometer		4458 independent reflections
Radiation source: fine-focus sealed tube3027 reflections with I > 2σ(I)
graphiteRint = 0.030
φ and ω scansθmax = 27.0°, θmin = 1.8°
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)		h = −9→9
Tmin = 0.730, Tmax = 0.868k = −25→24
15814 measured reflectionsl = −17→12
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0805P)2]
where P = (Fo2 + 2Fc2)/3
4458 reflections(Δ/σ)max = 0.001
226 parametersΔρmax = 0.50 e Å−3
0 restraintsΔρmin = −0.29 e Å−3
Crystal data top
[ZnCl2(C20H20N2)]V = 2052.4 (4) Å3
Mr = 424.65Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.2140 (8) ŵ = 1.46 mm−1
b = 20.265 (2) ÅT = 300 K
c = 14.0906 (16) Å0.23 × 0.20 × 0.10 mm
β = 94.913 (2)°
Data collection top
Bruker SMART CCD
diffractometer		4458 independent reflections
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)		3027 reflections with I > 2σ(I)
Tmin = 0.730, Tmax = 0.868Rint = 0.030
15814 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.132Δρmax = 0.50 e Å−3
S = 0.99Δρmin = −0.29 e Å−3
4458 reflectionsAbsolute structure: ?
226 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Zn10.09704 (4)0.575283 (15)0.83248 (3)0.06115 (16)
C10.2380 (5)0.84830 (15)0.8767 (2)0.0731 (8)
C20.2309 (7)0.91286 (17)0.9108 (3)0.0965 (13)
H20.12600.92740.93870.116*
C30.3789 (9)0.9553 (2)0.9034 (4)0.1214 (18)
H30.37360.99820.92640.146*
C40.5311 (10)0.9345 (3)0.8629 (4)0.1234 (19)
H40.63030.96330.85850.148*
C50.5423 (6)0.8711 (2)0.8278 (3)0.1013 (12)
H50.64820.85740.80000.122*
C60.3962 (5)0.82863 (17)0.8343 (2)0.0822 (9)
H60.40290.78610.81000.099*
C70.0772 (4)0.80522 (15)0.8855 (2)0.0706 (8)
H7−0.02860.82500.90600.085*
C80.0665 (4)0.74079 (14)0.8672 (2)0.0674 (8)
H80.17050.71950.84710.081*
C9−0.0972 (4)0.70302 (14)0.8772 (2)0.0637 (7)
H9−0.20260.72480.89470.076*
C10−0.2802 (4)0.60569 (14)0.8766 (2)0.0694 (8)
H10A−0.38570.63480.86260.083*
H10B−0.28030.59120.94220.083*
C11−0.2957 (4)0.54701 (14)0.8112 (2)0.0673 (8)
H11A−0.39800.51900.82670.081*
H11B−0.31940.56150.74570.081*
C12−0.1214 (4)0.44778 (15)0.8336 (2)0.0630 (7)
H12−0.23640.42680.83000.076*
C130.0416 (4)0.40785 (14)0.8503 (2)0.0624 (7)
H130.15780.42800.85370.075*
C140.0320 (4)0.34316 (14)0.8611 (2)0.0661 (7)
H14−0.08740.32550.85440.079*
C150.1802 (5)0.29590 (14)0.8818 (2)0.0685 (8)
C160.1377 (6)0.22894 (16)0.8800 (2)0.0884 (10)
H160.01540.21520.86600.106*
C170.2773 (10)0.1826 (2)0.8991 (3)0.1219 (18)
H170.24770.13800.89770.146*
C180.4567 (9)0.2015 (3)0.9198 (3)0.131 (2)
H180.54960.17000.93070.158*
C190.5004 (6)0.2675 (3)0.9245 (3)0.1094 (14)
H190.62280.28030.94050.131*
C200.3652 (5)0.31469 (18)0.9059 (2)0.0784 (9)
H200.39670.35920.90930.094*
Cl10.20858 (16)0.59354 (5)0.69366 (8)0.1081 (4)
Cl20.30022 (11)0.55861 (5)0.95630 (7)0.0897 (3)
N1−0.1064 (3)0.64122 (11)0.86341 (17)0.0614 (6)
N2−0.1194 (3)0.51002 (10)0.82321 (16)0.0593 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0504 (2)0.0597 (2)0.0751 (3)0.00295 (13)0.01574 (16)0.00885 (15)
C10.096 (2)0.0645 (18)0.0562 (18)−0.0083 (16)−0.0095 (16)0.0046 (14)
C20.141 (4)0.070 (2)0.074 (3)−0.011 (2)−0.012 (2)−0.0016 (17)
C30.186 (6)0.079 (3)0.091 (3)−0.042 (3)−0.033 (3)0.002 (2)
C40.158 (5)0.115 (4)0.088 (3)−0.066 (3)−0.040 (3)0.030 (3)
C50.104 (3)0.116 (3)0.081 (3)−0.037 (2)−0.015 (2)0.021 (2)
C60.088 (2)0.084 (2)0.073 (2)−0.0153 (19)−0.0024 (18)0.0062 (18)
C70.079 (2)0.0661 (18)0.066 (2)0.0042 (15)0.0032 (15)−0.0019 (15)
C80.0682 (18)0.0607 (18)0.074 (2)0.0033 (13)0.0079 (15)0.0016 (15)
C90.0599 (17)0.0656 (18)0.066 (2)0.0055 (13)0.0109 (14)0.0036 (14)
C100.0510 (16)0.0672 (17)0.093 (2)−0.0010 (13)0.0202 (15)−0.0057 (16)
C110.0497 (15)0.0717 (18)0.080 (2)0.0018 (13)0.0009 (14)0.0018 (16)
C120.0601 (17)0.0664 (17)0.0626 (19)−0.0061 (13)0.0053 (14)−0.0033 (14)
C130.0569 (16)0.0596 (16)0.070 (2)−0.0013 (12)0.0027 (14)−0.0044 (14)
C140.0681 (18)0.0637 (18)0.0661 (19)−0.0057 (14)0.0036 (14)−0.0026 (14)
C150.089 (2)0.0611 (18)0.0550 (18)0.0098 (15)0.0066 (16)−0.0031 (14)
C160.132 (3)0.067 (2)0.064 (2)0.006 (2)−0.010 (2)−0.0051 (16)
C170.213 (6)0.073 (2)0.075 (3)0.047 (3)−0.016 (3)−0.0095 (19)
C180.164 (5)0.140 (4)0.088 (3)0.091 (4)−0.003 (3)−0.008 (3)
C190.093 (3)0.159 (4)0.076 (3)0.046 (3)0.006 (2)0.003 (3)
C200.075 (2)0.091 (2)0.070 (2)0.0096 (18)0.0065 (16)0.0062 (17)
Cl10.1177 (8)0.1124 (7)0.1025 (8)0.0353 (6)0.0584 (6)0.0377 (6)
Cl20.0556 (5)0.1233 (7)0.0894 (6)−0.0061 (4)0.0012 (4)0.0130 (5)
N10.0555 (13)0.0600 (14)0.0702 (16)0.0012 (10)0.0137 (11)0.0006 (11)
N20.0549 (13)0.0592 (14)0.0641 (15)0.0023 (10)0.0068 (11)0.0023 (11)
Geometric parameters (Å, °) top
Zn1—N22.042 (2)C10—H10A0.970
Zn1—N12.059 (2)C10—H10B0.970
Zn1—Cl22.2064 (10)C11—N21.473 (3)
Zn1—Cl12.2092 (10)C11—H11A0.970
C1—C61.391 (4)C11—H11B0.970
C1—C21.396 (5)C12—N21.270 (3)
C1—C71.465 (4)C12—C131.431 (4)
C2—C31.382 (6)C12—H120.930
C2—H20.930C13—C141.322 (4)
C3—C41.348 (7)C13—H130.930
C3—H30.930C14—C151.447 (4)
C4—C51.381 (7)C14—H140.930
C4—H40.930C15—C161.391 (4)
C5—C61.370 (5)C15—C201.402 (4)
C5—H50.930C16—C171.386 (6)
C6—H60.930C16—H160.930
C7—C81.332 (4)C17—C181.357 (7)
C7—H70.930C17—H170.930
C8—C91.424 (4)C18—C191.373 (7)
C8—H80.930C18—H180.930
C9—N11.268 (3)C19—C201.375 (5)
C9—H90.930C19—H190.930
C10—N11.471 (3)C20—H200.930
C10—C111.503 (4)
N2—Zn1—N183.04 (9)N2—C11—C10108.3 (2)
N2—Zn1—Cl2113.83 (7)N2—C11—H11A110.0
N1—Zn1—Cl2111.68 (7)C10—C11—H11A110.0
N2—Zn1—Cl1112.73 (8)N2—C11—H11B110.0
N1—Zn1—Cl1113.52 (7)C10—C11—H11B110.0
Cl2—Zn1—Cl1117.26 (4)H11A—C11—H11B108.4
C6—C1—C2118.2 (4)N2—C12—C13124.3 (3)
C6—C1—C7123.4 (3)N2—C12—H12117.8
C2—C1—C7118.5 (4)C13—C12—H12117.8
C3—C2—C1120.4 (5)C14—C13—C12121.9 (3)
C3—C2—H2119.8C14—C13—H13119.0
C1—C2—H2119.8C12—C13—H13119.0
C4—C3—C2120.0 (5)C13—C14—C15129.4 (3)
C4—C3—H3120.0C13—C14—H14115.3
C2—C3—H3120.0C15—C14—H14115.3
C3—C4—C5121.2 (5)C16—C15—C20118.2 (3)
C3—C4—H4119.4C16—C15—C14119.0 (3)
C5—C4—H4119.4C20—C15—C14122.8 (3)
C6—C5—C4119.4 (5)C17—C16—C15120.1 (4)
C6—C5—H5120.3C17—C16—H16119.9
C4—C5—H5120.3C15—C16—H16119.9
C5—C6—C1120.9 (4)C18—C17—C16121.0 (4)
C5—C6—H6119.6C18—C17—H17119.5
C1—C6—H6119.6C16—C17—H17119.5
C8—C7—C1126.9 (3)C17—C18—C19119.7 (4)
C8—C7—H7116.5C17—C18—H18120.1
C1—C7—H7116.5C19—C18—H18120.1
C7—C8—C9122.9 (3)C18—C19—C20120.8 (4)
C7—C8—H8118.6C18—C19—H19119.6
C9—C8—H8118.6C20—C19—H19119.6
N1—C9—C8123.3 (3)C19—C20—C15120.1 (4)
N1—C9—H9118.4C19—C20—H20119.9
C8—C9—H9118.4C15—C20—H20119.9
N1—C10—C11109.2 (2)C9—N1—C10119.9 (2)
N1—C10—H10A109.8C9—N1—Zn1130.1 (2)
C11—C10—H10A109.8C10—N1—Zn1109.86 (16)
N1—C10—H10B109.8C12—N2—C11120.0 (2)
C11—C10—H10B109.8C12—N2—Zn1130.7 (2)
H10A—C10—H10B108.3C11—N2—Zn1109.00 (16)
C6—C1—C2—C3−0.9 (5)C16—C15—C20—C191.8 (5)
C7—C1—C2—C3−179.6 (3)C14—C15—C20—C19−179.8 (3)
C1—C2—C3—C40.2 (7)C8—C9—N1—C10179.1 (3)
C2—C3—C4—C50.3 (7)C8—C9—N1—Zn14.1 (4)
C3—C4—C5—C60.0 (7)C11—C10—N1—C9150.3 (3)
C4—C5—C6—C1−0.8 (5)C11—C10—N1—Zn1−33.8 (3)
C2—C1—C6—C51.2 (5)N2—Zn1—N1—C9−176.0 (3)
C7—C1—C6—C5179.8 (3)Cl2—Zn1—N1—C971.1 (3)
C6—C1—C7—C89.5 (5)Cl1—Zn1—N1—C9−64.2 (3)
C2—C1—C7—C8−171.8 (3)N2—Zn1—N1—C108.69 (19)
C1—C7—C8—C9−179.4 (3)Cl2—Zn1—N1—C10−104.23 (19)
C7—C8—C9—N1−177.3 (3)Cl1—Zn1—N1—C10120.48 (19)
N1—C10—C11—N250.0 (3)C13—C12—N2—C11−176.8 (3)
N2—C12—C13—C14179.6 (3)C13—C12—N2—Zn1−3.6 (4)
C12—C13—C14—C15−177.5 (3)C10—C11—N2—C12132.9 (3)
C13—C14—C15—C16−173.3 (3)C10—C11—N2—Zn1−41.7 (3)
C13—C14—C15—C208.3 (5)N1—Zn1—N2—C12−155.4 (3)
C20—C15—C16—C17−1.8 (5)Cl2—Zn1—N2—C12−44.7 (3)
C14—C15—C16—C17179.7 (3)Cl1—Zn1—N2—C1292.0 (3)
C15—C16—C17—C180.1 (6)N1—Zn1—N2—C1118.43 (19)
C16—C17—C18—C191.8 (7)Cl2—Zn1—N2—C11129.09 (17)
C17—C18—C19—C20−1.9 (7)Cl1—Zn1—N2—C11−94.19 (18)
C18—C19—C20—C150.0 (6)
Acknowledgements top

The authors thank Dr Zhi-Dong Lin for assistance with the data.

references
References top

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

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Tolman, W. B., Liu, S., Bentsen, J. G. & Lippard, S. J. (1991). J. Am. Chem. Soc. 113, 152–164

Wang, F.-W., Wei, Y.-J. & Zhu, Q.-Y. (2007). Acta Cryst. E63, m1084–m1085.