[N,N′-Bis(4-chloro­benz­yl)ethane-1,2-diamine]dichloridozinc(II)

Shu-Ping Yang; Li-Jun Han; Da-Qi Wang; Hai-Tao Xia

doi:10.1107/S1600536807063088

. 2007 Dec 6;64(Pt 1):m62. doi: 10.1107/S1600536807063088

[N,N′-Bis(4-chlorobenzyl)ethane-1,2-diamine]dichloridozinc(II)

Shu-Ping Yang ^a,^*, Li-Jun Han ^b, Da-Qi Wang ^c, Hai-Tao Xia ^a

PMCID: PMC2914944 PMID: 21200633

Abstract

In the title complex, [ZnCl₂(C₁₆H₁₈Cl₂N₂)], the asymmetric unit contains one molecule and two half-molecules, which have similar geometric parameters; in the latter two molecules each Zn atom lies on a twofold rotation axis. The environment about each Zn^II atom is distorted tetrahedral with coordination of two terminal Cl atoms and two N atoms of the N,N′-bis(4-chlorobenzyl)ethane-1,2-diamine ligand. Four N—H⋯Cl hydrogen bonds link the molecules into a chain of R ₂ ²(8) rings in the [001] direction.

Related literature

For related literature, see: Han et al. (2006 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

[ZnCl₂(C₁₆H₁₈Cl₂N₂)]
M _r = 445.49
Monoclinic,
a = 32.753 (3) Å
b = 6.9774 (1) Å
c = 21.365 (2) Å
β = 127.062 (2)°
V = 3896.2 (5) Å³
Z = 8
Mo Kα radiation
μ = 1.81 mm⁻¹
T = 298 (2) K
0.56 × 0.43 × 0.40 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.431, T _max = 0.532 (expected range = 0.393–0.485)
9226 measured reflections
6408 independent reflections
4023 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.190
S = 1.06
6408 reflections
417 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −1.37 e Å⁻³
Absolute structure: Flack (1983 ▶), 2750 Freidel pairs
Flack parameter: 0.02 (3)

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a ▶); molecular graphics: SHELXTL (Sheldrick, 1997b ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807063088/bv2076sup1.cif

e-64-00m62-sup1.cif^{(29.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063088/bv2076Isup2.hkl

e-64-00m62-Isup2.hkl^{(175.3KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Zn1—N1	2.056 (9)
Zn1—N2	2.081 (8)
Zn1—Cl2	2.202 (3)
Zn1—Cl1	2.232 (3)
Zn2—N3	2.04 (1)
Zn2—Cl5	2.224 (3)
Zn3—N4	2.06 (1)
Zn3—Cl7	2.205 (3)

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N1—Zn1—N2	87.9 (4)
N1—Zn1—Cl2	111.0 (3)
N2—Zn1—Cl2	112.7 (2)
N1—Zn1—Cl1	111.2 (2)
N2—Zn1—Cl1	110.4 (3)
Cl2—Zn1—Cl1	119.4 (1)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl7	0.91	2.43	3.279 (9)	155
N2—H2⋯Cl5	0.91	2.46	3.328 (9)	161
N3—H3⋯Cl2ⁱ	0.91	2.45	3.295 (9)	155
N4—H4⋯Cl1ⁱⁱ	0.91	2.49	3.352 (9)	158

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We acknowledge the financial support of the Huaihai Institute of Technology Science Foundation.

supplementary crystallographic information

Comment

We have reported recently the crystal structure of a Zn^II complex (Han et al., 2006). As part of our study of Zn^II complexes with diamine derivatives, we report here the crystal structure of a new Zn^IIcomplex, dichloro-bis[N,N'-bis(4-chlorobenzyl)-1,2-ethanediamine]zinc(II), (I).

Complex (I) crystallizes in the monoclinic space group C2, with two half-molecules and one molecule in the asymmetric unit (Fig. 1). The central zinc ion is in a distorted tetrahedral environment (Fig.1), coordinated by two terminal Cl atoms and two N atoms of the N,N-bis(4-chlorobenzyl)ethane-1,2-diamine; the bond lengths and angles around the metal centre are listed in table 1. It can be seen that the molecules exhibit similar geometric values, the average values of the Zn—Cl and Zn—N bond lengths are 2.232 (3) Å and 2.06 (5) Å, respectively, which are similar to the Zn^IIcomplex previously reported (Zn—Cl of 2.2213 (9) Å and Zn—N of 2.056 (2) Å; Han et al., 2006); the average value of the dihedral angles enclosed by the N/Zn/N planes and Cl/Zn/Cl planes is 88.9 (4)°.

The molecules are linked by four N—H···Cl hydrogen bonds into a chain of R₂²(8) rings (Bernstein et al., 1995) in the [0 0 1] direction (Table 2 and Fig. 2).

Experimental

To a solution containing N,N-bis(4-chlorobenzyl)ethane-1,2-diamine (1.53 g, 5 mmol) and ethanol (30 ml), a solution of zinc chloride (0.68 g, 5 mmol) and ethanol (10 ml) was added with stirring for 6 h at room temperature (298–300 K); the solid obtained was filtered off, washed successively with chloroform and ethanol, and dried at room temperature. Colourless crystals of (I) suitable for X-ray structure analysis were obtained by slow evaporation of a DMF-ethanol (1:10) solution containing the product over a period of two weeks (M.p.562– 564 K).