Bis(2,1,3-benzoselenadiazole-κN)dichloridozinc(II)

Hoong-Kun Fun; Annada C Maity; Sibaprasad Maity; Shyamaprosad Goswami; Suchada Chantrapromma

doi:10.1107/S1600536808026366

. 2008 Aug 20;64(Pt 9):m1188. doi: 10.1107/S1600536808026366

Bis(2,1,3-benzoselenadiazole-κN)dichloridozinc(II)

Hoong-Kun Fun ^a,^*, Annada C Maity ^b, Sibaprasad Maity ^b, Shyamaprosad Goswami ^b, Suchada Chantrapromma ^c,^‡

PMCID: PMC2960704 PMID: 21201628

Abstract

In the title complex, [ZnCl₂(C₆H₄N₂Se)₂], the Zn^II center is tetracoordinated by a Cl₂N₂ donor set in a distorted tetrahedral geometry. Some of the distortion from the ideal tetrahedral geometry might be ascribed to two agostic Z⋯H interactions The two 2,1,3-benzoselenadiazole ligands are each essentially planar and form a dihedral angle of 35.06 (9)°. An interesting feature of the crystal packing is the observation of short intermolecular contacts between Se and Se, Se and N, and N and N atoms. These arise as a result of three-center bridging of adjacent molecules into chains along the b axis. The crystal structure is stablilized by π–π interactions [minimum centroid–centroid distance = 3.5694 (18) Å].

Related literature

For related literature and applications of the 2,1,3-benzoselenadiazole molecule and its metal complexes, see, for example: Galet et al. (1994 ▶); Grivas (2000 ▶); Iwaoka & Tomoda (1994 ▶, 2000 ▶); Saiki et al. (1997 ▶); Zhou et al. (2005 ▶).

Experimental

Crystal data

[ZnCl₂(C₆H₄N₂Se)₂]
M _r = 502.43
Triclinic,
a = 7.5593 (2) Å
b = 9.7269 (3) Å
c = 10.6083 (3) Å
α = 95.103 (1)°
β = 92.581 (1)°
γ = 101.713 (1)°
V = 759.15 (4) Å³
Z = 2
Mo Kα radiation
μ = 6.76 mm⁻¹
T = 297 (2) K
0.48 × 0.32 × 0.30 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.141, T _max = 0.236 (expected range = 0.079–0.132)
17787 measured reflections
4425 independent reflections
3836 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.094
S = 1.06
4425 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808026366/tk2296sup1.cif

e-64-m1188-sup1.cif^{(19KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808026366/tk2296Isup2.hkl

e-64-m1188-Isup2.hkl^{(216.8KB, hkl)}

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

Table 1. Selected interatomic distances (Å).

Se1⋯Se2ⁱ	3.7002 (4)
Se1⋯N4ⁱ	2.893 (2)
Se2⋯N2ⁱⁱ	2.918 (2)
N2⋯N4ⁱ	2.882 (3)
Se1⋯Cl1	3.4111 (8)
Se2⋯Cl2	3.4192 (9)
Cl1⋯N1	3.293 (2)
Zn1⋯H2B	3.23
Zn1⋯H8B	3.26

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

Acknowledgments

We thank the DST [SR/S1/OC-13/2005], Government of India, for financial support. ACM and SM thank the Government of India for their fellowships. The authors also thank the Malaysian Government and Universiti Sains Malaysia for Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Metal complexes of 2,1,3-benzoselenadiazole continue to attract the interest of inorganic chemists (e.g. Grivas, 2000). Organoselenium derivatives stabilized by non-bonded Se···N interactions (Galet et al., 1994); Iwaoka & Tomoda, 1994; 2000; Saiki et al., 1997) are also of interest because of their vital roles in many chemical phenomena, such as molecular recognition and molecular packing in crystal phases as well as due to their biological roles (Zhou et al., 2005). The reaction of 2,1,3-benzoselenadiazole with ZnCl₂ results in the formation of the title zinc(II) complex (I).

The structure of (I) comprises a neutral ZnCl₂L₂ molecule (L= 2,1,3-benzoselenadiazole ligand), Fig. 1. The Zn^II ion is tetra-coordinated by two Cl^- ions and two N atoms derived from the L ligands. The L ligands are each essentially planar with the maximum deviation of 0.028 (2)Å being for atom N1 in one ligand and 0.044 (2) Å for the N3 atom in the other ligand. The dihedral angle between the their mean planes is 35.06 (9)°. The distorted tetrahedral geometry can be indicated by the bond angles subtended at Zn: N—Zn—N = 111.13 (9)°, Cl—Zn—Cl = 122.58 (4)°, and N—Zn—Cl in the range of 100.70 (6) - 110.81 (7)°. Some of the distortion from the ideal tetrahedral geometry might be ascribed to two agostic Zn···H interactions, Table 1.

The interesting feature of the crystal packing is the observation of short intermolecular contacts between Se and Se, Se and N, and N and N atoms (Table 1). These arise as a result of three-center bridging of adjacent molecules into chains along the b-axis, Fig. 2. The crystal is further stabilized by π–π interactions with the shortest of these being 3.5694 (18) Å for Cg(C7/C12/N4/Se2/N3)···Cg(C7–C12)ⁱ for i: -x, 2-y, -z.

Experimental

A slurry of 2,1,3-benzoselenadiazole (1 g, 5.4 mmol) and anhydrous zinc chloride (270 mg, 2.72 mmol) in dry methanol (15 ml) was heated at 343–353 K for 2 h. After completion of the reaction, the mixture was allowed to cool to room temperature and the precipitate (I) was collected by filtration. Recrystallization of (I) from 40% methanol in chloroform afforded a yellow microcrystalline solid (1.16 g, 85% yield).