catena-Poly[[dichloridomercury(II)]-μ-{N-[(E)-pyridin-2-yl­methyl­idene-κN]pyridin-3-amine-κ2 N 1:N 3}]

Ali Mahmoudi; Saeed Dehghanpour; Leila Najafi; Mohammad Khalafbeigi

doi:10.1107/S1600536812035775

. 2012 Sep 5;68(Pt 10):m1244. doi: 10.1107/S1600536812035775

catena-Poly[[dichloridomercury(II)]-μ-{N-[(E)-pyridin-2-ylmethylidene-κN]pyridin-3-amine-κ² N ¹:N ³}]

Ali Mahmoudi ^a,^*, Saeed Dehghanpour ^b, Leila Najafi ^a, Mohammad Khalafbeigi ^a

PMCID: PMC3470133 PMID: 23125577

Abstract

In the title coordination polymer, [HgCl₂(C₁₁H₉N₃)]_n, the Hg^II ion is coordinated by three N atoms from two N-[(E)-pyridin-2-ylmethylidene]pyridin-3-amine (L) ligands and two chloride anions in a distorted trigonal–bipyramidal geometry. The two pyridine rings in L form a dihedral angle of 50.0 (2)°. L ligands bridge adjacent HgCl₂ units into polymeric chains propagating in [010]. The crystal packing is further stabilized by weak intermolecular C—H⋯Cl hydrogen bonds and π–π interactions between the pyridine rings, with a centroid–centroid separation of 3.529 (9) Å.

Related literature

For related structures and applications of coordination polymers, see: Moulton & Zaworotko (2001 ▶); Fei et al. (2000 ▶). For the synthesis of the ligand and the index of trigonality, see: Dehghanpour et al. (2012 ▶).

Experimental

Crystal data

[HgCl₂(C₁₁H₉N₃)]
M _r = 454.70
Monoclinic,
a = 7.5645 (5) Å
b = 13.1057 (9) Å
c = 12.7017 (5) Å
β = 96.077 (4)°
V = 1252.15 (13) Å³
Z = 4
Mo Kα radiation
μ = 12.70 mm⁻¹
T = 150 K
0.15 × 0.08 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.566, T _max = 0.889
8560 measured reflections
2837 independent reflections
2164 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.116
S = 1.09
2837 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 2.45 e Å⁻³
Δρ_min = −3.10 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812035775/cv5327sup1.cif

e-68-m1244-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035775/cv5327Isup2.hkl

e-68-m1244-Isup2.hkl^{(139.3KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯Cl2ⁱ	0.95	2.82	3.700 (8)	154
C6—H6A⋯Cl2ⁱ	0.95	2.79	3.666 (7)	154
C10—H10A⋯Cl2ⁱⁱ	0.95	2.83	3.545 (8)	132

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

Acknowledgments

The authors acknowledge the Islamic Azad University University Research Councils for partial support of this work.

supplementary crystallographic information

Comment

Many studies has recently been focused on coordination polymers due to their useful properties applicable to catalysis, chirality, conductivity, luminescence (Moulton & Zaworotko, 2001). Nitrogen heterocyclic ligands have been employed in the design and synthesis of many novel coordination polymers (Fei et al., 2000). Herewith we report the synthesis and crystal structure of a novel Hg(II) complex based on pyridin-3-ylpyridin-2-ylmethyleneamine (PyPy).

The asymmetric unit of the title polymeric complex, consisting of one Hg(II) ion, one PyPy ligand and two chloride anions, is shown in Fig. 1. The coordination geometry around Hg(II) is a distorted trigonal–bipyramidal geometry, with the Hg (II) ion being surrounded by two Cl, two N atoms from one PyPy ligand and one N atom from adjacent PyPy ligand. The structural index τ, (Dehghanpour et al., 2012) which is a measure of trigonal distortion, is 0.59 for the title structure indicating a distorted trigonal–bipyramidal environment of Hg(II).

The interplanar angles between the chelate ring (N1—C5—C6—N2) and pyridine ring (N1—C1—C2—C3—C4—C5) is 0.92 (3)° and interplanar angles between the two pyridine rings in the ligand (N1—C1—C2—C3—C4—C5 ring and N3—C11—C7—C8—C9—C10 ring) is 50.0 (2)°. Each PyPy ligand has been chelate HgCl₂ unit (via N, N' atoms) and also bridge to another HgCl₂ unit (with N" atom), resulting into a chain propagated in [010].

These chains interact viaπ–π interactions between adjacent pyridine ringe (N3/C7—C11) related by inversion center, and the distance between their centroids is equal to 3.529 (9) Å. The C—H···Cl interactions (Table 1) are also observed in the crystal structure.

Experimental

The title complex was prepared by the reaction of HgCl₂ (27.1 mg, 0.1 mmol) and pyridin-3-ylpyridin-2-ylmethyleneamine (18.3 mg, 0.1 mmol) in 25 ml of acetonitrile at room temperature. The solution was allowed to stand at room temperature and yellow crystals of the title compound suitable for X-ray analysis precipitated within few days.