Dichlorido(di-2-pyridylamine)mercury(II)

Mohammad Yousefi; Mohammad Reza Allahgholi Ghasri; Amene Heidari; Vahid Amani

doi:10.1107/S1600536808040294

. 2008 Dec 6;65(Pt 1):m9–m10. doi: 10.1107/S1600536808040294

Dichlorido(di-2-pyridylamine)mercury(II)

Mohammad Yousefi ^a, Mohammad Reza Allahgholi Ghasri ^a, Amene Heidari ^b, Vahid Amani ^a,^*

PMCID: PMC2967852 PMID: 21581552

Abstract

In the molecule of the title compound, [HgCl₂(C₁₀H₉N₃)], the Hg^II atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from the chelating di-2-pyridylamine ligand and by two Cl atoms. In the crystal structure, intermolecular N—H⋯Cl hydrogen bonds link the molecules into centrosymmetric dimers. There is a π–π contact between the pyridine rings [centroid–centroid distance = 3.896 (5) Å].

Related literature

For related literature, see: Ahmadi et al. (2008 ▶); Kalateh, Ebadi et al. (2008 ▶); Kalateh, Norouzi et al. (2008 ▶); Khavasi et al. (2008 ▶); Tadayon Pour et al. (2008 ▶); Yousefi, Rashidi Vahid et al. (2008 ▶); Yousefi, Tadayon Pour et al. (2008 ▶). For related structures, see: Chen et al. (2006 ▶); Liu et al. (2004 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[HgCl₂(C₁₀H₉N₃)]
M _r = 442.69
Triclinic,
a = 8.0268 (12) Å
b = 8.6127 (11) Å
c = 9.6118 (14) Å
α = 110.606 (11)°
β = 98.958 (12)°
γ = 96.862 (11)°
V = 603.38 (15) Å³
Z = 2
Mo Kα radiation
μ = 13.17 mm⁻¹
T = 298 (2) K
0.24 × 0.21 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi scan (SADABS; Sheldrick, 1998 ▶) T _min = 0.061, T _max = 0.142
7105 measured reflections
3214 independent reflections
2806 reflections with I > 2σ(I)
R _int = 0.069

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.126
S = 1.05
3214 reflections
150 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.43 e Å⁻³
Δρ_min = −2.08 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808040294/hk2588sup1.cif

e-65-000m9-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040294/hk2588Isup2.hkl

e-65-000m9-Isup2.hkl^{(154.4KB, hkl)}

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

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

Cl1—Hg1	2.3875 (19)
Cl2—Hg1	2.4579 (19)
N1—Hg1	2.369 (6)
N3—Hg1	2.290 (6)

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N1—Hg1—Cl1	112.30 (15)
N1—Hg1—Cl2	94.92 (15)
N3—Hg1—Cl1	112.21 (15)
N3—Hg1—Cl2	123.92 (14)
N3—Hg1—N1	82.4 (2)
Cl1—Hg1—Cl2	120.14 (7)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯Cl2ⁱ	0.95 (16)	2.41 (16)	3.345 (6)	169 (13)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We are grateful to the Islamic Azad University, Shahr-e-Rey Branch, for financial support.

supplementary crystallographic information

Comment

Recently, we reported the synthes and crystal structures of [Hg(NH(py)₂)Br₂], (II), (Kalateh, Norouzi et al., 2008), [Hg(4,4'-dmbpy)I₂], (III), (Yousefi, Tadayon Pour et al., 2008), [Hg(5,5'-dmbpy)I₂], (IV), (Tadayon Pour et al., 2008), [Hg(dmphen)I₂], (V), (Yousefi, Rashidi Vahid et al., 2008), {[HgCl(dm4bt)]₂(µ-Cl)₂}, (VI), (Khavasi et al., 2008), [Hg(6-mbpy)Cl₂], (VII), (Ahmadi et al., 2008) and [{HgBr(4,4'-dmbpy)}₂(µ-Br)₂], (VIII), (Kalateh, Ebadi et al., 2008) [where NH(py)₂ is di-2-pyridylamine, 4,4'-dmbpy is 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine, 6-mbpy is 6-methyl-2,2'-bipyridine, dmphen is 4,7-diphenyl- 1,10-phenanthroline and dm4bt is 2,2'-dimethyl-4,4'-bithiazole].

There are several Hg^II complexes, with formula, [Hg(N—N)Cl₂], such as [Hg(bipy)Cl₂], (IX), and [Hg(bipy)Cl₂][HgCl₂], (X), (Chen et al., 2006) and [Hg(dpdmbip) Cl₂].CH₂Cl₂, (XI), (Liu et al., 2004) [where bipy is 2,2'-bipyridine and dpdmbip is 4,4'-diphenyl-6,6'-dimethyl-2,2'-bipyrimidine] have been synthesized and characterized by single-crystal X-ray diffraction methods. We report herein the synthesis and crystal structure of the title compound, (I).

In the title compound, (Fig. 1), the Hg^II atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from di-2-pyridylamine and two Cl atoms. The Hg-Cl and Hg-N bond lengths (Allen et al., 1987) and angles (Table 1) are within normal ranges.

In the crystal structure, intermolecular N-H···Cl hydrogen bonds (Table 2) link the molecules into centrosymmetric dimers, in which they may be effective in the stabilization of the crystal structure (Fig. 2). The π-π contact between the pyridine rings, Cg2···Cg3ⁱ [symmetry code: (i) -x, 1 - y, 1 - z, where Cg2 and Cg3 are centroids of the rings A (N1/C1-C5) and B (N3/C6-C10), respectively] may further stabilize the structure, with centroid-centroid distance of 3.896 (5)%A.

Experimental

For the preparation of the title compound, (I), a solution of di-2-pyridylamine (0.25 g, 1.43 mmol) in methanol (20 ml) was added to a solution of HgCl₂ (0.39 g, 1.43 mmol) in acetonitrile (20 ml) and the resulting colorless solution was stirred for 20 min at 313 K. This solution was left to evaporate slowly at room temperature. After one week, colorless block crystals of the title compound were isolated (yield; 0.47 g, 74.3%).