Dibromido(di-2-pyridylamine-κ2 N,N′)mercury(II)

Khadijeh Kalateh; Ali Norouzi; Amin Ebadi; Roya Ahmadi; Vahid Amani

doi:10.1107/S1600536808038129

. 2008 Nov 20;64(Pt 12):m1583–m1584. doi: 10.1107/S1600536808038129

Dibromido(di-2-pyridylamine-κ² N,N′)mercury(II)

Khadijeh Kalateh ^a, Ali Norouzi ^b, Amin Ebadi ^c, Roya Ahmadi ^a, Vahid Amani ^a,^*

PMCID: PMC2960074 PMID: 21581184

Abstract

In the molecule of the title compound, [HgBr₂(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 Br atoms. In the crystal structure, intermolecular N—H⋯Br hydrogen bonds link the molecules into centrosymmetric dimers. There are π–π contacts between the pyridine rings [centroid–centroid distances = 3.9662 (5) and 3.9321 (4) Å]. There also exists a C—H⋯π contact between the pyridine CH group and a pyridine ring.

Related literature

For related literature, see: Ahmadi et al. (2008 ▶); Kalateh 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: Xie et al. (2004 ▶); Hughes et al. (1985 ▶).

Experimental

Crystal data

[HgBr₂(C₁₀H₉N₃)]
M _r = 531.59
Triclinic,
a = 8.1284 (16) Å
b = 8.7645 (18) Å
c = 9.912 (2) Å
α = 113.45 (3)°
β = 98.41 (3)°
γ = 97.79 (3)°
V = 626.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 18.65 mm⁻¹
T = 120 (2) K
0.40 × 0.35 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: numerical (shape of crystal determined optically) (X-SHAPE and X-RED; Stoe & Cie, 2005 ▶)T _min = 0.016, T _max = 0.080
7839 measured reflections
3350 independent reflections
3234 reflections with I > 2σ(I)
R _int = 0.087

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.140
S = 1.15
3350 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 4.33 e Å⁻³
Δρ_min = −6.54 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/S1600536808038129/hk2575sup1.cif

e-64-m1583-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038129/hk2575Isup2.hkl

e-64-m1583-Isup2.hkl^{(161KB, hkl)}

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

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

Br1—Hg1	2.5106 (11)
Br2—Hg1	2.5549 (11)
N1—Hg1	2.301 (7)
N3—Hg1	2.350 (7)

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N1—Hg1—N3	81.1 (2)
N1—Hg1—Br1	109.13 (17)
N3—Hg1—Br1	117.16 (17)
N1—Hg1—Br2	125.41 (17)
N3—Hg1—Br2	96.23 (18)
Br1—Hg1—Br2	119.68 (3)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Br2ⁱ	0.86	2.62	3.472 (3)	170
C2—H2⋯Cg3ⁱⁱ	0.93	3.20	3.587 (3)	107

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Symmetry codes: (i) Inline graphic ; (ii) . Cg3 is the centroid of the N3/C6–C10 ring.

Acknowledgments

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

supplementary crystallographic information

Comment

Recently, we reported the syntheses and crystal structures of [Hg(4,4'-dmbpy) I₂], (II), (Yousefi, Tadayon Pour et al., 2008), [Hg(5,5'-dmbpy)I₂], (III), (Tadayon Pour, et al., 2008), [Hg(dmphen)I₂], (IV), (Yousefi, Rashidi Vahid et al., 2008), {[HgCl(dm4bt)]₂(µ-Cl)₂}, (V), (Khavasi et al., 2008), [Hg(6-mbpy)Cl₂], (VI), (Ahmadi et al., 2008) and [{HgBr(4,4'-dmbpy)}₂(µ-Br)₂], (VII), (Kalateh et al., 2008) [where 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 two Hg^II complexes, with formula, [Hg(N—N)Br₂], such as [Hg(TPA)Br₂], (VIII), (Xie et al., 2004) and [Hg(TPD)Br₂], (IX), (Hughes et al., 1985) [where TPA is tris(2-pyridyl)amine and TPD is N,N,N',N'-Tetramethyl-o-phenylenediamine] 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 Br atoms. The Hg-Br and Hg-N bond lengths and angles (Table 1) are within normal ranges, as in (VIII).

In the crystal structure, intermolecular N-H···Br hydrogen bonds link the molecules into centrosymmetric dimers (Fig. 2), in which they may be effective in the stabilization of the structure. The π-π contacts between the pyridine rings Cg2···Cg2ⁱ and Cg2···Cg3ⁱⁱ [symmetry codes: (i) x, -y, 2 - z, (ii) 1 - x,- y, 2 - 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 distances of 3.9662 (5) %A and 3.9321 (4) %A, respectively. There also exists a C—H···π contact (Table 1) between the pyridine CH group and pyridine ring.

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 HgBr₂ (0.51 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 prismatic crystals of the title compound were isolated (yield; 0.55 g, 72.3%).