[Bis(pyridin-2-yl) selenide-κ2 N,N′]tetra­chloridotin(IV)

Gunay Z Mammadova; Zhanna V Matsulevich; Vladimir K Osmanov; Alexander V Borisov; Victor N Khrustalev

doi:10.1107/S160053681202586X

. 2012 Jun 30;68(Pt 7):m983. doi: 10.1107/S160053681202586X

[Bis(pyridin-2-yl) selenide-κ² N,N′]tetrachloridotin(IV)

Gunay Z Mammadova ^a,^*, Zhanna V Matsulevich ^b, Vladimir K Osmanov ^b, Alexander V Borisov ^b, Victor N Khrustalev ^c

PMCID: PMC3393232 PMID: 22807800

Abstract

The title compound, [SnCl₄(C₁₀H₈N₂Se)], was obtained by the reaction of 2,2′-dipyridyl diselenide with tin tetrachloride. The Sn^IV ion is coordinated by two N atoms [Sn—N = 2.266 (2) and 2.274 (2) Å] from the bis(2-pyridyl)selenide ligand and four chloride anions [Sn—Cl = 2.3717 (6)–2.3939 (6) Å] in a distorted octahedral geometry. The central six-membered chelate ring has a boat conformation with the Se and Sn atoms deviating by 0.692 (3) and 0.855 (3) Å, respectively, from the mean plane through the remaining four ring atoms. The pyridine rings are inclined to each other by a dihedral angle of 49.62 (8)°. The crystal packing exhibits short intermolecular Se⋯Cl contacts [3.5417 (7) and 3.5648 (7) Å], weak C—H⋯Cl hydrogen bonds and π–π stacking interactions between the pyridine rings with a centroid–centroid distance of 3.683 (3) Å.

Related literature

For the crystal structure of the 2,2′-dipyridyl-selenide ligand, see: Dunne et al. (1995 ▶). For the crystal structures of related compounds, see: Tresoldi et al. (1992 ▶); Kondo et al. (1995 ▶); Blake et al. (2002 ▶); Teles et al. (2006 ▶); Zhao et al. (2007 ▶); Wriedt et al. (2008a ▶,b ▶,c ▶).

Experimental

Crystal data

[SnCl₄(C₁₀H₈N₂Se)]
M _r = 495.63
Monoclinic,
a = 8.0835 (4) Å
b = 12.2153 (5) Å
c = 14.4710 (6) Å
β = 101.208 (1)°
V = 1401.65 (11) Å³
Z = 4
Mo Kα radiation
μ = 5.16 mm⁻¹
T = 100 K
0.30 × 0.24 × 0.15 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: multi-scan [SADABS; Sheldrick, 1998 ▶) T _min = 0.306, T _max = 0.511
16245 measured reflections
4096 independent reflections
3723 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.058
S = 1.00
4096 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 1.64 e Å⁻³
Δρ_min = −1.10 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: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681202586X/cv5309sup1.cif

e-68-0m983-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202586X/cv5309Isup2.hkl

e-68-0m983-Isup2.hkl^{(200.8KB, 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
C3—H3⋯Cl3ⁱ	0.95	2.79	3.3965 (18)	122
C8—H8⋯Cl2ⁱⁱ	0.95	2.83	3.3126 (18)	113

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

Acknowledgments

We thank Professor Abel M. Maharramov for fruitful discussions and help in this work.

supplementary crystallographic information

Comment

2,2'-Dipyridyl sulfide plays prominent role as useful ligand in coordination chemistry (Tresoldi et al., 1992; Kondo et al., 1995; Blake et al., 2002; Teles et al., 2006; Zhao et al., 2007; Wriedt et al., 2008a, 2008b, 2008c). The important structural feature of these complexes is the practically unchangeable bond angle at sulfur atom. On the other hand, the most labile geometrical parameters in them are the dihedral angle between two pyridine rings as well as the deviation of metal atom from the mean plane of the central six-membered chelate ring passed through the two nitrogen and two carbon atoms due to the different coordination environment. It is interesting to note that 2,2'-dipyridyl selenide is also known (Dunne et al., 1995), however, no structurally characterized metal complexes with this ligand were reported till now.

This article is dedicated to the first structural characterization of metal complex with 2,2'-dipyridyl selenide ligand - [bis(2-pyridyl)selenide-k²N,N')]tetrachlorido-tin(IV), C₁₀H₈Cl₄N₂SeSn (I), which was obtained by the reaction of 2,2'-dipyridyl diselenide with tin tetrachloride (Figure 1).

The molecule of I possesses overall intrinsic C_s (m) symmetry (Figure 2). The tin ion is coordinated by two N atoms [Sn—N 2.266 (2), 2.274 (2) Å] from bis(2-pyridyl)selenide ligand and four chloride anions [Sn—Cl 2.3717 (6)–2.3939 (6) Å] in a distorted octahedral geometry. The central six-membered chelate ring has a boat conformation with the Se and Sn atoms deviating from the mean plane passed through the rest four atoms of the ring at 0.692 (3) and 0.855 (3) Å, respectively. Two pyridine rings are inclined to each other with a dihedral angle of 49.62 (8)°. Remarkably, the value of the bond angle at selenium atom in I (101.51 (10)°) is almost equal to that in the free 2,2'-dipyridyl selenide ligand (101.9 (2)°) (Dunne et al., 1995).

In the crystal, the molecules of I form the chains along the a axis by the attractive intermolecular Se1···Cl2ⁱ [3.5417 (7) Å] and Se1···Cl4ⁱ [3.5648 (7) Å] interactions. The chains are further linked into a three-dimensional framework by weak C—H···Cl hydrogen bonds (Table 1) and π···π stacking interactions between the pyridine rings with a centroid-centroid distance of 3.683 (3) Å. Symmetry code: (i) x - 1, y, z.

Experimental

A solution of SnCl₄ (0.13 g, 0.5 mmol) in CH₂Cl₂ (25 ml) was added to a solution of 2,2'-dipyridyl diselenide (0.16 g, 0.5 mmol) in CH₂Cl₂ (25 ml) with stirring at room temperature. After 10 min, solvent was evaporated in vacuo. An attempt to re-crystallization of the solid residue from CH₃CN led to formation of the powder Se which was separated by filtration of hot solution. The filtrate was concentrated in vacuo. The solid was re-crystallized from CH₃CN to give I as yellow crystals. Yield is 82%. M.p. = 541–543 K. ¹H NMR (DMSO-d₆, 300 MHz, 302 K): δ = 8.48 (d, 2H, J = 4.8), 7.70 (t, 2H, J = 7.8), 7.55 (d, 2H, J = 7.8), 7.28 (dd, 2H, J = 7.8, J = 4.8). Anal. Calcd for C₁₀H₈Cl₄N₂SeSn: C, 24.23; H, 1.63; N, 5.65. Found: C, 24.14;H, 1.59; N, 5.57.