Hydrogen-bonding and π–π stacking inter­actions in tris­(1,10-phenanthroline-κ2 N,N′)nickel(II) bis­{[1-tert-butyl­imidazole-2(3H)-thione-κS]trichloridonickelate(II)} acetonitrile disolvate

Udai P Singh; Vaibhave Aggarwal

doi:10.1107/S1600536808018060

. 2008 Jun 19;64(Pt 7):m935–m936. doi: 10.1107/S1600536808018060

Hydrogen-bonding and π–π stacking interactions in tris(1,10-phenanthroline-κ² N,N′)nickel(II) bis{[1-tert-butylimidazole-2(3H)-thione-κS]trichloridonickelate(II)} acetonitrile disolvate

Udai P Singh ^a,^*, Vaibhave Aggarwal ^a

PMCID: PMC2961703 PMID: 21202789

Abstract

The asymmetric unit of the title complex, [Ni(C₁₂H₈N₂)₃][NiCl₃(C₇H₁₂N₂S)]₂·2CH₃CN, consists of one anion, one-half of a cation and one acetonitrile molecule. The Ni^II atom in the [Ni(phen)₃]²⁺ cation (phen is 1,10-phenanthroline) lies on an inversion centre in an octahedral environment, whereas in the [NiCl₃(tm)]⁻ anion [tm is 1-tert-butylimidazole-2(3H)-thione], the geometry is distorted tetrahedral. In the crystal structure, intermolecular C—H⋯Cl hydrogen bonds and π–π stacking interactions (centroid–centroid distance = 3.52 Å) lead to the formation of a three-dimensional framework. One of the methyl groups of the tert-butyl group of N-tert-butyl-2-thioimidazole is disordered between two equally populated positions.

Related literature

For general background, see: Fatimi et al. (1994 ▶); Iradyan et al. (1987 ▶); Suescun et al. (1999 ▶); Yu et al. (2003 ▶); Fang & Dai (2006 ▶); Chen et al., (2007 ▶); Senda et al. (2006 ▶). For synthesis details, see: Kister et al. (1979 ▶).

Experimental

Crystal data

[Ni(C₁₂H₈N₂)₃][NiCl₃(C₇H₁₂N₂S)]₂·2C₂H₃N
M _r = 1324.04
Monoclinic,
a = 22.8953 (15) Å
b = 15.2934 (10) Å
c = 19.9417 (19) Å
β = 123.543 (3)°
V = 5819.7 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.36 mm⁻¹
T = 298 (2) K
0.24 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.737, T _max = 0.792
30921 measured reflections
5178 independent reflections
3346 reflections with I > 2σ(I)
R _int = 0.076

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.157
S = 1.07
5178 reflections
370 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.24 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018060/su2050sup1.cif

e-64-0m935-sup1.cif^{(27.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018060/su2050Isup2.hkl

e-64-0m935-Isup2.hkl^{(224KB, 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
N4—H4⋯Cl2	0.85 (6)	2.37 (7)	3.178 (6)	160 (6)
C2—H2⋯Cl3ⁱ	0.82 (7)	2.77 (7)	3.552 (8)	160 (4)
C5—H5C⋯S1	0.96	2.75	3.402 (9)	126
C7—H7A⋯S1	0.96	2.68	3.409 (8)	133
C10—H10⋯Cl3ⁱⁱ	0.93	2.72	3.557 (7)	151
C25—H25⋯N6ⁱⁱⁱ	0.93	2.60	3.502 (9)	162

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

Acknowledgments

The authors thank the CSIR, New Delhi, for financial support.

supplementary crystallographic information

Comment

2-Thioimidazole (N,N,S donors) and its alkyl derivatives have antithyroid activity and platelet inhibitory effects. (Fatimi et al., 1994; Iradyan et al., 1987). The literature revealed the presence of various nickel(II) complexes with phenanthroline (Suescun et al., 1999; Yu et al. (2003); Fang & Dai, 2006; Chen et al., 2007) but none with N-tert-butyl-2-thioimidazole, except the one reported recently (Senda et al., 2006). The present work reports the first structure of a nickel(II) complex with N-tert-butyl-2-thioimidazole and 1,10 phenanthroline, containing a tetrahedral anion, [Ni(tm)(Cl)₃]^-, and an octahedral cation, [Ni(phen)₃]²⁺.

The title complex (I) is centrosymmetric, ionic in nature and comprises of one complex cation [Ni(phen)₃]²⁺ and two complex anions [Ni(tm)(Cl)₃]^- in the unit cell (Fig. 1). The metal centre in [Ni(phen)₃]²⁺ is in an octahedral environment, the equatorial plane of which is formed by four phen nitrogen atoms, and the axial positions are occupied by another two nitrogen atoms of phen, with Ni1—N bond distances in the range of 2.079 (4)–2.100 (4) Å. The dihedral angles between the meanplanes of the neighboring phen rings are 77.53°, 86.07° and 85.97°. The cis-angles in the octahedron deviate only slightly from 90° and the trans angle in the axial position is almost linear i.e. 170.54 (15)°. The nickel(II) atom in the [Ni(tm)(Cl)₃]^- anion is coordinated by three chlorine atoms and one sulfur atom of tm in a distorted tetrahedral geometry. The Ni—Cl bond distances are in the range of 2.251 (15) to 2.275 (15) Å. In the anion the two short bond distances (Ni2—Cl3 and Ni2—Cl1 of 2.2507 (15) and 2.253 (2) Å, respectively) and two long bond distances (Ni2—S1 and Ni2—Cl2 of 2.3054 (17) and 2.2753 (16) Å, respectively) make the geometry distorted tetrahedral.

Due to the presence of several intermolecular interactions between the three chloride ions bonded to atom Ni2 and the hydrogen atoms present on the phen rings, the complex cation is linked to six complex anions (Fig. 2 and Table 1), whereas the complex anions are linked to four complex cations through C—H···Cl hydrogen bonds (Fig. 3 and Table 1). In the crystal packing of complex (I) two layers are linked by hydrogen bonds in the bc plane. The [Ni(phen)₃]²⁺ cations and the [Ni(tm)(Cl)₃]^- anions interact with each other via hydrogen bonds formed by the terminally coordinated chloride ions of the complex anion (Cl1, Cl2 and Cl3) and the hydrogen atoms present on the phen ligands (Fig. 4). The two complex anions also interact with one another through π–π stacking, with a separation of ca. 3.52 Å, and intermolecular C—H···Cl and C—H···N interactions involving the hydrogen atom of the middle ring of phenanthroline and the nitrogen atom of the acetonitrile molecule present in the lattice (Table 1).

Experimental

All the reagents were of commercial grade and were used as received. N-tert-butyl-thioimidazole (tm) was synthesized by a literature method (Kister et al., 1979). To a solution of NiCl₂.6H₂O (1.0 mmol) in 5 ml methanol, a methanolic solution of N-tert-butyl-2-thioimidazole (1.0 mmol) was added and the mixture stirred for 40 minutes. This mixture was then added to the solution obtained by mixing NiCl₂.6H₂O (1.0 mmol) in methanol with a methanolic solution of 1,10-phenanthroline (3.0 mmol). The whole reaction mixture was stirred for a further 30 minutes. The clear solution obtained was filtered and evaporated to dryness. The solid compound obtained was dissolved in acetonitrile and green single crystals, suitable for X-ray analysis, were obtained by slow evaporation at room temperature. Yield 62%. Analysis calculated for C₅₀H₄₈N₁₀S₂Cl₆Ni₃: C 48.30, H 3.86, N 11.27, S 5.15%; found: C 48.24, H 3.78, N 11.21, S 5.12%. Selected IR frequencies (KBr, ν, cm^-1): 725 (s), 849 (s), 1369 (w), 1575 (m), 1623 (w), 3060 (w), 3412 (s).