Dichlorido(5,5′-dimethyl-2,2′-bipyridine-κ2 N,N′)zinc(II)

Aida Khalighi; Roya Ahmadi; Vahid Amani; Hamid Reza Khavasi

doi:10.1107/S1600536808027104

. 2008 Aug 30;64(Pt 9):m1211–m1212. doi: 10.1107/S1600536808027104

Dichlorido(5,5′-dimethyl-2,2′-bipyridine-κ² N,N′)zinc(II)

Aida Khalighi ^a, Roya Ahmadi ^a, Vahid Amani ^a,^*, Hamid Reza Khavasi ^b

PMCID: PMC2960607 PMID: 21201646

Abstract

The asymmetric unit of the title compound, [ZnCl₂(C₁₂H₁₂N₂)], contains two independent molecules. The Zn^II atoms are four-coordinated in distorted tetrahedral configurations by two N atoms from 5,5′-dimethyl-2,2′-bipyridine and two terminal Cl atoms. In the crystal structure, intermolecular C—H⋯Cl hydrogen bonds link the molecules. There are C—H⋯π contacts between the methyl groups and the pyridine and five-membered rings containing Zn^II atoms; π–π contacts also exist between the pyridine rings [centroid–centroid distances = 3.665 (5) and 3.674 (5) Å].

Related literature

For related literature, see: Gruia et al. (2007 ▶); Khan & Tuck (1984 ▶); Khavasi et al. (2008 ▶); Kozhevnikov et al. (2006 ▶); Liu et al. (2004 ▶); Lundberg (1966 ▶); Preston & Kennard (1969 ▶); Qin et al. (1999 ▶); Reimann et al. (1966 ▶); Steffen & Palenik (1976 ▶, 1977 ▶).

Experimental

Crystal data

[ZnCl₂(C₁₂H₁₂N₂)]
M _r = 320.53
Orthorhombic,
a = 16.267 (2) Å
b = 11.1704 (16) Å
c = 14.9328 (14) Å
V = 2713.4 (6) Å³
Z = 8
Mo Kα radiation
μ = 2.18 mm⁻¹
T = 298 (2) K
0.28 × 0.20 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ▶) T _min = 0.612, T _max = 0.860
14309 measured reflections
7167 independent reflections
4463 reflections with I > 2σ(I)
R _int = 0.066

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.150
S = 1.07
7167 reflections
307 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ▶), 3320 Friedel pairs
Flack parameter: 0.07 (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/S1600536808027104/hk2517sup1.cif

e-64-m1211-sup1.cif^{(24.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808027104/hk2517Isup2.hkl

e-64-m1211-Isup2.hkl^{(343.6KB, hkl)}

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

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

Zn1—Cl1	2.206 (2)
Zn1—Cl2	2.215 (2)
Zn2—Cl3	2.211 (2)
Zn2—Cl4	2.207 (3)
Zn1—N1	2.058 (6)
Zn1—N2	2.057 (6)
Zn2—N3	2.063 (6)
Zn2—N4	2.066 (6)

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N1—Zn1—N2	80.5 (2)
N1—Zn1—Cl1	112.2 (2)
N1—Zn1—Cl2	117.23 (18)
N2—Zn1—Cl1	115.64 (18)
N2—Zn1—Cl2	111.4 (2)
Cl1—Zn1—Cl2	115.28 (10)
N3—Zn2—N4	79.7 (3)
N3—Zn2—Cl3	112.09 (18)
N3—Zn2—Cl4	114.47 (17)
N4—Zn2—Cl4	112.8 (2)
N4—Zn2—Cl3	115.01 (18)
Cl4—Zn2—Cl3	117.19 (9)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl3ⁱ	0.93	2.82	3.516 (8)	132
C16—H16⋯Cl3ⁱⁱ	0.93	2.83	3.638 (10)	146
C3—H3A⋯Cg5	0.96	3.10	3.719 (6)	124
C11—H11A⋯Cg2ⁱⁱⁱ	0.96	2.83	3.688 (5)	150
C15—H15C⋯Cg1^iv	0.96	2.84	3.704 (6)	150
C23—H23C⋯Cg4	0.96	3.11	3.690 (6)	120

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg1, Cg2, Cg4 and Cg5 are the centroids of atoms Zn1/N1/C6/C7/N2, N1/C1/C2/C4–C6, Zn2/N3/C18/C19/N4 and N3/C13/C14/C16–C18, respectively.

Acknowledgments

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

supplementary crystallographic information

Comment

There are several Zn^II complexes, with formula, [ZnCl₂(N—N)], such as [ZnCl₂(bipy)], (II), (Khan & Tuck, 1984), [ZnCl₂(biim)], (III), (Gruia et al., 2007), [ZnCl₂(phbipy)], (IV), (Kozhevnikov et al., 2006), [ZnCl₂(phen)], (V), (Reimann et al., 1966), [ZnCl₂(dmphen)], (VI), (Preston & Kennard, 1969), [ZnCl₂(dpdmbip)], (VII), (Liu et al., 2004) and [ZnCl₂(dm4bt)], (VIII), (Khavasi et al., 2008) [where bipy is 2,2'-bipyridine, biim is 2,2'-biimidazole, phbipy is 5-phenyl-2,2'-bi- pyridine, phen is 1,10-phenanthroline, dmphen is 2,9-dimethyl-1,10-phenanthro- line, dpdmbip is 4,4'-diphenyl-6,6'-dimethyl-2,2'-bipyrimidine and dm4bt is 2,2'-dimethyl-4,4'-bithiazole] have been synthesized and characterized by single-crystal X-ray diffraction methods. There are also several Zn^II complexes, with formula, [ZnCl₂L₂], such as [ZnCl₂(py)₂], (IX), (Steffen & Palenik, 1976), [ZnCl₂(4-cypy)₂], (X), (Steffen & Palenik, 1977), [ZnCl₂(2-ampy)₂], (XI), (Qin et al., 1999) and [ZnCl₂(im)₂], (XII), (Lundberg, 1966), [where py is pyridine, 4-cypy is 4-cyanopyridine, 2-ampy is 2-aminopyridine and im is imidazole] 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).

The asymmetric unit of (I), (Fig. 1), contains two independent molecules. The Zn^II atoms are four-coordinated in distorted tetrahedral configurations (Table 1) by two N atoms from 5,5'-dimethyl-2,2'-bipyridine and two terminal Cl. The Zn-Cl and Zn-N bond lengths and angles (Table 1) are within normal ranges, as in (II), (V) and (VIII).

In the crystal structure, intermolecular C-H···Cl hydrogen bonds (Table 2) link the molecules, in which they may be effective in the stabilization of the structure. There also exist C—H···π contacts (Table 1) between the methyl groups and pyridine, (Zn1/N1/N2/C6/C7) and (Zn2/N3/N4/C18/C19) rings. The π—π contacts between the pyridine rings, Cg3···Cg6ⁱ and Cg4···Cg5ⁱⁱ [symmetry codes: (i) x, y, z; (ii) x, 1 + y, z, where Cg3, Cg4, Cg5 and Cg6 are centroids of the rings (N1/C1/C2/C4-C6), (N2/C7-C10/C12), (N3/C13/C14/C16-C18) and (N4/C19-C22/C24), respectively] further stabilize the structure, with centroid-centroid distances of 3.665 (5) and 3.674 (5) Å, respectively.

Experimental

For the preparation of the title compound, a solution of 5,5'-dimethyl-2,2' -bipyridine (0.25 g, 1.33 mmol) in methanol (100 ml) was added to a solution of ZnCl₂ (0.18 g, 1.33 mmol) in methanol (100 ml) and the resulting colorless solution was stirred for 5 min at room temperature, and then left to evaporate slowly at room temperature. After one week, colorless block crystals of the title compound were isolated (yield; 0.32 g, 73.4%, m.p. < 573 K).