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Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): m1266.
Published online 2008 September 13. doi:  10.1107/S1600536808028894
PMCID: PMC2959229

Dichlorido(6-methyl-2,2′-bipyridine-κ2 N,N′)zinc(II)

Abstract

In the mol­ecule of the title compound, [ZnCl2(C11H10N2)], the ZnII atom is four-coordinated in a distorted tetra­hedral configuration by two N atoms from the 6-methyl-2,2′-bipyridine ligand and by two Cl atoms. There are π–π contacts between the pyridine ring and the five-membered ring, and also between the pyridine rings, [centroid–centroid distances = 3.685 (3) and 3.757 (3) Å, respectively].

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-m1266-scheme1.jpg

Experimental

Crystal data

  • [ZnCl2(C11H10N2)]
  • M r = 306.50
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1266-efi1.jpg
  • a = 7.4674 (15) Å
  • b = 9.5105 (17) Å
  • c = 17.656 (4) Å
  • β = 96.551 (18)°
  • V = 1245.7 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.37 mm−1
  • T = 298 (2) K
  • 0.30 × 0.15 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1998 [triangle]) T min = 0.668, T max = 0.802
  • 10401 measured reflections
  • 3358 independent reflections
  • 2576 reflections with I > 2σ(I)
  • R int = 0.078

Refinement

  • R[F 2 > 2σ(F 2)] = 0.060
  • wR(F 2) = 0.130
  • S = 1.17
  • 3358 reflections
  • 145 parameters
  • H-atom parameters constrained
  • Δρmax = 1.04 e Å−3
  • Δρmin = −0.70 e Å−3

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

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536808028894/hk2529sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028894/hk2529Isup2.hkl

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

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 [Cd(5,5'-dmbpy)(µ-Cl)2]n, (II), (Ahmadi et al., 2008) and [Hg(4,4'-dmbpy)I2], (III), (Yousefi et al., 2008) [where 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine and 4,4'-dmbpy is 4,4'-dimethyl-2,2'-bi- pyridine]. There are several ZnII complexes, with formula, [ZnCl2(N-N)], such as [ZnCl2(bipy)], (IV), (Khan & Tuck, 1984), [ZnCl2(biim)], (V), (Gruia et al., 2007), [ZnCl2(phbipy)], (VI), (Kozhevnikov et al., 2006), [ZnCl2(phen)], (VII), (Reimann et al., 1966), [ZnCl2(dmphen)], (VIII), (Preston & Kennard, 1969), [ZnCl2(dpdmbip)], (IX), (Liu et al., 2004), [ZnCl2(dm4bt)], (X), (Khavasi et al., 2008) and [Zn(5,5'-dmbpy)Cl2], (XI), (Khalighi et al., 2008) [where bipy is 2,2'-bipyridine, biim is 2,2'-biimidazole, phbipy is 5-phenyl-2,2'-bipyridine, phen is 1,10-phenanthroline, dmphen is 2,9-dimethyl-1,10-phenanthroline, 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 several ZnII complexes, with formula, [ZnCl2L2], such as [ZnCl2(py)2], (XII), (Steffen & Palenik, 1976), [ZnCl2(4-cypy)2], (XIII), (Steffen & Palenik, 1977), [ZnCl2(2-ampy)2], (XIV), (Qin et al., 1999) and [ZnCl2(im)2], (XV), (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).

In the title compound, (I), (Fig. 1), the ZnII atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from 6-methyl-2,2'-bi- pyridine and two Cl atoms. The Zn-Cl and Zn-N bond lengths and angles (Table 1) are within normal ranges, as in (IV), (VII), (X) and (XI).

In the crystal structure, the π—π contacts (Fig. 2) between the rings A (Zn1/N1/N2/C5/C6) and C (N2/C6-C10), and also between the pyridine rings B (N1/C1-C5) and C, Cg1···Cg3i and Cg2···Cg3ii [symmetry codes: (i) -x, -y, -z; (ii) 1 - x, -y, -z, where Cg1, Cg2 and Cg3 are the centroids of the rings A (Zn1/N1/N2/C5/C6), B (N1/C1-C5) and C (N2/C6-C10), respectively] may stabilize the structure, with centroid-centroid distances of 3.685 (3) Å and 3.757 (3) Å, respectively.

Experimental

For the preparation of the title compound, (I), a solution of 6-methyl-2,2' -bipyridine (0.15 g, 0.88 mmol) in methanol (10 ml) was added to a solution of ZnCl2 (0.12 g, 0.88 mmol) in acetonitrile (30 ml) and the resulting colorless solution was stirred for 20 min at at 313 K, and then it was left to evaporate slowly at room temperature. After one week, colorless block crystals of the title compound were isolated (yield; 0.19 g, 70.4%).

Refinement

H atoms were positioned geometrically, with C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
Fig. 2.
A packing diagram of the title compound.

Crystal data

[ZnCl2(C11H10N2)]F(000) = 616
Mr = 306.50Dx = 1.634 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1987 reflections
a = 7.4674 (15) Åθ = 2.3–29.2°
b = 9.5105 (17) ŵ = 2.37 mm1
c = 17.656 (4) ÅT = 298 K
β = 96.551 (18)°Block, colorless
V = 1245.7 (4) Å30.30 × 0.15 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer3358 independent reflections
Radiation source: fine-focus sealed tube2576 reflections with I > 2σ(I)
graphiteRint = 0.078
[var phi] and ω scansθmax = 29.2°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)h = −10→10
Tmin = 0.668, Tmax = 0.802k = −12→13
10401 measured reflectionsl = −24→24

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H-atom parameters constrained
S = 1.17w = 1/[σ2(Fo2) + (0.0315P)2 + 1.9318P] where P = (Fo2 + 2Fc2)/3
3358 reflections(Δ/σ)max = 0.004
145 parametersΔρmax = 1.05 e Å3
0 restraintsΔρmin = −0.70 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Zn10.26730 (7)0.26879 (5)0.08829 (3)0.04730 (16)
Cl10.53626 (17)0.30874 (16)0.15251 (8)0.0708 (4)
Cl20.04386 (18)0.40228 (15)0.11668 (9)0.0701 (4)
N10.2881 (5)0.2367 (4)−0.0261 (2)0.0494 (8)
N20.2225 (5)0.0559 (4)0.0820 (2)0.0460 (8)
C10.3141 (7)0.3363 (6)−0.0782 (3)0.0619 (12)
H10.31450.4304−0.06390.074*
C20.3400 (8)0.3028 (7)−0.1517 (3)0.0741 (16)
H20.35730.3733−0.18670.089*
C30.3401 (8)0.1653 (7)−0.1730 (3)0.0726 (16)
H30.35900.1414−0.22260.087*
C40.3121 (6)0.0608 (6)−0.1210 (3)0.0626 (13)
H40.3120−0.0335−0.13500.075*
C50.2840 (5)0.1004 (5)−0.0466 (2)0.0465 (9)
C60.2434 (5)−0.0003 (5)0.0127 (3)0.0469 (9)
C70.2248 (7)−0.1435 (5)0.0005 (3)0.0606 (12)
H70.2412−0.1824−0.04650.073*
C80.1819 (7)−0.2268 (6)0.0589 (4)0.0698 (15)
H80.1668−0.32300.05120.084*
C90.1608 (7)−0.1700 (6)0.1293 (4)0.0679 (14)
H90.1323−0.22680.16920.082*
C100.1834 (6)−0.0254 (5)0.1392 (3)0.0566 (11)
C110.1652 (11)0.0450 (7)0.2132 (3)0.091 (2)
H11A0.06990.11320.20630.109*
H11B0.27630.09120.23110.109*
H11C0.1376−0.02390.24980.109*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0498 (3)0.0446 (3)0.0483 (3)−0.0009 (2)0.0092 (2)−0.0117 (2)
Cl10.0512 (6)0.0826 (9)0.0770 (9)0.0013 (6)0.0008 (6)−0.0358 (7)
Cl20.0599 (7)0.0712 (8)0.0801 (9)0.0137 (6)0.0111 (6)−0.0207 (7)
N10.0449 (18)0.056 (2)0.0475 (19)0.0037 (16)0.0055 (15)−0.0037 (17)
N20.0411 (18)0.0465 (18)0.050 (2)−0.0016 (14)0.0053 (15)−0.0024 (15)
C10.060 (3)0.068 (3)0.059 (3)0.005 (2)0.012 (2)0.007 (2)
C20.078 (4)0.096 (5)0.051 (3)0.004 (3)0.015 (3)0.010 (3)
C30.068 (3)0.107 (5)0.044 (3)0.010 (3)0.011 (2)−0.004 (3)
C40.052 (3)0.077 (3)0.056 (3)0.014 (2)−0.001 (2)−0.023 (3)
C50.0370 (19)0.058 (2)0.043 (2)0.0091 (18)−0.0018 (16)−0.0112 (18)
C60.0346 (19)0.048 (2)0.056 (2)0.0026 (17)−0.0032 (17)−0.0144 (19)
C70.057 (3)0.049 (3)0.074 (3)0.001 (2)0.004 (2)−0.014 (2)
C80.058 (3)0.043 (2)0.106 (4)0.000 (2)0.001 (3)−0.009 (3)
C90.057 (3)0.058 (3)0.088 (4)−0.003 (2)0.003 (3)0.022 (3)
C100.050 (2)0.060 (3)0.059 (3)0.002 (2)0.003 (2)0.002 (2)
C110.129 (6)0.093 (5)0.053 (3)−0.010 (4)0.025 (4)0.013 (3)

Geometric parameters (Å, °)

Zn1—N12.066 (4)C5—C61.475 (7)
Zn1—N22.053 (4)C6—N21.360 (5)
Zn1—Cl12.2236 (15)C6—C71.384 (6)
Zn1—Cl22.1995 (13)C7—C81.367 (8)
C1—N11.350 (6)C7—H70.9300
C1—C21.371 (7)C8—C91.381 (8)
C1—H10.9300C8—H80.9300
C2—C31.361 (9)C9—C101.394 (7)
C2—H20.9300C9—H90.9300
C3—C41.385 (8)C10—N21.329 (6)
C3—H30.9300C10—C111.488 (8)
C4—C51.406 (6)C11—H11A0.9600
C4—H40.9300C11—H11B0.9600
C5—N11.345 (6)C11—H11C0.9600
N1—Zn1—Cl1111.08 (11)N1—C5—C4120.5 (5)
N2—Zn1—Cl1109.16 (11)N1—C5—C6115.8 (4)
Cl2—Zn1—Cl1116.72 (5)C4—C5—C6123.7 (4)
N1—Zn1—Cl2116.84 (11)N2—C6—C7120.5 (5)
N2—Zn1—Cl2117.28 (10)N2—C6—C5115.9 (4)
N2—Zn1—N180.31 (15)C7—C6—C5123.6 (4)
C1—N1—Zn1126.6 (3)C8—C7—C6118.7 (5)
C5—N1—Zn1113.8 (3)C8—C7—H7120.6
C5—N1—C1119.6 (4)C6—C7—H7120.6
C6—N2—Zn1113.6 (3)C7—C8—C9120.9 (5)
C10—N2—Zn1125.5 (3)C7—C8—H8119.5
C10—N2—C6120.8 (4)C9—C8—H8119.5
N1—C1—C2121.9 (5)C8—C9—C10118.2 (5)
N1—C1—H1119.0C8—C9—H9120.9
C2—C1—H1119.0C10—C9—H9120.9
C3—C2—C1119.3 (5)N2—C10—C9120.9 (5)
C3—C2—H2120.3N2—C10—C11117.1 (5)
C1—C2—H2120.3C9—C10—C11122.1 (5)
C2—C3—C4120.1 (5)C10—C11—H11A109.5
C2—C3—H3120.0C10—C11—H11B109.5
C4—C3—H3120.0H11A—C11—H11B109.5
C3—C4—C5118.5 (5)C10—C11—H11C109.5
C3—C4—H4120.7H11A—C11—H11C109.5
C5—C4—H4120.7H11B—C11—H11C109.5
N2—Zn1—N1—C5−6.9 (3)C6—C5—N1—Zn17.2 (5)
Cl2—Zn1—N1—C5−122.7 (3)C6—C5—N1—C1−176.3 (4)
Cl1—Zn1—N1—C5100.0 (3)N1—C5—C6—N2−2.7 (5)
N2—Zn1—N1—C1176.9 (4)C4—C5—C6—N2179.1 (4)
Cl2—Zn1—N1—C161.1 (4)N1—C5—C6—C7176.6 (4)
Cl1—Zn1—N1—C1−76.2 (4)C4—C5—C6—C7−1.6 (7)
Cl1—Zn1—N2—C1073.8 (4)C5—C6—N2—Zn1−3.3 (4)
Cl2—Zn1—N2—C10−61.8 (4)C5—C6—N2—C10179.1 (4)
N1—Zn1—N2—C10−177.1 (4)C7—C6—N2—Zn1177.4 (3)
Cl1—Zn1—N2—C6−103.7 (3)C7—C6—N2—C10−0.2 (6)
Cl2—Zn1—N2—C6120.7 (3)N2—C6—C7—C81.2 (7)
N1—Zn1—N2—C65.4 (3)C5—C6—C7—C8−178.1 (4)
C2—C1—N1—C5−1.2 (7)C6—C7—C8—C9−1.2 (8)
C2—C1—N1—Zn1174.8 (4)C7—C8—C9—C100.3 (8)
N1—C1—C2—C3−0.2 (9)C8—C9—C10—N20.7 (8)
C1—C2—C3—C40.8 (9)C8—C9—C10—C11−179.4 (6)
C2—C3—C4—C50.0 (8)C9—C10—N2—Zn1−178.0 (4)
C3—C4—C5—N1−1.4 (7)C9—C10—N2—C6−0.7 (7)
C3—C4—C5—C6176.7 (4)C11—C10—N2—Zn12.0 (6)
C4—C5—N1—Zn1−174.5 (3)C11—C10—N2—C6179.3 (5)
C4—C5—N1—C12.0 (6)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2529).

References

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