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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): m1250.
Published online 2009 September 26. doi:  10.1107/S1600536809038215
PMCID: PMC2970226

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

Abstract

In the title compound, [ZnCl2(C12H12N2)], the complete mol­ecule is generated by crystallographic mirror symmetry, with the Zn atom and both chloride ions lying on the reflecting plane, yielding a distorted ZnN2Cl2 tetra­hedral coordination for the metal ion. In the crystal, there are π–π contacts between the pyridine rings [centroid–centroid distance = 3.7857 (17) Å].

Related literature

For related structures containing Zn bonded to two chloride ions and a phenanthroline/bipyridine derivative, see: Ahmadi et al. (2008 [triangle], 2009a [triangle],b [triangle]); Alizadeh et al. (2009 [triangle]); Gruia et al. (2007 [triangle]); Khalighi et al. (2008 [triangle]); Khan & Tuck (1984 [triangle]); Khavasi et al. (2008 [triangle]); Khoshtarkib et al. (2009 [triangle]); Kozhevnikov et al. (2006 [triangle]); Liu et al. (2004 [triangle]); Preston & Kennard (1969 [triangle]); Reimann et al. (1966 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1250-scheme1.jpg

Experimental

Crystal data

  • [ZnCl2(C12H12N2)]
  • M r = 320.53
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1250-efi2.jpg
  • a = 7.6957 (15) Å
  • b = 11.266 (2) Å
  • c = 8.1431 (16) Å
  • β = 110.61 (3)°
  • V = 660.8 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.24 mm−1
  • T = 298 K
  • 0.40 × 0.33 × 0.30 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1998 [triangle]) T min = 0.421, T max = 0.512
  • 8852 measured reflections
  • 2075 independent reflections
  • 1972 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.101
  • S = 1.26
  • 2075 reflections
  • 83 parameters
  • H-atom parameters constrained
  • Δρmax = 0.70 e Å−3
  • Δρmin = −0.55 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 (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, global. DOI: 10.1107/S1600536809038215/hb5106sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038215/hb5106Isup2.hkl

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

Acknowledgments

We are grateful to the Damghan University of Basic Sciences and Islamic Azad University, Shahr-e-Rey Branch, for financial support.

supplementary crystallographic information

Comment

Recently, we reported the synthes and crystal structure of [ZnCl2(phend)], (II), (Khoshtarkib et al., 2009), [HgBr2(2,9-dmphen)], (III), (Alizadeh et al., 2009), [HgCl2(2,9-dmPh2phen)].0.5 CH3CN, (IV) (Ahmadi, et al., 2009a) and [Pb4(NO3)8(6-mbpy)4], (V), (Ahmadi, et al., 2009b) [where phend is phenanthridine, 2,9-dmphen is 2,9-dimethyl-1,10-phenanthroline, 2,9-dmPh2phen is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and 6-mbpy is 6-methyl-2,2'-bipyridine].

There are several ZnII complexes, with formula, [ZnCl2(N—N)], such as [ZnCl2(bipy)], (VI), (Khan & Tuck, 1984), [ZnCl2(biim)], (VII), (Gruia et al., 2007), [ZnCl2(phbipy)], (IIX), (Kozhevnikov et al., 2006), [ZnCl2(phen)], (IX), (Reimann et al., 1966), [ZnCl2(dmphen)], (X), (Preston & Kennard, 1969), [ZnCl2(dpdmbip)], (XI), (Liu et al., 2004), [ZnCl2(dm4bt)], (XII), (Khavasi et al., 2008), [ZnCl2(5,5'-dmbpy)], (XIII), (Khalighi et al., 2008) and [ZnCl2(6-mbpy)], (XIV), (Ahmadi, Kalateh, Ebadi 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, dm4bt is 2,2'-dimethyl-4,4'-bithiazole and 5,5'-dmbpy 5,5'-dimethyl-2,2'-bipyridine] 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 the title compound, (I), (Fig. 1), contains half molecule. The ZnII atom is four-coordinated in distorted tetrahedral configurations by two N atoms from one 6,6'-dimethyl-2,2'-bipyridine and two terminal Cl atoms. The Zn—Cl and Zn—N bond lengths and angles are collected in Table 1.

In the crystal structure, the π-π contacts between the rings A (N1/C2—C6) and rings A, Cg2···Cg2i [distance = 3.7857 (17) Å, symmetry cods: 1-X,2-Y,1-Z]. It seems this π-π stacking is effective in the stabilization of the crystal structure (Fig. 2).

Experimental

A solution of 6,6'-dimethyl-2,2'-bipyridine (0.20 g, 1.10 mmol) in methanol (10 ml) was added to a solution of ZnCl2 (0.15 g, 0.88 mmol) in acetonitrile (10 ml) and the resulting colourless solution was stirred for 20 min at at 313 K. This solution was left to evaporate slowly at room temperature. After one week, colorless prisms of (I) were isolated (yield 0.26 g, 73.7%).

Refinement

All H atoms were positioned geometrically, with C—H = 0.93–0.96Å and constrained to ride on their parent atoms, with Uiso(H)=1.2Ueq(C) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (a) x,-y + 3/2,z]
Fig. 2.
Tha unit-cell packing of (I).

Crystal data

[ZnCl2(C12H12N2)]F(000) = 324
Mr = 320.53Dx = 1.611 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 1170 reflections
a = 7.6957 (15) Åθ = 2.8–30.6°
b = 11.266 (2) ŵ = 2.24 mm1
c = 8.1431 (16) ÅT = 298 K
β = 110.61 (3)°Prism, colourless
V = 660.8 (3) Å30.40 × 0.33 × 0.30 mm
Z = 2

Data collection

Bruker SMART CCD diffractometer2075 independent reflections
Radiation source: fine-focus sealed tube1972 reflections with I > 2σ(I)
graphiteRint = 0.043
ω scansθmax = 30.6°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)h = −10→10
Tmin = 0.421, Tmax = 0.512k = −16→16
8852 measured reflectionsl = −11→10

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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 1.26w = 1/[σ2(Fo2) + (0.036P)2 + 0.4143P] where P = (Fo2 + 2Fc2)/3
2075 reflections(Δ/σ)max < 0.001
83 parametersΔρmax = 0.70 e Å3
0 restraintsΔρmin = −0.55 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
C10.9103 (5)1.0397 (3)0.7493 (4)0.0605 (7)
H1A0.86261.01610.83860.091*
H1B0.90851.12470.74050.091*
H1C1.03551.01170.77930.091*
C20.7921 (3)0.9875 (2)0.5768 (3)0.0415 (5)
C30.6959 (4)1.0566 (2)0.4331 (4)0.0525 (6)
H30.70411.13890.44130.063*
C40.5891 (4)1.0046 (3)0.2791 (4)0.0524 (6)
H40.52461.05120.18250.063*
C50.5776 (3)0.8820 (2)0.2679 (3)0.0424 (5)
H50.50530.84490.16440.051*
C60.6762 (3)0.81599 (18)0.4143 (3)0.0317 (4)
N10.7813 (2)0.86822 (16)0.5661 (2)0.0330 (3)
Cl11.20088 (11)0.75000.88188 (13)0.0521 (2)
Cl20.74082 (14)0.75000.94980 (13)0.0511 (2)
Zn10.89560 (5)0.75000.76788 (4)0.03392 (12)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0688 (19)0.0401 (13)0.0625 (17)−0.0094 (12)0.0104 (15)−0.0154 (12)
C20.0457 (12)0.0306 (10)0.0480 (12)−0.0039 (8)0.0162 (10)−0.0032 (8)
C30.0694 (17)0.0281 (10)0.0616 (16)0.0033 (10)0.0249 (14)0.0063 (10)
C40.0641 (16)0.0434 (13)0.0473 (13)0.0122 (12)0.0168 (12)0.0161 (11)
C50.0453 (12)0.0424 (12)0.0342 (10)0.0048 (9)0.0074 (9)0.0057 (9)
C60.0326 (9)0.0308 (9)0.0300 (8)0.0014 (7)0.0091 (7)0.0016 (7)
N10.0341 (8)0.0288 (8)0.0328 (8)−0.0010 (6)0.0075 (6)−0.0002 (6)
Cl10.0325 (4)0.0642 (6)0.0492 (5)0.0000.0014 (3)0.000
Cl20.0548 (5)0.0567 (5)0.0479 (4)0.0000.0255 (4)0.000
Zn10.03172 (18)0.03621 (19)0.02830 (18)0.0000.00368 (12)0.000

Geometric parameters (Å, °)

C1—C21.499 (4)C4—H40.9300
C1—H1A0.9600C5—C61.383 (3)
C1—H1B0.9600C5—H50.9300
C1—H1C0.9600C6—N11.350 (3)
C2—N11.347 (3)C6—C6i1.487 (4)
C2—C31.384 (4)Zn1—N12.0569 (18)
C3—C41.366 (4)Zn1—Cl12.2013 (11)
C3—H30.9300Zn1—Cl22.2035 (10)
C4—C51.386 (4)Zn1—N1i2.0569 (18)
C2—C1—H1A109.5C6—C5—C4118.4 (2)
C2—C1—H1B109.5C6—C5—H5120.8
H1A—C1—H1B109.5C4—C5—H5120.8
C2—C1—H1C109.5N1—C6—C5121.6 (2)
H1A—C1—H1C109.5N1—C6—C6i115.83 (11)
H1B—C1—H1C109.5C5—C6—C6i122.51 (14)
N1—C2—C3120.3 (2)C2—N1—C6119.82 (19)
N1—C2—C1117.1 (2)C2—N1—Zn1126.50 (16)
C3—C2—C1122.6 (2)C6—N1—Zn1113.51 (13)
C4—C3—C2120.3 (2)N1i—Zn1—N180.71 (10)
C4—C3—H3119.8N1i—Zn1—Cl1115.45 (6)
C2—C3—H3119.8N1—Zn1—Cl1115.45 (6)
C3—C4—C5119.5 (2)N1i—Zn1—Cl2110.90 (6)
C3—C4—H4120.3N1—Zn1—Cl2110.90 (6)
C5—C4—H4120.3Cl1—Zn1—Cl2117.76 (5)
N1—C2—C3—C40.0 (4)C5—C6—N1—C2−0.2 (3)
C1—C2—C3—C4−179.6 (3)C6i—C6—N1—C2178.78 (16)
C2—C3—C4—C50.1 (5)C5—C6—N1—Zn1175.34 (17)
C3—C4—C5—C6−0.2 (4)C6i—C6—N1—Zn1−5.7 (3)
C4—C5—C6—N10.3 (4)C2—N1—Zn1—N1i−178.10 (16)
C4—C5—C6—C6i−178.63 (19)C6—N1—Zn1—N1i6.69 (17)
C3—C2—N1—C60.0 (4)C2—N1—Zn1—Cl1−64.2 (2)
C1—C2—N1—C6179.7 (2)C6—N1—Zn1—Cl1120.55 (13)
C3—C2—N1—Zn1−174.88 (19)C2—N1—Zn1—Cl273.0 (2)
C1—C2—N1—Zn14.7 (3)C6—N1—Zn1—Cl2−102.24 (14)

Symmetry codes: (i) x, −y+3/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5106).

References

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