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Acta Cryst. (2008). E64, m511    [ doi:10.1107/S1600536808005382 ]

Bis(2,6-dimethylpyrazine-[kappa]N4)diiodidozinc(II)

S. H. Lee, S.-H. Kim, P.-G. Kim, C. Kim and Y. Kim

Abstract top

In the title compound, [ZnI2(C6H8N2)2], the ZnII ion is coordinated by two iodide anions and two N atoms from 2,6-dimethylpyrazine in a distorted tetrahedral geometry.

Comment top

Much interest has recently been focused on the rational design and construction of novel discrete and polymeric metal-organic complexes, not only due to their structural and topological novelty (Batten & Robson, 1998, Moler et al., 2001, Moulton & Zaworotko, 2001), but also for their potential applications as functional materials such as catalysis, molecular recognition, separation, and nonlinear optics (Hong et al., 2004, Evans & Lin, 2002, Kasai et al. 2000, Kitagawa et al., 2004). It has shown that many factors such as the coordination geometry of metal ions (Chi et al.,2006), the structure of organic ligands (Wang et al.,2006), the solvent system (Ryu et al., 2005), the counteranion (Luan et al., 2006), and the ratio of ligands to metal ions (Blake et al., 1999, Saalfrank et al., 2001) influence highly on the structure of metal-organic complexes. In addition, it has been considered that the secondary forces such as hydrogen-bonding, pi-pi stacking, and host–guest interactions are of importance as well (Luan et al., 2005, Janaik & Scharmann, 2003, Janiak, 2003). For obtaining novel structural motifs with predictable properties, therefore, a large number of organic ligands were designed and utilized. Among them, 2,6-dimethylpyrazine was often selected. We have also reacted ZnI2 with 2,6-dimethylpyrazine to form a new zinc complex and report here on the crystal structure of diiodobis(2,6-dimethylpyrazine)zinc(II).

Asymmetric unit contains a whole molecule (Fig. 1). ZnII ion is coordinated by two iodide anions and two nitrogen atoms from 2,6-dimethylpyrazine to form a distorted tetrahedral geometry (Fig. 1). Zn—I bond distances are 2.5393 (7) and 2.5442 (6) Å, and I—Zn—I and N—Zn—N bond angles are 122.78 (2) and 101.39 (14)°, respectively.

Related literature top

For background information, see: Batten & Robson (1998); Chi et al. (2006); Evans & Lin (2002); Hong et al. (2004); Janiak (2003); Janaik & Scharmann (2003); Kasai et al. (2000); Kitagawa et al. (2004); Luan et al. (2005, 2006); Moler et al. (2001); Moulton & Zaworotko (2001); Ryu et al. (2005); Wang et al. (2006); Blake et al. (1999); Saalfrank et al. (2001).

Experimental top

244.29 mg (0.75 mmol) of ZnI2 were dissolved in 4 ml water and carefully layered by 4 ml e thanol solution of 2,6-dimethylpyrazine ligand (165.52 mg, 1.5 mmol). Suitable crystals of the title compound for X-ray analysis were obtained in a few weeks.

Refinement top

(type here to add refinement details)

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Fig. 1 The structure of the title compound showing the atom-labeling scheme. Displacement ellipsoids are shown at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
Bis(2,6-dimethylpyrazine-κN4)diiodidozinc(II) top
Crystal data top
[ZnI2(C6H8N2)2]F000 = 1008
Mr = 535.48Dx = 2.080 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2888 reflections
a = 9.1825 (7) Åθ = 2.7–25.6º
b = 13.8144 (10) ŵ = 5.04 mm−1
c = 13.6242 (10) ÅT = 170 (2) K
β = 98.3810 (10)ºRod, colorless
V = 1709.8 (2) Å30.10 × 0.05 × 0.05 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		2518 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.109
Monochromator: graphiteθmax = 26.0º
T = 170(2) Kθmin = 2.1º
φ and ω scansh = −11→11
Absorption correction: nonek = −17→16
9413 measured reflectionsl = −9→16
3344 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.069  w = 1/[σ2(Fo2) + (0.0147P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.81(Δ/σ)max = 0.001
3344 reflectionsΔρmax = 0.81 e Å−3
176 parametersΔρmin = −1.27 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[ZnI2(C6H8N2)2]V = 1709.8 (2) Å3
Mr = 535.48Z = 4
Monoclinic, P21/cMo Kα
a = 9.1825 (7) ŵ = 5.04 mm−1
b = 13.8144 (10) ÅT = 170 (2) K
c = 13.6242 (10) Å0.10 × 0.05 × 0.05 mm
β = 98.3810 (10)º
Data collection top
Bruker SMART CCD
diffractometer		3344 independent reflections
Absorption correction: none2518 reflections with I > 2σ(I)
9413 measured reflectionsRint = 0.109
Refinement top
R[F2 > 2σ(F2)] = 0.032176 parameters
wR(F2) = 0.069H-atom parameters constrained
S = 0.81Δρmax = 0.81 e Å−3
3344 reflectionsΔρmin = −1.27 e Å−3
Special details top

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) top
xyzUiso*/Ueq
Zn10.07870 (6)0.24556 (4)0.76694 (4)0.02508 (15)
I10.07868 (4)0.15009 (3)0.60725 (2)0.03357 (11)
I20.19801 (4)0.41101 (3)0.79495 (2)0.03516 (11)
N11−0.1362 (4)0.2579 (3)0.7987 (3)0.0244 (9)
N12−0.4102 (4)0.2602 (3)0.8610 (3)0.0290 (10)
N210.1716 (4)0.1540 (3)0.8789 (3)0.0247 (9)
N220.3046 (4)0.0275 (3)1.0237 (3)0.0283 (10)
C11−0.2359 (5)0.1893 (4)0.7695 (3)0.0262 (11)
H11−0.21150.13870.72760.031*
C12−0.3750 (5)0.1903 (4)0.7992 (3)0.0274 (11)
C13−0.3120 (5)0.3282 (4)0.8896 (3)0.0280 (12)
C14−0.1739 (5)0.3274 (4)0.8575 (3)0.0278 (11)
H14−0.10580.37780.87810.033*
C15−0.4843 (5)0.1130 (4)0.7682 (4)0.0361 (13)
H15A−0.50430.07680.82670.054*
H15B−0.44500.06880.72220.054*
H15C−0.57580.14220.73510.054*
C16−0.3539 (5)0.4070 (4)0.9555 (4)0.0438 (15)
H16A−0.45660.42580.93400.066*
H16B−0.28980.46310.95150.066*
H16C−0.34290.38371.02410.066*
C210.1310 (5)0.0616 (4)0.8802 (3)0.0278 (12)
H210.05660.03850.82990.033*
C220.1950 (5)−0.0025 (4)0.9535 (3)0.0302 (12)
C230.3442 (5)0.1193 (4)1.0219 (3)0.0277 (12)
C240.2793 (5)0.1839 (4)0.9502 (3)0.0265 (11)
H240.31120.24940.95150.032*
C250.1460 (6)−0.1051 (4)0.9560 (4)0.0391 (14)
H25A0.1946−0.14360.90980.059*
H25B0.0390−0.10850.93660.059*
H25C0.1720−0.13081.02340.059*
C260.4667 (6)0.1544 (4)1.1002 (3)0.0406 (14)
H26A0.42610.17141.16060.061*
H26B0.51330.21151.07560.061*
H26C0.54010.10301.11520.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0246 (3)0.0250 (3)0.0258 (3)0.0006 (2)0.0044 (2)0.0019 (3)
I10.0398 (2)0.0359 (2)0.02578 (18)0.00179 (16)0.00728 (14)−0.00169 (16)
I20.0342 (2)0.0259 (2)0.0448 (2)−0.00311 (15)0.00379 (16)0.00327 (16)
N110.023 (2)0.027 (2)0.023 (2)0.0031 (18)0.0014 (17)0.0060 (19)
N120.028 (2)0.034 (3)0.026 (2)0.005 (2)0.0062 (18)0.001 (2)
N210.025 (2)0.027 (3)0.0217 (19)−0.0010 (18)0.0039 (16)0.0008 (19)
N220.028 (2)0.030 (3)0.026 (2)0.002 (2)0.0014 (18)0.000 (2)
C110.022 (3)0.028 (3)0.027 (2)0.004 (2)−0.001 (2)−0.002 (2)
C120.023 (3)0.029 (3)0.028 (3)0.003 (2)0.000 (2)0.007 (2)
C130.029 (3)0.030 (3)0.025 (3)0.004 (2)0.004 (2)0.003 (2)
C140.028 (3)0.026 (3)0.028 (3)0.001 (2)0.000 (2)0.000 (2)
C150.024 (3)0.038 (3)0.045 (3)−0.006 (3)0.003 (2)−0.008 (3)
C160.032 (3)0.049 (4)0.051 (3)0.001 (3)0.009 (3)−0.011 (3)
C210.029 (3)0.028 (3)0.026 (3)−0.003 (2)0.004 (2)−0.004 (2)
C220.032 (3)0.029 (3)0.030 (3)0.000 (2)0.008 (2)−0.001 (2)
C230.030 (3)0.032 (3)0.021 (2)−0.003 (2)0.004 (2)−0.004 (2)
C240.023 (2)0.029 (3)0.029 (3)−0.001 (2)0.008 (2)−0.002 (2)
C250.050 (3)0.030 (3)0.034 (3)−0.002 (3)−0.003 (3)0.007 (3)
C260.041 (3)0.045 (4)0.033 (3)−0.008 (3)−0.006 (2)0.002 (3)
Geometric parameters (Å, °) top
Zn1—N212.068 (4)C15—H15A0.9800
Zn1—N112.088 (4)C15—H15B0.9800
Zn1—I22.5393 (7)C15—H15C0.9800
Zn1—I12.5442 (6)C16—H16A0.9800
N11—C141.328 (6)C16—H16B0.9800
N11—C111.337 (6)C16—H16C0.9800
N12—C131.321 (6)C21—C221.398 (7)
N12—C121.351 (6)C21—H210.9500
N21—C211.331 (6)C22—C251.489 (7)
N21—C241.346 (5)C23—C241.392 (6)
N22—C231.321 (6)C23—C261.513 (6)
N22—C221.348 (6)C24—H240.9500
C11—C121.395 (7)C25—H25A0.9800
C11—H110.9500C25—H25B0.9800
C12—C151.485 (7)C25—H25C0.9800
C13—C141.401 (7)C26—H26A0.9800
C13—C161.496 (7)C26—H26B0.9800
C14—H140.9500C26—H26C0.9800
N21—Zn1—N11101.39 (14)H15B—C15—H15C109.5
N21—Zn1—I2108.49 (11)C13—C16—H16A109.5
N11—Zn1—I2107.19 (12)C13—C16—H16B109.5
N21—Zn1—I1105.22 (11)H16A—C16—H16B109.5
N11—Zn1—I1109.72 (10)C13—C16—H16C109.5
I2—Zn1—I1122.78 (2)H16A—C16—H16C109.5
C14—N11—C11117.7 (4)H16B—C16—H16C109.5
C14—N11—Zn1121.4 (3)N21—C21—C22121.8 (4)
C11—N11—Zn1120.5 (3)N21—C21—H21119.1
C13—N12—C12118.6 (4)C22—C21—H21119.1
C21—N21—C24117.6 (4)N22—C22—C21120.3 (5)
C21—N21—Zn1120.7 (3)N22—C22—C25118.2 (4)
C24—N21—Zn1121.7 (3)C21—C22—C25121.5 (5)
C23—N22—C22117.5 (4)N22—C23—C24122.5 (4)
N11—C11—C12121.5 (5)N22—C23—C26118.2 (4)
N11—C11—H11119.2C24—C23—C26119.2 (5)
C12—C11—H11119.2N21—C24—C23120.3 (5)
N12—C12—C11120.0 (5)N21—C24—H24119.9
N12—C12—C15118.6 (4)C23—C24—H24119.9
C11—C12—C15121.3 (5)C22—C25—H25A109.5
N12—C13—C14120.8 (5)C22—C25—H25B109.5
N12—C13—C16118.1 (4)H25A—C25—H25B109.5
C14—C13—C16121.1 (5)C22—C25—H25C109.5
N11—C14—C13121.4 (5)H25A—C25—H25C109.5
N11—C14—H14119.3H25B—C25—H25C109.5
C13—C14—H14119.3C23—C26—H26A109.5
C12—C15—H15A109.5C23—C26—H26B109.5
C12—C15—H15B109.5H26A—C26—H26B109.5
H15A—C15—H15B109.5C23—C26—H26C109.5
C12—C15—H15C109.5H26A—C26—H26C109.5
H15A—C15—H15C109.5H26B—C26—H26C109.5
Acknowledgements top

Financial support from the Environmental Technology Educational Innovation Program (2006) of the Ministry of Environment and THE SEOUL R & BD Program is gratefully acknowledged.

references
References top

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