Bis(2,6-dimethyl­pyrazine-κN4)diiodidozinc(II)

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

doi:10.1107/S1600536808005382

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page m511

doi:10.1107/S1600536808005382

Open

access

Bis(2,6-dimethylpyrazine-κN⁴)diiodidozinc(II)

Sun Hwa Lee,^a Sea-Hyun Kim,^b Pan-Gi Kim,^c Cheal Kim ^a ^* and Youngmee Kim ^d ^*

^aDepartment of Fine Chemistry and Eco-Products and Materials Education Center, Seoul National University of Technology, Seoul 139-743, Republic of Korea, ^bTree Breeding Division, Korea Forest Research Institute, Suwon 441-350, Republic of Korea, ^cDepartment of Forest Resources and Environment, Kyungpook National University, Sangju 742-711, Republic of Korea, and ^dDivision of Nano Sciences, Ewha Womans University, Seoul 120-750, Republic of Korea
^*Correspondence e-mail: chealkim@sunt.ac.kr, ymeekim@ewha.ac.kr

(Received 21 February 2008; accepted 26 February 2008; online 5 March 2008)

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

Related literature

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

Crystal data

[ZnI₂(C₆H₈N₂)₂]
M_r = 535.48
Monoclinic, P 2₁ /c
a = 9.1825 (7) Å
b = 13.8144 (10) Å
c = 13.6242 (10) Å
β = 98.381 (1)°
V = 1709.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 5.04 mm⁻¹
T = 170 (2) K
0.10 × 0.05 × 0.05 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
9413 measured reflections
3344 independent reflections
2518 reflections with I > 2σ(I)
R_int = 0.109

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.069
S = 0.81
3344 reflections
176 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −1.27 e Å⁻³

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808005382/dn2320sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808005382/dn2320Isup2.hkl

checkCIF report

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 ZnI₂with 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). Zn^II 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.

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

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]	F(000) = 1008
M_r = 535.48	D_x = 2.080 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2888 reflections
a = 9.1825 (7) Å	θ = 2.7–25.6°
b = 13.8144 (10) Å	µ = 5.04 mm⁻¹
c = 13.6242 (10) Å	T = 170 K
β = 98.381 (1)°	Rod, colorless
V = 1709.8 (2) Å³	0.10 × 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 tube	R_int = 0.109
Graphite monochromator	θ_max = 26.0°, θ_min = 2.1°
ϕ and ω scans	h = −11→11
9413 measured reflections	k = −17→16
3344 independent reflections	l = −9→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H-atom parameters constrained
S = 0.81	w = 1/[σ²(F_o²) + (0.0147P)²] where P = (F_o² + 2F_c²)/3
3344 reflections	(Δ/σ)_max = 0.001
176 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −1.28 e Å⁻³

Crystal data top

[ZnI₂(C₆H₈N₂)₂]	V = 1709.8 (2) Å³
M_r = 535.48	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.1825 (7) Å	µ = 5.04 mm⁻¹
b = 13.8144 (10) Å	T = 170 K
c = 13.6242 (10) Å	0.10 × 0.05 × 0.05 mm
β = 98.381 (1)°

Data collection top

Bruker SMART CCD diffractometer	2518 reflections with I > 2σ(I)
9413 measured reflections	R_int = 0.109
3344 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.069	H-atom parameters constrained
S = 0.81	Δρ_max = 0.81 e Å⁻³
3344 reflections	Δρ_min = −1.28 e Å⁻³
176 parameters

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

	x	y	z	U_iso*/U_eq
Zn1	0.07870 (6)	0.24556 (4)	0.76694 (4)	0.02508 (15)
I1	0.07868 (4)	0.15009 (3)	0.60725 (2)	0.03357 (11)
I2	0.19801 (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)
N21	0.1716 (4)	0.1540 (3)	0.8789 (3)	0.0247 (9)
N22	0.3046 (4)	0.0275 (3)	1.0237 (3)	0.0283 (10)
C11	−0.2359 (5)	0.1893 (4)	0.7695 (3)	0.0262 (11)
H11	−0.2115	0.1387	0.7276	0.031*
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	−0.1058	0.3778	0.8781	0.033*
C15	−0.4843 (5)	0.1130 (4)	0.7682 (4)	0.0361 (13)
H15A	−0.5043	0.0768	0.8267	0.054*
H15B	−0.4450	0.0688	0.7222	0.054*
H15C	−0.5758	0.1422	0.7351	0.054*
C16	−0.3539 (5)	0.4070 (4)	0.9555 (4)	0.0438 (15)
H16A	−0.4566	0.4258	0.9340	0.066*
H16B	−0.2898	0.4631	0.9515	0.066*
H16C	−0.3429	0.3837	1.0241	0.066*
C21	0.1310 (5)	0.0616 (4)	0.8802 (3)	0.0278 (12)
H21	0.0566	0.0385	0.8299	0.033*
C22	0.1950 (5)	−0.0025 (4)	0.9535 (3)	0.0302 (12)
C23	0.3442 (5)	0.1193 (4)	1.0219 (3)	0.0277 (12)
C24	0.2793 (5)	0.1839 (4)	0.9502 (3)	0.0265 (11)
H24	0.3112	0.2494	0.9515	0.032*
C25	0.1460 (6)	−0.1051 (4)	0.9560 (4)	0.0391 (14)
H25A	0.1946	−0.1436	0.9098	0.059*
H25B	0.0390	−0.1085	0.9366	0.059*
H25C	0.1720	−0.1308	1.0234	0.059*
C26	0.4667 (6)	0.1544 (4)	1.1002 (3)	0.0406 (14)
H26A	0.4261	0.1714	1.1606	0.061*
H26B	0.5133	0.2115	1.0756	0.061*
H26C	0.5401	0.1030	1.1152	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0246 (3)	0.0250 (3)	0.0258 (3)	0.0006 (2)	0.0044 (2)	0.0019 (3)
I1	0.0398 (2)	0.0359 (2)	0.02578 (18)	0.00179 (16)	0.00728 (14)	−0.00169 (16)
I2	0.0342 (2)	0.0259 (2)	0.0448 (2)	−0.00311 (15)	0.00379 (16)	0.00327 (16)
N11	0.023 (2)	0.027 (2)	0.023 (2)	0.0031 (18)	0.0014 (17)	0.0060 (19)
N12	0.028 (2)	0.034 (3)	0.026 (2)	0.005 (2)	0.0062 (18)	0.001 (2)
N21	0.025 (2)	0.027 (3)	0.0217 (19)	−0.0010 (18)	0.0039 (16)	0.0008 (19)
N22	0.028 (2)	0.030 (3)	0.026 (2)	0.002 (2)	0.0014 (18)	0.000 (2)
C11	0.022 (3)	0.028 (3)	0.027 (2)	0.004 (2)	−0.001 (2)	−0.002 (2)
C12	0.023 (3)	0.029 (3)	0.028 (3)	0.003 (2)	0.000 (2)	0.007 (2)
C13	0.029 (3)	0.030 (3)	0.025 (3)	0.004 (2)	0.004 (2)	0.003 (2)
C14	0.028 (3)	0.026 (3)	0.028 (3)	0.001 (2)	0.000 (2)	0.000 (2)
C15	0.024 (3)	0.038 (3)	0.045 (3)	−0.006 (3)	0.003 (2)	−0.008 (3)
C16	0.032 (3)	0.049 (4)	0.051 (3)	0.001 (3)	0.009 (3)	−0.011 (3)
C21	0.029 (3)	0.028 (3)	0.026 (3)	−0.003 (2)	0.004 (2)	−0.004 (2)
C22	0.032 (3)	0.029 (3)	0.030 (3)	0.000 (2)	0.008 (2)	−0.001 (2)
C23	0.030 (3)	0.032 (3)	0.021 (2)	−0.003 (2)	0.004 (2)	−0.004 (2)
C24	0.023 (2)	0.029 (3)	0.029 (3)	−0.001 (2)	0.008 (2)	−0.002 (2)
C25	0.050 (3)	0.030 (3)	0.034 (3)	−0.002 (3)	−0.003 (3)	0.007 (3)
C26	0.041 (3)	0.045 (4)	0.033 (3)	−0.008 (3)	−0.006 (2)	0.002 (3)

Geometric parameters (Å, º) top

Zn1—N21	2.068 (4)	C15—H15A	0.9800
Zn1—N11	2.088 (4)	C15—H15B	0.9800
Zn1—I2	2.5393 (7)	C15—H15C	0.9800
Zn1—I1	2.5442 (6)	C16—H16A	0.9800
N11—C14	1.328 (6)	C16—H16B	0.9800
N11—C11	1.337 (6)	C16—H16C	0.9800
N12—C13	1.321 (6)	C21—C22	1.398 (7)
N12—C12	1.351 (6)	C21—H21	0.9500
N21—C21	1.331 (6)	C22—C25	1.489 (7)
N21—C24	1.346 (5)	C23—C24	1.392 (6)
N22—C23	1.321 (6)	C23—C26	1.513 (6)
N22—C22	1.348 (6)	C24—H24	0.9500
C11—C12	1.395 (7)	C25—H25A	0.9800
C11—H11	0.9500	C25—H25B	0.9800
C12—C15	1.485 (7)	C25—H25C	0.9800
C13—C14	1.401 (7)	C26—H26A	0.9800
C13—C16	1.496 (7)	C26—H26B	0.9800
C14—H14	0.9500	C26—H26C	0.9800

N21—Zn1—N11	101.39 (14)	H15B—C15—H15C	109.5
N21—Zn1—I2	108.49 (11)	C13—C16—H16A	109.5
N11—Zn1—I2	107.19 (12)	C13—C16—H16B	109.5
N21—Zn1—I1	105.22 (11)	H16A—C16—H16B	109.5
N11—Zn1—I1	109.72 (10)	C13—C16—H16C	109.5
I2—Zn1—I1	122.78 (2)	H16A—C16—H16C	109.5
C14—N11—C11	117.7 (4)	H16B—C16—H16C	109.5
C14—N11—Zn1	121.4 (3)	N21—C21—C22	121.8 (4)
C11—N11—Zn1	120.5 (3)	N21—C21—H21	119.1
C13—N12—C12	118.6 (4)	C22—C21—H21	119.1
C21—N21—C24	117.6 (4)	N22—C22—C21	120.3 (5)
C21—N21—Zn1	120.7 (3)	N22—C22—C25	118.2 (4)
C24—N21—Zn1	121.7 (3)	C21—C22—C25	121.5 (5)
C23—N22—C22	117.5 (4)	N22—C23—C24	122.5 (4)
N11—C11—C12	121.5 (5)	N22—C23—C26	118.2 (4)
N11—C11—H11	119.2	C24—C23—C26	119.2 (5)
C12—C11—H11	119.2	N21—C24—C23	120.3 (5)
N12—C12—C11	120.0 (5)	N21—C24—H24	119.9
N12—C12—C15	118.6 (4)	C23—C24—H24	119.9
C11—C12—C15	121.3 (5)	C22—C25—H25A	109.5
N12—C13—C14	120.8 (5)	C22—C25—H25B	109.5
N12—C13—C16	118.1 (4)	H25A—C25—H25B	109.5
C14—C13—C16	121.1 (5)	C22—C25—H25C	109.5
N11—C14—C13	121.4 (5)	H25A—C25—H25C	109.5
N11—C14—H14	119.3	H25B—C25—H25C	109.5
C13—C14—H14	119.3	C23—C26—H26A	109.5
C12—C15—H15A	109.5	C23—C26—H26B	109.5
C12—C15—H15B	109.5	H26A—C26—H26B	109.5
H15A—C15—H15B	109.5	C23—C26—H26C	109.5
C12—C15—H15C	109.5	H26A—C26—H26C	109.5
H15A—C15—H15C	109.5	H26B—C26—H26C	109.5

Experimental details

Crystal data
Chemical formula	[ZnI₂(C₆H₈N₂)₂]
M_r	535.48
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	170
a, b, c (Å)	9.1825 (7), 13.8144 (10), 13.6242 (10)
β (°)	98.381 (1)
V (Å³)	1709.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.04
Crystal size (mm)	0.10 × 0.05 × 0.05

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9413, 3344, 2518
R_int	0.109
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.069, 0.81
No. of reflections	3344
No. of parameters	176
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −1.28

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

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

Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460–1494. Web of Science CrossRef Google Scholar
Blake, A. J., Brooks, N. R., Champness, N. R., Cooke, P. A., Deveson, A. M., Fenske, D., Hubberstey, P. & Schröder, M. (1999). J. Chem. Soc. Dalton Trans. pp. 2103–2110. Web of Science CSD CrossRef Google Scholar
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chi, Y.-N., Huang, K.-L., Cui, F.-Y., Xu, Y.-Q. & Hu, C.-W. (2006). Inorg. Chem. 45, 10605–10612. Web of Science CSD CrossRef PubMed CAS Google Scholar
Evans, O. R. & Lin, W. (2002). Acc. Chem. Res. 35, 511–522. Web of Science CrossRef PubMed CAS Google Scholar
Hong, S. J., Ryu, J. Y., Lee, J. Y., Kim, C., Kim, S.-J. & Kim, Y. (2004). Dalton Trans. pp. 2697–2701. Web of Science CSD CrossRef Google Scholar
Janaik, C. & Scharmann, T. G. (2003). Polyhedron, 22, 1123–1133. Web of Science CrossRef Google Scholar
Janiak, C. (2003). Dalton Trans. pp. 2781–2804. Web of Science CrossRef Google Scholar
Kasai, K., Aoyagi, M. & Fujita, M. (2000). J. Am. Chem. Soc. 122, 2140–2141. Web of Science CSD CrossRef CAS Google Scholar
Kitagawa, S., Kitaura, R. & Noro, S.-I. (2004). Angew. Chem. Int. Ed. 43, 2334–2375. Web of Science CrossRef CAS Google Scholar
Luan, X.-J., Cai, X.-H., Wang, Y.-Y., Li, D.-S., Wang, C.-J., Liu, P., Hu, H.-M., Shi, Q.-Z. & Peng, S.-M. (2006). Chem. Eur. J. 12, 6281–6289. Web of Science CSD CrossRef PubMed CAS Google Scholar
Luan, X.-J., Wang, Y.-Y., Li, D.-S., Liu, P., Hu, H.-M., Shi, Q.-Z. & Peng, S.-M. (2005). Angew. Chem. Int. Ed. 44, 3864–3867. Web of Science CSD CrossRef CAS Google Scholar
Moler, D. B., Chen, H., Li, B., Reineke, T. M., O'Keeffe, M. & Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319–330. Web of Science PubMed Google Scholar
Moulton, B. & Zaworotko, M. J. (2001). Chem. Rev. 101, 1629–1658. Web of Science CrossRef PubMed CAS Google Scholar
Ryu, J. Y., Han, J. H., Lee, J. Y., Hong, S. J., Choi, S. H., Kim, C., Kim, S.-J. & Kim, Y. (2005). Inorg. Chim. Acta, 358, 3659–3670. Web of Science CSD CrossRef CAS Google Scholar
Saalfrank, R. W., Bernt, I., Chowdhry, M. M., Hampel, F. & Vaughan, G. B. M. (2001). Chem. Eur. J. 7, 2765–2769. CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, X.-Y., Wang, L., Wang, Z.-M. & Gao, S. (2006). J. Am. Chem. Soc. 128, 674–675. Web of Science CSD CrossRef PubMed CAS Google Scholar