Acta Cryst. (2009). E65, m1439-m1440 [ doi:10.1107/S1600536809043049 ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
2N,N')diiodidozinc(II)The complete molecule of the title compound, [ZnI2(C12H12N2)], is generated by crystallograpic twofold symmetry, with the ZnII atom lying on the rotation axis. The ZnII atom is coordinated by the N,N-bidentate 6,6'-dimethyl-2,2'-bipyridine ligand and two iodide ions, resulting in a distorted ZnN2I2 tetrahedral geometry for the metal. In the crystal, there are weak ![[pi]](/logos/entities/pi_rmgif.gif)
- contacts between the pyridine rings [centroid-centroid distance = 3.978 (3) Å].
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 ZnI2 (0.35 g, 1.10 mmol) in acetonitrile (10 ml) and the resulting colourless solution was stirred for 20 min at 313 K. This solution was left to evaporate slowly at room temperature. After one week, colourless needles of (I) were isolated (yield 0.41 g, 74.1%).
All H atoms were positioned geometrically, with C—H = 0.93–0.96Å and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./hb5152fig1thm.gif)
| Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level. |
![[Figure 2]](./hb5152fig2thm.gif)
| Fig. 2. Unit-cell packing diagram for (I). |
| [ZnI2(C12H12N2)] | F(000) = 936 |
| Mr = 503.43 | Dx = 2.224 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 896 reflections |
| a = 13.421 (2) Å | θ = 2.9–29.2° |
| b = 8.441 (2) Å | µ = 5.72 mm−1 |
| c = 13.752 (3) Å | T = 298 K |
| β = 105.140 (14)° | Needle, colourless |
| V = 1503.8 (5) Å3 | 0.48 × 0.12 × 0.11 mm |
| Z = 4 |
| Bruker SMART CCD diffractometer | 1997 independent reflections |
| Radiation source: fine-focus sealed tube | 1748 reflections with I > 2σ(I) |
| graphite | Rint = 0.076 |
| ω scans | θmax = 29.2°, θmin = 2.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −18→18 |
| Tmin = 0.425, Tmax = 0.539 | k = −9→11 |
| 5694 measured reflections | l = −18→18 |
| 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.127 | H-atom parameters constrained |
| S = 1.12 | w = 1/[σ2(Fo2) + (0.0623P)2 + 3.240P] where P = (Fo2 + 2Fc2)/3 |
| 1997 reflections | (Δ/σ)max < 0.001 |
| 79 parameters | Δρmax = 1.23 e Å−3 |
| 0 restraints | Δρmin = −0.85 e Å−3 |
| [ZnI2(C12H12N2)] | V = 1503.8 (5) Å3 |
| Mr = 503.43 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 13.421 (2) Å | µ = 5.72 mm−1 |
| b = 8.441 (2) Å | T = 298 K |
| c = 13.752 (3) Å | 0.48 × 0.12 × 0.11 mm |
| β = 105.140 (14)° |
| Bruker SMART CCD diffractometer | 1997 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 1998) | 1748 reflections with I > 2σ(I) |
| Tmin = 0.425, Tmax = 0.539 | Rint = 0.076 |
| 5694 measured reflections | θmax = 29.2° |
| R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
| wR(F2) = 0.127 | Δρmax = 1.23 e Å−3 |
| S = 1.12 | Δρmin = −0.85 e Å−3 |
| 1997 reflections | Absolute structure: ? |
| 79 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.1171 (5) | 0.2312 (7) | 0.4901 (4) | 0.0650 (14) | |
| H1A | 0.1495 | 0.1657 | 0.4501 | 0.078* | |
| H1B | 0.0518 | 0.1858 | 0.4914 | 0.078* | |
| H1C | 0.1607 | 0.2378 | 0.5575 | 0.078* | |
| C2 | 0.1003 (4) | 0.3936 (6) | 0.4452 (3) | 0.0498 (9) | |
| C3 | 0.1376 (4) | 0.5282 (8) | 0.5028 (4) | 0.0624 (13) | |
| H3 | 0.1737 | 0.5192 | 0.5702 | 0.075* | |
| C4 | 0.1190 (5) | 0.6766 (8) | 0.4564 (5) | 0.0677 (14) | |
| H4 | 0.1435 | 0.7680 | 0.4925 | 0.081* | |
| C5 | 0.0640 (4) | 0.6862 (6) | 0.3567 (4) | 0.0581 (11) | |
| H5 | 0.0499 | 0.7842 | 0.3251 | 0.070* | |
| C6 | 0.0304 (4) | 0.5486 (5) | 0.3045 (3) | 0.0466 (9) | |
| N1 | 0.0498 (3) | 0.4055 (4) | 0.3488 (3) | 0.0429 (7) | |
| Zn1 | 0.0000 | 0.22134 (8) | 0.2500 | 0.0467 (2) | |
| I1 | 0.15441 (3) | 0.07347 (4) | 0.21872 (3) | 0.06177 (17) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.061 (3) | 0.082 (4) | 0.049 (3) | 0.010 (3) | 0.010 (2) | 0.017 (2) |
| C2 | 0.045 (2) | 0.062 (3) | 0.043 (2) | 0.0025 (19) | 0.0125 (17) | −0.0009 (18) |
| C3 | 0.051 (2) | 0.086 (4) | 0.047 (2) | −0.001 (3) | 0.0064 (19) | −0.017 (2) |
| C4 | 0.062 (3) | 0.068 (3) | 0.073 (3) | −0.009 (3) | 0.017 (3) | −0.030 (3) |
| C5 | 0.058 (3) | 0.046 (2) | 0.068 (3) | −0.003 (2) | 0.011 (2) | −0.011 (2) |
| C6 | 0.050 (2) | 0.0395 (19) | 0.052 (2) | −0.0028 (16) | 0.0149 (18) | −0.0068 (16) |
| N1 | 0.0444 (17) | 0.0428 (17) | 0.0406 (16) | 0.0000 (14) | 0.0097 (13) | −0.0026 (13) |
| Zn1 | 0.0570 (4) | 0.0354 (3) | 0.0469 (4) | 0.000 | 0.0121 (3) | 0.000 |
| I1 | 0.0680 (3) | 0.0582 (2) | 0.0608 (2) | 0.01460 (14) | 0.01977 (18) | −0.00003 (13) |
| C1—C2 | 1.496 (8) | C4—H4 | 0.9300 |
| C1—H1A | 0.9600 | C5—C6 | 1.378 (6) |
| C1—H1B | 0.9600 | C5—H5 | 0.9300 |
| C1—H1C | 0.9600 | C6—N1 | 1.347 (6) |
| C2—N1 | 1.327 (6) | C6—C6i | 1.508 (9) |
| C2—C3 | 1.400 (8) | Zn1—N1 | 2.058 (3) |
| C3—C4 | 1.398 (9) | Zn1—N1i | 2.058 (3) |
| C3—H3 | 0.9300 | Zn1—I1i | 2.5501 (6) |
| C4—C5 | 1.379 (8) | Zn1—I1 | 2.5501 (6) |
| C2—C1—H1A | 109.5 | C6—C5—C4 | 119.0 (5) |
| C2—C1—H1B | 109.5 | C6—C5—H5 | 120.5 |
| H1A—C1—H1B | 109.5 | C4—C5—H5 | 120.5 |
| C2—C1—H1C | 109.5 | N1—C6—C5 | 121.5 (5) |
| H1A—C1—H1C | 109.5 | N1—C6—C6i | 116.1 (2) |
| H1B—C1—H1C | 109.5 | C5—C6—C6i | 122.4 (3) |
| N1—C2—C3 | 121.2 (5) | C2—N1—C6 | 120.5 (4) |
| N1—C2—C1 | 117.7 (4) | C2—N1—Zn1 | 126.6 (3) |
| C3—C2—C1 | 121.2 (5) | C6—N1—Zn1 | 112.8 (3) |
| C4—C3—C2 | 118.3 (5) | N1—Zn1—N1i | 81.9 (2) |
| C4—C3—H3 | 120.8 | N1—Zn1—I1i | 113.38 (10) |
| C2—C3—H3 | 120.8 | N1i—Zn1—I1i | 110.04 (10) |
| C5—C4—C3 | 119.5 (5) | N1—Zn1—I1 | 110.04 (10) |
| C5—C4—H4 | 120.3 | N1i—Zn1—I1 | 113.38 (10) |
| C3—C4—H4 | 120.3 | I1i—Zn1—I1 | 121.39 (3) |
| N1—C2—C3—C4 | 0.9 (7) | C5—C6—N1—C2 | 1.6 (7) |
| C1—C2—C3—C4 | −179.8 (5) | C6i—C6—N1—C2 | −178.1 (5) |
| C2—C3—C4—C5 | 0.8 (8) | C5—C6—N1—Zn1 | −175.7 (4) |
| C3—C4—C5—C6 | −1.3 (8) | C6i—C6—N1—Zn1 | 4.7 (6) |
| C4—C5—C6—N1 | 0.1 (8) | C2—N1—Zn1—N1i | −178.8 (5) |
| C4—C5—C6—C6i | 179.8 (6) | C6—N1—Zn1—N1i | −1.7 (2) |
| C3—C2—N1—C6 | −2.1 (7) | C2—N1—Zn1—I1i | 72.8 (4) |
| C1—C2—N1—C6 | 178.6 (4) | C6—N1—Zn1—I1i | −110.1 (3) |
| C3—C2—N1—Zn1 | 174.7 (3) | C2—N1—Zn1—I1 | −66.8 (4) |
| C1—C2—N1—Zn1 | −4.6 (6) | C6—N1—Zn1—I1 | 110.3 (3) |
| Symmetry codes: (i) −x, y, −z+1/2. |
| Zn1—N1 | 2.058 (3) | Zn1—I1 | 2.5501 (6) |
| N1—Zn1—N1i | 81.9 (2) |
| Symmetry codes: (i) −x, y, −z+1/2. |
We are grateful to the Damghan University of Basic Sciences and Islamic Azad University, Shahr-e-Rey Branch, for financial support.
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Recently, we reported the synthes and crystal structure of [ZnCl2(phend)], (II), (Khoshtarkib et al., 2009), [HgBr2(2,9-dmphen)], (III), (Alizadeh, Heidari et al., 2009) and [Pb4(NO3)8(6-mbpy)4], (IV), (Ahmadi, Kalateh, Alizadeh et al., 2009) [where phend is phenanthridine, 2,9-dmphen is 2,9-dimethyl-1,10-phenanthroline and 6-mbpy is 6-methyl-2,2'-bipyridine].
There are several ZnII complexes, with formula, [ZnX2(N—N)], (X = Cl, Br and I), such as [ZnCl2(bipy)], (V), (Khan & Tuck, 1984), [ZnCl2(phen)], (VI), (Reimann et al., 1966), [ZnCl2(dm4bt)], (VII), (Khavasi et al., 2008), [ZnCl2(5,5'-dmbpy)], (VIII), (khalighi et al., 2008), [ZnCl2(6-mbpy)], (IX), (Ahmadi, Kalateh, Ebadi et al., 2008), [ZnCl2(6,6'-dmbpy)], (X), (Alizadeh, Kalateh et al., 2009), [ZnCl2(PBD)]}, (XI), (Marjani et al., 2009), [ZnBr2(4,4'-(dtbpy)].(Et2O), (XII), (Blake et al., 2007), {ZnBr2[NH(py)2]},(XIII), (Lee et al., 2007), {ZnBr2[S(py)2]}, (XIV) (Wriedt et al., 2008), [ZnBr2(6,6'-dmbpy)], (XV), (Alizadeh, Khoshtarkib et al., 2009), [ZnI2(2,9-dmphen)], (XVI), (Seebacher et al., 2004) and {ZnI2[NH(py)2]}, (XVII) (Kwak et al., 2008) [where bipy is 2,2'-bipyridine, phen is 1,10-phenanthroline, dm4bt is 2,2'-dimethyl-4,4'-bithiazole, 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine, 6,6'-dmbpy is 6,6'-dimethyl-2,2'-bipyridine, PBD is N-(pyridin-2-ylmethylene)benzene-1,4-diamine, dtbpy is 4,4'-di-tert-butyl-2,2'-bipyridine, NH(py)2 is bis(2-pyridyl)amine, S(py)2 is bis(2-pyridyl)sulfide and NH(py)2 is bis(2-pyridyl)amine] 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 molecule of the title compound, (I), (Fig. 1), 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 I atoms. The Zn—I and Zn—I bond lengths and angles (Table 1) are within normal range (XVI).
The π-π contacts between the pyridine rings, Cg2···Cg2i [symmetry cods: (i) –X,1-Y,1-Z, where, Cg2 is centroids of the ring (N1/C2—C6)] further stabilize the structure, with centroid-centroid distance of 3.978 (3) Å. It seems this π-π stacking is effective in the stabilization of the crystal structure (Fig. 2).