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Acta Cryst. (2008). E64, m1305    [ doi:10.1107/S160053680802953X ]

(5,5'-Dimethyl-2,2'-bipyridine-[kappa]2N,N')diiodidomercury(II)

N. Tadayon Pour, A. Ebadi, A. Abedi, V. Amani and H. R. Khavasi

Abstract top

In the molecule of the title compound, [HgI2(C12H12N2)], the HgII atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from 5,5'-dimethyl-2,2'-bipyridine and two I atoms. There is a [pi]-[pi] contact between pyridine rings of adjacent molecules [centroid-centroid distance = 3.723 (5) Å].

Comment top

Recently, we reported the syntheses and crystal structures of [Zn(5,5'-dmbpy)Cl2], (II), (Khalighi et al., 2008), [Zn(6-mbpy)Cl2], (III), (Ahmadi, Kalateh et al., 2008), [Cd(5,5'-dmbpy)(µ-Cl)2]n, (IV), (Ahmadi, Khalighi et al., 2008), [Cu(5,5'-dcbpy)(en)(H2O)2].2.5H2O, (V), (Yousefi, Khalighi et al., 2008) and {[HgCl(dm4bt)]2(µ-Cl)2}, (VI), (Khavasi et al., 2008) [where 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine, 6-mbpy is 6-methyl-2,2' -bipyridine, 5,5'-dcbpy is 2,2'-bipyridine-5,5'-dicarboxylate, en is ethylene- diamine and dm4bt is 2,2'-dimethyl-4,4'-bithiazole]. There are several HgII complexes, with formula, [HgI2(N—N)], such as [HgI2(bipy)], (VII), [HgI2(phen)], (VIII) and [HgI2(2,9-dmphen)], (IX), (Freire et al., 1999), [HgI2(bipy)][HgI2], (X), (Chen et al., 2006), [HgI2(4,4'-dmbpy)], (XI), (Yousefi, Tadayon Pour et al., 2008) and [HgI2(TMDA)], (XII), (Htoon & Ladd, 1976) [where bipy is 2,2'-bipyridine, phen is 1,10-phenanthroline, dmphen is 2,9-dimethyl-1,10-phenanthroline, 4,4'-dmbpy is 4,4'-dimethyl-2,2'-bipyridine and TMDA is tetramethylethylene- diamine] 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, (Fig. 1), the HgII atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from 5,5'-dimethyl-2,2'-bi- pyridine and two I atoms. The Hg—I and Hg—N bond lengths and angles (Table 1) are within normal ranges, as in (VII), (VIII) and (XI).

In the crystal structure, the π-π contact (Fig. 2) between the pyridine rings, Cg2···Cg3i [symmetry code: (i) x, 1 - y, 1 - z, where Cg2 and Cg3 are centroids of the rings (N1/C1/C2/C4-C6) and (N2/C7-C10/C12), respectively] may stabilize the structure, with centroid-centroid distance of 3.723 (5) Å.

Related literature top

For related literature, see: Ahmadi, Kalateh et al. (2008); Ahmadi, Khalighi et al. (2008); Chen et al. (2006); Freire et al. (1999); Htoon & Ladd (1976); Khalighi et al. (2008); Khavasi et al. (2008); Yousefi, Khalighi, et al. (2008); Yousefi, Tadayon Pour et al. (2008).

Experimental top

For the preparation of the title compound, (I), a solution of 5,5'-dimethyl -2,2'-bipyridine (0.25 g, 1.33 mmol) in methanol (10 ml) was added to a solution of HgI2 (0.61 g, 1.33 mmol) in methanol (5 ml) at room temperature. The suitable crystals for X-ray analysis were isolated after one week by methanol diffusion to a colorless solution in DMSO (yield; 0.62 g, 72.9%).

Refinement top

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).

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. A packing diagram of the title compound.
(5,5'-Dimethyl-2,2'-bipyridine-κ2N,N')diiodidomercury(II) top
Crystal data top
[HgI2(C12H12N2)]F(000) = 2272
Mr = 638.63Dx = 2.665 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1768 reflections
a = 15.0325 (8) Åθ = 2.4–29.3°
b = 15.0654 (8) ŵ = 13.53 mm−1
c = 14.0579 (10) ÅT = 298 K
V = 3183.7 (3) Å3Prism, colorless
Z = 80.35 × 0.31 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		4306 independent reflections
Radiation source: fine-focus sealed tube3418 reflections with I > 2σ(I)
graphiteRint = 0.083
φ and ω scansθmax = 29.3°, θmin = 2.4°
Absorption correction: numerical
shape of crystal determined optically (X-SHAPE and X-RED32; Stoe& Cie, 2005)		h = −20→19
Tmin = 0.015, Tmax = 0.075k = −20→17
23007 measured reflectionsl = −19→19
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H-atom parameters constrained
S = 1.19 w = 1/[σ2(Fo2) + (0.0347P)2 + 17.4498P]
where P = (Fo2 + 2Fc2)/3
4306 reflections(Δ/σ)max = 0.010
154 parametersΔρmax = 1.44 e Å−3
0 restraintsΔρmin = −1.51 e Å−3
Crystal data top
[HgI2(C12H12N2)]V = 3183.7 (3) Å3
Mr = 638.63Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 15.0325 (8) ŵ = 13.53 mm−1
b = 15.0654 (8) ÅT = 298 K
c = 14.0579 (10) Å0.35 × 0.31 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		4306 independent reflections
Absorption correction: numerical
shape of crystal determined optically (X-SHAPE and X-RED32; Stoe& Cie, 2005)		3418 reflections with I > 2σ(I)
Tmin = 0.015, Tmax = 0.075Rint = 0.083
23007 measured reflectionsθmax = 29.3°
Refinement top
R[F2 > 2σ(F2)] = 0.055 w = 1/[σ2(Fo2) + (0.0347P)2 + 17.4498P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.124Δρmax = 1.44 e Å−3
S = 1.19Δρmin = −1.51 e Å−3
4306 reflectionsAbsolute structure: ?
154 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
H-atom parameters constrained
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
Hg10.11964 (2)0.71065 (2)0.60202 (3)0.05197 (12)
I10.00810 (7)0.80915 (5)0.50004 (7)0.0859 (3)
I20.25140 (5)0.76000 (5)0.71769 (6)0.0687 (2)
N10.1696 (4)0.5812 (5)0.5214 (5)0.0403 (14)
N20.0387 (4)0.5836 (4)0.6554 (5)0.0381 (13)
C10.2371 (5)0.5833 (6)0.4598 (6)0.0463 (18)
H10.26330.63770.44600.056*
C20.2697 (6)0.5082 (7)0.4155 (6)0.049 (2)
C30.3485 (8)0.5156 (9)0.3481 (9)0.077 (3)
H3A0.39860.53990.38160.093*
H3B0.33330.55380.29590.093*
H3C0.36350.45780.32430.093*
C40.2299 (7)0.4279 (7)0.4391 (8)0.063 (3)
H40.25060.37550.41210.076*
C50.1604 (7)0.4257 (6)0.5019 (7)0.053 (2)
H50.13240.37230.51620.063*
C60.1322 (5)0.5044 (5)0.5440 (5)0.0387 (16)
C70.0586 (5)0.5057 (5)0.6156 (5)0.0378 (15)
C80.0140 (6)0.4291 (6)0.6412 (7)0.054 (2)
H80.02700.37540.61180.065*
C9−0.0503 (6)0.4341 (6)0.7113 (7)0.054 (2)
H9−0.08050.38290.72970.065*
C10−0.0703 (6)0.5135 (6)0.7542 (6)0.0477 (19)
C11−0.1370 (7)0.5206 (8)0.8337 (8)0.069 (3)
H11A−0.18310.56150.81590.083*
H11B−0.10780.54170.89010.083*
H11C−0.16250.46330.84580.083*
C12−0.0244 (5)0.5873 (6)0.7226 (6)0.0465 (18)
H12−0.03790.64220.74920.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.0544 (2)0.04113 (17)0.0603 (2)0.00092 (15)0.00422 (17)−0.00082 (14)
I10.0978 (6)0.0521 (4)0.1078 (7)0.0131 (4)−0.0354 (5)0.0050 (4)
I20.0660 (4)0.0555 (4)0.0845 (5)0.0031 (3)−0.0154 (4)−0.0110 (3)
N10.039 (3)0.044 (3)0.037 (3)0.001 (3)0.003 (3)−0.002 (3)
N20.035 (3)0.039 (3)0.041 (3)0.002 (3)0.000 (3)0.001 (3)
C10.040 (4)0.053 (5)0.046 (4)−0.002 (4)0.009 (3)−0.006 (4)
C20.041 (4)0.072 (6)0.035 (4)0.012 (4)0.000 (3)−0.002 (4)
C30.061 (6)0.098 (9)0.073 (7)0.016 (6)0.029 (6)−0.004 (6)
C40.070 (7)0.058 (6)0.062 (6)0.019 (5)0.001 (5)−0.020 (5)
C50.058 (5)0.045 (4)0.056 (5)0.003 (4)0.004 (4)−0.002 (4)
C60.038 (4)0.038 (4)0.040 (4)0.001 (3)−0.004 (3)−0.002 (3)
C70.039 (4)0.040 (4)0.035 (4)0.003 (3)−0.009 (3)−0.001 (3)
C80.057 (5)0.047 (5)0.058 (5)−0.009 (4)−0.004 (4)−0.002 (4)
C90.051 (5)0.051 (5)0.062 (6)−0.016 (4)0.003 (4)0.007 (4)
C100.038 (4)0.057 (5)0.048 (5)−0.001 (4)−0.005 (3)0.010 (4)
C110.059 (6)0.080 (7)0.067 (6)−0.001 (5)0.031 (5)0.000 (5)
C120.042 (4)0.048 (4)0.050 (5)0.003 (4)0.009 (4)−0.003 (4)
Geometric parameters (Å, °) top
Hg1—I12.6587 (9)C6—N11.325 (10)
Hg1—I22.6684 (8)C6—C71.496 (11)
Hg1—N12.377 (7)C7—N21.335 (10)
Hg1—N22.389 (6)C7—C81.382 (12)
C1—N11.335 (10)C8—C91.384 (14)
C1—C21.380 (13)C8—H80.9300
C1—H10.9300C9—C101.373 (13)
C2—C41.390 (15)C9—H90.9300
C2—C31.521 (13)C10—C121.382 (12)
C3—H3A0.9600C10—C111.505 (13)
C3—H3B0.9600C11—H11A0.9600
C3—H3C0.9600C11—H11B0.9600
C4—C51.368 (14)C11—H11C0.9600
C4—H40.9300C12—N21.339 (10)
C5—C61.392 (11)C12—H120.9300
C5—H50.9300
I1—Hg1—I2129.89 (3)C4—C5—C6119.1 (9)
N1—Hg1—I1113.59 (16)C4—C5—H5120.5
N1—Hg1—N269.7 (2)C6—C5—H5120.5
N1—Hg1—I2106.53 (16)N1—C6—C5120.9 (8)
N2—Hg1—I1107.15 (15)N1—C6—C7117.6 (7)
N2—Hg1—I2114.22 (15)C5—C6—C7121.5 (7)
C1—N1—Hg1122.0 (6)N2—C7—C8121.1 (8)
C6—N1—Hg1117.9 (5)N2—C7—C6117.4 (7)
C6—N1—C1119.9 (7)C8—C7—C6121.5 (7)
C7—N2—Hg1117.3 (5)C7—C8—C9118.7 (9)
C7—N2—C12119.4 (7)C7—C8—H8120.7
C12—N2—Hg1123.3 (5)C9—C8—H8120.7
N1—C1—C2122.9 (9)C10—C9—C8120.8 (8)
N1—C1—H1118.5C10—C9—H9119.6
C2—C1—H1118.5C8—C9—H9119.6
C1—C2—C4116.9 (8)C9—C10—C12116.8 (8)
C1—C2—C3119.9 (10)C9—C10—C11122.3 (9)
C4—C2—C3123.2 (9)C12—C10—C11120.9 (9)
C2—C3—H3A109.5C10—C11—H11A109.5
C2—C3—H3B109.5C10—C11—H11B109.5
H3A—C3—H3B109.5H11A—C11—H11B109.5
C2—C3—H3C109.5C10—C11—H11C109.5
H3A—C3—H3C109.5H11A—C11—H11C109.5
H3B—C3—H3C109.5H11B—C11—H11C109.5
C5—C4—C2120.3 (9)N2—C12—C10123.2 (8)
C5—C4—H4119.8N2—C12—H12118.4
C2—C4—H4119.8C10—C12—H12118.4
I1—Hg1—N1—C182.9 (6)C5—C6—N1—C1−2.1 (12)
I1—Hg1—N1—C6−101.5 (5)C7—C6—N1—C1178.3 (7)
I2—Hg1—N1—C1−66.4 (6)C5—C6—N1—Hg1−177.8 (6)
I2—Hg1—N1—C6109.2 (5)C7—C6—N1—Hg12.6 (9)
N2—Hg1—N1—C1−176.7 (7)N1—C6—C7—N2−3.3 (11)
N2—Hg1—N1—C6−1.1 (5)C5—C6—C7—N2177.1 (8)
I1—Hg1—N2—C7108.7 (5)N1—C6—C7—C8178.0 (8)
I1—Hg1—N2—C12−71.7 (6)C5—C6—C7—C8−1.6 (12)
I2—Hg1—N2—C7−100.3 (5)C8—C7—N2—C121.4 (12)
I2—Hg1—N2—C1279.3 (6)C6—C7—N2—C12−177.3 (7)
N1—Hg1—N2—C7−0.8 (5)C8—C7—N2—Hg1−179.0 (6)
N1—Hg1—N2—C12178.9 (7)C6—C7—N2—Hg12.3 (9)
C2—C1—N1—C61.5 (13)N2—C7—C8—C9−1.9 (13)
C2—C1—N1—Hg1177.0 (6)C6—C7—C8—C9176.7 (8)
N1—C1—C2—C4−1.1 (13)C7—C8—C9—C100.6 (15)
N1—C1—C2—C3−178.3 (9)C8—C9—C10—C121.2 (14)
C1—C2—C4—C51.4 (14)C8—C9—C10—C11−177.2 (9)
C3—C2—C4—C5178.5 (10)C9—C10—C12—N2−1.8 (13)
C2—C4—C5—C6−2.1 (15)C11—C10—C12—N2176.6 (9)
C4—C5—C6—N12.5 (14)C10—C12—N2—C70.6 (13)
C4—C5—C6—C7−178.0 (8)C10—C12—N2—Hg1−179.1 (6)
Table 1
Selected geometric parameters (Å, °) top
Hg1—I12.6587 (9)Hg1—N12.377 (7)
Hg1—I22.6684 (8)Hg1—N22.389 (6)
I1—Hg1—I2129.89 (3)N1—Hg1—I2106.53 (16)
N1—Hg1—I1113.59 (16)N2—Hg1—I1107.15 (15)
N1—Hg1—N269.7 (2)N2—Hg1—I2114.22 (15)
Acknowledgements top

We are grateful to the Islamic Azad University, Shahr-e-Rey Branch, for financial support.

references
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