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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): m1397–m1398.
Published online 2008 October 15. doi:  10.1107/S1600536808032510
PMCID: PMC2959555

Di-μ-bromido-bis­[bromido(4,4′-dimethyl-2,2′-bipyridine-κ2 N,N′)mercury(II)]

Abstract

The asymmetric unit of the title compound, [Hg2Br4(C12H12N2)2], contains one half-mol­ecule. The HgII atom is five-coordinated in a trigonal–bipyramidal configuration by two N atoms from the chelating 4,4′-dimethyl-2,2′-bipyridine ligand, two bridging Br and one terminal Br atom, leading to a centrosymmetric dimeric mol­ecule. There is a π–π contact between the pyridine rings [centroid-to-centroid distance = 3.756 (5) Å].

Related literature

For related literature, see: Ahmadi, Kalateh, Ebadi et al. (2008 [triangle]); Ahmadi, Khalighi et al. (2008 [triangle]); Ahmadi, Kalateh, Abedi et al. (2008 [triangle]); Kalateh et al. (2008 [triangle]); Khalighi et al. (2008 [triangle]); Khavasi et al. (2008 [triangle]); Tadayon Pour et al. (2008 [triangle]); Yousefi, Rashidi Vahid et al. (2008 [triangle]); Yousefi, Tadayon Pour et al. (2008 [triangle]); Yousefi, Khalighi et al. (2008 [triangle]). For related structures, see: Craig et al. (1974 [triangle]); Perlepes et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1397-scheme1.jpg

Experimental

Crystal data

  • [Hg2Br4(C12H12N2)2]
  • M r = 1089.25
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1397-efi1.jpg
  • a = 7.3187 (15) Å
  • b = 9.2647 (19) Å
  • c = 11.345 (2) Å
  • α = 103.50 (3)°
  • β = 102.02 (3)°
  • γ = 107.87 (3)°
  • V = 678.6 (3) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 17.21 mm−1
  • T = 120 (2) K
  • 0.45 × 0.25 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: numerical; shape of crystal determined optically (X-SHAPE and X-RED; Stoe & Cie, 2005 [triangle]) T min = 0.008, T max = 0.180
  • 8289 measured reflections
  • 3632 independent reflections
  • 3504 reflections with I > 2σ(I)
  • R int = 0.073

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.165
  • S = 1.07
  • 3632 reflections
  • 155 parameters
  • H-atom parameters constrained
  • Δρmax = 2.11 e Å−3
  • Δρmin = −1.85 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 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808032510/hk2544sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808032510/hk2544Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

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, Ebadi et al., 2008), [HgI2(4,4'-dmbpy)], (IV), (Yousefi, Tadayon Pour et al., 2008), [Cd(5,5'-dmbpy)(µ-Cl)2]n, (V), (Ahmadi, Khalighi et al., 2008), [Hg(5,5'-dmbpy)I2], (VI), (Tadayon Pour et al., 2008), [Cu(5,5'-dcbpy)(en)(H2O)2].2.5H2O, (VII), (Yousefi, Khalighi et al., 2008), [Hg(dmphen)I2], (VIII), (Yousefi, Rashidi Vahid et al., 2008), [In(4,4'-dmbpy)Cl3(DMSO)], (IX), (Ahmadi, Kalateh, Abedi et al., 2008), [In(5,5'-dmbpy)Cl3(MeOH)], (X), (Kalateh et al., 2008) and {[HgCl(dm4bt)]2(µ-Cl)2}, (XI), (Khavasi et al., 2008) [where 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine, 6-mbpy is 6-methyl-2,2'-bipyridine, 4,4'-dmbpy is 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dcbpy is 2,2'-bipyridine-5,5'-dicarboxylate, en is ethylenediamine, dmphen is 4,7-diphenyl-1,10-phenanthroline, DMSO is dimethyl sulfoxide and dm4bt is 2,2'-dimethyl-4,4'-bithiazole]. There are two HgII dimer complexes, with formula, [{HgBr(N—N)}2(µ-Br)2], such as [{HgBr(bipy)}2(µ-Br)2], (XII), (Craig et al., 1974) and [{HgBr(pquin)}2(µ-Br)2], (XIII), (Perlepes et al., 1995) [where bipy is 2,2'-bipyridine and pquin is 2-(2'-pyridyl)quinoxaline] 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), contains one half-molecule (Fig. 1). The HgII atom is five-coordinated in a trigonal–bipyramidal configuration by two N atoms from the chelating 4,4'-dimethyl-2,2'-bipyridine ligand, two bridging Br and one terminal Br atoms. The Hg—Br and Hg—N bond lengths and angles (Table 1) are within normal ranges, as in (XII) and (XIII).

In the crystal structure, the π–π contact (Fig. 2) between the pyridine rings, Cg3–Cg4i [symmetry code: (i) 2 - x, 2 - y, -z, where Cg3 and Cg4 are centroids of the rings (N1/C1–C3/C5–C6) and (N2/C7–C9/C11–C12), respectively] may stabilize the structure, with centroid–centroid distance of 3.756 (5) Å.

Experimental

For the preparation of the title compound, (I), a solution of 4,4'-dimethyl-2,2'-bipyridine (0.20 g, 1.10 mmol) in methanol (5 ml) was added to a solution of HgBr2 (0.40 g, 1.10 mmol) in methanol (5 ml) at room temperature. The suitable crystals for X-ray analysis were obtained by methanol diffusion to a colorless solution in DMSO. Suitable crystals were isolated after one week (yield; 0.44 g, 73.4%).

Refinement

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).

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
A partial packing diagram of the title compound.

Crystal data

[Hg2Br4(C12H12N2)2]Z = 1
Mr = 1089.25F(000) = 496
Triclinic, P1Dx = 2.665 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.3187 (15) ÅCell parameters from 1005 reflections
b = 9.2647 (19) Åθ = 1.9–29.2°
c = 11.345 (2) ŵ = 17.21 mm1
α = 103.50 (3)°T = 120 K
β = 102.02 (3)°Block, colourless
γ = 107.87 (3)°0.45 × 0.25 × 0.10 mm
V = 678.6 (3) Å3

Data collection

Bruker SMART CCD area-detector diffractometer3632 independent reflections
Radiation source: fine-focus sealed tube3504 reflections with I > 2σ(I)
graphiteRint = 0.073
[var phi] and ω scansθmax = 29.2°, θmin = 1.9°
Absorption correction: numerical shape of crystal determined optically (X-SHAPE and X-RED; Stoe & Cie, 2005)h = −9→10
Tmin = 0.008, Tmax = 0.180k = −12→12
8289 measured reflectionsl = −15→15

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.165w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.037
3632 reflectionsΔρmax = 2.11 e Å3
155 parametersΔρmin = −1.85 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 1998), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.025 (3)

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
Hg10.53006 (3)0.61812 (3)−0.12572 (2)0.0245 (2)
Br10.40249 (13)0.40548 (9)−0.34549 (8)0.0325 (2)
Br20.23799 (9)0.50603 (8)−0.01775 (7)0.0255 (2)
N10.6268 (10)0.8331 (7)−0.2132 (6)0.0274 (12)
N20.6826 (10)0.8668 (7)0.0356 (7)0.0259 (13)
C10.5951 (13)0.8128 (9)−0.3382 (7)0.0315 (15)
H10.52670.7096−0.39510.038*
C20.6580 (13)0.9356 (10)−0.3863 (7)0.0293 (15)
H20.63410.9144−0.47350.035*
C30.7570 (11)1.0912 (8)−0.3051 (7)0.0241 (12)
C40.8350 (13)1.2322 (10)−0.3489 (8)0.0309 (15)
H4A0.97881.2815−0.31260.037*
H4B0.77551.3082−0.32210.037*
H4C0.80091.1972−0.43990.037*
C50.7909 (11)1.1122 (9)−0.1742 (7)0.0242 (13)
H50.85911.2142−0.11540.029*
C60.7238 (10)0.9826 (8)−0.1321 (7)0.0228 (12)
C70.7541 (9)0.9998 (8)0.0047 (7)0.0224 (12)
C80.8549 (10)1.1479 (8)0.0993 (7)0.0237 (13)
H80.90951.23900.07740.028*
C90.8745 (11)1.1602 (8)0.2269 (7)0.0252 (13)
C100.9781 (15)1.3215 (9)0.3311 (9)0.0369 (18)
H10A0.90881.39110.31530.044*
H10B1.11521.36820.33190.044*
H10C0.97571.30710.41190.044*
C110.8008 (11)1.0223 (8)0.2559 (7)0.0272 (14)
H110.81581.02560.34000.033*
C120.7042 (12)0.8786 (9)0.1588 (9)0.0300 (14)
H120.65160.78600.17920.036*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Hg10.0272 (3)0.0176 (2)0.0256 (3)0.00731 (15)0.00742 (15)0.00320 (15)
Br10.0424 (4)0.0215 (4)0.0268 (4)0.0077 (3)0.0097 (3)0.0018 (3)
Br20.0214 (4)0.0225 (4)0.0329 (4)0.0098 (3)0.0094 (3)0.0064 (3)
N10.032 (3)0.018 (3)0.021 (3)0.005 (2)0.001 (2)−0.002 (2)
N20.028 (3)0.019 (2)0.028 (3)0.006 (2)0.010 (2)0.005 (2)
C10.043 (4)0.023 (3)0.019 (3)0.006 (3)0.005 (3)0.002 (2)
C20.036 (4)0.026 (4)0.025 (3)0.011 (3)0.009 (3)0.007 (3)
C30.026 (3)0.016 (3)0.031 (3)0.010 (2)0.011 (3)0.005 (2)
C40.037 (4)0.025 (3)0.031 (4)0.009 (3)0.013 (3)0.010 (3)
C50.029 (3)0.021 (3)0.023 (3)0.010 (2)0.010 (3)0.005 (3)
C60.025 (3)0.014 (3)0.024 (3)0.007 (2)0.002 (2)0.002 (2)
C70.016 (2)0.018 (3)0.024 (3)0.006 (2)−0.003 (2)−0.001 (2)
C80.023 (3)0.020 (3)0.021 (3)0.007 (2)0.002 (2)0.001 (2)
C90.030 (3)0.025 (3)0.023 (3)0.015 (2)0.007 (2)0.005 (2)
C100.052 (5)0.021 (3)0.033 (4)0.017 (3)0.007 (3)0.000 (3)
C110.028 (3)0.024 (3)0.025 (3)0.012 (3)0.005 (3)0.001 (3)
C120.030 (3)0.025 (3)0.030 (4)0.008 (3)0.009 (3)0.004 (3)

Geometric parameters (Å, °)

Hg1—Br2i2.7884 (11)C5—H50.9300
Br1—Hg12.5645 (15)C6—N11.341 (8)
Br2—Hg12.7331 (11)C6—C71.484 (10)
Br2—Hg1i2.7884 (11)C7—N21.341 (10)
N1—Hg12.409 (7)C7—C81.393 (9)
N2—Hg12.346 (6)C8—C91.399 (10)
C1—C21.370 (11)C8—H80.9300
C1—N11.347 (10)C9—C111.371 (10)
C1—H10.9300C9—C101.520 (10)
C2—C31.383 (10)C10—H10A0.9600
C2—H20.9300C10—H10B0.9600
C3—C51.410 (11)C10—H10C0.9600
C3—C41.497 (10)C11—C121.377 (10)
C4—H4A0.9600C11—H110.9300
C4—H4B0.9600C12—N21.348 (11)
C4—H4C0.9600C12—H120.9300
C5—C61.383 (10)
Br1—Hg1—Br2102.48 (4)H4A—C4—H4C109.5
Br1—Hg1—Br2i101.32 (4)H4B—C4—H4C109.5
Br2—Hg1—Br2i87.29 (3)C6—C5—C3120.7 (7)
N1—Hg1—Br192.18 (15)C6—C5—H5119.9
N1—Hg1—Br2135.51 (16)C3—C5—H5119.4
N1—Hg1—Br2i130.97 (16)N1—C6—C5121.7 (7)
N2—Hg1—Br1161.0 (2)N1—C6—C7115.9 (6)
N2—Hg1—Br293.17 (18)C5—C6—C7122.4 (6)
N2—Hg1—Br2i89.92 (18)N2—C7—C8120.3 (7)
N2—Hg1—N169.0 (2)N2—C7—C6117.8 (6)
Hg1—Br2—Hg1i92.71 (3)C8—C7—C6121.9 (6)
C1—N1—Hg1124.3 (5)C7—C8—C9120.3 (7)
C6—N1—Hg1118.0 (5)C7—C8—H8119.8
C6—N1—C1117.6 (7)C9—C8—H8119.9
C7—N2—Hg1119.1 (5)C11—C9—C8118.1 (7)
C12—N2—Hg1121.6 (5)C11—C9—C10120.8 (7)
C12—N2—C7119.3 (6)C8—C9—C10121.1 (7)
C2—C1—N1123.7 (7)C9—C10—H10A109.4
C2—C1—H1117.9C9—C10—H10B109.3
N1—C1—H1118.4H10A—C10—H10B109.5
C1—C2—C3120.0 (7)C9—C10—H10C109.7
C1—C2—H2120.2H10A—C10—H10C109.5
C3—C2—H2119.8H10B—C10—H10C109.5
C2—C3—C5116.2 (7)C9—C11—C12119.2 (7)
C2—C3—C4123.6 (7)C9—C11—H11120.9
C5—C3—C4120.1 (6)C12—C11—H11119.9
C3—C4—H4A109.7N2—C12—C11122.7 (7)
C3—C4—H4B109.0N2—C12—H12118.6
H4A—C4—H4B109.5C11—C12—H12118.7
C3—C4—H4C109.7
Hg1i—Br2—Hg1—Br1101.00 (4)C3—C5—C6—N10.8 (11)
Hg1i—Br2—Hg1—Br2i0.0C3—C5—C6—C7−179.2 (6)
Hg1i—Br2—Hg1—N1−152.7 (2)N1—C6—C7—N2−0.2 (9)
Hg1i—Br2—Hg1—N2−89.77 (18)C5—C6—C7—N2179.7 (7)
C1—N1—Hg1—Br13.2 (7)N1—C6—C7—C8179.1 (6)
C6—N1—Hg1—Br1−174.7 (5)C5—C6—C7—C8−0.9 (10)
C1—N1—Hg1—Br2−107.1 (6)N2—C7—C8—C9−2.9 (10)
C1—N1—Hg1—Br2i110.3 (6)C6—C7—C8—C9177.8 (6)
C6—N1—Hg1—Br274.9 (6)C7—C8—C9—C113.2 (10)
C6—N1—Hg1—Br2i−67.7 (6)C7—C8—C9—C10−178.0 (6)
C6—N1—Hg1—N22.7 (5)C8—C9—C11—C12−2.5 (10)
C1—N1—Hg1—N2−179.3 (7)C10—C9—C11—C12178.7 (7)
C7—N2—Hg1—Br14.9 (9)C9—C11—C12—N21.6 (11)
C12—N2—Hg1—Br1−173.5 (4)C5—C6—N1—C1−0.4 (11)
C7—N2—Hg1—Br2−140.9 (5)C7—C6—N1—C1179.5 (6)
C7—N2—Hg1—Br2i131.8 (5)C5—C6—N1—Hg1177.7 (5)
C12—N2—Hg1—Br240.6 (6)C7—C6—N1—Hg1−2.4 (8)
C12—N2—Hg1—Br2i−46.7 (6)C2—C1—N1—C60.6 (13)
C7—N2—Hg1—N1−2.9 (5)C2—C1—N1—Hg1−177.3 (7)
C12—N2—Hg1—N1178.7 (6)C11—C12—N2—C7−1.3 (11)
N1—C1—C2—C3−1.2 (13)C11—C12—N2—Hg1177.1 (5)
C1—C2—C3—C51.4 (12)C8—C7—N2—C121.9 (10)
C1—C2—C3—C4178.6 (8)C6—C7—N2—C12−178.7 (6)
C2—C3—C5—C6−1.2 (11)C8—C7—N2—Hg1−176.5 (5)
C4—C3—C5—C6−178.5 (7)C6—C7—N2—Hg12.8 (8)

Symmetry codes: (i) −x+1, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2544).

References

  • Ahmadi, R., Kalateh, K., Abedi, A., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1306–m1307. [PMC free article] [PubMed]
  • Ahmadi, R., Kalateh, K., Ebadi, A., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1266. [PMC free article] [PubMed]
  • Ahmadi, R., Khalighi, A., Kalateh, K., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1233. [PMC free article] [PubMed]
  • Bruker (1998). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Craig, D. C., Farhangi, Y., Graddon, D. P. & Stephenson, N. C. (1974). Cryst. Struct. Commun.3, 155–158.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Kalateh, K., Ahmadi, R., Ebadi, A., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1353–m1354. [PMC free article] [PubMed]
  • Khalighi, A., Ahmadi, R., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1211–m1212. [PMC free article] [PubMed]
  • Khavasi, H. R., Abedi, A., Amani, V., Notash, B. & Safari, N. (2008). Polyhedron, 27, 1848–1854.
  • Perlepes, S. P., Kasselouri, S., Garoufis, A., Lutz, F., Bau, R. & Hadjiliadis, N. (1995). Polyhedron, 14, 1461–1470.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stoe & Cie (2005). X-SHAPE and X-RED Stoe & Cie, Darmstadt, Germany.
  • Tadayon Pour, N., Ebadi, A., Abedi, A., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1305. [PMC free article] [PubMed]
  • Yousefi, M., Khalighi, A., Tadayon Pour, N., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1284–m1285. [PMC free article] [PubMed]
  • Yousefi, M., Rashidi Vahid, R., Amani, V., Arab Chamjangali, M. & Khavasi, H. R. (2008). Acta Cryst. E64, m1339–m1340. [PMC free article] [PubMed]
  • Yousefi, M., Tadayon Pour, N., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1259. [PMC free article] [PubMed]

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