PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): m1311.
Published online 2009 October 7. doi:  10.1107/S1600536809039610
PMCID: PMC2971289

Dibromido(6,6′-dimethyl-2,2′-bipyridine-κ2 N,N′)zinc(II)

Abstract

In the title compound, [ZnBr2(C12H12N2)], the ZnII atom is four-coordinated in a distorted tetra­hedral arrangement by an N,N′-bidentate 6,6′-dimethyl-2,2′-bipyridine ligand and two bromide ions. In the crystal, there are aromatic π–π contacts between the pyridine rings [centroid–centroid distances = 3.818 (3) and 3.728 (4) Å].

Related literature

For related crystal structures containing a Zn atom coordin­ated by an N,N-bidentate bipyridine or phenanthroline-type ligand and two halide ions, see: Ahmadi et al. (2008 [triangle], 2009 [triangle]); Alizadeh, Heidari, et al. (2009 [triangle]); Alizadeh, Kalateh, et al. (2009 [triangle]); Blake et al. (2007 [triangle]); Khalighi et al. (2008 [triangle]); Khan & Tuck (1984 [triangle]); Khavasi et al. (2008 [triangle]); Khoshtarkib et al. (2009 [triangle]); Lee et al. (2007 [triangle]); Marjani et al. (2009 [triangle]); Reimann et al. (1966 [triangle]); Wriedt et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1311-scheme1.jpg

Experimental

Crystal data

  • [ZnBr2(C12H12N2)]
  • M r = 409.43
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1311-efi1.jpg
  • a = 7.6506 (15) Å
  • b = 10.279 (2) Å
  • c = 18.023 (4) Å
  • β = 95.93 (3)°
  • V = 1409.8 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 7.39 mm−1
  • T = 298 K
  • 0.17 × 0.16 × 0.12 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1998 [triangle]) T min = 0.300, T max = 0.418
  • 11390 measured reflections
  • 3822 independent reflections
  • 2717 reflections with I > 2σ(I)
  • R int = 0.068

Refinement

  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.126
  • S = 1.11
  • 3822 reflections
  • 154 parameters
  • H-atom parameters constrained
  • Δρmax = 0.81 e Å−3
  • Δρmin = −0.68 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 (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809039610/hb5122sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039610/hb5122Isup2.hkl

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

Acknowledgments

We are grateful to Damghan University of Basic Sciences and the Islamic Azad University, Shahr-e-Rey Branch, for financial support.

supplementary crystallographic information

Comment

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 and Br), 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) and {ZnBr2[S(py)2]}, (XIV) (Wriedt 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 and S(py)2 is bis(2-pyridyl)sulfide] 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 Br atoms. The Zn—Br and Zn—N bond lengths and angles are collected in Table 1.

The π-π contacts between the pyridine rings, Cg1···Cg3i and Cg2···Cg3ii [symmetry cods: (i) 1-X,2-Y,-Z, (ii) –X,2-Y,-Z, where Cg1, Cg2 and Cg3 are centroids of the rings (Zn1/N1/C6—C7/N2), (N1/C2—C6) and (N2/C7—C11), respectively] further stabilize the structure, with centroid-centroid distance of 3.818 (3) and 3.728 (4) Å, respectively. It seems this π-π stacking is effective in the stabilization of the crystal structure (Fig. 2).

Experimental

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 ZnBr2 (0.25 g, 1.10 mmol) in acetonitrile (10 ml) and the resulting colourless solution was stirred for 20 min at at 313 K. This solution was left to evaporate slowly at room temperature. After one week, colorless prisms of (I) were isolated (yield 0.33 g, 73.7%).

Refinement

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).

Figures

Fig. 1.
The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
Unit-cell packing diagram for (I).

Crystal data

[ZnBr2(C12H12N2)]F(000) = 792
Mr = 409.43Dx = 1.929 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1342 reflections
a = 7.6506 (15) Åθ = 2.3–29.3°
b = 10.279 (2) ŵ = 7.39 mm1
c = 18.023 (4) ÅT = 298 K
β = 95.93 (3)°Prism, colourless
V = 1409.8 (5) Å30.17 × 0.16 × 0.12 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer3822 independent reflections
Radiation source: fine-focus sealed tube2717 reflections with I > 2σ(I)
graphiteRint = 0.068
[var phi] and ω scansθmax = 29.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)h = −9→10
Tmin = 0.300, Tmax = 0.418k = −14→14
11390 measured reflectionsl = −24→24

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H-atom parameters constrained
S = 1.11w = 1/[σ2(Fo2) + (0.0419P)2 + 2.306P] where P = (Fo2 + 2Fc2)/3
3822 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.81 e Å3
0 restraintsΔρmin = −0.68 e Å3

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
C10.1523 (12)0.9316 (8)0.2403 (4)0.077 (2)
H1A0.26610.89400.25380.092*
H1B0.06790.86350.22880.092*
H1C0.11850.98240.28120.092*
C20.1591 (7)1.0167 (6)0.1736 (3)0.0486 (13)
C30.1234 (9)1.1474 (7)0.1764 (4)0.0614 (16)
H30.09461.18510.22040.074*
C40.1306 (9)1.2221 (6)0.1134 (4)0.0654 (18)
H40.10551.31050.11440.078*
C50.1755 (8)1.1645 (6)0.0485 (4)0.0578 (15)
H50.18011.21380.00540.069*
C60.2132 (7)1.0330 (5)0.0485 (3)0.0425 (11)
C70.2666 (6)0.9633 (5)−0.0177 (3)0.0388 (11)
C80.2796 (8)1.0242 (6)−0.0855 (3)0.0535 (14)
H80.25101.1117−0.09190.064*
C90.3356 (9)0.9530 (8)−0.1428 (4)0.0668 (19)
H90.34550.9926−0.18860.080*
C100.3770 (8)0.8238 (8)−0.1333 (3)0.0581 (16)
H100.41560.7754−0.17200.070*
C110.3597 (8)0.7663 (6)−0.0638 (3)0.0490 (13)
C120.3987 (12)0.6258 (7)−0.0493 (4)0.074 (2)
H12A0.29420.5824−0.03710.089*
H12B0.48890.6177−0.00840.089*
H12C0.43800.5868−0.09300.089*
N10.2039 (6)0.9612 (4)0.1102 (2)0.0394 (9)
N20.3051 (6)0.8366 (4)−0.0080 (2)0.0390 (9)
Zn10.26913 (8)0.76759 (6)0.09736 (3)0.04134 (17)
Br10.03105 (10)0.62512 (7)0.10150 (4)0.0682 (2)
Br20.52344 (8)0.69964 (7)0.17038 (3)0.05791 (19)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.119 (6)0.070 (5)0.045 (3)0.017 (5)0.023 (4)−0.006 (3)
C20.048 (3)0.047 (3)0.051 (3)0.006 (2)0.007 (2)−0.010 (2)
C30.064 (4)0.052 (4)0.067 (4)0.014 (3)0.002 (3)−0.018 (3)
C40.071 (4)0.036 (3)0.085 (5)0.012 (3)−0.009 (4)−0.013 (3)
C50.058 (3)0.041 (3)0.070 (4)0.004 (3)−0.014 (3)0.015 (3)
C60.039 (3)0.034 (3)0.053 (3)0.000 (2)−0.003 (2)0.004 (2)
C70.036 (2)0.038 (3)0.042 (3)−0.004 (2)−0.001 (2)0.009 (2)
C80.057 (3)0.054 (3)0.048 (3)−0.005 (3)−0.001 (3)0.017 (3)
C90.074 (4)0.083 (5)0.044 (3)−0.013 (4)0.008 (3)0.020 (3)
C100.055 (3)0.083 (5)0.036 (3)−0.003 (3)0.005 (2)−0.001 (3)
C110.055 (3)0.056 (3)0.036 (3)−0.005 (3)0.006 (2)−0.002 (2)
C120.117 (6)0.054 (4)0.052 (4)0.022 (4)0.017 (4)−0.006 (3)
N10.043 (2)0.035 (2)0.040 (2)0.0048 (17)0.0054 (18)0.0015 (17)
N20.047 (2)0.039 (2)0.0310 (19)−0.0009 (18)0.0045 (17)0.0043 (17)
Zn10.0537 (4)0.0344 (3)0.0365 (3)0.0041 (3)0.0078 (2)0.0059 (2)
Br10.0718 (4)0.0582 (4)0.0742 (4)−0.0162 (3)0.0053 (3)0.0207 (3)
Br20.0605 (4)0.0634 (4)0.0489 (3)0.0125 (3)0.0017 (3)0.0138 (3)

Geometric parameters (Å, °)

C1—C21.492 (9)C8—C91.370 (10)
C1—H1A0.9600C8—H80.9300
C1—H1B0.9600C9—C101.372 (11)
C1—H1C0.9600C9—H90.9300
C2—N11.352 (7)C10—C111.403 (8)
C2—C31.373 (8)C10—H100.9300
C3—C41.376 (10)C11—N21.340 (7)
C3—H30.9300C11—C121.492 (9)
C4—C51.386 (10)C12—H12A0.9600
C4—H40.9300C12—H12B0.9600
C5—C61.383 (8)C12—H12C0.9600
C5—H50.9300Zn1—N12.071 (4)
C6—N11.342 (7)Zn1—N22.072 (4)
C6—C71.486 (8)Zn1—Br22.3400 (11)
C7—N21.343 (7)Zn1—Br12.3444 (10)
C7—C81.384 (7)
C2—C1—H1A109.5C8—C9—C10120.6 (6)
C2—C1—H1B109.5C8—C9—H9119.7
H1A—C1—H1B109.5C10—C9—H9119.7
C2—C1—H1C109.5C9—C10—C11118.5 (6)
H1A—C1—H1C109.5C9—C10—H10120.7
H1B—C1—H1C109.5C11—C10—H10120.7
N1—C2—C3120.8 (6)N2—C11—C10120.5 (6)
N1—C2—C1117.8 (5)N2—C11—C12117.5 (5)
C3—C2—C1121.4 (6)C10—C11—C12121.9 (6)
C2—C3—C4119.4 (6)C11—C12—H12A109.5
C2—C3—H3120.3C11—C12—H12B109.5
C4—C3—H3120.3H12A—C12—H12B109.5
C3—C4—C5119.5 (6)C11—C12—H12C109.5
C3—C4—H4120.2H12A—C12—H12C109.5
C5—C4—H4120.2H12B—C12—H12C109.5
C6—C5—C4119.1 (6)C6—N1—C2120.5 (5)
C6—C5—H5120.4C6—N1—Zn1113.7 (3)
C4—C5—H5120.4C2—N1—Zn1125.8 (4)
N1—C6—C5120.6 (5)C11—N2—C7120.4 (4)
N1—C6—C7116.3 (4)C11—N2—Zn1125.8 (4)
C5—C6—C7123.1 (5)C7—N2—Zn1113.8 (3)
N2—C7—C8121.2 (5)N1—Zn1—N280.22 (17)
N2—C7—C6116.0 (4)N1—Zn1—Br2114.82 (13)
C8—C7—C6122.8 (5)N2—Zn1—Br2115.86 (12)
C9—C8—C7118.7 (6)N1—Zn1—Br1113.58 (12)
C9—C8—H8120.7N2—Zn1—Br1114.84 (13)
C7—C8—H8120.7Br2—Zn1—Br1113.53 (4)
N1—C2—C3—C41.1 (10)C3—C2—N1—Zn1178.0 (5)
C1—C2—C3—C4−179.7 (7)C1—C2—N1—Zn1−1.2 (8)
C2—C3—C4—C5−0.7 (10)C10—C11—N2—C7−0.2 (8)
C3—C4—C5—C6−0.4 (10)C12—C11—N2—C7−179.5 (6)
C4—C5—C6—N11.0 (9)C10—C11—N2—Zn1179.2 (4)
C4—C5—C6—C7−178.5 (5)C12—C11—N2—Zn1−0.1 (8)
N1—C6—C7—N2−2.0 (7)C8—C7—N2—C110.9 (8)
C5—C6—C7—N2177.6 (5)C6—C7—N2—C11−178.0 (5)
N1—C6—C7—C8179.2 (5)C8—C7—N2—Zn1−178.5 (4)
C5—C6—C7—C8−1.3 (8)C6—C7—N2—Zn12.6 (6)
N2—C7—C8—C9−1.0 (9)C6—N1—Zn1—N20.8 (4)
C6—C7—C8—C9177.9 (6)C2—N1—Zn1—N2−177.8 (5)
C7—C8—C9—C100.3 (10)C6—N1—Zn1—Br2114.9 (3)
C8—C9—C10—C110.4 (10)C2—N1—Zn1—Br2−63.7 (5)
C9—C10—C11—N2−0.5 (9)C6—N1—Zn1—Br1−112.2 (3)
C9—C10—C11—C12178.8 (7)C2—N1—Zn1—Br169.3 (5)
C5—C6—N1—C2−0.6 (8)C11—N2—Zn1—N1178.7 (5)
C7—C6—N1—C2179.0 (5)C7—N2—Zn1—N1−1.9 (4)
C5—C6—N1—Zn1−179.3 (4)C11—N2—Zn1—Br265.8 (5)
C7—C6—N1—Zn10.3 (6)C7—N2—Zn1—Br2−114.8 (3)
C3—C2—N1—C6−0.4 (9)C11—N2—Zn1—Br1−69.7 (5)
C1—C2—N1—C6−179.7 (6)C7—N2—Zn1—Br1109.7 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5122).

References

  • Ahmadi, R., Kalateh, K., Alizadeh, R., Khoshtarkib, Z. & Amani, V. (2009). Acta Cryst. E65, m848–m849. [PMC free article] [PubMed]
  • Ahmadi, R., Kalateh, K., Ebadi, A., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1266. [PMC free article] [PubMed]
  • Alizadeh, R., Heidari, A., Ahmadi, R. & Amani, V. (2009). Acta Cryst. E65, m483–m484. [PMC free article] [PubMed]
  • Alizadeh, R., Kalateh, K., Ebadi, A., Ahmadi, R. & Amani, V. (2009). Acta Cryst. E65, m1250. [PMC free article] [PubMed]
  • Blake, A. J., Giunta, D., Shannon, J., Solinas, M., Walzer, F. & Woodward, S. (2007). Collect. Czech. Chem. Commun.72, 1107–1121.
  • Bruker (1998). SMART, SAINT and SADABS Bruker AXS, Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Khalighi, A., Ahmadi, R., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1211–m1212. [PMC free article] [PubMed]
  • Khan, M. A. & Tuck, D. G. (1984). Acta Cryst. C40, 60–62.
  • Khavasi, H. R., Abedi, A., Amani, V., Notash, B. & Safari, N. (2008). Polyhedron, 27, 1848–1854.
  • Khoshtarkib, Z., Ebadi, A., Alizadeh, R., Ahmadi, R. & Amani, V. (2009). Acta Cryst. E65, m739–m740. [PMC free article] [PubMed]
  • Lee, Y. M., Hong, S. J., Kim, H. J., Lee, S. H., Kwak, H., Kim, C., Kim, S. J. & Kim, Y. (2007). Inorg. Chem. Commun.10, 287–291.
  • Marjani, K., Asgarian, J., Mousavi, M. & Amani, V. (2009). Z. Anorg. Allg. Chem.635, 1633–1637.
  • Reimann, C. W., Block, S. & Perloff, A. (1966). Inorg. Chem.5, 1185–1189.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wriedt, M., Jess, I. & Näther, C. (2008). Acta Cryst. E64, m315. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography