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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): m677.
Published online 2010 May 22. doi:  10.1107/S1600536810017551
PMCID: PMC2979554

(2,2′-Bipyridine-κ2 N,N′)dibromido(dimethyl sulfoxide-κO)zinc(II)

Abstract

In the mol­ecule of the title compound, [ZnBr2(C10H8N2)(C2H6OS)], the ZnII atom is five-coordinated in a distorted trigonal–bipyramidal configuration by two N atoms from one 2,2′-bipyridine, one O atom from one dimethyl­sulfoxide molecule and two Br atoms. Inter­molecular π–π stacking between parallel pyridine rings [face-to-face distance 3.32 (4) Å] and C—H(...)Br and C—H(...)O hydrogen-bonding interactions are present in the crystal structure.

Related literature

For related structures, see: Ahmadi et al. (2008 [triangle]); Alizadeh, Kalateh, Ebadi et al. (2009 [triangle]); Alizadeh, Kalateh, Khoshtarkib et al. (2009 [triangle]); Alizadeh, Khoshtarkib et al. (2009 [triangle]); Blake et al. (2007 [triangle]); Khan & Tuck (1984 [triangle]); Marjani et al. (2007 [triangle]); Khalighi et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m677-scheme1.jpg

Experimental

Crystal data

  • [ZnBr2(C10H8N2)(C2H6OS)]
  • M r = 459.51
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m677-efi1.jpg
  • a = 9.4802 (10) Å
  • b = 8.3449 (7) Å
  • c = 19.989 (2) Å
  • β = 95.185 (8)°
  • V = 1574.9 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 6.76 mm−1
  • T = 298 K
  • 0.30 × 0.25 × 0.20 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.148, T max = 0.260
  • 12674 measured reflections
  • 4245 independent reflections
  • 3229 reflections with I > 2σ(I)
  • R int = 0.078

Refinement

  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.140
  • S = 1.13
  • 4245 reflections
  • 175 parameters
  • H-atom parameters constrained
  • Δρmax = 1.08 e Å−3
  • Δρmin = −1.46 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); 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)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017551/xu2761sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017551/xu2761Isup2.hkl

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

Acknowledgments

The author is grateful to the University of Urmiyeh for financial support.

supplementary crystallographic information

Comment

There are several ZnII complexes containing 2,2'-bipyridine and 2,2'-bipyridine derivatives such as, [ZnCl2(bipy)], (II), (Khan & Tuck, 1984), [ZnCl2(5,5'-dmbpy)], (III), (Khalighi et al., 2008), [ZnCl2(6-mbpy)], (IV), (Ahmadi, et al., 2008), [ZnCl2(6,6'-dmbpy)], (V), (Alizadeh, Kalateh, Ebadi, et al., 2009), [ZnBr2(6,6'-dmbpy)], (VI), (Alizadeh, Khoshtarkib et al., 2009), [ZnI2(6,6'-dmbpy)], (VII), (Alizadeh, Kalateh, Khoshtarkib et al., 2009), [ZnCl2(bipy)(DMSO)], (VIII), (Marjani et al., 2007) and [ZnBr2(4,4'-(dtbpy)].(Et2O), (IX), (Blake et al., 2007) [where bipy is 2,2'-bipyridine, 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine, 6,6'-dmbpy is 6,6'-dimethyl-2,2'-bipyridine, DMSO is dimethyl sulfoxide and dtbpy is 4,4'-di-tert-butyl-2,2'-bipyridine] 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 five-coordinate in a distorted trigonal-bipyramidal configurations by two N atoms from one 2,2'-bipyridine, one atom from one dimethyl sulfoxide and two Br atoms. The Zn—N and Zn—O bond lengths and angles (Table 1) are within normal range (VIII) and Zn—Br bond lengths and angles are within normal range (VI).

The π-π contacts between the pyridine rings, Cg1···Cg3i, Cg2···Cg2ii, Cg2···Cg3i, Cg3···Cg1i and Cg3···Cg2i [symmetry cods: (i) 1-X,1-Y,1-Z, (ii) 1-X,-Y,1-Z, where Cg1, Cg2 and Cg3 are centroids of the rings (Zn1/N1/C5—C6/N2), (N1/C1—C5) and (N2/C6—C10), respectively] with centroid-centroid distance of 3.475 (3), 3.661 (3), 3.721 (3), 3.476 (3) and 3.721 (3) Å, respectively, and intramolecular C—H···O and C—H···Br hydrogen bonding it seems effective in the stabilization of the crystal structure (Fig. 2).

Experimental

For the preparation of the title compound, (I), a solution of 2,2'-bipyridine (0.17 g, 1.10 mmol) in methanol (10 ml) was added to a solution of ZnBr2 (0.25 g, 1.10 mmol) in methanol (5 ml) at room temperature. The suitable crystals for X-ray diffraction experiment were obtained by methanol diffusion to a colorless solution in DMSO. Suitable crystals were isolated after one week (yield; 0.36 g, 71.2%).

Refinement

H atoms were positioned geometrically with C—H = 0.93 Å for aromatic and 0.96 Å for methyl, 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 30% probability level.
Fig. 2.
Unit-cell packing diagram for (I).

Crystal data

[ZnBr2(C10H8N2)(C2H6OS)]F(000) = 896
Mr = 459.51Dx = 1.938 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 653 reflections
a = 9.4802 (10) Åθ = 2.1–29.2°
b = 8.3449 (7) ŵ = 6.76 mm1
c = 19.989 (2) ÅT = 298 K
β = 95.185 (8)°Block, colorless
V = 1574.9 (3) Å30.30 × 0.25 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer4245 independent reflections
Radiation source: fine-focus sealed tube3229 reflections with I > 2σ(I)
graphiteRint = 0.078
[var phi] and ω scansθmax = 29.2°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −12→12
Tmin = 0.148, Tmax = 0.260k = −11→11
12674 measured reflectionsl = −27→25

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.140w = 1/[σ2(Fo2) + (0.0602P)2 + 1.8278P] where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max = 0.005
4245 reflectionsΔρmax = 1.08 e Å3
175 parametersΔρmin = −1.46 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0087 (7)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C10.5556 (5)0.1151 (7)0.3831 (3)0.0377 (10)
H10.52860.09800.33780.045*
C20.6783 (5)0.0424 (7)0.4117 (3)0.0425 (12)
H20.7333−0.02080.38590.051*
C30.7166 (6)0.0660 (7)0.4788 (3)0.0462 (13)
H30.79820.01850.49920.055*
C40.6335 (5)0.1603 (6)0.5155 (3)0.0383 (10)
H40.65810.17720.56110.046*
C50.5129 (5)0.2297 (6)0.4840 (2)0.0295 (9)
C60.4154 (5)0.3323 (6)0.5190 (2)0.0311 (9)
C70.4311 (6)0.3600 (7)0.5883 (2)0.0406 (11)
H70.50560.31370.61500.049*
C80.3346 (6)0.4570 (7)0.6166 (3)0.0432 (12)
H80.34330.47710.66250.052*
C90.2254 (5)0.5234 (7)0.5759 (3)0.0422 (12)
H90.15890.58890.59390.051*
C100.2162 (5)0.4915 (7)0.5085 (3)0.0395 (11)
H100.14210.53660.48120.047*
C110.2234 (7)0.7783 (10)0.2635 (4)0.0621 (18)
H11A0.31670.74120.25640.075*
H11B0.23020.86830.29350.075*
H11C0.17500.80990.22130.075*
C12−0.0109 (6)0.7414 (10)0.3256 (4)0.0650 (19)
H12A0.02810.82810.35290.078*
H12B−0.06980.67650.35140.078*
H12C−0.06650.78380.28720.078*
N10.4750 (4)0.2084 (5)0.41813 (19)0.0324 (8)
N20.3090 (4)0.3984 (5)0.48005 (19)0.0324 (8)
O10.2163 (4)0.5774 (5)0.36384 (18)0.0440 (9)
Zn10.29167 (5)0.33824 (7)0.37552 (3)0.03244 (16)
Br10.37506 (6)0.34269 (8)0.26199 (3)0.04918 (19)
Br20.07887 (6)0.17861 (8)0.37356 (3)0.05171 (19)
S10.12833 (14)0.62307 (17)0.29876 (7)0.0413 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.040 (2)0.040 (3)0.033 (2)0.006 (2)0.0043 (19)−0.001 (2)
C20.042 (3)0.038 (3)0.049 (3)0.009 (2)0.012 (2)−0.001 (2)
C30.041 (3)0.044 (3)0.052 (3)0.009 (2)−0.002 (2)0.008 (3)
C40.038 (2)0.041 (3)0.035 (2)−0.001 (2)−0.0051 (18)0.004 (2)
C50.032 (2)0.028 (2)0.028 (2)−0.0061 (17)0.0007 (16)0.0022 (17)
C60.0297 (19)0.031 (2)0.032 (2)−0.0062 (17)0.0025 (16)−0.0013 (19)
C70.043 (3)0.047 (3)0.031 (2)−0.006 (2)−0.0026 (19)−0.001 (2)
C80.052 (3)0.049 (3)0.029 (2)−0.008 (2)0.008 (2)−0.003 (2)
C90.046 (3)0.040 (3)0.043 (3)0.000 (2)0.018 (2)−0.001 (2)
C100.037 (2)0.043 (3)0.039 (2)0.005 (2)0.0079 (19)0.004 (2)
C110.047 (3)0.080 (5)0.060 (4)−0.005 (3)0.010 (3)0.026 (4)
C120.040 (3)0.071 (5)0.086 (5)0.006 (3)0.014 (3)0.022 (4)
N10.0333 (18)0.034 (2)0.0299 (18)0.0003 (15)0.0015 (14)0.0026 (16)
N20.0278 (17)0.039 (2)0.0309 (18)−0.0022 (15)0.0029 (14)−0.0005 (17)
O10.053 (2)0.041 (2)0.0352 (18)0.0093 (16)−0.0089 (15)0.0020 (16)
Zn10.0303 (3)0.0378 (3)0.0285 (3)0.0010 (2)−0.00125 (19)0.0005 (2)
Br10.0467 (3)0.0704 (4)0.0309 (2)0.0102 (3)0.0059 (2)0.0055 (3)
Br20.0373 (3)0.0562 (4)0.0604 (4)−0.0122 (2)−0.0025 (2)−0.0009 (3)
S10.0409 (6)0.0409 (7)0.0397 (6)0.0015 (5)−0.0084 (5)0.0036 (5)

Geometric parameters (Å, °)

C1—N11.333 (6)C9—H90.9300
C1—C21.388 (7)C10—N21.338 (6)
C1—H10.9300C10—H100.9300
C2—C31.372 (8)C11—S11.761 (7)
C2—H20.9300C11—H11A0.9600
C3—C41.372 (8)C11—H11B0.9600
C3—H30.9300C11—H11C0.9600
C4—C51.382 (6)C12—S11.770 (7)
C4—H40.9300C12—H12A0.9600
C5—N11.345 (6)C12—H12B0.9600
C5—C61.480 (6)C12—H12C0.9600
C6—N21.336 (6)Zn1—N12.157 (4)
C6—C71.401 (6)Zn1—N22.141 (4)
C7—C81.380 (8)S1—O11.529 (4)
C7—H70.9300Zn1—O12.125 (4)
C8—C91.374 (8)Zn1—Br12.4701 (8)
C8—H80.9300Zn1—Br22.4148 (8)
C9—C101.369 (7)
N1—C1—C2122.6 (5)S1—C11—H11B109.5
N1—C1—H1118.7H11A—C11—H11B109.5
C2—C1—H1118.7S1—C11—H11C109.5
C3—C2—C1118.5 (5)H11A—C11—H11C109.5
C3—C2—H2120.7H11B—C11—H11C109.5
C1—C2—H2120.7S1—C12—H12A109.5
C2—C3—C4119.4 (5)S1—C12—H12B109.5
C2—C3—H3120.3H12A—C12—H12B109.5
C4—C3—H3120.3S1—C12—H12C109.5
C3—C4—C5119.2 (5)H12A—C12—H12C109.5
C3—C4—H4120.4H12B—C12—H12C109.5
C5—C4—H4120.4C1—N1—C5118.4 (4)
N1—C5—C4121.8 (5)C1—N1—Zn1124.5 (3)
N1—C5—C6114.5 (4)C5—N1—Zn1117.1 (3)
C4—C5—C6123.6 (4)C6—N2—C10118.9 (4)
N2—C6—C7121.0 (4)C6—N2—Zn1117.3 (3)
N2—C6—C5115.8 (4)C10—N2—Zn1123.7 (3)
C7—C6—C5123.2 (4)S1—O1—Zn1118.7 (2)
C8—C7—C6119.1 (5)O1—Zn1—N283.24 (15)
C8—C7—H7120.4O1—Zn1—N1139.98 (15)
C6—C7—H7120.4N2—Zn1—N175.19 (15)
C9—C8—C7119.1 (5)O1—Zn1—Br2104.13 (11)
C9—C8—H8120.4N2—Zn1—Br297.80 (11)
C7—C8—H8120.4N1—Zn1—Br2111.81 (11)
C10—C9—C8118.8 (5)O1—Zn1—Br190.99 (11)
C10—C9—H9120.6N2—Zn1—Br1152.93 (11)
C8—C9—H9120.6N1—Zn1—Br193.27 (11)
N2—C10—C9123.1 (5)Br2—Zn1—Br1109.25 (3)
N2—C10—H10118.5O1—S1—C11105.3 (3)
C9—C10—H10118.5O1—S1—C12104.2 (3)
S1—C11—H11A109.5C11—S1—C1297.7 (4)
N1—C1—C2—C31.0 (9)C9—C10—N2—C60.4 (8)
C1—C2—C3—C4−0.2 (9)C9—C10—N2—Zn1177.1 (4)
C2—C3—C4—C5−0.1 (8)S1—O1—Zn1—N2−159.5 (3)
C3—C4—C5—N1−0.5 (8)S1—O1—Zn1—N1143.3 (2)
C3—C4—C5—C6179.5 (5)S1—O1—Zn1—Br2−63.2 (3)
N1—C5—C6—N2−4.3 (6)S1—O1—Zn1—Br147.0 (3)
C4—C5—C6—N2175.7 (4)C6—N2—Zn1—O1−146.3 (4)
N1—C5—C6—C7175.5 (4)C10—N2—Zn1—O136.9 (4)
C4—C5—C6—C7−4.5 (7)C6—N2—Zn1—N1−0.3 (3)
N2—C6—C7—C80.1 (8)C10—N2—Zn1—N1−177.1 (4)
C5—C6—C7—C8−179.7 (5)C6—N2—Zn1—Br2110.3 (3)
C6—C7—C8—C90.2 (8)C10—N2—Zn1—Br2−66.5 (4)
C7—C8—C9—C10−0.2 (8)C6—N2—Zn1—Br1−67.5 (5)
C8—C9—C10—N2−0.1 (8)C10—N2—Zn1—Br1115.7 (4)
C2—C1—N1—C5−1.5 (8)C1—N1—Zn1—O1−119.4 (4)
C2—C1—N1—Zn1175.5 (4)C5—N1—Zn1—O157.6 (4)
C4—C5—N1—C11.2 (7)C1—N1—Zn1—N2−179.1 (4)
C6—C5—N1—C1−178.8 (4)C5—N1—Zn1—N2−2.2 (3)
C4—C5—N1—Zn1−175.9 (4)C1—N1—Zn1—Br288.3 (4)
C6—C5—N1—Zn14.0 (5)C5—N1—Zn1—Br2−94.7 (3)
C7—C6—N2—C10−0.4 (7)C1—N1—Zn1—Br1−24.0 (4)
C5—C6—N2—C10179.4 (4)C5—N1—Zn1—Br1153.0 (3)
C7—C6—N2—Zn1−177.3 (4)Zn1—O1—S1—C11−120.4 (4)
C5—C6—N2—Zn12.5 (5)Zn1—O1—S1—C12137.3 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1···Br10.932.863.413 (6)119
C10—H10···O10.932.532.979 (7)110

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2761).

References

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  • 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]
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