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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o843.
Published online 2009 March 25. doi:  10.1107/S160053680900974X
PMCID: PMC2969055

2,5-Dibromo­pyridine

Abstract

In the title compound, C5H3Br2N, C—H(...)N hydrogen-bonding inter­actions and Br(...)Br inter­actions [3.9418 (3) and 3.8986 (3) Å] connect the mol­ecules into planar sheets stacked perpendicular to the b axis. In addition, pyrid­yl–pyridyl inter­sheet π–π stacking inter­actions [centroid–centroid distance = 4.12 (1) Å] result in a three-dimensional network.

Related literature

For hydrogen bonding, see: Desiraju (1997 [triangle]). For related structures, see: Al-Far & Ali (2007 [triangle], 2008 [triangle]); Ali & Al-Far (2008 [triangle]); Ali et al. (2008a [triangle],b [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For theoretical analysis, see: Awwadi et al. (2006 [triangle], 2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o843-scheme1.jpg

Experimental

Crystal data

  • C5H3Br2N
  • M r = 236.90
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o843-efi1.jpg
  • a = 6.1063 (4) Å
  • b = 6.5442 (4) Å
  • c = 15.8196 (9) Å
  • V = 632.17 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 12.71 mm−1
  • T = 90 K
  • 0.46 × 0.21 × 0.14 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: numerical (SADABS; Bruker, 2004 [triangle]) T min = 0.053, T max = 0.170
  • 8997 measured reflections
  • 996 independent reflections
  • 887 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.021
  • wR(F 2) = 0.054
  • S = 1.05
  • 996 reflections
  • 49 parameters
  • H-atom parameters constrained
  • Δρmax = 0.68 e Å−3
  • Δρmin = −0.77 e Å−3

Data collection: SMART (Bruker, 2006 [triangle]); cell refinement: SAINT-Plus (Bruker, 2006 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 [triangle]); molecular graphics: XP (Bruker, 2004 [triangle]) and SHELXTL; software used to prepare material for publication: XCIF (Bruker, 2004 [triangle]) and SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680900974X/pv2146sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900974X/pv2146Isup2.hkl

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

Acknowledgments

Al-Balqa’a Applied University and Al al-Bayt University are thanked for financial support.

supplementary crystallographic information

Comment

Non-covalent interactions play an important role in organizing structural units in both natural and artificial systems (Desiraju, 1997). The interactions governing the crystal organization are expected to affect the packing and specific properties of solids. Intermolecular interactions are the essence of supramolecular chemistry, and the field of crystal supramolecularity seeks to understand intermolecular interactions by analyses of crystal packing. We are presently interested in the synthesis and the structural aspects of halo-metal anion salts containing different organic cations (Al-Far & Ali 2007, 2008; Ali et al. 2008a, b; Ali & Al-Far 2008). The title compound, (I), arose accidentally when attempting to crystallize CdBr42- with 2,5-bibromopyridinium cation. The compound had not been reported previously, thus, the structure of (I) has been characterized crystallographically and is presented here.

The bond distances and angles within the molecule of (I) (Fig. 1) are normal (Allen et al., 1987). There is a non-classical hydrogen bonding interaction of the type C—H···N in the crystal structure which links molecules into one-dimensional chains (Fig. 2) parallel to the a-axis. The strength of the hydrogen bonds is represented by relatively short D···A distance and D—H···A angle (H···A = 2.38 Å, D—H···A 175°, Table 1). The resulting chains are further connected through Br···Br interactions in a zig zag arrangement to form sheets in the ac plane (Fig. 2); the Br···Br separation being 3.9418 (3) and 3.8986 (3) Å. The sheets are stacked along the b-axis with pyridyl···pyridyl π···π stacking intermolecular inreactions with distance between the centroids of the rings being 4.12 (1) Å. It is noteworthy that structural and theoritical results (Awwadi et al., 2006; Awwadi et al., 2007), show the significance of Br···Br bonding synthons in influencing structures of crystalline materials and in use as potential building blocks in crystal engineering via supramolecular synthesis.

Experimental

The title compound crystallized during a reaction aiming to crystallize the anion [CuBr4]2- with 2,5-dibromopyridinium cation. Colorless diamond like crystals of the title compound were obtained from an ethanolic solution of the reaction which involved a sequential addition to excess 2,5-dibrormopyridine (2.25 mmole) in ethanol of CdCl2 (1 mmole) and 60% HBr (1 ml) in ethanol.

Refinement

Hydrogen atoms were positioned geometrically, with C—H = 0.95 Å, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
A molecular drawing of (I) shown with 50% probability ellipsoids.
Fig. 2.
Packing diagram of (I) down the b-axis. Hydrogen bonding and Br···Br interactions are shown as dashed lines.

Crystal data

C5H3Br2NF(000) = 440
Mr = 236.90Dx = 2.489 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 5485 reflections
a = 6.1063 (4) Åθ = 2.6–30.0°
b = 6.5442 (4) ŵ = 12.71 mm1
c = 15.8196 (9) ÅT = 90 K
V = 632.17 (7) Å3Diamond, colourless
Z = 40.46 × 0.21 × 0.14 mm

Data collection

Bruker SMART APEX diffractometer996 independent reflections
Radiation source: fine-focus sealed tube887 reflections with I > 2σ(I)
graphiteRint = 0.030
Detector resolution: 8.3 pixels mm-1θmax = 30.0°, θmin = 3.6°
ω scansh = −8→8
Absorption correction: numerical (SADABS; Bruker, 2004)k = −9→9
Tmin = 0.053, Tmax = 0.170l = −22→22
8997 measured reflections

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)] = 0.021Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0364P)2 + 0.1337P] where P = (Fo2 + 2Fc2)/3
996 reflections(Δ/σ)max < 0.001
49 parametersΔρmax = 0.68 e Å3
0 restraintsΔρmin = −0.77 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
Br20.41023 (4)0.75000.171199 (12)0.01101 (9)
N10.4781 (3)0.7500−0.00105 (12)0.0077 (4)
Br50.98268 (4)0.7500−0.173378 (13)0.01214 (9)
C20.5860 (4)0.75000.07141 (12)0.0063 (4)
C30.8124 (3)0.75000.07962 (13)0.0089 (4)
H3A0.88080.75000.13360.011*
C40.9342 (4)0.75000.00590 (14)0.0088 (4)
H4A1.08970.75000.00770.011*
C50.8236 (4)0.7500−0.07079 (12)0.0074 (4)
C60.5958 (4)0.7500−0.07196 (12)0.0083 (4)
H6A0.52210.7500−0.12480.010*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br20.01285 (15)0.01709 (15)0.00310 (12)0.0000.00345 (7)0.000
N10.0081 (9)0.0110 (9)0.0041 (8)0.0000.0000 (6)0.000
Br50.01335 (15)0.01839 (15)0.00466 (13)0.0000.00480 (7)0.000
C20.0095 (11)0.0078 (10)0.0015 (8)0.0000.0012 (7)0.000
C30.0087 (10)0.0114 (10)0.0066 (9)0.000−0.0024 (8)0.000
C40.0067 (9)0.0114 (10)0.0084 (10)0.000−0.0018 (8)0.000
C50.0088 (10)0.0096 (10)0.0040 (9)0.0000.0026 (7)0.000
C60.0100 (11)0.0100 (11)0.0048 (9)0.000−0.0019 (7)0.000

Geometric parameters (Å, °)

Br2—C21.909 (2)C3—H3A0.9500
N1—C21.322 (3)C4—C51.389 (3)
N1—C61.332 (3)C4—H4A0.9500
Br5—C51.891 (2)C5—C61.391 (3)
C2—C31.389 (3)C6—H6A0.9500
C3—C41.383 (3)
C2—N1—C6117.43 (19)C3—C4—H4A120.8
N1—C2—C3125.27 (19)C5—C4—H4A120.8
N1—C2—Br2115.88 (16)C4—C5—C6119.87 (19)
C3—C2—Br2118.85 (15)C4—C5—Br5119.98 (17)
C4—C3—C2117.15 (19)C6—C5—Br5120.15 (16)
C4—C3—H3A121.4N1—C6—C5121.91 (19)
C2—C3—H3A121.4N1—C6—H6A119.0
C3—C4—C5118.38 (19)C5—C6—H6A119.0
C6—N1—C2—C30.0C3—C4—C5—C60.0
C6—N1—C2—Br2180.0C3—C4—C5—Br5180.0
N1—C2—C3—C40.0C2—N1—C6—C50.0
Br2—C2—C3—C4180.0C4—C5—C6—N10.0
C2—C3—C4—C50.0Br5—C5—C6—N1180.0

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C4—H4A···N1i0.952.383.323 (3)175

Symmetry codes: (i) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2146).

References

  • Al-Far, R. & Ali, B. F. (2007). J. Chem. Crystallogr.37, 333-341.
  • Al-Far, R. & Ali, B. F. (2008). J. Chem. Crystallogr.38, 373-379.
  • Ali, B. F. & R. Al-Far, R. (2008). J. Chem. Crystallogr.37, 689–693.
  • Ali, B. F., Al-Far, R. H. & Haddad, S. F. (2008a). Acta Cryst. E64, m485–m486. [PMC free article] [PubMed]
  • Ali, B. F., Al-Far, R. H. & Haddad, S. F. (2008b). Acta Cryst. E64, m751–m752. [PMC free article] [PubMed]
  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L. A. G., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Awwadi, F. F., Willett, R. D., Peterson, K. A. & Twamley, B. (2006). Chem. Eur. J.12, 8952–8960. [PubMed]
  • Awwadi, F. F., Willett, R. D., Peterson, K. A. & Twamley, B. (2007). J. Phys. Chem. A, 111, 2319–2328. [PubMed]
  • Bruker (2004). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2006). SMART and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Desiraju, G. R. (1997). Chem. Commun. pp. 1475–1482.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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