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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o467.
Published online 2008 January 18. doi:  10.1107/S1600536808000913
PMCID: PMC2960452

1,1′-(Butane-1,4-di­yl)dipyridinium dibromide dihydrate

Abstract

The organic cation in the title compound, C14H18N2 2+·2Br·2H2O, is situated on an inversion centre. The cations, anions and water mol­ecules are linked via O—H(...)Br, C—H(...)Br and C—H(...)O hydrogen bonds, and π–π stacking inter­actions between adjacent pyridine rings, with a centroid–centroid separation of 3.8518 (17) Å.

Related literature

For general background, see: Day et al. (2000 [triangle], 2002 [triangle]); Freeman et al. (1981 [triangle]); Kim et al. (2000 [triangle]).

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Object name is e-64-0o467-scheme1.jpg

Experimental

Crystal data

  • C14H18N2 2+·2Br·2H2O
  • M r = 410.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o467-efi1.jpg
  • a = 11.0068 (13) Å
  • b = 7.1484 (8) Å
  • c = 12.0607 (13) Å
  • β = 111.602 (7)°
  • V = 882.30 (18) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 4.60 mm−1
  • T = 293 (2) K
  • 0.21 × 0.18 × 0.16 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.393, T max = 0.478
  • 7189 measured reflections
  • 1723 independent reflections
  • 1483 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.074
  • S = 1.06
  • 1723 reflections
  • 92 parameters
  • 3 restraints
  • H-atom parameters constrained
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.45 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [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
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808000913/fb2085sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808000913/fb2085Isup2.hkl

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

Acknowledgments

We acknowledge the support of the National Natural Science Foundation of China (No. 20662003) and the Foundation of the Governor of Guizhou Province, China.

supplementary crystallographic information

Comment

As a part of our ongoing investigation of polyaromatic compounds, we present a structure determination of the compound containing the pyridyl or alkyl groups that can be involved in intermolecular interactions with cucurbit[n]urils (CB[n]) (Freeman et al., 1981; Day et al., 2000; Day et al., 2002; Kim et al., 2000).

The organic cations in the title structure are situated on the inversion centres (Fig. 1) which coincide with the midpoint of the C7—C7i bond [the symmetry code: (i) 1 - x,-y,1 - z]. The angle between the plane of the pyridine ring and the plane through C6,C7,C7i,C6i chain is 86.57 (13)°. The anions and water molecules are linked via O—H···Br, C—H···Br, C—H···O hydrogen bonds (Table 1). In addition, the π···π stacking interactions occur between the adjacent pyridine rings, with the centroid-centroid separation being 3.8518 (17)Å [the symmetry code: (ii) 3/2 - x,-1/2 + y,1/2 - z].

Experimental

A solution of 1,4-dibromine-butadinol (2.16 g, 0.01 mol) was added to a stirred solution of pyridine (1.98 g, 0.025 mol) in 1,4-dioxane (50 ml) at 110°C for 5 h. After cooling to room temperature, the mixture was filtered. The solid product was dissolved in 80 ml of water, and then set aside for three weeks to obtain colourless diamond-like crystals with average dimensions about 0.2 mm.

Refinement

All the H atoms were located in the difference Fourier map. The H atoms attached to the carbon atoms were situated into the idealized positions and refined in a riding-atom approximation. The constraints: C—Haryl=0.93 and C—Hmethylene=0.97 Å; Uiso(H) = 1.2Ueq(C).

The positional parameters of water H atoms were restrained with the distances O—H equal to 0.85 (1)Å while with the distance between both H atoms equal to 1.35 (2) Å. The water H atoms were refined as riding with Uiso(H) = 1.2Ueq(O).

Figures

Fig. 1.
The molecular structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Symmetry code of C7a: -x + 1, -y, -z + 1.

Crystal data

C14H18N22+·2Br·2H2OF000 = 412
Mr = 410.14Dx = 1.544 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1730 reflections
a = 11.0068 (13) Åθ = 0.5–0.6º
b = 7.1484 (8) ŵ = 4.60 mm1
c = 12.0607 (13) ÅT = 293 (2) K
β = 111.602 (7)ºDiamond, colourless
V = 882.30 (18) Å30.21 × 0.18 × 0.16 mm
Z = 2

Data collection

Bruker CCD area-detector diffractometer1723 independent reflections
Radiation source: fine-focus sealed tube1483 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.041
T = 293(2) Kθmax = 26.0º
[var phi] and ω scansθmin = 2.1º
Absorption correction: multi-scan(SADABS; Bruker, 2005)h = −13→13
Tmin = 0.393, Tmax = 0.478k = −8→8
7189 measured reflectionsl = −14→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.074  w = 1/[σ2(Fo2) + (0.0377P)2 + 0.1891P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
1723 reflectionsΔρmax = 0.48 e Å3
92 parametersΔρmin = −0.45 e Å3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
38 constraintsExtinction coefficient: 0.073 (3)
Primary atom site location: structure-invariant direct methods

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
C10.6134 (3)0.1783 (4)0.2544 (2)0.0512 (6)
H10.52280.18030.21750.061*
C20.6896 (3)0.1660 (4)0.1867 (2)0.0602 (7)
H20.65090.15980.10400.072*
C30.8220 (3)0.1629 (4)0.2408 (3)0.0627 (8)
H30.87410.15530.19530.075*
C40.8782 (3)0.1710 (5)0.3631 (3)0.0655 (8)
H40.96860.16870.40120.079*
C50.7990 (3)0.1826 (4)0.4285 (2)0.0515 (6)
H50.83590.18700.51140.062*
C60.5845 (2)0.1926 (3)0.4453 (2)0.0458 (6)
H6A0.50900.27110.40590.055*
H6B0.63290.24620.52290.055*
C70.5400 (2)−0.0023 (3)0.46040 (19)0.0389 (5)
H7A0.6155−0.08260.49590.047*
H7B0.4875−0.05340.38300.047*
N10.66903 (18)0.1874 (3)0.37309 (16)0.0393 (5)
O1W0.6333 (2)0.5305 (3)0.7900 (2)0.0762 (6)
H1WA0.64610.41490.80700.091*
H1WB0.67350.55220.74370.091*
Br10.69404 (3)0.09270 (4)0.88751 (2)0.05201 (16)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0517 (15)0.0538 (15)0.0443 (13)0.0009 (12)0.0133 (12)0.0042 (12)
C20.087 (2)0.0545 (16)0.0457 (14)0.0055 (15)0.0326 (15)0.0043 (13)
C30.086 (2)0.0498 (15)0.077 (2)−0.0030 (15)0.0598 (19)0.0006 (15)
C40.0500 (17)0.0680 (18)0.087 (2)−0.0151 (15)0.0353 (16)−0.0133 (17)
C50.0428 (15)0.0613 (16)0.0487 (14)−0.0095 (12)0.0148 (12)−0.0098 (13)
C60.0466 (14)0.0484 (14)0.0492 (13)−0.0010 (11)0.0253 (12)−0.0008 (11)
C70.0359 (12)0.0449 (13)0.0359 (11)−0.0006 (10)0.0133 (10)0.0009 (10)
N10.0417 (12)0.0374 (11)0.0421 (10)−0.0042 (8)0.0193 (9)−0.0015 (8)
O1W0.0797 (15)0.0731 (13)0.0922 (15)0.0221 (12)0.0509 (14)0.0232 (13)
Br10.0555 (2)0.0537 (2)0.0485 (2)0.00237 (12)0.02118 (15)0.00144 (11)

Geometric parameters (Å, °)

C1—N11.335 (3)C5—H50.9300
C1—C21.372 (4)C6—N11.490 (3)
C1—H10.9300C6—C71.510 (3)
C2—C31.359 (4)C6—H6A0.9700
C2—H20.9300C6—H6B0.9700
C3—C41.375 (4)C7—C7i1.519 (4)
C3—H30.9300C7—H7A0.9700
C4—C51.377 (4)C7—H7B0.9700
C4—H40.9300O1W—H1WA0.8507
C5—N11.338 (3)O1W—H1WB0.8454
N1—C1—C2120.1 (3)N1—C6—H6A109.6
N1—C1—H1120.0C7—C6—H6A109.6
C2—C1—H1120.0N1—C6—H6B109.6
C3—C2—C1119.9 (3)C7—C6—H6B109.6
C3—C2—H2120.1H6A—C6—H6B108.1
C1—C2—H2120.1C6—C7—C7i110.2 (2)
C2—C3—C4119.6 (2)C6—C7—H7A109.6
C2—C3—H3120.2C7i—C7—H7A109.6
C4—C3—H3120.2C6—C7—H7B109.6
C3—C4—C5119.2 (3)C7i—C7—H7B109.6
C3—C4—H4120.4H7A—C7—H7B108.1
C5—C4—H4120.4C1—N1—C5121.2 (2)
N1—C5—C4120.1 (3)C1—N1—C6119.3 (2)
N1—C5—H5120.0C5—N1—C6119.4 (2)
C4—C5—H5120.0H1WA—O1W—H1WB104.9
N1—C6—C7110.37 (19)
N1—C1—C2—C30.1 (4)C2—C1—N1—C6−177.4 (2)
C1—C2—C3—C40.4 (5)C4—C5—N1—C11.0 (4)
C2—C3—C4—C5−0.1 (5)C4—C5—N1—C6177.7 (3)
C3—C4—C5—N1−0.6 (4)C7—C6—N1—C181.1 (3)
N1—C6—C7—C7i176.9 (2)C7—C6—N1—C5−95.6 (3)
C2—C1—N1—C5−0.8 (4)

Symmetry codes: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H1WA···Br10.852.483.323 (2)172
O1W—H1WB···Br1ii0.852.533.375 (2)175
C2—H2···Br1iii0.932.863.664 (3)145
C5—H5···O1Wiv0.932.553.376 (3)148

Symmetry codes: (ii) −x+3/2, y+1/2, −z+3/2; (iii) x, y, z−1; (iv) −x+3/2, y−1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FB2085).

References

  • Bruker (2005). APEX2, SADABS and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Day, A. I., Arnold, A. P. & Blanch, R. J. (2000). Patent No. WO/2000/068232.
  • Day, A. I., Blanch, R. J., Arnold, A. P., Lorenzo, S., Lewis, G. R. & Dance, I. (2002). Angew. Chem. Int. Ed.41, 275–277. [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Freeman, W. A., Mock, W. L. & Shih, N. Y. (1981). J. Am. Chem. Soc.103, 7367–7368.
  • Kim, J., Jung, I.-S., Kim, S.-Y., Lee, E., Kang, J.-K., Sakamoto, S., Yamaguchi, K. & Kim, K. (2000). J. Am. Chem. Soc.122, 540–541.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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