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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o183.
Published online 2007 December 6. doi:  10.1107/S1600536807063970
PMCID: PMC2915246

Octane-1,8-diyldipyridinium dibromide dihydrate

Abstract

The asymmetric unit of the title compound, C18H26N2 2+·2Br·2H2O, consists of one-half of the organic cation, one Br anion and one water mol­ecule. The organic cation is situated on a centre of inversion. The dihedral angle between the pyridine ring and the plane of the central linkage is 59.3 (1)°. The cations, anions and water mol­ecules are linked via O—H(...)Br, C—H(...)Br and C—H(...)O hydrogen bonds, forming a three-dimensional framework.

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-64-0o183-scheme1.jpg

Experimental

Crystal data

  • C18H26N2 2+·2Br·2H2O
  • M r = 466.26
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o183-efi1.jpg
  • a = 9.8329 (7) Å
  • b = 13.3000 (11) Å
  • c = 16.5688 (13) Å
  • V = 2166.8 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 3.75 mm−1
  • T = 273 (2) K
  • 0.32 × 0.24 × 0.19 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.380, T max = 0.536 (expected range = 0.347–0.490)
  • 21410 measured reflections
  • 2503 independent reflections
  • 1842 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.077
  • S = 1.01
  • 2503 reflections
  • 109 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.39 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, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [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/S1600536807063970/ci2531sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063970/ci2531Isup2.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 part of our ongoing investigation on bipyridyl compounds, we present here the crystal structure of the title compound, (I), which can develop strong intermolecular interactions with cucurbit[n]urils (CB[n]) (Freeman et al., 1981; Day et al., 2000, 2002; Kim et al., 2000).

The asymmetric unit of compound (I) (Fig. 1) consists of one-half of the organic cation, one Br- anion and one lattice water molecule. The organic cation is situated on a centre of inversion which coincides with the midpoint of the C9—C9i bond [symmetry code: (i) 1 - x, 1 - y, -z]. The two pyridine rings are parallel by virtue of the centre of symmetry. The dihedral angle between the pyridine ring and the central C6—C9/C6i—C9i chain is 59.3 (1)°. The cations, anions and water molecules are linked via O—H···Br, C—H···Br and C—H···O hydrogen bonds (Table 1) forming a three-dimensional framework.

Experimental

A solution of 1,8-dibromine-octane (2.72 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 383 K for 5 h. After cooling to room temperature, the mixture was filtered. The solid product was dissolved in 80 ml water, and then set aside for four weeks to obtain colourless crystals of the title compound.

Refinement

Water H atoms were located in a difference Fourier map and refined as riding in their as-found positions relative to the parent O atom, with Uiso(H) = 1.2Ueq(O). All other H atoms were placed in calculated positions and refined as riding, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of (I), showing the atom-labelling scheme for the asymmetric unit. Displacement ellipsoids are drawn at the 50% probability level. unlabelled atoms are related to labelled atoms by the symmetry operation (1 - x, 1 - y, -z). Symmetry ...

Crystal data

C18H26N22+·2(Br)·2H2OF000 = 952
Mr = 466.26Dx = 1.429 Mg m3
Orthorhombic, PbcaMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 21410 reflections
a = 9.8329 (7) Åθ = 2.5–27.6º
b = 13.3000 (11) ŵ = 3.75 mm1
c = 16.5688 (13) ÅT = 273 (2) K
V = 2166.8 (3) Å3Prism, colourless
Z = 40.32 × 0.24 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer2503 independent reflections
Radiation source: fine-focus sealed tube1842 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 273(2) Kθmax = 27.6º
[var phi] and ω scansθmin = 2.5º
Absorption correction: multi-scan(SADABS; Bruker, 2005)h = −12→12
Tmin = 0.380, Tmax = 0.536k = −17→17
21410 measured reflectionsl = −15→21

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.077  w = 1/[σ2(Fo2) + (0.0352P)2 + 0.8723P] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
2503 reflectionsΔρmax = 0.25 e Å3
109 parametersΔρmin = −0.39 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
Br10.28891 (2)0.652327 (19)0.328729 (15)0.05280 (11)
N10.44180 (18)0.35645 (13)0.32104 (10)0.0376 (4)
C10.3916 (3)0.40288 (17)0.38614 (14)0.0507 (6)
H10.32460.45170.38010.061*
C20.4380 (3)0.3791 (2)0.46131 (16)0.0642 (8)
H20.40140.41050.50650.077*
C30.5389 (3)0.3088 (2)0.46995 (16)0.0660 (8)
H30.57250.29310.52090.079*
C40.5895 (3)0.2622 (2)0.40288 (15)0.0588 (7)
H40.65820.21460.40770.071*
C50.5382 (2)0.28617 (18)0.32886 (13)0.0475 (6)
H50.57070.25320.28320.057*
C60.3864 (2)0.37965 (18)0.23978 (13)0.0455 (5)
H6A0.31370.42850.24530.055*
H6B0.34760.31890.21700.055*
C70.4916 (2)0.42052 (18)0.18213 (12)0.0432 (5)
H7A0.56330.37120.17490.052*
H7B0.53200.48080.20480.052*
C80.4286 (2)0.44515 (19)0.10078 (13)0.0444 (5)
H8A0.38650.38500.07910.053*
H8B0.35770.49500.10840.053*
C90.5310 (2)0.48488 (17)0.04014 (12)0.0408 (5)
H9A0.57660.54280.06330.049*
H9B0.59920.43350.03060.049*
O1W0.1270 (2)0.6061 (2)0.15455 (12)0.0973 (8)
H1WA0.04420.61310.16470.117*
H1WB0.16890.61170.19650.117*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.04958 (16)0.05876 (17)0.05006 (17)0.00012 (12)−0.00083 (11)0.01642 (11)
N10.0424 (10)0.0428 (10)0.0277 (9)−0.0036 (8)0.0058 (7)0.0044 (7)
C10.0627 (14)0.0464 (13)0.0429 (14)0.0058 (12)0.0161 (12)0.0025 (11)
C20.094 (2)0.0637 (16)0.0345 (14)−0.0017 (16)0.0104 (14)−0.0069 (12)
C30.081 (2)0.0830 (19)0.0341 (14)−0.0090 (17)−0.0084 (14)0.0108 (14)
C40.0601 (15)0.0672 (17)0.0492 (15)0.0092 (13)−0.0038 (13)0.0141 (13)
C50.0528 (14)0.0527 (14)0.0368 (13)0.0072 (11)0.0061 (11)0.0008 (11)
C60.0437 (12)0.0601 (13)0.0326 (12)−0.0035 (11)−0.0004 (10)0.0098 (11)
C70.0447 (12)0.0539 (13)0.0311 (12)−0.0047 (11)0.0010 (10)0.0064 (10)
C80.0437 (12)0.0590 (14)0.0305 (11)−0.0035 (10)−0.0010 (10)0.0069 (10)
C90.0402 (11)0.0540 (13)0.0281 (11)−0.0067 (10)−0.0031 (9)0.0036 (10)
O1W0.0625 (12)0.177 (3)0.0519 (12)0.0086 (16)−0.0006 (10)−0.0161 (14)

Geometric parameters (Å, °)

N1—C11.337 (3)C6—H6A0.97
N1—C51.337 (3)C6—H6B0.97
N1—C61.485 (3)C7—C81.520 (3)
C1—C21.364 (4)C7—H7A0.97
C1—H10.93C7—H7B0.97
C2—C31.370 (4)C8—C91.518 (3)
C2—H20.93C8—H8A0.97
C3—C41.366 (4)C8—H8B0.97
C3—H30.93C9—C9i1.518 (4)
C4—C51.364 (3)C9—H9A0.97
C4—H40.93C9—H9B0.97
C5—H50.93O1W—H1WA0.84
C6—C71.509 (3)O1W—H1WB0.81
C1—N1—C5120.42 (19)C7—C6—H6B108.9
C1—N1—C6120.0 (2)H6A—C6—H6B107.7
C5—N1—C6119.53 (18)C6—C7—C8111.07 (19)
N1—C1—C2120.4 (2)C6—C7—H7A109.4
N1—C1—H1119.8C8—C7—H7A109.4
C2—C1—H1119.8C6—C7—H7B109.4
C1—C2—C3119.7 (2)C8—C7—H7B109.4
C1—C2—H2120.1H7A—C7—H7B108.0
C3—C2—H2120.1C9—C8—C7113.04 (18)
C4—C3—C2119.2 (2)C9—C8—H8A109.0
C4—C3—H3120.4C7—C8—H8A109.0
C2—C3—H3120.4C9—C8—H8B109.0
C5—C4—C3119.4 (2)C7—C8—H8B109.0
C5—C4—H4120.3H8A—C8—H8B107.8
C3—C4—H4120.3C9i—C9—C8113.9 (2)
N1—C5—C4120.8 (2)C9i—C9—H9A108.8
N1—C5—H5119.6C8—C9—H9A108.8
C4—C5—H5119.6C9i—C9—H9B108.8
N1—C6—C7113.42 (17)C8—C9—H9B108.8
N1—C6—H6A108.9H9A—C9—H9B107.7
C7—C6—H6A108.9H1WA—O1W—H1WB108.2
N1—C6—H6B108.9
C5—N1—C1—C20.0 (3)C3—C4—C5—N11.8 (4)
C6—N1—C1—C2177.4 (2)C1—N1—C6—C7120.1 (2)
N1—C1—C2—C31.5 (4)C5—N1—C6—C7−62.5 (3)
C1—C2—C3—C4−1.3 (4)N1—C6—C7—C8−178.7 (2)
C2—C3—C4—C5−0.3 (4)C6—C7—C8—C9−179.0 (2)
C1—N1—C5—C4−1.6 (3)C7—C8—C9—C9i−177.0 (2)
C6—N1—C5—C4−179.0 (2)

Symmetry codes: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H1WB···Br10.812.553.353 (2)173
O1W—H1WA···Br1ii0.842.573.392 (2)169
C1—H1···Br10.932.823.596 (2)141
C2—H2···O1Wiii0.932.483.271 (3)143
C5—H5···Br1iv0.932.673.588 (2)168

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2531).

References

  • Bruker (2005). APEX2, SAINT and SADABS 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. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.

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