organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Octane-1,8-diyldipyridinium dibromide dihydrate

aKey Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, People's Republic of China, and bInstitute of Applied Chemistry, Guizhou University, Guiyang 550025, People's Republic of China
*Correspondence e-mail: sci.yqzhang@gzu.edu.cn

(Received 23 November 2007; accepted 28 November 2007; online 6 December 2007)

The asymmetric unit of the title compound, C18H26N22+·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[Day, A. I., Arnold, A. P. & Blanch, R. J. (2000). Patent No. WO/2000/068232.], 2002[Day, A. I., Blanch, R. J., Arnold, A. P., Lorenzo, S., Lewis, G. R. & Dance, I. (2002). Angew. Chem. Int. Ed. 41, 275-277.]); Freeman et al. (1981[Freeman, W. A., Mock, W. L. & Shih, N. Y. (1981). J. Am. Chem. Soc. 103, 7367-7368.]); Kim et al. (2000[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.]).

[Scheme 1]

Experimental

Crystal data
  • C18H26N22+·2Br·2H2O

  • Mr = 466.26

  • Orthorhombic, P b c a

  • 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[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS, Inc., Madison, Wisconsin, USA.]) Tmin = 0.380, Tmax = 0.536 (expected range = 0.347–0.490)

  • 21410 measured reflections

  • 2503 independent reflections

  • 1842 reflections with I > 2σ(I)

  • Rint = 0.034

Refinement
  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1W—H1WB⋯Br1 0.81 2.55 3.353 (2) 173
O1W—H1WA⋯Br1i 0.84 2.57 3.392 (2) 169
C1—H1⋯Br1 0.93 2.82 3.596 (2) 141
C2—H2⋯O1Wii 0.93 2.48 3.271 (3) 143
C5—H5⋯Br1iii 0.93 2.67 3.588 (2) 168
Symmetry codes: (i) [x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]; (ii) [-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]; (iii) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS, Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS, Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

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.

Related literature top

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

Experimental top

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 top

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).

Structure description top

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.

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

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] 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 related bromide ion and water molecule are not shown.
Octane-1,8-diyldipyridinium dibromide dihydrate top
Crystal data top
C18H26N22+·2(Br)·2H2OF(000) = 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 = 2.5–27.6°
b = 13.3000 (11) ŵ = 3.75 mm1
c = 16.5688 (13) ÅT = 273 K
V = 2166.8 (3) Å3Prism, colourless
Z = 40.32 × 0.24 × 0.19 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2503 independent reflections
Radiation source: fine-focus sealed tube1842 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
φ and ω scansθmax = 27.6°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 1212
Tmin = 0.380, Tmax = 0.536k = 1717
21410 measured reflectionsl = 1521
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0352P)2 + 0.8723P]
where P = (Fo2 + 2Fc2)/3
2503 reflections(Δ/σ)max = 0.001
109 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.39 e Å3
Crystal data top
C18H26N22+·2(Br)·2H2OV = 2166.8 (3) Å3
Mr = 466.26Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 9.8329 (7) ŵ = 3.75 mm1
b = 13.3000 (11) ÅT = 273 K
c = 16.5688 (13) Å0.32 × 0.24 × 0.19 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2503 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
1842 reflections with I > 2σ(I)
Tmin = 0.380, Tmax = 0.536Rint = 0.034
21410 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.077H-atom parameters constrained
S = 1.01Δρmax = 0.25 e Å3
2503 reflectionsΔρmin = 0.39 e Å3
109 parameters
Special details top

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) top
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) top
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, º) top
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—C762.5 (3)
C1—C2—C3—C41.3 (4)N1—C6—C7—C8178.7 (2)
C2—C3—C4—C50.3 (4)C6—C7—C8—C9179.0 (2)
C1—N1—C5—C41.6 (3)C7—C8—C9—C9i177.0 (2)
C6—N1—C5—C4179.0 (2)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
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) x1/2, y, z+1/2; (iii) x+1/2, y+1, z+1/2; (iv) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC18H26N22+·2(Br)·2H2O
Mr466.26
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)273
a, b, c (Å)9.8329 (7), 13.3000 (11), 16.5688 (13)
V3)2166.8 (3)
Z4
Radiation typeMo Kα
µ (mm1)3.75
Crystal size (mm)0.32 × 0.24 × 0.19
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.380, 0.536
No. of measured, independent and
observed [I > 2σ(I)] reflections
21410, 2503, 1842
Rint0.034
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.077, 1.01
No. of reflections2503
No. of parameters109
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.39

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···Br10.812.553.353 (2)173
O1W—H1WA···Br1i0.842.573.392 (2)169
C1—H1···Br10.932.823.596 (2)141
C2—H2···O1Wii0.932.483.271 (3)143
C5—H5···Br1iii0.932.673.588 (2)168
Symmetry codes: (i) x1/2, y, z+1/2; (ii) x+1/2, y+1, z+1/2; (iii) x+1, y1/2, z+1/2.
 

Acknowledgements

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

References

First citationBruker (2005). APEX2, SAINT and SADABS. Bruker AXS, Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDay, A. I., Arnold, A. P. & Blanch, R. J. (2000). Patent No. WO/2000/068232.  Google Scholar
First citationDay, A. I., Blanch, R. J., Arnold, A. P., Lorenzo, S., Lewis, G. R. & Dance, I. (2002). Angew. Chem. Int. Ed. 41, 275–277.  Web of Science CSD CrossRef CAS Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationFreeman, W. A., Mock, W. L. & Shih, N. Y. (1981). J. Am. Chem. Soc. 103, 7367–7368.  CSD CrossRef CAS Web of Science Google Scholar
First citationKim, 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.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar

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ISSN: 2056-9890
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