Octane-1,8-diyldipyridinium dibromide dihydrate

Xiao, X.; Jiang, P.-Y.; Zhang, Y.-Q.; Xue, S.-F.; Zhu, Q.-J.

doi:10.1107/S1600536807063970

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o183

https://doi.org/10.1107/S1600536807063970

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Octane-1,8-diyldipyridinium dibromide dihydrate

Xin Xiao,^a Ping-Yue Jiang,^a Yun-Qian Zhang,^a ^* Sai-Feng Xue ^b and Qian-Jiang Zhu ^b

^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 , 2002 ); Freeman et al. (1981 ); Kim et al. (2000 ).

Experimental

Crystal data

C₁₈H₂₆N₂²⁺·2Br⁻·2H₂O
M_r = 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 ) 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[F² > 2σ(F²)] = 0.029
wR(F²) = 0.077
S = 1.01
2503 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807063970/ci2531sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063970/ci2531Isup2.hkl

checkCIF report

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.

Structure description top

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

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⁻)·2H₂O	F(000) = 952
M_r = 466.26	D_x = 1.429 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 21410 reflections
a = 9.8329 (7) Å	θ = 2.5–27.6°
b = 13.3000 (11) Å	µ = 3.75 mm⁻¹
c = 16.5688 (13) Å	T = 273 K
V = 2166.8 (3) Å³	Prism, colourless
Z = 4	0.32 × 0.24 × 0.19 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2503 independent reflections
Radiation source: fine-focus sealed tube	1842 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
φ and ω scans	θ_max = 27.6°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→12
T_min = 0.380, T_max = 0.536	k = −17→17
21410 measured reflections	l = −15→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0352P)² + 0.8723P] where P = (F_o² + 2F_c²)/3
2503 reflections	(Δ/σ)_max = 0.001
109 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₁₈H₂₆N₂²⁺·2(Br⁻)·2H₂O	V = 2166.8 (3) Å³
M_r = 466.26	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 9.8329 (7) Å	µ = 3.75 mm⁻¹
b = 13.3000 (11) Å	T = 273 K
c = 16.5688 (13) Å	0.32 × 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)
T_min = 0.380, T_max = 0.536	R_int = 0.034
21410 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.01	Δρ_max = 0.25 e Å⁻³
2503 reflections	Δρ_min = −0.39 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Br1	0.28891 (2)	0.652327 (19)	0.328729 (15)	0.05280 (11)
N1	0.44180 (18)	0.35645 (13)	0.32104 (10)	0.0376 (4)
C1	0.3916 (3)	0.40288 (17)	0.38614 (14)	0.0507 (6)
H1	0.3246	0.4517	0.3801	0.061*
C2	0.4380 (3)	0.3791 (2)	0.46131 (16)	0.0642 (8)
H2	0.4014	0.4105	0.5065	0.077*
C3	0.5389 (3)	0.3088 (2)	0.46995 (16)	0.0660 (8)
H3	0.5725	0.2931	0.5209	0.079*
C4	0.5895 (3)	0.2622 (2)	0.40288 (15)	0.0588 (7)
H4	0.6582	0.2146	0.4077	0.071*
C5	0.5382 (2)	0.28617 (18)	0.32886 (13)	0.0475 (6)
H5	0.5707	0.2532	0.2832	0.057*
C6	0.3864 (2)	0.37965 (18)	0.23978 (13)	0.0455 (5)
H6A	0.3137	0.4285	0.2453	0.055*
H6B	0.3476	0.3189	0.2170	0.055*
C7	0.4916 (2)	0.42052 (18)	0.18213 (12)	0.0432 (5)
H7A	0.5633	0.3712	0.1749	0.052*
H7B	0.5320	0.4808	0.2048	0.052*
C8	0.4286 (2)	0.44515 (19)	0.10078 (13)	0.0444 (5)
H8A	0.3865	0.3850	0.0791	0.053*
H8B	0.3577	0.4950	0.1084	0.053*
C9	0.5310 (2)	0.48488 (17)	0.04014 (12)	0.0408 (5)
H9A	0.5766	0.5428	0.0633	0.049*
H9B	0.5992	0.4335	0.0306	0.049*
O1W	0.1270 (2)	0.6061 (2)	0.15455 (12)	0.0973 (8)
H1WA	0.0442	0.6131	0.1647	0.117*
H1WB	0.1689	0.6117	0.1965	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.04958 (16)	0.05876 (17)	0.05006 (17)	0.00012 (12)	−0.00083 (11)	0.01642 (11)
N1	0.0424 (10)	0.0428 (10)	0.0277 (9)	−0.0036 (8)	0.0058 (7)	0.0044 (7)
C1	0.0627 (14)	0.0464 (13)	0.0429 (14)	0.0058 (12)	0.0161 (12)	0.0025 (11)
C2	0.094 (2)	0.0637 (16)	0.0345 (14)	−0.0017 (16)	0.0104 (14)	−0.0069 (12)
C3	0.081 (2)	0.0830 (19)	0.0341 (14)	−0.0090 (17)	−0.0084 (14)	0.0108 (14)
C4	0.0601 (15)	0.0672 (17)	0.0492 (15)	0.0092 (13)	−0.0038 (13)	0.0141 (13)
C5	0.0528 (14)	0.0527 (14)	0.0368 (13)	0.0072 (11)	0.0061 (11)	0.0008 (11)
C6	0.0437 (12)	0.0601 (13)	0.0326 (12)	−0.0035 (11)	−0.0004 (10)	0.0098 (11)
C7	0.0447 (12)	0.0539 (13)	0.0311 (12)	−0.0047 (11)	0.0010 (10)	0.0064 (10)
C8	0.0437 (12)	0.0590 (14)	0.0305 (11)	−0.0035 (10)	−0.0010 (10)	0.0069 (10)
C9	0.0402 (11)	0.0540 (13)	0.0281 (11)	−0.0067 (10)	−0.0031 (9)	0.0036 (10)
O1W	0.0625 (12)	0.177 (3)	0.0519 (12)	0.0086 (16)	−0.0006 (10)	−0.0161 (14)

Geometric parameters (Å, º) top

N1—C1	1.337 (3)	C6—H6A	0.97
N1—C5	1.337 (3)	C6—H6B	0.97
N1—C6	1.485 (3)	C7—C8	1.520 (3)
C1—C2	1.364 (4)	C7—H7A	0.97
C1—H1	0.93	C7—H7B	0.97
C2—C3	1.370 (4)	C8—C9	1.518 (3)
C2—H2	0.93	C8—H8A	0.97
C3—C4	1.366 (4)	C8—H8B	0.97
C3—H3	0.93	C9—C9ⁱ	1.518 (4)
C4—C5	1.364 (3)	C9—H9A	0.97
C4—H4	0.93	C9—H9B	0.97
C5—H5	0.93	O1W—H1WA	0.84
C6—C7	1.509 (3)	O1W—H1WB	0.81

C1—N1—C5	120.42 (19)	C7—C6—H6B	108.9
C1—N1—C6	120.0 (2)	H6A—C6—H6B	107.7
C5—N1—C6	119.53 (18)	C6—C7—C8	111.07 (19)
N1—C1—C2	120.4 (2)	C6—C7—H7A	109.4
N1—C1—H1	119.8	C8—C7—H7A	109.4
C2—C1—H1	119.8	C6—C7—H7B	109.4
C1—C2—C3	119.7 (2)	C8—C7—H7B	109.4
C1—C2—H2	120.1	H7A—C7—H7B	108.0
C3—C2—H2	120.1	C9—C8—C7	113.04 (18)
C4—C3—C2	119.2 (2)	C9—C8—H8A	109.0
C4—C3—H3	120.4	C7—C8—H8A	109.0
C2—C3—H3	120.4	C9—C8—H8B	109.0
C5—C4—C3	119.4 (2)	C7—C8—H8B	109.0
C5—C4—H4	120.3	H8A—C8—H8B	107.8
C3—C4—H4	120.3	C9ⁱ—C9—C8	113.9 (2)
N1—C5—C4	120.8 (2)	C9ⁱ—C9—H9A	108.8
N1—C5—H5	119.6	C8—C9—H9A	108.8
C4—C5—H5	119.6	C9ⁱ—C9—H9B	108.8
N1—C6—C7	113.42 (17)	C8—C9—H9B	108.8
N1—C6—H6A	108.9	H9A—C9—H9B	107.7
C7—C6—H6A	108.9	H1WA—O1W—H1WB	108.2
N1—C6—H6B	108.9

C5—N1—C1—C2	0.0 (3)	C3—C4—C5—N1	1.8 (4)
C6—N1—C1—C2	177.4 (2)	C1—N1—C6—C7	120.1 (2)
N1—C1—C2—C3	1.5 (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 code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···Br1	0.81	2.55	3.353 (2)	173
O1W—H1WA···Br1ⁱⁱ	0.84	2.57	3.392 (2)	169
C1—H1···Br1	0.93	2.82	3.596 (2)	141
C2—H2···O1Wⁱⁱⁱ	0.93	2.48	3.271 (3)	143
C5—H5···Br1^iv	0.93	2.67	3.588 (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.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₆N₂²⁺·2(Br⁻)·2H₂O
M_r	466.26
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	273
a, b, c (Å)	9.8329 (7), 13.3000 (11), 16.5688 (13)
V (Å³)	2166.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.75
Crystal size (mm)	0.32 × 0.24 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.380, 0.536
No. of measured, independent and observed [I > 2σ(I)] reflections	21410, 2503, 1842
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.077, 1.01
No. of reflections	2503
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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−1/2, y, −z+1/2; (ii) −x+1/2, −y+1, z+1/2; (iii) −x+1, y−1/2, −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.

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