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

Wu, M.-Q.; Xiao, X.; Zhang, Y.-Q.; Xue, S.-F.; Zhu, Q.-J.

doi:10.1107/S1600536808000913

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o467

doi:10.1107/S1600536808000913

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

Ming-Qiang Wu,^a Xin Xiao,^a Yun-Qian Zhang,^a ^* Sai-Feng Xue ^a 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 17 December 2007; accepted 10 January 2008; online 18 January 2008)

The organic cation in the title compound, C₁₄H₁₈N₂²⁺·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 , 2002 ); Freeman et al. (1981 ); Kim et al. (2000 ).

Experimental

Crystal data

C₁₄H₁₈N₂²⁺·2Br⁻·2H₂O
M_r = 410.14
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.030
wR(F²) = 0.074
S = 1.06
1723 reflections
92 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯Br1	0.85	2.48	3.323 (2)	172
O1W—H1WB⋯Br1ⁱ	0.85	2.53	3.375 (2)	175
C2—H2⋯Br1ⁱⁱ	0.93	2.86	3.664 (3)	145
C5—H5⋯O1Wⁱⁱⁱ	0.93	2.55	3.376 (3)	148
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y, z-1; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); 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: 10.1107/S1600536808000913/fb2085sup1.cif

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

checkCIF report

Comment top

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].

Related literature top

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

Experimental top

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.

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, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); 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. Displacement ellipsoids are drawn at the 50% probability level. Symmetry code of C7^a: -x + 1, -y, -z + 1.

1,1'-(Butane-1,4-diyl)dipyridinium dibromide dihydrate top

Crystal data top

C₁₄H₁₈N₂²⁺·2Br⁻·2H₂O	F(000) = 412
M_r = 410.14	D_x = 1.544 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1730 reflections
a = 11.0068 (13) Å	θ = 0.5–0.6°
b = 7.1484 (8) Å	µ = 4.60 mm⁻¹
c = 12.0607 (13) Å	T = 293 K
β = 111.602 (7)°	Diamond, colourless
V = 882.30 (18) Å³	0.21 × 0.18 × 0.16 mm
Z = 2

Data collection top

Bruker CCD area-detector diffractometer	1723 independent reflections
Radiation source: fine-focus sealed tube	1483 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→13
T_min = 0.393, T_max = 0.478	k = −8→8
7189 measured reflections	l = −14→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0377P)² + 0.1891P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
1723 reflections	Δρ_max = 0.48 e Å⁻³
92 parameters	Δρ_min = −0.45 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
38 constraints	Extinction coefficient: 0.073 (3)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₄H₁₈N₂²⁺·2Br⁻·2H₂O	V = 882.30 (18) Å³
M_r = 410.14	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.0068 (13) Å	µ = 4.60 mm⁻¹
b = 7.1484 (8) Å	T = 293 K
c = 12.0607 (13) Å	0.21 × 0.18 × 0.16 mm
β = 111.602 (7)°

Data collection top

Bruker CCD area-detector diffractometer	1723 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1483 reflections with I > 2σ(I)
T_min = 0.393, T_max = 0.478	R_int = 0.041
7189 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	3 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.06	Δρ_max = 0.48 e Å⁻³
1723 reflections	Δρ_min = −0.45 e Å⁻³
92 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
C1	0.6134 (3)	0.1783 (4)	0.2544 (2)	0.0512 (6)
H1	0.5228	0.1803	0.2175	0.061*
C2	0.6896 (3)	0.1660 (4)	0.1867 (2)	0.0602 (7)
H2	0.6509	0.1598	0.1040	0.072*
C3	0.8220 (3)	0.1629 (4)	0.2408 (3)	0.0627 (8)
H3	0.8741	0.1553	0.1953	0.075*
C4	0.8782 (3)	0.1710 (5)	0.3631 (3)	0.0655 (8)
H4	0.9686	0.1687	0.4012	0.079*
C5	0.7990 (3)	0.1826 (4)	0.4285 (2)	0.0515 (6)
H5	0.8359	0.1870	0.5114	0.062*
C6	0.5845 (2)	0.1926 (3)	0.4453 (2)	0.0458 (6)
H6A	0.5090	0.2711	0.4059	0.055*
H6B	0.6329	0.2462	0.5229	0.055*
C7	0.5400 (2)	−0.0023 (3)	0.46040 (19)	0.0389 (5)
H7A	0.6155	−0.0826	0.4959	0.047*
H7B	0.4875	−0.0534	0.3830	0.047*
N1	0.66903 (18)	0.1874 (3)	0.37309 (16)	0.0393 (5)
O1W	0.6333 (2)	0.5305 (3)	0.7900 (2)	0.0762 (6)
H1WA	0.6461	0.4149	0.8070	0.091*
H1WB	0.6735	0.5522	0.7437	0.091*
Br1	0.69404 (3)	0.09270 (4)	0.88751 (2)	0.05201 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0517 (15)	0.0538 (15)	0.0443 (13)	0.0009 (12)	0.0133 (12)	0.0042 (12)
C2	0.087 (2)	0.0545 (16)	0.0457 (14)	0.0055 (15)	0.0326 (15)	0.0043 (13)
C3	0.086 (2)	0.0498 (15)	0.077 (2)	−0.0030 (15)	0.0598 (19)	0.0006 (15)
C4	0.0500 (17)	0.0680 (18)	0.087 (2)	−0.0151 (15)	0.0353 (16)	−0.0133 (17)
C5	0.0428 (15)	0.0613 (16)	0.0487 (14)	−0.0095 (12)	0.0148 (12)	−0.0098 (13)
C6	0.0466 (14)	0.0484 (14)	0.0492 (13)	−0.0010 (11)	0.0253 (12)	−0.0008 (11)
C7	0.0359 (12)	0.0449 (13)	0.0359 (11)	−0.0006 (10)	0.0133 (10)	0.0009 (10)
N1	0.0417 (12)	0.0374 (11)	0.0421 (10)	−0.0042 (8)	0.0193 (9)	−0.0015 (8)
O1W	0.0797 (15)	0.0731 (13)	0.0922 (15)	0.0221 (12)	0.0509 (14)	0.0232 (13)
Br1	0.0555 (2)	0.0537 (2)	0.0485 (2)	0.00237 (12)	0.02118 (15)	0.00144 (11)

Geometric parameters (Å, º) top

C1—N1	1.335 (3)	C5—H5	0.9300
C1—C2	1.372 (4)	C6—N1	1.490 (3)
C1—H1	0.9300	C6—C7	1.510 (3)
C2—C3	1.359 (4)	C6—H6A	0.9700
C2—H2	0.9300	C6—H6B	0.9700
C3—C4	1.375 (4)	C7—C7ⁱ	1.519 (4)
C3—H3	0.9300	C7—H7A	0.9700
C4—C5	1.377 (4)	C7—H7B	0.9700
C4—H4	0.9300	O1W—H1WA	0.8507
C5—N1	1.338 (3)	O1W—H1WB	0.8454

N1—C1—C2	120.1 (3)	N1—C6—H6A	109.6
N1—C1—H1	120.0	C7—C6—H6A	109.6
C2—C1—H1	120.0	N1—C6—H6B	109.6
C3—C2—C1	119.9 (3)	C7—C6—H6B	109.6
C3—C2—H2	120.1	H6A—C6—H6B	108.1
C1—C2—H2	120.1	C6—C7—C7ⁱ	110.2 (2)
C2—C3—C4	119.6 (2)	C6—C7—H7A	109.6
C2—C3—H3	120.2	C7ⁱ—C7—H7A	109.6
C4—C3—H3	120.2	C6—C7—H7B	109.6
C3—C4—C5	119.2 (3)	C7ⁱ—C7—H7B	109.6
C3—C4—H4	120.4	H7A—C7—H7B	108.1
C5—C4—H4	120.4	C1—N1—C5	121.2 (2)
N1—C5—C4	120.1 (3)	C1—N1—C6	119.3 (2)
N1—C5—H5	120.0	C5—N1—C6	119.4 (2)
C4—C5—H5	120.0	H1WA—O1W—H1WB	104.9
N1—C6—C7	110.37 (19)

N1—C1—C2—C3	0.1 (4)	C2—C1—N1—C6	−177.4 (2)
C1—C2—C3—C4	0.4 (5)	C4—C5—N1—C1	1.0 (4)
C2—C3—C4—C5	−0.1 (5)	C4—C5—N1—C6	177.7 (3)
C3—C4—C5—N1	−0.6 (4)	C7—C6—N1—C1	81.1 (3)
N1—C6—C7—C7ⁱ	176.9 (2)	C7—C6—N1—C5	−95.6 (3)
C2—C1—N1—C5	−0.8 (4)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···Br1	0.85	2.48	3.323 (2)	172
O1W—H1WB···Br1ⁱⁱ	0.85	2.53	3.375 (2)	175
C2—H2···Br1ⁱⁱⁱ	0.93	2.86	3.664 (3)	145
C5—H5···O1W^iv	0.93	2.55	3.376 (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.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈N₂²⁺·2Br⁻·2H₂O
M_r	410.14
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	11.0068 (13), 7.1484 (8), 12.0607 (13)
β (°)	111.602 (7)
V (Å³)	882.30 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.60
Crystal size (mm)	0.21 × 0.18 × 0.16

Data collection
Diffractometer	Bruker CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.393, 0.478
No. of measured, independent and observed [I > 2σ(I)] reflections	7189, 1723, 1483
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.074, 1.06
No. of reflections	1723
No. of parameters	92
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.45

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), 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—H1WA···Br1	0.85	2.48	3.323 (2)	171.6
O1W—H1WB···Br1ⁱ	0.85	2.53	3.375 (2)	175.0
C2—H2···Br1ⁱⁱ	0.93	2.86	3.664 (3)	145.3
C5—H5···O1Wⁱⁱⁱ	0.93	2.55	3.376 (3)	148.0

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

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

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