1,1′-(Butane-1,4-di­yl)diimidazolium dinitrate

Jin, S.; Wang, D.

doi:10.1107/S1600536807063751

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o169

https://doi.org/10.1107/S1600536807063751

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1,1′-(Butane-1,4-diyl)diimidazolium dinitrate

Shouwen Jin ^a ^* and Daqi Wang ^b

^aFaculty of Science, ZheJiang Forestry University, Lin'An 311300, People's Republic of China, and ^bDepartment of Chemistry, Liaocheng University, Liaocheng, Shandong 252059, People's Republic of China
^*Correspondence e-mail: jinsw@zjfc.edu.cn

(Received 30 October 2007; accepted 27 November 2007; online 6 December 2007)

In the title compound, C₁₀H₁₆N₄²⁺·2NO₃⁻, the organic cation is located around an inversion centre. The imidazolium ring forms a dihedral angle of 62.7 (3)° with the plane defined by the C atoms of the –(CH₂)₄– aliphatic linker. Two anions bind to the cation via three-centre N—H⋯O hydrogen bonds and thus discrete hydrogen-bonded ion triples are formed. The nitrate is approximately coplanar with the imidazolium ring to which it binds.

Related literature

For related literature, see: Gould (1986 ); Holman et al. (2001 ); Jin & Chen (2007a ,b ); Jin et al. (2007 ); Królikowska & Garbarczyk (2005 ).

Experimental

Crystal data

C₁₀H₁₆N₄²⁺·2NO₃⁻
M_r = 316.29
Monoclinic, P 2₁ /n
a = 7.788 (2) Å
b = 10.482 (3) Å
c = 9.363 (3) Å
β = 110.649 (4)°
V = 715.3 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 (2) K
0.43 × 0.40 × 0.31 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.949, T_max = 0.963
3629 measured reflections
1257 independent reflections
913 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.115
S = 1.06
1257 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.86	2.59	3.157 (2)	124
N2—H2⋯O2ⁱ	0.86	1.90	2.762 (2)	175
Symmetry code: (i) x, y, z+1.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807063751/gk2116sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063751/gk2116Isup2.hkl

checkCIF report

Comment top

Intermolecular hydrogen bonds are a well known and efficient tool used to regulate molecular arrangement in crystals (Holman et al., 2001). Salt formation can be driven by hydrogen bond as well (Gould, 1986). As an extension of our study on supramolecular assembly through weak interactions (Jin & Chen, 2007a,b; Jin et al., 2007), here we report synthesis and crystal structure of 1,1'-(1,4-butanediyl)bis(imidazolium) dinitrate. The crystal structure of the organic base and its 1:2 salt with hydrochloric acid has been already reported (Królikowska & Garbarczyk, 2005).

The title compound was prepared by reacting ferric nitrate nonahydrate with 1-(4-(1H-imidazol-1-yl) butyl)-1H-imidazole. The hydrolysis of ferric nitrate nonahydrate led to nitric acid formation, which, in turn, reacted with 1-(4-(1H-imidazol-1-yl)butyl)-1H-imidazole present in the reaction medium to give 2:1 salt (Fig. 1).

The protonated imidazolium rings interact with the anion via a three-center hydrogen bond with one strong and one weak component (Table 1) and the nitrate ion is practically coplanar with the imidazolium ring. On the other hand, the heterocyclic rings and nitrate anions form double-stacks extending along the [100] direction with the alternating anionic and cationic species (Fig. 2).

Related literature top

For related literature, see: Gould (1986); Holman et al. (2001); Jin & Chen (2007a,b); Jin et al. (2007); Królikowska & Garbarczyk (2005).

Experimental top

All reagents and solvents were used as obtained without further purification. The CHN elemental analyses were performed on a Perkin-Elmer model 2400 elemental analyzer.

Ferric nitrate nonahydrate (40.4 mg, 0.1 mmol) and 1-(4-(1H-imidazol-1-yl) butyl)-1H-imidazole (57 mg, 0.3 mmol) in ethanol (10 ml) were mixed and after several minutes a yellow precipitate formed. The precipitate was filtered off to yield colorless solution and the colorless solution was left standing at room temperature. In a few days colorless block crystals appeared. Yield based on 1-(4-(1H-imidazol-1-yl) butyl)-1H-imidazole: 21.3 mg, 28%. Anal. Calculated for C₁₀H₁₆N₆O₆: C, 37.94; H, 5.06; N, 26.56. Found: C, 37.88; H, 5.02; N, 26.51.

Structure description top

For related literature, see: Gould (1986); Holman et al. (2001); Jin & Chen (2007a,b); Jin et al. (2007); Królikowska & Garbarczyk (2005).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top

	Fig. 1. The structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing of the hydrgen-bonded assemblies in the crystal structure of the title compound (dashed lines indicate hydrogen bonds, hydrogen atoms were omitted for clarity).

1,1'-(Butane-1,4-diyl)diimidazolium dinitrate top

Crystal data top

C₁₀H₁₆N₄²⁺·2NO₃⁻	F(000) = 332
M_r = 316.29	D_x = 1.469 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1224 reflections
a = 7.788 (2) Å	θ = 2.8–24.0°
b = 10.482 (3) Å	µ = 0.12 mm⁻¹
c = 9.363 (3) Å	T = 298 K
β = 110.649 (4)°	Block, colourless
V = 715.3 (4) Å³	0.43 × 0.40 × 0.31 mm
Z = 2

Data collection top

Bruker SMART APEXII CCD diffractometer	1257 independent reflections
Radiation source: fine-focus sealed tube	913 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
φ and ω scans	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.949, T_max = 0.963	k = −12→10
3629 measured reflections	l = −11→8

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0497P)² + 0.1767P] where P = (F_o² + 2F_c²)/3
1257 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₀H₁₆N₄²⁺·2NO₃⁻	V = 715.3 (4) Å³
M_r = 316.29	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.788 (2) Å	µ = 0.12 mm⁻¹
b = 10.482 (3) Å	T = 298 K
c = 9.363 (3) Å	0.43 × 0.40 × 0.31 mm
β = 110.649 (4)°

Data collection top

Bruker SMART APEXII CCD diffractometer	1257 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	913 reflections with I > 2σ(I)
T_min = 0.949, T_max = 0.963	R_int = 0.036
3629 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	Δρ_max = 0.21 e Å⁻³
1257 reflections	Δρ_min = −0.20 e Å⁻³
100 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
N1	0.6076 (2)	0.66149 (16)	0.79775 (17)	0.0408 (4)
N2	0.5677 (2)	0.72628 (16)	1.00094 (19)	0.0483 (5)
H2	0.5670	0.7281	1.0925	0.058*
N3	0.6173 (2)	0.84419 (17)	0.3487 (2)	0.0458 (5)
O1	0.6683 (3)	0.92237 (15)	0.27403 (18)	0.0673 (5)
O2	0.5460 (2)	0.74148 (15)	0.28855 (17)	0.0623 (5)
O3	0.6379 (3)	0.86529 (19)	0.4822 (2)	0.0934 (7)
C1	0.6268 (3)	0.6310 (2)	0.9390 (2)	0.0465 (5)
H1	0.6744	0.5546	0.9872	0.056*
C2	0.5079 (3)	0.8216 (2)	0.8959 (2)	0.0472 (5)
H2A	0.4590	0.8996	0.9098	0.057*
C3	0.5331 (3)	0.78137 (19)	0.7687 (2)	0.0440 (5)
H3	0.5051	0.8264	0.6778	0.053*
C4	0.6486 (3)	0.5788 (2)	0.6874 (2)	0.0509 (6)
H4A	0.7079	0.5016	0.7385	0.061*
H4B	0.7332	0.6223	0.6488	0.061*
C5	0.4777 (3)	0.54372 (19)	0.5556 (2)	0.0423 (5)
H5A	0.4195	0.6207	0.5030	0.051*
H5B	0.3920	0.5014	0.5941	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0393 (9)	0.0461 (10)	0.0335 (9)	−0.0006 (8)	0.0086 (7)	−0.0054 (7)
N2	0.0578 (12)	0.0535 (11)	0.0342 (9)	−0.0049 (9)	0.0167 (8)	−0.0053 (8)
N3	0.0479 (10)	0.0514 (11)	0.0390 (10)	0.0031 (9)	0.0168 (8)	0.0011 (9)
O1	0.0972 (14)	0.0527 (10)	0.0581 (10)	−0.0080 (9)	0.0349 (10)	0.0098 (8)
O2	0.0810 (12)	0.0549 (10)	0.0557 (10)	−0.0154 (9)	0.0298 (9)	−0.0085 (8)
O3	0.1370 (18)	0.1073 (16)	0.0490 (11)	−0.0433 (14)	0.0491 (11)	−0.0251 (10)
C1	0.0503 (13)	0.0439 (12)	0.0398 (12)	−0.0001 (10)	0.0090 (10)	−0.0012 (9)
C2	0.0500 (12)	0.0408 (11)	0.0470 (13)	−0.0010 (10)	0.0125 (10)	−0.0054 (10)
C3	0.0470 (12)	0.0419 (12)	0.0390 (11)	−0.0035 (10)	0.0100 (9)	0.0007 (9)
C4	0.0453 (13)	0.0594 (14)	0.0469 (13)	0.0037 (11)	0.0148 (10)	−0.0142 (10)
C5	0.0407 (11)	0.0446 (11)	0.0409 (11)	−0.0020 (9)	0.0136 (9)	−0.0062 (9)

Geometric parameters (Å, º) top

N1—C1	1.317 (2)	C2—C3	1.342 (3)
N1—C3	1.371 (3)	C2—H2A	0.9300
N1—C4	1.467 (2)	C3—H3	0.9300
N2—C1	1.316 (3)	C4—C5	1.507 (3)
N2—C2	1.364 (3)	C4—H4A	0.9700
N2—H2	0.8600	C4—H4B	0.9700
N3—O3	1.223 (2)	C5—C5ⁱ	1.518 (4)
N3—O1	1.231 (2)	C5—H5A	0.9700
N3—O2	1.251 (2)	C5—H5B	0.9700
C1—H1	0.9300

C1—N1—C3	108.15 (16)	C2—C3—N1	107.24 (18)
C1—N1—C4	126.02 (18)	C2—C3—H3	126.4
C3—N1—C4	125.73 (17)	N1—C3—H3	126.4
C1—N2—C2	108.78 (18)	N1—C4—C5	111.83 (16)
C1—N2—H2	125.6	N1—C4—H4A	109.3
C2—N2—H2	125.6	C5—C4—H4A	109.3
O3—N3—O1	120.54 (19)	N1—C4—H4B	109.3
O3—N3—O2	119.56 (18)	C5—C4—H4B	109.3
O1—N3—O2	119.90 (18)	H4A—C4—H4B	107.9
N2—C1—N1	108.97 (18)	C4—C5—C5ⁱ	111.1 (2)
N2—C1—H1	125.5	C4—C5—H5A	109.4
N1—C1—H1	125.5	C5ⁱ—C5—H5A	109.4
C3—C2—N2	106.86 (19)	C4—C5—H5B	109.4
C3—C2—H2A	126.6	C5ⁱ—C5—H5B	109.4
N2—C2—H2A	126.6	H5A—C5—H5B	108.0

C2—N2—C1—N1	0.1 (2)	C1—N1—C3—C2	−0.1 (2)
C3—N1—C1—N2	0.0 (2)	C4—N1—C3—C2	176.60 (18)
C4—N1—C1—N2	−176.70 (17)	C1—N1—C4—C5	113.5 (2)
C1—N2—C2—C3	−0.2 (2)	C3—N1—C4—C5	−62.7 (3)
N2—C2—C3—N1	0.2 (2)	N1—C4—C5—C5ⁱ	−179.0 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱⁱ	0.86	2.59	3.157 (2)	124
N2—H2···O2ⁱⁱ	0.86	1.90	2.762 (2)	175

Symmetry code: (ii) x, y, z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₆N₄²⁺·2NO₃⁻
M_r	316.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	7.788 (2), 10.482 (3), 9.363 (3)
β (°)	110.649 (4)
V (Å³)	715.3 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.43 × 0.40 × 0.31

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.949, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	3629, 1257, 913
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.115, 1.06
No. of reflections	1257
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.59	3.157 (2)	124.3
N2—H2···O2ⁱ	0.86	1.90	2.762 (2)	174.8

Symmetry code: (i) x, y, z+1.

Acknowledgements

The authors thank the Zhejiang Forestry University Science Foundation for financial support.

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