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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o169.
Published online 2007 December 6. doi:  10.1107/S1600536807063751
PMCID: PMC2915236

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

Abstract

In the title compound, C10H16N4 2+·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 [triangle]); Holman et al. (2001 [triangle]); Jin & Chen (2007a [triangle],b [triangle]); Jin et al. (2007 [triangle]); Królikowska & Garbarczyk (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o169-scheme1.jpg

Experimental

Crystal data

  • C10H16N4 2+·2NO3
  • M r = 316.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o169-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.115
  • S = 1.06
  • 1257 reflections
  • 100 parameters
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [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: SHELXTL (Bruker, 2001 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063751/gk2116Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H atoms were located in a difference Fourier map. H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms (C—H = 0.93–0.97 Å, N—H = 0.86 Å) with Uiso(H) = 1.2Ueq(C, N).

Figures

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).

Crystal data

C10H16N42+·2NO3F000 = 332
Mr = 316.29Dx = 1.469 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1224 reflections
a = 7.788 (2) Åθ = 2.8–24.0º
b = 10.482 (3) ŵ = 0.12 mm1
c = 9.363 (3) ÅT = 298 (2) K
β = 110.649 (4)ºBlock, colourless
V = 715.3 (4) Å30.43 × 0.40 × 0.31 mm
Z = 2

Data collection

Bruker SMART APEXII CCD diffractometer1257 independent reflections
Radiation source: fine-focus sealed tube913 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.036
T = 298(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 2.9º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.949, Tmax = 0.963k = −12→10
3629 measured reflectionsl = −11→8

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.115  w = 1/[σ2(Fo2) + (0.0497P)2 + 0.1767P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1257 reflectionsΔρmax = 0.21 e Å3
100 parametersΔρmin = −0.20 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
N10.6076 (2)0.66149 (16)0.79775 (17)0.0408 (4)
N20.5677 (2)0.72628 (16)1.00094 (19)0.0483 (5)
H20.56700.72811.09250.058*
N30.6173 (2)0.84419 (17)0.3487 (2)0.0458 (5)
O10.6683 (3)0.92237 (15)0.27403 (18)0.0673 (5)
O20.5460 (2)0.74148 (15)0.28855 (17)0.0623 (5)
O30.6379 (3)0.86529 (19)0.4822 (2)0.0934 (7)
C10.6268 (3)0.6310 (2)0.9390 (2)0.0465 (5)
H10.67440.55460.98720.056*
C20.5079 (3)0.8216 (2)0.8959 (2)0.0472 (5)
H2A0.45900.89960.90980.057*
C30.5331 (3)0.78137 (19)0.7687 (2)0.0440 (5)
H30.50510.82640.67780.053*
C40.6486 (3)0.5788 (2)0.6874 (2)0.0509 (6)
H4A0.70790.50160.73850.061*
H4B0.73320.62230.64880.061*
C50.4777 (3)0.54372 (19)0.5556 (2)0.0423 (5)
H5A0.41950.62070.50300.051*
H5B0.39200.50140.59410.051*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0393 (9)0.0461 (10)0.0335 (9)−0.0006 (8)0.0086 (7)−0.0054 (7)
N20.0578 (12)0.0535 (11)0.0342 (9)−0.0049 (9)0.0167 (8)−0.0053 (8)
N30.0479 (10)0.0514 (11)0.0390 (10)0.0031 (9)0.0168 (8)0.0011 (9)
O10.0972 (14)0.0527 (10)0.0581 (10)−0.0080 (9)0.0349 (10)0.0098 (8)
O20.0810 (12)0.0549 (10)0.0557 (10)−0.0154 (9)0.0298 (9)−0.0085 (8)
O30.1370 (18)0.1073 (16)0.0490 (11)−0.0433 (14)0.0491 (11)−0.0251 (10)
C10.0503 (13)0.0439 (12)0.0398 (12)−0.0001 (10)0.0090 (10)−0.0012 (9)
C20.0500 (12)0.0408 (11)0.0470 (13)−0.0010 (10)0.0125 (10)−0.0054 (10)
C30.0470 (12)0.0419 (12)0.0390 (11)−0.0035 (10)0.0100 (9)0.0007 (9)
C40.0453 (13)0.0594 (14)0.0469 (13)0.0037 (11)0.0148 (10)−0.0142 (10)
C50.0407 (11)0.0446 (11)0.0409 (11)−0.0020 (9)0.0136 (9)−0.0062 (9)

Geometric parameters (Å, °)

N1—C11.317 (2)C2—C31.342 (3)
N1—C31.371 (3)C2—H2A0.9300
N1—C41.467 (2)C3—H30.9300
N2—C11.316 (3)C4—C51.507 (3)
N2—C21.364 (3)C4—H4A0.9700
N2—H20.8600C4—H4B0.9700
N3—O31.223 (2)C5—C5i1.518 (4)
N3—O11.231 (2)C5—H5A0.9700
N3—O21.251 (2)C5—H5B0.9700
C1—H10.9300
C1—N1—C3108.15 (16)C2—C3—N1107.24 (18)
C1—N1—C4126.02 (18)C2—C3—H3126.4
C3—N1—C4125.73 (17)N1—C3—H3126.4
C1—N2—C2108.78 (18)N1—C4—C5111.83 (16)
C1—N2—H2125.6N1—C4—H4A109.3
C2—N2—H2125.6C5—C4—H4A109.3
O3—N3—O1120.54 (19)N1—C4—H4B109.3
O3—N3—O2119.56 (18)C5—C4—H4B109.3
O1—N3—O2119.90 (18)H4A—C4—H4B107.9
N2—C1—N1108.97 (18)C4—C5—C5i111.1 (2)
N2—C1—H1125.5C4—C5—H5A109.4
N1—C1—H1125.5C5i—C5—H5A109.4
C3—C2—N2106.86 (19)C4—C5—H5B109.4
C3—C2—H2A126.6C5i—C5—H5B109.4
N2—C2—H2A126.6H5A—C5—H5B108.0
C2—N2—C1—N10.1 (2)C1—N1—C3—C2−0.1 (2)
C3—N1—C1—N20.0 (2)C4—N1—C3—C2176.60 (18)
C4—N1—C1—N2−176.70 (17)C1—N1—C4—C5113.5 (2)
C1—N2—C2—C3−0.2 (2)C3—N1—C4—C5−62.7 (3)
N2—C2—C3—N10.2 (2)N1—C4—C5—C5i−179.0 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O1ii0.862.593.157 (2)124
N2—H2···O2ii0.861.902.762 (2)175

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2116).

References

  • Bruker (1997). SAINT and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2001). SHELXTL Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Gould, P. J. (1986). Int. J. Pharm.33, 201–217.
  • Holman, K. T., Pivovar, A. M., Swift, J. A. & Ward, M. D. (2001). Acc. Chem. Res.34, 107–118. [PubMed]
  • Jin, S. W. & Chen, W. Z. (2007a). Polyhedron, 26, 3074–3084.
  • Jin, S. W. & Chen, W. Z. (2007b). Inorg. Chim. Acta, 12, 3756–3764.
  • Jin, S. W., Wang, D. Q. & Chen, W. Z. (2007). Inorg. Chem. Commun.10, 685–689.
  • Królikowska, M. & Garbarczyk, J. (2005). Z. Kristallogr. New Cryst. Struct.220, 103–104.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (1997). SHELXL97 and SHELXS97 University of Göttingen, Germany.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography