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

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ISSN: 2056-9890

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

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[Gould, P. J. (1986). Int. J. Pharm. 33, 201-217.]); Holman et al. (2001[Holman, K. T., Pivovar, A. M., Swift, J. A. & Ward, M. D. (2001). Acc. Chem. Res. 34, 107-118.]); Jin & Chen (2007a[Jin, S. W. & Chen, W. Z. (2007a). Polyhedron, 26, 3074-3084.],b[Jin, S. W. & Chen, W. Z. (2007b). Inorg. Chim. Acta, 12, 3756-3764.]); Jin et al. (2007[Jin, S. W., Wang, D. Q. & Chen, W. Z. (2007). Inorg. Chem. Commun. 10, 685-689.]); Królikowska & Garbarczyk (2005[Królikowska, M. & Garbarczyk, J. (2005). Z. Kristallogr. New Cryst. Struct. 220, 103-104.]).

[Scheme 1]

Experimental

Crystal data
  • C10H16N42+·2NO3

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.949, Tmax = 0.963

  • 3629 measured reflections

  • 1257 independent reflections

  • 913 reflections with I > 2σ(I)

  • Rint = 0.036

Refinement
  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (1997). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.]); molecular graphics: SHELXTL (Bruker, 2001[Bruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

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).

Structure description 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).

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
[Figure 1] Fig. 1. The structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] 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+·2NO3F(000) = 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 = 2.8–24.0°
b = 10.482 (3) ŵ = 0.12 mm1
c = 9.363 (3) ÅT = 298 K
β = 110.649 (4)°Block, colourless
V = 715.3 (4) Å30.43 × 0.40 × 0.31 mm
Z = 2
Data collection top
Bruker SMART APEXII CCD
diffractometer
1257 independent reflections
Radiation source: fine-focus sealed tube913 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
φ and ω scansθmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.949, Tmax = 0.963k = 1210
3629 measured reflectionsl = 118
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0497P)2 + 0.1767P]
where P = (Fo2 + 2Fc2)/3
1257 reflections(Δ/σ)max < 0.001
100 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C10H16N42+·2NO3V = 715.3 (4) Å3
Mr = 316.29Z = 2
Monoclinic, P21/nMo Kα radiation
a = 7.788 (2) ŵ = 0.12 mm1
b = 10.482 (3) ÅT = 298 K
c = 9.363 (3) Å0.43 × 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)
Tmin = 0.949, Tmax = 0.963Rint = 0.036
3629 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.115H-atom parameters constrained
S = 1.06Δρmax = 0.21 e Å3
1257 reflectionsΔρmin = 0.20 e Å3
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
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) top
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, º) top
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—C20.1 (2)
C3—N1—C1—N20.0 (2)C4—N1—C3—C2176.60 (18)
C4—N1—C1—N2176.70 (17)C1—N1—C4—C5113.5 (2)
C1—N2—C2—C30.2 (2)C3—N1—C4—C562.7 (3)
N2—C2—C3—N10.2 (2)N1—C4—C5—C5i179.0 (2)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
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 code: (ii) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC10H16N42+·2NO3
Mr316.29
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)7.788 (2), 10.482 (3), 9.363 (3)
β (°) 110.649 (4)
V3)715.3 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.43 × 0.40 × 0.31
Data collection
DiffractometerBruker SMART APEXII CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.949, 0.963
No. of measured, independent and
observed [I > 2σ(I)] reflections
3629, 1257, 913
Rint0.036
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.115, 1.06
No. of reflections1257
No. of parameters100
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H2···O1i0.862.593.157 (2)124.3
N2—H2···O2i0.861.902.762 (2)174.8
Symmetry code: (i) x, y, z+1.
 

Acknowledgements

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

References

First citationBruker (1997). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationGould, P. J. (1986). Int. J. Pharm. 33, 201–217.  CrossRef CAS Web of Science Google Scholar
First citationHolman, K. T., Pivovar, A. M., Swift, J. A. & Ward, M. D. (2001). Acc. Chem. Res. 34, 107–118.  Web of Science CrossRef PubMed CAS Google Scholar
First citationJin, S. W. & Chen, W. Z. (2007a). Polyhedron, 26, 3074–3084.  Web of Science CSD CrossRef CAS Google Scholar
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First citationJin, S. W., Wang, D. Q. & Chen, W. Z. (2007). Inorg. Chem. Commun. 10, 685–689.  Web of Science CSD CrossRef CAS Google Scholar
First citationKrólikowska, M. & Garbarczyk, J. (2005). Z. Kristallogr. New Cryst. Struct. 220, 103–104.  Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.  Google Scholar

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ISSN: 2056-9890
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