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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1561.
Published online 2008 July 19. doi:  10.1107/S1600536808022393
PMCID: PMC2962153

3,3′-(Butane-1,4-di­yl)diimidazole-1,1′-diium bis­(triiodide)

Abstract

The cations and anions of the salt, C10H16N4 2+·2I3 , are linked by N—H(...)I hydrogen bonds and π–π stacking inter­actions(with interplanar distances of 3.575 and 3.528 Å) into a three-dimensional supra­molecular network. The asymmetric unit contains two anions and two half-cations; each cation is centrosymmetric.

Related literature

For literature on 1,1′-(1,4-butanedi­yl)diimidazole, see: Ma et al. (2003 [triangle]). For the structure of another 1,1′-(1,4-butanedi­yl)diimidazole-3,3′-diium salt, see: Yu et al. (2008 [triangle]).

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Object name is e-64-o1561-scheme1.jpg

Experimental

Crystal data

  • C10H16N4 2+·2I3
  • M r = 953.67
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1561-efi1.jpg
  • a = 8.4753 (17) Å
  • b = 9.7177 (19) Å
  • c = 14.110 (3) Å
  • α = 95.77 (3)°
  • β = 92.82 (3)°
  • γ = 107.17 (3)°
  • V = 1100.9 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 8.46 mm−1
  • T = 291 (2) K
  • 0.21 × 0.20 × 0.18 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.266, T max = 0.306 (expected range = 0.189–0.218)
  • 8492 measured reflections
  • 3831 independent reflections
  • 3045 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.087
  • S = 1.10
  • 3831 reflections
  • 178 parameters
  • H-atom parameters constrained
  • Δρmax = 1.19 e Å−3
  • Δρmin = −0.86 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808022393/ng2463sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022393/ng2463Isup2.hkl

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

Acknowledgments

The authors thank Heilongjiang University for supporting this study.

supplementary crystallographic information

Comment

The 1,1'-(1,4-butanediyl)diimidazole can be used as a flexible ligand to construct coordination polymer materials (Ma et al., 2003; Yu et al., 2008). In our attempt to synthesize the copper(I) iodide complex with the 1,1'-(1,4-butanediyl)diimidazole, we unexpectedly obtained the title compound (I). Herein, we report its crystal structure.

The asymmetric unit of (I) consists of two halfs of two independent centrosymmetric molecules of 1,1'-(1,4-Butanediyl)diimidazole-3,3'-diium cation and two triiodide anions (Figure 1). The remarkable π-π stacking interactions are observed, with the distance between the π-π stacking planes are 3.575 Å (cations); 3.528 Å (Figure 2),

In the crystal, intermolecular N—H···I, C—H···I hydrogen bonds and π-π stacking interactions link all cations and anions into three-dimensional supramolecular network (Table 1).

Experimental

1,1'-(1,4-Butanediyl)diimidazole was prepared of imidazole and 1,4-dibromobutane in dimethylsulfoxide solution (Ma et al.., 2003). CuI (0.380 g, 2 mmol) and 1,1'-(1,4-butanediyl)diimidazole (0.380 g, 2 mmol) were dissolved in hot methanol solution (15 ml) and added two drops hydrochloric acid then a clear solution was obtained. The resulting solution was allowed to stand in a desiccator at room temperature for several days. Yellow crystals of (I) were obtained. Unexpectedly, the salt-type adducts of this ligands was crystallized from solution.

Refinement

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (Caromatic); C—H = 0.97 Å (methylene) and with Uiso(H) = 1.2Ueq(C). The N-bound H atoms were located in a difference Fourier map and refined with N—H = 0.85 Å, Uiso(H) = 1.2Ueq(N). The final different Fourier map had a large peak in the vicinity of the iodine atoms.

Figures

Fig. 1.
The molecular structure of (I), showing displacement ellipsoids at the 30% probability level for non-H atoms.
Fig. 2.
A partial packing view, showing π-π interactions. Dashed lines indicate the hydrogen-bonding interactions and π-π interactions. H atoms not involved in hydrogen bonds have been omitted for clarity.

Crystal data

C10H16N42+·2I3Z = 2
Mr = 953.67F000 = 844
Triclinic, P1Dx = 2.877 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 8.4753 (17) ÅCell parameters from 7434 reflections
b = 9.7177 (19) Åθ = 3.0–27.5º
c = 14.110 (3) ŵ = 8.46 mm1
α = 95.77 (3)ºT = 291 (2) K
β = 92.82 (3)ºBlock, yellow
γ = 107.17 (3)º0.21 × 0.20 × 0.18 mm
V = 1100.9 (4) Å3

Data collection

Rigaku R-AXIS RAPID diffractometer3831 independent reflections
Radiation source: fine-focus sealed tube3045 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.031
T = 291(2) Kθmax = 25.0º
ω scansθmin = 3.0º
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)h = −10→10
Tmin = 0.266, Tmax = 0.307k = −11→11
8492 measured reflectionsl = −16→16

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.087  w = 1/[σ2(Fo2) + (0.0254P)2 + 5.2161P] where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
3831 reflectionsΔρmax = 1.19 e Å3
178 parametersΔρmin = −0.86 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
C10.6046 (11)0.3684 (10)0.5506 (6)0.049 (2)
H10.71420.38300.53690.058*
C20.5511 (12)0.4469 (11)0.6176 (7)0.055 (2)
H20.61590.52680.65850.066*
C30.3377 (12)0.2777 (12)0.5469 (7)0.056 (2)
H40.22930.21910.53050.067*
C40.4772 (13)0.1552 (11)0.4282 (6)0.057 (3)
H60.54580.20280.38080.069*
H50.36640.10900.39770.069*
C50.5466 (12)0.0400 (11)0.4628 (7)0.062 (3)
H80.5474−0.02930.40850.075*
H70.66050.08600.48840.075*
C61.0068 (12)0.3316 (11)0.1048 (7)0.055 (2)
H90.93620.29150.14990.066*
C71.1312 (11)0.4573 (11)0.1195 (8)0.057 (3)
H101.16360.52080.17580.068*
C81.1230 (13)0.3611 (11)−0.0302 (7)0.056 (3)
H121.14900.3477−0.09300.067*
C90.8858 (8)0.1352 (8)−0.0341 (6)0.055 (2)
H130.89750.1278−0.10230.066*
H140.77340.1358−0.02470.066*
C100.9139 (8)0.0029 (8)0.0049 (6)0.079 (4)
H150.89230.00550.07180.094*
H160.8364−0.0844−0.02930.094*
I10.55146 (9)0.37444 (7)0.15451 (5)0.05732 (19)
I20.54230 (7)0.06704 (6)0.16015 (4)0.04222 (15)
I30.53942 (8)−0.22804 (7)0.16387 (5)0.0602 (2)
I40.96410 (8)0.34498 (8)0.37380 (5)0.0608 (2)
I50.99004 (7)0.05335 (7)0.33765 (4)0.05118 (17)
I61.03499 (9)−0.23842 (8)0.31071 (5)0.0636 (2)
N11.0024 (9)0.2733 (8)0.0121 (5)0.0471 (18)
N21.1981 (10)0.4712 (9)0.0356 (6)0.060 (2)
H111.29060.52580.02110.072*
N30.4708 (8)0.2639 (8)0.5063 (5)0.0443 (17)
N40.3853 (10)0.3886 (9)0.6146 (6)0.058 (2)
H30.31110.40940.64800.070*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.039 (5)0.053 (6)0.048 (5)0.005 (4)0.007 (4)0.002 (5)
C20.054 (6)0.052 (6)0.049 (6)0.006 (5)−0.003 (5)−0.002 (5)
C30.050 (6)0.068 (7)0.052 (6)0.021 (5)0.009 (5)0.007 (5)
C40.062 (6)0.074 (7)0.038 (5)0.027 (6)0.005 (5)−0.001 (5)
C50.060 (6)0.063 (7)0.067 (7)0.023 (6)0.017 (5)0.002 (5)
C60.052 (6)0.067 (7)0.049 (6)0.026 (6)0.004 (5)−0.003 (5)
C70.039 (5)0.049 (6)0.072 (7)0.005 (5)−0.010 (5)−0.012 (5)
C80.067 (6)0.061 (7)0.050 (6)0.034 (6)0.006 (5)0.011 (5)
C90.051 (5)0.045 (6)0.060 (6)0.003 (5)−0.006 (5)0.006 (5)
C100.056 (6)0.037 (6)0.121 (10)−0.018 (5)−0.001 (7)0.009 (6)
I10.0714 (4)0.0472 (4)0.0598 (4)0.0265 (3)0.0108 (3)0.0079 (3)
I20.0397 (3)0.0447 (3)0.0383 (3)0.0090 (3)0.0015 (2)−0.0012 (2)
I30.0601 (4)0.0393 (4)0.0767 (5)0.0106 (3)−0.0034 (3)0.0040 (3)
I40.0584 (4)0.0562 (4)0.0616 (4)0.0098 (3)0.0076 (3)−0.0007 (3)
I50.0415 (3)0.0630 (4)0.0443 (3)0.0107 (3)−0.0010 (3)0.0020 (3)
I60.0660 (4)0.0729 (5)0.0604 (4)0.0338 (4)0.0089 (3)0.0062 (4)
N10.051 (4)0.048 (5)0.049 (5)0.022 (4)0.004 (4)0.014 (4)
N20.049 (5)0.061 (6)0.075 (6)0.024 (4)0.006 (5)0.017 (5)
N30.040 (4)0.048 (5)0.043 (4)0.009 (4)0.003 (3)0.008 (3)
N40.054 (5)0.065 (6)0.055 (5)0.015 (4)0.015 (4)0.004 (4)

Geometric parameters (Å, °)

C1—C21.335 (13)C7—N21.340 (13)
C1—N31.354 (11)C7—H100.9300
C1—H10.9300C8—N11.332 (12)
C2—N41.348 (12)C8—N21.324 (12)
C2—H20.9300C8—H120.9300
C3—N41.317 (12)C9—N11.477 (10)
C3—N31.326 (11)C9—C101.5246
C3—H40.9300C9—H130.9700
C4—N31.462 (11)C9—H140.9700
C4—C51.519 (13)C10—C10ii1.489
C4—H60.9700C10—H150.9700
C4—H50.9700C10—H160.9700
C5—C5i1.487 (19)I1—I22.9745 (10)
C5—H80.9700I2—I32.8662 (10)
C5—H70.9700I4—I52.9031 (11)
C6—C71.347 (13)I5—I62.9604 (11)
C6—N11.367 (11)N2—H110.8544
C6—H90.9300N4—H30.8628
C2—C1—N3107.7 (8)N1—C8—H12127.1
C2—C1—H1126.2N2—C8—H12127.1
N3—C1—H1126.2N1—C9—C10112.9
C1—C2—N4107.1 (9)N1—C9—H13109.0
C1—C2—H2126.5C10—C9—H13109.0
N4—C2—H2126.5N1—C9—H14109.0
N4—C3—N3108.2 (9)C10—C9—H14109.0
N4—C3—H4125.9H13—C9—H14107.8
N3—C3—H4125.9C10ii—C10—C9112.0 (5)
N3—C4—C5112.1 (8)C10ii—C10—H15109.2
N3—C4—H6109.2C9—C10—H15109.2
C5—C4—H6109.2C10ii—C10—H16109.2
N3—C4—H5109.2C9—C10—H16109.2
C5—C4—H5109.2H15—C10—H16107.9
H6—C4—H5107.9I3—I2—I1178.89 (3)
C5i—C5—C4114.5 (10)I4—I5—I6176.21 (3)
C5i—C5—H8108.6C8—N1—C6108.7 (9)
C4—C5—H8108.6C8—N1—C9125.1 (8)
C5i—C5—H7108.6C6—N1—C9126.2 (8)
C4—C5—H7108.6C8—N2—C7112.3 (9)
H8—C5—H7107.6C8—N2—H11114.7
C7—C6—N1108.1 (9)C7—N2—H11131.3
C7—C6—H9125.9C3—N3—C1108.0 (8)
N1—C6—H9125.9C3—N3—C4127.3 (8)
C6—C7—N2105.0 (9)C1—N3—C4124.6 (7)
C6—C7—H10127.5C3—N4—C2109.0 (8)
N2—C7—H10127.5C3—N4—H3118.4
N1—C8—N2105.9 (9)C2—N4—H3132.6

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H11···I3iii0.853.143.690 (9)124
N2—H11···I1iv0.852.993.666 (9)138
N4—H3···I1v0.863.253.714 (9)116
N4—H3···I6i0.863.033.679 (8)134
C6—H9···I40.933.133.823 (10)132

Symmetry codes: (iii) x+1, y+1, z; (iv) −x+2, −y+1, −z; (v) −x+1, −y+1, −z+1; (i) −x+1, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2463).

References

  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Ma, J.-F., Yang, J., Zheng, G.-L. & Liu, J.-F. (2003). Inorg. Chem.42, 7531–7534. [PubMed]
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Yu, Y.-H., Shi, A.-E., Su, Y., Hou, G.-F. & Gao, J.-S. (2008). Acta Cryst. E64, m628. [PMC free article] [PubMed]

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