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

Shi, A.-E.; Yu, Y.-H.; Hou, G.-F.; Gao, J.-S.

doi:10.1107/S1600536808022393

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1561

doi:10.1107/S1600536808022393

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

Ai-E. Shi,^a Ying-Hui Yu,^a Guang-Feng Hou ^a and Jin-Sheng Gao ^a ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: hgf1000@163.com

(Received 9 June 2008; accepted 17 July 2008; online 19 July 2008)

The cations and anions of the salt, C₁₀H₁₆N₄²⁺·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 ). For the structure of another 1,1′-(1,4-butanediyl)diimidazole-3,3′-diium salt, see: Yu et al. (2008 ).

Experimental

Crystal data

C₁₀H₁₆N₄²⁺·2I₃⁻
M_r = 953.67
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.087
S = 1.10
3831 reflections
178 parameters
H-atom parameters constrained
Δρ_max = 1.19 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H11⋯I3ⁱ	0.85	3.14	3.690 (9)	124
N2—H11⋯I1ⁱⁱ	0.85	2.99	3.666 (9)	138
N4—H3⋯I1ⁱⁱⁱ	0.86	3.25	3.714 (9)	116
N4—H3⋯I6^iv	0.86	3.03	3.679 (8)	134
Symmetry codes: (i) x+1, y+1, z; (ii) -x+2, -y+1, -z; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y, -z+1.

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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.

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

Crystal data top

C₁₀H₁₆N₄²⁺·2I₃⁻	Z = 2
M_r = 953.67	F(000) = 844
Triclinic, P1	D_x = 2.877 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4753 (17) Å	Cell parameters from 7434 reflections
b = 9.7177 (19) Å	θ = 3.0–27.5°
c = 14.110 (3) Å	µ = 8.46 mm⁻¹
α = 95.77 (3)°	T = 291 K
β = 92.82 (3)°	Block, yellow
γ = 107.17 (3)°	0.21 × 0.20 × 0.18 mm
V = 1100.9 (4) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	3831 independent reflections
Radiation source: fine-focus sealed tube	3045 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.266, T_max = 0.307	k = −11→11
8492 measured reflections	l = −16→16

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0254P)² + 5.2161P] where P = (F_o² + 2F_c²)/3
3831 reflections	(Δ/σ)_max = 0.001
178 parameters	Δρ_max = 1.19 e Å⁻³
0 restraints	Δρ_min = −0.86 e Å⁻³

Crystal data top

C₁₀H₁₆N₄²⁺·2I₃⁻	γ = 107.17 (3)°
M_r = 953.67	V = 1100.9 (4) Å³
Triclinic, P1	Z = 2
a = 8.4753 (17) Å	Mo Kα radiation
b = 9.7177 (19) Å	µ = 8.46 mm⁻¹
c = 14.110 (3) Å	T = 291 K
α = 95.77 (3)°	0.21 × 0.20 × 0.18 mm
β = 92.82 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3831 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3045 reflections with I > 2σ(I)
T_min = 0.266, T_max = 0.307	R_int = 0.031
8492 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.10	Δρ_max = 1.19 e Å⁻³
3831 reflections	Δρ_min = −0.86 e Å⁻³
178 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	0.6046 (11)	0.3684 (10)	0.5506 (6)	0.049 (2)
H1	0.7142	0.3830	0.5369	0.058*
C2	0.5511 (12)	0.4469 (11)	0.6176 (7)	0.055 (2)
H2	0.6159	0.5268	0.6585	0.066*
C3	0.3377 (12)	0.2777 (12)	0.5469 (7)	0.056 (2)
H4	0.2293	0.2191	0.5305	0.067*
C4	0.4772 (13)	0.1552 (11)	0.4282 (6)	0.057 (3)
H6	0.5458	0.2028	0.3808	0.069*
H5	0.3664	0.1090	0.3977	0.069*
C5	0.5466 (12)	0.0400 (11)	0.4628 (7)	0.062 (3)
H8	0.5474	−0.0293	0.4085	0.075*
H7	0.6605	0.0860	0.4884	0.075*
C6	1.0068 (12)	0.3316 (11)	0.1048 (7)	0.055 (2)
H9	0.9362	0.2915	0.1499	0.066*
C7	1.1312 (11)	0.4573 (11)	0.1195 (8)	0.057 (3)
H10	1.1636	0.5208	0.1758	0.068*
C8	1.1230 (13)	0.3611 (11)	−0.0302 (7)	0.056 (3)
H12	1.1490	0.3477	−0.0930	0.067*
C9	0.8858 (8)	0.1352 (8)	−0.0341 (6)	0.055 (2)
H13	0.8975	0.1278	−0.1023	0.066*
H14	0.7734	0.1358	−0.0247	0.066*
C10	0.9139 (8)	0.0029 (8)	0.0049 (6)	0.079 (4)
H15	0.8923	0.0055	0.0718	0.094*
H16	0.8364	−0.0844	−0.0293	0.094*
I1	0.55146 (9)	0.37444 (7)	0.15451 (5)	0.05732 (19)
I2	0.54230 (7)	0.06704 (6)	0.16015 (4)	0.04222 (15)
I3	0.53942 (8)	−0.22804 (7)	0.16387 (5)	0.0602 (2)
I4	0.96410 (8)	0.34498 (8)	0.37380 (5)	0.0608 (2)
I5	0.99004 (7)	0.05335 (7)	0.33765 (4)	0.05118 (17)
I6	1.03499 (9)	−0.23842 (8)	0.31071 (5)	0.0636 (2)
N1	1.0024 (9)	0.2733 (8)	0.0121 (5)	0.0471 (18)
N2	1.1981 (10)	0.4712 (9)	0.0356 (6)	0.060 (2)
H11	1.2906	0.5258	0.0211	0.072*
N3	0.4708 (8)	0.2639 (8)	0.5063 (5)	0.0443 (17)
N4	0.3853 (10)	0.3886 (9)	0.6146 (6)	0.058 (2)
H3	0.3111	0.4094	0.6480	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.039 (5)	0.053 (6)	0.048 (5)	0.005 (4)	0.007 (4)	0.002 (5)
C2	0.054 (6)	0.052 (6)	0.049 (6)	0.006 (5)	−0.003 (5)	−0.002 (5)
C3	0.050 (6)	0.068 (7)	0.052 (6)	0.021 (5)	0.009 (5)	0.007 (5)
C4	0.062 (6)	0.074 (7)	0.038 (5)	0.027 (6)	0.005 (5)	−0.001 (5)
C5	0.060 (6)	0.063 (7)	0.067 (7)	0.023 (6)	0.017 (5)	0.002 (5)
C6	0.052 (6)	0.067 (7)	0.049 (6)	0.026 (6)	0.004 (5)	−0.003 (5)
C7	0.039 (5)	0.049 (6)	0.072 (7)	0.005 (5)	−0.010 (5)	−0.012 (5)
C8	0.067 (6)	0.061 (7)	0.050 (6)	0.034 (6)	0.006 (5)	0.011 (5)
C9	0.051 (5)	0.045 (6)	0.060 (6)	0.003 (5)	−0.006 (5)	0.006 (5)
C10	0.056 (6)	0.037 (6)	0.121 (10)	−0.018 (5)	−0.001 (7)	0.009 (6)
I1	0.0714 (4)	0.0472 (4)	0.0598 (4)	0.0265 (3)	0.0108 (3)	0.0079 (3)
I2	0.0397 (3)	0.0447 (3)	0.0383 (3)	0.0090 (3)	0.0015 (2)	−0.0012 (2)
I3	0.0601 (4)	0.0393 (4)	0.0767 (5)	0.0106 (3)	−0.0034 (3)	0.0040 (3)
I4	0.0584 (4)	0.0562 (4)	0.0616 (4)	0.0098 (3)	0.0076 (3)	−0.0007 (3)
I5	0.0415 (3)	0.0630 (4)	0.0443 (3)	0.0107 (3)	−0.0010 (3)	0.0020 (3)
I6	0.0660 (4)	0.0729 (5)	0.0604 (4)	0.0338 (4)	0.0089 (3)	0.0062 (4)
N1	0.051 (4)	0.048 (5)	0.049 (5)	0.022 (4)	0.004 (4)	0.014 (4)
N2	0.049 (5)	0.061 (6)	0.075 (6)	0.024 (4)	0.006 (5)	0.017 (5)
N3	0.040 (4)	0.048 (5)	0.043 (4)	0.009 (4)	0.003 (3)	0.008 (3)
N4	0.054 (5)	0.065 (6)	0.055 (5)	0.015 (4)	0.015 (4)	0.004 (4)

Geometric parameters (Å, º) top

C1—C2	1.335 (13)	C7—N2	1.340 (13)
C1—N3	1.354 (11)	C7—H10	0.9300
C1—H1	0.9300	C8—N1	1.332 (12)
C2—N4	1.348 (12)	C8—N2	1.324 (12)
C2—H2	0.9300	C8—H12	0.9300
C3—N4	1.317 (12)	C9—N1	1.477 (10)
C3—N3	1.326 (11)	C9—C10	1.5246
C3—H4	0.9300	C9—H13	0.9700
C4—N3	1.462 (11)	C9—H14	0.9700
C4—C5	1.519 (13)	C10—C10ⁱⁱ	1.489
C4—H6	0.9700	C10—H15	0.9700
C4—H5	0.9700	C10—H16	0.9700
C5—C5ⁱ	1.487 (19)	I1—I2	2.9745 (10)
C5—H8	0.9700	I2—I3	2.8662 (10)
C5—H7	0.9700	I4—I5	2.9031 (11)
C6—C7	1.347 (13)	I5—I6	2.9604 (11)
C6—N1	1.367 (11)	N2—H11	0.8544
C6—H9	0.9300	N4—H3	0.8628

C2—C1—N3	107.7 (8)	N1—C8—H12	127.1
C2—C1—H1	126.2	N2—C8—H12	127.1
N3—C1—H1	126.2	N1—C9—C10	112.9
C1—C2—N4	107.1 (9)	N1—C9—H13	109.0
C1—C2—H2	126.5	C10—C9—H13	109.0
N4—C2—H2	126.5	N1—C9—H14	109.0
N4—C3—N3	108.2 (9)	C10—C9—H14	109.0
N4—C3—H4	125.9	H13—C9—H14	107.8
N3—C3—H4	125.9	C10ⁱⁱ—C10—C9	112.0 (5)
N3—C4—C5	112.1 (8)	C10ⁱⁱ—C10—H15	109.2
N3—C4—H6	109.2	C9—C10—H15	109.2
C5—C4—H6	109.2	C10ⁱⁱ—C10—H16	109.2
N3—C4—H5	109.2	C9—C10—H16	109.2
C5—C4—H5	109.2	H15—C10—H16	107.9
H6—C4—H5	107.9	I3—I2—I1	178.89 (3)
C5ⁱ—C5—C4	114.5 (10)	I4—I5—I6	176.21 (3)
C5ⁱ—C5—H8	108.6	C8—N1—C6	108.7 (9)
C4—C5—H8	108.6	C8—N1—C9	125.1 (8)
C5ⁱ—C5—H7	108.6	C6—N1—C9	126.2 (8)
C4—C5—H7	108.6	C8—N2—C7	112.3 (9)
H8—C5—H7	107.6	C8—N2—H11	114.7
C7—C6—N1	108.1 (9)	C7—N2—H11	131.3
C7—C6—H9	125.9	C3—N3—C1	108.0 (8)
N1—C6—H9	125.9	C3—N3—C4	127.3 (8)
C6—C7—N2	105.0 (9)	C1—N3—C4	124.6 (7)
C6—C7—H10	127.5	C3—N4—C2	109.0 (8)
N2—C7—H10	127.5	C3—N4—H3	118.4
N1—C8—N2	105.9 (9)	C2—N4—H3	132.6

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H11···I3ⁱⁱⁱ	0.85	3.14	3.690 (9)	124
N2—H11···I1^iv	0.85	2.99	3.666 (9)	138
N4—H3···I1^v	0.86	3.25	3.714 (9)	116
N4—H3···I6ⁱ	0.86	3.03	3.679 (8)	134
C6—H9···I4	0.93	3.13	3.823 (10)	132

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₆N₄²⁺·2I₃⁻
M_r	953.67
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	8.4753 (17), 9.7177 (19), 14.110 (3)
α, β, γ (°)	95.77 (3), 92.82 (3), 107.17 (3)
V (Å³)	1100.9 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	8.46
Crystal size (mm)	0.21 × 0.20 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.266, 0.307
No. of measured, independent and observed [I > 2σ(I)] reflections	8492, 3831, 3045
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.087, 1.10
No. of reflections	3831
No. of parameters	178
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.19, −0.86

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H11···I3ⁱ	0.85	3.14	3.690 (9)	124.3
N2—H11···I1ⁱⁱ	0.85	2.99	3.666 (9)	138.0
N4—H3···I1ⁱⁱⁱ	0.86	3.25	3.714 (9)	116.0
N4—H3···I6^iv	0.86	3.03	3.679 (8)	133.6

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

Acknowledgements

The authors thank Heilongjiang University for supporting this study.

References

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Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
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