1,1′-(Butane-1,4-di­yl)bis­(imidazolium) bis­(perchlorate)

The asymmetric unit of the title compound, C₁₀H₁₆N₄²⁺·2ClO₄⁻, consists of half of a centrosymmetric 1,1′-(butane-1,4-di­yl)bis­(imidazolium) cation and one perchlorate anion. These ions are linked to each other by inter­molecular bifurcated N—H...O hydrogen bonds to form infinite chains, which are further connected to each other by weak C—H...O hydrogen bonds to build up a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.035
• wR factor = 0.095
• Data-to-parameter ratio = 13.5

checkCIF/PLATON results

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Alert level C
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Cl1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In recent years, metal coordination polymers with flexible bis(imidazole) ligands has been a rapidly developing area of research, because of its intriguing structures and potential applications in functional materials(Moulton & Zaworotko, 2001), such as 1,4'-bis(imidazol-1-ylmethyl)benzene (Fan et al., 2006; Hoskins et al., 1997), 1,1'-(1,2-ethanediyl)bis(imidazole) (Ding et al., 2006), 1,1'-(butane-1,4-diyl)bis(imidazole) (bim; Yang et al., 2006). Some others have been widely studied on their properties of bifunctional di(imidazole) templates of varying geometry (Dhal & Arnold, 1992) and imidazolium salts (Sato et al.,1999). In our previous studies, we have synthesized coordination polymer and imidazolium with 1,3'-bis(imidazol-1-ylmethyl)-5-methylbenzene (Ma et al., 2003; Yao et al., 2003).

In order to understand the influence of protonation of imidazole ring on the configuration of the bim molecule, the title compound (I) has been structurally characterized. The cation of (I) lies on an inversion center(Fig. 1). The protonation of imidazole groups have resulted in the changes of the bond parameters and configurations in comparison to known compounds (Krolikowska & Garbarczyk, 2005). The C—N bond lengths are in the range 1.325 (3)–1.478 (3) Å. The bimH₂ and perchlorate are linked to each other by intermolecular bifurcated N—H···O hydrogen bonds to form chains wich are further connected by weak C—H···O hydrogen bonds to build up a three-dimensional supramolecular structure (table 1).

Related literature

For related literature, see: Dhal & Arnold (1992); Ding et al. (2006); Fan et al. (2006); Hoskins et al. (1997); Krolikowska & Garbarczyk (2005); Ma et al. (2000, 2003); Moulton & Zaworotko (2001); Sato et al. (1999); Yang et al. (2006); Yao et al. (2003).

S2. Experimental

All reagents were of AR grade and were used without further purification. 1,1'-(butane-1,4-diyl)bis(imidazole) was prepared following the literature method (Ma, et al., 2000). An ethanol solution of bim (1 mmol) was reacted with an aqueous solution of perchloric acid (2 mmol) that had been neutralized with sodium hydroxide (2 mmol). The mixture was treated with 0.05 M perchloric acid to a pH of 1–2 and was refluxed for 8 h, colorless crystals of the title compound separated from the filtrate after several days. Analysis calculated for C10H16Cl2N4O8: C 30.71, H 4.12, N 14.32%; found: C 31.21, H 4.14, N 14.98%.

S3. Refinement

All H atoms were treated as riding on their parent atoms, with C—H = 0.930 Å (aromatic), 0.970Å (CH₂) and N—H= 0.86Å and with U_iso(H) = 1.2U_eq(C,N).

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. Molecular view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii. N—H···O hydrogen bonds are shown as dashed lines. [Symmetry code: (i) 1 - x, 1 - y, -z]

1,1'-(Butane-1,4-diyl)bis(imidazolium) bis(perchlorate)

Crystal data

C10H16N4^2+·2ClO4^−	Z = 1
Mr = 391.17	F(000) = 202
Triclinic, P1	Dx = 1.620 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.557 (1) Å	Cell parameters from 2535 reflections
b = 7.6280 (14) Å	θ = 2.7–28.2°
c = 9.6139 (17) Å	µ = 0.45 mm^−1
α = 95.273 (2)°	T = 291 K
β = 96.074 (2)°	BLOCK, yellow
γ = 95.853 (2)°	0.48 × 0.38 × 0.37 mm
V = 400.93 (13) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	1475 independent reflections
Radiation source: fine-focus sealed tube	1396 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
φ and ω scans	θmax = 25.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −6→6
Tmin = 0.813, Tmax = 0.849	k = −9→9
2949 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0424P)^2 + 0.2168P] where P = (Fo^2 + 2Fc^2)/3
1475 reflections	(Δ/σ)max = 0.001
109 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.08600 (9)	0.78746 (6)	0.73164 (5)	0.03864 (19)
O1	0.0172 (4)	0.8598 (2)	0.86226 (18)	0.0652 (5)
O2	−0.0516 (4)	0.6196 (2)	0.6882 (2)	0.0732 (6)
O3	0.0428 (4)	0.9096 (2)	0.62750 (18)	0.0639 (5)
O4	0.3407 (3)	0.7663 (3)	0.74746 (18)	0.0616 (5)
N1	0.5280 (3)	0.7551 (2)	0.21145 (17)	0.0378 (4)
N2	0.3307 (4)	0.8272 (3)	0.3850 (2)	0.0569 (5)
H2	0.2264	0.8723	0.4335	0.068*
C1	0.5040 (5)	0.7278 (3)	0.4347 (2)	0.0488 (5)
H1	0.5315	0.6969	0.5259	0.059*
C2	0.6280 (4)	0.6827 (3)	0.3267 (2)	0.0435 (5)
H2A	0.7579	0.6149	0.3295	0.052*
C3	0.3476 (4)	0.8438 (3)	0.2504 (3)	0.0502 (6)
H3	0.2504	0.9066	0.1929	0.060*
C4	0.6119 (5)	0.7460 (3)	0.0705 (2)	0.0499 (6)
H4A	0.7726	0.8112	0.0768	0.060*
H4B	0.5024	0.8024	0.0079	0.060*
C5	0.6226 (4)	0.5566 (3)	0.0085 (2)	0.0431 (5)
H5A	0.7381	0.5024	0.0690	0.052*
H5B	0.6820	0.5587	−0.0827	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0467 (3)	0.0361 (3)	0.0359 (3)	0.0107 (2)	0.0101 (2)	0.00608 (19)
O1	0.0902 (14)	0.0611 (11)	0.0498 (10)	0.0131 (10)	0.0330 (9)	0.0013 (8)
O2	0.0756 (13)	0.0462 (10)	0.0915 (15)	−0.0008 (9)	0.0017 (10)	−0.0088 (9)
O3	0.0812 (13)	0.0673 (11)	0.0549 (10)	0.0354 (10)	0.0171 (9)	0.0279 (9)
O4	0.0482 (10)	0.0834 (13)	0.0590 (11)	0.0187 (9)	0.0095 (8)	0.0211 (9)
N1	0.0487 (10)	0.0310 (8)	0.0332 (9)	0.0046 (7)	0.0051 (7)	−0.0002 (6)
N2	0.0592 (13)	0.0520 (12)	0.0606 (13)	0.0085 (10)	0.0234 (10)	−0.0106 (10)
C1	0.0647 (15)	0.0474 (12)	0.0339 (11)	0.0038 (11)	0.0096 (10)	0.0001 (9)
C2	0.0515 (12)	0.0423 (11)	0.0379 (11)	0.0122 (9)	0.0040 (9)	0.0035 (9)
C3	0.0490 (13)	0.0399 (11)	0.0610 (15)	0.0126 (10)	0.0006 (10)	0.0012 (10)
C4	0.0732 (16)	0.0398 (11)	0.0352 (11)	−0.0069 (10)	0.0129 (10)	0.0034 (9)
C5	0.0541 (13)	0.0428 (11)	0.0326 (10)	−0.0015 (9)	0.0155 (9)	0.0002 (8)

Geometric parameters (Å, º)

Cl1—O2	1.4262 (19)	C1—C2	1.343 (3)
Cl1—O1	1.4301 (17)	C1—H1	0.9300
Cl1—O4	1.4346 (18)	C2—H2A	0.9300
Cl1—O3	1.4471 (17)	C3—H3	0.9300
N1—C3	1.332 (3)	C4—C5	1.520 (3)
N1—C2	1.373 (3)	C4—H4A	0.9700
N1—C4	1.478 (3)	C4—H4B	0.9700
N2—C3	1.325 (3)	C5—C5^i	1.522 (4)
N2—C1	1.360 (3)	C5—H5A	0.9700
N2—H2	0.8600	C5—H5B	0.9700
O2—Cl1—O1	109.83 (12)	N1—C2—H2A	126.2
O2—Cl1—O4	109.42 (12)	N2—C3—N1	108.2 (2)
O1—Cl1—O4	109.85 (12)	N2—C3—H3	125.9
O2—Cl1—O3	110.53 (13)	N1—C3—H3	125.9
O1—Cl1—O3	108.80 (11)	N1—C4—C5	112.46 (17)
O4—Cl1—O3	108.39 (11)	N1—C4—H4A	109.1
C3—N1—C2	108.00 (18)	C5—C4—H4A	109.1
C3—N1—C4	125.27 (19)	N1—C4—H4B	109.1
C2—N1—C4	126.65 (19)	C5—C4—H4B	109.1
C3—N2—C1	109.38 (19)	H4A—C4—H4B	107.8
C3—N2—H2	125.3	C4—C5—C5^i	113.3 (2)
C1—N2—H2	125.3	C4—C5—H5A	108.9
C2—C1—N2	106.8 (2)	C5^i—C5—H5A	108.9
C2—C1—H1	126.6	C4—C5—H5B	108.9
N2—C1—H1	126.6	C5^i—C5—H5B	108.9
C1—C2—N1	107.6 (2)	H5A—C5—H5B	107.7
C1—C2—H2A	126.2

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3	0.86	2.23	3.019 (3)	153
N2—H2···O3^ii	0.86	2.42	3.032 (3)	129
C1—H1···O4	0.93	2.51	3.228 (3)	134
C3—H3···O1^ii	0.93	2.49	3.363 (3)	156
C2—H2A···O2^iii	0.93	2.55	3.464 (3)	169
C4—H4B···O4^iv	0.97	2.55	3.329 (3)	138

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