Bis(2-methyl­imidazolium) chloranilate

Jia, L.-H.; Mu, Z.-E.; Liu, Z.-L.

doi:10.1107/S1600536807048374

organic compounds

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Volume 64| Part 1| January 2008| Page o32

https://doi.org/10.1107/S1600536807048374

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Bis(2-methylimidazolium) chloranilate

Li-Hui Jia,^a ^* Zong-E Mu ^a and Zu-Li Liu ^a

^aDepartment of Physics, Huazhong University of Science and Technology, Wuhan 430074, People's Republic of China
^*Correspondence e-mail: jialihui715@gmail.com

(Received 21 September 2007; accepted 2 October 2007; online 6 December 2007)

The asymmetric unit of the title structure, 2C₄H₇N₂⁺·C₆Cl₂O₄²⁻, consists of one 2-methylimidazolium cation and one-half of a chloranilate anion, the formula unit being generated by crystallographic inversion symmetry. N—H⋯O hydrogen bonds link the ions into a two-dimensional framework parallel to the (102) plane. No π–π stacking or C—H⋯π interactions are observed in the crystal structure.

Related literature

For related literature, see: Bernstein et al. (1995 ); Ishida & Kashino (2001 ); Ishida (2004a ,b ); Meng & Qian (2006 ); Min et al. (2006 ); Wang & Wei (2005 ).

Experimental

Crystal data

2C₄H₇N₂⁺·C₆Cl₂O₄²⁻
M_r = 373.20
Monoclinic, P 2₁ /c
a = 8.5092 (10) Å
b = 7.6658 (9) Å
c = 12.7204 (16) Å
β = 91.204 (2)°
V = 829.57 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 296 (2) K
0.12 × 0.05 × 0.02 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.942, T_max = 0.992
9164 measured reflections
1880 independent reflections
1150 reflections with I > 2σ(I)
R_int = 0.067

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.132
S = 1.01
1880 reflections
116 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.99 (3)	1.73 (3)	2.713 (3)	172 (2)
N2—H2A⋯O2ⁱ	0.82 (3)	1.96 (3)	2.719 (3)	152 (3)
N2—H2A⋯O1ⁱ	0.82 (3)	2.40 (3)	3.014 (3)	132 (3)
Symmetry code: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807048374/lh2514sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807048374/lh2514Isup2.hkl

checkCIF report

Comment top

Chloranilic acid (CA) is a potential bridging ligand which is often used in the synthesis of metal organic frameworks (Min et al., 2006). Also some organic salts containing chloranilate have been reported recently (Ishida, 2004a,b; Ishida & Kashino, 2001; Wang & Wei, 2005, Meng & Qian, 2006). In the hydrothermal process using equimolar amounts of CA, 2-Methylimidazole (2-MeIm) and copper nitrate, we unexpectedly obtained the title compound, and report herein its crystal structure.

The asymmetric unit contains one 2-methylimidazolium cation, half of a chloranilate anion the formula unit being generated by crystallogrphic inversion symmetry (Fig. 1). A proton has been transferred from the hydroxyl group in CA to the 2-MeIm N atom, forming the 1:2 organic salt.

In the crystal structure, by a combination of three N—H···O hydrogen bonds (Table 1) the molecules are linked into a two-dimensional framework (Fig. 2) built from the R²₁(5) and R⁶₈(32) rings (Bernstein et al., 1995) running parallel to the (102) plane. Two such networks pass through the cell and analysis using PLATON (Spek, 2003) shows that there are no direction-specific interactions such as π–π and C–H···π interactions observed in the packing of the structure.

Related literature top

For related literature, see: Bernstein et al. (1995); Ishida & Kashino (2001); Ishida (2004a,b); Meng & Qian (2006); Min et al. (2006); Wang & Wei (2005).

Experimental top

All the reagents and solvents were used as obtained without further purification. Equivalent molar amount of CA (0.2 mmol, 41.4 mg), 2-MeIm (0.2 mmol, 16.2 mg) and Cu(NO₃)₂.3(H₂O)(0.2 mmol, 48 mg) in 10 ml water solvent sealed in a 25 ml Teflon-lined autoclave. The mixture was heated to 393 K and maintained for 48 h. After slowly cooling to room temperature with the rate of 5°/h, dark red crystals suitable for single-crystal X-ray diffraction analysis were obtained. The crystals were filtered and washed with distilled water and dried in air.

Structure description top

For related literature, see: Bernstein et al. (1995); Ishida & Kashino (2001); Ishida (2004a,b); Meng & Qian (2006); Min et al. (2006); Wang & Wei (2005).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. Molecular structure, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H-bonds are shown as dashed lines.
	Fig. 2. Part of the crystal structure, showing the formation of the two-dimensional network by N—H···O hydrogen bonds. H-bonds are shown as dashed lines.

Bis(2-methylimidazolium) chloranilate top

Crystal data top

2C₄H₇N₂⁺·C₆Cl₂O₄²⁻	F(000) = 384
M_r = 373.20	D_x = 1.494 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 863 reflections
a = 8.5092 (10) Å	θ = 2.4–19.5°
b = 7.6658 (9) Å	µ = 0.42 mm⁻¹
c = 12.7204 (16) Å	T = 296 K
β = 91.204 (2)°	Plate, red
V = 829.57 (17) Å³	0.12 × 0.05 × 0.02 mm
Z = 2

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1880 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	1150 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
0.3° wide ω exposures scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.942, T_max = 0.992	k = −9→9
9164 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0635P)²] where P = (F_o² + 2F_c²)/3
1880 reflections	(Δ/σ)_max < 0.001
116 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

2C₄H₇N₂⁺·C₆Cl₂O₄²⁻	V = 829.57 (17) Å³
M_r = 373.20	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5092 (10) Å	µ = 0.42 mm⁻¹
b = 7.6658 (9) Å	T = 296 K
c = 12.7204 (16) Å	0.12 × 0.05 × 0.02 mm
β = 91.204 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1880 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1150 reflections with I > 2σ(I)
T_min = 0.942, T_max = 0.992	R_int = 0.067
9164 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.28 e Å⁻³
1880 reflections	Δρ_min = −0.23 e Å⁻³
116 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	0.9935 (3)	0.3795 (3)	0.1722 (2)	0.0386 (7)
C2	0.8754 (4)	0.2917 (4)	0.0266 (2)	0.0472 (7)
H2	0.8591	0.2450	−0.0403	0.057*
C3	0.7656 (3)	0.3549 (4)	0.0898 (2)	0.0457 (7)
H3	0.6582	0.3609	0.0751	0.055*
C4	1.1147 (4)	0.4178 (5)	0.2537 (2)	0.0614 (9)
H4A	1.1663	0.3116	0.2745	0.092*
H4B	1.0661	0.4695	0.3136	0.092*
H4C	1.1905	0.4974	0.2260	0.092*
C5	0.5122 (3)	0.3827 (3)	0.41260 (19)	0.0346 (6)
C6	0.6258 (3)	0.5121 (3)	0.42497 (17)	0.0310 (6)
C7	0.6127 (3)	0.6382 (3)	0.51780 (19)	0.0336 (6)
Cl1	0.52835 (9)	0.23376 (10)	0.31053 (5)	0.0543 (3)
N1	0.8402 (3)	0.4086 (3)	0.17996 (17)	0.0404 (6)
H1A	0.794 (3)	0.452 (3)	0.246 (2)	0.049*
N2	1.0162 (3)	0.3091 (3)	0.07907 (18)	0.0419 (6)
H2A	1.105 (4)	0.275 (4)	0.066 (2)	0.050*
O1	0.7415 (2)	0.5352 (2)	0.36643 (13)	0.0413 (5)
O2	0.7146 (2)	0.7533 (3)	0.52727 (15)	0.0512 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0307 (16)	0.0390 (16)	0.0466 (16)	−0.0006 (13)	0.0121 (12)	−0.0012 (12)
C2	0.0474 (19)	0.0524 (18)	0.0419 (15)	−0.0007 (15)	0.0054 (14)	−0.0076 (14)
C3	0.0331 (16)	0.0542 (18)	0.0500 (17)	0.0010 (14)	0.0045 (14)	−0.0066 (14)
C4	0.0455 (19)	0.074 (2)	0.065 (2)	0.0006 (17)	−0.0009 (16)	−0.0138 (17)
C5	0.0292 (14)	0.0381 (15)	0.0370 (13)	−0.0020 (12)	0.0105 (11)	−0.0084 (11)
C6	0.0245 (14)	0.0386 (15)	0.0299 (12)	0.0022 (11)	0.0042 (11)	0.0018 (11)
C7	0.0285 (14)	0.0361 (15)	0.0363 (13)	−0.0010 (12)	0.0059 (11)	0.0007 (11)
Cl1	0.0482 (5)	0.0624 (5)	0.0532 (5)	−0.0135 (4)	0.0227 (4)	−0.0260 (4)
N1	0.0347 (14)	0.0444 (14)	0.0428 (13)	0.0027 (11)	0.0158 (11)	−0.0063 (11)
N2	0.0347 (14)	0.0450 (15)	0.0468 (13)	0.0075 (11)	0.0177 (12)	−0.0038 (11)
O1	0.0315 (11)	0.0521 (12)	0.0409 (10)	−0.0071 (9)	0.0177 (8)	−0.0033 (9)
O2	0.0441 (12)	0.0547 (13)	0.0557 (12)	−0.0212 (10)	0.0237 (10)	−0.0174 (10)

Geometric parameters (Å, º) top

C1—N2	1.319 (3)	C4—H4C	0.9600
C1—N1	1.329 (3)	C5—C6	1.392 (3)
C1—C4	1.477 (4)	C5—C7ⁱ	1.406 (3)
C2—C3	1.337 (4)	C5—Cl1	1.737 (2)
C2—N2	1.366 (4)	C6—O1	1.259 (3)
C2—H2	0.9300	C6—C7	1.532 (3)
C3—N1	1.363 (3)	C7—O2	1.242 (3)
C3—Cl1	3.613 (3)	C7—C5ⁱ	1.406 (3)
C3—H3	0.9300	N1—H1A	0.99 (3)
C4—H4A	0.9600	N2—H2A	0.82 (3)
C4—H4B	0.9600

N2—C1—N1	107.3 (2)	H4B—C4—H4C	109.5
N2—C1—C4	126.8 (3)	C6—C5—C7ⁱ	122.8 (2)
N1—C1—C4	125.9 (3)	C6—C5—Cl1	119.15 (18)
C3—C2—N2	106.7 (3)	C7ⁱ—C5—Cl1	117.96 (19)
C3—C2—H2	126.7	O1—C6—C5	125.7 (2)
N2—C2—H2	126.7	O1—C6—C7	115.9 (2)
C2—C3—N1	107.3 (3)	C5—C6—C7	118.4 (2)
C2—C3—Cl1	141.6 (2)	O2—C7—C5ⁱ	123.7 (2)
N1—C3—Cl1	71.46 (15)	O2—C7—C6	117.5 (2)
C2—C3—H3	126.4	C5ⁱ—C7—C6	118.8 (2)
N1—C3—H3	126.4	C5—Cl1—C3	117.80 (10)
Cl1—C3—H3	66.9	C1—N1—C3	109.1 (2)
C1—C4—H4A	109.5	C1—N1—H1A	121.6 (15)
C1—C4—H4B	109.5	C3—N1—H1A	129.0 (15)
H4A—C4—H4B	109.5	C1—N2—C2	109.6 (2)
C1—C4—H4C	109.5	C1—N2—H2A	118 (2)
H4A—C4—H4C	109.5	C2—N2—H2A	132 (2)

N2—C2—C3—N1	−0.4 (3)	C7ⁱ—C5—Cl1—C3	161.62 (18)
N2—C2—C3—Cl1	−82.1 (4)	C2—C3—Cl1—C5	135.2 (3)
C7ⁱ—C5—C6—O1	178.7 (2)	N1—C3—Cl1—C5	40.6 (2)
Cl1—C5—C6—O1	1.6 (4)	N2—C1—N1—C3	0.2 (3)
C7ⁱ—C5—C6—C7	−0.7 (4)	C4—C1—N1—C3	−179.3 (3)
Cl1—C5—C6—C7	−177.85 (17)	C2—C3—N1—C1	0.2 (3)
O1—C6—C7—O2	0.9 (3)	Cl1—C3—N1—C1	139.7 (2)
C5—C6—C7—O2	−179.6 (2)	N1—C1—N2—C2	−0.4 (3)
O1—C6—C7—C5ⁱ	−178.8 (2)	C4—C1—N2—C2	179.1 (3)
C5—C6—C7—C5ⁱ	0.7 (4)	C3—C2—N2—C1	0.5 (3)
C6—C5—Cl1—C3	−21.1 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.99 (3)	1.73 (3)	2.713 (3)	172 (2)
N2—H2A···O2ⁱⁱ	0.82 (3)	1.96 (3)	2.719 (3)	152 (3)
N2—H2A···O1ⁱⁱ	0.82 (3)	2.40 (3)	3.014 (3)	132 (3)

Symmetry code: (ii) −x+2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	2C₄H₇N₂⁺·C₆Cl₂O₄²⁻
M_r	373.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.5092 (10), 7.6658 (9), 12.7204 (16)
β (°)	91.204 (2)
V (Å³)	829.57 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.12 × 0.05 × 0.02

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.942, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	9164, 1880, 1150
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.132, 1.01
No. of reflections	1880
No. of parameters	116
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.23

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.99 (3)	1.73 (3)	2.713 (3)	172 (2)
N2—H2A···O2ⁱ	0.82 (3)	1.96 (3)	2.719 (3)	152 (3)
N2—H2A···O1ⁱ	0.82 (3)	2.40 (3)	3.014 (3)	132 (3)

Symmetry code: (i) −x+2, y−1/2, −z+1/2.

Acknowledgements

The authors acknowledge support from the Key Project of the National Natural Science Foundation of China (grant No. 20490210) and from National Natural Science Foundation of China (grant Nos. 10574047 and 10574048). This work was also supported by the National 973 Project under grant No. 2006CB921600 and by the Programme on Major International Cooperation Projects (grant No. 2003DF000034).

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