2-Phenyl-1H-imidazol-3-ium hydrogen oxalate

Song, J.-N.

doi:10.1107/S1600536811023300

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1773

doi:10.1107/S1600536811023300

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2-Phenyl-1H-imidazol-3-ium hydrogen oxalate

Jin-Na Song ^a ^*

^aSchool of Biological and Agricultural Engineering, Jilin University, Changchun 130022, People's Republic of China
^*Correspondence e-mail: songjn2010@jlu.edu.cn

(Received 12 June 2011; accepted 15 June 2011; online 22 June 2011)

In the title molecular salt, C₉H₉N₂⁺·C₂HO₄⁻, the dihedral angle between the aromatic rings of the cation is 17.5 (3)° and the dihedral angle between the –CO₂H and –CO₂ groups of the anion is 38.6 (2)°. In the crystal, the components interact by way of O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For backgrond to 2-phenylimidazole as a ligand, see: Liu et al. (2008 ). For a related 2-phenylimidazolium nitrate structure, see: Zhang et al. (2007 ).

Experimental

Crystal data

C₉H₉N₂⁺·C₂HO₄⁻
M_r = 234.21
Triclinic, $[P \overline 1]$
a = 5.571 (4) Å
b = 9.216 (5) Å
c = 11.918 (6) Å
α = 70.262 (5)°
β = 80.460 (1)°
γ = 74.871 (5)°
V = 554.0 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.15 mm

Data collection

Oxford Diffraction Gemini R Ultra CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.38, T_max = 0.57
4030 measured reflections
2505 independent reflections
1629 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.104
S = 0.93
2505 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O4ⁱ	0.82	1.76	2.5793 (19)	172
N2—H2⋯O3ⁱⁱ	0.86	1.90	2.732 (2)	164
N1—H1⋯O4ⁱ	0.86	1.93	2.777 (2)	169
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811023300/hb5908sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811023300/hb5908Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811023300/hb5908Isup3.cml

checkCIF report

Comment top

2-Phenylimidazole has been extensively used to build supramolecular architectures because of its excellent coordinating abilities and fruitful aromatic systems, (Liu et al., 2008). The 2-phenylimidazolium nitrate structure has been reported as a hemihydrate (Zhang et al., 2007). In this work, we will report the synthesis and crystal structure of the 2-phenylimidazolium hydrogen oxalate, namely, C₁₁H₁₀N₂O₄.

The asymmetric unit of the title compound contains one 2-phenylimidazolium cation and one hydrogen oxalate anion (Fig. 1). There are O—H···O and N—H···O hydrogen-bonding interactions in the structure (Table I).

Related literature top

For backgrond to 2-phenylimidazole as a ligand, see: Liu et al. (2008). For a related 2-phenylimidazolium nitrate structure, see: Zhang et al. (2007).

Experimental top

A mixture of 2-phenylimidazole (0.3 mmol), oxalic acid (0.3 mmol) and H₂O (8 ml) was mixed. After one week, colorless blocks of the title compound were obtained at room temperature.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of (I), showing displacement ellipsoids drawn at the 30% probability level.

2-Phenyl-1H-imidazol-3-ium hydrogen oxalate top

Crystal data top

C₉H₉N₂⁺·C₂HO₄⁻	Z = 2
M_r = 234.21	F(000) = 244
Triclinic, P1	D_x = 1.404 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.571 (4) Å	Cell parameters from 2505 reflections
b = 9.216 (5) Å	θ = 1.8–29.1°
c = 11.918 (6) Å	µ = 0.11 mm⁻¹
α = 70.262 (5)°	T = 293 K
β = 80.460 (1)°	Block, colorless
γ = 74.871 (5)°	0.22 × 0.20 × 0.15 mm
V = 554.0 (6) Å³

Data collection top

Oxford Diffraction Gemini R Ultra CCD diffractometer	2505 independent reflections
Radiation source: fine-focus sealed tube	1629 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 10.0 pixels mm^-1	θ_max = 29.1°, θ_min = 1.8°
ω scans	h = −5→7
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −9→11
T_min = 0.38, T_max = 0.57	l = −14→16
4030 measured reflections

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0587P)²] where P = (F_o² + 2F_c²)/3
2505 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₉H₉N₂⁺·C₂HO₄⁻	γ = 74.871 (5)°
M_r = 234.21	V = 554.0 (6) Å³
Triclinic, P1	Z = 2
a = 5.571 (4) Å	Mo Kα radiation
b = 9.216 (5) Å	µ = 0.11 mm⁻¹
c = 11.918 (6) Å	T = 293 K
α = 70.262 (5)°	0.22 × 0.20 × 0.15 mm
β = 80.460 (1)°

Data collection top

Oxford Diffraction Gemini R Ultra CCD diffractometer	2505 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	1629 reflections with I > 2σ(I)
T_min = 0.38, T_max = 0.57	R_int = 0.031
4030 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 0.93	Δρ_max = 0.20 e Å⁻³
2505 reflections	Δρ_min = −0.38 e Å⁻³
154 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	−0.1534 (2)	0.24120 (16)	0.80993 (12)	0.0329 (3)
C2	0.0697 (2)	0.30067 (16)	0.82279 (12)	0.0351 (3)
C3	0.2653 (3)	0.6592 (2)	0.61457 (15)	0.0559 (4)
H3	0.4206	0.5901	0.6257	0.067*
C4	0.1280 (4)	0.6664 (2)	0.52534 (17)	0.0712 (6)
H4	0.1910	0.6018	0.4770	0.085*
C5	−0.1001 (4)	0.7681 (2)	0.50819 (16)	0.0685 (5)
H5	−0.1925	0.7726	0.4484	0.082*
C6	−0.1917 (3)	0.8628 (2)	0.57895 (16)	0.0605 (5)
H6	−0.3468	0.9319	0.5669	0.073*
C7	−0.0578 (3)	0.85767 (18)	0.66808 (14)	0.0463 (4)
H7	−0.1221	0.9234	0.7154	0.056*
C8	0.1728 (3)	0.75450 (16)	0.68720 (12)	0.0364 (3)
C9	0.3166 (2)	0.74777 (15)	0.78093 (12)	0.0329 (3)
C11	0.4589 (3)	0.81235 (18)	0.91542 (13)	0.0451 (4)
H11	0.4762	0.8682	0.9645	0.054*
C10	0.5995 (3)	0.67346 (17)	0.91074 (13)	0.0414 (4)
H10	0.7336	0.6140	0.9556	0.050*
N1	0.5092 (2)	0.63481 (12)	0.82744 (10)	0.0363 (3)
H1	0.5683	0.5498	0.8079	0.044*
N2	0.2843 (2)	0.85814 (13)	0.83489 (11)	0.0409 (3)
H2	0.1713	0.9444	0.8211	0.049*
O1	0.04670 (19)	0.40133 (14)	0.86821 (12)	0.0591 (3)
O2	0.27912 (17)	0.22797 (13)	0.78035 (11)	0.0565 (3)
H2A	0.3941	0.2626	0.7889	0.085*
O3	−0.12709 (18)	0.09884 (11)	0.82754 (11)	0.0547 (3)
O4	−0.35046 (16)	0.34460 (11)	0.78500 (9)	0.0420 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0231 (6)	0.0340 (8)	0.0460 (8)	−0.0023 (6)	−0.0051 (6)	−0.0198 (6)
C2	0.0249 (7)	0.0331 (8)	0.0510 (9)	−0.0015 (6)	−0.0098 (6)	−0.0183 (7)
C3	0.0585 (11)	0.0547 (10)	0.0585 (10)	−0.0027 (8)	−0.0167 (8)	−0.0242 (8)
C4	0.0890 (15)	0.0786 (14)	0.0595 (11)	−0.0185 (12)	−0.0179 (11)	−0.0330 (10)
C5	0.0738 (14)	0.0881 (15)	0.0521 (11)	−0.0333 (12)	−0.0248 (10)	−0.0119 (10)
C6	0.0459 (10)	0.0726 (12)	0.0573 (10)	−0.0132 (9)	−0.0182 (8)	−0.0063 (9)
C7	0.0400 (8)	0.0490 (9)	0.0468 (9)	−0.0089 (7)	−0.0087 (7)	−0.0094 (7)
C8	0.0383 (8)	0.0332 (8)	0.0379 (8)	−0.0103 (6)	−0.0067 (6)	−0.0080 (6)
C9	0.0322 (7)	0.0257 (7)	0.0399 (8)	−0.0042 (6)	−0.0030 (6)	−0.0106 (6)
C11	0.0470 (9)	0.0474 (9)	0.0493 (9)	−0.0059 (7)	−0.0126 (7)	−0.0252 (7)
C10	0.0403 (8)	0.0394 (8)	0.0453 (8)	−0.0024 (7)	−0.0139 (7)	−0.0142 (7)
N1	0.0371 (6)	0.0279 (6)	0.0441 (7)	0.0010 (5)	−0.0094 (5)	−0.0148 (5)
N2	0.0380 (7)	0.0308 (6)	0.0551 (8)	0.0034 (5)	−0.0114 (6)	−0.0195 (6)
O1	0.0379 (6)	0.0655 (8)	0.0974 (9)	−0.0077 (5)	−0.0096 (6)	−0.0560 (7)
O2	0.0216 (5)	0.0618 (7)	0.1047 (9)	−0.0057 (5)	−0.0051 (5)	−0.0522 (7)
O3	0.0314 (5)	0.0331 (6)	0.1060 (9)	−0.0020 (4)	−0.0108 (6)	−0.0311 (6)
O4	0.0235 (5)	0.0358 (6)	0.0717 (7)	0.0009 (4)	−0.0142 (5)	−0.0241 (5)

Geometric parameters (Å, º) top

C1—O3	1.2291 (17)	C7—C8	1.385 (2)
C1—O4	1.2541 (16)	C7—H7	0.9300
C1—C2	1.531 (2)	C8—C9	1.455 (2)
C2—O1	1.1934 (17)	C9—N1	1.3293 (18)
C2—O2	1.3003 (16)	C9—N2	1.3374 (17)
C3—C8	1.384 (2)	C11—C10	1.329 (2)
C3—C4	1.385 (2)	C11—N2	1.366 (2)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.368 (3)	C10—N1	1.3649 (19)
C4—H4	0.9300	C10—H10	0.9300
C5—C6	1.362 (3)	N1—H1	0.8600
C5—H5	0.9300	N2—H2	0.8600
C6—C7	1.378 (2)	O2—H2A	0.8200
C6—H6	0.9300

O3—C1—O4	126.05 (12)	C8—C7—H7	120.0
O3—C1—C2	118.29 (11)	C3—C8—C7	118.80 (14)
O4—C1—C2	115.64 (12)	C3—C8—C9	120.56 (14)
O1—C2—O2	125.70 (13)	C7—C8—C9	120.64 (13)
O1—C2—C1	122.10 (12)	N1—C9—N2	106.32 (12)
O2—C2—C1	112.19 (12)	N1—C9—C8	127.46 (12)
C8—C3—C4	120.32 (17)	N2—C9—C8	126.19 (12)
C8—C3—H3	119.8	C10—C11—N2	107.50 (13)
C4—C3—H3	119.8	C10—C11—H11	126.3
C5—C4—C3	120.15 (18)	N2—C11—H11	126.3
C5—C4—H4	119.9	C11—C10—N1	106.80 (13)
C3—C4—H4	119.9	C11—C10—H10	126.6
C6—C5—C4	119.83 (17)	N1—C10—H10	126.6
C6—C5—H5	120.1	C9—N1—C10	110.07 (11)
C4—C5—H5	120.1	C9—N1—H1	125.0
C5—C6—C7	120.91 (17)	C10—N1—H1	125.0
C5—C6—H6	119.5	C9—N2—C11	109.30 (12)
C7—C6—H6	119.5	C9—N2—H2	125.3
C6—C7—C8	120.00 (16)	C11—N2—H2	125.3
C6—C7—H7	120.0	C2—O2—H2A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O4ⁱ	0.82	1.76	2.5793 (19)	172
N2—H2···O3ⁱⁱ	0.86	1.90	2.732 (2)	164
N1—H1···O4ⁱ	0.86	1.93	2.777 (2)	169

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

Experimental details

Crystal data
Chemical formula	C₉H₉N₂⁺·C₂HO₄⁻
M_r	234.21
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.571 (4), 9.216 (5), 11.918 (6)
α, β, γ (°)	70.262 (5), 80.460 (1), 74.871 (5)
V (Å³)	554.0 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.22 × 0.20 × 0.15

Data collection
Diffractometer	Oxford Diffraction Gemini R Ultra CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.38, 0.57
No. of measured, independent and observed [I > 2σ(I)] reflections	4030, 2505, 1629
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.104, 0.93
No. of reflections	2505
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.38

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), 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
O2—H2A···O4ⁱ	0.82	1.76	2.5793 (19)	172
N2—H2···O3ⁱⁱ	0.86	1.90	2.732 (2)	164
N1—H1···O4ⁱ	0.86	1.93	2.777 (2)	169

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

Acknowledgements

This work was supported by the Specialized Research Fund for the Doctoral Program of Higher Education (20100061120071), the Young Scientific Research Foundation of Jilin Province (201101068) and the Natural Science Foundation of Jilin University (201003051).

References

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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