1H-Pyrazol-2-ium hydrogen oxalate

Yu, C.-H.; Zhu, R.-Q.

doi:10.1107/S1600536812023136

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1911

doi:10.1107/S1600536812023136

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1H-Pyrazol-2-ium hydrogen oxalate

Chun-Hua Yu ^a ^* and Run-Qiang Zhu ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: zhurunqiang@163.com

(Received 6 May 2012; accepted 21 May 2012; online 26 May 2012)

In the title compound, C₃H₅N₂⁺·C₂HO₄⁻, the anions form centrosymmetric dimers through cyclic O—H⋯O hydrogen-bonding associations [graph set R₂²(10)]. These dimers are then linked through a cyclic R₄²(10) N—H⋯O hydrogen-bonding association involving two cations and the carboxyl O-atom acceptors of separate anions, giving chain structures extending across the (111) plane.

Related literature

For general background to ferroelectric organic frameworks, see: Fu et al. (2009 ); Ye et al. (2006 ); Zhang et al. (2008 , 2010 ). For graph-set analysis, see: Etter et al. (1990 ).

Experimental

Crystal data

C₃H₅N₂⁺·C₂HO₄⁻
M_r = 158.12
Triclinic, $[P \overline 1]$
a = 3.7286 (7) Å
b = 9.836 (2) Å
c = 10.487 (2) Å
α = 117.35 (3)°
β = 97.01 (3)°
γ = 93.65 (3)°
V = 335.92 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 293 K
0.26 × 0.22 × 0.14 mm

Data collection

Rigaku SCXmini CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.965, T_max = 0.993
3484 measured reflections
1527 independent reflections
702 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.095
wR(F²) = 0.285
S = 1.07
1527 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	1.86	2.709 (5)	170
N2—H2A⋯O1ⁱⁱ	0.86	1.92	2.715 (5)	153
O4—H4⋯O3ⁱⁱⁱ	0.82	1.95	2.679 (5)	147
Symmetry codes: (i) x+1, y-1, z; (ii) -x+2, -y+1, -z+1; (iii) -x, -y+1, -z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812023136/zs2209sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023136/zs2209Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812023136/zs2209Isup3.cml

checkCIF report

Comment top

As a contribution to a search for new ferroelectric materials (Fu et al., 2009; Ye et al., 2006; Zhang et al., 2008, 2010), we have synthesized the title salt, C₃H₅N₂⁺. C₂HO₄^- from a 1:1 stoichiometric reaction of pyrazole with oxalic acid and the structure is reported here.

In the structure of the title compound (Fig.1) the molecules are organized in a one-dimensional chain structure involving both inter-anionic and cation–anion hydrogen-bonding associations (Table 1). The anions form centrosymmetric dimers through cyclic O—H···O hydrogen-bonding associations [graph set R²₂(10) (Etter et al., 1990)]. These dimers are then linked through a cyclic R²₄(10) N—H···O hydrogen-bonding association involving two cations and the carboxyl O-atom acceptors of separate anions, giving one-dimensional chain structures extending across the (111) plane (Fig. 2).

Related literature top

For general background to ferroelectric organic frameworks, see: Fu et al. (2009); Ye et al. (2006); Zhang et al. (2008, 2010). For graph-set analysis, see: Etter et al. (1990).

Experimental top

A mixture of pyrazole (0.68 g, 10 mmol) and oxalic acid (0.95 g, 10 mmol) in water was stirred for several days at ambient temperature. Colourless crystal plates of the title compound suitable for X-ray analysis were obtained.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure and atom-numbering scheme for the title compound, with the displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The packing of the title compound in the unit cell viewed down the a axis. Hydrogen bonds are shown as dashed lines.

1H-Pyrazol-2-ium hydrogen oxalate top

Crystal data top

C₃H₅N₂⁺·C₂HO₄⁻	Z = 2
M_r = 158.12	F(000) = 164
Triclinic, P1	D_x = 1.563 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.7286 (7) Å	Cell parameters from 1527 reflections
b = 9.836 (2) Å	θ = 2.4–27.5°
c = 10.487 (2) Å	µ = 0.14 mm⁻¹
α = 117.35 (3)°	T = 293 K
β = 97.01 (3)°	Sheet, colourless
γ = 93.65 (3)°	0.26 × 0.22 × 0.14 mm
V = 335.92 (14) Å³

Data collection top

Rigaku SCXmini CCD diffractometer	1527 independent reflections
Radiation source: fine-focus sealed tube	702 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
CCD_Profile_fitting scans	θ_max = 27.5°, θ_min = 3.9°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −4→4
T_min = 0.965, T_max = 0.993	k = −12→12
3484 measured reflections	l = −13→13

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)] = 0.095	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.285	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1349P)² + 0.0952P] where P = (F_o² + 2F_c²)/3
1527 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₃H₅N₂⁺·C₂HO₄⁻	γ = 93.65 (3)°
M_r = 158.12	V = 335.92 (14) Å³
Triclinic, P1	Z = 2
a = 3.7286 (7) Å	Mo Kα radiation
b = 9.836 (2) Å	µ = 0.14 mm⁻¹
c = 10.487 (2) Å	T = 293 K
α = 117.35 (3)°	0.26 × 0.22 × 0.14 mm
β = 97.01 (3)°

Data collection top

Rigaku SCXmini CCD diffractometer	1527 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	702 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.993	R_int = 0.063
3484 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.095	0 restraints
wR(F²) = 0.285	H-atom parameters constrained
S = 1.07	Δρ_max = 0.48 e Å⁻³
1527 reflections	Δρ_min = −0.29 e Å⁻³
101 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
N1	1.0872 (11)	0.0136 (5)	0.3057 (4)	0.0416 (11)
H1A	1.1595	−0.0585	0.3230	0.050*
N2	1.1523 (11)	0.1643 (5)	0.3992 (4)	0.0412 (11)
H2A	1.2729	0.2054	0.4865	0.049*
C1	0.9992 (15)	0.2395 (6)	0.3352 (6)	0.0493 (15)
H1	1.0047	0.3461	0.3773	0.059*
C2	0.8307 (15)	0.1355 (7)	0.1967 (6)	0.0505 (15)
H2	0.7020	0.1567	0.1277	0.061*
C3	0.8931 (15)	−0.0076 (7)	0.1818 (6)	0.0477 (14)
H3	0.8131	−0.1021	0.0993	0.057*
O1	0.3997 (10)	0.8001 (4)	0.3600 (3)	0.0475 (10)
O2	0.6353 (11)	0.5351 (4)	0.3418 (4)	0.0577 (12)
O3	0.0807 (11)	0.6588 (4)	0.1355 (4)	0.0581 (11)
O4	0.3270 (11)	0.4012 (4)	0.1179 (4)	0.0554 (11)
H4	0.1905	0.4187	0.0612	0.083*
C4	0.2907 (14)	0.6762 (6)	0.2446 (5)	0.0402 (13)
C5	0.4374 (14)	0.5304 (6)	0.2400 (5)	0.0425 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.049 (3)	0.033 (2)	0.041 (2)	0.0045 (19)	−0.0029 (19)	0.019 (2)
N2	0.048 (3)	0.034 (2)	0.031 (2)	0.005 (2)	−0.0023 (19)	0.0087 (19)
C1	0.053 (3)	0.045 (3)	0.056 (4)	0.011 (3)	0.006 (3)	0.029 (3)
C2	0.053 (4)	0.052 (4)	0.048 (3)	0.010 (3)	−0.002 (3)	0.027 (3)
C3	0.047 (3)	0.042 (3)	0.041 (3)	0.004 (2)	−0.006 (2)	0.011 (3)
O1	0.062 (2)	0.033 (2)	0.037 (2)	0.0087 (17)	−0.0074 (17)	0.0110 (18)
O2	0.076 (3)	0.043 (2)	0.045 (2)	0.0122 (19)	−0.0127 (19)	0.018 (2)
O3	0.077 (3)	0.042 (2)	0.044 (2)	0.0123 (19)	−0.0126 (19)	0.0155 (19)
O4	0.075 (3)	0.032 (2)	0.045 (2)	0.0098 (19)	−0.0082 (19)	0.0113 (19)
C4	0.047 (3)	0.032 (3)	0.035 (3)	0.005 (2)	0.005 (2)	0.011 (2)
C5	0.050 (3)	0.033 (3)	0.039 (3)	0.003 (2)	0.004 (3)	0.013 (3)

Geometric parameters (Å, º) top

N1—C3	1.325 (6)	C2—H2	0.9300
N1—N2	1.333 (5)	C3—H3	0.9300
N1—H1A	0.8601	O1—C4	1.256 (6)
N2—C1	1.319 (6)	O2—C5	1.202 (6)
N2—H2A	0.8600	O3—C4	1.239 (6)
C1—C2	1.372 (7)	O4—C5	1.317 (6)
C1—H1	0.9300	O4—H4	0.8200
C2—C3	1.380 (8)	C4—C5	1.549 (7)

C3—N1—N2	109.3 (4)	C3—C2—H2	127.4
C3—N1—H1A	125.3	N1—C3—C2	108.0 (5)
N2—N1—H1A	125.4	N1—C3—H3	126.0
C1—N2—N1	108.4 (4)	C2—C3—H3	126.0
C1—N2—H2A	125.8	C5—O4—H4	109.5
N1—N2—H2A	125.8	O3—C4—O1	127.0 (5)
N2—C1—C2	109.1 (5)	O3—C4—C5	117.3 (4)
N2—C1—H1	125.4	O1—C4—C5	115.7 (4)
C2—C1—H1	125.4	O2—C5—O4	122.4 (5)
C1—C2—C3	105.2 (5)	O2—C5—C4	122.1 (5)
C1—C2—H2	127.4	O4—C5—C4	115.4 (4)

C3—N1—N2—C1	0.1 (6)	O3—C4—C5—O2	−178.2 (5)
N1—N2—C1—C2	0.0 (6)	O1—C4—C5—O2	1.9 (8)
N2—C1—C2—C3	0.0 (6)	O3—C4—C5—O4	1.0 (7)
N2—N1—C3—C2	−0.1 (6)	O1—C4—C5—O4	−178.9 (4)
C1—C2—C3—N1	0.1 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	1.86	2.709 (5)	170
N2—H2A···O1ⁱⁱ	0.86	1.92	2.715 (5)	153
O4—H4···O3ⁱⁱⁱ	0.82	1.95	2.679 (5)	147

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

Experimental details

Crystal data
Chemical formula	C₃H₅N₂⁺·C₂HO₄⁻
M_r	158.12
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	3.7286 (7), 9.836 (2), 10.487 (2)
α, β, γ (°)	117.35 (3), 97.01 (3), 93.65 (3)
V (Å³)	335.92 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.26 × 0.22 × 0.14

Data collection
Diffractometer	Rigaku SCXmini CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.965, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	3484, 1527, 702
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.095, 0.285, 1.07
No. of reflections	1527
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.29

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	1.86	2.709 (5)	169.6
N2—H2A···O1ⁱⁱ	0.86	1.92	2.715 (5)	152.7
O4—H4···O3ⁱⁱⁱ	0.82	1.95	2.679 (5)	147.4

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

Acknowledgements

This work was supported by Southeast University.

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994–997. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ye, Q., Song, Y.-M., Wang, G.-X., Chen, K. & Fu, D.-W. (2006). J. Am. Chem. Soc. 128, 6554–6555. Web of Science CSD CrossRef PubMed CAS Google Scholar
Zhang, W., Xiong, R.-G. & Huang, S.-P. D. (2008). J. Am. Chem. Soc. 130, 10468–10469. Web of Science CSD CrossRef PubMed CAS Google Scholar
Zhang, W., Ye, H.-Y., Cai, H.-L., Ge, J.-Z. & Xiong, R.-G. (2010). J. Am. Chem. Soc. 132, 7300–7302. Web of Science CSD CrossRef CAS PubMed Google Scholar