3-Cyano­anilinium hydrogen oxalate hemihydrate

Chen, X.-Y.

doi:10.1107/S1600536812019824

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1678

doi:10.1107/S1600536812019824

Open

access

3-Cyanoanilinium hydrogen oxalate hemihydrate

Xin-Yuan Chen ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: chenxinyuanseu@yahoo.com.cn

(Received 26 April 2012; accepted 3 May 2012; online 12 May 2012)

In the title hydrated molecular salt, C₇H₇N₂⁺·C₂HO₄⁻·0.5H₂O, contains a 3-cyanoanilinium cation, a hydrogen oxalate anion and half a water molecule in an asymmetric unit. The dihedral angle between the CO₂(H) and CO₂ planes of the hydrogen oxalate ion is 7.96 (1)°. In the crystal, the components are linked by N—H⋯O and O—H⋯O hydrogen bonds, forming a layer lying parallel to the ac plane.

Related literature

For the properties of related compounds, see: Chen et al. (2000 ); Liu et al. (1999 ); Zhao et al. (2003 ). For the structures of related compounds, see: Dai & Chen (2011 ); Xu et al. (2011 ); Zheng (2011 ).

Experimental

Crystal data

C₇H₇N₂⁺·C₂HO₄⁻·0.5H₂O
M_r = 217.18
Monoclinic, P 2/c
a = 15.1221 (7) Å
b = 5.6518 (1) Å
c = 13.6926 (6) Å
β = 113.22 (4)°
V = 1075.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 173 K
0.10 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury2 (2 × 2 bin mode) diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
7209 measured reflections
2446 independent reflections
1906 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.156
S = 1.07
2446 reflections
142 parameters
5 restraints
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O1ⁱ	0.82	1.96	2.767 (2)	166
N1—H1A⋯O1ⁱⁱ	0.89	1.91	2.797 (2)	172
N1—H1C⋯O2ⁱⁱⁱ	0.89	1.96	2.778 (2)	152
O3—H3⋯O2ⁱⁱⁱ	0.82	1.74	2.559 (2)	178
N1—H1B⋯O1W	0.89	1.91	2.788 (2)	167
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812019824/pv2542sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812019824/pv2542Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812019824/pv2542Isup3.cml

checkCIF report

Comment top

Salts of amide attracted more attention as phase transition dielectric materials for its application in micro-electronics, memory storage (Chen et al., 2000; Liu, et al. 1999; Zhao, et al. 2003). With the purpose of obtaining phase transition crystals of 3-aminobenzonitrile salts, its interaction with various acids has been studied and we have elaborated a serie of new materials with this organic molecule (Dai & Chen 2011; Xu, et al. 2011; Zheng 2011). In this paper, we describe the crystal structure of the title compound.

The asymmetric unit is composed of a 3-cyanoanilinium cation, a carboxyformate anion, and a half molecule of water (Fig. 1). The geometric parameters of the title compound agree well with reported similar structure (Dai & Chen 2011). The cation is almost planar (r.m.s. deviation 0.0062 Å, benzene ring as the best plane).

The cations are surrounded by the anions and water molecules via hydrogen bonds which play an important role in stabilizing the crystal structure. In the crystal structure, all the amino H atoms are involved in N—H···O hydrogen bonds with carboxyformate anion and water molecule with the distances of 2.797 (2) Å, 2.778 (2) Å and 2.788 (2) Å, respectively. In addition, the H atoms of water molecule and carboxyformate anion are involved in the O—H···O H-bonding interactions. In the crystal structure, those H-bonds link the ionic units into a two-dimensional sheets parallel to the ac plane (Table 1 and Fig. 2).

Related literature top

For applications of amide salts in micro-electronics and memory storage, see: Chen et al. (2000); Liu et al. (1999); Zhao et al. (2003). For the structures of related compounds, see: Dai & Chen (2011); Xu et al. (2011); Zheng (2011).

Experimental top

The commercial 3-aminobenzonitrile (3 mmol, 324 mg) and oxalic acid (3 mmol, 270 mg) were dissolved in 50 ml water/MeOH solution (1:1 v/v). The solvent was slowly evaporated in air affording colourless block-shaped crystals of the title compound suitable for X-ray analysis.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewing along the b-axis, showing the two-dimensional hydrogen-bonded network.

3-Cyanoanilinium hydrogen oxalate hemihydrate top

Crystal data top

C₇H₇N₂⁺·C₂HO₄⁻·0.5H₂O	F(000) = 452
M_r = 217.18	D_x = 1.341 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 2446 reflections
a = 15.1221 (7) Å	θ = 2.9–27.5°
b = 5.6518 (1) Å	µ = 0.11 mm⁻¹
c = 13.6926 (6) Å	T = 173 K
β = 113.22 (4)°	Block, colorless
V = 1075.5 (3) Å³	0.10 × 0.05 × 0.05 mm
Z = 4

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	2446 independent reflections
Radiation source: fine-focus sealed tube	1906 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.9°
CCD profile fitting scans	h = −18→19
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −7→7
T_min = 0.910, T_max = 1.000	l = −17→17
7209 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0872P)² + 0.1364P] where P = (F_o² + 2F_c²)/3
2446 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 0.28 e Å⁻³
5 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₇H₇N₂⁺·C₂HO₄⁻·0.5H₂O	V = 1075.5 (3) Å³
M_r = 217.18	Z = 4
Monoclinic, P2/c	Mo Kα radiation
a = 15.1221 (7) Å	µ = 0.11 mm⁻¹
b = 5.6518 (1) Å	T = 173 K
c = 13.6926 (6) Å	0.10 × 0.05 × 0.05 mm
β = 113.22 (4)°

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	2446 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1906 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.034
7209 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	5 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 1.07	Δρ_max = 0.28 e Å⁻³
2446 reflections	Δρ_min = −0.24 e Å⁻³
142 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
O1W	0.5000	0.3943 (3)	0.7500	0.0237 (4)
H1WA	0.4708	0.3063	0.6999	0.036*
N1	0.63809 (11)	0.7280 (2)	0.75668 (11)	0.0247 (4)
H1A	0.6328	0.8305	0.8034	0.037*
H1B	0.5962	0.6106	0.7469	0.037*
H1C	0.6258	0.8012	0.6952	0.037*
C1	0.73556 (13)	0.6324 (3)	0.79701 (14)	0.0278 (4)
C6	0.75806 (14)	0.4443 (3)	0.86683 (15)	0.0312 (4)
H6A	0.7120	0.3818	0.8888	0.037*
C5	0.85041 (16)	0.3490 (4)	0.90408 (18)	0.0449 (6)
C7	0.87338 (18)	0.1547 (5)	0.9797 (2)	0.0579 (7)
C3	0.8941 (2)	0.6365 (8)	0.8017 (3)	0.0843 (11)
H3A	0.9400	0.7024	0.7805	0.101*
C2	0.80292 (17)	0.7312 (5)	0.7645 (2)	0.0547 (7)
H2A	0.7870	0.8596	0.7183	0.066*
N2	0.89001 (19)	0.0051 (5)	1.0408 (2)	0.0826 (9)
C4	0.9188 (2)	0.4440 (7)	0.8704 (2)	0.0730 (9)
H4A	0.9802	0.3793	0.8937	0.088*
O1	0.60131 (9)	−0.0466 (2)	0.39238 (9)	0.0266 (3)
O2	0.60400 (10)	−0.1979 (2)	0.54425 (9)	0.0294 (3)
O3	0.60355 (10)	0.3895 (2)	0.46709 (9)	0.0302 (3)
H3	0.6034	0.5206	0.4927	0.045*
O4	0.62804 (10)	0.2420 (2)	0.62874 (9)	0.0298 (3)
C9	0.61454 (12)	0.2186 (3)	0.53599 (13)	0.0216 (4)
C8	0.60611 (12)	−0.0294 (3)	0.48550 (13)	0.0210 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1W	0.0349 (10)	0.0193 (8)	0.0149 (8)	0.000	0.0076 (7)	0.000
N1	0.0353 (9)	0.0215 (7)	0.0201 (7)	−0.0007 (6)	0.0140 (6)	−0.0001 (6)
C1	0.0285 (10)	0.0333 (10)	0.0223 (8)	−0.0041 (7)	0.0107 (7)	−0.0045 (7)
C6	0.0315 (10)	0.0308 (10)	0.0305 (10)	−0.0006 (7)	0.0115 (8)	−0.0024 (8)
C5	0.0347 (12)	0.0507 (14)	0.0439 (13)	0.0079 (10)	0.0097 (9)	0.0010 (10)
C7	0.0420 (14)	0.0564 (16)	0.0646 (17)	0.0147 (11)	0.0097 (12)	0.0095 (14)
C3	0.0396 (16)	0.146 (3)	0.076 (2)	0.0062 (17)	0.0328 (15)	0.039 (2)
C2	0.0386 (13)	0.0800 (19)	0.0483 (14)	−0.0052 (11)	0.0200 (11)	0.0215 (13)
N2	0.0643 (16)	0.0727 (18)	0.092 (2)	0.0214 (13)	0.0107 (14)	0.0307 (15)
C4	0.0335 (14)	0.118 (3)	0.0714 (19)	0.0210 (15)	0.0244 (13)	0.0192 (19)
O1	0.0457 (8)	0.0193 (6)	0.0186 (6)	−0.0043 (5)	0.0168 (5)	−0.0029 (5)
O2	0.0541 (9)	0.0158 (6)	0.0209 (6)	−0.0013 (5)	0.0177 (6)	0.0005 (5)
O3	0.0592 (9)	0.0138 (6)	0.0219 (6)	−0.0003 (5)	0.0205 (6)	0.0005 (5)
O4	0.0505 (9)	0.0228 (7)	0.0177 (6)	−0.0020 (5)	0.0154 (5)	−0.0032 (5)
C9	0.0320 (9)	0.0166 (8)	0.0170 (8)	−0.0012 (6)	0.0105 (7)	0.0001 (6)
C8	0.0304 (9)	0.0158 (8)	0.0176 (8)	−0.0006 (6)	0.0104 (6)	0.0000 (6)

Geometric parameters (Å, º) top

O1W—H1WA	0.8207	C3—C2	1.376 (4)
N1—C1	1.459 (2)	C3—C4	1.389 (5)
N1—H1A	0.8900	C3—H3A	0.9300
N1—H1B	0.8900	C2—H2A	0.9300
N1—H1C	0.8900	C4—H4A	0.9300
C1—C6	1.380 (3)	O1—C8	1.2521 (19)
C1—C2	1.380 (3)	O2—C8	1.255 (2)
C6—C5	1.392 (3)	O3—C9	1.314 (2)
C6—H6A	0.9300	O3—H3	0.8205
C5—C4	1.395 (4)	O4—C9	1.211 (2)
C5—C7	1.454 (4)	C9—C8	1.546 (2)
C7—N2	1.146 (4)

C1—N1—H1A	109.5	C2—C3—C4	121.2 (3)
C1—N1—H1B	109.5	C2—C3—H3A	119.4
H1A—N1—H1B	109.5	C4—C3—H3A	119.4
C1—N1—H1C	109.5	C3—C2—C1	118.8 (2)
H1A—N1—H1C	109.5	C3—C2—H2A	120.6
H1B—N1—H1C	109.5	C1—C2—H2A	120.6
C6—C1—C2	121.57 (19)	C3—C4—C5	119.3 (2)
C6—C1—N1	118.97 (16)	C3—C4—H4A	120.3
C2—C1—N1	119.46 (18)	C5—C4—H4A	120.3
C1—C6—C5	119.32 (19)	C9—O3—H3	112.2
C1—C6—H6A	120.3	O4—C9—O3	126.41 (15)
C5—C6—H6A	120.3	O4—C9—C8	121.21 (15)
C6—C5—C4	119.8 (2)	O3—C9—C8	112.36 (13)
C6—C5—C7	118.5 (2)	O1—C8—O2	125.99 (15)
C4—C5—C7	121.7 (2)	O1—C8—C9	119.18 (14)
N2—C7—C5	177.9 (3)	O2—C8—C9	114.83 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1ⁱ	0.82	1.96	2.767 (2)	166
N1—H1A···O1ⁱⁱ	0.89	1.91	2.797 (2)	172
N1—H1C···O2ⁱⁱⁱ	0.89	1.96	2.778 (2)	152
O3—H3···O2ⁱⁱⁱ	0.82	1.74	2.559 (2)	178
N1—H1B···O1W	0.89	1.91	2.788 (2)	167

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

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·C₂HO₄⁻·0.5H₂O
M_r	217.18
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	173
a, b, c (Å)	15.1221 (7), 5.6518 (1), 13.6926 (6)
β (°)	113.22 (4)
V (Å³)	1075.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.10 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury2 (2x2 bin mode) diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7209, 2446, 1906
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.156, 1.07
No. of reflections	2446
No. of parameters	142
No. of restraints	5
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.24

Computer programs: CrystalClear (Rigaku, 2005), 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
O1W—H1WA···O1ⁱ	0.82	1.96	2.767 (2)	166
N1—H1A···O1ⁱⁱ	0.89	1.91	2.797 (2)	172
N1—H1C···O2ⁱⁱⁱ	0.89	1.96	2.778 (2)	152
O3—H3···O2ⁱⁱⁱ	0.82	1.74	2.559 (2)	178
N1—H1B···O1W	0.89	1.91	2.788 (2)	167

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

Acknowledgements

This work was supported by a start-up Grant from Southeast University, People's Republic of China.

References

Chen, Z.-F., Xiong, R.-G., Zhang, J., Zuo, J.-L., You, X.-Z., Che, C.-M. & Fun, H.-K. (2000). J. Chem. Soc. Dalton Trans. pp. 4010–4012. Web of Science CrossRef Google Scholar
Dai, J. & Chen, X.-Y. (2011). Acta Cryst. E67, o287. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liu, C.-M., Yu, Z., Xiong, R.-G., Liu, K. & You, X.-Z. (1999). Inorg. Chem. Commun. 2, 31–34. 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
Xu, R.-J., Fu, D.-W., Dai, J., Zhang, Y., Ge, J.-Z. & Ye, H.-Y. (2011). Inorg. Chem. Commun. 14, 1093–1096. Web of Science CSD CrossRef CAS Google Scholar
Zhao, H., Qu, Z.-R., Ye, Q., Abrahams, B. F., Wang, Y.-P., Liu, Z.-G., Xue, Z.-L., Xiong, R.-G. & You, X.-Z. (2003). Chem. Mater. 15, 4166. Web of Science CSD CrossRef Google Scholar
Zheng, W.-N. (2011). Acta Cryst. E67, m344. Web of Science CSD CrossRef IUCr Journals Google Scholar