4-Chloro­anilinium hydrogen oxalate hemihydrate

Rahmouni, H.; Smirani, W.; Rzaigui, M.; Al-Deyab, S.S.

doi:10.1107/S160053681001144X

organic compounds

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Volume 66| Part 4| April 2010| Page o993

doi:10.1107/S160053681001144X

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4-Chloroanilinium hydrogen oxalate hemihydrate

Hajer Rahmouni,^a Wajda Smirani,^a ^* Mohamed Rzaigui ^a,^b and Salem S. Al-Deyab ^b

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, and ^bPetrochemical Research Chair, College of Science, King Saud University, Riyadh, Saudi Arabia
^*Correspondence e-mail: wajda_sta@yahoo.fr

(Received 25 March 2010; accepted 25 March 2010; online 31 March 2010)

In the title hydrated molecular salt, C₆H₇ClN⁺·C₂HO₄⁻·0.5H₂O, the water O atom lies on a crystallographic twofold axis. In the crystal, the anions are linked by O—H⋯O hydrogen bonds, forming chains propagating along the b axis. These chains are interconnected through O—H⋯O hydrogen bonds from the water molecules and N—H⋯O hydrogen bonds from the cations, building layers parallel to the ab plane.

Related literature

For background to supramolecular networks, see: Subramanian & Zawarotko (1994 ). For related structures, see: Akriche & Rzaigui (2009 ); Dhaouadi et al. (2008 ).

Experimental

Crystal data

C₆H₇ClN⁺·C₂HO₄⁻·0.5H₂O
M_r = 226.61
Monoclinic, C 2/c
a = 26.739 (2) Å
b = 5.701 (3) Å
c = 13.859 (2) Å
β = 111.02 (3)°
V = 1972.0 (11) Å³
Z = 8
Ag Kα radiation
λ = 0.56085 Å
μ = 0.20 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
5686 measured reflections
4806 independent reflections
2341 reflections with I > 2σ(I)
R_int = 0.021
2 standard reflections every 120 min intensity decay: 5%

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.174
S = 1.01
4806 reflections
136 parameters
H-atom parameters not refined
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H1⋯O1ⁱ	0.81 (2)	1.97 (2)	2.762 (2)	169 (2)
O3—H3⋯O2ⁱⁱ	0.82	1.79	2.606 (2)	173
N1—H1A⋯O5	0.89	1.93	2.802 (3)	165
N1—H1B⋯O1ⁱⁱⁱ	0.89	1.98	2.792 (3)	151
N1—H1C⋯O2	0.89	1.92	2.790 (2)	167
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y-1, z; (iii) $[x, -y, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681001144X/hb5378sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681001144X/hb5378Isup2.hkl

checkCIF report

Comment top

Hydrogen bonding is by far the most well- studied interaction which is employed to control the conformational and topological features of the molecular assembly in the solid state (Subramanian, S. & Zawarotko, J., 1994) . In this paper, we report the synthesis and the X-ray study of the title compound, (I), a new oxalate of para-chloroanilinium hemi-hydrate, C₆H₇NCl⁺.HC₂O₄^-.0.5H₂O. The asymmetric unit contains one oxalate anion, one para-chloroanilinium cation and a water molecule (Fig. 1).

The crystal structure of the title compound is characterized by the existence of inorganic layers, built by HC₂O₄^-anions, ammonium cations and water molecules. Each anion is connected to its adjacent neighbours by O—H···O strong hydrogen bond to form chains along b axis. These chains are interconnected through O—H···O hydrogen bonds of the water molecules and N—H···O of the ammonium cations to build layers parallel to the (ab) planes at z = 0 and z = 1/2 (Fig. 2).

The protonated p-chloroaniline molecule is localized in the interlayer space, and neutralizes the negative charge of the anionic part. These groups are oriented in the same direction forming so intermolecular van der Waals interactions between them and establishing particularly hydrogen bonds with oxygen atoms of the anionic layers.

The C—C, C—O distances and O—C—O, C—C—O angles in oxalate anion have standard values (Akriche, S. & Rzaigui, M., 2009). The examination of the organic molecule shows that the N—C, C—C and C—Cl distances and C—C—C, C—C—N and C—C—Cl angles are comparable with those obtained in other salts associated to the same protonated amine (Dhaouadi, H. et al. 2008).

Related literature top

For background to supramolecular networks, see: Subramanian & Zawarotko (1994). For related structures, see: Akriche & Rzaigui (2009); Dhaouadi et al. (2008).

Experimental top

An ethanolic solution of p-chloroaniline (50 mmol, in 50 ml) was added under stirring to 100 ml of an aqueous solution of oxalate acid (1 M). Pink blocks of (I) appeared after few days of evaporation at room temperature.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids for non-H atoms drawn at the 30% probability level.
	Fig. 2. A perspective view of packing of (I).

4-Chloroanilinium hydrogen oxalate hemihydrate top

Crystal data top

C₆H₇ClN⁺·C₂HO₄⁻·0.5H₂O	F(000) = 936
M_r = 226.61	D_x = 1.527 Mg m⁻³
Monoclinic, C2/c	Ag Kα radiation, λ = 0.56085 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 26.739 (2) Å	θ = 9–11°
b = 5.701 (3) Å	µ = 0.20 mm⁻¹
c = 13.859 (2) Å	T = 293 K
β = 111.02 (3)°	Block, pink
V = 1972.0 (11) Å³	0.30 × 0.20 × 0.20 mm
Z = 8

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.021
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.4°
Graphite monochromator	h = −5→44
non–profiled ω scans	k = 0→9
5686 measured reflections	l = −23→22
4806 independent reflections	2 standard reflections every 120 min
2341 reflections with I > 2σ(I)	intensity decay: 5%

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.174	H-atom parameters not refined
S = 1.01	w = 1/[σ²(F_o²) + (0.0711P)² + 0.8804P] where P = (F_o² + 2F_c²)/3
4806 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

C₆H₇ClN⁺·C₂HO₄⁻·0.5H₂O	V = 1972.0 (11) Å³
M_r = 226.61	Z = 8
Monoclinic, C2/c	Ag Kα radiation, λ = 0.56085 Å
a = 26.739 (2) Å	µ = 0.20 mm⁻¹
b = 5.701 (3) Å	T = 293 K
c = 13.859 (2) Å	0.30 × 0.20 × 0.20 mm
β = 111.02 (3)°

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.021
5686 measured reflections	2 standard reflections every 120 min
4806 independent reflections	intensity decay: 5%
2341 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.174	H-atom parameters not refined
S = 1.01	Δρ_max = 0.41 e Å⁻³
4806 reflections	Δρ_min = −0.52 e Å⁻³
136 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
H1	0.5152 (9)	0.705 (4)	0.2959 (17)	0.047 (7)*
Cl1	0.19472 (2)	0.44325 (17)	0.06451 (5)	0.0743 (3)
O5	0.5000	0.6144 (3)	0.2500	0.0321 (4)
O2	0.44106 (6)	0.1863 (2)	0.46326 (9)	0.0360 (3)
C7	0.44211 (7)	0.0194 (3)	0.52200 (12)	0.0249 (3)
O3	0.44333 (6)	−0.3952 (2)	0.54031 (10)	0.0405 (3)
H3	0.4408	−0.5227	0.5116	0.061*
C8	0.43716 (6)	−0.2276 (3)	0.47280 (12)	0.0254 (3)
O1	0.44687 (6)	0.0354 (2)	0.61417 (9)	0.0401 (3)
N1	0.42789 (6)	0.2638 (3)	0.25679 (11)	0.0304 (3)
H1A	0.4460	0.3837	0.2442	0.046*
H1B	0.4353	0.1338	0.2289	0.046*
H1C	0.4374	0.2445	0.3248	0.046*
O4	0.42904 (6)	−0.2531 (2)	0.38251 (9)	0.0389 (3)
C1	0.37061 (7)	0.3117 (3)	0.21167 (12)	0.0299 (3)
C6	0.35291 (8)	0.5162 (4)	0.15786 (16)	0.0430 (5)
H6	0.3773	0.6259	0.1516	0.052*
C4	0.26302 (8)	0.3917 (5)	0.12275 (15)	0.0463 (5)
C2	0.33516 (9)	0.1479 (4)	0.22190 (16)	0.0449 (5)
H2	0.3477	0.0105	0.2588	0.054*
C5	0.29834 (9)	0.5574 (4)	0.11304 (19)	0.0522 (6)
H5	0.2857	0.6955	0.0768	0.063*
C3	0.28077 (9)	0.1887 (5)	0.17710 (18)	0.0523 (6)
H3A	0.2564	0.0793	0.1838	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0367 (3)	0.1244 (7)	0.0581 (4)	0.0117 (3)	0.0125 (2)	−0.0091 (4)
O5	0.0451 (10)	0.0241 (8)	0.0239 (8)	0.000	0.0084 (7)	0.000
O2	0.0605 (8)	0.0192 (5)	0.0290 (6)	−0.0017 (6)	0.0167 (6)	0.0022 (4)
C7	0.0327 (7)	0.0186 (6)	0.0235 (6)	−0.0026 (6)	0.0102 (6)	−0.0021 (5)
O3	0.0757 (10)	0.0167 (5)	0.0308 (6)	−0.0014 (6)	0.0212 (7)	0.0012 (4)
C8	0.0325 (8)	0.0186 (6)	0.0243 (7)	−0.0015 (6)	0.0094 (6)	−0.0005 (5)
O1	0.0714 (9)	0.0255 (6)	0.0286 (6)	−0.0124 (6)	0.0243 (6)	−0.0070 (5)
N1	0.0357 (7)	0.0295 (7)	0.0264 (6)	0.0009 (6)	0.0117 (6)	0.0000 (5)
O4	0.0616 (9)	0.0292 (6)	0.0242 (5)	0.0026 (6)	0.0134 (6)	−0.0036 (5)
C1	0.0354 (8)	0.0305 (8)	0.0235 (7)	0.0009 (7)	0.0102 (6)	−0.0026 (6)
C6	0.0426 (10)	0.0331 (9)	0.0466 (11)	−0.0019 (8)	0.0079 (8)	0.0051 (8)
C4	0.0343 (9)	0.0695 (15)	0.0343 (9)	0.0042 (10)	0.0112 (7)	−0.0095 (10)
C2	0.0476 (11)	0.0448 (11)	0.0454 (11)	−0.0042 (9)	0.0207 (9)	0.0099 (9)
C5	0.0462 (12)	0.0451 (12)	0.0532 (12)	0.0098 (10)	0.0031 (10)	0.0055 (10)
C3	0.0443 (11)	0.0651 (15)	0.0511 (12)	−0.0100 (11)	0.0216 (10)	0.0033 (11)

Geometric parameters (Å, º) top

Cl1—C4	1.736 (2)	N1—H1C	0.8900
O5—H1	0.81 (2)	C1—C6	1.374 (3)
O2—C7	1.2460 (19)	C1—C2	1.373 (3)
C7—O1	1.2407 (19)	C6—C5	1.385 (3)
C7—C8	1.549 (2)	C6—H6	0.9300
O3—C8	1.3055 (19)	C4—C3	1.370 (3)
O3—H3	0.8200	C4—C5	1.376 (4)
C8—O4	1.1996 (19)	C2—C3	1.381 (3)
N1—C1	1.457 (2)	C2—H2	0.9300
N1—H1A	0.8900	C5—H5	0.9300
N1—H1B	0.8900	C3—H3A	0.9300

O1—C7—O2	125.89 (15)	C1—C6—C5	119.3 (2)
O1—C7—C8	118.75 (14)	C1—C6—H6	120.3
O2—C7—C8	115.36 (13)	C5—C6—H6	120.3
C8—O3—H3	109.5	C3—C4—C5	121.3 (2)
O4—C8—O3	126.01 (15)	C3—C4—Cl1	119.84 (19)
O4—C8—C7	121.60 (14)	C5—C4—Cl1	118.87 (19)
O3—C8—C7	112.39 (13)	C1—C2—C3	119.6 (2)
C1—N1—H1A	109.5	C1—C2—H2	120.2
C1—N1—H1B	109.5	C3—C2—H2	120.2
H1A—N1—H1B	109.5	C4—C5—C6	119.3 (2)
C1—N1—H1C	109.5	C4—C5—H5	120.3
H1A—N1—H1C	109.5	C6—C5—H5	120.3
H1B—N1—H1C	109.5	C4—C3—C2	119.4 (2)
C6—C1—C2	121.13 (18)	C4—C3—H3A	120.3
C6—C1—N1	119.76 (16)	C2—C3—H3A	120.3
C2—C1—N1	119.09 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O1ⁱ	0.81 (2)	1.97 (2)	2.762 (2)	169 (2)
O3—H3···O2ⁱⁱ	0.82	1.79	2.606 (2)	173
N1—H1A···O5	0.89	1.93	2.802 (3)	165
N1—H1B···O1ⁱⁱⁱ	0.89	1.98	2.792 (3)	151
N1—H1C···O2	0.89	1.92	2.790 (2)	167

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

Experimental details

Crystal data
Chemical formula	C₆H₇ClN⁺·C₂HO₄⁻·0.5H₂O
M_r	226.61
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	26.739 (2), 5.701 (3), 13.859 (2)
β (°)	111.02 (3)
V (Å³)	1972.0 (11)
Z	8
Radiation type	Ag Kα, λ = 0.56085 Å
µ (mm⁻¹)	0.20
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5686, 4806, 2341
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.836

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.174, 1.01
No. of reflections	4806
No. of parameters	136
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.52

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O1ⁱ	0.81 (2)	1.97 (2)	2.762 (2)	169 (2)
O3—H3···O2ⁱⁱ	0.82	1.79	2.606 (2)	173
N1—H1A···O5	0.89	1.93	2.802 (3)	165
N1—H1B···O1ⁱⁱⁱ	0.89	1.98	2.792 (3)	151
N1—H1C···O2	0.89	1.92	2.790 (2)	167

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

References

Akriche, S. & Rzaigui, M. (2009). Acta Cryst. E65, o793. Web of Science CSD CrossRef IUCr Journals Google Scholar
Dhaouadi, H., Marouani, H., Rzaigui, M. & Madani, A. (2008). Mater. Res. Bull. 43, 3234–3244. Web of Science CSD CrossRef CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Subramanian, S. & Zawarotko, J. (1994). Coord. Chem. Rev. 137, 357–401. CrossRef CAS Web of Science Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o993

doi:10.1107/S160053681001144X

Open

access