3-Chloro-2-methyl­anilinium chloride monohydrate

Maroua, A.; Lamia, K.; Ahmed, H.; Mohamed, R.

doi:10.1107/S1600536814009921

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page o643

doi:10.1107/S1600536814009921

Open

access

3-Chloro-2-methylanilinium chloride monohydrate

Arbi Maroua,^a Khederi Lamia,^a ^* Hamdi Ahmed ^a and Rzaigui Mohamed ^a

^aLaboratory of Materials Chemistry, Faculty of Sciences of Bizerte, 7021 Zarzouna, Bizerte, Tunisia
^*Correspondence e-mail: Lamia.khederi@fsb.rnu.tn

Edited by L. Farrugia, University of Glasgow, Scotland (Received 7 April 2014; accepted 2 May 2014; online 10 May 2014)

In the title hydrated salt, C₇H₉ClN⁺·Cl⁻·H₂O, the organic cations, anions and water molecules are connected by N—H⋯Cl, N—H⋯O and O—H⋯Cl hydrogen bonds. These interactions lead to the formation of layers parallel to the ac plane.

CCDC reference: 1000637

Related literature

For hydrogen bonds, see: Steiner (2002 ); Jayaraman et al. (2002 ). For the crystal structure of a related protonated amine, see: Hamdi et al. (2014 ). For related structures containing the 3-chloro-2-methylanilinium cation, see: Khemiri et al. (2008 ); Bel Haj Salah et al. (2014 ). For geometrical features, see: Oueslati et al. (2005 ).

Experimental

Crystal data

C₇H₉ClN⁺·Cl⁻·H₂O
M_r = 196.07
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.434 (4) Å
b = 7.475 (3) Å
c = 16.785 (2) Å
V = 932.7 (6) Å³
Z = 4
Ag Kα radiation
λ = 0.56087 Å
μ = 0.33 mm⁻¹
T = 293 K
0.50 × 0.25 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
5019 measured reflections
3947 independent reflections
1804 reflections with I > 2σ(I)
R_int = 0.035
2 standard reflections every 120 min intensity decay: 6%

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.163
S = 0.92
3947 reflections
100 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.42 e Å⁻³
Absolute structure: Flack (1983 ), unique data only
Absolute structure parameter: −0.04 (19)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯Cl2ⁱ	0.86	2.28	3.129 (3)	169
O1W—H2W1⋯Cl2	0.86	2.36	3.139 (3)	151
N1—H1A⋯Cl2ⁱⁱ	0.89	2.70	3.178 (3)	115
N1—H1A⋯O1Wⁱⁱⁱ	0.89	2.30	2.667 (4)	105
N1—H1B⋯Cl2^iv	0.89	2.68	3.187 (3)	117
N1—H1B⋯O1Wⁱⁱⁱ	0.89	2.28	2.667 (4)	106
N1—H1C⋯Cl2ⁱⁱ	0.89	2.83	3.178 (3)	105
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (ii) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 1000637

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814009921/fj2671sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814009921/fj2671Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814009921/fj2671Isup3.cml

checkCIF report

Comment top

Hydrogen bonding is of interest because of their prevalent occurrence in biological systems (Steiner 2002; Jayaraman et al., 2002). Therefore, it is extremely useful to search simple molecules allowing understanding the configuration and the function of some complex macromolecules. The title compound, was prepared as part of our ongoing studies of hydrogen-bonding interactions in the crystal structure of protonated amines (Hamdi et al., 2014). Structures containing the 3-chloro-2-methylanilinium cation have been already reported with dihydrogenphosphate (Khemiri et al., 2008) and cyclohexaphosphate (Bel Haj Salah et al., 2014).

The asymmetric unit of the title compound (I), illustrated in Fig. 1, consists of one organic cation, one Cl^- anion and one water molecule. All bond distances and angles are within the ranges of accepted values. Moreover, they are close to respect the geometrical features observed in the crystal structure of 5-chloro-2-methylanilinium chloride (Oueslati et al., 2005). Components of the asymmetric unit develop different H-bonds, N—H···Cl, N—H···OW and OW—H···Cl (Fig. 2) that keep them in a state where the aromatic rings of organic buildings are oriented in the direction of the bc planes to form centro-symmetric pairs interconnected by hydrogen bonds in the direction of the b axis (Fig. 2). The resulting sequences are alternated to form the crystal packing of the title compound (Fig. 3).

Related literature top

For hydrogen bonds, see: Steiner (2002); Jayaraman et al. (2002). For the crystal structures of a related protonated amine, see: Hamdi et al. (2014). For related structures containing the 3-chloro-2-methylanilinium cation, see: Khemiri et al. (2008); Bel Haj Salah et al. (2014). For geometrical features, see: Oueslati et al. (2005).

Experimental top

An aqueous solution of AlCl₃ (1 mmol) and 3-chloro-2-methylaniline (2 mmol) in hydrochloric acid was stirred for several minutes at room temperature and slowly evaporated to dryness for two weeks. White single crystals of the title compound were carefully isolated under polarizing microscope for X-ray diffraction analysis.

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 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. ORTEP drawing of the asymmetric unit of title compound with displacement ellipsoids drawn at 40% probability level. [Symmetry code: (i) x, y, z]
	Fig. 2. A view of the atomic arrangement of the title compound along the a axis with H bonds shown as dashed lines.
	Fig. 3. A diagram of the crystal packing in the title compound, viewed down the b axis.

3-Chloro-2-methylanilinium chloride monohydrate top

Crystal data top

C₇H₉ClN⁺·Cl⁻·H₂O	F(000) = 408
M_r = 196.07	D_x = 1.396 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Ag Kα radiation, λ = 0.56087 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 7.434 (4) Å	θ = 9–11°
b = 7.475 (3) Å	µ = 0.33 mm⁻¹
c = 16.785 (2) Å	T = 293 K
V = 932.7 (6) Å³	Rectangular, colorless
Z = 4	0.50 × 0.25 × 0.15 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.035
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.4°
Graphite monochromator	h = −3→12
non–profiled ω scans	k = −3→12
5019 measured reflections	l = −2→28
3947 independent reflections	2 standard reflections every 120 min
1804 reflections with I > 2σ(I)	intensity decay: 6%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.055	H-atom parameters constrained
wR(F²) = 0.163	w = 1/[σ²(F_o²) + (0.0841P)²] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max < 0.001
3947 reflections	Δρ_max = 0.35 e Å⁻³
100 parameters	Δρ_min = −0.42 e Å⁻³
3 restraints	Absolute structure: Flack (1983), unique data only
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.04 (19)

Crystal data top

C₇H₉ClN⁺·Cl⁻·H₂O	V = 932.7 (6) Å³
M_r = 196.07	Z = 4
Orthorhombic, P2₁2₁2₁	Ag Kα radiation, λ = 0.56087 Å
a = 7.434 (4) Å	µ = 0.33 mm⁻¹
b = 7.475 (3) Å	T = 293 K
c = 16.785 (2) Å	0.50 × 0.25 × 0.15 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.035
5019 measured reflections	2 standard reflections every 120 min
3947 independent reflections	intensity decay: 6%
1804 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.055	H-atom parameters constrained
wR(F²) = 0.163	Δρ_max = 0.35 e Å⁻³
S = 0.92	Δρ_min = −0.42 e Å⁻³
3947 reflections	Absolute structure: Flack (1983), unique data only
100 parameters	Absolute structure parameter: −0.04 (19)
3 restraints

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
Cl1	0.21684 (13)	0.68978 (12)	0.14721 (5)	0.0605 (3)
N1	0.2400 (3)	0.3630 (3)	0.41835 (13)	0.0397 (7)
C1	0.2542 (4)	0.3587 (4)	0.33084 (16)	0.0375 (8)
C2	0.2248 (4)	0.5163 (4)	0.28915 (15)	0.0368 (7)
C3	0.2477 (4)	0.5022 (5)	0.20642 (15)	0.0429 (8)
C4	0.2959 (5)	0.3453 (4)	0.16946 (19)	0.0520 (10)
C5	0.3203 (5)	0.1946 (5)	0.2135 (2)	0.0581 (10)
C6	0.3010 (4)	0.2003 (4)	0.29557 (18)	0.0435 (8)
C7	0.1793 (5)	0.6906 (4)	0.3283 (2)	0.0551 (10)
O1W	0.5280 (3)	0.0960 (3)	0.01902 (16)	0.0676 (9)
Cl2	0.62142 (10)	0.50337 (10)	0.00015 (4)	0.0469 (2)
H1A	0.20910	0.47250	0.43403	0.0477*
H1B	0.34559	0.33388	0.43972	0.0477*
H1C	0.15674	0.28516	0.43419	0.0477*
H3	0.31954	0.09820	0.32617	0.0522*
H4	0.35005	0.08749	0.18857	0.0698*
H5	0.31181	0.34223	0.11452	0.0624*
H7A	0.16524	0.78143	0.28835	0.0825*
H7B	0.27430	0.72387	0.36406	0.0825*
H7C	0.06902	0.67814	0.35757	0.0825*
H1W1	0.42091	0.05452	0.01130	0.0825*
H2W1	0.52857	0.20105	−0.00122	0.0825*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0707 (6)	0.0555 (5)	0.0553 (4)	0.0060 (5)	−0.0007 (4)	0.0165 (4)
N1	0.0420 (14)	0.0319 (11)	0.0452 (11)	0.0055 (11)	0.0059 (11)	0.0037 (9)
C1	0.0382 (16)	0.0326 (12)	0.0417 (12)	0.0018 (12)	0.0008 (12)	−0.0010 (10)
C2	0.0342 (13)	0.0304 (12)	0.0458 (13)	0.0014 (13)	−0.0018 (12)	−0.0004 (11)
C3	0.0385 (16)	0.0449 (14)	0.0452 (13)	0.0025 (16)	0.0000 (12)	0.0064 (14)
C4	0.0593 (19)	0.0548 (19)	0.0419 (14)	0.006 (2)	0.0005 (15)	−0.0039 (14)
C5	0.074 (2)	0.0428 (16)	0.0576 (18)	0.012 (2)	0.0078 (18)	−0.0144 (16)
C6	0.0456 (16)	0.0296 (12)	0.0554 (15)	0.0057 (15)	0.0021 (14)	−0.0023 (13)
C7	0.073 (2)	0.0393 (16)	0.0529 (16)	0.0120 (19)	0.0011 (16)	−0.0014 (16)
O1W	0.0608 (15)	0.0390 (12)	0.103 (2)	−0.0020 (11)	−0.0192 (16)	0.0113 (13)
Cl2	0.0476 (3)	0.0359 (3)	0.0573 (4)	−0.0004 (3)	−0.0068 (4)	0.0006 (4)

Geometric parameters (Å, º) top

Cl1—C3	1.734 (4)	C2—C3	1.403 (4)
O1W—H2W1	0.8600	C3—C4	1.374 (5)
O1W—H1W1	0.8600	C4—C5	1.360 (5)
N1—C1	1.473 (4)	C5—C6	1.386 (5)
N1—H1A	0.8900	C4—H5	0.9300
N1—H1C	0.8900	C5—H4	0.9300
N1—H1B	0.8900	C6—H3	0.9300
C1—C2	1.388 (4)	C7—H7C	0.9600
C1—C6	1.369 (4)	C7—H7A	0.9600
C2—C7	1.498 (4)	C7—H7B	0.9600

H1W1—O1W—H2W1	106.00	C3—C4—C5	119.8 (3)
H1A—N1—H1C	109.00	C4—C5—C6	120.1 (3)
H1B—N1—H1C	109.00	C1—C6—C5	118.9 (3)
C1—N1—H1B	109.00	C3—C4—H5	120.00
C1—N1—H1C	109.00	C5—C4—H5	120.00
C1—N1—H1A	109.00	C6—C5—H4	120.00
H1A—N1—H1B	109.00	C4—C5—H4	120.00
C2—C1—C6	123.8 (3)	C1—C6—H3	121.00
N1—C1—C2	118.2 (2)	C5—C6—H3	121.00
N1—C1—C6	117.9 (3)	C2—C7—H7B	109.00
C1—C2—C7	123.6 (2)	C2—C7—H7C	109.00
C3—C2—C7	121.8 (3)	C2—C7—H7A	109.00
C1—C2—C3	114.6 (3)	H7A—C7—H7C	109.00
Cl1—C3—C4	117.8 (2)	H7B—C7—H7C	109.00
C2—C3—C4	122.9 (3)	H7A—C7—H7B	109.00
Cl1—C3—C2	119.4 (3)

N1—C1—C2—C3	177.7 (3)	C1—C2—C3—C4	−0.2 (5)
N1—C1—C2—C7	0.2 (4)	C7—C2—C3—Cl1	−1.8 (4)
C6—C1—C2—C3	−0.3 (4)	C7—C2—C3—C4	177.6 (3)
C6—C1—C2—C7	−178.0 (3)	Cl1—C3—C4—C5	−179.5 (3)
N1—C1—C6—C5	−178.1 (3)	C2—C3—C4—C5	1.2 (5)
C2—C1—C6—C5	−0.2 (5)	C3—C4—C5—C6	−1.6 (5)
C1—C2—C3—Cl1	−179.5 (2)	C4—C5—C6—C1	1.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···Cl2ⁱ	0.8600	2.2800	3.129 (3)	169.00
O1W—H2W1···Cl2	0.8600	2.3600	3.139 (3)	151.00
N1—H1A···Cl2ⁱⁱ	0.8900	2.7000	3.178 (3)	115.00
N1—H1A···O1Wⁱⁱⁱ	0.8900	2.3000	2.667 (4)	105.00
N1—H1B···Cl2^iv	0.8900	2.6800	3.187 (3)	117.00
N1—H1B···O1Wⁱⁱⁱ	0.8900	2.2800	2.667 (4)	106.00
N1—H1C···Cl2ⁱⁱ	0.8900	2.8300	3.178 (3)	105.00
C7—H7A···Cl1	0.9600	2.5000	3.053 (4)	117.00

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···Cl2ⁱ	0.8600	2.2800	3.129 (3)	169.00
O1W—H2W1···Cl2	0.8600	2.3600	3.139 (3)	151.00
N1—H1A···Cl2ⁱⁱ	0.8900	2.7000	3.178 (3)	115.00
N1—H1A···O1Wⁱⁱⁱ	0.8900	2.3000	2.667 (4)	105.00
N1—H1B···Cl2^iv	0.8900	2.6800	3.187 (3)	117.00
N1—H1B···O1Wⁱⁱⁱ	0.8900	2.2800	2.667 (4)	106.00
N1—H1C···Cl2ⁱⁱ	0.8900	2.8300	3.178 (3)	105.00

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

References

Bel Haj Salah, R., Khederi, L. & Rzaigui, M. (2014). Acta Cryst. E70, o61. CSD CrossRef IUCr Journals Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hamdi, A., Khederi, L. & Rzaigui, M. (2014). Acta Cryst. E70, o342–o343. CSD CrossRef CAS IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Jayaraman, K., Choudhury, A. & Rao, C. N. R. (2002). Solid State Sci. 4, 413–422. Web of Science CSD CrossRef CAS Google Scholar
Khemiri, H., Akriche, S. & Rzaigui, M. (2008). Acta Cryst. E64, o526. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oueslati, A., Rayes, A., Ben Nasr, C. & Rzaigui, M. (2005). Z. Kristallogr. New Cryst. Struct. 220, 105–106. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steiner, T. (2002). Angew. Chem. Int. Ed. 41, 48–76. Web of Science CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page o643

doi:10.1107/S1600536814009921

Open

access