3-Chloro-2-methyl-anilinium chloride monohydrate.

In the title hydrated salt, C7H9ClN(+)·Cl(-)·H2O, the organic cations, anions and water mol-ecules are connected by N-H⋯Cl, N-H⋯O and O-H⋯Cl hydrogen bonds. These inter-actions lead to the formation of layers parallel to the ac plane.

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 = 196.07

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.163

S = 0.92

3947 reflections

100 parameters

3 restraints

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.42 e Å−3

Absolute structure: Flack (1983 ▶), unique data only

Absolute structure parameter: −0.04 (19)

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 ▶).

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

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

Click here for additional data file.

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

CCDC reference: 1000637

Additional supporting information: crystallographic information; 3D view; checkCIF report

C7H9ClN+·Cl−·H2O	F(000) = 408
Mr = 196.07	Dx = 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

Enraf–Nonius CAD-4 diffractometer	Rint = 0.035
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 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 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(Fo2) + (0.0841P)2] where P = (Fo2 + 2Fc2)/3
S = 0.92	(Δ/σ)max < 0.001
3947 reflections	Δρmax = 0.35 e Å−3
100 parameters	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···Cl2iv	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

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⋯O1W iii	0.89	2.30	2.667 (4)	105
N1—H1B⋯Cl2iv	0.89	2.68	3.187 (3)	117
N1—H1B⋯O1W iii	0.89	2.28	2.667 (4)	106
N1—H1C⋯Cl2ii	0.89	2.83	3.178 (3)	105

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .