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Acta Cryst. (2007). E63, o3682-o3683    [ doi:10.1107/S1600536807037117 ]

2-Methylanilinium chloride monohydrate

M. Benslimane, H. Merazig, S. Bouacida, S. Denbri, A. Beghidja and L. Ouahab

Abstract top

The asymmetric unit of the title compound, C7H10N+·Cl-·H2O, contains a 2-methylanilinium cation, a chloride anion and one molecule of water. The crystal structure consists of alternating layers of hydrophobic and hydrophilic zones of o-toluidine along the c axis. The water molecules and the chloride anions are sandwiched between these layers. A large number of cation-anion, cation-water and water-anion hydrogen bonds result in a two-dimensional network which reinforces the cohesion of the ionic structure.

Comment top

Organic–inorganic hybrid materials have attracted a great deal of attention over the past few decades (Koutselas et al., 1996; Mitzi et al., 1998; Mayer et al., 1999; Mazeaud et al., 2000) because of their ionic, electrical, magnetic and optical properties (Hill, 1998; Kagan et al., 1999; Raptopoulou et al., 2002).

The methylanilinium is already reported with nitrate (Benali-Cherif et al., 2007), picrate (Muthamizhchelvan et al., 2005) and dihydrogenphosphate (Fábry et al., 2002).

In the course of our ongoing program related to the synthesis and structural study of hybrid compounds based on tin and amines (Bouacida et al., 2007; Bouacida et al., 2006; Bouacida et al., 2005a; Bouacida et al., 2005b; Bouacida et al., 2005c), we report here the synthesis and crystal structure of 2-Methylanilinium chloride monohydrate, (I).

The molecular geometry and the atom-numbering scheme of (I) are shown in Fig. 1. The asymmetric unit of the title compound consist of a2-methylanilinium cation, a chloride anion and one molecule of water. The crystal structure consists of alternating layers of 2-methylanilinium. The chloride ions and water molecules are sandwiched between layers of hydrophobic and hydrophilic zones of 2-methylanilinium(Fig. 2). In this structure, three types of classical hydrogen bonds are observed, viz.cation–anion, cation–water and water-anion, with the N atom of the cation and O of water acting as donors (Fig.3, Table 1).

Related literature top

For related literature, see: Benali-Cherif et al. (2007); Bouacida et al. (2005a, 2005b, 2005c, 2006, 2007); Fábry et al. (2002); Hill (1998); Kagan et al. (1999); Koutselas et al. (1996); Mayer et al. (1999); Mazeaud et al. (2000); Mitzi et al. (1998); Muthamizhchelvan et al. (2005); Raptopoulou et al. (2002).

Experimental top

Crystals were grown from aqueous solutions that were obtained by dissolving 1 mmol SnCl2·2H2O, 2 mmol 2-methylaniline in hydrochloric acid. The solutions were slowly evaporated to dryness for a couple of weeks. Some red crystals were carefully isolated under polarizing microscope for analysis by X-ray diffraction.

Refinement top

All H atoms were localized in Fourier maps but introduced in calculated positions and treated as riding on their parent C and N atoms with C—H = 0.93–0.96Å and N—H = 0.89Å and Uiso(H) =1.2–1.5 (carrier atom), except for H1W and H2W were located in a difference Fourier map and refined isotropically.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg et al., 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The packing of (I), viewed down the C axis, showing layers of molecule.
[Figure 3] Fig. 3. A view of the ionic stacking, showing the hydrogen bonds as dashed lines.
2-Methylanilinium chloride monohydrate top
Crystal data top
C7H10N+·Cl–·H2OF000 = 344
Mr = 161.63Dx = 1.205 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5072 reflections
a = 8.1871 (5) Åθ = 1.0–25.0º
b = 7.4046 (4) ŵ = 0.37 mm−1
c = 14.7415 (5) ÅT = 173 (2) K
β = 94.600 (4)ºPrism, red
V = 890.78 (8) Å30.10 × 0.08 × 0.06 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer		1203 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.016
T = 100(2) Kθmax = 25.0º
φ and ω scansθmin = 2.5º
Absorption correction: noneh = −9→9
2895 measured reflectionsk = −8→8
1508 independent reflectionsl = −16→16
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.040  w = 1/[σ2(Fo2) + (0.0907P)2 + 0.0493P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.141(Δ/σ)max = 0.001
S = 1.11Δρmax = 0.27 e Å−3
1508 reflectionsΔρmin = −0.19 e Å−3
100 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.116 (18)
Secondary atom site location: difference Fourier map
Crystal data top
C7H10N+·Cl–·H2OV = 890.78 (8) Å3
Mr = 161.63Z = 4
Monoclinic, P21/cMo Kα
a = 8.1871 (5) ŵ = 0.37 mm−1
b = 7.4046 (4) ÅT = 173 (2) K
c = 14.7415 (5) Å0.10 × 0.08 × 0.06 mm
β = 94.600 (4)º
Data collection top
Nonius KappaCCD
diffractometer		1508 independent reflections
Absorption correction: none1203 reflections with I > 2σ(I)
2895 measured reflectionsRint = 0.016
Refinement top
R[F2 > 2σ(F2)] = 0.040100 parameters
wR(F2) = 0.141H atoms treated by a mixture of
independent and constrained refinement
S = 1.11Δρmax = 0.27 e Å−3
1508 reflectionsΔρmin = −0.19 e Å−3
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
xyzUiso*/Ueq
N10.2974 (2)0.3362 (2)0.44034 (12)0.0545 (6)
C10.1203 (3)0.3087 (3)0.44239 (15)0.0524 (7)
C20.0621 (3)0.2488 (3)0.52207 (15)0.0606 (8)
C3−0.1035 (3)0.2160 (4)0.5250 (2)0.0759 (10)
C4−0.2066 (3)0.2427 (4)0.4493 (2)0.0818 (11)
C5−0.1480 (4)0.3034 (4)0.3699 (2)0.0791 (11)
C60.0189 (3)0.3381 (3)0.36395 (16)0.0643 (9)
C70.0874 (4)0.4069 (5)0.27810 (17)0.0932 (11)
O1W0.4013 (3)0.0788 (3)0.32831 (14)0.0917 (9)
Cl10.50523 (7)0.17364 (8)0.13149 (3)0.0628 (3)
H1A0.345650.324730.496340.0817*
H1B0.316280.446330.419370.0817*
H1C0.337830.254190.404090.0817*
H20.133600.230520.573500.0727*
H3−0.144230.175830.578590.0910*
H4−0.317940.219780.451200.0981*
H5−0.220820.321740.319040.0949*
H7A0.149650.514820.291570.1397*
H7B−0.001030.432970.233280.1397*
H7C0.157150.316440.254980.1397*
H1W0.424 (3)0.098 (3)0.2830 (17)0.0500*
H2W0.442 (3)−0.008 (4)0.3448 (16)0.0500*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0624 (12)0.0549 (11)0.0463 (10)0.0004 (8)0.0053 (8)−0.0004 (7)
C10.0586 (13)0.0458 (12)0.0527 (12)0.0065 (9)0.0035 (9)−0.0069 (8)
C20.0653 (15)0.0590 (14)0.0581 (13)0.0029 (11)0.0096 (10)−0.0041 (10)
C30.0702 (18)0.0810 (18)0.0789 (18)−0.0004 (13)0.0212 (13)−0.0104 (13)
C40.0610 (16)0.088 (2)0.097 (2)0.0064 (14)0.0095 (14)−0.0251 (16)
C50.0688 (17)0.0814 (19)0.0839 (19)0.0181 (13)−0.0132 (14)−0.0224 (13)
C60.0764 (17)0.0592 (14)0.0559 (14)0.0133 (11)−0.0042 (11)−0.0084 (9)
C70.117 (2)0.104 (2)0.0556 (16)0.0058 (19)−0.0109 (14)0.0130 (14)
O1W0.142 (2)0.0740 (13)0.0642 (12)0.0295 (13)0.0406 (12)0.0094 (10)
Cl10.0757 (5)0.0641 (5)0.0492 (4)0.0006 (3)0.0085 (3)−0.0042 (2)
Geometric parameters (Å, °) top
O1W—H1W0.72 (3)C4—C51.376 (4)
O1W—H2W0.76 (3)C5—C61.400 (4)
N1—C11.467 (3)C6—C71.513 (4)
N1—H1B0.8900C2—H20.9300
N1—H1A0.8900C3—H30.9300
N1—H1C0.8900C4—H40.9300
C1—C21.376 (3)C5—H50.9300
C1—C61.386 (3)C7—H7C0.9600
C2—C31.381 (3)C7—H7A0.9600
C3—C41.359 (4)C7—H7B0.9600
Cl1···N1i3.2015 (17)C6···C2v3.578 (3)
Cl1···O1W3.167 (2)C7···H1C2.8800
Cl1···N1ii3.1736 (18)C7···H1B2.7000
Cl1···O1Wiii3.141 (2)H1A···Cl1iv2.2900
Cl1···H2Wiii2.42 (3)H1A···H22.2600
Cl1···H1W2.45 (2)H1B···C72.7000
Cl1···H1Aii2.2900H1B···Cl1iii2.3900
Cl1···H1Bi2.3900H1B···H7A2.2900
O1W···C13.412 (3)H1C···H7C2.5900
O1W···Cl13.167 (2)H1C···H2W2.3200
O1W···N12.704 (3)H1C···C72.8800
O1W···Cl1i3.141 (2)H1C···H1W2.2900
O1W···H7C2.8100H1C···O1W1.8200
O1W···H1C1.8200H1W···H1C2.2900
N1···O1W2.704 (3)H1W···Cl12.45 (2)
N1···Cl1iv3.1736 (18)H2···H1A2.2600
N1···Cl1iii3.2015 (17)H2W···Cl1i2.42 (3)
N1···H7C2.8800H2W···H1C2.3200
N1···H7A2.7600H5···H7B2.4200
C1···O1W3.412 (3)H7A···H1B2.2900
C1···C3v3.556 (4)H7A···N12.7600
C2···C6v3.578 (3)H7B···H52.4200
C2···C3vi3.533 (4)H7C···O1W2.8100
C3···C2vi3.533 (4)H7C···N12.8800
C3···C1v3.556 (4)H7C···H1C2.5900
H1W—O1W—H2W109 (3)C5—C6—C7122.9 (2)
H1B—N1—H1C109.00C3—C2—H2120.00
C1—N1—H1C109.00C1—C2—H2120.00
C1—N1—H1A109.00C2—C3—H3120.00
C1—N1—H1B110.00C4—C3—H3120.00
H1A—N1—H1B109.00C5—C4—H4120.00
H1A—N1—H1C109.00C3—C4—H4120.00
C2—C1—C6122.5 (2)C4—C5—H5119.00
N1—C1—C6119.2 (2)C6—C5—H5119.00
N1—C1—C2118.2 (2)C6—C7—H7B109.00
C1—C2—C3119.4 (2)C6—C7—H7C109.00
C2—C3—C4119.7 (3)C6—C7—H7A109.00
C3—C4—C5120.7 (3)H7A—C7—H7C109.00
C4—C5—C6121.5 (3)H7B—C7—H7C109.00
C1—C6—C5116.2 (2)H7A—C7—H7B109.00
C1—C6—C7120.9 (2)
N1—C1—C2—C3−177.9 (2)C1—C2—C3—C40.2 (4)
C6—C1—C2—C30.1 (4)C2—C3—C4—C5−0.5 (4)
N1—C1—C6—C5177.9 (2)C3—C4—C5—C60.6 (5)
N1—C1—C6—C7−3.1 (3)C4—C5—C6—C1−0.3 (4)
C2—C1—C6—C50.0 (3)C4—C5—C6—C7−179.3 (3)
C2—C1—C6—C7179.0 (2)
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+1/2, z+1/2; (v) −x, −y+1, −z+1; (vi) −x, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1iv0.89002.29003.1736 (18)170.00
N1—H1B···Cl1iii0.89002.39003.2015 (17)152.00
N1—H1C···O1W0.89001.82002.704 (3)175.00
O1W—H1W···Cl10.72 (3)2.45 (2)3.167 (2)177.9 (14)
O1W—H2W···Cl1i0.76 (3)2.42 (3)3.141 (2)161 (3)
Symmetry codes: (iv) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+1/2; (i) −x+1, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.89002.29003.1736 (18)170.00
N1—H1B···Cl1ii0.89002.39003.2015 (17)152.00
N1—H1C···O1W0.89001.82002.704 (3)175.00
O1W—H1W···Cl10.72 (3)2.45 (2)3.167 (2)177.9 (14)
O1W—H2W···Cl1iii0.76 (3)2.42 (3)3.141 (2)161 (3)
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2.
Acknowledgements top

This work was supported by Mentouri-Constantine University, Algeria.

references
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