2,5-Dimethyl­anilinium chloride monohydrate

Smirani, W.; Rzaigui, M.

doi:10.1107/S1600536808041287

organic compounds

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Volume 65| Part 1| January 2009| Page o83

doi:10.1107/S1600536808041287

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2,5-Dimethylanilinium chloride monohydrate

Wajda Smirani ^a ^* and Mohamed Rzaigui ^a

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna, Bizerte, Tunisia
^*Correspondence e-mail: wajda_sta@yahoo.fr

(Received 4 December 2008; accepted 6 December 2008; online 10 December 2008)

In the title compound, C₈H₁₂N⁺·Cl⁻·H₂O, the crystal packing is influenced by O—H⋯Cl, N—H⋯Cl and N—H⋯O hydrogen bonds, resulting in a two-dimensional network propagating parallel to (001).

Related literature

For related literature, see: Aloui et al. (2006 ); Masse et al. (1993 ); Blessing (1986 ).

Experimental

Crystal data

C₈H₁₂N⁺·Cl⁻·H₂O
M_r = 175.65
Monoclinic, P 2₁
a = 7.515 (4) Å
b = 7.441 (3) Å
c = 9.019 (2) Å
β = 102.87 (3)°
V = 491.7 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 (2) K
0.50 × 0.30 × 0.20 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction: none
2058 measured reflections
1260 independent reflections
1166 reflections with I > 2σ(I)
R_int = 0.025
2 standard reflections frequency: 120 min intensity decay: 5%

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.081
S = 1.10
1260 reflections
111 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.14 e Å⁻³
Absolute structure: Flack (1983 ), unique data only
Flack parameter: 0.17 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H30⋯Cl1ⁱ	0.81 (4)	2.37 (4)	3.168 (3)	171 (4)
O1—H31⋯Cl1	0.78 (4)	2.44 (4)	3.219 (3)	174 (5)
N1—H1A⋯O1ⁱⁱ	0.89	1.82	2.705 (4)	171
N1—H1B⋯Cl1ⁱⁱⁱ	0.89	2.29	3.167 (2)	169
N1—H1C⋯Cl1^iv	0.89	2.30	3.189 (3)	173
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+2]$ ; (iii) $[-x+2, y+{\script{1\over 2}}, -z+2]$ ; (iv) x, y, z+1.

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 publication routines (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808041287/hb2876sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041287/hb2876Isup2.hkl

checkCIF report

Comment top

The preparation of inorganic anion and organic cation salts continues to be a focus area in chemistry and material science because of their abilities to combine the properties of organic and inorganic compounds within one single molecular scale, so as to exhibit some interesting crystal structure and some special properties, such as second-order nonlinear optical response, magnetism, luminescence, and even multifunctional properties (Masse et al., 1993). It is therefore vital to design and synthesize novel salts with inorganic anions and organic cations so as to explore their various properties. In this context, we report the synthesis and the crystal structure of a the title compound, (I), (Fig. 1). The crystal packing can be described as a typical layered organization. A projection of such a layer shows that the Cl^- anions are linked to the water molecules by O—H···Cl hydrogen bonds to form infinite corrugated chains along the b direction (Fig. 2). These chains are themselves connected via N—H···O and N—H···Cl hydrogen bonds originating from NH₃⁺groups, so as to built inorganic layers spreading around the (a,b) plane. The 2,5-xylidinium cations are anchored onto the successive inorganic layers via hydrogen bonds and electrostatic interactions, to compensate their negative charges.

The examination of the organic cation shows that the values of the N—C, C—C distances and N—C—C, C—C—C angles range from 1.376 (3) to 1.503 (3) Å and 115.72 (19) to 122.80 (19)°, respectively. These values show no significant difference from those obtained in other organic materials associated with the same organic groups (Aloui et al., 2006).

In this structure, the water molecule play a very important role in the cohesion of the various groups. It participates with the organic cation and chloride anion in an H-bonding scheme of N—H···O and O—H···Cl interactions in the asymmetrical unit. Among these five H-bonds, only one could be considered to be strong according to the well known criterion of Blessing and Brown: N···O = 2.705 (4)Å (Blessing, 1986). The four remaining hydrogen bonds are relatively weak, and their donor···acceptor distances vary from 3.167 (2) to 3.219 (3) Å. Thus, these different interactions (hydrogen bonds, Van der Waals, and electrostatic) form a stable three-dimensional network.

Related literature top

For related literature, see: Aloui et al. (2006); Masse et al. (1993); Blessing (1986).

Experimental top

The title compound was prepared by slow addition, at room temperature, of an aqueous hydrochloric acid solution to an alcoholic solution of 2,5-xylidine in a 1:1 molar ratio. A crystalline precipitate was formed. After dissolution by adding H₂O, the solution was slowly evaporated at room temperature over several days resulting in the formation of transparent plates of (I).

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 publication routines (Farrugia, 1999).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids for non-H atoms drawn at the 30% probability level.
	Fig. 2. A view of the atomic arrangement of the title compound along the b axis with H bonds shown as dashed lines.

2,5-Dimethylanilinium chloride monohydrate top

Crystal data top

C₈H₁₂N⁺·Cl⁻·H₂O	F(000) = 188
M_r = 175.65	D_x = 1.187 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 7.515 (4) Å	θ = 9.0–10.8°
b = 7.441 (3) Å	µ = 0.34 mm⁻¹
c = 9.019 (2) Å	T = 293 K
β = 102.87 (3)°	Plate, colourless
V = 491.7 (4) Å³	0.50 × 0.30 × 0.20 mm
Z = 2

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.025
Radiation source: Enraf Nonius FR590	θ_max = 28.0°, θ_min = 2.3°
Graphite monochromator	h = −9→9
non–profiled ω scans	k = 0→9
2058 measured reflections	l = −5→11
1260 independent reflections	2 standard reflections every 120 min
1166 reflections with I > 2σ(I)	intensity decay: 5%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap and geom
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0515P)² + 0.0061P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1260 reflections	Δρ_max = 0.20 e Å⁻³
111 parameters	Δρ_min = −0.14 e Å⁻³
1 restraint	Absolute structure: Flack (1983), unique data only
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.17 (9)

Crystal data top

C₈H₁₂N⁺·Cl⁻·H₂O	V = 491.7 (4) Å³
M_r = 175.65	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.515 (4) Å	µ = 0.34 mm⁻¹
b = 7.441 (3) Å	T = 293 K
c = 9.019 (2) Å	0.50 × 0.30 × 0.20 mm
β = 102.87 (3)°

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.025
2058 measured reflections	2 standard reflections every 120 min
1260 independent reflections	intensity decay: 5%
1166 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.081	Δρ_max = 0.20 e Å⁻³
S = 1.10	Δρ_min = −0.14 e Å⁻³
1260 reflections	Absolute structure: Flack (1983), unique data only
111 parameters	Absolute structure parameter: 0.17 (9)
1 restraint

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
H30	0.343 (5)	0.410 (6)	0.541 (3)	0.068 (9)*
H31	0.467 (5)	0.287 (7)	0.548 (4)	0.101 (13)*
Cl1	0.77059 (6)	0.20498 (11)	0.51544 (5)	0.05039 (16)
C1	0.7901 (2)	0.5395 (3)	1.1684 (2)	0.0384 (4)
N1	0.8345 (2)	0.5589 (3)	1.33479 (17)	0.0417 (4)
H1A	0.7624	0.6418	1.3617	0.062*
H1B	0.9505	0.5923	1.3660	0.062*
H1C	0.8174	0.4543	1.3774	0.062*
C6	0.9259 (3)	0.5724 (3)	1.0904 (2)	0.0431 (4)
H6	1.0405	0.6101	1.1431	0.052*
C2	0.6147 (2)	0.4859 (3)	1.0962 (2)	0.0427 (4)
C5	0.8914 (3)	0.5491 (3)	0.9335 (3)	0.0487 (5)
C3	0.5844 (3)	0.4628 (4)	0.9399 (2)	0.0541 (5)
H3	0.4698	0.4248	0.8873	0.065*
C7	0.4674 (3)	0.4531 (4)	1.1817 (3)	0.0560 (6)
H7A	0.5086	0.3654	1.2599	0.084*
H7B	0.3597	0.4097	1.1128	0.084*
H7C	0.4399	0.5634	1.2271	0.084*
C4	0.7171 (3)	0.4937 (4)	0.8597 (3)	0.0551 (6)
H4	0.6902	0.4773	0.7548	0.066*
O1	0.3659 (3)	0.3043 (4)	0.5526 (3)	0.0783 (6)
C8	1.0363 (4)	0.5817 (4)	0.8458 (3)	0.0682 (7)
H8A	1.1339	0.6502	0.9071	0.102*
H8B	0.9850	0.6472	0.7546	0.102*
H8C	1.0828	0.4687	0.8197	0.102*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0441 (2)	0.0462 (2)	0.0622 (3)	0.0054 (3)	0.01468 (18)	0.0086 (3)
C1	0.0394 (9)	0.0301 (8)	0.0461 (9)	−0.0005 (7)	0.0105 (7)	−0.0040 (7)
N1	0.0388 (7)	0.0414 (8)	0.0458 (8)	−0.0036 (7)	0.0115 (6)	−0.0009 (7)
C6	0.0421 (9)	0.0341 (9)	0.0555 (11)	−0.0039 (8)	0.0157 (8)	−0.0023 (9)
C2	0.0378 (8)	0.0371 (9)	0.0541 (11)	−0.0006 (8)	0.0120 (8)	−0.0042 (9)
C5	0.0574 (11)	0.0372 (9)	0.0567 (11)	−0.0024 (9)	0.0237 (9)	−0.0033 (10)
C3	0.0486 (11)	0.0568 (14)	0.0545 (12)	−0.0063 (11)	0.0064 (9)	−0.0123 (11)
C7	0.0400 (10)	0.0655 (16)	0.0649 (14)	−0.0104 (11)	0.0169 (9)	−0.0068 (12)
C4	0.0658 (13)	0.0554 (13)	0.0450 (11)	−0.0011 (12)	0.0143 (9)	−0.0082 (10)
O1	0.0586 (11)	0.0618 (13)	0.1229 (18)	0.0097 (10)	0.0381 (11)	0.0362 (12)
C8	0.0852 (18)	0.0626 (17)	0.0694 (15)	−0.0123 (15)	0.0439 (14)	−0.0039 (14)

Geometric parameters (Å, º) top

C1—C6	1.383 (3)	C3—C4	1.376 (3)
C1—C2	1.393 (3)	C3—H3	0.9300
C1—N1	1.470 (2)	C7—H7A	0.9600
N1—H1A	0.8900	C7—H7B	0.9600
N1—H1B	0.8900	C7—H7C	0.9600
N1—H1C	0.8900	C4—H4	0.9300
C6—C5	1.391 (3)	O1—H30	0.80 (4)
C6—H6	0.9300	O1—H31	0.78 (4)
C2—C3	1.388 (3)	C8—H8A	0.9600
C2—C7	1.503 (3)	C8—H8B	0.9600
C5—C4	1.393 (3)	C8—H8C	0.9600
C5—C8	1.501 (3)

C6—C1—C2	122.80 (19)	C4—C3—H3	118.7
C6—C1—N1	118.46 (17)	C2—C3—H3	118.7
C2—C1—N1	118.73 (18)	C2—C7—H7A	109.5
C1—N1—H1A	109.5	C2—C7—H7B	109.5
C1—N1—H1B	109.5	H7A—C7—H7B	109.5
H1A—N1—H1B	109.5	C2—C7—H7C	109.5
C1—N1—H1C	109.5	H7A—C7—H7C	109.5
H1A—N1—H1C	109.5	H7B—C7—H7C	109.5
H1B—N1—H1C	109.5	C3—C4—C5	120.8 (2)
C1—C6—C5	120.3 (2)	C3—C4—H4	119.6
C1—C6—H6	119.9	C5—C4—H4	119.6
C5—C6—H6	119.9	H30—O1—H31	110 (4)
C3—C2—C1	115.72 (19)	C5—C8—H8A	109.5
C3—C2—C7	121.90 (19)	C5—C8—H8B	109.5
C1—C2—C7	122.38 (19)	H8A—C8—H8B	109.5
C6—C5—C4	117.7 (2)	C5—C8—H8C	109.5
C6—C5—C8	121.6 (2)	H8A—C8—H8C	109.5
C4—C5—C8	120.7 (2)	H8B—C8—H8C	109.5
C4—C3—C2	122.7 (2)

C2—C1—C6—C5	−1.2 (3)	C1—C6—C5—C8	−179.4 (2)
N1—C1—C6—C5	177.61 (19)	C1—C2—C3—C4	−1.2 (4)
C6—C1—C2—C3	1.5 (3)	C7—C2—C3—C4	179.4 (3)
N1—C1—C2—C3	−177.3 (2)	C2—C3—C4—C5	0.6 (4)
C6—C1—C2—C7	−179.1 (2)	C6—C5—C4—C3	−0.2 (4)
N1—C1—C2—C7	2.1 (3)	C8—C5—C4—C3	179.7 (3)
C1—C6—C5—C4	0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H30···Cl1ⁱ	0.81 (4)	2.37 (4)	3.168 (3)	171 (4)
O1—H31···Cl1	0.78 (4)	2.44 (4)	3.219 (3)	174 (5)
N1—H1A···O1ⁱⁱ	0.89	1.82	2.705 (4)	171
N1—H1B···Cl1ⁱⁱⁱ	0.89	2.29	3.167 (2)	169
N1—H1C···Cl1^iv	0.89	2.30	3.189 (3)	173

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂N⁺·Cl⁻·H₂O
M_r	175.65
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	7.515 (4), 7.441 (3), 9.019 (2)
β (°)	102.87 (3)
V (Å³)	491.7 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.50 × 0.30 × 0.20

Data collection
Diffractometer	Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2058, 1260, 1166
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.081, 1.10
No. of reflections	1260
No. of parameters	111
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.14
Absolute structure	Flack (1983), unique data only
Absolute structure parameter	0.17 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H30···Cl1ⁱ	0.81 (4)	2.37 (4)	3.168 (3)	171 (4)
O1—H31···Cl1	0.78 (4)	2.44 (4)	3.219 (3)	174 (5)
N1—H1A···O1ⁱⁱ	0.89	1.82	2.705 (4)	171
N1—H1B···Cl1ⁱⁱⁱ	0.89	2.29	3.167 (2)	169
N1—H1C···Cl1^iv	0.89	2.30	3.189 (3)	173

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

References

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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
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Masse, R., Bagieu-Beucher, M., Pecault, J., Levy, J. P. & Zyss, J. (1993). Nonlin. Opt. 5, 413–423. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o83

doi:10.1107/S1600536808041287

Open

access