2,6-Dimethyl­anilinium chloride monohydrate

Smirani, W.; Amri, O.; Rzaigui, M.

doi:10.1107/S1600536808039159

organic compounds

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Volume 64| Part 12| December 2008| Page o2463

doi:10.1107/S1600536808039159

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2,6-Dimethylanilinium chloride monohydrate

Wajda Smirani,^a ^* Olfa Amri ^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 20 November 2008; accepted 21 November 2008; online 29 November 2008)

In the title hydrated molecular salt, C₈H₁₂N⁺·Cl⁻·H₂O, the component species interact by way of N—H⋯O, N—H⋯Cl and O—H⋯Cl hydrogen bonds, resulting in a three-dimensional network.

Related literature

For related structures, see: Abid et al. (2007 ); Mrad et al. (2006 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₁₂N⁺·Cl⁻·H₂O
M_r = 175.65
Monoclinic, P 2₁ /c
a = 8.676 (3) Å
b = 14.144 (3) Å
c = 7.913 (6) Å
β = 101.88 (5)°
V = 950.2 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 293 (2) K
0.20 × 0.13 × 0.10 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction: none
3722 measured reflections
2244 independent reflections
1827 reflections with I > 2σ(I)
R_int = 0.033
2 standard reflections frequency: 120 min intensity decay: 5%

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.080
S = 1.04
2244 reflections
156 parameters
H-atom parameters not refined
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl1	0.90 (2)	2.41 (2)	3.305 (3)	173 (2)
O1—H2⋯Cl1ⁱ	0.87 (3)	2.32 (3)	3.163 (3)	165 (2)
N1—H6⋯Cl1ⁱⁱ	0.893 (18)	2.392 (18)	3.235 (3)	157.5 (15)
N1—H7⋯O1	0.896 (16)	1.835 (16)	2.731 (3)	177.3 (17)
N1—H8⋯Cl1ⁱⁱⁱ	0.883 (16)	2.414 (16)	3.265 (3)	162.8 (15)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) 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 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808039159/hb2860sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039159/hb2860Isup2.hkl

checkCIF report

Comment top

As part of our ongoing studies of organic-inorganic hybrid networks containing the 2,6-xylidinium cation (Mrad et al., 2006; Abid et al., 2007) we now report the synthesis and structure of the title compound, (I).

As shown in Fig. 1, the asymmetric unit of (I) contains a 2,6-xylidinium cation, a chloride anion and a water molecule. A perspective view of the structure along the a axis is given in Fig. 2. It shows that two 2,6-xylidinium cations are interconnected through two chloride anions into dimers via two N—H···Cl bonds, characterized by N···Cl separations of 3.264 (3) and 3.235 (3) Å) and forming an 8-membered ring with graph-set R₂⁴(8) (Bernstein et al., 1995).

The title compound is a crystalline hydrate including one water of crystallization, which interconnect these dimers to each other to form layers parallel to the (b, c) plane, through N—H···O and O—H···Cl hydrogen bonds (Table 1).

Hydrogen bonds, electrostatic and van der Waals interactions participate to the cohesion of the three-dimensional network and add stability to this compound (Fig. 2). An examination of the organic group moiety geometrical features shows that the C—C and C—N bond lengths and the C—C—C and C—C—N angles are in the range usually found for this molecule (Abid et al., 2007).

Related literature top

For related structures, see: Abid et al. (2007); Mrad et al. (2006). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

2,6-xylidinie and HCl were mixed in water in a 1: 1 molar ratio. The obtained solution was slowly evapored at room temperature to yield colourless blocks 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 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids for non-H atoms drawn at the 30% probability level (arbitrary spheres for the H atoms).
	Fig. 2. A perspective view of the packing in (I).

2,6-Dimethylanilinium chloride monohydrate top

Crystal data top

C₈H₁₂N⁺·Cl⁻·H₂O	F(000) = 376
M_r = 175.65	D_x = 1.228 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.676 (3) Å	θ = 9.2–10.8°
b = 14.144 (3) Å	µ = 0.35 mm⁻¹
c = 7.913 (6) Å	T = 293 K
β = 101.88 (5)°	Block, colourless
V = 950.2 (8) Å³	0.20 × 0.13 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.033
Radiation source: Enraf Nonius FR590	θ_max = 28.0°, θ_min = 2.8°
Graphite monochromator	h = −5→11
Non–profiled ω scans	k = −18→0
3722 measured reflections	l = −10→10
2244 independent reflections	2 standard reflections every 120 min
1827 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters not refined
S = 1.04	w = 1/[σ²(F_o²) + (0.0408P)² + 0.1063P] where P = (F_o² + 2F_c²)/3
2244 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₈H₁₂N⁺·Cl⁻·H₂O	V = 950.2 (8) Å³
M_r = 175.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.676 (3) Å	µ = 0.35 mm⁻¹
b = 14.144 (3) Å	T = 293 K
c = 7.913 (6) Å	0.20 × 0.13 × 0.10 mm
β = 101.88 (5)°

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.033
3722 measured reflections	2 standard reflections every 120 min
2244 independent reflections	intensity decay: 5%
1827 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.080	H-atom parameters not refined
S = 1.04	Δρ_max = 0.17 e Å⁻³
2244 reflections	Δρ_min = −0.24 e Å⁻³
156 parameters

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
H8	0.3326 (19)	0.0879 (11)	0.050 (2)	0.048 (4)*
H7	0.3721 (19)	0.1013 (11)	0.233 (2)	0.045 (4)*
H5	−0.159 (2)	0.2065 (13)	0.033 (2)	0.058 (4)*
H6	0.3494 (19)	0.0085 (13)	0.161 (2)	0.053 (4)*
H3	−0.121 (2)	−0.0291 (12)	0.318 (2)	0.055 (4)*
H13	0.171 (2)	0.2037 (14)	−0.109 (2)	0.066 (5)*
H11	0.265 (2)	−0.0493 (14)	0.427 (3)	0.070 (6)*
H17	0.056 (2)	0.2698 (15)	−0.066 (2)	0.073 (5)*
H2	0.488 (3)	0.2297 (19)	0.405 (3)	0.083 (7)*
H4	−0.278 (2)	0.0943 (13)	0.191 (2)	0.067 (5)*
H1	0.472 (3)	0.1562 (17)	0.518 (3)	0.090 (7)*
H10	0.215 (2)	−0.1099 (13)	0.268 (2)	0.062 (5)*
H9	0.124 (2)	−0.1045 (14)	0.406 (3)	0.071 (6)*
H12	0.215 (3)	0.2560 (15)	0.065 (3)	0.087 (7)*
N1	0.31170 (12)	0.06739 (8)	0.14878 (14)	0.0353 (2)
C7	0.1308 (2)	0.22609 (11)	−0.0155 (2)	0.0510 (3)
C8	0.1800 (2)	−0.07172 (12)	0.3454 (2)	0.0512 (3)
C1	0.14475 (13)	0.07516 (8)	0.15925 (14)	0.0322 (2)
C6	0.05793 (14)	0.15126 (9)	0.07822 (14)	0.0359 (3)
C5	−0.09996 (16)	0.15637 (10)	0.08975 (17)	0.0435 (3)
C2	0.08245 (14)	0.00745 (9)	0.25368 (15)	0.0367 (3)
C3	−0.07586 (16)	0.01607 (10)	0.26089 (17)	0.0445 (3)
C4	−0.16594 (15)	0.08936 (11)	0.18003 (18)	0.0466 (3)
O1	0.48995 (14)	0.16863 (9)	0.41224 (15)	0.0580 (3)
Cl1	0.45854 (4)	0.11499 (2)	0.81025 (4)	0.04716 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0319 (5)	0.0398 (5)	0.0364 (5)	0.0052 (4)	0.0125 (4)	0.0025 (4)
C7	0.0553 (9)	0.0467 (7)	0.0546 (8)	0.0130 (7)	0.0200 (7)	0.0119 (6)
C8	0.0580 (9)	0.0523 (8)	0.0493 (8)	0.0100 (7)	0.0253 (7)	0.0123 (7)
C1	0.0282 (5)	0.0398 (6)	0.0296 (5)	0.0024 (4)	0.0083 (4)	−0.0058 (4)
C6	0.0370 (6)	0.0389 (6)	0.0318 (5)	0.0050 (5)	0.0074 (4)	−0.0049 (4)
C5	0.0356 (6)	0.0504 (7)	0.0428 (6)	0.0102 (6)	0.0039 (5)	−0.0091 (6)
C2	0.0378 (6)	0.0416 (6)	0.0328 (5)	0.0007 (5)	0.0121 (4)	−0.0047 (5)
C3	0.0402 (7)	0.0524 (8)	0.0452 (6)	−0.0068 (6)	0.0186 (5)	−0.0077 (6)
C4	0.0298 (6)	0.0602 (8)	0.0508 (7)	−0.0003 (5)	0.0107 (5)	−0.0145 (6)
O1	0.0654 (7)	0.0543 (7)	0.0509 (6)	0.0072 (5)	0.0039 (5)	−0.0041 (5)
Cl1	0.04621 (19)	0.04719 (19)	0.0534 (2)	0.01013 (14)	0.02267 (14)	0.00643 (13)

Geometric parameters (Å, º) top

N1—C1	1.4718 (16)	C1—C2	1.3907 (17)
N1—H8	0.883 (18)	C1—C6	1.3921 (17)
N1—H7	0.896 (17)	C6—C5	1.3934 (18)
N1—H6	0.893 (18)	C5—C4	1.380 (2)
C7—C6	1.504 (2)	C5—H5	0.935 (18)
C7—H13	0.93 (2)	C2—C3	1.3917 (18)
C7—H17	0.92 (2)	C3—C4	1.374 (2)
C7—H12	0.96 (2)	C3—H3	0.918 (18)
C8—C2	1.498 (2)	C4—H4	1.00 (2)
C8—H11	0.93 (2)	O1—H2	0.87 (3)
C8—H10	0.92 (2)	O1—H1	0.90 (3)
C8—H9	0.88 (2)

C1—N1—H8	114.1 (10)	C2—C1—N1	118.34 (11)
C1—N1—H7	110.5 (10)	C6—C1—N1	118.50 (11)
H8—N1—H7	106.5 (15)	C1—C6—C5	117.13 (12)
C1—N1—H6	114.0 (11)	C1—C6—C7	121.91 (11)
H8—N1—H6	105.3 (15)	C5—C6—C7	120.95 (12)
H7—N1—H6	105.9 (14)	C4—C5—C6	121.09 (13)
C6—C7—H13	114.5 (12)	C4—C5—H5	121.5 (11)
C6—C7—H17	110.9 (13)	C6—C5—H5	117.4 (11)
H13—C7—H17	103.3 (16)	C1—C2—C3	117.24 (12)
C6—C7—H12	108.9 (13)	C1—C2—C8	122.14 (12)
H13—C7—H12	108.2 (18)	C3—C2—C8	120.62 (12)
H17—C7—H12	111.0 (18)	C4—C3—C2	121.22 (13)
C2—C8—H11	111.7 (12)	C4—C3—H3	119.6 (11)
C2—C8—H10	110.5 (11)	C2—C3—H3	119.2 (11)
H11—C8—H10	109.9 (17)	C3—C4—C5	120.15 (12)
C2—C8—H9	109.7 (13)	C3—C4—H4	118.9 (11)
H11—C8—H9	104.3 (18)	C5—C4—H4	120.9 (11)
H10—C8—H9	110.5 (17)	H2—O1—H1	105 (2)
C2—C1—C6	123.14 (11)

C2—C1—C6—C5	−2.12 (17)	N1—C1—C2—C3	−179.68 (10)
N1—C1—C6—C5	179.69 (10)	C6—C1—C2—C8	−177.60 (12)
C2—C1—C6—C7	176.85 (12)	N1—C1—C2—C8	0.60 (18)
N1—C1—C6—C7	−1.34 (17)	C1—C2—C3—C4	−0.96 (18)
C1—C6—C5—C4	0.94 (17)	C8—C2—C3—C4	178.78 (14)
C7—C6—C5—C4	−178.04 (13)	C2—C3—C4—C5	−0.1 (2)
C6—C1—C2—C3	2.13 (17)	C6—C5—C4—C3	0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1	0.90 (2)	2.41 (2)	3.305 (3)	173 (2)
O1—H2···Cl1ⁱ	0.87 (3)	2.32 (3)	3.163 (3)	165 (2)
N1—H6···Cl1ⁱⁱ	0.893 (18)	2.392 (18)	3.235 (3)	157.5 (15)
N1—H7···O1	0.896 (16)	1.835 (16)	2.731 (3)	177.3 (17)
N1—H8···Cl1ⁱⁱⁱ	0.883 (16)	2.414 (16)	3.265 (3)	162.8 (15)

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂N⁺·Cl⁻·H₂O
M_r	175.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.676 (3), 14.144 (3), 7.913 (6)
β (°)	101.88 (5)
V (Å³)	950.2 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.20 × 0.13 × 0.10

Data collection
Diffractometer	Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3722, 2244, 1827
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.080, 1.04
No. of reflections	2244
No. of parameters	156
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.24

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1	0.90 (2)	2.41 (2)	3.305 (3)	173 (2)
O1—H2···Cl1ⁱ	0.87 (3)	2.32 (3)	3.163 (3)	165 (2)
N1—H6···Cl1ⁱⁱ	0.893 (18)	2.392 (18)	3.235 (3)	157.5 (15)
N1—H7···O1	0.896 (16)	1.835 (16)	2.731 (3)	177.3 (17)
N1—H8···Cl1ⁱⁱⁱ	0.883 (16)	2.414 (16)	3.265 (3)	162.8 (15)

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

References

Abid, S., Hemissi, H. & Rzaigui, M. (2007). Acta Cryst. E63, o3117. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., David, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science 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
Mrad, M. L., Ben Nasr, C. & Rzaigui, M. (2006). Anal. Sci. 22, x227–x228. 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 64| Part 12| December 2008| Page o2463

doi:10.1107/S1600536808039159

Open

access