2,4-Dimethyl­anilinium chloride

Yao, J.-Y.

doi:10.1107/S1600536810020568

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1563

doi:10.1107/S1600536810020568

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2,4-Dimethylanilinium chloride

Ji-Yuan Yao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: yaojiyuan520@163.com

(Received 19 May 2010; accepted 31 May 2010; online 5 June 2010)

In the crystal structure of the title compound, C₈H₁₂N⁺·Cl⁻, all H atoms bonded to the ammonium N atom are hydrogen bonded to the chloride ions, with N⋯Cl distances in the range 3.080 (2)–3.136 (2) Å, resulting in 16-membered macrocyclic rings involving four formula units of the title compound.

Related literature

For background to phase transition materials see: Li et al. (2008 ); Zhang et al. (2009 ).

Experimental

Crystal data

C₈H₁₂N⁺·Cl⁻
M_r = 157.64
Monoclinic, P 2₁ /c
a = 9.4739 (19) Å
b = 9.894 (2) Å
c = 9.6709 (19) Å
β = 96.31 (3)°
V = 901.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 293 K
0.4 × 0.3 × 0.2 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.880, T_max = 0.932
9081 measured reflections
2068 independent reflections
1585 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.150
S = 1.01
2068 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.89	2.27	3.136 (2)	164
N1—H1B⋯Cl1ⁱⁱ	0.89	2.27	3.128 (2)	163
N1—H1C⋯Cl1	0.89	2.20	3.080 (2)	170
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810020568/pv2285sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810020568/pv2285Isup2.hkl

checkCIF report

Comment top

There has been interest in the study of phase transition materials, including organic ligands, metal-organic coordination compounds, organic-inorganic hybrids, etc. (Li et al., 2008; Zhang et al., 2009). Exploring the phase transition materials, the dielectric properties of the title compound, have been investigated in my laboratory. Unfortunately, there was no distinct anomaly observed from 93 K to 380 K, (m.p. 408 K-410 K). In this article, the crystal structure of the title compound has been presented.

The asymmetric unit of the title compound contains a 2,4-dimethylanilinium cation and a chloride anion (Fig. 1). The non-H atoms of the 2,4-dimethylanilinium cation are essentially coplanar. In the crystal structure, all hydrogen atoms bonded to the ammonium nitrogen (N1) are hydrogen bonded to the chloride ions with N···Cl distances in the range 3.080 (2) - 3.136 (2) Å; four formula units of the title compound are hydrogen bonded to form sixteen membered macrocyclic rings in the bc-plane (Tab. 1, Fig. 2).

Related literature top

For background to this study, see: Li et al. (2008); Zhang et al. (2009).

Experimental top

The title compound was prepared by the reaction of 2,4-dimethylbenzenamine (1.21 g, 10 mmol) and hydrochloric acid solution (1.01 g, 10 mmol) in 30 ml methanol. The reaction mixture was filtered and left at room temperature for 4 days. Colorless crystals were obtained by slow evaporation.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the packing of the title compound, showing H-bonded bands along the c-axis; dashed lines indicate hydrogen bonds.

2,4-Dimethylanilinium chloride top

Crystal data top

C₈H₁₂N⁺·Cl⁻	F(000) = 336
M_r = 157.64	D_x = 1.162 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7851 reflections
a = 9.4739 (19) Å	θ = 3.2–27.5°
b = 9.894 (2) Å	µ = 0.35 mm⁻¹
c = 9.6709 (19) Å	T = 293 K
β = 96.31 (3)°	Prism, colourless
V = 901.0 (3) Å³	0.4 × 0.3 × 0.2 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	2068 independent reflections
Radiation source: fine-focus sealed tube	1585 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.5°
CCD_Profile_fitting scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
T_min = 0.880, T_max = 0.932	l = −12→12
9081 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0863P)² + 0.190P] where P = (F_o² + 2F_c²)/3
2068 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₈H₁₂N⁺·Cl⁻	V = 901.0 (3) Å³
M_r = 157.64	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.4739 (19) Å	µ = 0.35 mm⁻¹
b = 9.894 (2) Å	T = 293 K
c = 9.6709 (19) Å	0.4 × 0.3 × 0.2 mm
β = 96.31 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2068 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1585 reflections with I > 2σ(I)
T_min = 0.880, T_max = 0.932	R_int = 0.038
9081 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.01	Δρ_max = 0.38 e Å⁻³
2068 reflections	Δρ_min = −0.28 e Å⁻³
91 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
N1	0.61300 (18)	0.39383 (17)	0.84555 (17)	0.0480 (4)
H1A	0.5798	0.4779	0.8370	0.072*
H1B	0.5968	0.3608	0.9279	0.072*
H1C	0.5694	0.3426	0.7783	0.072*
C1	0.7662 (2)	0.39422 (18)	0.8348 (2)	0.0436 (5)
C3	0.9610 (2)	0.4527 (2)	0.7141 (2)	0.0538 (5)
H3A	0.9972	0.4933	0.6388	0.065*
C2	0.8145 (2)	0.4537 (2)	0.7185 (2)	0.0473 (5)
C6	0.8563 (2)	0.3347 (2)	0.9380 (2)	0.0533 (5)
H6A	0.8205	0.2946	1.0138	0.064*
C4	1.0551 (2)	0.3944 (2)	0.8157 (2)	0.0562 (5)
C5	1.0013 (3)	0.3352 (2)	0.9280 (3)	0.0609 (6)
H5A	1.0628	0.2951	0.9977	0.073*
C8	0.7157 (3)	0.5163 (3)	0.6043 (2)	0.0658 (7)
H8A	0.6591	0.5843	0.6427	0.099*
H8B	0.6547	0.4478	0.5600	0.099*
H8C	0.7700	0.5567	0.5370	0.099*
C7	1.2133 (3)	0.3985 (3)	0.8049 (3)	0.0834 (9)
H7A	1.2629	0.3545	0.8843	0.125*
H7B	1.2440	0.4908	0.8018	0.125*
H7C	1.2332	0.3529	0.7216	0.125*
Cl1	0.49251 (6)	0.19132 (5)	0.62110 (6)	0.0603 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0525 (10)	0.0481 (9)	0.0456 (9)	−0.0007 (7)	0.0146 (7)	−0.0017 (7)
C1	0.0499 (11)	0.0389 (10)	0.0434 (10)	0.0000 (8)	0.0116 (8)	−0.0035 (7)
C3	0.0564 (12)	0.0585 (13)	0.0494 (11)	−0.0015 (10)	0.0185 (9)	−0.0012 (9)
C2	0.0545 (12)	0.0456 (10)	0.0436 (10)	0.0024 (8)	0.0126 (8)	0.0004 (8)
C6	0.0638 (14)	0.0515 (12)	0.0454 (11)	0.0031 (9)	0.0090 (10)	0.0047 (9)
C4	0.0512 (12)	0.0599 (13)	0.0583 (12)	0.0030 (10)	0.0098 (10)	−0.0126 (10)
C5	0.0619 (14)	0.0652 (14)	0.0542 (12)	0.0134 (11)	−0.0002 (10)	−0.0005 (11)
C8	0.0661 (14)	0.0782 (16)	0.0543 (13)	0.0066 (12)	0.0122 (11)	0.0231 (12)
C7	0.0516 (14)	0.111 (2)	0.0883 (19)	0.0052 (14)	0.0084 (13)	−0.0130 (17)
Cl1	0.0705 (4)	0.0570 (4)	0.0571 (4)	−0.0126 (2)	0.0235 (3)	−0.0140 (2)

Geometric parameters (Å, º) top

N1—C1	1.466 (3)	C6—H6A	0.9300
N1—H1A	0.8900	C4—C5	1.380 (3)
N1—H1B	0.8900	C4—C7	1.514 (3)
N1—H1C	0.8900	C5—H5A	0.9300
C1—C6	1.372 (3)	C8—H8A	0.9600
C1—C2	1.391 (3)	C8—H8B	0.9600
C3—C4	1.379 (3)	C8—H8C	0.9600
C3—C2	1.394 (3)	C7—H7A	0.9600
C3—H3A	0.9300	C7—H7B	0.9600
C2—C8	1.500 (3)	C7—H7C	0.9600
C6—C5	1.388 (3)

C1—N1—H1A	109.5	C3—C4—C5	118.2 (2)
C1—N1—H1B	109.5	C3—C4—C7	120.4 (2)
H1A—N1—H1B	109.5	C5—C4—C7	121.4 (2)
C1—N1—H1C	109.5	C4—C5—C6	120.7 (2)
H1A—N1—H1C	109.5	C4—C5—H5A	119.7
H1B—N1—H1C	109.5	C6—C5—H5A	119.7
C6—C1—C2	122.39 (19)	C2—C8—H8A	109.5
C6—C1—N1	119.27 (17)	C2—C8—H8B	109.5
C2—C1—N1	118.33 (18)	H8A—C8—H8B	109.5
C4—C3—C2	123.4 (2)	C2—C8—H8C	109.5
C4—C3—H3A	118.3	H8A—C8—H8C	109.5
C2—C3—H3A	118.3	H8B—C8—H8C	109.5
C1—C2—C3	116.01 (19)	C4—C7—H7A	109.5
C1—C2—C8	122.39 (19)	C4—C7—H7B	109.5
C3—C2—C8	121.60 (19)	H7A—C7—H7B	109.5
C1—C6—C5	119.3 (2)	C4—C7—H7C	109.5
C1—C6—H6A	120.3	H7A—C7—H7C	109.5
C5—C6—H6A	120.3	H7B—C7—H7C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.89	2.27	3.136 (2)	164
N1—H1B···Cl1ⁱⁱ	0.89	2.27	3.128 (2)	163
N1—H1C···Cl1	0.89	2.20	3.080 (2)	170

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₁₂N⁺·Cl⁻
M_r	157.64
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.4739 (19), 9.894 (2), 9.6709 (19)
β (°)	96.31 (3)
V (Å³)	901.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.4 × 0.3 × 0.2

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.880, 0.932
No. of measured, independent and observed [I > 2σ(I)] reflections	9081, 2068, 1585
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.150, 1.01
No. of reflections	2068
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.28

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.89	2.27	3.136 (2)	164
N1—H1B···Cl1ⁱⁱ	0.89	2.27	3.128 (2)	163
N1—H1C···Cl1	0.89	2.20	3.080 (2)	170

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+1/2, z+1/2.

Acknowledgements

The author is grateful to the starter fund of Southeast University for financial support to purchase the diffractometer.

References

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