2,4-Dimethyl­anilinium perchlorate

Liang, W.-X.

doi:10.1107/S1600536810017253

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1575

doi:10.1107/S1600536810017253

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2,4-Dimethylanilinium perchlorate

Wen-Xian Liang ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: lwx927lh@163.com

(Received 9 May 2010; accepted 11 May 2010; online 5 June 2010)

The crystal packing of the title compound, C₈H₁₂N⁺·ClO₄⁻, is stabilized by N—H⋯O hydrogen bonds, the protonated amine group acting as a hydrogen-bond donor with the perchlorate O atoms as acceptors. These connect neighbouring cations and anions, forming a two-dimensional network. Variable-temperature dielectric constant measurements on the salt indicated that no distinct phase transition occurred within the measured temperature range of 80–293 K.

Related literature

For the synthesis and characterization of 2,4-dimethylanilinium phosphate, see: Fábry et al. (2001 ). For the structure of 2,4,6-trimethylanilinium iodide, see: Lemmerer & Billing (2007 ).

Experimental

Crystal data

C₈H₁₂N⁺·ClO₄⁻
M_r = 221.64
Monoclinic, P 2₁ /c
a = 9.3299 (19) Å
b = 7.1947 (14) Å
c = 15.176 (3) Å
β = 97.43 (3)°
V = 1010.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 293 K
0.45 × 0.30 × 0.15 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.884, T_max = 0.950
9986 measured reflections
2318 independent reflections
1970 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.122
S = 1.09
2318 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1ⁱ	0.89	2.24	3.002 (3)	143
N1—H1B⋯O4ⁱ	0.89	2.53	3.236 (3)	137
N1—H1A⋯O2ⁱⁱ	0.89	2.16	2.983 (3)	153
N1—H1C⋯O3	0.89	2.15	2.994 (3)	159
Symmetry codes: (i) x, y+1, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536810017253/sj2798sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810017253/sj2798Isup2.hkl

checkCIF report

Comment top

Recently, Fábry et al. (2001) reported the synthesis and characterization of the 2,4-dimethylanilinium phosphate. Lemmerer & Billing (2007) researched the crystal structure of the 2,4,6-trimethylanilinium iodide. This paper reports the crystal structure and dielectric properties of the related salt 2,4-dimethylanilinium perchlorate. The asymmetric unit of title compound, C₈H₁₂N⁺.ClO₄^-, contains a 2,4-dimethylanilinium cation and one perchlorate anion (Fig.1). The ammonium cations stack head-to-tail with no π-π interactions. The crystal packing is stabilized by N—H···O hydrogen bonds, the protonated amine group acting as a hydrogen-bond donor with the perchlorate O atoms as acceptors. These connect neighbouring cations and anions to form a two-dimensional network (Fig.2). In addition, the dielectric constant of title compound as a function of temperature indicates that the permittivity is basically temperature-independent (dielectric constant equaling to 2.6 to 4.5) from 80k to 293k, suggesting that no distinct phase transition occurred within the measured temperature range.

Related literature top

For the synthesis and characterization of 2,4-dimethylanilinium phosphate, see: Fábry et al. (2001). For the structure of 2,4,6-trimethylanilinium iodide, see: Lemmerer & Billing (2007).

Experimental top

2,4-dimethylbenzenamine (1.21 g, 10 mmol) and perchloric acid (1 g, 10 mmol) were mixed and the 2,4-dimethylbenzenamine perchlorate was obtained, then it was dissolved in water (3 ml), ethanol (20 ml), and the solution was filtered. After slowly evaporating over a period of 3 d, colorless prism crystals of the title compound suitable for diffraction were isolated. CAUTION: Although no problems were encountered in this work, perchlorate compounds are potentially explosive. They should be prepared in small amounts and handled with care.

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 asymmetric unit of the title compound, with the displacement ellipsoids were drawn at the 30% probability level. A hydrogen bond is shown as a dashed line.
	Fig. 2. Packing diagram of the title compound, showing the structure along the a axis. Hydrogen bonds are shown as dashed lines.

2,4-Dimethylanilinium perchlorate top

Crystal data top

C₈H₁₂N⁺·ClO₄⁻	F(000) = 464
M_r = 221.64	D_x = 1.457 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1970 reflections
a = 9.3299 (19) Å	θ = 3.1–27.5°
b = 7.1947 (14) Å	µ = 0.37 mm⁻¹
c = 15.176 (3) Å	T = 293 K
β = 97.43 (3)°	Prism, colorless
V = 1010.2 (3) Å³	0.45 × 0.30 × 0.15 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2318 independent reflections
Radiation source: fine-focus sealed tube	1970 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD_Profile_fitting scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
T_min = 0.884, T_max = 0.950	l = −19→19
9986 measured reflections

Refinement top

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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.122	w = 1/[σ²(F_o²) + (0.0568P)² + 0.4369P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2318 reflections	Δρ_max = 0.22 e Å⁻³
130 parameters	Δρ_min = −0.38 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0014 (1)

Crystal data top

C₈H₁₂N⁺·ClO₄⁻	V = 1010.2 (3) Å³
M_r = 221.64	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.3299 (19) Å	µ = 0.37 mm⁻¹
b = 7.1947 (14) Å	T = 293 K
c = 15.176 (3) Å	0.45 × 0.30 × 0.15 mm
β = 97.43 (3)°

Data collection top

Rigaku SCXmini diffractometer	2318 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1970 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.950	R_int = 0.030
9986 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.09	Δρ_max = 0.22 e Å⁻³
2318 reflections	Δρ_min = −0.38 e Å⁻³
130 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cl1	0.44022 (5)	0.20914 (6)	0.11652 (3)	0.03993 (17)
N1	0.37293 (19)	0.7004 (2)	0.12219 (13)	0.0489 (5)
H1A	0.4247	0.6911	0.1755	0.073*
H1B	0.3888	0.8107	0.0986	0.073*
H1C	0.3987	0.6108	0.0870	0.073*
C5	0.1146 (2)	0.7244 (3)	0.05939 (13)	0.0400 (4)
O2	0.47637 (18)	0.3056 (2)	0.19934 (10)	0.0576 (4)
C6	−0.0291 (2)	0.7058 (3)	0.07285 (14)	0.0453 (5)
H6	−0.1004	0.7328	0.0259	0.054*
O3	0.4530 (2)	0.3369 (2)	0.04594 (11)	0.0687 (5)
C1	0.2174 (2)	0.6817 (2)	0.13112 (13)	0.0374 (4)
C3	0.0362 (2)	0.6056 (3)	0.22160 (14)	0.0508 (5)
H3	0.0108	0.5647	0.2756	0.061*
C2	0.1796 (2)	0.6221 (3)	0.21116 (14)	0.0489 (5)
H2	0.2508	0.5931	0.2579	0.059*
O1	0.5376 (2)	0.0565 (2)	0.11199 (14)	0.0717 (5)
C4	−0.0713 (2)	0.6491 (3)	0.15282 (14)	0.0447 (5)
O4	0.29667 (19)	0.1392 (3)	0.11030 (13)	0.0764 (6)
C8	0.1543 (3)	0.7883 (4)	−0.02867 (16)	0.0648 (7)
H8A	0.0687	0.7957	−0.0711	0.097*
H8B	0.2206	0.7014	−0.0493	0.097*
H8C	0.1989	0.9086	−0.0219	0.097*
C7	−0.2294 (3)	0.6367 (5)	0.1648 (2)	0.0716 (8)
H7A	−0.2563	0.7443	0.1962	0.107*
H7B	−0.2455	0.5269	0.1981	0.107*
H7C	−0.2869	0.6309	0.1076	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0472 (3)	0.0343 (3)	0.0378 (3)	−0.00671 (19)	0.00362 (19)	0.00247 (18)
N1	0.0431 (10)	0.0372 (9)	0.0668 (12)	−0.0048 (7)	0.0083 (8)	−0.0034 (8)
C5	0.0499 (11)	0.0324 (9)	0.0376 (10)	−0.0001 (8)	0.0056 (8)	−0.0034 (8)
O2	0.0645 (10)	0.0629 (11)	0.0441 (9)	−0.0085 (8)	0.0022 (7)	−0.0104 (7)
C6	0.0447 (11)	0.0460 (11)	0.0425 (11)	0.0061 (9)	−0.0051 (8)	−0.0041 (9)
O3	0.1083 (15)	0.0501 (9)	0.0500 (9)	−0.0033 (10)	0.0185 (9)	0.0161 (8)
C1	0.0360 (9)	0.0281 (9)	0.0475 (11)	−0.0009 (7)	0.0035 (8)	−0.0033 (8)
C3	0.0580 (13)	0.0563 (14)	0.0386 (10)	−0.0109 (11)	0.0086 (9)	0.0008 (10)
C2	0.0499 (12)	0.0486 (12)	0.0449 (11)	−0.0038 (10)	−0.0067 (9)	0.0094 (10)
O1	0.0846 (13)	0.0446 (9)	0.0855 (13)	0.0141 (9)	0.0097 (10)	−0.0015 (9)
C4	0.0407 (10)	0.0450 (11)	0.0490 (11)	−0.0020 (9)	0.0087 (8)	−0.0127 (10)
O4	0.0571 (11)	0.0905 (14)	0.0783 (12)	−0.0318 (10)	−0.0041 (9)	−0.0005 (11)
C8	0.0829 (18)	0.0708 (17)	0.0423 (12)	−0.0117 (14)	0.0141 (11)	0.0031 (12)
C7	0.0469 (13)	0.090 (2)	0.0805 (18)	−0.0010 (14)	0.0197 (12)	−0.0212 (16)

Geometric parameters (Å, º) top

Cl1—O4	1.4225 (17)	C1—C2	1.377 (3)
Cl1—O3	1.4281 (16)	C3—C2	1.373 (3)
Cl1—O1	1.4326 (18)	C3—C4	1.386 (3)
Cl1—O2	1.4372 (16)	C3—H3	0.9300
N1—C1	1.481 (2)	C2—H2	0.9300
N1—H1A	0.8900	C4—C7	1.512 (3)
N1—H1B	0.8900	C8—H8A	0.9600
N1—H1C	0.8900	C8—H8B	0.9600
C5—C6	1.388 (3)	C8—H8C	0.9600
C5—C1	1.389 (3)	C7—H7A	0.9600
C5—C8	1.504 (3)	C7—H7B	0.9600
C6—C4	1.385 (3)	C7—H7C	0.9600
C6—H6	0.9300

O4—Cl1—O3	110.33 (13)	C2—C3—C4	121.0 (2)
O4—Cl1—O1	108.85 (13)	C2—C3—H3	119.5
O3—Cl1—O1	110.01 (12)	C4—C3—H3	119.5
O4—Cl1—O2	109.96 (11)	C3—C2—C1	119.57 (19)
O3—Cl1—O2	108.19 (11)	C3—C2—H2	120.2
O1—Cl1—O2	109.48 (11)	C1—C2—H2	120.2
C1—N1—H1A	109.5	C6—C4—C3	117.8 (2)
C1—N1—H1B	109.5	C6—C4—C7	121.0 (2)
H1A—N1—H1B	109.5	C3—C4—C7	121.2 (2)
C1—N1—H1C	109.5	C5—C8—H8A	109.5
H1A—N1—H1C	109.5	C5—C8—H8B	109.5
H1B—N1—H1C	109.5	H8A—C8—H8B	109.5
C6—C5—C1	116.46 (18)	C5—C8—H8C	109.5
C6—C5—C8	120.9 (2)	H8A—C8—H8C	109.5
C1—C5—C8	122.6 (2)	H8B—C8—H8C	109.5
C4—C6—C5	123.14 (19)	C4—C7—H7A	109.5
C4—C6—H6	118.4	C4—C7—H7B	109.5
C5—C6—H6	118.4	H7A—C7—H7B	109.5
C2—C1—C5	122.05 (19)	C4—C7—H7C	109.5
C2—C1—N1	118.36 (18)	H7A—C7—H7C	109.5
C5—C1—N1	119.58 (18)	H7B—C7—H7C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.89	2.24	3.002 (3)	143
N1—H1B···O4ⁱ	0.89	2.53	3.236 (3)	137
N1—H1A···O2ⁱⁱ	0.89	2.16	2.983 (3)	153
N1—H1C···O3	0.89	2.15	2.994 (3)	159

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂N⁺·ClO₄⁻
M_r	221.64
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.3299 (19), 7.1947 (14), 15.176 (3)
β (°)	97.43 (3)
V (Å³)	1010.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.45 × 0.30 × 0.15

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.884, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	9986, 2318, 1970
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.122, 1.09
No. of reflections	2318
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.38

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—H1B···O1ⁱ	0.89	2.24	3.002 (3)	143.1
N1—H1B···O4ⁱ	0.89	2.53	3.236 (3)	136.8
N1—H1A···O2ⁱⁱ	0.89	2.16	2.983 (3)	152.8
N1—H1C···O3	0.89	2.15	2.994 (3)	158.7

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

Acknowledgements

This work was supported by Southeast University.

References

Fábry, J., Krupková, R. & Vaněk, P. (2001). Acta Cryst. E57, o1058–o1060. CSD CrossRef IUCr Journals Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Lemmerer, A. & Billing, D. G. (2007). Acta Cryst. E63, o929–o931. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar