2,4-Dimethyl­anilinium perchlorate

Abstract

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,

• a = 9.3299 (19) Å

• b = 7.1947 (14) Å

• c = 15.176 (3) Å

• β = 97.43 (3)°

• V = 1010.2 (3) ų

• 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[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 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

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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C, N atoms to which they are bonded, with C—H = 0.93 to 0.97 Å, U_iso(H) = 1.2 Ueq(C), N—H = 0.89 Å, U_iso(H)= 1.5 U_eq(N).

Figures

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.

Crystal data

C8H12N+·ClO4−	F(000) = 464
Mr = 221.64	Dx = 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

Rigaku SCXmini diffractometer	2318 independent reflections
Radiation source: fine-focus sealed tube	1970 reflections with I > 2σ(I)
graphite	Rint = 0.030
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.1°
CCD_Profile_fitting scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.884, Tmax = 0.950	l = −19→19
9986 measured reflections

Refinement

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(Fo2) + (0.0568P)2 + 0.4369P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
2318 reflections	Δρmax = 0.22 e Å−3
130 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.