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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1563.
Published online 2010 June 5. doi:  10.1107/S1600536810020568
PMCID: PMC3006738

2,4-Dimethyl­anilinium chloride

Abstract

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 [triangle]); Zhang et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1563-scheme1.jpg

Experimental

Crystal data

  • C8H12N+·Cl
  • M r = 157.64
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1563-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.150
  • S = 1.01
  • 2068 reflections
  • 91 parameters
  • H-atom parameters constrained
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.28 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Positional parameters of all H atoms were calculated geometrically and were allowed to ride on the atoms to which they are bonded, with N—H = 0.89 Å and C—H = 0.93 and 0.96 Å, for aryl and methyl type H-atoms, respectively, Uiso(H) = 1.2 to 1.5Ueq(C/N).

Figures

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.

Crystal data

C8H12N+·ClF(000) = 336
Mr = 157.64Dx = 1.162 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7851 reflections
a = 9.4739 (19) Åθ = 3.2–27.5°
b = 9.894 (2) ŵ = 0.35 mm1
c = 9.6709 (19) ÅT = 293 K
β = 96.31 (3)°Prism, colourless
V = 901.0 (3) Å30.4 × 0.3 × 0.2 mm
Z = 4

Data collection

Rigaku Mercury2 diffractometer2068 independent reflections
Radiation source: fine-focus sealed tube1585 reflections with I > 2σ(I)
graphiteRint = 0.038
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.5°
CCD_Profile_fitting scansh = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −12→12
Tmin = 0.880, Tmax = 0.932l = −12→12
9081 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0863P)2 + 0.190P] where P = (Fo2 + 2Fc2)/3
2068 reflections(Δ/σ)max < 0.001
91 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = −0.28 e Å3

Special details

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)

xyzUiso*/Ueq
N10.61300 (18)0.39383 (17)0.84555 (17)0.0480 (4)
H1A0.57980.47790.83700.072*
H1B0.59680.36080.92790.072*
H1C0.56940.34260.77830.072*
C10.7662 (2)0.39422 (18)0.8348 (2)0.0436 (5)
C30.9610 (2)0.4527 (2)0.7141 (2)0.0538 (5)
H3A0.99720.49330.63880.065*
C20.8145 (2)0.4537 (2)0.7185 (2)0.0473 (5)
C60.8563 (2)0.3347 (2)0.9380 (2)0.0533 (5)
H6A0.82050.29461.01380.064*
C41.0551 (2)0.3944 (2)0.8157 (2)0.0562 (5)
C51.0013 (3)0.3352 (2)0.9280 (3)0.0609 (6)
H5A1.06280.29510.99770.073*
C80.7157 (3)0.5163 (3)0.6043 (2)0.0658 (7)
H8A0.65910.58430.64270.099*
H8B0.65470.44780.56000.099*
H8C0.77000.55670.53700.099*
C71.2133 (3)0.3985 (3)0.8049 (3)0.0834 (9)
H7A1.26290.35450.88430.125*
H7B1.24400.49080.80180.125*
H7C1.23320.35290.72160.125*
Cl10.49251 (6)0.19132 (5)0.62110 (6)0.0603 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0525 (10)0.0481 (9)0.0456 (9)−0.0007 (7)0.0146 (7)−0.0017 (7)
C10.0499 (11)0.0389 (10)0.0434 (10)0.0000 (8)0.0116 (8)−0.0035 (7)
C30.0564 (12)0.0585 (13)0.0494 (11)−0.0015 (10)0.0185 (9)−0.0012 (9)
C20.0545 (12)0.0456 (10)0.0436 (10)0.0024 (8)0.0126 (8)0.0004 (8)
C60.0638 (14)0.0515 (12)0.0454 (11)0.0031 (9)0.0090 (10)0.0047 (9)
C40.0512 (12)0.0599 (13)0.0583 (12)0.0030 (10)0.0098 (10)−0.0126 (10)
C50.0619 (14)0.0652 (14)0.0542 (12)0.0134 (11)−0.0002 (10)−0.0005 (11)
C80.0661 (14)0.0782 (16)0.0543 (13)0.0066 (12)0.0122 (11)0.0231 (12)
C70.0516 (14)0.111 (2)0.0883 (19)0.0052 (14)0.0084 (13)−0.0130 (17)
Cl10.0705 (4)0.0570 (4)0.0571 (4)−0.0126 (2)0.0235 (3)−0.0140 (2)

Geometric parameters (Å, °)

N1—C11.466 (3)C6—H6A0.9300
N1—H1A0.8900C4—C51.380 (3)
N1—H1B0.8900C4—C71.514 (3)
N1—H1C0.8900C5—H5A0.9300
C1—C61.372 (3)C8—H8A0.9600
C1—C21.391 (3)C8—H8B0.9600
C3—C41.379 (3)C8—H8C0.9600
C3—C21.394 (3)C7—H7A0.9600
C3—H3A0.9300C7—H7B0.9600
C2—C81.500 (3)C7—H7C0.9600
C6—C51.388 (3)
C1—N1—H1A109.5C3—C4—C5118.2 (2)
C1—N1—H1B109.5C3—C4—C7120.4 (2)
H1A—N1—H1B109.5C5—C4—C7121.4 (2)
C1—N1—H1C109.5C4—C5—C6120.7 (2)
H1A—N1—H1C109.5C4—C5—H5A119.7
H1B—N1—H1C109.5C6—C5—H5A119.7
C6—C1—C2122.39 (19)C2—C8—H8A109.5
C6—C1—N1119.27 (17)C2—C8—H8B109.5
C2—C1—N1118.33 (18)H8A—C8—H8B109.5
C4—C3—C2123.4 (2)C2—C8—H8C109.5
C4—C3—H3A118.3H8A—C8—H8C109.5
C2—C3—H3A118.3H8B—C8—H8C109.5
C1—C2—C3116.01 (19)C4—C7—H7A109.5
C1—C2—C8122.39 (19)C4—C7—H7B109.5
C3—C2—C8121.60 (19)H7A—C7—H7B109.5
C1—C6—C5119.3 (2)C4—C7—H7C109.5
C1—C6—H6A120.3H7A—C7—H7C109.5
C5—C6—H6A120.3H7B—C7—H7C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.892.273.136 (2)164
N1—H1B···Cl1ii0.892.273.128 (2)163
N1—H1C···Cl10.892.203.080 (2)170

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2285).

References

  • Ferguson, G. (1999). PRPKAPPA University of Guelph, Canada.
  • Li, X. Z., Qu, Z. R. & Xiong, R. G. (2008). Chin. J. Chem.11, 1959–1962.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhang, W., Chen, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. D. (2009). J. Am. Chem. Soc.131, 12544–12545. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography