A second monoclinic polymorph of 2,4-dimethyl­anilinium chloride

Hossein Zadeh, S.; Talei Bavil Olyai, M.R.; Biglari Mazlaghani, H.; Notash, B.

doi:10.1107/S160053681104551X

organic compounds

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Volume 67| Part 12| December 2011| Page o3190

https://doi.org/10.1107/S160053681104551X

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A second monoclinic polymorph of 2,4-dimethylanilinium chloride

Soudeh Hossein Zadeh,^a Mohamad Reza Talei Bavil Olyai,^b ^* Hossein Biglari Mazlaghani ^a and Behrouz Notash ^c

^aDepartment of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran, ^bDepartment of Chemistry, Islamic Azad University, South Tehran Branch, Tehran, Iran, and ^cDepartment of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
^*Correspondence e-mail: talei3@gmail.com

(Received 14 October 2011; accepted 29 October 2011; online 5 November 2011)

A second monoclinic polymorph of 2,4-dimethylanilinium chloride, C₈H₁₂N⁺·Cl⁻, (I), is reported. The unit-cell dimensions differ from those of the first reported monoclinic form, (II) [Yao (2010 ). Acta Cryst. E66, o1563]. Nevertheless, both compounds crystallize in the monoclinic space group P2₁/n. As in (II), the protonated amine group in (I) acts as a hydrogen-bond donor to the chloride ion, forming three N—H⋯Cl hydrogen bonds. The result is a two-dimensional network in the ac plane. The difference in the hydrogen-bond pattern is that in (I) only 12-membered rings are formed whereas in (II), eight-membered and 16-membered rings are formed.

Related literature

For another monoclinic polymorph of the title compound, see: Yao (2010). For properties of compounds containing inorganic anions and organic cations, see: Masse et al. (1993 ); Xiao et al. (2005 ).

Experimental

Crystal data

C₈H₁₂N⁺·Cl⁻
M_r = 157.64
Monoclinic, P 2₁ /n
a = 5.3651 (11) Å
b = 18.631 (4) Å
c = 8.5428 (17) Å
β = 94.48 (3)°
V = 851.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 298 K
0.45 × 0.4 × 0.34 mm

Data collection

Stoe IPDS 2T diffractometer
5557 measured reflections
2276 independent reflections
1838 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.104
S = 1.09
2276 reflections
105 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.91 (2)	2.28 (2)	3.1721 (17)	164.4 (17)
N1—H1B⋯Cl1ⁱⁱ	0.88 (2)	2.35 (2)	3.2228 (17)	172.1 (18)
N1—H1C⋯Cl1ⁱⁱⁱ	0.94 (2)	2.23 (2)	3.1630 (16)	172.8 (19)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{3\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x+1, y, z.

Data collection: X-AREA (Stoe & Cie, 2005 ); cell refinement: X-AREA; data reduction: X-AREA; 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: https://doi.org/10.1107/S160053681104551X/bt5679sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681104551X/bt5679Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681104551X/bt5679Isup3.cml

checkCIF report

Comment top

The combination of organic cations and inorganic anions is important in material science and chemistry because of their abilities to join the properties of organic and inorganic molecules, exhibiting some interesting crystal structures with special properties, such as luminescence, magnetism, and multifunctional properties (Masse et al., 1993). Furthermore these hybrid materials have a great interest due to their numerous varieties of intriguing structural topologies (Xiao et al., 2005).

The title compound, (I), is a second monoclinic polymorph of the structure of 2,4-dimethylanilinium chloride which crystallizes in the space group P2₁/n. A different structure, (II), in the space group P2₁/c was described earlier by (Yao, 2010).

The asymmetric unit of the title compound contains one 2,4-dimethylanilinium cation and one chloride anion (Fig. 1). The cell parameters of the current monoclinic polymorph vary significantly from the earlier polymorph [a = 9.4739 (19) Å, b = 9.894 (2) Å, c = 9.6709 (19) Å and β = 96.31 (3)°]. The C—N bond length is 1.465 (2) Å. The C—N bond length for previous crystal structure was given 1.466 (3) Å (Yao, 2010). Inside lattice, each Cl^- anion is linked to three organic species through N–H···Cl hydrogen bonds (Table 1).

The two-dimensional arrangement of the chloride anions and 2,4-dimethylanilinum cations in the unit cell is shown in Fig. 2.

Related literature top

For another monoclinic polymorph of the title compound, see: Yao (2010). For properties of compounds containing inorganic anions and organic cations, see: Masse et al. (1993); Xiao et al. (2005).

Experimental top

An ethanolic solution of 2,4-dimethylaniline (1.21 g, 10 mmol in 10 ml) was added dropwise to a magnetically stirred of aqueous hydrochloric acid solution (1.01 g, 10 mmol) a 1:1 molar ratio. The achieved solution is then filtered to eliminate the colorless crystals precipitated formed and then stirred for 2 hrs. After stirring, the obtained solution was slowly evaporated at room temperature over several days resulting in the formation of 2,4-dimethylanilinium chloride crystals.

Structure description top

The two-dimensional arrangement of the chloride anions and 2,4-dimethylanilinum cations in the unit cell is shown in Fig. 2.

For another monoclinic polymorph of the title compound, see: Yao (2010). For properties of compounds containing inorganic anions and organic cations, see: Masse et al. (1993); Xiao et al. (2005).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); 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. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram of the title compound showing intermolecular N—H···Cl hydrogen bonding.

2,4-dimethylanilinium chloride top

Crystal data top

C₈H₁₂N⁺·Cl⁻	F(000) = 336
M_r = 157.64	D_x = 1.230 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2276 reflections
a = 5.3651 (11) Å	θ = 2.2–29.1°
b = 18.631 (4) Å	µ = 0.38 mm⁻¹
c = 8.5428 (17) Å	T = 298 K
β = 94.48 (3)°	Block, colorless
V = 851.3 (3) Å³	0.45 × 0.4 × 0.34 mm
Z = 4

Data collection top

Stoe IPDS 2T diffractometer	1838 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 29.1°, θ_min = 2.2°
Detector resolution: 0.15 mm pixels mm^-1	h = −7→6
rotation method scans	k = −22→25
5557 measured reflections	l = −11→11
2276 independent 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0462P)² + 0.1562P] where P = (F_o² + 2F_c²)/3
2276 reflections	(Δ/σ)_max < 0.001
105 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₈H₁₂N⁺·Cl⁻	V = 851.3 (3) Å³
M_r = 157.64	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.3651 (11) Å	µ = 0.38 mm⁻¹
b = 18.631 (4) Å	T = 298 K
c = 8.5428 (17) Å	0.45 × 0.4 × 0.34 mm
β = 94.48 (3)°

Data collection top

Stoe IPDS 2T diffractometer	1838 reflections with I > 2σ(I)
5557 measured reflections	R_int = 0.031
2276 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.22 e Å⁻³
2276 reflections	Δρ_min = −0.17 e Å⁻³
105 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
C8	0.9245 (5)	0.39088 (11)	0.1976 (3)	0.0692 (6)
H8A	1.0616	0.3635	0.2452	0.104*
H8B	0.9148	0.3842	0.0858	0.104*
H8C	0.7715	0.3750	0.2376	0.104*
C7	0.6327 (3)	0.64679 (10)	0.1382 (2)	0.0533 (4)
H7A	0.6040	0.6834	0.2139	0.080*
H7B	0.4783	0.6227	0.1078	0.080*
H7C	0.6969	0.6683	0.0475	0.080*
Cl1	0.08615 (7)	0.78443 (2)	0.04928 (5)	0.04796 (14)
N1	1.0561 (3)	0.68899 (8)	0.35343 (16)	0.0406 (3)
C1	1.0245 (3)	0.61337 (8)	0.30934 (16)	0.0367 (3)
C2	0.8198 (3)	0.59328 (9)	0.20976 (17)	0.0407 (3)
C3	0.7952 (3)	0.52034 (10)	0.17611 (19)	0.0477 (4)
H3	0.6585	0.5053	0.1107	0.057*
C5	1.1683 (3)	0.49210 (10)	0.3321 (2)	0.0502 (4)
H5	1.2861	0.4589	0.3719	0.060*
C4	0.9645 (3)	0.46926 (9)	0.23530 (19)	0.0478 (4)
C6	1.1980 (3)	0.56416 (9)	0.37005 (19)	0.0458 (4)
H6	1.3341	0.5792	0.4360	0.055*
H1A	0.932 (4)	0.7056 (11)	0.411 (3)	0.057 (6)*
H1C	1.060 (4)	0.7208 (11)	0.268 (3)	0.062 (6)*
H1B	1.192 (5)	0.6971 (11)	0.415 (2)	0.057 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C8	0.0840 (16)	0.0542 (12)	0.0681 (12)	0.0007 (11)	−0.0025 (11)	−0.0061 (9)
C7	0.0395 (9)	0.0614 (11)	0.0569 (10)	0.0008 (8)	−0.0108 (7)	0.0054 (8)
Cl1	0.0356 (2)	0.0578 (3)	0.0501 (2)	−0.00034 (18)	0.00128 (14)	0.01375 (18)
N1	0.0323 (7)	0.0494 (8)	0.0397 (7)	−0.0023 (6)	0.0003 (5)	0.0018 (6)
C1	0.0299 (7)	0.0462 (8)	0.0342 (6)	−0.0031 (6)	0.0036 (5)	0.0034 (6)
C2	0.0325 (7)	0.0526 (9)	0.0366 (7)	−0.0016 (7)	0.0001 (5)	0.0035 (6)
C3	0.0437 (9)	0.0567 (10)	0.0415 (8)	−0.0067 (7)	−0.0051 (6)	−0.0019 (7)
C5	0.0442 (9)	0.0532 (10)	0.0525 (9)	0.0065 (8)	−0.0007 (7)	0.0080 (7)
C4	0.0530 (10)	0.0499 (9)	0.0406 (8)	−0.0012 (8)	0.0048 (7)	0.0010 (7)
C6	0.0345 (8)	0.0553 (10)	0.0462 (8)	−0.0017 (7)	−0.0056 (6)	0.0062 (7)

Geometric parameters (Å, º) top

C8—C4	1.507 (3)	N1—H1B	0.88 (2)
C8—H8A	0.9600	C1—C6	1.379 (2)
C8—H8B	0.9600	C1—C2	1.387 (2)
C8—H8C	0.9600	C2—C3	1.393 (2)
C7—C2	1.509 (2)	C3—C4	1.383 (2)
C7—H7A	0.9600	C3—H3	0.9300
C7—H7B	0.9600	C5—C4	1.385 (3)
C7—H7C	0.9600	C5—C6	1.387 (3)
N1—C1	1.465 (2)	C5—H5	0.9300
N1—H1A	0.91 (2)	C6—H6	0.9300
N1—H1C	0.94 (2)

C4—C8—H8A	109.5	C6—C1—C2	122.02 (15)
C4—C8—H8B	109.5	C6—C1—N1	118.79 (14)
H8A—C8—H8B	109.5	C2—C1—N1	119.18 (14)
C4—C8—H8C	109.5	C1—C2—C3	116.57 (15)
H8A—C8—H8C	109.5	C1—C2—C7	122.66 (15)
H8B—C8—H8C	109.5	C3—C2—C7	120.76 (15)
C2—C7—H7A	109.5	C4—C3—C2	123.15 (16)
C2—C7—H7B	109.5	C4—C3—H3	118.4
H7A—C7—H7B	109.5	C2—C3—H3	118.4
C2—C7—H7C	109.5	C4—C5—C6	120.51 (16)
H7A—C7—H7C	109.5	C4—C5—H5	119.7
H7B—C7—H7C	109.5	C6—C5—H5	119.7
C1—N1—H1A	112.9 (13)	C3—C4—C5	118.14 (16)
C1—N1—H1C	114.4 (12)	C3—C4—C8	120.66 (17)
H1A—N1—H1C	105.4 (18)	C5—C4—C8	121.19 (18)
C1—N1—H1B	113.2 (13)	C1—C6—C5	119.59 (15)
H1A—N1—H1B	103.1 (18)	C1—C6—H6	120.2
H1C—N1—H1B	106.9 (18)	C5—C6—H6	120.2

C6—C1—C2—C3	1.2 (2)	C2—C3—C4—C8	178.59 (17)
N1—C1—C2—C3	−177.97 (14)	C6—C5—C4—C3	1.1 (2)
C6—C1—C2—C7	−178.00 (15)	C6—C5—C4—C8	−177.79 (17)
N1—C1—C2—C7	2.9 (2)	C2—C1—C6—C5	−0.4 (2)
C1—C2—C3—C4	−0.8 (2)	N1—C1—C6—C5	178.72 (15)
C7—C2—C3—C4	178.37 (15)	C4—C5—C6—C1	−0.7 (3)
C2—C3—C4—C5	−0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.91 (2)	2.28 (2)	3.1721 (17)	164.4 (17)
N1—H1B···Cl1ⁱⁱ	0.88 (2)	2.35 (2)	3.2228 (17)	172.1 (18)
N1—H1C···Cl1ⁱⁱⁱ	0.94 (2)	2.23 (2)	3.1630 (16)	172.8 (19)

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂N⁺·Cl⁻
M_r	157.64
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	5.3651 (11), 18.631 (4), 8.5428 (17)
β (°)	94.48 (3)
V (Å³)	851.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.45 × 0.4 × 0.34

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5557, 2276, 1838
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.104, 1.09
No. of reflections	2276
No. of parameters	105
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.17

Computer programs: X-AREA (Stoe & Cie, 2005), 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
N1—H1A···Cl1ⁱ	0.91 (2)	2.28 (2)	3.1721 (17)	164.4 (17)
N1—H1B···Cl1ⁱⁱ	0.88 (2)	2.35 (2)	3.2228 (17)	172.1 (18)
N1—H1C···Cl1ⁱⁱⁱ	0.94 (2)	2.23 (2)	3.1630 (16)	172.8 (19)

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

Acknowledgements

The authors wish to acknowledge Islamic Azad University, Karaj Branch for financial support.

References

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