Dibenzyl­aza­nium chloride

Selvakumaran, N.; Karvembu, R.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536812003777

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o577

doi:10.1107/S1600536812003777

Open

access

Dibenzylazanium chloride

N. Selvakumaran,^a R. Karvembu,^a ‡ Seik Weng Ng ^b,^c and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, National Institute of Technology, Tiruchirappalli 620 015, India, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 28 January 2012; accepted 28 January 2012; online 4 February 2012)

In the title salt, C₁₄H₁₆N⁺·Cl⁻, the complete cation and complete anion are generated by the application of mirror symmetry. The molecule is nonplanar, as seen in the dihedral angle between the terminal phenyl rings [70.92 (5)°]. In the crystal, N—H⋯Cl hydrogen bonds involving both azanium H atoms link the ions into a zigzag supramolecular chain along [100].

Related literature

For the crystal structure of the isostructural bromide salt, see: Polamo et al. (1997 ).

Experimental

Crystal data

C₁₄H₁₆N⁺·Cl⁻
M_r = 233.73
Orthorhombic, P n m a
a = 10.1524 (9) Å
b = 23.8858 (17) Å
c = 5.0922 (4) Å
V = 1234.85 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 100 K
0.25 × 0.25 × 0.15 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.933, T_max = 0.959
3840 measured reflections
1449 independent reflections
1092 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.125
S = 1.05
1449 reflections
82 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯Cl1	1.00 (4)	2.19 (4)	3.173 (2)	167 (3)
N1—H2n⋯Cl1ⁱ	0.99 (4)	2.16 (4)	3.104 (2)	160 (3)
Symmetry code: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812003777/hg5170sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003777/hg5170Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812003777/hg5170Isup3.cml

checkCIF report

Comment top

The title compound, (I), was obtained as an unexpected product from a reaction mixture containing dibenzylamine, isophthaloyl dichloride and potassium thiocyanate in acetone under reflux conditions, a reaction designed to form a thiourea derivative. Crystals were grown from a solution of the compound in ethylacetate / petroleum ether (1:3) mixture.

The NH₂ atoms of the cation and Cl anion in (I), Fig. 1, lie on a crystallographic mirror plane. The dihedral angle between the symmetry related phenyl rings is 70.92 (5)°. Both ammonium-H atoms form hydrogen bonds to the Cl anion resulting in a supramolecular zigzag chains along [100], Fig. 2 and Table 1. Chains assemble into layers in the ac plane which stack along the b axis with no specific intermolecular interactions being present.

The structure of (I) is isostructural with the bromide salt (Polamo et al., 1997).

Related literature top

For the crystal structure of the isostructural bromide salt, see: Polamo et al. (1997).

Experimental top

A solution of isophthaloyl dichloride in acetone was added drop wise to a suspension of potassium thiocyanate in anhydrous acetone. The reaction mixture was heated under reflux for 45 minutes and then cooled to room temperature. A solution of dibenzylamine in acetone was added and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 ml) was added and the resulting white solid was filtered, washed with water and dried in vacuo. Single crystals were grown at room temperature from ethylacetate / petroleum ether (1:3) mixture.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structures of the ions comprising (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. The ions lie on a mirror plane and unlabeled atoms are related by x, 1/2 - y, z.
	Fig. 2. A supramolecular chain along [100] in (I) mediated by N—H···Cl hydrogen bonding shown as orange dashed lines.

Dibenzylazanium chloride top

Crystal data top

C₁₄H₁₆N⁺·Cl⁻	F(000) = 496
M_r = 233.73	D_x = 1.257 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 977 reflections
a = 10.1524 (9) Å	θ = 2.6–27.5°
b = 23.8858 (17) Å	µ = 0.28 mm⁻¹
c = 5.0922 (4) Å	T = 100 K
V = 1234.85 (17) Å³	Prism, colourless
Z = 4	0.25 × 0.25 × 0.15 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1449 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1092 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.046
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.6°, θ_min = 4.1°
ω scan	h = −10→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −30→27
T_min = 0.933, T_max = 0.959	l = −6→4
3840 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0542P)² + 0.3264P] where P = (F_o² + 2F_c²)/3
1449 reflections	(Δ/σ)_max < 0.001
82 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₄H₁₆N⁺·Cl⁻	V = 1234.85 (17) Å³
M_r = 233.73	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 10.1524 (9) Å	µ = 0.28 mm⁻¹
b = 23.8858 (17) Å	T = 100 K
c = 5.0922 (4) Å	0.25 × 0.25 × 0.15 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1449 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1092 reflections with I > 2σ(I)
T_min = 0.933, T_max = 0.959	R_int = 0.046
3840 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.37 e Å⁻³
1449 reflections	Δρ_min = −0.23 e Å⁻³
82 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
Cl1	0.57091 (7)	0.2500	0.22464 (13)	0.0232 (2)
N1	0.8159 (2)	0.2500	0.6115 (5)	0.0190 (5)
C1	0.8343 (2)	0.30217 (8)	0.7718 (4)	0.0209 (5)
H1A	0.9290	0.3068	0.8128	0.025*
H1B	0.7862	0.2982	0.9398	0.025*
C2	0.7854 (2)	0.35355 (8)	0.6298 (4)	0.0203 (4)
C3	0.8515 (2)	0.37583 (8)	0.4155 (4)	0.0232 (5)
H3	0.9302	0.3587	0.3547	0.028*
C4	0.8031 (2)	0.42314 (9)	0.2893 (4)	0.0267 (5)
H4	0.8485	0.4382	0.1422	0.032*
C5	0.6883 (2)	0.44844 (9)	0.3782 (4)	0.0296 (5)
H5	0.6551	0.4807	0.2916	0.035*
C6	0.6222 (2)	0.42665 (9)	0.5932 (4)	0.0297 (5)
H6	0.5438	0.4440	0.6545	0.036*
C7	0.6708 (2)	0.37950 (9)	0.7183 (4)	0.0245 (5)
H7	0.6254	0.3647	0.8660	0.029*
H1n	0.730 (4)	0.2500	0.515 (7)	0.043 (10)*
H2n	0.882 (4)	0.2500	0.468 (6)	0.039 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0175 (4)	0.0287 (4)	0.0235 (4)	0.000	−0.0025 (3)	0.000
N1	0.0158 (12)	0.0218 (12)	0.0194 (12)	0.000	−0.0001 (10)	0.000
C1	0.0218 (11)	0.0208 (10)	0.0200 (10)	−0.0022 (8)	−0.0015 (8)	−0.0033 (8)
C2	0.0185 (10)	0.0206 (9)	0.0217 (10)	−0.0014 (8)	−0.0034 (8)	−0.0040 (8)
C3	0.0217 (11)	0.0243 (10)	0.0236 (10)	−0.0008 (8)	−0.0020 (8)	−0.0032 (8)
C4	0.0290 (12)	0.0247 (11)	0.0264 (11)	−0.0024 (9)	−0.0007 (9)	0.0004 (9)
C5	0.0342 (13)	0.0228 (10)	0.0317 (12)	0.0050 (9)	−0.0082 (10)	−0.0031 (9)
C6	0.0224 (11)	0.0318 (11)	0.0349 (12)	0.0058 (10)	0.0002 (10)	−0.0081 (10)
C7	0.0218 (11)	0.0271 (11)	0.0247 (10)	−0.0041 (8)	0.0021 (9)	−0.0042 (9)

Geometric parameters (Å, º) top

N1—C1	1.501 (2)	C3—C4	1.390 (3)
N1—C1ⁱ	1.501 (2)	C3—H3	0.9500
N1—H1n	1.00 (4)	C4—C5	1.389 (3)
N1—H2n	0.99 (4)	C4—H4	0.9500
C1—C2	1.508 (3)	C5—C6	1.386 (3)
C1—H1A	0.9900	C5—H5	0.9500
C1—H1B	0.9900	C6—C7	1.385 (3)
C2—C3	1.387 (3)	C6—H6	0.9500
C2—C7	1.394 (3)	C7—H7	0.9500

C1—N1—C1ⁱ	112.2 (2)	C2—C3—C4	120.3 (2)
C1—N1—H1n	112.1 (9)	C2—C3—H3	119.8
C1ⁱ—N1—H1n	112.1 (9)	C4—C3—H3	119.8
C1—N1—H2n	108.5 (10)	C5—C4—C3	120.0 (2)
C1ⁱ—N1—H2n	108.5 (10)	C5—C4—H4	120.0
H1n—N1—H2n	103 (3)	C3—C4—H4	120.0
N1—C1—C2	111.96 (17)	C6—C5—C4	120.0 (2)
N1—C1—H1A	109.2	C6—C5—H5	120.0
C2—C1—H1A	109.2	C4—C5—H5	120.0
N1—C1—H1B	109.2	C7—C6—C5	119.8 (2)
C2—C1—H1B	109.2	C7—C6—H6	120.1
H1A—C1—H1B	107.9	C5—C6—H6	120.1
C3—C2—C7	119.18 (19)	C6—C7—C2	120.7 (2)
C3—C2—C1	122.01 (19)	C6—C7—H7	119.7
C7—C2—C1	118.81 (18)	C2—C7—H7	119.7

C1ⁱ—N1—C1—C2	−166.69 (13)	C3—C4—C5—C6	0.2 (3)
N1—C1—C2—C3	−71.7 (2)	C4—C5—C6—C7	−0.2 (3)
N1—C1—C2—C7	108.7 (2)	C5—C6—C7—C2	−0.2 (3)
C7—C2—C3—C4	−0.6 (3)	C3—C2—C7—C6	0.6 (3)
C1—C2—C3—C4	179.77 (18)	C1—C2—C7—C6	−179.77 (18)
C2—C3—C4—C5	0.2 (3)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···Cl1	1.00 (4)	2.19 (4)	3.173 (2)	167 (3)
N1—H2n···Cl1ⁱⁱ	0.99 (4)	2.16 (4)	3.104 (2)	160 (3)

Symmetry code: (ii) x+1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆N⁺·Cl⁻
M_r	233.73
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	100
a, b, c (Å)	10.1524 (9), 23.8858 (17), 5.0922 (4)
V (Å³)	1234.85 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.25 × 0.25 × 0.15

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.933, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	3840, 1449, 1092
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.125, 1.05
No. of reflections	1449
No. of parameters	82
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.23

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···Cl1	1.00 (4)	2.19 (4)	3.173 (2)	167 (3)
N1—H2n···Cl1ⁱ	0.99 (4)	2.16 (4)	3.104 (2)	160 (3)

Symmetry code: (i) x+1/2, y, −z+1/2.

Footnotes

‡Additional correspondence author, e-mail: kar@nitt.edu.

Acknowledgements

NS thanks NITT for a Fellowship. The authors thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

References

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Polamo, M., Klinga, M. & Leskela, M. (1997). Z. Kristallogr. New Cryst. Struct. 212, 200. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar