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ISSN: 2056-9890

Di­benzyl­aza­nium chloride

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[Polamo, M., Klinga, M. & Leskela, M. (1997). Z. Kristallogr. New Cryst. Struct. 212, 200.]).

[Scheme 1]

Experimental

Crystal data
  • C14H16N+·Cl

  • Mr = 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[Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.]) Tmin = 0.933, Tmax = 0.959

  • 3840 measured reflections

  • 1449 independent reflections

  • 1092 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.37 e Å−3

  • Δρmin = −0.23 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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.

Refinement top

The H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Uequiv(C). The ammonium-H atoms were refined without restraint.

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
[Figure 1] 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.
[Figure 2] 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+·ClF(000) = 496
Mr = 233.73Dx = 1.257 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 977 reflections
a = 10.1524 (9) Åθ = 2.6–27.5°
b = 23.8858 (17) ŵ = 0.28 mm1
c = 5.0922 (4) ÅT = 100 K
V = 1234.85 (17) Å3Prism, colourless
Z = 40.25 × 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 Source1092 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.046
Detector resolution: 10.4041 pixels mm-1θmax = 27.6°, θmin = 4.1°
ω scanh = 1013
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2010)
k = 3027
Tmin = 0.933, Tmax = 0.959l = 64
3840 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0542P)2 + 0.3264P]
where P = (Fo2 + 2Fc2)/3
1449 reflections(Δ/σ)max < 0.001
82 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C14H16N+·ClV = 1234.85 (17) Å3
Mr = 233.73Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 10.1524 (9) ŵ = 0.28 mm1
b = 23.8858 (17) ÅT = 100 K
c = 5.0922 (4) Å0.25 × 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)
Tmin = 0.933, Tmax = 0.959Rint = 0.046
3840 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.125H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.37 e Å3
1449 reflectionsΔρmin = 0.23 e Å3
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
xyzUiso*/Ueq
Cl10.57091 (7)0.25000.22464 (13)0.0232 (2)
N10.8159 (2)0.25000.6115 (5)0.0190 (5)
C10.8343 (2)0.30217 (8)0.7718 (4)0.0209 (5)
H1A0.92900.30680.81280.025*
H1B0.78620.29820.93980.025*
C20.7854 (2)0.35355 (8)0.6298 (4)0.0203 (4)
C30.8515 (2)0.37583 (8)0.4155 (4)0.0232 (5)
H30.93020.35870.35470.028*
C40.8031 (2)0.42314 (9)0.2893 (4)0.0267 (5)
H40.84850.43820.14220.032*
C50.6883 (2)0.44844 (9)0.3782 (4)0.0296 (5)
H50.65510.48070.29160.035*
C60.6222 (2)0.42665 (9)0.5932 (4)0.0297 (5)
H60.54380.44400.65450.036*
C70.6708 (2)0.37950 (9)0.7183 (4)0.0245 (5)
H70.62540.36470.86600.029*
H1n0.730 (4)0.25000.515 (7)0.043 (10)*
H2n0.882 (4)0.25000.468 (6)0.039 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0175 (4)0.0287 (4)0.0235 (4)0.0000.0025 (3)0.000
N10.0158 (12)0.0218 (12)0.0194 (12)0.0000.0001 (10)0.000
C10.0218 (11)0.0208 (10)0.0200 (10)0.0022 (8)0.0015 (8)0.0033 (8)
C20.0185 (10)0.0206 (9)0.0217 (10)0.0014 (8)0.0034 (8)0.0040 (8)
C30.0217 (11)0.0243 (10)0.0236 (10)0.0008 (8)0.0020 (8)0.0032 (8)
C40.0290 (12)0.0247 (11)0.0264 (11)0.0024 (9)0.0007 (9)0.0004 (9)
C50.0342 (13)0.0228 (10)0.0317 (12)0.0050 (9)0.0082 (10)0.0031 (9)
C60.0224 (11)0.0318 (11)0.0349 (12)0.0058 (10)0.0002 (10)0.0081 (10)
C70.0218 (11)0.0271 (11)0.0247 (10)0.0041 (8)0.0021 (9)0.0042 (9)
Geometric parameters (Å, º) top
N1—C11.501 (2)C3—C41.390 (3)
N1—C1i1.501 (2)C3—H30.9500
N1—H1n1.00 (4)C4—C51.389 (3)
N1—H2n0.99 (4)C4—H40.9500
C1—C21.508 (3)C5—C61.386 (3)
C1—H1A0.9900C5—H50.9500
C1—H1B0.9900C6—C71.385 (3)
C2—C31.387 (3)C6—H60.9500
C2—C71.394 (3)C7—H70.9500
C1—N1—C1i112.2 (2)C2—C3—C4120.3 (2)
C1—N1—H1n112.1 (9)C2—C3—H3119.8
C1i—N1—H1n112.1 (9)C4—C3—H3119.8
C1—N1—H2n108.5 (10)C5—C4—C3120.0 (2)
C1i—N1—H2n108.5 (10)C5—C4—H4120.0
H1n—N1—H2n103 (3)C3—C4—H4120.0
N1—C1—C2111.96 (17)C6—C5—C4120.0 (2)
N1—C1—H1A109.2C6—C5—H5120.0
C2—C1—H1A109.2C4—C5—H5120.0
N1—C1—H1B109.2C7—C6—C5119.8 (2)
C2—C1—H1B109.2C7—C6—H6120.1
H1A—C1—H1B107.9C5—C6—H6120.1
C3—C2—C7119.18 (19)C6—C7—C2120.7 (2)
C3—C2—C1122.01 (19)C6—C7—H7119.7
C7—C2—C1118.81 (18)C2—C7—H7119.7
C1i—N1—C1—C2166.69 (13)C3—C4—C5—C60.2 (3)
N1—C1—C2—C371.7 (2)C4—C5—C6—C70.2 (3)
N1—C1—C2—C7108.7 (2)C5—C6—C7—C20.2 (3)
C7—C2—C3—C40.6 (3)C3—C2—C7—C60.6 (3)
C1—C2—C3—C4179.77 (18)C1—C2—C7—C6179.77 (18)
C2—C3—C4—C50.2 (3)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1n···Cl11.00 (4)2.19 (4)3.173 (2)167 (3)
N1—H2n···Cl1ii0.99 (4)2.16 (4)3.104 (2)160 (3)
Symmetry code: (ii) x+1/2, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC14H16N+·Cl
Mr233.73
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)100
a, b, c (Å)10.1524 (9), 23.8858 (17), 5.0922 (4)
V3)1234.85 (17)
Z4
Radiation typeMo Kα
µ (mm1)0.28
Crystal size (mm)0.25 × 0.25 × 0.15
Data collection
DiffractometerAgilent SuperNova Dual
diffractometer with an Atlas detector
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2010)
Tmin, Tmax0.933, 0.959
No. of measured, independent and
observed [I > 2σ(I)] reflections
3840, 1449, 1092
Rint0.046
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.125, 1.05
No. of reflections1449
No. of parameters82
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1n···Cl11.00 (4)2.19 (4)3.173 (2)167 (3)
N1—H2n···Cl1i0.99 (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

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

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ISSN: 2056-9890
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