organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

3-Acetyl-2,4-di­methyl­quinolin-1-ium chloride

aDepartment of Chemistry, BITS, Pilani - K. K. Birla Goa Campus, Goa 403 726, 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 17 June 2013; accepted 17 June 2013; online 22 June 2013)

In the title salt, C13H14NO+·Cl, the dihedral angle between the fused ring system (r.m.s. deviation = 0.039 Å) and the attached aldehyde group is 75.27 (16)°. In the crystal, the cation and anion are linked by an N—H⋯Cl hydrogen bond and the resulting pairs are connected into four-ion aggregates by ππ inter­actions between the C6 and pyridinium rings [3.6450 (9) Å] of inversion-related quinolinium residues.

Related literature

For background details and biological applications of quinoline and quinoline chalcones, see: Joshi et al. (2011[Joshi, R. S., Mandhane, P. G., Khan, W. & Gill, C. H. (2011). J. Heterocycl. Chem. 48, 872-876.]); Prasath et al. (2013a[Prasath, R., Bhavana, P., Ng, S. W. & Tiekink, E. R. T. (2013a). J. Organomet. Chem. 726, 62-70.]). For a related structure, see: Prasath et al. (2013b[Prasath, R., Bhavana, P., Ng, S. W. & Tiekink, E. R. T. (2013b). Acta Cryst. E69, o428-o429.]).

[Scheme 1]

Experimental

Crystal data
  • C13H14NO+·Cl

  • Mr = 235.70

  • Orthorhombic, P b c a

  • a = 12.8221 (6) Å

  • b = 10.7281 (4) Å

  • c = 16.3785 (6) Å

  • V = 2252.97 (16) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.32 mm−1

  • T = 100 K

  • 0.50 × 0.40 × 0.30 mm

Data collection
  • Agilent SuperNova Dual diffractometer with an Atlas detector

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013[Agilent (2013). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA.]) Tmin = 0.956, Tmax = 1.000

  • 8404 measured reflections

  • 2597 independent reflections

  • 2207 reflections with I > 2σ(I)

  • Rint = 0.030

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.099

  • S = 1.04

  • 2597 reflections

  • 152 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.29 e Å−3

  • Δρmin = −0.29 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯Cl1 0.91 (2) 2.13 (2) 3.0374 (13) 175.4 (17)

Data collection: CrysAlis PRO (Agilent, 2013[Agilent (2013). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA.]); 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 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) 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

Nitrogen-containing heterocyclic analogues are found to be valuable intermediates in organic synthesis and exhibit a multitude of photophysical properties. In particular, quinoline analogues have received significant attention owing to their bio-activity such as anti-bacterial, anti-fungal, anti-malarial and anti-cancer activities (Prasath et al., 2013a; Joshi et al., 2011). As a continuation of structural studies in this area (Prasath et al., 2013b), the title salt, (I), was investigated.

The fused-ring system of the cation in (I), Fig. 1, is almost planar with the r.m.s. deviation of the fitted atoms being 0.039 Å; maximum deviations are 0.051 (1) Å for the C3 atom and -0.044 (2) Å for the C5 atom. The aldehyde group is almost perpendicular to this plane, forming a C10—C9—C12—O1 torsion angle of 73.64 (18)°.

In the crystal, ions are linked by a N—H···Cl hydrogen bond, Table 1, and connected into four-ion aggregates by ππ interactions between the C6 and pyridinium rings [inter-centorid distance 3.6450 (9) Å for symmetry operation 1 - x, 1 - y, 1 - z] of centrosymmetrically related quinolinyl residues, Fig. 2. These pack with no specific interactions between them.

Related literature top

For background details and biological applications of quinoline and quinoline chalcones, see: Joshi et al. (2011); Prasath et al. (2013a). For a related structure, see: Prasath et al. (2013b).

Experimental top

A mixture of 2-aminoacetophenone (0.68 g, 0.005 M), acetylacetone (0.5 g, 0.005 M) and 1 N HCl (20 ml) was stirred at 363 K for 45 minutes. To the resulting mixture, chloroform (20 ml) was added and the organic layer was passed through anhydrous Na2SO4. Re-crystallization was by slow evaporation of chloroform solution of (I) which yielded yellow blocks. M.pt. 393–395 K. Yield: 90%.

Refinement top

The C-bound H atoms were geometrically placed (C—H = 0.95–0.98 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C). The N-bound H atom was refined freely.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); 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, 2012) 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 in (I) showing displacement ellipsoids at the 70% probability level.
[Figure 2] Fig. 2. A view in projection down the a axis of the unit-cell contents of (I). The N—H···Cl and ππ interactions are shown as blue and purple dashed lines, respectively.
3-Acetyl-2,4-dimethylquinolin-1-ium chloride top
Crystal data top
C13H14NO+·ClF(000) = 992
Mr = 235.70Dx = 1.390 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3252 reflections
a = 12.8221 (6) Åθ = 3.0–27.5°
b = 10.7281 (4) ŵ = 0.32 mm1
c = 16.3785 (6) ÅT = 100 K
V = 2252.97 (16) Å3Block, yellow
Z = 80.50 × 0.40 × 0.30 mm
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector
2597 independent reflections
Radiation source: SuperNova (Mo) X-ray Source2207 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.030
Detector resolution: 10.4041 pixels mm-1θmax = 27.6°, θmin = 3.0°
ω scanh = 1116
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)
k = 1310
Tmin = 0.956, Tmax = 1.000l = 1921
8404 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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0514P)2 + 0.7427P]
where P = (Fo2 + 2Fc2)/3
2597 reflections(Δ/σ)max < 0.001
152 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C13H14NO+·ClV = 2252.97 (16) Å3
Mr = 235.70Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 12.8221 (6) ŵ = 0.32 mm1
b = 10.7281 (4) ÅT = 100 K
c = 16.3785 (6) Å0.50 × 0.40 × 0.30 mm
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector
2597 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)
2207 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 1.000Rint = 0.030
8404 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.29 e Å3
2597 reflectionsΔρmin = 0.29 e Å3
152 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
Cl10.38171 (3)0.29410 (3)0.31279 (2)0.01712 (13)
O10.78490 (9)0.68933 (10)0.36335 (7)0.0257 (3)
N10.56888 (10)0.39336 (11)0.40603 (7)0.0127 (3)
H10.5145 (17)0.3655 (19)0.3755 (12)0.035 (5)*
C10.56522 (12)0.36700 (12)0.48826 (8)0.0130 (3)
C20.47740 (12)0.30581 (13)0.52035 (8)0.0156 (3)
H20.42160.28110.48580.019*
C30.47406 (13)0.28251 (13)0.60294 (9)0.0177 (3)
H30.41410.24410.62600.021*
C40.55806 (13)0.31479 (13)0.65333 (9)0.0185 (3)
H40.55550.29500.70980.022*
C50.64371 (13)0.37435 (14)0.62260 (8)0.0174 (3)
H50.69990.39560.65770.021*
C60.64893 (12)0.40465 (13)0.53813 (8)0.0140 (3)
C70.73191 (11)0.47481 (13)0.50274 (8)0.0139 (3)
C80.81628 (12)0.52547 (14)0.55698 (9)0.0192 (3)
H8A0.86700.57150.52390.029*
H8B0.85150.45640.58480.029*
H8C0.78550.58150.59760.029*
C90.72892 (11)0.49922 (13)0.41992 (8)0.0134 (3)
C100.64623 (11)0.45412 (12)0.37091 (8)0.0125 (3)
C110.64361 (12)0.47075 (13)0.28065 (8)0.0159 (3)
H11A0.57970.43340.25870.024*
H11B0.70450.43000.25620.024*
H11C0.64490.55990.26760.024*
C120.80915 (12)0.58304 (13)0.37971 (8)0.0155 (3)
C130.91308 (13)0.52994 (14)0.35969 (9)0.0205 (3)
H13A0.96220.59780.34850.031*
H13B0.90720.47640.31140.031*
H13C0.93840.48060.40600.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0144 (2)0.0191 (2)0.01791 (19)0.00141 (14)0.00107 (14)0.00348 (12)
O10.0198 (6)0.0158 (5)0.0415 (6)0.0027 (5)0.0034 (5)0.0074 (5)
N10.0120 (6)0.0124 (5)0.0138 (5)0.0001 (5)0.0011 (5)0.0007 (4)
C10.0140 (7)0.0103 (6)0.0148 (6)0.0020 (5)0.0018 (6)0.0002 (5)
C20.0150 (8)0.0120 (6)0.0197 (7)0.0007 (6)0.0010 (6)0.0012 (5)
C30.0186 (8)0.0133 (6)0.0211 (7)0.0005 (6)0.0071 (6)0.0020 (5)
C40.0247 (9)0.0154 (6)0.0153 (6)0.0041 (6)0.0035 (7)0.0023 (5)
C50.0206 (8)0.0171 (7)0.0146 (6)0.0029 (6)0.0016 (6)0.0003 (5)
C60.0145 (7)0.0125 (6)0.0150 (6)0.0022 (6)0.0005 (6)0.0012 (5)
C70.0129 (7)0.0127 (6)0.0162 (6)0.0030 (6)0.0006 (6)0.0019 (5)
C80.0168 (8)0.0247 (8)0.0162 (6)0.0040 (7)0.0024 (6)0.0006 (6)
C90.0124 (8)0.0121 (6)0.0157 (6)0.0014 (5)0.0001 (6)0.0006 (5)
C100.0122 (7)0.0111 (6)0.0142 (6)0.0020 (6)0.0004 (5)0.0004 (5)
C110.0168 (8)0.0177 (7)0.0132 (6)0.0016 (6)0.0005 (6)0.0008 (5)
C120.0160 (8)0.0174 (7)0.0131 (6)0.0038 (6)0.0033 (6)0.0005 (5)
C130.0173 (8)0.0192 (7)0.0249 (7)0.0023 (6)0.0036 (7)0.0023 (6)
Geometric parameters (Å, º) top
O1—C121.2119 (18)C7—C91.3821 (18)
N1—C101.3188 (19)C7—C81.502 (2)
N1—C11.3769 (17)C8—H8A0.9800
N1—H10.91 (2)C8—H8B0.9800
C1—C21.405 (2)C8—H8C0.9800
C1—C61.408 (2)C9—C101.415 (2)
C2—C31.3762 (19)C9—C121.517 (2)
C2—H20.9500C10—C111.4894 (18)
C3—C41.400 (2)C11—H11A0.9800
C3—H30.9500C11—H11B0.9800
C4—C51.367 (2)C11—H11C0.9800
C4—H40.9500C12—C131.486 (2)
C5—C61.4228 (18)C13—H13A0.9800
C5—H50.9500C13—H13B0.9800
C6—C71.426 (2)C13—H13C0.9800
C10—N1—C1123.63 (13)H8A—C8—H8B109.5
C10—N1—H1120.0 (12)C7—C8—H8C109.5
C1—N1—H1116.4 (12)H8A—C8—H8C109.5
N1—C1—C2119.28 (13)H8B—C8—H8C109.5
N1—C1—C6118.85 (13)C7—C9—C10120.84 (13)
C2—C1—C6121.86 (12)C7—C9—C12121.31 (13)
C3—C2—C1118.51 (14)C10—C9—C12117.68 (12)
C3—C2—H2120.7N1—C10—C9119.01 (12)
C1—C2—H2120.7N1—C10—C11118.37 (12)
C2—C3—C4120.69 (14)C9—C10—C11122.61 (13)
C2—C3—H3119.7C10—C11—H11A109.5
C4—C3—H3119.7C10—C11—H11B109.5
C5—C4—C3121.10 (13)H11A—C11—H11B109.5
C5—C4—H4119.4C10—C11—H11C109.5
C3—C4—H4119.4H11A—C11—H11C109.5
C4—C5—C6120.19 (14)H11B—C11—H11C109.5
C4—C5—H5119.9O1—C12—C13122.82 (14)
C6—C5—H5119.9O1—C12—C9118.68 (14)
C1—C6—C7118.97 (12)C13—C12—C9118.47 (12)
C1—C6—C5117.56 (13)C12—C13—H13A109.5
C7—C6—C5123.42 (13)C12—C13—H13B109.5
C9—C7—C6118.56 (13)H13A—C13—H13B109.5
C9—C7—C8122.14 (13)C12—C13—H13C109.5
C6—C7—C8119.21 (12)H13A—C13—H13C109.5
C7—C8—H8A109.5H13B—C13—H13C109.5
C7—C8—H8B109.5
C10—N1—C1—C2177.60 (13)C5—C6—C7—C83.1 (2)
C10—N1—C1—C61.1 (2)C6—C7—C9—C100.9 (2)
N1—C1—C2—C3178.66 (12)C8—C7—C9—C10177.57 (13)
C6—C1—C2—C30.0 (2)C6—C7—C9—C12174.34 (13)
C1—C2—C3—C42.4 (2)C8—C7—C9—C122.3 (2)
C2—C3—C4—C52.5 (2)C1—N1—C10—C92.3 (2)
C3—C4—C5—C60.1 (2)C1—N1—C10—C11176.77 (12)
N1—C1—C6—C73.45 (19)C7—C9—C10—N13.3 (2)
C2—C1—C6—C7175.19 (13)C12—C9—C10—N1172.12 (12)
N1—C1—C6—C5179.02 (12)C7—C9—C10—C11175.71 (13)
C2—C1—C6—C52.3 (2)C12—C9—C10—C118.8 (2)
C4—C5—C6—C12.3 (2)C7—C9—C12—O1101.78 (17)
C4—C5—C6—C7175.13 (13)C10—C9—C12—O173.64 (18)
C1—C6—C7—C92.4 (2)C7—C9—C12—C1380.14 (17)
C5—C6—C7—C9179.80 (13)C10—C9—C12—C13104.45 (15)
C1—C6—C7—C8174.32 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.91 (2)2.13 (2)3.0374 (13)175.4 (17)

Experimental details

Crystal data
Chemical formulaC13H14NO+·Cl
Mr235.70
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)100
a, b, c (Å)12.8221 (6), 10.7281 (4), 16.3785 (6)
V3)2252.97 (16)
Z8
Radiation typeMo Kα
µ (mm1)0.32
Crystal size (mm)0.50 × 0.40 × 0.30
Data collection
DiffractometerAgilent SuperNova Dual
diffractometer with an Atlas detector
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2013)
Tmin, Tmax0.956, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
8404, 2597, 2207
Rint0.030
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.099, 1.04
No. of reflections2597
No. of parameters152
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.29, 0.29

Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.91 (2)2.13 (2)3.0374 (13)175.4 (17)
 

Footnotes

Additional correspondence author, e-mail: juliebhavana@gmail.com.

Acknowledgements

PB and RP gratefully acknowledge the Council of Scientific and Industrial Research (CSIR), India, for research grant 02 (0076)/12/EMR-II and Senior Research Fellowship (09/919/(0014)/2012 EMR-I), respectively. We also 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 (2013). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA.
First citationBrandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals
First citationJoshi, R. S., Mandhane, P. G., Khan, W. & Gill, C. H. (2011). J. Heterocycl. Chem. 48, 872–876.  Web of Science CrossRef CAS
First citationPrasath, R., Bhavana, P., Ng, S. W. & Tiekink, E. R. T. (2013a). J. Organomet. Chem. 726, 62–70.  Web of Science CSD CrossRef CAS
First citationPrasath, R., Bhavana, P., Ng, S. W. & Tiekink, E. R. T. (2013b). Acta Cryst. E69, o428–o429.  CSD CrossRef CAS IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals

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