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Acta Cryst. (2012). E68, o2706-o2707    [ doi:10.1107/S1600536812035271 ]

N-[2-(4-Methylbenzoyl)ethyl]propan-2-aminium chloride

A. Aydin, M. Akkurt, H. I. Gul, E. Mete and E. Sahin

Abstract top

In the title compound, C13H20NO+·Cl-, the protonated amino N atom is hydrogen bonded to the chloride anion. N-H...Cl hydrogen bonds link the anions and cations into dimers, which are connected by C-H...O hydrogen bonds, forming supramolecular chains extending along [100].

Comment top

Mannich bases are generally formed by the reaction between formaldehyde, a secondary amine and a compound containing reactive hydrogen atoms. On occasion, aldehydes other than formaldehyde may be employed and the secondary amine may be replaced by ammonia and primary amines. This process is known as the Mannich reaction (Dimmock & Kumar, 1997).

Mannich bases display varied biological activities such as antimicrobial (Gul et al., 2005; Mete et al., 2011a), cytotoxic (Gul et al., 2005; Mete et al., 2011b; Kucukoglu et al., 2011; Canturk et al., 2008), anticancer (Dimmock & Kumar, 1997; Chen et al., 1991; Gul, 2005), antiinflammatory (Suleyman et al., 2007; Gul et al., 2009), anticonvulsant (Gul et al., 2004) and DNA topoisomerase I inhibiting properties (Canturk et al., 2008).

In the title compound (I), (Fig. 1), bond lengths and bond angles are within the range of expected values for this type of compound (Allen et al., 1987; Abonia et al., 2011; Tuzina et al., 2006). The protonated N1 atom forms a hydrogen bond to Cl1 (Table 1).

Intra- and intermolecular N—H···Cl hydrogen-bonding interactions between the free chloride anion and the organic cation link the molecules into hydrogen-bond dimers, forming a R22(6) motif (Bernstein et al., 1995; Etter, 1990). The dimers are connected by C—H···O hydrogen bonds into chains extended along the a axis (Table 1, Fig. 2).

Related literature top

For the details of the pharmacological effects of Mannich bases and for their synthesis, see: Dimmock & Kumar (1997); Gul et al. (2004; 2005a,b; 2009); Gul (2005); Mete et al. (2011a,b); Kucukoglu et al. (2011); Canturk et al. (2008); Chen et al. (1991); Suleyman et al. (2007); Plastino et al. (1962, 1964). For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995); Etter (1990). For some related structures, see: Abonia et al. (2011); Tuzina et al. (2006).

Experimental top

A mixture of the appropriate ketone (50 mmol), paraformaldehyde (50 mmol), and isopropylamine hydrochloride (27 mmol) was heated in an oil bath at 403 K. The reaction vessel was then removed from the oil bath and when the temperature of the mixture dropped to 338 K, ethyl acetate (40–80 ml) was added. The mixture was stirred at room temperature for 24 h and the resultant precipitate was then collected and were recrystallized from ether/methanol. The melting point and yield of this compound was: 443–444 K (lit. Plastino et al., 1962, 1964; m.p. 444–445 K), 58% (Mete et al., 2011b).

1H-NMR δ 1.50 (d, J = 6.6 Hz, 6H, CH(CH3)2), 2.34 (s, 3H, ArCH3), 3.36–3.46 (m, 3H, CH(CH3)2 and 2 x H-2), 3.74 (t, J = 7.3 Hz, 2H, 2 x H-3), 7.14 (d, J = 8.1 Hz, 2H, H-3'/5'), 7.79 (d, J = 8.1 Hz, 2H, H-2'/6'), 9.54 (brs, 2H, NH2+); 13C-NMR δ 19.4 (CH(CH3)2), 21.9, 35.1, 40.5, 51.2, 128.5, 129.6, 133.6, 144.9, 196.6; MS (EI) m/z (%): 190.1 (M–CH3)+, 205.3 (M+). IR (KBr, cm-1): 2461 (NH2+), 1679 (CO). Calcd. for C13H20ClNO (241.76): C, 64.59: H, 8.34; N, 5.79. Found: C, 64.39; H, 8.45; N, 5.53.

Refinement top

H atoms were positioned geometrically, with N—H = 0.90 Å, C—H = 0.93(aromatic), 0.97(methylene) and 0.98 Å (methine), and refined as riding with Uiso(H) = 1.5Ueq(O) for methyl H and 1.2Ueq(C) for the others.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 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) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The title molecule with the atom numbering scheme. Displacement ellipsoids fornon-H atoms are drawn at the 30% probability level.
[Figure 2] Fig. 2. The packing and hydrogen bonding of the title compound viewed down the baxis. H atoms not involved in hydrogen bondings are omitted for clarity.
N-[2-(4-Methylbenzoyl)ethyl]propan-2-aminium chloride top
Crystal data top
C13H20NO+·Cl−F(000) = 520
Mr = 241.75Dx = 1.180 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4594 reflections
a = 7.786 (5) Åθ = 2.6–26.5°
b = 7.511 (5) ŵ = 0.26 mm−1
c = 23.365 (5) ÅT = 294 K
β = 95.362 (5)°Block, white
V = 1360.4 (13) Å30.17 × 0.11 × 0.10 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID-S
diffractometer		2800 independent reflections
Radiation source: Sealed Tube2007 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.066
Detector resolution: 10.0000 pixels mm-1θmax = 26.4°, θmin = 2.6°
dtprofit.ref scansh = −9→9
Absorption correction: multi-scan
(Blessing, 1995)		k = −8→9
Tmin = 0.966, Tmax = 0.974l = −29→29
26900 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.151 w = 1/[σ2(Fo2) + (0.0681P)2 + 0.2172P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2800 reflectionsΔρmax = 0.21 e Å−3
149 parametersΔρmin = −0.18 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.010 (3)
Crystal data top
C13H20NO+·Cl−V = 1360.4 (13) Å3
Mr = 241.75Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.786 (5) ŵ = 0.26 mm−1
b = 7.511 (5) ÅT = 294 K
c = 23.365 (5) Å0.17 × 0.11 × 0.10 mm
β = 95.362 (5)°
Data collection top
Rigaku R-AXIS RAPID-S
diffractometer		2800 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)		2007 reflections with I > 2σ(I)
Tmin = 0.966, Tmax = 0.974Rint = 0.066
26900 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.151Δρmax = 0.21 e Å−3
S = 1.06Δρmin = −0.18 e Å−3
2800 reflectionsAbsolute structure: ?
149 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
O10.7123 (2)0.2422 (3)0.57107 (8)0.0903 (8)
N10.7916 (2)0.0622 (2)0.74056 (7)0.0555 (6)
C11.2949 (3)0.1740 (3)0.53020 (10)0.0722 (9)
C21.2627 (3)0.2488 (3)0.47633 (10)0.0653 (8)
C31.0947 (3)0.2961 (3)0.45820 (9)0.0680 (9)
C40.9644 (3)0.2737 (3)0.49337 (9)0.0659 (8)
C50.9974 (3)0.2024 (3)0.54815 (9)0.0563 (7)
C61.1652 (3)0.1501 (3)0.56544 (10)0.0658 (8)
C70.8564 (3)0.1895 (3)0.58624 (9)0.0616 (8)
C80.8956 (3)0.1133 (3)0.64590 (9)0.0623 (8)
C90.7524 (3)0.1489 (3)0.68361 (9)0.0606 (8)
C100.6625 (3)0.0981 (3)0.78362 (9)0.0611 (8)
C110.6888 (4)0.2830 (4)0.80850 (12)0.0807 (10)
C120.6811 (4)−0.0436 (4)0.82927 (12)0.0864 (10)
C131.4074 (4)0.2830 (5)0.43891 (12)0.0913 (11)
Cl11.17234 (7)0.15576 (7)0.78840 (2)0.0665 (2)
H11.406600.139100.542900.0870*
H31.069500.343700.421600.0820*
H40.852500.306900.480300.0790*
H61.190100.098100.601400.0790*
H8A0.91290−0.014200.643100.0750*
H8B1.001800.165200.663500.0750*
H9A0.739800.276200.688700.0730*
H9B0.644500.102900.665300.0730*
H100.546100.090700.763800.0730*
H11A0.596500.310800.831500.1210*
H11B0.689800.367900.777800.1210*
H11C0.796700.287800.831900.1210*
H12A0.66880−0.158800.811600.1290*
H12B0.59360−0.027900.855200.1290*
H12C0.79290−0.034400.850200.1290*
H13A1.438200.406700.440900.1370*
H13B1.370100.251800.399900.1370*
H13C1.505700.212100.452200.1370*
H14A0.896100.099200.755600.0670*
H14B0.79790−0.056200.735200.0670*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0562 (10)0.1386 (17)0.0763 (11)0.0110 (11)0.0077 (8)0.0214 (11)
N10.0530 (10)0.0541 (10)0.0609 (10)−0.0019 (8)0.0135 (8)0.0028 (8)
C10.0545 (13)0.0940 (19)0.0683 (15)0.0016 (12)0.0076 (11)0.0037 (13)
C20.0651 (14)0.0730 (15)0.0596 (13)−0.0076 (12)0.0152 (10)−0.0054 (11)
C30.0723 (16)0.0783 (16)0.0541 (13)−0.0016 (12)0.0094 (10)0.0048 (11)
C40.0618 (14)0.0764 (15)0.0596 (13)−0.0001 (12)0.0057 (10)0.0003 (11)
C50.0553 (12)0.0579 (12)0.0555 (12)−0.0054 (10)0.0048 (9)−0.0023 (9)
C60.0625 (14)0.0774 (16)0.0577 (12)0.0004 (11)0.0066 (10)0.0071 (11)
C70.0557 (13)0.0684 (14)0.0609 (13)−0.0038 (11)0.0059 (10)−0.0008 (10)
C80.0574 (13)0.0718 (14)0.0588 (13)−0.0014 (11)0.0111 (10)0.0039 (11)
C90.0584 (13)0.0630 (14)0.0614 (13)0.0002 (10)0.0103 (10)0.0041 (10)
C100.0535 (12)0.0672 (14)0.0653 (13)0.0004 (10)0.0195 (10)0.0012 (10)
C110.0901 (19)0.0698 (16)0.0871 (18)0.0072 (13)0.0350 (14)−0.0041 (13)
C120.108 (2)0.0767 (17)0.0808 (17)0.0039 (15)0.0418 (15)0.0138 (13)
C130.0797 (18)0.120 (2)0.0775 (18)−0.0034 (17)0.0253 (14)0.0074 (16)
Cl10.0631 (4)0.0604 (4)0.0756 (4)0.0010 (3)0.0046 (3)−0.0014 (3)
Geometric parameters (Å, º) top
O1—C71.211 (3)C3—H30.9300
N1—C91.487 (3)C4—H40.9300
N1—C101.511 (3)C6—H60.9300
N1—H14B0.9000C8—H8A0.9700
N1—H14A0.9000C8—H8B0.9700
C1—C61.373 (3)C9—H9A0.9700
C1—C21.380 (3)C9—H9B0.9700
C2—C31.383 (3)C10—H100.9800
C2—C131.511 (4)C11—H11A0.9600
C3—C41.374 (3)C11—H11B0.9600
C4—C51.389 (3)C11—H11C0.9600
C5—C71.480 (3)C12—H12A0.9600
C5—C61.388 (3)C12—H12B0.9600
C7—C81.511 (3)C12—H12C0.9600
C8—C91.508 (3)C13—H13A0.9600
C10—C121.504 (4)C13—H13B0.9600
C10—C111.512 (4)C13—H13C0.9600
C1—H10.9300
C9—N1—C10115.08 (16)C7—C8—H8A109.00
H14A—N1—H14B107.00C7—C8—H8B109.00
C9—N1—H14B109.00C9—C8—H8A109.00
C10—N1—H14A109.00C9—C8—H8B109.00
C9—N1—H14A108.00H8A—C8—H8B108.00
C10—N1—H14B108.00N1—C9—H9A110.00
C2—C1—C6121.3 (2)N1—C9—H9B110.00
C1—C2—C13121.0 (2)C8—C9—H9A110.00
C1—C2—C3118.0 (2)C8—C9—H9B110.00
C3—C2—C13120.9 (2)H9A—C9—H9B108.00
C2—C3—C4121.0 (2)N1—C10—H10109.00
C3—C4—C5121.0 (2)C11—C10—H10109.00
C6—C5—C7122.5 (2)C12—C10—H10109.00
C4—C5—C7119.7 (2)C10—C11—H11A109.00
C4—C5—C6117.7 (2)C10—C11—H11B109.00
C1—C6—C5120.9 (2)C10—C11—H11C109.00
O1—C7—C5121.5 (2)H11A—C11—H11B109.00
C5—C7—C8118.8 (2)H11A—C11—H11C110.00
O1—C7—C8119.7 (2)H11B—C11—H11C109.00
C7—C8—C9112.03 (19)C10—C12—H12A109.00
N1—C9—C8110.12 (18)C10—C12—H12B109.00
N1—C10—C12108.65 (19)C10—C12—H12C109.00
C11—C10—C12112.1 (2)H12A—C12—H12B110.00
N1—C10—C11110.19 (19)H12A—C12—H12C109.00
C2—C1—H1119.00H12B—C12—H12C109.00
C6—C1—H1119.00C2—C13—H13A109.00
C2—C3—H3119.00C2—C13—H13B109.00
C4—C3—H3119.00C2—C13—H13C109.00
C3—C4—H4119.00H13A—C13—H13B110.00
C5—C4—H4120.00H13A—C13—H13C109.00
C1—C6—H6120.00H13B—C13—H13C109.00
C5—C6—H6120.00
C9—N1—C10—C11−76.7 (2)C3—C4—C5—C7176.5 (2)
C9—N1—C10—C12160.08 (19)C4—C5—C6—C12.2 (3)
C10—N1—C9—C8176.31 (17)C7—C5—C6—C1−176.0 (2)
C6—C1—C2—C3−1.3 (3)C6—C5—C7—C8−1.2 (3)
C6—C1—C2—C13177.0 (2)C4—C5—C7—O1−1.1 (3)
C2—C1—C6—C5−0.7 (4)C4—C5—C7—C8−179.4 (2)
C13—C2—C3—C4−176.6 (2)C6—C5—C7—O1177.1 (2)
C1—C2—C3—C41.7 (3)O1—C7—C8—C9−11.9 (3)
C2—C3—C4—C5−0.2 (3)C5—C7—C8—C9166.46 (19)
C3—C4—C5—C6−1.8 (3)C7—C8—C9—N1176.54 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H14A···Cl10.902.263.148 (3)172
N1—H14B···Cl1i0.902.253.145 (3)173
C1—H1···O1ii0.932.533.340 (4)146
Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H14A···Cl10.902.263.148 (3)172
N1—H14B···Cl1i0.902.253.145 (3)173
C1—H1···O1ii0.932.533.340 (4)146
Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) x+1, y, z.
Acknowledgements top

The authors are indebted to the Department of Chemistry, Atatürk University, Erzurum, Turkey, for use of the X-ray diffractometer purchased under grant No. 2003/219 of the University Research Fund.

references
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