N-[2-(4-Bromo­benzo­yl)eth­yl]isopropyl­aminium chloride

Abdullah Aydın; Mehmet Akkurt; Halise Inci Gul; Ebru Mete; Ertan Sahin

doi:10.1107/S1600536811052640

. 2011 Dec 10;68(Pt 1):o71. doi: 10.1107/S1600536811052640

N-[2-(4-Bromobenzoyl)ethyl]isopropylaminium chloride

Abdullah Aydın ^a,^*, Mehmet Akkurt ^b, Halise Inci Gul ^c, Ebru Mete ^d, Ertan Sahin ^d

PMCID: PMC3254426 PMID: 22259572

Abstract

The crystal structure of the title compound, C₁₂H₁₇BrNO⁺·Cl⁻, is stabilized by N—H⋯Cl and C—H⋯O hydrogen bonds, forming a three-dimensional network. The interactions framework is completed by C—H⋯π contacts between a methylene group and the benzene ring of a symmetry-related molecule.

Related literature

For details of the pharmacological effects of Mannich bases and for the synthesis, see: Dimmock & Kumar (1997 ▶); Gul, Gul, et al. (2005 ▶); Gul, Sahin et al. (2005 ▶); Gul et al. (2007 ▶); Mete et al. (2011 ▶); Kucukoglu et al. (2011 ▶); Canturk et al. (2008 ▶); Chen et al. (1991 ▶); Suleyman et al. (2007 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₂H₁₇BrNO⁺·Cl⁻
M _r = 306.62
Tetragonal,
a = 19.7122 (4) Å
c = 7.1738 (2) Å
V = 2787.53 (11) Å³
Z = 8
Mo Kα radiation
μ = 3.12 mm⁻¹
T = 294 K
0.15 × 0.13 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer
Absorption correction: multi-scan (Blessing, 1995 ▶) T _min = 0.632, T _max = 0.709
50060 measured reflections
2836 independent reflections
1617 reflections with I > 2σ(I)
R _int = 0.151

Refinement

R[F ² > 2σ(F ²)] = 0.076
wR(F ²) = 0.181
S = 1.07
2836 reflections
153 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); 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 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811052640/bh2400sup1.cif

e-68-00o71-sup1.cif^{(16.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811052640/bh2400Isup2.hkl

e-68-00o71-Isup2.hkl^{(139.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811052640/bh2400Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—HN2⋯Cl1	0.86 (4)	2.26 (4)	3.102 (4)	166 (5)
N1—HN1⋯Cl1ⁱ	0.86 (6)	2.27 (6)	3.133 (5)	177 (9)
C12—H12B⋯O1ⁱⁱ	0.96	2.60	3.378 (7)	139
C9—H9B⋯Cg1ⁱⁱⁱ	0.97	3.00	3.943 (6)	164

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

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.

supplementary crystallographic information

Comment

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, Sahin, et al., 2005), cytotoxic (Gul, Gul et al., 2005; Gul et al., 2007; Mete et al., 2011; Kucukoglu et al., 2011), anticancer (Dimmock & Kumar, 1997; Chen et al., 1991), anti-inflammatory (Suleyman et al., 2007), and DNA topoisomerase I inhibiting properties (Canturk et al., 2008).

A Mannich base having at least one hydrogen atom at the β position of amine group can undergo a deamination process to generate an α,β-unsaturated ketone moiety.

In the molecule of the tile compound (Fig. 1), the bond lengths are within normal ranges (Allen et al., 1987), as well as bond angles.

In the crystal structure, molecules are linked via intermolecular N—H···Cl and C—H···O hydrogen bonds (Table 1, Fig. 2), forming a three dimensional network. Furthermore, a C—H···π interaction (Table 1) contributes to the stabilization of the crystal packing.

Experimental

A mixture of the appropriate ketone (50 mmol), para-formaldehyde (50 mmol), and iso-propylamine 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 resulting precipitates were then collected and the Mannich base (I) was passed through a column of silica gel 60 (70–230 mesh) using methanol as eluent. After evaporation of the solvent, the product was recrystallized from methanol. M.p.: 447–449 K. Yield: 38%. ¹H-NMR (CDCl₃) δ 1.49 (d, J = 6.8 Hz, 6H, CH(CH₃)₂), 3.34–3.38 (m, 3H, CH(CH₃)₂ and 2 x H-2), 3.73 (t, J = 7.3 Hz, 2H, 2 x H-3), 7.50 (d, J = 8.4 Hz, 2H, H-3'/5'), 7.76 (d, 2H, J = 8.4 Hz, H-2'/6'), 9.55 (brs, 2H, NH₂⁺). ¹³C-NMR (CDCl₃) δ 19.4 (CH(CH₃)₂), 35.3, 40.2, 51.3, 129.4, 129.8, 132.3, 134.7, 195.8 (CO); MS (EI) m/z: 254 (M - CH₃)⁺, 256 (M - CH₃ + 2)⁺, 270.2 (M + H)⁺, 272.2 (M + H + 2)⁺. IR (KBr, cm^-1): 2462 (NH₂⁺), 1684 (CO). Calcd. for C₁₂H₁₇BrClNO (306.63): C 47.00, H 5.59, N 4.57. Found: C 46.74, H 5.52, N 4.59 (Mete et al., 2011).