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Acta Crystallogr Sect E Struct Rep Online. Oct 1, 2012; 68(Pt 10): o2987.
Published online Sep 22, 2012. doi:  10.1107/S1600536812039645
PMCID: PMC3470349
2-(4-Meth­oxy­phenyl)-2-oxoethan­aminium chloride
Hoong-Kun Fun,ab* Wan-Sin Loh,a§ S. Viveka,c Dinesha,c and G. K. Nagarajac
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
bDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, PO Box 2457, Riyadh 11451, Saudi Arabia
cDepartment of Chemistry, Mangalore University, Karnataka, India
Correspondence e-mail: hkfun/at/usm.my
Thomson Reuters ResearcherID: A-3561-2009.
§Thomson Reuters ResearcherID: C-7581-2009.
Received September 12, 2012; Accepted September 18, 2012.
Abstract
In the cation of the title compound, C9H12NO2 +·Cl, the dihedral angle between the 2-oxoethanaminium N—C—C(=O)– plane [maximum deviation = 0.0148 (12) Å] and the benzene ring is 7.98 (8)°. The meth­oxy group is approximately in-plane with the benzene ring, with a C—O—C—C torsion angle of −2.91 (18)°. In the crystal, the cations and chloride anions are connected by N—H(...)Cl and C—H(...)Cl hydrogen bonds, forming a layer parallel to the bc plane. A C—H(...)π inter­action further links the layers.
Related literature  
For syntheses and applications of nitro­gen-containing heterocyclic compounds, see: Alvarez-Builla et al. (2011 [triangle]); Katritzky et al. (2010 [triangle]); Chen et al. (2011 [triangle]). For a related structure, see: Zhang et al. (2009 [triangle]). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 [triangle]).
An external file that holds a picture, illustration, etc.
Object name is e-68-o2987-scheme1.jpg Object name is e-68-o2987-scheme1.jpg
Crystal data  
  • C9H12NO2 +·Cl
  • M r = 201.65
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-o2987-efi1.jpg
  • a = 12.2822 (8) Å
  • b = 7.1605 (4) Å
  • c = 11.1226 (7) Å
  • β = 92.435 (1)°
  • V = 977.31 (10) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.36 mm−1
  • T = 100 K
  • 0.40 × 0.24 × 0.17 mm
Data collection  
  • Bruker SMART APEXII DUO CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.870, T max = 0.942
  • 10764 measured reflections
  • 2871 independent reflections
  • 2622 reflections with I > 2σ(I)
  • R int = 0.019
Refinement  
  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.099
  • S = 1.08
  • 2871 reflections
  • 132 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.66 e Å−3
  • Δρmin = −0.31 e Å−3
Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).
Table 1
Table 1
Hydrogen-bond geometry (Å, °)
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812039645/is5194sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039645/is5194Isup2.hkl
Supplementary material file. DOI: 10.1107/S1600536812039645/is5194Isup3.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
HKF and WSL thank Universiti Sains Malaysia (USM) for a Research University Grant (1001/PFIZIK/811160). WSL also thanks the Malaysian government and USM for the position of Research Officer under the Research University Grant No. 1001/PFIZIK/811160.
supplementary crystallographic information
Comment
The synthesis of nitrogen-containing heterocycles has long been a topic of intense research (Alvarez-Builla et al., 2011; Katritzky et al., 2010). This is due, in large part, to the importance of these compounds as drug candidates. The vast majority of new molecular entities (NMEs) contain at least one nitrogen atom in the chemical structure. A subcategory of these compounds are imidazoles, which are notable pharmacophores in a number of areas of discovery chemistry research (Chen et al., 2011). Appropriately, numerous synthetic approaches to these compounds have been published in the literature (Alvarez-Builla et al., 2011). Phenacyl amines are the key intermediate in the synthesis of various ketoamides and also provides a robust synthetic route toward 1H-4-substituted imidazole developed using phenacyl amines. Herein we report the synthesis and crystal structure of 2-(4-methoxyphenyl)-2-oxoethanaminium chloride.
The asymmetric unit of the title compound as shown in Fig. 1 consists of one 2-(4-methoxyphenyl)-2-oxoethanaminium cation and one chloride anion. One proton is transferred from the hydrochloric acid to the N atom. The ketone side chain and the methoxy group are coplanar with the benzene ring (C2–C7) with the torsion angles of C6—C5—C8—C9 = 173.82 (11)° and C1—O1—C2—C7 = -2.91 (18)°, respectively. The bond lengths and angles are similar to a related structure (Zhang et al., 2009).
The crystal structure (Fig. 2) is mainly stabilized by N—H···Cl and C—H···Cl hydrogen bonds (Table 1). In the crystal structure, the amine N atom acts as donor whereas the chloride anion acts as acceptor, linking them into a layer parallel to the bc plane. A C—H···π interaction (Table 1), involving the benzene ring, further consolidates the crystal structure.
Experimental
A 40 ml ethanolic solution of 5 mmol 4-methoxy phenacyl bromide was stirred with 5 mmol of HMTA for 10 h. The solid precipitated was filtered and the precipitate was dissolved in HCl and evaporated to dryness to get the crystals. M.p.: 433 K.
Refinement
N-bound H atoms were located in a difference Fourier map and were refined freely [N—H = 0.95 (2) to 0.98 (2) Å]. The remaining H atoms were positioned geometrically (C—H = 0.95 to 0.99 Å) and refined with a riding model with Uiso(H) = 1.2 or 1.5 Ueq(C). A rotating group model was applied to the methyl group. In the final refinement, one outliner, 1 0 0, was omitted.
Figures
Fig. 1.
Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids.
Fig. 2.
Fig. 2.
The crystal packing of the title compound, viewed along the a axis, showing the layer parallel to the bc plane. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.
Crystal data
C9H12NO2+·ClF(000) = 424
Mr = 201.65Dx = 1.370 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6587 reflections
a = 12.2822 (8) Åθ = 3.3–30.1°
b = 7.1605 (4) ŵ = 0.36 mm1
c = 11.1226 (7) ÅT = 100 K
β = 92.435 (1)°Block, yellow
V = 977.31 (10) Å30.40 × 0.24 × 0.17 mm
Z = 4
Data collection
Bruker SMART APEXII DUO CCD area-detector diffractometer2871 independent reflections
Radiation source: fine-focus sealed tube2622 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
[var phi] and ω scansθmax = 30.2°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −17→17
Tmin = 0.870, Tmax = 0.942k = −10→10
10764 measured reflectionsl = −15→15
Refinement
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.099w = 1/[σ2(Fo2) + (0.0509P)2 + 0.5579P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
2871 reflectionsΔρmax = 0.66 e Å3
132 parametersΔρmin = −0.31 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.027 (3)
Special details
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.
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)
xyzUiso*/Ueq
O10.31506 (8)0.43288 (14)0.83094 (9)0.0240 (2)
O20.77620 (8)0.12046 (16)1.02231 (9)0.0271 (2)
N10.93861 (9)0.16996 (19)0.87460 (10)0.0224 (2)
C10.22952 (11)0.3669 (2)0.90447 (13)0.0252 (3)
H1A0.16010.42270.87670.038*
H1B0.24570.40230.98840.038*
H1C0.22450.23060.89840.038*
C20.41825 (10)0.37782 (18)0.86212 (11)0.0187 (2)
C30.49898 (10)0.43820 (18)0.78563 (11)0.0198 (2)
H3A0.47950.51370.71790.024*
C40.60660 (10)0.38863 (18)0.80810 (11)0.0191 (2)
H4A0.66070.42970.75550.023*
C50.63640 (10)0.27779 (17)0.90828 (11)0.0176 (2)
C60.55558 (10)0.22213 (17)0.98526 (11)0.0186 (2)
H6A0.57540.15041.05460.022*
C70.44689 (11)0.26912 (17)0.96292 (11)0.0192 (2)
H7A0.39280.22801.01540.023*
C80.74917 (10)0.21092 (17)0.93292 (11)0.0189 (2)
C90.83234 (11)0.25722 (18)0.84067 (11)0.0202 (2)
H9A0.80640.21110.76060.024*
H9B0.84120.39440.83550.024*
Cl11.05551 (2)0.22239 (4)0.63026 (2)0.01705 (10)
H1N10.9649 (18)0.215 (3)0.952 (2)0.041 (6)*
H2N10.9365 (14)0.037 (3)0.8780 (16)0.029 (5)*
H3N10.9882 (18)0.196 (3)0.810 (2)0.040 (6)*
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
O10.0205 (4)0.0274 (5)0.0244 (4)0.0012 (4)0.0030 (3)0.0044 (4)
O20.0252 (5)0.0328 (5)0.0232 (5)0.0012 (4)0.0017 (4)0.0083 (4)
N10.0209 (5)0.0255 (6)0.0210 (5)0.0000 (4)0.0023 (4)0.0003 (4)
C10.0207 (6)0.0270 (7)0.0281 (6)−0.0017 (5)0.0041 (5)0.0015 (5)
C20.0211 (5)0.0171 (5)0.0180 (5)0.0001 (4)0.0018 (4)−0.0018 (4)
C30.0242 (6)0.0186 (6)0.0166 (5)0.0008 (4)0.0026 (4)0.0019 (4)
C40.0231 (6)0.0184 (5)0.0161 (5)−0.0016 (4)0.0040 (4)0.0010 (4)
C50.0200 (5)0.0171 (5)0.0157 (5)−0.0016 (4)0.0015 (4)−0.0010 (4)
C60.0235 (6)0.0175 (5)0.0150 (5)−0.0013 (4)0.0018 (4)0.0004 (4)
C70.0223 (6)0.0189 (6)0.0168 (5)−0.0021 (4)0.0043 (4)−0.0002 (4)
C80.0215 (5)0.0178 (5)0.0176 (5)−0.0022 (4)0.0018 (4)−0.0005 (4)
C90.0209 (6)0.0209 (6)0.0189 (5)−0.0001 (4)0.0028 (4)0.0010 (4)
Cl10.02011 (15)0.01794 (16)0.01333 (15)0.00302 (9)0.00337 (9)0.00102 (9)
Geometric parameters (Å, º)
O1—C21.3582 (15)C3—C41.3812 (17)
O1—C11.4384 (16)C3—H3A0.9500
O2—C81.2208 (16)C4—C51.4039 (17)
N1—C91.4814 (17)C4—H4A0.9500
N1—H1N10.96 (2)C5—C61.3962 (17)
N1—H2N10.95 (2)C5—C81.4800 (17)
N1—H3N10.98 (2)C6—C71.3888 (18)
C1—H1A0.9800C6—H6A0.9500
C1—H1B0.9800C7—H7A0.9500
C1—H1C0.9800C8—C91.5150 (18)
C2—C71.3975 (17)C9—H9A0.9900
C2—C31.4020 (17)C9—H9B0.9900
C2—O1—C1117.11 (10)C3—C4—H4A119.9
C9—N1—H1N1110.3 (13)C5—C4—H4A119.9
C9—N1—H2N1114.0 (11)C6—C5—C4118.68 (11)
H1N1—N1—H2N1107.7 (16)C6—C5—C8118.57 (11)
C9—N1—H3N1107.4 (13)C4—C5—C8122.70 (11)
H1N1—N1—H3N1113.7 (19)C7—C6—C5121.61 (11)
H2N1—N1—H3N1103.8 (17)C7—C6—H6A119.2
O1—C1—H1A109.5C5—C6—H6A119.2
O1—C1—H1B109.5C6—C7—C2119.06 (11)
H1A—C1—H1B109.5C6—C7—H7A120.5
O1—C1—H1C109.5C2—C7—H7A120.5
H1A—C1—H1C109.5O2—C8—C5122.85 (11)
H1B—C1—H1C109.5O2—C8—C9119.99 (12)
O1—C2—C7124.53 (11)C5—C8—C9117.16 (10)
O1—C2—C3115.59 (11)N1—C9—C8110.32 (10)
C7—C2—C3119.88 (12)N1—C9—H9A109.6
C4—C3—C2120.47 (11)C8—C9—H9A109.6
C4—C3—H3A119.8N1—C9—H9B109.6
C2—C3—H3A119.8C8—C9—H9B109.6
C3—C4—C5120.27 (11)H9A—C9—H9B108.1
C1—O1—C2—C7−2.91 (18)C5—C6—C7—C2−1.25 (19)
C1—O1—C2—C3177.42 (11)O1—C2—C7—C6−179.90 (12)
O1—C2—C3—C4−179.30 (11)C3—C2—C7—C6−0.23 (18)
C7—C2—C3—C41.01 (19)C6—C5—C8—O2−5.45 (19)
C2—C3—C4—C5−0.31 (19)C4—C5—C8—O2177.16 (12)
C3—C4—C5—C6−1.13 (18)C6—C5—C8—C9173.82 (11)
C3—C4—C5—C8176.25 (11)C4—C5—C8—C9−3.57 (17)
C4—C5—C6—C71.93 (19)O2—C8—C9—N13.06 (17)
C8—C5—C6—C7−175.56 (11)C5—C8—C9—N1−176.23 (11)
Hydrogen-bond geometry (Å, º)
Cg1 is the centroid of the C2–C7 ring.
D—H···AD—HH···AD···AD—H···A
N1—H2N1···Cl1i0.95 (2)2.26 (2)3.2061 (14)173.6 (15)
N1—H3N1···Cl10.99 (2)2.19 (2)3.1496 (12)162.6 (19)
N1—H1N1···Cl1ii0.97 (2)2.27 (2)3.2240 (12)168.4 (19)
C9—H9B···Cl1iii0.992.693.6135 (13)156
C3—H3A···Cg1iv0.952.533.3909 (14)150
Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) x, −y+1/2, z+1/2; (iii) −x+2, y+1/2, −z+3/2; (iv) −x+1, y+1/2, −z+3/2.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS5194).
  • Alvarez-Builla, J., Vaquero, J. J. & Barluenga, J. (2011). Editors. Modern Heterocyclic Chemistry, Vol. 2, pp. 635–1047. Weinheim: Wiley-VCH.
  • Bruker (2009). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, S. B., Tan, J. H., Ou, T. M., Huang, S. L., An, L. K., Luo, H. B., Li, D., Gu, L. Q. & Huang, Z. S. (2011). Bioorg. Med. Chem. Lett. 21, 1004–1009. [PubMed]
  • Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.
  • Katritzky, A. R., Ramsden, C. A., Joule, J. A. & Zhdankin, V. V. (2010). Handbook of Heterocyclic Chemistry, 3rd ed. Oxford: Elsevier.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Zhang, J., Zhuang, L. & Wang, G. (2009). Acta Cryst. E65, o2245. [PMC free article] [PubMed]
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