2-(4-Meth­oxy­phenyl)-2-oxoethan­aminium chloride

doi:10.1107/S1600536812039645

Acta Crystallogr Sect E Struct Rep Online. 2012 October 1; 68(Pt 10): o2987.

Published online 2012 September 22. doi: 10.1107/S1600536812039645

PMCID: PMC3470349

2-(4-Methoxyphenyl)-2-oxoethanaminium chloride

Hoong-Kun Fun,^a^b^*^‡ Wan-Sin Loh,^a^§ S. Viveka,^c Dinesha,^c and G. K. Nagaraja^c

^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.

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

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

); Katritzky et al. (2010

); Chen et al. (2011

). For a related structure, see: Zhang et al. (2009

). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986

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

Experimental

Crystal data

C₉H₁₂NO₂ ⁺·Cl⁻
M _r = 201.65
Monoclinic,
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 ) 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
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2009

); cell refinement: SAINT (Bruker, 2009

); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008

); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009

Table 1

Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812039645/is5194sup1.cif

Click here to view.^{(21K, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039645/is5194Isup2.hkl

Click here to view.^{(141K, 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.

Figures

Fig. 1.

The molecular structure of the title compound, showing 50% probability displacement ellipsoids.

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⁺·Cl⁻	F(000) = 424
M_r = 201.65	D_x = 1.370 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6587 reflections
a = 12.2822 (8) Å	θ = 3.3–30.1°
b = 7.1605 (4) Å	µ = 0.36 mm⁻¹
c = 11.1226 (7) Å	T = 100 K
β = 92.435 (1)°	Block, yellow
V = 977.31 (10) Å³	0.40 × 0.24 × 0.17 mm
Z = 4

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer	2871 independent reflections
Radiation source: fine-focus sealed tube	2622 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
and ω scans	θ_max = 30.2°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −17→17
T_min = 0.870, T_max = 0.942	k = −10→10
10764 measured reflections	l = −15→15

Refinement

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0509P)² + 0.5579P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2871 reflections	Δρ_max = 0.66 e Å⁻³
132 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction 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)

	x	y	z	U_iso*/U_eq
O1	0.31506 (8)	0.43288 (14)	0.83094 (9)	0.0240 (2)
O2	0.77620 (8)	0.12046 (16)	1.02231 (9)	0.0271 (2)
N1	0.93861 (9)	0.16996 (19)	0.87460 (10)	0.0224 (2)
C1	0.22952 (11)	0.3669 (2)	0.90447 (13)	0.0252 (3)
H1A	0.1601	0.4227	0.8767	0.038*
H1B	0.2457	0.4023	0.9884	0.038*
H1C	0.2245	0.2306	0.8984	0.038*
C2	0.41825 (10)	0.37782 (18)	0.86212 (11)	0.0187 (2)
C3	0.49898 (10)	0.43820 (18)	0.78563 (11)	0.0198 (2)
H3A	0.4795	0.5137	0.7179	0.024*
C4	0.60660 (10)	0.38863 (18)	0.80810 (11)	0.0191 (2)
H4A	0.6607	0.4297	0.7555	0.023*
C5	0.63640 (10)	0.27779 (17)	0.90828 (11)	0.0176 (2)
C6	0.55558 (10)	0.22213 (17)	0.98526 (11)	0.0186 (2)
H6A	0.5754	0.1504	1.0546	0.022*
C7	0.44689 (11)	0.26912 (17)	0.96292 (11)	0.0192 (2)
H7A	0.3928	0.2280	1.0154	0.023*
C8	0.74917 (10)	0.21092 (17)	0.93292 (11)	0.0189 (2)
C9	0.83234 (11)	0.25722 (18)	0.84067 (11)	0.0202 (2)
H9A	0.8064	0.2111	0.7606	0.024*
H9B	0.8412	0.3944	0.8355	0.024*
Cl1	1.05551 (2)	0.22239 (4)	0.63026 (2)	0.01705 (10)
H1N1	0.9649 (18)	0.215 (3)	0.952 (2)	0.041 (6)*
H2N1	0.9365 (14)	0.037 (3)	0.8780 (16)	0.029 (5)*
H3N1	0.9882 (18)	0.196 (3)	0.810 (2)	0.040 (6)*

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0205 (4)	0.0274 (5)	0.0244 (4)	0.0012 (4)	0.0030 (3)	0.0044 (4)
O2	0.0252 (5)	0.0328 (5)	0.0232 (5)	0.0012 (4)	0.0017 (4)	0.0083 (4)
N1	0.0209 (5)	0.0255 (6)	0.0210 (5)	0.0000 (4)	0.0023 (4)	0.0003 (4)
C1	0.0207 (6)	0.0270 (7)	0.0281 (6)	−0.0017 (5)	0.0041 (5)	0.0015 (5)
C2	0.0211 (5)	0.0171 (5)	0.0180 (5)	0.0001 (4)	0.0018 (4)	−0.0018 (4)
C3	0.0242 (6)	0.0186 (6)	0.0166 (5)	0.0008 (4)	0.0026 (4)	0.0019 (4)
C4	0.0231 (6)	0.0184 (5)	0.0161 (5)	−0.0016 (4)	0.0040 (4)	0.0010 (4)
C5	0.0200 (5)	0.0171 (5)	0.0157 (5)	−0.0016 (4)	0.0015 (4)	−0.0010 (4)
C6	0.0235 (6)	0.0175 (5)	0.0150 (5)	−0.0013 (4)	0.0018 (4)	0.0004 (4)
C7	0.0223 (6)	0.0189 (6)	0.0168 (5)	−0.0021 (4)	0.0043 (4)	−0.0002 (4)
C8	0.0215 (5)	0.0178 (5)	0.0176 (5)	−0.0022 (4)	0.0018 (4)	−0.0005 (4)
C9	0.0209 (6)	0.0209 (6)	0.0189 (5)	−0.0001 (4)	0.0028 (4)	0.0010 (4)
Cl1	0.02011 (15)	0.01794 (16)	0.01333 (15)	0.00302 (9)	0.00337 (9)	0.00102 (9)

Geometric parameters (Å, º)

O1—C2	1.3582 (15)	C3—C4	1.3812 (17)
O1—C1	1.4384 (16)	C3—H3A	0.9500
O2—C8	1.2208 (16)	C4—C5	1.4039 (17)
N1—C9	1.4814 (17)	C4—H4A	0.9500
N1—H1N1	0.96 (2)	C5—C6	1.3962 (17)
N1—H2N1	0.95 (2)	C5—C8	1.4800 (17)
N1—H3N1	0.98 (2)	C6—C7	1.3888 (18)
C1—H1A	0.9800	C6—H6A	0.9500
C1—H1B	0.9800	C7—H7A	0.9500
C1—H1C	0.9800	C8—C9	1.5150 (18)
C2—C7	1.3975 (17)	C9—H9A	0.9900
C2—C3	1.4020 (17)	C9—H9B	0.9900

C2—O1—C1	117.11 (10)	C3—C4—H4A	119.9
C9—N1—H1N1	110.3 (13)	C5—C4—H4A	119.9
C9—N1—H2N1	114.0 (11)	C6—C5—C4	118.68 (11)
H1N1—N1—H2N1	107.7 (16)	C6—C5—C8	118.57 (11)
C9—N1—H3N1	107.4 (13)	C4—C5—C8	122.70 (11)
H1N1—N1—H3N1	113.7 (19)	C7—C6—C5	121.61 (11)
H2N1—N1—H3N1	103.8 (17)	C7—C6—H6A	119.2
O1—C1—H1A	109.5	C5—C6—H6A	119.2
O1—C1—H1B	109.5	C6—C7—C2	119.06 (11)
H1A—C1—H1B	109.5	C6—C7—H7A	120.5
O1—C1—H1C	109.5	C2—C7—H7A	120.5
H1A—C1—H1C	109.5	O2—C8—C5	122.85 (11)
H1B—C1—H1C	109.5	O2—C8—C9	119.99 (12)
O1—C2—C7	124.53 (11)	C5—C8—C9	117.16 (10)
O1—C2—C3	115.59 (11)	N1—C9—C8	110.32 (10)
C7—C2—C3	119.88 (12)	N1—C9—H9A	109.6
C4—C3—C2	120.47 (11)	C8—C9—H9A	109.6
C4—C3—H3A	119.8	N1—C9—H9B	109.6
C2—C3—H3A	119.8	C8—C9—H9B	109.6
C3—C4—C5	120.27 (11)	H9A—C9—H9B	108.1

C1—O1—C2—C7	−2.91 (18)	C5—C6—C7—C2	−1.25 (19)
C1—O1—C2—C3	177.42 (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—C4	1.01 (19)	C6—C5—C8—O2	−5.45 (19)
C2—C3—C4—C5	−0.31 (19)	C4—C5—C8—O2	177.16 (12)
C3—C4—C5—C6	−1.13 (18)	C6—C5—C8—C9	173.82 (11)
C3—C4—C5—C8	176.25 (11)	C4—C5—C8—C9	−3.57 (17)
C4—C5—C6—C7	1.93 (19)	O2—C8—C9—N1	3.06 (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···A	D—H	H···A	D···A	D—H···A
N1—H2N1···Cl1ⁱ	0.95 (2)	2.26 (2)	3.2061 (14)	173.6 (15)
N1—H3N1···Cl1	0.99 (2)	2.19 (2)	3.1496 (12)	162.6 (19)
N1—H1N1···Cl1ⁱⁱ	0.97 (2)	2.27 (2)	3.2240 (12)	168.4 (19)
C9—H9B···Cl1ⁱⁱⁱ	0.99	2.69	3.6135 (13)	156
C3—H3A···Cg1^iv	0.95	2.53	3.3909 (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).

References

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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]
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Katritzky, A. R., Ramsden, C. A., Joule, J. A. & Zhdankin, V. V. (2010). Handbook of Heterocyclic Chemistry, 3rd ed. Oxford: Elsevier.
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