N-Methyl-2-oxo-1-phenyl­propan-1-aminium chloride

Wang, S.J.

doi:10.1107/S1600536811024032

organic compounds

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Volume 67| Part 7| July 2011| Page o1855

doi:10.1107/S1600536811024032

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N-Methyl-2-oxo-1-phenylpropan-1-aminium chloride

Shi Juan Wang ^a ^*

^aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: wsj@njcc.edu.cn

(Received 19 March 2011; accepted 20 June 2011; online 30 June 2011)

In the structure of the title compound, C₁₀H₁₄NO⁺·Cl⁻, both H atoms bound to nitrogen are involved in N—H⋯Cl hydrogen-bonding interactions. These interactions join the cations and anions into dimeric units (two cations and two anions) with R₄²(8) motifs lying about inversion centers.

Related literature

For the screening of molecular salts with physicochemical properties, see: Tong & Whitesell et al. (1998 ); Shanker (1994 ). Over 40% of commercially available salts are hydrochlorides (Gould et al., 1986 ), and this trend is reflected in the available set of salt structures included in the Cambridge Structural Database (Allen et al., 2002 ). For a closely related structure, see: Au & Tafeenko (1986 ).

Experimental

Crystal data

C₁₀H₁₄NO⁺·Cl⁻
M_r = 199.67
Monoclinic, P 2₁ /c
a = 12.631 (3) Å
b = 8.2564 (17) Å
c = 11.423 (2) Å
β = 114.63 (3)°
V = 1082.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury 2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002 ) T_min = 0.825, T_max = 1.000
10899 measured reflections
2486 independent reflections
1858 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.172
S = 1.12
2486 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1	0.90	2.26	3.1345 (19)	163
N1—H1E⋯Cl1ⁱ	0.90	2.19	3.0747 (19)	167
Symmetry code: (i) -x+2, -y+1, -z+2.

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811024032/yk2004sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024032/yk2004Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811024032/yk2004Isup3.cml

checkCIF report

Comment top

The importance of molecular salts as solid forms in pharmaceutical formulations is well known. For a given active ingredient, the isolation and selection of a salt with the appropriate physicochemical properties involves significant screening activity and has been discussed at some length in the literature (Tong & Whitesell et al., 1998; Shanker et al., 1994). It is apparent that over 40% of marketed salts are hydrochlorides (Gould et al., 1986), and this trend is reflected in the available set of salt structures provided by the Cambridge Structural Database (Allen et al., 2002). Here we report the synthesis and crystal structure of the title compound, N-methyl-2-oxo-1-phenylpropan-1-aminium chloride (Fig. 1).

The bond distances and angles in the structure of the title compound agree very well with the corresponding distances and angles reported for a closely related compound (Au & Tafeenko et al., 1986). It is noteworthy that both H-atoms bonded to one nitrogen (N1) are involved in hydrogen bonding interactions of the type N—H···Cl hydrogen bonds, forming dimers lying about inversion centers according to R₂²(4) motifs in graph set notation (Tab.1, Fig.2). Dipole-dipole and van der Waals interactions are effective in the molecular packing.

Related literature top

For the screening of molecular salts with physicochemical properties, see: Tong & Whitesell et al. (1998); Shanker (1994). Over 40% of marketed salts are hydrochlorides (Gould et al., 1986), and this trend is reflected in the available set of salt structures included in the Cambridge Structural Database (Allen et al., 2002). For a closely related structure, see: Au & Tafeenko (1986).

Experimental top

To a stirred solution of 1-(methylamino)-1-phenylpropan-2-one (2.445 g, 0.015 mol) in 30 mL of dry THF, hydrochloric acid (1.52 g, 0.015 mol) was added at the room temperature. The precipitate was filtered and washed with a small amount of ethanol 95%. Single crystals suitable for X-ray diffraction analysis were obtained from slow evaporation of a solution of the title compound in water at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the asymmetric unit of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the b axis showing the hydrogen bonds N—H···Cl (dotted lines).

N-Methyl-2-oxo-1-phenylpropan-1-aminium chloride top

Crystal data top

C₁₀H₁₄NO⁺·Cl⁻	F(000) = 424
M_r = 199.67	D_x = 1.225 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2486 reflections
a = 12.631 (3) Å	θ = 2.6–27.5°
b = 8.2564 (17) Å	µ = 0.32 mm⁻¹
c = 11.423 (2) Å	T = 293 K
β = 114.63 (3)°	Prism, colorless
V = 1082.9 (4) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury 2 diffractometer	2486 independent reflections
Radiation source: fine-focus sealed tube	1858 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	k = −10→10
T_min = 0.825, T_max = 1.000	l = −14→14
10899 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.1P)² + 0.0P] where P = (F_o² + 2F_c²)/3
2486 reflections	(Δ/σ)_max = 0.001
118 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₀H₁₄NO⁺·Cl⁻	V = 1082.9 (4) Å³
M_r = 199.67	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.631 (3) Å	µ = 0.32 mm⁻¹
b = 8.2564 (17) Å	T = 293 K
c = 11.423 (2) Å	0.20 × 0.20 × 0.20 mm
β = 114.63 (3)°

Data collection top

Rigaku Mercury 2 diffractometer	2486 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	1858 reflections with I > 2σ(I)
T_min = 0.825, T_max = 1.000	R_int = 0.053
10899 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.12	Δρ_max = 0.27 e Å⁻³
2486 reflections	Δρ_min = −0.20 e Å⁻³
118 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

	x	y	z	U_iso*/U_eq
Cl1	0.84648 (5)	0.60715 (7)	1.05463 (5)	0.0477 (2)
N1	0.88712 (14)	0.4261 (2)	0.83566 (16)	0.0372 (4)
H1A	0.8633	0.4628	0.8949	0.045*
H1E	0.9638	0.4049	0.8764	0.045*
C4	0.6325 (2)	0.3894 (3)	0.7610 (2)	0.0557 (7)
H4A	0.6721	0.4438	0.8384	0.067*
C5	0.82470 (17)	0.2721 (2)	0.78105 (19)	0.0371 (5)
H5A	0.8544	0.2286	0.7207	0.045*
C7	0.85316 (19)	0.1511 (3)	0.8920 (2)	0.0429 (5)
C8	0.69366 (18)	0.2949 (3)	0.7093 (2)	0.0396 (5)
C9	0.5129 (2)	0.4023 (4)	0.6973 (3)	0.0725 (9)
H9A	0.4724	0.4663	0.7317	0.087*
C10	0.8142 (3)	−0.0187 (3)	0.8562 (3)	0.0646 (8)
H10A	0.8363	−0.0829	0.9329	0.097*
H10B	0.8501	−0.0618	0.8036	0.097*
H10C	0.7311	−0.0212	0.8091	0.097*
C11	0.6337 (2)	0.2185 (3)	0.5944 (2)	0.0606 (7)
H11A	0.6737	0.1578	0.5574	0.073*
C12	0.5143 (3)	0.2308 (4)	0.5332 (3)	0.0782 (10)
H12A	0.4746	0.1759	0.4561	0.094*
C13	0.4533 (2)	0.3214 (4)	0.5833 (3)	0.0747 (9)
H13A	0.3727	0.3286	0.5412	0.090*
C1	0.8697 (2)	0.5566 (3)	0.7395 (2)	0.0535 (6)
H1B	0.9126	0.6511	0.7824	0.080*
H1C	0.7884	0.5826	0.6970	0.080*
H1D	0.8970	0.5202	0.6771	0.080*
O2	0.90399 (18)	0.1954 (2)	1.00174 (16)	0.0685 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0439 (4)	0.0545 (4)	0.0443 (4)	0.0016 (2)	0.0181 (3)	−0.0090 (2)
N1	0.0367 (10)	0.0430 (10)	0.0320 (9)	0.0007 (7)	0.0144 (8)	0.0012 (7)
C4	0.0402 (13)	0.081 (2)	0.0412 (14)	0.0042 (12)	0.0126 (11)	−0.0107 (12)
C5	0.0380 (11)	0.0403 (11)	0.0351 (11)	0.0030 (9)	0.0174 (9)	0.0010 (9)
C7	0.0411 (12)	0.0458 (12)	0.0444 (13)	0.0062 (10)	0.0206 (10)	0.0087 (10)
C8	0.0359 (11)	0.0461 (13)	0.0330 (11)	−0.0001 (9)	0.0106 (9)	0.0020 (9)
C9	0.0463 (15)	0.104 (3)	0.0649 (18)	0.0143 (15)	0.0204 (14)	−0.0088 (16)
C10	0.0814 (19)	0.0464 (15)	0.0628 (18)	−0.0013 (13)	0.0269 (15)	0.0096 (12)
C11	0.0575 (16)	0.0673 (17)	0.0466 (14)	0.0056 (13)	0.0114 (12)	−0.0156 (12)
C12	0.0593 (18)	0.091 (2)	0.0570 (17)	−0.0015 (16)	−0.0033 (14)	−0.0222 (16)
C13	0.0389 (15)	0.103 (2)	0.0652 (19)	0.0037 (15)	0.0045 (13)	−0.0044 (18)
C1	0.0651 (16)	0.0445 (13)	0.0481 (14)	−0.0040 (12)	0.0208 (12)	0.0077 (10)
O2	0.0939 (15)	0.0638 (13)	0.0361 (10)	0.0005 (10)	0.0155 (9)	0.0099 (8)

Geometric parameters (Å, º) top

N1—C1	1.488 (3)	C9—C13	1.375 (4)
N1—C5	1.489 (3)	C9—H9A	0.9300
N1—H1A	0.9000	C10—H10A	0.9600
N1—H1E	0.9000	C10—H10B	0.9600
C4—C9	1.380 (3)	C10—H10C	0.9600
C4—C8	1.391 (3)	C11—C12	1.376 (4)
C4—H4A	0.9300	C11—H11A	0.9300
C5—C8	1.522 (3)	C12—C13	1.359 (4)
C5—C7	1.534 (3)	C12—H12A	0.9300
C5—H5A	0.9800	C13—H13A	0.9300
C7—O2	1.203 (3)	C1—H1B	0.9600
C7—C10	1.486 (4)	C1—H1C	0.9600
C8—C11	1.366 (3)	C1—H1D	0.9600

C1—N1—C5	114.80 (17)	C4—C9—H9A	119.7
C1—N1—H1A	108.6	C7—C10—H10A	109.5
C5—N1—H1A	108.6	C7—C10—H10B	109.5
C1—N1—H1E	108.6	H10A—C10—H10B	109.5
C5—N1—H1E	108.6	C7—C10—H10C	109.5
H1A—N1—H1E	107.5	H10A—C10—H10C	109.5
C9—C4—C8	119.9 (2)	H10B—C10—H10C	109.5
C9—C4—H4A	120.0	C8—C11—C12	120.4 (3)
C8—C4—H4A	120.0	C8—C11—H11A	119.8
N1—C5—C8	112.75 (17)	C12—C11—H11A	119.8
N1—C5—C7	108.00 (17)	C13—C12—C11	121.3 (3)
C8—C5—C7	110.70 (17)	C13—C12—H12A	119.3
N1—C5—H5A	108.4	C11—C12—H12A	119.3
C8—C5—H5A	108.4	C12—C13—C9	118.9 (3)
C7—C5—H5A	108.4	C12—C13—H13A	120.6
O2—C7—C10	123.0 (2)	C9—C13—H13A	120.6
O2—C7—C5	120.2 (2)	N1—C1—H1B	109.5
C10—C7—C5	116.8 (2)	N1—C1—H1C	109.5
C11—C8—C4	118.9 (2)	H1B—C1—H1C	109.5
C11—C8—C5	120.2 (2)	N1—C1—H1D	109.5
C4—C8—C5	120.9 (2)	H1B—C1—H1D	109.5
C13—C9—C4	120.6 (3)	H1C—C1—H1D	109.5
C13—C9—H9A	119.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.90	2.26	3.1345 (19)	163
N1—H1E···Cl1ⁱ	0.90	2.19	3.0747 (19)	167

Symmetry code: (i) −x+2, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₄NO⁺·Cl⁻
M_r	199.67
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.631 (3), 8.2564 (17), 11.423 (2)
β (°)	114.63 (3)
V (Å³)	1082.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury 2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2002)
T_min, T_max	0.825, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10899, 2486, 1858
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.172, 1.12
No. of reflections	2486
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.20

Computer programs: CrystalClear (Rigaku, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.90	2.26	3.1345 (19)	163
N1—H1E···Cl1ⁱ	0.90	2.19	3.0747 (19)	167

Symmetry code: (i) −x+2, −y+1, −z+2.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Au, O. & Tafeenko, V. (1986). Rev. Cubana Quim. 2, 65–74. CAS Google Scholar
Brandenburg, K. (1998). DIAMOND. University of Bonn, Germany. Google Scholar
Gould, P. L. (1986). Int. J. Pharm. 33, 201–217. CrossRef CAS Web of Science Google Scholar
Rigaku (2002). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Shanker, R. (1994). Pharm. Res. 11, S–236. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tong, W. & Whitesell, G. (1998). Pharm. Dev. Technol. 3, 215–223. CrossRef CAS PubMed Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1855

doi:10.1107/S1600536811024032

Open

access