3-Meth­oxy-3-oxopropanaminium chloride

Gruber, T.; Schofield, C.J.; Thompson, A.L.

doi:10.1107/S1600536812003297

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o595

doi:10.1107/S1600536812003297

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3-Methoxy-3-oxopropanaminium chloride

Tobias Gruber,^a ‡ Christopher J. Schofield ^a and Amber L. Thompson ^b ^*

^aChemistry Research Laboratory, Department of Chemistry, University of Oxford, Mansfield Road, Oxford OX1 3TA, England, and ^bChemical Crystallography, Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Mansfield Road, Oxford OX1 3TA, England
^*Correspondence e-mail: amber.thompson@chem.ox.ac.uk

(Received 18 November 2011; accepted 25 January 2012; online 4 February 2012)

In the title compound, C₄H₁₀NO₂⁺·Cl⁻, the central ethylene bond of the cation adopts a gauche conformation. The three H atoms of the –NH₃⁺ group are engaged in strong and highly directional intermolecular N—H⋯Cl hydrogen bonds, which result in a tape-like arrangement along [010] of the respective ion pairs. In addition, weak intermolecular C—H⋯Cl and C—H⋯O interactions are present.

Related literature

For the synthesis of the title compound, see: Hansen (1963 ). For related structures, see: Akkerman et al. (2003 ); Robinson et al. (2004 ); Vilela et al. (2009 ); Tarafdar & Swamy (2010 ); Gossage et al. (2010 ); He et al. (2010 ). For information on the gauche effect, see: Amos et al. (1992 ). For details of the H-atom treatment, see: Cooper et al. (2010 ). For the weighting scheme used in the refinement, see: Watkin (1994 ); Prince (1982 ).

Experimental

Crystal data

C₄H₁₀NO₂⁺·Cl⁻
M_r = 139.58
Monoclinic, P 2₁ /c
a = 9.8469 (2) Å
b = 5.3263 (1) Å
c = 13.2804 (2) Å
β = 99.4638 (10)°
V = 687.04 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 150 K
0.28 × 0.13 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997 ) T_min = 0.94, T_max = 0.96
14336 measured reflections
1563 independent reflections
1413 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.080
S = 0.93
1563 reflections
73 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N8—H81⋯Cl1ⁱ	0.90	2.26	3.1456 (12)	171 (1)
N8—H82⋯Cl1	0.92	2.29	3.1910 (12)	171 (1)
N8—H83⋯Cl1ⁱⁱ	0.90	2.35	3.1923 (12)	157 (1)
C5—H53⋯O4ⁱⁱⁱ	0.96	2.67	3.5965 (18)	163 (1)
C7—H72⋯Cl1^iv	0.96	2.84	3.4708 (14)	124 (1)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y+2, -z+1; (iv) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 2001 ).; cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: CAMERON (Watkin et al., 1996 ); software used to prepare material for publication: CRYSTALS and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812003297/lh5384sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003297/lh5384Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812003297/lh5384Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536812003297/lh5384Isup4.cml

checkCIF report

Comment top

The asymmetic unit of the title compound, (I), consists of a 2-acetoxy-ethyl-ammonium cation and a chloride ion as shown in Figure 1. The ester motif [atoms C6/O2/C3/O4/C5] is approximately planar with the largest deviation from the mean plane for O2 (d = 0.029 Å). The central —CH₂—CH₂— unit is not in the often favoured antiperiplanar conformation, instead adopting a gauche conformation with a torsion angle of 57.42 (14)° for atoms O2—C6—C7—N8. This may be attributed to the stereoselective gauche effect (Amos et al., 1992), though an influence of the crystal packing on the molecular conformation of (I) cannot be ruled out. For comparison, the observed torsion angle is 67.6° in 1,2-difluoroethane (Akkerman et al., 2003), 73.7° for O-stearoylethanolamine hydrochloride (Tarafdar & Swamy, 2010) and 71.7° in 2-(benzoyloxy)ethanaminium nitrate (Gossage et al., 2010).

The three N—H units of (I) are engaged in apparently strong and highly directional N⁺—H···Cl^- hydrogen bonds with three symmetry-related Cl^- ions (Table 1). These interactions result in a tape-like arrangement of the respective ion pairs parallel to the crystallographic b axis (Figure 2). In the packing, the corrugated two dimensional supramolecular network defined by the N—H···Cl interactions is connected with neighbouring strands via weak C—H···Cl and C—H···O contacts (Table 1) in the direction of the crystallographic c and a axes, respectively. Interestingly, the observed packing behaviour is very similar to the structure of glycine ethyl ester hydrochloride (He et al., 2010), an isomer of (I), and the analogous glycine methyl ester (Vilela et al., 2009).

Related literature top

For the synthesis of the title compound, see: Hansen (1963). For related structures, see: Akkerman et al. (2003); Robinson et al. (2004); Vilela et al. (2009); Tarafdar & Swamy (2010); Gossage et al. (2010); He et al. (2010). For information on the gauche effect, see: Amos et al. (1992). For details of the H-atom treatment, see: Cooper et al. (2010). For the weighting scheme used in the refinement, see: Watkin (1994); Prince (1982).

Experimental top

The title compound was prepared from 2-aminoethanol and acetyl chloride according to the literature (Hansen, 1963). Crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of (I) in chloroform.

Computing details top

Data collection: COLLECT (Nonius, 2001).; cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of (I) with displacement ellipsoids drawn at 50% probability. The dotted line indicates a hydrogen bond.
	Fig. 2. The corrugated two dimensional supramolecular network defined by the N—H···Cl interactions forming tapes [i: 2 - x,1/2 + y,3/2 - z; ii: 2 - x,-1/2 + y,3/2 - z].

3-Methoxy-3-oxopropanaminium chloride top

Crystal data top

C₄H₁₀NO₂⁺·Cl⁻	F(000) = 296
M_r = 139.58	D_x = 1.349 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1729 reflections
a = 9.8469 (2) Å	θ = 5–27°
b = 5.3263 (1) Å	µ = 0.47 mm⁻¹
c = 13.2804 (2) Å	T = 150 K
β = 99.4638 (10)°	Block, clear_pale_colourless
V = 687.04 (2) Å³	0.28 × 0.13 × 0.08 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	1413 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ω scans	θ_max = 27.5°, θ_min = 5.2°
Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997)	h = −12→12
T_min = 0.94, T_max = 0.96	k = −6→6
14336 measured reflections	l = −17→17
1563 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.080	Method, part 1, Chebychev polynomial, (Watkin, 1994; Prince, 1982) [weight] = 1.0/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)] where A_i are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] [1-(deltaF/6*sigmaF)²]² A_i are: 37.6 62.5 38.0 16.9 4.31
S = 0.93	(Δ/σ)_max = 0.001
1563 reflections	Δρ_max = 0.25 e Å⁻³
73 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints

Crystal data top

C₄H₁₀NO₂⁺·Cl⁻	V = 687.04 (2) Å³
M_r = 139.58	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.8469 (2) Å	µ = 0.47 mm⁻¹
b = 5.3263 (1) Å	T = 150 K
c = 13.2804 (2) Å	0.28 × 0.13 × 0.08 mm
β = 99.4638 (10)°

Data collection top

Nonius KappaCCD diffractometer	1563 independent reflections
Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997)	1413 reflections with I > 2σ(I)
T_min = 0.94, T_max = 0.96	R_int = 0.014
14336 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 0.93	Δρ_max = 0.25 e Å⁻³
1563 reflections	Δρ_min = −0.28 e Å⁻³
73 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.92411 (3)	0.72604 (6)	0.59816 (2)	0.0244
O2	0.72167 (10)	1.11170 (19)	0.75243 (7)	0.0236
C3	0.62577 (14)	1.0662 (3)	0.66935 (11)	0.0241
O4	0.53381 (11)	0.9165 (2)	0.66871 (8)	0.0335
C5	0.64993 (16)	1.2257 (3)	0.58178 (12)	0.0307
C6	0.70489 (15)	0.9789 (3)	0.84455 (10)	0.0257
C7	0.76188 (14)	0.7166 (3)	0.84666 (10)	0.0240
N8	0.91018 (12)	0.7208 (2)	0.83652 (9)	0.0235
H51	0.7403	1.1944	0.5697	0.0451*
H52	0.6422	1.3972	0.6003	0.0448*
H53	0.5842	1.1883	0.5224	0.0448*
H61	0.7569	1.0756	0.8995	0.0291*
H62	0.6067	0.9749	0.8523	0.0288*
H71	0.7136	0.6156	0.7909	0.0287*
H72	0.7551	0.6399	0.9112	0.0286*
H81	0.9506	0.5763	0.8594	0.0342*
H82	0.9161	0.7420	0.7690	0.0341*
H83	0.9517	0.8494	0.8726	0.0346*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02820 (19)	0.02258 (18)	0.02136 (18)	−0.00083 (12)	0.00108 (12)	−0.00105 (12)
O2	0.0248 (5)	0.0223 (5)	0.0222 (5)	−0.0002 (4)	−0.0009 (4)	0.0002 (4)
C3	0.0238 (6)	0.0228 (6)	0.0243 (6)	0.0016 (5)	−0.0005 (5)	−0.0012 (5)
O4	0.0303 (5)	0.0348 (6)	0.0329 (6)	−0.0080 (5)	−0.0025 (4)	0.0039 (5)
C5	0.0332 (8)	0.0305 (8)	0.0268 (7)	−0.0027 (6)	0.0000 (6)	0.0047 (6)
C6	0.0292 (7)	0.0278 (7)	0.0200 (6)	0.0021 (6)	0.0041 (5)	−0.0010 (5)
C7	0.0268 (7)	0.0229 (6)	0.0215 (6)	−0.0016 (5)	0.0017 (5)	0.0021 (5)
N8	0.0287 (6)	0.0202 (5)	0.0208 (5)	0.0032 (4)	0.0015 (4)	0.0012 (4)

Geometric parameters (Å, º) top

O2—C3	1.3509 (16)	C6—H61	0.968
O2—C6	1.4459 (17)	C6—H62	0.989
C3—O4	1.2057 (18)	C7—N8	1.4886 (18)
C3—C5	1.490 (2)	C7—H71	0.973
C5—H51	0.945	C7—H72	0.961
C5—H52	0.952	N8—H81	0.896
C5—H53	0.955	N8—H82	0.915
C6—C7	1.504 (2)	N8—H83	0.895

C3—O2—C6	116.20 (11)	C7—C6—H62	110.2
O2—C3—O4	123.21 (13)	H61—C6—H62	109.8
O2—C3—C5	110.81 (12)	C6—C7—N8	110.65 (11)
O4—C3—C5	125.98 (13)	C6—C7—H71	111.4
C3—C5—H51	107.9	N8—C7—H71	107.7
C3—C5—H52	108.4	C6—C7—H72	109.3
H51—C5—H52	109.3	N8—C7—H72	107.5
C3—C5—H53	110.6	H71—C7—H72	110.2
H51—C5—H53	110.7	C7—N8—H81	110.1
H52—C5—H53	109.9	C7—N8—H82	108.2
O2—C6—C7	112.08 (11)	H81—N8—H82	110.0
O2—C6—H61	104.9	C7—N8—H83	109.3
C7—C6—H61	109.3	H81—N8—H83	109.7
O2—C6—H62	110.3	H82—N8—H83	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H81···Cl1ⁱ	0.90	2.26	3.1456 (12)	171 (1)
N8—H82···Cl1	0.92	2.29	3.1910 (12)	171 (1)
N8—H83···Cl1ⁱⁱ	0.90	2.35	3.1923 (12)	157 (1)
C5—H53···O4ⁱⁱⁱ	0.96	2.67	3.5965 (18)	163 (1)
C7—H72···Cl1^iv	0.96	2.84	3.4708 (14)	124 (1)

Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+1, −y+2, −z+1; (iv) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₄H₁₀NO₂⁺·Cl⁻
M_r	139.58
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	9.8469 (2), 5.3263 (1), 13.2804 (2)
β (°)	99.4638 (10)
V (Å³)	687.04 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.28 × 0.13 × 0.08

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997)
T_min, T_max	0.94, 0.96
No. of measured, independent and observed [I > 2σ(I)] reflections	14336, 1563, 1413
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.080, 0.93
No. of reflections	1563
No. of parameters	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.28

Computer programs: COLLECT (Nonius, 2001)., DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), CAMERON (Watkin et al., 1996), CRYSTALS (Betteridge et al., 2003) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H81···Cl1ⁱ	0.896	2.2566	3.1456 (12)	171.32 (3)
N8—H82···Cl1	0.915	2.2851	3.1910 (12)	170.64 (3)
N8—H83···Cl1ⁱⁱ	0.895	2.3484	3.1923 (12)	157.11 (3)
C5—H53···O4ⁱⁱⁱ	0.955	2.6710	3.5965 (18)	163.27 (4)
C7—H72···Cl1^iv	0.961	2.8438	3.4708 (14)	123.70 (3)

Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+1, −y+2, −z+1; (iv) x, −y+3/2, z+1/2.

Footnotes

‡Present address: Institut für Organische Chemie, TU Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany.

Acknowledgements

TG thanks Deutsche Forschungsgemeinschaft (DFG), Germany, for generous funding (GR 3693/1–1:1).

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