1-Meth­oxy-2-methyl­propan-2-aminium 2,2,2-trifluoro­acetate

Wang, K.; Li, Y.-F.; Song, X.-H.; Feng, M.-L.; Zhu, H.-J.

doi:10.1107/S1600536810019100

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1487

https://doi.org/10.1107/S1600536810019100

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1-Methoxy-2-methylpropan-2-aminium 2,2,2-trifluoroacetate

Kai Wang,^a Yu-Feng Li,^a Xiang-Hua Song,^a Mei-Li Feng ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhj@njut.edu.cn

(Received 4 May 2010; accepted 21 May 2010; online 29 May 2010)

In the title salt, C₅H₁₄NO⁺·C₂F₃O₂⁻, the cation and anion are linked by N—H⋯O and O—H⋯N hydrogen bonds, generating a three-dimensional network.

Related literature

The title compound is an intermediate in the synthesis of 1-methoxy-N,2-dimethylpropan-2-amine. For the synthesis of the title compound, see: Maeda et al. (2004 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₅H₁₄NO⁺·C₂F₃O₂⁻
M_r = 217.19
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.6680 (13) Å
b = 8.9900 (18) Å
c = 17.862 (4) Å
V = 1070.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 293 K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.961, T_max = 0.987
1861 measured reflections
1150 independent reflections
784 reflections with I > 2σ(I)
R_int = 0.038
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.183
S = 1.01
1150 reflections
121 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0A⋯O2	0.89	1.99	2.854 (5)	163
N—H0B⋯O2ⁱ	0.89	2.00	2.859 (5)	161
N—H0C⋯O3ⁱⁱ	0.89	1.92	2.802 (6)	169
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810019100/jh2152sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810019100/jh2152Isup2.hkl

checkCIF report

Comment top

The title compound, 1-methoxy-2-methylpropan-2-aminium 2,2,2-trifluoroacetate is an important intermediate for the synthesis of 1-methoxy-N,2-dimethylpropan-2-amine. We herein report its crystal structure.

The molecular structure of (I) is shown in Fig. 1, and the selected geometric parameters are given in Table 1. The bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987).

In the molecule of (I), (Fig.1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. The crystal of this compound was connected together via C—H···O, and N—H···O inter- and intramolecular hydrogen bonds to form a three dimensional network, which seems to be very effective in the stabilization of the crystal structure.

As can be seen from the packing diagram, (Fig. 2), the molecules are stacked along the a axis.

Related literature top

The title compound is an important intermediate for the synthesis of 1-methoxy-N,2-dimethylpropan-2-amine. For the synthesis of the title compound, see: Maeda et al. (2004); For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was synthesized according to the literature (Maeda et al., 2004). The crystals were obtained by dissolving (I) (0.52 g, 2.4 mmol) in 25 ml me thanol and evaporating the solvent slowly at room temperature for about 4 d.

Structure description top

The molecular structure of (I) is shown in Fig. 1, and the selected geometric parameters are given in Table 1. The bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987).

As can be seen from the packing diagram, (Fig. 2), the molecules are stacked along the a axis.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

1-Methoxy-2-methylpropan-2-aminium 2,2,2-trifluoroacetate top

Crystal data top

C₅H₁₄NO⁺·C₂F₃O₂⁻	F(000) = 456
M_r = 217.19	D_x = 1.347 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 6.6680 (13) Å	θ = 9–12°
b = 8.9900 (18) Å	µ = 0.14 mm⁻¹
c = 17.862 (4) Å	T = 293 K
V = 1070.7 (4) Å³	Block, colourless
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	784 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
Graphite monochromator	θ_max = 25.3°, θ_min = 2.3°
ω/2θ scans	h = −7→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.961, T_max = 0.987	l = 0→21
1861 measured reflections	3 standard reflections every 200 reflections
1150 independent reflections	intensity decay: 1%

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.183	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1P)² + 0.350P] where P = (F_o² + 2F_c²)/3
1150 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.39 e Å⁻³
2 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₅H₁₄NO⁺·C₂F₃O₂⁻	V = 1070.7 (4) Å³
M_r = 217.19	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.6680 (13) Å	µ = 0.14 mm⁻¹
b = 8.9900 (18) Å	T = 293 K
c = 17.862 (4) Å	0.30 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	784 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.038
T_min = 0.961, T_max = 0.987	3 standard reflections every 200 reflections
1861 measured reflections	intensity decay: 1%
1150 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	2 restraints
wR(F²) = 0.183	H-atom parameters constrained
S = 1.01	Δρ_max = 0.39 e Å⁻³
1150 reflections	Δρ_min = −0.27 e Å⁻³
121 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
N	0.4436 (6)	0.2188 (5)	0.4225 (2)	0.0507 (10)
H0A	0.4554	0.1919	0.4702	0.076*
H0B	0.3281	0.2667	0.4159	0.076*
H0C	0.5450	0.2784	0.4102	0.076*
O1	0.2833 (6)	−0.0471 (5)	0.4723 (2)	0.0789 (13)
C1	0.1216 (11)	−0.1286 (9)	0.5000 (4)	0.093 (2)
H1A	0.1419	−0.1486	0.5522	0.139*
H1B	0.1112	−0.2209	0.4732	0.139*
H1C	0.0003	−0.0725	0.4935	0.139*
C2	0.2708 (9)	−0.0130 (8)	0.3959 (3)	0.0674 (16)
H2A	0.1465	0.0392	0.3857	0.081*
H2B	0.2719	−0.1040	0.3667	0.081*
C3	0.4477 (8)	0.0837 (6)	0.3739 (3)	0.0557 (12)
C4	0.4273 (10)	0.1332 (8)	0.2930 (3)	0.0755 (18)
H4A	0.2998	0.1808	0.2861	0.113*
H4B	0.4365	0.0482	0.2607	0.113*
H4C	0.5328	0.2020	0.2812	0.113*
C5	0.6472 (9)	0.0065 (9)	0.3891 (4)	0.084 (2)
H5A	0.6533	−0.0230	0.4407	0.126*
H5B	0.7554	0.0737	0.3784	0.126*
H5C	0.6586	−0.0799	0.3578	0.126*
F1	0.5540 (9)	0.0216 (7)	0.7374 (2)	0.139 (2)
F2	0.7402 (6)	−0.0271 (7)	0.6453 (4)	0.159 (3)
F3	0.4744 (7)	−0.1451 (5)	0.6637 (3)	0.1188 (17)
O2	0.5367 (5)	0.1809 (4)	0.5773 (2)	0.0642 (10)
O3	0.2549 (5)	0.1057 (5)	0.6350 (2)	0.0685 (11)
C6	0.5543 (12)	−0.0119 (9)	0.6655 (4)	0.088
C7	0.4376 (8)	0.1040 (6)	0.6208 (3)	0.0526 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0321 (18)	0.067 (2)	0.053 (2)	−0.004 (2)	−0.0039 (18)	0.008 (2)
O1	0.058 (2)	0.095 (3)	0.084 (3)	−0.028 (2)	−0.0068 (19)	0.018 (2)
C1	0.068 (4)	0.104 (5)	0.106 (4)	−0.029 (4)	0.003 (4)	0.024 (5)
C2	0.053 (3)	0.069 (4)	0.080 (4)	−0.011 (3)	−0.006 (3)	−0.009 (3)
C3	0.039 (2)	0.067 (3)	0.062 (3)	0.001 (3)	0.004 (2)	−0.004 (3)
C4	0.069 (4)	0.105 (4)	0.053 (3)	0.001 (4)	0.008 (3)	−0.011 (3)
C5	0.052 (3)	0.086 (5)	0.114 (5)	0.018 (4)	0.017 (3)	0.004 (4)
F1	0.149 (4)	0.191 (5)	0.078 (3)	0.032 (5)	−0.040 (3)	0.025 (3)
F2	0.048 (2)	0.199 (6)	0.230 (6)	0.051 (3)	0.044 (3)	0.126 (5)
F3	0.112 (4)	0.077 (2)	0.167 (4)	0.017 (3)	0.007 (3)	0.035 (3)
O2	0.0486 (19)	0.088 (3)	0.056 (2)	−0.018 (2)	−0.0095 (17)	0.021 (2)
O3	0.0305 (18)	0.090 (3)	0.085 (3)	0.0088 (19)	0.0031 (16)	0.021 (2)
C6	0.088	0.088	0.088	0.000	0.000	0.000
C7	0.049 (3)	0.060 (3)	0.049 (3)	0.002 (3)	−0.003 (2)	0.010 (3)

Geometric parameters (Å, º) top

N—C3	1.493 (7)	C3—C5	1.525 (8)
N—H0A	0.8900	C4—H4A	0.9600
N—H0B	0.8900	C4—H4B	0.9600
N—H0C	0.8900	C4—H4C	0.9600
O1—C1	1.394 (7)	C5—H5A	0.9600
O1—C2	1.402 (7)	C5—H5B	0.9600
C1—H1A	0.9600	C5—H5C	0.9600
C1—H1B	0.9600	F1—C6	1.319 (8)
C1—H1C	0.9600	F2—C6	1.298 (9)
C2—C3	1.517 (8)	F3—C6	1.311 (9)
C2—H2A	0.9700	O2—C7	1.232 (6)
C2—H2B	0.9700	O3—C7	1.244 (6)
C3—C4	1.518 (8)	C6—C7	1.526 (9)

C3—N—H0A	109.5	C2—C3—C5	111.8 (4)
C3—N—H0B	109.5	C4—C3—C5	112.4 (5)
H0A—N—H0B	109.5	C3—C4—H4A	109.5
C3—N—H0C	109.5	C3—C4—H4B	109.5
H0A—N—H0C	109.5	H4A—C4—H4B	109.5
H0B—N—H0C	109.5	C3—C4—H4C	109.5
C1—O1—C2	114.4 (5)	H4A—C4—H4C	109.5
O1—C1—H1A	109.5	H4B—C4—H4C	109.5
O1—C1—H1B	109.5	C3—C5—H5A	109.5
H1A—C1—H1B	109.5	C3—C5—H5B	109.5
O1—C1—H1C	109.5	H5A—C5—H5B	109.5
H1A—C1—H1C	109.5	C3—C5—H5C	109.5
H1B—C1—H1C	109.5	H5A—C5—H5C	109.5
O1—C2—C3	109.3 (4)	H5B—C5—H5C	109.5
O1—C2—H2A	109.8	F2—C6—F3	106.6 (7)
C3—C2—H2A	109.8	F2—C6—F1	107.2 (7)
O1—C2—H2B	109.8	F3—C6—F1	103.4 (7)
C3—C2—H2B	109.8	F2—C6—C7	114.4 (6)
H2A—C2—H2B	108.3	F3—C6—C7	113.8 (6)
N—C3—C2	107.6 (4)	F1—C6—C7	110.6 (6)
N—C3—C4	108.2 (5)	O2—C7—O3	130.3 (5)
C2—C3—C4	110.2 (5)	O2—C7—C6	116.1 (5)
N—C3—C5	106.4 (5)	O3—C7—C6	113.6 (5)

C1—O1—C2—C3	176.4 (5)	F3—C6—C7—O2	−130.9 (6)
O1—C2—C3—N	−57.2 (6)	F1—C6—C7—O2	113.3 (7)
O1—C2—C3—C4	−175.0 (5)	F2—C6—C7—O3	172.5 (7)
O1—C2—C3—C5	59.3 (6)	F3—C6—C7—O3	49.6 (8)
F2—C6—C7—O2	−8.0 (9)	F1—C6—C7—O3	−66.3 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O1	0.89	2.44	2.766 (6)	102
N—H0A···O2	0.89	1.99	2.854 (5)	163
N—H0B···O2ⁱ	0.89	2.00	2.859 (5)	161
N—H0C···O3ⁱⁱ	0.89	1.92	2.802 (6)	169
C5—H5A···O1	0.96	2.54	2.886 (8)	101

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

Experimental details

Crystal data
Chemical formula	C₅H₁₄NO⁺·C₂F₃O₂⁻
M_r	217.19
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	6.6680 (13), 8.9900 (18), 17.862 (4)
V (Å³)	1070.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.961, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	1861, 1150, 784
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.183, 1.01
No. of reflections	1150
No. of parameters	121
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.27

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O1	0.8900	2.4400	2.766 (6)	102.00
N—H0A···O2	0.8900	1.9900	2.854 (5)	163.00
N—H0B···O2ⁱ	0.8900	2.0000	2.859 (5)	161.00
N—H0C···O3ⁱⁱ	0.8900	1.9200	2.802 (6)	169.00
C5—H5A···O1	0.9600	2.5400	2.886 (8)	101.00

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for the support.

References

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