1-Hydroxymethyl-1-methylethan­aminium chloride

Li, Y.-F.; Feng, M.-L.; Liu, S.; Yang, H.-Y.; Zhu, H.-J.

doi:10.1107/S1600536808015018

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1150

doi:10.1107/S1600536808015018

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1-Hydroxymethyl-1-methylethanaminium chloride

Yu-Feng Li,^a Mei-Li Feng,^a Shan Liu,^a Hai-Yu Yang ^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 14 May 2008; accepted 18 May 2008; online 24 May 2008)

The asymmetric unit of the title compound, C₄H₁₂NO⁺·Cl⁻, contains two independent ion pairs. Weak intramolecular C—H⋯O and N—H⋯O hydrogen bonds result in the formation of three five-membered rings, which have envelope conformations. The crystal structure contains intermolecular O—H⋯Cl, N—H⋯O, N—H⋯Cl and O—H⋯O hydrogen bonds.

Related literature

For related literature, see: Senkus (1948 ). For general background, see: Pazenok (2007 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₄H₁₂NO⁺·Cl⁻
M_r = 125.60
Monoclinic, P 2₁ /n
a = 6.4940 (13) Å
b = 9.5230 (19) Å
c = 21.903 (4) Å
β = 91.88 (3)°
V = 1353.8 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 298 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf-Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.874, T_max = 0.913
2651 measured reflections
2421 independent reflections
1857 reflections with I > 2σ(I)
R_int = 0.020
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.153
S = 1.01
2421 reflections
131 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 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
O1—H1A⋯Cl1	0.82 (3)	2.25 (4)	3.067 (2)	174 (3)
N1—H1B⋯O2	0.89	2.02	2.876 (3)	161
N1—H1C⋯Cl1ⁱ	0.89	2.33	3.216 (3)	171
N1—H1G⋯Cl1ⁱⁱ	0.89	2.42	3.261 (2)	157
O2—H2D⋯O1ⁱⁱⁱ	0.82	1.91	2.731 (3)	175
N2—H2E⋯Cl1	0.89	2.53	3.391 (2)	163
N2—H2E⋯O2	0.89	2.49	2.811 (3)	102
N2—H2F⋯Cl2^iv	0.89	2.24	3.130 (2)	177
N2—H2G⋯Cl2	0.89	2.27	3.144 (2)	169
C2—H2A⋯O1	0.96	2.53	2.880 (4)	102
C6—H6A⋯O2	0.96	2.59	2.933 (4)	101
Symmetry codes: (i) x+1, y, z; (ii) -x, -y, -z+1; (iii) -x, -y+1, -z+1; (iv) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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: 10.1107/S1600536808015018/hk2463sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015018/hk2463Isup2.hkl

checkCIF report

Comment top

The title compound, (I), is an important intermediate for the synthesis of 2-amino-2-methylpropylsulfate, which can be used to synthese 2-methyl-1-(methyl- thio)propane-2-amine (Pazenok, 2007). We report herein the crystal structure of the title compound, (I).

The asymmetric unit of (I) contains two independent molecules (Fig. 1). The bond lengths (Allen et al., 1987) and angles are within normal ranges . The weak intramolecular C-H···O and N-H···O hydrogen bonds (Table 1) result in the formation of three five-membered rings A (C2-C4/O1/H2A), B (C6-C8/O2/H6A) and C (C7/C8/O2/N2/H2E). They adopt envelope conformations, with C3 and C7 atoms displaced by -0.637 (3), -0.686 (4) and 0.711 (3) Å from the planes of the other ring atoms, respectively.

In the crystal structure, intramolecular O-H···Cl, N-H···O and N-H···Cl and intermolecular N-H···Cl and O-H···O hydrogen bonds (Table 1) link the molecules to form a three dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For related literature, see: Senkus (1948). For general background, see: Pazenok (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I), was synthesized according to the literature method (Senkus, 1948). Crystals suitable for X-ray analysis were obtained by dissolving (I) (0.30 g, 2.4 mmol) in methanol (25 ml) and evaporating the solvent slowly at room temperature for about 4 d.

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 the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Hydrogen bonds are shown as dashed lines.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

1-Hydroxymethyl-1-methylethanaminium chloride top

Crystal data top

C₄H₁₂NO⁺·Cl⁻	F(000) = 544
M_r = 125.60	D_x = 1.232 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 6.4940 (13) Å	θ = 11–14°
b = 9.5230 (19) Å	µ = 0.46 mm⁻¹
c = 21.903 (4) Å	T = 298 K
β = 91.88 (3)°	Block, colorless
V = 1353.8 (5) Å³	0.30 × 0.20 × 0.20 mm
Z = 8

Data collection top

Enraf-Nonius CAD-4 diffractometer	1857 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 25.2°, θ_min = 1.9°
ω/2θ scans	h = 0→7
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
T_min = 0.874, T_max = 0.913	l = −26→26
2651 measured reflections	3 standard reflections every 120 min
2421 independent reflections	intensity decay: none

Refinement top

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.154	w = 1/[σ²(F_o²) + (0.1P)² + 0.25P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
2421 reflections	Δρ_max = 0.26 e Å⁻³
131 parameters	Δρ_min = −0.28 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (4)

Crystal data top

C₄H₁₂NO⁺·Cl⁻	V = 1353.8 (5) Å³
M_r = 125.60	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.4940 (13) Å	µ = 0.46 mm⁻¹
b = 9.5230 (19) Å	T = 298 K
c = 21.903 (4) Å	0.30 × 0.20 × 0.20 mm
β = 91.88 (3)°

Data collection top

Enraf-Nonius CAD-4 diffractometer	1857 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.020
T_min = 0.874, T_max = 0.913	3 standard reflections every 120 min
2651 measured reflections	intensity decay: none
2421 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.26 e Å⁻³
2421 reflections	Δρ_min = −0.28 e Å⁻³
131 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 > 2sigma(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	−0.24225 (12)	0.14202 (8)	0.53408 (3)	0.0414 (3)
Cl2	−0.24989 (15)	0.01158 (9)	0.76365 (4)	0.0527 (3)
O1	−0.0723 (3)	0.3564 (2)	0.44418 (11)	0.0468 (6)
H1A	−0.121 (6)	0.304 (4)	0.4694 (14)	0.070*
O2	0.1531 (3)	0.3696 (2)	0.58458 (8)	0.0383 (5)
H2D	0.1269	0.4503	0.5738	0.057*
N1	0.2905 (4)	0.1957 (2)	0.48659 (10)	0.0313 (6)
H1B	0.2196	0.2435	0.5138	0.047*
H1C	0.4221	0.1910	0.4990	0.047*
H1G	0.2393	0.1093	0.4830	0.047*
N2	−0.0750 (4)	0.2407 (2)	0.67597 (10)	0.0304 (6)
H2E	−0.1178	0.2352	0.6370	0.046*
H2F	−0.1221	0.3195	0.6923	0.046*
H2G	−0.1221	0.1672	0.6964	0.046*
C1	0.3962 (6)	0.1829 (4)	0.38056 (15)	0.0485 (9)
H1D	0.3885	0.2266	0.3411	0.073*
H1E	0.3397	0.0899	0.3777	0.073*
H1F	0.5376	0.1778	0.3947	0.073*
C2	0.3599 (5)	0.4154 (3)	0.43319 (14)	0.0410 (7)
H2A	0.2787	0.4665	0.4615	0.061*
H2B	0.3559	0.4628	0.3945	0.061*
H2C	0.4998	0.4101	0.4486	0.061*
C3	0.2741 (4)	0.2692 (3)	0.42531 (12)	0.0300 (6)
C4	0.0495 (5)	0.2723 (3)	0.40505 (14)	0.0383 (7)
H4A	0.0375	0.3090	0.3638	0.046*
H4B	−0.0039	0.1771	0.4044	0.046*
C5	0.2240 (5)	0.2504 (4)	0.74660 (14)	0.0467 (8)
H5A	0.1744	0.3366	0.7635	0.070*
H5B	0.3717	0.2483	0.7502	0.070*
H5C	0.1685	0.1724	0.7684	0.070*
C6	0.2298 (5)	0.1056 (3)	0.65041 (15)	0.0464 (8)
H6A	0.1841	0.1034	0.6083	0.070*
H6B	0.1740	0.0265	0.6714	0.070*
H6C	0.3776	0.1016	0.6530	0.070*
C7	0.1566 (4)	0.2409 (3)	0.67977 (12)	0.0305 (6)
C8	0.2295 (5)	0.3699 (3)	0.64625 (13)	0.0369 (7)
H8A	0.1820	0.4536	0.6667	0.044*
H8B	0.3789	0.3717	0.6470	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0418 (5)	0.0385 (5)	0.0435 (5)	−0.0061 (3)	−0.0065 (3)	0.0059 (3)
Cl2	0.0708 (6)	0.0471 (5)	0.0406 (5)	−0.0228 (4)	0.0074 (4)	0.0050 (3)
O1	0.0390 (12)	0.0394 (13)	0.0628 (15)	0.0087 (10)	0.0117 (11)	0.0180 (10)
O2	0.0545 (13)	0.0310 (11)	0.0296 (11)	0.0003 (10)	0.0050 (9)	0.0044 (8)
N1	0.0321 (13)	0.0338 (12)	0.0281 (12)	0.0047 (10)	0.0007 (10)	0.0042 (10)
N2	0.0340 (13)	0.0274 (12)	0.0299 (12)	0.0009 (10)	0.0042 (10)	−0.0003 (9)
C1	0.059 (2)	0.053 (2)	0.0340 (16)	0.0105 (17)	0.0127 (15)	−0.0028 (14)
C2	0.0424 (18)	0.0367 (17)	0.0435 (17)	−0.0089 (14)	−0.0020 (14)	0.0048 (13)
C3	0.0355 (15)	0.0314 (15)	0.0230 (13)	−0.0019 (12)	0.0018 (11)	0.0026 (11)
C4	0.0381 (17)	0.0379 (16)	0.0385 (16)	−0.0033 (14)	−0.0065 (13)	0.0047 (13)
C5	0.052 (2)	0.057 (2)	0.0313 (16)	−0.0046 (17)	−0.0061 (14)	0.0075 (14)
C6	0.056 (2)	0.0366 (17)	0.0473 (19)	0.0154 (15)	0.0069 (16)	0.0066 (14)
C7	0.0299 (14)	0.0332 (15)	0.0284 (14)	0.0004 (12)	0.0029 (11)	0.0015 (11)
C8	0.0416 (17)	0.0365 (16)	0.0328 (15)	−0.0097 (14)	0.0020 (13)	0.0024 (12)

Geometric parameters (Å, º) top

O1—C4	1.430 (4)	O2—C8	1.424 (3)
O1—H1A	0.82 (3)	O2—H2D	0.8200
N1—C3	1.515 (3)	N2—C7	1.503 (4)
N1—H1B	0.8900	N2—H2E	0.8900
N1—H1C	0.8900	N2—H2F	0.8900
N1—H1G	0.8900	N2—H2G	0.8900
C1—C3	1.522 (4)	C5—C7	1.517 (4)
C1—H1D	0.9600	C5—H5A	0.9600
C1—H1E	0.9600	C5—H5B	0.9600
C1—H1F	0.9600	C5—H5C	0.9600
C2—C3	1.507 (4)	C6—C7	1.523 (4)
C2—H2A	0.9600	C6—H6A	0.9600
C2—H2B	0.9600	C6—H6B	0.9600
C2—H2C	0.9600	C6—H6C	0.9600
C3—C4	1.511 (4)	C7—C8	1.515 (4)
C4—H4A	0.9700	C8—H8A	0.9700
C4—H4B	0.9700	C8—H8B	0.9700

C4—O1—H1A	107 (3)	C8—O2—H2D	109.5
C3—N1—H1B	109.5	C7—N2—H2E	109.5
C3—N1—H1C	109.5	C7—N2—H2F	109.5
H1B—N1—H1C	109.5	H2E—N2—H2F	109.5
C3—N1—H1G	109.5	C7—N2—H2G	109.5
H1B—N1—H1G	109.5	H2E—N2—H2G	109.5
H1C—N1—H1G	109.5	H2F—N2—H2G	109.5
C3—C1—H1D	109.5	C7—C5—H5A	109.5
C3—C1—H1E	109.5	C7—C5—H5B	109.5
H1D—C1—H1E	109.5	H5A—C5—H5B	109.5
C3—C1—H1F	109.5	C7—C5—H5C	109.5
H1D—C1—H1F	109.5	H5A—C5—H5C	109.5
H1E—C1—H1F	109.5	H5B—C5—H5C	109.5
C3—C2—H2A	109.5	C7—C6—H6A	109.5
C3—C2—H2B	109.5	C7—C6—H6B	109.5
H2A—C2—H2B	109.5	H6A—C6—H6B	109.5
C3—C2—H2C	109.5	C7—C6—H6C	109.5
H2A—C2—H2C	109.5	H6A—C6—H6C	109.5
H2B—C2—H2C	109.5	H6B—C6—H6C	109.5
C2—C3—C4	111.4 (2)	N2—C7—C8	107.6 (2)
C2—C3—N1	108.1 (2)	N2—C7—C5	108.1 (2)
C4—C3—N1	107.9 (2)	C8—C7—C5	109.5 (2)
C2—C3—C1	112.0 (3)	N2—C7—C6	107.5 (2)
C4—C3—C1	109.9 (3)	C8—C7—C6	112.0 (2)
N1—C3—C1	107.3 (2)	C5—C7—C6	112.0 (2)
O1—C4—C3	112.5 (2)	O2—C8—C7	110.7 (2)
O1—C4—H4A	109.1	O2—C8—H8A	109.5
C3—C4—H4A	109.1	C7—C8—H8A	109.5
O1—C4—H4B	109.1	O2—C8—H8B	109.5
C3—C4—H4B	109.1	C7—C8—H8B	109.5
H4A—C4—H4B	107.8	H8A—C8—H8B	108.1

C2—C3—C4—O1	−53.1 (3)	N2—C7—C8—O2	−57.7 (3)
N1—C3—C4—O1	65.4 (3)	C5—C7—C8—O2	−174.9 (2)
C1—C3—C4—O1	−177.8 (2)	C6—C7—C8—O2	60.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl1	0.82 (3)	2.25 (4)	3.067 (2)	174 (3)
N1—H1B···O2	0.89	2.02	2.876 (3)	161
N1—H1C···Cl1ⁱ	0.89	2.33	3.216 (3)	171
N1—H1G···Cl1ⁱⁱ	0.89	2.42	3.261 (2)	157
O2—H2D···O1ⁱⁱⁱ	0.82	1.91	2.731 (3)	175
N2—H2E···Cl1	0.89	2.53	3.391 (2)	163
N2—H2E···O2	0.89	2.49	2.811 (3)	102
N2—H2F···Cl2^iv	0.89	2.24	3.130 (2)	177
N2—H2G···Cl2	0.89	2.27	3.144 (2)	169
C2—H2A···O1	0.96	2.53	2.880 (4)	102
C6—H6A···O2	0.96	2.59	2.933 (4)	101

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

Experimental details

Crystal data
Chemical formula	C₄H₁₂NO⁺·Cl⁻
M_r	125.60
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	6.4940 (13), 9.5230 (19), 21.903 (4)
β (°)	91.88 (3)
V (Å³)	1353.8 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf-Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.874, 0.913
No. of measured, independent and observed [I > 2σ(I)] reflections	2651, 2421, 1857
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.154, 1.01
No. of reflections	2421
No. of parameters	131
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.28

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
O1—H1A···Cl1	0.82 (3)	2.25 (4)	3.067 (2)	174 (3)
N1—H1B···O2	0.8900	2.0200	2.876 (3)	161.00
N1—H1C···Cl1ⁱ	0.8900	2.3300	3.216 (3)	171.00
N1—H1G···Cl1ⁱⁱ	0.8900	2.4200	3.261 (2)	157.00
O2—H2D···O1ⁱⁱⁱ	0.8200	1.9100	2.731 (3)	175.00
N2—H2E···Cl1	0.8900	2.5300	3.391 (2)	163.00
N2—H2E···O2	0.8900	2.4900	2.811 (3)	102.00
N2—H2F···Cl2^iv	0.8900	2.2400	3.130 (2)	177.00
N2—H2G···Cl2	0.8900	2.2700	3.144 (2)	169.00
C2—H2A···O1	0.9600	2.5300	2.880 (4)	102.00
C6—H6A···O2	0.9600	2.5900	2.933 (4)	101.00

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

Acknowledgements

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

References

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