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1-Hydroxymethyl-1-methylethan­aminium chloride

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[Senkus, M. (1948). Ind. Engineering Chem. 40, 506-508.]). For general background, see: Pazenok (2007[Pazenok, S. (2007). Bayer Cropscience A.-G., Germany. WO patent 2007 022 900.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data
  • C4H12NO+·Cl

  • Mr = 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[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.874, Tmax = 0.913

  • 2651 measured reflections

  • 2421 independent reflections

  • 1857 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.26 e Å−3

  • Δρmin = −0.28 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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⋯Cl2iv 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[Enraf-Nonius (1985). CAD-4 Software. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

H1A atom (for OH) was located in a difference syntheses and refined [O1-H1A = 0.82 (3) Å and Uiso(H) = 0.070 Å2]. The remaining H atoms were positioned geometrically, with O-H = 0.82 Å (for OH), N-H = 0.89 Å (for NH3) and C-H = 0.97 and 0.96 Å for methylene and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C,O,N), where x = 1.2 for methylene H, and x = 1.5 for all other H atoms.

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
[Figure 1] 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.
[Figure 2] Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.
1-Hydroxymethyl-1-methylethanaminium chloride top
Crystal data top
C4H12NO+·ClF(000) = 544
Mr = 125.60Dx = 1.232 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 6.4940 (13) Åθ = 11–14°
b = 9.5230 (19) ŵ = 0.46 mm1
c = 21.903 (4) ÅT = 298 K
β = 91.88 (3)°Block, colorless
V = 1353.8 (5) Å30.30 × 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 tubeRint = 0.020
Graphite monochromatorθmax = 25.2°, θmin = 1.9°
ω/2θ scansh = 07
Absorption correction: ψ scan
(North et al., 1968)
k = 011
Tmin = 0.874, Tmax = 0.913l = 2626
2651 measured reflections3 standard reflections every 120 min
2421 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.154 w = 1/[σ2(Fo2) + (0.1P)2 + 0.25P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
2421 reflectionsΔρmax = 0.26 e Å3
131 parametersΔρmin = 0.28 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.018 (4)
Crystal data top
C4H12NO+·ClV = 1353.8 (5) Å3
Mr = 125.60Z = 8
Monoclinic, P21/nMo Kα radiation
a = 6.4940 (13) ŵ = 0.46 mm1
b = 9.5230 (19) ÅT = 298 K
c = 21.903 (4) Å0.30 × 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)
Rint = 0.020
Tmin = 0.874, Tmax = 0.9133 standard reflections every 120 min
2651 measured reflections intensity decay: none
2421 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0401 restraint
wR(F2) = 0.154H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.26 e Å3
2421 reflectionsΔρmin = 0.28 e Å3
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
xyzUiso*/Ueq
Cl10.24225 (12)0.14202 (8)0.53408 (3)0.0414 (3)
Cl20.24989 (15)0.01158 (9)0.76365 (4)0.0527 (3)
O10.0723 (3)0.3564 (2)0.44418 (11)0.0468 (6)
H1A0.121 (6)0.304 (4)0.4694 (14)0.070*
O20.1531 (3)0.3696 (2)0.58458 (8)0.0383 (5)
H2D0.12690.45030.57380.057*
N10.2905 (4)0.1957 (2)0.48659 (10)0.0313 (6)
H1B0.21960.24350.51380.047*
H1C0.42210.19100.49900.047*
H1G0.23930.10930.48300.047*
N20.0750 (4)0.2407 (2)0.67597 (10)0.0304 (6)
H2E0.11780.23520.63700.046*
H2F0.12210.31950.69230.046*
H2G0.12210.16720.69640.046*
C10.3962 (6)0.1829 (4)0.38056 (15)0.0485 (9)
H1D0.38850.22660.34110.073*
H1E0.33970.08990.37770.073*
H1F0.53760.17780.39470.073*
C20.3599 (5)0.4154 (3)0.43319 (14)0.0410 (7)
H2A0.27870.46650.46150.061*
H2B0.35590.46280.39450.061*
H2C0.49980.41010.44860.061*
C30.2741 (4)0.2692 (3)0.42531 (12)0.0300 (6)
C40.0495 (5)0.2723 (3)0.40505 (14)0.0383 (7)
H4A0.03750.30900.36380.046*
H4B0.00390.17710.40440.046*
C50.2240 (5)0.2504 (4)0.74660 (14)0.0467 (8)
H5A0.17440.33660.76350.070*
H5B0.37170.24830.75020.070*
H5C0.16850.17240.76840.070*
C60.2298 (5)0.1056 (3)0.65041 (15)0.0464 (8)
H6A0.18410.10340.60830.070*
H6B0.17400.02650.67140.070*
H6C0.37760.10160.65300.070*
C70.1566 (4)0.2409 (3)0.67977 (12)0.0305 (6)
C80.2295 (5)0.3699 (3)0.64625 (13)0.0369 (7)
H8A0.18200.45360.66670.044*
H8B0.37890.37170.64700.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0418 (5)0.0385 (5)0.0435 (5)0.0061 (3)0.0065 (3)0.0059 (3)
Cl20.0708 (6)0.0471 (5)0.0406 (5)0.0228 (4)0.0074 (4)0.0050 (3)
O10.0390 (12)0.0394 (13)0.0628 (15)0.0087 (10)0.0117 (11)0.0180 (10)
O20.0545 (13)0.0310 (11)0.0296 (11)0.0003 (10)0.0050 (9)0.0044 (8)
N10.0321 (13)0.0338 (12)0.0281 (12)0.0047 (10)0.0007 (10)0.0042 (10)
N20.0340 (13)0.0274 (12)0.0299 (12)0.0009 (10)0.0042 (10)0.0003 (9)
C10.059 (2)0.053 (2)0.0340 (16)0.0105 (17)0.0127 (15)0.0028 (14)
C20.0424 (18)0.0367 (17)0.0435 (17)0.0089 (14)0.0020 (14)0.0048 (13)
C30.0355 (15)0.0314 (15)0.0230 (13)0.0019 (12)0.0018 (11)0.0026 (11)
C40.0381 (17)0.0379 (16)0.0385 (16)0.0033 (14)0.0065 (13)0.0047 (13)
C50.052 (2)0.057 (2)0.0313 (16)0.0046 (17)0.0061 (14)0.0075 (14)
C60.056 (2)0.0366 (17)0.0473 (19)0.0154 (15)0.0069 (16)0.0066 (14)
C70.0299 (14)0.0332 (15)0.0284 (14)0.0004 (12)0.0029 (11)0.0015 (11)
C80.0416 (17)0.0365 (16)0.0328 (15)0.0097 (14)0.0020 (13)0.0024 (12)
Geometric parameters (Å, º) top
O1—C41.430 (4)O2—C81.424 (3)
O1—H1A0.82 (3)O2—H2D0.8200
N1—C31.515 (3)N2—C71.503 (4)
N1—H1B0.8900N2—H2E0.8900
N1—H1C0.8900N2—H2F0.8900
N1—H1G0.8900N2—H2G0.8900
C1—C31.522 (4)C5—C71.517 (4)
C1—H1D0.9600C5—H5A0.9600
C1—H1E0.9600C5—H5B0.9600
C1—H1F0.9600C5—H5C0.9600
C2—C31.507 (4)C6—C71.523 (4)
C2—H2A0.9600C6—H6A0.9600
C2—H2B0.9600C6—H6B0.9600
C2—H2C0.9600C6—H6C0.9600
C3—C41.511 (4)C7—C81.515 (4)
C4—H4A0.9700C8—H8A0.9700
C4—H4B0.9700C8—H8B0.9700
C4—O1—H1A107 (3)C8—O2—H2D109.5
C3—N1—H1B109.5C7—N2—H2E109.5
C3—N1—H1C109.5C7—N2—H2F109.5
H1B—N1—H1C109.5H2E—N2—H2F109.5
C3—N1—H1G109.5C7—N2—H2G109.5
H1B—N1—H1G109.5H2E—N2—H2G109.5
H1C—N1—H1G109.5H2F—N2—H2G109.5
C3—C1—H1D109.5C7—C5—H5A109.5
C3—C1—H1E109.5C7—C5—H5B109.5
H1D—C1—H1E109.5H5A—C5—H5B109.5
C3—C1—H1F109.5C7—C5—H5C109.5
H1D—C1—H1F109.5H5A—C5—H5C109.5
H1E—C1—H1F109.5H5B—C5—H5C109.5
C3—C2—H2A109.5C7—C6—H6A109.5
C3—C2—H2B109.5C7—C6—H6B109.5
H2A—C2—H2B109.5H6A—C6—H6B109.5
C3—C2—H2C109.5C7—C6—H6C109.5
H2A—C2—H2C109.5H6A—C6—H6C109.5
H2B—C2—H2C109.5H6B—C6—H6C109.5
C2—C3—C4111.4 (2)N2—C7—C8107.6 (2)
C2—C3—N1108.1 (2)N2—C7—C5108.1 (2)
C4—C3—N1107.9 (2)C8—C7—C5109.5 (2)
C2—C3—C1112.0 (3)N2—C7—C6107.5 (2)
C4—C3—C1109.9 (3)C8—C7—C6112.0 (2)
N1—C3—C1107.3 (2)C5—C7—C6112.0 (2)
O1—C4—C3112.5 (2)O2—C8—C7110.7 (2)
O1—C4—H4A109.1O2—C8—H8A109.5
C3—C4—H4A109.1C7—C8—H8A109.5
O1—C4—H4B109.1O2—C8—H8B109.5
C3—C4—H4B109.1C7—C8—H8B109.5
H4A—C4—H4B107.8H8A—C8—H8B108.1
C2—C3—C4—O153.1 (3)N2—C7—C8—O257.7 (3)
N1—C3—C4—O165.4 (3)C5—C7—C8—O2174.9 (2)
C1—C3—C4—O1177.8 (2)C6—C7—C8—O260.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···Cl10.82 (3)2.25 (4)3.067 (2)174 (3)
N1—H1B···O20.892.022.876 (3)161
N1—H1C···Cl1i0.892.333.216 (3)171
N1—H1G···Cl1ii0.892.423.261 (2)157
O2—H2D···O1iii0.821.912.731 (3)175
N2—H2E···Cl10.892.533.391 (2)163
N2—H2E···O20.892.492.811 (3)102
N2—H2F···Cl2iv0.892.243.130 (2)177
N2—H2G···Cl20.892.273.144 (2)169
C2—H2A···O10.962.532.880 (4)102
C6—H6A···O20.962.592.933 (4)101
Symmetry codes: (i) x+1, y, z; (ii) x, y, z+1; (iii) x, y+1, z+1; (iv) x1/2, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC4H12NO+·Cl
Mr125.60
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)6.4940 (13), 9.5230 (19), 21.903 (4)
β (°) 91.88 (3)
V3)1353.8 (5)
Z8
Radiation typeMo Kα
µ (mm1)0.46
Crystal size (mm)0.30 × 0.20 × 0.20
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.874, 0.913
No. of measured, independent and
observed [I > 2σ(I)] reflections
2651, 2421, 1857
Rint0.020
(sin θ/λ)max1)0.598
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.154, 1.01
No. of reflections2421
No. of parameters131
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O1—H1A···Cl10.82 (3)2.25 (4)3.067 (2)174 (3)
N1—H1B···O20.89002.02002.876 (3)161.00
N1—H1C···Cl1i0.89002.33003.216 (3)171.00
N1—H1G···Cl1ii0.89002.42003.261 (2)157.00
O2—H2D···O1iii0.82001.91002.731 (3)175.00
N2—H2E···Cl10.89002.53003.391 (2)163.00
N2—H2E···O20.89002.49002.811 (3)102.00
N2—H2F···Cl2iv0.89002.24003.130 (2)177.00
N2—H2G···Cl20.89002.27003.144 (2)169.00
C2—H2A···O10.96002.53002.880 (4)102.00
C6—H6A···O20.96002.59002.933 (4)101.00
Symmetry codes: (i) x+1, y, z; (ii) x, y, z+1; (iii) x, y+1, z+1; (iv) x1/2, y+1/2, z+3/2.
 

Acknowledgements

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

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
First citationEnraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.  Google Scholar
First citationHarms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.  Google Scholar
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science Google Scholar
First citationPazenok, S. (2007). Bayer Cropscience A.-G., Germany. WO patent 2007 022 900.  Google Scholar
First citationSenkus, M. (1948). Ind. Engineering Chem. 40, 506–508.  CrossRef CAS Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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