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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1150.
Published online 2008 May 24. doi:  10.1107/S1600536808015018
PMCID: PMC2961394

1-Hydroxymethyl-1-methylethan­aminium chloride

Abstract

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 [triangle]). For general background, see: Pazenok (2007 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-o1150-scheme1.jpg

Experimental

Crystal data

  • C4H12NO+·Cl
  • M r = 125.60
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1150-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 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

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015018/hk2463sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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

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.

Figures

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.

Crystal data

C4H12NO+·ClF000 = 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 = 11–14º
b = 9.5230 (19) ŵ = 0.46 mm1
c = 21.903 (4) ÅT = 298 (2) K
β = 91.88 (3)ºBlock, colorless
V = 1353.8 (5) Å30.30 × 0.20 × 0.20 mm
Z = 8

Data collection

Enraf-Nonius CAD-4 diffractometerRint = 0.020
Radiation source: fine-focus sealed tubeθmax = 25.2º
Monochromator: graphiteθmin = 1.9º
T = 298(2) Kh = 0→7
ω/2θ scansk = 0→11
Absorption correction: ψ scan(North et al., 1968)l = −26→26
Tmin = 0.874, Tmax = 0.9133 standard reflections
2651 measured reflections every 120 min
2421 independent reflections intensity decay: none
1857 reflections with I > 2σ(I)

Refinement

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)

Special details

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)

xyzUiso*/Ueq
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*
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*
N2−0.0750 (4)0.2407 (2)0.67597 (10)0.0304 (6)
H2E−0.11780.23520.63700.046*
H2F−0.12210.31950.69230.046*
H2G−0.12210.16720.69640.046*
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*
H4B−0.00390.17710.40440.046*
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)

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, °)

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—O1−53.1 (3)N2—C7—C8—O2−57.7 (3)
N1—C3—C4—O165.4 (3)C5—C7—C8—O2−174.9 (2)
C1—C3—C4—O1−177.8 (2)C6—C7—C8—O260.2 (3)

Hydrogen-bond geometry (Å, °)

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) −x−1/2, y+1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2463).

References

  • 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.
  • Enraf–Nonius (1985). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Pazenok, S. (2007). Bayer Cropscience A.-G., Germany. WO patent 2007 022 900.
  • Senkus, M. (1948). Ind. Engineering Chem 40, 506–508.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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