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Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o2013.
Published online 2008 September 27. doi:  10.1107/S1600536808030201
PMCID: PMC2959247

4-Allyl-4-ethyl­morpholinium chloride

Abstract

In the title molecular salt, C9H18NO+·Cl, the morpholine ring adopts a chair conformation. In the crystal structure, intra­molecular C—H(...)Cl bonds occur and inter­molecular C—H(...)O and C—H(...)Cl hydrogen bonds link the mol­ecules.

Related literature

For general background, see: Abedin et al. (2004 [triangle], 2005 [triangle]); Kim et al. (2005 [triangle], 2006 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For ring puckering parameters, see: Cremer & Pople (1975 [triangle]).

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Object name is e-64-o2013-scheme1.jpg

Experimental

Crystal data

  • C9H18NO+·Cl
  • M r = 191.69
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2013-efi1.jpg
  • a = 8.5414 (17) Å
  • b = 9.0391 (18) Å
  • c = 13.124 (3) Å
  • β = 91.03 (3)°
  • V = 1013.1 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.33 mm−1
  • T = 133 (2) K
  • 0.12 × 0.10 × 0.04 mm

Data collection

  • Rigaku Saturn diffractometer
  • Absorption correction: multi-scan (Jacobson, 1998 [triangle]) T min = 0.961, T max = 0.987
  • 5624 measured reflections
  • 1779 independent reflections
  • 1605 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.079
  • S = 1.07
  • 1779 reflections
  • 110 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL 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/S1600536808030201/hk2524sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808030201/hk2524Isup2.hkl

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

Acknowledgments

The authors thank Tianjin Natural Science Foundation (grant No. 07JCYBJC02200) for financial support.

supplementary crystallographic information

Comment

Quaternary morpholine halides are valuable precursors for the preparation of ionic liquids (ILs) by ion metathesis (Kim et al., 2005). The excellent conductivity, broad electrochemical window, thermal stability, and low volatility of ILs have made them promising media for electrochemical processes (Abedin et al., 2004; Abedin et al., 2005). In particular, ILs based on the morpholinium cation are favored because of their low cost, easy synthesis and electrochemical stability (Kim et al., 2006). So far, only a few crystallographic studies have been performed on salts. We report herein the crystal structure of the title compound.

In the molecule of the title compound, (Fig. 1), the bond lengths (Allen et al., 1987) and angles are generally within normal ranges. The morpholine ring (O1/N1/C1-C4) is, of course, not planar, having total puckering amplitude, QT, of 1.085 (3) and chair conformation [[var phi] = -154.63 (3)° and θ = 122.70 (3)°] (Cremer & Pople, 1975).

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

Experimental

Under vigorous stirring, allyl chloride (0.1 mol) was added to a solution of 4-ethylmorpholine (0.1 mol) in acetonitrile (20 ml). The mixture was stirred at 333 K for 2 h. The mixture was filtered to remove excess N-ethyl morpholine and allyl chloride and washed with acetone to give the title compound. It was crystallized from ethanol/acetone mixture (1:20) by slow evaporation.

Refinement

H atoms were positioned geometrically, with C-H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 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 30% probability level.
Fig. 2.
A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C9H18NO+·ClF(000) = 416
Mr = 191.69Dx = 1.257 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1775 reflections
a = 8.5414 (17) Åθ = 2.1–27.8°
b = 9.0391 (18) ŵ = 0.33 mm1
c = 13.124 (3) ÅT = 133 K
β = 91.03 (3)°Prism, colorless
V = 1013.1 (4) Å30.12 × 0.10 × 0.04 mm
Z = 4

Data collection

Rigaku Saturn diffractometer1779 independent reflections
Radiation source: fine-focus sealed tube1605 reflections with I > 2σ(I)
confocalRint = 0.028
Detector resolution: 27.571 pixels mm-1θmax = 25.0°, θmin = 2.7°
ω scansh = −10→10
Absorption correction: multi-scan (Jacobson, 1998)k = −10→10
Tmin = 0.961, Tmax = 0.987l = −15→7
5624 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0427P)2 + 0.2964P] where P = (Fo2 + 2Fc2)/3
1779 reflections(Δ/σ)max < 0.001
110 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = −0.21 e Å3

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 > 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)

xyzUiso*/Ueq
Cl10.25140 (4)0.17741 (4)0.39587 (3)0.01833 (14)
O11.03933 (11)0.39901 (11)0.64961 (8)0.0178 (2)
N10.76318 (13)0.27908 (13)0.54538 (9)0.0132 (3)
C10.79277 (17)0.44310 (15)0.56086 (11)0.0152 (3)
H1A0.84480.48240.50160.018*
H1B0.69320.49370.56680.018*
C20.89224 (17)0.47404 (15)0.65487 (11)0.0169 (3)
H2A0.91010.57970.66090.020*
H2B0.83730.44150.71490.020*
C31.01221 (17)0.24347 (15)0.64773 (11)0.0177 (3)
H3A0.95650.21490.70840.021*
H3B1.11190.19200.64840.021*
C40.91803 (16)0.19804 (15)0.55435 (11)0.0164 (3)
H4A0.89830.09240.55710.020*
H4B0.97870.21770.49410.020*
C50.65242 (16)0.21894 (15)0.62513 (11)0.0140 (3)
H5A0.64380.11260.61690.017*
H5B0.69700.23780.69240.017*
C60.49194 (17)0.28520 (16)0.61896 (11)0.0177 (3)
H60.42920.26680.56170.021*
C70.43728 (18)0.36865 (18)0.69216 (12)0.0242 (4)
H7A0.49880.38800.74980.029*
H7B0.33710.40840.68630.029*
C80.69654 (17)0.25945 (16)0.43820 (11)0.0177 (3)
H8A0.59810.31270.43280.021*
H8B0.76800.30410.39050.021*
C90.66857 (19)0.10082 (16)0.40710 (11)0.0220 (4)
H9A0.76620.04810.40850.033*
H9B0.62410.09800.33940.033*
H9C0.59760.05540.45360.033*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0215 (2)0.0166 (2)0.0169 (2)0.00409 (13)−0.00052 (15)−0.00080 (13)
O10.0150 (6)0.0159 (5)0.0223 (6)−0.0008 (4)−0.0006 (4)−0.0002 (4)
N10.0141 (6)0.0130 (6)0.0126 (6)0.0005 (5)0.0015 (5)0.0012 (5)
C10.0168 (7)0.0107 (7)0.0182 (7)0.0006 (5)0.0024 (6)0.0021 (6)
C20.0179 (8)0.0136 (7)0.0192 (7)0.0007 (6)0.0020 (6)−0.0005 (6)
C30.0156 (7)0.0141 (7)0.0234 (8)0.0024 (5)−0.0008 (6)0.0013 (6)
C40.0137 (8)0.0151 (7)0.0204 (8)0.0034 (5)0.0028 (6)−0.0006 (6)
C50.0154 (7)0.0138 (6)0.0130 (7)−0.0020 (5)0.0021 (6)0.0009 (6)
C60.0138 (7)0.0213 (7)0.0179 (8)−0.0033 (6)−0.0012 (6)0.0027 (6)
C70.0171 (8)0.0290 (8)0.0263 (9)0.0036 (6)0.0008 (7)−0.0017 (7)
C80.0199 (8)0.0213 (8)0.0118 (7)0.0011 (6)−0.0003 (6)0.0013 (6)
C90.0256 (9)0.0241 (8)0.0161 (8)−0.0025 (6)−0.0018 (6)−0.0025 (6)

Geometric parameters (Å, °)

O1—C21.4305 (17)C4—H4B0.9700
O1—C31.4250 (17)C5—H5A0.9700
N1—C11.5170 (17)C5—H5B0.9700
N1—C41.5146 (17)C6—C51.497 (2)
N1—C51.5237 (18)C6—C71.314 (2)
N1—C81.5183 (18)C6—H60.9300
C1—C21.511 (2)C7—H7A0.9300
C1—H1A0.9700C7—H7B0.9300
C1—H1B0.9700C8—C91.509 (2)
C2—H2A0.9700C8—H8A0.9700
C2—H2B0.9700C8—H8B0.9700
C3—C41.511 (2)C9—H9A0.9600
C3—H3A0.9700C9—H9B0.9600
C3—H3B0.9700C9—H9C0.9600
C4—H4A0.9700
C3—O1—C2109.02 (10)C3—C4—H4A109.1
C1—N1—C5111.15 (11)C3—C4—H4B109.1
C1—N1—C8107.28 (10)H4A—C4—H4B107.8
C4—N1—C1108.61 (10)N1—C5—H5A108.9
C4—N1—C5109.04 (11)N1—C5—H5B108.9
C4—N1—C8109.13 (11)C6—C5—N1113.54 (11)
C8—N1—C5111.57 (11)C6—C5—H5A108.9
N1—C1—H1A109.1C6—C5—H5B108.9
N1—C1—H1B109.1H5A—C5—H5B107.7
H1A—C1—H1B107.9C7—C6—C5121.82 (14)
C2—C1—N1112.33 (11)C7—C6—H6119.1
C2—C1—H1A109.1C5—C6—H6119.1
C2—C1—H1B109.1C6—C7—H7A120.0
O1—C2—C1110.74 (12)C6—C7—H7B120.0
O1—C2—H2A109.5H7A—C7—H7B120.0
O1—C2—H2B109.5N1—C8—H8A108.6
C1—C2—H2A109.5N1—C8—H8B108.6
C1—C2—H2B109.5C9—C8—N1114.62 (11)
H2A—C2—H2B108.1C9—C8—H8A108.6
O1—C3—C4111.49 (11)C9—C8—H8B108.6
O1—C3—H3A109.3H8A—C8—H8B107.6
O1—C3—H3B109.3C8—C9—H9A109.5
C4—C3—H3A109.3C8—C9—H9B109.5
C4—C3—H3B109.3H9A—C9—H9B109.5
H3A—C3—H3B108.0C8—C9—H9C109.5
N1—C4—H4A109.1H9A—C9—H9C109.5
N1—C4—H4B109.1H9B—C9—H9C109.5
C3—C4—N1112.52 (11)
N1—C1—C2—O157.87 (15)C1—N1—C5—C663.78 (14)
C3—O1—C2—C1−63.03 (14)C4—N1—C5—C6−176.51 (11)
C2—O1—C3—C462.46 (15)C8—N1—C5—C6−55.91 (15)
C4—N1—C1—C2−49.24 (15)C1—N1—C8—C9176.57 (12)
C5—N1—C1—C270.72 (14)C4—N1—C8—C959.07 (15)
C8—N1—C1—C2−167.07 (12)C5—N1—C8—C9−61.48 (15)
C1—N1—C4—C348.38 (15)O1—C3—C4—N1−56.48 (16)
C5—N1—C4—C3−72.88 (14)C7—C6—C5—N1−114.26 (16)
C8—N1—C4—C3165.03 (11)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1A···O1i0.972.483.4446 (19)175.
C2—H2A···Cl1ii0.972.693.4417 (15)135.
C2—H2B···Cl1iii0.972.723.6690 (17)166.
C4—H4A···Cl1iv0.972.833.7513 (16)160.
C4—H4B···Cl1v0.972.713.5612 (18)147.
C5—H5A···Cl1iv0.972.783.6871 (16)157.
C5—H5B···Cl1iii0.972.813.7562 (16)166.
C6—H6···Cl10.932.753.6777 (18)173.
C7—H7A···Cl1iii0.932.923.776 (2)154.
C7—H7B···O1vi0.932.583.4456 (19)155.
C9—H9B···O1vii0.962.583.5359 (19)173.

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2524).

References

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  • Abedin, S. Z. E., Farag, H. K., Moustafa, E. M., Welz-Biermann, U. & Endres, F. (2005). Phys. Chem. Chem. Phys.7, 2333–2339. [PubMed]
  • 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.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Jacobson, R. (1998). Private communication to the Rigaku Corporation, Tokyo, Japan.
  • Kim, K. S., Choi, S., Cha, J. H., Yeon, S. H. & Lee, H. (2006). J. Mater. Chem.16, 1315–1317.
  • Kim, K. S., Park, S. Y., Yeon, S. H. & Lee, H. (2005). Electrochim. Acta, 50, 5673–5678.
  • Rigaku/MSC (2005). CrystalClear Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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