4-Allyl-4-ethyl­morpholinium chloride

Wang, M.-L.; Zang, H.-J.; Cheng, B.-W.

doi:10.1107/S1600536808030201

organic compounds

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Volume 64| Part 10| October 2008| Page o2013

doi:10.1107/S1600536808030201

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4-Allyl-4-ethylmorpholinium chloride

Mei-Ling Wang,^a Hong-Jun Zang ^a ^* and Bo-Wen Cheng ^a

^aSchool of Materials and Chemical Engineering and Key Laboratory of Hollow Fiber Membrane Materials & Membrane Processes, Tianjin Polytechnic University, Tianjin 300160, People's Republic of China
^*Correspondence e-mail: chemhong@126.com

(Received 4 September 2008; accepted 19 September 2008; online 27 September 2008)

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 , 2005 ); Kim et al. (2005 , 2006 ). For bond-length data, see: Allen et al. (1987 ). For ring puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₉H₁₈NO⁺·Cl⁻
M_r = 191.69
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.029
wR(F²) = 0.079
S = 1.07
1779 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O1ⁱ	0.97	2.48	3.4446 (19)	175
C2—H2A⋯Cl1ⁱⁱ	0.97	2.69	3.4417 (15)	135
C2—H2B⋯Cl1ⁱⁱⁱ	0.97	2.72	3.6690 (17)	166
C4—H4A⋯Cl1^iv	0.97	2.83	3.7513 (16)	160
C4—H4B⋯Cl1^v	0.97	2.71	3.5612 (18)	147
C5—H5A⋯Cl1^iv	0.97	2.78	3.6871 (16)	157
C5—H5B⋯Cl1ⁱⁱⁱ	0.97	2.81	3.7562 (16)	166
C6—H6⋯Cl1	0.93	2.75	3.6777 (18)	173
C7—H7A⋯Cl1ⁱⁱⁱ	0.93	2.92	3.776 (2)	154
C7—H7B⋯O1^vi	0.93	2.58	3.4456 (19)	155
C9—H9B⋯O1^vii	0.96	2.58	3.5359 (19)	173
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y+1, -z+1; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x+1, -y, -z+1; (v) x+1, y, z; (vi) x-1, y, z; (vii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030201/hk2524sup1.cif

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

checkCIF report

Comment top

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, Q_T, of 1.085 (3) and chair conformation [ϕ = -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.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 30% probability level.
	Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

4-Allyl-4-ethylmorpholinium chloride top

Crystal data top

C₉H₁₈NO⁺·Cl⁻	F(000) = 416
M_r = 191.69	D_x = 1.257 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1775 reflections
a = 8.5414 (17) Å	θ = 2.1–27.8°
b = 9.0391 (18) Å	µ = 0.33 mm⁻¹
c = 13.124 (3) Å	T = 133 K
β = 91.03 (3)°	Prism, colorless
V = 1013.1 (4) Å³	0.12 × 0.10 × 0.04 mm
Z = 4

Data collection top

Rigaku Saturn diffractometer	1779 independent reflections
Radiation source: fine-focus sealed tube	1605 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.028
Detector resolution: 27.571 pixels mm^-1	θ_max = 25.0°, θ_min = 2.7°
ω scans	h = −10→10
Absorption correction: multi-scan (Jacobson, 1998)	k = −10→10
T_min = 0.961, T_max = 0.987	l = −15→7
5624 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0427P)² + 0.2964P] where P = (F_o² + 2F_c²)/3
1779 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₉H₁₈NO⁺·Cl⁻	V = 1013.1 (4) Å³
M_r = 191.69	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.5414 (17) Å	µ = 0.33 mm⁻¹
b = 9.0391 (18) Å	T = 133 K
c = 13.124 (3) Å	0.12 × 0.10 × 0.04 mm
β = 91.03 (3)°

Data collection top

Rigaku Saturn diffractometer	1779 independent reflections
Absorption correction: multi-scan (Jacobson, 1998)	1605 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.987	R_int = 0.028
5624 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.08	Δρ_max = 0.24 e Å⁻³
1779 reflections	Δρ_min = −0.21 e Å⁻³
110 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
Cl1	0.25140 (4)	0.17741 (4)	0.39587 (3)	0.01833 (14)
O1	1.03933 (11)	0.39901 (11)	0.64961 (8)	0.0178 (2)
N1	0.76318 (13)	0.27908 (13)	0.54538 (9)	0.0132 (3)
C1	0.79277 (17)	0.44310 (15)	0.56086 (11)	0.0152 (3)
H1A	0.8448	0.4824	0.5016	0.018*
H1B	0.6932	0.4937	0.5668	0.018*
C2	0.89224 (17)	0.47404 (15)	0.65487 (11)	0.0169 (3)
H2A	0.9101	0.5797	0.6609	0.020*
H2B	0.8373	0.4415	0.7149	0.020*
C3	1.01221 (17)	0.24347 (15)	0.64773 (11)	0.0177 (3)
H3A	0.9565	0.2149	0.7084	0.021*
H3B	1.1119	0.1920	0.6484	0.021*
C4	0.91803 (16)	0.19804 (15)	0.55435 (11)	0.0164 (3)
H4A	0.8983	0.0924	0.5571	0.020*
H4B	0.9787	0.2177	0.4941	0.020*
C5	0.65242 (16)	0.21894 (15)	0.62513 (11)	0.0140 (3)
H5A	0.6438	0.1126	0.6169	0.017*
H5B	0.6970	0.2378	0.6924	0.017*
C6	0.49194 (17)	0.28520 (16)	0.61896 (11)	0.0177 (3)
H6	0.4292	0.2668	0.5617	0.021*
C7	0.43728 (18)	0.36865 (18)	0.69216 (12)	0.0242 (4)
H7A	0.4988	0.3880	0.7498	0.029*
H7B	0.3371	0.4084	0.6863	0.029*
C8	0.69654 (17)	0.25945 (16)	0.43820 (11)	0.0177 (3)
H8A	0.5981	0.3127	0.4328	0.021*
H8B	0.7680	0.3041	0.3905	0.021*
C9	0.66857 (19)	0.10082 (16)	0.40710 (11)	0.0220 (4)
H9A	0.7662	0.0481	0.4085	0.033*
H9B	0.6241	0.0980	0.3394	0.033*
H9C	0.5976	0.0554	0.4536	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0215 (2)	0.0166 (2)	0.0169 (2)	0.00409 (13)	−0.00052 (15)	−0.00080 (13)
O1	0.0150 (6)	0.0159 (5)	0.0223 (6)	−0.0008 (4)	−0.0006 (4)	−0.0002 (4)
N1	0.0141 (6)	0.0130 (6)	0.0126 (6)	0.0005 (5)	0.0015 (5)	0.0012 (5)
C1	0.0168 (7)	0.0107 (7)	0.0182 (7)	0.0006 (5)	0.0024 (6)	0.0021 (6)
C2	0.0179 (8)	0.0136 (7)	0.0192 (7)	0.0007 (6)	0.0020 (6)	−0.0005 (6)
C3	0.0156 (7)	0.0141 (7)	0.0234 (8)	0.0024 (5)	−0.0008 (6)	0.0013 (6)
C4	0.0137 (8)	0.0151 (7)	0.0204 (8)	0.0034 (5)	0.0028 (6)	−0.0006 (6)
C5	0.0154 (7)	0.0138 (6)	0.0130 (7)	−0.0020 (5)	0.0021 (6)	0.0009 (6)
C6	0.0138 (7)	0.0213 (7)	0.0179 (8)	−0.0033 (6)	−0.0012 (6)	0.0027 (6)
C7	0.0171 (8)	0.0290 (8)	0.0263 (9)	0.0036 (6)	0.0008 (7)	−0.0017 (7)
C8	0.0199 (8)	0.0213 (8)	0.0118 (7)	0.0011 (6)	−0.0003 (6)	0.0013 (6)
C9	0.0256 (9)	0.0241 (8)	0.0161 (8)	−0.0025 (6)	−0.0018 (6)	−0.0025 (6)

Geometric parameters (Å, º) top

O1—C2	1.4305 (17)	C4—H4B	0.9700
O1—C3	1.4250 (17)	C5—H5A	0.9700
N1—C1	1.5170 (17)	C5—H5B	0.9700
N1—C4	1.5146 (17)	C6—C5	1.497 (2)
N1—C5	1.5237 (18)	C6—C7	1.314 (2)
N1—C8	1.5183 (18)	C6—H6	0.9300
C1—C2	1.511 (2)	C7—H7A	0.9300
C1—H1A	0.9700	C7—H7B	0.9300
C1—H1B	0.9700	C8—C9	1.509 (2)
C2—H2A	0.9700	C8—H8A	0.9700
C2—H2B	0.9700	C8—H8B	0.9700
C3—C4	1.511 (2)	C9—H9A	0.9600
C3—H3A	0.9700	C9—H9B	0.9600
C3—H3B	0.9700	C9—H9C	0.9600
C4—H4A	0.9700

C3—O1—C2	109.02 (10)	C3—C4—H4A	109.1
C1—N1—C5	111.15 (11)	C3—C4—H4B	109.1
C1—N1—C8	107.28 (10)	H4A—C4—H4B	107.8
C4—N1—C1	108.61 (10)	N1—C5—H5A	108.9
C4—N1—C5	109.04 (11)	N1—C5—H5B	108.9
C4—N1—C8	109.13 (11)	C6—C5—N1	113.54 (11)
C8—N1—C5	111.57 (11)	C6—C5—H5A	108.9
N1—C1—H1A	109.1	C6—C5—H5B	108.9
N1—C1—H1B	109.1	H5A—C5—H5B	107.7
H1A—C1—H1B	107.9	C7—C6—C5	121.82 (14)
C2—C1—N1	112.33 (11)	C7—C6—H6	119.1
C2—C1—H1A	109.1	C5—C6—H6	119.1
C2—C1—H1B	109.1	C6—C7—H7A	120.0
O1—C2—C1	110.74 (12)	C6—C7—H7B	120.0
O1—C2—H2A	109.5	H7A—C7—H7B	120.0
O1—C2—H2B	109.5	N1—C8—H8A	108.6
C1—C2—H2A	109.5	N1—C8—H8B	108.6
C1—C2—H2B	109.5	C9—C8—N1	114.62 (11)
H2A—C2—H2B	108.1	C9—C8—H8A	108.6
O1—C3—C4	111.49 (11)	C9—C8—H8B	108.6
O1—C3—H3A	109.3	H8A—C8—H8B	107.6
O1—C3—H3B	109.3	C8—C9—H9A	109.5
C4—C3—H3A	109.3	C8—C9—H9B	109.5
C4—C3—H3B	109.3	H9A—C9—H9B	109.5
H3A—C3—H3B	108.0	C8—C9—H9C	109.5
N1—C4—H4A	109.1	H9A—C9—H9C	109.5
N1—C4—H4B	109.1	H9B—C9—H9C	109.5
C3—C4—N1	112.52 (11)

N1—C1—C2—O1	57.87 (15)	C1—N1—C5—C6	63.78 (14)
C3—O1—C2—C1	−63.03 (14)	C4—N1—C5—C6	−176.51 (11)
C2—O1—C3—C4	62.46 (15)	C8—N1—C5—C6	−55.91 (15)
C4—N1—C1—C2	−49.24 (15)	C1—N1—C8—C9	176.57 (12)
C5—N1—C1—C2	70.72 (14)	C4—N1—C8—C9	59.07 (15)
C8—N1—C1—C2	−167.07 (12)	C5—N1—C8—C9	−61.48 (15)
C1—N1—C4—C3	48.38 (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—C3	165.03 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱ	0.97	2.48	3.4446 (19)	175
C2—H2A···Cl1ⁱⁱ	0.97	2.69	3.4417 (15)	135
C2—H2B···Cl1ⁱⁱⁱ	0.97	2.72	3.6690 (17)	166
C4—H4A···Cl1^iv	0.97	2.83	3.7513 (16)	160
C4—H4B···Cl1^v	0.97	2.71	3.5612 (18)	147
C5—H5A···Cl1^iv	0.97	2.78	3.6871 (16)	157
C5—H5B···Cl1ⁱⁱⁱ	0.97	2.81	3.7562 (16)	166
C6—H6···Cl1	0.93	2.75	3.6777 (18)	173
C7—H7A···Cl1ⁱⁱⁱ	0.93	2.92	3.776 (2)	154
C7—H7B···O1^vi	0.93	2.58	3.4456 (19)	155
C9—H9B···O1^vii	0.96	2.58	3.5359 (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.

Experimental details

Crystal data
Chemical formula	C₉H₁₈NO⁺·Cl⁻
M_r	191.69
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	133
a, b, c (Å)	8.5414 (17), 9.0391 (18), 13.124 (3)
β (°)	91.03 (3)
V (Å³)	1013.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.12 × 0.10 × 0.04

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (Jacobson, 1998)
T_min, T_max	0.961, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	5624, 1779, 1605
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.079, 1.08
No. of reflections	1779
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.21

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱ	0.97	2.48	3.4446 (19)	174.9
C2—H2A···Cl1ⁱⁱ	0.97	2.69	3.4417 (15)	134.6
C2—H2B···Cl1ⁱⁱⁱ	0.97	2.72	3.6690 (17)	166.2
C4—H4A···Cl1^iv	0.97	2.83	3.7513 (16)	159.5
C4—H4B···Cl1^v	0.97	2.71	3.5612 (18)	147.2
C5—H5A···Cl1^iv	0.97	2.78	3.6871 (16)	156.7
C5—H5B···Cl1ⁱⁱⁱ	0.97	2.81	3.7562 (16)	165.6
C6—H6···Cl1	0.93	2.75	3.6777 (18)	173.2
C7—H7A···Cl1ⁱⁱⁱ	0.93	2.92	3.776 (2)	153.6
C7—H7B···O1^vi	0.93	2.58	3.4456 (19)	154.8
C9—H9B···O1^vii	0.96	2.58	3.5359 (19)	172.7

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.

Acknowledgements

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

References

Abedin, S. Z. E., Borissenko, N. & Endres, F. (2004). Electrochem. Commun. 6, 510–514. Web of Science CrossRef Google Scholar
Abedin, S. Z. E., Farag, H. K., Moustafa, E. M., Welz-Biermann, U. & Endres, F. (2005). Phys. Chem. Chem. Phys. 7, 2333–2339. Web of Science PubMed Google Scholar
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. CrossRef Web of Science Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Jacobson, R. (1998). Private communication to the Rigaku Corporation, Tokyo, Japan. Google Scholar
Kim, K. S., Choi, S., Cha, J. H., Yeon, S. H. & Lee, H. (2006). J. Mater. Chem. 16, 1315–1317. Web of Science CrossRef CAS Google Scholar
Kim, K. S., Park, S. Y., Yeon, S. H. & Lee, H. (2005). Electrochim. Acta, 50, 5673–5678. Web of Science CrossRef CAS Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar