N-Benzyl-N-ethyl­morpholinium chloride

Bian, Y.-J.

doi:10.1107/S1600536808041846

organic compounds

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Volume 65| Part 1| January 2009| Page o105

doi:10.1107/S1600536808041846

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N-Benzyl-N-ethylmorpholinium chloride

Yan-Jiang Bian ^a ^*

^aFaculty of Chemistry and Material Science, Langfang Teachers' College, Hebei, Langfang 065000, People's Republic of China
^*Correspondence e-mail: biany@126.com

(Received 2 December 2008; accepted 9 December 2008; online 13 December 2008)

In the crystal structure of the title compound, C₁₃H₂₀NO⁺·Cl⁻, the morpholine ring is in a chair conformation and the molecules are linked by weak intermolecular C—H⋯Cl hydrogen bonding.

Related literature

For details of the importance of quaternary morpholine halides see: Kim et al. (2005 , 2006 ).

Experimental

Crystal data

C₁₃H₂₀NO⁺·Cl⁻
M_r = 241.75
Monoclinic, P 2₁ /c
a = 13.179 (3) Å
b = 8.4176 (17) Å
c = 12.255 (3) Å
β = 108.48 (3)°
V = 1289.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 113 (2) K
0.16 × 0.16 × 0.06 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.957, T_max = 0.984
7151 measured reflections
2266 independent reflections
2017 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.090
S = 1.07
2266 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯Cl1ⁱ	0.99	2.74	3.4724 (16)	131
C5—H5B⋯Cl1ⁱⁱ	0.99	2.61	3.5500 (16)	158
C11—H11⋯Cl1	0.95	2.66	3.5501 (16)	156
C12—H12B⋯Cl1ⁱⁱⁱ	0.99	2.61	3.5062 (16)	151
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{5\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXS97 (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/S1600536808041846/nc2129sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041846/nc2129Isup2.hkl

checkCIF report

Comment top

Quaternary morpholine halides are valuable precursors for the preparation of ionic liquids by ion metathesis (Kim et al.,2005). Ionic liquids based on the morpholinium cation are favored becaused of their low cost, easy synthesis, and electrochemical stability (Kim et al.,2006). Here we report a new structure of this class of compounds.

In the crystal structure the morpholine ring adopts a chair conformation (Fig. 1). The cations and anions are connected via weak C—H···Cl hydrogen bonding into a three-dimensional network (Tab 1).

Related literature top

For related literature on the importance of quaternary morpholine halides see: Kim et al. (2005, 2006).

Experimental top

Benzyl chloride(0.12 mol) was added to a solution of 4-ethylmorpholine(0.1 mol) in 20 ml of acetonitrile under stirring. The mixture was stirred at 60 °C for 5 h. The solvent was removed under reduced pressure. The remaining brownish, viscous liquid crystallized slowly at room temperature in a mixture of ethanol and acetone [1/20(v/v)]. Single-crystals were obtained by slow evaporation of the solvewnt from a solution in a mixture of ethanol and acetone [1/20(v/v)].

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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Crystal structure of the title compound with the atom-numbering scheme and displacement ellipsoids drawn at the 30% probability level.

N-Benzyl-N-ethylmorpholinium chloride top

Crystal data top

C₁₃H₂₀NO⁺·Cl⁻	F(000) = 520
M_r = 241.75	D_x = 1.245 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.179 (3) Å	Cell parameters from 3736 reflections
b = 8.4176 (17) Å	θ = 1.6–27.9°
c = 12.255 (3) Å	µ = 0.28 mm⁻¹
β = 108.48 (3)°	T = 113 K
V = 1289.5 (4) Å³	Prism, colorless
Z = 4	0.16 × 0.16 × 0.06 mm

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2266 independent reflections
Radiation source: rotating anode	2017 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.031
ω and ϕ scans	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −15→14
T_min = 0.957, T_max = 0.984	k = −9→10
7151 measured reflections	l = −7→14

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0545P)² + 0.1492P] where P = (F_o² + 2F_c²)/3
2266 reflections	(Δ/σ)_max = 0.002
146 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₃H₂₀NO⁺·Cl⁻	V = 1289.5 (4) Å³
M_r = 241.75	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.179 (3) Å	µ = 0.28 mm⁻¹
b = 8.4176 (17) Å	T = 113 K
c = 12.255 (3) Å	0.16 × 0.16 × 0.06 mm
β = 108.48 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2266 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2017 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.984	R_int = 0.031
7151 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.07	Δρ_max = 0.21 e Å⁻³
2266 reflections	Δρ_min = −0.19 e Å⁻³
146 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	0.31149 (3)	1.03231 (4)	0.23458 (3)	0.02272 (14)
O1	0.37595 (8)	0.96775 (12)	0.89939 (8)	0.0230 (3)
N1	0.30801 (9)	0.93219 (13)	0.64941 (10)	0.0165 (3)
C1	0.41986 (11)	0.89933 (18)	0.72853 (12)	0.0199 (3)
H1A	0.4258	0.7859	0.7509	0.024*
H1B	0.4718	0.9204	0.6870	0.024*
C2	0.44732 (12)	1.00099 (18)	0.83543 (12)	0.0220 (3)
H2A	0.5218	0.9794	0.8838	0.026*
H2B	0.4420	1.1146	0.8135	0.026*
C3	0.27034 (12)	1.00809 (18)	0.83116 (13)	0.0227 (3)
H3A	0.2674	1.1225	0.8116	0.027*
H3B	0.2208	0.9892	0.8760	0.027*
C4	0.23423 (11)	0.91112 (18)	0.72105 (12)	0.0201 (3)
H4A	0.2319	0.7974	0.7407	0.024*
H4B	0.1610	0.9438	0.6752	0.024*
C5	0.28285 (11)	0.80630 (17)	0.55463 (12)	0.0198 (3)
H5A	0.3283	0.8261	0.5054	0.024*
H5B	0.3025	0.7008	0.5908	0.024*
C6	0.16760 (11)	0.80131 (16)	0.47930 (12)	0.0182 (3)
C7	0.09501 (12)	0.70572 (17)	0.51050 (13)	0.0224 (3)
H7	0.1174	0.6504	0.5817	0.027*
C8	−0.00926 (12)	0.69048 (18)	0.43888 (13)	0.0260 (4)
H8	−0.0586	0.6273	0.4620	0.031*
C9	−0.04183 (12)	0.76705 (18)	0.33380 (13)	0.0263 (4)
H9	−0.1128	0.7536	0.2834	0.032*
C10	0.02947 (12)	0.86372 (19)	0.30209 (13)	0.0268 (4)
H10	0.0068	0.9180	0.2304	0.032*
C11	0.13372 (12)	0.88136 (18)	0.37469 (12)	0.0224 (3)
H11	0.1820	0.9483	0.3529	0.027*
C12	0.29561 (12)	1.09797 (17)	0.59839 (12)	0.0227 (3)
H12A	0.2232	1.1076	0.5417	0.027*
H12B	0.3008	1.1757	0.6606	0.027*
C13	0.37708 (14)	1.1417 (2)	0.53976 (13)	0.0328 (4)
H13A	0.4493	1.1329	0.5950	0.049*
H13B	0.3646	1.2512	0.5113	0.049*
H13C	0.3700	1.0695	0.4751	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0235 (2)	0.0170 (2)	0.0296 (2)	−0.00200 (13)	0.01123 (17)	−0.00037 (14)
O1	0.0241 (6)	0.0242 (6)	0.0192 (5)	−0.0001 (4)	0.0046 (5)	0.0020 (4)
N1	0.0168 (6)	0.0128 (6)	0.0188 (6)	−0.0008 (5)	0.0043 (5)	−0.0006 (5)
C1	0.0151 (7)	0.0203 (8)	0.0219 (7)	0.0008 (6)	0.0023 (6)	0.0000 (6)
C2	0.0194 (7)	0.0230 (8)	0.0213 (7)	−0.0024 (6)	0.0035 (6)	−0.0002 (6)
C3	0.0225 (8)	0.0234 (8)	0.0227 (8)	−0.0002 (6)	0.0080 (6)	−0.0017 (6)
C4	0.0178 (7)	0.0189 (8)	0.0250 (8)	−0.0014 (6)	0.0086 (6)	−0.0012 (6)
C5	0.0205 (7)	0.0140 (7)	0.0243 (7)	−0.0012 (6)	0.0065 (6)	−0.0044 (6)
C6	0.0195 (7)	0.0127 (7)	0.0216 (7)	0.0000 (6)	0.0054 (6)	−0.0052 (6)
C7	0.0266 (8)	0.0139 (7)	0.0247 (8)	−0.0027 (6)	0.0053 (7)	0.0001 (6)
C8	0.0223 (8)	0.0187 (8)	0.0362 (9)	−0.0044 (6)	0.0082 (7)	−0.0017 (7)
C9	0.0203 (7)	0.0208 (8)	0.0325 (8)	0.0022 (6)	0.0007 (7)	−0.0042 (7)
C10	0.0298 (8)	0.0251 (9)	0.0221 (8)	0.0047 (7)	0.0034 (7)	0.0010 (6)
C11	0.0262 (8)	0.0200 (8)	0.0226 (8)	−0.0018 (6)	0.0100 (7)	−0.0017 (6)
C12	0.0305 (8)	0.0122 (7)	0.0210 (7)	−0.0014 (6)	0.0020 (6)	0.0012 (6)
C13	0.0501 (10)	0.0252 (9)	0.0227 (8)	−0.0146 (8)	0.0108 (8)	0.0002 (7)

Geometric parameters (Å, º) top

O1—C3	1.4191 (18)	C5—H5B	0.9900
O1—C2	1.4300 (17)	C6—C11	1.391 (2)
N1—C1	1.5111 (18)	C6—C7	1.393 (2)
N1—C4	1.5129 (18)	C7—C8	1.382 (2)
N1—C12	1.5167 (18)	C7—H7	0.9500
N1—C5	1.5290 (18)	C8—C9	1.381 (2)
C1—C2	1.510 (2)	C8—H8	0.9500
C1—H1A	0.9900	C9—C10	1.388 (2)
C1—H1B	0.9900	C9—H9	0.9500
C2—H2A	0.9900	C10—C11	1.388 (2)
C2—H2B	0.9900	C10—H10	0.9500
C3—C4	1.519 (2)	C11—H11	0.9500
C3—H3A	0.9900	C12—C13	1.515 (2)
C3—H3B	0.9900	C12—H12A	0.9900
C4—H4A	0.9900	C12—H12B	0.9900
C4—H4B	0.9900	C13—H13A	0.9800
C5—C6	1.507 (2)	C13—H13B	0.9800
C5—H5A	0.9900	C13—H13C	0.9800

C3—O1—C2	108.83 (11)	C6—C5—H5B	108.6
C1—N1—C4	106.37 (10)	N1—C5—H5B	108.6
C1—N1—C12	112.87 (11)	H5A—C5—H5B	107.6
C4—N1—C12	110.00 (10)	C11—C6—C7	119.02 (14)
C1—N1—C5	107.05 (11)	C11—C6—C5	121.18 (13)
C4—N1—C5	109.58 (10)	C7—C6—C5	119.63 (13)
C12—N1—C5	110.82 (11)	C8—C7—C6	120.69 (14)
C2—C1—N1	111.70 (12)	C8—C7—H7	119.7
C2—C1—H1A	109.3	C6—C7—H7	119.7
N1—C1—H1A	109.3	C9—C8—C7	120.09 (14)
C2—C1—H1B	109.3	C9—C8—H8	120.0
N1—C1—H1B	109.3	C7—C8—H8	120.0
H1A—C1—H1B	107.9	C8—C9—C10	119.78 (14)
O1—C2—C1	110.26 (12)	C8—C9—H9	120.1
O1—C2—H2A	109.6	C10—C9—H9	120.1
C1—C2—H2A	109.6	C11—C10—C9	120.23 (14)
O1—C2—H2B	109.6	C11—C10—H10	119.9
C1—C2—H2B	109.6	C9—C10—H10	119.9
H2A—C2—H2B	108.1	C10—C11—C6	120.17 (14)
O1—C3—C4	111.57 (12)	C10—C11—H11	119.9
O1—C3—H3A	109.3	C6—C11—H11	119.9
C4—C3—H3A	109.3	C13—C12—N1	114.80 (13)
O1—C3—H3B	109.3	C13—C12—H12A	108.6
C4—C3—H3B	109.3	N1—C12—H12A	108.6
H3A—C3—H3B	108.0	C13—C12—H12B	108.6
N1—C4—C3	112.00 (11)	N1—C12—H12B	108.6
N1—C4—H4A	109.2	H12A—C12—H12B	107.5
C3—C4—H4A	109.2	C12—C13—H13A	109.5
N1—C4—H4B	109.2	C12—C13—H13B	109.5
C3—C4—H4B	109.2	H13A—C13—H13B	109.5
H4A—C4—H4B	107.9	C12—C13—H13C	109.5
C6—C5—N1	114.73 (11)	H13A—C13—H13C	109.5
C6—C5—H5A	108.6	H13B—C13—H13C	109.5
N1—C5—H5A	108.6

C4—N1—C1—C2	−54.32 (14)	N1—C5—C6—C11	95.68 (15)
C12—N1—C1—C2	66.40 (15)	N1—C5—C6—C7	−89.09 (16)
C5—N1—C1—C2	−171.41 (11)	C11—C6—C7—C8	−0.1 (2)
C3—O1—C2—C1	−62.64 (15)	C5—C6—C7—C8	−175.43 (13)
N1—C1—C2—O1	61.35 (15)	C6—C7—C8—C9	1.7 (2)
C2—O1—C3—C4	61.11 (15)	C7—C8—C9—C10	−2.2 (2)
C1—N1—C4—C3	52.26 (15)	C8—C9—C10—C11	1.1 (2)
C12—N1—C4—C3	−70.29 (15)	C9—C10—C11—C6	0.5 (2)
C5—N1—C4—C3	167.65 (12)	C7—C6—C11—C10	−1.0 (2)
O1—C3—C4—N1	−57.89 (16)	C5—C6—C11—C10	174.27 (13)
C1—N1—C5—C6	169.51 (11)	C1—N1—C12—C13	52.59 (16)
C4—N1—C5—C6	54.55 (15)	C4—N1—C12—C13	171.21 (12)
C12—N1—C5—C6	−67.02 (15)	C5—N1—C12—C13	−67.46 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl1ⁱ	0.99	2.74	3.4724 (16)	131
C5—H5B···Cl1ⁱⁱ	0.99	2.61	3.5500 (16)	158
C11—H11···Cl1	0.95	2.66	3.5501 (16)	156
C12—H12B···Cl1ⁱⁱⁱ	0.99	2.61	3.5062 (16)	151

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x, −y+5/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₂₀NO⁺·Cl⁻
M_r	241.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	13.179 (3), 8.4176 (17), 12.255 (3)
β (°)	108.48 (3)
V (Å³)	1289.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.16 × 0.16 × 0.06

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.957, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	7151, 2266, 2017
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.090, 1.07
No. of reflections	2266
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl1ⁱ	0.99	2.74	3.4724 (16)	131.3
C5—H5B···Cl1ⁱⁱ	0.99	2.61	3.5500 (16)	157.7
C11—H11···Cl1	0.95	2.66	3.5501 (16)	156.0
C12—H12B···Cl1ⁱⁱⁱ	0.99	2.61	3.5062 (16)	150.8

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x, −y+5/2, z+1/2.

References

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

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doi:10.1107/S1600536808041846

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