N-Benzyl-N-methyl­morpholinium chloride

Bian, Y.-J.

doi:10.1107/S1600536808040506

organic compounds

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Volume 65| Part 1| January 2009| Page o38

doi:10.1107/S1600536808040506

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N-Benzyl-N-methylmorpholinium chloride

Yan-Jiang Bian ^a ^*

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

(Received 30 November 2008; accepted 2 December 2008; online 6 December 2008)

In the title compound, C₁₂H₁₈NO⁺·Cl⁻, the cations and anions are interconnected by weak C—H⋯Cl hydrogen bonds. The morpholine ring system adopts a chair conformation.

Related literature

For general background to ionic liquids, see: Abedin et al. (2004 , 2005 ); Kim et al. (2005 , 2006 ).

Experimental

Crystal data

C₁₂H₁₈NO⁺·Cl⁻
M_r = 227.72
Orthorhombic, P b c a
a = 9.8693 (8) Å
b = 9.5732 (8) Å
c = 24.989 (2) Å
V = 2361.0 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 113 (2) K
0.22 × 0.20 × 0.16 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.937, T_max = 0.954
23984 measured reflections
2806 independent reflections
2658 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.103
S = 1.14
2806 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯Cl1ⁱ	0.99	2.70	3.6610 (14)	163
C5—H5A⋯Cl1ⁱⁱ	0.99	2.74	3.6304 (14)	150
C5—H5B⋯Cl1	0.99	2.63	3.5373 (14)	152
C9—H9⋯Cl1ⁱⁱⁱ	0.95	2.80	3.5599 (16)	138
C12—H12A⋯Cl1ⁱⁱ	0.98	2.70	3.6085 (14)	155
C12—H12B⋯Cl1	0.98	2.78	3.6566 (14)	149
C12—H12C⋯Cl1^iv	0.98	2.68	3.6380 (14)	166
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

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/S1600536808040506/bt2824sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808040506/bt2824Isup2.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). We report here a new example structure of this class.

The molecular structure of the title compound is illustrated in Fig. 1. The morpholine unit adopts a chair conformation. The bond distances and angles in the cation are normal within experimental error.

The crystal packing is illustrated in Fig. 2. The Cl^-anion is involved in weak C—H···Cl hydrogen bonds. Each cation forms a network of weak C—H···Cl hydrogen bonds to surrounding chloride ions.

Related literature top

For general background on ionic liquids, see: Abedin et al. (2004, 2005); Kim et al. (2005, 2006).

Experimental top

Under vigorous stirring, benzyl chloride (0.12 mol) was added to a solution of 4-methylmorpholine (0.1 mol) in 20 ml of acetonitrile. 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 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. A view of the molecular structure of the title compund, showing the atom-numbering scheme. Dispacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The packing of the title compound, showing hydrogen-bond interactions as dashed lines.

N-Benzyl-N-methylmorpholinium chloride top

Crystal data top

C₁₂H₁₈NO⁺·Cl⁻	D_x = 1.281 Mg m⁻³
M_r = 227.72	Mo Kα radiation, λ = 0.71070 Å
Orthorhombic, Pbca	Cell parameters from 5341 reflections
a = 9.8693 (8) Å	θ = 1.6–27.9°
b = 9.5732 (8) Å	µ = 0.30 mm⁻¹
c = 24.989 (2) Å	T = 113 K
V = 2361.0 (4) Å³	Prism, colorless
Z = 8	0.22 × 0.20 × 0.16 mm
F(000) = 976

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2806 independent reflections
Radiation source: rotating anode	2658 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.045
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.9°, θ_min = 1.6°
ω and ϕ scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −12→12
T_min = 0.937, T_max = 0.954	l = −32→32
23984 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0504P)² + 0.8783P] where P = (F_o² + 2F_c²)/3
2806 reflections	(Δ/σ)_max = 0.001
137 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₂H₁₈NO⁺·Cl⁻	V = 2361.0 (4) Å³
M_r = 227.72	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.8693 (8) Å	µ = 0.30 mm⁻¹
b = 9.5732 (8) Å	T = 113 K
c = 24.989 (2) Å	0.22 × 0.20 × 0.16 mm

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2806 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2658 reflections with I > 2σ(I)
T_min = 0.937, T_max = 0.954	R_int = 0.045
23984 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.14	Δρ_max = 0.26 e Å⁻³
2806 reflections	Δρ_min = −0.37 e Å⁻³
137 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	0.06425 (3)	0.24262 (3)	0.579326 (12)	0.01816 (12)
O1	0.67612 (10)	0.15043 (10)	0.57658 (4)	0.0243 (2)
N1	0.44588 (10)	0.33344 (11)	0.59493 (4)	0.0150 (2)
C1	0.59109 (13)	0.37790 (14)	0.60368 (5)	0.0188 (3)
H1A	0.6158	0.3622	0.6416	0.023*
H1B	0.5997	0.4791	0.5962	0.023*
C2	0.68808 (14)	0.29772 (15)	0.56803 (6)	0.0215 (3)
H2A	0.6683	0.3193	0.5301	0.026*
H2B	0.7822	0.3275	0.5757	0.026*
C3	0.54189 (14)	0.10657 (14)	0.56303 (6)	0.0224 (3)
H3A	0.5349	0.0039	0.5668	0.027*
H3B	0.5228	0.1307	0.5252	0.027*
C4	0.43833 (13)	0.17620 (14)	0.59888 (5)	0.0178 (3)
H4A	0.3464	0.1448	0.5886	0.021*
H4B	0.4543	0.1475	0.6364	0.021*
C5	0.35303 (13)	0.40397 (14)	0.63597 (5)	0.0183 (3)
H5A	0.3710	0.5057	0.6352	0.022*
H5B	0.2580	0.3899	0.6245	0.022*
C6	0.36606 (13)	0.35467 (14)	0.69294 (5)	0.0181 (3)
C7	0.28094 (14)	0.24900 (14)	0.71151 (6)	0.0210 (3)
H7	0.2193	0.2053	0.6876	0.025*
C8	0.28540 (15)	0.20693 (17)	0.76477 (6)	0.0278 (3)
H8	0.2272	0.1346	0.7770	0.033*
C9	0.37464 (16)	0.27038 (17)	0.79996 (6)	0.0295 (3)
H9	0.3784	0.2411	0.8363	0.035*
C10	0.45814 (16)	0.37636 (18)	0.78209 (6)	0.0301 (4)
H10	0.5188	0.4203	0.8063	0.036*
C11	0.45410 (14)	0.41926 (16)	0.72890 (6)	0.0240 (3)
H11	0.5115	0.4927	0.7171	0.029*
C12	0.39548 (14)	0.38154 (14)	0.54104 (5)	0.0193 (3)
H12A	0.3981	0.4838	0.5394	0.029*
H12B	0.3021	0.3494	0.5358	0.029*
H12C	0.4534	0.3427	0.5129	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01759 (19)	0.01818 (19)	0.01873 (18)	0.00039 (11)	−0.00043 (10)	0.00056 (11)
O1	0.0205 (5)	0.0204 (5)	0.0320 (5)	0.0046 (4)	0.0022 (4)	0.0013 (4)
N1	0.0162 (5)	0.0133 (5)	0.0156 (5)	0.0002 (4)	−0.0003 (4)	0.0007 (4)
C1	0.0169 (6)	0.0186 (6)	0.0209 (6)	−0.0027 (5)	0.0002 (5)	−0.0015 (5)
C2	0.0178 (6)	0.0211 (7)	0.0257 (7)	−0.0011 (5)	0.0023 (5)	0.0020 (5)
C3	0.0251 (7)	0.0154 (6)	0.0267 (7)	0.0002 (5)	0.0023 (5)	−0.0025 (5)
C4	0.0212 (6)	0.0114 (6)	0.0209 (6)	−0.0020 (5)	0.0020 (5)	0.0019 (5)
C5	0.0191 (6)	0.0173 (6)	0.0183 (6)	0.0031 (5)	0.0018 (5)	−0.0001 (5)
C6	0.0175 (6)	0.0193 (6)	0.0175 (6)	0.0045 (5)	0.0005 (5)	−0.0013 (5)
C7	0.0194 (6)	0.0250 (7)	0.0187 (6)	−0.0002 (5)	0.0004 (5)	−0.0006 (5)
C8	0.0292 (7)	0.0310 (8)	0.0233 (7)	0.0037 (6)	0.0055 (6)	0.0055 (6)
C9	0.0317 (8)	0.0398 (9)	0.0171 (6)	0.0156 (7)	−0.0001 (6)	0.0008 (6)
C10	0.0285 (7)	0.0394 (9)	0.0226 (7)	0.0094 (6)	−0.0078 (6)	−0.0121 (6)
C11	0.0226 (7)	0.0236 (7)	0.0257 (7)	0.0008 (5)	−0.0008 (5)	−0.0075 (6)
C12	0.0212 (6)	0.0202 (6)	0.0166 (6)	0.0002 (5)	−0.0008 (5)	0.0027 (5)

Geometric parameters (Å, º) top

O1—C3	1.4304 (17)	C5—H5A	0.9900
O1—C2	1.4310 (17)	C5—H5B	0.9900
N1—C12	1.5075 (16)	C6—C7	1.3943 (19)
N1—C4	1.5104 (18)	C6—C11	1.3946 (19)
N1—C1	1.5109 (16)	C7—C8	1.3914 (19)
N1—C5	1.5321 (16)	C7—H7	0.9500
C1—C2	1.5164 (19)	C8—C9	1.385 (2)
C1—H1A	0.9900	C8—H8	0.9500
C1—H1B	0.9900	C9—C10	1.381 (2)
C2—H2A	0.9900	C9—H9	0.9500
C2—H2B	0.9900	C10—C11	1.392 (2)
C3—C4	1.5138 (18)	C10—H10	0.9500
C3—H3A	0.9900	C11—H11	0.9500
C3—H3B	0.9900	C12—H12A	0.9800
C4—H4A	0.9900	C12—H12B	0.9800
C4—H4B	0.9900	C12—H12C	0.9800
C5—C6	1.5056 (17)

C3—O1—C2	109.28 (10)	C6—C5—N1	116.35 (10)
C12—N1—C4	110.28 (10)	C6—C5—H5A	108.2
C12—N1—C1	110.87 (10)	N1—C5—H5A	108.2
C4—N1—C1	108.54 (10)	C6—C5—H5B	108.2
C12—N1—C5	105.42 (9)	N1—C5—H5B	108.2
C4—N1—C5	111.47 (9)	H5A—C5—H5B	107.4
C1—N1—C5	110.26 (10)	C7—C6—C11	118.87 (12)
N1—C1—C2	111.78 (11)	C7—C6—C5	119.38 (12)
N1—C1—H1A	109.3	C11—C6—C5	121.57 (12)
C2—C1—H1A	109.3	C8—C7—C6	120.61 (13)
N1—C1—H1B	109.3	C8—C7—H7	119.7
C2—C1—H1B	109.3	C6—C7—H7	119.7
H1A—C1—H1B	107.9	C9—C8—C7	120.04 (14)
O1—C2—C1	111.04 (11)	C9—C8—H8	120.0
O1—C2—H2A	109.4	C7—C8—H8	120.0
C1—C2—H2A	109.4	C10—C9—C8	119.76 (14)
O1—C2—H2B	109.4	C10—C9—H9	120.1
C1—C2—H2B	109.4	C8—C9—H9	120.1
H2A—C2—H2B	108.0	C9—C10—C11	120.56 (14)
O1—C3—C4	110.85 (11)	C9—C10—H10	119.7
O1—C3—H3A	109.5	C11—C10—H10	119.7
C4—C3—H3A	109.5	C10—C11—C6	120.15 (14)
O1—C3—H3B	109.5	C10—C11—H11	119.9
C4—C3—H3B	109.5	C6—C11—H11	119.9
H3A—C3—H3B	108.1	N1—C12—H12A	109.5
N1—C4—C3	111.52 (10)	N1—C12—H12B	109.5
N1—C4—H4A	109.3	H12A—C12—H12B	109.5
C3—C4—H4A	109.3	N1—C12—H12C	109.5
N1—C4—H4B	109.3	H12A—C12—H12C	109.5
C3—C4—H4B	109.3	H12B—C12—H12C	109.5
H4A—C4—H4B	108.0

C12—N1—C1—C2	−70.18 (14)	C1—N1—C5—C6	−70.30 (14)
C4—N1—C1—C2	51.09 (13)	N1—C5—C6—C7	−93.35 (14)
C5—N1—C1—C2	173.45 (10)	N1—C5—C6—C11	91.63 (15)
C3—O1—C2—C1	61.86 (14)	C11—C6—C7—C8	−1.1 (2)
N1—C1—C2—O1	−57.37 (14)	C5—C6—C7—C8	−176.30 (12)
C2—O1—C3—C4	−62.50 (14)	C6—C7—C8—C9	0.2 (2)
C12—N1—C4—C3	70.00 (13)	C7—C8—C9—C10	0.6 (2)
C1—N1—C4—C3	−51.64 (13)	C8—C9—C10—C11	−0.5 (2)
C5—N1—C4—C3	−173.26 (11)	C9—C10—C11—C6	−0.5 (2)
O1—C3—C4—N1	58.57 (14)	C7—C6—C11—C10	1.3 (2)
C12—N1—C5—C6	169.98 (11)	C5—C6—C11—C10	176.32 (12)
C4—N1—C5—C6	50.32 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···Cl1ⁱ	0.99	2.70	3.6610 (14)	163
C5—H5A···Cl1ⁱⁱ	0.99	2.74	3.6304 (14)	150
C5—H5B···Cl1	0.99	2.63	3.5373 (14)	152
C9—H9···Cl1ⁱⁱⁱ	0.95	2.80	3.5599 (16)	138
C12—H12A···Cl1ⁱⁱ	0.98	2.70	3.6085 (14)	155
C12—H12B···Cl1	0.98	2.78	3.6566 (14)	149
C12—H12C···Cl1^iv	0.98	2.68	3.6380 (14)	166

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₈NO⁺·Cl⁻
M_r	227.72
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	113
a, b, c (Å)	9.8693 (8), 9.5732 (8), 24.989 (2)
V (Å³)	2361.0 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.22 × 0.20 × 0.16

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.937, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	23984, 2806, 2658
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.103, 1.14
No. of reflections	2806
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.37

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
C3—H3A···Cl1ⁱ	0.99	2.70	3.6610 (14)	162.7
C5—H5A···Cl1ⁱⁱ	0.99	2.74	3.6304 (14)	150.1
C5—H5B···Cl1	0.99	2.63	3.5373 (14)	152.4
C9—H9···Cl1ⁱⁱⁱ	0.95	2.80	3.5599 (16)	138.1
C12—H12A···Cl1ⁱⁱ	0.98	2.70	3.6085 (14)	155.0
C12—H12B···Cl1	0.98	2.78	3.6566 (14)	148.9
C12—H12C···Cl1^iv	0.98	2.68	3.6380 (14)	166.4

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

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
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/S1600536808040506

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