4-(2-Chloro­ethyl)­morpholinium chloride

Narasegowda, R.S.; Yathirajan, H.S.; Nagaraja, P.; Lynch, D.E.

doi:10.1107/S1600536805006136

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 4| April 2005| Pages o849-o850

https://doi.org/10.1107/S1600536805006136

4-(2-Chloroethyl)morpholinium chloride

Rajenahally S. Narasegowda,^a Hemmige S. Yathirajan,^a Padmarajaiah Nagaraja ^a and Daniel E. Lynch ^b ^*

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^bSchool of Science and the Environment, Coventry University, Coventry CV1 5FB, England
^*Correspondence e-mail: apx106@coventry.ac.uk

(Received 22 February 2005; accepted 25 February 2005; online 4 March 2005)

The structure of the title compound, C₆H₁₃ClNO⁺·Cl⁻, comprises a cation with the morpholine ring in the chair conformation, and a single hydrogen-bonding association between the morpholinium NH group and the Cl⁻ anion.

Comment

The title compound, (I), is used as an intermediate for the synthesis of the antispasmodic drug pinaverium bromide, and is also used as an intermediate for the synthesis of biologically active heterocycles (Baronnet et al., 1974 ). A search of the Cambridge Structural Database (Version 5.26; Allen, 2002 ) reveals that there are 90 known structures that contain the morpholinium cation. Of these there are 24 that have an N-ethyl chain, or longer, including the structure of 4-(2-fluoroethyl)morpholinium chloride (Briggs et al., 2004 ). This compound crystallizes in monoclinic space group P2₁/n, with the morpholine ring in the chair conformation and a single hydrogen-bonding association between the morpholinium NH group and the Cl⁻ anion (N⋯Cl = 3.036 Å).

The structure of the title compound comprises a cation with the morpholine ring also in the chair conformation (Fig. 1), and a single hydrogen-bonding association similarly between the morpholinium NH group and the Cl⁻ anion (Table 1). Three torsion angles that define the conformation of the chloroethyl chain are C2—C3—N4—C7 [−177.50 (12)°], C3—N4—C7—C8 [162.71 (13)°] and N4—C7—C8—Cl1 [86.66 (15)°]. The equivalent angles in the fluoro analogue are 178.46, −78.85 and −173.68°, respectively.

Figure 1
The molecular configuration and atom-numbering scheme for (I

). Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as spheres of arbitrary radius.

Experimental

An equimolar mixture of morpholine (0.87 g, 10 mmol), anhydrous K₂CO₃ (1.38 g, 10 mmol) and 1-bromo-2-chloroethane (1.43 g, 10 mmol) was stirred at room temperature in dimethylformamide (10 ml) for 6 h. The collected product was subsequently converted to the hydrochloride salt using isopropyl alcohol and HCl (80:20). Crystals of compound (I) were grown from methanol.

Crystal data

C₆H₁₃ClNO⁺·Cl⁻
M_r = 186.07
Triclinic, $[P\overline 1]$
a = 6.9876 (3) Å
b = 8.1549 (4) Å
c = 8.6495 (3) Å
α = 63.530 (2)°
β = 85.004 (3)°
γ = 85.179 (2)°
V = 438.97 (3) Å³
Z = 2
D_x = 1.408 Mg m⁻³
Mo Kα radiation
Cell parameters from 1914 reflections
θ = 2.9–27.5°
μ = 0.68 mm⁻¹
T = 120 (2) K
Plate, colourless
0.28 × 0.24 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.833, T_max = 0.961
7581 measured reflections
1716 independent reflections
1494 reflections with I > 2σ(I)
R_int = 0.032
θ_max = 26.0°
h = −8 → 8
k = −10 → 9
l = −10 → 10

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.078
S = 0.94
1716 reflections
94 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0469P)² + 0.2143P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯Cl2	0.883 (19)	2.16 (2)	3.0435 (14)	178 (2)

The H atom attached to the N atom was located in a difference Fourier synthesis and its positional parameters were refined. Other H atoms were included in the refinement at calculated positions, in the riding-model approximation, with a C—H distance of 0.99 Å. The isotropic displacement parameters for all H atoms were set equal to 1.25U_eq of the carrier atom.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805006136/is6056sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805006136/is6056Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

4-(2-Chloroethyl)morpholinium chloride top

Crystal data top

C₆H₁₃ClNO⁺·Cl⁻	Z = 2
M_r = 186.07	F(000) = 196
Triclinic, P1	D_x = 1.408 Mg m⁻³
Hall symbol: -P 1	Melting point: 458 K
a = 6.9876 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1549 (4) Å	Cell parameters from 1914 reflections
c = 8.6495 (3) Å	θ = 2.9–27.5°
α = 63.530 (2)°	µ = 0.68 mm⁻¹
β = 85.004 (3)°	T = 120 K
γ = 85.179 (2)°	Plate, colourless
V = 438.97 (3) Å³	0.28 × 0.24 × 0.06 mm

Data collection top

Nonius KappaCCD diffractometer	1716 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1494 reflections with I > 2σ(I)
10 cm confocal mirrors monochromator	R_int = 0.032
Detector resolution: 9.091 pixels mm^-1	θ_max = 26.0°, θ_min = 3.8°
φ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −10→9
T_min = 0.833, T_max = 0.961	l = −10→10
7581 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ²(F_o²) + (0.0469P)² + 0.2143P] where P = (F_o² + 2F_c²)/3
1716 reflections	(Δ/σ)_max < 0.001
94 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.31450 (17)	−0.10081 (15)	0.17258 (14)	0.0211 (3)
C2	0.2513 (2)	0.0634 (2)	0.0296 (2)	0.0206 (4)
H21	0.3005	0.0597	−0.0797	0.026*
H22	0.1090	0.0712	0.0319	0.026*
C3	0.3210 (2)	0.2316 (2)	0.0350 (2)	0.0171 (3)
H31	0.2755	0.3437	−0.0652	0.021*
H32	0.4634	0.2269	0.0287	0.021*
N4	0.24469 (19)	0.23719 (18)	0.20020 (17)	0.0133 (3)
H4	0.118 (3)	0.243 (2)	0.203 (2)	0.017*
C5	0.3049 (2)	0.0621 (2)	0.3499 (2)	0.0159 (3)
H51	0.4467	0.0529	0.3546	0.020*
H52	0.2479	0.0611	0.4592	0.020*
C6	0.2391 (2)	−0.0999 (2)	0.3312 (2)	0.0193 (4)
H61	0.0968	−0.0946	0.3346	0.024*
H62	0.2820	−0.2151	0.4295	0.024*
C7	0.3033 (2)	0.4064 (2)	0.2071 (2)	0.0176 (3)
H71	0.4406	0.3899	0.2337	0.022*
H72	0.2906	0.5116	0.0917	0.022*
C8	0.1861 (3)	0.4513 (2)	0.3400 (2)	0.0222 (4)
H81	0.1832	0.5855	0.3010	0.028*
H82	0.0522	0.4168	0.3460	0.028*
Cl1	0.27566 (7)	0.33778 (6)	0.55327 (6)	0.02923 (15)
Cl2	−0.19260 (5)	0.24738 (5)	0.21272 (5)	0.02018 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0271 (7)	0.0174 (6)	0.0196 (6)	−0.0017 (5)	0.0038 (5)	−0.0097 (5)
C2	0.0225 (9)	0.0226 (9)	0.0188 (8)	−0.0015 (7)	−0.0008 (7)	−0.0110 (7)
C3	0.0183 (8)	0.0189 (8)	0.0115 (7)	−0.0003 (6)	0.0018 (6)	−0.0048 (6)
N4	0.0105 (6)	0.0147 (7)	0.0139 (6)	−0.0015 (5)	−0.0008 (5)	−0.0054 (5)
C5	0.0188 (8)	0.0135 (8)	0.0130 (8)	−0.0014 (6)	−0.0011 (6)	−0.0036 (6)
C6	0.0227 (9)	0.0157 (8)	0.0179 (8)	−0.0043 (7)	0.0039 (7)	−0.0063 (7)
C7	0.0195 (8)	0.0124 (8)	0.0185 (8)	−0.0042 (6)	−0.0010 (6)	−0.0042 (7)
C8	0.0217 (9)	0.0188 (9)	0.0291 (9)	0.0020 (7)	−0.0040 (7)	−0.0133 (8)
Cl1	0.0381 (3)	0.0306 (3)	0.0224 (2)	−0.0013 (2)	−0.00025 (19)	−0.0151 (2)
Cl2	0.0122 (2)	0.0228 (2)	0.0189 (2)	−0.00099 (16)	−0.00073 (15)	−0.00332 (18)

Geometric parameters (Å, º) top

N4—C5	1.496 (2)	C6—C5	1.513 (2)
N4—C7	1.4995 (19)	C6—H61	0.99
N4—C3	1.4994 (19)	C6—H62	0.99
N4—H4	0.883 (19)	C5—H51	0.99
C2—C3	1.515 (2)	C5—H52	0.99
C3—H31	0.99	C7—C8	1.512 (2)
C3—H32	0.99	C7—H71	0.99
C2—O1	1.427 (2)	C7—H72	0.99
C2—H21	0.99	C8—Cl1	1.7980 (18)
C2—H22	0.99	C8—H81	0.99
O1—C6	1.4289 (19)	C8—H82	0.99

C5—N4—C7	114.05 (12)	O1—C6—H62	109.4
C5—N4—C3	109.14 (12)	C5—C6—H62	109.4
C7—N4—C3	110.77 (12)	H61—C6—H62	108.0
C5—N4—H4	107.2 (12)	N4—C5—C6	110.00 (13)
C7—N4—H4	106.9 (11)	N4—C5—H51	109.7
C3—N4—H4	108.6 (11)	C6—C5—H51	109.7
N4—C3—C2	109.09 (13)	N4—C5—H52	109.7
N4—C3—H31	109.9	C6—C5—H52	109.7
C2—C3—H31	109.9	H51—C5—H52	108.2
N4—C3—H32	109.9	N4—C7—C8	113.63 (13)
C2—C3—H32	109.9	N4—C7—H71	108.8
H31—C3—H32	108.3	C8—C7—H71	108.8
O1—C2—C3	111.28 (13)	N4—C7—H72	108.8
O1—C2—H21	109.4	C8—C7—H72	108.8
C3—C2—H21	109.4	H71—C7—H72	107.7
O1—C2—H22	109.4	C7—C8—Cl1	114.08 (12)
C3—C2—H22	109.4	C7—C8—H81	108.7
H21—C2—H22	108.0	Cl1—C8—H81	108.7
C2—O1—C6	109.92 (12)	C7—C8—H82	108.7
O1—C6—C5	111.36 (13)	Cl1—C8—H82	108.7
O1—C6—H61	109.4	H81—C8—H82	107.6
C5—C6—H61	109.4

C5—N4—C3—C2	56.13 (16)	C3—N4—C5—C6	−55.60 (16)
C7—N4—C3—C2	−177.50 (12)	O1—C6—C5—N4	57.83 (17)
N4—C3—C2—O1	−59.50 (17)	C5—N4—C7—C8	−73.70 (17)
C3—C2—O1—C6	60.97 (17)	C3—N4—C7—C8	162.71 (13)
C2—O1—C6—C5	−59.89 (17)	N4—C7—C8—Cl1	86.66 (15)
C7—N4—C5—C6	179.93 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···Cl2	0.883 (19)	2.16 (2)	3.0435 (14)	178 (2)

Acknowledgements

The authors thank the EPSRC National Crystallography Service (Southampton, England) and acknowledge the use of the EPSRC's Chemical Database Service at Daresbury (Fletcher et al., 1996 ).

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