4-Allyl­morpholin-4-ium bromide

Han, M.T.

doi:10.1107/S1600536812010793

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1089

doi:10.1107/S1600536812010793

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4-Allylmorpholin-4-ium bromide

Meng Ting Han ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical, Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: saltfish777@gmail.com

(Received 21 February 2012; accepted 12 March 2012; online 17 March 2012)

The title compound, C₇H₁₄NO⁺·Br⁻, was formed by reaction of 4-allylmorpholine and hydrogen bromide. In the crystal, molecules are connected via N—H⋯Br and C—H⋯Br hydrogen bonds, forming a three-dimensional network.

Related literature

For selected sources of ferroelectric materials, see: Haertling (1999 ); Homes et al. (2001 ); Fu et al. (2009 ); Hang et al. (2009 ).

Experimental

Crystal data

C₇H₁₄NO⁺·Br⁻
M_r = 208.10
Triclinic, $[P \overline 1]$
a = 7.4115 (15) Å
b = 7.9727 (16) Å
c = 8.7948 (18) Å
α = 66.43 (3)°
β = 82.14 (3)°
γ = 85.78 (3)°
V = 471.75 (17) Å³
Z = 2
Mo Kα radiation
μ = 4.30 mm⁻¹
T = 293 K
0.33 × 0.28 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.252, T_max = 0.423
4897 measured reflections
2155 independent reflections
1786 reflections with I > 2σ(I)
R_int = 0.043
2 standard reflections every 150 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.099
S = 1.07
2155 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯Br1ⁱ	0.91	2.31	3.218 (2)	175
C1—H1A⋯Br1ⁱⁱ	0.97	2.93	3.846 (4)	158
C5—H5B⋯Br1ⁱⁱⁱ	0.97	2.86	3.796 (3)	162
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y-1, z+1; (iii) -x, -y+1, -z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (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/S1600536812010793/mw2056sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812010793/mw2056Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812010793/mw2056Isup3.cml

checkCIF report

Comment top

At present, much attention in ferroelectric material field is focused on developing ferroelectric pure organic or inorganic compounds (Haertling et al. 1999; Homes et al. 2001). Recently we have reported the synthesis of a variety of compounds (Fu et al., 2009; Hang et al., 2009), which have potential piezoelectric and ferroelectric properties. In order to find more dielectric ferroelectric materials, we investigate the physical properties of the title compound (Fig. 1). The dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent (dielectric constant equaling to 0.6 to 1.42), suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range. Similarly, below the melting point (408 K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed (dielectric constant equaling to 0.6 to 1.42).Herein, we report the synthesis and crystal structure of the title compound.

As can be seen from the packing diagram (Fig. 2), molecules are connected via intermolecular N—H···Br and C—H···Br hydrogen bonds to form a three-dimensional network. Dipole–dipole and van der Waals interactions are also operative in organizing the molecular packing.

Related literature top

For selected sources of ferroelectric materials see: Haertling et al. (1999); Homes et al. (2001); Fu et al. (2009); Hang et al. (2009).

Experimental top

A mix of 4-allylmorpholine (0.762 g, 0.006 mol) and hydrogen bromide (1.212 g, 0.006 mol) in water (20 ml) was stirred until clear. After several days, the title compound was formed and recrystallized from solution to afford red prismatic crystals suitable for X-ray analysis.

Structure description top

For selected sources of ferroelectric materials see: Haertling et al. (1999); Homes et al. (2001); Fu et al. (2009); Hang et al. (2009).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the a axis showing the hydrogen bonding network. Some of the H-atoms have been ommitted for clarity.

4-Allylmorpholin-4-ium bromide top

Crystal data top

C₇H₁₄NO⁺·Br⁻	Z = 2
M_r = 208.10	F(000) = 212
Triclinic, P1	D_x = 1.465 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4115 (15) Å	Cell parameters from 2158 reflections
b = 7.9727 (16) Å	θ = 2.3–27.5°
c = 8.7948 (18) Å	µ = 4.30 mm⁻¹
α = 66.43 (3)°	T = 293 K
β = 82.14 (3)°	Prismatic, red
γ = 85.78 (3)°	0.33 × 0.28 × 0.20 mm
V = 471.75 (17) Å³

Data collection top

Rigaku SCXmini diffractometer	1786 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.043
Graphite monochromator	θ_max = 27.5°, θ_min = 3.5°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.252, T_max = 0.423	l = −11→11
4897 measured reflections	2 standard reflections every 150 reflections
2155 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0469P)² + 0.0113P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
2155 reflections	Δρ_max = 0.59 e Å⁻³
92 parameters	Δρ_min = −0.42 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.193 (10)

Crystal data top

C₇H₁₄NO⁺·Br⁻	γ = 85.78 (3)°
M_r = 208.10	V = 471.75 (17) Å³
Triclinic, P1	Z = 2
a = 7.4115 (15) Å	Mo Kα radiation
b = 7.9727 (16) Å	µ = 4.30 mm⁻¹
c = 8.7948 (18) Å	T = 293 K
α = 66.43 (3)°	0.33 × 0.28 × 0.20 mm
β = 82.14 (3)°

Data collection top

Rigaku SCXmini diffractometer	1786 reflections with I > 2σ(I)
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	R_int = 0.043
T_min = 0.252, T_max = 0.423	2 standard reflections every 150 reflections
4897 measured reflections	intensity decay: none
2155 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.07	Δρ_max = 0.59 e Å⁻³
2155 reflections	Δρ_min = −0.42 e Å⁻³
92 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
O1	0.2009 (4)	0.5927 (3)	0.8606 (3)	0.0636 (7)
N1	0.2630 (3)	0.2655 (3)	0.7998 (3)	0.0367 (5)
H1C	0.3863	0.2567	0.7988	0.044*
C1	0.1820 (5)	0.2637 (5)	0.9663 (4)	0.0509 (8)
H1A	0.2179	0.1515	1.0548	0.061*
H1B	0.0501	0.2684	0.9729	0.061*
C2	0.2476 (6)	0.4268 (5)	0.9881 (5)	0.0620 (10)
H2A	0.1941	0.4260	1.0955	0.074*
H2B	0.3789	0.4176	0.9876	0.074*
C3	0.2827 (5)	0.5971 (4)	0.7029 (4)	0.0573 (9)
H3A	0.4141	0.5878	0.7018	0.069*
H3B	0.2531	0.7132	0.6158	0.069*
C4	0.2186 (4)	0.4436 (4)	0.6671 (4)	0.0468 (7)
H4A	0.0880	0.4555	0.6626	0.056*
H4B	0.2773	0.4495	0.5596	0.056*
C5	0.2028 (4)	0.1047 (4)	0.7716 (4)	0.0468 (8)
H5A	0.2321	−0.0079	0.8630	0.056*
H5B	0.0718	0.1119	0.7706	0.056*
C6	0.2918 (5)	0.1003 (5)	0.6127 (5)	0.0550 (9)
H6A	0.4171	0.0794	0.6028	0.066*
C7	0.2073 (8)	0.1237 (6)	0.4856 (6)	0.0848 (14)
H7A	0.0820	0.1449	0.4911	0.102*
H7B	0.2721	0.1192	0.3889	0.102*
Br1	0.29920 (3)	0.76037 (4)	0.22722 (4)	0.0524 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0796 (17)	0.0498 (14)	0.0661 (16)	0.0035 (12)	0.0026 (13)	−0.0323 (12)
N1	0.0285 (10)	0.0366 (13)	0.0429 (13)	0.0007 (9)	−0.0024 (9)	−0.0142 (10)
C1	0.0496 (17)	0.0539 (19)	0.0436 (18)	0.0032 (15)	0.0002 (14)	−0.0160 (15)
C2	0.070 (2)	0.072 (3)	0.051 (2)	0.001 (2)	−0.0022 (18)	−0.034 (2)
C3	0.070 (2)	0.0361 (17)	0.061 (2)	−0.0049 (16)	0.0035 (18)	−0.0178 (16)
C4	0.0537 (18)	0.0369 (16)	0.0455 (18)	−0.0008 (14)	−0.0055 (14)	−0.0121 (14)
C5	0.0414 (16)	0.0361 (16)	0.062 (2)	−0.0020 (13)	−0.0098 (14)	−0.0172 (15)
C6	0.0551 (19)	0.0498 (19)	0.069 (2)	0.0016 (16)	−0.0125 (17)	−0.0316 (18)
C7	0.110 (4)	0.075 (3)	0.086 (3)	0.007 (3)	−0.029 (3)	−0.044 (3)
Br1	0.0324 (2)	0.0604 (3)	0.0540 (3)	0.00297 (15)	−0.00786 (14)	−0.01133 (17)

Geometric parameters (Å, º) top

O1—C2	1.407 (4)	C3—H3A	0.9700
O1—C3	1.424 (4)	C3—H3B	0.9700
N1—C4	1.483 (3)	C4—H4A	0.9700
N1—C1	1.500 (4)	C4—H4B	0.9700
N1—C5	1.508 (4)	C5—C6	1.474 (5)
N1—H1C	0.9100	C5—H5A	0.9700
C1—C2	1.511 (5)	C5—H5B	0.9700
C1—H1A	0.9700	C6—C7	1.298 (5)
C1—H1B	0.9700	C6—H6A	0.9300
C2—H2A	0.9700	C7—H7A	0.9300
C2—H2B	0.9700	C7—H7B	0.9300
C3—C4	1.503 (5)

C2—O1—C3	109.7 (3)	O1—C3—H3B	109.3
C4—N1—C1	109.1 (2)	C4—C3—H3B	109.3
C4—N1—C5	112.6 (2)	H3A—C3—H3B	108.0
C1—N1—C5	111.8 (2)	N1—C4—C3	109.7 (3)
C4—N1—H1C	107.7	N1—C4—H4A	109.7
C1—N1—H1C	107.7	C3—C4—H4A	109.7
C5—N1—H1C	107.7	N1—C4—H4B	109.7
N1—C1—C2	109.4 (3)	C3—C4—H4B	109.7
N1—C1—H1A	109.8	H4A—C4—H4B	108.2
C2—C1—H1A	109.8	C6—C5—N1	111.6 (3)
N1—C1—H1B	109.8	C6—C5—H5A	109.3
C2—C1—H1B	109.8	N1—C5—H5A	109.3
H1A—C1—H1B	108.2	C6—C5—H5B	109.3
O1—C2—C1	111.7 (3)	N1—C5—H5B	109.3
O1—C2—H2A	109.3	H5A—C5—H5B	108.0
C1—C2—H2A	109.3	C7—C6—C5	124.5 (4)
O1—C2—H2B	109.3	C7—C6—H6A	117.7
C1—C2—H2B	109.3	C5—C6—H6A	117.7
H2A—C2—H2B	107.9	C6—C7—H7A	120.0
O1—C3—C4	111.6 (3)	C6—C7—H7B	120.0
O1—C3—H3A	109.3	H7A—C7—H7B	120.0
C4—C3—H3A	109.3

C4—N1—C1—C2	−55.2 (3)	C5—N1—C4—C3	−179.8 (3)
C5—N1—C1—C2	179.7 (3)	O1—C3—C4—N1	−58.9 (4)
C3—O1—C2—C1	−60.5 (4)	C4—N1—C5—C6	60.5 (3)
N1—C1—C2—O1	58.5 (4)	C1—N1—C5—C6	−176.4 (3)
C2—O1—C3—C4	60.7 (4)	N1—C5—C6—C7	−113.9 (4)
C1—N1—C4—C3	55.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Br1ⁱ	0.91	2.31	3.218 (2)	175
C1—H1A···Br1ⁱⁱ	0.97	2.93	3.846 (4)	158
C5—H5B···Br1ⁱⁱⁱ	0.97	2.86	3.796 (3)	162

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

Experimental details

Crystal data
Chemical formula	C₇H₁₄NO⁺·Br⁻
M_r	208.10
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.4115 (15), 7.9727 (16), 8.7948 (18)
α, β, γ (°)	66.43 (3), 82.14 (3), 85.78 (3)
V (Å³)	471.75 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.30
Crystal size (mm)	0.33 × 0.28 × 0.20

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.252, 0.423
No. of measured, independent and observed [I > 2σ(I)] reflections	4897, 2155, 1786
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.099, 1.07
No. of reflections	2155
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.42

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Br1ⁱ	0.91	2.31	3.218 (2)	175
C1—H1A···Br1ⁱⁱ	0.97	2.93	3.846 (4)	158
C5—H5B···Br1ⁱⁱⁱ	0.97	2.86	3.796 (3)	162

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

Acknowledgements

The authors are grateful to the starter fund of Southeast University for financial support to buy the X-ray diffractometer.

References

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