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4-Allyl­morpholin-4-ium bromide

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[Haertling, G. H. (1999). J. Am. Ceram. Soc. 82, 797-810.]); Homes et al. (2001[Homes, C. C., Vogt, T., Shapiro, S. M., Wakimoto, S. & Ramirez, A. P. (2001). Science, 293, 673-676.]); Fu et al. (2009[Fu, D. W., Ge, J. Z., Dai, J., Ye, H. Y. & Qu, Z. R. (2009). Inorg. Chem. Commun. 12, 994-997.]); Hang et al. (2009[Hang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. 9, 2026-2029.]).

[Scheme 1]

Experimental

Crystal data
  • C7H14NO+·Br

  • Mr = 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.252, Tmax = 0.423

  • 4897 measured reflections

  • 2155 independent reflections

  • 1786 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.59 e Å−3

  • Δρmin = −0.42 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.97 Å and Uiso(H) = 1.2eq(C).

Structure description 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.

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
[Figure 1] Fig. 1. Perspective structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] 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+·BrZ = 2
Mr = 208.10F(000) = 212
Triclinic, P1Dx = 1.465 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.4115 (15) ÅCell parameters from 2158 reflections
b = 7.9727 (16) Åθ = 2.3–27.5°
c = 8.7948 (18) ŵ = 4.30 mm1
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 tubeRint = 0.043
Graphite monochromatorθmax = 27.5°, θmin = 3.5°
ω scansh = 99
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1010
Tmin = 0.252, Tmax = 0.423l = 1111
4897 measured reflections2 standard reflections every 150 reflections
2155 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.099 w = 1/[σ2(Fo2) + (0.0469P)2 + 0.0113P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
2155 reflectionsΔρmax = 0.59 e Å3
92 parametersΔρmin = 0.42 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.193 (10)
Crystal data top
C7H14NO+·Brγ = 85.78 (3)°
Mr = 208.10V = 471.75 (17) Å3
Triclinic, P1Z = 2
a = 7.4115 (15) ÅMo Kα radiation
b = 7.9727 (16) ŵ = 4.30 mm1
c = 8.7948 (18) ÅT = 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)
Rint = 0.043
Tmin = 0.252, Tmax = 0.4232 standard reflections every 150 reflections
4897 measured reflections intensity decay: none
2155 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.07Δρmax = 0.59 e Å3
2155 reflectionsΔρmin = 0.42 e Å3
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
xyzUiso*/Ueq
O10.2009 (4)0.5927 (3)0.8606 (3)0.0636 (7)
N10.2630 (3)0.2655 (3)0.7998 (3)0.0367 (5)
H1C0.38630.25670.79880.044*
C10.1820 (5)0.2637 (5)0.9663 (4)0.0509 (8)
H1A0.21790.15151.05480.061*
H1B0.05010.26840.97290.061*
C20.2476 (6)0.4268 (5)0.9881 (5)0.0620 (10)
H2A0.19410.42601.09550.074*
H2B0.37890.41760.98760.074*
C30.2827 (5)0.5971 (4)0.7029 (4)0.0573 (9)
H3A0.41410.58780.70180.069*
H3B0.25310.71320.61580.069*
C40.2186 (4)0.4436 (4)0.6671 (4)0.0468 (7)
H4A0.08800.45550.66260.056*
H4B0.27730.44950.55960.056*
C50.2028 (4)0.1047 (4)0.7716 (4)0.0468 (8)
H5A0.23210.00790.86300.056*
H5B0.07180.11190.77060.056*
C60.2918 (5)0.1003 (5)0.6127 (5)0.0550 (9)
H6A0.41710.07940.60280.066*
C70.2073 (8)0.1237 (6)0.4856 (6)0.0848 (14)
H7A0.08200.14490.49110.102*
H7B0.27210.11920.38890.102*
Br10.29920 (3)0.76037 (4)0.22722 (4)0.0524 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0796 (17)0.0498 (14)0.0661 (16)0.0035 (12)0.0026 (13)0.0323 (12)
N10.0285 (10)0.0366 (13)0.0429 (13)0.0007 (9)0.0024 (9)0.0142 (10)
C10.0496 (17)0.0539 (19)0.0436 (18)0.0032 (15)0.0002 (14)0.0160 (15)
C20.070 (2)0.072 (3)0.051 (2)0.001 (2)0.0022 (18)0.034 (2)
C30.070 (2)0.0361 (17)0.061 (2)0.0049 (16)0.0035 (18)0.0178 (16)
C40.0537 (18)0.0369 (16)0.0455 (18)0.0008 (14)0.0055 (14)0.0121 (14)
C50.0414 (16)0.0361 (16)0.062 (2)0.0020 (13)0.0098 (14)0.0172 (15)
C60.0551 (19)0.0498 (19)0.069 (2)0.0016 (16)0.0125 (17)0.0316 (18)
C70.110 (4)0.075 (3)0.086 (3)0.007 (3)0.029 (3)0.044 (3)
Br10.0324 (2)0.0604 (3)0.0540 (3)0.00297 (15)0.00786 (14)0.01133 (17)
Geometric parameters (Å, º) top
O1—C21.407 (4)C3—H3A0.9700
O1—C31.424 (4)C3—H3B0.9700
N1—C41.483 (3)C4—H4A0.9700
N1—C11.500 (4)C4—H4B0.9700
N1—C51.508 (4)C5—C61.474 (5)
N1—H1C0.9100C5—H5A0.9700
C1—C21.511 (5)C5—H5B0.9700
C1—H1A0.9700C6—C71.298 (5)
C1—H1B0.9700C6—H6A0.9300
C2—H2A0.9700C7—H7A0.9300
C2—H2B0.9700C7—H7B0.9300
C3—C41.503 (5)
C2—O1—C3109.7 (3)O1—C3—H3B109.3
C4—N1—C1109.1 (2)C4—C3—H3B109.3
C4—N1—C5112.6 (2)H3A—C3—H3B108.0
C1—N1—C5111.8 (2)N1—C4—C3109.7 (3)
C4—N1—H1C107.7N1—C4—H4A109.7
C1—N1—H1C107.7C3—C4—H4A109.7
C5—N1—H1C107.7N1—C4—H4B109.7
N1—C1—C2109.4 (3)C3—C4—H4B109.7
N1—C1—H1A109.8H4A—C4—H4B108.2
C2—C1—H1A109.8C6—C5—N1111.6 (3)
N1—C1—H1B109.8C6—C5—H5A109.3
C2—C1—H1B109.8N1—C5—H5A109.3
H1A—C1—H1B108.2C6—C5—H5B109.3
O1—C2—C1111.7 (3)N1—C5—H5B109.3
O1—C2—H2A109.3H5A—C5—H5B108.0
C1—C2—H2A109.3C7—C6—C5124.5 (4)
O1—C2—H2B109.3C7—C6—H6A117.7
C1—C2—H2B109.3C5—C6—H6A117.7
H2A—C2—H2B107.9C6—C7—H7A120.0
O1—C3—C4111.6 (3)C6—C7—H7B120.0
O1—C3—H3A109.3H7A—C7—H7B120.0
C4—C3—H3A109.3
C4—N1—C1—C255.2 (3)C5—N1—C4—C3179.8 (3)
C5—N1—C1—C2179.7 (3)O1—C3—C4—N158.9 (4)
C3—O1—C2—C160.5 (4)C4—N1—C5—C660.5 (3)
N1—C1—C2—O158.5 (4)C1—N1—C5—C6176.4 (3)
C2—O1—C3—C460.7 (4)N1—C5—C6—C7113.9 (4)
C1—N1—C4—C355.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···Br1i0.912.313.218 (2)175
C1—H1A···Br1ii0.972.933.846 (4)158
C5—H5B···Br1iii0.972.863.796 (3)162
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y1, z+1; (iii) x, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC7H14NO+·Br
Mr208.10
Crystal system, space groupTriclinic, 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)
V3)471.75 (17)
Z2
Radiation typeMo Kα
µ (mm1)4.30
Crystal size (mm)0.33 × 0.28 × 0.20
Data collection
DiffractometerRigaku SCXmini
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.252, 0.423
No. of measured, independent and
observed [I > 2σ(I)] reflections
4897, 2155, 1786
Rint0.043
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.099, 1.07
No. of reflections2155
No. of parameters92
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1C···Br1i0.912.313.218 (2)175
C1—H1A···Br1ii0.972.933.846 (4)158
C5—H5B···Br1iii0.972.863.796 (3)162
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y1, 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

First citationFu, D. W., Ge, J. Z., Dai, J., Ye, H. Y. & Qu, Z. R. (2009). Inorg. Chem. Commun. 12, 994–997.  Web of Science CSD CrossRef CAS
First citationHaertling, G. H. (1999). J. Am. Ceram. Soc. 82, 797–810.  CrossRef CAS
First citationHang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. 9, 2026–2029.  Web of Science CSD CrossRef CAS
First citationHomes, C. C., Vogt, T., Shapiro, S. M., Wakimoto, S. & Ramirez, A. P. (2001). Science, 293, 673–676.  Web of Science CrossRef PubMed CAS
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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ISSN: 2056-9890
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