organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

4-Methyl­morpholinium bromide

aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: yaojiyuan520@163.com

(Received 8 May 2010; accepted 12 May 2010; online 15 May 2010)

The six-membered ring in the title salt, C5H12NO+·Br, has a chair conformation. In the crystal, the cations are linked to the anions by N—H⋯Br hydrogen bonds.

Related literature

For background to phase transition materials, see: Hang et al. (2009[Hang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. 5, 2026-2029.]); Zhang et al. (2009[Zhang, W., Chen, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. D. (2009). J. Am. Chem. Soc. 131, 12544-12545.]).

[Scheme 1]

Experimental

Crystal data
  • C5H12NO+·Br

  • Mr = 182.07

  • Monoclinic, P 21 /m

  • a = 7.3282 (15) Å

  • b = 7.4170 (15) Å

  • c = 7.3928 (15) Å

  • β = 92.72 (3)°

  • V = 401.37 (14) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 5.04 mm−1

  • T = 293 K

  • 0.40 × 0.30 × 0.20 mm

Data collection
  • Rigaku Mercury2 diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.178, Tmax = 0.365

  • 4192 measured reflections

  • 995 independent reflections

  • 866 reflections with I > 2σ(I)

  • Rint = 0.046

Refinement
  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.098

  • S = 0.97

  • 995 reflections

  • 50 parameters

  • H-atom parameters constrained

  • Δρmax = 0.33 e Å−3

  • Δρmin = −0.72 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1B⋯Br1 0.90 2.30 3.202 (4) 179

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/PC (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


Comment top

As a study of phase transition materials, including organic ligands ( Hang et al. 2009 ), metal-organic coordination compounds (Zhang et al., 2009 ), organic-inorganic hybrids, we studied the dielectric properties of the title compound, but there was no distinct anomaly observed from 90 K to 420 K, (m.p. 450 K) unfortunately. In this article, the crystal structure of (I) is showed.

The structure is composed of the N-Methylmorpholinium cations, hydrobromide anions (Fig. 1). in space group P21/m.

Packing structure of the title compound along b-axis are shown in Figure 2. N-Methylmorpholinium molecules are linked via hydrogen bonds of the type N—H···Br hydrogen bonds forming a two-dimensional planar sheets with hydrobromide anions. The hydrogen bonds are given in Table 1. The H atom of the protonated ring N atom (H1b) is donated to the Brl- anions, being involved in a strong N—H···Br hydrogen bond. Br- anions take part in electrostatics equilibrium with the N-Methylmorpholinium cations. The associated distances and angles are: Br···H—N 3.202 (4) Å, and 179.3°.

Related literature top

For background to phase transition materials, see: Hang et al. (2009); Zhang et al. (2009)

Experimental top

The title compound was prepared by reaction of stoichiometric amounts of N-Methylmorpholinium and concentrated hydrobromic acid in methanol. The obtained solution was filtered, and left at room temperature for 5 days. colorless crystals were obtained by slow evaporation.

Refinement top

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C, N atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C),

Uiso(H) = 1.2Ueq(N).

Structure description top

As a study of phase transition materials, including organic ligands ( Hang et al. 2009 ), metal-organic coordination compounds (Zhang et al., 2009 ), organic-inorganic hybrids, we studied the dielectric properties of the title compound, but there was no distinct anomaly observed from 90 K to 420 K, (m.p. 450 K) unfortunately. In this article, the crystal structure of (I) is showed.

The structure is composed of the N-Methylmorpholinium cations, hydrobromide anions (Fig. 1). in space group P21/m.

Packing structure of the title compound along b-axis are shown in Figure 2. N-Methylmorpholinium molecules are linked via hydrogen bonds of the type N—H···Br hydrogen bonds forming a two-dimensional planar sheets with hydrobromide anions. The hydrogen bonds are given in Table 1. The H atom of the protonated ring N atom (H1b) is donated to the Brl- anions, being involved in a strong N—H···Br hydrogen bond. Br- anions take part in electrostatics equilibrium with the N-Methylmorpholinium cations. The associated distances and angles are: Br···H—N 3.202 (4) Å, and 179.3°.

For background to phase transition materials, see: Hang et al. (2009); Zhang 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/PC (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level, and all H atoms have been omitted for clarity.
[Figure 2] Fig. 2. A view of the packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.
4-Methylmorpholinium bromide top
Crystal data top
C5H12NO+·BrF(000) = 184
Mr = 182.07Dx = 1.506 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 0 reflections
a = 7.3282 (15) Åθ = 3.8–27.5°
b = 7.4170 (15) ŵ = 5.04 mm1
c = 7.3928 (15) ÅT = 293 K
β = 92.72 (3)°Prism, colourless
V = 401.37 (14) Å30.40 × 0.30 × 0.20 mm
Z = 2
Data collection top
Rigaku Mercury2
diffractometer
995 independent reflections
Radiation source: fine-focus sealed tube866 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.8°
CCD_Profile_fitting scansh = 99
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 99
Tmin = 0.178, Tmax = 0.365l = 99
4192 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0636P)2 + 0.1157P]
where P = (Fo2 + 2Fc2)/3
995 reflections(Δ/σ)max < 0.001
50 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.72 e Å3
Crystal data top
C5H12NO+·BrV = 401.37 (14) Å3
Mr = 182.07Z = 2
Monoclinic, P21/mMo Kα radiation
a = 7.3282 (15) ŵ = 5.04 mm1
b = 7.4170 (15) ÅT = 293 K
c = 7.3928 (15) Å0.40 × 0.30 × 0.20 mm
β = 92.72 (3)°
Data collection top
Rigaku Mercury2
diffractometer
995 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
866 reflections with I > 2σ(I)
Tmin = 0.178, Tmax = 0.365Rint = 0.046
4192 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.098H-atom parameters constrained
S = 0.97Δρmax = 0.33 e Å3
995 reflectionsΔρmin = 0.72 e Å3
50 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O10.5268 (5)0.75000.3399 (6)0.0810 (14)
N10.1476 (4)0.75000.2465 (5)0.0352 (7)
H1B0.15070.75000.12500.062 (16)*
C10.4418 (5)0.5939 (7)0.2671 (6)0.0749 (13)
H1A0.44780.59680.13770.096 (16)*
H1C0.50540.48840.31060.110 (18)*
C20.2434 (4)0.5854 (5)0.3149 (5)0.0488 (8)
H2A0.18640.48100.26040.054 (10)*
H2B0.23590.57650.44380.059 (11)*
C50.0464 (6)0.75000.2948 (7)0.0484 (11)
H5A0.10580.64490.24550.061 (11)*
H5B0.05340.75000.42340.059 (16)*
Br10.15472 (6)0.75000.18624 (5)0.0464 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0332 (17)0.143 (4)0.066 (3)0.0000.0037 (18)0.000
N10.0288 (16)0.047 (2)0.0300 (17)0.0000.0003 (13)0.000
C10.047 (2)0.116 (4)0.062 (3)0.034 (2)0.0023 (18)0.007 (3)
C20.0464 (17)0.0512 (19)0.0482 (19)0.0130 (15)0.0023 (13)0.0017 (15)
C50.032 (2)0.056 (3)0.057 (3)0.0000.004 (2)0.000
Br10.0608 (3)0.0470 (3)0.0314 (3)0.0000.0005 (2)0.000
Geometric parameters (Å, º) top
O1—C11.409 (5)C1—H1A0.9600
O1—C1i1.409 (5)C1—H1C0.9578
N1—C51.482 (5)C2—H2A0.9597
N1—C2i1.485 (4)C2—H2B0.9596
N1—C21.485 (4)C5—H5A0.9562
N1—H1B0.8997C5—H5B0.9550
C1—C21.514 (5)
C1—O1—C1i110.5 (4)C2—C1—H1C110.2
C5—N1—C2i111.2 (2)H1A—C1—H1C108.0
C5—N1—C2111.2 (2)N1—C2—C1109.3 (3)
C2i—N1—C2110.6 (3)N1—C2—H2A109.3
C5—N1—H1B108.1C1—C2—H2A109.9
C2i—N1—H1B107.8N1—C2—H2B110.3
C2—N1—H1B107.8C1—C2—H2B109.6
O1—C1—C2110.9 (3)H2A—C2—H2B108.4
O1—C1—H1A108.8N1—C5—H5A109.4
C2—C1—H1A108.9N1—C5—H5B109.7
O1—C1—H1C110.1H5A—C5—H5B109.5
C1i—O1—C1—C261.8 (5)C2i—N1—C2—C154.4 (4)
C5—N1—C2—C1178.4 (3)O1—C1—C2—N157.8 (4)
Symmetry code: (i) x, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Br10.902.303.202 (4)179

Experimental details

Crystal data
Chemical formulaC5H12NO+·Br
Mr182.07
Crystal system, space groupMonoclinic, P21/m
Temperature (K)293
a, b, c (Å)7.3282 (15), 7.4170 (15), 7.3928 (15)
β (°) 92.72 (3)
V3)401.37 (14)
Z2
Radiation typeMo Kα
µ (mm1)5.04
Crystal size (mm)0.40 × 0.30 × 0.20
Data collection
DiffractometerRigaku Mercury2
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.178, 0.365
No. of measured, independent and
observed [I > 2σ(I)] reflections
4192, 995, 866
Rint0.046
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.098, 0.97
No. of reflections995
No. of parameters50
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.72

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Br10.902.303.202 (4)179.3
 

Acknowledgements

The author is grateful to the starter fund of Southeast University for supporting the purchase of a diffractometer.

References

First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
First citationHang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. 5, 2026–2029.  Web of Science CSD CrossRef Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhang, W., Chen, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. D. (2009). J. Am. Chem. Soc. 131, 12544–12545.  Web of Science CSD CrossRef PubMed CAS Google Scholar

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COMMUNICATIONS
ISSN: 2056-9890
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