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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1375.
Published online 2010 May 15. doi:  10.1107/S1600536810017447
PMCID: PMC2979363

4-Methyl­morpholinium bromide

Abstract

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 [triangle]); Zhang et al. (2009 [triangle]).

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Object name is e-66-o1375-scheme1.jpg

Experimental

Crystal data

  • C5H12NO+·Br
  • M r = 182.07
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1375-efi1.jpg
  • 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 [triangle]) T min = 0.178, T max = 0.365
  • 4192 measured reflections
  • 995 independent reflections
  • 866 reflections with I > 2σ(I)
  • R int = 0.046

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 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

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL/PC (Sheldrick, 2008 [triangle]); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017447/ng2770sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017447/ng2770Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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°.

Experimental

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

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).

Figures

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.
Fig. 2.
A view of the packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.

Crystal data

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

Rigaku Mercury2 diffractometer995 independent reflections
Radiation source: fine-focus sealed tube866 reflections with I > 2σ(I)
graphiteRint = 0.046
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.8°
CCD_Profile_fitting scansh = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −9→9
Tmin = 0.178, Tmax = 0.365l = −9→9
4192 measured reflections

Refinement

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 = 0.97w = 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

Special details

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)

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)*
C5−0.0464 (6)0.75000.2948 (7)0.0484 (11)
H5A−0.10580.64490.24550.061 (11)*
H5B−0.05340.75000.42340.059 (16)*
Br10.15472 (6)0.7500−0.18624 (5)0.0464 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0332 (17)0.143 (4)0.066 (3)0.000−0.0037 (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, °)

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—C2−61.8 (5)C2i—N1—C2—C1−54.4 (4)
C5—N1—C2—C1−178.4 (3)O1—C1—C2—N157.8 (4)

Symmetry codes: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1B···Br10.902.303.202 (4)179

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2770).

References

  • Ferguson, G. (1999). PRPKAPPA University of Guelph, Canada.
  • Hang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des.5, 2026–2029.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhang, W., Chen, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. D. (2009). J. Am. Chem. Soc.131, 12544–12545. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography