4-Methyl­morpholinium bromide

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.037
• wR factor = 0.098
• Data-to-parameter ratio = 19.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        150 Ang.
PLAT194_ALERT_1_C Missing _cell_measurement_reflns_used datum ....          ?
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              Br

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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°.

Related literature

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

S2. 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.

S3. 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 U_iso(H) = 1.2U_eq(C),

U_iso(H) = 1.2U_eq(N).

Computing details

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

	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.

4-Methylmorpholinium bromide

Crystal data

C5H12NO^+·Br^−	F(000) = 184
Mr = 182.07	Dx = 1.506 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 0 reflections
a = 7.3282 (15) Å	θ = 3.8–27.5°
b = 7.4170 (15) Å	µ = 5.04 mm^−1
c = 7.3928 (15) Å	T = 293 K
β = 92.72 (3)°	Prism, colourless
V = 401.37 (14) Å^3	0.40 × 0.30 × 0.20 mm
Z = 2

Data collection

Rigaku Mercury2 diffractometer	995 independent reflections
Radiation source: fine-focus sealed tube	866 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.8°
CCD_Profile_fitting scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.178, Tmax = 0.365	l = −9→9
4192 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0636P)^2 + 0.1157P] where P = (Fo^2 + 2Fc^2)/3
995 reflections	(Δ/σ)max < 0.001
50 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.72 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.5268 (5)	0.7500	0.3399 (6)	0.0810 (14)
N1	0.1476 (4)	0.7500	0.2465 (5)	0.0352 (7)
H1B	0.1507	0.7500	0.1250	0.062 (16)*
C1	0.4418 (5)	0.5939 (7)	0.2671 (6)	0.0749 (13)
H1A	0.4478	0.5968	0.1377	0.096 (16)*
H1C	0.5054	0.4884	0.3106	0.110 (18)*
C2	0.2434 (4)	0.5854 (5)	0.3149 (5)	0.0488 (8)
H2A	0.1864	0.4810	0.2604	0.054 (10)*
H2B	0.2359	0.5765	0.4438	0.059 (11)*
C5	−0.0464 (6)	0.7500	0.2948 (7)	0.0484 (11)
H5A	−0.1058	0.6449	0.2455	0.061 (11)*
H5B	−0.0534	0.7500	0.4234	0.059 (16)*
Br1	0.15472 (6)	0.7500	−0.18624 (5)	0.0464 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0332 (17)	0.143 (4)	0.066 (3)	0.000	−0.0037 (18)	0.000
N1	0.0288 (16)	0.047 (2)	0.0300 (17)	0.000	0.0003 (13)	0.000
C1	0.047 (2)	0.116 (4)	0.062 (3)	0.034 (2)	0.0023 (18)	−0.007 (3)
C2	0.0464 (17)	0.0512 (19)	0.0482 (19)	0.0130 (15)	−0.0023 (13)	−0.0017 (15)
C5	0.032 (2)	0.056 (3)	0.057 (3)	0.000	0.004 (2)	0.000
Br1	0.0608 (3)	0.0470 (3)	0.0314 (3)	0.000	0.0005 (2)	0.000

Geometric parameters (Å, º)

O1—C1	1.409 (5)	C1—H1A	0.9600
O1—C1^i	1.409 (5)	C1—H1C	0.9578
N1—C5	1.482 (5)	C2—H2A	0.9597
N1—C2^i	1.485 (4)	C2—H2B	0.9596
N1—C2	1.485 (4)	C5—H5A	0.9562
N1—H1B	0.8997	C5—H5B	0.9550
C1—C2	1.514 (5)
C1—O1—C1^i	110.5 (4)	C2—C1—H1C	110.2
C5—N1—C2^i	111.2 (2)	H1A—C1—H1C	108.0
C5—N1—C2	111.2 (2)	N1—C2—C1	109.3 (3)
C2^i—N1—C2	110.6 (3)	N1—C2—H2A	109.3
C5—N1—H1B	108.1	C1—C2—H2A	109.9
C2^i—N1—H1B	107.8	N1—C2—H2B	110.3
C2—N1—H1B	107.8	C1—C2—H2B	109.6
O1—C1—C2	110.9 (3)	H2A—C2—H2B	108.4
O1—C1—H1A	108.8	N1—C5—H5A	109.4
C2—C1—H1A	108.9	N1—C5—H5B	109.7
O1—C1—H1C	110.1	H5A—C5—H5B	109.5
C1^i—O1—C1—C2	−61.8 (5)	C2^i—N1—C2—C1	−54.4 (4)
C5—N1—C2—C1	−178.4 (3)	O1—C1—C2—N1	57.8 (4)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

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