(1-Hy­droxy­ethyl­idene)(meth­yl)aza­nium bromide–N-methyl­acetamide (1/1)

Wei, B.

doi:10.1107/S1600536812016984

organic compounds

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Volume 68| Part 5| May 2012| Page o1491

doi:10.1107/S1600536812016984

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(1-Hydroxyethylidene)(methyl)azanium bromide–N-methylacetamide (1/1)

Bin Wei ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: seuwei@126.com

(Received 8 March 2012; accepted 18 April 2012; online 21 April 2012)

The asymmetric unit of the organic hybrid salt, C₃H₈NO⁺·Br⁻·C₃H₇NO, comprises an N-methylacetamide cation, a N-methylacetamide molecule and a bromide anion. The amide species are linked head-to-head through a short O⋯H⋯O hydrogen bond, giving a monocation, which is extended by N—H⋯Br hydrogen bonds into chains along the b-axis direction.

Related literature

For general background to frameworks and structural phase transitions, see: Ye et al. (2009 ); Zhang et al. (2009 ). For the structure of the hemihydrochloride of N-methylacetamide, see: Jaber et al. (1983 ).

Experimental

Crystal data

C₃H₈NO⁺·Br⁻·C₃H₇NO
M_r = 227.11
Orthorhombic, C m c a
a = 6.8830 (14) Å
b = 23.029 (5) Å
c = 13.291 (3) Å
V = 2106.7 (8) Å³
Z = 8
Mo Kα radiation
μ = 3.87 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.461, T_max = 0.480
10344 measured reflections
1311 independent reflections
858 reflections with I > 2σ(I)
R_int = 0.073

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.101
S = 1.06
1311 reflections
80 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Br1ⁱ	0.89 (5)	2.51 (5)	3.402 (5)	178 (5)
O1—H3⋯O2	1.16 (7)	1.27 (7)	2.437 (4)	179 (6)
N1—H1⋯Br1	0.83 (4)	2.48 (5)	3.304 (4)	174 (5)
Symmetry code: (i) $[x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812016984/zs2188sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016984/zs2188Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812016984/zs2188Isup3.cml

checkCIF report

Comment top

Recent studies have revealed that small molecular compounds which have one or more amidogens may possess dielectric-ferroelectric properties (Ye et al., 2009; Zhang et al., 2009). Our research has been aimed at the synthesis of aromatic amidogen-containing compounds which may possess these properties. As part of our ongoing studies, we report here the crystal structure of the title compound, C₆H₁₅N₂⁺ Br^-, the hydrobromide of N-methylacetamide The structure of the analogous hydrochloride of N-methylacetamide has previously been reported (Jaber et al., 1983).

The structure of the title compound, determined at ambient temperature (298 K), reveals that the asymmetric unit contains an N-methylacetamide cation, a N-methylacetamide molecule and a bromide anion (Fig. 1). The transferred proton is found within a short O1···H···O2 hydrogen bond (Table 1) linking the two molecules head-to-head in the monocation. These cations and the bromide anions form N—H···Br hydrogen-bonding associations giving one-dimensional chains which extend along the b-cell direction (Fig. 2). Unfortunately, the dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent below the melting point (368-369 K) and that it has no dielectric disuniform from 80 K to 405 K.

Related literature top

For general background to frameworks and structural phase transitions, see: Ye et al. (2009); Zhang et al. (2009). For the structure of the hemihydrochloride of N-methylacetamide, see: Jaber et al. (1983). Scheme should show the correct components

Experimental top

The N-methylacetamide(1.46 g, 20 mmol) and hydrobromic acid (1.62 g, 20 mmol) was combined in 30 ml of aqueous solution. The mixture was stirred for 30 min to allow complete reaction and good quality blocky single crystals were obtained by slow evaporation after ca. two weeks (yield, 42%)

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound, with the inter-species hydrogen bonds shown as dashed lines. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the packing of the title compound, showing the hydrogen-bonded chain extension along the b axis. Dashed lines indicate hydrogen bonds.

(1-Hydroxyethylidene)(methyl)azanium bromide–N-methylacetamide (1/1) top

Crystal data top

C₃H₈NO⁺·Br⁻·C₃H₇NO	F(000) = 928
M_r = 227.11	D_x = 1.432 Mg m⁻³
Orthorhombic, Cmca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2	Cell parameters from 3638 reflections
a = 6.8830 (14) Å	θ = 3.0–27.5°
b = 23.029 (5) Å	µ = 3.87 mm⁻¹
c = 13.291 (3) Å	T = 298 K
V = 2106.7 (8) Å³	Block, colorless
Z = 8	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	858 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.073
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −29→29
T_min = 0.461, T_max = 0.480	l = −17→17
10344 measured reflections	2 standard reflections every 150 reflections
1311 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0445P)² + 0.3335P] where P = (F_o² + 2F_c²)/3
1311 reflections	(Δ/σ)_max < 0.001
80 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₃H₈NO⁺·Br⁻·C₃H₇NO	V = 2106.7 (8) Å³
M_r = 227.11	Z = 8
Orthorhombic, Cmca	Mo Kα radiation
a = 6.8830 (14) Å	µ = 3.87 mm⁻¹
b = 23.029 (5) Å	T = 298 K
c = 13.291 (3) Å	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	858 reflections with I > 2σ(I)
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	R_int = 0.073
T_min = 0.461, T_max = 0.480	2 standard reflections every 150 reflections
10344 measured reflections	intensity decay: none
1311 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.40 e Å⁻³
1311 reflections	Δρ_min = −0.25 e Å⁻³
80 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	Occ. (<1)
Br1	0.5000	0.147343 (18)	0.08336 (4)	0.0651 (3)
H1	0.5000	0.233 (2)	0.196 (4)	0.069 (16)*
N1	0.5000	0.25929 (16)	0.2388 (3)	0.0553 (10)
O1	0.5000	0.35425 (13)	0.2661 (3)	0.0714 (10)
C2	0.5000	0.4921 (2)	0.2594 (4)	0.0578 (12)
H2	0.5000	0.573 (2)	0.277 (4)	0.092 (19)*
N2	0.5000	0.54618 (17)	0.2301 (3)	0.0635 (11)
O2	0.5000	0.45173 (14)	0.1949 (3)	0.0717 (10)
C5	0.5000	0.31197 (19)	0.2038 (3)	0.0506 (11)
C6	0.5000	0.24321 (19)	0.3449 (3)	0.0658 (14)
H7A	0.5414	0.2758	0.3846	0.099*	0.50
H7B	0.5874	0.2113	0.3552	0.099*	0.50
H7C	0.3712	0.2320	0.3647	0.099*	0.50
C4	0.5000	0.3231 (2)	0.0925 (3)	0.0695 (15)
H8A	0.5940	0.3526	0.0769	0.104*	0.50
H8B	0.3734	0.3359	0.0719	0.104*	0.50
H8C	0.5326	0.2880	0.0575	0.104*	0.50
C3	0.5000	0.4790 (2)	0.3693 (4)	0.0724 (15)
H9A	0.4649	0.5133	0.4061	0.109*	0.50
H9B	0.6273	0.4666	0.3894	0.109*	0.50
H9C	0.4078	0.4488	0.3831	0.109*	0.50
C1	0.5000	0.5647 (2)	0.1246 (4)	0.0804 (16)
H10A	0.6291	0.5759	0.1053	0.121*	0.50
H10B	0.4138	0.5972	0.1165	0.121*	0.50
H10C	0.4571	0.5332	0.0828	0.121*	0.50
H3	0.5000	0.401 (3)	0.231 (5)	0.15 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0934 (5)	0.0415 (3)	0.0606 (4)	0.000	0.000	−0.0013 (2)
N1	0.074 (3)	0.039 (2)	0.052 (2)	0.000	0.000	−0.001 (2)
O1	0.124 (3)	0.0397 (18)	0.051 (2)	0.000	0.000	−0.0049 (15)
C2	0.060 (3)	0.046 (3)	0.068 (3)	0.000	0.000	−0.005 (3)
N2	0.077 (3)	0.042 (2)	0.071 (3)	0.000	0.000	−0.007 (2)
O2	0.115 (3)	0.0394 (17)	0.061 (2)	0.000	0.000	−0.0052 (16)
C5	0.054 (3)	0.045 (3)	0.052 (3)	0.000	0.000	−0.002 (2)
C6	0.084 (4)	0.054 (3)	0.059 (3)	0.000	0.000	0.008 (2)
C4	0.099 (4)	0.057 (3)	0.052 (3)	0.000	0.000	0.003 (2)
C3	0.104 (4)	0.055 (3)	0.058 (3)	0.000	0.000	−0.003 (3)
C1	0.100 (4)	0.062 (3)	0.080 (4)	0.000	0.000	0.022 (3)

Geometric parameters (Å, º) top

N1—C5	1.299 (5)	C6—H7B	0.9600
N1—C6	1.458 (6)	C6—H7C	0.9600
N1—H1	0.83 (4)	C4—H8A	0.9600
O1—C5	1.278 (5)	C4—H8B	0.9600
O1—H3	1.16 (7)	C4—H8C	0.9600
C2—O2	1.266 (5)	C3—H9A	0.9600
C2—N2	1.304 (5)	C3—H9B	0.9600
C2—C3	1.491 (6)	C3—H9C	0.9600
N2—C1	1.466 (6)	C1—H10A	0.9600
N2—H2	0.89 (5)	C1—H10B	0.9600
C5—C4	1.502 (6)	C1—H10C	0.9600
C6—H7A	0.9600

C5—N1—C6	125.7 (4)	H7B—C6—H7C	109.5
C5—N1—H1	116 (4)	C5—C4—H8A	109.5
C6—N1—H1	118 (4)	C5—C4—H8B	109.5
C5—O1—H3	116 (3)	H8A—C4—H8B	109.5
O2—C2—N2	119.9 (5)	C5—C4—H8C	109.5
O2—C2—C3	121.0 (4)	H8A—C4—H8C	109.5
N2—C2—C3	119.0 (4)	H8B—C4—H8C	109.5
C2—N2—C1	124.3 (5)	C2—C3—H9A	109.5
C2—N2—H2	118 (4)	C2—C3—H9B	109.5
C1—N2—H2	118 (4)	H9A—C3—H9B	109.5
C2—O2—H3	115 (3)	C2—C3—H9C	109.5
O1—C5—N1	118.6 (4)	H9A—C3—H9C	109.5
O1—C5—C4	120.6 (4)	H9B—C3—H9C	109.5
N1—C5—C4	120.8 (4)	N2—C1—H10A	109.5
N1—C6—H7A	109.5	N2—C1—H10B	109.5
N1—C6—H7B	109.5	H10A—C1—H10B	109.5
H7A—C6—H7B	109.5	N2—C1—H10C	109.5
N1—C6—H7C	109.5	H10A—C1—H10C	109.5
H7A—C6—H7C	109.5	H10B—C1—H10C	109.5

C6—N1—C5—O1	0.00	C1—N2—C2—O2	0.00
C6—N1—C5—C4	180.00	C1—N2—C2—C3	180.00

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Br1ⁱ	0.89 (5)	2.51 (5)	3.402 (5)	178 (5)
O1—H3···O2	1.16 (7)	1.27 (7)	2.437 (4)	179 (6)
N1—H1···Br1	0.83 (4)	2.48 (5)	3.304 (4)	174 (5)

Symmetry code: (i) x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₃H₈NO⁺·Br⁻·C₃H₇NO
M_r	227.11
Crystal system, space group	Orthorhombic, Cmca
Temperature (K)	298
a, b, c (Å)	6.8830 (14), 23.029 (5), 13.291 (3)
V (Å³)	2106.7 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.87
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.461, 0.480
No. of measured, independent and observed [I > 2σ(I)] reflections	10344, 1311, 858
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.101, 1.06
No. of reflections	1311
No. of parameters	80
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.25

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Br1ⁱ	0.89 (5)	2.51 (5)	3.402 (5)	178 (5)
O1—H3···O2	1.16 (7)	1.27 (7)	2.437 (4)	179 (6)
N1—H1···Br1	0.83 (4)	2.48 (5)	3.304 (4)	174 (5)

Symmetry code: (i) x, y+1/2, −z+1/2.

Acknowledgements

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

References

Jaber, M., Guilhem, J. & Loiseleur, H. (1983). Acta Cryst. C39, 485–487. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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