2-Methyl­piperidinium bromide

Xu, Q.

doi:10.1107/S1600536812022878

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1962

doi:10.1107/S1600536812022878

Open

access

2-Methylpiperidinium bromide

Qian Xu ^a ^*

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

(Received 12 April 2012; accepted 19 May 2012; online 31 May 2012)

In the title organic–inorganic hybrid salt, C₆H₁₄N⁺·Br⁻, N—H⋯Br hydrogen bonds link the cations and anions, forming extended hydrogen-bonded chains along the c axis.

Related literature

For general background to ferroelectric organic frameworks, see: Ye et al. (2006 ); Zhang et al. (2008 , 2010 ).

Experimental

Crystal data

C₆H₁₄N⁺·Br⁻
M_r = 180.09
Orthorhombic, P b c n
a = 22.137 (4) Å
b = 9.918 (2) Å
c = 7.5853 (15) Å
V = 1665.5 (6) Å³
Z = 8
Mo Kα radiation
μ = 4.85 mm⁻¹
T = 293 K
0.55 × 0.44 × 0.36 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.134, T_max = 0.223
15678 measured reflections
1907 independent reflections
1142 reflections with I > 2σ(I)
R_int = 0.109

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.118
S = 1.05
1907 reflections
75 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1	0.90	2.34	3.238 (4)	176
N1—H1B⋯Br1ⁱ	0.90	2.36	3.262 (3)	176
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SCXmini (Rigaku, 2006 ); cell refinement: SCXmini; data reduction: SCXmini; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812022878/fy2056sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022878/fy2056Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812022878/fy2056Isup3.cml

checkCIF report

Comment top

Dielectric-ferroelectrics constitute an interesting class of materials, comprising organic ligands,metal-organic coordination compounds and organic-inorganic hybrids.(Zhang et al., 2010; Zhang et al., 2008; Ye et al., 2006). 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 of the compound (428-429K). We have found that title compound has no dielectric disuniformity from 80 K to 405 K. Herein we descibe the crystal structure of this compound.

Regarding its crystal structure, the asymmetric unit of the title compound consists of a 2-methylpiperidinium cation and a bromide anion (Fig. 1). The cations and anions are connected by N—H···Br hydrogen bonds, which make a great contribution to the stability of the crystal structure (Fig. 2 and Table 1).

Related literature top

For general background to ferroelectric organic frameworks, see: Ye et al. (2006); Zhang et al. (2008, 2010).

Experimental top

The title compound was obtained by the addition of hydrobromic acid (0.8 g, 0.01 mol) to a solution of 2-methylpiperidine (0.97 g, 0.01 mol) in water, i.e., in the stoichiometric ratio of 1:1. Good quality single crystals were obtained by slow evaporation of water after two days (the chemical yield is 65%).

Computing details top

Data collection: SCXmini (Rigaku, 2006); cell refinement: SCXmini (Rigaku, 2006); data reduction: SCXmini (Rigaku, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates a hydrogen bond.
	Fig. 2. A view of the packing of the title compound along the a axis. Dashed lines indicate hydrogen bonds.

2-Methylpiperidinium bromide top

Crystal data top

C₆H₁₄N⁺·Br⁻	F(000) = 736
M_r = 180.09	D_x = 1.436 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 3638 reflections
a = 22.137 (4) Å	θ = 3.0–27.5°
b = 9.918 (2) Å	µ = 4.85 mm⁻¹
c = 7.5853 (15) Å	T = 293 K
V = 1665.5 (6) Å³	Block, colorless
Z = 8	0.55 × 0.44 × 0.36 mm

Data collection top

Rigaku SCXmini diffractometer	1907 independent reflections
Radiation source: fine-focus sealed tube	1142 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.109
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
ω scans	h = −28→28
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
T_min = 0.134, T_max = 0.223	l = −9→9
15678 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0407P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
1907 reflections	Δρ_max = 0.38 e Å⁻³
75 parameters	Δρ_min = −0.48 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0022 (5)

Crystal data top

C₆H₁₄N⁺·Br⁻	V = 1665.5 (6) Å³
M_r = 180.09	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 22.137 (4) Å	µ = 4.85 mm⁻¹
b = 9.918 (2) Å	T = 293 K
c = 7.5853 (15) Å	0.55 × 0.44 × 0.36 mm

Data collection top

Rigaku SCXmini diffractometer	1907 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1142 reflections with I > 2σ(I)
T_min = 0.134, T_max = 0.223	R_int = 0.109
15678 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.05	Δρ_max = 0.38 e Å⁻³
1907 reflections	Δρ_min = −0.48 e Å⁻³
75 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
C1	0.6672 (2)	0.7098 (5)	0.0449 (6)	0.0546 (13)
H1	0.6680	0.6902	0.1715	0.065*
C2	0.6608 (3)	0.8597 (6)	0.0205 (7)	0.0817 (19)
H2A	0.6633	0.8808	−0.1041	0.098*
H2B	0.6939	0.9049	0.0797	0.098*
C3	0.6018 (3)	0.9124 (6)	0.0922 (8)	0.097 (2)
H3A	0.6007	0.8994	0.2189	0.117*
H3B	0.5988	1.0082	0.0686	0.117*
C4	0.5503 (3)	0.8414 (6)	0.0099 (7)	0.0799 (18)
H4A	0.5128	0.8733	0.0615	0.096*
H4B	0.5494	0.8611	−0.1153	0.096*
C5	0.5556 (2)	0.6950 (5)	0.0365 (6)	0.0594 (13)
H5A	0.5226	0.6497	−0.0231	0.071*
H5B	0.5528	0.6747	0.1613	0.071*
C6	0.7220 (2)	0.6499 (6)	−0.0376 (8)	0.104 (2)
H6A	0.7210	0.5536	−0.0242	0.156*
H6B	0.7575	0.6850	0.0189	0.156*
H6C	0.7229	0.6722	−0.1607	0.156*
N1	0.61363 (14)	0.6448 (4)	−0.0327 (4)	0.0436 (9)
H1A	0.6158	0.5554	−0.0128	0.052*
H1B	0.6143	0.6574	−0.1502	0.052*
Br1	0.61324 (2)	0.32302 (5)	0.03937 (6)	0.0540 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.055 (3)	0.060 (3)	0.049 (3)	−0.010 (2)	−0.014 (2)	0.001 (2)
C2	0.100 (5)	0.071 (4)	0.075 (4)	−0.040 (4)	−0.030 (4)	0.017 (3)
C3	0.160 (7)	0.043 (3)	0.088 (5)	0.015 (4)	0.003 (5)	−0.002 (3)
C4	0.095 (5)	0.062 (4)	0.082 (4)	0.027 (3)	0.012 (3)	0.004 (3)
C5	0.050 (3)	0.060 (3)	0.068 (3)	0.008 (2)	0.013 (2)	0.003 (3)
C6	0.046 (4)	0.143 (6)	0.121 (6)	0.003 (3)	0.000 (3)	0.027 (4)
N1	0.048 (2)	0.041 (2)	0.042 (2)	0.0030 (16)	0.0024 (18)	0.0000 (16)
Br1	0.0752 (4)	0.0440 (3)	0.0427 (3)	0.0012 (2)	−0.0015 (2)	−0.0005 (2)

Geometric parameters (Å, º) top

C1—N1	1.473 (5)	C4—H4A	0.9700
C1—C6	1.488 (7)	C4—H4B	0.9700
C1—C2	1.504 (7)	C5—N1	1.475 (5)
C1—H1	0.9800	C5—H5A	0.9700
C2—C3	1.507 (8)	C5—H5B	0.9700
C2—H2A	0.9700	C6—H6A	0.9600
C2—H2B	0.9700	C6—H6B	0.9600
C3—C4	1.478 (8)	C6—H6C	0.9600
C3—H3A	0.9700	N1—H1A	0.9000
C3—H3B	0.9700	N1—H1B	0.9000
C4—C5	1.471 (6)

N1—C1—C6	108.2 (4)	C5—C4—H4B	109.5
N1—C1—C2	107.9 (4)	C3—C4—H4B	109.5
C6—C1—C2	114.9 (4)	H4A—C4—H4B	108.1
N1—C1—H1	108.6	C4—C5—N1	110.7 (4)
C6—C1—H1	108.6	C4—C5—H5A	109.5
C2—C1—H1	108.6	N1—C5—H5A	109.5
C1—C2—C3	112.4 (4)	C4—C5—H5B	109.5
C1—C2—H2A	109.1	N1—C5—H5B	109.5
C3—C2—H2A	109.1	H5A—C5—H5B	108.1
C1—C2—H2B	109.1	C1—C6—H6A	109.5
C3—C2—H2B	109.1	C1—C6—H6B	109.5
H2A—C2—H2B	107.9	H6A—C6—H6B	109.5
C4—C3—C2	110.5 (5)	C1—C6—H6C	109.5
C4—C3—H3A	109.5	H6A—C6—H6C	109.5
C2—C3—H3A	109.5	H6B—C6—H6C	109.5
C4—C3—H3B	109.5	C1—N1—C5	114.3 (4)
C2—C3—H3B	109.5	C1—N1—H1A	108.7
H3A—C3—H3B	108.1	C5—N1—H1A	108.7
C5—C4—C3	110.5 (5)	C1—N1—H1B	108.7
C5—C4—H4A	109.5	C5—N1—H1B	108.7
C3—C4—H4A	109.5	H1A—N1—H1B	107.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1	0.90	2.34	3.238 (4)	176
N1—H1B···Br1ⁱ	0.90	2.36	3.262 (3)	176

Symmetry code: (i) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₁₄N⁺·Br⁻
M_r	180.09
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	22.137 (4), 9.918 (2), 7.5853 (15)
V (Å³)	1665.5 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.85
Crystal size (mm)	0.55 × 0.44 × 0.36

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.134, 0.223
No. of measured, independent and observed [I > 2σ(I)] reflections	15678, 1907, 1142
R_int	0.109
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.118, 1.05
No. of reflections	1907
No. of parameters	75
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.48

Computer programs: SCXmini (Rigaku, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1	0.90	2.34	3.238 (4)	175.5
N1—H1B···Br1ⁱ	0.90	2.36	3.262 (3)	176.3

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

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

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2006). SCXmini Benchtop Crystallography System Software. Rigaku Americas Corporation, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ye, Q., Song, Y.-M., Wang, G.-X., Chen, K. & Fu, D.-W. (2006). J. Am. Chem. Soc. 128, 6554–6555. Web of Science CSD CrossRef PubMed CAS Google Scholar
Zhang, W., Xiong, R.-G. & Huang, S.-P. D. (2008). J. Am. Chem. Soc. 130, 10468–10469. Web of Science CSD CrossRef PubMed CAS Google Scholar
Zhang, W., Ye, H.-Y., Cai, H.-L., Ge, J.-Z. & Xiong, R.-G. (2010). J. Am. Chem. Soc. 132, 7300–7302. Web of Science CSD CrossRef CAS PubMed Google Scholar