3-Methyl­piperidinium bromide

Xu, Q.

doi:10.1107/S160053681201971X

organic compounds

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Volume 68| Part 6| June 2012| Page o1654

doi:10.1107/S160053681201971X

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3-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 2 May 2012; online 5 May 2012)

In the crystal structure of the title molecular salt, C₆H₁₄N⁺·Br⁻, N—H⋯Br hydrogen bonds link the cations and anions to form a one-dimensional network.

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
Monoclinic, C 2/c
a = 23.134 (5) Å
b = 9.997 (2) Å
c = 7.7214 (15) Å
β = 107.90 (3)°
V = 1699.3 (6) Å³
Z = 8
Mo Kα radiation
μ = 4.75 mm⁻¹
T = 293 K
0.55 × 0.44 × 0.36 mm

Data collection

Rigaku Mercury70 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.134, T_max = 0.223
8544 measured reflections
1946 independent reflections
1327 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.091
S = 1.09
1946 reflections
74 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯Br1	0.90	2.38	3.273 (3)	175
N1—H1C⋯Br1ⁱ	0.90	2.36	3.255 (3)	173
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/S160053681201971X/ds2192sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681201971X/ds2192Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681201971X/ds2192Isup3.cml

checkCIF report

Comment top

Dielectric-ferroelectric 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 (428k-429k) of the compound, we have found that title compound has no dielectric disuniform 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 3-methylpiperidinium cation, a bromide anion (Fig. 1). The cations and anions were connected by hydrogen bonds involving N—H···Br which makes great contribution to the stability of the crystal structure,and these hydrogen bonds link the cations and anions into stable crystal structure (Fig. 2 and Tab. 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 3-methylpiperidine (0.97 g, 0.01 mol) in water, in the stoichiometric ratio 1: 1. Good quality single crystals were obtained by slow evaporation 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. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicate intramolecular hydrogen bond.
	Fig. 2. A view of the packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds.

3-Methylpiperidinium bromide top

Crystal data top

C₆H₁₄N⁺·Br⁻	F(000) = 736
M_r = 180.09	D_x = 1.408 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1946 reflections
a = 23.134 (5) Å	θ = 3.0–27.5°
b = 9.997 (2) Å	µ = 4.75 mm⁻¹
c = 7.7214 (15) Å	T = 293 K
β = 107.90 (3)°	Block, colorless
V = 1699.3 (6) Å³	0.55 × 0.44 × 0.36 mm
Z = 8

Data collection top

Rigaku Mercury70 CCD diffractometer	1946 independent reflections
Radiation source: fine-focus sealed tube	1327 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ω scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −30→30
T_min = 0.134, T_max = 0.223	k = −12→12
8544 measured reflections	l = −10→10

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)] = 0.043	H-atom parameters constrained
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.035P)² + 0.5231P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1946 reflections	Δρ_max = 0.37 e Å⁻³
74 parameters	Δρ_min = −0.57 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0

Crystal data top

C₆H₁₄N⁺·Br⁻	V = 1699.3 (6) Å³
M_r = 180.09	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 23.134 (5) Å	µ = 4.75 mm⁻¹
b = 9.997 (2) Å	T = 293 K
c = 7.7214 (15) Å	0.55 × 0.44 × 0.36 mm
β = 107.90 (3)°

Data collection top

Rigaku Mercury70 CCD diffractometer	1946 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1327 reflections with I > 2σ(I)
T_min = 0.134, T_max = 0.223	R_int = 0.057
8544 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.09	Δρ_max = 0.37 e Å⁻³
1946 reflections	Δρ_min = −0.57 e Å⁻³
74 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
N1	0.11379 (15)	0.3573 (3)	0.1464 (4)	0.0570 (9)
H1C	0.1188	0.4456	0.1332	0.068*
H1D	0.1141	0.3431	0.2618	0.068*
C1	0.16511 (17)	0.2840 (4)	0.1151 (5)	0.0513 (9)
H1A	0.2027	0.3117	0.2043	0.062*
H1B	0.1676	0.3057	−0.0048	0.062*
C2	0.15735 (16)	0.1344 (3)	0.1290 (5)	0.0468 (9)
H2	0.1575	0.1135	0.2531	0.056*
C3	0.09709 (15)	0.0903 (4)	−0.0014 (5)	0.0523 (9)
H3A	0.0916	−0.0047	0.0134	0.063*
H3B	0.0969	0.1057	−0.1256	0.063*
C4	0.04502 (18)	0.1672 (4)	0.0339 (6)	0.0634 (11)
H4A	0.0070	0.1406	−0.0543	0.076*
H4B	0.0430	0.1456	0.1543	0.076*
C5	0.05371 (18)	0.3159 (4)	0.0204 (6)	0.0641 (11)
H5A	0.0514	0.3390	−0.1036	0.077*
H5B	0.0216	0.3632	0.0511	0.077*
C6	0.21027 (17)	0.0600 (4)	0.0926 (6)	0.0775 (13)
H6A	0.2043	−0.0346	0.0993	0.116*
H6B	0.2476	0.0854	0.1821	0.116*
H6C	0.2120	0.0827	−0.0265	0.116*
Br1	0.120008 (18)	0.32311 (4)	0.57328 (5)	0.05608 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.091 (3)	0.0367 (17)	0.0462 (18)	−0.0022 (16)	0.0255 (17)	0.0003 (15)
C1	0.054 (2)	0.049 (2)	0.047 (2)	−0.0167 (18)	0.0104 (18)	−0.0017 (18)
C2	0.053 (2)	0.0416 (19)	0.045 (2)	−0.0015 (17)	0.0131 (17)	0.0016 (17)
C3	0.053 (2)	0.040 (2)	0.061 (2)	−0.0077 (17)	0.0138 (19)	−0.0038 (19)
C4	0.052 (2)	0.053 (2)	0.085 (3)	−0.0089 (19)	0.020 (2)	0.004 (2)
C5	0.061 (3)	0.055 (2)	0.074 (3)	0.007 (2)	0.017 (2)	0.006 (2)
C6	0.059 (3)	0.080 (3)	0.090 (3)	0.002 (2)	0.017 (2)	−0.009 (3)
Br1	0.0834 (3)	0.0399 (2)	0.0459 (2)	−0.00318 (19)	0.0213 (2)	−0.00200 (18)

Geometric parameters (Å, º) top

N1—C1	1.477 (5)	C3—H3A	0.9700
N1—C5	1.490 (5)	C3—H3B	0.9700
N1—H1C	0.9000	C4—C5	1.507 (5)
N1—H1D	0.9000	C4—H4A	0.9700
C1—C2	1.514 (5)	C4—H4B	0.9700
C1—H1A	0.9700	C5—H5A	0.9700
C1—H1B	0.9700	C5—H5B	0.9700
C2—C3	1.512 (5)	C6—H6A	0.9600
C2—C6	1.530 (5)	C6—H6B	0.9600
C2—H2	0.9800	C6—H6C	0.9600
C3—C4	1.523 (5)

C1—N1—C5	113.0 (3)	C2—C3—H3B	109.5
C1—N1—H1C	109.3	C4—C3—H3B	109.5
C5—N1—H1C	109.0	H3A—C3—H3B	108.1
C1—N1—H1D	108.7	C5—C4—C3	110.8 (3)
C5—N1—H1D	109.0	C5—C4—H4A	109.5
H1C—N1—H1D	107.8	C3—C4—H4A	109.5
N1—C1—C2	111.1 (3)	C5—C4—H4B	109.5
N1—C1—H1A	109.4	C3—C4—H4B	109.5
C2—C1—H1A	109.4	H4A—C4—H4B	108.1
N1—C1—H1B	109.4	N1—C5—C4	110.3 (3)
C2—C1—H1B	109.4	N1—C5—H5A	109.6
H1A—C1—H1B	108.0	C4—C5—H5A	109.6
C3—C2—C1	110.2 (3)	N1—C5—H5B	109.6
C3—C2—C6	111.2 (3)	C4—C5—H5B	109.6
C1—C2—C6	110.4 (3)	H5A—C5—H5B	108.1
C3—C2—H2	108.3	C2—C6—H6A	109.5
C1—C2—H2	108.3	C2—C6—H6B	109.5
C6—C2—H2	108.3	H6A—C6—H6B	109.5
C2—C3—C4	110.6 (3)	C2—C6—H6C	109.5
C2—C3—H3A	109.5	H6A—C6—H6C	109.5
C4—C3—H3A	109.5	H6B—C6—H6C	109.5

C5—N1—C1—C2	−56.3 (4)	C6—C2—C3—C4	−178.8 (3)
N1—C1—C2—C3	55.7 (4)	C2—C3—C4—C5	56.6 (5)
N1—C1—C2—C6	178.9 (3)	C1—N1—C5—C4	56.1 (4)
C1—C2—C3—C4	−56.1 (4)	C3—C4—C5—N1	−55.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···Br1	0.90	2.38	3.273 (3)	175
N1—H1C···Br1ⁱ	0.90	2.36	3.255 (3)	173

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	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	23.134 (5), 9.997 (2), 7.7214 (15)
β (°)	107.90 (3)
V (Å³)	1699.3 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.75
Crystal size (mm)	0.55 × 0.44 × 0.36

Data collection
Diffractometer	Rigaku Mercury70 CCD 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	8544, 1946, 1327
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.091, 1.09
No. of reflections	1946
No. of parameters	74
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.57

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—H1D···Br1	0.90	2.38	3.273 (3)	175.0
N1—H1C···Br1ⁱ	0.90	2.36	3.255 (3)	173.1

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. 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