p-Phenyl­enedimethanaminium dibromide

Zhang, Y.; Han, M.T.

doi:10.1107/S1600536810024840

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1865

doi:10.1107/S1600536810024840

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p-Phenylenedimethanaminium dibromide

Yuan Zhang ^a ^* and Meng Ting Han ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: zhangshelley86@hotmail.com

(Received 14 June 2010; accepted 24 June 2010; online 30 June 2010)

In the title salt, C₈H₁₄N₂²⁺·2Br⁻, the cation has a crystallographically imposed centre of symmetry. The compound is isostructural with the chloride analogue. In the crystal structure, the cations and anions are connected via N—H⋯Br hydrogen bonds, forming layers parallel to the bc plane.

Related literature

For the synthesis, structures and properties of ferroelectric organic or inorganic compounds, see: Haertling (1999 ); Homes et al. (2001 ); Fu et al. (2009 ); Hang et al. (2009 ). For the structure of the isostructural chloride salt, see: Arkenbout et al. (2007 ).

Experimental

Crystal data

C₈H₁₄N₂²⁺·2Br⁻
M_r = 298.01
Triclinic, $[P \overline 1]$
a = 4.4462 (9) Å
b = 6.0331 (12) Å
c = 10.347 (2) Å
α = 101.90 (3)°
β = 99.79 (3)°
γ = 94.29 (3)°
V = 265.89 (9) Å³
Z = 1
Mo Kα radiation
μ = 7.58 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.837, T_max = 1.000
2767 measured reflections
1213 independent reflections
1107 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.084
S = 1.10
1213 reflections
56 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1ⁱ	0.89	2.49	3.359 (3)	167
N1—H1B⋯Br1ⁱⁱ	0.88	2.59	3.363 (3)	146
N1—H1C⋯Br1ⁱⁱⁱ	0.89	2.55	3.422 (3)	167
Symmetry codes: (i) -x, -y+1, -z+2; (ii) x+1, y+1, z; (iii) x+1, y, z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810024840/rz2469sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810024840/rz2469Isup2.hkl

checkCIF report

Comment top

At present, much attention in ferroelectric material field is focused on developing ferroelectric pure organic or inorganic compounds (Haertling, 1999; Homes et al., 2001). Recently we have reported the synthesis of a variety of compounds (Fu et al., 2009; Hang et al., 2009), which have potential piezoelectric and ferroelectric properties. In order to develop new materials of this kind, we investigated the physical properties of the title compound. Its dielectric constant as a function of temperature (93-440 K) indicates that the permittivity is basically temperature-independent (dielectric constant ranging from 3.2 to 4.4), suggesting that this compound should be not a real ferroelectrics or that no distinct phase transition occurred within the measured temperature range. Herein, we report the synthesis and crystal structure of the title compound (Fig. 1).

The cation of the title compound possesses crystallographically imposed centre of symmetry. The compound is isostructural to the chloride analogue (Arkenbout et al., 2007). Bond lengths and angles are within their normal ranges. In the crystal packing (Fig. 2), cations and anions are connected via intermolecular N—H···Br hydrogen bonds (Table 1) to form layers parallel to the bc plane. Contrary to what observed in the chloride salt, the separation between the centroids of stacked aromatic rings (4.446 (2) Å) suggests that no π···π stacking interactions are present.

Related literature top

For the synthesis, structures and properties of ferroelectric pure organic or inorganic compounds, see: Haertling (1999); Homes et al. (2001); Fu et al. (2009); Hang et al. (2009). For the structure of the isostructural chloride salt, see: Arkenbout et al. (2007).

Experimental top

Hydrobromic acid (4.05 g, 40%) was added slowly to a solution of 1,4-phenylenedimethanamine (2.72 g, 0.02 mol) in methanol. After several days, colourless prismatic crystals of the title compound suitable for X-ray analysis were obtained on slow evaporation of the solvent.

Computing details top

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: SHELXTL/PC (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms labelled with the suffix A are related by the symmetry code (1-x, 1-y, 1-z).
	Fig. 2. Crystal packing of the title compound approximately viewed along the b axis, showing the hydrogen bondings network.

p-Phenylenedimethanaminium dibromide top

Crystal data top

C₈H₁₄N₂²⁺·2Br⁻	Z = 1
M_r = 298.01	F(000) = 146
Triclinic, P1	D_x = 1.861 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.4462 (9) Å	Cell parameters from 1213 reflections
b = 6.0331 (12) Å	θ = 2.6–27.5°
c = 10.347 (2) Å	µ = 7.58 mm⁻¹
α = 101.90 (3)°	T = 293 K
β = 99.79 (3)°	Prism, colorless
γ = 94.29 (3)°	0.20 × 0.20 × 0.20 mm
V = 265.89 (9) Å³

Data collection top

Rigaku Mercury2 diffractometer	1213 independent reflections
Radiation source: fine-focus sealed tube	1107 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.5°
CCD_Profile_fitting scans	h = −5→5
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −7→7
T_min = 0.837, T_max = 1.000	l = −13→13
2767 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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0314P)²] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1213 reflections	Δρ_max = 0.59 e Å⁻³
56 parameters	Δρ_min = −0.68 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: 0.102 (8)

Crystal data top

C₈H₁₄N₂²⁺·2Br⁻	γ = 94.29 (3)°
M_r = 298.01	V = 265.89 (9) Å³
Triclinic, P1	Z = 1
a = 4.4462 (9) Å	Mo Kα radiation
b = 6.0331 (12) Å	µ = 7.58 mm⁻¹
c = 10.347 (2) Å	T = 293 K
α = 101.90 (3)°	0.20 × 0.20 × 0.20 mm
β = 99.79 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1213 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1107 reflections with I > 2σ(I)
T_min = 0.837, T_max = 1.000	R_int = 0.053
2767 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.10	Δρ_max = 0.59 e Å⁻³
1213 reflections	Δρ_min = −0.68 e Å⁻³
56 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	0.5050 (7)	0.6880 (4)	0.8667 (3)	0.0352 (6)
H1A	0.4270	0.7394	0.9393	0.042*
H1B	0.6628	0.7845	0.8646	0.042*
H1C	0.5668	0.5525	0.8698	0.042*
C2	0.2679 (7)	0.6652 (6)	0.7437 (3)	0.0354 (8)
H2D	0.1943	0.8121	0.7417	0.042*
H2E	0.0952	0.5593	0.7466	0.042*
C5	0.3474 (8)	0.3493 (5)	0.5579 (3)	0.0345 (7)
H5A	0.2447	0.2476	0.5965	0.041*
C7	0.3911 (7)	0.5816 (5)	0.6174 (3)	0.0293 (7)
C10	0.4567 (8)	0.2702 (6)	0.4418 (3)	0.0353 (8)
H10A	0.4276	0.1150	0.4028	0.042*
Br1	−0.14338 (7)	0.20342 (5)	0.87105 (3)	0.03667 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0523 (17)	0.0363 (15)	0.0199 (14)	0.0134 (12)	0.0156 (11)	0.0027 (12)
C2	0.0390 (17)	0.0412 (19)	0.0265 (17)	0.0107 (14)	0.0140 (13)	0.0005 (15)
C5	0.0451 (18)	0.0314 (17)	0.0300 (19)	0.0020 (13)	0.0145 (14)	0.0088 (15)
C7	0.0343 (16)	0.0345 (17)	0.0197 (16)	0.0071 (12)	0.0074 (12)	0.0040 (14)
C10	0.055 (2)	0.0265 (16)	0.0249 (18)	0.0067 (14)	0.0131 (15)	0.0013 (14)
Br1	0.0478 (3)	0.0329 (3)	0.0303 (3)	0.00763 (15)	0.01254 (16)	0.00384 (18)

Geometric parameters (Å, º) top

N1—C2	1.483 (4)	C5—C10	1.380 (4)
N1—H1A	0.8880	C5—C7	1.394 (4)
N1—H1B	0.8839	C5—H5A	0.9300
N1—H1C	0.8865	C7—C10ⁱ	1.382 (5)
C2—C7	1.509 (4)	C10—C7ⁱ	1.382 (5)
C2—H2D	0.9700	C10—H10A	0.9300
C2—H2E	0.9700

C2—N1—H1A	109.9	H2D—C2—H2E	107.9
C2—N1—H1B	109.6	C10—C5—C7	120.0 (3)
H1A—N1—H1B	109.3	C10—C5—H5A	120.0
C2—N1—H1C	109.0	C7—C5—H5A	120.0
H1A—N1—H1C	109.4	C10ⁱ—C7—C5	119.1 (3)
H1B—N1—H1C	109.6	C10ⁱ—C7—C2	121.7 (3)
N1—C2—C7	111.9 (2)	C5—C7—C2	119.3 (3)
N1—C2—H2D	109.2	C5—C10—C7ⁱ	120.9 (3)
C7—C2—H2D	109.2	C5—C10—H10A	119.5
N1—C2—H2E	109.2	C7ⁱ—C10—H10A	119.5
C7—C2—H2E	109.2

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ⁱⁱ	0.89	2.49	3.359 (3)	167
N1—H1B···Br1ⁱⁱⁱ	0.88	2.59	3.363 (3)	146
N1—H1C···Br1^iv	0.89	2.55	3.422 (3)	167

Symmetry codes: (ii) −x, −y+1, −z+2; (iii) x+1, y+1, z; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₈H₁₄N₂²⁺·2Br⁻
M_r	298.01
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	4.4462 (9), 6.0331 (12), 10.347 (2)
α, β, γ (°)	101.90 (3), 99.79 (3), 94.29 (3)
V (Å³)	265.89 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	7.58
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.837, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2767, 1213, 1107
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.084, 1.10
No. of reflections	1213
No. of parameters	56
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.68

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ⁱ	0.89	2.49	3.359 (3)	167.1
N1—H1B···Br1ⁱⁱ	0.88	2.59	3.363 (3)	146.2
N1—H1C···Br1ⁱⁱⁱ	0.89	2.55	3.422 (3)	167.3

Symmetry codes: (i) −x, −y+1, −z+2; (ii) x+1, y+1, z; (iii) x+1, y, z.

Acknowledgements

The authors are grateful to the Starter Fund of Southeast University for financial support to buy the X-ray diffractometer.

References

Arkenbout, A. H., Meetsma, A. & Palstra, T. T. M. (2007). Acta Cryst. E63, o869–o870. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fu, D. W., Ge, J. Z., Dai, J., Ye, H. Y. & Qu, Z. R. (2009). Inorg. Chem. Commun. 12, 994–997. Web of Science CSD CrossRef CAS Google Scholar
Haertling, G. H. (1999). J. Am. Ceram. Soc. 82, 797–810. CrossRef CAS Google Scholar
Hang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. 5, 2026–2029. Web of Science CSD CrossRef Google Scholar
Homes, C. C., Vogt, T., Shapiro, S. M., Wakimoto, S. & Ramirez, A. P. (2001). Science, 293, 673–676. Web of Science CrossRef PubMed CAS 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