4,4′-(1,3,4-Oxadiazole-2,5-diyl)di­pyri­dinium dibromide monohydrate

Han, M.T.; Zhang, Y.

doi:10.1107/S1600536810046878

organic compounds

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Volume 66| Part 12| December 2010| Page o3212

https://doi.org/10.1107/S1600536810046878

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4,4′-(1,3,4-Oxadiazole-2,5-diyl)dipyridinium dibromide monohydrate

Meng Ting Han ^a and Yuan Zhang ^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 16 October 2010; accepted 12 November 2010; online 17 November 2010)

In the title compound, C₁₂H₁₀N₄O⁺·2Br⁻·H₂O, the cation is approximately planar: the terminal rings make a dihedral angle of 7.91 (6)° with each other and dihedral angles of 6.02 (1) and 6.50 (8)° with the central ring. It is linked to the bromide anions and water molecules by N—H⋯Br hydrogen bonds. In addition, O—H⋯Br and N—H⋯Br hydrogen bonds link these units into a three-dimensional network. C—H⋯N, C—H⋯Br and N—H⋯O interactions are also observed.

Related literature

For background to the development of ferroelectric pure organic or inorganic compounds, see: Haertling et al. (1999 ); Homes et al. (2001 ). For the synthesis of compounds with potential piezoelectric and ferroelectric properties, see: Ye et al. (2006 ); Zhang et al. (2008 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₀N₄O⁺·2Br⁻·H₂O
M_r = 404.08
Monoclinic, P 2₁ /n
a = 5.2917 (11) Å
b = 17.531 (4) Å
c = 15.909 (3) Å
β = 95.42 (3)°
V = 1469.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 5.52 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 = 0.863, T_max = 1.000
14787 measured reflections
3351 independent reflections
2057 reflections with I > 2σ(I)
R_int = 0.124

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.111
S = 1.06
3351 reflections
182 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯Br2	1.02	2.38	3.277 (6)	147
O2—H2A⋯Br2	1.02	2.38	3.277 (6)	147
N1—H1A⋯Br1ⁱ	0.86	2.36	3.158 (7)	155
C12—H12A⋯N3ⁱⁱ	0.93	2.40	3.311 (11)	167
C10—H10A⋯Br1ⁱⁱⁱ	0.93	2.75	3.595 (9)	151
N4—H4A⋯O2ⁱⁱⁱ	0.86	1.78	2.608 (9)	162
C1—H1B⋯Br1^iv	0.93	2.74	3.597 (9)	154
C9—H9A⋯Br2^iv	0.93	2.92	3.719 (8)	145
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+2; (iii) x-1, y, z; (iv) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S1600536810046878/jh2222sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046878/jh2222Isup2.hkl

checkCIF report

Comment top

At present, much attention in ferroelectric material field is focused on developing ferroelectric pure organic or inorganic compounds (Haertling et al. 1999; Homes et al. 2001). Recently we have reported the synthesis of a variety of compounds (Ye et al., 2006; Zhang et al., 2008), which have potential piezoelectric and ferroelectric. properties. In order to find more dielectric ferroelectric materials, we investigate the physical properties of the title compound(Fig. 1). The dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent (dielectric constant equaling to 3.6 to 4.7), suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range. Similarly, below the melting point (365 K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed (dielectric constant equaling to 3.5 to 4.6).Herein, we report the synthesis and crystal structure of the title compound.

The asymmetric unit of (I) consists of one bpo dication, two bromide anions and one water molecule, linked by hydrogen bonds (Fig. 2). The bond lengths and angles are in normal ranges (Allen et al., 1987). In the dication, rings A (N1/C1–C5), B (C6/N2/N3/C7/O1) and C (N4/C8–C12) are each planar. The dihedral angles between the rings are A/B = 6.02 (1), A/C =7.91 (6) and B/C =6.50 (8). As can be seen from the packing diagram (Fig. 2), molecules are connected via intermolecular N—H···Br and C—H···Br hydrogen bonds to form a three dimensional network. Dipole–dipole and van der Waals interactions are effective in the molecular packing.

Related literature top

For background to the development of ferroelectric pure organic or inorganic compounds, see: Haertling et al. (1999); Homes et al. (2001). For the synthesis of compounds with potential piezoelectric and ferroelectric. properties, see: Ye et al. (2006); Zhang et al. (2008). For bond-length data, see: Allen et al. (1987).

Experimental top

A mix of 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (2.24 g, 0.01 mol) and hydrobromic acid (4.05 g,0.02 mol) in methanol (20 ml) was stirred until clear. After several days, the title compound was formed and recrystallized from solution to afford colourlesss prismatic crystals suitable for X-ray analysis.

Structure description top

For background to the development of ferroelectric pure organic or inorganic compounds, see: Haertling et al. (1999); Homes et al. (2001). For the synthesis of compounds with potential piezoelectric and ferroelectric. properties, see: Ye et al. (2006); Zhang et al. (2008). For bond-length data, see: Allen et al. (1987).

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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the a axis showing the hydrogen bondings network. Some of the H atoms have been ommitted for clarity.

4,4'-(1,3,4-Oxadiazole-2,5-diyl)dipyridinium dibromide monohydrate top

Crystal data top

C₁₂H₁₀N₄O⁺·2Br⁻·H₂O	F(000) = 792
M_r = 404.08	D_x = 1.827 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3351 reflections
a = 5.2917 (11) Å	θ = 2.6–27.5°
b = 17.531 (4) Å	µ = 5.52 mm⁻¹
c = 15.909 (3) Å	T = 293 K
β = 95.42 (3)°	Prism, colorless
V = 1469.3 (5) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	3351 independent reflections
Radiation source: fine-focus sealed tube	2057 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.124
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.5°
CCD_Profile_fitting scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −22→22
T_min = 0.863, T_max = 1.000	l = −20→20
14787 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)] = 0.061	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0181P)² + 0.7564P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3351 reflections	Δρ_max = 0.50 e Å⁻³
182 parameters	Δρ_min = −0.56 e Å⁻³
4 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0179 (12)

Crystal data top

C₁₂H₁₀N₄O⁺·2Br⁻·H₂O	V = 1469.3 (5) Å³
M_r = 404.08	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.2917 (11) Å	µ = 5.52 mm⁻¹
b = 17.531 (4) Å	T = 293 K
c = 15.909 (3) Å	0.20 × 0.20 × 0.20 mm
β = 95.42 (3)°

Data collection top

Rigaku Mercury2 diffractometer	3351 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2057 reflections with I > 2σ(I)
T_min = 0.863, T_max = 1.000	R_int = 0.124
14787 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	4 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.06	Δρ_max = 0.50 e Å⁻³
3351 reflections	Δρ_min = −0.56 e Å⁻³
182 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
Br1	0.18714 (17)	0.55914 (5)	0.63099 (6)	0.0437 (3)
O1	0.0187 (10)	0.3400 (3)	0.9429 (3)	0.0319 (13)
C12	0.1428 (16)	0.5397 (5)	0.8894 (5)	0.037 (2)
H12A	0.2942	0.5478	0.9229	0.044*
N1	0.0017 (14)	0.0806 (4)	1.0711 (5)	0.043 (2)
H1A	−0.0375	0.0360	1.0885	0.051*
N3	0.3649 (13)	0.4071 (4)	0.9798 (5)	0.0391 (18)
C7	0.1437 (15)	0.4071 (5)	0.9364 (5)	0.031 (2)
N2	0.3954 (13)	0.3359 (4)	1.0176 (5)	0.0390 (18)
C2	−0.0995 (16)	0.1868 (4)	0.9865 (6)	0.039 (2)
H2B	−0.2092	0.2117	0.9463	0.047*
N4	−0.1899 (14)	0.5864 (4)	0.7948 (5)	0.0413 (19)
H4A	−0.2572	0.6235	0.7653	0.050*
C4	0.2829 (16)	0.1829 (5)	1.0785 (5)	0.038 (2)
H4B	0.4331	0.2056	1.1010	0.045*
C6	0.1883 (15)	0.2988 (4)	0.9944 (5)	0.033 (2)
C9	−0.2029 (15)	0.4591 (5)	0.8382 (6)	0.039 (2)
H9A	−0.2838	0.4119	0.8365	0.046*
C1	−0.1564 (16)	0.1146 (5)	1.0141 (6)	0.040 (2)
H1B	−0.3048	0.0903	0.9926	0.048*
C3	0.1220 (15)	0.2216 (4)	1.0193 (5)	0.032 (2)
C8	0.0254 (15)	0.4693 (4)	0.8867 (5)	0.031 (2)
C11	0.0294 (18)	0.5977 (5)	0.8412 (6)	0.043 (2)
H11A	0.1069	0.6453	0.8411	0.052*
C10	−0.3083 (17)	0.5193 (5)	0.7925 (6)	0.042 (2)
H10A	−0.4624	0.5133	0.7599	0.050*
C5	0.2213 (17)	0.1121 (5)	1.1036 (6)	0.043 (2)
H5A	0.3293	0.0856	1.1428	0.051*
Br2	0.19209 (18)	0.82026 (5)	0.74803 (7)	0.0527 (4)
O2	0.6881 (12)	0.7150 (3)	0.7191 (4)	0.0601 (19)
H2D	0.6726	0.7611	0.7028	0.072*
H2A	0.5106	0.7367	0.7060	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0439 (6)	0.0500 (6)	0.0366 (6)	0.0134 (5)	0.0010 (4)	−0.0015 (4)
O1	0.033 (3)	0.037 (3)	0.026 (3)	−0.001 (3)	0.000 (3)	0.001 (3)
C12	0.032 (5)	0.042 (5)	0.036 (6)	−0.007 (4)	0.001 (4)	0.000 (4)
N1	0.048 (5)	0.040 (4)	0.041 (5)	−0.001 (4)	0.010 (4)	0.005 (4)
N3	0.037 (4)	0.035 (4)	0.043 (5)	−0.006 (4)	−0.009 (4)	0.004 (4)
C7	0.032 (5)	0.039 (5)	0.022 (5)	−0.009 (4)	0.000 (4)	−0.003 (4)
N2	0.038 (4)	0.039 (4)	0.038 (5)	−0.005 (4)	−0.007 (4)	0.004 (4)
C2	0.038 (5)	0.043 (5)	0.034 (6)	0.001 (4)	−0.001 (4)	−0.002 (4)
N4	0.042 (5)	0.049 (5)	0.033 (5)	0.017 (4)	0.004 (4)	0.006 (4)
C4	0.037 (5)	0.047 (5)	0.029 (6)	−0.003 (4)	−0.002 (4)	0.000 (4)
C6	0.036 (5)	0.036 (5)	0.026 (5)	−0.003 (4)	0.007 (4)	0.001 (4)
C9	0.035 (5)	0.048 (5)	0.033 (5)	−0.009 (5)	0.002 (4)	−0.004 (4)
C1	0.037 (5)	0.041 (5)	0.043 (6)	−0.008 (4)	0.005 (5)	−0.006 (5)
C3	0.035 (5)	0.038 (5)	0.026 (5)	−0.002 (4)	0.007 (4)	−0.003 (4)
C8	0.032 (5)	0.034 (5)	0.027 (5)	0.002 (4)	0.005 (4)	0.005 (4)
C11	0.050 (6)	0.040 (5)	0.042 (6)	0.000 (5)	0.010 (5)	0.003 (5)
C10	0.034 (5)	0.058 (6)	0.033 (6)	0.006 (5)	0.001 (4)	−0.007 (5)
C5	0.048 (6)	0.047 (6)	0.034 (6)	0.006 (5)	0.008 (5)	0.005 (4)
Br2	0.0432 (6)	0.0618 (7)	0.0532 (8)	0.0114 (5)	0.0060 (5)	0.0022 (5)
O2	0.061 (4)	0.046 (4)	0.073 (5)	0.022 (4)	0.002 (4)	0.016 (4)

Geometric parameters (Å, º) top

O1—C7	1.359 (9)	N4—C10	1.331 (10)
O1—C6	1.364 (9)	N4—H4A	0.8600
C12—C11	1.376 (11)	C4—C5	1.353 (11)
C12—C8	1.382 (10)	C4—C3	1.386 (11)
C12—H12A	0.9300	C4—H4B	0.9300
N1—C1	1.318 (10)	C6—C3	1.463 (11)
N1—C5	1.345 (11)	C9—C10	1.371 (11)
N1—H1A	0.8600	C9—C8	1.383 (11)
N3—C7	1.301 (10)	C9—H9A	0.9300
N3—N2	1.388 (9)	C1—H1B	0.9300
C7—C8	1.453 (11)	C11—H11A	0.9300
N2—C6	1.297 (10)	C10—H10A	0.9300
C2—C3	1.379 (11)	C5—H5A	0.9300
C2—C1	1.382 (11)	O2—H2D	0.8501
C2—H2B	0.9300	O2—H2A	1.0162
N4—C11	1.331 (11)

C7—O1—C6	101.9 (6)	O1—C6—C3	119.4 (7)
C11—C12—C8	118.1 (8)	C10—C9—C8	119.2 (8)
C11—C12—H12A	120.9	C10—C9—H9A	120.4
C8—C12—H12A	120.9	C8—C9—H9A	120.4
C1—N1—C5	123.2 (8)	N1—C1—C2	119.4 (8)
C1—N1—H1A	118.4	N1—C1—H1B	120.3
C5—N1—H1A	118.4	C2—C1—H1B	120.3
C7—N3—N2	106.9 (6)	C2—C3—C4	119.2 (8)
N3—C7—O1	112.3 (7)	C2—C3—C6	121.6 (8)
N3—C7—C8	127.5 (7)	C4—C3—C6	119.3 (8)
O1—C7—C8	120.2 (7)	C12—C8—C9	120.0 (8)
C6—N2—N3	105.5 (7)	C12—C8—C7	118.9 (7)
C3—C2—C1	119.1 (9)	C9—C8—C7	121.1 (7)
C3—C2—H2B	120.4	N4—C11—C12	120.7 (8)
C1—C2—H2B	120.4	N4—C11—H11A	119.6
C11—N4—C10	122.0 (8)	C12—C11—H11A	119.6
C11—N4—H4A	119.0	N4—C10—C9	119.9 (8)
C10—N4—H4A	119.0	N4—C10—H10A	120.0
C5—C4—C3	120.0 (8)	C9—C10—H10A	120.0
C5—C4—H4B	120.0	N1—C5—C4	119.2 (9)
C3—C4—H4B	120.0	N1—C5—H5A	120.4
N2—C6—O1	113.3 (7)	C4—C5—H5A	120.4
N2—C6—C3	127.2 (8)	H2D—O2—H2A	61.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···Br2	1.02	2.38	3.277 (6)	147
O2—H2A···Br2	1.02	2.38	3.277 (6)	147
N1—H1A···Br1ⁱ	0.86	2.36	3.158 (7)	155
C12—H12A···N3ⁱⁱ	0.93	2.40	3.311 (11)	167
C10—H10A···Br1ⁱⁱⁱ	0.93	2.75	3.595 (9)	151
N4—H4A···O2ⁱⁱⁱ	0.86	1.78	2.608 (9)	162
C1—H1B···Br1^iv	0.93	2.74	3.597 (9)	154
C9—H9A···Br2^iv	0.93	2.92	3.719 (8)	145

Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+2; (iii) x−1, y, z; (iv) −x−1/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₄O⁺·2Br⁻·H₂O
M_r	404.08
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	5.2917 (11), 17.531 (4), 15.909 (3)
β (°)	95.42 (3)
V (Å³)	1469.3 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.52
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury2
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.863, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	14787, 3351, 2057
R_int	0.124
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.111, 1.06
No. of reflections	3351
No. of parameters	182
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.56

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···Br2	1.02	2.38	3.277 (6)	147.1
O2—H2A···Br2	1.02	2.38	3.277 (6)	147.1
N1—H1A···Br1ⁱ	0.86	2.36	3.158 (7)	155.4
C12—H12A···N3ⁱⁱ	0.93	2.40	3.311 (11)	167.1
C10—H10A···Br1ⁱⁱⁱ	0.93	2.75	3.595 (9)	151.2
N4—H4A···O2ⁱⁱⁱ	0.86	1.78	2.608 (9)	162.3
C1—H1B···Br1^iv	0.93	2.74	3.597 (9)	153.7
C9—H9A···Br2^iv	0.93	2.92	3.719 (8)	145.2

Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+2; (iii) x−1, y, z; (iv) −x−1/2, y−1/2, −z+3/2.

Acknowledgements

The authors are grateful to the starter fund of Southeast University for financial support to purchase the X-ray diffractometer.

References

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