Redetermination of 2,2′-bipyridine-1,1′-diium dibromide

Ali, B.F.; Al-Far, R.; Haddad, S.F.

doi:10.1107/S1600536812040214

organic compounds

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Volume 68| Part 10| October 2012| Page o3033

https://doi.org/10.1107/S1600536812040214

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Redetermination of 2,2′-bipyridine-1,1′-diium dibromide

Basem F. Ali,^a ^* Rawhi Al-Far ^b and Salim F. Haddad ^c

^aDepartment of Chemistry, Al al-Bayt University, Mafraq 25113, Jordan, ^bFaculty of Science and IT, Al-Balqa'a Applied University, Salt, Jordan, and ^cDepartment of Chemistry, The University of Jordan, Amman 11942, Jordan
^*Correspondence e-mail: bfali@aabu.edu.jo

(Received 7 September 2012; accepted 22 September 2012; online 29 September 2012)

In the title molecular salt, C₁₀H₁₀N₂²⁺·2Br⁻, the dihedral angle between the aromatic rings is 20.83 (14)° and the N—H groups have a transoid conformaton [N—C—C—N = 158.5 (3)°]. In the crystal, the cations are linked to the anions by two N—H⋯Br and five C—H⋯Br hydrogen bonds, generating corrugated sheets incorporating R₂¹(7), R₄²(10), R₄²(11) and two different R₄²(12) loops. This structure was originally reported by Nakatsu et al. [Acta Cryst (1972), A28, S24], but no atomic coordinates are available.

Related literature

For the previous report of this structure as a conference abstract, see: Nakatsu et al. (1972 ). For related structures of 2,2′-bipyridium dication salts, see: Ma et al. (2000 ). For structures containing dicationic 2,2′-bipyridyl derivative salts, see: Amarante et al. (2011 ); Eckensberger et al. (2008 ). For structures of monocationic 2,2′-bipyridinium salts, see: Kavitha et al. (2006 ). For ring motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₀H₁₀N₂²⁺·2Br⁻
M_r = 318.00
Monoclinic, P 2₁ /c
a = 7.5568 (6) Å
b = 9.7747 (7) Å
c = 15.3533 (12) Å
β = 95.830 (7)°
V = 1128.21 (15) Å³
Z = 4
Mo Kα radiation
μ = 7.15 mm⁻¹
T = 293 K
0.20 × 0.15 × 0.10 mm

Data collection

Agilent Xcalibur EOS diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.287, T_max = 0.489
5425 measured reflections
3054 independent reflections
1884 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.073
S = 1.03
3054 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.50 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—H1A⋯Br2	0.86	2.37	3.178 (3)	156
N2—H2A⋯Br1ⁱ	0.86	2.35	3.145 (3)	154
C1—H1B⋯Br1	0.93	2.83	3.611 (4)	143
C9—H9A⋯Br2	0.93	2.81	3.675 (4)	155
C6—H6A⋯Br2ⁱ	0.93	2.84	3.619 (4)	142
C4—H4A⋯Br1ⁱ	0.93	2.86	3.697 (4)	150
C3—H3A⋯Br1ⁱⁱ	0.93	2.85	3.677 (4)	149
Symmetry codes: (i) x, y+1, z; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, global. DOI: https://doi.org/10.1107/S1600536812040214/hb6957sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812040214/hb6957Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812040214/hb6957Isup3.cml

checkCIF report

Comment top

2,2'-bipyridine can form two types of salts monocationic, see for example (Kavitha et al., 2006) or dicationic bipyridinium (see for example Ma et al., 2000). Herein we report the title salt, (I), Figure 1. This structure was reported by Nakatsu et al. (1972), but no atomic coordinates are available. The bipyridinium cation in (I) has a transoid configuration with the N—C—C—N torsion angle is 158.5 (3)°, and the C—C bond distance between the two rings being 1.464 (4) Å. Within the dication, geometrical dimensions are in normal range and agree with reported values (Ma et al., 2000; Eckensberger et al. 2008; Amarante et al. 2011).

The ions in (I) are linked by a combination of seven hydrogen bonds of the types N—H···Br and C—H···Br, Table 1, into complex corrugated sheets, Figure 2. These sheets composed of R¹₂(7), R²₄(10), R²₄(11) and two different R²₄(12) graph set motifs (Bernstein et al. 1995), Figure 3. With the overall coordination around each bromide anion being 4 (three C—H···Br and one N—H···Br interactions), Figure 3.

Related literature top

For the previous report of this structure as a conference abstract, see: Nakatsu et al. (1972). For related structures of 2,2'-bipyridium dication salts, see: Ma et al. (2000). For structures containing dicationic 2,2'-bipyridyl derivative salts, see: Amarante et al. (2011); Eckensberger et al. (2008). For structures of monocationic 2,2'-bipyridinium salts, see: Kavitha et al. (2006). For ring motifs, see: Bernstein et al. (1995).

Experimental top

A solution of MnCl₂ (0.1258 g, 1 mmol) dissolved in 95% EtOH (10 ml) solution was added to a mixture of 2,2'-bipyridine (0.1562 g, 1 mmol) dissolved in 95% EtOH (10 ml) and 60% HBr (2 ml). The resulting mixture was heated to few min, then treated with molecular bromine (2–3 drops), then refluxed for 1.5 hr. On slow evaporation at room temperature colourless chunks of the title salt were formed.

Structure description top

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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. The molecular stucture of the title salt with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Packing diagram of the title salt showing the sheets of cations···anions hydrogen bonded species. Interspecies C/N–H···Br hydrogen bonds are shown as dashed lines. H atoms have been omitted for clarity, except for those involved in hydrogen bonds (shown as dashed lines).
	Fig. 3. A view of one hydrogen bonded sheet contains the different graph-set motifs in the title salt.

2,2'-Bipyridine-1,1'-diium; dibromide top

Crystal data top

C₁₀H₁₀N₂²⁺·2Br⁻	F(000) = 616
M_r = 318.00	D_x = 1.872 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1832 reflections
a = 7.5568 (6) Å	θ = 2.9–29.1°
b = 9.7747 (7) Å	µ = 7.15 mm⁻¹
c = 15.3533 (12) Å	T = 293 K
β = 95.830 (7)°	Chunk, colourless
V = 1128.21 (15) Å³	0.20 × 0.15 × 0.10 mm
Z = 4

Data collection top

Agilent Xcalibur EOS diffractometer	3054 independent reflections
Radiation source: Enhance (Mo) x-ray source	1884 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 16.0534 pixels mm^-1	θ_max = 29.2°, θ_min = 3.4°
ω scans	h = −7→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→10
T_min = 0.287, T_max = 0.489	l = −21→16
5425 measured reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.025P)²] where P = (F_o² + 2F_c²)/3
3054 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

C₁₀H₁₀N₂²⁺·2Br⁻	V = 1128.21 (15) Å³
M_r = 318.00	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5568 (6) Å	µ = 7.15 mm⁻¹
b = 9.7747 (7) Å	T = 293 K
c = 15.3533 (12) Å	0.20 × 0.15 × 0.10 mm
β = 95.830 (7)°

Data collection top

Agilent Xcalibur EOS diffractometer	3054 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1884 reflections with I > 2σ(I)
T_min = 0.287, T_max = 0.489	R_int = 0.032
5425 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.03	Δρ_max = 0.50 e Å⁻³
3054 reflections	Δρ_min = −0.57 e Å⁻³
127 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	0.23397 (5)	0.03486 (4)	0.67326 (2)	0.04534 (13)
N1	0.4480 (4)	0.4858 (3)	0.63133 (16)	0.0384 (7)
H1A	0.5366	0.4580	0.6051	0.046*
C1	0.3257 (6)	0.3947 (4)	0.6491 (2)	0.0507 (10)
H1B	0.3369	0.3036	0.6330	0.061*
N2	0.5392 (4)	0.8449 (3)	0.61771 (15)	0.0369 (7)
H2A	0.4378	0.8714	0.6323	0.044*
C2	0.1841 (6)	0.4356 (4)	0.6909 (2)	0.0554 (11)
H2B	0.0950	0.3739	0.7013	0.066*
Br2	0.74405 (5)	0.29766 (4)	0.55966 (2)	0.04749 (13)
C3	0.1749 (5)	0.5695 (4)	0.7175 (2)	0.0532 (11)
H3A	0.0822	0.5979	0.7488	0.064*
C4	0.3033 (5)	0.6619 (4)	0.6978 (2)	0.0429 (9)
H4A	0.2968	0.7526	0.7154	0.051*
C5	0.4402 (4)	0.6197 (3)	0.65239 (19)	0.0314 (7)
C6	0.6477 (5)	0.9395 (4)	0.5912 (2)	0.0446 (9)
H6A	0.6141	1.0311	0.5898	0.054*
C7	0.8083 (6)	0.9019 (4)	0.5662 (2)	0.0505 (10)
H7A	0.8851	0.9671	0.5470	0.061*
C8	0.8553 (5)	0.7657 (4)	0.5698 (2)	0.0509 (10)
H8A	0.9641	0.7383	0.5524	0.061*
C9	0.7398 (5)	0.6683 (4)	0.5997 (2)	0.0449 (9)
H9A	0.7723	0.5765	0.6035	0.054*
C10	0.5767 (4)	0.7105 (3)	0.62330 (19)	0.0324 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0395 (2)	0.0378 (2)	0.0598 (2)	0.00431 (18)	0.01032 (17)	−0.00318 (18)
N1	0.0397 (19)	0.0320 (17)	0.0441 (16)	−0.0004 (14)	0.0068 (13)	0.0021 (13)
C1	0.058 (3)	0.035 (2)	0.058 (2)	−0.013 (2)	0.001 (2)	0.0056 (18)
N2	0.0309 (17)	0.0316 (17)	0.0483 (17)	−0.0033 (14)	0.0055 (13)	0.0014 (13)
C2	0.043 (3)	0.056 (3)	0.067 (3)	−0.019 (2)	0.008 (2)	0.016 (2)
Br2	0.0500 (3)	0.0356 (2)	0.0580 (2)	0.00351 (19)	0.01070 (18)	−0.00453 (16)
C3	0.036 (2)	0.060 (3)	0.067 (2)	0.004 (2)	0.0223 (19)	0.018 (2)
C4	0.037 (2)	0.036 (2)	0.057 (2)	0.0052 (17)	0.0111 (18)	0.0031 (17)
C5	0.0301 (19)	0.0260 (18)	0.0379 (17)	−0.0007 (16)	0.0022 (14)	0.0036 (14)
C6	0.045 (3)	0.037 (2)	0.052 (2)	−0.0067 (19)	0.0020 (18)	0.0054 (17)
C7	0.048 (3)	0.052 (3)	0.053 (2)	−0.015 (2)	0.0113 (19)	0.0052 (19)
C8	0.034 (2)	0.065 (3)	0.056 (2)	−0.005 (2)	0.0157 (17)	−0.002 (2)
C9	0.038 (2)	0.038 (2)	0.060 (2)	0.0053 (18)	0.0112 (18)	0.0026 (17)
C10	0.0304 (19)	0.0319 (19)	0.0349 (17)	0.0001 (16)	0.0033 (14)	0.0023 (14)

Geometric parameters (Å, º) top

N1—C1	1.331 (4)	C4—C5	1.369 (4)
N1—C5	1.351 (4)	C4—H4A	0.9300
N1—H1A	0.8600	C5—C10	1.464 (4)
C1—C2	1.363 (6)	C6—C7	1.360 (5)
C1—H1B	0.9300	C6—H6A	0.9300
N2—C6	1.326 (4)	C7—C8	1.378 (5)
N2—C10	1.345 (4)	C7—H7A	0.9300
N2—H2A	0.8600	C8—C9	1.399 (5)
C2—C3	1.375 (5)	C8—H8A	0.9300
C2—H2B	0.9300	C9—C10	1.383 (5)
C3—C4	1.382 (5)	C9—H9A	0.9300
C3—H3A	0.9300

C1—N1—C5	123.5 (3)	N1—C5—C4	117.8 (3)
C1—N1—H1A	118.3	N1—C5—C10	117.7 (3)
C5—N1—H1A	118.3	C4—C5—C10	124.4 (3)
N1—C1—C2	119.6 (4)	N2—C6—C7	119.7 (4)
N1—C1—H1B	120.2	N2—C6—H6A	120.1
C2—C1—H1B	120.2	C7—C6—H6A	120.1
C6—N2—C10	124.6 (3)	C6—C7—C8	118.9 (4)
C6—N2—H2A	117.7	C6—C7—H7A	120.6
C10—N2—H2A	117.7	C8—C7—H7A	120.6
C1—C2—C3	119.0 (4)	C7—C8—C9	120.3 (4)
C1—C2—H2B	120.5	C7—C8—H8A	119.9
C3—C2—H2B	120.5	C9—C8—H8A	119.9
C2—C3—C4	119.9 (4)	C10—C9—C8	119.0 (3)
C2—C3—H3A	120.0	C10—C9—H9A	120.5
C4—C3—H3A	120.0	C8—C9—H9A	120.5
C5—C4—C3	120.0 (3)	N2—C10—C9	117.6 (3)
C5—C4—H4A	120.0	N2—C10—C5	117.5 (3)
C3—C4—H4A	120.0	C9—C10—C5	125.0 (3)

C5—N1—C1—C2	−0.2 (5)	C6—C7—C8—C9	−0.7 (5)
N1—C1—C2—C3	−2.9 (6)	C7—C8—C9—C10	1.6 (5)
C1—C2—C3—C4	3.3 (6)	C6—N2—C10—C9	−0.1 (5)
C2—C3—C4—C5	−0.5 (5)	C6—N2—C10—C5	−178.9 (3)
C1—N1—C5—C4	3.0 (5)	C8—C9—C10—N2	−1.2 (5)
C1—N1—C5—C10	−175.6 (3)	C8—C9—C10—C5	177.6 (3)
C3—C4—C5—N1	−2.6 (5)	N1—C5—C10—N2	158.5 (3)
C3—C4—C5—C10	175.9 (3)	C4—C5—C10—N2	−20.1 (5)
C10—N2—C6—C7	1.0 (5)	N1—C5—C10—C9	−20.3 (5)
N2—C6—C7—C8	−0.6 (5)	C4—C5—C10—C9	161.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br2	0.86	2.37	3.178 (3)	156
N2—H2A···Br1ⁱ	0.86	2.35	3.145 (3)	154
C1—H1B···Br1	0.93	2.83	3.611 (4)	143
C9—H9A···Br2	0.93	2.81	3.675 (4)	155
C6—H6A···Br2ⁱ	0.93	2.84	3.619 (4)	142
C4—H4A···Br1ⁱ	0.93	2.86	3.697 (4)	150
C3—H3A···Br1ⁱⁱ	0.93	2.85	3.677 (4)	149

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₂²⁺·2Br⁻
M_r	318.00
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.5568 (6), 9.7747 (7), 15.3533 (12)
β (°)	95.830 (7)
V (Å³)	1128.21 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.15
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Agilent Xcalibur EOS
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.287, 0.489
No. of measured, independent and observed [I > 2σ(I)] reflections	5425, 3054, 1884
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.073, 1.03
No. of reflections	3054
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.57

Computer programs: CrysAlis PRO (Agilent, 2011), 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
N1—H1A···Br2	0.86	2.37	3.178 (3)	156
N2—H2A···Br1ⁱ	0.86	2.35	3.145 (3)	154
C1—H1B···Br1	0.93	2.83	3.611 (4)	143
C9—H9A···Br2	0.93	2.81	3.675 (4)	155
C6—H6A···Br2ⁱ	0.93	2.84	3.619 (4)	142
C4—H4A···Br1ⁱ	0.93	2.86	3.697 (4)	150
C3—H3A···Br1ⁱⁱ	0.93	2.85	3.677 (4)	149

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

Acknowledgements

The structure was determined at the Hamdi Mango Center for Scientific Research at the University of Jordan, Amman, Jordan. RA-F would like to thank Al-Balqa'a Applied University (Jordan) for financial support (sabbatical leave).

References

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