1,1′-Dimethyl-4,4′-bipyridinium bis­(triiodide)

Hu, T.

doi:10.1107/S1600536809015207

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1162

doi:10.1107/S1600536809015207

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1,1′-Dimethyl-4,4′-bipyridinium bis(triiodide)

Tuoping Hu ^a ^*

^aDepartment of Chemistry, North University of China, Taiyuan, Shanxi 030051, People's Republic of China
^*Correspondence e-mail: hutuopingsx@yahoo.com.cn

(Received 3 March 2009; accepted 23 April 2009; online 30 April 2009)

In the title compound, C₁₂H₁₄N₂²⁺·2I₃⁻, the 1,1′-dimethyl-4,4′-bipyridinium (DMBP) dication is charge balanced by two triiodide ions. The DMBP dication is planar within 0.010 (5) Å. The asymmetric unit contains only half of the dication, the other half being generated by an inversion center. Weak C—H⋯I interactions link the ions into sheets parallel to (121).

Related literature

For a dication with similar geometry, see: Russell & Wallwork (1972 ). For anions with comparable geometry, see: Marsh (2004 ); Madsen et al. (1999 ).

Experimental

Crystal data

C₁₂H₁₄N₂²⁺·2I₃⁻
M_r = 947.65
Triclinic, $[P \overline 1]$
a = 7.5457 (4) Å
b = 7.9541 (6) Å
c = 9.3029 (6) Å
α = 90.306 (5)°
β = 94.192 (4)°
γ = 102.332 (5)°
V = 543.88 (6) Å³
Z = 1
Mo Kα radiation
μ = 8.56 mm⁻¹
T = 296 K
0.22 × 0.16 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.211, T_max = 0.504
12956 measured reflections
2683 independent reflections
1468 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.073
S = 1.02
2683 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 0.97 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

I1—I2	2.9341 (8)
I2—I3	2.9061 (8)

I3—I2—I1	177.49 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯I3ⁱ	0.93	3.05	3.951 (8)	163
C2—H2⋯I1ⁱⁱ	0.93	3.16	4.066 (8)	164
C5—H5⋯I2ⁱ	0.93	3.13	3.839 (7)	135
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z+2.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; 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 global, I. DOI: 10.1107/S1600536809015207/ez2167sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015207/ez2167Isup2.hkl

checkCIF report

Comment top

The title compound, (I), was obtained by chance when we tried to prepare the salt of the Pb(II) cation and DMBP in MeOH. This paper provides the first crystal structure of the DMBP dication with two triiodide anions.

Only half of the dication of DMBP is contained in the asymmetric unit, while the other half is generated by the inversion center at (1/2,1/2,1/2) (Fig 1.). The N,N'-dimethyl-4,4'bipyridylium(II) dication has an essentially planar conformation, the maximum deviation of the C1 atom (the methyl group) from its mean plane being 0.010 (5) Å. The geometry of the dication is similar to the one observed in Russell & Wallwork (1972). Meanwhile, the geometry of the anion is comparable to that described in Marsh (2004) and Madsen et al. (1999).

Weak C3—H3···I3 interactions link two I₃ anions to each dication. A weaker C2—I2···H1 interaction links each anion to a further DMBP cation, to form sheets parallel to (121). Adjacent sheets are packed into a three-dimensional motif (Fig. 2).

Related literature top

For a dication with similar geometrt, see: Russell & Wallwork (1972). For anions with comparable geometry, see: Marsh (2004); Madsen et al. (1999).

Experimental top

C₁₂H₁₄N₂.4Cl (0.5 mmol, 128 mg) and KI (10 mmol, 1660 mg) were added to 50 ml of CH₃CN. After stirring and refluxing for 12 h, the mixture was filtered, and the clear solution was allowed to evaporate slowly under inert atmosphere. Prismatic crystals of the title compound were obtained after 5 days. The crystals were filtered, washed by cool EtOH and dried in air.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); 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. Molecular structure showing 50% probability displacement ellipsoids. The atoms marked with A are derived from the reference atoms by means of the (1 - x, 1 - y, 1 - z) symmetry transformation..
	Fig. 2. Packing diagram viewed down the a axis. Weak C—H···I interactions are shown as dotted lines.

1,1'-Dimethyl-4,4'-bipyridinium bis(triiodide) top

Crystal data top

C₁₂H₁₄N₂²⁺·2I₃⁻	Z = 1
M_r = 947.65	F(000) = 418
Triclinic, P1	D_x = 2.893 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5457 (4) Å	Cell parameters from 4412 reflections
b = 7.9541 (6) Å	θ = 2.6–27.6°
c = 9.3029 (6) Å	µ = 8.56 mm⁻¹
α = 90.306 (5)°	T = 296 K
β = 94.192 (4)°	Prism, black
γ = 102.332 (5)°	0.22 × 0.16 × 0.08 mm
V = 543.88 (6) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2683 independent reflections
Radiation source: fine-focus sealed tube	1468 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ϕ and ω scans	θ_max = 28.3°, θ_min = 3.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.211, T_max = 0.504	k = −10→10
12956 measured reflections	l = −11→12

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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.005P)² + 2.2853P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2683 reflections	Δρ_max = 0.97 e Å⁻³
93 parameters	Δρ_min = −0.86 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: 0.0028 (3)

Crystal data top

C₁₂H₁₄N₂²⁺·2I₃⁻	γ = 102.332 (5)°
M_r = 947.65	V = 543.88 (6) Å³
Triclinic, P1	Z = 1
a = 7.5457 (4) Å	Mo Kα radiation
b = 7.9541 (6) Å	µ = 8.56 mm⁻¹
c = 9.3029 (6) Å	T = 296 K
α = 90.306 (5)°	0.22 × 0.16 × 0.08 mm
β = 94.192 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2683 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1468 reflections with I > 2σ(I)
T_min = 0.211, T_max = 0.504	R_int = 0.052
12956 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.02	Δρ_max = 0.97 e Å⁻³
2683 reflections	Δρ_min = −0.86 e Å⁻³
93 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
I1	0.11371 (7)	0.64766 (7)	0.84204 (6)	0.0705 (2)
I2	0.19121 (6)	0.80427 (6)	0.56237 (6)	0.05927 (17)
I3	0.25337 (8)	0.96496 (8)	0.28546 (6)	0.0816 (2)
N1	0.3773 (9)	0.2800 (7)	0.8128 (7)	0.0588 (16)
C1	0.3276 (13)	0.1852 (11)	0.9438 (9)	0.085 (3)
H1A	0.4248	0.2166	1.0179	0.128*
H1B	0.3064	0.0638	0.9235	0.128*
H1C	0.2190	0.2131	0.9758	0.128*
C2	0.5358 (12)	0.3875 (11)	0.8116 (9)	0.074 (2)
H2	0.6149	0.4034	0.8944	0.088*
C3	0.2652 (11)	0.2566 (10)	0.6956 (10)	0.072 (2)
H3	0.1526	0.1813	0.6969	0.086*
C4	0.5864 (9)	0.4764 (10)	0.6903 (8)	0.061 (2)
H4	0.6984	0.5532	0.6924	0.074*
C5	0.3120 (10)	0.3414 (10)	0.5722 (8)	0.066 (2)
H5	0.2309	0.3216	0.4906	0.079*
C6	0.4743 (8)	0.4540 (7)	0.5658 (7)	0.0396 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0689 (4)	0.0899 (4)	0.0576 (3)	0.0291 (3)	0.0010 (3)	0.0076 (3)
I2	0.0503 (3)	0.0648 (3)	0.0672 (3)	0.0224 (2)	0.0040 (2)	0.0045 (2)
I3	0.0838 (4)	0.0895 (4)	0.0816 (4)	0.0335 (3)	0.0267 (3)	0.0292 (3)
N1	0.066 (4)	0.051 (4)	0.063 (4)	0.016 (3)	0.016 (4)	0.010 (3)
C1	0.106 (7)	0.076 (6)	0.075 (6)	0.017 (5)	0.017 (5)	0.015 (5)
C2	0.071 (6)	0.088 (6)	0.061 (5)	0.020 (5)	−0.011 (4)	0.015 (5)
C3	0.062 (5)	0.066 (5)	0.078 (6)	−0.010 (4)	0.011 (5)	−0.003 (5)
C4	0.039 (4)	0.077 (5)	0.058 (5)	−0.004 (4)	−0.016 (3)	0.006 (4)
C5	0.052 (5)	0.080 (6)	0.054 (5)	−0.007 (4)	−0.003 (4)	−0.001 (4)
C6	0.031 (3)	0.032 (3)	0.054 (4)	0.005 (3)	−0.002 (3)	−0.003 (3)

Geometric parameters (Å, º) top

I1—I2	2.9341 (8)	C2—H2	0.9300
I2—I3	2.9061 (8)	C3—C5	1.364 (10)
N1—C2	1.314 (9)	C3—H3	0.9300
N1—C3	1.317 (9)	C4—C6	1.371 (8)
N1—C1	1.467 (9)	C4—H4	0.9300
C1—H1A	0.9600	C5—C6	1.359 (9)
C1—H1B	0.9600	C5—H5	0.9300
C1—H1C	0.9600	C6—C6ⁱ	1.464 (12)
C2—C4	1.370 (10)

I3—I2—I1	177.49 (2)	N1—C3—C5	120.9 (7)
C2—N1—C3	119.7 (7)	N1—C3—H3	119.5
C2—N1—C1	119.8 (7)	C5—C3—H3	119.5
C3—N1—C1	120.5 (7)	C2—C4—C6	121.0 (6)
N1—C1—H1A	109.5	C2—C4—H4	119.5
N1—C1—H1B	109.5	C6—C4—H4	119.5
H1A—C1—H1B	109.5	C6—C5—C3	121.6 (7)
N1—C1—H1C	109.5	C6—C5—H5	119.2
H1A—C1—H1C	109.5	C3—C5—H5	119.2
H1B—C1—H1C	109.5	C5—C6—C4	115.9 (6)
N1—C2—C4	121.0 (7)	C5—C6—C6ⁱ	122.1 (7)
N1—C2—H2	119.5	C4—C6—C6ⁱ	122.1 (7)
C4—C2—H2	119.5

C3—N1—C2—C4	0.3 (12)	N1—C3—C5—C6	−0.7 (13)
C1—N1—C2—C4	179.4 (7)	C3—C5—C6—C4	0.0 (11)
C2—N1—C3—C5	0.6 (12)	C3—C5—C6—C6ⁱ	−179.8 (8)
C1—N1—C3—C5	−178.5 (7)	C2—C4—C6—C5	0.9 (11)
N1—C2—C4—C6	−1.0 (12)	C2—C4—C6—C6ⁱ	−179.3 (8)

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
C3—H3···I3ⁱⁱ	0.93	3.05	3.951 (8)	163
C2—H2···I1ⁱⁱⁱ	0.93	3.16	4.066 (8)	164
C5—H5···I2ⁱⁱ	0.93	3.13	3.839 (7)	135

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₂²⁺·2I₃⁻
M_r	947.65
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.5457 (4), 7.9541 (6), 9.3029 (6)
α, β, γ (°)	90.306 (5), 94.192 (4), 102.332 (5)
V (Å³)	543.88 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	8.56
Crystal size (mm)	0.22 × 0.16 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.211, 0.504
No. of measured, independent and observed [I > 2σ(I)] reflections	12956, 2683, 1468
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.073, 1.02
No. of reflections	2683
No. of parameters	93
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.97, −0.86

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

I1—I2	2.9341 (8)	I2—I3	2.9061 (8)

I3—I2—I1	177.49 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···I3ⁱ	0.93	3.05	3.951 (8)	162.8
C2—H2···I1ⁱⁱ	0.93	3.16	4.066 (8)	164.4
C5—H5···I2ⁱ	0.93	3.13	3.839 (7)	134.5

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

Acknowledgements

The author is grateful for funding support from the Natural Science Foundation of Shanxi Province (2007011033), the Program of Technological Industrialization at the University of Shanxi Province (20070308) and the start-up fund of North University of China.

References

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