1,1′-Dimethyl-4,4′-(propane-1,3-di­yl)dipyridinium tetra­bromidocadmate(II)

Li, F.-F.; Li, Z.-G.; Deng, J.-C.; Xu, J.-W.

doi:10.1107/S1600536808030092

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page m1317

doi:10.1107/S1600536808030092

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1,1′-Dimethyl-4,4′-(propane-1,3-diyl)dipyridinium tetrabromidocadmate(II)

Fei-Fei Li,^a Zhi-Gang Li,^b,^c Jian-Cheng Deng ^a ^* and Jing-Wei Xu ^b,^c ^*

^aThe College of Chemistry, Xiangtan University, Hunan 411105, People's Republic of China, ^bNational Analytical Research Center of Electrochemistry and Spectroscopy, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China, and ^cGraduate School of Chinese Academy of Sciences, Beijing 100039, People's Republic of China
^*Correspondence e-mail: djcwye@163.com, jwxu@ciac.jl.cn

(Received 29 August 2008; accepted 18 September 2008; online 24 September 2008)

In the cation of the title compound, (C₁₅H₂₀N₂)[CdBr₄], the dihedral angle between the two pyridine rings is 70.85 (5)°. An intermolecular π–π interaction between the pyridine rings [centroid–centroid distance = 3.900 (4) Å] is observed. The Cd^II atom has a distorted tetrahedral coordination.

Related literature

For related structures, see: Dou et al. (2007 ); Yang et al. (2008 ).

Experimental

Crystal data

(C₁₅H₂₀N₂)[CdBr₄]
M_r = 660.37
Monoclinic, P 2₁ /c
a = 15.422 (2) Å
b = 15.382 (2) Å
c = 8.9885 (14) Å
β = 105.171 (3)°
V = 2058.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 8.82 mm⁻¹
T = 293 (2) K
0.28 × 0.19 × 0.11 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.148, T_max = 0.379
11428 measured reflections
4042 independent reflections
2181 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.112
S = 1.01
4042 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 1.23 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT-Plus (Bruker, 2003 ); 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/S1600536808030092/is2330sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030092/is2330Isup2.hkl

checkCIF report

Comment top

Dou et al. (2007) and Yang et al. (2008) have reported crystal structures of two related compounds synthesized by in situ reaction under hydrothermal condition, in which pyridine N atoms were covalently bonded to methyl groups and the counterions were ClO₄^- and BF₄^- anions. Here, we report the structure of the title compound, (I), synthesized by the same method, in which the counter-ion is tetrabromocadmate(II).

Compound (I), as shown in Fig. 1, consists of a 1,3-bis(1-methyl-4-pyridinium)propane cation and a tetrabormocadmate anion. As result of the flexible propane chain, the two pyridine rings have seriously torsion with the dihedral angle of 70.85 (5)°. The Cd^II atom is coordinated by four Br atoms to a tetrahedral divalent anion.

The crystal structure is stabilized by a weak π–π stacking interaction between adjacent pyridine rings, the shortest atom-to-atomⁱ, centroid-centroidⁱ and interplanar distances being 3.678 (4), 3.900 (4) and 3.638 (3) Å, respectively [symmetry code: (i) -x, 1 - y, 1 - z]. The pyridine rings also contact to each other, the shortest atom-to-atomⁱⁱ being 3.621 (3) Å [symmetry code: (ii) x, 3/2 - y, -1/2 + z], which leads to a supramolecular chain (Fig. 2).

Related literature top

For related structures, see: Dou et al. (2007); Yang et al. (2008).

Experimental top

Compound (I) was solvothermally prepared from a reaction mixture of CdBr₂ (0.2 mmol), 1,3-bis(4-pyridyl)propane (0.1 mmol), methanol (3 ml) and distilled water (8 ml); the pH value was adjusted to 4.6 with trimethylamine and acetic acid. The mixture was stirred for 20 min at room temperature and then sealed in a Teflon-lined stainless steel autoclave with a 23 ml capacity at 428 K for 72 h. After cooling to room temperature, the filtered solution was slowly evaporates and 7 days later colourless block-shaped crystals were obtained; these were washed with deionized water, filtered, and dried in air (yield 46% based on Cd).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); 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 structure of (I), with the atom-labeling scheme and 30% probability displacement ellipsoids.
	Fig. 2. A partial packing view of (I) along the c axis. For the sake of clarity, H atoms have been omitted.

1,1'-Dimethyl-4,4'-(propane-1,3-diyl)dipyridinium tetrabromidocadmate(II) top

Crystal data top

(C₁₅H₂₀N₂)[CdBr₄]	F(000) = 1248
M_r = 660.37	D_x = 2.131 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1386 reflections
a = 15.422 (2) Å	θ = 2.7–19.5°
b = 15.382 (2) Å	µ = 8.83 mm⁻¹
c = 8.9885 (14) Å	T = 293 K
β = 105.171 (3)°	Block, white
V = 2058.0 (5) Å³	0.28 × 0.19 × 0.11 mm
Z = 4

Data collection top

Bruker APEX CCD area-detector diffractometer	4042 independent reflections
Radiation source: fine-focus sealed tube	2181 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ϕ and ω scans	θ_max = 26.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −19→18
T_min = 0.148, T_max = 0.379	k = −19→18
11428 measured reflections	l = −11→5

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0341P)² + 0.3024P] where P = (F_o² + 2F_c²)/3
4042 reflections	(Δ/σ)_max = 0.003
201 parameters	Δρ_max = 1.23 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

(C₁₅H₂₀N₂)[CdBr₄]	V = 2058.0 (5) Å³
M_r = 660.37	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.422 (2) Å	µ = 8.83 mm⁻¹
b = 15.382 (2) Å	T = 293 K
c = 8.9885 (14) Å	0.28 × 0.19 × 0.11 mm
β = 105.171 (3)°

Data collection top

Bruker APEX CCD area-detector diffractometer	4042 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2181 reflections with I > 2σ(I)
T_min = 0.148, T_max = 0.379	R_int = 0.066
11428 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.01	Δρ_max = 1.23 e Å⁻³
4042 reflections	Δρ_min = −0.42 e Å⁻³
201 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
Cd	0.24235 (4)	0.02630 (4)	0.65224 (8)	0.0576 (2)
Br1	0.36144 (6)	0.00463 (5)	0.49814 (12)	0.0704 (3)
Br2	0.32230 (7)	0.00571 (6)	0.94342 (11)	0.0768 (3)
Br3	0.17908 (7)	0.18161 (6)	0.59855 (12)	0.0768 (3)
Br4	0.11503 (7)	−0.08446 (7)	0.58003 (13)	0.0872 (4)
N1	0.5535 (4)	0.7487 (5)	0.6414 (8)	0.0596 (19)
N2	−0.0832 (5)	0.6007 (4)	0.4141 (8)	0.0561 (18)
C1	0.6335 (6)	0.7530 (6)	0.5741 (13)	0.090 (3)
H1A	0.6335	0.8077	0.5227	0.135*
H1B	0.6301	0.7065	0.5016	0.135*
H1C	0.6878	0.7475	0.6553	0.135*
C2	0.5137 (6)	0.8200 (5)	0.6755 (11)	0.069 (3)
H2	0.5361	0.8743	0.6591	0.083*
C3	0.4410 (6)	0.8150 (5)	0.7338 (10)	0.064 (2)
H3	0.4151	0.8658	0.7584	0.077*
C4	0.4045 (5)	0.7344 (5)	0.7575 (9)	0.051 (2)
C5	0.4487 (6)	0.6626 (5)	0.7242 (9)	0.058 (2)
H5	0.4286	0.6075	0.7420	0.070*
C6	0.5217 (5)	0.6701 (5)	0.6652 (10)	0.064 (2)
H6	0.5496	0.6203	0.6414	0.077*
C7	0.3210 (5)	0.7281 (5)	0.8100 (10)	0.061 (2)
H7A	0.3059	0.7850	0.8426	0.073*
H7B	0.3309	0.6891	0.8977	0.073*
C8	0.2434 (5)	0.6944 (5)	0.6807 (10)	0.063 (2)
H8A	0.2598	0.6388	0.6449	0.076*
H8B	0.2319	0.7348	0.5949	0.076*
C9	0.1586 (6)	0.6836 (6)	0.7355 (10)	0.070 (3)
H9A	0.1716	0.6427	0.8206	0.083*
H9B	0.1453	0.7391	0.7757	0.083*
C10	0.0753 (5)	0.6531 (5)	0.6192 (10)	0.048 (2)
C11	−0.0041 (6)	0.6486 (5)	0.6605 (11)	0.064 (2)
H11	−0.0055	0.6634	0.7601	0.076*
C12	−0.0813 (6)	0.6226 (5)	0.5567 (11)	0.063 (2)
H12	−0.1342	0.6202	0.5877	0.075*
C13	−0.0069 (6)	0.6036 (5)	0.3678 (10)	0.062 (2)
H13	−0.0074	0.5884	0.2674	0.075*
C14	0.0719 (6)	0.6293 (5)	0.4708 (11)	0.061 (2)
H14	0.1245	0.6305	0.4385	0.073*
C15	−0.1667 (6)	0.5751 (6)	0.3004 (11)	0.078 (3)
H15A	−0.2122	0.5625	0.3526	0.117*
H15B	−0.1558	0.5244	0.2457	0.117*
H15C	−0.1867	0.6219	0.2288	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd	0.0653 (4)	0.0532 (4)	0.0608 (4)	0.0054 (3)	0.0283 (3)	0.0055 (3)
Br1	0.0749 (6)	0.0653 (5)	0.0857 (7)	0.0108 (4)	0.0469 (6)	0.0137 (5)
Br2	0.0856 (7)	0.0841 (6)	0.0634 (7)	0.0073 (5)	0.0244 (6)	0.0206 (5)
Br3	0.0986 (7)	0.0574 (5)	0.0807 (7)	0.0206 (5)	0.0345 (6)	0.0085 (5)
Br4	0.0920 (7)	0.0907 (7)	0.0933 (8)	−0.0277 (6)	0.0496 (7)	−0.0219 (6)
N1	0.048 (4)	0.063 (5)	0.064 (5)	−0.004 (4)	0.008 (4)	0.015 (4)
N2	0.064 (5)	0.054 (4)	0.054 (5)	0.001 (3)	0.022 (4)	0.004 (4)
C1	0.072 (6)	0.083 (7)	0.117 (9)	−0.013 (5)	0.027 (7)	0.013 (6)
C2	0.075 (6)	0.047 (5)	0.089 (8)	0.004 (5)	0.029 (6)	0.018 (5)
C3	0.074 (6)	0.054 (5)	0.067 (7)	0.005 (5)	0.023 (5)	0.001 (5)
C4	0.055 (5)	0.051 (5)	0.042 (5)	−0.005 (4)	0.008 (4)	0.004 (4)
C5	0.076 (6)	0.040 (5)	0.064 (6)	−0.013 (4)	0.027 (5)	−0.009 (4)
C6	0.065 (6)	0.055 (5)	0.075 (7)	−0.007 (4)	0.020 (5)	0.000 (5)
C7	0.067 (6)	0.058 (5)	0.062 (6)	−0.003 (4)	0.022 (5)	0.002 (5)
C8	0.071 (6)	0.063 (5)	0.062 (7)	−0.006 (5)	0.029 (5)	0.005 (5)
C9	0.079 (6)	0.076 (6)	0.056 (6)	−0.009 (5)	0.021 (6)	0.001 (5)
C10	0.059 (5)	0.047 (4)	0.045 (5)	0.003 (4)	0.028 (5)	0.008 (4)
C11	0.069 (6)	0.073 (6)	0.055 (6)	0.008 (5)	0.026 (6)	−0.006 (5)
C12	0.064 (6)	0.075 (6)	0.058 (7)	0.011 (5)	0.032 (6)	0.003 (5)
C13	0.074 (6)	0.069 (5)	0.052 (6)	−0.006 (5)	0.031 (6)	0.000 (5)
C14	0.053 (6)	0.074 (6)	0.067 (7)	−0.008 (4)	0.033 (5)	−0.006 (5)
C15	0.075 (6)	0.086 (7)	0.068 (7)	−0.006 (5)	0.009 (6)	0.006 (6)

Geometric parameters (Å, º) top

Cd—Br4	2.5520 (11)	C6—H6	0.9300
Cd—Br3	2.5779 (11)	C7—C8	1.524 (10)
Cd—Br1	2.5951 (11)	C7—H7A	0.9700
Cd—Br2	2.6041 (12)	C7—H7B	0.9700
N1—C2	1.332 (10)	C8—C9	1.522 (10)
N1—C6	1.342 (9)	C8—H8A	0.9700
N1—C1	1.512 (11)	C8—H8B	0.9700
N2—C12	1.318 (10)	C9—C10	1.503 (11)
N2—C13	1.347 (10)	C9—H9A	0.9700
N2—C15	1.473 (10)	C9—H9B	0.9700
C1—H1A	0.9600	C10—C14	1.370 (10)
C1—H1B	0.9600	C10—C11	1.373 (10)
C1—H1C	0.9600	C11—C12	1.365 (11)
C2—C3	1.359 (11)	C11—H11	0.9300
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.401 (10)	C13—C14	1.380 (11)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.371 (10)	C14—H14	0.9300
C4—C7	1.486 (10)	C15—H15A	0.9600
C5—C6	1.370 (11)	C15—H15B	0.9600
C5—H5	0.9300	C15—H15C	0.9600

Br4—Cd—Br3	110.04 (4)	C4—C7—H7B	109.5
Br4—Cd—Br1	112.55 (4)	C8—C7—H7B	109.5
Br3—Cd—Br1	107.77 (4)	H7A—C7—H7B	108.1
Br4—Cd—Br2	107.75 (4)	C7—C8—C9	111.1 (7)
Br3—Cd—Br2	110.93 (4)	C7—C8—H8A	109.4
Br1—Cd—Br2	107.80 (4)	C9—C8—H8A	109.4
C2—N1—C6	119.8 (8)	C7—C8—H8B	109.4
C2—N1—C1	122.0 (7)	C9—C8—H8B	109.4
C6—N1—C1	118.3 (8)	H8A—C8—H8B	108.0
C12—N2—C13	119.6 (8)	C10—C9—C8	117.3 (7)
C12—N2—C15	122.4 (8)	C10—C9—H9A	108.0
C13—N2—C15	118.0 (8)	C8—C9—H9A	108.0
N1—C1—H1A	109.5	C10—C9—H9B	108.0
N1—C1—H1B	109.5	C8—C9—H9B	108.0
H1A—C1—H1B	109.5	H9A—C9—H9B	107.2
N1—C1—H1C	109.5	C14—C10—C11	116.1 (8)
H1A—C1—H1C	109.5	C14—C10—C9	124.7 (8)
H1B—C1—H1C	109.5	C11—C10—C9	119.2 (8)
N1—C2—C3	121.2 (8)	C12—C11—C10	120.7 (8)
N1—C2—H2	119.4	C12—C11—H11	119.7
C3—C2—H2	119.4	C10—C11—H11	119.7
C2—C3—C4	121.0 (8)	N2—C12—C11	122.2 (8)
C2—C3—H3	119.5	N2—C12—H12	118.9
C4—C3—H3	119.5	C11—C12—H12	118.9
C5—C4—C3	115.9 (7)	N2—C13—C14	119.3 (8)
C5—C4—C7	122.6 (7)	N2—C13—H13	120.4
C3—C4—C7	121.5 (8)	C14—C13—H13	120.4
C4—C5—C6	121.5 (7)	C10—C14—C13	122.2 (8)
C4—C5—H5	119.2	C10—C14—H14	118.9
C6—C5—H5	119.2	C13—C14—H14	118.9
N1—C6—C5	120.6 (8)	N2—C15—H15A	109.5
N1—C6—H6	119.7	N2—C15—H15B	109.5
C5—C6—H6	119.7	H15A—C15—H15B	109.5
C4—C7—C8	110.6 (7)	N2—C15—H15C	109.5
C4—C7—H7A	109.5	H15A—C15—H15C	109.5
C8—C7—H7A	109.5	H15B—C15—H15C	109.5

Experimental details

Crystal data
Chemical formula	(C₁₅H₂₀N₂)[CdBr₄]
M_r	660.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	15.422 (2), 15.382 (2), 8.9885 (14)
β (°)	105.171 (3)
V (Å³)	2058.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.83
Crystal size (mm)	0.28 × 0.19 × 0.11

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.148, 0.379
No. of measured, independent and observed [I > 2σ(I)] reflections	11428, 4042, 2181
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.112, 1.01
No. of reflections	4042
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.23, −0.42

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the National Analytical Research Center of Electrochemistry and Spectroscopy, Changchun Institute of Applied Chemistry, China.

References

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