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Acta Cryst. (2008). E64, m1317    [ doi:10.1107/S1600536808030092 ]

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

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

Abstract top

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

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 CdII 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).

Refinement top

H atoms were placed geometrically (C—H = 0.93–0.97 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C) . The highest residual electron density peak is located at 1.223 (3) Å from Cd atom.

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
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-labeling scheme and 30% probability displacement ellipsoids.
[Figure 2] 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
Mr = 660.37Dx = 2.131 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1386 reflections
a = 15.422 (2) Åθ = 2.7–19.5°
b = 15.382 (2) ŵ = 8.83 mm−1
c = 8.9885 (14) ÅT = 293 K
β = 105.171 (3)°Block, white
V = 2058.0 (5) Å30.28 × 0.19 × 0.11 mm
Z = 4
Data collection top
Bruker APEX CCD area-detector
diffractometer		4042 independent reflections
Radiation source: fine-focus sealed tube2181 reflections with I > 2σ(I)
graphiteRint = 0.066
φ and ω scansθmax = 26.1°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −19→18
Tmin = 0.148, Tmax = 0.379k = −19→18
11428 measured reflectionsl = −11→5
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0341P)2 + 0.3024P]
where P = (Fo2 + 2Fc2)/3
4042 reflections(Δ/σ)max = 0.003
201 parametersΔρmax = 1.23 e Å−3
0 restraintsΔρmin = −0.42 e Å−3
Crystal data top
(C15H20N2)[CdBr4]V = 2058.0 (5) Å3
Mr = 660.37Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.422 (2) ŵ = 8.83 mm−1
b = 15.382 (2) ÅT = 293 K
c = 8.9885 (14) Å0.28 × 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)
Tmin = 0.148, Tmax = 0.379Rint = 0.066
11428 measured reflectionsθmax = 26.1°
Refinement top
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.112Δρmax = 1.23 e Å−3
S = 1.01Δρmin = −0.42 e Å−3
4042 reflectionsAbsolute structure: ?
201 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Cd0.24235 (4)0.02630 (4)0.65224 (8)0.0576 (2)
Br10.36144 (6)0.00463 (5)0.49814 (12)0.0704 (3)
Br20.32230 (7)0.00571 (6)0.94342 (11)0.0768 (3)
Br30.17908 (7)0.18161 (6)0.59855 (12)0.0768 (3)
Br40.11503 (7)−0.08446 (7)0.58003 (13)0.0872 (4)
N10.5535 (4)0.7487 (5)0.6414 (8)0.0596 (19)
N2−0.0832 (5)0.6007 (4)0.4141 (8)0.0561 (18)
C10.6335 (6)0.7530 (6)0.5741 (13)0.090 (3)
H1A0.63350.80770.52270.135*
H1B0.63010.70650.50160.135*
H1C0.68780.74750.65530.135*
C20.5137 (6)0.8200 (5)0.6755 (11)0.069 (3)
H20.53610.87430.65910.083*
C30.4410 (6)0.8150 (5)0.7338 (10)0.064 (2)
H30.41510.86580.75840.077*
C40.4045 (5)0.7344 (5)0.7575 (9)0.051 (2)
C50.4487 (6)0.6626 (5)0.7242 (9)0.058 (2)
H50.42860.60750.74200.070*
C60.5217 (5)0.6701 (5)0.6652 (10)0.064 (2)
H60.54960.62030.64140.077*
C70.3210 (5)0.7281 (5)0.8100 (10)0.061 (2)
H7A0.30590.78500.84260.073*
H7B0.33090.68910.89770.073*
C80.2434 (5)0.6944 (5)0.6807 (10)0.063 (2)
H8A0.25980.63880.64490.076*
H8B0.23190.73480.59490.076*
C90.1586 (6)0.6836 (6)0.7355 (10)0.070 (3)
H9A0.17160.64270.82060.083*
H9B0.14530.73910.77570.083*
C100.0753 (5)0.6531 (5)0.6192 (10)0.048 (2)
C11−0.0041 (6)0.6486 (5)0.6605 (11)0.064 (2)
H11−0.00550.66340.76010.076*
C12−0.0813 (6)0.6226 (5)0.5567 (11)0.063 (2)
H12−0.13420.62020.58770.075*
C13−0.0069 (6)0.6036 (5)0.3678 (10)0.062 (2)
H13−0.00740.58840.26740.075*
C140.0719 (6)0.6293 (5)0.4708 (11)0.061 (2)
H140.12450.63050.43850.073*
C15−0.1667 (6)0.5751 (6)0.3004 (11)0.078 (3)
H15A−0.21220.56250.35260.117*
H15B−0.15580.52440.24570.117*
H15C−0.18670.62190.22880.117*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd0.0653 (4)0.0532 (4)0.0608 (4)0.0054 (3)0.0283 (3)0.0055 (3)
Br10.0749 (6)0.0653 (5)0.0857 (7)0.0108 (4)0.0469 (6)0.0137 (5)
Br20.0856 (7)0.0841 (6)0.0634 (7)0.0073 (5)0.0244 (6)0.0206 (5)
Br30.0986 (7)0.0574 (5)0.0807 (7)0.0206 (5)0.0345 (6)0.0085 (5)
Br40.0920 (7)0.0907 (7)0.0933 (8)−0.0277 (6)0.0496 (7)−0.0219 (6)
N10.048 (4)0.063 (5)0.064 (5)−0.004 (4)0.008 (4)0.015 (4)
N20.064 (5)0.054 (4)0.054 (5)0.001 (3)0.022 (4)0.004 (4)
C10.072 (6)0.083 (7)0.117 (9)−0.013 (5)0.027 (7)0.013 (6)
C20.075 (6)0.047 (5)0.089 (8)0.004 (5)0.029 (6)0.018 (5)
C30.074 (6)0.054 (5)0.067 (7)0.005 (5)0.023 (5)0.001 (5)
C40.055 (5)0.051 (5)0.042 (5)−0.005 (4)0.008 (4)0.004 (4)
C50.076 (6)0.040 (5)0.064 (6)−0.013 (4)0.027 (5)−0.009 (4)
C60.065 (6)0.055 (5)0.075 (7)−0.007 (4)0.020 (5)0.000 (5)
C70.067 (6)0.058 (5)0.062 (6)−0.003 (4)0.022 (5)0.002 (5)
C80.071 (6)0.063 (5)0.062 (7)−0.006 (5)0.029 (5)0.005 (5)
C90.079 (6)0.076 (6)0.056 (6)−0.009 (5)0.021 (6)0.001 (5)
C100.059 (5)0.047 (4)0.045 (5)0.003 (4)0.028 (5)0.008 (4)
C110.069 (6)0.073 (6)0.055 (6)0.008 (5)0.026 (6)−0.006 (5)
C120.064 (6)0.075 (6)0.058 (7)0.011 (5)0.032 (6)0.003 (5)
C130.074 (6)0.069 (5)0.052 (6)−0.006 (5)0.031 (6)0.000 (5)
C140.053 (6)0.074 (6)0.067 (7)−0.008 (4)0.033 (5)−0.006 (5)
C150.075 (6)0.086 (7)0.068 (7)−0.006 (5)0.009 (6)0.006 (6)
Geometric parameters (Å, °) top
Cd—Br42.5520 (11)C6—H60.9300
Cd—Br32.5779 (11)C7—C81.524 (10)
Cd—Br12.5951 (11)C7—H7A0.9700
Cd—Br22.6041 (12)C7—H7B0.9700
N1—C21.332 (10)C8—C91.522 (10)
N1—C61.342 (9)C8—H8A0.9700
N1—C11.512 (11)C8—H8B0.9700
N2—C121.318 (10)C9—C101.503 (11)
N2—C131.347 (10)C9—H9A0.9700
N2—C151.473 (10)C9—H9B0.9700
C1—H1A0.9600C10—C141.370 (10)
C1—H1B0.9600C10—C111.373 (10)
C1—H1C0.9600C11—C121.365 (11)
C2—C31.359 (11)C11—H110.9300
C2—H20.9300C12—H120.9300
C3—C41.401 (10)C13—C141.380 (11)
C3—H30.9300C13—H130.9300
C4—C51.371 (10)C14—H140.9300
C4—C71.486 (10)C15—H15A0.9600
C5—C61.370 (11)C15—H15B0.9600
C5—H50.9300C15—H15C0.9600
Br4—Cd—Br3110.04 (4)C4—C7—H7B109.5
Br4—Cd—Br1112.55 (4)C8—C7—H7B109.5
Br3—Cd—Br1107.77 (4)H7A—C7—H7B108.1
Br4—Cd—Br2107.75 (4)C7—C8—C9111.1 (7)
Br3—Cd—Br2110.93 (4)C7—C8—H8A109.4
Br1—Cd—Br2107.80 (4)C9—C8—H8A109.4
C2—N1—C6119.8 (8)C7—C8—H8B109.4
C2—N1—C1122.0 (7)C9—C8—H8B109.4
C6—N1—C1118.3 (8)H8A—C8—H8B108.0
C12—N2—C13119.6 (8)C10—C9—C8117.3 (7)
C12—N2—C15122.4 (8)C10—C9—H9A108.0
C13—N2—C15118.0 (8)C8—C9—H9A108.0
N1—C1—H1A109.5C10—C9—H9B108.0
N1—C1—H1B109.5C8—C9—H9B108.0
H1A—C1—H1B109.5H9A—C9—H9B107.2
N1—C1—H1C109.5C14—C10—C11116.1 (8)
H1A—C1—H1C109.5C14—C10—C9124.7 (8)
H1B—C1—H1C109.5C11—C10—C9119.2 (8)
N1—C2—C3121.2 (8)C12—C11—C10120.7 (8)
N1—C2—H2119.4C12—C11—H11119.7
C3—C2—H2119.4C10—C11—H11119.7
C2—C3—C4121.0 (8)N2—C12—C11122.2 (8)
C2—C3—H3119.5N2—C12—H12118.9
C4—C3—H3119.5C11—C12—H12118.9
C5—C4—C3115.9 (7)N2—C13—C14119.3 (8)
C5—C4—C7122.6 (7)N2—C13—H13120.4
C3—C4—C7121.5 (8)C14—C13—H13120.4
C4—C5—C6121.5 (7)C10—C14—C13122.2 (8)
C4—C5—H5119.2C10—C14—H14118.9
C6—C5—H5119.2C13—C14—H14118.9
N1—C6—C5120.6 (8)N2—C15—H15A109.5
N1—C6—H6119.7N2—C15—H15B109.5
C5—C6—H6119.7H15A—C15—H15B109.5
C4—C7—C8110.6 (7)N2—C15—H15C109.5
C4—C7—H7A109.5H15A—C15—H15C109.5
C8—C7—H7A109.5H15B—C15—H15C109.5
Acknowledgements top

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

references
References top

Bruker (1998). SMART. Bruker AXS, Inc., Madison, Wisconsion, USA.

Bruker (2003). SAINT-Plus. Bruker AXS, Inc., Madison, Wisconsion, USA.

Dou, Y.-L., Li, Z.-G., Xu, J.-W. & Zhang, W.-X. (2007). Acta Cryst. E63, o1874–o1875.

Sheldrick, G. M. (2003). SADABS. Bruker AXS, Inc., Madison, Wisconsion, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Yang, F., Deng, J.-C., Li, Z.-G. & Xu, J.-W. (2008). Acta Cryst. E64, o253.