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Acta Cryst. (2007). E63, m1781    [ doi:10.1107/S1600536807025597 ]

1,1'-(Propane-1,3-diyl)dipyridinium dibromidodichloridocadmate(II)

X.-C. Liu, J. Shi, Y.-Y. Niu, N. Xu and S. W. Ng

Abstract top

The Cd atom in the title compound, (C13H16N2)[CdBr2Cl2], is coordinated by four halogen atoms in a tetrahedral geometry. The four halogen atoms are each disordered between Br and Cl, with the Br:Cl ratios being approximately 0.5:0.5, 0.6:0.4, 0.4:0.6 and 0.8:0.2.

Comment top

The preceding paper reports the structure of the tetrahedral dibromidodichloridocadmate(II), which has been isolated as the 1,2-ethanedipyridinium salt (Liu et al., 2007). The structure of propyl-1,3-di(4-pyridinium) tetrabromidocadmate(II) has been reported in the non-centrosymmetric space group Cc (Kao & Chen, 2004). The title compound, [C13H16N2][CdBr2Cl2] is not, however, isostructural. The cadmium atom in the centrosymmetric structure is coordinated by four halogen atoms in a tetrahedral geometry; the halogen atoms are disordered (Fig. 1). The cations and anions do not have signification interactions with each other.

Related literature top

For related literature, see: Kao & Chen (2004); Liu et al. (2007).

Experimental top

The salt was synthesized from the reaction of 1,3-propanedipyridinium dibromide (0.036 g, 0.1 mmol) in methanol (5 ml) and cadmium dichloride (0.037 g, 0.2 mmol) in DMF (10 ml). The mixture was set aside for the formation of colourless crystals in 30% yield after several days.

Refinement top

The halogens lie in general positions; initial attempts to refine the structure with either four chlorines or four bromines gave unacceptably high R-indices (and large peaks/holes). The four halogen atoms were then refined as four (Br+Cl) mixtures; one attempt allowed the mixtures to have the same displacement parameters as well as to share the same site. A second attempt had the components having only the same displacement parameters. The second led to a formulation consisting of approximately 2.25 Br and 1.75 C l atoms for the anion. A special restraint was used that fixed the total number of Br and Cl atoms as exactly 2.25 Br and 1.75 C l. In the best disorder model, the site occupancy factors for the (Br+Cl) mixtures refined to 0.486 (2):0.514 (2), 0.561 (2):0.439 (2), 0.431 (2):0.569 (2) and 0.771 (2):0.229 (2).

The compound is [C13H16N2] [CdBr2.25Cl1.75] but because it has nearly equal numbers of bromine and chlorine atoms, it is regarded as [C13H16N2] [CdBr2Cl2] for the purpose of naming the compound. The CH&N elemental percentages are in fair agreement with the [C13H16N2] [CdBr2.25Cl1.75] formulation.

The disorder in the anion did not affect the cation. Carbon-bound H atoms were positioned geometrically (C—H 0.93 and 0.97 Å), and were included in the refinement in the riding model approximation, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. The structure of [C13H16N2][CdBr2Cl2], with displacement ellipsoids drawn at the 50% probability level. The bromine and chlorine atoms are disordered; the figure depicts the anion as a [CdX4]2− species. Hydrogen atoms are drawn as spheres of arbitrary radius.
Propane-1,3-diyldipyridinium dibromidodichloridocadmate(II) top
Crystal data top
(C13H16N2)[CdBr2Cl2]F000 = 1058
Mr = 554.51Dx = 2.003 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2441 reflections
a = 8.1159 (6) Åθ = 2.7–21.3º
b = 15.058 (1) ŵ = 6.32 mm−1
c = 15.103 (1) ÅT = 295 (2) K
β = 95.023 (1)ºBlock, colourless
V = 1838.6 (2) Å30.15 × 0.10 × 0.08 mm
Z = 4
Data collection top
Bruker APEX area-detector
diffractometer		3220 independent reflections
Radiation source: fine-focus sealed tube2287 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.409, Tmax = 0.632k = −17→17
10838 measured reflectionsl = −17→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.121  w = 1/[σ2(Fo2) + (0.0638P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
3220 reflectionsΔρmax = 0.82 e Å−3
201 parametersΔρmin = −0.63 e Å−3
6 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
(C13H16N2)[CdBr2Cl2]V = 1838.6 (2) Å3
Mr = 554.51Z = 4
Monoclinic, P21/cMo Kα
a = 8.1159 (6) ŵ = 6.32 mm−1
b = 15.058 (1) ÅT = 295 (2) K
c = 15.103 (1) Å0.15 × 0.10 × 0.08 mm
β = 95.023 (1)º
Data collection top
Bruker APEX area-detector
diffractometer		3220 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2287 reflections with I > 2σ(I)
Tmin = 0.409, Tmax = 0.632Rint = 0.034
10838 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0376 restraints
wR(F2) = 0.121H-atom parameters constrained
S = 1.08Δρmax = 0.82 e Å−3
3220 reflectionsΔρmin = −0.63 e Å−3
201 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cd10.25358 (6)0.20461 (3)0.28984 (3)0.0586 (2)
Br10.4650 (9)0.3290 (3)0.2721 (6)0.0757 (10)0.4863 (18)
Cl10.485 (2)0.3078 (9)0.2754 (14)0.0757 (10)0.5137 (18)
Br20.3988 (7)0.0714 (3)0.3716 (4)0.0712 (8)0.561 (2)
Cl20.416 (2)0.0906 (10)0.3671 (15)0.0712 (8)0.439 (2)
Br30.1618 (15)0.1511 (12)0.1337 (11)0.0651 (15)0.431 (2)
Cl30.135 (3)0.145 (2)0.139 (2)0.0651 (15)0.569 (2)
Br40.0147 (3)0.27032 (12)0.36647 (16)0.0712 (5)0.771 (2)
Cl4−0.011 (3)0.2488 (14)0.3558 (16)0.0712 (5)0.229 (2)
N10.6152 (5)0.1612 (3)0.0464 (3)0.0528 (12)
C10.6960 (9)0.1278 (5)−0.0181 (5)0.0695 (18)
H10.71190.1625−0.06760.083*
C20.7553 (10)0.0450 (6)−0.0135 (6)0.095 (3)
H20.81480.0240−0.05900.114*
C30.7317 (11)−0.0074 (6)0.0538 (8)0.098 (3)
H30.7691−0.06580.05510.118*
C40.6496 (10)0.0269 (6)0.1227 (7)0.096 (3)
H40.6339−0.00770.17230.115*
C50.5921 (8)0.1118 (5)0.1169 (5)0.073 (2)
H50.53620.13540.16280.088*
N20.9403 (6)0.3797 (3)0.1317 (3)0.0568 (13)
C61.0594 (8)0.3774 (5)0.0759 (4)0.0649 (17)
H61.06190.33150.03470.078*
C71.1779 (9)0.4426 (6)0.0793 (6)0.084 (2)
H71.26120.44160.04090.101*
C81.1712 (9)0.5093 (6)0.1404 (6)0.087 (2)
H81.25030.55410.14350.104*
C91.0487 (11)0.5103 (6)0.1970 (5)0.087 (2)
H91.04380.55550.23860.105*
C100.9341 (9)0.4443 (5)0.1915 (5)0.0731 (19)
H100.85050.44430.22990.088*
C110.5538 (8)0.2530 (4)0.0405 (5)0.0660 (18)
H11A0.48590.26400.08910.079*
H11B0.48470.2604−0.01470.079*
C120.6934 (8)0.3208 (4)0.0443 (5)0.0657 (18)
H12A0.75270.3149−0.00840.079*
H12B0.64700.38010.04460.079*
C130.8126 (8)0.3086 (5)0.1259 (5)0.073 (2)
H13A0.75240.31000.17860.087*
H13B0.86600.25110.12350.087*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0570 (3)0.0650 (3)0.0539 (3)0.0085 (2)0.0050 (2)−0.0107 (2)
Br10.077 (2)0.062 (3)0.0900 (11)−0.0072 (19)0.0218 (13)−0.022 (2)
Cl10.077 (2)0.062 (3)0.0900 (11)−0.0072 (19)0.0218 (13)−0.022 (2)
Br20.0635 (15)0.056 (2)0.0904 (11)0.0047 (14)−0.0153 (10)0.0029 (17)
Cl20.0635 (15)0.056 (2)0.0904 (11)0.0047 (14)−0.0153 (10)0.0029 (17)
Br30.067 (4)0.072 (3)0.056 (2)0.003 (3)0.004 (2)−0.0156 (17)
Cl30.067 (4)0.072 (3)0.056 (2)0.003 (3)0.004 (2)−0.0156 (17)
Br40.0762 (11)0.0748 (13)0.0660 (9)0.0202 (8)0.0252 (7)0.0008 (8)
Cl40.0762 (11)0.0748 (13)0.0660 (9)0.0202 (8)0.0252 (7)0.0008 (8)
N10.051 (3)0.056 (3)0.051 (3)−0.005 (2)0.001 (2)0.006 (2)
C10.085 (5)0.064 (5)0.062 (4)−0.008 (4)0.018 (4)−0.010 (4)
C20.099 (7)0.077 (6)0.111 (7)−0.005 (5)0.025 (5)−0.025 (5)
C30.083 (6)0.056 (5)0.150 (9)−0.001 (4)−0.025 (6)−0.015 (6)
C40.092 (6)0.076 (6)0.112 (7)−0.019 (5)−0.028 (5)0.043 (6)
C50.060 (4)0.092 (6)0.069 (5)−0.013 (4)0.012 (3)0.009 (4)
N20.052 (3)0.060 (3)0.057 (3)0.010 (3)−0.001 (2)0.005 (3)
C60.060 (4)0.071 (5)0.065 (4)0.007 (4)0.012 (3)−0.006 (3)
C70.076 (5)0.094 (6)0.085 (6)−0.001 (5)0.020 (4)0.009 (5)
C80.068 (5)0.075 (5)0.114 (7)−0.008 (4)−0.014 (5)0.011 (5)
C90.090 (6)0.075 (6)0.091 (6)0.017 (5)−0.018 (5)−0.018 (5)
C100.065 (4)0.088 (5)0.065 (4)0.020 (4)0.001 (3)−0.006 (4)
C110.057 (4)0.063 (4)0.076 (5)0.002 (3)−0.004 (3)0.009 (4)
C120.072 (4)0.052 (4)0.070 (4)0.004 (3)−0.011 (3)0.005 (3)
C130.062 (4)0.073 (5)0.081 (5)−0.006 (4)−0.002 (4)0.015 (4)
Geometric parameters (Å, °) top
Cd1—Cl22.404 (19)N2—C101.331 (8)
Cd1—Cl12.46 (2)N2—C61.338 (8)
Cd1—Br32.540 (17)N2—C131.488 (8)
Cd1—Br42.544 (2)C6—C71.373 (10)
Cd1—Cl42.53 (2)C6—H60.9300
Cd1—Cl32.55 (3)C7—C81.368 (11)
Cd1—Br12.570 (8)C7—H70.9300
Cd1—Br22.585 (5)C8—C91.366 (11)
N1—C11.320 (8)C8—H80.9300
N1—C51.327 (8)C9—C101.358 (10)
N1—C111.469 (8)C9—H90.9300
C1—C21.336 (11)C10—H100.9300
C1—H10.9300C11—C121.522 (9)
C2—C31.314 (12)C11—H11A0.9700
C2—H20.9300C11—H11B0.9700
C3—C41.383 (12)C12—C131.511 (9)
C3—H30.9300C12—H12A0.9700
C4—C51.362 (11)C12—H12B0.9700
C4—H40.9300C13—H13A0.9700
C5—H50.9300C13—H13B0.9700
Cl2—Cd1—Cl195.9 (5)C5—C4—H4120.4
Cl2—Cd1—Br3109.1 (7)C3—C4—H4120.4
Cl1—Cd1—Br3106.4 (6)N1—C5—C4120.4 (7)
Cl2—Cd1—Br4117.7 (6)N1—C5—H5119.8
Cl1—Cd1—Br4114.4 (3)C4—C5—H5119.8
Br3—Cd1—Br4111.9 (3)C10—N2—C6121.3 (6)
Cl2—Cd1—Cl4116.4 (8)C10—N2—C13119.9 (6)
Cl1—Cd1—Cl4123.3 (6)C6—N2—C13118.8 (6)
Br3—Cd1—Cl4105.0 (6)N2—C6—C7119.9 (7)
Br4—Cd1—Cl49.3 (5)N2—C6—H6120.0
Cl2—Cd1—Cl3109.2 (9)C7—C6—H6120.0
Cl1—Cd1—Cl3112.1 (8)C8—C7—C6118.8 (7)
Br3—Cd1—Cl35.9 (7)C8—C7—H7120.6
Br4—Cd1—Cl3107.3 (6)C6—C7—H7120.6
Cl4—Cd1—Cl3100.1 (7)C7—C8—C9120.3 (8)
Cl2—Cd1—Br1103.2 (4)C7—C8—H8119.9
Cl1—Cd1—Br17.9 (4)C9—C8—H8119.9
Br3—Cd1—Br1106.2 (4)C10—C9—C8119.0 (8)
Br4—Cd1—Br1107.84 (13)C10—C9—H9120.5
Cl4—Cd1—Br1116.5 (5)C8—C9—H9120.5
Cl3—Cd1—Br1111.6 (6)N2—C10—C9120.6 (7)
Cl2—Cd1—Br26.4 (5)N2—C10—H10119.7
Cl1—Cd1—Br2102.2 (4)C9—C10—H10119.7
Br3—Cd1—Br2106.4 (4)N1—C11—C12112.4 (5)
Br4—Cd1—Br2114.72 (16)N1—C11—H11A109.1
Cl4—Cd1—Br2112.5 (6)C12—C11—H11A109.1
Cl3—Cd1—Br2105.8 (8)N1—C11—H11B109.1
Br1—Cd1—Br2109.55 (17)C12—C11—H11B109.1
C1—N1—C5119.6 (6)H11A—C11—H11B107.9
C1—N1—C11120.1 (5)C13—C12—C11111.8 (6)
C5—N1—C11120.3 (6)C13—C12—H12A109.3
N1—C1—C2121.1 (7)C11—C12—H12A109.3
N1—C1—H1119.4C13—C12—H12B109.3
C2—C1—H1119.4C11—C12—H12B109.3
C3—C2—C1121.7 (8)H12A—C12—H12B107.9
C3—C2—H2119.2N2—C13—C12110.7 (6)
C1—C2—H2119.2N2—C13—H13A109.5
C2—C3—C4118.0 (8)C12—C13—H13A109.5
C2—C3—H3121.0N2—C13—H13B109.5
C4—C3—H3121.0C12—C13—H13B109.5
C5—C4—C3119.2 (8)H13A—C13—H13B108.1
C5—N1—C1—C2−0.2 (10)C6—C7—C8—C90.2 (12)
C11—N1—C1—C2178.9 (7)C7—C8—C9—C100.0 (12)
N1—C1—C2—C32.1 (13)C6—N2—C10—C90.4 (10)
C1—C2—C3—C4−3.0 (13)C13—N2—C10—C9−179.2 (6)
C2—C3—C4—C52.1 (12)C8—C9—C10—N2−0.3 (11)
C1—N1—C5—C4−0.7 (9)C1—N1—C11—C12−66.1 (7)
C11—N1—C5—C4−179.7 (6)C5—N1—C11—C12112.9 (7)
C3—C4—C5—N1−0.3 (11)N1—C11—C12—C13−54.8 (8)
C10—N2—C6—C7−0.2 (10)C10—N2—C13—C12106.4 (7)
C13—N2—C6—C7179.4 (6)C6—N2—C13—C12−73.3 (8)
N2—C6—C7—C8−0.1 (11)C11—C12—C13—N2−175.6 (5)
Acknowledgements top

The authors thank the National Natural Science Foundation of China (grant No. 20671083), the Henan Province Excellent Young Foundation (grant No. 0612002800), Zhengzhou University and the University of Malaya for supporting this work. We thank Central China Normal University for the diffraction measurements.

references
References top

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