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Acta Cryst. (2007). E63, m1893    [ doi:10.1107/S1600536807027456 ]

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

X.-C. Liu, M.-C. Wang, Y.-Y. Niu, F.-K. Zhao and S. W. Ng

Abstract top

The Hg atom in the title compound, (C13H16N2)[HgBr2I2], is coordinated by four halogen atoms in a tetrahedral geometry. The four halogen atoms are each disordered between I and Br, with the I:Br ratios being 0.228 (3):0.772 (3), 0.333 (6):0.667 (6), 0.346 (6):0.654 (6) and 0.843 (7):0.157 (7).

Comment top

The preceding study reports the structure of a tetrahedral dibromidodichloridomercurate(II), which has been isolated as the 1,2-ethanedipyridinium salt (Wang et al., 2007). Replacing the cation by 1,3-propanedipyridinium furnishes a similar tetrahalomercurate. The anion of the salt is composed 2.25 bromines and 1.75 iodines; the metal atom shows tetrahedral coordination (Fig. 1). Selected bond distances are given in Table 1.

Related literature top

For related tetrahalogenomercurates, see the preceding paper by Wang et al. (2007).

Experimental top

The salt was synthesized from the reaction of propane-1,3-dipyridinium dibromide (0.036 g, 0.1 mmol) in methanol (5 ml) and mercuric iodide (0.091 g, 0.2 mmol) in DMF (10 ml). The mixture was set aside for the formation of colorless crystals in 30% yield after several days.

Refinement top

The four halogens lie in general positions. Initial attempts to refine the structure with either four bromines or four iodines gave unacceptably high R-indices and large peaks/deep holes. The four halogen atoms were then refined as four (Br+I) mixtures; one attempt allowed the mixtures to have the same displacement parameters as well as sharing the same site. A second attempt had the components having the same displacement parameters only. The second led to a formulation consisting of approximately of 2.25 Br and 1.75 I atoms. The use of a restraint that fixed the number of Br and I atoms as exactly 2.25 Br and 1.75 I led to occupancies of 0.772 (3), 0.667 (6), 0.654 (6) and 0.157 (7), respectively, for Br1, Br2, Br3 and Br4, and 0.228 (3), 0.333 (6), 0.346 (6) and 0.843 (7), respectively, for I1, I2, I3 and I4.

The anion is [HgBr2.25I1.75]2−, but because it has nearly two bromine and two iodine atoms, it is regarded as [HgBr2I2] for the purpose of naming the compound. The formulation is in fair agreement with CH&N elemental analysis. The refinement for a [C13H16N2] [HgBr2.5I1.5] formulation is not significantly distinguishable in the R index, however.

Disorder also affected the cation; the pyridyl ring was refined as a rigid hexagon (C—C = C—N = 1.39 Å). The C(sp3)—C(sp3) distance was restrained to 1.50 (1) Å, and the N···C(sp3) distance to 2.45 (1) Å. The displacement parameters of atoms of the cation were restrained to be nearly isotropic. C-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).

The final difference Fourier map had a large peak at 0.93 Å from Hg1, but was otherwise featureless.

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 molecular structure of [C13H16N2][HgBr2I2]. Displacement ellipsoids drawn at the 50% probability level. The bromine and iodine atoms are disordered; the figure depicts the anion as an [HgX4]2− species. Hydrogen atoms are drawn as spheres of arbitrary radius.
1,1'-(Propane-1,3-diyl)dipyridinium dibromidodiiodidomercurate(II) top
Crystal data top
(C13H16N2)[HgBr2I2]F000 = 1438
Mr = 802.74Dx = 2.690 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3755 reflections
a = 8.297 (2) Åθ = 2.6–23.5º
b = 15.431 (4) ŵ = 15.02 mm−1
c = 15.563 (4) ÅT = 295 (2) K
β = 95.984 (5)ºBlock, colourless
V = 1981.8 (9) Å30.30 × 0.30 × 0.26 mm
Z = 4
Data collection top
Bruker APEX area-detector
diffractometer		3482 independent reflections
Radiation source: fine-focus sealed tube2630 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.046
T = 295(2) Kθmax = 25.0º
φ and ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.011, Tmax = 0.111k = −18→18
14070 measured reflectionsl = −18→18
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)] = 0.039H-atom parameters constrained
wR(F2) = 0.100  w = 1/[σ2(Fo2) + (0.0445P)2 + 4.75P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
3482 reflectionsΔρmax = 1.19 e Å−3
173 parametersΔρmin = −0.75 e Å−3
96 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
(C13H16N2)[HgBr2I2]V = 1981.8 (9) Å3
Mr = 802.74Z = 4
Monoclinic, P21/cMo Kα
a = 8.297 (2) ŵ = 15.02 mm−1
b = 15.431 (4) ÅT = 295 (2) K
c = 15.563 (4) Å0.30 × 0.30 × 0.26 mm
β = 95.984 (5)º
Data collection top
Bruker APEX area-detector
diffractometer		3482 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2630 reflections with I > 2σ(I)
Tmin = 0.011, Tmax = 0.111Rint = 0.046
14070 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03996 restraints
wR(F2) = 0.100H-atom parameters constrained
S = 1.01Δρmax = 1.19 e Å−3
3482 reflectionsΔρmin = −0.75 e Å−3
173 parameters
Special details top

Experimental. The crystals do not have well formed faces for a numerical correction. The value is somewhat larger than the cutoff of 3.0, but as the structure seems to have refined smoothly, the correction is alright.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Hg10.25202 (5)0.20536 (2)0.28986 (2)0.06365 (15)
I10.478 (3)0.3426 (13)0.2693 (18)0.0854 (11)0.228 (3)
I20.419 (2)0.0865 (8)0.3686 (12)0.0679 (12)0.333 (6)
I30.134 (3)0.1381 (19)0.1346 (19)0.0669 (17)0.346 (6)
I40.0046 (2)0.27339 (11)0.36694 (10)0.0720 (5)0.843 (7)
Br10.4644 (13)0.3249 (5)0.2738 (7)0.0854 (11)0.772 (3)
Br20.4084 (16)0.0665 (5)0.3778 (9)0.0679 (12)0.667 (6)
Br30.164 (2)0.1474 (15)0.1304 (15)0.0669 (17)0.654 (6)
Br4−0.0355 (19)0.2486 (10)0.3560 (10)0.0720 (5)0.157 (7)
N10.6071 (6)0.1678 (3)0.0538 (4)0.0562 (18)
C10.6774 (8)0.1293 (5)−0.0139 (4)0.089 (3)
H10.68730.1603−0.06430.106*
C20.7330 (9)0.0444 (5)−0.0062 (6)0.118 (5)
H20.78010.0186−0.05150.142*
C30.7182 (10)−0.0020 (3)0.0691 (8)0.116 (5)
H30.7554−0.05880.07420.139*
C40.6479 (10)0.0366 (5)0.1368 (6)0.106 (4)
H40.63800.00550.18720.127*
C50.5923 (8)0.1215 (5)0.1292 (3)0.075 (3)
H50.54530.14720.17440.090*
N20.9334 (6)0.3771 (3)0.1315 (4)0.0609 (19)
C61.0535 (7)0.3751 (4)0.0756 (4)0.073 (3)
H61.05770.32950.03680.087*
C71.1673 (7)0.4414 (5)0.0775 (5)0.082 (3)
H71.24760.44010.04010.098*
C81.1611 (8)0.5096 (4)0.1354 (5)0.095 (4)
H81.23720.55390.13670.114*
C91.0410 (10)0.5116 (4)0.1913 (5)0.087 (3)
H91.03680.55720.23010.104*
C100.9272 (7)0.4453 (4)0.1894 (4)0.073 (3)
H100.84680.44660.22680.087*
C110.5536 (10)0.2563 (6)0.0483 (7)0.075 (3)
H11A0.49130.26840.09630.090*
H11B0.48230.2639−0.00460.090*
C120.6891 (10)0.3202 (5)0.0496 (6)0.068 (3)
H12A0.64500.37850.04880.081*
H12B0.74420.3128−0.00190.081*
C130.8085 (10)0.3095 (6)0.1278 (5)0.067 (3)
H13A0.75230.31250.17930.081*
H13B0.85930.25300.12630.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.0598 (2)0.0770 (3)0.0551 (2)0.00921 (18)0.01045 (17)−0.01326 (18)
I10.084 (2)0.079 (3)0.0980 (15)−0.025 (2)0.0357 (12)−0.027 (3)
I20.0654 (16)0.055 (4)0.080 (3)0.006 (3)−0.0092 (15)0.007 (3)
I30.064 (5)0.081 (4)0.0569 (19)−0.001 (3)0.011 (3)−0.016 (2)
I40.0786 (10)0.0844 (10)0.0582 (6)0.0220 (6)0.0310 (6)0.0064 (6)
Br10.084 (2)0.079 (3)0.0980 (15)−0.025 (2)0.0357 (12)−0.027 (3)
Br20.0654 (16)0.055 (4)0.080 (3)0.006 (3)−0.0092 (15)0.007 (3)
Br30.064 (5)0.081 (4)0.0569 (19)−0.001 (3)0.011 (3)−0.016 (2)
Br40.0786 (10)0.0844 (10)0.0582 (6)0.0220 (6)0.0310 (6)0.0064 (6)
N10.048 (4)0.070 (5)0.051 (4)−0.007 (4)0.005 (3)0.002 (4)
C10.101 (9)0.105 (9)0.065 (7)−0.037 (7)0.031 (6)−0.015 (6)
C20.119 (11)0.089 (9)0.152 (14)−0.017 (8)0.041 (10)−0.057 (9)
C30.090 (9)0.069 (8)0.184 (16)−0.016 (7)−0.013 (10)−0.020 (10)
C40.096 (9)0.088 (9)0.127 (12)−0.025 (7)−0.015 (9)0.029 (8)
C50.073 (7)0.094 (8)0.060 (7)−0.007 (6)0.011 (5)0.013 (6)
N20.055 (5)0.071 (5)0.058 (5)0.005 (4)0.009 (4)0.002 (4)
C60.069 (7)0.080 (7)0.072 (7)0.007 (5)0.020 (5)0.002 (5)
C70.069 (7)0.098 (8)0.082 (8)−0.004 (6)0.023 (6)0.019 (6)
C80.078 (8)0.098 (9)0.106 (10)−0.010 (7)−0.009 (7)0.004 (8)
C90.091 (8)0.078 (7)0.087 (8)0.006 (6)−0.009 (7)−0.027 (6)
C100.068 (7)0.095 (8)0.057 (6)0.022 (6)0.008 (5)−0.004 (5)
C110.069 (7)0.076 (7)0.077 (7)0.005 (6)−0.007 (6)0.008 (5)
C120.065 (6)0.063 (6)0.073 (7)−0.001 (5)−0.007 (5)0.010 (5)
C130.061 (6)0.083 (7)0.060 (6)0.001 (5)0.016 (5)0.007 (5)
Geometric parameters (Å, °) top
Hg1—I22.534 (14)N2—C61.39
Hg1—Br12.582 (6)N2—C101.39
Hg1—Br22.79 (1)N2—C131.467 (9)
Hg1—Br32.67 (2)C6—C71.39
Hg1—Br42.78 (1)C6—H60.93
Hg1—I42.6963 (14)C7—C81.39
Hg1—I32.72 (3)C7—H70.93
Hg1—I12.868 (16)C8—C91.39
N1—C11.39C8—H80.93
N1—C51.39C9—C101.39
N1—C111.435 (11)C9—H90.93
C1—C21.39C10—H100.93
C1—H10.93C11—C121.494 (7)
C2—C31.39C11—H11A0.97
C2—H20.93C11—H11B0.97
C3—C41.39C12—C131.495 (8)
C3—H30.93C12—H12A0.97
C4—C51.39C12—H12B0.97
C4—H40.93C13—H13A0.97
C5—H50.93C13—H13B0.97
I2—Hg1—Br1102.8 (4)C5—C4—C3120.0
I2—Hg1—Br3106.8 (7)C5—C4—H4120.0
Br1—Hg1—Br3105.8 (4)C3—C4—H4120.0
I2—Hg1—I4118.0 (4)C4—C5—N1120.0
Br1—Hg1—I4108.9 (2)C4—C5—H5120.0
Br3—Hg1—I4113.4 (4)N1—C5—H5120.0
I2—Hg1—I3106.3 (8)C6—N2—C10120.0
Br1—Hg1—I3111.9 (5)C6—N2—C13120.6 (6)
Br3—Hg1—I36.3 (6)C10—N2—C13119.3 (6)
I4—Hg1—I3108.9 (5)C7—C6—N2120.0
I2—Hg1—Br4116.2 (5)C7—C6—H6120.0
Br1—Hg1—Br4119.1 (4)N2—C6—H6120.0
Br3—Hg1—Br4105.3 (5)C6—C7—C8120.0
I4—Hg1—Br410.9 (3)C6—C7—H7120.0
I3—Hg1—Br4100.3 (6)C8—C7—H7120.0
I2—Hg1—Br25.3 (6)C9—C8—C7120.0
Br1—Hg1—Br2108.0 (4)C9—C8—H8120.0
Br3—Hg1—Br2105.5 (6)C7—C8—H8120.0
I4—Hg1—Br2114.7 (3)C8—C9—C10120.0
I3—Hg1—Br2104.4 (7)C8—C9—H9120.0
Br4—Hg1—Br2112.1 (4)C10—C9—H9120.0
I2—Hg1—I1105.0 (7)C9—C10—N2120.0
Br1—Hg1—I12.3 (9)C9—C10—H10120.0
Br3—Hg1—I1105.2 (6)N2—C10—H10120.0
I4—Hg1—I1107.4 (5)N1—C11—C12113.5 (7)
I3—Hg1—I1111.2 (7)N1—C11—H11A108.9
Br4—Hg1—I1117.4 (6)C12—C11—H11A108.9
Br2—Hg1—I1110.3 (6)N1—C11—H11B108.9
Br4—I4—Hg193.3 (16)C12—C11—H11B108.9
I4—Br4—Hg175.8 (16)H11A—C11—H11B107.7
C1—N1—C5120.0C11—C12—C13111.9 (6)
C1—N1—C11120.9 (6)C11—C12—H12A109.2
C5—N1—C11119.1 (6)C13—C12—H12A109.2
C2—C1—N1120.0C11—C12—H12B109.2
C2—C1—H1120.0C13—C12—H12B109.2
N1—C1—H1120.0H12A—C12—H12B107.9
C1—C2—C3120.0N2—C13—C12111.1 (6)
C1—C2—H2120.0N2—C13—H13A109.4
C3—C2—H2120.0C12—C13—H13A109.4
C2—C3—C4120.0N2—C13—H13B109.4
C2—C3—H3120.0C12—C13—H13B109.4
C4—C3—H3120.0H13A—C13—H13B108.0
I2—Hg1—I4—Br4−83.3 (19)I1—Hg1—Br4—I4−23 (2)
Br1—Hg1—I4—Br4160.2 (18)C11—N1—C1—C2178.0 (6)
Br3—Hg1—I4—Br442.6 (19)C11—N1—C5—C4−178.0 (6)
I3—Hg1—I4—Br437.9 (19)C13—N2—C6—C7177.5 (6)
Br2—Hg1—I4—Br4−78.7 (19)C13—N2—C10—C9−177.5 (6)
I1—Hg1—I4—Br4158.4 (19)C1—N1—C11—C12−68.6 (9)
I2—Hg1—Br4—I4102.2 (18)C5—N1—C11—C12109.4 (8)
Br1—Hg1—Br4—I4−22 (2)N1—C11—C12—C13−55.9 (12)
Br3—Hg1—Br4—I4−139.9 (18)C6—N2—C13—C12−73.2 (9)
I3—Hg1—Br4—I4−143.8 (19)C10—N2—C13—C12104.3 (8)
Br2—Hg1—Br4—I4105.9 (18)C11—C12—C13—N2−175.5 (8)
Selected geometric parameters (Å) top
Hg1—I22.534 (14)Hg1—Br42.78 (1)
Hg1—Br12.582 (6)Hg1—I42.6963 (14)
Hg1—Br22.79 (1)Hg1—I32.72 (3)
Hg1—Br32.67 (2)Hg1—I12.868 (16)
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

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2004). SAINT (Version 6.45a) and SMART (Version 6.45a). Bruker AXS Inc., Madison, Winconsin, USA. [These programs do not have concurrent version numbers - please provide correct values]

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Wang, Q.-L., Yang, C.-C., Niu, Y.-Y., Liu, X.-C. & Ng, S. W. (2007). Acta Cryst. E63, mXXXX-mXXXX. [CI2386]

Westrip, S. P. (2007). publCIF. In preparation.