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Acta Cryst. (2007). E63, m1896    [ doi:10.1107/S1600536807027481 ]

1,1'-(p-Phenylenedimethylene)dipyridinium trichloridoiodidomercurate(II)

Z.-H. He, M.-S. Tang, Y.-Y. Niu, X.-R. Lv and S. W. Ng

Abstract top

The Hg atom in the title compound, (C18H18N2)[HgCl2.75I1.25], is coordinated by four halogen atoms in a tetrahedral geometry. Two of the four halogen atoms are each disordered between I and Cl, with the I:Cl ratios being 0.5793 (15):0.4208 (15) and 0.6708 (15):0.3292 (15). The two independent cations lie on different inversion centres.

Comment top

The preceding study reports the structure of a tetrahedral dibromodichloromercurate(II), which was isolated as a 1,2-ethanedipyridinium salt (Wang et al., 2007). Replacing the cation by α,α'-4-xylyldipyridinium furnishes a similar tetrahalomercurate. The anion of the salt is of composed 2.75 chlorines and 1.25 iodines (Fig. 1); the metal atom shows tetrahedral coordination. Selected bond distances are given in Table 1.

Related literature top

For related literature of tetrahalogenomercurates, see: Wang et al. (2007). For the synthesis of the organic component, see: Sindelar et al. (2004).

Experimental top

The salt was synthesized from the reaction of α,α'-4-xylyldipyridinium dichloride (0.033 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. The organic reactant was synthesized by using a literature method (Sindelar et al., 2004).

Refinement top

The four halogens lie in general positions. Initial attempts to refine the structure with either four iodines or four chlorines gave unacceptably high R-indices and large peaks/holes. The four halogen atoms were then refined as four (I+Cl) mixtures, with same displacement parameters. This led to a formulation consisting of approximately 1.25 I and 2.75 C l atoms. The use of a restraint that fixed the number of I and Cl atoms as exactly 1.25 I and 2.75 C l led to the occupancy of I1 as 0.6 and that of I2 as 0.7; the occupancies of I3 and I4 were nearly zero. As such, the Cl3 and Cl4 atoms were each assigned full occupancy, so that only the I1/Cl1 and I2/Cl2 halogen atoms were disordered.

The anion is [HgCl2.75I1.25]2−, but because it has nearly integral numbers of chlorine and iodine atoms, it is regarded as [HgCl3I] for the purpose of naming the compound. The formulation is, however, in poor agreement with CH&N elemental analysis, so that the synthesis probably yielded a range of tetrahalogenmercurates. Other formulations led to somewhat larger peaks/deep holes.

The disorder affected the cation; the pyridyl ring was refined as a rigid hexagon (C—C = C—N = 1.39 Å). C-bound H atoms were generated geometrically (C–H 0.93 Å), and were included in the refinement in the riding-model approximation, with U(H) set to 1.2Ueq(C).

The final difference Fourier map had a large peak at 0.91 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 [C18H18N2][HgCl2.75I1.25]. Displacement ellipsoids are drawn at the 50% probability level. Labels X1 and X2 denote the disordered I and Cl atoms (I1, I2, Cl1 and Cl2). Hydrogen atoms are drawn as spheres of arbitrary radius. [Symmetry code (i): 1 − x, 1 − y, 2 − z; (ii) 2 − x, −1 − y, 2 − z.]
1,1'-(p-Phenylenedimethylene)dipyridinium trichloridoiodidomercurate(II) top
Crystal data top
(C18H18N2)[HgCl2.75I1.25]F000 = 1332
Mr = 719.05Dx = 2.210 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4098 reflections
a = 14.2901 (9) Åθ = 2.5–22.8º
b = 9.4764 (6) ŵ = 9.25 mm−1
c = 16.151 (1) ÅT = 295 (2) K
β = 98.785 (1)ºBlock, colourless
V = 2161.5 (2) Å30.20 × 0.15 × 0.12 mm
Z = 4
Data collection top
Bruker APEX area-detector
diffractometer		3792 independent reflections
Radiation source: fine-focus sealed tube3097 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.037
T = 295(2) Kθmax = 25.0º
φ and ω scansθmin = 1.4º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −16→16
Tmin = 0.089, Tmax = 0.400k = −11→11
15087 measured reflectionsl = −19→19
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)] = 0.042H-atom parameters constrained
wR(F2) = 0.113  w = 1/[σ2(Fo2) + (0.0609P)2 + 2.8764P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3792 reflectionsΔρmax = 1.10 e Å−3
224 parametersΔρmin = −0.57 e Å−3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
(C18H18N2)[HgCl2.75I1.25]V = 2161.5 (2) Å3
Mr = 719.05Z = 4
Monoclinic, P21/cMo Kα
a = 14.2901 (9) ŵ = 9.25 mm−1
b = 9.4764 (6) ÅT = 295 (2) K
c = 16.151 (1) Å0.20 × 0.15 × 0.12 mm
β = 98.785 (1)º
Data collection top
Bruker APEX area-detector
diffractometer		3792 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3097 reflections with I > 2σ(I)
Tmin = 0.089, Tmax = 0.400Rint = 0.037
15087 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0424 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.05Δρmax = 1.10 e Å−3
3792 reflectionsΔρmin = −0.57 e Å−3
224 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Hg10.74880 (2)0.42222 (4)0.68910 (2)0.06253 (16)
I10.8501 (3)0.1938 (3)0.6478 (3)0.0731 (6)0.5793 (15)
Cl10.8430 (17)0.2326 (13)0.6529 (17)0.077 (4)0.4208 (15)
I20.6700 (2)0.3885 (4)0.83326 (16)0.0613 (5)0.6708 (15)
Cl20.6851 (19)0.386 (3)0.8131 (13)0.058 (4)0.3292 (15)
Cl30.62488 (15)0.4902 (2)0.56647 (12)0.0617 (5)
Cl40.84520 (15)0.6549 (2)0.69693 (14)0.0646 (5)
N10.3671 (4)0.3819 (5)0.7986 (2)0.0523 (16)
C10.4004 (4)0.2569 (4)0.7687 (3)0.063 (2)
H10.40480.17610.80170.075*
C20.4271 (4)0.2529 (5)0.6895 (3)0.071 (2)
H20.44940.16930.66950.085*
C30.4205 (5)0.3738 (6)0.6402 (2)0.071 (3)
H30.43840.37110.58730.085*
C40.3871 (5)0.4987 (5)0.6701 (3)0.078 (3)
H40.38270.57960.63720.094*
C50.3604 (4)0.5028 (4)0.7493 (3)0.069 (2)
H50.33810.58630.76930.082*
C60.3432 (7)0.3870 (9)0.8825 (5)0.065 (2)
H6A0.32740.29280.89940.078*
H6B0.28790.44640.88270.078*
C70.4251 (6)0.4449 (8)0.9450 (4)0.054 (2)
C80.4980 (7)0.3591 (8)0.9794 (5)0.060 (2)
H80.49660.26380.96550.072*
C90.4264 (7)0.5878 (9)0.9654 (5)0.063 (2)
H90.37720.64680.94240.076*
N20.8607 (4)−0.1805 (4)0.9319 (4)0.0560 (16)
C100.8258 (5)−0.0683 (7)0.9734 (4)0.100 (4)
H100.7900−0.08541.01590.120*
C110.8443 (7)0.0696 (5)0.9515 (5)0.113 (5)
H110.82090.14470.97920.136*
C120.8977 (6)0.0953 (5)0.8880 (6)0.104 (4)
H120.91010.18750.87330.125*
C130.9327 (6)−0.0170 (7)0.8465 (5)0.119 (5)
H130.96840.00020.80400.143*
C140.9142 (5)−0.1549 (6)0.8685 (4)0.093 (3)
H140.9375−0.23000.84070.111*
C150.8358 (7)−0.3242 (10)0.9509 (8)0.092 (3)
H15A0.7977−0.36520.90190.110*
H15B0.7980−0.32300.99590.110*
C160.9223 (7)−0.4144 (8)0.9763 (7)0.067 (3)
C170.9533 (8)−0.5048 (10)0.9197 (7)0.078 (3)
H170.9219−0.50870.86490.094*
C180.9696 (8)−0.4109 (9)1.0562 (7)0.074 (3)
H180.9491−0.35011.09490.089*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.0675 (3)0.0560 (2)0.0639 (2)0.00375 (15)0.00949 (17)0.00970 (15)
I10.0721 (11)0.0430 (16)0.1092 (11)0.0162 (12)0.0297 (8)0.0095 (15)
Cl10.092 (6)0.017 (5)0.129 (8)0.030 (4)0.041 (5)0.017 (5)
I20.0767 (13)0.0561 (7)0.0568 (13)−0.0089 (8)0.0283 (9)0.0031 (9)
Cl20.087 (9)0.049 (5)0.050 (8)−0.001 (5)0.050 (5)0.002 (5)
Cl30.0677 (13)0.0627 (12)0.0528 (11)0.0040 (10)0.0031 (9)0.0056 (9)
Cl40.0588 (13)0.0624 (12)0.0726 (13)−0.0014 (10)0.0106 (10)0.0147 (10)
N10.070 (5)0.047 (3)0.043 (3)−0.010 (3)0.017 (3)−0.007 (3)
C10.074 (6)0.067 (5)0.049 (4)−0.007 (4)0.013 (4)0.002 (4)
C20.079 (6)0.071 (6)0.066 (6)−0.002 (5)0.024 (5)−0.007 (5)
C30.083 (7)0.081 (6)0.050 (5)−0.019 (5)0.013 (5)0.002 (5)
C40.118 (8)0.073 (6)0.044 (5)−0.004 (6)0.011 (5)0.012 (4)
C50.091 (7)0.061 (5)0.053 (5)0.003 (5)0.008 (4)−0.002 (4)
C60.085 (6)0.065 (5)0.049 (5)−0.020 (5)0.025 (4)−0.006 (4)
C70.078 (6)0.049 (4)0.036 (4)−0.014 (4)0.018 (4)−0.005 (3)
C80.098 (7)0.041 (4)0.044 (4)−0.008 (5)0.019 (4)0.003 (3)
C90.083 (7)0.056 (5)0.053 (5)0.004 (4)0.015 (5)0.002 (4)
N20.052 (4)0.043 (4)0.072 (4)0.003 (3)0.008 (3)0.006 (3)
C100.133 (11)0.102 (9)0.075 (7)0.034 (7)0.043 (7)0.014 (6)
C110.185 (15)0.066 (7)0.088 (8)0.033 (8)0.021 (9)−0.011 (6)
C120.099 (9)0.046 (6)0.160 (13)0.006 (5)−0.004 (8)0.011 (7)
C130.138 (12)0.088 (8)0.148 (12)0.012 (8)0.073 (10)0.049 (8)
C140.124 (9)0.058 (6)0.109 (8)0.010 (6)0.057 (7)−0.001 (6)
C150.068 (6)0.060 (6)0.150 (10)0.003 (5)0.022 (6)0.031 (6)
C160.063 (6)0.038 (4)0.098 (7)−0.013 (4)0.010 (5)0.018 (4)
C170.092 (8)0.056 (6)0.084 (7)−0.008 (5)0.006 (6)0.008 (5)
C180.087 (7)0.051 (5)0.088 (7)0.006 (5)0.025 (6)0.007 (5)
Geometric parameters (Å, °) top
Hg1—Cl12.371 (13)C8—H80.93
Hg1—Cl22.347 (13)C9—C8i1.386 (13)
Hg1—Cl32.530 (2)C9—H90.93
Hg1—Cl42.593 (2)N2—C101.39
Hg1—I12.742 (3)N2—C141.39
Hg1—I22.755 (2)N2—C151.452 (10)
N1—C11.39C10—C111.39
N1—C51.39C10—H100.93
N1—C61.447 (8)C11—C121.39
C1—C21.39C11—H110.93
C1—H10.93C12—C131.39
C2—C31.39C12—H120.93
C2—H20.93C13—C141.39
C3—C41.39C13—H130.93
C3—H30.93C14—H140.93
C4—C51.39C15—C161.508 (13)
C4—H40.93C15—H15A0.97
C5—H50.93C15—H15B0.97
C6—C71.527 (12)C16—C181.361 (15)
C6—H6A0.97C16—C171.375 (14)
C6—H6B0.97C17—C18ii1.369 (14)
C7—C81.371 (12)C17—H170.93
C7—C91.393 (10)C18—C17ii1.369 (14)
C8—C9i1.386 (13)C18—H180.93
Cl2—Hg1—Cl1114.2 (9)C9—C7—C6119.2 (8)
Cl2—Hg1—Cl3112.9 (7)C7—C8—C9i121.0 (8)
Cl1—Hg1—Cl3110.8 (7)C7—C8—H8119.5
Cl2—Hg1—Cl4110.7 (7)C9i—C8—H8119.5
Cl1—Hg1—Cl4109.8 (6)C8i—C9—C7119.1 (8)
Cl3—Hg1—Cl497.16 (7)C8i—C9—H9120.5
Cl2—Hg1—I1112.4 (7)C7—C9—H9120.5
Cl1—Hg1—I12.9 (6)C10—N2—C14120.0
Cl3—Hg1—I1110.05 (11)C10—N2—C15119.9 (6)
Cl4—Hg1—I1112.76 (10)C14—N2—C15120.0 (6)
Cl2—Hg1—I22.0 (8)N2—C10—C11120.0
Cl1—Hg1—I2116.2 (6)N2—C10—H10120.0
Cl3—Hg1—I2111.32 (9)C11—C10—H10120.0
Cl4—Hg1—I2109.89 (9)C12—C11—C10120.0
I1—Hg1—I2114.39 (12)C12—C11—H11120.0
C1—N1—C5120.0C10—C11—H11120.0
C1—N1—C6119.7 (5)C11—C12—C13120.0
C5—N1—C6120.2 (5)C11—C12—H12120.0
C2—C1—N1120.0C13—C12—H12120.0
C2—C1—H1120.0C14—C13—C12120.0
N1—C1—H1120.0C14—C13—H13120.0
C1—C2—C3120.0C12—C13—H13120.0
C1—C2—H2120.0C13—C14—N2120.0
C3—C2—H2120.0C13—C14—H14120.0
C4—C3—C2120.0N2—C14—H14120.0
C4—C3—H3120.0N2—C15—C16111.8 (7)
C2—C3—H3120.0N2—C15—H15A109.3
C5—C4—C3120.0C16—C15—H15A109.3
C5—C4—H4120.0N2—C15—H15B109.3
C3—C4—H4120.0C16—C15—H15B109.3
C4—C5—N1120.0H15A—C15—H15B107.9
C4—C5—H5120.0C18—C16—C17118.9 (9)
N1—C5—H5120.0C18—C16—C15120.8 (10)
N1—C6—C7111.4 (7)C17—C16—C15120.4 (10)
N1—C6—H6A109.4C18ii—C17—C16120.0 (10)
C7—C6—H6A109.4C18ii—C17—H17120.0
N1—C6—H6B109.4C16—C17—H17120.0
C7—C6—H6B109.4C16—C18—C17ii121.1 (10)
H6A—C6—H6B108.0C16—C18—H18119.4
C8—C7—C9119.9 (8)C17ii—C18—H18119.4
C8—C7—C6120.9 (7)
C6—N1—C1—C2−177.4 (6)C15—N2—C10—C11−175.7 (7)
C6—N1—C5—C4177.4 (6)C15—N2—C14—C13175.6 (7)
C1—N1—C6—C796.1 (7)C10—N2—C15—C16−124.6 (8)
C5—N1—C6—C7−81.2 (8)C14—N2—C15—C1659.7 (12)
N1—C6—C7—C8−82.8 (9)N2—C15—C16—C1881.6 (12)
N1—C6—C7—C995.7 (9)N2—C15—C16—C17−100.2 (11)
C9—C7—C8—C9i−0.1 (13)C18—C16—C17—C18ii0.0 (15)
C6—C7—C8—C9i178.4 (7)C15—C16—C17—C18ii−178.3 (8)
C8—C7—C9—C8i0.1 (13)C17—C16—C18—C17ii0.0 (15)
C6—C7—C9—C8i−178.4 (7)C15—C16—C18—C17ii178.3 (8)
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+2, −y−1, −z+2.
Selected geometric parameters (Å) top
Hg1—Cl12.371 (13)Hg1—Cl42.593 (2)
Hg1—Cl22.347 (13)Hg1—I12.742 (3)
Hg1—Cl32.530 (2)Hg1—I22.755 (2)
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, Wisconsin, 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.

Sindelar, V., Moon, K. & Kaifer, A. E. (2004). Org. Lett. 6, 2665–2668.

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.