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The structure of (Et4N)2[Hg4Cl10] contains dinuclear [Hg2Cl6]2- anions and HgCl2 mol­ecules, with definite interactions so that the anion can also be formulated as [Hg4Cl10]2-. Alternatively the compound can be written as (Et4N)2[Hg2Cl6][HgCl2]2. Charge balance is achieved by ordered [Et4N]+ cations. An inversion centre is situated at the centre of the [Hg2Cl6]2- anions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016094/bt6188sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016094/bt6188Isup2.hkl
Contains datablock I

CCDC reference: 198298

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.016 Å
  • R factor = 0.037
  • wR factor = 0.080
  • Data-to-parameter ratio = 25.5

checkCIF results

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ADDSYM reports no extra symmetry








Comment top

Chloromercurate(II) anions show a wide variety of stereochemical arrangements, dependent on the charge and size of the counter cation and the stoichiometry (House et al., 1994; Serezhkin et al., 2001).

Three phases are reported for the system (Et4N)Cl / HgCl2. (Et4N)[HgCl3] exhibits a trigonal bipyramid around Hg(II) connected to infinite chains (Sandström & Liem, 1978). The structure of (Et4N)2[HgCl4] consists of isolated [HgCl4]2− tetrahedra (Mahoui et al., 1996). Finally, (Et4N)2[Hg3Cl8] forms [Hg3Cl8]2− units with distorted trigonal bipyramids surrounding Hg(II) (Pabst et al., 1994).

We have recently reported the structure of (Et4N)2Hg3Br8 with isolated bitetrahedral [Hg2Br6]2− units consisting of two tetrahedra sharing one common edge (Nockemann & Meyer, 2002). Additionally, the structure contains molecular digonal Br—Hg—Br units; there are no interactions between the anions and these linear units.

The crystal structure of (Et4N)2[Hg4Cl10] or (Et4N)2[Hg2Cl6][HgCl2]2, (I), also contains bitetrahedral [Hg2Cl6]2− units consisting of two tetrahedra sharing one common edge. Two additional HgCl2 units, with Cl—Hg—Cl angles around 170°, are found to interact with the [Hg2Cl6]2− units so that, in total, one could formulate the anion as [Hg4Cl10]2−. The bitetrahedral [Hg2Cl6]2− units exhibit two short bonds of 2.450 (2) Å and two long bonds of 2.840 (2) Å to the bridging chloride ions. The distorted tetrahedral coordination sphere of Hg2 is completed by two Hg—Cl bonds of 2.414 (3) and 2.447 (3) Å, respectively. The angle to the bridging chloride ions is 85.30 (8)°, while the other angle, Cl3—Hg2—Cl5, amounts to 111.24 (9)°. Such a [Hg2Cl6]2− anion is quite unusual because it can be derived from two interacting trigonal [HgCl3] units, while most other known [Hg2Cl6]2− units need to be considered as HgCl2 units bridged by Cl anions with long Hg···Cl contacts, e.g. as in (Bu4N)[HgCl3] (Goggin et al., 1982).

The HgCl2 units within the [Hg4Cl10]2− unit exhibit short covalent Hg—Cl bonds [2.314 (2) Å and 2.327 (2) Å] and interact with the [Hg2Cl6]2− units by long Hg—Cl contacts of 2.939 (3) Å, which are only slightly longer than the bridging Hg2—Cl1 contacts of 2.840 (2) Å. The angle Cl2—Hg1—Cl4 with 170.64 (9)° is one further evidence for this interaction: The coordination sphere of Hg2 is adjusted to T-shaped units. In (Et4N)2[Hg4Cl10] charge balance is achieved by ordered [Et4N]+ cations, which are located between the Hg4Cl102− layers.

Experimental top

1 mmol (0.1657 g) of tetraethylammonium chloride, (Et4)NCl, and 2 mmol (0.5430 g) of mercuric chloride HgCl2, were dissolved by stirring in 50 ml me thanol at 50°C until a clear solution was obtained. Single crystals were obtained when the solution was allowed to sit at room temperature for 2 d.

Computing details top

Data collection: X-AREA (STOE & Cie, 2001); cell refinement: X-STEP32 1.06f (STOE & Cie, 2000); data reduction: X-RED 1.22 (STOE & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. : Packing diagram of (Et4N)2[Hg4Cl10], viewed down the a axis.
[Figure 2] Fig. 2. : View on the [Hg4Cl10]2− anions, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 3] Fig. 3. : View on the [Et4N]+ cation, showing 50% probability displacement ellipsoids.
(I) top
Crystal data top
(C8H20N)2[Hg4Cl10]Z = 1
Mr = 1417.36F(000) = 640
Triclinic, P1Dx = 2.742 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.3409 (15) ÅCell parameters from 12624 reflections
b = 10.5043 (18) Åθ = 2.7–27.0°
c = 11.039 (2) ŵ = 18.62 mm1
α = 105.537 (14)°T = 293 K
β = 96.467 (15)°Prism, colourless
γ = 109.182 (14)°0.2 × 0.15 × 0.1 mm
V = 858.4 (3) Å3
Data collection top
STOE Imaging Plate Diffraction System, IPDS-I
diffractometer
3750 independent reflections
Radiation source: fine-focus sealed tube2408 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.084
ϕ scansθmax = 27.0°, θmin = 2.7°
Absorption correction: numerical
(X-SHAPE; STOE & Cie, 1998)
h = 1010
Tmin = 0.047, Tmax = 0.155k = 1312
12624 measured reflectionsl = 1414
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) = 0.080 w = 1/[σ2(Fo2) + (0.0358P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.82(Δ/σ)max < 0.001
3750 reflectionsΔρmax = 1.36 e Å3
147 parametersΔρmin = 1.61 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0148 (5)
Crystal data top
(C8H20N)2[Hg4Cl10]γ = 109.182 (14)°
Mr = 1417.36V = 858.4 (3) Å3
Triclinic, P1Z = 1
a = 8.3409 (15) ÅMo Kα radiation
b = 10.5043 (18) ŵ = 18.62 mm1
c = 11.039 (2) ÅT = 293 K
α = 105.537 (14)°0.2 × 0.15 × 0.1 mm
β = 96.467 (15)°
Data collection top
STOE Imaging Plate Diffraction System, IPDS-I
diffractometer
3750 independent reflections
Absorption correction: numerical
(X-SHAPE; STOE & Cie, 1998)
2408 reflections with I > 2σ(I)
Tmin = 0.047, Tmax = 0.155Rint = 0.084
12624 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.080H-atom parameters constrained
S = 0.82Δρmax = 1.36 e Å3
3750 reflectionsΔρmin = 1.61 e Å3
147 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
xyzUiso*/Ueq
Hg10.74186 (5)0.00676 (4)0.01655 (4)0.04859 (16)
Hg21.03983 (6)0.05220 (5)0.34614 (4)0.05201 (16)
Cl10.9344 (3)0.1762 (3)0.3865 (2)0.0437 (5)
Cl20.9854 (3)0.1513 (3)0.0548 (2)0.0437 (5)
Cl31.3272 (3)0.1773 (3)0.3209 (3)0.0523 (6)
Cl40.4890 (3)0.1833 (3)0.0142 (3)0.0492 (6)
Cl50.8282 (3)0.1405 (3)0.2629 (2)0.0491 (6)
N10.2903 (8)0.6007 (7)0.2957 (6)0.0276 (14)
C10.1435 (11)0.4727 (10)0.2004 (9)0.042 (2)
H1B0.17550.45370.11750.050*
H1A0.13190.39070.22840.050*
C20.2540 (13)0.6324 (11)0.4296 (8)0.040 (2)
H2B0.15410.66030.42800.048*
H2A0.35300.71310.48780.048*
C30.3125 (12)0.7317 (10)0.2541 (9)0.041 (2)
H3B0.32050.70830.16440.049*
H3A0.20930.75440.26000.049*
C40.4552 (12)0.5683 (11)0.3000 (9)0.042 (2)
H4B0.43410.48170.32210.051*
H4A0.54650.64500.36850.051*
C50.4695 (15)0.8619 (11)0.3320 (12)0.060 (3)
H5C0.47370.93940.30030.072*
H5B0.57290.84190.32450.072*
H5A0.46190.88760.42080.072*
C60.2189 (15)0.5090 (13)0.4838 (11)0.060 (3)
H6C0.19730.53800.56850.072*
H6B0.31830.48210.48840.072*
H6A0.11900.42920.42850.072*
C70.5201 (15)0.5501 (14)0.1768 (11)0.059 (3)
H7C0.62410.53030.18840.071*
H7B0.54480.63610.15500.071*
H7A0.43250.47240.10860.071*
C80.0311 (12)0.4860 (12)0.1821 (10)0.051 (3)
H8C0.11530.39990.12020.061*
H8B0.02290.56490.15160.061*
H8A0.06660.50180.26280.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.0391 (2)0.0454 (3)0.0648 (3)0.01096 (18)0.01501 (19)0.0281 (2)
Hg20.0553 (3)0.0534 (3)0.0475 (3)0.0140 (2)0.0129 (2)0.0239 (2)
Cl10.0603 (14)0.0346 (12)0.0363 (11)0.0169 (11)0.0156 (10)0.0106 (10)
Cl20.0443 (12)0.0390 (13)0.0431 (12)0.0079 (10)0.0151 (9)0.0135 (10)
Cl30.0424 (13)0.0575 (17)0.0493 (14)0.0106 (12)0.0123 (10)0.0146 (12)
Cl40.0430 (12)0.0440 (14)0.0619 (15)0.0096 (11)0.0172 (11)0.0253 (12)
Cl50.0509 (13)0.0515 (15)0.0431 (12)0.0183 (11)0.0015 (10)0.0171 (11)
N10.030 (3)0.025 (4)0.026 (3)0.011 (3)0.005 (3)0.006 (3)
C10.038 (5)0.033 (5)0.044 (5)0.005 (4)0.002 (4)0.011 (4)
C20.051 (5)0.049 (6)0.024 (4)0.022 (4)0.008 (4)0.012 (4)
C30.047 (5)0.039 (5)0.047 (5)0.020 (4)0.012 (4)0.023 (4)
C40.037 (5)0.048 (6)0.044 (5)0.021 (4)0.005 (4)0.012 (5)
C50.061 (7)0.034 (6)0.077 (8)0.007 (5)0.011 (6)0.021 (6)
C60.068 (7)0.073 (9)0.059 (7)0.029 (6)0.026 (6)0.045 (7)
C70.054 (6)0.065 (8)0.060 (7)0.031 (6)0.024 (5)0.007 (6)
C80.034 (5)0.053 (7)0.052 (6)0.004 (5)0.001 (4)0.018 (5)
Geometric parameters (Å, º) top
Hg1—Cl42.314 (2)C3—C51.504 (14)
Hg1—Cl22.327 (2)C3—H3B0.9700
Hg1—Cl52.939 (3)C3—H3A0.9700
Hg2—Cl32.414 (3)C4—C71.508 (14)
Hg2—Cl52.447 (3)C4—H4B0.9700
Hg2—Cl12.450 (2)C4—H4A0.9700
Hg2—Cl1i2.840 (2)C5—H5C0.9600
Cl1—Hg2i2.840 (2)C5—H5B0.9600
N1—C21.514 (10)C5—H5A0.9600
N1—C41.521 (11)C6—H6C0.9600
N1—C11.512 (11)C6—H6B0.9600
N1—C31.526 (11)C6—H6A0.9600
C1—C81.505 (14)C7—H7C0.9600
C1—H1B0.9700C7—H7B0.9600
C1—H1A0.9700C7—H7A0.9600
C2—C61.526 (13)C8—H8C0.9600
C2—H2B0.9700C8—H8B0.9600
C2—H2A0.9700C8—H8A0.9600
Cl4—Hg1—Cl2170.64 (9)N1—C3—H3A108.6
Cl4—Hg1—Cl594.59 (9)H3B—C3—H3A107.6
Cl2—Hg1—Cl594.76 (8)N1—C4—C7115.2 (8)
Cl3—Hg2—Cl5111.24 (9)N1—C4—H4B108.5
Cl3—Hg2—Cl1127.49 (10)C7—C4—H4B108.5
Cl5—Hg2—Cl1119.03 (9)N1—C4—H4A108.5
Cl3—Hg2—Cl1i102.17 (9)C7—C4—H4A108.5
Cl5—Hg2—Cl1i98.23 (8)H4B—C4—H4A107.5
Cl1—Hg2—Cl1i85.30 (8)C3—C5—H5C109.5
Hg2—Cl1—Hg2i94.70 (8)C3—C5—H5B109.5
Hg2—Cl5—Hg1103.59 (10)H5C—C5—H5B109.5
C2—N1—C4108.7 (6)C3—C5—H5A109.5
C2—N1—C1111.5 (7)H5C—C5—H5A109.5
C4—N1—C1108.1 (7)H5B—C5—H5A109.5
C2—N1—C3107.9 (7)C2—C6—H6C109.5
C4—N1—C3110.8 (7)C2—C6—H6B109.5
C1—N1—C3109.7 (6)H6C—C6—H6B109.5
C8—C1—N1115.7 (8)C2—C6—H6A109.5
C8—C1—H1B108.4H6C—C6—H6A109.5
N1—C1—H1B108.4H6B—C6—H6A109.5
C8—C1—H1A108.4C4—C7—H7C109.5
N1—C1—H1A108.4C4—C7—H7B109.5
H1B—C1—H1A107.4H7C—C7—H7B109.5
N1—C2—C6114.9 (8)C4—C7—H7A109.5
N1—C2—H2B108.5H7C—C7—H7A109.5
C6—C2—H2B108.5H7B—C7—H7A109.5
N1—C2—H2A108.5C1—C8—H8C109.5
C6—C2—H2A108.5C1—C8—H8B109.5
H2B—C2—H2A107.5H8C—C8—H8B109.5
C5—C3—N1114.6 (8)C1—C8—H8A109.5
C5—C3—H3B108.6H8C—C8—H8A109.5
N1—C3—H3B108.6H8B—C8—H8A109.5
C5—C3—H3A108.6
Symmetry code: (i) x+2, y, z+1.

Experimental details

Crystal data
Chemical formula(C8H20N)2[Hg4Cl10]
Mr1417.36
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)8.3409 (15), 10.5043 (18), 11.039 (2)
α, β, γ (°)105.537 (14), 96.467 (15), 109.182 (14)
V3)858.4 (3)
Z1
Radiation typeMo Kα
µ (mm1)18.62
Crystal size (mm)0.2 × 0.15 × 0.1
Data collection
DiffractometerSTOE Imaging Plate Diffraction System, IPDS-I
diffractometer
Absorption correctionNumerical
(X-SHAPE; STOE & Cie, 1998)
Tmin, Tmax0.047, 0.155
No. of measured, independent and
observed [I > 2σ(I)] reflections
12624, 3750, 2408
Rint0.084
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.080, 0.82
No. of reflections3750
No. of parameters147
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.36, 1.61

Computer programs: X-AREA (STOE & Cie, 2001), X-STEP32 1.06f (STOE & Cie, 2000), X-RED 1.22 (STOE & Cie, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), SHELXL97.

Selected geometric parameters (Å, º) top
Hg1—Cl42.314 (2)N1—C41.521 (11)
Hg1—Cl22.327 (2)N1—C11.512 (11)
Hg1—Cl52.939 (3)N1—C31.526 (11)
Hg2—Cl32.414 (3)C1—C81.505 (14)
Hg2—Cl52.447 (3)C2—C61.526 (13)
Hg2—Cl12.450 (2)C3—C51.504 (14)
Hg2—Cl1i2.840 (2)C4—C71.508 (14)
N1—C21.514 (10)
Cl4—Hg1—Cl2170.64 (9)C2—N1—C1111.5 (7)
Cl4—Hg1—Cl594.59 (9)C4—N1—C1108.1 (7)
Cl2—Hg1—Cl594.76 (8)C2—N1—C3107.9 (7)
Cl3—Hg2—Cl5111.24 (9)C4—N1—C3110.8 (7)
Cl3—Hg2—Cl1i102.17 (9)C1—N1—C3109.7 (6)
Cl5—Hg2—Cl1i98.23 (8)C8—C1—N1115.7 (8)
Cl1—Hg2—Cl1i85.30 (8)N1—C2—C6114.9 (8)
Hg2—Cl1—Hg2i94.70 (8)C5—C3—N1114.6 (8)
Hg2—Cl5—Hg1103.59 (10)N1—C4—C7115.2 (8)
C2—N1—C4108.7 (6)
Symmetry code: (i) x+2, y, z+1.
 

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