Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016094/bt6188sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016094/bt6188Isup2.hkl |
CCDC reference: 198298
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.
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.
(C8H20N)2[Hg4Cl10] | Z = 1 |
Mr = 1417.36 | F(000) = 640 |
Triclinic, P1 | Dx = 2.742 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3409 (15) Å | Cell parameters from 12624 reflections |
b = 10.5043 (18) Å | θ = 2.7–27.0° |
c = 11.039 (2) Å | µ = 18.62 mm−1 |
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 |
STOE Imaging Plate Diffraction System, IPDS-I diffractometer | 3750 independent reflections |
Radiation source: fine-focus sealed tube | 2408 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.084 |
ϕ scans | θmax = 27.0°, θmin = 2.7° |
Absorption correction: numerical (X-SHAPE; STOE & Cie, 1998) | h = −10→10 |
Tmin = 0.047, Tmax = 0.155 | k = −13→12 |
12624 measured reflections | l = −14→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-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 reflections | Δρmax = 1.36 e Å−3 |
147 parameters | Δρmin = −1.61 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0148 (5) |
(C8H20N)2[Hg4Cl10] | γ = 109.182 (14)° |
Mr = 1417.36 | V = 858.4 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.3409 (15) Å | Mo Kα radiation |
b = 10.5043 (18) Å | µ = 18.62 mm−1 |
c = 11.039 (2) Å | T = 293 K |
α = 105.537 (14)° | 0.2 × 0.15 × 0.1 mm |
β = 96.467 (15)° |
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 = 0.155 | Rint = 0.084 |
12624 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 0.82 | Δρmax = 1.36 e Å−3 |
3750 reflections | Δρmin = −1.61 e Å−3 |
147 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Hg1 | 0.74186 (5) | −0.00676 (4) | −0.01655 (4) | 0.04859 (16) | |
Hg2 | 1.03983 (6) | 0.05220 (5) | 0.34614 (4) | 0.05201 (16) | |
Cl1 | 0.9344 (3) | −0.1762 (3) | 0.3865 (2) | 0.0437 (5) | |
Cl2 | 0.9854 (3) | 0.1513 (3) | −0.0548 (2) | 0.0437 (5) | |
Cl3 | 1.3272 (3) | 0.1773 (3) | 0.3209 (3) | 0.0523 (6) | |
Cl4 | 0.4890 (3) | −0.1833 (3) | −0.0142 (3) | 0.0492 (6) | |
Cl5 | 0.8282 (3) | 0.1405 (3) | 0.2629 (2) | 0.0491 (6) | |
N1 | 0.2903 (8) | 0.6007 (7) | 0.2957 (6) | 0.0276 (14) | |
C1 | 0.1435 (11) | 0.4727 (10) | 0.2004 (9) | 0.042 (2) | |
H1B | 0.1755 | 0.4537 | 0.1175 | 0.050* | |
H1A | 0.1319 | 0.3907 | 0.2284 | 0.050* | |
C2 | 0.2540 (13) | 0.6324 (11) | 0.4296 (8) | 0.040 (2) | |
H2B | 0.1541 | 0.6603 | 0.4280 | 0.048* | |
H2A | 0.3530 | 0.7131 | 0.4878 | 0.048* | |
C3 | 0.3125 (12) | 0.7317 (10) | 0.2541 (9) | 0.041 (2) | |
H3B | 0.3205 | 0.7083 | 0.1644 | 0.049* | |
H3A | 0.2093 | 0.7544 | 0.2600 | 0.049* | |
C4 | 0.4552 (12) | 0.5683 (11) | 0.3000 (9) | 0.042 (2) | |
H4B | 0.4341 | 0.4817 | 0.3221 | 0.051* | |
H4A | 0.5465 | 0.6450 | 0.3685 | 0.051* | |
C5 | 0.4695 (15) | 0.8619 (11) | 0.3320 (12) | 0.060 (3) | |
H5C | 0.4737 | 0.9394 | 0.3003 | 0.072* | |
H5B | 0.5729 | 0.8419 | 0.3245 | 0.072* | |
H5A | 0.4619 | 0.8876 | 0.4208 | 0.072* | |
C6 | 0.2189 (15) | 0.5090 (13) | 0.4838 (11) | 0.060 (3) | |
H6C | 0.1973 | 0.5380 | 0.5685 | 0.072* | |
H6B | 0.3183 | 0.4821 | 0.4884 | 0.072* | |
H6A | 0.1190 | 0.4292 | 0.4285 | 0.072* | |
C7 | 0.5201 (15) | 0.5501 (14) | 0.1768 (11) | 0.059 (3) | |
H7C | 0.6241 | 0.5303 | 0.1884 | 0.071* | |
H7B | 0.5448 | 0.6361 | 0.1550 | 0.071* | |
H7A | 0.4325 | 0.4724 | 0.1086 | 0.071* | |
C8 | −0.0311 (12) | 0.4860 (12) | 0.1821 (10) | 0.051 (3) | |
H8C | −0.1153 | 0.3999 | 0.1202 | 0.061* | |
H8B | −0.0229 | 0.5649 | 0.1516 | 0.061* | |
H8A | −0.0666 | 0.5018 | 0.2628 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.0391 (2) | 0.0454 (3) | 0.0648 (3) | 0.01096 (18) | 0.01501 (19) | 0.0281 (2) |
Hg2 | 0.0553 (3) | 0.0534 (3) | 0.0475 (3) | 0.0140 (2) | 0.0129 (2) | 0.0239 (2) |
Cl1 | 0.0603 (14) | 0.0346 (12) | 0.0363 (11) | 0.0169 (11) | 0.0156 (10) | 0.0106 (10) |
Cl2 | 0.0443 (12) | 0.0390 (13) | 0.0431 (12) | 0.0079 (10) | 0.0151 (9) | 0.0135 (10) |
Cl3 | 0.0424 (13) | 0.0575 (17) | 0.0493 (14) | 0.0106 (12) | 0.0123 (10) | 0.0146 (12) |
Cl4 | 0.0430 (12) | 0.0440 (14) | 0.0619 (15) | 0.0096 (11) | 0.0172 (11) | 0.0253 (12) |
Cl5 | 0.0509 (13) | 0.0515 (15) | 0.0431 (12) | 0.0183 (11) | 0.0015 (10) | 0.0171 (11) |
N1 | 0.030 (3) | 0.025 (4) | 0.026 (3) | 0.011 (3) | 0.005 (3) | 0.006 (3) |
C1 | 0.038 (5) | 0.033 (5) | 0.044 (5) | 0.005 (4) | −0.002 (4) | 0.011 (4) |
C2 | 0.051 (5) | 0.049 (6) | 0.024 (4) | 0.022 (4) | 0.008 (4) | 0.012 (4) |
C3 | 0.047 (5) | 0.039 (5) | 0.047 (5) | 0.020 (4) | 0.012 (4) | 0.023 (4) |
C4 | 0.037 (5) | 0.048 (6) | 0.044 (5) | 0.021 (4) | 0.005 (4) | 0.012 (5) |
C5 | 0.061 (7) | 0.034 (6) | 0.077 (8) | 0.007 (5) | 0.011 (6) | 0.021 (6) |
C6 | 0.068 (7) | 0.073 (9) | 0.059 (7) | 0.029 (6) | 0.026 (6) | 0.045 (7) |
C7 | 0.054 (6) | 0.065 (8) | 0.060 (7) | 0.031 (6) | 0.024 (5) | 0.007 (6) |
C8 | 0.034 (5) | 0.053 (7) | 0.052 (6) | 0.004 (5) | −0.001 (4) | 0.018 (5) |
Hg1—Cl4 | 2.314 (2) | C3—C5 | 1.504 (14) |
Hg1—Cl2 | 2.327 (2) | C3—H3B | 0.9700 |
Hg1—Cl5 | 2.939 (3) | C3—H3A | 0.9700 |
Hg2—Cl3 | 2.414 (3) | C4—C7 | 1.508 (14) |
Hg2—Cl5 | 2.447 (3) | C4—H4B | 0.9700 |
Hg2—Cl1 | 2.450 (2) | C4—H4A | 0.9700 |
Hg2—Cl1i | 2.840 (2) | C5—H5C | 0.9600 |
Cl1—Hg2i | 2.840 (2) | C5—H5B | 0.9600 |
N1—C2 | 1.514 (10) | C5—H5A | 0.9600 |
N1—C4 | 1.521 (11) | C6—H6C | 0.9600 |
N1—C1 | 1.512 (11) | C6—H6B | 0.9600 |
N1—C3 | 1.526 (11) | C6—H6A | 0.9600 |
C1—C8 | 1.505 (14) | C7—H7C | 0.9600 |
C1—H1B | 0.9700 | C7—H7B | 0.9600 |
C1—H1A | 0.9700 | C7—H7A | 0.9600 |
C2—C6 | 1.526 (13) | C8—H8C | 0.9600 |
C2—H2B | 0.9700 | C8—H8B | 0.9600 |
C2—H2A | 0.9700 | C8—H8A | 0.9600 |
Cl4—Hg1—Cl2 | 170.64 (9) | N1—C3—H3A | 108.6 |
Cl4—Hg1—Cl5 | 94.59 (9) | H3B—C3—H3A | 107.6 |
Cl2—Hg1—Cl5 | 94.76 (8) | N1—C4—C7 | 115.2 (8) |
Cl3—Hg2—Cl5 | 111.24 (9) | N1—C4—H4B | 108.5 |
Cl3—Hg2—Cl1 | 127.49 (10) | C7—C4—H4B | 108.5 |
Cl5—Hg2—Cl1 | 119.03 (9) | N1—C4—H4A | 108.5 |
Cl3—Hg2—Cl1i | 102.17 (9) | C7—C4—H4A | 108.5 |
Cl5—Hg2—Cl1i | 98.23 (8) | H4B—C4—H4A | 107.5 |
Cl1—Hg2—Cl1i | 85.30 (8) | C3—C5—H5C | 109.5 |
Hg2—Cl1—Hg2i | 94.70 (8) | C3—C5—H5B | 109.5 |
Hg2—Cl5—Hg1 | 103.59 (10) | H5C—C5—H5B | 109.5 |
C2—N1—C4 | 108.7 (6) | C3—C5—H5A | 109.5 |
C2—N1—C1 | 111.5 (7) | H5C—C5—H5A | 109.5 |
C4—N1—C1 | 108.1 (7) | H5B—C5—H5A | 109.5 |
C2—N1—C3 | 107.9 (7) | C2—C6—H6C | 109.5 |
C4—N1—C3 | 110.8 (7) | C2—C6—H6B | 109.5 |
C1—N1—C3 | 109.7 (6) | H6C—C6—H6B | 109.5 |
C8—C1—N1 | 115.7 (8) | C2—C6—H6A | 109.5 |
C8—C1—H1B | 108.4 | H6C—C6—H6A | 109.5 |
N1—C1—H1B | 108.4 | H6B—C6—H6A | 109.5 |
C8—C1—H1A | 108.4 | C4—C7—H7C | 109.5 |
N1—C1—H1A | 108.4 | C4—C7—H7B | 109.5 |
H1B—C1—H1A | 107.4 | H7C—C7—H7B | 109.5 |
N1—C2—C6 | 114.9 (8) | C4—C7—H7A | 109.5 |
N1—C2—H2B | 108.5 | H7C—C7—H7A | 109.5 |
C6—C2—H2B | 108.5 | H7B—C7—H7A | 109.5 |
N1—C2—H2A | 108.5 | C1—C8—H8C | 109.5 |
C6—C2—H2A | 108.5 | C1—C8—H8B | 109.5 |
H2B—C2—H2A | 107.5 | H8C—C8—H8B | 109.5 |
C5—C3—N1 | 114.6 (8) | C1—C8—H8A | 109.5 |
C5—C3—H3B | 108.6 | H8C—C8—H8A | 109.5 |
N1—C3—H3B | 108.6 | H8B—C8—H8A | 109.5 |
C5—C3—H3A | 108.6 |
Symmetry code: (i) −x+2, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C8H20N)2[Hg4Cl10] |
Mr | 1417.36 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 858.4 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 18.62 |
Crystal size (mm) | 0.2 × 0.15 × 0.1 |
Data collection | |
Diffractometer | STOE Imaging Plate Diffraction System, IPDS-I diffractometer |
Absorption correction | Numerical (X-SHAPE; STOE & Cie, 1998) |
Tmin, Tmax | 0.047, 0.155 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12624, 3750, 2408 |
Rint | 0.084 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.080, 0.82 |
No. of reflections | 3750 |
No. of parameters | 147 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
Hg1—Cl4 | 2.314 (2) | N1—C4 | 1.521 (11) |
Hg1—Cl2 | 2.327 (2) | N1—C1 | 1.512 (11) |
Hg1—Cl5 | 2.939 (3) | N1—C3 | 1.526 (11) |
Hg2—Cl3 | 2.414 (3) | C1—C8 | 1.505 (14) |
Hg2—Cl5 | 2.447 (3) | C2—C6 | 1.526 (13) |
Hg2—Cl1 | 2.450 (2) | C3—C5 | 1.504 (14) |
Hg2—Cl1i | 2.840 (2) | C4—C7 | 1.508 (14) |
N1—C2 | 1.514 (10) | ||
Cl4—Hg1—Cl2 | 170.64 (9) | C2—N1—C1 | 111.5 (7) |
Cl4—Hg1—Cl5 | 94.59 (9) | C4—N1—C1 | 108.1 (7) |
Cl2—Hg1—Cl5 | 94.76 (8) | C2—N1—C3 | 107.9 (7) |
Cl3—Hg2—Cl5 | 111.24 (9) | C4—N1—C3 | 110.8 (7) |
Cl3—Hg2—Cl1i | 102.17 (9) | C1—N1—C3 | 109.7 (6) |
Cl5—Hg2—Cl1i | 98.23 (8) | C8—C1—N1 | 115.7 (8) |
Cl1—Hg2—Cl1i | 85.30 (8) | N1—C2—C6 | 114.9 (8) |
Hg2—Cl1—Hg2i | 94.70 (8) | C5—C3—N1 | 114.6 (8) |
Hg2—Cl5—Hg1 | 103.59 (10) | N1—C4—C7 | 115.2 (8) |
C2—N1—C4 | 108.7 (6) |
Symmetry code: (i) −x+2, −y, −z+1. |
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.