Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015325/bt6181sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015325/bt6181Isup2.hkl |
CCDC reference: 198295
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.019 Å
- R factor = 0.023
- wR factor = 0.058
- Data-to-parameter ratio = 17.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
DIFF_019 Alert A _diffrn_standards_number is missing Number of standards used in measurement. DIFF_020 Alert A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards. DIFF_022 Alert A _diffrn_standards_decay_% is missing Percentage decrease in standards intensity. General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.99 From the CIF: _reflns_number_total 1426 Count of symmetry unique reflns 746 Completeness (_total/calc) 191.15% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 680 Fraction of Friedel pairs measured 0.912 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
3 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check
A solution of 1 mmol (0.1717 g) trimethylphenylammonium chloride, [(CH3)3(C6H5)N]Cl, and 1 mmol (0.2715 g) HgCl2 in a mixture of 20 ml water and 30 ml me thanol was stirred at 333 K for 3 h. Colourless 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 (Stoe & Cie, 2000); data reduction: X-RED (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, Bonn, 1999); software used to prepare material for publication: SHELXL97.
(C9H14N)[HgCl3] | F(000) = 824 |
Mr = 443.15 | Dx = 2.180 Mg m−3 |
Orthorhombic, Ama2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: Am-2a | Cell parameters from 7398 reflections |
a = 7.4699 (19) Å | θ = 2.2–32.3° |
b = 14.379 (2) Å | µ = 11.96 mm−1 |
c = 12.5687 (10) Å | T = 293 K |
V = 1350.0 (4) Å3 | Prism, colourless |
Z = 4 | 0.4 × 0.3 × 0.2 mm |
Stoe Imaging Plate Diffraction System (IPDS-I) diffractometer | 1426 independent reflections |
Radiation source: fine-focus sealed tube | 1249 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.086 |
ϕ scans | θmax = 26.0°, θmin = 2.2° |
Absorption correction: numerical X-SHAPE (Stoe & Cie, 1998) | h = −9→7 |
Tmin = 0.034, Tmax = 0.585 | k = −17→17 |
7398 measured reflections | l = −15→15 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.023 | w = 1/[σ2(Fo2) + (0.0241P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.058 | (Δ/σ)max = 0.003 |
S = 1.00 | Δρmax = 0.98 e Å−3 |
1426 reflections | Δρmin = −1.08 e Å−3 |
82 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.00312 (19) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 0000 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.015 (12) |
(C9H14N)[HgCl3] | V = 1350.0 (4) Å3 |
Mr = 443.15 | Z = 4 |
Orthorhombic, Ama2 | Mo Kα radiation |
a = 7.4699 (19) Å | µ = 11.96 mm−1 |
b = 14.379 (2) Å | T = 293 K |
c = 12.5687 (10) Å | 0.4 × 0.3 × 0.2 mm |
Stoe Imaging Plate Diffraction System (IPDS-I) diffractometer | 1426 independent reflections |
Absorption correction: numerical X-SHAPE (Stoe & Cie, 1998) | 1249 reflections with I > 2σ(I) |
Tmin = 0.034, Tmax = 0.585 | Rint = 0.086 |
7398 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | H-atom parameters constrained |
wR(F2) = 0.058 | Δρmax = 0.98 e Å−3 |
S = 1.00 | Δρmin = −1.08 e Å−3 |
1426 reflections | Absolute structure: Flack (1983), 0000 Friedel pairs |
82 parameters | Absolute structure parameter: −0.015 (12) |
1 restraint |
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 | 0.7500 | 0.05238 (2) | 0.47189 (2) | 0.05358 (15) | |
Cl1 | 0.7500 | 0.21826 (13) | 0.4742 (6) | 0.0685 (6) | |
Cl2 | 0.7500 | −0.06360 (17) | 0.33530 (19) | 0.0571 (6) | |
Cl3 | 0.5000 | 0.0000 | 0.60303 (16) | 0.0479 (5) | |
N1 | 0.7500 | 0.1914 (5) | 0.1247 (6) | 0.0459 (17) | |
C1 | 0.7500 | 0.1323 (7) | 0.0296 (10) | 0.045 (3) | |
C2 | 0.7500 | 0.1696 (12) | −0.0714 (10) | 0.067 (4) | |
H2A | 0.7500 | 0.2336 | −0.0815 | 0.080* | |
C3 | 0.7500 | 0.1084 (12) | −0.1595 (9) | 0.083 (4) | |
H3A | 0.7500 | 0.1325 | −0.2281 | 0.100* | |
C4 | 0.7500 | 0.0158 (12) | −0.1453 (12) | 0.082 (5) | |
H4A | 0.7500 | −0.0238 | −0.2038 | 0.099* | |
C5 | 0.7500 | −0.0190 (10) | −0.0470 (14) | 0.078 (5) | |
H5A | 0.7500 | −0.0833 | −0.0382 | 0.094* | |
C6 | 0.7500 | 0.0365 (7) | 0.0417 (10) | 0.059 (3) | |
H6A | 0.7500 | 0.0102 | 0.1092 | 0.071* | |
C7 | 0.7500 | 0.2939 (7) | 0.0983 (12) | 0.078 (4) | |
H7A | 0.7500 | 0.3305 | 0.1631 | 0.094* | |
H7B | 0.8655 | 0.3002 | 0.0611 | 0.094* | |
C8 | 0.5869 (10) | 0.1715 (6) | 0.1917 (6) | 0.0633 (19) | |
H8C | 0.5933 | 0.2068 | 0.2564 | 0.076* | |
H8B | 0.5825 | 0.1064 | 0.2082 | 0.076* | |
H8A | 0.4812 | 0.1888 | 0.1530 | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.0694 (2) | 0.03912 (17) | 0.05226 (18) | 0.000 | 0.000 | −0.0048 (4) |
Cl1 | 0.0960 (16) | 0.0336 (9) | 0.0757 (12) | 0.000 | 0.000 | −0.002 (3) |
Cl2 | 0.0735 (16) | 0.0493 (13) | 0.0485 (11) | 0.000 | 0.000 | −0.0115 (10) |
Cl3 | 0.0415 (11) | 0.0583 (14) | 0.0439 (10) | 0.0018 (11) | 0.000 | 0.000 |
N1 | 0.055 (5) | 0.036 (4) | 0.047 (4) | 0.000 | 0.000 | 0.002 (3) |
C1 | 0.050 (6) | 0.041 (6) | 0.044 (6) | 0.000 | 0.000 | 0.004 (5) |
C2 | 0.075 (9) | 0.076 (10) | 0.049 (6) | 0.000 | 0.000 | 0.011 (6) |
C3 | 0.093 (10) | 0.117 (12) | 0.039 (5) | 0.000 | 0.000 | −0.003 (7) |
C4 | 0.104 (11) | 0.073 (9) | 0.070 (9) | 0.000 | 0.000 | −0.025 (8) |
C5 | 0.101 (9) | 0.055 (5) | 0.078 (15) | 0.000 | 0.000 | −0.016 (7) |
C6 | 0.083 (8) | 0.039 (6) | 0.056 (7) | 0.000 | 0.000 | 0.004 (5) |
C7 | 0.108 (10) | 0.030 (5) | 0.096 (8) | 0.000 | 0.000 | 0.000 (5) |
C8 | 0.053 (4) | 0.078 (5) | 0.058 (4) | 0.003 (4) | 0.005 (3) | −0.006 (4) |
Hg1—Cl1 | 2.385 (2) | C3—C4 | 1.34 (2) |
Hg1—Cl2 | 2.393 (2) | C3—H3A | 0.9300 |
Hg1—Cl3i | 2.6022 (14) | C4—C5 | 1.33 (2) |
Hg1—Cl3 | 2.6022 (14) | C4—H4A | 0.9300 |
Cl3—Hg1ii | 2.6022 (14) | C5—C6 | 1.37 (2) |
N1—C1 | 1.466 (14) | C5—H5A | 0.9300 |
N1—C7 | 1.510 (13) | C6—H6A | 0.9300 |
N1—C8i | 1.508 (9) | C7—H7A | 0.970 (14) |
N1—C8 | 1.508 (9) | C7—H7B | 0.986 (7) |
C1—C2 | 1.379 (13) | C8—H8C | 0.9600 |
C1—C6 | 1.385 (14) | C8—H8B | 0.9600 |
C2—C3 | 1.41 (2) | C8—H8A | 0.9600 |
C2—H2A | 0.9300 | ||
Cl1—Hg1—Cl2 | 134.88 (18) | C4—C3—H3A | 119.6 |
Cl1—Hg1—Cl3i | 106.36 (11) | C2—C3—H3A | 119.6 |
Cl2—Hg1—Cl3i | 104.64 (5) | C3—C4—C5 | 119.7 (14) |
Cl1—Hg1—Cl3 | 106.36 (11) | C3—C4—H4A | 120.1 |
Cl2—Hg1—Cl3 | 104.64 (5) | C5—C4—H4A | 120.1 |
Cl3i—Hg1—Cl3 | 91.72 (6) | C4—C5—C6 | 122.3 (15) |
Hg1ii—Cl3—Hg1 | 101.40 (7) | C4—C5—H5A | 118.9 |
C1—N1—C7 | 112.8 (9) | C6—C5—H5A | 118.9 |
C1—N1—C8i | 110.2 (5) | C5—C6—C1 | 119.4 (12) |
C7—N1—C8i | 107.9 (6) | C5—C6—H6A | 120.3 |
C1—N1—C8 | 110.2 (5) | C1—C6—H6A | 120.3 |
C7—N1—C8 | 107.9 (6) | N1—C7—H7A | 110.3 (12) |
C8i—N1—C8 | 107.8 (7) | N1—C7—H7B | 101.2 (7) |
C2—C1—C6 | 119.1 (11) | H7A—C7—H7B | 110.4 (7) |
C2—C1—N1 | 121.7 (9) | N1—C8—H8C | 109.5 |
C6—C1—N1 | 119.2 (10) | N1—C8—H8B | 109.5 |
C1—C2—C3 | 118.6 (14) | H8C—C8—H8B | 109.5 |
C1—C2—H2A | 120.7 | N1—C8—H8A | 109.5 |
C3—C2—H2A | 120.7 | H8C—C8—H8A | 109.5 |
C4—C3—C2 | 120.9 (13) | H8B—C8—H8A | 109.5 |
Symmetry codes: (i) −x+3/2, y, z; (ii) −x+1, −y, z. |
Experimental details
Crystal data | |
Chemical formula | (C9H14N)[HgCl3] |
Mr | 443.15 |
Crystal system, space group | Orthorhombic, Ama2 |
Temperature (K) | 293 |
a, b, c (Å) | 7.4699 (19), 14.379 (2), 12.5687 (10) |
V (Å3) | 1350.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 11.96 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Stoe Imaging Plate Diffraction System (IPDS-I) diffractometer |
Absorption correction | Numerical X-SHAPE (Stoe & Cie, 1998) |
Tmin, Tmax | 0.034, 0.585 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7398, 1426, 1249 |
Rint | 0.086 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.058, 1.00 |
No. of reflections | 1426 |
No. of parameters | 82 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.98, −1.08 |
Absolute structure | Flack (1983), 0000 Friedel pairs |
Absolute structure parameter | −0.015 (12) |
Computer programs: X-AREA (Stoe & Cie, 2001), X-STEP32 (Stoe & Cie, 2000), X-RED (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, Bonn, 1999), SHELXL97.
Hg1—Cl1 | 2.385 (2) | C1—C2 | 1.379 (13) |
Hg1—Cl2 | 2.393 (2) | C1—C6 | 1.385 (14) |
Hg1—Cl3 | 2.6022 (14) | C2—C3 | 1.41 (2) |
N1—C1 | 1.466 (14) | C3—C4 | 1.34 (2) |
N1—C7 | 1.510 (13) | C4—C5 | 1.33 (2) |
N1—C8 | 1.508 (9) | C5—C6 | 1.37 (2) |
Cl1—Hg1—Cl2 | 134.88 (18) | C8i—N1—C8 | 107.8 (7) |
Cl1—Hg1—Cl3i | 106.36 (11) | C2—C1—C6 | 119.1 (11) |
Cl2—Hg1—Cl3i | 104.64 (5) | C2—C1—N1 | 121.7 (9) |
Cl1—Hg1—Cl3 | 106.36 (11) | C6—C1—N1 | 119.2 (10) |
Cl2—Hg1—Cl3 | 104.64 (5) | C1—C2—C3 | 118.6 (14) |
Hg1ii—Cl3—Hg1 | 101.40 (7) | C4—C3—C2 | 120.9 (13) |
C1—N1—C7 | 112.8 (9) | C3—C4—C5 | 119.7 (14) |
C1—N1—C8 | 110.2 (5) | C4—C5—C6 | 122.3 (15) |
C7—N1—C8 | 107.9 (6) | C5—C6—C1 | 119.4 (12) |
Symmetry codes: (i) −x+3/2, y, z; (ii) −x+1, −y, z. |
Coordination polyhedra of chloromercurate(II) anions exhibit a surprisingly wide variety. No less than 252 crystallographically distinct HgII species were listed in a recent overview (Serezhkin et al., 2001). The trichloromercurate(II) anion, [HgCl3]−, is only rarely found as an isolated anion. The same is true for the dimeric unit, [Hg2Cl6]2−, which occurs as two tetrahedra sharing one common edge. In most cases, however, [3 + 2]n and [2 + 4]n chains are observed depending upon size and charge of the counter-cation(s) (House et al., 1994).
The structure of (Me3PhN)[HgCl3], (I), consists essentially of [(CH3)3(C6H5)N]+ cations and chains of distorted vertex-sharing [HgCl4]2− tetrahedra. The HgIIion has a distorted tetrahedral coordination, with two chloride ligands with short Hg2+···Cl− bond lengths of 2.385 (2) and 2.393 (2) Å, and two bridging chloride ligands with considerably longer Hg2+···Cl− distances of 2.602 (1) Å. These tetrahedra build vertex-sharing chains parallel to [100]. The angle involving the bridging chloride ligands, Cl3—Hg—Cl3, and the angle involving the two other Cl ligands, Cl1—Hg—Cl2, show distinct deviations from the ideal tetrahedral geometry, with values of 91.72 (6) and 134.9 (2)°, respectively. The Hg atoms, the Cl1 and Cl2 ligands, and the plane of the phenyl ring lie on a mirror plane perpendicular to the a axis.