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The crystal structure of (Me3PhN)[HgCl3] contains [(CH3)3(C6H5)N]+ cations and chains of distorted vertex-sharing [HgCl4]2- tetrahedra running parallel to [100]. The tetrahedra around mercury(II) are distorted, exhibiting a [2+2] coordination. Apart from one of the Cl atoms, which is located on a twofold rotation axis, and a pair of symmetry-related methyl C atoms, which are located in general positions, all non H-atoms lie on mirror planes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015325/bt6181sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015325/bt6181Isup2.hkl
Contains datablock I

CCDC reference: 198295

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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


Red Alert 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

Comment top

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.

Experimental top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Packing diagram viewed down the a axis.
[Figure 2] Fig. 2. Cutout of vertex sharing chains of [HgCl4]2− tetrahedra. Displacement ellipsoids are at the 50% probability level.
[Figure 3] Fig. 3. The [Me3PhN]+ cation. Displacement ellipsoids are at the 50% probability level.
(I) top
Crystal data top
(C9H14N)[HgCl3]F(000) = 824
Mr = 443.15Dx = 2.180 Mg m3
Orthorhombic, Ama2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: Am-2aCell parameters from 7398 reflections
a = 7.4699 (19) Åθ = 2.2–32.3°
b = 14.379 (2) ŵ = 11.96 mm1
c = 12.5687 (10) ÅT = 293 K
V = 1350.0 (4) Å3Prism, colourless
Z = 40.4 × 0.3 × 0.2 mm
Data collection top
Stoe Imaging Plate Diffraction System (IPDS-I)
diffractometer
1426 independent reflections
Radiation source: fine-focus sealed tube1249 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.086
ϕ scansθmax = 26.0°, θmin = 2.2°
Absorption correction: numerical
X-SHAPE (Stoe & Cie, 1998)
h = 97
Tmin = 0.034, Tmax = 0.585k = 1717
7398 measured reflectionsl = 1515
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-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 = 1.00Δρmax = 0.98 e Å3
1426 reflectionsΔρmin = 1.08 e Å3
82 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.00312 (19)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 0000 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.015 (12)
Crystal data top
(C9H14N)[HgCl3]V = 1350.0 (4) Å3
Mr = 443.15Z = 4
Orthorhombic, Ama2Mo Kα radiation
a = 7.4699 (19) ŵ = 11.96 mm1
b = 14.379 (2) ÅT = 293 K
c = 12.5687 (10) Å0.4 × 0.3 × 0.2 mm
Data collection top
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 = 0.585Rint = 0.086
7398 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.058Δρmax = 0.98 e Å3
S = 1.00Δρmin = 1.08 e Å3
1426 reflectionsAbsolute structure: Flack (1983), 0000 Friedel pairs
82 parametersAbsolute structure parameter: 0.015 (12)
1 restraint
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
Hg10.75000.05238 (2)0.47189 (2)0.05358 (15)
Cl10.75000.21826 (13)0.4742 (6)0.0685 (6)
Cl20.75000.06360 (17)0.33530 (19)0.0571 (6)
Cl30.50000.00000.60303 (16)0.0479 (5)
N10.75000.1914 (5)0.1247 (6)0.0459 (17)
C10.75000.1323 (7)0.0296 (10)0.045 (3)
C20.75000.1696 (12)0.0714 (10)0.067 (4)
H2A0.75000.23360.08150.080*
C30.75000.1084 (12)0.1595 (9)0.083 (4)
H3A0.75000.13250.22810.100*
C40.75000.0158 (12)0.1453 (12)0.082 (5)
H4A0.75000.02380.20380.099*
C50.75000.0190 (10)0.0470 (14)0.078 (5)
H5A0.75000.08330.03820.094*
C60.75000.0365 (7)0.0417 (10)0.059 (3)
H6A0.75000.01020.10920.071*
C70.75000.2939 (7)0.0983 (12)0.078 (4)
H7A0.75000.33050.16310.094*
H7B0.86550.30020.06110.094*
C80.5869 (10)0.1715 (6)0.1917 (6)0.0633 (19)
H8C0.59330.20680.25640.076*
H8B0.58250.10640.20820.076*
H8A0.48120.18880.15300.076*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.0694 (2)0.03912 (17)0.05226 (18)0.0000.0000.0048 (4)
Cl10.0960 (16)0.0336 (9)0.0757 (12)0.0000.0000.002 (3)
Cl20.0735 (16)0.0493 (13)0.0485 (11)0.0000.0000.0115 (10)
Cl30.0415 (11)0.0583 (14)0.0439 (10)0.0018 (11)0.0000.000
N10.055 (5)0.036 (4)0.047 (4)0.0000.0000.002 (3)
C10.050 (6)0.041 (6)0.044 (6)0.0000.0000.004 (5)
C20.075 (9)0.076 (10)0.049 (6)0.0000.0000.011 (6)
C30.093 (10)0.117 (12)0.039 (5)0.0000.0000.003 (7)
C40.104 (11)0.073 (9)0.070 (9)0.0000.0000.025 (8)
C50.101 (9)0.055 (5)0.078 (15)0.0000.0000.016 (7)
C60.083 (8)0.039 (6)0.056 (7)0.0000.0000.004 (5)
C70.108 (10)0.030 (5)0.096 (8)0.0000.0000.000 (5)
C80.053 (4)0.078 (5)0.058 (4)0.003 (4)0.005 (3)0.006 (4)
Geometric parameters (Å, º) top
Hg1—Cl12.385 (2)C3—C41.34 (2)
Hg1—Cl22.393 (2)C3—H3A0.9300
Hg1—Cl3i2.6022 (14)C4—C51.33 (2)
Hg1—Cl32.6022 (14)C4—H4A0.9300
Cl3—Hg1ii2.6022 (14)C5—C61.37 (2)
N1—C11.466 (14)C5—H5A0.9300
N1—C71.510 (13)C6—H6A0.9300
N1—C8i1.508 (9)C7—H7A0.970 (14)
N1—C81.508 (9)C7—H7B0.986 (7)
C1—C21.379 (13)C8—H8C0.9600
C1—C61.385 (14)C8—H8B0.9600
C2—C31.41 (2)C8—H8A0.9600
C2—H2A0.9300
Cl1—Hg1—Cl2134.88 (18)C4—C3—H3A119.6
Cl1—Hg1—Cl3i106.36 (11)C2—C3—H3A119.6
Cl2—Hg1—Cl3i104.64 (5)C3—C4—C5119.7 (14)
Cl1—Hg1—Cl3106.36 (11)C3—C4—H4A120.1
Cl2—Hg1—Cl3104.64 (5)C5—C4—H4A120.1
Cl3i—Hg1—Cl391.72 (6)C4—C5—C6122.3 (15)
Hg1ii—Cl3—Hg1101.40 (7)C4—C5—H5A118.9
C1—N1—C7112.8 (9)C6—C5—H5A118.9
C1—N1—C8i110.2 (5)C5—C6—C1119.4 (12)
C7—N1—C8i107.9 (6)C5—C6—H6A120.3
C1—N1—C8110.2 (5)C1—C6—H6A120.3
C7—N1—C8107.9 (6)N1—C7—H7A110.3 (12)
C8i—N1—C8107.8 (7)N1—C7—H7B101.2 (7)
C2—C1—C6119.1 (11)H7A—C7—H7B110.4 (7)
C2—C1—N1121.7 (9)N1—C8—H8C109.5
C6—C1—N1119.2 (10)N1—C8—H8B109.5
C1—C2—C3118.6 (14)H8C—C8—H8B109.5
C1—C2—H2A120.7N1—C8—H8A109.5
C3—C2—H2A120.7H8C—C8—H8A109.5
C4—C3—C2120.9 (13)H8B—C8—H8A109.5
Symmetry codes: (i) x+3/2, y, z; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula(C9H14N)[HgCl3]
Mr443.15
Crystal system, space groupOrthorhombic, Ama2
Temperature (K)293
a, b, c (Å)7.4699 (19), 14.379 (2), 12.5687 (10)
V3)1350.0 (4)
Z4
Radiation typeMo Kα
µ (mm1)11.96
Crystal size (mm)0.4 × 0.3 × 0.2
Data collection
DiffractometerStoe Imaging Plate Diffraction System (IPDS-I)
diffractometer
Absorption correctionNumerical
X-SHAPE (Stoe & Cie, 1998)
Tmin, Tmax0.034, 0.585
No. of measured, independent and
observed [I > 2σ(I)] reflections
7398, 1426, 1249
Rint0.086
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.058, 1.00
No. of reflections1426
No. of parameters82
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.98, 1.08
Absolute structureFlack (1983), 0000 Friedel pairs
Absolute structure parameter0.015 (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.

Selected geometric parameters (Å, º) top
Hg1—Cl12.385 (2)C1—C21.379 (13)
Hg1—Cl22.393 (2)C1—C61.385 (14)
Hg1—Cl32.6022 (14)C2—C31.41 (2)
N1—C11.466 (14)C3—C41.34 (2)
N1—C71.510 (13)C4—C51.33 (2)
N1—C81.508 (9)C5—C61.37 (2)
Cl1—Hg1—Cl2134.88 (18)C8i—N1—C8107.8 (7)
Cl1—Hg1—Cl3i106.36 (11)C2—C1—C6119.1 (11)
Cl2—Hg1—Cl3i104.64 (5)C2—C1—N1121.7 (9)
Cl1—Hg1—Cl3106.36 (11)C6—C1—N1119.2 (10)
Cl2—Hg1—Cl3104.64 (5)C1—C2—C3118.6 (14)
Hg1ii—Cl3—Hg1101.40 (7)C4—C3—C2120.9 (13)
C1—N1—C7112.8 (9)C3—C4—C5119.7 (14)
C1—N1—C8110.2 (5)C4—C5—C6122.3 (15)
C7—N1—C8107.9 (6)C5—C6—C1119.4 (12)
Symmetry codes: (i) x+3/2, y, z; (ii) x+1, y, z.
 

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