Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015048/na1445sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015048/na1445Isup2.hkl |
CCDC reference: 142738
[2-(Pyridin-2-yl)phenyl]mercury acetate (21.6 mg, 0.052 mmol) and dicyclohexyldithiophosphinic acid (13.7 mg, 0.052 mmol) were dissolved in chloroform at 273 K. Slow evaporation in the refrigerator gave colourless crystals suitable for X-ray analysis.
Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: Please specify; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: Please specify.
[Hg(C11H8N)(C12H22PS2)] | F(000) = 1208 |
Mr = 616.16 | Dx = 1.758 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 14.923 (2) Å | Cell parameters from 25 reflections |
b = 9.9557 (10) Å | θ = 8–15° |
c = 15.728 (2) Å | µ = 6.87 mm−1 |
β = 95.088 (10)° | T = 293 K |
V = 2327.5 (5) Å3 | Block, colourless |
Z = 4 | 0.25 × 0.25 × 0.15 mm |
Enraf Nonius CAD4 diffractometer | 2272 reflections with I > 2σ(I) |
Radiation source: Enraf Nonius FR590 | Rint = 0.060 |
Graphite monochromator | θmax = 25.0°, θmin = 1.8° |
non–profiled ω/2θ scans | h = −17→17 |
Absorption correction: analytical (Alcock, 1970) | k = 0→11 |
Tmin = 0.428, Tmax = 0.709 | l = 0→18 |
4252 measured reflections | 1 standard reflections every 30 min |
4094 independent reflections | intensity decay: −3% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Calculated w = 1/[σ2(Fo2) + (0.0266P)2] where P = (Fo2 + 2Fc2)/3 |
4094 reflections | (Δ/σ)max < 0.001 |
253 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.72 e Å−3 |
[Hg(C11H8N)(C12H22PS2)] | V = 2327.5 (5) Å3 |
Mr = 616.16 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.923 (2) Å | µ = 6.87 mm−1 |
b = 9.9557 (10) Å | T = 293 K |
c = 15.728 (2) Å | 0.25 × 0.25 × 0.15 mm |
β = 95.088 (10)° |
Enraf Nonius CAD4 diffractometer | 2272 reflections with I > 2σ(I) |
Absorption correction: analytical (Alcock, 1970) | Rint = 0.060 |
Tmin = 0.428, Tmax = 0.709 | 1 standard reflections every 30 min |
4252 measured reflections | intensity decay: −3% |
4094 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.103 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.67 e Å−3 |
4094 reflections | Δρmin = −0.72 e Å−3 |
253 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. The structure was solved by direct methods, followed by usual difference Fourier techniques and refinement (on F2) by full-matrix least squares with unit weights and anisotropic displacement parameters for non-H atoms (Sheldrick, 1997). |
x | y | z | Uiso*/Ueq | ||
Hg | −0.12353 (3) | 0.44555 (4) | 0.63039 (2) | 0.04210 (13) | |
P | −0.09353 (18) | 0.2849 (3) | 0.81997 (15) | 0.0336 (6) | |
S2 | 0.00580 (19) | 0.4126 (3) | 0.81338 (18) | 0.0466 (7) | |
S1 | −0.1802 (2) | 0.2686 (3) | 0.71043 (16) | 0.0433 (7) | |
N | −0.2159 (7) | 0.4408 (11) | 0.4753 (5) | 0.055 (2) | |
C2 | −0.2693 (9) | 0.3463 (13) | 0.4371 (7) | 0.062 (3) | |
H2 | −0.3024 | 0.2916 | 0.4706 | 0.074* | |
C3 | −0.2772 (8) | 0.3268 (15) | 0.3495 (8) | 0.068 (4) | |
H3 | −0.3150 | 0.2608 | 0.3245 | 0.082* | |
C4 | −0.2283 (9) | 0.4067 (15) | 0.3013 (8) | 0.072 (4) | |
H4 | −0.2318 | 0.3950 | 0.2425 | 0.087* | |
C5 | −0.1738 (8) | 0.5045 (15) | 0.3388 (7) | 0.064 (4) | |
H5 | −0.1421 | 0.5618 | 0.3056 | 0.077* | |
C6 | −0.1663 (7) | 0.5172 (10) | 0.4274 (6) | 0.042 (3) | |
C7 | −0.1046 (7) | 0.6159 (11) | 0.4725 (7) | 0.046 (3) | |
C12 | −0.0684 (9) | 0.7200 (14) | 0.4275 (8) | 0.062 (4) | |
H12 | −0.0858 | 0.7288 | 0.3695 | 0.074* | |
C11 | −0.0080 (9) | 0.8102 (12) | 0.4658 (8) | 0.063 (4) | |
H11 | 0.0134 | 0.8803 | 0.4341 | 0.076* | |
C10 | 0.0210 (9) | 0.7969 (13) | 0.5511 (8) | 0.063 (4) | |
H10 | 0.0623 | 0.8573 | 0.5773 | 0.075* | |
C9 | −0.0128 (7) | 0.6904 (11) | 0.5979 (7) | 0.049 (3) | |
H9 | 0.0077 | 0.6787 | 0.6550 | 0.059* | |
C8 | −0.0758 (8) | 0.6038 (11) | 0.5599 (7) | 0.047 (3) | |
C111 | −0.0545 (6) | 0.1122 (9) | 0.8426 (6) | 0.032 (2) | |
H111 | −0.0128 | 0.1170 | 0.8943 | 0.039* | |
C112 | −0.1285 (7) | 0.0148 (9) | 0.8620 (7) | 0.036 (2) | |
H11A | −0.1585 | 0.0481 | 0.9101 | 0.044* | |
H11B | −0.1727 | 0.0092 | 0.8131 | 0.044* | |
C113 | −0.0908 (8) | −0.1227 (11) | 0.8826 (7) | 0.054 (3) | |
H11C | −0.1400 | −0.1840 | 0.8904 | 0.065* | |
H11D | −0.0529 | −0.1188 | 0.9359 | 0.065* | |
C114 | −0.0367 (8) | −0.1764 (11) | 0.8138 (8) | 0.057 (3) | |
H11E | −0.0761 | −0.1912 | 0.7622 | 0.068* | |
H11F | −0.0104 | −0.2621 | 0.8317 | 0.068* | |
C115 | 0.0371 (8) | −0.0802 (12) | 0.7950 (8) | 0.058 (3) | |
H11G | 0.0684 | −0.1151 | 0.7483 | 0.069* | |
H11H | 0.0801 | −0.0733 | 0.8448 | 0.069* | |
C116 | 0.0001 (7) | 0.0591 (11) | 0.7715 (6) | 0.043 (3) | |
H11I | −0.0379 | 0.0544 | 0.7183 | 0.052* | |
H11J | 0.0495 | 0.1199 | 0.7635 | 0.052* | |
C121 | −0.1666 (6) | 0.3264 (9) | 0.9048 (5) | 0.030 (2) | |
H121 | −0.2159 | 0.2611 | 0.9016 | 0.036* | |
C122 | −0.1162 (7) | 0.3148 (11) | 0.9930 (5) | 0.040 (3) | |
H12A | −0.0661 | 0.3773 | 0.9976 | 0.048* | |
H12B | −0.0923 | 0.2247 | 1.0011 | 0.048* | |
C123 | −0.1801 (8) | 0.3462 (12) | 1.0632 (6) | 0.052 (3) | |
H12C | −0.2257 | 0.2768 | 1.0631 | 0.063* | |
H12D | −0.1460 | 0.3456 | 1.1186 | 0.063* | |
C124 | −0.2245 (9) | 0.4795 (12) | 1.0490 (7) | 0.060 (3) | |
H12E | −0.1794 | 0.5496 | 1.0569 | 0.072* | |
H12F | −0.2672 | 0.4925 | 1.0913 | 0.072* | |
C125 | −0.2741 (8) | 0.4927 (13) | 0.9591 (7) | 0.058 (3) | |
H12G | −0.3233 | 0.4289 | 0.9525 | 0.069* | |
H12H | −0.2988 | 0.5824 | 0.9513 | 0.069* | |
C126 | −0.2075 (7) | 0.4652 (11) | 0.8918 (6) | 0.048 (3) | |
H12I | −0.2386 | 0.4714 | 0.8351 | 0.057* | |
H12J | −0.1602 | 0.5323 | 0.8964 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg | 0.0508 (2) | 0.0434 (2) | 0.0326 (2) | 0.0071 (3) | 0.00657 (16) | 0.0083 (2) |
P | 0.0383 (15) | 0.0327 (14) | 0.0298 (13) | 0.0016 (13) | 0.0021 (11) | 0.0042 (11) |
S2 | 0.0465 (16) | 0.0410 (18) | 0.0534 (16) | −0.0112 (13) | 0.0104 (13) | 0.0034 (13) |
S1 | 0.0473 (17) | 0.0469 (17) | 0.0339 (13) | −0.0053 (13) | −0.0058 (12) | 0.0060 (12) |
N | 0.072 (6) | 0.054 (6) | 0.040 (5) | −0.010 (6) | 0.013 (5) | 0.008 (5) |
C2 | 0.090 (10) | 0.056 (8) | 0.039 (6) | −0.005 (8) | 0.004 (6) | 0.007 (6) |
C3 | 0.056 (8) | 0.086 (11) | 0.060 (8) | −0.002 (8) | −0.008 (7) | 0.005 (8) |
C4 | 0.075 (9) | 0.103 (13) | 0.040 (7) | 0.004 (9) | 0.007 (7) | 0.003 (7) |
C5 | 0.058 (8) | 0.094 (11) | 0.042 (7) | 0.002 (7) | 0.019 (6) | 0.009 (7) |
C6 | 0.051 (7) | 0.038 (7) | 0.039 (6) | 0.023 (5) | 0.018 (5) | 0.010 (5) |
C7 | 0.048 (7) | 0.043 (7) | 0.047 (6) | 0.008 (6) | 0.017 (5) | 0.006 (5) |
C12 | 0.070 (9) | 0.070 (9) | 0.049 (7) | 0.009 (8) | 0.024 (7) | 0.031 (7) |
C11 | 0.076 (9) | 0.045 (8) | 0.074 (9) | −0.001 (7) | 0.035 (8) | 0.010 (7) |
C10 | 0.074 (9) | 0.045 (8) | 0.072 (9) | 0.001 (7) | 0.021 (7) | 0.005 (7) |
C9 | 0.041 (6) | 0.052 (8) | 0.054 (7) | 0.012 (6) | 0.005 (5) | 0.003 (6) |
C8 | 0.053 (7) | 0.045 (7) | 0.044 (6) | 0.006 (6) | 0.016 (5) | 0.003 (5) |
C111 | 0.040 (6) | 0.024 (5) | 0.032 (5) | 0.009 (4) | −0.001 (4) | 0.000 (4) |
C112 | 0.043 (6) | 0.019 (5) | 0.047 (6) | −0.008 (4) | 0.003 (5) | 0.007 (4) |
C113 | 0.060 (8) | 0.039 (7) | 0.062 (7) | 0.002 (6) | 0.004 (6) | −0.003 (6) |
C114 | 0.069 (8) | 0.029 (7) | 0.069 (8) | 0.000 (6) | −0.011 (7) | 0.000 (6) |
C115 | 0.056 (7) | 0.058 (9) | 0.062 (7) | 0.026 (7) | 0.017 (6) | −0.010 (6) |
C116 | 0.055 (6) | 0.034 (6) | 0.044 (6) | 0.004 (6) | 0.020 (5) | −0.003 (6) |
C121 | 0.038 (5) | 0.025 (5) | 0.026 (5) | −0.001 (4) | 0.002 (4) | 0.003 (4) |
C122 | 0.052 (6) | 0.044 (7) | 0.023 (5) | 0.004 (5) | 0.001 (4) | 0.002 (5) |
C123 | 0.065 (8) | 0.062 (8) | 0.033 (5) | 0.006 (7) | 0.017 (5) | 0.004 (6) |
C124 | 0.074 (9) | 0.051 (9) | 0.055 (7) | 0.019 (7) | 0.011 (7) | −0.003 (6) |
C125 | 0.063 (8) | 0.058 (8) | 0.052 (7) | 0.020 (6) | 0.005 (6) | 0.004 (6) |
C126 | 0.059 (7) | 0.047 (8) | 0.038 (5) | 0.010 (6) | 0.005 (5) | 0.009 (5) |
Hg—C8 | 2.088 (11) | C7—C12 | 1.391 (15) |
Hg—S1 | 2.365 (3) | C7—C8 | 1.407 (15) |
Hg—N | 2.694 (9) | C12—C11 | 1.373 (17) |
Hg—S2 | 3.336 (3) | C11—C10 | 1.379 (17) |
Hg—C12i | 3.495 (12) | C10—C9 | 1.410 (15) |
Hg—C11i | 3.626 (11) | C9—C8 | 1.374 (15) |
Hg—C7i | 3.945 (10) | C111—C112 | 1.521 (13) |
P—C111 | 1.839 (9) | C111—C116 | 1.535 (12) |
P—C121 | 1.843 (8) | C112—C113 | 1.505 (13) |
P—S2 | 1.963 (4) | C113—C114 | 1.505 (15) |
P—S1 | 2.066 (4) | C114—C115 | 1.508 (15) |
N—C6 | 1.338 (13) | C115—C116 | 1.525 (14) |
N—C2 | 1.342 (15) | C121—C126 | 1.518 (13) |
C2—C3 | 1.385 (15) | C121—C122 | 1.522 (12) |
C3—C4 | 1.355 (17) | C122—C123 | 1.553 (12) |
C4—C5 | 1.369 (17) | C123—C124 | 1.491 (15) |
C5—C6 | 1.393 (14) | C124—C125 | 1.542 (15) |
C6—C7 | 1.484 (15) | C125—C126 | 1.538 (13) |
C8—Hg—S1 | 178.9 (3) | C4—C3—C2 | 118.1 (14) |
C8—Hg—N | 72.7 (4) | C3—C4—C5 | 120.4 (12) |
S1—Hg—N | 106.9 (2) | C4—C5—C6 | 119.2 (12) |
C8—Hg—S2 | 109.5 (3) | N—C6—C5 | 120.8 (12) |
S1—Hg—S2 | 70.99 (8) | N—C6—C7 | 117.2 (9) |
N—Hg—S2 | 171.8 (2) | C5—C6—C7 | 122.0 (10) |
C8—Hg—C12i | 83.8 (3) | C12—C7—C8 | 117.5 (11) |
S1—Hg—C12i | 97.3 (2) | C12—C7—C6 | 120.1 (10) |
N—Hg—C12i | 96.9 (3) | C8—C7—C6 | 122.2 (10) |
S2—Hg—C12i | 75.7 (2) | C11—C12—C7 | 122.3 (12) |
C8—Hg—C11i | 94.9 (3) | C12—C11—C10 | 120.1 (12) |
S1—Hg—C11i | 86.0 (2) | C11—C10—C9 | 119.0 (13) |
N—Hg—C11i | 82.1 (3) | C8—C9—C10 | 120.5 (11) |
S2—Hg—C11i | 89.9 (2) | C9—C8—C7 | 120.6 (10) |
C12i—Hg—C11i | 22.1 (3) | C9—C8—Hg | 119.7 (8) |
C8—Hg—C7i | 63.3 (3) | C7—C8—Hg | 119.6 (9) |
S1—Hg—C7i | 117.71 (17) | C112—C111—C116 | 111.6 (8) |
N—Hg—C7i | 90.9 (3) | C112—C111—P | 114.3 (7) |
S2—Hg—C7i | 83.37 (17) | C116—C111—P | 111.1 (7) |
C12i—Hg—C7i | 20.4 (2) | C113—C112—C111 | 111.0 (8) |
C11i—Hg—C7i | 37.0 (3) | C112—C113—C114 | 112.5 (10) |
C111—P—C121 | 105.5 (4) | C113—C114—C115 | 111.3 (10) |
C111—P—S2 | 112.8 (3) | C114—C115—C116 | 111.7 (9) |
C121—P—S2 | 113.0 (3) | C115—C116—C111 | 109.9 (8) |
C111—P—S1 | 104.6 (3) | C126—C121—C122 | 110.6 (8) |
C121—P—S1 | 104.8 (3) | C126—C121—P | 111.3 (6) |
S2—P—S1 | 115.24 (17) | C122—C121—P | 111.5 (6) |
P—S2—Hg | 74.18 (11) | C121—C122—C123 | 110.4 (8) |
P—S1—Hg | 99.12 (13) | C124—C123—C122 | 111.5 (9) |
C6—N—C2 | 118.9 (9) | C123—C124—C125 | 112.6 (10) |
C6—N—Hg | 103.6 (7) | C126—C125—C124 | 109.2 (9) |
C2—N—Hg | 130.9 (7) | C121—C126—C125 | 110.3 (8) |
N—C2—C3 | 122.6 (12) | ||
C111—P—S2—Hg | 125.4 (3) | C12—C11—C10—C9 | −0.4 (18) |
C121—P—S2—Hg | −115.1 (3) | C11—C10—C9—C8 | −2.0 (17) |
S1—P—S2—Hg | 5.35 (15) | C10—C9—C8—C7 | 3.0 (16) |
C8—Hg—S2—P | 174.5 (3) | C10—C9—C8—Hg | 179.3 (8) |
S1—Hg—S2—P | −4.47 (12) | C12—C7—C8—C9 | −1.4 (16) |
N—Hg—S2—P | −80.9 (14) | C6—C7—C8—C9 | 174.5 (9) |
C12i—Hg—S2—P | −107.6 (2) | C12—C7—C8—Hg | −177.7 (8) |
C11i—Hg—S2—P | −90.3 (2) | C6—C7—C8—Hg | −1.8 (13) |
C7i—Hg—S2—P | −126.8 (2) | S1—Hg—C8—C9 | 105 (17) |
C111—P—S1—Hg | −131.8 (3) | N—Hg—C8—C9 | 176.1 (9) |
C121—P—S1—Hg | 117.5 (3) | S2—Hg—C8—C9 | −12.1 (9) |
S2—P—S1—Hg | −7.4 (2) | C12i—Hg—C8—C9 | −84.6 (9) |
C8—Hg—S1—P | −113 (17) | C11i—Hg—C8—C9 | −103.7 (9) |
N—Hg—S1—P | 175.9 (2) | C7i—Hg—C8—C9 | −83.8 (9) |
S2—Hg—S1—P | 4.14 (12) | S1—Hg—C8—C7 | −79 (17) |
C12i—Hg—S1—P | 76.3 (3) | N—Hg—C8—C7 | −7.5 (8) |
C11i—Hg—S1—P | 95.4 (3) | S2—Hg—C8—C7 | 164.2 (7) |
C7i—Hg—S1—P | 75.5 (2) | C12i—Hg—C8—C7 | 91.8 (8) |
C8—Hg—N—C6 | 16.6 (7) | C11i—Hg—C8—C7 | 72.6 (9) |
S1—Hg—N—C6 | −164.4 (6) | C7i—Hg—C8—C7 | 92.6 (8) |
S2—Hg—N—C6 | −90.6 (16) | C121—P—C111—C112 | 47.0 (8) |
C12i—Hg—N—C6 | −64.6 (7) | S2—P—C111—C112 | 170.8 (6) |
C11i—Hg—N—C6 | −81.1 (7) | S1—P—C111—C112 | −63.2 (7) |
C7i—Hg—N—C6 | −45.0 (7) | C121—P—C111—C116 | 174.5 (7) |
C8—Hg—N—C2 | 166.8 (11) | S2—P—C111—C116 | −61.7 (8) |
S1—Hg—N—C2 | −14.3 (11) | S1—P—C111—C116 | 64.3 (7) |
S2—Hg—N—C2 | 59.5 (19) | C116—C111—C112—C113 | 54.7 (11) |
C12i—Hg—N—C2 | 85.6 (11) | P—C111—C112—C113 | −178.2 (7) |
C11i—Hg—N—C2 | 69.1 (11) | C111—C112—C113—C114 | −54.5 (12) |
C7i—Hg—N—C2 | 105.1 (11) | C112—C113—C114—C115 | 55.0 (13) |
C6—N—C2—C3 | −1.8 (19) | C113—C114—C115—C116 | −55.7 (13) |
Hg—N—C2—C3 | −148.3 (10) | C114—C115—C116—C111 | 55.6 (12) |
N—C2—C3—C4 | 0 (2) | C112—C111—C116—C115 | −55.1 (12) |
C2—C3—C4—C5 | −1 (2) | P—C111—C116—C115 | 176.1 (7) |
C3—C4—C5—C6 | 3 (2) | C111—P—C121—C126 | −177.4 (7) |
C2—N—C6—C5 | 3.7 (17) | S2—P—C121—C126 | 59.0 (8) |
Hg—N—C6—C5 | 158.3 (9) | S1—P—C121—C126 | −67.3 (7) |
C2—N—C6—C7 | −177.0 (10) | C111—P—C121—C122 | 58.6 (8) |
Hg—N—C6—C7 | −22.4 (10) | S2—P—C121—C122 | −65.1 (7) |
C4—C5—C6—N | −4.2 (18) | S1—P—C121—C122 | 168.7 (6) |
C4—C5—C6—C7 | 176.5 (11) | C126—C121—C122—C123 | 57.2 (11) |
N—C6—C7—C12 | −163.9 (10) | P—C121—C122—C123 | −178.3 (7) |
C5—C6—C7—C12 | 15.4 (16) | C121—C122—C123—C124 | −54.4 (13) |
N—C6—C7—C8 | 20.3 (15) | C122—C123—C124—C125 | 54.4 (14) |
C5—C6—C7—C8 | −160.4 (11) | C123—C124—C125—C126 | −56.0 (14) |
C8—C7—C12—C11 | −1.1 (18) | C122—C121—C126—C125 | −60.1 (11) |
C6—C7—C12—C11 | −177.1 (11) | P—C121—C126—C125 | 175.4 (7) |
C7—C12—C11—C10 | 2 (2) | C124—C125—C126—C121 | 58.0 (13) |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Hg(C11H8N)(C12H22PS2)] |
Mr | 616.16 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 14.923 (2), 9.9557 (10), 15.728 (2) |
β (°) | 95.088 (10) |
V (Å3) | 2327.5 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 6.87 |
Crystal size (mm) | 0.25 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Enraf Nonius CAD4 diffractometer |
Absorption correction | Analytical (Alcock, 1970) |
Tmin, Tmax | 0.428, 0.709 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4252, 4094, 2272 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.103, 0.96 |
No. of reflections | 4094 |
No. of parameters | 253 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.67, −0.72 |
Computer programs: CAD-4 EXPRESS (Enraf Nonius, 1994), XCAD4 (Harms & Wocadlo, 1996), Please specify, SHELXL97 (Sheldrick, 1997).
Hg—C8 | 2.088 (11) | P—C111 | 1.839 (9) |
Hg—S1 | 2.365 (3) | P—C121 | 1.843 (8) |
Hg—N | 2.694 (9) | P—S2 | 1.963 (4) |
Hg—S2 | 3.336 (3) | P—S1 | 2.066 (4) |
C8—Hg—S1 | 178.9 (3) | C111—P—S2 | 112.8 (3) |
C8—Hg—N | 72.7 (4) | C121—P—S2 | 113.0 (3) |
S1—Hg—N | 106.9 (2) | C111—P—S1 | 104.6 (3) |
C8—Hg—S2 | 109.5 (3) | C121—P—S1 | 104.8 (3) |
S1—Hg—S2 | 70.99 (8) | S2—P—S1 | 115.24 (17) |
N—Hg—S2 | 171.8 (2) | P—S2—Hg | 74.18 (11) |
C111—P—C121 | 105.5 (4) | P—S1—Hg | 99.12 (13) |
In the reaction of [2-(pyridin-2-yl)phenyl]mercury(II) acetate, [Hg(PhPy)(OAc)], with diphenyldithiophosphinic acid, HS2PPh2, the C—Hg bond is broken to afford phenylpyridine and [Hg2(S2PPh2)4] (Casas et al., 1997). The reaction of dicyclohexyldithiophosphinic acid, HS2PCy2, with an appropriate mole ratio of TlPh2+ cation in chloroform likewise produces protodemetallation (i.e. the loss of one or more alkyl or aryl groups from the metal with formation of an alkane or arene), affording Tl3+ species and benzene (Casas et al., 1995). To explore this type of process further, we reacted [Hg(PhPy)(OAc)] with HS2PCy2. At room temperature the reaction afforded a black solid which probably contains HgS but at near 273 K, in an ice bath, it yielded a product from which colourless crystals of the title organomercury dithiophosphinato, [Hg(PhPy)(S2PCy2)], (I), were isolated, showing that no protodemetallation process had occurred. \scheme
Fig. 1 shows the molecular structure of (I) as drawn by ZORTEP (Zsolnai & Huttner, 1994), and the atom-numbering scheme used. Selected interatomic distances and angles are listed in Table 1. The Hg atom is strongly coordinated to C8, the carbon at position 2 of the phenyl group [Hg—C8 = 2.088 (11) Å], and to one of the dithiophosphinate sulfur atoms (S1). The C8—Hg—S1 fragment is almost linear [178.9 (3)°], as is usual in monoorganomercuric thiolate derivatives (Casas et al., 1999). The Hg—S1 distance [2.365 (3) Å] lies in the range observed for other organomercury(II) dithiophosphates and dithiophosphinates (Zukerman-Schpector et al., 1991; Vázquez-López et al., 1992; Casas et al., 1994). The Hg—N distance of 2.694 (9) Å is also shorter than the sum of the Van der Waals radii (3.55 Å; Casas et al., 1999; Bondi, 1964); it is close to the values found in [Hg(PhPy)Cl] [2.63 (1) and 2.67 (1) Å; Constable et al., 1989], but is clearly shorter than in [Hg(PhPy)(AcO)] [2.727 (9) Å; Casas et al., 1996] and longer than in [Hg(PhPy)(Hstsc)] [2.576 (6) Å; H2stsc = 2-formyl-(2-hydroxy-benzene)thiosemicarbazone; Lobana et al., 1998]. The phenyl and pyridinyl rings of the [Hg(PhPy)]+ moiety in (I) are not coplanar but form a dihedral angle of 19.3 (6)°, and the interplanar angle is narrower than in the acetate derivative (Casas et al., 1996).
The other dithiophosphinato sulfur, S2, lies 3.336 (3) Å from the Hg atom. This distance, too, is shorter than the sum of the corresponding van der Waals radii (3.8 Å; Casas et al., 1999; Bondi, 1964), and though longer than that observed in [HgPh (S2PEt2)] [3.182 (3) Å; Casas et al., 1994], is within the usual range for secondary Hg···S bonds in monoorganomercury dithiophosphates and dithiophosphinates. Taking this Hg···S interaction into account, the coordination geometry around the Hg atom can be described as of a distorted square planar kind [the largest displacement from the least squares plane through Hg/N/C8/S1/S2 is for N, which is 0.35 (1) Å out of it].
Secondary Hg···S bonds in monoorganomercury dithiophosphates and dithiophosphinates are generally intermolecular, organizing the molecules into centrosymmetric dimers, as in [HgMe(S2PPh2)] (Zukerman-Schpector et al., 1991) and [HgPh{S2P(OEt)2}] (Vázquez-López et al., 1992), or in linear chains of identically oriented monomers, as in [HgPh(S2PEt2)]. In the case of (I), these possibilities are probably prevented by steric hindrance. The structure of this compound is probably most similar to that of the 2-formyl-(2-hydroxybenzene)thiosemicarbazonate, [Hg(PhPy)(Hstsc)] (Lobana et al., 1998). The lattices of these compounds consist of molecules which have no intermolecular interactions and in which the Hg atom has two primary bonds [Hg—C8, Hg—S1 and C8—Hg—S1 in the dithiophosphinate complex, (I) (Table 1); Hg—C = 2.083 (7) and Hg—S = 2.357 Å, and C—Hg—S = 177.7 (2)° in the thiosemicarbazonate] and two secondary bonds [Hg—N and Hg—S2 in (I) (Table 1); two Hg—N bonds with distances 2.576 (6) and 3.126 (6) Å in the thiosemicarbazonate]. Finally, the S2PCy2− ligand is more anisobidentate in (I) (see Table 1) than in [TlPh2(S2PCy2)] [Tl—S1 = 2.789 (3) and Tl—S2 = 2.816 (3) Å; Casas et al., 1995]. In keeping with this, the P—S1 bond, corresponding to S strongly coordinated to metal, is longer and the P—S2 bond shorter in (I) (Δ/σ = 18.2) than in the latter compound.