metal-organic compounds
Bis[μ-O-isopropyl (4-ethoxyphenyl)dithiophosphonato-κ2S:S′]bis{[O-isopropyl (4-ethoxyphenyl)dithiophosphonato-κ2S,S′]mercury(II)}
aSchool of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa
*Correspondence e-mail: vanzylw@ukzn.ac.za
The title compound, [Hg2(C11H16O2PS2)4], is a dinuclear complex with a distorted tetrahedral geometry around each HgII atom. Although the two HgII atoms are surrounded by the same ligand, two different coordination modes are observed: one is chelating and the other bridging. The Hg—S bonds form two distinct pairs of long and short bonds. One pair includes both chelating and bridging Hg—S bonds with approximately equal bond lengths of 2.4042 (8) and 2.3997 (7) Å, respectively. The other pair is significantly longer at 2.9361 (9) and 2.8105 (8) Å, respectively. This pattern forms a center of inversion through the molecule with an equal and opposite effect occurring at the other HgII atom. The S—Hg—S angles vary widely from 76.26 (2) to 154.65 (3)°, indicative of a distorted tetrahedral arrangement of the S atoms around the HgII atom. The P—S bond lengths are 1.9681 (10) and 2.0519 (11)°, clearly indicating partial double-bond character in the former. The molecule contains an inversion center situated between the two HgII atoms.
Related literature
For information on dithiophosphonate compounds, see: Van Zyl & Fackler (2000); Van Zyl (2010). For examples of mercury(II) dithiophosphonate complexes, see: Gray et al. (2004a,b); Devillanova et al. (2006).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2006); cell SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812046624/ff2088sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812046624/ff2088Isup2.hkl
A colorless methanol (40 ml) solution of NH4[S2P(OiPr)(4-C6H4OEt)] (1.322 g, 4.506 mmol) was prepared. A second colorless solution of Hg(NO3)2.H20 (0.772 g, 2.253 mmol) in deionized water (20 ml) was prepared, and added to the ligand solution with stirring over a period of 5 min. This resulted in a white precipitate indicating the formation of the title complex. The precipitate was collected by vacuum filtration, washed with water (3 x 10 ml) to remove NH4NO3 and allowed to dry under vacuum for a period of 3 hrs, yielding a dry, free-flowing white powder. Colourless crystals suitable for X-ray analysis were grown by the slow diffusion of hexane into a dichloromethane solution of the title complex. Yield: 76%. M.p. 117–118°C.
31P NMR (CDCl3): δ (p.p.m.): 100.73. 1H NMR (CDCl3): δ (p.p.m.): 7.93 (2H, dd, J(31P-1H) = 14.46 Hz, J(1H -1H) = 8.82 Hz, o-ArH), 6.91 (2H, dd, J(31P-1H) = 8.84 Hz, J(1H -1H) = 3.40 Hz, m-ArH), 5.23 (1H, d quart, J(31P-1H) = 20.82 Hz, J(1H -1H) = 6.19 Hz, CH), 4.05 (2H, quart, J(1H -1H) = 6.96 Hz, ArOCH2), 1.42 (6H, d, J(1H -1H) = 6.2 Hz, CH3), 1.39 (3H, t, J(1H -1H) = 6.96 Hz, ArOCH2CH3). 13C NMR (CDCl3): δ (p.p.m.): 162.27 (p-ArC), 132.15 (m-ArC), 130.40 (Ar—C1), 114.32 (o-ArC), 72.22 (CH), 64.03 (ArOCH2), 24.27 (CH3), 14.91 (ArOCH2CH3).
All hydrogen atoms were placed in idealized positions and refined with geometrical constraints and Ueq of 1.20–1.50 of parent C atom.. The structure was refined to
factor of 0.0227.Data collection: APEX2 (Bruker, 2006); cell
SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008.[Hg2(C11H16O2PS2)4] | Z = 1 |
Mr = 1502.49 | F(000) = 740 |
Triclinic, P1 | Dx = 1.745 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.079 (3) Å | Cell parameters from 34157 reflections |
b = 11.985 (3) Å | θ = 1.9–27.4° |
c = 12.253 (3) Å | µ = 5.81 mm−1 |
α = 62.908 (4)° | T = 173 K |
β = 84.418 (4)° | Block, colourless |
γ = 80.862 (4)° | 0.15 × 0.15 × 0.12 mm |
V = 1429.5 (6) Å3 |
Bruker Kappa DUO APEXII diffractometer | 6382 independent reflections |
Radiation source: fine-focus sealed tube | 5622 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.077 |
0.5° ϕ scans and ω scans | θmax = 27.4°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −14→14 |
Tmin = 0.476, Tmax = 0.542 | k = −15→15 |
34157 measured reflections | l = −15→15 |
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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.049 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.017P)2] where P = (Fo2 + 2Fc2)/3 |
6382 reflections | (Δ/σ)max = 0.002 |
304 parameters | Δρmax = 0.87 e Å−3 |
0 restraints | Δρmin = −1.02 e Å−3 |
[Hg2(C11H16O2PS2)4] | γ = 80.862 (4)° |
Mr = 1502.49 | V = 1429.5 (6) Å3 |
Triclinic, P1 | Z = 1 |
a = 11.079 (3) Å | Mo Kα radiation |
b = 11.985 (3) Å | µ = 5.81 mm−1 |
c = 12.253 (3) Å | T = 173 K |
α = 62.908 (4)° | 0.15 × 0.15 × 0.12 mm |
β = 84.418 (4)° |
Bruker Kappa DUO APEXII diffractometer | 6382 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | 5622 reflections with I > 2σ(I) |
Tmin = 0.476, Tmax = 0.542 | Rint = 0.077 |
34157 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.049 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.87 e Å−3 |
6382 reflections | Δρmin = −1.02 e Å−3 |
304 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 | 0.406211 (9) | 0.860930 (11) | 0.068281 (10) | 0.03450 (5) | |
S1 | 0.21870 (6) | 0.87000 (7) | −0.02079 (7) | 0.03184 (16) | |
S2 | 0.33676 (6) | 0.60580 (7) | 0.21177 (6) | 0.02963 (15) | |
S3 | 0.47011 (6) | 1.09499 (7) | −0.19071 (6) | 0.02882 (15) | |
S4 | 0.61332 (6) | 0.79500 (7) | −0.05226 (6) | 0.03264 (16) | |
P1 | 0.21046 (6) | 0.68074 (7) | 0.08684 (6) | 0.02416 (15) | |
P2 | 0.59057 (6) | 0.95292 (7) | −0.20573 (6) | 0.02505 (15) | |
O1 | 0.24135 (16) | 0.4936 (2) | −0.28729 (18) | 0.0369 (5) | |
O2 | 0.07486 (14) | 0.66471 (17) | 0.13934 (16) | 0.0283 (4) | |
O3 | 1.05424 (16) | 1.14120 (19) | −0.45478 (18) | 0.0370 (5) | |
O4 | 0.54046 (15) | 0.93611 (17) | −0.31346 (16) | 0.0286 (4) | |
C1 | 0.2184 (2) | 0.6092 (2) | −0.0143 (2) | 0.0243 (6) | |
C2 | 0.1144 (2) | 0.6060 (3) | −0.0679 (2) | 0.0339 (7) | |
H2 | 0.0358 | 0.6332 | −0.0434 | 0.041* | |
C3 | 0.1250 (2) | 0.5637 (3) | −0.1559 (3) | 0.0366 (7) | |
H3 | 0.0537 | 0.5607 | −0.1911 | 0.044* | |
C4 | 0.2396 (2) | 0.5255 (3) | −0.1936 (2) | 0.0280 (6) | |
C5 | 0.3435 (2) | 0.5230 (3) | −0.1371 (3) | 0.0284 (6) | |
H5 | 0.4219 | 0.4926 | −0.1590 | 0.034* | |
C6 | 0.3305 (2) | 0.5655 (3) | −0.0487 (3) | 0.0293 (6) | |
H6 | 0.4015 | 0.5645 | −0.0104 | 0.035* | |
C7 | 0.3573 (2) | 0.4493 (3) | −0.3265 (3) | 0.0349 (7) | |
H7A | 0.3947 | 0.3713 | −0.2581 | 0.042* | |
H7B | 0.4134 | 0.5141 | −0.3530 | 0.042* | |
C8 | 0.3361 (3) | 0.4232 (4) | −0.4312 (3) | 0.0503 (9) | |
H8A | 0.2828 | 0.3568 | −0.4033 | 0.075* | |
H8B | 0.4146 | 0.3952 | −0.4611 | 0.075* | |
H8C | 0.2972 | 0.5004 | −0.4975 | 0.075* | |
C9 | 0.0212 (2) | 0.7226 (3) | 0.2196 (3) | 0.0328 (7) | |
H9 | 0.0767 | 0.7807 | 0.2197 | 0.039* | |
C10 | −0.0988 (3) | 0.7978 (3) | 0.1647 (3) | 0.0507 (9) | |
H10A | −0.0837 | 0.8647 | 0.0824 | 0.076* | |
H10B | −0.1397 | 0.8359 | 0.2167 | 0.076* | |
H10C | −0.1511 | 0.7419 | 0.1595 | 0.076* | |
C11 | 0.0099 (3) | 0.6180 (3) | 0.3468 (3) | 0.0403 (7) | |
H11A | −0.0408 | 0.5584 | 0.3459 | 0.060* | |
H11B | −0.0283 | 0.6534 | 0.4017 | 0.060* | |
H11C | 0.0913 | 0.5737 | 0.3758 | 0.060* | |
C12 | 0.7306 (2) | 1.0142 (3) | −0.2752 (2) | 0.0267 (6) | |
C13 | 0.7268 (2) | 1.1228 (3) | −0.3845 (3) | 0.0338 (7) | |
H13 | 0.6497 | 1.1674 | −0.4171 | 0.041* | |
C14 | 0.8323 (2) | 1.1688 (3) | −0.4480 (3) | 0.0343 (7) | |
H14 | 0.8275 | 1.2432 | −0.5240 | 0.041* | |
C15 | 0.9455 (2) | 1.1049 (3) | −0.3994 (3) | 0.0307 (6) | |
C16 | 0.9506 (2) | 0.9983 (3) | −0.2874 (3) | 0.0347 (7) | |
H16 | 1.0276 | 0.9565 | −0.2525 | 0.042* | |
C17 | 0.8446 (2) | 0.9522 (3) | −0.2259 (3) | 0.0331 (6) | |
H17 | 0.8493 | 0.8780 | −0.1498 | 0.040* | |
C18 | 1.0515 (3) | 1.2395 (3) | −0.5783 (3) | 0.0378 (7) | |
H18A | 1.0037 | 1.3180 | −0.5815 | 0.045* | |
H18B | 1.0125 | 1.2142 | −0.6316 | 0.045* | |
C19 | 1.1816 (3) | 1.2612 (3) | −0.6217 (3) | 0.0503 (9) | |
H19A | 1.2200 | 1.2835 | −0.5669 | 0.075* | |
H19B | 1.1821 | 1.3303 | −0.7052 | 0.075* | |
H19C | 1.2271 | 1.1839 | −0.6213 | 0.075* | |
C20 | 0.4382 (2) | 0.8642 (3) | −0.2971 (3) | 0.0314 (7) | |
H20 | 0.4191 | 0.8146 | −0.2077 | 0.038* | |
C21 | 0.3287 (3) | 0.9560 (3) | −0.3587 (3) | 0.0468 (8) | |
H21A | 0.3069 | 1.0137 | −0.3213 | 0.070* | |
H21B | 0.2598 | 0.9097 | −0.3487 | 0.070* | |
H21C | 0.3479 | 1.0047 | −0.4462 | 0.070* | |
C22 | 0.4828 (3) | 0.7755 (3) | −0.3523 (3) | 0.0415 (8) | |
H22A | 0.5113 | 0.8238 | −0.4371 | 0.062* | |
H22B | 0.4159 | 0.7305 | −0.3512 | 0.062* | |
H22C | 0.5504 | 0.7144 | −0.3045 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.03746 (7) | 0.03923 (8) | 0.03315 (8) | −0.02021 (5) | 0.00380 (5) | −0.01779 (6) |
S1 | 0.0325 (4) | 0.0254 (4) | 0.0331 (4) | −0.0065 (3) | −0.0045 (3) | −0.0077 (3) |
S2 | 0.0288 (3) | 0.0303 (4) | 0.0288 (4) | −0.0053 (3) | −0.0040 (3) | −0.0112 (3) |
S3 | 0.0272 (3) | 0.0276 (4) | 0.0345 (4) | −0.0068 (3) | 0.0003 (3) | −0.0155 (3) |
S4 | 0.0339 (4) | 0.0301 (4) | 0.0283 (4) | −0.0051 (3) | 0.0038 (3) | −0.0090 (3) |
P1 | 0.0220 (3) | 0.0250 (4) | 0.0266 (4) | −0.0065 (3) | 0.0011 (3) | −0.0119 (3) |
P2 | 0.0260 (3) | 0.0271 (4) | 0.0240 (4) | −0.0085 (3) | 0.0018 (3) | −0.0120 (3) |
O1 | 0.0292 (10) | 0.0557 (15) | 0.0360 (12) | −0.0048 (9) | 0.0007 (8) | −0.0298 (11) |
O2 | 0.0236 (9) | 0.0348 (12) | 0.0328 (11) | −0.0098 (8) | 0.0067 (7) | −0.0200 (9) |
O3 | 0.0271 (10) | 0.0425 (13) | 0.0369 (12) | −0.0111 (9) | 0.0067 (8) | −0.0133 (10) |
O4 | 0.0341 (10) | 0.0324 (12) | 0.0245 (10) | −0.0160 (8) | 0.0035 (8) | −0.0142 (9) |
C1 | 0.0239 (12) | 0.0243 (15) | 0.0235 (14) | −0.0060 (10) | −0.0003 (10) | −0.0089 (12) |
C2 | 0.0224 (13) | 0.0484 (19) | 0.0350 (17) | −0.0050 (12) | 0.0019 (11) | −0.0225 (15) |
C3 | 0.0250 (14) | 0.059 (2) | 0.0359 (17) | −0.0084 (13) | −0.0008 (11) | −0.0288 (16) |
C4 | 0.0303 (14) | 0.0290 (16) | 0.0255 (15) | −0.0074 (12) | 0.0009 (11) | −0.0120 (13) |
C5 | 0.0237 (13) | 0.0296 (16) | 0.0339 (16) | −0.0023 (11) | 0.0011 (11) | −0.0167 (13) |
C6 | 0.0230 (13) | 0.0343 (17) | 0.0349 (16) | −0.0031 (11) | −0.0036 (11) | −0.0189 (14) |
C7 | 0.0312 (14) | 0.0427 (19) | 0.0370 (17) | −0.0051 (13) | 0.0023 (12) | −0.0236 (15) |
C8 | 0.0424 (18) | 0.078 (3) | 0.043 (2) | −0.0038 (17) | 0.0040 (14) | −0.041 (2) |
C9 | 0.0346 (15) | 0.0348 (18) | 0.0380 (17) | −0.0109 (13) | 0.0089 (12) | −0.0238 (15) |
C10 | 0.0457 (19) | 0.038 (2) | 0.053 (2) | 0.0070 (15) | 0.0093 (16) | −0.0137 (17) |
C11 | 0.0387 (16) | 0.050 (2) | 0.0367 (18) | −0.0115 (14) | 0.0065 (13) | −0.0233 (16) |
C12 | 0.0282 (13) | 0.0327 (17) | 0.0240 (14) | −0.0092 (11) | 0.0026 (11) | −0.0158 (13) |
C13 | 0.0278 (14) | 0.0386 (18) | 0.0292 (16) | −0.0061 (12) | −0.0039 (11) | −0.0089 (14) |
C14 | 0.0317 (14) | 0.0370 (18) | 0.0263 (16) | −0.0104 (12) | 0.0000 (11) | −0.0055 (14) |
C15 | 0.0270 (14) | 0.0344 (17) | 0.0348 (17) | −0.0095 (12) | 0.0032 (11) | −0.0182 (14) |
C16 | 0.0245 (14) | 0.0361 (18) | 0.0390 (18) | −0.0012 (12) | −0.0015 (12) | −0.0135 (15) |
C17 | 0.0348 (15) | 0.0306 (17) | 0.0285 (16) | −0.0057 (12) | −0.0008 (12) | −0.0081 (13) |
C18 | 0.0398 (16) | 0.0410 (19) | 0.0348 (17) | −0.0145 (14) | 0.0088 (13) | −0.0179 (15) |
C19 | 0.0424 (18) | 0.056 (2) | 0.049 (2) | −0.0184 (16) | 0.0165 (15) | −0.0196 (18) |
C20 | 0.0314 (14) | 0.0397 (18) | 0.0285 (16) | −0.0188 (13) | 0.0034 (11) | −0.0162 (14) |
C21 | 0.0342 (16) | 0.061 (2) | 0.054 (2) | −0.0060 (15) | −0.0022 (14) | −0.0326 (19) |
C22 | 0.0429 (17) | 0.043 (2) | 0.048 (2) | −0.0182 (15) | 0.0028 (14) | −0.0249 (17) |
Hg1—S3i | 2.3997 (7) | C9—C11 | 1.499 (4) |
Hg1—S1 | 2.4042 (8) | C9—C10 | 1.509 (4) |
Hg1—S4 | 2.8105 (8) | C9—H9 | 1.0000 |
Hg1—S2 | 2.9361 (9) | C10—H10A | 0.9800 |
S1—P1 | 2.0519 (11) | C10—H10B | 0.9800 |
S2—P1 | 1.9681 (10) | C10—H10C | 0.9800 |
S3—P2 | 2.0568 (10) | C11—H11A | 0.9800 |
S3—Hg1i | 2.3998 (7) | C11—H11B | 0.9800 |
S4—P2 | 1.9699 (11) | C11—H11C | 0.9800 |
P1—O2 | 1.5807 (17) | C12—C13 | 1.377 (4) |
P1—C1 | 1.788 (3) | C12—C17 | 1.398 (4) |
P2—O4 | 1.5848 (18) | C13—C14 | 1.382 (4) |
P2—C12 | 1.791 (2) | C13—H13 | 0.9500 |
O1—C4 | 1.363 (3) | C14—C15 | 1.393 (4) |
O1—C7 | 1.435 (3) | C14—H14 | 0.9500 |
O2—C9 | 1.476 (3) | C15—C16 | 1.383 (4) |
O3—C15 | 1.357 (3) | C16—C17 | 1.380 (4) |
O3—C18 | 1.433 (3) | C16—H16 | 0.9500 |
O4—C20 | 1.475 (3) | C17—H17 | 0.9500 |
C1—C6 | 1.375 (3) | C18—C19 | 1.507 (4) |
C1—C2 | 1.395 (3) | C18—H18A | 0.9900 |
C2—C3 | 1.374 (4) | C18—H18B | 0.9900 |
C2—H2 | 0.9500 | C19—H19A | 0.9800 |
C3—C4 | 1.389 (4) | C19—H19B | 0.9800 |
C3—H3 | 0.9500 | C19—H19C | 0.9800 |
C4—C5 | 1.389 (3) | C20—C21 | 1.500 (4) |
C5—C6 | 1.379 (4) | C20—C22 | 1.501 (4) |
C5—H5 | 0.9500 | C20—H20 | 1.0000 |
C6—H6 | 0.9500 | C21—H21A | 0.9800 |
C7—C8 | 1.498 (4) | C21—H21B | 0.9800 |
C7—H7A | 0.9900 | C21—H21C | 0.9800 |
C7—H7B | 0.9900 | C22—H22A | 0.9800 |
C8—H8A | 0.9800 | C22—H22B | 0.9800 |
C8—H8B | 0.9800 | C22—H22C | 0.9800 |
C8—H8C | 0.9800 | ||
S3i—Hg1—S1 | 154.65 (3) | C10—C9—H9 | 109.5 |
S3i—Hg1—S4 | 91.92 (3) | C9—C10—H10A | 109.5 |
S1—Hg1—S4 | 112.32 (3) | C9—C10—H10B | 109.5 |
S3i—Hg1—S2 | 109.11 (2) | H10A—C10—H10B | 109.5 |
S1—Hg1—S2 | 76.26 (2) | C9—C10—H10C | 109.5 |
S4—Hg1—S2 | 97.22 (2) | H10A—C10—H10C | 109.5 |
P1—S1—Hg1 | 92.17 (3) | H10B—C10—H10C | 109.5 |
P1—S2—Hg1 | 79.38 (3) | C9—C11—H11A | 109.5 |
P2—S3—Hg1i | 97.48 (3) | C9—C11—H11B | 109.5 |
P2—S4—Hg1 | 94.61 (4) | H11A—C11—H11B | 109.5 |
O2—P1—C1 | 100.56 (10) | C9—C11—H11C | 109.5 |
O2—P1—S2 | 114.83 (8) | H11A—C11—H11C | 109.5 |
C1—P1—S2 | 114.39 (9) | H11B—C11—H11C | 109.5 |
O2—P1—S1 | 107.71 (8) | C13—C12—C17 | 118.5 (2) |
C1—P1—S1 | 106.96 (9) | C13—C12—P2 | 119.0 (2) |
S2—P1—S1 | 111.53 (4) | C17—C12—P2 | 122.4 (2) |
O4—P2—C12 | 100.50 (10) | C12—C13—C14 | 121.8 (3) |
O4—P2—S4 | 113.62 (8) | C12—C13—H13 | 119.1 |
C12—P2—S4 | 113.57 (10) | C14—C13—H13 | 119.1 |
O4—P2—S3 | 104.78 (8) | C13—C14—C15 | 119.2 (3) |
C12—P2—S3 | 108.57 (10) | C13—C14—H14 | 120.4 |
S4—P2—S3 | 114.56 (4) | C15—C14—H14 | 120.4 |
C4—O1—C7 | 117.9 (2) | O3—C15—C16 | 116.5 (2) |
C9—O2—P1 | 120.41 (15) | O3—C15—C14 | 124.0 (3) |
C15—O3—C18 | 117.1 (2) | C16—C15—C14 | 119.6 (2) |
C20—O4—P2 | 123.35 (15) | C17—C16—C15 | 120.6 (3) |
C6—C1—C2 | 118.4 (2) | C17—C16—H16 | 119.7 |
C6—C1—P1 | 119.55 (19) | C15—C16—H16 | 119.7 |
C2—C1—P1 | 121.8 (2) | C16—C17—C12 | 120.3 (3) |
C3—C2—C1 | 120.4 (2) | C16—C17—H17 | 119.9 |
C3—C2—H2 | 119.8 | C12—C17—H17 | 119.9 |
C1—C2—H2 | 119.8 | O3—C18—C19 | 107.8 (2) |
C2—C3—C4 | 120.3 (2) | O3—C18—H18A | 110.1 |
C2—C3—H3 | 119.8 | C19—C18—H18A | 110.1 |
C4—C3—H3 | 119.8 | O3—C18—H18B | 110.1 |
O1—C4—C5 | 124.2 (2) | C19—C18—H18B | 110.1 |
O1—C4—C3 | 116.0 (2) | H18A—C18—H18B | 108.5 |
C5—C4—C3 | 119.8 (2) | C18—C19—H19A | 109.5 |
C6—C5—C4 | 118.7 (2) | C18—C19—H19B | 109.5 |
C6—C5—H5 | 120.6 | H19A—C19—H19B | 109.5 |
C4—C5—H5 | 120.6 | C18—C19—H19C | 109.5 |
C1—C6—C5 | 122.2 (2) | H19A—C19—H19C | 109.5 |
C1—C6—H6 | 118.9 | H19B—C19—H19C | 109.5 |
C5—C6—H6 | 118.9 | O4—C20—C21 | 108.4 (2) |
O1—C7—C8 | 108.0 (2) | O4—C20—C22 | 105.6 (2) |
O1—C7—H7A | 110.1 | C21—C20—C22 | 113.5 (3) |
C8—C7—H7A | 110.1 | O4—C20—H20 | 109.7 |
O1—C7—H7B | 110.1 | C21—C20—H20 | 109.7 |
C8—C7—H7B | 110.1 | C22—C20—H20 | 109.7 |
H7A—C7—H7B | 108.4 | C20—C21—H21A | 109.5 |
C7—C8—H8A | 109.5 | C20—C21—H21B | 109.5 |
C7—C8—H8B | 109.5 | H21A—C21—H21B | 109.5 |
H8A—C8—H8B | 109.5 | C20—C21—H21C | 109.5 |
C7—C8—H8C | 109.5 | H21A—C21—H21C | 109.5 |
H8A—C8—H8C | 109.5 | H21B—C21—H21C | 109.5 |
H8B—C8—H8C | 109.5 | C20—C22—H22A | 109.5 |
O2—C9—C11 | 107.6 (2) | C20—C22—H22B | 109.5 |
O2—C9—C10 | 106.3 (2) | H22A—C22—H22B | 109.5 |
C11—C9—C10 | 114.4 (2) | C20—C22—H22C | 109.5 |
O2—C9—H9 | 109.5 | H22A—C22—H22C | 109.5 |
C11—C9—H9 | 109.5 | H22B—C22—H22C | 109.5 |
S3i—Hg1—S1—P1 | −110.80 (6) | C1—C2—C3—C4 | −0.9 (5) |
S4—Hg1—S1—P1 | 87.19 (4) | C7—O1—C4—C5 | 2.9 (4) |
S2—Hg1—S1—P1 | −5.07 (3) | C7—O1—C4—C3 | −177.9 (3) |
S3i—Hg1—S2—P1 | 159.53 (3) | C2—C3—C4—O1 | −175.5 (3) |
S1—Hg1—S2—P1 | 5.38 (3) | C2—C3—C4—C5 | 3.7 (4) |
S4—Hg1—S2—P1 | −105.91 (3) | O1—C4—C5—C6 | 175.7 (2) |
S3i—Hg1—S4—P2 | −104.88 (4) | C3—C4—C5—C6 | −3.5 (4) |
S1—Hg1—S4—P2 | 67.51 (4) | C2—C1—C6—C5 | 2.3 (4) |
S2—Hg1—S4—P2 | 145.58 (3) | P1—C1—C6—C5 | −172.3 (2) |
Hg1—S2—P1—O2 | −129.47 (8) | C4—C5—C6—C1 | 0.5 (4) |
Hg1—S2—P1—C1 | 114.96 (9) | C4—O1—C7—C8 | −178.8 (3) |
Hg1—S2—P1—S1 | −6.59 (4) | P1—O2—C9—C11 | −108.9 (2) |
Hg1—S1—P1—O2 | 134.79 (7) | P1—O2—C9—C10 | 128.1 (2) |
Hg1—S1—P1—C1 | −117.84 (8) | O4—P2—C12—C13 | 56.8 (2) |
Hg1—S1—P1—S2 | 7.92 (5) | S4—P2—C12—C13 | 178.5 (2) |
Hg1—S4—P2—O4 | −105.45 (8) | S3—P2—C12—C13 | −52.8 (2) |
Hg1—S4—P2—C12 | 140.49 (9) | O4—P2—C12—C17 | −119.7 (2) |
Hg1—S4—P2—S3 | 14.94 (4) | S4—P2—C12—C17 | 2.0 (3) |
Hg1i—S3—P2—O4 | −165.11 (7) | S3—P2—C12—C17 | 130.7 (2) |
Hg1i—S3—P2—C12 | −58.41 (10) | C17—C12—C13—C14 | 2.3 (4) |
Hg1i—S3—P2—S4 | 69.71 (4) | P2—C12—C13—C14 | −174.3 (2) |
C1—P1—O2—C9 | −173.8 (2) | C12—C13—C14—C15 | −1.1 (4) |
S2—P1—O2—C9 | 62.9 (2) | C18—O3—C15—C16 | 171.0 (3) |
S1—P1—O2—C9 | −62.0 (2) | C18—O3—C15—C14 | −9.7 (4) |
C12—P2—O4—C20 | 167.3 (2) | C13—C14—C15—O3 | 179.3 (3) |
S4—P2—O4—C20 | 45.6 (2) | C13—C14—C15—C16 | −1.4 (4) |
S3—P2—O4—C20 | −80.2 (2) | O3—C15—C16—C17 | −178.1 (2) |
O2—P1—C1—C6 | −158.7 (2) | C14—C15—C16—C17 | 2.5 (4) |
S2—P1—C1—C6 | −35.1 (2) | C15—C16—C17—C12 | −1.2 (4) |
S1—P1—C1—C6 | 89.0 (2) | C13—C12—C17—C16 | −1.2 (4) |
O2—P1—C1—C2 | 26.9 (2) | P2—C12—C17—C16 | 175.3 (2) |
S2—P1—C1—C2 | 150.5 (2) | C15—O3—C18—C19 | −178.4 (2) |
S1—P1—C1—C2 | −85.5 (2) | P2—O4—C20—C21 | 107.9 (2) |
C6—C1—C2—C3 | −2.1 (4) | P2—O4—C20—C22 | −130.0 (2) |
P1—C1—C2—C3 | 172.4 (2) |
Symmetry code: (i) −x+1, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Hg2(C11H16O2PS2)4] |
Mr | 1502.49 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 11.079 (3), 11.985 (3), 12.253 (3) |
α, β, γ (°) | 62.908 (4), 84.418 (4), 80.862 (4) |
V (Å3) | 1429.5 (6) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 5.81 |
Crystal size (mm) | 0.15 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Bruker Kappa DUO APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.476, 0.542 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34157, 6382, 5622 |
Rint | 0.077 |
(sin θ/λ)max (Å−1) | 0.646 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.049, 0.97 |
No. of reflections | 6382 |
No. of parameters | 304 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.87, −1.02 |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008.
Acknowledgements
The authors thank the National Research Foundation (NRF) and UKZN for financial support.
References
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The phosphor-1,1,-dithiolate class of compounds is the heavier and softer congener of the more popular phosphonate derivatives. It contains the S2P functionality as a common feature and several sub-categories are known which include the dithiophosphato [S2P(OR')2]¯, (R' = typically alkyl), dithiophosphinato [S2PR2]¯ (R = alkyl or aryl), and dithiophosphonato [S2PR(OR')]¯, (R = typically aryl or ferrocenyl, R' = alkyl) monoanionic ligands. The latter may be described as a hybrid of the former two, and are also much less developed.
All known Hg(II) complexes with this ligand type are structurally more or less similar, as shown in the Scheme. The complexes are all dinuclear, mercuric, neutral, and 4-coordinate around each metal atom.
General and convenient methods to prepare dithiophosphonate salt derivatives have been reported (Van Zyl & Fackler, 2000). The title complex was formed through the reaction between two Hg2+ cations and four [S2P(4—C6H4OEt)(OiPr)]¯ ligands, the formed complex feature an 8-membered Hg2P2S4 metallo-ring. Two of the ligands bind in a chelating manner and two ligands bind in a bridging manner, both types are anisobidentate, however, due to short and long pairings of the P—S bond and especially the Hg—S bonds.