Bis[μ-O-isopropyl (4-eth­oxy­phen­yl)dithio­phospho­nato-κ2S:S′]bis­{[O-iso­propyl (4-eth­oxy­phen­yl)dithio­phos­phonato-κ2S,S′]mercury(II)}

Sewpersad, S.; Van Zyl, W.E.

doi:10.1107/S1600536812046624

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Pages m1488-m1489

doi:10.1107/S1600536812046624

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Bis[μ-O-isopropyl (4-ethoxyphenyl)dithiophosphonato-κ²S:S′]bis{[O-isopropyl (4-ethoxyphenyl)dithiophosphonato-κ²S,S′]mercury(II)}

Shirveen Sewpersad ^a and Werner E. Van Zyl ^a ^*

^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

(Received 31 October 2012; accepted 12 November 2012; online 17 November 2012)

The title compound, [Hg₂(C₁₁H₁₆O₂PS₂)₄], is a dinuclear complex with a distorted tetrahedral geometry around each Hg^II atom. Although the two Hg^II 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 Hg^II 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 Hg^II 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 Hg^II 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

[Hg₂(C₁₁H₁₆O₂PS₂)₄]
M_r = 1502.49
Triclinic, $[P \overline 1]$
a = 11.079 (3) Å
b = 11.985 (3) Å
c = 12.253 (3) Å
α = 62.908 (4)°
β = 84.418 (4)°
γ = 80.862 (4)°
V = 1429.5 (6) Å³
Z = 1
Mo Kα radiation
μ = 5.81 mm⁻¹
T = 173 K
0.15 × 0.15 × 0.12 mm

Data collection

Bruker Kappa DUO APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.476, T_max = 0.542
34157 measured reflections
6382 independent reflections
5622 reflections with I > 2σ(I)
R_int = 0.077

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.049
S = 0.97
6382 reflections
304 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −1.02 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812046624/ff2088sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046624/ff2088Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: 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.

Figures top

Fig. 1. The ORTEP molecular structure of the title complex, shown with 50% probability.

Bis[µ-O-isopropyl (4-ethoxyphenyl)dithiophosphonato- κ²S:S']bis{[O-isopropyl (4-ethoxyphenyl)dithiophosphonato-κ²S,S']mercury(II)} top

Crystal data top

[Hg₂(C₁₁H₁₆O₂PS₂)₄]	Z = 1
M_r = 1502.49	F(000) = 740
Triclinic, P1	D_x = 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

Data collection top

Bruker Kappa DUO APEXII diffractometer	6382 independent reflections
Radiation source: fine-focus sealed tube	5622 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
0.5° ϕ scans and ω scans	θ_max = 27.4°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −14→14
T_min = 0.476, T_max = 0.542	k = −15→15
34157 measured reflections	l = −15→15

Refinement top

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(F_o²) + (0.017P)²] where P = (F_o² + 2F_c²)/3
6382 reflections	(Δ/σ)_max = 0.002
304 parameters	Δρ_max = 0.87 e Å⁻³
0 restraints	Δρ_min = −1.02 e Å⁻³

Crystal data top

[Hg₂(C₁₁H₁₆O₂PS₂)₄]	γ = 80.862 (4)°
M_r = 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)°

Data collection top

Bruker Kappa DUO APEXII diffractometer	6382 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	5622 reflections with I > 2σ(I)
T_min = 0.476, T_max = 0.542	R_int = 0.077
34157 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.049	H-atom parameters constrained
S = 0.97	Δρ_max = 0.87 e Å⁻³
6382 reflections	Δρ_min = −1.02 e Å⁻³
304 parameters

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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]
M_r	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)
T_min, T_max	0.476, 0.542
No. of measured, independent and observed [I > 2σ(I)] reflections	34157, 6382, 5622
R_int	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
Δρ_max, Δρ_min (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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