Two Cd and Hg peroxodisulfate complexes with aromatic amines

The crystal structures of two complexes containing the peroxodisulfate anion are reported, namely μ-peroxodisulf­ato-1κO:2κO′-bis­[(acetato-κ²O,O′)aqua­(2,2′:6′,2′′-terpyridine-κ³N,N′,N′′)cadmium(II)] hepta­hydrate, [Cd₂(C₂H₃O₂)₂(S₂O₈)(C₁₅H₁₁N₂)₂(H₂O)₂]·7H₂O, (I), and catena-poly[[[bis(2,2′-bipy­ridine-κ²N,N′)mercury(II)]-μ-peroxodisulfato-κ²O:O′] 0.4-hy­drate], {[Hg(C₁₀H₈N₂)₂(S₂O₈)]·0.4H₂O}_n, (II). In both structures, the anion behaves as a bridge, linking neighbouring coordination polyhedra in two different ways, either tightly bound to the hepta­coordinated Cd²⁺ cation forming neatly separated dimeric entities in (I) or across a shorter O—S—O path producing weakly connected chains by way of `semi­coordination' to the Hg²⁺ cations in (II).

S1. Comment

In two preceding articles by the authors (Harvey, Baggio, Garland, Burton & Baggio, 2001; Harvey, Baggio, Garland & Baggio, 2001) dealing with the binding behaviour of peroxodisulfate towards some group XII cations (Cd and Hg), this anion was shown to adopt a variety of different coordination modes (see scheme), namely monodentate (case a), chelate (case b), bridging polymeric (along the anion, case c) or bridging polymeric (across the anion, case d). Some experiments aimed at coordinating this anion to Zn have so far been unsuccessful, although they provide the first examples of peroxodisulfate complexes with the anion fullfilling the role of a stabilizing counterion (Harvey et al., 2004). Continuation of our synthetic trials with group XII metals in combination with nitrogenated ligands has now afforded two new structures, presented here, which display some slightly different binding modes for S₂O₈, viz. bridging dimeric (along the anion), as in [Cd(tpy)(H₂O)(ac)₂(S₂O₈)]·7H₂O, (I), and semicoordinated polymeric (across the anion), as in [Hg(bpy)₂(S₂O₈)]·0.4H₂O, (II), where tpy is 2,2':6',2''-terpyridine, bpy is 2,2'-bipyridine and ac is acetate.

Structure (I) consists of two independent though similarly formulated dinuclear units, each one built up of two symmetry-related [Cd(tpy)(ac)(H₂O)(S₂O₈)_0.5] groups. The symmetry centre halves the peroxodiusulfate anion, which acts as a link between the two cationic centres (Fig. 1). The Cd^II ion is coordinated in the form of a pentagonal bipyramid by the tridentate tpy group, through the amino N atoms N1n, N2n and N3n (n = A or B in the two different moieties), and the bidentate ac, through the carboxylate O atoms O1m and O2m (m = X or Y). The two planar groups bind in a coplanar fashion and define the (planar) pentagonal base, with a mean deviation from the best plane of 0.07 (1)/0.05 (1) Å for moieties A and B, respectively (in what follows, a solidus, /, will separate corresponding values for the independent moieties A and B, respectively). In addition, the two independent base planes are nearly parallel to each other, subtending a dihedral angle of 4.5 (1)°. The external apical position is occupied by one aqua ligand [Cd1—O1W 2.354 (4)/Cd2—O2W 2.328 (5) Å], while the internal one corresponds to the outermost O atom in the stretched peroxodisulfate [Cd1—O1A 2.486 (4)/Cd2—O1B 2.412 (4) Å]. These apical axes are nearly perpendicular to the basal planes, to which they subtend angles of 88.2 (1) and 85.7 (1)/88.6 (1) and 84.3 (1)°.

As observed in almost all the structures where they act as a ligand, the tridentate tpy groups are subject to some strain, being obliged to stretch inwards so as to be able to chelate the cation. Thus, all the sp² angles centred at C5, C6, C10 and C11 (A/B) show a clear asymmetry, those facing the cation being some 5° smaller than the other two. As a possible consequence of this, the tpy molecules deviate somewhat from planarity, mainly though rotations of the aromatic rings along the axis connecting them (maximum angles to the mean plane normal are 8.8 (1)/5.4 (1)° for A/B). Interactions to the metal (Cd—O distances) and the C—O bonds are also self-consistently similar.

Finally, the peroxodisulfate anions bridge the cationic centres, connecting them into the two similar dinuclear moieties building up the structure. There is, however, a qualitative conformational difference between them: each terminal SO₃ group in the anion leans towards its neighbouring aromatic amine in moiety A, but towards the opposite ac group, instead, in moiety B. This difference is shown in Fig. 2, with the least-squares superposition of both molecules. In structure B, internal atom O4B of the peroxodisulfate anion is slightly disordered over three clear positions, of which only the most populated one has been chosen for this representation (see below). The long molecular units [with a 14.79 (1)/14.75 (1) Å separation between outermost aqua O atoms] are linear and almost parallel to each other, the longest axes subtending 11.1 (2)° to each other. They pack with the bulky aromatic amines fitting into the voids of their neighbours, but without significant π–π interaction among pyridine groups. The crystal packing is stabilized through seven independent crystallization water molecules which, together with the two aqua ligands, provide a rich collection of H atoms to which the ac and S₂O₈ O atoms act as acceptors. Unfortunately, it was not possible to locate the hydration water H atoms with any degree of confidence, although it was possible to locate those corresponding to the bound water. In spite of this limitation, the three-dimensional linkages are clear, as shown in Fig. 3, where the water molecules can be seen in the zone z ~0.50. A l l the water O atoms take part in this hydrogen-bonded network, with O···O separations in the expected range of 2.75 (1)–3.11 (1) Å.

The structure bears striking similarities to an anhydrous Hg homologue, [Hg(tpy)(ac)₂(S₂O₈)] Please check brackets, (III) (case c; Harvey, Baggio, Garland & Baggio, 2001). Among the similarities, we note the behaviour of the central O atom in one the S₂O₈ units [O4B in (I) and O4F in (III)]: atom O4B is split over three different sites, while in its Hg counterpart, atom O4F presents an abnormally prolate displacement ellipsoid, some 2.5 times larger than those corresponding to the terminal O atoms. This suggests that the site might be located in a very shallow energy minimum. Both structures present two independent dinuclear entities formed by two hepta-coordinated cations with a pentagonal–bipyramidal environment, both having one tpy and one ac moiety in the planar base and a centrosymmetric S₂O₈ anion stretching all along and joining two cationic centres. However, in (III), these elemental units link to each other through one of the ac O atoms to determine infinite one-dimensional structures, while in (I), this polymeric link is prevented by the site being occupied by a `terminal' aqua ligand.

Structure (II) (Fig. 4) consists of a mercury(II) centre coordinated to two bpy groups, which lie about halfway between a parallel and a perpendicular disposition [the dihedral angle between the best planes is 41.8 (3)°]. A fractional hydration water molecule [site occupancy factor 0.40 (1)] completes the structure. As in the tpy ligands in (I), the bpy groups show chelation strain, both in the small value of the N—C—Csp² angle facing the cation and in the rotation of the pyridine groups around the C5—C6 bonds [4.1 (1)/5.2 (1)° for units A/B, respectively]. These four Hg—N interactions, in the range 2.229 (3)–2.340 (3) Å, provide most of the coordination involvement of Hg, as a bond-valence calculation (Brown & Altermatt, 1985) shows: the four amino N atoms provide ca 1.86 of the expected total of 2. The rest is provided by two peroxodisulfate O atoms lying at very long `semi-coordination' distances [2.703 (3)–2.953 (3) Å] from the cation. A search of the Cambridge Structural Database (CSD, Version?; Allen, 2002) revealed that tetra-coordinated Hg^II cations (according to CSD standard defaults) bound to four N atoms tend to display unusual coordination geometries (sometimes with semi-coordinated O or N ligands at distances in the range 2.70–3.00 Å), as well as bond-valence balances far less than ideal. In Table 5, we present a summary of the results found, which therefore define the HgN₄(O₂) configuration in (II) as normal.

These latter interactions link [Hg(bpy)₂] centres together to form chains along the a axis. The anion does not coordinate alongside, as in structure (I), but sideways, mainly along the shortest bridge, Hg—O1—S1—O3—Hg. A complementary interaction for chain stabilization is the hydrogen bonding, in which the water molecule takes part (Fig. 5 and Table 4), linking neighbouring S₂O₈ groups. A close relative to structure (II) is its Cd homologue [Cd(bpy)₂(S₂O₈)]·H₂O, (IV) (case d; Harvey, Baggio, Garland & Baggio, 2001). They share the same distorted basal coordination of the two bpy groups, while the main structural differences consist in the apical coordination of the anion, which in (IV) is a strong Cd—O bond with a distance only slightly longer than the basal ones. There is, in addition, a diffent character to the water-based (O1W) hydrogen bonds: while in (II) they are intra-chain and provide chain cohesion, in (IV) they are inter-chain, linking neighbouring chains together.

Being strictly centrosymmetric, the S₂O₈ anions in (I) share the property of presenting a perfectly planar S—O—O—S nucleus, which also contains one of the three terminal O atoms at each side (in a trans position to the core), configuring a six member O—S—O—O—S—O planar entity (see previous discussion in Parts 1 and 2 of this series; Harvey, Baggio, Garland, Burton & Baggio, 2001). These latter O atoms are special in that they subtend much smaller O_term—S1—O_core angles than the remaining two O_term terminal O atoms, as can be confirmed from the values reported in Table 1. That this must be a highly preferred conformation is also concluded from the fact that, even when the conformation is not well determined, as in the disordered B moiety in structure (I), the most populated orientation is precisely that which fulfils the referred conditions. The S₂O₈ anion in (II), instead, departs noticeably from planarity [S1—O4—O5—S2 − 54.4 (2)°]. What both compounds share, however, is the special characteristic of the `quasi-trans' O atoms, i.e. those subtending the smallest O_core—O_core—S—O_term torsion angle, also subtending the smallest O_term—S1—O_core angle (Table 3).

S2. Experimental

Compound (I) was obtained by direct mixing of a methanolic solution of 2,2':6',2''-terpyridine with an aqueous solution of cadmium acetate dihydrate and potassium peroxodisulfate in a 1:1:2 molar ratio. Irrespective of mixing order, the preparation readily gave well developed plates of the same compound, (I). Compound (II) was obtained through the slow diffusion of a methanolic solution of 2,2'-bipyridine and mercury(II) acetate into an aqueous solution of potassium peroxodisulfate, all of them 0.025 M. The preparation was kept in a dark environment in order to avoid undesiderable reactions of the Hg^II ion. Though very small colourless needles began to appear immediately at the interface of the two solutions, adequate crystals for X-ray diffraction required almost two months to grow. All starting materials were reagent quality and used without further purification.

S3. Refinement

H atoms defined by the stereochemistry were placed in their calculated positions and allowed to ride on their host C atoms, with C—H_arom = 0.93 and C—H_methyl = 0.96 Å, and with U_iso(H_arom) = 1.2U_eq(C) or U_iso(H_methyl) = 1.5U_eq(C). Those corresponding to aqua in (I) and to the partial hydration water molecule in (II) were located in a Fourier map and refined with similarity restraints and a riding displacement parameter, with O—H = 0.82 (4) and H···H = 1.40 (4) Å, and with U_iso(H_water) = 1.2U_eq(O) The remaining water H atoms in structure (I) could not be confidently located and were accordingly omitted from the model. The rather high residual peak in (II) appears at less than 1 Å from the cation. Four reflections affected by beamstop shadowing were excluded from the refinement in structure (I).

Computing details

For both compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2000); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-PC (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A molecular drawing of the two non-equivalent centrosymmetric dinuclear moieties in (I). Displacement ellipsoids are drawn at the 40% probability level. Full ellipsoids denote the independent atoms and empty ellipsoids the symmetry-related ones.
	Fig. 2. A schematic superposition diagram, showing the different orientation of the S2O8 anions in the independent moieties in (I).
	Fig. 3. A packing view of (I), showing the hydrogen-bonding scheme suggested by OW···OW contacts (see text for details).
	Fig. 4. A molecular drawing of the polymeric structure of (II). Displacement ellipsoids are drawn at the 40% probability level. Full ellipsoids denote the independent atoms and empty ellipsoids the symmetry-related ones. Note the intra-chain hydrogen bond in which atom O1W takes part. [Symmetry code: (i) 1 + x, y, z.]
	Fig. 5. A packing view of (II) down [100], showing the hydrogen-bonding contacts. Note that the O1W intra-chain bonds are almost vertical in this view and, accordingly, rather difficult to see.

(I) µ-peroxodisulfato-1κO:2κO'-bis[(acetato-κ²O,O')aqua(2,2':6',2''- terpyridine-κ³N,N',N'')cadmium(II) heptahydrate

Crystal data

[Cd2(C2H3O2)2(S2O8)(C15H11N3)(H2O)]·7H2O	Z = 2
Mr = 1163.69	F(000) = 1176
Triclinic, P1	Dx = 1.740 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.059 (6) Å	Cell parameters from 2134 reflections
b = 14.254 (7) Å	θ = 3.0–24.5°
c = 14.615 (8) Å	µ = 1.14 mm^−1
α = 87.526 (8)°	T = 297 K
β = 74.913 (8)°	Plate, colourless
γ = 87.249 (8)°	0.40 × 0.30 × 0.15 mm
V = 2221 (2) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	9478 independent reflections
Radiation source: fine-focus sealed tube	6121 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ϕ and ω scans	θmax = 28.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.68, Tmax = 0.84	k = −18→18
18276 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 0.87	w = 1/[σ^2(Fo^2) + (0.067P)^2] where P = (Fo^2 + 2Fc^2)/3
9474 reflections	(Δ/σ)max = 0.005
619 parameters	Δρmax = 0.67 e Å^−3
7 restraints	Δρmin = −0.47 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cd1	0.35588 (3)	1.03447 (2)	0.69944 (2)	0.03595 (11)
Cd2	0.76145 (3)	0.48370 (2)	0.74898 (2)	0.04497 (12)
S1A	0.35674 (10)	0.99955 (8)	0.94202 (8)	0.0353 (3)
O1A	0.4325 (3)	1.0134 (2)	0.8450 (2)	0.0460 (8)
O2A	0.2801 (3)	0.9195 (2)	0.9585 (2)	0.0498 (8)
O3A	0.2997 (3)	1.0846 (2)	0.9840 (2)	0.0546 (9)
O4A	0.4565 (3)	0.9617 (2)	1.0027 (2)	0.0467 (8)
S1B	0.95148 (12)	0.55572 (9)	0.88799 (10)	0.0532 (3)
O1B	0.8753 (3)	0.4851 (2)	0.8687 (3)	0.0602 (10)
O2B	0.8886 (4)	0.6428 (3)	0.9159 (3)	0.0799 (13)
O3B	1.0706 (3)	0.5621 (3)	0.8219 (3)	0.0823 (13)
O4B1	1.044 (2)	0.514 (3)	0.9536 (18)	0.049 (11)	0.22 (3)
O4B2	0.953 (2)	0.4762 (14)	0.9804 (18)	0.074 (9)	0.33 (3)
O4B3	0.9624 (14)	0.5439 (12)	1.0027 (15)	0.062 (6)	0.45 (3)
C1X	0.5622 (4)	1.1310 (4)	0.6000 (3)	0.0426 (11)
C2X	0.6722 (4)	1.1839 (4)	0.5428 (4)	0.0565 (14)
H2XA	0.6584	1.2497	0.5554	0.085*
H2XB	0.6819	1.1748	0.4766	0.085*
H2XC	0.7468	1.1612	0.5599	0.085*
O1X	0.4723 (3)	1.1734 (2)	0.6530 (3)	0.0613 (10)
O2X	0.5624 (3)	1.0428 (2)	0.5937 (3)	0.0567 (9)
C1Y	0.9606 (5)	0.5808 (3)	0.6349 (3)	0.0485 (12)
C2Y	1.0678 (5)	0.6359 (4)	0.5766 (4)	0.0653 (16)
H2YA	1.1322	0.5936	0.5424	0.098*
H2YB	1.1011	0.6722	0.6177	0.098*
H2YC	1.0388	0.6774	0.5326	0.098*
O1Y	0.8664 (3)	0.6239 (2)	0.6850 (3)	0.0586 (10)
O2Y	0.9645 (4)	0.4930 (2)	0.6334 (3)	0.0645 (11)
N1A	0.1922 (3)	1.1414 (3)	0.7766 (3)	0.0421 (9)
N2A	0.1808 (3)	0.9537 (2)	0.7820 (2)	0.0325 (8)
N3A	0.3957 (3)	0.8684 (2)	0.6868 (3)	0.0375 (9)
C1A	0.2008 (5)	1.2346 (3)	0.7741 (4)	0.0584 (15)
H1AA	0.2709	1.2610	0.7334	0.070*
C2A	0.1122 (5)	1.2929 (4)	0.8281 (4)	0.0671 (17)
H2AA	0.1218	1.3576	0.8235	0.081*
C3A	0.0102 (5)	1.2563 (4)	0.8885 (4)	0.0590 (15)
H3AA	−0.0503	1.2952	0.9267	0.071*
C4A	−0.0030 (4)	1.1610 (3)	0.8927 (3)	0.0487 (12)
H4AA	−0.0725	1.1342	0.9337	0.058*
C5A	0.0894 (4)	1.1053 (3)	0.8348 (3)	0.0368 (10)
C6A	0.0803 (4)	1.0009 (3)	0.8333 (3)	0.0371 (10)
C7A	−0.0263 (4)	0.9555 (3)	0.8824 (4)	0.0515 (13)
H7AA	−0.0960	0.9892	0.9172	0.062*
C8A	−0.0264 (4)	0.8599 (3)	0.8782 (4)	0.0545 (14)
H8AA	−0.0970	0.8278	0.9104	0.065*
C9A	0.0777 (4)	0.8109 (3)	0.8266 (4)	0.0519 (13)
H9AA	0.0785	0.7458	0.8240	0.062*
C10A	0.1808 (4)	0.8605 (3)	0.7790 (3)	0.0361 (10)
C11A	0.2995 (4)	0.8131 (3)	0.7246 (3)	0.0392 (10)
C12A	0.3111 (5)	0.7172 (3)	0.7154 (4)	0.0541 (14)
H12A	0.2427	0.6801	0.7410	0.065*
C13A	0.4249 (5)	0.6760 (4)	0.6680 (4)	0.0670 (17)
H13A	0.4344	0.6112	0.6616	0.080*
C14A	0.5229 (5)	0.7330 (4)	0.6309 (4)	0.0645 (16)
H14A	0.6010	0.7074	0.5997	0.077*
C15A	0.5047 (4)	0.8284 (3)	0.6402 (4)	0.0519 (13)
H15A	0.5711	0.8668	0.6129	0.062*
N1B	0.5981 (4)	0.5866 (2)	0.8370 (3)	0.0452 (10)
N2B	0.5880 (3)	0.3997 (2)	0.8353 (3)	0.0414 (9)
N3B	0.8003 (3)	0.3179 (2)	0.7326 (3)	0.0420 (9)
C1B	0.6081 (5)	0.6796 (3)	0.8392 (4)	0.0605 (15)
H1BA	0.6844	0.7057	0.8093	0.073*
C2B	0.5090 (5)	0.7385 (3)	0.8842 (4)	0.0643 (16)
H2BA	0.5188	0.8030	0.8842	0.077*
C3B	0.3988 (5)	0.7012 (4)	0.9277 (4)	0.0640 (16)
H3BA	0.3313	0.7400	0.9576	0.077*
C4B	0.3852 (5)	0.6054 (4)	0.9283 (4)	0.0573 (14)
H4BA	0.3095	0.5787	0.9585	0.069*
C5B	0.4883 (4)	0.5499 (3)	0.8821 (3)	0.0449 (12)
C6B	0.4827 (4)	0.4463 (3)	0.8802 (3)	0.0434 (11)
C7B	0.3758 (4)	0.3988 (4)	0.9249 (4)	0.0572 (14)
H7BA	0.3035	0.4317	0.9569	0.069*
C8B	0.3779 (5)	0.3021 (3)	0.9213 (4)	0.0590 (15)
H8BA	0.3070	0.2692	0.9511	0.071*
C9B	0.4852 (4)	0.2549 (3)	0.8734 (4)	0.0510 (13)
H9BA	0.4873	0.1899	0.8694	0.061*
C10B	0.5905 (4)	0.3055 (3)	0.8311 (3)	0.0412 (11)
C11B	0.7100 (4)	0.2607 (3)	0.7787 (3)	0.0379 (10)
C12B	0.7282 (5)	0.1640 (3)	0.7746 (4)	0.0498 (13)
H12B	0.6652	0.1254	0.8081	0.060*
C13B	0.8389 (5)	0.1245 (3)	0.7214 (4)	0.0532 (13)
H13B	0.8516	0.0596	0.7187	0.064*
C14B	0.9297 (5)	0.1831 (3)	0.6726 (4)	0.0516 (13)
H14B	1.0044	0.1587	0.6344	0.062*
C15B	0.9090 (4)	0.2780 (3)	0.6809 (3)	0.0471 (12)
H15B	0.9726	0.3172	0.6495	0.056*
O1W	0.2780 (3)	1.0387 (2)	0.5640 (2)	0.0470 (8)
H1WA	0.337 (2)	1.025 (3)	0.520 (2)	0.056*
H1WB	0.218 (2)	1.006 (3)	0.567 (3)	0.056*
O2W	0.6706 (4)	0.4928 (3)	0.6214 (3)	0.0748 (12)
H2WA	0.611 (4)	0.461 (4)	0.618 (3)	0.090*
H2WB	0.710 (4)	0.509 (4)	0.5676 (16)	0.090*
O3W	−0.0418 (4)	0.0421 (3)	0.4240 (3)	0.0880 (13)
O4W	0.1974 (4)	0.4100 (3)	0.5445 (3)	0.0844 (13)
O5W	0.1954 (3)	0.2159 (3)	0.5087 (3)	0.0740 (12)
O6W	0.4806 (5)	0.3732 (4)	0.6264 (4)	0.128 (2)
O7W	0.2725 (6)	0.4733 (4)	0.6943 (5)	0.155 (2)
O8W	0.3060 (3)	0.0777 (3)	0.1951 (3)	0.0775 (12)
O9W	0.1356 (4)	0.1810 (3)	0.3366 (3)	0.0721 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02895 (17)	0.03644 (19)	0.0384 (2)	−0.00362 (13)	−0.00098 (14)	−0.00216 (14)
Cd2	0.0454 (2)	0.03277 (19)	0.0466 (2)	−0.00636 (15)	0.00707 (17)	−0.00071 (15)
S1A	0.0300 (6)	0.0363 (6)	0.0376 (6)	−0.0022 (4)	−0.0047 (5)	−0.0015 (5)
O1A	0.0384 (18)	0.062 (2)	0.0364 (18)	−0.0088 (15)	−0.0067 (14)	−0.0013 (15)
O2A	0.0420 (18)	0.0464 (19)	0.061 (2)	−0.0143 (15)	−0.0111 (16)	0.0000 (16)
O3A	0.0425 (19)	0.0417 (19)	0.069 (2)	0.0047 (15)	0.0037 (17)	−0.0041 (17)
O4A	0.0496 (19)	0.0375 (18)	0.057 (2)	−0.0173 (14)	−0.0201 (17)	0.0100 (15)
S1B	0.0507 (8)	0.0527 (8)	0.0540 (9)	−0.0027 (6)	−0.0102 (6)	0.0017 (6)
O1B	0.070 (2)	0.045 (2)	0.066 (3)	−0.0109 (18)	−0.017 (2)	0.0060 (17)
O2B	0.071 (3)	0.059 (2)	0.094 (3)	−0.006 (2)	0.009 (2)	−0.021 (2)
O3B	0.051 (2)	0.081 (3)	0.104 (4)	−0.005 (2)	0.002 (2)	−0.017 (2)
O4B1	0.034 (13)	0.09 (2)	0.023 (14)	−0.003 (13)	−0.010 (9)	0.005 (12)
O4B2	0.084 (15)	0.062 (13)	0.095 (19)	−0.029 (9)	−0.052 (11)	0.013 (9)
O4B3	0.055 (8)	0.054 (9)	0.080 (12)	0.022 (6)	−0.023 (8)	−0.037 (8)
C1X	0.036 (3)	0.053 (3)	0.038 (3)	−0.011 (2)	−0.007 (2)	−0.003 (2)
C2X	0.044 (3)	0.066 (3)	0.053 (3)	−0.021 (3)	0.002 (2)	−0.003 (3)
O1X	0.047 (2)	0.059 (2)	0.066 (3)	−0.0091 (17)	0.0098 (18)	−0.0106 (19)
O2X	0.049 (2)	0.049 (2)	0.064 (2)	−0.0113 (16)	0.0025 (17)	−0.0058 (18)
C1Y	0.053 (3)	0.045 (3)	0.041 (3)	−0.009 (2)	−0.001 (2)	0.003 (2)
C2Y	0.054 (3)	0.054 (3)	0.074 (4)	−0.014 (3)	0.008 (3)	0.006 (3)
O1Y	0.060 (2)	0.047 (2)	0.059 (2)	−0.0070 (17)	0.0030 (19)	0.0037 (17)
O2Y	0.077 (3)	0.041 (2)	0.062 (3)	−0.0114 (18)	0.008 (2)	−0.0012 (17)
N1A	0.031 (2)	0.039 (2)	0.051 (3)	−0.0018 (16)	−0.0020 (17)	−0.0032 (18)
N2A	0.0283 (18)	0.037 (2)	0.031 (2)	−0.0003 (15)	−0.0058 (15)	−0.0033 (16)
N3A	0.0314 (19)	0.040 (2)	0.037 (2)	0.0014 (16)	−0.0021 (16)	−0.0022 (17)
C1A	0.041 (3)	0.039 (3)	0.086 (4)	−0.007 (2)	0.001 (3)	−0.004 (3)
C2A	0.055 (3)	0.044 (3)	0.093 (5)	−0.003 (3)	0.000 (3)	−0.017 (3)
C3A	0.046 (3)	0.049 (3)	0.075 (4)	0.007 (2)	−0.001 (3)	−0.022 (3)
C4A	0.043 (3)	0.049 (3)	0.049 (3)	0.004 (2)	−0.002 (2)	−0.008 (2)
C5A	0.030 (2)	0.041 (3)	0.039 (3)	0.0030 (19)	−0.0073 (19)	−0.006 (2)
C6A	0.028 (2)	0.043 (3)	0.039 (3)	−0.0041 (19)	−0.0072 (19)	0.001 (2)
C7A	0.033 (3)	0.045 (3)	0.066 (4)	−0.003 (2)	0.006 (2)	−0.002 (2)
C8A	0.035 (3)	0.047 (3)	0.071 (4)	−0.007 (2)	0.006 (2)	0.005 (3)
C9A	0.046 (3)	0.041 (3)	0.063 (4)	−0.010 (2)	−0.004 (3)	−0.001 (2)
C10A	0.030 (2)	0.040 (3)	0.036 (3)	−0.0027 (19)	−0.0051 (19)	−0.001 (2)
C11A	0.035 (2)	0.040 (3)	0.040 (3)	−0.003 (2)	−0.006 (2)	−0.004 (2)
C12A	0.047 (3)	0.043 (3)	0.065 (4)	−0.007 (2)	0.000 (3)	−0.004 (3)
C13A	0.059 (3)	0.037 (3)	0.093 (5)	0.005 (2)	0.002 (3)	−0.009 (3)
C14A	0.050 (3)	0.051 (3)	0.081 (4)	0.005 (3)	0.004 (3)	−0.003 (3)
C15A	0.040 (3)	0.044 (3)	0.063 (4)	−0.003 (2)	0.002 (2)	0.002 (2)
N1B	0.049 (2)	0.030 (2)	0.048 (2)	−0.0021 (17)	0.0036 (19)	−0.0042 (17)
N2B	0.042 (2)	0.033 (2)	0.041 (2)	−0.0038 (17)	0.0046 (18)	0.0013 (17)
N3B	0.044 (2)	0.033 (2)	0.044 (2)	−0.0069 (17)	−0.0014 (18)	−0.0006 (17)
C1B	0.062 (3)	0.041 (3)	0.067 (4)	−0.007 (3)	0.006 (3)	−0.001 (3)
C2B	0.072 (4)	0.031 (3)	0.078 (4)	−0.001 (3)	0.002 (3)	−0.008 (3)
C3B	0.071 (4)	0.039 (3)	0.070 (4)	0.013 (3)	0.003 (3)	−0.012 (3)
C4B	0.048 (3)	0.051 (3)	0.061 (4)	0.004 (2)	0.009 (3)	−0.006 (3)
C5B	0.045 (3)	0.038 (3)	0.044 (3)	0.000 (2)	0.004 (2)	−0.004 (2)
C6B	0.043 (3)	0.035 (2)	0.044 (3)	−0.005 (2)	0.003 (2)	0.000 (2)
C7B	0.039 (3)	0.058 (3)	0.061 (4)	−0.002 (2)	0.011 (2)	0.001 (3)
C8B	0.049 (3)	0.046 (3)	0.069 (4)	−0.018 (2)	0.009 (3)	0.003 (3)
C9B	0.052 (3)	0.038 (3)	0.056 (3)	−0.012 (2)	0.000 (2)	−0.001 (2)
C10B	0.045 (3)	0.034 (2)	0.039 (3)	−0.007 (2)	0.001 (2)	−0.001 (2)
C11B	0.042 (3)	0.031 (2)	0.037 (3)	−0.0048 (19)	−0.002 (2)	−0.0009 (19)
C12B	0.053 (3)	0.033 (3)	0.056 (3)	−0.004 (2)	−0.001 (2)	0.002 (2)
C13B	0.055 (3)	0.038 (3)	0.062 (4)	0.004 (2)	−0.007 (3)	−0.007 (2)
C14B	0.044 (3)	0.044 (3)	0.057 (3)	0.008 (2)	0.002 (2)	−0.003 (2)
C15B	0.042 (3)	0.043 (3)	0.047 (3)	−0.003 (2)	0.004 (2)	0.000 (2)
O1W	0.0407 (19)	0.057 (2)	0.040 (2)	−0.0060 (16)	−0.0038 (15)	−0.0029 (16)
O2W	0.073 (3)	0.087 (3)	0.060 (3)	−0.020 (2)	−0.009 (2)	0.013 (2)
O3W	0.069 (3)	0.090 (3)	0.101 (4)	−0.014 (2)	−0.015 (3)	0.004 (3)
O4W	0.099 (3)	0.071 (3)	0.064 (3)	−0.006 (2)	0.013 (2)	0.005 (2)
O5W	0.062 (2)	0.076 (3)	0.074 (3)	0.007 (2)	−0.003 (2)	0.008 (2)
O6W	0.119 (4)	0.093 (4)	0.160 (6)	−0.034 (3)	−0.007 (4)	−0.006 (4)
O7W	0.129 (5)	0.111 (5)	0.210 (7)	0.001 (4)	−0.019 (5)	−0.004 (4)
O8W	0.059 (2)	0.062 (2)	0.099 (3)	−0.0041 (19)	0.005 (2)	−0.020 (2)
O9W	0.078 (3)	0.064 (2)	0.065 (3)	−0.007 (2)	0.000 (2)	0.004 (2)

Geometric parameters (Å, º)

Cd1—N2A	2.326 (3)	C4A—H4AA	0.9300
Cd1—O1W	2.353 (4)	C5A—C6A	1.497 (6)
Cd1—N1A	2.385 (4)	C6A—C7A	1.384 (6)
Cd1—O1X	2.390 (3)	C7A—C8A	1.367 (7)
Cd1—N3A	2.393 (4)	C7A—H7AA	0.9300
Cd1—O2X	2.407 (3)	C8A—C9A	1.378 (6)
Cd1—O1A	2.489 (3)	C8A—H8AA	0.9300
Cd2—O2W	2.332 (4)	C9A—C10A	1.380 (6)
Cd2—N2B	2.352 (4)	C9A—H9AA	0.9300
Cd2—N3B	2.393 (4)	C10A—C11A	1.493 (6)
Cd2—O1Y	2.390 (3)	C11A—C12A	1.376 (6)
Cd2—N1B	2.402 (4)	C12A—C13A	1.386 (7)
Cd2—O1B	2.408 (4)	C12A—H12A	0.9300
Cd2—O2Y	2.439 (4)	C13A—C14A	1.367 (7)
S1A—O2A	1.428 (3)	C13A—H13A	0.9300
S1A—O3A	1.426 (3)	C14A—C15A	1.373 (7)
S1A—O1A	1.457 (3)	C14A—H14A	0.9300
S1A—O4A	1.645 (3)	C15A—H15A	0.9300
O4A—O4A^i	1.477 (5)	N1B—C1B	1.337 (6)
S1B—O2B	1.416 (4)	N1B—C5B	1.341 (5)
S1B—O3B	1.421 (4)	N2B—C10B	1.346 (5)
S1B—O1B	1.426 (4)	N2B—C6B	1.340 (5)
S1B—O4B1	1.65 (3)	N3B—C11B	1.340 (5)
S1B—O4B3	1.71 (2)	N3B—C15B	1.355 (6)
S1B—O4B2	1.73 (2)	C1B—C2B	1.387 (7)
O4B1—O4B1^ii	1.49 (5)	C1B—H1BA	0.9300
O4B2—O4B2^ii	1.51 (4)	C2B—C3B	1.344 (7)
O4B3—O4B3^ii	1.46 (3)	C2B—H2BA	0.9300
C1X—O1X	1.239 (5)	C3B—C4B	1.380 (7)
C1X—O2X	1.264 (6)	C3B—H3BA	0.9300
C1X—C2X	1.501 (6)	C4B—C5B	1.392 (6)
C2X—H2XA	0.9600	C4B—H4BA	0.9300
C2X—H2XB	0.9600	C5B—C6B	1.483 (6)
C2X—H2XC	0.9600	C6B—C7B	1.385 (6)
C1Y—O2Y	1.251 (6)	C7B—C8B	1.380 (7)
C1Y—O1Y	1.256 (6)	C7B—H7BA	0.9300
C1Y—C2Y	1.502 (6)	C8B—C9B	1.372 (7)
C2Y—H2YA	0.9600	C8B—H8BA	0.9300
C2Y—H2YB	0.9600	C9B—C10B	1.388 (6)
C2Y—H2YC	0.9600	C9B—H9BA	0.9300
N1A—C5A	1.340 (5)	C10B—C11B	1.474 (6)
N1A—C1A	1.335 (6)	C11B—C12B	1.386 (6)
N2A—C10A	1.331 (5)	C12B—C13B	1.377 (6)
N2A—C6A	1.338 (5)	C12B—H12B	0.9300
N3A—C15A	1.335 (5)	C13B—C14B	1.368 (6)
N3A—C11A	1.341 (5)	C13B—H13B	0.9300
C1A—C2A	1.361 (7)	C14B—C15B	1.366 (6)
C1A—H1AA	0.9300	C14B—H14B	0.9300
C2A—C3A	1.349 (7)	C15B—H15B	0.9300
C2A—H2AA	0.9300	O1W—H1WA	0.82 (4)
C3A—C4A	1.370 (7)	O1W—H1WB	0.82 (4)
C3A—H3AA	0.9300	O2W—H2WA	0.83 (4)
C4A—C5A	1.386 (6)	O2W—H2WB	0.82 (4)
N2A—Cd1—O1W	89.18 (12)	C3A—C2A—H2AA	120.2
N2A—Cd1—N1A	69.38 (12)	C1A—C2A—H2AA	120.2
O1W—Cd1—N1A	90.98 (13)	C2A—C3A—C4A	119.1 (5)
N2A—Cd1—O1X	153.26 (12)	C2A—C3A—H3AA	120.4
O1W—Cd1—O1X	94.13 (13)	C4A—C3A—H3AA	120.4
N1A—Cd1—O1X	84.02 (12)	C3A—C4A—C5A	118.7 (5)
N2A—Cd1—N3A	69.34 (12)	C3A—C4A—H4AA	120.6
O1W—Cd1—N3A	90.43 (12)	C5A—C4A—H4AA	120.6
N1A—Cd1—N3A	138.66 (12)	N1A—C5A—C4A	122.2 (4)
O1X—Cd1—N3A	137.03 (12)	N1A—C5A—C6A	115.9 (4)
N2A—Cd1—O2X	152.89 (12)	C4A—C5A—C6A	122.0 (4)
O1W—Cd1—O2X	87.39 (12)	N2A—C6A—C7A	121.6 (4)
N1A—Cd1—O2X	137.54 (12)	N2A—C6A—C5A	116.5 (4)
O1X—Cd1—O2X	53.85 (11)	C7A—C6A—C5A	121.9 (4)
N3A—Cd1—O2X	83.80 (11)	C8A—C7A—C6A	118.2 (4)
N2A—Cd1—O1A	86.75 (11)	C8A—C7A—H7AA	120.9
O1W—Cd1—O1A	174.31 (11)	C6A—C7A—H7AA	120.9
N1A—Cd1—O1A	91.30 (12)	C9A—C8A—C7A	120.3 (4)
O1X—Cd1—O1A	91.29 (12)	C9A—C8A—H8AA	119.9
N3A—Cd1—O1A	84.42 (12)	C7A—C8A—H8AA	119.9
O2X—Cd1—O1A	94.44 (12)	C8A—C9A—C10A	118.6 (5)
O2W—Cd2—N2B	88.23 (14)	C8A—C9A—H9AA	120.7
O2W—Cd2—N3B	91.36 (15)	C10A—C9A—H9AA	120.7
N2B—Cd2—N3B	68.73 (12)	N2A—C10A—C9A	121.3 (4)
O2W—Cd2—O1Y	87.31 (14)	N2A—C10A—C11A	116.3 (4)
N2B—Cd2—O1Y	153.80 (12)	C9A—C10A—C11A	122.3 (4)
N3B—Cd2—O1Y	137.16 (12)	N3A—C11A—C12A	121.4 (4)
O2W—Cd2—N1B	90.46 (16)	N3A—C11A—C10A	116.6 (4)
N2B—Cd2—N1B	68.42 (13)	C12A—C11A—C10A	121.9 (4)
N3B—Cd2—N1B	137.03 (12)	C11A—C12A—C13A	119.8 (5)
O1Y—Cd2—N1B	85.81 (13)	C11A—C12A—H12A	120.1
O2W—Cd2—O1B	173.10 (12)	C13A—C12A—H12A	120.1
N2B—Cd2—O1B	98.68 (13)	C14A—C13A—C12A	118.3 (5)
N3B—Cd2—O1B	91.28 (12)	C14A—C13A—H13A	120.8
O1Y—Cd2—O1B	86.42 (12)	C12A—C13A—H13A	120.8
N1B—Cd2—O1B	91.96 (13)	C13A—C14A—C15A	119.2 (5)
O2W—Cd2—O2Y	87.46 (15)	C13A—C14A—H14A	120.4
N2B—Cd2—O2Y	151.92 (12)	C15A—C14A—H14A	120.4
N3B—Cd2—O2Y	83.65 (12)	N3A—C15A—C14A	122.8 (5)
O1Y—Cd2—O2Y	53.52 (11)	N3A—C15A—H15A	118.6
N1B—Cd2—O2Y	139.33 (12)	C14A—C15A—H15A	118.6
O1B—Cd2—O2Y	86.49 (13)	C1B—N1B—C5B	117.9 (4)
O2A—S1A—O3A	116.5 (2)	C1B—N1B—Cd2	123.5 (3)
O2A—S1A—O1A	115.4 (2)	C5B—N1B—Cd2	118.4 (3)
O3A—S1A—O1A	113.2 (2)	C10B—N2B—C6B	120.1 (4)
O2A—S1A—O4A	97.83 (17)	C10B—N2B—Cd2	119.7 (3)
O3A—S1A—O4A	106.4 (2)	C6B—N2B—Cd2	119.8 (3)
O1A—S1A—O4A	105.07 (18)	C11B—N3B—C15B	117.9 (4)
S1A—O1A—Cd1	126.97 (17)	C11B—N3B—Cd2	118.1 (3)
O4A^i—O4A—S1A	106.2 (3)	C15B—N3B—Cd2	124.0 (3)
O2B—S1B—O3B	115.2 (2)	N1B—C1B—C2B	122.5 (5)
O2B—S1B—O1B	115.4 (2)	N1B—C1B—H1BA	118.7
O3B—S1B—O1B	114.6 (2)	C2B—C1B—H1BA	118.7
O2B—S1B—O4B1	115.6 (12)	C3B—C2B—C1B	119.0 (5)
O3B—S1B—O4B1	79.4 (8)	C3B—C2B—H2BA	120.5
O1B—S1B—O4B1	111.7 (13)	C1B—C2B—H2BA	120.5
O2B—S1B—O4B3	85.3 (5)	C2B—C3B—C4B	120.2 (5)
O3B—S1B—O4B3	112.4 (6)	C2B—C3B—H3BA	119.9
O1B—S1B—O4B3	110.4 (6)	C4B—C3B—H3BA	119.9
O2B—S1B—O4B2	114.7 (9)	C3B—C4B—C5B	118.0 (5)
O3B—S1B—O4B2	112.6 (8)	C3B—C4B—H4BA	121.0
O1B—S1B—O4B2	79.5 (7)	C5B—C4B—H4BA	121.0
S1B—O1B—Cd2	129.6 (2)	N1B—C5B—C4B	122.3 (4)
O4B1^ii—O4B1—S1B	105 (2)	N1B—C5B—C6B	116.1 (4)
O4B2^ii—O4B2—S1B	97.6 (16)	C4B—C5B—C6B	121.7 (4)
O4B3^ii—O4B3—S1B	100.0 (15)	N2B—C6B—C7B	121.0 (4)
O1X—C1X—O2X	120.5 (4)	N2B—C6B—C5B	116.7 (4)
O1X—C1X—C2X	120.2 (5)	C7B—C6B—C5B	122.3 (4)
O2X—C1X—C2X	119.3 (4)	C8B—C7B—C6B	119.1 (5)
C1X—C2X—H2XA	109.5	C8B—C7B—H7BA	120.4
C1X—C2X—H2XB	109.5	C6B—C7B—H7BA	120.4
H2XA—C2X—H2XB	109.5	C9B—C8B—C7B	119.6 (4)
C1X—C2X—H2XC	109.5	C9B—C8B—H8BA	120.2
H2XA—C2X—H2XC	109.5	C7B—C8B—H8BA	120.2
H2XB—C2X—H2XC	109.5	C8B—C9B—C10B	119.1 (4)
C1X—O1X—Cd1	93.5 (3)	C8B—C9B—H9BA	120.4
C1X—O2X—Cd1	92.1 (3)	C10B—C9B—H9BA	120.4
O2Y—C1Y—O1Y	120.3 (4)	N2B—C10B—C9B	120.9 (4)
O2Y—C1Y—C2Y	120.5 (5)	N2B—C10B—C11B	116.1 (4)
O1Y—C1Y—C2Y	119.2 (5)	C9B—C10B—C11B	122.9 (4)
C1Y—C2Y—H2YA	109.5	N3B—C11B—C12B	120.8 (4)
C1Y—C2Y—H2YB	109.5	N3B—C11B—C10B	117.1 (4)
H2YA—C2Y—H2YB	109.5	C12B—C11B—C10B	122.1 (4)
C1Y—C2Y—H2YC	109.5	C13B—C12B—C11B	120.6 (4)
H2YA—C2Y—H2YC	109.5	C13B—C12B—H12B	119.7
H2YB—C2Y—H2YC	109.5	C11B—C12B—H12B	119.7
C1Y—O1Y—Cd2	94.2 (3)	C14B—C13B—C12B	118.3 (5)
C1Y—O2Y—Cd2	92.0 (3)	C14B—C13B—H13B	120.8
C5A—N1A—C1A	117.1 (4)	C12B—C13B—H13B	120.8
C5A—N1A—Cd1	117.8 (3)	C15B—C14B—C13B	119.1 (5)
C1A—N1A—Cd1	124.7 (3)	C15B—C14B—H14B	120.5
C10A—N2A—C6A	119.9 (4)	C13B—C14B—H14B	120.5
C10A—N2A—Cd1	120.2 (3)	N3B—C15B—C14B	123.2 (4)
C6A—N2A—Cd1	119.9 (3)	N3B—C15B—H15B	118.4
C15A—N3A—C11A	118.5 (4)	C14B—C15B—H15B	118.4
C15A—N3A—Cd1	124.2 (3)	Cd1—O1W—H1WA	106 (3)
C11A—N3A—Cd1	117.2 (3)	Cd1—O1W—H1WB	116 (3)
N1A—C1A—C2A	123.3 (5)	H1WA—O1W—H1WB	112 (4)
N1A—C1A—H1AA	118.4	Cd2—O2W—H2WA	124 (4)
C2A—C1A—H1AA	118.4	Cd2—O2W—H2WB	122 (4)
C3A—C2A—C1A	119.5 (5)	H2WA—O2W—H2WB	109 (4)
O1A—S1A—O4A—O4A^iii	−15.33 (13)	O1B—S1B—O4B2—O4B2^iv	−22.0 (6)
O2A—S1A—O4A—O4A^iii	103.69 (16)	O2B—S1B—O4B2—O4B2^iv	91.3 (6)
O3A—S1A—O4A—O4A^iii	−135.63 (18)	O3B—S1B—O4B2—O4B2^iv	−134.3 (7)
O1B—S1B—O4B1—O4B1^iv	−11.9 (14)	O1B—S1B—O4B3—O4B3^iv	−42.5 (4)
O2B—S1B—O4B1—O4B1^iv	122.7 (18)	O2B—S1B—O4B3—O4B3^iv	72.9 (5)
O3B—S1B—O4B1—O4B1^iv	−124.3 (16)	O3B—S1B—O4B3—O4B3^iv	−171.7 (7)

Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+2, −y+1, −z+2; (iii) −x+1, −y+2, −z+1; (iv) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2X^iii	0.82 (4)	1.99 (4)	2.774 (5)	159 (4)
O1W—H1WB···O3W^iv	0.82 (4)	2.07 (4)	2.866 (5)	165 (5)
O2W—H2WA···O6W	0.83 (4)	1.93 (4)	2.754 (6)	171 (6)
O2W—H2WB···O4W^v	0.82 (4)	2.04 (4)	2.827 (6)	161 (6)

Symmetry codes: (iii) −x+1, −y+2, −z+1; (iv) −x, −y+1, −z+1; (v) −x+1, −y+1, −z+1.

(II) catena-poly[[[bis(2,2'-bipyridine-κ²N,N')mercury(II)]-µ-peroxodisulfato- κ²O:O'] 0.4-hydrate]

Crystal data

[Hg(C10H8N2)2(O8S2)]·0.4H2O	F(000) = 1376
Mr = 712.28	Dx = 2.112 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2344 reflections
a = 7.3340 (11) Å	θ = 3.1–22.7°
b = 30.125 (6) Å	µ = 7.12 mm^−1
c = 10.4340 (17) Å	T = 297 K
β = 103.689 (15)°	Needle, colourless
V = 2239.8 (7) Å^3	0.50 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	4938 independent reflections
Radiation source: fine-focus sealed tube	4000 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 28.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.20, Tmax = 0.50	k = −37→39
13178 measured reflections	l = −13→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 0.84	w = 1/[σ^2(Fo^2) + (0.035P)^2] where P = (Fo^2 + 2Fc^2)/3
4938 reflections	(Δ/σ)max = 0.012
332 parameters	Δρmax = 1.41 e Å^−3
4 restraints	Δρmin = −0.72 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Hg1	0.58598 (2)	0.134014 (4)	0.411176 (15)	0.03693 (6)
S1	0.11191 (13)	0.13232 (3)	0.40925 (9)	0.0345 (2)
S2	−0.15321 (16)	0.10384 (3)	0.06340 (10)	0.0411 (2)
O1	0.2183 (4)	0.15490 (9)	0.3295 (3)	0.0469 (7)
O2	0.2204 (4)	0.10251 (9)	0.5050 (3)	0.0495 (7)
O3	−0.0162 (4)	0.16044 (8)	0.4552 (3)	0.0466 (7)
O4	−0.0180 (4)	0.09509 (7)	0.3123 (2)	0.0384 (6)
O5	−0.1627 (4)	0.11929 (9)	0.2149 (3)	0.0435 (7)
O6	0.0108 (5)	0.12427 (11)	0.0378 (3)	0.0677 (10)
O7	−0.1519 (5)	0.05695 (9)	0.0632 (3)	0.0673 (9)
O8	−0.3275 (5)	0.12412 (11)	−0.0029 (3)	0.0717 (10)
N1A	0.5151 (4)	0.06822 (9)	0.3137 (3)	0.0349 (7)
N2A	0.7551 (4)	0.08067 (9)	0.5529 (3)	0.0377 (7)
C1A	0.3953 (6)	0.06403 (14)	0.1958 (4)	0.0440 (10)
H1AA	0.3278	0.0887	0.1576	0.053*
C2A	0.3692 (6)	0.02447 (14)	0.1300 (4)	0.0514 (11)
H2AA	0.2845	0.0223	0.0483	0.062*
C3A	0.4693 (6)	−0.01192 (13)	0.1856 (5)	0.0492 (11)
H3AA	0.4566	−0.0389	0.1410	0.059*
C4A	0.5899 (6)	−0.00806 (12)	0.3095 (4)	0.0426 (10)
H4AA	0.6555	−0.0327	0.3498	0.051*
C5A	0.6120 (5)	0.03268 (11)	0.3727 (4)	0.0331 (8)
C6A	0.7366 (5)	0.03912 (11)	0.5057 (4)	0.0322 (8)
C7A	0.8301 (6)	0.00434 (12)	0.5800 (4)	0.0394 (9)
H7AA	0.8168	−0.0244	0.5466	0.047*
C8A	0.9421 (6)	0.01231 (13)	0.7029 (4)	0.0468 (10)
H8AA	1.0046	−0.0109	0.7539	0.056*
C9A	0.9608 (6)	0.05524 (13)	0.7497 (4)	0.0475 (10)
H9AA	1.0372	0.0616	0.8323	0.057*
C10A	0.8647 (6)	0.08822 (13)	0.6725 (4)	0.0486 (11)
H10A	0.8762	0.1172	0.7045	0.058*
N1B	0.5838 (4)	0.20230 (9)	0.3285 (3)	0.0339 (7)
N2B	0.5553 (4)	0.18388 (9)	0.5769 (3)	0.0364 (7)
C1B	0.5835 (6)	0.20982 (13)	0.2020 (4)	0.0457 (10)
H1BA	0.5916	0.1857	0.1479	0.055*
C2B	0.5717 (7)	0.25141 (14)	0.1495 (4)	0.0553 (12)
H2BA	0.5697	0.2556	0.0609	0.066*
C3B	0.5629 (7)	0.28699 (13)	0.2299 (5)	0.0561 (12)
H3BA	0.5573	0.3157	0.1968	0.067*
C4B	0.5625 (6)	0.27972 (12)	0.3599 (4)	0.0432 (10)
H4BA	0.5560	0.3036	0.4152	0.052*
C5B	0.5717 (5)	0.23702 (12)	0.4077 (4)	0.0336 (8)
C6B	0.5667 (5)	0.22705 (11)	0.5458 (4)	0.0340 (8)
C7B	0.5678 (6)	0.25949 (12)	0.6389 (4)	0.0466 (10)
H7BA	0.5737	0.2893	0.6166	0.056*
C8B	0.5601 (7)	0.24782 (13)	0.7644 (4)	0.0574 (12)
H8BA	0.5622	0.2696	0.8280	0.069*
C9B	0.5493 (7)	0.20356 (13)	0.7958 (4)	0.0554 (12)
H9BA	0.5438	0.1949	0.8804	0.066*
C10B	0.5468 (6)	0.17285 (13)	0.6996 (4)	0.0466 (10)
H10B	0.5389	0.1430	0.7201	0.056*
O1W	0.2977 (19)	0.1213 (5)	−0.1050 (15)	0.128 (4)	0.3994 (10)
H1WA	0.27 (2)	0.139 (6)	−0.054 (17)	0.154*	0.3994 (10)
H1WB	0.412 (5)	0.118 (6)	−0.089 (19)	0.154*	0.3994 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Hg1	0.04327 (10)	0.02325 (8)	0.04336 (11)	0.00279 (6)	0.00844 (7)	0.00078 (6)
S1	0.0390 (6)	0.0278 (5)	0.0351 (5)	0.0003 (4)	0.0054 (4)	−0.0021 (4)
S2	0.0516 (6)	0.0358 (5)	0.0330 (5)	0.0024 (4)	0.0040 (4)	0.0005 (4)
O1	0.0392 (16)	0.0450 (15)	0.0570 (19)	−0.0038 (13)	0.0124 (14)	0.0051 (14)
O2	0.0594 (19)	0.0376 (14)	0.0429 (17)	0.0054 (13)	−0.0053 (14)	0.0054 (13)
O3	0.0510 (18)	0.0391 (15)	0.0501 (18)	0.0054 (13)	0.0131 (14)	−0.0085 (13)
O4	0.0490 (16)	0.0290 (13)	0.0340 (15)	−0.0018 (12)	0.0031 (12)	0.0004 (12)
O5	0.0371 (16)	0.0517 (15)	0.0402 (17)	0.0106 (13)	0.0065 (13)	−0.0001 (14)
O6	0.072 (2)	0.085 (2)	0.050 (2)	−0.0136 (18)	0.0240 (19)	−0.0036 (18)
O7	0.101 (3)	0.0375 (16)	0.049 (2)	−0.0026 (17)	−0.0110 (18)	−0.0052 (14)
O8	0.069 (2)	0.077 (2)	0.054 (2)	0.0233 (18)	−0.0142 (18)	0.0052 (18)
N1A	0.0354 (18)	0.0310 (15)	0.0391 (19)	0.0021 (13)	0.0103 (15)	−0.0013 (14)
N2A	0.0401 (19)	0.0259 (15)	0.045 (2)	0.0010 (13)	0.0054 (15)	−0.0023 (14)
C1A	0.042 (2)	0.046 (2)	0.043 (3)	0.0014 (18)	0.007 (2)	0.003 (2)
C2A	0.052 (3)	0.057 (3)	0.044 (3)	−0.007 (2)	0.010 (2)	−0.008 (2)
C3A	0.058 (3)	0.037 (2)	0.055 (3)	−0.004 (2)	0.018 (2)	−0.013 (2)
C4A	0.043 (2)	0.034 (2)	0.053 (3)	0.0008 (17)	0.015 (2)	−0.0035 (19)
C5A	0.032 (2)	0.0304 (18)	0.041 (2)	−0.0008 (15)	0.0171 (17)	−0.0009 (17)
C6A	0.031 (2)	0.0288 (18)	0.040 (2)	0.0002 (14)	0.0142 (17)	0.0004 (16)
C7A	0.048 (2)	0.0273 (18)	0.047 (3)	0.0045 (17)	0.018 (2)	0.0050 (18)
C8A	0.050 (3)	0.044 (2)	0.047 (3)	0.0125 (19)	0.014 (2)	0.014 (2)
C9A	0.043 (2)	0.052 (3)	0.044 (3)	0.001 (2)	0.003 (2)	0.005 (2)
C10A	0.052 (3)	0.037 (2)	0.054 (3)	−0.0051 (19)	0.008 (2)	−0.006 (2)
N1B	0.0344 (18)	0.0281 (15)	0.0388 (19)	0.0045 (13)	0.0079 (14)	0.0019 (14)
N2B	0.0454 (19)	0.0287 (15)	0.0334 (18)	−0.0009 (13)	0.0063 (15)	0.0022 (14)
C1B	0.059 (3)	0.038 (2)	0.042 (3)	0.0080 (19)	0.014 (2)	−0.0005 (19)
C2B	0.079 (4)	0.051 (3)	0.038 (3)	0.011 (2)	0.019 (2)	0.010 (2)
C3B	0.079 (4)	0.037 (2)	0.056 (3)	0.012 (2)	0.024 (3)	0.014 (2)
C4B	0.061 (3)	0.030 (2)	0.039 (2)	0.0057 (18)	0.012 (2)	0.0018 (18)
C5B	0.030 (2)	0.0314 (18)	0.037 (2)	0.0026 (15)	0.0044 (16)	0.0011 (16)
C6B	0.035 (2)	0.0282 (18)	0.037 (2)	0.0015 (15)	0.0058 (17)	0.0015 (16)
C7B	0.063 (3)	0.032 (2)	0.046 (3)	−0.0003 (19)	0.014 (2)	−0.0017 (19)
C8B	0.092 (4)	0.041 (2)	0.043 (3)	−0.002 (2)	0.023 (3)	−0.009 (2)
C9B	0.088 (4)	0.039 (2)	0.041 (3)	0.000 (2)	0.020 (2)	0.005 (2)
C10B	0.060 (3)	0.039 (2)	0.041 (3)	0.0007 (19)	0.011 (2)	0.0069 (19)
O1W	0.086 (8)	0.159 (13)	0.133 (12)	−0.015 (9)	0.011 (8)	0.047 (10)

Geometric parameters (Å, º)

Hg1—N1B	2.229 (3)	C7A—H7AA	0.9300
Hg1—N1A	2.232 (3)	C8A—C9A	1.378 (5)
Hg1—N2A	2.332 (3)	C8A—H8AA	0.9300
Hg1—N2B	2.341 (3)	C9A—C10A	1.366 (5)
Hg1—O1	2.703 (3)	C9A—H9AA	0.9300
Hg1—O3^i	2.953 (3)	C10A—H10A	0.9300
S1—O3	1.430 (3)	N1B—C1B	1.338 (5)
S1—O2	1.436 (3)	N1B—C5B	1.349 (4)
S1—O1	1.439 (3)	N2B—C10B	1.339 (5)
S1—O4	1.653 (3)	N2B—C6B	1.348 (4)
S2—O7	1.413 (3)	C1B—C2B	1.362 (5)
S2—O6	1.431 (3)	C1B—H1BA	0.9300
S2—O8	1.438 (3)	C2B—C3B	1.372 (6)
S2—O5	1.665 (3)	C2B—H2BA	0.9300
O4—O5	1.477 (3)	C3B—C4B	1.374 (6)
N1A—C1A	1.338 (5)	C3B—H3BA	0.9300
N1A—C5A	1.350 (4)	C4B—C5B	1.376 (5)
N2A—C10A	1.334 (5)	C4B—H4BA	0.9300
N2A—C6A	1.340 (4)	C5B—C6B	1.481 (5)
C1A—C2A	1.366 (5)	C6B—C7B	1.376 (5)
C1A—H1AA	0.9300	C7B—C8B	1.370 (5)
C2A—C3A	1.370 (6)	C7B—H7BA	0.9300
C2A—H2AA	0.9300	C8B—C9B	1.380 (5)
C3A—C4A	1.387 (6)	C8B—H8BA	0.9300
C3A—H3AA	0.9300	C9B—C10B	1.362 (5)
C4A—C5A	1.385 (5)	C9B—H9BA	0.9300
C4A—H4AA	0.9300	C10B—H10B	0.9300
C5A—C6A	1.482 (5)	O1W—H1WA	0.82 (2)
C6A—C7A	1.385 (5)	O1W—H1WB	0.82 (2)
C7A—C8A	1.371 (6)
N1B—Hg1—N1A	131.56 (12)	C8A—C7A—C6A	119.9 (4)
N1B—Hg1—N2A	146.65 (11)	C8A—C7A—H7AA	120.0
N1A—Hg1—N2A	73.05 (11)	C6A—C7A—H7AA	120.0
N1B—Hg1—N2B	72.59 (10)	C7A—C8A—C9A	118.9 (4)
N1A—Hg1—N2B	148.59 (11)	C7A—C8A—H8AA	120.6
N2A—Hg1—N2B	95.93 (11)	C9A—C8A—H8AA	120.6
N1B—Hg1—O1	75.40 (9)	C10A—C9A—C8A	118.7 (4)
N1A—Hg1—O1	87.47 (10)	C10A—C9A—H9AA	120.7
N2A—Hg1—O1	134.53 (9)	C8A—C9A—H9AA	120.7
N2B—Hg1—O1	79.65 (10)	N2A—C10A—C9A	122.7 (4)
O3—S1—O2	115.92 (18)	N2A—C10A—H10A	118.6
O3—S1—O1	113.78 (17)	C9A—C10A—H10A	118.6
O2—S1—O1	114.27 (17)	C1B—N1B—C5B	119.2 (3)
O3—S1—O4	106.13 (15)	C1B—N1B—Hg1	122.4 (2)
O2—S1—O4	98.38 (15)	C5B—N1B—Hg1	118.3 (2)
O1—S1—O4	106.24 (15)	C10B—N2B—C6B	119.3 (3)
O7—S2—O6	115.1 (2)	C10B—N2B—Hg1	125.6 (2)
O7—S2—O8	115.4 (2)	C6B—N2B—Hg1	114.8 (2)
O6—S2—O8	114.7 (2)	N1B—C1B—C2B	122.5 (4)
O7—S2—O5	106.41 (17)	N1B—C1B—H1BA	118.7
O6—S2—O5	106.43 (17)	C2B—C1B—H1BA	118.7
O8—S2—O5	96.09 (17)	C1B—C2B—C3B	118.7 (4)
S1—O1—Hg1	110.17 (15)	C1B—C2B—H2BA	120.7
O5—O4—S1	107.62 (17)	C3B—C2B—H2BA	120.7
O4—O5—S2	109.31 (18)	C2B—C3B—C4B	119.4 (4)
C1A—N1A—C5A	120.3 (3)	C2B—C3B—H3BA	120.3
C1A—N1A—Hg1	122.3 (3)	C4B—C3B—H3BA	120.3
C5A—N1A—Hg1	117.1 (2)	C3B—C4B—C5B	119.7 (4)
C10A—N2A—C6A	119.3 (3)	C3B—C4B—H4BA	120.2
C10A—N2A—Hg1	126.0 (3)	C5B—C4B—H4BA	120.2
C6A—N2A—Hg1	114.7 (3)	N1B—C5B—C4B	120.5 (3)
N1A—C1A—C2A	121.9 (4)	N1B—C5B—C6B	117.4 (3)
N1A—C1A—H1AA	119.1	C4B—C5B—C6B	122.1 (3)
C2A—C1A—H1AA	119.1	N2B—C6B—C7B	120.4 (3)
C1A—C2A—C3A	119.2 (4)	N2B—C6B—C5B	116.5 (3)
C1A—C2A—H2AA	120.4	C7B—C6B—C5B	123.0 (3)
C3A—C2A—H2AA	120.4	C8B—C7B—C6B	119.8 (4)
C2A—C3A—C4A	119.2 (4)	C8B—C7B—H7BA	120.1
C2A—C3A—H3AA	120.4	C6B—C7B—H7BA	120.1
C4A—C3A—H3AA	120.4	C7B—C8B—C9B	119.5 (4)
C5A—C4A—C3A	119.7 (4)	C7B—C8B—H8BA	120.3
C5A—C4A—H4AA	120.1	C9B—C8B—H8BA	120.3
C3A—C4A—H4AA	120.1	C10B—C9B—C8B	118.3 (4)
N1A—C5A—C4A	119.7 (4)	C10B—C9B—H9BA	120.9
N1A—C5A—C6A	117.7 (3)	C8B—C9B—H9BA	120.9
C4A—C5A—C6A	122.6 (3)	N2B—C10B—C9B	122.7 (4)
N2A—C6A—C7A	120.5 (4)	N2B—C10B—H10B	118.6
N2A—C6A—C5A	116.9 (3)	C9B—C10B—H10B	118.6
C7A—C6A—C5A	122.6 (3)	H1WA—O1W—H1WB	110 (3)
S1—O4—O5—S2	125.56 (17)	O6—S2—O4—O5	112.3 (3)
O1—S1—O4—O5	−69.8 (2)	O7—S2—O5—O4	49.3 (3)
O2—S1—O4—O5	171.8 (2)	O8—S2—O5—O4	168.1 (2)
O3—S1—O4—O5	51.6 (2)

Symmetry code: (i) x+1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O8^i	0.82 (2)	1.92 (7)	2.703 (13)	160 (16)
C7A—H7AA···O2^ii	0.93	2.41	3.336 (5)	171
C8A—H8AA···O7^ii	0.93	2.40	3.301 (5)	163
C1A—H1AA···O6	0.93	2.60	3.430 (5)	150

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z+1.