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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).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105009273/ga1102sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105009273/ga1102Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105009273/ga1102IIsup3.hkl
Contains datablock II

CCDC references: 250892; 250893

Comment top

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 CdII 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 ππ 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 HgII 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 Oterm—S1—Ocore angles than the remaining two Oterm 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 Ocore—Ocore—S—Oterm torsion angle, also subtending the smallest Oterm—S1—Ocore angle (Table 3).

Experimental top

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 HgII 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.

Refinement top

H atoms defined by the stereochemistry were placed in their calculated positions and allowed to ride on their host C atoms, with C—Harom = 0.93 and C—Hmethyl = 0.96 Å, and with Uiso(Harom) = 1.2Ueq(C) or Uiso(Hmethyl) = 1.5Ueq(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 Uiso(Hwater) = 1.2Ueq(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 top

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 top
[Figure 1] 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.
[Figure 2] Fig. 2. A schematic superposition diagram, showing the different orientation of the S2O8 anions in the independent moieties in (I).
[Figure 3] Fig. 3. A packing view of (I), showing the hydrogen-bonding scheme suggested by OW···OW contacts (see text for details).
[Figure 4] 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.]
[Figure 5] 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 top
Crystal data top
[Cd2(C2H3O2)2(S2O8)(C15H11N3)(H2O)]·7H2OZ = 2
Mr = 1163.69F(000) = 1176
Triclinic, P1Dx = 1.740 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 11.059 (6) ÅCell parameters from 2134 reflections
b = 14.254 (7) Åθ = 3.0–24.5°
c = 14.615 (8) ŵ = 1.14 mm1
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) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
9478 independent reflections
Radiation source: fine-focus sealed tube6121 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ϕ and ω scansθmax = 28.0°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1414
Tmin = 0.68, Tmax = 0.84k = 1818
18276 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H atoms treated by a mixture of independent and constrained refinement
S = 0.87 w = 1/[σ2(Fo2) + (0.067P)2]
where P = (Fo2 + 2Fc2)/3
9474 reflections(Δ/σ)max = 0.005
619 parametersΔρmax = 0.67 e Å3
7 restraintsΔρmin = 0.47 e Å3
Crystal data top
[Cd2(C2H3O2)2(S2O8)(C15H11N3)(H2O)]·7H2Oγ = 87.249 (8)°
Mr = 1163.69V = 2221 (2) Å3
Triclinic, P1Z = 2
a = 11.059 (6) ÅMo Kα radiation
b = 14.254 (7) ŵ = 1.14 mm1
c = 14.615 (8) ÅT = 297 K
α = 87.526 (8)°0.40 × 0.30 × 0.15 mm
β = 74.913 (8)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
9478 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
6121 reflections with I > 2σ(I)
Tmin = 0.68, Tmax = 0.84Rint = 0.037
18276 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0467 restraints
wR(F2) = 0.121H atoms treated by a mixture of independent and constrained refinement
S = 0.87Δρmax = 0.67 e Å3
9474 reflectionsΔρmin = 0.47 e Å3
619 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cd10.35588 (3)1.03447 (2)0.69944 (2)0.03595 (11)
Cd20.76145 (3)0.48370 (2)0.74898 (2)0.04497 (12)
S1A0.35674 (10)0.99955 (8)0.94202 (8)0.0353 (3)
O1A0.4325 (3)1.0134 (2)0.8450 (2)0.0460 (8)
O2A0.2801 (3)0.9195 (2)0.9585 (2)0.0498 (8)
O3A0.2997 (3)1.0846 (2)0.9840 (2)0.0546 (9)
O4A0.4565 (3)0.9617 (2)1.0027 (2)0.0467 (8)
S1B0.95148 (12)0.55572 (9)0.88799 (10)0.0532 (3)
O1B0.8753 (3)0.4851 (2)0.8687 (3)0.0602 (10)
O2B0.8886 (4)0.6428 (3)0.9159 (3)0.0799 (13)
O3B1.0706 (3)0.5621 (3)0.8219 (3)0.0823 (13)
O4B11.044 (2)0.514 (3)0.9536 (18)0.049 (11)0.22 (3)
O4B20.953 (2)0.4762 (14)0.9804 (18)0.074 (9)0.33 (3)
O4B30.9624 (14)0.5439 (12)1.0027 (15)0.062 (6)0.45 (3)
C1X0.5622 (4)1.1310 (4)0.6000 (3)0.0426 (11)
C2X0.6722 (4)1.1839 (4)0.5428 (4)0.0565 (14)
H2XA0.65841.24970.55540.085*
H2XB0.68191.17480.47660.085*
H2XC0.74681.16120.55990.085*
O1X0.4723 (3)1.1734 (2)0.6530 (3)0.0613 (10)
O2X0.5624 (3)1.0428 (2)0.5937 (3)0.0567 (9)
C1Y0.9606 (5)0.5808 (3)0.6349 (3)0.0485 (12)
C2Y1.0678 (5)0.6359 (4)0.5766 (4)0.0653 (16)
H2YA1.13220.59360.54240.098*
H2YB1.10110.67220.61770.098*
H2YC1.03880.67740.53260.098*
O1Y0.8664 (3)0.6239 (2)0.6850 (3)0.0586 (10)
O2Y0.9645 (4)0.4930 (2)0.6334 (3)0.0645 (11)
N1A0.1922 (3)1.1414 (3)0.7766 (3)0.0421 (9)
N2A0.1808 (3)0.9537 (2)0.7820 (2)0.0325 (8)
N3A0.3957 (3)0.8684 (2)0.6868 (3)0.0375 (9)
C1A0.2008 (5)1.2346 (3)0.7741 (4)0.0584 (15)
H1AA0.27091.26100.73340.070*
C2A0.1122 (5)1.2929 (4)0.8281 (4)0.0671 (17)
H2AA0.12181.35760.82350.081*
C3A0.0102 (5)1.2563 (4)0.8885 (4)0.0590 (15)
H3AA0.05031.29520.92670.071*
C4A0.0030 (4)1.1610 (3)0.8927 (3)0.0487 (12)
H4AA0.07251.13420.93370.058*
C5A0.0894 (4)1.1053 (3)0.8348 (3)0.0368 (10)
C6A0.0803 (4)1.0009 (3)0.8333 (3)0.0371 (10)
C7A0.0263 (4)0.9555 (3)0.8824 (4)0.0515 (13)
H7AA0.09600.98920.91720.062*
C8A0.0264 (4)0.8599 (3)0.8782 (4)0.0545 (14)
H8AA0.09700.82780.91040.065*
C9A0.0777 (4)0.8109 (3)0.8266 (4)0.0519 (13)
H9AA0.07850.74580.82400.062*
C10A0.1808 (4)0.8605 (3)0.7790 (3)0.0361 (10)
C11A0.2995 (4)0.8131 (3)0.7246 (3)0.0392 (10)
C12A0.3111 (5)0.7172 (3)0.7154 (4)0.0541 (14)
H12A0.24270.68010.74100.065*
C13A0.4249 (5)0.6760 (4)0.6680 (4)0.0670 (17)
H13A0.43440.61120.66160.080*
C14A0.5229 (5)0.7330 (4)0.6309 (4)0.0645 (16)
H14A0.60100.70740.59970.077*
C15A0.5047 (4)0.8284 (3)0.6402 (4)0.0519 (13)
H15A0.57110.86680.61290.062*
N1B0.5981 (4)0.5866 (2)0.8370 (3)0.0452 (10)
N2B0.5880 (3)0.3997 (2)0.8353 (3)0.0414 (9)
N3B0.8003 (3)0.3179 (2)0.7326 (3)0.0420 (9)
C1B0.6081 (5)0.6796 (3)0.8392 (4)0.0605 (15)
H1BA0.68440.70570.80930.073*
C2B0.5090 (5)0.7385 (3)0.8842 (4)0.0643 (16)
H2BA0.51880.80300.88420.077*
C3B0.3988 (5)0.7012 (4)0.9277 (4)0.0640 (16)
H3BA0.33130.74000.95760.077*
C4B0.3852 (5)0.6054 (4)0.9283 (4)0.0573 (14)
H4BA0.30950.57870.95850.069*
C5B0.4883 (4)0.5499 (3)0.8821 (3)0.0449 (12)
C6B0.4827 (4)0.4463 (3)0.8802 (3)0.0434 (11)
C7B0.3758 (4)0.3988 (4)0.9249 (4)0.0572 (14)
H7BA0.30350.43170.95690.069*
C8B0.3779 (5)0.3021 (3)0.9213 (4)0.0590 (15)
H8BA0.30700.26920.95110.071*
C9B0.4852 (4)0.2549 (3)0.8734 (4)0.0510 (13)
H9BA0.48730.18990.86940.061*
C10B0.5905 (4)0.3055 (3)0.8311 (3)0.0412 (11)
C11B0.7100 (4)0.2607 (3)0.7787 (3)0.0379 (10)
C12B0.7282 (5)0.1640 (3)0.7746 (4)0.0498 (13)
H12B0.66520.12540.80810.060*
C13B0.8389 (5)0.1245 (3)0.7214 (4)0.0532 (13)
H13B0.85160.05960.71870.064*
C14B0.9297 (5)0.1831 (3)0.6726 (4)0.0516 (13)
H14B1.00440.15870.63440.062*
C15B0.9090 (4)0.2780 (3)0.6809 (3)0.0471 (12)
H15B0.97260.31720.64950.056*
O1W0.2780 (3)1.0387 (2)0.5640 (2)0.0470 (8)
H1WA0.337 (2)1.025 (3)0.520 (2)0.056*
H1WB0.218 (2)1.006 (3)0.567 (3)0.056*
O2W0.6706 (4)0.4928 (3)0.6214 (3)0.0748 (12)
H2WA0.611 (4)0.461 (4)0.618 (3)0.090*
H2WB0.710 (4)0.509 (4)0.5676 (16)0.090*
O3W0.0418 (4)0.0421 (3)0.4240 (3)0.0880 (13)
O4W0.1974 (4)0.4100 (3)0.5445 (3)0.0844 (13)
O5W0.1954 (3)0.2159 (3)0.5087 (3)0.0740 (12)
O6W0.4806 (5)0.3732 (4)0.6264 (4)0.128 (2)
O7W0.2725 (6)0.4733 (4)0.6943 (5)0.155 (2)
O8W0.3060 (3)0.0777 (3)0.1951 (3)0.0775 (12)
O9W0.1356 (4)0.1810 (3)0.3366 (3)0.0721 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02895 (17)0.03644 (19)0.0384 (2)0.00362 (13)0.00098 (14)0.00216 (14)
Cd20.0454 (2)0.03277 (19)0.0466 (2)0.00636 (15)0.00707 (17)0.00071 (15)
S1A0.0300 (6)0.0363 (6)0.0376 (6)0.0022 (4)0.0047 (5)0.0015 (5)
O1A0.0384 (18)0.062 (2)0.0364 (18)0.0088 (15)0.0067 (14)0.0013 (15)
O2A0.0420 (18)0.0464 (19)0.061 (2)0.0143 (15)0.0111 (16)0.0000 (16)
O3A0.0425 (19)0.0417 (19)0.069 (2)0.0047 (15)0.0037 (17)0.0041 (17)
O4A0.0496 (19)0.0375 (18)0.057 (2)0.0173 (14)0.0201 (17)0.0100 (15)
S1B0.0507 (8)0.0527 (8)0.0540 (9)0.0027 (6)0.0102 (6)0.0017 (6)
O1B0.070 (2)0.045 (2)0.066 (3)0.0109 (18)0.017 (2)0.0060 (17)
O2B0.071 (3)0.059 (2)0.094 (3)0.006 (2)0.009 (2)0.021 (2)
O3B0.051 (2)0.081 (3)0.104 (4)0.005 (2)0.002 (2)0.017 (2)
O4B10.034 (13)0.09 (2)0.023 (14)0.003 (13)0.010 (9)0.005 (12)
O4B20.084 (15)0.062 (13)0.095 (19)0.029 (9)0.052 (11)0.013 (9)
O4B30.055 (8)0.054 (9)0.080 (12)0.022 (6)0.023 (8)0.037 (8)
C1X0.036 (3)0.053 (3)0.038 (3)0.011 (2)0.007 (2)0.003 (2)
C2X0.044 (3)0.066 (3)0.053 (3)0.021 (3)0.002 (2)0.003 (3)
O1X0.047 (2)0.059 (2)0.066 (3)0.0091 (17)0.0098 (18)0.0106 (19)
O2X0.049 (2)0.049 (2)0.064 (2)0.0113 (16)0.0025 (17)0.0058 (18)
C1Y0.053 (3)0.045 (3)0.041 (3)0.009 (2)0.001 (2)0.003 (2)
C2Y0.054 (3)0.054 (3)0.074 (4)0.014 (3)0.008 (3)0.006 (3)
O1Y0.060 (2)0.047 (2)0.059 (2)0.0070 (17)0.0030 (19)0.0037 (17)
O2Y0.077 (3)0.041 (2)0.062 (3)0.0114 (18)0.008 (2)0.0012 (17)
N1A0.031 (2)0.039 (2)0.051 (3)0.0018 (16)0.0020 (17)0.0032 (18)
N2A0.0283 (18)0.037 (2)0.031 (2)0.0003 (15)0.0058 (15)0.0033 (16)
N3A0.0314 (19)0.040 (2)0.037 (2)0.0014 (16)0.0021 (16)0.0022 (17)
C1A0.041 (3)0.039 (3)0.086 (4)0.007 (2)0.001 (3)0.004 (3)
C2A0.055 (3)0.044 (3)0.093 (5)0.003 (3)0.000 (3)0.017 (3)
C3A0.046 (3)0.049 (3)0.075 (4)0.007 (2)0.001 (3)0.022 (3)
C4A0.043 (3)0.049 (3)0.049 (3)0.004 (2)0.002 (2)0.008 (2)
C5A0.030 (2)0.041 (3)0.039 (3)0.0030 (19)0.0073 (19)0.006 (2)
C6A0.028 (2)0.043 (3)0.039 (3)0.0041 (19)0.0072 (19)0.001 (2)
C7A0.033 (3)0.045 (3)0.066 (4)0.003 (2)0.006 (2)0.002 (2)
C8A0.035 (3)0.047 (3)0.071 (4)0.007 (2)0.006 (2)0.005 (3)
C9A0.046 (3)0.041 (3)0.063 (4)0.010 (2)0.004 (3)0.001 (2)
C10A0.030 (2)0.040 (3)0.036 (3)0.0027 (19)0.0051 (19)0.001 (2)
C11A0.035 (2)0.040 (3)0.040 (3)0.003 (2)0.006 (2)0.004 (2)
C12A0.047 (3)0.043 (3)0.065 (4)0.007 (2)0.000 (3)0.004 (3)
C13A0.059 (3)0.037 (3)0.093 (5)0.005 (2)0.002 (3)0.009 (3)
C14A0.050 (3)0.051 (3)0.081 (4)0.005 (3)0.004 (3)0.003 (3)
C15A0.040 (3)0.044 (3)0.063 (4)0.003 (2)0.002 (2)0.002 (2)
N1B0.049 (2)0.030 (2)0.048 (2)0.0021 (17)0.0036 (19)0.0042 (17)
N2B0.042 (2)0.033 (2)0.041 (2)0.0038 (17)0.0046 (18)0.0013 (17)
N3B0.044 (2)0.033 (2)0.044 (2)0.0069 (17)0.0014 (18)0.0006 (17)
C1B0.062 (3)0.041 (3)0.067 (4)0.007 (3)0.006 (3)0.001 (3)
C2B0.072 (4)0.031 (3)0.078 (4)0.001 (3)0.002 (3)0.008 (3)
C3B0.071 (4)0.039 (3)0.070 (4)0.013 (3)0.003 (3)0.012 (3)
C4B0.048 (3)0.051 (3)0.061 (4)0.004 (2)0.009 (3)0.006 (3)
C5B0.045 (3)0.038 (3)0.044 (3)0.000 (2)0.004 (2)0.004 (2)
C6B0.043 (3)0.035 (2)0.044 (3)0.005 (2)0.003 (2)0.000 (2)
C7B0.039 (3)0.058 (3)0.061 (4)0.002 (2)0.011 (2)0.001 (3)
C8B0.049 (3)0.046 (3)0.069 (4)0.018 (2)0.009 (3)0.003 (3)
C9B0.052 (3)0.038 (3)0.056 (3)0.012 (2)0.000 (2)0.001 (2)
C10B0.045 (3)0.034 (2)0.039 (3)0.007 (2)0.001 (2)0.001 (2)
C11B0.042 (3)0.031 (2)0.037 (3)0.0048 (19)0.002 (2)0.0009 (19)
C12B0.053 (3)0.033 (3)0.056 (3)0.004 (2)0.001 (2)0.002 (2)
C13B0.055 (3)0.038 (3)0.062 (4)0.004 (2)0.007 (3)0.007 (2)
C14B0.044 (3)0.044 (3)0.057 (3)0.008 (2)0.002 (2)0.003 (2)
C15B0.042 (3)0.043 (3)0.047 (3)0.003 (2)0.004 (2)0.000 (2)
O1W0.0407 (19)0.057 (2)0.040 (2)0.0060 (16)0.0038 (15)0.0029 (16)
O2W0.073 (3)0.087 (3)0.060 (3)0.020 (2)0.009 (2)0.013 (2)
O3W0.069 (3)0.090 (3)0.101 (4)0.014 (2)0.015 (3)0.004 (3)
O4W0.099 (3)0.071 (3)0.064 (3)0.006 (2)0.013 (2)0.005 (2)
O5W0.062 (2)0.076 (3)0.074 (3)0.007 (2)0.003 (2)0.008 (2)
O6W0.119 (4)0.093 (4)0.160 (6)0.034 (3)0.007 (4)0.006 (4)
O7W0.129 (5)0.111 (5)0.210 (7)0.001 (4)0.019 (5)0.004 (4)
O8W0.059 (2)0.062 (2)0.099 (3)0.0041 (19)0.005 (2)0.020 (2)
O9W0.078 (3)0.064 (2)0.065 (3)0.007 (2)0.000 (2)0.004 (2)
Geometric parameters (Å, º) top
Cd1—N2A2.326 (3)C4A—H4AA0.9300
Cd1—O1W2.353 (4)C5A—C6A1.497 (6)
Cd1—N1A2.385 (4)C6A—C7A1.384 (6)
Cd1—O1X2.390 (3)C7A—C8A1.367 (7)
Cd1—N3A2.393 (4)C7A—H7AA0.9300
Cd1—O2X2.407 (3)C8A—C9A1.378 (6)
Cd1—O1A2.489 (3)C8A—H8AA0.9300
Cd2—O2W2.332 (4)C9A—C10A1.380 (6)
Cd2—N2B2.352 (4)C9A—H9AA0.9300
Cd2—N3B2.393 (4)C10A—C11A1.493 (6)
Cd2—O1Y2.390 (3)C11A—C12A1.376 (6)
Cd2—N1B2.402 (4)C12A—C13A1.386 (7)
Cd2—O1B2.408 (4)C12A—H12A0.9300
Cd2—O2Y2.439 (4)C13A—C14A1.367 (7)
S1A—O2A1.428 (3)C13A—H13A0.9300
S1A—O3A1.426 (3)C14A—C15A1.373 (7)
S1A—O1A1.457 (3)C14A—H14A0.9300
S1A—O4A1.645 (3)C15A—H15A0.9300
O4A—O4Ai1.477 (5)N1B—C1B1.337 (6)
S1B—O2B1.416 (4)N1B—C5B1.341 (5)
S1B—O3B1.421 (4)N2B—C10B1.346 (5)
S1B—O1B1.426 (4)N2B—C6B1.340 (5)
S1B—O4B11.65 (3)N3B—C11B1.340 (5)
S1B—O4B31.71 (2)N3B—C15B1.355 (6)
S1B—O4B21.73 (2)C1B—C2B1.387 (7)
O4B1—O4B1ii1.49 (5)C1B—H1BA0.9300
O4B2—O4B2ii1.51 (4)C2B—C3B1.344 (7)
O4B3—O4B3ii1.46 (3)C2B—H2BA0.9300
C1X—O1X1.239 (5)C3B—C4B1.380 (7)
C1X—O2X1.264 (6)C3B—H3BA0.9300
C1X—C2X1.501 (6)C4B—C5B1.392 (6)
C2X—H2XA0.9600C4B—H4BA0.9300
C2X—H2XB0.9600C5B—C6B1.483 (6)
C2X—H2XC0.9600C6B—C7B1.385 (6)
C1Y—O2Y1.251 (6)C7B—C8B1.380 (7)
C1Y—O1Y1.256 (6)C7B—H7BA0.9300
C1Y—C2Y1.502 (6)C8B—C9B1.372 (7)
C2Y—H2YA0.9600C8B—H8BA0.9300
C2Y—H2YB0.9600C9B—C10B1.388 (6)
C2Y—H2YC0.9600C9B—H9BA0.9300
N1A—C5A1.340 (5)C10B—C11B1.474 (6)
N1A—C1A1.335 (6)C11B—C12B1.386 (6)
N2A—C10A1.331 (5)C12B—C13B1.377 (6)
N2A—C6A1.338 (5)C12B—H12B0.9300
N3A—C15A1.335 (5)C13B—C14B1.368 (6)
N3A—C11A1.341 (5)C13B—H13B0.9300
C1A—C2A1.361 (7)C14B—C15B1.366 (6)
C1A—H1AA0.9300C14B—H14B0.9300
C2A—C3A1.349 (7)C15B—H15B0.9300
C2A—H2AA0.9300O1W—H1WA0.82 (4)
C3A—C4A1.370 (7)O1W—H1WB0.82 (4)
C3A—H3AA0.9300O2W—H2WA0.83 (4)
C4A—C5A1.386 (6)O2W—H2WB0.82 (4)
N2A—Cd1—O1W89.18 (12)C3A—C2A—H2AA120.2
N2A—Cd1—N1A69.38 (12)C1A—C2A—H2AA120.2
O1W—Cd1—N1A90.98 (13)C2A—C3A—C4A119.1 (5)
N2A—Cd1—O1X153.26 (12)C2A—C3A—H3AA120.4
O1W—Cd1—O1X94.13 (13)C4A—C3A—H3AA120.4
N1A—Cd1—O1X84.02 (12)C3A—C4A—C5A118.7 (5)
N2A—Cd1—N3A69.34 (12)C3A—C4A—H4AA120.6
O1W—Cd1—N3A90.43 (12)C5A—C4A—H4AA120.6
N1A—Cd1—N3A138.66 (12)N1A—C5A—C4A122.2 (4)
O1X—Cd1—N3A137.03 (12)N1A—C5A—C6A115.9 (4)
N2A—Cd1—O2X152.89 (12)C4A—C5A—C6A122.0 (4)
O1W—Cd1—O2X87.39 (12)N2A—C6A—C7A121.6 (4)
N1A—Cd1—O2X137.54 (12)N2A—C6A—C5A116.5 (4)
O1X—Cd1—O2X53.85 (11)C7A—C6A—C5A121.9 (4)
N3A—Cd1—O2X83.80 (11)C8A—C7A—C6A118.2 (4)
N2A—Cd1—O1A86.75 (11)C8A—C7A—H7AA120.9
O1W—Cd1—O1A174.31 (11)C6A—C7A—H7AA120.9
N1A—Cd1—O1A91.30 (12)C9A—C8A—C7A120.3 (4)
O1X—Cd1—O1A91.29 (12)C9A—C8A—H8AA119.9
N3A—Cd1—O1A84.42 (12)C7A—C8A—H8AA119.9
O2X—Cd1—O1A94.44 (12)C8A—C9A—C10A118.6 (5)
O2W—Cd2—N2B88.23 (14)C8A—C9A—H9AA120.7
O2W—Cd2—N3B91.36 (15)C10A—C9A—H9AA120.7
N2B—Cd2—N3B68.73 (12)N2A—C10A—C9A121.3 (4)
O2W—Cd2—O1Y87.31 (14)N2A—C10A—C11A116.3 (4)
N2B—Cd2—O1Y153.80 (12)C9A—C10A—C11A122.3 (4)
N3B—Cd2—O1Y137.16 (12)N3A—C11A—C12A121.4 (4)
O2W—Cd2—N1B90.46 (16)N3A—C11A—C10A116.6 (4)
N2B—Cd2—N1B68.42 (13)C12A—C11A—C10A121.9 (4)
N3B—Cd2—N1B137.03 (12)C11A—C12A—C13A119.8 (5)
O1Y—Cd2—N1B85.81 (13)C11A—C12A—H12A120.1
O2W—Cd2—O1B173.10 (12)C13A—C12A—H12A120.1
N2B—Cd2—O1B98.68 (13)C14A—C13A—C12A118.3 (5)
N3B—Cd2—O1B91.28 (12)C14A—C13A—H13A120.8
O1Y—Cd2—O1B86.42 (12)C12A—C13A—H13A120.8
N1B—Cd2—O1B91.96 (13)C13A—C14A—C15A119.2 (5)
O2W—Cd2—O2Y87.46 (15)C13A—C14A—H14A120.4
N2B—Cd2—O2Y151.92 (12)C15A—C14A—H14A120.4
N3B—Cd2—O2Y83.65 (12)N3A—C15A—C14A122.8 (5)
O1Y—Cd2—O2Y53.52 (11)N3A—C15A—H15A118.6
N1B—Cd2—O2Y139.33 (12)C14A—C15A—H15A118.6
O1B—Cd2—O2Y86.49 (13)C1B—N1B—C5B117.9 (4)
O2A—S1A—O3A116.5 (2)C1B—N1B—Cd2123.5 (3)
O2A—S1A—O1A115.4 (2)C5B—N1B—Cd2118.4 (3)
O3A—S1A—O1A113.2 (2)C10B—N2B—C6B120.1 (4)
O2A—S1A—O4A97.83 (17)C10B—N2B—Cd2119.7 (3)
O3A—S1A—O4A106.4 (2)C6B—N2B—Cd2119.8 (3)
O1A—S1A—O4A105.07 (18)C11B—N3B—C15B117.9 (4)
S1A—O1A—Cd1126.97 (17)C11B—N3B—Cd2118.1 (3)
O4Ai—O4A—S1A106.2 (3)C15B—N3B—Cd2124.0 (3)
O2B—S1B—O3B115.2 (2)N1B—C1B—C2B122.5 (5)
O2B—S1B—O1B115.4 (2)N1B—C1B—H1BA118.7
O3B—S1B—O1B114.6 (2)C2B—C1B—H1BA118.7
O2B—S1B—O4B1115.6 (12)C3B—C2B—C1B119.0 (5)
O3B—S1B—O4B179.4 (8)C3B—C2B—H2BA120.5
O1B—S1B—O4B1111.7 (13)C1B—C2B—H2BA120.5
O2B—S1B—O4B385.3 (5)C2B—C3B—C4B120.2 (5)
O3B—S1B—O4B3112.4 (6)C2B—C3B—H3BA119.9
O1B—S1B—O4B3110.4 (6)C4B—C3B—H3BA119.9
O2B—S1B—O4B2114.7 (9)C3B—C4B—C5B118.0 (5)
O3B—S1B—O4B2112.6 (8)C3B—C4B—H4BA121.0
O1B—S1B—O4B279.5 (7)C5B—C4B—H4BA121.0
S1B—O1B—Cd2129.6 (2)N1B—C5B—C4B122.3 (4)
O4B1ii—O4B1—S1B105 (2)N1B—C5B—C6B116.1 (4)
O4B2ii—O4B2—S1B97.6 (16)C4B—C5B—C6B121.7 (4)
O4B3ii—O4B3—S1B100.0 (15)N2B—C6B—C7B121.0 (4)
O1X—C1X—O2X120.5 (4)N2B—C6B—C5B116.7 (4)
O1X—C1X—C2X120.2 (5)C7B—C6B—C5B122.3 (4)
O2X—C1X—C2X119.3 (4)C8B—C7B—C6B119.1 (5)
C1X—C2X—H2XA109.5C8B—C7B—H7BA120.4
C1X—C2X—H2XB109.5C6B—C7B—H7BA120.4
H2XA—C2X—H2XB109.5C9B—C8B—C7B119.6 (4)
C1X—C2X—H2XC109.5C9B—C8B—H8BA120.2
H2XA—C2X—H2XC109.5C7B—C8B—H8BA120.2
H2XB—C2X—H2XC109.5C8B—C9B—C10B119.1 (4)
C1X—O1X—Cd193.5 (3)C8B—C9B—H9BA120.4
C1X—O2X—Cd192.1 (3)C10B—C9B—H9BA120.4
O2Y—C1Y—O1Y120.3 (4)N2B—C10B—C9B120.9 (4)
O2Y—C1Y—C2Y120.5 (5)N2B—C10B—C11B116.1 (4)
O1Y—C1Y—C2Y119.2 (5)C9B—C10B—C11B122.9 (4)
C1Y—C2Y—H2YA109.5N3B—C11B—C12B120.8 (4)
C1Y—C2Y—H2YB109.5N3B—C11B—C10B117.1 (4)
H2YA—C2Y—H2YB109.5C12B—C11B—C10B122.1 (4)
C1Y—C2Y—H2YC109.5C13B—C12B—C11B120.6 (4)
H2YA—C2Y—H2YC109.5C13B—C12B—H12B119.7
H2YB—C2Y—H2YC109.5C11B—C12B—H12B119.7
C1Y—O1Y—Cd294.2 (3)C14B—C13B—C12B118.3 (5)
C1Y—O2Y—Cd292.0 (3)C14B—C13B—H13B120.8
C5A—N1A—C1A117.1 (4)C12B—C13B—H13B120.8
C5A—N1A—Cd1117.8 (3)C15B—C14B—C13B119.1 (5)
C1A—N1A—Cd1124.7 (3)C15B—C14B—H14B120.5
C10A—N2A—C6A119.9 (4)C13B—C14B—H14B120.5
C10A—N2A—Cd1120.2 (3)N3B—C15B—C14B123.2 (4)
C6A—N2A—Cd1119.9 (3)N3B—C15B—H15B118.4
C15A—N3A—C11A118.5 (4)C14B—C15B—H15B118.4
C15A—N3A—Cd1124.2 (3)Cd1—O1W—H1WA106 (3)
C11A—N3A—Cd1117.2 (3)Cd1—O1W—H1WB116 (3)
N1A—C1A—C2A123.3 (5)H1WA—O1W—H1WB112 (4)
N1A—C1A—H1AA118.4Cd2—O2W—H2WA124 (4)
C2A—C1A—H1AA118.4Cd2—O2W—H2WB122 (4)
C3A—C2A—C1A119.5 (5)H2WA—O2W—H2WB109 (4)
O1A—S1A—O4A—O4Aiii15.33 (13)O1B—S1B—O4B2—O4B2iv22.0 (6)
O2A—S1A—O4A—O4Aiii103.69 (16)O2B—S1B—O4B2—O4B2iv91.3 (6)
O3A—S1A—O4A—O4Aiii135.63 (18)O3B—S1B—O4B2—O4B2iv134.3 (7)
O1B—S1B—O4B1—O4B1iv11.9 (14)O1B—S1B—O4B3—O4B3iv42.5 (4)
O2B—S1B—O4B1—O4B1iv122.7 (18)O2B—S1B—O4B3—O4B3iv72.9 (5)
O3B—S1B—O4B1—O4B1iv124.3 (16)O3B—S1B—O4B3—O4B3iv171.7 (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) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O2Xiii0.82 (4)1.99 (4)2.774 (5)159 (4)
O1W—H1WB···O3Wiv0.82 (4)2.07 (4)2.866 (5)165 (5)
O2W—H2WA···O6W0.83 (4)1.93 (4)2.754 (6)171 (6)
O2W—H2WB···O4Wv0.82 (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] top
Crystal data top
[Hg(C10H8N2)2(O8S2)]·0.4H2OF(000) = 1376
Mr = 712.28Dx = 2.112 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2344 reflections
a = 7.3340 (11) Åθ = 3.1–22.7°
b = 30.125 (6) ŵ = 7.12 mm1
c = 10.4340 (17) ÅT = 297 K
β = 103.689 (15)°Needle, colourless
V = 2239.8 (7) Å30.50 × 0.20 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
4938 independent reflections
Radiation source: fine-focus sealed tube4000 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ϕ and ω scansθmax = 28.1°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.20, Tmax = 0.50k = 3739
13178 measured reflectionsl = 1311
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H atoms treated by a mixture of independent and constrained refinement
S = 0.84 w = 1/[σ2(Fo2) + (0.035P)2]
where P = (Fo2 + 2Fc2)/3
4938 reflections(Δ/σ)max = 0.012
332 parametersΔρmax = 1.41 e Å3
4 restraintsΔρmin = 0.72 e Å3
Crystal data top
[Hg(C10H8N2)2(O8S2)]·0.4H2OV = 2239.8 (7) Å3
Mr = 712.28Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.3340 (11) ŵ = 7.12 mm1
b = 30.125 (6) ÅT = 297 K
c = 10.4340 (17) Å0.50 × 0.20 × 0.10 mm
β = 103.689 (15)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
4938 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
4000 reflections with I > 2σ(I)
Tmin = 0.20, Tmax = 0.50Rint = 0.033
13178 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0284 restraints
wR(F2) = 0.061H atoms treated by a mixture of independent and constrained refinement
S = 0.84Δρmax = 1.41 e Å3
4938 reflectionsΔρmin = 0.72 e Å3
332 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Hg10.58598 (2)0.134014 (4)0.411176 (15)0.03693 (6)
S10.11191 (13)0.13232 (3)0.40925 (9)0.0345 (2)
S20.15321 (16)0.10384 (3)0.06340 (10)0.0411 (2)
O10.2183 (4)0.15490 (9)0.3295 (3)0.0469 (7)
O20.2204 (4)0.10251 (9)0.5050 (3)0.0495 (7)
O30.0162 (4)0.16044 (8)0.4552 (3)0.0466 (7)
O40.0180 (4)0.09509 (7)0.3123 (2)0.0384 (6)
O50.1627 (4)0.11929 (9)0.2149 (3)0.0435 (7)
O60.0108 (5)0.12427 (11)0.0378 (3)0.0677 (10)
O70.1519 (5)0.05695 (9)0.0632 (3)0.0673 (9)
O80.3275 (5)0.12412 (11)0.0029 (3)0.0717 (10)
N1A0.5151 (4)0.06822 (9)0.3137 (3)0.0349 (7)
N2A0.7551 (4)0.08067 (9)0.5529 (3)0.0377 (7)
C1A0.3953 (6)0.06403 (14)0.1958 (4)0.0440 (10)
H1AA0.32780.08870.15760.053*
C2A0.3692 (6)0.02447 (14)0.1300 (4)0.0514 (11)
H2AA0.28450.02230.04830.062*
C3A0.4693 (6)0.01192 (13)0.1856 (5)0.0492 (11)
H3AA0.45660.03890.14100.059*
C4A0.5899 (6)0.00806 (12)0.3095 (4)0.0426 (10)
H4AA0.65550.03270.34980.051*
C5A0.6120 (5)0.03268 (11)0.3727 (4)0.0331 (8)
C6A0.7366 (5)0.03912 (11)0.5057 (4)0.0322 (8)
C7A0.8301 (6)0.00434 (12)0.5800 (4)0.0394 (9)
H7AA0.81680.02440.54660.047*
C8A0.9421 (6)0.01231 (13)0.7029 (4)0.0468 (10)
H8AA1.00460.01090.75390.056*
C9A0.9608 (6)0.05524 (13)0.7497 (4)0.0475 (10)
H9AA1.03720.06160.83230.057*
C10A0.8647 (6)0.08822 (13)0.6725 (4)0.0486 (11)
H10A0.87620.11720.70450.058*
N1B0.5838 (4)0.20230 (9)0.3285 (3)0.0339 (7)
N2B0.5553 (4)0.18388 (9)0.5769 (3)0.0364 (7)
C1B0.5835 (6)0.20982 (13)0.2020 (4)0.0457 (10)
H1BA0.59160.18570.14790.055*
C2B0.5717 (7)0.25141 (14)0.1495 (4)0.0553 (12)
H2BA0.56970.25560.06090.066*
C3B0.5629 (7)0.28699 (13)0.2299 (5)0.0561 (12)
H3BA0.55730.31570.19680.067*
C4B0.5625 (6)0.27972 (12)0.3599 (4)0.0432 (10)
H4BA0.55600.30360.41520.052*
C5B0.5717 (5)0.23702 (12)0.4077 (4)0.0336 (8)
C6B0.5667 (5)0.22705 (11)0.5458 (4)0.0340 (8)
C7B0.5678 (6)0.25949 (12)0.6389 (4)0.0466 (10)
H7BA0.57370.28930.61660.056*
C8B0.5601 (7)0.24782 (13)0.7644 (4)0.0574 (12)
H8BA0.56220.26960.82800.069*
C9B0.5493 (7)0.20356 (13)0.7958 (4)0.0554 (12)
H9BA0.54380.19490.88040.066*
C10B0.5468 (6)0.17285 (13)0.6996 (4)0.0466 (10)
H10B0.53890.14300.72010.056*
O1W0.2977 (19)0.1213 (5)0.1050 (15)0.128 (4)0.3994 (10)
H1WA0.27 (2)0.139 (6)0.054 (17)0.154*0.3994 (10)
H1WB0.412 (5)0.118 (6)0.089 (19)0.154*0.3994 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.04327 (10)0.02325 (8)0.04336 (11)0.00279 (6)0.00844 (7)0.00078 (6)
S10.0390 (6)0.0278 (5)0.0351 (5)0.0003 (4)0.0054 (4)0.0021 (4)
S20.0516 (6)0.0358 (5)0.0330 (5)0.0024 (4)0.0040 (4)0.0005 (4)
O10.0392 (16)0.0450 (15)0.0570 (19)0.0038 (13)0.0124 (14)0.0051 (14)
O20.0594 (19)0.0376 (14)0.0429 (17)0.0054 (13)0.0053 (14)0.0054 (13)
O30.0510 (18)0.0391 (15)0.0501 (18)0.0054 (13)0.0131 (14)0.0085 (13)
O40.0490 (16)0.0290 (13)0.0340 (15)0.0018 (12)0.0031 (12)0.0004 (12)
O50.0371 (16)0.0517 (15)0.0402 (17)0.0106 (13)0.0065 (13)0.0001 (14)
O60.072 (2)0.085 (2)0.050 (2)0.0136 (18)0.0240 (19)0.0036 (18)
O70.101 (3)0.0375 (16)0.049 (2)0.0026 (17)0.0110 (18)0.0052 (14)
O80.069 (2)0.077 (2)0.054 (2)0.0233 (18)0.0142 (18)0.0052 (18)
N1A0.0354 (18)0.0310 (15)0.0391 (19)0.0021 (13)0.0103 (15)0.0013 (14)
N2A0.0401 (19)0.0259 (15)0.045 (2)0.0010 (13)0.0054 (15)0.0023 (14)
C1A0.042 (2)0.046 (2)0.043 (3)0.0014 (18)0.007 (2)0.003 (2)
C2A0.052 (3)0.057 (3)0.044 (3)0.007 (2)0.010 (2)0.008 (2)
C3A0.058 (3)0.037 (2)0.055 (3)0.004 (2)0.018 (2)0.013 (2)
C4A0.043 (2)0.034 (2)0.053 (3)0.0008 (17)0.015 (2)0.0035 (19)
C5A0.032 (2)0.0304 (18)0.041 (2)0.0008 (15)0.0171 (17)0.0009 (17)
C6A0.031 (2)0.0288 (18)0.040 (2)0.0002 (14)0.0142 (17)0.0004 (16)
C7A0.048 (2)0.0273 (18)0.047 (3)0.0045 (17)0.018 (2)0.0050 (18)
C8A0.050 (3)0.044 (2)0.047 (3)0.0125 (19)0.014 (2)0.014 (2)
C9A0.043 (2)0.052 (3)0.044 (3)0.001 (2)0.003 (2)0.005 (2)
C10A0.052 (3)0.037 (2)0.054 (3)0.0051 (19)0.008 (2)0.006 (2)
N1B0.0344 (18)0.0281 (15)0.0388 (19)0.0045 (13)0.0079 (14)0.0019 (14)
N2B0.0454 (19)0.0287 (15)0.0334 (18)0.0009 (13)0.0063 (15)0.0022 (14)
C1B0.059 (3)0.038 (2)0.042 (3)0.0080 (19)0.014 (2)0.0005 (19)
C2B0.079 (4)0.051 (3)0.038 (3)0.011 (2)0.019 (2)0.010 (2)
C3B0.079 (4)0.037 (2)0.056 (3)0.012 (2)0.024 (3)0.014 (2)
C4B0.061 (3)0.030 (2)0.039 (2)0.0057 (18)0.012 (2)0.0018 (18)
C5B0.030 (2)0.0314 (18)0.037 (2)0.0026 (15)0.0044 (16)0.0011 (16)
C6B0.035 (2)0.0282 (18)0.037 (2)0.0015 (15)0.0058 (17)0.0015 (16)
C7B0.063 (3)0.032 (2)0.046 (3)0.0003 (19)0.014 (2)0.0017 (19)
C8B0.092 (4)0.041 (2)0.043 (3)0.002 (2)0.023 (3)0.009 (2)
C9B0.088 (4)0.039 (2)0.041 (3)0.000 (2)0.020 (2)0.005 (2)
C10B0.060 (3)0.039 (2)0.041 (3)0.0007 (19)0.011 (2)0.0069 (19)
O1W0.086 (8)0.159 (13)0.133 (12)0.015 (9)0.011 (8)0.047 (10)
Geometric parameters (Å, º) top
Hg1—N1B2.229 (3)C7A—H7AA0.9300
Hg1—N1A2.232 (3)C8A—C9A1.378 (5)
Hg1—N2A2.332 (3)C8A—H8AA0.9300
Hg1—N2B2.341 (3)C9A—C10A1.366 (5)
Hg1—O12.703 (3)C9A—H9AA0.9300
Hg1—O3i2.953 (3)C10A—H10A0.9300
S1—O31.430 (3)N1B—C1B1.338 (5)
S1—O21.436 (3)N1B—C5B1.349 (4)
S1—O11.439 (3)N2B—C10B1.339 (5)
S1—O41.653 (3)N2B—C6B1.348 (4)
S2—O71.413 (3)C1B—C2B1.362 (5)
S2—O61.431 (3)C1B—H1BA0.9300
S2—O81.438 (3)C2B—C3B1.372 (6)
S2—O51.665 (3)C2B—H2BA0.9300
O4—O51.477 (3)C3B—C4B1.374 (6)
N1A—C1A1.338 (5)C3B—H3BA0.9300
N1A—C5A1.350 (4)C4B—C5B1.376 (5)
N2A—C10A1.334 (5)C4B—H4BA0.9300
N2A—C6A1.340 (4)C5B—C6B1.481 (5)
C1A—C2A1.366 (5)C6B—C7B1.376 (5)
C1A—H1AA0.9300C7B—C8B1.370 (5)
C2A—C3A1.370 (6)C7B—H7BA0.9300
C2A—H2AA0.9300C8B—C9B1.380 (5)
C3A—C4A1.387 (6)C8B—H8BA0.9300
C3A—H3AA0.9300C9B—C10B1.362 (5)
C4A—C5A1.385 (5)C9B—H9BA0.9300
C4A—H4AA0.9300C10B—H10B0.9300
C5A—C6A1.482 (5)O1W—H1WA0.82 (2)
C6A—C7A1.385 (5)O1W—H1WB0.82 (2)
C7A—C8A1.371 (6)
N1B—Hg1—N1A131.56 (12)C8A—C7A—C6A119.9 (4)
N1B—Hg1—N2A146.65 (11)C8A—C7A—H7AA120.0
N1A—Hg1—N2A73.05 (11)C6A—C7A—H7AA120.0
N1B—Hg1—N2B72.59 (10)C7A—C8A—C9A118.9 (4)
N1A—Hg1—N2B148.59 (11)C7A—C8A—H8AA120.6
N2A—Hg1—N2B95.93 (11)C9A—C8A—H8AA120.6
N1B—Hg1—O175.40 (9)C10A—C9A—C8A118.7 (4)
N1A—Hg1—O187.47 (10)C10A—C9A—H9AA120.7
N2A—Hg1—O1134.53 (9)C8A—C9A—H9AA120.7
N2B—Hg1—O179.65 (10)N2A—C10A—C9A122.7 (4)
O3—S1—O2115.92 (18)N2A—C10A—H10A118.6
O3—S1—O1113.78 (17)C9A—C10A—H10A118.6
O2—S1—O1114.27 (17)C1B—N1B—C5B119.2 (3)
O3—S1—O4106.13 (15)C1B—N1B—Hg1122.4 (2)
O2—S1—O498.38 (15)C5B—N1B—Hg1118.3 (2)
O1—S1—O4106.24 (15)C10B—N2B—C6B119.3 (3)
O7—S2—O6115.1 (2)C10B—N2B—Hg1125.6 (2)
O7—S2—O8115.4 (2)C6B—N2B—Hg1114.8 (2)
O6—S2—O8114.7 (2)N1B—C1B—C2B122.5 (4)
O7—S2—O5106.41 (17)N1B—C1B—H1BA118.7
O6—S2—O5106.43 (17)C2B—C1B—H1BA118.7
O8—S2—O596.09 (17)C1B—C2B—C3B118.7 (4)
S1—O1—Hg1110.17 (15)C1B—C2B—H2BA120.7
O5—O4—S1107.62 (17)C3B—C2B—H2BA120.7
O4—O5—S2109.31 (18)C2B—C3B—C4B119.4 (4)
C1A—N1A—C5A120.3 (3)C2B—C3B—H3BA120.3
C1A—N1A—Hg1122.3 (3)C4B—C3B—H3BA120.3
C5A—N1A—Hg1117.1 (2)C3B—C4B—C5B119.7 (4)
C10A—N2A—C6A119.3 (3)C3B—C4B—H4BA120.2
C10A—N2A—Hg1126.0 (3)C5B—C4B—H4BA120.2
C6A—N2A—Hg1114.7 (3)N1B—C5B—C4B120.5 (3)
N1A—C1A—C2A121.9 (4)N1B—C5B—C6B117.4 (3)
N1A—C1A—H1AA119.1C4B—C5B—C6B122.1 (3)
C2A—C1A—H1AA119.1N2B—C6B—C7B120.4 (3)
C1A—C2A—C3A119.2 (4)N2B—C6B—C5B116.5 (3)
C1A—C2A—H2AA120.4C7B—C6B—C5B123.0 (3)
C3A—C2A—H2AA120.4C8B—C7B—C6B119.8 (4)
C2A—C3A—C4A119.2 (4)C8B—C7B—H7BA120.1
C2A—C3A—H3AA120.4C6B—C7B—H7BA120.1
C4A—C3A—H3AA120.4C7B—C8B—C9B119.5 (4)
C5A—C4A—C3A119.7 (4)C7B—C8B—H8BA120.3
C5A—C4A—H4AA120.1C9B—C8B—H8BA120.3
C3A—C4A—H4AA120.1C10B—C9B—C8B118.3 (4)
N1A—C5A—C4A119.7 (4)C10B—C9B—H9BA120.9
N1A—C5A—C6A117.7 (3)C8B—C9B—H9BA120.9
C4A—C5A—C6A122.6 (3)N2B—C10B—C9B122.7 (4)
N2A—C6A—C7A120.5 (4)N2B—C10B—H10B118.6
N2A—C6A—C5A116.9 (3)C9B—C10B—H10B118.6
C7A—C6A—C5A122.6 (3)H1WA—O1W—H1WB110 (3)
S1—O4—O5—S2125.56 (17)O6—S2—O4—O5112.3 (3)
O1—S1—O4—O569.8 (2)O7—S2—O5—O449.3 (3)
O2—S1—O4—O5171.8 (2)O8—S2—O5—O4168.1 (2)
O3—S1—O4—O551.6 (2)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O8i0.82 (2)1.92 (7)2.703 (13)160 (16)
C7A—H7AA···O2ii0.932.413.336 (5)171
C8A—H8AA···O7ii0.932.403.301 (5)163
C1A—H1AA···O60.932.603.430 (5)150
Symmetry codes: (i) x+1, y, z; (ii) x+1, y, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formula[Cd2(C2H3O2)2(S2O8)(C15H11N3)(H2O)]·7H2O[Hg(C10H8N2)2(O8S2)]·0.4H2O
Mr1163.69712.28
Crystal system, space groupTriclinic, P1Monoclinic, P21/n
Temperature (K)297297
a, b, c (Å)11.059 (6), 14.254 (7), 14.615 (8)7.3340 (11), 30.125 (6), 10.4340 (17)
α, β, γ (°)87.526 (8), 74.913 (8), 87.249 (8)90, 103.689 (15), 90
V3)2221 (2)2239.8 (7)
Z24
Radiation typeMo KαMo Kα
µ (mm1)1.147.12
Crystal size (mm)0.40 × 0.30 × 0.150.50 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Multi-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.68, 0.840.20, 0.50
No. of measured, independent and
observed [I > 2σ(I)] reflections
18276, 9478, 6121 13178, 4938, 4000
Rint0.0370.033
(sin θ/λ)max1)0.6600.662
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.121, 0.87 0.028, 0.061, 0.84
No. of reflections94744938
No. of parameters619332
No. of restraints74
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.67, 0.471.41, 0.72

Computer programs: SMART-NT (Bruker, 2001), SAINT-NT (Bruker, 2000), SAINT-NT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-PC (Sheldrick, 1994), SHELXL97.

Selected geometric parameters (Å, º) for (I) top
Cd1—N2A2.326 (3)Cd2—O1B2.408 (4)
Cd1—O1W2.353 (4)Cd2—O2Y2.439 (4)
Cd1—N1A2.385 (4)S1A—O2A1.428 (3)
Cd1—O1X2.390 (3)S1A—O3A1.426 (3)
Cd1—N3A2.393 (4)S1A—O1A1.457 (3)
Cd1—O2X2.407 (3)S1A—O4A1.645 (3)
Cd1—O1A2.489 (3)O4A—O4Ai1.477 (5)
Cd2—O2W2.332 (4)S1B—O2B1.416 (4)
Cd2—N2B2.352 (4)S1B—O3B1.421 (4)
Cd2—N3B2.393 (4)S1B—O1B1.426 (4)
Cd2—O1Y2.390 (3)S1B—O4B31.71 (2)
Cd2—N1B2.402 (4)O4B3—O4B3ii1.46 (3)
O2A—S1A—O4A97.83 (17)O2B—S1B—O4B385.3 (5)
O3A—S1A—O4A106.4 (2)O3B—S1B—O4B3112.4 (6)
O1A—S1A—O4A105.07 (18)O1B—S1B—O4B3110.4 (6)
O1A—S1A—O4A—O4Aiii15.33 (13)O1B—S1B—O4B3—O4B3iv42.5 (4)
O2A—S1A—O4A—O4Aiii103.69 (16)O2B—S1B—O4B3—O4B3iv72.9 (5)
O3A—S1A—O4A—O4Aiii135.63 (18)O3B—S1B—O4B3—O4B3iv171.7 (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) for (I) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O2Xiii0.82 (4)1.99 (4)2.774 (5)159 (4)
O1W—H1WB···O3Wiv0.82 (4)2.07 (4)2.866 (5)165 (5)
O2W—H2WA···O6W0.83 (4)1.93 (4)2.754 (6)171 (6)
O2W—H2WB···O4Wv0.82 (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.
Selected geometric parameters (Å, º) for (II) top
Hg1—N1B2.229 (3)S1—O11.439 (3)
Hg1—N1A2.232 (3)S1—O41.653 (3)
Hg1—N2A2.332 (3)S2—O71.413 (3)
Hg1—N2B2.341 (3)S2—O61.431 (3)
Hg1—O12.703 (3)S2—O81.438 (3)
Hg1—O3i2.953 (3)S2—O51.665 (3)
S1—O31.430 (3)O4—O51.477 (3)
S1—O21.436 (3)
O3—S1—O2115.92 (18)O7—S2—O6115.1 (2)
O3—S1—O1113.78 (17)O7—S2—O8115.4 (2)
O2—S1—O1114.27 (17)O6—S2—O8114.7 (2)
O3—S1—O4106.13 (15)O7—S2—O5106.41 (17)
O2—S1—O498.38 (15)O6—S2—O5106.43 (17)
O1—S1—O4106.24 (15)O8—S2—O596.09 (17)
S1—O4—O5—S2125.56 (17)O6—S2—O4—O5112.3 (3)
O1—S1—O4—O569.8 (2)O7—S2—O5—O449.3 (3)
O2—S1—O4—O5171.8 (2)O8—S2—O5—O4168.1 (2)
O3—S1—O4—O551.6 (2)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O8i0.82 (2)1.92 (7)2.703 (13)160 (16)
C7A—H7AA···O2ii0.932.413.336 (5)170.8
C8A—H8AA···O7ii0.932.403.301 (5)163.1
C1A—H1AA···O60.932.603.430 (5)149.5
Symmetry codes: (i) x+1, y, z; (ii) x+1, y, z+1.
Table 5. Miscellaneous information on structures with HgN4 centres top
CSD refcodeDA (°)*CN**BVS***
BAYPUN90.8N42.21
BPYRHG40.5N41.83
COKDUB80.4N41.83
DOMDIS1090.6N42.10
ENHGPC1062.7N41.70
ICIYEY41.0N42.30
MAPDIQ79.8N41.87
MUJXIY63.8N41.85
VANDAP77.8N42.15
ZEMRIS87.6N41.84
BOJXAZ83.2N4+O22.03 + 0.15
IKUGAW83.5N4+O22.02 + 0.13
NUGTUE34.9N4+O21.96 + 0.22
(2) in this work41.0N4+O21.86 + 0.16
*: Dihedral angle in the coordination polyhedron. **: Coordination core (O atoms in the last four entries lie in the range 2.70–3.00 Å) ***: Bond-valence sums, according to Brown & Altermatt (1985).
 

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