Dihydroxy­acetone (DHA) monomer complexes with CaBr₂ and CdCl₂

Two hydrated complexes of monomeric dihydroxy­acetone (DHA; the simplest ketose), viz. the calcium bromide complex bis­([mu]-dihydroxy­acetone)bis­[tetra­aqua­calcium(II)] tetra­brom­ide (isomorphous with the chlor­ide compound reported previously), [Ca₂(C₃H₆O₃)₂(H₂O)₈]Br₄, (2e), and the cadmium chloride complex poly[[bis­([mu]-dihydroxy­acetone)­bis­[bis­(dihy­droxy­acetone)cadmium(II)]] [diaqua­tetra­deca-[mu]-chlorido-di­chloridohexa­cadmium(II)] tetra­hydrate], {[Cd₂(C₃H₆O₃)₆][Cd₆Cl₁₆(H₂O)₂]·4H₂O}_n, (2f), are described. The Ca²⁺ or Cd²⁺ ions are bridged by the carbonyl O atoms from two DHA mol­ecules to form centrosymmetric dimers, with Ca...Ca distances of 4.334 (2) and 4.300 (2) Å in (2e), and a Cd...Cd distance of 4.195 (1) Å in (2f). Almost identical in shape, the eight-coordinate polyhedra of the Ca²⁺ and Cd²⁺ ions are composed of 2n O atoms from n DHA mol­ecules [n = 2 in (2e) and n = 4 in (2f)] and are completed by four water mol­ecules in (2e). DHA mol­ecules chelate the cations via both the hydroxyl and carbonyl groups and exist in an extended conformation, with both hydroxyl groups being synperiplanar to the carbonyl O atom. The crystal structures are stabilized by similar extensive O-H...X (X = Cl or Br) and O-H...O hydrogen-bond networks involving all hydroxyl groups and the water mol­ecules.

S1. Comment

The solid-state study of dihydroxyacetone, DHA (1,3-dihydroxy-2-propanone), the simplest ketose, was undertaken as part of the structural characterization of the intermediates on a chemical pathway, based on the synthesis described by Ferroni et al. (1999) and then modified (Ślepokura & Lis, 2004a; Ślepokura, 2008), leading from dihydroxyacetone to its phosphate ester, dihydroxyacetone phosphate, DHAP, which is a biochemical intermediate of great biological and chemical (synthetic) importance (Gijsen et al., 1996; Koeller & Wong, 2000; Machajewski & Wong, 2000; Fessner & Helaine, 2001). Previously, we have reported the crystal and molecular structures of the series of compounds occurring in the first six steps of the investigated pathway (Ślepokura & Lis, 2004a,b, 2006; Ślepokura, 2008).

DHA (ketotriose), along with D-glyceraldehyde (aldotriose), are the basis of carbohydrate chemistry. Nevertheless, until 2004, the dimeric structure of D-glyceraldehyde, described in 1973 by Senma et al. (1973), was the only crystal structure of a triose given in the literature. In contrast with five- and six-carbon sugars, trioses and tetroses were poorly characterized in terms of their solid-state structure [see, for example, the Cambridge Structural Database (CSD), Version? (Allen, 2002)]. It is known that the commercial solid dihydroxyacetone, which is 100% in dimeric form, dissociates in water solution into a mixture of two monomeric forms: a free carbonyl (ketone, K) and a hydrate (gem-diol, H) in a ratio of 4:1 (Davis, 1973; Ślepokura & Lis, 2004a). Kobayashi et al. (1976) stated that in the melted state DHA also exists as a mixture of monomeric and dimeric molecules, the monomer being predominant. Nevertheless, the solid-state structure of dihydroxyacetone had not been reported until very recently, when we described its crystal and molecular structures in dimeric form, DHA-dimer, C₆H₁₂O₆ [three polymorphous forms, (1a–c)], as well as in monomeric form [DHA, C₃H₆O₃, (2c)], along with two calcium chloride complexes of DHA, [Ca₂Cl₂(DHA)₄(H₂O)₂]Cl₂, (2a), and [Ca₂(DHA)₂(H₂O)₈]Cl₄, (2 b) (Ślepokura & Lis, 2004a).

Analysis of the dihydroxyacetone calcium chloride complexes, (2a) and (2 b), revealed very specific interactions between DHA molecules and Ca²⁺ cations. Although, from the structural point of view, calcium complexation by α-hydroxycarboxylates is well known, calcium complexation by α-hydroxyketones has only rarely been reported. The first crystallographic structural characterization of such a complex reported in the literature was the calcium complex of hydroxyacetophenone (phenacyl alcohol; Doxsee et al., 1993). The α-hydroxyketone moiety occurs in a number of important pharmaceutical compounds (including corticosteroids and tetracycline antibiotics) and there have been reports suggesting the potential interaction of such pharmaceuticals with Ca²⁺ cations in vivo (Monder et al., 1988; Lambs et al., 1988).

The analysis of the structures of the compounds (2a–c) reported by us previously (Ślepokura & Lis, 2004a) and those presented here, (2 e) and (2f), reveals a great similarity in the DHA molecules, regardless of whether they are coordinated to a metal centre or not. The overall molecular structure of monomeric dihydroxyacetone in the solid state is very rigid and hence almost identical in all its known compounds. The most important structural feature of all the DHA molecules is their planarity. The molecules exist in an extended (in-plane) conformation. with all of the non-H atoms lying in one plane, and with the hydroxyl H atoms being nearly coplanar in most cases. Both hydroxyl groups in compounds (2a–f) are in a synperiplanar (sp) orientation in relation to the carbonyl O atom. The molecular structures of the crystallographically independent DHA molecules, two in the calcium bromide complex (2 e) and three in the cadmium chloride complex (2f), are shown in Fig. 1. The relevant torsion angles for all of them are listed in Tables 1 and 4. It is to be noted here that the synperiplanar orientation of the DHA hydroxyl and carbonyl groups was proposed by Yaylayan & Ismail (1995) on the basis of solution FT–IR spectroscopy. The planarity of the α-hydroxyketone moiety in the solid state has been observed in some steroids, e.g. cortisone and its derivatives, sugar derivatives [of what?], methyl 2-acetamido-2-deoxy-β-D-hexafuranosid-5-ulose (CSD refcode? Compound reference?), and hydroxyacetophenone complexed to the Ca²⁺ cation (Doxsee et al., 1993). However, the steroid crystal structures show that when the two α-hydroxyl groups relative to the ketone functionality are present, one of them adopts the antiperiplanar (ap) orientation.

The crystal structure of (2 e) is isomorphous with that of (2 b) and consists of [Ca₂(DHA)₂(H₂O)₈]⁴⁺ cations with Br^- anions located between them. The crystal structure of (2f) is built up from [Cd₂(DHA)₆]⁴⁺ cations, inorganic polymeric [Cd₃Cl₈(H₂O)]_n^2n- anions described below and non-coordinated water of hydration. Two crystallographically independent Ca²⁺ cations in (2 e) form two independent but chemically identical complex cations in a manner shown in Fig. 2. Two symmetry-related Ca²⁺ or Cd²⁺ ions are linked by two carbonyl O bridges from two symmetry-related DHA molecules to form centrosymmetric dimers, with Ca···Ca distances of 4.334 (2) and 4.300 (2) Å in the two crystallographically independent dimers in (2 e) and a Cd···Cd distance of 4.195 (1) Å in (2f). As found in (2a) and (2 b) (Ślepokura & Lis, 2004a), the DHA molecules of the complex cations described here act as bridging as well as chelating ligands for two symmetry-related complex-forming metal centres (Figs. 2 and 3). Thus, the eight-coordinate polyhedra of each Ca²⁺ cation in (2 e) and one of the Cd²⁺ cations (Cd1) in (2f) are composed of O atoms from the differing number of DHA molecules coordinating to them [four O atoms from two DHA in (2 e) and eight O atoms from four DHA in (2f)]. The coordination environments of the Ca²⁺ cations in (2 e) are completed by four water molecules. The coordination polyhedra of the Ca²⁺ and Cd²⁺ metal centres may be described as distorted square antiprisms, with the longest of all the M···O distances being the bridging distance M···O2 (for geometry of the metal coordination spheres, see Tables 2 and 5). The same mode of coordination of the α-hydroxyketone moiety to Ca²⁺ or Cd²⁺ cations is observed in all the DHA complexes presented here and reported previously (Ślepokura & Lis, 2004a), as well as in hydroxyacetophenone complexed with CaCl₂ (Doxsee et al., 1993). This coordination pattern is typical for the α-chelation mode, which is a characteristic mode for the interactions of α-hydroxyacids with Ca²⁺ ions (Einspahr & Bugg, 1981). In all the DHA complexes, there is a strong tendency for the Ca²⁺ ion to lie in the plane of the α-hydroxycarbonyl group, and therefore in the plane of the DHA molecules. The Ca²⁺ cations are restricted to a narrow region, with Ca···O—C angles of about 110–130°, typical for the α-chelation mode: 120.4 (2)–122.7 (2)° in (2 e) and 117.8 (2)–122.4 (2)° in (2f).

The characteristic structural units of all the known DHA complexes are the complex cations, although these may be of three different types. Identical cations with a 1:1 Ca²⁺:DHA ratio (type I) are formed in the isomorphous crystal structures (2 b) and (2 e). Cations with a 1:2 Ca²⁺:DHA ratio (type II) are present in the CaCl₂ complex, (2a). [It is to be noted here that the model obtained for the crystal structure of the CaBr₂ complex, (2 d), reveals a similar complex cation.] The third type of dimeric cation is formed in the case of Cd centres, with a 1:3 C d²⁺:DHA ratio (type III). In all types of complex cation, the ligands (DHA and/or water molecules) are located on two almost perpendicular planes, intersecting each other along the line linking the two M²⁺ ions. The first of these is always built up from the two M²⁺ ions and two bridging DHA molecules to form the core of the dimeric complex cation. In general, the core plane is almost planar (deviations from the least-squares planes are less than 0.2 Å) in all the dimeric complex cations described. The second plane is composed of the same two M²⁺ ions and the other, chelating, DHA molecules and/or water molecules [Cl^- exceptionally in (2a)]. This plane is quite well defined in the complex cation of type II. The same plane in complex cations of types I (eight water molecules) and III (four DHA molecules) is much less well defined, with O6W water molecules in (2 b) and (2 e) being displaced from the plane by 0.4–0.5 Å, and with some of the atoms in (2f) deviating by 0.2–0.3 Å. The intersection angles between the two planes are 87.9 (1) and 88.1 (1)° in the two crystallographically independent complex cations formed by Ca1 and Ca2 in (2 e), and 83.3 (1)° in (2f).

The huge similarity in the building of Ca²⁺ and Cd²⁺ complex cations in (2a), (2 b), (2 e) and (2f) may have some biological justification. It is known that Cd²⁺ ions, despite their different chemical nature, may mimic Ca²⁺ ions in terms of their interactions with the sugar moiety, e.g. in nucleotide anions (Goodgame et al., 1975). Cadmium toxicity is also well known to cause kidney and liver dysfunction and brittle bones. Cadmium competes with calcium both in calcium channels and in intracellular calcium-binding proteins (Richardt et al., 1986; Hinkle et al., 1987).

As observed in the previously presented DHA complexes, as well as in free DHA crystals (Ślepokura & Lis, 2004a), all hydroxyl groups of the DHA molecules of the calcium bromide, (2 e), and cadmium chloride, (2f), complexes are involved in medium-strong and weak hydrogen bonds of diverse type, mainly as donors, but also as acceptors (Figs. 4–6; Tables 3 and 6). Adjacent complex dimers are linked to each other by two kinds of interactions, direct (between the dimers) and indirect (through the halide or/and water bridges). Although the overall crystal packing mode of (2f) seems to be different from that observed in the calcium halide complexes, due to the presence of polymeric inorganic anions, in fact they reveal great similarity, mainly in the geometry of the interdimeric interactions described in detail below.

Two of the calcium halide complexes, (2 b) and (2 e), are isomorphous and an analogous, almost identical, pattern of O—H···O, O—H···X and C—H···X hydrogen bonds is observed in their crystal structures. In general, both hydroxyl groups of the DHA molecules in the CaX₂ complexes, (2a), (2 b) and (2 e), form one O–H···X contact, except for one of the –OH groups in (2a), which is involved in interdimeric O—H···O interactions instead. The same halide anion is simultaneously linked to the other DHA or water molecule from an adjacent complex dimer. The DHA···X interactions are almost linear in most cases, which means that the halide anions lie almost in planes, in which the DHA molecules are located. Thus, the O—H···X network links adjacent cationic dimers via Cl^- or Br^- bridges. The water molecules are involved in similar O—H···X interactions linking adjacent complex cations. In (2 e), all the Br^- anions act as bridges between every three adjacent complex cations, forming different types of interdimeric O—H···Br···H—O interactions: water···Br···water (for Br1, Br2 and Br4), DHA···Br···water (Br1, Br3 and Br4) or DHA···Br···DHA (Br3). Thus, a three-dimensional network of furcated five- (for Br2, Br3 and Br4) or six-centred (for Br1) O—H···Br hydrogen bonds is formed. Additionally, each dimer is stabilized by intradimeric water···water O—H···O interactions (Fig. 4 and Table 3).

The chief characteristic of the packing mode in the cadmium chloride complex, (2f), is a three-dimensional network of O—H···O hydrogen bonds (Fig. 5 and Table 6). The counterions for the dimeric cations in (2f) are the inorganic polymeric anionic [Cd₃Cl₈(H₂O)]_n^2n- ribbons along the a axis, the structure of which consists of edge-sharing CdCl₆ (for Cd2 and Cd4) and CdCl₅(H₂O) (for Cd3) octahedra. Each ribbon is built up from two antiparallel chains by sharing the edges of the respective octahedra from the two chains in a manner shown in Fig. 3. The Cd—Cl distances are in the ranges 2.535 (1)–2.759 (1) and 2.541 (1)–2.792 (1) Å for the CdCl₆ units (Cd2 and Cd4), and 2.552 (1)–2.678 (1) Å for the hydrated unit (Cd3) (Table 5). Since all the Cl^- ions are coordinated to the Cd²⁺ cations forming the anionic ribbon, the role of the O—H···Cl interactions also present in the crystal structure is to link the organometallic and inorganic parts with each other. Thus, each complex cation is linked to the inorganic [Cd₃Cl₈(H₂O)]_n^2n- ribbon by means of three O—H···Cl interactions formed by two DHA molecules and one water molecule. Nevertheless, one can see several common features in all the calcium halide and cadmium chloride DHA complexes. Water molecules O2W and O3W in (2f) adopt the role played by Cl^- and Br^- ions in the crystal structures of the CaX₂ complexes. Adjacent dimeric cations are linked to each other by O—H···O2W···H—O (DHA···water···DHA) water bridges and interdimeric C—H···O (DHA···DHA) contacts to form columns along the a axis (Fig. 6). Adjacent organometallic columns are joined to each other by DHA···O3W···DHA and DHA···O2W···O3W···DHA interactions. Thus, water molecule O3W acts as an interdimeric as well as an inter-column bridge. Furthermore, it is involved in O1W—H2W···O3Wⁱ interactions joining the organometallic and inorganic parts of the compound, and hence is crucial for stabilizing the crystal structure of (2f). The DHA molecules within one complex cation of (2f) (located on the same plane) interact with each other by means of bifurcated three-centred intradimeric O—H···O hydrogen bonds (O1—H1···O22ⁱ and O1—H1···O32ⁱ, shown in Fig. 5 as O1ⁱⁱⁱ–H1ⁱⁱⁱ···O22^@ and O1ⁱⁱⁱ–H1ⁱⁱⁱ···O32^@).

Related literature

For related literature, see: Allen (2002); Davis (1973); Doxsee et al. (1993); Einspahr & Bugg (1981); Ferroni et al. (1999); Fessner & Helaine (2001); Gijsen et al. (1996); Goodgame et al. (1975); Hinkle et al. (1987); Kobayashi et al. (1976); Koeller & Wong (2000); Lambs et al. (1988); Machajewski & Wong (2000); Monder et al. (1988); Richardt et al. (1986); Senma et al. (1973); Yaylayan & Ismail (1995); Ślepokura (2008); Ślepokura & Lis (2004a, 2004b, 2006).

S2. Experimental

Large colourless plates of (2 e) were obtained by slow evaporation of an aqueous solution containing a 1:0.5 molar ratio mixture of commercial CaBr₂·2H₂O (131 mg) and DHA-dimer (50 mg) at 277 K. The specimen used for X-ray diffraction measurements was obtained by cutting an appropriate fragment from a large crystal of (2 e). When starting from substrate ratios of 1:1 and 1:2, another complex of DHA with CaBr₂ was formed, denoted (2 d). Differential scanning calorimetry experiments on crystals of (2 d) revealed a phase transition at about 200 K. It proceeds differently during cooling and heating of the crystals and reveals a series of several broad transitions. Nevertheless, the diffraction patterns obtained from the same or/and different crystals of (2 d) at different temperatures were always similar, regardless of the speed of change of the temperature. Analysis of the Ewald sphere revealed the systematic occurrence of weak reflections, trebling the cell volume. Most probably, these weak reflections result from modulation rather than from superstructure. Omitting all the weak reflections gave only an approximate model of the compound, with the formula [Ca₂(DHA)₄(H₂O)₄]Br₄·0.6H₂O, and this is not presented in this paper.

Slow evaporation at 277 K of aqueous solutions containing different mixtures of CdCl₂·2.5H₂O and commercial DHA-dimer (molar ratios 1:0.5, 1:1 and 1:2) always gave large colourless parallelepipeds (with a tendency to twinning) of a cadmium complex of DHA of the same composition, [Cd₂(DHA)₆][Cd₆Cl₁₆(H₂O)₂]·4H₂O, (2f). A small single-crystal from the 1:1 sample (63.4 mg C dC l₂·2.5H₂O and 50 mg DHA-dimer) was chosen for X-ray diffraction data collection.

S3. Refinement

Since the calcium bromide complex (2 e) is isomorphous with the calcium chloride complex (2 b), the cell setting of (2 e) was related to that in (2 b), which resulted in non-standard axial order. The refinement of the structure of (2 e) was started using the heavy-atom coordinates from (2 b). Two of the Br^- ions in (2 e) are slightly disordered into the Br1, Br10 and Br2, Br20 positions, with the occupancy factors being 0.975 (6) and 0.025 (6) for Br1 and Br10, respectively, and 0.982 (3) and 0.018 (3) for Br2 and Br20, respectively. Due to the low occupancy of Br10 and Br20, only the Br1 and Br2 positions are discussed. All of the non-H atoms were refined anisotropically, except for the low-occupied positions of the disordered atoms in (2 e), i.e. Br10 and Br20.

All H atoms in (2 d) and (2 e) [Should this be (2 e) and (2f)?] were found in difference Fourier maps. In the final refinement cycles, all O-bonded H atoms in (2 e) were refined isotropically, while the remaining H atoms in (2 e) and (2f) were positioned geometrically and treated as riding atoms, with C—H = 0.99 Å and O—H = 0.84 Å, and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(O). Water H atoms in (2f) were refined with U_iso = 1.5U_eq(O).

Computing details

For both compounds, data collection: CrysAlis CCD in KM-4 CCD Software (Oxford Diffraction, 2004); cell refinement: CrysAlis RED in KM-4 CCD Software (Oxford Diffraction, 2004); data reduction: CrysAlis RED in KM-4 CCD Software (Oxford Diffraction, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structures of the crystallographically independent DHA molecules (a) in (2 e) and (b) in (2f). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structures of the two crystallographically independent dimeric [Ca2(DHA)2(H2O)8]^4+ cations in (2 e), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. Symmetry codes are listed in Table 2.
	Fig. 3. The molecular structures of the dimeric [Cd2(DHA)6]^4+ cation and polymeric [Cd3Cl8(H2O)]n^2n- anion in (2f), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. The intra-ribbon O1W—H1W···Cl2 contacts in the anion are shown as dashed lines. Symmetry codes are listed in Table 5.
	Fig. 4. The arrangement of the complex dimers in (2 e), with the Br-bridged interdimeric O—H···Br···H—O linkages of the dimers shown as dashed lines. Symmetry codes are given in Table 3.
	Fig. 5. The arrangement of the complex dimers in (2f), with the water-bridged interdimeric interactions shown as dashed lines and the direct C12—H12B···O3^ii interactions shown as dotted lines. Symmetry codes are given in Table 6. Additionally, an `at' sign (@) denotes atoms generated by the symmetry operator (-x + 1/2, y - 1/2, -z + 1/2).
	Fig. 6. The crystal packing modes in the structures of (a) (2 e) and (b) (2f).

(2e) bis(µ-dihydroxyacetone)bis[tetraaquacalcium(II)] tetrabromide

Crystal data

[Ca2(C3H6O3)2(H2O)8]Br4	V = 1202.9 (5) Å^3
Mr = 724.08	Z = 2
Triclinic, P1	F(000) = 712
Hall symbol: -P 1	Dx = 1.999 Mg m^−3
a = 9.225 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.143 (2) Å	µ = 7.17 mm^−1
c = 14.504 (3) Å	T = 100 K
α = 90.73 (3)°	Plate, colourless
β = 100.01 (3)°	0.41 × 0.36 × 0.17 mm
γ = 92.84 (3)°

Data collection

Kuma KM4 κ-geometry diffractometer with Sapphire CCD camera	6788 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5914 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 30.0°, θmin = 3.3°
Absorption correction: analytical (CrysAlis RED in KM-4 CCD Software; Oxford Diffraction, 2004)	h = −12→12
Tmin = 0.100, Tmax = 0.283	k = −12→9
18605 measured reflections	l = −20→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.057	w = 1/[σ^2(Fo^2) + (0.0226P)^2 + 1.5084P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.002
6788 reflections	Δρmax = 0.56 e Å^−3
326 parameters	Δρmin = −0.51 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0042 (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.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca1	0.63285 (5)	0.70145 (5)	0.53599 (3)	0.00952 (9)
Ca2	0.86425 (5)	−0.14340 (5)	0.06977 (3)	0.00968 (9)
Br1	−0.08780 (13)	0.18346 (14)	0.60201 (4)	0.0187 (2)	0.975 (6)
Br10	−0.055 (3)	0.151 (2)	0.5945 (10)	0.008 (4)*	0.025 (6)
Br2	0.51783 (6)	0.55834 (7)	0.83392 (3)	0.01355 (13)	0.982 (4)
Br20	0.480 (4)	0.517 (4)	0.8217 (17)	0.023 (6)*	0.018 (4)
Br3	0.54270 (2)	1.05372 (2)	0.786199 (15)	0.01241 (6)
Br4	1.02493 (2)	0.62171 (2)	−0.200618 (15)	0.01209 (6)
O1	0.46396 (18)	0.80712 (18)	0.62929 (12)	0.0138 (3)
O2	0.39955 (17)	0.55151 (17)	0.54709 (11)	0.0112 (3)
O3	0.1726 (2)	0.37366 (19)	0.53995 (14)	0.0195 (4)
O11	0.66830 (19)	0.02448 (18)	0.06410 (13)	0.0156 (3)
O21	0.90772 (17)	0.10635 (16)	0.00636 (11)	0.0106 (3)
O31	0.98118 (18)	0.34748 (18)	−0.07075 (13)	0.0154 (3)
C1	0.3257 (2)	0.7400 (2)	0.64072 (17)	0.0132 (4)
C2	0.3080 (2)	0.5927 (2)	0.59223 (15)	0.0110 (4)
C3	0.1756 (3)	0.4967 (3)	0.60107 (18)	0.0175 (5)
C11	0.6734 (2)	0.1713 (2)	0.03371 (17)	0.0126 (4)
C21	0.8140 (2)	0.1973 (2)	−0.00252 (15)	0.0099 (4)
C31	0.8346 (2)	0.3368 (2)	−0.05349 (17)	0.0138 (4)
O1W	0.4665 (2)	0.7297 (2)	0.39579 (13)	0.0192 (4)
O2W	0.7011 (2)	0.53261 (19)	0.66324 (13)	0.0140 (3)
O3W	0.8466 (2)	0.8183 (2)	0.63258 (15)	0.0232 (4)
O4W	0.6571 (3)	0.9509 (2)	0.49154 (17)	0.0277 (5)
O5W	0.7991 (2)	−0.18762 (19)	−0.09965 (12)	0.0139 (3)
O6W	1.0636 (2)	−0.0472 (2)	0.18447 (13)	0.0183 (4)
O7W	0.6744 (2)	−0.3330 (2)	0.04917 (14)	0.0191 (4)
O8W	0.7946 (2)	−0.1919 (2)	0.22102 (13)	0.0202 (4)
H1	0.492 (4)	0.860 (4)	0.671 (3)	0.031 (10)*
H3	0.102 (4)	0.320 (4)	0.551 (3)	0.037 (10)*
H1A	0.2447	0.8017	0.6133	0.016*
H1B	0.3223	0.7288	0.7081	0.016*
H3A	0.1815	0.4644	0.6665	0.021*
H3B	0.0849	0.5509	0.5837	0.021*
H11	0.607 (4)	0.020 (4)	0.094 (3)	0.026 (9)*
H31	0.985 (4)	0.413 (4)	−0.105 (3)	0.032 (10)*
H11A	0.6698	0.2399	0.0865	0.015*
H11B	0.5882	0.1869	−0.0163	0.015*
H31A	0.7642	0.3360	−0.1134	0.017*
H31B	0.8163	0.4219	−0.0150	0.017*
H1W	0.466 (5)	0.777 (5)	0.351 (3)	0.053 (13)*
H2W	0.403 (4)	0.666 (4)	0.381 (3)	0.038 (11)*
H3W	0.786 (5)	0.530 (4)	0.691 (3)	0.036 (10)*
H4W	0.663 (5)	0.539 (4)	0.703 (3)	0.038 (11)*
H5W	0.895 (5)	0.786 (5)	0.682 (3)	0.053 (13)*
H6W	0.871 (4)	0.889 (5)	0.626 (3)	0.037 (11)*
H7W	0.601 (5)	0.993 (5)	0.458 (3)	0.044 (12)*
H8W	0.710 (5)	0.998 (5)	0.507 (3)	0.047 (14)*
H9W	0.859 (5)	−0.239 (5)	−0.118 (3)	0.058 (14)*
H10W	0.725 (5)	−0.216 (4)	−0.123 (3)	0.040 (11)*
H11W	1.093 (4)	−0.096 (5)	0.226 (3)	0.041 (11)*
H12W	1.132 (4)	0.005 (4)	0.170 (2)	0.027 (9)*
H13W	0.639 (4)	−0.364 (4)	−0.001 (3)	0.018 (8)*
H14W	0.640 (5)	−0.387 (5)	0.088 (3)	0.051 (12)*
H15W	0.854 (5)	−0.183 (5)	0.270 (3)	0.050 (12)*
H16W	0.719 (5)	−0.170 (4)	0.232 (3)	0.039 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0096 (2)	0.00916 (18)	0.0096 (2)	−0.00049 (14)	0.00141 (15)	0.00070 (15)
Ca2	0.00818 (19)	0.01002 (18)	0.0113 (2)	0.00057 (14)	0.00264 (15)	0.00216 (15)
Br1	0.0156 (3)	0.0215 (3)	0.01675 (15)	−0.0085 (3)	−0.00141 (15)	0.00596 (15)
Br2	0.01202 (18)	0.0156 (2)	0.01324 (14)	−0.00064 (15)	0.00322 (10)	0.00132 (11)
Br3	0.01319 (11)	0.01305 (10)	0.01134 (10)	−0.00063 (7)	0.00352 (8)	−0.00033 (8)
Br4	0.01207 (10)	0.01260 (10)	0.01153 (10)	0.00160 (7)	0.00157 (8)	0.00117 (8)
O1	0.0131 (8)	0.0130 (7)	0.0149 (8)	−0.0030 (6)	0.0028 (6)	−0.0058 (6)
O2	0.0123 (8)	0.0113 (7)	0.0105 (7)	0.0003 (6)	0.0035 (6)	−0.0007 (6)
O3	0.0158 (9)	0.0173 (8)	0.0270 (10)	−0.0096 (7)	0.0123 (7)	−0.0093 (7)
O11	0.0119 (8)	0.0158 (8)	0.0222 (9)	0.0036 (6)	0.0104 (7)	0.0065 (7)
O21	0.0097 (7)	0.0095 (7)	0.0130 (8)	0.0025 (5)	0.0027 (6)	0.0007 (6)
O31	0.0126 (8)	0.0109 (7)	0.0237 (9)	0.0018 (6)	0.0052 (7)	0.0068 (7)
C1	0.0117 (10)	0.0136 (10)	0.0155 (11)	0.0015 (8)	0.0059 (8)	−0.0010 (8)
C2	0.0114 (10)	0.0145 (10)	0.0063 (9)	0.0002 (8)	−0.0006 (7)	0.0016 (8)
C3	0.0163 (11)	0.0168 (11)	0.0214 (12)	−0.0029 (9)	0.0104 (9)	−0.0066 (9)
C11	0.0101 (10)	0.0130 (10)	0.0152 (11)	0.0027 (8)	0.0032 (8)	0.0016 (8)
C21	0.0102 (10)	0.0100 (9)	0.0091 (10)	0.0013 (7)	0.0002 (7)	−0.0021 (7)
C31	0.0114 (10)	0.0111 (9)	0.0190 (11)	0.0036 (8)	0.0022 (8)	0.0039 (8)
O1W	0.0221 (9)	0.0176 (8)	0.0144 (9)	−0.0073 (7)	−0.0048 (7)	0.0059 (7)
O2W	0.0119 (8)	0.0180 (8)	0.0119 (8)	−0.0006 (6)	0.0014 (7)	0.0027 (6)
O3W	0.0283 (10)	0.0130 (9)	0.0222 (10)	−0.0050 (7)	−0.0108 (8)	0.0036 (7)
O4W	0.0222 (10)	0.0156 (9)	0.0374 (13)	−0.0074 (8)	−0.0153 (9)	0.0108 (8)
O5W	0.0099 (8)	0.0164 (8)	0.0145 (8)	−0.0008 (6)	0.0007 (6)	−0.0015 (6)
O6W	0.0172 (9)	0.0213 (9)	0.0150 (9)	−0.0067 (7)	0.0004 (7)	0.0033 (7)
O7W	0.0190 (9)	0.0212 (9)	0.0165 (9)	−0.0078 (7)	0.0039 (7)	0.0010 (7)
O8W	0.0125 (9)	0.0338 (10)	0.0146 (9)	0.0009 (7)	0.0028 (7)	0.0040 (8)

Geometric parameters (Å, º)

Ca1—O1	2.458 (2)	C3—H3B	0.99
Ca1—O2	2.524 (2)	O11—C11	1.419 (3)
Ca1—O2^i	2.574 (2)	O11—H11	0.77 (4)
Ca1—O3^i	2.387 (2)	O21—C21	1.221 (3)
Ca1—O1W	2.351 (2)	O21—Ca2^ii	2.5505 (17)
Ca1—O2W	2.439 (2)	O31—C31	1.416 (3)
Ca1—O3W	2.405 (2)	O31—Ca2^ii	2.4025 (18)
Ca1—O4W	2.388 (2)	O31—H31	0.78 (4)
Ca1—Ca1^i	4.334 (2)	C11—C21	1.492 (3)
Ca2—O11	2.420 (2)	C11—H11A	0.99
Ca2—O21	2.512 (2)	C11—H11B	0.99
Ca2—O21^ii	2.550 (2)	C21—C31	1.503 (3)
Ca2—O31^ii	2.402 (2)	C31—H31A	0.99
Ca2—O5W	2.450 (2)	C31—H31B	0.99
Ca2—O6W	2.380 (2)	O1W—H1W	0.78 (5)
Ca2—O7W	2.380 (2)	O1W—H2W	0.80 (4)
Ca2—O8W	2.431 (2)	O2W—H3W	0.82 (4)
Ca2—Ca2^ii	4.300 (2)	O2W—H4W	0.73 (4)
O1—C1	1.425 (3)	O3W—H5W	0.84 (5)
O1—H1	0.77 (4)	O3W—H6W	0.69 (4)
O2—C2	1.225 (3)	O4W—H7W	0.77 (5)
O2—Ca1^i	2.5740 (18)	O4W—H8W	0.64 (5)
O3—C3	1.419 (3)	O5W—H9W	0.82 (5)
O3—Ca1^i	2.3867 (19)	O5W—H10W	0.74 (4)
O3—H3	0.84 (4)	O6W—H11W	0.77 (4)
C1—C2	1.500 (3)	O6W—H12W	0.83 (4)
C1—H1A	0.99	O7W—H13W	0.78 (4)
C1—H1B	0.99	O7W—H14W	0.85 (5)
C2—C3	1.493 (3)	O8W—H15W	0.82 (5)
C3—H3A	0.99	O8W—H16W	0.78 (4)
O1W—Ca1—O3^i	94.51 (7)	C1—O1—Ca1	124.54 (13)
O1W—Ca1—O4W	72.42 (8)	C1—O1—H1	109 (3)
O3^i—Ca1—O4W	93.81 (8)	Ca1—O1—H1	122 (3)
O1W—Ca1—O3W	141.91 (7)	C2—O2—Ca1	122.66 (14)
O3^i—Ca1—O3W	77.91 (7)	C2—O2—Ca1^i	120.83 (14)
O4W—Ca1—O3W	70.95 (8)	Ca1—O2—Ca1^i	116.45 (6)
O1W—Ca1—O2W	142.93 (7)	C3—O3—Ca1^i	127.14 (14)
O3^i—Ca1—O2W	91.42 (7)	C3—O3—H3	104 (3)
O4W—Ca1—O2W	143.62 (8)	Ca1^i—O3—H3	126 (3)
O3W—Ca1—O2W	75.06 (7)	O1—C1—C2	108.4 (2)
O1W—Ca1—O1	91.85 (7)	O1—C1—H1A	110.0
O3^i—Ca1—O1	170.43 (6)	C2—C1—H1A	110.0
O4W—Ca1—O1	81.29 (8)	O1—C1—H1B	110.0
O3W—Ca1—O1	92.68 (7)	C2—C1—H1B	110.0
O2W—Ca1—O1	87.79 (7)	H1A—C1—H1B	108.4
O1W—Ca1—O2	72.42 (7)	O2—C2—C1	121.2 (2)
O3^i—Ca1—O2	125.88 (6)	O2—C2—C3	120.8 (2)
O4W—Ca1—O2	128.07 (7)	C1—C2—C3	118.0 (2)
O3W—Ca1—O2	141.39 (7)	O3—C3—C2	107.6 (2)
O2W—Ca1—O2	74.51 (6)	O3—C3—H3A	110.2
O1—Ca1—O2	63.01 (6)	C2—C3—H3A	110.2
O1W—Ca1—O2^i	74.11 (7)	O3—C3—H3B	110.2
O3^i—Ca1—O2^i	62.36 (6)	C2—C3—H3B	110.2
O4W—Ca1—O2^i	136.73 (7)	H3A—C3—H3B	108.5
O3W—Ca1—O2^i	129.80 (7)	C11—O11—Ca2	125.62 (13)
O2W—Ca1—O2^i	76.50 (6)	C11—O11—H11	105 (3)
O1—Ca1—O2^i	126.52 (6)	Ca2—O11—H11	125 (3)
O2—Ca1—O2^i	63.55 (6)	C21—O21—Ca2	122.23 (14)
O1W—Ca1—Ca1^i	70.22 (6)	C21—O21—Ca2^ii	120.35 (14)
O3^i—Ca1—Ca1^i	93.77 (5)	Ca2—O21—Ca2^ii	116.28 (6)
O4W—Ca1—Ca1^i	142.32 (6)	C31—O31—Ca2^ii	124.21 (13)
O3W—Ca1—Ca1^i	146.64 (6)	C31—O31—H31	106 (3)
O2W—Ca1—Ca1^i	72.89 (5)	Ca2^ii—O31—H31	122 (3)
O1—Ca1—Ca1^i	95.11 (5)	O11—C11—C21	107.5 (2)
O2—Ca1—Ca1^i	32.12 (4)	O11—C11—H11A	110.2
O2^i—Ca1—Ca1^i	31.43 (4)	C21—C11—H11A	110.2
O6W—Ca2—O7W	140.44 (7)	O11—C11—H11B	110.2
O6W—Ca2—O31^ii	82.60 (7)	C21—C11—H11B	110.2
O7W—Ca2—O31^ii	82.32 (7)	H11A—C11—H11B	108.5
O6W—Ca2—O11	106.71 (7)	O21—C21—C11	121.2 (2)
O7W—Ca2—O11	86.08 (7)	O21—C21—C31	120.9 (2)
O31^ii—Ca2—O11	168.40 (6)	C11—C21—C31	117.9 (2)
O6W—Ca2—O8W	73.78 (7)	O31—C31—C21	108.3 (2)
O7W—Ca2—O8W	71.61 (7)	O31—C31—H31A	110.0
O31^ii—Ca2—O8W	95.67 (7)	C21—C31—H31A	110.0
O11—Ca2—O8W	80.73 (7)	O31—C31—H31B	110.0
O6W—Ca2—O5W	140.38 (7)	C21—C31—H31B	110.0
O7W—Ca2—O5W	74.42 (7)	H31A—C31—H31B	108.4
O31^ii—Ca2—O5W	86.22 (7)	Ca1—O1W—H1W	136 (3)
O11—Ca2—O5W	90.54 (7)	Ca1—O1W—H2W	117 (3)
O8W—Ca2—O5W	145.37 (7)	H1W—O1W—H2W	105 (4)
O6W—Ca2—O21	79.11 (7)	Ca1—O2W—H3W	122 (3)
O7W—Ca2—O21	137.71 (7)	Ca1—O2W—H4W	116 (3)
O31^ii—Ca2—O21	126.87 (6)	H3W—O2W—H4W	100 (4)
O11—Ca2—O21	62.93 (6)	Ca1—O3W—H5W	127 (3)
O8W—Ca2—O21	125.32 (7)	Ca1—O3W—H6W	123 (4)
O5W—Ca2—O21	77.67 (6)	H5W—O3W—H6W	110 (5)
O6W—Ca2—O21^ii	71.18 (6)	Ca1—O4W—H7W	127 (3)
O7W—Ca2—O21^ii	130.99 (6)	Ca1—O4W—H8W	127 (4)
O31^ii—Ca2—O21^ii	63.18 (6)	H7W—O4W—H8W	106 (5)
O11—Ca2—O21^ii	125.86 (6)	Ca2—O5W—H9W	110 (3)
O8W—Ca2—O21^ii	140.86 (7)	Ca2—O5W—H10W	123 (3)
O5W—Ca2—O21^ii	69.84 (6)	H9W—O5W—H10W	107 (4)
O21—Ca2—O21^ii	63.72 (6)	Ca2—O6W—H11W	118 (3)
O6W—Ca2—Ca2^ii	72.44 (5)	Ca2—O6W—H12W	122 (2)
O7W—Ca2—Ca2^ii	145.20 (6)	H11W—O6W—H12W	110 (4)
O31^ii—Ca2—Ca2^ii	94.76 (5)	Ca2—O7W—H13W	121 (2)
O11—Ca2—Ca2^ii	94.68 (5)	Ca2—O7W—H14W	131 (3)
O8W—Ca2—Ca2^ii	142.92 (6)	H13W—O7W—H14W	107 (4)
O5W—Ca2—Ca2^ii	70.78 (5)	Ca2—O8W—H15W	122 (3)
O21—Ca2—Ca2^ii	32.13 (4)	Ca2—O8W—H16W	122 (3)
O21^ii—Ca2—Ca2^ii	31.59 (4)	H15W—O8W—H16W	106 (4)
O1W—Ca1—O1—C1	67.17 (17)	O7W—Ca2—O11—C11	−152.38 (18)
O4W—Ca1—O1—C1	139.08 (18)	O31^ii—Ca2—O11—C11	−151.7 (3)
O3W—Ca1—O1—C1	−150.66 (17)	O8W—Ca2—O11—C11	135.64 (19)
O2W—Ca1—O1—C1	−75.73 (17)	O5W—Ca2—O11—C11	−78.03 (18)
O2—Ca1—O1—C1	−2.01 (15)	O21—Ca2—O11—C11	−2.19 (16)
O2^i—Ca1—O1—C1	−4.35 (19)	O21^ii—Ca2—O11—C11	−12.8 (2)
Ca1^i—Ca1—O1—C1	−3.13 (17)	Ca2^ii—Ca2—O11—C11	−7.27 (18)
O1W—Ca1—O2—C2	−102.08 (17)	O6W—Ca2—O21—C21	−117.90 (18)
O3^i—Ca1—O2—C2	175.23 (16)	O7W—Ca2—O21—C21	44.9 (2)
O4W—Ca1—O2—C2	−52.7 (2)	O31^ii—Ca2—O21—C21	170.05 (16)
O3W—Ca1—O2—C2	55.8 (2)	O11—Ca2—O21—C21	−2.61 (16)
O2W—Ca1—O2—C2	94.93 (17)	O8W—Ca2—O21—C21	−56.90 (19)
O1—Ca1—O2—C2	−0.59 (16)	O5W—Ca2—O21—C21	94.43 (17)
O2^i—Ca1—O2—C2	177.3 (2)	O21^ii—Ca2—O21—C21	167.8 (2)
Ca1^i—Ca1—O2—C2	177.3 (2)	Ca2^ii—Ca2—O21—C21	167.8 (2)
O1W—Ca1—O2—Ca1^i	80.61 (8)	O6W—Ca2—O21—Ca2^ii	74.26 (8)
O3^i—Ca1—O2—Ca1^i	−2.08 (10)	O7W—Ca2—O21—Ca2^ii	−122.97 (9)
O4W—Ca1—O2—Ca1^i	130.04 (9)	O31^ii—Ca2—O21—Ca2^ii	2.21 (10)
O3W—Ca1—O2—Ca1^i	−121.52 (10)	O11—Ca2—O21—Ca2^ii	−170.45 (9)
O2W—Ca1—O2—Ca1^i	−82.37 (8)	O8W—Ca2—O21—Ca2^ii	135.26 (8)
O1—Ca1—O2—Ca1^i	−177.90 (9)	O5W—Ca2—O21—Ca2^ii	−73.41 (8)
O2^i—Ca1—O2—Ca1^i	0.0	O21^ii—Ca2—O21—Ca2^ii	0.0
Ca1—O1—C1—C2	3.8 (2)	Ca2—O11—C11—C21	5.5 (3)
Ca1—O2—C2—C3	−176.63 (16)	Ca2—O21—C21—C11	6.8 (3)
Ca1^i—O2—C2—C3	0.6 (3)	Ca2^ii—O21—C21—C11	174.20 (15)
Ca1—O2—C2—C1	2.9 (3)	Ca2—O21—C21—C31	−170.94 (15)
Ca1^i—O2—C2—C1	−179.88 (15)	Ca2^ii—O21—C21—C31	−3.6 (3)
O1—C1—C2—O2	−4.2 (3)	O11—C11—C21—O21	−7.7 (3)
O1—C1—C2—C3	175.4 (2)	O11—C11—C21—C31	170.1 (2)
Ca1^i—O3—C3—C2	13.5 (3)	Ca2^ii—O31—C31—C21	20.0 (3)
O2—C2—C3—O3	−8.1 (3)	O21—C21—C31—O31	−9.6 (3)
C1—C2—C3—O3	172.3 (2)	C11—C21—C31—O31	172.6 (2)
O6W—Ca2—O11—C11	65.78 (19)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Br3	0.77 (4)	2.39 (4)	3.150 (2)	169 (4)
O3—H3···Br1	0.84 (4)	2.33 (4)	3.159 (2)	172 (4)
O11—H11···Br3^i	0.77 (4)	2.48 (4)	3.222 (2)	162 (3)
O31—H31···Br4	0.78 (4)	2.43 (4)	3.206 (2)	173 (4)
O1W—H1W···Br3^iii	0.78 (5)	2.53 (5)	3.312 (2)	175 (4)
O1W—H2W···O2W^i	0.80 (4)	2.06 (4)	2.828 (3)	161 (4)
O2W—H4W···Br2	0.73 (4)	2.52 (4)	3.244 (2)	177 (4)
O2W—H3W···Br4^iv	0.82 (4)	2.57 (4)	3.340 (2)	157 (3)
O3W—H6W···Br1^v	0.69 (4)	2.73 (4)	3.412 (2)	169 (4)
O3W—H5W···Br4^iv	0.84 (5)	2.47 (5)	3.288 (2)	163 (4)
O4W—H8W···Br1^v	0.64 (5)	2.64 (5)	3.276 (3)	169 (5)
O4W—H7W···O1^iii	0.77 (5)	2.28 (5)	2.979 (3)	152 (4)
O5W—H10W···Br2^vi	0.74 (4)	2.73 (4)	3.396 (2)	151 (4)
O5W—H9W···Br4^vii	0.82 (5)	2.49 (5)	3.298 (2)	170 (4)
O6W—H11W···Br1^viii	0.77 (4)	2.64 (4)	3.328 (2)	150 (4)
O6W—H12W···O5W^ii	0.83 (4)	2.10 (4)	2.840 (3)	149 (3)
O7W—H13W···Br2^vi	0.78 (4)	2.54 (4)	3.321 (2)	175 (3)
O7W—H14W···Br2^viii	0.85 (5)	2.50 (5)	3.322 (2)	164 (4)
O8W—H15W···Br1^viii	0.82 (5)	2.59 (5)	3.387 (2)	165 (4)
O8W—H16W···Br3^i	0.78 (4)	2.66 (4)	3.401 (2)	160 (4)
C1—H1B···Br2	0.99	2.87	3.526 (3)	125
C3—H3A···Br4^ix	0.99	3.00	3.602 (3)	121
C11—H11A···Br2^i	0.99	2.95	3.794 (3)	144
C11—H11B···Br3^vi	0.99	3.05	3.710 (3)	125
C31—H31A···Br2^x	0.99	3.13	3.785 (3)	125

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y, −z; (iii) −x+1, −y+2, −z+1; (iv) x, y, z+1; (v) x+1, y+1, z; (vi) x, y−1, z−1; (vii) x, y−1, z; (viii) −x+1, −y, −z+1; (ix) x−1, y, z+1; (x) x, y, z−1.

(2f) poly[{bis(µ-dihydroxyacetone)bis[bis(dihydroxyacetone)cadmium(II)} [diaquatetradeca-µ-chlorido-dichloridohexacadmium(II)] tetrahydrate]

Crystal data

[Cd2(C3H6O3)6][Cd6Cl16(H2O)2]·4H2O	Z = 2
Mr = 2114.96	F(000) = 2008
Monoclinic, P21/n	Dx = 2.594 Mg m^−3
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 11.170 (3) Å	µ = 3.94 mm^−1
b = 17.119 (3) Å	T = 100 K
c = 14.225 (3) Å	Parallelepiped, colourless
β = 95.42 (3)°	0.19 × 0.08 × 0.04 mm
V = 2707.9 (10) Å^3

Data collection

Kuma KM4 κ-geometry diffractometer with Sapphire CCD camera	7856 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5800 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
ω scans	θmax = 30.0°, θmin = 3.3°
Absorption correction: analytical (CrysAlis RED in KM-4 CCD Software; Oxford Diffraction, 2004)	h = −15→12
Tmin = 0.550, Tmax = 0.850	k = −24→24
38913 measured reflections	l = −20→20

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)] = 0.029	Hydrogen site location: difference Fourier map
wR(F^2) = 0.036	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.006P)^2] where P = (Fo^2 + 2Fc^2)/3
7856 reflections	(Δ/σ)max = 0.001
322 parameters	Δρmax = 1.02 e Å^−3
0 restraints	Δρmin = −0.60 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.

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 (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.319672 (18)	0.465334 (12)	0.498216 (16)	0.01027 (5)
Cd2	0.572487 (18)	0.087048 (13)	0.424834 (16)	0.01031 (5)
Cd3	0.24097 (2)	0.070741 (11)	0.425621 (17)	0.00993 (5)
Cd4	−0.091810 (18)	0.088855 (13)	0.421726 (16)	0.01013 (5)
Cl1	0.72384 (6)	0.07307 (4)	0.30044 (5)	0.01171 (15)
Cl2	0.54850 (6)	0.23422 (4)	0.42923 (6)	0.01488 (15)
Cl3	0.42159 (6)	0.07355 (4)	0.55909 (5)	0.01058 (16)
Cl4	0.39153 (6)	0.06458 (4)	0.30073 (5)	0.01283 (15)
Cl5	0.24202 (6)	−0.08493 (4)	0.44422 (5)	0.00965 (15)
Cl6	0.06281 (6)	0.07522 (4)	0.29948 (5)	0.01170 (15)
Cl7	0.08956 (6)	0.07314 (4)	0.55509 (5)	0.01012 (15)
Cl8	−0.08331 (7)	0.23712 (4)	0.41625 (6)	0.01763 (16)
O1	0.43080 (17)	0.37363 (11)	0.58599 (15)	0.0141 (5)
O2	0.19595 (17)	0.36586 (11)	0.55523 (14)	0.0131 (4)
O3	0.04632 (16)	0.25986 (12)	0.63366 (15)	0.0150 (4)
O11	0.27611 (16)	0.54872 (12)	0.62401 (14)	0.0151 (4)
O21	0.49360 (16)	0.54035 (11)	0.57673 (14)	0.0112 (4)
O31	0.69068 (17)	0.60571 (13)	0.64531 (16)	0.0199 (5)
O12	0.12527 (17)	0.51076 (10)	0.45451 (16)	0.0125 (4)
O22	0.32487 (16)	0.58577 (11)	0.41791 (14)	0.0122 (4)
O32	0.35247 (16)	0.73406 (12)	0.36360 (15)	0.0135 (4)
C1	0.3760 (2)	0.31223 (16)	0.6330 (2)	0.0120 (6)
C2	0.2424 (2)	0.31707 (16)	0.6096 (2)	0.0108 (6)
C3	0.1713 (2)	0.25687 (16)	0.6567 (2)	0.0132 (6)
C11	0.3643 (2)	0.58764 (18)	0.6860 (2)	0.0139 (6)
C21	0.4838 (2)	0.57800 (15)	0.6492 (2)	0.0102 (6)
C31	0.5926 (2)	0.61543 (17)	0.7005 (2)	0.0144 (6)
C12	0.1151 (2)	0.59239 (16)	0.4349 (2)	0.0111 (6)
C22	0.2328 (2)	0.62430 (16)	0.4086 (2)	0.0100 (6)
C32	0.2339 (2)	0.70740 (16)	0.3737 (2)	0.0147 (7)
O1W	0.2660 (2)	0.20634 (12)	0.43647 (16)	0.0155 (5)
O2W	0.0408 (2)	0.55934 (13)	0.67754 (17)	0.0179 (5)
O3W	0.8866 (2)	0.69741 (14)	0.69807 (17)	0.0230 (5)
H1	0.5052	0.3736	0.6019	0.021*
H3	0.0299	0.2450	0.5777	0.023*
H1A	0.3959	0.3170	0.7021	0.014*
H1B	0.4060	0.2612	0.6125	0.014*
H3A	0.2002	0.2045	0.6399	0.016*
H3B	0.1878	0.2629	0.7259	0.016*
H11	0.2078	0.5556	0.6428	0.023*
H31	0.7524	0.6263	0.6731	0.030*
H11A	0.3661	0.5651	0.7502	0.017*
H11B	0.3443	0.6438	0.6897	0.017*
H31A	0.5775	0.6717	0.7103	0.017*
H31B	0.6109	0.5906	0.7630	0.017*
H12	0.0754	0.4862	0.4178	0.019*
H32	0.3858	0.7473	0.4166	0.020*
H12A	0.0913	0.6202	0.4913	0.013*
H12B	0.0518	0.6012	0.3824	0.013*
H32A	0.1852	0.7110	0.3120	0.018*
H32B	0.1966	0.7417	0.4188	0.018*
H1W	0.336 (3)	0.2157 (19)	0.434 (2)	0.023*
H2W	0.232 (3)	0.233 (2)	0.401 (3)	0.023*
H3W	0.043 (3)	0.539 (2)	0.724 (3)	0.027*
H4W	0.008 (3)	0.597 (2)	0.687 (3)	0.027*
H5W	0.953 (3)	0.719 (2)	0.666 (3)	0.035*
H6W	0.872 (3)	0.706 (2)	0.748 (3)	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01022 (9)	0.00908 (9)	0.01143 (10)	−0.00043 (8)	0.00061 (7)	0.00044 (9)
Cd2	0.00842 (10)	0.01160 (11)	0.01089 (12)	0.00070 (8)	0.00087 (9)	0.00080 (9)
Cd3	0.00799 (10)	0.01115 (10)	0.01064 (11)	0.00033 (8)	0.00080 (9)	0.00086 (10)
Cd4	0.00818 (10)	0.01145 (11)	0.01078 (12)	−0.00005 (8)	0.00103 (9)	0.00050 (9)
Cl1	0.0098 (3)	0.0161 (4)	0.0094 (4)	0.0008 (3)	0.0015 (3)	0.0009 (3)
Cl2	0.0164 (3)	0.0114 (3)	0.0166 (4)	0.0000 (3)	0.0003 (3)	0.0011 (3)
Cl3	0.0094 (3)	0.0118 (4)	0.0105 (4)	−0.0002 (3)	0.0003 (3)	0.0007 (3)
Cl4	0.0093 (3)	0.0198 (4)	0.0094 (4)	0.0007 (3)	0.0009 (3)	0.0003 (3)
Cl5	0.0089 (3)	0.0095 (3)	0.0105 (4)	0.0005 (3)	0.0006 (3)	−0.0004 (3)
Cl6	0.0094 (3)	0.0170 (4)	0.0086 (4)	0.0019 (3)	0.0003 (3)	0.0006 (3)
Cl7	0.0091 (3)	0.0120 (4)	0.0092 (4)	0.0000 (2)	0.0008 (3)	−0.0008 (3)
Cl8	0.0232 (4)	0.0122 (4)	0.0184 (4)	−0.0012 (3)	0.0068 (3)	−0.0014 (3)
O1	0.0071 (9)	0.0157 (11)	0.0191 (13)	−0.0022 (8)	−0.0004 (9)	0.0074 (9)
O2	0.0132 (10)	0.0120 (10)	0.0135 (11)	−0.0002 (8)	−0.0016 (9)	0.0004 (9)
O3	0.0095 (9)	0.0169 (11)	0.0190 (12)	−0.0020 (8)	0.0028 (9)	−0.0020 (10)
O11	0.0125 (9)	0.0180 (11)	0.0150 (11)	−0.0030 (8)	0.0023 (8)	−0.0042 (9)
O21	0.0131 (9)	0.0116 (10)	0.0090 (10)	−0.0015 (8)	0.0012 (8)	−0.0012 (9)
O31	0.0129 (10)	0.0287 (13)	0.0182 (13)	−0.0057 (9)	0.0022 (9)	−0.0094 (10)
O12	0.0125 (10)	0.0080 (10)	0.0165 (12)	−0.0026 (7)	−0.0011 (9)	0.0019 (9)
O22	0.0107 (9)	0.0113 (10)	0.0149 (11)	0.0010 (8)	0.0020 (8)	0.0010 (9)
O32	0.0120 (10)	0.0142 (10)	0.0143 (11)	−0.0024 (8)	0.0020 (9)	0.0009 (9)
C1	0.0126 (14)	0.0107 (14)	0.0124 (15)	−0.0006 (11)	−0.0005 (12)	0.0010 (12)
C2	0.0125 (13)	0.0082 (13)	0.0117 (15)	0.0015 (11)	0.0004 (12)	−0.0043 (12)
C3	0.0110 (13)	0.0120 (14)	0.0165 (17)	−0.0026 (11)	0.0011 (12)	0.0008 (13)
C11	0.0162 (14)	0.0162 (15)	0.0093 (16)	−0.0006 (12)	0.0018 (12)	−0.0004 (13)
C21	0.0163 (14)	0.0063 (14)	0.0077 (14)	0.0009 (10)	−0.0008 (11)	0.0029 (12)
C31	0.0134 (14)	0.0172 (15)	0.0123 (16)	−0.0014 (11)	0.0003 (12)	−0.0019 (13)
C12	0.0117 (13)	0.0107 (13)	0.0105 (15)	0.0013 (11)	−0.0002 (11)	−0.0008 (12)
C22	0.0145 (14)	0.0121 (13)	0.0032 (15)	−0.0003 (11)	−0.0001 (12)	−0.0043 (12)
C32	0.0093 (13)	0.0127 (15)	0.0225 (18)	0.0002 (11)	0.0039 (13)	0.0020 (13)
O1W	0.0144 (11)	0.0153 (11)	0.0166 (13)	−0.0008 (8)	0.0007 (10)	0.0010 (9)
O2W	0.0200 (11)	0.0166 (12)	0.0172 (13)	0.0025 (9)	0.0028 (10)	0.0024 (11)
O3W	0.0242 (12)	0.0274 (13)	0.0185 (13)	−0.0084 (10)	0.0075 (11)	−0.0070 (11)

Geometric parameters (Å, º)

Cd1—O1	2.296 (2)	O3—C3	1.405 (3)
Cd1—O2	2.383 (2)	O3—H3	0.84
Cd1—O11	2.375 (2)	C1—C2	1.499 (4)
Cd1—O21	2.502 (2)	C1—H1A	0.99
Cd1—O12	2.335 (2)	C1—H1B	0.99
Cd1—O22	2.360 (2)	C2—C3	1.498 (4)
Cd1—O21^i	2.432 (2)	C3—H3A	0.99
Cd1—O31^i	2.370 (2)	C3—H3B	0.99
Cd1—Cd1^i	4.1954 (11)	O11—C11	1.424 (3)
Cd2—Cl1	2.5713 (10)	O11—H11	0.84
Cd2—Cl2	2.5350 (9)	O21—C21	1.229 (3)
Cd2—Cl3	2.6740 (11)	O21—Cd1^i	2.4324 (19)
Cd2—Cl4	2.5839 (11)	O31—C31	1.417 (3)
Cd2—Cl3^ii	2.7591 (9)	O31—H31	0.84
Cd2—Cl5^ii	2.6523 (12)	C11—C21	1.488 (4)
Cd3—O1W	2.341 (2)	C11—H11A	0.99
Cd3—Cl3	2.6370 (11)	C11—H11B	0.99
Cd3—Cl4	2.5613 (10)	C21—C31	1.501 (4)
Cd3—Cl5	2.6780 (8)	C31—H31A	0.99
Cd3—Cl6	2.5516 (11)	C31—H31B	0.99
Cd3—Cl7	2.6158 (11)	O12—C12	1.427 (3)
Cd4—Cl6	2.5746 (10)	O12—H12	0.84
Cd4—Cl7	2.6551 (12)	O22—C22	1.218 (3)
Cd4—Cl8	2.5414 (9)	O32—C32	1.421 (3)
Cd4—Cl1^iii	2.5726 (11)	O32—H32	0.84
Cd4—Cl5^iv	2.6572 (11)	C12—C22	1.504 (4)
Cd4—Cl7^iv	2.7925 (9)	C12—H12A	0.99
Cd2—Cd3	3.7147 (10)	C12—H12B	0.99
Cd3—Cd4	3.7252 (10)	C22—C32	1.507 (4)
Cd4—Cd2^iii	3.7544 (10)	C32—H32A	0.99
Cl1—Cd4^v	2.5726 (11)	C32—H32B	0.99
Cl3—Cd2^ii	2.7591 (9)	O1W—H1W	0.80 (3)
Cl5—Cd2^ii	2.6523 (12)	O1W—H2W	0.76 (4)
Cl5—Cd4^iv	2.6572 (11)	O2W—H3W	0.74 (4)
Cl7—Cd4^iv	2.7925 (9)	O2W—H4W	0.77 (3)
O1—C1	1.416 (3)	O3W—H5W	0.98 (4)
O1—H1	0.84	O3W—H6W	0.76 (4)
O2—C2	1.221 (3)
O22—Cd1—O31^i	91.88 (8)	Cd3—Cl7—Cd4	89.94 (3)
O22—Cd1—O2	146.14 (6)	Cd3—Cl7—Cd4^iv	93.92 (2)
O31^i—Cd1—O2	86.78 (7)	Cd4—Cl7—Cd4^iv	100.53 (2)
O22—Cd1—O21^i	76.20 (6)	C1—O1—H1	109.5
O31^i—Cd1—O21^i	64.91 (7)	C2—O2—Cd1	118.61 (17)
O2—Cd1—O21^i	132.02 (7)	C3—O3—H3	109.5
O22—Cd1—O21	73.39 (7)	O1—C1—C2	108.6 (2)
O31^i—Cd1—O21	128.36 (7)	O1—C1—H1A	110.0
O2—Cd1—O21	131.73 (7)	C2—C1—H1A	110.0
O21^i—Cd1—O21	63.53 (8)	O1—C1—H1B	110.0
Cl2—Cd2—Cl1	100.80 (2)	C2—C1—H1B	110.0
Cl2—Cd2—Cl4	95.00 (2)	H1A—C1—H1B	108.3
Cl1—Cd2—Cl4	92.22 (3)	O2—C2—C1	122.2 (3)
Cl2—Cd2—Cl5^ii	94.22 (2)	O2—C2—C3	122.8 (2)
Cl1—Cd2—Cl5^ii	87.78 (3)	C1—C2—C3	114.9 (2)
Cl4—Cd2—Cl5^ii	170.61 (2)	O3—C3—C2	115.3 (2)
Cl2—Cd2—Cl3	89.60 (2)	O3—C3—H3A	108.4
Cl1—Cd2—Cl3	169.50 (2)	C2—C3—H3A	108.4
Cl4—Cd2—Cl3	88.28 (3)	O3—C3—H3B	108.4
Cl5^ii—Cd2—Cl3	90.03 (3)	C2—C3—H3B	108.4
Cl2—Cd2—Cl3^ii	171.91 (2)	H3A—C3—H3B	107.5
Cl1—Cd2—Cl3^ii	87.25 (2)	C11—O11—H11	109.5
Cl4—Cd2—Cl3^ii	85.37 (2)	C21—O21—Cd1^i	122.45 (17)
Cl5^ii—Cd2—Cl3^ii	85.25 (2)	C21—O21—Cd1	121.09 (17)
Cl3—Cd2—Cl3^ii	82.33 (2)	Cd1^i—O21—Cd1	116.47 (8)
O1W—Cd3—Cl6	95.56 (6)	C31—O31—H31	109.5
O1W—Cd3—Cl4	90.26 (6)	O11—C11—C21	108.7 (2)
Cl6—Cd3—Cl4	91.89 (3)	O11—C11—H11A	109.9
O1W—Cd3—Cl7	91.09 (6)	C21—C11—H11A	109.9
Cl6—Cd3—Cl7	88.94 (3)	O11—C11—H11B	109.9
Cl4—Cd3—Cl7	178.34 (2)	C21—C11—H11B	109.9
O1W—Cd3—Cl3	81.72 (6)	H11A—C11—H11B	108.3
Cl6—Cd3—Cl3	176.93 (2)	O21—C21—C11	120.5 (2)
Cl4—Cd3—Cl3	89.56 (3)	O21—C21—C31	120.0 (3)
Cl7—Cd3—Cl3	89.68 (3)	C11—C21—C31	119.6 (2)
O1W—Cd3—Cl5	168.73 (6)	O31—C31—C21	108.3 (2)
Cl6—Cd3—Cl5	95.46 (2)	O31—C31—H31A	110.0
Cl4—Cd3—Cl5	91.75 (2)	C21—C31—H31A	110.0
Cl7—Cd3—Cl5	86.74 (2)	O31—C31—H31B	110.0
Cl3—Cd3—Cl5	87.20 (2)	C21—C31—H31B	110.0
Cl8—Cd4—Cl1^iii	96.56 (2)	H31A—C31—H31B	108.4
Cl8—Cd4—Cl6	92.32 (2)	C12—O12—H12	109.5
Cl1^iii—Cd4—Cl6	94.76 (3)	C22—O22—Cd1	117.81 (18)
Cl8—Cd4—Cl7	95.45 (2)	C32—O32—H32	109.5
Cl1^iii—Cd4—Cl7	167.66 (2)	O12—C12—C22	110.4 (2)
Cl6—Cd4—Cl7	87.60 (3)	O12—C12—H12A	109.6
Cl8—Cd4—Cl5^iv	94.31 (2)	C22—C12—H12A	109.6
Cl1^iii—Cd4—Cl5^iv	87.65 (3)	O12—C12—H12B	109.6
Cl6—Cd4—Cl5^iv	172.64 (2)	C22—C12—H12B	109.6
Cl7—Cd4—Cl5^iv	88.60 (3)	H12A—C12—H12B	108.1
Cl8—Cd4—Cl7^iv	174.54 (3)	O22—C22—C12	121.7 (3)
Cl1^iii—Cd4—Cl7^iv	88.43 (2)	O22—C22—C32	120.9 (2)
Cl6—Cd4—Cl7^iv	89.46 (2)	C12—C22—C32	117.4 (2)
Cl7—Cd4—Cl7^iv	79.47 (2)	O32—C32—C22	111.9 (2)
Cl5^iv—Cd4—Cl7^iv	83.65 (2)	O32—C32—H32A	109.2
Cd2—Cl1—Cd4^v	93.75 (3)	C22—C32—H32A	109.2
Cd3—Cl3—Cd2	88.76 (3)	O32—C32—H32B	109.2
Cd3—Cl3—Cd2^ii	92.99 (2)	C22—C32—H32B	109.2
Cd2—Cl3—Cd2^ii	97.67 (2)	H32A—C32—H32B	107.9
Cd3—Cl4—Cd2	92.43 (3)	Cd3—O1W—H1W	108 (2)
Cd2^ii—Cl5—Cd4^iv	90.00 (3)	Cd3—O1W—H2W	120 (3)
Cd2^ii—Cl5—Cd3	94.52 (2)	H1W—O1W—H2W	106 (4)
Cd4^iv—Cl5—Cd3	95.67 (2)	H3W—O2W—H4W	103 (4)
Cd3—Cl6—Cd4	93.22 (3)	H5W—O3W—H6W	127 (4)
Cl2—Cd2—Cl1—Cd4^v	86.87 (3)	Cl5—Cd3—Cl7—Cd4	−99.65 (2)
Cl4—Cd2—Cl1—Cd4^v	−177.61 (2)	O1W—Cd3—Cl7—Cd4^iv	−168.02 (6)
Cl5^ii—Cd2—Cl1—Cd4^v	−7.00 (2)	Cl6—Cd3—Cl7—Cd4^iv	96.44 (2)
Cl3—Cd2—Cl1—Cd4^v	−85.09 (14)	Cl3—Cd3—Cl7—Cd4^iv	−86.31 (2)
Cl3^ii—Cd2—Cl1—Cd4^v	−92.35 (2)	Cl5—Cd3—Cl7—Cd4^iv	0.91 (2)
O1W—Cd3—Cl3—Cd2	−82.97 (6)	Cl8—Cd4—Cl7—Cd3	−88.02 (2)
Cl4—Cd3—Cl3—Cd2	7.35 (2)	Cl1^iii—Cd4—Cl7—Cd3	105.46 (11)
Cl7—Cd3—Cl3—Cd2	−174.13 (2)	Cl6—Cd4—Cl7—Cd3	4.08 (2)
Cl5—Cd3—Cl3—Cd2	99.12 (2)	Cl5^iv—Cd4—Cl7—Cd3	177.78 (2)
O1W—Cd3—Cl3—Cd2^ii	179.41 (6)	Cl7^iv—Cd4—Cl7—Cd3	93.98 (3)
Cl4—Cd3—Cl3—Cd2^ii	−90.27 (2)	Cl8—Cd4—Cl7—Cd4^iv	178.00 (2)
Cl7—Cd3—Cl3—Cd2^ii	88.26 (2)	Cl1^iii—Cd4—Cl7—Cd4^iv	11.48 (12)
Cl5—Cd3—Cl3—Cd2^ii	1.50 (2)	Cl6—Cd4—Cl7—Cd4^iv	−89.90 (2)
Cl2—Cd2—Cl3—Cd3	87.72 (2)	Cl5^iv—Cd4—Cl7—Cd4^iv	83.80 (2)
Cl1—Cd2—Cl3—Cd3	−100.17 (14)	Cl7^iv—Cd4—Cl7—Cd4^iv	0.0
Cl4—Cd2—Cl3—Cd3	−7.29 (2)	O22—Cd1—O2—C2	−167.90 (19)
Cl5^ii—Cd2—Cl3—Cd3	−178.05 (2)	O31^i—Cd1—O2—C2	103.5 (2)
Cl3^ii—Cd2—Cl3—Cd3	−92.85 (2)	O21^i—Cd1—O2—C2	52.0 (2)
Cl2—Cd2—Cl3—Cd2^ii	−179.42 (2)	O21—Cd1—O2—C2	−38.0 (2)
Cl1—Cd2—Cl3—Cd2^ii	−7.32 (15)	Cd1—O2—C2—C3	174.0 (2)
Cl4—Cd2—Cl3—Cd2^ii	85.56 (2)	Cd1—O2—C2—C1	−7.1 (4)
Cl5^ii—Cd2—Cl3—Cd2^ii	−85.20 (2)	O1—C1—C2—O2	2.6 (4)
Cl3^ii—Cd2—Cl3—Cd2^ii	0.0	O1—C1—C2—C3	−178.3 (2)
O1W—Cd3—Cl4—Cd2	74.11 (6)	O2—C2—C3—O3	0.3 (4)
Cl6—Cd3—Cl4—Cd2	169.68 (2)	C1—C2—C3—O3	−178.7 (2)
Cl3—Cd3—Cl4—Cd2	−7.61 (2)	O22—Cd1—O21—C21	97.2 (2)
Cl5—Cd3—Cl4—Cd2	−94.80 (2)	O31^i—Cd1—O21—C21	176.15 (19)
Cl2—Cd2—Cl4—Cd3	−81.94 (3)	O2—Cd1—O21—C21	−56.3 (2)
Cl1—Cd2—Cl4—Cd3	177.02 (2)	O21^i—Cd1—O21—C21	179.8 (2)
Cl3—Cd2—Cl4—Cd3	7.51 (2)	O22—Cd1—O21—Cd1^i	−82.56 (9)
Cl3^ii—Cd2—Cl4—Cd3	89.95 (2)	O31^i—Cd1—O21—Cd1^i	−3.65 (13)
O1W—Cd3—Cl5—Cd2^ii	−12.2 (3)	O2—Cd1—O21—Cd1^i	123.92 (9)
Cl6—Cd3—Cl5—Cd2^ii	179.98 (2)	O21^i—Cd1—O21—Cd1^i	0.0
Cl4—Cd3—Cl5—Cd2^ii	87.91 (3)	Cd1^i—O21—C21—C11	172.57 (18)
Cl7—Cd3—Cl5—Cd2^ii	−91.40 (3)	Cd1—O21—C21—C11	−7.2 (3)
Cl3—Cd3—Cl5—Cd2^ii	−1.57 (2)	Cd1^i—O21—C21—C31	−6.7 (3)
O1W—Cd3—Cl5—Cd4^iv	78.2 (3)	Cd1—O21—C21—C31	173.50 (18)
Cl6—Cd3—Cl5—Cd4^iv	−89.57 (3)	O11—C11—C21—O21	−0.8 (4)
Cl4—Cd3—Cl5—Cd4^iv	178.36 (2)	O11—C11—C21—C31	178.5 (2)
Cl7—Cd3—Cl5—Cd4^iv	−0.95 (3)	O21—C21—C31—O31	6.4 (4)
Cl3—Cd3—Cl5—Cd4^iv	88.88 (3)	C11—C21—C31—O31	−172.9 (2)
O1W—Cd3—Cl6—Cd4	−86.75 (6)	O31^i—Cd1—O22—C22	102.8 (2)
Cl4—Cd3—Cl6—Cd4	−177.19 (2)	O2—Cd1—O22—C22	15.8 (3)
Cl7—Cd3—Cl6—Cd4	4.25 (2)	O21^i—Cd1—O22—C22	166.4 (2)
Cl5—Cd3—Cl6—Cd4	90.87 (2)	O21—Cd1—O22—C22	−127.5 (2)
Cl8—Cd4—Cl6—Cd3	91.17 (3)	Cd1—O22—C22—C12	−8.2 (3)
Cl1^iii—Cd4—Cl6—Cd3	−172.05 (2)	Cd1—O22—C22—C32	169.2 (2)
Cl7—Cd4—Cl6—Cd3	−4.19 (2)	O12—C12—C22—O22	−10.0 (4)
Cl7^iv—Cd4—Cl6—Cd3	−83.67 (2)	O12—C12—C22—C32	172.5 (2)
O1W—Cd3—Cl7—Cd4	91.43 (6)	O22—C22—C32—O32	−5.6 (4)
Cl6—Cd3—Cl7—Cd4	−4.11 (2)	C12—C22—C32—O32	171.9 (2)
Cl3—Cd3—Cl7—Cd4	173.14 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O22^i	0.84	2.07	2.822 (3)	150
O1—H1···O32^i	0.84	2.45	3.073 (3)	131
O3—H3···Cl8	0.84	2.52	3.312 (2)	158
O11—H11···O2W	0.84	1.98	2.810 (3)	172
O31—H31···O3W	0.84	1.94	2.740 (3)	160
O12—H12···O2W^vi	0.84	1.95	2.784 (3)	173
O32—H32···Cl2^i	0.84	2.27	3.096 (2)	169
O1W—H1W···Cl2	0.80 (3)	2.41 (3)	3.203 (2)	176 (3)
O1W—H2W···O3W^i	0.76 (4)	2.19 (4)	2.944 (3)	173 (4)
O2W—H3W···Cl4^vii	0.74 (4)	2.74 (4)	3.302 (3)	134 (3)
O2W—H4W···O3W^iii	0.77 (3)	2.20 (4)	2.955 (3)	170 (4)
O3W—H5W···Cl8^i	0.98 (4)	2.09 (4)	3.067 (3)	174 (3)
O3W—H6W···O32^viii	0.76 (4)	1.96 (4)	2.690 (3)	159 (4)
C1—H1A···Cl1^vii	0.99	3.11	3.630 (3)	114
C1—H1A···Cl6^ix	0.99	2.88	3.570 (3)	127
C1—H1A···Cl8^ix	0.99	3.17	4.099 (3)	157
C3—H3A···Cl7	0.99	2.79	3.545 (3)	134
C3—H3B···Cl1^vii	0.99	3.02	3.574 (3)	117
C11—H11B···Cl2^i	0.99	3.01	3.638 (3)	123
C11—H11A···Cl1^vii	0.99	2.97	3.628 (3)	125
C11—H11A···Cl7^x	0.99	2.77	3.679 (3)	153
C31—H31B···Cl5^ix	0.99	2.84	3.740 (3)	151
C31—H31B···Cl6^ix	0.99	2.94	3.582 (3)	123
C31—H31A···Cl2^i	0.99	2.83	3.459 (3)	122
C12—H12A···Cl8^vi	0.99	2.78	3.643 (3)	146
C12—H12B···Cl4^xi	0.99	2.81	3.379 (3)	117
C12—H12B···O3^vi	0.99	2.62	3.204 (3)	118
C32—H32B···Cl5^xii	0.99	3.03	3.693 (3)	126
C32—H32B···Cl8^vi	0.99	2.79	3.689 (3)	151
C32—H32A···Cl4^xi	0.99	3.05	3.667 (3)	121

Symmetry codes: (i) −x+1, −y+1, −z+1; (iii) x−1, y, z; (vi) −x, −y+1, −z+1; (vii) x−1/2, −y+1/2, z+1/2; (viii) x+1/2, −y+3/2, z+1/2; (ix) x+1/2, −y+1/2, z+1/2; (x) −x+1/2, y+1/2, −z+3/2; (xi) −x+1/2, y+1/2, −z+1/2; (xii) x, y+1, z.