Low-dimensional coordination polymeric structures in alkali metal complex salts of the herbicide (2,4-di­chloro­phen­oxy)acetic acid (2,4-D)

The Li, Rb and Cs complexes with the herbicide (2,4-di­­chloro­phen­oxy)acetic acid (2,4-D), namely poly[[aqua­[μ₃-(2,4-di­chloro­phen­oxy)acetato-κ³O¹:O¹:O^1′]lithium(I)] dihydrate], {[Li(C₈H₅Cl₂O₃)(H₂O)]·2H₂O}_n, (I), poly[μ-aqua-bis­[μ₃-(2,4-di­chloro­phen­oxy)acetato-κ⁴O¹:O^1′:O^1′,Cl²]dirubid­ium(I)], [Rb₂(C₈H₅Cl₂O₃)₂(H₂O)]_n, (II), and poly[μ-aqua-bis­[μ₃-(2,4-di­chloro­phen­oxy)acetato-κ⁵O¹:O^1′:O^1′,O²,Cl²]di­caesium(I)], [Cs₂(C₈H₅Cl₂O₃)₂(H₂O)]_n, (III), respectively, have been determined and their two-dimensional polymeric structures are described. In (I), the slightly distorted tetra­hedral LiO₄ coordination involves three carboxyl­ate O-atom donors, of which two are bridging, and a monodentate aqua ligand, together with two water mol­ecules of solvation. Conjoined six-membered ring systems generate a one-dimensional coordination polymeric chain which extends along b and interspecies water O—H...O hydrogen-bonding inter­actions give the overall two-dimensional layers which lie parallel to (001). In hemihydrate complex (II), the irregular octa­hedral RbO₅Cl coordination about Rb⁺ comprises a single bridging water mol­ecule which lies on a twofold rotation axis, a bidentate O_carb­oxy,Cl-chelate inter­action and three bridging carboxyl­ate O-atom bonding inter­actions from the 2,4-D ligand. A two-dimensional coordination polymeric layer structure lying parallel to (100) is formed through a number of conjoined cyclic bridges, including a centrosymmetric four-membered Rb₂O₂ ring system with an Rb...Rb separation of 4.3312 (5) Å. The coordinated water mol­ecule forms intra­layer aqua–carboxyl­ate O—H...O hydrogen bonds. Complex (III) comprises two crystallographically independent (Z′ = 2) irregular CsO₆Cl coordination centres, each comprising two O-atom donors (carboxyl­ate and phen­oxy) and a ring-substituted Cl-atom donor from the 2,4-D ligand species in a tridentate chelate mode, two O-atom donors from bridging carboxyl­ate groups and one from a bridging water mol­ecule. However, the two 2,4-D ligands are conformationally very dissimilar, with one phen­oxy­acetate side chain being synclinal and the other being anti­periplanar. The minimum Cs...Cs separation is 4.4463 (5) Å. Structure extension gives coordination polymeric layers which lie parallel to (001) and are stabilized by intra­layer water–carboxyl­ate O—H...O hy­dro­gen bonds.

S1. Introduction

The ring-substituted phen­oxy­alkanoic acids comprise an important group of chemical reagents having selective herbicidal properties which have resulted in their commercial utilization (Cobb & Reade, 2011). Of these, 2-(2,4-di­chloro­phen­oxy)­acetic acid (2,4-D) is considered one of the most prominent members (O'Neil, 2001). It also provides features which make it a good candidate for metal complex formation in having as an anion, along with the carboxyl­ate group, a stereochemically favourable phen­oxy O atom for potential chelate formation. Considering these factors, it is not surprising that 2,4-D has been combined with a wide range of metal types and the resulting characterized complex examples amount to more than 50 entries in the CSD (Groom & Allen, 2014). These include a number of mixed-ligand and mixed-metal complexes. However, there are only two examples of alkalai metal complex salts with 2,4-D, viz. (i) the hemihydrate potassium salt (Kennard et al., 1983), which forms a two-dimensional coordination polymeric complex structure, and (ii) the caesium complex salt with hydrogen bis­(2,4-di­chloro­phen­oxy)­acetate (Smith & Lynch, 2014). This second mentioned ligand species is analogous to the ligand in sodium hydrogen bis­(phen­oxy­acetate) (Evans et al., 2001a), as well as the hydrogen bis­(4-nitro­benzoate) species found in the early reported potassium salt (Srivastava & Speakman, 1961) and in the rubidium salts of hydrogen bis­(acetyl­salicylate) (Grimvall & Wengelin, 1967) and the isostructural rubidium hydrogen bis­(3-chloro­benzoate) and rubidium hydrogen bis­(3-bromo­benzoate) salts (Van Deun et al., 2005).

The structures of the salts of the alkali metals other than lithium with the phen­oxy­acetic acid analogues are generally not numerous in the crystallographic literature, comprising five other examples besides those previously mentioned for 2,4-D, i.e. sodium phen­oxy­acetate hemihydrate (Prout et al., 1971; Evans et al., 2001b), caesium phen­oxy­acetate (Smith, 2014), caesium (4-fluoro­phen­oxy)­acetate, caesium (4-chloro-2-methyl­phen­oxy)­acetate (Smith & Lynch, 2014) and caesium o-(phenyl­ene­dioxy)­diacetate dihydrate (Smith et al., 1989). With lithium, the structures of three complexes are known, i.e. with (2-chloro­phen­oxy)­acetic acid (O'Reilly et al., 1987), (2-carbamolyphen­oxy)­acetic acid (Mak et al., 1986) and o-(phenyl­ene­dioxy)­diacetic acid (Smith et al., 1986). These Li⁺ complexes, as with most lithium carboxyl­ates, have predominantly basic tetra­hedral LiO₄ coordination geometry in polymeric structures, e.g. [LiO₄]_n in anhydrous lithium 3,5-di­nitro­benzoate (Yang & Ng, 2007) or [LiO₂(H₂O)₂]_n in lithium salicylate (Wiesbrock & Schmidbaur, 2003).

In the structures of the alkali metal phen­oxy­acetates are found examples of both the bidentate chelate (O,O')_carb­oxy, and (O,O¹)_{carb­oxy/phen­oxy} metal–ligand inter­actions, forming sheet substructures. With the potassium–2,4-D salt (Kennard et al., 1983), a third characteristically phen­oxy bidentate chelate inter­action is found which involves a K—Cl bond to the ortho-Cl ring substituent of the ligand, generating an eight-membered chelate ring about K.

To investigate the modes of inter­action and the nature of the coordination complex structures found in the alkali metal compounds with 2,4-D, the salts with Li⁺, Na⁺, Rb⁺ and Cs⁺ were prepared and crystals of three of these (the Li⁺, Rb⁺ and Cs⁺ salts) were determined and the structures are reported herein. These are the trihydrate {[Li(2,4-D)(H₂O)].2H₂O}_n, (I), and the hemihydrates [Rb₂(2,4-D)₂(H₂O)]_n, (II), and [Cs₂(2,4-D)₂(H₂O)]_n, (III). With the previously reported structure of the Cs complex salt with hydrogen bis­[(2,4-di­chloro­phen­oxy)­acetate] (Smith & Lynch, 2014), the preparation involved the reaction of 2,4-D with CsCl, unlike our more usual preparations using CsOH, as was the case in the preparation of (III). Suitable crystals of the Na–2,4-D analogue could not be obtained.

S2. Experimental

S2.1. Synthesis and crystallization

The title compounds (I)–(III) were synthesized by heating together for 10 min, 1:1 stoichiometric qu­anti­ties of 2-(2,4-di­chloro­phen­oxy)­acetic acid (1.0 mmol, 220 mg) and, respectively, LiOH (1.0 mmol, 24 mg), Rb₂CO₃ (0.5 mmol, 125 mg) or CsOH (1.0 mmol, 150 mg), in an ethanol–water mixture (15 ml, 1:9 v/v). Partial room-temperature evaporation of the solutions gave in all cases, colourless crystal plates from which specimens were cleaved for the X-ray analyses. Crystals of (I) was found to be unstable in air, apparently losing water molecules of solvation.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in calculated positions (aromatic C—H = 0.95 Å and methyl­ene C—H = 0.99 Å) and were allowed to ride in the refinements, with U_iso(H) = 1.2U_eq(C). The water H atoms were located in difference Fourier maps. Their positions were refined, but for (I) and (III) the O—H and H···H distances were restrained to 0.88 (2) and 1.40 (4) Å, respectively, whilst for (II), the O—H distances were restrained to 0.90 (2) Å. For all water H atoms, U_iso(H) = 1.5U_eq(O). With (III), although of no significance in this achiral structure, the Flack absolute structure factor (Flack, 1983) was determined as 0.001 (16) for 2851 Friedel pairs.

S3. Results and discussion

All three structures, i.e. (I)–(III), give low-dimensional coordination polymers in which the core substructures comprise the metal–oxygen coordination chains or sheets with the aromatic rings of the ligands peripherally located between them. However, there are no inter-ring π–π inter­actions in any of the structures [minimun ring-centroid separations = 4.747 (1) Å in (I), 4.359 (15) Å in (II) and 5.640 (3) Å in (III)].

In the structure of the trihydrate Li⁺ salt with 2,4-D, (I), the asymmetric unit (Fig. 1) comprises the common slightly distorted tetra­hedral LiO₄ coordination unit [Li—O range = 1.931 (3)–1.986 (3) Å] and two water molecules of solvation (O2W and O3W). The coordination unit comprises one monodentate carboxyl­ate O-atom donor (O13) and a water molecule (O1W), while there are two bridging carboxyl­ate O-atom donors [O14ⁱ and O14ⁱⁱ[ symmetry codes: (i) x, y-1, z; (ii) -x+3/2, y-1/2, -z+3/2]. Conjoined six-membered ring systems in which the Li···Li separation is 3.045 (4) Å generate a one-dimensional coordination polymeric chain substructure which extends along b (Figs. 2 and 3). Hydrogen bonding involving both the coordinated and solvent water molecules and both carboxyl­ate and phen­oxy O-atom acceptors, as well as water–water inter­actions (Table 2), give an overall two-dimensional structure which lies parallel to (001) (Fig. 3).

The 2,4-D ligand has the synclinal phen­oxy­acetate side-chain conformation [defining torsion angle (about O11–C12) = 90±30°], with torsion angles C2—C1—O11—C12 = -171.51 (13)°, C1—O11—C12—O13 = 72.75 (17)° and O11—C12—C13—O14 = -174.58 (14)°, similar to that found in the parent acid (2,4-D), where the comparative defining value is 75.2° (Smith et al., 1976).

The hemihydrate Rb⁺ salt with 2,4-D, (II) (Fig. 4), comprises an RbO₅Cl complex unit with the bridging coordinated water molecule (O1W) lying on a crystallographic twofold rotation axis. In the very distorted o­cta­hedral coordination sphere about Rb1 [Rb—O range = 2.7909 (16)–2.946 (2) Å] (Table 3), an example of the bidentate chelate phen­oxy-Cl ligand–metal inter­action is found, involving a carboxyl­ate O13 donor and the ortho-related Cl ring-substitutuent (Cl2). This type of inter­action has no precedence in Rb–phen­oxy complex structures, but is similar to that found in the Cs–2,4-D structure (III) where the inter­mediate phen­oxy atom O11 is sufficiently close to the Cs to be considered coordinating, giving a tridentate inter­action. However, with (II), this Rb1···O11 distance [3.2789 (19) Å] is beyond an acceptable Rb—O bond range. Carboxyl­ate atoms O13 and O14 are also bridging, as is the coordinated water molecule (O1W) on the twofold axis, giving two-dimensional layers which lie parallel to (100) (Figs. 5 and 6). Within the polymer layers, the minimum Rb1···Rb1 ⁱⁱ separation is 4.3312 (5) Å within a centrosymmetric four-membered Rb₂O₂ ring. The water molecule is also involved in intra­layer O—H···O_{carboxyl­ate} hydrogen-bonding inter­actions (Table 4). The 2,4-D ligand adopts the anti­periplanar (torsion angle 180±30°) conformation, with the defining C1—O11—C12—C13 torsion angle of 173.03 (19)°.

It is of inter­est that the two-dimensional structures of the potassium 2,4-D salt (Kennard et al., 1983) (a hemihydrate with the bridging water molecule on a twofold axis), is similar in all respects to the structure of (II) and crystallizes with Z = 8 (space group C2/c) in an isomorphous cell with that of (II) [for K–2,4-D: a = 36.80 (1), b = 4.339 (1), c = 12.975 (7) Å, β = 102.03 (4)° and V = 2026 ų]. This similarity also extends to the two-dimensional ammonium 2,4-D hemihydrate structure (Liu et al., 2009), with crystals having a = 37.338 (8), b = 4.388 (9), c = 12.900 (3) Å, β = 103.82 (3)°, V = 2074.7 (8) ų and Z = 8, with space group C2/c. In this structure, the ammonium cation occupies an equivalent site to the Rb cation in the structure of (II), with the water molecule similarly on the twofold axis and forming intra­layer hydrogen bonds with the O14 carboxyl­ate O-atom acceptors of related 2,4-D anions.

For the Cs⁺ salt with 2,4-D, (III), the asymmetric unit comprises two irregular CsO₆Cl complex units (A and B), with the water molecule (O1W) bridging (Fig. 7). Each unit has identical donor components, i.e. two anion O atoms (carboxyl­ate O13A/B and phen­oxy O11A/B) and an ortho-substituted ring Cl-donor (Cl2A/B), in a tridentate chelate mode; two bridging carboxyl­ate O-atom donors (O13A/B and O14A/B) and the bridging water molecule. This 2,4-D coordination mode with the elongated Cs—Cl bond [3.6446 (16) (A) and 3.5146 (16) Å (B)] was also found in the Cs hydrogen bis­[(2,4-di­chloro­phen­oxy)­acetate complex species [Cs—Cl = 3.6035 (14) Å; Smith & Lynch, 2014]. However, in (III), there is a major conformational difference between ligands A and B, one having the anti­periplanar phen­oxy­acetate side-chain conformation [torsion angles C2A—C1A—O11A—O12A = -174.3 (4)°, C1A—O11A—C12A—O13A = 169.2 (4)° and O11A—C12A—C13A—O14A = 154.3 (4)°], comparing with the comparative angles in the B ligand [153.2 (5), -72.5 (5) and 155.7 (4)°], where the mid-angle is synclinal. This B-ligand conformation is quite similar to that of the parent acid (torsion angle = 75.2°; Smith et al., 1976), which is an unusual member of the phen­oxy­acetate acid series where the side-chain conformation is predominantly anti­periplanar (Lynch et al., 1999). The Cs—O11A/B bond lengths within the tridentate chelate ligand [3.331 (4) (A) and 3.423 (4) Å (B)] are longer than what is normally considered a typical Cs—O bond length, with the range for the other Cs—O bonds in (III) being 2.945 (4)–3.360 (4) Å (Table 5).

In the crystal, the bridging O and Cl atoms give a series of cyclic inter­actions resulting in an overall two-dimensional sheet structure which lies parallel to (001) (Figs. 8 and 9). Within this structure there are a number of conjoined cyclic inter­actions, including a Cs₂O₂ example in which the minimum Cs1···Cs2ⁱ separation is 4.4463 (5) Å. The coordinated water molecule provides intra­layer O—H···O hydrogen bonds to carboxyl­ate O-atom acceptors O14Aⁱ and O14Bⁱⁱ (Table 6).

The presence of coordinated ring-substituted Cl donors such as those found in (III) has precedence in two Cs⁺ complexes with aromatic carb­oxy­lic acids, viz. 4-amino-3,5,6-tri­chloro­pyridine-2-carb­oxy­lic acid [Cs—Cl = 3.6052 (11)–3.7151 (11) Å; Smith, 2013a] and 2,3-6-tri­chloro­phenyl­acetic acid [Cs—Cl = 3.646 (2) and 3.711 (2) Å; Smith, 2013b].

The present set of structures of the alkali metal salts of 2-(2,4-di­chloro­phen­oxy)­acetic acid show a trend common with phen­oxy­acetic acids for formation of two-dimensional polymers with an incidence of both O,O' and O,O¹-chelates and with Rb and Cs, formation of the uniquely phen­oxy bidentate (Rb) or tridentate (Cs) Cl,O,O¹-chelate inter­actions.

Computing details

For all compounds, data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013). Program(s) used to solve structure: SIR92 (Altomare et al., 1993) for (I), (III); SHELXS97 (Sheldrick, 2008) for (II). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The atom-numbering scheme and the molecular configuration of complex (I), with displacement ellipsoids drawn at the 40% probability level. Interspecies hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x, y-1, z; (ii) -x+3/2, y-1/2, -z+3/2.]
	Fig. 2. A view of the partially expanded coordination polymeric structure of (I), which extends along the b-cell direction, with non-associative H atoms omitted.
	Fig. 3. The packing of the two-dimensional hydrogen-bonded layered structure of compound (I) in the unit cell, viewed along a.
	Fig. 4. The atom-numbering scheme and the molecular configuration of the RbO5Cl coordination polyhedron in (II), with displacement ellipsoids drawn at the 40% probability level. The bridging water molecule (O1W) lies on a twofold rotation axis. For symmetry codes, see Table 3.
	Fig. 5. A view of the partially expanded polymeric extension of the structure of (II), viewed along the approximate b-cell direction, with non-associative H atoms omitted. [Symmetry codes: (iv) x, y-1, z; (v) -x, y, -z+1/2. For other codes, see Table 3.]
	Fig. 6. The packing of the layered structure of compound (II) in the unit cell, viewed along b. Hydrogen bonds are shown as dashed lines.
	Fig. 7. The atom-numbering scheme and the molecular configuration of the coordination polyhedra of the two independent CsO6Cl complex units in (III), with displacement ellipsoids drawn at the 40% probability level. For symmetry codes, see Table 5.
	Fig. 8. A view of the partially expanded polymeric extension of the structure of (III), with unassociative H atoms omitted. For symmetry codes, see Table 6.
	Fig. 9. The packing of the layered structure of compound (III) in the unit cell, viewed along b.

(I) Poly[[aqua[µ₃-2-(2,4-dichlorophenoxy)acetato-κ³O¹:O¹:O^1':]lithium(I)] dihydrate]

Crystal data

[Li(C8H5Cl2O3)(H2O)]·2H2O	F(000) = 576
Mr = 281.01	Dx = 1.534 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2663 reflections
a = 7.8705 (4) Å	θ = 4.0–28.2°
b = 4.9984 (3) Å	µ = 0.54 mm^−1
c = 30.9367 (17) Å	T = 200 K
β = 90.343 (5)°	Block, colourless
V = 1217.03 (12) Å^3	0.35 × 0.26 × 0.20 mm
Z = 4

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	2391 independent reflections
Radiation source: Enhance (Mo) X-ray source	2108 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.3°
ω scans	h = −9→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −5→6
Tmin = 0.930, Tmax = 0.981	l = −38→38
7126 measured reflections

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0269P)^2 + 0.6487P] where P = (Fo^2 + 2Fc^2)/3
2391 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.24 e Å^−3
7 restraints	Δρmin = −0.22 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
Cl2	1.27919 (6)	−0.12915 (9)	0.58911 (1)	0.0329 (2)
Cl4	0.69450 (7)	−0.32482 (12)	0.50398 (2)	0.0482 (2)
O1W	0.53927 (17)	−0.1305 (3)	0.68571 (4)	0.0315 (4)
O11	1.09103 (16)	0.2868 (2)	0.63187 (4)	0.0282 (4)
O13	0.91847 (14)	0.0867 (2)	0.70030 (4)	0.0234 (4)
O14	0.82594 (15)	0.4876 (2)	0.72053 (4)	0.0238 (4)
C1	0.9901 (2)	0.1520 (3)	0.60290 (5)	0.0233 (5)
C2	1.0678 (2)	−0.0509 (3)	0.57930 (5)	0.0232 (5)
C3	0.9783 (2)	−0.1965 (4)	0.54875 (6)	0.0283 (5)
C4	0.8087 (2)	−0.1391 (4)	0.54187 (6)	0.0311 (6)
C5	0.7290 (2)	0.0595 (4)	0.56468 (6)	0.0344 (6)
C6	0.8202 (2)	0.2046 (4)	0.59526 (6)	0.0328 (6)
C12	1.0111 (2)	0.4701 (3)	0.66080 (6)	0.0280 (5)
C13	0.9095 (2)	0.3348 (3)	0.69635 (5)	0.0188 (5)
Li1	0.7439 (4)	−0.1484 (5)	0.72192 (9)	0.0227 (8)
O2W	0.47121 (19)	0.3859 (3)	0.64621 (5)	0.0407 (5)
O3W	1.23705 (18)	−0.0636 (3)	0.73011 (5)	0.0357 (4)
H3	1.03270	−0.33390	0.53270	0.0340*
H5	0.61230	0.09750	0.55960	0.0410*
H6	0.76500	0.34180	0.61110	0.0390*
H11W	0.446 (2)	−0.115 (5)	0.6995 (7)	0.0470*
H12W	0.523 (3)	−0.279 (4)	0.6722 (7)	0.0470*
H121	0.93430	0.58810	0.64400	0.0340*
H122	1.09950	0.58420	0.67430	0.0340*
H21W	0.374 (2)	0.359 (5)	0.6351 (8)	0.0610*
H22W	0.498 (3)	0.233 (4)	0.6570 (8)	0.0610*
H31W	1.141 (2)	−0.038 (5)	0.7176 (7)	0.0530*
H32W	1.233 (3)	−0.213 (4)	0.7433 (8)	0.0530*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl2	0.0241 (2)	0.0360 (3)	0.0386 (3)	0.0039 (2)	−0.0013 (2)	−0.0050 (2)
Cl4	0.0470 (3)	0.0540 (3)	0.0433 (3)	−0.0124 (3)	−0.0187 (2)	−0.0015 (2)
O1W	0.0257 (7)	0.0304 (7)	0.0384 (8)	0.0007 (6)	−0.0044 (6)	−0.0051 (6)
O11	0.0259 (7)	0.0301 (7)	0.0286 (6)	−0.0052 (5)	0.0087 (5)	−0.0091 (5)
O13	0.0225 (6)	0.0153 (6)	0.0325 (7)	0.0003 (5)	0.0049 (5)	0.0012 (5)
O14	0.0298 (7)	0.0178 (6)	0.0239 (6)	0.0049 (5)	0.0073 (5)	0.0010 (5)
C1	0.0249 (9)	0.0236 (8)	0.0215 (8)	−0.0042 (7)	0.0066 (7)	0.0012 (7)
C2	0.0213 (9)	0.0261 (9)	0.0222 (8)	−0.0001 (7)	0.0031 (7)	0.0038 (7)
C3	0.0320 (10)	0.0290 (9)	0.0238 (9)	−0.0008 (8)	0.0024 (7)	−0.0021 (7)
C4	0.0326 (10)	0.0341 (10)	0.0264 (9)	−0.0090 (8)	−0.0046 (8)	0.0045 (8)
C5	0.0222 (9)	0.0408 (11)	0.0403 (11)	−0.0005 (8)	0.0003 (8)	0.0085 (9)
C6	0.0280 (10)	0.0337 (10)	0.0367 (10)	0.0020 (8)	0.0090 (8)	−0.0001 (8)
C12	0.0356 (10)	0.0198 (8)	0.0287 (9)	−0.0058 (7)	0.0123 (8)	−0.0039 (7)
C13	0.0160 (8)	0.0183 (8)	0.0221 (8)	−0.0006 (6)	−0.0004 (6)	0.0004 (6)
Li1	0.0238 (15)	0.0167 (13)	0.0276 (14)	−0.0002 (11)	0.0036 (12)	0.0000 (11)
O2W	0.0335 (8)	0.0298 (7)	0.0588 (10)	−0.0001 (6)	−0.0095 (7)	−0.0035 (7)
O3W	0.0268 (7)	0.0278 (7)	0.0523 (9)	0.0018 (6)	−0.0068 (6)	0.0009 (6)

Geometric parameters (Å, º)

Li1—O1W	1.958 (3)	O3W—H32W	0.85 (2)
Li1—O13	1.931 (3)	O3W—H31W	0.857 (17)
Li1—O14^i	1.931 (3)	C1—C6	1.382 (2)
Li1—O14^ii	1.986 (3)	C1—C2	1.393 (2)
Cl2—C2	1.7341 (16)	C2—C3	1.382 (2)
Cl4—C4	1.7409 (19)	C3—C4	1.381 (2)
O11—C1	1.371 (2)	C4—C5	1.372 (3)
O11—C12	1.429 (2)	C5—C6	1.389 (3)
O13—C13	1.2481 (18)	C12—C13	1.522 (2)
O14—C13	1.2575 (19)	C3—H3	0.9500
O1W—H11W	0.855 (18)	C5—H5	0.9500
O1W—H12W	0.86 (2)	C6—H6	0.9500
O2W—H21W	0.848 (18)	C12—H121	0.9900
O2W—H22W	0.86 (2)	C12—H122	0.9900
O1W—Li1—O14^i	107.71 (14)	C2—C3—C4	118.96 (17)
O1W—Li1—O14^ii	105.43 (15)	C3—C4—C5	121.04 (17)
O1W—Li1—O13	111.01 (14)	Cl4—C4—C5	119.76 (13)
O13—Li1—O14^ii	107.67 (13)	Cl4—C4—C3	119.20 (15)
O14^i—Li1—O14^ii	115.90 (14)	C4—C5—C6	119.49 (15)
O13—Li1—O14^i	109.09 (16)	C1—C6—C5	120.86 (17)
Li1^iii—O14—Li1^iv	102.01 (13)	O11—C12—C13	113.75 (12)
Li1—O1W—H11W	115.1 (14)	O13—C13—O14	125.08 (15)
Li1—O1W—H12W	111.0 (15)	O13—C13—C12	118.85 (14)
C1—O11—C12	117.96 (13)	O14—C13—C12	116.03 (13)
C13—O13—Li1	126.78 (13)	C2—C3—H3	121.00
C13—O14—Li1^iii	139.60 (14)	C4—C3—H3	121.00
C13—O14—Li1^iv	118.28 (12)	C4—C5—H5	120.00
H11W—O1W—H12W	101 (2)	C6—C5—H5	120.00
H21W—O2W—H22W	104 (2)	C5—C6—H6	120.00
H31W—O3W—H32W	108 (2)	C1—C6—H6	120.00
O11—C1—C2	116.48 (14)	O11—C12—H122	109.00
C2—C1—C6	118.44 (15)	C13—C12—H121	109.00
O11—C1—C6	125.07 (15)	C13—C12—H122	109.00
Cl2—C2—C3	119.03 (12)	H121—C12—H122	108.00
Cl2—C2—C1	119.75 (12)	O11—C12—H121	109.00
C1—C2—C3	121.20 (15)
C12—O11—C1—C2	−171.51 (13)	C13—O14—Li1^iv—O13^iv	−164.31 (13)
C12—O11—C1—C6	9.3 (2)	O11—C1—C2—Cl2	2.6 (2)
C1—O11—C12—C13	72.75 (17)	O11—C1—C2—C3	−178.98 (15)
Li1—O13—C13—O14	31.9 (3)	C6—C1—C2—Cl2	−178.14 (13)
Li1—O13—C13—C12	−150.39 (16)	C6—C1—C2—C3	0.3 (2)
C13—O13—Li1—O1W	61.1 (2)	O11—C1—C6—C5	178.96 (16)
C13—O13—Li1—O14^i	179.59 (14)	C2—C1—C6—C5	−0.2 (3)
C13—O13—Li1—O14^ii	−53.9 (2)	Cl2—C2—C3—C4	178.14 (14)
Li1^iii—O14—C13—O13	−166.17 (18)	C1—C2—C3—C4	−0.3 (3)
Li1^iii—O14—C13—C12	16.1 (3)	C2—C3—C4—Cl4	−179.11 (14)
Li1^iv—O14—C13—O13	18.3 (2)	C2—C3—C4—C5	0.2 (3)
Li1^iv—O14—C13—C12	−159.49 (14)	Cl4—C4—C5—C6	179.16 (15)
C13—O14—Li1^iii—O1W^iii	79.5 (2)	C3—C4—C5—C6	−0.2 (3)
C13—O14—Li1^iii—O13^iii	−41.1 (3)	C4—C5—C6—C1	0.2 (3)
C13—O14—Li1^iii—O14^iv	−162.81 (17)	O11—C12—C13—O13	7.5 (2)
C13—O14—Li1^iv—O14^ii	−41.9 (2)	O11—C12—C13—O14	−174.58 (14)
C13—O14—Li1^iv—O1W^iv	77.12 (17)

Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y−1/2, −z+3/2; (iii) x, y+1, z; (iv) −x+3/2, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O3W^v	0.86 (2)	1.92 (2)	2.774 (2)	178 (2)
O1W—H12W···O2W^i	0.86 (2)	1.90 (2)	2.760 (2)	175 (2)
O2W—H21W···O11^v	0.85 (2)	2.26 (2)	3.063 (2)	159 (2)
O2W—H22W···O1W	0.86 (2)	2.05 (2)	2.904 (2)	174 (2)
O3W—H31W···O13	0.86 (2)	1.93 (2)	2.7702 (18)	166 (2)
O3W—H32W···O3W^vi	0.85 (2)	1.95 (2)	2.793 (2)	170 (2)
C6—H6···O2W	0.95	2.57	3.302 (2)	134

Symmetry codes: (i) x, y−1, z; (v) x−1, y, z; (vi) −x+5/2, y−1/2, −z+3/2.

(II) Poly[µ-aqua-bis[µ₃-2-(2,4-dichlorophenoxy)acetato-κ⁴O¹:O^1':O^1',Cl]dirubidium(I)]

Crystal data

[Rb2(C8H5Cl2O3)2(H2O)]	F(000) = 1224
Mr = 629.01	Dx = 1.997 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2620 reflections
a = 37.254 (2) Å	θ = 3.4–28.7°
b = 4.3589 (3) Å	µ = 5.22 mm^−1
c = 13.2378 (10) Å	T = 200 K
β = 103.231 (7)°	Plate, colourless
V = 2092.6 (3) Å^3	0.35 × 0.20 × 0.10 mm
Z = 4

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	2057 independent reflections
Radiation source: Enhance (Mo) X-ray source	1809 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.2°
ω scans	h = −45→45
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −5→5
Tmin = 0.363, Tmax = 0.980	l = −13→16
6951 measured reflections

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0278P)^2] where P = (Fo^2 + 2Fc^2)/3
2057 reflections	(Δ/σ)max < 0.001
135 parameters	Δρmax = 0.42 e Å^−3
1 restraint	Δρmin = −0.47 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
Rb1	0.46619 (1)	0.24997 (5)	0.37141 (2)	0.0223 (1)
Cl2	0.37833 (2)	0.43136 (18)	0.27103 (5)	0.0371 (3)
Cl4	0.24780 (2)	0.67498 (18)	0.36032 (6)	0.0368 (2)
O1W	0.50000	−0.1821 (6)	0.25000	0.0290 (9)
O11	0.39401 (4)	0.0914 (4)	0.46469 (12)	0.0228 (6)
O13	0.45789 (5)	−0.2380 (3)	0.50066 (15)	0.0246 (6)
O14	0.44783 (5)	−0.4161 (4)	0.65027 (13)	0.0277 (6)
C1	0.36003 (7)	0.2255 (5)	0.4462 (2)	0.0196 (8)
C2	0.34901 (7)	0.3967 (6)	0.35509 (18)	0.0218 (8)
C3	0.31509 (7)	0.5390 (6)	0.32949 (18)	0.0245 (8)
C4	0.29135 (7)	0.5079 (6)	0.3946 (2)	0.0251 (8)
C5	0.30147 (7)	0.3470 (6)	0.4854 (2)	0.0269 (9)
C6	0.33576 (8)	0.2060 (6)	0.5112 (2)	0.0241 (9)
C12	0.40380 (6)	−0.0845 (6)	0.55864 (18)	0.0194 (8)
C13	0.43981 (8)	−0.2602 (5)	0.5690 (2)	0.0199 (8)
H5	0.34270	0.09430	0.57430	0.0290*
H1W	0.5182 (8)	−0.287 (6)	0.289 (2)	0.0550*
H3	0.30820	0.65690	0.26770	0.0290*
H6	0.28510	0.33190	0.53070	0.0320*
H121	0.38370	−0.23190	0.56050	0.0230*
H122	0.40610	0.05530	0.61870	0.0230*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.0233 (2)	0.0238 (2)	0.0207 (2)	0.0010 (1)	0.0072 (1)	0.0006 (1)
Cl2	0.0312 (4)	0.0596 (5)	0.0239 (4)	0.0127 (3)	0.0135 (3)	0.0139 (3)
Cl4	0.0255 (4)	0.0483 (4)	0.0365 (4)	0.0139 (3)	0.0070 (3)	0.0046 (3)
O1W	0.0279 (17)	0.0228 (15)	0.0353 (17)	0.0000	0.0049 (13)	0.0000
O11	0.0199 (10)	0.0319 (11)	0.0173 (9)	0.0073 (8)	0.0057 (7)	0.0063 (8)
O13	0.0226 (11)	0.0288 (12)	0.0241 (10)	0.0029 (7)	0.0089 (8)	−0.0002 (7)
O14	0.0308 (11)	0.0299 (11)	0.0210 (10)	0.0062 (8)	0.0032 (8)	0.0061 (8)
C1	0.0184 (15)	0.0206 (14)	0.0187 (13)	−0.0004 (10)	0.0023 (11)	−0.0042 (10)
C2	0.0215 (14)	0.0282 (15)	0.0167 (13)	0.0003 (11)	0.0063 (10)	−0.0008 (11)
C3	0.0266 (15)	0.0266 (15)	0.0190 (13)	0.0025 (12)	0.0023 (11)	0.0035 (11)
C4	0.0185 (14)	0.0268 (15)	0.0286 (14)	0.0041 (11)	0.0026 (11)	−0.0031 (12)
C5	0.0239 (15)	0.0326 (15)	0.0265 (15)	0.0027 (12)	0.0107 (12)	0.0002 (13)
C6	0.0261 (16)	0.0268 (15)	0.0202 (14)	0.0025 (11)	0.0070 (11)	0.0025 (11)
C12	0.0206 (14)	0.0225 (14)	0.0153 (12)	0.0015 (10)	0.0043 (10)	0.0013 (11)
C13	0.0212 (15)	0.0184 (14)	0.0189 (14)	−0.0025 (9)	0.0020 (11)	−0.0049 (10)

Geometric parameters (Å, º)

Rb1—Cl2	3.3335 (8)	O1W—H1W^iv	0.88 (3)
Rb1—O1W	2.9400 (17)	C1—C6	1.386 (4)
Rb1—O13	2.7909 (16)	C1—C2	1.398 (3)
Rb1—O13^i	2.8717 (16)	C2—C3	1.379 (4)
Rb1—O13^ii	2.946 (2)	C3—C4	1.376 (4)
Rb1—O14^iii	2.9403 (17)	C4—C5	1.368 (4)
Cl2—C2	1.735 (3)	C5—C6	1.388 (4)
Cl4—C4	1.741 (3)	C12—C13	1.523 (4)
O11—C1	1.365 (3)	C3—H3	0.9500
O11—C12	1.435 (3)	C5—H5	0.9500
O13—C13	1.249 (3)	C6—H6	0.9500
O14—C13	1.250 (3)	C12—H121	0.9900
O1W—H1W	0.88 (3)	C12—H122	0.9900
Cl2—Rb1—O1W	116.01 (2)	Rb1^iv—O1W—H1W^iv	112.4 (18)
Cl2—Rb1—O13	100.88 (4)	O11—C1—C2	117.4 (2)
Cl2—Rb1—O13^i	79.83 (4)	O11—C1—C6	124.9 (2)
Cl2—Rb1—O13^ii	163.59 (3)	C2—C1—C6	117.6 (2)
Cl2—Rb1—O14^iii	63.98 (4)	Cl2—C2—C1	119.8 (2)
O1W—Rb1—O13	88.19 (5)	C1—C2—C3	121.6 (2)
O1W—Rb1—O13^i	160.32 (5)	Cl2—C2—C3	118.64 (19)
O1W—Rb1—O13^ii	80.08 (3)	C2—C3—C4	119.1 (2)
O1W—Rb1—O14^iii	69.18 (4)	Cl4—C4—C5	119.8 (2)
O13—Rb1—O13^i	100.66 (5)	Cl4—C4—C3	119.3 (2)
O13—Rb1—O13^ii	81.98 (5)	C3—C4—C5	120.9 (2)
O13—Rb1—O14^iii	139.90 (5)	C4—C5—C6	119.8 (2)
O13^i—Rb1—O13^ii	83.76 (5)	C1—C6—C5	121.0 (2)
O13^i—Rb1—O14^iii	111.69 (5)	O11—C12—C13	112.98 (19)
O13^ii—Rb1—O14^iii	123.41 (5)	O13—C13—C12	120.4 (2)
Rb1—Cl2—C2	115.37 (9)	O14—C13—C12	112.5 (2)
Rb1—O1W—Rb1^iv	100.33 (8)	O13—C13—O14	127.1 (3)
C1—O11—C12	115.19 (18)	C2—C3—H3	120.00
Rb1—O13—C13	131.05 (14)	C4—C3—H3	120.00
Rb1—O13—Rb1^v	100.66 (6)	C4—C5—H5	120.00
Rb1—O13—Rb1^ii	98.02 (5)	C6—C5—H5	120.00
Rb1^v—O13—C13	121.38 (13)	C1—C6—H6	119.00
Rb1^ii—O13—C13	100.85 (17)	C5—C6—H6	120.00
Rb1^v—O13—Rb1^ii	96.24 (5)	O11—C12—H121	109.00
Rb1^vi—O14—C13	132.73 (15)	O11—C12—H122	109.00
Rb1^iv—O1W—H1W	106.5 (18)	C13—C12—H121	109.00
Rb1—O1W—H1W	112.4 (17)	C13—C12—H122	109.00
Rb1—O1W—H1W^iv	106.5 (19)	H121—C12—H122	108.00
H1W—O1W—H1W^iv	117 (3)
Cl2—Rb1—O1W—Rb1^iv	93.63 (3)	Rb1—Cl2—C2—C1	−16.8 (2)
O13—Rb1—O1W—Rb1^iv	−165.14 (4)	Rb1—Cl2—C2—C3	163.54 (18)
Cl2—Rb1—O13—C13	−51.6 (2)	C12—O11—C1—C2	−179.3 (2)
Cl2—Rb1—O13—Rb1^v	98.44 (5)	C12—O11—C1—C6	1.1 (3)
Cl2—Rb1—O13—Rb1^ii	−163.62 (4)	C1—O11—C12—C13	173.03 (19)
O1W—Rb1—O13—C13	−167.8 (2)	Rb1—O13—C13—O14	−147.62 (19)
O1W—Rb1—O13—Rb1^v	−17.71 (5)	Rb1—O13—C13—C12	32.0 (3)
O1W—Rb1—O13—Rb1^ii	80.24 (4)	Rb1^v—O13—C13—O14	67.5 (3)
O13^i—Rb1—O13—C13	30.0 (2)	Rb1^v—O13—C13—C12	−112.9 (2)
O13^i—Rb1—O13—Rb1^v	180.00 (6)	Rb1^ii—O13—C13—O14	−36.8 (3)
O13^i—Rb1—O13—Rb1^ii	−82.06 (6)	Rb1^ii—O13—C13—C12	142.8 (2)
O13^ii—Rb1—O13—C13	112.0 (2)	Rb1^vi—O14—C13—O13	115.4 (2)
O13^ii—Rb1—O13—Rb1^v	−97.94 (6)	Rb1^vi—O14—C13—C12	−64.3 (3)
O13^ii—Rb1—O13—Rb1^ii	0.00 (6)	O11—C1—C2—Cl2	0.0 (3)
O14^iii—Rb1—O13—C13	−113.9 (2)	O11—C1—C2—C3	179.6 (2)
O14^iii—Rb1—O13—Rb1^v	36.17 (11)	C6—C1—C2—Cl2	179.61 (19)
O14^iii—Rb1—O13—Rb1^ii	134.11 (7)	C6—C1—C2—C3	−0.7 (4)
Cl2—Rb1—O13^i—Rb1^i	−80.71 (5)	O11—C1—C6—C5	−179.2 (2)
Cl2—Rb1—O13^i—C13^i	73.12 (19)	C2—C1—C6—C5	1.2 (4)
O13—Rb1—O13^i—Rb1^i	180.00 (6)	Cl2—C2—C3—C4	178.7 (2)
O13—Rb1—O13^i—C13^i	−26.2 (2)	C1—C2—C3—C4	−0.9 (4)
O13—Rb1—O13^ii—Rb1^ii	0.00 (6)	C2—C3—C4—Cl4	−177.6 (2)
O13—Rb1—O13^ii—C13^ii	134.61 (13)	C2—C3—C4—C5	2.2 (4)
Cl2—Rb1—O14^iii—C13^iii	−95.6 (2)	Cl4—C4—C5—C6	178.1 (2)
O13—Rb1—O14^iii—C13^iii	−20.3 (3)	C3—C4—C5—C6	−1.7 (4)
O1W—Rb1—Cl2—C2	129.66 (11)	C4—C5—C6—C1	0.0 (4)
O13—Rb1—Cl2—C2	36.34 (11)	O11—C12—C13—O13	1.3 (3)
O13^i—Rb1—Cl2—C2	−62.68 (11)	O11—C12—C13—O14	−179.0 (2)
O14^iii—Rb1—Cl2—C2	176.96 (11)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O14^vii	0.88 (3)	1.86 (3)	2.723 (2)	166 (3)

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

(III) Poly[µ-aqua-bis[µ₃-2-(2,4-dichlorophenoxy)acetato-κ⁵O¹:O^1':O^1',O²:Cl]-dicaesium(I)]

Crystal data

[Cs2(C8H5Cl2O3)2(H2O)]	F(000) = 1368
Mr = 723.88	Dx = 2.219 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 5814 reflections
a = 8.9877 (4) Å	θ = 3.6–28.6°
b = 7.3441 (2) Å	µ = 3.89 mm^−1
c = 32.8250 (13) Å	T = 200 K
V = 2166.67 (14) Å^3	Plate, colourless
Z = 4	0.30 × 0.22 × 0.10 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	4519 independent reflections
Radiation source: Enhance (Mo) X-ray source	4259 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 16.077 pixels mm^-1	θmax = 29.0°, θmin = 3.6°
ω scans	h = −9→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −9→7
Tmin = 0.642, Tmax = 0.980	l = −43→34
15185 measured reflections

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: inferred from neighbouring sites
wR(F^2) = 0.059	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0226P)^2 + 0.4048P] where P = (Fo^2 + 2Fc^2)/3
4519 reflections	(Δ/σ)max = 0.001
268 parameters	Δρmax = 0.55 e Å^−3
4 restraints	Δρmin = −1.09 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
Cs1	0.39793 (3)	0.87227 (4)	0.61920 (1)	0.0234 (1)
Cs2	0.74246 (3)	0.56521 (4)	0.53580 (1)	0.0248 (1)
Cl2A	0.50500 (16)	1.12366 (16)	0.71033 (5)	0.0310 (4)
Cl2B	0.47449 (15)	0.38099 (16)	0.45046 (5)	0.0291 (4)
Cl4A	0.16789 (17)	0.7733 (2)	0.82087 (5)	0.0395 (5)
Cl4B	0.83358 (16)	0.7247 (2)	0.34450 (5)	0.0352 (5)
O1W	0.0857 (4)	0.7401 (6)	0.58531 (14)	0.0337 (14)
O11A	0.6309 (4)	0.7720 (5)	0.69486 (12)	0.0245 (11)
O11B	0.3286 (4)	0.7283 (5)	0.45830 (12)	0.0253 (11)
O13A	0.7332 (3)	0.7689 (4)	0.61976 (13)	0.0266 (10)
O13B	0.4738 (4)	0.7928 (5)	0.52898 (13)	0.0333 (14)
O14A	0.8847 (4)	0.5357 (5)	0.63378 (12)	0.0296 (11)
O14B	0.4191 (4)	1.0892 (5)	0.52555 (14)	0.0353 (14)
C1A	0.5314 (5)	0.7619 (7)	0.72640 (16)	0.0217 (16)
C1B	0.4481 (5)	0.7399 (7)	0.43267 (17)	0.0223 (16)
C2A	0.4591 (6)	0.9254 (7)	0.73655 (17)	0.0223 (16)
C2B	0.5247 (6)	0.5771 (7)	0.42413 (17)	0.0227 (16)
C3A	0.3483 (6)	0.9292 (7)	0.76539 (17)	0.0243 (17)
C3B	0.6411 (6)	0.5713 (7)	0.39706 (18)	0.0247 (17)
C4A	0.3125 (6)	0.7725 (7)	0.7852 (2)	0.0263 (17)
C4B	0.6854 (6)	0.7317 (8)	0.37813 (18)	0.0247 (17)
C5A	0.3880 (6)	0.6110 (7)	0.77779 (18)	0.0260 (17)
C5B	0.6145 (6)	0.8924 (7)	0.38618 (18)	0.0283 (17)
C6A	0.4983 (5)	0.6079 (7)	0.74849 (17)	0.0233 (16)
C6B	0.4955 (6)	0.8964 (7)	0.41329 (18)	0.0270 (16)
C12A	0.6962 (6)	0.6087 (6)	0.68103 (16)	0.0193 (16)
C12B	0.2939 (6)	0.8921 (7)	0.48090 (17)	0.0227 (17)
C13A	0.7779 (5)	0.6436 (6)	0.64165 (16)	0.0193 (16)
C13B	0.4066 (5)	0.9283 (7)	0.51428 (17)	0.0223 (17)
H3A	0.29760	1.03940	0.77140	0.0290*
H3B	0.69040	0.45970	0.39140	0.0300*
H5A	0.36420	0.50400	0.79270	0.0310*
H5B	0.64650	1.00140	0.37330	0.0340*
H6A	0.55170	0.49850	0.74350	0.0280*
H6B	0.44620	1.00840	0.41850	0.0320*
H11W	0.027 (5)	0.663 (7)	0.5969 (18)	0.0510*
H12A	0.61800	0.51570	0.67660	0.0230*
H12B	0.19370	0.88000	0.49320	0.0280*
H12W	0.022 (5)	0.804 (7)	0.5708 (18)	0.0510*
H13A	0.76630	0.56200	0.70180	0.0230*
H13B	0.29180	0.99710	0.46200	0.0280*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs1	0.0241 (1)	0.0202 (1)	0.0260 (2)	0.0005 (1)	−0.0033 (2)	−0.0002 (2)
Cs2	0.0244 (1)	0.0227 (1)	0.0274 (2)	0.0003 (1)	0.0023 (2)	−0.0002 (2)
Cl2A	0.0395 (8)	0.0186 (6)	0.0350 (8)	0.0022 (5)	0.0001 (7)	0.0027 (5)
Cl2B	0.0275 (7)	0.0238 (6)	0.0361 (8)	0.0009 (5)	0.0048 (6)	0.0038 (6)
Cl4A	0.0387 (8)	0.0452 (8)	0.0346 (9)	−0.0026 (6)	0.0148 (7)	−0.0071 (7)
Cl4B	0.0361 (8)	0.0394 (8)	0.0301 (8)	−0.0010 (6)	0.0125 (7)	0.0000 (6)
O1W	0.025 (2)	0.039 (2)	0.037 (3)	0.0017 (17)	−0.0004 (18)	0.0044 (19)
O11A	0.0242 (18)	0.0202 (17)	0.029 (2)	0.0008 (14)	0.0063 (17)	0.0014 (16)
O11B	0.0222 (18)	0.0258 (19)	0.028 (2)	−0.0028 (15)	0.0035 (17)	−0.0120 (17)
O13A	0.0262 (17)	0.0255 (17)	0.028 (2)	0.0017 (12)	0.002 (2)	0.0048 (19)
O13B	0.035 (2)	0.031 (2)	0.034 (3)	0.0141 (16)	−0.010 (2)	−0.0022 (19)
O14A	0.030 (2)	0.0257 (19)	0.033 (2)	0.0068 (15)	0.0058 (17)	0.0000 (16)
O14B	0.035 (2)	0.029 (2)	0.042 (3)	0.0012 (16)	−0.006 (2)	−0.0134 (19)
C1A	0.019 (2)	0.026 (3)	0.020 (3)	0.0054 (19)	−0.006 (2)	0.001 (2)
C1B	0.018 (2)	0.026 (3)	0.023 (3)	0.0014 (19)	−0.004 (2)	−0.008 (2)
C2A	0.029 (3)	0.020 (2)	0.018 (3)	0.000 (2)	−0.003 (2)	−0.001 (2)
C2B	0.023 (3)	0.023 (2)	0.022 (3)	−0.0037 (19)	−0.002 (2)	−0.002 (2)
C3A	0.024 (3)	0.027 (3)	0.022 (3)	0.005 (2)	−0.002 (2)	−0.010 (2)
C3B	0.024 (3)	0.024 (3)	0.026 (3)	0.005 (2)	−0.002 (2)	−0.004 (2)
C4A	0.029 (3)	0.029 (3)	0.021 (3)	−0.002 (2)	0.000 (3)	−0.009 (3)
C4B	0.021 (3)	0.031 (3)	0.022 (3)	0.003 (2)	0.002 (2)	0.003 (2)
C5A	0.027 (3)	0.026 (3)	0.025 (3)	0.001 (2)	−0.001 (2)	−0.001 (2)
C5B	0.032 (3)	0.025 (3)	0.028 (3)	−0.004 (2)	−0.009 (3)	0.002 (2)
C6A	0.023 (3)	0.021 (2)	0.026 (3)	0.002 (2)	−0.003 (2)	−0.004 (2)
C6B	0.029 (3)	0.019 (2)	0.033 (3)	0.002 (2)	0.001 (2)	−0.003 (2)
C12A	0.021 (3)	0.017 (2)	0.020 (3)	0.0005 (19)	−0.007 (2)	0.001 (2)
C12B	0.022 (3)	0.022 (3)	0.024 (3)	0.006 (2)	0.004 (2)	−0.006 (2)
C13A	0.022 (3)	0.016 (2)	0.020 (3)	−0.0068 (18)	0.002 (2)	−0.0020 (19)
C13B	0.021 (3)	0.028 (3)	0.018 (3)	0.003 (2)	0.004 (2)	−0.004 (2)

Geometric parameters (Å, º)

Cs1—Cl2A	3.6446 (16)	O1W—H12W	0.88 (5)
Cs1—O1W	3.171 (4)	O1W—H11W	0.86 (5)
Cs1—O11A	3.331 (4)	C1A—C2A	1.405 (7)
Cs1—O13A	3.108 (3)	C1A—C6A	1.376 (7)
Cs1—O13B	3.095 (4)	C1B—C6B	1.381 (7)
Cs1—O14A^i	3.037 (4)	C1B—C2B	1.408 (7)
Cs1—O13A^ii	3.023 (3)	C2A—C3A	1.374 (8)
Cs2—O13A	3.137 (4)	C2B—C3B	1.373 (8)
Cs2—O13B	2.945 (4)	C3A—C4A	1.360 (8)
Cs2—Cl2B^iii	3.5146 (16)	C3B—C4B	1.390 (8)
Cs2—O1W^iii	3.107 (4)	C4A—C5A	1.388 (7)
Cs2—O11B^iii	3.423 (4)	C4B—C5B	1.367 (8)
Cs2—O13B^iii	3.360 (4)	C5A—C6A	1.381 (8)
Cs2—O14B^iv	3.013 (4)	C5B—C6B	1.392 (8)
Cl2A—C2A	1.741 (5)	C12A—C13A	1.509 (7)
Cl2B—C2B	1.739 (5)	C12B—C13B	1.516 (7)
Cl4A—C4A	1.749 (6)	C3A—H3A	0.9500
Cl4B—C4B	1.731 (6)	C3B—H3B	0.9500
O11A—C1A	1.370 (6)	C5A—H5A	0.9500
O11A—C12A	1.410 (6)	C5B—H5B	0.9500
O11B—C1B	1.367 (6)	C6A—H6A	0.9500
O11B—C12B	1.447 (6)	C6B—H6B	0.9500
O13A—C13A	1.235 (6)	C12A—H12A	0.9900
O13B—C13B	1.260 (6)	C12A—H13A	0.9900
O14A—C13A	1.271 (6)	C12B—H12B	0.9900
O14B—C13B	1.243 (6)	C12B—H13B	0.9900
Cl2A—Cs1—O1W	132.59 (8)	Cs2^i—O13B—C13B	110.3 (3)
Cl2A—Cs1—O11A	48.24 (7)	Cs1^iii—O14A—C13A	132.6 (3)
Cl2A—Cs1—O13A	82.12 (8)	Cs2^ii—O14B—C13B	141.8 (3)
Cl2A—Cs1—O13B	145.37 (7)	H11W—O1W—H12W	101 (5)
Cl2A—Cs1—O14A^i	112.39 (8)	Cs1—O1W—H11W	126 (4)
Cl2A—Cs1—O13A^ii	71.50 (8)	Cs1—O1W—H12W	127 (3)
O1W—Cs1—O11A	138.61 (10)	Cs2^i—O1W—H11W	92 (4)
O1W—Cs1—O13A	141.76 (10)	Cs2^i—O1W—H12W	113 (4)
O1W—Cs1—O13B	78.55 (10)	O11A—C1A—C2A	115.8 (5)
O1W—Cs1—O14A^i	73.66 (11)	O11A—C1A—C6A	125.7 (5)
O1W—Cs1—O13A^ii	80.53 (10)	C2A—C1A—C6A	118.5 (5)
O11A—Cs1—O13A	48.09 (10)	C2B—C1B—C6B	117.7 (5)
O11A—Cs1—O13B	122.23 (9)	O11B—C1B—C2B	117.0 (5)
O11A—Cs1—O14A^i	71.88 (10)	O11B—C1B—C6B	125.3 (5)
O11A—Cs1—O13A^ii	119.74 (10)	C1A—C2A—C3A	121.0 (5)
O13A—Cs1—O13B	75.28 (10)	Cl2A—C2A—C3A	119.7 (4)
O13A—Cs1—O14A^i	78.23 (9)	Cl2A—C2A—C1A	119.2 (4)
O13A—Cs1—O13A^ii	133.46 (8)	Cl2B—C2B—C1B	118.5 (4)
O13B—Cs1—O14A^i	88.47 (10)	C1B—C2B—C3B	121.9 (5)
O13A^ii—Cs1—O13B	106.15 (11)	Cl2B—C2B—C3B	119.6 (4)
O13A^ii—Cs1—O14A^i	147.15 (9)	C2A—C3A—C4A	118.9 (5)
O13A—Cs2—O13B	76.96 (10)	C2B—C3B—C4B	118.8 (5)
Cl2B^iii—Cs2—O13A	131.48 (6)	Cl4A—C4A—C5A	118.9 (4)
O1W^iii—Cs2—O13A	82.68 (10)	C3A—C4A—C5A	121.6 (5)
O11B^iii—Cs2—O13A	163.58 (8)	Cl4A—C4A—C3A	119.5 (4)
O13A—Cs2—O13B^iii	116.63 (9)	Cl4B—C4B—C3B	118.7 (4)
O13A—Cs2—O14B^iv	73.16 (10)	Cl4B—C4B—C5B	120.5 (4)
Cl2B^iii—Cs2—O13B	111.23 (8)	C3B—C4B—C5B	120.8 (5)
O1W^iii—Cs2—O13B	94.45 (10)	C4A—C5A—C6A	119.1 (5)
O11B^iii—Cs2—O13B	119.10 (10)	C4B—C5B—C6B	120.0 (5)
O13B—Cs2—O13B^iii	161.17 (10)	C1A—C6A—C5A	120.6 (5)
O13B—Cs2—O14B^iv	86.87 (10)	C1B—C6B—C5B	120.9 (5)
Cl2B^iii—Cs2—O1W^iii	140.09 (8)	O11A—C12A—C13A	109.5 (4)
Cl2B^iii—Cs2—O11B^iii	49.02 (7)	O11B—C12B—C13B	111.9 (4)
Cl2B^iii—Cs2—O13B^iii	70.59 (7)	O13A—C13A—O14A	126.3 (5)
Cl2B^iii—Cs2—O14B^iv	60.24 (9)	O13A—C13A—C12A	117.8 (4)
O1W^iii—Cs2—O11B^iii	92.11 (10)	O14A—C13A—C12A	115.8 (4)
O1W^iii—Cs2—O13B^iii	75.56 (10)	O13B—C13B—C12B	117.3 (5)
O1W^iii—Cs2—O14B^iv	154.88 (12)	O14B—C13B—C12B	116.2 (4)
O11B^iii—Cs2—O13B^iii	46.97 (10)	O13B—C13B—O14B	126.4 (5)
O11B^iii—Cs2—O14B^iv	109.17 (10)	C2A—C3A—H3A	121.00
O13B^iii—Cs2—O14B^iv	109.01 (9)	C4A—C3A—H3A	121.00
Cs1—Cl2A—C2A	85.38 (19)	C2B—C3B—H3B	121.00
Cs2^i—Cl2B—C2B	117.19 (19)	C4B—C3B—H3B	121.00
Cs1—O1W—Cs2^i	90.18 (10)	C4A—C5A—H5A	120.00
Cs1—O11A—C1A	99.5 (3)	C6A—C5A—H5A	120.00
Cs1—O11A—C12A	102.1 (3)	C4B—C5B—H5B	120.00
C1A—O11A—C12A	118.0 (4)	C6B—C5B—H5B	120.00
C1B—O11B—C12B	115.7 (4)	C1A—C6A—H6A	120.00
Cs2^i—O11B—C1B	132.4 (3)	C5A—C6A—H6A	120.00
Cs2^i—O11B—C12B	95.4 (3)	C1B—C6B—H6B	120.00
Cs1—O13A—Cs2	97.88 (10)	C5B—C6B—H6B	119.00
Cs1—O13A—C13A	120.1 (3)	O11A—C12A—H12A	110.00
Cs1—O13A—Cs1^iv	105.19 (9)	O11A—C12A—H13A	110.00
Cs2—O13A—C13A	98.5 (3)	C13A—C12A—H12A	110.00
Cs1^iv—O13A—Cs2	113.42 (12)	C13A—C12A—H13A	110.00
Cs1^iv—O13A—C13A	119.6 (3)	H12A—C12A—H13A	108.00
Cs1—O13B—Cs2	102.41 (12)	O11B—C12B—H12B	109.00
Cs1—O13B—C13B	96.4 (3)	O11B—C12B—H13B	109.00
Cs1—O13B—Cs2^i	86.99 (10)	C13B—C12B—H12B	109.00
Cs2—O13B—C13B	150.5 (3)	C13B—C12B—H13B	109.00
Cs2—O13B—Cs2^i	93.34 (10)	H12B—C12B—H13B	108.00
O1W—Cs1—Cl2A—C2A	71.1 (2)	O14B^iv—Cs2—O13A—Cs1	111.29 (11)
O11A—Cs1—Cl2A—C2A	−52.0 (2)	O14B^iv—Cs2—O13A—C13A	−126.6 (3)
O13A—Cs1—Cl2A—C2A	−90.67 (19)	O14B^iv—Cs2—O13A—Cs1^iv	0.92 (10)
O13B—Cs1—Cl2A—C2A	−140.0 (2)	O13A—Cs2—O13B—Cs1	−21.03 (9)
O14A^i—Cs1—Cl2A—C2A	−16.9 (2)	O13A—Cs2—O13B—C13B	107.4 (7)
O13A^ii—Cs1—Cl2A—C2A	128.2 (2)	O13A—Cs2—O13B—Cs2^i	−108.67 (10)
Cl2A—Cs1—O1W—Cs2^i	−156.08 (5)	Cl2B^iii—Cs2—O13B—Cs1	−150.78 (7)
O11A—Cs1—O1W—Cs2^i	−85.06 (16)	Cl2B^iii—Cs2—O13B—C13B	−22.4 (7)
O13A—Cs1—O1W—Cs2^i	−6.2 (2)	Cl2B^iii—Cs2—O13B—Cs2^i	121.58 (7)
O13B—Cs1—O1W—Cs2^i	41.33 (10)	O1W^iii—Cs2—O13B—Cs1	60.39 (12)
O14A^i—Cs1—O1W—Cs2^i	−50.45 (10)	O1W^iii—Cs2—O13B—C13B	−171.2 (7)
O13A^ii—Cs1—O1W—Cs2^i	150.08 (12)	O1W^iii—Cs2—O13B—Cs2^i	−27.25 (12)
Cl2A—Cs1—O11A—C1A	65.0 (3)	O11B^iii—Cs2—O13B—Cs1	155.30 (9)
Cl2A—Cs1—O11A—C12A	−173.5 (3)	O11B^iii—Cs2—O13B—C13B	−76.3 (7)
O1W—Cs1—O11A—C1A	−46.0 (3)	O11B^iii—Cs2—O13B—Cs2^i	67.66 (13)
O1W—Cs1—O11A—C12A	75.5 (3)	O14B^iv—Cs2—O13B—Cs1	−94.46 (12)
O13A—Cs1—O11A—C1A	−171.3 (3)	O14B^iv—Cs2—O13B—C13B	34.0 (7)
O13A—Cs1—O11A—C12A	−49.8 (3)	O14B^iv—Cs2—O13B—Cs2^i	177.89 (12)
O13B—Cs1—O11A—C1A	−157.1 (3)	O13A—Cs2—Cl2B^iii—C2B^iii	143.5 (2)
O13B—Cs1—O11A—C12A	−35.7 (3)	O13B—Cs2—Cl2B^iii—C2B^iii	−125.3 (2)
O14A^i—Cs1—O11A—C1A	−81.0 (3)	O13A—Cs2—O1W^iii—Cs1^iii	−81.98 (10)
O14A^i—Cs1—O11A—C12A	40.5 (3)	O13B—Cs2—O1W^iii—Cs1^iii	−158.20 (11)
O13A^ii—Cs1—O11A—C1A	65.2 (3)	O13B—Cs2—O11B^iii—C1B^iii	118.2 (4)
O13A^ii—Cs1—O11A—C12A	−173.3 (3)	O13B—Cs2—O11B^iii—C12B^iii	−109.4 (3)
Cl2A—Cs1—O13A—Cs2	−173.28 (8)	O13A—Cs2—O13B^iii—Cs1^iii	34.79 (11)
Cl2A—Cs1—O13A—C13A	82.1 (4)	O13A—Cs2—O13B^iii—Cs2^iii	−67.48 (12)
Cl2A—Cs1—O13A—Cs1^iv	−56.33 (10)	O13A—Cs2—O13B^iii—C13B^iii	130.5 (3)
O1W—Cs1—O13A—Cs2	28.6 (2)	O13A—Cs2—O14B^iv—C13B^iv	−93.3 (6)
O1W—Cs1—O13A—C13A	−76.0 (4)	O13B—Cs2—O14B^iv—C13B^iv	−15.9 (6)
O1W—Cs1—O13A—Cs1^iv	145.54 (14)	Cs1—Cl2A—C2A—C1A	57.6 (4)
O11A—Cs1—O13A—Cs2	147.91 (14)	Cs1—Cl2A—C2A—C3A	−119.3 (5)
O11A—Cs1—O13A—C13A	43.3 (3)	Cs2^i—Cl2B—C2B—C1B	−12.7 (5)
O11A—Cs1—O13A—Cs1^iv	−95.14 (15)	Cs2^i—Cl2B—C2B—C3B	164.6 (4)
O13B—Cs1—O13A—Cs2	−19.74 (9)	Cs1—O11A—C1A—C2A	−65.1 (4)
O13B—Cs1—O13A—C13A	−124.3 (4)	Cs1—O11A—C1A—C6A	115.3 (5)
O13B—Cs1—O13A—Cs1^iv	97.22 (13)	C12A—O11A—C1A—C2A	−174.3 (4)
O14A^i—Cs1—O13A—Cs2	71.79 (10)	C12A—O11A—C1A—C6A	6.1 (7)
O14A^i—Cs1—O13A—C13A	−32.8 (4)	Cs1—O11A—C12A—C13A	61.5 (4)
O14A^i—Cs1—O13A—Cs1^iv	−171.26 (14)	C1A—O11A—C12A—C13A	169.2 (4)
O13A^ii—Cs1—O13A—Cs2	−118.21 (13)	C12B—O11B—C1B—C2B	153.2 (5)
O13A^ii—Cs1—O13A—C13A	137.2 (3)	C12B—O11B—C1B—C6B	−29.7 (7)
O13A^ii—Cs1—O13A—Cs1^iv	−1.3 (2)	Cs2^i—O11B—C1B—C2B	27.8 (7)
Cl2A—Cs1—O13B—Cs2	72.35 (16)	Cs2^i—O11B—C1B—C6B	−155.1 (4)
Cl2A—Cs1—O13B—C13B	−84.8 (3)	C1B—O11B—C12B—C13B	−72.5 (5)
Cl2A—Cs1—O13B—Cs2^i	165.11 (6)	Cs2^i—O11B—C12B—C13B	70.4 (4)
O1W—Cs1—O13B—Cs2	−130.46 (13)	Cs1—O13A—C13A—O14A	147.3 (4)
O1W—Cs1—O13B—C13B	72.4 (3)	Cs1—O13A—C13A—C12A	−30.5 (5)
O1W—Cs1—O13B—Cs2^i	−37.71 (9)	Cs2—O13A—C13A—O14A	43.0 (5)
O11A—Cs1—O13B—Cs2	10.55 (15)	Cs2—O13A—C13A—C12A	−134.8 (4)
O11A—Cs1—O13B—C13B	−146.6 (3)	Cs1^iv—O13A—C13A—O14A	−80.1 (6)
O11A—Cs1—O13B—Cs2^i	103.30 (10)	Cs1^iv—O13A—C13A—C12A	102.1 (4)
O13A—Cs1—O13B—Cs2	21.40 (9)	Cs1—O13B—C13B—O14B	50.3 (6)
O13A—Cs1—O13B—C13B	−135.8 (3)	Cs1—O13B—C13B—C12B	−126.6 (4)
O13A—Cs1—O13B—Cs2^i	114.15 (9)	Cs2—O13B—C13B—O14B	−79.3 (9)
O14A^i—Cs1—O13B—Cs2	−56.83 (11)	Cs2—O13B—C13B—C12B	103.8 (7)
O14A^i—Cs1—O13B—C13B	146.0 (3)	Cs2^i—O13B—C13B—O14B	139.5 (5)
O14A^i—Cs1—O13B—Cs2^i	35.93 (9)	Cs2^i—O13B—C13B—C12B	−37.4 (5)
O13A^ii—Cs1—O13B—Cs2	153.03 (9)	Cs1^iii—O14A—C13A—O13A	−115.5 (5)
O13A^ii—Cs1—O13B—C13B	−4.1 (3)	Cs1^iii—O14A—C13A—C12A	62.3 (6)
O13A^ii—Cs1—O13B—Cs2^i	−114.21 (8)	Cs2^ii—O14B—C13B—O13B	−145.3 (4)
Cl2A—Cs1—O14A^i—C13A^i	97.7 (4)	Cs2^ii—O14B—C13B—C12B	31.7 (8)
O1W—Cs1—O14A^i—C13A^i	−32.3 (4)	O11A—C1A—C2A—Cl2A	−2.2 (6)
O11A—Cs1—O14A^i—C13A^i	124.5 (5)	O11A—C1A—C2A—C3A	174.7 (5)
O13A—Cs1—O14A^i—C13A^i	173.9 (5)	C6A—C1A—C2A—Cl2A	177.4 (4)
O13B—Cs1—O14A^i—C13A^i	−110.8 (4)	C6A—C1A—C2A—C3A	−5.7 (8)
Cl2A—Cs1—O13A^ii—Cs1^ii	−120.74 (12)	O11A—C1A—C6A—C5A	−175.3 (5)
Cl2A—Cs1—O13A^ii—Cs2^ii	133.46 (9)	C2A—C1A—C6A—C5A	5.1 (8)
Cl2A—Cs1—O13A^ii—C13A^ii	18.0 (3)	O11B—C1B—C2B—Cl2B	−6.5 (7)
O1W—Cs1—O13A^ii—Cs1^ii	20.45 (12)	O11B—C1B—C2B—C3B	176.3 (5)
O1W—Cs1—O13A^ii—Cs2^ii	−85.35 (12)	C6B—C1B—C2B—Cl2B	176.2 (4)
O1W—Cs1—O13A^ii—C13A^ii	159.2 (4)	C6B—C1B—C2B—C3B	−1.0 (8)
O11A—Cs1—O13A^ii—Cs1^ii	−120.88 (11)	O11B—C1B—C6B—C5B	−176.9 (5)
O11A—Cs1—O13A^ii—Cs2^ii	133.32 (11)	C2B—C1B—C6B—C5B	0.2 (8)
O11A—Cs1—O13A^ii—C13A^ii	17.8 (4)	Cl2A—C2A—C3A—C4A	179.1 (4)
O13A—Cs1—O13A^ii—Cs1^ii	−179.65 (11)	C1A—C2A—C3A—C4A	2.2 (8)
O13A—Cs1—O13A^ii—Cs2^ii	74.55 (17)	Cl2B—C2B—C3B—C4B	−176.2 (4)
O13A—Cs1—O13A^ii—C13A^ii	−41.0 (4)	C1B—C2B—C3B—C4B	1.0 (8)
O13B—Cs1—O13A^ii—Cs1^ii	95.51 (12)	C2A—C3A—C4A—Cl4A	−178.0 (4)
O13B—Cs1—O13A^ii—Cs2^ii	−10.29 (12)	C2A—C3A—C4A—C5A	1.9 (9)
O13B—Cs1—O13A^ii—C13A^ii	−125.8 (4)	C2B—C3B—C4B—Cl4B	179.2 (4)
O13B—Cs2—O13A—Cs1	20.63 (9)	C2B—C3B—C4B—C5B	−0.1 (9)
O13B—Cs2—O13A—C13A	142.8 (3)	Cl4A—C4A—C5A—C6A	177.4 (4)
O13B—Cs2—O13A—Cs1^iv	−89.74 (11)	C3A—C4A—C5A—C6A	−2.5 (9)
Cl2B^iii—Cs2—O13A—Cs1	127.57 (6)	Cl4B—C4B—C5B—C6B	−180.0 (5)
Cl2B^iii—Cs2—O13A—C13A	−110.3 (3)	C3B—C4B—C5B—C6B	−0.7 (9)
Cl2B^iii—Cs2—O13A—Cs1^iv	17.20 (14)	C4A—C5A—C6A—C1A	−1.1 (8)
O1W^iii—Cs2—O13A—Cs1	−75.69 (10)	C4B—C5B—C6B—C1B	0.6 (9)
O1W^iii—Cs2—O13A—C13A	46.5 (3)	O11A—C12A—C13A—O13A	−27.7 (6)
O1W^iii—Cs2—O13A—Cs1^iv	173.94 (11)	O11A—C12A—C13A—O14A	154.3 (4)
O13B^iii—Cs2—O13A—Cs1	−145.47 (9)	O11B—C12B—C13B—O13B	−27.1 (6)
O13B^iii—Cs2—O13A—C13A	−23.3 (3)	O11B—C12B—C13B—O14B	155.7 (4)
O13B^iii—Cs2—O13A—Cs1^iv	104.16 (11)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O14A^v	0.86 (5)	1.99 (5)	2.837 (6)	166 (5)
O1W—H12W···O14B^ii	0.88 (5)	1.92 (6)	2.768 (6)	162 (5)
C12A—H12A···O14A^i	0.99	2.55	3.372 (6)	140

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