Two-dimensional coordination polymeric structures in caesium complexes with ring-substituted phen­oxy­acetic acids

The two-dimensional polymeric structures of the caesium com­plexes with the phen­oxy­acetic acid analogues (4-fluoro­phen­oxy)acetic acid, (3-chloro-2-methyl­phen­oxy)acetic acid and the herbicidally active (2,4-di­chloro­phen­oxy)acetic acid (2,4-D), namely poly[[μ₅-(4-fluoro­phen­oxy)acetato][μ₄-(4-fluoro­phen­oxy)acetato]­dicaesium], [Cs₂(C₈H₆FO₃)₂]_n, (I), poly[aqua­[μ₅-(3-chloro-2-methyl­phen­oxy)acetato]caesium], [Cs(C₉H₈ClO₃)(H₂O)]_n, (II), and poly[[μ₇-(2,4-di­chloro­phen­oxy)acetato][(2,4-dichlorphen­oxy)acetic acid]caesium], [Cs(C₈H₅Cl₂O₃)(C₈H₆Cl₂O₃)]_n, (III), are described. In (I), the Cs⁺ cations of the two individual irregular coordination polyhedra in the asymmetric unit (one CsO₇ and the other CsO₈) are linked by bridging carboxyl­ate O-atom donors from the two ligand mol­ecules, both of which are involved in bidentate chelate O_carboxy,O_phenoxy inter­actions, while only one has a bidentate carboxyl­ate O,O′-chelate inter­action. Polymeric extension is achieved through a number of carboxyl­ate O-atom bridges, with a minimum Cs...Cs separation of 4.3231 (9) Å, giving layers which lie parallel to (001). In hydrated complex (II), the irregular nine-coordination about the Cs⁺ cation comprises a single monodentate water mol­ecule, a bidentate O_carboxy,O_phenoxy chelate inter­action and six bridging carboxyl­ate O-atom bonding inter­actions, giving a Cs...Cs separation of 4.2473 (3) Å. The water mol­ecule forms intra­layer hydrogen bonds within the two-dimensional layers, which lie parallel to (100). In complex (III), the irregular centrosymmetric CsO₆Cl₂ coordination environment comprises two O-atom donors and two ring-substituted Cl-atom donors from two hydrogen bis­[(2,4-di­chloro­phen­oxy)acetate] ligand species in a bidentate chelate mode, and four O-atom donors from bridging carboxyl groups. The duplex ligand species lie across crystallographic inversion centres, linked through a short O—H...O hydrogen bond involving the single acid H atom. Structure extension gives layers which lie parallel to (001). The present set of structures of Cs salts of phen­oxy­acetic acids show previously demonstrated trends among the alkali metal salts of simple benzoic acids with no stereochemically favourable inter­active substituent groups for formation of two-dimensional coordination polymers.

S1. Introduction

The caesium salts of the carb­oxy­lic acids are of particular inter­est because of the ability of that metal to form expanded coordination polyhedra, as well as exhibiting bridging of metal centres through carboxyl O atoms and, when present, water molecules. Also common is the presence of bidentate carboxyl­ate O,O'-chelate inter­actions having a small bite angle at the metal centre. The structures so generated provide examples of stable coordination polymers which, with the aromatic acid having no inter­active secondary substituent groups, are two-dimensional, e.g. caesium hydrogen trans-cinnamate (Smith, 2014b). With a suitable ring-substituted group, the polymer may be expanded into three dimensions, such as is found in the caesium 4-nitro­benzoate monohydrate structure (Smith, 2013c) and in the caesium 3,5-di­nitro­benzoate dihydrate structure (Smith, 2012b), through Cs—O_nitro bonds. However, crystallographically characterized examples of these Cs salts of aromatic carb­oxy­lic acids are not common.

The structures of any alkali metal salts of the phen­oxy­acetic acid analogues are even more rare in the crystallographic literature, comprising just four examples: sodium phen­oxy­acetate hemihydrate (Prout et al., 1971; Evans et al., 2001), anhydrous caesium phen­oxy­acetate (Smith, 2014b), caesium o-phenyl­ene­dioxydi­acetate dihydrate (Smith et al., 1989) and the potassium salt of the herbicidally active (2,4-di­chloro­phen­oxy)­acetic acid (2,4-D) (a hemihydrate) (Kennard et al., 1983). Our previous work on the metal complexes of the phen­oxy­alkanoic acids has provided a large number of structures involving primarily those with the metals of the first transition series (e.g. Smith et al., 1980, 1985, 1993; Smith, 2012b). The metal–ligand inter­active modes with these common metals include monodentate and bidentate–bridging structures involving the chelate O_carb­oxy,O¹_phen­oxy [O,O)¹-chelate] inter­action, but only occasional examples of the bidentate carboxyl­ate O,O'-chelate inter­action have been found. The unique phen­oxy­alkanoate O,O¹-chelate inter­action was first reported for the monomeric copper(II) phen­oxy­acetate complex (Prout et al., 1968), and with the potassium–2,4-D salt (Kennard et al., 1983) a tridentate chelate inter­action is found which includes, in addition to the O,O¹-chelate, a K—Cl bond to the ortho-Cl ring substituent of the ligand.

To investigate the modes of inter­action and the nature of the coordination complex structures generated, the reaction of a number of ring-substituted phen­oxy­acetic acid analogues with CsOH in aqueous ethanol was completed, affording three examples of polymeric caesium salts, namely with (4-fluoro­phen­oxy)­acetic acid (PFPA), [Cs₂(C₈H₆FO₃)₂]_n, (I), with (3-chloro-2-methyl­phen­oxy)­acetic acid (2,3-MCPA), [Cs(C₉H₈ClO₃)(H₂O)]_n, (II), and with (2,4-di­chloro­phen­oxy)­acetic acid (2,4-D), [Cs(C₈H₅Cl₂O₃)(C₈H₆Cl₂O₃)]_n, (III), and their structures are reported herein. All three structures form two-dimensional layered coordination polymers in which the core sheet comprises the Cs—O [or in (III), Cs—O and Cs—Cl] complex network, with the aromatic rings of the ligands peripherally located between the layers. However, there are no π–π ring inter­actions in any of the structures.

S2. Experimental

S2.1. Synthesis and crystallization

Title compounds (I) and (II) were synthesized by heating together for 10 min CsOH (1.0 mmol, 15 mg) and (4-fluoro­phen­oxy)­acetic acid (1.0 mmol, 17 mg) [for (I)] or (3-chloro-2-methyl­phen­oxy)­acetic acid (1.0 mmol, 20 mg) [for (II)] in ethanol–water (15 ml, 1:9 v/v). Compound (III) was prepared by the addition of CsCl (17 mg, 1.0 mmol) to a solution of (2,4-di­chloro­phen­oxy)­acetic acid [22 mg (1.0 mmol) in 20 ml of 1:1 v/v ethanol–water]. Partial room-temperature evaporation of the solutions gave, in all cases, colourless crystal plates [Prism given for (II) in CIF tables - please clarify] from which specimens were cleaved for the X-ray analyses.

S2.2. Refinement

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 or methyl­ene C—H = 0.99 Å) and allowed to ride in the refinements, with U_iso(H) = 1.2U_eq(C). The water H atoms in (II) were located in a difference Fourier map but were allowed to ride in the refinement, with U_iso(H) = 1.5U_eq(O). The carb­oxy­lic acid H atom of the dimeric ligand unit in (III) was found to be delocalized at an inversion centre between two carboxyl O atoms and was subsequently fixed at that site, with U_iso(H) = 1.5U_eq(O). In (I), unusually large maximum and minimum refinement residual values were found (at 2.10 eÅ^-3, 0.75 Å from Cs1, and -2.75 eÅ^-3, 0.77 Å from Cs2).

S3. Results and discussion

In the structure of the anhydrous Cs salt with PFPA, (I), the dinuclear asymmetric unit (Fig. 1) comprises two separate irregular Cs coordination polyhedra, one CsO₆ [Cs1—O range = 3.026 (7)–3.166 (6) Å], the other CsO₇ [Cs2—O range, 3.003 (6)–3.297 (7) Å] (Table 2). Each Cs⁺ centre involves bidentate O,O¹-chelate coordination modes with the two phen­oxy­acetate ligands (A and B, respectively), while only Cs2 is involved in a bidentate O,O'-chelate inter­action, having a bite angle of 40.48 (17)°. The remaining coordination sites are occupied by bridging carboxyl O-atom donors, giving a Cs1···Cs2 separation of 4.4908 (9) Å among five similar short Cs···Cs bridges, the shortest of which is Cs1···Cs2^viii [4.3231 (9) Å; symmetry code: (viii) -x + 5/2, y + 1/2, -z + 1/2], in the two-dimensional polymeric structure which lies parallel to (001) (Figs. 2 and 3). Both PFPA ligands are similar, adopting the `planar' conformation, with minor variation in the phen­oxy side chains due to slight rotation of the carboxyl­ate group [defining torsion angle O11—C21—C31—O32 = 166.6 (8)° in the A ligand and -173.6 (8)° in the B ligand, which compare with 177° in the parent acid (Smith et al., 1992)]. The O,O¹-chelate bite angles for the two ligands are 49.98 (17) and 49.13 (18)° for the A and B ligands, respectively.

In the Cs salt of 2,3-MCPA, (II) (Fig. 4), the irregular CsO₉ coordination environment [Cs—O range = 3.0195 (19)–3.396 (2) Å; Table 3], like (I), involves a bidentate O,O¹-chelate inter­action with a bite angle of 47.45 (5)°. However, no bidentate O,O'-chelate inter­action is present, the two carboxyl­ate O atoms being involved in three additional bridging inter­actions. The single coordinated water molecule (O1W) is triply bridging, giving the two-dimensional layers which lie parallel to (100) (Figs. 5 and 6). Within the polymer, the minimum Cs1···Cs1ⁱⁱⁱ separation is 4.2474 (3) Å in an inversion-related duplex carboxyl­ate bridge [symmetry code: (iii) -x + 1, -y + 1, -z + 1]. The only other Cs···Cs separation is significantly longer [4.6034 (3) Å for Cs1···Cs1^iv; symmetry code: (iv) -x + 1, -y + 1, -z + 2]. The water molecule is also involved in intra-layer O—H···O_{carboxyl­ate} hydrogen-bonding inter­actions (Table 4). The 2,3-MCPA ligand adopts the `planar' conformation with a defining O11—C21—C31—O32 torsion angle of 171.9 (2)°, compared with 177.98 (17)° in the parent acid (Smith, 2013d).

For (III), the irregular CsO₆Cl₂ complex unit lies on a crystallographic inversion centre, the primary bonding with the 2,4-D ligand species being through a bidentate chelate inter­action involving a carboxyl O-atom donor and a ring-substituted ortho-Cl atom donor, completing an eight-membered ring about Cs1 (Fig. 7). The centrally located phen­oxy O atom (O11) lies 3.457 (3) Å from Cs1, a little longer than what is normally considered a typical Cs—O bond length. In (III), the Cs—O bond length range is 3.037 (3)–3.232(13 Å (Table 4). The hydrogen 2,4-D ligand species are inter-linked through a delocalized H atom lying on a crystallographic inversion centre within a short O32···H32···O32^vi hydrogen bond [2.457 (3) Å; symmetry code: (vi) -x + 3, -y + 2, -z + 1] (Table 5). Although the occurrence of any hydrogen bis­(phen­oxy­acetate) species such as those found in (III) has not been reported among salts or complexes of phenoxalkanoic acids, an analogous two-dimensional polymeric structure of Cs with trans-cinnamic acid is known [O···H···O = 2.462 (10) Å; Smith, 2014a]. It is also found in both ammonium hydrogen bis­(3-chloro­cinnamate) and ammonium hydrogen bis­(3-bromo­cinnamate) (Chowdhury & Kariuki, 2006) [O···H···O = 2.554 (6) and 2.466 (5) Å, respectively]. A coordinated dimeric hydrogen bis­(4-nitro­benzoate) ligand is present in the 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) (Van Deun et al., 2005).

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

In (III), both of the carboxyl O atoms quadruply bridge Cs centres and generate the two-dimensional polymer lying parallel to (001) (Figs. 8 and 9). No inter-ring π–π inter­actions are present in the structure [minimum ring centroid separation = 4.8756 (4) Å, the a cell parameter].

The linked 2,4-D species in complex (III) are close to coplanar, with the side-chain carboxyl group of the molecule rotated slightly out of the plane [torsion angle C1—O11—C21—O31 = -172.6 (3)°]. The anti­periplanar (torsion angle = 180±30°) conformation is quite unlike that of the parent acid, which in this respect is an unusual member of the phen­oxy­acetate acid series in having a synclinal side-chain conformation (torsion angle = 90±30°) [comparative torsion angle = 75.2°; Smith et al., 1976; Smith & Kennard, 1979; Lynch et al., 1999, 2003]. However, in the potassium salt (Kennard et al., 1983) and the ammonium salt (Liu et al., 2009) (both hemihydrates), the anti­periplanar conformation is found.

The present set of structures of the Cs salts of phen­oxy­acetic acids show previously demonstrated trends among the alkali metal or ammonium salts of simple benzoic acids with no stereochemically favourable inter­active substituent groups, for formation of two-dimensional coordination polymers. In these also are examples of both O,O' and O,O¹-chelates, and in the 2,4-D example, (III), the presence of the hydrogen bis­[(2,4-di­chloro­phen­oxy)­acetic acid] ligand species.

Related literature

For related literature, see: Chowdhury & Kariuki (2006); Evans et al. (2001); Kennard et al. (1983); Liu et al. (2009); Lynch et al. (1999, 2003); Prout et al. (1968, 1971); Smith (2012b, 2013a, 2013b, 2013c, 2013d, 2014a, 2014b); Smith & Kennard (1979); Smith et al. (1976, 1985, 1992, 1993); Srivastava & Speakman (1961); Van Deun, Ramaekers, Nockemann, Van Hecke, Van Meervelt & Binnemans (2005).

Computing details

For all compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SIR92 (Altomare et al., 1993) for (II), (III). 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 the two ligands (A and B) and the two Cs coordination polyhedra of (I), with displacement ellipsoids drawn at the 40% probability level. See Table 2 for symmetry codes.

Fig. 2. A view of the partially expanded polymeric extension of the structure of (I), viewed along the approximate a cell direction, with H atoms omitted. [Symmetry codes: (vi) x - 1, y, z; (vii) x, y - 1, z; see Table 2 for other codes.]

Fig. 3. The packing of the layered structure of (I) in the unit cell, viewed along b.

Fig. 4. The atom-numbering scheme and the molecular configuration of the CsO₉ coordination polyhedron in (II), with displacement ellipsoids drawn at the 40% probability level. See Table 3 for symmetry codes.

Fig. 5. A view of the partially expanded polymeric extension of the structure of (II), viewed along the approximate a cell direction, with non-associative H atoms omitted. [Symmetry code: (viii) -x + 1, y - 1/2, -z + 3/2; see Table 3 for other codes.]

Fig. 6. The packing of the layered structure of (II) in the unit cell, viewed along c. Hydrogen bonds are shown as dashed lines.

Fig. 7. The atom-numbering scheme and the molecular configuration of the CsO₆Cl₂ coordination polyhedron of (III), with displacement ellipsoids drawn at the 40% probability level. The dashed line indicates the bond to the delocalized atom H32. See Table 4 for symmetry codes.

Fig. 8. A view of the partially expanded polymeric extension of the structure of (III), with C-bound H atoms omitted. The delocalized acid atom H32 lies on a crystallographic inversion centre; its bonding is indicated by dashed lines. [Symmetry code: (vi) -x + 3, -y + 2, -z + 1; see Table 4 for other codes.]

Fig. 9. The packing of the layered structure of (III) in the unit cell, viewed along a.

(I) Poly[[µ₅-(4-fluorophenoxy)acetato][µ₄-(4-fluorophenoxy)acetato]dicaesium]

Crystal data

[Cs2(C8H6FO3)2]	F(000) = 1136
Mr = 604.08	Dx = 2.155 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4505 reflections
a = 6.8582 (2) Å	θ = 3.1–28.8°
b = 7.6183 (3) Å	µ = 3.96 mm^−1
c = 35.6746 (15) Å	T = 200 K
β = 92.778 (3)°	Plate, colourless
V = 1861.73 (12) Å^3	0.25 × 0.20 × 0.05 mm
Z = 4

Data collection

Oxford Gemini-S CCD area-detector diffractometer	3668 independent reflections
Radiation source: Enhance (Mo) X-ray source	3377 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.2°
ω scans	h = −7→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −9→9
Tmin = 0.559, Tmax = 0.980	l = −43→39
11999 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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.25	w = 1/[σ^2(Fo^2) + (0.0156P)^2 + 24.3P] where P = (Fo^2 + 2Fc^2)/3
3668 reflections	(Δ/σ)max < 0.001
235 parameters	Δρmax = 2.10 e Å^−3
0 restraints	Δρmin = −2.75 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	0.75958 (8)	0.42615 (7)	0.20660 (2)	0.0293 (2)
Cs2	1.23687 (8)	0.02363 (7)	0.21869 (2)	0.0292 (2)
F4A	0.8031 (10)	0.5637 (11)	−0.00079 (18)	0.067 (3)
F4B	1.3076 (11)	0.0195 (10)	0.0143 (2)	0.067 (3)
O11A	0.4758 (9)	0.4835 (9)	0.13500 (18)	0.033 (2)
O11B	0.9332 (10)	0.0287 (9)	0.14616 (19)	0.038 (2)
O31A	0.3015 (10)	0.4003 (8)	0.19784 (19)	0.034 (2)
O31B	0.7836 (11)	0.0407 (9)	0.2130 (2)	0.041 (3)
O32A	0.1230 (9)	0.6445 (9)	0.19599 (19)	0.035 (2)
O32B	0.5970 (10)	−0.1948 (8)	0.20193 (19)	0.034 (2)
C1A	0.5519 (13)	0.5127 (13)	0.1007 (3)	0.031 (3)
C1B	1.0205 (14)	0.0169 (13)	0.1124 (3)	0.033 (3)
C2A	0.7174 (14)	0.4145 (14)	0.0931 (3)	0.039 (3)
C2B	1.1839 (16)	0.1245 (15)	0.1086 (3)	0.046 (4)
C3A	0.8002 (16)	0.4308 (16)	0.0587 (3)	0.047 (4)
C3B	1.2799 (17)	0.1255 (15)	0.0758 (4)	0.049 (4)
C4A	0.7210 (16)	0.5461 (16)	0.0330 (3)	0.044 (4)
C4B	1.2118 (16)	0.0221 (15)	0.0468 (3)	0.043 (4)
C5A	0.5615 (15)	0.6475 (15)	0.0400 (3)	0.042 (3)
C5B	1.0525 (15)	−0.0855 (16)	0.0496 (3)	0.044 (4)
C6A	0.4752 (14)	0.6303 (13)	0.0743 (3)	0.035 (3)
C6B	0.9560 (15)	−0.0863 (15)	0.0829 (3)	0.041 (3)
C21A	0.3128 (13)	0.5848 (12)	0.1441 (3)	0.028 (3)
C21B	0.7808 (14)	−0.0955 (13)	0.1527 (3)	0.032 (3)
C31A	0.2411 (13)	0.5392 (12)	0.1827 (2)	0.026 (3)
C31B	0.7154 (13)	−0.0816 (11)	0.1928 (3)	0.028 (3)
H2A	0.77280	0.33670	0.11150	0.0480*
H2B	1.22850	0.19730	0.12890	0.0550*
H3A	0.91100	0.36270	0.05310	0.0560*
H3B	1.39190	0.19700	0.07330	0.0590*
H5A	0.51070	0.72820	0.02180	0.0500*
H5B	1.00940	−0.15800	0.02920	0.0530*
H6A	0.36420	0.69880	0.07960	0.0420*
H6B	0.84450	−0.15880	0.08530	0.0500*
H21A	0.20570	0.56520	0.12490	0.0340*
H21B	0.82860	−0.21590	0.14810	0.0390*
H22A	0.34810	0.71080	0.14350	0.0340*
H22B	0.66820	−0.07300	0.13490	0.0390*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs1	0.0249 (3)	0.0216 (3)	0.0412 (4)	−0.0020 (2)	0.0011 (2)	0.0018 (2)
Cs2	0.0307 (3)	0.0182 (3)	0.0385 (4)	0.0000 (2)	−0.0010 (2)	0.0016 (2)
F4A	0.059 (4)	0.103 (6)	0.040 (4)	−0.005 (4)	0.022 (3)	−0.002 (4)
F4B	0.063 (4)	0.075 (5)	0.064 (5)	−0.002 (4)	0.028 (4)	0.012 (4)
O11A	0.032 (3)	0.037 (4)	0.032 (4)	0.010 (3)	0.009 (3)	0.004 (3)
O11B	0.047 (4)	0.032 (4)	0.034 (4)	−0.017 (3)	−0.001 (3)	0.002 (3)
O31A	0.041 (4)	0.019 (3)	0.043 (4)	−0.003 (3)	0.010 (3)	0.007 (3)
O31B	0.058 (5)	0.027 (4)	0.039 (4)	−0.006 (3)	0.002 (3)	−0.010 (3)
O32A	0.026 (3)	0.033 (4)	0.046 (4)	−0.001 (3)	0.007 (3)	−0.002 (3)
O32B	0.034 (4)	0.028 (4)	0.041 (4)	−0.003 (3)	0.006 (3)	−0.001 (3)
C1A	0.028 (5)	0.032 (5)	0.033 (5)	−0.003 (4)	0.001 (4)	−0.003 (4)
C1B	0.035 (5)	0.027 (5)	0.036 (6)	−0.001 (4)	−0.003 (4)	0.006 (4)
C2A	0.032 (5)	0.041 (6)	0.045 (6)	0.006 (5)	0.003 (5)	−0.005 (5)
C2B	0.046 (6)	0.039 (6)	0.051 (7)	−0.013 (5)	−0.004 (5)	0.006 (5)
C3A	0.039 (6)	0.055 (7)	0.048 (7)	0.006 (5)	0.010 (5)	−0.013 (6)
C3B	0.039 (6)	0.037 (6)	0.073 (9)	−0.007 (5)	0.010 (6)	0.015 (6)
C4A	0.043 (6)	0.061 (7)	0.029 (6)	−0.013 (6)	0.013 (5)	−0.004 (5)
C4B	0.038 (6)	0.047 (6)	0.044 (7)	0.011 (5)	0.010 (5)	0.018 (5)
C5A	0.037 (6)	0.047 (6)	0.041 (6)	−0.006 (5)	0.001 (5)	0.006 (5)
C5B	0.039 (6)	0.055 (7)	0.037 (6)	−0.004 (5)	0.000 (5)	0.004 (5)
C6A	0.032 (5)	0.036 (5)	0.037 (6)	−0.003 (4)	0.003 (4)	0.000 (4)
C6B	0.034 (5)	0.053 (7)	0.037 (6)	−0.012 (5)	−0.001 (5)	0.003 (5)
C21A	0.027 (5)	0.023 (4)	0.033 (5)	0.006 (4)	−0.008 (4)	0.008 (4)
C21B	0.033 (5)	0.036 (5)	0.028 (5)	−0.001 (4)	0.006 (4)	−0.004 (4)
C31A	0.025 (4)	0.025 (5)	0.028 (5)	−0.010 (4)	0.001 (4)	−0.001 (4)
C31B	0.033 (5)	0.014 (4)	0.037 (5)	0.006 (4)	−0.006 (4)	0.004 (4)

Geometric parameters (Å, º)

Cs1—O11A	3.166 (6)	C1B—C2B	1.400 (15)
Cs1—O31A	3.148 (7)	C1B—C6B	1.370 (15)
Cs1—O31B	2.949 (7)	C2A—C3A	1.383 (15)
Cs1—O32B^i	3.097 (6)	C2B—C3B	1.370 (17)
Cs1—O32A^ii	3.036 (6)	C3A—C4A	1.363 (16)
Cs1—O31B^iii	3.026 (7)	C3B—C4B	1.365 (17)
Cs2—O11B	3.242 (7)	C4A—C5A	1.372 (16)
Cs2—O31B	3.108 (8)	C4B—C5B	1.373 (16)
Cs2—O32A^iv	3.090 (7)	C5A—C6A	1.391 (15)
Cs2—O31A^ii	3.003 (6)	C5B—C6B	1.388 (15)
Cs2—O32B^ii	3.061 (7)	C21A—C31A	1.525 (13)
Cs2—O31A^v	3.146 (7)	C21B—C31B	1.524 (15)
Cs2—O32A^v	3.279 (7)	C2A—H2A	0.9500
F4A—C4A	1.362 (13)	C2B—H2B	0.9500
F4B—C4B	1.360 (13)	C3A—H3A	0.9500
O11A—C1A	1.372 (12)	C3B—H3B	0.9500
O11A—C21A	1.409 (11)	C5A—H5A	0.9500
O11B—C1B	1.374 (12)	C5B—H5B	0.9500
O11B—C21B	1.437 (12)	C6A—H6A	0.9500
O31A—C31A	1.250 (11)	C6B—H6B	0.9500
O31B—C31B	1.254 (12)	C21A—H21A	0.9900
O32A—C31A	1.250 (11)	C21A—H22A	0.9900
O32B—C31B	1.239 (11)	C21B—H21B	0.9900
C1A—C2A	1.397 (14)	C21B—H22B	0.9900
C1A—C6A	1.385 (14)
O11A—Cs1—O31A	49.98 (17)	Cs2^vii—O32A—Cs2^iii	87.72 (17)
O11A—Cs1—O31B	103.28 (19)	Cs2^vi—O32B—C31B	102.6 (5)
O11A—Cs1—O32B^i	67.80 (18)	Cs1^viii—O32B—C31B	115.1 (6)
O11A—Cs1—O32A^ii	107.46 (17)	Cs1^viii—O32B—Cs2^vi	142.0 (2)
O11A—Cs1—O31B^iii	129.82 (18)	O11A—C1A—C2A	115.7 (9)
O31A—Cs1—O31B	89.84 (18)	O11A—C1A—C6A	124.3 (8)
O31A—Cs1—O32B^i	72.43 (17)	C2A—C1A—C6A	120.0 (10)
O31A—Cs1—O32A^ii	147.50 (17)	O11B—C1B—C2B	115.6 (9)
O31A—Cs1—O31B^iii	88.23 (19)	O11B—C1B—C6B	125.0 (9)
O31B—Cs1—O32B^i	162.01 (19)	C2B—C1B—C6B	119.5 (10)
O31B—Cs1—O32A^ii	120.81 (19)	C1A—C2A—C3A	119.8 (10)
O31B—Cs1—O31B^iii	102.80 (19)	C1B—C2B—C3B	120.4 (10)
O32A^ii—Cs1—O32B^i	77.17 (18)	C2A—C3A—C4A	119.2 (10)
O31B^iii—Cs1—O32B^i	74.37 (18)	C2B—C3B—C4B	118.9 (11)
O31B^iii—Cs1—O32A^ii	94.52 (19)	F4A—C4A—C3A	119.4 (10)
O11B—Cs2—O31B	49.13 (18)	F4A—C4A—C5A	118.3 (10)
O11B—Cs2—O32A^iv	69.97 (17)	C3A—C4A—C5A	122.4 (10)
O11B—Cs2—O31A^ii	83.55 (18)	F4B—C4B—C3B	119.5 (10)
O11B—Cs2—O32B^ii	110.10 (18)	F4B—C4B—C5B	118.2 (10)
O11B—Cs2—O31A^v	132.77 (17)	C3B—C4B—C5B	122.3 (11)
O11B—Cs2—O32A^v	152.31 (17)	C4A—C5A—C6A	119.0 (10)
O31B—Cs2—O32A^iv	77.45 (17)	C4B—C5B—C6B	118.6 (10)
O31A^ii—Cs2—O31B	95.91 (18)	C1A—C6A—C5A	119.7 (9)
O31B—Cs2—O32B^ii	145.48 (18)	C1B—C6B—C5B	120.4 (10)
O31A^v—Cs2—O31B	86.85 (18)	O11A—C21A—C31A	112.2 (8)
O31B—Cs2—O32A^v	107.23 (17)	O11B—C21B—C31B	110.9 (8)
O31A^ii—Cs2—O32A^iv	150.10 (18)	O31A—C31A—O32A	126.0 (8)
O32A^iv—Cs2—O32B^ii	68.70 (17)	O31A—C31A—C21A	118.0 (8)
O31A^v—Cs2—O32A^iv	86.40 (17)	O32A—C31A—C21A	116.1 (8)
O32A^iv—Cs2—O32A^v	124.39 (17)	O31B—C31B—O32B	126.7 (10)
O31A^ii—Cs2—O32B^ii	109.93 (18)	O31B—C31B—C21B	118.2 (8)
O31A^ii—Cs2—O31A^v	122.69 (17)	O32B—C31B—C21B	115.2 (8)
O31A^ii—Cs2—O32A^v	85.50 (18)	C1A—C2A—H2A	120.00
O31A^v—Cs2—O32B^ii	97.35 (17)	C3A—C2A—H2A	120.00
O32A^v—Cs2—O32B^ii	97.53 (17)	C1B—C2B—H2B	120.00
O31A^v—Cs2—O32A^v	40.48 (17)	C3B—C2B—H2B	120.00
Cs1—O11A—C1A	119.8 (5)	C2A—C3A—H3A	120.00
Cs1—O11A—C21A	110.7 (5)	C4A—C3A—H3A	120.00
C1A—O11A—C21A	117.2 (7)	C2B—C3B—H3B	121.00
Cs2—O11B—C1B	114.1 (5)	C4B—C3B—H3B	121.00
Cs2—O11B—C21B	107.9 (5)	C4A—C5A—H5A	121.00
C1B—O11B—C21B	116.8 (8)	C6A—C5A—H5A	120.00
Cs1—O31A—C31A	107.4 (5)	C4B—C5B—H5B	121.00
Cs1—O31A—Cs2^vi	101.17 (19)	C6B—C5B—H5B	121.00
Cs1—O31A—Cs2^iii	90.93 (18)	C1A—C6A—H6A	120.00
Cs2^vi—O31A—C31A	150.1 (6)	C5A—C6A—H6A	120.00
Cs2^iii—O31A—C31A	96.6 (5)	C1B—C6B—H6B	120.00
Cs2^vi—O31A—Cs2^iii	91.77 (18)	C5B—C6B—H6B	120.00
Cs1—O31B—Cs2	95.7 (2)	O11A—C21A—H21A	109.00
Cs1—O31B—C31B	132.6 (6)	O11A—C21A—H22A	109.00
Cs1—O31B—Cs1^v	110.7 (2)	C31A—C21A—H21A	109.00
Cs2—O31B—C31B	110.5 (6)	C31A—C21A—H22A	109.00
Cs1^v—O31B—Cs2	94.0 (2)	H21A—C21A—H22A	108.00
Cs1^v—O31B—C31B	106.2 (6)	O11B—C21B—H21B	109.00
Cs1^vi—O32A—C31A	104.3 (6)	O11B—C21B—H22B	109.00
Cs2^vii—O32A—C31A	122.6 (6)	C31B—C21B—H21B	110.00
Cs2^iii—O32A—C31A	90.3 (5)	C31B—C21B—H22B	110.00
Cs1^vi—O32A—Cs2^vii	132.7 (2)	H21B—C21B—H22B	108.00
Cs1^vi—O32A—Cs2^iii	86.32 (17)
O31A—Cs1—O11A—C1A	−174.8 (7)	O31A^v—Cs2—O31B—C31B	−108.4 (6)
O31A—Cs1—O11A—C21A	44.1 (5)	O31A^v—Cs2—O31B—Cs1^v	0.57 (18)
O31B—Cs1—O11A—C1A	−96.4 (6)	O32A^v—Cs2—O31B—Cs1	76.4 (2)
O31B—Cs1—O11A—C21A	122.4 (5)	O32A^v—Cs2—O31B—C31B	−143.9 (6)
O32B^i—Cs1—O11A—C1A	100.0 (6)	O32A^v—Cs2—O31B—Cs1^v	−34.9 (2)
O32B^i—Cs1—O11A—C21A	−41.1 (5)	O11B—Cs2—O32A^iv—Cs1^viii	−76.5 (3)
O32A^ii—Cs1—O11A—C1A	32.4 (7)	O11B—Cs2—O32A^iv—C31A^iv	111.7 (6)
O32A^ii—Cs1—O11A—C21A	−108.8 (5)	O31B—Cs2—O32A^iv—Cs1^viii	−25.7 (3)
O31B^iii—Cs1—O11A—C1A	144.1 (6)	O31B—Cs2—O32A^iv—C31A^iv	162.5 (6)
O31B^iii—Cs1—O11A—C21A	2.9 (6)	O11B—Cs2—O31A^ii—Cs1^ii	−135.9 (2)
O11A—Cs1—O31A—C31A	−51.8 (5)	O11B—Cs2—O31A^ii—C31A^ii	26.3 (11)
O11A—Cs1—O31A—Cs2^vi	119.0 (3)	O31B—Cs2—O31A^ii—Cs1^ii	176.50 (19)
O11A—Cs1—O31A—Cs2^iii	−149.0 (3)	O31B—Cs2—O31A^ii—C31A^ii	−21.3 (11)
O31B—Cs1—O31A—C31A	−159.4 (5)	O11B—Cs2—O32B^ii—Cs1^iv	−89.9 (4)
O31B—Cs1—O31A—Cs2^vi	11.4 (2)	O11B—Cs2—O32B^ii—C31B^ii	96.9 (6)
O31B—Cs1—O31A—Cs2^iii	103.37 (18)	O31B—Cs2—O32B^ii—Cs1^iv	−44.1 (6)
O32B^i—Cs1—O31A—C31A	23.6 (5)	O31B—Cs2—O32B^ii—C31B^ii	142.7 (6)
O32B^i—Cs1—O31A—Cs2^vi	−165.6 (2)	O11B—Cs2—O31A^v—Cs1^v	−19.9 (3)
O32B^i—Cs1—O31A—Cs2^iii	−73.60 (17)	O11B—Cs2—O31A^v—C31A^v	−127.5 (5)
O32A^ii—Cs1—O31A—C31A	2.1 (7)	O31B—Cs2—O31A^v—Cs1^v	−0.55 (17)
O32A^ii—Cs1—O31A—Cs2^vi	172.9 (2)	O31B—Cs2—O31A^v—C31A^v	−108.1 (5)
O32A^ii—Cs1—O31A—Cs2^iii	−95.1 (3)	O11B—Cs2—O32A^v—C31A^v	77.9 (6)
O31B^iii—Cs1—O31A—C31A	97.8 (5)	O31B—Cs2—O32A^v—C31A^v	50.0 (5)
O31B^iii—Cs1—O31A—Cs2^vi	−91.4 (2)	Cs1—O11A—C1A—C2A	39.1 (11)
O31B^iii—Cs1—O31A—Cs2^iii	0.56 (17)	Cs1—O11A—C1A—C6A	−140.9 (8)
O11A—Cs1—O31B—Cs2	129.01 (17)	C21A—O11A—C1A—C2A	177.9 (8)
O11A—Cs1—O31B—C31B	4.3 (9)	C21A—O11A—C1A—C6A	−2.2 (13)
O11A—Cs1—O31B—Cs1^v	−134.6 (2)	Cs1—O11A—C21A—C31A	−38.2 (8)
O31A—Cs1—O31B—Cs2	177.61 (19)	C1A—O11A—C21A—C31A	179.6 (8)
O31A—Cs1—O31B—C31B	52.9 (8)	Cs2—O11B—C1B—C2B	−45.4 (10)
O31A—Cs1—O31B—Cs1^v	−86.0 (2)	Cs2—O11B—C1B—C6B	136.6 (9)
O32A^ii—Cs1—O31B—Cs2	9.0 (3)	C21B—O11B—C1B—C2B	−172.4 (9)
O32A^ii—Cs1—O31B—C31B	−115.7 (8)	C21B—O11B—C1B—C6B	9.6 (14)
O32A^ii—Cs1—O31B—Cs1^v	105.5 (3)	Cs2—O11B—C21B—C31B	43.0 (8)
O31B^iii—Cs1—O31B—Cs2	−94.2 (2)	C1B—O11B—C21B—C31B	173.0 (8)
O31B^iii—Cs1—O31B—C31B	141.0 (8)	Cs1—O31A—C31A—O32A	−122.0 (8)
O31B^iii—Cs1—O31B—Cs1^v	2.2 (3)	Cs1—O31A—C31A—C21A	59.5 (8)
O11A—Cs1—O32B^i—Cs2^vii	80.9 (4)	Cs2^vi—O31A—C31A—O32A	76.3 (14)
O11A—Cs1—O32B^i—C31B^i	−106.4 (7)	Cs2^vi—O31A—C31A—C21A	−102.2 (12)
O31A—Cs1—O32B^i—Cs2^vii	27.7 (4)	Cs2^iii—O31A—C31A—O32A	−28.9 (10)
O31A—Cs1—O32B^i—C31B^i	−159.6 (7)	Cs2^iii—O31A—C31A—C21A	152.5 (7)
O11A—Cs1—O32A^ii—Cs2^i	91.4 (3)	Cs1—O31B—C31B—O32B	−117.7 (10)
O11A—Cs1—O32A^ii—C31A^ii	−95.8 (5)	Cs1—O31B—C31B—C21B	61.9 (11)
O31A—Cs1—O32A^ii—Cs2^i	50.9 (5)	Cs2—O31B—C31B—O32B	123.1 (9)
O31A—Cs1—O32A^ii—C31A^ii	−136.2 (5)	Cs2—O31B—C31B—C21B	−57.3 (9)
O31B—Cs1—O32A^ii—Cs2^i	−150.7 (3)	Cs1^v—O31B—C31B—O32B	22.4 (11)
O31B—Cs1—O32A^ii—C31A^ii	22.1 (6)	Cs1^v—O31B—C31B—C21B	−158.0 (7)
O11A—Cs1—O31B^iii—Cs1^iii	−67.8 (3)	Cs1^vi—O32A—C31A—O31A	−58.9 (10)
O11A—Cs1—O31B^iii—Cs2^iii	29.7 (3)	Cs1^vi—O32A—C31A—C21A	119.7 (7)
O11A—Cs1—O31B^iii—C31B^iii	142.5 (5)	Cs2^vii—O32A—C31A—O31A	114.9 (9)
O31A—Cs1—O31B^iii—Cs1^iii	−98.2 (2)	Cs2^vii—O32A—C31A—C21A	−66.5 (9)
O31A—Cs1—O31B^iii—Cs2^iii	−0.57 (17)	Cs2^iii—O32A—C31A—O31A	27.4 (9)
O31A—Cs1—O31B^iii—C31B^iii	112.1 (6)	Cs2^iii—O32A—C31A—C21A	−154.0 (7)
O31B—Cs1—O31B^iii—Cs1^iii	172.4 (2)	Cs2^vi—O32B—C31B—O31B	62.3 (10)
O31B—Cs1—O31B^iii—Cs2^iii	−90.0 (2)	Cs2^vi—O32B—C31B—C21B	−117.3 (7)
O31B—Cs1—O31B^iii—C31B^iii	22.7 (6)	Cs1^viii—O32B—C31B—O31B	−113.1 (9)
O31B—Cs2—O11B—C1B	−178.2 (7)	Cs1^viii—O32B—C31B—C21B	67.3 (9)
O31B—Cs2—O11B—C21B	−46.7 (5)	O11A—C1A—C2A—C3A	177.8 (9)
O32A^iv—Cs2—O11B—C1B	−87.6 (6)	C6A—C1A—C2A—C3A	−2.2 (15)
O32A^iv—Cs2—O11B—C21B	43.9 (5)	O11A—C1A—C6A—C5A	−178.7 (9)
O31A^ii—Cs2—O11B—C1B	78.3 (6)	C2A—C1A—C6A—C5A	1.2 (15)
O31A^ii—Cs2—O11B—C21B	−150.2 (6)	O11B—C1B—C2B—C3B	−178.8 (10)
O32B^ii—Cs2—O11B—C1B	−30.7 (6)	C6B—C1B—C2B—C3B	−0.6 (16)
O32B^ii—Cs2—O11B—C21B	100.9 (5)	O11B—C1B—C6B—C5B	178.5 (10)
O31A^v—Cs2—O11B—C1B	−152.3 (6)	C2B—C1B—C6B—C5B	0.5 (16)
O31A^v—Cs2—O11B—C21B	−20.8 (6)	C1A—C2A—C3A—C4A	1.5 (16)
O32A^v—Cs2—O11B—C1B	145.6 (6)	C1B—C2B—C3B—C4B	1.0 (17)
O32A^v—Cs2—O11B—C21B	−82.9 (6)	C2A—C3A—C4A—F4A	179.4 (10)
O11B—Cs2—O31B—Cs1	−86.9 (2)	C2A—C3A—C4A—C5A	0.1 (18)
O11B—Cs2—O31B—C31B	52.9 (6)	C2B—C3B—C4B—F4B	−178.9 (10)
O11B—Cs2—O31B—Cs1^v	161.8 (3)	C2B—C3B—C4B—C5B	−1.3 (18)
O32A^iv—Cs2—O31B—Cs1	−161.2 (2)	F4A—C4A—C5A—C6A	179.6 (10)
O32A^iv—Cs2—O31B—C31B	−21.4 (6)	C3A—C4A—C5A—C6A	−1.1 (17)
O32A^iv—Cs2—O31B—Cs1^v	87.58 (19)	F4B—C4B—C5B—C6B	178.8 (10)
O31A^ii—Cs2—O31B—Cs1	−10.8 (2)	C3B—C4B—C5B—C6B	1.1 (17)
O31A^ii—Cs2—O31B—C31B	129.0 (6)	C4A—C5A—C6A—C1A	0.4 (16)
O31A^ii—Cs2—O31B—Cs1^v	−121.99 (19)	C4B—C5B—C6B—C1B	−0.8 (17)
O32B^ii—Cs2—O31B—Cs1	−149.8 (2)	O11A—C21A—C31A—O31A	−14.7 (11)
O32B^ii—Cs2—O31B—C31B	−10.0 (8)	O11A—C21A—C31A—O32A	166.6 (8)
O32B^ii—Cs2—O31B—Cs1^v	99.0 (3)	O11B—C21B—C31B—O31B	6.7 (12)
O31A^v—Cs2—O31B—Cs1	111.81 (19)	O11B—C21B—C31B—O32B	−173.6 (8)

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

(II) Poly[aqua[µ₅-(3-chloro-2-methylphenoxy)acetato]caesium]

Crystal data

[Cs(C9H8ClO3)(H2O)]	F(000) = 672
Mr = 350.53	Dx = 2.045 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2801 reflections
a = 18.1357 (7) Å	θ = 3.2–28.9°
b = 8.8722 (4) Å	µ = 3.48 mm^−1
c = 7.0958 (3) Å	T = 200 K
β = 94.158 (4)°	Plate, colourless
V = 1138.73 (8) Å^3	0.30 × 0.20 × 0.15 mm
Z = 4

Data collection

Oxford Gemini-S CCD area-detector diffractometer	2230 independent reflections
Radiation source: Enhance (Mo) X-ray source	2024 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.2°
ω scans	h = −22→21
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −10→10
Tmin = 0.864, Tmax = 0.980	l = −8→8
6705 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.020	H-atom parameters constrained
wR(F^2) = 0.048	w = 1/[σ^2(Fo^2) + (0.0197P)^2 + 0.2986P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2230 reflections	Δρmax = 0.43 e Å^−3
137 parameters	Δρmin = −0.33 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: 0.0219 (7)

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	0.43536 (1)	0.43073 (2)	0.72238 (2)	0.0241 (1)
Cl3	0.11172 (5)	0.64082 (11)	1.00244 (12)	0.0480 (3)
O1W	0.56012 (11)	0.2745 (2)	0.9860 (3)	0.0325 (7)
O11	0.26794 (10)	0.4721 (2)	0.4811 (3)	0.0248 (6)
O31	0.38663 (11)	0.5439 (2)	0.2971 (3)	0.0305 (7)
O32	0.36286 (12)	0.3644 (2)	0.0831 (3)	0.0319 (7)
C1	0.20072 (15)	0.4599 (3)	0.5573 (4)	0.0217 (8)
C2	0.19296 (15)	0.5457 (3)	0.7203 (4)	0.0219 (8)
C3	0.12531 (17)	0.5364 (3)	0.7984 (4)	0.0274 (9)
C4	0.06705 (17)	0.4499 (3)	0.7242 (5)	0.0325 (10)
C5	0.07712 (16)	0.3652 (4)	0.5651 (4)	0.0338 (10)
C6	0.14362 (16)	0.3688 (3)	0.4810 (4)	0.0302 (9)
C21	0.27581 (15)	0.3959 (3)	0.3055 (4)	0.0237 (8)
C31	0.34809 (16)	0.4395 (3)	0.2239 (4)	0.0207 (8)
C211	0.25432 (15)	0.6459 (3)	0.7987 (4)	0.0292 (9)
H4	0.02120	0.44880	0.78110	0.0390*
H5	0.03790	0.30370	0.51270	0.0410*
H6	0.15020	0.30950	0.37200	0.0360*
H11W	0.58080	0.33400	0.90710	0.0490*
H12W	0.59700	0.21590	1.06020	0.0490*
H21	0.23390	0.42250	0.21450	0.0280*
H22	0.27480	0.28550	0.32620	0.0280*
H211	0.28830	0.66630	0.70050	0.0440*
H212	0.28120	0.59590	0.90600	0.0440*
H213	0.23360	0.74110	0.84080	0.0440*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs1	0.0253 (1)	0.0256 (1)	0.0217 (1)	0.0007 (1)	0.0038 (1)	0.0020 (1)
Cl3	0.0356 (5)	0.0630 (6)	0.0476 (5)	0.0023 (4)	0.0186 (4)	−0.0186 (4)
O1W	0.0294 (12)	0.0372 (12)	0.0311 (10)	−0.0009 (9)	0.0037 (9)	0.0106 (9)
O11	0.0207 (10)	0.0304 (10)	0.0238 (10)	−0.0038 (8)	0.0059 (8)	−0.0056 (9)
O31	0.0281 (12)	0.0336 (12)	0.0305 (11)	−0.0101 (9)	0.0069 (9)	−0.0066 (9)
O32	0.0420 (13)	0.0282 (11)	0.0272 (10)	−0.0002 (9)	0.0137 (9)	−0.0033 (9)
C1	0.0173 (14)	0.0215 (14)	0.0264 (14)	0.0026 (10)	0.0022 (11)	0.0058 (11)
C2	0.0197 (14)	0.0209 (14)	0.0252 (14)	0.0036 (11)	0.0032 (11)	0.0012 (11)
C3	0.0282 (17)	0.0271 (15)	0.0275 (15)	0.0069 (12)	0.0069 (12)	0.0034 (13)
C4	0.0197 (16)	0.0395 (19)	0.0393 (16)	−0.0007 (12)	0.0087 (13)	0.0079 (14)
C5	0.0223 (16)	0.0397 (17)	0.0389 (17)	−0.0102 (13)	−0.0010 (13)	0.0027 (15)
C6	0.0274 (16)	0.0313 (16)	0.0319 (15)	−0.0066 (13)	0.0031 (13)	−0.0030 (13)
C21	0.0251 (15)	0.0255 (14)	0.0208 (13)	−0.0015 (11)	0.0034 (11)	−0.0051 (12)
C31	0.0256 (15)	0.0175 (13)	0.0189 (13)	0.0027 (11)	0.0018 (11)	0.0047 (11)
C211	0.0234 (16)	0.0337 (16)	0.0309 (15)	−0.0018 (12)	0.0051 (12)	−0.0068 (13)

Geometric parameters (Å, º)

Cs1—O1W	3.151 (2)	C1—C2	1.400 (4)
Cs1—O11	3.3958 (19)	C1—C6	1.392 (4)
Cs1—O31	3.242 (2)	C2—C211	1.500 (4)
Cs1—O32^i	3.019 (2)	C2—C3	1.385 (4)
Cs1—O1W^ii	3.3931 (19)	C3—C4	1.379 (4)
Cs1—O31^iii	3.249 (2)	C4—C5	1.379 (4)
Cs1—O1W^iv	3.3322 (19)	C5—C6	1.384 (4)
Cs1—O1W^v	3.435 (2)	C21—C31	1.521 (4)
Cs1—O32^vi	3.0617 (19)	C4—H4	0.9500
Cl3—C3	1.751 (3)	C5—H5	0.9500
O11—C1	1.373 (3)	C6—H6	0.9500
O11—C21	1.434 (3)	C21—H21	0.9900
O31—C31	1.251 (3)	C21—H22	0.9900
O32—C31	1.246 (3)	C211—H211	0.9800
O1W—H11W	0.8700	C211—H212	0.9800
O1W—H12W	0.9700	C211—H213	0.9800
O1W—Cs1—O11	157.56 (5)	Cs1^iii—O31—C31	124.11 (17)
O1W—Cs1—O31	145.54 (5)	Cs1^viii—O32—C31	135.05 (17)
O1W—Cs1—O32^i	75.47 (6)	Cs1^v—O32—C31	108.11 (17)
O1W—Cs1—O1W^ii	127.97 (5)	Cs1^viii—O32—Cs1^v	103.72 (6)
O1W—Cs1—O31^iii	51.88 (5)	Cs1^vii—O1W—H12W	74.00
O1W—Cs1—O1W^iv	89.56 (5)	Cs1—O1W—H11W	71.00
O1W—Cs1—O1W^v	65.58 (5)	Cs1—O1W—H12W	174.00
O1W—Cs1—O32^vi	95.08 (5)	H11W—O1W—H12W	111.00
O11—Cs1—O31	47.45 (5)	Cs1^vii—O1W—H11W	104.00
O11—Cs1—O32^i	91.15 (5)	Cs1^iv—O1W—H11W	86.00
O1W^ii—Cs1—O11	74.46 (5)	Cs1^vi—O1W—H11W	164.00
O11—Cs1—O31^iii	145.68 (5)	Cs1^iv—O1W—H12W	96.00
O1W^iv—Cs1—O11	102.07 (5)	Cs1^vi—O1W—H12W	84.00
O1W^v—Cs1—O11	114.06 (5)	O11—C1—C2	115.3 (2)
O11—Cs1—O32^vi	65.31 (5)	C2—C1—C6	121.4 (3)
O31—Cs1—O32^i	138.03 (5)	O11—C1—C6	123.3 (2)
O1W^ii—Cs1—O31	47.90 (5)	C1—C2—C3	116.3 (2)
O31—Cs1—O31^iii	98.26 (5)	C1—C2—C211	120.8 (2)
O1W^iv—Cs1—O31	109.13 (5)	C3—C2—C211	122.8 (2)
O1W^v—Cs1—O31	81.63 (5)	Cl3—C3—C2	118.8 (2)
O31—Cs1—O32^vi	83.26 (5)	Cl3—C3—C4	117.4 (2)
O1W^ii—Cs1—O32^i	124.78 (5)	C2—C3—C4	123.8 (3)
O31^iii—Cs1—O32^i	123.01 (6)	C3—C4—C5	118.2 (3)
O1W^iv—Cs1—O32^i	67.61 (5)	C4—C5—C6	120.8 (3)
O1W^v—Cs1—O32^i	130.80 (5)	C1—C6—C5	119.5 (3)
O32^i—Cs1—O32^vi	84.47 (5)	O11—C21—C31	110.7 (2)
O1W^ii—Cs1—O31^iii	82.17 (5)	O32—C31—C21	114.2 (2)
O1W^ii—Cs1—O1W^iv	64.21 (5)	O31—C31—O32	125.7 (3)
O1W^ii—Cs1—O1W^v	103.07 (5)	O31—C31—C21	120.1 (2)
O1W^ii—Cs1—O32^vi	130.65 (5)	C3—C4—H4	121.00
O1W^iv—Cs1—O31^iii	89.56 (5)	C5—C4—H4	121.00
O1W^v—Cs1—O31^iii	47.49 (5)	C4—C5—H5	120.00
O31^iii—Cs1—O32^vi	116.76 (5)	C6—C5—H5	120.00
O1W^iv—Cs1—O1W^v	137.05 (5)	C1—C6—H6	120.00
O1W^iv—Cs1—O32^vi	149.58 (5)	C5—C6—H6	120.00
O1W^v—Cs1—O32^vi	70.83 (5)	O11—C21—H21	110.00
Cs1—O1W—Cs1^vii	100.12 (6)	O11—C21—H22	109.00
Cs1—O1W—Cs1^iv	90.44 (5)	C31—C21—H21	109.00
Cs1—O1W—Cs1^vi	93.04 (5)	C31—C21—H22	109.00
Cs1^vii—O1W—Cs1^iv	167.37 (7)	H21—C21—H22	108.00
Cs1^vii—O1W—Cs1^vi	76.93 (4)	C2—C211—H211	109.00
Cs1^iv—O1W—Cs1^vi	95.75 (5)	C2—C211—H212	110.00
Cs1—O11—C1	125.44 (16)	C2—C211—H213	109.00
Cs1—O11—C21	104.21 (14)	H211—C211—H212	109.00
C1—O11—C21	116.9 (2)	H211—C211—H213	109.00
Cs1—O31—C31	105.29 (16)	H212—C211—H213	109.00
Cs1—O31—Cs1^iii	81.74 (5)
O11—Cs1—O1W—Cs1^vii	51.09 (15)	O1W—Cs1—O1W^ii—Cs1^iii	69.07 (7)
O11—Cs1—O1W—Cs1^iv	−121.95 (12)	O11—Cs1—O1W^ii—Cs1^ii	157.50 (6)
O11—Cs1—O1W—Cs1^vi	−26.17 (15)	O11—Cs1—O1W^ii—Cs1^iii	−111.70 (5)
O31—Cs1—O1W—Cs1^vii	−62.34 (10)	O31—Cs1—O1W^ii—Cs1^ii	−156.51 (9)
O31—Cs1—O1W—Cs1^iv	124.62 (7)	O31—Cs1—O1W^ii—Cs1^iii	−65.72 (6)
O31—Cs1—O1W—Cs1^vi	−139.60 (7)	O1W—Cs1—O31^iii—Cs1^iii	160.94 (7)
O32^i—Cs1—O1W—Cs1^vii	106.09 (6)	O1W—Cs1—O31^iii—C31^iii	−96.2 (2)
O32^i—Cs1—O1W—Cs1^iv	−66.95 (5)	O11—Cs1—O31^iii—Cs1^iii	1.80 (9)
O32^i—Cs1—O1W—Cs1^vi	28.83 (5)	O11—Cs1—O31^iii—C31^iii	104.7 (2)
O1W^ii—Cs1—O1W—Cs1^vii	−130.87 (5)	O31—Cs1—O31^iii—Cs1^iii	0.00 (6)
O1W^ii—Cs1—O1W—Cs1^iv	56.09 (7)	O31—Cs1—O31^iii—C31^iii	102.9 (2)
O1W^ii—Cs1—O1W—Cs1^vi	151.87 (5)	O1W—Cs1—O1W^iv—Cs1^ii	93.10 (5)
O31^iii—Cs1—O1W—Cs1^vii	−97.18 (7)	O1W—Cs1—O1W^iv—Cs1^iv	0.00 (6)
O31^iii—Cs1—O1W—Cs1^iv	89.78 (6)	O11—Cs1—O1W^iv—Cs1^ii	−106.24 (5)
O31^iii—Cs1—O1W—Cs1^vi	−174.43 (8)	O11—Cs1—O1W^iv—Cs1^iv	160.66 (5)
O1W^iv—Cs1—O1W—Cs1^vii	173.04 (5)	O31—Cs1—O1W^iv—Cs1^ii	−57.37 (6)
O1W^iv—Cs1—O1W—Cs1^iv	0.00 (5)	O31—Cs1—O1W^iv—Cs1^iv	−150.47 (5)
O1W^iv—Cs1—O1W—Cs1^vi	95.78 (5)	O1W—Cs1—O1W^v—Cs1^vii	43.53 (5)
O1W^v—Cs1—O1W—Cs1^vii	−43.13 (5)	O1W—Cs1—O1W^v—Cs1^iii	−126.03 (5)
O1W^v—Cs1—O1W—Cs1^iv	143.83 (6)	O1W—Cs1—O1W^v—Cs1^v	134.28 (6)
O1W^v—Cs1—O1W—Cs1^vi	−120.38 (5)	O11—Cs1—O1W^v—Cs1^vii	−111.83 (5)
O32^vi—Cs1—O1W—Cs1^vii	23.15 (6)	O11—Cs1—O1W^v—Cs1^iii	78.61 (5)
O32^vi—Cs1—O1W—Cs1^iv	−149.89 (5)	O11—Cs1—O1W^v—Cs1^v	−21.08 (6)
O32^vi—Cs1—O1W—Cs1^vi	−54.11 (5)	O31—Cs1—O1W^v—Cs1^vii	−147.32 (5)
O1W—Cs1—O11—C1	53.6 (2)	O31—Cs1—O1W^v—Cs1^iii	43.12 (4)
O1W—Cs1—O11—C21	−85.2 (2)	O31—Cs1—O1W^v—Cs1^v	−56.57 (5)
O31—Cs1—O11—C1	−171.2 (2)	O1W—Cs1—O32^vi—Cs1^v	−93.46 (6)
O31—Cs1—O11—C21	49.97 (14)	O1W—Cs1—O32^vi—C31^vi	54.34 (19)
O32^i—Cs1—O11—C1	1.12 (18)	O11—Cs1—O32^vi—Cs1^v	97.89 (7)
O32^i—Cs1—O11—C21	−137.70 (14)	O11—Cs1—O32^vi—C31^vi	−114.31 (19)
O1W^ii—Cs1—O11—C1	−124.80 (18)	O31—Cs1—O32^vi—Cs1^v	51.93 (6)
O1W^ii—Cs1—O11—C21	96.38 (15)	O31—Cs1—O32^vi—C31^vi	−160.27 (19)
O31^iii—Cs1—O11—C1	−173.63 (16)	Cs1—O11—C1—C2	50.8 (3)
O31^iii—Cs1—O11—C21	47.55 (17)	Cs1—O11—C1—C6	−128.9 (2)
O1W^iv—Cs1—O11—C1	−66.22 (18)	C21—O11—C1—C2	−174.9 (2)
O1W^iv—Cs1—O11—C21	154.96 (14)	C21—O11—C1—C6	5.4 (4)
O1W^v—Cs1—O11—C1	137.57 (18)	Cs1—O11—C21—C31	−45.9 (2)
O1W^v—Cs1—O11—C21	−1.26 (15)	C1—O11—C21—C31	171.1 (2)
O32^vi—Cs1—O11—C1	84.51 (18)	Cs1—O31—C31—O32	−117.9 (3)
O32^vi—Cs1—O11—C21	−54.32 (14)	Cs1—O31—C31—C21	62.8 (3)
O1W—Cs1—O31—C31	96.21 (19)	Cs1^iii—O31—C31—O32	−27.6 (4)
O1W—Cs1—O31—Cs1^iii	−27.01 (9)	Cs1^iii—O31—C31—C21	153.14 (18)
O11—Cs1—O31—C31	−55.40 (17)	Cs1^viii—O32—C31—O31	−35.1 (4)
O11—Cs1—O31—Cs1^iii	−178.62 (7)	Cs1^viii—O32—C31—C21	144.2 (2)
O32^i—Cs1—O31—C31	−66.91 (19)	Cs1^v—O32—C31—O31	97.8 (3)
O32^i—Cs1—O31—Cs1^iii	169.87 (5)	Cs1^v—O32—C31—C21	−83.0 (2)
O1W^ii—Cs1—O31—C31	−165.3 (2)	O11—C1—C2—C3	179.3 (2)
O1W^ii—Cs1—O31—Cs1^iii	71.54 (6)	O11—C1—C2—C211	1.6 (4)
O31^iii—Cs1—O31—C31	123.22 (17)	C6—C1—C2—C3	−1.0 (4)
O31^iii—Cs1—O31—Cs1^iii	0.00 (6)	C6—C1—C2—C211	−178.7 (3)
O1W^iv—Cs1—O31—C31	−144.37 (17)	O11—C1—C6—C5	−178.9 (3)
O1W^iv—Cs1—O31—Cs1^iii	92.41 (5)	C2—C1—C6—C5	1.5 (4)
O1W^v—Cs1—O31—C31	78.58 (17)	C1—C2—C3—Cl3	−180.0 (2)
O1W^v—Cs1—O31—Cs1^iii	−44.64 (4)	C1—C2—C3—C4	−0.4 (4)
O32^vi—Cs1—O31—C31	7.05 (17)	C211—C2—C3—Cl3	−2.3 (4)
O32^vi—Cs1—O31—Cs1^iii	−116.17 (5)	C211—C2—C3—C4	177.2 (3)
O1W—Cs1—O32^i—C31^i	100.4 (3)	Cl3—C3—C4—C5	−179.1 (2)
O1W—Cs1—O32^i—Cs1^vi	−33.79 (5)	C2—C3—C4—C5	1.4 (5)
O11—Cs1—O32^i—C31^i	−97.8 (3)	C3—C4—C5—C6	−0.9 (5)
O11—Cs1—O32^i—Cs1^vi	127.99 (6)	C4—C5—C6—C1	−0.5 (5)
O31—Cs1—O32^i—C31^i	−89.4 (3)	O11—C21—C31—O31	−8.8 (4)
O31—Cs1—O32^i—Cs1^vi	136.44 (6)	O11—C21—C31—O32	171.9 (2)
O1W—Cs1—O1W^ii—Cs1^ii	−21.72 (8)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O31^iii	0.87	1.94	2.801 (3)	170
O1W—H12W···O31^vii	0.97	1.84	2.697 (3)	145
C211—H211···O11	0.98	2.33	2.757 (3)	105
C211—H213···Cl3	0.98	2.71	3.053 (3)	101

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

(III) Poly[[µ₇-(2,4-dichlorophenoxy)acetato][(2,4-dichlorphenoxy)acetic acid]caesium]

Crystal data

[Cs(C8H5Cl2O3)(C8H6Cl2O3)]	Z = 1
Mr = 573.96	F(000) = 278
Triclinic, P1	Dx = 1.876 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.8756 (4) Å	Cell parameters from 1960 reflections
b = 7.1876 (4) Å	θ = 3.1–28.8°
c = 15.3045 (10) Å	µ = 2.38 mm^−1
α = 96.223 (5)°	T = 200 K
β = 94.561 (6)°	Plate, colourless
γ = 106.450 (6)°	0.20 × 0.20 × 0.04 mm
V = 507.92 (6) Å^3

Data collection

Oxford Gemini-S CCD area-detector diffractometer	1977 independent reflections
Radiation source: Enhance (Mo) X-ray source	1859 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.1°
ω scans	h = −6→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −8→8
Tmin = 0.856, Tmax = 0.980	l = −18→18
6008 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.038P)^2] where P = (Fo^2 + 2Fc^2)/3
1977 reflections	(Δ/σ)max < 0.001
124 parameters	Δρmax = 1.01 e Å^−3
0 restraints	Δρmin = −0.79 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	0.50000	0.50000	0.50000	0.0311 (1)
Cl2	0.2495 (3)	0.37483 (17)	0.26721 (9)	0.0609 (5)
Cl4	−0.1949 (3)	0.7324 (2)	0.02731 (8)	0.0619 (5)
O11	0.6669 (5)	0.7505 (4)	0.32159 (18)	0.0307 (8)
O31	1.0711 (6)	0.7193 (4)	0.4423 (2)	0.0347 (9)
O32	1.3295 (6)	1.0313 (4)	0.44447 (19)	0.0313 (9)
C1	0.4770 (8)	0.7582 (6)	0.2530 (3)	0.0273 (12)
C2	0.2594 (9)	0.5862 (6)	0.2212 (3)	0.0360 (12)
C3	0.0536 (10)	0.5781 (7)	0.1528 (3)	0.0413 (17)
C4	0.0650 (9)	0.7435 (7)	0.1144 (3)	0.0393 (14)
C5	0.2782 (10)	0.9158 (7)	0.1433 (3)	0.0389 (16)
C6	0.4831 (9)	0.9234 (6)	0.2131 (3)	0.0342 (12)
C21	0.9022 (8)	0.9215 (5)	0.3495 (3)	0.0259 (11)
C31	1.1112 (8)	0.8795 (5)	0.4174 (3)	0.0255 (11)
H3	−0.09450	0.45950	0.13250	0.0490*
H5	0.28540	1.02900	0.11570	0.0470*
H6	0.62890	1.04290	0.23370	0.0410*
H21	0.83050	1.02850	0.37560	0.0310*
H22	1.00130	0.96440	0.29800	0.0310*
H32	1.50000	1.00000	0.50000	0.0470*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs1	0.0253 (2)	0.0206 (2)	0.0494 (3)	0.0065 (1)	0.0047 (2)	0.0139 (2)
Cl2	0.0754 (9)	0.0227 (6)	0.0691 (9)	−0.0037 (6)	−0.0176 (7)	0.0075 (6)
Cl4	0.0581 (8)	0.0781 (10)	0.0438 (7)	0.0209 (7)	−0.0181 (6)	−0.0008 (7)
O11	0.0260 (14)	0.0219 (14)	0.0416 (16)	0.0030 (12)	−0.0021 (12)	0.0089 (12)
O31	0.0259 (15)	0.0258 (15)	0.0539 (19)	0.0064 (12)	0.0018 (13)	0.0173 (13)
O32	0.0271 (14)	0.0189 (14)	0.0454 (17)	0.0037 (12)	−0.0042 (12)	0.0075 (12)
C1	0.027 (2)	0.025 (2)	0.029 (2)	0.0069 (17)	0.0022 (16)	0.0027 (16)
C2	0.037 (2)	0.027 (2)	0.040 (2)	0.0055 (19)	0.0013 (19)	0.0009 (18)
C3	0.039 (3)	0.037 (3)	0.038 (3)	0.002 (2)	−0.003 (2)	−0.007 (2)
C4	0.038 (2)	0.051 (3)	0.029 (2)	0.018 (2)	−0.0037 (18)	−0.002 (2)
C5	0.046 (3)	0.038 (3)	0.034 (2)	0.015 (2)	−0.002 (2)	0.0077 (19)
C6	0.032 (2)	0.029 (2)	0.039 (2)	0.0063 (18)	−0.0021 (18)	0.0048 (18)
C21	0.025 (2)	0.0196 (19)	0.032 (2)	0.0040 (16)	0.0027 (16)	0.0065 (16)
C31	0.0211 (19)	0.023 (2)	0.036 (2)	0.0091 (16)	0.0091 (16)	0.0080 (16)

Geometric parameters (Å, º)

Cs1—Cl2	3.6035 (14)	O32—H32	1.2200
Cs1—O31	3.037 (3)	C1—C6	1.387 (6)
Cs1—O32^i	3.232 (3)	C1—C2	1.391 (6)
Cs1—O31^ii	3.084 (3)	C2—C3	1.376 (7)
Cs1—Cl2^iii	3.6035 (14)	C3—C4	1.372 (7)
Cs1—O31^iii	3.037 (3)	C4—C5	1.374 (7)
Cs1—O31^iv	3.084 (3)	C5—C6	1.389 (7)
Cs1—O32^v	3.232 (3)	C21—C31	1.511 (6)
Cl2—C2	1.733 (4)	C3—H3	0.9500
Cl4—C4	1.744 (5)	C5—H5	0.9500
O11—C1	1.360 (5)	C6—H6	0.9500
O11—C21	1.421 (5)	C21—H21	0.9900
O31—C31	1.220 (5)	C21—H22	0.9900
O32—C31	1.292 (5)
Cl2—Cs1—O31	85.77 (6)	Cs1^vi—O31—C31	130.9 (3)
Cl2—Cs1—O32^i	69.94 (5)	Cs1^vii—O32—C31	142.0 (2)
Cl2—Cs1—O31^ii	68.14 (6)	C31—O32—H32	113.00
Cl2—Cs1—Cl2^iii	180.00	Cs1^vii—O32—H32	97.00
Cl2—Cs1—O31^iii	94.23 (6)	O11—C1—C2	116.9 (4)
Cl2—Cs1—O31^iv	111.86 (6)	C2—C1—C6	118.0 (4)
Cl2—Cs1—O32^v	110.06 (5)	O11—C1—C6	125.2 (4)
O31—Cs1—O32^i	113.38 (8)	Cl2—C2—C3	118.8 (3)
O31—Cs1—O31^ii	105.59 (8)	C1—C2—C3	121.7 (4)
Cl2^iii—Cs1—O31	94.23 (6)	Cl2—C2—C1	119.5 (3)
O31—Cs1—O31^iii	180.00	C2—C3—C4	119.1 (4)
O31—Cs1—O31^iv	74.41 (8)	Cl4—C4—C5	120.1 (4)
O31—Cs1—O32^v	66.62 (8)	Cl4—C4—C3	119.0 (4)
O31^ii—Cs1—O32^i	118.94 (8)	C3—C4—C5	120.9 (4)
Cl2^iii—Cs1—O32^i	110.06 (5)	C4—C5—C6	119.6 (4)
O31^iii—Cs1—O32^i	66.62 (8)	C1—C6—C5	120.7 (4)
O31^iv—Cs1—O32^i	61.07 (8)	O11—C21—C31	109.9 (3)
O32^i—Cs1—O32^v	180.00	O32—C31—C21	112.0 (3)
Cl2^iii—Cs1—O31^ii	111.86 (6)	O31—C31—O32	125.6 (4)
O31^ii—Cs1—O31^iii	74.41 (8)	O31—C31—C21	122.4 (4)
O31^ii—Cs1—O31^iv	180.00	C2—C3—H3	120.00
O31^ii—Cs1—O32^v	61.07 (8)	C4—C3—H3	120.00
Cl2^iii—Cs1—O31^iii	85.77 (6)	C4—C5—H5	120.00
Cl2^iii—Cs1—O31^iv	68.14 (6)	C6—C5—H5	120.00
Cl2^iii—Cs1—O32^v	69.94 (5)	C1—C6—H6	120.00
O31^iii—Cs1—O31^iv	105.59 (8)	C5—C6—H6	120.00
O31^iii—Cs1—O32^v	113.38 (8)	O11—C21—H21	110.00
O31^iv—Cs1—O32^v	118.94 (8)	O11—C21—H22	110.00
Cs1—Cl2—C2	109.50 (16)	C31—C21—H21	110.00
C1—O11—C21	116.9 (3)	C31—C21—H22	110.00
Cs1—O31—C31	122.2 (3)	H21—C21—H22	108.00
Cs1—O31—Cs1^vi	105.59 (8)
O31—Cs1—Cl2—C2	−63.25 (18)	Cs1^vi—O31—C31—O32	−33.5 (6)
O32^i—Cs1—Cl2—C2	179.97 (19)	Cs1^vi—O31—C31—C21	146.7 (3)
O31^ii—Cs1—Cl2—C2	45.42 (18)	Cs1^vii—O32—C31—O31	−139.3 (3)
O31^iii—Cs1—Cl2—C2	116.75 (18)	Cs1^vii—O32—C31—C21	40.6 (6)
O31^iv—Cs1—Cl2—C2	−134.58 (18)	O11—C1—C2—Cl2	−2.1 (6)
O32^v—Cs1—Cl2—C2	−0.03 (19)	O11—C1—C2—C3	179.2 (4)
Cl2—Cs1—O31—C31	77.8 (3)	C6—C1—C2—Cl2	178.3 (3)
Cl2—Cs1—O31—Cs1^vi	−114.10 (8)	C6—C1—C2—C3	−0.5 (7)
O32^i—Cs1—O31—C31	143.8 (3)	O11—C1—C6—C5	−179.9 (4)
O31^ii—Cs1—O31—C31	11.9 (3)	C2—C1—C6—C5	−0.3 (7)
Cl2^iii—Cs1—O31—C31	−102.2 (3)	Cl2—C2—C3—C4	−178.2 (4)
O31^iv—Cs1—O31—C31	−168.1 (3)	C1—C2—C3—C4	0.7 (7)
O32^v—Cs1—O31—C31	−36.2 (3)	C2—C3—C4—Cl4	179.6 (4)
Cs1—Cl2—C2—C1	34.4 (4)	C2—C3—C4—C5	0.0 (7)
Cs1—Cl2—C2—C3	−146.7 (3)	Cl4—C4—C5—C6	179.6 (4)
C21—O11—C1—C2	175.2 (4)	C3—C4—C5—C6	−0.8 (7)
C21—O11—C1—C6	−5.2 (6)	C4—C5—C6—C1	0.9 (7)
C1—O11—C21—C31	−172.6 (3)	O11—C21—C31—O31	−0.3 (6)
Cs1—O31—C31—O32	131.3 (4)	O11—C21—C31—O32	179.8 (3)
Cs1—O31—C31—C21	−48.6 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O32—H32···O32^viii	1.22	1.22	2.449 (4)	180

Symmetry code: (viii) −x+3, −y+2, −z+1.