Poly[di-μ-aqua-di­aqua­bis­(μ7-oxalato-κ9O1:O1:O1,O2:O2:O2′:O2′,O1′:O1′)calciumdicaesium]

Kherfi, H.; Hamadène, M.; Guehria-Laïdoudi, A.; Dahaoui, S.; Lecomte, C.

doi:10.1107/S1600536813022654

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 9| September 2013| Pages m493-m494

doi:10.1107/S1600536813022654

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Poly[di-μ-aqua-diaquabis(μ₇-oxalato-κ⁹O¹:O¹:O¹,O²:O²:O^2′:O^2′,O^1′:O^1′)calciumdicaesium]

Hamza Kherfi,^a Malika Hamadène,^a Achoura Guehria-Laïdoudi,^a ^* Slimane Dahaoui ^b and Claude Lecomte ^b

^aLaboratoire de Cristallographie-Thermodynamique, Faculté de Chimie USTHB BP 32 El-Alia, Bab Ezzouar 16111, Alger, Algeria, and ^bCRM2 UMR-CNRS 7036 Jean Barriol Institut, Lorraine Université BP 230, 54506 Vandoeuvre-lés-Nancy Cedex, France
^*Correspondence e-mail: guehria_laidoudi@yahoo.fr

(Received 29 July 2013; accepted 12 August 2013; online 17 August 2013)

In the title compound, [CaCs₂(C₂O₄)₂(H₂O)₄]_n, the Ca²⁺ ion, lying on a twofold rotation axis, is coordinated by four O atoms from two oxalate ligands and two bridging water molecules in an octahedral geometry. The Cs⁺ ion is coordinated by seven O atoms from six oxalate ligands, one bridging water and one terminal water molecule. The oxalate ligand displays a scarce high denticity. The structure contains parallel chain units runnig along [10-1], formed by two edge-sharing Cs polyhedra connected by CsO₉ polyhedra connected by a face-sharing CaO₆ octahedron. These chains are further linked by the oxalate ligands to build up a three-dimensional framework. O—H⋯O hydrogen bonds involving the water molecules and the carboxylate O atoms enhance the extended structure.

Related literature

For related compounds or structures, see: Chen et al. (2008 ); Hursthouse et al. (2004 ); Kolitsch (2004 ); Price et al. (1999 ); Schwendtner & Kolitsch (2004 ); Wu & Liu (2010 ).

Experimental

Crystal data

[CaCs₂(C₂O₄)₂(H₂O)₄]
M_r = 554.00
Monoclinic, C 2/c
a = 16.8808 (4) Å
b = 7.3212 (2) Å
c = 13.5268 (3) Å
β = 128.364 (1)°
V = 1310.79 (6) Å³
Z = 4
Mo Kα radiation
μ = 6.01 mm⁻¹
T = 100 K
0.26 × 0.22 × 0.16 mm

Data collection

Agilent Xcalibur EOS CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.229, T_max = 0.382
14337 measured reflections
2196 independent reflections
2189 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.060
S = 1.25
2196 reflections
104 parameters
6 restraints
All H-atom parameters refined
Δρ_max = 1.65 e Å⁻³
Δρ_min = −1.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1⋯O2ⁱ	0.81 (7)	1.91 (7)	2.714 (4)	172 (6)
O1W—H2⋯O3ⁱⁱ	0.81 (4)	1.95 (4)	2.736 (2)	163 (7)
O2W—H3⋯O1Wⁱⁱⁱ	0.82 (3)	1.89 (3)	2.680 (2)	164 (5)
O2W—H4⋯O4^iv	0.81 (4)	1.92 (3)	2.724 (3)	176 (7)
Symmetry codes: (i) $[-x, y, -z+{\script{1\over 2}}]$ ; (ii) -x, -y, -z; (iii) -x, -y+1, -z; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813022654/hy2635sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813022654/hy2635Isup2.hkl

checkCIF report

Comment top

In oxalates, A_xM(C₂O₄)₂(H₂O)_n, containing alkaline A, and alkaline-earth M, the A–Mg oxalates (A = Na; Cs) are isostructural with Co(II) analogue (Schwendtner & Kolitsch, 2004), owing to the corresponding ionic radii which are approximately equal [0.65 and 0.72 Å for Co(II) and Mg(II), respectively]. However, the single crystals are not easily obtained, and their growths require alternative reagents, which are not incorporated in the structure (Chen et al., 2008; Kolitsch, 2004). It is the case for the title bi-metallic Cs–Ca compound, where Cr(III) oxide used in synthesis mixture does not react but serves probably in process growth as enhancing inclusion. The same specific single-crystal synthesis conditions are noticed in a mono-metallic Sr oxalate, which needs divalent transition metal to favour single crystals growth (Price et al., 1999). The title compound, investigated at 100 K, is isostructural with the Mg(II) analogue (Kolitsch, 2004) and the Co(II) analogue (Schwendtner & Kolitsch, 2004) previously studied at room temperature. In the title compound, the binuclear Cs units, formed by two edge-sharing Cs polyhedra, are connected by a face-sharing Ca octahedron runnig along [101] (Fig. 1), with a nearly linear Cs—Ca—Cs and Cs—Cs—Ca chain [175.41 (6) and 172.26 (8)°, respectively]. The Cs and Ca ions have the smallest separation of 4.0528 (4) Å, whereas the longest distance [5.6889 (5) Å] occurs between the adjacent Cs atoms bridged by O4 atoms. As shown in Fig. 2, the alkaline atom is nona-coordinated by seven O atoms from six oxalate ligands, one bridging water and one terminal water molecule, while the alkaline-earth atom, which is located on a twofold rotation axis, is bound to two equivalent oxalate groups and two water molecules, the later being in a cis arrangement (Fig. 2). In the CaO₄(H₂O)₂ octahedron, the organic ligands are coordinate with the metal centre in an expected η⁴ chelation, observed usually with this rigid ligand. The two resulting five-membered rings are perpendicular, the dihedral angle being of 89.76 (6)°. The equatorial plane is defined by two equivalent aqua ligands in cis position and two equivalent O3 atoms, while the axial positions are occupied by O1 atoms. The maximum atomic deviation from the mean plane [O2w, Ca1, O3, O3ⁱⁱⁱ, O2wⁱⁱⁱ; symmetry code: (iii) -x, y, -z+1/2] is 0.165 (2) Å for the O3 donor. In connecting the Cs and Ca polyhedra, the oxalate ligand acts as bis-chelate, forming five-menbered rings with the both cations. Moreover, it bridges the metal atoms via all its O atoms, and is surrounded by six Cs and one Ca atoms through the two carboxylate groups. One group (O1, C1, O2) bridges five atoms (4 Cs and 1 Ca) and adopts an unusual µ₅:η³-η² coordination mode; the other group (O3, C2, O4) bridges four atoms (3 Cs and 1 Ca) and adopts a common µ₄:η²-η² coordination mode. As a result, the oxalate dianion displays an interesting nonadenticity in its chelating and bridging coordination modes, involving three triply bonding O atoms (O2, O3 and O4) and a tetrabonding one (O1). In the overall packing, the Cs polyhedra, linked alternately by one edge (O1···O1) and one corner (O2 atom) in a one-dimensional ladder running approximately along the [110] direction, are interconnected by the vertices to generate a two-dimensional network drawing small hexagonal cavities (Fig. 3). The adjacent pseudo-layers thus obtained, are stacked along [101] through O4···O4 edges, to give rise to a dense three-dimensional framework. Water molecules provide links between the both metallic atoms. O—H···O hydrogen bonds involving the water molecules and the carboxylate O atoms enhance the extended structure (Table 1, Fig. 4).

Related literature top

For related compounds or structures, see: Chen et al. (2008); Hursthouse et al. (2004); Kolitsch (2004); Price et al. (1999); Schwendtner & Kolitsch (2004); Wu & Liu (2010).

Experimental top

The synthetic preparation was carried out in an aqueous solution at room temperature. The starting materials, caesium carbonate, trivalent chromium oxide and oxalic acid dihydrate, in equal stoechiometric amounts (0.5 mmol) were dissolved in deionized water (20 ml) and the resulting dark pink solution was stirred for two hours. The title compound crystallizes from the slowly evaporated solution after about one month and then filtered from chromium oxide powder. A few light pink crystals with prismatic geometry and suitable size for X-ray analysis were found trapped in colourless crystals of oxalic acid, then isolated, filtered and washed with diethyl ether. The light pink colour, which can not be removed after several washing, shows that small Cr(III) inclusion is present but not incorporated in the structure.

Computing details top

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); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The chain built of Cs polyhedra and Ca octahedra.
	Fig. 2. The metal atom environments of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x+1/2, -y+1/2, -z+1; (ii) -x+1/2, y+1/2, -z+1/2; (iii) -x, y, -z+1/2; (iv) x, -y, z-1/2; (v) x, -y+1, z-1/2.]
	Fig. 3. The Cs polyhedra layer showing pseudo-hexagonal cavities.
	Fig. 4. The three-dimensional packing structure showing hydrogen bonds as dashed lines.

Poly[di-µ-aqua-diaquabis(µ₇-oxalato-κ⁹O¹:O¹:O¹,O²:O²:O^2':O^2',O^1':O^1')calciumdicaesium] top

Crystal data top

[CaCs₂(C₂O₄)₂(H₂O)₄]	F(000) = 1032
M_r = 554.00	D_x = 2.807 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1722 reflections
a = 16.8808 (4) Å	θ = 1.9–32.0°
b = 7.3212 (2) Å	µ = 6.01 mm⁻¹
c = 13.5268 (3) Å	T = 100 K
β = 128.364 (1)°	Prismatic, pink
V = 1310.79 (6) Å³	0.26 × 0.22 × 0.16 mm
Z = 4

Data collection top

Agilent Xcalibur EOS CCD diffractometer	2196 independent reflections
Radiation source: fine-focus sealed tube	2189 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
w scans	θ_max = 32.0°, θ_min = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −25→25
T_min = 0.229, T_max = 0.382	k = −10→10
14337 measured reflections	l = −20→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	All H-atom parameters refined
wR(F²) = 0.060	w = 1/[σ²(F_o²) + (0.0199P)² + 5.1138P] where P = (F_o² + 2F_c²)/3
S = 1.25	(Δ/σ)_max < 0.001
2196 reflections	Δρ_max = 1.65 e Å⁻³
104 parameters	Δρ_min = −1.14 e Å⁻³
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0048 (4)

Crystal data top

[CaCs₂(C₂O₄)₂(H₂O)₄]	V = 1310.79 (6) Å³
M_r = 554.00	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.8808 (4) Å	µ = 6.01 mm⁻¹
b = 7.3212 (2) Å	T = 100 K
c = 13.5268 (3) Å	0.26 × 0.22 × 0.16 mm
β = 128.364 (1)°

Data collection top

Agilent Xcalibur EOS CCD diffractometer	2196 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	2189 reflections with I > 2σ(I)
T_min = 0.229, T_max = 0.382	R_int = 0.056
14337 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	6 restraints
wR(F²) = 0.060	All H-atom parameters refined
S = 1.25	Δρ_max = 1.65 e Å⁻³
2196 reflections	Δρ_min = −1.14 e Å⁻³
104 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cs1	0.152844 (10)	0.314498 (19)	0.109026 (12)	0.01416 (8)
Ca1	0.0000	0.33665 (10)	0.2500	0.01801 (14)
C1	0.12874 (17)	0.1846 (3)	0.4980 (2)	0.0118 (4)
O1	0.06123 (14)	0.3069 (2)	0.43831 (17)	0.0135 (3)
O2	0.17036 (14)	0.1342 (3)	0.60819 (16)	0.0183 (3)
C2	0.15913 (16)	0.0871 (3)	0.4234 (2)	0.0114 (3)
O4	0.22599 (14)	−0.0311 (3)	0.47650 (17)	0.0179 (3)
O3	0.10886 (13)	0.1373 (2)	0.30886 (16)	0.0133 (3)
O1W	−0.03349 (15)	0.1582 (2)	−0.15099 (18)	0.0161 (3)
H1	−0.071 (3)	0.159 (6)	−0.133 (5)	0.033 (12)*
H2	−0.049 (4)	0.079 (5)	−0.202 (4)	0.037 (12)*
O2W	0.10155 (13)	0.5272 (2)	0.28003 (17)	0.0162 (3)
H3	0.088 (4)	0.632 (4)	0.254 (4)	0.027 (10)*
H4	0.154 (3)	0.532 (8)	0.351 (3)	0.050 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs1	0.01329 (9)	0.01645 (10)	0.01254 (9)	−0.00098 (4)	0.00792 (7)	−0.00063 (4)
Ca1	0.0185 (3)	0.0180 (3)	0.0172 (3)	0.000	0.0109 (3)	0.000
C1	0.0101 (8)	0.0146 (9)	0.0100 (9)	−0.0015 (6)	0.0060 (7)	−0.0013 (6)
O1	0.0136 (7)	0.0154 (7)	0.0114 (7)	0.0021 (5)	0.0077 (6)	−0.0001 (5)
O2	0.0168 (7)	0.0263 (9)	0.0110 (7)	0.0042 (7)	0.0082 (6)	0.0034 (6)
C2	0.0111 (8)	0.0115 (8)	0.0113 (8)	−0.0003 (7)	0.0068 (7)	−0.0013 (6)
O4	0.0160 (7)	0.0200 (8)	0.0154 (7)	0.0066 (6)	0.0086 (6)	0.0012 (6)
O3	0.0151 (7)	0.0138 (7)	0.0110 (7)	0.0018 (6)	0.0082 (6)	0.0005 (5)
O1W	0.0188 (8)	0.0156 (7)	0.0158 (8)	−0.0026 (6)	0.0117 (7)	−0.0031 (6)
O2W	0.0132 (7)	0.0142 (7)	0.0154 (7)	−0.0014 (6)	0.0060 (6)	0.0022 (6)

Geometric parameters (Å, º) top

Cs1—O2ⁱ	3.0837 (18)	Ca1—O1	2.0823 (18)
Cs1—O4ⁱⁱ	3.1206 (18)	C1—O2	1.246 (3)
Cs1—O1W	3.1369 (19)	C1—O1	1.269 (3)
Cs1—O1ⁱⁱⁱ	3.2557 (18)	C1—C2	1.559 (3)
Cs1—O2^iv	3.299 (2)	C2—O4	1.238 (3)
Cs1—O1^v	3.3124 (17)	C2—O3	1.275 (3)
Cs1—O2W	3.318 (2)	O1W—H1	0.81 (3)
Cs1—O4^iv	3.434 (2)	O1W—H2	0.81 (3)
Cs1—O3	3.4688 (17)	O2W—H3	0.82 (3)
Ca1—O2W	2.0456 (18)	O2W—H4	0.81 (3)
Ca1—O3	2.0797 (18)

O2ⁱ—Cs1—O4ⁱⁱ	93.63 (5)	O3ⁱⁱⁱ—Ca1—C2ⁱⁱⁱ	23.63 (6)
O2ⁱ—Cs1—O1W	163.78 (5)	O3—Ca1—C2ⁱⁱⁱ	91.29 (7)
O4ⁱⁱ—Cs1—O1W	98.53 (5)	O1—Ca1—C2ⁱⁱⁱ	115.82 (7)
O2ⁱ—Cs1—O1ⁱⁱⁱ	110.34 (5)	O1ⁱⁱⁱ—Ca1—C2ⁱⁱⁱ	55.35 (6)
O4ⁱⁱ—Cs1—O1ⁱⁱⁱ	146.74 (5)	C1ⁱⁱⁱ—Ca1—C2ⁱⁱⁱ	31.60 (6)
O1W—Cs1—O1ⁱⁱⁱ	63.58 (5)	C1—Ca1—C2ⁱⁱⁱ	110.84 (6)
O2ⁱ—Cs1—O2^iv	96.06 (5)	O2Wⁱⁱⁱ—Ca1—C2	147.17 (7)
O4ⁱⁱ—Cs1—O2^iv	106.19 (5)	O2W—Ca1—C2	91.60 (6)
O1W—Cs1—O2^iv	70.28 (5)	O3ⁱⁱⁱ—Ca1—C2	91.29 (7)
O1ⁱⁱⁱ—Cs1—O2^iv	94.20 (5)	O3—Ca1—C2	23.63 (6)
O2ⁱ—Cs1—O1^v	115.89 (5)	O1—Ca1—C2	55.35 (6)
O4ⁱⁱ—Cs1—O1^v	64.42 (5)	O1ⁱⁱⁱ—Ca1—C2	115.82 (7)
O1W—Cs1—O1^v	79.29 (5)	C1ⁱⁱⁱ—Ca1—C2	110.84 (6)
O1ⁱⁱⁱ—Cs1—O1^v	84.04 (4)	C1—Ca1—C2	31.60 (6)
O2^iv—Cs1—O1^v	146.60 (4)	C2ⁱⁱⁱ—Ca1—C2	100.91 (9)
O2ⁱ—Cs1—O2W	63.16 (5)	O2Wⁱⁱⁱ—Ca1—Cs1ⁱⁱⁱ	54.62 (5)
O4ⁱⁱ—Cs1—O2W	127.09 (5)	O2W—Ca1—Cs1ⁱⁱⁱ	129.31 (6)
O1W—Cs1—O2W	116.03 (5)	O3ⁱⁱⁱ—Ca1—Cs1ⁱⁱⁱ	58.85 (5)
O1ⁱⁱⁱ—Cs1—O2W	53.63 (4)	O3—Ca1—Cs1ⁱⁱⁱ	117.46 (5)
O2^iv—Cs1—O2W	122.16 (4)	O1—Ca1—Cs1ⁱⁱⁱ	52.98 (5)
O1^v—Cs1—O2W	83.25 (4)	O1ⁱⁱⁱ—Ca1—Cs1ⁱⁱⁱ	126.43 (5)
O2ⁱ—Cs1—O4^iv	109.66 (5)	C1ⁱⁱⁱ—Ca1—Cs1ⁱⁱⁱ	107.11 (5)
O4ⁱⁱ—Cs1—O4^iv	59.65 (6)	C1—Ca1—Cs1ⁱⁱⁱ	71.01 (5)
O1W—Cs1—O4^iv	68.25 (5)	C2ⁱⁱⁱ—Ca1—Cs1ⁱⁱⁱ	79.22 (4)
O1ⁱⁱⁱ—Cs1—O4^iv	127.01 (4)	C2—Ca1—Cs1ⁱⁱⁱ	97.83 (4)
O2^iv—Cs1—O4^iv	48.27 (4)	O2Wⁱⁱⁱ—Ca1—Cs1	129.31 (6)
O1^v—Cs1—O4^iv	107.77 (4)	O2W—Ca1—Cs1	54.62 (5)
O2W—Cs1—O4^iv	168.93 (4)	O3ⁱⁱⁱ—Ca1—Cs1	117.46 (5)
O2ⁱ—Cs1—O3	65.75 (5)	O3—Ca1—Cs1	58.85 (5)
O4ⁱⁱ—Cs1—O3	158.59 (4)	O1—Ca1—Cs1	126.43 (5)
O1W—Cs1—O3	100.76 (5)	O1ⁱⁱⁱ—Ca1—Cs1	52.98 (5)
O1ⁱⁱⁱ—Cs1—O3	53.03 (4)	C1ⁱⁱⁱ—Ca1—Cs1	71.01 (5)
O2^iv—Cs1—O3	72.14 (4)	C1—Ca1—Cs1	107.11 (5)
O1^v—Cs1—O3	128.54 (4)	C2ⁱⁱⁱ—Ca1—Cs1	97.83 (4)
O2W—Cs1—O3	50.03 (4)	C2—Ca1—Cs1	79.22 (4)
O4^iv—Cs1—O3	120.07 (4)	Cs1ⁱⁱⁱ—Ca1—Cs1	175.41 (2)
O2ⁱ—Cs1—C1^iv	112.56 (5)	O2Wⁱⁱⁱ—Ca1—H3	80.6 (9)
O4ⁱⁱ—Cs1—C1^iv	97.66 (5)	O2W—Ca1—H3	14.7 (9)
O1W—Cs1—C1^iv	55.28 (5)	O3ⁱⁱⁱ—Ca1—H3	161.3 (9)
O1ⁱⁱⁱ—Cs1—C1^iv	94.08 (4)	O3—Ca1—H3	102.5 (9)
O2^iv—Cs1—C1^iv	17.78 (4)	O1—Ca1—H3	102.7 (10)
O1^v—Cs1—C1^iv	128.86 (4)	O1ⁱⁱⁱ—Ca1—H3	87.3 (10)
O2W—Cs1—C1^iv	134.64 (5)	C1ⁱⁱⁱ—Ca1—H3	110.7 (10)
O4^iv—Cs1—C1^iv	38.09 (4)	C1—Ca1—H3	107.0 (10)
O3—Cs1—C1^iv	85.85 (4)	C2ⁱⁱⁱ—Ca1—H3	141.0 (10)
O2ⁱ—Cs1—C1^v	98.81 (5)	C2—Ca1—H3	106.2 (9)
O4ⁱⁱ—Cs1—C1^v	56.66 (5)	Cs1ⁱⁱⁱ—Ca1—H3	123.2 (10)
O1W—Cs1—C1^v	96.84 (5)	Cs1—Ca1—H3	61.3 (10)
O1ⁱⁱⁱ—Cs1—C1^v	95.90 (5)	O2Wⁱⁱⁱ—Ca1—H4	100.2 (12)
O2^iv—Cs1—C1^v	157.84 (5)	O2W—Ca1—H4	16.9 (10)
O1^v—Cs1—C1^v	18.14 (4)	O3ⁱⁱⁱ—Ca1—H4	169.1 (11)
O2W—Cs1—C1^v	79.44 (5)	O3—Ca1—H4	79.6 (12)
O4^iv—Cs1—C1^v	110.71 (4)	O1—Ca1—H4	80.4 (10)
O3—Cs1—C1^v	129.22 (4)	O1ⁱⁱⁱ—Ca1—H4	106.6 (10)
C1^iv—Cs1—C1^v	141.18 (6)	C1ⁱⁱⁱ—Ca1—H4	129.7 (10)
O2ⁱ—Cs1—C2^iv	119.80 (5)	C1—Ca1—H4	78.8 (10)
O4ⁱⁱ—Cs1—C2^iv	75.48 (5)	C2ⁱⁱⁱ—Ca1—H4	159.8 (11)
O1W—Cs1—C2^iv	54.11 (5)	C2—Ca1—H4	77.8 (11)
O1ⁱⁱⁱ—Cs1—C2^iv	109.27 (4)	Cs1ⁱⁱⁱ—Ca1—H4	121.0 (11)
O2^iv—Cs1—C2^iv	37.89 (4)	Cs1—Ca1—H4	62.0 (11)
O1^v—Cs1—C2^iv	111.62 (4)	H3—Ca1—H4	29.4 (14)
O2W—Cs1—C2^iv	157.40 (4)	O2—C1—O1	125.9 (2)
O4^iv—Cs1—C2^iv	17.93 (4)	O2—C1—C2	118.1 (2)
O3—Cs1—C2^iv	108.86 (4)	O1—C1—C2	116.0 (2)
C1^iv—Cs1—C2^iv	23.10 (5)	O2—C1—Ca1	166.71 (17)
C1^v—Cs1—C2^iv	119.95 (4)	C2—C1—Ca1	74.64 (12)
O2ⁱ—Cs1—H1	154.3 (7)	O2—C1—Cs1^vi	53.94 (13)
O4ⁱⁱ—Cs1—H1	111.6 (6)	O1—C1—Cs1^vi	138.48 (15)
O1W—Cs1—H1	14.1 (5)	C2—C1—Cs1^vi	79.72 (11)
O1ⁱⁱⁱ—Cs1—H1	49.6 (5)	Ca1—C1—Cs1^vi	130.00 (7)
O2^iv—Cs1—H1	72.7 (8)	O2—C1—Cs1^vii	88.32 (14)
O1^v—Cs1—H1	81.2 (8)	O1—C1—Cs1^vii	54.36 (11)
O2W—Cs1—H1	102.6 (6)	C2—C1—Cs1^vii	133.18 (13)
O4^iv—Cs1—H1	80.5 (6)	Ca1—C1—Cs1^vii	84.67 (5)
O3—Cs1—H1	88.6 (6)	Cs1^vi—C1—Cs1^vii	141.18 (6)
C1^iv—Cs1—H1	60.7 (8)	C1—O1—Ca1	114.80 (15)
C1^v—Cs1—H1	99.3 (8)	C1—O1—Cs1ⁱⁱⁱ	125.89 (14)
C2^iv—Cs1—H1	64.9 (6)	Ca1—O1—Cs1ⁱⁱⁱ	96.32 (6)
O2Wⁱⁱⁱ—Ca1—O2W	94.03 (11)	C1—O1—Cs1^vii	107.50 (14)
O2Wⁱⁱⁱ—Ca1—O3ⁱⁱⁱ	88.28 (7)	Ca1—O1—Cs1^vii	115.34 (7)
O2W—Ca1—O3ⁱⁱⁱ	170.75 (7)	Cs1ⁱⁱⁱ—O1—Cs1^vii	95.96 (4)
O2Wⁱⁱⁱ—Ca1—O3	170.75 (7)	C1—O2—Cs1ⁱ	147.27 (17)
O2W—Ca1—O3	88.28 (7)	C1—O2—Cs1^vi	108.28 (15)
O3ⁱⁱⁱ—Ca1—O3	90.86 (10)	Cs1ⁱ—O2—Cs1^vi	97.86 (5)
O2Wⁱⁱⁱ—Ca1—O1	91.87 (7)	O4—C2—O3	125.9 (2)
O2W—Ca1—O1	96.30 (7)	O4—C2—C1	119.50 (19)
O3ⁱⁱⁱ—Ca1—O1	92.57 (7)	O3—C2—C1	114.60 (18)
O3—Ca1—O1	78.97 (7)	O4—C2—Ca1	166.69 (16)
O2Wⁱⁱⁱ—Ca1—O1ⁱⁱⁱ	96.30 (7)	C1—C2—Ca1	73.76 (11)
O2W—Ca1—O1ⁱⁱⁱ	91.87 (7)	O4—C2—Cs1^vi	58.69 (13)
O3ⁱⁱⁱ—Ca1—O1ⁱⁱⁱ	78.97 (7)	O3—C2—Cs1^vi	137.27 (14)
O3—Ca1—O1ⁱⁱⁱ	92.57 (7)	C1—C2—Cs1^vi	77.18 (11)
O1—Ca1—O1ⁱⁱⁱ	168.01 (10)	Ca1—C2—Cs1^vi	128.24 (7)
O2Wⁱⁱⁱ—Ca1—C1ⁱⁱⁱ	95.70 (7)	C2—O4—Cs1^viii	127.57 (15)
O2W—Ca1—C1ⁱⁱⁱ	115.59 (7)	C2—O4—Cs1^vi	103.37 (14)
O3ⁱⁱⁱ—Ca1—C1ⁱⁱⁱ	55.22 (6)	Cs1^viii—O4—Cs1^vi	120.35 (6)
O3—Ca1—C1ⁱⁱⁱ	91.35 (7)	C2—O3—Ca1	115.54 (14)
O1—Ca1—C1ⁱⁱⁱ	146.48 (7)	C2—O3—Cs1	138.80 (14)
O1ⁱⁱⁱ—Ca1—C1ⁱⁱⁱ	23.78 (6)	Ca1—O3—Cs1	90.28 (6)
O2Wⁱⁱⁱ—Ca1—C1	115.59 (7)	Cs1—O1W—H1	95 (4)
O2W—Ca1—C1	95.70 (7)	Cs1—O1W—H2	141 (4)
O3ⁱⁱⁱ—Ca1—C1	91.35 (7)	H1—O1W—H2	111 (5)
O3—Ca1—C1	55.22 (6)	Ca1—O2W—Cs1	95.21 (6)
O1—Ca1—C1	23.78 (6)	Ca1—O2W—H3	126 (3)
O1ⁱⁱⁱ—Ca1—C1	146.48 (7)	Cs1—O2W—H3	105 (3)
C1ⁱⁱⁱ—Ca1—C1	134.14 (9)	Ca1—O2W—H4	116 (4)
O2Wⁱⁱⁱ—Ca1—C2ⁱⁱⁱ	91.60 (7)	Cs1—O2W—H4	106 (4)
O2W—Ca1—C2ⁱⁱⁱ	147.17 (7)	H3—O2W—H4	106 (5)

O2ⁱ—Cs1—Ca1—O2Wⁱⁱⁱ	115.19 (8)	O2—C1—O1—Cs1^vii	55.7 (3)
O4ⁱⁱ—Cs1—Ca1—O2Wⁱⁱⁱ	39.97 (10)	C2—C1—O1—Cs1^vii	−125.96 (15)
O1W—Cs1—Ca1—O2Wⁱⁱⁱ	−79.43 (7)	Ca1—C1—O1—Cs1^vii	−129.79 (16)
O1ⁱⁱⁱ—Cs1—Ca1—O2Wⁱⁱⁱ	−63.90 (9)	Cs1^vi—C1—O1—Cs1^vii	129.51 (16)
O2^iv—Cs1—Ca1—O2Wⁱⁱⁱ	−149.93 (7)	O2Wⁱⁱⁱ—Ca1—O1—C1	175.89 (16)
O1^v—Cs1—Ca1—O2Wⁱⁱⁱ	0.17 (7)	O2W—Ca1—O1—C1	−89.85 (17)
O2W—Cs1—Ca1—O2Wⁱⁱⁱ	61.95 (13)	O3ⁱⁱⁱ—Ca1—O1—C1	87.52 (16)
O4^iv—Cs1—Ca1—O2Wⁱⁱⁱ	−135.51 (8)	O3—Ca1—O1—C1	−2.85 (16)
O3—Cs1—Ca1—O2Wⁱⁱⁱ	174.67 (9)	O1ⁱⁱⁱ—Ca1—O1—C1	42.85 (15)
C1^iv—Cs1—Ca1—O2Wⁱⁱⁱ	−134.13 (7)	C1ⁱⁱⁱ—Ca1—O1—C1	72.6 (2)
C1^v—Cs1—Ca1—O2Wⁱⁱⁱ	18.20 (7)	C2ⁱⁱⁱ—Ca1—O1—C1	83.21 (17)
C2^iv—Cs1—Ca1—O2Wⁱⁱⁱ	−125.01 (8)	C2—Ca1—O1—C1	−2.27 (14)
O2ⁱ—Cs1—Ca1—O2W	53.23 (7)	Cs1ⁱⁱⁱ—Ca1—O1—C1	134.50 (17)
O4ⁱⁱ—Cs1—Ca1—O2W	−21.98 (10)	Cs1—Ca1—O1—C1	−39.83 (18)
O1W—Cs1—Ca1—O2W	−141.38 (7)	O2Wⁱⁱⁱ—Ca1—O1—Cs1ⁱⁱⁱ	41.39 (6)
O1ⁱⁱⁱ—Cs1—Ca1—O2W	−125.86 (9)	O2W—Ca1—O1—Cs1ⁱⁱⁱ	135.65 (6)
O2^iv—Cs1—Ca1—O2W	148.11 (7)	O3ⁱⁱⁱ—Ca1—O1—Cs1ⁱⁱⁱ	−46.97 (6)
O1^v—Cs1—Ca1—O2W	−61.78 (7)	O3—Ca1—O1—Cs1ⁱⁱⁱ	−137.35 (7)
O4^iv—Cs1—Ca1—O2W	162.53 (8)	O1ⁱⁱⁱ—Ca1—O1—Cs1ⁱⁱⁱ	−91.7 (5)
O3—Cs1—Ca1—O2W	112.72 (8)	C1ⁱⁱⁱ—Ca1—O1—Cs1ⁱⁱⁱ	−61.87 (12)
C1^iv—Cs1—Ca1—O2W	163.92 (7)	C1—Ca1—O1—Cs1ⁱⁱⁱ	−134.50 (18)
C1^v—Cs1—Ca1—O2W	−43.75 (7)	C2ⁱⁱⁱ—Ca1—O1—Cs1ⁱⁱⁱ	−51.29 (7)
C2^iv—Cs1—Ca1—O2W	173.04 (7)	C2—Ca1—O1—Cs1ⁱⁱⁱ	−136.77 (8)
O2ⁱ—Cs1—Ca1—O3ⁱⁱⁱ	−132.36 (7)	Cs1—Ca1—O1—Cs1ⁱⁱⁱ	−174.33 (3)
O4ⁱⁱ—Cs1—Ca1—O3ⁱⁱⁱ	152.42 (10)	O2Wⁱⁱⁱ—Ca1—O1—Cs1^vii	−58.29 (8)
O1W—Cs1—Ca1—O3ⁱⁱⁱ	33.02 (7)	O2W—Ca1—O1—Cs1^vii	35.97 (8)
O1ⁱⁱⁱ—Cs1—Ca1—O3ⁱⁱⁱ	48.55 (8)	O3ⁱⁱⁱ—Ca1—O1—Cs1^vii	−146.65 (8)
O2^iv—Cs1—Ca1—O3ⁱⁱⁱ	−37.49 (6)	O3—Ca1—O1—Cs1^vii	122.98 (8)
O1^v—Cs1—Ca1—O3ⁱⁱⁱ	112.62 (6)	O1ⁱⁱⁱ—Ca1—O1—Cs1^vii	168.7 (4)
O2W—Cs1—Ca1—O3ⁱⁱⁱ	174.40 (8)	C1ⁱⁱⁱ—Ca1—O1—Cs1^vii	−161.55 (9)
O4^iv—Cs1—Ca1—O3ⁱⁱⁱ	−23.07 (8)	C1—Ca1—O1—Cs1^vii	125.83 (19)
O3—Cs1—Ca1—O3ⁱⁱⁱ	−72.88 (11)	C2ⁱⁱⁱ—Ca1—O1—Cs1^vii	−150.97 (6)
C1^iv—Cs1—Ca1—O3ⁱⁱⁱ	−21.68 (7)	C2—Ca1—O1—Cs1^vii	123.55 (10)
C1^v—Cs1—Ca1—O3ⁱⁱⁱ	130.65 (7)	Cs1ⁱⁱⁱ—Ca1—O1—Cs1^vii	−99.68 (7)
C2^iv—Cs1—Ca1—O3ⁱⁱⁱ	−12.56 (7)	Cs1—Ca1—O1—Cs1^vii	86.00 (7)
O2ⁱ—Cs1—Ca1—O3	−59.48 (7)	O1—C1—O2—Cs1ⁱ	−90.7 (4)
O4ⁱⁱ—Cs1—Ca1—O3	−134.70 (10)	C2—C1—O2—Cs1ⁱ	91.0 (3)
O1W—Cs1—Ca1—O3	105.90 (7)	Ca1—C1—O2—Cs1ⁱ	−106.6 (7)
O1ⁱⁱⁱ—Cs1—Ca1—O3	121.43 (8)	Cs1^vi—C1—O2—Cs1ⁱ	141.3 (3)
O2^iv—Cs1—Ca1—O3	35.39 (7)	Cs1^vii—C1—O2—Cs1ⁱ	−48.5 (3)
O1^v—Cs1—Ca1—O3	−174.50 (6)	O1—C1—O2—Cs1^vi	128.0 (2)
O2W—Cs1—Ca1—O3	−112.72 (8)	C2—C1—O2—Cs1^vi	−50.3 (2)
O4^iv—Cs1—Ca1—O3	49.81 (8)	Ca1—C1—O2—Cs1^vi	112.1 (7)
C1^iv—Cs1—Ca1—O3	51.20 (7)	Cs1^vii—C1—O2—Cs1^vi	170.22 (7)
C1^v—Cs1—Ca1—O3	−156.47 (7)	O2—C1—C2—O4	−3.0 (3)
C2^iv—Cs1—Ca1—O3	60.32 (7)	O1—C1—C2—O4	178.5 (2)
O2ⁱ—Cs1—Ca1—O1	−15.86 (8)	Ca1—C1—C2—O4	−178.8 (2)
O4ⁱⁱ—Cs1—Ca1—O1	−91.08 (11)	Cs1^vi—C1—C2—O4	−42.18 (19)
O1W—Cs1—Ca1—O1	149.52 (7)	Cs1^vii—C1—C2—O4	114.1 (2)
O1ⁱⁱⁱ—Cs1—Ca1—O1	165.05 (12)	O2—C1—C2—O3	175.6 (2)
O2^iv—Cs1—Ca1—O1	79.01 (7)	O1—C1—C2—O3	−2.9 (3)
O1^v—Cs1—Ca1—O1	−130.88 (6)	Ca1—C1—C2—O3	−0.25 (16)
O2W—Cs1—Ca1—O1	−69.10 (9)	Cs1^vi—C1—C2—O3	136.42 (18)
O4^iv—Cs1—Ca1—O1	93.43 (8)	Cs1^vii—C1—C2—O3	−67.3 (2)
O3—Cs1—Ca1—O1	43.62 (8)	O2—C1—C2—Ca1	175.9 (2)
C1^iv—Cs1—Ca1—O1	94.82 (7)	O1—C1—C2—Ca1	−2.63 (16)
C1^v—Cs1—Ca1—O1	−112.85 (7)	Cs1^vi—C1—C2—Ca1	136.67 (5)
C2^iv—Cs1—Ca1—O1	103.94 (7)	Cs1^vii—C1—C2—Ca1	−67.05 (14)
O2ⁱ—Cs1—Ca1—O1ⁱⁱⁱ	179.09 (7)	O2—C1—C2—Cs1^vi	39.20 (19)
O4ⁱⁱ—Cs1—Ca1—O1ⁱⁱⁱ	103.88 (10)	O1—C1—C2—Cs1^vi	−139.29 (19)
O1W—Cs1—Ca1—O1ⁱⁱⁱ	−15.53 (7)	Ca1—C1—C2—Cs1^vi	−136.67 (5)
O2^iv—Cs1—Ca1—O1ⁱⁱⁱ	−86.03 (7)	Cs1^vii—C1—C2—Cs1^vi	156.28 (15)
O1^v—Cs1—Ca1—O1ⁱⁱⁱ	64.08 (8)	O2Wⁱⁱⁱ—Ca1—C2—O4	174.0 (7)
O2W—Cs1—Ca1—O1ⁱⁱⁱ	125.86 (9)	O2W—Ca1—C2—O4	−86.1 (7)
O4^iv—Cs1—Ca1—O1ⁱⁱⁱ	−71.61 (8)	O3ⁱⁱⁱ—Ca1—C2—O4	85.2 (7)
O3—Cs1—Ca1—O1ⁱⁱⁱ	−121.43 (8)	O3—Ca1—C2—O4	−4.0 (7)
C1^iv—Cs1—Ca1—O1ⁱⁱⁱ	−70.23 (7)	O1—Ca1—C2—O4	177.4 (8)
C1^v—Cs1—Ca1—O1ⁱⁱⁱ	82.10 (7)	O1ⁱⁱⁱ—Ca1—C2—O4	6.8 (7)
C2^iv—Cs1—Ca1—O1ⁱⁱⁱ	−61.11 (7)	C1ⁱⁱⁱ—Ca1—C2—O4	32.2 (7)
O2ⁱ—Cs1—Ca1—C1ⁱⁱⁱ	−163.20 (6)	C1—Ca1—C2—O4	175.6 (8)
O4ⁱⁱ—Cs1—Ca1—C1ⁱⁱⁱ	121.58 (10)	C2ⁱⁱⁱ—Ca1—C2—O4	63.4 (7)
O1W—Cs1—Ca1—C1ⁱⁱⁱ	2.18 (6)	Cs1ⁱⁱⁱ—Ca1—C2—O4	143.9 (7)
O1ⁱⁱⁱ—Cs1—Ca1—C1ⁱⁱⁱ	17.71 (7)	Cs1—Ca1—C2—O4	−32.6 (7)
O2^iv—Cs1—Ca1—C1ⁱⁱⁱ	−68.32 (6)	O2Wⁱⁱⁱ—Ca1—C2—O3	178.02 (16)
O1^v—Cs1—Ca1—C1ⁱⁱⁱ	81.78 (6)	O2W—Ca1—C2—O3	−82.03 (17)
O2W—Cs1—Ca1—C1ⁱⁱⁱ	143.56 (8)	O3ⁱⁱⁱ—Ca1—C2—O3	89.18 (18)
O4^iv—Cs1—Ca1—C1ⁱⁱⁱ	−53.90 (7)	O1—Ca1—C2—O3	−178.59 (19)
O3—Cs1—Ca1—C1ⁱⁱⁱ	−103.72 (7)	O1ⁱⁱⁱ—Ca1—C2—O3	10.82 (18)
C1^iv—Cs1—Ca1—C1ⁱⁱⁱ	−52.52 (7)	C1ⁱⁱⁱ—Ca1—C2—O3	36.19 (17)
C1^v—Cs1—Ca1—C1ⁱⁱⁱ	99.81 (5)	C1—Ca1—C2—O3	179.7 (2)
C2^iv—Cs1—Ca1—C1ⁱⁱⁱ	−43.40 (6)	C2ⁱⁱⁱ—Ca1—C2—O3	67.45 (15)
O2ⁱ—Cs1—Ca1—C1	−31.54 (6)	Cs1ⁱⁱⁱ—Ca1—C2—O3	147.91 (15)
O4ⁱⁱ—Cs1—Ca1—C1	−106.76 (10)	Cs1—Ca1—C2—O3	−28.54 (15)
O1W—Cs1—Ca1—C1	133.84 (6)	O2Wⁱⁱⁱ—Ca1—C2—C1	−1.64 (19)
O1ⁱⁱⁱ—Cs1—Ca1—C1	149.37 (8)	O2W—Ca1—C2—C1	98.31 (12)
O2^iv—Cs1—Ca1—C1	63.34 (6)	O3ⁱⁱⁱ—Ca1—C2—C1	−90.48 (12)
O1^v—Cs1—Ca1—C1	−146.56 (6)	O3—Ca1—C2—C1	−179.7 (2)
O2W—Cs1—Ca1—C1	−84.78 (8)	O1—Ca1—C2—C1	1.75 (11)
O4^iv—Cs1—Ca1—C1	77.76 (7)	O1ⁱⁱⁱ—Ca1—C2—C1	−168.84 (11)
O3—Cs1—Ca1—C1	27.94 (7)	C1ⁱⁱⁱ—Ca1—C2—C1	−143.47 (10)
C1^iv—Cs1—Ca1—C1	79.14 (4)	C2ⁱⁱⁱ—Ca1—C2—C1	−112.21 (12)
C1^v—Cs1—Ca1—C1	−128.53 (6)	Cs1ⁱⁱⁱ—Ca1—C2—C1	−31.75 (11)
C2^iv—Cs1—Ca1—C1	88.26 (6)	Cs1—Ca1—C2—C1	151.80 (11)
O2ⁱ—Cs1—Ca1—C2ⁱⁱⁱ	−146.25 (6)	O2Wⁱⁱⁱ—Ca1—C2—Cs1^vi	56.78 (16)
O4ⁱⁱ—Cs1—Ca1—C2ⁱⁱⁱ	138.54 (9)	O2W—Ca1—C2—Cs1^vi	156.73 (9)
O1W—Cs1—Ca1—C2ⁱⁱⁱ	19.14 (6)	O3ⁱⁱⁱ—Ca1—C2—Cs1^vi	−32.05 (9)
O1ⁱⁱⁱ—Cs1—Ca1—C2ⁱⁱⁱ	34.66 (7)	O3—Ca1—C2—Cs1^vi	−121.23 (19)
O2^iv—Cs1—Ca1—C2ⁱⁱⁱ	−51.37 (5)	O1—Ca1—C2—Cs1^vi	60.17 (9)
O1^v—Cs1—Ca1—C2ⁱⁱⁱ	98.74 (5)	O1ⁱⁱⁱ—Ca1—C2—Cs1^vi	−110.41 (9)
O2W—Cs1—Ca1—C2ⁱⁱⁱ	160.52 (8)	C1ⁱⁱⁱ—Ca1—C2—Cs1^vi	−85.05 (9)
O4^iv—Cs1—Ca1—C2ⁱⁱⁱ	−36.95 (7)	C1—Ca1—C2—Cs1^vi	58.42 (11)
O3—Cs1—Ca1—C2ⁱⁱⁱ	−86.76 (7)	C2ⁱⁱⁱ—Ca1—C2—Cs1^vi	−53.78 (6)
C1^iv—Cs1—Ca1—C2ⁱⁱⁱ	−35.56 (6)	Cs1ⁱⁱⁱ—Ca1—C2—Cs1^vi	26.67 (8)
C1^v—Cs1—Ca1—C2ⁱⁱⁱ	116.76 (6)	Cs1—Ca1—C2—Cs1^vi	−149.78 (8)
C2^iv—Cs1—Ca1—C2ⁱⁱⁱ	−26.45 (8)	O3—C2—O4—Cs1^viii	18.6 (3)
O2ⁱ—Cs1—Ca1—C2	−46.56 (6)	C1—C2—O4—Cs1^viii	−163.01 (13)
O4ⁱⁱ—Cs1—Ca1—C2	−121.77 (9)	Ca1—C2—O4—Cs1^viii	21.8 (8)
O1W—Cs1—Ca1—C2	118.83 (6)	Cs1^vi—C2—O4—Cs1^viii	146.96 (19)
O1ⁱⁱⁱ—Cs1—Ca1—C2	134.35 (7)	O3—C2—O4—Cs1^vi	−128.4 (2)
O2^iv—Cs1—Ca1—C2	48.32 (5)	C1—C2—O4—Cs1^vi	50.0 (2)
O1^v—Cs1—Ca1—C2	−161.57 (5)	Ca1—C2—O4—Cs1^vi	−125.2 (7)
O2W—Cs1—Ca1—C2	−99.79 (7)	O4—C2—O3—Ca1	178.86 (19)
O4^iv—Cs1—Ca1—C2	62.74 (7)	C1—C2—O3—Ca1	0.4 (2)
O3—Cs1—Ca1—C2	12.93 (7)	Cs1^vi—C2—O3—Ca1	98.19 (19)
C1^iv—Cs1—Ca1—C2	64.13 (6)	O4—C2—O3—Cs1	−57.5 (3)
C1^v—Cs1—Ca1—C2	−143.54 (6)	C1—C2—O3—Cs1	123.99 (18)
C2^iv—Cs1—Ca1—C2	73.24 (2)	Ca1—C2—O3—Cs1	123.6 (2)
O2Wⁱⁱⁱ—Ca1—C1—O2	15.1 (8)	Cs1^vi—C2—O3—Cs1	−138.18 (13)
O2W—Ca1—C1—O2	112.3 (7)	O2W—Ca1—O3—C2	97.94 (16)
O3ⁱⁱⁱ—Ca1—C1—O2	−73.7 (8)	O3ⁱⁱⁱ—Ca1—O3—C2	−91.27 (16)
O3—Ca1—C1—O2	−163.8 (8)	O1—Ca1—O3—C2	1.18 (16)
O1—Ca1—C1—O2	19.6 (7)	O1ⁱⁱⁱ—Ca1—O3—C2	−170.26 (16)
O1ⁱⁱⁱ—Ca1—C1—O2	−145.6 (7)	C1ⁱⁱⁱ—Ca1—O3—C2	−146.50 (16)
C1ⁱⁱⁱ—Ca1—C1—O2	−113.1 (8)	C1—Ca1—O3—C2	−0.22 (14)
C2ⁱⁱⁱ—Ca1—C1—O2	−87.4 (7)	C2ⁱⁱⁱ—Ca1—O3—C2	−114.89 (16)
C2—Ca1—C1—O2	−164.0 (8)	Cs1ⁱⁱⁱ—Ca1—O3—C2	−36.38 (17)
Cs1ⁱⁱⁱ—Ca1—C1—O2	−17.4 (7)	Cs1—Ca1—O3—C2	146.74 (17)
Cs1—Ca1—C1—O2	167.0 (7)	O2W—Ca1—O3—Cs1	−48.80 (6)
O2Wⁱⁱⁱ—Ca1—C1—O1	−4.56 (18)	O3ⁱⁱⁱ—Ca1—O3—Cs1	121.99 (6)
O2W—Ca1—C1—O1	92.68 (17)	O1—Ca1—O3—Cs1	−145.56 (6)
O3ⁱⁱⁱ—Ca1—C1—O1	−93.30 (16)	O1ⁱⁱⁱ—Ca1—O3—Cs1	43.00 (6)
O3—Ca1—C1—O1	176.60 (19)	C1ⁱⁱⁱ—Ca1—O3—Cs1	66.76 (5)
O1ⁱⁱⁱ—Ca1—C1—O1	−165.18 (13)	C1—Ca1—O3—Cs1	−146.96 (8)
C1ⁱⁱⁱ—Ca1—C1—O1	−132.75 (17)	C2ⁱⁱⁱ—Ca1—O3—Cs1	98.37 (5)
C2ⁱⁱⁱ—Ca1—C1—O1	−106.99 (16)	C2—Ca1—O3—Cs1	−146.74 (17)
C2—Ca1—C1—O1	176.4 (2)	Cs1ⁱⁱⁱ—Ca1—O3—Cs1	176.877 (14)
Cs1ⁱⁱⁱ—Ca1—C1—O1	−37.03 (15)	O2ⁱ—Cs1—O3—C2	−19.6 (2)
Cs1—Ca1—C1—O1	147.37 (15)	O4ⁱⁱ—Cs1—O3—C2	−3.0 (3)
O2Wⁱⁱⁱ—Ca1—C1—C2	179.01 (11)	O1W—Cs1—O3—C2	150.9 (2)
O2W—Ca1—C1—C2	−83.74 (12)	O1ⁱⁱⁱ—Cs1—O3—C2	−164.4 (2)
O3ⁱⁱⁱ—Ca1—C1—C2	90.27 (12)	O2^iv—Cs1—O3—C2	85.8 (2)
O3—Ca1—C1—C2	0.17 (11)	O1^v—Cs1—O3—C2	−124.3 (2)
O1—Ca1—C1—C2	−176.4 (2)	O2W—Cs1—O3—C2	−94.1 (2)
O1ⁱⁱⁱ—Ca1—C1—C2	18.39 (18)	O4^iv—Cs1—O3—C2	79.9 (2)
C1ⁱⁱⁱ—Ca1—C1—C2	50.82 (10)	C1^iv—Cs1—O3—C2	97.4 (2)
C2ⁱⁱⁱ—Ca1—C1—C2	76.58 (14)	C1^v—Cs1—O3—C2	−101.0 (2)
Cs1ⁱⁱⁱ—Ca1—C1—C2	146.54 (11)	C2^iv—Cs1—O3—C2	95.3 (2)
Cs1—Ca1—C1—C2	−29.06 (11)	O2ⁱ—Cs1—O3—Ca1	111.65 (7)
O2Wⁱⁱⁱ—Ca1—C1—Cs1^vi	117.19 (10)	O4ⁱⁱ—Cs1—O3—Ca1	128.25 (11)
O2W—Ca1—C1—Cs1^vi	−145.57 (10)	O1W—Cs1—O3—Ca1	−77.83 (6)
O3ⁱⁱⁱ—Ca1—C1—Cs1^vi	28.45 (10)	O1ⁱⁱⁱ—Cs1—O3—Ca1	−33.05 (5)
O3—Ca1—C1—Cs1^vi	−61.65 (9)	O2^iv—Cs1—O3—Ca1	−142.87 (7)
O1—Ca1—C1—Cs1^vi	121.8 (2)	O1^v—Cs1—O3—Ca1	6.97 (8)
O1ⁱⁱⁱ—Ca1—C1—Cs1^vi	−43.43 (17)	O2W—Cs1—O3—Ca1	37.23 (5)
C1ⁱⁱⁱ—Ca1—C1—Cs1^vi	−11.00 (6)	O4^iv—Cs1—O3—Ca1	−148.82 (5)
C2ⁱⁱⁱ—Ca1—C1—Cs1^vi	14.76 (11)	C1^iv—Cs1—O3—Ca1	−131.32 (6)
C2—Ca1—C1—Cs1^vi	−61.82 (11)	C1^v—Cs1—O3—Ca1	30.32 (8)
Cs1ⁱⁱⁱ—Ca1—C1—Cs1^vi	84.72 (8)	C2^iv—Cs1—O3—Ca1	−133.39 (5)
Cs1—Ca1—C1—Cs1^vi	−90.88 (8)	O2Wⁱⁱⁱ—Ca1—O2W—Cs1	−136.80 (8)
O2Wⁱⁱⁱ—Ca1—C1—Cs1^vii	−43.40 (8)	O3—Ca1—O2W—Cs1	52.16 (6)
O2W—Ca1—C1—Cs1^vii	53.84 (7)	O1—Ca1—O2W—Cs1	130.87 (6)
O3ⁱⁱⁱ—Ca1—C1—Cs1^vii	−132.14 (6)	O1ⁱⁱⁱ—Ca1—O2W—Cs1	−40.35 (6)
O3—Ca1—C1—Cs1^vii	137.76 (8)	C1ⁱⁱⁱ—Ca1—O2W—Cs1	−38.51 (8)
O1—Ca1—C1—Cs1^vii	−38.84 (15)	C1—Ca1—O2W—Cs1	106.96 (6)
O1ⁱⁱⁱ—Ca1—C1—Cs1^vii	155.98 (10)	C2ⁱⁱⁱ—Ca1—O2W—Cs1	−37.56 (14)
C1ⁱⁱⁱ—Ca1—C1—Cs1^vii	−171.59 (5)	C2—Ca1—O2W—Cs1	75.56 (5)
C2ⁱⁱⁱ—Ca1—C1—Cs1^vii	−145.83 (5)	Cs1ⁱⁱⁱ—Ca1—O2W—Cs1	177.031 (16)
C2—Ca1—C1—Cs1^vii	137.59 (12)	O2ⁱ—Cs1—O2W—Ca1	−117.98 (8)
Cs1ⁱⁱⁱ—Ca1—C1—Cs1^vii	−75.87 (3)	O4ⁱⁱ—Cs1—O2W—Ca1	169.09 (5)
Cs1—Ca1—C1—Cs1^vii	108.53 (3)	O1W—Cs1—O2W—Ca1	43.91 (7)
O2—C1—O1—Ca1	−174.53 (19)	O1ⁱⁱⁱ—Cs1—O2W—Ca1	30.93 (5)
C2—C1—O1—Ca1	3.8 (2)	O2^iv—Cs1—O2W—Ca1	−38.25 (8)
Cs1^vi—C1—O1—Ca1	−100.7 (2)	O1^v—Cs1—O2W—Ca1	118.48 (6)
Cs1^vii—C1—O1—Ca1	129.79 (16)	O4^iv—Cs1—O2W—Ca1	−66.5 (2)
O2—C1—O1—Cs1ⁱⁱⁱ	−55.6 (3)	O3—Cs1—O2W—Ca1	−38.14 (5)
C2—C1—O1—Cs1ⁱⁱⁱ	122.78 (17)	C1^iv—Cs1—O2W—Ca1	−21.98 (9)
Ca1—C1—O1—Cs1ⁱⁱⁱ	118.94 (19)	C1^v—Cs1—O2W—Ca1	136.42 (7)
Cs1^vi—C1—O1—Cs1ⁱⁱⁱ	18.2 (3)	C2^iv—Cs1—O2W—Ca1	−14.46 (15)
Cs1^vii—C1—O1—Cs1ⁱⁱⁱ	−111.26 (16)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1···O2ⁱⁱⁱ	0.81 (7)	1.91 (7)	2.714 (4)	172 (6)
O1W—H2···O3^ix	0.81 (4)	1.95 (4)	2.736 (2)	163 (7)
O2W—H3···O1W^x	0.82 (3)	1.89 (3)	2.680 (2)	164 (5)
O2W—H4···O4ⁱ	0.81 (4)	1.92 (3)	2.724 (3)	176 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1···O2ⁱ	0.81 (7)	1.91 (7)	2.714 (4)	172 (6)
O1W—H2···O3ⁱⁱ	0.81 (4)	1.95 (4)	2.736 (2)	163 (7)
O2W—H3···O1Wⁱⁱⁱ	0.82 (3)	1.89 (3)	2.680 (2)	164 (5)
O2W—H4···O4^iv	0.81 (4)	1.92 (3)	2.724 (3)	176 (7)

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

Acknowledgements

The authors thank E. Wenger, Service Commun de Diffractométrie, CRM2 UMR-CNRS 7036, Jean Barriol Institut, Lorraine Université BP 230, 54506 Vandoeuvre-lés-Nancy Cedex France, for X-ray data collection. We are grateful for financial support from the project CMEP-TASSILI programme (MESRS-Algeria and MDU-France).

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