Caesium sodium bis­(formate)

Alcock, N.W.; Wilson, M.P.; Rodger, P.M.

doi:10.1107/S1600536806003047

metal-organic compounds

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ISSN: 2056-9890

Volume 62| Part 2| February 2006| Pages m388-m390

https://doi.org/10.1107/S1600536806003047

Caesium sodium bis(formate)

Nathaniel W. Alcock,^a Michael P. Wilson ^a and P. Mark Rodger ^a ^*

^aDepartment of Chemistry, University of Warwick, Coventry CV4 7AL, England
^*Correspondence e-mail: msrbb@csv.warwick.ac.uk

(Received 18 January 2006; accepted 25 January 2006; online 31 January 2006)

The title compound, CsNa(CHO₂)₂, was obtained from the crystallization of caesium formate in a glass container. It has a complex structure, with sodium ions octahedrally coordinated and caesium ions irregularly eight-coordinated by the formate O atoms. One Cs cation and four formate C atoms have site symmetry m and one Na cation has site symmetry $[\overline{1}]$ , resulting in the unusual situation of Z = 12 for an orthorhombic structure.

Comment

During a study of the crystal structure of caesium formate (Wilson et al., 2006 ), it was found that, if the crystallization of caesium formate by diffusion is carried out in a glass container, the crystals formed are of a mixed caesium sodium salt, CsNa(C₂HO₂)₂, (I).

The sodium ions were identified from the crystal structure analysis. After initial location of the Cs atoms, the chemical identity of two medium height electron-density peaks was tested by refinement. Only the assignment of Na to the peaks both satisfied stoichiometric requirements and gave satisfactory displacement parameters (as well as providing much the best R value). It is inferred that their source is the glass vials used for crystallization, and it has been shown (Wilson et al., 2006) that recrystallization from polythene vials gives unchanged caesium formate. Similar extraction of sodium cations by formate solutions has been reported by Robinet et al. (2004 ).

In the structure of (I) (Fig. 1), both Na ions are octahedrally coordinated, with Na—O distances (Table 1) in the range 2.243 (4)–2.678 (3) Å (Fig. 2). The coordination of the Cs ions (Fig. 3) is best regarded as eight-coordinate, with Cs1 having square-antiprismatic geometry and Cs2 a less regular arrangement of ligand O atoms [Cs—O = 3.007 (3)–3.550 (4) Å], but with additional O atoms within 0.3 Å. The overall packing (Fig. 4) can be described as including chains of cations bridged by formate ions.

Figure 1
View of the asymmetric unit of (I)

(with formate ions completed by symmetry), showing 50% displacement ellipsoids (arbitrary spheres for the H atoms). Cs, H, Na and O atoms are green (large), green (small), blue and red, respectively. [Symmetry codes: x, − $[{1\over 2}]$ − y, z (for O2A and O4A); x, $[{1\over 2}]$ − y, z (for O3A and O5A)].

Figure 2
The structure with the Na ion coordination completed. Atom colouring as in Fig. 1

. [Symmetry codes: x, − $[{1\over 2}]$ − y, z (O2A and O4A); x, $[{1\over 2}]$ − y, z (O3A, O5A, O11A, O12A and C1A); 2 − x, −y, 1 − z (C4A, O4B, O5B and C5A); 2 − x, $[{1\over 2}]$ − y, 1 − z (O4AA and O5AA); $[{1\over 2}]$ + x, y, $[{3\over 2}]$ − z (O11B, O12B and C1B)].

Figure 3
The structure with the Cs ion coordination completed. Atom colouring as in Fig. 1

. [Symmetry codes: x, − $[{1\over 2}]$ − y, z (O2A and O4A); x, $[{1\over 2}]$ − y, z (O3A and O5A); $[{1\over 2}]$ + x, y, $[{3\over 2}]$ − z (O11A, C1, O12C, O12B, C1C, O11C, O2D and C2C); $[{1\over 2}]$ + x, −1 + y, $[{3\over 2}]$ − z (O2C and C2B); $[{3\over 2}]$ − x, −y, − $[{1\over 2}]$ − z (O2B and C2A); 1 − x, −y, 1 − z (O3B and C3A); 2 − x, −y, 1 − z (O11B, C1B and O12A); $[{3\over 2}]$ − x, −y, − $[{1\over 2}]$ − z (O2AA); − $[{1\over 2}]$ + x, − $[{1\over 2}]$ − y, $[{3\over 2}]$ − z (O2AB); $[{1\over 2}]$ + x, − $[{1\over 2}]$ − y, $[{3\over 2}]$ − z (O2AC); $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, $[{1\over 2}]$ − z (O3AB); 1 − x, − $[{1\over 2}]$ + y, 1 − z (O3AA); 1 + x, y, z (O3C and C3B)].

Figure 4
The packing, viewed down the b axis. Atom colouring as in Fig. 1

Experimental

AR standard caesium formate (Aldrich) was dissolved in a minimum volume of methanol in a glass vial. This (open) container was then placed inside a larger vial containing a small amount of 1-butanol and the whole system sealed immediately. Crystallization proceeded with occasional swirling of the suspension over a two-week period.

Crystal data

CsNa(CHO₂)₂
M_r = 245.94
Orthorhombic, P n m a
a = 12.5812 (3) Å
b = 11.0509 (3) Å
c = 12.6024 (3) Å
V = 1752.16 (8) Å³
Z = 12
D_x = 2.797 Mg m⁻³
Mo Kα radiation
Cell parameters from 8192 reflections
θ = 3–25°
μ = 6.34 mm⁻¹
T = 180 (2) K
Block, colourless
0.20 × 0.20 × 0.15 mm

Data collection

Siemens SMART diffractometer
ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 1996 )T_min = 0.202, T_max = 0.387
10798 measured reflections
2324 independent reflections
1867 reflections with I > 2σ(I)
R_int = 0.042
θ_max = 29.1°
h = −15 → 16
k = −15 → 14
l = −14 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.090
S = 1.03
2324 reflections
119 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.055P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.003
Δρ_max = 1.59 e Å⁻³
Δρ_min = −1.59 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.0039 (3)

Table 1
Selected bond lengths (Å)

Cs1—O11	3.193 (3)
Cs1—O12	3.294 (4)
Cs1—O4ⁱ	3.389 (3)
Cs1—O3	3.441 (3)
Cs1—O2ⁱⁱ	3.642 (4)
Cs2—O4ⁱⁱⁱ	3.007 (3)
Cs2—O5	3.015 (3)
Cs2—O3^iv	3.027 (3)
Cs2—O12	3.206 (4)
Cs2—O4	3.386 (3)
Cs2—O5ⁱⁱⁱ	3.510 (5)
Cs2—O12^iv	3.516 (4)
Cs2—O2	3.550 (4)
Na1—O11	2.298 (3)
Na1—O2ⁱⁱ	2.350 (3)
Na1—O3	2.553 (3)
Na2—O12^iv	2.243 (4)
Na2—O11ⁱⁱⁱ	2.313 (3)
Na2—O5	2.354 (4)
Na2—O4	2.416 (3)
Na2—O2^iv	2.443 (3)
Na2—O3^v	2.678 (3)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+{\script{3\over 2}}, -y, z-{\script{1\over 2}}]$ ; (iii) -x+2, -y, -z+1; (iv) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (v) x+1, y, z.

H atoms were placed in calculated positions and refined using a riding model [C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C)]. The highest and lowest peaks on the difference map are all close to the Cs positions.

Data collection: SMART (Siemens, 1995 ); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806003047/hb6315sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806003047/hb6315Isup2.hkl

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL.

Caesium sodium bis(formate) top

Crystal data top

CsNa(CHO₂)₂	F(000) = 1344
M_r = 245.94	D_x = 2.797 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 8192 reflections
a = 12.5812 (3) Å	θ = 3–25°
b = 11.0509 (3) Å	µ = 6.34 mm⁻¹
c = 12.6024 (3) Å	T = 180 K
V = 1752.16 (8) Å³	Block, colourless
Z = 12	0.20 × 0.20 × 0.15 mm

Data collection top

Siemens SMART diffractometer	2324 independent reflections
Radiation source: normal-focus sealed tube	1867 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 8.192 pixels mm^-1	θ_max = 29.1°, θ_min = 2.3°
ω scans	h = −15→16
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→14
T_min = 0.202, T_max = 0.387	l = −14→16
10798 measured reflections

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.055P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.003
2324 reflections	Δρ_max = 1.59 e Å⁻³
119 parameters	Δρ_min = −1.59 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0039 (3)

Special details top

Experimental. The temperature of the crystal was controlled using the Oxford Cryosystems Cryostream Cooler (Cosier & Glazer, 1986). The data collection nominally covered over a hemisphere of reciprocal space, by a combination of three sets of exposures with different φ angles for the crystal; each 10 s exposure covered 0.3° in ω. The crystal-to-detector distance was 5.0 cm. Coverage of the unique set is over 97% complete to at least 26° in θ. Crystal decay was found to be negligible by repeating the initial frames at t data collection and analyzing the duplicate reflections.

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	0.68069 (3)	0.2500	0.66245 (3)	0.03135 (14)
Cs2	0.95906 (2)	0.00768 (2)	0.66158 (2)	0.02852 (12)
Na1	0.5000	0.0000	0.5000	0.0219 (4)
Na2	1.26514 (12)	−0.00181 (12)	0.58246 (11)	0.0216 (3)
C1	0.6791 (3)	−0.0706 (4)	0.6696 (3)	0.0272 (9)
H1A	0.6570	−0.1525	0.6762	0.033*
O11	0.6608 (3)	−0.0238 (3)	0.5840 (2)	0.0320 (7)
O12	0.7211 (3)	−0.0284 (4)	0.7467 (3)	0.0585 (11)
C2	0.8986 (5)	−0.2500	0.8641 (5)	0.0286 (12)
H2A	0.8783	−0.2500	0.7914	0.034*
O2	0.9093 (2)	−0.1489 (3)	0.9025 (3)	0.0378 (8)
C3	0.4057 (4)	0.2500	0.5962 (4)	0.0237 (11)
H3A	0.3742	0.2500	0.5277	0.028*
O3	0.4236 (3)	0.1483 (3)	0.6353 (2)	0.0330 (7)
C4	1.1312 (5)	−0.2500	0.5582 (5)	0.0300 (12)
H4A	1.1165	−0.2500	0.6321	0.036*
O4	1.1394 (2)	−0.1491 (3)	0.5170 (3)	0.0355 (7)
C5	1.1395 (5)	0.2500	0.5225 (6)	0.0334 (13)
H5A	1.1458	0.2500	0.4474	0.040*
O5	1.1363 (3)	0.1506 (3)	0.5604 (4)	0.0616 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs1	0.0343 (2)	0.0192 (2)	0.0405 (2)	0.000	0.00677 (16)	0.000
Cs2	0.03137 (19)	0.02912 (18)	0.02506 (18)	0.00280 (10)	0.00471 (10)	−0.00124 (9)
Na1	0.0216 (11)	0.0223 (11)	0.0217 (11)	−0.0020 (8)	−0.0006 (9)	0.0033 (8)
Na2	0.0230 (8)	0.0227 (8)	0.0192 (8)	0.0023 (6)	0.0031 (6)	0.0016 (5)
C1	0.040 (2)	0.020 (2)	0.0210 (19)	0.0007 (16)	−0.0003 (16)	0.0029 (14)
O11	0.0387 (18)	0.0389 (17)	0.0183 (14)	−0.0030 (13)	−0.0049 (12)	0.0040 (12)
O12	0.077 (3)	0.070 (3)	0.0280 (19)	−0.007 (2)	−0.0244 (19)	−0.0006 (17)
C2	0.039 (3)	0.025 (3)	0.022 (3)	0.000	0.000 (2)	0.000
O2	0.0317 (16)	0.0254 (16)	0.056 (2)	0.0023 (12)	−0.0121 (14)	−0.0159 (14)
C3	0.028 (3)	0.023 (3)	0.020 (3)	0.000	−0.002 (2)	0.000
O3	0.0466 (18)	0.0256 (16)	0.0268 (15)	0.0034 (13)	−0.0036 (13)	0.0048 (12)
C4	0.037 (3)	0.027 (3)	0.026 (3)	0.000	−0.001 (2)	0.000
O4	0.0402 (16)	0.0232 (15)	0.0433 (17)	−0.0059 (12)	−0.0114 (14)	0.0087 (13)
C5	0.024 (3)	0.031 (3)	0.046 (4)	0.000	0.004 (3)	0.000
O5	0.0313 (18)	0.0275 (18)	0.126 (4)	0.0071 (14)	0.013 (2)	0.028 (2)

Geometric parameters (Å, º) top

Cs1—O11	3.193 (3)	Na2—O3^viii	2.678 (3)
Cs1—O11ⁱ	3.193 (3)	C1—O12	1.201 (5)
Cs1—O12	3.294 (4)	C1—O11	1.217 (4)
Cs1—O12ⁱ	3.294 (4)	C1—H1A	0.9500
Cs1—O4ⁱⁱ	3.389 (3)	O11—Na2ⁱⁱⁱ	2.313 (3)
Cs1—O4ⁱⁱⁱ	3.389 (3)	O12—Na2^vii	2.243 (4)
Cs1—O3	3.441 (3)	O12—Cs2^vii	3.516 (4)
Cs1—O3ⁱ	3.441 (3)	C2—O2	1.225 (4)
Cs1—O2^iv	3.642 (4)	C2—O2^ix	1.225 (4)
Cs2—O4ⁱⁱⁱ	3.007 (3)	C2—H2A	0.9500
Cs2—O5	3.015 (3)	O2—Na1^x	2.350 (3)
Cs2—O3^v	3.027 (3)	O2—Na2^vii	2.443 (3)
Cs2—O12	3.206 (4)	O2—Cs1^x	3.642 (4)
Cs2—O4	3.386 (3)	C3—O3ⁱ	1.248 (4)
Cs2—O5ⁱⁱⁱ	3.510 (5)	C3—O3	1.248 (4)
Cs2—O12^v	3.516 (4)	C3—H3A	0.9500
Cs2—O2	3.550 (4)	O3—Na2^xi	2.678 (3)
Na1—O11^vi	2.298 (3)	O3—Cs2^vii	3.027 (3)
Na1—O11	2.298 (3)	C4—O4^ix	1.233 (4)
Na1—O2^vii	2.350 (3)	C4—O4	1.233 (4)
Na1—O2^iv	2.350 (3)	C4—H4A	0.9500
Na1—O3^vi	2.553 (3)	O4—Cs2ⁱⁱⁱ	3.007 (3)
Na1—O3	2.553 (3)	O4—Cs1ⁱⁱⁱ	3.389 (3)
Na2—O12^v	2.243 (4)	C5—O5ⁱ	1.199 (4)
Na2—O11ⁱⁱⁱ	2.313 (3)	C5—O5	1.199 (4)
Na2—O5	2.354 (4)	C5—H5A	0.9500
Na2—O4	2.416 (3)	O5—Cs2ⁱⁱⁱ	3.510 (5)
Na2—O2^v	2.443 (3)	O5—Cs1^v	3.704 (5)

O11—Cs1—O11ⁱ	142.76 (10)	O11ⁱⁱⁱ—Na2—O5	94.74 (14)
O11—Cs1—O12	39.35 (8)	O12^v—Na2—O4	94.44 (14)
O11ⁱ—Cs1—O12	175.52 (9)	O11ⁱⁱⁱ—Na2—O4	92.12 (12)
O11—Cs1—O12ⁱ	175.52 (9)	O5—Na2—O4	89.47 (13)
O11ⁱ—Cs1—O12ⁱ	39.35 (8)	O12^v—Na2—O2^v	91.25 (14)
O12—Cs1—O12ⁱ	138.13 (12)	O11ⁱⁱⁱ—Na2—O2^v	81.55 (11)
O11—Cs1—O4ⁱⁱ	99.06 (7)	O5—Na2—O2^v	175.20 (13)
O11ⁱ—Cs1—O4ⁱⁱ	62.23 (8)	O4—Na2—O2^v	93.69 (12)
O12—Cs1—O4ⁱⁱ	114.79 (9)	O12^v—Na2—O3^viii	91.51 (14)
O12ⁱ—Cs1—O4ⁱⁱ	78.75 (9)	O11ⁱⁱⁱ—Na2—O3^viii	81.36 (10)
O11—Cs1—O4ⁱⁱⁱ	62.23 (8)	O5—Na2—O3^viii	95.68 (13)
O11ⁱ—Cs1—O4ⁱⁱⁱ	99.06 (7)	O4—Na2—O3^viii	171.99 (12)
O12—Cs1—O4ⁱⁱⁱ	78.75 (9)	O2^v—Na2—O3^viii	80.80 (11)
O12ⁱ—Cs1—O4ⁱⁱⁱ	114.79 (9)	O12—C1—O11	129.4 (5)
O4ⁱⁱ—Cs1—O4ⁱⁱⁱ	38.40 (10)	O12—C1—H1A	115.3
O11—Cs1—O3	65.55 (8)	O11—C1—H1A	115.3
O11ⁱ—Cs1—O3	101.84 (8)	C1—O11—Na1	128.5 (3)
O12—Cs1—O3	82.64 (8)	C1—O11—Na2ⁱⁱⁱ	141.2 (3)
O12ⁱ—Cs1—O3	118.82 (9)	Na1—O11—Na2ⁱⁱⁱ	85.57 (10)
O4ⁱⁱ—Cs1—O3	132.00 (7)	C1—O11—Cs1	96.5 (2)
O4ⁱⁱⁱ—Cs1—O3	117.02 (7)	Na1—O11—Cs1	95.91 (10)
O11—Cs1—O3ⁱ	101.84 (8)	Na2ⁱⁱⁱ—O11—Cs1	97.64 (10)
O11ⁱ—Cs1—O3ⁱ	65.55 (8)	C1—O12—Na2^vii	159.5 (4)
O12—Cs1—O3ⁱ	118.82 (9)	C1—O12—Cs2	100.8 (3)
O12ⁱ—Cs1—O3ⁱ	82.64 (8)	Na2^vii—O12—Cs2	94.24 (12)
O4ⁱⁱ—Cs1—O3ⁱ	117.02 (7)	C1—O12—Cs1	92.0 (3)
O4ⁱⁱⁱ—Cs1—O3ⁱ	132.00 (7)	Na2^vii—O12—Cs1	103.02 (15)
O3—Cs1—O3ⁱ	38.13 (10)	Cs2—O12—Cs1	85.41 (10)
O11—Cs1—O2^iv	53.60 (7)	C1—O12—Cs2^vii	84.1 (3)
O11ⁱ—Cs1—O2^iv	89.30 (7)	Na2^vii—O12—Cs2^vii	84.34 (12)
O12—Cs1—O2^iv	92.95 (7)	Cs2—O12—Cs2^vii	166.34 (15)
O12ⁱ—Cs1—O2^iv	128.64 (8)	Cs1—O12—Cs2^vii	81.69 (10)
O4ⁱⁱ—Cs1—O2^iv	73.03 (7)	O2—C2—O2^ix	131.5 (6)
O4ⁱⁱⁱ—Cs1—O2^iv	60.42 (7)	O2^ix—C2—H2A	114.2
O3—Cs1—O2^iv	61.21 (7)	O2—C2—H2A	114.2
O3ⁱ—Cs1—O2^iv	73.66 (7)	C2—O2—Na1^x	154.0 (4)
C1—Cs1—O2^iv	73.40 (7)	C2—O2—Na2^vii	123.8 (4)
C1ⁱ—Cs1—O2^iv	109.12 (7)	Na1^x—O2—Na2^vii	81.59 (10)
C3—Cs1—O2^iv	59.13 (9)	C2—O2—Cs2	97.2 (3)
O4ⁱⁱⁱ—Cs2—O5	73.48 (10)	Na1^x—O2—Cs2	91.15 (10)
O4ⁱⁱⁱ—Cs2—O3^v	107.78 (9)	Na2^vii—O2—Cs2	82.70 (9)
O5—Cs2—O3^v	101.39 (11)	C2—O2—Cs1^x	92.4 (3)
O4ⁱⁱⁱ—Cs2—O12	86.02 (9)	Na1^x—O2—Cs1^x	83.99 (9)
O5—Cs2—O12	153.82 (10)	Na2^vii—O2—Cs1^x	84.46 (10)
O3^v—Cs2—O12	69.11 (9)	Cs2—O2—Cs1^x	166.81 (9)
O4ⁱⁱⁱ—Cs2—O4	98.00 (7)	O3ⁱ—C3—O3	128.5 (5)
O5—Cs2—O4	62.95 (9)	O3ⁱ—C3—H3A	115.8
O3^v—Cs2—O4	144.70 (8)	O3—C3—H3A	115.8
O12—Cs2—O4	137.91 (9)	C3—O3—Na1	112.5 (3)
O4ⁱⁱⁱ—Cs2—O5ⁱⁱⁱ	61.43 (8)	C3—O3—Na2^xi	108.9 (3)
O5—Cs2—O5ⁱⁱⁱ	100.17 (9)	Na1—O3—Na2^xi	73.52 (9)
O3^v—Cs2—O5ⁱⁱⁱ	151.55 (8)	C3—O3—Cs2^vii	145.4 (3)
O12—Cs2—O5ⁱⁱⁱ	83.43 (9)	Na1—O3—Cs2^vii	100.36 (10)
O4—Cs2—O5ⁱⁱⁱ	62.95 (7)	Na2^xi—O3—Cs2^vii	90.11 (9)
O4ⁱⁱⁱ—Cs2—O12^v	133.71 (8)	C3—O3—Cs1	85.1 (3)
O5—Cs2—O12^v	60.34 (10)	Na1—O3—Cs1	85.55 (9)
O3^v—Cs2—O12^v	85.31 (8)	Na2^xi—O3—Cs1	157.95 (12)
O12—Cs2—O12^v	138.74 (5)	Cs2^vii—O3—Cs1	86.87 (8)
O4—Cs2—O12^v	59.39 (8)	O4^ix—C4—O4	129.3 (6)
O5ⁱⁱⁱ—Cs2—O12^v	121.73 (8)	O4^ix—C4—H4A	115.4
O4ⁱⁱⁱ—Cs2—O2	145.17 (8)	O4—C4—H4A	115.4
O5—Cs2—O2	138.37 (9)	C4—O4—Na2	121.3 (3)
O3^v—Cs2—O2	60.09 (8)	C4—O4—Cs2ⁱⁱⁱ	138.6 (3)
O12—Cs2—O2	59.23 (8)	Na2—O4—Cs2ⁱⁱⁱ	100.07 (10)
O4—Cs2—O2	109.19 (7)	C4—O4—Cs2	100.4 (3)
O5ⁱⁱⁱ—Cs2—O2	112.23 (8)	Na2—O4—Cs2	84.85 (10)
O12^v—Cs2—O2	80.15 (7)	Cs2ⁱⁱⁱ—O4—Cs2	82.00 (7)
O11^vi—Na1—O11	180.0	C4—O4—Cs1ⁱⁱⁱ	92.2 (3)
O11^vi—Na1—O2^vii	83.90 (11)	Na2—O4—Cs1ⁱⁱⁱ	90.68 (10)
O11—Na1—O2^vii	96.10 (11)	Cs2ⁱⁱⁱ—O4—Cs1ⁱⁱⁱ	86.93 (8)
O11^vi—Na1—O2^iv	96.10 (11)	Cs2—O4—Cs1ⁱⁱⁱ	167.13 (10)
O11—Na1—O2^iv	83.90 (11)	O5ⁱ—C5—O5	132.8 (8)
O2^vii—Na1—O2^iv	180.0	O5—C5—H5A	113.6
O11^vi—Na1—O3^vi	95.57 (10)	O5ⁱ—C5—H5A	113.6
O11—Na1—O3^vi	84.43 (10)	C5—O5—Na2	132.8 (4)
O2^vii—Na1—O3^vi	94.74 (11)	C5—O5—Cs2	132.3 (4)
O2^iv—Na1—O3^vi	85.26 (11)	Na2—O5—Cs2	94.85 (12)
O11^vi—Na1—O3	84.43 (10)	C5—O5—Cs2ⁱⁱⁱ	98.7 (4)
O11—Na1—O3	95.57 (10)	Na2—O5—Cs2ⁱⁱⁱ	88.45 (13)
O2^vii—Na1—O3	85.27 (11)	Cs2—O5—Cs2ⁱⁱⁱ	79.83 (9)
O2^iv—Na1—O3	94.73 (11)	C5—O5—Cs1^v	95.7 (4)
O3^vi—Na1—O3	180.0	Na2—O5—Cs1^v	89.83 (13)
O12^v—Na2—O11ⁱⁱⁱ	170.56 (15)	Cs2—O5—Cs1^v	82.42 (10)
O12^v—Na2—O5	92.11 (16)	Cs2ⁱⁱⁱ—O5—Cs1^v	161.95 (11)

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

Acknowledgements

We thank Cabot Specialty Fluids for support of this work. EPSRC and Siemens plc generously supported the purchase of the SMART diffractometer.

References

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