Poly[μ5-{hydrogen bis­[(E)-cinnamato]}-caesium]

Smith, G.

doi:10.1107/S1600536814000804

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 2| February 2014| Pages m43-m44

doi:10.1107/S1600536814000804

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Poly[μ₅-{hydrogen bis[(E)-cinnamato]}-caesium]

Graham Smith ^a ^*

^aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

(Received 8 January 2014; accepted 13 January 2014; online 18 January 2014)

In the structure of the title polymeric complex, [Cs(C₉H₇O₂)(C₉H₈O₂)]_n, a caesium salt of trans-cinnamic acid, the Cs⁺ ions of the two individual irregular CsO₈ coordination polyhedra lie on twofold rotation axes and are linked by four bridging carboxyl O-atom donors from two cinnamate ligand species. These two ligand components are interlinked through a delocalized H atom within a short O⋯H⋯O hydrogen bond. Structure extension gives a two-dimensional coordination polymer which lies parallel to (001). The structure was determined from a crystal twinned by non-merohedry, with a twin component ratio of approximately 1:1.

CCDC reference: 981265

Related literature

For the structures of the ammonium salts of hydrogen bis(3-chlorocinnamate) and hydrogen bis(3-bromocinnamate), see: Chowdhury & Kariuki (2006 ). For structures of alkali metal salts of ring-substituted trans-cinnamic acid, see: Kariuki et al. (1994 , 1995 ); Crowther et al. (2008 ); Smith & Wermuth (2009 , 2011 ). For the structure of trans-cinnamic acid, see: Wierda et al. (1989 ); Abdelmoty et al. (2005 ).

Experimental

Crystal data

[Cs(C₉H₇O₂)(C₉H₈O₂)]
M_r = 428.21
Monoclinic, P 2/c
a = 7.8608 (6) Å
b = 5.6985 (7) Å
c = 38.817 (3) Å
β = 98.733 (6)°
V = 1718.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.17 mm⁻¹
T = 200 K
0.35 × 0.35 × 0.06 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ) T_min = 0.711, T_max = 0.980
6675 measured reflections
3353 independent reflections
2552 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.144
S = 1.19
3353 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 1.26 e Å⁻³
Δρ_min = −2.19 e Å⁻³

Table 1
Selected bond lengths (Å)

Cs1—O13B	3.060 (8)
Cs1—O14A	3.182 (8)
Cs1—O13Aⁱ	3.132 (9)
Cs1—O14Bⁱ	3.183 (9)
Cs1—O13Bⁱⁱ	3.060 (8)
Cs1—O14Aⁱⁱ	3.182 (8)
Cs1—O13Aⁱⁱⁱ	3.132 (9)
Cs1—O14Bⁱⁱⁱ	3.183 (9)
Cs2—O13B	3.063 (8)
Cs2—O14A	3.377 (9)
Cs2—O13Aⁱ	3.108 (9)
Cs2—O14Bⁱ	3.130 (9)
Cs2—O13B^iv	3.063 (8)
Cs2—O14A^iv	3.377 (9)
Cs2—O13A^v	3.108 (9)
Cs2—O14B^v	3.130 (9)
Symmetry codes: (i) x, y+1, z; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+1, -z+{\script{1\over 2}}]$ ; (iv) $[-x, y, -z+{\script{1\over 2}}]$ ; (v) $[-x, y+1, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O14B—H14B⋯O14A	1.21	1.25	2.462 (10)	180

Data collection: CrysAlis PRO (Agilent, 2013); 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) within WinGX (Farrugia, 2012 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

CCDC reference: 981265

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814000804/wm2798sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814000804/wm2798Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814000804/wm2798Isup3.cml

checkCIF report

Comment top

The crystal structure of trans-cinnamic acid was reported by Wierda et al. (1989) and Abdelmoty et al. (2005). The alkali metal salts of trans-cinnamic acid are unknown in the crystallographic literature although a limited number of examples of salts of ring-substituted cinnamates have been reported, e.g. the sodium salts of 2-nitrocinnamate [a dihydrate (Smith & Wermuth, 2009)], of 2-chlorocinnamate [a dihydrate (Kariuki et al., 1995)], of 3-chlorocinnamate [anhydrous (Crowther et al., 2008), of 4-chlorocinnamate [a dihydrate (Kariuki et al., 1994); potassium salts of 3-chloro- and 3-bromocinnamate [both anhydrous (Crowther et al., 2008)]; and a rubidium salt of 2-nitrocinnamate [a monohydrate (Smith & Wermuth, 2011)].

The reaction of trans-cinnamic acid with caesium hydroxide in aqueous ethanol afforded crystals of the title complex, [Cs(C₉H₇O₂)(C₉H₈O₂)]_n, (I), the structure of which is reported herein.

In the structure of (I) the asymmetric unit (Fig. 1) comprises two independent irregular CsO₈ coordination polyhedra [Cs1—O, 3.060 (8)–3.183 (9) Å; Cs2—O, 3.063 (9)–3.377 (9) Å: Table 1], in which the Cs⁺ ions lie on a twofold rotation axis and are linked by four bridging carboxyl O-donors from the two trans-cinnamate ligand species. These two ligand species are inter-linked through a delocalized H atom on an approximately central intermediate site within a short O14A···H14B··· O14B hydrogen bond [2.462 (10) Å] (Table 2). Although this phenomenon involving coordinating dimeric carboxylate species is not known among the alkali metal substituted-cinnamate structures, it is found in both ammonium hydrogen bis(3-chlorocinnamate) and ammonium hydrogen bis(3-bromocinnamate) (Chowdhury & Kariuki, 2006), with the O···H···O values [2.554 (6) Å for the 3-Cl-analogue and 2.466 (5) Å for the 3-Br-analogue] similar to that in the structure of (I). In this complex, the two Cs⁺ ions are quadruply bridged giving a Cs1···Cs2 separation of 3.9318 (3) Å and generate an overall two-dimensional coordination polymer lying parallel to (001) (Figs. 2, 3). No inter-ring π–π interactions are present in the structure [minimun ring centroid separation = 4.826 (8) Å].

The two linked cinnamate species in the title complex are close to coplanar [inter-ring dihedral angle = 3.9 (6)°], with the side chain carboxyl group of the A ligand component slightly rotated out of the plane [torsion angle C11A—C12A— C13A—O13A = 169.0 (13)°] compared to that of the B ligand component [torsion angle C11B—C12B— C13B—O14B = -179.2 (11)°]. With the analogous ammonium hydrogen salts of the 3-chloro- and 3-bromocinnamates (Chowdhury & Kariuki, 2006), the two cinnamate components are related either by crystallographic inversion symmetry (3-Cl) with the two benzene rings essentially planar, or by twofold rotational symmetry (3-Br) with the two rings significantly rotated out of the least-squares plane [inter-ring dihedral angle = 29.8 (2)°].

Related literature top

For the structures of the ammonium salts of hydrogen bis(3-chlorocinnamate) and hydrogen bis(3-bromocinnamate), see: Chowdhury & Kariuki (2006). For structures of alkali metal salts of ring-substituted trans-cinnamic acid, see: Kariuki et al. (1994, 1995); Crowther et al. (2008); Smith & Wermuth (2009, 2011). For the structure of trans-cinnamic acid, see: Wierda et al. (1989); Abdelmoty et al. (2005).

Experimental top

The title compound was synthesized by heating together for 10 minutes, 148 mg (1.0 mmol) of trans-cinnamic acid and 75 mg (0.5 mmol) of CsOH in 15 ml of an 1:9 (vol/vol) ethanol–water mixture. Partial room temperature evaporation of the solution gave colourless elongated crystals of the title complex from which a specimen was cleaved for the X-ray analysis. These crystals were invariably twinned, a feature identified in the later structure solution and refinement routines.

Structure description top

For the structures of the ammonium salts of hydrogen bis(3-chlorocinnamate) and hydrogen bis(3-bromocinnamate), see: Chowdhury & Kariuki (2006). For structures of alkali metal salts of ring-substituted trans-cinnamic acid, see: Kariuki et al. (1994, 1995); Crowther et al. (2008); Smith & Wermuth (2009, 2011). For the structure of trans-cinnamic acid, see: Wierda et al. (1989); Abdelmoty et al. (2005).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); 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 top

	Fig. 1. The atom-numbering scheme and the molecular configuration of the two ligands and the two CsO₈ coordination polyhedra of the title complex, with non-H atoms drawn with displacement ellipsoids at the 40% probability level. The two Cs⁺ cations lie on twofold rotation axes. The O14A···O14B hydrogen bond with the delocalized H atom (H14B) is shown as a dashed link. [For symmetry codes: see Table 1].
	Fig. 2. A view of the partially expanded polymeric extension of the structure viewed along the approximate a-cell direction. C-bound H atoms are omitted. A and B denote the two different ligand components.
	Fig. 3. The packing of the layered structure of compound (I) viewed along b.

Poly[µ₅-{hydrogen bis[(E)-cinnamato]}-caesium] top

Crystal data top

[Cs(C₉H₇O₂)(C₉H₈O₂)]	F(000) = 840
M_r = 428.21	D_x = 1.655 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 1674 reflections
a = 7.8608 (6) Å	θ = 3.6–28.2°
b = 5.6985 (7) Å	µ = 2.17 mm⁻¹
c = 38.817 (3) Å	T = 200 K
β = 98.733 (6)°	Plate, colourless
V = 1718.6 (3) Å³	0.35 × 0.35 × 0.06 mm
Z = 4

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	3353 independent reflections
Radiation source: Enhance (Mo) X-ray source	2552 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −7→7
T_min = 0.711, T_max = 0.980	l = −11→47
6675 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H-atom parameters constrained
S = 1.19	w = 1/[σ²(F_o²) + (0.020P)² + 18.34P] where P = (F_o² + 2F_c²)/3
3353 reflections	(Δ/σ)_max = 0.001
210 parameters	Δρ_max = 1.26 e Å⁻³
0 restraints	Δρ_min = −2.19 e Å⁻³

Crystal data top

[Cs(C₉H₇O₂)(C₉H₈O₂)]	V = 1718.6 (3) Å³
M_r = 428.21	Z = 4
Monoclinic, P2/c	Mo Kα radiation
a = 7.8608 (6) Å	µ = 2.17 mm⁻¹
b = 5.6985 (7) Å	T = 200 K
c = 38.817 (3) Å	0.35 × 0.35 × 0.06 mm
β = 98.733 (6)°

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	3353 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	2552 reflections with I > 2σ(I)
T_min = 0.711, T_max = 0.980	R_int = 0.046
6675 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 1.19	w = 1/[σ²(F_o²) + (0.020P)² + 18.34P] where P = (F_o² + 2F_c²)/3
3353 reflections	Δρ_max = 1.26 e Å⁻³
210 parameters	Δρ_min = −2.19 e Å⁻³

Special details top

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 e.s.d.'s 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 > 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	0.50000	0.6438 (2)	0.25000	0.0261 (3)
Cs2	0.00000	0.6257 (2)	0.25000	0.0300 (3)
O13A	0.2828 (13)	−0.1322 (15)	0.3028 (2)	0.037 (3)
O13B	0.2180 (12)	0.3903 (14)	0.20079 (19)	0.030 (3)
O14A	0.3036 (12)	0.2355 (14)	0.28374 (18)	0.029 (3)
O14B	0.2197 (13)	0.0396 (14)	0.22718 (18)	0.033 (3)
C1A	0.5037 (15)	0.4316 (19)	0.3905 (3)	0.025 (3)
C1B	0.0000 (15)	0.079 (2)	0.1031 (3)	0.025 (3)
C2A	0.5963 (19)	0.636 (2)	0.3964 (3)	0.035 (4)
C2B	0.0132 (16)	0.208 (2)	0.0728 (3)	0.028 (3)
C3A	0.6620 (19)	0.707 (2)	0.4301 (4)	0.042 (5)
C3B	−0.0664 (16)	0.128 (3)	0.0403 (3)	0.040 (4)
C4A	0.6346 (18)	0.574 (3)	0.4585 (3)	0.042 (5)
C4B	−0.1524 (18)	−0.082 (2)	0.0373 (3)	0.041 (4)
C5A	0.5426 (19)	0.373 (3)	0.4529 (3)	0.039 (4)
C5B	−0.1628 (16)	−0.210 (2)	0.0668 (3)	0.035 (4)
C6A	0.4764 (15)	0.299 (2)	0.4191 (3)	0.029 (4)
C6B	−0.0870 (15)	−0.133 (2)	0.0997 (3)	0.031 (4)
C11A	0.4356 (17)	0.359 (2)	0.3541 (3)	0.032 (4)
C11B	0.0831 (14)	0.173 (2)	0.1369 (3)	0.025 (3)
C12A	0.3722 (13)	0.155 (2)	0.3444 (3)	0.023 (3)
C12B	0.1178 (15)	0.054 (2)	0.1672 (3)	0.026 (3)
C13A	0.3148 (16)	0.076 (2)	0.3078 (3)	0.028 (4)
C13B	0.1901 (15)	0.176 (2)	0.1998 (3)	0.027 (4)
H2A	0.61560	0.73090	0.37720	0.0410*
H2B	0.07640	0.35110	0.07440	0.0340*
H3A	0.72650	0.84820	0.43360	0.0510*
H3B	−0.06090	0.21990	0.02000	0.0480*
H4A	0.67930	0.62310	0.48150	0.0500*
H4B	−0.20410	−0.13800	0.01520	0.0490*
H5A	0.52280	0.28000	0.47230	0.0470*
H5B	−0.22320	−0.35490	0.06480	0.0410*
H6A	0.41240	0.15700	0.41580	0.0350*
H6B	−0.09500	−0.22560	0.11970	0.0370*
H11A	0.43910	0.47280	0.33640	0.0380*
H11B	0.11540	0.33430	0.13740	0.0290*
H12A	0.36110	0.04540	0.36230	0.0280*
H12B	0.09570	−0.10990	0.16760	0.0320*
H14B	0.26080	0.13620	0.25500	0.0500*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs1	0.0221 (5)	0.0212 (5)	0.0350 (5)	0.0000	0.0041 (5)	0.0000
Cs2	0.0232 (5)	0.0238 (6)	0.0438 (6)	0.0000	0.0075 (6)	0.0000
O13A	0.056 (5)	0.027 (5)	0.028 (4)	−0.001 (6)	0.003 (4)	−0.006 (4)
O13B	0.047 (5)	0.026 (4)	0.016 (4)	−0.004 (5)	0.000 (4)	0.000 (3)
O14A	0.046 (6)	0.033 (5)	0.006 (3)	−0.003 (4)	−0.006 (3)	−0.005 (3)
O14B	0.055 (5)	0.025 (4)	0.013 (4)	−0.004 (5)	−0.015 (4)	−0.005 (3)
C1A	0.022 (6)	0.022 (6)	0.030 (6)	0.003 (5)	0.006 (5)	−0.009 (5)
C1B	0.020 (5)	0.034 (6)	0.022 (5)	0.004 (6)	0.005 (5)	−0.007 (5)
C2A	0.038 (7)	0.027 (6)	0.039 (6)	−0.004 (7)	0.007 (6)	0.003 (6)
C2B	0.027 (6)	0.028 (6)	0.027 (6)	0.007 (6)	0.000 (5)	−0.003 (5)
C3A	0.044 (9)	0.021 (7)	0.059 (9)	0.012 (6)	−0.002 (7)	−0.024 (6)
C3B	0.043 (8)	0.050 (8)	0.027 (6)	0.026 (8)	0.005 (5)	0.000 (7)
C4A	0.031 (7)	0.059 (10)	0.033 (7)	0.006 (8)	−0.001 (6)	−0.022 (7)
C4B	0.037 (7)	0.053 (8)	0.030 (7)	−0.011 (8)	−0.003 (6)	−0.012 (6)
C5A	0.035 (7)	0.048 (7)	0.035 (6)	−0.003 (8)	0.005 (6)	0.012 (7)
C5B	0.029 (7)	0.021 (6)	0.054 (8)	−0.005 (6)	0.006 (6)	−0.004 (6)
C6A	0.031 (7)	0.027 (7)	0.030 (6)	−0.007 (6)	0.005 (5)	0.004 (5)
C6B	0.032 (7)	0.027 (6)	0.032 (6)	−0.002 (6)	0.002 (5)	−0.002 (6)
C11A	0.035 (7)	0.029 (6)	0.032 (6)	−0.002 (7)	0.006 (6)	0.002 (6)
C11B	0.030 (6)	0.021 (6)	0.021 (5)	−0.004 (5)	−0.001 (4)	0.001 (5)
C12A	0.036 (6)	0.017 (6)	0.016 (5)	−0.008 (5)	0.002 (4)	−0.008 (5)
C12B	0.038 (7)	0.013 (5)	0.027 (6)	−0.009 (5)	0.001 (5)	0.006 (5)
C13A	0.021 (6)	0.036 (8)	0.027 (6)	−0.002 (6)	0.003 (5)	0.002 (5)
C13B	0.023 (6)	0.043 (8)	0.015 (5)	0.000 (6)	−0.001 (5)	−0.010 (6)

Geometric parameters (Å, º) top

Cs1—O13B	3.060 (8)	C2A—C3A	1.392 (19)
Cs1—O14A	3.182 (8)	C2B—C3B	1.397 (17)
Cs1—O13Aⁱ	3.132 (9)	C3A—C4A	1.38 (2)
Cs1—O14Bⁱ	3.183 (9)	C3B—C4B	1.37 (2)
Cs1—O13Bⁱⁱ	3.060 (8)	C4A—C5A	1.35 (2)
Cs1—O14Aⁱⁱ	3.182 (8)	C4B—C5B	1.371 (16)
Cs1—O13Aⁱⁱⁱ	3.132 (9)	C5A—C6A	1.401 (17)
Cs1—O14Bⁱⁱⁱ	3.183 (9)	C5B—C6B	1.396 (16)
Cs2—O13B	3.063 (8)	C11A—C12A	1.298 (16)
Cs2—O14A	3.377 (9)	C11B—C12B	1.349 (16)
Cs2—O13Aⁱ	3.108 (9)	C12A—C13A	1.493 (16)
Cs2—O14Bⁱ	3.130 (9)	C12B—C13B	1.480 (16)
Cs2—O13B^iv	3.063 (8)	C2A—H2A	0.9500
Cs2—O14A^iv	3.377 (9)	C2B—H2B	0.9500
Cs2—O13A^v	3.108 (9)	C3A—H3A	0.9500
Cs2—O14B^v	3.130 (9)	C3B—H3B	0.9500
O13A—C13A	1.222 (14)	C4A—H4A	0.9500
O13B—C13B	1.240 (14)	C4B—H4B	0.9500
O14A—C13A	1.297 (14)	C5A—H5A	0.9500
O14B—C13B	1.309 (14)	C5B—H5B	0.9500
O14B—H14B	1.2100	C6A—H6A	0.9500
C1A—C11A	1.492 (16)	C6B—H6B	0.9500
C1A—C2A	1.374 (17)	C11A—H11A	0.9500
C1A—C6A	1.386 (16)	C11B—H11B	0.9500
C1B—C11B	1.475 (16)	C12A—H12A	0.9500
C1B—C6B	1.385 (16)	C12B—H12B	0.9500
C1B—C2B	1.404 (16)

O13B—Cs1—O14A	64.0 (2)	Cs2—O14A—C13A	135.0 (8)
O13Aⁱ—Cs1—O13B	100.7 (2)	Cs1^vi—O14B—C13B	132.6 (7)
O13B—Cs1—O14Bⁱ	75.9 (2)	Cs2^vi—O14B—C13B	129.8 (7)
O13B—Cs1—O13Bⁱⁱ	123.7 (2)	Cs1^vi—O14B—Cs2^vi	77.04 (18)
O13B—Cs1—O14Aⁱⁱ	75.4 (2)	Cs1—O14A—H14B	93.00
O13Aⁱⁱⁱ—Cs1—O13B	101.5 (2)	Cs2—O14A—H14B	83.00
O13B—Cs1—O14Bⁱⁱⁱ	155.98 (19)	Cs2^vi—O14B—H14B	100.00
O13Aⁱ—Cs1—O14A	71.5 (2)	Cs1^vi—O14B—H14B	90.00
O14A—Cs1—O14Bⁱ	105.9 (2)	C13B—O14B—H14B	116.00
O13Bⁱⁱ—Cs1—O14A	75.4 (2)	C6A—C1A—C11A	122.0 (10)
O14A—Cs1—O14Aⁱⁱ	86.0 (2)	C2A—C1A—C6A	118.1 (11)
O13Aⁱⁱⁱ—Cs1—O14A	156.1 (2)	C2A—C1A—C11A	119.9 (10)
O14A—Cs1—O14Bⁱⁱⁱ	139.65 (18)	C2B—C1B—C6B	118.4 (11)
O13Aⁱ—Cs1—O14Bⁱ	58.0 (2)	C2B—C1B—C11B	118.4 (10)
O13Aⁱ—Cs1—O13Bⁱⁱ	101.5 (2)	C6B—C1B—C11B	123.2 (10)
O13Aⁱ—Cs1—O14Aⁱⁱ	156.1 (2)	C1A—C2A—C3A	121.0 (11)
O13Aⁱ—Cs1—O13Aⁱⁱⁱ	131.9 (2)	C1B—C2B—C3B	120.4 (12)
O13Aⁱ—Cs1—O14Bⁱⁱⁱ	87.3 (2)	C2A—C3A—C4A	120.7 (12)
O13Bⁱⁱ—Cs1—O14Bⁱ	155.98 (19)	C2B—C3B—C4B	120.6 (12)
O14Aⁱⁱ—Cs1—O14Bⁱ	139.65 (18)	C3A—C4A—C5A	118.7 (12)
O13Aⁱⁱⁱ—Cs1—O14Bⁱ	87.3 (2)	C3B—C4B—C5B	119.0 (11)
O14Bⁱ—Cs1—O14Bⁱⁱⁱ	89.8 (2)	C4A—C5A—C6A	121.2 (12)
O13Bⁱⁱ—Cs1—O14Aⁱⁱ	64.0 (2)	C4B—C5B—C6B	121.7 (11)
O13Aⁱⁱⁱ—Cs1—O13Bⁱⁱ	100.7 (2)	C1A—C6A—C5A	120.4 (11)
O13Bⁱⁱ—Cs1—O14Bⁱⁱⁱ	75.9 (2)	C1B—C6B—C5B	119.8 (11)
O13Aⁱⁱⁱ—Cs1—O14Aⁱⁱ	71.5 (2)	C1A—C11A—C12A	126.2 (11)
O14Aⁱⁱ—Cs1—O14Bⁱⁱⁱ	105.9 (2)	C1B—C11B—C12B	126.6 (11)
O13Aⁱⁱⁱ—Cs1—O14Bⁱⁱⁱ	58.0 (2)	C11A—C12A—C13A	126.4 (11)
O13B—Cs2—O14A	61.58 (19)	C11B—C12B—C13B	120.7 (10)
O13Aⁱ—Cs2—O13B	101.2 (2)	O13A—C13A—C12A	118.0 (10)
O13B—Cs2—O14Bⁱ	76.6 (2)	O13A—C13A—O14A	125.2 (11)
O13B—Cs2—O13B^iv	128.1 (2)	O14A—C13A—C12A	116.9 (10)
O13B—Cs2—O14A^iv	84.2 (2)	O14B—C13B—C12B	114.4 (10)
O13A^v—Cs2—O13B	101.3 (2)	O13B—C13B—O14B	123.4 (10)
O13B—Cs2—O14B^v	153.1 (2)	O13B—C13B—C12B	122.2 (10)
O13Aⁱ—Cs2—O14A	69.2 (2)	C1A—C2A—H2A	120.00
O14A—Cs2—O14Bⁱ	102.6 (2)	C3A—C2A—H2A	119.00
O13B^iv—Cs2—O14A	84.2 (2)	C1B—C2B—H2B	120.00
O14A—Cs2—O14A^iv	97.7 (2)	C3B—C2B—H2B	120.00
O13A^v—Cs2—O14A	160.1 (2)	C2A—C3A—H3A	120.00
O14A—Cs2—O14B^v	140.74 (18)	C4A—C3A—H3A	120.00
O13Aⁱ—Cs2—O14Bⁱ	58.8 (2)	C2B—C3B—H3B	120.00
O13Aⁱ—Cs2—O13B^iv	101.3 (2)	C4B—C3B—H3B	120.00
O13Aⁱ—Cs2—O14A^iv	160.1 (2)	C3A—C4A—H4A	121.00
O13Aⁱ—Cs2—O13A^v	127.3 (2)	C5A—C4A—H4A	121.00
O13Aⁱ—Cs2—O14B^v	81.3 (2)	C3B—C4B—H4B	121.00
O13B^iv—Cs2—O14Bⁱ	153.1 (2)	C5B—C4B—H4B	120.00
O14A^iv—Cs2—O14Bⁱ	140.74 (18)	C4A—C5A—H5A	119.00
O13A^v—Cs2—O14Bⁱ	81.3 (2)	C6A—C5A—H5A	119.00
O14Bⁱ—Cs2—O14B^v	82.2 (2)	C4B—C5B—H5B	119.00
O13B^iv—Cs2—O14A^iv	61.58 (19)	C6B—C5B—H5B	119.00
O13A^v—Cs2—O13B^iv	101.2 (2)	C1A—C6A—H6A	120.00
O13B^iv—Cs2—O14B^v	76.6 (2)	C5A—C6A—H6A	120.00
O13A^v—Cs2—O14A^iv	69.2 (2)	C1B—C6B—H6B	120.00
O14A^iv—Cs2—O14B^v	102.6 (2)	C5B—C6B—H6B	120.00
O13A^v—Cs2—O14B^v	58.8 (2)	C1A—C11A—H11A	117.00
Cs1^vi—O13A—C13A	112.3 (8)	C12A—C11A—H11A	117.00
Cs2^vi—O13A—C13A	130.2 (8)	C1B—C11B—H11B	117.00
Cs1^vi—O13A—Cs2^vi	78.11 (18)	C12B—C11B—H11B	117.00
Cs1—O13B—Cs2	79.91 (18)	C11A—C12A—H12A	117.00
Cs1—O13B—C13B	126.3 (7)	C13A—C12A—H12A	117.00
Cs2—O13B—C13B	109.7 (7)	C11B—C12B—H12B	120.00
Cs1—O14A—Cs2	73.59 (16)	C13B—C12B—H12B	120.00
Cs1—O14A—C13A	145.6 (8)

O14A—Cs1—O13B—Cs2	65.6 (2)	O13B^iv—Cs2—O14A—Cs1	−160.72 (18)
O14A—Cs1—O13B—C13B	−41.6 (9)	O13B^iv—Cs2—O14A—C13A	−3.5 (9)
O13Aⁱ—Cs1—O13B—Cs2	2.5 (2)	O14A^iv—Cs2—O14A—Cs1	139.03 (16)
O13Aⁱ—Cs1—O13B—C13B	−104.7 (9)	O14A^iv—Cs2—O14A—C13A	−63.8 (10)
O14Bⁱ—Cs1—O13B—Cs2	−50.38 (19)	O14B^v—Cs2—O14A—Cs1	−100.2 (3)
O14Bⁱ—Cs1—O13B—C13B	−157.5 (9)	O14B^v—Cs2—O14A—C13A	57.0 (11)
O13Bⁱⁱ—Cs1—O13B—Cs2	114.2 (2)	O13B—Cs2—O13Aⁱ—Cs1	2.5 (2)
O13Bⁱⁱ—Cs1—O13B—C13B	7.0 (10)	O14A—Cs2—O13Aⁱ—Cs1	56.01 (18)
O14Aⁱⁱ—Cs1—O13B—Cs2	158.3 (2)	O13B—Cs2—O14Bⁱ—Cs1	−49.32 (18)
O14Aⁱⁱ—Cs1—O13B—C13B	51.2 (9)	O14A—Cs2—O14Bⁱ—Cs1	7.01 (18)
O13Aⁱⁱⁱ—Cs1—O13B—Cs2	−134.6 (2)	Cs1^vi—O13A—C13A—O14A	56.2 (15)
O13Aⁱⁱⁱ—Cs1—O13B—C13B	118.3 (9)	Cs1^vi—O13A—C13A—C12A	−123.5 (9)
O14Bⁱⁱⁱ—Cs1—O13B—Cs2	−105.2 (5)	Cs2^vi—O13A—C13A—O14A	−37.0 (18)
O14Bⁱⁱⁱ—Cs1—O13B—C13B	147.6 (9)	Cs2^vi—O13A—C13A—C12A	143.3 (8)
O13B—Cs1—O14A—Cs2	−57.9 (2)	Cs1—O13B—C13B—O14B	31.2 (16)
O13B—Cs1—O14A—C13A	151.0 (13)	Cs1—O13B—C13B—C12B	−149.6 (8)
O13Aⁱ—Cs1—O14A—Cs2	54.52 (19)	Cs2—O13B—C13B—O14B	−60.7 (13)
O13Aⁱ—Cs1—O14A—C13A	−96.5 (12)	Cs2—O13B—C13B—C12B	118.6 (10)
O14Bⁱ—Cs1—O14A—Cs2	7.10 (18)	Cs1—O14A—C13A—O13A	−125.8 (12)
O14Bⁱ—Cs1—O14A—C13A	−143.9 (12)	Cs1—O14A—C13A—C12A	54.0 (17)
O13Bⁱⁱ—Cs1—O14A—Cs2	162.23 (19)	Cs2—O14A—C13A—O13A	95.3 (14)
O13Bⁱⁱ—Cs1—O14A—C13A	11.2 (12)	Cs2—O14A—C13A—C12A	−85.0 (13)
O14Aⁱⁱ—Cs1—O14A—Cs2	−133.66 (17)	Cs1^vi—O14B—C13B—O13B	−109.4 (12)
O14Aⁱⁱ—Cs1—O14A—C13A	75.3 (12)	Cs1^vi—O14B—C13B—C12B	71.3 (13)
O13Aⁱⁱⁱ—Cs1—O14A—Cs2	−114.2 (5)	Cs2^vi—O14B—C13B—O13B	138.9 (10)
O13Aⁱⁱⁱ—Cs1—O14A—C13A	94.7 (13)	Cs2^vi—O14B—C13B—C12B	−40.4 (14)
O14Bⁱⁱⁱ—Cs1—O14A—Cs2	116.3 (3)	C6A—C1A—C2A—C3A	0.5 (19)
O14Bⁱⁱⁱ—Cs1—O14A—C13A	−34.7 (14)	C11A—C1A—C2A—C3A	−179.7 (12)
O13B—Cs1—O13Aⁱ—Cs2	−2.5 (2)	C2A—C1A—C6A—C5A	−0.2 (18)
O14A—Cs1—O13Aⁱ—Cs2	−60.15 (19)	C11A—C1A—C6A—C5A	179.9 (12)
O13B—Cs1—O14Bⁱ—Cs2	49.60 (18)	C2A—C1A—C11A—C12A	167.7 (13)
O14A—Cs1—O14Bⁱ—Cs2	−7.55 (19)	C6A—C1A—C11A—C12A	−13 (2)
O14A—Cs2—O13B—Cs1	−61.2 (2)	C6B—C1B—C2B—C3B	2.8 (18)
O14A—Cs2—O13B—C13B	63.9 (7)	C11B—C1B—C2B—C3B	−178.7 (11)
O13Aⁱ—Cs2—O13B—Cs1	−2.5 (2)	C2B—C1B—C6B—C5B	−1.7 (18)
O13Aⁱ—Cs2—O13B—C13B	122.6 (7)	C11B—C1B—C6B—C5B	179.8 (11)
O14Bⁱ—Cs2—O13B—Cs1	51.35 (19)	C2B—C1B—C11B—C12B	−164.0 (12)
O14Bⁱ—Cs2—O13B—C13B	176.5 (8)	C6B—C1B—C11B—C12B	14.4 (19)
O13B^iv—Cs2—O13B—Cs1	−116.5 (2)	C1A—C2A—C3A—C4A	0 (2)
O13B^iv—Cs2—O13B—C13B	8.6 (8)	C1B—C2B—C3B—C4B	−3 (2)
O14A^iv—Cs2—O13B—Cs1	−163.16 (19)	C2A—C3A—C4A—C5A	0 (2)
O14A^iv—Cs2—O13B—C13B	−38.1 (7)	C2B—C3B—C4B—C5B	2 (2)
O13A^v—Cs2—O13B—Cs1	129.5 (2)	C3A—C4A—C5A—C6A	0 (2)
O13A^v—Cs2—O13B—C13B	−105.4 (7)	C3B—C4B—C5B—C6B	−1 (2)
O14B^v—Cs2—O13B—Cs1	90.3 (5)	C4A—C5A—C6A—C1A	0 (2)
O14B^v—Cs2—O13B—C13B	−144.6 (7)	C4B—C5B—C6B—C1B	0.7 (19)
O13B—Cs2—O14A—Cs1	59.9 (2)	C1A—C11A—C12A—C13A	−175.6 (12)
O13B—Cs2—O14A—C13A	−142.9 (10)	C1B—C11B—C12B—C13B	−175.3 (11)
O13Aⁱ—Cs2—O14A—Cs1	−56.3 (2)	C11A—C12A—C13A—O13A	169.0 (13)
O13Aⁱ—Cs2—O14A—C13A	100.9 (10)	C11A—C12A—C13A—O14A	−10.7 (18)
O14Bⁱ—Cs2—O14A—Cs1	−7.12 (18)	C11B—C12B—C13B—O13B	1.6 (18)
O14Bⁱ—Cs2—O14A—C13A	150.1 (9)	C11B—C12B—C13B—O14B	−179.2 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O14B—H14B···O14A	1.21	1.25	2.462 (10)	180
C11B—H11B···O13B	0.95	2.49	2.830 (14)	101

Selected bond lengths (Å) top

Cs1—O13B	3.060 (8)	Cs2—O13B	3.063 (8)
Cs1—O14A	3.182 (8)	Cs2—O14A	3.377 (9)
Cs1—O13Aⁱ	3.132 (9)	Cs2—O13Aⁱ	3.108 (9)
Cs1—O14Bⁱ	3.183 (9)	Cs2—O14Bⁱ	3.130 (9)
Cs1—O13Bⁱⁱ	3.060 (8)	Cs2—O13B^iv	3.063 (8)
Cs1—O14Aⁱⁱ	3.182 (8)	Cs2—O14A^iv	3.377 (9)
Cs1—O13Aⁱⁱⁱ	3.132 (9)	Cs2—O13A^v	3.108 (9)
Cs1—O14Bⁱⁱⁱ	3.183 (9)	Cs2—O14B^v	3.130 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O14B—H14B···O14A	1.21	1.25	2.462 (10)	180

Acknowledgements

The author acknowledges financial support from the Science and Engineering Faculty and the University Library, Queensland University of Technology.

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