Bis(μ-trifluoromethanesulfonato-κ²O:O′)bis[aqua(1,4,7,10,13,16-hexaoxacyclo­octadecane-κ⁶O)barium(II)] bis(trifluoromethanesulfonate)

The crystal structure of the title compound, [Ba₂(CF₃O₃S)₂(C₁₂H₂₄O₆)₂(H₂O)₂](CF₃O₃S)₂, comprises a ten-coordinated Ba²⁺ cation that is coordinated by 18-crown-6, trifluoro­methane­sulfonate counter-ions and a water mol­ecule, and an uncoordinated counter-ion. The dinuclear cation lies on a center of inversion. Each coordinated triflate group chelates a Ba atom while being monodentate to the adjacent Ba atom. The uncoordinated counter-ion is hydrogen bonded to the cation. Hydrogen bonds form infinite tubular arrays.

Key indicators

• Single-crystal X-ray study
• T = 175 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.023
• wR factor = 0.022
• Data-to-parameter ratio = 19.6

checkCIF/PLATON results

No syntax errors found



Alert level C
CHEMW01_ALERT_1_C  The ratio of given/expected molecular weight as calculated
            from the _chemical_formula_sum lies outside
            the range 0.99 <> 1.01
            Calculated formula weight =   717.8020
            Formula weight given      =   732.6700
CHEMW01_ALERT_1_C  The difference between the given and expected weight for
            compound is greater 1 mass unit. Check that all hydrogen
            atoms have been taken into account.
CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as
            calculated from the _atom_site* data lies outside
            the range 0.99 <> 1.01
           From the CIF: _cell_formula_units_Z                    2
           From the CIF: _chemical_formula_weight           732.67
           TEST: Calculate formula weight from _atom_site_*
           atom     mass    num     sum
           C        12.01   14.00  168.15
           H         1.01   26.00   26.21
           O        16.00   13.00  207.99
           F        19.00    6.00  113.99
           S        32.07    2.00   64.13
           Ba      137.33    1.00  137.33
           Calculated formula weight              717.80
DENSD01_ALERT_1_C  The ratio of the submitted crystal density and that
            calculated from the formula is outside the range 0.99 <> 1.01
            Crystal density given    =      1.835
            Calculated crystal density =      1.873
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT043_ALERT_1_C Check Reported Molecular Weight ................     732.67
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT046_ALERT_1_C Reported Z, MW and D(calc) are Inconsistent ....       1.87
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.82
PLAT231_ALERT_4_C Hirshfeld Test (Solvent)   S10    -   C14     ..       6.23 su
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        S10
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C14

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.821
            Tmax scaled      0.821 Tmin scaled      0.739

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  13 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Macrocycle-cation-π-interactions are of particular biological interest (Dougherty, 1996). In an attempt to co-crystallize an aromatic derivative with a macrocyclic (18-crown-6).(BaTf₂) complex (Arnal-Hérault et al., 2005), the latter complex crystallized without the organic compound. Crown-ethers are well known complexants to metal cations, with selective recognition properties relative to the size of the ring. The structure of Ba(C₁₂O₈H₂₄).(H₂O),(CF₃SO₃)₂ is forming tubular arrays (Barboiu et al., 2003) made of crown ether rings. The oxygen atoms of the crown ether are coordinating the cation in equatorial position while the trifluoromethanesulfonate (CF₃SO₃ or Tf) anions are coordinating the Ba²⁺ in apical position. The second apical position is coordinated by a bridging water molecule which is simultaneously H-bonded to both trifluoromethanesulfonate anions (O(Tf)–O(H₂O) ≈ 2.805 Å) and coordinated to the Ba²⁺ cation (Ba–O(H₂O) = 2.689 (2) Å). Fig. 1 shows the full coordination pattern of barium ions. Trifluoromethanesulfonate anions are either coordinated to two barium cations, or to two water molecules, them-self coordinated to Ba²⁺ cations. Each barium cation has the same environment i.e. it is coordinating to ten oxygen atoms of which six from the 18 C6, three from two trifluoromethanesulfonate on one face of the 18 C6 and one from the water molecule on the other face of the 18 C6. The decahedral geometry of barium can be characterized as a sliced distorted tetrahedral environment as depicted in Fig. 2. Molecular columns of barium are formed with an average Ba–Ba distance of 8.5 Å between the anions inside one row (See Fig. 3). Each 18 C6 tube is closely packed to two others through hydrophobic contacts, forming planar sheets. About 7.5 Å separate two rows of barium of one sheet, while the distance between the rows of barium in two distinct sheets is about 9.9 Å. Trifluoromethanesulfonate fluoride atoms close contacts are observed between two sheets (Fig. 4) with F–F = 2.932 (2) Å. The overall packing of the title compound is unusual in the way the trifluoromethanesulfonate anions are inserted between the parallel crown ethers and form supramolecular polymers containing metal cations, counter anions and water molecules. In all crystal structures including trifluoromethanesulfonate and 18 C6, the ion is pushed away in the hydrophobic gaps between the crown ether tubular arrays and does not form an ionic bridge between two metal cations (Wei et al., 1988).

Related literature

For a similar Ba–18-crown-6 compound, see: Wei et al. (1988). For examples of macrocycle–cation π interactions, see: Arnal-Hérault et al. (2005). For biological and related applications, see: Dougherty (1996); Meyer et al. (2003); Ma & Dougherty (1997). For examples of tubular superstructures, see: Barboiu et al. (2003); Blondeau et al. (2005); Fromm & Bergougnant (2007).

S2. Experimental

The title compound was prepared by dissolving in acetone (10 ml), in equimolar proportions, 1-(1H-indol-5-yl)-3-phenylurea (0.100 g), 18 C6 (0.105 g) and barium trifluoromethanesulfonate (0.173 g). The metallo-organic compound was crystallized by layering this solution with isopropyl ether. The crystals were formed over two days, by slow diffusion of the non-solvent in the solvent phase. The initial goal of the work was to grow co-crystals of inclusion complexes of Ba-18 C6 bound to the ureido-derivative ligand through cation-π interaction. Indeed, Arnal-Hérault et al. (2005) previously showed that the cation was favourably coordinated by the crown ether while the counter-ion was complexing with the ureido moiety of the co-crystallized ligand.

S3. Refinement

The H atoms, including those of the water molecule, were all located in a difference map, and repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98, O—H = 0.87 Å) and U_iso(H) (in the range 1.2–1.5 times U_eq of the parent atom), after which the positions were refined with riding constraints.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SIR2004 (Burla et al., 2003); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996), Mercury (Macrae et al., 2006) and DrawXtl (Finger et al., 2007); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures

	Fig. 1. Representation of (1) with the numbering scheme adopted. The Ba atom is in dark-grey, the F atom in light-green, the S atom in yellow, the C atom in green, the O atoms in red and the H atom in grey. Displacement ellipsoids are drawn at the 50% level. Non-labelled atoms are related by inversion symmetry (-1 halfway the two sulfur and barium atoms) to labeled atoms.
	Fig. 2. Sliced distorted tetrahedron environment for the barium cation. The red balls represent oxygen atoms. The oxygen atoms forming the base of the tetrahedron belong to the trifluoromethanesulfonate ions and the oxygen atom at the summit is part of the water molecule.
	Fig. 3. Representation of the repeating pattern with sandwiched trifluoromethanesulfonate anions between crown ethers-barium motifs.
	Fig. 4. The three-dimensional packing showing discrete sheets of crown ether tubes.

Bis(µ-trifluoromethanesulfonato-κ²O:O')bis[aqua˘1,4,7,10,13,16-hexaoxacyclooctadecane-κ⁶O)barium(II)] bis(trifluoromethanesulfonate)

Crystal data

[Ba2(CF3O3S)2(C12H24O6)2(H2O)2](CF3O3S)2	Z = 1
Mr = 1465.34	F(000) = 712
Triclinic, P1	Dx = 1.835 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.942 (1) Å	Cell parameters from 23806 reflections
b = 12.3257 (16) Å	θ = 4–33°
c = 12.7431 (14) Å	µ = 1.79 mm^−1
α = 68.629 (12)°	T = 175 K
β = 87.576 (10)°	Needle, colourless
γ = 83.212 (10)°	0.35 × 0.16 × 0.11 mm
V = 1298.8 (3) Å^3

Data collection

Oxford Diffraction GEMINI diffractometer	9409 independent reflections
Radiation source: Enhance (Mo) X-ray Source	6364 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 16.0143 pixels mm^-1	θmax = 33.5°, θmin = 3.8°
ϕ & ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007); Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −18→19
Tmin = 0.90, Tmax = 1.00	l = −19→16
23806 measured reflections

Refinement

Refinement on F	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.023	H-atom parameters constrained
wR(F^2) = 0.022	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 19.2 -26.3 13.3 -3.95
S = 1.11	(Δ/σ)max = 0.001
6364 reflections	Δρmax = 0.45 e Å^−3
325 parameters	Δρmin = −0.48 e Å^−3
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ba1	0.823886 (15)	0.307417 (11)	0.715055 (11)	0.0197
S2	0.98425 (6)	0.57362 (4)	0.60939 (4)	0.0214
O3	0.82673 (17)	0.56535 (14)	0.59766 (13)	0.0280
O4	1.06495 (18)	0.46352 (14)	0.67793 (14)	0.0304
O5	1.0606 (2)	0.63842 (15)	0.50802 (14)	0.0329
C6	0.9852 (3)	0.6661 (2)	0.6942 (2)	0.0316
F7	0.92051 (19)	0.61984 (15)	0.79318 (13)	0.0447
F8	0.9110 (2)	0.77100 (14)	0.64130 (16)	0.0568
F9	1.1246 (2)	0.68206 (19)	0.71126 (17)	0.0593
S10	0.55301 (6)	0.83623 (5)	0.86965 (5)	0.0256
O11	0.4194 (2)	0.8629 (2)	0.92588 (16)	0.0484
O12	0.6165 (2)	0.71647 (15)	0.91215 (17)	0.0410
O13	0.6602 (2)	0.92020 (17)	0.84453 (19)	0.0479
C14	0.4807 (3)	0.8563 (2)	0.7315 (2)	0.0361
F15	0.4128 (2)	0.96364 (15)	0.67946 (14)	0.0525
F16	0.3796 (2)	0.78288 (17)	0.73984 (17)	0.0622
F17	0.5887 (2)	0.8363 (2)	0.66466 (17)	0.0740
O18	0.55879 (17)	0.42809 (13)	0.76730 (13)	0.0266
C19	0.5834 (3)	0.5078 (2)	0.8213 (2)	0.0308
C20	0.6720 (3)	0.4413 (2)	0.9258 (2)	0.0348
O21	0.81117 (19)	0.38901 (14)	0.89606 (13)	0.0302
C22	0.9059 (4)	0.3309 (3)	0.9923 (2)	0.0452
C23	1.0526 (3)	0.2859 (3)	0.9547 (3)	0.0488
O24	1.0229 (2)	0.20633 (16)	0.90171 (15)	0.0382
C25	1.1552 (3)	0.1405 (3)	0.8804 (3)	0.0544
C26	1.1083 (4)	0.0470 (3)	0.8449 (3)	0.0536
O27	1.0265 (2)	0.10039 (15)	0.74158 (15)	0.0378
C28	0.9786 (3)	0.0131 (2)	0.7045 (3)	0.0456
C29	0.8885 (3)	0.0720 (2)	0.5994 (2)	0.0430
O30	0.7606 (2)	0.13963 (14)	0.62381 (14)	0.0313
C31	0.6505 (3)	0.1803 (2)	0.5361 (2)	0.0362
C32	0.5118 (3)	0.2330 (2)	0.5771 (2)	0.0359
O33	0.54743 (17)	0.33276 (14)	0.59967 (13)	0.0269
C34	0.4159 (3)	0.3861 (3)	0.6381 (2)	0.0388
C35	0.4590 (3)	0.4808 (2)	0.6740 (2)	0.0340
H36	0.3703	0.5207	0.6964	0.0416*
H37	0.5078	0.5375	0.6122	0.0413*
H38	0.3740	0.3246	0.7009	0.0500*
H39	0.3438	0.4169	0.5780	0.0503*
H40	0.4765	0.1765	0.6458	0.0466*
H41	0.4322	0.2567	0.5207	0.0471*
H42	0.6903	0.2365	0.4685	0.0455*
H43	0.6257	0.1139	0.5185	0.0464*
H44	0.9487	0.1209	0.5398	0.0525*
H45	0.8550	0.0117	0.5767	0.0528*
H46	1.0667	−0.0352	0.6916	0.0524*
H47	0.9167	−0.0359	0.7628	0.0518*
H48	1.1964	−0.0017	0.8344	0.0574*
H49	1.0434	−0.0014	0.9024	0.0574*
H50	1.2142	0.1046	0.9496	0.0613*
H51	1.2145	0.1921	0.8223	0.0613*
H52	1.1166	0.2439	1.0196	0.0582*
H53	1.1021	0.3498	0.9018	0.0580*
H54	0.9236	0.3861	1.0276	0.0541*
H55	0.8569	0.2662	1.0459	0.0543*
H56	0.6949	0.4938	0.9634	0.0436*
H57	0.6147	0.3809	0.9773	0.0441*
H58	0.6369	0.5710	0.7702	0.0387*
H59	0.4879	0.5406	0.8420	0.0391*
O60	0.6654 (3)	0.14219 (16)	0.85835 (16)	0.0479
H61	0.6682	0.0712	0.8616	0.0500*
H62	0.6264	0.1452	0.9203	0.0500*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.02160 (5)	0.01736 (5)	0.01886 (5)	−0.00117 (3)	0.00021 (4)	−0.00535 (3)
S2	0.0234 (2)	0.0229 (2)	0.0205 (2)	−0.00578 (18)	0.00364 (17)	−0.01018 (18)
O3	0.0247 (7)	0.0310 (8)	0.0309 (8)	−0.0048 (6)	−0.0008 (6)	−0.0137 (6)
O4	0.0271 (8)	0.0287 (8)	0.0329 (8)	−0.0013 (6)	0.0007 (6)	−0.0086 (7)
O5	0.0442 (10)	0.0322 (8)	0.0262 (8)	−0.0151 (7)	0.0139 (7)	−0.0133 (7)
C6	0.0353 (12)	0.0341 (11)	0.0342 (12)	−0.0162 (9)	0.0110 (9)	−0.0203 (10)
F7	0.0561 (10)	0.0593 (10)	0.0333 (8)	−0.0285 (8)	0.0189 (7)	−0.0292 (7)
F8	0.0837 (14)	0.0319 (8)	0.0588 (11)	−0.0036 (8)	0.0180 (10)	−0.0240 (8)
F9	0.0455 (10)	0.0929 (15)	0.0712 (12)	−0.0395 (10)	0.0172 (9)	−0.0593 (12)
S10	0.0262 (2)	0.0247 (2)	0.0286 (3)	−0.00262 (19)	−0.0003 (2)	−0.0126 (2)
O11	0.0415 (11)	0.0666 (14)	0.0318 (9)	0.0138 (10)	0.0028 (8)	−0.0178 (9)
O12	0.0410 (10)	0.0279 (8)	0.0532 (12)	0.0017 (7)	−0.0108 (9)	−0.0143 (8)
O13	0.0494 (12)	0.0365 (10)	0.0630 (13)	−0.0178 (9)	−0.0062 (10)	−0.0195 (9)
C14	0.0395 (13)	0.0369 (12)	0.0349 (12)	−0.0054 (10)	0.0018 (10)	−0.0164 (10)
F15	0.0683 (12)	0.0403 (9)	0.0386 (9)	0.0014 (8)	−0.0133 (8)	−0.0030 (7)
F16	0.0720 (13)	0.0532 (11)	0.0662 (12)	−0.0212 (10)	−0.0296 (10)	−0.0198 (9)
F17	0.0673 (13)	0.1174 (19)	0.0463 (11)	0.0111 (13)	0.0071 (9)	−0.0475 (12)
O18	0.0282 (8)	0.0236 (7)	0.0288 (8)	0.0001 (6)	−0.0001 (6)	−0.0115 (6)
C19	0.0336 (12)	0.0257 (10)	0.0358 (12)	−0.0024 (9)	0.0083 (9)	−0.0156 (9)
C20	0.0477 (14)	0.0323 (11)	0.0307 (11)	−0.0103 (10)	0.0082 (10)	−0.0181 (10)
O21	0.0402 (9)	0.0306 (8)	0.0201 (7)	−0.0028 (7)	−0.0035 (6)	−0.0094 (6)
C22	0.0611 (18)	0.0471 (15)	0.0265 (12)	−0.0050 (13)	−0.0162 (12)	−0.0108 (11)
C23	0.0487 (16)	0.0527 (17)	0.0401 (15)	−0.0070 (13)	−0.0205 (13)	−0.0083 (13)
O24	0.0304 (9)	0.0394 (9)	0.0376 (9)	0.0031 (7)	−0.0103 (7)	−0.0063 (8)
C25	0.0251 (12)	0.079 (2)	0.0434 (16)	0.0120 (13)	−0.0069 (11)	−0.0086 (15)
C26	0.0485 (17)	0.0469 (16)	0.0449 (16)	0.0266 (13)	0.0000 (13)	−0.0022 (13)
O27	0.0385 (9)	0.0288 (8)	0.0356 (9)	0.0087 (7)	0.0044 (7)	−0.0034 (7)
C28	0.0454 (15)	0.0235 (11)	0.0596 (18)	0.0040 (10)	0.0164 (13)	−0.0094 (11)
C29	0.0556 (17)	0.0301 (12)	0.0480 (15)	−0.0016 (11)	0.0137 (13)	−0.0222 (11)
O30	0.0411 (9)	0.0247 (7)	0.0294 (8)	−0.0011 (7)	0.0044 (7)	−0.0127 (6)
C31	0.0523 (15)	0.0336 (12)	0.0288 (11)	−0.0124 (11)	−0.0006 (10)	−0.0160 (10)
C32	0.0392 (13)	0.0377 (12)	0.0345 (12)	−0.0141 (10)	−0.0030 (10)	−0.0142 (10)
O33	0.0242 (7)	0.0295 (8)	0.0288 (8)	−0.0040 (6)	−0.0024 (6)	−0.0120 (6)
C34	0.0229 (11)	0.0525 (16)	0.0444 (14)	−0.0021 (10)	−0.0009 (10)	−0.0220 (12)
C35	0.0269 (11)	0.0345 (12)	0.0387 (13)	0.0077 (9)	−0.0038 (9)	−0.0140 (10)
O60	0.0825 (15)	0.0312 (9)	0.0358 (10)	−0.0251 (10)	0.0259 (10)	−0.0161 (8)

Geometric parameters (Å, º)

Ba1—O3	2.9825 (17)	C22—C23	1.492 (4)
Ba1—O4	2.9669 (17)	C22—H54	0.972
Ba1—O5^i	2.8504 (16)	C22—H55	0.977
Ba1—O18	2.8336 (15)	C23—O24	1.431 (4)
Ba1—O21	2.8259 (16)	C23—H52	0.968
Ba1—O24	2.8375 (17)	C23—H53	0.970
Ba1—O27	2.8701 (17)	O24—C25	1.427 (3)
Ba1—O30	2.8344 (16)	C25—C26	1.490 (5)
Ba1—O33	2.8567 (15)	C25—H50	0.975
Ba1—O60	2.6916 (18)	C25—H51	0.969
O60—Ba1	2.6916 (18)	C26—O27	1.427 (3)
O60—O11^ii	2.801 (3)	C26—H48	0.967
O60—O13^iii	2.811 (3)	C26—H49	0.978
S2—O3	1.4420 (16)	O27—C28	1.436 (3)
S2—O4	1.4433 (17)	C28—C29	1.488 (4)
S2—O5	1.4406 (16)	C28—H46	0.975
S2—C6	1.835 (2)	C28—H47	0.969
C6—F7	1.321 (3)	C29—O30	1.425 (3)
C6—F8	1.329 (3)	C29—H44	0.968
C6—F9	1.323 (3)	C29—H45	0.971
S10—O11	1.4335 (19)	O30—C31	1.427 (3)
S10—O12	1.4282 (18)	C31—C32	1.494 (4)
S10—O13	1.4348 (19)	C31—H42	0.973
S10—C14	1.822 (3)	C31—H43	0.976
C14—F15	1.328 (3)	C32—O33	1.433 (3)
C14—F16	1.328 (3)	C32—H40	0.967
C14—F17	1.322 (3)	C32—H41	0.975
O18—C19	1.430 (3)	O33—C34	1.435 (3)
O18—C35	1.422 (3)	C34—C35	1.494 (4)
C19—C20	1.488 (4)	C34—H38	0.978
C19—H58	0.975	C34—H39	0.958
C19—H59	0.969	C35—H36	0.971
C20—O21	1.434 (3)	C35—H37	0.970
C20—H56	0.977	O60—H61	0.858
C20—H57	0.977	O60—H62	0.861
O21—C22	1.428 (3)
O3—Ba1—O4	47.65 (4)	O18—C19—H59	110.0
O3—Ba1—O5^i	68.86 (5)	C20—C19—H59	108.5
O4—Ba1—O5^i	70.15 (5)	H58—C19—H59	109.4
O3—Ba1—O18	69.95 (5)	C19—C20—O21	108.74 (19)
O4—Ba1—O18	106.62 (5)	C19—C20—H56	110.5
O5^i—Ba1—O18	123.16 (5)	O21—C20—H56	108.5
O3—Ba1—O21	77.40 (5)	C19—C20—H57	109.9
O4—Ba1—O21	72.76 (5)	O21—C20—H57	110.3
O5^i—Ba1—O21	140.95 (5)	H56—C20—H57	108.9
O18—Ba1—O21	57.87 (5)	C20—O21—C22	111.26 (19)
O3—Ba1—O24	114.31 (5)	O21—C22—C23	108.7 (2)
O4—Ba1—O24	72.98 (5)	O21—C22—H54	109.5
O5^i—Ba1—O24	119.71 (6)	C23—C22—H54	109.2
O18—Ba1—O24	112.12 (5)	O21—C22—H55	109.4
O21—Ba1—O24	58.03 (5)	C23—C22—H55	110.3
O3—Ba1—O27	136.71 (5)	H54—C22—H55	109.7
O4—Ba1—O27	94.93 (5)	C22—C23—O24	108.0 (2)
O5^i—Ba1—O27	79.00 (5)	C22—C23—H52	109.5
O18—Ba1—O27	153.05 (5)	O24—C23—H52	108.7
O21—Ba1—O27	116.26 (5)	C22—C23—H53	110.8
O3—Ba1—O30	128.43 (5)	O24—C23—H53	109.7
O4—Ba1—O30	134.15 (5)	H52—C23—H53	110.1
O5^i—Ba1—O30	68.81 (5)	C23—O24—C25	113.7 (2)
O18—Ba1—O30	112.40 (5)	O24—C25—C26	108.4 (2)
O21—Ba1—O30	150.20 (5)	O24—C25—H50	109.0
O3—Ba1—O33	86.75 (5)	C26—C25—H50	109.4
O4—Ba1—O33	132.11 (5)	O24—C25—H51	109.6
O5^i—Ba1—O33	81.31 (5)	C26—C25—H51	111.0
O18—Ba1—O33	58.91 (5)	H50—C25—H51	109.5
O21—Ba1—O33	116.52 (5)	C25—C26—O27	109.0 (2)
O3—Ba1—O60	143.63 (5)	C25—C26—H48	109.7
O4—Ba1—O60	149.11 (6)	O27—C26—H48	109.7
O5^i—Ba1—O60	136.56 (5)	C25—C26—H49	109.8
O18—Ba1—O60	73.70 (6)	O27—C26—H49	109.1
O21—Ba1—O60	82.49 (5)	H48—C26—H49	109.5
O24—Ba1—O27	58.58 (6)	C26—O27—C28	110.8 (2)
O24—Ba1—O30	111.57 (5)	O27—C28—C29	109.2 (2)
O27—Ba1—O30	57.95 (5)	O27—C28—H46	109.4
O24—Ba1—O33	153.87 (5)	C29—C28—H46	110.7
O27—Ba1—O33	116.84 (5)	O27—C28—H47	108.7
O30—Ba1—O33	58.94 (5)	C29—C28—H47	109.5
O24—Ba1—O60	78.38 (6)	H46—C28—H47	109.3
O27—Ba1—O60	79.49 (6)	C28—C29—O30	108.2 (2)
O30—Ba1—O60	67.77 (5)	C28—C29—H44	110.7
O3—S2—O4	112.80 (10)	O30—C29—H44	111.1
O3—S2—O5	116.11 (10)	C28—C29—H45	107.9
O4—S2—O5	115.10 (10)	O30—C29—H45	109.4
O3—S2—C6	104.15 (10)	H44—C29—H45	109.4
O4—S2—C6	103.97 (11)	C29—O30—C31	112.9 (2)
O5—S2—C6	102.62 (10)	O30—C31—C32	108.66 (19)
S2—C6—F7	111.90 (15)	O30—C31—H42	110.2
S2—C6—F8	110.42 (18)	C32—C31—H42	111.6
F7—C6—F8	107.6 (2)	O30—C31—H43	109.0
S2—C6—F9	110.85 (16)	C32—C31—H43	108.9
F7—C6—F9	108.3 (2)	H42—C31—H43	108.4
F8—C6—F9	107.6 (2)	C31—C32—O33	108.8 (2)
O11—S10—O12	115.32 (13)	C31—C32—H40	110.1
O11—S10—O13	114.89 (14)	O33—C32—H40	109.0
O12—S10—O13	114.95 (12)	C31—C32—H41	110.4
O11—S10—C14	102.02 (12)	O33—C32—H41	109.9
O12—S10—C14	103.74 (12)	H40—C32—H41	108.6
O13—S10—C14	103.41 (13)	C32—O33—C34	110.17 (18)
S10—C14—F15	112.46 (18)	O33—C34—C35	109.32 (19)
S10—C14—F16	111.11 (18)	O33—C34—H38	107.4
F15—C14—F16	106.6 (2)	C35—C34—H38	111.2
S10—C14—F17	111.77 (19)	O33—C34—H39	108.7
F15—C14—F17	107.8 (2)	C35—C34—H39	111.1
F16—C14—F17	106.8 (2)	H38—C34—H39	109.1
C19—O18—C35	112.02 (17)	C34—C35—O18	108.0 (2)
O18—C19—C20	108.15 (18)	C34—C35—H36	110.3
Ba1—O60—O11^ii	123.03 (8)	O18—C35—H36	109.5
Ba1—O60—O13^iii	122.84 (8)	C34—C35—H37	109.9
O11^ii—O60—O13^iii	110.59 (9)	O18—C35—H37	110.3
O18—C19—H58	109.6	H36—C35—H37	108.8
C20—C19—H58	111.1	H61—O60—H62	107.6
O(4)—Ba(1)—O(3)—S(2)	3.37 (7)	O(4)—Ba(1)—O(18)—C(19)	−29.00 (15)
O(24)—Ba(1)—O(3)—S(2)	35.53 (9)	Ba(1)—O(27)—C(26)—C(25)	−38.9 (3)
O(33)—Ba(1)—O(3)—S(2)	−160.50 (8)	C(26)—O(27)—C(28)—C(29)	177.7 (2)
O(3)—Ba(1)—O(4)—S(2)	−3.37 (7)	Ba(1)—O(30)—C(31)—C(32)	−52.9 (2)
O(24)—Ba(1)—O(4)—S(2)	−152.88 (10)	C(34)—O(33)—C(32)—C(31)	179.39 (19)
O(33)—Ba(1)—O(4)—S(2)	18.58 (12)	O(18)—C(19)—C(20)—O(21)	58.5 (3)
O(3)—Ba(1)—O(18)—C(19)	−59.98 (14)	O(27)—C(28)—C(29)—O(30)	−60.3 (3)
O(18)—Ba(1)—O(3)—S(2)	141.49 (9)	C(28)—O(27)—C(26)—C(25)	−179.8 (2)
O(27)—Ba(1)—O(3)—S(2)	−33.69 (11)	Ba(1)—O(30)—C(29)—C(28)	56.3 (2)
O(60)—Ba(1)—O(3)—S(2)	139.44 (9)	C(29)—O(30)—C(31)—C(32)	171.0 (2)
O(18)—Ba(1)—O(4)—S(2)	−44.24 (9)	Ba(1)—O(33)—C(34)—C(35)	36.3 (2)
O(27)—Ba(1)—O(4)—S(2)	152.13 (8)	O(21)—C(22)—C(23)—O(24)	−59.7 (3)
O(60)—Ba(1)—O(4)—S(2)	−130.14 (10)	O(30)—C(31)—C(32)—O(33)	63.1 (2)
O(3)—Ba(1)—O(18)—C(35)	70.12 (15)	Ba(1)—O(27)—C(28)—C(29)	37.2 (3)
O(21)—Ba(1)—O(3)—S(2)	81.40 (8)	C(31)—O(30)—C(29)—C(28)	−167.8 (2)
O(30)—Ba(1)—O(3)—S(2)	−115.32 (8)	Ba(1)—O(33)—C(32)—C(31)	−43.4 (2)
O(5)^i—Ba(1)—O(3)—S(2)	−78.56 (8)	C(32)—O(33)—C(34)—C(35)	173.37 (19)
O(21)—Ba(1)—O(4)—S(2)	−91.88 (9)	O(24)—C(25)—C(26)—O(27)	63.3 (3)
O(30)—Ba(1)—O(4)—S(2)	103.31 (9)	O(33)—C(34)—C(35)—O(18)	−63.6 (2)
O(5)^i—Ba(1)—O(4)—S(2)	75.70 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C28—H47···O13^iii	0.97	2.51	3.384 (4)	149
C26—H48···O11^iv	0.97	2.47	3.316 (4)	146
C20—H56···O12	0.98	2.59	3.310 (4)	130
O60—H61···O13^iii	0.86	1.96	2.811 (4)	171
O60—H62···O11^ii	0.86	1.95	2.801 (4)	168

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