research communications
κO)(ethanol-κO)[(9S,17S,21S,29S)-9,17,21,29-tetrahydroxy-18,30-dioxaoctacyclo[18.10.0.02,7.08,19.09,17.011,16.021,29.023,28]triaconta-1,3,5,7,11(16),12,14,19,23(28),24,26-undecaene-10,22-dione-κ3O18,O21,O22]caesium ethanol monosolvate
of (acetato-aInstitute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, 9190401, Israel, and bDepartment of Chemistry, Nuclear Research Centre Negev, Beer Sheva, 84190, Israel
*Correspondence e-mail: ravell.bengiat@mail.huji.ac.il
The title compound, [Cs(CH3COO)(C28H16O8)(C2H5OH)]·C2H5OH, is the product of the complexation between one vasarene analogue [1], bis ninhydrin naphthalene-1,3-diol and CsF, where the F− ion has reacted with residual acetic acid (AcOH), to form a [1]·CsOAc complex. The intermolecular interactions with the multiple oxygen-containing functional groups of the ligand, as well as O—H⋯O hydrogen bonds involving the ethanol solvent molecules, stabilize the complex, forming a chain along [100]. Additional parallel-displaced π–π stacking, with an interplanar distance of 3.669 (1) Å, connect several unit cells in a three-dimensional supramolecular structure, though, the larger size of AcO− (1.60 Å) compared to F− (1.33 Å) prevents the tight packing that was once achieved with other vasarene complexes of CsF.
CCDC reference: 1479382
1. Chemical context
The supramolecular reactions of ligands from the vasarene family with ion-pairs of type M+F−, provided M is a large monovalent cation, have been studied extensively by our group in the past years (Almog et al., 2009, 2012; Bengiat et al., 2016a,b,c). The prerequisite regarding the size of the cation rests in the key role of the fluoride ion in initiating the complex formation (Bengiat et al., 2016b), though the contribution of the F− ion to the stability of the complex once formed has yet to be explored. In several cases, however, the F− ions have been absent from the final complex which contained acetate ions instead. This observation can be explained by the presence of acetic acid (AcOH) residues from the synthesis of the ligand, but the exact mechanism is still unknown. Here, we review the structure of the title complex and the effect of the AcO− anion on its supramolecular features.
2. Structural commentary
The complex was formed in the reaction of the bis ninhydrin naphthalene-1,3-diol ligand [1] (Fig. 1) with CsF. As mentioned earlier, we suggest that the presence of residual AcOH results in a selective precipitation with AcO− rather than F− in the final complex. Similar to the original vasarene complexes with CsF (Almog et al., 2012; Bengiat et al., 2016b,c), the Cs+ ion is stabilized by several interactions with the oxygen-containing functional groups of the ligand: hydroxyl (O3), carbonyl (O4) and etheric (O5), as well as by the additional EtOH solvate molecule (O1E) and the acetate counter-ion (O1A) (Scheme, Fig. 2).
Fig. 2 shows the hydrogen bonding between the different unit cells (Table 1) involving a second solvent molecule of EtOH, O2E⋯H–O1E and O2E–H⋯O2A. Further stabilization of the lattice is achieved by the parallel-displaced π–π stacking between the aromatic rings of the `side-walls' of ligands in different unit cells with an inter-planar distance of 3.669 (1) Å (Janiak, 2000) (Fig. 3). In other complexes of the vasarane analogues with CsF, there has been an alternating arrangement of ligand and salt layers, forming `salt channels' that are held by supramolecular interactions of hydrogen bonds, cation–π and metal coordination with the ligands (Bengiat et al., 2016b,c). In this case, however, it is suggested that the difference in the ionic radius between the F− (1.33 Å) and AcO− (1.60 Å) (Shannon, 1976; Manku, 1980) results in that prevents the tight packing of the lattice (Figs. 4 and 5).
3. Database survey
The bowl-shaped compound formed upon reaction between ninhydrin and 1,3,5-benzenetriol was first reported by Kim and his co-workers (Na et al., 2005), while other groups attempted similar reactions involving ninhydrin and polyhydroxy aromatics (Kundu et al., 2004; Mahmood et al., 2011). Since then, the reaction has been thoroughly explored by our group, expanding the family of these ligands, which we have named vasarenes (Almog et al., 2009; Gil et al., 2014; Bengiat et al., 2016c,d). A comprehensive study of the supramolecular reactions of the vasarenes and their analogues with M+F− salts has also been carried out (Almog et al., 2012; Bengiat et al., 2016a,b,c). However, this is the first time that a complex with an anion other than fluoride has been reported.
4. Synthesis and crystallization
The ligand [1] was synthesized according to a recently reported procedure (Bengiat et al. 2016c) in a one-pot reaction in AcOH. Ligand [1] (151.0 mg, 0.314 mmol) was dissolved in warm EtOH (10 mL). An equivalent amount of CsF (50.1 mg, 0.329 mmol) was dissolved in warm EtOH (2 mL) with few drops of H2Odist. and added to the solution of [1]. Upon addition of the CsF solution an immediate color change to intense yellow was observed, later changing to bright orange. The mixture was left to crystallize at RT for a few days, forming a colorless crystalline precipitate suitable for single crystal X-ray diffraction.
5. Refinement
Crystal data, data collection and structure . Hydroxyl H atoms of the ligand molecules and H atoms of the EtOH molecule were located in a different Fourier map and all H-atom parameters refined. Other H atoms were placed in calculated positions with C—H = 0.95 (aromatic), 0.99 (methylene) and 0.98 Å (methyl), and refined in riding mode with Uiso(H) = 1.2Ueq(C) for aromatic and aliphatic H atoms and 1.5Ueq(C) for the methyl H atoms.
details are summarized in Table 2
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Supporting information
CCDC reference: 1479382
https://doi.org/10.1107/S2056989016008860/lh5813sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016008860/lh5813Isup2.hkl
Data collection: SMART (Bruker, 2002); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Cs(C2H3O2)(C28H16O8)(C2H6O)]·C2H6O | Z = 2 |
Mr = 764.50 | F(000) = 772 |
Triclinic, P1 | Dx = 1.576 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.609 (2) Å | Cell parameters from 7362 reflections |
b = 11.669 (2) Å | θ = 2.1–28.1° |
c = 14.319 (2) Å | µ = 1.21 mm−1 |
α = 74.741 (2)° | T = 173 K |
β = 70.932 (2)° | Prisme, colorless |
γ = 89.095 (2)° | 0.64 × 0.24 × 0.13 mm |
V = 1611.5 (4) Å3 |
Bruker SMART CCD diffractometer | 6917 independent reflections |
Radiation source: fine-focus sealed tube | 6818 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
φ and ω scans | θmax = 27.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −13→13 |
Tmin = 0.511, Tmax = 0.858 | k = −14→14 |
17584 measured reflections | l = −18→18 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0375P)2 + 1.213P] where P = (Fo2 + 2Fc2)/3 |
6917 reflections | (Δ/σ)max = 0.007 |
451 parameters | Δρmax = 1.72 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2002 (2) | 0.13669 (19) | 1.17244 (17) | 0.0175 (4) | |
C2 | 0.1777 (2) | 0.1095 (2) | 1.27587 (18) | 0.0199 (4) | |
C3 | 0.2805 (2) | 0.1067 (2) | 1.31994 (18) | 0.0209 (5) | |
C4 | 0.4154 (2) | 0.1316 (2) | 1.25043 (19) | 0.0213 (5) | |
C5 | 0.4384 (2) | 0.1527 (2) | 1.14390 (18) | 0.0194 (4) | |
C6 | 0.3334 (2) | 0.15554 (19) | 1.10705 (17) | 0.0181 (4) | |
C7 | 0.2532 (3) | 0.0832 (2) | 1.4266 (2) | 0.0264 (5) | |
H7 | 0.1638 | 0.0640 | 1.4725 | 0.032* | |
C8 | 0.3557 (3) | 0.0882 (3) | 1.4641 (2) | 0.0316 (6) | |
H8 | 0.3375 | 0.0731 | 1.5359 | 0.038* | |
C9 | 0.4886 (3) | 0.1158 (3) | 1.3959 (2) | 0.0327 (6) | |
H9 | 0.5586 | 0.1213 | 1.4226 | 0.039* | |
C10 | 0.5189 (3) | 0.1348 (2) | 1.2928 (2) | 0.0273 (5) | |
H10 | 0.6095 | 0.1502 | 1.2489 | 0.033* | |
C11 | −0.0331 (2) | 0.1068 (2) | 1.26594 (18) | 0.0204 (4) | |
C12 | 0.0699 (2) | 0.1299 (2) | 1.15298 (18) | 0.0186 (4) | |
C13 | 0.0413 (2) | 0.2535 (2) | 1.09573 (19) | 0.0211 (5) | |
C14 | −0.0449 (2) | 0.3084 (2) | 1.17370 (19) | 0.0230 (5) | |
C15 | −0.0903 (2) | 0.2250 (2) | 1.26866 (19) | 0.0225 (5) | |
C16 | −0.1744 (3) | 0.2560 (3) | 1.3541 (2) | 0.0307 (6) | |
H16 | −0.2059 | 0.1995 | 1.4195 | 0.037* | |
C17 | −0.2108 (3) | 0.3720 (3) | 1.3405 (2) | 0.0404 (7) | |
H17 | −0.2678 | 0.3952 | 1.3979 | 0.048* | |
C18 | −0.1660 (3) | 0.4555 (3) | 1.2449 (3) | 0.0404 (7) | |
H18 | −0.1931 | 0.5344 | 1.2380 | 0.049* | |
C19 | −0.0827 (3) | 0.4247 (2) | 1.1601 (2) | 0.0320 (6) | |
H19 | −0.0521 | 0.4811 | 1.0946 | 0.038* | |
C21 | 0.5131 (2) | 0.1982 (2) | 0.96238 (18) | 0.0196 (4) | |
C22 | 0.5672 (2) | 0.1622 (2) | 1.05530 (18) | 0.0208 (5) | |
C23 | 0.6674 (2) | 0.2676 (2) | 1.0343 (2) | 0.0259 (5) | |
C24 | 0.6405 (2) | 0.3677 (2) | 0.9577 (2) | 0.0251 (5) | |
C25 | 0.5503 (2) | 0.3302 (2) | 0.91796 (19) | 0.0220 (5) | |
C26 | 0.5078 (3) | 0.4087 (2) | 0.8450 (2) | 0.0290 (5) | |
H26 | 0.4445 | 0.3833 | 0.8192 | 0.035* | |
C27 | 0.5618 (3) | 0.5262 (3) | 0.8112 (2) | 0.0364 (6) | |
H27 | 0.5346 | 0.5824 | 0.7614 | 0.044* | |
C28 | 0.6550 (3) | 0.5628 (2) | 0.8490 (2) | 0.0380 (7) | |
H28 | 0.6919 | 0.6431 | 0.8232 | 0.046* | |
C29 | 0.6945 (3) | 0.4858 (2) | 0.9226 (2) | 0.0340 (6) | |
H29 | 0.7568 | 0.5119 | 0.9490 | 0.041* | |
Cs1 | 0.191153 (14) | 0.124796 (13) | 0.862730 (11) | 0.02585 (7) | |
O1 | 0.04685 (16) | 0.08256 (15) | 1.33507 (13) | 0.0226 (3) | |
O2 | −0.12922 (17) | 0.01494 (17) | 1.29727 (14) | 0.0243 (4) | |
H2O | −0.099 (3) | −0.041 (3) | 1.299 (3) | 0.034 (10)* | |
O3 | 0.06070 (17) | 0.04548 (16) | 1.10108 (13) | 0.0212 (3) | |
H3O | 0.093 (3) | −0.005 (3) | 1.122 (2) | 0.021 (8)* | |
O4 | 0.08513 (19) | 0.29564 (16) | 1.00382 (14) | 0.0289 (4) | |
O5 | 0.36872 (15) | 0.17430 (15) | 1.00338 (12) | 0.0197 (3) | |
O6 | 0.55495 (19) | 0.13249 (16) | 0.89154 (14) | 0.0229 (4) | |
H6O | 0.623 (4) | 0.137 (3) | 0.874 (3) | 0.031 (10)* | |
O7 | 0.63353 (19) | 0.05673 (17) | 1.06295 (15) | 0.0262 (4) | |
H7O | 0.584 (3) | 0.013 (3) | 1.071 (3) | 0.031 (10)* | |
O8 | 0.7534 (2) | 0.2654 (2) | 1.07278 (17) | 0.0417 (5) | |
C1A | −0.0995 (3) | 0.2127 (2) | 0.7471 (2) | 0.0292 (5) | |
C2A | −0.1497 (4) | 0.3298 (3) | 0.7045 (3) | 0.0605 (11) | |
H2A1 | −0.1226 | 0.3911 | 0.7310 | 0.091* | |
H2A2 | −0.2475 | 0.3214 | 0.7254 | 0.091* | |
H2A3 | −0.1116 | 0.3529 | 0.6293 | 0.091* | |
O1A | 0.02108 (18) | 0.19599 (17) | 0.70590 (15) | 0.0322 (4) | |
O2A | −0.18031 (18) | 0.13858 (16) | 0.82327 (15) | 0.0302 (4) | |
C1E | 0.4943 (4) | 0.3196 (4) | 0.5980 (3) | 0.0606 (10) | |
H1E1 | 0.5492 | 0.3891 | 0.5951 | 0.073* | |
H1E2 | 0.4918 | 0.3275 | 0.5281 | 0.073* | |
C2E | 0.5549 (5) | 0.2099 (5) | 0.6319 (3) | 0.0800 (15) | |
H2E1 | 0.5524 | 0.1999 | 0.7027 | 0.120* | |
H2E2 | 0.6479 | 0.2146 | 0.5869 | 0.120* | |
H2E3 | 0.5049 | 0.1418 | 0.6290 | 0.120* | |
O1E | 0.3619 (3) | 0.3185 (3) | 0.6666 (2) | 0.0576 (7) | |
H1E | 0.319 (4) | 0.340 (4) | 0.625 (3) | 0.063 (13)* | |
C3E | 0.2150 (3) | 0.3851 (3) | 0.4560 (2) | 0.0419 (7) | |
H3E1 | 0.2817 | 0.3271 | 0.4387 | 0.050* | |
H3E2 | 0.2551 | 0.4653 | 0.4122 | 0.050* | |
C4E | 0.0925 (4) | 0.3560 (3) | 0.4324 (3) | 0.0483 (8) | |
H4E1 | 0.0530 | 0.2762 | 0.4748 | 0.072* | |
H4E2 | 0.1180 | 0.3584 | 0.3596 | 0.072* | |
H4E3 | 0.0271 | 0.4146 | 0.4474 | 0.072* | |
O2E | 0.1861 (2) | 0.3825 (2) | 0.56062 (18) | 0.0436 (5) | |
H2E | 0.131 (4) | 0.329 (4) | 0.600 (3) | 0.056 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0179 (10) | 0.0144 (10) | 0.0202 (11) | 0.0014 (8) | −0.0073 (8) | −0.0036 (8) |
C2 | 0.0186 (10) | 0.0173 (10) | 0.0221 (11) | 0.0024 (8) | −0.0057 (9) | −0.0038 (9) |
C3 | 0.0225 (11) | 0.0184 (11) | 0.0210 (11) | 0.0028 (8) | −0.0088 (9) | −0.0025 (9) |
C4 | 0.0210 (11) | 0.0171 (11) | 0.0248 (12) | 0.0021 (8) | −0.0088 (9) | −0.0026 (9) |
C5 | 0.0169 (10) | 0.0157 (10) | 0.0244 (12) | −0.0002 (8) | −0.0060 (9) | −0.0048 (9) |
C6 | 0.0203 (11) | 0.0130 (10) | 0.0201 (11) | 0.0014 (8) | −0.0064 (9) | −0.0034 (8) |
C7 | 0.0258 (12) | 0.0272 (12) | 0.0239 (12) | 0.0045 (10) | −0.0082 (10) | −0.0035 (10) |
C8 | 0.0355 (14) | 0.0364 (15) | 0.0242 (13) | 0.0058 (11) | −0.0151 (11) | −0.0041 (11) |
C9 | 0.0318 (14) | 0.0391 (15) | 0.0314 (14) | 0.0029 (11) | −0.0194 (11) | −0.0053 (12) |
C10 | 0.0229 (12) | 0.0284 (13) | 0.0300 (13) | 0.0023 (10) | −0.0118 (10) | −0.0034 (10) |
C11 | 0.0173 (10) | 0.0225 (11) | 0.0206 (11) | 0.0017 (8) | −0.0057 (9) | −0.0055 (9) |
C12 | 0.0162 (10) | 0.0185 (11) | 0.0206 (11) | 0.0015 (8) | −0.0052 (8) | −0.0058 (9) |
C13 | 0.0185 (10) | 0.0198 (11) | 0.0256 (12) | 0.0024 (8) | −0.0091 (9) | −0.0053 (9) |
C14 | 0.0210 (11) | 0.0230 (12) | 0.0267 (12) | 0.0053 (9) | −0.0091 (9) | −0.0083 (10) |
C15 | 0.0178 (10) | 0.0238 (12) | 0.0278 (12) | 0.0019 (9) | −0.0079 (9) | −0.0099 (10) |
C16 | 0.0255 (12) | 0.0344 (14) | 0.0301 (14) | 0.0027 (10) | −0.0030 (10) | −0.0131 (11) |
C17 | 0.0386 (16) | 0.0392 (16) | 0.0418 (17) | 0.0116 (13) | −0.0039 (13) | −0.0211 (14) |
C18 | 0.0453 (17) | 0.0292 (15) | 0.0471 (18) | 0.0155 (12) | −0.0113 (14) | −0.0167 (13) |
C19 | 0.0349 (14) | 0.0252 (13) | 0.0349 (15) | 0.0079 (11) | −0.0108 (11) | −0.0080 (11) |
C21 | 0.0154 (10) | 0.0189 (11) | 0.0234 (11) | 0.0004 (8) | −0.0038 (8) | −0.0074 (9) |
C22 | 0.0179 (10) | 0.0184 (11) | 0.0247 (12) | 0.0014 (8) | −0.0065 (9) | −0.0043 (9) |
C23 | 0.0201 (11) | 0.0275 (13) | 0.0276 (13) | −0.0035 (9) | −0.0042 (9) | −0.0078 (10) |
C24 | 0.0224 (11) | 0.0237 (12) | 0.0256 (12) | −0.0026 (9) | −0.0023 (9) | −0.0079 (10) |
C25 | 0.0193 (11) | 0.0197 (11) | 0.0227 (12) | 0.0022 (8) | −0.0006 (9) | −0.0069 (9) |
C26 | 0.0291 (13) | 0.0259 (13) | 0.0275 (13) | 0.0048 (10) | −0.0055 (10) | −0.0048 (10) |
C27 | 0.0418 (16) | 0.0249 (13) | 0.0324 (15) | 0.0093 (11) | −0.0030 (12) | −0.0036 (11) |
C28 | 0.0459 (17) | 0.0169 (12) | 0.0388 (16) | −0.0022 (11) | 0.0014 (13) | −0.0066 (11) |
C29 | 0.0333 (14) | 0.0278 (14) | 0.0358 (15) | −0.0069 (11) | −0.0012 (11) | −0.0128 (12) |
Cs1 | 0.02629 (10) | 0.02675 (10) | 0.02485 (10) | 0.00161 (6) | −0.01049 (6) | −0.00509 (6) |
O1 | 0.0181 (8) | 0.0271 (9) | 0.0194 (8) | 0.0011 (6) | −0.0046 (6) | −0.0032 (7) |
O2 | 0.0197 (8) | 0.0216 (9) | 0.0273 (9) | −0.0019 (7) | −0.0034 (7) | −0.0053 (7) |
O3 | 0.0224 (8) | 0.0179 (8) | 0.0249 (9) | 0.0026 (7) | −0.0096 (7) | −0.0066 (7) |
O4 | 0.0327 (9) | 0.0260 (9) | 0.0232 (9) | 0.0066 (7) | −0.0065 (7) | −0.0026 (7) |
O5 | 0.0154 (7) | 0.0229 (8) | 0.0191 (8) | 0.0000 (6) | −0.0040 (6) | −0.0050 (6) |
O6 | 0.0181 (9) | 0.0226 (9) | 0.0262 (9) | 0.0009 (7) | −0.0022 (7) | −0.0099 (7) |
O7 | 0.0199 (9) | 0.0219 (9) | 0.0353 (10) | 0.0055 (7) | −0.0085 (7) | −0.0064 (8) |
O8 | 0.0324 (10) | 0.0480 (13) | 0.0437 (12) | −0.0132 (9) | −0.0196 (9) | −0.0014 (10) |
C1A | 0.0294 (13) | 0.0248 (13) | 0.0281 (13) | 0.0048 (10) | −0.0062 (10) | −0.0029 (10) |
C2A | 0.0462 (19) | 0.0423 (19) | 0.056 (2) | 0.0219 (15) | 0.0086 (16) | 0.0148 (16) |
O1A | 0.0236 (9) | 0.0261 (9) | 0.0361 (10) | 0.0034 (7) | −0.0023 (8) | −0.0003 (8) |
O2A | 0.0249 (9) | 0.0228 (9) | 0.0331 (10) | 0.0031 (7) | −0.0015 (7) | −0.0019 (8) |
C1E | 0.050 (2) | 0.068 (3) | 0.048 (2) | 0.0046 (18) | −0.0024 (16) | −0.0071 (19) |
C2E | 0.092 (3) | 0.105 (4) | 0.049 (2) | 0.049 (3) | −0.025 (2) | −0.033 (2) |
O1E | 0.0424 (13) | 0.0750 (19) | 0.0410 (14) | 0.0083 (13) | −0.0057 (11) | −0.0026 (13) |
C3E | 0.0445 (17) | 0.0315 (15) | 0.0380 (17) | 0.0020 (12) | −0.0029 (13) | −0.0036 (13) |
C4E | 0.055 (2) | 0.0434 (18) | 0.0427 (18) | 0.0000 (15) | −0.0115 (15) | −0.0115 (15) |
O2E | 0.0448 (13) | 0.0393 (12) | 0.0366 (12) | −0.0098 (10) | −0.0067 (10) | −0.0015 (10) |
C1—C2 | 1.369 (3) | C26—C27 | 1.392 (4) |
C1—C6 | 1.399 (3) | C26—H26 | 0.9500 |
C1—C12 | 1.504 (3) | C27—C28 | 1.392 (5) |
C2—O1 | 1.360 (3) | C27—H27 | 0.9500 |
C2—C3 | 1.423 (3) | C28—C29 | 1.368 (5) |
C3—C7 | 1.409 (3) | C28—H28 | 0.9500 |
C3—C4 | 1.434 (3) | C29—H29 | 0.9500 |
C4—C5 | 1.417 (3) | Cs1—O7i | 3.0101 (18) |
C4—C10 | 1.422 (3) | Cs1—O3 | 3.1163 (18) |
C5—C6 | 1.377 (3) | Cs1—O1E | 3.121 (3) |
C5—C22 | 1.512 (3) | Cs1—O4 | 3.1441 (18) |
C6—O5 | 1.364 (3) | Cs1—O3ii | 3.1744 (17) |
C7—C8 | 1.369 (4) | Cs1—O1A | 3.257 (2) |
C7—H7 | 0.9500 | Cs1—O5 | 3.3263 (16) |
C8—C9 | 1.412 (4) | Cs1—O2ii | 3.3650 (19) |
C8—H8 | 0.9500 | Cs1—Cs1ii | 4.9310 (5) |
C9—C10 | 1.361 (4) | Cs1—H3O | 3.43 (3) |
C9—H9 | 0.9500 | O2—Cs1ii | 3.3650 (19) |
C10—H10 | 0.9500 | O2—H2O | 0.72 (4) |
C11—O2 | 1.368 (3) | O3—Cs1ii | 3.1744 (17) |
C11—O1 | 1.474 (3) | O3—H3O | 0.72 (3) |
C11—C15 | 1.503 (3) | O6—H6O | 0.68 (4) |
C11—C12 | 1.584 (3) | O7—Cs1i | 3.0101 (18) |
C12—O3 | 1.402 (3) | O7—H7O | 0.70 (4) |
C12—C13 | 1.539 (3) | C1A—O1A | 1.258 (3) |
C13—O4 | 1.207 (3) | C1A—O2A | 1.261 (3) |
C13—C14 | 1.478 (3) | C1A—C2A | 1.507 (4) |
C14—C15 | 1.385 (4) | C2A—H2A1 | 0.9800 |
C14—C19 | 1.392 (4) | C2A—H2A2 | 0.9800 |
C15—C16 | 1.390 (3) | C2A—H2A3 | 0.9800 |
C16—C17 | 1.383 (4) | C1E—O1E | 1.424 (4) |
C16—H16 | 0.9500 | C1E—C2E | 1.462 (6) |
C17—C18 | 1.391 (5) | C1E—H1E1 | 0.9900 |
C17—H17 | 0.9500 | C1E—H1E2 | 0.9900 |
C18—C19 | 1.379 (4) | C2E—H2E1 | 0.9800 |
C18—H18 | 0.9500 | C2E—H2E2 | 0.9800 |
C19—H19 | 0.9500 | C2E—H2E3 | 0.9800 |
C21—O6 | 1.385 (3) | O1E—H1E | 0.84 (4) |
C21—O5 | 1.452 (3) | C3E—O2E | 1.420 (4) |
C21—C25 | 1.508 (3) | C3E—C4E | 1.509 (5) |
C21—C22 | 1.572 (3) | C3E—H3E1 | 0.9900 |
C22—O7 | 1.405 (3) | C3E—H3E2 | 0.9900 |
C22—C23 | 1.540 (3) | C4E—H4E1 | 0.9800 |
C23—O8 | 1.207 (3) | C4E—H4E2 | 0.9800 |
C23—C24 | 1.472 (4) | C4E—H4E3 | 0.9800 |
C24—C25 | 1.389 (4) | O2E—H1E | 1.92 (5) |
C24—C29 | 1.398 (4) | O2E—H2E | 0.82 (4) |
C25—C26 | 1.387 (4) | ||
C2—C1—C6 | 117.4 (2) | O3—Cs1—O4 | 54.35 (5) |
C2—C1—C12 | 110.02 (19) | O1E—Cs1—O4 | 97.22 (7) |
C6—C1—C12 | 132.4 (2) | O7i—Cs1—O3ii | 99.87 (5) |
O1—C2—C1 | 114.2 (2) | O3—Cs1—O3ii | 76.77 (5) |
O1—C2—C3 | 121.7 (2) | O1E—Cs1—O3ii | 130.26 (7) |
C1—C2—C3 | 124.1 (2) | O4—Cs1—O3ii | 105.68 (5) |
C7—C3—C2 | 122.5 (2) | O7i—Cs1—O1A | 143.97 (5) |
C7—C3—C4 | 120.5 (2) | O3—Cs1—O1A | 123.70 (5) |
C2—C3—C4 | 117.0 (2) | O1E—Cs1—O1A | 71.34 (6) |
C5—C4—C10 | 123.7 (2) | O4—Cs1—O1A | 101.41 (5) |
C5—C4—C3 | 118.6 (2) | O3ii—Cs1—O1A | 61.26 (5) |
C10—C4—C3 | 117.7 (2) | O7i—Cs1—O5 | 58.07 (5) |
C6—C5—C4 | 120.9 (2) | O3—Cs1—O5 | 61.73 (4) |
C6—C5—C22 | 108.2 (2) | O1E—Cs1—O5 | 93.43 (6) |
C4—C5—C22 | 130.6 (2) | O4—Cs1—O5 | 61.33 (4) |
O5—C6—C5 | 115.3 (2) | O3ii—Cs1—O5 | 136.30 (4) |
O5—C6—C1 | 122.8 (2) | O1A—Cs1—O5 | 156.10 (4) |
C5—C6—C1 | 121.9 (2) | O7i—Cs1—O2ii | 95.85 (5) |
C8—C7—C3 | 119.9 (2) | O3—Cs1—O2ii | 124.63 (4) |
C8—C7—H7 | 120.1 | O1E—Cs1—O2ii | 86.84 (7) |
C3—C7—H7 | 120.1 | O4—Cs1—O2ii | 146.21 (5) |
C7—C8—C9 | 120.0 (2) | O3ii—Cs1—O2ii | 50.73 (4) |
C7—C8—H8 | 120.0 | O1A—Cs1—O2ii | 48.17 (5) |
C9—C8—H8 | 120.0 | O5—Cs1—O2ii | 152.22 (4) |
C10—C9—C8 | 121.6 (2) | O7i—Cs1—Cs1ii | 86.79 (4) |
C10—C9—H9 | 119.2 | O3—Cs1—Cs1ii | 38.81 (3) |
C8—C9—H9 | 119.2 | O1E—Cs1—Cs1ii | 162.27 (5) |
C9—C10—C4 | 120.3 (2) | O4—Cs1—Cs1ii | 78.79 (4) |
C9—C10—H10 | 119.9 | O3ii—Cs1—Cs1ii | 37.97 (3) |
C4—C10—H10 | 119.9 | O1A—Cs1—Cs1ii | 92.36 (3) |
O2—C11—O1 | 108.65 (18) | O5—Cs1—Cs1ii | 99.56 (3) |
O2—C11—C15 | 113.02 (19) | O2ii—Cs1—Cs1ii | 87.23 (3) |
O1—C11—C15 | 107.72 (19) | O7i—Cs1—H3O | 63.4 (5) |
O2—C11—C12 | 116.42 (19) | O3—Cs1—H3O | 11.5 (5) |
O1—C11—C12 | 106.32 (17) | O1E—Cs1—H3O | 150.9 (5) |
C15—C11—C12 | 104.20 (19) | O4—Cs1—H3O | 63.9 (5) |
O3—C12—C1 | 114.48 (18) | O3ii—Cs1—H3O | 78.1 (5) |
O3—C12—C13 | 110.29 (19) | O1A—Cs1—H3O | 131.6 (5) |
C1—C12—C13 | 110.50 (18) | O5—Cs1—H3O | 58.5 (5) |
O3—C12—C11 | 115.78 (18) | O2ii—Cs1—H3O | 121.5 (5) |
C1—C12—C11 | 100.72 (18) | Cs1ii—Cs1—H3O | 41.2 (5) |
C13—C12—C11 | 104.30 (18) | C2—O1—C11 | 107.60 (17) |
O4—C13—C14 | 127.9 (2) | C11—O2—Cs1ii | 123.60 (14) |
O4—C13—C12 | 124.6 (2) | C11—O2—H2O | 110 (3) |
C14—C13—C12 | 107.4 (2) | Cs1ii—O2—H2O | 68 (3) |
C15—C14—C19 | 121.5 (2) | C12—O3—Cs1 | 116.40 (13) |
C15—C14—C13 | 110.2 (2) | C12—O3—Cs1ii | 128.36 (13) |
C19—C14—C13 | 128.3 (2) | Cs1—O3—Cs1ii | 103.23 (5) |
C14—C15—C16 | 120.6 (2) | C12—O3—H3O | 105 (2) |
C14—C15—C11 | 112.3 (2) | Cs1—O3—H3O | 110 (2) |
C16—C15—C11 | 127.1 (2) | Cs1ii—O3—H3O | 90 (2) |
C17—C16—C15 | 117.7 (3) | C13—O4—Cs1 | 118.88 (15) |
C17—C16—H16 | 121.1 | C6—O5—C21 | 106.32 (17) |
C15—C16—H16 | 121.1 | C6—O5—Cs1 | 130.11 (13) |
C16—C17—C18 | 121.7 (3) | C21—O5—Cs1 | 122.45 (12) |
C16—C17—H17 | 119.2 | C21—O6—H6O | 107 (3) |
C18—C17—H17 | 119.2 | C22—O7—Cs1i | 156.51 (16) |
C19—C18—C17 | 120.6 (3) | C22—O7—H7O | 104 (3) |
C19—C18—H18 | 119.7 | Cs1i—O7—H7O | 92 (3) |
C17—C18—H18 | 119.7 | O1A—C1A—O2A | 124.0 (2) |
C18—C19—C14 | 117.9 (3) | O1A—C1A—C2A | 118.1 (2) |
C18—C19—H19 | 121.1 | O2A—C1A—C2A | 118.0 (2) |
C14—C19—H19 | 121.1 | C1A—C2A—H2A1 | 109.5 |
O6—C21—O5 | 104.28 (18) | C1A—C2A—H2A2 | 109.5 |
O6—C21—C25 | 114.35 (19) | H2A1—C2A—H2A2 | 109.5 |
O5—C21—C25 | 110.50 (18) | C1A—C2A—H2A3 | 109.5 |
O6—C21—C22 | 115.48 (19) | H2A1—C2A—H2A3 | 109.5 |
O5—C21—C22 | 107.60 (18) | H2A2—C2A—H2A3 | 109.5 |
C25—C21—C22 | 104.53 (18) | C1A—O1A—Cs1 | 114.97 (17) |
O7—C22—C5 | 113.06 (19) | O1E—C1E—C2E | 110.5 (4) |
O7—C22—C23 | 108.95 (19) | O1E—C1E—H1E1 | 109.6 |
C5—C22—C23 | 115.6 (2) | C2E—C1E—H1E1 | 109.6 |
O7—C22—C21 | 115.02 (19) | O1E—C1E—H1E2 | 109.6 |
C5—C22—C21 | 100.30 (17) | C2E—C1E—H1E2 | 109.6 |
C23—C22—C21 | 103.53 (19) | H1E1—C1E—H1E2 | 108.1 |
O8—C23—C24 | 127.4 (2) | C1E—C2E—H2E1 | 109.5 |
O8—C23—C22 | 125.3 (2) | C1E—C2E—H2E2 | 109.5 |
C24—C23—C22 | 107.3 (2) | H2E1—C2E—H2E2 | 109.5 |
C25—C24—C29 | 120.6 (3) | C1E—C2E—H2E3 | 109.5 |
C25—C24—C23 | 110.6 (2) | H2E1—C2E—H2E3 | 109.5 |
C29—C24—C23 | 128.8 (2) | H2E2—C2E—H2E3 | 109.5 |
C26—C25—C24 | 121.5 (2) | C1E—O1E—Cs1 | 131.0 (2) |
C26—C25—C21 | 127.6 (2) | C1E—O1E—H1E | 101 (3) |
C24—C25—C21 | 110.9 (2) | Cs1—O1E—H1E | 111 (3) |
C25—C26—C27 | 117.3 (3) | O2E—C3E—C4E | 112.8 (3) |
C25—C26—H26 | 121.4 | O2E—C3E—H3E1 | 109.0 |
C27—C26—H26 | 121.4 | C4E—C3E—H3E1 | 109.0 |
C26—C27—C28 | 121.1 (3) | O2E—C3E—H3E2 | 109.0 |
C26—C27—H27 | 119.5 | C4E—C3E—H3E2 | 109.0 |
C28—C27—H27 | 119.5 | H3E1—C3E—H3E2 | 107.8 |
C29—C28—C27 | 121.5 (3) | C3E—C4E—H4E1 | 109.5 |
C29—C28—H28 | 119.2 | C3E—C4E—H4E2 | 109.5 |
C27—C28—H28 | 119.2 | H4E1—C4E—H4E2 | 109.5 |
C28—C29—C24 | 118.0 (3) | C3E—C4E—H4E3 | 109.5 |
C28—C29—H29 | 121.0 | H4E1—C4E—H4E3 | 109.5 |
C24—C29—H29 | 121.0 | H4E2—C4E—H4E3 | 109.5 |
O7i—Cs1—O3 | 74.74 (5) | C3E—O2E—H1E | 120.1 (14) |
O7i—Cs1—O1E | 110.43 (6) | C3E—O2E—H2E | 113 (3) |
O3—Cs1—O1E | 148.09 (7) | H1E—O2E—H2E | 96 (3) |
O7i—Cs1—O4 | 113.67 (5) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O1Aii | 0.72 (4) | 1.98 (4) | 2.704 (3) | 175 (4) |
O3—H3O···O2Aii | 0.72 (3) | 1.92 (3) | 2.643 (3) | 179 (4) |
O6—H6O···O2Aiii | 0.68 (4) | 1.98 (4) | 2.650 (3) | 175 (4) |
O7—H7O···O6i | 0.70 (4) | 2.10 (4) | 2.798 (3) | 173 (4) |
O1E—H1E···O2E | 0.84 (4) | 1.92 (5) | 2.747 (4) | 166 (4) |
O2E—H2E···O1A | 0.82 (4) | 1.93 (4) | 2.736 (3) | 170 (4) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x, −y, −z+2; (iii) x+1, y, z. |
Acknowledgements
This research was supported by the Pazy Research Foundation.
References
Almog, J., Gavish-Abramovich, I., Rozin, R., Cohen, S., Yardeni, G. & Zilbermann, I. (2012). Eur. J. Inorg. Chem. pp. 4427–4432. Web of Science CSD CrossRef Google Scholar
Almog, J., Rozin, R., Klein, A., Shamuilov-Levinton, G. & Cohen, S. (2009). Tetrahedron, 65, 7954–7962. Web of Science CSD CrossRef CAS Google Scholar
Bengiat, R., Gil, M., Klein, A., Bogoslavsky, B., Cohen, S. & Almog, J. (2016a). Acta Cryst. E72, 399–402. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bengiat, R., Gil, M., Klein, A., Bogoslavsky, B., Cohen, S., Dubnikova, F., Yardeni, G., Zilbermann, I. & Almog, J. (2016b). Dalton Trans. 45, 8734–8739. CSD CrossRef CAS PubMed Google Scholar
Bengiat, R., Gil, M., Klein, A., Cohen, O., Bogoslavsky, B., Cohen, S., Dubnikova, F. & Almog, J. (2016c). Tetrahedron, 72, 2429–2439. Web of Science CSD CrossRef CAS Google Scholar
Bengiat, R., Klein, A., Gil, M., Bogoslavsky, B., Cohen, S., Yardeni, G., Zilbermann, I. & Almog, J. (2016d). IUCrData, 1, x160261. Google Scholar
Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gil, M., Almog, J., Dubnikova, F., Bogoslavski, B. & Cohen, S. (2014). Acta Cryst. E70, o506. CSD CrossRef IUCr Journals Google Scholar
Janiak, C. (2000). J. Chem. Soc. Dalton Trans. pp. 3885–3896. Web of Science CrossRef Google Scholar
Kundu, S. K., Patra, A. & Pramanik, A. (2004). ChemInform, 35, 604–611. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mahmood, K., Yaqub, M., Tahir, M. N., Shafiq, Z. & Qureshi, A. M. (2011). Acta Cryst. E67, o910–o911. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Manku, G. S. (1980). In Theoretical Principles of Inorganic Chemistry. Tata McGraw-Hill. Google Scholar
Na, J. E., Lee, K. Y., Seo, J. & Kim, J. N. (2005). Tetrahedron Lett. 46, 4505–4508. Web of Science CSD CrossRef CAS Google Scholar
Shannon, R. D. (1976). Acta Cryst. A32, 751–767. CrossRef CAS IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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