Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011916/cf6095sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011916/cf6095Isup2.hkl |
CCDC reference: 170870
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.006 Å
- R factor = 0.028
- wR factor = 0.075
- Data-to-parameter ratio = 23.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
ABSTM_02 Alert A Test not performed as the _exptl_absorpt_correction_type has not been identified. See test ABSTY_01. ABSTY_01 Alert A The absorption correction should be one of the following * none * analytical * integration * numerical * gaussian * empirical * psi-scan * multi-scan * refdelf * sphere * cylinder
2 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check
Equimolar amounts of caesium iodide and 18-crown-6 were dissolved in anhydrous methanol followed by addition of p-xylene. Slow evaporation in a calcium chloride desiccator yielded crystals suitable for X-ray analysis.
The C—H atoms were added at their calculated positions (U = 1.2 times that of the corresponding C atom) and refined using a riding model.
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXTL (Siemens, 1996); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C24H48Cs2I2O12·C8H10 | F(000) = 1124 |
Mr = 1154.40 | Dx = 1.743 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
a = 15.436 (1) Å | Cell parameters from 7131 reflections |
b = 17.4317 (11) Å | θ = 1.8–28.3° |
c = 8.1756 (5) Å | µ = 3.11 mm−1 |
β = 91.195 (1)° | T = 298 K |
V = 2199.4 (2) Å3 | Plate, colourless |
Z = 2 | 0.50 × 0.25 × 0.15 mm |
CCD area-detector diffractometer | 2742 independent reflections |
Radiation source: fine-focus sealed tube | 2385 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ϕ and ω scans | θmax = 28.3°, θmin = 1.8° |
Absorption correction: multi-scan (XPREP, Siemens, 1996) | h = −18→19 |
Tmin = 0.386, Tmax = 0.627 | k = −23→16 |
7131 measured reflections | l = −10→10 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0345P)2 + 2.918P] where P = (Fo2 + 2Fc2)/3 |
2742 reflections | (Δ/σ)max < 0.001 |
115 parameters | Δρmax = 1.20 e Å−3 |
0 restraints | Δρmin = −1.08 e Å−3 |
C24H48Cs2I2O12·C8H10 | V = 2199.4 (2) Å3 |
Mr = 1154.40 | Z = 2 |
Monoclinic, C2/m | Mo Kα radiation |
a = 15.436 (1) Å | µ = 3.11 mm−1 |
b = 17.4317 (11) Å | T = 298 K |
c = 8.1756 (5) Å | 0.50 × 0.25 × 0.15 mm |
β = 91.195 (1)° |
CCD area-detector diffractometer | 2742 independent reflections |
Absorption correction: multi-scan (XPREP, Siemens, 1996) | 2385 reflections with I > 2σ(I) |
Tmin = 0.386, Tmax = 0.627 | Rint = 0.037 |
7131 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.20 e Å−3 |
2742 reflections | Δρmin = −1.08 e Å−3 |
115 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cs1 | 0.170972 (16) | 0.0000 | 0.36783 (3) | 0.04777 (9) | |
I1 | 0.0000 | 0.150813 (17) | 0.5000 | 0.05492 (10) | |
O1 | 0.3636 (3) | 0.0000 | 0.5128 (6) | 0.0904 (13) | |
O2 | 0.29407 (16) | 0.14338 (15) | 0.4161 (4) | 0.0693 (7) | |
O3 | 0.20804 (17) | 0.14078 (15) | 0.1049 (3) | 0.0672 (6) | |
O4 | 0.1305 (2) | 0.0000 | 0.0011 (4) | 0.0645 (9) | |
C1 | 0.3762 (3) | 0.0690 (3) | 0.6022 (6) | 0.0924 (15) | |
H1A | 0.4309 | 0.0667 | 0.6626 | 0.111* | |
H1B | 0.3302 | 0.0750 | 0.6801 | 0.111* | |
C2 | 0.3764 (3) | 0.1343 (3) | 0.4910 (6) | 0.0806 (12) | |
H2A | 0.3918 | 0.1805 | 0.5511 | 0.097* | |
H2B | 0.4194 | 0.1263 | 0.4078 | 0.097* | |
C3 | 0.2924 (3) | 0.2057 (2) | 0.3048 (5) | 0.0711 (10) | |
H3A | 0.3405 | 0.2014 | 0.2308 | 0.085* | |
H3B | 0.2986 | 0.2536 | 0.3645 | 0.085* | |
C4 | 0.2104 (3) | 0.2058 (2) | 0.2110 (5) | 0.0711 (10) | |
H4A | 0.1621 | 0.2037 | 0.2850 | 0.085* | |
H4B | 0.2054 | 0.2525 | 0.1471 | 0.085* | |
C5 | 0.1301 (3) | 0.1360 (2) | 0.0124 (5) | 0.0774 (11) | |
H5A | 0.1225 | 0.1821 | −0.0530 | 0.093* | |
H5B | 0.0814 | 0.1318 | 0.0850 | 0.093* | |
C6 | 0.1333 (3) | 0.0680 (3) | −0.0955 (5) | 0.0792 (12) | |
H6A | 0.0845 | 0.0688 | −0.1721 | 0.095* | |
H6B | 0.1862 | 0.0688 | −0.1575 | 0.095* | |
C7 | 0.0000 | 0.3329 (4) | 0.0000 | 0.096 (2) | |
H7A | 0.0556 | 0.3145 | −0.0330 | 0.115* | 0.50 |
H7B | −0.0440 | 0.3145 | −0.0750 | 0.115* | 0.50 |
H7C | −0.0116 | 0.3145 | 0.1080 | 0.115* | 0.50 |
C8 | 0.0000 | 0.4192 (3) | 0.0000 | 0.0596 (11) | |
C9 | 0.0726 (2) | 0.4604 (2) | −0.0427 (4) | 0.0598 (8) | |
H9 | 0.1225 | 0.4342 | −0.0720 | 0.072* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cs1 | 0.04634 (15) | 0.04223 (14) | 0.05461 (16) | 0.000 | −0.00198 (10) | 0.000 |
I1 | 0.04822 (16) | 0.04972 (17) | 0.0672 (2) | 0.000 | 0.00949 (13) | 0.000 |
O1 | 0.100 (3) | 0.073 (3) | 0.097 (3) | 0.000 | −0.046 (3) | 0.000 |
O2 | 0.0538 (13) | 0.0588 (14) | 0.0953 (19) | −0.0105 (11) | 0.0046 (13) | −0.0034 (13) |
O3 | 0.0611 (14) | 0.0547 (13) | 0.0859 (18) | 0.0076 (11) | 0.0078 (13) | 0.0026 (12) |
O4 | 0.079 (2) | 0.066 (2) | 0.0484 (17) | 0.000 | −0.0109 (16) | 0.000 |
C1 | 0.077 (3) | 0.122 (4) | 0.077 (3) | −0.026 (3) | −0.025 (2) | −0.004 (3) |
C2 | 0.062 (2) | 0.071 (2) | 0.108 (3) | −0.015 (2) | −0.006 (2) | −0.025 (2) |
C3 | 0.072 (2) | 0.0459 (18) | 0.097 (3) | −0.0115 (16) | 0.027 (2) | −0.0073 (18) |
C4 | 0.077 (2) | 0.0413 (16) | 0.096 (3) | 0.0063 (16) | 0.029 (2) | 0.0049 (17) |
C5 | 0.081 (3) | 0.068 (2) | 0.083 (3) | 0.017 (2) | −0.001 (2) | 0.027 (2) |
C6 | 0.083 (3) | 0.094 (3) | 0.060 (2) | 0.009 (2) | −0.0113 (19) | 0.019 (2) |
C7 | 0.112 (5) | 0.059 (3) | 0.118 (5) | 0.000 | 0.035 (4) | 0.000 |
C8 | 0.068 (3) | 0.060 (3) | 0.051 (2) | 0.000 | 0.005 (2) | 0.000 |
C9 | 0.0523 (17) | 0.072 (2) | 0.0554 (17) | 0.0096 (15) | 0.0059 (14) | −0.0001 (15) |
Cs1—O4 | 3.050 (3) | O1—C1i | 1.418 (5) |
Cs1—O2 | 3.159 (2) | O2—C2 | 1.408 (5) |
Cs1—O2i | 3.159 (2) | O2—C3 | 1.417 (5) |
Cs1—O1 | 3.178 (4) | O3—C5 | 1.410 (5) |
Cs1—O3i | 3.320 (3) | O3—C4 | 1.427 (5) |
Cs1—O3 | 3.320 (3) | O4—C6i | 1.425 (4) |
Cs1—C5i | 3.793 (4) | O4—C6 | 1.425 (4) |
Cs1—C5 | 3.793 (4) | C1—C2 | 1.457 (7) |
Cs1—C1 | 3.860 (4) | C3—C4 | 1.466 (6) |
Cs1—C1i | 3.860 (4) | C5—C6 | 1.480 (6) |
Cs1—C4i | 3.862 (4) | C7—C8 | 1.504 (8) |
Cs1—C4 | 3.862 (4) | C8—C9 | 1.382 (4) |
Cs1—I1 | 3.8940 (3) | C8—C9ii | 1.382 (4) |
O1—C1 | 1.418 (5) | C9—C9iii | 1.381 (8) |
O4—Cs1—O2 | 103.47 (7) | O1—Cs1—C4i | 88.35 (8) |
O4—Cs1—O2i | 103.47 (7) | O3i—Cs1—C4i | 21.24 (8) |
O2—Cs1—O2i | 104.57 (10) | O3—Cs1—C4i | 116.18 (8) |
O4—Cs1—O1 | 122.51 (12) | C5i—Cs1—C4i | 35.89 (10) |
O2—Cs1—O1 | 52.97 (5) | C5—Cs1—C4i | 110.55 (10) |
O2i—Cs1—O1 | 52.97 (5) | C1—Cs1—C4i | 108.71 (11) |
O4—Cs1—O3i | 52.99 (6) | C1i—Cs1—C4i | 75.05 (11) |
O2—Cs1—O3i | 123.66 (7) | O4—Cs1—C4 | 72.78 (7) |
O2i—Cs1—O3i | 52.03 (7) | O2—Cs1—C4 | 37.64 (9) |
O1—Cs1—O3i | 93.95 (8) | O2i—Cs1—C4 | 132.66 (8) |
O4—Cs1—O3 | 52.99 (6) | O1—Cs1—C4 | 88.35 (8) |
O2—Cs1—O3 | 52.03 (7) | O3i—Cs1—C4 | 116.18 (8) |
O2i—Cs1—O3 | 123.66 (7) | O3—Cs1—C4 | 21.24 (8) |
O1—Cs1—O3 | 93.95 (8) | C5i—Cs1—C4 | 110.55 (10) |
O3i—Cs1—O3 | 95.33 (9) | C5—Cs1—C4 | 35.89 (10) |
O4—Cs1—C5i | 38.69 (7) | C1—Cs1—C4 | 75.05 (11) |
O2—Cs1—C5i | 132.85 (9) | C1i—Cs1—C4 | 108.71 (11) |
O2i—Cs1—C5i | 72.00 (9) | C4i—Cs1—C4 | 136.51 (12) |
O1—Cs1—C5i | 115.15 (10) | I1—Cs1—I1i | 84.929 (10) |
O3i—Cs1—C5i | 21.57 (8) | Cs1—I1—Cs1iv | 95.071 (10) |
O3—Cs1—C5i | 89.67 (9) | C1—O1—C1i | 116.0 (5) |
O4—Cs1—C5 | 38.69 (7) | C1—O1—Cs1 | 108.0 (3) |
O2—Cs1—C5 | 72.00 (9) | C1i—O1—Cs1 | 108.0 (3) |
O2i—Cs1—C5 | 132.85 (9) | C2—O2—C3 | 111.7 (3) |
O1—Cs1—C5 | 115.15 (10) | C2—O2—Cs1 | 120.0 (2) |
O3i—Cs1—C5 | 89.67 (9) | C3—O2—Cs1 | 121.6 (2) |
O3—Cs1—C5 | 21.57 (8) | C5—O3—C4 | 112.5 (3) |
C5i—Cs1—C5 | 77.38 (15) | C5—O3—Cs1 | 98.5 (2) |
O4—Cs1—C1 | 129.57 (10) | C4—O3—Cs1 | 101.3 (2) |
O2—Cs1—C1 | 37.47 (10) | C6i—O4—C6 | 112.5 (4) |
O2i—Cs1—C1 | 72.50 (10) | C6i—O4—Cs1 | 122.5 (2) |
O1—Cs1—C1 | 20.45 (10) | C6—O4—Cs1 | 122.5 (2) |
O3i—Cs1—C1 | 113.64 (10) | O1—C1—C2 | 110.1 (4) |
O3—Cs1—C1 | 86.58 (9) | O1—C1—Cs1 | 51.5 (2) |
C5i—Cs1—C1 | 134.16 (11) | C2—C1—Cs1 | 86.9 (2) |
C5—Cs1—C1 | 107.89 (11) | O2—C2—C1 | 110.2 (3) |
O4—Cs1—C1i | 129.57 (10) | O2—C3—C4 | 109.9 (3) |
O2—Cs1—C1i | 72.50 (10) | O3—C4—C3 | 109.2 (3) |
O2i—Cs1—C1i | 37.47 (10) | O3—C4—Cs1 | 57.45 (17) |
O1—Cs1—C1i | 20.45 (10) | C3—C4—Cs1 | 88.1 (2) |
O3i—Cs1—C1i | 86.58 (9) | O3—C5—C6 | 109.1 (3) |
O3—Cs1—C1i | 113.64 (10) | O3—C5—Cs1 | 59.96 (17) |
C5i—Cs1—C1i | 107.89 (11) | C6—C5—Cs1 | 87.0 (2) |
C5—Cs1—C1i | 134.16 (11) | O4—C6—C5 | 109.6 (3) |
C1—Cs1—C1i | 36.30 (17) | C9—C8—C9ii | 117.4 (5) |
O4—Cs1—C4i | 72.78 (7) | C9—C8—C7 | 121.3 (2) |
O2—Cs1—C4i | 132.66 (8) | C9ii—C8—C7 | 121.3 (2) |
O2i—Cs1—C4i | 37.64 (9) | C9iii—C9—C8 | 121.3 (2) |
Symmetry codes: (i) x, −y, z; (ii) −x, y, −z; (iii) x, −y+1, z; (iv) −x, y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C24H48Cs2I2O12·C8H10 |
Mr | 1154.40 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 298 |
a, b, c (Å) | 15.436 (1), 17.4317 (11), 8.1756 (5) |
β (°) | 91.195 (1) |
V (Å3) | 2199.4 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.11 |
Crystal size (mm) | 0.50 × 0.25 × 0.15 |
Data collection | |
Diffractometer | CCD area-detector diffractometer |
Absorption correction | Multi-scan (XPREP, Siemens, 1996) |
Tmin, Tmax | 0.386, 0.627 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7131, 2742, 2385 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.075, 1.09 |
No. of reflections | 2742 |
No. of parameters | 115 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.20, −1.08 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXTL (Siemens, 1996), SHELXTL.
Cs1—O4 | 3.050 (3) | Cs1—O3 | 3.320 (3) |
Cs1—O2 | 3.159 (2) | Cs1—C5 | 3.793 (4) |
Cs1—O1 | 3.178 (4) | Cs1—I1 | 3.8940 (3) |
I1—Cs1—I1i | 84.929 (10) | Cs1—I1—Cs1ii | 95.071 (10) |
Symmetry codes: (i) x, −y, z; (ii) −x, y, −z+1. |
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The chemistry of macrocyclic complexes of alkali metal cations has developed intensively since the end of the 1960's because of the strong complexing properties of crown ethers. In this case, the complementarity of the macrocyclic cavity and the cation substrate determines the type of complex (Dietrich et al., 1993). A caesium ion is too large for the 18-crown-6 cavity, thus giving a sandwich dimer complex bridged by SCN- anions (Dobler & Phizackerley, 1974) or water molecules (Rusanova et al., 1999). We report here the sandwich dimer structure of the title compound (I) with bridging iodide ions.
The title compound adopts a molecular dimeric array consisting of two [Cs(18-crown-6)]+ units linked via two iodide ions as shown in Figure 1. Two caesium cations are positioned on a mirror plane and two iodide ions are located on a twofold symmetry axis perpendicular to the mirror plane. The asymmetric unit, therefore, consists of a quarter of Cs2(18-crown-6)2I2.
Important bond distances and angles are presented in Table 1. The caesium ion adopts eightfold coordination. The bond distances between Cs and O atoms in the crown ether span a range of 3.050 (3)–3.320 (3) Å and the average distance is 3.198 Å. The caesium ion is located 1.520 (2) Å above the mean O plane of the crown ring, which has a mean deviation of 0.22 Å. This value is slightly larger than those reported previously for the related complexes, 1.44 Å in [Cs2(18-crown-6)2(SCN)2] (Dobler & Phizackerley, 1974) and 1.48 Å in [Cs2(18-crown-6)2(H2O)2] (Rusanova et al., 1999). The dihedral angle between the plane consisting of two caesium and two iodide ions and the mean O plane of the crown ether is 76.75 (4)°.
The p-xylene molecules are packed in the voids between the dimer complexes. The centre of p-xylene is located on a position of 2/m symmetry. We also determined the crystal structure of Cs2(18-crown-6)2I2.toluene. The structure is nearly identical to that of the title compound. The toluene molecule is also located at a special position of 2/m symmetry in the C2/m unit cell, so that the non-centrosymmetric toluene molecules are disordered over the inversion centre to give an image like the p-xylene molecule.