Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030151/hb6269sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030151/hb6269IVsup2.hkl |
CCDC reference: 287569
To a stirred solution of potassium chlorochromate (241 mg, 1.38 mmol) in dry ethyl acetate (10 ml) at room temperature was added a solution of [1.5]dibenzo-18-crown-6 (497 mg, 1.38 mmol) in dry ethyl acetate (7 ml). The reaction mixture was stirred for 10 min and the yellow–orange precipitate which formed was filtered off, washed with cold ethyl acetate (2 ml) and diethyl ether (2 ml), dried at reduced pressure and heated at 313 K to constant weight (yield 65%, 480 mg). Transparent yellow crystals of (IV), suitable for X-ray investigation [m.p. 417–420 K (decomposition)] were obtained by evaporation of a dichloromethane solution. Analysis, calculated for C20H24O9ClCrK: C 44.90, H 4.52, Cl 6.63, Cr 9.72%; found: C 44.99, H 4.38, Cl 6.56, Cr 9.60%. The crystals are soluble in dichloromethane, dimethyl sulfoxide, dimethyl formamide and acetone, and sparingly soluble in chloroform.
The disordered atoms which occupy neighbouring sites (O8' and Cl1, and O8 and Cl1') were constrained to have the same Uij components and their site occupancies were constrained to sum to unity. The Cr1—O8 and Cr1—O8' bond lengths were restrained to 1.59 (1) Å. All H atoms were placed in calculated positions and included in the refnement in the riding-model approximation, with C—H distances in the range 0.97–0.98 Å and with Uiso(H) = 1.2Ueq(C).
Data collection: P3/PC (Siemens, 1989); cell refinement: P3/PC; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. A view of (IV), with displacement ellipsoids drawn at the 50% probability level. The minor disorder component of the anion is indicated by primed atoms. |
[K(C20H24O6)][CrClO3] | Z = 2 |
Mr = 534.94 | F(000) = 552 |
Triclinic, P1 | Dx = 1.490 Mg m−3 |
Hall symbol: -P 1 | Melting point: 417 K |
a = 10.139 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.649 (4) Å | Cell parameters from 24 reflections |
c = 12.138 (3) Å | θ = 12–16° |
α = 95.34 (3)° | µ = 0.81 mm−1 |
β = 94.11 (2)° | T = 295 K |
γ = 113.05 (2)° | Block, yellow |
V = 1192.3 (7) Å3 | 0.30 × 0.20 × 0.20 mm |
Siemens P3/PC diffractometer | Rint = 0.069 |
Radiation source: fine-focus sealed tube | θmax = 25.1°, θmin = 1.7° |
Graphite monochromator | h = 0→12 |
θ/2θ scans | k = −12→11 |
4317 measured reflections | l = −14→14 |
4067 independent reflections | 2 standard reflections every 98 reflections |
2703 reflections with I > 2σ(I) | intensity decay: 3% |
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.197 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.1033P)2 + 1.1342P] where P = (Fo2 + 2Fc2)/3 |
4067 reflections | (Δ/σ)max = 0.003 |
296 parameters | Δρmax = 0.76 e Å−3 |
2 restraints | Δρmin = −0.39 e Å−3 |
[K(C20H24O6)][CrClO3] | γ = 113.05 (2)° |
Mr = 534.94 | V = 1192.3 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.139 (3) Å | Mo Kα radiation |
b = 10.649 (4) Å | µ = 0.81 mm−1 |
c = 12.138 (3) Å | T = 295 K |
α = 95.34 (3)° | 0.30 × 0.20 × 0.20 mm |
β = 94.11 (2)° |
Siemens P3/PC diffractometer | Rint = 0.069 |
4317 measured reflections | 2 standard reflections every 98 reflections |
4067 independent reflections | intensity decay: 3% |
2703 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.068 | 2 restraints |
wR(F2) = 0.197 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.76 e Å−3 |
4067 reflections | Δρmin = −0.39 e Å−3 |
296 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) | |
Cl1 | 0.5525 (4) | 0.1504 (6) | 0.5885 (3) | 0.1460 (18) | 0.729 (8) |
O8 | 0.4662 (15) | 0.3387 (14) | 0.7385 (15) | 0.104 (2) | 0.729 (8) |
O8' | 0.607 (3) | 0.204 (4) | 0.6318 (13) | 0.1460 (18) | 0.271 (8) |
Cl1' | 0.4607 (17) | 0.3847 (15) | 0.7242 (17) | 0.104 (2) | 0.271 (8) |
Cr1 | 0.55972 (10) | 0.24649 (10) | 0.74816 (9) | 0.0804 (4) | |
K1 | 0.20725 (11) | 0.14150 (11) | 0.81423 (9) | 0.0561 (3) | |
O1 | 0.1217 (4) | −0.1193 (3) | 0.7012 (3) | 0.0617 (9) | |
O2 | −0.0312 (3) | 0.0115 (3) | 0.6384 (2) | 0.0515 (8) | |
O3 | 0.0070 (4) | 0.2567 (3) | 0.7651 (3) | 0.0606 (9) | |
O4 | 0.2200 (5) | 0.3702 (5) | 0.9467 (4) | 0.1040 (16) | |
O5 | 0.2414 (4) | 0.1445 (4) | 1.0448 (3) | 0.0709 (10) | |
O6 | 0.1958 (3) | −0.1054 (3) | 0.9163 (3) | 0.0594 (8) | |
O7 | 0.7201 (5) | 0.3310 (5) | 0.8044 (6) | 0.1233 (19) | |
O9 | 0.4772 (5) | 0.1297 (5) | 0.8221 (5) | 0.1136 (17) | |
C1 | −0.0168 (5) | −0.2010 (5) | 0.6513 (4) | 0.0493 (10) | |
C2 | −0.0745 (6) | −0.3412 (5) | 0.6371 (4) | 0.0656 (13) | |
H2A | −0.0211 | −0.3886 | 0.6627 | 0.079* | |
C3 | −0.2147 (7) | −0.4130 (6) | 0.5839 (5) | 0.0834 (18) | |
H3A | −0.2547 | −0.5087 | 0.5735 | 0.100* | |
C4 | −0.2927 (6) | −0.3433 (7) | 0.5472 (6) | 0.0865 (18) | |
H4A | −0.3857 | −0.3918 | 0.5112 | 0.104* | |
C5 | −0.2355 (5) | −0.2021 (6) | 0.5627 (4) | 0.0665 (14) | |
H5A | −0.2899 | −0.1557 | 0.5368 | 0.080* | |
C6 | −0.0977 (5) | −0.1282 (5) | 0.6167 (4) | 0.0478 (10) | |
C7 | −0.1178 (5) | 0.0868 (5) | 0.6123 (4) | 0.0596 (12) | |
H7A | −0.2030 | 0.0568 | 0.6512 | 0.071* | |
H7B | −0.1486 | 0.0705 | 0.5329 | 0.071* | |
C8 | −0.0287 (6) | 0.2356 (6) | 0.6477 (4) | 0.0649 (13) | |
H8A | 0.0587 | 0.2645 | 0.6114 | 0.078* | |
H8B | −0.0822 | 0.2896 | 0.6269 | 0.078* | |
C9 | 0.0641 (6) | 0.3971 (5) | 0.8105 (5) | 0.0725 (15) | |
H9A | −0.0088 | 0.4336 | 0.7984 | 0.087* | |
H9B | 0.1462 | 0.4489 | 0.7734 | 0.087* | |
C10 | 0.1093 (7) | 0.4120 (6) | 0.9300 (5) | 0.0776 (16) | |
H10A | 0.1406 | 0.5074 | 0.9619 | 0.093* | |
H10B | 0.0284 | 0.3568 | 0.9667 | 0.093* | |
C11 | 0.2769 (9) | 0.3792 (8) | 1.0587 (6) | 0.104 (2) | |
H11A | 0.2603 | 0.4504 | 1.1038 | 0.125* | |
H11B | 0.3804 | 0.4060 | 1.0622 | 0.125* | |
C12 | 0.2119 (7) | 0.2475 (8) | 1.1063 (5) | 0.091 (2) | |
H12A | 0.2527 | 0.2605 | 1.1833 | 0.109* | |
H12B | 0.1085 | 0.2203 | 1.1045 | 0.109* | |
C13 | 0.1984 (7) | 0.0204 (7) | 1.0887 (5) | 0.0880 (19) | |
H13A | 0.0939 | −0.0248 | 1.0796 | 0.106* | |
H13B | 0.2321 | 0.0374 | 1.1677 | 0.106* | |
C14 | 0.2589 (7) | −0.0697 (6) | 1.0304 (4) | 0.0787 (18) | |
H14A | 0.3629 | −0.0220 | 1.0343 | 0.094* | |
H14B | 0.2377 | −0.1523 | 1.0658 | 0.094* | |
C15 | 0.2535 (5) | −0.1726 (5) | 0.8458 (4) | 0.0537 (12) | |
C16 | 0.3499 (6) | −0.2289 (6) | 0.8784 (6) | 0.0755 (17) | |
H16A | 0.3781 | −0.2250 | 0.9536 | 0.091* | |
C17 | 0.4037 (6) | −0.2901 (7) | 0.7997 (7) | 0.089 (2) | |
H17A | 0.4675 | −0.3286 | 0.8226 | 0.107* | |
C18 | 0.3666 (8) | −0.2962 (7) | 0.6899 (7) | 0.097 (2) | |
H18A | 0.4060 | −0.3364 | 0.6377 | 0.116* | |
C19 | 0.2695 (7) | −0.2421 (6) | 0.6557 (5) | 0.0807 (17) | |
H19A | 0.2431 | −0.2458 | 0.5801 | 0.097* | |
C20 | 0.2119 (5) | −0.1826 (5) | 0.7335 (4) | 0.0577 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.121 (3) | 0.265 (5) | 0.076 (2) | 0.114 (3) | −0.0048 (16) | −0.010 (2) |
O8 | 0.093 (3) | 0.089 (8) | 0.154 (6) | 0.054 (4) | 0.022 (3) | 0.039 (6) |
O8' | 0.121 (3) | 0.265 (5) | 0.076 (2) | 0.114 (3) | −0.0048 (16) | −0.010 (2) |
Cl1' | 0.093 (3) | 0.089 (8) | 0.154 (6) | 0.054 (4) | 0.022 (3) | 0.039 (6) |
Cr1 | 0.0608 (6) | 0.0776 (7) | 0.1049 (8) | 0.0287 (5) | 0.0013 (5) | 0.0246 (6) |
K1 | 0.0531 (6) | 0.0621 (6) | 0.0551 (6) | 0.0281 (5) | −0.0007 (5) | 0.0002 (5) |
O1 | 0.073 (2) | 0.0586 (19) | 0.059 (2) | 0.0409 (18) | −0.0250 (17) | −0.0041 (15) |
O2 | 0.0516 (17) | 0.0592 (19) | 0.0512 (18) | 0.0310 (15) | −0.0032 (14) | 0.0109 (14) |
O3 | 0.077 (2) | 0.054 (2) | 0.059 (2) | 0.0333 (17) | 0.0035 (17) | 0.0158 (16) |
O4 | 0.125 (4) | 0.126 (4) | 0.081 (3) | 0.086 (3) | −0.024 (3) | −0.025 (3) |
O5 | 0.077 (2) | 0.084 (3) | 0.0461 (19) | 0.027 (2) | 0.0114 (17) | 0.0056 (18) |
O6 | 0.0578 (19) | 0.067 (2) | 0.0475 (18) | 0.0199 (17) | −0.0085 (15) | 0.0111 (16) |
O7 | 0.067 (3) | 0.091 (3) | 0.191 (6) | 0.018 (2) | −0.013 (3) | 0.004 (3) |
O9 | 0.078 (3) | 0.114 (4) | 0.159 (5) | 0.038 (3) | 0.012 (3) | 0.073 (3) |
C1 | 0.053 (3) | 0.059 (3) | 0.038 (2) | 0.026 (2) | 0.0011 (19) | 0.007 (2) |
C2 | 0.084 (4) | 0.060 (3) | 0.058 (3) | 0.034 (3) | 0.004 (3) | 0.014 (2) |
C3 | 0.083 (4) | 0.058 (3) | 0.091 (4) | 0.009 (3) | 0.009 (3) | 0.009 (3) |
C4 | 0.052 (3) | 0.079 (4) | 0.109 (5) | 0.011 (3) | −0.006 (3) | 0.001 (4) |
C5 | 0.051 (3) | 0.079 (4) | 0.069 (3) | 0.026 (3) | −0.003 (2) | 0.009 (3) |
C6 | 0.054 (3) | 0.054 (3) | 0.039 (2) | 0.025 (2) | 0.0064 (19) | 0.0105 (19) |
C7 | 0.066 (3) | 0.079 (4) | 0.051 (3) | 0.047 (3) | 0.002 (2) | 0.018 (2) |
C8 | 0.079 (3) | 0.076 (4) | 0.057 (3) | 0.046 (3) | 0.010 (3) | 0.025 (3) |
C9 | 0.078 (4) | 0.056 (3) | 0.088 (4) | 0.030 (3) | 0.006 (3) | 0.015 (3) |
C10 | 0.090 (4) | 0.063 (3) | 0.087 (4) | 0.041 (3) | 0.010 (3) | 0.000 (3) |
C11 | 0.125 (6) | 0.108 (6) | 0.081 (5) | 0.066 (5) | −0.029 (4) | −0.032 (4) |
C12 | 0.080 (4) | 0.133 (6) | 0.050 (3) | 0.042 (4) | −0.004 (3) | −0.029 (4) |
C13 | 0.094 (4) | 0.100 (5) | 0.048 (3) | 0.014 (4) | 0.013 (3) | 0.018 (3) |
C14 | 0.096 (4) | 0.071 (4) | 0.049 (3) | 0.014 (3) | −0.015 (3) | 0.022 (3) |
C15 | 0.044 (2) | 0.048 (3) | 0.063 (3) | 0.013 (2) | −0.009 (2) | 0.014 (2) |
C16 | 0.063 (3) | 0.061 (3) | 0.094 (4) | 0.021 (3) | −0.025 (3) | 0.021 (3) |
C17 | 0.062 (4) | 0.081 (4) | 0.130 (6) | 0.040 (3) | −0.016 (4) | 0.016 (4) |
C18 | 0.097 (5) | 0.094 (5) | 0.126 (6) | 0.067 (4) | 0.019 (4) | 0.008 (4) |
C19 | 0.099 (4) | 0.087 (4) | 0.074 (4) | 0.058 (4) | 0.002 (3) | 0.011 (3) |
C20 | 0.061 (3) | 0.055 (3) | 0.062 (3) | 0.032 (2) | −0.007 (2) | 0.006 (2) |
Cr1—Cl1 | 2.088 (4) | C4—H4A | 0.9300 |
Cr1—O8 | 1.617 (8) | C5—C6 | 1.383 (7) |
Cr1—O8' | 1.605 (10) | C5—H5A | 0.9300 |
Cr1—Cl1' | 2.110 (11) | C7—C8 | 1.486 (7) |
Cr1—O7 | 1.581 (5) | C7—H7A | 0.9700 |
Cr1—O9 | 1.597 (5) | C7—H7B | 0.9700 |
K1—O1 | 2.753 (3) | C8—H8A | 0.9700 |
K1—O2 | 2.899 (3) | C8—H8B | 0.9700 |
K1—O3 | 2.810 (3) | C9—C10 | 1.464 (8) |
K1—O4 | 2.744 (4) | C9—H9A | 0.9700 |
K1—O5 | 2.791 (4) | C9—H9B | 0.9700 |
K1—O6 | 2.975 (4) | C10—H10A | 0.9700 |
K1—O8 | 2.922 (15) | C10—H10B | 0.9700 |
K1—O9 | 2.784 (5) | C11—C12 | 1.489 (10) |
K1—Cl1' | 3.197 (14) | C11—H11A | 0.9700 |
C1—O1 | 1.385 (5) | C11—H11B | 0.9700 |
C20—O1 | 1.388 (5) | C12—H12A | 0.9700 |
O2—C6 | 1.362 (5) | C12—H12B | 0.9700 |
O2—C7 | 1.439 (5) | C13—C14 | 1.480 (9) |
O3—C9 | 1.413 (6) | C13—H13A | 0.9700 |
O3—C8 | 1.419 (6) | C13—H13B | 0.9700 |
O4—C10 | 1.369 (7) | C14—H14A | 0.9700 |
O4—C11 | 1.417 (8) | C14—H14B | 0.9700 |
O5—C13 | 1.390 (7) | C15—C20 | 1.379 (7) |
O5—C12 | 1.409 (7) | C15—C16 | 1.385 (7) |
O6—C15 | 1.368 (6) | C16—C17 | 1.368 (9) |
O6—C14 | 1.434 (6) | C16—H16A | 0.9300 |
C1—C2 | 1.361 (7) | C17—C18 | 1.348 (10) |
C1—C6 | 1.400 (6) | C17—H17A | 0.9300 |
C2—C3 | 1.395 (8) | C18—C19 | 1.379 (9) |
C2—H2A | 0.9300 | C18—H18A | 0.9300 |
C3—C4 | 1.358 (9) | C19—C20 | 1.375 (8) |
C3—H3A | 0.9300 | C19—H19A | 0.9300 |
C4—C5 | 1.371 (8) | ||
Cr1—O8—K1 | 95.8 (5) | O1—C1—C6 | 114.7 (4) |
Cr1—Cl1'—K1 | 79.1 (4) | C1—C2—C3 | 119.4 (5) |
O7—Cr1—O9 | 109.4 (3) | C1—C2—H2A | 120.3 |
O7—Cr1—O8' | 94.1 (11) | C3—C2—H2A | 120.3 |
O9—Cr1—O8' | 119.6 (14) | C4—C3—C2 | 120.1 (5) |
O7—Cr1—O8 | 113.6 (6) | C4—C3—H3A | 119.9 |
O9—Cr1—O8 | 106.1 (6) | C2—C3—H3A | 119.9 |
O8'—Cr1—O8 | 113.8 (13) | C3—C4—C5 | 120.6 (5) |
O7—Cr1—Cl1 | 111.9 (3) | C3—C4—H4A | 119.7 |
O9—Cr1—Cl1 | 107.9 (3) | C5—C4—H4A | 119.7 |
O8'—Cr1—Cl1 | 18.1 (12) | C4—C5—C6 | 120.6 (5) |
O8—Cr1—Cl1 | 107.7 (7) | C4—C5—H5A | 119.7 |
O7—Cr1—Cl1' | 108.8 (5) | C6—C5—H5A | 119.7 |
O9—Cr1—Cl1' | 113.9 (5) | O2—C6—C5 | 125.6 (4) |
O8'—Cr1—Cl1' | 108.9 (13) | O2—C6—C1 | 116.1 (4) |
O8—Cr1—Cl1' | 7.9 (9) | C5—C6—C1 | 118.3 (4) |
Cl1—Cr1—Cl1' | 104.9 (6) | O2—C7—C8 | 108.1 (4) |
O4—K1—O1 | 164.36 (15) | O2—C7—H7A | 110.1 |
O4—K1—O9 | 110.88 (17) | C8—C7—H7A | 110.1 |
O1—K1—O9 | 82.04 (14) | O2—C7—H7B | 110.1 |
O4—K1—O5 | 62.08 (13) | C8—C7—H7B | 110.1 |
O1—K1—O5 | 112.23 (12) | H7A—C7—H7B | 108.4 |
O9—K1—O5 | 85.03 (15) | O3—C8—C7 | 108.5 (4) |
O4—K1—O3 | 60.20 (12) | O3—C8—H8A | 110.0 |
O1—K1—O3 | 111.63 (10) | C7—C8—H8A | 110.0 |
O9—K1—O3 | 154.65 (12) | O3—C8—H8B | 110.0 |
O5—K1—O3 | 107.59 (11) | C7—C8—H8B | 110.0 |
O4—K1—O2 | 118.11 (12) | H8A—C8—H8B | 108.4 |
O1—K1—O2 | 54.19 (9) | O3—C9—C10 | 110.1 (4) |
O9—K1—O2 | 127.03 (15) | O3—C9—H9A | 109.3 |
O5—K1—O2 | 135.09 (11) | C10—C9—H9A | 109.8 |
O3—K1—O2 | 58.15 (9) | O3—C9—H9B | 109.9 |
O4—K1—O8 | 83.1 (3) | C10—C9—H9B | 109.5 |
O1—K1—O8 | 112.3 (3) | H9A—C9—H9B | 108.2 |
O9—K1—O8 | 53.43 (18) | O4—C10—C9 | 109.9 (5) |
O5—K1—O8 | 111.3 (4) | O4—C10—H10A | 109.7 |
O3—K1—O8 | 101.22 (18) | C9—C10—H10A | 109.7 |
O2—K1—O8 | 113.2 (4) | O4—C10—H10B | 109.7 |
O4—K1—O6 | 119.89 (13) | C9—C10—H10B | 109.7 |
O1—K1—O6 | 54.71 (9) | H10A—C10—H10B | 108.2 |
O9—K1—O6 | 70.69 (12) | O4—C11—C12 | 113.0 (6) |
O5—K1—O6 | 58.20 (11) | O4—C11—H11A | 109.0 |
O3—K1—O6 | 134.66 (10) | C12—C11—H11A | 109.0 |
O2—K1—O6 | 99.63 (9) | O4—C11—H11B | 109.0 |
O8—K1—O6 | 124.12 (18) | C12—C11—H11B | 109.0 |
O4—K1—Cl1' | 77.7 (4) | H11A—C11—H11B | 107.8 |
O1—K1—Cl1' | 117.1 (4) | O5—C12—C11 | 109.7 (5) |
O9—K1—Cl1' | 62.4 (2) | O5—C12—H12A | 109.5 |
O5—K1—Cl1' | 114.0 (4) | C11—C12—H12A | 109.3 |
O3—K1—Cl1' | 92.2 (2) | O5—C12—H12B | 110.3 |
O2—K1—Cl1' | 109.2 (4) | C11—C12—H12B | 109.9 |
O8—K1—Cl1' | 9.0 (3) | H12A—C12—H12B | 108.1 |
O6—K1—Cl1' | 133.1 (2) | O5—C13—C14 | 109.7 (5) |
O4—K1—Cr1 | 101.85 (12) | O5—C13—H13A | 109.7 |
O1—K1—Cr1 | 93.59 (9) | C14—C13—H13A | 109.7 |
O9—K1—Cr1 | 26.70 (10) | O5—C13—H13B | 109.7 |
O5—K1—Cr1 | 102.81 (9) | C14—C13—H13B | 109.7 |
O3—K1—Cr1 | 128.18 (8) | H13A—C13—H13B | 108.2 |
O2—K1—Cr1 | 119.41 (8) | O6—C14—C13 | 108.8 (5) |
O8—K1—Cr1 | 27.52 (15) | O6—C14—H14A | 109.9 |
O6—K1—Cr1 | 97.02 (8) | C13—C14—H14A | 109.9 |
Cl1'—K1—Cr1 | 36.5 (2) | O6—C14—H14B | 109.9 |
C1—O1—C20 | 118.6 (4) | C13—C14—H14B | 109.9 |
C1—O1—K1 | 125.2 (3) | H14A—C14—H14B | 108.3 |
C20—O1—K1 | 112.1 (3) | O6—C15—C20 | 116.2 (4) |
C6—O2—C7 | 116.5 (4) | O6—C15—C16 | 125.3 (5) |
C6—O2—K1 | 120.4 (2) | C20—C15—C16 | 118.5 (5) |
C7—O2—K1 | 117.1 (3) | C17—C16—C15 | 120.0 (6) |
C9—O3—C8 | 113.0 (4) | C17—C16—H16A | 120.0 |
C9—O3—K1 | 110.1 (3) | C15—C16—H16A | 120.0 |
C8—O3—K1 | 108.0 (3) | C18—C17—C16 | 121.6 (6) |
C10—O4—C11 | 116.9 (5) | C18—C17—H17A | 119.2 |
C10—O4—K1 | 118.1 (4) | C16—C17—H17A | 119.2 |
C11—O4—K1 | 113.2 (4) | C17—C18—C19 | 119.4 (7) |
C13—O5—C12 | 114.7 (5) | C17—C18—H18A | 120.3 |
C13—O5—K1 | 119.3 (3) | C19—C18—H18A | 120.3 |
C12—O5—K1 | 114.4 (4) | C20—C19—C18 | 119.9 (6) |
C15—O6—C14 | 116.9 (4) | C20—C19—H19A | 120.0 |
C15—O6—K1 | 106.2 (2) | C18—C19—H19A | 120.0 |
C14—O6—K1 | 111.5 (3) | C19—C20—C15 | 120.6 (5) |
Cr1—O9—K1 | 101.8 (2) | C19—C20—O1 | 120.9 (5) |
C2—C1—O1 | 124.4 (4) | C15—C20—O1 | 118.1 (4) |
C2—C1—C6 | 120.9 (4) | ||
K1—O8—Cr1—O7 | −135.5 (4) | O8—K1—O5—C13 | −134.6 (4) |
K1—O8—Cr1—O9 | −15.2 (7) | O6—K1—O5—C13 | −16.8 (4) |
K1—O8—Cr1—O8' | 118.4 (15) | Cl1'—K1—O5—C13 | −143.9 (5) |
K1—O8—Cr1—Cl1 | 100.1 (5) | Cr1—K1—O5—C13 | −107.1 (4) |
K1—O8—Cr1—Cl1' | 170 (9) | O4—K1—O5—C12 | 14.8 (4) |
K1—Cl1'—Cr1—O7 | −137.2 (3) | O1—K1—O5—C12 | −149.1 (4) |
K1—Cl1'—Cr1—O9 | −14.8 (6) | O9—K1—O5—C12 | 131.6 (4) |
K1—Cl1'—Cr1—O8' | 121.5 (13) | O3—K1—O5—C12 | −25.9 (4) |
K1—Cl1'—Cr1—O8 | −9 (8) | O2—K1—O5—C12 | −88.2 (4) |
K1—Cl1'—Cr1—Cl1 | 103.0 (3) | O8—K1—O5—C12 | 84.1 (4) |
Cr1—O8—K1—O4 | 132.9 (7) | O6—K1—O5—C12 | −158.1 (4) |
Cr1—O8—K1—O1 | −50.3 (8) | Cl1'—K1—O5—C12 | 74.7 (5) |
Cr1—O8—K1—O9 | 10.4 (5) | Cr1—K1—O5—C12 | 111.5 (4) |
Cr1—O8—K1—O5 | 76.5 (8) | O4—K1—O6—C15 | −153.7 (3) |
Cr1—O8—K1—O3 | −169.4 (6) | O1—K1—O6—C15 | 43.8 (2) |
Cr1—O8—K1—O2 | −109.5 (7) | O9—K1—O6—C15 | −50.1 (3) |
Cr1—O8—K1—O6 | 11.2 (10) | O5—K1—O6—C15 | −146.4 (3) |
Cr1—O8—K1—Cl1' | −175 (5) | O3—K1—O6—C15 | 130.1 (3) |
Cr1—Cl1'—K1—O4 | 130.4 (6) | O2—K1—O6—C15 | 75.9 (3) |
Cr1—Cl1'—K1—O1 | −55.0 (6) | O8—K1—O6—C15 | −50.9 (5) |
Cr1—Cl1'—K1—O9 | 8.7 (4) | Cl1'—K1—O6—C15 | −52.1 (6) |
Cr1—Cl1'—K1—O5 | 78.9 (6) | Cr1—K1—O6—C15 | −45.7 (3) |
Cr1—Cl1'—K1—O3 | −170.8 (5) | O4—K1—O6—C14 | −25.2 (4) |
Cr1—Cl1'—K1—O2 | −113.8 (5) | O1—K1—O6—C14 | 172.2 (4) |
Cr1—Cl1'—K1—O8 | 4 (4) | O9—K1—O6—C14 | 78.3 (4) |
Cr1—Cl1'—K1—O6 | 10.8 (9) | O5—K1—O6—C14 | −17.9 (4) |
O4—K1—O1—C1 | 38.5 (6) | O3—K1—O6—C14 | −101.5 (4) |
O9—K1—O1—C1 | −174.8 (3) | O2—K1—O6—C14 | −155.7 (4) |
O5—K1—O1—C1 | 103.9 (3) | O8—K1—O6—C14 | 77.6 (6) |
O3—K1—O1—C1 | −17.0 (3) | Cl1'—K1—O6—C14 | 76.4 (6) |
O2—K1—O1—C1 | −26.5 (3) | Cr1—K1—O6—C14 | 82.8 (4) |
O8—K1—O1—C1 | −129.8 (4) | O7—Cr1—O9—K1 | 139.2 (3) |
O6—K1—O1—C1 | 113.3 (3) | O8'—Cr1—O9—K1 | −114.1 (11) |
Cl1'—K1—O1—C1 | −121.4 (4) | O8—Cr1—O9—K1 | 16.3 (7) |
Cr1—K1—O1—C1 | −150.7 (3) | Cl1—Cr1—O9—K1 | −98.9 (2) |
O4—K1—O1—C20 | −118.3 (5) | Cl1'—Cr1—O9—K1 | 17.1 (7) |
O9—K1—O1—C20 | 28.4 (3) | O4—K1—O9—Cr1 | −74.4 (3) |
O5—K1—O1—C20 | −52.9 (3) | O1—K1—O9—Cr1 | 114.7 (3) |
O3—K1—O1—C20 | −173.7 (3) | O5—K1—O9—Cr1 | −132.0 (3) |
O2—K1—O1—C20 | 176.7 (3) | O3—K1—O9—Cr1 | −10.3 (6) |
O8—K1—O1—C20 | 73.4 (4) | O2—K1—O9—Cr1 | 82.5 (3) |
O6—K1—O1—C20 | −43.5 (3) | O8—K1—O9—Cr1 | −10.7 (5) |
Cl1'—K1—O1—C20 | 81.8 (4) | O6—K1—O9—Cr1 | 170.1 (3) |
Cr1—K1—O1—C20 | 52.5 (3) | Cl1'—K1—O9—Cr1 | −11.6 (5) |
O4—K1—O2—C6 | −139.6 (3) | K1—O1—C1—C2 | −151.5 (4) |
O1—K1—O2—C6 | 24.3 (3) | C20—O1—C1—C6 | −177.1 (4) |
O9—K1—O2—C6 | 65.0 (3) | K1—O1—C1—C6 | 27.5 (5) |
O5—K1—O2—C6 | −62.1 (3) | O1—C1—C2—C3 | −178.9 (5) |
O3—K1—O2—C6 | −145.2 (3) | C6—C1—C2—C3 | 2.2 (8) |
O8—K1—O2—C6 | 125.8 (3) | C1—C2—C3—C4 | −0.4 (9) |
O6—K1—O2—C6 | −8.0 (3) | C2—C3—C4—C5 | −0.5 (10) |
Cl1'—K1—O2—C6 | 134.5 (4) | C3—C4—C5—C6 | −0.4 (10) |
Cr1—K1—O2—C6 | 95.8 (3) | C7—O2—C6—C5 | 6.3 (6) |
O4—K1—O2—C7 | 12.3 (3) | K1—O2—C6—C5 | 158.4 (4) |
O1—K1—O2—C7 | 176.2 (3) | C7—O2—C6—C1 | −174.6 (4) |
O9—K1—O2—C7 | −143.1 (3) | K1—O2—C6—C1 | −22.6 (5) |
O5—K1—O2—C7 | 89.8 (3) | C4—C5—C6—O2 | −178.7 (5) |
O3—K1—O2—C7 | 6.6 (3) | C4—C5—C6—C1 | 2.2 (8) |
O8—K1—O2—C7 | −82.4 (4) | C2—C1—C6—O2 | 177.7 (4) |
O6—K1—O2—C7 | 143.9 (3) | C2—C1—C6—C5 | −3.1 (7) |
Cl1'—K1—O2—C7 | −73.7 (4) | O1—C1—C6—C5 | 177.9 (4) |
Cr1—K1—O2—C7 | −112.4 (3) | C6—O2—C7—C8 | 176.9 (4) |
O4—K1—O3—C9 | 23.8 (3) | K1—O2—C7—C8 | 23.9 (5) |
O1—K1—O3—C9 | −171.0 (3) | C9—O3—C8—C7 | −167.0 (4) |
O9—K1—O3—C9 | −51.7 (5) | K1—O3—C8—C7 | 71.0 (4) |
O5—K1—O3—C9 | 65.4 (3) | C8—O3—C9—C10 | −175.4 (5) |
O2—K1—O3—C9 | −161.9 (3) | K1—O3—C9—C10 | −54.6 (5) |
O8—K1—O3—C9 | −51.4 (5) | C11—O4—C10—C9 | 179.6 (6) |
O6—K1—O3—C9 | 127.8 (3) | K1—O4—C10—C9 | −39.8 (6) |
Cl1'—K1—O3—C9 | −50.6 (5) | C10—O4—C11—C12 | 95.3 (7) |
Cr1—K1—O3—C9 | −57.6 (3) | K1—O4—C11—C12 | −47.1 (7) |
O4—K1—O3—C8 | 147.6 (3) | C13—O5—C12—C11 | 173.8 (5) |
O1—K1—O3—C8 | −47.2 (3) | K1—O5—C12—C11 | −43.1 (6) |
O9—K1—O3—C8 | 72.1 (5) | C12—O5—C13—C14 | −169.4 (5) |
O5—K1—O3—C8 | −170.8 (3) | K1—O5—C13—C14 | 49.4 (6) |
O2—K1—O3—C8 | −38.1 (3) | C15—O6—C14—C13 | 171.2 (4) |
O8—K1—O3—C8 | 72.4 (5) | K1—O6—C14—C13 | 48.7 (5) |
O6—K1—O3—C8 | −108.4 (3) | C14—O6—C15—C20 | −167.8 (4) |
Cl1'—K1—O3—C8 | 73.2 (5) | K1—O6—C15—C20 | −42.6 (4) |
Cr1—K1—O3—C8 | 66.2 (3) | C14—O6—C15—C16 | 11.4 (7) |
O1—K1—O4—C10 | −53.0 (7) | K1—O6—C15—C16 | 136.7 (4) |
O9—K1—O4—C10 | 162.6 (4) | O6—C15—C16—C17 | −178.0 (5) |
O5—K1—O4—C10 | −125.2 (5) | C20—C15—C16—C17 | 1.2 (8) |
O3—K1—O4—C10 | 9.0 (4) | C15—C16—C17—C18 | 0.8 (10) |
O2—K1—O4—C10 | 3.5 (5) | C16—C17—C18—C19 | −1.5 (11) |
O8—K1—O4—C10 | 116.2 (5) | C17—C18—C19—C20 | 0.1 (10) |
O6—K1—O4—C10 | −118.2 (4) | C18—C19—C20—C15 | 2.0 (9) |
Cl1'—K1—O4—C10 | 108.8 (5) | C18—C19—C20—O1 | 175.6 (5) |
Cr1—K1—O4—C10 | 136.4 (4) | O6—C15—C20—C19 | 176.7 (5) |
O1—K1—O4—C11 | 89.0 (6) | C16—C15—C20—C19 | −2.6 (8) |
O9—K1—O4—C11 | −55.4 (5) | C16—C15—C20—O1 | −176.4 (4) |
O5—K1—O4—C11 | 16.7 (5) | K1—O1—C20—C19 | −129.4 (5) |
O3—K1—O4—C11 | 150.9 (6) | C1—O1—C20—C15 | −114.1 (5) |
O2—K1—O4—C11 | 145.4 (5) | K1—O1—C20—C15 | 44.4 (5) |
O8—K1—O4—C11 | −101.9 (6) | O1—C1—C6—O2 | −1.3 (6) |
O6—K1—O4—C11 | 23.7 (6) | O2—C7—C8—O3 | −63.3 (5) |
Cl1'—K1—O4—C11 | −109.2 (6) | O3—C9—C10—O4 | 64.3 (7) |
Cr1—K1—O4—C11 | −81.6 (5) | O4—C11—C12—O5 | 61.6 (7) |
O4—K1—O5—C13 | 156.1 (5) | O5—C13—C14—O6 | −65.5 (6) |
O1—K1—O5—C13 | −7.8 (4) | O6—C15—C20—O1 | 2.9 (6) |
O9—K1—O5—C13 | −87.1 (4) | C20—O1—C1—C2 | 3.9 (7) |
O3—K1—O5—C13 | 115.4 (4) | C1—O1—C20—C19 | 72.1 (6) |
O2—K1—O5—C13 | 53.2 (5) |
Experimental details
Crystal data | |
Chemical formula | [K(C20H24O6)][CrClO3] |
Mr | 534.94 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 10.139 (3), 10.649 (4), 12.138 (3) |
α, β, γ (°) | 95.34 (3), 94.11 (2), 113.05 (2) |
V (Å3) | 1192.3 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.81 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Siemens P3/PC diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4317, 4067, 2703 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.197, 1.04 |
No. of reflections | 4067 |
No. of parameters | 296 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.76, −0.39 |
Computer programs: P3/PC (Siemens, 1989), P3/PC, XDISK (Siemens, 1991), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
K1—O1 | 2.753 (3) | K1—O8 | 2.922 (15) |
K1—O2 | 2.899 (3) | K1—O9 | 2.784 (5) |
K1—O3 | 2.810 (3) | K1—Cl1' | 3.197 (14) |
K1—O4 | 2.744 (4) | C1—O1 | 1.385 (5) |
K1—O5 | 2.791 (4) | C20—O1 | 1.388 (5) |
K1—O6 | 2.975 (4) | ||
C1—O1—C20 | 118.6 (4) | C10—O4—C11 | 116.9 (5) |
C6—O2—C7 | 116.5 (4) | C13—O5—C12 | 114.7 (5) |
C9—O3—C8 | 113.0 (4) | C15—O6—C14 | 116.9 (4) |
C7—O2—C6—C1 | −174.6 (4) |
There are three possible isomers of dibenzo-18-crown-6, namely [3.3]dibenzo-18-crown-6, (I), [2.4]dibenzo-18-crown-6, (II) and [1.5]dibenzo-18-crown-6, (III), which differ in terms of the positions of the aromatic rings. With regard to the ability of these crown ether (CE) molecules to form complexes with cations and neutral guest molecules, the [1.5]dibenzo-18-crown-6 molecule, (III), is, in our opinion, the most interesting. In particular, it has the minimum distance between benzene rings of only one bridging O atom. Restricted rotation around the Car—O bonds may result in selectivity in complex formation, which was recently confirmed by us (Kotlyar, Fonari et al., 2005; Ganin et al., 2005).
We now report the crystal structure of the title complex, (IV), of [1.5]dibenzo-18-crown-6 with potassium chlorochromate (Fig. 1), obtained by mixing KCrO3Cl and CE ethyl acetate solutions in a 1:1 ratio at room temperature.
The CE molecule in (IV) possesses the crown-like conformation, which is somewhat strained due to the presence of the two benzene rings. The C1—O1 and C20—O1 bonds are geometrically non-equivalent. The C20—O1—C1—C2 torsion angle of 3.9 (7)° implies the existence of electronic conjugation between the lone pairs of the O atom and the π system of the C1–C6 ring. The C1—O1 bond has a syn-clinal conformation with respect to the C15–C20 benzene ring [C1—O1—C20—C19 = 72.1 (6)°], so the conjugation of this ring with the lone pairs of atom O1 is disrupted. Nevertheless, the C1—O1 and C20—O1 bond lengths are practically the same (Table 1). This could be caused by elongation of the C1—O1 bond due to the presence of a short C20···H2 intramolecular contact of 2.54 Å (van der Waals radius sum for C and H = 2.86 Å; Zefirov & Zorky, 1989). The C2—C1—C20—C19 pseudo-dihedral angle in (IV) of 62.3 (5)° is somewhat smaller than that in the free [1.5]dibenzo-18-crown-6 ligand (89.3°; Kotlyar, Fonari et al., 2005). Based on this fact, we can suggest that the complexation probably leads to some flattening of the Ar–O–Ar fragment.
The K+ cation is coordinated by all six O atoms of the CE molecule. The K—O(ether) bond distances are within the range 2.744 (4)–2.975 (4) Å (Table 1). The bridging O atom between the benzene rings, O1, lies opposite atom O4. The cation is shifted from the mean plane of the CE O atoms by 0.849 (2) Å toward the anion, due to the formation of bonds with the anion.
The anion is disordered over two positions [occupancy ratio 0.729 (8):0.271 (8)] as a result of rotation around the bisector of the O7—Cr1—O9 bond angle. The minor disorder component of Cl1 (marked Cl1' in Fig. 1) lies near atom O8, and consequently atom O8' lies near atom Cl1. In contrast with previously reported structures of CE complexes with potassium chlorochromate (Kotlyar, Zubatyuk, Shishkin et al., 2004; Kotlyar, Zubatyuk, Zhygalko et al., 2004; Kotlyar, Fonari et al., 2005 or Kotlyar, Zubatyuk et al., 2005?), the Cl atom of the anion also participates in the formation of complex (IV).