Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039796/lh6551sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039796/lh6551Isup2.hkl |
CCDC reference: 296605
Key indicators
- Single-crystal X-ray study
- T = 164 K
- Mean (C-C) = 0.008 Å
- Disorder in main residue
- R factor = 0.079
- wR factor = 0.213
- Data-to-parameter ratio = 14.3
checkCIF/PLATON results
No syntax errors found
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.105 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.10 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.40 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.51 Ratio PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 3.38 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O7A PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O7B PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O9A PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O9B PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Cr1 PLAT301_ALERT_3_C Main Residue Disorder ......................... 9.00 Perc. PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 8
Alert level G ABSTM02_ALERT_3_G The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.352 0.620 Tmin and Tmax expected: 0.284 0.589 RR = 1.178 Please check that your absorption correction is appropriate.
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 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion
checkCIF publication errors
Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
Author Response: All autors made significant contribution in this work. The idea of synthesis belongs to Kamalov and Kotlyar. The synthesis was performed by Chuprin and Kiriyak. X-ray diffraction experiment was performed by Shishkina. The analysis of diffraction data was performed by Shishkin. |
1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing
The title complex, (I), was prepared in 78% yield (10.1 g) according to the previously described procedure (Kotlyar et al., 2005b), by mixing the ethyl acetate solutions of potassium chlorochromate (4.0 g, 22.9 mmol) and 4-bromobenzo-18-crown-6 (8.97 g, 22.9 mmol) at room temperature. Transparent yellow crystals of (I) suitable for X-ray analysis were obtained by evaporation from dichloromethane solution [m.p. 435–437 K (decomposition)]. Analysis calculated for C16H23BrClCrKO9: C 33.97, H 4.10, Cr 9.19%; found: C 34.05, H 4.11, Cr 9.25%. The crystals are soluble in dichloromethane, chloroform, dimethyl sulfoxide and dimethyl formamide, less soluble in acetone and 1,4-dioxane, and practically insoluble in benzene and toluene.
All H atoms were placed in calculated positions, with C—H distances of 0.95 and 0.99 Å. They were included in the refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C). In the disordered anion values of the Cr—O bond lengths were all constrained to 1.600 (1) Å and values of anisotropic displacement parameters of equivalent O atoms were constrained using the EADP command in SHELXL97 (Sheldrick, 1997). No restraints were applied to the K—O distances involving the anion, and hence the disorder of O7A/O7B has led to differnces between the bond lengths K1—O7A and K1—O7A (Table 1). For typical K—O distances in related compounds see Kotlyar et al. (2004b, 2005a) and Kotlyar, Zubatyuk, Zhigalko et al. (2004).
Data collection: P3 (Siemens, 1989); cell refinement: P3; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1991); software used to prepare material for publication: SHELXL97.
[K(C16H23BrO6)][CrClO3] | F(000) = 1144 |
Mr = 565.79 | Dx = 1.679 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 12 reflections |
a = 11.102 (3) Å | θ = 2–25° |
b = 14.930 (4) Å | µ = 2.64 mm−1 |
c = 13.552 (3) Å | T = 164 K |
β = 94.676 (18)° | Plate, yellow |
V = 2238.8 (10) Å3 | 0.50 × 0.50 × 0.20 mm |
Z = 4 |
Siemens P3/PC diffractometer | 2598 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.105 |
Graphite monochromator | θmax = 25.1°, θmin = 2.0° |
ω–2θ scans | h = −10→13 |
Absorption correction: analytical (Alcock, 1970) | k = 0→17 |
Tmin = 0.352, Tmax = 0.620 | l = −16→16 |
4083 measured reflections | 2 standard reflections every 98 reflections |
3875 independent reflections | intensity decay: 5% |
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)] = 0.079 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.213 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.1318P)2 + 1.9879P] where P = (Fo2 + 2Fc2)/3 |
3875 reflections | (Δ/σ)max < 0.001 |
271 parameters | Δρmax = 2.00 e Å−3 |
4 restraints | Δρmin = −0.83 e Å−3 |
[K(C16H23BrO6)][CrClO3] | V = 2238.8 (10) Å3 |
Mr = 565.79 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.102 (3) Å | µ = 2.64 mm−1 |
b = 14.930 (4) Å | T = 164 K |
c = 13.552 (3) Å | 0.50 × 0.50 × 0.20 mm |
β = 94.676 (18)° |
Siemens P3/PC diffractometer | 2598 reflections with I > 2σ(I) |
Absorption correction: analytical (Alcock, 1970) | Rint = 0.105 |
Tmin = 0.352, Tmax = 0.620 | 2 standard reflections every 98 reflections |
4083 measured reflections | intensity decay: 5% |
3875 independent reflections |
R[F2 > 2σ(F2)] = 0.079 | 4 restraints |
wR(F2) = 0.213 | H-atom parameters constrained |
S = 1.05 | Δρmax = 2.00 e Å−3 |
3875 reflections | Δρmin = −0.83 e Å−3 |
271 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) | |
Br1 | 0.77251 (5) | 0.25074 (4) | 0.80610 (4) | 0.03400 (14) | |
Cr1 | 0.69654 (5) | 0.60941 (5) | 1.24411 (6) | 0.0398 (3) | |
K1 | 0.74759 (11) | 0.73746 (8) | 0.99307 (11) | 0.0405 (3) | |
Cl1 | 0.74037 (19) | 0.47546 (12) | 1.29940 (16) | 0.0648 (6) | |
O1 | 0.6841 (3) | 0.5888 (2) | 0.8776 (3) | 0.0275 (9) | |
O2 | 0.5080 (3) | 0.6997 (3) | 0.9585 (3) | 0.0372 (10) | |
O3 | 0.5808 (4) | 0.8717 (3) | 1.0303 (3) | 0.0439 (11) | |
O4 | 0.8216 (4) | 0.8820 (3) | 1.1147 (3) | 0.0468 (12) | |
O5 | 0.9864 (3) | 0.7848 (2) | 1.0010 (3) | 0.0301 (9) | |
O6 | 0.9103 (3) | 0.6337 (2) | 0.8924 (3) | 0.0257 (9) | |
O7A | 0.7579 (10) | 0.6258 (8) | 1.1399 (7) | 0.069 (3) | 0.50 |
O8A | 0.55200 (7) | 0.6121 (6) | 1.2351 (8) | 0.055 (2) | 0.50 |
O9A | 0.7595 (3) | 0.68858 (13) | 1.3090 (2) | 0.087 (2) | 0.50 |
O7B | 0.7143 (10) | 0.5925 (9) | 1.1269 (8) | 0.069 (3) | 0.50 |
O8B | 0.55892 (10) | 0.6373 (3) | 1.2542 (6) | 0.055 (2) | 0.50 |
O9B | 0.78137 (19) | 0.66368 (19) | 1.3244 (2) | 0.087 (2) | 0.50 |
C1 | 0.8875 (4) | 0.5447 (3) | 0.8737 (4) | 0.0209 (11) | |
C2 | 0.9735 (4) | 0.4827 (4) | 0.8586 (4) | 0.0266 (13) | |
H2 | 1.0562 | 0.4997 | 0.8620 | 0.032* | |
C3 | 0.9405 (4) | 0.3938 (4) | 0.8380 (4) | 0.0245 (12) | |
H3 | 1.0000 | 0.3499 | 0.8275 | 0.029* | |
C4 | 0.8189 (5) | 0.3712 (3) | 0.8333 (4) | 0.0266 (13) | |
C5 | 0.7326 (4) | 0.4326 (3) | 0.8470 (4) | 0.0254 (12) | |
H5 | 0.6502 | 0.4148 | 0.8439 | 0.031* | |
C6 | 0.7631 (4) | 0.5210 (3) | 0.8657 (4) | 0.0220 (12) | |
C7 | 0.5578 (4) | 0.5648 (4) | 0.8784 (5) | 0.0324 (14) | |
H7A | 0.5445 | 0.5314 | 0.9397 | 0.039* | |
H7B | 0.5335 | 0.5259 | 0.8210 | 0.039* | |
C8 | 0.4837 (5) | 0.6487 (4) | 0.8733 (5) | 0.0374 (15) | |
H8A | 0.5022 | 0.6842 | 0.8147 | 0.045* | |
H8B | 0.3968 | 0.6331 | 0.8660 | 0.045* | |
C9 | 0.4303 (5) | 0.7763 (5) | 0.9617 (6) | 0.0524 (19) | |
H9A | 0.3461 | 0.7561 | 0.9664 | 0.063* | |
H9B | 0.4331 | 0.8112 | 0.8999 | 0.063* | |
C10 | 0.4680 (5) | 0.8338 (5) | 1.0476 (5) | 0.0532 (19) | |
H10A | 0.4075 | 0.8815 | 1.0548 | 0.064* | |
H10B | 0.4753 | 0.7977 | 1.1091 | 0.064* | |
C11 | 0.6214 (6) | 0.9353 (4) | 1.1061 (5) | 0.0498 (18) | |
H11A | 0.6141 | 0.9091 | 1.1724 | 0.060* | |
H11B | 0.5712 | 0.9901 | 1.0999 | 0.060* | |
C12 | 0.7508 (6) | 0.9579 (4) | 1.0935 (5) | 0.0426 (16) | |
H12A | 0.7594 | 0.9777 | 1.0247 | 0.051* | |
H12B | 0.7777 | 1.0073 | 1.1388 | 0.051* | |
C13 | 0.9470 (6) | 0.8961 (4) | 1.1186 (5) | 0.0440 (17) | |
H13A | 0.9872 | 0.8565 | 1.1697 | 0.053* | |
H13B | 0.9647 | 0.9588 | 1.1386 | 0.053* | |
C14 | 0.9995 (5) | 0.8781 (4) | 1.0195 (4) | 0.0346 (15) | |
H14A | 0.9552 | 0.9130 | 0.9660 | 0.042* | |
H14B | 1.0858 | 0.8954 | 1.0231 | 0.042* | |
C15 | 1.0391 (5) | 0.7598 (4) | 0.9121 (4) | 0.0291 (13) | |
H15A | 1.1240 | 0.7806 | 0.9150 | 0.035* | |
H15B | 0.9941 | 0.7884 | 0.8543 | 0.035* | |
C16 | 1.0347 (4) | 0.6612 (4) | 0.9012 (4) | 0.0266 (13) | |
H16B | 1.0743 | 0.6429 | 0.8415 | 0.032* | |
H16A | 1.0780 | 0.6324 | 0.9596 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0274 (3) | 0.0289 (3) | 0.0454 (3) | −0.0034 (2) | 0.0013 (2) | −0.0054 (3) |
Cr1 | 0.0266 (4) | 0.0473 (5) | 0.0448 (6) | −0.0028 (4) | −0.0020 (4) | −0.0063 (5) |
K1 | 0.0221 (6) | 0.0376 (7) | 0.0620 (8) | 0.0002 (5) | 0.0038 (6) | −0.0130 (6) |
Cl1 | 0.0694 (12) | 0.0487 (9) | 0.0755 (13) | 0.0051 (9) | 0.0011 (10) | 0.0163 (9) |
O1 | 0.0124 (15) | 0.0336 (19) | 0.036 (2) | 0.0000 (14) | 0.0001 (14) | −0.0024 (16) |
O2 | 0.0181 (17) | 0.053 (2) | 0.039 (2) | 0.0055 (17) | −0.0025 (16) | −0.010 (2) |
O3 | 0.041 (2) | 0.053 (2) | 0.039 (2) | 0.0022 (19) | 0.0100 (18) | −0.0193 (19) |
O4 | 0.044 (2) | 0.047 (2) | 0.049 (3) | 0.006 (2) | 0.000 (2) | −0.009 (2) |
O5 | 0.0343 (19) | 0.0351 (19) | 0.0204 (18) | −0.0059 (17) | −0.0012 (15) | −0.0021 (16) |
O6 | 0.0177 (16) | 0.0307 (18) | 0.0282 (19) | −0.0023 (14) | −0.0006 (14) | 0.0014 (15) |
O7A | 0.068 (5) | 0.103 (7) | 0.039 (3) | 0.009 (5) | 0.027 (3) | 0.026 (4) |
O8A | 0.029 (2) | 0.044 (4) | 0.090 (5) | 0.004 (2) | −0.006 (3) | −0.046 (4) |
O9A | 0.075 (4) | 0.045 (4) | 0.132 (6) | 0.003 (4) | −0.041 (4) | −0.034 (4) |
O7B | 0.068 (5) | 0.103 (7) | 0.039 (3) | 0.009 (5) | 0.027 (3) | 0.026 (4) |
O8B | 0.029 (2) | 0.044 (4) | 0.090 (5) | 0.004 (2) | −0.006 (3) | −0.046 (4) |
O9B | 0.075 (4) | 0.045 (4) | 0.132 (6) | 0.003 (4) | −0.041 (4) | −0.034 (4) |
C1 | 0.014 (2) | 0.030 (2) | 0.019 (2) | −0.0052 (19) | 0.0002 (19) | 0.003 (2) |
C2 | 0.018 (2) | 0.036 (3) | 0.026 (3) | −0.003 (2) | 0.002 (2) | −0.001 (2) |
C3 | 0.017 (2) | 0.035 (3) | 0.022 (2) | 0.000 (2) | 0.0008 (19) | 0.000 (2) |
C4 | 0.035 (3) | 0.027 (3) | 0.017 (2) | −0.002 (2) | −0.001 (2) | 0.005 (2) |
C5 | 0.017 (2) | 0.030 (3) | 0.030 (3) | −0.005 (2) | 0.000 (2) | −0.001 (2) |
C6 | 0.017 (2) | 0.028 (2) | 0.020 (2) | −0.004 (2) | −0.0017 (19) | 0.001 (2) |
C7 | 0.015 (2) | 0.039 (3) | 0.043 (3) | −0.004 (2) | 0.003 (2) | 0.002 (3) |
C8 | 0.025 (3) | 0.044 (3) | 0.043 (3) | 0.002 (2) | −0.004 (2) | −0.012 (3) |
C9 | 0.024 (3) | 0.068 (4) | 0.065 (4) | 0.015 (3) | 0.001 (3) | −0.021 (4) |
C10 | 0.027 (3) | 0.072 (4) | 0.062 (4) | 0.007 (3) | 0.015 (3) | −0.019 (4) |
C11 | 0.047 (4) | 0.052 (4) | 0.053 (4) | −0.002 (3) | 0.019 (3) | −0.025 (3) |
C12 | 0.039 (3) | 0.046 (3) | 0.044 (3) | 0.000 (3) | 0.006 (3) | −0.011 (3) |
C13 | 0.049 (4) | 0.042 (3) | 0.038 (3) | 0.004 (3) | −0.009 (3) | −0.014 (3) |
C14 | 0.033 (3) | 0.034 (3) | 0.036 (3) | 0.000 (2) | −0.008 (2) | −0.008 (3) |
C15 | 0.022 (2) | 0.037 (3) | 0.027 (3) | −0.011 (2) | −0.004 (2) | −0.005 (2) |
C16 | 0.013 (2) | 0.037 (3) | 0.030 (3) | −0.005 (2) | 0.003 (2) | 0.002 (2) |
Br1—C4 | 1.899 (5) | C1—C6 | 1.421 (7) |
Cr1—O9A | 1.5998 (10) | C2—C3 | 1.399 (7) |
Cr1—O9B | 1.5998 (10) | C2—H2 | 0.9500 |
Cr1—O8A | 1.6000 (9) | C3—C4 | 1.388 (7) |
Cr1—O8B | 1.6000 (10) | C3—H3 | 0.9500 |
Cr1—O7A | 1.635 (10) | C4—C5 | 1.349 (7) |
Cr1—O7B | 1.636 (11) | C5—C6 | 1.382 (7) |
Cr1—Cl1 | 2.177 (2) | C5—H5 | 0.9500 |
K1—O7A | 2.591 (11) | C7—C8 | 1.498 (8) |
K1—O2 | 2.722 (4) | C7—H7A | 0.9900 |
K1—O5 | 2.737 (4) | C7—H7B | 0.9900 |
K1—O9Ai | 2.741 (3) | C8—H8A | 0.9900 |
K1—O9Bi | 2.772 (3) | C8—H8B | 0.9900 |
K1—O1 | 2.774 (4) | C9—C10 | 1.479 (10) |
K1—O4 | 2.798 (4) | C9—H9A | 0.9900 |
K1—O3 | 2.802 (4) | C9—H9B | 0.9900 |
K1—O6 | 2.815 (4) | C10—H10A | 0.9900 |
K1—O7B | 2.867 (12) | C10—H10B | 0.9900 |
O1—C6 | 1.357 (6) | C11—C12 | 1.498 (9) |
O1—C7 | 1.448 (6) | C11—H11A | 0.9900 |
O2—C8 | 1.390 (7) | C11—H11B | 0.9900 |
O2—C9 | 1.435 (7) | C12—H12A | 0.9900 |
O3—C10 | 1.412 (8) | C12—H12B | 0.9900 |
O3—C11 | 1.443 (8) | C13—C14 | 1.530 (9) |
O4—C12 | 1.395 (7) | C13—H13A | 0.9900 |
O4—C13 | 1.405 (8) | C13—H13B | 0.9900 |
O5—C14 | 1.420 (6) | C14—H14A | 0.9900 |
O5—C15 | 1.431 (6) | C14—H14B | 0.9900 |
O6—C1 | 1.373 (6) | C15—C16 | 1.480 (7) |
O6—C16 | 1.437 (6) | C15—H15A | 0.9900 |
O9A—K1ii | 2.741 (3) | C15—H15B | 0.9900 |
O9B—K1ii | 2.772 (3) | C16—H16B | 0.9900 |
C1—C2 | 1.358 (7) | C16—H16A | 0.9900 |
O9A—Cr1—O9B | 17.33 (15) | Cr1—O7A—K1 | 139.8 (6) |
O9A—Cr1—O8A | 114.4 (3) | Cr1—O9A—K1ii | 138.30 (19) |
O9B—Cr1—O8A | 124.8 (4) | Cr1—O7B—K1 | 122.0 (6) |
O9A—Cr1—O8B | 97.97 (18) | Cr1—O9B—K1ii | 135.94 (14) |
O9B—Cr1—O8B | 108.9 (2) | C2—C1—O6 | 124.5 (4) |
O8A—Cr1—O8B | 16.5 (4) | C2—C1—C6 | 120.7 (5) |
O9A—Cr1—O7A | 99.8 (4) | O6—C1—C6 | 114.7 (4) |
O9B—Cr1—O7A | 104.3 (4) | C1—C2—C3 | 120.1 (5) |
O8A—Cr1—O7A | 114.6 (6) | C1—C2—H2 | 120.0 |
O8B—Cr1—O7A | 120.1 (5) | C3—C2—H2 | 120.0 |
O9A—Cr1—O7B | 124.5 (5) | C4—C3—C2 | 118.5 (5) |
O9B—Cr1—O7B | 128.9 (4) | C4—C3—H3 | 120.7 |
O8A—Cr1—O7B | 97.4 (6) | C2—C3—H3 | 120.7 |
O8B—Cr1—O7B | 108.3 (5) | C5—C4—C3 | 121.8 (5) |
O7A—Cr1—O7B | 25.0 (6) | C5—C4—Br1 | 119.1 (4) |
O9A—Cr1—Cl1 | 114.47 (12) | C3—C4—Br1 | 119.1 (4) |
O9B—Cr1—Cl1 | 97.39 (14) | C4—C5—C6 | 120.6 (5) |
O8A—Cr1—Cl1 | 104.1 (3) | C4—C5—H5 | 119.7 |
O8B—Cr1—Cl1 | 113.4 (2) | C6—C5—H5 | 119.7 |
O7A—Cr1—Cl1 | 109.7 (4) | O1—C6—C5 | 125.7 (4) |
O7B—Cr1—Cl1 | 98.7 (5) | O1—C6—C1 | 116.1 (4) |
O7A—K1—O2 | 88.9 (3) | C5—C6—C1 | 118.3 (4) |
O7A—K1—O5 | 98.9 (3) | O1—C7—C8 | 108.7 (4) |
O2—K1—O5 | 171.84 (13) | O1—C7—H7A | 109.9 |
O7A—K1—O9Ai | 162.9 (3) | C8—C7—H7A | 109.9 |
O2—K1—O9Ai | 92.61 (11) | O1—C7—H7B | 109.9 |
O5—K1—O9Ai | 79.24 (10) | C8—C7—H7B | 109.9 |
O7A—K1—O9Bi | 167.3 (3) | H7A—C7—H7B | 108.3 |
O2—K1—O9Bi | 99.44 (11) | O2—C8—C7 | 110.6 (5) |
O5—K1—O9Bi | 72.49 (9) | O2—C8—H8A | 109.5 |
O7A—K1—O1 | 84.9 (3) | C7—C8—H8A | 109.5 |
O2—K1—O1 | 62.43 (11) | O2—C8—H8B | 109.5 |
O5—K1—O1 | 115.45 (11) | C7—C8—H8B | 109.5 |
O9Ai—K1—O1 | 80.66 (10) | H8A—C8—H8B | 108.1 |
O9Bi—K1—O1 | 90.34 (11) | O2—C9—C10 | 110.7 (5) |
O7A—K1—O4 | 92.9 (3) | O2—C9—H9A | 109.5 |
O2—K1—O4 | 119.80 (13) | C10—C9—H9A | 109.5 |
O5—K1—O4 | 62.66 (12) | O2—C9—H9B | 109.5 |
O9Ai—K1—O4 | 101.05 (12) | C10—C9—H9B | 109.5 |
O9Bi—K1—O4 | 91.27 (12) | H9A—C9—H9B | 108.1 |
O1—K1—O4 | 176.95 (12) | O3—C10—C9 | 107.5 (5) |
O7A—K1—O3 | 108.1 (3) | O3—C10—H10A | 110.2 |
O2—K1—O3 | 61.87 (12) | C9—C10—H10A | 110.2 |
O5—K1—O3 | 117.38 (13) | O3—C10—H10B | 110.2 |
O9Ai—K1—O3 | 87.54 (11) | C9—C10—H10B | 110.2 |
O9Bi—K1—O3 | 84.45 (11) | H10A—C10—H10B | 108.5 |
O1—K1—O3 | 122.19 (12) | O3—C11—C12 | 108.3 (5) |
O4—K1—O3 | 60.57 (13) | O3—C11—H11A | 110.0 |
O7A—K1—O6 | 91.6 (3) | C12—C11—H11A | 110.0 |
O2—K1—O6 | 117.33 (12) | O3—C11—H11B | 110.0 |
O5—K1—O6 | 60.24 (11) | C12—C11—H11B | 110.0 |
O9Ai—K1—O6 | 72.55 (10) | H11A—C11—H11B | 108.4 |
O9Bi—K1—O6 | 75.99 (10) | O4—C12—C11 | 108.8 (5) |
O1—K1—O6 | 55.24 (10) | O4—C12—H12A | 109.9 |
O4—K1—O6 | 122.74 (12) | C11—C12—H12A | 109.9 |
O3—K1—O6 | 160.09 (13) | O4—C12—H12B | 109.9 |
O7A—K1—O7B | 13.7 (3) | C11—C12—H12B | 109.9 |
O2—K1—O7B | 77.2 (2) | H12A—C12—H12B | 108.3 |
O5—K1—O7B | 110.2 (2) | O4—C13—C14 | 112.8 (5) |
O9Ai—K1—O7B | 153.9 (3) | O4—C13—H13A | 109.0 |
O9Bi—K1—O7B | 163.1 (3) | C14—C13—H13A | 109.0 |
O1—K1—O7B | 73.3 (3) | O4—C13—H13B | 109.0 |
O4—K1—O7B | 104.9 (3) | C14—C13—H13B | 109.0 |
O3—K1—O7B | 107.8 (3) | H13A—C13—H13B | 107.8 |
O6—K1—O7B | 90.7 (3) | O5—C14—C13 | 106.7 (5) |
C6—O1—C7 | 116.9 (4) | O5—C14—H14A | 110.4 |
C6—O1—K1 | 121.8 (3) | C13—C14—H14A | 110.4 |
C7—O1—K1 | 113.3 (3) | O5—C14—H14B | 110.4 |
C8—O2—C9 | 112.6 (4) | C13—C14—H14B | 110.4 |
C8—O2—K1 | 112.2 (3) | H14A—C14—H14B | 108.6 |
C9—O2—K1 | 114.3 (3) | O5—C15—C16 | 109.4 (4) |
C10—O3—C11 | 112.1 (5) | O5—C15—H15A | 109.8 |
C10—O3—K1 | 110.5 (4) | C16—C15—H15A | 109.8 |
C11—O3—K1 | 115.2 (3) | O5—C15—H15B | 109.8 |
C12—O4—C13 | 115.2 (5) | C16—C15—H15B | 109.8 |
C12—O4—K1 | 111.8 (3) | H15A—C15—H15B | 108.2 |
C13—O4—K1 | 112.3 (3) | O6—C16—C15 | 108.4 (4) |
C14—O5—C15 | 111.2 (4) | O6—C16—H16B | 110.0 |
C14—O5—K1 | 110.2 (3) | C15—C16—H16B | 110.0 |
C15—O5—K1 | 111.1 (3) | O6—C16—H16A | 110.0 |
C1—O6—C16 | 116.9 (4) | C15—C16—H16A | 110.0 |
C1—O6—K1 | 120.4 (3) | H16B—C16—H16A | 108.4 |
C16—O6—K1 | 117.0 (3) | ||
O7A—K1—O1—C6 | −67.0 (4) | O3—K1—O6—C16 | 89.9 (5) |
O2—K1—O1—C6 | −158.4 (4) | O7B—K1—O6—C16 | −111.8 (4) |
O5—K1—O1—C6 | 30.4 (4) | O9A—Cr1—O7A—K1 | −72.3 (9) |
O9Ai—K1—O1—C6 | 103.6 (3) | O9B—Cr1—O7A—K1 | −89.4 (9) |
O9Bi—K1—O1—C6 | 101.1 (3) | O8A—Cr1—O7A—K1 | 50.4 (11) |
O3—K1—O1—C6 | −175.3 (3) | O8B—Cr1—O7A—K1 | 32.9 (11) |
O6—K1—O1—C6 | 28.5 (3) | O7B—Cr1—O7A—K1 | 100.1 (18) |
O7B—K1—O1—C6 | −74.4 (4) | Cl1—Cr1—O7A—K1 | 167.1 (7) |
O7A—K1—O1—C7 | 80.7 (4) | O2—K1—O7A—Cr1 | −58.5 (9) |
O2—K1—O1—C7 | −10.7 (3) | O5—K1—O7A—Cr1 | 124.1 (9) |
O5—K1—O1—C7 | 178.1 (3) | O9Ai—K1—O7A—Cr1 | −153.7 (5) |
O9Ai—K1—O1—C7 | −108.6 (3) | O9Bi—K1—O7A—Cr1 | 170.4 (4) |
O9Bi—K1—O1—C7 | −111.2 (3) | O1—K1—O7A—Cr1 | −120.9 (9) |
O3—K1—O1—C7 | −27.5 (4) | O4—K1—O7A—Cr1 | 61.3 (9) |
O6—K1—O1—C7 | 176.2 (4) | O3—K1—O7A—Cr1 | 1.4 (10) |
O7B—K1—O1—C7 | 73.3 (4) | O6—K1—O7A—Cr1 | −175.8 (9) |
O7A—K1—O2—C8 | −108.0 (4) | O7B—K1—O7A—Cr1 | −89.6 (18) |
O9Ai—K1—O2—C8 | 54.9 (4) | C14—K1—O7A—Cr1 | 103.3 (9) |
O9Bi—K1—O2—C8 | 62.3 (4) | C8—K1—O7A—Cr1 | −79.1 (9) |
O1—K1—O2—C8 | −23.1 (3) | O9B—Cr1—O9A—K1ii | −78.2 (6) |
O4—K1—O2—C8 | 159.2 (3) | O8A—Cr1—O9A—K1ii | 52.1 (5) |
O3—K1—O2—C8 | 140.7 (4) | O8B—Cr1—O9A—K1ii | 52.3 (4) |
O6—K1—O2—C8 | −16.7 (4) | O7A—Cr1—O9A—K1ii | 174.9 (4) |
O7B—K1—O2—C8 | −100.8 (4) | O7B—Cr1—O9A—K1ii | 171.0 (5) |
O7A—K1—O2—C9 | 122.2 (5) | Cl1—Cr1—O9A—K1ii | −68.0 (2) |
O9Ai—K1—O2—C9 | −74.8 (4) | K1—Cr1—O9A—K1ii | 151.32 (19) |
O9Bi—K1—O2—C9 | −67.5 (4) | O9A—Cr1—O7B—K1 | −33.5 (8) |
O1—K1—O2—C9 | −152.9 (4) | O9B—Cr1—O7B—K1 | −54.5 (8) |
O4—K1—O2—C9 | 29.5 (4) | O8A—Cr1—O7B—K1 | 93.0 (6) |
O3—K1—O2—C9 | 11.0 (4) | O8B—Cr1—O7B—K1 | 80.3 (6) |
O6—K1—O2—C9 | −146.5 (4) | O7A—Cr1—O7B—K1 | −42.5 (13) |
O7B—K1—O2—C9 | 129.4 (5) | Cl1—Cr1—O7B—K1 | −161.4 (5) |
O7A—K1—O3—C10 | −55.0 (5) | O7A—K1—O7B—Cr1 | 49.4 (14) |
O2—K1—O3—C10 | 23.6 (4) | O2—K1—O7B—Cr1 | −98.6 (6) |
O5—K1—O3—C10 | −165.6 (4) | O5—K1—O7B—Cr1 | 85.1 (6) |
O9Ai—K1—O3—C10 | 117.8 (4) | O9Ai—K1—O7B—Cr1 | −167.6 (3) |
O9Bi—K1—O3—C10 | 127.4 (4) | O9Bi—K1—O7B—Cr1 | −178.8 (2) |
O1—K1—O3—C10 | 40.5 (4) | O1—K1—O7B—Cr1 | −163.3 (7) |
O4—K1—O3—C10 | −138.0 (4) | O4—K1—O7B—Cr1 | 19.2 (7) |
O6—K1—O3—C10 | 116.6 (5) | O3—K1—O7B—Cr1 | −44.1 (7) |
O7B—K1—O3—C10 | −40.6 (5) | O6—K1—O7B—Cr1 | 143.5 (6) |
O7A—K1—O3—C11 | 73.3 (5) | O9A—Cr1—O9B—K1ii | 67.8 (5) |
O2—K1—O3—C11 | 151.9 (4) | O8A—Cr1—O9B—K1ii | 10.0 (6) |
O5—K1—O3—C11 | −37.3 (4) | O8B—Cr1—O9B—K1ii | 15.0 (4) |
O9Ai—K1—O3—C11 | −113.8 (4) | O7A—Cr1—O9B—K1ii | 144.4 (5) |
O9Bi—K1—O3—C11 | −104.3 (4) | O7B—Cr1—O9B—K1ii | 149.6 (6) |
O1—K1—O3—C11 | 168.8 (4) | Cl1—Cr1—O9B—K1ii | −102.9 (2) |
O4—K1—O3—C11 | −9.7 (4) | C16—O6—C1—C2 | −3.2 (7) |
O6—K1—O3—C11 | −115.1 (5) | K1—O6—C1—C2 | −155.9 (4) |
O7B—K1—O3—C11 | 87.7 (5) | C16—O6—C1—C6 | −180.0 (4) |
O7A—K1—O4—C12 | −134.5 (5) | K1—O6—C1—C6 | 27.4 (5) |
O2—K1—O4—C12 | −44.1 (4) | O6—C1—C2—C3 | −178.7 (4) |
O5—K1—O4—C12 | 127.0 (4) | C6—C1—C2—C3 | −2.1 (7) |
O9Ai—K1—O4—C12 | 55.4 (4) | C1—C2—C3—C4 | 0.2 (7) |
O9Bi—K1—O4—C12 | 57.5 (4) | C2—C3—C4—C5 | 0.6 (8) |
O3—K1—O4—C12 | −25.4 (4) | C2—C3—C4—Br1 | −179.7 (4) |
O6—K1—O4—C12 | 131.6 (4) | C3—C4—C5—C6 | 0.5 (8) |
O7B—K1—O4—C12 | −127.7 (4) | Br1—C4—C5—C6 | −179.2 (4) |
O7A—K1—O4—C13 | 94.1 (4) | C7—O1—C6—C5 | 5.1 (7) |
O2—K1—O4—C13 | −175.5 (4) | K1—O1—C6—C5 | 151.8 (4) |
O5—K1—O4—C13 | −4.3 (4) | C7—O1—C6—C1 | −174.7 (4) |
O9Ai—K1—O4—C13 | −76.0 (4) | K1—O1—C6—C1 | −28.1 (5) |
O9Bi—K1—O4—C13 | −73.8 (4) | C4—C5—C6—O1 | 177.8 (5) |
O3—K1—O4—C13 | −156.7 (4) | C4—C5—C6—C1 | −2.4 (7) |
O6—K1—O4—C13 | 0.3 (4) | C2—C1—C6—O1 | −177.0 (4) |
O7B—K1—O4—C13 | 101.0 (4) | O6—C1—C6—O1 | −0.1 (6) |
O7A—K1—O5—C14 | −118.6 (4) | C2—C1—C6—C5 | 3.2 (7) |
O9Ai—K1—O5—C14 | 78.7 (3) | O6—C1—C6—C5 | −179.9 (4) |
O9Bi—K1—O5—C14 | 71.0 (3) | C6—O1—C7—C8 | −169.7 (4) |
O1—K1—O5—C14 | 152.8 (3) | K1—O1—C7—C8 | 40.9 (5) |
O4—K1—O5—C14 | −29.9 (3) | C9—O2—C8—C7 | −174.0 (5) |
O3—K1—O5—C14 | −2.9 (4) | K1—O2—C8—C7 | 55.4 (5) |
O6—K1—O5—C14 | 154.6 (3) | C9—O2—C8—K1 | 130.6 (5) |
O7B—K1—O5—C14 | −126.7 (4) | O1—C7—C8—O2 | −65.7 (6) |
O7A—K1—O5—C15 | 117.6 (4) | O1—C7—C8—K1 | −28.8 (4) |
O9Ai—K1—O5—C15 | −45.1 (3) | C8—O2—C9—C10 | −173.7 (5) |
O9Bi—K1—O5—C15 | −52.7 (3) | K1—O2—C9—C10 | −44.2 (7) |
O1—K1—O5—C15 | 29.0 (3) | C11—O3—C10—C9 | 175.1 (5) |
O4—K1—O5—C15 | −153.6 (3) | K1—O3—C10—C9 | −54.9 (6) |
O3—K1—O5—C15 | −126.6 (3) | O2—C9—C10—O3 | 67.9 (7) |
O6—K1—O5—C15 | 30.8 (3) | C10—O3—C11—C12 | 168.7 (5) |
O7B—K1—O5—C15 | 109.6 (4) | K1—O3—C11—C12 | 41.2 (6) |
O7A—K1—O6—C1 | 54.6 (4) | C13—O4—C12—C11 | −172.1 (5) |
O2—K1—O6—C1 | −35.0 (3) | K1—O4—C12—C11 | 58.1 (6) |
O5—K1—O6—C1 | 153.9 (3) | O3—C11—C12—O4 | −67.0 (7) |
O9Ai—K1—O6—C1 | −118.8 (3) | C12—O4—C13—C14 | −93.1 (6) |
O9Bi—K1—O6—C1 | −128.5 (3) | K1—O4—C13—C14 | 36.5 (6) |
O1—K1—O6—C1 | −28.1 (3) | C15—O5—C14—C13 | −176.8 (4) |
O4—K1—O6—C1 | 149.1 (3) | K1—O5—C14—C13 | 59.5 (4) |
O3—K1—O6—C1 | −117.5 (4) | C15—O5—C14—K1 | 123.7 (4) |
O7B—K1—O6—C1 | 40.9 (4) | O4—C13—C14—O5 | −66.5 (6) |
O7A—K1—O6—C16 | −98.1 (4) | O4—C13—C14—K1 | −26.5 (4) |
O2—K1—O6—C16 | 172.3 (3) | C14—O5—C15—C16 | 174.2 (4) |
O5—K1—O6—C16 | 1.2 (3) | K1—O5—C15—C16 | −62.6 (4) |
O9Ai—K1—O6—C16 | 88.6 (3) | C14—O5—C15—K1 | −123.2 (4) |
O9Bi—K1—O6—C16 | 78.8 (3) | C1—O6—C16—C15 | 175.0 (4) |
O1—K1—O6—C16 | 179.2 (3) | K1—O6—C16—C15 | −31.4 (5) |
O4—K1—O6—C16 | −3.5 (4) | O5—C15—C16—O6 | 62.2 (5) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [K(C16H23BrO6)][CrClO3] |
Mr | 565.79 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 164 |
a, b, c (Å) | 11.102 (3), 14.930 (4), 13.552 (3) |
β (°) | 94.676 (18) |
V (Å3) | 2238.8 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.64 |
Crystal size (mm) | 0.50 × 0.50 × 0.20 |
Data collection | |
Diffractometer | Siemens P3/PC diffractometer |
Absorption correction | Analytical (Alcock, 1970) |
Tmin, Tmax | 0.352, 0.620 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4083, 3875, 2598 |
Rint | 0.105 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.079, 0.213, 1.05 |
No. of reflections | 3875 |
No. of parameters | 271 |
No. of restraints | 4 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.00, −0.83 |
Computer programs: P3 (Siemens, 1989), P3, XDISK (Siemens, 1991), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1991), SHELXL97.
K1—O7A | 2.591 (11) | K1—O1 | 2.774 (4) |
K1—O2 | 2.722 (4) | K1—O4 | 2.798 (4) |
K1—O5 | 2.737 (4) | K1—O3 | 2.802 (4) |
K1—O9Ai | 2.741 (3) | K1—O6 | 2.815 (4) |
K1—O9Bi | 2.772 (3) | K1—O7B | 2.867 (12) |
O6—C1—C6—O1 | −0.1 (6) | O3—C11—C12—O4 | −67.0 (7) |
O1—C7—C8—O2 | −65.7 (6) | O4—C13—C14—O5 | −66.5 (6) |
O2—C9—C10—O3 | 67.9 (7) | O5—C15—C16—O6 | 62.2 (5) |
Symmetry code: (i) x, −y+3/2, z−1/2. |
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Complexes of aliphatic, mono- and dicycloaliphatic CEs (CE = crown ether) are easily crystallized from acid aqueous solutions and we have determined several crystal structures of these compounds (Kotlyar et al., 2004a,b; Kotlyar, Zubatyuk, Zhigalko et al., 2004; Kotlyar et al., 2005a). Pure crystalline complexes of benzo- and dibenzo CE with halogenochromates were obtained for the first time by mixing ethyl acetate solutions of inorganic salt and ligand at room or increased temperature (Kotlyar et al., 2000). Thus, the complexes of isomeric [3.3]-, [2.4]- and [1.5]-dibenzo-18-crown-6 with potassium chlorochromate were synthesized in the ratio 1:1, and the crystal structure of [1.5]dibenzo-18-crown-6 with potassium chlorochromate was reported by us recently (Kotlyar et al., 2005b). Furthermore, we are interestred in the influence of centain aromatic ring substituents (F, Br, NO2, NH2 etc.) on the crystal structures of benzo- and dibenzo CE.
We report here the crystal structure of the title complex, (I), obtained by mixing KCrO3Cl and CE ethyl acetate solutions in a 1:1 ratio at room temperature. The title compound is the complex formed by a K cation with one crown ether molecule and a chlorochromate anion (Fig. 1). In the molecule, a K atom is coordinated equatorially by six macrocycle O atoms, and axially by atom O7 of one anion and atom O9 of a symmetry-related anion. Hence, in the crystal structure, molecules form polymeric chains in the [001] direction (Fig. 2). The macrocycle has a crown-like conformation. The O—C—C—O fragments have alternating +sc and -sc conformations (Table 1). Atoms O1, O2, O5, O6 and K1 form a plane, and atoms O3 and O4 are displaced from this plane by 0.68 and −0.31 Å, respectively. Typical for this type of molecule is a repulsion between the aromatic ring and the atoms of the macrocycle, which gives short intramolecular contacts, e.g. H5···C7 = 2.51 Å [sum of the van der Waals radii = 2.87 Å (Zefirov & Zorky, 1995 or 1989??)], H5···H7b = 2.09 Å (sum of van der Waals radii = 2.34 Å), H2···C16 = 2.49 Å, H2···H16a = 2.17 Å, H7b···C5 = 2.60 Å, H16a···C2 = 2.66 Å and H16b···C2 = 2.84 Å. Close contacts between H atoms are also observed in the macrocycle, e.g. H12b···H13b = 2.21 Å and H14a···H15a = 2.32 Å. Atoms O7, O8 and O9 of the anion are disordered over two sites (denoted by the label suffixes A and B), with equal occupancies, as a result of rotational disorder about the Cr1—Cl1 bond. In the crystal structure, there are close intermolecular contacts: Br1···Cl1(x, 1/2 − y, 1/2 + z) = 3.40 Å (sum of van der Waals radii = 3.87 Å), Br1···H10b(2 − x, 1 − y, 1 − z) = 3.14 Å (sum of van der Waals radii = 3.23 Å), Br1···H13a(1 − x, 1 − y, 1 − z) = 3.11 Å, Br1···H16a(1 − x, −1/2 + y, 3/2 − z) = 3.18 Å, H16b···C3(1 − x, 1 − y, 1 − z) = 2.77 Å, Cl1···H10a(2 − x, −1/2 − y, 1/2 − z) = 3.02 Å.