Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039244/ci2434sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039244/ci2434Isup2.hkl |
CCDC reference: 660277
The title compound was prepared by the reaction of dicyclohexano-18-crown-6 (0.384 g, 1 mmol) and europium nitrate (0.443 g 1 mmol) in the presence of hydrogen bromide (2 ml, 12.5 M, 25 mmol) in 20 ml mixed acetronitrile–methanol (1:1 v/v) solution. The resulting solution was left to evaporate at room temperature. Orange crystals suitable for X-ray diffraction were collected after 3 weeks (yield 75%; m.p. 430.4–436.8 K). Elemental analysis data: Found (calculated) C 37.17 (38.02) and H 5.55 (6.0)%.
The oxonium H atoms were located in a difference Fourier map and refined with O—H and H···H distance restraints of 0.82 (5) Å and 1.37 (1) Å, respectively, and with Uiso(H) = 1.5Ueq(O). The remaining H atoms were positioned geometrically and treated as riding, with C—H = 0.97–0.98 Å, and with Uiso(H) = 1.2Ueq(C). Because of racemic twinning, the TWIN and BASF instructions were used in the final refinement.
The complexation of dicyclohexano-18-crown-6 (DCH18C6) with some lanthanide ions normally leads to the formation of a complex via metal–oxygen chelation such as {La(NO3)3(DCH18C6)]} (Harman et al., 1976) and {[Eu(NO3)2(DCH18C6)]2[Eu(NO3)5]} (Nicoló et al., 1987) and salt-type compounds namely [Ln(Pic)2(DCH18C6)]+(Pic)- for Ln = La and Ce and also [Ln(Pic)2(DCH18C6)]+(Pic)-·0.5(DCH18C6) for Ln = Pr and Nd (Kusrini, 2006). However, different products without lanthanide coordination with crown ethers have also been observed namely (15-crown-5)triaquadichlorodioxouranium (Hassaballa et al., 1998) and [Gd(NO3)3(OH2)3].18-crown-6 (Backer-Dirks et al., 1980).
In our study, no complexation product was obtained from a solution mixture containing dicyclohexano-18-crown-6, europium nitrate and hydrogen bromide. Instead, the formation of a tribromide anion along with a hydroxonium ion occurred. A similar product, namely, bis(2,3-dibromo-6,7,9,10,12,13,15,16-octahydro- 5,8,11,14,17-pentaoxabenzocyclopentadecene)hydroxonium tribromide has been reported (Saleh et al., 2006).
Bond lengths and angles are in normal ranges (Allen et al., 1987). The macrocyclic strand of the molecule displays a series of anti and gauche torsion angles for C—O and C—C bonds (Fig. 1). The individual O—C—C—O segments are ag+a, ag-a, ag+a, ag-a, ag+a and ag-a. Relevant torsion angles are listed in Table 1. Both cyclohexane rings adopt chair conformations, with puckering parameters Q = 0.578 (6) Å, θ = 0.0 (6)° and φ = 8(20)° for the C5–C10 ring, and Q = 0.568 (7) Å, θ = 176.2 (7)° and φ = 200 (10)° for the C15–C20 ring (Cremer & Pople, 1975).
The crystal structure is stabilized by O—H···Br and O—H···O hydrogen bonds (Table 2, Fig. 2).
For bond-length data, see: Allen et al. (1987). For related literature, see Harman et al. (1976); Nicoló et al. (1987); Kusrini (2006); Hassaballa et al. (1998); Backer-Dirks et al. (1980); Saleh et al. (2006). For ring conformations, see: Cremer & Pople (1975).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).
C20H36O6·H3O+·Br3− | F(000) = 1280 |
Mr = 631.24 | Dx = 1.645 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 5411 reflections |
a = 8.2703 (9) Å | θ = 1.7–24.5° |
b = 13.1939 (14) Å | µ = 4.78 mm−1 |
c = 23.363 (3) Å | T = 100 K |
V = 2549.3 (5) Å3 | Needle, orange |
Z = 4 | 0.41 × 0.11 × 0.11 mm |
Bruker SMART APEX2 CCD area-detector diffractometer | 5850 independent reflections |
Radiation source: fine-focus sealed tube | 4248 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.089 |
Detector resolution: 8.33 pixels mm-1 | θmax = 27.5°, θmin = 1.7° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −17→17 |
Tmin = 0.248, Tmax = 0.629 | l = −30→30 |
31119 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.0578P)2 + 1.0999P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
5850 reflections | Δρmax = 0.87 e Å−3 |
281 parameters | Δρmin = −0.81 e Å−3 |
6 restraints | Absolute structure: Flack (1983), with 2535 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.638 (14) |
C20H36O6·H3O+·Br3− | V = 2549.3 (5) Å3 |
Mr = 631.24 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.2703 (9) Å | µ = 4.78 mm−1 |
b = 13.1939 (14) Å | T = 100 K |
c = 23.363 (3) Å | 0.41 × 0.11 × 0.11 mm |
Bruker SMART APEX2 CCD area-detector diffractometer | 5850 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 4248 reflections with I > 2σ(I) |
Tmin = 0.248, Tmax = 0.629 | Rint = 0.089 |
31119 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.122 | Δρmax = 0.87 e Å−3 |
S = 1.09 | Δρmin = −0.81 e Å−3 |
5850 reflections | Absolute structure: Flack (1983), with 2535 Friedel pairs |
281 parameters | Absolute structure parameter: 0.638 (14) |
6 restraints |
Experimental. The data was collected with the Oxford Cyrosystem Cobra low-temperature attachment. |
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 | ||
Br1 | 0.50581 (7) | 0.45651 (5) | 0.20640 (2) | 0.02836 (15) | |
Br2 | 0.46209 (9) | 0.57409 (6) | 0.28793 (3) | 0.0431 (2) | |
Br3 | 0.54389 (9) | 0.33108 (5) | 0.11935 (3) | 0.03887 (19) | |
O1 | 0.9888 (5) | 0.5804 (3) | 0.13934 (16) | 0.0259 (9) | |
O2 | 0.9961 (5) | 0.4629 (3) | 0.03717 (16) | 0.0253 (8) | |
O3 | 0.7158 (4) | 0.4708 (3) | −0.03546 (17) | 0.0230 (9) | |
O4 | 0.5259 (4) | 0.6398 (3) | −0.02434 (15) | 0.0196 (8) | |
O5 | 0.5170 (5) | 0.7480 (3) | 0.07877 (15) | 0.0212 (8) | |
O6 | 0.7817 (5) | 0.7404 (3) | 0.15891 (17) | 0.0238 (9) | |
C1 | 1.1254 (7) | 0.5219 (5) | 0.1214 (3) | 0.0303 (15) | |
H1A | 1.1872 | 0.5008 | 0.1546 | 0.036* | |
H1B | 1.1948 | 0.5629 | 0.0973 | 0.036* | |
C2 | 1.0695 (7) | 0.4312 (5) | 0.0892 (3) | 0.0281 (14) | |
H2A | 1.1607 | 0.3872 | 0.0810 | 0.034* | |
H2B | 0.9923 | 0.3934 | 0.1120 | 0.034* | |
C3 | 0.9354 (7) | 0.3796 (5) | 0.0057 (2) | 0.0257 (13) | |
H3A | 0.8548 | 0.3441 | 0.0282 | 0.031* | |
H3B | 1.0226 | 0.3327 | −0.0026 | 0.031* | |
C4 | 0.8615 (7) | 0.4154 (5) | −0.0490 (3) | 0.0282 (14) | |
H4A | 0.9367 | 0.4588 | −0.0693 | 0.034* | |
H4B | 0.8360 | 0.3579 | −0.0733 | 0.034* | |
C5 | 0.6289 (6) | 0.5088 (4) | −0.0847 (2) | 0.0193 (12) | |
H5A | 0.6950 | 0.5600 | −0.1041 | 0.023* | |
C6 | 0.5845 (7) | 0.4259 (5) | −0.1271 (2) | 0.0249 (13) | |
H6A | 0.6821 | 0.3938 | −0.1412 | 0.030* | |
H6B | 0.5280 | 0.4554 | −0.1594 | 0.030* | |
C7 | 0.4765 (8) | 0.3463 (4) | −0.0985 (3) | 0.0290 (14) | |
H7A | 0.4443 | 0.2960 | −0.1265 | 0.035* | |
H7B | 0.5366 | 0.3121 | −0.0685 | 0.035* | |
C8 | 0.3263 (7) | 0.3961 (5) | −0.0729 (3) | 0.0303 (15) | |
H8A | 0.2601 | 0.4232 | −0.1036 | 0.036* | |
H8B | 0.2632 | 0.3453 | −0.0529 | 0.036* | |
C9 | 0.3699 (7) | 0.4806 (5) | −0.0318 (3) | 0.0238 (14) | |
H9A | 0.4249 | 0.4525 | 0.0012 | 0.029* | |
H9B | 0.2721 | 0.5137 | −0.0186 | 0.029* | |
C10 | 0.4794 (7) | 0.5582 (4) | −0.0611 (2) | 0.0227 (12) | |
H10A | 0.4193 | 0.5872 | −0.0933 | 0.027* | |
C11 | 0.3958 (7) | 0.7063 (5) | −0.0104 (3) | 0.0261 (14) | |
H11A | 0.3113 | 0.6686 | 0.0090 | 0.031* | |
H11B | 0.3505 | 0.7344 | −0.0453 | 0.031* | |
C12 | 0.4534 (7) | 0.7904 (4) | 0.0272 (2) | 0.0230 (13) | |
H12A | 0.5366 | 0.8290 | 0.0078 | 0.028* | |
H12B | 0.3645 | 0.8356 | 0.0361 | 0.028* | |
C13 | 0.5503 (7) | 0.8242 (5) | 0.1199 (2) | 0.0231 (12) | |
H13A | 0.4511 | 0.8591 | 0.1301 | 0.028* | |
H13B | 0.6248 | 0.8735 | 0.1040 | 0.028* | |
C14 | 0.6237 (7) | 0.7760 (5) | 0.1725 (3) | 0.0268 (14) | |
H14A | 0.6296 | 0.8253 | 0.2032 | 0.032* | |
H14B | 0.5567 | 0.7200 | 0.1852 | 0.032* | |
C15 | 0.8604 (7) | 0.6903 (5) | 0.2066 (3) | 0.0259 (13) | |
H15A | 0.7941 | 0.6332 | 0.2196 | 0.031* | |
C16 | 0.8918 (8) | 0.7619 (5) | 0.2565 (3) | 0.0309 (15) | |
H16A | 0.7895 | 0.7876 | 0.2707 | 0.037* | |
H16B | 0.9433 | 0.7246 | 0.2874 | 0.037* | |
C17 | 0.9985 (9) | 0.8501 (5) | 0.2396 (2) | 0.0310 (14) | |
H17A | 1.0187 | 0.8925 | 0.2727 | 0.037* | |
H17B | 0.9438 | 0.8908 | 0.2109 | 0.037* | |
C18 | 1.1579 (7) | 0.8118 (5) | 0.2156 (3) | 0.0328 (16) | |
H18A | 1.2188 | 0.7795 | 0.2461 | 0.039* | |
H18B | 1.2206 | 0.8690 | 0.2020 | 0.039* | |
C19 | 1.1349 (7) | 0.7362 (5) | 0.1667 (3) | 0.0276 (14) | |
H19A | 1.0902 | 0.7709 | 0.1337 | 0.033* | |
H19B | 1.2388 | 0.7081 | 0.1558 | 0.033* | |
C20 | 1.0221 (7) | 0.6514 (4) | 0.1847 (2) | 0.0233 (13) | |
H20A | 1.0743 | 0.6141 | 0.2160 | 0.028* | |
O7 | 0.6958 (5) | 0.5617 (4) | 0.0781 (2) | 0.0392 (12) | |
H7OA | 0.703 (8) | 0.539 (4) | 0.0434 (10) | 0.059* | |
H7OB | 0.655 (8) | 0.512 (3) | 0.097 (2) | 0.059* | |
H7OC | 0.622 (6) | 0.608 (4) | 0.077 (3) | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0157 (2) | 0.0360 (3) | 0.0334 (3) | −0.0008 (3) | −0.0016 (2) | 0.0130 (3) |
Br2 | 0.0440 (4) | 0.0503 (4) | 0.0349 (4) | 0.0017 (3) | 0.0087 (3) | 0.0050 (3) |
Br3 | 0.0446 (4) | 0.0289 (3) | 0.0431 (4) | −0.0083 (3) | 0.0040 (3) | 0.0028 (3) |
O1 | 0.0150 (19) | 0.024 (2) | 0.039 (2) | 0.0024 (19) | −0.0083 (18) | −0.0019 (17) |
O2 | 0.0186 (18) | 0.025 (2) | 0.032 (2) | 0.002 (2) | −0.0020 (18) | 0.0023 (17) |
O3 | 0.0146 (19) | 0.028 (2) | 0.026 (2) | 0.0076 (18) | 0.0023 (16) | 0.0007 (19) |
O4 | 0.0102 (19) | 0.023 (2) | 0.025 (2) | 0.0016 (17) | −0.0028 (16) | −0.0025 (15) |
O5 | 0.017 (2) | 0.022 (2) | 0.0242 (19) | 0.0011 (18) | −0.0041 (17) | −0.0007 (15) |
O6 | 0.016 (2) | 0.031 (3) | 0.025 (2) | 0.0010 (18) | −0.0008 (16) | 0.0019 (19) |
C1 | 0.012 (3) | 0.033 (4) | 0.046 (4) | 0.009 (3) | −0.007 (3) | 0.002 (3) |
C2 | 0.020 (3) | 0.026 (3) | 0.038 (3) | 0.012 (3) | 0.001 (3) | 0.004 (3) |
C3 | 0.020 (3) | 0.023 (3) | 0.034 (3) | 0.003 (3) | 0.007 (3) | 0.004 (3) |
C4 | 0.019 (3) | 0.029 (4) | 0.036 (4) | 0.010 (3) | 0.010 (3) | −0.002 (3) |
C5 | 0.011 (3) | 0.023 (3) | 0.025 (3) | −0.005 (2) | 0.001 (2) | 0.005 (3) |
C6 | 0.021 (3) | 0.027 (3) | 0.026 (3) | −0.003 (3) | 0.004 (2) | −0.004 (3) |
C7 | 0.029 (3) | 0.020 (3) | 0.038 (3) | −0.003 (3) | 0.009 (3) | −0.006 (3) |
C8 | 0.018 (3) | 0.029 (4) | 0.044 (4) | −0.006 (3) | 0.003 (3) | 0.000 (3) |
C9 | 0.018 (3) | 0.023 (3) | 0.030 (3) | 0.001 (2) | 0.005 (2) | 0.002 (3) |
C10 | 0.025 (3) | 0.020 (3) | 0.024 (3) | 0.001 (3) | 0.004 (2) | −0.002 (2) |
C11 | 0.013 (3) | 0.028 (4) | 0.037 (4) | 0.005 (3) | −0.004 (3) | 0.003 (3) |
C12 | 0.013 (3) | 0.027 (3) | 0.029 (3) | 0.007 (2) | −0.001 (2) | 0.000 (2) |
C13 | 0.013 (3) | 0.032 (3) | 0.024 (3) | 0.000 (3) | 0.001 (2) | 0.001 (3) |
C14 | 0.013 (3) | 0.040 (4) | 0.028 (3) | −0.001 (3) | 0.002 (2) | −0.002 (3) |
C15 | 0.024 (3) | 0.026 (3) | 0.028 (3) | 0.000 (3) | −0.003 (3) | 0.006 (3) |
C16 | 0.027 (3) | 0.037 (4) | 0.029 (3) | −0.006 (3) | −0.005 (3) | 0.008 (3) |
C17 | 0.034 (3) | 0.035 (4) | 0.024 (3) | −0.005 (3) | −0.006 (3) | 0.000 (2) |
C18 | 0.022 (3) | 0.036 (4) | 0.040 (4) | −0.007 (3) | −0.009 (3) | 0.005 (3) |
C19 | 0.018 (3) | 0.030 (4) | 0.035 (4) | −0.003 (3) | −0.005 (3) | 0.007 (3) |
C20 | 0.018 (3) | 0.024 (3) | 0.028 (3) | −0.003 (3) | −0.009 (3) | 0.006 (2) |
O7 | 0.033 (2) | 0.044 (3) | 0.041 (3) | 0.002 (2) | 0.004 (2) | 0.002 (2) |
Br1—Br2 | 2.4831 (9) | C8—H8B | 0.97 |
Br1—Br3 | 2.6408 (9) | C9—C10 | 1.528 (8) |
O1—C1 | 1.430 (7) | C9—H9A | 0.97 |
O1—C20 | 1.442 (7) | C9—H9B | 0.97 |
O2—C3 | 1.415 (7) | C10—H10A | 0.98 |
O2—C2 | 1.422 (7) | C11—C12 | 1.494 (8) |
O3—C4 | 1.444 (7) | C11—H11A | 0.97 |
O3—C5 | 1.446 (7) | C11—H11B | 0.97 |
O4—C11 | 1.427 (7) | C12—H12A | 0.97 |
O4—C10 | 1.429 (6) | C12—H12B | 0.97 |
O5—C13 | 1.418 (7) | C13—C14 | 1.511 (8) |
O5—C12 | 1.428 (7) | C13—H13A | 0.97 |
O6—C14 | 1.425 (7) | C13—H13B | 0.97 |
O6—C15 | 1.450 (7) | C14—H14A | 0.97 |
C1—C2 | 1.488 (9) | C14—H14B | 0.97 |
C1—H1A | 0.97 | C15—C20 | 1.521 (8) |
C1—H1B | 0.97 | C15—C16 | 1.522 (9) |
C2—H2A | 0.97 | C15—H15A | 0.98 |
C2—H2B | 0.97 | C16—C17 | 1.513 (9) |
C3—C4 | 1.492 (8) | C16—H16A | 0.97 |
C3—H3A | 0.97 | C16—H16B | 0.97 |
C3—H3B | 0.97 | C17—C18 | 1.519 (9) |
C4—H4A | 0.97 | C17—H17A | 0.97 |
C4—H4B | 0.97 | C17—H17B | 0.97 |
C5—C10 | 1.503 (8) | C18—C19 | 1.530 (9) |
C5—C6 | 1.521 (8) | C18—H18A | 0.97 |
C5—H5A | 0.98 | C18—H18B | 0.97 |
C6—C7 | 1.531 (8) | C19—C20 | 1.518 (8) |
C6—H6A | 0.97 | C19—H19A | 0.97 |
C6—H6B | 0.97 | C19—H19B | 0.97 |
C7—C8 | 1.527 (8) | C20—H20A | 0.98 |
C7—H7A | 0.97 | O7—H7OA | 0.87 (3) |
C7—H7B | 0.97 | O7—H7OB | 0.86 (5) |
C8—C9 | 1.516 (9) | O7—H7OC | 0.86 (5) |
C8—H8A | 0.97 | ||
Br2—Br1—Br3 | 178.48 (4) | C5—C10—H10A | 107.7 |
C1—O1—C20 | 114.5 (4) | C9—C10—H10A | 107.7 |
C3—O2—C2 | 111.6 (4) | O4—C11—C12 | 110.5 (5) |
C4—O3—C5 | 114.6 (4) | O4—C11—H11A | 109.5 |
C11—O4—C10 | 113.4 (4) | C12—C11—H11A | 109.5 |
C13—O5—C12 | 111.4 (4) | O4—C11—H11B | 109.5 |
C14—O6—C15 | 113.0 (4) | C12—C11—H11B | 109.5 |
O1—C1—C2 | 109.7 (5) | H11A—C11—H11B | 108.1 |
O1—C1—H1A | 109.7 | O5—C12—C11 | 108.9 (5) |
C2—C1—H1A | 109.7 | O5—C12—H12A | 109.9 |
O1—C1—H1B | 109.7 | C11—C12—H12A | 109.9 |
C2—C1—H1B | 109.7 | O5—C12—H12B | 109.9 |
H1A—C1—H1B | 108.2 | C11—C12—H12B | 109.9 |
O2—C2—C1 | 109.2 (5) | H12A—C12—H12B | 108.3 |
O2—C2—H2A | 109.8 | O5—C13—C14 | 109.3 (5) |
C1—C2—H2A | 109.8 | O5—C13—H13A | 109.8 |
O2—C2—H2B | 109.8 | C14—C13—H13A | 109.8 |
C1—C2—H2B | 109.8 | O5—C13—H13B | 109.8 |
H2A—C2—H2B | 108.3 | C14—C13—H13B | 109.8 |
O2—C3—C4 | 110.2 (5) | H13A—C13—H13B | 108.3 |
O2—C3—H3A | 109.6 | O6—C14—C13 | 109.0 (5) |
C4—C3—H3A | 109.6 | O6—C14—H14A | 109.9 |
O2—C3—H3B | 109.6 | C13—C14—H14A | 109.9 |
C4—C3—H3B | 109.6 | O6—C14—H14B | 109.9 |
H3A—C3—H3B | 108.1 | C13—C14—H14B | 109.9 |
O3—C4—C3 | 108.3 (5) | H14A—C14—H14B | 108.3 |
O3—C4—H4A | 110.0 | O6—C15—C20 | 106.8 (5) |
C3—C4—H4A | 110.0 | O6—C15—C16 | 112.5 (5) |
O3—C4—H4B | 110.0 | C20—C15—C16 | 108.5 (5) |
C3—C4—H4B | 110.0 | O6—C15—H15A | 109.6 |
H4A—C4—H4B | 108.4 | C20—C15—H15A | 109.6 |
O3—C5—C10 | 105.5 (4) | C16—C15—H15A | 109.6 |
O3—C5—C6 | 112.8 (5) | C17—C16—C15 | 112.0 (5) |
C10—C5—C6 | 110.6 (4) | C17—C16—H16A | 109.2 |
O3—C5—H5A | 109.3 | C15—C16—H16A | 109.2 |
C10—C5—H5A | 109.3 | C17—C16—H16B | 109.2 |
C6—C5—H5A | 109.3 | C15—C16—H16B | 109.2 |
C5—C6—C7 | 110.5 (5) | H16A—C16—H16B | 107.9 |
C5—C6—H6A | 109.5 | C16—C17—C18 | 110.3 (5) |
C7—C6—H6A | 109.5 | C16—C17—H17A | 109.6 |
C5—C6—H6B | 109.5 | C18—C17—H17A | 109.6 |
C7—C6—H6B | 109.5 | C16—C17—H17B | 109.6 |
H6A—C6—H6B | 108.1 | C18—C17—H17B | 109.6 |
C8—C7—C6 | 110.5 (5) | H17A—C17—H17B | 108.1 |
C8—C7—H7A | 109.6 | C17—C18—C19 | 112.6 (5) |
C6—C7—H7A | 109.6 | C17—C18—H18A | 109.1 |
C8—C7—H7B | 109.6 | C19—C18—H18A | 109.1 |
C6—C7—H7B | 109.6 | C17—C18—H18B | 109.1 |
H7A—C7—H7B | 108.1 | C19—C18—H18B | 109.1 |
C9—C8—C7 | 111.8 (5) | H18A—C18—H18B | 107.8 |
C9—C8—H8A | 109.3 | C20—C19—C18 | 110.4 (5) |
C7—C8—H8A | 109.3 | C20—C19—H19A | 109.6 |
C9—C8—H8B | 109.3 | C18—C19—H19A | 109.6 |
C7—C8—H8B | 109.3 | C20—C19—H19B | 109.6 |
H8A—C8—H8B | 107.9 | C18—C19—H19B | 109.6 |
C8—C9—C10 | 110.5 (5) | H19A—C19—H19B | 108.1 |
C8—C9—H9A | 109.5 | O1—C20—C19 | 113.1 (5) |
C10—C9—H9A | 109.5 | O1—C20—C15 | 107.4 (4) |
C8—C9—H9B | 109.5 | C19—C20—C15 | 112.6 (5) |
C10—C9—H9B | 109.5 | O1—C20—H20A | 107.8 |
H9A—C9—H9B | 108.1 | C19—C20—H20A | 107.8 |
O4—C10—C5 | 109.0 (4) | C15—C20—H20A | 107.8 |
O4—C10—C9 | 113.3 (4) | H7OA—O7—H7OB | 104 (5) |
C5—C10—C9 | 111.2 (5) | H7OA—O7—H7OC | 105 (6) |
O4—C10—H10A | 107.7 | H7OB—O7—H7OC | 106 (6) |
C20—O1—C1—C2 | 162.0 (5) | C10—O4—C11—C12 | −179.1 (4) |
C3—O2—C2—C1 | −177.9 (5) | C13—O5—C12—C11 | −170.8 (4) |
O1—C1—C2—O2 | 66.3 (6) | O4—C11—C12—O5 | −60.2 (6) |
C2—O2—C3—C4 | −179.1 (4) | C12—O5—C13—C14 | −177.6 (4) |
C5—O3—C4—C3 | −179.0 (5) | C15—O6—C14—C13 | −178.5 (5) |
O2—C3—C4—O3 | −69.0 (6) | O5—C13—C14—O6 | 69.3 (6) |
C4—O3—C5—C10 | 177.1 (5) | C14—O6—C15—C20 | 176.7 (5) |
C4—O3—C5—C6 | 56.2 (6) | C14—O6—C15—C16 | −64.3 (6) |
O3—C5—C6—C7 | 60.0 (6) | O6—C15—C16—C17 | −59.5 (7) |
C10—C5—C6—C7 | −57.9 (6) | C20—C15—C16—C17 | 58.5 (7) |
C5—C6—C7—C8 | 56.1 (7) | C15—C16—C17—C18 | −57.3 (7) |
C6—C7—C8—C9 | −55.2 (7) | C16—C17—C18—C19 | 53.9 (7) |
C7—C8—C9—C10 | 55.0 (7) | C17—C18—C19—C20 | −52.6 (7) |
C11—O4—C10—C5 | 166.1 (5) | C1—O1—C20—C19 | 66.7 (6) |
C11—O4—C10—C9 | −69.6 (6) | C1—O1—C20—C15 | −168.4 (5) |
O3—C5—C10—O4 | 61.3 (5) | C18—C19—C20—O1 | 176.9 (5) |
C6—C5—C10—O4 | −176.4 (4) | C18—C19—C20—C15 | 54.9 (6) |
O3—C5—C10—C9 | −64.3 (6) | O6—C15—C20—O1 | −61.0 (6) |
C6—C5—C10—C9 | 58.1 (6) | C16—C15—C20—O1 | 177.4 (4) |
C8—C9—C10—O4 | −179.6 (5) | O6—C15—C20—C19 | 64.1 (6) |
C8—C9—C10—C5 | −56.4 (6) | C16—C15—C20—C19 | −57.4 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7OA···O3 | 0.87 (3) | 2.05 (3) | 2.916 (6) | 174 (6) |
O7—H7OA···O4 | 0.87 (3) | 2.53 (5) | 2.960 (6) | 111 (5) |
O7—H7OB···Br3 | 0.86 (5) | 2.61 (4) | 3.430 (5) | 160 (4) |
O7—H7OC···O4 | 0.86 (5) | 2.53 (7) | 2.960 (6) | 112 (5) |
O7—H7OC···O5 | 0.86 (5) | 2.04 (5) | 2.869 (6) | 160 (5) |
Experimental details
Crystal data | |
Chemical formula | C20H36O6·H3O+·Br3− |
Mr | 631.24 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 8.2703 (9), 13.1939 (14), 23.363 (3) |
V (Å3) | 2549.3 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.78 |
Crystal size (mm) | 0.41 × 0.11 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART APEX2 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.248, 0.629 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 31119, 5850, 4248 |
Rint | 0.089 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.122, 1.09 |
No. of reflections | 5850 |
No. of parameters | 281 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.87, −0.81 |
Absolute structure | Flack (1983), with 2535 Friedel pairs |
Absolute structure parameter | 0.638 (14) |
Computer programs: APEX2 (Bruker, 2005), APEX2, SAINT (Bruker, 2005), SHELXTL (Sheldrick, 1998), SHELXTL and PLATON (Spek, 2003).
C20—O1—C1—C2 | 162.0 (5) | C10—O4—C11—C12 | −179.1 (4) |
C3—O2—C2—C1 | −177.9 (5) | C13—O5—C12—C11 | −170.8 (4) |
O1—C1—C2—O2 | 66.3 (6) | O4—C11—C12—O5 | −60.2 (6) |
C2—O2—C3—C4 | −179.1 (4) | C12—O5—C13—C14 | −177.6 (4) |
C5—O3—C4—C3 | −179.0 (5) | C15—O6—C14—C13 | −178.5 (5) |
O2—C3—C4—O3 | −69.0 (6) | O5—C13—C14—O6 | 69.3 (6) |
C4—O3—C5—C10 | 177.1 (5) | C14—O6—C15—C20 | 176.7 (5) |
C4—O3—C5—C6 | 56.2 (6) | C1—O1—C20—C15 | −168.4 (5) |
C11—O4—C10—C5 | 166.1 (5) | O6—C15—C20—O1 | −61.0 (6) |
O3—C5—C10—O4 | 61.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7OA···O3 | 0.87 (3) | 2.05 (3) | 2.916 (6) | 174 (6) |
O7—H7OA···O4 | 0.87 (3) | 2.53 (5) | 2.960 (6) | 111 (5) |
O7—H7OB···Br3 | 0.86 (5) | 2.61 (4) | 3.430 (5) | 160 (4) |
O7—H7OC···O4 | 0.86 (5) | 2.53 (7) | 2.960 (6) | 112 (5) |
O7—H7OC···O5 | 0.86 (5) | 2.04 (5) | 2.869 (6) | 160 (5) |
The complexation of dicyclohexano-18-crown-6 (DCH18C6) with some lanthanide ions normally leads to the formation of a complex via metal–oxygen chelation such as {La(NO3)3(DCH18C6)]} (Harman et al., 1976) and {[Eu(NO3)2(DCH18C6)]2[Eu(NO3)5]} (Nicoló et al., 1987) and salt-type compounds namely [Ln(Pic)2(DCH18C6)]+(Pic)- for Ln = La and Ce and also [Ln(Pic)2(DCH18C6)]+(Pic)-·0.5(DCH18C6) for Ln = Pr and Nd (Kusrini, 2006). However, different products without lanthanide coordination with crown ethers have also been observed namely (15-crown-5)triaquadichlorodioxouranium (Hassaballa et al., 1998) and [Gd(NO3)3(OH2)3].18-crown-6 (Backer-Dirks et al., 1980).
In our study, no complexation product was obtained from a solution mixture containing dicyclohexano-18-crown-6, europium nitrate and hydrogen bromide. Instead, the formation of a tribromide anion along with a hydroxonium ion occurred. A similar product, namely, bis(2,3-dibromo-6,7,9,10,12,13,15,16-octahydro- 5,8,11,14,17-pentaoxabenzocyclopentadecene)hydroxonium tribromide has been reported (Saleh et al., 2006).
Bond lengths and angles are in normal ranges (Allen et al., 1987). The macrocyclic strand of the molecule displays a series of anti and gauche torsion angles for C—O and C—C bonds (Fig. 1). The individual O—C—C—O segments are ag+a, ag-a, ag+a, ag-a, ag+a and ag-a. Relevant torsion angles are listed in Table 1. Both cyclohexane rings adopt chair conformations, with puckering parameters Q = 0.578 (6) Å, θ = 0.0 (6)° and φ = 8(20)° for the C5–C10 ring, and Q = 0.568 (7) Å, θ = 176.2 (7)° and φ = 200 (10)° for the C15–C20 ring (Cremer & Pople, 1975).
The crystal structure is stabilized by O—H···Br and O—H···O hydrogen bonds (Table 2, Fig. 2).