Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100018473/bj1007sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100018473/bj1007Isup2.hkl |
CCDC reference: 162570
To a refluxing suspension of 95% sodium hydride (0.132 g, 5.50 mmol) in tetrahydrofuran (THF; 50 ml) was added dropwise a solution of 1,2,4,5-tetrakis(bromomethyl)benzene (1.00 g, 2.20 mmol) and 1,5-bis(2-hydroxyphenoxy)-3-oxapentane (0.580 g, 2.00 mmol) in THF (50 ml) for 3 h under N2 atmosphere. The reaction mixture was refluxed for an additional 24 h. After cooling to room temperature, 10% aqueous hydrochloric acid was added. The solvent (THF) was removed under reduced pressure, and the aqueous layer was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and evaporated in vacuo. The crude product was chromatographed on a silica gel using a mixed solvent of ethyl acetate and n-hexane (1:1) as an eluent, and recrystallized from dichloromethane/n-hexane (1:20, V/V). Crystalline (I) was obtained in 30% yield (0.35 g), m.p. 455–456 K. Found: C 54.67, H 4.65%. C26H26Br2O5 requires C 54.00, H 4.53%); IR (KBr pellet) 2929, 1599, 1506, 1452, 1260, 1212, 1128, 749 and 610 cm-1; 1H NMR (CDCl3): δ 7.65 (s, 2 H, arom.), 7.06–6.85 (m, 8 H, arom.), 5.20 (s, 4 H, OCH2Ar), 4.71 (s, 4H, ArCH2Br), 4.15(t, 4 H, ArOCH2CH2O) and 3.85) t.4 H, ArOCH2CH2O); 13C NMR (CDCl3) δ 150.562, 147.841, 137.211, 135.607, 130.644, 123.331, 120.957, 119.278 and 112.842 (Ar), 70.399, 69.514 and 67.818 (CH2O) and 30.032 (CH2Br). MS(m/z) 578(M+), 307, 182, 154, 136, 107.
Atoms C12, and C13 in benzene ring B and C21, C22, C23, C24 in benzene ring C were disordered into two positions, respectively, and refined isotropically with the occupancy 0.49 (6) for the unprimed atoms and 0.51 (6) for the primed atoms using both the TWIN and BASF instructions. All H atoms were fixed geometrically and allowed to ride on their attached atoms and their isotropic displacement parameters were fixed at 1.2 times the equivalent isotropic displacement parameters of their parent atoms. The largest peak in the final electron-density map is 0.58 e Å3 at (0.0979, 0.3736, 0.0350), 1.24 Å from the Br2 atom.
Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).
C26H26Br2O5 | Dx = 1.565 Mg m−3 |
Mr = 578.29 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 8.141 (2) Å | θ = 11.4–13.8° |
b = 13.7976 (16) Å | µ = 3.34 mm−1 |
c = 21.852 (2) Å | T = 293 K |
V = 2454.6 (7) Å3 | Plate, colorless |
Z = 4 | 0.53 × 0.36 × 0.13 mm |
F(000) = 1168 |
Enraf Nonius CAD4 diffractometer | 1137 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 25.0°, θmin = 2.4° |
non–profiled ω/2θ scans | h = −2→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −4→16 |
Tmin = 0.247, Tmax = 0.644 | l = −6→25 |
2564 measured reflections | 3 standard reflections every 300 min |
2516 independent 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)] = 0.064 | H-atom parameters constrained |
wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.0403P)2 + 1.4141P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
2516 reflections | Δρmax = 0.58 e Å−3 |
294 parameters | Δρmin = −0.42 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.33 (3) |
C26H26Br2O5 | V = 2454.6 (7) Å3 |
Mr = 578.29 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.141 (2) Å | µ = 3.34 mm−1 |
b = 13.7976 (16) Å | T = 293 K |
c = 21.852 (2) Å | 0.53 × 0.36 × 0.13 mm |
Enraf Nonius CAD4 diffractometer | 2516 independent reflections |
Absorption correction: ψ scan (North et al., 1968) | 1137 reflections with I > 2σ(I) |
Tmin = 0.247, Tmax = 0.644 | Rint = 0.013 |
2564 measured reflections | 3 standard reflections every 300 min |
R[F2 > 2σ(F2)] = 0.064 | H-atom parameters constrained |
wR(F2) = 0.123 | Δρmax = 0.58 e Å−3 |
S = 1.01 | Δρmin = −0.42 e Å−3 |
2516 reflections | Absolute structure: Flack (1983) |
294 parameters | Absolute structure parameter: 0.33 (3) |
0 restraints |
Experimental. H atoms treated by constrained refinement |
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 | −0.35852 (19) | 0.12183 (11) | 0.11245 (7) | 0.0895 (6) | |
Br2 | −0.3442 (2) | 0.13257 (11) | −0.08749 (8) | 0.0979 (6) | |
O1 | 0.2557 (11) | −0.0494 (6) | 0.1410 (5) | 0.066 (3) | |
O2 | 0.3377 (12) | −0.2384 (6) | 0.1168 (4) | 0.066 (3) | |
O3 | 0.3539 (11) | −0.3224 (5) | −0.0018 (5) | 0.072 (3) | |
O4 | 0.3295 (12) | −0.2149 (7) | −0.1140 (4) | 0.075 (3) | |
O5 | 0.2500 (12) | −0.0241 (7) | −0.1188 (5) | 0.070 (3) | |
C1 | −0.1668 (17) | 0.1962 (8) | 0.0906 (6) | 0.073 (4) | |
H1A | −0.2007 | 0.2543 | 0.0691 | 0.088* | |
H1B | −0.1099 | 0.2159 | 0.1276 | 0.088* | |
C2 | −0.0508 (16) | 0.1389 (10) | 0.0506 (7) | 0.054 (4) | |
C3 | −0.0540 (14) | 0.1448 (8) | −0.0136 (8) | 0.051 (3) | |
C4 | −0.1722 (18) | 0.2084 (8) | −0.0484 (6) | 0.077 (4) | |
H4A | −0.1125 | 0.2445 | −0.0793 | 0.092* | |
H4B | −0.2216 | 0.2546 | −0.0205 | 0.092* | |
C5 | 0.0575 (16) | 0.0911 (8) | −0.0458 (6) | 0.051 (4) | |
H5 | 0.0577 | 0.0971 | −0.0882 | 0.061* | |
C6 | 0.1691 (15) | 0.0288 (7) | −0.0199 (7) | 0.041 (3) | |
C7 | 0.1692 (16) | 0.0212 (8) | 0.0434 (7) | 0.046 (3) | |
C8 | 0.0636 (17) | 0.0769 (9) | 0.0758 (7) | 0.055 (4) | |
H8 | 0.0685 | 0.0730 | 0.1183 | 0.066* | |
C9 | 0.2874 (15) | −0.0452 (8) | 0.0760 (6) | 0.058 (4) | |
H9A | 0.2785 | −0.1099 | 0.0589 | 0.070* | |
H9B | 0.3987 | −0.0226 | 0.0693 | 0.070* | |
C10 | 0.372 (2) | −0.0963 (10) | 0.1754 (6) | 0.053 (4) | |
C11 | 0.4361 (19) | −0.0456 (11) | 0.2251 (7) | 0.075 (5) | |
H11 | 0.4171 | 0.0194 | 0.2339 | 0.090* | |
C12 | 0.536 (5) | −0.110 (4) | 0.2605 (19) | 0.068 (13)* | 0.49 (6) |
H12 | 0.5858 | −0.0835 | 0.2950 | 0.081* | 0.49 (6) |
C12' | 0.552 (5) | −0.070 (4) | 0.2686 (19) | 0.076 (16)* | 0.51 (6) |
H12' | 0.5949 | −0.0286 | 0.2983 | 0.091* | 0.51 (6) |
C13 | 0.567 (4) | −0.206 (3) | 0.2497 (18) | 0.049 (11)* | 0.49 (6) |
H13 | 0.6263 | −0.2438 | 0.2769 | 0.058* | 0.49 (6) |
C13' | 0.590 (5) | −0.164 (4) | 0.2601 (17) | 0.070 (14)* | 0.51 (6) |
H13' | 0.6657 | −0.1908 | 0.2871 | 0.084* | 0.51 (6) |
C14 | 0.515 (2) | −0.2365 (12) | 0.2057 (8) | 0.088 (6) | |
H14 | 0.5514 | −0.2982 | 0.1952 | 0.105* | |
C15 | 0.4061 (19) | −0.1944 (12) | 0.1658 (8) | 0.066 (5) | |
C16 | 0.373 (2) | −0.3376 (9) | 0.1056 (7) | 0.082 (5) | |
H16A | 0.3399 | −0.3768 | 0.1402 | 0.098* | |
H16B | 0.4901 | −0.3465 | 0.0991 | 0.098* | |
C17 | 0.2796 (16) | −0.3666 (9) | 0.0497 (8) | 0.082 (5) | |
H17A | 0.2814 | −0.4366 | 0.0452 | 0.098* | |
H17B | 0.1662 | −0.3459 | 0.0532 | 0.098* | |
C18 | 0.278 (2) | −0.3570 (10) | −0.0545 (8) | 0.096 (6) | |
H18A | 0.1637 | −0.3367 | −0.0550 | 0.115* | |
H18B | 0.2807 | −0.4272 | −0.0548 | 0.115* | |
C19 | 0.364 (2) | −0.3183 (10) | −0.1102 (7) | 0.087 (5) | |
H19A | 0.4817 | −0.3290 | −0.1067 | 0.104* | |
H19B | 0.3251 | −0.3511 | −0.1466 | 0.104* | |
C20 | 0.4062 (16) | −0.1618 (13) | −0.1570 (7) | 0.062 (5) | |
C21 | 0.508 (5) | −0.218 (3) | −0.1979 (16) | 0.060 (12)* | 0.49 (6) |
H21 | 0.5175 | −0.2852 | −0.1954 | 0.072* | 0.49 (6) |
C21' | 0.525 (5) | −0.178 (4) | −0.200 (2) | 0.068 (12)* | 0.51 (6) |
H21' | 0.5651 | −0.2408 | −0.2022 | 0.082* | 0.51 (6) |
C22 | 0.589 (5) | −0.165 (4) | −0.2403 (17) | 0.060 (13)* | 0.49 (6) |
H22 | 0.6622 | −0.1941 | −0.2671 | 0.072* | 0.49 (6) |
C22' | 0.594 (5) | −0.112 (4) | −0.2404 (17) | 0.067 (15)* | 0.51 (6) |
H22' | 0.6777 | −0.1315 | −0.2670 | 0.080* | 0.51 (6) |
C23 | 0.563 (6) | −0.067 (4) | −0.2436 (18) | 0.065 (15)* | 0.49 (6) |
H23 | 0.6209 | −0.0288 | −0.2711 | 0.077* | 0.49 (6) |
C23' | 0.537 (4) | −0.019 (3) | −0.2405 (15) | 0.057 (12)* | 0.51 (6) |
H23' | 0.5719 | 0.0222 | −0.2717 | 0.069* | 0.51 (6) |
C24 | 0.440 (5) | −0.024 (4) | −0.2027 (17) | 0.058 (12)* | 0.49 (6) |
H24 | 0.4148 | 0.0407 | −0.2106 | 0.070* | 0.49 (6) |
C24' | 0.429 (4) | 0.020 (3) | −0.1966 (15) | 0.056 (11)* | 0.51 (6) |
H24' | 0.4024 | 0.0849 | −0.1921 | 0.067* | 0.51 (6) |
C25 | 0.362 (2) | −0.0620 (11) | −0.1578 (7) | 0.059 (4) | |
C26 | 0.2845 (16) | −0.0322 (8) | −0.0559 (6) | 0.058 (4) | |
H26A | 0.3965 | −0.0117 | −0.0481 | 0.070* | |
H26B | 0.2741 | −0.0994 | −0.0433 | 0.070* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0573 (9) | 0.0883 (11) | 0.1229 (14) | −0.0099 (11) | 0.0183 (11) | −0.0094 (11) |
Br2 | 0.0803 (11) | 0.0716 (10) | 0.1416 (15) | 0.0107 (12) | −0.0439 (12) | −0.0041 (11) |
O1 | 0.082 (7) | 0.064 (6) | 0.052 (7) | 0.025 (6) | 0.007 (6) | 0.009 (5) |
O2 | 0.075 (7) | 0.055 (6) | 0.070 (7) | 0.006 (6) | −0.005 (7) | 0.009 (6) |
O3 | 0.069 (6) | 0.055 (5) | 0.092 (8) | −0.012 (5) | −0.003 (8) | −0.009 (6) |
O4 | 0.066 (7) | 0.081 (7) | 0.078 (7) | −0.001 (6) | 0.012 (7) | −0.012 (6) |
O5 | 0.062 (6) | 0.093 (7) | 0.056 (7) | 0.014 (6) | −0.003 (6) | 0.000 (7) |
C1 | 0.060 (10) | 0.053 (7) | 0.106 (12) | 0.003 (8) | 0.028 (11) | 0.009 (9) |
C2 | 0.056 (9) | 0.051 (9) | 0.054 (11) | −0.009 (9) | 0.012 (9) | −0.024 (10) |
C3 | 0.035 (7) | 0.025 (7) | 0.093 (12) | −0.003 (6) | −0.007 (9) | −0.014 (9) |
C4 | 0.074 (11) | 0.054 (8) | 0.102 (12) | −0.001 (9) | −0.013 (11) | 0.004 (8) |
C5 | 0.055 (9) | 0.033 (7) | 0.064 (10) | −0.005 (7) | −0.002 (9) | 0.018 (7) |
C6 | 0.046 (8) | 0.031 (7) | 0.046 (10) | −0.003 (7) | −0.002 (9) | −0.018 (7) |
C7 | 0.038 (9) | 0.049 (8) | 0.052 (10) | −0.017 (8) | 0.002 (9) | −0.008 (8) |
C8 | 0.052 (9) | 0.035 (8) | 0.077 (12) | −0.009 (7) | 0.009 (10) | −0.007 (8) |
C9 | 0.043 (9) | 0.063 (9) | 0.068 (12) | 0.020 (8) | −0.016 (9) | −0.009 (8) |
C10 | 0.064 (10) | 0.052 (9) | 0.043 (10) | 0.002 (9) | 0.003 (9) | 0.017 (8) |
C11 | 0.071 (12) | 0.091 (12) | 0.063 (12) | −0.016 (11) | 0.004 (9) | −0.018 (11) |
C14 | 0.095 (14) | 0.118 (15) | 0.051 (12) | 0.025 (12) | 0.024 (11) | 0.013 (12) |
C15 | 0.062 (12) | 0.077 (13) | 0.058 (12) | 0.005 (9) | 0.007 (10) | 0.021 (11) |
C16 | 0.098 (12) | 0.046 (10) | 0.102 (14) | 0.032 (9) | 0.020 (13) | 0.020 (9) |
C17 | 0.070 (10) | 0.038 (8) | 0.137 (14) | −0.006 (9) | 0.014 (12) | −0.017 (11) |
C18 | 0.119 (15) | 0.047 (10) | 0.122 (15) | 0.000 (11) | 0.008 (14) | −0.029 (11) |
C19 | 0.069 (11) | 0.057 (10) | 0.135 (16) | 0.021 (10) | −0.039 (13) | −0.044 (11) |
C20 | 0.027 (9) | 0.117 (16) | 0.042 (10) | 0.005 (9) | −0.006 (8) | −0.014 (10) |
C25 | 0.048 (10) | 0.081 (12) | 0.048 (11) | −0.001 (10) | −0.006 (10) | 0.008 (9) |
C26 | 0.055 (10) | 0.055 (9) | 0.065 (11) | 0.002 (8) | −0.004 (9) | −0.004 (8) |
Br1—C1 | 1.928 (12) | C10—C11 | 1.393 (16) |
Br2—C4 | 1.945 (13) | C10—C15 | 1.399 (16) |
O1—C10 | 1.372 (14) | C11—C12' | 1.38 (4) |
O1—C9 | 1.444 (13) | C11—C12 | 1.43 (5) |
O2—C15 | 1.351 (15) | C12—C13 | 1.37 (5) |
O2—C16 | 1.420 (13) | C12'—C13' | 1.35 (5) |
O3—C18 | 1.391 (14) | C13—C14 | 1.13 (4) |
O3—C17 | 1.416 (14) | C13'—C14 | 1.67 (5) |
O4—C20 | 1.344 (15) | C14—C15 | 1.373 (19) |
O4—C19 | 1.457 (14) | C16—C17 | 1.494 (15) |
O5—C25 | 1.354 (16) | C18—C19 | 1.504 (17) |
O5—C26 | 1.409 (13) | C20—C21' | 1.37 (4) |
C1—C2 | 1.510 (15) | C20—C25 | 1.424 (18) |
C2—C8 | 1.380 (15) | C20—C21 | 1.45 (4) |
C2—C3 | 1.406 (15) | C21—C22 | 1.36 (6) |
C3—C5 | 1.367 (14) | C21'—C22' | 1.38 (5) |
C3—C4 | 1.508 (15) | C22—C23 | 1.36 (5) |
C5—C6 | 1.373 (13) | C22'—C23' | 1.38 (5) |
C6—C7 | 1.386 (13) | C23—C24 | 1.47 (5) |
C6—C26 | 1.487 (15) | C23'—C24' | 1.41 (5) |
C7—C8 | 1.354 (15) | C24—C25 | 1.28 (4) |
C7—C9 | 1.508 (15) | C24'—C25 | 1.51 (4) |
C10—O1—C9 | 115.7 (10) | C13—C14—C15 | 129 (3) |
C15—O2—C16 | 119.0 (12) | C13—C14—C13' | 15 (3) |
C18—O3—C17 | 108.6 (12) | C15—C14—C13' | 116 (2) |
C20—O4—C19 | 119.0 (13) | O2—C15—C14 | 125.5 (16) |
C25—O5—C26 | 116.7 (11) | O2—C15—C10 | 118.2 (16) |
C2—C1—Br1 | 111.8 (8) | C14—C15—C10 | 116.1 (17) |
C8—C2—C3 | 116.5 (13) | O2—C16—C17 | 107.2 (11) |
C8—C2—C1 | 121.1 (14) | O3—C17—C16 | 108.4 (11) |
C3—C2—C1 | 122.4 (15) | O3—C18—C19 | 109.8 (14) |
C5—C3—C2 | 118.1 (13) | O4—C19—C18 | 107.7 (12) |
C5—C3—C4 | 118.6 (15) | O4—C20—C21' | 136 (3) |
C2—C3—C4 | 123.3 (14) | O4—C20—C25 | 114.8 (14) |
C3—C4—Br2 | 111.6 (8) | C21'—C20—C25 | 109 (3) |
C3—C5—C6 | 124.4 (13) | O4—C20—C21 | 114 (2) |
C5—C6—C7 | 117.4 (13) | C21'—C20—C21 | 23 (2) |
C5—C6—C26 | 123.6 (13) | C25—C20—C21 | 131 (3) |
C7—C6—C26 | 118.9 (14) | C22—C21—C20 | 114 (3) |
C8—C7—C6 | 118.6 (14) | C20—C21'—C22' | 129 (4) |
C8—C7—C9 | 120.1 (14) | C21—C22—C23 | 120 (4) |
C6—C7—C9 | 121.3 (14) | C23'—C22'—C21' | 118 (4) |
C7—C8—C2 | 124.9 (14) | C22—C23—C24 | 118 (4) |
O1—C9—C7 | 112.1 (11) | C22'—C23'—C24' | 125 (3) |
O1—C10—C11 | 116.7 (14) | C25—C24—C23 | 130 (4) |
O1—C10—C15 | 120.7 (15) | C23'—C24'—C25 | 109 (2) |
C11—C10—C15 | 122.0 (15) | C24—C25—O5 | 131 (3) |
C12'—C11—C10 | 132 (3) | C24—C25—C20 | 106 (3) |
C12'—C11—C12 | 24 (2) | O5—C25—C20 | 122.4 (14) |
C10—C11—C12 | 109 (2) | C24—C25—C24' | 24 (2) |
C13—C12—C11 | 128 (4) | O5—C25—C24' | 108 (2) |
C13'—C12'—C11 | 107 (3) | C20—C25—C24' | 130 (2) |
C14—C13—C12 | 116 (4) | O5—C26—C6 | 110.2 (11) |
C12'—C13'—C14 | 126 (3) | ||
Br1—C1—C2—C8 | −84.7 (13) | C11—C10—C15—O2 | 179.3 (12) |
Br1—C1—C2—C3 | 94.6 (13) | O1—C10—C15—C14 | −175.0 (12) |
C8—C2—C3—C5 | −1.5 (17) | C11—C10—C15—C14 | −4 (2) |
C1—C2—C3—C5 | 179.1 (9) | C15—O2—C16—C17 | 179.1 (11) |
C8—C2—C3—C4 | 179.5 (10) | C18—O3—C17—C16 | 174.1 (11) |
C1—C2—C3—C4 | 0.2 (19) | O2—C16—C17—O3 | 71.7 (13) |
C5—C3—C4—Br2 | 74.7 (12) | C17—O3—C18—C19 | −174.8 (11) |
C2—C3—C4—Br2 | −106.4 (12) | C20—O4—C19—C18 | 173.8 (12) |
C2—C3—C5—C6 | 2.5 (17) | O3—C18—C19—O4 | −70.2 (15) |
C4—C3—C5—C6 | −178.5 (10) | C19—O4—C20—C21' | −5 (3) |
C3—C5—C6—C7 | −0.8 (17) | C19—O4—C20—C25 | 179.0 (12) |
C3—C5—C6—C26 | 177.2 (10) | C19—O4—C20—C21 | 4 (2) |
C5—C6—C7—C8 | −1.8 (17) | O4—C20—C21—C22 | −178 (2) |
C26—C6—C7—C8 | −179.9 (9) | C21'—C20—C21—C22 | −15 (5) |
C5—C6—C7—C9 | −180.0 (9) | C25—C20—C21—C22 | 8 (4) |
C26—C6—C7—C9 | 2.0 (17) | O4—C20—C21'—C22' | −178 (3) |
C6—C7—C8—C2 | 2.8 (18) | C25—C20—C21'—C22' | −2 (4) |
C9—C7—C8—C2 | −179.1 (11) | C21—C20—C21'—C22' | 160 (9) |
C3—C2—C8—C7 | −1.0 (18) | C20—C21—C22—C23 | −4 (4) |
C1—C2—C8—C7 | 178.3 (11) | C20—C21'—C22'—C23' | −2 (5) |
C10—O1—C9—C7 | −170.5 (10) | C21—C22—C23—C24 | −3 (5) |
C8—C7—C9—O1 | 7.6 (16) | C21'—C22'—C23'—C24' | 9 (4) |
C6—C7—C9—O1 | −174.2 (10) | C22—C23—C24—C25 | 9 (6) |
C9—O1—C10—C11 | 127.0 (13) | C22'—C23'—C24'—C25 | −11 (4) |
C9—O1—C10—C15 | −61.7 (16) | C23—C24—C25—O5 | 179 (3) |
O1—C10—C11—C12' | 180 (2) | C23—C24—C25—C20 | −5 (4) |
C15—C10—C11—C12' | 9 (3) | C23—C24—C25—C24' | 162 (8) |
O1—C10—C11—C12 | 171.5 (19) | C26—O5—C25—C24 | −125 (3) |
C15—C10—C11—C12 | 0 (3) | C26—O5—C25—C20 | 59.8 (18) |
C12'—C11—C12—C13 | −165 (9) | C26—O5—C25—C24' | −117.9 (16) |
C10—C11—C12—C13 | 0 (4) | O4—C20—C25—C24 | −177.1 (18) |
C10—C11—C12'—C13' | −6 (4) | C21'—C20—C25—C24 | 6 (3) |
C12—C11—C12'—C13' | 13 (5) | C21—C20—C25—C24 | −3 (3) |
C11—C12—C13—C14 | 5 (5) | O4—C20—C25—O5 | −1 (2) |
C11—C12'—C13'—C14 | 1 (4) | C21'—C20—C25—O5 | −178 (2) |
C12—C13—C14—C15 | −10 (5) | C21—C20—C25—O5 | 173 (2) |
C12—C13—C14—C13' | 26 (8) | O4—C20—C25—C24' | 176.2 (19) |
C12'—C13'—C14—C13 | −148 (12) | C21'—C20—C25—C24' | −1 (3) |
C12'—C13'—C14—C15 | 1 (4) | C21—C20—C25—C24' | −10 (3) |
C16—O2—C15—C14 | 3 (2) | C23'—C24'—C25—C24 | −9 (5) |
C16—O2—C15—C10 | 178.9 (13) | C23'—C24'—C25—O5 | −175.8 (19) |
C13—C14—C15—O2 | −174 (3) | C23'—C24'—C25—C20 | 7 (3) |
C13'—C14—C15—O2 | 176.4 (17) | C25—O5—C26—C6 | 168.8 (11) |
C13—C14—C15—C10 | 10 (3) | C5—C6—C26—O5 | −6.2 (15) |
C13'—C14—C15—C10 | 0 (2) | C7—C6—C26—O5 | 171.8 (10) |
O1—C10—C15—O2 | 9 (2) |
Experimental details
Crystal data | |
Chemical formula | C26H26Br2O5 |
Mr | 578.29 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 8.141 (2), 13.7976 (16), 21.852 (2) |
V (Å3) | 2454.6 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.34 |
Crystal size (mm) | 0.53 × 0.36 × 0.13 |
Data collection | |
Diffractometer | Enraf Nonius CAD4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.247, 0.644 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2564, 2516, 1137 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.123, 1.01 |
No. of reflections | 2516 |
No. of parameters | 294 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.42 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.33 (3) |
Computer programs: CAD-4 EXPRESS (Enraf Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).
Since the first report on the synthesis and properties of crown ether (Pedersen, 1967), there has been tremendous interest in the synthesis and inclusion behavior of crown ethers (Pedersen, 1988; Cram, 1986; Lehn, 1988; Lnoue 1990; Weber et al., 1989). In spite of extensive studies on crown ethers, only a few common-nuclear biscrown compounds which contain a single benzene ring serving as a common aromatic unit have been explored (Loeb & Shimizu, 1992; Lee et al., 1992). In our previous papers, we have reported the synthesis and complexation behaviors of common-nuclear biscrown ethers (Lee et al., 1992; Lee et al., 1997). In this regard, we now report the preparation of new crown ether, (I), and its solid state structure, which could be a precursor of the common-nuclear biscrown ether bearing a benzene ring. \sch
The title compound with labelling scheme is shown in Fig. 1. The C—Br bond lengths are not significantly different and average to 1.937 (9) Å. Similarly, the Br—C—C angles do not differ significantly and average to a value of 111.7 (6)°. In the chain bridging benzo groups B and C, the average C—O—C angle is slightly larger than tetrahedral, while the O—C—C angle is very close to tetrahedral. In the A to B ring and A to C ring connectivities, the torsions C7—C9—O1—C10 and C6—C26—O5—C25 are 170.8 (11)° and 168.5 (12)° respectively, indicating the A ring is situated trans to both the B and C rings. The two O—C—C—O and four C—O—C—C torsion angles in the diethylene glycol group are gauche and trans, respectively, because there is one extra atom in the diethylene glycol back bond. Atom positions C12 and C13 in ring B and atom positions C21, C22, C23 and C24 atoms in ring C are disordered. Consequently, some of their bond lengths and angles differ considerably from the normal values. The interatomic distances O1···O3 = 4.96 (1) Å and O3···O5 = 4.92 (1) Å are too short to introduce guest atom inside the molecule.