Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801017020/cv6067sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801017020/cv6067Isup2.hkl |
CCDC reference: 176018
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.015 Å
- R factor = 0.069
- wR factor = 0.193
- Data-to-parameter ratio = 10.0
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level B:
PLAT_420 Alert B D-H Without Acceptor O(1) - H(1) ?
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.37 From the CIF: _reflns_number_total 1851 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2030 Completeness (_total/calc) 91.18% Alert C: < 95% complete General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.37 From the CIF: _reflns_number_total 1851 Count of symmetry unique reflns 2030 Completeness (_total/calc) 91.18% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
1 Alert Level C = Please check
(E)-1-(4-Bromophenyl)-7-methylocta-2,6-dien-1-one was oxidized by potassium permanganate under solid–liquid phase-transfer conditions using a chiral quaternary ammonium salt. Following a standard work-up and column chromatography, the product was recrystallized from ethanol/hexane to give colourless crystals of the title compound.
Hydrogen atoms were observed in a difference map, but were included in idealized positions with coordinates and thermal parameters riding on those of the parent atom. Refinement of a Flack parameter (Flack, 1983) indicated that the correct absolute structure had been identified.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: PLATON (Spek, 1990).
C15H19BrO4 | Dx = 1.48 Mg m−3 |
Mr = 343.21 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 1626 reflections |
a = 7.7184 (15) Å | θ = 2.9–27.5° |
b = 7.8674 (16) Å | µ = 2.68 mm−1 |
c = 25.374 (5) Å | T = 120 K |
V = 1540.8 (5) Å3 | Plate, colourless |
Z = 4 | 0.3 × 0.2 × 0.05 mm |
F(000) = 704 |
Nonius KappaCCD diffractometer | 1051 reflections with I > 2σ(I) |
ϕ and ω scans | Rint = 0.057 |
Absorption correction: multi-scan (Blessing, 1997) | θmax = 27.4°, θmin = 3.1° |
Tmin = 0.501, Tmax = 0.878 | h = −8→9 |
2895 measured reflections | k = −9→10 |
1851 independent reflections | l = −32→32 |
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0957P)2 + 0.1591P] where P = (Fo2 + 2Fc2)/3 |
Least-squares matrix: full | (Δ/σ)max = 0.015 |
R[F2 > 2σ(F2)] = 0.069 | Δρmax = 0.50 e Å−3 |
wR(F2) = 0.193 | Δρmin = −0.40 e Å−3 |
S = 1.04 | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1851 reflections | Extinction coefficient: 0.013 (3) |
186 parameters | Absolute structure: Flack (1983) |
0 restraints | Absolute structure parameter: 0.00 (3) |
H-atom parameters constrained |
C15H19BrO4 | V = 1540.8 (5) Å3 |
Mr = 343.21 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.7184 (15) Å | µ = 2.68 mm−1 |
b = 7.8674 (16) Å | T = 120 K |
c = 25.374 (5) Å | 0.3 × 0.2 × 0.05 mm |
Nonius KappaCCD diffractometer | 1851 independent reflections |
Absorption correction: multi-scan (Blessing, 1997) | 1051 reflections with I > 2σ(I) |
Tmin = 0.501, Tmax = 0.878 | Rint = 0.057 |
2895 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | H-atom parameters constrained |
wR(F2) = 0.193 | Δρmax = 0.50 e Å−3 |
S = 1.04 | Δρmin = −0.40 e Å−3 |
1851 reflections | Absolute structure: Flack (1983) |
186 parameters | Absolute structure parameter: 0.00 (3) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7695 (14) | −0.4045 (14) | 1.1468 (4) | 0.061 (3) | |
C2 | 0.7418 (18) | −0.4426 (16) | 1.0884 (4) | 0.087 (4) | |
H2A | 0.7067 | −0.5615 | 1.0841 | 0.13* | |
H2B | 0.8499 | −0.4226 | 1.0691 | 0.13* | |
H2C | 0.6509 | −0.3681 | 1.0744 | 0.13* | |
C3 | 0.9086 (14) | −0.5162 (15) | 1.1697 (5) | 0.083 (3) | |
H3A | 0.9014 | −0.5136 | 1.2083 | 0.124* | |
H3B | 1.0225 | −0.4746 | 1.1585 | 0.124* | |
H3C | 0.8925 | −0.6331 | 1.1573 | 0.124* | |
C4 | 0.8149 (13) | −0.2198 (11) | 1.1547 (4) | 0.055 (3) | |
H4 | 0.9158 | −0.1895 | 1.1318 | 0.066* | |
C5 | 0.8502 (16) | −0.1647 (11) | 1.2099 (4) | 0.060 (3) | |
H5A | 0.9752 | −0.1728 | 1.2183 | 0.072* | |
H5B | 0.7839 | −0.234 | 1.2355 | 0.072* | |
C6 | 0.7889 (14) | 0.0200 (15) | 1.2100 (4) | 0.074 (3) | |
H6A | 0.7495 | 0.0542 | 1.2456 | 0.089* | |
H6B | 0.8829 | 0.0972 | 1.1987 | 0.089* | |
C7 | 0.6404 (12) | 0.0230 (11) | 1.1713 (4) | 0.053 (2) | |
H7 | 0.647 | 0.1286 | 1.1495 | 0.064* | |
C8 | 0.4614 (14) | 0.0091 (16) | 1.1961 (3) | 0.063 (3) | |
H8 | 0.4312 | 0.1211 | 1.2123 | 0.076* | |
C9 | 0.3271 (13) | −0.0327 (14) | 1.1548 (4) | 0.060 (3) | |
C10 | 0.2766 (13) | 0.0988 (14) | 1.1159 (4) | 0.056 (3) | |
C11 | 0.1841 (14) | 0.0536 (16) | 1.0713 (5) | 0.074 (3) | |
H11 | 0.1525 | −0.0622 | 1.0668 | 0.089* | |
C12 | 0.1367 (16) | 0.1671 (19) | 1.0337 (4) | 0.084 (4) | |
H12 | 0.0679 | 0.1327 | 1.0045 | 0.101* | |
C13 | 0.1900 (14) | 0.3321 (18) | 1.0387 (4) | 0.073 (3) | |
C14 | 0.2785 (14) | 0.3849 (14) | 1.0825 (4) | 0.066 (3) | |
H14 | 0.3114 | 0.5007 | 1.0861 | 0.079* | |
C15 | 0.3194 (15) | 0.2699 (13) | 1.1213 (4) | 0.063 (3) | |
H15 | 0.3776 | 0.3075 | 1.1521 | 0.076* | |
O1 | 0.6096 (8) | −0.4402 (8) | 1.1742 (2) | 0.0582 (18) | |
H1 | 0.547 | −0.5032 | 1.1554 | 0.087* | |
O2 | 0.6638 (9) | −0.1220 (7) | 1.1384 (2) | 0.0539 (17) | |
O3 | 0.4575 (11) | −0.1164 (9) | 1.2358 (3) | 0.070 (2) | |
H3 | 0.4241 | −0.0727 | 1.2642 | 0.105* | |
O4 | 0.2737 (11) | −0.1769 (11) | 1.1503 (3) | 0.092 (3) | |
Br1 | 0.14740 (19) | 0.4869 (2) | 0.98345 (5) | 0.1088 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.062 (7) | 0.066 (7) | 0.055 (6) | −0.004 (6) | 0.016 (5) | 0.009 (5) |
C2 | 0.110 (10) | 0.086 (8) | 0.065 (7) | −0.005 (8) | 0.008 (7) | −0.009 (6) |
C3 | 0.074 (8) | 0.057 (7) | 0.117 (9) | 0.009 (8) | −0.008 (7) | 0.006 (7) |
C4 | 0.039 (6) | 0.052 (6) | 0.074 (6) | 0.002 (6) | 0.005 (5) | 0.014 (5) |
C5 | 0.052 (7) | 0.048 (6) | 0.079 (7) | 0.000 (7) | −0.018 (6) | 0.011 (5) |
C6 | 0.076 (7) | 0.059 (7) | 0.088 (7) | −0.018 (8) | −0.035 (6) | −0.003 (7) |
C7 | 0.054 (6) | 0.037 (5) | 0.068 (5) | −0.003 (7) | 0.001 (5) | 0.003 (5) |
C8 | 0.075 (7) | 0.063 (7) | 0.051 (5) | 0.001 (8) | 0.000 (5) | 0.002 (6) |
C9 | 0.048 (6) | 0.058 (7) | 0.075 (7) | −0.001 (8) | 0.019 (5) | 0.001 (5) |
C10 | 0.047 (6) | 0.069 (7) | 0.052 (6) | −0.021 (6) | −0.002 (5) | −0.012 (5) |
C11 | 0.055 (7) | 0.092 (8) | 0.075 (7) | −0.015 (8) | 0.006 (5) | −0.014 (7) |
C12 | 0.058 (8) | 0.134 (12) | 0.059 (7) | −0.028 (9) | −0.002 (6) | 0.005 (8) |
C13 | 0.044 (6) | 0.115 (10) | 0.060 (7) | 0.019 (8) | −0.005 (5) | 0.016 (7) |
C14 | 0.056 (7) | 0.067 (6) | 0.075 (7) | 0.013 (7) | 0.002 (6) | 0.004 (6) |
C15 | 0.059 (8) | 0.070 (7) | 0.060 (6) | −0.001 (7) | −0.005 (5) | 0.002 (5) |
O1 | 0.063 (4) | 0.047 (4) | 0.064 (4) | −0.027 (4) | 0.007 (3) | −0.010 (3) |
O2 | 0.043 (4) | 0.058 (4) | 0.060 (4) | 0.008 (4) | −0.003 (3) | −0.001 (3) |
O3 | 0.096 (6) | 0.053 (4) | 0.060 (4) | 0.020 (5) | 0.018 (4) | 0.003 (4) |
O4 | 0.078 (6) | 0.070 (5) | 0.127 (7) | −0.031 (5) | −0.017 (5) | 0.005 (5) |
Br1 | 0.0795 (9) | 0.1593 (15) | 0.0877 (10) | 0.0123 (13) | −0.0108 (7) | 0.0427 (9) |
C1—O1 | 1.444 (12) | C7—C8 | 1.522 (13) |
C1—C3 | 1.504 (15) | C7—H7 | 1 |
C1—C4 | 1.508 (13) | C8—O3 | 1.411 (12) |
C1—C2 | 1.528 (15) | C8—C9 | 1.509 (15) |
C2—H2A | 0.98 | C8—H8 | 1 |
C2—H2B | 0.98 | C9—O4 | 1.213 (12) |
C2—H2C | 0.98 | C9—C10 | 1.483 (14) |
C3—H3A | 0.98 | C10—C11 | 1.385 (14) |
C3—H3B | 0.98 | C10—C15 | 1.392 (13) |
C3—H3C | 0.98 | C11—C12 | 1.358 (15) |
C4—O2 | 1.457 (11) | C11—H11 | 0.95 |
C4—C5 | 1.491 (13) | C12—C13 | 1.367 (16) |
C4—H4 | 1 | C12—H12 | 0.95 |
C5—C6 | 1.528 (15) | C13—C14 | 1.370 (15) |
C5—H5A | 0.99 | C13—Br1 | 1.885 (11) |
C5—H5B | 0.99 | C14—C15 | 1.373 (14) |
C6—C7 | 1.511 (13) | C14—H14 | 0.95 |
C6—H6A | 0.99 | C15—H15 | 0.95 |
C6—H6B | 0.99 | O1—H1 | 0.84 |
C7—O2 | 1.425 (11) | O3—H3 | 0.84 |
O1—C1—C3 | 108.1 (8) | O2—C7—C6 | 105.8 (8) |
O1—C1—C4 | 108.8 (8) | O2—C7—C8 | 107.4 (8) |
C3—C1—C4 | 110.2 (9) | C6—C7—C8 | 114.8 (8) |
O1—C1—C2 | 108.0 (9) | O2—C7—H7 | 109.6 |
C3—C1—C2 | 111.1 (10) | C6—C7—H7 | 109.6 |
C4—C1—C2 | 110.5 (9) | C8—C7—H7 | 109.6 |
C1—C2—H2A | 109.5 | O3—C8—C9 | 109.2 (9) |
C1—C2—H2B | 109.5 | O3—C8—C7 | 111.4 (9) |
H2A—C2—H2B | 109.5 | C9—C8—C7 | 110.7 (7) |
C1—C2—H2C | 109.5 | O3—C8—H8 | 108.5 |
H2A—C2—H2C | 109.5 | C9—C8—H8 | 108.5 |
H2B—C2—H2C | 109.5 | C7—C8—H8 | 108.5 |
C1—C3—H3A | 109.5 | O4—C9—C10 | 120.0 (10) |
C1—C3—H3B | 109.5 | O4—C9—C8 | 120.2 (10) |
H3A—C3—H3B | 109.5 | C10—C9—C8 | 119.3 (9) |
C1—C3—H3C | 109.5 | C11—C10—C15 | 116.8 (11) |
H3A—C3—H3C | 109.5 | C11—C10—C9 | 120.0 (10) |
H3B—C3—H3C | 109.5 | C15—C10—C9 | 123.2 (9) |
O2—C4—C5 | 105.0 (7) | C12—C11—C10 | 123.0 (11) |
O2—C4—C1 | 106.6 (8) | C12—C11—H11 | 118.5 |
C5—C4—C1 | 116.6 (8) | C10—C11—H11 | 118.5 |
O2—C4—H4 | 109.5 | C11—C12—C13 | 118.5 (11) |
C5—C4—H4 | 109.5 | C11—C12—H12 | 120.7 |
C1—C4—H4 | 109.5 | C13—C12—H12 | 120.7 |
C4—C5—C6 | 102.8 (8) | C12—C13—C14 | 120.9 (11) |
C4—C5—H5A | 111.2 | C12—C13—Br1 | 119.4 (9) |
C6—C5—H5A | 111.2 | C14—C13—Br1 | 119.6 (10) |
C4—C5—H5B | 111.2 | C13—C14—C15 | 119.8 (11) |
C6—C5—H5B | 111.2 | C13—C14—H14 | 120.1 |
H5A—C5—H5B | 109.1 | C15—C14—H14 | 120.1 |
C7—C6—C5 | 104.4 (8) | C14—C15—C10 | 120.8 (10) |
C7—C6—H6A | 110.9 | C14—C15—H15 | 119.6 |
C5—C6—H6A | 110.9 | C10—C15—H15 | 119.6 |
C7—C6—H6B | 110.9 | C1—O1—H1 | 109.5 |
C5—C6—H6B | 110.9 | C7—O2—C4 | 111.0 (7) |
H6A—C6—H6B | 108.9 | C8—O3—H3 | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1i | 0.84 | 1.90 | 2.722 (9) | 167 |
C8—H8···O3i | 1.00 | 2.60 | 3.475 (8) | 146 |
Symmetry code: (i) −x+1, y+1/2, −z+5/2. |
Experimental details
Crystal data | |
Chemical formula | C15H19BrO4 |
Mr | 343.21 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 120 |
a, b, c (Å) | 7.7184 (15), 7.8674 (16), 25.374 (5) |
V (Å3) | 1540.8 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.68 |
Crystal size (mm) | 0.3 × 0.2 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (Blessing, 1997) |
Tmin, Tmax | 0.501, 0.878 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2895, 1851, 1051 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.647 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.193, 1.04 |
No. of reflections | 1851 |
No. of parameters | 186 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.40 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.00 (3) |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997b), PLATON (Spek, 1990).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1i | 0.84 | 1.90 | 2.722 (9) | 167.2 |
C8—H8···O3i | 1.00 | 2.60 | 3.475 (8) | 146.4 |
Symmetry code: (i) −x+1, y+1/2, −z+5/2. |
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During the development of chiral phase-transfer catalysed permanganate oxidations of 1,5-dienes the title compound, (I), was prepared (Brown & Keily, 2001). The molecular structure is given in Fig. 1. The structure is composed of a tetrahydrofuran (THF) ring substituted in the 2 and 5 positions by bromophenylhydroxyethanone and hydroxymethylethyl groups, respectively. The geometric parameters conform to standard values derived from a systematic study of similarly hybridized atoms in the Cambridge Structural Database (Allen & Kennard, 1993; Orpen et al., 1992).
The 2 position in the THF ring (C7) exhibits R chirality and the 5 position (C4) is S, whilst C8 is a centre of chirality (= S). The THF ring exhibits an envelope conformation about C5. Hydrogen bonding exists between the two hydroxyl groups in the structure where the donor–acceptor distance of O3—H3···O1i is 2.722 (6) Å [symmetry code: (i) -x + 1, y + 1/2, -z + 5/2]. Moreover, the hydroxyl group containing O3 is involved in a second, weaker intermolecular hydrogen bond, with a donor–acceptor distance C8—H8···O3i of 3.475 Å. These interactions form a one-dimensional-chain network in the crystal structure.