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The molecules of 2-benzoyl-1-benzofuran, C
15H
10O
2, (I), interact through double C-H
O hydrogen bonds, forming dimers that are further linked by C-H
O, C-H
and
-
interactions, resulting in a three-dimensional supramolecular network. The dihedral angle between the benzoyl and benzofuran fragments in (I) is 46.15 (3)°. The molecules of bis(5-bromo-1-benzofuran-2-yl) ketone, C
17H
8Br
2O
3, (II), exhibit
C2 symmetry, with the carbonyl group (C=O) lying along the twofold rotation axis, and are linked by a combination of C-H
O and C-H
interactions and Br
Br contacts to form sheets. The stability of the molecular packing in 3-mesityl-3-methylcyclobutyl 3-methylnaphtho[1,2-
b]furan-2-yl ketone, C
28H
28O
2, (III), arises from C-H
and
-
stacking interactions. The fused naphthofuran moiety in (III) is essentially planar and makes a dihedral angle of 81.61 (3)° with the mean plane of the trimethylbenzene ring.
Supporting information
CCDC references: 278563; 278564; 278565
A mixture of salicylaldehyde (12.21 g, 0.1 mol) and potassium carbonate (20.70 g, 0.15 mol) was strirred in dry acetone (250 ml) at room temperature for 2 h. A solution of phenacylbromide (19.90 g, 0.1 mol) in dry acetone (20 ml) was added to this mixture. The resulting solution was poured into water (250 ml) and reprecipitated twice from water. Suitable crystals of (I) were obtained by recrystallizing of the precipitate from acetone (yield 19.60 g, 89.1%). A mixture of 5-bromo-2-hydroxybenzaldehyde (20.10 g, 0.1 mol) and potassium carbonate (20.70 g, 0.15 mol) was stirred in dry acetone (250 ml) at room temperature for 2 h. A solution of 1,3-dichloroacetone (6.35 g, 0.05 mol) in dry acetone (20 ml) was added and this mixture was poured into water (250 ml). The separated solid was filtered, washed with water and recrystallized from THF to give (II) (yield 33.8 g, 80.5%). Hydroxynaphthophenone (1.86 g, 10 mmol), potassium carbonate (2.07 g, 15 mmol) and dry tetrahydrofuran (100 ml) were placed in a 500 ml two-necked flask fitted with a reflux condenser, and the mixture was stirred for 1 h at room temperature. To this solution, a solution of 1-mesityl-1-methyl-3-(2-chloro-1-oxoethyl)cyclobutane (2.64 g, 10 mmol) in acetonitrile (100 ml) was added dropwise over a period of about 30 min and the mixture was subsequently refluxed for 4 h. The progress of the reaction was monitored by IR spectroscopy. The mixture was allowed to cool to room temperature, and was poured into water (500 ml) and reprecipitated twice from water. The solid was filtered and recrystallized from tetrahydrofuran to obtain crystals of (III) (yield 2.85 g, 71.96%).
All H atoms were refined with a riding model, with C—H distances of 0.95–1.00 Å and Uiso(H) values of 1.2 Ueq(C).
For all compounds, data collection: COLLECT (Bruker, 2002); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: EVALCCD; program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
(I) 2-Benzoylbenzofuran
top
Crystal data top
C15H10O2 | Z = 2 |
Mr = 222.23 | F(000) = 232 |
Triclinic, P1 | Dx = 1.402 Mg m−3 |
Hall symbol: -P1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.1028 (5) Å | Cell parameters from 36 reflections |
b = 8.8010 (4) Å | θ = 6.0–20.0° |
c = 10.1195 (6) Å | µ = 0.09 mm−1 |
α = 97.700 (4)° | T = 100 K |
β = 93.710 (6)° | Prism, colorless |
γ = 101.073 (6)° | 0.34 × 0.31 × 0.28 mm |
V = 526.31 (6) Å3 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 2049 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.070 |
Graphite monochromator | θmax = 27.9°, θmin = 3.4° |
Detector resolution: 9 pixels mm-1 | h = −8→8 |
ϕ and ω scans | k = −11→11 |
17534 measured reflections | l = −13→13 |
2498 independent reflections | |
Refinement top
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0496P)2 + 0.1374P] where P = (Fo2 + 2Fc2)/3 |
2498 reflections | (Δ/σ)max = 0.001 |
154 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
Crystal data top
C15H10O2 | γ = 101.073 (6)° |
Mr = 222.23 | V = 526.31 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.1028 (5) Å | Mo Kα radiation |
b = 8.8010 (4) Å | µ = 0.09 mm−1 |
c = 10.1195 (6) Å | T = 100 K |
α = 97.700 (4)° | 0.34 × 0.31 × 0.28 mm |
β = 93.710 (6)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 2049 reflections with I > 2σ(I) |
17534 measured reflections | Rint = 0.070 |
2498 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.23 e Å−3 |
2498 reflections | Δρmin = −0.30 e Å−3 |
154 parameters | |
Special details top
Experimental. ϕ- and ω-rotations with 2.0 ° and 16 sec per frame ? |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.41842 (13) | 0.20228 (9) | 0.03269 (8) | 0.0151 (2) | |
O2 | 0.73731 (14) | 0.39489 (11) | 0.20751 (9) | 0.0213 (2) | |
C1 | 0.23671 (19) | 0.14212 (14) | −0.05891 (11) | 0.0135 (2) | |
C2 | 0.2104 (2) | 0.00550 (14) | −0.14903 (12) | 0.0166 (3) | |
H2A | 0.3211 | −0.0571 | −0.1534 | 0.020* | |
C3 | 0.0128 (2) | −0.03411 (14) | −0.23233 (12) | 0.0174 (3) | |
H3A | −0.0128 | −0.1263 | −0.2966 | 0.021* | |
C4 | −0.1513 (2) | 0.05844 (14) | −0.22445 (12) | 0.0176 (3) | |
H4A | −0.2845 | 0.0278 | −0.2838 | 0.021* | |
C5 | −0.12279 (19) | 0.19296 (14) | −0.13220 (12) | 0.0158 (3) | |
H5A | −0.2350 | 0.2543 | −0.1266 | 0.019* | |
C6 | 0.07652 (19) | 0.23638 (13) | −0.04711 (11) | 0.0133 (2) | |
C7 | 0.16727 (19) | 0.36055 (14) | 0.06015 (11) | 0.0138 (2) | |
H7A | 0.0990 | 0.4444 | 0.0936 | 0.017* | |
C8 | 0.37018 (19) | 0.33510 (13) | 0.10469 (12) | 0.0137 (3) | |
C9 | 0.54826 (19) | 0.42318 (14) | 0.20613 (12) | 0.0142 (3) | |
C10 | 0.49519 (19) | 0.54872 (13) | 0.30610 (11) | 0.0133 (3) | |
C11 | 0.28860 (19) | 0.53465 (14) | 0.36038 (11) | 0.0145 (3) | |
H11A | 0.1720 | 0.4464 | 0.3290 | 0.017* | |
C12 | 0.2544 (2) | 0.64960 (14) | 0.45996 (12) | 0.0169 (3) | |
H12A | 0.1149 | 0.6392 | 0.4979 | 0.020* | |
C13 | 0.4229 (2) | 0.78001 (14) | 0.50464 (12) | 0.0176 (3) | |
H13A | 0.3984 | 0.8585 | 0.5729 | 0.021* | |
C14 | 0.6274 (2) | 0.79578 (14) | 0.44957 (12) | 0.0175 (3) | |
H14A | 0.7417 | 0.8860 | 0.4790 | 0.021* | |
C15 | 0.6644 (2) | 0.67989 (14) | 0.35169 (12) | 0.0157 (3) | |
H15A | 0.8054 | 0.6897 | 0.3155 | 0.019* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0140 (4) | 0.0155 (4) | 0.0154 (4) | 0.0046 (3) | −0.0002 (3) | −0.0007 (3) |
O2 | 0.0120 (4) | 0.0272 (5) | 0.0236 (5) | 0.0052 (4) | 0.0004 (3) | −0.0014 (4) |
C1 | 0.0130 (5) | 0.0154 (6) | 0.0118 (5) | 0.0013 (4) | 0.0002 (4) | 0.0041 (5) |
C2 | 0.0204 (6) | 0.0147 (6) | 0.0156 (6) | 0.0052 (5) | 0.0033 (5) | 0.0027 (5) |
C3 | 0.0235 (6) | 0.0133 (6) | 0.0133 (6) | −0.0004 (5) | 0.0022 (5) | 0.0009 (5) |
C4 | 0.0166 (6) | 0.0194 (6) | 0.0149 (6) | −0.0017 (5) | −0.0012 (5) | 0.0048 (5) |
C5 | 0.0136 (6) | 0.0180 (6) | 0.0162 (6) | 0.0023 (5) | 0.0010 (5) | 0.0053 (5) |
C6 | 0.0141 (6) | 0.0133 (6) | 0.0130 (6) | 0.0020 (4) | 0.0035 (4) | 0.0041 (4) |
C7 | 0.0138 (6) | 0.0136 (6) | 0.0141 (6) | 0.0024 (4) | 0.0024 (4) | 0.0029 (4) |
C8 | 0.0152 (6) | 0.0121 (6) | 0.0143 (6) | 0.0033 (4) | 0.0040 (4) | 0.0020 (5) |
C9 | 0.0129 (6) | 0.0159 (6) | 0.0138 (6) | 0.0018 (4) | 0.0018 (4) | 0.0039 (5) |
C10 | 0.0136 (6) | 0.0142 (6) | 0.0120 (5) | 0.0023 (4) | −0.0013 (4) | 0.0031 (5) |
C11 | 0.0129 (6) | 0.0145 (6) | 0.0150 (6) | 0.0000 (4) | −0.0009 (4) | 0.0033 (5) |
C12 | 0.0156 (6) | 0.0193 (6) | 0.0166 (6) | 0.0043 (5) | 0.0024 (5) | 0.0039 (5) |
C13 | 0.0229 (6) | 0.0153 (6) | 0.0145 (6) | 0.0056 (5) | −0.0011 (5) | 0.0001 (5) |
C14 | 0.0189 (6) | 0.0136 (6) | 0.0174 (6) | −0.0017 (5) | −0.0036 (5) | 0.0029 (5) |
C15 | 0.0131 (6) | 0.0180 (6) | 0.0158 (6) | 0.0014 (5) | 0.0006 (4) | 0.0053 (5) |
Geometric parameters (Å, º) top
O1—C1 | 1.3709 (14) | C7—H7A | 0.9500 |
O1—C8 | 1.3841 (14) | C8—C9 | 1.4678 (17) |
O2—C9 | 1.2257 (14) | C9—C10 | 1.4932 (16) |
C1—C2 | 1.3843 (17) | C10—C15 | 1.3964 (17) |
C1—C6 | 1.3994 (16) | C10—C11 | 1.3981 (16) |
C2—C3 | 1.3838 (18) | C11—C12 | 1.3849 (17) |
C2—H2A | 0.9500 | C11—H11A | 0.9500 |
C3—C4 | 1.4068 (17) | C12—C13 | 1.3881 (18) |
C3—H3A | 0.9500 | C12—H12A | 0.9500 |
C4—C5 | 1.3809 (17) | C13—C14 | 1.3898 (17) |
C4—H4A | 0.9500 | C13—H13A | 0.9500 |
C5—C6 | 1.4017 (17) | C14—C15 | 1.3854 (17) |
C5—H5A | 0.9500 | C14—H14A | 0.9500 |
C6—C7 | 1.4321 (17) | C15—H15A | 0.9500 |
C7—C8 | 1.3595 (16) | | |
| | | |
C1—O1—C8 | 105.82 (9) | C7—C8—C9 | 133.25 (11) |
O1—C1—C2 | 125.37 (10) | O1—C8—C9 | 115.23 (10) |
O1—C1—C6 | 110.53 (10) | O2—C9—C8 | 120.40 (11) |
C2—C1—C6 | 124.08 (11) | O2—C9—C10 | 120.85 (11) |
C3—C2—C1 | 115.80 (11) | C8—C9—C10 | 118.74 (10) |
C3—C2—H2A | 122.1 | C15—C10—C11 | 119.59 (11) |
C1—C2—H2A | 122.1 | C15—C10—C9 | 117.96 (10) |
C2—C3—C4 | 121.80 (11) | C11—C10—C9 | 122.33 (10) |
C2—C3—H3A | 119.1 | C12—C11—C10 | 119.84 (11) |
C4—C3—H3A | 119.1 | C12—C11—H11A | 120.1 |
C5—C4—C3 | 121.32 (11) | C10—C11—H11A | 120.1 |
C5—C4—H4A | 119.3 | C11—C12—C13 | 120.34 (11) |
C3—C4—H4A | 119.3 | C11—C12—H12A | 119.8 |
C4—C5—C6 | 118.09 (11) | C13—C12—H12A | 119.8 |
C4—C5—H5A | 121.0 | C12—C13—C14 | 120.06 (11) |
C6—C5—H5A | 121.0 | C12—C13—H13A | 120.0 |
C1—C6—C5 | 118.90 (11) | C14—C13—H13A | 120.0 |
C1—C6—C7 | 105.57 (10) | C15—C14—C13 | 119.95 (11) |
C5—C6—C7 | 135.51 (11) | C15—C14—H14A | 120.0 |
C8—C7—C6 | 106.64 (10) | C13—C14—H14A | 120.0 |
C8—C7—H7A | 126.7 | C14—C15—C10 | 120.20 (11) |
C6—C7—H7A | 126.7 | C14—C15—H15A | 119.9 |
C7—C8—O1 | 111.42 (10) | C10—C15—H15A | 119.9 |
| | | |
C8—O1—C1—C2 | −177.65 (11) | C1—O1—C8—C9 | −177.58 (9) |
C8—O1—C1—C6 | 0.95 (12) | C7—C8—C9—O2 | −163.26 (12) |
O1—C1—C2—C3 | 179.70 (10) | O1—C8—C9—O2 | 12.65 (16) |
C6—C1—C2—C3 | 1.29 (17) | C7—C8—C9—C10 | 16.00 (19) |
C1—C2—C3—C4 | −0.60 (17) | O1—C8—C9—C10 | −168.09 (9) |
C2—C3—C4—C5 | −0.43 (18) | O2—C9—C10—C15 | 32.58 (16) |
C3—C4—C5—C6 | 0.80 (17) | C8—C9—C10—C15 | −146.68 (11) |
O1—C1—C6—C5 | −179.56 (10) | O2—C9—C10—C11 | −143.58 (12) |
C2—C1—C6—C5 | −0.94 (17) | C8—C9—C10—C11 | 37.16 (16) |
O1—C1—C6—C7 | −0.77 (12) | C15—C10—C11—C12 | −0.84 (17) |
C2—C1—C6—C7 | 177.85 (11) | C9—C10—C11—C12 | 175.26 (10) |
C4—C5—C6—C1 | −0.15 (16) | C10—C11—C12—C13 | 1.06 (17) |
C4—C5—C6—C7 | −178.49 (12) | C11—C12—C13—C14 | −0.06 (18) |
C1—C6—C7—C8 | 0.27 (12) | C12—C13—C14—C15 | −1.15 (18) |
C5—C6—C7—C8 | 178.76 (13) | C13—C14—C15—C10 | 1.36 (17) |
C6—C7—C8—O1 | 0.32 (13) | C11—C10—C15—C14 | −0.36 (17) |
C6—C7—C8—C9 | 176.34 (12) | C9—C10—C15—C14 | −176.63 (10) |
C1—O1—C8—C7 | −0.78 (12) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O1i | 0.95 | 2.57 | 3.4182 (14) | 149 |
C7—H7A···O2ii | 0.95 | 2.55 | 3.1449 (14) | 121 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x−1, y, z. |
(II) Bis(5-bromobenzofuran-2-yl) ketone
top
Crystal data top
C17H8Br2O3 | F(000) = 816 |
Mr = 420.05 | Dx = 1.994 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C2yc | Cell parameters from 89 reflections |
a = 29.644 (2) Å | θ = 6.0–20.0° |
b = 6.2536 (5) Å | µ = 5.80 mm−1 |
c = 7.8188 (8) Å | T = 100 K |
β = 105.091 (6)° | Irregular, colorless |
V = 1399.5 (2) Å3 | 0.25 × 0.24 × 0.16 mm |
Z = 4 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 1814 independent reflections |
Radiation source: fine-focus sealed tube | 1604 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 9 pixels mm-1 | θmax = 28.7°, θmin = 3.3° |
ϕ and ω scans | h = −40→40 |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | k = −8→8 |
Tmin = 0.262, Tmax = 0.398 | l = −10→10 |
19777 measured reflections | |
Refinement top
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)] = 0.019 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.043 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0084P)2 + 2.8382P] where P = (Fo2 + 2Fc2)/3 |
1814 reflections | (Δ/σ)max = 0.001 |
101 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
C17H8Br2O3 | V = 1399.5 (2) Å3 |
Mr = 420.05 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 29.644 (2) Å | µ = 5.80 mm−1 |
b = 6.2536 (5) Å | T = 100 K |
c = 7.8188 (8) Å | 0.25 × 0.24 × 0.16 mm |
β = 105.091 (6)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 1814 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1604 reflections with I > 2σ(I) |
Tmin = 0.262, Tmax = 0.398 | Rint = 0.046 |
19777 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.043 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.43 e Å−3 |
1814 reflections | Δρmin = −0.32 e Å−3 |
101 parameters | |
Special details top
Experimental. ϕ- and ω-rotations with 2.0 ° and 60 sec per frame |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.717962 (6) | 0.60233 (3) | 0.11795 (2) | 0.01751 (6) | |
O1 | 0.56490 (4) | −0.01371 (19) | 0.12336 (15) | 0.0133 (2) | |
O2 | 0.5000 | −0.2031 (3) | 0.2500 | 0.0177 (4) | |
C1 | 0.60023 (6) | 0.1165 (3) | 0.1029 (2) | 0.0125 (3) | |
C2 | 0.63717 (6) | 0.0520 (3) | 0.0368 (2) | 0.0146 (3) | |
H2A | 0.6387 | −0.0877 | −0.0092 | 0.018* | |
C3 | 0.67171 (6) | 0.2029 (3) | 0.0416 (2) | 0.0151 (3) | |
H3A | 0.6982 | 0.1666 | 0.0006 | 0.018* | |
C4 | 0.66779 (6) | 0.4090 (3) | 0.1069 (2) | 0.0145 (3) | |
C5 | 0.63009 (6) | 0.4749 (3) | 0.1667 (2) | 0.0140 (3) | |
H5A | 0.6278 | 0.6169 | 0.2068 | 0.017* | |
C6 | 0.59535 (6) | 0.3223 (3) | 0.1654 (2) | 0.0126 (3) | |
C7 | 0.55374 (6) | 0.3162 (3) | 0.2269 (2) | 0.0135 (3) | |
H7A | 0.5404 | 0.4312 | 0.2763 | 0.016* | |
C8 | 0.53734 (6) | 0.1131 (3) | 0.2003 (2) | 0.0129 (3) | |
C9 | 0.5000 | −0.0075 (4) | 0.2500 | 0.0133 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.01199 (8) | 0.01662 (9) | 0.02444 (10) | −0.00274 (7) | 0.00571 (6) | 0.00045 (7) |
O1 | 0.0122 (5) | 0.0112 (6) | 0.0177 (6) | 0.0000 (4) | 0.0061 (5) | −0.0012 (4) |
O2 | 0.0172 (8) | 0.0119 (8) | 0.0251 (9) | 0.000 | 0.0075 (7) | 0.000 |
C1 | 0.0116 (7) | 0.0128 (7) | 0.0126 (7) | −0.0014 (6) | 0.0023 (6) | 0.0009 (6) |
C2 | 0.0154 (8) | 0.0134 (8) | 0.0154 (8) | 0.0019 (6) | 0.0047 (6) | −0.0008 (6) |
C3 | 0.0119 (7) | 0.0182 (8) | 0.0160 (8) | 0.0019 (6) | 0.0051 (6) | 0.0014 (7) |
C4 | 0.0118 (7) | 0.0156 (8) | 0.0155 (8) | −0.0023 (6) | 0.0028 (6) | 0.0015 (6) |
C5 | 0.0137 (8) | 0.0126 (7) | 0.0150 (8) | −0.0004 (6) | 0.0026 (6) | 0.0000 (6) |
C6 | 0.0116 (7) | 0.0131 (7) | 0.0126 (8) | 0.0010 (6) | 0.0021 (6) | 0.0002 (6) |
C7 | 0.0117 (7) | 0.0129 (7) | 0.0158 (8) | 0.0011 (6) | 0.0036 (6) | −0.0010 (6) |
C8 | 0.0121 (7) | 0.0128 (7) | 0.0140 (7) | 0.0028 (6) | 0.0040 (6) | 0.0000 (6) |
C9 | 0.0127 (10) | 0.0141 (11) | 0.0120 (11) | 0.000 | 0.0012 (8) | 0.000 |
Geometric parameters (Å, º) top
Br1—C4 | 1.9010 (16) | C3—H3A | 0.9500 |
O1—C1 | 1.3683 (19) | C4—C5 | 1.382 (2) |
O1—C8 | 1.3835 (19) | C5—C6 | 1.402 (2) |
O2—C9 | 1.223 (3) | C5—H5A | 0.9500 |
C1—C2 | 1.387 (2) | C6—C7 | 1.436 (2) |
C1—C6 | 1.398 (2) | C7—C8 | 1.356 (2) |
C2—C3 | 1.386 (2) | C7—H7A | 0.9500 |
C2—H2A | 0.9500 | C8—C9 | 1.473 (2) |
C3—C4 | 1.402 (2) | C9—C8i | 1.473 (2) |
| | | |
C1—O1—C8 | 105.45 (12) | C4—C5—H5A | 121.6 |
O1—C1—C2 | 124.98 (15) | C6—C5—H5A | 121.6 |
O1—C1—C6 | 110.79 (14) | C1—C6—C5 | 119.13 (15) |
C2—C1—C6 | 124.17 (15) | C1—C6—C7 | 105.57 (14) |
C3—C2—C1 | 116.17 (15) | C5—C6—C7 | 135.15 (16) |
C3—C2—H2A | 121.9 | C8—C7—C6 | 106.17 (15) |
C1—C2—H2A | 121.9 | C8—C7—H7A | 126.9 |
C2—C3—C4 | 120.37 (15) | C6—C7—H7A | 126.9 |
C2—C3—H3A | 119.8 | C7—C8—O1 | 112.00 (14) |
C4—C3—H3A | 119.8 | C7—C8—C9 | 134.67 (16) |
C5—C4—C3 | 123.24 (15) | O1—C8—C9 | 112.99 (14) |
C5—C4—Br1 | 119.15 (13) | O2—C9—C8i | 120.81 (10) |
C3—C4—Br1 | 117.59 (12) | O2—C9—C8 | 120.81 (10) |
C4—C5—C6 | 116.86 (15) | C8i—C9—C8 | 118.4 (2) |
| | | |
C8—O1—C1—C2 | 177.24 (16) | C4—C5—C6—C1 | −0.8 (2) |
C8—O1—C1—C6 | −0.01 (17) | C4—C5—C6—C7 | 173.97 (18) |
O1—C1—C2—C3 | −174.22 (15) | C1—C6—C7—C8 | 0.78 (18) |
C6—C1—C2—C3 | 2.7 (2) | C5—C6—C7—C8 | −174.47 (18) |
C1—C2—C3—C4 | −1.4 (2) | C6—C7—C8—O1 | −0.83 (19) |
C2—C3—C4—C5 | −0.9 (3) | C6—C7—C8—C9 | 171.87 (16) |
C2—C3—C4—Br1 | 177.46 (13) | C1—O1—C8—C7 | 0.54 (18) |
C3—C4—C5—C6 | 2.0 (2) | C1—O1—C8—C9 | −173.83 (11) |
Br1—C4—C5—C6 | −176.33 (12) | C7—C8—C9—O2 | −160.61 (16) |
O1—C1—C6—C5 | 175.68 (14) | O1—C8—C9—O2 | 12.04 (15) |
C2—C1—C6—C5 | −1.6 (3) | C7—C8—C9—C8i | 19.39 (16) |
O1—C1—C6—C7 | −0.48 (18) | O1—C8—C9—C8i | −167.96 (15) |
C2—C1—C6—C7 | −177.76 (16) | | |
Symmetry code: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···O2ii | 0.95 | 2.56 | 3.429 (2) | 151 |
Symmetry code: (ii) x, y+1, z. |
(III) 3-mesityl-3-methylcyclobutyl 3-methylnaphtho[1,2-
b]furan-2-yl ketone
top
Crystal data top
C28H28O2 | F(000) = 848 |
Mr = 396.50 | Dx = 1.250 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2ybc | Cell parameters from 134 reflections |
a = 7.3816 (3) Å | θ = 6.0–20.0° |
b = 8.2874 (6) Å | µ = 0.08 mm−1 |
c = 34.591 (2) Å | T = 100 K |
β = 95.487 (5)° | Block, colorless |
V = 2106.4 (2) Å3 | 0.34 × 0.25 × 0.16 mm |
Z = 4 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 4182 independent reflections |
Radiation source: fine-focus sealed tube | 3360 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
Detector resolution: 9 pixels mm-1 | θmax = 26.4°, θmin = 3.5° |
ϕ and ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | k = −10→10 |
Tmin = 0.970, Tmax = 0.988 | l = −43→43 |
20365 measured reflections | |
Refinement top
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0429P)2 + 1.2434P] where P = (Fo2 + 2Fc2)/3 |
4182 reflections | (Δ/σ)max = 0.004 |
276 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C28H28O2 | V = 2106.4 (2) Å3 |
Mr = 396.50 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.3816 (3) Å | µ = 0.08 mm−1 |
b = 8.2874 (6) Å | T = 100 K |
c = 34.591 (2) Å | 0.34 × 0.25 × 0.16 mm |
β = 95.487 (5)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 4182 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 3360 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.988 | Rint = 0.032 |
20365 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.26 e Å−3 |
4182 reflections | Δρmin = −0.25 e Å−3 |
276 parameters | |
Special details top
Experimental. ϕ- and ω-rotations with 0.80 ° and 72 sec per frame |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.35269 (16) | 1.19691 (13) | 0.63289 (3) | 0.0250 (3) | |
O2 | 0.33251 (14) | 0.94790 (13) | 0.54892 (3) | 0.0180 (2) | |
C1 | 0.1302 (2) | 0.60782 (18) | 0.69920 (4) | 0.0162 (3) | |
C2 | 0.0324 (2) | 0.57522 (18) | 0.73095 (4) | 0.0172 (3) | |
H2A | −0.0790 | 0.5177 | 0.7267 | 0.021* | |
C3 | 0.0921 (2) | 0.62370 (18) | 0.76836 (4) | 0.0170 (3) | |
C4 | 0.2591 (2) | 0.70156 (18) | 0.77377 (4) | 0.0161 (3) | |
H4A | 0.3039 | 0.7338 | 0.7993 | 0.019* | |
C5 | 0.36378 (19) | 0.73429 (17) | 0.74308 (4) | 0.0145 (3) | |
C6 | 0.29542 (19) | 0.69371 (17) | 0.70468 (4) | 0.0141 (3) | |
C7 | 0.40305 (19) | 0.73378 (18) | 0.67044 (4) | 0.0153 (3) | |
C8 | 0.5336 (2) | 0.5962 (2) | 0.66262 (4) | 0.0208 (3) | |
H8A | 0.4637 | 0.4976 | 0.6562 | 0.031* | |
H8B | 0.6180 | 0.5776 | 0.6858 | 0.031* | |
H8C | 0.6026 | 0.6254 | 0.6408 | 0.031* | |
C9 | 0.5016 (2) | 0.90119 (19) | 0.67043 (4) | 0.0177 (3) | |
H9A | 0.4489 | 0.9834 | 0.6869 | 0.021* | |
H9B | 0.6352 | 0.8942 | 0.6764 | 0.021* | |
C10 | 0.2933 (2) | 0.78953 (19) | 0.63178 (4) | 0.0169 (3) | |
H10A | 0.2844 | 0.7063 | 0.6112 | 0.020* | |
H10B | 0.1721 | 0.8350 | 0.6354 | 0.020* | |
C11 | 0.4411 (2) | 0.91936 (19) | 0.62690 (4) | 0.0178 (3) | |
H11A | 0.5363 | 0.8775 | 0.6108 | 0.021* | |
C12 | 0.0543 (2) | 0.5382 (2) | 0.66041 (4) | 0.0209 (3) | |
H12A | −0.0386 | 0.4573 | 0.6646 | 0.031* | |
H12B | 0.1527 | 0.4876 | 0.6477 | 0.031* | |
H12C | −0.0004 | 0.6249 | 0.6439 | 0.031* | |
C13 | −0.0173 (2) | 0.5846 (2) | 0.80187 (4) | 0.0245 (4) | |
H13A | −0.1227 | 0.5186 | 0.7925 | 0.037* | |
H13B | −0.0592 | 0.6849 | 0.8131 | 0.037* | |
H13C | 0.0589 | 0.5248 | 0.8217 | 0.037* | |
C14 | 0.5516 (2) | 0.8038 (2) | 0.75348 (4) | 0.0191 (3) | |
H14A | 0.5862 | 0.7892 | 0.7813 | 0.029* | |
H14B | 0.5509 | 0.9192 | 0.7472 | 0.029* | |
H14C | 0.6395 | 0.7482 | 0.7386 | 0.029* | |
C15 | 0.3692 (2) | 1.07979 (19) | 0.61197 (4) | 0.0183 (3) | |
C16 | 0.3102 (2) | 1.08854 (19) | 0.57013 (4) | 0.0180 (3) | |
C17 | 0.2372 (2) | 1.2094 (2) | 0.54687 (4) | 0.0198 (3) | |
C18 | 0.2116 (2) | 1.1420 (2) | 0.50854 (4) | 0.0201 (3) | |
C19 | 0.1429 (2) | 1.2021 (2) | 0.47132 (5) | 0.0258 (4) | |
H19A | 0.0989 | 1.3096 | 0.4684 | 0.031* | |
C20 | 0.1420 (2) | 1.1022 (2) | 0.44004 (5) | 0.0276 (4) | |
H20A | 0.0971 | 1.1420 | 0.4152 | 0.033* | |
C21 | 0.2060 (2) | 0.9397 (2) | 0.44327 (4) | 0.0240 (4) | |
C22 | 0.2067 (2) | 0.8363 (3) | 0.41062 (5) | 0.0306 (4) | |
H22A | 0.1635 | 0.8759 | 0.3857 | 0.037* | |
C23 | 0.2680 (2) | 0.6813 (2) | 0.41424 (5) | 0.0312 (4) | |
H23A | 0.2678 | 0.6150 | 0.3918 | 0.037* | |
C24 | 0.3315 (2) | 0.6188 (2) | 0.45087 (5) | 0.0285 (4) | |
H24A | 0.3724 | 0.5103 | 0.4532 | 0.034* | |
C25 | 0.3342 (2) | 0.7147 (2) | 0.48332 (5) | 0.0226 (4) | |
H25A | 0.3777 | 0.6723 | 0.5080 | 0.027* | |
C26 | 0.2729 (2) | 0.8753 (2) | 0.48020 (4) | 0.0200 (3) | |
C27 | 0.27164 (19) | 0.9845 (2) | 0.51157 (4) | 0.0183 (3) | |
C28 | 0.1950 (2) | 1.3783 (2) | 0.55824 (5) | 0.0267 (4) | |
H28D | 0.2878 | 1.4155 | 0.5784 | 0.040* | |
H28A | 0.0753 | 1.3811 | 0.5682 | 0.040* | |
H28B | 0.1943 | 1.4489 | 0.5355 | 0.040* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0339 (7) | 0.0202 (6) | 0.0216 (6) | −0.0005 (5) | 0.0063 (5) | −0.0012 (5) |
O2 | 0.0204 (5) | 0.0193 (6) | 0.0142 (5) | −0.0021 (5) | 0.0005 (4) | 0.0018 (4) |
C1 | 0.0176 (7) | 0.0137 (8) | 0.0166 (7) | 0.0019 (6) | −0.0012 (6) | 0.0000 (6) |
C2 | 0.0141 (7) | 0.0156 (8) | 0.0217 (7) | −0.0008 (6) | 0.0008 (6) | 0.0019 (6) |
C3 | 0.0185 (8) | 0.0150 (8) | 0.0176 (7) | 0.0047 (6) | 0.0031 (6) | 0.0025 (6) |
C4 | 0.0208 (8) | 0.0134 (8) | 0.0137 (7) | 0.0031 (6) | −0.0013 (6) | −0.0013 (6) |
C5 | 0.0166 (7) | 0.0102 (7) | 0.0164 (7) | 0.0024 (6) | 0.0000 (6) | 0.0011 (6) |
C6 | 0.0162 (7) | 0.0102 (7) | 0.0156 (7) | 0.0021 (6) | 0.0007 (6) | 0.0004 (6) |
C7 | 0.0155 (7) | 0.0163 (8) | 0.0138 (7) | −0.0017 (6) | 0.0003 (6) | −0.0004 (6) |
C8 | 0.0205 (8) | 0.0229 (9) | 0.0193 (7) | 0.0029 (7) | 0.0029 (6) | −0.0005 (7) |
C9 | 0.0169 (7) | 0.0200 (8) | 0.0163 (7) | −0.0028 (6) | 0.0015 (6) | 0.0003 (6) |
C10 | 0.0191 (8) | 0.0176 (8) | 0.0138 (7) | −0.0012 (6) | 0.0011 (6) | −0.0003 (6) |
C11 | 0.0186 (8) | 0.0197 (8) | 0.0153 (7) | −0.0015 (7) | 0.0029 (6) | −0.0006 (6) |
C12 | 0.0207 (8) | 0.0217 (9) | 0.0198 (7) | −0.0059 (7) | −0.0012 (6) | −0.0022 (7) |
C13 | 0.0225 (8) | 0.0318 (10) | 0.0198 (8) | −0.0009 (7) | 0.0050 (6) | 0.0020 (7) |
C14 | 0.0208 (8) | 0.0200 (8) | 0.0157 (7) | −0.0033 (7) | −0.0029 (6) | 0.0005 (6) |
C15 | 0.0170 (8) | 0.0201 (8) | 0.0187 (7) | −0.0044 (6) | 0.0060 (6) | 0.0013 (6) |
C16 | 0.0174 (8) | 0.0173 (8) | 0.0200 (7) | −0.0026 (6) | 0.0055 (6) | 0.0005 (6) |
C17 | 0.0142 (7) | 0.0231 (9) | 0.0228 (8) | −0.0023 (7) | 0.0056 (6) | 0.0046 (7) |
C18 | 0.0135 (7) | 0.0253 (9) | 0.0219 (8) | −0.0027 (7) | 0.0035 (6) | 0.0056 (7) |
C19 | 0.0180 (8) | 0.0317 (10) | 0.0276 (9) | 0.0005 (7) | 0.0022 (6) | 0.0125 (7) |
C20 | 0.0188 (8) | 0.0438 (11) | 0.0196 (8) | −0.0030 (8) | −0.0015 (6) | 0.0108 (8) |
C21 | 0.0151 (8) | 0.0388 (10) | 0.0182 (8) | −0.0073 (7) | 0.0012 (6) | 0.0036 (7) |
C22 | 0.0205 (8) | 0.0552 (13) | 0.0159 (8) | −0.0088 (9) | −0.0003 (6) | 0.0005 (8) |
C23 | 0.0225 (9) | 0.0494 (12) | 0.0220 (8) | −0.0103 (9) | 0.0033 (7) | −0.0121 (8) |
C24 | 0.0207 (8) | 0.0337 (10) | 0.0314 (9) | −0.0067 (8) | 0.0048 (7) | −0.0087 (8) |
C25 | 0.0177 (8) | 0.0291 (10) | 0.0209 (8) | −0.0063 (7) | 0.0021 (6) | −0.0007 (7) |
C26 | 0.0134 (7) | 0.0290 (9) | 0.0178 (7) | −0.0064 (7) | 0.0018 (6) | 0.0019 (7) |
C27 | 0.0130 (7) | 0.0262 (9) | 0.0155 (7) | −0.0035 (7) | 0.0009 (6) | 0.0050 (6) |
C28 | 0.0257 (9) | 0.0244 (9) | 0.0309 (9) | 0.0028 (7) | 0.0079 (7) | 0.0054 (7) |
Geometric parameters (Å, º) top
O1—C15 | 1.2237 (19) | C12—H12C | 0.9800 |
O2—C27 | 1.3609 (17) | C13—H13A | 0.9800 |
O2—C16 | 1.3954 (19) | C13—H13B | 0.9800 |
C1—C2 | 1.397 (2) | C13—H13C | 0.9800 |
C1—C6 | 1.409 (2) | C14—H14A | 0.9800 |
C1—C12 | 1.517 (2) | C14—H14B | 0.9800 |
C2—C3 | 1.386 (2) | C14—H14C | 0.9800 |
C2—H2A | 0.9500 | C15—C16 | 1.473 (2) |
C3—C4 | 1.388 (2) | C16—C17 | 1.363 (2) |
C3—C13 | 1.510 (2) | C17—C18 | 1.434 (2) |
C4—C5 | 1.398 (2) | C17—C28 | 1.495 (2) |
C4—H4A | 0.9500 | C18—C27 | 1.379 (2) |
C5—C6 | 1.4156 (19) | C18—C19 | 1.428 (2) |
C5—C14 | 1.513 (2) | C19—C20 | 1.362 (2) |
C6—C7 | 1.525 (2) | C19—H19A | 0.9500 |
C7—C8 | 1.534 (2) | C20—C21 | 1.428 (3) |
C7—C10 | 1.5656 (19) | C20—H20A | 0.9500 |
C7—C9 | 1.566 (2) | C21—C22 | 1.418 (2) |
C8—H8A | 0.9800 | C21—C26 | 1.428 (2) |
C8—H8B | 0.9800 | C22—C23 | 1.363 (3) |
C8—H8C | 0.9800 | C22—H22A | 0.9500 |
C9—C11 | 1.5366 (19) | C23—C24 | 1.407 (2) |
C9—H9A | 0.9900 | C23—H23A | 0.9500 |
C9—H9B | 0.9900 | C24—C25 | 1.374 (2) |
C10—C11 | 1.553 (2) | C24—H24A | 0.9500 |
C10—H10A | 0.9900 | C25—C26 | 1.407 (2) |
C10—H10B | 0.9900 | C25—H25A | 0.9500 |
C11—C15 | 1.505 (2) | C26—C27 | 1.414 (2) |
C11—H11A | 1.0000 | C28—H28D | 0.9800 |
C12—H12A | 0.9800 | C28—H28A | 0.9800 |
C12—H12B | 0.9800 | C28—H28B | 0.9800 |
| | | |
C27—O2—C16 | 105.54 (12) | C3—C13—H13B | 109.5 |
C2—C1—C6 | 119.82 (13) | H13A—C13—H13B | 109.5 |
C2—C1—C12 | 116.53 (13) | C3—C13—H13C | 109.5 |
C6—C1—C12 | 123.55 (13) | H13A—C13—H13C | 109.5 |
C3—C2—C1 | 122.41 (14) | H13B—C13—H13C | 109.5 |
C3—C2—H2A | 118.8 | C5—C14—H14A | 109.5 |
C1—C2—H2A | 118.8 | C5—C14—H14B | 109.5 |
C2—C3—C4 | 117.35 (13) | H14A—C14—H14B | 109.5 |
C2—C3—C13 | 120.57 (14) | C5—C14—H14C | 109.5 |
C4—C3—C13 | 122.00 (13) | H14A—C14—H14C | 109.5 |
C3—C4—C5 | 122.41 (13) | H14B—C14—H14C | 109.5 |
C3—C4—H4A | 118.8 | O1—C15—C16 | 120.35 (14) |
C5—C4—H4A | 118.8 | O1—C15—C11 | 123.36 (13) |
C4—C5—C6 | 119.55 (13) | C16—C15—C11 | 116.25 (13) |
C4—C5—C14 | 116.98 (12) | C17—C16—O2 | 111.30 (13) |
C6—C5—C14 | 123.37 (13) | C17—C16—C15 | 132.80 (15) |
C1—C6—C5 | 118.20 (13) | O2—C16—C15 | 115.90 (13) |
C1—C6—C7 | 120.94 (12) | C16—C17—C18 | 105.62 (14) |
C5—C6—C7 | 120.78 (13) | C16—C17—C28 | 127.83 (14) |
C6—C7—C8 | 110.98 (12) | C18—C17—C28 | 126.55 (14) |
C6—C7—C10 | 117.54 (12) | C27—C18—C19 | 118.88 (15) |
C8—C7—C10 | 110.57 (12) | C27—C18—C17 | 106.58 (13) |
C6—C7—C9 | 118.00 (12) | C19—C18—C17 | 134.55 (16) |
C8—C7—C9 | 111.03 (12) | C20—C19—C18 | 118.58 (16) |
C10—C7—C9 | 86.61 (11) | C20—C19—H19A | 120.7 |
C7—C8—H8A | 109.5 | C18—C19—H19A | 120.7 |
C7—C8—H8B | 109.5 | C19—C20—C21 | 122.32 (15) |
H8A—C8—H8B | 109.5 | C19—C20—H20A | 118.8 |
C7—C8—H8C | 109.5 | C21—C20—H20A | 118.8 |
H8A—C8—H8C | 109.5 | C22—C21—C20 | 122.28 (15) |
H8B—C8—H8C | 109.5 | C22—C21—C26 | 117.33 (16) |
C11—C9—C7 | 89.75 (11) | C20—C21—C26 | 120.39 (15) |
C11—C9—H9A | 113.7 | C23—C22—C21 | 121.52 (16) |
C7—C9—H9A | 113.7 | C23—C22—H22A | 119.2 |
C11—C9—H9B | 113.7 | C21—C22—H22A | 119.2 |
C7—C9—H9B | 113.7 | C22—C23—C24 | 120.55 (16) |
H9A—C9—H9B | 110.9 | C22—C23—H23A | 119.7 |
C11—C10—C7 | 89.18 (11) | C24—C23—H23A | 119.7 |
C11—C10—H10A | 113.8 | C25—C24—C23 | 120.04 (18) |
C7—C10—H10A | 113.8 | C25—C24—H24A | 120.0 |
C11—C10—H10B | 113.8 | C23—C24—H24A | 120.0 |
C7—C10—H10B | 113.8 | C24—C25—C26 | 120.34 (15) |
H10A—C10—H10B | 111.0 | C24—C25—H25A | 119.8 |
C15—C11—C9 | 118.87 (13) | C26—C25—H25A | 119.8 |
C15—C11—C10 | 114.89 (12) | C25—C26—C27 | 124.93 (14) |
C9—C11—C10 | 88.09 (11) | C25—C26—C21 | 120.21 (15) |
C15—C11—H11A | 111.0 | C27—C26—C21 | 114.86 (15) |
C9—C11—H11A | 111.0 | O2—C27—C18 | 110.96 (13) |
C10—C11—H11A | 111.0 | O2—C27—C26 | 124.07 (14) |
C1—C12—H12A | 109.5 | C18—C27—C26 | 124.96 (14) |
C1—C12—H12B | 109.5 | C17—C28—H28D | 109.5 |
H12A—C12—H12B | 109.5 | C17—C28—H28A | 109.5 |
C1—C12—H12C | 109.5 | H28D—C28—H28A | 109.5 |
H12A—C12—H12C | 109.5 | C17—C28—H28B | 109.5 |
H12B—C12—H12C | 109.5 | H28D—C28—H28B | 109.5 |
C3—C13—H13A | 109.5 | H28A—C28—H28B | 109.5 |
| | | |
C6—C1—C2—C3 | −0.3 (2) | O1—C15—C16—C17 | 1.5 (3) |
C12—C1—C2—C3 | 176.27 (14) | C11—C15—C16—C17 | 178.95 (16) |
C1—C2—C3—C4 | −2.6 (2) | O1—C15—C16—O2 | −179.16 (13) |
C1—C2—C3—C13 | −179.50 (14) | C11—C15—C16—O2 | −1.69 (19) |
C2—C3—C4—C5 | 1.3 (2) | O2—C16—C17—C18 | −0.04 (17) |
C13—C3—C4—C5 | 178.18 (14) | C15—C16—C17—C18 | 179.35 (16) |
C3—C4—C5—C6 | 2.8 (2) | O2—C16—C17—C28 | −179.02 (14) |
C3—C4—C5—C14 | −173.74 (14) | C15—C16—C17—C28 | 0.4 (3) |
C2—C1—C6—C5 | 4.5 (2) | C16—C17—C18—C27 | −0.10 (16) |
C12—C1—C6—C5 | −171.86 (14) | C28—C17—C18—C27 | 178.91 (14) |
C2—C1—C6—C7 | −178.81 (13) | C16—C17—C18—C19 | −179.65 (17) |
C12—C1—C6—C7 | 4.8 (2) | C28—C17—C18—C19 | −0.7 (3) |
C4—C5—C6—C1 | −5.7 (2) | C27—C18—C19—C20 | −1.0 (2) |
C14—C5—C6—C1 | 170.65 (14) | C17—C18—C19—C20 | 178.55 (16) |
C4—C5—C6—C7 | 177.61 (13) | C18—C19—C20—C21 | 0.4 (2) |
C14—C5—C6—C7 | −6.0 (2) | C19—C20—C21—C22 | −179.33 (15) |
C1—C6—C7—C8 | −87.65 (16) | C19—C20—C21—C26 | 0.6 (2) |
C5—C6—C7—C8 | 88.95 (16) | C20—C21—C22—C23 | −179.85 (15) |
C1—C6—C7—C10 | 41.0 (2) | C26—C21—C22—C23 | 0.2 (2) |
C5—C6—C7—C10 | −142.42 (14) | C21—C22—C23—C24 | 0.5 (3) |
C1—C6—C7—C9 | 142.62 (14) | C22—C23—C24—C25 | −0.8 (2) |
C5—C6—C7—C9 | −40.78 (19) | C23—C24—C25—C26 | 0.3 (2) |
C6—C7—C9—C11 | −138.45 (13) | C24—C25—C26—C27 | −179.30 (15) |
C8—C7—C9—C11 | 91.85 (12) | C24—C25—C26—C21 | 0.5 (2) |
C10—C7—C9—C11 | −18.90 (11) | C22—C21—C26—C25 | −0.7 (2) |
C6—C7—C10—C11 | 138.66 (13) | C20—C21—C26—C25 | 179.36 (14) |
C8—C7—C10—C11 | −92.51 (13) | C22—C21—C26—C27 | 179.05 (14) |
C9—C7—C10—C11 | 18.69 (11) | C20—C21—C26—C27 | −0.9 (2) |
C7—C9—C11—C15 | 136.58 (13) | C16—O2—C27—C18 | −0.22 (15) |
C7—C9—C11—C10 | 19.03 (11) | C16—O2—C27—C26 | 178.96 (14) |
C7—C10—C11—C15 | −140.18 (12) | C19—C18—C27—O2 | 179.84 (13) |
C7—C10—C11—C9 | −19.05 (11) | C17—C18—C27—O2 | 0.20 (16) |
C9—C11—C15—O1 | −1.5 (2) | C19—C18—C27—C26 | 0.7 (2) |
C10—C11—C15—O1 | 100.90 (17) | C17—C18—C27—C26 | −178.97 (14) |
C9—C11—C15—C16 | −178.85 (13) | C25—C26—C27—O2 | 1.0 (2) |
C10—C11—C15—C16 | −76.49 (16) | C21—C26—C27—O2 | −178.82 (13) |
C27—O2—C16—C17 | 0.16 (16) | C25—C26—C27—C18 | −179.98 (15) |
C27—O2—C16—C15 | −179.34 (12) | C21—C26—C27—C18 | 0.3 (2) |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C15H10O2 | C17H8Br2O3 | C28H28O2 |
Mr | 222.23 | 420.05 | 396.50 |
Crystal system, space group | Triclinic, P1 | Monoclinic, C2/c | Monoclinic, P21/c |
Temperature (K) | 100 | 100 | 100 |
a, b, c (Å) | 6.1028 (5), 8.8010 (4), 10.1195 (6) | 29.644 (2), 6.2536 (5), 7.8188 (8) | 7.3816 (3), 8.2874 (6), 34.591 (2) |
α, β, γ (°) | 97.700 (4), 93.710 (6), 101.073 (6) | 90, 105.091 (6), 90 | 90, 95.487 (5), 90 |
V (Å3) | 526.31 (6) | 1399.5 (2) | 2106.4 (2) |
Z | 2 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 5.80 | 0.08 |
Crystal size (mm) | 0.34 × 0.31 × 0.28 | 0.25 × 0.24 × 0.16 | 0.34 × 0.25 × 0.16 |
|
Data collection |
Diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | – | Multi-scan (SADABS; Bruker, 2002) | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | – | 0.262, 0.398 | 0.970, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17534, 2498, 2049 | 19777, 1814, 1604 | 20365, 4182, 3360 |
Rint | 0.070 | 0.046 | 0.032 |
(sin θ/λ)max (Å−1) | 0.658 | 0.676 | 0.625 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.098, 1.06 | 0.019, 0.043, 1.08 | 0.044, 0.106, 1.03 |
No. of reflections | 2498 | 1814 | 4182 |
No. of parameters | 154 | 101 | 276 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.30 | 0.43, −0.32 | 0.26, −0.25 |
Selected geometric parameters (Å, º) for (I) topO2—C9 | 1.2257 (14) | C9—C10 | 1.4932 (16) |
C8—C9 | 1.4678 (17) | | |
| | | |
C8—C9—C10 | 118.74 (10) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O1i | 0.95 | 2.57 | 3.4182 (14) | 149 |
C7—H7A···O2ii | 0.95 | 2.55 | 3.1449 (14) | 121 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x−1, y, z. |
Selected geometric parameters (Å, º) for (II) topBr1—C4 | 1.9010 (16) | C8—C9 | 1.473 (2) |
O2—C9 | 1.223 (3) | | |
| | | |
O2—C9—C8i | 120.81 (10) | C8i—C9—C8 | 118.4 (2) |
O2—C9—C8 | 120.81 (10) | | |
Symmetry code: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···O2ii | 0.95 | 2.56 | 3.429 (2) | 151 |
Symmetry code: (ii) x, y+1, z. |
Selected bond lengths (Å) for (III) topO1—C15 | 1.2237 (19) | C15—C16 | 1.473 (2) |
C11—C15 | 1.505 (2) | | |
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Conventional `strong and directional' hydrogen bonds, such as O—H···O, N—H···O and O—H···N, have long been recognized as being of fundamental importance in determining the supramolecular structure of organic solids (Desiraju & Steiner, 1999). In molecules lacking these hydrogen-bond donors and acceptors, other types of weak and less directional forces, such as C—H···O, C—H···π and π–π interactions, become important in generating supramolecular architectures (Desiraju & Steiner, 1999; Hunder & Sanders, 1990; Nishio et al., 1998; Umezawa et al., 1998; Calhorda, 2000). Since many natural benzofurans have physiological, pharmacological and toxic properties, there is continuing interest in their synthesis (Kappe et al., 1997). Various benzofuran derivatives have been investigated as estrogen receptor ligands, because selective estrogen receptor modulators such as ralixofene have emerged as potential therapeutics for the prevention and treatment of osteoporosis (Sato et al., 1999; Smith et al., 2002). Amiodarone is a well known mitocondrial toxin containing a benzofuran ring. Amiodarone is used in the treatment and prophylaxis of both ventricular and superventricular arrhythmias, particularly in patients with heart insuffiency, because it has no significant negative inotropic effect (Spaniol et al., 2001). Although the synthesis of 2-benzoylbenzofuran, C15H10O2, (I), is known (Demirayak et al., 2002), a CSD literature search showed that its structural characterization has not been performed yet. In addition to (I), we report the molecular and supramolecular structures of two new furan derivatives, namely bis(5-bromo-benzofuran-2-yl)ketone, C17H8Br2O3, (II), and 1-(3-mesityl-3-methylcyclobutyl)(3-methylnaphtho[1,2-b]furan-2-yl)ketone, C28H28O2, (III).
Views of the molecular structures of compounds (I)–(III), including the atom-numbering scheme, are shown in Figs. 1–3. Selected bond distances and angles are listed in Tables 1–3. Compounds (I)–(III) consist mainly of a furan-2-yl moiety connected to another fragment by a carbonyl group. The C═ O bond distances and the C—C—C bond angles between two fragments are similar in all three compounds. The carbonyl group is known to coordinate to metal ions rather easily, and the presence of the furan O atom adjacent to the carbonyl group in (I)–(III) makes these compounds potential bidentate chelating agents, as reported for lanthanum (Benassi et al. 1987). In (I), the fused benzofuran ring is essentially planar and makes a dihedral angle of 46.15 (3)° with the planar benzoyl ring. The conformation of compound (I) is similar to that of corresponding benzoylbenzofuran derivatives (Benassi et al., 1987; Pei et al., 2005). The crystal packing of (I) is governed by a set of weak intermolecular interactions. A dimer is formed by a C2—H2A···O1 hydrogen bond and the dimeric units are held together by a C7—H7A···O2 hydrogen bond, two C—H···π interactions [C5—H5A···Cg2i = 3.28 Å and C15—H15A···Cg1ii = 2.80 Å, where Cg1 and Cg2 correspond to the centroids of the phenyl rings C1–C6 and C10–C15; symmetry codes: (i) −x, 1 − y, −z; (ii) 1 − x, 1 − y, −z], and two π–π interactions [Cg1···Cg1i = 3.561 (1) Å and Cg2···Cg2ii = 3.776 (1) Å; symmetry codes: (i) −x, −y, −z; (ii) 1 − x,1 − y,1 − z], resulting in a three-dimensional supramolecular network (Fig. 4).
The molecules of (II) contain two symmetry-related planar bromobenzofuran rings attached to the carbonyl group (C9═O2), being situated on the twofold rotation axis. The dihedral angle between the planes of the two equivalent bromobenzofuran ring moieties is 32.70 (4)°. In the packing of (II), the molecules are linked by a combination of a C—H···O hydrogen bond and a C—H···π interaction [C2—H2A···Cgi = 2.87 Å; Cg is the centroid of the C1–C6 ring; symmetry code: (i) x, 1 − y,-1/2 + z]. Each molecule accepts two hydrogen bonds and donates two hydrogen bonds, thus forming chains running parallel to the crystallographic b axis. These chains are further linked by relatively short Br···Br contacts [Br···Bri = 3.499 (2) Å; symmetry code: (i) 1/2 − x, 5/2 − y, −z], resulting in a two-dimensional layer architecture (Fig. 5). The C—Br···Br angle is 146.85 (12) Å, and the Br···Br interactions play a crucial role in determining the crystal packing and compete successfully with other kinds of weak intermolecular interactions.
Compound (III) consists of a fused naphthofuran moiety (O2/C16–C27), a cyclobutane ring (C7/C9–C11) and a mesityl group (C1–C6). The naphthofuran and mesityl ring systems are essentially planar, and the dihedral angle between their planes is 81.86 (3)°, differing from the values reported for 1-(1-benzofuran-2-yl)-2-mesitylethanone [89.08 (4)°; Arici et al., 2004] and (benzofuran-2-yl)(3-methyl-3-phenyl-cyclobutyl)methanone [73.63 (6)°; Yuksektepe et al., 2004]. These differences may be explained by the presence of the different substituents in these compounds. The cyclobutane ring significantly deviates from planarity, with a puckering parameter (q2) of 0.3972 (4) Å, and this finding is consistent with a similar benzofuran derivative containing a cyclobutane ring (Yuksektepe et al., 2004). However, a nearly planar cyclobutane ring was also reported by Ozdemir et al. (2004). The dihedral angles between the planes of the naphthofuran/cyclobutane and mesityl/cyclobutane ring systems are 52.15 (5) and 38.26 (8)°, respectively. In contrast to compounds (I) and (II), compound (III) does not exhibit C—H···O hydrogen bonds, and molecules of (III) are held together by C—H···π and π–π interactions. There are three C—H···π interactions between the H atoms of the methyl groups and phenyl rings [C13—H13A···Cg1i = 3.20 Å, C14—H14B···Cg1ii = 2.73 Å and C28—H28A···Cg2iii = 2.87 Å, where Cg1 and Cg2 are the C1–C6 and C21–C26 rings, respectively; symmetry codes: (i) −x, 1/2 + y, 1/2 − z; (ii) 1 − x, −1/2 + y, 1/2 − z; (iii) −x, 1 − y, −z]. In (III), the packing of the molecules is additionally reinforced by a π–π stacking interaction between adjacent naphthalene rings, with a Cg1···Cg1i distance of 3.695 (1) Å [symmetry code: (i) −x, 1 − y, −z].