research communications
S,2R)-6,6-dimethyl-4,8-dioxo-2-phenylspiro[2.5]octane-1-carbaldehyde
of (1aLudwig-Maximilians-Universität, Department, Butenandtstrasse 5–13, 81377 München, Germany, and bDepartment Chemie und Biochemie, Ludwig-Maximilians Universität, Butenandtstrasse 5–13 (Haus F), D-81377 München, Germany
*Correspondence e-mail: pemay@cup.uni-muenchen.de
In the title compound, C17H18O3, the two non-spiro C atoms of the cyclopropane ring bear a formyl and a phenyl substituent which are trans-oriented. In the crystal, molecules are linked by weak C—H⋯O and C—H⋯π contacts resulting in a three-dimensional supramolecular structure.
CCDC reference: 1450224
1. Chemical context
Apart from synthetic transformations, cyclopropane derivatives have attracted interest because of their biological and pharmaceutical applications (Wessjohann et al., 2003). They are present in numerous natural products and have been used extensively as reactive intermediates for the formation of complex structures (Reissig & Zimmer, 2003; Thibodeaux et al., 2012). During our studies on the reactivities of iodonium we have developed a new method for the synthesis of substituted spiro-cyclopropanes by the organocatalytic reaction of α,β-unsaturated with iodonium The title compound was obtained by the reaction of the cinnamaldehyde-derived iminium ion derived from MacMillan first generation catalyst and the dimedone-derived phenyliodonium ylide.
2. Structural commentary
The molecular structure of the title compound is depicted in Fig. 1. The central cyclopropane ring shares the C4 with a cyclohexane ring system while atoms C2 and C3 bear a formyl and a phenyl substituent, respectively. The latter two substituents are trans-oriented regarding the plane of the cyclopropane ring. The angles in the three-membered ring range from 58.80 (13)° (C2—C4—C3) to 61.67 (13)° (C3—C2—C4) being close to the ideal value of 60° for such a ring. The six-membered ring containing the C4 and ring atoms C5–C9 adopts a chair conformation with a puckering amplitude Q of 0.491 (2) Å and θ = 16.8 (2)°, which indicates a slight deviation from an ideal chair conformation with θ = 0°. The plane of the central cyclopropane ring forms dihedral angles of 66.89 (16) and 89.33 (16)°, respectively, with the plane of the phenyl ring and the mean plane of the cyclohexane ring [maximum deviation from this plane is 0.272 (2) Å for atom C7]. The latter two planes form a dihedral angle of 64.15 (10)°. The plane of the formyl group, consisting of atoms C1, H1 and O1, is almost normal to the cyclopropane ring with a dihedral angle of 81.3 (3)°.
3. Supramolecular features
The crystal packing of the title compound shows weak C—H⋯O and C—H⋯π interactions (Table 1 and Figs. 2 and 3). Two of the three different C—H⋯O contacts lead to the formation of double strands along [100]; Fig. 2. Single strands are formed by C8—H8B⋯O2 contacts (red dotted lines) which are further linked to double strands along the 21-screw axes along [100] by C3—H3⋯O1 contacts (blue dotted lines). The remaining C—H⋯O as well as the C—H⋯π interactions are displayed in Fig. 3, which shows details of the crystal packing viewed along [100]. Strands along [010] are established by C16—H16B⋯O3 contacts (green dotted lines). These strands are linked by two different C—H⋯π contacts (Table 1), both of which have one of the two sides of the phenyl ring (C10–C15) as π-acceptor (Cg is the centroid of this ring). Along [100] the strands are linked by C12—H12⋯Cgiv contacts (orange dotted lines) while along [001] the links are established by C17—H17B⋯Cgv interactions (violet dotted lines) enclosing angles between the C—H bond and the plane of the π-system of ca 39° and 75° respectively. As a result of these interactions, a three-dimensional supramolecular structure is formed.
4. Database survey
Structures of spiro[2.5]octane and 4-oxo-spiro[2.5]octane derivatives are numerous; however, there are merely two different structures featuring the 6,6-dimethyl-4,8-dioxo-spiro[2.5]octane moiety as is found in the title compound, namely 6,6-dimethyl-4,8-dioxo-1,1,2,2-tetracyano-spiro(2,5)octane 1,4-dioxane solvate (NOSMIR; Kayukova et al., 1998) and trans-1,2-bis(methoxycarbonyl)-6,6-dimethylspiro(2.5)octane-4,8-dione (GUHCUI; Maghsoodlou et al., 2009). Two more structures feature the 4,8-dioxo-spiro[2.5]octane building unit, namely. trispiro(2.1.2.1.2.1)dodecane-4,8,12-trione (DAZVEF; Hoffmann et al.,1985) and (2R*)-1,1-dichloro-6,6-dimethyl-2-[(1′S*)-1′-nitroethyl]spiro[2.5]octane-4,8-dione (YILXIC; Barkov et al., 2013). In NOSMIR, each of the two non-spiro-cyclopropane C atoms bears two cyano groups while in GUHCUI each of the C atoms bears a hydrogen atom and a methoxylcarbonyl group. The latter substituents are, as in the title compound, trans-oriented with respect to the plane of the cyclopropane ring.
5. Synthesis and crystallization
A 10 ml round-bottomed flask equipped with a magnetic stirring bar was charged with a solution of the (S,E)-5-benzyl-2,2,3-trimethyl-4-oxo-1-[(E)-3-phenylallylidene]-imidazolidin-1-ium hexafluorophosphate (239 mg, 0.5 mmol, 1eq) and phenyliodonium-4,4-dimethylcyclohexane-2,6-dione (171 mg, 0.5 mmol, 1eq) in acetonitrile (5 ml). After 24 h stirring at ambient temperature, water (10 ml) was added. The aqueous phase was extracted with CH2Cl2 (15 ml). The organic layers were combined, washed with brine, and dried over MgSO4. After evaporation of the solvent under vacuum, the crude product was purified by (n-pentane/Et2O: 7/3 and 6/4) to give the title compound (98 mg, 0.362 mmol, 72%) as colourless crystals (m.p. 397–399 K).
6. Refinement
Crystal data, data collection and structure . C-bound H atoms were positioned geometrically (C—H = 0.95–1.00 Å) and treated as riding on their parent atoms with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. The methyl groups were allowed to rotate along the C—C bonds to best fit the experimental electron density. As a result of the absence of anomalous scatterers and high angle data, the Flack test results can be considered meaningless. The synthesis resulted in a hence the structure was refined as an inversion twin.
details are summarized in Table 2
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Supporting information
CCDC reference: 1450224
10.1107/S205698901600164X/su5275sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S205698901600164X/su5275Isup2.hkl
Supporting information file. DOI: 10.1107/S205698901600164X/su5275Isup3.cml
Apart from synthetic transformations, cyclopropane derivatives have attracted interest because of their biological and pharmaceutical applications (Wessjohann et al., 2003). They are present in numerous natural products and have been used extensively as reactive intermediates for the formation of complex structures (Reissig & Zimmer, 2003; Thibodeaux et al., 2012). During our studies on the reactivities of iodonium α,β-unsaturated with iodonium The title compound was obtained by the reaction of the cinnamaldehyde-derived iminium ion derived from MacMillan first generation catalyst and the dimedone-derived phenyliodonium ylide.
we have developed a new method for the synthesis of substituted spiro-cyclopropanes by the organocatalytic reaction ofThe molecular structure of the title compound is depicted in Fig. 1. The central cyclopropane ring shares the θ = 16.8 (2)°, which indicates a slight deviation from an ideal chair conformation with θ = 0°. The plane of the central cyclopropane ring forms dihedral angles of 66.89 (16) and 89.33 (16)°, respectively, with the plane of the phenyl ring and the mean plane of the cyclohexane ring [maximum deviation from this plane is 0.272 (2) Å for atom C7]. The latter two planes form a dihedral angle of 64.15 (10)°. The plane of the formyl group, consisting of atoms C1, H1 and O1, is almost normal to the cyclopropane ring with a dihedral angle of 81.3 (3)°.
C4 with a cyclohexane ring system while atoms C2 and C3 bear a formyl and a phenyl substituent, respectively. The latter two substituents are trans-oriented regarding the plane of the cyclopropane ring. The angles in the three-membered ring range from 58.80 (13)° (C2—C4—C3) to 61.67 (13)° (C3—C2—C4) being close to the ideal value of 60° for such a ring. The six-membered ring containing the C4 and ring atoms C5–C9 adopts a chair conformation with a puckering amplitude Q of 0.491 (2) Å andThe crystal packing of the title compound shows weak C—H···O and C—H···π interactions (Table 1 and Figs. 2 and 3). Two of the three different C—H···O contacts lead to the formation of double strands along [100]; Fig. 2. Single strands are formed by C8—H8B···O2 contacts (red dotted lines) which are further linked to double strands along the 21-screw axes along [100] by C3—H3···O1 contacts (blue dotted lines). The remaining C—H···O as well as the C—H···π interactions are displayed in Fig. 3, which shows details of the crystal packing viewed along [100]. Strands along [010] are established by C16—H16B···O3 contacts (green dotted lines). These strands are linked by two different C—H···π contacts (Table 1), both of which have one of the two sides of the phenyl ring (C10–C15) as π-acceptor (Cg is the centroid of this ring). Along [100] the strands are linked by C12—H12···Cgiv contacts (orange dotted lines) while along [001] the links are established by C17—H17B···Cgv interactions (violet dotted lines) enclosing angles between the C—H bond and the plane of the π-system of ca 39° and 75° respectively. As a result of these interactions, a three-dimensional supramolecular structure is formed.
\ Structures of spiro[2.5]octane and 4-oxo-spiro[2.5]octane derivatives are numerous; however, there are merely two different structures featuring the 6,6-dimethyl-4,8-dioxo-spiro[2.5]octane moiety as is found in the title compound, namely 6,6-dimethyl-4,8-dioxo-1,1,2,2-tetracyano-spiro(2,5)octane 1,4-dioxane solvate (NOSMIR; Kayukova et al., 1998) and trans-1,2-bis(methoxycarbonyl)-6,6-dimethylspiro(2.5)octane-4,8-dione (GUHCUI; Maghsoodlou et al., 2009). Two more structures feature the 4,8-dioxo-spiro[2.5]octane building unit, namely. trispiro(2.1.2.1.2.1)dodecane-4,8,12-trione (DAZVEF; Hoffmann et al.,1985) and (2R*)-1,1-dichloro-6,6-dimethyl-2-[(1'S*)-1'-\ nitroethyl]spiro[2.5]octane-4,8-dione (YILXIC; Barkov et al., 2013). In NOSMIR, each of the two non-spiro-cyclopropane C atoms bears two cyano groups while in GUHCUI each of the C atoms bears a hydrogen atom and a methoxylcarbonyl group. The latter substituents are, as in the title compound, trans-oriented with respect to the plane of the cyclopropane ring.
\ A 10 ml round-bottomed flask equipped with a magnetic stirring bar was charged with a solution of the (S,E)-5-benzyl-2,2,3-trimethyl-4-oxo-1-[(E)-3-\ phenylallylidene]- imidazolidin-1-ium hexafluorophosphate (239 mg, 0.5 mmol, 1eq) and phenyliodonium-4,4-dimethylcyclohexane-2,6-dione (171 mg, 0.5 mmol, 1eq) in acetonitrile (5 ml). After 24 h stirring at ambient temperature, water (10 ml) was added. The aqueous phase was extracted with CH2Cl2 (15 ml). The organic layers were combined, washed with brine, and dried over MgSO4. After evaporation of the solvent under vacuum, the crude product was purified by
(n-pentane/Et2O: 7/3 and 6/4) to give the title compound (98 mg, 0.362 mmol, 72%) as colourless crystals (m.p. 397–399 K).C-bound H atoms were positioned geometrically (C—H = 0.95–1.00 Å) and treated as riding on their parent atoms with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. The methyl groups were allowed to rotate along the C—C bonds to best fit the experimental electron density. Due to the absence of anomalous scatterers and high angle data, the Flack test results can be considered meaningless. The synthesis resulted in a
hence the structure was refined as an inversion twin.Apart from synthetic transformations, cyclopropane derivatives have attracted interest because of their biological and pharmaceutical applications (Wessjohann et al., 2003). They are present in numerous natural products and have been used extensively as reactive intermediates for the formation of complex structures (Reissig & Zimmer, 2003; Thibodeaux et al., 2012). During our studies on the reactivities of iodonium α,β-unsaturated with iodonium The title compound was obtained by the reaction of the cinnamaldehyde-derived iminium ion derived from MacMillan first generation catalyst and the dimedone-derived phenyliodonium ylide.
we have developed a new method for the synthesis of substituted spiro-cyclopropanes by the organocatalytic reaction ofThe molecular structure of the title compound is depicted in Fig. 1. The central cyclopropane ring shares the θ = 16.8 (2)°, which indicates a slight deviation from an ideal chair conformation with θ = 0°. The plane of the central cyclopropane ring forms dihedral angles of 66.89 (16) and 89.33 (16)°, respectively, with the plane of the phenyl ring and the mean plane of the cyclohexane ring [maximum deviation from this plane is 0.272 (2) Å for atom C7]. The latter two planes form a dihedral angle of 64.15 (10)°. The plane of the formyl group, consisting of atoms C1, H1 and O1, is almost normal to the cyclopropane ring with a dihedral angle of 81.3 (3)°.
C4 with a cyclohexane ring system while atoms C2 and C3 bear a formyl and a phenyl substituent, respectively. The latter two substituents are trans-oriented regarding the plane of the cyclopropane ring. The angles in the three-membered ring range from 58.80 (13)° (C2—C4—C3) to 61.67 (13)° (C3—C2—C4) being close to the ideal value of 60° for such a ring. The six-membered ring containing the C4 and ring atoms C5–C9 adopts a chair conformation with a puckering amplitude Q of 0.491 (2) Å andThe crystal packing of the title compound shows weak C—H···O and C—H···π interactions (Table 1 and Figs. 2 and 3). Two of the three different C—H···O contacts lead to the formation of double strands along [100]; Fig. 2. Single strands are formed by C8—H8B···O2 contacts (red dotted lines) which are further linked to double strands along the 21-screw axes along [100] by C3—H3···O1 contacts (blue dotted lines). The remaining C—H···O as well as the C—H···π interactions are displayed in Fig. 3, which shows details of the crystal packing viewed along [100]. Strands along [010] are established by C16—H16B···O3 contacts (green dotted lines). These strands are linked by two different C—H···π contacts (Table 1), both of which have one of the two sides of the phenyl ring (C10–C15) as π-acceptor (Cg is the centroid of this ring). Along [100] the strands are linked by C12—H12···Cgiv contacts (orange dotted lines) while along [001] the links are established by C17—H17B···Cgv interactions (violet dotted lines) enclosing angles between the C—H bond and the plane of the π-system of ca 39° and 75° respectively. As a result of these interactions, a three-dimensional supramolecular structure is formed.
\ Structures of spiro[2.5]octane and 4-oxo-spiro[2.5]octane derivatives are numerous; however, there are merely two different structures featuring the 6,6-dimethyl-4,8-dioxo-spiro[2.5]octane moiety as is found in the title compound, namely 6,6-dimethyl-4,8-dioxo-1,1,2,2-tetracyano-spiro(2,5)octane 1,4-dioxane solvate (NOSMIR; Kayukova et al., 1998) and trans-1,2-bis(methoxycarbonyl)-6,6-dimethylspiro(2.5)octane-4,8-dione (GUHCUI; Maghsoodlou et al., 2009). Two more structures feature the 4,8-dioxo-spiro[2.5]octane building unit, namely. trispiro(2.1.2.1.2.1)dodecane-4,8,12-trione (DAZVEF; Hoffmann et al.,1985) and (2R*)-1,1-dichloro-6,6-dimethyl-2-[(1'S*)-1'-\ nitroethyl]spiro[2.5]octane-4,8-dione (YILXIC; Barkov et al., 2013). In NOSMIR, each of the two non-spiro-cyclopropane C atoms bears two cyano groups while in GUHCUI each of the C atoms bears a hydrogen atom and a methoxylcarbonyl group. The latter substituents are, as in the title compound, trans-oriented with respect to the plane of the cyclopropane ring.
\ A 10 ml round-bottomed flask equipped with a magnetic stirring bar was charged with a solution of the (S,E)-5-benzyl-2,2,3-trimethyl-4-oxo-1-[(E)-3-\ phenylallylidene]- imidazolidin-1-ium hexafluorophosphate (239 mg, 0.5 mmol, 1eq) and phenyliodonium-4,4-dimethylcyclohexane-2,6-dione (171 mg, 0.5 mmol, 1eq) in acetonitrile (5 ml). After 24 h stirring at ambient temperature, water (10 ml) was added. The aqueous phase was extracted with CH2Cl2 (15 ml). The organic layers were combined, washed with brine, and dried over MgSO4. After evaporation of the solvent under vacuum, the crude product was purified by
(n-pentane/Et2O: 7/3 and 6/4) to give the title compound (98 mg, 0.362 mmol, 72%) as colourless crystals (m.p. 397–399 K). detailsC-bound H atoms were positioned geometrically (C—H = 0.95–1.00 Å) and treated as riding on their parent atoms with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. The methyl groups were allowed to rotate along the C—C bonds to best fit the experimental electron density. Due to the absence of anomalous scatterers and high angle data, the Flack test results can be considered meaningless. The synthesis resulted in a
hence the structure was refined as an inversion twin.Data collection: COLLECT (Hooft, 2004); cell
SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: PLATON (Spek, 2009).Fig. 1. A view of the molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. A view of the double strands along [100] formed by two different weak C—H···O contacts (red and blue dashed lines; see Table 1 for details). | |
Fig. 3. The packing established by weak C—H···O contacts (green dotted lines) C—H···π contacts (violet and orange dotted lines) viewed along [100]; see Table 1 for details. Slashed dotted lines indicate bonds to a symmetry-related molecule. |
C17H18O3 | Dx = 1.273 Mg m−3 |
Mr = 270.31 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 5895 reflections |
a = 5.8831 (1) Å | θ = 3.1–27.5° |
b = 12.9095 (4) Å | µ = 0.09 mm−1 |
c = 18.5655 (5) Å | T = 173 K |
V = 1410.01 (6) Å3 | Rod, colourless |
Z = 4 | 0.24 × 0.08 × 0.04 mm |
F(000) = 576 |
Nonius KappaCCD diffractometer | 2714 reflections with I > 2σ(I) |
Radiation source: FR591 rotating anode generator | Rint = 0.042 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
CCD; rotation images; thick slices scans | h = −7→7 |
11599 measured reflections | k = −16→16 |
3227 independent reflections | l = −24→23 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.038P)2 + 0.2287P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.085 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.15 e Å−3 |
3227 reflections | Δρmin = −0.17 e Å−3 |
183 parameters | Absolute structure: Refined as a perfect inversion twin |
0 restraints | Absolute structure parameter: 0.5 |
C17H18O3 | V = 1410.01 (6) Å3 |
Mr = 270.31 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.8831 (1) Å | µ = 0.09 mm−1 |
b = 12.9095 (4) Å | T = 173 K |
c = 18.5655 (5) Å | 0.24 × 0.08 × 0.04 mm |
Nonius KappaCCD diffractometer | 2714 reflections with I > 2σ(I) |
11599 measured reflections | Rint = 0.042 |
3227 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.085 | Δρmax = 0.15 e Å−3 |
S = 1.05 | Δρmin = −0.17 e Å−3 |
3227 reflections | Absolute structure: Refined as a perfect inversion twin |
183 parameters | Absolute structure parameter: 0.5 |
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 | ||
O1 | 0.4197 (3) | −0.32107 (11) | 0.04731 (9) | 0.0342 (4) | |
O2 | 0.7409 (2) | 0.01619 (12) | 0.11016 (8) | 0.0263 (3) | |
O3 | 0.1647 (3) | −0.17348 (13) | 0.20019 (9) | 0.0393 (4) | |
C1 | 0.3171 (4) | −0.24439 (16) | 0.06610 (11) | 0.0266 (5) | |
H1 | 0.1638 | −0.2515 | 0.0814 | 0.032* | |
C2 | 0.4217 (4) | −0.13971 (16) | 0.06618 (11) | 0.0219 (4) | |
H2 | 0.5742 | −0.1348 | 0.0426 | 0.026* | |
C3 | 0.2601 (3) | −0.05158 (15) | 0.05003 (11) | 0.0200 (4) | |
H3 | 0.0965 | −0.0725 | 0.0501 | 0.024* | |
C4 | 0.3761 (3) | −0.06024 (15) | 0.12514 (10) | 0.0193 (4) | |
C5 | 0.5547 (3) | 0.02063 (16) | 0.13825 (10) | 0.0201 (4) | |
C6 | 0.4809 (4) | 0.10926 (16) | 0.18537 (11) | 0.0229 (5) | |
H6A | 0.3774 | 0.1545 | 0.1575 | 0.027* | |
H6B | 0.6162 | 0.1508 | 0.1985 | 0.027* | |
C7 | 0.3597 (3) | 0.07468 (16) | 0.25467 (11) | 0.0221 (4) | |
C8 | 0.1576 (3) | 0.00558 (16) | 0.23406 (11) | 0.0243 (5) | |
H8A | 0.0845 | −0.0204 | 0.2786 | 0.029* | |
H8B | 0.0443 | 0.0478 | 0.2077 | 0.029* | |
C9 | 0.2249 (4) | −0.08522 (17) | 0.18801 (11) | 0.0236 (5) | |
C10 | 0.3127 (3) | 0.03408 (15) | −0.00113 (10) | 0.0186 (4) | |
C11 | 0.1524 (3) | 0.11331 (15) | −0.00784 (11) | 0.0223 (4) | |
H11 | 0.0168 | 0.1111 | 0.0199 | 0.027* | |
C12 | 0.1900 (4) | 0.19527 (16) | −0.05476 (12) | 0.0256 (5) | |
H12 | 0.0811 | 0.2493 | −0.0586 | 0.031* | |
C13 | 0.3866 (4) | 0.19845 (16) | −0.09613 (12) | 0.0248 (5) | |
H13 | 0.4114 | 0.2541 | −0.1287 | 0.030* | |
C14 | 0.5461 (4) | 0.12027 (16) | −0.08971 (11) | 0.0241 (5) | |
H14 | 0.6812 | 0.1227 | −0.1177 | 0.029* | |
C15 | 0.5103 (3) | 0.03793 (15) | −0.04251 (11) | 0.0219 (4) | |
H15 | 0.6205 | −0.0156 | −0.0385 | 0.026* | |
C16 | 0.2732 (4) | 0.17058 (18) | 0.29458 (13) | 0.0330 (5) | |
H16A | 0.4007 | 0.2175 | 0.3041 | 0.049* | |
H16B | 0.2039 | 0.1495 | 0.3403 | 0.049* | |
H16C | 0.1598 | 0.2061 | 0.2649 | 0.049* | |
C17 | 0.5246 (4) | 0.01436 (18) | 0.30256 (12) | 0.0283 (5) | |
H17A | 0.5775 | −0.0474 | 0.2769 | 0.042* | |
H17B | 0.4470 | −0.0065 | 0.3470 | 0.042* | |
H17C | 0.6550 | 0.0583 | 0.3145 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0489 (10) | 0.0214 (8) | 0.0324 (9) | 0.0031 (7) | −0.0002 (8) | −0.0022 (7) |
O2 | 0.0174 (7) | 0.0365 (9) | 0.0249 (8) | −0.0033 (6) | 0.0021 (6) | −0.0018 (7) |
O3 | 0.0496 (10) | 0.0335 (9) | 0.0349 (9) | −0.0186 (8) | 0.0107 (8) | 0.0005 (7) |
C1 | 0.0348 (12) | 0.0242 (11) | 0.0208 (11) | −0.0024 (9) | −0.0013 (9) | 0.0010 (8) |
C2 | 0.0242 (10) | 0.0217 (10) | 0.0199 (10) | 0.0005 (8) | 0.0005 (8) | 0.0011 (8) |
C3 | 0.0190 (10) | 0.0206 (10) | 0.0204 (10) | −0.0011 (8) | −0.0013 (8) | −0.0026 (8) |
C4 | 0.0195 (10) | 0.0193 (10) | 0.0192 (10) | −0.0014 (8) | −0.0004 (8) | 0.0001 (8) |
C5 | 0.0199 (10) | 0.0243 (10) | 0.0160 (9) | −0.0008 (8) | −0.0016 (8) | 0.0049 (8) |
C6 | 0.0222 (10) | 0.0229 (10) | 0.0236 (11) | −0.0030 (8) | −0.0003 (9) | 0.0008 (8) |
C7 | 0.0204 (10) | 0.0259 (11) | 0.0200 (10) | 0.0022 (8) | 0.0008 (8) | −0.0018 (8) |
C8 | 0.0197 (10) | 0.0320 (11) | 0.0213 (11) | −0.0009 (9) | 0.0026 (8) | 0.0009 (9) |
C9 | 0.0193 (10) | 0.0301 (11) | 0.0214 (10) | −0.0062 (9) | −0.0006 (8) | 0.0014 (8) |
C10 | 0.0202 (10) | 0.0197 (9) | 0.0160 (9) | −0.0008 (8) | −0.0019 (8) | −0.0023 (8) |
C11 | 0.0203 (10) | 0.0253 (10) | 0.0214 (11) | 0.0017 (8) | 0.0001 (8) | −0.0012 (8) |
C12 | 0.0277 (11) | 0.0232 (10) | 0.0259 (11) | 0.0037 (9) | −0.0028 (9) | 0.0007 (9) |
C13 | 0.0303 (12) | 0.0235 (11) | 0.0207 (11) | −0.0019 (9) | −0.0016 (9) | 0.0019 (8) |
C14 | 0.0228 (11) | 0.0280 (11) | 0.0215 (11) | −0.0013 (9) | 0.0033 (9) | −0.0004 (9) |
C15 | 0.0213 (10) | 0.0223 (10) | 0.0220 (11) | 0.0028 (8) | −0.0014 (8) | −0.0026 (8) |
C16 | 0.0344 (12) | 0.0332 (12) | 0.0314 (12) | 0.0079 (10) | 0.0025 (11) | −0.0077 (10) |
C17 | 0.0290 (11) | 0.0332 (12) | 0.0226 (11) | 0.0050 (10) | −0.0017 (9) | −0.0020 (9) |
O1—C1 | 1.211 (3) | C8—C9 | 1.504 (3) |
O2—C5 | 1.214 (2) | C8—H8A | 0.9900 |
O3—C9 | 1.214 (3) | C8—H8B | 0.9900 |
C1—C2 | 1.485 (3) | C10—C15 | 1.394 (3) |
C1—H1 | 0.9500 | C10—C11 | 1.396 (3) |
C2—C3 | 1.513 (3) | C11—C12 | 1.388 (3) |
C2—C4 | 1.524 (3) | C11—H11 | 0.9500 |
C2—H2 | 1.0000 | C12—C13 | 1.389 (3) |
C3—C10 | 1.490 (3) | C12—H12 | 0.9500 |
C3—C4 | 1.557 (3) | C13—C14 | 1.383 (3) |
C3—H3 | 1.0000 | C13—H13 | 0.9500 |
C4—C5 | 1.501 (3) | C14—C15 | 1.394 (3) |
C4—C9 | 1.503 (3) | C14—H14 | 0.9500 |
C5—C6 | 1.504 (3) | C15—H15 | 0.9500 |
C6—C7 | 1.537 (3) | C16—H16A | 0.9800 |
C6—H6A | 0.9900 | C16—H16B | 0.9800 |
C6—H6B | 0.9900 | C16—H16C | 0.9800 |
C7—C17 | 1.529 (3) | C17—H17A | 0.9800 |
C7—C16 | 1.530 (3) | C17—H17B | 0.9800 |
C7—C8 | 1.535 (3) | C17—H17C | 0.9800 |
O1—C1—C2 | 122.5 (2) | C7—C8—H8A | 109.0 |
O1—C1—H1 | 118.7 | C9—C8—H8B | 109.0 |
C2—C1—H1 | 118.7 | C7—C8—H8B | 109.0 |
C1—C2—C3 | 115.08 (18) | H8A—C8—H8B | 107.8 |
C1—C2—C4 | 122.71 (18) | O3—C9—C4 | 121.2 (2) |
C3—C2—C4 | 61.67 (13) | O3—C9—C8 | 123.29 (19) |
C1—C2—H2 | 115.4 | C4—C9—C8 | 115.47 (18) |
C3—C2—H2 | 115.4 | C15—C10—C11 | 119.18 (18) |
C4—C2—H2 | 115.4 | C15—C10—C3 | 123.40 (17) |
C10—C3—C2 | 123.65 (17) | C11—C10—C3 | 117.42 (17) |
C10—C3—C4 | 122.23 (16) | C12—C11—C10 | 120.45 (19) |
C2—C3—C4 | 59.53 (12) | C12—C11—H11 | 119.8 |
C10—C3—H3 | 113.7 | C10—C11—H11 | 119.8 |
C2—C3—H3 | 113.7 | C11—C12—C13 | 120.14 (19) |
C4—C3—H3 | 113.7 | C11—C12—H12 | 119.9 |
C5—C4—C9 | 115.97 (17) | C13—C12—H12 | 119.9 |
C5—C4—C2 | 117.47 (17) | C14—C13—C12 | 119.72 (19) |
C9—C4—C2 | 121.17 (17) | C14—C13—H13 | 120.1 |
C5—C4—C3 | 113.71 (16) | C12—C13—H13 | 120.1 |
C9—C4—C3 | 116.85 (16) | C13—C14—C15 | 120.53 (19) |
C2—C4—C3 | 58.80 (13) | C13—C14—H14 | 119.7 |
O2—C5—C4 | 121.93 (19) | C15—C14—H14 | 119.7 |
O2—C5—C6 | 123.10 (19) | C14—C15—C10 | 119.97 (19) |
C4—C5—C6 | 114.90 (16) | C14—C15—H15 | 120.0 |
C5—C6—C7 | 113.56 (16) | C10—C15—H15 | 120.0 |
C5—C6—H6A | 108.9 | C7—C16—H16A | 109.5 |
C7—C6—H6A | 108.9 | C7—C16—H16B | 109.5 |
C5—C6—H6B | 108.9 | H16A—C16—H16B | 109.5 |
C7—C6—H6B | 108.9 | C7—C16—H16C | 109.5 |
H6A—C6—H6B | 107.7 | H16A—C16—H16C | 109.5 |
C17—C7—C16 | 109.97 (18) | H16B—C16—H16C | 109.5 |
C17—C7—C8 | 109.90 (17) | C7—C17—H17A | 109.5 |
C16—C7—C8 | 109.49 (17) | C7—C17—H17B | 109.5 |
C17—C7—C6 | 109.89 (17) | H17A—C17—H17B | 109.5 |
C16—C7—C6 | 108.94 (17) | C7—C17—H17C | 109.5 |
C8—C7—C6 | 108.63 (16) | H17A—C17—H17C | 109.5 |
C9—C8—C7 | 113.02 (16) | H17B—C17—H17C | 109.5 |
C9—C8—H8A | 109.0 | ||
O1—C1—C2—C3 | 147.4 (2) | C5—C6—C7—C8 | −55.6 (2) |
O1—C1—C2—C4 | −141.4 (2) | C17—C7—C8—C9 | −64.9 (2) |
C1—C2—C3—C10 | −134.23 (19) | C16—C7—C8—C9 | 174.16 (17) |
C4—C2—C3—C10 | 110.6 (2) | C6—C7—C8—C9 | 55.3 (2) |
C1—C2—C3—C4 | 115.2 (2) | C5—C4—C9—O3 | −141.2 (2) |
C1—C2—C4—C5 | 154.52 (19) | C2—C4—C9—O3 | 12.2 (3) |
C3—C2—C4—C5 | −102.42 (19) | C3—C4—C9—O3 | 80.3 (3) |
C1—C2—C4—C9 | 1.5 (3) | C5—C4—C9—C8 | 38.1 (2) |
C3—C2—C4—C9 | 104.5 (2) | C2—C4—C9—C8 | −168.43 (18) |
C1—C2—C4—C3 | −103.1 (2) | C3—C4—C9—C8 | −100.3 (2) |
C10—C3—C4—C5 | −4.1 (2) | C7—C8—C9—O3 | 131.5 (2) |
C2—C3—C4—C5 | 108.85 (19) | C7—C8—C9—C4 | −47.8 (2) |
C10—C3—C4—C9 | 135.3 (2) | C2—C3—C10—C15 | 4.1 (3) |
C2—C3—C4—C9 | −111.8 (2) | C4—C3—C10—C15 | 76.7 (2) |
C10—C3—C4—C2 | −112.9 (2) | C2—C3—C10—C11 | −176.62 (18) |
C9—C4—C5—O2 | 145.1 (2) | C4—C3—C10—C11 | −104.1 (2) |
C2—C4—C5—O2 | −9.3 (3) | C15—C10—C11—C12 | −0.4 (3) |
C3—C4—C5—O2 | −75.2 (2) | C3—C10—C11—C12 | −179.71 (18) |
C9—C4—C5—C6 | −37.9 (2) | C10—C11—C12—C13 | 0.8 (3) |
C2—C4—C5—C6 | 167.68 (17) | C11—C12—C13—C14 | −0.8 (3) |
C3—C4—C5—C6 | 101.85 (19) | C12—C13—C14—C15 | 0.5 (3) |
O2—C5—C6—C7 | −135.3 (2) | C13—C14—C15—C10 | −0.2 (3) |
C4—C5—C6—C7 | 47.7 (2) | C11—C10—C15—C14 | 0.1 (3) |
C5—C6—C7—C17 | 64.7 (2) | C3—C10—C15—C14 | 179.37 (18) |
C5—C6—C7—C16 | −174.76 (18) |
Cg is the centroid of the C10–C15 phenyl ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 1.00 | 2.50 | 3.159 (3) | 123 |
C8—H8B···O2ii | 0.99 | 2.58 | 3.365 (2) | 137 |
C16—H16C···O3iii | 0.98 | 2.55 | 3.271 (3) | 131 |
C12—H12···Cgiv | 0.95 | 2.97 | 3.688 (2) | 133 |
C17—H17B···Cgv | 0.98 | 2.97 | 3.916 (2) | 163 |
Symmetry codes: (i) x−1/2, −y−1/2, −z; (ii) x−1, y, z; (iii) −x, y+1/2, −z+1/2; (iv) x−1/2, −y+1/2, −z; (v) −x+1/2, −y, z+1/2. |
Cg is the centroid of the C10–C15 phenyl ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 1.00 | 2.50 | 3.159 (3) | 123 |
C8—H8B···O2ii | 0.99 | 2.58 | 3.365 (2) | 137 |
C16—H16C···O3iii | 0.98 | 2.55 | 3.271 (3) | 131 |
C12—H12···Cgiv | 0.95 | 2.97 | 3.688 (2) | 133 |
C17—H17B···Cgv | 0.98 | 2.97 | 3.916 (2) | 163 |
Symmetry codes: (i) x−1/2, −y−1/2, −z; (ii) x−1, y, z; (iii) −x, y+1/2, −z+1/2; (iv) x−1/2, −y+1/2, −z; (v) −x+1/2, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C17H18O3 |
Mr | 270.31 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 173 |
a, b, c (Å) | 5.8831 (1), 12.9095 (4), 18.5655 (5) |
V (Å3) | 1410.01 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.24 × 0.08 × 0.04 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11599, 3227, 2714 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.085, 1.05 |
No. of reflections | 3227 |
No. of parameters | 183 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.17 |
Absolute structure | Refined as a perfect inversion twin |
Absolute structure parameter | 0.5 |
Computer programs: COLLECT (Hooft, 2004), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL2014 (Sheldrick, 2015), ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 2009).
Acknowledgements
The authors thank the Department of Chemistry of the Ludwig-Maximilians Universität, Munich, for financial support.
References
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