research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 2| February 2016| Pages 266-268

Crystal structure of (1S,2R)-6,6-di­methyl-4,8-dioxo-2-phenyl­spiro­[2.5]octane-1-carbaldehyde

CROSSMARK_Color_square_no_text.svg

aLudwig-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

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 19 January 2016; accepted 27 January 2016; online 30 January 2016)

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.

1. Chemical context

Apart from synthetic transformations, cyclo­propane derivatives have attracted inter­est because of their biological and pharmaceutical applications (Wessjohann et al., 2003[Wessjohann, L. A., Brandt, W. & Thiemann, T. (2003). Chem. Rev. 103, 1625-1648.]). They are present in numerous natural products and have been used extensively as reactive inter­mediates for the formation of complex structures (Reissig & Zimmer, 2003[Reissig, H. U. & Zimmer, R. (2003). Chem. Rev. 103, 1151-1196.]; Thibodeaux et al., 2012[Thibodeaux, C. J., Chang, W.-C. & Liu, H.-W. (2012). Chem. Rev. 112, 1681-1709.]). During our studies on the reactivities of iodo­nium ylides, we have developed a new method for the synthesis of substituted spiro-cyclo­propanes by the organocatalytic reaction of α,β-unsaturated aldehydes with iodo­nium ylides. 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.

[Scheme 1]

2. Structural commentary

The mol­ecular structure of the title compound is depicted in Fig. 1[link]. The central cyclo­propane ring shares the spiro atom 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 spiro atom 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)°.

[Figure 1]
Figure 1
A view of the mol­ecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supra­molecular features

The crystal packing of the title compound shows weak C—H⋯O and C—H⋯π inter­actions (Table 1[link] and Figs. 2[link] and 3[link]). Two of the three different C—H⋯O contacts lead to the formation of double strands along [100]; Fig. 2[link]. 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[link], 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[link]), 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—H17BCgv 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.

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C10–C15 phenyl ring.

D—H⋯A D—H H⋯A DA 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—H17BCgv 0.98 2.97 3.916 (2) 163
Symmetry codes: (i) [x-{\script{1\over 2}}, -y-{\script{1\over 2}}, -z]; (ii) x-1, y, z; (iii) [-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]; (v) [-x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}].
[Figure 2]
Figure 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[link] for details).
[Figure 3]
Figure 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[link] for details. Slashed dotted lines indicate bonds to a symmetry-related mol­ecule.

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[Kayukova, O. V., Lukin, P. M., Kayukov, Ya. S., Nasakin, O. E., Khrustalev, V. N., Nesterov, V. N. & Antipin, M. Yu. (1998). Chem. Heterocycl. Compd. 34, 148-158.]) and trans-1,2-bis­(meth­oxy­carbon­yl)-6,6-di­methyl­spiro­(2.5)octane-4,8-dione (GUHCUI; Maghsoodlou et al., 2009[Maghsoodlou, M. T., Khorassani, S. M. H., Heydari, R., Charati, F. R., Hazeri, N., Lashkari, M., Rostamizadeh, M., Marandi, G., Sobolev, A. & Makha, M. (2009). Tetrahedron Lett. 50, 4439-4442.]). 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[Hoffmann, H. M. R., Walenta, A., Eggert, U. & Schomburg, D. (1985). Angew. Chem. Int. Ed. Engl. 24, 607-608.]) 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[Barkov, A. Y., Korotaev, V. Y. & Sosnovskikh, V. Y. (2013). Tetrahedron Lett. 54, 4181-4184.]). 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 column chromatography (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 refinement details are summarized in Table 2[link]. 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 racemic mixture, hence the structure was refined as an inversion twin.

Table 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)
V3) 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
No. of measured, independent and observed [I > 2σ(I)] reflections 11599, 3227, 2714
Rint 0.042
(sin θ/λ)max−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[Hooft, R. W. W. (2004). COLLECT. Bruker-Nonius BV, Delft, The Netherlands.]), DENZO and SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]), SIR97 (Altomare et al., 1999[Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), ORTEPIII (Burnett & Johnson, 1996[Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Chemical context top

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 ylides, we have developed a new method for the synthesis of substituted spiro-cyclo­propanes by the organocatalytic reaction of α,β-unsaturated aldehydes with iodo­nium ylides. 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.

Structural commentary top

The molecular structure of the title compound is depicted in Fig. 1. The central cyclo­propane ring shares the spiro atom 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 spiro atom 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)°.

Supra­molecular features top

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.

Database survey top

\ 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.

Synthesis and crystallization top

\ 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 column chromatography (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).

Refinement top

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 racemic mixture, hence the structure was refined as an inversion twin.

Structure description top

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 ylides, we have developed a new method for the synthesis of substituted spiro-cyclo­propanes by the organocatalytic reaction of α,β-unsaturated aldehydes with iodo­nium ylides. 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.

The molecular structure of the title compound is depicted in Fig. 1. The central cyclo­propane ring shares the spiro atom 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 spiro atom 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)°.

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.

\ 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.

Synthesis and crystallization top

\ 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 column chromatography (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).

Refinement details top

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 racemic mixture, hence the structure was refined as an inversion twin.

Computing details top

Data collection: COLLECT (Hooft, 2004); cell refinement: 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).

Figures top
[Figure 1] 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.
[Figure 2] 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).
[Figure 3] 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.
(1S,2R)-6,6-Dimethyl-4,8-dioxo-2-phenylspiro[2.5]octane-1-carbaldehyde top
Crystal data top
C17H18O3Dx = 1.273 Mg m3
Mr = 270.31Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 5895 reflections
a = 5.8831 (1) Åθ = 3.1–27.5°
b = 12.9095 (4) ŵ = 0.09 mm1
c = 18.5655 (5) ÅT = 173 K
V = 1410.01 (6) Å3Rod, colourless
Z = 40.24 × 0.08 × 0.04 mm
F(000) = 576
Data collection top
Nonius KappaCCD
diffractometer
2714 reflections with I > 2σ(I)
Radiation source: FR591 rotating anode generatorRint = 0.042
Detector resolution: 9 pixels mm-1θmax = 27.5°, θmin = 3.2°
CCD; rotation images; thick slices scansh = 77
11599 measured reflectionsk = 1616
3227 independent reflectionsl = 2423
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-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 = 1.05Δρmax = 0.15 e Å3
3227 reflectionsΔρmin = 0.17 e Å3
183 parametersAbsolute structure: Refined as a perfect inversion twin
0 restraintsAbsolute structure parameter: 0.5
Crystal data top
C17H18O3V = 1410.01 (6) Å3
Mr = 270.31Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.8831 (1) ŵ = 0.09 mm1
b = 12.9095 (4) ÅT = 173 K
c = 18.5655 (5) Å0.24 × 0.08 × 0.04 mm
Data collection top
Nonius KappaCCD
diffractometer
2714 reflections with I > 2σ(I)
11599 measured reflectionsRint = 0.042
3227 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.085Δρmax = 0.15 e Å3
S = 1.05Δρmin = 0.17 e Å3
3227 reflectionsAbsolute structure: Refined as a perfect inversion twin
183 parametersAbsolute structure parameter: 0.5
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.4197 (3)0.32107 (11)0.04731 (9)0.0342 (4)
O20.7409 (2)0.01619 (12)0.11016 (8)0.0263 (3)
O30.1647 (3)0.17348 (13)0.20019 (9)0.0393 (4)
C10.3171 (4)0.24439 (16)0.06610 (11)0.0266 (5)
H10.16380.25150.08140.032*
C20.4217 (4)0.13971 (16)0.06618 (11)0.0219 (4)
H20.57420.13480.04260.026*
C30.2601 (3)0.05158 (15)0.05003 (11)0.0200 (4)
H30.09650.07250.05010.024*
C40.3761 (3)0.06024 (15)0.12514 (10)0.0193 (4)
C50.5547 (3)0.02063 (16)0.13825 (10)0.0201 (4)
C60.4809 (4)0.10926 (16)0.18537 (11)0.0229 (5)
H6A0.37740.15450.15750.027*
H6B0.61620.15080.19850.027*
C70.3597 (3)0.07468 (16)0.25467 (11)0.0221 (4)
C80.1576 (3)0.00558 (16)0.23406 (11)0.0243 (5)
H8A0.08450.02040.27860.029*
H8B0.04430.04780.20770.029*
C90.2249 (4)0.08522 (17)0.18801 (11)0.0236 (5)
C100.3127 (3)0.03408 (15)0.00113 (10)0.0186 (4)
C110.1524 (3)0.11331 (15)0.00784 (11)0.0223 (4)
H110.01680.11110.01990.027*
C120.1900 (4)0.19527 (16)0.05476 (12)0.0256 (5)
H120.08110.24930.05860.031*
C130.3866 (4)0.19845 (16)0.09613 (12)0.0248 (5)
H130.41140.25410.12870.030*
C140.5461 (4)0.12027 (16)0.08971 (11)0.0241 (5)
H140.68120.12270.11770.029*
C150.5103 (3)0.03793 (15)0.04251 (11)0.0219 (4)
H150.62050.01560.03850.026*
C160.2732 (4)0.17058 (18)0.29458 (13)0.0330 (5)
H16A0.40070.21750.30410.049*
H16B0.20390.14950.34030.049*
H16C0.15980.20610.26490.049*
C170.5246 (4)0.01436 (18)0.30256 (12)0.0283 (5)
H17A0.57750.04740.27690.042*
H17B0.44700.00650.34700.042*
H17C0.65500.05830.31450.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0489 (10)0.0214 (8)0.0324 (9)0.0031 (7)0.0002 (8)0.0022 (7)
O20.0174 (7)0.0365 (9)0.0249 (8)0.0033 (6)0.0021 (6)0.0018 (7)
O30.0496 (10)0.0335 (9)0.0349 (9)0.0186 (8)0.0107 (8)0.0005 (7)
C10.0348 (12)0.0242 (11)0.0208 (11)0.0024 (9)0.0013 (9)0.0010 (8)
C20.0242 (10)0.0217 (10)0.0199 (10)0.0005 (8)0.0005 (8)0.0011 (8)
C30.0190 (10)0.0206 (10)0.0204 (10)0.0011 (8)0.0013 (8)0.0026 (8)
C40.0195 (10)0.0193 (10)0.0192 (10)0.0014 (8)0.0004 (8)0.0001 (8)
C50.0199 (10)0.0243 (10)0.0160 (9)0.0008 (8)0.0016 (8)0.0049 (8)
C60.0222 (10)0.0229 (10)0.0236 (11)0.0030 (8)0.0003 (9)0.0008 (8)
C70.0204 (10)0.0259 (11)0.0200 (10)0.0022 (8)0.0008 (8)0.0018 (8)
C80.0197 (10)0.0320 (11)0.0213 (11)0.0009 (9)0.0026 (8)0.0009 (9)
C90.0193 (10)0.0301 (11)0.0214 (10)0.0062 (9)0.0006 (8)0.0014 (8)
C100.0202 (10)0.0197 (9)0.0160 (9)0.0008 (8)0.0019 (8)0.0023 (8)
C110.0203 (10)0.0253 (10)0.0214 (11)0.0017 (8)0.0001 (8)0.0012 (8)
C120.0277 (11)0.0232 (10)0.0259 (11)0.0037 (9)0.0028 (9)0.0007 (9)
C130.0303 (12)0.0235 (11)0.0207 (11)0.0019 (9)0.0016 (9)0.0019 (8)
C140.0228 (11)0.0280 (11)0.0215 (11)0.0013 (9)0.0033 (9)0.0004 (9)
C150.0213 (10)0.0223 (10)0.0220 (11)0.0028 (8)0.0014 (8)0.0026 (8)
C160.0344 (12)0.0332 (12)0.0314 (12)0.0079 (10)0.0025 (11)0.0077 (10)
C170.0290 (11)0.0332 (12)0.0226 (11)0.0050 (10)0.0017 (9)0.0020 (9)
Geometric parameters (Å, º) top
O1—C11.211 (3)C8—C91.504 (3)
O2—C51.214 (2)C8—H8A0.9900
O3—C91.214 (3)C8—H8B0.9900
C1—C21.485 (3)C10—C151.394 (3)
C1—H10.9500C10—C111.396 (3)
C2—C31.513 (3)C11—C121.388 (3)
C2—C41.524 (3)C11—H110.9500
C2—H21.0000C12—C131.389 (3)
C3—C101.490 (3)C12—H120.9500
C3—C41.557 (3)C13—C141.383 (3)
C3—H31.0000C13—H130.9500
C4—C51.501 (3)C14—C151.394 (3)
C4—C91.503 (3)C14—H140.9500
C5—C61.504 (3)C15—H150.9500
C6—C71.537 (3)C16—H16A0.9800
C6—H6A0.9900C16—H16B0.9800
C6—H6B0.9900C16—H16C0.9800
C7—C171.529 (3)C17—H17A0.9800
C7—C161.530 (3)C17—H17B0.9800
C7—C81.535 (3)C17—H17C0.9800
O1—C1—C2122.5 (2)C7—C8—H8A109.0
O1—C1—H1118.7C9—C8—H8B109.0
C2—C1—H1118.7C7—C8—H8B109.0
C1—C2—C3115.08 (18)H8A—C8—H8B107.8
C1—C2—C4122.71 (18)O3—C9—C4121.2 (2)
C3—C2—C461.67 (13)O3—C9—C8123.29 (19)
C1—C2—H2115.4C4—C9—C8115.47 (18)
C3—C2—H2115.4C15—C10—C11119.18 (18)
C4—C2—H2115.4C15—C10—C3123.40 (17)
C10—C3—C2123.65 (17)C11—C10—C3117.42 (17)
C10—C3—C4122.23 (16)C12—C11—C10120.45 (19)
C2—C3—C459.53 (12)C12—C11—H11119.8
C10—C3—H3113.7C10—C11—H11119.8
C2—C3—H3113.7C11—C12—C13120.14 (19)
C4—C3—H3113.7C11—C12—H12119.9
C5—C4—C9115.97 (17)C13—C12—H12119.9
C5—C4—C2117.47 (17)C14—C13—C12119.72 (19)
C9—C4—C2121.17 (17)C14—C13—H13120.1
C5—C4—C3113.71 (16)C12—C13—H13120.1
C9—C4—C3116.85 (16)C13—C14—C15120.53 (19)
C2—C4—C358.80 (13)C13—C14—H14119.7
O2—C5—C4121.93 (19)C15—C14—H14119.7
O2—C5—C6123.10 (19)C14—C15—C10119.97 (19)
C4—C5—C6114.90 (16)C14—C15—H15120.0
C5—C6—C7113.56 (16)C10—C15—H15120.0
C5—C6—H6A108.9C7—C16—H16A109.5
C7—C6—H6A108.9C7—C16—H16B109.5
C5—C6—H6B108.9H16A—C16—H16B109.5
C7—C6—H6B108.9C7—C16—H16C109.5
H6A—C6—H6B107.7H16A—C16—H16C109.5
C17—C7—C16109.97 (18)H16B—C16—H16C109.5
C17—C7—C8109.90 (17)C7—C17—H17A109.5
C16—C7—C8109.49 (17)C7—C17—H17B109.5
C17—C7—C6109.89 (17)H17A—C17—H17B109.5
C16—C7—C6108.94 (17)C7—C17—H17C109.5
C8—C7—C6108.63 (16)H17A—C17—H17C109.5
C9—C8—C7113.02 (16)H17B—C17—H17C109.5
C9—C8—H8A109.0
O1—C1—C2—C3147.4 (2)C5—C6—C7—C855.6 (2)
O1—C1—C2—C4141.4 (2)C17—C7—C8—C964.9 (2)
C1—C2—C3—C10134.23 (19)C16—C7—C8—C9174.16 (17)
C4—C2—C3—C10110.6 (2)C6—C7—C8—C955.3 (2)
C1—C2—C3—C4115.2 (2)C5—C4—C9—O3141.2 (2)
C1—C2—C4—C5154.52 (19)C2—C4—C9—O312.2 (3)
C3—C2—C4—C5102.42 (19)C3—C4—C9—O380.3 (3)
C1—C2—C4—C91.5 (3)C5—C4—C9—C838.1 (2)
C3—C2—C4—C9104.5 (2)C2—C4—C9—C8168.43 (18)
C1—C2—C4—C3103.1 (2)C3—C4—C9—C8100.3 (2)
C10—C3—C4—C54.1 (2)C7—C8—C9—O3131.5 (2)
C2—C3—C4—C5108.85 (19)C7—C8—C9—C447.8 (2)
C10—C3—C4—C9135.3 (2)C2—C3—C10—C154.1 (3)
C2—C3—C4—C9111.8 (2)C4—C3—C10—C1576.7 (2)
C10—C3—C4—C2112.9 (2)C2—C3—C10—C11176.62 (18)
C9—C4—C5—O2145.1 (2)C4—C3—C10—C11104.1 (2)
C2—C4—C5—O29.3 (3)C15—C10—C11—C120.4 (3)
C3—C4—C5—O275.2 (2)C3—C10—C11—C12179.71 (18)
C9—C4—C5—C637.9 (2)C10—C11—C12—C130.8 (3)
C2—C4—C5—C6167.68 (17)C11—C12—C13—C140.8 (3)
C3—C4—C5—C6101.85 (19)C12—C13—C14—C150.5 (3)
O2—C5—C6—C7135.3 (2)C13—C14—C15—C100.2 (3)
C4—C5—C6—C747.7 (2)C11—C10—C15—C140.1 (3)
C5—C6—C7—C1764.7 (2)C3—C10—C15—C14179.37 (18)
C5—C6—C7—C16174.76 (18)
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C10–C15 phenyl ring.
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i1.002.503.159 (3)123
C8—H8B···O2ii0.992.583.365 (2)137
C16—H16C···O3iii0.982.553.271 (3)131
C12—H12···Cgiv0.952.973.688 (2)133
C17—H17B···Cgv0.982.973.916 (2)163
Symmetry codes: (i) x1/2, y1/2, z; (ii) x1, y, z; (iii) x, y+1/2, z+1/2; (iv) x1/2, y+1/2, z; (v) x+1/2, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C10–C15 phenyl ring.
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i1.002.503.159 (3)123
C8—H8B···O2ii0.992.583.365 (2)137
C16—H16C···O3iii0.982.553.271 (3)131
C12—H12···Cgiv0.952.973.688 (2)133
C17—H17B···Cgv0.982.973.916 (2)163
Symmetry codes: (i) x1/2, y1/2, z; (ii) x1, y, z; (iii) x, y+1/2, z+1/2; (iv) x1/2, y+1/2, z; (v) x+1/2, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC17H18O3
Mr270.31
Crystal system, space groupOrthorhombic, P212121
Temperature (K)173
a, b, c (Å)5.8831 (1), 12.9095 (4), 18.5655 (5)
V3)1410.01 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.24 × 0.08 × 0.04
Data collection
DiffractometerNonius KappaCCD
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
11599, 3227, 2714
Rint0.042
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.085, 1.05
No. of reflections3227
No. of parameters183
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.17
Absolute structureRefined as a perfect inversion twin
Absolute structure parameter0.5

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

First citationAltomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationBarkov, A. Y., Korotaev, V. Y. & Sosnovskikh, V. Y. (2013). Tetrahedron Lett. 54, 4181–4184.  CrossRef CAS Google Scholar
First citationBurnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.  Google Scholar
First citationHoffmann, H. M. R., Walenta, A., Eggert, U. & Schomburg, D. (1985). Angew. Chem. Int. Ed. Engl. 24, 607–608.  CrossRef Google Scholar
First citationHooft, R. W. W. (2004). COLLECT. Bruker–Nonius BV, Delft, The Netherlands.  Google Scholar
First citationKayukova, O. V., Lukin, P. M., Kayukov, Ya. S., Nasakin, O. E., Khrustalev, V. N., Nesterov, V. N. & Antipin, M. Yu. (1998). Chem. Heterocycl. Compd. 34, 148–158.  CrossRef CAS Google Scholar
First citationMaghsoodlou, M. T., Khorassani, S. M. H., Heydari, R., Charati, F. R., Hazeri, N., Lashkari, M., Rostamizadeh, M., Marandi, G., Sobolev, A. & Makha, M. (2009). Tetrahedron Lett. 50, 4439–4442.  CrossRef CAS Google Scholar
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
First citationReissig, H. U. & Zimmer, R. (2003). Chem. Rev. 103, 1151–1196.  CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationThibodeaux, C. J., Chang, W.-C. & Liu, H.-W. (2012). Chem. Rev. 112, 1681–1709.  CrossRef CAS PubMed Google Scholar
First citationWessjohann, L. A., Brandt, W. & Thiemann, T. (2003). Chem. Rev. 103, 1625–1648.  Web of Science CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 2| February 2016| Pages 266-268
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds