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

Chelli, S.; Troshin, K.; Lakhdar, S.; Mayr, H.; Mayer, P.

doi:10.1107/S205698901600164X

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 72| Part 2| February 2016| Pages 266-268

doi:10.1107/S205698901600164X

Open

access

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

Saloua Chelli,^a Konstantin Troshin,^a Sami Lakhdar,^a Herbert Mayr ^a and Peter Mayer ^b ^*

^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.

Keywords: crystal structure; substituted spiro-cyclopropanes; weak C—H⋯O and C—H⋯π interactions.

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 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.

2. Structural commentary

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)°.

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 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⋯Cgⁱ^v contacts (orange dotted lines) while along [001] the links are established by C17—H17B⋯Cg^v 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	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⋯Cg^iv	0.95	2.97	3.688 (2)	133
C17—H17B⋯Cg^v	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
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
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.

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 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. C-bound H atoms were positioned geometrically (C—H = 0.95–1.00 Å) and treated as riding on their parent atoms with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(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
M_r	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
No. of measured, independent and observed [I > 2σ(I)] reflections	11599, 3227, 2714
R_int	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
Δρ_max, Δρ_min (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 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1450224

Crystal structure: contains datablocks I, global. DOI: 10.1107/S205698901600164X/su5275sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S205698901600164X/su5275Isup2.hkl

Supporting information file. DOI: 10.1107/S205698901600164X/su5275Isup3.cml

checkCIF report

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

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···Cgⁱ^v contacts (orange dotted lines) while along [001] the links are established by C17—H17B···Cg^v 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 U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(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.

Synthesis and crystallization top

Refinement details top

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

	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.

(1S,2R)-6,6-Dimethyl-4,8-dioxo-2-phenylspiro[2.5]octane-1-carbaldehyde top

Crystal data top

C₁₇H₁₈O₃	D_x = 1.273 Mg m⁻³
M_r = 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

Data collection top

Nonius KappaCCD diffractometer	2714 reflections with I > 2σ(I)
Radiation source: FR591 rotating anode generator	R_int = 0.042
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
CCD; rotation images; thick slices scans	h = −7→7
11599 measured reflections	k = −16→16
3227 independent reflections	l = −24→23

Refinement top

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(F_o²) + (0.038P)² + 0.2287P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.085	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.15 e Å⁻³
3227 reflections	Δρ_min = −0.17 e Å⁻³
183 parameters	Absolute structure: Refined as a perfect inversion twin
0 restraints	Absolute structure parameter: 0.5

Crystal data top

C₁₇H₁₈O₃	V = 1410.01 (6) Å³
M_r = 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

Data collection top

Nonius KappaCCD diffractometer	2714 reflections with I > 2σ(I)
11599 measured reflections	R_int = 0.042
3227 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.085	Δρ_max = 0.15 e Å⁻³
S = 1.05	Δρ_min = −0.17 e Å⁻³
3227 reflections	Absolute structure: Refined as a perfect inversion twin
183 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···Cg^iv	0.95	2.97	3.688 (2)	133
C17—H17B···Cg^v	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.

Hydrogen-bond geometry (Å, º) top

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···Cg^iv	0.95	2.97	3.688 (2)	133
C17—H17B···Cg^v	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
M_r	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
R_int	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
Δρ_max, Δρ_min (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

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. Web of Science CrossRef CAS IUCr Journals Google Scholar
Barkov, A. Y., Korotaev, V. Y. & Sosnovskikh, V. Y. (2013). Tetrahedron Lett. 54, 4181–4184. CrossRef CAS Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Hoffmann, H. M. R., Walenta, A., Eggert, U. & Schomburg, D. (1985). Angew. Chem. Int. Ed. Engl. 24, 607–608. CrossRef Google Scholar
Hooft, R. W. W. (2004). COLLECT. Bruker–Nonius BV, Delft, The Netherlands. Google Scholar
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. CrossRef CAS Google Scholar
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. CrossRef CAS Google Scholar
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. Google Scholar
Reissig, H. U. & Zimmer, R. (2003). Chem. Rev. 103, 1151–1196. CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Thibodeaux, C. J., Chang, W.-C. & Liu, H.-W. (2012). Chem. Rev. 112, 1681–1709. CrossRef CAS PubMed Google Scholar
Wessjohann, 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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 72| Part 2| February 2016| Pages 266-268

doi:10.1107/S205698901600164X

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

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

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

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

3. Supramolecular features