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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 3| March 2016| Pages 300-303
doi:10.1107/S2056989016002085

Crystal structure of 2-[chloro­(4-meth­­oxy­phen­yl)meth­yl]-2-(4-meth­­oxy­phen­yl)-5,5-di­methyl­cyclo­hexane-1,3-dione

CROSSMARK_Color_square_no_text.svg
Saloua Chelli,a Konstantin Troshin,a Sami Lakhdar,a Herbert Mayra and Peter Mayera*

aDepartment Chemie und Biochemie, Ludwig-Maximilians-Universität, Butenandtstrasse 513, D-81377 München, Germany
*Correspondence e-mail: pemay@cup.uni-muenchen.de

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 25 January 2016; accepted 3 February 2016; online 6 February 2016)

In the title compound, C23H25ClO4, the cyclo­hexane ring adopts a chair conformation with the 4-meth­oxy­phenyl substituent in an axial position and the chloro­(4-meth­oxy­phen­yl)methyl substituent in an equatorial position. The packing features inversion dimers formed by pairs of C—H⋯O contacts and strands along [100] and [010] established by further C—H⋯O and C—H⋯Cl contacts, respectively.

CCDC reference: 1451618

1. Chemical context

Iodo­nium ylides, a subclass of hypervalent iodine compounds (Zhdankin & Stang, 2008[Zhdankin, V. V. & Stang, P. J. (2008). Chem. Rev. 108, 5299-5358.]), have a variety of synthetic applications due to their versatile reactivity pattern. The known transformations of these reagents include decomposition (Moriarty et al., 2008[Moriarty, R. M., Tyagi, S., Ivanov, D. & Constantinescu, M. (2008). J. Am. Chem. Soc. 130, 7564-7565.]; Lee & Jung, 2002[Lee, Y. R. & Jung, Y. U. (2002). J. Chem. Soc. Perkin Trans. 1, pp. 1309-1313.]) in various solvents, transylidation reactions (Hadjiarapoglou & Varvoglis, 1988[Hadjiarapoglou, L. & Varvoglis, A. (1988). Synthesis, pp. 913-915.]), C–H insertion reactions (Adam et al., 2003[Adam, W., Gogonas, E. P. & Hadjiarapoglou, L. P. (2003). Tetrahedron, 59, 7929-7934.]; Batsila et al., 2003[Batsila, C., Gogonas, E. P., Kostakis, G. & Hadjiarapoglou, L. P. (2003). Org. Lett. 5, 1511-1514.]) and intra- and inter­molecular cyclo­addition reactions under photochemical, thermal, or metal-catalysed activation (Goudreau et al., 2009[Goudreau, S. R., Marcoux, D. & Charette, A. B. (2009). J. Org. Chem. 74, 470-473.]). During our studies on the reactions of iodo­nium ylides with stabilized carbenium ions, we obtained the title compound, the structure of which provides valuable information on the mechanism of these reactions that will be discussed in a separate paper.

[Scheme 1]

2. Structural commentary

The title compound (Fig. 1[link]) comprises three six-membered rings: two benzene rings and a cyclo­hexane ring adopting a chair-conformation, with puckering amplitude Q = 0.5247 (19) Å and θ = 167.6 (2)° (Boeyens, 1978[Boeyens, J. C. A. (1978). J. Cryst. Mol. Struct. 8, 317-320.]; Cremer & Pople, 1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]). The maximum deviation from the mean plane is 0.269 (2) Å for atom C5. The 4-meth­oxy­phenyl substituent is in an axial position, while the chloro­(4-meth­oxy­phen­yl)methyl substituent is in an equatorial position. As expected, the two keto-C atoms are substituted in a trigonal–planar fashion. The C1—Cl1 bond is almost parallel to the axial C5—C8 bond (methyl substituent) with a C8—C5—C1—Cl1 torsion angle of −5.88 (11)°. The methyl C16 and the meth­oxy C23 carbon atoms have maximum deviations from the respective benzene rings, C10–C16 and C17–C22, of 0.085 (2) and 0.057 (2) Å, respectively, and hence are almost coplanar with them. The two benzene rings are inclined to one another by 41.38 (6)° and to the mean plane of the cyclohexane ring by 75.27 (9) and 43.40 (8)°, respectively.

[Figure 1]
Figure 1
The mol­ecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

3. Supra­molecular features

The packing of the title compound manifests weak C—H⋯O and C—H⋯Cl contacts (Table 1[link]), while π-stacking and C—H⋯π inter­actions are not present. Pairs of contacts of the type C14—H14⋯O2 between the benzene ring and a keto-group lead to the formation of inversion dimers with an R22(14) ring motif (Fig. 2[link]). Strands along [010] are established by weak C8–H8C⋯Cl1 contacts between the axial-oriented methyl substituent of the cyclo­hexane ring and the chloro substituent (Fig. 3[link]). Finally, strands along [100] are formed by C19—H19⋯O3 contacts between the benzene ring (C17–C22) and the methoxy group on benzene ring C10–C16 (Fig. 4[link]). The full packing including cell outlines is shown in Fig. 5[link].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C8—H8C⋯Cl1i 0.98 2.81 3.745 (2) 159
C14—H14⋯O2ii 0.95 2.52 3.394 (2) 153
C19—H19⋯O3iii 0.95 2.56 3.470 (2) 161
Symmetry codes: (i) [-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) -x, -y+2, -z+1; (iii) x-1, y, z.
[Figure 2]
Figure 2
A view of the inversion dimer formed by a pair of weak C—H⋯O contacts (blue dotted lines).
[Figure 3]
Figure 3
A view of the strands along [010] formed by weak C—H⋯Cl contacts (orange dotted lines).
[Figure 4]
Figure 4
A view along [010] of the strands along [100] formed by weak C—H⋯O contacts (green dotted lines).
[Figure 5]
Figure 5
Packing diagram of the title compound viewed along [010]. For clarity, all the weak inter­actions have been omitted.

4. Database survey

A CSD database (Version 5.36; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) search has been conducted for the three structure fragments A, B and C depicted in the following scheme.

[Scheme 2]

The search for fragment A yielded 21 hits; however, in 20 of them the cyclo­hexane ring is part of an annulated ring system and in the remaining hit it is part of a spiro-compound. Since none of the hits is really closely related to the title compound, they are not cited in detail. The search for fragment B led to six hits with the CSD refcodes CBZPOX (Noordik & Cillissen, 1981[Noordik, J. H. & Cillissen, P. J. M. (1981). Cryst. Struct. Commun. 10, 345-350.]), IYISAL (Sparr & Gilmour, 2011[Sparr, C. & Gilmour, R. (2011). Angew. Chem. Int. Ed. 50, 8391-8395.]), PAQKAV (Nair et al., 2012[Nair, R. P., Pineda-Lanorio, J. A. & Frost, B. J. (2012). Inorg. Chim. Acta, 380, 96-103.]), POMZOH (Unruh et al., 2008[Unruh, S., Karapetyan, G., Vogel, C. & Reinke, H. (2008). Private communication.]), UREKEI (Betz et al., 2011[Betz, R., McCleland, C. & Hosten, E. (2011). Acta Cryst. E67, o1199.]) and YUZPOZ (Kalyani et al., 2010[Kalyani, D., Satterfield, A. D. & Sanford, M. S. (2010). J. Am. Chem. Soc. 132, 8419-8427.]). Finally, the search for fragment C comprising the 5,5-di­methyl­cyclo­hexane-1,3-dione moiety produced 25 hits. In merely two of them fragment C is part of a non-spiro compound comparable to the title compound: CSD refcodes CETMCD (Roques et al., 1976[Roques, R., Guy, E. & Fourme, R. (1976). Acta Cryst. B32, 602-604.]) and FAWDEM (Ochiai et al., 1986[Ochiai, M., Kunishima, M., Nagao, Y., Fuji, K., Shiro, M. & Fujita, E. (1986). J. Am. Chem. Soc. 108, 8281-8283.]).

5. Synthesis and crystallization

Zinc chloride (114.2 mg, 699 µmol), tetra­butyl­ammonium chloride (190.2 mg, 684 µmol), diethyl ether (0.10 ml) and phenyl­iodo­nium-4,4-di­methyl­cyclo­hexane-2,6-dione (568.6 mg, 1.66 mmol) were dissolved in di­chloro­methane (6 ml) and cooled to 195 K. Then 4,4′-di­meth­oxy­benzhydryl chloride (417.2 mg, 1.59 mmol) in di­chloro­methane (4 ml) was added dropwise. The reaction solution was stirred at 195 K for 2 h. The resulting mixture was quenched with 2 M aqueous ammonia. Diethyl ether was added to the organic phase followed by washing with water and brine, drying (MgSO4), and evaporation of the solvents in a vacuum. The crude product was recrystallized from diethyl ether/pentane (1:1 v/v) affording the title compound (394 mg, 982 µmol; yield 62%).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. All H atoms were positioned geometrically (C—H = 0.98 Å for methyl-H, 0.99 Å for C—H2, 1.00 Å for aliphatic C—H, 0.95 Å for aromatic H) and treated as riding on their parent atoms, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. The methyl groups were allowed to rotate along the C—C bonds to best fit the experimental electron density.

Table 2
Experimental details

Crystal data
Chemical formula C23H25ClO4
Mr 400.88
Crystal system, space group Monoclinic, P21/n
Temperature (K) 100
a, b, c (Å) 10.0235 (5), 11.1997 (6), 19.0655 (12)
β (°) 100.429 (6)
V (Å3) 2104.9 (2)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.21
Crystal size (mm) 0.40 × 0.32 × 0.22
 
Data collection
Diffractometer Oxford Diffraction XCalibur3
Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England.])
Tmin, Tmax 0.982, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 11293, 4283, 3355
Rint 0.031
(sin θ/λ)max (Å−1) 0.625
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.102, 1.03
No. of reflections 4283
No. of parameters 257
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.27, −0.30
Computer programs: CrysAlis PRO (Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England.]), 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

CCDC reference: 1451618

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989016002085/rz5184sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016002085/rz5184Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989016002085/rz5184Isup3.cml

checkCIF report


Chemical context top

Iodo­nium ylides, a subclass of hypervalent iodine compounds (Zhdankin & Stang, 2008), have a variety of synthetic applications due to their versatile reactivity pattern. The known transformations of these reagents include decomposition (Moriarty et al., 2008; Lee & Jung, 2002) in various solvents, transylidation reactions (Hadjiarapoglou & Varvoglis, 1988), C–H insertion reactions (Adam et al., 2003; Batsila et al., 2003) and intra- and inter­molecular cyclo­addition reactions under photochemical, thermal, or metal-catalysed activation (Goudreau et al., 2009). During our studies on the reactions of iodo­nium ylides with stabilized carbenium ions, we obtained the title compound, the structure of which provides valuable information on the mechanism of these reactions that will be discussed in a separate paper.

Structural commentary top

The title compound (Fig. 1) comprises three six-membered rings: two planar phenyl rings and a cyclo­hexane ring adopting a chair-conformation, with puckering amplitude Q = 0.5247 (19) Å and θ = 167.6 (2)° (Boeyens, 1978; Cremer & Pople, 1975). The maximum deviation from the mean plane is 0.269 (2) Å for atom C5. The 4-meth­oxy­phenyl substituent is in axial position, while the chloro­(4-meth­oxy­phenyl)­methyl substituent is in equatorial position. As expected, the two keto-C atoms are substituted in a trigonal–planar fashion. The C1—Cl1 bond is almost parallel to the axial C5—C8 bond (methyl substituent) with a C8—C5—C1—Cl1 torsion angle of −5.88 (11)°. The methyl C16 and the meth­oxy C23 carbon atoms have maximum deviations from the respective phenyl planes of 0.085 (2) and 0.057 (2) Å, respectively, and hence are almost coplanar with them. The planes of the two phenyl rings enclose a dihedral angle of 41.38 (6)°. The dihedral angles formed by the planes of the C10–C15 and C17–C22 phenyl rings with the mean plane of the cyclo­ohexane ring are 75.27 (9) and 43.40 (8)°, respectively.

Supra­molecular features top

The packing of the title compound manifests weak C—H···O and C—H···Cl contacts (Table 1), while π-stacking and C—H···π inter­actions are not present. Pairs of contacts of the type C14—H14···O2 between the phenyl ring and a keto-group lead to the formation of 14-membered rings of R22(14) graph-set motif and accordingly to inversion-symmetric dimers (Fig. 2). Strands along [010] are established by weak C8–H8C···Cl1 contacts between the axial-oriented methyl substituent of the cyclo­hexane ring and the chloro substituent (Fig. 3). Finally, strands along [100] are formed by C19—H19···O3 contacts between phenyl and meth­oxy groups (Fig. 4). The full packing including cell outlines is shown in Fig. 5.

Database survey top

A CSD database (Version 5.36; Groom & Allen, 2014) search has been conducted for the three structure fragments A, B and C depicted in the following scheme.

The search for fragment A yielded 21 hits; however, in 20 of them the cyclo­hexane ring is part of an annulated ring system and in the remaining hit it is part of a spiro-compound. Since none of the hits is really closely related to the title compound, they are not cited in detail. The search for fragment B led to six hits with the CSD refcodes CBZPOX (Noordik & Cillissen, 1981), IYISAL (Sparr & Gilmour, 2011), PAQKAV (Nair et al., 2012), POMZOH (Unruh et al., 2008), UREKEI (Betz et al., 2011) and YUZPOZ (Kalyani et al., 2010). Finally, the search for fragment C comprising the 5,5-di­methyl­cyclo­hexane-1,3-dione moiety produced 25 hits. In merely two of them fragment C is part of a non-spiro compound comparable to the title compound: CSD refcodes CETMCD (Roques et al., 1976) and FAWDEM (Ochiai et al., 1986).

Synthesis and crystallization top

Zinc chloride (114.2 mg, 699 µmol), tetra­butyl­ammonium chloride (190.2 mg, 684 µmol), di­ethyl ether (0.10 ml) and phenyl­iodo­nium-4,4-di­methyl­cyclo­hexane-2,6-dione (568.6 mg, 1.66 mmol) were dissolved in di­chloro­methane (6 ml) and cooled to 195 K. Then 4,4'-di­meth­oxy­benzhydryl chloride (417.2 mg, 1.59 mmol) in di­chloro­methane (4 ml) was added dropwise. The reaction solution was stirred at 195 K for 2 h. The resulting mixture was quenched with 2 M aqueous ammonia. Di­ethyl ether was added to the organic phase followed by washing with water and brine, drying (MgSO4), and evaporation of the solvents in a vacuum. The crude product was recrystallized from di­ethyl ether/pentane (1:1 v/v) affording the title compound (394 mg, 982 µmol; yield 62%).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. A l l H atoms were positioned geometrically (C—H = 0.98 Å for methyl-H, 0.99 Å for C—H2, 1.00 Å for aliphatic C—H, 0.95 Å for aromatic H) and treated as riding on their parent atoms, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. The methyl groups were allowed to rotate along the C—C bonds to best fit the experimental electron density.

Structure description top

Iodo­nium ylides, a subclass of hypervalent iodine compounds (Zhdankin & Stang, 2008), have a variety of synthetic applications due to their versatile reactivity pattern. The known transformations of these reagents include decomposition (Moriarty et al., 2008; Lee & Jung, 2002) in various solvents, transylidation reactions (Hadjiarapoglou & Varvoglis, 1988), C–H insertion reactions (Adam et al., 2003; Batsila et al., 2003) and intra- and inter­molecular cyclo­addition reactions under photochemical, thermal, or metal-catalysed activation (Goudreau et al., 2009). During our studies on the reactions of iodo­nium ylides with stabilized carbenium ions, we obtained the title compound, the structure of which provides valuable information on the mechanism of these reactions that will be discussed in a separate paper.

The title compound (Fig. 1) comprises three six-membered rings: two planar phenyl rings and a cyclo­hexane ring adopting a chair-conformation, with puckering amplitude Q = 0.5247 (19) Å and θ = 167.6 (2)° (Boeyens, 1978; Cremer & Pople, 1975). The maximum deviation from the mean plane is 0.269 (2) Å for atom C5. The 4-meth­oxy­phenyl substituent is in axial position, while the chloro­(4-meth­oxy­phenyl)­methyl substituent is in equatorial position. As expected, the two keto-C atoms are substituted in a trigonal–planar fashion. The C1—Cl1 bond is almost parallel to the axial C5—C8 bond (methyl substituent) with a C8—C5—C1—Cl1 torsion angle of −5.88 (11)°. The methyl C16 and the meth­oxy C23 carbon atoms have maximum deviations from the respective phenyl planes of 0.085 (2) and 0.057 (2) Å, respectively, and hence are almost coplanar with them. The planes of the two phenyl rings enclose a dihedral angle of 41.38 (6)°. The dihedral angles formed by the planes of the C10–C15 and C17–C22 phenyl rings with the mean plane of the cyclo­ohexane ring are 75.27 (9) and 43.40 (8)°, respectively.

The packing of the title compound manifests weak C—H···O and C—H···Cl contacts (Table 1), while π-stacking and C—H···π inter­actions are not present. Pairs of contacts of the type C14—H14···O2 between the phenyl ring and a keto-group lead to the formation of 14-membered rings of R22(14) graph-set motif and accordingly to inversion-symmetric dimers (Fig. 2). Strands along [010] are established by weak C8–H8C···Cl1 contacts between the axial-oriented methyl substituent of the cyclo­hexane ring and the chloro substituent (Fig. 3). Finally, strands along [100] are formed by C19—H19···O3 contacts between phenyl and meth­oxy groups (Fig. 4). The full packing including cell outlines is shown in Fig. 5.

A CSD database (Version 5.36; Groom & Allen, 2014) search has been conducted for the three structure fragments A, B and C depicted in the following scheme.

The search for fragment A yielded 21 hits; however, in 20 of them the cyclo­hexane ring is part of an annulated ring system and in the remaining hit it is part of a spiro-compound. Since none of the hits is really closely related to the title compound, they are not cited in detail. The search for fragment B led to six hits with the CSD refcodes CBZPOX (Noordik & Cillissen, 1981), IYISAL (Sparr & Gilmour, 2011), PAQKAV (Nair et al., 2012), POMZOH (Unruh et al., 2008), UREKEI (Betz et al., 2011) and YUZPOZ (Kalyani et al., 2010). Finally, the search for fragment C comprising the 5,5-di­methyl­cyclo­hexane-1,3-dione moiety produced 25 hits. In merely two of them fragment C is part of a non-spiro compound comparable to the title compound: CSD refcodes CETMCD (Roques et al., 1976) and FAWDEM (Ochiai et al., 1986).

Synthesis and crystallization top

Zinc chloride (114.2 mg, 699 µmol), tetra­butyl­ammonium chloride (190.2 mg, 684 µmol), di­ethyl ether (0.10 ml) and phenyl­iodo­nium-4,4-di­methyl­cyclo­hexane-2,6-dione (568.6 mg, 1.66 mmol) were dissolved in di­chloro­methane (6 ml) and cooled to 195 K. Then 4,4'-di­meth­oxy­benzhydryl chloride (417.2 mg, 1.59 mmol) in di­chloro­methane (4 ml) was added dropwise. The reaction solution was stirred at 195 K for 2 h. The resulting mixture was quenched with 2 M aqueous ammonia. Di­ethyl ether was added to the organic phase followed by washing with water and brine, drying (MgSO4), and evaporation of the solvents in a vacuum. The crude product was recrystallized from di­ethyl ether/pentane (1:1 v/v) affording the title compound (394 mg, 982 µmol; yield 62%).

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. A l l H atoms were positioned geometrically (C—H = 0.98 Å for methyl-H, 0.99 Å for C—H2, 1.00 Å for aliphatic C—H, 0.95 Å for aromatic H) and treated as riding on their parent atoms, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. The methyl groups were allowed to rotate along the C—C bonds to best fit the experimental electron density.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); 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. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of the inversion-symmetric dimeric unit formed by a pair of weak C—H···O contacts (blue dotted lines).
[Figure 3] Fig. 3. A view of the strands along [010] formed by weak C—H···Cl contacts (orange dotted lines).
[Figure 4] Fig. 4. A view along [010] of the strands along [100] formed by weak C—H···O contacts (green dotted lines).
[Figure 5] Fig. 5. Packing diagram of the title compound viewed along [010]. For clarity, all the weak interactions have been omitted.
2-[Chloro(4-methoxyphenyl)methyl]-2-(4-methoxyphenyl)-5,5-dimethylcyclohexane-1,3-dione top
Crystal data top
C23H25ClO4F(000) = 848
Mr = 400.88Dx = 1.265 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
a = 10.0235 (5) ÅCell parameters from 3451 reflections
b = 11.1997 (6) Åθ = 4.4–28.5°
c = 19.0655 (12) ŵ = 0.21 mm−1
β = 100.429 (6)°T = 100 K
V = 2104.9 (2) Å3Block, colourless
Z = 40.40 × 0.32 × 0.22 mm
Data collection top
Oxford Diffraction XCalibur3
diffractometer		4283 independent reflections
Radiation source: fine-focus sealed tube3355 reflections with I > 2σ(I)
Detector resolution: 15.9809 pixels mm-1Rint = 0.031
ω scansθmax = 26.4°, θmin = 4.2°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)		h = −12→9
Tmin = 0.982, Tmax = 1.000k = −13→13
11293 measured reflectionsl = −23→22
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.102 w = 1/[σ2(Fo2) + (0.0382P)2 + 0.9962P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
4283 reflectionsΔρmax = 0.27 e Å−3
257 parametersΔρmin = −0.30 e Å−3
Crystal data top
C23H25ClO4V = 2104.9 (2) Å3
Mr = 400.88Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.0235 (5) ŵ = 0.21 mm−1
b = 11.1997 (6) ÅT = 100 K
c = 19.0655 (12) Å0.40 × 0.32 × 0.22 mm
β = 100.429 (6)°
Data collection top
Oxford Diffraction XCalibur3
diffractometer		4283 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)		3355 reflections with I > 2σ(I)
Tmin = 0.982, Tmax = 1.000Rint = 0.031
11293 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.102H-atom parameters constrained
S = 1.02Δρmax = 0.27 e Å−3
4283 reflectionsΔρmin = −0.30 e Å−3
257 parameters
Special details top

Experimental. Absorption correction: CrysAlis PRO (Agilent, 2014), Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
Cl1−0.20291 (4)0.62036 (4)0.34454 (3)0.03325 (14)
O10.08165 (13)0.59745 (11)0.29198 (7)0.0321 (3)
C1−0.04506 (17)0.66193 (15)0.40194 (9)0.0251 (4)
H10.01440.58980.40470.030*
O2−0.16483 (12)0.88985 (11)0.36243 (6)0.0272 (3)
C20.02730 (16)0.75977 (14)0.36481 (9)0.0216 (4)
O30.49570 (12)0.88680 (11)0.56782 (6)0.0280 (3)
C30.07764 (16)0.70477 (16)0.29949 (9)0.0245 (4)
O4−0.10111 (12)0.75401 (12)0.68822 (7)0.0326 (3)
C40.12691 (17)0.79029 (17)0.24936 (10)0.0281 (4)
H4A0.14720.74570.20770.034*
H4B0.21210.82790.27380.034*
C50.02225 (17)0.88830 (15)0.22329 (9)0.0251 (4)
C6−0.01011 (17)0.95395 (15)0.28892 (9)0.0248 (4)
H6A0.07270.99480.31370.030*
H6B−0.07971.01570.27310.030*
C7−0.06089 (16)0.87099 (15)0.34059 (9)0.0218 (3)
C8−0.10614 (18)0.83159 (17)0.18100 (10)0.0301 (4)
H8A−0.14370.77490.21150.045*
H8B−0.08390.78940.13960.045*
H8C−0.17320.89400.16480.045*
C90.0821 (2)0.97616 (18)0.17590 (10)0.0355 (5)
H9A0.01551.03870.15930.053*
H9B0.10500.93360.13480.053*
H9C0.16431.01250.20330.053*
C100.15436 (16)0.80039 (15)0.41729 (9)0.0215 (3)
C110.27367 (17)0.73249 (15)0.42612 (9)0.0244 (4)
H110.27790.66430.39700.029*
C120.38505 (17)0.76335 (15)0.47659 (9)0.0257 (4)
H120.46540.71670.48180.031*
C130.37996 (16)0.86264 (15)0.51996 (9)0.0225 (4)
C140.26248 (17)0.93041 (15)0.51276 (9)0.0237 (4)
H140.25800.99780.54250.028*
C150.15099 (17)0.89837 (15)0.46128 (9)0.0235 (4)
H150.07060.94490.45620.028*
C160.48994 (18)0.98232 (17)0.61706 (10)0.0308 (4)
H16A0.47061.05740.59080.046*
H16B0.57720.98870.64970.046*
H16C0.41800.96630.64440.046*
C17−0.06513 (16)0.68527 (15)0.47733 (9)0.0246 (4)
C18−0.17687 (17)0.74582 (16)0.49528 (10)0.0291 (4)
H18−0.24720.77290.45850.035*
C19−0.18604 (18)0.76657 (17)0.56548 (10)0.0312 (4)
H19−0.26250.80760.57660.037*
C20−0.08395 (17)0.72774 (15)0.62008 (10)0.0261 (4)
C210.02565 (17)0.66535 (15)0.60393 (10)0.0266 (4)
H210.09460.63670.64090.032*
C220.03362 (17)0.64505 (15)0.53272 (10)0.0261 (4)
H220.10910.60230.52180.031*
C23−0.00265 (19)0.70699 (18)0.74517 (10)0.0340 (4)
H23A−0.00060.61980.74150.051*
H23B−0.02680.72960.79090.051*
H23C0.08700.73940.74220.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0259 (2)0.0275 (2)0.0429 (3)−0.00490 (17)−0.00321 (18)0.0016 (2)
O10.0347 (7)0.0273 (7)0.0327 (7)0.0070 (5)0.0017 (5)−0.0067 (6)
C10.0197 (8)0.0210 (9)0.0334 (10)0.0007 (6)0.0014 (7)0.0008 (7)
O20.0245 (6)0.0263 (7)0.0330 (7)0.0066 (5)0.0108 (5)0.0034 (5)
C20.0195 (8)0.0191 (8)0.0262 (9)0.0021 (6)0.0043 (7)−0.0014 (7)
O30.0231 (6)0.0311 (7)0.0286 (7)0.0003 (5)0.0014 (5)−0.0054 (5)
C30.0177 (8)0.0268 (9)0.0273 (9)0.0049 (7)−0.0007 (7)−0.0039 (8)
O40.0291 (7)0.0366 (8)0.0349 (7)0.0034 (5)0.0129 (5)0.0039 (6)
C40.0215 (9)0.0349 (10)0.0286 (9)0.0046 (7)0.0068 (7)−0.0031 (8)
C50.0231 (9)0.0252 (9)0.0279 (9)0.0013 (7)0.0074 (7)−0.0001 (7)
C60.0248 (9)0.0213 (9)0.0291 (9)0.0006 (7)0.0066 (7)0.0015 (7)
C70.0222 (8)0.0207 (8)0.0220 (8)0.0000 (7)0.0024 (6)−0.0031 (7)
C80.0292 (10)0.0283 (10)0.0312 (10)0.0038 (7)0.0016 (7)−0.0010 (8)
C90.0350 (11)0.0382 (11)0.0361 (11)−0.0019 (8)0.0138 (8)0.0041 (9)
C100.0208 (8)0.0205 (8)0.0240 (8)−0.0004 (6)0.0064 (6)0.0011 (7)
C110.0260 (9)0.0217 (9)0.0267 (9)0.0038 (7)0.0076 (7)−0.0037 (7)
C120.0203 (8)0.0260 (9)0.0310 (9)0.0041 (7)0.0049 (7)−0.0018 (8)
C130.0219 (8)0.0239 (9)0.0222 (8)−0.0018 (7)0.0050 (6)0.0019 (7)
C140.0269 (9)0.0206 (8)0.0251 (9)0.0006 (7)0.0082 (7)−0.0032 (7)
C150.0213 (8)0.0234 (9)0.0268 (9)0.0034 (7)0.0073 (7)−0.0017 (7)
C160.0308 (10)0.0321 (10)0.0279 (9)−0.0026 (8)0.0015 (7)−0.0053 (8)
C170.0214 (8)0.0194 (8)0.0331 (10)−0.0018 (7)0.0053 (7)0.0044 (7)
C180.0206 (9)0.0298 (10)0.0376 (10)0.0027 (7)0.0069 (7)0.0105 (8)
C190.0231 (9)0.0322 (10)0.0416 (11)0.0072 (7)0.0144 (8)0.0103 (9)
C200.0251 (9)0.0227 (9)0.0329 (10)−0.0024 (7)0.0118 (7)0.0042 (8)
C210.0212 (9)0.0250 (9)0.0334 (10)0.0014 (7)0.0044 (7)0.0054 (8)
C220.0192 (8)0.0230 (9)0.0368 (10)0.0027 (7)0.0068 (7)0.0012 (8)
C230.0340 (10)0.0352 (11)0.0326 (10)−0.0017 (8)0.0058 (8)−0.0014 (9)
Geometric parameters (Å, º) top
Cl1—C11.8140 (17)C9—H9C0.9800
O1—C31.212 (2)C10—C151.385 (2)
C1—C171.510 (2)C10—C111.401 (2)
C1—C21.554 (2)C11—C121.379 (2)
C1—H11.0000C11—H110.9500
O2—C71.209 (2)C12—C131.392 (2)
C2—C101.539 (2)C12—H120.9500
C2—C71.549 (2)C13—C141.387 (2)
C2—C31.553 (2)C14—C151.394 (2)
O3—C131.3669 (19)C14—H140.9500
O3—C161.431 (2)C15—H150.9500
C3—C41.499 (3)C16—H16A0.9800
O4—C201.373 (2)C16—H16B0.9800
O4—C231.429 (2)C16—H16C0.9800
C4—C51.537 (2)C17—C221.385 (2)
C4—H4A0.9900C17—C181.404 (2)
C4—H4B0.9900C18—C191.378 (3)
C5—C81.528 (2)C18—H180.9500
C5—C91.530 (2)C19—C201.391 (3)
C5—C61.536 (2)C19—H190.9500
C6—C71.508 (2)C20—C211.383 (2)
C6—H6A0.9900C21—C221.393 (2)
C6—H6B0.9900C21—H210.9500
C8—H8A0.9800C22—H220.9500
C8—H8B0.9800C23—H23A0.9800
C8—H8C0.9800C23—H23B0.9800
C9—H9A0.9800C23—H23C0.9800
C9—H9B0.9800
C17—C1—C2117.73 (14)H9B—C9—H9C109.5
C17—C1—Cl1111.52 (12)C15—C10—C11118.09 (15)
C2—C1—Cl1109.52 (11)C15—C10—C2121.31 (14)
C17—C1—H1105.7C11—C10—C2120.36 (15)
C2—C1—H1105.7C12—C11—C10120.88 (16)
Cl1—C1—H1105.7C12—C11—H11119.6
C10—C2—C7108.45 (13)C10—C11—H11119.6
C10—C2—C3106.72 (12)C11—C12—C13120.16 (15)
C7—C2—C3109.30 (13)C11—C12—H12119.9
C10—C2—C1108.18 (13)C13—C12—H12119.9
C7—C2—C1114.51 (13)O3—C13—C14124.10 (15)
C3—C2—C1109.38 (13)O3—C13—C12115.89 (15)
C13—O3—C16117.10 (13)C14—C13—C12120.01 (15)
O1—C3—C4122.46 (16)C13—C14—C15119.14 (16)
O1—C3—C2120.70 (16)C13—C14—H14120.4
C4—C3—C2116.77 (14)C15—C14—H14120.4
C20—O4—C23116.90 (14)C10—C15—C14121.72 (15)
C3—C4—C5112.22 (14)C10—C15—H15119.1
C3—C4—H4A109.2C14—C15—H15119.1
C5—C4—H4A109.2O3—C16—H16A109.5
C3—C4—H4B109.2O3—C16—H16B109.5
C5—C4—H4B109.2H16A—C16—H16B109.5
H4A—C4—H4B107.9O3—C16—H16C109.5
C8—C5—C9109.80 (15)H16A—C16—H16C109.5
C8—C5—C6110.31 (14)H16B—C16—H16C109.5
C9—C5—C6109.66 (14)C22—C17—C18117.57 (17)
C8—C5—C4109.52 (14)C22—C17—C1117.99 (15)
C9—C5—C4109.41 (14)C18—C17—C1124.43 (16)
C6—C5—C4108.10 (14)C19—C18—C17120.98 (17)
C7—C6—C5112.54 (14)C19—C18—H18119.5
C7—C6—H6A109.1C17—C18—H18119.5
C5—C6—H6A109.1C18—C19—C20120.32 (16)
C7—C6—H6B109.1C18—C19—H19119.8
C5—C6—H6B109.1C20—C19—H19119.8
H6A—C6—H6B107.8O4—C20—C21124.02 (16)
O2—C7—C6122.10 (15)O4—C20—C19116.11 (15)
O2—C7—C2121.26 (15)C21—C20—C19119.87 (17)
C6—C7—C2116.65 (14)C20—C21—C22119.17 (16)
C5—C8—H8A109.5C20—C21—H21120.4
C5—C8—H8B109.5C22—C21—H21120.4
H8A—C8—H8B109.5C17—C22—C21122.05 (16)
C5—C8—H8C109.5C17—C22—H22119.0
H8A—C8—H8C109.5C21—C22—H22119.0
H8B—C8—H8C109.5O4—C23—H23A109.5
C5—C9—H9A109.5O4—C23—H23B109.5
C5—C9—H9B109.5H23A—C23—H23B109.5
H9A—C9—H9B109.5O4—C23—H23C109.5
C5—C9—H9C109.5H23A—C23—H23C109.5
H9A—C9—H9C109.5H23B—C23—H23C109.5
C17—C1—C2—C1046.58 (18)C7—C2—C10—C11−154.85 (15)
Cl1—C1—C2—C10175.35 (11)C3—C2—C10—C11−37.2 (2)
C17—C1—C2—C7−74.47 (19)C1—C2—C10—C1180.41 (18)
Cl1—C1—C2—C754.29 (16)C15—C10—C11—C12−0.8 (2)
C17—C1—C2—C3162.47 (14)C2—C10—C11—C12−175.36 (16)
Cl1—C1—C2—C3−68.77 (14)C10—C11—C12—C130.4 (3)
C10—C2—C3—O1102.75 (17)C16—O3—C13—C145.3 (2)
C7—C2—C3—O1−140.15 (16)C16—O3—C13—C12−174.99 (15)
C1—C2—C3—O1−14.1 (2)C11—C12—C13—O3−179.34 (15)
C10—C2—C3—C4−74.16 (17)C11—C12—C13—C140.3 (3)
C7—C2—C3—C442.94 (18)O3—C13—C14—C15179.02 (15)
C1—C2—C3—C4169.04 (13)C12—C13—C14—C15−0.6 (2)
O1—C3—C4—C5130.01 (17)C11—C10—C15—C140.5 (2)
C2—C3—C4—C5−53.14 (19)C2—C10—C15—C14175.01 (15)
C3—C4—C5—C8−62.80 (19)C13—C14—C15—C100.2 (3)
C3—C4—C5—C9176.80 (15)C2—C1—C17—C22−92.21 (19)
C3—C4—C5—C657.43 (18)Cl1—C1—C17—C22139.97 (14)
C8—C5—C6—C762.78 (18)C2—C1—C17—C1887.3 (2)
C9—C5—C6—C7−176.16 (14)Cl1—C1—C17—C18−40.5 (2)
C4—C5—C6—C7−56.94 (18)C22—C17—C18—C191.4 (3)
C5—C6—C7—O2−128.13 (17)C1—C17—C18—C19−178.16 (16)
C5—C6—C7—C252.09 (19)C17—C18—C19—C200.1 (3)
C10—C2—C7—O2−106.02 (17)C23—O4—C20—C21−3.9 (2)
C3—C2—C7—O2137.99 (16)C23—O4—C20—C19175.34 (16)
C1—C2—C7—O214.9 (2)C18—C19—C20—O4179.10 (16)
C10—C2—C7—C673.77 (18)C18—C19—C20—C21−1.6 (3)
C3—C2—C7—C6−42.22 (19)O4—C20—C21—C22−179.16 (16)
C1—C2—C7—C6−165.33 (14)C19—C20—C21—C221.7 (3)
C7—C2—C10—C1530.8 (2)C18—C17—C22—C21−1.4 (3)
C3—C2—C10—C15148.44 (15)C1—C17—C22—C21178.20 (16)
C1—C2—C10—C15−93.96 (18)C20—C21—C22—C17−0.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8C···Cl1i0.982.813.745 (2)159
C14—H14···O2ii0.952.523.394 (2)153
C19—H19···O3iii0.952.563.470 (2)161
Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) −x, −y+2, −z+1; (iii) x−1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8C···Cl1i0.982.813.745 (2)159
C14—H14···O2ii0.952.523.394 (2)153
C19—H19···O3iii0.952.563.470 (2)161
Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) −x, −y+2, −z+1; (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formulaC23H25ClO4
Mr400.88
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)10.0235 (5), 11.1997 (6), 19.0655 (12)
β (°) 100.429 (6)
V (Å3)2104.9 (2)
Z4
Radiation typeMo Kα
µ (mm−1)0.21
Crystal size (mm)0.40 × 0.32 × 0.22
Data collection
DiffractometerOxford Diffraction XCalibur3
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2014)
Tmin, Tmax0.982, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		11293, 4283, 3355
Rint0.031
(sin θ/λ)max (Å−1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.102, 1.02
No. of reflections4283
No. of parameters257
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.27, −0.30

Computer programs: CrysAlis PRO (Agilent, 2014), SIR97 (Altomare et al., 1999), SHELXL2014 (Sheldrick, 2015), ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 2009).

 

Acknowledgements

The authors thank Professor Thomas M. Klapötke for generous allocation of diffractometer time.

References

First citationAdam, W., Gogonas, E. P. & Hadjiarapoglou, L. P. (2003). Tetrahedron, 59, 7929–7934.  Web of Science CrossRef CAS Google Scholar
 First citationAgilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England.  Google Scholar
 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 citationBatsila, C., Gogonas, E. P., Kostakis, G. & Hadjiarapoglou, L. P. (2003). Org. Lett. 5, 1511–1514.  Web of Science CrossRef PubMed CAS Google Scholar
 First citationBetz, R., McCleland, C. & Hosten, E. (2011). Acta Cryst. E67, o1199.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationBoeyens, J. C. A. (1978). J. Cryst. Mol. Struct. 8, 317–320.  CrossRef Web of Science Google Scholar
 First citationBurnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.  Google Scholar
 First citationCremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.  CrossRef CAS Web of Science Google Scholar
 First citationGoudreau, S. R., Marcoux, D. & Charette, A. B. (2009). J. Org. Chem. 74, 470–473.  Web of Science CrossRef PubMed CAS Google Scholar
 First citationGroom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671.  Web of Science CSD CrossRef CAS Google Scholar
 First citationHadjiarapoglou, L. & Varvoglis, A. (1988). Synthesis, pp. 913–915.  CrossRef Google Scholar
 First citationKalyani, D., Satterfield, A. D. & Sanford, M. S. (2010). J. Am. Chem. Soc. 132, 8419–8427.  Web of Science CSD CrossRef CAS PubMed Google Scholar
 First citationLee, Y. R. & Jung, Y. U. (2002). J. Chem. Soc. Perkin Trans. 1, pp. 1309–1313.  Web of Science CrossRef Google Scholar
 First citationMoriarty, R. M., Tyagi, S., Ivanov, D. & Constantinescu, M. (2008). J. Am. Chem. Soc. 130, 7564–7565.  Web of Science CrossRef PubMed CAS Google Scholar
 First citationNair, R. P., Pineda-Lanorio, J. A. & Frost, B. J. (2012). Inorg. Chim. Acta, 380, 96–103.  Web of Science CrossRef CAS Google Scholar
 First citationNoordik, J. H. & Cillissen, P. J. M. (1981). Cryst. Struct. Commun. 10, 345–350.  CAS Google Scholar
 First citationOchiai, M., Kunishima, M., Nagao, Y., Fuji, K., Shiro, M. & Fujita, E. (1986). J. Am. Chem. Soc. 108, 8281–8283.  CSD CrossRef CAS Web of Science Google Scholar
 First citationRoques, R., Guy, E. & Fourme, R. (1976). Acta Cryst. B32, 602–604.  CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
 First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
 First citationSparr, C. & Gilmour, R. (2011). Angew. Chem. Int. Ed. 50, 8391–8395.  Web of Science CrossRef CAS Google Scholar
 First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationUnruh, S., Karapetyan, G., Vogel, C. & Reinke, H. (2008). Private communication.  Google Scholar
 First citationZhdankin, V. V. & Stang, P. J. (2008). Chem. Rev. 108, 5299–5358.  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 3| March 2016| Pages 300-303
doi:10.1107/S2056989016002085
Follow Acta Cryst. E
Sign up for e-alerts
E-alerts
Follow Acta Cryst. on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS