research communications
of 2-[chloro(4-methoxyphenyl)methyl]-2-(4-methoxyphenyl)-5,5-dimethylcyclohexane-1,3-dione
aDepartment Chemie und Biochemie, Ludwig-Maximilians-Universität, Butenandtstrasse 513, D-81377 München, Germany
*Correspondence e-mail: pemay@cup.uni-muenchen.de
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.
Keywords: crystal structure; weak C—H⋯O and C—H⋯Cl interactions.
CCDC reference: 1451618
1. Chemical context
Iodonium ), 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 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.
a subclass of hypervalent iodine compounds (Zhdankin & Stang, 20082. Structural commentary
The title compound (Fig. 1) 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; Cremer & Pople, 1975). 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.
3. Supramolecular features
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 benzene ring and a keto-group lead to the formation of inversion dimers with an R22(14) ring motif (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 the benzene ring (C17–C22) and the methoxy group on benzene ring C10–C16 (Fig. 4). The full packing including cell outlines is shown in Fig. 5.
4. Database survey
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).
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 . 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.
details are summarized in Table 2Supporting information
CCDC reference: 1451618
10.1107/S2056989016002085/rz5184sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016002085/rz5184Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016002085/rz5184Isup3.cml
Iodonium
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 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).
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%).
Crystal data, data collection and structure
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.Iodonium
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 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).
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%).
detailsCrystal data, data collection and structure
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.Data collection: CrysAlis PRO (Agilent, 2014); cell
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).Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. A view of the inversion-symmetric dimeric unit formed by a pair of weak C—H···O contacts (blue dotted lines). | |
Fig. 3. A view of the strands along [010] formed by weak C—H···Cl contacts (orange dotted lines). | |
Fig. 4. A view along [010] of the strands along [100] formed by weak C—H···O contacts (green dotted lines). | |
Fig. 5. Packing diagram of the title compound viewed along [010]. For clarity, all the weak interactions have been omitted. |
C23H25ClO4 | F(000) = 848 |
Mr = 400.88 | Dx = 1.265 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 10.0235 (5) Å | Cell parameters from 3451 reflections |
b = 11.1997 (6) Å | θ = 4.4–28.5° |
c = 19.0655 (12) Å | µ = 0.21 mm−1 |
β = 100.429 (6)° | T = 100 K |
V = 2104.9 (2) Å3 | Block, colourless |
Z = 4 | 0.40 × 0.32 × 0.22 mm |
Oxford Diffraction XCalibur3 diffractometer | 4283 independent reflections |
Radiation source: fine-focus sealed tube | 3355 reflections with I > 2σ(I) |
Detector resolution: 15.9809 pixels mm-1 | Rint = 0.031 |
ω scans | θmax = 26.4°, θmin = 4.2° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | h = −12→9 |
Tmin = 0.982, Tmax = 1.000 | k = −13→13 |
11293 measured reflections | l = −23→22 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-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 reflections | Δρmax = 0.27 e Å−3 |
257 parameters | Δρmin = −0.30 e Å−3 |
C23H25ClO4 | V = 2104.9 (2) Å3 |
Mr = 400.88 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.0235 (5) Å | µ = 0.21 mm−1 |
b = 11.1997 (6) Å | T = 100 K |
c = 19.0655 (12) Å | 0.40 × 0.32 × 0.22 mm |
β = 100.429 (6)° |
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 = 1.000 | Rint = 0.031 |
11293 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.27 e Å−3 |
4283 reflections | Δρmin = −0.30 e Å−3 |
257 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | −0.20291 (4) | 0.62036 (4) | 0.34454 (3) | 0.03325 (14) | |
O1 | 0.08165 (13) | 0.59745 (11) | 0.29198 (7) | 0.0321 (3) | |
C1 | −0.04506 (17) | 0.66193 (15) | 0.40194 (9) | 0.0251 (4) | |
H1 | 0.0144 | 0.5898 | 0.4047 | 0.030* | |
O2 | −0.16483 (12) | 0.88985 (11) | 0.36243 (6) | 0.0272 (3) | |
C2 | 0.02730 (16) | 0.75977 (14) | 0.36481 (9) | 0.0216 (4) | |
O3 | 0.49570 (12) | 0.88680 (11) | 0.56782 (6) | 0.0280 (3) | |
C3 | 0.07764 (16) | 0.70477 (16) | 0.29949 (9) | 0.0245 (4) | |
O4 | −0.10111 (12) | 0.75401 (12) | 0.68822 (7) | 0.0326 (3) | |
C4 | 0.12691 (17) | 0.79029 (17) | 0.24936 (10) | 0.0281 (4) | |
H4A | 0.1472 | 0.7457 | 0.2077 | 0.034* | |
H4B | 0.2121 | 0.8279 | 0.2738 | 0.034* | |
C5 | 0.02225 (17) | 0.88830 (15) | 0.22329 (9) | 0.0251 (4) | |
C6 | −0.01011 (17) | 0.95395 (15) | 0.28892 (9) | 0.0248 (4) | |
H6A | 0.0727 | 0.9948 | 0.3137 | 0.030* | |
H6B | −0.0797 | 1.0157 | 0.2731 | 0.030* | |
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 | −0.1437 | 0.7749 | 0.2115 | 0.045* | |
H8B | −0.0839 | 0.7894 | 0.1396 | 0.045* | |
H8C | −0.1732 | 0.8940 | 0.1648 | 0.045* | |
C9 | 0.0821 (2) | 0.97616 (18) | 0.17590 (10) | 0.0355 (5) | |
H9A | 0.0155 | 1.0387 | 0.1593 | 0.053* | |
H9B | 0.1050 | 0.9336 | 0.1348 | 0.053* | |
H9C | 0.1643 | 1.0125 | 0.2033 | 0.053* | |
C10 | 0.15436 (16) | 0.80039 (15) | 0.41729 (9) | 0.0215 (3) | |
C11 | 0.27367 (17) | 0.73249 (15) | 0.42612 (9) | 0.0244 (4) | |
H11 | 0.2779 | 0.6643 | 0.3970 | 0.029* | |
C12 | 0.38505 (17) | 0.76335 (15) | 0.47659 (9) | 0.0257 (4) | |
H12 | 0.4654 | 0.7167 | 0.4818 | 0.031* | |
C13 | 0.37996 (16) | 0.86264 (15) | 0.51996 (9) | 0.0225 (4) | |
C14 | 0.26248 (17) | 0.93041 (15) | 0.51276 (9) | 0.0237 (4) | |
H14 | 0.2580 | 0.9978 | 0.5425 | 0.028* | |
C15 | 0.15099 (17) | 0.89837 (15) | 0.46128 (9) | 0.0235 (4) | |
H15 | 0.0706 | 0.9449 | 0.4562 | 0.028* | |
C16 | 0.48994 (18) | 0.98232 (17) | 0.61706 (10) | 0.0308 (4) | |
H16A | 0.4706 | 1.0574 | 0.5908 | 0.046* | |
H16B | 0.5772 | 0.9887 | 0.6497 | 0.046* | |
H16C | 0.4180 | 0.9663 | 0.6444 | 0.046* | |
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 | −0.2472 | 0.7729 | 0.4585 | 0.035* | |
C19 | −0.18604 (18) | 0.76657 (17) | 0.56548 (10) | 0.0312 (4) | |
H19 | −0.2625 | 0.8076 | 0.5766 | 0.037* | |
C20 | −0.08395 (17) | 0.72774 (15) | 0.62008 (10) | 0.0261 (4) | |
C21 | 0.02565 (17) | 0.66535 (15) | 0.60393 (10) | 0.0266 (4) | |
H21 | 0.0946 | 0.6367 | 0.6409 | 0.032* | |
C22 | 0.03362 (17) | 0.64505 (15) | 0.53272 (10) | 0.0261 (4) | |
H22 | 0.1091 | 0.6023 | 0.5218 | 0.031* | |
C23 | −0.00265 (19) | 0.70699 (18) | 0.74517 (10) | 0.0340 (4) | |
H23A | −0.0006 | 0.6198 | 0.7415 | 0.051* | |
H23B | −0.0268 | 0.7296 | 0.7909 | 0.051* | |
H23C | 0.0870 | 0.7394 | 0.7422 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0259 (2) | 0.0275 (2) | 0.0429 (3) | −0.00490 (17) | −0.00321 (18) | 0.0016 (2) |
O1 | 0.0347 (7) | 0.0273 (7) | 0.0327 (7) | 0.0070 (5) | 0.0017 (5) | −0.0067 (6) |
C1 | 0.0197 (8) | 0.0210 (9) | 0.0334 (10) | 0.0007 (6) | 0.0014 (7) | 0.0008 (7) |
O2 | 0.0245 (6) | 0.0263 (7) | 0.0330 (7) | 0.0066 (5) | 0.0108 (5) | 0.0034 (5) |
C2 | 0.0195 (8) | 0.0191 (8) | 0.0262 (9) | 0.0021 (6) | 0.0043 (7) | −0.0014 (7) |
O3 | 0.0231 (6) | 0.0311 (7) | 0.0286 (7) | 0.0003 (5) | 0.0014 (5) | −0.0054 (5) |
C3 | 0.0177 (8) | 0.0268 (9) | 0.0273 (9) | 0.0049 (7) | −0.0007 (7) | −0.0039 (8) |
O4 | 0.0291 (7) | 0.0366 (8) | 0.0349 (7) | 0.0034 (5) | 0.0129 (5) | 0.0039 (6) |
C4 | 0.0215 (9) | 0.0349 (10) | 0.0286 (9) | 0.0046 (7) | 0.0068 (7) | −0.0031 (8) |
C5 | 0.0231 (9) | 0.0252 (9) | 0.0279 (9) | 0.0013 (7) | 0.0074 (7) | −0.0001 (7) |
C6 | 0.0248 (9) | 0.0213 (9) | 0.0291 (9) | 0.0006 (7) | 0.0066 (7) | 0.0015 (7) |
C7 | 0.0222 (8) | 0.0207 (8) | 0.0220 (8) | 0.0000 (7) | 0.0024 (6) | −0.0031 (7) |
C8 | 0.0292 (10) | 0.0283 (10) | 0.0312 (10) | 0.0038 (7) | 0.0016 (7) | −0.0010 (8) |
C9 | 0.0350 (11) | 0.0382 (11) | 0.0361 (11) | −0.0019 (8) | 0.0138 (8) | 0.0041 (9) |
C10 | 0.0208 (8) | 0.0205 (8) | 0.0240 (8) | −0.0004 (6) | 0.0064 (6) | 0.0011 (7) |
C11 | 0.0260 (9) | 0.0217 (9) | 0.0267 (9) | 0.0038 (7) | 0.0076 (7) | −0.0037 (7) |
C12 | 0.0203 (8) | 0.0260 (9) | 0.0310 (9) | 0.0041 (7) | 0.0049 (7) | −0.0018 (8) |
C13 | 0.0219 (8) | 0.0239 (9) | 0.0222 (8) | −0.0018 (7) | 0.0050 (6) | 0.0019 (7) |
C14 | 0.0269 (9) | 0.0206 (8) | 0.0251 (9) | 0.0006 (7) | 0.0082 (7) | −0.0032 (7) |
C15 | 0.0213 (8) | 0.0234 (9) | 0.0268 (9) | 0.0034 (7) | 0.0073 (7) | −0.0017 (7) |
C16 | 0.0308 (10) | 0.0321 (10) | 0.0279 (9) | −0.0026 (8) | 0.0015 (7) | −0.0053 (8) |
C17 | 0.0214 (8) | 0.0194 (8) | 0.0331 (10) | −0.0018 (7) | 0.0053 (7) | 0.0044 (7) |
C18 | 0.0206 (9) | 0.0298 (10) | 0.0376 (10) | 0.0027 (7) | 0.0069 (7) | 0.0105 (8) |
C19 | 0.0231 (9) | 0.0322 (10) | 0.0416 (11) | 0.0072 (7) | 0.0144 (8) | 0.0103 (9) |
C20 | 0.0251 (9) | 0.0227 (9) | 0.0329 (10) | −0.0024 (7) | 0.0118 (7) | 0.0042 (8) |
C21 | 0.0212 (9) | 0.0250 (9) | 0.0334 (10) | 0.0014 (7) | 0.0044 (7) | 0.0054 (8) |
C22 | 0.0192 (8) | 0.0230 (9) | 0.0368 (10) | 0.0027 (7) | 0.0068 (7) | 0.0012 (8) |
C23 | 0.0340 (10) | 0.0352 (11) | 0.0326 (10) | −0.0017 (8) | 0.0058 (8) | −0.0014 (9) |
Cl1—C1 | 1.8140 (17) | C9—H9C | 0.9800 |
O1—C3 | 1.212 (2) | C10—C15 | 1.385 (2) |
C1—C17 | 1.510 (2) | C10—C11 | 1.401 (2) |
C1—C2 | 1.554 (2) | C11—C12 | 1.379 (2) |
C1—H1 | 1.0000 | C11—H11 | 0.9500 |
O2—C7 | 1.209 (2) | C12—C13 | 1.392 (2) |
C2—C10 | 1.539 (2) | C12—H12 | 0.9500 |
C2—C7 | 1.549 (2) | C13—C14 | 1.387 (2) |
C2—C3 | 1.553 (2) | C14—C15 | 1.394 (2) |
O3—C13 | 1.3669 (19) | C14—H14 | 0.9500 |
O3—C16 | 1.431 (2) | C15—H15 | 0.9500 |
C3—C4 | 1.499 (3) | C16—H16A | 0.9800 |
O4—C20 | 1.373 (2) | C16—H16B | 0.9800 |
O4—C23 | 1.429 (2) | C16—H16C | 0.9800 |
C4—C5 | 1.537 (2) | C17—C22 | 1.385 (2) |
C4—H4A | 0.9900 | C17—C18 | 1.404 (2) |
C4—H4B | 0.9900 | C18—C19 | 1.378 (3) |
C5—C8 | 1.528 (2) | C18—H18 | 0.9500 |
C5—C9 | 1.530 (2) | C19—C20 | 1.391 (3) |
C5—C6 | 1.536 (2) | C19—H19 | 0.9500 |
C6—C7 | 1.508 (2) | C20—C21 | 1.383 (2) |
C6—H6A | 0.9900 | C21—C22 | 1.393 (2) |
C6—H6B | 0.9900 | C21—H21 | 0.9500 |
C8—H8A | 0.9800 | C22—H22 | 0.9500 |
C8—H8B | 0.9800 | C23—H23A | 0.9800 |
C8—H8C | 0.9800 | C23—H23B | 0.9800 |
C9—H9A | 0.9800 | C23—H23C | 0.9800 |
C9—H9B | 0.9800 | ||
C17—C1—C2 | 117.73 (14) | H9B—C9—H9C | 109.5 |
C17—C1—Cl1 | 111.52 (12) | C15—C10—C11 | 118.09 (15) |
C2—C1—Cl1 | 109.52 (11) | C15—C10—C2 | 121.31 (14) |
C17—C1—H1 | 105.7 | C11—C10—C2 | 120.36 (15) |
C2—C1—H1 | 105.7 | C12—C11—C10 | 120.88 (16) |
Cl1—C1—H1 | 105.7 | C12—C11—H11 | 119.6 |
C10—C2—C7 | 108.45 (13) | C10—C11—H11 | 119.6 |
C10—C2—C3 | 106.72 (12) | C11—C12—C13 | 120.16 (15) |
C7—C2—C3 | 109.30 (13) | C11—C12—H12 | 119.9 |
C10—C2—C1 | 108.18 (13) | C13—C12—H12 | 119.9 |
C7—C2—C1 | 114.51 (13) | O3—C13—C14 | 124.10 (15) |
C3—C2—C1 | 109.38 (13) | O3—C13—C12 | 115.89 (15) |
C13—O3—C16 | 117.10 (13) | C14—C13—C12 | 120.01 (15) |
O1—C3—C4 | 122.46 (16) | C13—C14—C15 | 119.14 (16) |
O1—C3—C2 | 120.70 (16) | C13—C14—H14 | 120.4 |
C4—C3—C2 | 116.77 (14) | C15—C14—H14 | 120.4 |
C20—O4—C23 | 116.90 (14) | C10—C15—C14 | 121.72 (15) |
C3—C4—C5 | 112.22 (14) | C10—C15—H15 | 119.1 |
C3—C4—H4A | 109.2 | C14—C15—H15 | 119.1 |
C5—C4—H4A | 109.2 | O3—C16—H16A | 109.5 |
C3—C4—H4B | 109.2 | O3—C16—H16B | 109.5 |
C5—C4—H4B | 109.2 | H16A—C16—H16B | 109.5 |
H4A—C4—H4B | 107.9 | O3—C16—H16C | 109.5 |
C8—C5—C9 | 109.80 (15) | H16A—C16—H16C | 109.5 |
C8—C5—C6 | 110.31 (14) | H16B—C16—H16C | 109.5 |
C9—C5—C6 | 109.66 (14) | C22—C17—C18 | 117.57 (17) |
C8—C5—C4 | 109.52 (14) | C22—C17—C1 | 117.99 (15) |
C9—C5—C4 | 109.41 (14) | C18—C17—C1 | 124.43 (16) |
C6—C5—C4 | 108.10 (14) | C19—C18—C17 | 120.98 (17) |
C7—C6—C5 | 112.54 (14) | C19—C18—H18 | 119.5 |
C7—C6—H6A | 109.1 | C17—C18—H18 | 119.5 |
C5—C6—H6A | 109.1 | C18—C19—C20 | 120.32 (16) |
C7—C6—H6B | 109.1 | C18—C19—H19 | 119.8 |
C5—C6—H6B | 109.1 | C20—C19—H19 | 119.8 |
H6A—C6—H6B | 107.8 | O4—C20—C21 | 124.02 (16) |
O2—C7—C6 | 122.10 (15) | O4—C20—C19 | 116.11 (15) |
O2—C7—C2 | 121.26 (15) | C21—C20—C19 | 119.87 (17) |
C6—C7—C2 | 116.65 (14) | C20—C21—C22 | 119.17 (16) |
C5—C8—H8A | 109.5 | C20—C21—H21 | 120.4 |
C5—C8—H8B | 109.5 | C22—C21—H21 | 120.4 |
H8A—C8—H8B | 109.5 | C17—C22—C21 | 122.05 (16) |
C5—C8—H8C | 109.5 | C17—C22—H22 | 119.0 |
H8A—C8—H8C | 109.5 | C21—C22—H22 | 119.0 |
H8B—C8—H8C | 109.5 | O4—C23—H23A | 109.5 |
C5—C9—H9A | 109.5 | O4—C23—H23B | 109.5 |
C5—C9—H9B | 109.5 | H23A—C23—H23B | 109.5 |
H9A—C9—H9B | 109.5 | O4—C23—H23C | 109.5 |
C5—C9—H9C | 109.5 | H23A—C23—H23C | 109.5 |
H9A—C9—H9C | 109.5 | H23B—C23—H23C | 109.5 |
C17—C1—C2—C10 | 46.58 (18) | C7—C2—C10—C11 | −154.85 (15) |
Cl1—C1—C2—C10 | 175.35 (11) | C3—C2—C10—C11 | −37.2 (2) |
C17—C1—C2—C7 | −74.47 (19) | C1—C2—C10—C11 | 80.41 (18) |
Cl1—C1—C2—C7 | 54.29 (16) | C15—C10—C11—C12 | −0.8 (2) |
C17—C1—C2—C3 | 162.47 (14) | C2—C10—C11—C12 | −175.36 (16) |
Cl1—C1—C2—C3 | −68.77 (14) | C10—C11—C12—C13 | 0.4 (3) |
C10—C2—C3—O1 | 102.75 (17) | C16—O3—C13—C14 | 5.3 (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—C14 | 0.3 (3) |
C7—C2—C3—C4 | 42.94 (18) | O3—C13—C14—C15 | 179.02 (15) |
C1—C2—C3—C4 | 169.04 (13) | C12—C13—C14—C15 | −0.6 (2) |
O1—C3—C4—C5 | 130.01 (17) | C11—C10—C15—C14 | 0.5 (2) |
C2—C3—C4—C5 | −53.14 (19) | C2—C10—C15—C14 | 175.01 (15) |
C3—C4—C5—C8 | −62.80 (19) | C13—C14—C15—C10 | 0.2 (3) |
C3—C4—C5—C9 | 176.80 (15) | C2—C1—C17—C22 | −92.21 (19) |
C3—C4—C5—C6 | 57.43 (18) | Cl1—C1—C17—C22 | 139.97 (14) |
C8—C5—C6—C7 | 62.78 (18) | C2—C1—C17—C18 | 87.3 (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—C19 | 1.4 (3) |
C5—C6—C7—O2 | −128.13 (17) | C1—C17—C18—C19 | −178.16 (16) |
C5—C6—C7—C2 | 52.09 (19) | C17—C18—C19—C20 | 0.1 (3) |
C10—C2—C7—O2 | −106.02 (17) | C23—O4—C20—C21 | −3.9 (2) |
C3—C2—C7—O2 | 137.99 (16) | C23—O4—C20—C19 | 175.34 (16) |
C1—C2—C7—O2 | 14.9 (2) | C18—C19—C20—O4 | 179.10 (16) |
C10—C2—C7—C6 | 73.77 (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—C22 | 1.7 (3) |
C7—C2—C10—C15 | 30.8 (2) | C18—C17—C22—C21 | −1.4 (3) |
C3—C2—C10—C15 | 148.44 (15) | C1—C17—C22—C21 | 178.20 (16) |
C1—C2—C10—C15 | −93.96 (18) | C20—C21—C22—C17 | −0.1 (3) |
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−1/2, y+1/2, −z+1/2; (ii) −x, −y+2, −z+1; (iii) x−1, y, z. |
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−1/2, y+1/2, −z+1/2; (ii) −x, −y+2, −z+1; (iii) x−1, y, z. |
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) |
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, 1.02 |
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), 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.
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