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

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1 research communications ISSN Crystal structure of 2-[chloro(4-methoxyphenyl)- methyl]-2-(4-methoxyphenyl)-5,5-dimethylcyclohexane-1,3-dione Saloua Chelli, Konstantin Troshin, Sami Lakhdar, Herbert Mayr and Peter Mayer* Received 25 January 2016 Accepted 3 February 2016 Edited by C. Rizzoli, Universita degli Studi di Parma, Italy Keywords: crystal structure; weak C HO and C HCl interactions. Department Chemie und Biochemie, Ludwig-Maximilians-Universität, Butenandtstrasse 513, D München, Germany. *Correspondence pemay@cup.uni-muenchen.de In the title compound, C 23 H 25 ClO 4, 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 HO contacts and strands along [100] and [010] established by further C HO and C HCl contacts, respectively. CCDC reference: Supporting information: this article has at journals.iucr.org/e 1. Chemical context 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. 2. 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 = (19) Å and = (2) (Boeyens, 1978; Cremer & Pople, 1975). The maximum deviation from the mean plane is (2) Å for atom C5. The 4-methoxyphenyl substituent is Acta Cryst. (2016). E72,

2 research communications Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA C8 H8CCl1 i (2) 159 C14 H14O2 ii (2) 153 C19 H19O3 iii (2) 161 Symmetry codes: (i) x 1 2 ; y þ 1 2 ; z þ 1 2 ; (ii) x; y þ 2; z þ 1; (iii) x 1; y; z. 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 (2) and (2) Å, respectively, and hence are almost coplanar with them. The two benzene rings are inclined to one another by (6) and to the mean plane of the cyclohexane ring by (9) and (8), respectively. Figure 3 A view of the strands along [010] formed by weak C HCl contacts (orange dotted lines). 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 HO and C HCl contacts (Table 1), while -stacking and C H interactions are not present. Pairs of contacts of the type C14 H14O2 between the benzene ring and a ketogroup lead to the formation of inversion dimers with an R 2 2(14) ring motif (Fig. 2). Strands along [010] are established by weak C8 H8CCl1 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 H19O3 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 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. Figure 2 A view of the inversion dimer formed by a pair of weak C HO contacts (blue dotted lines). Acta Cryst. (2016). E72, Chelli et al. C 23 H 25 ClO 4 301

3 research communications Figure 5 Packing diagram of the title compound viewed along [010]. For clarity, all the weak interactions have been omitted. 5. Synthesis and crystallization Zinc chloride (114.2 mg, 699 mmol), tetrabutylammonium chloride (190.2 mg, 684 mmol), 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 0 -dimethoxybenzhydryl chloride (417.2 mg, 1.59 mmol) in dichloromethane (4 ml) was Table 2 Experimental details. Figure 4 A view along [010] of the strands along [100] formed by weak C HO contacts (green dotted lines). 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). Crystal data Chemical formula C 23 H 25 ClO 4 M r Crystal system, space group Monoclinic, P2 1 /n Temperature (K) 100 a, b, c (Å) (5), (6), (12) ( ) (6) V (Å 3 ) (2) Z 4 Radiation type Mo K (mm 1 ) 0.21 Crystal size (mm) Data collection Diffractometer Oxford Diffraction XCalibur3 Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2014) T min, T max 0.982, No. of measured, independent and 11293, 4283, 3355 observed [I > 2(I)] reflections R int (sin /) max (Å 1 ) Refinement R[F 2 >2(F 2 )], wr(f 2 ), S 0.040, 0.102, 1.03 No. of reflections 4283 No. of parameters 257 H-atom treatment H-atom parameters constrained max, min (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) and PLATON (Spek, 2009). 302 Chelli et al. C 23 H 25 ClO 4 Acta Cryst. (2016). E72,

4 research communications 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 (MgSO 4 ), 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 mmol; yield 62%). 6. Refinement Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were positioned geometrically (C H = 0.98 Å for methyl-h, 0.99 Å for C H 2,1.00Åfor aliphatic C H, 0.95 Å for aromatic H) and treated as riding on their parent atoms, with U iso (H) = 1.2U eq (C) or 1.5U eq (C) for methyl H atoms. The methyl groups were allowed to rotate along the C C bonds to best fit the experimental electron density. Acknowledgements The authors thank Professor Thomas M. Klapötke for generous allocation of diffractometer time. References Adam, W., Gogonas, E. P. & Hadjiarapoglou, L. P. (2003). Tetrahedron, 59, Agilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England. 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, Batsila, C., Gogonas, E. P., Kostakis, G. & Hadjiarapoglou, L. P. (2003). Org. Lett. 5, Betz, R., McCleland, C. & Hosten, E. (2011). Acta Cryst. E67, o1199. Boeyens, J. C. A. (1978). J. Cryst. Mol. Struct. 8, Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL Oak Ridge National Laboratory, Tennessee, USA. Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, Goudreau, S. R., Marcoux, D. & Charette, A. B. (2009). J. Org. Chem. 74, Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, Hadjiarapoglou, L. & Varvoglis, A. (1988). Synthesis, pp Kalyani, D., Satterfield, A. D. & Sanford, M. S. (2010). J. Am. Chem. Soc. 132, Lee, Y. R. & Jung, Y. U. (2002). J. Chem. Soc. Perkin Trans. 1, pp Moriarty, R. M., Tyagi, S., Ivanov, D. & Constantinescu, M. (2008). J. Am. Chem. Soc. 130, Nair, R. P., Pineda-Lanorio, J. A. & Frost, B. J. (2012). Inorg. Chim. Acta, 380, Noordik, J. H. & Cillissen, P. J. M. (1981). Cryst. Struct. Commun. 10, Ochiai, M., Kunishima, M., Nagao, Y., Fuji, K., Shiro, M. & Fujita, E. (1986). J. Am. Chem. Soc. 108, Roques, R., Guy, E. & Fourme, R. (1976). Acta Cryst. B32, Sheldrick, G. M. (2015). Acta Cryst. C71, 3 8. Sparr, C. & Gilmour, R. (2011). Angew. Chem. Int. Ed. 50, Spek, A. L. (2009). Acta Cryst. D65, Unruh, S., Karapetyan, G., Vogel, C. & Reinke, H. (2008). Private communication. Zhdankin, V. V. & Stang, P. J. (2008). Chem. Rev. 108, Acta Cryst. (2016). E72, Chelli et al. C 23 H 25 ClO 4 303

5 [doi: /s ] Crystal structure of 2-[chloro(4-methoxyphenyl)methyl]-2-(4-methoxyphenyl)-5,5-dimethylcyclohexane-1,3-dione Saloua Chelli, Konstantin Troshin, Sami Lakhdar, Herbert Mayr and Peter Mayer Computing details 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). 2-[Chloro(4-methoxyphenyl)methyl]-2-(4-methoxyphenyl)-5,5-dimethylcyclohexane-1,3-dione Crystal data C 23 H 25 ClO 4 M r = Monoclinic, P2 1 /n a = (5) Å b = (6) Å c = (12) Å β = (6) V = (2) Å 3 Z = 4 Data collection Oxford Diffraction XCalibur3 diffractometer Radiation source: fine-focus sealed tube Detector resolution: pixels mm -1 ω scans Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) T min = 0.982, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 257 parameters 0 restraints F(000) = 848 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 3451 reflections θ = µ = 0.21 mm 1 T = 100 K Block, colourless mm measured reflections 4283 independent reflections 3355 reflections with I > 2σ(I) R int = θ max = 26.4, θ min = 4.2 h = 12 9 k = l = Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0382P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.27 e Å 3 Δρ min = 0.30 e Å 3 sup-1

6 Special details 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 (Å 2 ) x y z U iso */U eq Cl (4) (4) (3) (14) O (13) (11) (7) (3) C (17) (15) (9) (4) H * O (12) (11) (6) (3) C (16) (14) (9) (4) O (12) (11) (6) (3) C (16) (16) (9) (4) O (12) (12) (7) (3) C (17) (17) (10) (4) H4A * H4B * C (17) (15) (9) (4) C (17) (15) (9) (4) H6A * H6B * C (16) (15) (9) (3) C (18) (17) (10) (4) H8A * H8B * H8C * C (2) (18) (10) (5) H9A * H9B * H9C * C (16) (15) (9) (3) C (17) (15) (9) (4) H * C (17) (15) (9) (4) H * C (16) (15) (9) (4) C (17) (15) (9) (4) H * C (17) (15) (9) (4) H * C (18) (17) (10) (4) H16A * sup-2

7 H16B * H16C * C (16) (15) (9) (4) C (17) (16) (10) (4) H * C (18) (17) (10) (4) H * C (17) (15) (10) (4) C (17) (15) (10) (4) H * C (17) (15) (10) (4) H * C (19) (18) (10) (4) H23A * H23B * H23C * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Cl (2) (2) (3) (17) (18) (2) O (7) (7) (7) (5) (5) (6) C (8) (9) (10) (6) (7) (7) O (6) (7) (7) (5) (5) (5) C (8) (8) (9) (6) (7) (7) O (6) (7) (7) (5) (5) (5) C (8) (9) (9) (7) (7) (8) O (7) (8) (7) (5) (5) (6) C (9) (10) (9) (7) (7) (8) C (9) (9) (9) (7) (7) (7) C (9) (9) (9) (7) (7) (7) C (8) (8) (8) (7) (6) (7) C (10) (10) (10) (7) (7) (8) C (11) (11) (11) (8) (8) (9) C (8) (8) (8) (6) (6) (7) C (9) (9) (9) (7) (7) (7) C (8) (9) (9) (7) (7) (8) C (8) (9) (8) (7) (6) (7) C (9) (8) (9) (7) (7) (7) C (8) (9) (9) (7) (7) (7) C (10) (10) (9) (8) (7) (8) C (8) (8) (10) (7) (7) (7) C (9) (10) (10) (7) (7) (8) C (9) (10) (11) (7) (8) (9) C (9) (9) (10) (7) (7) (8) C (9) (9) (10) (7) (7) (8) C (8) (9) (10) (7) (7) (8) C (10) (11) (10) (8) (8) (9) sup-3

8 Geometric parameters (Å, º) Cl1 C (17) C9 H9C O1 C (2) C10 C (2) C1 C (2) C10 C (2) C1 C (2) C11 C (2) C1 H C11 H O2 C (2) C12 C (2) C2 C (2) C12 H C2 C (2) C13 C (2) C2 C (2) C14 C (2) O3 C (19) C14 H O3 C (2) C15 H C3 C (3) C16 H16A O4 C (2) C16 H16B O4 C (2) C16 H16C C4 C (2) C17 C (2) C4 H4A C17 C (2) C4 H4B C18 C (3) C5 C (2) C18 H C5 C (2) C19 C (3) C5 C (2) C19 H C6 C (2) C20 C (2) C6 H6A C21 C (2) C6 H6B C21 H C8 H8A C22 H C8 H8B C23 H23A C8 H8C C23 H23B C9 H9A C23 H23C C9 H9B C17 C1 C (14) H9B C9 H9C C17 C1 Cl (12) C15 C10 C (15) C2 C1 Cl (11) C15 C10 C (14) C17 C1 H C11 C10 C (15) C2 C1 H C12 C11 C (16) Cl1 C1 H C12 C11 H C10 C2 C (13) C10 C11 H C10 C2 C (12) C11 C12 C (15) C7 C2 C (13) C11 C12 H C10 C2 C (13) C13 C12 H C7 C2 C (13) O3 C13 C (15) C3 C2 C (13) O3 C13 C (15) C13 O3 C (13) C14 C13 C (15) O1 C3 C (16) C13 C14 C (16) O1 C3 C (16) C13 C14 H C4 C3 C (14) C15 C14 H C20 O4 C (14) C10 C15 C (15) sup-4

9 C3 C4 C (14) C10 C15 H C3 C4 H4A C14 C15 H C5 C4 H4A O3 C16 H16A C3 C4 H4B O3 C16 H16B C5 C4 H4B H16A C16 H16B H4A C4 H4B O3 C16 H16C C8 C5 C (15) H16A C16 H16C C8 C5 C (14) H16B C16 H16C C9 C5 C (14) C22 C17 C (17) C8 C5 C (14) C22 C17 C (15) C9 C5 C (14) C18 C17 C (16) C6 C5 C (14) C19 C18 C (17) C7 C6 C (14) C19 C18 H C7 C6 H6A C17 C18 H C5 C6 H6A C18 C19 C (16) C7 C6 H6B C18 C19 H C5 C6 H6B C20 C19 H H6A C6 H6B O4 C20 C (16) O2 C7 C (15) O4 C20 C (15) O2 C7 C (15) C21 C20 C (17) C6 C7 C (14) C20 C21 C (16) C5 C8 H8A C20 C21 H C5 C8 H8B C22 C21 H H8A C8 H8B C17 C22 C (16) C5 C8 H8C C17 C22 H H8A C8 H8C C21 C22 H H8B C8 H8C O4 C23 H23A C5 C9 H9A O4 C23 H23B C5 C9 H9B H23A C23 H23B H9A C9 H9B O4 C23 H23C C5 C9 H9C H23A C23 H23C H9A C9 H9C H23B C23 H23C C17 C1 C2 C (18) C7 C2 C10 C (15) Cl1 C1 C2 C (11) C3 C2 C10 C (2) C17 C1 C2 C (19) C1 C2 C10 C (18) Cl1 C1 C2 C (16) C15 C10 C11 C (2) C17 C1 C2 C (14) C2 C10 C11 C (16) Cl1 C1 C2 C (14) C10 C11 C12 C (3) C10 C2 C3 O (17) C16 O3 C13 C (2) C7 C2 C3 O (16) C16 O3 C13 C (15) C1 C2 C3 O (2) C11 C12 C13 O (15) C10 C2 C3 C (17) C11 C12 C13 C (3) C7 C2 C3 C (18) O3 C13 C14 C (15) C1 C2 C3 C (13) C12 C13 C14 C (2) O1 C3 C4 C (17) C11 C10 C15 C (2) C2 C3 C4 C (19) C2 C10 C15 C (15) C3 C4 C5 C (19) C13 C14 C15 C (3) sup-5

10 C3 C4 C5 C (15) C2 C1 C17 C (19) C3 C4 C5 C (18) Cl1 C1 C17 C (14) C8 C5 C6 C (18) C2 C1 C17 C (2) C9 C5 C6 C (14) Cl1 C1 C17 C (2) C4 C5 C6 C (18) C22 C17 C18 C (3) C5 C6 C7 O (17) C1 C17 C18 C (16) C5 C6 C7 C (19) C17 C18 C19 C (3) C10 C2 C7 O (17) C23 O4 C20 C (2) C3 C2 C7 O (16) C23 O4 C20 C (16) C1 C2 C7 O (2) C18 C19 C20 O (16) C10 C2 C7 C (18) C18 C19 C20 C (3) C3 C2 C7 C (19) O4 C20 C21 C (16) C1 C2 C7 C (14) C19 C20 C21 C (3) C7 C2 C10 C (2) C18 C17 C22 C (3) C3 C2 C10 C (15) C1 C17 C22 C (16) C1 C2 C10 C (18) C20 C21 C22 C (3) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A C8 H8C Cl1 i (2) 159 C14 H14 O2 ii (2) 153 C19 H19 O3 iii (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. sup-6