Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616001972/fn3214sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616001972/fn3214Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229616001972/fn3214sup3.pdf |
CCDC reference: 1451252
\ Single-crystal X-ray structural analysis is a definitive analytical technique that, in an `ideal world', requires no prior information about the source or nature of the compound under investigation. For example, Mueller et al. (2006) used X-ray diffraction to establish the structure of an adventitious rhenium(V) complex Re2(Cp*)2O2(µ2-O)21 (Cp* is pentamethylcyclopentadienyl), whose source proved impossible to determine. A crystalline lilac deposit from a swimming pool was determined to be disodium copper(II) tetrakis(isocyanurate) hexahydrate [Na2Cu(C3H2N3O3)4·6H2O; Hart et al., 1992] and subsequently purposefully synthesized (Falvello et al., 1997). Such examples are rare and, in practice, the crystallographer usually possesses information about the nature of the crystals as well as the synthons and solvents used during the chemical reaction and crystallization. When the structural solution reveals a compound different from the proposed one, typically a large portion of the structure contains correctly assigned elements at the correct positions. The much smaller `unknown' part of the structure is usually the cocrystallized solvent or counter-ion, whose nature and conformation are routinely deduced from the difference Fourier syntheses. Two interesting cases of structural analyses that had established the atomic connectivity in compounds of known origin include the bis(2,3-dihydro-1,3-diborole) complex [(EtC)2(EtB)2CHMe]2Pt, that took nearly 30 years to produce dark-red single crystals (Wadepohl et al., 2015), and an indazalone, that, in the absence of a crystal structure, was believed to be a 2,1-benzisoxazole (Kurth et al., 2005).
With the advent of programs such as Shake-and-Bake (Miller et al., 1994), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXD (Sheldrick, 2010), and SHELXT (Sheldrick, 2015a) that solve structures by performing Fourier transforms in the direct and reciprocal space, prior knowledge of the exact crystal composition has become optional (Feng, 2011). Ab initio structure solution by charge flipping requires no chemical or phase information (Oszlányi & Süto, 2004) and is well suited for ordered, disordered, and modulated structures. The dual-space recycling program SHELXT (Sheldrick, 2015a) takes advantage of the atomistic nature of ordered structures, utilizes the information about the nature of the chemical elements present, and introduces additional elements as necessary. It should be noted that a successful solution of a structure by either of these programs is not a substitute for elemental chemical analysis. Previously, we have had good success with the program SHELXT and were confident that the crystals of the inclusion compound (IV) = (I)·0.85(II)·0.15(III) could be crystallographically characterized (see Scheme). It was believed to be a hydrocarbon, but its origin, formula, and method of crystallization were and still remain unknown. Herein we report the structural and chemical characterization of (4R,5R)-4,5-bis(hydroxydiphenylmethyl)-2,2-dimethyl-1,3-\ dioxolane–4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one–4a-\ (hydroperoxymethyl)-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one (1/0.85/0.15), (IV), and propose an explanation for its appearance in the laboratory
1 Mueller et al. (2006) referenced a related ReV complex [(η5-C5Me5)Re(O)(µ2-O)]2·H2O, [(VII)·H2O] (Herrmann et al., 1988), in their pursuit to establish the metal identity of their Re2(η5-C5Me5)2O2(µ2-O)2 complex, (VII). The compositional difference between these two complexes is only the presence of a solvent water molecule in (VII)·H2O that connects the Re complexes into a one-dimensional chain. Yet an air-stable (VII) and `very oxygen-sensitive' (VII)·H2O have very different electronic structures and geometries. It is interesting to contrast several geometrical parameters in these complexes; the following parameters are reported pairwise for (VII) and (VII)·H2O: Re···Re separation = 2.724 and 3.14 Å; distance between the bridging O atoms = 3.025 and 2.34 Å; Re—centroid(η5-C5Me5) = 2.059 and 1.97 Å; Re—O(bridging) = 2.004 and 1.96 Å; Re═O = 1.714 and 1.70 Å. Thus, there is a metal–metal bond in (VII), whereas there appears to be no Re—Re bond in (VII)·H2O. These facts illustrate how difficult establishing the correct composition and structure might be. A density-functional theory (DFT) study of these systems is underway.
Clear colourless high-quality large centimetre-long parallelepiped-shaped crystals had been stored under air in an Erlenmeyer flask for over 10 years with no visible deterioration. No information about either their synthesis or crystallization was available, when a representative crystal was selected for a single-crystal X-ray structural characterization for the purpose of training a teaching assistant. The crystal composition was initially established crystallographyically and subsequently found to be consistent with its being a cocrystal of the TADDOL (α,α,α',α'-tetraaryl-2,2-disubstituted 1,3-dioxolane-4,5-dimethanol) host 4,5-bis(hydroxydiphenylmethyl)-2,2-dimethyl-1,3-dioxolane, (I), with 85.1 (4)% of 4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one, (II), and 14.9 (4)% of 4a-(hydroperoxymethyl)-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one, (III). It was not possible to identify the student who submitted the crystals; therefore, we can only speculate about their preparation.
TADDOL, (I), is a common chiral catalyst (Seeback et al., 2001) that could have been used in a chiral synthesis leading to the formation of the enone (II), possibly by Robinson annulation or another route. There also is a distinct possibility that the chiral (I) was used as a host cocrystallant for (II), which is an oil, in order to establish its absolute configuration in an undergraduate organic laboratory. An autoxidation of the weak C—H bond at the only chiral center (C32) of enone (II) with ambient air is believed to yield the organic hydroperoxide (III) that subsequently cocrystallized with (I) and (II) as a minor component. The autoxidation is presumed to have taken place in solution rather than in the solid state. Several data sets on different crystals of (IV) were acquired to confirm that their (II):(III) ratio remains invariant within experimental error. It is noteworthy that all the compounds were stable in the solid state, but the organic hydroperoxide, (III), once isolated as a waxy solid, degraded into a brown oil within days in air. If (I) was not used to physically separate enantiomers of (II), another possibility is that the crystals formed serendipitously in the flask used for an organic synthetic procedure and were brought to the laboratory because of their beauty and size, rather than their importance.
After the crystallographic characterization of (IV), we separated the compounds by physical means and chemically analyzed the pure compounds to further support the identity of each component. About 150 mg of a crystalline sample was subjected to flash-column chromatography on silica gel with a hexanes–ethyl acetate gradient (10% ethyl acetate to 30% ethyl acetate). The separated compounds (I)–(III) were analyzed by 1H and 13C NMR spectroscopy and high-resolution mass spectrometry. The bulk crystalline sample was also analyzed by X-ray fluorescence and the chemical composition of the crystals of solely C, H, and O was supported. The signal at 80.39 p.p.m. in the 13C NMR spectrum of impurity (III) is indicative of a C atom bound to an electronegative atom such as oxygen (atom C32). The broad singlet at 7.52 p.p.m. in the 1H NMR spectrum is due to the hydroxy H atom. The olefinic C—H signal is shifted downfield to 5.94 p.p.m., whereas the C—H signal of enone (II) is observed at 5.82 p.p.m. (See Supporting information for details of the X-ray fluorescence measurements, and NMR and MS data.)
Crystal data, data collection and structure refinement details are summarized in Table 1. There are three chemical moieties in the asymmetric unit. At one site, there is a fully occupied TADDOL host 4,5-bis(hydroxydiphenylmethyl)-2,2-dimethyl-1,3-dioxolane, (I). At the other site, there is compositional disorder between guest 4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one, (II), present 85.1 (4)% of the time, and impurity 4a-(hydroperoxymethyl)-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one, (III), observed 14.9 (4)% of the time. Most of the atoms in compounds (II) and (III) have the same coordinates; thus (II) and (III) differ only in the position of one CH2—CH2 link and the presence of the hydroperoxy group. Soft distance and thermal displacement parameter restraints were applied to the disordered part of the structure in order to achieve a chemically reasonable and computationally stable refinement.
The original goal of this work was to establish the crystal structure of an unknown, that proved to be compound (IV) (see Scheme), on the basis of X-ray diffraction data alone, as no prior chemical information was available. Due to the high quality of the data, this task proved to be straightforward; compounds (I) and (II) were readily identified and refined. However, two small peaks of electron density (ca 1.02 e Å−3) in the difference Fourier map in the vicinity of chiral center C32 in (II) (Fig. 1) suggested the presence of an additional species. These two peaks were tentatively assigned to be C atoms, and their presumed site occupancy was allowed to refine in the next series of least-squares cycles; the site-occupancy factor refined to ~0.20. Refinement with soft thermal displacement parameter restraints on the minor-disorder component was computationally stable; however, the C—C distance of 1.26 (2) Å was too short for a Csp3—Csp3 bond and the origin of this compound was hard to ascertain. An alternative refinement with an ethylene group in place of the ethyl group resulted in a C—C distance of 1.363 (18) Å and an occupancy factor of ~0.21. Neither model was chemically satisfactory. Both models required thermal displacement parameter restraints. An alternative structural model (III) (Fig. 2) involved a hydroperoxy group that has the same number of electrons as an ethyl group and whose formation could be explained via autoxidation of (II). A refinement of this presumed structure of (III) as the minor-crystal-disordered component proceeded smoothly to yield the final structure presented herein. No restraints were required for the hydroperoxy group. The refined O—O distance of 1.453 (17) Å in (III) is in good agreement with the average CO—OH distance of 1.463 (7) Å obtained by averaging the 101 distances in 82 structures of organic hydroperoxides listed in the Cambridge Structural Database (CSD, Version 5.36, updated May 2015; Groom & Allen, 2014); it falls well within the range of 1.447–1.463 Å. The C32—O6 distance to the hydroperoxy group of 1.560 (11) Å is substantially longer than the average C—O(O) bond of 1.429 (18) Å in 82 related structures, and the difference is statistically significant. Nevertheless, chemical analyses confirmed that the hydroperoxide (III) is the correct compound, and due to its low site occupancy (Fig. 3), the C32—O6 distance was considered to be acceptable and thereby refined without a restraint.
The C32—O6 bond direction in (III) is different from that of the C32—H32 bond in (II); the O6—C32—H32 angle is 24.5 (5)°. This implies an additional positional disorder of atoms C40 and C41, without which the tetrahedral geometry of atom C32 in (III) would have been excessively distorted. Indeed, the prolate displacement ellipsoids of atoms C40 and C41, and two small peaks of electron density (ca 0.5 e Å−3) in their vicinity substantiated this reasoning. The positional disorder of the C40—C41 link over two positions in an 85:15 ratio was refined with distance and anisotropic displacement parameter restraints.
Comparisons of the structure of (IV) with those of previously reported inclusion complexes of (I) will be restricted to two closely related complexes, namely (I):[(R)-6-methylbicyclo[4.4.0]dec-1-ene-3-one], (V), and (I):[(R)-6-methylbicyclo[4.4.0]dec-1-ene-3,7-dione], (VI) (Nassimbeni et al., 1991), that are isomorphous with each other and with (IV).
There are several hydrogen-bonding interactions of the O—H···O type in the crystal of (IV) (Table 2). In the major host–guest pair, i.e. (I):(II), there are strong host–host O3—H3···O4 [type S(7) [add reference for graph-set notation?]] and host–guest O4—H4···O5i [type D(2)] hydrogen bonds. The corresponding values in (V) are very similar to those in (VI), i.e. 2.676 (6)/171° and 2.687 Å/176°, versus 2.661 (6) Å/n/a (the hydroxy H atom is missing in the structure deposited to the CSD) and 2.694 Å/160°. When (III) is present as the guest, an additional host–guest hydrogen-bonding interaction, O7—H7···O3 [type D(2)], is formed. It should be noted that the position of atom H7 is less than 2.1 Å away from atom H3 and the H3—O3···H7 angle has an acute value of 78.4°, suggesting a suboptimal steric interaction between atoms H3 and H7. The positional parameters of H7 are considered to be acceptable due to the absence of hydrogen-bond acceptors other than atom O7 in the vicinity of atom O3.
The absolute configuration of the chiral centres C2, C3, and C32 was unambiguously established via anomalous dispersion effects as R. Whereas the Friedif value (Flack & Shmueli, 2007) that quantifies the magnitude of the resonant scattering effect for the crystal structure of (IV) is only 28.5, the Flack x = −0.01 (4) and Hooft y = 0.00 (5) parameters are quite conclusive. Had the synthesis of (II) and (III) been intentional, cocrystallization of (II) or (III) with (I) would have been proven to be a good means of optical resolution of the racemic mixture of (II) and its enantiomer, given the fact that (II) is an oil and (III) is a hard-to-crystallize solid under ambient conditions. The Friedif value for (I), computed as 28.4 is substantially lower than ~80, which is recommended for reliable elucidation of absolute structures (Flack & Bernardinelli, 2008); however, as our results illustrate, this value may be sufficient with high-quality low-temperature data sets.
We believe that the presence of (I) in the crystals of (IV) points to an intentional chiral crystallization of (II), due to the wide use of TADDOLs for such purposes (Seeback et al., 2001). TADDOL (I) has been widely utilized for optical resolution of chiral organic molecules because of its rigid structure and propensity to form hydrogen-bonding interactions (Nassimbeni et al., 1991; Seeback et al., 2001); to date, 42 host–guest structures with (I) as the host have been reported to the CSD. The enantiomeric selectivity of (I) depends on its conformation and the size of the lattice voids accommodating the guest molecules (Báthori & Nassimbeni, 2010). The light-stable compound (I) has been utilized as the host in crystals with the light-sensitive guest tropolone methyl ether (Lavy et al., 2004), and with a number of other compounds, such as ether, enones, pyrazole, pyridine, pyran, and furan derivatives (Groom & Allen, 2014). Additionally, diol (I) was structurally characterized in 1990 (Goldberg et al., 1990) and with a number of typical solvents, such as acetone, dimethylformamide, CCl4, and alcohols (Groom & Allen, 2014).
The structural study reported herein can be summarized as follows: the crystal structure of (IV) was solved ab initio, the compositional disorder was modeled crystallographically, the composition of (II) and (III) was substantiated by additional analytical techniques, and a plausible source of the crystals and the synthetic procedure were proposed with a high degree of confidence.
\ Single-crystal X-ray structural analysis is a definitive analytical technique that, in an `ideal world', requires no prior information about the source or nature of the compound under investigation. For example, Mueller et al. (2006) used X-ray diffraction to establish the structure of an adventitious rhenium(V) complex Re2(Cp*)2O2(µ2-O)21 (Cp* is pentamethylcyclopentadienyl), whose source proved impossible to determine. A crystalline lilac deposit from a swimming pool was determined to be disodium copper(II) tetrakis(isocyanurate) hexahydrate [Na2Cu(C3H2N3O3)4·6H2O; Hart et al., 1992] and subsequently purposefully synthesized (Falvello et al., 1997). Such examples are rare and, in practice, the crystallographer usually possesses information about the nature of the crystals as well as the synthons and solvents used during the chemical reaction and crystallization. When the structural solution reveals a compound different from the proposed one, typically a large portion of the structure contains correctly assigned elements at the correct positions. The much smaller `unknown' part of the structure is usually the cocrystallized solvent or counter-ion, whose nature and conformation are routinely deduced from the difference Fourier syntheses. Two interesting cases of structural analyses that had established the atomic connectivity in compounds of known origin include the bis(2,3-dihydro-1,3-diborole) complex [(EtC)2(EtB)2CHMe]2Pt, that took nearly 30 years to produce dark-red single crystals (Wadepohl et al., 2015), and an indazalone, that, in the absence of a crystal structure, was believed to be a 2,1-benzisoxazole (Kurth et al., 2005).
With the advent of programs such as Shake-and-Bake (Miller et al., 1994), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXD (Sheldrick, 2010), and SHELXT (Sheldrick, 2015a) that solve structures by performing Fourier transforms in the direct and reciprocal space, prior knowledge of the exact crystal composition has become optional (Feng, 2011). Ab initio structure solution by charge flipping requires no chemical or phase information (Oszlányi & Süto, 2004) and is well suited for ordered, disordered, and modulated structures. The dual-space recycling program SHELXT (Sheldrick, 2015a) takes advantage of the atomistic nature of ordered structures, utilizes the information about the nature of the chemical elements present, and introduces additional elements as necessary. It should be noted that a successful solution of a structure by either of these programs is not a substitute for elemental chemical analysis. Previously, we have had good success with the program SHELXT and were confident that the crystals of the inclusion compound (IV) = (I)·0.85(II)·0.15(III) could be crystallographically characterized (see Scheme). It was believed to be a hydrocarbon, but its origin, formula, and method of crystallization were and still remain unknown. Herein we report the structural and chemical characterization of (4R,5R)-4,5-bis(hydroxydiphenylmethyl)-2,2-dimethyl-1,3-\ dioxolane–4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one–4a-\ (hydroperoxymethyl)-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one (1/0.85/0.15), (IV), and propose an explanation for its appearance in the laboratory
1 Mueller et al. (2006) referenced a related ReV complex [(η5-C5Me5)Re(O)(µ2-O)]2·H2O, [(VII)·H2O] (Herrmann et al., 1988), in their pursuit to establish the metal identity of their Re2(η5-C5Me5)2O2(µ2-O)2 complex, (VII). The compositional difference between these two complexes is only the presence of a solvent water molecule in (VII)·H2O that connects the Re complexes into a one-dimensional chain. Yet an air-stable (VII) and `very oxygen-sensitive' (VII)·H2O have very different electronic structures and geometries. It is interesting to contrast several geometrical parameters in these complexes; the following parameters are reported pairwise for (VII) and (VII)·H2O: Re···Re separation = 2.724 and 3.14 Å; distance between the bridging O atoms = 3.025 and 2.34 Å; Re—centroid(η5-C5Me5) = 2.059 and 1.97 Å; Re—O(bridging) = 2.004 and 1.96 Å; Re═O = 1.714 and 1.70 Å. Thus, there is a metal–metal bond in (VII), whereas there appears to be no Re—Re bond in (VII)·H2O. These facts illustrate how difficult establishing the correct composition and structure might be. A density-functional theory (DFT) study of these systems is underway.
After the crystallographic characterization of (IV), we separated the compounds by physical means and chemically analyzed the pure compounds to further support the identity of each component. About 150 mg of a crystalline sample was subjected to flash-column chromatography on silica gel with a hexanes–ethyl acetate gradient (10% ethyl acetate to 30% ethyl acetate). The separated compounds (I)–(III) were analyzed by 1H and 13C NMR spectroscopy and high-resolution mass spectrometry. The bulk crystalline sample was also analyzed by X-ray fluorescence and the chemical composition of the crystals of solely C, H, and O was supported. The signal at 80.39 p.p.m. in the 13C NMR spectrum of impurity (III) is indicative of a C atom bound to an electronegative atom such as oxygen (atom C32). The broad singlet at 7.52 p.p.m. in the 1H NMR spectrum is due to the hydroxy H atom. The olefinic C—H signal is shifted downfield to 5.94 p.p.m., whereas the C—H signal of enone (II) is observed at 5.82 p.p.m. (See Supporting information for details of the X-ray fluorescence measurements, and NMR and MS data.)
The original goal of this work was to establish the crystal structure of an unknown, that proved to be compound (IV) (see Scheme), on the basis of X-ray diffraction data alone, as no prior chemical information was available. Due to the high quality of the data, this task proved to be straightforward; compounds (I) and (II) were readily identified and refined. However, two small peaks of electron density (ca 1.02 e Å−3) in the difference Fourier map in the vicinity of chiral center C32 in (II) (Fig. 1) suggested the presence of an additional species. These two peaks were tentatively assigned to be C atoms, and their presumed site occupancy was allowed to refine in the next series of least-squares cycles; the site-occupancy factor refined to ~0.20. Refinement with soft thermal displacement parameter restraints on the minor-disorder component was computationally stable; however, the C—C distance of 1.26 (2) Å was too short for a Csp3—Csp3 bond and the origin of this compound was hard to ascertain. An alternative refinement with an ethylene group in place of the ethyl group resulted in a C—C distance of 1.363 (18) Å and an occupancy factor of ~0.21. Neither model was chemically satisfactory. Both models required thermal displacement parameter restraints. An alternative structural model (III) (Fig. 2) involved a hydroperoxy group that has the same number of electrons as an ethyl group and whose formation could be explained via autoxidation of (II). A refinement of this presumed structure of (III) as the minor-crystal-disordered component proceeded smoothly to yield the final structure presented herein. No restraints were required for the hydroperoxy group. The refined O—O distance of 1.453 (17) Å in (III) is in good agreement with the average CO—OH distance of 1.463 (7) Å obtained by averaging the 101 distances in 82 structures of organic hydroperoxides listed in the Cambridge Structural Database (CSD, Version 5.36, updated May 2015; Groom & Allen, 2014); it falls well within the range of 1.447–1.463 Å. The C32—O6 distance to the hydroperoxy group of 1.560 (11) Å is substantially longer than the average C—O(O) bond of 1.429 (18) Å in 82 related structures, and the difference is statistically significant. Nevertheless, chemical analyses confirmed that the hydroperoxide (III) is the correct compound, and due to its low site occupancy (Fig. 3), the C32—O6 distance was considered to be acceptable and thereby refined without a restraint.
The C32—O6 bond direction in (III) is different from that of the C32—H32 bond in (II); the O6—C32—H32 angle is 24.5 (5)°. This implies an additional positional disorder of atoms C40 and C41, without which the tetrahedral geometry of atom C32 in (III) would have been excessively distorted. Indeed, the prolate displacement ellipsoids of atoms C40 and C41, and two small peaks of electron density (ca 0.5 e Å−3) in their vicinity substantiated this reasoning. The positional disorder of the C40—C41 link over two positions in an 85:15 ratio was refined with distance and anisotropic displacement parameter restraints.
Comparisons of the structure of (IV) with those of previously reported inclusion complexes of (I) will be restricted to two closely related complexes, namely (I):[(R)-6-methylbicyclo[4.4.0]dec-1-ene-3-one], (V), and (I):[(R)-6-methylbicyclo[4.4.0]dec-1-ene-3,7-dione], (VI) (Nassimbeni et al., 1991), that are isomorphous with each other and with (IV).
There are several hydrogen-bonding interactions of the O—H···O type in the crystal of (IV) (Table 2). In the major host–guest pair, i.e. (I):(II), there are strong host–host O3—H3···O4 [type S(7) [add reference for graph-set notation?]] and host–guest O4—H4···O5i [type D(2)] hydrogen bonds. The corresponding values in (V) are very similar to those in (VI), i.e. 2.676 (6)/171° and 2.687 Å/176°, versus 2.661 (6) Å/n/a (the hydroxy H atom is missing in the structure deposited to the CSD) and 2.694 Å/160°. When (III) is present as the guest, an additional host–guest hydrogen-bonding interaction, O7—H7···O3 [type D(2)], is formed. It should be noted that the position of atom H7 is less than 2.1 Å away from atom H3 and the H3—O3···H7 angle has an acute value of 78.4°, suggesting a suboptimal steric interaction between atoms H3 and H7. The positional parameters of H7 are considered to be acceptable due to the absence of hydrogen-bond acceptors other than atom O7 in the vicinity of atom O3.
The absolute configuration of the chiral centres C2, C3, and C32 was unambiguously established via anomalous dispersion effects as R. Whereas the Friedif value (Flack & Shmueli, 2007) that quantifies the magnitude of the resonant scattering effect for the crystal structure of (IV) is only 28.5, the Flack x = −0.01 (4) and Hooft y = 0.00 (5) parameters are quite conclusive. Had the synthesis of (II) and (III) been intentional, cocrystallization of (II) or (III) with (I) would have been proven to be a good means of optical resolution of the racemic mixture of (II) and its enantiomer, given the fact that (II) is an oil and (III) is a hard-to-crystallize solid under ambient conditions. The Friedif value for (I), computed as 28.4 is substantially lower than ~80, which is recommended for reliable elucidation of absolute structures (Flack & Bernardinelli, 2008); however, as our results illustrate, this value may be sufficient with high-quality low-temperature data sets.
We believe that the presence of (I) in the crystals of (IV) points to an intentional chiral crystallization of (II), due to the wide use of TADDOLs for such purposes (Seeback et al., 2001). TADDOL (I) has been widely utilized for optical resolution of chiral organic molecules because of its rigid structure and propensity to form hydrogen-bonding interactions (Nassimbeni et al., 1991; Seeback et al., 2001); to date, 42 host–guest structures with (I) as the host have been reported to the CSD. The enantiomeric selectivity of (I) depends on its conformation and the size of the lattice voids accommodating the guest molecules (Báthori & Nassimbeni, 2010). The light-stable compound (I) has been utilized as the host in crystals with the light-sensitive guest tropolone methyl ether (Lavy et al., 2004), and with a number of other compounds, such as ether, enones, pyrazole, pyridine, pyran, and furan derivatives (Groom & Allen, 2014). Additionally, diol (I) was structurally characterized in 1990 (Goldberg et al., 1990) and with a number of typical solvents, such as acetone, dimethylformamide, CCl4, and alcohols (Groom & Allen, 2014).
The structural study reported herein can be summarized as follows: the crystal structure of (IV) was solved ab initio, the compositional disorder was modeled crystallographically, the composition of (II) and (III) was substantiated by additional analytical techniques, and a plausible source of the crystals and the synthetic procedure were proposed with a high degree of confidence.
Clear colourless high-quality large centimetre-long parallelepiped-shaped crystals had been stored under air in an Erlenmeyer flask for over 10 years with no visible deterioration. No information about either their synthesis or crystallization was available, when a representative crystal was selected for a single-crystal X-ray structural characterization for the purpose of training a teaching assistant. The crystal composition was initially established crystallographyically and subsequently found to be consistent with its being a cocrystal of the TADDOL (α,α,α',α'-tetraaryl-2,2-disubstituted 1,3-dioxolane-4,5-dimethanol) host 4,5-bis(hydroxydiphenylmethyl)-2,2-dimethyl-1,3-dioxolane, (I), with 85.1 (4)% of 4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one, (II), and 14.9 (4)% of 4a-(hydroperoxymethyl)-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one, (III). It was not possible to identify the student who submitted the crystals; therefore, we can only speculate about their preparation.
TADDOL, (I), is a common chiral catalyst (Seeback et al., 2001) that could have been used in a chiral synthesis leading to the formation of the enone (II), possibly by Robinson annulation or another route. There also is a distinct possibility that the chiral (I) was used as a host cocrystallant for (II), which is an oil, in order to establish its absolute configuration in an undergraduate organic laboratory. An autoxidation of the weak C—H bond at the only chiral center (C32) of enone (II) with ambient air is believed to yield the organic hydroperoxide (III) that subsequently cocrystallized with (I) and (II) as a minor component. The autoxidation is presumed to have taken place in solution rather than in the solid state. Several data sets on different crystals of (IV) were acquired to confirm that their (II):(III) ratio remains invariant within experimental error. It is noteworthy that all the compounds were stable in the solid state, but the organic hydroperoxide, (III), once isolated as a waxy solid, degraded into a brown oil within days in air. If (I) was not used to physically separate enantiomers of (II), another possibility is that the crystals formed serendipitously in the flask used for an organic synthetic procedure and were brought to the laboratory because of their beauty and size, rather than their importance.
Crystal data, data collection and structure refinement details are summarized in Table 1. There are three chemical moieties in the asymmetric unit. At one site, there is a fully occupied TADDOL host 4,5-bis(hydroxydiphenylmethyl)-2,2-dimethyl-1,3-dioxolane, (I). At the other site, there is compositional disorder between guest 4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one, (II), present 85.1 (4)% of the time, and impurity 4a-(hydroperoxymethyl)-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one, (III), observed 14.9 (4)% of the time. Most of the atoms in compounds (II) and (III) have the same coordinates; thus (II) and (III) differ only in the position of one CH2—CH2 link and the presence of the hydroperoxy group. Soft distance and thermal displacement parameter restraints were applied to the disordered part of the structure in order to achieve a chemically reasonable and computationally stable refinement.
Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT-Plus (Bruker, 2014); data reduction: SAINT-Plus (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXTL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXTL2014 (Sheldrick, 2015b).
C31H30O4·0.85(C10H14O)·0.15(C10H14O3) | Dx = 1.249 Mg m−3 |
Mr = 621.56 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 9920 reflections |
a = 9.5183 (5) Å | θ = 3.7–72.9° |
b = 9.5950 (7) Å | µ = 0.64 mm−1 |
c = 36.207 (4) Å | T = 100 K |
V = 3306.7 (5) Å3 | Block, colourless |
Z = 4 | 0.4 × 0.3 × 0.2 mm |
F(000) = 1330 |
Bruker SMART APEXII area-detector diffractometer | 6592 independent reflections |
Radiation source: sealed X-ray tube, Siemens, K FFCU 2K 90 | 6442 reflections with I > 2σ(I) |
Equatorially mounted graphite monochromator | Rint = 0.035 |
Detector resolution: 7.9 pixels mm-1 | θmax = 73.4°, θmin = 2.4° |
0.60° ω and 0.6° φ scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | k = −11→11 |
Tmin = 0.714, Tmax = 0.754 | l = −41→44 |
50756 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.035 | w = 1/[σ2(Fo2) + (0.0471P)2 + 0.9649P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.088 | (Δ/σ)max = 0.001 |
S = 1.05 | Δρmax = 0.28 e Å−3 |
6592 reflections | Δρmin = −0.25 e Å−3 |
409 parameters | Absolute structure: Flack x determined using 2716 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
30 restraints | Absolute structure parameter: 0.00 (5) |
C31H30O4·0.85(C10H14O)·0.15(C10H14O3) | V = 3306.7 (5) Å3 |
Mr = 621.56 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 9.5183 (5) Å | µ = 0.64 mm−1 |
b = 9.5950 (7) Å | T = 100 K |
c = 36.207 (4) Å | 0.4 × 0.3 × 0.2 mm |
Bruker SMART APEXII area-detector diffractometer | 6592 independent reflections |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | 6442 reflections with I > 2σ(I) |
Tmin = 0.714, Tmax = 0.754 | Rint = 0.035 |
50756 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.088 | Δρmax = 0.28 e Å−3 |
S = 1.05 | Δρmin = −0.25 e Å−3 |
6592 reflections | Absolute structure: Flack x determined using 2716 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
409 parameters | Absolute structure parameter: 0.00 (5) |
30 restraints |
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 | Occ. (<1) | |
O1 | −0.02369 (14) | 0.38554 (13) | 0.66881 (3) | 0.0179 (3) | |
O2 | 0.16594 (14) | 0.38359 (14) | 0.63014 (4) | 0.0190 (3) | |
O3 | −0.14599 (15) | 0.72666 (15) | 0.63829 (4) | 0.0246 (3) | |
H3 | −0.0938 | 0.7206 | 0.6196 | 0.037* | |
O4 | 0.01624 (14) | 0.67637 (13) | 0.57936 (4) | 0.0185 (3) | |
H4 | 0.0716 | 0.7402 | 0.5730 | 0.028* | |
C1 | 0.0895 (2) | 0.3011 (2) | 0.65631 (5) | 0.0189 (4) | |
C2 | −0.04715 (19) | 0.4952 (2) | 0.64314 (5) | 0.0160 (4) | |
H2 | −0.1175 | 0.4639 | 0.6244 | 0.019* | |
C3 | 0.09733 (19) | 0.51397 (19) | 0.62415 (5) | 0.0154 (4) | |
H3A | 0.1508 | 0.5892 | 0.6371 | 0.019* | |
C4 | 0.0346 (2) | 0.1715 (2) | 0.63731 (6) | 0.0293 (5) | |
H4A | −0.0314 | 0.1983 | 0.6178 | 0.044* | |
H4B | −0.0136 | 0.1124 | 0.6554 | 0.044* | |
H4C | 0.1133 | 0.1199 | 0.6265 | 0.044* | |
C5 | 0.1825 (2) | 0.2687 (3) | 0.68916 (6) | 0.0313 (5) | |
H5A | 0.2611 | 0.2100 | 0.6812 | 0.047* | |
H5B | 0.1277 | 0.2193 | 0.7080 | 0.047* | |
H5C | 0.2189 | 0.3557 | 0.6996 | 0.047* | |
C6 | −0.10716 (19) | 0.62211 (19) | 0.66456 (5) | 0.0165 (4) | |
C7 | 0.00134 (12) | 0.67885 (13) | 0.69261 (3) | 0.0195 (4) | |
C8 | 0.03443 (13) | 0.60219 (11) | 0.72400 (3) | 0.0220 (4) | |
H8 | −0.0087 | 0.5142 | 0.7281 | 0.026* | |
C9 | 0.13061 (14) | 0.65419 (15) | 0.74938 (3) | 0.0301 (5) | |
H9 | 0.1532 | 0.6018 | 0.7708 | 0.036* | |
C10 | 0.19371 (13) | 0.78286 (15) | 0.74338 (4) | 0.0386 (6) | |
H10 | 0.2594 | 0.8184 | 0.7607 | 0.046* | |
C11 | 0.16062 (15) | 0.85953 (12) | 0.71199 (4) | 0.0385 (6) | |
H11 | 0.2037 | 0.9475 | 0.7079 | 0.046* | |
C12 | 0.06444 (15) | 0.80753 (12) | 0.68660 (3) | 0.0280 (5) | |
H12 | 0.0418 | 0.8599 | 0.6652 | 0.034* | |
C14 | −0.33814 (13) | 0.48623 (13) | 0.66902 (3) | 0.0241 (4) | |
H14 | −0.3094 | 0.4328 | 0.6483 | 0.029* | |
C15 | −0.47027 (12) | 0.46535 (14) | 0.68441 (4) | 0.0289 (5) | |
H15 | −0.5318 | 0.3977 | 0.6742 | 0.035* | |
C16 | −0.51232 (10) | 0.54345 (15) | 0.71480 (4) | 0.0277 (5) | |
H16 | −0.6026 | 0.5292 | 0.7253 | 0.033* | |
C17 | −0.42224 (13) | 0.64243 (14) | 0.72980 (3) | 0.0273 (4) | |
H17 | −0.4510 | 0.6958 | 0.7506 | 0.033* | |
C18 | −0.29011 (12) | 0.66331 (13) | 0.71441 (3) | 0.0234 (4) | |
H18 | −0.2285 | 0.7310 | 0.7247 | 0.028* | |
C13 | −0.24806 (10) | 0.58521 (14) | 0.68403 (3) | 0.0180 (4) | |
C19 | 0.0921 (2) | 0.54668 (19) | 0.58206 (5) | 0.0167 (4) | |
C21 | 0.36275 (13) | 0.55617 (15) | 0.58562 (3) | 0.0258 (4) | |
H21 | 0.3585 | 0.5318 | 0.6110 | 0.031* | |
C20 | 0.23991 (10) | 0.56605 (14) | 0.56503 (3) | 0.0192 (4) | |
C25 | 0.24619 (11) | 0.60165 (15) | 0.52785 (3) | 0.0241 (4) | |
H25 | 0.1622 | 0.6084 | 0.5138 | 0.029* | |
C24 | 0.37532 (14) | 0.62737 (15) | 0.51127 (3) | 0.0295 (5) | |
H24 | 0.3796 | 0.6517 | 0.4859 | 0.035* | |
C23 | 0.49817 (11) | 0.61748 (16) | 0.53186 (4) | 0.0314 (5) | |
H23 | 0.5864 | 0.6351 | 0.5205 | 0.038* | |
C22 | 0.49188 (11) | 0.58189 (16) | 0.56904 (4) | 0.0326 (5) | |
H22 | 0.5758 | 0.5751 | 0.5831 | 0.039* | |
C31 | −0.13531 (12) | 0.45078 (10) | 0.55597 (3) | 0.0199 (4) | |
H31 | −0.1800 | 0.5347 | 0.5634 | 0.024* | |
C30 | −0.21370 (10) | 0.34447 (13) | 0.53999 (4) | 0.0236 (4) | |
H30 | −0.3120 | 0.3558 | 0.5365 | 0.028* | |
C29 | −0.14830 (13) | 0.22163 (11) | 0.52910 (4) | 0.0259 (4) | |
H29 | −0.2019 | 0.1490 | 0.5182 | 0.031* | |
C28 | −0.00452 (13) | 0.20510 (10) | 0.53419 (4) | 0.0250 (4) | |
H28 | 0.0402 | 0.1211 | 0.5267 | 0.030* | |
C27 | 0.07387 (10) | 0.31142 (12) | 0.55017 (3) | 0.0221 (4) | |
H27 | 0.1721 | 0.3001 | 0.5536 | 0.027* | |
C26 | 0.00848 (12) | 0.43426 (10) | 0.56106 (3) | 0.0178 (4) | |
O5 | −0.83840 (16) | 0.89933 (15) | 0.55736 (4) | 0.0290 (3) | |
O6 | −0.3022 (11) | 0.9681 (12) | 0.5975 (3) | 0.033 (3) | 0.149 (4) |
O7 | −0.3126 (13) | 0.8316 (14) | 0.5803 (3) | 0.040 (3) | 0.149 (4) |
H7 | −0.2876 | 0.7701 | 0.5955 | 0.060* | 0.149 (4) |
C32 | −0.4525 (2) | 1.0326 (2) | 0.59873 (6) | 0.0274 (5) | |
H32 | −0.3747 | 0.9750 | 0.5882 | 0.033* | 0.851 (4) |
C33 | −0.3884 (3) | 1.1420 (3) | 0.62428 (7) | 0.0383 (6) | |
H33A | −0.4619 | 1.2100 | 0.6313 | 0.046* | |
H33B | −0.3140 | 1.1930 | 0.6108 | 0.046* | |
C34 | −0.3254 (3) | 1.0781 (3) | 0.65935 (8) | 0.0446 (7) | |
H34A | −0.2473 | 1.0148 | 0.6527 | 0.054* | |
H34B | −0.2874 | 1.1529 | 0.6753 | 0.054* | |
C35 | −0.4387 (3) | 0.9969 (3) | 0.68029 (6) | 0.0361 (5) | |
H35A | −0.3980 | 0.9562 | 0.7030 | 0.043* | |
H35B | −0.5155 | 1.0608 | 0.6876 | 0.043* | |
C36 | −0.4970 (2) | 0.8811 (2) | 0.65582 (6) | 0.0300 (5) | |
H36A | −0.4221 | 0.8119 | 0.6510 | 0.036* | |
H36B | −0.5743 | 0.8331 | 0.6690 | 0.036* | |
C37 | −0.5509 (2) | 0.9369 (2) | 0.61966 (5) | 0.0240 (4) | |
C38 | −0.6771 (2) | 0.9007 (2) | 0.60643 (6) | 0.0231 (4) | |
H38 | −0.7387 | 0.8492 | 0.6219 | 0.028* | |
C39 | −0.7241 (2) | 0.9366 (2) | 0.56952 (6) | 0.0245 (4) | |
C40 | −0.6206 (3) | 1.0102 (3) | 0.54461 (7) | 0.0302 (7) | 0.851 (4) |
H40A | −0.6723 | 1.0643 | 0.5257 | 0.036* | 0.851 (4) |
H40B | −0.5618 | 0.9404 | 0.5317 | 0.036* | 0.851 (4) |
C41 | −0.5274 (3) | 1.1075 (3) | 0.56677 (8) | 0.0331 (7) | 0.851 (4) |
H41A | −0.5852 | 1.1843 | 0.5769 | 0.040* | 0.851 (4) |
H41B | −0.4561 | 1.1490 | 0.5502 | 0.040* | 0.851 (4) |
C41A | −0.4917 (15) | 1.040 (2) | 0.5589 (3) | 0.038 (4) | 0.149 (4) |
H41C | −0.4714 | 0.9503 | 0.5463 | 0.045* | 0.149 (4) |
H41D | −0.4397 | 1.1152 | 0.5463 | 0.045* | 0.149 (4) |
C40A | −0.6470 (15) | 1.0691 (15) | 0.5590 (6) | 0.037 (4) | 0.149 (4) |
H40C | −0.6774 | 1.1005 | 0.5342 | 0.045* | 0.149 (4) |
H40D | −0.6686 | 1.1438 | 0.5770 | 0.045* | 0.149 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0185 (6) | 0.0177 (6) | 0.0175 (6) | 0.0010 (5) | 0.0050 (5) | 0.0033 (5) |
O2 | 0.0184 (6) | 0.0187 (6) | 0.0200 (6) | 0.0029 (5) | 0.0057 (5) | 0.0050 (5) |
O3 | 0.0275 (7) | 0.0253 (7) | 0.0210 (7) | 0.0092 (6) | 0.0083 (6) | 0.0089 (6) |
O4 | 0.0205 (7) | 0.0150 (6) | 0.0201 (6) | −0.0006 (5) | 0.0054 (5) | 0.0021 (5) |
C1 | 0.0164 (9) | 0.0196 (9) | 0.0205 (9) | 0.0008 (7) | 0.0045 (7) | 0.0046 (7) |
C2 | 0.0148 (8) | 0.0197 (9) | 0.0136 (8) | −0.0025 (7) | 0.0014 (7) | 0.0017 (7) |
C3 | 0.0133 (8) | 0.0155 (8) | 0.0174 (9) | 0.0000 (7) | 0.0018 (7) | −0.0008 (7) |
C4 | 0.0319 (11) | 0.0200 (10) | 0.0359 (12) | −0.0025 (9) | 0.0105 (9) | −0.0016 (8) |
C5 | 0.0205 (10) | 0.0451 (13) | 0.0283 (11) | 0.0025 (9) | 0.0020 (8) | 0.0153 (10) |
C6 | 0.0173 (8) | 0.0182 (9) | 0.0141 (8) | 0.0019 (7) | 0.0025 (7) | 0.0025 (7) |
C7 | 0.0168 (9) | 0.0206 (9) | 0.0210 (9) | −0.0004 (7) | 0.0070 (7) | −0.0050 (7) |
C8 | 0.0182 (9) | 0.0268 (10) | 0.0210 (9) | 0.0003 (8) | 0.0022 (7) | −0.0061 (8) |
C9 | 0.0187 (9) | 0.0439 (13) | 0.0276 (11) | 0.0066 (9) | −0.0014 (8) | −0.0131 (10) |
C10 | 0.0196 (10) | 0.0486 (15) | 0.0475 (14) | −0.0017 (10) | 0.0005 (10) | −0.0320 (13) |
C11 | 0.0286 (12) | 0.0293 (12) | 0.0576 (16) | −0.0100 (10) | 0.0136 (11) | −0.0217 (11) |
C12 | 0.0274 (11) | 0.0201 (10) | 0.0364 (11) | −0.0013 (8) | 0.0118 (9) | −0.0079 (9) |
C14 | 0.0203 (9) | 0.0285 (10) | 0.0233 (10) | 0.0002 (8) | 0.0046 (8) | −0.0029 (8) |
C15 | 0.0212 (10) | 0.0346 (12) | 0.0307 (11) | −0.0037 (9) | 0.0029 (8) | −0.0012 (9) |
C16 | 0.0171 (9) | 0.0405 (12) | 0.0256 (10) | 0.0038 (9) | 0.0062 (8) | 0.0065 (9) |
C17 | 0.0241 (10) | 0.0400 (12) | 0.0179 (9) | 0.0051 (9) | 0.0057 (8) | −0.0006 (9) |
C18 | 0.0212 (10) | 0.0310 (11) | 0.0180 (9) | 0.0016 (8) | 0.0006 (7) | 0.0006 (8) |
C13 | 0.0155 (8) | 0.0226 (9) | 0.0158 (8) | 0.0036 (7) | 0.0014 (7) | 0.0048 (7) |
C19 | 0.0187 (9) | 0.0153 (8) | 0.0161 (8) | −0.0006 (7) | 0.0029 (7) | 0.0013 (7) |
C21 | 0.0218 (10) | 0.0272 (10) | 0.0285 (11) | 0.0009 (8) | 0.0071 (8) | 0.0047 (8) |
C20 | 0.0216 (9) | 0.0145 (8) | 0.0216 (9) | −0.0021 (7) | 0.0075 (7) | −0.0025 (7) |
C25 | 0.0295 (10) | 0.0210 (10) | 0.0220 (9) | −0.0035 (8) | 0.0065 (8) | −0.0035 (8) |
C24 | 0.0386 (12) | 0.0236 (10) | 0.0263 (10) | −0.0033 (9) | 0.0163 (9) | −0.0014 (8) |
C23 | 0.0275 (11) | 0.0245 (10) | 0.0421 (12) | −0.0026 (9) | 0.0203 (10) | 0.0005 (9) |
C22 | 0.0206 (10) | 0.0335 (12) | 0.0438 (13) | 0.0015 (9) | 0.0076 (9) | 0.0061 (10) |
C31 | 0.0240 (10) | 0.0206 (9) | 0.0151 (8) | −0.0009 (8) | 0.0006 (7) | 0.0011 (7) |
C30 | 0.0236 (10) | 0.0284 (11) | 0.0188 (9) | −0.0041 (8) | −0.0025 (7) | 0.0020 (8) |
C29 | 0.0349 (11) | 0.0228 (10) | 0.0199 (10) | −0.0100 (9) | −0.0022 (9) | −0.0015 (8) |
C28 | 0.0352 (11) | 0.0194 (9) | 0.0204 (9) | −0.0010 (9) | 0.0031 (8) | −0.0016 (7) |
C27 | 0.0246 (10) | 0.0228 (9) | 0.0190 (9) | −0.0016 (8) | 0.0040 (7) | 0.0002 (8) |
C26 | 0.0231 (9) | 0.0187 (9) | 0.0116 (8) | −0.0037 (7) | 0.0026 (7) | 0.0020 (7) |
O5 | 0.0274 (7) | 0.0218 (7) | 0.0379 (8) | −0.0051 (6) | −0.0082 (6) | 0.0072 (6) |
O6 | 0.021 (5) | 0.040 (6) | 0.039 (6) | 0.002 (4) | 0.002 (4) | 0.001 (5) |
O7 | 0.042 (7) | 0.050 (7) | 0.028 (6) | −0.001 (5) | 0.009 (5) | −0.011 (5) |
C32 | 0.0260 (10) | 0.0315 (11) | 0.0248 (10) | −0.0078 (9) | 0.0002 (8) | −0.0010 (9) |
C33 | 0.0439 (14) | 0.0330 (12) | 0.0379 (13) | −0.0118 (11) | −0.0121 (11) | 0.0014 (10) |
C34 | 0.0488 (15) | 0.0448 (15) | 0.0402 (14) | −0.0116 (13) | −0.0216 (12) | −0.0002 (12) |
C35 | 0.0454 (14) | 0.0391 (13) | 0.0236 (11) | 0.0060 (11) | −0.0114 (10) | −0.0013 (10) |
C36 | 0.0313 (11) | 0.0318 (11) | 0.0267 (11) | 0.0024 (10) | −0.0001 (9) | 0.0054 (9) |
C37 | 0.0276 (10) | 0.0244 (10) | 0.0199 (9) | −0.0015 (8) | 0.0034 (8) | −0.0020 (8) |
C38 | 0.0252 (9) | 0.0227 (9) | 0.0214 (9) | −0.0041 (8) | 0.0056 (8) | 0.0006 (8) |
C39 | 0.0265 (10) | 0.0162 (9) | 0.0308 (11) | −0.0027 (8) | −0.0010 (8) | 0.0036 (8) |
C40 | 0.0414 (16) | 0.0342 (16) | 0.0150 (12) | −0.0170 (13) | −0.0037 (11) | 0.0059 (11) |
C41 | 0.0393 (16) | 0.0365 (17) | 0.0235 (14) | −0.0228 (14) | −0.0063 (12) | 0.0083 (12) |
C41A | 0.044 (7) | 0.046 (10) | 0.023 (5) | −0.021 (7) | 0.016 (6) | −0.008 (7) |
C40A | 0.046 (7) | 0.033 (8) | 0.034 (9) | −0.008 (6) | −0.012 (6) | 0.011 (7) |
O1—C1 | 1.422 (2) | C24—H24 | 0.9500 |
O1—C2 | 1.421 (2) | C24—C23 | 1.3900 |
O2—C1 | 1.433 (2) | C23—H23 | 0.9500 |
O2—C3 | 1.428 (2) | C23—C22 | 1.3900 |
O3—H3 | 0.8400 | C22—H22 | 0.9500 |
O3—C6 | 1.431 (2) | C31—H31 | 0.9500 |
O4—H4 | 0.8400 | C31—C30 | 1.3900 |
O4—C19 | 1.442 (2) | C31—C26 | 1.3900 |
C1—C4 | 1.514 (3) | C30—H30 | 0.9500 |
C1—C5 | 1.515 (3) | C30—C29 | 1.3900 |
C2—H2 | 1.0000 | C29—H29 | 0.9500 |
C2—C3 | 1.548 (2) | C29—C28 | 1.3900 |
C2—C6 | 1.553 (3) | C28—H28 | 0.9500 |
C3—H3A | 1.0000 | C28—C27 | 1.3900 |
C3—C19 | 1.557 (3) | C27—H27 | 0.9500 |
C4—H4A | 0.9800 | C27—C26 | 1.3900 |
C4—H4B | 0.9800 | O5—C39 | 1.227 (3) |
C4—H4C | 0.9800 | O6—O7 | 1.453 (17) |
C5—H5A | 0.9800 | O6—C32 | 1.560 (11) |
C5—H5B | 0.9800 | O7—H7 | 0.8400 |
C5—H5C | 0.9800 | C32—H32 | 1.0000 |
C6—C7 | 1.547 (2) | C32—C33 | 1.527 (3) |
C6—C13 | 1.5559 (19) | C32—C37 | 1.514 (3) |
C7—C8 | 1.3900 | C32—C41 | 1.537 (3) |
C7—C12 | 1.3900 | C32—C41A | 1.491 (11) |
C8—H8 | 0.9500 | C33—H33A | 0.9900 |
C8—C9 | 1.3900 | C33—H33B | 0.9900 |
C9—H9 | 0.9500 | C33—C34 | 1.532 (3) |
C9—C10 | 1.3900 | C34—H34A | 0.9900 |
C10—H10 | 0.9500 | C34—H34B | 0.9900 |
C10—C11 | 1.3900 | C34—C35 | 1.531 (4) |
C11—H11 | 0.9500 | C35—H35A | 0.9900 |
C11—C12 | 1.3900 | C35—H35B | 0.9900 |
C12—H12 | 0.9500 | C35—C36 | 1.526 (3) |
C14—H14 | 0.9500 | C36—H36A | 0.9900 |
C14—C15 | 1.3900 | C36—H36B | 0.9900 |
C14—C13 | 1.3900 | C36—C37 | 1.504 (3) |
C15—H15 | 0.9500 | C37—C38 | 1.339 (3) |
C15—C16 | 1.3900 | C38—H38 | 0.9500 |
C16—H16 | 0.9500 | C38—C39 | 1.451 (3) |
C16—C17 | 1.3900 | C39—C40 | 1.511 (3) |
C17—H17 | 0.9500 | C39—C40A | 1.516 (11) |
C17—C18 | 1.3900 | C40—H40A | 0.9900 |
C18—H18 | 0.9500 | C40—H40B | 0.9900 |
C18—C13 | 1.3900 | C40—C41 | 1.518 (4) |
C19—C20 | 1.547 (2) | C41—H41A | 0.9900 |
C19—C26 | 1.541 (2) | C41—H41B | 0.9900 |
C21—H21 | 0.9500 | C41A—H41C | 0.9900 |
C21—C20 | 1.3900 | C41A—H41D | 0.9900 |
C21—C22 | 1.3900 | C41A—C40A | 1.505 (13) |
C20—C25 | 1.3900 | C40A—H40C | 0.9900 |
C25—H25 | 0.9500 | C40A—H40D | 0.9900 |
C25—C24 | 1.3900 | ||
C2—O1—C1 | 109.43 (13) | C24—C23—C22 | 120.0 |
C3—O2—C1 | 110.61 (14) | C22—C23—H23 | 120.0 |
C6—O3—H3 | 109.5 | C21—C22—H22 | 120.0 |
C19—O4—H4 | 109.5 | C23—C22—C21 | 120.0 |
O1—C1—O2 | 106.28 (14) | C23—C22—H22 | 120.0 |
O1—C1—C4 | 110.58 (16) | C30—C31—H31 | 120.0 |
O1—C1—C5 | 108.06 (16) | C30—C31—C26 | 120.0 |
O2—C1—C4 | 109.16 (16) | C26—C31—H31 | 120.0 |
O2—C1—C5 | 109.61 (16) | C31—C30—H30 | 120.0 |
C4—C1—C5 | 112.92 (18) | C29—C30—C31 | 120.0 |
O1—C2—H2 | 109.1 | C29—C30—H30 | 120.0 |
O1—C2—C3 | 103.72 (14) | C30—C29—H29 | 120.0 |
O1—C2—C6 | 108.16 (14) | C30—C29—C28 | 120.0 |
C3—C2—H2 | 109.1 | C28—C29—H29 | 120.0 |
C3—C2—C6 | 117.19 (15) | C29—C28—H28 | 120.0 |
C6—C2—H2 | 109.1 | C27—C28—C29 | 120.0 |
O2—C3—C2 | 103.69 (14) | C27—C28—H28 | 120.0 |
O2—C3—H3A | 109.2 | C28—C27—H27 | 120.0 |
O2—C3—C19 | 109.87 (14) | C28—C27—C26 | 120.0 |
C2—C3—H3A | 109.2 | C26—C27—H27 | 120.0 |
C2—C3—C19 | 115.47 (15) | C31—C26—C19 | 119.62 (10) |
C19—C3—H3A | 109.2 | C27—C26—C19 | 120.13 (10) |
C1—C4—H4A | 109.5 | C27—C26—C31 | 120.0 |
C1—C4—H4B | 109.5 | O7—O6—C32 | 107.8 (8) |
C1—C4—H4C | 109.5 | O6—O7—H7 | 109.5 |
H4A—C4—H4B | 109.5 | C33—C32—O6 | 85.6 (5) |
H4A—C4—H4C | 109.5 | C33—C32—H32 | 108.3 |
H4B—C4—H4C | 109.5 | C33—C32—C41 | 108.7 (2) |
C1—C5—H5A | 109.5 | C37—C32—O6 | 109.9 (4) |
C1—C5—H5B | 109.5 | C37—C32—H32 | 108.3 |
C1—C5—H5C | 109.5 | C37—C32—C33 | 111.15 (18) |
H5A—C5—H5B | 109.5 | C37—C32—C41 | 111.95 (19) |
H5A—C5—H5C | 109.5 | C41—C32—H32 | 108.3 |
H5B—C5—H5C | 109.5 | C41A—C32—O6 | 102.8 (8) |
O3—C6—C2 | 108.24 (14) | C41A—C32—C33 | 130.9 (8) |
O3—C6—C7 | 111.22 (14) | C41A—C32—C37 | 110.9 (7) |
O3—C6—C13 | 103.77 (13) | C32—C33—H33A | 109.1 |
C2—C6—C13 | 111.39 (14) | C32—C33—H33B | 109.1 |
C7—C6—C2 | 110.99 (14) | C32—C33—C34 | 112.6 (2) |
C7—C6—C13 | 110.98 (13) | H33A—C33—H33B | 107.8 |
C8—C7—C6 | 120.11 (10) | C34—C33—H33A | 109.1 |
C8—C7—C12 | 120.0 | C34—C33—H33B | 109.1 |
C12—C7—C6 | 119.89 (10) | C33—C34—H34A | 109.7 |
C7—C8—H8 | 120.0 | C33—C34—H34B | 109.7 |
C7—C8—C9 | 120.0 | H34A—C34—H34B | 108.2 |
C9—C8—H8 | 120.0 | C35—C34—C33 | 109.8 (2) |
C8—C9—H9 | 120.0 | C35—C34—H34A | 109.7 |
C10—C9—C8 | 120.0 | C35—C34—H34B | 109.7 |
C10—C9—H9 | 120.0 | C34—C35—H35A | 109.7 |
C9—C10—H10 | 120.0 | C34—C35—H35B | 109.7 |
C11—C10—C9 | 120.0 | H35A—C35—H35B | 108.2 |
C11—C10—H10 | 120.0 | C36—C35—C34 | 109.8 (2) |
C10—C11—H11 | 120.0 | C36—C35—H35A | 109.7 |
C12—C11—C10 | 120.0 | C36—C35—H35B | 109.7 |
C12—C11—H11 | 120.0 | C35—C36—H36A | 109.3 |
C7—C12—H12 | 120.0 | C35—C36—H36B | 109.3 |
C11—C12—C7 | 120.0 | H36A—C36—H36B | 107.9 |
C11—C12—H12 | 120.0 | C37—C36—C35 | 111.73 (19) |
C15—C14—H14 | 120.0 | C37—C36—H36A | 109.3 |
C15—C14—C13 | 120.0 | C37—C36—H36B | 109.3 |
C13—C14—H14 | 120.0 | C36—C37—C32 | 116.12 (19) |
C14—C15—H15 | 120.0 | C38—C37—C32 | 122.19 (19) |
C14—C15—C16 | 120.0 | C38—C37—C36 | 121.67 (19) |
C16—C15—H15 | 120.0 | C37—C38—H38 | 118.5 |
C15—C16—H16 | 120.0 | C37—C38—C39 | 123.00 (19) |
C15—C16—C17 | 120.0 | C39—C38—H38 | 118.5 |
C17—C16—H16 | 120.0 | O5—C39—C38 | 122.32 (19) |
C16—C17—H17 | 120.0 | O5—C39—C40 | 120.0 (2) |
C18—C17—C16 | 120.0 | O5—C39—C40A | 125.7 (6) |
C18—C17—H17 | 120.0 | C38—C39—C40 | 117.39 (19) |
C17—C18—H18 | 120.0 | C38—C39—C40A | 106.3 (7) |
C17—C18—C13 | 120.0 | C39—C40—H40A | 109.5 |
C13—C18—H18 | 120.0 | C39—C40—H40B | 109.5 |
C14—C13—C6 | 120.68 (10) | C39—C40—C41 | 110.7 (2) |
C18—C13—C6 | 118.95 (10) | H40A—C40—H40B | 108.1 |
C18—C13—C14 | 120.0 | C41—C40—H40A | 109.5 |
O4—C19—C3 | 104.84 (14) | C41—C40—H40B | 109.5 |
O4—C19—C20 | 108.95 (13) | C32—C41—H41A | 109.1 |
O4—C19—C26 | 108.16 (14) | C32—C41—H41B | 109.1 |
C20—C19—C3 | 112.68 (14) | C40—C41—C32 | 112.4 (2) |
C26—C19—C3 | 110.99 (14) | C40—C41—H41A | 109.1 |
C26—C19—C20 | 110.92 (13) | C40—C41—H41B | 109.1 |
C20—C21—H21 | 120.0 | H41A—C41—H41B | 107.9 |
C20—C21—C22 | 120.0 | C32—C41A—H41C | 110.8 |
C22—C21—H21 | 120.0 | C32—C41A—H41D | 110.8 |
C21—C20—C19 | 122.87 (10) | C32—C41A—C40A | 104.6 (11) |
C21—C20—C25 | 120.0 | H41C—C41A—H41D | 108.9 |
C25—C20—C19 | 117.04 (10) | C40A—C41A—H41C | 110.8 |
C20—C25—H25 | 120.0 | C40A—C41A—H41D | 110.8 |
C24—C25—C20 | 120.0 | C39—C40A—H40C | 110.0 |
C24—C25—H25 | 120.0 | C39—C40A—H40D | 110.0 |
C25—C24—H24 | 120.0 | C41A—C40A—C39 | 108.6 (12) |
C25—C24—C23 | 120.0 | C41A—C40A—H40C | 110.0 |
C23—C24—H24 | 120.0 | C41A—C40A—H40D | 110.0 |
C24—C23—H23 | 120.0 | H40C—C40A—H40D | 108.4 |
O1—C2—C3—O2 | 21.91 (17) | C13—C6—C7—C8 | 53.96 (16) |
O1—C2—C3—C19 | 142.14 (15) | C13—C6—C7—C12 | −125.23 (12) |
O1—C2—C6—O3 | −173.43 (14) | C13—C14—C15—C16 | 0.0 |
O1—C2—C6—C7 | 64.26 (17) | C19—C20—C25—C24 | 176.83 (13) |
O1—C2—C6—C13 | −59.96 (18) | C21—C20—C25—C24 | 0.0 |
O2—C3—C19—O4 | 177.70 (13) | C20—C19—C26—C31 | −143.43 (11) |
O2—C3—C19—C20 | −63.95 (18) | C20—C19—C26—C27 | 42.29 (16) |
O2—C3—C19—C26 | 61.15 (18) | C20—C21—C22—C23 | 0.0 |
O3—C6—C7—C8 | 168.95 (10) | C20—C25—C24—C23 | 0.0 |
O3—C6—C7—C12 | −10.24 (17) | C25—C24—C23—C22 | 0.0 |
O3—C6—C13—C14 | 85.78 (15) | C24—C23—C22—C21 | 0.0 |
O3—C6—C13—C18 | −87.20 (14) | C22—C21—C20—C19 | −176.63 (14) |
O4—C19—C20—C21 | 115.36 (13) | C22—C21—C20—C25 | 0.0 |
O4—C19—C20—C25 | −61.36 (16) | C31—C30—C29—C28 | 0.0 |
O4—C19—C26—C31 | −24.00 (16) | C30—C31—C26—C19 | −174.29 (13) |
O4—C19—C26—C27 | 161.72 (10) | C30—C31—C26—C27 | 0.0 |
C1—O1—C2—C3 | −25.52 (18) | C30—C29—C28—C27 | 0.0 |
C1—O1—C2—C6 | −150.63 (14) | C29—C28—C27—C26 | 0.0 |
C1—O2—C3—C2 | −11.07 (18) | C28—C27—C26—C19 | 174.26 (13) |
C1—O2—C3—C19 | −135.03 (15) | C28—C27—C26—C31 | 0.0 |
C2—O1—C1—O2 | 19.26 (19) | C26—C19—C20—C21 | −125.69 (12) |
C2—O1—C1—C4 | −99.09 (18) | C26—C19—C20—C25 | 57.59 (15) |
C2—O1—C1—C5 | 136.85 (16) | C26—C31—C30—C29 | 0.0 |
C2—C3—C19—O4 | 60.90 (19) | O5—C39—C40—C41 | 151.4 (3) |
C2—C3—C19—C20 | 179.25 (14) | O5—C39—C40A—C41A | −144.8 (9) |
C2—C3—C19—C26 | −55.65 (19) | O6—C32—C33—C34 | −59.7 (5) |
C2—C6—C7—C8 | −70.48 (16) | O6—C32—C37—C36 | 46.6 (5) |
C2—C6—C7—C12 | 110.33 (13) | O6—C32—C37—C38 | −131.7 (5) |
C2—C6—C13—C14 | −30.46 (17) | O6—C32—C41A—C40A | 167.1 (11) |
C2—C6—C13—C18 | 156.56 (11) | O7—O6—C32—C33 | 168.6 (8) |
C3—O2—C1—O1 | −4.02 (19) | O7—O6—C32—C37 | 57.7 (9) |
C3—O2—C1—C4 | 115.27 (17) | O7—O6—C32—C41A | −60.4 (12) |
C3—O2—C1—C5 | −120.57 (18) | C32—C33—C34—C35 | −58.0 (3) |
C3—C2—C6—O3 | 69.88 (19) | C32—C37—C38—C39 | 7.1 (3) |
C3—C2—C6—C7 | −52.43 (19) | C32—C41A—C40A—C39 | −74.8 (17) |
C3—C2—C6—C13 | −176.65 (14) | C33—C32—C37—C36 | −46.4 (3) |
C3—C19—C20—C21 | −0.55 (19) | C33—C32—C37—C38 | 135.4 (2) |
C3—C19—C20—C25 | −177.28 (11) | C33—C32—C41—C40 | −167.5 (3) |
C3—C19—C26—C31 | 90.49 (14) | C33—C32—C41A—C40A | −97.7 (12) |
C3—C19—C26—C27 | −83.79 (15) | C33—C34—C35—C36 | 59.7 (3) |
C6—C2—C3—O2 | 140.99 (15) | C34—C35—C36—C37 | −55.3 (3) |
C6—C2—C3—C19 | −98.78 (19) | C35—C36—C37—C32 | 49.8 (3) |
C6—C7—C8—C9 | −179.19 (13) | C35—C36—C37—C38 | −131.9 (2) |
C6—C7—C12—C11 | 179.19 (13) | C36—C37—C38—C39 | −171.1 (2) |
C7—C6—C13—C14 | −154.68 (10) | C37—C32—C33—C34 | 50.0 (3) |
C7—C6—C13—C18 | 32.34 (16) | C37—C32—C41—C40 | −44.4 (4) |
C7—C8—C9—C10 | 0.0 | C37—C32—C41A—C40A | 49.7 (14) |
C8—C7—C12—C11 | 0.0 | C37—C38—C39—O5 | 177.8 (2) |
C8—C9—C10—C11 | 0.0 | C37—C38—C39—C40 | 3.9 (3) |
C9—C10—C11—C12 | 0.0 | C37—C38—C39—C40A | −27.4 (8) |
C10—C11—C12—C7 | 0.0 | C38—C39—C40—C41 | −34.6 (4) |
C12—C7—C8—C9 | 0.0 | C38—C39—C40A—C41A | 61.5 (14) |
C14—C15—C16—C17 | 0.0 | C39—C40—C41—C32 | 54.6 (4) |
C15—C14—C13—C6 | −172.91 (13) | C41—C32—C33—C34 | 173.6 (2) |
C15—C14—C13—C18 | 0.0 | C41—C32—C37—C36 | −168.1 (2) |
C15—C16—C17—C18 | 0.0 | C41—C32—C37—C38 | 13.6 (3) |
C16—C17—C18—C13 | 0.0 | C41A—C32—C33—C34 | −162.7 (8) |
C17—C18—C13—C6 | 173.04 (13) | C41A—C32—C37—C36 | 159.6 (8) |
C17—C18—C13—C14 | 0.0 | C41A—C32—C37—C38 | −18.7 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4 | 0.84 | 1.85 | 2.6777 (19) | 171 |
O4—H4···O5i | 0.84 | 1.84 | 2.6693 (19) | 169 |
O7—H7···O3 | 0.84 | 2.10 | 2.818 (13) | 144 |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C31H30O4·0.85(C10H14O)·0.15(C10H14O3) |
Mr | 621.56 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 9.5183 (5), 9.5950 (7), 36.207 (4) |
V (Å3) | 3306.7 (5) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Bruker SMART APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Krause et al., 2015) |
Tmin, Tmax | 0.714, 0.754 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 50756, 6592, 6442 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.621 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.088, 1.05 |
No. of reflections | 6592 |
No. of parameters | 409 |
No. of restraints | 30 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.25 |
Absolute structure | Flack x determined using 2716 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | 0.00 (5) |
Computer programs: APEX2 (Bruker, 2014), SAINT-Plus (Bruker, 2014), SHELXT (Sheldrick, 2015a), SHELXTL2014 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4 | 0.84 | 1.85 | 2.6777 (19) | 170.6 |
O4—H4···O5i | 0.84 | 1.84 | 2.6693 (19) | 168.9 |
O7—H7···O3 | 0.84 | 2.10 | 2.818 (13) | 143.6 |
Symmetry code: (i) x+1, y, z. |
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