Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616004885/wq3111sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616004885/wq3111Compound_1sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616004885/wq3111Compound_2sup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616004885/wq3111Compound_3sup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616004885/wq3111Compound_4sup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616004885/wq3111Compound_5asup6.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616004885/wq3111Compound_5bsup7.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229616004885/wq3111sup8.pdf |
CCDC references: 1470211; 1470210; 1470209; 1470208; 1470207; 1470206
\ Tetrahydro-1-benzazepines have been described as potential antiparasitic drugs for the treatment of chagas disease and leishmaniasis, two of the most important, so-called `forgotten tropical diseases' affecting South and Central America, caused by Trypanosoma cruzi and Leishmania chagasi parasites, respectively (Gómez-Ayala et al., 2010). A simple synthetic approach for the stereoselective synthesis of exo-2-aryl-1,4-epoxytetrahydro-1-benzazepines and the alcohol derivatives exo-2-aryl-1,4-tetrahydro-1-benzazepine-4-ols, through the selective oxidation of substituted ortho-allyl-N-benzylanilines and subsequent intramolecular 1,3-dipolar cycloaddition of the formed nitrones and posterior opening of the epoxide, was described (Gómez-Ayala et al., 2006; Acosta, Palma & Bahsas, 2010; Acosta et al., 2012) and systematically applied to prepare new compounds in the search for molecules with better biological activity against these parasites. Part of this systematic study of particularly active molecules (Acosta et al., 2009; Acosta et al., 2008; Acosta, Palma, Bahsas et al., 2010; Gómez et al., 2008, 2009, 2010, 2011; Sanabria et al., 2010; Blanco et al., 2012a,b,c; Yépes et al., 2012, 2013; Guerrero et al., 2014; Sanabría et al., 2014) included the crystal structure determination. Two series of structures are presented and their conformation and packing are described and compared in this paper: (2SR,4RS)-6,8-dimethyl-2-(naphthalen-1-yl)-2,3,4,5-tetrahydro-\ 1H-1,4-epoxy-1-benzazepine, (1), (2SR,4RS)-6,9-dimethyl-2-(naphthalen-1-yl)-2,3,4,5-tetrahydro-\ 1H-1,4-epoxy-1-benzazepine, (2), (2SR,4RS)-8,9-dimethyl-2-(naphthalen-1-yl)-2,3,4,5-tetrahydro-\ 1H-1,4-epoxy-1-benzazepine, (3), are epoxy-1-benzazepines differing only in the position of two methyl groups in the 6-, 8- and 9-positions in the fused benzene ring, and 7-fluoro-cis-2-[(E)-styryl]-2,3,4,5-tetrahydro-1H-1-\ benzazepin-4-ol, (4), and 7-fluoro-cis-2-[(E)-pent-1-enyl]-2,3,4,5-tetrahydro-1H-\ 1-benzazepin-4-ol, (5), are 1-benzazepin-4-ols replacing both methyl residues for fluorine at the 7-position 7, differing in the residues at the 2-position.
The syntheses of the compounds (1)–(5) were carried out following our previously estabished experimental conditions (Acosta, Palma & Bahsas, 2010; Acosta et al., 2012). Particular details are described as follows. Recrystallization of (1)–(3) by slow evaporation of a solution in heptane gave crystals of suitable size and quality for single-crystal X-ray diffraction. In the case of compounds (4) and (5), the recrystallization was performed from a heptane–ethyl acetate (1:1 v/v) mixture which also gave crystals suitable for single-crystal X-ray diffraction.
Sodium tungstate dihydrate, Na2WO4·2H2O (7 mol%), followed by 30% aqueous hydrogen peroxide solution (0.30 mol), were added to a stirred and cooled (273 K) solution of the appropriate dimethyl-substituted 2-allyl-N-(naphthalen-1-ylmethyl)aniline (0.10 mol) in methanol (20 ml). The resulting mixtures were then stirred at ambient temperature for 72 h. Each mixture was filtered and the solvent removed under reduced pressure. Toluene (30 ml) was added to the solid residue and the resulting solution was heated under reflux for 18 h. After cooling each solution to ambient temperature, the solvent was removed under reduced pressure and the crude product was purified by chromatography on silica using heptane–ethyl acetate (compositions ranged from 60:1 to 10:1 v/v) as eluent to give compounds (1)–(3) with yields of 69, 67 and 59%, respectively (see Scheme 1).
To stirred and ice-bath-cooled methanolic solutions of the 1,4-epoxy cycloadducts were added zinc powder (10 mmol), glacial acetic acid (7 mmol) and hydrochloric acid (7 mmol, 37% HCl). The resulting mixtures were stirred at 273 K for an additional 30 min and the crude products were filtered. Each filtrate was then basified with 25% aqueous NH4OH to pH 8, extracted with EtOAc (3 × 50 ml), and the combined organic layers were dried over anhydrous Na2SO4. The solvent was removed under reduced pressure and the crude product was purified by column chromatography (silica gel, heptane–EtOAc, 10:1 to 1:1 v/v) to give the compounds (4) and (5) with yields of 93 and 90%, respectively (see Scheme 2).
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in calculated positions (C—H = 0.93–1.00 Å) and included as riding contributions with isotropic displacement parameters set at 1.2-1.5 times of the Ueq value of the parent atom. H atoms belonging to OH and NH groups were located in difference density maps and refined freely. Some low-angle reflections strongly affected by the experiment, attenuated by the beam stop, for instance, were omitted for the final refinements, viz. for (1) 366 and 366, for (2) 011 and for (5) 120.
The two groups of compounds described show different conformational and packing characteristics due to the size and position of substituents and the different conformations of the benzodiazepine nucleus (rigid in the epoxides and more flexible in the alcohols).
The non-enantioselective synthesis pathway (Gómez-Ayala et al., 2010; Acosta, Palma & Bahsas, 2010; OR Acosta, Palma, Bahsas et al., 2010) that produce racemic mixtures of the structural isomers (1), (2) and (3), however, they crystallize in different forms. Compound (1) crystallizes as a racemate in the space group P21/c, with Z' = 2, where the two molecules in the asymmetric unit were selected to have the same absolute configuration [(2S, 4R), as shown in Fig. 1]. Compund (2) crystallizes in the Schonke space group P212121, selecting the same (2S,4R) absolute configuration for the refinement (Fig. 2a), and compound (3) crystallizes in the Sohncke space group P21 and the crystal selected for structure determination was the (2S, 4R) enantiomer (Fig. 2b). This crystallization behaviour of slightly different isomers in different space groups with different crystalline symmetries has been described previously for this kind of compound (Acosta et al., 2008; Acosta, Palma, Bahsas et al., 2010).
The A conformer in (1) is conformationally identical to molecules (2) and (3), since the epoxybenzazepine nucleus is rather rigid, as shown by the overlay of the nuclei of (1A) and (2) with (3) (atoms N1, O1, C2, C3, C4, C5, C5A, C6, C7, C8, C9 and C9A), that give r.m.s. deviations of 0.0345 and 0.0249 Å, respectively. The dihedral angle between the naphthyl and benzyl rings are 88.14 (6), 87.66 (9) and 85.74 (6)° in (1A), (2) and (3), respectively, which indicates that the orthogonal conformation of the rings is the most stable for these molecules. Considering the conformation of the fused rings in the nuclei of the molecules (1A), (2) and (3), the five- (O1/N1/C2–C4) and six-membered (O1/N1/C9A/C5A/C5/C4) rings adopt an intermediate conformation between half-chair and envelope (Table 2) (Cremer & Pople, 1975).
The (1B) conformer in (1) shows a similar but not identical conformation of the epoxybenzazepine nucleus with respect to (1A) [r.m.s. deviation = 0.045 Å, larger than that of (1A) and (2) with (3)] with slightly different puckering parameters for the five- and six-memebred rings than those observed between (1A), (2) and (3) (Table 2). The main difference between (1B) and the other molecules is the dihedral angle between the naphthyl and benzyl rings of 4.26 (6)°, indicating that both rings are almost parallel and that molecule (1B) shows a relatively planar arrangement.
Even though the three compounds show different space groups, a motif of intermolecular interactions seems to be common to the three structures that form chains of molecules related by a 21 screw axis in the three cases along b. In the three compunds, weak C—H···O and C—H···π interactions direct the formation of chains (Tables 3, 4 and 5). In (1A), one C2A—H2A···O1Ai [symmetry code: (i) -x+1, y+1/2] and one C5A—H5AA···Cg1A2ii [Cg1A2 is the centroid of the C20A–C24A/C29A ring; symmetry code: (ii) -x+1, y-1/2, -z+1/2] interaction connect molecules related by a 21 screw axis (Fig. 3a), in (2), only one weak C82—H82···O1i [symmetry code: (i) -x+1, y+1/2, ???] hydrogen bond connects consecutive molecules (Fig. 3b), and in (3), one C8—H8···O1iii [symmetry code: (iii) x, y+1, z] and two C27—H27···Cg31iv and C28—H28···Cg32iv [Cg31 and Cg32 are the centroids of the C20–C24/C29 and C24–C29 rings, respectively; symmetry code: (iv) -x, y+1/2, -z+1] connect consecutive molecules (Fig. 3c), with additional C—H···π or van der Waals interactions connecting parallel chains. The case of compound (1) is more complex, though, since the crystal is centrosymmetric, therefore inverted chains of (1A) (2R,4S) enantiomers also run parallel to the b axis; furthermore, molecule (1B), with a different conformation, is also present. It is interesting, however, that molecules (1A) pack in separate layers from (1B) which form inversion dimers through C4B—H4B···O1Bv [symmetry code: (v) -x+2, -y, -z+1] and each molecule stacks with another inverted molecule along b (Fig. 3a). Chains of dimers, related by the c-glide plane have an parallel disposition of the planar benzyl and naphthyl ring that allows for C—H···π interactions.
Compounds (4) and (5) crystallize as racemates in the centrosymmetric Pbca and R3 space groups, respectively; both compounds were studied at room temperature and at 100 K. Compound (4) shows the same structure at both temperatures, but compound (5) shows a phase transition between room temperature, i.e. compound (5RT), and 100 K, i.e. compound (5LT), as will be described below.
For both compounds, the seven-membered ring adopts a chair conformation (Table 2) with the hydroxy, and styryl/pentenyl substituents [in (4) and (5)] in equatorial positions and the fluorobenzyl ring in a bisectional conformation, as shown in Fig. 4. Even though the seven-memebered ring of the tetrahydrobenzazepine nucleus has conformational freedom, all the independent molecules in (4), (5RT) and (5LT) show a very consistent conformation, with a maximum average r.m.s. deviation of 0.0794 Å of the common 7-fluorotetrahydrobenzazepine nucleus (atoms N1, O1, C2, C3, C4, C5, C52, C6, C7, C8, C9 and C92) between the molecule in (4) and molecule 3 of (5LT).
In the molecule of (4), the C22–C28 plane containing the styryl group is oriented towards the 7-fluorotetrahydrobenzazepine nucleus, making a dihedral angle of 60.99 (5)° (Fig. 4a). This general conformation is conserved at room temperature and 100 K. In this molecule, the styryl group is not completely planar since the C24—C23—C22—C21 torsion angle, which has a value of 168.68 (13)°, is slightly distorted considering that only Csp2 atoms are involved. The heterocyclic ring (atoms N1/C2–C5/C5A/C9A) in both compounds has similar puckering parameters values (Table 2) (Cremer & Pople, 1975).
Atoms of the pentenyl chain of the room-temperature structure of compound (5), denoted (5RT), exhibited high anisotropic displacement ellipsoids in the initial refinement cycles consistent with positional disorder in two different conformations of the same chain, slightly rotated along the C2—C10 bond, and were modelled as such (Fig. 4b). This positional disorder turned out to be very important when a new data collection was performed at 100 K, denoted (5LT), where it was observed that this disorder would correspond to the co-existence of various possible conformations of the pentenyl residue (Fig. 4c). The disorder in the room-temperature structure was refined successfully assuming two pentenyl chains in the same conformation with refined occupancies of 48.3 (5) and 51.7 (5)%, and an average C11—C12—C13—C14 torsion angle of -167.9° (Fig. 4b). However, the data at 100 K revealed that in fact it is possible to differentiate a new conformation as result of a rotation in the C12—C13 bond giving rise to a structure with a Z' value of 4. The four independent molecules in the asymmetric unit, each with different degree of disorder, are the result of the averaging of different proportions of two main different conformation of the pentenyl chain [with one of the conformations showing two possible torsion angles as in (5RT)]. In this sense, molecules 1 (2R,4S) and 2 (2S,4R) (see Fig. 4c) correspond to two ordered conformers, with torsion angles (C111—C112—C113—C114 and C211—C212—C213—C214) of -179.22 (14) and 72.11 (16)°, respectively (called conformers α and β in Fig. S1 of the Supporting information). Molecule 3 (2S,4R) shows disorder, similar to that of (5RT), successfully described as the co-existence of two chains with the same α conformation but in slightly different positions, with occupancies of 84.1 (2) and 15.9 (2)% and torsion angles of 176.06 (19) and 174.5 (11)°. Molecule 4 (2S,4R) represents a mixture of both α and β conformers, with two orientations of the former, with occupancies of 31.9 (8) and 34.0 (8)%, and an average torsion angle of ~176.5°, and a third one corresponding to the β conformer having an occupancy of 34.2 (3) and a torsion angle of 71.5 (6)° (see Fig. S1 in the Supporting information). The molecular connectivity in (5) (Tables 6 and 7) is quite different from that in (4). At room temperature, six molecules are connected by N1—H1N···O1i [symmetry code: (i) x-y+2/3, x+1/3, -z+4/3] [not in Table 6, but in Table 8 for compound (4)?] hydrogen bonds in a racemic ring parallel to (001), leaving the pentenyl substituents oriented to the centre and the F atoms oriented outward, describing a threefold rotoinversion axis with [001] direction (Fig. 5a). Each six-membered ring is connected to six other equivalent structures along the three dimensions connected by six pairs of N1—H1N···O1i and O1—H1O···N1ii [symmetry code: (ii) -y+2/3, x-y+1/3, z+1/3] [not in Table 6, but in Table 8 for compound (4)?] hydrogen bonds generating R44(8) motifs (Fig. 5b). Each pair of enantiomers are also related by an inversion centre at (1/2, 1/2, 1/2) and connected between them by probably induced dipolar interactions involving the halogen substituent. In a supramolecular perspective, a view along [001] allows one to differentiate the centre of the rings at (2/3, 1/3, z) and (1/3, 2/3, z) (Fig. 5a). The structure at 100 K is transformed in a superstructure of the crystal structure at room temperature since the conformers (see Fig. S1 in the Supporting information) are perceptibly different. In this case, the molecular connectivity remains as room temperature and each individual molecule in the asymmetric unit constitutes a racemic sixfold molecular ring by N(1,2,3,4)1—H(1,2,3,4)N···O(3i,1ii,2iii,4iv)1 [symmetry codes: (i) x, y, z+1; (ii) -y+2/3, x-y+1/3, z-2/3; (iii) x-y+2/3, x+1/3, -z+1/3; (iv) y-1/3, -x+y+1/3, -z+4/3] hydrogen bonds (Table 7). However, the presence of both α and β conformers break half of the threefold rotoinversion axes observed at room temperature leaving a threefold screw axis with [001] direction in the centre of each molecular ring (Fig. 5c).
The supramolecular assembly of both molecules in their crystals differ significantly, as expected for the very different sizes of the styryl and pentenyl substituents. In compound (4), each molecule is connected to four equivalent molecules at the same z value by two pairs of N1—H1N···O1i and O1—H1O···N1ii [symmetry codes: (i) x, y-1, z; (ii) -x+3/2, y+1/2, z] hydrogen bonds (Table 8), where atoms N1 and O1 act each as donor and acceptor. Hydrogen-bonded molecules form enantiomorphic chains along the [010] direction (Fig. 6). The chains have a polar disposition, since all molecules in a chain are related by the b-glide plane normal to a (Fig. 6a). This makes the F atoms from all the molecules lie on the same side of the chain, leaving all nonpolar moieties on the other side. Each chain connects with an inverted chain on the [001] direction through weak C6—H6···F1iii [symmetry code: (iii) -x+1, -y+1, -z+1] dipolar interactions (2.47 Å) (Jelsch et al., 2015) (Figs. 6b and 6c). The interactions among double chains in the [100] and [001] directions are weak and probably dipolar or van der Waals in nature since no weak hydrogen bonds or π–π stacking interactions are detected.
Compund (5) shows different structures at room temperature and 100 K, with the low-temperature structure crystallizing in a klassengleiche subgroup of the room-temperature one, with a quadrupling of the unit-cell volume in the (110) plane. The descriptions of (5LT) could be obtained from that of (5RT) by the matrix P = [200 220 001] (International Tables for Crystallography, 2011). In order to confirm the group/subgroup relation of both structures and determine the degree of distortion of one respect to the other, the ordered part of the molecule in the (5RT) crystal was transformed into the subgroup of (5LT) using TRANSTRU program in the Bilbao Crystallography Server (Aroyo, Kirov et al., 2006; Aroyo, Perez-Mato et al., 2006; Aroyo et al., 2011) and the output structure, consisting of the ordered nuclei of the molecules was compared with the same nuclei in the (5LT) structure (all pentenyl residues, ordered and disordered, were removed) using COMPSTRU (Tasci et al., 2012) and an almost perfect overlap was obtained with an average/maximum atom displacement of 0.1667/0.2539 Å (for atom F1A). These deviations are very small considering the temperature difference and the fact that the room-temperature structure shows one molecule with the pentenyl chain split in two main positions, while the 100 K structure shows four independent molecules, two of them ordered and the other two displaying two and three different pentenyl chain conformations. This strongly suggests that the phase transition observed between room temperature and 100 K could be entirely explained by the partial ordering of the pentenly chains in half of the molecules, that breaks half of the 3 symmetry axes of the room-temperature structure on cooling. The refinement of the 100 K structure using the room-temperature model (R3 space group with halved a and b unit-cell parameters) using hkl data transformed using the inverse of the matrix above, provides a reasonable but significantly poorer model, with unreasonable displacement parameters (too high for a low-temperature model), a higher R factor and a much larger degree of disorder of the pentenyl chain that is very hard to model with less than three separate conformations. This clearly justifies the use of the subgroup to model the 100 K structure and again confirm that the ordering of the pentenyl chains is key to this phase transition.
\ Tetrahydro-1-benzazepines have been described as potential antiparasitic drugs for the treatment of chagas disease and leishmaniasis, two of the most important, so-called `forgotten tropical diseases' affecting South and Central America, caused by Trypanosoma cruzi and Leishmania chagasi parasites, respectively (Gómez-Ayala et al., 2010). A simple synthetic approach for the stereoselective synthesis of exo-2-aryl-1,4-epoxytetrahydro-1-benzazepines and the alcohol derivatives exo-2-aryl-1,4-tetrahydro-1-benzazepine-4-ols, through the selective oxidation of substituted ortho-allyl-N-benzylanilines and subsequent intramolecular 1,3-dipolar cycloaddition of the formed nitrones and posterior opening of the epoxide, was described (Gómez-Ayala et al., 2006; Acosta, Palma & Bahsas, 2010; Acosta et al., 2012) and systematically applied to prepare new compounds in the search for molecules with better biological activity against these parasites. Part of this systematic study of particularly active molecules (Acosta et al., 2009; Acosta et al., 2008; Acosta, Palma, Bahsas et al., 2010; Gómez et al., 2008, 2009, 2010, 2011; Sanabria et al., 2010; Blanco et al., 2012a,b,c; Yépes et al., 2012, 2013; Guerrero et al., 2014; Sanabría et al., 2014) included the crystal structure determination. Two series of structures are presented and their conformation and packing are described and compared in this paper: (2SR,4RS)-6,8-dimethyl-2-(naphthalen-1-yl)-2,3,4,5-tetrahydro-\ 1H-1,4-epoxy-1-benzazepine, (1), (2SR,4RS)-6,9-dimethyl-2-(naphthalen-1-yl)-2,3,4,5-tetrahydro-\ 1H-1,4-epoxy-1-benzazepine, (2), (2SR,4RS)-8,9-dimethyl-2-(naphthalen-1-yl)-2,3,4,5-tetrahydro-\ 1H-1,4-epoxy-1-benzazepine, (3), are epoxy-1-benzazepines differing only in the position of two methyl groups in the 6-, 8- and 9-positions in the fused benzene ring, and 7-fluoro-cis-2-[(E)-styryl]-2,3,4,5-tetrahydro-1H-1-\ benzazepin-4-ol, (4), and 7-fluoro-cis-2-[(E)-pent-1-enyl]-2,3,4,5-tetrahydro-1H-\ 1-benzazepin-4-ol, (5), are 1-benzazepin-4-ols replacing both methyl residues for fluorine at the 7-position 7, differing in the residues at the 2-position.
Sodium tungstate dihydrate, Na2WO4·2H2O (7 mol%), followed by 30% aqueous hydrogen peroxide solution (0.30 mol), were added to a stirred and cooled (273 K) solution of the appropriate dimethyl-substituted 2-allyl-N-(naphthalen-1-ylmethyl)aniline (0.10 mol) in methanol (20 ml). The resulting mixtures were then stirred at ambient temperature for 72 h. Each mixture was filtered and the solvent removed under reduced pressure. Toluene (30 ml) was added to the solid residue and the resulting solution was heated under reflux for 18 h. After cooling each solution to ambient temperature, the solvent was removed under reduced pressure and the crude product was purified by chromatography on silica using heptane–ethyl acetate (compositions ranged from 60:1 to 10:1 v/v) as eluent to give compounds (1)–(3) with yields of 69, 67 and 59%, respectively (see Scheme 1).
To stirred and ice-bath-cooled methanolic solutions of the 1,4-epoxy cycloadducts were added zinc powder (10 mmol), glacial acetic acid (7 mmol) and hydrochloric acid (7 mmol, 37% HCl). The resulting mixtures were stirred at 273 K for an additional 30 min and the crude products were filtered. Each filtrate was then basified with 25% aqueous NH4OH to pH 8, extracted with EtOAc (3 × 50 ml), and the combined organic layers were dried over anhydrous Na2SO4. The solvent was removed under reduced pressure and the crude product was purified by column chromatography (silica gel, heptane–EtOAc, 10:1 to 1:1 v/v) to give the compounds (4) and (5) with yields of 93 and 90%, respectively (see Scheme 2).
The two groups of compounds described show different conformational and packing characteristics due to the size and position of substituents and the different conformations of the benzodiazepine nucleus (rigid in the epoxides and more flexible in the alcohols).
The non-enantioselective synthesis pathway (Gómez-Ayala et al., 2010; Acosta, Palma & Bahsas, 2010; OR Acosta, Palma, Bahsas et al., 2010) that produce racemic mixtures of the structural isomers (1), (2) and (3), however, they crystallize in different forms. Compound (1) crystallizes as a racemate in the space group P21/c, with Z' = 2, where the two molecules in the asymmetric unit were selected to have the same absolute configuration [(2S, 4R), as shown in Fig. 1]. Compund (2) crystallizes in the Schonke space group P212121, selecting the same (2S,4R) absolute configuration for the refinement (Fig. 2a), and compound (3) crystallizes in the Sohncke space group P21 and the crystal selected for structure determination was the (2S, 4R) enantiomer (Fig. 2b). This crystallization behaviour of slightly different isomers in different space groups with different crystalline symmetries has been described previously for this kind of compound (Acosta et al., 2008; Acosta, Palma, Bahsas et al., 2010).
The A conformer in (1) is conformationally identical to molecules (2) and (3), since the epoxybenzazepine nucleus is rather rigid, as shown by the overlay of the nuclei of (1A) and (2) with (3) (atoms N1, O1, C2, C3, C4, C5, C5A, C6, C7, C8, C9 and C9A), that give r.m.s. deviations of 0.0345 and 0.0249 Å, respectively. The dihedral angle between the naphthyl and benzyl rings are 88.14 (6), 87.66 (9) and 85.74 (6)° in (1A), (2) and (3), respectively, which indicates that the orthogonal conformation of the rings is the most stable for these molecules. Considering the conformation of the fused rings in the nuclei of the molecules (1A), (2) and (3), the five- (O1/N1/C2–C4) and six-membered (O1/N1/C9A/C5A/C5/C4) rings adopt an intermediate conformation between half-chair and envelope (Table 2) (Cremer & Pople, 1975).
The (1B) conformer in (1) shows a similar but not identical conformation of the epoxybenzazepine nucleus with respect to (1A) [r.m.s. deviation = 0.045 Å, larger than that of (1A) and (2) with (3)] with slightly different puckering parameters for the five- and six-memebred rings than those observed between (1A), (2) and (3) (Table 2). The main difference between (1B) and the other molecules is the dihedral angle between the naphthyl and benzyl rings of 4.26 (6)°, indicating that both rings are almost parallel and that molecule (1B) shows a relatively planar arrangement.
Even though the three compounds show different space groups, a motif of intermolecular interactions seems to be common to the three structures that form chains of molecules related by a 21 screw axis in the three cases along b. In the three compunds, weak C—H···O and C—H···π interactions direct the formation of chains (Tables 3, 4 and 5). In (1A), one C2A—H2A···O1Ai [symmetry code: (i) -x+1, y+1/2] and one C5A—H5AA···Cg1A2ii [Cg1A2 is the centroid of the C20A–C24A/C29A ring; symmetry code: (ii) -x+1, y-1/2, -z+1/2] interaction connect molecules related by a 21 screw axis (Fig. 3a), in (2), only one weak C82—H82···O1i [symmetry code: (i) -x+1, y+1/2, ???] hydrogen bond connects consecutive molecules (Fig. 3b), and in (3), one C8—H8···O1iii [symmetry code: (iii) x, y+1, z] and two C27—H27···Cg31iv and C28—H28···Cg32iv [Cg31 and Cg32 are the centroids of the C20–C24/C29 and C24–C29 rings, respectively; symmetry code: (iv) -x, y+1/2, -z+1] connect consecutive molecules (Fig. 3c), with additional C—H···π or van der Waals interactions connecting parallel chains. The case of compound (1) is more complex, though, since the crystal is centrosymmetric, therefore inverted chains of (1A) (2R,4S) enantiomers also run parallel to the b axis; furthermore, molecule (1B), with a different conformation, is also present. It is interesting, however, that molecules (1A) pack in separate layers from (1B) which form inversion dimers through C4B—H4B···O1Bv [symmetry code: (v) -x+2, -y, -z+1] and each molecule stacks with another inverted molecule along b (Fig. 3a). Chains of dimers, related by the c-glide plane have an parallel disposition of the planar benzyl and naphthyl ring that allows for C—H···π interactions.
Compounds (4) and (5) crystallize as racemates in the centrosymmetric Pbca and R3 space groups, respectively; both compounds were studied at room temperature and at 100 K. Compound (4) shows the same structure at both temperatures, but compound (5) shows a phase transition between room temperature, i.e. compound (5RT), and 100 K, i.e. compound (5LT), as will be described below.
For both compounds, the seven-membered ring adopts a chair conformation (Table 2) with the hydroxy, and styryl/pentenyl substituents [in (4) and (5)] in equatorial positions and the fluorobenzyl ring in a bisectional conformation, as shown in Fig. 4. Even though the seven-memebered ring of the tetrahydrobenzazepine nucleus has conformational freedom, all the independent molecules in (4), (5RT) and (5LT) show a very consistent conformation, with a maximum average r.m.s. deviation of 0.0794 Å of the common 7-fluorotetrahydrobenzazepine nucleus (atoms N1, O1, C2, C3, C4, C5, C52, C6, C7, C8, C9 and C92) between the molecule in (4) and molecule 3 of (5LT).
In the molecule of (4), the C22–C28 plane containing the styryl group is oriented towards the 7-fluorotetrahydrobenzazepine nucleus, making a dihedral angle of 60.99 (5)° (Fig. 4a). This general conformation is conserved at room temperature and 100 K. In this molecule, the styryl group is not completely planar since the C24—C23—C22—C21 torsion angle, which has a value of 168.68 (13)°, is slightly distorted considering that only Csp2 atoms are involved. The heterocyclic ring (atoms N1/C2–C5/C5A/C9A) in both compounds has similar puckering parameters values (Table 2) (Cremer & Pople, 1975).
Atoms of the pentenyl chain of the room-temperature structure of compound (5), denoted (5RT), exhibited high anisotropic displacement ellipsoids in the initial refinement cycles consistent with positional disorder in two different conformations of the same chain, slightly rotated along the C2—C10 bond, and were modelled as such (Fig. 4b). This positional disorder turned out to be very important when a new data collection was performed at 100 K, denoted (5LT), where it was observed that this disorder would correspond to the co-existence of various possible conformations of the pentenyl residue (Fig. 4c). The disorder in the room-temperature structure was refined successfully assuming two pentenyl chains in the same conformation with refined occupancies of 48.3 (5) and 51.7 (5)%, and an average C11—C12—C13—C14 torsion angle of -167.9° (Fig. 4b). However, the data at 100 K revealed that in fact it is possible to differentiate a new conformation as result of a rotation in the C12—C13 bond giving rise to a structure with a Z' value of 4. The four independent molecules in the asymmetric unit, each with different degree of disorder, are the result of the averaging of different proportions of two main different conformation of the pentenyl chain [with one of the conformations showing two possible torsion angles as in (5RT)]. In this sense, molecules 1 (2R,4S) and 2 (2S,4R) (see Fig. 4c) correspond to two ordered conformers, with torsion angles (C111—C112—C113—C114 and C211—C212—C213—C214) of -179.22 (14) and 72.11 (16)°, respectively (called conformers α and β in Fig. S1 of the Supporting information). Molecule 3 (2S,4R) shows disorder, similar to that of (5RT), successfully described as the co-existence of two chains with the same α conformation but in slightly different positions, with occupancies of 84.1 (2) and 15.9 (2)% and torsion angles of 176.06 (19) and 174.5 (11)°. Molecule 4 (2S,4R) represents a mixture of both α and β conformers, with two orientations of the former, with occupancies of 31.9 (8) and 34.0 (8)%, and an average torsion angle of ~176.5°, and a third one corresponding to the β conformer having an occupancy of 34.2 (3) and a torsion angle of 71.5 (6)° (see Fig. S1 in the Supporting information). The molecular connectivity in (5) (Tables 6 and 7) is quite different from that in (4). At room temperature, six molecules are connected by N1—H1N···O1i [symmetry code: (i) x-y+2/3, x+1/3, -z+4/3] [not in Table 6, but in Table 8 for compound (4)?] hydrogen bonds in a racemic ring parallel to (001), leaving the pentenyl substituents oriented to the centre and the F atoms oriented outward, describing a threefold rotoinversion axis with [001] direction (Fig. 5a). Each six-membered ring is connected to six other equivalent structures along the three dimensions connected by six pairs of N1—H1N···O1i and O1—H1O···N1ii [symmetry code: (ii) -y+2/3, x-y+1/3, z+1/3] [not in Table 6, but in Table 8 for compound (4)?] hydrogen bonds generating R44(8) motifs (Fig. 5b). Each pair of enantiomers are also related by an inversion centre at (1/2, 1/2, 1/2) and connected between them by probably induced dipolar interactions involving the halogen substituent. In a supramolecular perspective, a view along [001] allows one to differentiate the centre of the rings at (2/3, 1/3, z) and (1/3, 2/3, z) (Fig. 5a). The structure at 100 K is transformed in a superstructure of the crystal structure at room temperature since the conformers (see Fig. S1 in the Supporting information) are perceptibly different. In this case, the molecular connectivity remains as room temperature and each individual molecule in the asymmetric unit constitutes a racemic sixfold molecular ring by N(1,2,3,4)1—H(1,2,3,4)N···O(3i,1ii,2iii,4iv)1 [symmetry codes: (i) x, y, z+1; (ii) -y+2/3, x-y+1/3, z-2/3; (iii) x-y+2/3, x+1/3, -z+1/3; (iv) y-1/3, -x+y+1/3, -z+4/3] hydrogen bonds (Table 7). However, the presence of both α and β conformers break half of the threefold rotoinversion axes observed at room temperature leaving a threefold screw axis with [001] direction in the centre of each molecular ring (Fig. 5c).
The supramolecular assembly of both molecules in their crystals differ significantly, as expected for the very different sizes of the styryl and pentenyl substituents. In compound (4), each molecule is connected to four equivalent molecules at the same z value by two pairs of N1—H1N···O1i and O1—H1O···N1ii [symmetry codes: (i) x, y-1, z; (ii) -x+3/2, y+1/2, z] hydrogen bonds (Table 8), where atoms N1 and O1 act each as donor and acceptor. Hydrogen-bonded molecules form enantiomorphic chains along the [010] direction (Fig. 6). The chains have a polar disposition, since all molecules in a chain are related by the b-glide plane normal to a (Fig. 6a). This makes the F atoms from all the molecules lie on the same side of the chain, leaving all nonpolar moieties on the other side. Each chain connects with an inverted chain on the [001] direction through weak C6—H6···F1iii [symmetry code: (iii) -x+1, -y+1, -z+1] dipolar interactions (2.47 Å) (Jelsch et al., 2015) (Figs. 6b and 6c). The interactions among double chains in the [100] and [001] directions are weak and probably dipolar or van der Waals in nature since no weak hydrogen bonds or π–π stacking interactions are detected.
Compund (5) shows different structures at room temperature and 100 K, with the low-temperature structure crystallizing in a klassengleiche subgroup of the room-temperature one, with a quadrupling of the unit-cell volume in the (110) plane. The descriptions of (5LT) could be obtained from that of (5RT) by the matrix P = [200 220 001] (International Tables for Crystallography, 2011). In order to confirm the group/subgroup relation of both structures and determine the degree of distortion of one respect to the other, the ordered part of the molecule in the (5RT) crystal was transformed into the subgroup of (5LT) using TRANSTRU program in the Bilbao Crystallography Server (Aroyo, Kirov et al., 2006; Aroyo, Perez-Mato et al., 2006; Aroyo et al., 2011) and the output structure, consisting of the ordered nuclei of the molecules was compared with the same nuclei in the (5LT) structure (all pentenyl residues, ordered and disordered, were removed) using COMPSTRU (Tasci et al., 2012) and an almost perfect overlap was obtained with an average/maximum atom displacement of 0.1667/0.2539 Å (for atom F1A). These deviations are very small considering the temperature difference and the fact that the room-temperature structure shows one molecule with the pentenyl chain split in two main positions, while the 100 K structure shows four independent molecules, two of them ordered and the other two displaying two and three different pentenyl chain conformations. This strongly suggests that the phase transition observed between room temperature and 100 K could be entirely explained by the partial ordering of the pentenly chains in half of the molecules, that breaks half of the 3 symmetry axes of the room-temperature structure on cooling. The refinement of the 100 K structure using the room-temperature model (R3 space group with halved a and b unit-cell parameters) using hkl data transformed using the inverse of the matrix above, provides a reasonable but significantly poorer model, with unreasonable displacement parameters (too high for a low-temperature model), a higher R factor and a much larger degree of disorder of the pentenyl chain that is very hard to model with less than three separate conformations. This clearly justifies the use of the subgroup to model the 100 K structure and again confirm that the ordering of the pentenyl chains is key to this phase transition.
The syntheses of the compounds (1)–(5) were carried out following our previously estabished experimental conditions (Acosta, Palma & Bahsas, 2010; Acosta et al., 2012). Particular details are described as follows. Recrystallization of (1)–(3) by slow evaporation of a solution in heptane gave crystals of suitable size and quality for single-crystal X-ray diffraction. In the case of compounds (4) and (5), the recrystallization was performed from a heptane–ethyl acetate (1:1 v/v) mixture which also gave crystals suitable for single-crystal X-ray diffraction.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in calculated positions (C—H = 0.93–1.00 Å) and included as riding contributions with isotropic displacement parameters set at 1.2-1.5 times of the Ueq value of the parent atom. H atoms belonging to OH and NH groups were located in difference density maps and refined freely. Some low-angle reflections strongly affected by the experiment, attenuated by the beam stop, for instance, were omitted for the final refinements, viz. for (1) 366 and 366, for (2) 011 and for (5) 120.
For all compounds, data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006). Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for Compound_1, Compound_2, Compound_4; SUPERFLIP (Palatinus & Chapuis, 2007) for Compound_3, Compound_5a, Compound_5b. Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) for Compound_1, Compound_3, Compound_4, Compound_5a, Compound_5b; SHELXL2014 (Sheldrick, 2008a, 2015b) for Compound_2. For all compounds, molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).
C22H21NO | F(000) = 1344 |
Mr = 315.40 | Dx = 1.300 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 24.8049 (10) Å | Cell parameters from 9740 reflections |
b = 10.7126 (5) Å | θ = 2.5–27.4° |
c = 12.1932 (4) Å | µ = 0.08 mm−1 |
β = 95.929 (1)° | T = 100 K |
V = 3222.7 (2) Å3 | Parallelipiped, less |
Z = 8 | 0.45 × 0.35 × 0.20 mm |
Bruker Kappa APEXII diffractometer | 6012 reflections with I > 2σ(I) |
π and ω scans | Rint = 0.040 |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | θmax = 27.5°, θmin = 2.1° |
Tmin = 0.640, Tmax = 0.746 | h = −32→29 |
48596 measured reflections | k = −12→13 |
7121 independent reflections | l = −11→15 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.0523P)2 + 2.1093P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
7121 reflections | Δρmax = 0.37 e Å−3 |
437 parameters | Δρmin = −0.26 e Å−3 |
C22H21NO | V = 3222.7 (2) Å3 |
Mr = 315.40 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 24.8049 (10) Å | µ = 0.08 mm−1 |
b = 10.7126 (5) Å | T = 100 K |
c = 12.1932 (4) Å | 0.45 × 0.35 × 0.20 mm |
β = 95.929 (1)° |
Bruker Kappa APEXII diffractometer | 7121 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 6012 reflections with I > 2σ(I) |
Tmin = 0.640, Tmax = 0.746 | Rint = 0.040 |
48596 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.37 e Å−3 |
7121 reflections | Δρmin = −0.26 e Å−3 |
437 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C28B | 0.90602 (6) | 0.47577 (14) | 0.66839 (12) | 0.0197 (3) | |
H28B | 0.9428 | 0.4893 | 0.6563 | 0.024* | |
C21B | 0.86514 (6) | 0.22394 (14) | 0.46455 (12) | 0.0209 (3) | |
H21B | 0.8796 | 0.1749 | 0.4096 | 0.025* | |
C22B | 0.81091 (6) | 0.20496 (15) | 0.48594 (12) | 0.0235 (3) | |
H22B | 0.7895 | 0.1438 | 0.4453 | 0.028* | |
C23B | 0.78897 (6) | 0.27362 (15) | 0.56446 (12) | 0.0219 (3) | |
H23B | 0.7524 | 0.2600 | 0.5782 | 0.026* | |
C27B | 0.88377 (6) | 0.54502 (15) | 0.74688 (12) | 0.0230 (3) | |
H27B | 0.9051 | 0.6056 | 0.7883 | 0.028* | |
C26B | 0.82940 (6) | 0.52654 (15) | 0.76618 (12) | 0.0239 (3) | |
H26B | 0.8141 | 0.5750 | 0.8204 | 0.029* | |
C25B | 0.79852 (6) | 0.43897 (15) | 0.70720 (12) | 0.0224 (3) | |
H25B | 0.7619 | 0.4271 | 0.7209 | 0.027* | |
C24B | 0.82058 (6) | 0.36549 (14) | 0.62571 (11) | 0.0193 (3) | |
C29B | 0.87542 (6) | 0.38444 (13) | 0.60482 (11) | 0.0178 (3) | |
C20B | 0.89752 (6) | 0.31156 (13) | 0.52118 (11) | 0.0172 (3) | |
C21A | 0.40742 (6) | 0.75903 (14) | 0.28172 (11) | 0.0183 (3) | |
H21A | 0.4300 | 0.7129 | 0.3349 | 0.022* | |
C22A | 0.35143 (6) | 0.76661 (14) | 0.29133 (12) | 0.0200 (3) | |
H22A | 0.3367 | 0.7245 | 0.3500 | 0.024* | |
C23A | 0.31807 (6) | 0.83392 (14) | 0.21706 (12) | 0.0190 (3) | |
H23A | 0.2804 | 0.8390 | 0.2247 | 0.023* | |
C24A | 0.33970 (6) | 0.89639 (13) | 0.12832 (11) | 0.0171 (3) | |
C25A | 0.30620 (6) | 0.96909 (14) | 0.05136 (12) | 0.0201 (3) | |
H25A | 0.2686 | 0.9765 | 0.0592 | 0.024* | |
C26A | 0.32723 (6) | 1.02862 (14) | −0.03388 (12) | 0.0219 (3) | |
H26A | 0.3043 | 1.0771 | −0.0845 | 0.026* | |
C27A | 0.38279 (6) | 1.01832 (14) | −0.04672 (12) | 0.0208 (3) | |
H27A | 0.3971 | 1.0590 | −0.1066 | 0.025* | |
C28A | 0.41652 (6) | 0.94975 (14) | 0.02680 (11) | 0.0179 (3) | |
H28A | 0.4540 | 0.9440 | 0.0173 | 0.021* | |
C29A | 0.39618 (6) | 0.88722 (13) | 0.11701 (11) | 0.0158 (3) | |
C20A | 0.43018 (6) | 0.81698 (13) | 0.19693 (11) | 0.0158 (3) | |
N1A | 0.52000 (5) | 0.75543 (11) | 0.28857 (9) | 0.0164 (3) | |
O1A | 0.51701 (4) | 0.62248 (9) | 0.26606 (8) | 0.0186 (2) | |
C2A | 0.49058 (6) | 0.80977 (13) | 0.18739 (11) | 0.0157 (3) | |
H2A | 0.5048 | 0.8954 | 0.1751 | 0.019* | |
C3A | 0.50543 (6) | 0.72134 (14) | 0.09308 (11) | 0.0185 (3) | |
H3AA | 0.4725 | 0.6922 | 0.0474 | 0.022* | |
H3AB | 0.5296 | 0.7636 | 0.0451 | 0.022* | |
C4A | 0.53460 (6) | 0.61237 (14) | 0.15643 (11) | 0.0190 (3) | |
H4A | 0.5226 | 0.5309 | 0.1220 | 0.023* | |
C5A | 0.59618 (6) | 0.62154 (14) | 0.16806 (11) | 0.0190 (3) | |
H5AA | 0.6121 | 0.5416 | 0.1965 | 0.023* | |
H5AB | 0.6089 | 0.6374 | 0.0949 | 0.023* | |
C6A | 0.66938 (6) | 0.76068 (14) | 0.26448 (11) | 0.0185 (3) | |
C7A | 0.68360 (6) | 0.86332 (15) | 0.33189 (12) | 0.0207 (3) | |
H7A | 0.7207 | 0.8867 | 0.3444 | 0.025* | |
C8A | 0.64515 (6) | 0.93285 (14) | 0.38160 (11) | 0.0199 (3) | |
C9A | 0.59144 (6) | 0.89464 (14) | 0.36574 (11) | 0.0184 (3) | |
H9A | 0.5646 | 0.9391 | 0.4001 | 0.022* | |
N1B | 0.99146 (5) | 0.27205 (11) | 0.59408 (9) | 0.0168 (3) | |
O1B | 0.99060 (4) | 0.14348 (9) | 0.55752 (8) | 0.0201 (2) | |
C2B | 0.95622 (6) | 0.33158 (13) | 0.50117 (11) | 0.0167 (3) | |
H2B | 0.9640 | 0.4231 | 0.4996 | 0.020* | |
C3B | 0.97530 (6) | 0.26920 (14) | 0.39758 (11) | 0.0187 (3) | |
H3BA | 0.9441 | 0.2473 | 0.3437 | 0.022* | |
H3BB | 1.0001 | 0.3246 | 0.3615 | 0.022* | |
C4B | 1.00495 (6) | 0.15132 (14) | 0.44408 (11) | 0.0203 (3) | |
H4B | 0.9923 | 0.0757 | 0.4008 | 0.024* | |
C5B | 1.06598 (6) | 0.16314 (15) | 0.45203 (12) | 0.0221 (3) | |
H5BA | 1.0773 | 0.1847 | 0.3789 | 0.027* | |
H5BB | 1.0829 | 0.0826 | 0.4756 | 0.027* | |
C6B | 1.13816 (6) | 0.30607 (15) | 0.54831 (12) | 0.0227 (3) | |
C7B | 1.15254 (6) | 0.40022 (16) | 0.62457 (12) | 0.0242 (3) | |
H7B | 1.1890 | 0.4285 | 0.6336 | 0.029* | |
C8B | 1.11508 (6) | 0.45440 (15) | 0.68815 (12) | 0.0227 (3) | |
C9B | 1.06216 (6) | 0.41094 (14) | 0.67492 (11) | 0.0193 (3) | |
H9B | 1.0360 | 0.4459 | 0.7177 | 0.023* | |
C5A2 | 0.61473 (6) | 0.72585 (14) | 0.24602 (11) | 0.0170 (3) | |
C6A2 | 0.71170 (6) | 0.69000 (15) | 0.20949 (13) | 0.0243 (3) | |
H6AA | 0.7475 | 0.7256 | 0.2320 | 0.036* | |
H6AB | 0.7038 | 0.6964 | 0.1293 | 0.036* | |
H6AC | 0.7113 | 0.6020 | 0.2315 | 0.036* | |
C8A2 | 0.66182 (7) | 1.04589 (15) | 0.45163 (13) | 0.0249 (3) | |
H8AA | 0.6303 | 1.0782 | 0.4849 | 0.037* | |
H8AB | 0.6758 | 1.1106 | 0.4053 | 0.037* | |
H8AC | 0.6901 | 1.0220 | 0.5099 | 0.037* | |
C9A2 | 0.57655 (6) | 0.79158 (14) | 0.29984 (11) | 0.0166 (3) | |
C5B2 | 1.08444 (6) | 0.26388 (14) | 0.53455 (11) | 0.0193 (3) | |
C6B2 | 1.17984 (7) | 0.25149 (18) | 0.48023 (13) | 0.0305 (4) | |
H6BA | 1.1802 | 0.1604 | 0.4879 | 0.046* | |
H6BB | 1.2157 | 0.2848 | 0.5060 | 0.046* | |
H6BC | 1.1707 | 0.2738 | 0.4026 | 0.046* | |
C8B2 | 1.13274 (7) | 0.55414 (16) | 0.77154 (13) | 0.0310 (4) | |
H8BA | 1.1487 | 0.6241 | 0.7344 | 0.046* | |
H8BB | 1.1597 | 0.5195 | 0.8278 | 0.046* | |
H8BC | 1.1013 | 0.5836 | 0.8066 | 0.046* | |
C9B2 | 1.04695 (6) | 0.31645 (13) | 0.59952 (11) | 0.0170 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C28B | 0.0206 (7) | 0.0186 (8) | 0.0196 (7) | 0.0005 (6) | 0.0012 (5) | 0.0010 (5) |
C21B | 0.0265 (8) | 0.0190 (8) | 0.0173 (7) | −0.0007 (6) | 0.0023 (6) | −0.0015 (5) |
C22B | 0.0253 (8) | 0.0220 (8) | 0.0224 (7) | −0.0053 (6) | −0.0018 (6) | −0.0007 (6) |
C23B | 0.0196 (7) | 0.0234 (8) | 0.0224 (7) | −0.0019 (6) | 0.0008 (6) | 0.0036 (6) |
C27B | 0.0290 (8) | 0.0201 (8) | 0.0196 (7) | 0.0013 (6) | 0.0001 (6) | −0.0027 (6) |
C26B | 0.0297 (8) | 0.0230 (8) | 0.0191 (7) | 0.0072 (6) | 0.0033 (6) | −0.0009 (6) |
C25B | 0.0226 (8) | 0.0256 (8) | 0.0191 (7) | 0.0041 (6) | 0.0029 (6) | 0.0034 (6) |
C24B | 0.0219 (7) | 0.0184 (7) | 0.0170 (6) | 0.0022 (6) | −0.0005 (5) | 0.0042 (5) |
C29B | 0.0223 (7) | 0.0152 (7) | 0.0154 (6) | 0.0010 (6) | −0.0002 (5) | 0.0036 (5) |
C20B | 0.0219 (7) | 0.0140 (7) | 0.0155 (6) | 0.0006 (6) | 0.0009 (5) | 0.0026 (5) |
C21A | 0.0218 (7) | 0.0175 (7) | 0.0152 (6) | 0.0009 (6) | 0.0003 (5) | 0.0015 (5) |
C22A | 0.0234 (8) | 0.0199 (8) | 0.0174 (7) | −0.0024 (6) | 0.0054 (5) | 0.0007 (6) |
C23A | 0.0164 (7) | 0.0199 (8) | 0.0212 (7) | −0.0011 (6) | 0.0044 (5) | −0.0030 (6) |
C24A | 0.0214 (7) | 0.0130 (7) | 0.0166 (6) | −0.0008 (5) | 0.0004 (5) | −0.0046 (5) |
C25A | 0.0197 (7) | 0.0185 (8) | 0.0214 (7) | 0.0020 (6) | −0.0007 (5) | −0.0037 (6) |
C26A | 0.0267 (8) | 0.0180 (8) | 0.0197 (7) | 0.0034 (6) | −0.0044 (6) | 0.0004 (6) |
C27A | 0.0272 (8) | 0.0178 (7) | 0.0170 (7) | −0.0018 (6) | 0.0003 (6) | 0.0025 (5) |
C28A | 0.0200 (7) | 0.0171 (7) | 0.0164 (6) | −0.0014 (6) | 0.0011 (5) | −0.0005 (5) |
C29A | 0.0204 (7) | 0.0125 (7) | 0.0141 (6) | −0.0012 (5) | 0.0003 (5) | −0.0023 (5) |
C20A | 0.0197 (7) | 0.0133 (7) | 0.0142 (6) | −0.0012 (5) | 0.0008 (5) | −0.0020 (5) |
N1A | 0.0197 (6) | 0.0146 (6) | 0.0147 (5) | 0.0001 (5) | −0.0001 (4) | 0.0015 (4) |
O1A | 0.0239 (5) | 0.0145 (5) | 0.0177 (5) | −0.0011 (4) | 0.0031 (4) | 0.0021 (4) |
C2A | 0.0198 (7) | 0.0155 (7) | 0.0116 (6) | −0.0008 (5) | 0.0005 (5) | 0.0019 (5) |
C3A | 0.0198 (7) | 0.0212 (8) | 0.0144 (6) | 0.0018 (6) | 0.0012 (5) | −0.0003 (5) |
C4A | 0.0233 (8) | 0.0173 (7) | 0.0161 (7) | −0.0004 (6) | 0.0015 (5) | −0.0010 (5) |
C5A | 0.0220 (8) | 0.0174 (7) | 0.0176 (7) | 0.0025 (6) | 0.0024 (5) | 0.0018 (5) |
C6A | 0.0200 (7) | 0.0190 (7) | 0.0166 (6) | 0.0017 (6) | 0.0014 (5) | 0.0076 (5) |
C7A | 0.0173 (7) | 0.0242 (8) | 0.0200 (7) | −0.0035 (6) | −0.0006 (5) | 0.0067 (6) |
C8A | 0.0245 (8) | 0.0204 (8) | 0.0140 (6) | −0.0019 (6) | −0.0011 (5) | 0.0034 (5) |
C9A | 0.0219 (7) | 0.0214 (8) | 0.0119 (6) | 0.0021 (6) | 0.0015 (5) | 0.0021 (5) |
N1B | 0.0231 (6) | 0.0115 (6) | 0.0157 (6) | 0.0002 (5) | 0.0021 (5) | 0.0004 (4) |
O1B | 0.0302 (6) | 0.0125 (5) | 0.0182 (5) | −0.0009 (4) | 0.0051 (4) | 0.0005 (4) |
C2B | 0.0225 (7) | 0.0142 (7) | 0.0133 (6) | −0.0005 (6) | 0.0006 (5) | 0.0010 (5) |
C3B | 0.0226 (7) | 0.0183 (7) | 0.0154 (6) | −0.0017 (6) | 0.0029 (5) | −0.0009 (5) |
C4B | 0.0311 (8) | 0.0155 (7) | 0.0148 (6) | −0.0004 (6) | 0.0041 (6) | −0.0027 (5) |
C5B | 0.0294 (8) | 0.0200 (8) | 0.0176 (7) | 0.0050 (6) | 0.0053 (6) | −0.0012 (6) |
C6B | 0.0239 (8) | 0.0275 (9) | 0.0166 (7) | 0.0028 (6) | 0.0022 (6) | 0.0088 (6) |
C7B | 0.0223 (8) | 0.0285 (9) | 0.0210 (7) | −0.0040 (6) | −0.0024 (6) | 0.0085 (6) |
C8B | 0.0298 (8) | 0.0210 (8) | 0.0158 (7) | −0.0030 (6) | −0.0044 (6) | 0.0054 (6) |
C9B | 0.0265 (8) | 0.0183 (8) | 0.0127 (6) | 0.0028 (6) | 0.0005 (5) | 0.0028 (5) |
C5A2 | 0.0203 (7) | 0.0174 (7) | 0.0132 (6) | 0.0009 (6) | 0.0011 (5) | 0.0050 (5) |
C6A2 | 0.0194 (8) | 0.0244 (8) | 0.0294 (8) | 0.0019 (6) | 0.0046 (6) | 0.0050 (6) |
C8A2 | 0.0280 (8) | 0.0229 (8) | 0.0227 (7) | −0.0052 (6) | −0.0023 (6) | 0.0008 (6) |
C9A2 | 0.0186 (7) | 0.0197 (7) | 0.0114 (6) | −0.0003 (6) | −0.0001 (5) | 0.0052 (5) |
C5B2 | 0.0251 (8) | 0.0184 (8) | 0.0144 (6) | 0.0023 (6) | 0.0019 (5) | 0.0039 (5) |
C6B2 | 0.0241 (8) | 0.0430 (11) | 0.0249 (8) | 0.0051 (7) | 0.0054 (6) | 0.0081 (7) |
C8B2 | 0.0384 (10) | 0.0273 (9) | 0.0247 (8) | −0.0075 (7) | −0.0091 (7) | 0.0005 (7) |
C9B2 | 0.0222 (7) | 0.0157 (7) | 0.0128 (6) | 0.0011 (6) | 0.0001 (5) | 0.0043 (5) |
C28B—C27B | 1.371 (2) | C2A—C3A | 1.5629 (19) |
C28B—C29B | 1.419 (2) | C3A—C4A | 1.539 (2) |
C21B—C20B | 1.374 (2) | C4A—C5A | 1.523 (2) |
C21B—C22B | 1.411 (2) | C5A—C5A2 | 1.508 (2) |
C22B—C23B | 1.364 (2) | C6A—C7A | 1.396 (2) |
C23B—C24B | 1.421 (2) | C6A—C5A2 | 1.402 (2) |
C27B—C26B | 1.407 (2) | C6A—C6A2 | 1.507 (2) |
C26B—C25B | 1.367 (2) | C7A—C8A | 1.397 (2) |
C25B—C24B | 1.421 (2) | C8A—C9A | 1.388 (2) |
C24B—C29B | 1.424 (2) | C8A—C8A2 | 1.514 (2) |
C29B—C20B | 1.437 (2) | C9A—C9A2 | 1.393 (2) |
C20B—C2B | 1.516 (2) | N1B—O1B | 1.4471 (15) |
C21A—C20A | 1.376 (2) | N1B—C9B2 | 1.4513 (18) |
C21A—C22A | 1.408 (2) | N1B—C2B | 1.4998 (17) |
C22A—C23A | 1.367 (2) | O1B—C4B | 1.4658 (16) |
C23A—C24A | 1.424 (2) | C2B—C3B | 1.5459 (19) |
C24A—C25A | 1.420 (2) | C3B—C4B | 1.540 (2) |
C24A—C29A | 1.425 (2) | C4B—C5B | 1.512 (2) |
C25A—C26A | 1.368 (2) | C5B—C5B2 | 1.514 (2) |
C26A—C27A | 1.407 (2) | C6B—C7B | 1.393 (2) |
C27A—C28A | 1.374 (2) | C6B—C5B2 | 1.401 (2) |
C28A—C29A | 1.4240 (19) | C6B—C6B2 | 1.509 (2) |
C29A—C20A | 1.4343 (19) | C7B—C8B | 1.397 (2) |
C20A—C2A | 1.517 (2) | C8B—C9B | 1.386 (2) |
N1A—C9A2 | 1.4480 (18) | C8B—C8B2 | 1.508 (2) |
N1A—O1A | 1.4509 (16) | C9B—C9B2 | 1.393 (2) |
N1A—C2A | 1.4858 (16) | C5A2—C9A2 | 1.397 (2) |
O1A—C4A | 1.4525 (17) | C5B2—C9B2 | 1.401 (2) |
C27B—C28B—C29B | 121.56 (14) | C5A—C4A—C3A | 114.40 (12) |
C20B—C21B—C22B | 121.63 (14) | C5A2—C5A—C4A | 110.14 (12) |
C23B—C22B—C21B | 120.60 (14) | C7A—C6A—C5A2 | 119.05 (14) |
C22B—C23B—C24B | 120.24 (14) | C7A—C6A—C6A2 | 120.83 (13) |
C28B—C27B—C26B | 120.17 (14) | C5A2—C6A—C6A2 | 120.10 (14) |
C25B—C26B—C27B | 120.21 (14) | C6A—C7A—C8A | 122.21 (14) |
C26B—C25B—C24B | 120.84 (14) | C9A—C8A—C7A | 118.09 (14) |
C25B—C24B—C23B | 121.32 (14) | C9A—C8A—C8A2 | 121.10 (14) |
C25B—C24B—C29B | 119.34 (14) | C7A—C8A—C8A2 | 120.80 (14) |
C23B—C24B—C29B | 119.34 (13) | C8A—C9A—C9A2 | 120.51 (14) |
C28B—C29B—C24B | 117.88 (13) | O1B—N1B—C9B2 | 108.04 (11) |
C28B—C29B—C20B | 122.73 (13) | O1B—N1B—C2B | 100.56 (10) |
C24B—C29B—C20B | 119.39 (13) | C9B2—N1B—C2B | 111.79 (11) |
C21B—C20B—C29B | 118.80 (13) | N1B—O1B—C4B | 103.82 (10) |
C21B—C20B—C2B | 122.47 (13) | N1B—C2B—C20B | 108.23 (11) |
C29B—C20B—C2B | 118.71 (12) | N1B—C2B—C3B | 103.27 (11) |
C20A—C21A—C22A | 121.42 (13) | C20B—C2B—C3B | 116.78 (12) |
C23A—C22A—C21A | 120.65 (13) | C4B—C3B—C2B | 103.21 (11) |
C22A—C23A—C24A | 120.10 (13) | O1B—C4B—C5B | 106.46 (11) |
C25A—C24A—C23A | 121.29 (13) | O1B—C4B—C3B | 103.96 (11) |
C25A—C24A—C29A | 119.20 (13) | C5B—C4B—C3B | 113.07 (12) |
C23A—C24A—C29A | 119.50 (13) | C4B—C5B—C5B2 | 109.53 (12) |
C26A—C25A—C24A | 120.98 (14) | C7B—C6B—C5B2 | 119.24 (14) |
C25A—C26A—C27A | 120.18 (13) | C7B—C6B—C6B2 | 120.32 (15) |
C28A—C27A—C26A | 120.43 (14) | C5B2—C6B—C6B2 | 120.43 (15) |
C27A—C28A—C29A | 121.00 (14) | C6B—C7B—C8B | 122.15 (14) |
C28A—C29A—C24A | 118.20 (12) | C9B—C8B—C7B | 118.17 (14) |
C28A—C29A—C20A | 122.77 (13) | C9B—C8B—C8B2 | 121.45 (15) |
C24A—C29A—C20A | 119.03 (13) | C7B—C8B—C8B2 | 120.34 (15) |
C21A—C20A—C29A | 119.28 (13) | C8B—C9B—C9B2 | 120.63 (14) |
C21A—C20A—C2A | 121.32 (12) | C9A2—C5A2—C6A | 118.79 (13) |
C29A—C20A—C2A | 119.39 (12) | C9A2—C5A2—C5A | 119.49 (13) |
C9A2—N1A—O1A | 108.10 (11) | C6A—C5A2—C5A | 121.70 (13) |
C9A2—N1A—C2A | 111.22 (11) | C9A—C9A2—C5A2 | 121.22 (13) |
O1A—N1A—C2A | 102.50 (10) | C9A—C9A2—N1A | 117.60 (13) |
N1A—O1A—C4A | 103.47 (10) | C5A2—C9A2—N1A | 121.17 (13) |
N1A—C2A—C20A | 111.14 (11) | C6B—C5B2—C9B2 | 118.79 (14) |
N1A—C2A—C3A | 103.92 (11) | C6B—C5B2—C5B | 121.89 (14) |
C20A—C2A—C3A | 113.39 (11) | C9B2—C5B2—C5B | 119.31 (13) |
C4A—C3A—C2A | 102.99 (11) | C9B—C9B2—C5B2 | 120.99 (14) |
O1A—C4A—C5A | 107.67 (11) | C9B—C9B2—N1B | 117.34 (13) |
O1A—C4A—C3A | 103.59 (11) | C5B2—C9B2—N1B | 121.63 (13) |
C20B—C21B—C22B—C23B | −0.2 (2) | C6A2—C6A—C7A—C8A | 178.20 (13) |
C21B—C22B—C23B—C24B | 0.1 (2) | C6A—C7A—C8A—C9A | 2.3 (2) |
C29B—C28B—C27B—C26B | 0.0 (2) | C6A—C7A—C8A—C8A2 | −178.25 (13) |
C28B—C27B—C26B—C25B | 0.4 (2) | C7A—C8A—C9A—C9A2 | −1.5 (2) |
C27B—C26B—C25B—C24B | −0.1 (2) | C8A2—C8A—C9A—C9A2 | 179.07 (13) |
C26B—C25B—C24B—C23B | 179.56 (14) | C9B2—N1B—O1B—C4B | −66.29 (12) |
C26B—C25B—C24B—C29B | −0.6 (2) | C2B—N1B—O1B—C4B | 50.95 (12) |
C22B—C23B—C24B—C25B | 179.42 (14) | O1B—N1B—C2B—C20B | 82.23 (12) |
C22B—C23B—C24B—C29B | −0.4 (2) | C9B2—N1B—C2B—C20B | −163.33 (11) |
C27B—C28B—C29B—C24B | −0.6 (2) | O1B—N1B—C2B—C3B | −42.17 (12) |
C27B—C28B—C29B—C20B | 179.27 (14) | C9B2—N1B—C2B—C3B | 72.27 (13) |
C25B—C24B—C29B—C28B | 0.9 (2) | C21B—C20B—C2B—N1B | −103.42 (15) |
C23B—C24B—C29B—C28B | −179.22 (13) | C29B—C20B—C2B—N1B | 74.69 (15) |
C25B—C24B—C29B—C20B | −179.01 (13) | C21B—C20B—C2B—C3B | 12.5 (2) |
C23B—C24B—C29B—C20B | 0.9 (2) | C29B—C20B—C2B—C3B | −169.40 (12) |
C22B—C21B—C20B—C29B | 0.6 (2) | N1B—C2B—C3B—C4B | 18.56 (14) |
C22B—C21B—C20B—C2B | 178.69 (13) | C20B—C2B—C3B—C4B | −100.06 (14) |
C28B—C29B—C20B—C21B | 179.16 (13) | N1B—O1B—C4B—C5B | 80.74 (13) |
C24B—C29B—C20B—C21B | −0.9 (2) | N1B—O1B—C4B—C3B | −38.89 (13) |
C28B—C29B—C20B—C2B | 1.0 (2) | C2B—C3B—C4B—O1B | 11.42 (14) |
C24B—C29B—C20B—C2B | −179.11 (12) | C2B—C3B—C4B—C5B | −103.62 (13) |
C20A—C21A—C22A—C23A | −1.0 (2) | O1B—C4B—C5B—C5B2 | −48.84 (15) |
C21A—C22A—C23A—C24A | 0.5 (2) | C3B—C4B—C5B—C5B2 | 64.69 (15) |
C22A—C23A—C24A—C25A | −178.65 (14) | C5B2—C6B—C7B—C8B | 0.0 (2) |
C22A—C23A—C24A—C29A | 0.6 (2) | C6B2—C6B—C7B—C8B | 179.14 (14) |
C23A—C24A—C25A—C26A | −179.84 (14) | C6B—C7B—C8B—C9B | 0.8 (2) |
C29A—C24A—C25A—C26A | 0.9 (2) | C6B—C7B—C8B—C8B2 | 178.66 (14) |
C24A—C25A—C26A—C27A | 0.1 (2) | C7B—C8B—C9B—C9B2 | −0.5 (2) |
C25A—C26A—C27A—C28A | −0.8 (2) | C8B2—C8B—C9B—C9B2 | −178.30 (13) |
C26A—C27A—C28A—C29A | 0.3 (2) | C7A—C6A—C5A2—C9A2 | −2.9 (2) |
C27A—C28A—C29A—C24A | 0.7 (2) | C6A2—C6A—C5A2—C9A2 | 178.76 (13) |
C27A—C28A—C29A—C20A | −178.61 (13) | C7A—C6A—C5A2—C5A | 175.77 (13) |
C25A—C24A—C29A—C28A | −1.35 (19) | C6A2—C6A—C5A2—C5A | −2.5 (2) |
C23A—C24A—C29A—C28A | 179.40 (13) | C4A—C5A—C5A2—C9A2 | 3.82 (17) |
C25A—C24A—C29A—C20A | 178.03 (12) | C4A—C5A—C5A2—C6A | −174.86 (12) |
C23A—C24A—C29A—C20A | −1.22 (19) | C8A—C9A—C9A2—C5A2 | −1.5 (2) |
C22A—C21A—C20A—C29A | 0.4 (2) | C8A—C9A—C9A2—N1A | 178.84 (12) |
C22A—C21A—C20A—C2A | 179.38 (13) | C6A—C5A2—C9A2—C9A | 3.8 (2) |
C28A—C29A—C20A—C21A | −179.91 (13) | C5A—C5A2—C9A2—C9A | −174.96 (12) |
C24A—C29A—C20A—C21A | 0.7 (2) | C6A—C5A2—C9A2—N1A | −176.61 (12) |
C28A—C29A—C20A—C2A | 1.1 (2) | C5A—C5A2—C9A2—N1A | 4.67 (19) |
C24A—C29A—C20A—C2A | −178.28 (12) | O1A—N1A—C9A2—C9A | −152.72 (11) |
C9A2—N1A—O1A—C4A | −68.06 (12) | C2A—N1A—C9A2—C9A | 95.49 (14) |
C2A—N1A—O1A—C4A | 49.48 (12) | O1A—N1A—C9A2—C5A2 | 27.63 (16) |
C9A2—N1A—C2A—C20A | −157.54 (12) | C2A—N1A—C9A2—C5A2 | −84.15 (15) |
O1A—N1A—C2A—C20A | 87.16 (12) | C7B—C6B—C5B2—C9B2 | −1.1 (2) |
C9A2—N1A—C2A—C3A | 80.15 (13) | C6B2—C6B—C5B2—C9B2 | 179.77 (13) |
O1A—N1A—C2A—C3A | −35.15 (13) | C7B—C6B—C5B2—C5B | 179.15 (13) |
C21A—C20A—C2A—N1A | −10.41 (18) | C6B2—C6B—C5B2—C5B | 0.0 (2) |
C29A—C20A—C2A—N1A | 168.59 (12) | C4B—C5B—C5B2—C6B | −171.67 (13) |
C21A—C20A—C2A—C3A | 106.23 (15) | C4B—C5B—C5B2—C9B2 | 8.55 (18) |
C29A—C20A—C2A—C3A | −74.77 (16) | C8B—C9B—C9B2—C5B2 | −0.6 (2) |
N1A—C2A—C3A—C4A | 9.28 (14) | C8B—C9B—C9B2—N1B | 177.22 (12) |
C20A—C2A—C3A—C4A | −111.52 (12) | C6B—C5B2—C9B2—C9B | 1.4 (2) |
N1A—O1A—C4A—C5A | 78.62 (12) | C5B—C5B2—C9B2—C9B | −178.81 (13) |
N1A—O1A—C4A—C3A | −42.92 (12) | C6B—C5B2—C9B2—N1B | −176.36 (12) |
C2A—C3A—C4A—O1A | 19.79 (14) | C5B—C5B2—C9B2—N1B | 3.4 (2) |
C2A—C3A—C4A—C5A | −97.11 (13) | O1B—N1B—C9B2—C9B | −152.18 (11) |
O1A—C4A—C5A—C5A2 | −44.43 (15) | C2B—N1B—C9B2—C9B | 98.08 (14) |
C3A—C4A—C5A—C5A2 | 70.10 (15) | O1B—N1B—C9B2—C5B2 | 25.66 (16) |
C5A2—C6A—C7A—C8A | −0.1 (2) | C2B—N1B—C9B2—C5B2 | −84.08 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2A—H2A···O1Ai | 1.00 | 2.61 | 3.4061 (17) | 137 |
C5A—H5AA···Cg1A2ii | 1.00 | 2.60 | 3.5600 (16) | 163 |
C4B—H4B···O1Biii | 1.00 | 2.43 | 3.1601 (18) | 129 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+2, −y, −z+1. |
C22H21NO | Dx = 1.217 Mg m−3 |
Mr = 315.40 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 9810 reflections |
a = 7.5541 (3) Å | θ = 2.8–23.6° |
b = 14.7914 (5) Å | µ = 0.07 mm−1 |
c = 15.4049 (5) Å | T = 298 K |
V = 1721.28 (11) Å3 | Parallelipiped, less |
Z = 4 | 0.51 × 0.32 × 0.25 mm |
F(000) = 672 |
Bruker Kappa APEXII diffractometer | 4013 reflections with I > 2σ(I) |
π and ω scans | Rint = 0.041 |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | θmax = 31.5°, θmin = 2.6° |
Tmin = 0.86, Tmax = 0.98 | h = −11→11 |
69991 measured reflections | k = −21→21 |
5630 independent reflections | l = −21→20 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.043 | w = 1/[σ2(Fo2) + (0.0474P)2 + 0.1943P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.109 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.17 e Å−3 |
5630 reflections | Δρmin = −0.16 e Å−3 |
220 parameters | Absolute structure: Refined as an inversion twin |
0 restraints | Absolute structure parameter: 0 (2) |
C22H21NO | V = 1721.28 (11) Å3 |
Mr = 315.40 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.5541 (3) Å | µ = 0.07 mm−1 |
b = 14.7914 (5) Å | T = 298 K |
c = 15.4049 (5) Å | 0.51 × 0.32 × 0.25 mm |
Bruker Kappa APEXII diffractometer | 5630 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 4013 reflections with I > 2σ(I) |
Tmin = 0.86, Tmax = 0.98 | Rint = 0.041 |
69991 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.109 | Δρmax = 0.17 e Å−3 |
S = 1.03 | Δρmin = −0.16 e Å−3 |
5630 reflections | Absolute structure: Refined as an inversion twin |
220 parameters | Absolute structure parameter: 0 (2) |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refined as a 2-component inversion twin |
x | y | z | Uiso*/Ueq | ||
N1 | 0.9800 (2) | 0.52882 (10) | 0.31021 (10) | 0.0423 (3) | |
O1 | 0.9286 (2) | 0.43694 (9) | 0.33014 (10) | 0.0568 (4) | |
C2 | 0.9364 (2) | 0.57663 (11) | 0.39184 (11) | 0.0377 (4) | |
H2 | 0.9125 | 0.6403 | 0.3788 | 0.045* | |
C3 | 0.7626 (3) | 0.53080 (15) | 0.42245 (13) | 0.0485 (4) | |
H3A | 0.7685 | 0.5151 | 0.4835 | 0.058* | |
H3B | 0.6614 | 0.5699 | 0.4129 | 0.058* | |
C4 | 0.7519 (3) | 0.44603 (14) | 0.36570 (14) | 0.0577 (5) | |
H4 | 0.7213 | 0.3931 | 0.4009 | 0.069* | |
C5 | 0.6282 (3) | 0.45441 (15) | 0.28903 (15) | 0.0612 (6) | |
H5A | 0.6195 | 0.3968 | 0.2592 | 0.073* | |
H5B | 0.5109 | 0.4713 | 0.3089 | 0.073* | |
C6 | 0.5982 (3) | 0.55849 (14) | 0.15960 (12) | 0.0501 (5) | |
H6 | 0.4869 | 0.5341 | 0.1488 | 0.060* | |
C7 | 0.6613 (3) | 0.62674 (14) | 0.10782 (13) | 0.0509 (5) | |
H7 | 0.5918 | 0.6478 | 0.0623 | 0.061* | |
C8 | 0.8273 (3) | 0.66520 (12) | 0.12205 (12) | 0.0461 (4) | |
C9 | 0.9331 (2) | 0.63197 (12) | 0.18904 (11) | 0.0407 (4) | |
C20 | 1.0829 (2) | 0.57094 (11) | 0.45868 (11) | 0.0392 (4) | |
C21 | 1.2146 (3) | 0.50741 (14) | 0.45314 (14) | 0.0492 (5) | |
H21 | 1.2173 | 0.4679 | 0.4062 | 0.059* | |
C22 | 1.3460 (3) | 0.50135 (16) | 0.51779 (16) | 0.0607 (6) | |
H22 | 1.4333 | 0.4572 | 0.5134 | 0.073* | |
C23 | 1.3470 (3) | 0.55880 (16) | 0.58620 (15) | 0.0601 (6) | |
H23 | 1.4357 | 0.5541 | 0.6278 | 0.072* | |
C24 | 1.2156 (3) | 0.62541 (14) | 0.59503 (13) | 0.0488 (5) | |
C25 | 1.2122 (4) | 0.68617 (16) | 0.66644 (14) | 0.0626 (6) | |
H25 | 1.2999 | 0.6821 | 0.7086 | 0.075* | |
C26 | 1.0850 (4) | 0.74953 (16) | 0.67460 (14) | 0.0661 (7) | |
H26 | 1.0858 | 0.7886 | 0.7219 | 0.079* | |
C27 | 0.9521 (4) | 0.75635 (14) | 0.61188 (14) | 0.0611 (6) | |
H27 | 0.8648 | 0.8003 | 0.6177 | 0.073* | |
C28 | 0.9485 (3) | 0.69931 (13) | 0.54195 (13) | 0.0499 (5) | |
H28 | 0.8584 | 0.7046 | 0.5012 | 0.060* | |
C82 | 0.8909 (4) | 0.74143 (16) | 0.06431 (15) | 0.0690 (7) | |
H82A | 0.9963 | 0.7230 | 0.0344 | 0.104* | |
H82B | 0.9161 | 0.7936 | 0.0992 | 0.104* | |
H82C | 0.8005 | 0.7560 | 0.0228 | 0.104* | |
C92 | 1.1147 (3) | 0.67050 (16) | 0.20596 (15) | 0.0568 (5) | |
H92A | 1.1760 | 0.6781 | 0.1519 | 0.085* | |
H92B | 1.1801 | 0.6299 | 0.2425 | 0.085* | |
H92C | 1.1034 | 0.7280 | 0.2343 | 0.085* | |
C29 | 1.0806 (2) | 0.63220 (12) | 0.53094 (11) | 0.0410 (4) | |
C5A | 0.6987 (3) | 0.52552 (12) | 0.22777 (12) | 0.0443 (4) | |
C9A | 0.8675 (2) | 0.56170 (11) | 0.24071 (11) | 0.0384 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0461 (8) | 0.0365 (7) | 0.0444 (8) | 0.0033 (6) | 0.0020 (7) | −0.0003 (6) |
O1 | 0.0657 (9) | 0.0355 (6) | 0.0692 (9) | 0.0050 (7) | −0.0012 (8) | 0.0036 (6) |
C2 | 0.0380 (8) | 0.0373 (8) | 0.0380 (8) | 0.0039 (7) | 0.0012 (7) | 0.0031 (7) |
C3 | 0.0395 (9) | 0.0625 (11) | 0.0435 (10) | −0.0025 (8) | −0.0005 (8) | 0.0102 (9) |
C4 | 0.0630 (13) | 0.0467 (11) | 0.0633 (13) | −0.0132 (10) | −0.0025 (10) | 0.0147 (10) |
C5 | 0.0634 (13) | 0.0558 (12) | 0.0645 (13) | −0.0229 (10) | −0.0061 (11) | 0.0019 (10) |
C6 | 0.0475 (11) | 0.0545 (10) | 0.0484 (10) | −0.0077 (9) | −0.0069 (9) | −0.0148 (9) |
C7 | 0.0582 (12) | 0.0535 (10) | 0.0410 (10) | 0.0029 (10) | −0.0102 (9) | −0.0068 (9) |
C8 | 0.0582 (12) | 0.0444 (9) | 0.0356 (9) | 0.0014 (8) | 0.0018 (8) | −0.0049 (8) |
C9 | 0.0433 (9) | 0.0424 (8) | 0.0363 (8) | −0.0003 (8) | 0.0039 (7) | −0.0072 (7) |
C20 | 0.0353 (8) | 0.0385 (8) | 0.0439 (9) | −0.0005 (7) | 0.0010 (7) | 0.0107 (7) |
C21 | 0.0407 (10) | 0.0476 (10) | 0.0593 (11) | 0.0042 (8) | 0.0019 (9) | 0.0096 (9) |
C22 | 0.0370 (10) | 0.0629 (13) | 0.0823 (16) | 0.0086 (9) | −0.0019 (10) | 0.0257 (12) |
C23 | 0.0427 (11) | 0.0694 (13) | 0.0682 (13) | −0.0091 (10) | −0.0185 (10) | 0.0267 (12) |
C24 | 0.0458 (10) | 0.0515 (10) | 0.0492 (10) | −0.0164 (9) | −0.0089 (9) | 0.0194 (9) |
C25 | 0.0709 (15) | 0.0672 (14) | 0.0496 (11) | −0.0296 (13) | −0.0192 (11) | 0.0122 (10) |
C26 | 0.0900 (18) | 0.0605 (13) | 0.0477 (11) | −0.0238 (14) | −0.0030 (12) | −0.0040 (10) |
C27 | 0.0774 (16) | 0.0526 (11) | 0.0533 (11) | −0.0014 (11) | 0.0038 (11) | −0.0043 (10) |
C28 | 0.0568 (12) | 0.0472 (10) | 0.0458 (10) | 0.0028 (9) | −0.0060 (9) | 0.0012 (8) |
C82 | 0.0864 (18) | 0.0655 (13) | 0.0552 (12) | −0.0094 (13) | −0.0058 (12) | 0.0149 (11) |
C92 | 0.0458 (11) | 0.0675 (13) | 0.0572 (12) | −0.0125 (10) | 0.0024 (10) | 0.0045 (10) |
C29 | 0.0425 (9) | 0.0407 (8) | 0.0397 (9) | −0.0071 (8) | −0.0034 (8) | 0.0108 (7) |
C5A | 0.0483 (10) | 0.0402 (8) | 0.0443 (9) | −0.0050 (8) | −0.0008 (8) | −0.0082 (7) |
C9A | 0.0422 (9) | 0.0359 (7) | 0.0371 (8) | 0.0034 (7) | 0.0023 (7) | −0.0085 (7) |
N1—O1 | 1.446 (2) | C9—C9A | 1.400 (2) |
N1—C9A | 1.451 (2) | C9—C92 | 1.508 (3) |
N1—C2 | 1.480 (2) | C20—C21 | 1.371 (3) |
O1—C4 | 1.450 (3) | C20—C29 | 1.435 (3) |
C2—C20 | 1.514 (2) | C21—C22 | 1.409 (3) |
C2—C3 | 1.551 (3) | C22—C23 | 1.354 (3) |
C3—C4 | 1.531 (3) | C23—C24 | 1.405 (3) |
C4—C5 | 1.511 (3) | C24—C25 | 1.421 (3) |
C5—C5A | 1.510 (3) | C24—C29 | 1.423 (3) |
C6—C7 | 1.372 (3) | C25—C26 | 1.348 (4) |
C6—C5A | 1.384 (3) | C26—C27 | 1.397 (4) |
C7—C8 | 1.395 (3) | C27—C28 | 1.369 (3) |
C8—C9 | 1.395 (3) | C28—C29 | 1.418 (3) |
C8—C82 | 1.514 (3) | C5A—C9A | 1.397 (3) |
O1—N1—C9A | 108.33 (14) | C21—C20—C2 | 121.75 (17) |
O1—N1—C2 | 102.06 (13) | C29—C20—C2 | 118.92 (15) |
C9A—N1—C2 | 109.66 (13) | C20—C21—C22 | 120.7 (2) |
N1—O1—C4 | 103.89 (14) | C23—C22—C21 | 121.0 (2) |
N1—C2—C20 | 112.86 (14) | C22—C23—C24 | 120.77 (19) |
N1—C2—C3 | 103.77 (14) | C23—C24—C25 | 122.1 (2) |
C20—C2—C3 | 112.82 (14) | C23—C24—C29 | 119.2 (2) |
C4—C3—C2 | 103.24 (16) | C25—C24—C29 | 118.6 (2) |
O1—C4—C5 | 106.37 (18) | C26—C25—C24 | 121.7 (2) |
O1—C4—C3 | 104.08 (16) | C25—C26—C27 | 119.9 (2) |
C5—C4—C3 | 114.32 (18) | C28—C27—C26 | 120.9 (2) |
C5A—C5—C4 | 109.11 (17) | C27—C28—C29 | 120.8 (2) |
C7—C6—C5A | 120.65 (19) | C28—C29—C24 | 118.09 (18) |
C6—C7—C8 | 121.40 (19) | C28—C29—C20 | 122.90 (16) |
C9—C8—C7 | 119.21 (18) | C24—C29—C20 | 119.01 (18) |
C9—C8—C82 | 121.02 (19) | C6—C5A—C9A | 118.28 (18) |
C7—C8—C82 | 119.77 (19) | C6—C5A—C5 | 121.72 (18) |
C8—C9—C9A | 118.63 (17) | C9A—C5A—C5 | 119.97 (18) |
C8—C9—C92 | 121.06 (17) | C5A—C9A—C9 | 121.78 (17) |
C9A—C9—C92 | 120.31 (17) | C5A—C9A—N1 | 120.77 (16) |
C21—C20—C29 | 119.30 (17) | C9—C9A—N1 | 117.44 (16) |
C9A—N1—O1—C4 | −66.50 (17) | C23—C24—C25—C26 | −179.6 (2) |
C2—N1—O1—C4 | 49.16 (17) | C29—C24—C25—C26 | −0.1 (3) |
O1—N1—C2—C20 | 84.80 (17) | C24—C25—C26—C27 | 0.2 (3) |
C9A—N1—C2—C20 | −160.50 (14) | C25—C26—C27—C28 | 0.1 (3) |
O1—N1—C2—C3 | −37.66 (16) | C26—C27—C28—C29 | −0.5 (3) |
C9A—N1—C2—C3 | 77.04 (16) | C27—C28—C29—C24 | 0.6 (3) |
N1—C2—C3—C4 | 13.45 (17) | C27—C28—C29—C20 | −179.87 (18) |
C20—C2—C3—C4 | −109.03 (17) | C23—C24—C29—C28 | 179.27 (18) |
N1—O1—C4—C5 | 81.05 (18) | C25—C24—C29—C28 | −0.3 (2) |
N1—O1—C4—C3 | −40.02 (18) | C23—C24—C29—C20 | −0.3 (2) |
C2—C3—C4—O1 | 15.50 (18) | C25—C24—C29—C20 | −179.85 (17) |
C2—C3—C4—C5 | −100.11 (19) | C21—C20—C29—C28 | −179.47 (18) |
O1—C4—C5—C5A | −49.5 (2) | C2—C20—C29—C28 | −1.2 (3) |
C3—C4—C5—C5A | 64.8 (2) | C21—C20—C29—C24 | 0.1 (2) |
C5A—C6—C7—C8 | −0.2 (3) | C2—C20—C29—C24 | 178.37 (15) |
C6—C7—C8—C9 | 1.6 (3) | C7—C6—C5A—C9A | −1.9 (3) |
C6—C7—C8—C82 | −179.03 (19) | C7—C6—C5A—C5 | 176.3 (2) |
C7—C8—C9—C9A | −0.9 (3) | C4—C5—C5A—C6 | −168.88 (18) |
C82—C8—C9—C9A | 179.70 (18) | C4—C5—C5A—C9A | 9.2 (3) |
C7—C8—C9—C92 | 179.07 (18) | C6—C5A—C9A—C9 | 2.5 (3) |
C82—C8—C9—C92 | −0.3 (3) | C5—C5A—C9A—C9 | −175.63 (17) |
N1—C2—C20—C21 | −17.7 (2) | C6—C5A—C9A—N1 | −178.99 (16) |
C3—C2—C20—C21 | 99.5 (2) | C5—C5A—C9A—N1 | 2.9 (3) |
N1—C2—C20—C29 | 164.02 (15) | C8—C9—C9A—C5A | −1.1 (2) |
C3—C2—C20—C29 | −78.74 (19) | C92—C9—C9A—C5A | 178.87 (17) |
C29—C20—C21—C22 | 0.6 (3) | C8—C9—C9A—N1 | −179.66 (15) |
C2—C20—C21—C22 | −177.71 (17) | C92—C9—C9A—N1 | 0.3 (2) |
C20—C21—C22—C23 | −1.0 (3) | O1—N1—C9A—C5A | 25.6 (2) |
C21—C22—C23—C24 | 0.7 (3) | C2—N1—C9A—C5A | −84.97 (19) |
C22—C23—C24—C25 | 179.44 (19) | O1—N1—C9A—C9 | −155.80 (14) |
C22—C23—C24—C29 | −0.1 (3) | C2—N1—C9A—C9 | 93.59 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C82—H82···O1i | 0.96 | 2.66 | 3.587 (3) | 164 |
Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
C22H21NO | F(000) = 336 |
Mr = 315.40 | Dx = 1.262 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2201 (2) Å | Cell parameters from 9843 reflections |
b = 7.8128 (3) Å | θ = 2.8–30.2° |
c = 14.7409 (5) Å | µ = 0.08 mm−1 |
β = 93.690 (2)° | T = 100 K |
V = 829.80 (5) Å3 | Paralelipiped, less |
Z = 2 | 0.30 × 0.30 × 0.15 mm |
Bruker Kappa APEXII diffractometer | 4638 reflections with I > 2σ(I) |
π and ω scans | Rint = 0.023 |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | θmax = 30.3°, θmin = 1.4° |
Tmin = 0.92, Tmax = 0.99 | h = −10→10 |
27947 measured reflections | k = −11→11 |
4874 independent reflections | l = −20→20 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0566P)2 + 0.1148P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
4874 reflections | Δρmax = 0.30 e Å−3 |
219 parameters | Δρmin = −0.19 e Å−3 |
1 restraint | Absolute structure: Flack x determined using 2066 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: iterative | Absolute structure parameter: −0.1 (3) |
C22H21NO | V = 829.80 (5) Å3 |
Mr = 315.40 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.2201 (2) Å | µ = 0.08 mm−1 |
b = 7.8128 (3) Å | T = 100 K |
c = 14.7409 (5) Å | 0.30 × 0.30 × 0.15 mm |
β = 93.690 (2)° |
Bruker Kappa APEXII diffractometer | 4874 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 4638 reflections with I > 2σ(I) |
Tmin = 0.92, Tmax = 0.99 | Rint = 0.023 |
27947 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.092 | Δρmax = 0.30 e Å−3 |
S = 1.04 | Δρmin = −0.19 e Å−3 |
4874 reflections | Absolute structure: Flack x determined using 2066 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
219 parameters | Absolute structure parameter: −0.1 (3) |
1 restraint |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.15129 (17) | 0.35804 (16) | 0.21245 (8) | 0.0165 (2) | |
O1 | 0.09164 (15) | 0.19439 (14) | 0.17551 (7) | 0.0205 (2) | |
C2 | 0.08542 (18) | 0.35174 (18) | 0.30555 (9) | 0.0150 (2) | |
H2 | 0.0643 | 0.4709 | 0.3274 | 0.018* | |
C3 | −0.10421 (19) | 0.2564 (2) | 0.29297 (10) | 0.0187 (3) | |
H3A | −0.1127 | 0.1637 | 0.3383 | 0.022* | |
H3B | −0.2094 | 0.3364 | 0.2983 | 0.022* | |
C4 | −0.1017 (2) | 0.1839 (2) | 0.19629 (10) | 0.0209 (3) | |
H4 | −0.1451 | 0.0624 | 0.1945 | 0.025* | |
C5 | −0.2114 (2) | 0.2901 (2) | 0.12504 (10) | 0.0227 (3) | |
H5A | −0.2169 | 0.2296 | 0.0659 | 0.027* | |
H5B | −0.3399 | 0.3060 | 0.1432 | 0.027* | |
C6 | −0.2051 (2) | 0.5930 (2) | 0.06265 (10) | 0.0230 (3) | |
C7 | −0.1176 (2) | 0.7511 (2) | 0.05942 (10) | 0.0254 (3) | |
H7 | −0.1746 | 0.8403 | 0.0238 | 0.030* | |
C8 | 0.0513 (2) | 0.7813 (2) | 0.10715 (10) | 0.0230 (3) | |
H8 | 0.1064 | 0.8915 | 0.1050 | 0.028* | |
C9 | 0.1414 (2) | 0.65198 (18) | 0.15833 (9) | 0.0189 (3) | |
C20 | 0.22202 (18) | 0.26185 (18) | 0.37162 (9) | 0.0149 (2) | |
C21 | 0.37597 (19) | 0.1793 (2) | 0.34334 (10) | 0.0189 (3) | |
H21 | 0.4001 | 0.1809 | 0.2807 | 0.023* | |
C22 | 0.4994 (2) | 0.0918 (2) | 0.40580 (11) | 0.0227 (3) | |
H22 | 0.6040 | 0.0340 | 0.3846 | 0.027* | |
C23 | 0.46936 (19) | 0.0897 (2) | 0.49629 (11) | 0.0218 (3) | |
H23 | 0.5533 | 0.0309 | 0.5376 | 0.026* | |
C24 | 0.31329 (18) | 0.17489 (19) | 0.52887 (9) | 0.0170 (3) | |
C25 | 0.2805 (2) | 0.1761 (2) | 0.62270 (10) | 0.0208 (3) | |
H25 | 0.3651 | 0.1193 | 0.6646 | 0.025* | |
C26 | 0.1294 (2) | 0.2575 (2) | 0.65411 (10) | 0.0220 (3) | |
H26 | 0.1100 | 0.2576 | 0.7172 | 0.026* | |
C27 | 0.0027 (2) | 0.3414 (2) | 0.59219 (10) | 0.0210 (3) | |
H27 | −0.1031 | 0.3966 | 0.6138 | 0.025* | |
C28 | 0.03096 (19) | 0.34389 (19) | 0.50090 (10) | 0.0178 (3) | |
H28 | −0.0552 | 0.4018 | 0.4603 | 0.021* | |
C62 | −0.3885 (2) | 0.5624 (3) | 0.01018 (12) | 0.0316 (4) | |
H62A | −0.4141 | 0.6570 | −0.0325 | 0.047* | |
H62B | −0.4874 | 0.5558 | 0.0525 | 0.047* | |
H62C | −0.3829 | 0.4547 | −0.0236 | 0.047* | |
C92 | 0.3224 (2) | 0.6848 (2) | 0.21182 (10) | 0.0230 (3) | |
H92A | 0.4071 | 0.5888 | 0.2037 | 0.035* | |
H92B | 0.3000 | 0.6965 | 0.2764 | 0.035* | |
H92C | 0.3779 | 0.7905 | 0.1902 | 0.035* | |
C29 | 0.18719 (18) | 0.26126 (18) | 0.46621 (9) | 0.0147 (2) | |
C5A | −0.1198 (2) | 0.46197 (19) | 0.11569 (9) | 0.0193 (3) | |
C9A | 0.0542 (2) | 0.49217 (18) | 0.16048 (9) | 0.0170 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0208 (5) | 0.0128 (5) | 0.0158 (5) | 0.0005 (4) | 0.0010 (4) | −0.0013 (4) |
O1 | 0.0228 (5) | 0.0150 (5) | 0.0240 (5) | −0.0001 (4) | 0.0026 (4) | −0.0053 (4) |
C2 | 0.0153 (5) | 0.0133 (6) | 0.0165 (5) | 0.0015 (5) | 0.0019 (4) | 0.0008 (5) |
C3 | 0.0171 (6) | 0.0178 (6) | 0.0210 (6) | −0.0004 (5) | 0.0003 (5) | 0.0013 (5) |
C4 | 0.0217 (6) | 0.0162 (6) | 0.0247 (6) | −0.0019 (5) | 0.0009 (5) | −0.0031 (6) |
C5 | 0.0229 (7) | 0.0239 (7) | 0.0208 (6) | −0.0028 (6) | −0.0030 (5) | −0.0036 (5) |
C6 | 0.0242 (7) | 0.0286 (8) | 0.0160 (6) | 0.0067 (6) | 0.0002 (5) | −0.0013 (6) |
C7 | 0.0318 (8) | 0.0257 (7) | 0.0188 (6) | 0.0095 (6) | 0.0031 (6) | 0.0045 (6) |
C8 | 0.0311 (7) | 0.0187 (7) | 0.0197 (6) | 0.0026 (6) | 0.0066 (6) | 0.0029 (5) |
C9 | 0.0230 (7) | 0.0187 (7) | 0.0154 (6) | −0.0001 (5) | 0.0033 (5) | 0.0003 (5) |
C20 | 0.0151 (5) | 0.0113 (5) | 0.0182 (6) | 0.0002 (5) | 0.0012 (4) | 0.0010 (5) |
C21 | 0.0176 (6) | 0.0160 (6) | 0.0234 (6) | 0.0014 (5) | 0.0048 (5) | 0.0015 (6) |
C22 | 0.0160 (6) | 0.0200 (7) | 0.0328 (8) | 0.0057 (6) | 0.0061 (5) | 0.0055 (6) |
C23 | 0.0161 (6) | 0.0191 (7) | 0.0299 (7) | 0.0026 (5) | −0.0009 (5) | 0.0067 (6) |
C24 | 0.0154 (6) | 0.0134 (6) | 0.0218 (6) | −0.0016 (5) | −0.0007 (5) | 0.0030 (5) |
C25 | 0.0233 (7) | 0.0178 (6) | 0.0208 (6) | −0.0055 (5) | −0.0030 (5) | 0.0049 (6) |
C26 | 0.0301 (7) | 0.0179 (6) | 0.0181 (6) | −0.0078 (6) | 0.0031 (5) | 0.0004 (5) |
C27 | 0.0250 (7) | 0.0161 (6) | 0.0227 (7) | −0.0012 (6) | 0.0075 (5) | −0.0008 (6) |
C28 | 0.0188 (6) | 0.0141 (6) | 0.0206 (6) | 0.0022 (5) | 0.0025 (5) | 0.0003 (5) |
C62 | 0.0271 (8) | 0.0422 (10) | 0.0246 (7) | 0.0097 (7) | −0.0056 (6) | −0.0028 (7) |
C92 | 0.0255 (7) | 0.0223 (7) | 0.0212 (6) | −0.0057 (6) | 0.0013 (5) | 0.0005 (6) |
C29 | 0.0150 (5) | 0.0108 (5) | 0.0183 (6) | −0.0009 (5) | 0.0013 (4) | 0.0009 (5) |
C5A | 0.0216 (6) | 0.0201 (7) | 0.0161 (6) | 0.0014 (5) | 0.0000 (5) | −0.0023 (5) |
C9A | 0.0209 (6) | 0.0167 (6) | 0.0136 (5) | 0.0022 (5) | 0.0014 (5) | −0.0004 (5) |
N1—O1 | 1.4445 (15) | C9—C9A | 1.400 (2) |
N1—C9A | 1.4516 (18) | C9—C92 | 1.504 (2) |
N1—C2 | 1.4819 (17) | C20—C21 | 1.3730 (19) |
O1—C4 | 1.4504 (18) | C20—C29 | 1.4328 (17) |
C2—C20 | 1.5135 (18) | C21—C22 | 1.415 (2) |
C2—C3 | 1.5591 (19) | C22—C23 | 1.365 (2) |
C3—C4 | 1.535 (2) | C23—C24 | 1.419 (2) |
C4—C5 | 1.520 (2) | C24—C25 | 1.4182 (19) |
C5—C5A | 1.507 (2) | C24—C29 | 1.4245 (17) |
C6—C7 | 1.390 (2) | C25—C26 | 1.369 (2) |
C6—C5A | 1.406 (2) | C26—C27 | 1.411 (2) |
C6—C62 | 1.509 (2) | C27—C28 | 1.374 (2) |
C7—C8 | 1.389 (2) | C28—C29 | 1.4229 (18) |
C8—C9 | 1.396 (2) | C5A—C9A | 1.4008 (19) |
O1—N1—C9A | 108.54 (10) | C21—C20—C2 | 121.96 (12) |
O1—N1—C2 | 102.36 (10) | C29—C20—C2 | 118.67 (11) |
C9A—N1—C2 | 109.87 (11) | C20—C21—C22 | 121.16 (13) |
N1—O1—C4 | 103.76 (10) | C23—C22—C21 | 120.57 (13) |
N1—C2—C20 | 112.13 (11) | C22—C23—C24 | 120.30 (13) |
N1—C2—C3 | 103.74 (11) | C25—C24—C23 | 121.29 (13) |
C20—C2—C3 | 112.69 (11) | C25—C24—C29 | 119.29 (12) |
C4—C3—C2 | 102.93 (11) | C23—C24—C29 | 119.42 (12) |
O1—C4—C5 | 106.80 (12) | C26—C25—C24 | 121.31 (13) |
O1—C4—C3 | 104.16 (11) | C25—C26—C27 | 119.64 (13) |
C5—C4—C3 | 113.79 (13) | C28—C27—C26 | 120.60 (14) |
C5A—C5—C4 | 109.70 (12) | C27—C28—C29 | 121.10 (13) |
C7—C6—C5A | 118.84 (14) | C28—C29—C24 | 118.05 (12) |
C7—C6—C62 | 120.59 (15) | C28—C29—C20 | 122.76 (12) |
C5A—C6—C62 | 120.57 (16) | C24—C29—C20 | 119.19 (11) |
C8—C7—C6 | 121.34 (15) | C9A—C5A—C6 | 119.15 (14) |
C7—C8—C9 | 120.94 (15) | C9A—C5A—C5 | 119.50 (13) |
C8—C9—C9A | 117.59 (14) | C6—C5A—C5 | 121.36 (14) |
C8—C9—C92 | 121.23 (14) | C9—C9A—C5A | 122.05 (13) |
C9A—C9—C92 | 121.14 (13) | C9—C9A—N1 | 116.95 (12) |
C21—C20—C29 | 119.36 (12) | C5A—C9A—N1 | 121.00 (13) |
C9A—N1—O1—C4 | −66.84 (13) | C24—C25—C26—C27 | 0.3 (2) |
C2—N1—O1—C4 | 49.28 (12) | C25—C26—C27—C28 | −0.9 (2) |
O1—N1—C2—C20 | 84.76 (12) | C26—C27—C28—C29 | 0.5 (2) |
C9A—N1—C2—C20 | −160.08 (11) | C27—C28—C29—C24 | 0.3 (2) |
O1—N1—C2—C3 | −37.12 (12) | C27—C28—C29—C20 | −179.63 (13) |
C9A—N1—C2—C3 | 78.04 (13) | C25—C24—C29—C28 | −0.81 (19) |
N1—C2—C3—C4 | 12.43 (14) | C23—C24—C29—C28 | 179.32 (14) |
C20—C2—C3—C4 | −109.07 (13) | C25—C24—C29—C20 | 179.14 (14) |
N1—O1—C4—C5 | 79.98 (13) | C23—C24—C29—C20 | −0.73 (19) |
N1—O1—C4—C3 | −40.73 (13) | C21—C20—C29—C28 | 179.95 (14) |
C2—C3—C4—O1 | 16.50 (15) | C2—C20—C29—C28 | −1.0 (2) |
C2—C3—C4—C5 | −99.41 (14) | C21—C20—C29—C24 | 0.01 (19) |
O1—C4—C5—C5A | −48.20 (15) | C2—C20—C29—C24 | 179.07 (12) |
C3—C4—C5—C5A | 66.15 (16) | C7—C6—C5A—C9A | −2.7 (2) |
C5A—C6—C7—C8 | 0.1 (2) | C62—C6—C5A—C9A | 177.31 (13) |
C62—C6—C7—C8 | −179.88 (14) | C7—C6—C5A—C5 | 177.46 (14) |
C6—C7—C8—C9 | 1.6 (2) | C62—C6—C5A—C5 | −2.5 (2) |
C7—C8—C9—C9A | −0.7 (2) | C4—C5—C5A—C9A | 8.16 (18) |
C7—C8—C9—C92 | −178.66 (14) | C4—C5—C5A—C6 | −172.01 (13) |
N1—C2—C20—C21 | −7.43 (19) | C8—C9—C9A—C5A | −1.9 (2) |
C3—C2—C20—C21 | 109.19 (15) | C92—C9—C9A—C5A | 176.00 (13) |
N1—C2—C20—C29 | 173.53 (12) | C8—C9—C9A—N1 | 178.78 (12) |
C3—C2—C20—C29 | −69.86 (16) | C92—C9—C9A—N1 | −3.28 (19) |
C29—C20—C21—C22 | 0.8 (2) | C6—C5A—C9A—C9 | 3.7 (2) |
C2—C20—C21—C22 | −178.19 (14) | C5—C5A—C9A—C9 | −176.48 (13) |
C20—C21—C22—C23 | −1.0 (2) | C6—C5A—C9A—N1 | −177.07 (12) |
C21—C22—C23—C24 | 0.2 (2) | C5—C5A—C9A—N1 | 2.8 (2) |
C22—C23—C24—C25 | −179.25 (14) | O1—N1—C9A—C9 | −154.16 (12) |
C22—C23—C24—C29 | 0.6 (2) | C2—N1—C9A—C9 | 94.67 (14) |
C23—C24—C25—C26 | −179.64 (14) | O1—N1—C9A—C5A | 26.55 (16) |
C29—C24—C25—C26 | 0.5 (2) | C2—N1—C9A—C5A | −84.62 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O1i | 0.95 | 2.59 | 3.3880 (19) | 142 |
C27—H27···Cg31ii | 0.95 | 2.86 | 3.6294 (16) | 139 |
C28—H28···Cg32ii | 0.95 | 2.90 | 3.6116 (16) | 133 |
Symmetry codes: (i) x, y+1, z; (ii) −x, y+1/2, −z+1. |
C18H18FNO | Dx = 1.281 Mg m−3 |
Mr = 283.33 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 9770 reflections |
a = 7.5932 (3) Å | θ = 2.4–29.8° |
b = 7.5859 (4) Å | µ = 0.09 mm−1 |
c = 51.010 (3) Å | T = 100 K |
V = 2938.2 (2) Å3 | Parallelepiped, less |
Z = 8 | 0.30 × 0.25 × 0.20 mm |
F(000) = 1200 |
Bruker Kappa APEXII diffractometer | 3407 reflections with I > 2σ(I) |
π and ω scans | Rint = 0.027 |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | θmax = 30.3°, θmin = 1.6° |
Tmin = 0.90, Tmax = 0.98 | h = −10→10 |
40696 measured reflections | k = −10→10 |
3764 independent reflections | l = −67→69 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: mixed |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0371P)2 + 2.0455P] where P = (Fo2 + 2Fc2)/3 |
3764 reflections | (Δ/σ)max = 0.001 |
198 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C18H18FNO | V = 2938.2 (2) Å3 |
Mr = 283.33 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.5932 (3) Å | µ = 0.09 mm−1 |
b = 7.5859 (4) Å | T = 100 K |
c = 51.010 (3) Å | 0.30 × 0.25 × 0.20 mm |
Bruker Kappa APEXII diffractometer | 3764 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 3407 reflections with I > 2σ(I) |
Tmin = 0.90, Tmax = 0.98 | Rint = 0.027 |
40696 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.32 e Å−3 |
3764 reflections | Δρmin = −0.23 e Å−3 |
198 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.58993 (12) | 0.76036 (12) | 0.39113 (2) | 0.0191 (2) | |
N1 | 0.52091 (13) | 0.18488 (14) | 0.39564 (2) | 0.0147 (2) | |
F1 | 0.41254 (14) | 0.24707 (13) | 0.50268 (2) | 0.0359 (2) | |
C2 | 0.42190 (15) | 0.29702 (16) | 0.37707 (2) | 0.0149 (2) | |
H2 | 0.3001 | 0.3145 | 0.3841 | 0.018* | |
C3 | 0.50905 (16) | 0.47789 (16) | 0.37386 (2) | 0.0159 (2) | |
H3A | 0.6324 | 0.4595 | 0.3682 | 0.019* | |
H3B | 0.4478 | 0.5417 | 0.3596 | 0.019* | |
C4 | 0.51013 (16) | 0.59518 (16) | 0.39810 (2) | 0.0163 (2) | |
H4 | 0.3853 | 0.6182 | 0.4033 | 0.020* | |
C5 | 0.60719 (16) | 0.51906 (16) | 0.42174 (2) | 0.0161 (2) | |
H5A | 0.7259 | 0.4823 | 0.4159 | 0.019* | |
H5B | 0.6234 | 0.6151 | 0.4347 | 0.019* | |
C6 | 0.49800 (17) | 0.37683 (17) | 0.46270 (2) | 0.0204 (3) | |
H6 | 0.5217 | 0.4839 | 0.4717 | 0.025* | |
C7 | 0.43774 (18) | 0.23177 (19) | 0.47628 (2) | 0.0230 (3) | |
C8 | 0.40179 (17) | 0.07342 (18) | 0.46443 (3) | 0.0213 (3) | |
H8 | 0.3626 | −0.0252 | 0.4743 | 0.026* | |
C9 | 0.42478 (16) | 0.06272 (17) | 0.43749 (2) | 0.0178 (2) | |
H9 | 0.3990 | −0.0447 | 0.4287 | 0.021* | |
C21 | 0.40917 (16) | 0.21035 (17) | 0.35058 (2) | 0.0175 (2) | |
H21 | 0.3378 | 0.2677 | 0.3379 | 0.021* | |
C22 | 0.48755 (16) | 0.06184 (17) | 0.34316 (2) | 0.0189 (3) | |
H22 | 0.5561 | 0.0026 | 0.3560 | 0.023* | |
C23 | 0.47892 (17) | −0.02029 (17) | 0.31701 (2) | 0.0194 (3) | |
C24 | 0.59407 (19) | −0.1587 (2) | 0.31126 (3) | 0.0260 (3) | |
H24 | 0.6742 | −0.1984 | 0.3243 | 0.031* | |
C25 | 0.5932 (2) | −0.2391 (2) | 0.28677 (3) | 0.0305 (3) | |
H25 | 0.6731 | −0.3322 | 0.2831 | 0.037* | |
C26 | 0.4756 (2) | −0.1834 (2) | 0.26774 (3) | 0.0287 (3) | |
H26 | 0.4751 | −0.2376 | 0.2510 | 0.034* | |
C27 | 0.3588 (2) | −0.04858 (19) | 0.27327 (3) | 0.0268 (3) | |
H27 | 0.2773 | −0.0113 | 0.2603 | 0.032* | |
C28 | 0.35978 (19) | 0.03281 (18) | 0.29769 (2) | 0.0230 (3) | |
H28 | 0.2788 | 0.1252 | 0.3013 | 0.028* | |
C5A | 0.52398 (15) | 0.36544 (16) | 0.43571 (2) | 0.0156 (2) | |
C9A | 0.48504 (15) | 0.20665 (16) | 0.42300 (2) | 0.0145 (2) | |
H1N | 0.503 (2) | 0.071 (2) | 0.3910 (3) | 0.016 (4)* | |
H1O | 0.705 (3) | 0.743 (3) | 0.3911 (3) | 0.038 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0207 (4) | 0.0099 (4) | 0.0268 (5) | −0.0010 (3) | −0.0003 (4) | 0.0033 (3) |
N1 | 0.0191 (5) | 0.0097 (5) | 0.0153 (5) | 0.0002 (4) | −0.0008 (4) | 0.0010 (4) |
F1 | 0.0618 (6) | 0.0304 (5) | 0.0156 (4) | −0.0003 (4) | 0.0054 (4) | 0.0026 (3) |
C2 | 0.0149 (5) | 0.0127 (6) | 0.0170 (5) | −0.0006 (4) | −0.0016 (4) | 0.0019 (4) |
C3 | 0.0172 (5) | 0.0124 (5) | 0.0181 (5) | −0.0004 (4) | −0.0010 (4) | 0.0034 (4) |
C4 | 0.0164 (5) | 0.0101 (5) | 0.0222 (6) | −0.0006 (4) | 0.0005 (4) | 0.0029 (4) |
C5 | 0.0182 (5) | 0.0115 (5) | 0.0185 (5) | −0.0013 (4) | −0.0012 (4) | −0.0002 (4) |
C6 | 0.0270 (6) | 0.0166 (6) | 0.0177 (6) | 0.0022 (5) | −0.0009 (5) | −0.0007 (5) |
C7 | 0.0297 (6) | 0.0251 (7) | 0.0142 (5) | 0.0032 (6) | 0.0006 (5) | 0.0039 (5) |
C8 | 0.0232 (6) | 0.0192 (6) | 0.0214 (6) | −0.0011 (5) | 0.0003 (5) | 0.0077 (5) |
C9 | 0.0177 (5) | 0.0145 (6) | 0.0213 (6) | −0.0017 (5) | −0.0027 (4) | 0.0028 (5) |
C21 | 0.0191 (5) | 0.0162 (6) | 0.0171 (5) | −0.0031 (5) | −0.0039 (4) | 0.0030 (4) |
C22 | 0.0198 (6) | 0.0200 (6) | 0.0168 (6) | −0.0003 (5) | −0.0034 (4) | 0.0011 (5) |
C23 | 0.0235 (6) | 0.0170 (6) | 0.0178 (6) | −0.0033 (5) | 0.0000 (5) | 0.0007 (5) |
C24 | 0.0275 (7) | 0.0266 (7) | 0.0240 (6) | 0.0029 (6) | −0.0017 (5) | −0.0016 (5) |
C25 | 0.0342 (7) | 0.0289 (8) | 0.0283 (7) | 0.0014 (6) | 0.0042 (6) | −0.0065 (6) |
C26 | 0.0407 (8) | 0.0270 (7) | 0.0184 (6) | −0.0099 (6) | 0.0042 (6) | −0.0034 (5) |
C27 | 0.0401 (8) | 0.0233 (7) | 0.0170 (6) | −0.0078 (6) | −0.0048 (5) | 0.0033 (5) |
C28 | 0.0311 (7) | 0.0180 (6) | 0.0200 (6) | −0.0015 (5) | −0.0036 (5) | 0.0018 (5) |
C5A | 0.0156 (5) | 0.0134 (6) | 0.0176 (5) | 0.0025 (4) | −0.0008 (4) | 0.0014 (4) |
C9A | 0.0131 (5) | 0.0146 (6) | 0.0158 (5) | 0.0012 (4) | −0.0014 (4) | 0.0016 (4) |
O1—C4 | 1.4367 (14) | C8—C9 | 1.3880 (17) |
N1—C9A | 1.4312 (15) | C9—C9A | 1.3957 (17) |
N1—C2 | 1.4786 (15) | C21—C22 | 1.3292 (18) |
F1—C7 | 1.3649 (14) | C22—C23 | 1.4739 (17) |
C2—C21 | 1.5058 (17) | C23—C28 | 1.3970 (18) |
C2—C3 | 1.5321 (16) | C23—C24 | 1.3974 (19) |
C3—C4 | 1.5235 (17) | C24—C25 | 1.390 (2) |
C4—C5 | 1.5264 (16) | C25—C26 | 1.385 (2) |
C5—C5A | 1.5050 (16) | C26—C27 | 1.382 (2) |
C6—C7 | 1.3785 (19) | C27—C28 | 1.3904 (18) |
C6—C5A | 1.3936 (17) | C5A—C9A | 1.3995 (17) |
C7—C8 | 1.372 (2) | ||
C9A—N1—C2 | 117.48 (10) | C21—C22—C23 | 126.59 (12) |
N1—C2—C21 | 110.88 (10) | C28—C23—C24 | 118.28 (12) |
N1—C2—C3 | 111.35 (9) | C28—C23—C22 | 123.04 (12) |
C21—C2—C3 | 108.83 (10) | C24—C23—C22 | 118.68 (12) |
C4—C3—C2 | 116.02 (10) | C25—C24—C23 | 121.02 (13) |
O1—C4—C3 | 108.10 (10) | C26—C25—C24 | 119.93 (14) |
O1—C4—C5 | 108.78 (10) | C27—C26—C25 | 119.75 (13) |
C3—C4—C5 | 115.01 (10) | C26—C27—C28 | 120.53 (13) |
C5A—C5—C4 | 117.65 (10) | C27—C28—C23 | 120.48 (13) |
C7—C6—C5A | 119.61 (12) | C6—C5A—C9A | 118.76 (11) |
F1—C7—C8 | 118.75 (12) | C6—C5A—C5 | 118.63 (11) |
F1—C7—C6 | 118.32 (12) | C9A—C5A—C5 | 122.40 (11) |
C8—C7—C6 | 122.92 (12) | C9—C9A—C5A | 119.82 (11) |
C7—C8—C9 | 117.54 (12) | C9—C9A—N1 | 119.24 (11) |
C8—C9—C9A | 121.33 (12) | C5A—C9A—N1 | 120.71 (11) |
C22—C21—C2 | 126.64 (11) | ||
C9A—N1—C2—C21 | −154.56 (10) | C22—C23—C24—C25 | −179.08 (13) |
C9A—N1—C2—C3 | 84.10 (12) | C23—C24—C25—C26 | −0.7 (2) |
N1—C2—C3—C4 | −65.54 (13) | C24—C25—C26—C27 | −0.4 (2) |
C21—C2—C3—C4 | 171.93 (10) | C25—C26—C27—C28 | 0.7 (2) |
C2—C3—C4—O1 | −177.68 (9) | C26—C27—C28—C23 | 0.1 (2) |
C2—C3—C4—C5 | 60.58 (14) | C24—C23—C28—C27 | −1.1 (2) |
O1—C4—C5—C5A | 168.01 (10) | C22—C23—C28—C27 | 179.41 (12) |
C3—C4—C5—C5A | −70.62 (14) | C7—C6—C5A—C9A | 1.06 (18) |
C5A—C6—C7—F1 | −179.62 (12) | C7—C6—C5A—C5 | −173.82 (12) |
C5A—C6—C7—C8 | 0.2 (2) | C4—C5—C5A—C6 | −126.84 (12) |
F1—C7—C8—C9 | 178.58 (12) | C4—C5—C5A—C9A | 58.48 (16) |
C6—C7—C8—C9 | −1.3 (2) | C8—C9—C9A—C5A | 0.20 (18) |
C7—C8—C9—C9A | 1.04 (19) | C8—C9—C9A—N1 | 174.73 (11) |
N1—C2—C21—C22 | −6.00 (17) | C6—C5A—C9A—C9 | −1.26 (17) |
C3—C2—C21—C22 | 116.81 (14) | C5—C5A—C9A—C9 | 173.41 (11) |
C2—C21—C22—C23 | −178.19 (12) | C6—C5A—C9A—N1 | −175.70 (11) |
C21—C22—C23—C28 | −11.9 (2) | C5—C5A—C9A—N1 | −1.03 (17) |
C21—C22—C23—C24 | 168.68 (13) | C2—N1—C9A—C9 | 120.88 (12) |
C28—C23—C24—C25 | 1.4 (2) | C2—N1—C9A—C5A | −64.65 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.904 (17) | 2.450 (16) | 3.2709 (14) | 151 (13) |
O1—H1O···N1ii | 0.88 (2) | 2.14 (2) | 3.0187 (14) | 172.9 (16) |
C5—H5A···N1ii | 0.99 | 2.67 | 3.3657 (16) | 128 |
C6—H6···F1iii | 0.95 | 2.47 | 3.4236 (16) | 177 |
C5—H5A···O1iv | 0.99 | 2.53 | 3.4027 (15) | 148 |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y+1/2, z; (iii) −x+1, −y+1, −z+1; (iv) −x+3/2, y−1/2, z. |
C15H20FNO | Dx = 1.207 Mg m−3 |
Mr = 249.32 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3:H | Cell parameters from 9421 reflections |
a = 25.119 (2) Å | θ = 2.8–22.2° |
c = 11.2812 (12) Å | µ = 0.08 mm−1 |
V = 6164.2 (12) Å3 | T = 298 K |
Z = 18 | Parallelepiped, less |
F(000) = 2412 | 0.30 × 0.25 × 0.20 mm |
Bruker Kappa APEXII diffractometer | 2024 reflections with I > 2σ(I) |
π and ω scans | Rint = 0.036 |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | θmax = 26.4°, θmin = 2.6° |
Tmin = 0.68, Tmax = 0.74 | h = −31→31 |
34372 measured reflections | k = −31→26 |
2814 independent reflections | l = −14→14 |
Refinement on F2 | Primary atom site location: iterative |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.066 | Hydrogen site location: mixed |
wR(F2) = 0.229 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1155P)2 + 11.0098P] where P = (Fo2 + 2Fc2)/3 |
2814 reflections | (Δ/σ)max < 0.001 |
212 parameters | Δρmax = 0.55 e Å−3 |
159 restraints | Δρmin = −0.41 e Å−3 |
C15H20FNO | Z = 18 |
Mr = 249.32 | Mo Kα radiation |
Trigonal, R3:H | µ = 0.08 mm−1 |
a = 25.119 (2) Å | T = 298 K |
c = 11.2812 (12) Å | 0.30 × 0.25 × 0.20 mm |
V = 6164.2 (12) Å3 |
Bruker Kappa APEXII diffractometer | 2814 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 2024 reflections with I > 2σ(I) |
Tmin = 0.68, Tmax = 0.74 | Rint = 0.036 |
34372 measured reflections |
R[F2 > 2σ(F2)] = 0.066 | 159 restraints |
wR(F2) = 0.229 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1155P)2 + 11.0098P] where P = (Fo2 + 2Fc2)/3 |
2814 reflections | Δρmax = 0.55 e Å−3 |
212 parameters | Δρmin = −0.41 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 0.44770 (10) | 0.47721 (10) | 0.65896 (18) | 0.0460 (5) | |
F1 | 0.53114 (10) | 0.41476 (10) | 1.06076 (18) | 0.0891 (7) | |
C2 | 0.39810 (12) | 0.49241 (11) | 0.6739 (2) | 0.0480 (6) | |
C3 | 0.33455 (11) | 0.43494 (12) | 0.6811 (2) | 0.0494 (6) | |
H3A | 0.3041 | 0.4480 | 0.6832 | 0.059* | |
H3B | 0.3279 | 0.4116 | 0.6087 | 0.059* | |
H1N | 0.4810 (14) | 0.5102 (14) | 0.634 (3) | 0.062 (8)* | |
C4 | 0.32254 (10) | 0.39220 (11) | 0.7848 (2) | 0.0448 (6) | |
H4 | 0.3283 | 0.4148 | 0.8589 | 0.054* | |
H2 | 0.4062 (13) | 0.5176 (13) | 0.745 (3) | 0.054 (7)* | |
C5 | 0.36406 (11) | 0.36420 (11) | 0.7852 (2) | 0.0454 (6) | |
H5A | 0.3460 | 0.3285 | 0.8366 | 0.055* | |
H5B | 0.3653 | 0.3502 | 0.7057 | 0.055* | |
C6 | 0.45135 (13) | 0.39216 (12) | 0.9261 (2) | 0.0530 (6) | |
H6 | 0.4260 | 0.3566 | 0.9687 | 0.064* | |
C7 | 0.51085 (14) | 0.43021 (14) | 0.9618 (3) | 0.0616 (7) | |
O7 | 0.25956 (8) | 0.34478 (9) | 0.77523 (17) | 0.0593 (6) | |
H7O | 0.2424 (9) | 0.3368 (13) | 0.846 (3) | 0.089* | |
C8 | 0.54992 (14) | 0.48273 (15) | 0.9022 (3) | 0.0675 (8) | |
H8 | 0.5902 | 0.5076 | 0.9276 | 0.081* | |
C9 | 0.52822 (12) | 0.49807 (13) | 0.8031 (3) | 0.0566 (7) | |
H9 | 0.5542 | 0.5338 | 0.7616 | 0.068* | |
C10A | 0.39929 (15) | 0.53013 (13) | 0.5698 (3) | 0.0644 (11) | 0.483 (5) |
H10A | 0.4025 | 0.5136 | 0.4981 | 0.077* | 0.483 (5) |
C11A | 0.3970 (8) | 0.5805 (5) | 0.5554 (10) | 0.089 (3) | 0.483 (5) |
H11A | 0.3990 | 0.6020 | 0.6241 | 0.107* | 0.483 (5) |
C12A | 0.3909 (5) | 0.6096 (6) | 0.4329 (11) | 0.118 (3) | 0.483 (5) |
H12A | 0.3870 | 0.6455 | 0.4493 | 0.141* | 0.483 (5) |
H12B | 0.3542 | 0.5798 | 0.3912 | 0.141* | 0.483 (5) |
C13A | 0.4515 (6) | 0.6295 (6) | 0.3498 (9) | 0.115 (3) | 0.483 (5) |
H13A | 0.4899 | 0.6515 | 0.3932 | 0.138* | 0.483 (5) |
H13B | 0.4497 | 0.5951 | 0.3070 | 0.138* | 0.483 (5) |
C14A | 0.4386 (9) | 0.6712 (6) | 0.2717 (14) | 0.148 (5) | 0.483 (5) |
H14A | 0.4390 | 0.6607 | 0.1900 | 0.222* | 0.483 (5) |
H14B | 0.4697 | 0.7132 | 0.2848 | 0.222* | 0.483 (5) |
H14C | 0.3990 | 0.6658 | 0.2912 | 0.222* | 0.483 (5) |
C10B | 0.39929 (15) | 0.53013 (13) | 0.5698 (3) | 0.0644 (11) | 0.517 (5) |
H10B | 0.3975 | 0.5162 | 0.4927 | 0.077* | 0.517 (5) |
C11B | 0.4029 (7) | 0.5829 (4) | 0.5902 (8) | 0.078 (2) | 0.517 (5) |
H11B | 0.4047 | 0.5958 | 0.6682 | 0.094* | 0.517 (5) |
C12B | 0.4042 (4) | 0.6253 (4) | 0.4865 (7) | 0.096 (2) | 0.517 (5) |
H12C | 0.4381 | 0.6667 | 0.4994 | 0.115* | 0.517 (5) |
H12D | 0.3664 | 0.6270 | 0.4885 | 0.115* | 0.517 (5) |
C13B | 0.4115 (6) | 0.6019 (5) | 0.3546 (8) | 0.112 (3) | 0.517 (5) |
H13C | 0.4457 | 0.5943 | 0.3592 | 0.134* | 0.517 (5) |
H13D | 0.3749 | 0.5624 | 0.3410 | 0.134* | 0.517 (5) |
C14B | 0.4214 (8) | 0.6408 (6) | 0.2428 (13) | 0.150 (4) | 0.517 (5) |
H14D | 0.4142 | 0.6159 | 0.1736 | 0.224* | 0.517 (5) |
H14E | 0.4629 | 0.6746 | 0.2416 | 0.224* | 0.517 (5) |
H14F | 0.3934 | 0.6563 | 0.2435 | 0.224* | 0.517 (5) |
C5A | 0.42899 (11) | 0.40696 (11) | 0.8254 (2) | 0.0435 (6) | |
C9A | 0.46799 (11) | 0.46087 (11) | 0.7641 (2) | 0.0438 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0457 (11) | 0.0416 (11) | 0.0437 (11) | 0.0167 (9) | 0.0038 (9) | 0.0029 (9) |
F1 | 0.0927 (14) | 0.1043 (15) | 0.0805 (13) | 0.0569 (12) | −0.0324 (11) | 0.0035 (11) |
C2 | 0.0540 (14) | 0.0443 (13) | 0.0463 (14) | 0.0251 (11) | −0.0033 (11) | 0.0000 (10) |
C3 | 0.0476 (13) | 0.0537 (14) | 0.0480 (14) | 0.0262 (11) | −0.0002 (10) | 0.0032 (11) |
C4 | 0.0407 (12) | 0.0495 (13) | 0.0398 (12) | 0.0192 (10) | 0.0006 (9) | −0.0003 (10) |
C5 | 0.0478 (13) | 0.0412 (12) | 0.0418 (13) | 0.0181 (10) | 0.0012 (10) | 0.0027 (9) |
C6 | 0.0587 (15) | 0.0557 (15) | 0.0513 (15) | 0.0337 (13) | −0.0018 (12) | 0.0029 (12) |
C7 | 0.0658 (17) | 0.0717 (18) | 0.0590 (17) | 0.0430 (16) | −0.0138 (14) | −0.0040 (14) |
O7 | 0.0418 (9) | 0.0710 (12) | 0.0495 (11) | 0.0166 (9) | 0.0016 (8) | 0.0092 (9) |
C8 | 0.0541 (16) | 0.0657 (18) | 0.081 (2) | 0.0289 (14) | −0.0206 (15) | −0.0135 (16) |
C9 | 0.0488 (14) | 0.0485 (14) | 0.0675 (18) | 0.0205 (11) | −0.0045 (12) | −0.0019 (12) |
C10A | 0.069 (2) | 0.0536 (17) | 0.0644 (19) | 0.0259 (15) | −0.0082 (15) | 0.0126 (14) |
C11A | 0.093 (4) | 0.084 (4) | 0.095 (5) | 0.047 (3) | −0.015 (4) | 0.024 (3) |
C12A | 0.120 (4) | 0.103 (4) | 0.116 (5) | 0.045 (3) | −0.017 (4) | 0.013 (4) |
C13A | 0.119 (5) | 0.110 (4) | 0.102 (4) | 0.046 (4) | −0.025 (4) | 0.022 (4) |
C14A | 0.156 (8) | 0.126 (8) | 0.134 (8) | 0.049 (7) | −0.023 (6) | 0.024 (6) |
C10B | 0.069 (2) | 0.0536 (17) | 0.0644 (19) | 0.0259 (15) | −0.0082 (15) | 0.0126 (14) |
C11B | 0.083 (4) | 0.074 (3) | 0.078 (4) | 0.040 (3) | −0.015 (4) | 0.021 (3) |
C12B | 0.113 (4) | 0.080 (3) | 0.092 (4) | 0.046 (3) | −0.035 (3) | 0.022 (3) |
C13B | 0.120 (5) | 0.107 (4) | 0.087 (4) | 0.040 (4) | −0.013 (4) | 0.019 (4) |
C14B | 0.175 (9) | 0.125 (8) | 0.137 (6) | 0.066 (7) | 0.002 (7) | 0.042 (6) |
C5A | 0.0465 (12) | 0.0452 (12) | 0.0430 (12) | 0.0260 (10) | 0.0003 (10) | −0.0019 (10) |
C9A | 0.0464 (13) | 0.0418 (12) | 0.0451 (13) | 0.0235 (10) | 0.0003 (10) | −0.0034 (10) |
N1—C9A | 1.430 (3) | C7—C8 | 1.365 (5) |
N1—C2 | 1.484 (3) | C8—C9 | 1.380 (4) |
F1—C7 | 1.361 (3) | C9—C9A | 1.393 (4) |
C2—C10A | 1.500 (4) | C10A—C11A | 1.306 (5) |
C2—C3 | 1.528 (4) | C11A—C12A | 1.606 (10) |
C3—C4 | 1.512 (3) | C12A—C13A | 1.639 (11) |
C4—O7 | 1.431 (3) | C13A—C14A | 1.522 (11) |
C4—C5 | 1.522 (3) | C11B—C12B | 1.572 (8) |
C5—C5A | 1.506 (3) | C12B—C13B | 1.645 (10) |
C6—C7 | 1.372 (4) | C13B—C14B | 1.537 (10) |
C6—C5A | 1.398 (4) | C5A—C9A | 1.395 (3) |
C9A—N1—C2 | 116.44 (19) | C8—C9—C9A | 121.1 (3) |
N1—C2—C10A | 108.6 (2) | C11A—C10A—C2 | 135.5 (6) |
N1—C2—C3 | 112.2 (2) | C10A—C11A—C12A | 127.5 (10) |
C10A—C2—C3 | 108.6 (2) | C11A—C12A—C13A | 110.2 (10) |
C4—C3—C2 | 117.1 (2) | C14A—C13A—C12A | 93.2 (11) |
O7—C4—C3 | 106.11 (19) | C11B—C12B—C13B | 113.5 (7) |
O7—C4—C5 | 110.1 (2) | C14B—C13B—C12B | 121.7 (10) |
C3—C4—C5 | 113.0 (2) | C9A—C5A—C6 | 118.7 (2) |
C5A—C5—C4 | 114.8 (2) | C9A—C5A—C5 | 121.8 (2) |
C7—C6—C5A | 119.8 (3) | C6—C5A—C5 | 119.4 (2) |
F1—C7—C8 | 119.3 (3) | C9—C9A—C5A | 119.6 (2) |
F1—C7—C6 | 118.4 (3) | C9—C9A—N1 | 119.5 (2) |
C8—C7—C6 | 122.3 (3) | C5A—C9A—N1 | 120.8 (2) |
C7—C8—C9 | 118.4 (3) | ||
C9A—N1—C2—C10A | 158.9 (2) | C10A—C11A—C12A—C13A | −63.7 (19) |
C9A—N1—C2—C3 | −81.0 (3) | C11A—C12A—C13A—C14A | −162.5 (10) |
N1—C2—C3—C4 | 63.2 (3) | C11B—C12B—C13B—C14B | −172.6 (12) |
C10A—C2—C3—C4 | −176.7 (2) | C7—C6—C5A—C9A | −0.6 (4) |
C2—C3—C4—O7 | 176.5 (2) | C7—C6—C5A—C5 | 178.6 (2) |
C2—C3—C4—C5 | −62.8 (3) | C4—C5—C5A—C9A | −62.1 (3) |
O7—C4—C5—C5A | −165.3 (2) | C4—C5—C5A—C6 | 118.6 (2) |
C3—C4—C5—C5A | 76.3 (3) | C8—C9—C9A—C5A | −0.5 (4) |
C5A—C6—C7—F1 | 179.5 (2) | C8—C9—C9A—N1 | −178.0 (3) |
C5A—C6—C7—C8 | −0.2 (4) | C6—C5A—C9A—C9 | 1.0 (4) |
F1—C7—C8—C9 | −179.1 (3) | C5—C5A—C9A—C9 | −178.3 (2) |
C6—C7—C8—C9 | 0.7 (5) | C6—C5A—C9A—N1 | 178.5 (2) |
C7—C8—C9—C9A | −0.3 (5) | C5—C5A—C9A—N1 | −0.8 (3) |
N1—C2—C10A—C11A | −133.6 (11) | C2—N1—C9A—C9 | −116.0 (3) |
C3—C2—C10A—C11A | 104.1 (12) | C2—N1—C9A—C5A | 66.5 (3) |
C2—C10A—C11A—C12A | −172.1 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O7i | 0.88 (3) | 2.49 (3) | 3.356 (3) | 171 (3) |
O7—H7O···N1ii | 0.88 | 2.02 | 2.889 (3) | 169 |
C9—H9···O7i | 0.93 | 2.63 | 3.451 (4) | 147 |
Symmetry codes: (i) x−y+2/3, x+1/3, −z+4/3; (ii) −y+2/3, x−y+1/3, z+1/3. |
C15H20FNO | Dx = 1.262 Mg m−3 |
Mr = 249.32 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3:H | Cell parameters from 9791 reflections |
a = 49.395 (2) Å | θ = 2.9–27.4° |
c = 11.1802 (5) Å | µ = 0.09 mm−1 |
V = 23623 (2) Å3 | T = 100 K |
Z = 72 | Parallelepiped, less |
F(000) = 9648 | 0.30 × 0.25 × 0.20 mm |
Bruker Kappa APEXII diffractometer | 8771 reflections with I > 2σ(I) |
π and ω scans | Rint = 0.043 |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | θmax = 27.5°, θmin = 1.4° |
Tmin = 0.89, Tmax = 0.98 | h = −62→62 |
124259 measured reflections | k = −63→64 |
12035 independent reflections | l = −14→13 |
Refinement on F2 | 459 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.048P)2 + 28.8932P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
12035 reflections | Δρmax = 0.44 e Å−3 |
786 parameters | Δρmin = −0.28 e Å−3 |
C15H20FNO | Z = 72 |
Mr = 249.32 | Mo Kα radiation |
Trigonal, R3:H | µ = 0.09 mm−1 |
a = 49.395 (2) Å | T = 100 K |
c = 11.1802 (5) Å | 0.30 × 0.25 × 0.20 mm |
V = 23623 (2) Å3 |
Bruker Kappa APEXII diffractometer | 12035 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 8771 reflections with I > 2σ(I) |
Tmin = 0.89, Tmax = 0.98 | Rint = 0.043 |
124259 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 459 restraints |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.048P)2 + 28.8932P] where P = (Fo2 + 2Fc2)/3 |
12035 reflections | Δρmax = 0.44 e Å−3 |
786 parameters | Δρmin = −0.28 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N11 | 0.34466 (3) | 0.40532 (3) | 1.00064 (10) | 0.0169 (2) | |
F11 | 0.27312 (2) | 0.37140 (2) | 0.58610 (7) | 0.0270 (2) | |
C411 | 0.29720 (4) | 0.59163 (4) | 0.57416 (16) | 0.0377 (4) | 0.319 (8) |
H11C | 0.2986 | 0.6002 | 0.6516 | 0.045* | 0.319 (8) |
C412 | 0.2953 (3) | 0.6093 (3) | 0.4671 (7) | 0.0305 (11) | 0.319 (8) |
H12E | 0.2812 | 0.6174 | 0.4885 | 0.037* | 0.319 (8) |
H12F | 0.3163 | 0.6276 | 0.4544 | 0.037* | 0.319 (8) |
C413 | 0.2844 (2) | 0.59265 (19) | 0.3497 (7) | 0.0308 (13) | 0.319 (8) |
H13E | 0.2641 | 0.5732 | 0.3605 | 0.037* | 0.319 (8) |
H13F | 0.2997 | 0.5870 | 0.3196 | 0.037* | 0.319 (8) |
C414 | 0.28076 (17) | 0.61383 (14) | 0.2595 (6) | 0.0300 (14) | 0.319 (8) |
H14G | 0.2715 | 0.6021 | 0.1857 | 0.045* | 0.319 (8) |
H14H | 0.3013 | 0.6319 | 0.2419 | 0.045* | 0.319 (8) |
H14I | 0.2672 | 0.6211 | 0.2931 | 0.045* | 0.319 (8) |
C415 | 0.29720 (4) | 0.59163 (4) | 0.57416 (16) | 0.0377 (4) | 0.341 (3) |
H15 | 0.2921 | 0.5936 | 0.6545 | 0.045* | 0.341 (3) |
C416 | 0.30233 (12) | 0.62061 (12) | 0.5067 (5) | 0.0299 (9) | 0.341 (3) |
H16A | 0.2848 | 0.6245 | 0.5204 | 0.036* | 0.341 (3) |
H16B | 0.3220 | 0.6393 | 0.5323 | 0.036* | 0.341 (3) |
C417 | 0.30403 (10) | 0.61315 (11) | 0.3761 (4) | 0.0273 (9) | 0.341 (3) |
H17A | 0.3190 | 0.6054 | 0.3676 | 0.033* | 0.341 (3) |
H17B | 0.3120 | 0.6325 | 0.3283 | 0.033* | 0.341 (3) |
C418 | 0.27235 (13) | 0.58869 (13) | 0.3269 (5) | 0.0323 (12) | 0.341 (3) |
H18A | 0.2744 | 0.5854 | 0.2416 | 0.048* | 0.341 (3) |
H18B | 0.2573 | 0.5959 | 0.3374 | 0.048* | 0.341 (3) |
H18C | 0.2650 | 0.5690 | 0.3700 | 0.048* | 0.341 (3) |
C419 | 0.29720 (4) | 0.59163 (4) | 0.57416 (16) | 0.0377 (4) | 0.340 (8) |
H19A | 0.2981 | 0.6011 | 0.6492 | 0.045* | 0.340 (8) |
C420 | 0.2958 (3) | 0.6069 (2) | 0.4514 (7) | 0.0306 (11) | 0.340 (8) |
H20A | 0.2784 | 0.6112 | 0.4580 | 0.037* | 0.340 (8) |
H20B | 0.3153 | 0.6274 | 0.4463 | 0.037* | 0.340 (8) |
C421 | 0.29209 (17) | 0.59085 (15) | 0.3319 (6) | 0.0289 (11) | 0.340 (8) |
H21A | 0.2725 | 0.5704 | 0.3329 | 0.035* | 0.340 (8) |
H21B | 0.3097 | 0.5870 | 0.3204 | 0.035* | 0.340 (8) |
C422 | 0.29106 (17) | 0.61025 (12) | 0.2260 (6) | 0.0293 (14) | 0.340 (8) |
H22A | 0.2890 | 0.5991 | 0.1511 | 0.044* | 0.340 (8) |
H22B | 0.3104 | 0.6306 | 0.2244 | 0.044* | 0.340 (8) |
H22C | 0.2731 | 0.6134 | 0.2352 | 0.044* | 0.340 (8) |
C410 | 0.29701 (4) | 0.56496 (4) | 0.56497 (14) | 0.0307 (4) | |
C49A | 0.26156 (3) | 0.49464 (3) | 0.76169 (12) | 0.0185 (3) | |
C49 | 0.23086 (3) | 0.48294 (3) | 0.80082 (13) | 0.0224 (3) | |
H9C | 0.2175 | 0.4883 | 0.7585 | 0.027* | |
C48 | 0.21945 (3) | 0.46363 (3) | 0.90032 (14) | 0.0254 (3) | |
H8C | 0.1985 | 0.4555 | 0.9261 | 0.030* | |
H2O | 0.2841 (4) | 0.4991 (5) | 0.5109 (18) | 0.050 (6)* | |
C47 | 0.23945 (3) | 0.45664 (3) | 0.96036 (13) | 0.0240 (3) | |
H3O | 0.3292 (4) | 0.4518 (4) | 0.1705 (17) | 0.041 (5)* | |
C46 | 0.26982 (3) | 0.46764 (3) | 0.92451 (12) | 0.0205 (3) | |
H6C | 0.2829 | 0.4622 | 0.9683 | 0.025* | |
H1O | 0.3815 (4) | 0.3372 (4) | 0.8117 (17) | 0.043 (5)* | |
C45A | 0.28138 (3) | 0.48676 (3) | 0.82365 (12) | 0.0178 (3) | |
H4O | 0.3758 (4) | 0.5448 (4) | 0.8477 (18) | 0.044 (5)* | |
C45 | 0.31449 (3) | 0.49801 (3) | 0.78342 (12) | 0.0175 (3) | |
H5CA | 0.3139 | 0.4901 | 0.7016 | 0.021* | |
H5CB | 0.3238 | 0.4889 | 0.8367 | 0.021* | |
C44 | 0.33575 (3) | 0.53372 (3) | 0.78294 (12) | 0.0178 (3) | |
H4C | 0.3324 | 0.5425 | 0.8585 | 0.021* | |
H2N | 0.3134 (4) | 0.4083 (4) | 0.2895 (14) | 0.026 (4)* | |
C43 | 0.32988 (3) | 0.54921 (3) | 0.67663 (12) | 0.0195 (3) | |
H3CA | 0.3329 | 0.5401 | 0.6026 | 0.023* | |
H3CB | 0.3459 | 0.5717 | 0.6772 | 0.023* | |
H1N | 0.3431 (3) | 0.4215 (4) | 1.0311 (14) | 0.023 (4)* | |
C42 | 0.29770 (3) | 0.54646 (3) | 0.67063 (12) | 0.0197 (3) | |
H2C | 0.2941 | 0.5553 | 0.7455 | 0.024* | |
H10C | 0.2965 (4) | 0.5564 (4) | 0.4860 (17) | 0.045 (5)* | |
H3N | 0.4201 (4) | 0.5736 (4) | −0.0348 (14) | 0.027 (4)* | |
H4N | 0.2554 (4) | 0.5138 (4) | 0.6247 (14) | 0.024 (4)* | |
O11 | 0.37855 (2) | 0.34202 (2) | 0.88342 (9) | 0.0209 (2) | |
N21 | 0.31433 (3) | 0.42554 (3) | 0.31909 (10) | 0.0169 (2) | |
F21 | 0.39145 (2) | 0.45825 (2) | 0.71821 (7) | 0.0300 (2) | |
O21 | 0.28801 (2) | 0.49469 (2) | 0.43828 (9) | 0.0223 (2) | |
C22 | 0.28152 (3) | 0.41842 (3) | 0.34093 (11) | 0.0173 (3) | |
H2B | 0.2741 | 0.4072 | 0.4191 | 0.021* | |
C12 | 0.37836 (3) | 0.41447 (3) | 0.99245 (12) | 0.0174 (3) | |
H2A | 0.3879 | 0.4283 | 0.9212 | 0.021* | |
N31 | 0.40300 (3) | 0.55637 (3) | −0.00756 (10) | 0.0185 (2) | |
F31 | 0.37125 (2) | 0.59685 (2) | 0.40456 (8) | 0.0333 (2) | |
O31 | 0.33407 (2) | 0.45989 (2) | 0.09972 (9) | 0.0210 (2) | |
N41 | 0.27191 (3) | 0.51345 (3) | 0.65589 (10) | 0.0193 (2) | |
F41 | 0.22883 (2) | 0.43795 (2) | 1.05925 (8) | 0.0328 (2) | |
O41 | 0.36780 (2) | 0.54157 (2) | 0.77562 (9) | 0.0221 (2) | |
C23 | 0.27900 (3) | 0.44792 (3) | 0.34420 (12) | 0.0187 (3) | |
H3BA | 0.2877 | 0.4595 | 0.2686 | 0.022* | |
H3BB | 0.2566 | 0.4416 | 0.3467 | 0.022* | |
C13 | 0.38308 (3) | 0.38618 (3) | 0.98311 (12) | 0.0181 (3) | |
H3A | 0.4058 | 0.3939 | 0.9826 | 0.022* | |
H3B | 0.3744 | 0.3734 | 1.0564 | 0.022* | |
C32 | 0.40991 (3) | 0.53030 (3) | 0.00136 (12) | 0.0186 (3) | |
H2D | 0.4223 | 0.5330 | 0.0758 | 0.022* | |
C24 | 0.29539 (3) | 0.47014 (3) | 0.44786 (12) | 0.0185 (3) | |
H4B | 0.2869 | 0.4587 | 0.5249 | 0.022* | |
C14 | 0.36875 (3) | 0.36484 (3) | 0.87580 (11) | 0.0175 (3) | |
H14 | 0.3773 | 0.3773 | 0.8008 | 0.021* | |
C33 | 0.38020 (3) | 0.49827 (3) | 0.00420 (12) | 0.0181 (3) | |
H3DA | 0.3681 | 0.4960 | −0.0695 | 0.022* | |
H3DB | 0.3864 | 0.4820 | 0.0019 | 0.022* | |
C34 | 0.35875 (3) | 0.49174 (3) | 0.11100 (12) | 0.0180 (3) | |
H4D | 0.3707 | 0.4941 | 0.1863 | 0.022* | |
C25 | 0.33097 (3) | 0.48406 (3) | 0.44610 (12) | 0.0184 (3) | |
H5BA | 0.3386 | 0.4912 | 0.3638 | 0.022* | |
H5BB | 0.3406 | 0.5026 | 0.4988 | 0.022* | |
C15 | 0.33288 (3) | 0.34862 (3) | 0.87380 (12) | 0.0176 (3) | |
H15A | 0.3247 | 0.3300 | 0.8215 | 0.021* | |
H15B | 0.3249 | 0.3413 | 0.9556 | 0.021* | |
C35 | 0.34482 (3) | 0.51345 (3) | 0.11627 (12) | 0.0183 (3) | |
H5DA | 0.3377 | 0.5150 | 0.0351 | 0.022* | |
H5DB | 0.3262 | 0.5038 | 0.1688 | 0.022* | |
C35A | 0.36701 (3) | 0.54597 (3) | 0.16138 (12) | 0.0187 (3) | |
C25A | 0.34204 (3) | 0.46199 (3) | 0.48536 (11) | 0.0176 (3) | |
C15A | 0.32065 (3) | 0.36931 (3) | 0.83032 (11) | 0.0166 (3) | |
C16 | 0.30230 (3) | 0.36121 (3) | 0.72687 (11) | 0.0185 (3) | |
H6A | 0.2976 | 0.3427 | 0.6843 | 0.022* | |
C17 | 0.29108 (3) | 0.38009 (3) | 0.68695 (12) | 0.0204 (3) | |
C36 | 0.35949 (3) | 0.55690 (3) | 0.26442 (12) | 0.0216 (3) | |
H6D | 0.3407 | 0.5437 | 0.3067 | 0.026* | |
C26 | 0.36144 (3) | 0.46957 (3) | 0.58553 (12) | 0.0205 (3) | |
H6B | 0.3671 | 0.4881 | 0.6294 | 0.025* | |
C18 | 0.29731 (3) | 0.40719 (3) | 0.74472 (12) | 0.0218 (3) | |
H8A | 0.2893 | 0.4199 | 0.7154 | 0.026* | |
C37 | 0.37940 (3) | 0.58679 (4) | 0.30412 (13) | 0.0253 (3) | |
C27 | 0.37238 (3) | 0.45005 (3) | 0.62031 (12) | 0.0224 (3) | |
C19 | 0.31558 (3) | 0.41541 (3) | 0.84723 (12) | 0.0199 (3) | |
H9A | 0.3202 | 0.4341 | 0.8884 | 0.024* | |
C38 | 0.40681 (3) | 0.60682 (3) | 0.24662 (13) | 0.0269 (3) | |
H8D | 0.4201 | 0.6274 | 0.2757 | 0.032* | |
C28 | 0.36511 (3) | 0.42299 (3) | 0.56027 (12) | 0.0219 (3) | |
H8B | 0.3732 | 0.4101 | 0.5855 | 0.026* | |
C19A | 0.32728 (3) | 0.39686 (3) | 0.89089 (11) | 0.0168 (3) | |
C39 | 0.41454 (3) | 0.59611 (3) | 0.14481 (13) | 0.0235 (3) | |
H9D | 0.4335 | 0.6095 | 0.1040 | 0.028* | |
C29 | 0.34556 (3) | 0.41512 (3) | 0.46162 (12) | 0.0199 (3) | |
H9B | 0.3400 | 0.3964 | 0.4193 | 0.024* | |
C110 | 0.39442 (3) | 0.43229 (3) | 1.10426 (12) | 0.0183 (3) | |
H10A | 0.3848 | 0.4236 | 1.1790 | 0.022* | |
C29A | 0.33387 (3) | 0.43422 (3) | 0.42330 (11) | 0.0169 (3) | |
C111 | 0.42101 (3) | 0.45923 (3) | 1.10490 (12) | 0.0207 (3) | |
H11A | 0.4297 | 0.4681 | 1.0292 | 0.025* | |
C39A | 0.39492 (3) | 0.56594 (3) | 0.10127 (12) | 0.0188 (3) | |
C210 | 0.26079 (3) | 0.39767 (3) | 0.24270 (12) | 0.0188 (3) | |
H10B | 0.2658 | 0.4047 | 0.1624 | 0.023* | |
C112 | 0.43889 (3) | 0.47726 (3) | 1.21326 (12) | 0.0240 (3) | |
H12A | 0.4428 | 0.4989 | 1.2061 | 0.029* | |
H12B | 0.4595 | 0.4784 | 1.2130 | 0.029* | |
C211 | 0.23589 (3) | 0.37001 (3) | 0.26272 (12) | 0.0201 (3) | |
H11B | 0.2329 | 0.3628 | 0.3430 | 0.024* | |
C113 | 0.42333 (3) | 0.46421 (3) | 1.33300 (12) | 0.0259 (3) | |
H13A | 0.4198 | 0.4428 | 1.3426 | 0.031* | |
H13B | 0.4027 | 0.4630 | 1.3347 | 0.031* | |
C212 | 0.21183 (3) | 0.34868 (3) | 0.17418 (12) | 0.0226 (3) | |
H12C | 0.1918 | 0.3476 | 0.1937 | 0.027* | |
H12D | 0.2087 | 0.3274 | 0.1851 | 0.027* | |
C114 | 0.44315 (4) | 0.48443 (4) | 1.43649 (13) | 0.0292 (3) | |
H14A | 0.4325 | 0.4752 | 1.5123 | 0.044* | |
H14B | 0.4462 | 0.5055 | 1.4285 | 0.044* | |
H14C | 0.4635 | 0.4856 | 1.4354 | 0.044* | |
C310 | 0.42927 (3) | 0.53233 (3) | −0.10552 (13) | 0.0246 (3) | 0.841 (2) |
H10D | 0.4221 | 0.5336 | −0.1831 | 0.029* | 0.841 (2) |
C311 | 0.45638 (4) | 0.53238 (5) | −0.09460 (18) | 0.0219 (4) | 0.841 (2) |
H11D | 0.4627 | 0.5306 | −0.0161 | 0.026* | 0.841 (2) |
C312 | 0.47778 (4) | 0.53507 (4) | −0.19651 (14) | 0.0243 (4) | 0.841 (2) |
H12G | 0.4996 | 0.5496 | −0.1717 | 0.029* | 0.841 (2) |
H12H | 0.4758 | 0.5143 | −0.2089 | 0.029* | 0.841 (2) |
C313 | 0.47219 (4) | 0.54616 (4) | −0.31500 (14) | 0.0263 (4) | 0.841 (2) |
H13G | 0.4730 | 0.5664 | −0.3036 | 0.032* | 0.841 (2) |
H13H | 0.4511 | 0.5309 | −0.3448 | 0.032* | 0.841 (2) |
C314 | 0.49656 (6) | 0.55001 (8) | −0.4072 (2) | 0.0279 (6) | 0.841 (2) |
H14J | 0.4935 | 0.5590 | −0.4806 | 0.042* | 0.841 (2) |
H14K | 0.4943 | 0.5296 | −0.4249 | 0.042* | 0.841 (2) |
H14L | 0.5175 | 0.5640 | −0.3753 | 0.042* | 0.841 (2) |
C315 | 0.42927 (3) | 0.53233 (3) | −0.10552 (13) | 0.0246 (3) | 0.159 (2) |
H15C | 0.4233 | 0.5396 | −0.1737 | 0.029* | 0.159 (2) |
C316 | 0.4522 (2) | 0.5269 (3) | −0.1319 (8) | 0.0275 (17) | 0.159 (2) |
H16C | 0.4632 | 0.5234 | −0.0696 | 0.033* | 0.159 (2) |
C317 | 0.46092 (17) | 0.5261 (2) | −0.2607 (7) | 0.0246 (13) | 0.159 (2) |
H17C | 0.4478 | 0.5308 | −0.3144 | 0.030* | 0.159 (2) |
H17D | 0.4576 | 0.5051 | −0.2810 | 0.030* | 0.159 (2) |
C318 | 0.49498 (18) | 0.5505 (2) | −0.2755 (8) | 0.0315 (16) | 0.159 (2) |
H18D | 0.5077 | 0.5469 | −0.2157 | 0.038* | 0.159 (2) |
H18E | 0.4978 | 0.5715 | −0.2617 | 0.038* | 0.159 (2) |
C319 | 0.5060 (4) | 0.5487 (5) | −0.4001 (9) | 0.032 (3) | 0.159 (2) |
H19D | 0.5044 | 0.5283 | −0.4116 | 0.049* | 0.159 (2) |
H19E | 0.5277 | 0.5653 | −0.4102 | 0.049* | 0.159 (2) |
H19F | 0.4928 | 0.5514 | −0.4592 | 0.049* | 0.159 (2) |
C214 | 0.24464 (4) | 0.35197 (4) | −0.00572 (13) | 0.0307 (4) | |
H14D | 0.2478 | 0.3573 | −0.0909 | 0.046* | |
H14E | 0.2385 | 0.3299 | 0.0048 | 0.046* | |
H14F | 0.2641 | 0.3652 | 0.0380 | 0.046* | |
C213 | 0.21896 (3) | 0.35743 (3) | 0.04241 (13) | 0.0248 (3) | |
H13C | 0.1997 | 0.3449 | −0.0050 | 0.030* | |
H13D | 0.2254 | 0.3798 | 0.0322 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N11 | 0.0186 (6) | 0.0182 (6) | 0.0144 (5) | 0.0096 (5) | −0.0010 (4) | −0.0021 (4) |
F11 | 0.0271 (4) | 0.0340 (5) | 0.0193 (4) | 0.0148 (4) | −0.0085 (3) | −0.0012 (4) |
C411 | 0.0301 (7) | 0.0378 (7) | 0.0467 (8) | 0.0181 (6) | 0.0053 (6) | 0.0203 (6) |
C412 | 0.0296 (15) | 0.0302 (15) | 0.0358 (15) | 0.0181 (13) | 0.0027 (14) | 0.0090 (13) |
C413 | 0.030 (2) | 0.0295 (17) | 0.0336 (17) | 0.0154 (15) | −0.0001 (17) | 0.0063 (15) |
C414 | 0.030 (3) | 0.036 (2) | 0.027 (2) | 0.018 (2) | 0.002 (2) | 0.0070 (19) |
C415 | 0.0301 (7) | 0.0378 (7) | 0.0467 (8) | 0.0181 (6) | 0.0053 (6) | 0.0203 (6) |
C416 | 0.0289 (15) | 0.0305 (15) | 0.0327 (15) | 0.0167 (12) | 0.0035 (13) | 0.0080 (13) |
C417 | 0.0280 (15) | 0.0272 (15) | 0.0289 (15) | 0.0155 (12) | 0.0036 (13) | 0.0020 (13) |
C418 | 0.031 (2) | 0.035 (2) | 0.032 (2) | 0.0180 (19) | 0.0005 (19) | 0.0049 (17) |
C419 | 0.0301 (7) | 0.0378 (7) | 0.0467 (8) | 0.0181 (6) | 0.0053 (6) | 0.0203 (6) |
C420 | 0.0308 (15) | 0.0290 (15) | 0.0352 (15) | 0.0174 (12) | 0.0023 (14) | 0.0081 (13) |
C421 | 0.0294 (18) | 0.0279 (16) | 0.0314 (16) | 0.0158 (14) | 0.0002 (15) | 0.0069 (14) |
C422 | 0.032 (3) | 0.027 (2) | 0.028 (2) | 0.0147 (18) | −0.001 (2) | 0.0059 (18) |
C410 | 0.0285 (8) | 0.0486 (10) | 0.0239 (8) | 0.0259 (8) | 0.0086 (6) | 0.0161 (7) |
C49A | 0.0208 (7) | 0.0175 (7) | 0.0174 (7) | 0.0096 (6) | −0.0010 (5) | −0.0049 (5) |
C49 | 0.0203 (7) | 0.0235 (7) | 0.0254 (7) | 0.0123 (6) | −0.0017 (6) | −0.0039 (6) |
C48 | 0.0193 (7) | 0.0215 (7) | 0.0328 (8) | 0.0082 (6) | 0.0059 (6) | −0.0010 (6) |
C47 | 0.0274 (8) | 0.0181 (7) | 0.0234 (7) | 0.0091 (6) | 0.0057 (6) | 0.0023 (6) |
C46 | 0.0224 (7) | 0.0174 (7) | 0.0213 (7) | 0.0096 (6) | −0.0011 (6) | −0.0020 (5) |
C45A | 0.0184 (7) | 0.0154 (6) | 0.0181 (7) | 0.0072 (5) | −0.0016 (5) | −0.0046 (5) |
C45 | 0.0187 (7) | 0.0186 (7) | 0.0164 (6) | 0.0102 (6) | −0.0013 (5) | −0.0018 (5) |
C44 | 0.0179 (7) | 0.0194 (7) | 0.0148 (6) | 0.0082 (6) | −0.0011 (5) | −0.0005 (5) |
C43 | 0.0213 (7) | 0.0196 (7) | 0.0166 (7) | 0.0095 (6) | −0.0015 (5) | 0.0008 (5) |
C42 | 0.0249 (7) | 0.0222 (7) | 0.0151 (6) | 0.0141 (6) | 0.0015 (5) | 0.0019 (5) |
O11 | 0.0280 (5) | 0.0257 (5) | 0.0157 (5) | 0.0184 (5) | −0.0018 (4) | −0.0022 (4) |
N21 | 0.0177 (6) | 0.0181 (6) | 0.0151 (5) | 0.0090 (5) | −0.0021 (4) | −0.0037 (5) |
F21 | 0.0293 (5) | 0.0378 (5) | 0.0230 (4) | 0.0168 (4) | −0.0125 (4) | −0.0041 (4) |
O21 | 0.0270 (5) | 0.0275 (5) | 0.0181 (5) | 0.0178 (5) | −0.0031 (4) | −0.0062 (4) |
C22 | 0.0164 (6) | 0.0189 (7) | 0.0143 (6) | 0.0071 (5) | 0.0000 (5) | −0.0008 (5) |
C12 | 0.0161 (6) | 0.0172 (7) | 0.0156 (6) | 0.0058 (5) | 0.0000 (5) | 0.0011 (5) |
N31 | 0.0185 (6) | 0.0178 (6) | 0.0163 (6) | 0.0069 (5) | 0.0011 (5) | 0.0011 (5) |
F31 | 0.0363 (5) | 0.0374 (5) | 0.0286 (5) | 0.0202 (4) | −0.0018 (4) | −0.0149 (4) |
O31 | 0.0231 (5) | 0.0174 (5) | 0.0166 (5) | 0.0056 (4) | 0.0019 (4) | 0.0003 (4) |
N41 | 0.0193 (6) | 0.0261 (6) | 0.0153 (6) | 0.0134 (5) | −0.0032 (5) | −0.0024 (5) |
F41 | 0.0324 (5) | 0.0291 (5) | 0.0334 (5) | 0.0127 (4) | 0.0128 (4) | 0.0121 (4) |
O41 | 0.0174 (5) | 0.0274 (5) | 0.0176 (5) | 0.0084 (4) | −0.0026 (4) | 0.0032 (4) |
C23 | 0.0163 (7) | 0.0215 (7) | 0.0172 (7) | 0.0087 (6) | −0.0010 (5) | −0.0026 (5) |
C13 | 0.0173 (7) | 0.0201 (7) | 0.0164 (6) | 0.0089 (6) | −0.0009 (5) | −0.0011 (5) |
C32 | 0.0175 (7) | 0.0214 (7) | 0.0160 (6) | 0.0091 (6) | −0.0005 (5) | 0.0008 (5) |
C24 | 0.0202 (7) | 0.0222 (7) | 0.0148 (6) | 0.0119 (6) | −0.0010 (5) | −0.0020 (5) |
C14 | 0.0212 (7) | 0.0203 (7) | 0.0139 (6) | 0.0126 (6) | −0.0002 (5) | 0.0006 (5) |
C33 | 0.0195 (7) | 0.0192 (7) | 0.0160 (6) | 0.0099 (6) | −0.0006 (5) | 0.0000 (5) |
C34 | 0.0176 (7) | 0.0176 (7) | 0.0156 (6) | 0.0064 (6) | −0.0012 (5) | −0.0004 (5) |
C25 | 0.0203 (7) | 0.0186 (7) | 0.0157 (6) | 0.0091 (6) | −0.0015 (5) | −0.0032 (5) |
C15 | 0.0200 (7) | 0.0178 (7) | 0.0144 (6) | 0.0091 (6) | −0.0002 (5) | −0.0009 (5) |
C35 | 0.0161 (6) | 0.0205 (7) | 0.0163 (6) | 0.0077 (6) | 0.0002 (5) | 0.0002 (5) |
C35A | 0.0195 (7) | 0.0209 (7) | 0.0176 (7) | 0.0115 (6) | −0.0039 (5) | −0.0004 (5) |
C25A | 0.0146 (6) | 0.0202 (7) | 0.0158 (6) | 0.0070 (5) | 0.0019 (5) | 0.0002 (5) |
C15A | 0.0151 (6) | 0.0190 (7) | 0.0141 (6) | 0.0072 (5) | 0.0023 (5) | 0.0011 (5) |
C16 | 0.0172 (7) | 0.0200 (7) | 0.0159 (6) | 0.0076 (6) | 0.0011 (5) | −0.0011 (5) |
C17 | 0.0159 (7) | 0.0275 (7) | 0.0140 (6) | 0.0079 (6) | −0.0019 (5) | 0.0016 (6) |
C36 | 0.0208 (7) | 0.0249 (7) | 0.0206 (7) | 0.0126 (6) | −0.0010 (6) | −0.0006 (6) |
C26 | 0.0176 (7) | 0.0217 (7) | 0.0177 (7) | 0.0065 (6) | −0.0001 (5) | −0.0019 (5) |
C18 | 0.0196 (7) | 0.0240 (7) | 0.0235 (7) | 0.0122 (6) | −0.0009 (6) | 0.0056 (6) |
C37 | 0.0292 (8) | 0.0308 (8) | 0.0211 (7) | 0.0190 (7) | −0.0041 (6) | −0.0081 (6) |
C27 | 0.0180 (7) | 0.0292 (8) | 0.0163 (7) | 0.0091 (6) | −0.0035 (5) | 0.0004 (6) |
C19 | 0.0200 (7) | 0.0194 (7) | 0.0191 (7) | 0.0089 (6) | 0.0002 (5) | 0.0013 (5) |
C38 | 0.0246 (8) | 0.0242 (8) | 0.0305 (8) | 0.0112 (6) | −0.0068 (6) | −0.0090 (6) |
C28 | 0.0190 (7) | 0.0247 (7) | 0.0226 (7) | 0.0114 (6) | −0.0008 (6) | 0.0033 (6) |
C19A | 0.0148 (6) | 0.0182 (7) | 0.0150 (6) | 0.0064 (5) | 0.0018 (5) | 0.0014 (5) |
C39 | 0.0205 (7) | 0.0229 (7) | 0.0242 (7) | 0.0088 (6) | −0.0035 (6) | −0.0025 (6) |
C29 | 0.0184 (7) | 0.0197 (7) | 0.0199 (7) | 0.0083 (6) | 0.0010 (5) | −0.0003 (5) |
C110 | 0.0214 (7) | 0.0192 (7) | 0.0148 (6) | 0.0105 (6) | −0.0005 (5) | 0.0004 (5) |
C29A | 0.0136 (6) | 0.0191 (7) | 0.0142 (6) | 0.0054 (5) | 0.0016 (5) | 0.0010 (5) |
C111 | 0.0221 (7) | 0.0214 (7) | 0.0180 (7) | 0.0103 (6) | 0.0011 (5) | −0.0006 (5) |
C39A | 0.0192 (7) | 0.0219 (7) | 0.0169 (7) | 0.0114 (6) | −0.0030 (5) | −0.0008 (5) |
C210 | 0.0212 (7) | 0.0204 (7) | 0.0156 (6) | 0.0110 (6) | −0.0032 (5) | −0.0024 (5) |
C112 | 0.0204 (7) | 0.0221 (7) | 0.0231 (7) | 0.0059 (6) | −0.0020 (6) | −0.0026 (6) |
C211 | 0.0219 (7) | 0.0221 (7) | 0.0176 (7) | 0.0120 (6) | −0.0007 (5) | −0.0007 (5) |
C113 | 0.0238 (7) | 0.0252 (8) | 0.0212 (7) | 0.0066 (6) | −0.0022 (6) | −0.0027 (6) |
C212 | 0.0188 (7) | 0.0223 (7) | 0.0242 (7) | 0.0084 (6) | −0.0034 (6) | −0.0036 (6) |
C114 | 0.0281 (8) | 0.0312 (8) | 0.0231 (8) | 0.0110 (7) | −0.0040 (6) | −0.0048 (6) |
C310 | 0.0286 (8) | 0.0210 (7) | 0.0206 (7) | 0.0098 (6) | 0.0049 (6) | 0.0006 (6) |
C311 | 0.0266 (9) | 0.0180 (10) | 0.0206 (9) | 0.0109 (8) | 0.0057 (7) | 0.0001 (8) |
C312 | 0.0243 (9) | 0.0282 (9) | 0.0239 (9) | 0.0158 (7) | 0.0041 (7) | 0.0039 (7) |
C313 | 0.0289 (9) | 0.0337 (10) | 0.0203 (8) | 0.0186 (8) | 0.0023 (7) | 0.0009 (7) |
C314 | 0.0274 (14) | 0.0324 (11) | 0.0222 (10) | 0.0137 (11) | 0.0009 (9) | −0.0014 (8) |
C315 | 0.0286 (8) | 0.0210 (7) | 0.0206 (7) | 0.0098 (6) | 0.0049 (6) | 0.0006 (6) |
C316 | 0.034 (2) | 0.022 (2) | 0.025 (2) | 0.0130 (17) | 0.0087 (19) | −0.004 (2) |
C317 | 0.028 (2) | 0.026 (2) | 0.021 (2) | 0.0145 (19) | 0.0042 (19) | 0.000 (2) |
C318 | 0.030 (2) | 0.033 (2) | 0.022 (2) | 0.009 (2) | 0.005 (2) | −0.003 (2) |
C319 | 0.032 (5) | 0.036 (5) | 0.019 (4) | 0.010 (5) | 0.009 (4) | −0.001 (4) |
C214 | 0.0352 (9) | 0.0323 (9) | 0.0230 (8) | 0.0157 (7) | 0.0017 (7) | −0.0036 (6) |
C213 | 0.0287 (8) | 0.0226 (7) | 0.0222 (7) | 0.0120 (6) | −0.0084 (6) | −0.0048 (6) |
N11—C19A | 1.4347 (16) | C32—C33 | 1.5283 (18) |
N11—C12 | 1.4938 (17) | C24—C25 | 1.5342 (18) |
F11—C17 | 1.3646 (15) | C14—C15 | 1.5370 (18) |
C411—C410 | 1.317 (2) | C33—C34 | 1.5201 (18) |
C411—C412 | 1.511 (9) | C34—C35 | 1.5378 (18) |
C412—C413 | 1.497 (10) | C25—C25A | 1.5084 (18) |
C413—C414 | 1.527 (8) | C15—C15A | 1.5041 (18) |
C416—C417 | 1.518 (6) | C35—C35A | 1.5085 (18) |
C417—C418 | 1.523 (6) | C35A—C36 | 1.3989 (19) |
C420—C421 | 1.515 (8) | C35A—C39A | 1.4016 (19) |
C421—C422 | 1.540 (7) | C25A—C26 | 1.3980 (18) |
C410—C42 | 1.5042 (19) | C25A—C29A | 1.4045 (19) |
C49A—C49 | 1.3956 (19) | C15A—C16 | 1.3989 (18) |
C49A—C45A | 1.4040 (19) | C15A—C19A | 1.4044 (18) |
C49A—N41 | 1.4313 (17) | C16—C17 | 1.3757 (19) |
C49—C48 | 1.388 (2) | C17—C18 | 1.375 (2) |
C48—C47 | 1.374 (2) | C36—C37 | 1.376 (2) |
C47—F41 | 1.3660 (16) | C26—C27 | 1.376 (2) |
C47—C46 | 1.375 (2) | C18—C19 | 1.3881 (19) |
C46—C45A | 1.3964 (19) | C37—C38 | 1.373 (2) |
C45A—C45 | 1.5091 (18) | C27—C28 | 1.373 (2) |
C45—C44 | 1.5368 (18) | C19—C19A | 1.3934 (19) |
C44—O41 | 1.4320 (16) | C38—C39 | 1.387 (2) |
C44—C43 | 1.5176 (18) | C28—C29 | 1.3873 (19) |
C43—C42 | 1.5276 (19) | C39—C39A | 1.3973 (19) |
C42—N41 | 1.4940 (18) | C29—C29A | 1.3972 (19) |
O11—C14 | 1.4340 (15) | C110—C111 | 1.3219 (19) |
N21—C29A | 1.4347 (16) | C111—C112 | 1.5015 (19) |
N21—C22 | 1.4970 (17) | C210—C211 | 1.3227 (19) |
F21—C27 | 1.3666 (15) | C112—C113 | 1.518 (2) |
O21—C24 | 1.4342 (16) | C211—C212 | 1.4999 (19) |
C22—C210 | 1.5016 (18) | C113—C114 | 1.5222 (19) |
C22—C23 | 1.5240 (18) | C212—C213 | 1.526 (2) |
C12—C110 | 1.5063 (18) | C310—C311 | 1.343 (2) |
C12—C13 | 1.5305 (18) | C311—C312 | 1.514 (2) |
N31—C39A | 1.4323 (17) | C312—C313 | 1.511 (2) |
N31—C32 | 1.4917 (17) | C313—C314 | 1.523 (2) |
F31—C37 | 1.3674 (16) | C316—C317 | 1.509 (4) |
O31—C34 | 1.4350 (16) | C317—C318 | 1.510 (4) |
C23—C24 | 1.5213 (18) | C318—C319 | 1.512 (4) |
C13—C14 | 1.5184 (18) | C214—C213 | 1.521 (2) |
C32—C310 | 1.5024 (19) | ||
C19A—N11—C12 | 116.72 (10) | C15A—C15—C14 | 113.62 (11) |
C410—C411—C412 | 122.9 (5) | C35A—C35—C34 | 114.54 (11) |
C413—C412—C411 | 119.1 (8) | C36—C35A—C39A | 118.74 (12) |
C412—C413—C414 | 109.6 (7) | C36—C35A—C35 | 119.63 (12) |
C416—C417—C418 | 112.3 (4) | C39A—C35A—C35 | 121.62 (12) |
C420—C421—C422 | 112.7 (6) | C26—C25A—C29A | 118.75 (12) |
C411—C410—C42 | 123.74 (16) | C26—C25A—C25 | 119.16 (12) |
C49—C49A—C45A | 119.63 (13) | C29A—C25A—C25 | 122.08 (12) |
C49—C49A—N41 | 119.29 (12) | C16—C15A—C19A | 118.67 (12) |
C45A—C49A—N41 | 121.02 (12) | C16—C15A—C15 | 119.72 (12) |
C48—C49—C49A | 121.30 (13) | C19A—C15A—C15 | 121.60 (11) |
C47—C48—C49 | 117.91 (13) | C17—C16—C15A | 119.82 (12) |
F41—C47—C48 | 118.94 (13) | F11—C17—C18 | 119.20 (12) |
F41—C47—C46 | 118.51 (13) | F11—C17—C16 | 118.28 (12) |
C48—C47—C46 | 122.54 (13) | C18—C17—C16 | 122.52 (12) |
C47—C46—C45A | 119.92 (13) | C37—C36—C35A | 119.64 (13) |
C46—C45A—C49A | 118.69 (12) | C27—C26—C25A | 119.71 (13) |
C46—C45A—C45 | 119.41 (12) | C17—C18—C19 | 117.96 (13) |
C49A—C45A—C45 | 121.90 (12) | F31—C37—C38 | 119.07 (13) |
C45A—C45—C44 | 114.61 (11) | F31—C37—C36 | 118.20 (13) |
O41—C44—C43 | 106.43 (10) | C38—C37—C36 | 122.72 (13) |
O41—C44—C45 | 109.82 (10) | F21—C27—C28 | 119.07 (12) |
C43—C44—C45 | 112.84 (11) | F21—C27—C26 | 118.20 (12) |
C44—C43—C42 | 116.23 (11) | C28—C27—C26 | 122.72 (13) |
N41—C42—C410 | 108.08 (12) | C18—C19—C19A | 121.31 (13) |
N41—C42—C43 | 112.55 (11) | C37—C38—C39 | 118.00 (13) |
C410—C42—C43 | 108.60 (11) | C27—C28—C29 | 117.90 (13) |
C29A—N21—C22 | 115.16 (10) | C19—C19A—C15A | 119.72 (12) |
N21—C22—C210 | 109.25 (10) | C19—C19A—N11 | 119.51 (12) |
N21—C22—C23 | 112.08 (11) | C15A—C19A—N11 | 120.70 (12) |
C210—C22—C23 | 108.45 (11) | C38—C39—C39A | 121.09 (14) |
N11—C12—C110 | 107.90 (10) | C28—C29—C29A | 121.29 (13) |
N11—C12—C13 | 112.54 (11) | C111—C110—C12 | 124.10 (12) |
C110—C12—C13 | 108.31 (10) | C29—C29A—C25A | 119.61 (12) |
C39A—N31—C32 | 116.73 (10) | C29—C29A—N21 | 119.36 (12) |
C49A—N41—C42 | 116.76 (10) | C25A—C29A—N21 | 121.00 (12) |
C24—C23—C22 | 116.08 (11) | C110—C111—C112 | 126.52 (13) |
C14—C13—C12 | 117.19 (11) | C39—C39A—C35A | 119.80 (13) |
N31—C32—C310 | 107.59 (11) | C39—C39A—N31 | 119.25 (12) |
N31—C32—C33 | 112.30 (11) | C35A—C39A—N31 | 120.89 (12) |
C310—C32—C33 | 109.59 (11) | C211—C210—C22 | 123.08 (12) |
O21—C24—C23 | 106.52 (10) | C111—C112—C113 | 115.91 (12) |
O21—C24—C25 | 109.80 (11) | C210—C211—C212 | 127.95 (13) |
C23—C24—C25 | 113.00 (11) | C112—C113—C114 | 111.64 (12) |
O11—C14—C13 | 105.99 (10) | C211—C212—C213 | 116.65 (12) |
O11—C14—C15 | 110.20 (10) | C311—C310—C32 | 121.91 (14) |
C13—C14—C15 | 112.89 (11) | C310—C311—C312 | 125.68 (17) |
C34—C33—C32 | 116.27 (11) | C313—C312—C311 | 116.45 (15) |
O31—C34—C33 | 106.46 (10) | C312—C313—C314 | 111.25 (16) |
O31—C34—C35 | 109.70 (10) | C316—C317—C318 | 107.7 (7) |
C33—C34—C35 | 112.93 (11) | C317—C318—C319 | 110.1 (9) |
C25A—C25—C24 | 114.85 (11) | C214—C213—C212 | 112.71 (12) |
C410—C411—C412—C413 | 16.5 (14) | C15—C15A—C16—C17 | 180.00 (12) |
C411—C412—C413—C414 | 173.5 (8) | C15A—C16—C17—F11 | −179.65 (11) |
C412—C411—C410—C42 | −177.6 (7) | C15A—C16—C17—C18 | 0.4 (2) |
C45A—C49A—C49—C48 | 0.1 (2) | C39A—C35A—C36—C37 | 0.2 (2) |
N41—C49A—C49—C48 | 177.53 (12) | C35—C35A—C36—C37 | −178.61 (13) |
C49A—C49—C48—C47 | 0.8 (2) | C29A—C25A—C26—C27 | 0.76 (19) |
C49—C48—C47—F41 | 179.33 (12) | C25—C25A—C26—C27 | −178.24 (12) |
C49—C48—C47—C46 | −0.9 (2) | F11—C17—C18—C19 | 179.85 (12) |
F41—C47—C46—C45A | 179.89 (12) | C16—C17—C18—C19 | −0.2 (2) |
C48—C47—C46—C45A | 0.2 (2) | C35A—C36—C37—F31 | 179.48 (12) |
C47—C46—C45A—C49A | 0.78 (19) | C35A—C36—C37—C38 | 0.0 (2) |
C47—C46—C45A—C45 | −178.47 (12) | C25A—C26—C27—F21 | 179.64 (12) |
C49—C49A—C45A—C46 | −0.91 (19) | C25A—C26—C27—C28 | 0.1 (2) |
N41—C49A—C45A—C46 | −178.27 (12) | C17—C18—C19—C19A | −0.1 (2) |
C49—C49A—C45A—C45 | 178.32 (12) | F31—C37—C38—C39 | −179.87 (12) |
N41—C49A—C45A—C45 | 0.96 (19) | C36—C37—C38—C39 | −0.4 (2) |
C46—C45A—C45—C44 | −119.35 (13) | F21—C27—C28—C29 | 179.62 (12) |
C49A—C45A—C45—C44 | 61.43 (16) | C26—C27—C28—C29 | −0.9 (2) |
C45A—C45—C44—O41 | 164.37 (11) | C18—C19—C19A—C15A | 0.2 (2) |
C45A—C45—C44—C43 | −77.07 (14) | C18—C19—C19A—N11 | −176.67 (12) |
O41—C44—C43—C42 | −175.04 (11) | C16—C15A—C19A—C19 | 0.00 (19) |
C45—C44—C43—C42 | 64.44 (15) | C15—C15A—C19A—C19 | 179.73 (12) |
C411—C410—C42—N41 | 129.58 (16) | C16—C15A—C19A—N11 | 176.83 (11) |
C411—C410—C42—C43 | −108.04 (17) | C15—C15A—C19A—N11 | −3.44 (19) |
C44—C43—C42—N41 | −64.28 (15) | C12—N11—C19A—C19 | −114.64 (13) |
C44—C43—C42—C410 | 176.10 (12) | C12—N11—C19A—C15A | 68.53 (16) |
C29A—N21—C22—C210 | −156.69 (11) | C37—C38—C39—C39A | 0.6 (2) |
C29A—N21—C22—C23 | 83.09 (13) | C27—C28—C29—C29A | 0.7 (2) |
C19A—N11—C12—C110 | 161.36 (11) | N11—C12—C110—C111 | −132.05 (14) |
C19A—N11—C12—C13 | −79.20 (14) | C13—C12—C110—C111 | 105.86 (15) |
C49—C49A—N41—C42 | 117.04 (14) | C28—C29—C29A—C25A | 0.1 (2) |
C45A—C49A—N41—C42 | −65.59 (16) | C28—C29—C29A—N21 | 178.50 (12) |
C410—C42—N41—C49A | −159.36 (12) | C26—C25A—C29A—C29 | −0.89 (19) |
C43—C42—N41—C49A | 80.71 (14) | C25—C25A—C29A—C29 | 178.08 (12) |
N21—C22—C23—C24 | −66.36 (14) | C26—C25A—C29A—N21 | −179.22 (12) |
C210—C22—C23—C24 | 172.95 (11) | C25—C25A—C29A—N21 | −0.25 (19) |
N11—C12—C13—C14 | 60.97 (15) | C22—N21—C29A—C29 | 116.14 (13) |
C110—C12—C13—C14 | −179.82 (11) | C22—N21—C29A—C25A | −65.52 (16) |
C39A—N31—C32—C310 | −158.27 (11) | C12—C110—C111—C112 | −176.79 (13) |
C39A—N31—C32—C33 | 81.05 (14) | C38—C39—C39A—C35A | −0.4 (2) |
C22—C23—C24—O21 | −175.67 (11) | C38—C39—C39A—N31 | 176.81 (13) |
C22—C23—C24—C25 | 63.68 (15) | C36—C35A—C39A—C39 | 0.0 (2) |
C12—C13—C14—O11 | 175.57 (11) | C35—C35A—C39A—C39 | 178.78 (12) |
C12—C13—C14—C15 | −63.70 (15) | C36—C35A—C39A—N31 | −177.17 (12) |
N31—C32—C33—C34 | −63.64 (15) | C35—C35A—C39A—N31 | 1.64 (19) |
C310—C32—C33—C34 | 176.84 (12) | C32—N31—C39A—C39 | 116.01 (14) |
C32—C33—C34—O31 | −175.46 (11) | C32—N31—C39A—C35A | −66.84 (16) |
C32—C33—C34—C35 | 64.10 (15) | N21—C22—C210—C211 | 122.85 (14) |
O21—C24—C25—C25A | 165.75 (10) | C23—C22—C210—C211 | −114.73 (14) |
C23—C24—C25—C25A | −75.49 (14) | C110—C111—C112—C113 | −5.0 (2) |
O11—C14—C15—C15A | −163.06 (10) | C22—C210—C211—C212 | 173.60 (13) |
C13—C14—C15—C15A | 78.65 (14) | C111—C112—C113—C114 | −179.24 (13) |
O31—C34—C35—C35A | 164.07 (11) | C210—C211—C212—C213 | 9.3 (2) |
C33—C34—C35—C35A | −77.36 (14) | N31—C32—C310—C311 | 128.42 (16) |
C34—C35—C35A—C36 | −119.81 (13) | C33—C32—C310—C311 | −109.21 (17) |
C34—C35—C35A—C39A | 61.39 (17) | C32—C310—C311—C312 | −178.55 (15) |
C24—C25—C25A—C26 | −118.94 (13) | C310—C311—C312—C313 | 15.3 (3) |
C24—C25—C25A—C29A | 62.09 (16) | C311—C312—C313—C314 | 176.05 (19) |
C14—C15—C15A—C16 | 118.18 (13) | C316—C317—C318—C319 | 174.7 (10) |
C14—C15—C15A—C19A | −61.55 (16) | C211—C212—C213—C214 | 72.12 (16) |
C19A—C15A—C16—C17 | −0.27 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H1N···O31i | 0.906 (16) | 2.287 (16) | 3.1897 (15) | 173.9 (13) |
N21—H2N···O11ii | 0.895 (16) | 2.370 (17) | 3.2455 (15) | 165.8 (13) |
N31—H3N···O21iii | 0.901 (17) | 2.326 (17) | 3.2208 (15) | 172.2 (14) |
N41—H4N···O41iv | 0.893 (16) | 2.310 (16) | 3.1952 (15) | 170.9 (14) |
O11—H1O···N11v | 0.869 (19) | 2.00 (2) | 2.8553 (15) | 166.1 (17) |
O21—H2O···N41 | 0.89 (2) | 1.98 (2) | 2.8542 (15) | 168.6 (18) |
O31—H3O···N21 | 0.864 (19) | 2.008 (19) | 2.8619 (15) | 169.5 (17) |
O41—H4O···N31i | 0.88 (2) | 2.00 (2) | 2.8570 (15) | 167.3 (17) |
Symmetry codes: (i) x, y, z+1; (ii) −y+2/3, x−y+1/3, z−2/3; (iii) x−y+2/3, x+1/3, −z+1/3; (iv) y−1/3, −x+y+1/3, −z+4/3; (v) −x+y+1/3, −x+2/3, z−1/3. |
Experimental details
(Compound_1) | (Compound_2) | (Compound_3) | |
Crystal data | |||
Chemical formula | C22H21NO | C22H21NO | C22H21NO |
Mr | 315.40 | 315.40 | 315.40 |
Crystal system, space group | Monoclinic, P21/c | Orthorhombic, P212121 | Monoclinic, P21 |
Temperature (K) | 100 | 298 | 100 |
a, b, c (Å) | 24.8049 (10), 10.7126 (5), 12.1932 (4) | 7.5541 (3), 14.7914 (5), 15.4049 (5) | 7.2201 (2), 7.8128 (3), 14.7409 (5) |
α, β, γ (°) | 90, 95.929 (1), 90 | 90, 90, 90 | 90, 93.690 (2), 90 |
V (Å3) | 3222.7 (2) | 1721.28 (11) | 829.80 (5) |
Z | 8 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.07 | 0.08 |
Crystal size (mm) | 0.45 × 0.35 × 0.20 | 0.51 × 0.32 × 0.25 | 0.30 × 0.30 × 0.15 |
Data collection | |||
Diffractometer | Bruker Kappa APEXII | Bruker Kappa APEXII | Bruker Kappa APEXII |
Absorption correction | Multi-scan (SADABS; Bruker, 2006) | Multi-scan (SADABS; Bruker, 2006) | Multi-scan (SADABS; Bruker, 2006) |
Tmin, Tmax | 0.640, 0.746 | 0.86, 0.98 | 0.92, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 48596, 7121, 6012 | 69991, 5630, 4013 | 27947, 4874, 4638 |
Rint | 0.040 | 0.041 | 0.023 |
(sin θ/λ)max (Å−1) | 0.649 | 0.734 | 0.709 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.122, 1.04 | 0.043, 0.109, 1.03 | 0.033, 0.092, 1.04 |
No. of reflections | 7121 | 5630 | 4874 |
No. of parameters | 437 | 220 | 219 |
No. of restraints | 0 | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0523P)2 + 2.1093P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0474P)2 + 0.1943P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0566P)2 + 0.1148P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.37, −0.26 | 0.17, −0.16 | 0.30, −0.19 |
Absolute structure | ? | Refined as an inversion twin | Flack x determined using 2066 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | ? | 0 (2) | −0.1 (3) |
(Compound_4) | (Compound_5a) | (Compound_5b) | |
Crystal data | |||
Chemical formula | C18H18FNO | C15H20FNO | C15H20FNO |
Mr | 283.33 | 249.32 | 249.32 |
Crystal system, space group | Orthorhombic, Pbca | Trigonal, R3:H | Trigonal, R3:H |
Temperature (K) | 100 | 298 | 100 |
a, b, c (Å) | 7.5932 (3), 7.5859 (4), 51.010 (3) | 25.119 (2), 25.119 (2), 11.2812 (12) | 49.395 (2), 49.395 (2), 11.1802 (5) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 120 | 90, 90, 120 |
V (Å3) | 2938.2 (2) | 6164.2 (12) | 23623 (2) |
Z | 8 | 18 | 72 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.08 | 0.09 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 | 0.30 × 0.25 × 0.20 | 0.30 × 0.25 × 0.20 |
Data collection | |||
Diffractometer | Bruker Kappa APEXII | Bruker Kappa APEXII | Bruker Kappa APEXII |
Absorption correction | Multi-scan (SADABS; Bruker, 2006) | Multi-scan (SADABS; Bruker, 2006) | Multi-scan (SADABS; Bruker, 2006) |
Tmin, Tmax | 0.90, 0.98 | 0.68, 0.74 | 0.89, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 40696, 3764, 3407 | 34372, 2814, 2024 | 124259, 12035, 8771 |
Rint | 0.027 | 0.036 | 0.043 |
(sin θ/λ)max (Å−1) | 0.709 | 0.625 | 0.649 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.108, 1.09 | 0.066, 0.229, 1.07 | 0.046, 0.122, 1.02 |
No. of reflections | 3764 | 2814 | 12035 |
No. of parameters | 198 | 212 | 786 |
No. of restraints | 0 | 159 | 459 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0371P)2 + 2.0455P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.1155P)2 + 11.0098P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.048P)2 + 28.8932P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.32, −0.23 | 0.55, −0.41 | 0.44, −0.28 |
Absolute structure | ? | ? | ? |
Absolute structure parameter | ? | ? | ? |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SIR92 (Altomare et al., 1994), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL2014 (Sheldrick, 2015), SHELXL2014 (Sheldrick, 2008a, 2015b), Mercury (Macrae et al., 2008).
For compounds (1)–(3), ring-puckering parameters in the five-membered rings refer to the atom sequence O1–N1–C2–C3–C4 and those in the six-membered rings refer to the atom sequence O1–N1–C9A–C5A–C5–C4. For compounds (4) and (5), ring-puckering parameters in the seven-membered rings refer to the atom sequence N1–C2–C3–C4–C5–C5A–C9A. |
Five-membered rings | |||
Molecule | Q2 | φ2 | |
(1A) | 0.4489 (14) | 191.38 (19) | |
(1B) | 0.4678 (14) | 202.91 (19) | |
(2) | 0.443 (2) | 197.0 (3) | |
(3) | 0.4431 (14) | 195.7 (2) | |
Idealized half-chair | 234° | ||
Idealized envelope | 180° | ||
Six-membered rings | |||
Molecule | Q | θ | φ |
(1A) | 0.6289 (13) | 55.02 (13) | 348.05 (17) |
(1B) | 0.6332 (14) | 53.46 (13) | 342.82 (17) |
(2) | 0.629 (2) | 53.01 (18) | 342.4 (2) |
(3) | 0.6260 (14) | 53.20 (13) | 343.83 (17) |
Idealized half-chair | 50.8° | 330° | |
Idealized envelope | 54.7° | 360° | |
Seven-membered rings | |||
Molecule | Q2 | φ2 | φ3 |
(4) | 0.3446 (12) | 164.5 (2) | 230.19 (11) |
(5RT) | 0.385 (3) | 154.7 (4) | 231.6 (2) |
(5LT), Molecule 1 | 0.4038 (15) | 148.8 (2) | 231.63 (13) |
(5LT), Molecule 2 | 0.3760 (15) | 158.2 (2) | 231.28 (13) |
(5LT), Molecule 3 | 0.3708 (15) | 153.3 (2) | 231.88 (14) |
(5LT), Molecule 4 | 0.3790 (15) | 152.7 (2) | 231.65 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2A—H2A···O1Ai | 1.00 | 2.61 | 3.4061 (17) | 137 |
C5A—H5AA···Cg1A2ii | 1.00 | 2.60 | 3.5600 (16) | 163 |
C4B—H4B···O1Biii | 1.00 | 2.43 | 3.1601 (18) | 129 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+2, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C82—H82···O1i | 0.959 | 2.66 | 3.587 (3) | 164 |
Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O1i | 0.95 | 2.59 | 3.3880 (19) | 141.9 |
C27—H27···Cg31ii | 0.95 | 2.86 | 3.6294 (16) | 139 |
C28—H28···Cg32ii | 0.95 | 2.90 | 3.6116 (16) | 133 |
Symmetry codes: (i) x, y+1, z; (ii) −x, y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.904 (17) | 2.450 (16) | 3.2709 (14) | 151 (13) |
O1—H1O···N1ii | 0.88 (2) | 2.14 (2) | 3.0187 (14) | 172.9 (16) |
C5—H5A···N1ii | 0.99 | 2.67 | 3.3657 (16) | 127.6 |
C6—H6···F1iii | 0.95 | 2.47 | 3.4236 (16) | 176.8 |
C5—H5A···O1iv | 0.99 | 2.53 | 3.4027 (15) | 147.5 |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y+1/2, z; (iii) −x+1, −y+1, −z+1; (iv) −x+3/2, y−1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O7i | 0.88 (3) | 2.49 (3) | 3.356 (3) | 171 (3) |
O7—H7O···N1ii | 0.88 | 2.02 | 2.889 (3) | 168.8 |
C9—H9···O7i | 0.93 | 2.63 | 3.451 (4) | 147.3 |
Symmetry codes: (i) x−y+2/3, x+1/3, −z+4/3; (ii) −y+2/3, x−y+1/3, z+1/3. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H1N···O31i | 0.906 (16) | 2.287 (16) | 3.1897 (15) | 173.9 (13) |
N21—H2N···O11ii | 0.895 (16) | 2.370 (17) | 3.2455 (15) | 165.8 (13) |
N31—H3N···O21iii | 0.901 (17) | 2.326 (17) | 3.2208 (15) | 172.2 (14) |
N41—H4N···O41iv | 0.893 (16) | 2.310 (16) | 3.1952 (15) | 170.9 (14) |
O11—H1O···N11v | 0.869 (19) | 2.00 (2) | 2.8553 (15) | 166.1 (17) |
O21—H2O···N41 | 0.89 (2) | 1.98 (2) | 2.8542 (15) | 168.6 (18) |
O31—H3O···N21 | 0.864 (19) | 2.008 (19) | 2.8619 (15) | 169.5 (17) |
O41—H4O···N31i | 0.88 (2) | 2.00 (2) | 2.8570 (15) | 167.3 (17) |
Symmetry codes: (i) x, y, z+1; (ii) −y+2/3, x−y+1/3, z−2/3; (iii) x−y+2/3, x+1/3, −z+1/3; (iv) y−1/3, −x+y+1/3, −z+4/3; (v) −x+y+1/3, −x+2/3, z−1/3. |