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In the structure of (6R*,11R*)-5-acetyl-11-ethyl-6,11-di­hydro-5H-dibenzo[b,e]azepine-6-carb­oxy­lic acid, C19H19NO3, (I), the mol­ecules are linked into sheets by a combination of O-H...O and C-H...O hydrogen bonds; in the structure of the monomethyl analogue (6RS,11SR)-5-acetyl-11-ethyl-2-methyl-6,11-di­hydro-5H-dibenzo[b,e]azepine-6-carb­oxy­lic acid, C20H21NO3, (II), the mol­ecules are linked into simple C(7) chains by O-H...O hydrogen bonds; and in the structure of the di­methyl analogue (6RS,11SR)-5-acetyl-11-ethyl-1,3-di­methyl-6,11-di­hydro-5H-dibenzo[b,e]azepine-6-carb­oxy­lic acid, C21H23NO3, (III), a combination of O-H...O, C-H...O and C-H...[pi](arene) hydrogen bonds links the mol­ecules into a three-dimensional framework structure. None of these structures exhibits the R22(8) dimer motif characteristic of simple carb­oxy­lic acids.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614003568/yf3057sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614003568/yf3057Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614003568/yf3057IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614003568/yf3057IIIsup4.hkl
Contains datablock III

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614003568/yf3057Isup5.cml
Supplementary material

CCDC references: 987415; 987416; 987417

Introduction top

The dibenzo[b,e]azepine ring is an important pharmacophore in drug discovery and many of its derivatives exhibit a broad spectrum of biological activities (Van der Burg et al., 1970; Brogden et al., 1978; Nickolson & Wieringa, 1981; Berger et al., 1989; De Boer et al., 1996; Roeder et al., 1998; Andrés et al., 2002; Wikström et al., 2002). Consequently, a significant number of synthetic methods have been developed for the synthesis of new derivatives of this heterocyclic system (Moriconi & Maniscalco, 1972; Sasakura & Sugasawa, 1981; Stappers et al., 2002). In this context, we have recently developed a simple and practical synthetic route to obtain novel series of 6,11-di­hydro­dibenzo[b,e]azepines from readily available 2-allyl-N-benzyl-substituted anilines (Palma et al., 2004, 2010). To broaden the scope of this route, and in continuation of our research programme on the preparation of new potentially bio-active molecules containing the di­hydro­dibenzo[b,e]azepine nucleus, we have achieved a simple synthesis of three previously unknown 5-acetyl-11-ethyl-6,11-di­hydro-5H-dibenzo[b,e]azepine-6-carb­oxy­lic acids. Here we report the molecular structures and supra­molecular assembly of three closely related compounds, namely (6R*,11R*)-5-acetyl-11-ethyl-6,11-di­hydro-5H-dibenzo[b,e]azepine-6-carb­oxy­lic acid, (I) (Fig. 1), (6RS,11SR)-5-acetyl-11-ethyl-2-methyl-6,11-di­hydro-5H- dibenzo[b,e]azepine-6-carb­oxy­lic acid, (II) (Fig. 2), and (6RS,11SR)-5-acetyl-11-ethyl-1,3-di­methyl-6,11-di­hydro- 5H-dibenzo[b,e]azepine-6-carb­oxy­lic acid, (III) (Fig. 3), the constitutions of which differ only in the presence of one methyl substituent in (II) and two in (III), while there are none in (I). The synthesis of compounds (I)–(III) was achieved by intra­molecular Friedel–Crafts alkyl­ation of the corresponding methyl 2-[N-(2-allyl­aryl)­acetamido]-2-phenyl­acetates using concentrated sulfuric acid at 373 K (see scheme).

Experimental top

Synthesis and crystallization top

For the synthesis of each of (I)–(III), a suspension of the appropriately substituted racemic methyl 2-[N-(2-allyl­aryl)­acetamido]-2-phenyl­acetate (see scheme) (1.0 g) in concentrated sulfuric acid (3 ml) was stirred at 373 K for 7 min. The reaction mixture was cooled to ambient temperature by the addition of ice and then extracted with ethyl acetate (3 × 50 ml). The combined organic extracts were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The resulting crude products were subjected to column chromatographic purification over silica gel using heptane–ethyl acetate–acetic acid (1:2:0.04 v/v/v). Crystallization from ethyl acetate–ethanol (30:1 v/v) at ambient temperature and in the presence of air gave colourless crystals of (I)–(III), suitable for single-crystal X-ray diffraction. Compound (I): yield 35%, m.p. 449–450 K, HRMS m/z [M]+ found 309.1366, C19H19NO3 requires 309.1365. Compound (II): yield 20%, m.p. 460–462 K, HRMS m/z [M]+ found 323.1525, C20H21NO3 requires 323.1521. Compound (III): yield 41%, m.p. 497–499 K, HRMS m/z [M]+ found 337.1653, C21H21NO3 requires 337.1678.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps and subsequently treated as riding atoms. C-bound H atoms were permitted to ride in geometrically idealized positions, with C—H = 0.95 (aromatic), 0.98 (CH3), 0.99 (CH2) or 1.00 Å (aliphatic C—H), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other C-bound H atoms. O-bound H atoms were permitted to ride at the positions located in difference maps with Uiso(H) = 1.5Ueq(O), giving the O—H distances shown in Table 3. Several low-angle reflections, which had been wholly or partially attenuated by the beam stop, were omitted from the final refinements. The value of the Flack x parameter (Flack, 1983) for (I) was indeterminate (Flack & Bernardinelli, 2000); accordingly, Friedel-equivalent reflections were merged prior to the final refinements. Examination of the refined structures using PLATON (Spek, 2009) showed the presence of two small cavities in the structure of (II), centred at (1/2, 0, 1/2) and (1/2, 1/2, 0) and each of volume 24 Å3; these cavities are far too small to contain any plausible solvent molecule but, nonetheless, the largest peak in the difference map, 0.68 e Å-3 at (0.523, 0.482, 0.064), was very close to one of the cavities. However, application of the SQUEEZE procedure in PLATON revealed only one excess electron per cavity. Accordingly, we regard both the difference peak and the excess electron count as minor artefacts of the data.

Results and discussion top

The molecules of (I)–(III) all contain two stereogenic centres at atoms C6 and C11 (Figs. 1–3). In (I), the exocyclcic substituents at atoms C6 and C11 have a cis arrangement relative to the azepine ring, while those in (II) and (III) have a trans arrangement. For each compound, the reference molecule was selected as one having the R configuration at atom C6. On this basis, the reference molecule of (I) has the R configuration at atom C11, while those of (II) and (III) have the S configuration at atom C11. Compounds (II) and (III) crystallize as racemic mixtures, as shown by the centrosymmetric space group, but (I) crystallizes in the Sohnke space group P21. Hence in the absence of twinning, for which no evidence was found, each crystal of (I) contains only one enanti­omorph. It was not possible to determine the absolute configuration of the molecules in the crystal of (I) which was selected for data collection, and hence the configuration of the reference molecule was set to have the R configuration at atom C6, just as for (II) and (III).

Since the methyl 2-[N-(2-allyl­aryl)­acetamido]-2-phenyl­acetates used as the precursors to (I)–(III) (see scheme) are all racemic, the crystallization of (II) and (III) as racemic mixtures is unsurprising, and the method of synthesis makes it probable that (I) is formed in solution as a racemic mixture, which then crystallizes as a conglomerate rather than as a racemate. More problematic is the difference in relative configurations at atoms C6 and C11 between (I), (6R*,11R*), on the one hand and (II) and (III), (6RS,11SR), on the other. Since the yields of the purified crystallized products are all significantly less than 50% (see Experimental), it is at least possible that the compounds may be formed as diastereoisomeric mixtures, and that the stereoisomers reported here are simply those which crystallized preferentially. However, it must be emphasized that there is no direct evidence on this point, and so this suggestion must be regarded as speculative.

Within the amide unit, the N5—C51 and C51—O51 distances (Table 2) are typical of those found in N,N-disubstituted amides (Allen et al., 1987), while the C—O distances in the carb­oxy­lic acid units are fully consistent with the locations of the carb­oxy­lic H atoms as found in difference maps. The remaining bond distances present no unusual values. In each of (I)–(III), the azepine ring adopts a conformation inter­mediate between the boat and twist-boat forms (Evans & Boeyens, 1989; Entrena et al., 1997). For (II) and (III), the ring-puckering parameters (Cremer & Pople, 1975) are very similar (Table 2), but the extent of the ring puckering, as shown by the overall puckering amplitude Q, is somewhat larger in (I) than in (II) and (III). This may be associated with the cis stereochemistry at atoms C6 and C11 in (I), compared with the trans arrangement in (II) and (III). The orientation of the amide unit relative to the azepine ring is very similar in all three compounds, as shown by the values of the torsion angles C6—N5—C51—O51 and C6—N5—C51—C52 (Table 2, and Figs. 1–3). By contrast, the orientation of the carb­oxy­lic acid unit varies widely, and this variation may be a consequence of the different hydrogen-bonding arrangements in the three structures. The conformations adopted by the ethyl group also vary widely, and since this substituent plays no part in the supra­molecular assembly it seems likely that these conformations are determined by the methyl groups based on atom C112 finding accommodation in whatever suitable spaces are available within the hydrogen-bonded structure.

Accordingly, despite their very similar constitutions, (I)–(III) differ not only in the relative configurations at their two stereogenic centres but also in their crystallization characteristics, i.e. as a conglomerate for (I) and as a racemate for each of (II) and (III), with Z values of 2, 4 and and 4, respectively, as well as in their molecular conformations. They also differ in their modes of supra­molecular assembly, with the formation of a simple hydrogen-bonded chain in (II), a hydrogen-bonded sheet in (I), and a three-dimensional framework structure in (III). It is convenient to discuss the supra­molecular assembly in the structures of (I)–(III) in the order of increasing complexity.

The O—H···O hydrogen bond in compound (II) (Table 3) links molecules related by the 21 screw axis along (1/2, y, 3/4) into a C(7) (Bernstein et al., 1995) chain running parallel to the [010] direction. (Fig. 4). The two shortest inter­molecular C—H···O contacts (Table 3) have H···O distances not significantly less than the sum of the van der Waals radii for H and O (2.61 Å; Bondi, 1964; Rowland & Taylor, 1996). In any event, both contacts have fairly small C—H···O angles (cf. Wood et al., 2009), so that neither can be regarded as structurally significant. Two chains of this type, related to one another by inversion, pass through each unit cell but there are no direction-specific inter­actions between adjacent chains.

The supra­molecular assembly in (I) and (III) can most readily be analysed in terms of a series of one-dimensional substructures (Ferguson et al., 1998a,b; Gregson et al., 2000). In (I), molecules related by a 21 screw axis are similarly linked by an O—H···O hydrogen bond to form a C(7) chain running parallel to the [010] direction but, in contrast with (II), chains in (I) which are related by translation along the [101] direction are linked by a C—H···O hydrogen bond to form a sheet of R34(26) rings parallel to (101) (Fig. 5). The only other short inter­molecular contact involves a low-acidity C—H bond from a methyl group and is thus unlikely to be structurally significant.

The molecules of (III) are linked into a three-dimensional framework structure by a combination of O—H···O, C—H···O and C—H···π(arene) hydrogen bonds (Table 3). The O—H···O hydrogen bond links molecules related by the n-glide plane at y = 3/4 to form a C(7) chain running parallel to the [101] direction (Fig. 6), and the C—H···O hydrogen bond links molecules related by a 21 screw axis along (3/4, y, 1/4) to form a C(8) chain running parallel to the [010] direction (Fig. 6). The combination of these two chains generates a sheet lying parallel to (101) and built from a single type of centrosymmetric R44(30) ring (Fig. 6). Sheets of this type are linked to form a continuous three-dimensional framework structure by the C—H···π(arene) hydrogen bond, which links molecules related by translation along the [100] direction (Fig. 7). The combination of chains along [100], [010] and [101] is sufficient to form a three-dimensional structure.

It is thus striking that none of (I)–(III) exhibits the R22(8) dimer motif so characteristic of simple carb­oxy­lic acids. Instead, all utilize atom O51 of the N-acetyl group as acceptor in an O—H···O hydrogen bond, and it is of inter­est briefly to compare the substructures which can be identified in the supra­molecular assemblies of (I)–(III). In each of the structures, a C(7) chain motif can be identified built from O—H···O hydrogen bonds. However, these chains differ in that those in (I) and (II) contain molecules related by a 21 screw axis, whereas that in (III) contains molecules related by an n-glide plane. Similarly, sheets built from a combination of O—H···O and C—H···O hydrogen bonds can be identified in the structures of (I) and (III) (Figs. 5 and 6). Both sheets exhibit (4,4) topology (Batten & Robson, 1998). The ring sizes in the sheets in (I) and (III) differ, as do the numbers of hydrogen-bond acceptors within these rings, since in (I) amide atom O51 acts as a double acceptor of hydrogen bonds, unlike that in (III). However, within the sheet in (III) the constituent rings are centrosymmetric, while those in (I) are not centrosymmetric. Chain formation by means of O—H···O hydrogen bonds has been extensively studied in keto acids, where the chain motif follows directly from the mutual disposition of the carboxyl and keto groups. Thus, γ-keto-acids form C(7) chains (e.g. Thompson et al., 2004; Malak et al., 2006), δ-keto acids form C(8) chains (e.g. Davison, Kikolski et al., 2004) and ε-keto acids form C(9) chains (e.g. Davison, Thompson et al., 2004), while longer chain motifs are generated in steroidal keto acids (e.g. Kikolski et al., 2006).

Related literature top

For related literature, see: Allen et al. (1987); Andrés et al. (2002); Batten & Robson (1998); Berger et al. (1989); Bernstein et al. (1995); Bondi (1964); Brogden et al. (1978); Cremer & Pople (1975); Davison, Kikolski, Lalancette & Thompson (2004); Davison, Thompson & Lalancette (2004); De Boer, Nefkens, van Helvoirt & van Delft (1996); Entrena et al. (1997); Evans & Boeyens (1989); Ferguson et al. (1998a, 1998b); Flack (1983); Flack & Bernardinelli (2000); Gregson et al. (2000); Kikolski et al. (2006); Malak et al. (2006); Moriconi & Maniscalco (1972); Nickolson & Wieringa (1981); Palma et al. (2004, 2010); Roeder et al. (1998); Rowland & Taylor (1996); Sasakura & Sugasawa (1981); Spek (2009); Stappers et al. (2002); Thompson et al. (2004); Van der Burg, Bonta, Delobelle, Ramon & Vargaftig (1970); Wikström et al. (2002); Wood et al. (2009).

Computing details top

For all compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003). Program(s) used to solve structure: SIR2004 (Burla et al., 2005) for (I), (II); SHELXS97 (Sheldrick, 2008) for (III). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the (6R,11R) enantiomer of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The molecular structure of the (6R,11S) enantiomer of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. The molecular structure of the (6R,11S) enantiomer of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 4] Fig. 4. Part of the crystal structure of (II), showing the formation of a hydrogen-bonded (dashed lines) chain parallel to [010]. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (-x + 1, y + 1/2, -z + 1/2), (-x + 1, y - 1/2, -z + 1/2), (x, y + 1, z) and (x, y - 1, z), respectively.
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded (dashed lines) sheet parallel to (101). For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
[Figure 6] Fig. 6. A stereoview of part of the crystal structure of (III), showing the formation of a hydrogen-bonded (dashed lines) sheet of R44(30) rings parallel to (101) and built from a combination of O—H···O and C—H···O hydrogen bonds. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
[Figure 7] Fig. 7. A stereoview of part of the crystal structure of (III), showing the formation of a chain parallel to [100] built from C—H···π(arene) hydrogen bonds (dashed lines). For the sake of clarity, H atoms not involved in the motif shown have been omitted.
(I) (6R*,11R*)-5-Acetyl-11-ethyl-6,11-dihydro-5H-dibenzo[b,e]azepine-6-carboxylic acid top
Crystal data top
C19H19NO3F(000) = 328
Mr = 309.35Dx = 1.342 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1853 reflections
a = 8.8053 (3) Åθ = 3.2–27.5°
b = 10.9821 (4) ŵ = 0.09 mm1
c = 9.0080 (6) ÅT = 120 K
β = 118.510 (3)°Rod, colourless
V = 765.45 (6) Å30.26 × 0.14 × 0.10 mm
Z = 2
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
1851 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1638 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.7°
φ and ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1414
Tmin = 0.977, Tmax = 0.991l = 1111
13276 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.15 w = 1/[σ2(Fo2) + (0.0351P)2 + 0.1657P]
where P = (Fo2 + 2Fc2)/3
1851 reflections(Δ/σ)max = 0.001
210 parametersΔρmax = 0.21 e Å3
1 restraintΔρmin = 0.24 e Å3
Crystal data top
C19H19NO3V = 765.45 (6) Å3
Mr = 309.35Z = 2
Monoclinic, P21Mo Kα radiation
a = 8.8053 (3) ŵ = 0.09 mm1
b = 10.9821 (4) ÅT = 120 K
c = 9.0080 (6) Å0.26 × 0.14 × 0.10 mm
β = 118.510 (3)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
1851 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1638 reflections with I > 2σ(I)
Tmin = 0.977, Tmax = 0.991Rint = 0.049
13276 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0361 restraint
wR(F2) = 0.081H-atom parameters constrained
S = 1.15Δρmax = 0.21 e Å3
1851 reflectionsΔρmin = 0.24 e Å3
210 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.6424 (3)0.5942 (2)0.7939 (3)0.0186 (5)
H10.65990.61540.90310.022*
C20.7828 (3)0.5595 (2)0.7731 (3)0.0211 (5)
H20.89530.55890.86780.025*
C30.7604 (3)0.5255 (2)0.6149 (3)0.0202 (5)
H30.85630.49930.60190.024*
C40.5955 (3)0.5306 (2)0.4757 (3)0.0166 (5)
H40.57800.50790.36690.020*
C4a0.4576 (3)0.5687 (2)0.4973 (3)0.0142 (5)
N50.2883 (2)0.58197 (17)0.3533 (2)0.0132 (4)
C60.1469 (3)0.4966 (2)0.3244 (3)0.0128 (4)
H60.03890.54610.28310.015*
C6a0.1714 (3)0.4295 (2)0.4842 (3)0.0145 (5)
C70.1243 (3)0.3077 (2)0.4737 (3)0.0174 (5)
H70.08840.26520.37040.021*
C80.1286 (3)0.2465 (2)0.6107 (3)0.0189 (5)
H80.09770.16280.60080.023*
C90.1780 (3)0.3073 (2)0.7616 (3)0.0188 (5)
H90.17590.26700.85400.023*
C100.2305 (3)0.4277 (2)0.7762 (3)0.0185 (5)
H100.26740.46850.88080.022*
C10a0.2307 (3)0.4909 (2)0.6412 (3)0.0151 (5)
C110.3097 (3)0.6185 (2)0.6677 (3)0.0150 (5)
H110.23070.66940.56860.018*
C11a0.4763 (3)0.5982 (2)0.6566 (3)0.0145 (5)
C510.2534 (3)0.6720 (2)0.2388 (3)0.0142 (5)
O510.10670 (19)0.68043 (16)0.11339 (19)0.0180 (4)
C520.3950 (3)0.7609 (2)0.2675 (3)0.0189 (5)
H52A0.47840.72190.23970.028*
H52B0.45370.78620.38620.028*
H52C0.34520.83240.19520.028*
C610.1208 (3)0.4093 (2)0.1806 (3)0.0145 (5)
O610.0387 (2)0.36474 (17)0.10291 (19)0.0186 (4)
H610.04870.31070.02970.028*
O620.2327 (2)0.38608 (17)0.1438 (2)0.0224 (4)
C1110.3325 (3)0.6837 (2)0.8280 (3)0.0202 (5)
H11A0.22470.67610.83620.024*
H11B0.42660.64400.92840.024*
C1120.3752 (3)0.8181 (2)0.8272 (3)0.0229 (5)
H12A0.48210.82600.81950.034*
H12B0.39050.85650.93170.034*
H12C0.28040.85830.73000.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0214 (12)0.0168 (12)0.0133 (11)0.0021 (10)0.0048 (10)0.0003 (10)
C20.0163 (12)0.0170 (13)0.0222 (13)0.0025 (9)0.0027 (10)0.0035 (10)
C30.0158 (11)0.0198 (13)0.0252 (13)0.0018 (10)0.0101 (11)0.0052 (10)
C40.0191 (11)0.0145 (12)0.0168 (11)0.0002 (9)0.0091 (10)0.0012 (9)
C4a0.0138 (11)0.0128 (12)0.0136 (11)0.0010 (8)0.0045 (10)0.0021 (9)
N50.0120 (9)0.0137 (10)0.0117 (9)0.0010 (7)0.0038 (8)0.0010 (8)
C60.0117 (10)0.0148 (11)0.0113 (10)0.0006 (8)0.0049 (9)0.0002 (9)
C6a0.0133 (11)0.0176 (12)0.0136 (11)0.0010 (9)0.0071 (9)0.0004 (9)
C70.0156 (11)0.0201 (12)0.0151 (11)0.0004 (9)0.0061 (9)0.0019 (9)
C80.0177 (12)0.0162 (12)0.0217 (12)0.0028 (10)0.0085 (10)0.0009 (10)
C90.0173 (12)0.0222 (13)0.0183 (12)0.0008 (10)0.0097 (10)0.0054 (10)
C100.0172 (12)0.0242 (13)0.0135 (11)0.0020 (10)0.0069 (10)0.0006 (10)
C10a0.0125 (10)0.0167 (11)0.0162 (11)0.0006 (9)0.0068 (9)0.0002 (9)
C110.0152 (11)0.0167 (12)0.0135 (11)0.0009 (9)0.0073 (9)0.0015 (9)
C11a0.0184 (12)0.0098 (10)0.0156 (11)0.0010 (9)0.0083 (10)0.0006 (9)
C510.0168 (11)0.0142 (11)0.0121 (11)0.0004 (9)0.0074 (9)0.0020 (9)
O510.0161 (8)0.0186 (9)0.0150 (8)0.0005 (7)0.0040 (7)0.0025 (7)
C520.0207 (12)0.0162 (12)0.0194 (12)0.0010 (10)0.0092 (10)0.0029 (10)
C610.0176 (11)0.0127 (11)0.0117 (10)0.0001 (9)0.0058 (9)0.0022 (9)
O610.0176 (8)0.0213 (9)0.0150 (8)0.0045 (7)0.0062 (7)0.0065 (7)
O620.0221 (9)0.0252 (10)0.0241 (9)0.0024 (7)0.0144 (8)0.0062 (8)
C1110.0243 (12)0.0195 (13)0.0176 (12)0.0018 (11)0.0106 (10)0.0036 (11)
C1120.0265 (13)0.0208 (13)0.0248 (13)0.0031 (10)0.0151 (11)0.0065 (10)
Geometric parameters (Å, º) top
C1—C21.388 (4)C9—C101.386 (3)
C1—C11a1.395 (3)C9—H90.9500
C1—H10.9500C10—C10a1.401 (3)
C2—C31.393 (4)C10—H100.9500
C2—H20.9500C10a—C111.532 (3)
C3—C41.395 (3)C11—C11a1.533 (3)
C3—H30.9500C11—C1111.536 (3)
C4—C4a1.383 (3)C11—H111.0000
C4—H40.9500C51—O511.249 (3)
C4a—C11a1.402 (3)C51—C521.506 (3)
C4a—N51.442 (3)C52—H52A0.9800
N5—C511.354 (3)C52—H52B0.9800
N5—C61.479 (3)C52—H52C0.9800
C6—C6a1.538 (3)C61—O621.207 (3)
C6—C611.538 (3)C61—O611.328 (3)
C6—H61.0000O61—H610.8602
C6a—C71.390 (3)C111—C1121.523 (4)
C6a—C10a1.423 (3)C111—H11A0.9900
C7—C81.390 (3)C111—H11B0.9900
C7—H70.9500C112—H12A0.9800
C8—C91.386 (3)C112—H12B0.9800
C8—H80.9500C112—H12C0.9800
C2—C1—C11a120.9 (2)C10a—C10—H10119.0
C2—C1—H1119.5C10—C10a—C6a118.4 (2)
C11a—C1—H1119.5C10—C10a—C11120.5 (2)
C1—C2—C3120.7 (2)C6a—C10a—C11120.8 (2)
C1—C2—H2119.6C10a—C11—C11a103.51 (18)
C3—C2—H2119.6C10a—C11—C111114.78 (19)
C2—C3—C4119.1 (2)C11a—C11—C111115.41 (19)
C2—C3—H3120.4C10a—C11—H11107.6
C4—C3—H3120.4C11a—C11—H11107.6
C4a—C4—C3119.6 (2)C111—C11—H11107.6
C4a—C4—H4120.2C1—C11a—C4a117.4 (2)
C3—C4—H4120.2C1—C11a—C11125.3 (2)
C4—C4a—C11a122.1 (2)C4a—C11a—C11116.87 (19)
C4—C4a—N5120.27 (19)O51—C51—N5120.3 (2)
C11a—C4a—N5117.61 (19)O51—C51—C52121.4 (2)
C51—N5—C4a121.36 (18)N5—C51—C52118.30 (19)
C51—N5—C6117.57 (18)C51—C52—H52A109.5
C4a—N5—C6121.06 (17)C51—C52—H52B109.5
N5—C6—C6a114.16 (18)H52A—C52—H52B109.5
N5—C6—C61108.54 (17)C51—C52—H52C109.5
C6a—C6—C61112.80 (19)H52A—C52—H52C109.5
N5—C6—H6107.0H52B—C52—H52C109.5
C6a—C6—H6107.0O62—C61—O61125.0 (2)
C61—C6—H6107.0O62—C61—C6123.3 (2)
C7—C6a—C10a118.7 (2)O61—C61—C6111.64 (18)
C7—C6a—C6119.6 (2)C61—O61—H61110.7
C10a—C6a—C6121.6 (2)C112—C111—C11111.7 (2)
C8—C7—C6a121.6 (2)C112—C111—H11A109.3
C8—C7—H7119.2C11—C111—H11A109.3
C6a—C7—H7119.2C112—C111—H11B109.3
C9—C8—C7120.0 (2)C11—C111—H11B109.3
C9—C8—H8120.0H11A—C111—H11B108.0
C7—C8—H8120.0C111—C112—H12A109.5
C8—C9—C10119.2 (2)C111—C112—H12B109.5
C8—C9—H9120.4H12A—C112—H12B109.5
C10—C9—H9120.4C111—C112—H12C109.5
C9—C10—C10a122.0 (2)H12A—C112—H12C109.5
C9—C10—H10119.0H12B—C112—H12C109.5
C11a—C1—C2—C31.3 (4)C7—C6a—C10a—C11170.7 (2)
C1—C2—C3—C42.1 (4)C6—C6a—C10a—C1113.4 (3)
C2—C3—C4—C4a0.1 (4)C10—C10a—C11—C11a108.4 (2)
C3—C4—C4a—C11a2.7 (4)C6a—C10a—C11—C11a65.6 (3)
C3—C4—C4a—N5176.0 (2)C10—C10a—C11—C11118.3 (3)
C4—C4a—N5—C5170.0 (3)C6a—C10a—C11—C111167.7 (2)
C11a—C4a—N5—C51108.7 (2)C2—C1—C11a—C4a1.4 (3)
C4—C4a—N5—C6109.3 (2)C2—C1—C11a—C11171.5 (2)
C11a—C4a—N5—C672.0 (3)C4—C4a—C11a—C13.4 (3)
C51—N5—C6—C6a158.55 (19)N5—C4a—C11a—C1175.3 (2)
C4a—N5—C6—C6a22.1 (3)C4—C4a—C11a—C11170.1 (2)
C51—N5—C6—C6174.7 (2)N5—C4a—C11a—C1111.2 (3)
C4a—N5—C6—C61104.7 (2)C10a—C11—C11a—C1103.1 (3)
N5—C6—C6a—C7141.2 (2)C111—C11—C11a—C123.1 (4)
C61—C6—C6a—C716.7 (3)C10a—C11—C11a—C4a69.8 (2)
N5—C6—C6a—C10a42.9 (3)C111—C11—C11a—C4a163.9 (2)
C61—C6—C6a—C10a167.43 (19)C4a—N5—C51—O51178.7 (2)
C10a—C6a—C7—C82.2 (3)C6—N5—C51—O510.7 (3)
C6—C6a—C7—C8173.8 (2)C4a—N5—C51—C521.5 (3)
C6a—C7—C8—C91.0 (4)C6—N5—C51—C52179.1 (2)
C7—C8—C9—C103.0 (3)N5—C6—C61—O6224.4 (3)
C8—C9—C10—C10a1.8 (3)C6a—C6—C61—O62103.1 (3)
C9—C10—C10a—C6a1.4 (3)N5—C6—C61—O61155.01 (18)
C9—C10—C10a—C11172.7 (2)C6a—C6—C61—O6177.5 (2)
C7—C6a—C10a—C103.4 (3)C10a—C11—C111—C112168.0 (2)
C6—C6a—C10a—C10172.6 (2)C11a—C11—C111—C11271.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O61—H61···O51i0.861.832.672 (2)167
C2—H2···O51ii0.952.493.309 (3)144
C112—H12A···O62iii0.982.463.418 (4)165
Symmetry codes: (i) x, y1/2, z; (ii) x+1, y, z+1; (iii) x+1, y+1/2, z+1.
(II) (6RS,11SR)-5-Acetyl-11-ethyl-2-methyl-6,11-dihydro-5H-dibenzo[b,e]azepine-6-carboxylic acid top
Crystal data top
C20H21NO3F(000) = 688
Mr = 323.38Dx = 1.262 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3906 reflections
a = 15.2894 (16) Åθ = 2.7–27.5°
b = 10.760 (2) ŵ = 0.09 mm1
c = 10.538 (2) ÅT = 120 K
β = 100.990 (11)°Block, colourless
V = 1701.9 (5) Å30.41 × 0.30 × 0.24 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3903 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode2589 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.092
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.3°
φ and ω scansh = 1919
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1313
Tmin = 0.966, Tmax = 0.980l = 1313
28096 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.155H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0624P)2 + 1.5377P]
where P = (Fo2 + 2Fc2)/3
3903 reflections(Δ/σ)max = 0.001
220 parametersΔρmax = 0.68 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C20H21NO3V = 1701.9 (5) Å3
Mr = 323.38Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.2894 (16) ŵ = 0.09 mm1
b = 10.760 (2) ÅT = 120 K
c = 10.538 (2) Å0.41 × 0.30 × 0.24 mm
β = 100.990 (11)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3903 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2589 reflections with I > 2σ(I)
Tmin = 0.966, Tmax = 0.980Rint = 0.092
28096 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0590 restraints
wR(F2) = 0.155H-atom parameters constrained
S = 1.05Δρmax = 0.68 e Å3
3903 reflectionsΔρmin = 0.29 e Å3
220 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.11423 (15)0.5736 (2)0.1081 (2)0.0183 (5)
H10.05510.56730.12340.022*
C20.13034 (15)0.6464 (2)0.0050 (2)0.0200 (5)
C30.21783 (16)0.6576 (2)0.0142 (2)0.0203 (5)
H30.23030.70890.08190.024*
C40.28655 (15)0.5946 (2)0.0642 (2)0.0189 (5)
H40.34590.60250.05020.023*
C4a0.26855 (14)0.5197 (2)0.1637 (2)0.0160 (5)
N50.33846 (12)0.45422 (17)0.24821 (17)0.0153 (4)
C60.36955 (15)0.5095 (2)0.3762 (2)0.0164 (5)
H60.41840.45430.42130.020*
C6a0.30137 (15)0.5169 (2)0.4643 (2)0.0166 (5)
C70.33741 (16)0.5563 (2)0.5908 (2)0.0216 (5)
H70.39890.57650.61230.026*
C80.28551 (17)0.5662 (2)0.6846 (2)0.0257 (5)
H80.31110.59300.76940.031*
C90.19597 (18)0.5366 (2)0.6534 (2)0.0267 (6)
H90.15940.54390.71650.032*
C100.15979 (16)0.4962 (2)0.5295 (2)0.0220 (5)
H100.09830.47540.50940.026*
C10a0.21130 (15)0.4849 (2)0.4325 (2)0.0176 (5)
C110.16359 (14)0.4346 (2)0.3022 (2)0.0180 (5)
H110.09850.44470.30140.022*
C11a0.18239 (15)0.5102 (2)0.1891 (2)0.0166 (5)
C210.05529 (16)0.7126 (2)0.0825 (2)0.0279 (6)
H21A0.07560.74090.16040.042*
H21B0.03660.78440.03710.042*
H21C0.00490.65560.10690.042*
C510.38517 (14)0.3587 (2)0.2100 (2)0.0182 (5)
O510.44856 (11)0.31255 (16)0.28673 (15)0.0231 (4)
C520.35754 (17)0.3077 (2)0.0754 (2)0.0265 (6)
H52A0.40640.31810.02820.040*
H52B0.30490.35260.03050.040*
H52C0.34330.21920.08000.040*
C610.41375 (15)0.6350 (2)0.3559 (2)0.0188 (5)
O610.47155 (11)0.61912 (15)0.27831 (17)0.0259 (4)
H610.49810.69360.26570.039*
O620.39924 (12)0.73197 (15)0.40492 (16)0.0270 (4)
C1110.17878 (16)0.2930 (2)0.2890 (2)0.0204 (5)
H11A0.15830.26810.19770.024*
H11B0.24340.27510.31250.024*
C1120.12941 (17)0.2163 (2)0.3747 (2)0.0254 (5)
H12A0.14780.24290.46480.038*
H12B0.14370.12810.36730.038*
H12C0.06510.22860.34720.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0180 (11)0.0202 (11)0.0166 (11)0.0000 (9)0.0034 (9)0.0008 (9)
C20.0249 (12)0.0211 (12)0.0128 (11)0.0011 (9)0.0008 (9)0.0013 (9)
C30.0278 (12)0.0210 (11)0.0117 (10)0.0006 (10)0.0026 (9)0.0011 (9)
C40.0209 (11)0.0231 (12)0.0137 (10)0.0016 (9)0.0063 (9)0.0007 (9)
C4a0.0189 (11)0.0173 (11)0.0117 (10)0.0005 (9)0.0026 (9)0.0007 (9)
N50.0161 (9)0.0180 (9)0.0118 (9)0.0001 (7)0.0026 (7)0.0007 (7)
C60.0189 (11)0.0188 (11)0.0110 (10)0.0003 (9)0.0012 (8)0.0014 (9)
C6a0.0236 (11)0.0138 (10)0.0134 (10)0.0017 (9)0.0057 (9)0.0013 (8)
C70.0279 (12)0.0214 (12)0.0150 (11)0.0016 (10)0.0028 (9)0.0002 (9)
C80.0385 (14)0.0260 (13)0.0129 (11)0.0029 (11)0.0055 (10)0.0007 (10)
C90.0374 (14)0.0294 (13)0.0170 (12)0.0032 (11)0.0144 (11)0.0013 (10)
C100.0256 (12)0.0234 (12)0.0190 (12)0.0039 (10)0.0092 (10)0.0008 (10)
C10a0.0230 (11)0.0164 (11)0.0139 (10)0.0005 (9)0.0049 (9)0.0004 (9)
C110.0168 (11)0.0241 (12)0.0128 (10)0.0001 (9)0.0026 (9)0.0025 (9)
C11a0.0198 (11)0.0185 (11)0.0117 (10)0.0024 (9)0.0032 (9)0.0015 (9)
C210.0264 (13)0.0319 (14)0.0240 (13)0.0011 (11)0.0008 (10)0.0079 (11)
C510.0175 (11)0.0200 (11)0.0181 (11)0.0007 (9)0.0055 (9)0.0001 (9)
O510.0236 (9)0.0262 (9)0.0190 (8)0.0066 (7)0.0026 (7)0.0024 (7)
C520.0298 (13)0.0286 (13)0.0216 (12)0.0045 (11)0.0058 (10)0.0070 (11)
C610.0197 (11)0.0220 (12)0.0141 (10)0.0007 (9)0.0018 (9)0.0018 (9)
O610.0279 (9)0.0218 (9)0.0323 (10)0.0053 (7)0.0166 (8)0.0036 (7)
O620.0377 (10)0.0196 (9)0.0256 (9)0.0007 (7)0.0111 (8)0.0024 (7)
C1110.0246 (12)0.0239 (12)0.0132 (11)0.0057 (10)0.0048 (9)0.0011 (9)
C1120.0310 (13)0.0257 (13)0.0197 (12)0.0060 (10)0.0054 (10)0.0040 (10)
Geometric parameters (Å, º) top
C1—C11a1.393 (3)C10—C10a1.409 (3)
C1—C21.398 (3)C10—H100.9500
C1—H10.9500C10a—C111.527 (3)
C2—C31.396 (3)C11—C11a1.515 (3)
C2—C211.507 (3)C11—C1111.551 (3)
C3—C41.384 (3)C11—H111.0000
C3—H30.9500C21—H21A0.9800
C4—C4a1.390 (3)C21—H21B0.9800
C4—H40.9500C21—H21C0.9800
C4a—C11a1.397 (3)C51—O511.241 (3)
C4a—N51.439 (3)C51—C521.504 (3)
N5—C511.356 (3)C52—H52A0.9800
N5—C61.468 (3)C52—H52B0.9800
C6—C6a1.524 (3)C52—H52C0.9800
C6—C611.543 (3)C61—O621.204 (3)
C6—H61.0000C61—O611.325 (3)
C6a—C10a1.397 (3)O61—H610.9200
C6a—C71.407 (3)C111—C1121.526 (3)
C7—C81.385 (3)C111—H11A0.9900
C7—H70.9500C111—H11B0.9900
C8—C91.383 (4)C112—H12A0.9800
C8—H80.9500C112—H12B0.9800
C9—C101.387 (3)C112—H12C0.9800
C9—H90.9500
C11a—C1—C2121.9 (2)C10—C10a—C11116.5 (2)
C11a—C1—H1119.1C11a—C11—C10a112.81 (19)
C2—C1—H1119.1C11a—C11—C111113.73 (18)
C3—C2—C1118.5 (2)C10a—C11—C111112.05 (18)
C3—C2—C21120.6 (2)C11a—C11—H11105.8
C1—C2—C21120.9 (2)C10a—C11—H11105.8
C4—C3—C2120.7 (2)C111—C11—H11105.8
C4—C3—H3119.7C1—C11a—C4a118.0 (2)
C2—C3—H3119.7C1—C11a—C11120.9 (2)
C3—C4—C4a119.8 (2)C4a—C11a—C11121.1 (2)
C3—C4—H4120.1C2—C21—H21A109.5
C4a—C4—H4120.1C2—C21—H21B109.5
C4—C4a—C11a121.1 (2)H21A—C21—H21B109.5
C4—C4a—N5121.3 (2)C2—C21—H21C109.5
C11a—C4a—N5117.50 (19)H21A—C21—H21C109.5
C51—N5—C4a123.97 (18)H21B—C21—H21C109.5
C51—N5—C6118.90 (18)O51—C51—N5120.0 (2)
C4a—N5—C6116.29 (17)O51—C51—C52120.8 (2)
N5—C6—C6a116.21 (18)N5—C51—C52119.2 (2)
N5—C6—C61107.51 (17)C51—C52—H52A109.5
C6a—C6—C61113.99 (18)C51—C52—H52B109.5
N5—C6—H6106.1H52A—C52—H52B109.5
C6a—C6—H6106.1C51—C52—H52C109.5
C61—C6—H6106.1H52A—C52—H52C109.5
C10a—C6a—C7119.4 (2)H52B—C52—H52C109.5
C10a—C6a—C6126.77 (19)O62—C61—O61125.2 (2)
C7—C6a—C6113.8 (2)O62—C61—C6125.3 (2)
C8—C7—C6a121.7 (2)O61—C61—C6109.52 (18)
C8—C7—H7119.2C61—O61—H61110.0
C6a—C7—H7119.2C112—C111—C11112.24 (19)
C9—C8—C7119.2 (2)C112—C111—H11A109.2
C9—C8—H8120.4C11—C111—H11A109.2
C7—C8—H8120.4C112—C111—H11B109.2
C8—C9—C10119.7 (2)C11—C111—H11B109.2
C8—C9—H9120.2H11A—C111—H11B107.9
C10—C9—H9120.2C111—C112—H12A109.5
C9—C10—C10a122.1 (2)C111—C112—H12B109.5
C9—C10—H10118.9H12A—C112—H12B109.5
C10a—C10—H10118.9C111—C112—H12C109.5
C6a—C10a—C10117.8 (2)H12A—C112—H12C109.5
C6a—C10a—C11125.67 (19)H12B—C112—H12C109.5
C11a—C1—C2—C31.7 (3)C6—C6a—C10a—C110.6 (4)
C11a—C1—C2—C21179.1 (2)C9—C10—C10a—C6a0.5 (3)
C1—C2—C3—C42.2 (3)C9—C10—C10a—C11177.7 (2)
C21—C2—C3—C4178.5 (2)C6a—C10a—C11—C11a48.5 (3)
C2—C3—C4—C4a0.3 (3)C10—C10a—C11—C11a133.4 (2)
C3—C4—C4a—C11a2.3 (3)C6a—C10a—C11—C11181.4 (3)
C3—C4—C4a—N5179.1 (2)C10—C10a—C11—C11196.7 (2)
C4—C4a—N5—C5167.9 (3)C2—C1—C11a—C4a0.8 (3)
C11a—C4a—N5—C51115.2 (2)C2—C1—C11a—C11178.4 (2)
C4—C4a—N5—C6101.4 (2)C4—C4a—C11a—C12.8 (3)
C11a—C4a—N5—C675.5 (2)N5—C4a—C11a—C1179.75 (19)
C51—N5—C6—C6a126.5 (2)C4—C4a—C11a—C11176.4 (2)
C4a—N5—C6—C6a63.6 (2)N5—C4a—C11a—C110.5 (3)
C51—N5—C6—C61104.4 (2)C10a—C11—C11a—C1116.4 (2)
C4a—N5—C6—C6165.5 (2)C111—C11—C11a—C1114.6 (2)
N5—C6—C6a—C10a4.9 (3)C10a—C11—C11a—C4a62.8 (3)
C61—C6—C6a—C10a121.0 (2)C111—C11—C11a—C4a66.2 (3)
N5—C6—C6a—C7172.59 (19)C4a—N5—C51—O51175.1 (2)
C61—C6—C6a—C761.5 (3)C6—N5—C51—O516.0 (3)
C10a—C6a—C7—C81.1 (3)C4a—N5—C51—C526.6 (3)
C6—C6a—C7—C8178.8 (2)C6—N5—C51—C52175.6 (2)
C6a—C7—C8—C90.0 (4)N5—C6—C61—O62131.7 (2)
C7—C8—C9—C100.8 (4)C6a—C6—C61—O621.4 (3)
C8—C9—C10—C10a0.6 (4)N5—C6—C61—O6149.6 (2)
C7—C6a—C10a—C101.3 (3)C6a—C6—C61—O61179.92 (18)
C6—C6a—C10a—C10178.6 (2)C11a—C11—C111—C112159.48 (19)
C7—C6a—C10a—C11176.7 (2)C10a—C11—C111—C11271.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O61—H61···O51i0.921.672.572 (2)167
C4—H4···O62ii0.952.583.220 (3)125
C8—H8···O62iii0.952.583.405 (3)145
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x, y+3/2, z1/2; (iii) x, y+3/2, z+1/2.
(III) (6RS,11SR)-5-Acetyl-11-ethyl-1,3-dimethyl-6,11-dihydro-5H-dibenzo[b,e]azepine-6-carboxylic acid top
Crystal data top
C21H23NO3F(000) = 720
Mr = 337.40Dx = 1.250 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3320 reflections
a = 9.2283 (11) Åθ = 2.8–25.5°
b = 16.691 (2) ŵ = 0.08 mm1
c = 11.9824 (18) ÅT = 120 K
β = 103.820 (11)°Block, colourless
V = 1792.2 (4) Å30.23 × 0.20 × 0.20 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3316 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode2090 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.139
Detector resolution: 9.091 pixels mm-1θmax = 25.5°, θmin = 3.9°
φ and ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 2019
Tmin = 0.981, Tmax = 0.984l = 1414
27558 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0317P)2 + 1.5359P]
where P = (Fo2 + 2Fc2)/3
3316 reflections(Δ/σ)max = 0.001
230 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C21H23NO3V = 1792.2 (4) Å3
Mr = 337.40Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.2283 (11) ŵ = 0.08 mm1
b = 16.691 (2) ÅT = 120 K
c = 11.9824 (18) Å0.23 × 0.20 × 0.20 mm
β = 103.820 (11)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3316 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2090 reflections with I > 2σ(I)
Tmin = 0.981, Tmax = 0.984Rint = 0.139
27558 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.120H-atom parameters constrained
S = 1.08Δρmax = 0.25 e Å3
3316 reflectionsΔρmin = 0.29 e Å3
230 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3227 (3)0.48561 (16)0.3898 (2)0.0174 (6)
C20.2439 (3)0.53647 (17)0.4458 (2)0.0197 (6)
H20.20720.51580.50760.024*
C30.2165 (3)0.61670 (17)0.4150 (2)0.0205 (6)
C40.2709 (3)0.64561 (17)0.3246 (2)0.0174 (6)
H40.25490.70010.30200.021*
C4a0.3486 (3)0.59547 (15)0.2670 (2)0.0141 (6)
N50.4052 (2)0.62796 (12)0.17360 (17)0.0132 (5)
C60.5661 (3)0.64307 (15)0.1962 (2)0.0146 (6)
H60.58170.66800.12410.018*
C6a0.6650 (3)0.56840 (16)0.2147 (2)0.0155 (6)
C70.8137 (3)0.58138 (16)0.2103 (2)0.0172 (6)
H70.84460.63420.19720.021*
C80.9167 (3)0.51994 (17)0.2243 (2)0.0206 (6)
H81.01730.53080.22280.025*
C90.8724 (3)0.44232 (17)0.2404 (2)0.0225 (7)
H90.94180.39930.25030.027*
C100.7248 (3)0.42871 (16)0.2419 (2)0.0194 (6)
H100.69400.37530.25100.023*
C10a0.6187 (3)0.49019 (16)0.2306 (2)0.0149 (6)
C110.4610 (3)0.46222 (16)0.2309 (2)0.0161 (6)
H110.47410.40970.27230.019*
C11a0.3770 (3)0.51523 (16)0.2974 (2)0.0148 (6)
C120.3465 (3)0.39932 (17)0.4299 (2)0.0256 (7)
H12A0.29680.39010.49250.038*
H12B0.45360.38890.45750.038*
H12C0.30450.36330.36580.038*
C310.1284 (4)0.67011 (19)0.4762 (3)0.0313 (8)
H31A0.09230.71690.42820.047*
H31B0.19250.68780.54950.047*
H31C0.04320.64030.49050.047*
C510.3141 (3)0.65751 (16)0.0762 (2)0.0163 (6)
O510.3684 (2)0.69395 (11)0.00503 (15)0.0212 (5)
C520.1502 (3)0.64286 (18)0.0543 (2)0.0231 (7)
H52A0.10630.68050.09970.035*
H52B0.13250.58790.07640.035*
H52C0.10420.65060.02750.035*
C610.6070 (3)0.70912 (16)0.2882 (2)0.0160 (6)
O610.7497 (2)0.70908 (11)0.34155 (16)0.0223 (5)
H610.76520.74740.39110.034*
O620.5169 (2)0.75766 (11)0.30369 (18)0.0268 (5)
C1110.3721 (3)0.44278 (17)0.1067 (2)0.0190 (6)
H11A0.35130.49330.06260.023*
H11B0.43430.40870.06910.023*
C1120.2253 (3)0.40005 (18)0.1024 (3)0.0273 (7)
H11C0.24490.34980.14570.041*
H11D0.17520.38850.02230.041*
H11E0.16120.43440.13650.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0145 (15)0.0211 (15)0.0154 (13)0.0016 (12)0.0008 (11)0.0038 (12)
C20.0160 (16)0.0306 (17)0.0129 (13)0.0002 (12)0.0044 (11)0.0035 (12)
C30.0161 (16)0.0286 (17)0.0157 (14)0.0010 (12)0.0016 (12)0.0018 (12)
C40.0174 (16)0.0171 (15)0.0165 (13)0.0010 (12)0.0017 (11)0.0019 (11)
C4a0.0119 (14)0.0192 (14)0.0095 (13)0.0024 (11)0.0011 (11)0.0001 (11)
N50.0127 (12)0.0133 (11)0.0129 (11)0.0004 (9)0.0014 (9)0.0021 (9)
C60.0131 (15)0.0160 (14)0.0142 (13)0.0015 (11)0.0022 (11)0.0026 (11)
C6a0.0185 (15)0.0173 (14)0.0103 (13)0.0000 (12)0.0026 (11)0.0020 (11)
C70.0188 (16)0.0189 (15)0.0151 (14)0.0031 (12)0.0063 (12)0.0019 (11)
C80.0163 (16)0.0257 (16)0.0199 (14)0.0034 (13)0.0048 (12)0.0067 (12)
C90.0192 (16)0.0247 (16)0.0232 (15)0.0058 (12)0.0040 (12)0.0013 (13)
C100.0230 (17)0.0159 (15)0.0199 (14)0.0009 (12)0.0063 (12)0.0012 (12)
C10a0.0176 (15)0.0166 (14)0.0102 (12)0.0011 (11)0.0026 (11)0.0008 (11)
C110.0177 (16)0.0137 (14)0.0165 (14)0.0002 (11)0.0032 (11)0.0002 (11)
C11a0.0123 (15)0.0176 (14)0.0134 (13)0.0004 (11)0.0011 (11)0.0003 (11)
C120.0296 (18)0.0251 (16)0.0242 (16)0.0015 (14)0.0101 (14)0.0099 (13)
C310.035 (2)0.0386 (19)0.0241 (16)0.0080 (15)0.0154 (14)0.0010 (14)
C510.0174 (16)0.0154 (14)0.0162 (14)0.0002 (11)0.0040 (12)0.0008 (11)
O510.0179 (11)0.0247 (11)0.0200 (10)0.0004 (9)0.0027 (8)0.0088 (9)
C520.0161 (16)0.0306 (17)0.0209 (15)0.0009 (13)0.0012 (12)0.0046 (13)
C610.0154 (16)0.0144 (14)0.0167 (14)0.0036 (12)0.0011 (11)0.0019 (11)
O610.0175 (11)0.0236 (11)0.0233 (10)0.0012 (8)0.0005 (8)0.0111 (9)
O620.0214 (12)0.0189 (11)0.0375 (12)0.0027 (9)0.0020 (9)0.0101 (9)
C1110.0190 (16)0.0210 (15)0.0175 (14)0.0034 (12)0.0051 (12)0.0051 (12)
C1120.0257 (18)0.0274 (17)0.0284 (17)0.0079 (14)0.0057 (14)0.0074 (13)
Geometric parameters (Å, º) top
C1—C21.390 (4)C10—H100.9500
C1—C11a1.408 (4)C10a—C111.529 (4)
C1—C121.518 (4)C11—C11a1.522 (4)
C2—C31.396 (4)C11—C1111.552 (4)
C2—H20.9500C11—H111.0000
C3—C41.384 (4)C12—H12A0.9800
C3—C311.509 (4)C12—H12B0.9800
C4—C4a1.389 (4)C12—H12C0.9800
C4—H40.9500C31—H31A0.9800
C4a—C11a1.396 (4)C31—H31B0.9800
C4a—N51.448 (3)C31—H31C0.9800
N5—C511.358 (3)C51—O511.246 (3)
N5—C61.466 (3)C51—C521.492 (4)
C6—C6a1.529 (4)C52—H52A0.9800
C6—C611.541 (4)C52—H52B0.9800
C6—H61.0000C52—H52C0.9800
C6a—C10a1.400 (4)C61—O621.207 (3)
C6a—C71.403 (4)C61—O611.319 (3)
C7—C81.381 (4)O61—H610.8604
C7—H70.9500C111—C1121.521 (4)
C8—C91.386 (4)C111—H11A0.9900
C8—H80.9500C111—H11B0.9900
C9—C101.385 (4)C112—H11C0.9800
C9—H90.9500C112—H11D0.9800
C10—C10a1.402 (4)C112—H11E0.9800
C2—C1—C11a119.3 (2)C10a—C11—C111110.3 (2)
C2—C1—C12118.6 (2)C11a—C11—H11105.4
C11a—C1—C12122.1 (2)C10a—C11—H11105.4
C1—C2—C3122.8 (3)C111—C11—H11105.4
C1—C2—H2118.6C4a—C11a—C1117.6 (2)
C3—C2—H2118.6C4a—C11a—C11120.5 (2)
C4—C3—C2117.7 (3)C1—C11a—C11121.9 (2)
C4—C3—C31120.8 (3)C1—C12—H12A109.5
C2—C3—C31121.5 (3)C1—C12—H12B109.5
C3—C4—C4a120.4 (3)H12A—C12—H12B109.5
C3—C4—H4119.8C1—C12—H12C109.5
C4a—C4—H4119.8H12A—C12—H12C109.5
C4—C4a—C11a122.3 (2)H12B—C12—H12C109.5
C4—C4a—N5118.9 (2)C3—C31—H31A109.5
C11a—C4a—N5118.8 (2)C3—C31—H31B109.5
C51—N5—C4a122.4 (2)H31A—C31—H31B109.5
C51—N5—C6119.2 (2)C3—C31—H31C109.5
C4a—N5—C6117.2 (2)H31A—C31—H31C109.5
N5—C6—C6a115.4 (2)H31B—C31—H31C109.5
N5—C6—C61108.6 (2)O51—C51—N5119.8 (2)
C6a—C6—C61116.3 (2)O51—C51—C52121.1 (2)
N5—C6—H6105.1N5—C51—C52119.0 (2)
C6a—C6—H6105.1C51—C52—H52A109.5
C61—C6—H6105.1C51—C52—H52B109.5
C10a—C6a—C7118.8 (2)H52A—C52—H52B109.5
C10a—C6a—C6126.1 (2)C51—C52—H52C109.5
C7—C6a—C6115.1 (2)H52A—C52—H52C109.5
C8—C7—C6a122.1 (3)H52B—C52—H52C109.5
C8—C7—H7118.9O62—C61—O61124.8 (2)
C6a—C7—H7118.9O62—C61—C6122.0 (2)
C7—C8—C9119.6 (3)O61—C61—C6113.1 (2)
C7—C8—H8120.2C61—O61—H61108.4
C9—C8—H8120.2C112—C111—C11113.2 (2)
C10—C9—C8118.6 (3)C112—C111—H11A108.9
C10—C9—H9120.7C11—C111—H11A108.9
C8—C9—H9120.7C112—C111—H11B108.9
C9—C10—C10a123.0 (3)C11—C111—H11B108.9
C9—C10—H10118.5H11A—C111—H11B107.8
C10a—C10—H10118.5C111—C112—H11C109.5
C6a—C10a—C10117.8 (2)C111—C112—H11D109.5
C6a—C10a—C11127.3 (2)H11C—C112—H11D109.5
C10—C10a—C11114.8 (2)C111—C112—H11E109.5
C11a—C11—C10a115.4 (2)H11C—C112—H11E109.5
C11a—C11—C111113.9 (2)H11D—C112—H11E109.5
C11a—C1—C2—C30.5 (4)C9—C10—C10a—C6a1.4 (4)
C12—C1—C2—C3180.0 (3)C9—C10—C10a—C11178.3 (2)
C1—C2—C3—C40.0 (4)C6a—C10a—C11—C11a43.6 (4)
C1—C2—C3—C31179.0 (3)C10—C10a—C11—C11a139.8 (2)
C2—C3—C4—C4a0.6 (4)C6a—C10a—C11—C11187.1 (3)
C31—C3—C4—C4a178.4 (3)C10—C10a—C11—C11189.4 (3)
C3—C4—C4a—C11a0.8 (4)C4—C4a—C11a—C10.4 (4)
C3—C4—C4a—N5179.4 (2)N5—C4a—C11a—C1179.0 (2)
C4—C4a—N5—C5162.8 (3)C4—C4a—C11a—C11179.3 (2)
C11a—C4a—N5—C51118.6 (3)N5—C4a—C11a—C112.1 (4)
C4—C4a—N5—C6105.2 (3)C2—C1—C11a—C4a0.2 (4)
C11a—C4a—N5—C673.5 (3)C12—C1—C11a—C4a179.8 (2)
C51—N5—C6—C6a123.6 (2)C2—C1—C11a—C11178.6 (2)
C4a—N5—C6—C6a68.0 (3)C12—C1—C11a—C110.9 (4)
C51—N5—C6—C61103.6 (3)C10a—C11—C11a—C4a59.8 (3)
C4a—N5—C6—C6164.8 (3)C111—C11—C11a—C4a69.3 (3)
N5—C6—C6a—C10a11.2 (4)C10a—C11—C11a—C1121.4 (3)
C61—C6—C6a—C10a117.9 (3)C111—C11—C11a—C1109.5 (3)
N5—C6—C6a—C7166.2 (2)C4a—N5—C51—O51170.9 (2)
C61—C6—C6a—C764.7 (3)C6—N5—C51—O513.1 (4)
C10a—C6a—C7—C81.8 (4)C4a—N5—C51—C5211.5 (4)
C6—C6a—C7—C8179.4 (2)C6—N5—C51—C52179.2 (2)
C6a—C7—C8—C91.6 (4)N5—C6—C61—O6224.6 (3)
C7—C8—C9—C100.1 (4)C6a—C6—C61—O62156.9 (2)
C8—C9—C10—C10a1.6 (4)N5—C6—C61—O61159.0 (2)
C7—C6a—C10a—C100.4 (4)C6a—C6—C61—O6126.7 (3)
C6—C6a—C10a—C10177.6 (2)C11a—C11—C111—C11259.2 (3)
C7—C6a—C10a—C11176.1 (2)C10a—C11—C111—C112169.2 (2)
C6—C6a—C10a—C111.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O61—H61···O51i0.861.762.575 (3)156
C9—H9···O62ii0.952.503.329 (3)145
C8—H8···Cg1iii0.952.753.569 (3)144
Symmetry codes: (i) x+1/2, y+3/2, z+1/2; (ii) x+3/2, y1/2, z+1/2; (iii) x+1, y, z.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC19H19NO3C20H21NO3C21H23NO3
Mr309.35323.38337.40
Crystal system, space groupMonoclinic, P21Monoclinic, P21/cMonoclinic, P21/n
Temperature (K)120120120
a, b, c (Å)8.8053 (3), 10.9821 (4), 9.0080 (6)15.2894 (16), 10.760 (2), 10.538 (2)9.2283 (11), 16.691 (2), 11.9824 (18)
β (°) 118.510 (3) 100.990 (11) 103.820 (11)
V3)765.45 (6)1701.9 (5)1792.2 (4)
Z244
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.090.090.08
Crystal size (mm)0.26 × 0.14 × 0.100.41 × 0.30 × 0.240.23 × 0.20 × 0.20
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.977, 0.9910.966, 0.9800.981, 0.984
No. of measured, independent and
observed [I > 2σ(I)] reflections
13276, 1851, 1638 28096, 3903, 2589 27558, 3316, 2090
Rint0.0490.0920.139
(sin θ/λ)max1)0.6500.6500.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.081, 1.15 0.059, 0.155, 1.05 0.058, 0.120, 1.08
No. of reflections185139033316
No. of parameters210220230
No. of restraints100
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.240.68, 0.290.25, 0.29

Computer programs: COLLECT (Nonius, 1998), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected geometric parameters (Å, °) for (I)–(III) top
Bond lengths and angles
Parameter(I)(II)(III)
N5—C511.354 (3)1.356 (3)1.358 (3)
C51—O511.249 (3)1.241 (3)1.246 (3)
C61—O611.328 (3)1.325 (3)1.319 (3)
C61—O621.207((3)1.204 (3)1.207 (3)
N5—C6—C61—O61-155.01 (18)-49.6 (2)159.0 (2)
N5—C6—C61—O6224.4 (3)131.7 (2)-24.6 (3)
C6—N5—C51—O510.7 (3)6.0 (3)3.1 (4)
C6—N5—C51—C52179.1 (2)-175.6 (2)-179.2 (2)
C10—C10a—C11—C111-18.3 (3)-96.7 (2)-89.4 (3)
C10a—C11—C111—C112-168.0 (2)71.1 (2)169.2 (2)
Puckering parameters for seven-membered rings
Q1.079 (3)0.842 (2)0.800 (3)
φ244.93 (14)23.01 (13)17.2 (2)
φ3274.6 (8)311.3 (4)313.2 (5)
Ring-puckering parameters are calculated for the atom sequence N5–C4a–C11a–C11–C10a—C6a—C6
Hydrogen bonds and short intermolecular contacts (Å, °) for (I)–(III) top
CompoundD—H···AD—HH···AD···AD—H···A
(I)O61—H61···O51i0.861.832.672 (2)167
C2—H2···O51ii0.952.493.309 (3)144
C112—H12A···O62iii0.982.463.418 (4)165
(II)O61—H61···O51iv0.921.672.572 (2)167
C4—H4···O62v0.952.583.220 (3)125
C8—H8···O62vi0.952.583.405 (3)145
(III)O61—H61···O51vii0.861.762.575 (3)156
C9—H9···O62viii0.952.503.329 (3)145
C8—H8···Cg1ix0.952.753.569 (3)144
Cg1 represents the centroid of the ring C1–C4/C4a/C11a. Symmetry codes: (i) -x, y - 1/2, -z; (ii) x + 1, y, z + 1; (iii) -x + 1, y + 1/2, -z + 1; (iv) -x + 1, y + 1/2, -z + 1/2; (v) x, -y + 3/2, z - 1/2; (vi) x, -y + 3/2, z + 1/2; (vii) x + 1/2, -y + 3/2, z + 1/2; (viii) -x + 3/2, y - 1/2, -z + 1/2; (ix) x + 1, y, z.
 

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