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Three quinolone compounds were synthesized and crystallized in an effort to study the structure-activity relationship of these calcium-channel antagonists. In all three quinolones, viz. ethyl 4-(4-bromo­phenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carboxyl­ate, (I), ethyl 4-(3-bromo­phenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-car­box­yl­ate, (II), and ethyl 4-(2-bromo­phenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carboxyl­ate, (III), all C21H24BrNO3, common structural features such as a flat boat conformation of the 1,4-di­hydro­pyridine (1,4-DHP) ring, an envelope conformation of the fused cyclo­hexa­none ring and a bromo­phenyl ring at the pseudo-axial position and orthogonal to the 1,4-DHP ring are retained. However, due to the different packing inter­actions in each compound, halogen bonds are observed in (I) and (III). Compound (III) crystallizes with two molecules in the asymmetric unit. All of the prepared derivatives satisfy the basic structural requirements to possess moderate activity as calcium-channel antagonists.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614015617/sf3233sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614015617/sf3233Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614015617/sf3233IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614015617/sf3233IIIsup4.hkl
Contains datablock III

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614015617/sf3233Isup5.cml
CML file for (I)

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614015617/sf3233IIsup6.cml
CML file for (II)

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614015617/sf3233IIIsup7.cml
CML file for (III)

CCDC references: 1012125; 1012126; 1012127

Introduction top

The 1,4-di­hydro­pyridine (1,4-DHP) heterocycle comprises a large family of medicinally important compounds. The substructure has garnered the most attention as calcium channel antagonists working as slow calcium channel blockers, which have been used in the treatment of angina pectoris and hypertension. The examination of Hantzsch 1,4-di­hydro­pyridine ester derivatives has produced more active and longer acting agents than the prototypical nifedipine molecule. Many other derivatives have been synthesized to yield compounds active as calcium agonists or antagonists (Martin-Leon et al., 1995; Rose, 1990; Rose & Draeger, 1992). A fused cyclo­hexanone ring is one of the modifications to 1,4-DHP compounds and this class has been shown to have moderate calcium antagonistic activity, as well as modest anti-inflammatory and stem cell differentiation properties, and has been implicated in slowing neurodegenerative disorders. Thus, further understanding of the structure–activity relationship of 1,4-DHP compounds and their derivatives will allow for the determination of off-target activity and the reduction of side effects. It has been proven that the flattened boat conformation of the 1,4-DHP ring is one factor that leads to higher calcium channel activity. Atoms N1 and C4 of the DHP ring can be marginally displaced from the mean plane of the boat (Linden et al., 2002). An aryl group in the 4-position of 1,4-DHP is essential for optimal activity. One study showed that an aryl ring with halogen or other electron-withdrawing groups exhibits higher receptor-binding activity (Takahashi et al., 2008). On the 1,4-DHP ring, ester groups are usually substituted at the 3- and 5-positions. It is suggested that at least one cis-ester is required for the calcium antagonistic effect and hydrogen bonding to the receptor (Fossheim, 1986). In an effort to find more active calcium channel antagonists in the 1,4-DHP genre, we have synthesized a series of 1,4-DHP fused-ring derivatives, hexa­hydro­quinolones. In this paper, we report three structures which have bromine substituted at the para-, meta- and ortho-positions on the phenyl ring attached to the 1,4-DHP ring, compounds (I)–(III).

Experimental top

Synthesis and crystallization top

An oven-dried 100 ml round-bottomed flask was charged with dimedone (0.757 g), ethyl aceto­acetate (0.703 g), ytterbium(III) tri­fluoro­methane­sulfonate (0.170 g) and a magenetic stirrer bar. The mixture was then taken up in absolute ethanol (13.5 ml), capped, placed under an inert atmosphere of argon and stirred at room temperature for 20 min. Homologues of bromo­benzaldehyde (1.0 g, 5.405 mmol) and a qu­antity of ammonium acetate (0.419 g) were added to the stirred solution, and it was stirred at room temperature for a further 48 h. Reaction progress was monitored via thin-layer chromatography (TLC). Once the reaction was complete, excess solvent was removed via rotary evaporation. The solution was then purified via silica-column chromatography. The products were recrystallized from hexane and ethyl acetate as white to light-yellow crystalline solids [for (I), yield 1.91 g, 4.57 mmol, 84.00%; for (II), yield 1.86 g, 4.45 mmol, 82.30%; for (III), yield 1.45 g, 3.466 mmol, 63.76%].

Characterization information top

Melting points were determined in open capillary tubes with a Mel-Temp melting point apparatus (200 W) and are uncorrected. Structures were confirmed with 1H and 13C NMR, and mass spectroscopy. 1H NMR spectra were obtained in chloro­form-d1 using a Bruker AMX 400 MHz spectrometer. Chemical shifts are reported as p.p.m. relative to tetra­methyl­silane (TMS). LC–MS (liquid chromatography–mass spectrometry) data were obtained using a Waters LCT Premier XE series spectrometer.

Compound (I). 1H NMR (CDCl3, δ, p.p.m.): 7.31 (d, J = 8.28 Hz, 2H), 7.20 (d, J = 8.28 Hz, 2H), 6.01 (bs, 1H), 5.02 (s, 1H), 4.05 (q, J = 7.03 Hz, 2H), 2.38 (s, 3H), 2.21 (s, 2H), 2.17 (s, 2H), 1.20 (t, J = 7.15 Hz, 3H), 1.08 (s, 3H), 0.93 (s, 6H); 13C NMR (CDCl3, δ, p.p.m.): 195.42, 167.19, 148.01, 146.07, 143.60, 130.96, 129.89, 119.82, 111.90, 105.72, 59.94, 50.69, 41.14, 36.33, 32.75, 29.44, 27.15, 19.49, 14.23. HRMS, calculated for C21H24NO3Br: 418.1018; found: 418.1024. MS, m/z = 418 ([M+1] 100), 419 ([M+2] 10), 420 ([M+3] 100). m.p. 527–528 K. TLC [SiO2, hexane–EtOAc (3:2 v/v)]: Rf = 0.19.

Compound (II). 1H NMR (CDCl3, δ, p.p.m.): 7.41 (s, 1H), 7.26 (d, J = 7.53 Hz, 1H), 7.22 (d, J = 8.53 Hz, 1H), 7.07 (t, J = 7.78 Hz, 1H), 6.09 (bs, 1H), 5.03 (s, 1H), 4.07 (m, J = 7.15 Hz, 2H), 2.38 (s, 3H), 2.31 (s, 2H), 2.22 (s, 2H), 1.21 (t, J = 7.15 Hz, 3H), 1.09 (s, 3H), 0.96 (s, 6H); 13C NMR (CDCl3, δ, p.p.m.): 195.39, 167.15, 149.30, 148.24, 143.79, 131.09, 129.17, 126.97, 122.10, 111.71, 105.60, 59.96, 50.69, 41.12, 36.64, 32.78, 29.40, 27.22, 19.51, 14.21. HRMS, calculated for C21H24NO3Br: 418.1018; found: 418.0979. MS, m/z = 418 ([M+1] 100), 419 ([M+2] 90). m.p. 508-509 K. TLC [SiO2, hexane–EtOAc (3:2 v/v)]: Rf = 0.12.

Compound (III). 1H NMR (CDCl3, δ, p.p.m.): 7.44 (dd, J = 7.91 Hz, 1H), 7.37 (dd, J = 7.78 Hz, 1H), 7.16 (tt, J = 7.53 Hz, 1H), 6.94 (tt, J = 7.91 Hz, 1H), 5.92 (bs, 1H), 5.37 (s, 1H), 4.08 (m, J = 7.15 Hz, 2H), 2.32 (s, 3H), 2.30 (s, 2H), 2.19 (s, 2H), 1.18 (t, J = 7.03 Hz 3H), 1.08 (s, 3H), 0.96 (s, 6H); 13C NMR (CDCl3, δ, p.p.m.): 195.30, 167.44, 148.04, 145.88, 143.22, 133.08, 132.03, 127.49, 126.97, 123.38, 111.74, 105.86, 59.84, 50.69, 41.29, 37.98, 32.58, 29.28, 27.38, 19.49, 14.36. HRMS, calculated for C21H24NO3Br: 418.1018; found: 418.1037. MS: m/z = 417 ([M] 100), 418 ([M+1] 100), 419 ([M+2] 30). m.p. 473–477 K. TLC [SiO2, hexane–EtOAc (3:2 v/v)]: Rf = 0.23.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The methyl H atoms were constrained to an ideal geometry, with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C), and were allowed to rotate freely about their C—C bonds. The remaining C-bound H atoms were placed in calculated positions, with C—H = 0.95–1.00 Å, and refined as riding, with Uiso(H) = 1.2Ueq(C). The positions of the amine H atoms were determined from difference Fourier maps and refined freely along with their isotropic displacement parameters. Two low-angle reflections of (I) and four of (III) were omitted from the refinement because their observed intensities were much lower than the calculated values as a result of being partially obscured by the beam stop.

Results and discussion top

Both ethyl 4-(4-bromo­phenyl)-2,7,7-tri­methyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3- carboxyl­ate, (I) (Fig. 1), and ethyl 4-(3-bromo­phenyl)-2,7,7-tri­methyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3- carboxyl­ate, (II) (Fig. 2), crystallize in the orthorhombic space group Pbcn with one molecule in the asymmetric unit. The asymmetric unit of ethyl 4-(2-bromo­phenyl)-2,7,7-tri­methyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3- carboxyl­ate, (III) (Fig. 3), is composed of two enanti­omers of (III), molecules (IIIA) and (IIIB), which crystallize in the monoclinic space group P21/c. All three compounds have very similar structural conformations, which accommodate the requirements for calcium channel antagonists.

In all three structures, the 1,4-DHP ring is characterized by a shallow or flattened boat conformation, which is one of the factors that leads to higher calcium channel activity. The boat conformation can be qu­anti­fied by ring puckering parameters (Cremer & Pople, 1975). An ideal boat would have θ = 90° and ϕ = n×60°. In (I), the puckering parameters are Q = 0.196 (2) Å, θ = 106.5 (6)° and ϕ = 5.2 (8)° for the atom sequence N1–C2–C3–C4–C10–C9. The corresponding parameters for (II) are Q = 0.3014 (17) Å, θ = 107.1 (3)° and ϕ = 0.9 (3)°, while for (III), two sets were obtained as QA = 0.162 (3) Å, θA = 67.3 (10)° and ϕA = 197.5 (10)°, and QB = 0.279 (3) Å, θB = 106.9 (6)° and ϕB = 3.9 (6)° for molecules A and B, respectively. The shallowness of the boat conformation is indicated by the marginal displacements of atoms N1 and C4 from the mean plane (the base of the boat) defined by the two double bonds [C2C3 and C10 C9]. The deviation of atom N1 from the base of the boat is generally smaller, between 0.00 and 0.19 Å, while the deviation of atom C4 is most frequently found around 0.3 Å (Linden et al., 2004, 2005). These are also observed in the title compounds: the deviations of atom N1 are 0.095 (3), 0.142 (2), 0.047 (3) and 0.134 (3) Å for (I), (II), (IIIA) and (IIIB), respectively; and the deviations of atom C4 are 0.235 (4), 0.365 (2), 0.207 (4) and 0.336 (4) Å for (I), (II), (IIIA) and (IIIB), respectively. The sum of the absolute values of the ring inter­nal torsion angles is also considered a qu­anti­tative measure of the `flatness' of the 1,4-DHP ring. A flattened or unpuckered ring shows a sum of 0° and 240° for an ideal boat conformation of the ring. Here, these sums are 67.74° for (I), 104.39° for (II), 55.72° for (IIIA) and 96.52° for (IIIB) [These vary over a range of nearly 50% - are any conclusions meaningful?], indicating flattened boat conformations, compared with a sum of 72° for nifedipine, the known standard for 1,4-DHPs.

The relationship between the 1,4-DHP pyridine ring and the aryl group attached at the C4 position is another key factor in the 1,4-DHP structure–activity relationship. It has been reported that the pseudo-axial position of the aryl ring is essential for pharmacological activity (Langs et al., 1987). In the title compounds, the bromo­phenyl rings are almost orthogonal to the base of the 1,4-DHP ring defined by atoms C2, C3, C10 and C9, with angles between the mean planes [plane C2/C3/C10/C9 to plane C17–22] of 86.32 (8), 88.46 (5), 99.37 (8) and 89.36 (9)° for (I), (II), (IIIA) and (IIIB), respectively. Another qu­anti­tative descriptive factor is the torsion angle between the N1—C4 axis and the bond in the phenyl group directly above the 1,4-DHP ring [C17—C18 in compounds (I) and (II), and C17—C22 in compound (III)]. The N1—C4—C17—C18 torsion angles are 6.75 (19) and 7.14 (12)° for (I) and (II), respectively. The corresponding torsion angles in (III) show an even more orthogonal configuration as the values are 1.88 (18) and 3.3 (2)° for (IIIA) and (IIIB), respectively. The ortho-bromo group is placed in a synperiplanar orientation with respect to the C4—H bond. Such an orientation has been observed in other ortho-substituted phenyl rings in 4-aryl-1,4-DHP compounds (Linden et al., 2004). It is worth noting that, although meta-NO2 substitution has been reported to be syn-periplanar to the H atom on C4 (Morales et al., 1996), the meta-bromine in (II) is in an anti-periplanar position. In the same manner as other reported ortho-substituted structures, compound (III) has the bromine pointing away from the 1,4-DHP.

Due to the electron delocalization of the conjugate system, each ester group on the 1,4-DHP is coplanar and at a cis orientation to the adjacent endocyclic double bond. The coplanes extend out through the ester chains in (I) and (II). However, in (III), because of the different packing pattern, the end methyl group in (IIIA) is curled up in the direction of the aryl group. As a result, it pushes the aryl group slightly away from the orthogonal position, thus making the angle between the 1,4-DHP and the aryl ring the most strongly deviating from 90° – 99.37 (8)° in (IIIA) versus 89.36 (9)° in (IIIB).

Again, Cremer & Pople's ring puckering parameters can be used to qu­antify the conformations of the fused cyclo­hexanone rings. In all three compounds, the cyclo­hexanone rings adopt the envelope conformation, which ideally would have θ = 54.7° (or θ = 125.3° in the case of an absolute configuration change) and ϕ = n×60°. For (I), the puckering parameters are Q = 0.447 (3) Å, θ = 57.4 (4)°, and ϕ = 178.6 (4)° for atom sequence C5–C10. For the same atom sequence in (II), (IIIA) and (IIIB), the corresponding puckering parameters are Q = 0.4595 (18) Å, θ = 59.4 (2)° and ϕ = 122.0 (3)° for (II), Q = 0.462 (3) Å, θ = 122.5 (4)° and ϕ = 2.9 (4)° for (IIIA), and Q = 0.477 (3) Å, θ = 59.4 (4)° and ϕ = 183.4 (4)° for (IIIB). All these parameters are very close to those of the ideal envelope conformation. Because of the almost perfect envelope conformation, atom C7 stands out from the plane formed by the rest of the atoms in the ring and points to the same side as the C4-aryl ring. It is also inter­esting that the axial methyl group on C7 is almost syn-periplanar to the bond that connects C4 and the aryl ring. The relationship can be shown by the C11—C7—C4—C17 torsion angle, which is 13.86 (17)° for (I), 4.51 (13)° for (II), 16.2 (2)° for (IIIA) and 5.5 (2)° for (IIIB).

One feature which has not been previously reported for this type of structure is inter­molecular halogen bonding between Br and the ester carbonyl O atom. A halogen bond is defined as a short C—X···O—Y inter­action, where the X···O distance is less than or equal to the sums of the respective van der Waals radii (3.37 Å for Br···O in this case; [Standard reference?]), with the C—X···O angle 165° and the X···O—Y angle 120° (Auffinger et al., 2004). Although (II) has an X···O distance of 3.4837 (14) Å, which is only slightly longer than the sum of the van der Waals radii, the angles of 166.17 (13)° for Br1···O2—C14 and 77.24 (6)° for C19—Br1···O2 are out of range for halogen bonds. However, the Br···O distance is 3.1976 (18) Å in (I), with C20—Br1···O2 = 152.24 (9)° and Br1···O2—C14 = 111.06 (15)°, while in (III), Br1A···O2B = 3.1764 (18) Å and the angles are Br1A···O2B—C14B = 106.79 (16)° and C18A—Br1A···O2B = 160.65 (8)°. These numbers are within the range for halogen bonds. Halogen bonding has been known for decades and has been found in biological systems, where the halogen acts as a Lewis acid and the inter­acting atom can be any electron-donating entity. For example, in addition to the backbone carbonyl O atom as the most prominent Lewis base involved in halogen bonds, hydroxyls and carboxyls in the side-chain groups can also form halogen bonds in protein binding sites (Wilcken et al., 2013). The possibility of halogen bonding from Br in these three compounds needs to be considered during the study of their structure–activity relationships.

In all three compounds, hydrogen bonds are formed between the N—H group of one molecule and the carbonyl O atom in the cyclo­hexanone ring of another molecule (Tables 2, 3, and 4). These hydrogen bonds link the molecules into extended chains running along the c axis in both (I) and (II), but along the a axis in (III) (Figs. 4, 5, and 6). In compound (I), the largest difference hole of -1.21 e Å-3, which is 0.68 Å away from Br1, may indicate a slight disorder of the Br atom.

In conclusion, the structures reported here demonstrate that the conformational features have been conserved in cyclo­hexanone-fused 1,4-DHP derivatives. As a promising base structure for calcium channel antagonists, different substitutions and more structural modifications are being carried out in our group; progress will be reported in due course.

Related literature top

For related literature, see: Auffinger et al. (2004); Cremer & Pople (1975); Fossheim (1986); Langs et al. (1987); Linden et al. (2002, 2004, 2005); Martin-Leon, Quinteiro, Seoane, Soto, Mora, Suarez, Ochoa, Morales & Bosque (1995); Morales et al. (1996); Rose (1990); Rose & Draeger (1992); Takahashi et al. (2008); Wilcken et al. (2013).

Computing details top

For all compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The asymmetric unit of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. The asymmetric unit of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 4] Fig. 4. Part of the crystal structure of (I), showing the formation of chains of molecules running along the c axis. Hydrogen bonds are indicated by dashed lines. For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted.
[Figure 5] Fig. 5. Part of the crystal structure of (II), showing the formation of chains of molecules running along the c axis. Hydrogen bonds are indicated by dashed lines. For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted.
[Figure 6] Fig. 6. Part of the crystal structure of (III), showing the formation of chains of molecules running along the a axis. Hydrogen bonds are indicated by dashed lines. For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted.
(I) Ethyl 4-(4-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate top
Crystal data top
C21H24BrNO3Dx = 1.400 Mg m3
Mr = 418.32Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcnCell parameters from 9956 reflections
a = 18.0371 (4) Åθ = 2.3–27.5°
b = 15.4309 (3) ŵ = 2.09 mm1
c = 14.2604 (3) ÅT = 100 K
V = 3969.08 (14) Å3Prism, light yellow
Z = 80.26 × 0.18 × 0.13 mm
F(000) = 1728
Data collection top
Bruker SMART BREEZE CCD area-detector
diffractometer
3391 reflections with I > 2σ(I)
Radiation source: 2 kW sealed X-ray tubeRint = 0.038
ϕ and ω scansθmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1923
Tmin = 0.909, Tmax = 1.000k = 2019
35271 measured reflectionsl = 1818
4558 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101 w = 1/[σ2(Fo2) + (0.0386P)2 + 5.4149P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
4558 reflectionsΔρmax = 1.49 e Å3
243 parametersΔρmin = 1.21 e Å3
0 restraints
Crystal data top
C21H24BrNO3V = 3969.08 (14) Å3
Mr = 418.32Z = 8
Orthorhombic, PbcnMo Kα radiation
a = 18.0371 (4) ŵ = 2.09 mm1
b = 15.4309 (3) ÅT = 100 K
c = 14.2604 (3) Å0.26 × 0.18 × 0.13 mm
Data collection top
Bruker SMART BREEZE CCD area-detector
diffractometer
4558 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
3391 reflections with I > 2σ(I)
Tmin = 0.909, Tmax = 1.000Rint = 0.038
35271 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 1.49 e Å3
4558 reflectionsΔρmin = 1.21 e Å3
243 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.01835 (2)0.08589 (2)0.60206 (2)0.03911 (12)
O10.39646 (10)0.02836 (11)0.63323 (11)0.0200 (4)
O20.35587 (10)0.33300 (11)0.41638 (12)0.0213 (4)
O30.34556 (10)0.27791 (11)0.56159 (11)0.0213 (4)
N10.39491 (12)0.07392 (13)0.32412 (14)0.0190 (5)
H10.4013 (16)0.0634 (19)0.264 (2)0.027 (8)*
C20.38319 (14)0.15957 (16)0.35057 (16)0.0178 (5)
C30.36618 (13)0.17953 (15)0.44025 (16)0.0148 (5)
C40.35425 (13)0.10862 (15)0.51345 (15)0.0137 (5)
H40.38080.12600.57210.016*
C50.40247 (13)0.04303 (16)0.54818 (16)0.0145 (5)
C60.43032 (14)0.13027 (15)0.51443 (16)0.0158 (5)
H6A0.41010.17570.55620.019*
H6B0.48500.13140.52070.019*
C70.41033 (14)0.15326 (16)0.41315 (15)0.0149 (5)
C80.42990 (14)0.07570 (15)0.35066 (16)0.0158 (5)
H8A0.48450.07210.34450.019*
H8B0.40900.08540.28730.019*
C90.40135 (13)0.00865 (15)0.38786 (15)0.0140 (5)
C100.38685 (13)0.02328 (15)0.47985 (15)0.0132 (5)
C110.32747 (14)0.17399 (17)0.40568 (17)0.0203 (5)
H11A0.29850.12300.42400.030*
H11B0.31540.22250.44740.030*
H11C0.31540.18980.34090.030*
C120.45589 (15)0.23200 (16)0.38188 (17)0.0210 (5)
H12A0.44440.24550.31630.031*
H12B0.44350.28190.42140.031*
H12C0.50880.21890.38790.031*
C130.39310 (19)0.22252 (18)0.27089 (17)0.0323 (7)
H13A0.41310.19190.21630.048*
H13B0.42750.26840.28980.048*
H13C0.34510.24820.25470.048*
C140.35600 (13)0.27062 (16)0.46787 (17)0.0166 (5)
C150.33581 (17)0.36583 (17)0.59609 (18)0.0254 (6)
H15A0.29750.39620.55880.030*
H15B0.38290.39840.59070.030*
C160.3126 (3)0.3606 (2)0.6959 (2)0.0582 (12)
H16A0.26560.32910.70040.087*
H16B0.30620.41930.72100.087*
H16C0.35070.33010.73210.087*
C170.27210 (13)0.09825 (14)0.53660 (16)0.0149 (5)
C180.22092 (14)0.08222 (16)0.46580 (17)0.0182 (5)
H180.23780.07550.40310.022*
C190.14545 (15)0.07577 (16)0.48494 (19)0.0226 (6)
H190.11090.06480.43610.027*
C200.12180 (15)0.08566 (17)0.5767 (2)0.0247 (6)
C210.17150 (15)0.09807 (17)0.64941 (19)0.0243 (6)
H210.15460.10210.71230.029*
C220.24660 (15)0.10459 (16)0.62882 (17)0.0204 (5)
H220.28110.11350.67820.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.02137 (16)0.03688 (19)0.0591 (2)0.00082 (14)0.01586 (14)0.01140 (15)
O10.0306 (10)0.0199 (10)0.0094 (7)0.0029 (8)0.0012 (7)0.0007 (7)
O20.0221 (10)0.0143 (9)0.0274 (9)0.0020 (8)0.0039 (7)0.0039 (8)
O30.0328 (11)0.0115 (9)0.0194 (8)0.0013 (8)0.0009 (8)0.0020 (7)
N10.0314 (12)0.0157 (11)0.0098 (9)0.0012 (9)0.0002 (8)0.0005 (8)
C20.0234 (13)0.0134 (12)0.0166 (11)0.0016 (10)0.0033 (10)0.0016 (10)
C30.0143 (12)0.0123 (12)0.0179 (11)0.0008 (10)0.0022 (9)0.0003 (9)
C40.0171 (12)0.0128 (12)0.0113 (10)0.0000 (10)0.0005 (9)0.0009 (9)
C50.0114 (11)0.0165 (12)0.0156 (11)0.0018 (10)0.0006 (9)0.0013 (10)
C60.0187 (12)0.0137 (12)0.0150 (11)0.0020 (10)0.0013 (9)0.0004 (9)
C70.0177 (12)0.0135 (12)0.0134 (11)0.0004 (10)0.0006 (9)0.0006 (9)
C80.0193 (12)0.0147 (13)0.0135 (11)0.0018 (10)0.0026 (9)0.0012 (9)
C90.0142 (11)0.0135 (12)0.0143 (11)0.0022 (10)0.0005 (9)0.0002 (9)
C100.0132 (11)0.0117 (12)0.0146 (11)0.0001 (9)0.0009 (9)0.0000 (9)
C110.0204 (13)0.0188 (13)0.0217 (12)0.0041 (11)0.0006 (10)0.0036 (11)
C120.0258 (13)0.0152 (13)0.0219 (12)0.0009 (11)0.0045 (10)0.0026 (10)
C130.062 (2)0.0193 (15)0.0159 (12)0.0038 (14)0.0004 (13)0.0046 (11)
C140.0108 (11)0.0176 (13)0.0214 (12)0.0017 (10)0.0014 (9)0.0011 (10)
C150.0377 (16)0.0134 (13)0.0250 (13)0.0011 (12)0.0002 (12)0.0038 (11)
C160.117 (4)0.0214 (17)0.0365 (18)0.014 (2)0.020 (2)0.0008 (15)
C170.0198 (12)0.0070 (11)0.0178 (11)0.0016 (10)0.0031 (9)0.0003 (9)
C180.0209 (13)0.0155 (12)0.0183 (11)0.0025 (11)0.0014 (10)0.0018 (10)
C190.0197 (13)0.0170 (13)0.0310 (14)0.0018 (11)0.0007 (11)0.0003 (11)
C200.0180 (13)0.0157 (13)0.0403 (15)0.0010 (11)0.0094 (11)0.0013 (12)
C210.0300 (15)0.0180 (14)0.0248 (13)0.0016 (11)0.0127 (11)0.0039 (11)
C220.0265 (14)0.0163 (13)0.0185 (11)0.0021 (11)0.0025 (10)0.0024 (10)
Geometric parameters (Å, º) top
Br1—C201.901 (3)C9—C101.357 (3)
O1—C51.239 (3)C11—H11A0.9800
O2—C141.211 (3)C11—H11B0.9800
O3—C141.354 (3)C11—H11C0.9800
O3—C151.454 (3)C12—H12A0.9800
N1—H10.89 (3)C12—H12B0.9800
N1—C21.391 (3)C12—H12C0.9800
N1—C91.362 (3)C13—H13A0.9800
C2—C31.351 (3)C13—H13B0.9800
C2—C131.505 (3)C13—H13C0.9800
C3—C41.528 (3)C15—H15A0.9900
C3—C141.471 (3)C15—H15B0.9900
C4—H41.0000C15—C161.485 (4)
C4—C101.520 (3)C16—H16A0.9800
C4—C171.526 (3)C16—H16B0.9800
C5—C61.515 (3)C16—H16C0.9800
C5—C101.441 (3)C17—C181.390 (3)
C6—H6A0.9900C17—C221.397 (3)
C6—H6B0.9900C18—H180.9500
C6—C71.530 (3)C18—C191.392 (4)
C7—C81.533 (3)C19—H190.9500
C7—C111.532 (3)C19—C201.385 (4)
C7—C121.533 (3)C20—C211.384 (4)
C8—H8A0.9900C21—H210.9500
C8—H8B0.9900C21—C221.390 (4)
C8—C91.497 (3)C22—H220.9500
C14—O3—C15115.35 (19)H11A—C11—H11C109.5
C2—N1—H1117.3 (19)H11B—C11—H11C109.5
C9—N1—H1120.2 (19)C7—C12—H12A109.5
C9—N1—C2122.3 (2)C7—C12—H12B109.5
N1—C2—C13113.0 (2)C7—C12—H12C109.5
C3—C2—N1120.5 (2)H12A—C12—H12B109.5
C3—C2—C13126.5 (2)H12A—C12—H12C109.5
C2—C3—C4121.0 (2)H12B—C12—H12C109.5
C2—C3—C14120.0 (2)C2—C13—H13A109.5
C14—C3—C4118.9 (2)C2—C13—H13B109.5
C3—C4—H4108.1C2—C13—H13C109.5
C10—C4—C3110.53 (18)H13A—C13—H13B109.5
C10—C4—H4108.1H13A—C13—H13C109.5
C10—C4—C17110.66 (19)H13B—C13—H13C109.5
C17—C4—C3111.08 (19)O2—C14—O3122.2 (2)
C17—C4—H4108.1O2—C14—C3126.7 (2)
O1—C5—C6120.2 (2)O3—C14—C3111.2 (2)
O1—C5—C10121.0 (2)O3—C15—H15A110.1
C10—C5—C6118.74 (19)O3—C15—H15B110.1
C5—C6—H6A108.4O3—C15—C16107.9 (2)
C5—C6—H6B108.4H15A—C15—H15B108.4
C5—C6—C7115.32 (19)C16—C15—H15A110.1
H6A—C6—H6B107.5C16—C15—H15B110.1
C7—C6—H6A108.4C15—C16—H16A109.5
C7—C6—H6B108.4C15—C16—H16B109.5
C6—C7—C8108.26 (19)C15—C16—H16C109.5
C6—C7—C11110.12 (19)H16A—C16—H16B109.5
C6—C7—C12109.4 (2)H16A—C16—H16C109.5
C11—C7—C8110.3 (2)H16B—C16—H16C109.5
C11—C7—C12109.7 (2)C18—C17—C4120.4 (2)
C12—C7—C8109.03 (19)C18—C17—C22118.5 (2)
C7—C8—H8A108.9C22—C17—C4121.1 (2)
C7—C8—H8B108.9C17—C18—H18119.3
H8A—C8—H8B107.8C17—C18—C19121.3 (2)
C9—C8—C7113.18 (19)C19—C18—H18119.3
C9—C8—H8A108.9C18—C19—H19120.7
C9—C8—H8B108.9C20—C19—C18118.6 (2)
N1—C9—C8115.85 (19)C20—C19—H19120.7
C10—C9—N1120.4 (2)C19—C20—Br1118.8 (2)
C10—C9—C8123.6 (2)C21—C20—Br1119.6 (2)
C5—C10—C4118.5 (2)C21—C20—C19121.6 (2)
C9—C10—C4121.6 (2)C20—C21—H21120.5
C9—C10—C5119.9 (2)C20—C21—C22118.9 (2)
C7—C11—H11A109.5C22—C21—H21120.5
C7—C11—H11B109.5C17—C22—H22119.5
C7—C11—H11C109.5C21—C22—C17121.0 (2)
H11A—C11—H11B109.5C21—C22—H22119.5
Br1—C20—C21—C22174.96 (19)C7—C8—C9—N1159.3 (2)
O1—C5—C6—C7159.3 (2)C7—C8—C9—C1024.9 (3)
O1—C5—C10—C47.0 (3)C8—C9—C10—C4176.9 (2)
O1—C5—C10—C9173.0 (2)C8—C9—C10—C53.2 (4)
N1—C2—C3—C44.1 (4)C9—N1—C2—C310.4 (4)
N1—C2—C3—C14178.3 (2)C9—N1—C2—C13168.4 (2)
N1—C9—C10—C47.5 (4)C10—C4—C17—C1867.8 (3)
N1—C9—C10—C5172.4 (2)C10—C4—C17—C22112.2 (2)
C2—N1—C9—C8167.3 (2)C10—C5—C6—C723.8 (3)
C2—N1—C9—C108.7 (4)C11—C7—C8—C972.0 (2)
C2—C3—C4—C1017.6 (3)C12—C7—C8—C9167.4 (2)
C2—C3—C4—C17105.7 (3)C13—C2—C3—C4177.2 (3)
C2—C3—C14—O25.8 (4)C13—C2—C3—C140.4 (4)
C2—C3—C14—O3174.8 (2)C14—O3—C15—C16170.6 (3)
C3—C4—C10—C5160.6 (2)C14—C3—C4—C10164.8 (2)
C3—C4—C10—C919.4 (3)C14—C3—C4—C1772.0 (3)
C3—C4—C17—C1855.4 (3)C15—O3—C14—O21.3 (3)
C3—C4—C17—C22124.6 (2)C15—O3—C14—C3179.3 (2)
C4—C3—C14—O2171.8 (2)C17—C4—C10—C575.9 (3)
C4—C3—C14—O37.6 (3)C17—C4—C10—C9104.1 (2)
C4—C17—C18—C19177.6 (2)C17—C18—C19—C200.0 (4)
C4—C17—C22—C21177.8 (2)C18—C17—C22—C212.2 (4)
C5—C6—C7—C848.7 (3)C18—C19—C20—Br1175.19 (19)
C5—C6—C7—C1172.0 (3)C18—C19—C20—C212.7 (4)
C5—C6—C7—C12167.4 (2)C19—C20—C21—C222.9 (4)
C6—C5—C10—C4176.1 (2)C20—C21—C22—C170.4 (4)
C6—C5—C10—C93.9 (3)C22—C17—C18—C192.4 (4)
C6—C7—C8—C948.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.89 (3)1.94 (3)2.812 (2)168 (3)
Symmetry code: (i) x, y, z1/2.
(II) Ethyl 4-(3-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate top
Crystal data top
C21H24BrNO3Dx = 1.474 Mg m3
Mr = 418.32Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcnCell parameters from 9015 reflections
a = 17.0813 (5) Åθ = 2.3–29.1°
b = 15.4877 (5) ŵ = 2.20 mm1
c = 14.2544 (5) ÅT = 100 K
V = 3771.0 (2) Å3Prism, light yellow
Z = 80.40 × 0.21 × 0.19 mm
F(000) = 1728
Data collection top
Bruker SMART BREEZE CCD area-detector
diffractometer
5055 independent reflections
Radiation source: 2 kW sealed X-ray tube4278 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ϕ and ω scansθmax = 29.1°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 2323
Tmin = 0.839, Tmax = 1.000k = 2121
55070 measured reflectionsl = 1919
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.084 w = 1/[σ2(Fo2) + (0.0428P)2 + 3.6244P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.002
5055 reflectionsΔρmax = 1.31 e Å3
243 parametersΔρmin = 0.38 e Å3
Crystal data top
C21H24BrNO3V = 3771.0 (2) Å3
Mr = 418.32Z = 8
Orthorhombic, PbcnMo Kα radiation
a = 17.0813 (5) ŵ = 2.20 mm1
b = 15.4877 (5) ÅT = 100 K
c = 14.2544 (5) Å0.40 × 0.21 × 0.19 mm
Data collection top
Bruker SMART BREEZE CCD area-detector
diffractometer
5055 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
4278 reflections with I > 2σ(I)
Tmin = 0.839, Tmax = 1.000Rint = 0.032
55070 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.084H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 1.31 e Å3
5055 reflectionsΔρmin = 0.38 e Å3
243 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.92434 (2)0.52663 (2)0.66172 (2)0.01998 (7)
O10.61002 (8)0.46449 (8)0.36349 (9)0.0170 (3)
O20.60547 (9)0.83120 (9)0.54611 (11)0.0273 (3)
O30.66301 (8)0.77388 (8)0.41978 (10)0.0235 (3)
N10.61112 (9)0.58166 (9)0.66708 (10)0.0132 (3)
C20.61780 (9)0.66563 (11)0.63433 (12)0.0132 (3)
C30.63546 (9)0.67997 (11)0.54285 (12)0.0132 (3)
C40.65961 (9)0.60546 (10)0.47927 (11)0.0117 (3)
H40.63970.61740.41460.014*
C100.62185 (9)0.52300 (10)0.51443 (11)0.0105 (3)
C90.60504 (9)0.51293 (10)0.60705 (11)0.0105 (3)
C80.57528 (9)0.43036 (11)0.64894 (11)0.0126 (3)
H8A0.51760.43350.65420.015*
H8B0.59680.42400.71300.015*
C70.59747 (10)0.35080 (10)0.59090 (12)0.0129 (3)
C60.57615 (10)0.36838 (11)0.48787 (12)0.0143 (3)
H6A0.59810.32140.44890.017*
H6B0.51850.36620.48160.017*
C50.60455 (9)0.45362 (11)0.44924 (11)0.0112 (3)
C110.68524 (11)0.33164 (12)0.59932 (14)0.0208 (4)
H11A0.69880.32280.66540.031*
H11B0.71520.38040.57430.031*
H11C0.69780.27940.56360.031*
C120.55061 (12)0.27318 (12)0.62687 (14)0.0217 (4)
H12A0.49460.28680.62520.033*
H12B0.56630.26020.69150.033*
H12C0.56100.22300.58690.033*
C130.60140 (11)0.73340 (12)0.70714 (13)0.0193 (4)
H13A0.59640.70600.76880.029*
H13B0.55250.76330.69160.029*
H13C0.64460.77510.70850.029*
C140.63211 (10)0.76888 (11)0.50625 (13)0.0172 (3)
C150.66536 (13)0.86167 (13)0.38140 (16)0.0281 (4)
H15A0.68130.90330.43050.034*
H15B0.61310.87850.35770.034*
C160.72312 (12)0.86129 (14)0.30382 (16)0.0285 (4)
H16A0.77390.84150.32750.043*
H16B0.72850.91980.27850.043*
H16C0.70520.82230.25410.043*
C170.74878 (10)0.59554 (10)0.47466 (11)0.0124 (3)
C180.78958 (9)0.56824 (11)0.55396 (11)0.0130 (3)
H180.76200.55470.60990.016*
C190.87044 (10)0.56085 (11)0.55114 (12)0.0137 (3)
C200.91306 (10)0.57960 (11)0.47084 (13)0.0161 (3)
H200.96850.57520.47020.019*
C210.87189 (11)0.60498 (12)0.39144 (13)0.0199 (4)
H210.89960.61680.33510.024*
C220.79094 (10)0.61342 (12)0.39305 (12)0.0177 (3)
H220.76400.63150.33810.021*
H10.6037 (14)0.5739 (15)0.7262 (18)0.021 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.01611 (10)0.02866 (11)0.01518 (10)0.00677 (7)0.00292 (6)0.00298 (7)
O10.0224 (6)0.0199 (6)0.0087 (5)0.0009 (5)0.0005 (5)0.0006 (5)
O20.0349 (8)0.0137 (6)0.0332 (8)0.0049 (6)0.0042 (6)0.0020 (6)
O30.0262 (7)0.0184 (6)0.0259 (7)0.0052 (5)0.0088 (6)0.0111 (5)
N10.0179 (7)0.0137 (7)0.0079 (6)0.0008 (5)0.0009 (5)0.0009 (5)
C20.0113 (7)0.0122 (7)0.0162 (8)0.0000 (6)0.0011 (6)0.0025 (6)
C30.0111 (7)0.0124 (7)0.0161 (8)0.0007 (6)0.0011 (6)0.0009 (6)
C40.0122 (7)0.0129 (7)0.0101 (7)0.0011 (6)0.0003 (6)0.0027 (6)
C100.0108 (7)0.0119 (7)0.0088 (7)0.0000 (5)0.0003 (5)0.0012 (6)
C90.0098 (7)0.0116 (7)0.0101 (7)0.0006 (5)0.0004 (5)0.0001 (6)
C80.0140 (7)0.0132 (8)0.0105 (7)0.0001 (6)0.0022 (6)0.0021 (6)
C70.0144 (7)0.0116 (7)0.0126 (8)0.0008 (6)0.0014 (6)0.0010 (6)
C60.0167 (8)0.0127 (7)0.0135 (8)0.0009 (6)0.0002 (6)0.0017 (6)
C50.0095 (7)0.0143 (7)0.0097 (7)0.0024 (6)0.0013 (6)0.0011 (6)
C110.0193 (8)0.0209 (9)0.0223 (9)0.0069 (7)0.0020 (7)0.0047 (7)
C120.0283 (9)0.0139 (8)0.0228 (9)0.0023 (7)0.0063 (8)0.0020 (7)
C130.0218 (9)0.0165 (8)0.0196 (9)0.0005 (7)0.0027 (7)0.0065 (7)
C140.0120 (7)0.0159 (8)0.0235 (9)0.0019 (6)0.0006 (7)0.0047 (7)
C150.0332 (11)0.0183 (9)0.0327 (11)0.0053 (8)0.0059 (9)0.0103 (8)
C160.0278 (10)0.0272 (10)0.0306 (11)0.0017 (8)0.0012 (9)0.0088 (9)
C170.0149 (7)0.0104 (7)0.0120 (7)0.0011 (6)0.0025 (6)0.0008 (6)
C180.0132 (7)0.0151 (8)0.0106 (7)0.0014 (6)0.0023 (6)0.0019 (6)
C190.0155 (7)0.0119 (7)0.0137 (8)0.0003 (6)0.0016 (6)0.0033 (6)
C200.0139 (8)0.0141 (8)0.0203 (9)0.0006 (6)0.0040 (6)0.0014 (6)
C210.0213 (9)0.0221 (9)0.0164 (8)0.0002 (7)0.0084 (7)0.0043 (7)
C220.0195 (8)0.0200 (8)0.0134 (8)0.0012 (7)0.0033 (6)0.0051 (6)
Geometric parameters (Å, º) top
Br1—C191.9009 (17)C6—C51.510 (2)
O1—C51.237 (2)C11—H11A0.9800
O2—C141.209 (2)C11—H11B0.9800
O3—C141.343 (2)C11—H11C0.9800
O3—C151.466 (2)C12—H12A0.9800
N1—C21.386 (2)C12—H12B0.9800
N1—C91.370 (2)C12—H12C0.9800
N1—H10.86 (2)C13—H13A0.9800
C2—C31.357 (2)C13—H13B0.9800
C2—C131.502 (2)C13—H13C0.9800
C3—C41.524 (2)C15—H15A0.9900
C3—C141.474 (2)C15—H15B0.9900
C4—H41.0000C15—C161.482 (3)
C4—C101.516 (2)C16—H16A0.9800
C4—C171.532 (2)C16—H16B0.9800
C10—C91.360 (2)C16—H16C0.9800
C10—C51.451 (2)C17—C181.394 (2)
C9—C81.500 (2)C17—C221.396 (2)
C8—H8A0.9900C18—H180.9500
C8—H8B0.9900C18—C191.386 (2)
C8—C71.532 (2)C19—C201.387 (2)
C7—C61.537 (2)C20—H200.9500
C7—C111.533 (2)C20—C211.389 (3)
C7—C121.533 (2)C21—H210.9500
C6—H6A0.9900C21—C221.389 (3)
C6—H6B0.9900C22—H220.9500
C14—O3—C15113.99 (15)H11A—C11—H11C109.5
C2—N1—H1118.2 (16)H11B—C11—H11C109.5
C9—N1—C2121.67 (14)C7—C12—H12A109.5
C9—N1—H1119.5 (16)C7—C12—H12B109.5
N1—C2—C13114.04 (15)C7—C12—H12C109.5
C3—C2—N1119.69 (15)H12A—C12—H12B109.5
C3—C2—C13126.23 (16)H12A—C12—H12C109.5
C2—C3—C4120.52 (15)H12B—C12—H12C109.5
C2—C3—C14118.99 (16)C2—C13—H13A109.5
C14—C3—C4120.49 (15)C2—C13—H13B109.5
C3—C4—H4108.4C2—C13—H13C109.5
C3—C4—C17111.75 (13)H13A—C13—H13B109.5
C10—C4—C3109.02 (13)H13A—C13—H13C109.5
C10—C4—H4108.4H13B—C13—H13C109.5
C10—C4—C17110.65 (13)O2—C14—O3122.23 (16)
C17—C4—H4108.4O2—C14—C3126.45 (17)
C9—C10—C4120.49 (14)O3—C14—C3111.32 (15)
C9—C10—C5119.58 (14)O3—C15—H15A110.3
C5—C10—C4119.92 (14)O3—C15—H15B110.3
N1—C9—C8116.08 (14)O3—C15—C16107.04 (16)
C10—C9—N1120.08 (15)H15A—C15—H15B108.6
C10—C9—C8123.76 (15)C16—C15—H15A110.3
C9—C8—H8A109.0C16—C15—H15B110.3
C9—C8—H8B109.0C15—C16—H16A109.5
C9—C8—C7112.76 (13)C15—C16—H16B109.5
H8A—C8—H8B107.8C15—C16—H16C109.5
C7—C8—H8A109.0H16A—C16—H16B109.5
C7—C8—H8B109.0H16A—C16—H16C109.5
C8—C7—C6108.35 (13)H16B—C16—H16C109.5
C8—C7—C11110.82 (14)C18—C17—C4119.53 (14)
C8—C7—C12108.72 (14)C18—C17—C22118.56 (15)
C11—C7—C6109.92 (14)C22—C17—C4121.91 (15)
C12—C7—C6109.56 (14)C17—C18—H18120.0
C12—C7—C11109.43 (14)C19—C18—C17119.98 (15)
C7—C6—H6A108.5C19—C18—H18120.0
C7—C6—H6B108.5C18—C19—Br1118.78 (13)
H6A—C6—H6B107.5C18—C19—C20121.97 (16)
C5—C6—C7115.28 (14)C20—C19—Br1119.24 (13)
C5—C6—H6A108.5C19—C20—H20121.1
C5—C6—H6B108.5C19—C20—C21117.76 (16)
O1—C5—C10121.10 (15)C21—C20—H20121.1
O1—C5—C6120.22 (15)C20—C21—H21119.4
C10—C5—C6118.63 (14)C22—C21—C20121.13 (16)
C7—C11—H11A109.5C22—C21—H21119.4
C7—C11—H11B109.5C17—C22—H22119.7
C7—C11—H11C109.5C21—C22—C17120.58 (17)
H11A—C11—H11B109.5C21—C22—H22119.7
Br1—C19—C20—C21179.58 (13)C9—C10—C5—C66.4 (2)
N1—C2—C3—C48.9 (2)C9—C8—C7—C649.12 (18)
N1—C2—C3—C14171.99 (15)C9—C8—C7—C1171.56 (18)
N1—C9—C8—C7159.09 (14)C9—C8—C7—C12168.13 (14)
C2—N1—C9—C1013.9 (2)C8—C7—C6—C549.17 (18)
C2—N1—C9—C8162.93 (14)C7—C6—C5—O1160.14 (15)
C2—C3—C4—C1028.5 (2)C7—C6—C5—C1022.5 (2)
C2—C3—C4—C1794.13 (18)C5—C10—C9—N1171.17 (14)
C2—C3—C14—O210.1 (3)C5—C10—C9—C85.4 (2)
C2—C3—C14—O3170.08 (15)C11—C7—C6—C572.07 (18)
C3—C4—C10—C928.9 (2)C12—C7—C6—C5167.65 (14)
C3—C4—C10—C5152.04 (14)C13—C2—C3—C4173.19 (16)
C3—C4—C17—C1868.23 (19)C13—C2—C3—C145.9 (3)
C3—C4—C17—C22111.52 (18)C14—O3—C15—C16161.23 (17)
C4—C3—C14—O2170.86 (17)C14—C3—C4—C10152.46 (14)
C4—C3—C14—O39.0 (2)C14—C3—C4—C1784.92 (18)
C4—C10—C9—N19.8 (2)C15—O3—C14—O23.3 (3)
C4—C10—C9—C8173.61 (14)C15—O3—C14—C3176.83 (15)
C4—C10—C5—O110.0 (2)C17—C4—C10—C994.34 (18)
C4—C10—C5—C6172.64 (14)C17—C4—C10—C584.68 (17)
C4—C17—C18—C19178.60 (15)C17—C18—C19—Br1178.21 (12)
C4—C17—C22—C21179.09 (16)C17—C18—C19—C200.3 (3)
C10—C4—C17—C1853.5 (2)C18—C17—C22—C210.7 (3)
C10—C4—C17—C22126.79 (17)C18—C19—C20—C211.1 (3)
C10—C9—C8—C724.2 (2)C19—C20—C21—C221.6 (3)
C9—N1—C2—C314.3 (2)C20—C21—C22—C170.7 (3)
C9—N1—C2—C13163.81 (15)C22—C17—C18—C191.1 (2)
C9—C10—C5—O1170.98 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.86 (2)2.05 (2)2.8896 (19)166 (2)
Symmetry code: (i) x, y+1, z+1/2.
(III) Ethyl 4-(2-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate top
Crystal data top
C21H24BrNO3F(000) = 1728
Mr = 418.32Dx = 1.445 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 14.5012 (18) ÅCell parameters from 9934 reflections
b = 18.299 (2) Åθ = 2.2–27.7°
c = 15.1952 (19) ŵ = 2.16 mm1
β = 107.5262 (15)°T = 100 K
V = 3844.9 (8) Å3Prism, translucent yellow
Z = 80.34 × 0.16 × 0.08 mm
Data collection top
Bruker SMART BREEZE CCD area-detector
diffractometer
6859 reflections with I > 2σ(I)
Radiation source: 2 kW sealed X-ray tubeRint = 0.065
ϕ and ω scansθmax = 27.7°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1818
Tmin = 0.866, Tmax = 1.000k = 2323
45465 measured reflectionsl = 1919
8935 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.081 w = 1/[σ2(Fo2) + (0.0324P)2 + 2.2792P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
8935 reflectionsΔρmax = 1.46 e Å3
485 parametersΔρmin = 0.47 e Å3
0 restraints
Crystal data top
C21H24BrNO3V = 3844.9 (8) Å3
Mr = 418.32Z = 8
Monoclinic, P21/cMo Kα radiation
a = 14.5012 (18) ŵ = 2.16 mm1
b = 18.299 (2) ÅT = 100 K
c = 15.1952 (19) Å0.34 × 0.16 × 0.08 mm
β = 107.5262 (15)°
Data collection top
Bruker SMART BREEZE CCD area-detector
diffractometer
8935 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
6859 reflections with I > 2σ(I)
Tmin = 0.866, Tmax = 1.000Rint = 0.065
45465 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 1.46 e Å3
8935 reflectionsΔρmin = 0.47 e Å3
485 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br1A0.39565 (2)0.30789 (2)0.25454 (2)0.01430 (7)
O1A0.28043 (11)0.45760 (9)0.12019 (11)0.0122 (4)
O2A0.04711 (13)0.20468 (10)0.24987 (15)0.0262 (5)
O3A0.20232 (12)0.23877 (9)0.29061 (12)0.0148 (4)
N1A0.01715 (15)0.42917 (11)0.17929 (14)0.0110 (4)
C2A0.00080 (17)0.35786 (13)0.21030 (16)0.0117 (5)
C3A0.08940 (16)0.32797 (13)0.22333 (16)0.0100 (5)
C4A0.17328 (16)0.37166 (13)0.20857 (16)0.0096 (5)
H4A0.20550.34160.17140.012*
C10A0.13654 (16)0.44210 (13)0.15653 (16)0.0094 (5)
C9A0.04751 (17)0.46991 (13)0.15143 (16)0.0099 (5)
C8A0.01507 (17)0.54547 (13)0.11637 (17)0.0113 (5)
H8AA0.02550.56590.15240.014*
H8AB0.02540.54220.05110.014*
C7A0.10023 (17)0.59772 (13)0.12310 (17)0.0114 (5)
C6A0.17181 (17)0.55891 (13)0.08212 (16)0.0111 (5)
H6AA0.14220.55490.01450.013*
H6AB0.23050.58950.09340.013*
C5A0.20149 (17)0.48342 (13)0.12076 (16)0.0104 (5)
C11A0.15088 (18)0.61815 (14)0.22402 (17)0.0160 (5)
H11A0.10350.63870.25150.024*
H11B0.20140.65440.22670.024*
H11C0.18010.57440.25840.024*
C12A0.06180 (18)0.66689 (14)0.06839 (18)0.0168 (6)
H12A0.02990.65410.00370.025*
H12B0.11560.70030.07200.025*
H12C0.01520.69070.09420.025*
C13A0.08558 (18)0.32166 (14)0.22696 (19)0.0171 (6)
H13A0.12820.35900.23980.026*
H13B0.06390.28850.27990.026*
H13C0.12090.29380.17200.026*
C14A0.10710 (17)0.25154 (14)0.25480 (17)0.0133 (5)
C15A0.23069 (18)0.16497 (13)0.32241 (18)0.0155 (5)
H15A0.29530.15440.31600.019*
H15B0.18410.12980.28330.019*
C16A0.2338 (2)0.15485 (15)0.42185 (18)0.0205 (6)
H16A0.16930.16330.42790.031*
H16B0.27960.18980.46070.031*
H16C0.25470.10490.44150.031*
C17A0.24881 (17)0.39335 (13)0.29969 (16)0.0099 (5)
C18A0.34612 (17)0.37375 (14)0.32615 (16)0.0129 (5)
C19A0.41183 (18)0.40080 (14)0.40664 (17)0.0155 (5)
H19A0.47770.38620.42360.019*
C20A0.38027 (19)0.44895 (15)0.46146 (17)0.0181 (6)
H20A0.42500.46830.51560.022*
C21A0.28354 (19)0.46919 (14)0.43783 (17)0.0167 (6)
H21A0.26190.50220.47570.020*
C22A0.21920 (18)0.44091 (13)0.35874 (17)0.0142 (5)
H22A0.15290.45400.34370.017*
Br1B0.08223 (2)0.00989 (2)0.13780 (2)0.01685 (7)
O1B0.21907 (11)0.03473 (9)0.35984 (12)0.0139 (4)
O2B0.41353 (12)0.16979 (9)0.13408 (12)0.0158 (4)
O3B0.26479 (11)0.12336 (9)0.11364 (11)0.0130 (4)
N1B0.51999 (15)0.01424 (12)0.30637 (14)0.0116 (4)
C2B0.48978 (17)0.04219 (13)0.24329 (16)0.0104 (5)
C3B0.39436 (17)0.05815 (13)0.21022 (16)0.0094 (5)
C4B0.31871 (16)0.01002 (13)0.23282 (16)0.0090 (5)
H4B0.26580.04210.24050.011*
C10B0.36467 (16)0.02951 (13)0.32331 (16)0.0090 (5)
C9B0.46114 (17)0.04440 (13)0.35161 (16)0.0096 (5)
C8B0.50953 (17)0.09235 (13)0.43263 (16)0.0114 (5)
H8BA0.54070.06120.48670.014*
H8BB0.56070.12140.41820.014*
C7B0.43782 (17)0.14455 (13)0.45732 (16)0.0117 (5)
C6B0.35073 (17)0.09960 (13)0.46295 (16)0.0109 (5)
H6BA0.30120.13330.47240.013*
H6BB0.37150.06730.51760.013*
C5B0.30492 (17)0.05315 (13)0.37865 (16)0.0110 (5)
C12B0.48777 (19)0.17893 (15)0.55204 (18)0.0182 (6)
H12D0.54110.21010.54760.027*
H12E0.44090.20840.57150.027*
H12F0.51310.14020.59740.027*
C11B0.40569 (19)0.20507 (14)0.38480 (18)0.0165 (6)
H11D0.37420.18320.32430.025*
H11E0.36010.23760.40170.025*
H11F0.46230.23320.38200.025*
C13B0.57203 (17)0.07931 (14)0.22026 (18)0.0155 (5)
H13D0.59370.12140.26110.023*
H13E0.55040.09590.15590.023*
H13F0.62570.04480.22870.023*
C14B0.36205 (17)0.12248 (13)0.15021 (16)0.0112 (5)
C15B0.22766 (18)0.18339 (14)0.05020 (18)0.0164 (6)
H15C0.25650.18220.00110.020*
H15D0.24400.23070.08270.020*
C16B0.11964 (19)0.17455 (16)0.0134 (2)0.0240 (6)
H16D0.09240.21410.03010.036*
H16E0.09180.17630.06470.036*
H16F0.10430.12740.01830.036*
C17B0.27431 (17)0.04582 (13)0.15652 (16)0.0107 (5)
C18B0.17577 (17)0.05192 (14)0.10999 (17)0.0128 (5)
C19B0.13963 (19)0.10322 (15)0.04075 (18)0.0196 (6)
H19B0.07210.10600.01030.023*
C20B0.2024 (2)0.15016 (15)0.01647 (19)0.0233 (6)
H20B0.17840.18470.03170.028*
C21B0.3010 (2)0.14683 (15)0.06268 (18)0.0200 (6)
H21B0.34440.17970.04710.024*
C22B0.33544 (18)0.09546 (13)0.13130 (17)0.0136 (5)
H22B0.40290.09370.16250.016*
H1B0.576 (2)0.0236 (14)0.3237 (18)0.011 (7)*
H1A0.0714 (19)0.4467 (14)0.1738 (17)0.006 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br1A0.01041 (12)0.01685 (13)0.01641 (13)0.00394 (10)0.00521 (10)0.00192 (10)
O1A0.0075 (8)0.0155 (9)0.0138 (9)0.0009 (7)0.0033 (7)0.0011 (7)
O2A0.0129 (10)0.0128 (10)0.0512 (14)0.0007 (8)0.0070 (9)0.0065 (9)
O3A0.0091 (8)0.0111 (9)0.0223 (10)0.0021 (7)0.0019 (7)0.0042 (7)
N1A0.0059 (10)0.0129 (11)0.0156 (11)0.0031 (9)0.0054 (8)0.0037 (9)
C2A0.0118 (12)0.0130 (13)0.0102 (12)0.0011 (10)0.0031 (10)0.0002 (10)
C3A0.0080 (11)0.0102 (12)0.0113 (12)0.0009 (9)0.0021 (9)0.0012 (9)
C4A0.0079 (11)0.0107 (12)0.0100 (11)0.0023 (9)0.0024 (9)0.0006 (10)
C10A0.0079 (11)0.0115 (12)0.0080 (11)0.0007 (9)0.0012 (9)0.0011 (9)
C9A0.0096 (11)0.0125 (12)0.0068 (11)0.0006 (10)0.0013 (9)0.0010 (9)
C8A0.0088 (12)0.0124 (13)0.0134 (12)0.0021 (10)0.0044 (10)0.0008 (10)
C7A0.0093 (12)0.0105 (12)0.0147 (13)0.0007 (10)0.0041 (10)0.0012 (10)
C6A0.0125 (12)0.0100 (12)0.0118 (12)0.0008 (10)0.0049 (10)0.0004 (10)
C5A0.0083 (11)0.0148 (13)0.0067 (11)0.0008 (10)0.0004 (9)0.0027 (10)
C11A0.0143 (13)0.0136 (13)0.0193 (14)0.0028 (11)0.0040 (11)0.0018 (11)
C12A0.0154 (13)0.0129 (13)0.0230 (14)0.0012 (11)0.0069 (11)0.0046 (11)
C13A0.0121 (13)0.0152 (14)0.0261 (15)0.0030 (10)0.0092 (11)0.0059 (11)
C14A0.0087 (12)0.0153 (13)0.0173 (13)0.0011 (10)0.0063 (10)0.0013 (11)
C15A0.0124 (12)0.0077 (12)0.0257 (15)0.0040 (10)0.0044 (11)0.0003 (11)
C16A0.0233 (15)0.0165 (14)0.0209 (15)0.0048 (12)0.0052 (12)0.0017 (11)
C17A0.0123 (12)0.0083 (12)0.0094 (12)0.0016 (10)0.0036 (9)0.0037 (9)
C18A0.0135 (12)0.0143 (13)0.0123 (12)0.0007 (10)0.0062 (10)0.0023 (10)
C19A0.0103 (12)0.0217 (14)0.0133 (13)0.0039 (11)0.0017 (10)0.0050 (11)
C20A0.0200 (14)0.0240 (15)0.0092 (12)0.0067 (12)0.0028 (11)0.0015 (11)
C21A0.0222 (14)0.0181 (14)0.0111 (13)0.0026 (11)0.0069 (11)0.0020 (11)
C22A0.0152 (13)0.0125 (13)0.0145 (13)0.0009 (10)0.0038 (10)0.0037 (10)
Br1B0.00708 (12)0.02538 (15)0.01687 (13)0.00182 (10)0.00179 (9)0.00505 (11)
O1B0.0066 (8)0.0185 (10)0.0172 (9)0.0003 (7)0.0046 (7)0.0005 (8)
O2B0.0155 (9)0.0108 (9)0.0220 (10)0.0021 (7)0.0071 (8)0.0020 (7)
O3B0.0105 (8)0.0124 (9)0.0145 (9)0.0021 (7)0.0014 (7)0.0051 (7)
N1B0.0045 (10)0.0172 (12)0.0133 (11)0.0020 (9)0.0031 (8)0.0025 (9)
C2B0.0103 (12)0.0105 (12)0.0115 (12)0.0000 (10)0.0049 (10)0.0003 (10)
C3B0.0104 (12)0.0095 (12)0.0074 (11)0.0011 (9)0.0010 (9)0.0026 (9)
C4B0.0072 (11)0.0101 (12)0.0092 (11)0.0012 (9)0.0018 (9)0.0009 (9)
C10B0.0077 (11)0.0101 (12)0.0092 (11)0.0006 (9)0.0023 (9)0.0001 (9)
C9B0.0116 (12)0.0084 (12)0.0095 (12)0.0002 (10)0.0040 (9)0.0016 (9)
C8B0.0100 (12)0.0125 (13)0.0117 (12)0.0011 (10)0.0034 (10)0.0030 (10)
C7B0.0124 (12)0.0122 (13)0.0106 (12)0.0005 (10)0.0036 (10)0.0027 (10)
C6B0.0109 (12)0.0125 (13)0.0101 (12)0.0016 (10)0.0043 (10)0.0009 (10)
C5B0.0102 (12)0.0117 (13)0.0104 (12)0.0034 (10)0.0022 (9)0.0062 (10)
C12B0.0170 (13)0.0199 (15)0.0177 (14)0.0014 (11)0.0052 (11)0.0069 (11)
C11B0.0175 (13)0.0140 (14)0.0183 (14)0.0002 (11)0.0057 (11)0.0022 (11)
C13B0.0111 (12)0.0193 (14)0.0177 (13)0.0011 (11)0.0070 (10)0.0042 (11)
C14B0.0109 (12)0.0128 (13)0.0105 (12)0.0011 (10)0.0041 (9)0.0031 (10)
C15B0.0195 (14)0.0107 (13)0.0177 (13)0.0029 (11)0.0035 (11)0.0055 (11)
C16B0.0187 (14)0.0223 (15)0.0276 (16)0.0073 (12)0.0016 (12)0.0115 (12)
C17B0.0122 (12)0.0105 (12)0.0095 (12)0.0029 (10)0.0033 (10)0.0031 (10)
C18B0.0104 (12)0.0137 (13)0.0145 (13)0.0002 (10)0.0041 (10)0.0044 (10)
C19B0.0163 (14)0.0196 (15)0.0190 (14)0.0071 (11)0.0005 (11)0.0015 (11)
C20B0.0330 (16)0.0161 (14)0.0178 (14)0.0082 (12)0.0032 (12)0.0046 (11)
C21B0.0263 (15)0.0146 (14)0.0191 (14)0.0030 (12)0.0069 (12)0.0027 (11)
C22B0.0133 (12)0.0121 (13)0.0137 (13)0.0017 (10)0.0013 (10)0.0026 (10)
Geometric parameters (Å, º) top
Br1A—C18A1.904 (2)Br1B—C18B1.909 (2)
O1A—C5A1.241 (3)O1B—C5B1.237 (3)
O2A—C14A1.208 (3)O2B—C14B1.215 (3)
O3A—C14A1.343 (3)O3B—C14B1.351 (3)
O3A—C15A1.451 (3)O3B—C15B1.454 (3)
N1A—C2A1.385 (3)N1B—C2B1.387 (3)
N1A—C9A1.361 (3)N1B—C9B1.363 (3)
N1A—H1A0.83 (3)N1B—H1B0.80 (3)
C2A—C3A1.355 (3)C2B—C3B1.354 (3)
C2A—C13A1.504 (3)C2B—C13B1.503 (3)
C3A—C4A1.528 (3)C3B—C4B1.524 (3)
C3A—C14A1.475 (3)C3B—C14B1.476 (3)
C4A—H4A1.0000C4B—H4B1.0000
C4A—C10A1.522 (3)C4B—C10B1.519 (3)
C4A—C17A1.537 (3)C4B—C17B1.534 (3)
C10A—C9A1.368 (3)C10B—C9B1.362 (3)
C10A—C5A1.436 (3)C10B—C5B1.443 (3)
C9A—C8A1.505 (3)C9B—C8B1.503 (3)
C8A—H8AA0.9900C8B—H8BA0.9900
C8A—H8AB0.9900C8B—H8BB0.9900
C8A—C7A1.541 (3)C8B—C7B1.539 (3)
C7A—C6A1.536 (3)C7B—C6B1.531 (3)
C7A—C11A1.534 (3)C7B—C12B1.538 (3)
C7A—C12A1.525 (3)C7B—C11B1.532 (3)
C6A—H6AA0.9900C6B—H6BA0.9900
C6A—H6AB0.9900C6B—H6BB0.9900
C6A—C5A1.512 (3)C6B—C5B1.514 (3)
C11A—H11A0.9800C12B—H12D0.9800
C11A—H11B0.9800C12B—H12E0.9800
C11A—H11C0.9800C12B—H12F0.9800
C12A—H12A0.9800C11B—H11D0.9800
C12A—H12B0.9800C11B—H11E0.9800
C12A—H12C0.9800C11B—H11F0.9800
C13A—H13A0.9800C13B—H13D0.9800
C13A—H13B0.9800C13B—H13E0.9800
C13A—H13C0.9800C13B—H13F0.9800
C15A—H15A0.9900C15B—H15C0.9900
C15A—H15B0.9900C15B—H15D0.9900
C15A—C16A1.509 (4)C15B—C16B1.505 (4)
C16A—H16A0.9800C16B—H16D0.9800
C16A—H16B0.9800C16B—H16E0.9800
C16A—H16C0.9800C16B—H16F0.9800
C17A—C18A1.393 (3)C17B—C18B1.395 (3)
C17A—C22A1.407 (3)C17B—C22B1.401 (3)
C18A—C19A1.395 (3)C18B—C19B1.390 (4)
C19A—H19A0.9500C19B—H19B0.9500
C19A—C20A1.382 (4)C19B—C20B1.381 (4)
C20A—H20A0.9500C20B—H20B0.9500
C20A—C21A1.389 (4)C20B—C21B1.391 (4)
C21A—H21A0.9500C21B—H21B0.9500
C21A—C22A1.381 (3)C21B—C22B1.381 (4)
C22A—H22A0.9500C22B—H22B0.9500
C14A—O3A—C15A116.77 (19)C14B—O3B—C15B114.45 (19)
C2A—N1A—H1A118.2 (17)C2B—N1B—H1B117.8 (19)
C9A—N1A—C2A123.0 (2)C9B—N1B—C2B122.3 (2)
C9A—N1A—H1A118.6 (17)C9B—N1B—H1B118.8 (19)
N1A—C2A—C13A113.0 (2)N1B—C2B—C13B112.9 (2)
C3A—C2A—N1A120.2 (2)C3B—C2B—N1B119.5 (2)
C3A—C2A—C13A126.8 (2)C3B—C2B—C13B127.6 (2)
C2A—C3A—C4A121.9 (2)C2B—C3B—C4B121.1 (2)
C2A—C3A—C14A119.7 (2)C2B—C3B—C14B120.0 (2)
C14A—C3A—C4A118.4 (2)C14B—C3B—C4B118.9 (2)
C3A—C4A—H4A108.9C3B—C4B—H4B108.5
C3A—C4A—C17A112.70 (19)C3B—C4B—C17B112.42 (19)
C10A—C4A—C3A110.48 (19)C10B—C4B—C3B109.25 (19)
C10A—C4A—H4A108.9C10B—C4B—H4B108.5
C10A—C4A—C17A107.00 (19)C10B—C4B—C17B109.69 (19)
C17A—C4A—H4A108.9C17B—C4B—H4B108.5
C9A—C10A—C4A121.4 (2)C9B—C10B—C4B120.7 (2)
C9A—C10A—C5A119.9 (2)C9B—C10B—C5B119.7 (2)
C5A—C10A—C4A118.4 (2)C5B—C10B—C4B119.6 (2)
N1A—C9A—C10A120.4 (2)N1B—C9B—C8B116.2 (2)
N1A—C9A—C8A116.2 (2)C10B—C9B—N1B120.0 (2)
C10A—C9A—C8A123.4 (2)C10B—C9B—C8B123.9 (2)
C9A—C8A—H8AA109.0C9B—C8B—H8BA109.1
C9A—C8A—H8AB109.0C9B—C8B—H8BB109.1
C9A—C8A—C7A112.81 (19)C9B—C8B—C7B112.27 (19)
H8AA—C8A—H8AB107.8H8BA—C8B—H8BB107.9
C7A—C8A—H8AA109.0C7B—C8B—H8BA109.1
C7A—C8A—H8AB109.0C7B—C8B—H8BB109.1
C6A—C7A—C8A108.19 (19)C6B—C7B—C8B108.03 (19)
C11A—C7A—C8A110.5 (2)C6B—C7B—C12B109.36 (19)
C11A—C7A—C6A109.8 (2)C6B—C7B—C11B110.6 (2)
C12A—C7A—C8A108.96 (19)C12B—C7B—C8B108.64 (19)
C12A—C7A—C6A110.1 (2)C11B—C7B—C8B110.8 (2)
C12A—C7A—C11A109.2 (2)C11B—C7B—C12B109.4 (2)
C7A—C6A—H6AA108.7C7B—C6B—H6BA108.7
C7A—C6A—H6AB108.7C7B—C6B—H6BB108.7
H6AA—C6A—H6AB107.6H6BA—C6B—H6BB107.6
C5A—C6A—C7A114.4 (2)C5B—C6B—C7B114.42 (19)
C5A—C6A—H6AA108.7C5B—C6B—H6BA108.7
C5A—C6A—H6AB108.7C5B—C6B—H6BB108.7
O1A—C5A—C10A120.9 (2)O1B—C5B—C10B121.5 (2)
O1A—C5A—C6A120.0 (2)O1B—C5B—C6B120.2 (2)
C10A—C5A—C6A119.1 (2)C10B—C5B—C6B118.3 (2)
C7A—C11A—H11A109.5C7B—C12B—H12D109.5
C7A—C11A—H11B109.5C7B—C12B—H12E109.5
C7A—C11A—H11C109.5C7B—C12B—H12F109.5
H11A—C11A—H11B109.5H12D—C12B—H12E109.5
H11A—C11A—H11C109.5H12D—C12B—H12F109.5
H11B—C11A—H11C109.5H12E—C12B—H12F109.5
C7A—C12A—H12A109.5C7B—C11B—H11D109.5
C7A—C12A—H12B109.5C7B—C11B—H11E109.5
C7A—C12A—H12C109.5C7B—C11B—H11F109.5
H12A—C12A—H12B109.5H11D—C11B—H11E109.5
H12A—C12A—H12C109.5H11D—C11B—H11F109.5
H12B—C12A—H12C109.5H11E—C11B—H11F109.5
C2A—C13A—H13A109.5C2B—C13B—H13D109.5
C2A—C13A—H13B109.5C2B—C13B—H13E109.5
C2A—C13A—H13C109.5C2B—C13B—H13F109.5
H13A—C13A—H13B109.5H13D—C13B—H13E109.5
H13A—C13A—H13C109.5H13D—C13B—H13F109.5
H13B—C13A—H13C109.5H13E—C13B—H13F109.5
O2A—C14A—O3A122.3 (2)O2B—C14B—O3B122.5 (2)
O2A—C14A—C3A127.0 (2)O2B—C14B—C3B126.3 (2)
O3A—C14A—C3A110.7 (2)O3B—C14B—C3B111.2 (2)
O3A—C15A—H15A109.3O3B—C15B—H15C110.2
O3A—C15A—H15B109.3O3B—C15B—H15D110.2
O3A—C15A—C16A111.6 (2)O3B—C15B—C16B107.5 (2)
H15A—C15A—H15B108.0H15C—C15B—H15D108.5
C16A—C15A—H15A109.3C16B—C15B—H15C110.2
C16A—C15A—H15B109.3C16B—C15B—H15D110.2
C15A—C16A—H16A109.5C15B—C16B—H16D109.5
C15A—C16A—H16B109.5C15B—C16B—H16E109.5
C15A—C16A—H16C109.5C15B—C16B—H16F109.5
H16A—C16A—H16B109.5H16D—C16B—H16E109.5
H16A—C16A—H16C109.5H16D—C16B—H16F109.5
H16B—C16A—H16C109.5H16E—C16B—H16F109.5
C18A—C17A—C4A125.4 (2)C18B—C17B—C4B124.7 (2)
C18A—C17A—C22A116.9 (2)C18B—C17B—C22B116.4 (2)
C22A—C17A—C4A117.6 (2)C22B—C17B—C4B118.9 (2)
C17A—C18A—Br1A121.46 (18)C17B—C18B—Br1B121.88 (19)
C17A—C18A—C19A121.8 (2)C19B—C18B—Br1B115.91 (19)
C19A—C18A—Br1A116.74 (18)C19B—C18B—C17B122.2 (2)
C18A—C19A—H19A120.3C18B—C19B—H19B120.2
C20A—C19A—C18A119.5 (2)C20B—C19B—C18B119.6 (2)
C20A—C19A—H19A120.3C20B—C19B—H19B120.2
C19A—C20A—H20A119.8C19B—C20B—H20B120.1
C19A—C20A—C21A120.4 (2)C19B—C20B—C21B119.9 (2)
C21A—C20A—H20A119.8C21B—C20B—H20B120.1
C20A—C21A—H21A120.3C20B—C21B—H21B120.2
C22A—C21A—C20A119.3 (2)C22B—C21B—C20B119.6 (2)
C22A—C21A—H21A120.3C22B—C21B—H21B120.2
C17A—C22A—H22A119.0C17B—C22B—H22B118.9
C21A—C22A—C17A122.1 (2)C21B—C22B—C17B122.2 (2)
C21A—C22A—H22A119.0C21B—C22B—H22B118.9
Br1A—C18A—C19A—C20A179.88 (19)Br1B—C18B—C19B—C20B179.9 (2)
N1A—C2A—C3A—C4A2.6 (4)N1B—C2B—C3B—C4B6.8 (3)
N1A—C2A—C3A—C14A178.9 (2)N1B—C2B—C3B—C14B174.0 (2)
N1A—C9A—C8A—C7A157.0 (2)N1B—C9B—C8B—C7B159.6 (2)
C2A—N1A—C9A—C10A2.6 (4)C2B—N1B—C9B—C10B12.6 (4)
C2A—N1A—C9A—C8A177.8 (2)C2B—N1B—C9B—C8B166.5 (2)
C2A—C3A—C4A—C10A14.1 (3)C2B—C3B—C4B—C10B25.5 (3)
C2A—C3A—C4A—C17A105.6 (3)C2B—C3B—C4B—C17B96.5 (3)
C2A—C3A—C14A—O2A19.8 (4)C2B—C3B—C14B—O2B9.1 (4)
C2A—C3A—C14A—O3A160.9 (2)C2B—C3B—C14B—O3B171.1 (2)
C3A—C4A—C10A—C9A18.3 (3)C3B—C4B—C10B—C9B27.2 (3)
C3A—C4A—C10A—C5A168.2 (2)C3B—C4B—C10B—C5B154.4 (2)
C3A—C4A—C17A—C18A120.5 (2)C3B—C4B—C17B—C18B122.8 (2)
C3A—C4A—C17A—C22A64.0 (3)C3B—C4B—C17B—C22B58.0 (3)
C4A—C3A—C14A—O2A161.7 (2)C4B—C3B—C14B—O2B171.8 (2)
C4A—C3A—C14A—O3A17.7 (3)C4B—C3B—C14B—O3B8.1 (3)
C4A—C10A—C9A—N1A11.2 (3)C4B—C10B—C9B—N1B10.1 (3)
C4A—C10A—C9A—C8A168.4 (2)C4B—C10B—C9B—C8B170.9 (2)
C4A—C10A—C5A—O1A10.3 (3)C4B—C10B—C5B—O1B8.5 (3)
C4A—C10A—C5A—C6A170.6 (2)C4B—C10B—C5B—C6B173.4 (2)
C4A—C17A—C18A—Br1A6.1 (3)C4B—C17B—C18B—Br1B0.6 (3)
C4A—C17A—C18A—C19A174.5 (2)C4B—C17B—C18B—C19B179.4 (2)
C4A—C17A—C22A—C21A173.7 (2)C4B—C17B—C22B—C21B179.4 (2)
C10A—C4A—C17A—C18A117.9 (2)C10B—C4B—C17B—C18B115.4 (2)
C10A—C4A—C17A—C22A57.6 (3)C10B—C4B—C17B—C22B63.7 (3)
C10A—C9A—C8A—C7A22.6 (3)C10B—C9B—C8B—C7B21.4 (3)
C9A—N1A—C2A—C3A7.0 (4)C9B—N1B—C2B—C3B14.3 (4)
C9A—N1A—C2A—C13A173.5 (2)C9B—N1B—C2B—C13B165.5 (2)
C9A—C10A—C5A—O1A176.1 (2)C9B—C10B—C5B—O1B173.1 (2)
C9A—C10A—C5A—C6A3.0 (3)C9B—C10B—C5B—C6B5.0 (3)
C9A—C8A—C7A—C6A48.6 (3)C9B—C8B—C7B—C6B49.2 (3)
C9A—C8A—C7A—C11A71.7 (3)C9B—C8B—C7B—C12B167.8 (2)
C9A—C8A—C7A—C12A168.2 (2)C9B—C8B—C7B—C11B72.0 (3)
C8A—C7A—C6A—C5A51.3 (3)C8B—C7B—C6B—C5B52.6 (3)
C7A—C6A—C5A—O1A154.2 (2)C7B—C6B—C5B—O1B155.3 (2)
C7A—C6A—C5A—C10A26.7 (3)C7B—C6B—C5B—C10B26.5 (3)
C5A—C10A—C9A—N1A175.5 (2)C5B—C10B—C9B—N1B171.5 (2)
C5A—C10A—C9A—C8A4.9 (4)C5B—C10B—C9B—C8B7.5 (4)
C11A—C7A—C6A—C5A69.5 (3)C12B—C7B—C6B—C5B170.7 (2)
C12A—C7A—C6A—C5A170.2 (2)C11B—C7B—C6B—C5B68.8 (3)
C13A—C2A—C3A—C4A176.8 (2)C13B—C2B—C3B—C4B173.5 (2)
C13A—C2A—C3A—C14A1.7 (4)C13B—C2B—C3B—C14B5.7 (4)
C14A—O3A—C15A—C16A88.5 (3)C14B—O3B—C15B—C16B177.9 (2)
C14A—C3A—C4A—C10A167.4 (2)C14B—C3B—C4B—C10B155.3 (2)
C14A—C3A—C4A—C17A73.0 (3)C14B—C3B—C4B—C17B82.7 (3)
C15A—O3A—C14A—O2A0.9 (3)C15B—O3B—C14B—O2B2.9 (3)
C15A—O3A—C14A—C3A178.5 (2)C15B—O3B—C14B—C3B177.29 (19)
C17A—C4A—C10A—C9A104.7 (2)C17B—C4B—C10B—C9B96.4 (3)
C17A—C4A—C10A—C5A68.8 (3)C17B—C4B—C10B—C5B82.0 (3)
C17A—C18A—C19A—C20A0.7 (4)C17B—C18B—C19B—C20B0.1 (4)
C18A—C17A—C22A—C21A2.2 (4)C18B—C17B—C22B—C21B1.4 (4)
C18A—C19A—C20A—C21A1.3 (4)C18B—C19B—C20B—C21B1.3 (4)
C19A—C20A—C21A—C22A0.2 (4)C19B—C20B—C21B—C22B1.3 (4)
C20A—C21A—C22A—C17A1.6 (4)C20B—C21B—C22B—C17B0.1 (4)
C22A—C17A—C18A—Br1A178.40 (17)C22B—C17B—C18B—Br1B178.55 (17)
C22A—C17A—C18A—C19A1.0 (3)C22B—C17B—C18B—C19B1.4 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1B—H1B···O1Ai0.80 (3)2.02 (3)2.818 (3)174 (3)
N1A—H1A···O1Bii0.83 (3)2.07 (3)2.884 (3)165 (2)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x, y+1/2, z+1/2.

Experimental details

For all structures: C21H24BrNO3, Mr = 418.32, Z = 8. Experiments were carried out at 100 K with Mo Kα radiation using a Bruker SMART BREEZE CCD area-detector diffractometer. Absorption was corrected for by multi-scan methods, (SADABS; Bruker, 2008). H atoms were treated by a mixture of independent and constrained refinement.

(I)(II)(III)
Crystal data
Crystal system, space groupOrthorhombic, PbcnOrthorhombic, PbcnMonoclinic, P21/c
a, b, c (Å)18.0371 (4), 15.4309 (3), 14.2604 (3)17.0813 (5), 15.4877 (5), 14.2544 (5)14.5012 (18), 18.299 (2), 15.1952 (19)
α, β, γ (°)90, 90, 9090, 90, 9090, 107.5262 (15), 90
V3)3969.08 (14)3771.0 (2)3844.9 (8)
µ (mm1)2.092.202.16
Crystal size (mm)0.26 × 0.18 × 0.130.40 × 0.21 × 0.190.34 × 0.16 × 0.08
Data collection
Tmin, Tmax0.909, 1.0000.839, 1.0000.866, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
35271, 4558, 3391 55070, 5055, 4278 45465, 8935, 6859
Rint0.0380.0320.065
(sin θ/λ)max1)0.6500.6840.653
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.101, 1.04 0.032, 0.084, 1.03 0.036, 0.081, 1.02
No. of reflections455850558935
No. of parameters243243485
Δρmax, Δρmin (e Å3)1.49, 1.211.31, 0.381.46, 0.47

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.89 (3)1.94 (3)2.812 (2)168 (3)
Symmetry code: (i) x, y, z1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.86 (2)2.05 (2)2.8896 (19)166 (2)
Symmetry code: (i) x, y+1, z+1/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1B—H1B···O1Ai0.80 (3)2.02 (3)2.818 (3)174 (3)
N1A—H1A···O1Bii0.83 (3)2.07 (3)2.884 (3)165 (2)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x, y+1/2, z+1/2.
 

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