Relation between photochromic properties and molecular structures in salicylideneaniline crystals

Johmoto, K.; Ishida, T.; Sekine, A.; Uekusa, H.; Ohashi, Y.

doi:10.1107/S0108768112010993

research papers

STRUCTURAL SCIENCE
CRYSTAL ENGINEERING
MATERIALS

ISSN: 2052-5206

Volume 68| Part 3| June 2012| Pages 297-304

doi:10.1107/S0108768112010993

Relation between photochromic properties and molecular structures in salicylideneaniline crystals

Kohei Johmoto,^a ^* Takashi Ishida,^a Akiko Sekine,^a Hidehiro Uekusa ^a and Yuji Ohashi ^a,^b

^aDepartment of Chemistry and Material Science, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 153-8902, Japan, and ^bIbaraki Quantum Beam Research Center, Shirakata, Tokai, Ibaraki 319-1106, Japan
^*Correspondence e-mail: johmoto@chem.titech.ac.jp

(Received 10 January 2012; accepted 13 March 2012; online 4 May 2012)

The crystal structures of the salicylideneaniline derivatives N-salicylidene-4-tert-butyl-aniline (1), N-3,5-di-tert-butyl-salicylidene-3-methoxyaniline (2), N-3,5-di-tert-butyl-salicylidene-3-bromoaniline (3), N-3,5-di-tert-butyl-salicylidene-3-chloroaniline (4), N-3,5-di-tert-butyl-salicylidene-4-bromoaniline (5), N-3,5-di-tert-butyl-salicylidene-aniline (6), N-3,5-di-tert-butyl-salicylidene-4-carboxyaniline (7) and N-salicylidene-2-chloroaniline (8) were analyzed by X-ray diffraction analysis at ambient temperature to investigate the relationship between their photochromic properties and molecular structures. A clear correlation between photochromism and the dihedral angle of the two benzene rings in the salicylideneaniline derivatives was observed. Crystals with dihedral angles less than 20° were non-photochromic, whereas those with dihedral angles greater than 30° were photochromic. Crystals with dihedral angles between 20 and 30° could be either photochromic or non-photochromic. Inhibition of the pedal motion by intra- or intermolecular steric hindrance, however, can result in non-photochromic behaviour even if the dihedral angle is larger than 30°.

Keywords: photochromism; salicylideneaniline; pedal motion; dihedral angle.

1. Introduction

Photochromic compounds undergo reversible colour changes upon photoirradiation as a consequence of an associated chemical transformation. This in turn leads to changes in the physicochemical properties of such compounds including absorption, fluorescence, refraction index and electric permittivity (Duerr & Bouas-Laurent, 1990 ; Crano & Guglielmetti, 1999 ). Photochromic compounds have attracted considerable attention because of their application in a variety of areas including photochromic lenses (Armistead & Stookey, 1964 ), rewritable papers (Sousa & Kashnow, 1969 ), photo-switching materials (Fukaminato et al., 2004 ), optical data storages (Kawata & Kawata, 2000 ) and biological sensors (Mizuno et al., 2008 ).

Salicylideneaniline (SA) derivatives are well known as photochromic compounds, undergoing a colour change from yellow to red upon irradiation with UV light and the reverse colour change upon exposure to visible light or heat (thermal fading). These compounds can be readily synthesized according to a procedure first reported in 1909, involving the condensation reaction of salicylaldehydes and anilines (Senir & Shepheard, 1909 ; Senir et al., 1912 ). Furthermore, SA derivatives have demonstrated a high resistance to fatigue and this is an important property for any prospective photochromic compound to have (Andes & Manikowski, 1968 ). Following a systematic investigation into the relationship between the structural and physical properties of SA derivatives, it was proposed that crystals with a non-planar molecular conformation would exhibit photochromic properties and that those with a planar molecular conformation would be non-photochromic and exhibit thermochromic properties (Cohen & Schmidt, 1962 ). Further consideration later led to the assertion that photochromic and thermochromic properties were mutually exclusive (Cohen, Hirshberg & Schmidt, 1964 ; Cohen, Schmidt & Flavian, 1964 ; Bregman et al., 1964 ; refcode CHILSAN). More recently, however, it was revealed that, as a consequence of tautomerization between the enol and cis-keto forms, the majority of SA derivatives have thermochromic properties, regardless of their photochromic properties (Ogawa et al., 1998 ; Fujiwara et al., 2004 ; Harada et al., 2007 ).

In light of the many controversies surrounding the understanding of photochromic properties (Duerr & Bouas-Laurent, 1990), we clearly demonstrated that the metastable red-coloured species in photo-irradiated SA crystals takes the trans-keto form (Harada et al., 1999 ) by X-ray crystal structure analysis using two-photon excitation. Thus, from a mechanistic perspective, this provided an illustration that photochromism involves the transfer of a proton from the phenolic OH group of the enol form to the N atom of the imine group, generating the cis-keto form that is subsequently converted into the red-coloured trans-keto form, as shown in Scheme 1. Since the photochromic molecular transformation from enol to trans-keto forms occurs without destroying the single-crystal form, it was assumed that the transformation occurs via pedal motion in a manner similar to the thermal motion of azobenzene crystals (Harada et al., 1997 ; Harada & Ogawa, 2009 ), which is known as a space-efficient motion in crystals.

Furthermore, there is no consistency in the thermal fading reaction rates of SA derivatives from the red-coloured trans-keto form to the original pale-yellow enol form. In a recent publication, we clearly demonstrated using keto-form structures of polymorphic crystals that thermal fading reaction rates were dependent upon intermolecular hydrogen bonding between the NH group of the trans-keto form and hydrogen-bond acceptors on neighbouring molecules (Johmoto et al., 2009 ). These results were in good agreement with the ab initio calculation (Mikami & Nakamura, 2004 ).

Although it has long been accepted that molecular planarity plays an important role in photochromic reactions, there have been few reports investigating threshold values for the planarity (Haneda et al., 2007 ). Furthermore, several SA derivatives with dihedral angles of approximately 90° have recently been reported that did not exhibit photochromism (Fukuda et al., 2003 ). Given the range of conflicting experimental information and opinion, further investigation into the relationship between the planar conformations of SA derivatives and their photochromic properties is required. In this study we report the crystal structures of eight SA derivatives to obtain a quantitative threshold value relating the non-planarity of SA crystals to the occurrence of photochromic and non-photochromic behaviour. The SA crystals reported so far in the literature were also included in the study.

2. Experimental

2.1. Preparation of salicylideneaniline derivatives

Salicylaldehyde (1.0 mmol) and aniline (1.0 mmol) were dissolved in methanol (50 ml) at 298 K. The resulting solution was stirred for 10 min and evaporated under reduced pressure until the crude condensation product was precipitated from solution and collected by filtration. Pure crystals were obtained by recrystallization from ethanol at 298 K. The salicylideneanilines (1)–(8) were obtained according to the same methodology by condensation of the corresponding salicylaldehydes and anilines, which have the substituents corresponding to the final products (Scheme 2).

2.2. Identification of photochromism by UV–vis spectrum

The UV–vis spectra of the SA crystals were measured at 298 K with a JASCO V-560 spectrometer equipped with the option (ISV-469) for diffuse reflectance spectroscopy. Analytical samples were prepared by mixing the SA crystals (7 mg) with BaSO₄ powder (350 mg). Photoirradiation was carried out through a glass filter (HOYA UV360) at 298 K with a high-pressure Hg lamp transmitting at a wavelength of 365 nm. Measurements were taken before and after photoirradiation.

2.3. Single-crystal X-ray diffraction analysis

Single-crystal X-ray diffraction data were collected at ambient temperature in ω-scan mode with R-AXIS RAPID and R-AXIS RAPID II imaging plate cameras (Rigaku) using graphite-monochromated Mo Kα radiation (λ = 0.71075 Å) obtained from a rotating anode source and Cu Kα radiation (λ = 1.54186 Å) from a rotating anode source with a confocal multilayer mirror. The data were collected at ambient temperature to correspond with the conditions of the photochromic reaction. The integrated and scaled data were empirically corrected for absorption effects with ABSCOR (Higashi, 1995 ). The initial structures were solved by direct methods with SHELXS97 (Sheldrick, 2008 ) and refined on F₀² with SHELXL97 (Sheldrick, 2008). With the exception of the disordered C atoms of the tert-butyl group, the non-H atoms were refined anisotropically, and all of the H atoms were obtained geometrically and included in the calculations using the riding atom model. The dihedral angles between the two benzene rings of SA molecules were calculated using SHELXL97 (Sheldrick, 2008). Although a crystal structure for (6) had already been reported at 223 K (Ahmad et al., 2011 ), in the interest of consistency and direct comparison the structure was also analysed at ambient temperature. The crystallographic data and experimental details are summarized in Table 1.

Table 1
Experimental details

For all structures: Z = 4. H-atom parameters were constrained.

	(1)	(2)	(3)	(4)
Crystal data
Chemical formula	C_17.12H_19.35NO	C₂₂H₂₉NO₂	C₂₁H₂₆BrNO	C₂₁H₂₆ClNO
M_r	255.13	339.46	388.34	343.88
Crystal system, space group	Monoclinic, P21/c	Triclinic, $[P\bar 1]$	Triclinic, $[P\bar 1]$	Triclinic, $[P\bar 1]$
Temperature (K)	296	293	296	296
a, b, c (Å)	14.3711 (8), 6.4227 (4), 17.9938 (9)	10.814 (2), 12.011 (2), 15.727 (3)	10.7505 (6), 11.5008 (7), 16.3284 (8)	10.7392 (12), 11.5369 (15), 16.1292 (19)
α, β, γ (°)	90, 116.819 (4), 90	89.25 (3), 81.21 (3), 89.97 (3)	87.9590 (10), 83.166 (2), 89.536 (2)	88.032 (3), 82.446 (3), 89.642 (3)
V (Å³)	1482.20 (14)	2018.7 (7)	2003.20 (19)	1979.8 (4)
F(000)	544	736	808	7364
D_x (Mg m⁻³)	1.135	1.117	1.288	1.154
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	0.07	0.07	2.06	0.20
Crystal size (mm)	0.34 × 0.30 × 0.18	0.34 × 0.26 × 0.06	0.18 × 0.17 × 0.04	0.15 × 0.07 × 0.03

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area detector	Bruker SMART CCD area detector	Rigaku R-AXIS RAPID IP area detector	Rigaku R-AXIS RAPID IP area detector
Absorption correction	Multi-scan, absorption was corrected by ABSCOR	Multi-scan, absorption was corrected by SADABS	Multi-scan, absorption was corrected by ABSCOR	Multi-scan, absorption was corrected by ABSCOR
T_min, T_max	0.885, 0.988	0.976, 0.996	0.189, 0.928	0.729, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	23 765, 3381, 2187	29 048, 10 049, 5423	19 830, 9015, 4719	16 014, 7172, 2946
R_int	0.036	0.036	0.054	0.079
θ values (°)	θ_max = 27.5, θ_min = 3.0	θ_max = 28.4, θ_min = 1.3	θ_max = 27.4, θ_min = 3.0	θ_max = 25.3, θ_min = 3.0
(sin θ/λ)_max (Å⁻¹)	0.649	0.668	0.648	0.602
Completeness to θ	99.5% for 27.48°	99.5% for 28.35°	98.9% for 27.43°	99.1% for 25.34°

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.190, 1.13	0.044, 0.128, 0.92	0.043, 0.143, 1.08	0.064, 0.164, 1.02
No. of reflections	3381	10 049	9015	7172
No. of parameters	194	482	445	461
No. of restraints	0	0	0	0
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.21	0.24, −0.16	0.87, −0.78	0.20, −0.19
Extinction method	SHELXL	SHELXL	None	None
Extinction coefficient	0.023 (4)	0.0230 (19)	–	–

	(5)	(6)	(7)	(8)
Crystal data
Chemical formula	C_21.05H_26.14BrNO	C₂₁H₂₇NO	C₂₂H₂₇NO₃	C₁₃H₁₀ClNO
M_r	388.34	309.44	353.45	231.67
Crystal system, space group	Monoclinic, P2₁/c	Orthorhombic, Pna2₁	Monoclinic, P2₁/c	Monoclinic, P2₁/c
Temperature (K)	296	296	293	293
a, b, c (Å)	18.0699 (14), 10.5997 (10), 10.3838 (9)	12.4043 (6), 8.9918 (5), 16.6903 (7)	6.1482 (4), 19.5491 (13), 17.0976 (13)	4.6868 (1), 18.9497 (4), 12.8231 (2)
β (°)	92.858 (2)	90	109.453 (3)	105.9680 (10)
V (Å³)	1986.4 (3)	1861.59 (16)	1937.7 (2)	1094.92 (4)
F(000)	808	672	760	480
D_x (Mg m⁻³)	1.299	1.104	1.212	1.405
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	2.08	0.07	0.08	2.88
Crystal size (mm)	0.20 × 0.14 × 0.06	0.50 × 0.35 × 0.15	0.40 × 0.30 × 0.02	0.33 × 0.10 × 0.06

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area detector	Rigaku R-AXIS RAPID IP area detector	Rigaku R-AXIS RAPID IP area detector	Rigaku VM-SPIDER IP area detector
Absorption correction	Multi-scan, absorption was corrected by ABSCOR	Multi-scan, absorption was corrected by ABSCOR	Multi-scan, absorption was corrected by ABSCOR	Multi-scan, absorption was corrected by ABSCOR
T_min, T_max	0.559, 0.884	0.798, 0.990	0.627, 0.998	0.340, 0.837
No. of measured, independent and observed [I > 2σ(I)] reflections	18 792, 4500, 1915	17 422, 2193, 1955	17 354, 4410, 2938	12 241, 1976, 1565
R_int	0.109	0.032	0.087	0.046
θ values (°)	θ_max = 27.5, θ_min = 3.0	θ_max = 27.4, θ_min = 3.1	θ_max = 27.5, θ_min = 2.1	θ_max = 68.2, θ_min = 4.3
(sin θ/λ)_max (Å⁻¹)	0.649	0.648	0.649	0.602
Completeness to θ	99.0% for 27.46°	99.8% for 27.42°	98.9% for 27.43°	98.3% for 68.22°

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.147, 1.02	0.039, 0.101, 1.06	0.072, 0.206, 1.03	0.056, 0.170, 1.08
No. of reflections	4500	2193	4410	1976
No. of parameters	241	214	272	145
No. of restraints	1	1	0	0
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.38	0.22, −0.14	0.33, −0.27	0.33, −0.21
Computer programs used: PROCESS-AUTO (Rigaku, 1998 ), SMART (Siemens, 1996 ), SAINT (Siemens, 1994a ), SADABS (Sheldrick, 1996 ), SHELXL97, SHELXS97 (Sheldrick, 2008), ORTEP3 (Farrugia, 2008 ), SHELXTL (Siemens, 1994b ).

3. Results

3.1. Crystal and molecular structures before photoirradiation

The molecular and crystal structures of (1) are shown in Figs. 1 and 2. The tert-butyl group of (1) is disordered and can exist in three different conformations. The conformation with the largest occupancy is depicted. There is a strong intramolecular hydrogen bond of O1—H⋯N1, occurring over a short O1⋯N1 distance of 2.612 (2) Å. This leads to the observed planar conformation in the O1—C2—C1—C7—N1 moiety. The torsion angles of the C2—C1—C7—N1 and C1—C7—N1—C8 moieties are 5.7 (3) and −178.8 (2)°. However, the torsion angle of C7—N1—C8—C9 is significantly large, 43.5 (3)°, leading to the large observed dihedral angle of 49.12 (7)° between the two terminal benzene rings. No unusually short contacts were observed in the crystal structure and the loose contacts between the tert-butyl groups of neighbouring molecules led to the disordered structure of the group. The crystals of (2)–(4) were composed of two crystallographically independent molecules, A and B, in their unit cells. The molecular structures of (2A), (2B), (3A), (3B), (4A), (4B) and (5) were found to be similar to that of (1), with the corresponding dihedral angles between the two benzene rings observed to be 48.44 (6), 46.40 (6), 45.07 (12), 45.29 (12), 44.37 (15), 44.66 (14) and 27.25 (19)°. The molecular structure of (6) is shown in Fig. 3. The bond distances and angles, the intramolecular hydrogen-bond distance and the torsion angles of the C2—C1—C7—N1 and C1—C7—N1—C8 moieties were found to be similar to those observed in the crystal structures of (1)–(5). Both the torsion angle of the C7—N1—C8—C9 moiety and the dihedral angle between the two terminal benzene rings, however, were found to be smaller at 25.0 (3) and 21.56 (12)°.

Figure 1
Molecular structure of N-salicylidene-4-tert-butylaniline (1). The displacement ellipsoids are drawn at the 50% probability level. The hydrogen bond is drawn in a dotted line. The tert-butyl group with the highest occupancy is shown.

Figure 2
Crystal structure of N-salicylidene-4-tert-butylaniline (1) viewed along the b axis. H atoms are omitted for clarity.

Figure 3
Molecular structure of N-3,5-di-tert-butylsalicylideneaniline (6). The displacement ellipsoids are drawn at the 50% probability level. The hydrogen bond is drawn as a dotted line.

The molecular and crystal structures of (8) are shown in Figs. 4 and 5. The bond distances and angles were found to be as anticipated. A strong intramolecular hydrogen bond of O1—H⋯N1 was observed over a short O1⋯N1 distance of 2.621 (3) Å. Compound (8) was found to be whole planar. The torsion angles of the C2—C1—C7—N1, C1—C7—N1—C8 and C7—N1—C8—C9 moieties were −3.3 (5), −178.3 (3) and 2.0 (5)°, and the dihedral angle between the two benzene rings was found to be 2.82 (20)°. These planar molecules are stacked as a sheet along the a and b axes and the sheets themselves are stacked alternately along the c axis. The crystals of (7) were also revealed to be whole planar in structure, in a similar manner to that observed in (8). It has been reported that (8) can exist in another polymorphic form, (8′) (Bregman et al., 1964; refcode CHILSAN). Whilst the reported crystal of (8′) reveals that the bond distances, bond angles and torsion angles of the C2—C1—C7—N1 and C1—C7—N1—C8 moieties are similar to those observed in (8), the aniline moiety of (8′) is twisted out of the plane resulting in the larger dihedral angle between the two terminal benzene rings of 51.1°. It is known that the ortho position atom of the aniline ring has an influence on the planarity in SA derivative molecules such as N-salicylidene-2-aminopyridine (Moustakali-Mavridis et al., 1978 , 1980 ), which is caused by the absence or presence of steric hindrance between azomethine H and the aniline ring. Similar hindrance would occur when the ortho-substituent is situated near the azomethine H. However, in this work the ortho-substituent of the aniline ring of (8) directs to the opposite direction to azomethine H. The only possible intramolecular interaction is between aniline and azomethine H atoms, which is expected for all ortho-, meta- and para- substituted SA molecules. Thus, it has almost equal influence on the molecular conformation among all mono-substituted SAs. The different dihedral angles in polymorphic crystals of (8) and (8′), as described above, clearly indicate that the molecular conformation is determined by the molecular packing and intermolecular interactions. The eight SA crystals with various dihedral angles in this study may be a good choice to discuss the relationship between the structures and photochromic characters, although the intramolecular hindrance may be an important factor to govern the relationship for the di-ortho-substituted SA crystals, which will be discussed in the following section.

Figure 4
Molecular structure of N-salicylidene-2-chloroaniline (8). The displacement ellipsoids are drawn at the 50% probability level. The hydrogen bond is drawn as a dotted line.

Figure 5
Crystal structure of N-salicylidene-2-chloroaniline (8) viewed along the c axis. H atoms are omitted for clarity.

3.2. Photochromic reactivity

The UV–vis absorption spectra for crystals of (1) and (8) are shown in Figs. 6(a) and (b). Following the photoirradiation of (1), a significant difference was observed in the spectrum between 400 and 600 nm. Spectral changes similar to those observed in (1) also occurred for crystals of (2)–(5) in the range 450–550 nm. In contrast to these observations, photoirradiation of (8) did not result in any discernible difference and the spectrum remained unchanged. Crystals of (6) and (7) also behaved in the same way as (8). This indicated that the crystals of (1)–(5) were photochromic and that those of (6)–(8) were non-photochromic. Interestingly, crystals of (8′), another polymorphic form of (8), were reported to be photochromic (Bregman et al., 1964; refcode CHILSAN).

Figure 6
Reflectance spectra (a) for (1) and (b) for (8). Dashed and full curves indicate before and after photoirradiation.

4. Discussion

The selected bond distances, bond angles, intramolecular hydrogen-bond lengths, torsion angles of the C2—C1—C7—N1, C1—C7—N1—C8 and C7—N1—C8—C9 moieties and the dihedral angles of the two benzene rings of (1)–(8) are summarized in Table 2. Each parameter is averaged across the 11 molecules except for the torsion angle of the C7—N1—C8—C9 moiety and the dihedral angle. The corresponding distances and angles are in good agreement with one another. The relation between the dihedral angles of the two terminal benzene rings and the photochromic properties is shown in Fig. 7. There are two polymorphic crystal forms, (8) and (8′), which are non-photochromic and photochromic, respectively. Previously we reported that the compound N-3,5-di-tert-butyl-salicylideneaniline-3-carboxyaniline (9) could exist in one of three polymorphic crystal forms, α, β and γ. The crystals of (9α) and (9β) exhibit photochromism and had dihedral angles of 60.95 (4) and 37.34 (6)°, respectively, whereas crystals of (9γ) were non-photochromic and had a dihedral angle of 28.90 (4)°. From Fig. 7 it is clear that the threshold value of the dihedral angle in relation to the occurrence of photochromic behaviour is 20 to 30°.

Table 2
Selected bond distances (Å), angles, torsion angles and dihedral angles (°) of the SA derivatives (1)–(8) and (8′)

	(1)	(2A)†	(2B)†	(3A)†	(3B)†	(4A)†	(4B)†
O1—C2	1.350 (3)	1.357 (2)	1.358 (2)	1.359 (4)	1.350 (4)	1.358 (4)	1.360 (4)
C2—C1	1.408 (3)	1.410 (2)	1.412 (2)	1.413 (4)	1.406 (5)	1.415 (5)	1.412 (5)
C1—C7	1.450 (3)	1.450 (2)	1.453 (2)	1.452 (5)	1.457 (5)	1.449 (5)	1.447 (5)
C7—N1	1.280 (3)	1.284 (2)	1.283 (2)	1.278 (5)	1.271 (4)	1.281 (4)	1.280 (4)
N1—C8	1.421 (3)	1.420 (2)	1.424 (2)	1.420 (4)	1.420 (4)	1.429 (4)	1.424 (5)
N1⋯O1	2.612 (2)	2.582 (2)	2.608 (2)	2.580 (4)	2.596 (3)	2.599 (4)	2.578 (4)
C1—C7—N1	121.8 (2)	122.5 (1)	123.2 (1)	122.1 (3)	122.8 (3)	122.8 (3)	122.8 (3)
C7—N1—C8	120.4 (2)	121.1 (1)	119.9 (1)	121.0 (3)	120.6 (3)	119.8 (3)	120.8 (3)
C2—C1—C7—N1	5.7 (3)	−1.8 (2)	0.8 (2)	0.3 (5)	0.5 (5)	−0.3 (6)	1.5 (5)
C1—C7—N1—C8	−178.8 (2)	173.6 (1)	−173.1 (1)	−178.0 (3)	−177.4 (3)	178.5 (3)	−179.5 (3)
C7—N1—C8—C9	43.5 (3)	−46.2 (2)	45.4 (2)	45.4 (5)	46.1 (5)	−46.5 (5)	45.5 (5)
Dihedral angle (φ)	49.12 (7)	48.44 (6)	46.40 (6)	45.07 (12)	45.29 (12)	44.37 (15)	44.66 (14)

	(5)	(6)	(7)	(8)	(8′)	Average (1)–(8)
O1—C2	1.361 (5)	1.352 (2)	1.344 (2)	1.354 (3)	1.3709	1.356 (5)
C2—C1	1.394 (6)	1.409 (3)	1.401 (3)	1.402 (4)	1.3960	1.407 (6)
C1—C7	1.464 (6)	1.457 (3)	1.444 (3)	1.452 (5)	1.4563	1.453 (6)
C7—N1	1.278 (5)	1.279 (3)	1.266 (3)	1.276 (4)	1.2812	1.278 (5)
N1—C8	1.432 (5)	1.422 (2)	1.421 (3)	1.412 (4)	1.4272	1.423 (5)
N1⋯O1	2.621 (5)	2.563 (2)	2.610 (2)	2.621 (3)	2.614	2.599 (5)
C1—C7—N1	123.5 (4)	121.7 (2)	123.5 (2)	121.4 (3)	121.46	122.5 (4)
C7—N1—C8	119.6 (4)	123.4 (2)	121.0 (2)	121.8 (3)	118.62	120.7 (4)
C2—C1—C7—N1	−0.4 (7)	−2.5 (3)	−2.2 (4)	−3.3 (5)	−3.84	–
C1—C7—N1—C8	179.0 (4)	−179.9 (2)	−175.6 (2)	−178.3 (3)	175.07	–
C7—N1—C8—C9	27.5 (6)	25.0 (3)	7.7 (4)	2.0 (5)	−46.99	–
Dihedral angle (φ)	27.25 (19)	21.56 (12)	8.74 (12)	2.82 (20)	51.1	–

†(2A), (2B), (3A), (3B), (4A) and (4B) are crystallographically independent molecules.

Figure 7
The relationship between photochromic properties and dihedral angles of SA derivatives. Each SA derivative corresponds to an open circle that indicates the photochromic property and the intramolecular dihedral angle between two benzene rings. The dihedral angles of SA derivative crystals are classified into photochromic (upper row) and non-photochromic (lower row) ones. Both types of photochromic and non-photochromic crystals are observed between 20 and 30°.

Recently it was reported that the twisted SA derivatives substituted with either methyl or tert-butyl groups at both ortho positions of the aniline ring were non-photochromic in spite of their large dihedral angles of 63.5 and 82.9°. In contrast, it was also reported in the same publication that SA derivatives substituted with either ethyl or isopropyl groups at the two ortho positions of the aniline ring exhibited photochromism and had dihedral angles of 82.3 and 73.6° (Fukuda et al., 2003). Based upon these observations, the authors claimed that crystal packing was responsible for the observed photochromic behaviour rather than the non-planarity of the molecules.

As discussed in the previous paper (Johmoto et al., 2009), photochromism occurs as a consequence of a structural change between enol and trans-keto forms (Cohen & Schmidt, 1962; Cohen et al., 1964; Harada et al., 1999), which is schematically depicted in Fig. 8. During the transformation from the enol to the trans-keto form, the H atom bonded to the OH group is transferred to the N atom and the cis-keto form is produced. The central single —(H)N—C(H)— bond of the cis-keto form rotates by 180° around an axis connecting the two benzene rings. The benzene rings slide up and down maintaining the conformation. Given that this pedal-like motion does not lead to large movements in the peripheral atoms of the molecule, the crystal structure is sustained in the photochromic reaction. However, if both of the ortho positions of the aniline rings are substituted with tert-butyl groups, it is impossible for the conformation to change from the cis-keto to the trans-keto form due to steric repulsion between the tert-butyl groups and the H atoms of the methine and imino groups, as depicted in Fig. 9(a) in which the distances between the N atom and four methyl C atoms of the tert-butyl group close to the N atom were 2.870 (6) Å for N1⋯C28, 3.000 (7) Å for N1⋯C12, 3.224 (8) Å for N1⋯C11 and 3.509 (7) Å for N1⋯C27, respectively. In contrast, for SA derivatives substituted at both ortho positions of the aniline ring with isopropyl and ethyl groups, the pedal motion can still occur without intramolecular steric hindrance, as shown in Fig. 9(b), in which the distances between the N atom and four methyl C atoms of the iso-propyl group were 3.715 (7) Å for N2⋯C38, 3.838 (6) Å for N2⋯C31, 4.043 (5) Å for N2⋯C30 and 4.137 (5) Å for N2⋯C37. For SA derivatives substituted at both ortho positions of the aniline ring with methyl groups, there are both photochromic and non-photochromic crystals. For the photochromic crystals, pedal motion can easily occur as observed in the crystals with diisopropyl and diethyl groups. For the non-photochromic crystals, on the other hand, pedal motion appears to be restricted by the close contact of neighbouring molecules, as shown in Fig. 9(c). The slide motion of the benzene ring is hindered by the short intermolecular contact distance between the OH and CH₃ groups, where O⋯C is 3.204 (3) Å. Such a short contact is not observed in the crystal structures of (1)–(5) (the shortest intermolecular C⋯C, C⋯O, C⋯N distances being greater than 3.5 Å).

Figure 8
A schematic drawing of the pedal motion. Two benzene rings only move as pedals of a bicycle as the central NH—CH plane turns upside down in the transformation from enol to the trans-keto form.

Figure 9
Schematic drawings of intramolecular steric hindrances for the SA molecules with (a) ortho-di-tert-butyl groups and (b) ortho-diisopropyl groups in the aniline rings. The distance ranges between the N atom and the nearest methyl C atoms of ⁱPr/^tBu were included (Fukuda et al., 2003

). (c) Steric hindrance between the methyl group at the ortho position and the phenol group of the neighbouring molecule. There is an unusually short contact between the OH and the CH₃ groups in a non-photochromic crystal with ortho-dimethyl groups in the aniline rings, the C⋯O distance being 3.204 (3) Å (Fukuda et al., 2003

These observations clearly indicate that the non-planarity of the SA derivatives is necessary to initiate pedal motion; localizing the π-electrons into the two terminal benzene rings and the central CH=NH group. The threshold value for non-planarity resulting in photochromic behaviour is a dihedral angle of at least 30° between the two terminal benzene rings. However, the impact of intra- and intermolecular steric hindrance upon pedal motion inhibition represents an important factor in determining photochromism.

Supporting information

Crystal structure: contains datablocks global, 2, 3, 4, 5, 6, 7, 8, 1. DOI: 10.1107/S0108768112010993/og5057sup1.cif

Structure factors: contains datablock shelxl. DOI: 10.1107/S0108768112010993/og50571sup2.hkl

Structure factors: contains datablock shelxl. DOI: 10.1107/S0108768112010993/og50572sup3.hkl

Structure factors: contains datablock shelxl. DOI: 10.1107/S0108768112010993/og50573sup4.hkl

Structure factors: contains datablock shelxl. DOI: 10.1107/S0108768112010993/og50574sup5.hkl

Structure factors: contains datablock shelxl. DOI: 10.1107/S0108768112010993/og50575sup6.hkl

Structure factors: contains datablock shelxl. DOI: 10.1107/S0108768112010993/og50576sup7.hkl

Structure factors: contains datablock shelxl. DOI: 10.1107/S0108768112010993/og50577sup8.hkl

Structure factors: contains datablock shelxl. DOI: 10.1107/S0108768112010993/og50578sup9.hkl

Reflectance spectra. DOI: 10.1107/S0108768112010993/og5057sup10.pdf

Computing details top

Data collection: Bruker SMART for (2); PROCESS-AUTO (Rigaku, 1998) for (3), (4), (5), (6), (7), (8), (1). Cell refinement: Bruker SAINT for (2); PROCESS-AUTO (Rigaku, 1998) for (3), (4), (5), (6), (7), (8), (1). Data reduction: Bruker SAINT & SADABS for (2); PROCESS-AUTO (Rigaku, 1998) for (3), (4), (5), (6), (7), (8), (1). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: Siemens SHELXTL for (2); ORTEP-3 (Farrugia, 2008) for (3), (4), (5), (6), (7), (8), (1). Software used to prepare material for publication: Siemens SHELXTL for (2); SHELXL97 (Sheldrick, 1997) for (3), (4), (5), (6), (7), (8), (1).

Figures top

(2) top

Crystal data top

C₂₂H₂₉NO₂	V = 2018.7 (7) Å³
M_r = 339.46	Z = 4
Triclinic, P1	F(000) = 736
a = 10.814 (2) Å	D_x = 1.117 Mg m⁻³
b = 12.011 (2) Å	Mo Kα radiation, λ = 0.71073 Å
c = 15.727 (3) Å	µ = 0.07 mm⁻¹
α = 89.25 (3)°	T = 293 K
β = 81.21 (3)°	0.34 × 0.26 × 0.06 mm
γ = 89.97 (3)°

Data collection top

Bruker SMART CCD area detector system diffractometer	10049 independent reflections
Radiation source: rotating anode X-ray tube	5423 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω scans	θ_max = 28.4°, θ_min = 1.3°
Absorption correction: multi-scan Absorption was corrected by SADABS	h = −14→14
T_min = 0.976, T_max = 0.996	k = −16→16
29048 measured reflections	l = −20→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.070P)²] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max < 0.001
10049 reflections	Δρ_max = 0.24 e Å⁻³
482 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0230 (19)

Crystal data top

C₂₂H₂₉NO₂	γ = 89.97 (3)°
M_r = 339.46	V = 2018.7 (7) Å³
Triclinic, P1	Z = 4
a = 10.814 (2) Å	Mo Kα radiation
b = 12.011 (2) Å	µ = 0.07 mm⁻¹
c = 15.727 (3) Å	T = 293 K
α = 89.25 (3)°	0.34 × 0.26 × 0.06 mm
β = 81.21 (3)°

Data collection top

Bruker SMART CCD area detector system diffractometer	10049 independent reflections
Absorption correction: multi-scan Absorption was corrected by SADABS	5423 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.996	R_int = 0.036
29048 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 0.92	Δρ_max = 0.24 e Å⁻³
10049 reflections	Δρ_min = −0.16 e Å⁻³
482 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1A	0.26160 (9)	0.91706 (9)	0.30225 (6)	0.0575 (3)
H1A	0.2289	0.8774	0.3423	0.086*
O2A	0.11999 (10)	0.50309 (9)	0.59327 (6)	0.0615 (3)
N1A	0.08533 (11)	0.82448 (10)	0.40939 (7)	0.0493 (3)
C1A	0.04400 (12)	0.94569 (11)	0.29462 (9)	0.0436 (3)
C2A	0.17138 (12)	0.96591 (11)	0.26341 (8)	0.0426 (3)
C3A	0.20680 (12)	1.03807 (10)	0.19246 (8)	0.0409 (3)
C4A	0.11019 (13)	1.08733 (11)	0.15609 (9)	0.0463 (3)
H4A	0.1320	1.1347	0.1089	0.056*
C5A	−0.01745 (13)	1.07052 (11)	0.18561 (9)	0.0473 (3)
C6A	−0.04779 (13)	0.99881 (11)	0.25485 (9)	0.0489 (3)
H6A	−0.1317	0.9853	0.2758	0.059*
C7A	0.00611 (13)	0.87464 (11)	0.36927 (9)	0.0478 (3)
H7A	−0.0788	0.8650	0.3889	0.057*
C8A	0.04573 (12)	0.76462 (11)	0.48721 (8)	0.0447 (3)
C9A	−0.03946 (14)	0.80885 (13)	0.55320 (10)	0.0531 (4)
H9A	−0.0766	0.8775	0.5460	0.064*
C10A	−0.06840 (15)	0.74973 (13)	0.62976 (10)	0.0567 (4)
H10A	−0.1255	0.7790	0.6740	0.068*
C11A	−0.01413 (14)	0.64866 (13)	0.64124 (9)	0.0533 (4)
H11A	−0.0345	0.6097	0.6930	0.064*
C12A	0.07160 (12)	0.60438 (12)	0.57536 (9)	0.0452 (3)
C13A	0.10287 (12)	0.66291 (11)	0.49848 (8)	0.0450 (3)
H13A	0.1616	0.6343	0.4548	0.054*
C14A	0.34548 (12)	1.06197 (11)	0.15895 (9)	0.0454 (3)
C15A	0.41406 (15)	0.95337 (13)	0.13126 (11)	0.0615 (4)
H15A	0.5006	0.9692	0.1108	0.092*
H15B	0.3767	0.9201	0.0862	0.092*
H15C	0.4079	0.9029	0.1796	0.092*
C16A	0.40614 (15)	1.11831 (14)	0.22982 (11)	0.0663 (4)
H16A	0.3662	1.1886	0.2437	0.099*
H16B	0.4935	1.1302	0.2097	0.099*
H16C	0.3965	1.0713	0.2802	0.099*
C17A	0.36138 (15)	1.13961 (14)	0.07972 (11)	0.0654 (5)
H17A	0.3200	1.2090	0.0945	0.098*
H17B	0.3253	1.1054	0.0344	0.098*
H17C	0.4488	1.1530	0.0607	0.098*
C18A	−0.11994 (14)	1.13033 (14)	0.14451 (11)	0.0604 (4)
C19A	−0.0694 (3)	1.2127 (3)	0.0753 (3)	0.1221 (16)	0.781 (3)
H19A	−0.1376	1.2476	0.0527	0.183*	0.781 (3)
H19B	−0.0171	1.1748	0.0299	0.183*	0.781 (3)
H19C	−0.0212	1.2683	0.0989	0.183*	0.781 (3)
C20A	−0.2047 (2)	1.1983 (2)	0.21690 (18)	0.0891 (9)	0.781 (3)
H20A	−0.1540	1.2512	0.2412	0.134*	0.781 (3)
H20B	−0.2427	1.1480	0.2612	0.134*	0.781 (3)
H20C	−0.2687	1.2368	0.1922	0.134*	0.781 (3)
C21A	−0.2069 (3)	1.0478 (2)	0.1134 (2)	0.0994 (11)	0.781 (3)
H21A	−0.2700	1.0869	0.0882	0.149*	0.781 (3)
H21B	−0.2459	1.0031	0.1611	0.149*	0.781 (3)
H21C	−0.1604	1.0008	0.0712	0.149*	0.781 (3)
C19C	−0.0946 (9)	1.0854 (8)	0.0395 (5)	0.077 (3)*	0.219 (3)
H19G	−0.1566	1.1171	0.0088	0.115*	0.219 (3)
H19H	−0.1003	1.0056	0.0389	0.115*	0.219 (3)
H19I	−0.0129	1.1084	0.0124	0.115*	0.219 (3)
C20C	−0.2449 (11)	1.0963 (10)	0.1751 (8)	0.105 (4)*	0.219 (3)
H20G	−0.2626	1.1063	0.2362	0.157*	0.219 (3)
H20H	−0.2547	1.0192	0.1623	0.157*	0.219 (3)
H20I	−0.3018	1.1404	0.1476	0.157*	0.219 (3)
C21C	−0.0980 (11)	1.2472 (9)	0.1402 (8)	0.098 (4)*	0.219 (3)
H21G	−0.1493	1.2812	0.1025	0.148*	0.219 (3)
H21H	−0.0115	1.2613	0.1186	0.148*	0.219 (3)
H21I	−0.1185	1.2778	0.1967	0.148*	0.219 (3)
C22A	0.20307 (15)	0.44936 (13)	0.52776 (10)	0.0614 (4)
H22A	0.1636	0.4421	0.4774	0.092*
H22B	0.2237	0.3769	0.5478	0.092*
H22C	0.2780	0.4929	0.5138	0.092*
O1B	0.32685 (9)	0.41505 (9)	0.30108 (7)	0.0609 (3)
H1B	0.3391	0.3749	0.3415	0.091*
O2B	0.33447 (10)	−0.00283 (9)	0.59826 (7)	0.0653 (3)
N1B	0.44893 (11)	0.31879 (10)	0.41261 (7)	0.0504 (3)
C1B	0.54690 (13)	0.44130 (11)	0.29978 (9)	0.0448 (3)
C2B	0.43631 (13)	0.46334 (11)	0.26513 (9)	0.0464 (3)
C3B	0.43825 (13)	0.53654 (11)	0.19456 (9)	0.0466 (3)
C4B	0.55188 (13)	0.58686 (11)	0.16310 (9)	0.0486 (3)
H4B	0.5543	0.6353	0.1163	0.058*
C5B	0.66331 (13)	0.56998 (11)	0.19678 (9)	0.0456 (3)
C6B	0.65786 (13)	0.49516 (11)	0.26468 (9)	0.0472 (3)
H6B	0.7304	0.4801	0.2878	0.057*
C7B	0.54721 (14)	0.36846 (11)	0.37421 (9)	0.0488 (3)
H7B	0.6223	0.3573	0.3950	0.059*
C8B	0.45342 (12)	0.25857 (11)	0.49065 (9)	0.0452 (3)
C9B	0.50991 (14)	0.30282 (13)	0.55602 (10)	0.0535 (4)
H9B	0.5500	0.3715	0.5484	0.064*
C10B	0.50633 (15)	0.24424 (14)	0.63257 (10)	0.0576 (4)
H10B	0.5441	0.2739	0.6765	0.069*
C11B	0.44782 (14)	0.14301 (13)	0.64438 (9)	0.0552 (4)
H11B	0.4465	0.1041	0.6960	0.066*
C12B	0.39044 (12)	0.09817 (12)	0.57931 (9)	0.0467 (3)
C13B	0.39176 (12)	0.15650 (12)	0.50226 (9)	0.0466 (3)
H13B	0.3519	0.1277	0.4590	0.056*
C14B	0.31869 (15)	0.56142 (13)	0.15527 (11)	0.0585 (4)
C15B	0.26165 (17)	0.45300 (14)	0.12800 (12)	0.0738 (5)
H15D	0.3215	0.4161	0.0864	0.111*
H15E	0.1880	0.4698	0.1031	0.111*
H15F	0.2398	0.4053	0.1775	0.111*
C16B	0.22373 (17)	0.62104 (16)	0.22195 (14)	0.0878 (6)
H16D	0.1475	0.6329	0.1989	0.132*
H16E	0.2574	0.6915	0.2353	0.132*
H16F	0.2069	0.5760	0.2733	0.132*
C17B	0.34671 (19)	0.63563 (16)	0.07397 (13)	0.0878 (6)
H17D	0.4048	0.5984	0.0314	0.132*
H17E	0.3823	0.7048	0.0883	0.132*
H17F	0.2705	0.6499	0.0515	0.132*
C18B	0.78544 (14)	0.63148 (12)	0.16191 (9)	0.0525 (4)
C19B	0.76534 (19)	0.72396 (17)	0.09788 (14)	0.0935 (7)
H19D	0.7026	0.7744	0.1244	0.140*
H19E	0.7384	0.6920	0.0481	0.140*
H19F	0.8424	0.7636	0.0808	0.140*
C20B	0.88011 (19)	0.54865 (17)	0.11728 (14)	0.0923 (6)
H20D	0.9557	0.5872	0.0940	0.138*
H20E	0.8459	0.5133	0.0716	0.138*
H20F	0.8983	0.4933	0.1582	0.138*
C21B	0.84038 (17)	0.68501 (16)	0.23530 (12)	0.0770 (5)
H21D	0.7789	0.7325	0.2670	0.116*
H21E	0.9126	0.7283	0.2122	0.116*
H21F	0.8642	0.6279	0.2729	0.116*
C22B	0.28247 (15)	−0.05866 (13)	0.53324 (11)	0.0646 (4)
H22D	0.2149	−0.0154	0.5171	0.097*
H22E	0.2515	−0.1302	0.5546	0.097*
H22F	0.3457	−0.0683	0.4840	0.097*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.0441 (6)	0.0710 (7)	0.0574 (6)	0.0081 (5)	−0.0094 (5)	0.0195 (5)
O2A	0.0678 (7)	0.0624 (7)	0.0543 (6)	0.0170 (5)	−0.0101 (5)	0.0110 (5)
N1A	0.0473 (7)	0.0511 (7)	0.0485 (7)	−0.0003 (5)	−0.0047 (5)	0.0093 (6)
C1A	0.0414 (7)	0.0431 (7)	0.0460 (8)	0.0002 (6)	−0.0059 (6)	0.0036 (6)
C2A	0.0410 (7)	0.0434 (7)	0.0439 (8)	0.0056 (6)	−0.0085 (6)	0.0014 (6)
C3A	0.0402 (7)	0.0396 (7)	0.0423 (7)	0.0011 (6)	−0.0044 (6)	−0.0013 (6)
C4A	0.0456 (8)	0.0461 (8)	0.0470 (8)	0.0011 (6)	−0.0073 (6)	0.0062 (6)
C5A	0.0410 (8)	0.0469 (8)	0.0546 (9)	0.0025 (6)	−0.0101 (6)	0.0057 (7)
C6A	0.0376 (7)	0.0503 (8)	0.0585 (9)	−0.0018 (6)	−0.0067 (6)	0.0059 (7)
C7A	0.0435 (8)	0.0493 (8)	0.0493 (8)	−0.0015 (6)	−0.0032 (6)	0.0034 (7)
C8A	0.0408 (7)	0.0502 (8)	0.0432 (8)	−0.0041 (6)	−0.0079 (6)	0.0043 (6)
C9A	0.0532 (9)	0.0507 (8)	0.0550 (9)	0.0068 (7)	−0.0066 (7)	−0.0013 (7)
C10A	0.0554 (9)	0.0665 (10)	0.0455 (8)	0.0065 (8)	0.0017 (7)	−0.0048 (7)
C11A	0.0534 (9)	0.0665 (10)	0.0392 (8)	−0.0009 (7)	−0.0047 (6)	0.0053 (7)
C12A	0.0422 (7)	0.0518 (8)	0.0435 (8)	−0.0002 (6)	−0.0133 (6)	0.0031 (6)
C13A	0.0383 (7)	0.0554 (8)	0.0409 (8)	0.0027 (6)	−0.0051 (6)	0.0006 (6)
C14A	0.0389 (7)	0.0459 (8)	0.0495 (8)	0.0028 (6)	−0.0010 (6)	0.0011 (6)
C15A	0.0557 (9)	0.0604 (10)	0.0641 (10)	0.0131 (8)	0.0045 (7)	−0.0037 (8)
C16A	0.0504 (9)	0.0716 (11)	0.0762 (11)	−0.0089 (8)	−0.0068 (8)	−0.0107 (9)
C17A	0.0536 (9)	0.0651 (10)	0.0719 (11)	0.0007 (8)	0.0069 (8)	0.0176 (9)
C18A	0.0461 (9)	0.0629 (10)	0.0747 (11)	0.0020 (7)	−0.0193 (8)	0.0191 (8)
C19A	0.0641 (16)	0.158 (3)	0.141 (3)	0.0204 (18)	−0.0125 (17)	0.105 (3)
C20A	0.0744 (17)	0.0896 (19)	0.106 (2)	0.0367 (14)	−0.0239 (15)	−0.0056 (15)
C21A	0.092 (2)	0.091 (2)	0.132 (3)	0.0083 (16)	−0.073 (2)	−0.0083 (18)
C22A	0.0545 (9)	0.0582 (9)	0.0734 (11)	0.0094 (8)	−0.0158 (8)	−0.0024 (8)
O1B	0.0450 (6)	0.0709 (7)	0.0681 (7)	−0.0068 (5)	−0.0136 (5)	0.0122 (6)
O2B	0.0674 (7)	0.0662 (7)	0.0615 (7)	−0.0176 (6)	−0.0082 (5)	0.0123 (6)
N1B	0.0499 (7)	0.0522 (7)	0.0503 (7)	−0.0022 (6)	−0.0117 (6)	0.0066 (6)
C1B	0.0465 (8)	0.0427 (7)	0.0467 (8)	0.0022 (6)	−0.0122 (6)	0.0031 (6)
C2B	0.0437 (8)	0.0440 (8)	0.0529 (8)	0.0000 (6)	−0.0122 (6)	−0.0022 (7)
C3B	0.0506 (8)	0.0409 (7)	0.0525 (8)	0.0047 (6)	−0.0206 (6)	−0.0036 (6)
C4B	0.0581 (9)	0.0423 (8)	0.0483 (8)	0.0016 (7)	−0.0175 (7)	0.0037 (6)
C5B	0.0486 (8)	0.0442 (8)	0.0458 (8)	0.0010 (6)	−0.0130 (6)	0.0023 (6)
C6B	0.0445 (8)	0.0484 (8)	0.0509 (8)	0.0017 (6)	−0.0143 (6)	0.0046 (7)
C7B	0.0464 (8)	0.0487 (8)	0.0528 (8)	0.0021 (7)	−0.0132 (7)	0.0020 (7)
C8B	0.0398 (7)	0.0510 (8)	0.0449 (8)	0.0044 (6)	−0.0066 (6)	0.0032 (6)
C9B	0.0542 (9)	0.0525 (9)	0.0544 (9)	−0.0045 (7)	−0.0099 (7)	−0.0035 (7)
C10B	0.0576 (9)	0.0706 (10)	0.0474 (9)	−0.0005 (8)	−0.0166 (7)	−0.0069 (8)
C11B	0.0523 (9)	0.0704 (10)	0.0431 (8)	0.0026 (8)	−0.0083 (7)	0.0074 (7)
C12B	0.0382 (7)	0.0525 (8)	0.0477 (8)	0.0016 (6)	−0.0017 (6)	0.0033 (7)
C13B	0.0381 (7)	0.0579 (9)	0.0447 (8)	−0.0013 (6)	−0.0090 (6)	−0.0009 (7)
C14B	0.0579 (9)	0.0506 (9)	0.0743 (11)	0.0049 (7)	−0.0333 (8)	−0.0028 (8)
C15B	0.0784 (12)	0.0674 (11)	0.0852 (13)	−0.0044 (9)	−0.0426 (10)	−0.0080 (9)
C16B	0.0661 (12)	0.0837 (13)	0.1221 (17)	0.0279 (10)	−0.0396 (11)	−0.0277 (12)
C17B	0.0908 (14)	0.0792 (13)	0.1077 (15)	−0.0036 (10)	−0.0630 (12)	0.0277 (11)
C18B	0.0507 (8)	0.0555 (9)	0.0515 (9)	−0.0016 (7)	−0.0090 (7)	0.0104 (7)
C19B	0.0795 (13)	0.0980 (15)	0.1046 (16)	−0.0216 (11)	−0.0234 (11)	0.0506 (13)
C20B	0.0705 (13)	0.0915 (14)	0.1068 (16)	0.0015 (11)	0.0132 (11)	−0.0078 (12)
C21B	0.0693 (11)	0.0839 (13)	0.0789 (12)	−0.0235 (10)	−0.0151 (9)	0.0049 (10)
C22B	0.0542 (9)	0.0570 (10)	0.0828 (12)	−0.0067 (8)	−0.0105 (8)	−0.0027 (9)

Geometric parameters (Å, º) top

O1A—C2A	1.3569 (16)	C18A—C19C	1.726 (8)
O2A—C12A	1.3669 (17)	O1B—C2B	1.3583 (17)
O2A—C22A	1.4210 (19)	O2B—C12B	1.3649 (17)
N1A—C7A	1.2843 (18)	O2B—C22B	1.4162 (19)
N1A—C8A	1.4197 (17)	N1B—C7B	1.2827 (18)
C1A—C6A	1.4008 (19)	N1B—C8B	1.4236 (17)
C1A—C2A	1.4101 (19)	C1B—C6B	1.397 (2)
C1A—C7A	1.4497 (19)	C1B—C2B	1.4114 (19)
C2A—C3A	1.4098 (18)	C1B—C7B	1.4527 (19)
C3A—C4A	1.3935 (19)	C2B—C3B	1.405 (2)
C3A—C14A	1.5376 (19)	C3B—C4B	1.388 (2)
C4A—C5A	1.4014 (19)	C3B—C14B	1.543 (2)
C5A—C6A	1.379 (2)	C4B—C5B	1.4020 (19)
C5A—C18A	1.539 (2)	C5B—C6B	1.3810 (19)
C8A—C9A	1.389 (2)	C5B—C18B	1.536 (2)
C8A—C13A	1.3901 (19)	C8B—C9B	1.385 (2)
C9A—C10A	1.384 (2)	C8B—C13B	1.3924 (19)
C10A—C11A	1.370 (2)	C9B—C10B	1.382 (2)
C11A—C12A	1.391 (2)	C10B—C11B	1.368 (2)
C12A—C13A	1.3870 (19)	C11B—C12B	1.390 (2)
C14A—C15A	1.535 (2)	C12B—C13B	1.3900 (19)
C14A—C17A	1.535 (2)	C14B—C15B	1.535 (2)
C14A—C16A	1.541 (2)	C14B—C16B	1.535 (2)
C18A—C20C	1.422 (11)	C14B—C17B	1.541 (2)
C18A—C21C	1.422 (11)	C18B—C21B	1.526 (2)
C18A—C19A	1.501 (3)	C18B—C20B	1.526 (2)
C18A—C21A	1.503 (3)	C18B—C19B	1.527 (2)
C18A—C20A	1.583 (3)

C12A—O2A—C22A	118.76 (11)	C5A—C18A—C20A	108.34 (14)
C7A—N1A—C8A	121.09 (12)	C20C—C18A—C19C	103.6 (6)
C6A—C1A—C2A	119.36 (13)	C21C—C18A—C19C	105.9 (6)
C6A—C1A—C7A	119.31 (13)	C19A—C18A—C19C	62.0 (3)
C2A—C1A—C7A	121.29 (12)	C21A—C18A—C19C	59.3 (3)
O1A—C2A—C3A	119.13 (12)	C5A—C18A—C19C	103.5 (3)
O1A—C2A—C1A	120.20 (12)	C20A—C18A—C19C	148.0 (3)
C3A—C2A—C1A	120.67 (12)	C12B—O2B—C22B	118.84 (12)
C4A—C3A—C2A	116.61 (12)	C7B—N1B—C8B	119.95 (12)
C4A—C3A—C14A	122.41 (12)	C6B—C1B—C2B	119.43 (13)
C2A—C3A—C14A	120.97 (12)	C6B—C1B—C7B	118.81 (13)
C3A—C4A—C5A	124.58 (13)	C2B—C1B—C7B	121.67 (13)
C6A—C5A—C4A	116.82 (13)	O1B—C2B—C3B	119.70 (13)
C6A—C5A—C18A	121.00 (13)	O1B—C2B—C1B	119.90 (13)
C4A—C5A—C18A	122.17 (13)	C3B—C2B—C1B	120.39 (13)
C5A—C6A—C1A	121.95 (13)	C4B—C3B—C2B	116.91 (13)
N1A—C7A—C1A	122.54 (13)	C4B—C3B—C14B	121.76 (13)
C9A—C8A—C13A	120.35 (13)	C2B—C3B—C14B	121.32 (13)
C9A—C8A—N1A	121.88 (13)	C3B—C4B—C5B	124.78 (13)
C13A—C8A—N1A	117.57 (12)	C6B—C5B—C4B	116.34 (13)
C10A—C9A—C8A	119.30 (14)	C6B—C5B—C18B	120.94 (12)
C11A—C10A—C9A	120.93 (14)	C4B—C5B—C18B	122.71 (12)
C10A—C11A—C12A	119.89 (14)	C5B—C6B—C1B	122.11 (13)
O2A—C12A—C13A	124.70 (13)	N1B—C7B—C1B	123.20 (13)
O2A—C12A—C11A	115.24 (13)	C9B—C8B—C13B	120.35 (13)
C13A—C12A—C11A	120.06 (13)	C9B—C8B—N1B	121.41 (13)
C12A—C13A—C8A	119.46 (13)	C13B—C8B—N1B	118.10 (13)
C15A—C14A—C17A	106.84 (12)	C10B—C9B—C8B	119.58 (14)
C15A—C14A—C3A	110.18 (12)	C11B—C10B—C9B	120.71 (14)
C17A—C14A—C3A	111.70 (12)	C10B—C11B—C12B	120.12 (14)
C15A—C14A—C16A	110.33 (13)	O2B—C12B—C11B	115.11 (13)
C17A—C14A—C16A	108.17 (13)	O2B—C12B—C13B	124.89 (13)
C3A—C14A—C16A	109.56 (11)	C11B—C12B—C13B	119.99 (14)
C20C—C18A—C21C	116.0 (7)	C12B—C13B—C8B	119.23 (13)
C20C—C18A—C19A	130.7 (5)	C15B—C14B—C16B	109.89 (15)
C21C—C18A—C19A	44.4 (5)	C15B—C14B—C17B	106.78 (14)
C20C—C18A—C21A	46.5 (5)	C16B—C14B—C17B	108.87 (15)
C21C—C18A—C21A	138.4 (5)	C15B—C14B—C3B	110.40 (12)
C19A—C18A—C21A	111.8 (2)	C16B—C14B—C3B	109.25 (13)
C20C—C18A—C5A	115.8 (5)	C17B—C14B—C3B	111.62 (14)
C21C—C18A—C5A	110.4 (5)	C21B—C18B—C20B	108.68 (15)
C19A—C18A—C5A	113.48 (15)	C21B—C18B—C19B	107.44 (15)
C21A—C18A—C5A	110.93 (15)	C20B—C18B—C19B	108.81 (15)
C20C—C18A—C20A	59.3 (5)	C21B—C18B—C5B	110.39 (12)
C21C—C18A—C20A	65.8 (5)	C20B—C18B—C5B	109.30 (13)
C19A—C18A—C20A	106.7 (2)	C19B—C18B—C5B	112.13 (13)
C21A—C18A—C20A	105.05 (19)

C6A—C1A—C2A—O1A	178.60 (12)	C4A—C5A—C18A—C20A	−122.34 (18)
C7A—C1A—C2A—O1A	1.2 (2)	C6A—C5A—C18A—C19C	−120.2 (4)
C6A—C1A—C2A—C3A	−0.5 (2)	C4A—C5A—C18A—C19C	61.0 (4)
C7A—C1A—C2A—C3A	−177.92 (12)	C6B—C1B—C2B—O1B	−177.22 (13)
O1A—C2A—C3A—C4A	−178.93 (12)	C7B—C1B—C2B—O1B	−0.6 (2)
C1A—C2A—C3A—C4A	0.20 (19)	C6B—C1B—C2B—C3B	1.6 (2)
O1A—C2A—C3A—C14A	−0.10 (19)	C7B—C1B—C2B—C3B	178.25 (12)
C1A—C2A—C3A—C14A	179.03 (12)	O1B—C2B—C3B—C4B	177.30 (12)
C2A—C3A—C4A—C5A	0.5 (2)	C1B—C2B—C3B—C4B	−1.6 (2)
C14A—C3A—C4A—C5A	−178.29 (13)	O1B—C2B—C3B—C14B	−1.5 (2)
C3A—C4A—C5A—C6A	−0.9 (2)	C1B—C2B—C3B—C14B	179.66 (12)
C3A—C4A—C5A—C18A	177.99 (14)	C2B—C3B—C4B—C5B	−0.2 (2)
C4A—C5A—C6A—C1A	0.5 (2)	C14B—C3B—C4B—C5B	178.57 (13)
C18A—C5A—C6A—C1A	−178.36 (14)	C3B—C4B—C5B—C6B	1.8 (2)
C2A—C1A—C6A—C5A	0.1 (2)	C3B—C4B—C5B—C18B	−177.40 (14)
C7A—C1A—C6A—C5A	177.59 (13)	C4B—C5B—C6B—C1B	−1.7 (2)
C8A—N1A—C7A—C1A	173.59 (12)	C18B—C5B—C6B—C1B	177.51 (13)
C6A—C1A—C7A—N1A	−179.19 (14)	C2B—C1B—C6B—C5B	0.1 (2)
C2A—C1A—C7A—N1A	−1.8 (2)	C7B—C1B—C6B—C5B	−176.61 (13)
C7A—N1A—C8A—C9A	−46.2 (2)	C8B—N1B—C7B—C1B	−173.09 (12)
C7A—N1A—C8A—C13A	138.88 (14)	C6B—C1B—C7B—N1B	177.39 (14)
C13A—C8A—C9A—C10A	−1.1 (2)	C2B—C1B—C7B—N1B	0.8 (2)
N1A—C8A—C9A—C10A	−175.82 (14)	C7B—N1B—C8B—C9B	45.41 (19)
C8A—C9A—C10A—C11A	0.1 (2)	C7B—N1B—C8B—C13B	−138.92 (14)
C9A—C10A—C11A—C12A	0.1 (2)	C13B—C8B—C9B—C10B	0.9 (2)
C22A—O2A—C12A—C13A	−3.8 (2)	N1B—C8B—C9B—C10B	176.51 (13)
C22A—O2A—C12A—C11A	176.65 (13)	C8B—C9B—C10B—C11B	0.1 (2)
C10A—C11A—C12A—O2A	−179.83 (13)	C9B—C10B—C11B—C12B	−0.4 (2)
C10A—C11A—C12A—C13A	0.6 (2)	C22B—O2B—C12B—C11B	−175.01 (13)
O2A—C12A—C13A—C8A	178.93 (13)	C22B—O2B—C12B—C13B	5.8 (2)
C11A—C12A—C13A—C8A	−1.5 (2)	C10B—C11B—C12B—O2B	−179.67 (13)
C9A—C8A—C13A—C12A	1.8 (2)	C10B—C11B—C12B—C13B	−0.4 (2)
N1A—C8A—C13A—C12A	176.72 (12)	O2B—C12B—C13B—C8B	−179.36 (12)
C4A—C3A—C14A—C15A	−121.68 (14)	C11B—C12B—C13B—C8B	1.4 (2)
C2A—C3A—C14A—C15A	59.56 (17)	C9B—C8B—C13B—C12B	−1.7 (2)
C4A—C3A—C14A—C17A	−3.09 (18)	N1B—C8B—C13B—C12B	−177.42 (12)
C2A—C3A—C14A—C17A	178.15 (12)	C4B—C3B—C14B—C15B	124.90 (16)
C4A—C3A—C14A—C16A	116.75 (15)	C2B—C3B—C14B—C15B	−56.38 (19)
C2A—C3A—C14A—C16A	−62.01 (16)	C4B—C3B—C14B—C16B	−114.15 (17)
C6A—C5A—C18A—C20C	−7.6 (7)	C2B—C3B—C14B—C16B	64.57 (18)
C4A—C5A—C18A—C20C	173.6 (6)	C4B—C3B—C14B—C17B	6.3 (2)
C6A—C5A—C18A—C21C	126.8 (6)	C2B—C3B—C14B—C17B	−174.98 (14)
C4A—C5A—C18A—C21C	−52.0 (6)	C6B—C5B—C18B—C21B	−50.43 (19)
C6A—C5A—C18A—C19A	174.8 (2)	C4B—C5B—C18B—C21B	128.77 (15)
C4A—C5A—C18A—C19A	−4.0 (3)	C6B—C5B—C18B—C20B	69.06 (18)
C6A—C5A—C18A—C21A	−58.3 (2)	C4B—C5B—C18B—C20B	−111.74 (17)
C4A—C5A—C18A—C21A	122.9 (2)	C6B—C5B—C18B—C19B	−170.19 (15)
C6A—C5A—C18A—C20A	56.5 (2)	C4B—C5B—C18B—C19B	9.0 (2)

(3) top

Crystal data top

C₂₁H₂₆BrNO	Z = 4
M_r = 388.34	F(000) = 808
Triclinic, P1	D_x = 1.288 Mg m⁻³
a = 10.7505 (6) Å	Mo Kα radiation, λ = 0.71075 Å
b = 11.5008 (7) Å	Cell parameters from 12241 reflections
c = 16.3284 (8) Å	θ = 3.0–27.4°
α = 87.959 (1)°	µ = 2.06 mm⁻¹
β = 83.166 (2)°	T = 296 K
γ = 89.536 (2)°	Block, yellow
V = 2003.20 (19) Å³	0.18 × 0.17 × 0.04 mm

Data collection top

Rigaku R-AXIS RAPID IP Area Detector System diffractometer	9015 independent reflections
Radiation source: rotating anode X-ray tube	4719 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ω scans	θ_max = 27.4°, θ_min = 3.0°
Absorption correction: multi-scan Absorption was corrected by ABSCOR	h = −13→13
T_min = 0.189, T_max = 0.928	k = −14→14
19830 measured reflections	l = −21→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0608P)²] where P = (F_o² + 2F_c²)/3
9015 reflections	(Δ/σ)_max = 0.001
445 parameters	Δρ_max = 0.87 e Å⁻³
0 restraints	Δρ_min = −0.78 e Å⁻³

Crystal data top

C₂₁H₂₆BrNO	γ = 89.536 (2)°
M_r = 388.34	V = 2003.20 (19) Å³
Triclinic, P1	Z = 4
a = 10.7505 (6) Å	Mo Kα radiation
b = 11.5008 (7) Å	µ = 2.06 mm⁻¹
c = 16.3284 (8) Å	T = 296 K
α = 87.959 (1)°	0.18 × 0.17 × 0.04 mm
β = 83.166 (2)°

Data collection top

Rigaku R-AXIS RAPID IP Area Detector System diffractometer	9015 independent reflections
Absorption correction: multi-scan Absorption was corrected by ABSCOR	4719 reflections with I > 2σ(I)
T_min = 0.189, T_max = 0.928	R_int = 0.054
19830 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.08	Δρ_max = 0.87 e Å⁻³
9015 reflections	Δρ_min = −0.78 e Å⁻³
445 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1A	0.67859 (4)	0.53468 (3)	0.56212 (2)	0.06671 (15)
O1A	0.7848 (2)	0.0614 (2)	0.30884 (14)	0.0556 (6)
H1A	0.7518	0.0995	0.3471	0.083*
N1A	0.6084 (3)	0.1570 (2)	0.40508 (16)	0.0492 (7)
C1A	0.5672 (3)	0.0401 (3)	0.29328 (19)	0.0433 (8)
C2A	0.6949 (3)	0.0180 (3)	0.26676 (19)	0.0429 (8)
C3A	0.7301 (3)	−0.0490 (3)	0.19788 (19)	0.0427 (7)
C4A	0.6337 (3)	−0.0954 (3)	0.1594 (2)	0.0460 (8)
H4A	0.6558	−0.1412	0.1141	0.055*
C5A	0.5057 (3)	−0.0779 (3)	0.1842 (2)	0.0465 (8)
C6A	0.4758 (3)	−0.0084 (3)	0.2507 (2)	0.0482 (8)
H6A	0.3919	0.0069	0.2679	0.058*
C7A	0.5290 (3)	0.1109 (3)	0.36385 (19)	0.0466 (8)
H7A	0.4440	0.1232	0.3795	0.056*
C8A	0.5685 (3)	0.2228 (3)	0.47549 (19)	0.0457 (8)
C9A	0.4735 (3)	0.1848 (3)	0.5362 (2)	0.0519 (9)
H9A	0.4319	0.1154	0.5307	0.062*
C10A	0.4422 (4)	0.2508 (3)	0.6039 (2)	0.0629 (10)
H10A	0.3793	0.2251	0.6445	0.075*
C11A	0.5023 (4)	0.3554 (3)	0.6134 (2)	0.0584 (10)
H11A	0.4800	0.4000	0.6594	0.070*
C12A	0.5958 (3)	0.3912 (3)	0.5529 (2)	0.0478 (8)
C13A	0.6308 (3)	0.3259 (3)	0.48403 (19)	0.0469 (8)
H13A	0.6951	0.3510	0.4443	0.056*
C14A	0.8681 (3)	−0.0719 (3)	0.1666 (2)	0.0469 (8)
C15A	0.9312 (4)	−0.1404 (3)	0.2339 (2)	0.0656 (10)
H15A	0.8915	−0.2147	0.2448	0.098*
H15B	0.9230	−0.0973	0.2836	0.098*
H15C	1.0184	−0.1516	0.2151	0.098*
C16A	0.9368 (4)	0.0440 (3)	0.1451 (2)	0.0641 (10)
H16A	1.0241	0.0290	0.1291	0.096*
H16B	0.9274	0.0919	0.1924	0.096*
H16C	0.9017	0.0834	0.1003	0.096*
C17A	0.8844 (4)	−0.1430 (4)	0.0897 (2)	0.0709 (11)
H17A	0.8469	−0.2181	0.1018	0.106*
H17B	0.9720	−0.1524	0.0715	0.106*
H17C	0.8445	−0.1036	0.0469	0.106*
C18A	0.4025 (3)	−0.1354 (3)	0.1425 (2)	0.0555 (9)
C19A	0.4528 (4)	−0.2085 (4)	0.0702 (3)	0.0953 (15)
H19A	0.4964	−0.1594	0.0276	0.143*
H19B	0.3844	−0.2460	0.0490	0.143*
H19C	0.5093	−0.2664	0.0883	0.143*
C20A	0.3134 (5)	−0.0438 (4)	0.1133 (4)	0.1050 (18)
H20A	0.3588	0.0086	0.0736	0.157*
H20B	0.2765	−0.0010	0.1596	0.157*
H20C	0.2485	−0.0810	0.0883	0.157*
C21A	0.3272 (5)	−0.2176 (4)	0.2059 (3)	0.0960 (16)
H21A	0.2640	−0.2559	0.1800	0.144*
H21B	0.2881	−0.1735	0.2508	0.144*
H21C	0.3825	−0.2747	0.2264	0.144*
Br1B	0.20327 (4)	−0.04446 (3)	0.43395 (3)	0.06602 (15)
O1B	0.2162 (2)	0.4350 (2)	0.68663 (14)	0.0587 (6)
H1B	0.1986	0.3964	0.6483	0.088*
N1B	0.0774 (3)	0.3360 (2)	0.58981 (16)	0.0481 (7)
C1B	−0.0066 (3)	0.4563 (3)	0.70015 (19)	0.0439 (8)
C2B	0.1102 (3)	0.4790 (3)	0.72681 (19)	0.0431 (8)
C3B	0.1178 (3)	0.5481 (3)	0.79514 (19)	0.0434 (8)
C4B	0.0063 (3)	0.5959 (3)	0.8311 (2)	0.0476 (8)
H4B	0.0102	0.6435	0.8756	0.057*
C5B	−0.1117 (3)	0.5779 (3)	0.80544 (19)	0.0443 (8)
C6B	−0.1152 (3)	0.5058 (3)	0.74019 (19)	0.0456 (8)
H6B	−0.1920	0.4896	0.7223	0.055*
C7B	−0.0169 (3)	0.3834 (3)	0.63013 (19)	0.0461 (8)
H7B	−0.0958	0.3709	0.6143	0.055*
C8B	0.0630 (3)	0.2696 (3)	0.51993 (19)	0.0445 (8)
C9B	−0.0088 (3)	0.3087 (3)	0.4589 (2)	0.0518 (9)
H9B	−0.0506	0.3797	0.4634	0.062*
C10B	−0.0177 (4)	0.2414 (3)	0.3914 (2)	0.0588 (10)
H10B	−0.0665	0.2674	0.3510	0.071*
C11B	0.0440 (3)	0.1371 (3)	0.3831 (2)	0.0539 (9)
H11B	0.0373	0.0921	0.3376	0.065*
C12B	0.1166 (3)	0.1001 (3)	0.44353 (19)	0.0471 (8)
C13B	0.1276 (3)	0.1650 (3)	0.51120 (19)	0.0463 (8)
H13B	0.1779	0.1392	0.5508	0.056*
C14B	0.2434 (3)	0.5713 (3)	0.8278 (2)	0.0520 (9)
C15B	0.3314 (4)	0.6394 (3)	0.7609 (3)	0.0780 (13)
H15D	0.3435	0.5958	0.7115	0.117*
H15E	0.4109	0.6511	0.7807	0.117*
H15F	0.2944	0.7135	0.7492	0.117*
C16B	0.3061 (4)	0.4560 (3)	0.8500 (2)	0.0643 (10)
H16D	0.2521	0.4141	0.8918	0.096*
H16E	0.3842	0.4716	0.8704	0.096*
H16F	0.3211	0.4102	0.8018	0.096*
C17B	0.2279 (4)	0.6430 (4)	0.9050 (3)	0.0822 (13)
H17D	0.1966	0.7189	0.8918	0.123*
H17E	0.3075	0.6502	0.9254	0.123*
H17F	0.1699	0.6050	0.9465	0.123*
C18B	−0.2322 (3)	0.6349 (3)	0.8461 (2)	0.0513 (8)
C19B	−0.2088 (4)	0.7085 (4)	0.9189 (3)	0.0830 (13)
H19D	−0.2872	0.7375	0.9449	0.125*
H19E	−0.1554	0.7726	0.8995	0.125*
H19F	−0.1692	0.6614	0.9582	0.125*
C20B	−0.3284 (4)	0.5428 (4)	0.8771 (3)	0.0888 (14)
H20D	−0.4004	0.5792	0.9062	0.133*
H20E	−0.2925	0.4883	0.9136	0.133*
H20F	−0.3531	0.5027	0.8311	0.133*
C21B	−0.2858 (5)	0.7152 (4)	0.7821 (3)	0.0907 (15)
H21D	−0.3067	0.6701	0.7373	0.136*
H21E	−0.2246	0.7726	0.7616	0.136*
H21F	−0.3598	0.7530	0.8074	0.136*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1A	0.0751 (3)	0.0594 (2)	0.0714 (3)	0.0029 (2)	−0.0278 (2)	−0.01885 (19)
O1A	0.0447 (14)	0.0662 (15)	0.0586 (14)	−0.0007 (12)	−0.0094 (11)	−0.0280 (12)
N1A	0.0517 (18)	0.0475 (16)	0.0478 (16)	0.0017 (14)	−0.0010 (13)	−0.0090 (13)
C1A	0.041 (2)	0.0419 (17)	0.0467 (18)	−0.0031 (15)	0.0002 (14)	−0.0104 (15)
C2A	0.042 (2)	0.0430 (17)	0.0437 (17)	−0.0039 (15)	−0.0030 (14)	−0.0076 (14)
C3A	0.0425 (19)	0.0414 (17)	0.0443 (17)	−0.0045 (15)	−0.0039 (14)	−0.0050 (14)
C4A	0.046 (2)	0.0461 (18)	0.0454 (18)	−0.0034 (16)	−0.0021 (15)	−0.0103 (15)
C5A	0.042 (2)	0.0480 (18)	0.0502 (19)	−0.0045 (15)	−0.0061 (15)	−0.0085 (16)
C6A	0.0363 (19)	0.0499 (19)	0.058 (2)	−0.0022 (15)	−0.0018 (15)	−0.0102 (16)
C7A	0.047 (2)	0.0439 (18)	0.0472 (18)	−0.0038 (16)	0.0011 (16)	−0.0043 (15)
C8A	0.047 (2)	0.0495 (19)	0.0406 (17)	0.0109 (16)	−0.0049 (14)	−0.0084 (15)
C9A	0.060 (2)	0.0457 (19)	0.0483 (19)	0.0056 (17)	0.0024 (16)	−0.0065 (16)
C10A	0.064 (3)	0.070 (3)	0.050 (2)	0.007 (2)	0.0113 (18)	0.0027 (19)
C11A	0.064 (3)	0.065 (2)	0.046 (2)	0.018 (2)	−0.0055 (18)	−0.0123 (18)
C12A	0.043 (2)	0.054 (2)	0.0485 (19)	0.0084 (16)	−0.0138 (15)	−0.0088 (16)
C13A	0.047 (2)	0.054 (2)	0.0405 (17)	0.0069 (16)	−0.0055 (14)	−0.0104 (15)
C14A	0.041 (2)	0.0513 (19)	0.0478 (18)	−0.0033 (16)	−0.0002 (15)	−0.0098 (16)
C15A	0.057 (2)	0.066 (2)	0.073 (3)	0.013 (2)	−0.006 (2)	−0.001 (2)
C16A	0.051 (2)	0.060 (2)	0.077 (3)	−0.0097 (18)	0.0087 (19)	−0.007 (2)
C17A	0.057 (3)	0.083 (3)	0.071 (3)	−0.001 (2)	0.006 (2)	−0.030 (2)
C18A	0.047 (2)	0.056 (2)	0.066 (2)	−0.0026 (18)	−0.0134 (17)	−0.0169 (18)
C19A	0.072 (3)	0.116 (4)	0.106 (4)	−0.003 (3)	−0.027 (3)	−0.059 (3)
C20A	0.096 (4)	0.085 (3)	0.149 (5)	0.016 (3)	−0.071 (4)	−0.027 (3)
C21A	0.090 (4)	0.096 (3)	0.105 (4)	−0.046 (3)	−0.014 (3)	−0.014 (3)
Br1B	0.0634 (3)	0.0557 (2)	0.0761 (3)	0.00218 (19)	0.0079 (2)	−0.01765 (19)
O1B	0.0480 (15)	0.0694 (16)	0.0605 (15)	0.0056 (12)	−0.0072 (12)	−0.0265 (13)
N1B	0.0516 (18)	0.0485 (16)	0.0452 (15)	0.0006 (14)	−0.0065 (13)	−0.0122 (13)
C1B	0.052 (2)	0.0402 (17)	0.0414 (17)	0.0021 (15)	−0.0100 (15)	−0.0071 (14)
C2B	0.044 (2)	0.0408 (17)	0.0458 (18)	0.0024 (15)	−0.0093 (15)	−0.0042 (15)
C3B	0.050 (2)	0.0406 (17)	0.0415 (17)	−0.0013 (15)	−0.0113 (15)	−0.0036 (14)
C4B	0.055 (2)	0.0426 (18)	0.0472 (18)	−0.0022 (16)	−0.0112 (16)	−0.0098 (15)
C5B	0.048 (2)	0.0420 (17)	0.0435 (17)	0.0015 (15)	−0.0061 (15)	−0.0090 (15)
C6B	0.044 (2)	0.0457 (18)	0.0494 (18)	0.0000 (15)	−0.0128 (15)	−0.0109 (15)
C7B	0.048 (2)	0.0470 (18)	0.0445 (18)	−0.0019 (16)	−0.0115 (16)	−0.0054 (15)
C8B	0.045 (2)	0.0483 (19)	0.0402 (17)	−0.0068 (16)	−0.0025 (14)	−0.0071 (15)
C9B	0.064 (2)	0.0431 (18)	0.050 (2)	−0.0039 (17)	−0.0114 (17)	−0.0011 (16)
C10B	0.072 (3)	0.062 (2)	0.046 (2)	−0.002 (2)	−0.0182 (18)	−0.0014 (17)
C11B	0.062 (2)	0.057 (2)	0.0436 (19)	−0.0087 (19)	−0.0066 (17)	−0.0140 (16)
C12B	0.044 (2)	0.0505 (19)	0.0447 (18)	−0.0090 (16)	0.0077 (15)	−0.0110 (15)
C13B	0.0393 (19)	0.054 (2)	0.0449 (18)	0.0029 (16)	−0.0024 (14)	−0.0063 (16)
C14B	0.050 (2)	0.0506 (19)	0.059 (2)	−0.0015 (17)	−0.0206 (17)	−0.0061 (17)
C15B	0.067 (3)	0.070 (3)	0.099 (3)	−0.026 (2)	−0.023 (2)	0.015 (2)
C16B	0.067 (3)	0.061 (2)	0.070 (2)	0.003 (2)	−0.028 (2)	0.000 (2)
C17B	0.082 (3)	0.087 (3)	0.089 (3)	0.010 (3)	−0.047 (3)	−0.032 (3)
C18B	0.047 (2)	0.052 (2)	0.055 (2)	0.0007 (16)	−0.0035 (16)	−0.0148 (17)
C19B	0.067 (3)	0.097 (3)	0.083 (3)	−0.002 (3)	0.010 (2)	−0.044 (3)
C20B	0.066 (3)	0.081 (3)	0.115 (4)	−0.013 (2)	0.019 (3)	−0.024 (3)
C21B	0.092 (4)	0.090 (3)	0.088 (3)	0.042 (3)	−0.004 (3)	−0.010 (3)

Geometric parameters (Å, º) top

Br1A—C12A	1.901 (3)	Br1B—C12B	1.902 (3)
O1A—C2A	1.358 (4)	O1B—C2B	1.350 (4)
O1A—H1A	0.8200	O1B—H1B	0.8200
N1A—C7A	1.277 (4)	N1B—C7B	1.271 (4)
N1A—C8A	1.421 (4)	N1B—C8B	1.419 (4)
C1A—C6A	1.400 (4)	C1B—C6B	1.396 (5)
C1A—C2A	1.414 (4)	C1B—C2B	1.406 (4)
C1A—C7A	1.452 (4)	C1B—C7B	1.457 (4)
C2A—C3A	1.399 (4)	C2B—C3B	1.403 (4)
C3A—C4A	1.394 (4)	C3B—C4B	1.389 (5)
C3A—C14A	1.534 (5)	C3B—C14B	1.538 (4)
C4A—C5A	1.402 (4)	C4B—C5B	1.401 (4)
C4A—H4A	0.9300	C4B—H4B	0.9300
C5A—C6A	1.377 (5)	C5B—C6B	1.378 (4)
C5A—C18A	1.534 (4)	C5B—C18B	1.537 (5)
C6A—H6A	0.9300	C6B—H6B	0.9300
C7A—H7A	0.9300	C7B—H7B	0.9300
C8A—C13A	1.386 (5)	C8B—C13B	1.388 (4)
C8A—C9A	1.397 (5)	C8B—C9B	1.392 (4)
C9A—C10A	1.372 (5)	C9B—C10B	1.380 (5)
C9A—H9A	0.9300	C9B—H9B	0.9300
C10A—C11A	1.393 (5)	C10B—C11B	1.369 (5)
C10A—H10A	0.9300	C10B—H10B	0.9300
C11A—C12A	1.378 (5)	C11B—C12B	1.382 (5)
C11A—H11A	0.9300	C11B—H11B	0.9300
C12A—C13A	1.386 (5)	C12B—C13B	1.372 (4)
C13A—H13A	0.9300	C13B—H13B	0.9300
C14A—C17A	1.516 (5)	C14B—C17B	1.523 (5)
C14A—C16A	1.539 (4)	C14B—C16B	1.533 (5)
C14A—C15A	1.548 (5)	C14B—C15B	1.551 (5)
C15A—H15A	0.9600	C15B—H15D	0.9600
C15A—H15B	0.9600	C15B—H15E	0.9600
C15A—H15C	0.9600	C15B—H15F	0.9600
C16A—H16A	0.9600	C16B—H16D	0.9600
C16A—H16B	0.9600	C16B—H16E	0.9600
C16A—H16C	0.9600	C16B—H16F	0.9600
C17A—H17A	0.9600	C17B—H17D	0.9600
C17A—H17B	0.9600	C17B—H17E	0.9600
C17A—H17C	0.9600	C17B—H17F	0.9600
C18A—C19A	1.518 (6)	C18B—C20B	1.517 (5)
C18A—C20A	1.521 (5)	C18B—C21B	1.529 (5)
C18A—C21A	1.537 (5)	C18B—C19B	1.530 (5)
C19A—H19A	0.9600	C19B—H19D	0.9600
C19A—H19B	0.9600	C19B—H19E	0.9600
C19A—H19C	0.9600	C19B—H19F	0.9600
C20A—H20A	0.9600	C20B—H20D	0.9600
C20A—H20B	0.9600	C20B—H20E	0.9600
C20A—H20C	0.9600	C20B—H20F	0.9600
C21A—H21A	0.9600	C21B—H21D	0.9600
C21A—H21B	0.9600	C21B—H21E	0.9600
C21A—H21C	0.9600	C21B—H21F	0.9600

C2A—O1A—H1A	109.5	C2B—O1B—H1B	109.5
C7A—N1A—C8A	121.0 (3)	C7B—N1B—C8B	120.7 (3)
C6A—C1A—C2A	119.0 (3)	C6B—C1B—C2B	119.8 (3)
C6A—C1A—C7A	119.5 (3)	C6B—C1B—C7B	118.8 (3)
C2A—C1A—C7A	121.5 (3)	C2B—C1B—C7B	121.3 (3)
O1A—C2A—C3A	119.4 (3)	O1B—C2B—C3B	119.3 (3)
O1A—C2A—C1A	119.8 (3)	O1B—C2B—C1B	120.3 (3)
C3A—C2A—C1A	120.8 (3)	C3B—C2B—C1B	120.4 (3)
C4A—C3A—C2A	116.8 (3)	C4B—C3B—C2B	116.5 (3)
C4A—C3A—C14A	121.4 (3)	C4B—C3B—C14B	121.7 (3)
C2A—C3A—C14A	121.8 (3)	C2B—C3B—C14B	121.7 (3)
C3A—C4A—C5A	124.6 (3)	C3B—C4B—C5B	125.0 (3)
C3A—C4A—H4A	117.7	C3B—C4B—H4B	117.5
C5A—C4A—H4A	117.7	C5B—C4B—H4B	117.5
C6A—C5A—C4A	116.4 (3)	C6B—C5B—C4B	116.3 (3)
C6A—C5A—C18A	120.7 (3)	C6B—C5B—C18B	120.6 (3)
C4A—C5A—C18A	122.9 (3)	C4B—C5B—C18B	123.1 (3)
C5A—C6A—C1A	122.4 (3)	C5B—C6B—C1B	121.8 (3)
C5A—C6A—H6A	118.8	C5B—C6B—H6B	119.1
C1A—C6A—H6A	118.8	C1B—C6B—H6B	119.1
N1A—C7A—C1A	122.1 (3)	N1B—C7B—C1B	122.8 (3)
N1A—C7A—H7A	118.9	N1B—C7B—H7B	118.6
C1A—C7A—H7A	118.9	C1B—C7B—H7B	118.6
C13A—C8A—C9A	120.3 (3)	C13B—C8B—C9B	119.6 (3)
C13A—C8A—N1A	117.5 (3)	C13B—C8B—N1B	118.3 (3)
C9A—C8A—N1A	122.3 (3)	C9B—C8B—N1B	122.1 (3)
C10A—C9A—C8A	119.3 (3)	C10B—C9B—C8B	119.7 (3)
C10A—C9A—H9A	120.3	C10B—C9B—H9B	120.2
C8A—C9A—H9A	120.3	C8B—C9B—H9B	120.2
C9A—C10A—C11A	121.5 (3)	C11B—C10B—C9B	121.1 (3)
C9A—C10A—H10A	119.2	C11B—C10B—H10B	119.5
C11A—C10A—H10A	119.2	C9B—C10B—H10B	119.5
C12A—C11A—C10A	118.2 (3)	C10B—C11B—C12B	118.7 (3)
C12A—C11A—H11A	120.9	C10B—C11B—H11B	120.7
C10A—C11A—H11A	120.9	C12B—C11B—H11B	120.7
C11A—C12A—C13A	121.9 (3)	C13B—C12B—C11B	121.7 (3)
C11A—C12A—Br1A	119.7 (3)	C13B—C12B—Br1B	118.6 (3)
C13A—C12A—Br1A	118.4 (3)	C11B—C12B—Br1B	119.8 (3)
C8A—C13A—C12A	118.9 (3)	C12B—C13B—C8B	119.3 (3)
C8A—C13A—H13A	120.6	C12B—C13B—H13B	120.4
C12A—C13A—H13A	120.6	C8B—C13B—H13B	120.4
C17A—C14A—C3A	112.8 (3)	C17B—C14B—C16B	107.3 (3)
C17A—C14A—C16A	107.2 (3)	C17B—C14B—C3B	112.4 (3)
C3A—C14A—C16A	110.1 (3)	C16B—C14B—C3B	110.3 (3)
C17A—C14A—C15A	107.4 (3)	C17B—C14B—C15B	107.6 (3)
C3A—C14A—C15A	109.7 (3)	C16B—C14B—C15B	109.4 (3)
C16A—C14A—C15A	109.6 (3)	C3B—C14B—C15B	109.7 (3)
C14A—C15A—H15A	109.5	C14B—C15B—H15D	109.5
C14A—C15A—H15B	109.5	C14B—C15B—H15E	109.5
H15A—C15A—H15B	109.5	H15D—C15B—H15E	109.5
C14A—C15A—H15C	109.5	C14B—C15B—H15F	109.5
H15A—C15A—H15C	109.5	H15D—C15B—H15F	109.5
H15B—C15A—H15C	109.5	H15E—C15B—H15F	109.5
C14A—C16A—H16A	109.5	C14B—C16B—H16D	109.5
C14A—C16A—H16B	109.5	C14B—C16B—H16E	109.5
H16A—C16A—H16B	109.5	H16D—C16B—H16E	109.5
C14A—C16A—H16C	109.5	C14B—C16B—H16F	109.5
H16A—C16A—H16C	109.5	H16D—C16B—H16F	109.5
H16B—C16A—H16C	109.5	H16E—C16B—H16F	109.5
C14A—C17A—H17A	109.5	C14B—C17B—H17D	109.5
C14A—C17A—H17B	109.5	C14B—C17B—H17E	109.5
H17A—C17A—H17B	109.5	H17D—C17B—H17E	109.5
C14A—C17A—H17C	109.5	C14B—C17B—H17F	109.5
H17A—C17A—H17C	109.5	H17D—C17B—H17F	109.5
H17B—C17A—H17C	109.5	H17E—C17B—H17F	109.5
C19A—C18A—C20A	109.1 (4)	C20B—C18B—C21B	109.2 (4)
C19A—C18A—C5A	113.4 (3)	C20B—C18B—C19B	108.2 (3)
C20A—C18A—C5A	110.4 (3)	C21B—C18B—C19B	107.8 (3)
C19A—C18A—C21A	106.8 (3)	C20B—C18B—C5B	110.4 (3)
C20A—C18A—C21A	108.2 (4)	C21B—C18B—C5B	108.8 (3)
C5A—C18A—C21A	108.8 (3)	C19B—C18B—C5B	112.4 (3)
C18A—C19A—H19A	109.5	C18B—C19B—H19D	109.5
C18A—C19A—H19B	109.5	C18B—C19B—H19E	109.5
H19A—C19A—H19B	109.5	H19D—C19B—H19E	109.5
C18A—C19A—H19C	109.5	C18B—C19B—H19F	109.5
H19A—C19A—H19C	109.5	H19D—C19B—H19F	109.5
H19B—C19A—H19C	109.5	H19E—C19B—H19F	109.5
C18A—C20A—H20A	109.5	C18B—C20B—H20D	109.5
C18A—C20A—H20B	109.5	C18B—C20B—H20E	109.5
H20A—C20A—H20B	109.5	H20D—C20B—H20E	109.5
C18A—C20A—H20C	109.5	C18B—C20B—H20F	109.5
H20A—C20A—H20C	109.5	H20D—C20B—H20F	109.5
H20B—C20A—H20C	109.5	H20E—C20B—H20F	109.5
C18A—C21A—H21A	109.5	C18B—C21B—H21D	109.5
C18A—C21A—H21B	109.5	C18B—C21B—H21E	109.5
H21A—C21A—H21B	109.5	H21D—C21B—H21E	109.5
C18A—C21A—H21C	109.5	C18B—C21B—H21F	109.5
H21A—C21A—H21C	109.5	H21D—C21B—H21F	109.5
H21B—C21A—H21C	109.5	H21E—C21B—H21F	109.5

C6A—C1A—C2A—O1A	−178.0 (3)	C6B—C1B—C2B—O1B	−177.6 (3)
C7A—C1A—C2A—O1A	1.5 (4)	C7B—C1B—C2B—O1B	1.2 (4)
C6A—C1A—C2A—C3A	1.5 (5)	C6B—C1B—C2B—C3B	2.1 (4)
C7A—C1A—C2A—C3A	−179.0 (3)	C7B—C1B—C2B—C3B	−179.1 (3)
O1A—C2A—C3A—C4A	177.3 (3)	O1B—C2B—C3B—C4B	176.7 (3)
C1A—C2A—C3A—C4A	−2.2 (4)	C1B—C2B—C3B—C4B	−3.0 (4)
O1A—C2A—C3A—C14A	−1.9 (4)	O1B—C2B—C3B—C14B	−2.4 (4)
C1A—C2A—C3A—C14A	178.6 (3)	C1B—C2B—C3B—C14B	177.9 (3)
C2A—C3A—C4A—C5A	1.0 (5)	C2B—C3B—C4B—C5B	1.6 (4)
C14A—C3A—C4A—C5A	−179.8 (3)	C14B—C3B—C4B—C5B	−179.3 (3)
C3A—C4A—C5A—C6A	0.9 (5)	C3B—C4B—C5B—C6B	0.9 (4)
C3A—C4A—C5A—C18A	−177.0 (3)	C3B—C4B—C5B—C18B	−178.6 (3)
C4A—C5A—C6A—C1A	−1.8 (5)	C4B—C5B—C6B—C1B	−2.0 (4)
C18A—C5A—C6A—C1A	176.3 (3)	C18B—C5B—C6B—C1B	177.6 (3)
C2A—C1A—C6A—C5A	0.6 (5)	C2B—C1B—C6B—C5B	0.6 (4)
C7A—C1A—C6A—C5A	−178.9 (3)	C7B—C1B—C6B—C5B	−178.3 (3)
C8A—N1A—C7A—C1A	−177.9 (3)	C8B—N1B—C7B—C1B	−177.4 (3)
C6A—C1A—C7A—N1A	179.8 (3)	C6B—C1B—C7B—N1B	179.3 (3)
C2A—C1A—C7A—N1A	0.3 (5)	C2B—C1B—C7B—N1B	0.4 (5)
C7A—N1A—C8A—C13A	−136.9 (3)	C7B—N1B—C8B—C13B	−136.8 (3)
C7A—N1A—C8A—C9A	45.4 (4)	C7B—N1B—C8B—C9B	46.1 (4)
C13A—C8A—C9A—C10A	0.4 (5)	C13B—C8B—C9B—C10B	1.8 (5)
N1A—C8A—C9A—C10A	178.0 (3)	N1B—C8B—C9B—C10B	178.9 (3)
C8A—C9A—C10A—C11A	0.5 (6)	C8B—C9B—C10B—C11B	−0.7 (5)
C9A—C10A—C11A—C12A	−0.5 (5)	C9B—C10B—C11B—C12B	−0.3 (5)
C10A—C11A—C12A—C13A	−0.2 (5)	C10B—C11B—C12B—C13B	0.1 (5)
C10A—C11A—C12A—Br1A	178.9 (3)	C10B—C11B—C12B—Br1B	179.8 (3)
C9A—C8A—C13A—C12A	−1.1 (5)	C11B—C12B—C13B—C8B	0.9 (5)
N1A—C8A—C13A—C12A	−178.8 (3)	Br1B—C12B—C13B—C8B	−178.8 (2)
C11A—C12A—C13A—C8A	1.0 (5)	C9B—C8B—C13B—C12B	−1.9 (5)
Br1A—C12A—C13A—C8A	−178.1 (2)	N1B—C8B—C13B—C12B	−179.1 (3)
C4A—C3A—C14A—C17A	2.8 (4)	C4B—C3B—C14B—C17B	4.0 (4)
C2A—C3A—C14A—C17A	−178.0 (3)	C2B—C3B—C14B—C17B	−176.9 (3)
C4A—C3A—C14A—C16A	122.4 (3)	C4B—C3B—C14B—C16B	123.7 (3)
C2A—C3A—C14A—C16A	−58.4 (4)	C2B—C3B—C14B—C16B	−57.2 (4)
C4A—C3A—C14A—C15A	−116.8 (3)	C4B—C3B—C14B—C15B	−115.7 (3)
C2A—C3A—C14A—C15A	62.3 (4)	C2B—C3B—C14B—C15B	63.3 (4)
C6A—C5A—C18A—C19A	179.8 (3)	C6B—C5B—C18B—C20B	57.3 (4)
C4A—C5A—C18A—C19A	−2.3 (5)	C4B—C5B—C18B—C20B	−123.2 (4)
C6A—C5A—C18A—C20A	57.1 (5)	C6B—C5B—C18B—C21B	−62.6 (4)
C4A—C5A—C18A—C20A	−125.1 (4)	C4B—C5B—C18B—C21B	117.0 (4)
C6A—C5A—C18A—C21A	−61.6 (4)	C6B—C5B—C18B—C19B	178.2 (3)
C4A—C5A—C18A—C21A	116.3 (4)	C4B—C5B—C18B—C19B	−2.3 (4)

(4) top

Crystal data top

C₂₁H₂₆ClNO	V = 1979.8 (4) Å³
M_r = 343.88	Z = 4
Triclinic, P1	F(000) = 736
a = 10.7392 (12) Å	D_x = 1.154 Mg m⁻³
b = 11.5369 (15) Å	Mo Kα radiation, λ = 0.71075 Å
c = 16.1292 (19) Å	µ = 0.20 mm⁻¹
α = 88.032 (3)°	T = 296 K
β = 82.446 (3)°	Platelet, yellow
γ = 89.642 (3)°	0.15 × 0.07 × 0.03 mm

Data collection top

Rigaku R-AXIS RAPID IP Area Detector System diffractometer	7172 independent reflections
Radiation source: rotating anode X-ray tube	2946 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.079
ω scans	θ_max = 25.3°, θ_min = 3.0°
Absorption correction: multi-scan Absorption was corrected by ABSCOR	h = −12→12
T_min = 0.729, T_max = 0.994	k = −13→13
16014 measured reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.164	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0544P)² + 0.3548P] where P = (F_o² + 2F_c²)/3
7172 reflections	(Δ/σ)_max = 0.020
461 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂₁H₂₆ClNO	γ = 89.642 (3)°
M_r = 343.88	V = 1979.8 (4) Å³
Triclinic, P1	Z = 4
a = 10.7392 (12) Å	Mo Kα radiation
b = 11.5369 (15) Å	µ = 0.20 mm⁻¹
c = 16.1292 (19) Å	T = 296 K
α = 88.032 (3)°	0.15 × 0.07 × 0.03 mm
β = 82.446 (3)°

Data collection top

Rigaku R-AXIS RAPID IP Area Detector System diffractometer	7172 independent reflections
Absorption correction: multi-scan Absorption was corrected by ABSCOR	2946 reflections with I > 2σ(I)
T_min = 0.729, T_max = 0.994	R_int = 0.079
16014 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.164	H-atom parameters constrained
S = 1.02	Δρ_max = 0.20 e Å⁻³
7172 reflections	Δρ_min = −0.19 e Å⁻³
461 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1A	0.29775 (10)	0.53750 (10)	0.56057 (8)	0.0816 (4)
O1A	0.2913 (2)	0.0621 (2)	0.31207 (17)	0.0664 (8)
H1A	0.3065	0.1002	0.3515	0.100*
N1A	0.4238 (3)	0.1645 (3)	0.4116 (2)	0.0564 (8)
C1A	0.5150 (3)	0.0423 (3)	0.3023 (2)	0.0496 (10)
C2A	0.4000 (3)	0.0182 (3)	0.2725 (2)	0.0499 (10)
C3A	0.3979 (3)	−0.0505 (3)	0.2032 (2)	0.0507 (10)
C4A	0.5120 (3)	−0.0984 (3)	0.1685 (2)	0.0545 (10)
H4A	0.5115	−0.1452	0.1227	0.065*
C5A	0.6265 (3)	−0.0806 (3)	0.1979 (2)	0.0498 (9)
C6A	0.6254 (3)	−0.0082 (3)	0.2640 (2)	0.0521 (10)
H6A	0.7007	0.0076	0.2839	0.062*
C7A	0.5210 (4)	0.1162 (3)	0.3725 (2)	0.0549 (10)
H7A	0.5988	0.1291	0.3900	0.066*
C8A	0.4364 (3)	0.2341 (3)	0.4816 (2)	0.0525 (10)
C9A	0.5054 (4)	0.1977 (4)	0.5445 (3)	0.0649 (11)
H9A	0.5468	0.1266	0.5418	0.078*
C10A	0.5119 (4)	0.2679 (4)	0.6111 (3)	0.0714 (12)
H10A	0.5595	0.2441	0.6528	0.086*
C11A	0.4496 (4)	0.3727 (4)	0.6174 (3)	0.0674 (12)
H11A	0.4551	0.4198	0.6624	0.081*
C12A	0.3791 (3)	0.4056 (3)	0.5554 (3)	0.0567 (10)
C13A	0.3705 (3)	0.3381 (4)	0.4871 (2)	0.0559 (10)
H13A	0.3219	0.3618	0.4459	0.067*
C14A	0.2739 (3)	−0.0737 (3)	0.1672 (3)	0.0608 (11)
C15A	0.2109 (4)	0.0415 (4)	0.1452 (3)	0.0768 (13)
H15A	0.1342	0.0257	0.1231	0.115*
H15B	0.2665	0.0847	0.1041	0.115*
H15C	0.1928	0.0858	0.1946	0.115*
C16A	0.1854 (4)	−0.1447 (4)	0.2314 (3)	0.0889 (16)
H16A	0.1114	−0.1644	0.2074	0.133*
H16B	0.1621	−0.0999	0.2801	0.133*
H16C	0.2271	−0.2144	0.2469	0.133*
C17A	0.2962 (4)	−0.1415 (4)	0.0867 (3)	0.0935 (16)
H17A	0.3302	−0.2165	0.0985	0.140*
H17B	0.3543	−0.0999	0.0462	0.140*
H17C	0.2180	−0.1506	0.0648	0.140*
C18A	0.7484 (3)	−0.1387 (3)	0.1601 (3)	0.0584 (11)
C19A	0.7282 (4)	−0.2186 (5)	0.0897 (4)	0.1087 (19)
H19A	0.6764	−0.2827	0.1121	0.163*
H19B	0.8079	−0.2471	0.0643	0.163*
H19C	0.6877	−0.1763	0.0485	0.163*
C20A	0.8429 (4)	−0.0474 (4)	0.1233 (4)	0.1066 (18)
H20A	0.8073	−0.0002	0.0822	0.160*
H20B	0.9176	−0.0846	0.0975	0.160*
H20C	0.8637	0.0005	0.1671	0.160*
C21A	0.8034 (4)	−0.2112 (5)	0.2270 (3)	0.1036 (18)
H21A	0.8228	−0.1619	0.2703	0.155*
H21B	0.8788	−0.2487	0.2024	0.155*
H21C	0.7435	−0.2687	0.2504	0.155*
Cl1B	0.17617 (11)	1.02923 (10)	0.55715 (8)	0.0819 (4)
O1B	0.2852 (2)	0.5591 (2)	0.30932 (16)	0.0643 (8)
H1B	0.2524	0.5968	0.3486	0.096*
N1B	0.1099 (3)	0.6583 (3)	0.4069 (2)	0.0575 (9)
C1B	0.0668 (3)	0.5382 (3)	0.2959 (2)	0.0496 (10)
C2B	0.1945 (3)	0.5159 (3)	0.2677 (2)	0.0485 (9)
C3B	0.2286 (3)	0.4482 (3)	0.1980 (2)	0.0475 (9)
C4B	0.1320 (3)	0.4013 (3)	0.1605 (2)	0.0538 (10)
H4B	0.1536	0.3554	0.1145	0.065*
C5B	0.0034 (3)	0.4186 (3)	0.1876 (2)	0.0531 (10)
C6B	−0.0255 (3)	0.4884 (3)	0.2556 (2)	0.0551 (10)
H6B	−0.1094	0.5025	0.2751	0.066*
C7B	0.0301 (3)	0.6097 (3)	0.3670 (2)	0.0553 (10)
H7B	−0.0550	0.6208	0.3845	0.066*
C8B	0.0695 (3)	0.7271 (3)	0.4771 (2)	0.0529 (10)
C9B	−0.0246 (4)	0.6919 (4)	0.5397 (3)	0.0648 (11)
H9B	−0.0663	0.6221	0.5363	0.078*
C10B	−0.0562 (4)	0.7617 (4)	0.6074 (3)	0.0752 (13)
H10B	−0.1191	0.7379	0.6497	0.090*
C11B	0.0036 (4)	0.8655 (4)	0.6134 (3)	0.0716 (13)
H11B	−0.0197	0.9128	0.6584	0.086*
C12B	0.0982 (4)	0.8979 (4)	0.5517 (3)	0.0601 (11)
C13B	0.1326 (3)	0.8305 (4)	0.4836 (2)	0.0559 (10)
H13B	0.1972	0.8540	0.4424	0.067*
C14B	0.3678 (3)	0.4258 (3)	0.1661 (2)	0.0518 (10)
C15B	0.4303 (4)	0.3572 (4)	0.2321 (3)	0.0734 (13)
H15D	0.3887	0.2839	0.2439	0.110*
H15E	0.4243	0.4002	0.2824	0.110*
H15F	0.5171	0.3444	0.2116	0.110*
C16B	0.3837 (4)	0.3553 (4)	0.0860 (3)	0.0753 (13)
H16D	0.4715	0.3471	0.0662	0.113*
H16E	0.3426	0.3949	0.0438	0.113*
H16F	0.3470	0.2800	0.0981	0.113*
C17B	0.4373 (3)	0.5413 (4)	0.1430 (3)	0.0729 (13)
H17D	0.5242	0.5259	0.1242	0.109*
H17E	0.4307	0.5885	0.1912	0.109*
H17F	0.4002	0.5814	0.0991	0.109*
C18B	−0.0997 (3)	0.3615 (4)	0.1459 (3)	0.0631 (11)
C19B	−0.0489 (5)	0.2854 (5)	0.0734 (4)	0.092 (2)	0.898 (7)
H19D	0.0076	0.2286	0.0924	0.138*	0.898 (7)
H19E	−0.0048	0.3329	0.0291	0.138*	0.898 (7)
H19F	−0.1174	0.2470	0.0531	0.138*	0.898 (7)
C20B	−0.1862 (5)	0.4525 (5)	0.1148 (5)	0.099 (2)	0.898 (7)
H20D	−0.2511	0.4153	0.0897	0.148*	0.898 (7)
H20E	−0.1389	0.5031	0.0739	0.148*	0.898 (7)
H20F	−0.2236	0.4969	0.1609	0.148*	0.898 (7)
C21B	−0.1780 (5)	0.2816 (5)	0.2119 (4)	0.098 (2)	0.898 (7)
H21D	−0.2402	0.2418	0.1860	0.147*	0.898 (7)
H21E	−0.2188	0.3275	0.2561	0.147*	0.898 (7)
H21F	−0.1237	0.2259	0.2346	0.147*	0.898 (7)
C19C	−0.075 (4)	0.419 (5)	0.045 (3)	0.081 (16)*	0.102 (7)
H19G	0.0015	0.3891	0.0169	0.122*	0.102 (7)
H19H	−0.0703	0.5020	0.0468	0.122*	0.102 (7)
H19I	−0.1440	0.3983	0.0163	0.122*	0.102 (7)
C20C	−0.228 (5)	0.405 (6)	0.183 (4)	0.098 (19)*	0.102 (7)
H20G	−0.2916	0.3723	0.1538	0.147*	0.102 (7)
H20H	−0.2309	0.4882	0.1768	0.147*	0.102 (7)
H20I	−0.2440	0.3824	0.2410	0.147*	0.102 (7)
C21C	−0.071 (4)	0.240 (4)	0.147 (3)	0.068 (14)*	0.102 (7)
H21G	0.0125	0.2284	0.1182	0.102*	0.102 (7)
H21H	−0.1301	0.1997	0.1185	0.102*	0.102 (7)
H21I	−0.0754	0.2109	0.2033	0.102*	0.102 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1A	0.0818 (7)	0.0631 (8)	0.0956 (9)	0.0106 (6)	0.0080 (6)	−0.0215 (7)
O1A	0.0544 (15)	0.071 (2)	0.076 (2)	0.0102 (14)	−0.0108 (14)	−0.0249 (16)
N1A	0.062 (2)	0.047 (2)	0.061 (2)	0.0062 (16)	−0.0092 (17)	−0.0119 (18)
C1A	0.056 (2)	0.036 (2)	0.058 (3)	0.0047 (18)	−0.0131 (19)	−0.007 (2)
C2A	0.048 (2)	0.040 (2)	0.063 (3)	0.0102 (17)	−0.0097 (19)	−0.006 (2)
C3A	0.054 (2)	0.036 (2)	0.063 (3)	0.0037 (17)	−0.0158 (19)	−0.005 (2)
C4A	0.064 (2)	0.044 (3)	0.058 (3)	0.0047 (19)	−0.016 (2)	−0.012 (2)
C5A	0.055 (2)	0.041 (2)	0.054 (3)	0.0030 (17)	−0.0076 (19)	−0.008 (2)
C6A	0.054 (2)	0.042 (2)	0.062 (3)	0.0027 (18)	−0.0143 (19)	−0.006 (2)
C7A	0.059 (2)	0.047 (3)	0.062 (3)	0.007 (2)	−0.019 (2)	−0.008 (2)
C8A	0.054 (2)	0.048 (3)	0.056 (3)	−0.0027 (19)	−0.0051 (19)	−0.010 (2)
C9A	0.077 (3)	0.051 (3)	0.069 (3)	−0.001 (2)	−0.017 (2)	−0.001 (2)
C10A	0.087 (3)	0.065 (3)	0.066 (3)	−0.002 (3)	−0.025 (2)	−0.005 (3)
C11A	0.078 (3)	0.067 (3)	0.058 (3)	−0.010 (2)	−0.008 (2)	−0.016 (2)
C12A	0.053 (2)	0.052 (3)	0.062 (3)	−0.0046 (19)	0.006 (2)	−0.015 (2)
C13A	0.051 (2)	0.061 (3)	0.056 (3)	0.004 (2)	−0.0066 (18)	−0.013 (2)
C14A	0.066 (3)	0.048 (3)	0.073 (3)	0.002 (2)	−0.028 (2)	−0.003 (2)
C15A	0.085 (3)	0.061 (3)	0.091 (3)	0.012 (2)	−0.037 (3)	0.001 (3)
C16A	0.084 (3)	0.071 (4)	0.117 (4)	−0.019 (3)	−0.035 (3)	0.019 (3)
C17A	0.099 (3)	0.085 (4)	0.110 (4)	0.018 (3)	−0.057 (3)	−0.041 (3)
C18A	0.057 (2)	0.052 (3)	0.066 (3)	0.000 (2)	−0.001 (2)	−0.018 (2)
C19A	0.080 (3)	0.111 (5)	0.136 (5)	0.007 (3)	−0.003 (3)	−0.067 (4)
C20A	0.078 (3)	0.083 (4)	0.148 (5)	−0.009 (3)	0.028 (3)	−0.017 (4)
C21A	0.101 (4)	0.107 (5)	0.101 (4)	0.055 (3)	−0.008 (3)	−0.005 (4)
Cl1B	0.0960 (8)	0.0657 (8)	0.0911 (9)	0.0071 (6)	−0.0341 (7)	−0.0227 (7)
O1B	0.0527 (15)	0.069 (2)	0.0725 (19)	0.0015 (13)	−0.0083 (13)	−0.0259 (16)
N1B	0.0585 (19)	0.049 (2)	0.065 (2)	0.0049 (16)	−0.0031 (17)	−0.0160 (18)
C1B	0.048 (2)	0.042 (2)	0.058 (3)	0.0045 (17)	−0.0018 (18)	−0.011 (2)
C2B	0.052 (2)	0.041 (2)	0.054 (2)	0.0007 (18)	−0.0109 (19)	−0.009 (2)
C3B	0.046 (2)	0.041 (2)	0.056 (3)	0.0019 (17)	−0.0045 (18)	−0.008 (2)
C4B	0.060 (2)	0.046 (3)	0.056 (3)	0.0047 (19)	−0.007 (2)	−0.012 (2)
C5B	0.050 (2)	0.044 (2)	0.067 (3)	0.0018 (18)	−0.0089 (19)	−0.014 (2)
C6B	0.047 (2)	0.046 (3)	0.071 (3)	0.0023 (18)	−0.0029 (19)	−0.007 (2)
C7B	0.053 (2)	0.049 (3)	0.060 (3)	0.0053 (19)	0.004 (2)	−0.005 (2)
C8B	0.061 (2)	0.046 (3)	0.051 (3)	0.017 (2)	−0.006 (2)	−0.006 (2)
C9B	0.078 (3)	0.052 (3)	0.061 (3)	0.008 (2)	0.002 (2)	−0.003 (2)
C10B	0.084 (3)	0.071 (4)	0.066 (3)	0.013 (3)	0.010 (2)	−0.006 (3)
C11B	0.085 (3)	0.071 (4)	0.058 (3)	0.029 (3)	−0.007 (3)	−0.015 (3)
C12B	0.071 (3)	0.053 (3)	0.060 (3)	0.019 (2)	−0.020 (2)	−0.013 (2)
C13B	0.059 (2)	0.055 (3)	0.055 (3)	0.008 (2)	−0.0083 (19)	−0.008 (2)
C14B	0.047 (2)	0.043 (2)	0.066 (3)	0.0022 (17)	−0.0043 (18)	−0.011 (2)
C15B	0.062 (2)	0.073 (3)	0.085 (3)	0.018 (2)	−0.009 (2)	0.001 (3)
C16B	0.062 (3)	0.080 (3)	0.082 (3)	−0.001 (2)	0.007 (2)	−0.031 (3)
C17B	0.060 (2)	0.064 (3)	0.090 (3)	−0.007 (2)	0.009 (2)	−0.008 (3)
C18B	0.056 (2)	0.058 (3)	0.077 (3)	0.006 (2)	−0.015 (2)	−0.014 (3)
C19B	0.076 (3)	0.103 (5)	0.104 (5)	−0.004 (3)	−0.025 (3)	−0.055 (4)
C20B	0.092 (4)	0.082 (4)	0.136 (6)	0.014 (3)	−0.063 (4)	−0.014 (4)
C21B	0.090 (4)	0.088 (5)	0.116 (5)	−0.041 (3)	−0.013 (4)	−0.010 (4)

Geometric parameters (Å, º) top

Cl1A—C12A	1.749 (4)	C1B—C2B	1.412 (5)
O1A—C2A	1.358 (4)	C1B—C7B	1.447 (5)
O1A—H1A	0.8200	C2B—C3B	1.400 (5)
N1A—C7A	1.281 (4)	C3B—C4B	1.389 (5)
N1A—C8A	1.428 (4)	C3B—C14B	1.538 (5)
C1A—C6A	1.396 (5)	C4B—C5B	1.407 (5)
C1A—C2A	1.416 (5)	C4B—H4B	0.9300
C1A—C7A	1.449 (5)	C5B—C6B	1.385 (5)
C2A—C3A	1.395 (5)	C5B—C18B	1.532 (5)
C3A—C4A	1.397 (5)	C6B—H6B	0.9300
C3A—C14A	1.548 (5)	C7B—H7B	0.9300
C4A—C5A	1.394 (5)	C8B—C9B	1.384 (5)
C4A—H4A	0.9300	C8B—C13B	1.390 (5)
C5A—C6A	1.376 (5)	C9B—C10B	1.385 (5)
C5A—C18A	1.531 (5)	C9B—H9B	0.9300
C6A—H6A	0.9300	C10B—C11B	1.375 (6)
C7A—H7A	0.9300	C10B—H10B	0.9300
C8A—C9A	1.386 (5)	C11B—C12B	1.370 (6)
C8A—C13A	1.389 (5)	C11B—H11B	0.9300
C9A—C10A	1.376 (5)	C12B—C13B	1.377 (5)
C9A—H9A	0.9300	C13B—H13B	0.9300
C10A—C11A	1.379 (6)	C14B—C15B	1.528 (5)
C10A—H10A	0.9300	C14B—C16B	1.539 (5)
C11A—C12A	1.374 (5)	C14B—C17B	1.542 (5)
C11A—H11A	0.9300	C15B—H15D	0.9600
C12A—C13A	1.384 (5)	C15B—H15E	0.9600
C13A—H13A	0.9300	C15B—H15F	0.9600
C14A—C16A	1.529 (6)	C16B—H16D	0.9600
C14A—C17A	1.531 (6)	C16B—H16E	0.9600
C14A—C15A	1.540 (5)	C16B—H16F	0.9600
C15A—H15A	0.9600	C17B—H17D	0.9600
C15A—H15B	0.9600	C17B—H17E	0.9600
C15A—H15C	0.9600	C17B—H17F	0.9600
C16A—H16A	0.9600	C18B—C21C	1.43 (4)
C16A—H16B	0.9600	C18B—C20B	1.515 (6)
C16A—H16C	0.9600	C18B—C20C	1.52 (5)
C17A—H17A	0.9600	C18B—C19B	1.528 (6)
C17A—H17B	0.9600	C18B—C21B	1.548 (6)
C17A—H17C	0.9600	C18B—C19C	1.72 (4)
C18A—C20A	1.518 (6)	C19B—H19D	0.9600
C18A—C21A	1.521 (6)	C19B—H19E	0.9600
C18A—C19A	1.525 (5)	C19B—H19F	0.9600
C19A—H19A	0.9600	C20B—H20D	0.9600
C19A—H19B	0.9600	C20B—H20E	0.9600
C19A—H19C	0.9600	C20B—H20F	0.9600
C20A—H20A	0.9600	C21B—H21D	0.9600
C20A—H20B	0.9600	C21B—H21E	0.9600
C20A—H20C	0.9600	C21B—H21F	0.9600
C21A—H21A	0.9600	C19C—H19G	0.9600
C21A—H21B	0.9600	C19C—H19H	0.9600
C21A—H21C	0.9600	C19C—H19I	0.9600
Cl1B—C12B	1.746 (4)	C20C—H20G	0.9600
O1B—C2B	1.359 (4)	C20C—H20H	0.9600
O1B—H1B	0.8200	C20C—H20I	0.9600
N1B—C7B	1.280 (4)	C21C—H21G	0.9600
N1B—C8B	1.424 (5)	C21C—H21H	0.9600
C1B—C6B	1.392 (5)	C21C—H21I	0.9600

C2A—O1A—H1A	109.5	C3B—C4B—H4B	117.8
C7A—N1A—C8A	119.7 (3)	C5B—C4B—H4B	117.8
C6A—C1A—C2A	119.1 (3)	C6B—C5B—C4B	116.3 (3)
C6A—C1A—C7A	119.1 (3)	C6B—C5B—C18B	121.4 (3)
C2A—C1A—C7A	121.8 (3)	C4B—C5B—C18B	122.3 (3)
O1A—C2A—C3A	120.1 (3)	C5B—C6B—C1B	122.2 (3)
O1A—C2A—C1A	119.5 (3)	C5B—C6B—H6B	118.9
C3A—C2A—C1A	120.4 (3)	C1B—C6B—H6B	118.9
C2A—C3A—C4A	117.1 (3)	N1B—C7B—C1B	122.7 (3)
C2A—C3A—C14A	121.2 (3)	N1B—C7B—H7B	118.6
C4A—C3A—C14A	121.7 (4)	C1B—C7B—H7B	118.6
C5A—C4A—C3A	124.4 (4)	C9B—C8B—C13B	119.8 (4)
C5A—C4A—H4A	117.8	C9B—C8B—N1B	122.5 (4)
C3A—C4A—H4A	117.8	C13B—C8B—N1B	117.6 (4)
C6A—C5A—C4A	116.7 (3)	C8B—C9B—C10B	119.3 (4)
C6A—C5A—C18A	120.7 (3)	C8B—C9B—H9B	120.4
C4A—C5A—C18A	122.6 (3)	C10B—C9B—H9B	120.4
C5A—C6A—C1A	122.3 (3)	C11B—C10B—C9B	121.3 (4)
C5A—C6A—H6A	118.9	C11B—C10B—H10B	119.4
C1A—C6A—H6A	118.9	C9B—C10B—H10B	119.4
N1A—C7A—C1A	122.9 (3)	C12B—C11B—C10B	118.6 (4)
N1A—C7A—H7A	118.6	C12B—C11B—H11B	120.7
C1A—C7A—H7A	118.6	C10B—C11B—H11B	120.7
C9A—C8A—C13A	120.5 (4)	C11B—C12B—C13B	121.7 (4)
C9A—C8A—N1A	122.1 (4)	C11B—C12B—Cl1B	119.9 (4)
C13A—C8A—N1A	117.3 (3)	C13B—C12B—Cl1B	118.4 (4)
C10A—C9A—C8A	119.3 (4)	C12B—C13B—C8B	119.2 (4)
C10A—C9A—H9A	120.4	C12B—C13B—H13B	120.4
C8A—C9A—H9A	120.4	C8B—C13B—H13B	120.4
C9A—C10A—C11A	121.6 (4)	C15B—C14B—C3B	110.4 (3)
C9A—C10A—H10A	119.2	C15B—C14B—C16B	107.5 (3)
C11A—C10A—H10A	119.2	C3B—C14B—C16B	111.9 (3)
C12A—C11A—C10A	118.1 (4)	C15B—C14B—C17B	110.3 (3)
C12A—C11A—H11A	120.9	C3B—C14B—C17B	110.5 (3)
C10A—C11A—H11A	120.9	C16B—C14B—C17B	106.2 (3)
C11A—C12A—C13A	122.3 (4)	C14B—C15B—H15D	109.5
C11A—C12A—Cl1A	120.0 (3)	C14B—C15B—H15E	109.5
C13A—C12A—Cl1A	117.7 (3)	H15D—C15B—H15E	109.5
C12A—C13A—C8A	118.3 (4)	C14B—C15B—H15F	109.5
C12A—C13A—H13A	120.9	H15D—C15B—H15F	109.5
C8A—C13A—H13A	120.9	H15E—C15B—H15F	109.5
C16A—C14A—C17A	108.0 (4)	C14B—C16B—H16D	109.5
C16A—C14A—C15A	110.1 (4)	C14B—C16B—H16E	109.5
C17A—C14A—C15A	106.7 (3)	H16D—C16B—H16E	109.5
C16A—C14A—C3A	109.5 (3)	C14B—C16B—H16F	109.5
C17A—C14A—C3A	112.0 (3)	H16D—C16B—H16F	109.5
C15A—C14A—C3A	110.4 (3)	H16E—C16B—H16F	109.5
C14A—C15A—H15A	109.5	C14B—C17B—H17D	109.5
C14A—C15A—H15B	109.5	C14B—C17B—H17E	109.5
H15A—C15A—H15B	109.5	H17D—C17B—H17E	109.5
C14A—C15A—H15C	109.5	C14B—C17B—H17F	109.5
H15A—C15A—H15C	109.5	H17D—C17B—H17F	109.5
H15B—C15A—H15C	109.5	H17E—C17B—H17F	109.5
C14A—C16A—H16A	109.5	C21C—C18B—C20B	143.8 (17)
C14A—C16A—H16B	109.5	C21C—C18B—C20C	121 (3)
H16A—C16A—H16B	109.5	C20B—C18B—C20C	48 (2)
C14A—C16A—H16C	109.5	C21C—C18B—C19B	51 (2)
H16A—C16A—H16C	109.5	C20B—C18B—C19B	109.0 (4)
H16B—C16A—H16C	109.5	C20C—C18B—C19B	136 (2)
C14A—C17A—H17A	109.5	C21C—C18B—C5B	105.5 (17)
C14A—C17A—H17B	109.5	C20B—C18B—C5B	110.5 (4)
H17A—C17A—H17B	109.5	C20C—C18B—C5B	110 (2)
C14A—C17A—H17C	109.5	C19B—C18B—C5B	113.5 (3)
H17A—C17A—H17C	109.5	C21C—C18B—C21B	62 (2)
H17B—C17A—H17C	109.5	C20B—C18B—C21B	108.4 (4)
C20A—C18A—C21A	109.5 (4)	C20C—C18B—C21B	63 (3)
C20A—C18A—C19A	107.2 (4)	C19B—C18B—C21B	106.8 (4)
C21A—C18A—C19A	107.7 (4)	C5B—C18B—C21B	108.5 (4)
C20A—C18A—C5A	110.1 (3)	C21C—C18B—C19C	110 (3)
C21A—C18A—C5A	110.0 (3)	C20B—C18B—C19C	58.0 (16)
C19A—C18A—C5A	112.3 (3)	C20C—C18B—C19C	105 (3)
C18A—C19A—H19A	109.5	C19B—C18B—C19C	59.8 (18)
C18A—C19A—H19B	109.5	C5B—C18B—C19C	103.0 (15)
H19A—C19A—H19B	109.5	C21B—C18B—C19C	148.6 (15)
C18A—C19A—H19C	109.5	C18B—C19B—H19D	109.5
H19A—C19A—H19C	109.5	C18B—C19B—H19E	109.5
H19B—C19A—H19C	109.5	C18B—C19B—H19F	109.5
C18A—C20A—H20A	109.5	C18B—C20B—H20D	109.5
C18A—C20A—H20B	109.5	C18B—C20B—H20E	109.5
H20A—C20A—H20B	109.5	C18B—C20B—H20F	109.5
C18A—C20A—H20C	109.5	C18B—C21B—H21D	109.5
H20A—C20A—H20C	109.5	C18B—C21B—H21E	109.5
H20B—C20A—H20C	109.5	C18B—C21B—H21F	109.5
C18A—C21A—H21A	109.5	C18B—C19C—H19G	109.5
C18A—C21A—H21B	109.5	C18B—C19C—H19H	109.5
H21A—C21A—H21B	109.5	H19G—C19C—H19H	109.5
C18A—C21A—H21C	109.5	C18B—C19C—H19I	109.5
H21A—C21A—H21C	109.5	H19G—C19C—H19I	109.5
H21B—C21A—H21C	109.5	H19H—C19C—H19I	109.5
C2B—O1B—H1B	109.5	C18B—C20C—H20G	109.5
C7B—N1B—C8B	120.8 (3)	C18B—C20C—H20H	109.5
C6B—C1B—C2B	119.3 (3)	H20G—C20C—H20H	109.5
C6B—C1B—C7B	119.4 (3)	C18B—C20C—H20I	109.5
C2B—C1B—C7B	121.3 (3)	H20G—C20C—H20I	109.5
O1B—C2B—C3B	119.6 (3)	H20H—C20C—H20I	109.5
O1B—C2B—C1B	119.8 (3)	C18B—C21C—H21G	109.5
C3B—C2B—C1B	120.6 (3)	C18B—C21C—H21H	109.5
C4B—C3B—C2B	117.2 (3)	H21G—C21C—H21H	109.5
C4B—C3B—C14B	122.2 (3)	C18B—C21C—H21I	109.5
C2B—C3B—C14B	120.6 (3)	H21G—C21C—H21I	109.5
C3B—C4B—C5B	124.3 (4)	H21H—C21C—H21I	109.5

C6A—C1A—C2A—O1A	176.7 (3)	C7B—C1B—C2B—C3B	−178.9 (4)
C7A—C1A—C2A—O1A	−2.1 (5)	O1B—C2B—C3B—C4B	176.7 (3)
C6A—C1A—C2A—C3A	−3.2 (5)	C1B—C2B—C3B—C4B	−2.4 (5)
C7A—C1A—C2A—C3A	178.0 (4)	O1B—C2B—C3B—C14B	−2.2 (5)
O1A—C2A—C3A—C4A	−176.4 (3)	C1B—C2B—C3B—C14B	178.7 (3)
C1A—C2A—C3A—C4A	3.4 (5)	C2B—C3B—C4B—C5B	0.8 (6)
O1A—C2A—C3A—C14A	2.8 (5)	C14B—C3B—C4B—C5B	179.6 (3)
C1A—C2A—C3A—C14A	−177.4 (3)	C3B—C4B—C5B—C6B	0.7 (6)
C2A—C3A—C4A—C5A	−0.9 (6)	C3B—C4B—C5B—C18B	−177.8 (4)
C14A—C3A—C4A—C5A	179.9 (3)	C4B—C5B—C6B—C1B	−0.5 (6)
C3A—C4A—C5A—C6A	−1.9 (6)	C18B—C5B—C6B—C1B	178.0 (4)
C3A—C4A—C5A—C18A	177.5 (4)	C2B—C1B—C6B—C5B	−1.0 (6)
C4A—C5A—C6A—C1A	2.2 (6)	C7B—C1B—C6B—C5B	−179.6 (4)
C18A—C5A—C6A—C1A	−177.2 (3)	C8B—N1B—C7B—C1B	−179.5 (3)
C2A—C1A—C6A—C5A	0.2 (6)	C6B—C1B—C7B—N1B	−179.9 (4)
C7A—C1A—C6A—C5A	179.1 (4)	C2B—C1B—C7B—N1B	1.6 (6)
C8A—N1A—C7A—C1A	178.6 (3)	C7B—N1B—C8B—C9B	45.5 (5)
C6A—C1A—C7A—N1A	−179.1 (4)	C7B—N1B—C8B—C13B	−137.7 (4)
C2A—C1A—C7A—N1A	−0.3 (6)	C13B—C8B—C9B—C10B	1.2 (6)
C7A—N1A—C8A—C9A	−46.6 (5)	N1B—C8B—C9B—C10B	177.9 (3)
C7A—N1A—C8A—C13A	137.0 (4)	C8B—C9B—C10B—C11B	0.4 (6)
C13A—C8A—C9A—C10A	−2.5 (6)	C9B—C10B—C11B—C12B	−1.7 (7)
N1A—C8A—C9A—C10A	−178.7 (4)	C10B—C11B—C12B—C13B	1.4 (6)
C8A—C9A—C10A—C11A	1.2 (7)	C10B—C11B—C12B—Cl1B	180.0 (3)
C9A—C10A—C11A—C12A	0.5 (6)	C11B—C12B—C13B—C8B	0.2 (6)
C10A—C11A—C12A—C13A	−0.9 (6)	Cl1B—C12B—C13B—C8B	−178.4 (3)
C10A—C11A—C12A—Cl1A	179.8 (3)	C9B—C8B—C13B—C12B	−1.4 (5)
C11A—C12A—C13A—C8A	−0.3 (6)	N1B—C8B—C13B—C12B	−178.4 (3)
Cl1A—C12A—C13A—C8A	178.9 (3)	C4B—C3B—C14B—C15B	−115.2 (4)
C9A—C8A—C13A—C12A	2.1 (6)	C2B—C3B—C14B—C15B	63.6 (4)
N1A—C8A—C13A—C12A	178.5 (3)	C4B—C3B—C14B—C16B	4.4 (5)
C2A—C3A—C14A—C16A	−65.5 (5)	C2B—C3B—C14B—C16B	−176.7 (4)
C4A—C3A—C14A—C16A	113.6 (4)	C4B—C3B—C14B—C17B	122.5 (4)
C2A—C3A—C14A—C17A	174.7 (4)	C2B—C3B—C14B—C17B	−58.7 (5)
C4A—C3A—C14A—C17A	−6.2 (5)	C6B—C5B—C18B—C21C	−125 (2)
C2A—C3A—C14A—C15A	55.9 (5)	C4B—C5B—C18B—C21C	53 (2)
C4A—C3A—C14A—C15A	−125.0 (4)	C6B—C5B—C18B—C20B	58.7 (6)
C6A—C5A—C18A—C20A	−62.8 (5)	C4B—C5B—C18B—C20B	−122.8 (5)
C4A—C5A—C18A—C20A	117.9 (4)	C6B—C5B—C18B—C20C	7 (3)
C6A—C5A—C18A—C21A	57.9 (5)	C4B—C5B—C18B—C20C	−175 (3)
C4A—C5A—C18A—C21A	−121.4 (4)	C6B—C5B—C18B—C19B	−178.5 (5)
C6A—C5A—C18A—C19A	177.9 (4)	C4B—C5B—C18B—C19B	−0.1 (6)
C4A—C5A—C18A—C19A	−1.5 (6)	C6B—C5B—C18B—C21B	−60.0 (5)
C6B—C1B—C2B—O1B	−176.5 (3)	C4B—C5B—C18B—C21B	118.4 (5)
C7B—C1B—C2B—O1B	2.0 (5)	C6B—C5B—C18B—C19C	119.1 (18)
C6B—C1B—C2B—C3B	2.5 (6)	C4B—C5B—C18B—C19C	−62.5 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···N1A	0.82	1.86	2.599 (4)	149
O1B—H1B···N1B	0.82	1.84	2.578 (4)	149

(5) top

Crystal data top

C_21.05H_26.14BrNO	F(000) = 808
M_r = 388.34	D_x = 1.299 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
a = 18.0699 (14) Å	Cell parameters from 9961 reflections
b = 10.5997 (10) Å	θ = 3.0–27.4°
c = 10.3838 (9) Å	µ = 2.08 mm⁻¹
β = 92.858 (2)°	T = 296 K
V = 1986.4 (3) Å³	Platelet, yellow
Z = 4	0.20 × 0.14 × 0.06 mm

Data collection top

Rigaku R-AXIS RAPID IP Area Detector System diffractometer	4500 independent reflections
Radiation source: rotating anode X-ray tube	1915 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.109
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan Absorption was corrected by ABSCOR	h = −23→23
T_min = 0.559, T_max = 0.884	k = −13→13
18792 measured reflections	l = −12→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0495P)² + 0.7378P] where P = (F_o² + 2F_c²)/3
4500 reflections	(Δ/σ)_max = 0.001
241 parameters	Δρ_max = 0.30 e Å⁻³
1 restraint	Δρ_min = −0.39 e Å⁻³

Crystal data top

C_21.05H_26.14BrNO	V = 1986.4 (3) Å³
M_r = 388.34	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.0699 (14) Å	µ = 2.08 mm⁻¹
b = 10.5997 (10) Å	T = 296 K
c = 10.3838 (9) Å	0.20 × 0.14 × 0.06 mm
β = 92.858 (2)°

Data collection top

Rigaku R-AXIS RAPID IP Area Detector System diffractometer	4500 independent reflections
Absorption correction: multi-scan Absorption was corrected by ABSCOR	1915 reflections with I > 2σ(I)
T_min = 0.559, T_max = 0.884	R_int = 0.109
18792 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	1 restraint
wR(F²) = 0.147	H-atom parameters constrained
S = 1.02	Δρ_max = 0.30 e Å⁻³
4500 reflections	Δρ_min = −0.39 e Å⁻³
241 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.63428 (3)	0.94478 (5)	0.78959 (5)	0.0846 (3)
O1	0.31975 (16)	0.5115 (3)	0.3426 (3)	0.0675 (8)
H1	0.3493	0.5499	0.3906	0.101*
N1	0.38417 (19)	0.7042 (3)	0.4600 (3)	0.0621 (10)
C1	0.2712 (2)	0.7202 (4)	0.3264 (4)	0.0539 (11)
C2	0.2675 (2)	0.5929 (4)	0.2929 (4)	0.0526 (11)
C3	0.2104 (2)	0.5486 (4)	0.2085 (4)	0.0493 (10)
C4	0.1588 (2)	0.6372 (4)	0.1616 (4)	0.0527 (11)
H4	0.1209	0.6091	0.1049	0.063*
C5	0.1598 (2)	0.7651 (4)	0.1937 (4)	0.0535 (11)
C6	0.2176 (2)	0.8048 (4)	0.2772 (4)	0.0586 (11)
H6	0.2207	0.8894	0.3008	0.070*
C7	0.3313 (2)	0.7713 (5)	0.4106 (4)	0.0637 (12)
H7	0.3310	0.8571	0.4292	0.076*
C8	0.4413 (2)	0.7628 (5)	0.5396 (4)	0.0601 (12)
C9	0.4299 (3)	0.8713 (5)	0.6096 (5)	0.0860 (16)
H9	0.3833	0.9085	0.6076	0.103*
C10	0.4878 (3)	0.9242 (5)	0.6824 (5)	0.0882 (17)
H10	0.4798	0.9979	0.7283	0.106*
C11	0.5559 (2)	0.8711 (5)	0.6884 (4)	0.0605 (12)
C12	0.5674 (2)	0.7614 (5)	0.6213 (5)	0.0754 (14)
H12	0.6139	0.7234	0.6258	0.090*
C13	0.5101 (2)	0.7076 (5)	0.5471 (5)	0.0738 (14)
H13	0.5182	0.6334	0.5020	0.089*
C14	0.2046 (2)	0.4088 (4)	0.1694 (4)	0.0570 (11)
C15	0.1986 (3)	0.3261 (4)	0.2895 (4)	0.0738 (14)
H15A	0.2405	0.3412	0.3480	0.111*
H15B	0.1977	0.2388	0.2647	0.111*
H15C	0.1538	0.3464	0.3311	0.111*
C16	0.2737 (3)	0.3707 (5)	0.0962 (4)	0.0768 (14)
H16A	0.2762	0.4211	0.0198	0.115*
H16B	0.2702	0.2832	0.0728	0.115*
H16C	0.3175	0.3840	0.1507	0.115*
C17	0.1361 (3)	0.3813 (5)	0.0797 (4)	0.0796 (15)
H17A	0.0922	0.4073	0.1209	0.119*
H17B	0.1335	0.2926	0.0618	0.119*
H17C	0.1399	0.4270	0.0005	0.119*
C18	0.1004 (2)	0.8578 (4)	0.1401 (4)	0.0586 (11)
C19A	0.1124 (9)	0.8889 (17)	0.0083 (13)	0.070 (5)*	0.366 (13)
H19A	0.1105	0.8134	−0.0428	0.105*	0.366 (13)
H19B	0.1600	0.9280	0.0028	0.105*	0.366 (13)
H19C	0.0745	0.9462	−0.0234	0.105*	0.366 (13)
C20A	0.0191 (8)	0.7867 (13)	0.1417 (19)	0.074 (5)*	0.366 (13)
H20A	0.0115	0.7555	0.2268	0.110*	0.366 (13)
H20B	0.0178	0.7177	0.0818	0.110*	0.366 (13)
H20C	−0.0194	0.8458	0.1173	0.110*	0.366 (13)
C21A	0.0922 (11)	0.9728 (17)	0.2220 (18)	0.081 (6)*	0.366 (13)
H21A	0.0483	1.0177	0.1937	0.122*	0.366 (13)
H21B	0.1346	1.0264	0.2145	0.122*	0.366 (13)
H21C	0.0886	0.9481	0.3104	0.122*	0.366 (13)
C19B	0.1388 (9)	0.952 (2)	0.0459 (19)	0.068 (6)*	0.325 (16)
H19D	0.1541	0.9062	−0.0282	0.101*	0.325 (16)
H19E	0.1813	0.9893	0.0898	0.101*	0.325 (16)
H19F	0.1044	1.0165	0.0188	0.101*	0.325 (16)
C20B	0.0351 (10)	0.7909 (15)	0.063 (2)	0.070 (6)*	0.325 (16)
H20D	−0.0015	0.8524	0.0360	0.106*	0.325 (16)
H20E	0.0131	0.7293	0.1170	0.106*	0.325 (16)
H20F	0.0536	0.7500	−0.0114	0.106*	0.325 (16)
C21B	0.0692 (9)	0.9361 (18)	0.2506 (13)	0.044 (4)*	0.325 (16)
H21D	0.1083	0.9856	0.2912	0.066*	0.325 (16)
H21E	0.0492	0.8804	0.3128	0.066*	0.325 (16)
H21F	0.0309	0.9910	0.2162	0.066*	0.325 (16)
C19C	0.1409 (11)	0.9921 (19)	0.119 (2)	0.092 (7)*	0.325 (12)
H19G	0.1793	0.9818	0.0590	0.139*	0.325 (12)
H19H	0.1623	1.0218	0.1999	0.139*	0.325 (12)
H19I	0.1053	1.0523	0.0854	0.139*	0.325 (12)
C20C	0.0441 (11)	0.875 (2)	0.2302 (18)	0.088 (7)*	0.325 (12)
H20G	0.0076	0.9330	0.1954	0.132*	0.325 (12)
H20H	0.0658	0.9078	0.3095	0.132*	0.325 (12)
H20I	0.0210	0.7952	0.2463	0.132*	0.325 (12)
C21C	0.0730 (10)	0.8211 (16)	0.0048 (15)	0.064 (5)*	0.325 (12)
H21G	0.0379	0.8827	−0.0279	0.096*	0.325 (12)
H21H	0.0496	0.7399	0.0069	0.096*	0.325 (12)
H21I	0.1141	0.8176	−0.0501	0.096*	0.325 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0727 (4)	0.0862 (4)	0.0924 (4)	−0.0136 (3)	−0.0205 (3)	−0.0036 (3)
O1	0.0636 (19)	0.0562 (19)	0.080 (2)	0.0091 (15)	−0.0204 (16)	0.0033 (16)
N1	0.056 (2)	0.063 (3)	0.067 (2)	0.0015 (19)	−0.0115 (19)	0.0083 (19)
C1	0.054 (2)	0.050 (3)	0.057 (3)	−0.003 (2)	−0.009 (2)	0.006 (2)
C2	0.048 (2)	0.055 (3)	0.054 (2)	0.005 (2)	−0.002 (2)	0.007 (2)
C3	0.051 (2)	0.050 (3)	0.047 (2)	0.000 (2)	0.002 (2)	0.000 (2)
C4	0.053 (3)	0.057 (3)	0.046 (2)	0.004 (2)	−0.006 (2)	−0.001 (2)
C5	0.054 (3)	0.056 (3)	0.050 (2)	0.007 (2)	−0.001 (2)	0.004 (2)
C6	0.060 (3)	0.051 (3)	0.063 (3)	−0.002 (2)	−0.006 (2)	0.004 (2)
C7	0.065 (3)	0.060 (3)	0.064 (3)	−0.004 (2)	−0.010 (2)	0.004 (2)
C8	0.056 (3)	0.067 (3)	0.057 (3)	−0.002 (2)	−0.003 (2)	0.000 (2)
C9	0.058 (3)	0.112 (5)	0.086 (3)	0.021 (3)	−0.018 (3)	−0.028 (3)
C10	0.074 (4)	0.094 (4)	0.095 (4)	0.020 (3)	−0.016 (3)	−0.036 (3)
C11	0.052 (3)	0.068 (3)	0.060 (3)	0.001 (2)	−0.006 (2)	−0.002 (2)
C12	0.051 (3)	0.081 (4)	0.093 (4)	0.007 (3)	−0.013 (3)	0.001 (3)
C13	0.063 (3)	0.067 (3)	0.089 (3)	0.011 (3)	−0.016 (3)	−0.012 (3)
C14	0.064 (3)	0.052 (3)	0.054 (2)	−0.001 (2)	0.001 (2)	0.001 (2)
C15	0.092 (4)	0.059 (3)	0.071 (3)	−0.008 (3)	0.001 (3)	0.010 (3)
C16	0.091 (4)	0.063 (3)	0.077 (3)	0.009 (3)	0.013 (3)	−0.004 (3)
C17	0.087 (4)	0.067 (3)	0.083 (3)	−0.007 (3)	−0.018 (3)	−0.015 (3)
C18	0.062 (3)	0.064 (3)	0.050 (2)	0.013 (2)	−0.002 (2)	0.001 (2)

Geometric parameters (Å, º) top

Br1—C11	1.890 (4)	C17—H17C	0.9600
O1—C2	1.361 (4)	C18—C20C	1.428 (17)
O1—H1	0.8200	C18—C19A	1.435 (13)
N1—C7	1.277 (5)	C18—C21A	1.498 (16)
N1—C8	1.432 (5)	C18—C21C	1.517 (14)
C1—C2	1.395 (5)	C18—C21B	1.544 (15)
C1—C6	1.398 (5)	C18—C20B	1.564 (15)
C1—C7	1.464 (5)	C18—C19B	1.580 (17)
C2—C3	1.401 (5)	C18—C19C	1.621 (19)
C3—C4	1.394 (5)	C18—C20A	1.653 (15)
C3—C14	1.539 (6)	C19A—H19A	0.9600
C4—C5	1.396 (6)	C19A—H19B	0.9600
C4—H4	0.9300	C19A—H19C	0.9600
C5—C6	1.389 (5)	C20A—H20A	0.9600
C5—C18	1.538 (5)	C20A—H20B	0.9600
C6—H6	0.9300	C20A—H20C	0.9600
C7—H7	0.9300	C21A—H21A	0.9600
C8—C13	1.373 (6)	C21A—H21B	0.9600
C8—C9	1.380 (6)	C21A—H21C	0.9600
C9—C10	1.379 (6)	C19B—H19D	0.9600
C9—H9	0.9300	C19B—H19E	0.9600
C10—C11	1.352 (6)	C19B—H19F	0.9600
C10—H10	0.9300	C20B—H20D	0.9600
C11—C12	1.377 (6)	C20B—H20E	0.9600
C12—C13	1.383 (6)	C20B—H20F	0.9600
C12—H12	0.9300	C21B—H21D	0.9600
C13—H13	0.9300	C21B—H21E	0.9600
C14—C15	1.533 (6)	C21B—H21F	0.9600
C14—C17	1.539 (6)	C19C—H19G	0.9600
C14—C16	1.547 (6)	C19C—H19H	0.9600
C15—H15A	0.9600	C19C—H19I	0.9600
C15—H15B	0.9600	C20C—H20G	0.9600
C15—H15C	0.9600	C20C—H20H	0.9600
C16—H16A	0.9600	C20C—H20I	0.9600
C16—H16B	0.9600	C21C—H21G	0.9600
C16—H16C	0.9600	C21C—H21H	0.9600
C17—H17A	0.9600	C21C—H21I	0.9600
C17—H17B	0.9600

C2—O1—H1	109.5	C21A—C18—C5	113.7 (7)
C7—N1—C8	119.5 (4)	C21C—C18—C5	111.2 (6)
C2—C1—C6	120.4 (4)	C20C—C18—C21B	31.5 (9)
C2—C1—C7	122.1 (4)	C19A—C18—C21B	131.5 (9)
C6—C1—C7	117.5 (4)	C21A—C18—C21B	24.7 (8)
O1—C2—C1	119.7 (4)	C21C—C18—C21B	135.3 (8)
O1—C2—C3	120.0 (4)	C5—C18—C21B	110.4 (6)
C1—C2—C3	120.3 (4)	C20C—C18—C20B	81.3 (11)
C4—C3—C2	116.9 (4)	C19A—C18—C20B	76.2 (10)
C4—C3—C14	121.4 (3)	C21A—C18—C20B	124.5 (10)
C2—C3—C14	121.7 (3)	C21C—C18—C20B	37.4 (9)
C3—C4—C5	124.8 (4)	C5—C18—C20B	113.0 (7)
C3—C4—H4	117.6	C21B—C18—C20B	109.3 (9)
C5—C4—H4	117.6	C20C—C18—C19B	132.5 (11)
C6—C5—C4	116.4 (4)	C19A—C18—C19B	34.2 (8)
C6—C5—C18	121.4 (4)	C21A—C18—C19B	84.1 (10)
C4—C5—C18	122.2 (4)	C21C—C18—C19B	73.8 (10)
C5—C6—C1	121.3 (4)	C5—C18—C19B	107.8 (6)
C5—C6—H6	119.4	C21B—C18—C19B	108.0 (10)
C1—C6—H6	119.4	C20B—C18—C19B	108.2 (9)
N1—C7—C1	123.4 (4)	C20C—C18—C19C	108.6 (11)
N1—C7—H7	118.3	C19A—C18—C19C	65.1 (11)
C1—C7—H7	118.3	C21A—C18—C19C	54.6 (11)
C13—C8—C9	118.9 (4)	C21C—C18—C19C	103.2 (10)
C13—C8—N1	118.2 (4)	C5—C18—C19C	107.4 (7)
C9—C8—N1	123.0 (4)	C21B—C18—C19C	79.2 (10)
C10—C9—C8	120.0 (5)	C20B—C18—C19C	131.6 (10)
C10—C9—H9	120.0	C19B—C18—C19C	31.5 (8)
C8—C9—H9	120.0	C20C—C18—C20A	52.2 (11)
C11—C10—C9	121.3 (5)	C19A—C18—C20A	106.9 (9)
C11—C10—H10	119.4	C21A—C18—C20A	104.6 (9)
C9—C10—H10	119.4	C21C—C18—C20A	69.0 (9)
C10—C11—C12	119.3 (4)	C5—C18—C20A	108.1 (6)
C10—C11—Br1	120.5 (4)	C21B—C18—C20A	83.1 (9)
C12—C11—Br1	120.2 (3)	C20B—C18—C20A	31.7 (8)
C11—C12—C13	120.1 (4)	C19B—C18—C20A	135.3 (8)
C11—C12—H12	119.9	C19C—C18—C20A	144.1 (9)
C13—C12—H12	119.9	C18—C19A—H19A	109.5
C8—C13—C12	120.5 (5)	C18—C19A—H19B	109.5
C8—C13—H13	119.8	C18—C19A—H19C	109.5
C12—C13—H13	119.8	C18—C20A—H20A	109.5
C15—C14—C17	107.3 (4)	C18—C20A—H20B	109.5
C15—C14—C3	110.1 (3)	C18—C20A—H20C	109.5
C17—C14—C3	112.6 (3)	C18—C21A—H21A	109.5
C15—C14—C16	110.0 (4)	C18—C21A—H21B	109.5
C17—C14—C16	107.3 (4)	C18—C21A—H21C	109.5
C3—C14—C16	109.6 (3)	C18—C19B—H19D	109.5
C14—C15—H15A	109.5	C18—C19B—H19E	109.5
C14—C15—H15B	109.5	H19D—C19B—H19E	109.5
H15A—C15—H15B	109.5	C18—C19B—H19F	109.5
C14—C15—H15C	109.5	H19D—C19B—H19F	109.5
H15A—C15—H15C	109.5	H19E—C19B—H19F	109.5
H15B—C15—H15C	109.5	C18—C20B—H20D	109.5
C14—C16—H16A	109.5	C18—C20B—H20E	109.5
C14—C16—H16B	109.5	H20D—C20B—H20E	109.5
H16A—C16—H16B	109.5	C18—C20B—H20F	109.5
C14—C16—H16C	109.5	H20D—C20B—H20F	109.5
H16A—C16—H16C	109.5	H20E—C20B—H20F	109.5
H16B—C16—H16C	109.5	C18—C21B—H21D	109.5
C14—C17—H17A	109.5	C18—C21B—H21E	109.5
C14—C17—H17B	109.5	H21D—C21B—H21E	109.5
H17A—C17—H17B	109.5	C18—C21B—H21F	109.5
C14—C17—H17C	109.5	H21D—C21B—H21F	109.5
H17A—C17—H17C	109.5	H21E—C21B—H21F	109.5
H17B—C17—H17C	109.5	C18—C19C—H19G	109.5
C20C—C18—C19A	137.9 (10)	C18—C19C—H19H	109.5
C20C—C18—C21A	55.3 (12)	C18—C19C—H19I	109.5
C19A—C18—C21A	112.2 (10)	C18—C20C—H20G	109.5
C20C—C18—C21C	115.3 (10)	C18—C20C—H20H	109.5
C19A—C18—C21C	39.9 (9)	C18—C20C—H20I	109.5
C21A—C18—C21C	134.2 (9)	C18—C21C—H21G	109.5
C20C—C18—C5	110.6 (8)	C18—C21C—H21H	109.5
C19A—C18—C5	110.9 (6)	C18—C21C—H21I	109.5

C6—C1—C2—O1	−179.3 (4)	C9—C8—C13—C12	−1.5 (7)
C7—C1—C2—O1	2.2 (6)	N1—C8—C13—C12	179.1 (4)
C6—C1—C2—C3	0.6 (6)	C11—C12—C13—C8	0.0 (8)
C7—C1—C2—C3	−177.9 (4)	C4—C3—C14—C15	−121.4 (4)
O1—C2—C3—C4	179.8 (4)	C2—C3—C14—C15	58.5 (5)
C1—C2—C3—C4	−0.1 (6)	C4—C3—C14—C17	−1.7 (6)
O1—C2—C3—C14	−0.1 (6)	C2—C3—C14—C17	178.1 (4)
C1—C2—C3—C14	−180.0 (4)	C4—C3—C14—C16	117.6 (4)
C2—C3—C4—C5	−0.7 (6)	C2—C3—C14—C16	−62.6 (5)
C14—C3—C4—C5	179.2 (4)	C6—C5—C18—C20C	−83.4 (12)
C3—C4—C5—C6	0.9 (6)	C4—C5—C18—C20C	96.6 (12)
C3—C4—C5—C18	−179.1 (4)	C6—C5—C18—C19A	104.2 (10)
C4—C5—C6—C1	−0.4 (6)	C4—C5—C18—C19A	−75.8 (11)
C18—C5—C6—C1	179.6 (4)	C6—C5—C18—C21A	−23.3 (11)
C2—C1—C6—C5	−0.3 (7)	C4—C5—C18—C21A	156.7 (10)
C7—C1—C6—C5	178.2 (4)	C6—C5—C18—C21C	147.1 (9)
C8—N1—C7—C1	179.0 (4)	C4—C5—C18—C21C	−32.9 (10)
C2—C1—C7—N1	−0.4 (7)	C6—C5—C18—C21B	−49.8 (10)
C6—C1—C7—N1	−178.9 (4)	C4—C5—C18—C21B	130.3 (9)
C7—N1—C8—C13	−153.2 (4)	C6—C5—C18—C20B	−172.5 (11)
C7—N1—C8—C9	27.5 (7)	C4—C5—C18—C20B	7.5 (12)
C13—C8—C9—C10	1.9 (8)	C6—C5—C18—C19B	68.0 (10)
N1—C8—C9—C10	−178.7 (5)	C4—C5—C18—C19B	−112.0 (10)
C8—C9—C10—C11	−0.9 (9)	C6—C5—C18—C19C	34.9 (10)
C9—C10—C11—C12	−0.6 (8)	C4—C5—C18—C19C	−145.1 (10)
C9—C10—C11—Br1	−179.6 (4)	C6—C5—C18—C20A	−139.0 (8)
C10—C11—C12—C13	1.0 (7)	C4—C5—C18—C20A	41.0 (9)
Br1—C11—C12—C13	−179.9 (4)

(6) top

Crystal data top

C₂₁H₂₇NO	D_x = 1.104 Mg m⁻³
M_r = 309.44	Mo Kα radiation, λ = 0.71075 Å
Orthorhombic, Pna2₁	Cell parameters from 15059 reflections
a = 12.4043 (6) Å	θ = 3.1–27.4°
b = 8.9918 (5) Å	µ = 0.07 mm⁻¹
c = 16.6903 (7) Å	T = 296 K
V = 1861.59 (16) Å³	Block, yellow
Z = 4	0.50 × 0.35 × 0.15 mm
F(000) = 672

Data collection top

Rigaku R-AXIS RAPID IP Area Detector System diffractometer	2193 independent reflections
Radiation source: rotating anode X-ray tube	1955 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 27.4°, θ_min = 3.1°
Absorption correction: multi-scan Absorption was corrected by ABSCOR	h = −16→15
T_min = 0.798, T_max = 0.990	k = −11→11
17422 measured reflections	l = −21→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0635P)² + 0.1242P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2193 reflections	Δρ_max = 0.22 e Å⁻³
214 parameters	Δρ_min = −0.14 e Å⁻³
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₁H₂₇NO	V = 1861.59 (16) Å³
M_r = 309.44	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 12.4043 (6) Å	µ = 0.07 mm⁻¹
b = 8.9918 (5) Å	T = 296 K
c = 16.6903 (7) Å	0.50 × 0.35 × 0.15 mm

Data collection top

Rigaku R-AXIS RAPID IP Area Detector System diffractometer	2193 independent reflections
Absorption correction: multi-scan Absorption was corrected by ABSCOR	1955 reflections with I > 2σ(I)
T_min = 0.798, T_max = 0.990	R_int = 0.032
17422 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.101	H-atom parameters constrained
S = 1.06	Δρ_max = 0.22 e Å⁻³
2193 reflections	Δρ_min = −0.14 e Å⁻³
214 parameters	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	−0.84007 (12)	−0.63129 (15)	−0.09389 (9)	0.0426 (3)
H1	−0.8852	−0.5749	−0.0748	0.064*
N1	−0.94351 (13)	−0.38858 (18)	−0.06977 (10)	0.0374 (4)
C1	−0.81743 (15)	−0.4166 (2)	−0.17701 (12)	0.0337 (4)
C2	−0.79029 (15)	−0.5638 (2)	−0.15614 (10)	0.0327 (4)
C3	−0.70898 (16)	−0.6406 (2)	−0.19846 (11)	0.0347 (4)
C4	−0.66127 (16)	−0.5665 (2)	−0.26238 (11)	0.0368 (4)
H4	−0.6075	−0.6158	−0.2908	0.044*
C5	−0.68902 (16)	−0.4218 (2)	−0.28688 (11)	0.0346 (4)
C6	−0.76649 (16)	−0.3483 (2)	−0.24299 (12)	0.0354 (4)
H6	−0.7856	−0.2518	−0.2571	0.043*
C7	−0.89474 (17)	−0.3316 (2)	−0.12988 (12)	0.0364 (4)
H7	−0.9090	−0.2335	−0.1439	0.044*
C8	−1.01957 (15)	−0.3096 (2)	−0.02234 (12)	0.0351 (4)
C9	−1.0794 (2)	−0.1892 (3)	−0.04932 (14)	0.0497 (5)
H9	−1.0699	−0.1531	−0.1011	0.060*
C10	−1.1536 (2)	−0.1231 (3)	0.00167 (16)	0.0579 (6)
H10	−1.1933	−0.0418	−0.0161	0.070*
C11	−1.1695 (2)	−0.1755 (3)	0.07772 (15)	0.0566 (6)
H11	−1.2194	−0.1297	0.1111	0.068*
C12	−1.1114 (2)	−0.2960 (3)	0.10484 (14)	0.0544 (6)
H12	−1.1223	−0.3322	0.1564	0.065*
C13	−1.03672 (19)	−0.3627 (2)	0.05471 (13)	0.0458 (5)
H13	−0.9975	−0.4442	0.0729	0.055*
C14	−0.67344 (18)	−0.7978 (2)	−0.17227 (12)	0.0425 (5)
C15	−0.7690 (2)	−0.9068 (3)	−0.17628 (19)	0.0612 (7)
H15A	−0.7962	−0.9107	−0.2301	0.092*
H15B	−0.8251	−0.8737	−0.1409	0.092*
H15C	−0.7454	−1.0041	−0.1604	0.092*
C16	−0.6288 (2)	−0.7910 (3)	−0.08601 (14)	0.0571 (6)
H16A	−0.6111	−0.8896	−0.0683	0.086*
H16B	−0.6824	−0.7491	−0.0511	0.086*
H16C	−0.5653	−0.7301	−0.0850	0.086*
C17	−0.5829 (2)	−0.8579 (3)	−0.22615 (15)	0.0571 (6)
H17A	−0.6073	−0.8609	−0.2807	0.086*
H17B	−0.5636	−0.9564	−0.2091	0.086*
H17C	−0.5211	−0.7940	−0.2223	0.086*
C18	−0.63177 (17)	−0.3514 (2)	−0.35952 (13)	0.0424 (5)
C19	−0.6395 (3)	−0.4555 (3)	−0.43250 (15)	0.0662 (7)
H19A	−0.6030	−0.5471	−0.4209	0.099*
H19B	−0.6065	−0.4087	−0.4780	0.099*
H19C	−0.7140	−0.4755	−0.4441	0.099*
C20	−0.6825 (2)	−0.2033 (3)	−0.38308 (16)	0.0584 (6)
H20A	−0.7572	−0.2183	−0.3958	0.088*
H20B	−0.6457	−0.1638	−0.4290	0.088*
H20C	−0.6765	−0.1347	−0.3393	0.088*
C21	−0.5130 (2)	−0.3240 (4)	−0.3386 (2)	0.0792 (9)
H21A	−0.5084	−0.2533	−0.2957	0.119*
H21B	−0.4761	−0.2858	−0.3848	0.119*
H21C	−0.4802	−0.4159	−0.3223	0.119*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0466 (8)	0.0398 (7)	0.0414 (7)	0.0060 (6)	0.0123 (6)	0.0088 (6)
N1	0.0363 (8)	0.0377 (8)	0.0381 (8)	0.0039 (7)	0.0031 (7)	−0.0029 (6)
C1	0.0309 (9)	0.0369 (9)	0.0332 (8)	0.0022 (7)	−0.0006 (7)	−0.0003 (7)
C2	0.0331 (9)	0.0366 (9)	0.0283 (8)	0.0009 (7)	−0.0014 (7)	0.0026 (7)
C3	0.0365 (10)	0.0357 (9)	0.0320 (9)	0.0050 (7)	−0.0025 (7)	0.0010 (8)
C4	0.0346 (10)	0.0440 (10)	0.0316 (9)	0.0073 (8)	0.0030 (7)	−0.0002 (7)
C5	0.0349 (9)	0.0389 (9)	0.0301 (8)	−0.0016 (7)	−0.0004 (7)	0.0049 (7)
C6	0.0365 (9)	0.0327 (8)	0.0371 (9)	0.0017 (7)	−0.0007 (8)	0.0056 (7)
C7	0.0366 (10)	0.0329 (8)	0.0397 (9)	0.0047 (8)	0.0005 (8)	0.0005 (8)
C8	0.0306 (9)	0.0374 (9)	0.0374 (9)	0.0014 (7)	0.0007 (7)	−0.0060 (7)
C9	0.0508 (13)	0.0592 (13)	0.0392 (10)	0.0136 (10)	0.0003 (9)	0.0032 (10)
C10	0.0527 (14)	0.0629 (14)	0.0581 (14)	0.0271 (12)	−0.0028 (11)	−0.0066 (12)
C11	0.0464 (13)	0.0737 (16)	0.0498 (13)	0.0149 (11)	0.0067 (10)	−0.0175 (11)
C12	0.0559 (14)	0.0696 (15)	0.0377 (10)	0.0075 (12)	0.0102 (10)	0.0006 (11)
C13	0.0473 (12)	0.0454 (11)	0.0447 (12)	0.0065 (9)	0.0042 (9)	0.0038 (9)
C14	0.0525 (12)	0.0367 (10)	0.0383 (10)	0.0116 (8)	0.0057 (9)	0.0035 (8)
C15	0.0760 (17)	0.0378 (10)	0.0698 (15)	−0.0020 (11)	0.0100 (15)	0.0003 (11)
C16	0.0669 (15)	0.0620 (14)	0.0425 (11)	0.0262 (12)	−0.0019 (11)	0.0106 (10)
C17	0.0679 (17)	0.0520 (12)	0.0515 (13)	0.0277 (12)	0.0103 (12)	0.0052 (10)
C18	0.0410 (11)	0.0498 (11)	0.0363 (9)	−0.0022 (9)	0.0046 (8)	0.0082 (9)
C19	0.095 (2)	0.0655 (16)	0.0380 (11)	−0.0017 (14)	0.0178 (12)	0.0040 (11)
C20	0.0714 (16)	0.0548 (13)	0.0490 (13)	0.0003 (12)	0.0109 (11)	0.0197 (11)
C21	0.0447 (14)	0.113 (2)	0.0804 (19)	−0.0178 (15)	0.0040 (14)	0.0296 (18)

Geometric parameters (Å, º) top

O1—C2	1.352 (2)	C13—H13	0.9300
O1—H1	0.8200	C14—C17	1.537 (3)
N1—C7	1.279 (3)	C14—C15	1.540 (4)
N1—C8	1.421 (2)	C14—C16	1.544 (3)
C1—C2	1.409 (3)	C15—H15A	0.9600
C1—C6	1.410 (3)	C15—H15B	0.9600
C1—C7	1.457 (3)	C15—H15C	0.9600
C2—C3	1.412 (3)	C16—H16A	0.9600
C3—C4	1.390 (3)	C16—H16B	0.9600
C3—C14	1.543 (3)	C16—H16C	0.9600
C4—C5	1.406 (3)	C17—H17A	0.9600
C4—H4	0.9300	C17—H17B	0.9600
C5—C6	1.377 (3)	C17—H17C	0.9600
C5—C18	1.541 (3)	C18—C20	1.524 (3)
C6—H6	0.9300	C18—C21	1.534 (4)
C7—H7	0.9300	C18—C19	1.539 (3)
C8—C13	1.388 (3)	C19—H19A	0.9600
C8—C9	1.388 (3)	C19—H19B	0.9600
C9—C10	1.387 (3)	C19—H19C	0.9600
C9—H9	0.9300	C20—H20A	0.9600
C10—C11	1.368 (4)	C20—H20B	0.9600
C10—H10	0.9300	C20—H20C	0.9600
C11—C12	1.377 (4)	C21—H21A	0.9600
C11—H11	0.9300	C21—H21B	0.9600
C12—C13	1.385 (3)	C21—H21C	0.9600
C12—H12	0.9300

C2—O1—H1	109.5	C15—C14—C16	110.0 (2)
C7—N1—C8	123.43 (17)	C3—C14—C16	109.30 (17)
C2—C1—C6	119.65 (17)	C14—C15—H15A	109.5
C2—C1—C7	121.09 (17)	C14—C15—H15B	109.5
C6—C1—C7	119.22 (17)	H15A—C15—H15B	109.5
O1—C2—C1	120.14 (16)	C14—C15—H15C	109.5
O1—C2—C3	119.41 (16)	H15A—C15—H15C	109.5
C1—C2—C3	120.42 (16)	H15B—C15—H15C	109.5
C4—C3—C2	116.98 (16)	C14—C16—H16A	109.5
C4—C3—C14	122.32 (17)	C14—C16—H16B	109.5
C2—C3—C14	120.68 (16)	H16A—C16—H16B	109.5
C3—C4—C5	124.22 (17)	C14—C16—H16C	109.5
C3—C4—H4	117.9	H16A—C16—H16C	109.5
C5—C4—H4	117.9	H16B—C16—H16C	109.5
C6—C5—C4	117.38 (17)	C14—C17—H17A	109.5
C6—C5—C18	122.87 (17)	C14—C17—H17B	109.5
C4—C5—C18	119.74 (17)	H17A—C17—H17B	109.5
C5—C6—C1	121.27 (17)	C14—C17—H17C	109.5
C5—C6—H6	119.4	H17A—C17—H17C	109.5
C1—C6—H6	119.4	H17B—C17—H17C	109.5
N1—C7—C1	121.66 (17)	C20—C18—C21	108.4 (2)
N1—C7—H7	119.2	C20—C18—C19	107.5 (2)
C1—C7—H7	119.2	C21—C18—C19	109.7 (2)
C13—C8—C9	119.12 (19)	C20—C18—C5	111.82 (19)
C13—C8—N1	116.49 (17)	C21—C18—C5	109.26 (19)
C9—C8—N1	124.33 (18)	C19—C18—C5	110.11 (18)
C10—C9—C8	119.3 (2)	C18—C19—H19A	109.5
C10—C9—H9	120.3	C18—C19—H19B	109.5
C8—C9—H9	120.3	H19A—C19—H19B	109.5
C11—C10—C9	121.1 (2)	C18—C19—H19C	109.5
C11—C10—H10	119.4	H19A—C19—H19C	109.5
C9—C10—H10	119.4	H19B—C19—H19C	109.5
C10—C11—C12	120.1 (2)	C18—C20—H20A	109.5
C10—C11—H11	120.0	C18—C20—H20B	109.5
C12—C11—H11	120.0	H20A—C20—H20B	109.5
C11—C12—C13	119.5 (2)	C18—C20—H20C	109.5
C11—C12—H12	120.3	H20A—C20—H20C	109.5
C13—C12—H12	120.3	H20B—C20—H20C	109.5
C12—C13—C8	120.9 (2)	C18—C21—H21A	109.5
C12—C13—H13	119.6	C18—C21—H21B	109.5
C8—C13—H13	119.6	H21A—C21—H21B	109.5
C17—C14—C15	108.3 (2)	C18—C21—H21C	109.5
C17—C14—C3	111.42 (17)	H21A—C21—H21C	109.5
C15—C14—C3	110.53 (19)	H21B—C21—H21C	109.5
C17—C14—C16	107.31 (19)

C6—C1—C2—O1	−178.79 (17)	C13—C8—C9—C10	1.0 (3)
C7—C1—C2—O1	3.3 (3)	N1—C8—C9—C10	178.2 (2)
C6—C1—C2—C3	3.0 (3)	C8—C9—C10—C11	−0.6 (4)
C7—C1—C2—C3	−174.90 (17)	C9—C10—C11—C12	−0.1 (4)
O1—C2—C3—C4	179.40 (17)	C10—C11—C12—C13	0.4 (4)
C1—C2—C3—C4	−2.4 (3)	C11—C12—C13—C8	0.1 (4)
O1—C2—C3—C14	−2.5 (3)	C9—C8—C13—C12	−0.8 (3)
C1—C2—C3—C14	175.78 (18)	N1—C8—C13—C12	−178.2 (2)
C2—C3—C4—C5	−0.1 (3)	C4—C3—C14—C17	−1.0 (3)
C14—C3—C4—C5	−178.16 (18)	C2—C3—C14—C17	−179.0 (2)
C3—C4—C5—C6	1.8 (3)	C4—C3—C14—C15	−121.4 (2)
C3—C4—C5—C18	−179.10 (19)	C2—C3—C14—C15	60.6 (2)
C4—C5—C6—C1	−1.2 (3)	C4—C3—C14—C16	117.4 (2)
C18—C5—C6—C1	179.78 (18)	C2—C3—C14—C16	−60.6 (2)
C2—C1—C6—C5	−1.2 (3)	C6—C5—C18—C20	−8.2 (3)
C7—C1—C6—C5	176.78 (18)	C4—C5—C18—C20	172.7 (2)
C8—N1—C7—C1	−179.89 (17)	C6—C5—C18—C21	111.7 (3)
C2—C1—C7—N1	−2.5 (3)	C4—C5—C18—C21	−67.3 (3)
C6—C1—C7—N1	179.63 (19)	C6—C5—C18—C19	−127.7 (2)
C7—N1—C8—C13	−157.8 (2)	C4—C5—C18—C19	53.3 (3)
C7—N1—C8—C9	25.0 (3)

(7) top

Crystal data top

C₂₂H₂₇NO₃	F(000) = 760
M_r = 353.45	D_x = 1.212 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
a = 6.1482 (4) Å	Cell parameters from 18571 reflections
b = 19.5491 (13) Å	θ = 1.0–27.5°
c = 17.0976 (13) Å	µ = 0.08 mm⁻¹
β = 109.453 (3)°	T = 293 K
V = 1937.7 (2) Å³	Platelet, orange
Z = 4	0.40 × 0.30 × 0.02 mm

Data collection top

Rigaku R-AXIS RAPID IP Area Detector System diffractometer	4410 independent reflections
Radiation source: rotating anode X-ray tube	2938 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.087
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan Absorption was corrected by ABSCOR	h = −7→7
T_min = 0.627, T_max = 0.998	k = −25→25
17354 measured reflections	l = −22→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.206	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0926P)² + 0.5402P] where P = (F_o² + 2F_c²)/3
4410 reflections	(Δ/σ)_max < 0.001
272 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₂₂H₂₇NO₃	V = 1937.7 (2) Å³
M_r = 353.45	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.1482 (4) Å	µ = 0.08 mm⁻¹
b = 19.5491 (13) Å	T = 293 K
c = 17.0976 (13) Å	0.40 × 0.30 × 0.02 mm
β = 109.453 (3)°

Data collection top

Rigaku R-AXIS RAPID IP Area Detector System diffractometer	4410 independent reflections
Absorption correction: multi-scan Absorption was corrected by ABSCOR	2938 reflections with I > 2σ(I)
T_min = 0.627, T_max = 0.998	R_int = 0.087
17354 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	0 restraints
wR(F²) = 0.206	H-atom parameters constrained
S = 1.03	Δρ_max = 0.33 e Å⁻³
4410 reflections	Δρ_min = −0.27 e Å⁻³
272 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	−0.4657 (3)	0.23698 (9)	−0.18159 (9)	0.0615 (5)
H1	−0.3519	0.2618	−0.1654	0.092*
O2	0.7434 (3)	0.47770 (9)	−0.08567 (11)	0.0684 (5)
H2	0.8669	0.4981	−0.0725	0.103*
O3	0.8699 (3)	0.45015 (9)	0.04739 (11)	0.0658 (5)
N1	−0.0947 (3)	0.29279 (10)	−0.07873 (11)	0.0521 (5)
C1	−0.3453 (3)	0.21927 (11)	−0.03639 (13)	0.0477 (5)
C2	−0.4985 (4)	0.20599 (11)	−0.11625 (13)	0.0459 (5)
C3	−0.6832 (3)	0.16083 (10)	−0.12809 (12)	0.0447 (5)
C4	−0.7052 (3)	0.13130 (11)	−0.05756 (12)	0.0461 (5)
H4	−0.8280	0.1015	−0.0642	0.055*
C5	−0.5563 (4)	0.14309 (11)	0.02274 (13)	0.0465 (5)
C6	−0.3787 (4)	0.18771 (12)	0.03124 (13)	0.0515 (5)
H6	−0.2771	0.1972	0.0841	0.062*
C7	−0.1486 (4)	0.26393 (12)	−0.02147 (14)	0.0534 (5)
H7	−0.0564	0.2719	0.0331	0.064*
C8	0.1099 (4)	0.33241 (11)	−0.06053 (14)	0.0484 (5)
C9	0.2771 (4)	0.33657 (13)	0.01716 (15)	0.0614 (6)
H9	0.2568	0.3133	0.0617	0.074*
C10	0.4724 (4)	0.37475 (13)	0.02876 (15)	0.0594 (6)
H10	0.5825	0.3776	0.0814	0.071*
C11	0.5073 (3)	0.40867 (10)	−0.03596 (14)	0.0474 (5)
C12	0.3406 (4)	0.40443 (14)	−0.11328 (15)	0.0638 (6)
H12	0.3611	0.4274	−0.1579	0.077*
C13	0.1446 (4)	0.36659 (14)	−0.12471 (15)	0.0644 (7)
H13	0.0336	0.3642	−0.1772	0.077*
C14	0.7227 (4)	0.44754 (11)	−0.02130 (14)	0.0490 (5)
C15	−0.8470 (4)	0.14290 (12)	−0.21475 (13)	0.0531 (5)
C16	−0.7092 (5)	0.11059 (16)	−0.26513 (16)	0.0739 (8)
H16A	−0.8119	0.0987	−0.3193	0.111*
H16B	−0.6327	0.0702	−0.2374	0.111*
H16C	−0.5965	0.1427	−0.2703	0.111*
C17	−1.0311 (5)	0.09187 (15)	−0.21197 (16)	0.0730 (8)
H17A	−1.1213	0.1110	−0.1811	0.110*
H17B	−0.9586	0.0505	−0.1856	0.110*
H17C	−1.1294	0.0818	−0.2674	0.110*
C18	−0.9705 (5)	0.20695 (14)	−0.25910 (16)	0.0680 (7)
H18A	−0.8587	0.2392	−0.2647	0.102*
H18B	−1.0565	0.2272	−0.2274	0.102*
H18C	−1.0737	0.1947	−0.3131	0.102*
C19	−0.5867 (4)	0.10678 (12)	0.09775 (14)	0.0544 (6)
C20A	−0.3883 (14)	0.1148 (6)	0.1783 (4)	0.086 (3)	0.482 (9)
H20A	−0.4094	0.0842	0.2191	0.129*	0.482 (9)
H20B	−0.3837	0.1611	0.1976	0.129*	0.482 (9)
H20C	−0.2459	0.1043	0.1693	0.129*	0.482 (9)
C21A	−0.606 (2)	0.0267 (3)	0.0805 (4)	0.094 (3)	0.482 (9)
H21A	−0.6420	0.0039	0.1244	0.141*	0.482 (9)
H21B	−0.4622	0.0098	0.0778	0.141*	0.482 (9)
H21C	−0.7262	0.0180	0.0287	0.141*	0.482 (9)
C22A	−0.8069 (15)	0.1275 (5)	0.1091 (5)	0.098 (4)	0.482 (9)
H22A	−0.9331	0.1179	0.0593	0.147*	0.482 (9)
H22B	−0.8030	0.1755	0.1210	0.147*	0.482 (9)
H22C	−0.8270	0.1023	0.1544	0.147*	0.482 (9)
C20B	−0.6311 (19)	0.1644 (4)	0.1544 (4)	0.099 (3)	0.518 (9)
H20D	−0.7750	0.1867	0.1260	0.149*	0.518 (9)
H20E	−0.5082	0.1973	0.1670	0.149*	0.518 (9)
H20F	−0.6371	0.1446	0.2050	0.149*	0.518 (9)
C21B	−0.3629 (14)	0.0723 (5)	0.1440 (6)	0.103 (3)	0.518 (9)
H21D	−0.3808	0.0460	0.1889	0.155*	0.518 (9)
H21E	−0.2454	0.1062	0.1657	0.155*	0.518 (9)
H21F	−0.3193	0.0426	0.1071	0.155*	0.518 (9)
C22B	−0.7817 (16)	0.0594 (5)	0.0753 (4)	0.099 (4)	0.518 (9)
H22D	−0.7945	0.0389	0.1247	0.149*	0.518 (9)
H22E	−0.7576	0.0242	0.0399	0.149*	0.518 (9)
H22F	−0.9211	0.0838	0.0468	0.149*	0.518 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0599 (9)	0.0816 (11)	0.0441 (8)	−0.0189 (8)	0.0187 (7)	0.0040 (8)
O2	0.0570 (9)	0.0774 (11)	0.0698 (11)	−0.0211 (9)	0.0199 (8)	0.0092 (9)
O3	0.0484 (9)	0.0782 (11)	0.0648 (10)	−0.0132 (8)	0.0110 (8)	0.0091 (9)
N1	0.0472 (10)	0.0588 (11)	0.0523 (11)	−0.0072 (8)	0.0193 (8)	−0.0047 (8)
C1	0.0453 (10)	0.0525 (12)	0.0479 (11)	−0.0068 (9)	0.0189 (9)	−0.0049 (9)
C2	0.0469 (11)	0.0518 (11)	0.0431 (11)	0.0000 (9)	0.0204 (9)	0.0024 (9)
C3	0.0418 (10)	0.0515 (11)	0.0409 (10)	−0.0003 (9)	0.0139 (8)	0.0000 (9)
C4	0.0434 (10)	0.0497 (11)	0.0462 (11)	−0.0054 (9)	0.0163 (9)	−0.0010 (9)
C5	0.0483 (11)	0.0504 (11)	0.0438 (11)	−0.0009 (9)	0.0191 (9)	−0.0008 (9)
C6	0.0514 (12)	0.0618 (13)	0.0416 (11)	−0.0090 (10)	0.0157 (9)	−0.0044 (9)
C7	0.0547 (12)	0.0596 (13)	0.0471 (12)	−0.0088 (11)	0.0184 (10)	−0.0043 (10)
C8	0.0421 (10)	0.0506 (11)	0.0545 (12)	−0.0044 (9)	0.0186 (9)	−0.0066 (9)
C9	0.0545 (13)	0.0739 (16)	0.0560 (14)	−0.0117 (12)	0.0187 (11)	0.0093 (12)
C10	0.0496 (12)	0.0698 (15)	0.0544 (13)	−0.0100 (11)	0.0117 (10)	0.0060 (11)
C11	0.0419 (10)	0.0452 (11)	0.0567 (12)	−0.0025 (9)	0.0184 (9)	−0.0025 (9)
C12	0.0607 (14)	0.0766 (16)	0.0527 (13)	−0.0158 (13)	0.0169 (11)	0.0046 (12)
C13	0.0586 (14)	0.0810 (17)	0.0500 (13)	−0.0209 (13)	0.0132 (11)	0.0002 (12)
C14	0.0455 (11)	0.0458 (11)	0.0574 (13)	−0.0002 (9)	0.0192 (10)	−0.0002 (10)
C15	0.0495 (11)	0.0654 (13)	0.0409 (11)	−0.0041 (10)	0.0103 (9)	0.0011 (10)
C16	0.0752 (17)	0.0907 (19)	0.0536 (14)	−0.0021 (15)	0.0185 (13)	−0.0184 (13)
C17	0.0631 (15)	0.0868 (19)	0.0568 (14)	−0.0239 (14)	0.0034 (12)	0.0005 (13)
C18	0.0619 (14)	0.0805 (17)	0.0547 (14)	0.0010 (13)	0.0099 (11)	0.0115 (12)
C19	0.0588 (13)	0.0644 (13)	0.0448 (11)	−0.0005 (11)	0.0235 (10)	0.0054 (10)
C20A	0.084 (5)	0.132 (7)	0.038 (3)	−0.023 (5)	0.016 (3)	0.016 (3)
C21A	0.139 (8)	0.068 (4)	0.072 (4)	0.003 (4)	0.031 (5)	0.023 (3)
C22A	0.097 (5)	0.133 (8)	0.090 (5)	0.039 (6)	0.067 (5)	0.040 (6)
C20B	0.170 (9)	0.086 (4)	0.066 (4)	0.006 (5)	0.071 (5)	0.002 (3)
C21B	0.109 (5)	0.123 (7)	0.088 (6)	0.030 (5)	0.046 (5)	0.057 (5)
C22B	0.121 (7)	0.116 (7)	0.067 (4)	−0.055 (6)	0.041 (4)	0.012 (4)

Geometric parameters (Å, º) top

O1—C2	1.344 (2)	C16—H16A	0.9600
O1—H1	0.8200	C16—H16B	0.9600
O2—C14	1.292 (3)	C16—H16C	0.9600
O2—H2	0.8200	C17—H17A	0.9600
O3—C14	1.222 (3)	C17—H17B	0.9600
N1—C7	1.266 (3)	C17—H17C	0.9600
N1—C8	1.421 (3)	C18—H18A	0.9600
C1—C6	1.385 (3)	C18—H18B	0.9600
C1—C2	1.401 (3)	C18—H18C	0.9600
C1—C7	1.444 (3)	C19—C22B	1.462 (7)
C2—C3	1.399 (3)	C19—C22A	1.486 (7)
C3—C4	1.384 (3)	C19—C21B	1.500 (8)
C3—C15	1.529 (3)	C19—C20A	1.514 (6)
C4—C5	1.393 (3)	C19—C20B	1.568 (6)
C4—H4	0.9300	C19—C21A	1.590 (7)
C5—C6	1.367 (3)	C20A—H20A	0.9600
C5—C19	1.531 (3)	C20A—H20B	0.9600
C6—H6	0.9300	C20A—H20C	0.9600
C7—H7	0.9300	C21A—H21A	0.9600
C8—C13	1.361 (3)	C21A—H21B	0.9600
C8—C9	1.385 (3)	C21A—H21C	0.9600
C9—C10	1.371 (3)	C22A—H22A	0.9600
C9—H9	0.9300	C22A—H22B	0.9600
C10—C11	1.367 (3)	C22A—H22C	0.9600
C10—H10	0.9300	C20B—H20D	0.9600
C11—C12	1.380 (3)	C20B—H20E	0.9600
C11—C14	1.474 (3)	C20B—H20F	0.9600
C12—C13	1.371 (3)	C21B—H21D	0.9600
C12—H12	0.9300	C21B—H21E	0.9600
C13—H13	0.9300	C21B—H21F	0.9600
C15—C17	1.521 (3)	C22B—H22D	0.9600
C15—C18	1.528 (3)	C22B—H22E	0.9600
C15—C16	1.531 (4)	C22B—H22F	0.9600

C2—O1—H1	109.5	H17A—C17—H17B	109.5
C14—O2—H2	109.5	C15—C17—H17C	109.5
C7—N1—C8	120.94 (19)	H17A—C17—H17C	109.5
C6—C1—C2	119.52 (19)	H17B—C17—H17C	109.5
C6—C1—C7	118.05 (19)	C15—C18—H18A	109.5
C2—C1—C7	122.41 (19)	C15—C18—H18B	109.5
O1—C2—C3	120.23 (18)	H18A—C18—H18B	109.5
O1—C2—C1	119.24 (18)	C15—C18—H18C	109.5
C3—C2—C1	120.52 (18)	H18A—C18—H18C	109.5
C4—C3—C2	116.59 (18)	H18B—C18—H18C	109.5
C4—C3—C15	121.65 (18)	C22B—C19—C22A	60.2 (5)
C2—C3—C15	121.72 (18)	C22B—C19—C21B	112.4 (5)
C3—C4—C5	124.54 (19)	C22A—C19—C21B	140.3 (4)
C3—C4—H4	117.7	C22B—C19—C20A	130.3 (4)
C5—C4—H4	117.7	C22A—C19—C20A	110.2 (5)
C6—C5—C4	116.75 (19)	C21B—C19—C20A	41.1 (4)
C6—C5—C19	121.53 (19)	C22B—C19—C5	113.1 (3)
C4—C5—C19	121.70 (19)	C22A—C19—C5	110.7 (3)
C5—C6—C1	122.06 (19)	C21B—C19—C5	107.7 (3)
C5—C6—H6	119.0	C20A—C19—C5	115.3 (3)
C1—C6—H6	119.0	C22B—C19—C20B	108.7 (5)
N1—C7—C1	123.5 (2)	C22A—C19—C20B	51.0 (4)
N1—C7—H7	118.2	C21B—C19—C20B	108.4 (5)
C1—C7—H7	118.2	C20A—C19—C20B	67.4 (5)
C13—C8—C9	118.6 (2)	C5—C19—C20B	106.2 (3)
C13—C8—N1	117.14 (19)	C22B—C19—C21A	47.4 (4)
C9—C8—N1	124.2 (2)	C22A—C19—C21A	106.0 (6)
C10—C9—C8	120.3 (2)	C21B—C19—C21A	69.8 (5)
C10—C9—H9	119.8	C20A—C19—C21A	105.1 (5)
C8—C9—H9	119.8	C5—C19—C21A	108.9 (3)
C11—C10—C9	120.9 (2)	C20B—C19—C21A	143.5 (4)
C11—C10—H10	119.6	C19—C20A—H20A	109.5
C9—C10—H10	119.6	C19—C20A—H20B	109.5
C10—C11—C12	118.6 (2)	C19—C20A—H20C	109.5
C10—C11—C14	119.1 (2)	C19—C21A—H21A	109.5
C12—C11—C14	122.2 (2)	C19—C21A—H21B	109.5
C13—C12—C11	120.4 (2)	C19—C21A—H21C	109.5
C13—C12—H12	119.8	C19—C22A—H22A	109.5
C11—C12—H12	119.8	C19—C22A—H22B	109.5
C8—C13—C12	121.1 (2)	C19—C22A—H22C	109.5
C8—C13—H13	119.5	C19—C20B—H20D	109.5
C12—C13—H13	119.5	C19—C20B—H20E	109.5
O3—C14—O2	123.2 (2)	H20D—C20B—H20E	109.5
O3—C14—C11	121.4 (2)	C19—C20B—H20F	109.5
O2—C14—C11	115.36 (19)	H20D—C20B—H20F	109.5
C17—C15—C18	107.5 (2)	H20E—C20B—H20F	109.5
C17—C15—C3	112.13 (19)	C19—C21B—H21D	109.5
C18—C15—C3	110.54 (19)	C19—C21B—H21E	109.5
C17—C15—C16	107.7 (2)	H21D—C21B—H21E	109.5
C18—C15—C16	109.6 (2)	C19—C21B—H21F	109.5
C3—C15—C16	109.29 (18)	H21D—C21B—H21F	109.5
C15—C16—H16A	109.5	H21E—C21B—H21F	109.5
C15—C16—H16B	109.5	C19—C22B—H22D	109.5
H16A—C16—H16B	109.5	C19—C22B—H22E	109.5
C15—C16—H16C	109.5	H22D—C22B—H22E	109.5
H16A—C16—H16C	109.5	C19—C22B—H22F	109.5
H16B—C16—H16C	109.5	H22D—C22B—H22F	109.5
C15—C17—H17A	109.5	H22E—C22B—H22F	109.5
C15—C17—H17B	109.5

C6—C1—C2—O1	179.7 (2)	C14—C11—C12—C13	178.7 (2)
C7—C1—C2—O1	−1.6 (3)	C9—C8—C13—C12	0.0 (4)
C6—C1—C2—C3	−0.5 (3)	N1—C8—C13—C12	−178.1 (2)
C7—C1—C2—C3	178.2 (2)	C11—C12—C13—C8	−0.1 (4)
O1—C2—C3—C4	−179.75 (19)	C10—C11—C14—O3	−0.2 (3)
C1—C2—C3—C4	0.5 (3)	C12—C11—C14—O3	−179.2 (2)
O1—C2—C3—C15	2.5 (3)	C10—C11—C14—O2	179.5 (2)
C1—C2—C3—C15	−177.3 (2)	C12—C11—C14—O2	0.5 (3)
C2—C3—C4—C5	−0.6 (3)	C4—C3—C15—C17	1.3 (3)
C15—C3—C4—C5	177.1 (2)	C2—C3—C15—C17	178.9 (2)
C3—C4—C5—C6	0.8 (3)	C4—C3—C15—C18	121.2 (2)
C3—C4—C5—C19	−178.0 (2)	C2—C3—C15—C18	−61.1 (3)
C4—C5—C6—C1	−0.8 (3)	C4—C3—C15—C16	−118.0 (2)
C19—C5—C6—C1	178.0 (2)	C2—C3—C15—C16	59.6 (3)
C2—C1—C6—C5	0.6 (3)	C6—C5—C19—C22B	−177.9 (5)
C7—C1—C6—C5	−178.1 (2)	C4—C5—C19—C22B	0.8 (6)
C8—N1—C7—C1	−175.6 (2)	C6—C5—C19—C22A	116.7 (5)
C6—C1—C7—N1	176.4 (2)	C4—C5—C19—C22A	−64.6 (6)
C2—C1—C7—N1	−2.2 (4)	C6—C5—C19—C21B	−53.0 (6)
C7—N1—C8—C13	−174.4 (2)	C4—C5—C19—C21B	125.6 (5)
C7—N1—C8—C9	7.6 (4)	C6—C5—C19—C20A	−9.4 (6)
C13—C8—C9—C10	0.4 (4)	C4—C5—C19—C20A	169.3 (5)
N1—C8—C9—C10	178.4 (2)	C6—C5—C19—C20B	62.9 (5)
C8—C9—C10—C11	−0.8 (4)	C4—C5—C19—C20B	−118.4 (5)
C9—C10—C11—C12	0.8 (4)	C6—C5—C19—C21A	−127.1 (5)
C9—C10—C11—C14	−178.3 (2)	C4—C5—C19—C21A	51.6 (5)
C10—C11—C12—C13	−0.3 (4)

(8) top

Crystal data top

C₁₃H₁₀ClNO	F(000) = 480
M_r = 231.67	D_x = 1.405 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54186 Å
a = 4.6868 (1) Å	Cell parameters from 6946 reflections
b = 18.9497 (4) Å	θ = 3.1–68.2°
c = 12.8231 (2) Å	µ = 2.88 mm⁻¹
β = 105.968 (1)°	T = 293 K
V = 1094.92 (4) Å³	Needle, yellow
Z = 4	0.33 × 0.10 × 0.06 mm

Data collection top

Rigaku VM-SPIDER IP Area Detector System diffractometer	1976 independent reflections
Radiation source: rotating anode X-ray tube	1565 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ω scans	θ_max = 68.2°, θ_min = 4.3°
Absorption correction: multi-scan Absorption was corrected by ABSCOR	h = −5→5
T_min = 0.340, T_max = 0.837	k = −22→22
12241 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.170	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0674P)² + 0.9889P] where P = (F_o² + 2F_c²)/3
1976 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₃H₁₀ClNO	V = 1094.92 (4) Å³
M_r = 231.67	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 4.6868 (1) Å	µ = 2.88 mm⁻¹
b = 18.9497 (4) Å	T = 293 K
c = 12.8231 (2) Å	0.33 × 0.10 × 0.06 mm
β = 105.968 (1)°

Data collection top

Rigaku VM-SPIDER IP Area Detector System diffractometer	1976 independent reflections
Absorption correction: multi-scan Absorption was corrected by ABSCOR	1565 reflections with I > 2σ(I)
T_min = 0.340, T_max = 0.837	R_int = 0.046
12241 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 1.08	Δρ_max = 0.33 e Å⁻³
1976 reflections	Δρ_min = −0.21 e Å⁻³
145 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	1.1485 (3)	0.43020 (5)	0.42965 (7)	0.0781 (4)
O1	0.6479 (6)	0.28079 (13)	0.41658 (17)	0.0680 (7)
H1	0.7491	0.3061	0.3890	0.102*
N1	0.8377 (6)	0.33312 (13)	0.25858 (19)	0.0485 (6)
C1	0.4969 (7)	0.23728 (15)	0.2327 (2)	0.0457 (7)
C2	0.4830 (7)	0.23663 (16)	0.3405 (2)	0.0508 (7)
C3	0.2954 (8)	0.18914 (18)	0.3716 (3)	0.0595 (9)
H3	0.2853	0.1884	0.4430	0.071*
C4	0.1245 (8)	0.14309 (18)	0.2968 (3)	0.0601 (9)
H4	−0.0007	0.1116	0.3183	0.072*
C5	0.1362 (8)	0.14294 (18)	0.1909 (3)	0.0612 (9)
H5	0.0199	0.1117	0.1411	0.073*
C6	0.3220 (8)	0.18958 (17)	0.1593 (3)	0.0573 (8)
H6	0.3310	0.1893	0.0877	0.069*
C7	0.6862 (7)	0.28631 (15)	0.1956 (2)	0.0486 (7)
H7	0.6973	0.2835	0.1244	0.058*
C8	1.0163 (7)	0.38220 (15)	0.2224 (2)	0.0455 (7)
C9	1.0413 (8)	0.38690 (17)	0.1171 (3)	0.0536 (8)
H9	0.9357	0.3556	0.0647	0.064*
C10	1.2201 (9)	0.43715 (17)	0.0889 (3)	0.0621 (9)
H10	1.2343	0.4393	0.0181	0.075*
C11	1.3777 (8)	0.48413 (18)	0.1653 (3)	0.0625 (9)
H11	1.4970	0.5181	0.1459	0.075*
C12	1.3585 (8)	0.48083 (17)	0.2696 (3)	0.0618 (9)
H12	1.4661	0.5122	0.3214	0.074*
C13	1.1792 (7)	0.43085 (16)	0.2981 (3)	0.0517 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1048 (8)	0.0824 (7)	0.0478 (5)	−0.0182 (5)	0.0221 (5)	−0.0120 (4)
O1	0.0794 (17)	0.0824 (17)	0.0444 (13)	−0.0233 (13)	0.0206 (12)	−0.0071 (11)
N1	0.0529 (15)	0.0482 (14)	0.0456 (14)	−0.0005 (11)	0.0153 (12)	0.0012 (11)
C1	0.0477 (17)	0.0451 (15)	0.0444 (16)	0.0042 (13)	0.0128 (13)	0.0026 (12)
C2	0.0536 (19)	0.0516 (17)	0.0457 (17)	0.0020 (14)	0.0114 (14)	0.0027 (13)
C3	0.065 (2)	0.065 (2)	0.0508 (18)	0.0003 (17)	0.0202 (17)	0.0120 (15)
C4	0.057 (2)	0.0525 (18)	0.072 (2)	−0.0024 (15)	0.0188 (17)	0.0108 (16)
C5	0.064 (2)	0.0530 (18)	0.065 (2)	−0.0094 (16)	0.0149 (17)	−0.0046 (15)
C6	0.065 (2)	0.0559 (18)	0.0507 (18)	−0.0017 (16)	0.0162 (16)	−0.0043 (14)
C7	0.0538 (18)	0.0501 (16)	0.0417 (16)	0.0048 (14)	0.0131 (14)	0.0025 (13)
C8	0.0490 (17)	0.0426 (15)	0.0456 (16)	0.0054 (13)	0.0143 (13)	0.0019 (12)
C9	0.060 (2)	0.0538 (17)	0.0475 (17)	−0.0014 (15)	0.0160 (15)	−0.0003 (13)
C10	0.075 (2)	0.060 (2)	0.058 (2)	0.0027 (17)	0.0289 (18)	0.0096 (16)
C11	0.066 (2)	0.0502 (18)	0.076 (2)	−0.0028 (16)	0.0265 (19)	0.0069 (16)
C12	0.067 (2)	0.0469 (17)	0.068 (2)	−0.0037 (16)	0.0137 (18)	−0.0032 (15)
C13	0.0564 (19)	0.0491 (16)	0.0487 (17)	0.0062 (14)	0.0127 (14)	0.0016 (13)

Geometric parameters (Å, º) top

Cl1—C13	1.732 (3)	C5—H5	0.9300
O1—C2	1.355 (4)	C6—H6	0.9300
O1—H1	0.8200	C7—H7	0.9300
N1—C7	1.276 (4)	C8—C9	1.390 (4)
N1—C8	1.413 (4)	C8—C13	1.403 (4)
C1—C6	1.397 (4)	C9—C10	1.381 (5)
C1—C2	1.402 (4)	C9—H9	0.9300
C1—C7	1.452 (4)	C10—C11	1.378 (5)
C2—C3	1.391 (5)	C10—H10	0.9300
C3—C4	1.379 (5)	C11—C12	1.367 (5)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.373 (5)	C12—C13	1.380 (5)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.378 (5)

C2—O1—H1	109.5	N1—C7—H7	119.3
C7—N1—C8	121.8 (3)	C1—C7—H7	119.3
C6—C1—C2	118.7 (3)	C9—C8—C13	117.1 (3)
C6—C1—C7	119.5 (3)	C9—C8—N1	125.3 (3)
C2—C1—C7	121.8 (3)	C13—C8—N1	117.7 (3)
O1—C2—C3	118.3 (3)	C10—C9—C8	121.2 (3)
O1—C2—C1	122.2 (3)	C10—C9—H9	119.4
C3—C2—C1	119.5 (3)	C8—C9—H9	119.4
C4—C3—C2	120.1 (3)	C11—C10—C9	120.3 (3)
C4—C3—H3	119.9	C11—C10—H10	119.8
C2—C3—H3	119.9	C9—C10—H10	119.8
C5—C4—C3	121.0 (3)	C12—C11—C10	119.9 (3)
C5—C4—H4	119.5	C12—C11—H11	120.0
C3—C4—H4	119.5	C10—C11—H11	120.0
C4—C5—C6	119.3 (3)	C11—C12—C13	119.9 (3)
C4—C5—H5	120.3	C11—C12—H12	120.0
C6—C5—H5	120.3	C13—C12—H12	120.0
C5—C6—C1	121.2 (3)	C12—C13—C8	121.5 (3)
C5—C6—H6	119.4	C12—C13—Cl1	118.8 (3)
C1—C6—H6	119.4	C8—C13—Cl1	119.6 (2)
N1—C7—C1	121.4 (3)

C6—C1—C2—O1	179.4 (3)	C7—N1—C8—C9	2.1 (5)
C7—C1—C2—O1	−1.0 (5)	C7—N1—C8—C13	−178.8 (3)
C6—C1—C2—C3	−0.3 (5)	C13—C8—C9—C10	0.3 (5)
C7—C1—C2—C3	179.3 (3)	N1—C8—C9—C10	179.4 (3)
O1—C2—C3—C4	−179.8 (3)	C8—C9—C10—C11	−0.2 (5)
C1—C2—C3—C4	0.0 (5)	C9—C10—C11—C12	0.3 (5)
C2—C3—C4—C5	0.2 (5)	C10—C11—C12—C13	−0.6 (5)
C3—C4—C5—C6	0.0 (5)	C11—C12—C13—C8	0.7 (5)
C4—C5—C6—C1	−0.4 (5)	C11—C12—C13—Cl1	−177.5 (3)
C2—C1—C6—C5	0.6 (5)	C9—C8—C13—C12	−0.5 (5)
C7—C1—C6—C5	−179.0 (3)	N1—C8—C13—C12	−179.7 (3)
C8—N1—C7—C1	−178.3 (3)	C9—C8—C13—Cl1	177.7 (2)
C6—C1—C7—N1	176.3 (3)	N1—C8—C13—Cl1	−1.5 (4)
C2—C1—C7—N1	−3.3 (5)

(1) top

Crystal data top

C_17.12H_19.35NO	F(000) = 544
M_r = 255.13	D_x = 1.135 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
a = 14.3711 (8) Å	Cell parameters from 15484 reflections
b = 6.4227 (4) Å	θ = 3.0–27.5°
c = 17.9938 (9) Å	µ = 0.07 mm⁻¹
β = 116.819 (4)°	T = 296 K
V = 1482.20 (14) Å³	Block, yellow
Z = 4	0.34 × 0.30 × 0.18 mm

Data collection top

Rigaku R-AXIS RAPID IP Area Detector System diffractometer	3381 independent reflections
Radiation source: rotating anode X-ray tube	2187 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan Absorption was corrected by ABSCOR	h = −17→18
T_min = 0.885, T_max = 0.988	k = −8→8
23765 measured reflections	l = −23→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.190	w = 1/[σ²(F_o²) + (0.0905P)² + 0.1529P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max = 0.002
3381 reflections	Δρ_max = 0.22 e Å⁻³
194 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.023 (4)

Crystal data top

C_17.12H_19.35NO	V = 1482.20 (14) Å³
M_r = 255.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.3711 (8) Å	µ = 0.07 mm⁻¹
b = 6.4227 (4) Å	T = 296 K
c = 17.9938 (9) Å	0.34 × 0.30 × 0.18 mm
β = 116.819 (4)°

Data collection top

Rigaku R-AXIS RAPID IP Area Detector System diffractometer	3381 independent reflections
Absorption correction: multi-scan Absorption was corrected by ABSCOR	2187 reflections with I > 2σ(I)
T_min = 0.885, T_max = 0.988	R_int = 0.036
23765 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.190	H-atom parameters constrained
S = 1.13	Δρ_max = 0.22 e Å⁻³
3381 reflections	Δρ_min = −0.21 e Å⁻³
194 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.19001 (12)	0.1106 (2)	0.35065 (9)	0.0918 (5)
H1	0.2112	0.1798	0.3231	0.138*
N1	0.20174 (11)	0.4307 (2)	0.26577 (9)	0.0677 (4)
C1	0.09283 (12)	0.4273 (3)	0.33406 (9)	0.0601 (4)
C2	0.12003 (14)	0.2230 (3)	0.36456 (10)	0.0670 (5)
C3	0.07406 (16)	0.1330 (3)	0.41036 (12)	0.0801 (5)
H3	0.0926	−0.0011	0.4313	0.096*
C4	0.00164 (17)	0.2414 (4)	0.42460 (12)	0.0844 (6)
H4	−0.0287	0.1794	0.4551	0.101*
C5	−0.02717 (16)	0.4412 (3)	0.39448 (12)	0.0815 (6)
H5	−0.0769	0.5131	0.4041	0.098*
C6	0.01872 (14)	0.5321 (3)	0.35013 (10)	0.0692 (5)
H6	−0.0001	0.6670	0.3303	0.083*
C7	0.13993 (12)	0.5281 (3)	0.28719 (9)	0.0621 (4)
H7	0.1248	0.6672	0.2723	0.075*
C8	0.24819 (12)	0.5348 (3)	0.22120 (11)	0.0639 (4)
C9	0.29023 (15)	0.7326 (3)	0.24101 (12)	0.0741 (5)
H9	0.2860	0.8064	0.2839	0.089*
C10	0.33839 (15)	0.8207 (3)	0.19744 (12)	0.0764 (5)
H10	0.3668	0.9533	0.2123	0.092*
C11	0.34605 (13)	0.7192 (3)	0.13224 (10)	0.0651 (4)
C12	0.30135 (16)	0.5221 (3)	0.11268 (13)	0.0770 (5)
H12	0.3028	0.4499	0.0684	0.092*
C13	0.25522 (15)	0.4310 (3)	0.15669 (13)	0.0779 (5)
H13	0.2282	0.2971	0.1429	0.093*
C14	0.40060 (15)	0.8134 (3)	0.08426 (12)	0.0746 (5)
C15A	0.4587 (5)	1.0294 (10)	0.1274 (4)	0.0765 (18)*	0.402 (8)
H15A	0.5083	1.0032	0.1841	0.115*	0.402 (8)
H15B	0.4080	1.1285	0.1261	0.115*	0.402 (8)
H15C	0.4942	1.0841	0.0974	0.115*	0.402 (8)
C16A	0.4906 (7)	0.6690 (11)	0.0906 (6)	0.092 (2)*	0.402 (8)
H16A	0.5250	0.7306	0.0609	0.137*	0.402 (8)
H16B	0.4627	0.5359	0.0667	0.137*	0.402 (8)
H16C	0.5398	0.6515	0.1480	0.137*	0.402 (8)
C17A	0.3280 (6)	0.8537 (15)	−0.0027 (4)	0.099 (2)*	0.402 (8)
H17A	0.2731	0.9431	−0.0053	0.149*	0.402 (8)
H17B	0.2989	0.7246	−0.0302	0.149*	0.402 (8)
H17C	0.3644	0.9201	−0.0297	0.149*	0.402 (8)
C15B	0.3564 (6)	0.7232 (14)	−0.0095 (5)	0.095 (2)*	0.335 (7)
H15D	0.3882	0.7964	−0.0386	0.143*	0.335 (7)
H15E	0.2821	0.7420	−0.0381	0.143*	0.335 (7)
H15F	0.3724	0.5775	−0.0073	0.143*	0.335 (7)
C16B	0.3911 (8)	1.0433 (14)	0.0746 (7)	0.119 (3)*	0.335 (7)
H16D	0.4282	1.1081	0.1281	0.179*	0.335 (7)
H16E	0.3189	1.0821	0.0508	0.179*	0.335 (7)
H16F	0.4202	1.0882	0.0386	0.179*	0.335 (7)
C17B	0.5155 (6)	0.7413 (14)	0.1247 (6)	0.097 (3)*	0.335 (7)
H17D	0.5495	0.7955	0.0935	0.145*	0.335 (7)
H17E	0.5182	0.5919	0.1248	0.145*	0.335 (7)
H17F	0.5503	0.7916	0.1809	0.145*	0.335 (7)
C15C	0.4890 (9)	0.938 (2)	0.1377 (7)	0.116 (4)*	0.302 (8)
H15G	0.5223	0.9931	0.1060	0.174*	0.302 (8)
H15H	0.5377	0.8541	0.1823	0.174*	0.302 (8)
H15I	0.4659	1.0514	0.1602	0.174*	0.302 (8)
C16C	0.3117 (6)	0.9437 (15)	0.0135 (5)	0.083 (2)*	0.302 (8)
H16G	0.2829	1.0407	0.0381	0.125*	0.302 (8)
H16H	0.2579	0.8515	−0.0230	0.125*	0.302 (8)
H16I	0.3403	1.0184	−0.0177	0.125*	0.302 (8)
C17C	0.4359 (10)	0.6434 (15)	0.0439 (8)	0.109 (3)*	0.302 (8)
H17G	0.4798	0.7028	0.0221	0.163*	0.302 (8)
H17H	0.3760	0.5807	−0.0006	0.163*	0.302 (8)
H17I	0.4741	0.5395	0.0847	0.163*	0.302 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1083 (10)	0.0687 (8)	0.1079 (11)	0.0250 (7)	0.0570 (9)	0.0195 (7)
N1	0.0675 (8)	0.0652 (8)	0.0701 (9)	0.0032 (7)	0.0306 (7)	0.0031 (7)
C1	0.0632 (9)	0.0600 (9)	0.0485 (8)	0.0014 (7)	0.0175 (7)	−0.0017 (6)
C2	0.0730 (10)	0.0622 (10)	0.0580 (9)	0.0025 (8)	0.0226 (8)	0.0018 (7)
C3	0.0963 (14)	0.0724 (11)	0.0649 (10)	−0.0050 (10)	0.0305 (10)	0.0069 (9)
C4	0.0943 (14)	0.0988 (15)	0.0627 (10)	−0.0155 (12)	0.0376 (10)	−0.0006 (10)
C5	0.0825 (12)	0.0986 (15)	0.0663 (10)	0.0039 (11)	0.0360 (10)	−0.0064 (10)
C6	0.0761 (11)	0.0694 (10)	0.0588 (9)	0.0054 (8)	0.0274 (8)	−0.0013 (8)
C7	0.0646 (9)	0.0588 (9)	0.0547 (8)	0.0022 (7)	0.0196 (7)	0.0016 (7)
C8	0.0598 (9)	0.0610 (9)	0.0675 (10)	0.0036 (7)	0.0257 (8)	0.0030 (7)
C9	0.0832 (12)	0.0691 (11)	0.0719 (11)	−0.0060 (9)	0.0367 (10)	−0.0093 (8)
C10	0.0829 (12)	0.0646 (10)	0.0793 (12)	−0.0113 (9)	0.0344 (10)	−0.0077 (9)
C11	0.0589 (9)	0.0647 (10)	0.0644 (9)	0.0049 (7)	0.0215 (8)	0.0057 (7)
C12	0.0886 (12)	0.0701 (11)	0.0824 (12)	−0.0066 (9)	0.0475 (11)	−0.0123 (9)
C13	0.0877 (12)	0.0612 (10)	0.0927 (13)	−0.0097 (9)	0.0478 (11)	−0.0136 (9)
C14	0.0748 (11)	0.0745 (11)	0.0712 (11)	−0.0033 (9)	0.0301 (9)	0.0067 (9)

Geometric parameters (Å, º) top

O1—C2	1.350 (2)	C14—C16A	1.553 (7)
O1—H1	0.8200	C14—C16C	1.577 (8)
N1—C7	1.280 (2)	C14—C15B	1.617 (8)
N1—C8	1.421 (2)	C14—C15A	1.625 (6)
C1—C6	1.396 (2)	C15A—H15A	0.9600
C1—C2	1.408 (2)	C15A—H15B	0.9600
C1—C7	1.450 (2)	C15A—H15C	0.9600
C2—C3	1.393 (3)	C16A—H16A	0.9600
C3—C4	1.369 (3)	C16A—H16B	0.9600
C3—H3	0.9300	C16A—H16C	0.9600
C4—C5	1.382 (3)	C17A—H17A	0.9600
C4—H4	0.9300	C17A—H17B	0.9600
C5—C6	1.374 (3)	C17A—H17C	0.9600
C5—H5	0.9300	C15B—H15D	0.9600
C6—H6	0.9300	C15B—H15E	0.9600
C7—H7	0.9300	C15B—H15F	0.9600
C8—C13	1.381 (2)	C16B—H16D	0.9600
C8—C9	1.382 (2)	C16B—H16E	0.9600
C9—C10	1.380 (3)	C16B—H16F	0.9600
C9—H9	0.9300	C17B—H17D	0.9600
C10—C11	1.389 (2)	C17B—H17E	0.9600
C10—H10	0.9300	C17B—H17F	0.9600
C11—C12	1.391 (2)	C15C—H15G	0.9600
C11—C14	1.529 (2)	C15C—H15H	0.9600
C12—C13	1.372 (2)	C15C—H15I	0.9600
C12—H12	0.9300	C16C—H16G	0.9600
C13—H13	0.9300	C16C—H16H	0.9600
C14—C15C	1.443 (10)	C16C—H16I	0.9600
C14—C17A	1.459 (7)	C17C—H17G	0.9600
C14—C16B	1.486 (9)	C17C—H17H	0.9600
C14—C17C	1.519 (9)	C17C—H17I	0.9600
C14—C17B	1.545 (8)

C2—O1—H1	109.5	C17B—C14—C16A	27.0 (4)
C7—N1—C8	120.45 (15)	C15C—C14—C16C	113.0 (6)
C6—C1—C2	118.16 (15)	C17A—C14—C16C	27.5 (4)
C6—C1—C7	120.36 (15)	C16B—C14—C16C	51.7 (5)
C2—C1—C7	121.47 (15)	C17C—C14—C16C	108.6 (5)
O1—C2—C3	118.66 (16)	C11—C14—C16C	103.4 (3)
O1—C2—C1	121.68 (16)	C17B—C14—C16C	147.5 (4)
C3—C2—C1	119.66 (17)	C16A—C14—C16C	136.1 (4)
C4—C3—C2	120.23 (19)	C15C—C14—C15B	135.1 (5)
C4—C3—H3	119.9	C17A—C14—C15B	36.0 (4)
C2—C3—H3	119.9	C16B—C14—C15B	105.2 (5)
C3—C4—C5	121.15 (19)	C17C—C14—C15B	45.8 (5)
C3—C4—H4	119.4	C11—C14—C15B	112.7 (3)
C5—C4—H4	119.4	C17B—C14—C15B	102.6 (4)
C6—C5—C4	119.00 (18)	C16A—C14—C15B	77.6 (4)
C6—C5—H5	120.5	C16C—C14—C15B	63.5 (5)
C4—C5—H5	120.5	C15C—C14—C15A	25.6 (5)
C5—C6—C1	121.79 (18)	C17A—C14—C15A	109.0 (4)
C5—C6—H6	119.1	C16B—C14—C15A	37.6 (4)
C1—C6—H6	119.1	C17C—C14—C15A	129.1 (5)
N1—C7—C1	121.79 (15)	C11—C14—C15A	110.6 (2)
N1—C7—H7	119.1	C17B—C14—C15A	79.7 (4)
C1—C7—H7	119.1	C16A—C14—C15A	104.0 (4)
C13—C8—C9	118.10 (16)	C16C—C14—C15A	89.2 (4)
C13—C8—N1	118.58 (15)	C15B—C14—C15A	132.8 (4)
C9—C8—N1	123.28 (15)	C14—C15A—H15A	109.5
C10—C9—C8	120.23 (16)	C14—C15A—H15B	109.5
C10—C9—H9	119.9	C14—C15A—H15C	109.5
C8—C9—H9	119.9	C14—C16A—H16A	109.5
C9—C10—C11	122.57 (17)	C14—C16A—H16B	109.5
C9—C10—H10	118.7	C14—C16A—H16C	109.5
C11—C10—H10	118.7	C14—C17A—H17A	109.5
C10—C11—C12	115.93 (16)	C14—C17A—H17B	109.5
C10—C11—C14	123.19 (16)	C14—C17A—H17C	109.5
C12—C11—C14	120.88 (16)	C14—C15B—H15D	109.5
C13—C12—C11	122.03 (17)	C14—C15B—H15E	109.5
C13—C12—H12	119.0	H15D—C15B—H15E	109.5
C11—C12—H12	119.0	C14—C15B—H15F	109.5
C12—C13—C8	121.11 (17)	H15D—C15B—H15F	109.5
C12—C13—H13	119.4	H15E—C15B—H15F	109.5
C8—C13—H13	119.4	C14—C16B—H16D	109.5
C15C—C14—C17A	127.1 (6)	C14—C16B—H16E	109.5
C15C—C14—C16B	62.0 (7)	H16D—C16B—H16E	109.5
C17A—C14—C16B	73.4 (6)	C14—C16B—H16F	109.5
C15C—C14—C17C	109.6 (6)	H16D—C16B—H16F	109.5
C17A—C14—C17C	81.2 (5)	H16E—C16B—H16F	109.5
C16B—C14—C17C	133.7 (5)	C14—C17B—H17D	109.5
C15C—C14—C11	111.5 (4)	C14—C17B—H17E	109.5
C17A—C14—C11	112.0 (3)	H17D—C17B—H17E	109.5
C16B—C14—C11	114.6 (4)	C14—C17B—H17F	109.5
C17C—C14—C11	110.6 (4)	H17D—C17B—H17F	109.5
C15C—C14—C17B	54.6 (7)	H17E—C17B—H17F	109.5
C17A—C14—C17B	130.8 (5)	C14—C15C—H15G	109.5
C16B—C14—C17B	112.0 (5)	C14—C15C—H15H	109.5
C17C—C14—C17B	59.6 (6)	C14—C15C—H15I	109.5
C11—C14—C17B	109.1 (3)	C14—C16C—H16G	109.5
C15C—C14—C16A	80.2 (6)	C14—C16C—H16H	109.5
C17A—C14—C16A	110.7 (4)	C14—C16C—H16I	109.5
C16B—C14—C16A	129.1 (5)	C14—C17C—H17G	109.5
C17C—C14—C16A	32.8 (4)	C14—C17C—H17H	109.5
C11—C14—C16A	110.2 (3)	C14—C17C—H17I	109.5

C6—C1—C2—O1	179.11 (16)	C14—C11—C12—C13	177.63 (18)
C7—C1—C2—O1	−0.9 (2)	C11—C12—C13—C8	2.1 (3)
C6—C1—C2—C3	−0.9 (2)	C9—C8—C13—C12	−0.8 (3)
C7—C1—C2—C3	179.06 (15)	N1—C8—C13—C12	−178.56 (17)
O1—C2—C3—C4	−179.03 (17)	C10—C11—C14—C15C	34.4 (7)
C1—C2—C3—C4	1.0 (3)	C12—C11—C14—C15C	−145.1 (7)
C2—C3—C4—C5	−0.3 (3)	C10—C11—C14—C17A	−114.8 (5)
C3—C4—C5—C6	−0.5 (3)	C12—C11—C14—C17A	65.7 (5)
C4—C5—C6—C1	0.6 (3)	C10—C11—C14—C16B	−33.7 (5)
C2—C1—C6—C5	0.1 (2)	C12—C11—C14—C16B	146.9 (5)
C7—C1—C6—C5	−179.85 (15)	C10—C11—C14—C17C	156.6 (6)
C8—N1—C7—C1	−178.82 (14)	C12—C11—C14—C17C	−22.9 (6)
C6—C1—C7—N1	−174.33 (15)	C10—C11—C14—C17B	92.8 (5)
C2—C1—C7—N1	5.7 (2)	C12—C11—C14—C17B	−86.6 (4)
C7—N1—C8—C13	−138.90 (18)	C10—C11—C14—C16A	121.5 (4)
C7—N1—C8—C9	43.5 (2)	C12—C11—C14—C16A	−58.0 (5)
C13—C8—C9—C10	−0.6 (3)	C10—C11—C14—C16C	−87.3 (4)
N1—C8—C9—C10	177.05 (16)	C12—C11—C14—C16C	93.2 (4)
C8—C9—C10—C11	0.7 (3)	C10—C11—C14—C15B	−153.9 (4)
C9—C10—C11—C12	0.4 (3)	C12—C11—C14—C15B	26.6 (4)
C9—C10—C11—C14	−179.03 (17)	C10—C11—C14—C15A	7.0 (4)
C10—C11—C12—C13	−1.9 (3)	C12—C11—C14—C15A	−172.5 (3)

Experimental details

	(2)	(3)	(4)	(5)
Crystal data
Chemical formula	C₂₂H₂₉NO₂	C₂₁H₂₆BrNO	C₂₁H₂₆ClNO	C_21.05H_26.14BrNO
M_r	339.46	388.34	343.88	388.34
Crystal system, space group	Triclinic, P1	Triclinic, P1	Triclinic, P1	Monoclinic, P2₁/c
Temperature (K)	293	296	296	296
a, b, c (Å)	10.814 (2), 12.011 (2), 15.727 (3)	10.7505 (6), 11.5008 (7), 16.3284 (8)	10.7392 (12), 11.5369 (15), 16.1292 (19)	18.0699 (14), 10.5997 (10), 10.3838 (9)
α, β, γ (°)	89.25 (3), 81.21 (3), 89.97 (3)	87.959 (1), 83.166 (2), 89.536 (2)	88.032 (3), 82.446 (3), 89.642 (3)	90, 92.858 (2), 90
V (Å³)	2018.7 (7)	2003.20 (19)	1979.8 (4)	1986.4 (3)
Z	4	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.07	2.06	0.20	2.08
Crystal size (mm)	0.34 × 0.26 × 0.06	0.18 × 0.17 × 0.04	0.15 × 0.07 × 0.03	0.20 × 0.14 × 0.06

Data collection
Diffractometer	Bruker SMART CCD area detector system diffractometer	Rigaku R-AXIS RAPID IP Area Detector System diffractometer	Rigaku R-AXIS RAPID IP Area Detector System diffractometer	Rigaku R-AXIS RAPID IP Area Detector System diffractometer
Absorption correction	Multi-scan Absorption was corrected by SADABS	Multi-scan Absorption was corrected by ABSCOR	Multi-scan Absorption was corrected by ABSCOR	Multi-scan Absorption was corrected by ABSCOR
T_min, T_max	0.976, 0.996	0.189, 0.928	0.729, 0.994	0.559, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	29048, 10049, 5423	19830, 9015, 4719	16014, 7172, 2946	18792, 4500, 1915
R_int	0.036	0.054	0.079	0.109
(sin θ/λ)_max (Å⁻¹)	0.668	0.648	0.602	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.128, 0.92	0.043, 0.143, 1.08	0.064, 0.164, 1.02	0.059, 0.147, 1.02
No. of reflections	10049	9015	7172	4500
No. of parameters	482	445	461	241
No. of restraints	0	0	0	1
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.16	0.87, −0.78	0.20, −0.19	0.30, −0.39
Absolute structure	?	?	?	?

	(6)	(7)	(8)	(1)
Crystal data
Chemical formula	C₂₁H₂₇NO	C₂₂H₂₇NO₃	C₁₃H₁₀ClNO	C_17.12H_19.35NO
M_r	309.44	353.45	231.67	255.13
Crystal system, space group	Orthorhombic, Pna2₁	Monoclinic, P2₁/c	Monoclinic, P2₁/c	Monoclinic, P2₁/c
Temperature (K)	296	293	293	296
a, b, c (Å)	12.4043 (6), 8.9918 (5), 16.6903 (7)	6.1482 (4), 19.5491 (13), 17.0976 (13)	4.6868 (1), 18.9497 (4), 12.8231 (2)	14.3711 (8), 6.4227 (4), 17.9938 (9)
α, β, γ (°)	90, 90, 90	90, 109.453 (3), 90	90, 105.968 (1), 90	90, 116.819 (4), 90
V (Å³)	1861.59 (16)	1937.7 (2)	1094.92 (4)	1482.20 (14)
Z	4	4	4	4
Radiation type	Mo Kα	Mo Kα	Cu Kα	Mo Kα
µ (mm⁻¹)	0.07	0.08	2.88	0.07
Crystal size (mm)	0.50 × 0.35 × 0.15	0.40 × 0.30 × 0.02	0.33 × 0.10 × 0.06	0.34 × 0.30 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP Area Detector System diffractometer	Rigaku R-AXIS RAPID IP Area Detector System diffractometer	Rigaku VM-SPIDER IP Area Detector System diffractometer	Rigaku R-AXIS RAPID IP Area Detector System diffractometer
Absorption correction	Multi-scan Absorption was corrected by ABSCOR	Multi-scan Absorption was corrected by ABSCOR	Multi-scan Absorption was corrected by ABSCOR	Multi-scan Absorption was corrected by ABSCOR
T_min, T_max	0.798, 0.990	0.627, 0.998	0.340, 0.837	0.885, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	17422, 2193, 1955	17354, 4410, 2938	12241, 1976, 1565	23765, 3381, 2187
R_int	0.032	0.087	0.046	0.036
(sin θ/λ)_max (Å⁻¹)	0.648	0.649	0.602	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.101, 1.06	0.072, 0.206, 1.03	0.056, 0.170, 1.08	0.057, 0.190, 1.13
No. of reflections	2193	4410	1976	3381
No. of parameters	214	272	145	194
No. of restraints	1	0	0	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.14	0.33, −0.27	0.33, −0.21	0.22, −0.21
Absolute structure	Flack H D (1983), Acta Cryst. A39, 876-881	?	?	?

Computer programs: Bruker SMART, PROCESS-AUTO (Rigaku, 1998), Bruker SAINT & SADABS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), Siemens SHELXTL, ORTEP-3 (Farrugia, 2008).

Hydrogen-bond geometry (Å, º) for (4) top

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···N1A	0.82	1.86	2.599 (4)	149.3
O1B—H1B···N1B	0.82	1.84	2.578 (4)	149.2

Acknowledgements

This work was supported by Grant-in-Aid for Scientific Research from the Japan Society for Promotion of Science.

References

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Volume 68| Part 3| June 2012| Pages 297-304

doi:10.1107/S0108768112010993