Crystal structures of salts of bedaquiline

Bedaquiline [systematic name: 1-(6-bromo-2-meth­oxy­quinolin-3-yl)-4-(di­methyl­amino)-2-(naphthalen-1-yl)-1-phenyl­butan-2-ol, C₃₂H₃₁BrN₂O₂] is one of two important new drugs for the treatment of drug-resistant tuberculosis (TB). It is marketed in the US as its fumarate salt {systematic name: [4-(6-bromo-2-meth­oxy­quinolin-3-yl)-3-hy­droxy-3-(naphthalen-1-yl)-4-phenyl­but­yl]di­methyl­aza­nium 3-carb­oxy­prop-2-enoate, C₃₂H₃₂BrN₂O₂⁺·C₄H₃O₄⁻}, and about a dozen other salts of bedaquiline have been described in patent literature, but none have so far been structurally described. In a first communication, we present the crystal structure of bedaquilinium fumarate and of two new benzoate salts, as well as that of a degradation product of the reaction of bedaquilinium fumarate with sodium ethoxide, 3-benzyl-6-bromo-2-meth­oxy­quinoline, C₁₇H₁₄BrNO. The fumarate and benzoate salts both feature cations monoprotonated at the di­methyl­amino group. The much less basic quinoline N atom remains unprotonated. Both salts feature a 1:1 cation-to-anion ratio, with the fumarate being present as monoanionic hydro­fumarate. The conformations of the cations are com­pared to that of free base bedaquiline and with each other. The flexible backbone of the bedaquiline structure leads to a landscape of conformations with little commonalities between the bedaquiline entities in the various structures. The conformations are distinctively different for the two independent mol­ecules of the free base, the two independent mol­ecules of the hydro­fumarate salt, and the one unique cation of the benzoate salt. Packing of the salts is dominated by hydrogen bonding. Hydrogen-bonding motifs, as well as the larger hydrogen-bonded entities within the salts, are quite similar for the salts, despite the vastly differing conformations of the cations, and both the hydro­fumarate and the benzoate structure feature chains of hydrogen-bonded anions that are surrounded by and hydrogen bonded to the larger bedaquilinium cations, leading to infinite broad ribbons of anions, cations, and (for the benzoate salt) water mol­ecules. The benzoate salt was isolated in two forms: as a 1.17-hydrate (C₃₂H₃₂BrN₂O₂⁺·C₇H₅O₂⁻·1.166H₂O), obtained from acetone or propanol solution, with one fully occupied water mol­ecule tightly integrated into the hydrogen-bonding network of anions and cations, and one partially occupied water mol­ecule [refined occupancy 16.6 (7)%], only loosely hydrogen bonded to the quinoline N atom. The second form is an aceto­nitrile solvate (C₃₂H₃₂BrN₂O₂⁺·C₇H₅O₂⁻·0.742CH₃CN·H₂O), in which the partially occupied water mol­ecule is replaced by a 74.2 (7)%-occupied aceto­nitrile mol­ecule. The partial occupancy induces disorder for the benzoate phenyl ring. The aceto­nitrile solvate is unstable in atmosphere and converts into a form not distinguishable by powder XRD from the 1.17-hydrate.

1. Introduction

Bedaquiline, 1, is one of two important new drugs for the treatment of drug-resistant tuberculosis (TB). Bedaquiline is marketed in the US as the fumarate salt (2) with the trade name Sirturo (Brigden et al., 2015). The fumarate salt is described in US Patent 8 546 428 (Hegyi et al., 2013). The citrate, sulfate, phosphate, and tartrate salts are described in two other patents (Zvatora, Dammer, Krejcik et al., 2016; Zvatora, Dammer, Ridvan et al., 2016). However, none of these salts has been structurally described in detail. For the fumarate, as well as one each of the two sulfate and citrate salts, well-resolved powder X-ray patterns have been reported, but the structures were not solved and no single-crystal data are reported. For the remaining salts (the phosphate and tartrate salts, and the second sulfate and citrate polymorphs), the powder patterns indicate the samples to have either extremely small particle distributions or to be entirely amorphous. Detailed structural data are reported solely for the free base form of bedaquiline (Petit et al., 2007).

Bedaquiline features two basic N atoms that are amenable to protonation, i.e. the tertiary amine appended to the dangling ethyl­ene group and the pyridine N atom. The two sites have distinctly different basicities and selective proton­ation of only the more basic amine site should be possible. Salts of both mono- and dicationic bedaquilinium ions can thus be formed, depending on the strength and amount of acid used for salt formation. The formation of cocrystals (with no or incom­plete proton transfer) can also be imagined.

The NMR data reported in the patent publications indicate bedaquilinium fumarate to have a 1:1 anion-to-cation ratio. Whether the bedaquiline is protonated once or twice (and the fumarate deprotonated once or twice) had not been disclosed. For the sulfate salts, a 1:1 molar ratio of bedaquiline-to-sulfuric acid was used, but the anion-to-cation ratio in the salt was not determined. The given reaction yields, assuming a 1:1 salt, are around 33%, which would allow formation of a 1:2, a 1:1, or a 2:1 salt. The patent specifically states a wide range for the molar ratio of bedaquiline to sulfuric acid: `The molar ratio of bedaquiline:sulfuric acid may be in the range of 10:1 to 1:3, preferably 1:1, 2:1, and 1:2'. Similar statements have been made for the tartrate salts, one of the citrate salts, and the phosphate salt. No elemental analysis data are given to support any of the possible ratios, thus leaving the stoi­chi­om­etry and the overall nature of the presented salts in question. The possibility of hydrate or solvate formation was also not properly addressed in the patent claims.

This lack of structural knowledge and even of basic chemical com­position frustrates the understanding of the chemical, physical, and physiological properties of bedaquiline and its derivatives. To reduce this paucity of information on the bedaquiline system, there is inter­est in developing additional salts of bedaquiline and obtaining detailed analysis and structural data for these com­pounds, to better understand and possibly improve their properties, such as solubility, which in turn affect pharmacokinetics and dosage. Additional reasons for this study include finding a bedaquiline salt with improved stability and hygroscopicity.

2. Experimental

Melting points were determined using a Thomas Hoover Capillary Melting Point apparatus and are uncorrected. NMR data were collected in aceto­nitrile-d₃ (ACN-d₃) using a Bruker DRX-500 spectrometer and were referenced against the residual nondeuterated solvent peak.

Benzoic acid was purchased from Mallinckrodt, acetone from Fischer Chemicals, and aceto­nitrile from VWR Chemicals. Hydro­chloride in methanol 1.25 M was obtained from Fluka. Bedaquiline fumarate was obtained from Johnson & Johnson. All chemicals were used as received without further purification.

Polarized light microscopy images were collected using an Olympus Series BX51TRF (Olympus America Inc., Melville, NY) polarized light microscope equipped with 12 V/100 W illumination; an Achromat 0.9 NA polarized-light condenser; Olympus Series UPlanFL N objectives: 40X/0.75 NA, 20X/0.50 NA, 10X/0.30 NA, and 4X/0.13 NA; an inter­mediate tube with variable position analyzer and com­pensator; and a tri­nocular viewing head with a Lumenera Series Infinity X (Teledyne Lumenera, Ottawa, Ontario, Canada) digital camera using Infinity (Version 6.5.6) and Infinity Analyze software (Version 7.0.2.930, Build date 01-Feb-2020). A small portion of sample was placed on a cleaned microscope slide and a No. 1 1/2-cover glass placed over the sample. Mineral oil, USP (CAS: 8042-47-5), was allowed to cover the sample by capillarity. Images were acquired as a collection of three: (i) plane polarized light, (ii) crossed polarized light, and (iii) crossed polarized light with a first-order red com­pensator. Microscopy observations revealed crystal habits for bedaquilinium benzoate powders as birefringent platy anhedral agglomerates that are softly bound and easily dispersed under light pressure from a tungsten needle on the cover glass. A representative collection of images is given in the supporting information.

IR microspectroscopy experiments were conducted using a Smiths Detection (Danbury, CT) IlluminatIR 1.5 IR Microspectrometer accessory on an Olympus Series BX41TF polarized-light microscope (Olympus America Inc., Melville, NY), which provided the base optical platform. The IlluminatIR 1.5 is equipped with a gray-body ceramic IR source, a 60° Michelson Inter­ferometer with a zinc–selenide (ZnSe) beam splitter, a 4 wavenumber (cm⁻¹) spectral resolution, and a 0.25 × 0.25 mm liquid-nitro­gen-cooled mercury cadmium telluride (MCT) photoconductive detector, and the sample area was defined using a fixed circular 100 µm aperture. The IlluminatIR 1.5 is com­puter-inter­faced using universal serial bus (USB) communications with Smiths Detection QualID App (Version 2.51, 2005) software. Advanced data processing was conducted using either Thermo Galactic spectral analysis software packages GRAMS/AI and SpectralID, or Thermo Fisher Scientific OMNIC software (Version 9.11.706, 2020). IR analyses were performed by reflection/absorption (R/A) using an all-reflecting objective (ARO, 15X, 0.88 NA). A small amount of sample was transferred to a low-E microscope slide (Smiths Detection P/N: 006-4013) and dispersed to a thin layer. IR microprobe analyses were conducted on what appeared microscopically to be a single crystal. An FT–IR spectral background was collected immediately prior to each sample spectral analysis.

Powder X-ray diffraction (XRD) data were collected in focusing mode on a PANalytical Empyrean X-ray diffrac­tometer equipped with Bragg–Brentano HD optics, a sealed-tube copper X-ray source (λ = 1.54178 Å), Soller slits on both the incident and receiving optics sides, and a PixCel3D Medipix detector. Samples were hand ground using an agate mortar and pestle, and packed into a silicon single-crystal zero-background sample holder, 16 mm wide and 0.25 mm deep. Anti­scatter slits and divergence slits, as well as the mask, were chosen based on sample area and starting θ angle. Data were collected between 4 and 40° in 2θ under ambient conditions using the PANalytical Data Collector software (PANalytical, 2015). Rietveld refinements were performed against the 150 K models of the single-crystal structure data sets using HighScore (PANalytical, 2015) software. Refinement of preferred orientation was included using a spherical harmonics model. Plots of Rietveld fits for all com­pounds are given in the supporting information.

2.1. Synthesis and crystallization

2.1.1. Free base bedaquiline (1)

The free base used during synthesis was prepared by extracting a CH₂Cl₂ solution of the fumarate three times with saturated NaHCO₃ solution (Rombouts et al., 2016). The identity and purity of the free base thus afforded from the material supplied by Johnson & Johnson was verified using NMR spectroscopy [m.p. 175–176 °C; literature value 181°C (Zvatora, Dammer, Ridvan et al., 2016)]. ¹H NMR (500 MHz, ACN-d₃): δ 8.82 (s, 1H), 8.66 (d, J = 8.7 Hz, 1H), 8.03 (s, 1H), 8.02 (d, J = 7.3 Hz, 1H), 7.87 (d, J = 8.0 Hz, 1H), 7.66 (t, J = 7.7 Hz, 4H), 7.49 (t, J = 7.7 Hz, 1H), 7.30 (m, 3H), 6.87 (m, 3H), 5.88 (s, 1H), 4.20 (s, 3H), 2.52 (d, J = 14.6 Hz, 1H), 2.01 (m, 2H), 1.89 (m, 7H).

Single crystals were grown by dissolving bedaquiline (30 mg, 0.054 mmol) in acetone (1 ml) in a 5 ml scintillation vial and the solution was allowed to evaporate slowly to obtain medium-sized plate-shaped crystals of 1.

2.1.2. Decom­position of bedaquiline fumarate by sodium ethoxide

Sodium ethoxide (1.5 g, 22.0 mmol) was dissolved in EtOH (20 ml). The resulting solution was added to a solution of bedaquiline fumarate (5 g, 7.44 mmol) in ACN/EtOH (50 ml, 1:1 v/v). After 1 h, water was added slowly and the resulting mixture extracted with EtOAc. The combined organic layers were dried (MgSO₄) and then concentrated to provide a colorless crystalline material that was found by IR and NMR spectroscopies to not match free base bedaquiline. Individual crystals were identified as 3-benzyl-6-bromo-2-meth­oxy­quinoline (3) by single-crystal X-ray diffraction, and no further analyses were performed.

2.1.3. Bedaquilinium fumarate (2)

Bedaquiline (30 mg, 0.054 mmol) was mixed with fumaric acid (6.3 mg, 0.054 mmol) dissolved in acetone (1 ml) in a 10 ml scintillation vial. Propyl alcohol (5 ml) was then added and the mixture was allowed to evaporate slowly to obtain large colorless block-shaped crystals that were analyzed by single-crystal and powder X-ray diffraction. ¹H NMR (500 MHz, ACN-d₃): δ 8.68 (d, J = 8.3 Hz, 1H), 8.55 (s, 1H), 8.05 (d, J = 7.2 Hz, 1H), 7.97 (s, 1H), 7.88 (d, J = 7.9 Hz, 1H), 7.66 (m, 4H), 7.51 (t, J = 7.2 Hz, 1H), 7.32 (m, 3H), 6.89 (m, 3H), 6.32 (s, 2H), 5.89 (s, 1H), 4.21 (s, 3H), 3.02 (m, 1H), 2.69 (m, 1H), 2.24 (s, 7H), 2.09 (m, 2H).

2.1.4. Bedaquilinium benzoates 4a and 4b

Bedaquiline (30 mg, 0.054 mmol) was mixed with benzoic acid (6.7 mg, 0.055 mmol). The mixture was dissolved in acetone (2 ml) in a 5 ml scintillation vial and was allowed to evaporate. The 1.17-hydrate 4a was obtained in the form of colorless rod-shaped crystals (m.p. 127–129 °C). ¹H NMR (500 MHz, ACN-d₃): δ 8.75 (d, J = 8.4 Hz, 1H), 8.67 (s, 1H), 8.12 (d, J = 7.1 Hz, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.86 (m, 3H), 7.75 (d, J = 8.0 Hz, 2H), 7.56 (m, 4H), 7.38 (m, 5H), 6.93 (m, 3H), 5.95 (s, 1H), 4.26 (s, 3H), 3.05 (m, 1H), 2.96 (m, 1H), 2.25 (m, 7H), 1.96 (m, 2H). An identical material with the same water content was obtained when crystallization was carried out from 2-propanol instead of acetone.

Bedaquiline (30 mg, 0.054 mmol) was mixed with benzoic acid (6.8 mg, 0.056 mmol) in aceto­nitrile (10 ml) and was allowed to evaporate slowly. The aceto­nitrile solvate monohydrate 4b was obtained in the form of thin colorless needles (m.p. 127–129 °C).

2.2. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 1. The two benzoate salt structures 4a and 4b are isomorphous, differing from each other only in the nature of part of the solvent mol­ecules and some slight shifts to other atoms, and they were refined against a common structural model, with the structure of 4b being solved by isomorphous replacement from that of 4a. The atom-naming scheme for the published bedaquiline free base structure (Petit et al., 2007), as deposited in the Cambridge Structural Database (CSD; Groom et al., 2016; refcode KIDWAW), was used for the remeasured 150 K data of free base bedaquiline 1 and was also adopted for the bedaquilinium cations in the two benzoate salts 4a and 4b, and fumarate salt 2.

Table 1
Experimental details

Experiments were carried out at 150 K. Absorption was corrected for by multi-scan methods (SADABS2016; Krause et al., 2015).

	1	2	3
Crystal data
Chemical formula	C32H31BrN2O2	C32H32BrN2O2^+·C4H3O4^−	C17H14BrNO
Mr	555.50	671.57	328.20
Crystal system, space group	Orthorhombic, P212121	Monoclinic, P21	Orthorhombic, P212121
a, b, c (Å)	11.1584 (8), 13.6425 (14), 36.061 (4)	16.4556 (6), 10.3205 (3), 20.1636 (8)	4.3606 (6), 10.820 (2), 29.886 (11)
α, β, γ (°)	90, 90, 90	90, 109.1832 (15), 90	90, 90, 90
V (Å^3)	5489.5 (9)	3234.2 (2)	1410.1 (6)
Z	8	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm^−1)	1.53	1.32	2.91
Crystal size (mm)	0.21 × 0.13 × 0.05	0.45 × 0.37 × 0.17	0.41 × 0.06 × 0.05
Data collection
Diffractometer	Bruker D8 Quest diffractometer with PhotonII charge-integrating pixel array detector (CPAD)	Bruker D8 Quest diffractometer with PhotonII charge-integrating pixel array detector (CPAD)	Bruker D8 Quest diffractometer with PhotonII charge-integrating pixel array detector (CPAD)
Tmin, Tmax	0.603, 0.747	0.438, 0.495	0.658, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	66520, 17893, 12296	115858, 24622, 18572	28030, 5125, 4504
Rint	0.052	0.040	0.037
(sin θ/λ)max (Å^−1)	0.770	0.771	0.768
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.044, 0.111, 1.03	0.043, 0.117, 1.06	0.023, 0.057, 1.05
No. of reflections	17893	24622	5125
No. of parameters	675	837	196
No. of restraints	0	1	0
H-atom treatment	H-atom parameters constrained	H atoms treated by a mixture of independent and constrained refinement	Only H-atom displacement parameters refined
Δρmax, Δρmin (e Å^−3)	0.48, −0.58	1.23, −1.28	0.28, −0.38
Absolute structure	Flack x determined using 4397 quotients [(I^+) − (I^−)]/[(I^+) + (I^−)] (Parsons et al., 2013)	Flack x determined using 7327 quotients [(I^+) − (I^−)]/[(I^+) + (I^−)] (Parsons et al., 2013)	Flack x determined using 1685 quotients [(I^+) − (I^−)]/[(I^+) + (I^−)] (Parsons et al., 2013)
Absolute structure parameter	0.034 (3)	−0.0144 (14)	−0.011 (3)

	4a	4b
Crystal data
Chemical formula	C32H32BrN2O2^+·C7H5O2^−·1.166H2O	C32H32BrN2O2^+·C7H5O2^−·0.742C2H3N·H2O
Mr	698.70	726.10
Crystal system, space group	Monoclinic, P21	Monoclinic, P21
a, b, c (Å)	12.6384 (5), 7.9259 (3), 17.5249 (8)	12.8661 (8), 8.0386 (5), 17.4704 (10)
α, β, γ (°)	90, 99.8450 (17), 90	90, 101.093 (3), 90
V (Å^3)	1729.63 (12)	1773.13 (19)
Z	2	2
Radiation type	Mo Kα	Cu Kα
μ (mm^−1)	1.24	1.97
Crystal size (mm)	0.55 × 0.21 × 0.13	0.31 × 0.05 × 0.05
Data collection
Diffractometer	Bruker D8 Quest diffractometer with PhotonII charge-integrating pixel array detector (CPAD)	Bruker D8 Quest diffractometer with PhotonIII_C14 charge-integrating and photon counting pixel array detector
Tmin, Tmax	0.638, 0.746	0.599, 0.754
No. of measured, independent and observed [I > 2σ(I)] reflections	80228, 13080, 10456	39739, 7360, 6750
Rint	0.049	0.060
(sin θ/λ)max (Å^−1)	0.770	0.639
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.032, 0.073, 1.03	0.035, 0.085, 1.06
No. of reflections	13080	7360
No. of parameters	445	515
No. of restraints	5	195
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å^−3)	0.36, −0.48	0.40, −0.50
Absolute structure	Flack x determined using 4051 quotients [(I^+) − (I^−)]/[(I^+) + (I^−)] (Parsons et al., 2013)	Flack x determined using 2778 quotients [(I^+) − (I^−)]/[(I^+) + (I^−)] (Parsons et al., 2013)
Absolute structure parameter	0.006 (3)	0.004 (8)
Computer programs: APEX3 (Bruker, 2019), SAINT (Bruker, 2019), SHELXS97 (Sheldrick, 2008), SHELXL2018 (Sheldrick, 2015), shelXle (Hübschle et al., 2011), Mercury (Macrae et al., 2020) and publCIF (Westrip, 2010).

For powder X-ray data collection and refinement, see the Experimental (§2).

2.2.1. H-atom treatment

C-bound H atoms were added in calculated positions and refined using a riding model. C—H bond distances were constrained to 0.95 Å for aromatic C—H moieties, and to 1.00, 0.99, and 0.98 Å for aliphatic C—H, CH₂, and CH₃ moieties, respectively. Alcohol O—H and ammonium NR₃H N—H bond distances were either freely refined (for 2) or were constrained to 0.84 and 1.00 Å, respectively. Methyl CH₃ and hy­droxy H atoms were allowed to rotate but not to tip to best fit the experimental electron density. The positions of the carboxyl­ate H atoms (in 2) were refined freely. The positions of the fully occupied water H atoms were refined freely and O—H distances were restrained to 0.84 (2) Å. The H atoms of the partially occupied water mol­ecule in 4a were initially refined and O—H and H⋯H distances were restrained to 0.84 (2) and 1.36 (2) Å, respectively, while a damping factor was applied. The position of water atom H6E (in 4a) was further restrained based on hydrogen-bonding considerations, i.e. to be hydrogen bonded to the pyridine H atom, with the H⋯N distance restrained to 2.35 (2) Å. In the final refinement cycles, the damping factor was removed and the H atoms were set to ride on the parent O atom. For all structures, the U_iso(H) values were set to a multiple of U_eq(C), being 1.5 for CH₃ and OH, and 1.2 for C—H, CH₂, and N—H groups, respectively.

2.2.2. Disorder modeling

In the structure of 4a, one fully occupied and one partially occupied water mol­ecule are present in the lattice. The occupancy ratio refined to 0.166 (7). In 4b, the partially occupied water mol­ecule is replaced by an approximately three-quarter-occupied aceto­nitrile mol­ecule. In the absence of the aceto­nitrile mol­ecule, the neighboring benzene ring of the benzoate anion tilts slightly to move towards the void left by the absent solvent mol­ecule. The two disordered benzene moieties were restrained to have similar geometries. The U^ij com­ponents of the anisotropic displacement parameters (ADPs) for disordered atoms closer to each other than 2.0 Å were restrained to be similar. The ADPs of the ipso C atoms, which occupy nearly identical positions, were constrained to be identical. Subject to these conditions, the occupancy ratio refined to 0.742 (7):0.258 (7) in favor of the aceto­nitrile mol­ecule being present.

3. Salt screening and methods

Salt screening is a com­plex and challenging endeavor involving potentially millions of experiments. For bases like bedaquiline, these experiments can involve up to 50 commonly used salt formers in various ratios, as well as crystallizations from up to 60 different solvents by varying temperature, concentration, agitation, pH, and other factors. Further mixtures of these solvents can be used. Anti­solvent crystallization using these solvents is also of inter­est and introduces even more variables.

For bedaquiline, the first step in screening for additional salts involved recovering bedaquiline free base from the commercially available bedaquilinium fumarate. This was first attempted by deprotonation of the bedaquilinium cation of the fumarate salt using the base sodium ethoxide. However, the alkoxide, when used in excess, proved to be too strong a base and led to fragmentation of the bedaquiline mol­ecule. One of the products of the decom­position reaction was isolated by crystallization and identified, by single-crystal X-ray diffraction, as 3-benzyl-6-bromo-2-meth­oxy­quinoline (3) (Fig. 1) and its structure will be described below. The other half of the decom­position reaction was not recovered or identified, but is assumed to be the ketone elimination product of the remaining bedaquiline fragment, 4-(di­methyl­amino)-1-(naphthalen-1-yl)butan-2-one. The reaction most likely pro­ceeds through initial deprotonation of all acidic groups by the ethoxide, including the central alcohol of bedaquiline. The tertiary alkoxide thus formed can undergo a reverse Grignard reaction (Zook et al., 1959), under elimination of the ketone and the carbanion of 3. Using much less basic sodium bicarbonate as the neutralizing agent avoids this decom­position reaction. Bedaquiline free base could be recovered that way from the fumarate salt, following the procedure described by Rombouts et al. (2016), thus allowing us to proceed to use the free base in salt screening experiments (Fig. 1).

Figure 1 Isolation of free base bedaquiline (1) from commercially available bedaquilinium fumarate (2), and decom­position to 3.

Because the fumarate, citrate, sulfate, phosphate, and tartrate salts were known, salt formation screening focused on the crystallization of salts such as acetate, benzoate, ben­zene­sulfonate, hydro­bromide, succinate (1:1 and 1:2), hydro­chloride, tartrate (1:1 and 1:2), lactate, maleate (1:1 and 1:2), malate (1:1 and 1:2), and mesylate. In general, the crystallizations involved mixing stoichiometric amounts of bedaquiline with the acids at either 1:1 or 1:2 molar ratios in acetone, aceto­nitrile, tetra­hydro­furan, and ethyl acetate, either with or without the anti­solvents water and hexane. The solvents were evaporated either slowly or rapidly, and materials were typically first screened using polarized-light microscopy (PLM) to ensure that a crystalline material had formed, and that the sample was uniform. Samples that passed the first screening step were submitted for further analysis. Crystals were analyzed by NMR (dissolved in an appropriate solvent) to confirm the presence of both com­ponents in the material. In the next step, materials were further screened using IR microspectroscopy, to confirm that the material was indeed a new substance (a salt or a cocrystal), and not just a mixture of the two com­ponents. Although some investigators have advanced the theory that Raman spectroscopy is the best method for analysis and determination of salt formation (e.g. Kojima et al., 2010), we found IR microspectroscopy had better specificity than Raman microscopy for the bedaquiline free base and salts; therefore, screening materials via Raman methods was abandoned. IR microspectroscopy proved to be a superior method to determine the formation of bedaquilinium salts. Materials that passed these screening steps (PLM, NMR, and IR spectroscopy) were then analyzed by powder X-ray diffraction. Rietveld refinement was used to identify known crystal phases. For samples for which suitable crystals could be obtained, single-crystal X-ray diffraction was used to determine the structures of phases not yet structurally described.

Example IR spectra com­paring bedaquilinium benzoate and free base bedaquiline are given in Fig. 2; see Fig. 3 for the synthesis. The spectra are distinctly different, indicating transformation of the free base into a material containing both benzoate and bedaquiline fragments. A range of bands in the fingerprint region indicate the presence of a bedaquiline com­ponent in both com­pounds. A shoulder near 1700 cm⁻¹ in the bedaquiline benzoate spectrum can be assigned to the C=O stretch of benzoate, confirming the formation of the salt. Further evidence for the formation of a salt, rather than a simple mixture of the two starting materials, is provided by the absence of bands in the range 2830–2760 cm⁻¹. Tertiary amines (of which the free base is one) have a characteristic N—CH₂ in-phase stretch that occurs in this range (Colthup et al., 1990). The bands in this range of the free base spectrum are not present in the bedaquiline benzoate spectrum, suggesting the formation of a salt. Note: the free base spectrum contains some spectral features due to ethanol, which was used in the synthesis process.

Figure 2 IR spectra of bedaquilinium benzoate (4a) (blue) and bedaquiline free base (1) (red).

Figure 3 Synthesis of bedaquilinium benzoate (4).

In the course of our investigations, we had been so far able to determine the single-crystal structures of bedaquilinium fumarate (2), the commercially available form of bedaquiline, as well as isolate and characterize two other previously unknown bedaquilinium salts: the mono-benzoate salt, in the form of its 1.17-hydrate (4a), and a mixed hydrate aceto­nitrile solvate (4b). Their structures, as well as that of the degradation product from reaction of bedaquilinium fumarate with sodium ethoxide, 3-benzyl-6-bromo-2-meth­oxy­quinoline (3), will be described below. The structure of free base bedaquiline (1) was re-recorded at 150 K for easier com­parison with the low-temperature data of 2, 4a, and 4b. Implications for the larger bedaquiline system will be discussed.

4. Results and discussion

3-Benzyl-6-bromo-2-meth­oxy­quinoline (3), the solvolysis pro­duct from reaction of bedaquiline with sodium ethoxide, lacks an easy-to-identify NMR signature and was identified by single-crystal X-ray diffraction. It crystallized from aceto­nitrile in the ortho­rhom­bic and chiral space group P2₁2₁2₁ (Fig. 4). The starting bedaquilinium fumarate is a chiral com­pound and an enanti­opure sample was used. This chiral information and all chiral centers are, however, lost in the degradation reaction to 3-benzyl-6-bromo-2-meth­oxy­quino­line (3). In the solid state, the mol­ecule does, however, exhibit chirality, and the crystal analyzed was found to be enanti­opure, with a Flack parameter of −0.011 (3). In solution, the material is expected to be a rapidly inter­converting racemic mixture, as simple rotation of the benzyl group to the other side of the mean plane of the mol­ecule creates the inversion-related enanti­omer. Mol­ecules of 3 are divided into two planar fragments: the benzyl group and the 6-bromo-2-meth­oxy­quinoline moiety. Both fragments are close to ideally flat, with r.m.s. deviations from planarity of only 0.0052 and 0.0194 Å, respectively. The meth­oxy group is thus ideally coplanar with the remainder of the bromo­quinoline fragment. It points away from the benzyl CH₂ group to avoid steric inter­actions. The torsion angle between the two mean planes is 73.01 (4)°.

Figure 4 The structure of decom­position product 3 (50% probability displacement ellipsoids).

The structures of the three bedaquilinium salts, i.e. fumarate 2, and benzoates 4a and 4b, are substanti­ally more com­plicated (Figs. 5 and 6), but they share some commonalities. In all three salt structures, the bedaquilinium cation is singly protonated at the di­methyl­amino fragment, with 1:1 anion-to-cation ratios. In the structure of 2, the fumarate anions remain singly protonated hydro­fumarate(1−) anions, thus being monoanionic, as are the benzoate anions. The quinoline N atoms remain unprotonated, even though there are additional acidic protons available in the structure of 2. At first glance, this might be surprising, since many pyridinium salts of both benzoic and fumaric acids have been reported [973 pyridinium benzoate derivatives and 44 pyridinium fumarate salts are reported in the CSD (Groom et al., 2016), accessed August 2020]. The behaviour is, however, in agreement with the pK_a values of the acids and with the reduced basicity of the quinoline N atom of bedaquiline, com­pared to ordinary pyridine. The first pK_a of fumaric acid is 3.053, the second is 4.494, and that of benzoic acid is 4.202 (Martell & Smith, 1976), which are easily sufficient to protonate the amine moiety of bedaquiline [the pK_a of tri­alkyl­ammonium ions are around 10–11 (Bioquest, 2020)]. The pK_a of the conjugated acid of bedaquiline protonated at the quinoline N atom is not reported but can be estimated from the known values for quinoline, pyridine, and 2-meth­oxy­pyridine, which are 4.9, 5.23, and 3.06, respectively (Bioquest, 2020). Meth­oxy substitution in the 2-position to the N atom substanti­ally reduces the basicity of the N atom (the pK_a of the conjugated acid drops by 2.17 between pyridine and 2-meth­oxy­pyridine). Assuming other effects to be negligible yields a pK_a value of 2.73 for 2-meth­oxy­quinolinium. The quinoline N atom of bedaquiline is thus not basic enough to be protonated by medium-strength acids, such as benzoic or fumaric acid, in agreement with the findings from the crystal structures for 2, 4a, and 4b. Stronger acids, such as mineral acids or maleic acid (first pK_a is 1.94; Bioquest, 2020), might be able to double protonate bedaquiline if used in sufficient excess. Experiments in this direction are ongoing in our laboratories.

Figure 5 Single-crystal structure of fumarate salt 2 (50% probability displacement ellipsoids).

Figure 6 Single-crystal structures of benzoate salts of 4a (left) and 4b (right) (50% probability displacement ellipsoids). Hydrogen bonds are shown as turquoise dashed lines.

All three salts do crystallize in the chiral monoclinic space group P2₁. The core of the bedaquilinium cation in the three structures is formed by the ethyl­ene moiety of atoms C1 and C2, from which the four major substituents radiate off: the phenyl ring and the bromo­(meth­oxy)quinoline group from C1, and the naphthyl and (di­methyl­amino)­ethyl fragments from C2. The hy­droxy group is also attached to C2, while C1 also carries a single H atom. Atoms C1 and C2 are also the chiral centers of the bedaquilinium cation, which were modeled to have R and S chiralities, respectively, in agreement with the reported absolute structure for free base bedaquiline (Petit et al., 2007). The Flack parameters refined to −0.014 (1) for 2, and to 0.006 (3) and 0.004 (8) for 4a and 4b, respectively, confirming that the crystals were enanti­opure.

The arrangement of anions and cations, and packing inter­actions, however, vary substanti­ally between the fumarate and the two benzoate salts. The fumarate salt crystallized in an anhydrous and unsolvated form. Two crystallographically unique ion pairs are present in the lattice (i.e. Z′ = 2 for com­pound 2). The structure obtained agrees with the reported powder patterns of commercially available bedaquilinium fumarate (see Fig. 7 for a Rietveld refinement plot).

Figure 7 Powder XRD pattern (ambient temperature) of bedaquilinium fumarate (Johnson & Johnson) with a Rietveld refinement fit against the single-crystal structure of 2. The room-temperature unit-cell parameters refined to a = 16.5879 (2), b = 10.4952 (8), c = 20.183 (2) Å, β = 109.238 (2)° and V = 3317.4 (4) Å^3. Rietveld fits for 4a and 4b are given in the supporting information.

The two newly isolated benzoate salts are distinctly different from 2, both being solvates, but they are very similar to each other, and are indeed isomorphous (the aceto­nitrile solvate was solved by isomorphous replacement from the hydrate). Both structures feature one tightly bound water mol­ecule (atom O5). A second inter­stitial site does, however, differ between the two phases. In 4a, it is occupied by a second water mol­ecule, which is partially occupied. In 4b, on the other hand, this site is partially occupied by a disordered aceto­nitrile mol­ecule, which in turn induces disorder in the phenyl ring of the benzoate anion [see Refinement (§2.2.2) for disorder details].

The ethane backbone of the bedaquiline core gives the cations a three-dimensional (3D) shape, but the individual aromatic fragments remain planar. Similar to 3, the 6-bromo-2-meth­oxy­quinoline moiety is planar, with the meth­oxy group pointing away from the core of the cation. The r.m.s. deviations from planarity are 0.1127 and 0.1363 for the two cations in 2 (Z′ = 2), 0.1019 Å in 4a, and 0.0922 Å in 4b.

The ethane backbone and the malleable ethyl­amine fragment gives the bedaquilinium cations a high degree of con­formational flexibility. Differing packing arrangements, induced by the presence (or absence) of varying anions and solvent mol­ecules, led to a landscape of conformations observed for the cations in 2, 4a, and 4b, as well as free base bedaquiline 1. The dihedral angles between the mean planes of the 6-bromo-2-meth­oxy-quinoline fragment (plane 1), the phenyl ring (plane 2), and the naphthyl group (plane 3), as well as the torsion angles along the ethane backbone and the ethyl­amine fragment, are given in Table 2. Besides the obvious similarities between the values for isomorphous 4a and 4b, no general trend is observed. The conformations vary not only between the four structures, but even between independent mol­ecules within the same structure (both free base 1 and fumarate 2 are Z′ = 2 structures). The two C1—C2—C3—C4 torsion angles in fumarate salt 2, for example, are −63.8 (3) and 174.92 (19)°, which are distinctly different from each other. However, some similarities can be observed: the inter­planar angles between the phenyl and 6-bromo-2-meth­oxy­quinoline planes are between 70 and 90° in all structures, and the torsion angles involving the ethane backbone and the ipso phenyl atom (C17—C1—C2—C3) are close to anti­periplanar (`trans') in all the com­pounds. No other similarities common to all four structures can be found and the overall trend is one of pronounced flexibility and variability.

Table 2
Selected torsion angles (°) for free base bedaquiline 1, fumarate salt 2, and benzoate salts 4a and 4b

	1^a,b	2^b	4a^a	4b^a
τ plane 1 versus plane 2^c	73.29 (7), 81.37 (7)	85.33 (9), 86.02 (8)	77.31 (6)	76.2 (1)
τ plane 2 versus plane 3^c	86.13 (8) 76.95 (7)	89.7 (1), 89.74 (9)	45.62 (6)	44.2 (1)
τ plane 1 versus plane 3^c	14.0 (1), 8.16 (9)	8.71 (3), 16.67 (4)	37.50 (6)	36.7 (1)
τ C1—C2—C3—C4	175.7 (3), 177.0 (3)	−63.8 (3), 174.92 (19)	166.84 (14)	165.1 (3)
τ C2—C3—C4—N1	58.7 (4), 63.0 (4)	137.2 (2), 133.7 (2)	164.04 (15)	165.5 (3)
τ C17—C1—C2—C3	169.0 (3), 178.8 (3)	169.7 (2), 171.38 (19)	174.44 (14)	174.1 (3)
Notes: (a) measured at 150 K; (b) Z′ = 2; (c) plane 1 = 6-bromo-2-meth­oxy­quinoline, plane 2 = phenyl, and plane 3 = naphthyl.

While the geometries and conformations in the four bedaquiline structures do not follow any general trend, there are some differences between the geometries of free base bedaquiline and its salts that can be rationalized. Directional inter­actions that differ between the free base and the salts play a major role. In bedaquiline, only one actual hydrogen bond is present, and this is an intra­molecular O—H⋯N hydrogen bond (Table 3). It induces the amine N atoms to turn towards the hy­droxy group, thus enforcing a gauche geometry of the (di­methyl­amino)­ethyl group (see torsion angle C2—C3—C4—N1 in Table 2). Inter­molecular inter­actions between mol­ecules in 1 are limited to weaker and less directional inter­actions, specifically Br⋯Br inter­actions and π-stacking, which had been discussed in detail by Petit et al. (2007). In the fumarate and benzoate salts 2 and 4, the opposite is observed. The amine moiety, being protonated, is unable to act as the acceptor for an O—H⋯N hydrogen bond, and it takes up the role of a hydrogen-bond donor towards the benzoate or fumarate anions. This releases the amine from the gauche conformation enforced by the intra­molecular O—H⋯N hydrogen bond in 1, and the ethyl­amine instead extends into a more relaxed conformation, approaching anti in 4 and close to eclipsed in 2 (see torsion angle C2—C3—C4—N1 in Table 2). The hy­droxy groups in the salts are freed up to also form inter­molecular hydrogen bonds. In 4, they hydrogen bond with the fully occupied water mol­ecule, and in 2 with a fumarate carboxyl­ate group. The water mol­ecule in 4 in turn extends hydrogen bonds to the O atoms of two neighboring benzoate anions, and the fumarate anions in 2 are involved in a series of hydrogen bonds among each other, forming an infinite chain of hydrogen-bonded anions along the b-axis direction (Fig. 8). Thus, one intra­molecular hydrogen bond in free base bedaquiline 1 is converted into a whole series of strong inter­molecular hydrogen bonds (Tables 4, 5 and 6), creating for the salts a much stronger cohesion between neighboring structural entities than what was observed in the free base structure. Weaker inter­actions that dominate for bedaquiline, such as Br⋯Br halogen bonds and π-stacking, are not observed for the salts, but the strong hydrogen bonds are augmented by a range of other not-as-strong directional inter­actions, such as C—H⋯O and C—H⋯Br hydrogen bonds (see hydrogen-bond Tables 4, 5, and 6 for a full listing).

Table 3
Hydrogen-bond geometry (Å, °) for 1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N1	0.84	1.94	2.696 (4)	150
C1—H1⋯O2	1.00	2.24	2.763 (4)	111
O3—H3O⋯N3	0.84	1.93	2.685 (4)	149
C33—H33⋯O4	1.00	2.23	2.773 (4)	112

Table 4
Hydrogen-bond geometry (Å, °) for 2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1A—H1AB⋯O4A	0.86 (4)	1.88 (4)	2.699 (3)	159 (4)
O5A—H5A⋯O4B	1.04 (4)	1.58 (4)	2.603 (3)	169 (4)
N1A—H1AN⋯O3A	0.98 (4)	1.68 (4)	2.641 (3)	163 (3)
C1A—H1A⋯O2A	1.00	2.23	2.767 (3)	112
C3A—H3AB⋯Br1B^i	0.99	3.01	3.850 (3)	143
C5A—H5AA⋯O1A^ii	0.98	2.58	3.501 (3)	157
C5A—H5AC⋯Br1B^i	0.98	2.82	3.612 (3)	139
C26A—H26A⋯O5B^iii	0.95	2.54	3.459 (4)	163
C34A—H34A⋯O5B^iii	0.95	2.52	3.379 (3)	151
O1B—H1B⋯O4B^iv	0.89 (4)	1.88 (4)	2.741 (3)	160 (4)
O6B—H6B⋯O4A^v	0.86 (5)	1.80 (5)	2.625 (3)	159 (4)
N1B—H1BN⋯O3B^iv	0.85 (4)	1.83 (4)	2.632 (3)	158 (4)
C5B—H5BA⋯O1B^vi	0.98	2.42	3.337 (4)	156
C5B—H5BB⋯Br1A	0.98	2.88	3.468 (3)	119
C5B—H5BB⋯O6A	0.98	2.42	3.287 (4)	148
Symmetry codes: (i) x+1, y, z+1; (ii) ; (iii) ; (iv) ; (v) x, y+1, z; (vi) .

Table 5
Hydrogen-bond geometry (Å, °) for 4a

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O5	0.84	1.87	2.681 (2)	164
O5—H5D⋯O4^i	0.90 (4)	1.85 (4)	2.724 (2)	163 (3)
O5—H5E⋯O3	0.77 (3)	1.96 (3)	2.724 (2)	172 (4)
O6—H6E⋯N2	0.87	2.38	3.148 (13)	147
N1—H1⋯O4^i	1.00	1.64	2.643 (2)	178
C5—H5C⋯Br1^ii	0.98	3.09	3.910 (2)	142
C6—H6A⋯O3	0.98	2.53	3.465 (3)	161
C6—H6B⋯O6^iii	0.98	2.28	3.249 (13)	169
C28—H28⋯O5^ii	0.95	2.59	3.421 (3)	146
Symmetry codes: (i) ; (ii) ; (iii) .

Table 6
Hydrogen-bond geometry (Å, °) for 4b

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O5	0.77	1.94	2.691 (4)	163
O5—H5D⋯O4^i	0.86 (3)	1.89 (3)	2.738 (4)	168 (6)
O5—H5E⋯O3	0.82 (3)	1.92 (3)	2.734 (4)	172 (6)
N1—H1⋯O4^i	1.00	1.62	2.619 (4)	178
C5—H5C⋯Br1^ii	0.98	3.13	3.964 (4)	144
C6—H6A⋯O3	0.98	2.63	3.562 (6)	159
C28—H28⋯O5^ii	0.95	2.66	3.498 (5)	148
Symmetry codes: (i) ; (ii) .

Figure 8 Hydrogen-bonding pattern in 2. (Top) Chains along b created by hydro­fumarate anions. For clarity, only the 3-di­methyl­aza­niumyl-1-hy­droxy­propyl fragments of the cations are shown, and H atoms not involved in hydrogen bonds have been omitted. (Bottom) Segment of an entire ribbon, including full cations. Color coding: O, N, and Br atoms are shown with 50% probability displacement ellipsoids, with all other atoms in capped-stick mode and color coded by the symmetry equivalence of their anion and cation (A and B cations in light and dark green, and A and B anions in orange and red). Hydrogen bonds are shown as turquoise and red dashed lines.

In the aceto­nitrile solvate 4b, an H atom of the naphthyl group inter­acts in a C—H⋯N hydrogen-like bond with the solvent mol­ecule, when present. In its absence, the phenyl ring of the benzoate anion relaxes towards the void created, inducing disorder for the anion [see Refinement (§2.2.2) for details]. For the 1.17-hydrate 4a, the partially occupied water mol­ecule is hydrogen bonded to the pyridine N atom and acts as an acceptor for a C—H⋯O inter­action. There is, however, no second possible hydrogen-bond acceptor near the partially occupied water mol­ecule, and the second water H atom is not involved in any recognizable inter­action. This is energetically unfavorable, which helps to explain why this position is occupied less than 20% of the time [the refined value is 16.6 (7)%], while the other solvent water mol­ecule, tightly hydrogen bonded on all sides, is fully occupied. Lack of space appears to be no issue, as the larger aceto­nitrile mol­ecule in 4b has a higher occupancy of around three-quarters [refined value 74.2 (7)%]. Kinetic factors during crystal growth (a lack of water mol­ecules during crystallization from mostly dry solvents for 4a, but no lack of aceto­nitrile mol­ecules for 4b) seem to dominate. The presence or absence of either water or aceto­nitrile in this void does not appear to hinder continuation of crystal growth, while this cannot be said for the tightly incorporated O5 water mol­ecule present in both structures, which appears to be essential for the formation of this structure. The larger size of aceto­nitrile versus water, and the low prevalence of the second water mol­ecule in 4a, lead to a slightly larger unit-cell volume for 4b com­pared to 4a, i.e. 1773.13 (19) versus 1729.63 (12) ų. The visually most obvious difference between the two structures is the difference in the β angle, which is expanded by slightly more than 1° in 4b, leading to a significant offset between atoms in the two structures when the unit cells are overlaid (Fig. 9). The same is evident when com­paring the powder patterns of 4a and 4b simulated from the 150 K single-crystal data, which are distinctively different (see supporting information).

Figure 9 Least-squares overlay of the structures of 4a (red) and 4b (blue) using the non-H atoms for one of the two ion pairs of the asymmetric unit (r.m.s. fit value = 0.152), ignoring water and solvent mol­ecules, and disorder. When extending the fit to the atoms of both ion pairs of the unit cell, the r.m.s. value increases to 0.195, showing the lattice mismatch between 4a and 4b.

Observations based on powder XRD data indicate that the samples of 4b quickly desolvate, even under ambient conditions. The powder patterns of 4b more closely match the parameters of hydrate 4a than would be expected for aceto­nitrile solvate 4b, even if the data were collected on samples exposed to air only for a few minutes prior to data collection (Table 7). Rietveld refinements of samples of 4b yield β angles that match those of 4a (at both room temperature and 150 K), and the room-temperature volume of 4b is actually slightly smaller than that of 4a, in agreement with the assumption that all the aceto­nitrile in the structure of 4b is lost when exposed to the atmosphere, while the solvent water mol­ecules of 4a, being hydrogen bound, do remain in the lattice under these conditions. These observations will be further investigated in a more detailed upcoming study, focusing on a larger series of bedaquilinium salts, including their solvation properties, thermal stability, and responses to ambient moisture.

Table 7
150 K and room-temperature (RT) unit-cell dimensions for 1, 2, 4a, and 4b

RT data were obtained from powder XRD patterns via Rietveld refinement (see supporting information for Rietveld plots).

	1, 150 K	1, RT	2, 150 K	2, RT
a (Å)	11.1584 (8)	11.230 (1)	16.4556 (6)	16.5879 (2)
b (Å)	13.6425 (14)	13.766 (1)	10.3205 (3)	10.4952 (8)
c (Å)	36.061 (4)	36.455 (3)	20.1636 (8)	20.183 (2)
β (°)	90	90	109.1832 (15)	109.238 (2)
V (Å^3)	5489.5 (9)	5636 (1)	3234.2 (2)	3317.4 (4)
ρ (Mg m^−3)	1.344	1.309	1.379	1.344
Rwp (%)		19.99		20.48
Rexp  (%)		15.67		13.27
S		1.27		1.54
	4a, 150 K	4a, RT	4b, 150 K	4b, RT^a
a (Å)	12.6384 (5)	12.7267 (4)	12.8661 (8)	12.720 (1)	12.7242 (8)
b (Å)	7.9259 (3)	8.0157 (3)	8.0386 (5)	8.0094 (5)	8.0116 (6)
c (Å)	17.5249 (8)	17.6438 (7)	17.4704 (10)	17.626 (2)	17.632 (1)
β (°)	99.8450 (17)	99.7928 (6)	101.093 (3)	99.836 (2)	99.813 (1)
V (Å^3)	1729.63 (12)	1773.7 (1)	1773.13 (19)	1769.4 (3)	1771.2 (2)
ρ (Mg m^−3)	1.342	1.309	1.360	1.311	1.361
Rwp (%)		5.57		30.65	28.65
Rexp  (%)		10.78		10.50	14.26
S		1.94		2.12	2.01
Note: (a) data from two independent samples and Rietveld refinements.

The structure of 2, on the other hand, is solvent free. Like 4, the main inter­molecular inter­actions are strong hydrogen bonds, already briefly discussed, with the bedaquilinium cation always acting as a hydrogen-bond donor, and the hydro­fumarate anions acting as both H-atom acceptors and donors. The quinoline N atom does not act as an acceptor for a hydrogen bond, in agreement with its reduced basicity, already discussed. Originating from the cation are N—H⋯O hydrogen bonds, formed by the ammonium cations, and O—H⋯O hydrogen bonds, originating from the alcohol moieties. The N—H⋯O and O—H⋯O hydrogen bonds from one cation are towards the two O atoms of the same fully deprotonated carboxyl­ate group, yielding an R₂²(10) hydrogen-bonding graph-set motif. This motif is identical for the two crystallographically independent ion pairs in 2. The remaining strong hydrogen bonds are between the hydro­fumarate anions. The hydrogen-bond donors are the carb­oxy­lic acid groups of each hydro­fumarate anion, while the hydrogen-bond acceptor is always the O atom also hydrogen bonded to the bedaquilinium alcohol group, thus tying fumarate anions together in a head-to-tail fashion, forming infinite chains that extend along the b-axis direction (Fig. 8). The individual hydrogen-bonding motifs for these hydrogen bonds are D(2). The hydro­fumarate anion chains bridge between bedaquilinium cations connecting anions and cations into ribbons that extend along the b-axis direction.

These strong hydrogen bonds in 2 are again augmented by a series of other not-as-strong directional inter­actions, such as C—H⋯O and C—H⋯Br hydrogen bonds (Table 4) that inter­connect between ribbons to create a fully 3D network and structure. Segments of neighboring ribbons do also inter­digitate with each other, further stabilizing the overall structure.

The arrangement of anions and cations in 4a and 4b, and their connection via hydrogen-bonding inter­actions, follows a similar pattern to that in 2, but it is augmented by the solvate water mol­ecules, which play a similar role as the protonated fumarate carb­oxy­lic acid groups do in 2 in connecting anions and cations with each other into infinite ribbons (Fig. 10). Bedaquilinium cations and water mol­ecules act as hydrogen-bond donors and the benzoate anions act as hydrogen-bond acceptors. The N—H⋯O hydrogen bond from the cation is towards one O atom of the benzoate carboxyl­ate group and the O—H⋯O hydrogen bond is towards the water mol­ecule, which in turn is hydrogen bonded to the same benzoate O atom as the ammonium fragment. The R₂²(10) graph-set motif in 2 is thus converted in 4 into an R₃³(10) motif, but otherwise fulfils the same function as in 2, connecting the hy­droxy and ammonium segments of one cation to the same carboxyl­ate group. The fully occupied water mol­ecules in 4 assume the role of the carb­oxy­lic acid groups in 2, acting as bridges between anions [C₂²(6) hydrogen-bonding motif], creating infinite benzoate–water chains that extend along the b-axis direction. Wrapped around these chains, and connected to them via O—H⋯O and N—H⋯O hydrogen bonds, are the bedaquiline cations, thus creating wider ribbons of cations, anions, and solvent water mol­ecules (Fig. 10), emulating the pattern already observed for 2. The partially occupied water mol­ecules are located on the outer rim of the ribbon, hydrogen bonded to the quinoline N atom but not bridging or con­necting between any structural entities.

Figure 10 Hydrogen-bonding pattern in 4a. (Top) Chains along b created by benzoate anions and water mol­ecules. For clarity, only the 3-di­methyl­aza­niumyl-1-hy­droxy­propyl fragments of the cations are shown, and H atoms not involved in hydrogen bonds have been omitted. (Bottom) Segment of an entire ribbon, including cations and partially occupied water mol­ecules. Color coding: O, N, and Br atoms are shown with 50% probability displacement ellipsoids, and all other atoms are in capped-stick mode and color coded by the symmetry equivalence of their anion and cation (cations in dark green and benzoate anions in orange). Hydrogen bonds are shown as turquoise and red dashed lines.

The strong inter­molecular inter­actions present in 4a and 4b do com­pensate for the presence of the only partially or not at all filled voids present, and the packing efficiency for the salts of 4 is com­parable to that of free base bedaquiline. Indeed, the density for the 1.17-hydrate is, at 1.342 Mg m⁻³, virtually identical to that of the free base of 1.344 Mg m⁻³ (both measured at 150 K), and the aceto­nitrile solvate is, at 1.360 Mg m⁻³, even denser than the solvent-free base. The best packing efficiency is, however, observed for fumarate salt 2, featuring a multitude of strong hydrogen bonds, and having neither incorporated solvent mol­ecules nor unoccupied void space. Its density, at 150 K, is 1.379 Mg m⁻³ (Table 7).

Supporting information

Computing details

For all structures, data collection: APEX3 (Bruker, 2019); cell refinement: SAINT (Bruker, 2019); data reduction: SAINT (Bruker, 2019); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015) and shelXle (Hübschle et al., 2011); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

1-(6-Bromo-2-methoxyquinolin-3-yl)-4-(dimethylamino)- 2-(naphthalen-1-yl)-1-phenylbutan-2-ol (1)

Crystal data

C32H31BrN2O2	Dx = 1.344 Mg m^−3
Mr = 555.50	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 9979 reflections
a = 11.1584 (8) Å	θ = 2.4–28.7°
b = 13.6425 (14) Å	µ = 1.53 mm^−1
c = 36.061 (4) Å	T = 150 K
V = 5489.5 (9) Å^3	Plate, colourless
Z = 8	0.21 × 0.13 × 0.05 mm
F(000) = 2304

Data collection

Bruker D8 Quest diffractometer with PhotonII charge-integrating pixel array detector (CPAD)	17893 independent reflections
Radiation source: fine focus sealed tube X-ray source	12296 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromator	Rint = 0.052
Detector resolution: 7.4074 pixels mm^-1	θmax = 33.2°, θmin = 2.3°
ω and phi scans	h = −14→17
Absorption correction: multi-scan (SADABS2016; Krause et al., 2015)	k = −20→17
Tmin = 0.603, Tmax = 0.747	l = −55→52
66520 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.0298P)^2 + 2.4789P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
17893 reflections	Δρmax = 0.48 e Å^−3
675 parameters	Δρmin = −0.58 e Å^−3
0 restraints	Absolute structure: Flack x determined using 4397 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.034 (3)

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	−0.22418 (4)	0.59893 (4)	0.93403 (2)	0.04766 (11)
O1	0.3238 (2)	0.60084 (19)	0.79619 (6)	0.0300 (5)
H1O	0.296203	0.640769	0.780645	0.045*
O2	0.4828 (2)	0.72509 (17)	0.90856 (6)	0.0311 (5)
N1	0.3008 (3)	0.7681 (3)	0.75701 (9)	0.0374 (7)
N2	0.2968 (2)	0.7233 (2)	0.93579 (8)	0.0289 (6)
C1	0.4337 (3)	0.5908 (2)	0.85326 (9)	0.0249 (6)
H1	0.511656	0.613215	0.863960	0.030*
C2	0.4218 (3)	0.6444 (2)	0.81522 (9)	0.0261 (6)
C3	0.3911 (3)	0.7541 (2)	0.81996 (10)	0.0287 (7)
H3A	0.311884	0.760086	0.832083	0.034*
H3B	0.451320	0.784829	0.836451	0.034*
C4	0.3885 (3)	0.8096 (3)	0.78309 (10)	0.0330 (7)
H4A	0.368347	0.879127	0.787832	0.040*
H4B	0.469185	0.807406	0.771700	0.040*
C5	0.1807 (4)	0.8058 (4)	0.76442 (14)	0.0549 (12)
H5A	0.181362	0.877472	0.762872	0.082*
H5B	0.155422	0.785688	0.789317	0.082*
H5C	0.124585	0.779366	0.746042	0.082*
C6	0.3352 (5)	0.7891 (4)	0.71826 (12)	0.0540 (12)
H6A	0.274637	0.761942	0.701453	0.081*
H6B	0.413095	0.759038	0.712972	0.081*
H6C	0.340535	0.860126	0.714641	0.081*
C7	0.5377 (3)	0.6349 (2)	0.79184 (10)	0.0292 (7)
C8	0.5303 (3)	0.5879 (3)	0.75814 (10)	0.0358 (8)
H8	0.459085	0.553241	0.752149	0.043*
C9	0.6254 (4)	0.5894 (3)	0.73209 (11)	0.0437 (9)
H9	0.617529	0.555399	0.709222	0.052*
C10	0.7269 (4)	0.6388 (3)	0.73966 (12)	0.0479 (10)
H10	0.788893	0.641601	0.721614	0.058*
C11	0.7426 (3)	0.6867 (3)	0.77407 (13)	0.0431 (10)
C12	0.8498 (4)	0.7363 (4)	0.78199 (17)	0.0594 (14)
H12	0.910315	0.740322	0.763505	0.071*
C13	0.8689 (4)	0.7790 (4)	0.81573 (18)	0.0624 (14)
H13	0.942439	0.811591	0.820635	0.075*
C14	0.7811 (4)	0.7748 (3)	0.84279 (15)	0.0529 (11)
H14	0.795439	0.803479	0.866381	0.064*
C15	0.6736 (4)	0.7297 (3)	0.83590 (12)	0.0377 (8)
H15	0.613991	0.729114	0.854720	0.045*
C16	0.6489 (3)	0.6837 (3)	0.80140 (11)	0.0338 (8)
C17	0.4406 (3)	0.4791 (2)	0.85227 (9)	0.0271 (6)
C18	0.5242 (3)	0.4342 (3)	0.87547 (11)	0.0361 (8)
H18	0.578525	0.473635	0.889212	0.043*
C19	0.5296 (4)	0.3329 (3)	0.87886 (13)	0.0455 (10)
H19	0.586943	0.304062	0.894989	0.055*
C20	0.4523 (4)	0.2738 (3)	0.85897 (14)	0.0468 (10)
H20	0.455743	0.204480	0.861264	0.056*
C21	0.3706 (4)	0.3174 (3)	0.83584 (13)	0.0453 (10)
H21	0.317076	0.277449	0.821984	0.054*
C22	0.3643 (4)	0.4183 (3)	0.83226 (12)	0.0374 (8)
H22	0.307030	0.446401	0.815903	0.045*
C23	0.3375 (3)	0.6233 (2)	0.88094 (9)	0.0255 (6)
C24	0.2215 (3)	0.5925 (2)	0.88015 (9)	0.0266 (6)
H24	0.196272	0.548059	0.861430	0.032*
C25	0.1375 (3)	0.6260 (2)	0.90703 (9)	0.0262 (6)
C26	0.0151 (3)	0.5984 (3)	0.90691 (9)	0.0303 (6)
H26	−0.014665	0.554893	0.888515	0.036*
C27	−0.0594 (3)	0.6349 (3)	0.93353 (11)	0.0333 (7)
C28	−0.0190 (3)	0.6997 (3)	0.96125 (10)	0.0369 (8)
H28	−0.073061	0.724205	0.979370	0.044*
C29	0.0990 (3)	0.7270 (3)	0.96179 (10)	0.0342 (8)
H29	0.126805	0.770477	0.980477	0.041*
C30	0.1804 (3)	0.6910 (2)	0.93480 (9)	0.0279 (6)
C31	0.3688 (3)	0.6911 (2)	0.90978 (9)	0.0260 (6)
C32	0.5181 (3)	0.7945 (3)	0.93649 (11)	0.0380 (8)
H32A	0.601622	0.813868	0.932406	0.057*
H32B	0.510293	0.764395	0.961050	0.057*
H32C	0.466450	0.852445	0.935054	0.057*
Br2	1.50319 (4)	0.52837 (3)	0.98077 (2)	0.04694 (11)
O3	1.1137 (2)	0.17437 (18)	0.87033 (7)	0.0340 (5)
H3O	1.149698	0.120544	0.872362	0.051*
O4	0.8318 (2)	0.3046 (2)	0.95890 (8)	0.0422 (6)
N3	1.1594 (3)	−0.0081 (2)	0.89439 (9)	0.0374 (7)
N4	0.9864 (3)	0.3925 (2)	0.98480 (8)	0.0365 (7)
C33	0.9444 (3)	0.2672 (2)	0.89183 (9)	0.0295 (7)
H33	0.859615	0.258280	0.900123	0.035*
C34	0.9919 (3)	0.1632 (2)	0.88238 (9)	0.0291 (6)
C35	0.9948 (3)	0.0969 (2)	0.91712 (9)	0.0321 (7)
H35A	1.050174	0.125785	0.935591	0.039*
H35B	0.913825	0.095086	0.928300	0.039*
C36	1.0347 (3)	−0.0074 (3)	0.90853 (11)	0.0365 (8)
H36A	1.029756	−0.047775	0.931298	0.044*
H36B	0.980637	−0.036456	0.889749	0.044*
C37	1.2456 (4)	−0.0081 (4)	0.92483 (14)	0.0522 (11)
H37A	1.327104	−0.004144	0.914792	0.078*
H37B	1.237028	−0.068711	0.939203	0.078*
H37C	1.230662	0.048388	0.940944	0.078*
C38	1.1821 (4)	−0.0913 (3)	0.86971 (13)	0.0510 (11)
H38A	1.126162	−0.089017	0.848772	0.077*
H38B	1.170719	−0.152677	0.883403	0.077*
H38C	1.264538	−0.087986	0.860431	0.077*
C39	0.9167 (3)	0.1173 (2)	0.85070 (10)	0.0331 (8)
C40	0.9708 (4)	0.1040 (3)	0.81713 (11)	0.0480 (10)
H40	1.050579	0.126813	0.814025	0.058*
C41	0.9141 (5)	0.0580 (4)	0.78685 (12)	0.0572 (13)
H41	0.955036	0.052016	0.763861	0.069*
C42	0.8021 (4)	0.0226 (3)	0.79045 (11)	0.0489 (11)
H42	0.764721	−0.009785	0.770191	0.059*
C43	0.7401 (4)	0.0336 (3)	0.82435 (10)	0.0370 (8)
C44	0.6229 (4)	−0.0050 (3)	0.82814 (12)	0.0438 (9)
H44	0.587964	−0.039705	0.808023	0.053*
C45	0.5592 (4)	0.0068 (3)	0.86000 (13)	0.0468 (10)
H45	0.481437	−0.020876	0.862275	0.056*
C46	0.6092 (4)	0.0603 (3)	0.88956 (11)	0.0389 (8)
H46	0.563583	0.070801	0.911439	0.047*
C47	0.7224 (3)	0.0971 (3)	0.88713 (9)	0.0328 (7)
H47	0.754336	0.132226	0.907619	0.039*
C48	0.7944 (3)	0.0846 (2)	0.85485 (10)	0.0319 (7)
C49	0.9402 (3)	0.3399 (2)	0.85952 (10)	0.0283 (7)
C50	0.8419 (3)	0.4007 (3)	0.85705 (11)	0.0366 (8)
H50	0.777022	0.391304	0.873727	0.044*
C51	0.8348 (4)	0.4754 (3)	0.83090 (12)	0.0438 (9)
H51	0.766337	0.516697	0.830043	0.053*
C52	0.9274 (4)	0.4890 (3)	0.80626 (12)	0.0442 (9)
H52	0.922986	0.539544	0.788192	0.053*
C53	1.0272 (4)	0.4288 (3)	0.80792 (11)	0.0459 (10)
H53	1.091198	0.438060	0.790888	0.055*
C54	1.0343 (3)	0.3547 (3)	0.83440 (11)	0.0376 (8)
H54	1.103315	0.313947	0.835444	0.045*
C55	1.0098 (3)	0.3161 (2)	0.92410 (9)	0.0280 (6)
C56	1.1266 (3)	0.3448 (2)	0.92281 (9)	0.0298 (7)
H56	1.173876	0.328393	0.901803	0.036*
C57	1.1792 (3)	0.3992 (3)	0.95242 (9)	0.0291 (7)
C58	1.2989 (3)	0.4300 (3)	0.95237 (10)	0.0315 (7)
H58	1.350752	0.411765	0.932661	0.038*
C59	1.3406 (3)	0.4866 (3)	0.98087 (11)	0.0353 (7)
C60	1.2659 (4)	0.5160 (3)	1.01026 (10)	0.0410 (9)
H60	1.296029	0.556768	1.029467	0.049*
C61	1.1491 (4)	0.4850 (3)	1.01081 (10)	0.0414 (9)
H61	1.098304	0.504605	1.030619	0.050*
C62	1.1029 (3)	0.4246 (2)	0.98254 (10)	0.0320 (7)
C63	0.9454 (3)	0.3401 (3)	0.95731 (10)	0.0316 (7)
C64	0.7628 (4)	0.3276 (4)	0.99162 (13)	0.0553 (12)
H64A	0.755306	0.398868	0.994016	0.083*
H64B	0.803387	0.301156	1.013550	0.083*
H64C	0.682908	0.298312	0.989498	0.083*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.02814 (17)	0.0671 (3)	0.0478 (2)	−0.00323 (18)	0.00642 (17)	−0.0063 (2)
O1	0.0292 (11)	0.0352 (12)	0.0256 (12)	−0.0012 (10)	−0.0035 (9)	−0.0023 (10)
O2	0.0302 (13)	0.0367 (12)	0.0264 (11)	−0.0050 (10)	−0.0010 (10)	−0.0094 (10)
N1	0.0375 (18)	0.0485 (19)	0.0262 (15)	0.0042 (14)	−0.0004 (12)	0.0038 (14)
N2	0.0315 (15)	0.0329 (14)	0.0223 (13)	−0.0007 (11)	0.0021 (11)	−0.0026 (12)
C1	0.0232 (14)	0.0247 (15)	0.0269 (15)	−0.0009 (12)	0.0017 (11)	−0.0013 (13)
C2	0.0264 (15)	0.0260 (16)	0.0258 (16)	−0.0017 (12)	0.0012 (12)	−0.0015 (13)
C3	0.0282 (16)	0.0296 (17)	0.0285 (17)	0.0027 (13)	0.0001 (13)	−0.0026 (13)
C4	0.0321 (18)	0.0327 (18)	0.0344 (19)	0.0013 (14)	0.0026 (14)	0.0046 (15)
C5	0.037 (2)	0.078 (3)	0.050 (3)	0.010 (2)	−0.0086 (19)	0.005 (2)
C6	0.072 (3)	0.062 (3)	0.029 (2)	0.005 (2)	0.002 (2)	0.010 (2)
C7	0.0307 (17)	0.0271 (16)	0.0298 (17)	0.0035 (12)	0.0046 (13)	0.0022 (13)
C8	0.043 (2)	0.0351 (19)	0.0295 (17)	0.0049 (15)	0.0079 (14)	−0.0011 (15)
C9	0.051 (2)	0.042 (2)	0.037 (2)	0.0125 (19)	0.0171 (17)	0.0035 (18)
C10	0.046 (2)	0.052 (2)	0.045 (2)	0.013 (2)	0.023 (2)	0.0110 (19)
C11	0.033 (2)	0.040 (2)	0.056 (3)	0.0050 (15)	0.0146 (17)	0.0145 (19)
C12	0.033 (2)	0.059 (3)	0.086 (4)	−0.001 (2)	0.020 (2)	0.020 (3)
C13	0.033 (2)	0.059 (3)	0.096 (4)	−0.010 (2)	0.007 (2)	0.005 (3)
C14	0.036 (2)	0.052 (2)	0.071 (3)	−0.015 (2)	−0.004 (2)	0.007 (2)
C15	0.0329 (19)	0.0330 (19)	0.047 (2)	−0.0018 (15)	−0.0004 (16)	0.0034 (17)
C16	0.0319 (18)	0.0290 (18)	0.040 (2)	0.0031 (14)	0.0044 (15)	0.0076 (15)
C17	0.0270 (15)	0.0264 (16)	0.0279 (16)	0.0022 (13)	0.0045 (12)	−0.0035 (13)
C18	0.037 (2)	0.0321 (17)	0.039 (2)	0.0034 (14)	0.0005 (15)	0.0015 (15)
C19	0.041 (2)	0.036 (2)	0.059 (3)	0.0074 (16)	0.0006 (18)	0.0106 (19)
C20	0.043 (2)	0.0276 (18)	0.070 (3)	0.0073 (16)	0.014 (2)	0.0029 (19)
C21	0.043 (2)	0.0295 (19)	0.064 (3)	−0.0002 (16)	0.003 (2)	−0.0094 (18)
C22	0.038 (2)	0.0273 (18)	0.047 (2)	−0.0003 (14)	−0.0023 (16)	−0.0066 (16)
C23	0.0311 (16)	0.0241 (15)	0.0213 (15)	0.0004 (12)	0.0019 (12)	−0.0010 (12)
C24	0.0297 (15)	0.0251 (15)	0.0251 (15)	−0.0003 (13)	0.0014 (13)	−0.0024 (13)
C25	0.0264 (15)	0.0256 (16)	0.0265 (16)	0.0001 (12)	0.0001 (12)	0.0025 (12)
C26	0.0284 (16)	0.0324 (16)	0.0301 (16)	0.0025 (14)	0.0030 (13)	−0.0006 (14)
C27	0.0232 (15)	0.0424 (19)	0.0342 (18)	0.0026 (13)	0.0019 (14)	0.0022 (16)
C28	0.0317 (19)	0.049 (2)	0.0299 (18)	0.0033 (15)	0.0058 (14)	−0.0046 (15)
C29	0.0317 (18)	0.044 (2)	0.0270 (17)	0.0024 (15)	0.0028 (14)	−0.0069 (15)
C30	0.0316 (16)	0.0300 (16)	0.0220 (15)	0.0037 (12)	0.0000 (13)	0.0022 (14)
C31	0.0255 (15)	0.0282 (16)	0.0242 (15)	−0.0005 (12)	−0.0035 (12)	0.0007 (13)
C32	0.0321 (18)	0.047 (2)	0.0349 (18)	−0.0078 (15)	−0.0054 (15)	−0.0130 (16)
Br2	0.0435 (2)	0.0550 (2)	0.0423 (2)	−0.00769 (19)	−0.00983 (19)	−0.00133 (19)
O3	0.0301 (12)	0.0305 (12)	0.0415 (14)	0.0025 (10)	0.0129 (11)	−0.0005 (11)
O4	0.0351 (14)	0.0499 (16)	0.0415 (16)	−0.0055 (12)	0.0175 (12)	−0.0080 (13)
N3	0.0394 (17)	0.0342 (17)	0.0387 (17)	0.0073 (13)	0.0039 (14)	−0.0059 (13)
N4	0.0492 (18)	0.0350 (15)	0.0253 (14)	0.0036 (14)	0.0091 (13)	0.0005 (12)
C33	0.0293 (16)	0.0318 (17)	0.0274 (17)	0.0002 (13)	0.0044 (13)	−0.0012 (13)
C34	0.0295 (16)	0.0280 (15)	0.0298 (16)	−0.0017 (13)	0.0078 (14)	−0.0003 (12)
C35	0.0337 (16)	0.0310 (16)	0.0316 (16)	0.0022 (15)	0.0063 (14)	0.0028 (13)
C36	0.0364 (19)	0.0334 (18)	0.040 (2)	0.0002 (14)	0.0039 (15)	0.0014 (15)
C37	0.040 (2)	0.058 (3)	0.059 (3)	0.0083 (18)	−0.0011 (19)	−0.009 (2)
C38	0.066 (3)	0.037 (2)	0.049 (2)	0.011 (2)	0.011 (2)	−0.0114 (19)
C39	0.043 (2)	0.0280 (18)	0.0279 (17)	−0.0008 (14)	0.0087 (14)	0.0006 (14)
C40	0.054 (3)	0.055 (2)	0.036 (2)	−0.013 (2)	0.0160 (18)	−0.0104 (19)
C41	0.075 (3)	0.066 (3)	0.031 (2)	−0.017 (2)	0.013 (2)	−0.014 (2)
C42	0.069 (3)	0.047 (2)	0.031 (2)	−0.009 (2)	0.0019 (18)	−0.0097 (18)
C43	0.047 (2)	0.0289 (17)	0.0348 (18)	−0.0035 (16)	−0.0022 (15)	−0.0009 (15)
C44	0.048 (2)	0.040 (2)	0.044 (2)	−0.0053 (17)	−0.0108 (18)	−0.0002 (17)
C45	0.045 (2)	0.042 (2)	0.053 (3)	−0.0093 (17)	−0.009 (2)	0.0095 (19)
C46	0.0363 (19)	0.042 (2)	0.039 (2)	−0.0012 (16)	0.0024 (16)	0.0106 (16)
C47	0.0379 (17)	0.0302 (16)	0.0302 (17)	−0.0001 (16)	0.0023 (14)	0.0024 (14)
C48	0.041 (2)	0.0246 (16)	0.0305 (17)	−0.0002 (14)	0.0021 (14)	0.0027 (13)
C49	0.0282 (16)	0.0276 (16)	0.0290 (17)	−0.0015 (13)	0.0010 (13)	−0.0028 (13)
C50	0.0339 (18)	0.0365 (19)	0.039 (2)	0.0036 (16)	0.0004 (15)	−0.0022 (17)
C51	0.045 (2)	0.041 (2)	0.044 (2)	0.0093 (18)	−0.0049 (17)	0.0024 (19)
C52	0.051 (2)	0.043 (2)	0.039 (2)	0.0023 (18)	−0.0076 (18)	0.0110 (17)
C53	0.041 (2)	0.058 (3)	0.039 (2)	0.0013 (18)	0.0032 (16)	0.0168 (18)
C54	0.0289 (18)	0.047 (2)	0.037 (2)	0.0062 (15)	0.0027 (14)	0.0085 (16)
C55	0.0308 (16)	0.0248 (14)	0.0283 (16)	0.0043 (13)	0.0044 (13)	0.0014 (12)
C56	0.0375 (18)	0.0282 (17)	0.0236 (16)	−0.0006 (13)	0.0062 (13)	−0.0008 (13)
C57	0.0353 (17)	0.0286 (16)	0.0234 (15)	0.0026 (14)	0.0032 (13)	0.0040 (14)
C58	0.0327 (18)	0.0343 (18)	0.0275 (17)	0.0014 (13)	0.0011 (13)	0.0023 (14)
C59	0.0399 (19)	0.0352 (18)	0.0309 (17)	−0.0005 (14)	−0.0068 (15)	0.0049 (16)
C60	0.055 (2)	0.042 (2)	0.0260 (17)	0.0029 (19)	−0.0049 (16)	−0.0027 (15)
C61	0.061 (3)	0.039 (2)	0.0234 (17)	0.0043 (18)	0.0039 (16)	−0.0042 (15)
C62	0.0422 (19)	0.0289 (16)	0.0250 (16)	0.0041 (14)	0.0035 (15)	0.0022 (14)
C63	0.0336 (17)	0.0299 (17)	0.0312 (18)	0.0020 (14)	0.0080 (14)	0.0022 (14)
C64	0.047 (3)	0.070 (3)	0.049 (3)	−0.002 (2)	0.030 (2)	−0.004 (2)

Geometric parameters (Å, º)

Br1—C27	1.903 (3)	Br2—C59	1.902 (4)
O1—C2	1.421 (4)	O3—C34	1.435 (4)
O1—H1O	0.8400	O3—H3O	0.8400
O2—C31	1.354 (4)	O4—C63	1.358 (4)
O2—C32	1.437 (4)	O4—C64	1.443 (4)
N1—C5	1.461 (5)	N3—C37	1.460 (6)
N1—C4	1.470 (5)	N3—C38	1.464 (5)
N1—C6	1.477 (5)	N3—C36	1.482 (5)
N2—C31	1.311 (4)	N4—C63	1.305 (5)
N2—C30	1.372 (4)	N4—C62	1.374 (5)
C1—C17	1.526 (4)	C33—C55	1.526 (5)
C1—C23	1.531 (4)	C33—C49	1.531 (5)
C1—C2	1.560 (5)	C33—C34	1.552 (5)
C1—H1	1.0000	C33—H33	1.0000
C2—C3	1.545 (5)	C34—C35	1.546 (5)
C2—C7	1.550 (5)	C34—C39	1.550 (5)
C3—C4	1.530 (5)	C35—C36	1.524 (5)
C3—H3A	0.9900	C35—H35A	0.9900
C3—H3B	0.9900	C35—H35B	0.9900
C4—H4A	0.9900	C36—H36A	0.9900
C4—H4B	0.9900	C36—H36B	0.9900
C5—H5A	0.9800	C37—H37A	0.9800
C5—H5B	0.9800	C37—H37B	0.9800
C5—H5C	0.9800	C37—H37C	0.9800
C6—H6A	0.9800	C38—H38A	0.9800
C6—H6B	0.9800	C38—H38B	0.9800
C6—H6C	0.9800	C38—H38C	0.9800
C7—C8	1.377 (5)	C39—C40	1.365 (5)
C7—C16	1.449 (5)	C39—C48	1.443 (5)
C8—C9	1.417 (5)	C40—C41	1.409 (6)
C8—H8	0.9500	C40—H40	0.9500
C9—C10	1.346 (7)	C41—C42	1.347 (7)
C9—H9	0.9500	C41—H41	0.9500
C10—C11	1.413 (6)	C42—C43	1.412 (6)
C10—H10	0.9500	C42—H42	0.9500
C11—C12	1.404 (7)	C43—C44	1.416 (6)
C11—C16	1.438 (5)	C43—C48	1.436 (5)
C12—C13	1.366 (8)	C44—C45	1.360 (6)
C12—H12	0.9500	C44—H44	0.9500
C13—C14	1.384 (7)	C45—C46	1.407 (6)
C13—H13	0.9500	C45—H45	0.9500
C14—C15	1.371 (6)	C46—C47	1.362 (5)
C14—H14	0.9500	C46—H46	0.9500
C15—C16	1.420 (6)	C47—C48	1.425 (5)
C15—H15	0.9500	C47—H47	0.9500
C17—C22	1.391 (5)	C49—C50	1.378 (5)
C17—C18	1.395 (5)	C49—C54	1.402 (5)
C18—C19	1.388 (5)	C50—C51	1.390 (6)
C18—H18	0.9500	C50—H50	0.9500
C19—C20	1.382 (6)	C51—C52	1.376 (6)
C19—H19	0.9500	C51—H51	0.9500
C20—C21	1.372 (6)	C52—C53	1.385 (6)
C20—H20	0.9500	C52—H52	0.9500
C21—C22	1.385 (5)	C53—C54	1.393 (5)
C21—H21	0.9500	C53—H53	0.9500
C22—H22	0.9500	C54—H54	0.9500
C23—C24	1.361 (5)	C55—C56	1.362 (5)
C23—C31	1.435 (4)	C55—C63	1.435 (5)
C24—C25	1.424 (4)	C56—C57	1.426 (5)
C24—H24	0.9500	C56—H56	0.9500
C25—C26	1.416 (5)	C57—C58	1.400 (5)
C25—C30	1.421 (5)	C57—C62	1.423 (5)
C26—C27	1.365 (5)	C58—C59	1.367 (5)
C26—H26	0.9500	C58—H58	0.9500
C27—C28	1.409 (5)	C59—C60	1.406 (6)
C28—C29	1.369 (5)	C60—C61	1.371 (6)
C28—H28	0.9500	C60—H60	0.9500
C29—C30	1.418 (5)	C61—C62	1.409 (5)
C29—H29	0.9500	C61—H61	0.9500
C32—H32A	0.9800	C64—H64A	0.9800
C32—H32B	0.9800	C64—H64B	0.9800
C32—H32C	0.9800	C64—H64C	0.9800
C2—O1—H1O	109.5	C34—O3—H3O	109.5
C31—O2—C32	117.4 (3)	C63—O4—C64	117.1 (3)
C5—N1—C4	111.0 (3)	C37—N3—C38	110.1 (3)
C5—N1—C6	110.1 (4)	C37—N3—C36	111.1 (3)
C4—N1—C6	111.0 (3)	C38—N3—C36	112.1 (3)
C31—N2—C30	117.1 (3)	C63—N4—C62	117.5 (3)
C17—C1—C23	109.9 (3)	C55—C33—C49	108.2 (3)
C17—C1—C2	116.8 (3)	C55—C33—C34	113.8 (3)
C23—C1—C2	112.2 (3)	C49—C33—C34	115.8 (3)
C17—C1—H1	105.7	C55—C33—H33	106.1
C23—C1—H1	105.7	C49—C33—H33	106.1
C2—C1—H1	105.7	C34—C33—H33	106.1
O1—C2—C3	106.7 (3)	O3—C34—C35	106.7 (3)
O1—C2—C7	110.2 (3)	O3—C34—C39	109.5 (3)
C3—C2—C7	109.0 (3)	C35—C34—C39	111.8 (3)
O1—C2—C1	107.1 (3)	O3—C34—C33	107.0 (3)
C3—C2—C1	112.1 (3)	C35—C34—C33	111.3 (3)
C7—C2—C1	111.7 (3)	C39—C34—C33	110.3 (3)
C4—C3—C2	112.8 (3)	C36—C35—C34	112.8 (3)
C4—C3—H3A	109.0	C36—C35—H35A	109.0
C2—C3—H3A	109.0	C34—C35—H35A	109.0
C4—C3—H3B	109.0	C36—C35—H35B	109.0
C2—C3—H3B	109.0	C34—C35—H35B	109.0
H3A—C3—H3B	107.8	H35A—C35—H35B	107.8
N1—C4—C3	112.2 (3)	N3—C36—C35	110.5 (3)
N1—C4—H4A	109.2	N3—C36—H36A	109.5
C3—C4—H4A	109.2	C35—C36—H36A	109.5
N1—C4—H4B	109.2	N3—C36—H36B	109.5
C3—C4—H4B	109.2	C35—C36—H36B	109.5
H4A—C4—H4B	107.9	H36A—C36—H36B	108.1
N1—C5—H5A	109.5	N3—C37—H37A	109.5
N1—C5—H5B	109.5	N3—C37—H37B	109.5
H5A—C5—H5B	109.5	H37A—C37—H37B	109.5
N1—C5—H5C	109.5	N3—C37—H37C	109.5
H5A—C5—H5C	109.5	H37A—C37—H37C	109.5
H5B—C5—H5C	109.5	H37B—C37—H37C	109.5
N1—C6—H6A	109.5	N3—C38—H38A	109.5
N1—C6—H6B	109.5	N3—C38—H38B	109.5
H6A—C6—H6B	109.5	H38A—C38—H38B	109.5
N1—C6—H6C	109.5	N3—C38—H38C	109.5
H6A—C6—H6C	109.5	H38A—C38—H38C	109.5
H6B—C6—H6C	109.5	H38B—C38—H38C	109.5
C8—C7—C16	118.4 (3)	C40—C39—C48	118.0 (4)
C8—C7—C2	118.0 (3)	C40—C39—C34	117.9 (3)
C16—C7—C2	123.2 (3)	C48—C39—C34	124.1 (3)
C7—C8—C9	122.2 (4)	C39—C40—C41	123.2 (4)
C7—C8—H8	118.9	C39—C40—H40	118.4
C9—C8—H8	118.9	C41—C40—H40	118.4
C10—C9—C8	120.2 (4)	C42—C41—C40	120.1 (4)
C10—C9—H9	119.9	C42—C41—H41	119.9
C8—C9—H9	119.9	C40—C41—H41	119.9
C9—C10—C11	120.9 (4)	C41—C42—C43	120.0 (4)
C9—C10—H10	119.5	C41—C42—H42	120.0
C11—C10—H10	119.5	C43—C42—H42	120.0
C12—C11—C10	120.4 (4)	C42—C43—C44	119.8 (4)
C12—C11—C16	119.6 (4)	C42—C43—C48	120.5 (4)
C10—C11—C16	119.9 (4)	C44—C43—C48	119.7 (4)
C13—C12—C11	121.3 (4)	C45—C44—C43	121.3 (4)
C13—C12—H12	119.4	C45—C44—H44	119.3
C11—C12—H12	119.4	C43—C44—H44	119.3
C12—C13—C14	120.0 (4)	C44—C45—C46	119.6 (4)
C12—C13—H13	120.0	C44—C45—H45	120.2
C14—C13—H13	120.0	C46—C45—H45	120.2
C15—C14—C13	120.7 (5)	C47—C46—C45	120.7 (4)
C15—C14—H14	119.7	C47—C46—H46	119.7
C13—C14—H14	119.7	C45—C46—H46	119.7
C14—C15—C16	121.8 (4)	C46—C47—C48	122.1 (4)
C14—C15—H15	119.1	C46—C47—H47	119.0
C16—C15—H15	119.1	C48—C47—H47	119.0
C15—C16—C11	116.5 (4)	C47—C48—C43	116.5 (3)
C15—C16—C7	125.3 (3)	C47—C48—C39	125.5 (3)
C11—C16—C7	118.2 (4)	C43—C48—C39	118.0 (3)
C22—C17—C18	117.3 (3)	C50—C49—C54	117.9 (3)
C22—C17—C1	125.2 (3)	C50—C49—C33	117.6 (3)
C18—C17—C1	117.3 (3)	C54—C49—C33	124.2 (3)
C19—C18—C17	121.3 (4)	C49—C50—C51	122.0 (4)
C19—C18—H18	119.4	C49—C50—H50	119.0
C17—C18—H18	119.4	C51—C50—H50	119.0
C20—C19—C18	120.5 (4)	C52—C51—C50	119.6 (4)
C20—C19—H19	119.7	C52—C51—H51	120.2
C18—C19—H19	119.7	C50—C51—H51	120.2
C21—C20—C19	118.5 (4)	C51—C52—C53	119.7 (4)
C21—C20—H20	120.7	C51—C52—H52	120.1
C19—C20—H20	120.7	C53—C52—H52	120.1
C20—C21—C22	121.4 (4)	C52—C53—C54	120.4 (4)
C20—C21—H21	119.3	C52—C53—H53	119.8
C22—C21—H21	119.3	C54—C53—H53	119.8
C21—C22—C17	120.9 (4)	C53—C54—C49	120.3 (3)
C21—C22—H22	119.5	C53—C54—H54	119.8
C17—C22—H22	119.5	C49—C54—H54	119.8
C24—C23—C31	116.5 (3)	C56—C55—C63	116.2 (3)
C24—C23—C1	124.3 (3)	C56—C55—C33	123.8 (3)
C31—C23—C1	119.2 (3)	C63—C55—C33	119.8 (3)
C23—C24—C25	120.8 (3)	C55—C56—C57	121.2 (3)
C23—C24—H24	119.6	C55—C56—H56	119.4
C25—C24—H24	119.6	C57—C56—H56	119.4
C26—C25—C30	119.6 (3)	C58—C57—C62	119.9 (3)
C26—C25—C24	123.1 (3)	C58—C57—C56	123.2 (3)
C30—C25—C24	117.3 (3)	C62—C57—C56	116.9 (3)
C27—C26—C25	119.2 (3)	C59—C58—C57	119.6 (3)
C27—C26—H26	120.4	C59—C58—H58	120.2
C25—C26—H26	120.4	C57—C58—H58	120.2
C26—C27—C28	122.2 (3)	C58—C59—C60	121.7 (4)
C26—C27—Br1	120.1 (3)	C58—C59—Br2	119.5 (3)
C28—C27—Br1	117.7 (3)	C60—C59—Br2	118.8 (3)
C29—C28—C27	119.3 (3)	C61—C60—C59	119.1 (4)
C29—C28—H28	120.4	C61—C60—H60	120.4
C27—C28—H28	120.4	C59—C60—H60	120.4
C28—C29—C30	120.8 (3)	C60—C61—C62	121.2 (4)
C28—C29—H29	119.6	C60—C61—H61	119.4
C30—C29—H29	119.6	C62—C61—H61	119.4
N2—C30—C29	118.5 (3)	N4—C62—C61	119.3 (3)
N2—C30—C25	122.5 (3)	N4—C62—C57	122.3 (3)
C29—C30—C25	118.9 (3)	C61—C62—C57	118.4 (4)
N2—C31—O2	119.0 (3)	N4—C63—O4	119.4 (3)
N2—C31—C23	125.8 (3)	N4—C63—C55	125.7 (3)
O2—C31—C23	115.2 (3)	O4—C63—C55	114.9 (3)
O2—C32—H32A	109.5	O4—C64—H64A	109.5
O2—C32—H32B	109.5	O4—C64—H64B	109.5
H32A—C32—H32B	109.5	H64A—C64—H64B	109.5
O2—C32—H32C	109.5	O4—C64—H64C	109.5
H32A—C32—H32C	109.5	H64A—C64—H64C	109.5
H32B—C32—H32C	109.5	H64B—C64—H64C	109.5
C17—C1—C2—O1	52.3 (4)	C55—C33—C34—O3	−63.8 (3)
C23—C1—C2—O1	−75.9 (3)	C49—C33—C34—O3	62.5 (4)
C17—C1—C2—C3	169.0 (3)	C55—C33—C34—C35	52.5 (4)
C23—C1—C2—C3	40.8 (4)	C49—C33—C34—C35	178.8 (3)
C17—C1—C2—C7	−68.4 (4)	C55—C33—C34—C39	177.2 (3)
C23—C1—C2—C7	163.4 (3)	C49—C33—C34—C39	−56.5 (4)
O1—C2—C3—C4	−67.4 (3)	O3—C34—C35—C36	−66.6 (4)
C7—C2—C3—C4	51.6 (4)	C39—C34—C35—C36	53.1 (4)
C1—C2—C3—C4	175.7 (3)	C33—C34—C35—C36	177.0 (3)
C5—N1—C4—C3	83.1 (4)	C37—N3—C36—C35	84.3 (4)
C6—N1—C4—C3	−154.1 (3)	C38—N3—C36—C35	−152.0 (3)
C2—C3—C4—N1	58.7 (4)	C34—C35—C36—N3	63.0 (4)
O1—C2—C7—C8	−0.5 (4)	O3—C34—C39—C40	−5.9 (5)
C3—C2—C7—C8	−117.3 (3)	C35—C34—C39—C40	−123.9 (4)
C1—C2—C7—C8	118.3 (3)	C33—C34—C39—C40	111.6 (4)
O1—C2—C7—C16	171.3 (3)	O3—C34—C39—C48	171.9 (3)
C3—C2—C7—C16	54.5 (4)	C35—C34—C39—C48	53.8 (4)
C1—C2—C7—C16	−69.8 (4)	C33—C34—C39—C48	−70.7 (4)
C16—C7—C8—C9	−2.8 (5)	C48—C39—C40—C41	−1.6 (7)
C2—C7—C8—C9	169.4 (3)	C34—C39—C40—C41	176.3 (4)
C7—C8—C9—C10	−0.8 (6)	C39—C40—C41—C42	−1.6 (8)
C8—C9—C10—C11	2.5 (6)	C40—C41—C42—C43	1.5 (8)
C9—C10—C11—C12	178.7 (4)	C41—C42—C43—C44	−179.2 (5)
C9—C10—C11—C16	−0.6 (6)	C41—C42—C43—C48	1.6 (7)
C10—C11—C12—C13	−176.8 (5)	C42—C43—C44—C45	−178.0 (4)
C16—C11—C12—C13	2.4 (7)	C48—C43—C44—C45	1.2 (6)
C11—C12—C13—C14	−0.7 (8)	C43—C44—C45—C46	1.5 (6)
C12—C13—C14—C15	−1.2 (8)	C44—C45—C46—C47	−2.5 (6)
C13—C14—C15—C16	1.5 (7)	C45—C46—C47—C48	0.8 (6)
C14—C15—C16—C11	0.2 (6)	C46—C47—C48—C43	1.9 (5)
C14—C15—C16—C7	−179.7 (4)	C46—C47—C48—C39	−177.0 (3)
C12—C11—C16—C15	−2.1 (6)	C42—C43—C48—C47	176.4 (4)
C10—C11—C16—C15	177.2 (4)	C44—C43—C48—C47	−2.8 (5)
C12—C11—C16—C7	177.8 (4)	C42—C43—C48—C39	−4.7 (5)
C10—C11—C16—C7	−2.9 (5)	C44—C43—C48—C39	176.2 (3)
C8—C7—C16—C15	−175.6 (4)	C40—C39—C48—C47	−176.6 (4)
C2—C7—C16—C15	12.6 (6)	C34—C39—C48—C47	5.7 (5)
C8—C7—C16—C11	4.6 (5)	C40—C39—C48—C43	4.5 (5)
C2—C7—C16—C11	−167.3 (3)	C34—C39—C48—C43	−173.2 (3)
C23—C1—C17—C22	81.5 (4)	C55—C33—C49—C50	−91.5 (4)
C2—C1—C17—C22	−47.9 (5)	C34—C33—C49—C50	139.4 (3)
C23—C1—C17—C18	−93.4 (4)	C55—C33—C49—C54	82.5 (4)
C2—C1—C17—C18	137.3 (3)	C34—C33—C49—C54	−46.6 (5)
C22—C17—C18—C19	−1.0 (6)	C54—C49—C50—C51	−0.6 (6)
C1—C17—C18—C19	174.2 (4)	C33—C49—C50—C51	173.8 (4)
C17—C18—C19—C20	0.5 (6)	C49—C50—C51—C52	0.8 (6)
C18—C19—C20—C21	0.1 (7)	C50—C51—C52—C53	−0.5 (7)
C19—C20—C21—C22	−0.1 (7)	C51—C52—C53—C54	−0.1 (7)
C20—C21—C22—C17	−0.4 (7)	C52—C53—C54—C49	0.4 (6)
C18—C17—C22—C21	0.9 (6)	C50—C49—C54—C53	0.0 (6)
C1—C17—C22—C21	−173.9 (4)	C33—C49—C54—C53	−174.0 (4)
C17—C1—C23—C24	−54.5 (4)	C49—C33—C55—C56	−63.1 (4)
C2—C1—C23—C24	77.3 (4)	C34—C33—C55—C56	67.1 (4)
C17—C1—C23—C31	126.0 (3)	C49—C33—C55—C63	112.6 (3)
C2—C1—C23—C31	−102.2 (3)	C34—C33—C55—C63	−117.2 (3)
C31—C23—C24—C25	−0.6 (5)	C63—C55—C56—C57	−2.4 (5)
C1—C23—C24—C25	179.8 (3)	C33—C55—C56—C57	173.4 (3)
C23—C24—C25—C26	178.3 (3)	C55—C56—C57—C58	179.8 (3)
C23—C24—C25—C30	−1.1 (5)	C55—C56—C57—C62	−2.1 (5)
C30—C25—C26—C27	0.1 (5)	C62—C57—C58—C59	−1.7 (5)
C24—C25—C26—C27	−179.3 (3)	C56—C57—C58—C59	176.3 (3)
C25—C26—C27—C28	0.1 (5)	C57—C58—C59—C60	−0.8 (5)
C25—C26—C27—Br1	−180.0 (3)	C57—C58—C59—Br2	180.0 (3)
C26—C27—C28—C29	−0.3 (6)	C58—C59—C60—C61	1.7 (6)
Br1—C27—C28—C29	179.8 (3)	Br2—C59—C60—C61	−179.1 (3)
C27—C28—C29—C30	0.2 (6)	C59—C60—C61—C62	−0.1 (6)
C31—N2—C30—C29	−177.9 (3)	C63—N4—C62—C61	177.2 (3)
C31—N2—C30—C25	−0.3 (5)	C63—N4—C62—C57	−2.6 (5)
C28—C29—C30—N2	177.8 (3)	C60—C61—C62—N4	177.9 (3)
C28—C29—C30—C25	0.0 (5)	C60—C61—C62—C57	−2.4 (5)
C26—C25—C30—N2	−177.8 (3)	C58—C57—C62—N4	−177.0 (3)
C24—C25—C30—N2	1.6 (5)	C56—C57—C62—N4	4.8 (5)
C26—C25—C30—C29	−0.2 (5)	C58—C57—C62—C61	3.3 (5)
C24—C25—C30—C29	179.3 (3)	C56—C57—C62—C61	−174.9 (3)
C30—N2—C31—O2	176.5 (3)	C62—N4—C63—O4	178.1 (3)
C30—N2—C31—C23	−1.7 (5)	C62—N4—C63—C55	−2.6 (5)
C32—O2—C31—N2	0.6 (5)	C64—O4—C63—N4	−0.1 (5)
C32—O2—C31—C23	179.0 (3)	C64—O4—C63—C55	−179.4 (3)
C24—C23—C31—N2	2.1 (5)	C56—C55—C63—N4	5.1 (5)
C1—C23—C31—N2	−178.3 (3)	C33—C55—C63—N4	−170.9 (3)
C24—C23—C31—O2	−176.1 (3)	C56—C55—C63—O4	−175.6 (3)
C1—C23—C31—O2	3.5 (4)	C33—C55—C63—O4	8.4 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.84	1.94	2.696 (4)	150
C1—H1···O2	1.00	2.24	2.763 (4)	111
O3—H3O···N3	0.84	1.93	2.685 (4)	149
C33—H33···O4	1.00	2.23	2.773 (4)	112

[4-(6-Bromo-2-methoxyquinolin-3-yl)-3-hydroxy-3-(naphthalen-1-yl)-4-phenylbutyl]dimethylazanium 3-carboxyprop-2-enoate (2)

Crystal data

C32H32BrN2O2^+·C4H3O4^−	F(000) = 1392
Mr = 671.57	Dx = 1.379 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 16.4556 (6) Å	Cell parameters from 9891 reflections
b = 10.3205 (3) Å	θ = 2.9–31.4°
c = 20.1636 (8) Å	µ = 1.32 mm^−1
β = 109.1832 (15)°	T = 150 K
V = 3234.2 (2) Å^3	Block, colourless
Z = 4	0.45 × 0.37 × 0.17 mm

Data collection

Bruker D8 Quest diffractometer with PhotonII charge-integrating pixel array detector (CPAD)	24622 independent reflections
Radiation source: fine focus sealed tube X-ray source	18572 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromator	Rint = 0.040
Detector resolution: 7.4074 pixels mm^-1	θmax = 33.2°, θmin = 2.3°
ω and phi scans	h = −25→25
Absorption correction: multi-scan (SADABS2016; Krause et al., 2015)	k = −15→15
Tmin = 0.438, Tmax = 0.495	l = −28→31
115858 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.0609P)^2 + 0.4737P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
24622 reflections	Δρmax = 1.23 e Å^−3
837 parameters	Δρmin = −1.28 e Å^−3
1 restraint	Absolute structure: Flack x determined using 7327 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.0144 (14)

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1A	0.58678 (3)	0.47935 (4)	0.22528 (2)	0.06533 (14)
O1A	0.82483 (12)	−0.01085 (19)	0.51792 (10)	0.0278 (3)
H1AB	0.828 (2)	0.039 (4)	0.485 (2)	0.042*
O2A	0.77472 (16)	0.3652 (3)	0.64605 (13)	0.0484 (6)
O3A	0.93472 (13)	0.2628 (2)	0.42487 (10)	0.0344 (4)
O4A	0.84664 (14)	0.09248 (19)	0.40198 (9)	0.0349 (4)
O5A	0.81194 (14)	0.52568 (19)	0.20888 (11)	0.0350 (4)
H5A	0.763 (3)	0.555 (4)	0.164 (2)	0.052*
O6A	0.76176 (14)	0.3298 (2)	0.16731 (10)	0.0373 (4)
N1A	1.03839 (12)	0.1521 (2)	0.53959 (11)	0.0244 (4)
H1AN	0.993 (2)	0.179 (4)	0.4961 (19)	0.029*
N2A	0.73312 (15)	0.4780 (3)	0.54157 (16)	0.0405 (6)
C1A	0.75797 (15)	0.1203 (3)	0.58725 (12)	0.0253 (4)
H1A	0.771592	0.149992	0.636934	0.030*
C2A	0.84239 (15)	0.0560 (2)	0.58297 (13)	0.0239 (4)
C3A	0.91264 (15)	0.1580 (2)	0.58576 (14)	0.0262 (4)
H3AA	0.892408	0.215552	0.544294	0.031*
H3AB	0.923897	0.211845	0.628457	0.031*
C4A	0.99581 (16)	0.0896 (3)	0.58663 (15)	0.0314 (5)
H4AA	1.036546	0.089161	0.635301	0.038*
H4AB	0.982420	−0.001652	0.571907	0.038*
C5A	1.0918 (2)	0.2647 (3)	0.57295 (16)	0.0404 (7)
H5AA	1.115756	0.304971	0.539441	0.061*
H5AB	1.138756	0.235812	0.614397	0.061*
H5AC	1.056186	0.327915	0.587129	0.061*
C6A	1.0901 (2)	0.0563 (3)	0.5157 (2)	0.0441 (7)
H6AA	1.051580	−0.006000	0.483812	0.066*
H6AB	1.128727	0.010308	0.556399	0.066*
H6AC	1.124180	0.101322	0.491018	0.066*
C7A	0.87611 (15)	−0.0436 (3)	0.64224 (14)	0.0283 (5)
C8A	0.8828 (2)	−0.1710 (3)	0.62370 (17)	0.0364 (6)
H8A	0.864922	−0.192956	0.575279	0.044*
C9A	0.9150 (2)	−0.2694 (3)	0.6737 (2)	0.0479 (8)
H9A	0.918640	−0.355840	0.658637	0.058*
C10A	0.9408 (2)	−0.2416 (4)	0.7432 (2)	0.0483 (8)
H10A	0.961810	−0.308627	0.776728	0.058*
C11A	0.93654 (19)	−0.1126 (3)	0.76586 (16)	0.0407 (7)
C12A	0.9655 (2)	−0.0838 (5)	0.83857 (17)	0.0526 (9)
H12A	0.986902	−0.151708	0.871500	0.063*
C13A	0.9633 (3)	0.0384 (5)	0.86202 (19)	0.0597 (11)
H13A	0.983221	0.055843	0.911000	0.072*
C14A	0.9313 (2)	0.1395 (4)	0.81378 (16)	0.0479 (8)
H14A	0.929246	0.225084	0.830529	0.058*
C15A	0.90318 (19)	0.1164 (3)	0.74297 (15)	0.0357 (6)
H15A	0.882490	0.186537	0.711397	0.043*
C16A	0.90432 (16)	−0.0111 (3)	0.71559 (14)	0.0316 (5)
C17A	0.67859 (15)	0.0327 (3)	0.57224 (13)	0.0277 (5)
C18A	0.6128 (2)	0.0787 (4)	0.5946 (2)	0.0497 (8)
H18A	0.620591	0.157373	0.620373	0.060*
C19A	0.5355 (2)	0.0117 (4)	0.5799 (2)	0.0569 (10)
H19A	0.490525	0.046866	0.594292	0.068*
C20A	0.52354 (19)	−0.1032 (4)	0.54536 (18)	0.0475 (8)
H20A	0.470901	−0.149129	0.535924	0.057*
C21A	0.5879 (2)	−0.1517 (4)	0.52446 (18)	0.0487 (8)
H21A	0.580561	−0.232974	0.501099	0.058*
C22A	0.66510 (19)	−0.0831 (4)	0.53697 (17)	0.0461 (8)
H22A	0.708730	−0.117411	0.520735	0.055*
C23A	0.73471 (15)	0.2414 (2)	0.54251 (14)	0.0272 (5)
C24A	0.70146 (15)	0.2396 (2)	0.47090 (14)	0.0264 (5)
H24A	0.689599	0.159083	0.446837	0.032*
C25A	0.68451 (16)	0.3567 (3)	0.43217 (16)	0.0307 (5)
C26A	0.64932 (18)	0.3588 (3)	0.35808 (16)	0.0360 (6)
H26A	0.635255	0.280285	0.332208	0.043*
C27A	0.6359 (2)	0.4759 (3)	0.32424 (19)	0.0442 (7)
C28A	0.6564 (2)	0.5939 (3)	0.3598 (2)	0.0473 (8)
H28A	0.648076	0.673357	0.334619	0.057*
C29A	0.68871 (19)	0.5927 (3)	0.4315 (2)	0.0455 (8)
H29A	0.702150	0.672378	0.456212	0.055*
C30A	0.70257 (16)	0.4748 (3)	0.46960 (17)	0.0348 (6)
C31A	0.74691 (17)	0.3681 (3)	0.57451 (17)	0.0361 (6)
C32A	0.7682 (3)	0.4825 (5)	0.6821 (2)	0.0641 (12)
H32A	0.800334	0.551543	0.668372	0.096*
H32B	0.792178	0.468439	0.732896	0.096*
H32C	0.707587	0.507649	0.669651	0.096*
C33A	0.87369 (16)	0.1975 (3)	0.38480 (12)	0.0264 (4)
C34A	0.82928 (16)	0.2472 (3)	0.31203 (13)	0.0267 (5)
H34A	0.779369	0.202920	0.283576	0.032*
C35A	0.85588 (16)	0.3491 (3)	0.28539 (13)	0.0269 (5)
H35A	0.907626	0.391592	0.311789	0.032*
C36A	0.80515 (16)	0.3986 (2)	0.21389 (13)	0.0280 (5)
Br1B	0.03711 (2)	0.42464 (3)	−0.28802 (2)	0.04720 (9)
O1B	0.33662 (11)	0.00508 (18)	0.02269 (9)	0.0267 (3)
H1B	0.327 (2)	0.060 (4)	−0.013 (2)	0.040*
O2B	0.27505 (14)	0.3816 (2)	0.13215 (11)	0.0392 (5)
O3B	0.57136 (13)	0.7488 (3)	0.07837 (11)	0.0460 (6)
O4B	0.68777 (12)	0.62216 (19)	0.10440 (9)	0.0294 (4)
O5B	0.64680 (14)	1.0698 (2)	0.27053 (14)	0.0453 (5)
O6B	0.75267 (14)	0.9246 (2)	0.31105 (10)	0.0398 (5)
H6B	0.771 (3)	0.989 (5)	0.339 (2)	0.060*
N1B	0.53663 (13)	0.1951 (2)	0.04729 (12)	0.0283 (4)
H1BN	0.502 (2)	0.191 (4)	0.006 (2)	0.034*
N2B	0.22630 (13)	0.4745 (2)	0.02299 (12)	0.0303 (4)
C1B	0.25543 (14)	0.1260 (2)	0.08575 (12)	0.0230 (4)
H1BA	0.264502	0.161026	0.133894	0.028*
C2B	0.34548 (14)	0.0737 (2)	0.08604 (12)	0.0229 (4)
C3B	0.40925 (15)	0.1858 (3)	0.08942 (14)	0.0267 (5)
H3BA	0.387922	0.239023	0.046308	0.032*
H3BB	0.413490	0.242027	0.130194	0.032*
C4B	0.49810 (15)	0.1312 (3)	0.09628 (14)	0.0294 (5)
H4BA	0.536885	0.143220	0.145135	0.035*
H4BB	0.493009	0.036984	0.086459	0.035*
C5B	0.55983 (19)	0.3328 (3)	0.06465 (17)	0.0405 (6)
H5BA	0.576770	0.372420	0.026984	0.061*
H5BB	0.607907	0.337836	0.108886	0.061*
H5BC	0.510149	0.379233	0.069535	0.061*
C6B	0.61290 (18)	0.1223 (4)	0.04453 (18)	0.0426 (7)
H6BA	0.597246	0.031375	0.033235	0.064*
H6BB	0.658496	0.127597	0.090215	0.064*
H6BC	0.633488	0.159756	0.008298	0.064*
C7B	0.38230 (15)	−0.0216 (3)	0.14727 (13)	0.0262 (4)
C8B	0.39567 (17)	−0.1480 (3)	0.13133 (16)	0.0331 (5)
H8B	0.379285	−0.172851	0.083366	0.040*
C9B	0.4325 (2)	−0.2415 (3)	0.18302 (19)	0.0416 (7)
H9B	0.440569	−0.327656	0.169875	0.050*
C10B	0.4565 (2)	−0.2081 (3)	0.25186 (19)	0.0447 (8)
H10B	0.480564	−0.271730	0.286887	0.054*
C11B	0.44597 (19)	−0.0799 (4)	0.27190 (15)	0.0408 (6)
C12B	0.4749 (3)	−0.0458 (5)	0.34383 (18)	0.0598 (11)
H12B	0.499686	−0.110313	0.378138	0.072*
C13B	0.4677 (3)	0.0782 (6)	0.36478 (18)	0.0675 (12)
H13B	0.488485	0.100209	0.413208	0.081*
C14B	0.4294 (3)	0.1732 (4)	0.31411 (18)	0.0557 (9)
H14B	0.423864	0.259353	0.328671	0.067*
C15B	0.3998 (2)	0.1431 (3)	0.24405 (15)	0.0378 (6)
H15B	0.373284	0.208679	0.210960	0.045*
C16B	0.40786 (17)	0.0161 (3)	0.21970 (14)	0.0312 (5)
C17B	0.18258 (14)	0.0260 (2)	0.07173 (12)	0.0240 (4)
C18B	0.17658 (17)	−0.0904 (3)	0.03616 (16)	0.0362 (6)
H18B	0.222145	−0.116942	0.020048	0.043*
C19B	0.10414 (19)	−0.1690 (3)	0.02384 (17)	0.0403 (6)
H19B	0.101668	−0.249542	0.000471	0.048*
C20B	0.03663 (18)	−0.1320 (3)	0.04485 (16)	0.0375 (6)
H20B	−0.013176	−0.184875	0.035055	0.045*
C21B	0.0420 (2)	−0.0165 (4)	0.0805 (2)	0.0458 (7)
H21B	−0.004282	0.010201	0.095651	0.055*
C22B	0.11428 (19)	0.0607 (3)	0.09440 (17)	0.0368 (6)
H22B	0.117436	0.138935	0.119927	0.044*
C23B	0.22633 (14)	0.2390 (2)	0.03590 (13)	0.0239 (4)
C24B	0.18545 (14)	0.2252 (2)	−0.03469 (12)	0.0231 (4)
H24B	0.170904	0.141171	−0.054186	0.028*
C25B	0.16467 (14)	0.3353 (2)	−0.07890 (13)	0.0245 (4)
C26B	0.12002 (16)	0.3252 (3)	−0.15184 (14)	0.0270 (5)
H26B	0.102173	0.243203	−0.173015	0.032*
C27B	0.10314 (16)	0.4359 (3)	−0.19113 (13)	0.0305 (5)
C28B	0.13093 (17)	0.5590 (3)	−0.16304 (16)	0.0325 (5)
H28B	0.120889	0.633205	−0.192502	0.039*
C29B	0.17314 (16)	0.5698 (3)	−0.09175 (16)	0.0321 (5)
H29B	0.191820	0.652478	−0.071822	0.039*
C30B	0.18881 (14)	0.4591 (2)	−0.04815 (14)	0.0270 (5)
C31B	0.24184 (15)	0.3705 (3)	0.06140 (14)	0.0284 (5)
C32B	0.2775 (3)	0.5082 (4)	0.1616 (2)	0.0605 (11)
H32D	0.312393	0.565497	0.143091	0.091*
H32E	0.302792	0.503171	0.212812	0.091*
H32F	0.218838	0.542620	0.149019	0.091*
C33B	0.64439 (16)	0.7125 (3)	0.11789 (12)	0.0275 (5)
C34B	0.68382 (16)	0.7862 (3)	0.18508 (12)	0.0262 (4)
H34B	0.740262	0.764391	0.214460	0.039 (9)*
C35B	0.64195 (16)	0.8809 (3)	0.20449 (13)	0.0270 (5)
H35B	0.583327	0.894093	0.177285	0.036 (9)*
C36B	0.67970 (16)	0.9671 (3)	0.26520 (14)	0.0294 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1A	0.0876 (3)	0.0599 (2)	0.0575 (2)	0.0371 (2)	0.0360 (2)	0.02961 (19)
O1A	0.0325 (9)	0.0275 (9)	0.0287 (8)	−0.0026 (7)	0.0171 (7)	−0.0036 (7)
O2A	0.0461 (12)	0.0492 (14)	0.0444 (12)	0.0007 (10)	0.0073 (10)	−0.0244 (11)
O3A	0.0314 (9)	0.0409 (11)	0.0239 (8)	−0.0039 (8)	−0.0006 (7)	0.0011 (8)
O4A	0.0513 (12)	0.0284 (9)	0.0209 (8)	−0.0064 (8)	0.0065 (8)	−0.0016 (7)
O5A	0.0397 (10)	0.0264 (9)	0.0319 (9)	−0.0017 (8)	0.0024 (8)	0.0014 (7)
O6A	0.0427 (11)	0.0284 (9)	0.0300 (9)	0.0029 (8)	−0.0027 (8)	−0.0046 (7)
N1A	0.0175 (8)	0.0260 (9)	0.0287 (9)	−0.0018 (7)	0.0061 (7)	0.0007 (8)
N2A	0.0254 (10)	0.0290 (11)	0.0671 (17)	−0.0033 (9)	0.0154 (11)	−0.0140 (12)
C1A	0.0206 (10)	0.0325 (12)	0.0239 (10)	0.0019 (9)	0.0089 (8)	−0.0032 (9)
C2A	0.0199 (9)	0.0269 (11)	0.0270 (11)	0.0006 (8)	0.0104 (8)	−0.0003 (8)
C3A	0.0206 (10)	0.0269 (11)	0.0309 (11)	−0.0004 (8)	0.0082 (9)	0.0004 (9)
C4A	0.0233 (11)	0.0325 (13)	0.0417 (14)	0.0030 (9)	0.0150 (10)	0.0121 (11)
C5A	0.0407 (15)	0.0458 (17)	0.0348 (14)	−0.0224 (13)	0.0125 (12)	−0.0103 (12)
C6A	0.0382 (15)	0.0335 (14)	0.071 (2)	0.0077 (12)	0.0326 (15)	0.0071 (15)
C7A	0.0209 (10)	0.0325 (13)	0.0342 (12)	0.0000 (9)	0.0129 (9)	0.0030 (9)
C8A	0.0437 (15)	0.0316 (13)	0.0409 (15)	0.0007 (11)	0.0237 (12)	0.0043 (11)
C9A	0.060 (2)	0.0337 (15)	0.060 (2)	0.0086 (14)	0.0344 (17)	0.0150 (14)
C10A	0.0437 (17)	0.0495 (19)	0.056 (2)	0.0096 (14)	0.0227 (15)	0.0258 (16)
C11A	0.0295 (12)	0.0538 (19)	0.0378 (14)	−0.0025 (12)	0.0098 (11)	0.0151 (13)
C12A	0.0464 (17)	0.072 (2)	0.0335 (14)	−0.0056 (18)	0.0047 (13)	0.0172 (17)
C13A	0.054 (2)	0.087 (3)	0.0293 (15)	−0.015 (2)	0.0020 (14)	0.0067 (17)
C14A	0.0524 (18)	0.059 (2)	0.0281 (13)	−0.0158 (16)	0.0079 (13)	−0.0067 (13)
C15A	0.0344 (13)	0.0455 (16)	0.0257 (12)	−0.0101 (12)	0.0080 (10)	−0.0030 (11)
C16A	0.0227 (10)	0.0420 (14)	0.0291 (11)	−0.0035 (10)	0.0072 (9)	0.0052 (11)
C17A	0.0212 (10)	0.0394 (14)	0.0241 (10)	0.0016 (9)	0.0095 (8)	0.0059 (9)
C18A	0.0367 (15)	0.0452 (18)	0.082 (3)	0.0018 (13)	0.0390 (17)	−0.0005 (17)
C19A	0.0343 (15)	0.062 (2)	0.087 (3)	0.0035 (15)	0.0370 (18)	0.012 (2)
C20A	0.0255 (12)	0.066 (2)	0.0507 (17)	−0.0085 (13)	0.0119 (12)	0.0184 (16)
C21A	0.0395 (15)	0.068 (2)	0.0419 (16)	−0.0241 (16)	0.0185 (13)	−0.0132 (16)
C22A	0.0339 (13)	0.064 (2)	0.0487 (16)	−0.0199 (14)	0.0249 (12)	−0.0228 (16)
C23A	0.0212 (10)	0.0268 (11)	0.0352 (12)	0.0016 (9)	0.0116 (9)	−0.0069 (9)
C24A	0.0231 (10)	0.0244 (11)	0.0346 (12)	0.0041 (8)	0.0132 (9)	−0.0011 (9)
C25A	0.0225 (10)	0.0277 (12)	0.0462 (14)	0.0036 (9)	0.0171 (10)	0.0020 (11)
C26A	0.0356 (13)	0.0339 (14)	0.0445 (15)	0.0123 (11)	0.0211 (12)	0.0072 (12)
C27A	0.0404 (15)	0.0391 (15)	0.0610 (19)	0.0167 (13)	0.0274 (14)	0.0155 (15)
C28A	0.0340 (14)	0.0332 (15)	0.081 (3)	0.0102 (12)	0.0274 (16)	0.0152 (16)
C29A	0.0277 (13)	0.0251 (13)	0.087 (3)	0.0011 (10)	0.0228 (15)	0.0017 (15)
C30A	0.0206 (10)	0.0264 (11)	0.0600 (17)	0.0009 (9)	0.0167 (11)	−0.0022 (12)
C31A	0.0233 (11)	0.0355 (14)	0.0487 (16)	−0.0014 (10)	0.0108 (11)	−0.0159 (12)
C32A	0.064 (2)	0.060 (2)	0.073 (3)	−0.016 (2)	0.029 (2)	−0.044 (2)
C33A	0.0292 (11)	0.0269 (11)	0.0209 (10)	0.0030 (9)	0.0053 (8)	−0.0026 (8)
C34A	0.0243 (10)	0.0285 (11)	0.0234 (10)	0.0001 (9)	0.0025 (8)	−0.0008 (9)
C35A	0.0249 (10)	0.0270 (11)	0.0244 (10)	0.0002 (9)	0.0020 (8)	−0.0009 (9)
C36A	0.0286 (11)	0.0251 (12)	0.0275 (11)	0.0021 (9)	0.0057 (9)	−0.0014 (8)
Br1B	0.0713 (2)	0.03731 (15)	0.03003 (13)	0.00847 (15)	0.01267 (13)	0.00635 (12)
O1B	0.0293 (8)	0.0296 (9)	0.0256 (8)	0.0064 (7)	0.0151 (7)	0.0038 (7)
O2B	0.0409 (10)	0.0350 (10)	0.0348 (10)	0.0019 (8)	0.0031 (8)	−0.0121 (8)
O3B	0.0293 (10)	0.0694 (16)	0.0297 (10)	0.0111 (10)	−0.0034 (8)	−0.0150 (10)
O4B	0.0356 (9)	0.0289 (9)	0.0230 (8)	0.0020 (7)	0.0084 (7)	−0.0004 (7)
O5B	0.0342 (10)	0.0326 (11)	0.0631 (14)	0.0041 (8)	0.0079 (10)	−0.0164 (10)
O6B	0.0472 (11)	0.0280 (9)	0.0306 (9)	0.0058 (9)	−0.0054 (8)	−0.0075 (9)
N1B	0.0164 (8)	0.0402 (12)	0.0255 (9)	−0.0009 (8)	0.0031 (7)	0.0079 (9)
N2B	0.0229 (9)	0.0247 (9)	0.0402 (12)	−0.0008 (8)	0.0063 (8)	−0.0054 (9)
C1B	0.0193 (9)	0.0272 (11)	0.0233 (10)	0.0022 (8)	0.0083 (8)	0.0006 (8)
C2B	0.0193 (9)	0.0284 (11)	0.0221 (10)	0.0043 (8)	0.0081 (8)	0.0057 (8)
C3B	0.0196 (10)	0.0290 (12)	0.0322 (11)	0.0016 (8)	0.0095 (9)	0.0081 (9)
C4B	0.0201 (10)	0.0364 (13)	0.0319 (12)	0.0031 (9)	0.0089 (9)	0.0121 (10)
C5B	0.0310 (13)	0.0404 (15)	0.0454 (16)	−0.0101 (11)	0.0064 (12)	0.0031 (13)
C6B	0.0250 (12)	0.059 (2)	0.0458 (16)	0.0085 (12)	0.0149 (11)	0.0128 (15)
C7B	0.0194 (9)	0.0311 (12)	0.0288 (11)	0.0012 (9)	0.0088 (8)	0.0057 (10)
C8B	0.0300 (12)	0.0300 (13)	0.0422 (14)	0.0041 (10)	0.0160 (11)	0.0092 (11)
C9B	0.0358 (14)	0.0357 (15)	0.0560 (18)	0.0083 (12)	0.0188 (13)	0.0171 (13)
C10B	0.0351 (14)	0.0460 (18)	0.0516 (18)	0.0116 (13)	0.0121 (13)	0.0282 (15)
C11B	0.0343 (13)	0.0529 (17)	0.0312 (12)	−0.0013 (13)	0.0055 (10)	0.0153 (14)
C12B	0.060 (2)	0.078 (3)	0.0307 (14)	0.004 (2)	0.0002 (14)	0.0205 (17)
C13B	0.077 (3)	0.088 (3)	0.0234 (14)	−0.006 (2)	−0.0024 (16)	0.0039 (17)
C14B	0.067 (2)	0.059 (2)	0.0308 (15)	−0.0105 (18)	0.0022 (15)	−0.0046 (15)
C15B	0.0381 (14)	0.0442 (16)	0.0267 (12)	−0.0045 (12)	0.0047 (11)	0.0014 (11)
C16B	0.0236 (11)	0.0400 (14)	0.0275 (11)	−0.0009 (10)	0.0052 (9)	0.0083 (10)
C17B	0.0207 (10)	0.0295 (11)	0.0225 (10)	0.0029 (8)	0.0081 (8)	0.0042 (8)
C18B	0.0282 (11)	0.0403 (15)	0.0452 (14)	−0.0070 (11)	0.0189 (11)	−0.0112 (12)
C19B	0.0354 (14)	0.0434 (16)	0.0445 (16)	−0.0130 (12)	0.0163 (12)	−0.0110 (13)
C20B	0.0278 (12)	0.0474 (17)	0.0382 (14)	−0.0103 (11)	0.0120 (11)	0.0046 (13)
C21B	0.0317 (13)	0.0533 (19)	0.063 (2)	−0.0026 (13)	0.0302 (14)	0.0012 (17)
C22B	0.0330 (13)	0.0365 (14)	0.0499 (16)	−0.0005 (11)	0.0259 (12)	−0.0019 (12)
C23B	0.0187 (9)	0.0231 (10)	0.0309 (11)	0.0022 (8)	0.0093 (8)	−0.0017 (8)
C24B	0.0193 (9)	0.0220 (10)	0.0277 (10)	0.0029 (8)	0.0074 (8)	−0.0002 (8)
C25B	0.0188 (9)	0.0242 (11)	0.0309 (11)	0.0030 (8)	0.0088 (8)	0.0014 (9)
C26B	0.0273 (11)	0.0247 (11)	0.0313 (12)	0.0028 (9)	0.0127 (9)	0.0021 (9)
C27B	0.0309 (11)	0.0313 (13)	0.0317 (11)	0.0055 (10)	0.0136 (9)	0.0061 (10)
C28B	0.0293 (12)	0.0269 (12)	0.0454 (15)	0.0029 (10)	0.0180 (11)	0.0089 (11)
C29B	0.0233 (11)	0.0232 (11)	0.0519 (16)	−0.0007 (9)	0.0151 (11)	0.0020 (11)
C30B	0.0177 (9)	0.0224 (11)	0.0410 (13)	0.0008 (8)	0.0096 (9)	0.0008 (9)
C31B	0.0203 (10)	0.0284 (12)	0.0345 (12)	0.0007 (9)	0.0063 (9)	−0.0061 (10)
C32B	0.072 (3)	0.044 (2)	0.051 (2)	−0.0037 (17)	0.0006 (18)	−0.0245 (16)
C33B	0.0273 (11)	0.0343 (13)	0.0196 (10)	0.0008 (9)	0.0059 (8)	−0.0007 (9)
C34B	0.0241 (10)	0.0299 (12)	0.0223 (10)	0.0010 (9)	0.0043 (8)	−0.0013 (9)
C35B	0.0242 (10)	0.0263 (11)	0.0277 (11)	0.0007 (9)	0.0048 (9)	0.0004 (9)
C36B	0.0295 (11)	0.0245 (11)	0.0330 (12)	0.0004 (9)	0.0085 (9)	−0.0015 (9)

Geometric parameters (Å, º)

Br1A—C27A	1.891 (4)	Br1B—C27B	1.902 (3)
O1A—C2A	1.425 (3)	O1B—C2B	1.425 (3)
O1A—H1AB	0.86 (4)	O1B—H1B	0.89 (4)
O2A—C31A	1.363 (4)	O2B—C31B	1.354 (3)
O2A—C32A	1.434 (4)	O2B—C32B	1.430 (4)
O3A—C33A	1.258 (3)	O3B—C33B	1.261 (3)
O4A—C33A	1.263 (3)	O4B—C33B	1.257 (3)
O5A—C36A	1.323 (3)	O5B—C36B	1.211 (3)
O5A—H5A	1.04 (4)	O6B—C36B	1.326 (3)
O6A—C36A	1.206 (3)	O6B—H6B	0.86 (5)
N1A—C5A	1.478 (3)	N1B—C6B	1.479 (4)
N1A—C6A	1.485 (4)	N1B—C5B	1.484 (4)
N1A—C4A	1.498 (3)	N1B—C4B	1.491 (3)
N1A—H1AN	0.98 (4)	N1B—H1BN	0.85 (4)
N2A—C31A	1.296 (4)	N2B—C31B	1.299 (4)
N2A—C30A	1.371 (4)	N2B—C30B	1.372 (4)
C1A—C23A	1.514 (4)	C1B—C23B	1.511 (3)
C1A—C17A	1.535 (3)	C1B—C17B	1.536 (3)
C1A—C2A	1.568 (3)	C1B—C2B	1.576 (3)
C1A—H1A	1.0000	C1B—H1BA	1.0000
C2A—C7A	1.535 (4)	C2B—C7B	1.539 (3)
C2A—C3A	1.551 (3)	C2B—C3B	1.548 (3)
C3A—C4A	1.535 (3)	C3B—C4B	1.530 (3)
C3A—H3AA	0.9900	C3B—H3BA	0.9900
C3A—H3AB	0.9900	C3B—H3BB	0.9900
C4A—H4AA	0.9900	C4B—H4BA	0.9900
C4A—H4AB	0.9900	C4B—H4BB	0.9900
C5A—H5AA	0.9800	C5B—H5BA	0.9800
C5A—H5AB	0.9800	C5B—H5BB	0.9800
C5A—H5AC	0.9800	C5B—H5BC	0.9800
C6A—H6AA	0.9800	C6B—H6BA	0.9800
C6A—H6AB	0.9800	C6B—H6BB	0.9800
C6A—H6AC	0.9800	C6B—H6BC	0.9800
C7A—C8A	1.381 (4)	C7B—C8B	1.378 (4)
C7A—C16A	1.437 (4)	C7B—C16B	1.434 (4)
C8A—C9A	1.406 (4)	C8B—C9B	1.403 (4)
C8A—H8A	0.9500	C8B—H8B	0.9500
C9A—C10A	1.355 (6)	C9B—C10B	1.357 (5)
C9A—H9A	0.9500	C9B—H9B	0.9500
C10A—C11A	1.417 (6)	C10B—C11B	1.411 (6)
C10A—H10A	0.9500	C10B—H10B	0.9500
C11A—C12A	1.416 (5)	C11B—C12B	1.414 (5)
C11A—C16A	1.432 (4)	C11B—C16B	1.432 (4)
C12A—C13A	1.351 (7)	C12B—C13B	1.365 (7)
C12A—H12A	0.9500	C12B—H12B	0.9500
C13A—C14A	1.406 (6)	C13B—C14B	1.407 (6)
C13A—H13A	0.9500	C13B—H13B	0.9500
C14A—C15A	1.369 (4)	C14B—C15B	1.370 (4)
C14A—H14A	0.9500	C14B—H14B	0.9500
C15A—C16A	1.430 (5)	C15B—C16B	1.421 (4)
C15A—H15A	0.9500	C15B—H15B	0.9500
C17A—C22A	1.371 (4)	C17B—C18B	1.387 (4)
C17A—C18A	1.387 (4)	C17B—C22B	1.392 (3)
C18A—C19A	1.391 (5)	C18B—C19B	1.395 (4)
C18A—H18A	0.9500	C18B—H18B	0.9500
C19A—C20A	1.357 (6)	C19B—C20B	1.367 (4)
C19A—H19A	0.9500	C19B—H19B	0.9500
C20A—C21A	1.357 (5)	C20B—C21B	1.380 (5)
C20A—H20A	0.9500	C20B—H20B	0.9500
C21A—C22A	1.403 (4)	C21B—C22B	1.381 (4)
C21A—H21A	0.9500	C21B—H21B	0.9500
C22A—H22A	0.9500	C22B—H22B	0.9500
C23A—C24A	1.366 (4)	C23B—C24B	1.367 (3)
C23A—C31A	1.443 (4)	C23B—C31B	1.444 (3)
C24A—C25A	1.415 (4)	C24B—C25B	1.415 (3)
C24A—H24A	0.9500	C24B—H24B	0.9500
C25A—C30A	1.413 (4)	C25B—C26B	1.415 (4)
C25A—C26A	1.414 (4)	C25B—C30B	1.419 (4)
C26A—C27A	1.370 (4)	C26B—C27B	1.366 (4)
C26A—H26A	0.9500	C26B—H26B	0.9500
C27A—C28A	1.397 (5)	C27B—C28B	1.404 (4)
C28A—C29A	1.366 (6)	C28B—C29B	1.380 (4)
C28A—H28A	0.9500	C28B—H28B	0.9500
C29A—C30A	1.417 (5)	C29B—C30B	1.413 (4)
C29A—H29A	0.9500	C29B—H29B	0.9500
C32A—H32A	0.9800	C32B—H32D	0.9800
C32A—H32B	0.9800	C32B—H32E	0.9800
C32A—H32C	0.9800	C32B—H32F	0.9800
C33A—C34A	1.498 (3)	C33B—C34B	1.502 (3)
C34A—C35A	1.320 (4)	C34B—C35B	1.327 (4)
C34A—H34A	0.9500	C34B—H34B	0.9500
C35A—C36A	1.498 (3)	C35B—C36B	1.476 (4)
C35A—H35A	0.9500	C35B—H35B	0.9500
C2A—O1A—H1AB	112 (3)	C2B—O1B—H1B	111 (3)
C31A—O2A—C32A	117.6 (3)	C31B—O2B—C32B	117.4 (3)
C36A—O5A—H5A	107 (3)	C36B—O6B—H6B	105 (3)
C5A—N1A—C6A	110.7 (2)	C6B—N1B—C5B	109.8 (2)
C5A—N1A—C4A	112.5 (2)	C6B—N1B—C4B	110.6 (2)
C6A—N1A—C4A	110.8 (2)	C5B—N1B—C4B	113.6 (2)
C5A—N1A—H1AN	110 (2)	C6B—N1B—H1BN	104 (3)
C6A—N1A—H1AN	104 (2)	C5B—N1B—H1BN	109 (3)
C4A—N1A—H1AN	108 (2)	C4B—N1B—H1BN	109 (3)
C31A—N2A—C30A	117.5 (3)	C31B—N2B—C30B	117.4 (2)
C23A—C1A—C17A	109.67 (19)	C23B—C1B—C17B	109.78 (18)
C23A—C1A—C2A	111.83 (19)	C23B—C1B—C2B	111.04 (18)
C17A—C1A—C2A	116.8 (2)	C17B—C1B—C2B	116.5 (2)
C23A—C1A—H1A	105.9	C23B—C1B—H1BA	106.3
C17A—C1A—H1A	105.9	C17B—C1B—H1BA	106.3
C2A—C1A—H1A	105.9	C2B—C1B—H1BA	106.3
O1A—C2A—C7A	107.7 (2)	O1B—C2B—C7B	107.4 (2)
O1A—C2A—C3A	106.58 (19)	O1B—C2B—C3B	106.19 (18)
C7A—C2A—C3A	110.6 (2)	C7B—C2B—C3B	111.09 (19)
O1A—C2A—C1A	109.90 (19)	O1B—C2B—C1B	110.36 (18)
C7A—C2A—C1A	109.93 (19)	C7B—C2B—C1B	110.11 (18)
C3A—C2A—C1A	112.0 (2)	C3B—C2B—C1B	111.5 (2)
C4A—C3A—C2A	109.8 (2)	C4B—C3B—C2B	110.0 (2)
C4A—C3A—H3AA	109.7	C4B—C3B—H3BA	109.7
C2A—C3A—H3AA	109.7	C2B—C3B—H3BA	109.7
C4A—C3A—H3AB	109.7	C4B—C3B—H3BB	109.7
C2A—C3A—H3AB	109.7	C2B—C3B—H3BB	109.7
H3AA—C3A—H3AB	108.2	H3BA—C3B—H3BB	108.2
N1A—C4A—C3A	113.3 (2)	N1B—C4B—C3B	112.3 (2)
N1A—C4A—H4AA	108.9	N1B—C4B—H4BA	109.2
C3A—C4A—H4AA	108.9	C3B—C4B—H4BA	109.2
N1A—C4A—H4AB	108.9	N1B—C4B—H4BB	109.2
C3A—C4A—H4AB	108.9	C3B—C4B—H4BB	109.2
H4AA—C4A—H4AB	107.7	H4BA—C4B—H4BB	107.9
N1A—C5A—H5AA	109.5	N1B—C5B—H5BA	109.5
N1A—C5A—H5AB	109.5	N1B—C5B—H5BB	109.5
H5AA—C5A—H5AB	109.5	H5BA—C5B—H5BB	109.5
N1A—C5A—H5AC	109.5	N1B—C5B—H5BC	109.5
H5AA—C5A—H5AC	109.5	H5BA—C5B—H5BC	109.5
H5AB—C5A—H5AC	109.5	H5BB—C5B—H5BC	109.5
N1A—C6A—H6AA	109.5	N1B—C6B—H6BA	109.5
N1A—C6A—H6AB	109.5	N1B—C6B—H6BB	109.5
H6AA—C6A—H6AB	109.5	H6BA—C6B—H6BB	109.5
N1A—C6A—H6AC	109.5	N1B—C6B—H6BC	109.5
H6AA—C6A—H6AC	109.5	H6BA—C6B—H6BC	109.5
H6AB—C6A—H6AC	109.5	H6BB—C6B—H6BC	109.5
C8A—C7A—C16A	118.2 (3)	C8B—C7B—C16B	118.6 (2)
C8A—C7A—C2A	117.8 (2)	C8B—C7B—C2B	117.9 (2)
C16A—C7A—C2A	123.9 (2)	C16B—C7B—C2B	123.3 (2)
C7A—C8A—C9A	122.6 (3)	C7B—C8B—C9B	122.7 (3)
C7A—C8A—H8A	118.7	C7B—C8B—H8B	118.6
C9A—C8A—H8A	118.7	C9B—C8B—H8B	118.6
C10A—C9A—C8A	120.3 (3)	C10B—C9B—C8B	119.7 (3)
C10A—C9A—H9A	119.9	C10B—C9B—H9B	120.2
C8A—C9A—H9A	119.9	C8B—C9B—H9B	120.2
C9A—C10A—C11A	120.1 (3)	C9B—C10B—C11B	120.6 (3)
C9A—C10A—H10A	120.0	C9B—C10B—H10B	119.7
C11A—C10A—H10A	120.0	C11B—C10B—H10B	119.7
C12A—C11A—C10A	119.7 (3)	C10B—C11B—C12B	119.7 (3)
C12A—C11A—C16A	120.0 (3)	C10B—C11B—C16B	120.3 (3)
C10A—C11A—C16A	120.3 (3)	C12B—C11B—C16B	120.0 (4)
C13A—C12A—C11A	121.3 (3)	C13B—C12B—C11B	121.1 (3)
C13A—C12A—H12A	119.4	C13B—C12B—H12B	119.5
C11A—C12A—H12A	119.4	C11B—C12B—H12B	119.5
C12A—C13A—C14A	119.8 (3)	C12B—C13B—C14B	119.5 (3)
C12A—C13A—H13A	120.1	C12B—C13B—H13B	120.3
C14A—C13A—H13A	120.1	C14B—C13B—H13B	120.3
C15A—C14A—C13A	120.9 (4)	C15B—C14B—C13B	120.9 (4)
C15A—C14A—H14A	119.6	C15B—C14B—H14B	119.6
C13A—C14A—H14A	119.6	C13B—C14B—H14B	119.6
C14A—C15A—C16A	121.3 (3)	C14B—C15B—C16B	121.6 (3)
C14A—C15A—H15A	119.3	C14B—C15B—H15B	119.2
C16A—C15A—H15A	119.3	C16B—C15B—H15B	119.2
C15A—C16A—C11A	116.6 (3)	C15B—C16B—C11B	116.9 (3)
C15A—C16A—C7A	124.8 (3)	C15B—C16B—C7B	125.0 (2)
C11A—C16A—C7A	118.5 (3)	C11B—C16B—C7B	118.1 (3)
C22A—C17A—C18A	117.2 (3)	C18B—C17B—C22B	117.7 (2)
C22A—C17A—C1A	126.7 (2)	C18B—C17B—C1B	126.6 (2)
C18A—C17A—C1A	116.0 (3)	C22B—C17B—C1B	115.6 (2)
C17A—C18A—C19A	121.2 (4)	C17B—C18B—C19B	120.5 (3)
C17A—C18A—H18A	119.4	C17B—C18B—H18B	119.8
C19A—C18A—H18A	119.4	C19B—C18B—H18B	119.8
C20A—C19A—C18A	120.7 (3)	C20B—C19B—C18B	121.1 (3)
C20A—C19A—H19A	119.6	C20B—C19B—H19B	119.4
C18A—C19A—H19A	119.6	C18B—C19B—H19B	119.4
C21A—C20A—C19A	119.1 (3)	C19B—C20B—C21B	118.9 (3)
C21A—C20A—H20A	120.5	C19B—C20B—H20B	120.6
C19A—C20A—H20A	120.5	C21B—C20B—H20B	120.6
C20A—C21A—C22A	120.7 (4)	C20B—C21B—C22B	120.5 (3)
C20A—C21A—H21A	119.6	C20B—C21B—H21B	119.8
C22A—C21A—H21A	119.6	C22B—C21B—H21B	119.8
C17A—C22A—C21A	121.1 (3)	C21B—C22B—C17B	121.3 (3)
C17A—C22A—H22A	119.5	C21B—C22B—H22B	119.3
C21A—C22A—H22A	119.5	C17B—C22B—H22B	119.3
C24A—C23A—C31A	115.7 (3)	C24B—C23B—C31B	115.9 (2)
C24A—C23A—C1A	123.6 (2)	C24B—C23B—C1B	123.5 (2)
C31A—C23A—C1A	120.7 (2)	C31B—C23B—C1B	120.5 (2)
C23A—C24A—C25A	120.7 (2)	C23B—C24B—C25B	120.4 (2)
C23A—C24A—H24A	119.7	C23B—C24B—H24B	119.8
C25A—C24A—H24A	119.7	C25B—C24B—H24B	119.8
C30A—C25A—C26A	119.5 (3)	C24B—C25B—C26B	122.1 (2)
C30A—C25A—C24A	118.2 (3)	C24B—C25B—C30B	118.2 (2)
C26A—C25A—C24A	122.3 (3)	C26B—C25B—C30B	119.7 (2)
C27A—C26A—C25A	118.9 (3)	C27B—C26B—C25B	118.6 (2)
C27A—C26A—H26A	120.6	C27B—C26B—H26B	120.7
C25A—C26A—H26A	120.6	C25B—C26B—H26B	120.7
C26A—C27A—C28A	122.8 (3)	C26B—C27B—C28B	123.1 (2)
C26A—C27A—Br1A	119.0 (3)	C26B—C27B—Br1B	118.9 (2)
C28A—C27A—Br1A	118.2 (3)	C28B—C27B—Br1B	118.0 (2)
C29A—C28A—C27A	118.6 (3)	C29B—C28B—C27B	118.6 (2)
C29A—C28A—H28A	120.7	C29B—C28B—H28B	120.7
C27A—C28A—H28A	120.7	C27B—C28B—H28B	120.7
C28A—C29A—C30A	121.3 (3)	C28B—C29B—C30B	120.6 (3)
C28A—C29A—H29A	119.4	C28B—C29B—H29B	119.7
C30A—C29A—H29A	119.4	C30B—C29B—H29B	119.7
N2A—C30A—C25A	121.7 (3)	N2B—C30B—C29B	119.0 (2)
N2A—C30A—C29A	119.4 (3)	N2B—C30B—C25B	121.8 (2)
C25A—C30A—C29A	118.9 (3)	C29B—C30B—C25B	119.3 (2)
N2A—C31A—O2A	120.2 (3)	N2B—C31B—O2B	119.4 (2)
N2A—C31A—C23A	126.1 (3)	N2B—C31B—C23B	126.0 (2)
O2A—C31A—C23A	113.7 (3)	O2B—C31B—C23B	114.7 (2)
O2A—C32A—H32A	109.5	O2B—C32B—H32D	109.5
O2A—C32A—H32B	109.5	O2B—C32B—H32E	109.5
H32A—C32A—H32B	109.5	H32D—C32B—H32E	109.5
O2A—C32A—H32C	109.5	O2B—C32B—H32F	109.5
H32A—C32A—H32C	109.5	H32D—C32B—H32F	109.5
H32B—C32A—H32C	109.5	H32E—C32B—H32F	109.5
O3A—C33A—O4A	124.3 (2)	O4B—C33B—O3B	125.1 (2)
O3A—C33A—C34A	118.4 (2)	O4B—C33B—C34B	117.6 (2)
O4A—C33A—C34A	117.4 (2)	O3B—C33B—C34B	117.3 (2)
C35A—C34A—C33A	123.4 (2)	C35B—C34B—C33B	121.8 (2)
C35A—C34A—H34A	118.3	C35B—C34B—H34B	119.1
C33A—C34A—H34A	118.3	C33B—C34B—H34B	119.1
C34A—C35A—C36A	120.6 (2)	C34B—C35B—C36B	124.8 (2)
C34A—C35A—H35A	119.7	C34B—C35B—H35B	117.6
C36A—C35A—H35A	119.7	C36B—C35B—H35B	117.6
O6A—C36A—O5A	124.6 (2)	O5B—C36B—O6B	123.8 (3)
O6A—C36A—C35A	123.3 (2)	O5B—C36B—C35B	121.5 (2)
O5A—C36A—C35A	112.1 (2)	O6B—C36B—C35B	114.6 (2)
C23A—C1A—C2A—O1A	−76.0 (3)	C23B—C1B—C2B—O1B	−73.1 (2)
C17A—C1A—C2A—O1A	51.5 (3)	C17B—C1B—C2B—O1B	53.6 (3)
C23A—C1A—C2A—C7A	165.5 (2)	C23B—C1B—C2B—C7B	168.5 (2)
C17A—C1A—C2A—C7A	−67.0 (3)	C17B—C1B—C2B—C7B	−64.8 (3)
C23A—C1A—C2A—C3A	42.2 (3)	C23B—C1B—C2B—C3B	44.7 (3)
C17A—C1A—C2A—C3A	169.7 (2)	C17B—C1B—C2B—C3B	171.38 (19)
O1A—C2A—C3A—C4A	−63.8 (3)	O1B—C2B—C3B—C4B	−64.8 (2)
C7A—C2A—C3A—C4A	53.1 (3)	C7B—C2B—C3B—C4B	51.7 (3)
C1A—C2A—C3A—C4A	176.0 (2)	C1B—C2B—C3B—C4B	174.92 (19)
C5A—N1A—C4A—C3A	82.3 (3)	C6B—N1B—C4B—C3B	−168.1 (2)
C6A—N1A—C4A—C3A	−153.2 (2)	C5B—N1B—C4B—C3B	67.9 (3)
C2A—C3A—C4A—N1A	137.2 (2)	C2B—C3B—C4B—N1B	133.7 (2)
O1A—C2A—C7A—C8A	−0.2 (3)	O1B—C2B—C7B—C8B	−2.6 (3)
C3A—C2A—C7A—C8A	−116.3 (3)	C3B—C2B—C7B—C8B	−118.3 (2)
C1A—C2A—C7A—C8A	119.5 (2)	C1B—C2B—C7B—C8B	117.6 (2)
O1A—C2A—C7A—C16A	177.1 (2)	O1B—C2B—C7B—C16B	173.7 (2)
C3A—C2A—C7A—C16A	61.0 (3)	C3B—C2B—C7B—C16B	58.0 (3)
C1A—C2A—C7A—C16A	−63.1 (3)	C1B—C2B—C7B—C16B	−66.1 (3)
C16A—C7A—C8A—C9A	0.8 (4)	C16B—C7B—C8B—C9B	0.6 (4)
C2A—C7A—C8A—C9A	178.3 (3)	C2B—C7B—C8B—C9B	177.1 (2)
C7A—C8A—C9A—C10A	0.2 (5)	C7B—C8B—C9B—C10B	−0.1 (4)
C8A—C9A—C10A—C11A	−0.8 (5)	C8B—C9B—C10B—C11B	−1.0 (5)
C9A—C10A—C11A—C12A	−178.6 (3)	C9B—C10B—C11B—C12B	−177.2 (3)
C9A—C10A—C11A—C16A	0.5 (5)	C9B—C10B—C11B—C16B	1.5 (5)
C10A—C11A—C12A—C13A	179.2 (4)	C10B—C11B—C12B—C13B	178.2 (4)
C16A—C11A—C12A—C13A	0.2 (5)	C16B—C11B—C12B—C13B	−0.5 (6)
C11A—C12A—C13A—C14A	0.3 (6)	C11B—C12B—C13B—C14B	1.3 (7)
C12A—C13A—C14A—C15A	−0.7 (6)	C12B—C13B—C14B—C15B	−0.6 (7)
C13A—C14A—C15A—C16A	0.7 (5)	C13B—C14B—C15B—C16B	−1.0 (6)
C14A—C15A—C16A—C11A	−0.2 (4)	C14B—C15B—C16B—C11B	1.8 (5)
C14A—C15A—C16A—C7A	−179.9 (3)	C14B—C15B—C16B—C7B	−176.9 (3)
C12A—C11A—C16A—C15A	−0.2 (4)	C10B—C11B—C16B—C15B	−179.8 (3)
C10A—C11A—C16A—C15A	−179.3 (3)	C12B—C11B—C16B—C15B	−1.1 (4)
C12A—C11A—C16A—C7A	179.5 (3)	C10B—C11B—C16B—C7B	−0.9 (4)
C10A—C11A—C16A—C7A	0.4 (4)	C12B—C11B—C16B—C7B	177.8 (3)
C8A—C7A—C16A—C15A	178.6 (3)	C8B—C7B—C16B—C15B	178.6 (3)
C2A—C7A—C16A—C15A	1.3 (4)	C2B—C7B—C16B—C15B	2.4 (4)
C8A—C7A—C16A—C11A	−1.1 (4)	C8B—C7B—C16B—C11B	−0.1 (4)
C2A—C7A—C16A—C11A	−178.4 (2)	C2B—C7B—C16B—C11B	−176.4 (2)
C23A—C1A—C17A—C22A	108.7 (3)	C23B—C1B—C17B—C18B	103.0 (3)
C2A—C1A—C17A—C22A	−19.8 (4)	C2B—C1B—C17B—C18B	−24.3 (3)
C23A—C1A—C17A—C18A	−68.6 (3)	C23B—C1B—C17B—C22B	−73.6 (3)
C2A—C1A—C17A—C18A	162.8 (3)	C2B—C1B—C17B—C22B	159.1 (2)
C22A—C17A—C18A—C19A	−1.8 (5)	C22B—C17B—C18B—C19B	0.1 (4)
C1A—C17A—C18A—C19A	175.8 (3)	C1B—C17B—C18B—C19B	−176.4 (3)
C17A—C18A—C19A—C20A	2.3 (6)	C17B—C18B—C19B—C20B	1.6 (5)
C18A—C19A—C20A—C21A	−0.7 (6)	C18B—C19B—C20B—C21B	−1.8 (5)
C19A—C20A—C21A—C22A	−1.3 (6)	C19B—C20B—C21B—C22B	0.3 (5)
C18A—C17A—C22A—C21A	−0.2 (5)	C20B—C21B—C22B—C17B	1.4 (5)
C1A—C17A—C22A—C21A	−177.6 (3)	C18B—C17B—C22B—C21B	−1.6 (4)
C20A—C21A—C22A—C17A	1.8 (6)	C1B—C17B—C22B—C21B	175.3 (3)
C17A—C1A—C23A—C24A	−57.4 (3)	C17B—C1B—C23B—C24B	−46.9 (3)
C2A—C1A—C23A—C24A	73.8 (3)	C2B—C1B—C23B—C24B	83.4 (3)
C17A—C1A—C23A—C31A	122.5 (2)	C17B—C1B—C23B—C31B	133.8 (2)
C2A—C1A—C23A—C31A	−106.3 (3)	C2B—C1B—C23B—C31B	−95.9 (3)
C31A—C23A—C24A—C25A	2.7 (3)	C31B—C23B—C24B—C25B	3.2 (3)
C1A—C23A—C24A—C25A	−177.3 (2)	C1B—C23B—C24B—C25B	−176.1 (2)
C23A—C24A—C25A—C30A	−0.3 (3)	C23B—C24B—C25B—C26B	−178.0 (2)
C23A—C24A—C25A—C26A	−179.3 (2)	C23B—C24B—C25B—C30B	1.2 (3)
C30A—C25A—C26A—C27A	1.8 (4)	C24B—C25B—C26B—C27B	−179.3 (2)
C24A—C25A—C26A—C27A	−179.1 (3)	C30B—C25B—C26B—C27B	1.6 (3)
C25A—C26A—C27A—C28A	0.8 (4)	C25B—C26B—C27B—C28B	2.5 (4)
C25A—C26A—C27A—Br1A	−178.82 (19)	C25B—C26B—C27B—Br1B	−176.19 (17)
C26A—C27A—C28A—C29A	−2.2 (4)	C26B—C27B—C28B—C29B	−3.7 (4)
Br1A—C27A—C28A—C29A	177.4 (2)	Br1B—C27B—C28B—C29B	175.05 (19)
C27A—C28A—C29A—C30A	0.9 (4)	C27B—C28B—C29B—C30B	0.7 (4)
C31A—N2A—C30A—C25A	1.5 (4)	C31B—N2B—C30B—C29B	−178.3 (2)
C31A—N2A—C30A—C29A	−178.4 (2)	C31B—N2B—C30B—C25B	2.3 (3)
C26A—C25A—C30A—N2A	177.1 (2)	C28B—C29B—C30B—N2B	−176.1 (2)
C24A—C25A—C30A—N2A	−2.1 (4)	C28B—C29B—C30B—C25B	3.3 (4)
C26A—C25A—C30A—C29A	−3.0 (3)	C24B—C25B—C30B—N2B	−4.2 (3)
C24A—C25A—C30A—C29A	177.9 (2)	C26B—C25B—C30B—N2B	175.0 (2)
C28A—C29A—C30A—N2A	−178.4 (3)	C24B—C25B—C30B—C29B	176.4 (2)
C28A—C29A—C30A—C25A	1.7 (4)	C26B—C25B—C30B—C29B	−4.4 (3)
C30A—N2A—C31A—O2A	−178.0 (2)	C30B—N2B—C31B—O2B	−176.9 (2)
C30A—N2A—C31A—C23A	1.3 (4)	C30B—N2B—C31B—C23B	2.6 (4)
C32A—O2A—C31A—N2A	14.6 (4)	C32B—O2B—C31B—N2B	10.6 (4)
C32A—O2A—C31A—C23A	−164.7 (3)	C32B—O2B—C31B—C23B	−169.0 (3)
C24A—C23A—C31A—N2A	−3.5 (4)	C24B—C23B—C31B—N2B	−5.4 (4)
C1A—C23A—C31A—N2A	176.6 (2)	C1B—C23B—C31B—N2B	173.9 (2)
C24A—C23A—C31A—O2A	175.9 (2)	C24B—C23B—C31B—O2B	174.1 (2)
C1A—C23A—C31A—O2A	−4.1 (3)	C1B—C23B—C31B—O2B	−6.6 (3)
O3A—C33A—C34A—C35A	6.7 (4)	O4B—C33B—C34B—C35B	−178.3 (3)
O4A—C33A—C34A—C35A	−173.8 (3)	O3B—C33B—C34B—C35B	3.8 (4)
C33A—C34A—C35A—C36A	−176.1 (2)	C33B—C34B—C35B—C36B	−172.7 (2)
C34A—C35A—C36A—O6A	−30.1 (4)	C34B—C35B—C36B—O5B	161.3 (3)
C34A—C35A—C36A—O5A	148.2 (3)	C34B—C35B—C36B—O6B	−16.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1AB···O4A	0.86 (4)	1.88 (4)	2.699 (3)	159 (4)
O5A—H5A···O4B	1.04 (4)	1.58 (4)	2.603 (3)	169 (4)
N1A—H1AN···O3A	0.98 (4)	1.68 (4)	2.641 (3)	163 (3)
C1A—H1A···O2A	1.00	2.23	2.767 (3)	112
C3A—H3AB···Br1B^i	0.99	3.01	3.850 (3)	143
C5A—H5AA···O1A^ii	0.98	2.58	3.501 (3)	157
C5A—H5AC···Br1B^i	0.98	2.82	3.612 (3)	139
C26A—H26A···O5B^iii	0.95	2.54	3.459 (4)	163
C34A—H34A···O5B^iii	0.95	2.52	3.379 (3)	151
O1B—H1B···O4B^iv	0.89 (4)	1.88 (4)	2.741 (3)	160 (4)
O6B—H6B···O4A^v	0.86 (5)	1.80 (5)	2.625 (3)	159 (4)
N1B—H1BN···O3B^iv	0.85 (4)	1.83 (4)	2.632 (3)	158 (4)
C5B—H5BA···O1B^vi	0.98	2.42	3.337 (4)	156
C5B—H5BB···Br1A	0.98	2.88	3.468 (3)	119
C5B—H5BB···O6A	0.98	2.42	3.287 (4)	148

Symmetry codes: (i) x+1, y, z+1; (ii) −x+2, y+1/2, −z+1; (iii) x, y−1, z; (iv) −x+1, y−1/2, −z; (v) x, y+1, z; (vi) −x+1, y+1/2, −z.

3-Benzyl-6-bromo-2-methoxyquinoline (3)

Crystal data

C17H14BrNO	Dx = 1.546 Mg m^−3
Mr = 328.20	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 9920 reflections
a = 4.3606 (6) Å	θ = 2.3–32.7°
b = 10.820 (2) Å	µ = 2.91 mm^−1
c = 29.886 (11) Å	T = 150 K
V = 1410.1 (6) Å^3	Needle, colourless
Z = 4	0.41 × 0.06 × 0.05 mm
F(000) = 664

Data collection

Bruker D8 Quest diffractometer with PhotonII charge-integrating pixel array detector (CPAD)	5125 independent reflections
Radiation source: fine focus sealed tube X-ray source	4504 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromator	Rint = 0.037
Detector resolution: 7.4074 pixels mm^-1	θmax = 33.1°, θmin = 2.8°
ω and phi scans	h = −6→5
Absorption correction: multi-scan (SADABS2016; Krause et al., 2015)	k = −16→16
Tmin = 0.658, Tmax = 0.747	l = −45→40
28030 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.023	Only H-atom displacement parameters refined
wR(F^2) = 0.057	w = 1/[σ^2(Fo^2) + (0.0308P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
5125 reflections	Δρmax = 0.28 e Å^−3
196 parameters	Δρmin = −0.38 e Å^−3
0 restraints	Absolute structure: Flack x determined using 1685 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.011 (3)

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.33234 (5)	1.09654 (2)	0.10466 (2)	0.03579 (6)
O1	0.9170 (3)	0.38638 (11)	0.08083 (4)	0.0283 (3)
N1	0.6613 (3)	0.56540 (12)	0.06323 (4)	0.0214 (2)
C1	0.8442 (4)	0.50555 (14)	0.09018 (5)	0.0214 (3)
C2	0.9779 (3)	0.55404 (15)	0.13019 (6)	0.0206 (3)
C3	0.9145 (3)	0.67422 (16)	0.14000 (6)	0.0212 (3)
H3	1.003058	0.711254	0.165763	0.027 (5)*
C4	0.7166 (3)	0.74501 (15)	0.11205 (5)	0.0191 (3)
C5	0.6405 (4)	0.86982 (15)	0.12085 (6)	0.0227 (3)
H5	0.724285	0.911329	0.146058	0.028 (5)*
C6	0.4437 (4)	0.92991 (14)	0.09234 (6)	0.0236 (3)
C7	0.3168 (4)	0.87254 (15)	0.05471 (6)	0.0247 (3)
H7	0.181534	0.916658	0.035583	0.034 (6)*
C8	0.3902 (4)	0.75158 (16)	0.04576 (6)	0.0229 (3)
H8	0.303981	0.711802	0.020373	0.031 (5)*
C9	0.5927 (3)	0.68571 (14)	0.07392 (5)	0.0192 (3)
C10	0.7927 (6)	0.33696 (18)	0.04034 (7)	0.0386 (5)
H10A	0.873753	0.383151	0.014732	0.045 (7)*
H10B	0.568653	0.344120	0.040923	0.051 (8)*
H10C	0.850322	0.249746	0.037603	0.048 (7)*
C11	1.1699 (4)	0.47323 (16)	0.16067 (6)	0.0240 (3)
H11A	1.325806	0.524748	0.175900	0.034 (6)*
H11B	1.278720	0.410507	0.142523	0.049 (7)*
C12	0.9739 (3)	0.40881 (15)	0.19546 (5)	0.0205 (3)
C13	0.8353 (4)	0.29555 (14)	0.18642 (6)	0.0246 (3)
H13	0.866613	0.256921	0.158245	0.022 (5)*
C14	0.6512 (4)	0.23861 (15)	0.21838 (6)	0.0294 (3)
H14	0.556300	0.161713	0.211782	0.055 (8)*
C15	0.6057 (4)	0.29308 (18)	0.25961 (7)	0.0310 (4)
H15	0.481362	0.253555	0.281437	0.035 (6)*
C16	0.7424 (4)	0.40577 (18)	0.26897 (6)	0.0302 (4)
H16	0.711861	0.443543	0.297316	0.035 (6)*
C17	0.9236 (4)	0.46362 (16)	0.23709 (6)	0.0267 (4)
H17	1.014500	0.541330	0.243665	0.051 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.04286 (10)	0.02454 (8)	0.03998 (11)	0.00613 (8)	−0.00053 (9)	−0.00279 (8)
O1	0.0374 (6)	0.0241 (6)	0.0233 (6)	0.0055 (5)	−0.0016 (5)	−0.0014 (5)
N1	0.0230 (6)	0.0238 (6)	0.0175 (6)	0.0004 (5)	−0.0001 (6)	−0.0002 (5)
C1	0.0220 (6)	0.0235 (7)	0.0188 (7)	0.0006 (6)	0.0033 (6)	0.0004 (5)
C2	0.0155 (6)	0.0279 (7)	0.0185 (7)	−0.0020 (5)	0.0015 (5)	0.0044 (6)
C3	0.0180 (6)	0.0278 (8)	0.0178 (7)	−0.0033 (5)	0.0000 (5)	0.0014 (6)
C4	0.0177 (6)	0.0243 (7)	0.0153 (7)	−0.0016 (5)	0.0025 (5)	0.0010 (5)
C5	0.0237 (7)	0.0254 (7)	0.0190 (7)	−0.0023 (6)	0.0022 (6)	−0.0016 (5)
C6	0.0244 (7)	0.0221 (7)	0.0242 (8)	0.0006 (5)	0.0061 (6)	0.0006 (6)
C7	0.0241 (7)	0.0286 (7)	0.0215 (8)	0.0026 (6)	0.0024 (7)	0.0049 (6)
C8	0.0229 (7)	0.0295 (8)	0.0164 (7)	−0.0005 (6)	−0.0005 (5)	0.0004 (6)
C9	0.0182 (6)	0.0234 (7)	0.0159 (7)	−0.0011 (5)	0.0030 (5)	0.0017 (6)
C10	0.0623 (13)	0.0286 (9)	0.0250 (9)	0.0078 (9)	−0.0066 (9)	−0.0059 (7)
C11	0.0165 (6)	0.0319 (8)	0.0237 (8)	0.0022 (6)	−0.0013 (7)	0.0036 (6)
C12	0.0169 (6)	0.0242 (7)	0.0205 (7)	0.0047 (6)	−0.0025 (5)	0.0039 (6)
C13	0.0252 (7)	0.0236 (7)	0.0251 (8)	0.0041 (7)	−0.0031 (7)	0.0005 (6)
C14	0.0300 (8)	0.0236 (7)	0.0345 (9)	−0.0001 (7)	−0.0037 (8)	0.0073 (7)
C15	0.0275 (8)	0.0345 (9)	0.0311 (9)	0.0036 (7)	0.0018 (7)	0.0131 (7)
C16	0.0335 (8)	0.0354 (9)	0.0216 (8)	0.0077 (7)	0.0013 (6)	0.0021 (7)
C17	0.0296 (8)	0.0260 (8)	0.0246 (9)	0.0011 (6)	−0.0038 (6)	−0.0011 (7)

Geometric parameters (Å, º)

Br1—C6	1.9030 (16)	C8—H8	0.9500
O1—C1	1.3570 (19)	C10—H10A	0.9800
O1—C10	1.430 (2)	C10—H10B	0.9800
N1—C1	1.305 (2)	C10—H10C	0.9800
N1—C9	1.373 (2)	C11—C12	1.516 (2)
C1—C2	1.430 (2)	C11—H11A	0.9900
C2—C3	1.361 (2)	C11—H11B	0.9900
C2—C11	1.515 (2)	C12—C13	1.393 (2)
C3—C4	1.424 (2)	C12—C17	1.396 (2)
C3—H3	0.9500	C13—C14	1.391 (3)
C4—C9	1.415 (2)	C13—H13	0.9500
C4—C5	1.415 (2)	C14—C15	1.380 (3)
C5—C6	1.373 (2)	C14—H14	0.9500
C5—H5	0.9500	C15—C16	1.386 (3)
C6—C7	1.399 (3)	C15—H15	0.9500
C7—C8	1.374 (2)	C16—C17	1.387 (3)
C7—H7	0.9500	C16—H16	0.9500
C8—C9	1.413 (2)	C17—H17	0.9500
C1—O1—C10	116.15 (14)	O1—C10—H10B	109.5
C1—N1—C9	117.37 (14)	H10A—C10—H10B	109.5
N1—C1—O1	119.16 (14)	O1—C10—H10C	109.5
N1—C1—C2	125.67 (15)	H10A—C10—H10C	109.5
O1—C1—C2	115.16 (14)	H10B—C10—H10C	109.5
C3—C2—C1	116.59 (15)	C2—C11—C12	111.49 (13)
C3—C2—C11	122.27 (16)	C2—C11—H11A	109.3
C1—C2—C11	121.09 (15)	C12—C11—H11A	109.3
C2—C3—C4	120.69 (15)	C2—C11—H11B	109.3
C2—C3—H3	119.7	C12—C11—H11B	109.3
C4—C3—H3	119.7	H11A—C11—H11B	108.0
C9—C4—C5	119.53 (14)	C13—C12—C17	118.60 (15)
C9—C4—C3	117.37 (15)	C13—C12—C11	121.08 (15)
C5—C4—C3	123.10 (15)	C17—C12—C11	120.30 (15)
C6—C5—C4	118.88 (15)	C14—C13—C12	120.44 (16)
C6—C5—H5	120.6	C14—C13—H13	119.8
C4—C5—H5	120.6	C12—C13—H13	119.8
C5—C6—C7	122.42 (15)	C15—C14—C13	120.45 (16)
C5—C6—Br1	119.21 (13)	C15—C14—H14	119.8
C7—C6—Br1	118.36 (12)	C13—C14—H14	119.8
C8—C7—C6	119.15 (16)	C14—C15—C16	119.61 (17)
C8—C7—H7	120.4	C14—C15—H15	120.2
C6—C7—H7	120.4	C16—C15—H15	120.2
C7—C8—C9	120.69 (16)	C15—C16—C17	120.23 (17)
C7—C8—H8	119.7	C15—C16—H16	119.9
C9—C8—H8	119.7	C17—C16—H16	119.9
N1—C9—C8	118.41 (15)	C16—C17—C12	120.66 (16)
N1—C9—C4	122.27 (14)	C16—C17—H17	119.7
C8—C9—C4	119.32 (15)	C12—C17—H17	119.7
O1—C10—H10A	109.5
C9—N1—C1—O1	179.86 (14)	C1—N1—C9—C4	1.0 (2)
C9—N1—C1—C2	0.5 (2)	C7—C8—C9—N1	−179.29 (15)
C10—O1—C1—N1	2.2 (2)	C7—C8—C9—C4	1.0 (2)
C10—O1—C1—C2	−178.34 (16)	C5—C4—C9—N1	179.02 (14)
N1—C1—C2—C3	−2.0 (2)	C3—C4—C9—N1	−1.0 (2)
O1—C1—C2—C3	178.66 (14)	C5—C4—C9—C8	−1.2 (2)
N1—C1—C2—C11	175.74 (16)	C3—C4—C9—C8	178.69 (14)
O1—C1—C2—C11	−3.6 (2)	C3—C2—C11—C12	88.62 (19)
C1—C2—C3—C4	1.9 (2)	C1—C2—C11—C12	−88.96 (19)
C11—C2—C3—C4	−175.82 (14)	C2—C11—C12—C13	87.29 (18)
C2—C3—C4—C9	−0.5 (2)	C2—C11—C12—C17	−91.38 (18)
C2—C3—C4—C5	179.43 (14)	C17—C12—C13—C14	−0.1 (2)
C9—C4—C5—C6	1.0 (2)	C11—C12—C13—C14	−178.79 (15)
C3—C4—C5—C6	−178.96 (15)	C12—C13—C14—C15	−0.6 (3)
C4—C5—C6—C7	−0.4 (3)	C13—C14—C15—C16	0.6 (3)
C4—C5—C6—Br1	178.51 (11)	C14—C15—C16—C17	0.1 (3)
C5—C6—C7—C8	0.1 (3)	C15—C16—C17—C12	−0.7 (3)
Br1—C6—C7—C8	−178.82 (13)	C13—C12—C17—C16	0.7 (2)
C6—C7—C8—C9	−0.4 (2)	C11—C12—C17—C16	179.44 (15)
C1—N1—C9—C8	−178.70 (15)

[4-(6-Bromo-2-methoxyquinolin-3-yl)-3-hydroxy-3-(naphthalen-1-yl)-4-phenylbutyl]dimethylazanium benzoate hydrate (4a)

Crystal data

C32H32BrN2O2^+·C7H5O2^−·1.166H2O	F(000) = 727
Mr = 698.70	Dx = 1.342 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 12.6384 (5) Å	Cell parameters from 9883 reflections
b = 7.9259 (3) Å	θ = 2.4–31.0°
c = 17.5249 (8) Å	µ = 1.24 mm^−1
β = 99.8450 (17)°	T = 150 K
V = 1729.63 (12) Å^3	Rod, colourless
Z = 2	0.55 × 0.21 × 0.13 mm

Data collection

Bruker D8 Quest diffractometer with PhotonII charge-integrating pixel array detector (CPAD)	13080 independent reflections
Radiation source: fine focus sealed tube X-ray source	10456 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromator	Rint = 0.049
Detector resolution: 7.4074 pixels mm^-1	θmax = 33.2°, θmin = 2.4°
ω and phi scans	h = −19→19
Absorption correction: multi-scan (SADABS2016; Krause et al., 2015)	k = −11→12
Tmin = 0.638, Tmax = 0.746	l = −26→26
80228 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.073	w = 1/[σ^2(Fo^2) + (0.0275P)^2 + 0.0775P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
13080 reflections	Δρmax = 0.36 e Å^−3
445 parameters	Δρmin = −0.48 e Å^−3
5 restraints	Absolute structure: Flack x determined using 4051 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.006 (3)

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	1.08589 (2)	0.23491 (3)	−0.10932 (2)	0.03179 (6)
O1	0.75158 (11)	0.32496 (17)	0.21175 (8)	0.0226 (3)
H1B	0.726 (2)	0.2891 (12)	0.1673 (15)	0.034*
O2	1.09216 (11)	0.03313 (19)	0.34490 (8)	0.0250 (3)
O3	0.45306 (14)	0.2726 (2)	0.05187 (10)	0.0416 (4)
O4	0.33269 (13)	0.4451 (2)	−0.01531 (8)	0.0313 (3)
O5	0.67059 (14)	0.2732 (2)	0.06194 (9)	0.0333 (4)
H5D	0.678 (3)	0.173 (5)	0.0399 (18)	0.050*
H5E	0.609 (3)	0.282 (4)	0.0580 (18)	0.050*
O6	1.3652 (11)	−0.1662 (18)	0.2755 (8)	0.061 (5)	0.166 (7)
H6D	1.381796	−0.060138	0.281851	0.091*	0.166 (7)
H6E	1.295716	−0.160377	0.260652	0.091*	0.166 (7)
N1	0.59081 (12)	−0.1394 (2)	0.14129 (9)	0.0209 (3)
H1	0.621515	−0.107941	0.094301	0.025*
N2	1.14361 (13)	0.0185 (2)	0.22591 (10)	0.0245 (3)
C1	0.89931 (14)	0.1917 (2)	0.29663 (10)	0.0177 (3)
H1A	0.912833	0.105727	0.338929	0.021*
C2	0.77558 (14)	0.1863 (2)	0.26328 (10)	0.0183 (3)
C3	0.74525 (14)	0.0197 (2)	0.21876 (10)	0.0189 (3)
H3A	0.773132	0.022355	0.169312	0.023*
H3B	0.779760	−0.075971	0.249780	0.023*
C4	0.62435 (14)	−0.0081 (3)	0.20190 (10)	0.0211 (3)
H4A	0.599796	−0.042486	0.250303	0.025*
H4B	0.588573	0.099757	0.184672	0.025*
C5	0.62902 (18)	−0.3115 (3)	0.16528 (14)	0.0318 (5)
H5A	0.607261	−0.390295	0.122359	0.048*
H5B	0.597537	−0.346948	0.210080	0.048*
H5C	0.707487	−0.311025	0.179237	0.048*
C6	0.47158 (16)	−0.1387 (3)	0.11978 (13)	0.0306 (4)
H6A	0.447484	−0.027521	0.099337	0.046*
H6B	0.439568	−0.163370	0.165684	0.046*
H6C	0.449243	−0.224808	0.080161	0.046*
C7	0.71486 (13)	0.2170 (3)	0.33194 (9)	0.0202 (3)
C8	0.66495 (17)	0.3697 (3)	0.33479 (12)	0.0292 (4)
H8	0.666506	0.447440	0.293730	0.035*
C9	0.6113 (2)	0.4171 (3)	0.39581 (13)	0.0376 (5)
H9	0.578160	0.524760	0.395368	0.045*
C10	0.6071 (2)	0.3088 (3)	0.45499 (13)	0.0365 (5)
H10	0.571006	0.340816	0.496032	0.044*
C11	0.65593 (18)	0.1492 (3)	0.45603 (12)	0.0315 (5)
C12	0.6518 (2)	0.0367 (4)	0.51821 (15)	0.0478 (7)
H12	0.615365	0.070222	0.558867	0.057*
C13	0.6981 (3)	−0.1164 (4)	0.52119 (18)	0.0583 (8)
H13	0.693912	−0.189679	0.563465	0.070*
C14	0.7528 (2)	−0.1682 (4)	0.46177 (16)	0.0469 (7)
H14	0.785004	−0.276756	0.463796	0.056*
C15	0.75993 (18)	−0.0622 (3)	0.40071 (12)	0.0304 (4)
H15	0.798548	−0.098306	0.361670	0.036*
C16	0.71136 (16)	0.0992 (3)	0.39441 (11)	0.0239 (4)
C17	0.93134 (14)	0.3615 (2)	0.33346 (10)	0.0187 (3)
C18	0.93961 (18)	0.3834 (3)	0.41341 (11)	0.0268 (4)
H18	0.925381	0.291144	0.444733	0.032*
C19	0.9683 (2)	0.5381 (3)	0.44745 (11)	0.0327 (5)
H19	0.973412	0.551193	0.501838	0.039*
C20	0.98963 (19)	0.6738 (3)	0.40278 (11)	0.0314 (5)
H20	1.010481	0.779369	0.426327	0.038*
C21	0.98022 (19)	0.6541 (3)	0.32309 (11)	0.0292 (4)
H21	0.993225	0.747126	0.291782	0.035*
C22	0.95196 (17)	0.4994 (3)	0.28939 (11)	0.0254 (4)
H22	0.946527	0.487081	0.234939	0.031*
C23	0.97303 (14)	0.1486 (2)	0.23939 (10)	0.0188 (3)
C24	0.95734 (14)	0.1960 (2)	0.16317 (10)	0.0199 (4)
H24	0.894360	0.256618	0.141861	0.024*
C25	1.03406 (14)	0.1555 (3)	0.11563 (11)	0.0209 (3)
C26	1.02197 (14)	0.2073 (3)	0.03709 (10)	0.0230 (4)
H26	0.961896	0.272839	0.014304	0.028*
C27	1.09881 (16)	0.1605 (3)	−0.00506 (11)	0.0239 (4)
C28	1.18724 (16)	0.0604 (3)	0.02554 (12)	0.0282 (4)
H28	1.237701	0.026726	−0.005945	0.034*
C29	1.19988 (17)	0.0116 (3)	0.10170 (13)	0.0289 (4)
H29	1.259621	−0.056265	0.123021	0.035*
C30	1.12503 (15)	0.0612 (3)	0.14873 (11)	0.0226 (4)
C31	1.07295 (15)	0.0640 (2)	0.26745 (11)	0.0207 (3)
C32	1.19411 (18)	−0.0419 (3)	0.37533 (14)	0.0364 (5)
H32A	1.197179	−0.156057	0.354303	0.055*
H32B	1.202846	−0.047604	0.431923	0.055*
H32C	1.251863	0.026661	0.360523	0.055*
C33	0.37747 (16)	0.3748 (3)	0.04720 (12)	0.0258 (4)
C34	0.33351 (16)	0.4182 (3)	0.11951 (11)	0.0244 (4)
C35	0.23897 (19)	0.5090 (3)	0.11598 (13)	0.0331 (5)
H35	0.202051	0.548308	0.067447	0.040*
C36	0.1981 (2)	0.5426 (4)	0.18289 (15)	0.0487 (7)
H36	0.133006	0.603990	0.179969	0.058*
C37	0.2515 (2)	0.4876 (5)	0.25356 (15)	0.0531 (8)
H37	0.223153	0.510905	0.299262	0.064*
C38	0.3462 (2)	0.3986 (4)	0.25814 (14)	0.0523 (8)
H38	0.383205	0.360736	0.306920	0.063*
C39	0.3871 (2)	0.3647 (4)	0.19136 (13)	0.0394 (6)
H39	0.452599	0.304104	0.194674	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.03261 (10)	0.04237 (12)	0.02255 (8)	−0.00372 (11)	0.01087 (6)	−0.00332 (10)
O1	0.0289 (7)	0.0205 (7)	0.0173 (6)	0.0052 (5)	0.0002 (5)	0.0021 (5)
O2	0.0232 (6)	0.0262 (7)	0.0241 (6)	0.0044 (5)	−0.0002 (5)	0.0040 (6)
O3	0.0426 (9)	0.0432 (12)	0.0433 (9)	0.0160 (8)	0.0199 (7)	0.0064 (7)
O4	0.0368 (8)	0.0339 (8)	0.0242 (7)	0.0011 (7)	0.0077 (6)	0.0028 (6)
O5	0.0398 (8)	0.0321 (10)	0.0241 (7)	−0.0038 (7)	−0.0054 (6)	0.0037 (6)
O6	0.062 (9)	0.057 (9)	0.070 (10)	0.003 (6)	0.029 (7)	−0.006 (7)
N1	0.0207 (7)	0.0233 (8)	0.0181 (7)	−0.0019 (6)	0.0012 (6)	−0.0003 (6)
N2	0.0190 (7)	0.0245 (9)	0.0302 (8)	0.0031 (6)	0.0047 (6)	0.0034 (7)
C1	0.0204 (7)	0.0174 (9)	0.0154 (7)	0.0014 (6)	0.0036 (6)	0.0016 (6)
C2	0.0196 (7)	0.0195 (9)	0.0159 (7)	0.0018 (6)	0.0032 (6)	−0.0006 (6)
C3	0.0189 (8)	0.0194 (9)	0.0186 (7)	0.0017 (6)	0.0035 (6)	−0.0004 (6)
C4	0.0192 (8)	0.0245 (9)	0.0199 (8)	0.0000 (7)	0.0044 (6)	−0.0035 (7)
C5	0.0311 (10)	0.0230 (11)	0.0404 (11)	−0.0007 (8)	0.0036 (9)	0.0005 (8)
C6	0.0209 (9)	0.0387 (12)	0.0301 (10)	−0.0047 (8)	−0.0022 (8)	0.0033 (9)
C7	0.0202 (7)	0.0236 (10)	0.0166 (6)	0.0026 (8)	0.0023 (5)	−0.0022 (7)
C8	0.0322 (10)	0.0302 (11)	0.0265 (9)	0.0085 (9)	0.0091 (8)	0.0004 (8)
C9	0.0412 (12)	0.0380 (13)	0.0367 (12)	0.0113 (10)	0.0158 (10)	−0.0068 (10)
C10	0.0343 (11)	0.0499 (14)	0.0285 (10)	0.0041 (10)	0.0144 (9)	−0.0078 (10)
C11	0.0292 (11)	0.0426 (13)	0.0251 (9)	−0.0040 (10)	0.0112 (8)	−0.0013 (9)
C12	0.0601 (17)	0.0552 (17)	0.0344 (12)	0.0006 (14)	0.0257 (12)	0.0081 (12)
C13	0.080 (2)	0.0565 (19)	0.0468 (16)	0.0065 (16)	0.0342 (15)	0.0234 (14)
C14	0.0606 (17)	0.0397 (15)	0.0450 (14)	0.0093 (12)	0.0225 (12)	0.0186 (12)
C15	0.0355 (11)	0.0291 (11)	0.0284 (10)	0.0000 (9)	0.0105 (8)	0.0047 (8)
C16	0.0234 (9)	0.0281 (10)	0.0205 (8)	−0.0027 (7)	0.0050 (7)	−0.0008 (7)
C17	0.0206 (8)	0.0189 (8)	0.0159 (7)	0.0014 (7)	0.0008 (6)	0.0010 (6)
C18	0.0401 (11)	0.0225 (10)	0.0165 (8)	−0.0047 (8)	0.0008 (7)	0.0027 (7)
C19	0.0522 (13)	0.0290 (11)	0.0154 (8)	−0.0069 (10)	0.0018 (8)	−0.0016 (8)
C20	0.0500 (13)	0.0219 (10)	0.0209 (9)	−0.0066 (9)	0.0020 (8)	−0.0027 (8)
C21	0.0471 (12)	0.0200 (10)	0.0206 (8)	−0.0058 (9)	0.0058 (8)	0.0013 (7)
C22	0.0379 (11)	0.0223 (10)	0.0169 (8)	−0.0046 (8)	0.0068 (7)	0.0003 (7)
C23	0.0179 (8)	0.0164 (9)	0.0220 (8)	0.0001 (6)	0.0032 (6)	−0.0011 (7)
C24	0.0184 (7)	0.0212 (10)	0.0204 (7)	0.0026 (6)	0.0042 (6)	0.0005 (6)
C25	0.0188 (8)	0.0212 (9)	0.0238 (8)	−0.0004 (7)	0.0063 (6)	−0.0015 (7)
C26	0.0221 (8)	0.0252 (11)	0.0223 (7)	0.0006 (7)	0.0054 (6)	−0.0013 (7)
C27	0.0259 (9)	0.0238 (9)	0.0237 (8)	−0.0052 (7)	0.0093 (7)	−0.0043 (8)
C28	0.0222 (9)	0.0302 (11)	0.0349 (11)	−0.0013 (8)	0.0125 (8)	−0.0059 (9)
C29	0.0212 (9)	0.0293 (11)	0.0378 (11)	0.0035 (8)	0.0100 (8)	0.0003 (9)
C30	0.0195 (8)	0.0209 (9)	0.0283 (9)	0.0004 (7)	0.0062 (7)	0.0001 (7)
C31	0.0200 (8)	0.0174 (8)	0.0238 (8)	−0.0014 (7)	0.0013 (7)	0.0011 (7)
C32	0.0299 (11)	0.0417 (14)	0.0333 (11)	0.0097 (10)	−0.0070 (9)	0.0046 (10)
C33	0.0273 (9)	0.0243 (10)	0.0272 (9)	−0.0023 (8)	0.0083 (7)	0.0008 (8)
C34	0.0254 (9)	0.0241 (10)	0.0240 (9)	0.0001 (7)	0.0049 (7)	−0.0013 (7)
C35	0.0313 (11)	0.0417 (14)	0.0259 (10)	0.0102 (10)	0.0042 (8)	0.0009 (9)
C36	0.0409 (13)	0.0683 (19)	0.0383 (13)	0.0234 (13)	0.0110 (11)	−0.0028 (13)
C37	0.0581 (17)	0.076 (2)	0.0279 (11)	0.0201 (15)	0.0141 (11)	−0.0082 (13)
C38	0.0554 (16)	0.076 (2)	0.0248 (11)	0.0252 (15)	0.0053 (11)	0.0020 (12)
C39	0.0383 (12)	0.0507 (15)	0.0294 (11)	0.0190 (11)	0.0061 (9)	0.0023 (10)

Geometric parameters (Å, º)

Br1—C27	1.900 (2)	C13—C14	1.406 (4)
O1—C2	1.422 (2)	C13—H13	0.9500
O1—H1B	0.84 (3)	C14—C15	1.375 (3)
O2—C31	1.360 (2)	C14—H14	0.9500
O2—C32	1.437 (2)	C15—C16	1.414 (3)
O3—C33	1.244 (3)	C15—H15	0.9500
O4—C33	1.273 (3)	C17—C22	1.388 (3)
O5—H5D	0.90 (4)	C17—C18	1.398 (3)
O5—H5E	0.77 (3)	C18—C19	1.385 (3)
O6—H6D	0.8692	C18—H18	0.9500
O6—H6E	0.8735	C19—C20	1.383 (3)
N1—C5	1.484 (3)	C19—H19	0.9500
N1—C6	1.489 (2)	C20—C21	1.390 (3)
N1—C4	1.495 (2)	C20—H20	0.9500
N1—H1	1.0000	C21—C22	1.381 (3)
N2—C31	1.296 (2)	C21—H21	0.9500
N2—C30	1.375 (3)	C22—H22	0.9500
C1—C17	1.517 (2)	C23—C24	1.369 (2)
C1—C23	1.520 (2)	C23—C31	1.440 (3)
C1—C2	1.574 (2)	C24—C25	1.419 (2)
C1—H1A	1.0000	C24—H24	0.9500
C2—C3	1.548 (3)	C25—C30	1.410 (3)
C2—C7	1.553 (2)	C25—C26	1.419 (3)
C3—C4	1.522 (2)	C26—C27	1.368 (3)
C3—H3A	0.9900	C26—H26	0.9500
C3—H3B	0.9900	C27—C28	1.401 (3)
C4—H4A	0.9900	C28—C29	1.372 (3)
C4—H4B	0.9900	C28—H28	0.9500
C5—H5A	0.9800	C29—C30	1.413 (3)
C5—H5B	0.9800	C29—H29	0.9500
C5—H5C	0.9800	C32—H32A	0.9800
C6—H6A	0.9800	C32—H32B	0.9800
C6—H6B	0.9800	C32—H32C	0.9800
C6—H6C	0.9800	C33—C34	1.508 (3)
C7—C8	1.369 (3)	C34—C35	1.387 (3)
C7—C16	1.446 (3)	C34—C39	1.390 (3)
C8—C9	1.412 (3)	C35—C36	1.385 (3)
C8—H8	0.9500	C35—H35	0.9500
C9—C10	1.354 (4)	C36—C37	1.376 (4)
C9—H9	0.9500	C36—H36	0.9500
C10—C11	1.406 (3)	C37—C38	1.380 (4)
C10—H10	0.9500	C37—H37	0.9500
C11—C12	1.416 (3)	C38—C39	1.384 (3)
C11—C16	1.440 (3)	C38—H38	0.9500
C12—C13	1.345 (5)	C39—H39	0.9500
C12—H12	0.9500
C2—O1—H1B	109.5	C15—C16—C7	125.05 (18)
C31—O2—C32	116.16 (16)	C11—C16—C7	118.14 (19)
H5D—O5—H5E	103 (3)	C22—C17—C18	118.08 (17)
H6D—O6—H6E	101.2	C22—C17—C1	121.56 (15)
C5—N1—C6	109.94 (17)	C18—C17—C1	120.36 (16)
C5—N1—C4	113.54 (15)	C19—C18—C17	120.74 (18)
C6—N1—C4	109.21 (16)	C19—C18—H18	119.6
C5—N1—H1	108.0	C17—C18—H18	119.6
C6—N1—H1	108.0	C20—C19—C18	120.44 (18)
C4—N1—H1	108.0	C20—C19—H19	119.8
C31—N2—C30	117.76 (16)	C18—C19—H19	119.8
C17—C1—C23	109.33 (14)	C19—C20—C21	119.3 (2)
C17—C1—C2	110.99 (14)	C19—C20—H20	120.3
C23—C1—C2	115.54 (14)	C21—C20—H20	120.3
C17—C1—H1A	106.8	C22—C21—C20	120.05 (19)
C23—C1—H1A	106.8	C22—C21—H21	120.0
C2—C1—H1A	106.8	C20—C21—H21	120.0
O1—C2—C3	109.36 (14)	C21—C22—C17	121.36 (17)
O1—C2—C7	106.90 (15)	C21—C22—H22	119.3
C3—C2—C7	114.32 (15)	C17—C22—H22	119.3
O1—C2—C1	107.77 (14)	C24—C23—C31	115.67 (16)
C3—C2—C1	110.81 (14)	C24—C23—C1	125.41 (16)
C7—C2—C1	107.42 (13)	C31—C23—C1	118.68 (16)
C4—C3—C2	112.06 (15)	C23—C24—C25	120.77 (16)
C4—C3—H3A	109.2	C23—C24—H24	119.6
C2—C3—H3A	109.2	C25—C24—H24	119.6
C4—C3—H3B	109.2	C30—C25—C24	117.98 (17)
C2—C3—H3B	109.2	C30—C25—C26	119.80 (16)
H3A—C3—H3B	107.9	C24—C25—C26	122.23 (17)
N1—C4—C3	113.09 (15)	C27—C26—C25	118.48 (18)
N1—C4—H4A	109.0	C27—C26—H26	120.8
C3—C4—H4A	109.0	C25—C26—H26	120.8
N1—C4—H4B	109.0	C26—C27—C28	122.72 (19)
C3—C4—H4B	109.0	C26—C27—Br1	118.87 (16)
H4A—C4—H4B	107.8	C28—C27—Br1	118.41 (14)
N1—C5—H5A	109.5	C29—C28—C27	118.98 (18)
N1—C5—H5B	109.5	C29—C28—H28	120.5
H5A—C5—H5B	109.5	C27—C28—H28	120.5
N1—C5—H5C	109.5	C28—C29—C30	120.7 (2)
H5A—C5—H5C	109.5	C28—C29—H29	119.6
H5B—C5—H5C	109.5	C30—C29—H29	119.6
N1—C6—H6A	109.5	N2—C30—C25	121.68 (17)
N1—C6—H6B	109.5	N2—C30—C29	119.12 (18)
H6A—C6—H6B	109.5	C25—C30—C29	119.19 (18)
N1—C6—H6C	109.5	N2—C31—O2	119.21 (17)
H6A—C6—H6C	109.5	N2—C31—C23	125.87 (17)
H6B—C6—H6C	109.5	O2—C31—C23	114.92 (16)
C8—C7—C16	118.01 (16)	O2—C32—H32A	109.5
C8—C7—C2	117.30 (17)	O2—C32—H32B	109.5
C16—C7—C2	124.64 (18)	H32A—C32—H32B	109.5
C7—C8—C9	123.1 (2)	O2—C32—H32C	109.5
C7—C8—H8	118.4	H32A—C32—H32C	109.5
C9—C8—H8	118.4	H32B—C32—H32C	109.5
C10—C9—C8	119.9 (2)	O3—C33—O4	124.42 (19)
C10—C9—H9	120.1	O3—C33—C34	118.83 (19)
C8—C9—H9	120.1	O4—C33—C34	116.74 (18)
C9—C10—C11	120.4 (2)	C35—C34—C39	118.76 (19)
C9—C10—H10	119.8	C35—C34—C33	121.28 (18)
C11—C10—H10	119.8	C39—C34—C33	119.95 (19)
C10—C11—C12	120.2 (2)	C36—C35—C34	120.3 (2)
C10—C11—C16	120.5 (2)	C36—C35—H35	119.8
C12—C11—C16	119.3 (2)	C34—C35—H35	119.8
C13—C12—C11	121.7 (2)	C37—C36—C35	120.3 (2)
C13—C12—H12	119.2	C37—C36—H36	119.9
C11—C12—H12	119.2	C35—C36—H36	119.9
C12—C13—C14	120.0 (2)	C36—C37—C38	120.1 (2)
C12—C13—H13	120.0	C36—C37—H37	120.0
C14—C13—H13	120.0	C38—C37—H37	120.0
C15—C14—C13	120.3 (3)	C37—C38—C39	119.7 (2)
C15—C14—H14	119.9	C37—C38—H38	120.1
C13—C14—H14	119.9	C39—C38—H38	120.1
C14—C15—C16	121.9 (2)	C38—C39—C34	120.8 (2)
C14—C15—H15	119.1	C38—C39—H39	119.6
C16—C15—H15	119.1	C34—C39—H39	119.6
C15—C16—C11	116.81 (19)
C17—C1—C2—O1	54.82 (17)	C19—C20—C21—C22	−1.3 (4)
C23—C1—C2—O1	−70.37 (18)	C20—C21—C22—C17	0.7 (3)
C17—C1—C2—C3	174.44 (14)	C18—C17—C22—C21	0.2 (3)
C23—C1—C2—C3	49.3 (2)	C1—C17—C22—C21	179.44 (19)
C17—C1—C2—C7	−60.05 (19)	C17—C1—C23—C24	−87.3 (2)
C23—C1—C2—C7	174.77 (16)	C2—C1—C23—C24	38.7 (2)
O1—C2—C3—C4	−74.49 (18)	C17—C1—C23—C31	86.83 (19)
C7—C2—C3—C4	45.3 (2)	C2—C1—C23—C31	−147.14 (16)
C1—C2—C3—C4	166.84 (14)	C31—C23—C24—C25	2.7 (3)
C5—N1—C4—C3	65.8 (2)	C1—C23—C24—C25	177.00 (17)
C6—N1—C4—C3	−171.11 (16)	C23—C24—C25—C30	1.8 (3)
C2—C3—C4—N1	164.04 (15)	C23—C24—C25—C26	−177.98 (18)
O1—C2—C7—C8	−7.6 (2)	C30—C25—C26—C27	1.3 (3)
C3—C2—C7—C8	−128.77 (19)	C24—C25—C26—C27	−178.92 (18)
C1—C2—C7—C8	107.84 (18)	C25—C26—C27—C28	1.7 (3)
O1—C2—C7—C16	175.18 (17)	C25—C26—C27—Br1	−178.04 (14)
C3—C2—C7—C16	54.0 (2)	C26—C27—C28—C29	−2.4 (3)
C1—C2—C7—C16	−69.4 (2)	Br1—C27—C28—C29	177.34 (17)
C16—C7—C8—C9	0.4 (3)	C27—C28—C29—C30	0.0 (3)
C2—C7—C8—C9	−177.0 (2)	C31—N2—C30—C25	1.8 (3)
C7—C8—C9—C10	−0.4 (4)	C31—N2—C30—C29	−179.23 (19)
C8—C9—C10—C11	0.0 (4)	C24—C25—C30—N2	−4.3 (3)
C9—C10—C11—C12	179.7 (3)	C26—C25—C30—N2	175.47 (18)
C9—C10—C11—C16	0.3 (3)	C24—C25—C30—C29	176.72 (18)
C10—C11—C12—C13	−179.6 (3)	C26—C25—C30—C29	−3.5 (3)
C16—C11—C12—C13	−0.2 (4)	C28—C29—C30—N2	−176.2 (2)
C11—C12—C13—C14	0.3 (5)	C28—C29—C30—C25	2.8 (3)
C12—C13—C14—C15	0.5 (5)	C30—N2—C31—O2	−175.89 (17)
C13—C14—C15—C16	−1.4 (4)	C30—N2—C31—C23	3.4 (3)
C14—C15—C16—C11	1.4 (3)	C32—O2—C31—N2	3.0 (3)
C14—C15—C16—C7	−179.7 (2)	C32—O2—C31—C23	−176.38 (18)
C10—C11—C16—C15	178.8 (2)	C24—C23—C31—N2	−5.7 (3)
C12—C11—C16—C15	−0.6 (3)	C1—C23—C31—N2	179.65 (18)
C10—C11—C16—C7	−0.2 (3)	C24—C23—C31—O2	173.63 (16)
C12—C11—C16—C7	−179.6 (2)	C1—C23—C31—O2	−1.1 (2)
C8—C7—C16—C15	−179.1 (2)	O3—C33—C34—C35	−169.4 (2)
C2—C7—C16—C15	−1.9 (3)	O4—C33—C34—C35	9.7 (3)
C8—C7—C16—C11	−0.2 (3)	O3—C33—C34—C39	9.6 (3)
C2—C7—C16—C11	177.02 (17)	O4—C33—C34—C39	−171.3 (2)
C23—C1—C17—C22	46.1 (2)	C39—C34—C35—C36	−1.2 (4)
C2—C1—C17—C22	−82.5 (2)	C33—C34—C35—C36	177.8 (3)
C23—C1—C17—C18	−134.71 (18)	C34—C35—C36—C37	0.6 (5)
C2—C1—C17—C18	96.7 (2)	C35—C36—C37—C38	0.1 (5)
C22—C17—C18—C19	−0.5 (3)	C36—C37—C38—C39	−0.1 (5)
C1—C17—C18—C19	−179.7 (2)	C37—C38—C39—C34	−0.5 (5)
C17—C18—C19—C20	−0.2 (4)	C35—C34—C39—C38	1.1 (4)
C18—C19—C20—C21	1.1 (4)	C33—C34—C39—C38	−177.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O5	0.84	1.87	2.681 (2)	164
O5—H5D···O4^i	0.90 (4)	1.85 (4)	2.724 (2)	163 (3)
O5—H5E···O3	0.77 (3)	1.96 (3)	2.724 (2)	172 (4)
O6—H6E···N2	0.87	2.38	3.148 (13)	147
N1—H1···O4^i	1.00	1.64	2.643 (2)	178
C5—H5C···Br1^ii	0.98	3.09	3.910 (2)	142
C6—H6A···O3	0.98	2.53	3.465 (3)	161
C6—H6B···O6^iii	0.98	2.28	3.249 (13)	169
C28—H28···O5^ii	0.95	2.59	3.421 (3)	146

Symmetry codes: (i) −x+1, y−1/2, −z; (ii) −x+2, y−1/2, −z; (iii) x−1, y, z.

[4-(6-Bromo-2-methoxyquinolin-3-yl)-3-hydroxy-3-(naphthalen-1-yl)-4-phenylbutyl]dimethylazanium benzoate acetonitrile 0.742-solvate monohydrate (4b)

Crystal data

C32H32BrN2O2^+·C7H5O2^−·0.742C2H3N·H2O	F(000) = 757
Mr = 726.10	Dx = 1.360 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
a = 12.8661 (8) Å	Cell parameters from 9023 reflections
b = 8.0386 (5) Å	θ = 2.6–79.1°
c = 17.4704 (10) Å	µ = 1.97 mm^−1
β = 101.093 (3)°	T = 150 K
V = 1773.13 (19) Å^3	Needle, colourless
Z = 2	0.31 × 0.05 × 0.05 mm

Data collection

Bruker D8 Quest diffractometer with PhotonIII_C14 charge-integrating and photon counting pixel array detector	7360 independent reflections
Radiation source: I-mu-S microsource X-ray tube	6750 reflections with I > 2σ(I)
Laterally graded multilayer (Goebel) mirror monochromator	Rint = 0.060
Detector resolution: 7.4074 pixels mm^-1	θmax = 80.1°, θmin = 2.6°
ω and phi scans	h = −16→16
Absorption correction: multi-scan (SADABS2016; Krause et al., 2015)	k = −8→10
Tmin = 0.599, Tmax = 0.754	l = −22→22
39739 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.085	w = 1/[σ^2(Fo^2) + (0.0233P)^2 + 1.042P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
7360 reflections	Δρmax = 0.40 e Å^−3
515 parameters	Δρmin = −0.50 e Å^−3
195 restraints	Absolute structure: Flack x determined using 2778 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: isomorphous structure methods	Absolute structure parameter: 0.004 (8)

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	1.09186 (3)	0.23149 (6)	−0.10436 (2)	0.04184 (12)
O1	0.7542 (2)	0.3259 (3)	0.20992 (15)	0.0271 (5)
H1B	0.734 (4)	0.292 (2)	0.168 (3)	0.041*
O2	1.08646 (19)	0.0320 (3)	0.35039 (14)	0.0297 (5)
O3	0.4583 (2)	0.2868 (4)	0.05847 (18)	0.0497 (8)
O4	0.3385 (2)	0.4448 (4)	−0.01724 (15)	0.0373 (6)
O5	0.6707 (3)	0.2738 (4)	0.05844 (16)	0.0387 (7)
H5D	0.674 (5)	0.174 (4)	0.041 (3)	0.058*
H5E	0.607 (2)	0.288 (7)	0.058 (3)	0.058*
N1	0.5911 (2)	−0.1342 (4)	0.14353 (17)	0.0272 (6)
H1	0.618783	−0.106871	0.095314	0.033*
N2	1.1414 (2)	0.0196 (4)	0.23270 (18)	0.0292 (6)
C1	0.9000 (2)	0.1962 (4)	0.29767 (17)	0.0228 (7)
H1A	0.913127	0.113403	0.341185	0.027*
C2	0.7781 (3)	0.1907 (4)	0.26263 (18)	0.0228 (7)
C3	0.7471 (3)	0.0265 (4)	0.21840 (19)	0.0234 (7)
H3A	0.772164	0.028938	0.168253	0.028*
H3B	0.782695	−0.067448	0.249584	0.028*
C4	0.6277 (3)	−0.0017 (5)	0.20251 (19)	0.0249 (7)
H4A	0.605984	−0.032128	0.252035	0.030*
H4B	0.591887	0.103914	0.184090	0.030*
C5	0.6308 (3)	−0.3018 (5)	0.1703 (2)	0.0391 (9)
H5A	0.605300	−0.383658	0.129406	0.059*
H5B	0.604938	−0.331264	0.217728	0.059*
H5C	0.708438	−0.301159	0.181360	0.059*
C6	0.4732 (3)	−0.1344 (6)	0.1230 (2)	0.0366 (9)
H6A	0.448325	−0.025168	0.102189	0.055*
H6B	0.444151	−0.158068	0.169733	0.055*
H6C	0.449601	−0.219985	0.083535	0.055*
C7	0.7184 (2)	0.2225 (5)	0.33036 (16)	0.0237 (6)
C8	0.6696 (3)	0.3737 (5)	0.3321 (2)	0.0322 (8)
H8	0.670541	0.448836	0.290297	0.039*
C9	0.6182 (3)	0.4236 (6)	0.3928 (2)	0.0391 (9)
H9	0.586471	0.530466	0.391630	0.047*
C10	0.6143 (3)	0.3178 (6)	0.4529 (2)	0.0371 (9)
H10	0.578544	0.350206	0.493248	0.045*
C11	0.6629 (3)	0.1604 (5)	0.4556 (2)	0.0328 (8)
C12	0.6601 (4)	0.0520 (6)	0.5190 (2)	0.0464 (11)
H12	0.624115	0.086173	0.559045	0.056*
C13	0.7070 (5)	−0.0985 (7)	0.5241 (3)	0.0578 (14)
H13	0.704267	−0.168798	0.567337	0.069*
C14	0.7601 (4)	−0.1511 (6)	0.4650 (3)	0.0477 (11)
H14	0.793019	−0.257285	0.468543	0.057*
C15	0.7646 (3)	−0.0505 (5)	0.4024 (2)	0.0329 (8)
H15	0.800873	−0.088643	0.363250	0.040*
C16	0.7167 (3)	0.1088 (5)	0.3945 (2)	0.0261 (7)
C17	0.9317 (3)	0.3644 (4)	0.33358 (19)	0.0243 (7)
C18	0.9390 (3)	0.3895 (5)	0.41323 (19)	0.0287 (7)
H18	0.925588	0.299474	0.445188	0.034*
C19	0.9654 (3)	0.5436 (5)	0.4466 (2)	0.0319 (8)
H19	0.970429	0.558180	0.501130	0.038*
C20	0.9846 (3)	0.6768 (5)	0.4009 (2)	0.0340 (8)
H20	1.002007	0.782928	0.423684	0.041*
C21	0.9780 (3)	0.6530 (5)	0.3214 (2)	0.0341 (8)
H21	0.991414	0.743347	0.289646	0.041*
C22	0.9520 (3)	0.4987 (5)	0.2883 (2)	0.0301 (8)
H22	0.947839	0.484164	0.233828	0.036*
C23	0.9726 (3)	0.1487 (4)	0.2416 (2)	0.0241 (7)
C24	0.9580 (3)	0.1938 (4)	0.16468 (18)	0.0242 (7)
H24	0.896018	0.253246	0.141633	0.029*
C25	1.0347 (3)	0.1528 (5)	0.1189 (2)	0.0263 (7)
C26	1.0240 (3)	0.2018 (5)	0.04000 (19)	0.0289 (8)
H26	0.964322	0.264196	0.015139	0.035*
C27	1.1014 (3)	0.1574 (5)	0.0004 (2)	0.0312 (8)
C28	1.1884 (3)	0.0584 (5)	0.0338 (2)	0.0361 (9)
H28	1.238547	0.023743	0.003564	0.043*
C29	1.2000 (3)	0.0124 (6)	0.1104 (3)	0.0378 (9)
H29	1.259208	−0.052812	0.133734	0.045*
C30	1.1246 (3)	0.0612 (5)	0.1550 (2)	0.0285 (7)
C31	1.0703 (3)	0.0644 (4)	0.2727 (2)	0.0251 (7)
C32	1.1850 (3)	−0.0452 (6)	0.3846 (3)	0.0427 (10)
H32A	1.191281	−0.152129	0.358991	0.064*
H32B	1.187118	−0.063515	0.440374	0.064*
H32C	1.243771	0.027348	0.377926	0.064*
C33	0.3819 (3)	0.3840 (5)	0.0484 (2)	0.0310 (8)
C34	0.3376 (12)	0.439 (3)	0.1162 (6)	0.030 (2)	0.742 (7)
C35	0.2342 (10)	0.5018 (15)	0.1055 (5)	0.0338 (19)	0.742 (7)
H35	0.193862	0.513732	0.054183	0.041*	0.742 (7)
C36	0.1905 (9)	0.5461 (17)	0.1683 (5)	0.047 (2)	0.742 (7)
H36	0.118077	0.577683	0.160811	0.057*	0.742 (7)
C37	0.2530 (7)	0.5447 (12)	0.2437 (5)	0.0531 (19)	0.742 (7)
H37	0.225227	0.586384	0.286502	0.064*	0.742 (7)
C38	0.3550 (6)	0.4828 (10)	0.2555 (4)	0.0467 (16)	0.742 (7)
H38	0.396204	0.475671	0.306703	0.056*	0.742 (7)
C39	0.3966 (5)	0.4313 (9)	0.1920 (4)	0.0371 (14)	0.742 (7)
H39	0.466935	0.389697	0.200206	0.044*	0.742 (7)
C34B	0.331 (4)	0.429 (8)	0.1208 (16)	0.0242 (7)	0.258 (7)
C35B	0.239 (3)	0.526 (5)	0.1165 (17)	0.035 (4)	0.258 (7)
H35B	0.202750	0.564683	0.067136	0.042*	0.258 (7)
C36B	0.202 (3)	0.567 (5)	0.1825 (16)	0.044 (4)	0.258 (7)
H36B	0.150076	0.651410	0.181779	0.053*	0.258 (7)
C37B	0.2432 (18)	0.479 (3)	0.2514 (14)	0.047 (3)	0.258 (7)
H37B	0.205535	0.477535	0.293157	0.056*	0.258 (7)
C38B	0.3375 (16)	0.396 (3)	0.2586 (11)	0.047 (3)	0.258 (7)
H38B	0.373369	0.359002	0.308434	0.057*	0.258 (7)
C39B	0.3805 (17)	0.365 (3)	0.1932 (11)	0.039 (3)	0.258 (7)
H39B	0.443068	0.299799	0.197365	0.047*	0.258 (7)
N3	0.4791 (5)	−0.2008 (8)	0.3556 (4)	0.0620 (18)	0.742 (7)
C40	0.4502 (5)	−0.0703 (9)	0.3379 (4)	0.0477 (16)	0.742 (7)
C41	0.4178 (6)	0.0985 (10)	0.3164 (5)	0.063 (2)	0.742 (7)
H41A	0.473979	0.155009	0.295727	0.12 (4)*	0.742 (7)
H41B	0.404449	0.158210	0.362451	0.14 (5)*	0.742 (7)
H41C	0.352857	0.096518	0.276432	0.06 (2)*	0.742 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0403 (2)	0.0597 (3)	0.02848 (18)	−0.0089 (2)	0.01393 (14)	−0.0069 (2)
O1	0.0346 (14)	0.0229 (13)	0.0218 (12)	0.0020 (10)	0.0004 (10)	0.0026 (9)
O2	0.0255 (12)	0.0329 (14)	0.0287 (13)	0.0057 (10)	−0.0002 (10)	0.0040 (11)
O3	0.0501 (17)	0.053 (2)	0.0513 (17)	0.0218 (14)	0.0217 (14)	0.0106 (14)
O4	0.0429 (16)	0.0428 (17)	0.0267 (13)	0.0012 (13)	0.0080 (11)	0.0042 (12)
O5	0.0430 (15)	0.0396 (19)	0.0296 (14)	0.0001 (12)	−0.0030 (12)	0.0026 (11)
N1	0.0259 (15)	0.0300 (17)	0.0247 (14)	−0.0036 (12)	0.0020 (11)	−0.0002 (12)
N2	0.0236 (14)	0.0298 (17)	0.0348 (16)	0.0020 (12)	0.0075 (12)	−0.0010 (13)
C1	0.0249 (15)	0.025 (2)	0.0189 (14)	0.0024 (13)	0.0057 (11)	0.0019 (12)
C2	0.0264 (15)	0.0230 (19)	0.0186 (14)	0.0018 (12)	0.0036 (12)	0.0011 (12)
C3	0.0253 (16)	0.0233 (17)	0.0216 (15)	0.0032 (13)	0.0043 (12)	−0.0013 (13)
C4	0.0269 (17)	0.0279 (19)	0.0200 (16)	−0.0004 (14)	0.0049 (13)	−0.0038 (13)
C5	0.042 (2)	0.030 (2)	0.044 (2)	−0.0019 (17)	0.0062 (16)	0.0004 (17)
C6	0.0284 (19)	0.046 (2)	0.0318 (19)	−0.0067 (16)	−0.0032 (15)	0.0013 (17)
C7	0.0213 (13)	0.0262 (17)	0.0226 (13)	0.0029 (16)	0.0014 (10)	−0.0024 (16)
C8	0.0338 (19)	0.034 (2)	0.0292 (18)	0.0083 (16)	0.0055 (15)	0.0040 (15)
C9	0.042 (2)	0.037 (2)	0.038 (2)	0.0124 (18)	0.0085 (17)	−0.0050 (17)
C10	0.036 (2)	0.046 (2)	0.032 (2)	0.0070 (18)	0.0116 (17)	−0.0042 (17)
C11	0.0315 (19)	0.042 (2)	0.0249 (18)	0.0011 (16)	0.0068 (15)	0.0003 (15)
C12	0.056 (3)	0.054 (3)	0.035 (2)	0.006 (2)	0.025 (2)	0.007 (2)
C13	0.077 (3)	0.062 (3)	0.043 (3)	0.015 (3)	0.033 (2)	0.023 (2)
C14	0.064 (3)	0.043 (3)	0.041 (2)	0.011 (2)	0.023 (2)	0.0151 (19)
C15	0.037 (2)	0.031 (2)	0.0324 (19)	0.0024 (16)	0.0111 (16)	0.0040 (15)
C16	0.0240 (16)	0.0307 (19)	0.0239 (17)	0.0004 (13)	0.0052 (13)	0.0014 (13)
C17	0.0229 (16)	0.0269 (18)	0.0223 (16)	0.0006 (13)	0.0022 (12)	0.0014 (13)
C18	0.0379 (19)	0.0275 (19)	0.0197 (16)	−0.0008 (15)	0.0027 (14)	0.0023 (13)
C19	0.044 (2)	0.031 (2)	0.0197 (16)	−0.0037 (16)	0.0048 (15)	−0.0011 (14)
C20	0.048 (2)	0.027 (2)	0.0261 (17)	−0.0024 (15)	0.0028 (15)	−0.0029 (13)
C21	0.049 (2)	0.029 (2)	0.0240 (17)	−0.0065 (17)	0.0074 (15)	0.0036 (15)
C22	0.041 (2)	0.030 (2)	0.0204 (16)	−0.0047 (15)	0.0078 (14)	−0.0004 (14)
C23	0.0220 (16)	0.0228 (17)	0.0275 (17)	0.0007 (13)	0.0045 (13)	−0.0019 (13)
C24	0.0239 (14)	0.0259 (19)	0.0232 (14)	0.0014 (12)	0.0060 (12)	−0.0018 (12)
C25	0.0244 (16)	0.0262 (18)	0.0300 (18)	−0.0026 (13)	0.0091 (13)	−0.0038 (14)
C26	0.0284 (16)	0.034 (2)	0.0251 (15)	−0.0016 (14)	0.0087 (12)	−0.0039 (14)
C27	0.0326 (19)	0.034 (2)	0.0287 (18)	−0.0096 (16)	0.0104 (15)	−0.0061 (15)
C28	0.0308 (19)	0.039 (2)	0.043 (2)	−0.0012 (16)	0.0185 (16)	−0.0075 (17)
C29	0.0283 (19)	0.038 (2)	0.049 (2)	0.0038 (16)	0.0120 (17)	−0.0006 (18)
C30	0.0250 (17)	0.0272 (19)	0.0341 (19)	−0.0004 (14)	0.0074 (14)	−0.0022 (15)
C31	0.0253 (16)	0.0220 (17)	0.0270 (17)	−0.0010 (13)	0.0025 (13)	0.0024 (13)
C32	0.030 (2)	0.051 (3)	0.042 (2)	0.0104 (18)	−0.0054 (17)	0.0067 (19)
C33	0.0353 (19)	0.029 (2)	0.0299 (18)	−0.0005 (15)	0.0096 (15)	0.0002 (15)
C34	0.030 (3)	0.035 (4)	0.027 (3)	−0.001 (3)	0.006 (2)	−0.001 (2)
C35	0.034 (3)	0.035 (4)	0.032 (3)	0.004 (3)	0.006 (3)	−0.005 (3)
C36	0.041 (4)	0.060 (5)	0.042 (4)	0.012 (4)	0.010 (3)	−0.013 (4)
C37	0.065 (4)	0.058 (5)	0.040 (3)	0.010 (4)	0.019 (3)	−0.009 (3)
C38	0.056 (3)	0.053 (4)	0.030 (3)	0.002 (3)	0.005 (2)	−0.007 (3)
C39	0.036 (3)	0.040 (4)	0.034 (3)	0.000 (3)	0.003 (2)	−0.001 (3)
C34B	0.0239 (14)	0.0259 (19)	0.0232 (14)	0.0014 (12)	0.0060 (12)	−0.0018 (12)
C35B	0.031 (6)	0.042 (7)	0.030 (6)	0.003 (6)	0.003 (5)	−0.006 (6)
C36B	0.044 (6)	0.052 (7)	0.037 (6)	0.009 (6)	0.012 (6)	−0.017 (6)
C37B	0.053 (6)	0.055 (7)	0.036 (6)	0.003 (6)	0.018 (5)	−0.009 (6)
C38B	0.052 (6)	0.056 (7)	0.036 (5)	0.004 (6)	0.012 (5)	−0.003 (6)
C39B	0.040 (6)	0.044 (6)	0.033 (5)	0.004 (6)	0.008 (5)	−0.004 (6)
N3	0.077 (4)	0.038 (3)	0.078 (4)	0.002 (3)	0.030 (3)	0.015 (3)
C40	0.045 (3)	0.053 (4)	0.051 (4)	−0.008 (3)	0.024 (3)	−0.002 (3)
C41	0.049 (4)	0.055 (4)	0.092 (6)	0.009 (3)	0.032 (4)	0.007 (4)

Geometric parameters (Å, º)

Br1—C27	1.905 (4)	C18—H18	0.9500
O1—C2	1.419 (4)	C19—C20	1.386 (5)
O1—H1B	0.77 (5)	C19—H19	0.9500
O2—C31	1.358 (4)	C20—C21	1.387 (5)
O2—C32	1.434 (4)	C20—H20	0.9500
O3—C33	1.241 (5)	C21—C22	1.383 (5)
O4—C33	1.273 (5)	C21—H21	0.9500
O5—H5D	0.86 (3)	C22—H22	0.9500
O5—H5E	0.82 (3)	C23—C24	1.370 (5)
N1—C5	1.484 (5)	C23—C31	1.440 (5)
N1—C6	1.490 (5)	C24—C25	1.423 (5)
N1—C4	1.494 (4)	C24—H24	0.9500
N1—H1	1.0000	C25—C30	1.413 (5)
N2—C31	1.305 (5)	C25—C26	1.415 (5)
N2—C30	1.374 (5)	C26—C27	1.365 (5)
C1—C17	1.513 (5)	C26—H26	0.9500
C1—C23	1.526 (4)	C27—C28	1.406 (6)
C1—C2	1.572 (4)	C28—C29	1.369 (6)
C1—H1A	1.0000	C28—H28	0.9500
C2—C3	1.543 (5)	C29—C30	1.412 (5)
C2—C7	1.551 (4)	C29—H29	0.9500
C3—C4	1.525 (5)	C32—H32A	0.9800
C3—H3A	0.9900	C32—H32B	0.9800
C3—H3B	0.9900	C32—H32C	0.9800
C4—H4A	0.9900	C33—C34	1.478 (12)
C4—H4B	0.9900	C33—C34B	1.57 (3)
C5—H5A	0.9800	C34—C39	1.395 (11)
C5—H5B	0.9800	C34—C35	1.401 (10)
C5—H5C	0.9800	C35—C36	1.373 (9)
C6—H6A	0.9800	C35—H35	0.9500
C6—H6B	0.9800	C36—C37	1.405 (10)
C6—H6C	0.9800	C36—H36	0.9500
C7—C8	1.370 (6)	C37—C38	1.381 (10)
C7—C16	1.449 (5)	C37—H37	0.9500
C8—C9	1.411 (5)	C38—C39	1.385 (8)
C8—H8	0.9500	C38—H38	0.9500
C9—C10	1.359 (6)	C39—H39	0.9500
C9—H9	0.9500	C34B—C39B	1.40 (2)
C10—C11	1.408 (6)	C34B—C35B	1.41 (2)
C10—H10	0.9500	C35B—C36B	1.37 (2)
C11—C12	1.416 (6)	C35B—H35B	0.9500
C11—C16	1.440 (5)	C36B—C37B	1.41 (2)
C12—C13	1.347 (7)	C36B—H36B	0.9500
C12—H12	0.9500	C37B—C38B	1.37 (2)
C13—C14	1.408 (6)	C37B—H37B	0.9500
C13—H13	0.9500	C38B—C39B	1.384 (19)
C14—C15	1.370 (5)	C38B—H38B	0.9500
C14—H14	0.9500	C39B—H39B	0.9500
C15—C16	1.417 (5)	N3—C40	1.136 (9)
C15—H15	0.9500	C40—C41	1.448 (10)
C17—C18	1.391 (5)	C41—H41A	0.9800
C17—C22	1.393 (5)	C41—H41B	0.9800
C18—C19	1.383 (5)	C41—H41C	0.9800
C2—O1—H1B	109.5	C22—C21—C20	120.4 (3)
C31—O2—C32	116.9 (3)	C22—C21—H21	119.8
H5D—O5—H5E	104 (5)	C20—C21—H21	119.8
C5—N1—C6	110.4 (3)	C21—C22—C17	121.0 (3)
C5—N1—C4	112.7 (3)	C21—C22—H22	119.5
C6—N1—C4	109.8 (3)	C17—C22—H22	119.5
C5—N1—H1	107.9	C24—C23—C31	116.1 (3)
C6—N1—H1	107.9	C24—C23—C1	125.3 (3)
C4—N1—H1	107.9	C31—C23—C1	118.2 (3)
C31—N2—C30	117.9 (3)	C23—C24—C25	120.7 (3)
C17—C1—C23	109.9 (3)	C23—C24—H24	119.6
C17—C1—C2	110.9 (3)	C25—C24—H24	119.6
C23—C1—C2	115.5 (3)	C30—C25—C26	119.9 (3)
C17—C1—H1A	106.7	C30—C25—C24	117.8 (3)
C23—C1—H1A	106.7	C26—C25—C24	122.4 (3)
C2—C1—H1A	106.7	C27—C26—C25	118.6 (3)
O1—C2—C3	109.1 (3)	C27—C26—H26	120.7
O1—C2—C7	107.0 (3)	C25—C26—H26	120.7
C3—C2—C7	113.9 (3)	C26—C27—C28	122.5 (4)
O1—C2—C1	107.8 (3)	C26—C27—Br1	119.2 (3)
C3—C2—C1	111.2 (3)	C28—C27—Br1	118.3 (3)
C7—C2—C1	107.6 (2)	C29—C28—C27	119.1 (3)
C4—C3—C2	111.8 (3)	C29—C28—H28	120.4
C4—C3—H3A	109.2	C27—C28—H28	120.4
C2—C3—H3A	109.2	C28—C29—C30	120.6 (4)
C4—C3—H3B	109.2	C28—C29—H29	119.7
C2—C3—H3B	109.2	C30—C29—H29	119.7
H3A—C3—H3B	107.9	N2—C30—C29	118.9 (3)
N1—C4—C3	113.9 (3)	N2—C30—C25	121.9 (3)
N1—C4—H4A	108.8	C29—C30—C25	119.2 (3)
C3—C4—H4A	108.8	N2—C31—O2	119.6 (3)
N1—C4—H4B	108.8	N2—C31—C23	125.4 (3)
C3—C4—H4B	108.8	O2—C31—C23	115.0 (3)
H4A—C4—H4B	107.7	O2—C32—H32A	109.5
N1—C5—H5A	109.5	O2—C32—H32B	109.5
N1—C5—H5B	109.5	H32A—C32—H32B	109.5
H5A—C5—H5B	109.5	O2—C32—H32C	109.5
N1—C5—H5C	109.5	H32A—C32—H32C	109.5
H5A—C5—H5C	109.5	H32B—C32—H32C	109.5
H5B—C5—H5C	109.5	O3—C33—O4	124.6 (4)
N1—C6—H6A	109.5	O3—C33—C34	119.5 (5)
N1—C6—H6B	109.5	O4—C33—C34	115.9 (5)
H6A—C6—H6B	109.5	O3—C33—C34B	118.1 (11)
N1—C6—H6C	109.5	O4—C33—C34B	117.2 (11)
H6A—C6—H6C	109.5	C39—C34—C35	118.2 (9)
H6B—C6—H6C	109.5	C39—C34—C33	121.6 (9)
C8—C7—C16	117.8 (3)	C35—C34—C33	120.2 (9)
C8—C7—C2	117.3 (3)	C36—C35—C34	120.7 (8)
C16—C7—C2	124.7 (3)	C36—C35—H35	119.6
C7—C8—C9	123.5 (4)	C34—C35—H35	119.6
C7—C8—H8	118.3	C35—C36—C37	119.9 (8)
C9—C8—H8	118.3	C35—C36—H36	120.1
C10—C9—C8	119.6 (4)	C37—C36—H36	120.1
C10—C9—H9	120.2	C38—C37—C36	119.9 (7)
C8—C9—H9	120.2	C38—C37—H37	120.0
C9—C10—C11	120.4 (4)	C36—C37—H37	120.0
C9—C10—H10	119.8	C37—C38—C39	119.4 (6)
C11—C10—H10	119.8	C37—C38—H38	120.3
C10—C11—C12	120.1 (4)	C39—C38—H38	120.3
C10—C11—C16	120.5 (4)	C38—C39—C34	121.6 (7)
C12—C11—C16	119.5 (4)	C38—C39—H39	119.2
C13—C12—C11	121.7 (4)	C34—C39—H39	119.2
C13—C12—H12	119.2	C39B—C34B—C35B	119 (2)
C11—C12—H12	119.2	C39B—C34B—C33	117 (2)
C12—C13—C14	119.8 (4)	C35B—C34B—C33	124 (2)
C12—C13—H13	120.1	C36B—C35B—C34B	121 (2)
C14—C13—H13	120.1	C36B—C35B—H35B	119.6
C15—C14—C13	120.6 (4)	C34B—C35B—H35B	119.6
C15—C14—H14	119.7	C35B—C36B—C37B	118 (2)
C13—C14—H14	119.7	C35B—C36B—H36B	121.2
C14—C15—C16	121.8 (4)	C37B—C36B—H36B	121.2
C14—C15—H15	119.1	C38B—C37B—C36B	120 (2)
C16—C15—H15	119.1	C38B—C37B—H37B	119.8
C15—C16—C11	116.7 (3)	C36B—C37B—H37B	119.8
C15—C16—C7	125.1 (3)	C37B—C38B—C39B	120.0 (17)
C11—C16—C7	118.2 (3)	C37B—C38B—H38B	120.0
C18—C17—C22	118.1 (3)	C39B—C38B—H38B	120.0
C18—C17—C1	120.3 (3)	C38B—C39B—C34B	119.7 (19)
C22—C17—C1	121.5 (3)	C38B—C39B—H39B	120.2
C19—C18—C17	121.0 (3)	C34B—C39B—H39B	120.2
C19—C18—H18	119.5	N3—C40—C41	177.7 (8)
C17—C18—H18	119.5	C40—C41—H41A	109.5
C18—C19—C20	120.4 (3)	C40—C41—H41B	109.5
C18—C19—H19	119.8	H41A—C41—H41B	109.5
C20—C19—H19	119.8	C40—C41—H41C	109.5
C19—C20—C21	119.1 (4)	H41A—C41—H41C	109.5
C19—C20—H20	120.4	H41B—C41—H41C	109.5
C21—C20—H20	120.4
C17—C1—C2—O1	54.5 (3)	C17—C1—C23—C31	87.0 (4)
C23—C1—C2—O1	−71.4 (3)	C2—C1—C23—C31	−146.7 (3)
C17—C1—C2—C3	174.1 (3)	C31—C23—C24—C25	2.2 (5)
C23—C1—C2—C3	48.2 (4)	C1—C23—C24—C25	175.4 (3)
C17—C1—C2—C7	−60.6 (3)	C23—C24—C25—C30	1.3 (5)
C23—C1—C2—C7	173.6 (3)	C23—C24—C25—C26	−178.0 (3)
O1—C2—C3—C4	−76.1 (3)	C30—C25—C26—C27	0.6 (5)
C7—C2—C3—C4	43.4 (4)	C24—C25—C26—C27	179.9 (3)
C1—C2—C3—C4	165.1 (3)	C25—C26—C27—C28	3.2 (6)
C5—N1—C4—C3	65.3 (4)	C25—C26—C27—Br1	−177.0 (3)
C6—N1—C4—C3	−171.3 (3)	C26—C27—C28—C29	−4.1 (6)
C2—C3—C4—N1	165.5 (3)	Br1—C27—C28—C29	176.1 (3)
O1—C2—C7—C8	−8.1 (4)	C27—C28—C29—C30	1.1 (6)
C3—C2—C7—C8	−128.8 (3)	C31—N2—C30—C29	−179.3 (4)
C1—C2—C7—C8	107.5 (3)	C31—N2—C30—C25	1.4 (5)
O1—C2—C7—C16	176.3 (3)	C28—C29—C30—N2	−176.9 (4)
C3—C2—C7—C16	55.6 (4)	C28—C29—C30—C25	2.4 (6)
C1—C2—C7—C16	−68.1 (4)	C26—C25—C30—N2	176.0 (3)
C16—C7—C8—C9	−0.1 (6)	C24—C25—C30—N2	−3.3 (5)
C2—C7—C8—C9	−175.9 (3)	C26—C25—C30—C29	−3.3 (6)
C7—C8—C9—C10	−0.9 (6)	C24—C25—C30—C29	177.4 (3)
C8—C9—C10—C11	1.2 (6)	C30—N2—C31—O2	−177.1 (3)
C9—C10—C11—C12	178.9 (4)	C30—N2—C31—C23	2.6 (5)
C9—C10—C11—C16	−0.5 (6)	C32—O2—C31—N2	2.4 (5)
C10—C11—C12—C13	−179.1 (5)	C32—O2—C31—C23	−177.3 (3)
C16—C11—C12—C13	0.4 (7)	C24—C23—C31—N2	−4.4 (5)
C11—C12—C13—C14	−0.3 (8)	C1—C23—C31—N2	−178.2 (3)
C12—C13—C14—C15	0.1 (8)	C24—C23—C31—O2	175.3 (3)
C13—C14—C15—C16	0.0 (7)	C1—C23—C31—O2	1.5 (5)
C14—C15—C16—C11	0.1 (6)	O3—C33—C34—C39	21 (2)
C14—C15—C16—C7	179.7 (4)	O4—C33—C34—C39	−157.5 (13)
C10—C11—C16—C15	179.2 (4)	O3—C33—C34—C35	−159.2 (14)
C12—C11—C16—C15	−0.3 (6)	O4—C33—C34—C35	22 (2)
C10—C11—C16—C7	−0.5 (5)	C39—C34—C35—C36	−3 (3)
C12—C11—C16—C7	−179.9 (4)	C33—C34—C35—C36	177.0 (13)
C8—C7—C16—C15	−178.9 (4)	C34—C35—C36—C37	6 (2)
C2—C7—C16—C15	−3.3 (5)	C35—C36—C37—C38	−6.6 (17)
C8—C7—C16—C11	0.7 (5)	C36—C37—C38—C39	3.6 (14)
C2—C7—C16—C11	176.3 (3)	C37—C38—C39—C34	−0.6 (16)
C23—C1—C17—C18	−135.1 (3)	C35—C34—C39—C38	0 (2)
C2—C1—C17—C18	95.9 (4)	C33—C34—C39—C38	180.0 (12)
C23—C1—C17—C22	46.4 (4)	O3—C33—C34B—C39B	4 (6)
C2—C1—C17—C22	−82.5 (4)	O4—C33—C34B—C39B	−179 (3)
C22—C17—C18—C19	0.1 (5)	O3—C33—C34B—C35B	−175 (5)
C1—C17—C18—C19	−178.4 (3)	O4—C33—C34B—C35B	2 (7)
C17—C18—C19—C20	0.4 (6)	C39B—C34B—C35B—C36B	4 (8)
C18—C19—C20—C21	−0.7 (6)	C33—C34B—C35B—C36B	−177 (4)
C19—C20—C21—C22	0.4 (6)	C34B—C35B—C36B—C37B	−14 (6)
C20—C21—C22—C17	0.1 (6)	C35B—C36B—C37B—C38B	19 (5)
C18—C17—C22—C21	−0.3 (6)	C36B—C37B—C38B—C39B	−15 (4)
C1—C17—C22—C21	178.2 (3)	C37B—C38B—C39B—C34B	5 (5)
C17—C1—C23—C24	−86.1 (4)	C35B—C34B—C39B—C38B	1 (8)
C2—C1—C23—C24	40.2 (5)	C33—C34B—C39B—C38B	−178 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O5	0.77	1.94	2.691 (4)	163
O5—H5D···O4^i	0.86 (3)	1.89 (3)	2.738 (4)	168 (6)
O5—H5E···O3	0.82 (3)	1.92 (3)	2.734 (4)	172 (6)
N1—H1···O4^i	1.00	1.62	2.619 (4)	178
C5—H5C···Br1^ii	0.98	3.13	3.964 (4)	144
C6—H6A···O3	0.98	2.63	3.562 (6)	159
C28—H28···O5^ii	0.95	2.66	3.498 (5)	148

Symmetry codes: (i) −x+1, y−1/2, −z; (ii) −x+2, y−1/2, −z.