research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

Maleate salts of bedaquiline

aDepartment of Chemistry, Purdue University, 560 Oval Dr., W. Lafayette, IN 47907-2084, USA, bRavine Pharmaceuticals LLC, 3425 DuBois St., West Lafayette, IN 47906, USA, cLeading with Smart Science LLC, 5315 Shootingstar Ln, West Lafayette, IN 47906, USA, dChemical Microscopy LLC, 1281 Win Hentschel Blvd., West Lafayette, IN 47906, USA, eBiotechnology Innovation and Regulatory Science Center, Lilly Hall of Life Sciences, 915 State Street, Purdue University, West Lafayette, IN 47906, USA, fAgricultural & Biological Engineering, Purdue University, 225 South University Street, West Lafayette, IN 47907, USA, gIndustrial and Physical Pharmacy, Purdue University, 575 Stadium Mall, West Lafayette, IN 47906, USA, and hImproved Pharma LLC, 1281 Win Hentschel Blvd. Suite 1565, West Lafayette, IN 47906, USA
*Correspondence e-mail: zeller4@purdue.edu

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 5 March 2021; accepted 22 March 2021; online 26 March 2021)

Bedaquiline 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, but only a few salts of bedaquiline have been structurally described so far. We present here five crystal structures of bedaquilinium maleate {systematic name: [4-(6-bromo-2-meth­oxy­quinolin-3-yl)-3-hy­droxy-3-(naphthalen-1-yl)-4-phenyl­but­yl]di­methyl­aza­nium 3-carb­oxy­prop-2-enoate}, C32H32BrN2O2+·C4H3O4, namely, a hemihydrate, a tetra­hydro­furan (THF) solvate, a mixed acetone/hexane solvate, an ethyl acetate solvate, and a solvate-free structure obtained from the acetone/hexane solvate by in situ single-crystal-to-single-crystal desolvation. All salts exhibit a 1:1 cation-to-anion ratio, with the anion present as monoanionic hydro­maleate and a singly protonated bedaquilinium cation. The maleate exhibits the strong intra­molecular hydrogen bond typical for cis-di­carb­oxy­lic acid anions. The conformations of the cations and packing inter­actions in the maleate salts are compared to those of free base bedaquiline and other bedaquilinium salts.

1. Chemical context

Bedaquiline is one of two important new drugs for the treatment of drug-resistant tuberculosis (TB). It is marketed in the US as the fumarate salt with the trade name SirturoTM (Brigden et al., 2015[Brigden, G., Hewison, C. & Varaine, F. (2015). Infect. Drug Resist. 8, 367-378.]) and described in US Patent 8,546,428 (Hegyi et al., 2013[Hegyi, J. F. A. L., Aelterman, W. A. A., Lang, Y. L., Stokbroekx, S. C. M., Leys, C., Van Remoortere, P. J. M. & Faure, A. (2013). United States Patent US 8,546,428, Janssen Pharmaceuticals, USA.]). A number of other bedaquilinium salts have been reported since the emergence of its pharmacolog­ical relevance, but until recently only free base bedaquiline had been fully structurally described (Petit et al., 2007[Petit, S., Coquerel, G., Meyer, C. & Guillemont, J. (2007). J. Mol. Struct. 837, 252-256.]). To fill this gap, which severely hampers understanding of the chemical, physical and physiological properties of bedaquiline and its derivatives, we have recently reported and analyzed the single-crystal structures of several bedaquilinium salts, including that of the commercially traded fumarate as well as two differently solvated benzoate salts (Okezue et al., 2020[Okezue, M., Smith, D., Zeller, M., Byrn, S. R., Smith, P., Bogandowich-Knipp, S., Purcell, D. K. & Clase, K. L. (2020). Acta Cryst. C76, 1010-1023.]). This study revealed that bedaquiline and its salts have a very rich and diverse structural chemistry. Depending on the nature of the anion (fumarate, benzoate or none for free base bedaquiline), different mol­ecular conformations and structural motifs are observed. In free base bedaquiline, the amine moiety is engaged in an intra­molecular O—H⋯N hydrogen bond, limiting the formation of inter­molecular hydrogen-bonding inter­actions. The packing is instead dominated by weaker and less directional inter­actions such as Br⋯Br inter­actions and π-stacking (Petit et al., 2007[Petit, S., Coquerel, G., Meyer, C. & Guillemont, J. (2007). J. Mol. Struct. 837, 252-256.]). In the fumarate and benzoate salts, the protonated amine moiety is available as a hydrogen-bond donor and forms bonds with the benzoate or fumarate anions, and these salts are dominated by a multitude of N—H⋯O and O—H⋯O hydrogen-bonding inter­actions that connect the cations and anions into strongly hydrogen-bonded ribbon-like structures. The ethane backbone and the malleable ethyl­amine fragment of the bedaquiline core result in a high degree of flexibility, and mol­ecular conformations vary not only widely between the bedaquiline and bedaquilinium structures, but even between independent mol­ecules within the same structure (both the free base and the fumarate are Z′ = 2 structures). For a pharmaceutically relevant material, it is essential that a crystalline material can be obtained in a stable and well-defined form. The formation of solvates is generally undesirable, especially if the incorpor­ated solvent mol­ecules are volatile or not generally recognized as safe (GRAS) for human consumption. For the bedaquilinum system, the pronounced conformational flexibility makes any predictions about how a bedaquilinium anion pair might crystallize, and whether solvates are formed and of which kind, extremely difficult. In silico crystal-structure prediction, even if only intended as a screening to narrow down a list of anion and solvent candidates, is not yet a viable option for this system; therefore, the best recourse for the bedaquiline system remains experimental screening of combinations of anions, solvents and crystallization conditions to establish which combinations will yield stable and well-defined crystal forms for potential use in pharmaceutical formulations. To this end, we have investigated the combination of bedaquiline with maleate as the anion. Via screening of solvents and crystallization conditions, we were able to establish the structures of several of its solvates: a hemihydrate, a THF solvate, an acetone/hexane solvate and an ethyl acetate solvate. A solvate-free form obtained by in situ desolvation of the acetone/hexane solvate will also be described. The influence of the incorporated solvents on the crystal structures and their stability will be discussed.

[Scheme 1]

2. Structural commentary

Probability ellipsoid plots with selected atom labels and solvate mol­ecules (where present) are shown in Figs. 1[link]–5[link][link][link][link]. The atom-naming scheme was adopted from the one used for the fumarate and benzoate structures and used for all solvates. Refinement details, including disorder refinement strategies (where present) are given in the Refinement section.

[Figure 1]
Figure 1
Probability ellipsoid plot (50% probability) of the hemihydrate. C-bound H atoms and H-atom labels are omitted for clarity. Water mol­ecules O7 and O8 are partially occupied [0.276 (17) for O7 and 0.40 (4) for O8].
[Figure 2]
Figure 2
Probability ellipsoid plot (50% probability) of the THF solvate (see Fig. 1[link] for cation and anion carbon-atom labels). C-bound H atoms and labels for C and H atoms are omitted for clarity. THF mol­ecules are disordered around a twofold axis (O7) or in a general position (O8).
[Figure 3]
Figure 3
Probability ellipsoid plot (50% probability) of the acetone/hexane solvate (see Fig. 1[link] for cation and anion carbon-atom labels). C-bound H atoms and labels for C and H atoms are omitted for clarity. Acetone mol­ecules are disordered: fourfold around a twofold axis plus general disorder (O8, disorder by the twofold axis not shown for clarity) or with a hexane mol­ecule (O7, the hexane mol­ecule is located on a twofold axis).
[Figure 4]
Figure 4
Probability ellipsoid plot (50% probability) of the ethyl acetate solvate, showing both ion pairs (suffixes A and B) related by pseudo-translation (see Fig. 1[link] for cation and anion carbon-atom labels). C-bound H atoms, labels for C and H atoms and disorder of ethyl acetate mol­ecules are omitted for clarity.
[Figure 5]
Figure 5
Probability ellipsoid plot (50% probability) of the desolvated structure (see Fig. 1[link] for cation and anion carbon-atom labels). C-bound H atoms and labels for C and H atoms are omitted for clarity.

Similar to the other three bedaquilinum salts reported thus far, the maleate salt features a singly protonated bedaquilin­ium cation with a 1:1 anion-to-cation ratio. Like in the fumarate and benzoate salts, the protonation site is the dimethyl amine fragment. The second basic site, the quinoline nitro­gen atoms, remained unprotonated, in agreement with the second pKa of maleic acid (6.22, European Chemical Agency, 2015[European Chemical Agency (2015). Maleic Acid (CAS 110-16-7). Registered Substances Dossier. European Chemical Agency. Available from http://echa.europa.eu/]), which is not sufficiently basic for a proton transfer to this site. The first pKa of maleic acid (1.94, European Chemical Agency, 2015[European Chemical Agency (2015). Maleic Acid (CAS 110-16-7). Registered Substances Dossier. European Chemical Agency. Available from http://echa.europa.eu/]) should be sufficient to protonate the quinoline site if higher ratios of maleic acid to bedaquiline are used (Okezue et al., 2020[Okezue, M., Smith, D., Zeller, M., Byrn, S. R., Smith, P., Bogandowich-Knipp, S., Purcell, D. K. & Clase, K. L. (2020). Acta Cryst. C76, 1010-1023.]). We were, however, unable to identify or isolate any different crystalline materials when increasing the amounts of acid (screening was done by powder XRD).

The four bedaquilinium maleate structures presented here were found to be isomorphous or nearly isomorphous, differing mostly only in the nature of the incorporated solvate mol­ecules. One of the structures, the ethyl acetate solvate, also shows a pronounced modulation of the bedaquilinium maleate, leading to breaking of the crystallographic symmetry observed for the other structures (see the Supra­molecular features section for a detailed discussion). Similar isomorphous structures were also found for samples obtained from other solvent systems such as iso­propanol or n-propanol, as evidenced by their powder XRD patterns. However, no single crystals of high enough quality for a full structural analysis could be obtained thus far.

The ethane backbone and the malleable ethyl­amine fragment gives the bedaquilinium cation a high degree of flexibility that allows the cations to respond readily to crystal-packing forces. In the previously reported structures, the conformations did vary widely not only from structure to structure, but even between independent mol­ecules within the same structure (both the free base and the fumarate are Z′ = 2 structures). For these structures, the torsion angles involving the ethyl­amine fragment adopted conformations ranging between gauche and trans (Table 1[link]), with the observation for gauche found mostly for free base bedaquiline, where it was induced by an intra­molecular O—H⋯N hydrogen bond. However, one of the two mol­ecules in the fumarate salt also featured a single gauche angle (for the C1—C2—C3—C4 torsion angle), and two angles in between gauche and trans [C2—C3—C4—N1 for the two fumarate mol­ecules, with values of 137.2 (2) and 133.7 (2)°, respectively]. All other torsion angles involving the ethyl­amine group adopted trans conformations with various degrees of slight distortions, ranging from 164.04 (15) to 178.8 (3)°. The maleate salts follow the same trend. The torsion angles are all slightly distorted trans and range from −164.4 (7) to 176.4 (3)° (C17—C1—C2—C3 and C1—C2—C3—C4 angles, extreme values are for each one of the two mol­ecules of the ethyl acetate solvate).

Table 1
Selected torsion angles for bedaquilinium maleate structures

  hemihydrate THF ethyl acetate acetone/hexa­ne desolvated
τ plane 1 vs plane 2 71.31 (7) 64.3 (1) 67.78 (7), 63.0 (2) 70.00 (6) 70.34 (5)
τ plane 2 vs plane 3 65.35 (9) 63.7 (1) 65.8 (1), 64.0 (2) 66.60 (7) 64.89 (6)
τ plane 1 vs plane 3 32.62 (9) 26.4 (1) 31.7 (1), 31.50 (9) 29.47 (7) 32.06 (6)
τ C1—C2—C3—C4 175.6 (3) 174.1 (4) 176.4 (3), 175.9 (3) 176.2 (2) 175.85 (18)
τ C2—C3—C4—N1 169.4 (3) 174.3 (4) 173.9 (3), 174.6 (3) 172.86 (19) 169.78 (18)
τ C17—C1—C2—C3 −170.8 (3) −169.8 (4) −172.0 (3), −164.4 (7) −172.3 (2) −171.37 (19)

The other free variables that determine the overall mol­ecular structure of the cations are the torsion angles between the rigid planes of bedaquiline, i.e. the 6-bromo-2-meth­oxy­quinoline, phenyl and naphthyl planes (Table 1[link]). Variations of only a few degrees can be seen between equivalent angles of the various inter­planar angles in the cations, as would be expected for mostly isomorphous structures. The 6-bromo-2-meth­oxy­quinoline vs phenyl angle ranges from 63.0 (2) to 71.31 (7)°, which is slightly smaller but similar to what was observed in the previously reported structures [73.29 (7) to 86.02 (8)°; Petit et al., 2007[Petit, S., Coquerel, G., Meyer, C. & Guillemont, J. (2007). J. Mol. Struct. 837, 252-256.]; Okezue et al., 2020[Okezue, M., Smith, D., Zeller, M., Byrn, S. R., Smith, P., Bogandowich-Knipp, S., Purcell, D. K. & Clase, K. L. (2020). Acta Cryst. C76, 1010-1023.]]. Phenyl to naphthyl angles are between 63.7 (1) and 66.60 (7)°. Previously reported values span a much wider range, from 44.2 (1) to 89.74 (9)°. The bromo-2-meth­oxy­quinoline vs naphthyl angles are between 26.4 (1) and 32.62 (9)°, compared to 8.16 (9) to 37.50 (6)° for the other known bedaquiline structures.

Numerical variations between the four structures are thus clearly resolved. They are not, however, large enough to substanti­ally alter the overall shape and appearance of the cations, as can be seen in a least-squares overlay based on the atoms C1, C2, C7, C17 and C23 around the center of the cation (Fig. 6[link]). The structures clearly still have the same overall conformation, just slightly modulated by inter­actions with solvate mol­ecules and small differences in unit cell dimensions. The largest variations in the overlay can be seen for the outer atoms of the 6-bromo-2-meth­oxy­quinoline plane, especially the bromine atom, the meth­oxy group, the outer atoms of the naphthyl group, and to a lesser degree for the dimethyl ammonium fragment.

[Figure 6]
Figure 6
Least-squares overlay based on the atoms C1, C2, C7, C17 and C23. Color coding: hemihydrate – orange; THF solvate – green; ethyl acetate solvate – red and pink (two independent mol­ecules); acetone/hexane solvate – blue; desolvated structure – cyan.

3. Supra­molecular features

Packing and inter­molecular inter­actions not involving solvate mol­ecules are essentially identical between the four structures, a virtue of their isomorphous or nearly isomorphous nature. Unless stated otherwise, all distances in the following discussion will be those of the hemihydrate structure.

The main directional forces that are involved in stabilizing crystals of bedaquilinium maleate are hydrogen bonds (Tables 2[link]–7[link][link][link][link][link]) and ππ stacking inter­actions. One hydrogen bond is intra­molecular and connects the carb­oxy­lic acid and carboxyl­ate groups of the hydro­maleate anion, which shows the very strong and close to symmetrical hydrogen bonding typical for cis-di­carb­oxy­lic acid anions (Fig. 7[link]). The acidic maleate hydrogen atoms are well resolved in all five structures and their positions were freely refined. The position of the H atom varies slightly between the five structures. It is close to symmetric, with a slight deviation towards oxygen atom O5 in all but the THF solvate (see Table 8[link] for numerical details). The more accurately measured carbon–oxygen bond distances confirm the slight asymmetry for the hydro­maleate, with the C33—O4 bond being on average 0.02 Å shorter than the C36—O5 bond. This includes the THF solvate, for which the H atom was found slightly closer to O4, indicating that the H-atom position is not measured sufficiently accurately to reliably determine its actual position (among the five structures, the THF solvate has the largest estimated standard deviations for atom positions, and within its s.u., the position of H5 is symmetric between O4 and O5).

Table 2
Hydrogen-bond geometry (Å, °) for the hemihydrate[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1O⋯O6i 0.84 1.98 2.822 (4) 175
O5—H5⋯O4 1.13 (6) 1.29 (6) 2.417 (4) 169 (5)
N1—H1⋯O3 1.00 1.71 2.707 (4) 172
N1—H1⋯O4 1.00 2.49 3.174 (4) 125
C3—H3A⋯O6i 0.99 2.57 3.308 (4) 131
C6—H6B⋯O4ii 0.98 2.61 3.257 (5) 124
O7—H7A⋯O3 0.84 2.31 3.139 (16) 172
O8—H8A⋯O7 0.94 2.13 3.02 (2) 158
Symmetry codes: (i) [x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]; (ii) [-x+1, y, -z].

Table 3
Hydrogen-bond geometry (Å, °) for the THF solvate[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1O⋯O6i 0.84 1.99 2.824 (5) 176
O4—H5⋯O5 1.15 (8) 1.28 (8) 2.422 (5) 171 (7)
N1—H1⋯O3 1.00 1.70 2.699 (5) 175
N1—H1⋯O4 1.00 2.63 3.310 (6) 125
C3—H3A⋯O6i 0.99 2.53 3.258 (6) 130
C3—H3B⋯O3 0.99 2.65 3.314 (6) 125
C6—H6B⋯O4ii 0.98 2.55 3.173 (7) 122
C26—H26⋯O8Bi 0.95 2.57 3.44 (3) 152
C42—H42B⋯O3iii 0.99 2.67 3.478 (17) 138
Symmetry codes: (i) [x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]; (ii) [-x+1, y, -z]; (iii) [x+{\script{1\over 2}}, y-{\script{1\over 2}}, z].

Table 4
Hydrogen-bond geometry (Å, °) for the ethyl acetate solvate[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O1A—H1AB⋯O6Bi 0.84 (6) 1.98 (6) 2.791 (4) 160 (6)
O5A—H5A⋯O4A 1.11 (10) 1.33 (10) 2.426 (5) 171 (9)
N1A—H1A⋯O3A 1.00 1.71 2.707 (4) 175
N1A—H1A⋯O4A 1.00 2.54 3.211 (4) 125
O1B—H1BB⋯O6A 0.92 (6) 1.91 (6) 2.812 (4) 168 (6)
O5B—H5B⋯O4B 1.17 (8) 1.29 (8) 2.429 (4) 164 (6)
N1B—H1B⋯O3B 1.00 1.70 2.701 (4) 174
N1B—H1B⋯O4B 1.00 2.52 3.204 (4) 125
C3A—H3AA⋯O6Bi 0.99 2.56 3.251 (4) 127
C5A—H5AC⋯O3ii 0.98 2.60 3.391 (15) 138
C6A—H6AA⋯O4Biii 0.98 2.59 3.218 (5) 122
C32A—H32A⋯O1iv 0.98 2.59 3.220 (7) 122
C1B—H1BA⋯O2B 1.00 2.26 2.780 (4) 111
C3B—H3BA⋯O6A 0.99 2.58 3.284 (4) 128
C6B—H6BA⋯O4Av 0.98 2.58 3.190 (5) 121
C2E—H2EB⋯O3Avi 0.98 2.34 2.96 (2) 120
C4E—H4EB⋯O1E 0.98 2.37 2.91 (5) 114
C7—H7A⋯O4Aiii 0.99 2.29 3.068 (15) 134
C8E—H8EC⋯O5Aiii 0.98 2.65 3.57 (3) 157
C8G—H8GB⋯O1Av 0.98 2.05 2.90 (5) 145
Symmetry codes: (i) [x-1, y-1, z]; (ii) [x-1, y, z]; (iii) [-x+1, y-{\script{1\over 2}}, -z]; (iv) [-x+1, y+{\script{1\over 2}}, -z+1]; (v) [-x+1, y+{\script{1\over 2}}, -z]; (vi) [-x+1, y-{\script{1\over 2}}, -z+1].

Table 5
Hydrogen-bond geometry (Å, °) for the acetone/hexane solvate[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1O⋯O6i 0.84 1.98 2.816 (3) 175
O5—H5⋯O4 1.18 (5) 1.24 (5) 2.422 (3) 175 (5)
N1—H1⋯O3 1.00 1.71 2.709 (3) 174
N1—H1⋯O4 1.00 2.54 3.212 (3) 125
C32—H32B⋯O7 0.98 2.60 3.337 (8) 132
C34—H34⋯O7 0.95 2.66 3.600 (9) 171
Symmetry code: (i) [x-{\script{1\over 2}}, y-{\script{1\over 2}}, z].

Table 6
Hydrogen-bond geometry (Å, °) for the desolvated structure[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1O⋯O6i 0.84 1.98 2.818 (3) 180
O5—H5⋯O4 0.99 (5) 1.43 (5) 2.419 (3) 172 (5)
N1—H1⋯O3 1.00 1.71 2.704 (3) 172
N1—H1⋯O4 1.00 2.51 3.188 (3) 125
Symmetry code: (i) [x-{\script{1\over 2}}, y-{\script{1\over 2}}, z].

Table 7
Hydrogen-bond geometry (Å, °) for the desolvated structure (SQUEEZE applied)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1O⋯O6i 0.84 1.98 2.820 (2) 180
O5—H5⋯O4 1.01 (4) 1.42 (4) 2.420 (3) 169 (4)
N1—H1⋯O3 1.00 1.71 2.705 (2) 172
N1—H1⋯O4 1.00 2.51 3.186 (2) 125
Symmetry code: (i) [x-{\script{1\over 2}}, y-{\script{1\over 2}}, z].

Table 8
Bond distances and angles involving the intra­molecular O⋯H⋯O hydrogen bond of the hydro­maleate anions (Å, °)

  hemihydrate THF ethyl acetate acetone/hexa­ne desolvated
O5—H5 1.13 (6) 1.28 (8) 1.11 (10) A 1.17 (8) B 1.18 (5) 0.99 (5)
O4—H5 1.29 (6) 1.15 (8) 1.33 (10) A 1.29 (8) B 1.24 (5) 1.43 (5)
O5⋯H5⋯O6 169 (5) 171 (7) 171 (9) A 164 (6) B 175 (5) 172 (5)
C33—O4 1.275 (5) 1.275 (7) 1.246 (3) A 1.266 (5) B 1.271 (3) 1.276 (3)
C36—O5 1.290 (5) 1.301 (6) 1.292 (5) A 1.293 (5) B 1.283 (3) 1.283 (3)
C33—O3 1.237 (5) 1.234 (6) 1.245 (5) A 1.241 (5) B 1.230 (3) 1.238 (3)
C36—O6 1.231 (5) 1.217 (6) 1.216 (5) A 1.216 (5) B 1.222 (3) 1.233 (3)
[Figure 7]
Figure 7
The main hydrogen-bonding inter­actions in common to all structures (turquoise and red dashed lines). Shown is the hemihydrate. Partially occupied water mol­ecules, C-bound H atoms and labels for C-bound H atoms are omitted for clarity. Probability ellipsoids are at the 50% level. Symmetry codes: (i) −[{1\over 2}] + x, −[{1\over 2}] + y, z; (ii) [{1\over 2}] + x, [{1\over 2}] + y, z; (iii) [{1\over 2}] + x, [{1\over 2}] + y, z.

The not quite symmetric nature of the hydro­maleate anion could be a result of asymmetric inter­molecular hydrogen bonding towards the two ends of the anion. Oxygen atom O3 acts as a hydrogen-bond acceptor towards the ammonium cation, while O6 plays the same role for the hydroxyl group of another cation (at [{1\over 2}] + x, [{1\over 2}] + y, +z). The N—H⋯O hydrogen bond, being charge assisted, is slightly shorter and stronger than its O—H⋯O equivalent on the other side of the anion, inducing the negative charge of the anion to be localized more on the O3/O4 carboxyl­ate group, and the positive proton being slightly delocalized towards O5.

The individual graph-set motifs (Etter et al., 1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]) for the inter­molecular O—H⋯O and N+—H⋯O hydrogen-bonding inter­actions common to all structures are as follows (Fig. 7[link]): a linear D11(2) motif for the O—H⋯O hydrogen bond with one hydrogen-bond acceptor and one hydrogen-bond donor and a bifurcated R21(4) motif towards both O3 and O4 of the maleate for the N+—H⋯O bond. The latter inter­action is, however, quite asymmetric, with the N1⋯O3 distance substanti­ally shorter than the N1⋯O4 distance [2.707 (4) and 3.174 (4) Å in the hemihydrate structure], thus making a description as D11(2) more suitable. Together, the N—H⋯O and O—H⋯O hydrogen bonds connect the cations and anions into infinite chains. The graph-set motif of these chains is C22(13). This means that including the connecting carbon atoms of the maleate and the propyl­ene backbone of the beadquilinium cation expands the graph-set motif from individual linear D hydrogen bonds into infinite 1D chains with a repeat unit that includes two hydrogen-bond acceptors, two donors and thirteen atoms in total (seven carbon atoms in addition to the N—H⋯O and O—H⋯O moieties), thus C22(13).

The 1D chains formed in that way extend diagonally through the lattice along the [110] and the [[\overline{1}]10] directions. Neighboring chains thus do not run in parallel, but are split into chains with two different propagation directions, related to each other by the twofold rotation of the C2 space group (red and blue chains in Fig. 8[link]). Cations and anions along the chain are related to each other via half-unit translations of the C-centered cell (±[{1\over 2}] + x, ±[{1\over 2}] + y, +z). This differentiates the maleate structures described here from the other previously described bedaquilinium salt structures, the fumarate and benzoate structures, in which hydrogen-bonding inter­actions between cations and anions led to formation of layered structures (Okezue et al., 2020[Okezue, M., Smith, D., Zeller, M., Byrn, S. R., Smith, P., Bogandowich-Knipp, S., Purcell, D. K. & Clase, K. L. (2020). Acta Cryst. C76, 1010-1023.]). For highly solvated structures such as the maleate salts described here, the formation of 1D rather than 2D structures can be of relevance for the resilience of the lattice upon removal of solvent, or the persistence of the packing motif if a different solvent is used. Inter­actions within the layers or chains, mediated via hydrogen bonds, are likely to be strong and persistent. The stability of the entire lattice thus depends on how these layers or chains are connected with each other. Are they tightly inter­woven or connected in other ways to ensure stability of the lattice after removal or exchange of solvate mol­ecules? Or can layers or chains easily move past each other, thus allowing easy movement of the secondary building units and either collapse or undergo a complete rearrangement of the entire structure?

[Figure 8]
Figure 8
Packing view of the hemihydrate structure showing the propagation directions of the hydrogen-bonded chains. In the lower half of the unit cell, chains propagate horizontally (right–left, along [110]; in the upper half they propagate longitudinally (forward–backward, along [[\overline{1}]10]). Hydrogen bonds are shown as turquoise dashed lines. Green dashed lines connect the centroids of the bromo­quinoline substituents [3.432 (14) Å]. Partially occupied water mol­ecules shown as spheres of arbitrary radius. For all other atoms, probability ellipsoids are at the 50% level. C-bound H atoms and labels for C H atoms are omitted for clarity.

In the maleate salts, inter­actions between individual chains is facilitated through effective inter­locking of neighboring chains as well as a number of directional inter­actions, such as C—H⋯O, C—H⋯N and C—H⋯π inter­actions. Importantly, neighboring chains that are rotated against each other by the twofold axis are inter­digitating with each other via ππ stacking inter­actions of the bromo­quinoline rings, preventing easy slippage of chains against each other. The stacked quinoline rings are thus related to each other through a twofold rotation (1 − x, +y, 1 − z). They are not exactly coplanar but their planes are angled against each other by 19.43 (8)°. As a result, no exact inter­planar distance can be defined, but the 3.432 (14) Å centroid-to-centroid distance between the quinoline rings (measured for the hemihydrate) indicates an efficient stacking inter­action. The closest atom-to-atom distance is 3.252 (7) Å for the two atoms C30 related by the twofold axis.

Additional weaker inter­actions within the 1D chains and between parallel chains as well as chains that are inclined with respect to each other are provided by C—H⋯O and C—H⋯N inter­actions involving the quinoline nitro­gen and several of the hydro­maleate oxygen atoms as well as by several C—H⋯π inter­actions towards the naphthyl and quinoline π-systems. The para C—H group of the phenyl ring forms a C—H⋯N hydrogen bond with the quinoline nitro­gen atom of a neighboring mol­ecule (at [{1\over 2}] + x, −[{1\over 2}] + y, +z). C—H⋯O bonds towards the maleate O atom O6 are established by both C3 and C6, being the methyl­ene and methyl groups of the dangling dimethyl propyl­ene ammonium group. O6 also acts as the hydrogen-bond acceptor for the hydroxyl O—H⋯O bond, and these C—H⋯O bonds thus just reinforce this connection within the hydrogen-bonded chains, and do not provide any new connection between chains. Atoms O4 and O5 of the maleate, on the other hand, act as C—H⋯O acceptors towards the methyl C6 and naphthyl C10 atoms from cations in neighboring chains, thus providing some stabilization for the overall 3D lattice. Another C—H⋯O inter­action towards O4, originating from another methyl C6 atom, does provide reinforcement for the N—H⋯O bond and no connection between neighboring chains. The meth­oxy and hydroxyl O atoms do not act as acceptors for intra­molecular C—H⋯O bonds. Finally, a number of inter­molecular C—H⋯π inter­actions towards the naphthyl and quinoline π-systems are observed: from naphthyl C14 and maleate C35 towards quinoline density (these inter­actions are within the 1D chains and assist in stabilizing the hydrogen bonds), from phenyl C19 towards maleate C35 (this is an inter-chain inter­action), and a weaker inter­action from methyl C6 towards naphthyl C10 (this is an inter-chain inter­action, but the geometry of this inter­action makes it unlikely to be very stabilizing). The sum of these inter­actions, especially the inter­locking of the stacked quinolones, is likely to prevent slippage of hydrogen-bonded chains against each other, which stabilizes the three-dimensional arrangement against collapse, even upon complete removal of all solvate mol­ecules.

Additional inter­molecular inter­actions towards the various solvate mol­ecules are observed. These are generally much weaker than the inter­actions described so far, with the possible exception of the water mol­ecules in the hemihydrate, which are partially hydrogen bonded to the main lattice. The partial occupancy of the water mol­ecules does, however, indicate that these hydrogen bonds are not essential in any way to sustain the overall structure, despite being individually quite strong. It appears that the water mol­ecules simply occupy the positions most suitable for them, but that they do not influence the overall structure much. This is further substanti­ated by the fact that the hemihydrate is isomorphous to the other solvates, with no indication that the structure is modulated much by the presence of the water mol­ecules. Their partial occupancy does, for example, not lead to disorder of the cations or anions, but the 1D chains are unfazed by the presence or absence of the water mol­ecules.

When the water mol­ecules are present, then they are located such that they are hydrogen bonded (Fig. 8[link]). One of the mol­ecules, associated with O7 and about one quarter occupied [refined occupancy 0.276 (17)] is located in a general position and is hydrogen bonded to the maleate C=O group of O3 (which is also hydrogen bonded to the ammonium cation). The second solvate water mol­ecule, associated with O8, is located on a twofold axis, and is in hydrogen-bonding distance to the other water mol­ecule. It features a higher occupancy rate, 0.40 (4), but less than double that of the first water mol­ecule, indicating that it is hydrogen bonded to either O7 or to its symmetry-related counterpart by the twofold axis, but not to both at the same time. Its large displacement ellipsoid indicates possible unresolved disorder resulting from the varying environments and/or large thermal libration due to the absence of a second hydrogen-bonding partner and the presence of an unoccupied void space instead. No second acceptor site for the first water mol­ecule is present, which indicates that the overall structure is not well suited for inclusion of water in its lattice. A PLATON SQUEEZE analysis (van der Sluis & Spek, 1990[Sluis, P. van der & Spek, A. L. (1990). Acta Cryst. A46, 194-201.]; Spek, 2015[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]) revealed 6.9% of additional void space not occupied by any solvate mol­ecules (even partially occupied). Crystals of the hemihydrate were grown from aceto­nitrile by evaporation with only trace amounts of water available from the solvent and the surrounding atmosphere, and crystals were exposed to atmosphere prior to analysis. Thus presence of additional aceto­nitrile solvate mol­ecules in the original crystals, which were subsequently lost, is likely. Attempts to grow single crystals from solvents with more available water have so far been unsuccessful, which indicates that the presence of larger amounts of water might result in formation of a different type of maleate salt. Further single crystal and powder XRD experiments are under way to investigate this possibility.

The less-than-ideal nature of the overall structure to host hydrogen-bonded guest solvate mol­ecules is supported by the ready formation of solvate structures with aprotic solvents, such as THF and acetone/hexane resulting in isomorphous structures with little or no modulation. Well-formed crystals could readily be grown from these solvents up to millimeters in size, showing how readily accessible this structural motif is.

THF mol­ecules in that solvate are only loosely bonded to anions and cations. Two sites occupied by THF mol­ecules were found. One located on a twofold axis and intrinsically 1:1 disordered. It is encapsulated between four different naphthyl groups and is weakly hydrogen bonded to all of them via C—H⋯O inter­actions originating from C9 and C12. The other mol­ecule is in a general position and exhibits no directional inter­actions with any neighboring entities at all, thus simply taking up the space provided by the lattice. The mol­ecule is disordered, in a refined ratio of 0.587 (16) to 0.413 (16), further supporting the absence of any steering inter­actions with its neighbors in space.

Acetone and hexane mol­ecules also do not strongly inter­act with the cations and anions in this solvate. Two distinct solvate-occupied sites are present in the lattice. One site is occupied by only acetone. This mol­ecule is located on and disordered around a twofold axis and is additionally disordered by a slight tilt of the mol­ecule. Occupancies refined to two × 0.230 (11) and two × 0.270 (11) for this site. The other solvate site is occupied by both acetone and hexane, with either one hexane mol­ecule located on another twofold axis, or two acetone mol­ecules being symmetry equivalent by this axis. The occupancy rates refined to 0.505 (9) and 0.495 (9) in slight favor of the acetone mol­ecules. The acetone mol­ecules of this site are weakly bound via a C—H⋯O inter­action to the meth­oxy methyl group and to one of the maleate C—H groups. No other directional inter­actions of either acetone or hexane with anions or cations are observed.

Inter­actions with solvate mol­ecules are more pronounced in the ethyl acetate solvate, but the exact nature of the inter­actions is obscured by substantial disorder, with up to fivefold disorder refined for one solvate cluster. Solvate disorder induces disorder of a cation phenyl group and a cation naphthyl group (see the Refinement section for a more detailed discussion of disorder). Some C—H⋯O inter­actions appear evident for the major disordered moieties though, which will be discussed below. The larger extent of the solvate inter­action with the main structure, when compared to the hemihydrate, THF and acetone/hexane solvates, is also supported by the fact that the ethyl acetate solvate is not exactly isomorphous with the other three solvates, but is modulated and crystallizes with lower symmetry than the other structures. C-centered and twofold symmetry are broken, resulting in a structure with a similar unit-cell size and shape, but with a primitive lattice and space group P21. Exact translation and twofold symmetry for the ethyl acetate solvate is broken by ordering of the solvate mol­ecules and by a slight modulation of cations and anions (see Refinement section for more details).

The ethyl acetate mol­ecules are arranged into two clusters with light and severe disorder, refined as twofold and fivefold disorder, with partial overlap between the two clusters. Total occupancy for the severely disordered site refined to less than unity, just above 60% [0.641 (6)], inducing disorder for the surrounding naphthyl and phenyl groups. Additional unresolved disorder cannot be ruled out for this site. Despite the pseudo-translational symmetry, the two solvate sites are clearly distinct from each other, with little to no correlation effects between the two sites, and the differences between the two solvent sites appear to be the main reason for modulation and breaking of the C2 symmetry.

In the less disordered and fully occupied solvate site, the major moiety ethyl acetate [87.4 (3)% occupancy] is hydrogen bonded via its keto group to the meth­oxy methyl group, C32A. The major moiety mol­ecule of the other site, on the other hand, exhibits C–H⋯O bonds originating from methyl ammonium C5A and naphthyl C12B. The same inter­action is observed for one of the minor moieties at this site, with a combined occupancy rate of 35.4%, or more than half of the total site occupancy. No C—H⋯O inter­action originating from the meth­oxy methyl group C32B is present.

4. Stability and desolvation, solvent-free salt

The stronger inter­action of the ethyl acetate solvate mol­ecules with the framework mol­ecules, when compared to their THF and acetone/hexane analogues, also translates into the stabil­ity of the solvates. The THF and acetone/hexane analogues readily loose most of their solvate mol­ecules under ambient conditions, and crystals become opaque within a few hours. Crystals of the ethyl acetate solvate, under the same conditions, do not change in appearance. When taken out of solution and stored overnight, exposed to normal atmosphere, crystals of the ethyl acetate solvate are visually unchanged, and data collected from single crystals are unchanged from data collected from a crystal fresh out of mother liquor. Solvate mol­ecules are still clearly resolved, the disorder pattern is not changed noticeably, and occupancy rates are unchanged. The modulation of the main mol­ecule framework is preserved, unit-cell parameters are virtually unchanged (reduction by 0.3%), and mosaicity is essentially unchanged (0.73° and 0.77°, respectively; see supporting information, Fig. S1).

Crystals of the THF and acetone/hexane solvate behave differently. Crystals of either compound become milky within a few minutes of being taken out of mother liquor, and even the cores of large crystals (up to 1 mm) completely lose transparency within a few hours when stored in air outside the mother liquor. Crystals do, however, retain crystallinity, despite becoming opaque and white in appearance. Single-crystal data for such a crystal obtained from the acetone/hexane solvate did diffract well, with little to no loss of diffraction power compared to the solvated crystals or the ethyl acetate solvate (Fig. S1 in the supporting information), and there was only a small increase in mosaicity from 0.71° to 0.85° after storing in air for 14 h.

Hot stage microscopy showed that if the crystals are crushed, solvent loss is rapid for both the acetone/hexane as well as the ethyl acetate samples. When single crystals were crushed on a microscope slide and heated at 10.0°C min−1 to 110.0°C, then at 5.0°C min−1 to 120.0°C and then finally at 2.0°C min−1 to 140.0°C, no loss of solvate mol­ecules was observable for either the acetone/hexane nor the ethyl acetate crystals for either a dry sample or immersed in mineral oil. Onset of melting was observed between 122.1 and 124.5°C, and melting was complete at 128.3 to 133.7°C, with no noticeable difference between the acetone/hexane and the ethyl acetate sample (Table 9[link], selected figures shown in the supporting information). The comparable melting temperatures of these materials support the finding from XRD that the crystal structures of the maleate solvates are isomorphically related and that the presence of solvate is not required to maintain these structures. This indicates that for smaller particles, solvate mol­ecules are rapidly lost for both solvates, possibly before start of the hot stage microscopy experiment, while larger crystals of the ethyl acetate solvate (> 200 µm3 such as used for single-crystal diffraction) do not desolvate readily and retain most of their solvate mol­ecules.

Table 9
Hot stage optical microscopy data for the acetone/hexane and the ethyl acetate crystals

  Run 1 Run 2 Run 3 (in mineral oil)
acetone/hexane solvate, onset and end of melting 124.5°C, 133.7°C 122.1°C, 133.7°C 119.9°C, 128.8°C
ethyl acetate solvate, onset and end of melting 122.1°C, 133.6°C 122.8°C, 133.6°C 118.4°C, 128.3°C

For the acetone/hexane sample stored in atmosphere overnight, when analyzed by SC-XRD, a noticeable change of the unit-cell dimensions was observed, accompanied by a decrease in volume by ca 3.5% [from 3733.9 (3) to 3603.0 (5) Å3]. An overlay of the structure before and after desolvation is shown in the supporting information (Fig. S2). Changes of unit-cell parameters and a slight shifting of functional groups are perceptible, but the overall magnitude of those changes is small.

The decrease of the unit-cell volume is, however, substanti­ally less than the 20.9% of the volume taken up by solvate mol­ecules in the acetone/hexane solvate, Fig. 9[link]. Indeed, a PLATON SQUEEZE analysis (van der Sluis & Spek, 1990[Sluis, P. van der & Spek, A. L. (1990). Acta Cryst. A46, 194-201.]; Spek, 2015[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]) reveals a residual void space of 16.8% of the unit-cell volume, Fig. 10[link]. This indicates that either a substantial fraction of the solvate mol­ecules is retained, or that the hydrogen-bonded framework is stable enough to withstand collapse, even without any solvate mol­ecules in the void space between the bedaquilinium maleate framework. A future in-depth analysis of several bedaquilinium salts, including the various solvates of the maleate system, will focus on their thermal stability and physical properties, and will include thermal gravimetric analysis, porosity measurements of the desolvated salts and surface-area measurements. The single-crystal structure of the acetone/hexane crystals stored under ambient conditions does, however, already provide some first insights. Analysis of the data revealed a well-defined bedaquilinium maleate framework, with barely any increased libration, but a completely featureless electron-density difference map for the areas previously taken up by the acetone/hexane mol­ecules. The largest difference-electron peaks inside the void area are less than 0.5 e Å3. A solvate SQUEEZE analysis performed using the program PLATON revealed some residual electron density, but substanti­ally less than what would be expected for full occupancy. The SQUEEZE procedure corrected for 66 electrons within the solvent-accessible voids, equivalent to 1.14 mol­ecules of acetone per unit cell, or 0.28 acetone per cation–anion pair. Prior to desolvation, one mol­ecule of acetone and half a mol­ecule of hexane were present per cation–anion pair, equivalent to 202 electrons per unit cell. Thus, there seems to be some retention of solvate mol­ecules within the voids (ca one third based on the SQUEEZE data), but those solvate mol­ecules appear to be completely disordered and equally distributed within the solvate-accessible area. The bedaquil­inium maleate framework is not affected by the residual solvate. No disorder is observed for either cation or anion, nor any increased libration, indicating that any residual solvate has negligible inter­action with the framework, and that desolvation is homogeneous throughout the whole crystal. Thermal gravimetric analysis and surface measurements, to be reported in an upcoming publication, will provide more insight as to how much or if any residual solvates are indeed present in the void area.

[Figure 9]
Figure 9
Residual void space in the acetone/hexane structure after artificial removal of solvent mol­ecules. The solvent-accessible volume would be 781 Å3 [20.9% of the unit-cell volume; probe radius 1.2 Å; numerical values from PLATON SQUEEZE calculation (van der Sluis & Spek, 1990[Sluis, P. van der & Spek, A. L. (1990). Acta Cryst. A46, 194-201.]; Spek, 2015[Spek, A. L. (2015). Acta Cryst. C71, 9-18.])]. Probability ellipsoids are at the 50% level.
[Figure 10]
Figure 10
Residual void space in the desolvated structure. The solvent-accessible volume is 607 Å3 [16.8% of the unit cell volume; probe radius 1.2 Å; numerical values from PLATON SQUEEZE calculation (van der Sluis & Spek, 1990[Sluis, P. van der & Spek, A. L. (1990). Acta Cryst. A46, 194-201.]; Spek, 2015[Spek, A. L. (2015). Acta Cryst. C71, 9-18.])]. Probability ellipsoids are at the 50% level.

5. Database survey

Only four structures of bedaquiline or its salts have been previously reported in the literature (Cambridge Structural Database; Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]), viz. free base bedaquiline (Petit et al., 2007[Petit, S., Coquerel, G., Meyer, C. & Guillemont, J. (2007). J. Mol. Struct. 837, 252-256.]), the fumarate salt (Okezue et al., 2020[Okezue, M., Smith, D., Zeller, M., Byrn, S. R., Smith, P., Bogandowich-Knipp, S., Purcell, D. K. & Clase, K. L. (2020). Acta Cryst. C76, 1010-1023.]), and two isomorphous solvates of the benzoate salt (Okezue et al., 2020[Okezue, M., Smith, D., Zeller, M., Byrn, S. R., Smith, P., Bogandowich-Knipp, S., Purcell, D. K. & Clase, K. L. (2020). Acta Cryst. C76, 1010-1023.]). The structures of the salts are dominated by a multitude of N—H⋯O and O—H⋯O hydrogen-bonding inter­actions that connect the cations and anions into strongly hydrogen-bonded motifs, while in free base bedaquiline the packing is dominated by weaker and less directional inter­actions such as Br⋯Br inter­actions and π-stacking (Petit et al., 2016[Petit, S., Coquerel, G., Meyer, C. & Guillemont, J. (2007). J. Mol. Struct. 837, 252-256.]). In all structures, the ethane backbone and the malleable ethyl­amine fragment of the bedaquiline core give the cations a high degree of flexibility, and mol­ecular conformations not only vary widely between the bedaquiline and bedaquilinium structures, but even between independent mol­ecules within the same structure (both the free base and the fumarate are Z′ = 2 structures). The fumarate salt was solvent free. The benzoate salt formed a hydrate with one strongly bound solvate water mol­ecule, and a second solvate site occupied either partially by water (occupancy 17%) or by disordered aceto­nitrile. The aceto­nitrile solvate was prone to desolvation and converted quickly into a simple monohydrate once taken out of solution. In both of the salts, the anions and cations are bridged via hydrogen atoms into 2D ribbons in which the bedaquilinum cations wrap around a single strand of anions (fumarate) or around anions and water mol­ecules (benzoate). This differentiates the fumarate and benzoate salts from the maleates, which exhibit simpler 1D chains of anions and cations.

6. Methods and procedures

Maleic acid was purchased from BTC, THF from VWR chemicals, acetone from VWR chemicals, ethyl acetate from Macron, and aceto­nitrile from VWR Chemicals. Bedaquil­inium fumarate was obtained from Johnson & Johnson. All chemicals were used as received without further purification. Free base bedaquiline was prepared by extracting a CH2Cl2 solution of the fumarate three times with saturated NaHCO3 solution (Rombouts et al., 2016[Rombouts, J. A., Veenboer, R. P., Villellas, C., Lu, P., Ehlers, A. W., Andries, K., Koul, A., Lill, H., Ruijter, E., Orru, R. V. A., Lammertsma, K., Bald, D. & Slootweg, J. C. (2016). RSC Adv. 6, 108708-108716.]).

7. Hot stage optical microscopy

Analyses were completed using an Olympus Series BX51TRF microscope (Olympus America Inc., Melville, NY) equipped with 12V/100W illumination, an achromat 0.9 NA polarized light condenser, a 20X, 0.40 Numerical Aperture, LM PLAN FL N objective, an inter­mediate tube with variable position analyzer and first-order red compensator, a trinocular viewing head with a Lumenera Series Infinity X (Teledyne Lumenera, Ottawa, Ontario, Canada) digital camera using Infinity software version 6.5.6 and Infinity Analyze software version 7.0.2.930 (build date 01-Feb-2020). Heating was conducted with a Linkam LTS420 hot stage with a T95 LinkPad system controller. A single crystal of either the acetone/hexa­nes or ethyl acetate (200 µm3) was removed from the solvent and crushed on a clean microscope slide under a No. 1 1/2 cover glass. A small portion of each sample was transferred to three individual clean microscope slides under a No. 1 1/2 cover glass for analysis. A preset heating program ramp was used during each individual analysis using the hot stage system controller programmed with a ramp of 10.0°C min−1 to 110.0°C, at 5.0°C min−1 to 120.0°C, and at 2.0°C min−1 to 140.0°C. The system calibration was verified with melting-point standards prior to analyses. Samples were analyzed in triplicate, twice as dry mounts and once in mineral oil, USP (CAS: 8042-47-5), which was allowed to cover the sample by capillarity. Sample and thermomicroscopy information is given in Table 9[link], selected images are given in the supporting information.

8. Synthesis and crystallization

Hemihydrate, C32H32BrN2O2·C4H3O4·0.5H2O: Bedaquiline free base (400.3 mg) was weighed into a 20 mL glass scintillation vial and dissolved in 3 mL of THF. Maleic acid (85.6 mg) was added and the contents mixed. The solution was allowed to evaporate slowly at ambient conditions. White crystals that appeared dry were evident within two days in the vial. Approximately 14 mg of this dried material was weighed into a 2 dram glass vial, re-dissolved in 800 µL ACN by vortexing/sonicating until just dissolved, and wrapped in aluminum foil. An 18 gauge needle was placed into the top of the conical-shaped foil to allow for slow evaporation at ambient conditions until solids were evident and the sample appeared dry.

THF solvate, C32H32BrN2O2·C4H3O4·1.5C4H8O: Bedaquiline free base (400.3 mg) was weighed into a 20 mL glass scintillation vial and dissolved in 3 mL THF. Maleic acid (85.6 mg) was added and the contents mixed. The solution was allowed to evaporate slowly at ambient conditions. White crystals that appeared dry were evident within two days in the vial. Approximately 16 mg of this dried material was weighed into a 2 dram glass vial, re-dissolved in 1200 µL THF, and wrapped in aluminum foil. An 18 gauge needle was inserted into the top of the aluminum foil to allow for slow evaporation at ambient conditions until solids were evident and the sample appeared dry.

Acetone/hexane solvate, C32H32BrN2O2·C4H3O4·C2H6O2·0.25C6H14: Bedaquiline maleate (23.1 mg) was weighed into a glass vial and dissolved in acetone (3 mL). A layer of n-hexa­nes was gently streamed onto the top of the solution. The vial contents were capped and placed under a hood at ambient conditions. After two days, clear crystals were evident in the vial.

Desolvated structure, C32H32BrN2O2·C4H3O4: Crystals of the solvent-free compound were obtained from the monoacetone quadrant-hexane solvate by drying in air on a microscope slide. Crystals become milky overnight when taken out of mother liquor solution and left to dry in air, but retain crystallinity. Data collection revealed a solvent-free structure.

Ethyl acetate solvate, C32H32BrN2O2·C4H3O4·0.821C4H8O2: Bedaquiline maleate (22.3 mg) was weighed into glass vial and dissolved in ethyl acetate (4 mL). A layer of n-hexa­nes was gently streamed onto the top of the solution. The vial contents were capped and allowed to equilibrate at ambient conditions. After two days, clear crystals were evident in the vial.

9. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 10[link].

Table 10
Experimental details

  hemihydrate THF solvate ethyl acetate solvate acetone/hexane solvate
Crystal data
Chemical formula C32H32BrN2O2+·C4H3O4·0.476H2O 2C32H32BrN2O2+·2C4H3O4·3C4H8O C32H32BrN2O2+·C4H3O4·0.821C4H8O2 2C32H32BrN2O2+·2C4H3O4·0.495C6H14·2.01C3H6O
Mr 680.17 1559.45 743.88 1502.51
Crystal system, space group Monoclinic, C2 Monoclinic, C2 Monoclinic, P21 Monoclinic, C2
Temperature (K) 150 150 150 150
a, b, c (Å) 15.7469 (5), 13.2627 (4), 17.8602 (6) 16.4119 (6), 13.5643 (6), 17.8475 (8) 16.1525 (10), 13.5353 (9), 17.8572 (11) 16.0678 (9), 13.6440 (8), 17.8720 (8)
β (°) 106.3762 (13) 107.318 (3) 107.359 (2) 107.6347 (18)
V3) 3578.7 (2) 3793.0 (3) 3726.3 (4) 3733.9 (3)
Z 4 2 4 2
Radiation type Cu Kα Cu Kα Mo Kα Mo Kα
μ (mm−1) 1.94 1.92 1.16 1.15
Crystal size (mm) 0.21 × 0.17 × 0.13 0.33 × 0.19 × 0.16 0.45 × 0.43 × 0.37 0.48 × 0.35 × 0.21
 
Data collection
Diffractometer Bruker AXS D8 Quest with PhotonIII C14 CPAD Bruker AXS D8 Quest with PhotonIII C14 CPAD Bruker AXS D8 Quest with PhotonII CPAD Bruker AXS D8 Quest with PhotonII CPAD
Absorption correction Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.]) Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.]) Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.]) Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.])
Tmin, Tmax 0.646, 0.754 0.254, 0.391 0.670, 0.742 0.439, 0.498
No. of measured, independent and observed [I > 2σ(I)] reflections 15060, 7003, 6474 18660, 7473, 6615 153291, 28338, 15758 73087, 14074, 9700
Rint 0.040 0.049 0.082 0.059
(sin θ/λ)max−1) 0.638 0.639 0.770 0.769
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.107, 1.08 0.054, 0.127, 1.05 0.062, 0.200, 1.03 0.047, 0.126, 1.03
No. of reflections 7003 7473 28338 14074
No. of parameters 430 551 1359 558
No. of restraints 8 223 1870 407
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.35, −0.46 0.46, −0.52 0.88, −1.03 0.61, −0.62
Absolute structure Flack x determined using 2633 quotients [(I+)−(I)]/[(I+)+(I)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.]) Refined as an inversion twin Flack x determined using 5601 quotients [(I+)−(I)]/[(I+)+(I)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.]). Flack x determined using 3753 quotients [(I+)−(I)]/[(I+)+(I)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])
Absolute structure parameter 0.019 (8) 0.03 (3) 0.020 (4) 0.006 (3)
  desolvated structure desolvated structure (SQUEEZE applied)
Crystal data
Chemical formula C32H32BrN2O2+·C4H3O4 C32H32BrN2O2+·C4H3O4
Mr 671.56 671.56
Crystal system, space group Monoclinic, C2 Monoclinic, C2
Temperature (K) 150 150
a, b, c (Å) 15.7494 (12), 13.3568 (11), 17.8634 (14) 15.7494 (12), 13.3568 (11), 17.8634 (14)
β (°) 106.500 (3) 106.500 (3)
V3) 3603.0 (5) 3603.0 (5)
Z 4 4
Radiation type Mo Kα Mo Kα
μ (mm−1) 1.19 1.19
Crystal size (mm) 0.48 × 0.35 × 0.21 0.48 × 0.35 × 0.21
 
Data collection
Diffractometer Bruker AXS D8 Quest with PhotonII CPAD Bruker AXS D8 Quest with PhotonII CPAD
Absorption correction Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.]) Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.])
Tmin, Tmax 0.678, 0.740 0.678, 0.740
No. of measured, independent and observed [I > 2σ(I)] reflections 78980, 13641, 10348 78970, 13639, 10346
Rint 0.049 0.049
(sin θ/λ)max−1) 0.769 0.769
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.142, 1.06 0.042, 0.119, 1.06
No. of reflections 13641 13639
No. of parameters 418 418
No. of restraints 1 1
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) 0.89, −0.74 0.76, −0.63
Absolute structure Flack x determined using 4138 quotients [(I+)−(I)]/[(I+)+(I)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.]) Flack x determined using 4139 quotients [(I+)−(I)]/[(I+)+(I)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])
Absolute structure parameter 0.044 (3) 0.044 (3)
Computer programs: APEX3 and SAINT (Bruker, 2020[Bruker (2020). APEX3 and SAINT. Bruker Nano Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2018/3 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]), shelXle (Hübschle et al., 2011[Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281-1284.]), Mercury (Macrae et al., 2020[Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226-235.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

The structures of the four solvates and of the solvent-free salt are closely related. The hemihydrate, THF solvate, the acetone/hexane solvate and the solvate-free salt derived from the acetone/hexane solvate are isomorphous in space group C2. In the ethyl acetate solvate, C-centered and twofold symmetry is broken and the salt crystallizes in P21, but the structure is closely related to the other C-centered structures.

The four isomorphous structures were refined using a common model for the non-solvate part of the structures, with the THF solvate, the acetone/hexane solvate and the desolvated structure solved by isomorphous replacement. The ethyl acetate solvate was solved independently, by dual Patterson/direct methods, but the atom-naming scheme from the other structures was adopted and augmented by suffixes A and B to distinguish between the two cation–anion pairs related by pseudo-translation.

Hydrogen-atom treatment: C—H bond distances were constrained to 0.95 Å for aromatic and alkene C—H moieties, and to 1.00, 0.99 and 0.98 Å for aliphatic C—H, CH2 and CH3 moieties, respectively. N—H bond distances were constrained to 1.00 Å for pyramidal (sp3 hybridized) ammonium R3H+ groups. O—H distances of alcohols were constrained to 0.84 Å. Methyl CH3 and hydroxyl H atoms were allowed to rotate but not to tip to best fit the experimental electron density. The positions of hydro­maleate acidic hydrogen atoms were freely refined. Water H-atom positions in the hemihydrate were refined and O—H and H⋯H distances were restrained to 0.84 (2) and 1.36 (2) Å, respectively. H-atom positions were further restrained based on hydrogen-bonding considerations. A damping factor was applied during refinement. In the final refinement cycles, the damping factor was removed and the water H atoms were constrained to ride on their carrier oxygen atoms. Uiso(H) values were set to a multiple of Ueq(C/O/N) with 1.5 for CH3 and OH, and 1.2 for C—H, CH2 and N—H units, respectively.

Disorder and solvate refinement, handling of void space:

In the hemihydrate, two partially occupied water mol­ecules are situated in the asymmetric part of the unit cell. One is in a general position, the other located on a twofold axis. They are hydrogen bonded to each other, and the one in the general position is also hydrogen bonded to atom O3 of the hydro­maleate anion. Water H-atom positions were refined as described above. Occupancy rates refined to 0.276 (17) for O7 (in the general position) and 0.40 (4) for O8 (on the twofold axis).

Additional solvent-accessible space is present in the crystal lattice (two × 123 Å3 or 6.9% of the unit-cell volume). No electron density was found inside the void space [a PLATON SQUEEZE analysis (van der Sluis & Spek, 1990[Sluis, P. van der & Spek, A. L. (1990). Acta Cryst. A46, 194-201.]; Spek, 2015[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]) found eight electrons in the combined void space], and the content of the void space was ignored.

In the THF solvate, two THF mol­ecules were refined as disordered, one in a 1:1 ratio around a twofold rotation axis, the other in a general position. The three disordered moieties were restrained to have similar geometries. Uij components of ADPs for disordered atoms closer to each other than 2.0 Å were restrained to be similar. Subject to these conditions, the occupancy ratio for the mol­ecule in the general position refined to 0.587 (16) to 0.413 (16).

In the acetone/hexane solvate, two symmetry-equivalent acetone mol­ecules are disordered with a hexane mol­ecule located on a twofold axis. Another acetone mol­ecule is located on and disordered around a twofold axis and additionally disordered by a slight tilt of the mol­ecule. All acetone moieties were restrained to have similar geometries and to be close to planar. The two C—C bond distances within the acetone were restrained to be similar to each other. C—C bond distances of the hexane mol­ecule were restrained to target values [1.55 (1) Å] and hexane C—C—C angles were restrained to be similar. Uij components of ADPs for disordered atoms closer to each other than 2.0 Å were restrained to be similar. Subject to these conditions, the occupancy rates refined to 0.505 (9) and 0.495 (9) for the acetone/hexane disorder, and two × 0.230 (11) and two × 0.270 (11) for the disordered acetone.

The structure of the ethyl acetate solvate exhibits pseudo C-centered symmetry emulating space group C2 as observed for the hemihydrate, THF and acetone/hexane solvates and the solvent-free salt derived from the acetone/hexane solvate. Exact translation and twofold symmetry for the ethyl acetate solvate is broken by the solvate mol­ecules and by a slight modulation of cations and anions. The mean intensity for reflections that should be systematically absent in C2 was 1.8, vs 6.9 for all reflections (2.2 vs 2.9 for mean intensity/σ).

Ethyl acetate mol­ecules are arranged into two clusters with light and severe disorder. Solvate disorder induces disorder of a cation phenyl and a cation naphthyl group. The site associated with the ethyl acetate mol­ecule of O1/O2 was refined as twofold disordered and as fully occupied. The site associated with the ethyl acetate mol­ecule of O3/O4 was refined as fivefold disordered and only partially occupied. One of the moieties of O3/O4 (suffix F) extends away from the main cluster. It induces the disorder of the O1/O2 ethyl acetate, and for the naphthyl group of cation A. A common occupancy ratio was used for these three entities. Disorder of the phenyl group of cation B is correlated with multiple disordered moieties of the severely disordered ethyl acetate and was refined independently.

All ethyl acetate moieties were restrained to have similar geometries. The acetate sections were restrained to be close to planar. The ethyl C—C bond distances were restrained to a target value [1.55 (2) Å]. Disordered phenyl and naphthyl groups were restrained to have similar geometries as their not disordered counterparts in the other cation. Uij components of ADPs for disordered atoms closer to each other than 2.0 Å were restrained to be similar. Subject to these conditions, the occupancy rates refined to 0.874 (3) to 0.126 (3) for the twofold-disordered ethyl acetate of O1/O2 (shared with the naphthyl disorder of cation A). The occupancy rates for the partially occupied site refined to 0.171 (7), 0.183 (7), 0.126 (3) (the same as minor moiety of O1/O2 ethyl acetate), 0.074 (6) and 0.087 (6), for a total occupancy of 0.641. The occupancy ratio of the phenyl disorder of cation B refined to 0.573 (17) to 0.427 (17).

Crystals of the solvate-free salt were obtained from the acetone/hexane solvate by drying on a glass slide in air overnight. In the solvated structure, acetone and hexane mol­ecules are located in infinite channels and slowly vacate the crystal lattice. Crystals become milky overnight when taken out of mother liquor solution and left to dry in air, but retain crystallinity.

No substantial electron density was found in the previously solvate-occupied channels (largest void peaks are less than 0.5 electrons per cubic Ångstrom), and the residual electron-density peaks are not arranged in an inter­pretable pattern. The structure was refined both with and without correction of residual electron density, with only marginally different results. In the second approach, the structure factors were augmented via reverse Fourier transform methods using the SQUEEZE routine (van der Sluis & Spek, 1990[Sluis, P. van der & Spek, A. L. (1990). Acta Cryst. A46, 194-201.]; Spek, 2015[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]) as implemented in the program PLATON. The resultant FAB file containing the structure-factor contribution from the electron content of the void space was used together with the original hkl file in the further refinement. (The FAB file with details of the SQUEEZE results is appended to the CIF). The SQUEEZE procedure corrected for 66 electrons within the solvent-accessible voids, equivalent to 1.14 mol­ecules of acetone per unit cell, or 0.28 acetone per cation–anion pair. Prior to desolvation, one mol­ecule of acetone and a quarter mol­ecule of hexane were determined per cation–anion pair [the F(000) values of the solvated and unsolvated structures differ by 178 electrons].

Supporting information


Computing details top

For all structures, data collection: APEX3 (Bruker, 2020); cell refinement: SAINT (Bruker, 2020); data reduction: SAINT (Bruker, 2020). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for hemihydrate, THF, acetone_hexane, desolvated, desolvated_sq; SHELXT (Sheldrick, 2015a) for ethyl_acetate. For all structures, program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b), shelXle (Hübschle et al., 2011); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

[4-(6-bromo-2-methoxyquinolin-3-yl)-3-hydroxy-3-(naphthalen-1-yl)-4-phenylbutyl]dimethylazanium 3-carboxyprop-2-enoate 0.476-hydrate (hemihydrate) top
Crystal data top
C32H32BrN2O2+·C4H3O4·0.476H2OF(000) = 1411
Mr = 680.17Dx = 1.262 Mg m3
Monoclinic, C2Cu Kα radiation, λ = 1.54178 Å
a = 15.7469 (5) ÅCell parameters from 9805 reflections
b = 13.2627 (4) Åθ = 2.6–79.1°
c = 17.8602 (6) ŵ = 1.94 mm1
β = 106.3762 (13)°T = 150 K
V = 3578.7 (2) Å3Block, colourless
Z = 40.21 × 0.17 × 0.13 mm
Data collection top
Bruker AXS D8 Quest with PhotonIII_C14 CPAD
diffractometer
7003 independent reflections
Radiation source: I-mu-S microsource X-ray tube6474 reflections with I > 2σ(I)
Laterally graded multilayer (Goebel) mirror monochromatorRint = 0.040
Detector resolution: 7.4074 pixels mm-1θmax = 79.8°, θmin = 2.6°
ω and phi scansh = 1919
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
k = 1616
Tmin = 0.646, Tmax = 0.754l = 1822
15060 measured reflections
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.041 w = 1/[σ2(Fo2) + (0.0255P)2 + 3.0883P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.107(Δ/σ)max < 0.001
S = 1.08Δρmax = 0.35 e Å3
7003 reflectionsΔρmin = 0.46 e Å3
430 parametersExtinction correction: SHELXL2018/3 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
8 restraintsExtinction coefficient: 0.00103 (15)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack x determined using 2633 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.019 (8)
Special details top

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

Refinement. The position of the hydromaleate acidic hydrogen atom was freely refined.

Two partially occupied water molecules are situated in the asymmetric part of the unit cell. One in a general position, the other located on a twofold axis. They are hydrogen bonded to each other, and the one ion the general position is also H-bonded to O3 of the hydromaleate anion. Water H atom positions were refined and O-H and H···H distances were restrained to 0.84 (2) and 1.36 (2) Angstrom, respectively, and H atom positions were further restrained based on hydrogen bonding considerations. A damping factor was applied during refinement. In the final refinement cycles the damping factor was removed and the water H atoms were set to ride on their carrier oxygen atoms. Subject to these conditions the occupancy rates refined to 0.276 (17) for O7 (general position) and 0.40 (4) for O8 (twofold axis).

Additional solvent accessible space is present in the crystal lattice (two times 123 cubic Angstrom, or 6.9% of the unit cell volume). No electron density was found inside the void space (A Platon Squeeze analysis corrected for 8 electrons in the combined void space), and the content of the void space was ignored.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.30375 (5)0.01666 (6)0.48115 (4)0.0839 (3)
O10.48764 (16)0.27255 (18)0.16376 (15)0.0333 (5)
H1O0.4406780.2885340.1742940.040*
O20.56686 (17)0.48680 (18)0.36191 (15)0.0366 (6)
O30.48874 (18)0.6977 (2)0.21055 (18)0.0454 (7)
O40.5661 (2)0.7107 (3)0.12579 (16)0.0555 (9)
O50.7100 (2)0.7702 (3)0.12234 (17)0.0541 (8)
H50.642 (4)0.739 (4)0.118 (3)0.065*
O60.83376 (18)0.8188 (2)0.20818 (18)0.0459 (7)
N10.39765 (18)0.5691 (2)0.09891 (17)0.0289 (6)
H10.4309170.6208890.1365860.035*
N20.46061 (19)0.4070 (3)0.40605 (17)0.0343 (7)
C10.6050 (2)0.3244 (3)0.27938 (19)0.0298 (7)
H1A0.6434440.3842400.2990180.036*
C20.5524 (2)0.3481 (3)0.1918 (2)0.0289 (7)
C30.5040 (2)0.4505 (3)0.18735 (18)0.0278 (7)
H3A0.4594790.4459090.2167730.033*
H3B0.5473080.5033110.2120950.033*
C40.4581 (2)0.4805 (3)0.10285 (19)0.0296 (7)
H4A0.5033600.4977100.0761160.036*
H4B0.4234220.4226230.0751960.036*
C50.3164 (2)0.5436 (3)0.1216 (2)0.0381 (8)
H5A0.2814060.4941760.0847790.057*
H5B0.2811230.6047310.1206110.057*
H5C0.3329400.5150030.1743310.057*
C60.3746 (2)0.6148 (3)0.0197 (2)0.0356 (8)
H6A0.3488690.5631920.0193490.053*
H6B0.4282090.6421510.0096740.053*
H6C0.3316720.6692210.0165970.053*
C70.6162 (2)0.3460 (3)0.14034 (19)0.0295 (7)
C80.5999 (3)0.2769 (3)0.0803 (2)0.0359 (8)
H80.5504780.2330130.0725700.043*
C90.6545 (3)0.2695 (3)0.0299 (2)0.0423 (9)
H90.6402990.2222960.0118470.051*
C100.7265 (3)0.3288 (3)0.0404 (2)0.0430 (9)
H100.7630790.3222130.0064980.052*
C110.7480 (3)0.4006 (3)0.1014 (2)0.0401 (9)
C120.8229 (3)0.4631 (4)0.1120 (3)0.0544 (11)
H120.8598110.4544990.0785290.065*
C130.8443 (3)0.5352 (4)0.1683 (3)0.0560 (12)
H130.8948330.5768370.1739120.067*
C140.7905 (3)0.5467 (3)0.2176 (3)0.0471 (10)
H140.8048870.5966590.2572880.056*
C150.7170 (2)0.4875 (3)0.2103 (2)0.0375 (8)
H150.6818370.4977280.2450510.045*
C160.6919 (2)0.4111 (3)0.1521 (2)0.0316 (7)
C170.6665 (2)0.2338 (3)0.2887 (2)0.0340 (7)
C180.6427 (3)0.1422 (3)0.2516 (2)0.0415 (9)
H180.5861400.1350210.2149260.050*
C190.7002 (3)0.0608 (4)0.2671 (3)0.0558 (12)
H190.6828970.0013800.2408400.067*
C200.7823 (4)0.0694 (4)0.3204 (3)0.0641 (14)
H200.8214730.0134250.3311890.077*
C210.8069 (3)0.1597 (5)0.3579 (3)0.0659 (15)
H210.8630770.1657850.3952770.079*
C220.7503 (3)0.2422 (4)0.3417 (2)0.0476 (10)
H220.7688040.3047560.3668770.057*
C230.5424 (2)0.3152 (3)0.33007 (19)0.0301 (7)
C240.5058 (2)0.2271 (3)0.34449 (19)0.0321 (7)
H240.5207830.1660810.3233200.039*
C250.4456 (2)0.2245 (3)0.3907 (2)0.0361 (8)
C260.4097 (3)0.1350 (4)0.4095 (2)0.0434 (9)
H260.4264660.0719680.3927850.052*
C270.3499 (3)0.1392 (4)0.4524 (2)0.0511 (11)
C280.3230 (3)0.2303 (4)0.4767 (2)0.0511 (11)
H280.2802670.2313050.5050790.061*
C290.3584 (3)0.3182 (4)0.4597 (2)0.0441 (10)
H290.3398940.3804290.4762750.053*
C300.4221 (2)0.3183 (3)0.4178 (2)0.0359 (8)
C310.5198 (2)0.4035 (3)0.36758 (19)0.0309 (7)
C320.5519 (3)0.5748 (3)0.4034 (3)0.0503 (10)
H32A0.4932570.6026280.3775970.075*
H32B0.5972640.6254860.4035430.075*
H32C0.5549390.5564470.4571970.075*
C330.5569 (2)0.7229 (3)0.1938 (2)0.0363 (8)
C340.6313 (3)0.7650 (3)0.2571 (2)0.0377 (8)
H340.6188400.7737060.3057690.045*
C350.7131 (2)0.7926 (3)0.2566 (2)0.0369 (8)
H350.7498260.8154440.3054300.044*
C360.7555 (3)0.7933 (3)0.1923 (2)0.0372 (8)
O70.4482 (13)0.8469 (14)0.3326 (10)0.106 (9)0.276 (17)
H7A0.4614170.8034390.3037380.159*0.276 (17)
H7B0.4778410.8991990.3315240.159*0.276 (17)
O80.5000000.777 (3)0.5000000.30 (4)0.40 (4)
H8A0.4881520.8152450.4543440.443*0.40 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0824 (4)0.0920 (5)0.0923 (5)0.0330 (3)0.0492 (4)0.0030 (4)
O10.0317 (11)0.0322 (12)0.0336 (12)0.0002 (10)0.0051 (10)0.0007 (10)
O20.0427 (13)0.0362 (13)0.0312 (13)0.0063 (10)0.0106 (11)0.0011 (10)
O30.0404 (14)0.0510 (16)0.0496 (16)0.0108 (13)0.0203 (13)0.0087 (13)
O40.0459 (15)0.089 (2)0.0337 (14)0.0255 (16)0.0139 (12)0.0177 (16)
O50.0492 (16)0.082 (2)0.0334 (14)0.0239 (16)0.0148 (12)0.0089 (15)
O60.0356 (13)0.0453 (15)0.0565 (17)0.0048 (12)0.0127 (12)0.0015 (14)
N10.0260 (13)0.0298 (13)0.0302 (14)0.0031 (11)0.0070 (11)0.0032 (12)
N20.0307 (14)0.0485 (18)0.0224 (13)0.0099 (13)0.0054 (11)0.0009 (13)
C10.0298 (15)0.0347 (17)0.0240 (15)0.0022 (13)0.0060 (13)0.0035 (14)
C20.0278 (15)0.0303 (16)0.0275 (16)0.0045 (12)0.0056 (13)0.0004 (13)
C30.0282 (15)0.0314 (15)0.0231 (15)0.0043 (13)0.0062 (12)0.0011 (13)
C40.0320 (16)0.0317 (16)0.0247 (15)0.0066 (13)0.0072 (13)0.0016 (13)
C50.0270 (16)0.044 (2)0.045 (2)0.0047 (14)0.0143 (15)0.0101 (17)
C60.0380 (18)0.0365 (18)0.0315 (17)0.0084 (15)0.0085 (15)0.0090 (16)
C70.0342 (16)0.0324 (17)0.0222 (15)0.0123 (13)0.0083 (13)0.0030 (13)
C80.0397 (18)0.0392 (18)0.0273 (16)0.0089 (16)0.0070 (14)0.0010 (15)
C90.057 (2)0.044 (2)0.0264 (17)0.0229 (19)0.0123 (16)0.0017 (16)
C100.052 (2)0.044 (2)0.040 (2)0.0228 (18)0.0229 (18)0.0118 (18)
C110.0384 (18)0.046 (2)0.042 (2)0.0151 (16)0.0202 (16)0.0127 (17)
C120.045 (2)0.061 (3)0.065 (3)0.012 (2)0.029 (2)0.018 (2)
C130.040 (2)0.057 (3)0.075 (3)0.0041 (19)0.023 (2)0.007 (3)
C140.0392 (19)0.045 (2)0.055 (2)0.0032 (16)0.0099 (18)0.0038 (19)
C150.0373 (18)0.0398 (19)0.0357 (19)0.0027 (15)0.0108 (15)0.0031 (16)
C160.0306 (16)0.0357 (17)0.0293 (16)0.0075 (14)0.0095 (13)0.0040 (14)
C170.0342 (17)0.0414 (19)0.0275 (16)0.0115 (15)0.0105 (14)0.0094 (16)
C180.047 (2)0.0392 (19)0.043 (2)0.0153 (17)0.0190 (17)0.0099 (17)
C190.062 (3)0.044 (2)0.069 (3)0.021 (2)0.031 (2)0.011 (2)
C200.066 (3)0.070 (3)0.063 (3)0.044 (3)0.029 (2)0.023 (3)
C210.044 (2)0.099 (4)0.054 (3)0.035 (3)0.011 (2)0.018 (3)
C220.0377 (19)0.066 (3)0.0372 (19)0.0149 (19)0.0075 (16)0.006 (2)
C230.0257 (15)0.0408 (18)0.0225 (15)0.0070 (14)0.0045 (12)0.0018 (14)
C240.0319 (16)0.0405 (19)0.0247 (15)0.0064 (15)0.0092 (13)0.0016 (15)
C250.0291 (16)0.053 (2)0.0238 (15)0.0030 (16)0.0038 (13)0.0018 (16)
C260.0382 (19)0.056 (2)0.0350 (19)0.0059 (18)0.0094 (16)0.0017 (19)
C270.040 (2)0.079 (3)0.036 (2)0.019 (2)0.0122 (17)0.002 (2)
C280.0354 (19)0.089 (3)0.0308 (18)0.010 (2)0.0126 (16)0.004 (2)
C290.0325 (18)0.074 (3)0.0251 (17)0.0032 (18)0.0075 (14)0.0065 (19)
C300.0286 (16)0.056 (2)0.0199 (15)0.0046 (16)0.0025 (13)0.0013 (16)
C310.0303 (16)0.0412 (18)0.0203 (15)0.0076 (14)0.0057 (13)0.0024 (14)
C320.055 (2)0.041 (2)0.055 (3)0.0068 (19)0.016 (2)0.009 (2)
C330.0380 (18)0.0346 (18)0.0379 (18)0.0070 (15)0.0133 (15)0.0048 (16)
C340.0439 (19)0.0418 (19)0.0281 (17)0.0080 (16)0.0114 (15)0.0054 (15)
C350.0365 (18)0.042 (2)0.0298 (17)0.0049 (15)0.0059 (15)0.0035 (16)
C360.0394 (18)0.0325 (18)0.040 (2)0.0046 (15)0.0117 (16)0.0009 (15)
O70.109 (15)0.086 (13)0.146 (19)0.007 (10)0.073 (14)0.001 (12)
O80.32 (7)0.14 (3)0.33 (7)0.0000.07 (5)0.000
Geometric parameters (Å, º) top
Br1—C271.909 (5)C12—C131.360 (8)
O1—C21.417 (4)C12—H120.9500
O1—H1O0.8400C13—C141.392 (7)
O2—C311.349 (5)C13—H130.9500
O2—C321.437 (5)C14—C151.374 (6)
O3—C331.237 (5)C14—H140.9500
O4—C331.275 (5)C15—C161.425 (5)
O4—H51.29 (6)C15—H150.9500
O5—C361.290 (5)C17—C181.383 (6)
O5—H51.13 (6)C17—C221.395 (6)
O6—C361.231 (5)C18—C191.386 (6)
N1—C51.487 (4)C18—H180.9500
N1—C61.487 (5)C19—C201.376 (8)
N1—C41.501 (4)C19—H190.9500
N1—H11.0000C20—C211.373 (9)
N2—C311.306 (5)C20—H200.9500
N2—C301.366 (5)C21—C221.388 (7)
C1—C231.520 (5)C21—H210.9500
C1—C171.523 (5)C22—H220.9500
C1—C21.581 (5)C23—C241.359 (5)
C1—H1A1.0000C23—C311.443 (5)
C2—C71.541 (5)C24—C251.423 (5)
C2—C31.548 (5)C24—H240.9500
C3—C41.531 (4)C25—C261.395 (6)
C3—H3A0.9900C25—C301.420 (6)
C3—H3B0.9900C26—C271.372 (6)
C4—H4A0.9900C26—H260.9500
C4—H4B0.9900C27—C281.390 (8)
C5—H5A0.9800C28—C291.363 (7)
C5—H5B0.9800C28—H280.9500
C5—H5C0.9800C29—C301.410 (5)
C6—H6A0.9800C29—H290.9500
C6—H6B0.9800C32—H32A0.9800
C6—H6C0.9800C32—H32B0.9800
C7—C81.379 (5)C32—H32C0.9800
C7—C161.439 (5)C33—C341.488 (5)
C8—C91.413 (5)C34—C351.342 (5)
C8—H80.9500C34—H340.9500
C9—C101.349 (7)C35—C361.482 (6)
C9—H90.9500C35—H350.9500
C10—C111.416 (6)O7—H7A0.8370
C10—H100.9500O7—H7B0.8394
C11—C121.411 (7)O8—H8A0.9355
C11—C161.438 (5)O8—H8Ai0.9355
C2—O1—H1O109.5C14—C15—C16121.9 (4)
C31—O2—C32117.0 (3)C14—C15—H15119.1
C33—O4—H5115 (3)C16—C15—H15119.1
C36—O5—H5114 (3)C15—C16—C11115.8 (3)
C5—N1—C6110.8 (3)C15—C16—C7125.5 (3)
C5—N1—C4113.1 (3)C11—C16—C7118.7 (3)
C6—N1—C4110.2 (3)C18—C17—C22118.2 (4)
C5—N1—H1107.5C18—C17—C1124.2 (3)
C6—N1—H1107.5C22—C17—C1117.5 (4)
C4—N1—H1107.5C17—C18—C19121.0 (4)
C31—N2—C30117.7 (3)C17—C18—H18119.5
C23—C1—C17111.8 (3)C19—C18—H18119.5
C23—C1—C2111.0 (3)C20—C19—C18120.4 (5)
C17—C1—C2113.9 (3)C20—C19—H19119.8
C23—C1—H1A106.6C18—C19—H19119.8
C17—C1—H1A106.6C21—C20—C19119.4 (4)
C2—C1—H1A106.6C21—C20—H20120.3
O1—C2—C7107.5 (3)C19—C20—H20120.3
O1—C2—C3107.9 (3)C20—C21—C22120.6 (5)
C7—C2—C3112.3 (3)C20—C21—H21119.7
O1—C2—C1109.5 (3)C22—C21—H21119.7
C7—C2—C1109.8 (3)C21—C22—C17120.5 (5)
C3—C2—C1109.8 (3)C21—C22—H22119.8
C4—C3—C2111.6 (3)C17—C22—H22119.8
C4—C3—H3A109.3C24—C23—C31115.9 (3)
C2—C3—H3A109.3C24—C23—C1124.2 (3)
C4—C3—H3B109.3C31—C23—C1119.8 (3)
C2—C3—H3B109.3C23—C24—C25121.2 (3)
H3A—C3—H3B108.0C23—C24—H24119.4
N1—C4—C3111.5 (3)C25—C24—H24119.4
N1—C4—H4A109.3C26—C25—C30120.1 (3)
C3—C4—H4A109.3C26—C25—C24122.8 (4)
N1—C4—H4B109.3C30—C25—C24117.2 (4)
C3—C4—H4B109.3C27—C26—C25119.2 (4)
H4A—C4—H4B108.0C27—C26—H26120.4
N1—C5—H5A109.5C25—C26—H26120.4
N1—C5—H5B109.5C26—C27—C28121.8 (4)
H5A—C5—H5B109.5C26—C27—Br1119.3 (4)
N1—C5—H5C109.5C28—C27—Br1118.9 (3)
H5A—C5—H5C109.5C29—C28—C27119.6 (4)
H5B—C5—H5C109.5C29—C28—H28120.2
N1—C6—H6A109.5C27—C28—H28120.2
N1—C6—H6B109.5C28—C29—C30121.0 (4)
H6A—C6—H6B109.5C28—C29—H29119.5
N1—C6—H6C109.5C30—C29—H29119.5
H6A—C6—H6C109.5N2—C30—C29119.6 (4)
H6B—C6—H6C109.5N2—C30—C25122.2 (3)
C8—C7—C16118.5 (3)C29—C30—C25118.2 (4)
C8—C7—C2117.9 (3)N2—C31—O2120.0 (3)
C16—C7—C2123.7 (3)N2—C31—C23125.3 (4)
C7—C8—C9122.0 (4)O2—C31—C23114.7 (3)
C7—C8—H8119.0O2—C32—H32A109.5
C9—C8—H8119.0O2—C32—H32B109.5
C10—C9—C8120.6 (4)H32A—C32—H32B109.5
C10—C9—H9119.7O2—C32—H32C109.5
C8—C9—H9119.7H32A—C32—H32C109.5
C9—C10—C11120.6 (4)H32B—C32—H32C109.5
C9—C10—H10119.7O3—C33—O4122.4 (3)
C11—C10—H10119.7O3—C33—C34117.9 (3)
C12—C11—C10120.5 (4)O4—C33—C34119.6 (3)
C12—C11—C16119.9 (4)C35—C34—C33130.5 (3)
C10—C11—C16119.6 (4)C35—C34—H34114.8
C13—C12—C11122.4 (4)C33—C34—H34114.8
C13—C12—H12118.8C34—C35—C36130.6 (3)
C11—C12—H12118.8C34—C35—H35114.7
C12—C13—C14118.5 (4)C36—C35—H35114.7
C12—C13—H13120.8O6—C36—O5122.3 (4)
C14—C13—H13120.8O6—C36—C35117.6 (4)
C15—C14—C13121.7 (4)O5—C36—C35120.0 (3)
C15—C14—H14119.2H7A—O7—H7B108.6
C13—C14—H14119.2H8A—O8—H8Ai113.8
C23—C1—C2—O156.3 (4)C1—C17—C18—C19175.4 (4)
C17—C1—C2—O170.9 (4)C17—C18—C19—C200.4 (7)
C23—C1—C2—C7174.1 (3)C18—C19—C20—C210.3 (8)
C17—C1—C2—C746.9 (4)C19—C20—C21—C220.9 (8)
C23—C1—C2—C362.0 (4)C20—C21—C22—C171.9 (7)
C17—C1—C2—C3170.8 (3)C18—C17—C22—C211.7 (6)
O1—C2—C3—C465.2 (4)C1—C17—C22—C21174.5 (4)
C7—C2—C3—C453.1 (4)C17—C1—C23—C2436.4 (4)
C1—C2—C3—C4175.6 (3)C2—C1—C23—C2491.9 (4)
C5—N1—C4—C371.8 (4)C17—C1—C23—C31142.4 (3)
C6—N1—C4—C3163.7 (3)C2—C1—C23—C3189.3 (4)
C2—C3—C4—N1169.4 (3)C31—C23—C24—C253.1 (5)
O1—C2—C7—C80.5 (4)C1—C23—C24—C25178.1 (3)
C3—C2—C7—C8118.0 (3)C23—C24—C25—C26177.2 (3)
C1—C2—C7—C8119.5 (3)C23—C24—C25—C303.0 (5)
O1—C2—C7—C16178.8 (3)C30—C25—C26—C271.8 (5)
C3—C2—C7—C1662.7 (4)C24—C25—C26—C27178.0 (4)
C1—C2—C7—C1659.8 (4)C25—C26—C27—C280.9 (6)
C16—C7—C8—C90.9 (5)C25—C26—C27—Br1177.9 (3)
C2—C7—C8—C9179.8 (3)C26—C27—C28—C291.8 (6)
C7—C8—C9—C101.8 (6)Br1—C27—C28—C29177.0 (3)
C8—C9—C10—C111.0 (6)C27—C28—C29—C300.1 (6)
C9—C10—C11—C12179.5 (4)C31—N2—C30—C29179.4 (3)
C9—C10—C11—C160.6 (6)C31—N2—C30—C251.0 (5)
C10—C11—C12—C13177.9 (4)C28—C29—C30—N2175.7 (3)
C16—C11—C12—C131.0 (7)C28—C29—C30—C252.8 (5)
C11—C12—C13—C140.7 (7)C26—C25—C30—N2174.9 (3)
C12—C13—C14—C150.2 (7)C24—C25—C30—N25.3 (5)
C13—C14—C15—C160.1 (6)C26—C25—C30—C293.6 (5)
C14—C15—C16—C110.5 (5)C24—C25—C30—C29176.2 (3)
C14—C15—C16—C7179.9 (4)C30—N2—C31—O2172.6 (3)
C12—C11—C16—C150.9 (5)C30—N2—C31—C236.0 (5)
C10—C11—C16—C15178.0 (3)C32—O2—C31—N23.5 (5)
C12—C11—C16—C7179.6 (4)C32—O2—C31—C23175.3 (3)
C10—C11—C16—C71.4 (5)C24—C23—C31—N28.1 (5)
C8—C7—C16—C15178.7 (3)C1—C23—C31—N2173.0 (3)
C2—C7—C16—C152.0 (5)C24—C23—C31—O2170.6 (3)
C8—C7—C16—C110.7 (5)C1—C23—C31—O28.3 (4)
C2—C7—C16—C11178.6 (3)O3—C33—C34—C35175.8 (4)
C23—C1—C17—C1880.4 (4)O4—C33—C34—C351.8 (7)
C2—C1—C17—C1846.3 (5)C33—C34—C35—C362.2 (8)
C23—C1—C17—C2295.5 (4)C34—C35—C36—O6177.1 (4)
C2—C1—C17—C22137.7 (3)C34—C35—C36—O54.6 (7)
C22—C17—C18—C190.5 (6)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O6ii0.841.982.822 (4)175
O5—H5···O41.13 (6)1.29 (6)2.417 (4)169 (5)
N1—H1···O31.001.712.707 (4)172
N1—H1···O41.002.493.174 (4)125
C3—H3A···O6ii0.992.573.308 (4)131
C6—H6B···O4iii0.982.613.257 (5)124
O7—H7A···O30.842.313.139 (16)172
O8—H8A···O70.942.133.02 (2)158
Symmetry codes: (ii) x1/2, y1/2, z; (iii) x+1, y, z.
[4-(6-bromo-2-methoxyquinolin-3-yl)-3-hydroxy-3-(naphthalen-1-yl)-4-phenylbutyl]dimethylazanium 3-carboxyprop-2-enoate tetrahydrofuran sesquihydrate (THF) top
Crystal data top
2C32H32BrN2O2+·2C4H3O4·3C4H8OF(000) = 1632
Mr = 1559.45Dx = 1.365 Mg m3
Monoclinic, C2Cu Kα radiation, λ = 1.54178 Å
a = 16.4119 (6) ÅCell parameters from 9944 reflections
b = 13.5643 (6) Åθ = 2.6–78.6°
c = 17.8475 (8) ŵ = 1.92 mm1
β = 107.318 (3)°T = 150 K
V = 3793.0 (3) Å3Fragment, colourless
Z = 20.33 × 0.19 × 0.16 mm
Data collection top
Bruker AXS D8 Quest with PhotonIII_C14 CPAD
diffractometer
7473 independent reflections
Radiation source: I-mu-S microsource X-ray tube6615 reflections with I > 2σ(I)
Laterally graded multilayer (Goebel) mirror monochromatorRint = 0.049
Detector resolution: 7.4074 pixels mm-1θmax = 79.9°, θmin = 2.6°
ω and phi scansh = 1820
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
k = 1617
Tmin = 0.254, Tmax = 0.391l = 2221
18660 measured reflections
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.054 w = 1/[σ2(Fo2) + 6.5774P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.127(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.46 e Å3
7473 reflectionsΔρmin = 0.52 e Å3
551 parametersExtinction correction: SHELXL2018/3 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
223 restraintsExtinction coefficient: 0.00079 (10)
Primary atom site location: isomorphous structure methodsAbsolute structure: Refined as an inversion twin
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.03 (3)
Special details top

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

Refinement. Refined as a two-component inversion twin

The position of the hydromaleate acidic hydrogen atom was freely refined.

The structure was solved from its 0.5 hydrate analogue by isomorphous replacement. Two THF molecules were refined as disordered. One in a 1:1 ratio around a two-fold axis, the other in a general position. The three disordered moieties were restrained to have similar geometries. Uij components of ADPs for disordered atoms closer to each other than 2.0 Angstrom were restrained to be similar. Subject to these conditions the occupancy ratio for the molecule in the general position refined to 0.587 (16) to 0.413 (16).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.26058 (6)0.03336 (7)0.44125 (5)0.0900 (4)
O10.4801 (2)0.2596 (2)0.1676 (2)0.0393 (8)
H1O0.4353930.2749030.1786280.047*
O20.5566 (2)0.4767 (3)0.3637 (2)0.0431 (8)
O30.5052 (2)0.6774 (3)0.2100 (2)0.0474 (9)
O40.5714 (3)0.6982 (4)0.1204 (2)0.0562 (11)
O50.7069 (3)0.7612 (4)0.1131 (2)0.0580 (11)
H50.636 (5)0.732 (6)0.121 (4)0.087*
O60.8266 (2)0.8159 (3)0.1967 (3)0.0542 (10)
N10.4013 (2)0.5583 (3)0.1018 (2)0.0354 (9)
H10.4382730.6056990.1399730.042*
N20.4546 (3)0.4009 (3)0.4074 (2)0.0393 (9)
C10.5937 (3)0.3139 (4)0.2833 (3)0.0346 (10)
H1A0.6299840.3733270.3022150.042*
C20.5429 (3)0.3346 (3)0.1955 (3)0.0347 (10)
C30.4961 (3)0.4347 (4)0.1881 (3)0.0347 (10)
H3A0.4528730.4305040.2166280.042*
H3B0.5379200.4859630.2141370.042*
C40.4524 (3)0.4665 (4)0.1047 (3)0.0375 (11)
H4A0.4959960.4781980.0774330.045*
H4B0.4144200.4130290.0767400.045*
C50.3232 (3)0.5425 (5)0.1264 (4)0.0515 (14)
H5A0.2881800.4906670.0939910.077*
H5B0.2903070.6038510.1198120.077*
H5C0.3396130.5224520.1816760.077*
C60.3793 (4)0.6057 (4)0.0235 (3)0.0452 (12)
H6A0.3488410.5583750.0166070.068*
H6B0.4316300.6269460.0125470.068*
H6C0.3427180.6630020.0228050.068*
C70.6027 (3)0.3295 (4)0.1431 (3)0.0356 (10)
C80.5881 (4)0.2595 (4)0.0854 (3)0.0423 (12)
H80.5407220.2166670.0786410.051*
C90.6398 (4)0.2478 (5)0.0356 (3)0.0514 (15)
H90.6273960.1972590.0029690.062*
C100.7074 (4)0.3088 (5)0.0429 (3)0.0525 (15)
H100.7418430.3013650.0089190.063*
C110.7262 (3)0.3826 (5)0.1004 (3)0.0454 (13)
C120.7952 (4)0.4487 (5)0.1066 (4)0.0577 (16)
H120.8289000.4406700.0719700.069*
C130.8147 (4)0.5224 (6)0.1599 (4)0.0598 (16)
H130.8613750.5651560.1628410.072*
C140.7653 (3)0.5345 (5)0.2101 (3)0.0498 (13)
H140.7787670.5863140.2476140.060*
C150.6974 (3)0.4737 (4)0.2071 (3)0.0411 (11)
H150.6650970.4843570.2426050.049*
C160.6744 (3)0.3949 (4)0.1517 (3)0.0384 (11)
C170.6542 (3)0.2269 (4)0.2958 (3)0.0376 (11)
C180.6305 (4)0.1353 (4)0.2593 (4)0.0459 (13)
H180.5745830.1262230.2247280.055*
C190.6887 (4)0.0576 (4)0.2735 (4)0.0574 (16)
H190.6728350.0040310.2481120.069*
C200.7703 (4)0.0711 (5)0.3255 (4)0.0644 (19)
H200.8098730.0180290.3355970.077*
C210.7936 (4)0.1583 (6)0.3613 (4)0.0618 (17)
H210.8491790.1666750.3967980.074*
C220.7358 (3)0.2363 (5)0.3460 (3)0.0488 (14)
H220.7531610.2979220.3710140.059*
C230.5332 (3)0.3070 (4)0.3332 (3)0.0341 (10)
C240.4933 (3)0.2239 (4)0.3446 (3)0.0383 (11)
H240.5060520.1636200.3234780.046*
C250.4326 (3)0.2237 (4)0.3873 (3)0.0403 (12)
C260.3881 (4)0.1378 (5)0.3977 (3)0.0494 (14)
H260.4008080.0754820.3795550.059*
C270.3263 (4)0.1467 (6)0.4344 (4)0.0595 (17)
C280.3074 (4)0.2364 (6)0.4640 (3)0.0587 (17)
H280.2648570.2395370.4902400.070*
C290.3505 (3)0.3197 (5)0.4551 (3)0.0513 (14)
H290.3379740.3808390.4751080.062*
C300.4137 (3)0.3149 (4)0.4161 (3)0.0415 (12)
C310.5119 (3)0.3938 (4)0.3702 (3)0.0369 (11)
C320.5344 (5)0.5659 (4)0.3965 (4)0.0616 (17)
H32A0.4759800.5849840.3674990.092*
H32B0.5738820.6185590.3927270.092*
H32C0.5384020.5548670.4517670.092*
C330.5672 (3)0.7063 (4)0.1903 (3)0.0399 (11)
C340.6399 (3)0.7506 (4)0.2525 (3)0.0438 (12)
H340.6312930.7555720.3027300.053*
C350.7151 (3)0.7844 (4)0.2489 (3)0.0419 (12)
H350.7504740.8111230.2967250.050*
C360.7533 (3)0.7875 (4)0.1829 (3)0.0423 (12)
O70.4370 (6)0.0263 (8)0.0209 (6)0.075 (3)0.5
C370.5084 (18)0.034 (3)0.0604 (14)0.100 (10)0.5
H37A0.5520480.0064610.0977660.120*0.5
H37B0.4895090.0860550.0907480.120*0.5
C380.5450 (14)0.080 (2)0.0055 (13)0.128 (8)0.5
H38A0.5374020.1520820.0049580.154*0.5
H38B0.6066660.0645790.0187600.154*0.5
C390.4956 (13)0.034 (2)0.0747 (14)0.073 (6)0.5
H39A0.5252680.0239940.0874470.087*0.5
H39B0.4855230.0830610.1177220.087*0.5
C400.4133 (8)0.0059 (9)0.0577 (8)0.059 (3)0.5
H40A0.3838930.0475100.0933280.071*0.5
H40B0.3745340.0633510.0649570.071*0.5
O81.0606 (9)0.3358 (13)0.4220 (9)0.126 (5)0.587 (16)
C410.9722 (12)0.3162 (15)0.3956 (11)0.094 (5)0.587 (16)
H41A0.9442480.3473430.4317630.113*0.587 (16)
H41B0.9626180.2442060.3961350.113*0.587 (16)
C420.9349 (11)0.3530 (12)0.3185 (9)0.082 (4)0.587 (16)
H42A0.8812180.3885150.3152660.099*0.587 (16)
H42B0.9217470.2981300.2802340.099*0.587 (16)
C430.9983 (11)0.4216 (12)0.3012 (10)0.078 (4)0.587 (16)
H43A0.9719750.4860750.2822000.093*0.587 (16)
H43B1.0228120.3931460.2616180.093*0.587 (16)
C441.0658 (12)0.4317 (14)0.3806 (11)0.090 (5)0.587 (16)
H44A1.1231550.4406870.3741670.108*0.587 (16)
H44B1.0530890.4883800.4102450.108*0.587 (16)
O8B0.9965 (13)0.4595 (16)0.3290 (13)0.108 (6)0.413 (16)
C41B1.0619 (16)0.4729 (15)0.4031 (15)0.082 (6)0.413 (16)
H41C1.1087370.5131320.3947420.098*0.413 (16)
H41D1.0375900.5093400.4395970.098*0.413 (16)
C42B1.0957 (17)0.3804 (15)0.4381 (15)0.094 (6)0.413 (16)
H42C1.1088830.3820410.4959290.112*0.413 (16)
H42D1.1475250.3612850.4240510.112*0.413 (16)
C43B1.018 (2)0.3092 (17)0.3993 (18)0.098 (6)0.413 (16)
H43C1.0356810.2566960.3686630.117*0.413 (16)
H43D0.9967160.2781650.4398840.117*0.413 (16)
C44B0.9520 (17)0.374 (2)0.347 (2)0.115 (6)0.413 (16)
H44C0.9215330.3383000.2982830.138*0.413 (16)
H44D0.9099140.3943390.3738390.138*0.413 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0831 (6)0.1175 (7)0.0827 (6)0.0585 (5)0.0450 (4)0.0131 (5)
O10.0297 (17)0.0386 (18)0.049 (2)0.0031 (14)0.0107 (16)0.0029 (15)
O20.0391 (19)0.0431 (19)0.049 (2)0.0031 (16)0.0167 (17)0.0042 (16)
O30.040 (2)0.047 (2)0.060 (3)0.0115 (17)0.0223 (19)0.0055 (18)
O40.042 (2)0.087 (3)0.042 (2)0.021 (2)0.0153 (18)0.012 (2)
O50.045 (2)0.088 (3)0.045 (2)0.017 (2)0.0200 (19)0.006 (2)
O60.033 (2)0.058 (2)0.075 (3)0.0104 (17)0.0207 (19)0.003 (2)
N10.0256 (18)0.035 (2)0.045 (2)0.0037 (15)0.0094 (17)0.0040 (17)
N20.026 (2)0.054 (2)0.038 (2)0.0008 (18)0.0093 (18)0.0001 (19)
C10.024 (2)0.041 (3)0.040 (3)0.0020 (19)0.011 (2)0.000 (2)
C20.022 (2)0.035 (2)0.047 (3)0.0028 (18)0.010 (2)0.002 (2)
C30.026 (2)0.039 (2)0.039 (3)0.0022 (19)0.011 (2)0.002 (2)
C40.031 (2)0.038 (2)0.042 (3)0.006 (2)0.008 (2)0.000 (2)
C50.030 (2)0.055 (3)0.074 (4)0.005 (2)0.021 (3)0.011 (3)
C60.039 (3)0.048 (3)0.045 (3)0.003 (2)0.007 (2)0.010 (2)
C70.030 (2)0.041 (3)0.037 (3)0.005 (2)0.011 (2)0.001 (2)
C80.043 (3)0.045 (3)0.039 (3)0.008 (2)0.012 (2)0.003 (2)
C90.057 (4)0.060 (4)0.040 (3)0.025 (3)0.018 (3)0.001 (3)
C100.048 (3)0.070 (4)0.047 (3)0.023 (3)0.026 (3)0.013 (3)
C110.035 (3)0.062 (3)0.046 (3)0.016 (2)0.022 (2)0.009 (3)
C120.040 (3)0.081 (4)0.063 (4)0.014 (3)0.032 (3)0.018 (3)
C130.035 (3)0.074 (4)0.074 (4)0.004 (3)0.021 (3)0.014 (4)
C140.030 (2)0.055 (3)0.061 (3)0.001 (3)0.009 (2)0.009 (3)
C150.035 (3)0.046 (3)0.043 (3)0.003 (2)0.014 (2)0.002 (2)
C160.029 (2)0.047 (3)0.041 (3)0.007 (2)0.014 (2)0.005 (2)
C170.031 (2)0.043 (3)0.042 (3)0.004 (2)0.016 (2)0.006 (2)
C180.040 (3)0.041 (3)0.057 (3)0.006 (2)0.016 (3)0.002 (2)
C190.061 (4)0.044 (3)0.076 (4)0.014 (3)0.034 (3)0.011 (3)
C200.061 (4)0.070 (4)0.069 (4)0.034 (3)0.030 (3)0.016 (3)
C210.038 (3)0.086 (5)0.060 (4)0.022 (3)0.013 (3)0.010 (4)
C220.031 (3)0.066 (4)0.049 (3)0.008 (2)0.012 (2)0.006 (3)
C230.026 (2)0.043 (3)0.035 (2)0.0018 (19)0.0109 (19)0.004 (2)
C240.027 (2)0.048 (3)0.042 (3)0.003 (2)0.013 (2)0.002 (2)
C250.029 (2)0.060 (3)0.033 (3)0.007 (2)0.012 (2)0.000 (2)
C260.039 (3)0.065 (4)0.046 (3)0.014 (3)0.015 (3)0.001 (3)
C270.039 (3)0.092 (5)0.048 (3)0.027 (3)0.014 (3)0.004 (3)
C280.038 (3)0.102 (5)0.040 (3)0.018 (3)0.017 (3)0.006 (3)
C290.035 (3)0.084 (4)0.037 (3)0.010 (3)0.013 (2)0.006 (3)
C300.026 (2)0.064 (3)0.033 (2)0.002 (2)0.0067 (19)0.001 (2)
C310.027 (2)0.047 (3)0.036 (3)0.001 (2)0.007 (2)0.001 (2)
C320.073 (4)0.045 (3)0.078 (5)0.004 (3)0.041 (4)0.010 (3)
C330.031 (2)0.041 (3)0.048 (3)0.002 (2)0.013 (2)0.004 (2)
C340.040 (3)0.048 (3)0.045 (3)0.000 (2)0.014 (2)0.004 (2)
C350.035 (3)0.044 (3)0.044 (3)0.002 (2)0.008 (2)0.001 (2)
C360.032 (3)0.044 (3)0.051 (3)0.004 (2)0.013 (2)0.002 (2)
O70.081 (6)0.071 (6)0.084 (7)0.018 (6)0.039 (5)0.017 (6)
C370.12 (2)0.114 (17)0.061 (12)0.050 (15)0.021 (12)0.013 (12)
C380.110 (14)0.167 (18)0.125 (15)0.086 (13)0.060 (13)0.063 (14)
C390.062 (11)0.088 (13)0.085 (13)0.028 (10)0.047 (10)0.018 (11)
C400.054 (7)0.049 (7)0.081 (9)0.004 (6)0.031 (7)0.001 (6)
O80.104 (9)0.139 (10)0.121 (9)0.043 (8)0.014 (7)0.011 (8)
C410.075 (9)0.096 (9)0.100 (9)0.039 (9)0.010 (9)0.002 (8)
C420.074 (8)0.085 (8)0.092 (9)0.027 (6)0.032 (7)0.040 (7)
C430.060 (7)0.074 (8)0.095 (10)0.004 (7)0.018 (7)0.018 (7)
C440.069 (7)0.092 (10)0.099 (10)0.014 (8)0.009 (7)0.021 (8)
O8B0.078 (8)0.121 (11)0.115 (11)0.026 (9)0.014 (9)0.008 (9)
C41B0.062 (9)0.064 (10)0.101 (12)0.013 (9)0.002 (9)0.010 (9)
C42B0.102 (12)0.065 (10)0.105 (12)0.014 (10)0.017 (11)0.011 (10)
C43B0.094 (12)0.075 (9)0.116 (11)0.048 (10)0.019 (11)0.007 (9)
C44B0.092 (10)0.105 (11)0.128 (12)0.032 (10)0.000 (10)0.007 (10)
Geometric parameters (Å, º) top
Br1—C271.903 (6)C22—H220.9500
O1—C21.427 (5)C23—C241.349 (7)
O1—H1O0.8400C23—C311.443 (7)
O2—C311.367 (6)C24—C251.422 (7)
O2—C321.437 (7)C24—H240.9500
O3—C331.234 (6)C25—C301.409 (8)
O4—C331.275 (7)C25—C261.418 (8)
O4—H51.15 (8)C26—C271.365 (9)
O5—C361.301 (6)C26—H260.9500
O5—H51.28 (8)C27—C281.399 (10)
O6—C361.217 (6)C28—C291.367 (9)
N1—C61.482 (7)C28—H280.9500
N1—C51.490 (6)C29—C301.411 (8)
N1—C41.493 (6)C29—H290.9500
N1—H11.0000C32—H32A0.9800
N2—C311.305 (6)C32—H32B0.9800
N2—C301.378 (7)C32—H32C0.9800
C1—C171.516 (7)C33—C341.493 (7)
C1—C231.521 (7)C34—C351.337 (8)
C1—C21.566 (7)C34—H340.9500
C1—H1A1.0000C35—C361.490 (8)
C2—C71.545 (7)C35—H350.9500
C2—C31.546 (6)O7—C401.408 (15)
C3—C41.511 (7)O7—C371.43 (2)
C3—H3A0.9900C37—C381.43 (2)
C3—H3B0.9900C37—H37A0.9900
C4—H4A0.9900C37—H37B0.9900
C4—H4B0.9900C38—C391.55 (2)
C5—H5A0.9800C38—H38A0.9900
C5—H5B0.9800C38—H38B0.9900
C5—H5C0.9800C39—C401.52 (2)
C6—H6A0.9800C39—H39A0.9900
C6—H6B0.9800C39—H39B0.9900
C6—H6C0.9800C40—H40A0.9900
C7—C81.368 (7)C40—H40B0.9900
C7—C161.444 (7)O8—C411.411 (17)
C8—C91.408 (8)O8—C441.510 (18)
C8—H80.9500C41—C421.42 (2)
C9—C101.359 (9)C41—H41A0.9900
C9—H90.9500C41—H41B0.9900
C10—C111.400 (9)C42—C431.494 (19)
C10—H100.9500C42—H42A0.9900
C11—C121.423 (9)C42—H42B0.9900
C11—C161.435 (7)C43—C441.523 (19)
C12—C131.351 (10)C43—H43A0.9900
C12—H120.9500C43—H43B0.9900
C13—C141.385 (8)C44—H44A0.9900
C13—H130.9500C44—H44B0.9900
C14—C151.375 (8)O8B—C41B1.45 (2)
C14—H140.9500O8B—C44B1.46 (2)
C15—C161.428 (8)C41B—C42B1.44 (2)
C15—H150.9500C41B—H41C0.9900
C17—C221.378 (7)C41B—H41D0.9900
C17—C181.402 (8)C42B—C43B1.58 (2)
C18—C191.393 (8)C42B—H42C0.9900
C18—H180.9500C42B—H42D0.9900
C19—C201.396 (9)C43B—C44B1.49 (2)
C19—H190.9500C43B—H43C0.9900
C20—C211.345 (10)C43B—H43D0.9900
C20—H200.9500C44B—H44C0.9900
C21—C221.393 (8)C44B—H44D0.9900
C21—H210.9500
C2—O1—H1O109.5C26—C27—Br1118.4 (6)
C31—O2—C32116.8 (4)C28—C27—Br1119.0 (5)
C33—O4—H5106 (4)C29—C28—C27119.6 (6)
C36—O5—H5106 (3)C29—C28—H28120.2
C6—N1—C5110.5 (4)C27—C28—H28120.2
C6—N1—C4111.8 (4)C28—C29—C30120.1 (6)
C5—N1—C4113.2 (4)C28—C29—H29119.9
C6—N1—H1107.0C30—C29—H29119.9
C5—N1—H1107.0N2—C30—C25122.2 (5)
C4—N1—H1107.0N2—C30—C29118.2 (5)
C31—N2—C30116.4 (5)C25—C30—C29119.6 (5)
C17—C1—C23112.3 (4)N2—C31—O2117.9 (5)
C17—C1—C2114.7 (4)N2—C31—C23127.0 (5)
C23—C1—C2110.6 (4)O2—C31—C23115.0 (4)
C17—C1—H1A106.2O2—C32—H32A109.5
C23—C1—H1A106.2O2—C32—H32B109.5
C2—C1—H1A106.2H32A—C32—H32B109.5
O1—C2—C7106.3 (4)O2—C32—H32C109.5
O1—C2—C3107.9 (4)H32A—C32—H32C109.5
C7—C2—C3112.1 (4)H32B—C32—H32C109.5
O1—C2—C1109.5 (4)O3—C33—O4122.7 (5)
C7—C2—C1110.6 (4)O3—C33—C34117.4 (5)
C3—C2—C1110.2 (4)O4—C33—C34119.9 (5)
C4—C3—C2114.4 (4)C35—C34—C33130.3 (5)
C4—C3—H3A108.7C35—C34—H34114.8
C2—C3—H3A108.7C33—C34—H34114.8
C4—C3—H3B108.7C34—C35—C36131.3 (5)
C2—C3—H3B108.7C34—C35—H35114.4
H3A—C3—H3B107.6C36—C35—H35114.4
N1—C4—C3111.7 (4)O6—C36—O5122.8 (5)
N1—C4—H4A109.3O6—C36—C35118.1 (5)
C3—C4—H4A109.3O5—C36—C35119.1 (4)
N1—C4—H4B109.3C40—O7—C37104.8 (14)
C3—C4—H4B109.3C38—C37—O7110.9 (16)
H4A—C4—H4B107.9C38—C37—H37A109.5
N1—C5—H5A109.5O7—C37—H37A109.5
N1—C5—H5B109.5C38—C37—H37B109.5
H5A—C5—H5B109.5O7—C37—H37B109.5
N1—C5—H5C109.5H37A—C37—H37B108.0
H5A—C5—H5C109.5C37—C38—C39104.5 (13)
H5B—C5—H5C109.5C37—C38—H38A110.8
N1—C6—H6A109.5C39—C38—H38A110.8
N1—C6—H6B109.5C37—C38—H38B110.8
H6A—C6—H6B109.5C39—C38—H38B110.8
N1—C6—H6C109.5H38A—C38—H38B108.9
H6A—C6—H6C109.5C40—C39—C3899.7 (15)
H6B—C6—H6C109.5C40—C39—H39A111.8
C8—C7—C16117.5 (5)C38—C39—H39A111.8
C8—C7—C2119.1 (5)C40—C39—H39B111.8
C16—C7—C2123.5 (4)C38—C39—H39B111.8
C7—C8—C9123.4 (6)H39A—C39—H39B109.6
C7—C8—H8118.3O7—C40—C39106.2 (13)
C9—C8—H8118.3O7—C40—H40A110.5
C10—C9—C8119.9 (6)C39—C40—H40A110.5
C10—C9—H9120.0O7—C40—H40B110.5
C8—C9—H9120.0C39—C40—H40B110.5
C9—C10—C11120.1 (5)H40A—C40—H40B108.7
C9—C10—H10120.0C41—O8—C44101.6 (13)
C11—C10—H10120.0O8—C41—C42111.1 (14)
C10—C11—C12120.3 (5)O8—C41—H41A109.4
C10—C11—C16120.5 (5)C42—C41—H41A109.4
C12—C11—C16119.1 (5)O8—C41—H41B109.4
C13—C12—C11122.5 (6)C42—C41—H41B109.4
C13—C12—H12118.7H41A—C41—H41B108.0
C11—C12—H12118.7C41—C42—C43107.0 (12)
C12—C13—C14118.8 (6)C41—C42—H42A110.3
C12—C13—H13120.6C43—C42—H42A110.3
C14—C13—H13120.6C41—C42—H42B110.3
C15—C14—C13121.8 (6)C43—C42—H42B110.3
C15—C14—H14119.1H42A—C42—H42B108.6
C13—C14—H14119.1C42—C43—C44102.8 (13)
C14—C15—C16121.3 (5)C42—C43—H43A111.2
C14—C15—H15119.3C44—C43—H43A111.2
C16—C15—H15119.3C42—C43—H43B111.2
C15—C16—C11116.4 (5)C44—C43—H43B111.2
C15—C16—C7125.0 (5)H43A—C43—H43B109.1
C11—C16—C7118.6 (5)O8—C44—C43104.2 (13)
C22—C17—C18117.7 (5)O8—C44—H44A110.9
C22—C17—C1119.4 (5)C43—C44—H44A110.9
C18—C17—C1122.8 (5)O8—C44—H44B110.9
C19—C18—C17120.4 (5)C43—C44—H44B110.9
C19—C18—H18119.8H44A—C44—H44B108.9
C17—C18—H18119.8C41B—O8B—C44B100.5 (16)
C18—C19—C20119.5 (6)C42B—C41B—O8B111.9 (16)
C18—C19—H19120.3C42B—C41B—H41C109.2
C20—C19—H19120.3O8B—C41B—H41C109.2
C21—C20—C19120.8 (6)C42B—C41B—H41D109.2
C21—C20—H20119.6O8B—C41B—H41D109.2
C19—C20—H20119.6H41C—C41B—H41D107.9
C20—C21—C22119.6 (6)C41B—C42B—C43B100.8 (16)
C20—C21—H21120.2C41B—C42B—H42C111.6
C22—C21—H21120.2C43B—C42B—H42C111.6
C17—C22—C21122.0 (6)C41B—C42B—H42D111.6
C17—C22—H22119.0C43B—C42B—H42D111.6
C21—C22—H22119.0H42C—C42B—H42D109.4
C24—C23—C31114.7 (4)C44B—C43B—C42B104.9 (17)
C24—C23—C1124.8 (5)C44B—C43B—H43C110.8
C31—C23—C1120.5 (4)C42B—C43B—H43C110.8
C23—C24—C25122.1 (5)C44B—C43B—H43D110.8
C23—C24—H24119.0C42B—C43B—H43D110.8
C25—C24—H24119.0H43C—C43B—H43D108.8
C30—C25—C26119.7 (5)O8B—C44B—C43B106.7 (18)
C30—C25—C24117.4 (5)O8B—C44B—H44C110.4
C26—C25—C24122.8 (5)C43B—C44B—H44C110.4
C27—C26—C25118.4 (6)O8B—C44B—H44D110.4
C27—C26—H26120.8C43B—C44B—H44D110.4
C25—C26—H26120.8H44C—C44B—H44D108.6
C26—C27—C28122.6 (6)
C17—C1—C2—O171.7 (5)C17—C1—C23—C2442.3 (6)
C23—C1—C2—O156.5 (5)C2—C1—C23—C2487.2 (6)
C17—C1—C2—C745.2 (5)C17—C1—C23—C31140.2 (5)
C23—C1—C2—C7173.4 (4)C2—C1—C23—C3190.3 (5)
C17—C1—C2—C3169.8 (4)C31—C23—C24—C252.3 (7)
C23—C1—C2—C362.0 (5)C1—C23—C24—C25175.3 (4)
O1—C2—C3—C466.4 (5)C23—C24—C25—C301.6 (7)
C7—C2—C3—C450.4 (5)C23—C24—C25—C26177.9 (5)
C1—C2—C3—C4174.1 (4)C30—C25—C26—C271.3 (8)
C6—N1—C4—C3163.5 (4)C24—C25—C26—C27175.0 (5)
C5—N1—C4—C370.9 (5)C25—C26—C27—C282.0 (9)
C2—C3—C4—N1174.3 (4)C25—C26—C27—Br1175.3 (4)
O1—C2—C7—C81.2 (6)C26—C27—C28—C291.4 (10)
C3—C2—C7—C8118.9 (5)Br1—C27—C28—C29175.9 (4)
C1—C2—C7—C8117.6 (5)C27—C28—C29—C300.0 (9)
O1—C2—C7—C16179.0 (4)C31—N2—C30—C250.4 (7)
C3—C2—C7—C1661.3 (6)C31—N2—C30—C29179.2 (5)
C1—C2—C7—C1662.1 (6)C26—C25—C30—N2179.6 (5)
C16—C7—C8—C90.9 (8)C24—C25—C30—N23.2 (7)
C2—C7—C8—C9178.9 (5)C26—C25—C30—C290.0 (7)
C7—C8—C9—C101.0 (8)C24—C25—C30—C29176.5 (5)
C8—C9—C10—C110.7 (8)C28—C29—C30—N2179.0 (5)
C9—C10—C11—C12178.0 (5)C28—C29—C30—C250.7 (8)
C9—C10—C11—C160.4 (8)C30—N2—C31—O2177.0 (4)
C10—C11—C12—C13178.4 (6)C30—N2—C31—C234.2 (7)
C16—C11—C12—C130.8 (9)C32—O2—C31—N21.8 (7)
C11—C12—C13—C140.4 (10)C32—O2—C31—C23177.2 (5)
C12—C13—C14—C150.0 (9)C24—C23—C31—N25.6 (7)
C13—C14—C15—C160.1 (8)C1—C23—C31—N2172.1 (5)
C14—C15—C16—C110.5 (7)C24—C23—C31—O2175.6 (4)
C14—C15—C16—C7178.1 (5)C1—C23—C31—O26.7 (6)
C10—C11—C16—C15178.5 (5)O3—C33—C34—C35177.4 (6)
C12—C11—C16—C150.8 (7)O4—C33—C34—C351.5 (9)
C10—C11—C16—C70.3 (8)C33—C34—C35—C361.7 (10)
C12—C11—C16—C7177.9 (5)C34—C35—C36—O6174.5 (6)
C8—C7—C16—C15178.1 (5)C34—C35—C36—O56.4 (9)
C2—C7—C16—C152.2 (8)C40—O7—C37—C3818 (3)
C8—C7—C16—C110.5 (7)O7—C37—C38—C395 (3)
C2—C7—C16—C11179.2 (5)C37—C38—C39—C4025 (3)
C23—C1—C17—C2298.2 (5)C37—O7—C40—C3935 (2)
C2—C1—C17—C22134.4 (5)C38—C39—C40—O737 (2)
C23—C1—C17—C1880.6 (6)C44—O8—C41—C4232 (2)
C2—C1—C17—C1846.7 (7)O8—C41—C42—C4314 (2)
C22—C17—C18—C190.6 (8)C41—C42—C43—C449.4 (19)
C1—C17—C18—C19179.4 (5)C41—O8—C44—C4336 (2)
C17—C18—C19—C201.1 (9)C42—C43—C44—O827.9 (18)
C18—C19—C20—C210.6 (10)C44B—O8B—C41B—C42B39 (3)
C19—C20—C21—C220.4 (11)O8B—C41B—C42B—C43B25 (3)
C18—C17—C22—C210.4 (9)C41B—C42B—C43B—C44B0 (4)
C1—C17—C22—C21178.5 (5)C41B—O8B—C44B—C43B37 (3)
C20—C21—C22—C170.9 (10)C42B—C43B—C44B—O8B23 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O6i0.841.992.824 (5)176
O4—H5···O51.15 (8)1.28 (8)2.422 (5)171 (7)
N1—H1···O31.001.702.699 (5)175
N1—H1···O41.002.633.310 (6)125
C3—H3A···O6i0.992.533.258 (6)130
C3—H3B···O30.992.653.314 (6)125
C6—H6B···O4ii0.982.553.173 (7)122
C26—H26···O8Bi0.952.573.44 (3)152
C42—H42B···O3iii0.992.673.478 (17)138
Symmetry codes: (i) x1/2, y1/2, z; (ii) x+1, y, z; (iii) x+1/2, y1/2, z.
[4-(6-bromo-2-methoxyquinolin-3-yl)-3-hydroxy-3-(naphthalen-1-yl)-4-phenylbutyl]dimethylazanium 3-carboxyprop-2-enoate ethyl acetate 0.821-solvate (ethyl_acetate) top
Crystal data top
C32H32BrN2O2+·C4H3O4·0.821C4H8O2F(000) = 1550
Mr = 743.88Dx = 1.326 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 16.1525 (10) ÅCell parameters from 9891 reflections
b = 13.5353 (9) Åθ = 2.5–30.9°
c = 17.8572 (11) ŵ = 1.16 mm1
β = 107.359 (2)°T = 150 K
V = 3726.3 (4) Å3Block, colourless
Z = 40.45 × 0.43 × 0.37 mm
Data collection top
Bruker AXS D8 Quest with PhotonII CPAD
diffractometer
28338 independent reflections
Radiation source: fine focus sealed tube X-ray source15758 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromatorRint = 0.082
ω and phi scansθmax = 33.2°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
h = 2224
Tmin = 0.670, Tmax = 0.742k = 2020
153291 measured reflectionsl = 2727
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.062H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.200 w = 1/[σ2(Fo2) + (0.0795P)2 + 0.9081P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.003
28338 reflectionsΔρmax = 0.88 e Å3
1359 parametersΔρmin = 1.03 e Å3
1870 restraintsAbsolute structure: Flack x determined using 5601 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013).
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.020 (4)
Special details top

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

Refinement. The structure exhibits pseudo C-centered symmetry emulating space group C2. C2 symmetry was observed for the related hemihydrate and acetone / hexane solvates. Exact translation and two-fold symmetry for the ethyl acetate solvate is broken by the solvate molecules and by a slight modulation of cations and anions. Mean intensity is 1.8 for reflections that should be systematically absent for C2, vs 6.9 for all reflections (2.2 vs 2.9 for mean intensity / sigma).

Ethyl acetate molecules are arranged into two clusters with light and severe disorder. Solvate disorder induces disorder of a cation phenyl and a cation naphtyl group.

The site associated with the ethyl acetate molecule of O1/O2 was refined as two-fold disordered and as fully occupied. The site associated with the ethyl acetate molecule of O3/O4 was refined as five-fold disordered and only partially occupied. One of the moieties of O3/O4 (suffix F) extends away from the main cluster. It induces the disorder of the O1/O2 ethyl acetate, and for the naphtyl group of cation A. A common occupancy ratio was used for these three entities. Disorder of the phenyl group of cation B is correlated with multiple disordered moieties of the severely disordered ethyl acetate and was refined independently.

All ethyl acetate moieties were restrained to have similar geometries. The acetate sections were restrained to be close to planar. The ethyl C-C bond distances were restrained to a target value (1.55 (2) Angstrom). Disordered phenyl and naphtyl groups were restrained to have similar geometries as their not disordered counterparts in the other cation. Uij components of ADPs for disordered atoms closer to each other than 2.0 Angstrom were restrained to be similar. Subject to these conditions the occupancy rates refined to 0.874 (3) to 0.126 (3) for the two-fold disordered ethyl acetate of O1/O2 (shared with the naphtyl disorder of cation A). The occupancy rates for the partially occupied site refined to 0.171 (7), 0.183 (7), 0.126 (3) (same as minor moiety of O1/O2 ethyl acetate), 0.074 (6) and 0.087 (6), for a total occupancy of 0.641. The occupancy ratio of the phenyl disorder of cation B refined to 0.573 (17) to 0.427 (17).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br1A0.02899 (4)0.1368 (3)0.47002 (5)0.0853 (2)
O1A0.23412 (18)0.0834 (4)0.16595 (15)0.0384 (6)
H1AB0.190 (4)0.088 (5)0.182 (3)0.058*
O2A0.31927 (16)0.2987 (4)0.36367 (14)0.0343 (5)
O3A0.25764 (18)0.5025 (4)0.21465 (17)0.0430 (6)
O4A0.3323 (2)0.5009 (5)0.12996 (19)0.0776 (14)
O5A0.4687 (3)0.5653 (5)0.1195 (2)0.0789 (14)
H5A0.410 (6)0.531 (7)0.128 (5)0.118*
O6A0.58605 (19)0.6327 (4)0.19870 (19)0.0508 (7)
N1A0.15387 (17)0.3824 (4)0.10491 (16)0.0290 (5)
H1A0.1921270.4296100.1429260.035*
N2A0.21055 (18)0.2293 (4)0.40474 (16)0.0309 (6)
C1A0.3501 (2)0.1343 (4)0.28290 (18)0.0295 (6)
H1AA0.3894280.1919360.3020460.035*
C2A0.2981 (2)0.1569 (4)0.19441 (19)0.0305 (6)
C3A0.2523 (2)0.2579 (4)0.18924 (18)0.0280 (6)
H3AA0.2099970.2546030.2194900.034*
H3AB0.2959070.3088140.2138550.034*
C4A0.2051 (2)0.2892 (4)0.10544 (19)0.0320 (7)
H4AA0.2477710.3004170.0764370.038*
H4AB0.1654220.2357090.0786180.038*
C5A0.0750 (2)0.3651 (5)0.1305 (2)0.0423 (8)
H5AA0.0453110.4280100.1312940.063*
H5AB0.0921830.3360780.1831650.063*
H5AC0.0358120.3197040.0937300.063*
C6A0.1289 (3)0.4300 (5)0.0261 (2)0.0406 (8)
H6AA0.1812440.4519690.0138790.061*
H6AB0.0915370.4870250.0261000.061*
H6AC0.0975680.3822910.0135310.061*
C7A0.3613 (3)0.1571 (5)0.1439 (3)0.0343 (10)0.874 (3)
C8A0.3446 (4)0.0912 (5)0.0821 (3)0.0432 (11)0.874 (3)
H8A0.2951570.0496490.0725970.052*0.874 (3)
C9A0.3980 (4)0.0828 (6)0.0324 (3)0.0508 (13)0.874 (3)
H9A0.3843850.0363390.0093330.061*0.874 (3)
C10A0.4694 (4)0.1420 (6)0.0449 (4)0.0604 (14)0.874 (3)
H10A0.5052100.1366020.0114930.072*0.874 (3)
C11A0.4905 (4)0.2108 (6)0.1068 (4)0.0623 (14)0.874 (3)
C12A0.5640 (5)0.2752 (8)0.1180 (6)0.091 (2)0.874 (3)
H12A0.5991520.2692220.0840660.109*0.874 (3)
C13A0.5843 (5)0.3433 (8)0.1748 (6)0.096 (2)0.874 (3)
H13A0.6336020.3843860.1809430.115*0.874 (3)
C14A0.5335 (4)0.3540 (7)0.2248 (5)0.0773 (17)0.874 (3)
H14A0.5483790.4019960.2654190.093*0.874 (3)
C15A0.4603 (4)0.2942 (6)0.2155 (4)0.0519 (12)0.874 (3)
H15A0.4258380.3034290.2497350.062*0.874 (3)
C16A0.4361 (3)0.2208 (6)0.1569 (3)0.0456 (11)0.874 (3)
C7C0.3427 (19)0.132 (2)0.1331 (17)0.041 (4)0.126 (3)
C8C0.3206 (19)0.056 (2)0.0799 (16)0.041 (4)0.126 (3)
H8C0.2736490.0139880.0794590.049*0.126 (3)
C9C0.367 (2)0.042 (2)0.0258 (16)0.042 (4)0.126 (3)
H9C0.3506680.0095390.0121490.050*0.126 (3)
C10C0.437 (2)0.100 (2)0.0273 (19)0.046 (4)0.126 (3)
H10C0.4677590.0900040.0097340.056*0.126 (3)
C11C0.463 (2)0.176 (2)0.0845 (19)0.052 (3)0.126 (3)
C12C0.533 (2)0.240 (3)0.084 (2)0.068 (4)0.126 (3)
H12C0.5692950.2212620.0529870.081*0.126 (3)
C13C0.550 (3)0.325 (3)0.125 (3)0.076 (4)0.126 (3)
H13C0.5874270.3738980.1144130.091*0.126 (3)
C14C0.510 (3)0.339 (3)0.183 (3)0.073 (3)0.126 (3)
H14C0.5295440.3907970.2199890.088*0.126 (3)
C15C0.442 (3)0.278 (3)0.189 (2)0.060 (4)0.126 (3)
H15C0.4129380.2931040.2265470.072*0.126 (3)
C16C0.416 (2)0.195 (3)0.140 (2)0.047 (3)0.126 (3)
C17A0.4079 (2)0.0434 (4)0.2939 (2)0.0350 (7)
C18A0.3816 (3)0.0471 (5)0.2559 (3)0.0456 (9)
H18A0.3254100.0535270.2195380.055*
C19A0.4386 (3)0.1282 (5)0.2718 (3)0.0564 (11)
H19A0.4208330.1890450.2454210.068*
C20A0.5198 (3)0.1203 (5)0.3249 (3)0.0591 (13)
H20A0.5576450.1756750.3361630.071*
C21A0.5452 (3)0.0320 (6)0.3613 (3)0.0649 (15)
H21A0.6014300.0261920.3977500.078*
C22A0.4905 (3)0.0499 (5)0.3463 (2)0.0504 (11)
H22A0.5099580.1106310.3722670.060*
C23A0.2886 (2)0.1306 (4)0.33303 (17)0.0275 (6)
C24A0.2493 (2)0.0476 (4)0.34742 (19)0.0311 (6)
H24A0.2624930.0141510.3284030.037*
C25A0.1885 (2)0.0516 (4)0.39060 (19)0.0316 (7)
C26A0.1467 (2)0.0334 (5)0.4085 (2)0.0401 (8)
H26A0.1610540.0971650.3940240.048*
C27A0.0858 (3)0.0227 (5)0.4466 (2)0.0442 (9)
C28A0.0625 (2)0.0697 (5)0.4696 (2)0.0437 (9)
H28A0.0190730.0749020.4953670.052*
C29A0.1037 (2)0.1529 (5)0.4540 (2)0.0381 (8)
H29A0.0885760.2159250.4692690.046*
C30A0.1683 (2)0.1456 (4)0.41547 (18)0.0307 (7)
C31A0.2695 (2)0.2206 (4)0.36887 (18)0.0287 (6)
C32A0.3048 (3)0.3891 (4)0.4001 (2)0.0456 (9)
H32A0.3493580.4374090.3982640.068*
H32B0.3078340.3761970.4548340.068*
H32C0.2473920.4153090.3719670.068*
C33A0.3246 (3)0.5217 (5)0.1966 (2)0.0427 (9)
C34A0.3976 (2)0.5695 (4)0.2579 (2)0.0389 (8)
H34A0.3881110.5786120.3074810.047*
C35A0.4743 (3)0.6012 (4)0.2532 (2)0.0408 (8)
H35A0.5107150.6290670.3004180.049*
C36A0.5130 (3)0.6005 (5)0.1868 (2)0.0432 (9)
Br1B0.54606 (5)0.3491 (3)0.47124 (6)0.0999 (3)
O1B0.74520 (18)0.5862 (4)0.17331 (16)0.0383 (5)
H1BB0.694 (4)0.594 (5)0.186 (3)0.057*
O2B0.81300 (16)0.8084 (4)0.36580 (14)0.0355 (5)
O3B0.7527 (2)1.0064 (4)0.21261 (19)0.0519 (7)
O4B0.8241 (2)1.0126 (5)0.12531 (18)0.0597 (9)
O5B0.9612 (2)1.0754 (4)0.11490 (18)0.0575 (9)
H5B0.901 (5)1.044 (6)0.130 (4)0.086*
O6B1.0803 (2)1.1377 (4)0.19574 (19)0.0508 (7)
N1B0.65378 (17)0.8812 (4)0.10484 (16)0.0319 (6)
H1B0.6903810.9307310.1416970.038*
N2B0.70866 (19)0.7295 (4)0.40698 (16)0.0342 (6)
C1B0.8576 (2)0.6475 (4)0.28897 (19)0.0314 (7)
H1BA0.8880290.7117120.3060930.038*
C2B0.8061 (2)0.6645 (4)0.1995 (2)0.0303 (6)
C3B0.7553 (2)0.7625 (4)0.19154 (18)0.0275 (6)
H3BA0.7124410.7569920.2209960.033*
H3BB0.7962400.8161300.2158340.033*
C4B0.7083 (2)0.7905 (4)0.10731 (19)0.0322 (7)
H4BA0.7511210.8033330.0787030.039*
H4BB0.6708340.7350650.0810390.039*
C5B0.5752 (2)0.8621 (5)0.1307 (3)0.0468 (9)
H5BA0.5443870.9243530.1310850.070*
H5BB0.5930430.8337660.1836160.070*
H5BC0.5368610.8156790.0943540.070*
C6B0.6272 (3)0.9261 (5)0.0248 (2)0.0501 (10)
H6BA0.6788930.9472450.0111970.075*
H6BB0.5898320.9833410.0241860.075*
H6BC0.5953400.8771400.0134300.075*
C7B0.8673 (2)0.6619 (4)0.1480 (2)0.0336 (7)
C8B0.8527 (3)0.5916 (5)0.0892 (2)0.0406 (8)
H8B0.8059530.5466010.0828200.049*
C9B0.9045 (3)0.5840 (5)0.0383 (2)0.0471 (10)
H9B0.8913130.5357410.0021520.057*
C10B0.9730 (3)0.6453 (5)0.0468 (2)0.0484 (10)
H10B1.0079150.6391930.0125720.058*
C11B0.9932 (3)0.7192 (5)0.1068 (3)0.0457 (9)
C12B1.0638 (3)0.7849 (5)0.1143 (3)0.0582 (12)
H12B1.0979210.7780830.0795330.070*
C13B1.0839 (3)0.8564 (6)0.1691 (3)0.0614 (13)
H13B1.1322100.8985130.1736000.074*
C14B1.0325 (3)0.8681 (5)0.2194 (3)0.0497 (9)
H14B1.0453390.9194720.2573730.060*
C15B0.9629 (2)0.8052 (4)0.2145 (2)0.0408 (8)
H15B0.9300250.8139860.2501040.049*
C16B0.9394 (2)0.7285 (4)0.1579 (2)0.0363 (7)
C17B0.9295 (9)0.5716 (10)0.3094 (10)0.035 (2)0.573 (17)
C18B0.9119 (7)0.4729 (10)0.2814 (8)0.050 (2)0.573 (17)
H18B0.8557480.4553490.2488410.060*0.573 (17)
C19B0.9782 (8)0.4019 (9)0.3025 (8)0.057 (2)0.573 (17)
H19B0.9672120.3364620.2827850.068*0.573 (17)
C20B1.0582 (7)0.4260 (9)0.3508 (8)0.048 (2)0.573 (17)
H20B1.1022660.3771410.3654000.057*0.573 (17)
C21B1.0752 (6)0.5208 (9)0.3784 (7)0.046 (2)0.573 (17)
H21B1.1309960.5368810.4125020.055*0.573 (17)
C22B1.0118 (7)0.5936 (9)0.3570 (7)0.0351 (19)0.573 (17)
H22B1.0252050.6592660.3754750.042*0.573 (17)
C17D0.9151 (10)0.5534 (13)0.2970 (11)0.030 (3)0.427 (17)
C18D0.8899 (10)0.4626 (11)0.2593 (9)0.038 (2)0.427 (17)
H18D0.8338580.4538340.2230110.045*0.427 (17)
C19D0.9505 (10)0.3852 (11)0.2772 (9)0.047 (2)0.427 (17)
H19D0.9339420.3221690.2541710.057*0.427 (17)
C20D1.0328 (11)0.3976 (12)0.3271 (8)0.047 (3)0.427 (17)
H20D1.0713940.3429410.3391890.056*0.427 (17)
C21D1.0601 (10)0.4885 (13)0.3596 (9)0.049 (3)0.427 (17)
H21D1.1182370.4991510.3909610.059*0.427 (17)
C22D0.9989 (10)0.5646 (12)0.3448 (10)0.040 (3)0.427 (17)
H22D1.0158720.6269670.3688020.048*0.427 (17)
C23B0.7955 (2)0.6383 (4)0.33776 (19)0.0316 (7)
C24B0.7586 (2)0.5520 (4)0.3511 (2)0.0359 (7)
H24B0.7745920.4917030.3318950.043*
C25B0.6964 (2)0.5511 (5)0.3935 (2)0.0386 (8)
C26B0.6586 (3)0.4623 (5)0.4101 (3)0.0504 (10)
H26B0.6763120.3999910.3956420.060*
C27B0.5956 (3)0.4685 (5)0.4476 (3)0.0554 (11)
C28B0.5681 (3)0.5580 (5)0.4700 (2)0.0495 (10)
H28B0.5238400.5594340.4950260.059*
C29B0.6057 (2)0.6449 (5)0.4557 (2)0.0419 (9)
H29B0.5874130.7061910.4712190.050*
C30B0.6717 (2)0.6430 (5)0.41775 (18)0.0350 (7)
C31B0.7691 (2)0.7254 (4)0.37173 (18)0.0306 (6)
C32B0.7903 (3)0.8970 (5)0.3988 (3)0.0513 (10)
H32D0.8313110.9495650.3966500.077*
H32E0.7926810.8850690.4535250.077*
H32F0.7314920.9171390.3688210.077*
C33B0.8175 (3)1.0299 (4)0.1929 (2)0.0432 (9)
C34B0.8909 (3)1.0788 (4)0.2532 (2)0.0437 (9)
H34B0.8814851.0883320.3027440.052*
C35B0.9672 (3)1.1112 (4)0.2490 (2)0.0412 (8)
H35B1.0028381.1408660.2957860.049*
C36B1.0061 (3)1.1087 (4)0.1827 (2)0.0413 (8)
O10.6549 (4)0.1187 (5)0.5572 (4)0.118 (2)0.874 (3)
O20.7608 (4)0.1996 (6)0.5280 (4)0.0972 (16)0.874 (3)
C10.7171 (5)0.1724 (6)0.5806 (5)0.088 (2)0.874 (3)
C20.7566 (7)0.2127 (8)0.6606 (5)0.119 (3)0.874 (3)
H2A0.7581000.1610790.6995320.178*0.874 (3)
H2B0.7220340.2685920.6692800.178*0.874 (3)
H2C0.8158510.2349030.6659790.178*0.874 (3)
C30.7233 (6)0.1654 (8)0.4500 (5)0.110 (3)0.874 (3)
H3A0.6668650.1985170.4262150.131*0.874 (3)
H3B0.7131230.0932880.4500410.131*0.874 (3)
C40.7838 (7)0.1883 (10)0.4041 (6)0.129 (4)0.874 (3)
H4A0.8416610.1629560.4318550.155*0.874 (3)
H4B0.7867160.2599580.3976550.155*0.874 (3)
H4C0.7629790.1569360.3523430.155*0.874 (3)
O1E0.8165 (19)0.1948 (18)0.5815 (15)0.109 (8)0.126 (3)
O2E0.7400 (17)0.0863 (19)0.4952 (10)0.112 (5)0.126 (3)
C1E0.7688 (14)0.1239 (16)0.5705 (9)0.107 (5)0.126 (3)
C2E0.729 (2)0.075 (3)0.6260 (13)0.124 (9)0.126 (3)
H2EA0.6936510.0191490.5996790.186*0.126 (3)
H2EB0.7753790.0506780.6715520.186*0.126 (3)
H2EC0.6930920.1223120.6433090.186*0.126 (3)
C3E0.7575 (15)0.147 (3)0.4366 (10)0.106 (5)0.126 (3)
H3EA0.7492410.2171060.4473950.127*0.126 (3)
H3EB0.7172560.1298710.3844350.127*0.126 (3)
C4E0.8485 (17)0.129 (4)0.437 (2)0.108 (11)0.126 (3)
H4EA0.8617170.1701580.3972860.129*0.126 (3)
H4EB0.8878240.1461970.4891460.129*0.126 (3)
H4EC0.8559480.0592580.4264000.129*0.126 (3)
O30.8705 (10)0.2818 (19)0.0451 (13)0.081 (6)0.171 (7)
O40.7393 (9)0.2293 (13)0.0417 (9)0.072 (4)0.171 (7)
C50.8128 (9)0.2850 (15)0.0752 (10)0.075 (4)0.171 (7)
C60.8104 (16)0.338 (2)0.1475 (12)0.077 (6)0.171 (7)
H6A0.7543810.3260230.1567280.115*0.171 (7)
H6B0.8571740.3131720.1922750.115*0.171 (7)
H6C0.8181050.4087100.1411130.115*0.171 (7)
C70.7350 (15)0.1865 (12)0.0320 (10)0.075 (5)0.171 (7)
H7A0.6936410.1305220.0432050.090*0.171 (7)
H7B0.7927850.1612190.0312200.090*0.171 (7)
C80.706 (3)0.264 (2)0.0934 (11)0.077 (6)0.171 (7)
H8D0.7025690.2353150.1447210.116*0.171 (7)
H8E0.6485700.2878480.0939290.116*0.171 (7)
H8F0.7473790.3184420.0819840.116*0.171 (7)
O3E0.8603 (8)0.3188 (19)0.0493 (12)0.081 (5)0.183 (7)
O4E0.7167 (8)0.3265 (17)0.0171 (8)0.077 (4)0.183 (7)
C5E0.7968 (8)0.3108 (17)0.0715 (8)0.075 (4)0.183 (7)
C6E0.7921 (15)0.294 (2)0.1523 (8)0.078 (6)0.183 (7)
H6EA0.7312000.2911740.1513940.118*0.183 (7)
H6EB0.8210060.2320080.1726360.118*0.183 (7)
H6EC0.8209740.3488910.1861340.118*0.183 (7)
C7E0.7173 (13)0.3305 (12)0.0622 (8)0.072 (4)0.183 (7)
H7EA0.7714460.3622050.0653660.087*0.183 (7)
H7EB0.6675110.3699190.0938340.087*0.183 (7)
C8E0.712 (3)0.2280 (15)0.0930 (14)0.072 (6)0.183 (7)
H8EA0.7120150.2293640.1477250.108*0.183 (7)
H8EB0.7613640.1896680.0615300.108*0.183 (7)
H8EC0.6577800.1973560.0899020.108*0.183 (7)
O3F0.7477 (16)0.2910 (16)0.2656 (11)0.091 (10)0.126 (3)
O4F0.7156 (12)0.2037 (12)0.1554 (8)0.067 (5)0.126 (3)
C5F0.7074 (12)0.2223 (13)0.2290 (9)0.066 (7)0.126 (3)
C6F0.6446 (14)0.1559 (15)0.2500 (14)0.066 (9)0.126 (3)
H6FA0.6226510.1072160.2082150.099*0.126 (3)
H6FB0.6735590.1217390.2992760.099*0.126 (3)
H6FC0.5961210.1950140.2565370.099*0.126 (3)
C7F0.7750 (13)0.266 (2)0.1332 (10)0.073 (4)0.126 (3)
H7FA0.8284250.2290010.1351490.088*0.126 (3)
H7FB0.7910670.3228070.1696790.088*0.126 (3)
C8F0.733 (2)0.302 (3)0.0522 (14)0.077 (5)0.126 (3)
H8FA0.7728820.3451600.0357910.116*0.126 (3)
H8FB0.7174140.2453910.0164070.116*0.126 (3)
H8FC0.6801820.3388810.0508210.116*0.126 (3)
O3G0.744 (3)0.1657 (14)0.0058 (19)0.081 (8)0.074 (6)
O4G0.7632 (14)0.3233 (17)0.0192 (14)0.074 (4)0.074 (6)
C5G0.765 (2)0.2471 (13)0.0328 (11)0.076 (4)0.074 (6)
C6G0.797 (5)0.278 (3)0.1163 (11)0.073 (6)0.074 (6)
H6GA0.8083010.3489880.1192760.109*0.074 (6)
H6GB0.7539390.2617240.1427330.109*0.074 (6)
H6GC0.8514230.2424280.1419430.109*0.074 (6)
C7G0.6795 (16)0.348 (3)0.0692 (17)0.076 (5)0.074 (6)
H7GA0.6500690.3933080.0417080.092*0.074 (6)
H7GB0.6437800.2877390.0840690.092*0.074 (6)
C8G0.690 (3)0.397 (4)0.1404 (16)0.082 (10)0.074 (6)
H8GA0.6324820.4145960.1756040.123*0.074 (6)
H8GB0.7248400.4567880.1251670.123*0.074 (6)
H8GC0.7185720.3515760.1673850.123*0.074 (6)
O3H0.7694 (17)0.1976 (16)0.010 (2)0.076 (6)0.087 (6)
O4H0.7174 (14)0.3438 (16)0.009 (2)0.077 (4)0.087 (6)
C5H0.7824 (12)0.2734 (14)0.0270 (15)0.078 (4)0.087 (6)
C6H0.8594 (16)0.302 (3)0.093 (2)0.064 (6)0.087 (6)
H6HA0.8504490.3686990.1109520.097*0.087 (6)
H6HB0.8677690.2551930.1357740.097*0.087 (6)
H6HC0.9109390.3027340.0743220.097*0.087 (6)
C7H0.6405 (15)0.3158 (19)0.050 (3)0.073 (5)0.087 (6)
H7HA0.6129140.2590280.0315910.088*0.087 (6)
H7HB0.6545850.2958660.0978810.088*0.087 (6)
C8H0.5805 (18)0.402 (2)0.067 (3)0.083 (11)0.087 (6)
H8HA0.5270440.3835670.1073100.124*0.087 (6)
H8HB0.5667000.4205250.0186690.124*0.087 (6)
H8HC0.6082300.4572380.0847360.124*0.087 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br1A0.0836 (4)0.0720 (5)0.1236 (5)0.0269 (4)0.0664 (4)0.0048 (4)
O1A0.0426 (14)0.0320 (12)0.0367 (13)0.0050 (11)0.0058 (11)0.0062 (10)
O2A0.0394 (13)0.0299 (12)0.0345 (12)0.0012 (10)0.0123 (10)0.0056 (10)
O3A0.0420 (14)0.0427 (15)0.0509 (15)0.0125 (12)0.0238 (12)0.0111 (12)
O4A0.062 (2)0.134 (4)0.0467 (17)0.056 (2)0.0310 (16)0.046 (2)
O5A0.065 (2)0.134 (4)0.0478 (18)0.052 (2)0.0327 (16)0.028 (2)
O6A0.0372 (14)0.0554 (18)0.0620 (18)0.0131 (13)0.0181 (13)0.0024 (14)
N1A0.0275 (12)0.0277 (13)0.0323 (13)0.0048 (10)0.0097 (10)0.0043 (11)
N2A0.0322 (13)0.0332 (14)0.0268 (13)0.0064 (11)0.0082 (10)0.0030 (11)
C1A0.0289 (15)0.0336 (16)0.0262 (14)0.0083 (12)0.0082 (12)0.0034 (12)
C2A0.0335 (16)0.0327 (16)0.0265 (14)0.0090 (13)0.0106 (12)0.0002 (12)
C3A0.0281 (14)0.0293 (15)0.0273 (14)0.0058 (12)0.0095 (12)0.0007 (12)
C4A0.0350 (16)0.0327 (16)0.0286 (15)0.0101 (13)0.0099 (13)0.0025 (13)
C5A0.0288 (15)0.043 (2)0.060 (2)0.0067 (16)0.0202 (15)0.0150 (18)
C6A0.0410 (19)0.043 (2)0.0377 (18)0.0074 (16)0.0113 (15)0.0130 (16)
C7A0.040 (2)0.038 (2)0.0272 (19)0.0172 (18)0.0143 (17)0.0034 (16)
C8A0.054 (3)0.047 (3)0.0301 (19)0.021 (2)0.0143 (18)0.0014 (19)
C9A0.069 (3)0.058 (3)0.030 (2)0.030 (3)0.022 (2)0.005 (2)
C10A0.072 (3)0.067 (3)0.056 (3)0.028 (3)0.042 (3)0.010 (3)
C11A0.063 (3)0.068 (3)0.073 (3)0.013 (3)0.047 (3)0.001 (3)
C12A0.078 (4)0.106 (5)0.115 (5)0.011 (4)0.070 (4)0.017 (4)
C13A0.078 (4)0.107 (5)0.128 (5)0.028 (4)0.069 (4)0.028 (4)
C14A0.064 (3)0.083 (4)0.101 (4)0.023 (3)0.048 (3)0.024 (4)
C15A0.044 (3)0.055 (3)0.066 (3)0.005 (2)0.032 (2)0.009 (2)
C16A0.044 (2)0.052 (3)0.050 (3)0.008 (2)0.029 (2)0.002 (2)
C7C0.046 (7)0.044 (7)0.039 (6)0.019 (6)0.022 (6)0.003 (6)
C8C0.050 (7)0.045 (7)0.031 (6)0.024 (6)0.017 (6)0.004 (6)
C9C0.055 (8)0.047 (8)0.027 (6)0.028 (7)0.017 (6)0.008 (7)
C10C0.059 (8)0.054 (8)0.037 (7)0.029 (7)0.031 (7)0.007 (7)
C11C0.058 (6)0.061 (6)0.049 (6)0.019 (5)0.037 (5)0.000 (6)
C12C0.066 (7)0.083 (7)0.076 (7)0.002 (6)0.053 (6)0.004 (7)
C13C0.063 (6)0.090 (7)0.099 (6)0.014 (6)0.060 (6)0.011 (6)
C14C0.062 (6)0.081 (6)0.091 (6)0.013 (6)0.047 (6)0.011 (6)
C15C0.053 (6)0.068 (7)0.072 (7)0.005 (6)0.037 (6)0.010 (7)
C16C0.050 (5)0.053 (5)0.049 (5)0.010 (5)0.031 (5)0.000 (5)
C17A0.0354 (17)0.0407 (19)0.0325 (16)0.0158 (15)0.0157 (13)0.0082 (14)
C18A0.047 (2)0.043 (2)0.049 (2)0.0174 (17)0.0167 (18)0.0028 (17)
C19A0.065 (3)0.041 (2)0.071 (3)0.022 (2)0.032 (2)0.010 (2)
C20A0.062 (3)0.065 (3)0.059 (3)0.040 (3)0.031 (2)0.023 (2)
C21A0.042 (2)0.089 (4)0.061 (3)0.031 (3)0.012 (2)0.015 (3)
C22A0.0366 (19)0.070 (3)0.045 (2)0.022 (2)0.0127 (16)0.005 (2)
C23A0.0287 (14)0.0304 (15)0.0226 (13)0.0070 (12)0.0062 (11)0.0004 (12)
C24A0.0322 (16)0.0330 (16)0.0282 (15)0.0058 (13)0.0093 (12)0.0006 (13)
C25A0.0284 (15)0.0373 (17)0.0284 (15)0.0025 (13)0.0074 (12)0.0011 (13)
C26A0.0352 (18)0.043 (2)0.0417 (19)0.0009 (15)0.0105 (15)0.0024 (16)
C27A0.0369 (19)0.054 (2)0.044 (2)0.0100 (17)0.0156 (16)0.0009 (18)
C28A0.0356 (18)0.065 (3)0.0338 (18)0.0029 (18)0.0156 (14)0.0026 (17)
C29A0.0305 (16)0.056 (2)0.0291 (16)0.0044 (15)0.0108 (13)0.0076 (15)
C30A0.0254 (14)0.0433 (19)0.0220 (14)0.0052 (13)0.0049 (11)0.0009 (13)
C31A0.0299 (15)0.0303 (16)0.0254 (14)0.0060 (12)0.0073 (12)0.0018 (12)
C32A0.057 (2)0.0321 (19)0.049 (2)0.0020 (16)0.0189 (18)0.0102 (16)
C33A0.046 (2)0.047 (2)0.0398 (19)0.0182 (17)0.0204 (16)0.0123 (16)
C34A0.0427 (19)0.043 (2)0.0336 (17)0.0117 (16)0.0160 (14)0.0074 (15)
C35A0.0419 (19)0.044 (2)0.0361 (18)0.0135 (16)0.0111 (15)0.0076 (15)
C36A0.0405 (19)0.048 (2)0.043 (2)0.0133 (17)0.0145 (16)0.0021 (17)
Br1B0.0847 (4)0.0803 (6)0.1601 (7)0.0043 (4)0.0751 (5)0.0374 (5)
O1B0.0402 (13)0.0300 (12)0.0476 (14)0.0008 (11)0.0175 (11)0.0049 (11)
O2B0.0367 (13)0.0376 (13)0.0344 (12)0.0057 (10)0.0139 (10)0.0007 (10)
O3B0.0568 (18)0.0490 (17)0.0620 (18)0.0169 (14)0.0362 (15)0.0149 (14)
O4B0.0549 (19)0.084 (3)0.0479 (17)0.0317 (17)0.0275 (14)0.0251 (16)
O5B0.0510 (17)0.085 (2)0.0420 (15)0.0259 (17)0.0226 (13)0.0086 (15)
O6B0.0419 (15)0.0460 (16)0.0649 (18)0.0101 (13)0.0162 (14)0.0042 (14)
N1B0.0288 (12)0.0358 (15)0.0325 (13)0.0077 (11)0.0115 (10)0.0083 (12)
N2B0.0304 (13)0.0457 (17)0.0252 (13)0.0082 (12)0.0065 (10)0.0014 (12)
C1B0.0300 (15)0.0336 (17)0.0320 (16)0.0095 (13)0.0114 (13)0.0069 (13)
C2B0.0326 (16)0.0279 (15)0.0333 (16)0.0071 (12)0.0142 (13)0.0016 (12)
C3B0.0273 (14)0.0295 (15)0.0257 (14)0.0077 (12)0.0081 (11)0.0014 (12)
C4B0.0336 (16)0.0310 (16)0.0317 (16)0.0066 (13)0.0094 (13)0.0012 (13)
C5B0.0339 (17)0.052 (2)0.061 (2)0.0102 (18)0.0239 (16)0.016 (2)
C6B0.048 (2)0.061 (3)0.042 (2)0.016 (2)0.0154 (17)0.0232 (19)
C7B0.0347 (17)0.0351 (17)0.0338 (17)0.0110 (14)0.0146 (14)0.0031 (13)
C8B0.047 (2)0.041 (2)0.0349 (18)0.0100 (17)0.0148 (15)0.0038 (15)
C9B0.056 (2)0.050 (2)0.0381 (19)0.021 (2)0.0189 (17)0.0019 (17)
C10B0.054 (2)0.055 (2)0.047 (2)0.025 (2)0.0320 (19)0.0110 (18)
C11B0.0411 (19)0.048 (2)0.056 (2)0.0145 (17)0.0265 (18)0.0106 (18)
C12B0.048 (2)0.067 (3)0.071 (3)0.006 (2)0.035 (2)0.016 (3)
C13B0.043 (2)0.066 (3)0.084 (3)0.003 (2)0.031 (2)0.008 (3)
C14B0.044 (2)0.046 (2)0.060 (2)0.0028 (19)0.0175 (18)0.004 (2)
C15B0.0354 (18)0.043 (2)0.046 (2)0.0044 (16)0.0153 (15)0.0038 (17)
C16B0.0343 (16)0.0372 (18)0.0420 (19)0.0118 (14)0.0185 (14)0.0074 (15)
C17B0.030 (4)0.034 (4)0.043 (5)0.008 (3)0.014 (3)0.009 (4)
C18B0.036 (4)0.043 (4)0.062 (5)0.011 (3)0.001 (4)0.001 (4)
C19B0.045 (5)0.043 (4)0.074 (5)0.014 (4)0.004 (4)0.003 (4)
C20B0.036 (4)0.044 (5)0.064 (5)0.015 (4)0.016 (4)0.013 (4)
C21B0.034 (4)0.047 (5)0.055 (5)0.014 (3)0.011 (3)0.007 (4)
C22B0.025 (3)0.036 (4)0.043 (4)0.006 (3)0.009 (3)0.007 (3)
C17D0.029 (5)0.034 (5)0.031 (5)0.019 (4)0.016 (4)0.008 (4)
C18D0.041 (5)0.032 (4)0.042 (5)0.020 (4)0.014 (4)0.000 (4)
C19D0.048 (5)0.045 (5)0.052 (5)0.025 (4)0.018 (4)0.003 (4)
C20D0.045 (6)0.046 (5)0.049 (5)0.025 (4)0.013 (4)0.006 (4)
C21D0.041 (5)0.046 (6)0.056 (5)0.022 (5)0.007 (4)0.003 (5)
C22D0.035 (5)0.043 (6)0.045 (5)0.014 (4)0.014 (4)0.003 (5)
C23B0.0289 (15)0.0360 (17)0.0308 (15)0.0129 (13)0.0101 (12)0.0070 (13)
C24B0.0342 (17)0.0365 (18)0.0382 (18)0.0105 (14)0.0125 (14)0.0094 (14)
C25B0.0307 (16)0.051 (2)0.0335 (17)0.0069 (15)0.0086 (13)0.0112 (16)
C26B0.040 (2)0.052 (2)0.061 (3)0.0063 (18)0.0179 (18)0.018 (2)
C27B0.048 (2)0.068 (3)0.051 (2)0.005 (2)0.0160 (19)0.022 (2)
C28B0.0349 (19)0.078 (3)0.0365 (19)0.005 (2)0.0121 (15)0.011 (2)
C29B0.0323 (17)0.066 (3)0.0276 (16)0.0048 (17)0.0095 (13)0.0051 (16)
C30B0.0279 (15)0.052 (2)0.0231 (14)0.0088 (14)0.0044 (12)0.0075 (14)
C31B0.0268 (14)0.0378 (17)0.0252 (14)0.0088 (13)0.0047 (11)0.0037 (13)
C32B0.058 (3)0.046 (2)0.054 (2)0.0049 (19)0.023 (2)0.0095 (19)
C33B0.054 (2)0.0350 (18)0.048 (2)0.0104 (17)0.0260 (18)0.0118 (16)
C34B0.056 (2)0.041 (2)0.0410 (19)0.0078 (17)0.0252 (17)0.0093 (16)
C35B0.048 (2)0.0385 (19)0.0367 (18)0.0057 (16)0.0117 (15)0.0069 (15)
C36B0.045 (2)0.0349 (18)0.047 (2)0.0070 (16)0.0173 (16)0.0031 (15)
O10.110 (4)0.072 (4)0.160 (6)0.016 (3)0.024 (4)0.036 (4)
O20.081 (3)0.084 (3)0.140 (4)0.010 (3)0.054 (3)0.014 (3)
C10.078 (4)0.048 (3)0.143 (6)0.010 (3)0.043 (4)0.013 (4)
C20.125 (7)0.096 (6)0.149 (8)0.048 (6)0.061 (6)0.008 (6)
C30.097 (5)0.098 (6)0.144 (7)0.001 (5)0.052 (5)0.020 (5)
C40.113 (7)0.128 (8)0.167 (9)0.012 (6)0.072 (7)0.047 (7)
O1E0.084 (13)0.096 (13)0.150 (14)0.017 (13)0.037 (13)0.001 (13)
O2E0.101 (8)0.090 (8)0.149 (9)0.001 (8)0.045 (8)0.009 (8)
C1E0.092 (8)0.079 (8)0.153 (9)0.006 (8)0.041 (8)0.003 (8)
C2E0.118 (14)0.084 (14)0.163 (15)0.010 (14)0.031 (14)0.009 (14)
C3E0.094 (9)0.096 (9)0.143 (9)0.004 (8)0.057 (9)0.020 (8)
C4E0.101 (19)0.094 (19)0.137 (19)0.007 (17)0.050 (18)0.051 (18)
O30.045 (8)0.070 (10)0.130 (10)0.002 (8)0.027 (8)0.004 (9)
O40.049 (6)0.057 (6)0.109 (7)0.003 (5)0.021 (5)0.006 (6)
C50.050 (6)0.059 (7)0.110 (7)0.002 (6)0.019 (6)0.002 (6)
C60.059 (10)0.067 (11)0.099 (11)0.003 (10)0.014 (10)0.008 (10)
C70.052 (7)0.061 (8)0.109 (9)0.003 (7)0.018 (7)0.006 (7)
C80.050 (9)0.058 (11)0.110 (11)0.006 (10)0.003 (9)0.017 (10)
O3E0.038 (7)0.057 (9)0.143 (11)0.005 (7)0.022 (8)0.014 (9)
O4E0.053 (5)0.061 (6)0.111 (7)0.003 (5)0.014 (5)0.008 (6)
C5E0.050 (6)0.061 (7)0.111 (7)0.004 (5)0.018 (6)0.000 (6)
C6E0.053 (9)0.050 (10)0.115 (11)0.004 (9)0.002 (10)0.011 (10)
C7E0.048 (6)0.063 (7)0.104 (8)0.003 (6)0.020 (6)0.005 (7)
C8E0.050 (9)0.050 (10)0.106 (11)0.004 (10)0.007 (9)0.002 (9)
O3F0.067 (17)0.083 (19)0.11 (2)0.020 (15)0.000 (16)0.005 (17)
O4F0.052 (8)0.063 (10)0.095 (10)0.013 (8)0.035 (8)0.006 (9)
C5F0.045 (11)0.065 (13)0.090 (14)0.015 (11)0.025 (11)0.001 (12)
C6F0.058 (18)0.057 (18)0.09 (2)0.019 (15)0.032 (17)0.004 (17)
C7F0.050 (6)0.059 (7)0.109 (8)0.006 (6)0.020 (6)0.005 (7)
C8F0.054 (8)0.062 (9)0.112 (10)0.004 (8)0.019 (8)0.004 (9)
O3G0.053 (12)0.068 (13)0.113 (13)0.003 (11)0.013 (12)0.002 (12)
O4G0.050 (6)0.060 (7)0.109 (7)0.001 (5)0.019 (6)0.005 (6)
C5G0.050 (6)0.061 (7)0.112 (7)0.000 (5)0.018 (6)0.005 (6)
C6G0.048 (8)0.059 (9)0.111 (10)0.004 (8)0.023 (9)0.005 (9)
C7G0.053 (7)0.062 (8)0.108 (9)0.000 (7)0.014 (7)0.005 (8)
C8G0.055 (16)0.065 (17)0.121 (18)0.002 (16)0.020 (16)0.014 (17)
O3H0.048 (10)0.058 (10)0.112 (11)0.008 (9)0.011 (9)0.003 (10)
O4H0.053 (6)0.062 (7)0.110 (8)0.001 (6)0.014 (6)0.005 (6)
C5H0.053 (6)0.062 (7)0.114 (7)0.002 (5)0.016 (6)0.003 (6)
C6H0.036 (9)0.054 (10)0.110 (11)0.005 (9)0.032 (9)0.001 (10)
C7H0.049 (7)0.059 (8)0.107 (9)0.002 (7)0.016 (7)0.005 (7)
C8H0.057 (18)0.07 (2)0.11 (2)0.019 (17)0.019 (18)0.002 (19)
Geometric parameters (Å, º) top
Br1A—C27A1.906 (4)C10B—H10B0.9500
O1A—C2A1.415 (5)C11B—C12B1.420 (7)
O1A—H1AB0.84 (6)C11B—C16B1.441 (5)
O2A—C31A1.348 (4)C12B—C13B1.346 (8)
O2A—C32A1.437 (4)C12B—H12B0.9500
O3A—C33A1.245 (5)C13B—C14B1.403 (6)
O4A—C33A1.265 (5)C13B—H13B0.9500
O4A—H5A1.33 (10)C14B—C15B1.391 (6)
O5A—C36A1.292 (5)C14B—H14B0.9500
O5A—H5A1.11 (10)C15B—C16B1.420 (6)
O6A—C36A1.216 (5)C15B—H15B0.9500
N1A—C6A1.490 (4)C17B—C22B1.379 (11)
N1A—C5A1.494 (4)C17B—C18B1.424 (13)
N1A—C4A1.508 (4)C18B—C19B1.405 (12)
N1A—H1A1.0000C18B—H18B0.9500
N2A—C31A1.302 (4)C19B—C20B1.361 (12)
N2A—C30A1.365 (5)C19B—H19B0.9500
C1A—C17A1.521 (5)C20B—C21B1.373 (12)
C1A—C23A1.523 (4)C20B—H20B0.9500
C1A—C2A1.582 (4)C21B—C22B1.390 (10)
C1A—H1AA1.0000C21B—H21B0.9500
C2A—C7C1.52 (2)C22B—H22B0.9500
C2A—C3A1.544 (4)C17D—C22D1.375 (14)
C2A—C7A1.550 (5)C17D—C18D1.402 (15)
C3A—C4A1.523 (4)C18D—C19D1.405 (12)
C3A—H3AA0.9900C18D—H18D0.9500
C3A—H3AB0.9900C19D—C20D1.372 (15)
C4A—H4AA0.9900C19D—H19D0.9500
C4A—H4AB0.9900C20D—C21D1.376 (16)
C5A—H5AA0.9800C20D—H20D0.9500
C5A—H5AB0.9800C21D—C22D1.397 (14)
C5A—H5AC0.9800C21D—H21D0.9500
C6A—H6AA0.9800C22D—H22D0.9500
C6A—H6AB0.9800C23B—C24B1.364 (5)
C6A—H6AC0.9800C23B—C31B1.447 (5)
C7A—C8A1.382 (6)C24B—C25B1.429 (5)
C7A—C16A1.445 (7)C24B—H24B0.9500
C8A—C9A1.414 (7)C25B—C30B1.412 (6)
C8A—H8A0.9500C25B—C26B1.419 (6)
C9A—C10A1.366 (10)C26B—C27B1.377 (6)
C9A—H9A0.9500C26B—H26B0.9500
C10A—C11A1.407 (9)C27B—C28B1.389 (8)
C10A—H10A0.9500C28B—C29B1.382 (7)
C11A—C16A1.436 (6)C28B—H28B0.9500
C11A—C12A1.438 (10)C29B—C30B1.423 (5)
C12A—C13A1.336 (12)C29B—H29B0.9500
C12A—H12A0.9500C32B—H32D0.9800
C13A—C14A1.390 (9)C32B—H32E0.9800
C13A—H13A0.9500C32B—H32F0.9800
C14A—C15A1.401 (8)C33B—C34B1.497 (6)
C14A—H14A0.9500C34B—C35B1.331 (6)
C15A—C16A1.410 (8)C34B—H34B0.9500
C15A—H15A0.9500C35B—C36B1.497 (6)
C7C—C8C1.37 (2)C35B—H35B0.9500
C7C—C16C1.42 (2)O1—C11.209 (8)
C8C—C9C1.41 (2)O2—C11.382 (8)
C8C—H8C0.9500O2—C31.421 (10)
C9C—C10C1.37 (2)C1—C21.484 (10)
C9C—H9C0.9500C2—H2A0.9800
C10C—C11C1.42 (2)C2—H2B0.9800
C10C—H10C0.9500C2—H2C0.9800
C11C—C12C1.42 (2)C3—C41.484 (8)
C11C—C16C1.44 (2)C3—H3A0.9900
C12C—C13C1.36 (2)C3—H3B0.9900
C12C—H12C0.9500C4—H4A0.9800
C13C—C14C1.39 (2)C4—H4B0.9800
C13C—H13C0.9500C4—H4C0.9800
C14C—C15C1.40 (2)O1E—C1E1.209 (8)
C14C—H14C0.9500O2E—C1E1.383 (8)
C15C—C16C1.41 (2)O2E—C3E1.421 (10)
C15C—H15C0.9500C1E—C2E1.485 (10)
C17A—C22A1.384 (6)C2E—H2EA0.9800
C17A—C18A1.403 (6)C2E—H2EB0.9800
C18A—C19A1.406 (5)C2E—H2EC0.9800
C18A—H18A0.9500C3E—C4E1.485 (8)
C19A—C20A1.374 (7)C3E—H3EA0.9900
C19A—H19A0.9500C3E—H3EB0.9900
C20A—C21A1.365 (8)C4E—H4EA0.9800
C20A—H20A0.9500C4E—H4EB0.9800
C21A—C22A1.392 (6)C4E—H4EC0.9800
C21A—H21A0.9500O3—C51.209 (8)
C22A—H22A0.9500O4—C51.383 (8)
C23A—C24A1.353 (5)O4—C71.421 (10)
C23A—C31A1.451 (4)C5—C61.484 (10)
C24A—C25A1.419 (5)C6—H6A0.9800
C24A—H24A0.9500C6—H6B0.9800
C25A—C30A1.416 (5)C6—H6C0.9800
C25A—C26A1.418 (5)C7—C81.485 (8)
C26A—C27A1.360 (6)C7—H7A0.9900
C26A—H26A0.9500C7—H7B0.9900
C27A—C28A1.402 (7)C8—H8D0.9800
C28A—C29A1.378 (6)C8—H8E0.9800
C28A—H28A0.9500C8—H8F0.9800
C29A—C30A1.413 (5)O3E—C5E1.209 (8)
C29A—H29A0.9500O4E—C5E1.383 (8)
C32A—H32A0.9800O4E—C7E1.421 (10)
C32A—H32B0.9800C5E—C6E1.485 (10)
C32A—H32C0.9800C6E—H6EA0.9800
C33A—C34A1.495 (5)C6E—H6EB0.9800
C34A—C35A1.337 (5)C6E—H6EC0.9800
C34A—H34A0.9500C7E—C8E1.485 (8)
C35A—C36A1.497 (5)C7E—H7EA0.9900
C35A—H35A0.9500C7E—H7EB0.9900
Br1B—C27B1.906 (5)C8E—H8EA0.9800
O1B—C2B1.427 (4)C8E—H8EB0.9800
O1B—H1BB0.92 (6)C8E—H8EC0.9800
O2B—C31B1.350 (4)O3F—C5F1.209 (8)
O2B—C32B1.432 (5)O4F—C5F1.383 (8)
O3B—C33B1.241 (5)O4F—C7F1.421 (10)
O4B—C33B1.266 (5)C5F—C6F1.484 (10)
O4B—H5B1.29 (8)C6F—H6FA0.9800
O5B—C36B1.293 (5)C6F—H6FB0.9800
O5B—H5B1.17 (8)C6F—H6FC0.9800
O6B—C36B1.216 (5)C7F—C8F1.485 (8)
N1B—C6B1.493 (5)C7F—H7FA0.9900
N1B—C5B1.496 (4)C7F—H7FB0.9900
N1B—C4B1.504 (4)C8F—H8FA0.9800
N1B—H1B1.0000C8F—H8FB0.9800
N2B—C31B1.311 (4)C8F—H8FC0.9800
N2B—C30B1.354 (5)O3G—C5G1.209 (8)
C1B—C17B1.512 (14)O4G—C5G1.383 (8)
C1B—C23B1.518 (5)O4G—C7G1.421 (10)
C1B—C17D1.558 (16)C5G—C6G1.484 (10)
C1B—C2B1.582 (5)C6G—H6GA0.9800
C1B—H1BA1.0000C6G—H6GB0.9800
C2B—C7B1.539 (5)C6G—H6GC0.9800
C2B—C3B1.543 (4)C7G—C8G1.485 (8)
C3B—C4B1.517 (4)C7G—H7GA0.9900
C3B—H3BA0.9900C7G—H7GB0.9900
C3B—H3BB0.9900C8G—H8GA0.9800
C4B—H4BA0.9900C8G—H8GB0.9800
C4B—H4BB0.9900C8G—H8GC0.9800
C5B—H5BA0.9800O3H—C5H1.209 (8)
C5B—H5BB0.9800O4H—C5H1.383 (8)
C5B—H5BC0.9800O4H—C7H1.421 (10)
C6B—H6BA0.9800C5H—C6H1.484 (10)
C6B—H6BB0.9800C6H—H6HA0.9800
C6B—H6BC0.9800C6H—H6HB0.9800
C7B—C8B1.385 (5)C6H—H6HC0.9800
C7B—C16B1.440 (5)C7H—C8H1.485 (8)
C8B—C9B1.411 (5)C7H—H7HA0.9900
C8B—H8B0.9500C7H—H7HB0.9900
C9B—C10B1.354 (7)C8H—H8HA0.9800
C9B—H9B0.9500C8H—H8HB0.9800
C10B—C11B1.431 (7)C8H—H8HC0.9800
C2A—O1A—H1AB115 (4)C15B—C14B—H14B119.6
C31A—O2A—C32A117.1 (3)C13B—C14B—H14B119.6
C33A—O4A—H5A109 (4)C14B—C15B—C16B122.2 (4)
C36A—O5A—H5A107 (4)C14B—C15B—H15B118.9
C6A—N1A—C5A110.0 (3)C16B—C15B—H15B118.9
C6A—N1A—C4A111.2 (3)C15B—C16B—C7B125.4 (3)
C5A—N1A—C4A112.5 (3)C15B—C16B—C11B115.5 (4)
C6A—N1A—H1A107.7C7B—C16B—C11B119.1 (4)
C5A—N1A—H1A107.7C22B—C17B—C18B118.3 (9)
C4A—N1A—H1A107.7C22B—C17B—C1B122.1 (9)
C31A—N2A—C30A117.6 (3)C18B—C17B—C1B119.6 (8)
C17A—C1A—C23A112.3 (3)C19B—C18B—C17B119.4 (9)
C17A—C1A—C2A114.1 (3)C19B—C18B—H18B120.3
C23A—C1A—C2A110.4 (3)C17B—C18B—H18B120.3
C17A—C1A—H1AA106.5C20B—C19B—C18B120.6 (9)
C23A—C1A—H1AA106.5C20B—C19B—H19B119.7
C2A—C1A—H1AA106.5C18B—C19B—H19B119.7
O1A—C2A—C7C92.3 (11)C19B—C20B—C21B120.2 (8)
O1A—C2A—C3A108.3 (3)C19B—C20B—H20B119.9
C7C—C2A—C3A118.3 (13)C21B—C20B—H20B119.9
O1A—C2A—C7A109.2 (3)C20B—C21B—C22B120.8 (8)
C3A—C2A—C7A110.6 (3)C20B—C21B—H21B119.6
O1A—C2A—C1A109.6 (3)C22B—C21B—H21B119.6
C7C—C2A—C1A117.0 (13)C17B—C22B—C21B120.8 (9)
C3A—C2A—C1A109.5 (3)C17B—C22B—H22B119.6
C7A—C2A—C1A109.6 (3)C21B—C22B—H22B119.6
C4A—C3A—C2A113.3 (3)C22D—C17D—C18D119.1 (11)
C4A—C3A—H3AA108.9C22D—C17D—C1B114.6 (11)
C2A—C3A—H3AA108.9C18D—C17D—C1B126.3 (11)
C4A—C3A—H3AB108.9C17D—C18D—C19D117.5 (11)
C2A—C3A—H3AB108.9C17D—C18D—H18D121.3
H3AA—C3A—H3AB107.7C19D—C18D—H18D121.3
N1A—C4A—C3A110.6 (2)C20D—C19D—C18D122.1 (11)
N1A—C4A—H4AA109.5C20D—C19D—H19D119.0
C3A—C4A—H4AA109.5C18D—C19D—H19D119.0
N1A—C4A—H4AB109.5C19D—C20D—C21D120.7 (10)
C3A—C4A—H4AB109.5C19D—C20D—H20D119.7
H4AA—C4A—H4AB108.1C21D—C20D—H20D119.7
N1A—C5A—H5AA109.5C20D—C21D—C22D117.4 (11)
N1A—C5A—H5AB109.5C20D—C21D—H21D121.3
H5AA—C5A—H5AB109.5C22D—C21D—H21D121.3
N1A—C5A—H5AC109.5C17D—C22D—C21D123.1 (12)
H5AA—C5A—H5AC109.5C17D—C22D—H22D118.4
H5AB—C5A—H5AC109.5C21D—C22D—H22D118.4
N1A—C6A—H6AA109.5C24B—C23B—C31B115.2 (3)
N1A—C6A—H6AB109.5C24B—C23B—C1B124.6 (3)
H6AA—C6A—H6AB109.5C31B—C23B—C1B120.1 (3)
N1A—C6A—H6AC109.5C23B—C24B—C25B120.8 (3)
H6AA—C6A—H6AC109.5C23B—C24B—H24B119.6
H6AB—C6A—H6AC109.5C25B—C24B—H24B119.6
C8A—C7A—C16A117.9 (4)C30B—C25B—C26B120.3 (4)
C8A—C7A—C2A117.3 (4)C30B—C25B—C24B117.6 (4)
C16A—C7A—C2A124.8 (4)C26B—C25B—C24B122.1 (4)
C7A—C8A—C9A122.9 (6)C27B—C26B—C25B118.3 (5)
C7A—C8A—H8A118.6C27B—C26B—H26B120.8
C9A—C8A—H8A118.6C25B—C26B—H26B120.8
C10A—C9A—C8A119.6 (5)C26B—C27B—C28B122.7 (4)
C10A—C9A—H9A120.2C26B—C27B—Br1B118.4 (4)
C8A—C9A—H9A120.2C28B—C27B—Br1B118.9 (3)
C9A—C10A—C11A120.8 (5)C29B—C28B—C27B119.5 (4)
C9A—C10A—H10A119.6C29B—C28B—H28B120.3
C11A—C10A—H10A119.6C27B—C28B—H28B120.3
C10A—C11A—C16A120.1 (6)C28B—C29B—C30B120.4 (4)
C10A—C11A—C12A120.5 (5)C28B—C29B—H29B119.8
C16A—C11A—C12A119.3 (6)C30B—C29B—H29B119.8
C13A—C12A—C11A122.0 (6)N2B—C30B—C25B122.7 (3)
C13A—C12A—H12A119.0N2B—C30B—C29B118.5 (4)
C11A—C12A—H12A119.0C25B—C30B—C29B118.8 (4)
C12A—C13A—C14A120.0 (7)N2B—C31B—O2B119.1 (3)
C12A—C13A—H13A120.0N2B—C31B—C23B126.2 (3)
C14A—C13A—H13A120.0O2B—C31B—C23B114.6 (3)
C13A—C14A—C15A120.2 (7)O2B—C32B—H32D109.5
C13A—C14A—H14A119.9O2B—C32B—H32E109.5
C15A—C14A—H14A119.9H32D—C32B—H32E109.5
C14A—C15A—C16A122.2 (5)O2B—C32B—H32F109.5
C14A—C15A—H15A118.9H32D—C32B—H32F109.5
C16A—C15A—H15A118.9H32E—C32B—H32F109.5
C15A—C16A—C11A116.3 (5)O3B—C33B—O4B122.8 (4)
C15A—C16A—C7A125.0 (4)O3B—C33B—C34B117.7 (4)
C11A—C16A—C7A118.8 (5)O4B—C33B—C34B119.5 (4)
C8C—C7C—C16C123 (2)C35B—C34B—C33B130.8 (4)
C8C—C7C—C2A126 (2)C35B—C34B—H34B114.6
C16C—C7C—C2A111.5 (18)C33B—C34B—H34B114.6
C7C—C8C—C9C120 (2)C34B—C35B—C36B130.6 (4)
C7C—C8C—H8C120.0C34B—C35B—H35B114.7
C9C—C8C—H8C120.0C36B—C35B—H35B114.7
C10C—C9C—C8C121 (2)O6B—C36B—O5B122.5 (4)
C10C—C9C—H9C119.7O6B—C36B—C35B117.6 (4)
C8C—C9C—H9C119.7O5B—C36B—C35B119.9 (3)
C9C—C10C—C11C120 (2)C1—O2—C3115.1 (6)
C9C—C10C—H10C120.1O1—C1—O2117.7 (7)
C11C—C10C—H10C120.1O1—C1—C2128.9 (7)
C12C—C11C—C10C120 (2)O2—C1—C2113.3 (6)
C12C—C11C—C16C119 (2)C1—C2—H2A109.5
C10C—C11C—C16C121 (2)C1—C2—H2B109.5
C13C—C12C—C11C123 (2)H2A—C2—H2B109.5
C13C—C12C—H12C118.6C1—C2—H2C109.5
C11C—C12C—H12C118.6H2A—C2—H2C109.5
C12C—C13C—C14C117 (3)H2B—C2—H2C109.5
C12C—C13C—H13C121.5O2—C3—C4108.4 (7)
C14C—C13C—H13C121.5O2—C3—H3A110.0
C13C—C14C—C15C122 (3)C4—C3—H3A110.0
C13C—C14C—H14C119.1O2—C3—H3B110.0
C15C—C14C—H14C119.1C4—C3—H3B110.0
C14C—C15C—C16C121 (2)H3A—C3—H3B108.4
C14C—C15C—H15C119.3C3—C4—H4A109.5
C16C—C15C—H15C119.3C3—C4—H4B109.5
C15C—C16C—C7C128 (2)H4A—C4—H4B109.5
C15C—C16C—C11C116 (2)C3—C4—H4C109.5
C7C—C16C—C11C116 (2)H4A—C4—H4C109.5
C22A—C17A—C18A118.3 (4)H4B—C4—H4C109.5
C22A—C17A—C1A117.8 (4)C1E—O2E—C3E114.9 (6)
C18A—C17A—C1A123.9 (3)O1E—C1E—O2E117.6 (7)
C17A—C18A—C19A119.9 (4)O1E—C1E—C2E128.8 (7)
C17A—C18A—H18A120.1O2E—C1E—C2E113.4 (6)
C19A—C18A—H18A120.1C1E—C2E—H2EA109.5
C20A—C19A—C18A120.8 (5)C1E—C2E—H2EB109.5
C20A—C19A—H19A119.6H2EA—C2E—H2EB109.5
C18A—C19A—H19A119.6C1E—C2E—H2EC109.5
C21A—C20A—C19A119.1 (4)H2EA—C2E—H2EC109.5
C21A—C20A—H20A120.5H2EB—C2E—H2EC109.5
C19A—C20A—H20A120.5O2E—C3E—C4E108.3 (7)
C20A—C21A—C22A121.5 (5)O2E—C3E—H3EA110.0
C20A—C21A—H21A119.2C4E—C3E—H3EA110.0
C22A—C21A—H21A119.2O2E—C3E—H3EB110.0
C17A—C22A—C21A120.5 (5)C4E—C3E—H3EB110.0
C17A—C22A—H22A119.8H3EA—C3E—H3EB108.4
C21A—C22A—H22A119.8C3E—C4E—H4EA109.5
C24A—C23A—C31A116.1 (3)C3E—C4E—H4EB109.5
C24A—C23A—C1A124.4 (3)H4EA—C4E—H4EB109.5
C31A—C23A—C1A119.6 (3)C3E—C4E—H4EC109.5
C23A—C24A—C25A120.8 (3)H4EA—C4E—H4EC109.5
C23A—C24A—H24A119.6H4EB—C4E—H4EC109.5
C25A—C24A—H24A119.6C5—O4—C7115.0 (6)
C30A—C25A—C26A119.2 (3)O3—C5—O4117.7 (7)
C30A—C25A—C24A117.8 (3)O3—C5—C6128.8 (7)
C26A—C25A—C24A123.0 (3)O4—C5—C6113.4 (6)
C27A—C26A—C25A119.4 (4)C5—C6—H6A109.5
C27A—C26A—H26A120.3C5—C6—H6B109.5
C25A—C26A—H26A120.3H6A—C6—H6B109.5
C26A—C27A—C28A122.5 (4)C5—C6—H6C109.5
C26A—C27A—Br1A119.4 (3)H6A—C6—H6C109.5
C28A—C27A—Br1A118.1 (3)H6B—C6—H6C109.5
C29A—C28A—C27A118.8 (3)O4—C7—C8108.3 (7)
C29A—C28A—H28A120.6O4—C7—H7A110.0
C27A—C28A—H28A120.6C8—C7—H7A110.0
C28A—C29A—C30A120.8 (4)O4—C7—H7B110.0
C28A—C29A—H29A119.6C8—C7—H7B110.0
C30A—C29A—H29A119.6H7A—C7—H7B108.4
N2A—C30A—C29A118.8 (3)C7—C8—H8D109.5
N2A—C30A—C25A122.0 (3)C7—C8—H8E109.5
C29A—C30A—C25A119.2 (3)H8D—C8—H8E109.5
N2A—C31A—O2A120.1 (3)C7—C8—H8F109.5
N2A—C31A—C23A125.2 (3)H8D—C8—H8F109.5
O2A—C31A—C23A114.7 (3)H8E—C8—H8F109.5
O2A—C32A—H32A109.5C5E—O4E—C7E114.9 (6)
O2A—C32A—H32B109.5O3E—C5E—O4E117.6 (7)
H32A—C32A—H32B109.5O3E—C5E—C6E128.8 (7)
O2A—C32A—H32C109.5O4E—C5E—C6E113.4 (6)
H32A—C32A—H32C109.5C5E—C6E—H6EA109.5
H32B—C32A—H32C109.5C5E—C6E—H6EB109.5
O3A—C33A—O4A122.3 (4)H6EA—C6E—H6EB109.5
O3A—C33A—C34A117.2 (3)C5E—C6E—H6EC109.5
O4A—C33A—C34A120.5 (4)H6EA—C6E—H6EC109.5
C35A—C34A—C33A129.4 (3)H6EB—C6E—H6EC109.5
C35A—C34A—H34A115.3O4E—C7E—C8E108.3 (7)
C33A—C34A—H34A115.3O4E—C7E—H7EA110.0
C34A—C35A—C36A131.4 (3)C8E—C7E—H7EA110.0
C34A—C35A—H35A114.3O4E—C7E—H7EB110.0
C36A—C35A—H35A114.3C8E—C7E—H7EB110.0
O6A—C36A—O5A122.3 (4)H7EA—C7E—H7EB108.4
O6A—C36A—C35A118.1 (4)C7E—C8E—H8EA109.5
O5A—C36A—C35A119.5 (3)C7E—C8E—H8EB109.5
C2B—O1B—H1BB115 (4)H8EA—C8E—H8EB109.5
C31B—O2B—C32B117.4 (3)C7E—C8E—H8EC109.5
C33B—O4B—H5B103 (3)H8EA—C8E—H8EC109.5
C36B—O5B—H5B101 (3)H8EB—C8E—H8EC109.5
C6B—N1B—C5B109.7 (3)C5F—O4F—C7F115.0 (6)
C6B—N1B—C4B111.0 (3)O3F—C5F—O4F117.7 (7)
C5B—N1B—C4B113.1 (3)O3F—C5F—C6F128.8 (7)
C6B—N1B—H1B107.6O4F—C5F—C6F113.4 (6)
C5B—N1B—H1B107.6C5F—C6F—H6FA109.5
C4B—N1B—H1B107.6C5F—C6F—H6FB109.5
C31B—N2B—C30B117.0 (3)H6FA—C6F—H6FB109.5
C17B—C1B—C23B113.4 (8)C5F—C6F—H6FC109.5
C23B—C1B—C17D111.0 (9)H6FA—C6F—H6FC109.5
C17B—C1B—C2B118.5 (7)H6FB—C6F—H6FC109.5
C23B—C1B—C2B110.7 (3)O4F—C7F—C8F108.3 (7)
C17D—C1B—C2B109.3 (7)O4F—C7F—H7FA110.0
C17B—C1B—H1BA104.2C8F—C7F—H7FA110.0
C23B—C1B—H1BA104.2O4F—C7F—H7FB110.0
C2B—C1B—H1BA104.2C8F—C7F—H7FB110.0
O1B—C2B—C7B106.8 (3)H7FA—C7F—H7FB108.4
O1B—C2B—C3B108.2 (3)C7F—C8F—H8FA109.5
C7B—C2B—C3B112.5 (3)C7F—C8F—H8FB109.5
O1B—C2B—C1B109.1 (3)H8FA—C8F—H8FB109.5
C7B—C2B—C1B111.2 (3)C7F—C8F—H8FC109.5
C3B—C2B—C1B108.9 (3)H8FA—C8F—H8FC109.5
C4B—C3B—C2B113.7 (3)H8FB—C8F—H8FC109.5
C4B—C3B—H3BA108.8C5G—O4G—C7G114.9 (6)
C2B—C3B—H3BA108.8O3G—C5G—O4G117.6 (7)
C4B—C3B—H3BB108.8O3G—C5G—C6G128.9 (7)
C2B—C3B—H3BB108.8O4G—C5G—C6G113.4 (6)
H3BA—C3B—H3BB107.7C5G—C6G—H6GA109.5
N1B—C4B—C3B110.4 (3)C5G—C6G—H6GB109.5
N1B—C4B—H4BA109.6H6GA—C6G—H6GB109.5
C3B—C4B—H4BA109.6C5G—C6G—H6GC109.5
N1B—C4B—H4BB109.6H6GA—C6G—H6GC109.5
C3B—C4B—H4BB109.6H6GB—C6G—H6GC109.5
H4BA—C4B—H4BB108.1O4G—C7G—C8G108.3 (7)
N1B—C5B—H5BA109.5O4G—C7G—H7GA110.0
N1B—C5B—H5BB109.5C8G—C7G—H7GA110.0
H5BA—C5B—H5BB109.5O4G—C7G—H7GB110.0
N1B—C5B—H5BC109.5C8G—C7G—H7GB110.0
H5BA—C5B—H5BC109.5H7GA—C7G—H7GB108.4
H5BB—C5B—H5BC109.5C7G—C8G—H8GA109.5
N1B—C6B—H6BA109.5C7G—C8G—H8GB109.5
N1B—C6B—H6BB109.5H8GA—C8G—H8GB109.5
H6BA—C6B—H6BB109.5C7G—C8G—H8GC109.5
N1B—C6B—H6BC109.5H8GA—C8G—H8GC109.5
H6BA—C6B—H6BC109.5H8GB—C8G—H8GC109.5
H6BB—C6B—H6BC109.5C5H—O4H—C7H114.9 (6)
C8B—C7B—C16B118.1 (3)O3H—C5H—O4H117.6 (7)
C8B—C7B—C2B118.3 (3)O3H—C5H—C6H128.9 (7)
C16B—C7B—C2B123.5 (3)O4H—C5H—C6H113.4 (6)
C7B—C8B—C9B122.6 (4)C5H—C6H—H6HA109.5
C7B—C8B—H8B118.7C5H—C6H—H6HB109.5
C9B—C8B—H8B118.7H6HA—C6H—H6HB109.5
C10B—C9B—C8B120.4 (4)C5H—C6H—H6HC109.5
C10B—C9B—H9B119.8H6HA—C6H—H6HC109.5
C8B—C9B—H9B119.8H6HB—C6H—H6HC109.5
C9B—C10B—C11B120.5 (3)O4H—C7H—C8H108.4 (7)
C9B—C10B—H10B119.7O4H—C7H—H7HA110.0
C11B—C10B—H10B119.7C8H—C7H—H7HA110.0
C12B—C11B—C10B120.3 (4)O4H—C7H—H7HB110.0
C12B—C11B—C16B120.3 (4)C8H—C7H—H7HB110.0
C10B—C11B—C16B119.3 (4)H7HA—C7H—H7HB108.4
C13B—C12B—C11B122.1 (4)C7H—C8H—H8HA109.5
C13B—C12B—H12B118.9C7H—C8H—H8HB109.5
C11B—C12B—H12B118.9H8HA—C8H—H8HB109.5
C12B—C13B—C14B119.1 (4)C7H—C8H—H8HC109.5
C12B—C13B—H13B120.5H8HA—C8H—H8HC109.5
C14B—C13B—H13B120.5H8HB—C8H—H8HC109.5
C15B—C14B—C13B120.8 (5)
C17A—C1A—C2A—O1A69.3 (4)C23B—C1B—C2B—C7B173.4 (3)
C23A—C1A—C2A—O1A58.3 (3)C17D—C1B—C2B—C7B50.8 (8)
C17A—C1A—C2A—C7C33.9 (13)C17B—C1B—C2B—C3B164.4 (7)
C23A—C1A—C2A—C7C161.5 (13)C23B—C1B—C2B—C3B62.1 (4)
C17A—C1A—C2A—C3A172.0 (3)C17D—C1B—C2B—C3B175.3 (8)
C23A—C1A—C2A—C3A60.3 (4)O1B—C2B—C3B—C4B65.7 (4)
C17A—C1A—C2A—C7A50.6 (4)C7B—C2B—C3B—C4B52.1 (4)
C23A—C1A—C2A—C7A178.2 (3)C1B—C2B—C3B—C4B175.9 (3)
O1A—C2A—C3A—C4A64.2 (4)C6B—N1B—C4B—C3B164.1 (3)
C7C—C2A—C3A—C4A38.9 (14)C5B—N1B—C4B—C3B72.0 (4)
C7A—C2A—C3A—C4A55.5 (4)C2B—C3B—C4B—N1B174.6 (3)
C1A—C2A—C3A—C4A176.4 (3)O1B—C2B—C7B—C8B1.3 (4)
C6A—N1A—C4A—C3A163.4 (3)C3B—C2B—C7B—C8B117.3 (4)
C5A—N1A—C4A—C3A72.8 (4)C1B—C2B—C7B—C8B120.2 (3)
C2A—C3A—C4A—N1A173.9 (3)O1B—C2B—C7B—C16B178.4 (3)
O1A—C2A—C7A—C8A1.4 (5)C3B—C2B—C7B—C16B63.0 (4)
C3A—C2A—C7A—C8A117.7 (4)C1B—C2B—C7B—C16B59.5 (4)
C1A—C2A—C7A—C8A121.5 (4)C16B—C7B—C8B—C9B1.1 (6)
O1A—C2A—C7A—C16A178.5 (4)C2B—C7B—C8B—C9B179.2 (3)
C3A—C2A—C7A—C16A62.4 (5)C7B—C8B—C9B—C10B1.6 (6)
C1A—C2A—C7A—C16A58.4 (5)C8B—C9B—C10B—C11B0.7 (6)
C16A—C7A—C8A—C9A1.0 (7)C9B—C10B—C11B—C12B178.4 (4)
C2A—C7A—C8A—C9A178.9 (4)C9B—C10B—C11B—C16B0.6 (6)
C7A—C8A—C9A—C10A0.2 (7)C10B—C11B—C12B—C13B178.8 (5)
C8A—C9A—C10A—C11A0.2 (8)C16B—C11B—C12B—C13B1.0 (7)
C9A—C10A—C11A—C16A1.0 (9)C11B—C12B—C13B—C14B1.4 (8)
C9A—C10A—C11A—C12A177.9 (7)C12B—C13B—C14B—C15B1.6 (8)
C10A—C11A—C12A—C13A178.1 (9)C13B—C14B—C15B—C16B1.4 (7)
C16A—C11A—C12A—C13A1.2 (14)C14B—C15B—C16B—C7B178.6 (4)
C11A—C12A—C13A—C14A0.5 (16)C14B—C15B—C16B—C11B0.9 (6)
C12A—C13A—C14A—C15A0.6 (15)C8B—C7B—C16B—C15B179.3 (4)
C13A—C14A—C15A—C16A1.0 (12)C2B—C7B—C16B—C15B1.0 (6)
C14A—C15A—C16A—C11A0.3 (10)C8B—C7B—C16B—C11B0.2 (5)
C14A—C15A—C16A—C7A179.7 (6)C2B—C7B—C16B—C11B179.4 (3)
C10A—C11A—C16A—C15A177.6 (6)C12B—C11B—C16B—C15B0.7 (6)
C12A—C11A—C16A—C15A0.8 (10)C10B—C11B—C16B—C15B178.5 (4)
C10A—C11A—C16A—C7A1.8 (9)C12B—C11B—C16B—C7B178.9 (4)
C12A—C11A—C16A—C7A178.7 (7)C10B—C11B—C16B—C7B1.1 (5)
C8A—C7A—C16A—C15A177.7 (5)C23B—C1B—C17B—C22B99.8 (14)
C2A—C7A—C16A—C15A2.5 (8)C2B—C1B—C17B—C22B127.9 (12)
C8A—C7A—C16A—C11A1.7 (7)C23B—C1B—C17B—C18B77.7 (15)
C2A—C7A—C16A—C11A178.2 (5)C2B—C1B—C17B—C18B54.6 (16)
O1A—C2A—C7C—C8C4.6 (19)C22B—C17B—C18B—C19B0 (2)
C3A—C2A—C7C—C8C116.8 (16)C1B—C17B—C18B—C19B178.1 (13)
C1A—C2A—C7C—C8C108.8 (17)C17B—C18B—C19B—C20B1.7 (19)
O1A—C2A—C7C—C16C179 (3)C18B—C19B—C20B—C21B1.2 (17)
C3A—C2A—C7C—C16C67 (3)C19B—C20B—C21B—C22B0.6 (16)
C1A—C2A—C7C—C16C68 (3)C18B—C17B—C22B—C21B1 (2)
C16C—C7C—C8C—C9C4 (2)C1B—C17B—C22B—C21B176.3 (13)
C2A—C7C—C8C—C9C180 (3)C20B—C21B—C22B—C17B1.8 (17)
C7C—C8C—C9C—C10C2 (2)C23B—C1B—C17D—C22D103.6 (14)
C8C—C9C—C10C—C11C1 (4)C2B—C1B—C17D—C22D134.0 (13)
C9C—C10C—C11C—C12C177 (3)C23B—C1B—C17D—C18D78.0 (18)
C9C—C10C—C11C—C16C2 (6)C2B—C1B—C17D—C18D44.4 (19)
C10C—C11C—C12C—C13C166 (4)C22D—C17D—C18D—C19D5 (2)
C16C—C11C—C12C—C13C10 (6)C1B—C17D—C18D—C19D177.1 (15)
C11C—C12C—C13C—C14C15 (7)C17D—C18D—C19D—C20D3 (2)
C12C—C13C—C14C—C15C13 (7)C18D—C19D—C20D—C21D2 (2)
C13C—C14C—C15C—C16C6 (8)C19D—C20D—C21D—C22D5 (2)
C14C—C15C—C16C—C7C173 (4)C18D—C17D—C22D—C21D2 (3)
C14C—C15C—C16C—C11C0 (7)C1B—C17D—C22D—C21D179.6 (15)
C8C—C7C—C16C—C15C176 (4)C20D—C21D—C22D—C17D3 (2)
C2A—C7C—C16C—C15C7 (6)C17B—C1B—C23B—C24B47.9 (7)
C8C—C7C—C16C—C11C3 (5)C17D—C1B—C23B—C24B33.5 (8)
C2A—C7C—C16C—C11C180 (3)C2B—C1B—C23B—C24B88.1 (4)
C12C—C11C—C16C—C15C2 (6)C17B—C1B—C23B—C31B134.3 (6)
C10C—C11C—C16C—C15C174 (4)C17D—C1B—C23B—C31B148.7 (7)
C12C—C11C—C16C—C7C176 (4)C2B—C1B—C23B—C31B89.7 (4)
C10C—C11C—C16C—C7C0 (6)C31B—C23B—C24B—C25B2.1 (5)
C23A—C1A—C17A—C22A96.5 (4)C1B—C23B—C24B—C25B175.8 (3)
C2A—C1A—C17A—C22A136.9 (4)C23B—C24B—C25B—C30B2.9 (5)
C23A—C1A—C17A—C18A81.6 (4)C23B—C24B—C25B—C26B178.3 (4)
C2A—C1A—C17A—C18A45.1 (5)C30B—C25B—C26B—C27B2.3 (6)
C22A—C17A—C18A—C19A0.2 (6)C24B—C25B—C26B—C27B176.5 (4)
C1A—C17A—C18A—C19A177.8 (4)C25B—C26B—C27B—C28B0.3 (7)
C17A—C18A—C19A—C20A0.8 (7)C25B—C26B—C27B—Br1B179.1 (3)
C18A—C19A—C20A—C21A1.2 (7)C26B—C27B—C28B—C29B1.0 (7)
C19A—C20A—C21A—C22A0.6 (8)Br1B—C27B—C28B—C29B177.7 (3)
C18A—C17A—C22A—C21A0.8 (6)C27B—C28B—C29B—C30B0.4 (6)
C1A—C17A—C22A—C21A177.4 (4)C31B—N2B—C30B—C25B0.7 (5)
C20A—C21A—C22A—C17A0.4 (8)C31B—N2B—C30B—C29B179.8 (3)
C17A—C1A—C23A—C24A37.5 (4)C26B—C25B—C30B—N2B176.6 (3)
C2A—C1A—C23A—C24A91.1 (4)C24B—C25B—C30B—N2B4.5 (5)
C17A—C1A—C23A—C31A142.3 (3)C26B—C25B—C30B—C29B2.8 (5)
C2A—C1A—C23A—C31A89.1 (3)C24B—C25B—C30B—C29B176.0 (3)
C31A—C23A—C24A—C25A4.3 (4)C28B—C29B—C30B—N2B178.0 (3)
C1A—C23A—C24A—C25A175.9 (3)C28B—C29B—C30B—C25B1.5 (5)
C23A—C24A—C25A—C30A2.2 (5)C30B—N2B—C31B—O2B174.3 (3)
C23A—C24A—C25A—C26A178.8 (3)C30B—N2B—C31B—C23B5.1 (5)
C30A—C25A—C26A—C27A2.4 (5)C32B—O2B—C31B—N2B0.1 (5)
C24A—C25A—C26A—C27A176.6 (3)C32B—O2B—C31B—C23B179.6 (3)
C25A—C26A—C27A—C28A0.2 (6)C24B—C23B—C31B—N2B6.5 (5)
C25A—C26A—C27A—Br1A179.5 (3)C1B—C23B—C31B—N2B171.5 (3)
C26A—C27A—C28A—C29A1.0 (6)C24B—C23B—C31B—O2B172.9 (3)
Br1A—C27A—C28A—C29A179.2 (3)C1B—C23B—C31B—O2B9.1 (4)
C27A—C28A—C29A—C30A0.1 (5)O3B—C33B—C34B—C35B179.8 (5)
C31A—N2A—C30A—C29A179.8 (3)O4B—C33B—C34B—C35B1.0 (8)
C31A—N2A—C30A—C25A1.5 (4)C33B—C34B—C35B—C36B0.9 (8)
C28A—C29A—C30A—N2A176.7 (3)C34B—C35B—C36B—O6B175.1 (5)
C28A—C29A—C30A—C25A2.0 (5)C34B—C35B—C36B—O5B4.1 (7)
C26A—C25A—C30A—N2A175.4 (3)C3—O2—C1—O13.9 (11)
C24A—C25A—C30A—N2A5.5 (5)C3—O2—C1—C2177.9 (8)
C26A—C25A—C30A—C29A3.3 (5)C1—O2—C3—C4172.1 (8)
C24A—C25A—C30A—C29A175.8 (3)C3E—O2E—C1E—O1E11 (3)
C30A—N2A—C31A—O2A173.3 (3)C3E—O2E—C1E—C2E164 (3)
C30A—N2A—C31A—C23A5.9 (5)C1E—O2E—C3E—C4E81 (3)
C32A—O2A—C31A—N2A1.0 (5)C7—O4—C5—O39 (3)
C32A—O2A—C31A—C23A178.3 (3)C7—O4—C5—C6173.5 (18)
C24A—C23A—C31A—N2A8.9 (5)C5—O4—C7—C880 (3)
C1A—C23A—C31A—N2A171.2 (3)C7E—O4E—C5E—O3E12 (3)
C24A—C23A—C31A—O2A170.4 (3)C7E—O4E—C5E—C6E172.6 (19)
C1A—C23A—C31A—O2A9.5 (4)C5E—O4E—C7E—C8E85 (2)
O3A—C33A—C34A—C35A177.0 (4)C7F—O4F—C5F—O3F3 (3)
O4A—C33A—C34A—C35A4.0 (8)C7F—O4F—C5F—C6F180 (2)
C33A—C34A—C35A—C36A0.3 (8)C5F—O4F—C7F—C8F133 (3)
C34A—C35A—C36A—O6A178.6 (5)C7G—O4G—C5G—O3G66 (4)
C34A—C35A—C36A—O5A0.8 (8)C7G—O4G—C5G—C6G117 (4)
C17B—C1B—C2B—O1B77.7 (7)C5G—O4G—C7G—C8G156 (3)
C23B—C1B—C2B—O1B55.8 (3)C7H—O4H—C5H—O3H2 (5)
C17D—C1B—C2B—O1B66.8 (8)C7H—O4H—C5H—C6H176 (4)
C17B—C1B—C2B—C7B39.9 (8)C5H—O4H—C7H—C8H175 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1AB···O6Bi0.84 (6)1.98 (6)2.791 (4)160 (6)
O5A—H5A···O4A1.11 (10)1.33 (10)2.426 (5)171 (9)
N1A—H1A···O3A1.001.712.707 (4)175
N1A—H1A···O4A1.002.543.211 (4)125
O1B—H1BB···O6A0.92 (6)1.91 (6)2.812 (4)168 (6)
O5B—H5B···O4B1.17 (8)1.29 (8)2.429 (4)164 (6)
N1B—H1B···O3B1.001.702.701 (4)174
N1B—H1B···O4B1.002.523.204 (4)125
C3A—H3AA···O6Bi0.992.563.251 (4)127
C5A—H5AC···O3ii0.982.603.391 (15)138
C6A—H6AA···O4Biii0.982.593.218 (5)122
C32A—H32A···O1iv0.982.593.220 (7)122
C1B—H1BA···O2B1.002.262.780 (4)111
C3B—H3BA···O6A0.992.583.284 (4)128
C6B—H6BA···O4Av0.982.583.190 (5)121
C2E—H2EB···O3Avi0.982.342.96 (2)120
C4E—H4EB···O1E0.982.372.91 (5)114
C7—H7A···O4Aiii0.992.293.068 (15)134
C8E—H8EC···O5Aiii0.982.653.57 (3)157
C8G—H8GB···O1Av0.982.052.90 (5)145
Symmetry codes: (i) x1, y1, z; (ii) x1, y, z; (iii) x+1, y1/2, z; (iv) x+1, y+1/2, z+1; (v) x+1, y+1/2, z; (vi) x+1, y1/2, z+1.
[4-(6-bromo-2-methoxyquinolin-3-yl)-3-hydroxy-3-(naphthalen-1-yl)-4-phenylbutyl]dimethylazanium 3-carboxyprop-2-enoate–hexane–acetone (1/0.248/1) (acetone_hexane) top
Crystal data top
2C32H32BrN2O2+·2C4H3O4·0.495C6H14·2.01C3H6OF(000) = 1570.1
Mr = 1502.51Dx = 1.336 Mg m3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
a = 16.0678 (9) ÅCell parameters from 9698 reflections
b = 13.6440 (8) Åθ = 2.5–31.7°
c = 17.8720 (8) ŵ = 1.15 mm1
β = 107.6347 (18)°T = 150 K
V = 3733.9 (3) Å3Block, colourless
Z = 20.48 × 0.35 × 0.21 mm
Data collection top
Bruker AXS D8 Quest with PhotonII CPAD
diffractometer
14074 independent reflections
Radiation source: fine focus sealed tube X-ray source9700 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromatorRint = 0.059
Detector resolution: 7.4074 pixels mm-1θmax = 33.1°, θmin = 2.4°
ω and phi scansh = 2424
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
k = 2020
Tmin = 0.439, Tmax = 0.498l = 2722
73087 measured reflections
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.047 w = 1/[σ2(Fo2) + (0.0357P)2 + 1.6623P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.126(Δ/σ)max < 0.001
S = 1.03Δρmax = 0.61 e Å3
14074 reflectionsΔρmin = 0.62 e Å3
558 parametersExtinction correction: SHELXL2018/3 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
407 restraintsExtinction coefficient: 0.0034 (10)
Primary atom site location: isomorphous structure methodsAbsolute structure: Flack x determined using 3753 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.006 (3)
Special details top

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

Refinement. The structure was solved by isomorphous replacement from its hemi- hydrate analogue (structure code RPI_46_1_2).

Two symmetry equivalent acetone molecules are disordered with a hexane molecule located on a two-fold axis. Another acetone molecule is located on and disordered around a two-fold axis and additionally disordered by a slight tilt of the molecule. All acetone moieties were restrained to have similar geometries and to be close to planar. The two C-C bond distances within all acetone were restrained to be similar. C-C bond distances of the hexane molecule were restrained to target values (1.55 (1) Angstrom) and hexane C-C-C angles were restrained to be similar. Uij components of ADPs for disordered atoms closer to each other than 2.0 Angstrom were restrained to be similar. Subject to these conditions the occupancy rates refined to 0.505 (9) and 0.495 (9) for the acetone / hexane disorder, and two times 0.230 (11) and two times 0.270 (11) for the disordered acetone.

Acetone and hexane molecules are located in infinite channels and slowly vacate the crystal lattice. Crystals become milky overnight when taken out of mother liquor solution and left to dry in air, but retain crystallinity. Data collection reveals a solvent free structure (see dataset 91_2_dry).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.28108 (4)0.03150 (4)0.45830 (4)0.1050 (2)
O10.48565 (12)0.26573 (13)0.16549 (10)0.0360 (4)
H1O0.4406440.2799370.1778240.043*
O20.56438 (12)0.47869 (14)0.36251 (10)0.0366 (4)
O30.50234 (13)0.68019 (15)0.21207 (12)0.0437 (4)
O40.57291 (17)0.6900 (3)0.12449 (13)0.0702 (8)
O50.70949 (16)0.7561 (2)0.11557 (13)0.0668 (8)
H50.642 (3)0.727 (4)0.122 (3)0.080*
O60.82960 (13)0.81698 (18)0.19657 (14)0.0513 (5)
N10.40093 (12)0.55897 (14)0.10162 (11)0.0292 (4)
H10.4376870.6070630.1397560.035*
N20.45948 (13)0.40362 (16)0.40492 (11)0.0328 (4)
C10.60196 (15)0.31733 (18)0.28231 (13)0.0309 (4)
H1A0.6408800.3749820.3019230.037*
C20.54990 (15)0.33968 (17)0.19372 (12)0.0293 (4)
C30.50225 (15)0.43881 (17)0.18800 (12)0.0282 (4)
H3A0.4591760.4344830.2174510.034*
H3B0.5452340.4900920.2130990.034*
C40.45543 (16)0.46892 (18)0.10393 (13)0.0312 (4)
H4A0.4989510.4820570.0760720.037*
H4B0.4175050.4145690.0765350.037*
C50.32133 (17)0.5395 (2)0.12599 (18)0.0437 (6)
H5A0.2842670.4915200.0902220.066*
H5B0.2887710.6006200.1240980.066*
H5C0.3387470.5134540.1796180.066*
C60.37641 (18)0.6054 (2)0.02278 (15)0.0388 (5)
H6A0.3456480.5575390.0168920.058*
H6B0.4292300.6275980.0112720.058*
H6C0.3381600.6615740.0219210.058*
C70.61170 (16)0.33633 (18)0.14255 (13)0.0334 (5)
C80.5954 (2)0.2673 (2)0.08362 (14)0.0426 (6)
H80.5468890.2244600.0759880.051*
C90.6497 (2)0.2587 (3)0.03370 (15)0.0533 (8)
H90.6368360.2103350.0064250.064*
C100.7186 (2)0.3182 (3)0.04292 (17)0.0529 (8)
H100.7541510.3116430.0092990.063*
C110.7386 (2)0.3900 (3)0.10180 (17)0.0477 (7)
C120.8104 (2)0.4549 (3)0.1104 (2)0.0638 (10)
H120.8454340.4471080.0764330.077*
C130.8306 (2)0.5266 (4)0.1644 (2)0.0657 (9)
H130.8783840.5692560.1680700.079*
C140.7799 (2)0.5372 (3)0.2152 (2)0.0537 (7)
H140.7942720.5870190.2541090.064*
C150.70973 (18)0.4770 (2)0.20992 (16)0.0415 (6)
H150.6766950.4865010.2453240.050*
C160.68507 (16)0.4007 (2)0.15300 (14)0.0360 (5)
C170.66129 (17)0.2277 (2)0.29397 (14)0.0374 (5)
C180.6378 (2)0.1398 (2)0.2548 (2)0.0508 (7)
H180.5819320.1335100.2169720.061*
C190.6951 (3)0.0602 (3)0.2700 (2)0.0641 (9)
H190.6784860.0009480.2414960.077*
C200.7750 (3)0.0670 (3)0.3256 (2)0.0708 (11)
H200.8134480.0122760.3370270.085*
C210.7987 (3)0.1538 (4)0.3645 (3)0.0800 (13)
H210.8542030.1592680.4030260.096*
C220.7429 (2)0.2343 (3)0.34874 (19)0.0566 (8)
H220.7610070.2942800.3758230.068*
C230.54033 (15)0.31153 (18)0.33221 (12)0.0298 (4)
C240.50170 (16)0.22692 (18)0.34487 (13)0.0321 (4)
H240.5156310.1669070.3245040.039*
C250.44064 (16)0.2275 (2)0.38831 (13)0.0341 (5)
C260.39966 (19)0.1409 (2)0.40278 (17)0.0440 (6)
H260.4147430.0791580.3859470.053*
C270.3380 (2)0.1469 (3)0.4413 (2)0.0521 (7)
C280.31484 (19)0.2374 (3)0.46714 (17)0.0495 (7)
H280.2713200.2401530.4931100.059*
C290.35541 (16)0.3215 (2)0.45464 (14)0.0404 (6)
H290.3403000.3824110.4727270.048*
C300.41953 (15)0.3185 (2)0.41512 (12)0.0326 (5)
C310.51833 (15)0.39829 (18)0.36816 (12)0.0302 (4)
C320.5439 (2)0.5672 (2)0.39697 (19)0.0495 (7)
H32A0.4849980.5890460.3673370.074*
H32B0.5862260.6182030.3954650.074*
H32C0.5463360.5545230.4515820.074*
C330.56682 (18)0.7043 (2)0.19291 (15)0.0391 (5)
C340.64121 (18)0.7502 (2)0.25429 (14)0.0388 (5)
H340.6326570.7566150.3043750.047*
C350.71764 (18)0.7835 (2)0.25022 (15)0.0392 (5)
H350.7543380.8104220.2978460.047*
C360.75529 (18)0.7859 (2)0.18370 (16)0.0398 (5)
O70.5989 (5)0.8015 (5)0.4370 (5)0.097 (3)0.505 (9)
C370.5409 (12)0.8497 (16)0.3963 (12)0.119 (4)0.505 (9)
C380.4480 (8)0.8322 (11)0.3707 (11)0.128 (4)0.505 (9)
H38A0.4299390.8096160.3160770.193*0.505 (9)
H38B0.4171340.8930120.3745910.193*0.505 (9)
H38C0.4337070.7819110.4040540.193*0.505 (9)
C390.5660 (10)0.9345 (9)0.3579 (11)0.125 (5)0.505 (9)
H39A0.6269670.9276400.3587300.187*0.505 (9)
H39B0.5594510.9944710.3858230.187*0.505 (9)
H39C0.5283460.9383350.3033830.187*0.505 (9)
C430.4921 (13)0.9070 (14)0.3204 (10)0.147 (6)0.495 (9)
H43A0.5320670.9030500.2885550.220*0.495 (9)
H43B0.4822840.9759650.3306750.220*0.495 (9)
H43C0.4363290.8763330.2920350.220*0.495 (9)
C440.5325 (15)0.853 (2)0.3990 (11)0.131 (4)0.495 (9)
H44A0.5361580.7823580.3883010.157*0.495 (9)
H44B0.5927520.8774630.4230740.157*0.495 (9)
C450.4823 (10)0.8658 (17)0.4569 (4)0.151 (5)0.495 (9)
H45A0.4508160.9288050.4430220.181*0.495 (9)
H45B0.4369740.8140580.4439510.181*0.495 (9)
O8A0.4373 (18)1.0370 (17)0.0198 (16)0.134 (7)0.230 (11)
C40A0.489 (2)0.9735 (18)0.0008 (19)0.087 (5)0.230 (11)
C41A0.482 (3)0.8753 (17)0.038 (2)0.089 (6)0.230 (11)
H41A0.4518930.8812290.0944920.133*0.230 (11)
H41B0.4490480.8312250.0143040.133*0.230 (11)
H41C0.5407330.8487550.0301750.133*0.230 (11)
C42A0.563 (2)0.979 (3)0.071 (2)0.103 (8)0.230 (11)
H42A0.6150910.9523390.0608290.155*0.230 (11)
H42B0.5500700.9416090.1127430.155*0.230 (11)
H42C0.5735591.0479750.0872160.155*0.230 (11)
O8B0.4818 (16)1.0511 (9)0.0406 (11)0.120 (6)0.270 (11)
C40B0.4889 (18)0.9844 (15)0.0016 (16)0.085 (5)0.270 (11)
C41B0.532 (3)0.896 (2)0.044 (2)0.107 (7)0.270 (11)
H41D0.5922180.8931310.0434660.160*0.270 (11)
H41E0.5002480.8374230.0188150.160*0.270 (11)
H41F0.5304230.8990330.0987100.160*0.270 (11)
C42B0.454 (2)0.973 (3)0.0838 (13)0.092 (7)0.270 (11)
H42D0.4963370.9371410.1031460.138*0.270 (11)
H42E0.4427851.0371690.1087070.138*0.270 (11)
H42F0.3992230.9353050.0965390.138*0.270 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.1091 (4)0.0780 (3)0.1620 (6)0.0348 (3)0.0922 (4)0.0104 (3)
O10.0413 (9)0.0297 (8)0.0340 (8)0.0002 (7)0.0066 (7)0.0033 (7)
O20.0459 (10)0.0336 (9)0.0320 (8)0.0020 (7)0.0145 (7)0.0046 (7)
O30.0448 (10)0.0444 (11)0.0476 (10)0.0094 (8)0.0225 (8)0.0078 (8)
O40.0614 (14)0.117 (2)0.0389 (10)0.0493 (15)0.0251 (10)0.0328 (13)
O50.0608 (13)0.105 (2)0.0407 (10)0.0419 (14)0.0249 (10)0.0199 (12)
O60.0368 (10)0.0504 (12)0.0654 (13)0.0100 (9)0.0135 (9)0.0034 (10)
N10.0278 (8)0.0297 (9)0.0293 (8)0.0043 (7)0.0073 (7)0.0050 (7)
N20.0332 (10)0.0397 (11)0.0237 (8)0.0079 (8)0.0058 (7)0.0006 (8)
C10.0319 (11)0.0335 (11)0.0272 (9)0.0072 (9)0.0090 (8)0.0021 (8)
C20.0347 (11)0.0293 (10)0.0228 (9)0.0059 (8)0.0068 (8)0.0002 (8)
C30.0305 (10)0.0282 (10)0.0243 (9)0.0062 (8)0.0060 (8)0.0012 (8)
C40.0359 (11)0.0309 (11)0.0263 (9)0.0075 (9)0.0084 (8)0.0019 (8)
C50.0320 (11)0.0484 (15)0.0547 (15)0.0064 (11)0.0192 (11)0.0153 (13)
C60.0430 (13)0.0387 (13)0.0335 (11)0.0078 (11)0.0098 (10)0.0118 (10)
C70.0415 (12)0.0341 (12)0.0250 (9)0.0138 (10)0.0107 (9)0.0016 (8)
C80.0583 (16)0.0399 (13)0.0279 (10)0.0186 (12)0.0105 (10)0.0007 (10)
C90.079 (2)0.0529 (17)0.0287 (11)0.0348 (16)0.0167 (12)0.0011 (11)
C100.0640 (18)0.0645 (19)0.0388 (13)0.0340 (16)0.0285 (13)0.0141 (13)
C110.0468 (14)0.0612 (17)0.0418 (13)0.0246 (13)0.0233 (11)0.0156 (12)
C120.0468 (16)0.089 (3)0.068 (2)0.0153 (17)0.0352 (15)0.020 (2)
C130.0440 (16)0.085 (2)0.076 (2)0.0010 (17)0.0295 (16)0.010 (2)
C140.0432 (14)0.0616 (18)0.0577 (17)0.0046 (14)0.0175 (13)0.0035 (15)
C150.0381 (13)0.0490 (15)0.0399 (12)0.0044 (11)0.0156 (10)0.0013 (11)
C160.0359 (11)0.0444 (13)0.0295 (10)0.0149 (10)0.0124 (9)0.0067 (9)
C170.0384 (12)0.0451 (14)0.0321 (10)0.0159 (10)0.0159 (9)0.0099 (10)
C180.0550 (17)0.0400 (14)0.0583 (17)0.0217 (12)0.0185 (14)0.0082 (13)
C190.081 (2)0.0482 (18)0.072 (2)0.0319 (17)0.0356 (19)0.0179 (16)
C200.075 (2)0.077 (2)0.069 (2)0.052 (2)0.0355 (18)0.0317 (19)
C210.055 (2)0.111 (3)0.067 (2)0.049 (2)0.0085 (17)0.010 (2)
C220.0408 (14)0.080 (2)0.0472 (15)0.0257 (15)0.0108 (12)0.0031 (15)
C230.0309 (10)0.0346 (11)0.0229 (9)0.0086 (8)0.0063 (8)0.0029 (8)
C240.0342 (11)0.0330 (11)0.0285 (10)0.0069 (9)0.0083 (8)0.0011 (8)
C250.0311 (11)0.0431 (13)0.0257 (9)0.0041 (9)0.0050 (8)0.0019 (9)
C260.0408 (14)0.0491 (15)0.0427 (14)0.0008 (11)0.0133 (11)0.0000 (12)
C270.0450 (15)0.0615 (19)0.0522 (16)0.0118 (13)0.0185 (13)0.0012 (14)
C280.0369 (13)0.074 (2)0.0393 (13)0.0030 (13)0.0145 (11)0.0012 (13)
C290.0313 (11)0.0598 (17)0.0290 (10)0.0045 (11)0.0075 (9)0.0051 (11)
C300.0279 (10)0.0456 (13)0.0204 (8)0.0058 (9)0.0015 (7)0.0009 (9)
C310.0308 (10)0.0340 (11)0.0225 (9)0.0076 (8)0.0034 (8)0.0016 (8)
C320.0688 (19)0.0355 (13)0.0488 (15)0.0022 (13)0.0248 (14)0.0090 (12)
C330.0454 (13)0.0387 (13)0.0357 (11)0.0106 (10)0.0160 (10)0.0075 (10)
C340.0463 (13)0.0410 (13)0.0304 (10)0.0052 (11)0.0136 (10)0.0033 (9)
C350.0437 (13)0.0387 (13)0.0312 (10)0.0066 (10)0.0054 (9)0.0032 (9)
C360.0394 (12)0.0355 (13)0.0438 (13)0.0078 (10)0.0117 (10)0.0004 (10)
O70.093 (5)0.061 (4)0.142 (7)0.014 (3)0.045 (4)0.007 (4)
C370.115 (7)0.095 (6)0.166 (8)0.002 (6)0.071 (6)0.022 (6)
C380.102 (7)0.100 (8)0.198 (11)0.003 (7)0.068 (8)0.023 (8)
C390.109 (8)0.066 (6)0.206 (13)0.016 (6)0.058 (9)0.005 (7)
C430.130 (10)0.128 (10)0.167 (11)0.064 (8)0.021 (9)0.019 (9)
C440.123 (7)0.102 (7)0.174 (8)0.011 (6)0.057 (7)0.028 (7)
C450.125 (8)0.147 (8)0.189 (10)0.011 (8)0.059 (8)0.016 (8)
O8A0.165 (13)0.079 (10)0.129 (12)0.018 (10)0.005 (11)0.007 (10)
C40A0.111 (10)0.044 (7)0.105 (8)0.016 (8)0.030 (8)0.015 (9)
C41A0.109 (13)0.041 (9)0.100 (11)0.003 (9)0.006 (10)0.007 (9)
C42A0.120 (14)0.058 (11)0.115 (13)0.006 (12)0.013 (12)0.003 (12)
O8B0.180 (13)0.047 (7)0.119 (10)0.007 (7)0.022 (9)0.023 (6)
C40B0.112 (9)0.039 (6)0.101 (7)0.013 (8)0.027 (8)0.011 (9)
C41B0.114 (12)0.082 (13)0.109 (11)0.007 (12)0.010 (11)0.021 (12)
C42B0.107 (12)0.066 (11)0.091 (11)0.001 (10)0.011 (10)0.013 (10)
Geometric parameters (Å, º) top
Br1—C271.891 (3)C21—H210.9500
O1—C21.422 (3)C22—H220.9500
O1—H1O0.8400C23—C241.362 (4)
O2—C311.344 (3)C23—C311.441 (3)
O2—C321.438 (3)C24—C251.424 (3)
O3—C331.230 (3)C24—H240.9500
O4—C331.271 (3)C25—C301.410 (4)
O4—H51.24 (5)C25—C261.414 (4)
O5—C361.283 (3)C26—C271.370 (4)
O5—H51.18 (5)C26—H260.9500
O6—C361.222 (3)C27—C281.407 (5)
N1—C61.485 (3)C28—C291.371 (5)
N1—C51.495 (3)C28—H280.9500
N1—C41.502 (3)C29—C301.415 (3)
N1—H11.0000C29—H290.9500
N2—C311.307 (3)C32—H32A0.9800
N2—C301.365 (3)C32—H32B0.9800
C1—C231.522 (3)C32—H32C0.9800
C1—C171.526 (3)C33—C341.493 (4)
C1—C21.580 (3)C34—C351.332 (4)
C1—H1A1.0000C34—H340.9500
C2—C71.541 (3)C35—C361.489 (4)
C2—C31.542 (3)C35—H350.9500
C3—C41.519 (3)O7—C371.19 (2)
C3—H3A0.9900C37—C381.443 (19)
C3—H3B0.9900C37—C391.463 (19)
C4—H4A0.9900C38—H38A0.9800
C4—H4B0.9900C38—H38B0.9800
C5—H5A0.9800C38—H38C0.9800
C5—H5B0.9800C39—H39A0.9800
C5—H5C0.9800C39—H39B0.9800
C6—H6A0.9800C39—H39C0.9800
C6—H6B0.9800C43—C441.544 (13)
C6—H6C0.9800C43—H43A0.9800
C7—C81.377 (4)C43—H43B0.9800
C7—C161.436 (4)C43—H43C0.9800
C8—C91.429 (4)C44—C451.501 (13)
C8—H80.9500C44—H44A0.9900
C9—C101.343 (6)C44—H44B0.9900
C9—H90.9500C45—C45i1.473 (13)
C10—C111.402 (5)C45—H45A0.9900
C10—H100.9500C45—H45B0.9900
C11—C121.426 (5)O8A—C40A1.17 (2)
C11—C161.440 (3)C40A—C42A1.47 (2)
C12—C131.344 (7)C40A—C41A1.486 (19)
C12—H120.9500C41A—H41A0.9800
C13—C141.398 (5)C41A—H41B0.9800
C13—H130.9500C41A—H41C0.9800
C14—C151.375 (4)C42A—H42A0.9800
C14—H140.9500C42A—H42B0.9800
C15—C161.425 (4)C42A—H42C0.9800
C15—H150.9500O8B—C40B1.17 (2)
C17—C221.381 (4)C40B—C42B1.47 (2)
C17—C181.382 (5)C40B—C41B1.479 (19)
C18—C191.396 (4)C41B—H41D0.9800
C18—H180.9500C41B—H41E0.9800
C19—C201.369 (6)C41B—H41F0.9800
C19—H190.9500C42B—H42D0.9800
C20—C211.368 (7)C42B—H42E0.9800
C20—H200.9500C42B—H42F0.9800
C21—C221.392 (5)
C2—O1—H1O109.5C30—C25—C24117.8 (2)
C31—O2—C32116.7 (2)C26—C25—C24122.1 (2)
C33—O4—H5108 (2)C27—C26—C25119.3 (3)
C36—O5—H5107 (2)C27—C26—H26120.3
C6—N1—C5110.35 (19)C25—C26—H26120.3
C6—N1—C4111.08 (18)C26—C27—C28121.4 (3)
C5—N1—C4112.93 (19)C26—C27—Br1119.3 (3)
C6—N1—H1107.4C28—C27—Br1119.3 (2)
C5—N1—H1107.4C29—C28—C27119.7 (3)
C4—N1—H1107.4C29—C28—H28120.2
C31—N2—C30117.4 (2)C27—C28—H28120.2
C23—C1—C17111.64 (19)C28—C29—C30120.8 (3)
C23—C1—C2110.87 (18)C28—C29—H29119.6
C17—C1—C2114.25 (19)C30—C29—H29119.6
C23—C1—H1A106.5N2—C30—C25122.2 (2)
C17—C1—H1A106.5N2—C30—C29119.0 (2)
C2—C1—H1A106.5C25—C30—C29118.8 (3)
O1—C2—C7107.30 (18)N2—C31—O2119.4 (2)
O1—C2—C3107.82 (18)N2—C31—C23125.6 (2)
C7—C2—C3112.52 (19)O2—C31—C23115.0 (2)
O1—C2—C1108.99 (19)O2—C32—H32A109.5
C7—C2—C1110.39 (18)O2—C32—H32B109.5
C3—C2—C1109.70 (17)H32A—C32—H32B109.5
C4—C3—C2112.94 (18)O2—C32—H32C109.5
C4—C3—H3A109.0H32A—C32—H32C109.5
C2—C3—H3A109.0H32B—C32—H32C109.5
C4—C3—H3B109.0O3—C33—O4122.9 (3)
C2—C3—H3B109.0O3—C33—C34117.5 (2)
H3A—C3—H3B107.8O4—C33—C34119.6 (2)
N1—C4—C3110.99 (18)C35—C34—C33130.5 (2)
N1—C4—H4A109.4C35—C34—H34114.8
C3—C4—H4A109.4C33—C34—H34114.8
N1—C4—H4B109.4C34—C35—C36130.9 (2)
C3—C4—H4B109.4C34—C35—H35114.5
H4A—C4—H4B108.0C36—C35—H35114.5
N1—C5—H5A109.5O6—C36—O5122.4 (3)
N1—C5—H5B109.5O6—C36—C35117.9 (3)
H5A—C5—H5B109.5O5—C36—C35119.8 (2)
N1—C5—H5C109.5O7—C37—C38130.1 (18)
H5A—C5—H5C109.5O7—C37—C39116.6 (15)
H5B—C5—H5C109.5C38—C37—C39112.9 (17)
N1—C6—H6A109.5C37—C38—H38A109.5
N1—C6—H6B109.5C37—C38—H38B109.5
H6A—C6—H6B109.5H38A—C38—H38B109.5
N1—C6—H6C109.5C37—C38—H38C109.5
H6A—C6—H6C109.5H38A—C38—H38C109.5
H6B—C6—H6C109.5H38B—C38—H38C109.5
C8—C7—C16118.5 (2)C37—C39—H39A109.5
C8—C7—C2117.8 (2)C37—C39—H39B109.5
C16—C7—C2123.8 (2)H39A—C39—H39B109.5
C7—C8—C9121.5 (3)C37—C39—H39C109.5
C7—C8—H8119.3H39A—C39—H39C109.5
C9—C8—H8119.3H39B—C39—H39C109.5
C10—C9—C8120.7 (3)C44—C43—H43A109.5
C10—C9—H9119.6C44—C43—H43B109.5
C8—C9—H9119.6H43A—C43—H43B109.5
C9—C10—C11120.5 (3)C44—C43—H43C109.5
C9—C10—H10119.8H43A—C43—H43C109.5
C11—C10—H10119.8H43B—C43—H43C109.5
C10—C11—C12120.5 (3)C45—C44—C43114.0 (15)
C10—C11—C16120.2 (3)C45—C44—H44A108.8
C12—C11—C16119.2 (3)C43—C44—H44A108.8
C13—C12—C11122.7 (3)C45—C44—H44B108.8
C13—C12—H12118.6C43—C44—H44B108.8
C11—C12—H12118.6H44A—C44—H44B107.6
C12—C13—C14118.7 (4)C45i—C45—C44127.1 (17)
C12—C13—H13120.6C45i—C45—H45A105.5
C14—C13—H13120.6C44—C45—H45A105.5
C15—C14—C13121.4 (4)C45i—C45—H45B105.5
C15—C14—H14119.3C44—C45—H45B105.5
C13—C14—H14119.3H45A—C45—H45B106.1
C14—C15—C16122.0 (3)O8A—C40A—C42A122 (3)
C14—C15—H15119.0O8A—C40A—C41A126 (3)
C16—C15—H15119.0C42A—C40A—C41A112 (2)
C15—C16—C7125.4 (2)C40A—C41A—H41A109.5
C15—C16—C11115.9 (3)C40A—C41A—H41B109.5
C7—C16—C11118.7 (3)H41A—C41A—H41B109.5
C22—C17—C18118.1 (3)C40A—C41A—H41C109.5
C22—C17—C1117.6 (3)H41A—C41A—H41C109.5
C18—C17—C1124.3 (2)H41B—C41A—H41C109.5
C17—C18—C19120.9 (3)C40A—C42A—H42A109.5
C17—C18—H18119.6C40A—C42A—H42B109.5
C19—C18—H18119.6H42A—C42A—H42B109.5
C20—C19—C18120.5 (4)C40A—C42A—H42C109.5
C20—C19—H19119.7H42A—C42A—H42C109.5
C18—C19—H19119.7H42B—C42A—H42C109.5
C21—C20—C19118.8 (3)O8B—C40B—C42B129 (2)
C21—C20—H20120.6O8B—C40B—C41B116 (3)
C19—C20—H20120.6C42B—C40B—C41B115 (2)
C20—C21—C22121.2 (4)C40B—C41B—H41D109.5
C20—C21—H21119.4C40B—C41B—H41E109.5
C22—C21—H21119.4H41D—C41B—H41E109.5
C17—C22—C21120.4 (4)C40B—C41B—H41F109.5
C17—C22—H22119.8H41D—C41B—H41F109.5
C21—C22—H22119.8H41E—C41B—H41F109.5
C24—C23—C31115.9 (2)C40B—C42B—H42D109.5
C24—C23—C1123.5 (2)C40B—C42B—H42E109.5
C31—C23—C1120.6 (2)H42D—C42B—H42E109.5
C23—C24—C25120.7 (2)C40B—C42B—H42F109.5
C23—C24—H24119.7H42D—C42B—H42F109.5
C25—C24—H24119.7H42E—C42B—H42F109.5
C30—C25—C26120.1 (2)
C23—C1—C2—O157.4 (2)C1—C17—C18—C19178.5 (3)
C17—C1—C2—O169.8 (3)C17—C18—C19—C201.7 (5)
C23—C1—C2—C7175.0 (2)C18—C19—C20—C211.7 (6)
C17—C1—C2—C747.8 (3)C19—C20—C21—C220.4 (7)
C23—C1—C2—C360.5 (3)C18—C17—C22—C211.1 (5)
C17—C1—C2—C3172.3 (2)C1—C17—C22—C21177.3 (3)
O1—C2—C3—C465.2 (2)C20—C21—C22—C171.1 (6)
C7—C2—C3—C452.9 (3)C17—C1—C23—C2438.3 (3)
C1—C2—C3—C4176.2 (2)C2—C1—C23—C2490.3 (3)
C6—N1—C4—C3163.3 (2)C17—C1—C23—C31142.8 (2)
C5—N1—C4—C372.1 (3)C2—C1—C23—C3188.6 (2)
C2—C3—C4—N1172.86 (19)C31—C23—C24—C252.7 (3)
O1—C2—C7—C80.4 (3)C1—C23—C24—C25176.2 (2)
C3—C2—C7—C8118.9 (2)C23—C24—C25—C302.2 (3)
C1—C2—C7—C8118.2 (2)C23—C24—C25—C26179.7 (2)
O1—C2—C7—C16179.7 (2)C30—C25—C26—C271.5 (4)
C3—C2—C7—C1661.3 (3)C24—C25—C26—C27176.5 (3)
C1—C2—C7—C1661.6 (3)C25—C26—C27—C280.3 (5)
C16—C7—C8—C90.2 (4)C25—C26—C27—Br1178.4 (2)
C2—C7—C8—C9179.6 (2)C26—C27—C28—C290.9 (5)
C7—C8—C9—C100.1 (4)Br1—C27—C28—C29179.6 (2)
C8—C9—C10—C110.0 (4)C27—C28—C29—C300.8 (4)
C9—C10—C11—C12178.4 (3)C31—N2—C30—C250.7 (3)
C9—C10—C11—C160.1 (4)C31—N2—C30—C29180.0 (2)
C10—C11—C12—C13178.1 (4)C26—C25—C30—N2177.7 (2)
C16—C11—C12—C130.2 (5)C24—C25—C30—N24.1 (3)
C11—C12—C13—C141.0 (6)C26—C25—C30—C291.6 (3)
C12—C13—C14—C151.0 (6)C24—C25—C30—C29176.5 (2)
C13—C14—C15—C160.2 (5)C28—C29—C30—N2178.9 (2)
C14—C15—C16—C7178.5 (3)C28—C29—C30—C250.4 (3)
C14—C15—C16—C110.5 (4)C30—N2—C31—O2174.54 (19)
C8—C7—C16—C15178.7 (2)C30—N2—C31—C234.9 (3)
C2—C7—C16—C151.5 (4)C32—O2—C31—N21.1 (3)
C8—C7—C16—C110.3 (3)C32—O2—C31—C23179.4 (2)
C2—C7—C16—C11179.5 (2)C24—C23—C31—N26.6 (3)
C10—C11—C16—C15178.8 (3)C1—C23—C31—N2172.3 (2)
C12—C11—C16—C150.6 (4)C24—C23—C31—O2172.82 (19)
C10—C11—C16—C70.3 (4)C1—C23—C31—O28.2 (3)
C12—C11—C16—C7178.6 (3)O3—C33—C34—C35179.5 (3)
C23—C1—C17—C2294.4 (3)O4—C33—C34—C351.9 (5)
C2—C1—C17—C22138.8 (3)C33—C34—C35—C360.6 (5)
C23—C1—C17—C1883.9 (3)C34—C35—C36—O6176.7 (3)
C2—C1—C17—C1842.9 (4)C34—C35—C36—O53.6 (5)
C22—C17—C18—C190.2 (5)C43—C44—C45—C45i149.8 (15)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O6ii0.841.982.816 (3)175
O5—H5···O41.18 (5)1.24 (5)2.422 (3)175 (5)
N1—H1···O31.001.712.709 (3)174
N1—H1···O41.002.543.212 (3)125
C32—H32B···O70.982.603.337 (8)132
C34—H34···O70.952.663.600 (9)171
Symmetry code: (ii) x1/2, y1/2, z.
[4-(6-bromo-2-methoxyquinolin-3-yl)-3-hydroxy-3-(naphthalen-1-yl)-4-phenylbutyl]dimethylazanium 3-carboxyprop-2-enoate (desolvated) top
Crystal data top
C32H32BrN2O2+·C4H3O4F(000) = 1392
Mr = 671.56Dx = 1.238 Mg m3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
a = 15.7494 (12) ÅCell parameters from 9787 reflections
b = 13.3568 (11) Åθ = 2.5–31.6°
c = 17.8634 (14) ŵ = 1.19 mm1
β = 106.500 (3)°T = 150 K
V = 3603.0 (5) Å3Block, white
Z = 40.48 × 0.35 × 0.21 mm
Data collection top
Bruker AXS D8 Quest with PhotonII CPAD
diffractometer
13641 independent reflections
Radiation source: fine focus sealed tube X-ray source10348 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromatorRint = 0.049
Detector resolution: 7.4074 pixels mm-1θmax = 33.1°, θmin = 2.5°
ω and phi scansh = 2424
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
k = 2020
Tmin = 0.678, Tmax = 0.740l = 2727
78980 measured reflections
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0725P)2 + 0.899P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.048(Δ/σ)max = 0.001
wR(F2) = 0.142Δρmax = 0.89 e Å3
S = 1.06Δρmin = 0.74 e Å3
13641 reflectionsExtinction correction: SHELXL2018/3 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
418 parametersExtinction coefficient: 0.0113 (14)
1 restraintAbsolute structure: Flack x determined using 4138 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: isomorphous structure methodsAbsolute structure parameter: 0.044 (3)
Hydrogen site location: mixed
Special details top

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

Refinement. Crystals were obtained from the acetone / hexane solvate by drying on a glass slide in air over night. In the solavted structure acetone and hexane molecules are located in infinite channels and slowly vacate the crystal lattice. Crystals become milky overnight when taken out of mother liquor solution and left to dry in air, but retain crystallinity.

The structure was solved by isomorphous replacement from the acetone / hexane solvate (structure code 91_2). No substantial electron density was found in the previously solvate occupied channels (largest void peaks are less than 0.5 electrons per cubic Angstrom). Residual electron density was not corrected for. An alternative refinement using the Squeeze algorithm is appended below this cif file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.30125 (4)0.01859 (5)0.48058 (3)0.0879 (2)
O10.48670 (11)0.26945 (13)0.16346 (10)0.0303 (3)
H1O0.4410240.2832210.1768020.036*
O20.56663 (13)0.48363 (14)0.36126 (10)0.0353 (4)
O30.48998 (13)0.69083 (16)0.21057 (12)0.0413 (4)
O40.56590 (16)0.7068 (2)0.12480 (12)0.0564 (7)
O50.70940 (16)0.7676 (2)0.12134 (12)0.0530 (6)
H50.648 (3)0.747 (4)0.119 (3)0.064*
O60.83299 (13)0.81615 (17)0.20737 (13)0.0435 (4)
N10.39732 (12)0.56474 (15)0.09851 (10)0.0256 (3)
H10.4307460.6158250.1364850.031*
N20.46078 (14)0.40519 (19)0.40536 (11)0.0344 (4)
C10.60435 (14)0.32110 (18)0.27931 (12)0.0275 (4)
H1A0.6432970.3801590.2990450.033*
C20.55201 (14)0.34533 (16)0.19164 (12)0.0248 (4)
C30.50343 (14)0.44634 (17)0.18665 (12)0.0260 (4)
H3A0.4588700.4415730.2159840.031*
H3B0.5465850.4988460.2115740.031*
C40.45729 (15)0.47679 (17)0.10240 (12)0.0277 (4)
H4A0.5025270.4936990.0756600.033*
H4B0.4223370.4195060.0745780.033*
C50.31566 (15)0.5397 (2)0.12082 (16)0.0365 (5)
H5A0.2817580.4888480.0850360.055*
H5B0.2794690.6000290.1177960.055*
H5C0.3319850.5136070.1742960.055*
C60.37408 (17)0.6109 (2)0.01963 (14)0.0341 (5)
H6A0.3514080.5592730.0199700.051*
H6B0.4269400.6417720.0109330.051*
H6C0.3285580.6622110.0158850.051*
C70.61578 (15)0.34283 (17)0.14019 (12)0.0270 (4)
C80.59948 (17)0.2735 (2)0.08053 (13)0.0332 (5)
H80.5501120.2299090.0729300.040*
C90.6545 (2)0.2657 (2)0.03022 (14)0.0405 (6)
H90.6407430.2184800.0112450.049*
C100.7269 (2)0.3254 (2)0.04101 (15)0.0410 (6)
H100.7640080.3186350.0076650.049*
C110.74727 (17)0.3971 (2)0.10125 (15)0.0372 (5)
C120.8226 (2)0.4605 (3)0.1115 (2)0.0514 (7)
H120.8597680.4517300.0784460.062*
C130.8427 (2)0.5325 (3)0.1668 (2)0.0540 (8)
H130.8924960.5747580.1717140.065*
C140.7884 (2)0.5441 (2)0.21744 (19)0.0449 (6)
H140.8026620.5938000.2571280.054*
C150.71535 (16)0.4843 (2)0.20964 (15)0.0344 (5)
H150.6797620.4942820.2439390.041*
C160.69118 (15)0.40772 (18)0.15192 (13)0.0298 (4)
C170.66522 (16)0.2308 (2)0.28868 (13)0.0323 (5)
C180.6404 (2)0.1395 (2)0.25147 (17)0.0405 (6)
H180.5835560.1324230.2150750.049*
C190.6984 (3)0.0582 (3)0.2672 (2)0.0528 (8)
H190.6807330.0035450.2411140.063*
C200.7808 (3)0.0663 (3)0.3199 (2)0.0640 (11)
H200.8193340.0101080.3314270.077*
C210.8068 (2)0.1574 (4)0.3561 (2)0.0649 (11)
H210.8641780.1638000.3916930.078*
C220.74995 (18)0.2406 (3)0.34113 (16)0.0457 (7)
H220.7686920.3027370.3662530.055*
C230.54190 (14)0.31290 (19)0.33007 (12)0.0283 (4)
C240.50509 (16)0.2257 (2)0.34414 (13)0.0318 (4)
H240.5197690.1649560.3231110.038*
C250.44446 (15)0.2244 (2)0.39028 (12)0.0347 (5)
C260.40766 (19)0.1342 (3)0.40905 (16)0.0439 (6)
H260.4238110.0714230.3921360.053*
C270.3479 (2)0.1395 (3)0.45243 (17)0.0510 (8)
C280.32176 (19)0.2313 (3)0.47678 (15)0.0518 (8)
H280.2790700.2331320.5051280.062*
C290.35797 (17)0.3182 (3)0.45956 (14)0.0437 (7)
H290.3400710.3802240.4762920.052*
C300.42187 (15)0.3178 (2)0.41712 (12)0.0352 (5)
C310.51945 (15)0.40092 (19)0.36697 (12)0.0299 (4)
C320.5516 (3)0.5718 (3)0.4008 (2)0.0502 (7)
H32A0.4917380.5969370.3761210.075*
H32B0.5950470.6230670.3978560.075*
H32C0.5577400.5559140.4556710.075*
C330.55716 (17)0.71776 (19)0.19320 (14)0.0340 (5)
C340.63126 (18)0.7609 (2)0.25666 (14)0.0361 (5)
H340.6189570.7690930.3053730.043*
C350.71202 (17)0.7897 (2)0.25575 (14)0.0351 (5)
H350.7485330.8134710.3043850.042*
C360.75461 (17)0.79078 (19)0.19096 (15)0.0343 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0857 (3)0.1020 (4)0.0935 (4)0.0386 (3)0.0537 (3)0.0023 (3)
O10.0275 (7)0.0320 (8)0.0306 (7)0.0008 (6)0.0072 (6)0.0025 (6)
O20.0405 (9)0.0364 (8)0.0298 (8)0.0055 (7)0.0111 (7)0.0013 (7)
O30.0372 (9)0.0457 (10)0.0450 (10)0.0101 (8)0.0182 (8)0.0100 (8)
O40.0453 (11)0.0926 (19)0.0346 (9)0.0313 (12)0.0168 (8)0.0209 (11)
O50.0469 (11)0.0836 (17)0.0327 (9)0.0259 (12)0.0184 (8)0.0088 (10)
O60.0305 (9)0.0483 (11)0.0535 (11)0.0052 (8)0.0146 (8)0.0024 (9)
N10.0236 (7)0.0280 (8)0.0255 (7)0.0031 (6)0.0073 (6)0.0021 (6)
N20.0287 (9)0.0520 (12)0.0221 (8)0.0112 (8)0.0064 (7)0.0002 (8)
C10.0254 (9)0.0347 (10)0.0226 (8)0.0063 (8)0.0071 (7)0.0028 (7)
C20.0244 (8)0.0284 (9)0.0214 (8)0.0036 (7)0.0064 (7)0.0003 (7)
C30.0253 (9)0.0304 (9)0.0219 (8)0.0067 (7)0.0061 (7)0.0012 (7)
C40.0280 (9)0.0312 (9)0.0232 (8)0.0087 (8)0.0064 (7)0.0013 (7)
C50.0242 (9)0.0441 (13)0.0437 (12)0.0039 (9)0.0139 (9)0.0103 (10)
C60.0333 (11)0.0378 (12)0.0302 (10)0.0073 (9)0.0074 (8)0.0085 (9)
C70.0290 (9)0.0315 (10)0.0214 (8)0.0086 (8)0.0087 (7)0.0027 (7)
C80.0369 (11)0.0386 (12)0.0238 (9)0.0105 (9)0.0080 (8)0.0007 (8)
C90.0529 (15)0.0447 (13)0.0256 (10)0.0206 (12)0.0141 (10)0.0022 (9)
C100.0478 (14)0.0484 (14)0.0343 (11)0.0228 (12)0.0234 (10)0.0121 (10)
C110.0342 (11)0.0453 (13)0.0370 (11)0.0131 (10)0.0181 (9)0.0110 (10)
C120.0421 (14)0.0610 (19)0.0604 (18)0.0074 (13)0.0295 (13)0.0152 (15)
C130.0372 (13)0.0572 (18)0.072 (2)0.0033 (13)0.0230 (14)0.0087 (16)
C140.0361 (12)0.0448 (15)0.0529 (15)0.0046 (10)0.0112 (11)0.0022 (12)
C150.0313 (10)0.0385 (11)0.0341 (11)0.0017 (9)0.0103 (8)0.0019 (9)
C160.0273 (9)0.0361 (11)0.0276 (9)0.0074 (8)0.0103 (7)0.0053 (8)
C170.0295 (10)0.0427 (12)0.0273 (9)0.0131 (9)0.0121 (8)0.0099 (9)
C180.0428 (13)0.0393 (12)0.0435 (13)0.0148 (11)0.0191 (11)0.0105 (11)
C190.0625 (19)0.0432 (15)0.0626 (18)0.0229 (14)0.0338 (16)0.0147 (13)
C200.064 (2)0.073 (2)0.0621 (19)0.0466 (19)0.0299 (16)0.0284 (18)
C210.0435 (16)0.098 (3)0.0519 (18)0.0396 (19)0.0105 (13)0.0207 (19)
C220.0313 (11)0.0681 (18)0.0374 (12)0.0196 (12)0.0092 (10)0.0089 (12)
C230.0244 (9)0.0389 (11)0.0211 (8)0.0065 (8)0.0057 (7)0.0018 (8)
C240.0293 (10)0.0424 (12)0.0239 (8)0.0034 (9)0.0079 (7)0.0023 (9)
C250.0253 (9)0.0568 (15)0.0215 (8)0.0000 (10)0.0057 (7)0.0017 (9)
C260.0369 (12)0.0637 (18)0.0328 (11)0.0080 (12)0.0126 (10)0.0021 (12)
C270.0396 (14)0.080 (2)0.0355 (12)0.0165 (15)0.0143 (11)0.0000 (14)
C280.0312 (11)0.098 (3)0.0290 (11)0.0093 (14)0.0125 (9)0.0069 (14)
C290.0285 (11)0.080 (2)0.0238 (10)0.0015 (12)0.0084 (8)0.0063 (11)
C300.0225 (9)0.0622 (16)0.0193 (8)0.0060 (10)0.0035 (7)0.0003 (9)
C310.0281 (10)0.0399 (11)0.0203 (8)0.0082 (8)0.0047 (7)0.0021 (8)
C320.0598 (18)0.0423 (14)0.0522 (16)0.0058 (13)0.0219 (14)0.0097 (13)
C330.0350 (11)0.0358 (11)0.0327 (10)0.0072 (9)0.0120 (9)0.0062 (9)
C340.0392 (12)0.0422 (12)0.0290 (10)0.0094 (10)0.0132 (9)0.0066 (9)
C350.0336 (11)0.0424 (12)0.0288 (10)0.0060 (9)0.0079 (8)0.0024 (9)
C360.0341 (11)0.0344 (11)0.0365 (11)0.0045 (9)0.0138 (9)0.0014 (9)
Geometric parameters (Å, º) top
Br1—C271.900 (4)C11—C121.426 (5)
O1—C21.430 (3)C11—C161.440 (3)
O1—H1O0.8400C12—C131.350 (6)
O2—C311.351 (3)C12—H120.9500
O2—C321.427 (3)C13—C141.419 (5)
O3—C331.238 (3)C13—H130.9500
O4—C331.276 (3)C14—C151.376 (4)
O4—H51.43 (5)C14—H140.9500
O5—C361.283 (3)C15—C161.425 (4)
O5—H50.99 (5)C15—H150.9500
O6—C361.233 (3)C17—C181.391 (4)
N1—C61.486 (3)C17—C221.402 (4)
N1—C51.489 (3)C18—C191.395 (4)
N1—C41.497 (3)C18—H180.9500
N1—H11.0000C19—C201.374 (6)
N2—C311.299 (3)C19—H190.9500
N2—C301.363 (4)C20—C211.384 (7)
C1—C231.519 (3)C20—H200.9500
C1—C171.520 (3)C21—C221.404 (5)
C1—C21.582 (3)C21—H210.9500
C1—H1A1.0000C22—H220.9500
C2—C31.541 (3)C23—C241.356 (4)
C2—C71.542 (3)C23—C311.440 (3)
C3—C41.529 (3)C24—C251.428 (3)
C3—H3A0.9900C24—H240.9500
C3—H3B0.9900C25—C301.417 (4)
C4—H4A0.9900C25—C261.418 (4)
C4—H4B0.9900C26—C271.381 (4)
C5—H5A0.9800C26—H260.9500
C5—H5B0.9800C27—C281.402 (6)
C5—H5C0.9800C28—C291.366 (5)
C6—H6A0.9800C28—H280.9500
C6—H6B0.9800C29—C301.422 (3)
C6—H6C0.9800C29—H290.9500
C7—C81.380 (3)C32—H32A0.9800
C7—C161.437 (3)C32—H32B0.9800
C8—C91.419 (3)C32—H32C0.9800
C8—H80.9500C33—C341.493 (3)
C9—C101.358 (5)C34—C351.333 (4)
C9—H90.9500C34—H340.9500
C10—C111.408 (4)C35—C361.493 (4)
C10—H100.9500C35—H350.9500
C2—O1—H1O109.5C13—C14—H14119.7
C31—O2—C32117.7 (2)C14—C15—C16122.3 (2)
C33—O4—H5111.7 (19)C14—C15—H15118.8
C36—O5—H5112 (3)C16—C15—H15118.8
C6—N1—C5110.39 (18)C15—C16—C7125.3 (2)
C6—N1—C4110.62 (17)C15—C16—C11116.1 (2)
C5—N1—C4113.13 (18)C7—C16—C11118.6 (2)
C6—N1—H1107.5C18—C17—C22119.1 (2)
C5—N1—H1107.5C18—C17—C1124.1 (2)
C4—N1—H1107.5C22—C17—C1116.8 (3)
C31—N2—C30117.5 (2)C17—C18—C19120.4 (3)
C23—C1—C17111.85 (18)C17—C18—H18119.8
C23—C1—C2111.21 (17)C19—C18—H18119.8
C17—C1—C2113.98 (17)C20—C19—C18121.0 (4)
C23—C1—H1A106.4C20—C19—H19119.5
C17—C1—H1A106.4C18—C19—H19119.5
C2—C1—H1A106.4C19—C20—C21119.0 (3)
O1—C2—C3107.73 (17)C19—C20—H20120.5
O1—C2—C7107.45 (17)C21—C20—H20120.5
C3—C2—C7112.40 (17)C20—C21—C22121.3 (3)
O1—C2—C1108.90 (17)C20—C21—H21119.4
C3—C2—C1110.30 (16)C22—C21—H21119.4
C7—C2—C1109.94 (16)C17—C22—C21119.2 (4)
C4—C3—C2112.29 (17)C17—C22—H22120.4
C4—C3—H3A109.1C21—C22—H22120.4
C2—C3—H3A109.1C24—C23—C31116.3 (2)
C4—C3—H3B109.1C24—C23—C1123.8 (2)
C2—C3—H3B109.1C31—C23—C1119.9 (2)
H3A—C3—H3B107.9C23—C24—C25120.6 (2)
N1—C4—C3111.83 (17)C23—C24—H24119.7
N1—C4—H4A109.3C25—C24—H24119.7
C3—C4—H4A109.3C30—C25—C26120.6 (2)
N1—C4—H4B109.3C30—C25—C24117.2 (2)
C3—C4—H4B109.3C26—C25—C24122.2 (3)
H4A—C4—H4B107.9C27—C26—C25118.6 (3)
N1—C5—H5A109.5C27—C26—H26120.7
N1—C5—H5B109.5C25—C26—H26120.7
H5A—C5—H5B109.5C26—C27—C28121.7 (3)
N1—C5—H5C109.5C26—C27—Br1118.8 (3)
H5A—C5—H5C109.5C28—C27—Br1119.5 (2)
H5B—C5—H5C109.5C29—C28—C27119.7 (3)
N1—C6—H6A109.5C29—C28—H28120.1
N1—C6—H6B109.5C27—C28—H28120.1
H6A—C6—H6B109.5C28—C29—C30121.4 (3)
N1—C6—H6C109.5C28—C29—H29119.3
H6A—C6—H6C109.5C30—C29—H29119.3
H6B—C6—H6C109.5N2—C30—C25122.3 (2)
C8—C7—C16118.8 (2)N2—C30—C29119.7 (3)
C8—C7—C2117.7 (2)C25—C30—C29117.9 (3)
C16—C7—C2123.44 (19)N2—C31—O2119.5 (2)
C7—C8—C9121.7 (3)N2—C31—C23125.5 (2)
C7—C8—H8119.1O2—C31—C23114.9 (2)
C9—C8—H8119.1O2—C32—H32A109.5
C10—C9—C8120.4 (2)O2—C32—H32B109.5
C10—C9—H9119.8H32A—C32—H32B109.5
C8—C9—H9119.8O2—C32—H32C109.5
C9—C10—C11120.5 (2)H32A—C32—H32C109.5
C9—C10—H10119.7H32B—C32—H32C109.5
C11—C10—H10119.7O3—C33—O4122.6 (2)
C10—C11—C12120.2 (3)O3—C33—C34117.5 (2)
C10—C11—C16120.0 (3)O4—C33—C34119.9 (2)
C12—C11—C16119.8 (3)C35—C34—C33130.2 (2)
C13—C12—C11122.1 (3)C35—C34—H34114.9
C13—C12—H12119.0C33—C34—H34114.9
C11—C12—H12119.0C34—C35—C36130.7 (2)
C12—C13—C14119.1 (3)C34—C35—H35114.6
C12—C13—H13120.5C36—C35—H35114.6
C14—C13—H13120.5O6—C36—O5122.6 (2)
C15—C14—C13120.7 (3)O6—C36—C35117.3 (2)
C15—C14—H14119.7O5—C36—C35120.1 (2)
C23—C1—C2—O156.9 (2)C1—C17—C18—C19175.7 (2)
C17—C1—C2—O170.6 (2)C17—C18—C19—C200.4 (5)
C23—C1—C2—C361.1 (2)C18—C19—C20—C211.7 (5)
C17—C1—C2—C3171.37 (19)C19—C20—C21—C221.4 (6)
C23—C1—C2—C7174.42 (19)C18—C17—C22—C211.4 (4)
C17—C1—C2—C746.9 (3)C1—C17—C22—C21175.7 (3)
O1—C2—C3—C465.4 (2)C20—C21—C22—C170.1 (5)
C7—C2—C3—C452.8 (2)C17—C1—C23—C2436.6 (3)
C1—C2—C3—C4175.85 (18)C2—C1—C23—C2492.1 (2)
C6—N1—C4—C3163.58 (19)C17—C1—C23—C31142.8 (2)
C5—N1—C4—C372.0 (2)C2—C1—C23—C3188.5 (2)
C2—C3—C4—N1169.78 (18)C31—C23—C24—C252.8 (3)
O1—C2—C7—C80.3 (3)C1—C23—C24—C25177.8 (2)
C3—C2—C7—C8118.1 (2)C23—C24—C25—C302.8 (3)
C1—C2—C7—C8118.7 (2)C23—C24—C25—C26177.2 (2)
O1—C2—C7—C16178.93 (19)C30—C25—C26—C271.5 (4)
C3—C2—C7—C1662.7 (2)C24—C25—C26—C27178.5 (2)
C1—C2—C7—C1660.5 (3)C25—C26—C27—C281.2 (4)
C16—C7—C8—C90.8 (3)C25—C26—C27—Br1178.0 (2)
C2—C7—C8—C9180.0 (2)C26—C27—C28—C292.0 (4)
C7—C8—C9—C101.7 (4)Br1—C27—C28—C29177.2 (2)
C8—C9—C10—C111.3 (4)C27—C28—C29—C300.1 (4)
C9—C10—C11—C12179.1 (3)C31—N2—C30—C251.1 (3)
C9—C10—C11—C160.1 (4)C31—N2—C30—C29179.3 (2)
C10—C11—C12—C13177.7 (3)C26—C25—C30—N2174.9 (2)
C16—C11—C12—C131.4 (5)C24—C25—C30—N25.1 (3)
C11—C12—C13—C141.4 (5)C26—C25—C30—C293.3 (3)
C12—C13—C14—C151.1 (5)C24—C25—C30—C29176.7 (2)
C13—C14—C15—C160.8 (4)C28—C29—C30—N2175.8 (2)
C14—C15—C16—C7179.7 (2)C28—C29—C30—C252.5 (3)
C14—C15—C16—C110.7 (4)C30—N2—C31—O2172.82 (19)
C8—C7—C16—C15178.4 (2)C30—N2—C31—C235.4 (3)
C2—C7—C16—C152.4 (3)C32—O2—C31—N22.3 (3)
C8—C7—C16—C110.6 (3)C32—O2—C31—C23176.1 (2)
C2—C7—C16—C11178.6 (2)C24—C23—C31—N27.4 (3)
C10—C11—C16—C15178.1 (2)C1—C23—C31—N2173.1 (2)
C12—C11—C16—C150.9 (3)C24—C23—C31—O2170.88 (19)
C10—C11—C16—C71.0 (3)C1—C23—C31—O28.6 (3)
C12—C11—C16—C7180.0 (2)O3—C33—C34—C35175.3 (3)
C23—C1—C17—C1880.4 (3)O4—C33—C34—C352.3 (5)
C2—C1—C17—C1846.8 (3)C33—C34—C35—C361.6 (5)
C23—C1—C17—C2296.6 (3)C34—C35—C36—O6175.9 (3)
C2—C1—C17—C22136.2 (2)C34—C35—C36—O55.4 (5)
C22—C17—C18—C191.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O6i0.841.982.818 (3)180
O5—H5···O40.99 (5)1.43 (5)2.419 (3)172 (5)
N1—H1···O31.001.712.704 (3)172
N1—H1···O41.002.513.188 (3)125
Symmetry code: (i) x1/2, y1/2, z.
[4-(6-bromo-2-methoxyquinolin-3-yl)-3-hydroxy-3-(naphthalen-1-yl)-4-phenylbutyl]dimethylazanium 3-carboxyprop-2-enoate (desolvated_sq) top
Crystal data top
C32H32BrN2O2+·C4H3O4F(000) = 1392
Mr = 671.56Dx = 1.238 Mg m3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
a = 15.7494 (12) ÅCell parameters from 9787 reflections
b = 13.3568 (11) Åθ = 2.5–31.6°
c = 17.8634 (14) ŵ = 1.19 mm1
β = 106.500 (3)°T = 150 K
V = 3603.0 (5) Å3Block, white
Z = 40.48 × 0.35 × 0.21 mm
Data collection top
Bruker AXS D8 Quest with PhotonII CPAD
diffractometer
13639 independent reflections
Radiation source: fine focus sealed tube X-ray source10346 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromatorRint = 0.049
Detector resolution: 7.4074 pixels mm-1θmax = 33.1°, θmin = 2.5°
ω and phi scansh = 2424
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
k = 2020
Tmin = 0.678, Tmax = 0.740l = 2727
78970 measured reflections
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0554P)2 + 0.5224P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.042(Δ/σ)max = 0.011
wR(F2) = 0.119Δρmax = 0.76 e Å3
S = 1.06Δρmin = 0.63 e Å3
13639 reflectionsExtinction correction: SHELXL2018/3 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
418 parametersExtinction coefficient: 0.0076 (12)
1 restraintAbsolute structure: Flack x determined using 4139 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: isomorphous structure methodsAbsolute structure parameter: 0.044 (3)
Hydrogen site location: mixed
Special details top

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

Refinement. Crystals were obtained from the acetone / hexane solvate by drying on a glass slide in air over night. In the solavted structure acetone and hexane molecules are located in infinite channels and slowly vacate the crystal lattice. Crystals become milky overnight when taken out of mother liquor solution and left to dry in air, but retain crystallinity.

The structure was solved by isomorphous replacement from the acetone / hexane solvate (structure code 91_2).

The structure contains solvent accessible voids of 607 Ang3 combined. No substantial electron density peaks were found in the solvent accessible voids (less than 0.5 electron per cubic Angstrom) and the residual electron density peaks are not arranged in an interpretable pattern. The structure factors were instead augmented via reverse Fourier transform methods using the SQUEEZE routine (P. van der Sluis & A.L. Spek (1990). Acta Cryst. A46, 194-201) as implemented in the program Platon. The resultant FAB file containing the structure factor contribution from the electron content of the void space was used in together with the original hkl file in the further refinement. (The FAB file with details of the Squeeze results is appended to this cif file). The Squeeze procedure corrected for 66 electrons within the solvent accessible voids, equivalent to 1.14 molecules of acetone per unit cell, or 0.28 acetone per cation / anion pair. Prior to desolvation, 1 molecule of acetone and half a molecule of hexane were determined per cation / anion pair (equivalent to 202 electrons per unit cell).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.30118 (3)0.01862 (4)0.48056 (3)0.08775 (18)
O10.48679 (9)0.26938 (11)0.16351 (8)0.0299 (3)
H1O0.4409100.2833920.1764510.036*
O20.56679 (11)0.48352 (12)0.36136 (9)0.0353 (3)
O30.49001 (11)0.69078 (14)0.21060 (10)0.0412 (4)
O40.56582 (13)0.7067 (2)0.12477 (10)0.0561 (6)
O50.70934 (14)0.76777 (19)0.12131 (10)0.0527 (5)
H50.647 (3)0.747 (3)0.117 (2)0.063*
O60.83287 (11)0.81603 (15)0.20731 (11)0.0433 (4)
N10.39737 (10)0.56465 (13)0.09851 (9)0.0253 (3)
H10.4308370.6157190.1364720.030*
N20.46071 (12)0.40514 (16)0.40537 (10)0.0341 (4)
C10.60427 (12)0.32105 (15)0.27931 (10)0.0273 (3)
H1A0.6432060.3801480.2989570.033*
C20.55192 (12)0.34523 (14)0.19163 (10)0.0246 (3)
C30.50350 (12)0.44640 (15)0.18668 (10)0.0260 (3)
H3A0.4590110.4418020.2160960.031*
H3B0.5467650.4988510.2115020.031*
C40.45728 (13)0.47672 (15)0.10240 (10)0.0274 (3)
H4A0.5024690.4935650.0755930.033*
H4B0.4222920.4194150.0746550.033*
C50.31575 (13)0.53959 (18)0.12091 (14)0.0361 (4)
H5A0.2801490.4916100.0834110.054*
H5B0.2812130.6006550.1207860.054*
H5C0.3321570.5100160.1732680.054*
C60.37409 (14)0.61089 (17)0.01966 (12)0.0337 (4)
H6A0.3509530.5593500.0199280.051*
H6B0.4270360.6412830.0107920.051*
H6C0.3289130.6625300.0161060.051*
C70.61572 (13)0.34273 (15)0.14022 (10)0.0266 (3)
C80.59959 (15)0.27345 (17)0.08056 (11)0.0333 (4)
H80.5502960.2297130.0729550.040*
C90.65464 (18)0.26575 (19)0.03025 (12)0.0399 (5)
H90.6408230.2185760.0112550.048*
C100.72683 (17)0.3253 (2)0.04103 (13)0.0406 (5)
H100.7639340.3185240.0076700.049*
C110.74731 (15)0.39708 (19)0.10124 (13)0.0374 (5)
C120.82271 (18)0.4602 (2)0.11175 (18)0.0514 (6)
H120.8601300.4512010.0789030.062*
C130.84281 (18)0.5327 (3)0.16696 (19)0.0530 (6)
H130.8924980.5751230.1718450.064*
C140.78832 (17)0.5440 (2)0.21732 (17)0.0447 (5)
H140.8024540.5937570.2569620.054*
C150.71539 (14)0.48429 (17)0.20974 (13)0.0345 (4)
H150.6798960.4942500.2441180.041*
C160.69124 (13)0.40771 (16)0.15184 (11)0.0294 (4)
C170.66524 (14)0.23088 (18)0.28874 (11)0.0320 (4)
C180.64028 (17)0.13930 (19)0.25149 (14)0.0404 (5)
H180.5833920.1321370.2151850.048*
C190.6984 (2)0.0582 (2)0.26725 (19)0.0524 (7)
H190.6808850.0035620.2410760.063*
C200.7809 (2)0.0665 (3)0.3203 (2)0.0636 (9)
H200.8195050.0103660.3318500.076*
C210.8066 (2)0.1569 (3)0.35611 (19)0.0645 (10)
H210.8639560.1632960.3917980.077*
C220.74975 (16)0.2403 (2)0.34109 (14)0.0453 (6)
H220.7685770.3023920.3662570.054*
C230.54206 (12)0.31305 (16)0.33015 (10)0.0278 (4)
C240.50506 (13)0.22578 (18)0.34412 (11)0.0313 (4)
H240.5196250.1650580.3229530.038*
C250.44448 (13)0.2244 (2)0.39030 (11)0.0341 (4)
C260.40745 (17)0.1344 (2)0.40884 (14)0.0434 (5)
H260.4234750.0717360.3917090.052*
C270.34766 (18)0.1393 (3)0.45222 (15)0.0509 (7)
C280.32165 (16)0.2313 (3)0.47676 (13)0.0517 (7)
H280.2790780.2331550.5052300.062*
C290.35782 (15)0.3182 (2)0.45953 (12)0.0433 (6)
H290.3399120.3801710.4762480.052*
C300.42172 (13)0.3177 (2)0.41708 (11)0.0350 (4)
C310.51959 (13)0.40074 (16)0.36695 (10)0.0297 (4)
C320.5520 (2)0.5719 (2)0.40070 (17)0.0498 (6)
H32A0.4928490.5983470.3748960.075*
H32B0.5966790.6222110.3990670.075*
H32C0.5561690.5558020.4551610.075*
C330.55723 (15)0.71778 (17)0.19319 (12)0.0339 (4)
C340.63133 (15)0.76090 (18)0.25665 (12)0.0359 (4)
H340.6190220.7689850.3053700.043*
C350.71187 (15)0.78980 (18)0.25582 (12)0.0351 (4)
H350.7482190.8138250.3044320.042*
C360.75467 (15)0.79076 (17)0.19113 (13)0.0343 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0858 (3)0.1017 (3)0.0933 (3)0.0388 (2)0.0538 (2)0.0023 (2)
O10.0269 (6)0.0317 (7)0.0303 (6)0.0008 (5)0.0069 (5)0.0023 (5)
O20.0412 (8)0.0359 (7)0.0296 (7)0.0055 (6)0.0113 (6)0.0013 (6)
O30.0368 (8)0.0462 (9)0.0446 (8)0.0102 (7)0.0180 (7)0.0101 (7)
O40.0447 (9)0.0925 (16)0.0338 (8)0.0314 (10)0.0156 (7)0.0205 (9)
O50.0471 (10)0.0827 (14)0.0326 (8)0.0262 (10)0.0185 (7)0.0094 (8)
O60.0304 (7)0.0481 (9)0.0533 (10)0.0050 (7)0.0150 (7)0.0025 (8)
N10.0229 (6)0.0280 (7)0.0253 (7)0.0031 (5)0.0072 (5)0.0022 (5)
N20.0282 (8)0.0520 (11)0.0215 (7)0.0112 (7)0.0062 (6)0.0002 (7)
C10.0249 (8)0.0346 (9)0.0226 (7)0.0061 (7)0.0071 (6)0.0028 (7)
C20.0240 (7)0.0288 (8)0.0211 (7)0.0036 (6)0.0064 (6)0.0001 (6)
C30.0250 (8)0.0306 (8)0.0220 (7)0.0070 (6)0.0060 (6)0.0014 (6)
C40.0280 (8)0.0308 (8)0.0229 (7)0.0089 (7)0.0066 (6)0.0013 (6)
C50.0240 (8)0.0438 (12)0.0432 (11)0.0043 (8)0.0137 (8)0.0108 (9)
C60.0331 (9)0.0371 (10)0.0299 (9)0.0074 (8)0.0072 (7)0.0084 (8)
C70.0282 (8)0.0311 (9)0.0213 (7)0.0091 (7)0.0084 (6)0.0029 (6)
C80.0372 (10)0.0389 (10)0.0235 (8)0.0108 (8)0.0082 (7)0.0007 (7)
C90.0530 (13)0.0430 (11)0.0255 (8)0.0200 (10)0.0142 (8)0.0022 (8)
C100.0471 (12)0.0477 (12)0.0342 (10)0.0225 (10)0.0235 (9)0.0124 (9)
C110.0343 (10)0.0463 (12)0.0368 (10)0.0138 (9)0.0184 (8)0.0111 (9)
C120.0410 (12)0.0619 (16)0.0602 (15)0.0081 (11)0.0286 (11)0.0153 (13)
C130.0360 (11)0.0566 (16)0.0704 (17)0.0023 (11)0.0213 (11)0.0092 (14)
C140.0355 (11)0.0449 (13)0.0524 (13)0.0048 (9)0.0101 (9)0.0017 (10)
C150.0315 (9)0.0389 (10)0.0334 (9)0.0017 (8)0.0098 (7)0.0023 (8)
C160.0271 (8)0.0355 (9)0.0271 (8)0.0070 (7)0.0100 (7)0.0054 (7)
C170.0293 (9)0.0423 (10)0.0270 (8)0.0125 (8)0.0122 (7)0.0098 (8)
C180.0421 (12)0.0399 (11)0.0436 (11)0.0151 (9)0.0194 (9)0.0108 (9)
C190.0627 (16)0.0422 (13)0.0624 (16)0.0219 (12)0.0341 (13)0.0142 (12)
C200.0639 (18)0.073 (2)0.0621 (17)0.0466 (17)0.0304 (14)0.0281 (16)
C210.0434 (14)0.095 (3)0.0527 (15)0.0388 (16)0.0102 (12)0.0213 (16)
C220.0311 (10)0.0676 (16)0.0369 (10)0.0193 (10)0.0088 (8)0.0091 (11)
C230.0237 (8)0.0385 (10)0.0207 (7)0.0063 (7)0.0053 (6)0.0013 (7)
C240.0288 (8)0.0418 (10)0.0235 (7)0.0032 (8)0.0078 (6)0.0025 (7)
C250.0250 (8)0.0558 (13)0.0210 (7)0.0003 (8)0.0056 (6)0.0016 (8)
C260.0366 (11)0.0622 (15)0.0329 (10)0.0079 (11)0.0121 (8)0.0018 (10)
C270.0390 (12)0.081 (2)0.0347 (11)0.0167 (13)0.0134 (9)0.0007 (12)
C280.0309 (10)0.098 (2)0.0289 (9)0.0091 (13)0.0121 (8)0.0074 (12)
C290.0285 (9)0.0788 (18)0.0234 (8)0.0011 (10)0.0085 (7)0.0066 (10)
C300.0226 (8)0.0617 (14)0.0191 (7)0.0067 (8)0.0034 (6)0.0006 (8)
C310.0279 (8)0.0398 (10)0.0202 (7)0.0079 (7)0.0048 (6)0.0020 (7)
C320.0591 (16)0.0417 (12)0.0522 (14)0.0046 (12)0.0217 (12)0.0106 (11)
C330.0352 (9)0.0351 (10)0.0331 (9)0.0075 (8)0.0126 (8)0.0062 (8)
C340.0389 (10)0.0424 (11)0.0285 (8)0.0089 (9)0.0129 (8)0.0067 (8)
C350.0335 (10)0.0425 (11)0.0286 (9)0.0053 (8)0.0076 (7)0.0028 (8)
C360.0347 (10)0.0338 (10)0.0367 (10)0.0050 (8)0.0135 (8)0.0012 (8)
Geometric parameters (Å, º) top
Br1—C271.897 (3)C11—C121.425 (4)
O1—C21.428 (2)C11—C161.439 (3)
O1—H1O0.8400C12—C131.353 (5)
O2—C311.352 (3)C12—H120.9500
O2—C321.426 (3)C13—C141.417 (4)
O3—C331.239 (3)C13—H130.9500
O4—C331.276 (3)C14—C151.373 (3)
O4—H51.42 (4)C14—H140.9500
O5—C361.286 (3)C15—C161.427 (3)
O5—H51.01 (4)C15—H150.9500
O6—C361.230 (3)C17—C181.395 (4)
N1—C61.485 (2)C17—C221.398 (3)
N1—C51.489 (2)C18—C191.394 (3)
N1—C41.496 (2)C18—H180.9500
N1—H11.0000C19—C201.378 (5)
N2—C311.302 (3)C19—H190.9500
N2—C301.363 (3)C20—C211.373 (6)
C1—C231.517 (3)C20—H200.9500
C1—C171.520 (3)C21—C221.406 (4)
C1—C21.582 (2)C21—H210.9500
C1—H1A1.0000C22—H220.9500
C2—C31.542 (3)C23—C241.358 (3)
C2—C71.542 (3)C23—C311.436 (3)
C3—C41.529 (2)C24—C251.428 (3)
C3—H3A0.9900C24—H240.9500
C3—H3B0.9900C25—C261.415 (4)
C4—H4A0.9900C25—C301.418 (4)
C4—H4B0.9900C26—C271.381 (4)
C5—H5A0.9800C26—H260.9500
C5—H5B0.9800C27—C281.405 (5)
C5—H5C0.9800C28—C291.365 (5)
C6—H6A0.9800C28—H280.9500
C6—H6B0.9800C29—C301.422 (3)
C6—H6C0.9800C29—H290.9500
C7—C81.380 (3)C32—H32A0.9800
C7—C161.439 (3)C32—H32B0.9800
C8—C91.418 (3)C32—H32C0.9800
C8—H80.9500C33—C341.492 (3)
C9—C101.356 (4)C34—C351.330 (3)
C9—H90.9500C34—H340.9500
C10—C111.408 (4)C35—C361.494 (3)
C10—H100.9500C35—H350.9500
C2—O1—H1O109.5C13—C14—H14119.5
C31—O2—C32118.04 (19)C14—C15—C16122.1 (2)
C33—O4—H5112.6 (16)C14—C15—H15119.0
C36—O5—H5113 (2)C16—C15—H15119.0
C6—N1—C5110.41 (15)C15—C16—C7125.18 (17)
C6—N1—C4110.68 (15)C15—C16—C11116.2 (2)
C5—N1—C4113.10 (16)C7—C16—C11118.64 (19)
C6—N1—H1107.5C18—C17—C22118.9 (2)
C5—N1—H1107.5C18—C17—C1123.96 (19)
C4—N1—H1107.5C22—C17—C1117.0 (2)
C31—N2—C30117.48 (19)C19—C18—C17120.3 (3)
C23—C1—C17111.90 (16)C19—C18—H18119.8
C23—C1—C2111.31 (15)C17—C18—H18119.8
C17—C1—C2113.99 (15)C20—C19—C18120.9 (3)
C23—C1—H1A106.3C20—C19—H19119.5
C17—C1—H1A106.3C18—C19—H19119.5
C2—C1—H1A106.3C21—C20—C19119.1 (2)
O1—C2—C3107.91 (15)C21—C20—H20120.5
O1—C2—C7107.43 (15)C19—C20—H20120.5
C3—C2—C7112.34 (15)C20—C21—C22121.4 (3)
O1—C2—C1108.89 (15)C20—C21—H21119.3
C3—C2—C1110.23 (14)C22—C21—H21119.3
C7—C2—C1109.92 (14)C17—C22—C21119.4 (3)
C4—C3—C2112.22 (15)C17—C22—H22120.3
C4—C3—H3A109.2C21—C22—H22120.3
C2—C3—H3A109.2C24—C23—C31116.22 (18)
C4—C3—H3B109.2C24—C23—C1123.66 (18)
C2—C3—H3B109.2C31—C23—C1120.11 (19)
H3A—C3—H3B107.9C23—C24—C25120.6 (2)
N1—C4—C3111.81 (14)C23—C24—H24119.7
N1—C4—H4A109.3C25—C24—H24119.7
C3—C4—H4A109.3C26—C25—C30120.5 (2)
N1—C4—H4B109.3C26—C25—C24122.3 (2)
C3—C4—H4B109.3C30—C25—C24117.3 (2)
H4A—C4—H4B107.9C27—C26—C25118.9 (3)
N1—C5—H5A109.5C27—C26—H26120.5
N1—C5—H5B109.5C25—C26—H26120.5
H5A—C5—H5B109.5C26—C27—C28121.5 (3)
N1—C5—H5C109.5C26—C27—Br1119.1 (3)
H5A—C5—H5C109.5C28—C27—Br1119.43 (19)
H5B—C5—H5C109.5C29—C28—C27119.7 (2)
N1—C6—H6A109.5C29—C28—H28120.1
N1—C6—H6B109.5C27—C28—H28120.1
H6A—C6—H6B109.5C28—C29—C30121.4 (3)
N1—C6—H6C109.5C28—C29—H29119.3
H6A—C6—H6C109.5C30—C29—H29119.3
H6B—C6—H6C109.5N2—C30—C25122.26 (18)
C8—C7—C16118.65 (18)N2—C30—C29119.8 (2)
C8—C7—C2117.80 (18)C25—C30—C29117.9 (2)
C16—C7—C2123.55 (16)N2—C31—O2119.39 (19)
C7—C8—C9121.8 (2)N2—C31—C23125.7 (2)
C7—C8—H8119.1O2—C31—C23114.91 (17)
C9—C8—H8119.1O2—C32—H32A109.5
C10—C9—C8120.4 (2)O2—C32—H32B109.5
C10—C9—H9119.8H32A—C32—H32B109.5
C8—C9—H9119.8O2—C32—H32C109.5
C9—C10—C11120.58 (19)H32A—C32—H32C109.5
C9—C10—H10119.7H32B—C32—H32C109.5
C11—C10—H10119.7O3—C33—O4122.5 (2)
C10—C11—C12120.4 (2)O3—C33—C34117.47 (19)
C10—C11—C16119.9 (2)O4—C33—C34120.0 (2)
C12—C11—C16119.7 (2)C35—C34—C33130.2 (2)
C13—C12—C11122.2 (2)C35—C34—H34114.9
C13—C12—H12118.9C33—C34—H34114.9
C11—C12—H12118.9C34—C35—C36130.7 (2)
C12—C13—C14118.7 (3)C34—C35—H35114.6
C12—C13—H13120.6C36—C35—H35114.6
C14—C13—H13120.6O6—C36—O5122.4 (2)
C15—C14—C13121.0 (3)O6—C36—C35117.5 (2)
C15—C14—H14119.5O5—C36—C35119.99 (19)
C23—C1—C2—O157.1 (2)C1—C17—C18—C19175.8 (2)
C17—C1—C2—O170.6 (2)C17—C18—C19—C200.7 (4)
C23—C1—C2—C361.1 (2)C18—C19—C20—C211.9 (5)
C17—C1—C2—C3171.18 (17)C19—C20—C21—C221.4 (5)
C23—C1—C2—C7174.55 (16)C18—C17—C22—C211.4 (4)
C17—C1—C2—C746.8 (2)C1—C17—C22—C21175.6 (2)
O1—C2—C3—C465.28 (19)C20—C21—C22—C170.2 (4)
C7—C2—C3—C453.0 (2)C17—C1—C23—C2437.0 (2)
C1—C2—C3—C4175.92 (16)C2—C1—C23—C2491.9 (2)
C6—N1—C4—C3163.50 (17)C17—C1—C23—C31142.75 (18)
C5—N1—C4—C372.0 (2)C2—C1—C23—C3188.4 (2)
C2—C3—C4—N1169.68 (16)C31—C23—C24—C252.6 (3)
O1—C2—C7—C80.3 (2)C1—C23—C24—C25177.69 (17)
C3—C2—C7—C8118.21 (19)C23—C24—C25—C26177.30 (19)
C1—C2—C7—C8118.66 (18)C23—C24—C25—C303.1 (3)
O1—C2—C7—C16178.92 (16)C30—C25—C26—C271.1 (3)
C3—C2—C7—C1662.6 (2)C24—C25—C26—C27178.4 (2)
C1—C2—C7—C1660.6 (2)C25—C26—C27—C281.3 (4)
C16—C7—C8—C90.8 (3)C25—C26—C27—Br1177.66 (17)
C2—C7—C8—C9179.92 (18)C26—C27—C28—C291.9 (4)
C7—C8—C9—C101.8 (3)Br1—C27—C28—C29177.10 (18)
C8—C9—C10—C111.3 (3)C27—C28—C29—C300.1 (3)
C9—C10—C11—C12179.3 (2)C31—N2—C30—C251.2 (3)
C9—C10—C11—C160.1 (3)C31—N2—C30—C29179.20 (18)
C10—C11—C12—C13177.4 (3)C26—C25—C30—N2175.10 (19)
C16—C11—C12—C131.8 (4)C24—C25—C30—N25.3 (3)
C11—C12—C13—C141.8 (4)C26—C25—C30—C293.0 (3)
C12—C13—C14—C151.2 (4)C24—C25—C30—C29176.64 (18)
C13—C14—C15—C160.6 (4)C28—C29—C30—N2175.7 (2)
C14—C15—C16—C7179.7 (2)C28—C29—C30—C252.4 (3)
C14—C15—C16—C110.5 (3)C30—N2—C31—O2172.83 (16)
C8—C7—C16—C15178.55 (19)C30—N2—C31—C235.4 (3)
C2—C7—C16—C152.2 (3)C32—O2—C31—N22.3 (3)
C8—C7—C16—C110.6 (3)C32—O2—C31—C23176.2 (2)
C2—C7—C16—C11178.63 (17)C24—C23—C31—N27.4 (3)
C10—C11—C16—C15178.2 (2)C1—C23—C31—N2172.90 (17)
C12—C11—C16—C151.0 (3)C24—C23—C31—O2170.95 (16)
C10—C11—C16—C71.1 (3)C1—C23—C31—O28.8 (2)
C12—C11—C16—C7179.7 (2)O3—C33—C34—C35175.4 (3)
C23—C1—C17—C1880.5 (2)O4—C33—C34—C352.2 (4)
C2—C1—C17—C1846.9 (3)C33—C34—C35—C361.3 (5)
C23—C1—C17—C2296.3 (2)C34—C35—C36—O6175.7 (3)
C2—C1—C17—C22136.30 (19)C34—C35—C36—O55.8 (4)
C22—C17—C18—C190.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O6i0.841.982.820 (2)180
O5—H5···O41.01 (4)1.42 (4)2.420 (3)169 (4)
N1—H1···O31.001.712.705 (2)172
N1—H1···O41.002.513.186 (2)125
Symmetry code: (i) x1/2, y1/2, z.
Selected torsion angles for bedaquilinium maleate structures top
hemihydrateTHFethyl acetateacetone/hexanedesolvated
τ plane 1 vs plane 271.31 (7)64.3 (1)67.78 (7), 63.0 (2)70.00 (6)70.34 (5)
τ plane 2 vs plane 365.35 (9)63.7 (1)65.8 (1), 64.0 (2)66.60 (7)64.89 (6)
τ plane 1 vs plane 332.62 (9)26.4 (1)31.7 (1), 31.50 (9)29.47 (7)32.06 (6)
τ C1—C2—C3—C4175.6 (3)174.1 (4)176.4 (3), 175.9 (3)176.2 (2)175.85 (18)
τ C2—C3—C4—N1169.4 (3)174.3 (4)173.9 (3), 174.6 (3)172.86 (19)169.78 (18)
τ C17—C1—C2—C3-170.8 (3)-169.8 (4)-172.0 (3), -164.4 (7)-172.3 (2)-171.37 (19)
Bond distances and angles involving the intramolecular O···H···O hydrogen bond of the hydromaleate anions (Å, °) top
hemihydrateTHFethyl acetateacetone/hexanedesolvated
O5—H51.13 (6)1.28 (8)1.11 (10) A 1.17 (8) B1.18 (5)0.99 (5)
O4—H51.29 (6)1.15 (8)1.33 (10) A 1.29 (8) B1.24 (5)1.43 (5)
O5···H5···O6169 (5)171 (7)171 (9) A 164 (6) B175 (5)172 (5)
C33—O41.275 (5)1.275 (7)1.246 (3) A 1.266 (5) B1.271 (3)1.276 (3)
C36—O51.290 (5)1.301 (6)1.292 (5) A 1.293 (5) B1.283 (3)1.283 (3)
C33—O31.237 (5)1.234 (6)1.245 (5) A 1.241 (5) B1.230 (3)1.238 (3)
C36—O61.231 (5)1.217 (6)1.216 (5) A 1.216 (5) B1.222 (3)1.233 (3)
Hot stage optical microscopy data for the acetone/hexane and the ethyl acetate crystals top
Run 1Run 2Run 3 (in mineral oil)
acetone/hexane solvate, onset and end of melting124.5°C, 133.7°C122.1°C, 133.7°C119.9°C, 128.8°C
ethyl acetate solvate, onset and end of melting122.1°C, 133.6°C122.8°C, 133.6°C118.4°C, 128.3°C
 

Funding information

The Bill and Melinda Gates Foundation (grant No. INV-017799 to SRB) is thanked for funding. This material is based upon work supported by the National Science Foundation through the Major Research Instrumentation Program under grant No. CHE 1625543 (funding for the single-crystal X-ray diffractometer).

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