The effect of bromine scanning around the phenyl group of 4-phenyl-quinolone derivatives

Article abstract of DOI:10.1107/S2053229614015617

Three quinolone compounds were synthesized and crystallized in an effort to study the structure-activity relationship of these calcium-channel antagonists. In all three quinolones, viz. ethyl 4-(4-bromo-phenyl)-2,7,7-trimethyl-5-oxo-1, 4,5,6,7,8-hexa-hydr

Full text of DOI:10.1107/S2053229614015617

research papers
Acta Crystallographica Section C
derivatives have been synthesized to yield compounds active
as calcium-channel agonists or antagonists (Martin-Leon et al.,
1995; Rose, 1990; Rose & Draeger, 1992). A fused cyclo-
hexanone ring is one of the modifications to 1,4-DHP
compounds and this class has been shown to have moderate
calcium-channel antagonistic activity, as well as modest anti-
inflammatory and stem-cell differentiation properties, and has
been implicated in slowing neurodegenerative disorders
(Tippier et al., 2014). Thus, further understanding of the
structure–activity relationship of 1,4-DHP compounds and
their derivatives will allow for the determination of off-target
activity and the reduction of side effects. It has been proven
that the flattened boat conformation of the 1,4-DHP ring is
one factor that leads to higher calcium-channel activity
(Linden et al., 2014). Atoms N1 and C4 of the 1,4-DHP ring
can be marginally displaced from the mean plane of the boat
(Linden et al., 2002). An aryl group in the 4-position of the 1,4-
DHP ring is essential for optimal activity (Shaldam et al.,
2014). One study showed that an aryl ring with halogen or
other electron-withdrawing groups exhibits higher receptor-
binding activity (Takahashi et al., 2008). On the 1,4-DHP ring,
ester groups are usually substituted at the 3- and 5-positions. It
has been suggested that at least one cis-ester is required for
the calcium-channel antagonistic effect and hydrogen bonding
to the receptor (Fossheim, 1986). In an effort to find more
active calcium-channel antagonists in the 1,4-DHP genre, we
have synthesized a series of 1,4-DHP fused-ring derivatives,
i.e. hexahydroquinolones. In this paper, we report three
structures which have bromine substituted at the para-, meta-
and ortho-positions on the phenyl ring attached to the 1,4-
DHP ring, viz. compounds (I)–(III).
Structural Chemistry
ISSN 2053-2296
The effect of bromine scanning around
the phenyl group of 4-phenylquinolone
derivatives
Scott A. Steiger,a Anthony J. Monacelli,b Chun Li,b Janet L.
Huntingb and Nicholas R. Natalea*
aDepartment of Biomedical and Pharmaceutical Sciences, University of Montana,
32 Campus Drive, Missoula, MT 59812, USA, and bDepartment of Chemistry, Ithaca
College, 953 Danby Road, Ithaca, NY 14850, USA
Correspondence e-mail: nicholas.natale@mso.umt.edu
Received 25 April 2014
Accepted 4 July 2014
Three quinolone compounds were synthesized and crystal-
lized in an effort to study the structure–activity relationship of
these calcium-channel antagonists. In all three quinolones, viz.
ethyl 4-(4-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexa-
hydroquinoline-3-carboxylate, (I), ethyl 4-(3-bromophenyl)-
2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carbox-
ylate, (II), and ethyl 4-(2-bromophenyl)-2,7,7-trimethyl-5-oxo-
1,4,5,6,7,8-hexahydroquinoline-3-carboxylate, (III), all C21H24-
BrNO3, common structural features such as a flat boat
conformation of the 1,4-dihydropyridine (1,4-DHP) ring, an
envelope conformation of the fused cyclohexanone ring and a
bromophenyl ring at the pseudo-axial position and orthogonal
to the 1,4-DHP ring are retained. However, due to the
different packing interactions in each compound, halogen
bonds are observed in (I) and (III). Compound (III)
crystallizes with two molecules in the asymmetric unit. All
of the prepared derivatives satisfy the basic structural
requirements to possess moderate activity as calcium-channel
antagonists.
Keywords: crystal structure; structure–activity relationships;
calcium-channel antagonists; quinolone compounds; halogen
bonding; 1,4-dihydropyridine rings; hydrogen bonding; bromine
scanning.
1. Introduction
The 1,4-dihydropyridine (1,4-DHP) heterocycle comprises a
large family of medicinally important compounds. The
substructure has garnered the most attention as a class of
calcium-channel antagonists working as slow calcium-channel
blockers, which have been used in the treatment of angina
pectoris and hypertension (Wishart et al., 2006). The exam-
ination of Hantzsch 1,4-dihydropyridine ester derivatives has
produced more active and longer-acting agents than the
prototypical nifedipine molecule (Triggle, 2003). Many other
2. Experimental
2.1. Synthesis and crystallization
An oven-dried 100 ml round-bottomed flask was charged
with dimedone (0.757 g), ethyl acetoacetate (0.703 g), ytter-
bium(III) trifluoromethanesulfonate (0.170 g) and a magnetic
stirrer bar. The mixture was then taken up in absolute ethanol
(13.5 ml), capped, placed under an inert atmosphere of argon
and stirred at room temperature for 20 min. Homologues of
790 # 2014 International Union of Crystallography
doi:10.1107/S2053229614015617
Acta Cryst. (2014). C70, 790–795

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Table 1
Experimental details.
For all structures: C21H24BrNO3, Mr = 418.32, Z = 8. Experiments were carried out at 100 K with Mo Kꢁ radiation using a Bruker SMART BREEZE CCD area-
detector diffractometer. Absorption was corrected for by multi-scan methods (SADABS; Bruker, 2008). H atoms were treated by a mixture of independent and
constrained refinement.
(I)
(II)
(III)
Crystal data
Crystal system, space group
Orthorhombic, Pbcn
18.0371 (4), 15.4309 (3), 14.2604 (3)
90, 90, 90
3969.08 (14)
2.09
Orthorhombic, Pbcn
17.0813 (5), 15.4877 (5), 14.2544 (5)
90, 90, 90
3771.0 (2)
2.20
Monoclinic, P21/c
14.5012 (18), 18.299 (2), 15.1952 (19)
90, 107.5262 (15), 90
3844.9 (8)
2.16
0.34 ꢃ 0.16 ꢃ 0.08
˚
a, b, c (A)
ꢁ, ꢂ, ꢃ (ꢁ)
3
˚
V (A )
ꢄ (mmꢂ1
Crystal size (mm)
)
0.26 ꢃ 0.18 ꢃ 0.13
0.40 ꢃ 0.21 ꢃ 0.19
Data collection
Tmin, Tmax
0.909, 1.000
35271, 4558, 3391
0.839, 1.000
55070, 5055, 4278
0.866, 1.000
45465, 8935, 6859
No. of measured, independent and
observed [I > 2ꢅ(I)] reflections
Rint
0.038
0.650
0.032
0.684
0.065
0.653
ꢂ1
˚
(sin ꢆ/ꢇ)max (A
)
Refinement
R[F2 > 2ꢅ(F2)], wR(F2), S
No. of reflections
No. of parameters
0.042, 0.101, 1.04
4558
243
1.49, ꢂ1.21
0.032, 0.084, 1.03
5055
243
1.31, ꢂ0.38
0.036, 0.081, 1.02
8935
485
ꢂ3
˚
Áꢈmax, Áꢈmin (e A
)
1.46, ꢂ0.47
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and OLEX2 (Dolomanov et al., 2009).
bromobenzaldehyde (1.0 g, 5.405 mmol) and a quantity of
ammonium acetate (0.419 g) were added to the stirred solu-
tion, and stirring was continued at room temperature for a
further 48 h. The progress of the reaction was monitored via
thin-layer chromatography (TLC). Once the reaction was
complete, excess solvent was removed via rotary evaporation.
The solution was then purified via silica-column chromato-
graphy. The products were recrystallized from hexane and
ethyl acetate (1:4 v/v) as white to light-yellow crystalline solids
[for (I): yield 1.91 g, 4.57 mmol, 84.00%; for (II): yield 1.86 g,
4.45 mmol, 82.30%; for (III): yield 1.45 g, 3.466 mmol,
63.76%]. Analytical samples of the products were again re-
crystallized from a minimum of warm hexane and ethyl
acetate (1:4 v/v), to which hexane was added dropwise to a
faint opalescence, and slow evaporation produced diffraction-
quality crystals as white to light-yellow crystalline solids.
29.44, 27.15, 19.49, 14.23. HRMS calculated for C21H24BrNO3:
418.1018; found: 418.1024. MS, m/z = 418 ([M + 1] 100), 419
([M + 2] 10), 420 ([M + 3] 100). M.p. 527–528 K. TLC [SiO2,
hexane–EtOAc (3:2 v/v)]: RF = 0.19.
Compound (II). 1H NMR (CDCl3): ꢀ 7.41 (s, 1H), 7.26 (d, J=
7.53 Hz, 1H), 7.22 (d, J = 8.53 Hz, 1H), 7.07 (t, J = 7.78 Hz, 1H),
6.09 (bs, 1H), 5.03 (s, 1H), 4.07 (m, J = 7.15 Hz, 2H), 2.38 (s,
3H), 2.31 (s, 2H), 2.22 (s, 2H), 1.21 (t, J = 7.15 Hz, 3H), 1.09 (s,
3H), 0.96 (s, 6H); 13C NMR (CDCl3): ꢀ 195.39, 167.15, 149.30,
148.24, 143.79, 131.09, 129.17, 126.97, 122.10, 111.71, 105.60,
59.96, 50.69, 41.12, 36.64, 32.78, 29.40, 27.22, 19.51, 14.21.
HRMS calculated for C21H24BrNO3: 418.1018; found:
418.0979. MS, m/z = 418 ([M + 1] 100), 419 ([M + 2] 90). M.p.
508–509 K. TLC [SiO2, hexane–EtOAc (3:2 v/v)]: RF = 0.12.
Compound (III). 1H NMR (CDCl3): ꢀ 7.44 (dd, J = 7.91 Hz,
1H), 7.37 (dd, J = 7.78 Hz, 1H), 7.16 (tt, J = 7.53 Hz, 1H), 6.94
(tt, J = 7.91 Hz, 1H), 5.92 (bs, 1H), 5.37 (s, 1H), 4.08 (m, J =
7.15 Hz, 2H), 2.32 (s, 3H), 2.30 (s, 2H), 2.19 (s, 2H), 1.18 (t, J =
7.03 Hz, 3H), 1.08 (s, 3H), 0.96 (s, 6H); 13C NMR (CDCl3): ꢀ
195.30, 167.44, 148.04, 145.88, 143.22, 133.08, 132.03, 127.49,
126.97, 123.38, 111.74, 105.86, 59.84, 50.69, 41.29, 37.98, 32.58,
29.28, 27.38, 19.49, 14.36. HRMS calculated for C21H24BrNO3:
418.1018; found: 418.1037. MS: m/z = 417 ([M] 100), 418
([M + 1] 100), 419 ([M + 2] 30). M.p. 473–477 K. TLC [SiO2,
hexane–EtOAc (3:2 v/v)]: RF = 0.23.
2.2. Characterization information
Melting points were determined in open capillary tubes
with a Mel-Temp melting point apparatus (200 W) and are
uncorrected. Structures were confirmed with 1H and 13C NMR,
1
and mass spectroscopy. H NMR spectra were obtained in
chloroform-d1 using a Bruker AMX 400 MHz spectrometer.
Chemical shifts are reported as p.p.m. relative to tetra-
methylsilane (TMS). LC–MS (liquid chromatography–mass
spectrometry) data were obtained using a Waters LCT
Premier XE series spectrometer.
2.3. Refinement
1
Compound (I). H NMR (CDCl3): ꢀ 7.31 (d, J = 8.28 Hz,
Crystal data, data collection and structure refinement
details are summarized in Table 1. The methyl H atoms were
˚
constrained to an ideal geometry, with C—H = 0.98 A and
Uiso(H) = 1.5Ueq(C), and were allowed to rotate freely about
their C—C bonds. The remaining C-bound H atoms were
˚
placed in calculated positions, with C—H = 0.95–1.00 A, and
2H), 7.20 (d, J = 8.28 Hz, 2H), 6.01 (bs, 1H), 5.02 (s, 1H), 4.05
(q, J = 7.03 Hz, 2H), 2.38 (s, 3H), 2.21 (s, 2H), 2.17 (s, 2H), 1.20
(t, J = 7.15 Hz, 3H), 1.08 (s, 3H), 0.93 (s, 6H); 13C NMR
(CDCl3): ꢀ 195.42, 167.19, 148.01, 146.07, 143.60, 130.96,
129.89, 119.82, 111.90, 105.72, 59.94, 50.69, 41.14, 36.33, 32.75,
ꢀ
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Three homologues of C21H24BrNO3 791

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refined as riding, with Uiso(H) = 1.2Ueq(C). The positions of
the amine H atoms were determined from difference Fourier
maps and refined freely along with their isotropic displace-
ment parameters. Two low-angle reflections of (I) and four of
(III) were omitted from the refinement because their observed
intensities were much lower than the calculated values as a
result of being partially obscured by the beam stop.
3. Results and discussion
Both ethyl 4-(4-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-
hexahydroquinoline-3-carboxylate, (I) (Fig. 1), and ethyl
4-(3-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydro-
quinoline-3-carboxylate, (II) (Fig. 2), crystallize in the ortho-
rhombic space group Pbcn with one molecule in the
asymmetric unit. The asymmetric unit of ethyl 4-(2-bromo-
phenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-
3-carboxylate, (III) (Fig. 3), is composed of two symmetry-
independent molecules, (IIIA) and (IIIB), which crystallize in
the monoclinic space group P21/c. All three compounds have
very similar structural conformations, which accommodate the
requirements for calcium-channel antagonists.
Figure 1
The asymmetric unit of (I), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level.
In all three structures, the 1,4-DHP ring is characterized by
a shallow or flattened boat conformation, which is one of the
factors that leads to higher calcium-channel activity. The boat
conformation can be quantified by ring-puckering parameters
(Cremer & Pople, 1975). An ideal boat would have ꢆ = 90ꢁ and
’ = n ꢃ 60ꢁ. Calculated using PLATON (Spek, 2009), the
ꢁ
˚
puckering parameters in (I) are Q = 0.196 (2) A, ꢆ = 106.5 (6)
and ’ = 5.2 (8)ꢁ for the atom sequence N1–C2–C3–C4–C10–
C9. The corresponding parameters for (II) are Q =
ꢁ
ꢁ
˚
0.3014 (17) A, ꢆ = 107.1 (3) and ’ = 0.9 (3) , while for (III),
ꢁ
˚
two sets were obtaꢁined as QA = 0.162 (3) A, ꢆA = 67.3 ꢁ(10)
˚
and ’A = 197.5 (10) , and QB = 0.279 (3) A, ꢆB = 106.9 (6) and
’B = 3.9 (6)ꢁ for molecules A and B, respectively. The shal-
lowness of the boat conformation is indicated by the marginal
displacements of atoms N1 and C4 from the mean plane (the
base of the boat) defined by the two double bonds (C2 C3
and C10 C9). The deviation of atom N1 from the base of the
Figure 2
The asymmetric unit of (II), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level.
Figure 3
The asymmetric unit of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
ꢀ
792 Steiger et al.
Three homologues of C21H24BrNO3
Acta Cryst. (2014). C70, 790–795

research papers
Figure 4
Part of the crystal structure of (I), showing the formation of chains of
molecules running along the c axis. Hydrogen bonds are indicated by
dashed lines. For the sake of clarity, H atoms not involved in hydrogen
bonding have been omitted.
Figure 5
Part of the crystal structure of (II), showing the formation of chains of
molecules running along the c axis. Hydrogen bonds are indicated by
dashed lines. For the sake of clarity, H atoms not involved in hydrogen
bonding have been omitted.
Table 2
Hydrogen-bond geometry (A, ) for (I).
ꢁ
˚
Table 3
Hydrogen-bond geometry (A, ) for (II).
ꢁ
˚
D—Hꢄ ꢄ ꢄA
D—H
Hꢄ ꢄ ꢄA
Dꢄ ꢄ ꢄA
D—Hꢄ ꢄ ꢄA
N1—H1ꢄ ꢄ ꢄO1i
Symmetry code: (i) x; ꢂy; z ꢂ .
0.89 (3)
1.94 (3)
2.812 (2)
168 (3)
D—Hꢄ ꢄ ꢄA
N1—H1ꢄ ꢄ ꢄO1i
Symmetry code: (i) x; ꢂy þ 1; z þ .
D—H
Hꢄ ꢄ ꢄA
Dꢄ ꢄ ꢄA
D—Hꢄ ꢄ ꢄA
1
2
0.86 (2)
2.05 (2)
2.8896 (19)
166 (2)
1
2
˚
boat is generally smaller, between 0.00 and 0.19 A, while the
˚
deviation of atom C4 is most frequently found around 0.3 A
(Linden et al., 2004, 2005). These are also observed in the title
compounds: the deviations of atom N1 are 0.095 (3), 0.142 (2),
˚
0.047 (3) and 0.134 (3) A for (I), (II), (IIIA) and (IIIB),
respectively; and the deviations of atom C4 are 0.235 (4),
88.46 (5), 99.37 (8) and 89.36 (9)ꢁ for (I), (II), (IIIA) and
(IIIB), respectively. Another quantitative descriptive factor is
the pseudo-torsion angle between the N1ꢄ ꢄ ꢄC4 axis and the
bond in the phenyl group directly above the 1,4-DHP ring
[C17—C18 in compounds (I) and (II), and C17—C22 in
compound (III)]. The N1ꢄ ꢄ ꢄC4—C17—C18 pseudo-torsion
angles are ꢂ6.75 (19) and 7.14 (17)ꢁ for (I) and (II), respec-
tively. The corresponding pseudo-torsion angles in (III) show
an even more orthogonal configuration, as the values are
ꢂ2.0 (3) and ꢂ3.3 (3)ꢁ for (IIIA) and (IIIB), respectively. The
ortho-bromo group is placed in a synperiplanar orientation
with respect to the C4—H bond. Such an orientation has been
observed in other ortho-substituted phenyl rings in 4-aryl-1,4-
DHP compounds (Linden et al., 2004). It is worth noting that,
although meta-NO2 substitution has been reported to be
synperiplanar to the H atom on C4 (Morales et al., 1996), the
meta-Br in (II) is in an antiperiplanar position. As in other
reported ortho-substituted structures, compound (III) has the
Br pointing away from the 1,4-DHP ring.
˚
0.365 (2), 0.207 (4) and 0.336 (4) A for (I), (II), (IIIA) and
(IIIB), respectively. The sum of the absolute values of the
internal ring torsion angles is also considered a quantitative
measure of the ‘flatness’ of the 1,4-DHP ring (Rowan & Holt,
1995). A flattened or unpuckered ring shows a sum of 0 and
240ꢁ for an ideal boat conformation of the ring (Triggle et al.,
1989). Here, this sum is 67.7 (9)ꢁ for (I), 104.3 (5)ꢁ for (II),
55.8 (9)ꢁ for (IIIA) and 96.5 (8)ꢁ for (IIIB), indicating flat-
tened boat conformations, compared with a sum of 72ꢁ for
nifedipine, the known standard for 1,4-DHPs.
The relationship between the 1,4-DHP pyridine ring and
the aryl group attached at the C4 position is another key factor
in the 1,4-DHP structure–activity relationship. It has been
reported that the pseudo-axial position of the aryl ring is
essential for pharmacological activity (Langs et al., 1987). In
the title compounds, the bromophenyl rings are almost
orthogonal to the base of the 1,4-DHP ring defined by atoms
C2, C3, C10 and C9, with dihedral angles between the mean
planes (plane C2/C3/C10/C9 to plane C17–C22) of 86.32 (8),
Due to the electron delocalization of the conjugate system,
each ester group is coplanar with the mean plane of the 1,4-
DHP ring and at a cis orientation to the adjacent endocyclic
double bond. The planarity extends out through the ester
chains in (I) and (II). However, in (III), because of the
ꢀ
Acta Cryst. (2014). C70, 790–795
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Three homologues of C21H24BrNO3 793

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Table 4
Hydrogen-bond geometry (A, ) for (III).
ꢁ
˚
D—Hꢄ ꢄ ꢄA
D—H
Hꢄ ꢄ ꢄA
Dꢄ ꢄ ꢄA
D—Hꢄ ꢄ ꢄA
N1B—H1Bꢄ ꢄ ꢄO1Ai
0.80 (3)
0.83 (3)
2.02 (3)
2.07 (3)
2.818 (3)
2.884 (3)
174 (3)
165 (2)
N1A—H1Aꢄ ꢄ ꢄO1Bii
1
2
1
2
1
2
1
2
Symmetry codes: (i) ꢂx þ 1; y ꢂ ; ꢂz þ ; (ii) ꢂx; y þ ; ꢂz þ .
of halogen bond range. However, the Brꢄ ꢄ ꢄO distance is
iii
3.1976 (18) A in (I), with C20—Br1ꢄ ꢄ ꢄO2 = 152.24 (9)ꢁ and
˚
Br1ꢄ ꢄ ꢄO2iii—C14iii = 111.06 (15)ꢁ, while in (III), Br1Aꢄ ꢄ ꢄO2B =
˚
Figure 6
3.1764 (18) A and the angles are Br1Aꢄ ꢄ ꢄO2B—C14B =
106.79 (16)ꢁ and C18A—Br1Aꢄ ꢄ ꢄO2B = 160.65 (8)ꢁ [symmetry
Part of the crystal structure of (III), showing the formation of chains of
molecules running along the a axis. Hydrogen bonds are indicated by
dashed lines. For the sake of clarity, H atoms not involved in hydrogen
bonding have been omitted.
codes: (ii) ꢂx + 32, y ꢂ , z; (iii) x ꢂ , ꢂy + 21, ꢂz + 1]. These
1
1
2
2
values are within the range for halogen bonds. Halogen
bonding has been known for decades and has been found in
biological systems, where the halogen acts as a Lewis acid and
the interacting atom can be any electron-donating entity. For
example, in addition to the backbone carbonyl O atom as the
most prominent Lewis base involved in halogen bonds,
hydroxy and carboxyl substituents in the side-chain groups can
also form halogen bonds in protein-binding sites (Wilcken et
al., 2013). The possibility of halogen bonding from Br in these
three compounds needs to be considered during the study of
their structure–activity relationships.
different packing pattern, the end methyl group in (IIIA) is
curled up in the direction of the aryl group. As a result, it
pushes the aryl group slightly away from the orthogonal
position, thus making the dihedral angle between the 1,4-DHP
ring and the aryl ring the most strongly deviating from 90ꢁ:
99.37 (8)ꢁ in (IIIA) versus 89.36 (9)ꢁ in (IIIB).
Again, Cremer & Pople’s ring puckering parameters can be
used to quantify the conformations of the fused cyclo-
hexanone rings. In all three compounds, the cyclohexanone
rings adopt the envelope conformation, which ideally would
have ꢆ = 54.7ꢁ (or ꢆ = 125.3ꢁ in the case of an absolute
configuration change) and ’ = n ꢃ 60ꢁ. For (I), the puckering
In all three compounds, hydrogen bonds are formed
between the N—H group of one molecule and the carbonyl O
atom in the cyclohexanone ring of another molecule (Tables 2,
3 and 4). These hydrogen bonds link the molecules into
extended chains running along the c axis in both (I) and (II),
but along the a axis in (III) (Figs. 4, 5 and 6). In compound (I),
ꢁ
˚
parameters are Q = 0.447 (3) A, ꢆ = 57.4 (4) and ’ =
178.6 (4)ꢁ for the atom sequence C5–C10. For the same atom
sequence in (II), (IIIA) and (IIIB), the corresponding puck-
ꢂ3
˚
˚
the largest difference hole of ꢂ1.21 e A , which is 0.68 A
from atom Br1, may indicate a slight disorder of the Br atom.
In conclusion, the structures reported here demonstrate
that the usually observed conformational features have been
conserved in cyclohexanone-fused 1,4-DHP derivatives. As a
promising base structure for calcium-channel antagonists,
different substitutions and more structural modifications are
being carried out in our group; progress will be reported in
due course.
ꢁ
˚
ering parameters are Q = 0.4595 (18) A, ꢆ = 59.4 (2ꢁ) and ’ =
ꢁ
˚
122.0 (3) for (II), Q = 0.462 (3) A, ꢆ = 122.5 (4) and ’ =
ꢁ
ꢁ
˚
2.9 (4) for (IIIA), and Q = 0.477 (3) A, ꢆ = 59.4 (4) and ’ =
183.4 (4)ꢁ for (IIIB). All these parameters are very close to
those of the ideal envelope conformation. Because of the
almost perfect envelope conformation, atom C7 stands out
from the plane formed by the rest of the atoms in the ring and
lies on the same side of the ring plane as the C4-aryl ring. It is
also interesting that the axial methyl group on C7 is almost
synperiplanar to the bond that connects atom C4 to the aryl
ring. The relationship can be shown by the C11—C7ꢄ ꢄ ꢄC4—
C17 pseudo-torsion angle, which is 13.86 (17)ꢁ for (I),
4.51 (13)ꢁ for (II), ꢂ16.2 (2)ꢁ for (IIIA) and 5.5 (2)ꢁ for (IIIB).
One feature which has not been reported previously for this
type of structure is intermolecular halogen bonding between
Br and the ester carbonyl O atom. A halogen bond is defined
as a short C—Xꢄ ꢄ ꢄO—Y interaction, where the Xꢄ ꢄ ꢄO
distance is less than or equal to the sums of the respective van
SS, CL and NRN thank the National Institutes of Health for
grants NINDS P20RR015583 Center for Structural and
Functional Neuroscience (CSFN) and P20RR017670 Center
for Environmental Health Sciences (CEHS). NRN also thanks
the University of Montana Grant Program (NN).
Supporting information for this paper is available from the IUCr
electronic archives (Reference: SF3233).
˚
der Waals radii (3.37 A for Brꢄ ꢄ ꢄO), with the C—Xꢄ ꢄ ꢄO angle
References
’ 165ꢁ and the Xꢄ ꢄ ꢄO—Yangle ’ 120ꢁ (Auffinger et al., 2004).
Auffinger, P., Hays, F. A., Westhof, E. & Ho, P. S. (2004). Proc. Natl Acad. Sci.
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Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann,
H. (2009). J. Appl. Cryst. 42, 339–341.
˚
Although (II) has an Xꢄ ꢄ ꢄO distance of 3.4837 (14) A, which is
only slightly longer than the sum of the van der Waals radii,
the angles of 166.17 (13)ꢁ for Br1ꢄ ꢄ ꢄO2—C14ii and 77.24 (6)ꢁ
for C19—Br1ꢄ ꢄ ꢄO2ii are out of the range for halogen bonds.
˚
Also in (III), the distance of Br1Bꢄ ꢄ ꢄO2A at 4.048 (2) A is out
ꢀ
794 Steiger et al.
Three homologues of C21H24BrNO3
Acta Cryst. (2014). C70, 790–795

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ꢀ
Acta Cryst. (2014). C70, 790–795
Steiger et al.
Three homologues of C21H24BrNO3 795

supporting information
supporting information
Acta Cryst. (2014). C70, 790-795 [doi:10.1107/S2053229614015617]
The effect of bromine scanning around the phenyl group of 4-phenylquinolone
derivatives
Scott A. Steiger, Anthony J. Monacelli, Chun Li, Janet L. Hunting and Nicholas R. Natale
Computing details
For all compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction:
SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare
material for publication: OLEX2 (Dolomanov et al., 2009).
(I) Ethyl 4-(4-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate
Crystal data
C21H24BrNO3
Dx = 1.400 Mg m−3
Mr = 418.32
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9956 reflections
θ = 2.3–27.5°
Orthorhombic, Pbcn
a = 18.0371 (4) Å
b = 15.4309 (3) Å
c = 14.2604 (3) Å
V = 3969.08 (14) Å3
Z = 8
µ = 2.09 mm−1
T = 100 K
Prism, light yellow
0.26 × 0.18 × 0.13 mm
F(000) = 1728
Data collection
Bruker SMART BREEZE CCD area-detector
diffractometer
Radiation source: 2 kW sealed X-ray tube
φ and ω scans
4558 independent reflections
3391 reflections with I > 2σ(I)
Rint = 0.038
θ
max = 27.5°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = −19→23
k = −20→19
l = −18→18
T
min = 0.909, Tmax = 1.000
35271 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.042
wR(F2) = 0.101
S = 1.04
4558 reflections
243 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Hydrogen site location: mixed
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0386P)2 + 5.4149P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 1.49 e Å−3
Δρmin = −1.21 e Å−3
Acta Cryst. (2014). C70, 790-795
sup-1

supporting information
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Br1
0.01835 (2)
0.39646 (10)
0.35587 (10)
0.34556 (10)
0.39491 (12)
0.4013 (16)
0.38319 (14)
0.36618 (13)
0.35425 (13)
0.3808
0.08589 (2)
−0.02836 (11)
0.33300 (11)
0.27791 (11)
0.07392 (13)
0.0634 (19)
0.15957 (16)
0.17953 (15)
0.10862 (15)
0.1260
0.60206 (2)
0.63323 (11)
0.41638 (12)
0.56159 (11)
0.32412 (14)
0.264 (2)
0.35057 (16)
0.44025 (16)
0.51345 (15)
0.5721
0.03911 (12)
0.0200 (4)
0.0213 (4)
0.0213 (4)
0.0190 (5)
0.027 (8)*
0.0178 (5)
0.0148 (5)
0.0137 (5)
0.016*
O1
O2
O3
N1
H1
C2
C3
C4
H4
C5
0.40247 (13)
0.43032 (14)
0.4101
−0.04303 (16)
−0.13027 (15)
−0.1757
0.54818 (16)
0.51443 (16)
0.5562
0.0145 (5)
0.0158 (5)
0.019*
C6
H6A
H6B
C7
0.4850
−0.1314
0.5207
0.019*
0.41033 (14)
0.42990 (14)
0.4845
−0.15326 (16)
−0.07570 (15)
−0.0721
0.41315 (15)
0.35066 (16)
0.3445
0.0149 (5)
0.0158 (5)
0.019*
C8
H8A
H8B
C9
0.4090
−0.0854
0.2873
0.019*
0.40135 (13)
0.38685 (13)
0.32747 (14)
0.2985
0.00865 (15)
0.02328 (15)
−0.17399 (17)
−0.1230
0.38786 (15)
0.47985 (15)
0.40568 (17)
0.4240
0.0140 (5)
0.0132 (5)
0.0203 (5)
0.030*
C10
C11
H11A
H11B
H11C
C12
H12A
H12B
H12C
C13
H13A
H13B
H13C
C14
C15
H15A
H15B
C16
H16A
H16B
0.3154
−0.2225
0.4474
0.030*
0.3154
−0.1898
0.3409
0.030*
0.45589 (15)
0.4444
−0.23200 (16)
−0.2455
0.38188 (17)
0.3163
0.0210 (5)
0.031*
0.4435
−0.2819
0.4214
0.031*
0.5088
−0.2189
0.3879
0.031*
0.39310 (19)
0.4131
0.22252 (18)
0.1919
0.27089 (17)
0.2163
0.0323 (7)
0.048*
0.4275
0.2684
0.2898
0.048*
0.3451
0.2482
0.2547
0.048*
0.35600 (13)
0.33581 (17)
0.2975
0.27062 (16)
0.36583 (17)
0.3962
0.46787 (17)
0.59609 (18)
0.5588
0.0166 (5)
0.0254 (6)
0.030*
0.3829
0.3984
0.5907
0.030*
0.3126 (3)
0.2656
0.3606 (2)
0.3291
0.6959 (2)
0.7004
0.0582 (12)
0.087*
0.3062
0.4193
0.7210
0.087*
Acta Cryst. (2014). C70, 790-795
sup-2

supporting information
H16C
C17
C18
H18
C19
H19
C20
C21
H21
C22
H22
0.3507
0.3301
0.7321
0.087*
0.27210 (13)
0.22092 (14)
0.2378
0.09825 (14)
0.08222 (16)
0.0755
0.53660 (16)
0.46580 (17)
0.4031
0.0149 (5)
0.0182 (5)
0.022*
0.14545 (15)
0.1109
0.07577 (16)
0.0648
0.48494 (19)
0.4361
0.0226 (6)
0.027*
0.12180 (15)
0.17150 (15)
0.1546
0.08566 (17)
0.09807 (17)
0.1021
0.5767 (2)
0.64941 (19)
0.7123
0.0247 (6)
0.0243 (6)
0.029*
0.24660 (15)
0.2811
0.10459 (16)
0.1135
0.62882 (17)
0.6782
0.0204 (5)
0.025*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Br1
O1
0.02137 (16)
0.0306 (10)
0.0221 (10)
0.0328 (11)
0.0314 (12)
0.0234 (13)
0.0143 (12)
0.0171 (12)
0.0114 (11)
0.0187 (12)
0.0177 (12)
0.0193 (12)
0.0142 (11)
0.0132 (11)
0.0204 (13)
0.0258 (13)
0.062 (2)
0.03688 (19)
0.0199 (10)
0.0143 (9)
0.0591 (2)
0.0094 (7)
0.0274 (9)
0.0194 (8)
0.0098 (9)
0.0166 (11)
0.0179 (11)
0.0113 (10)
0.0156 (11)
0.0150 (11)
0.0134 (11)
0.0135 (11)
0.0143 (11)
0.0146 (11)
0.0217 (12)
0.0219 (12)
0.0159 (12)
0.0214 (12)
0.0250 (13)
0.0365 (18)
0.0178 (11)
0.0183 (11)
0.0310 (14)
0.0403 (15)
0.0248 (13)
0.0185 (11)
−0.00082 (14)
0.0029 (8)
0.01586 (14)
−0.0012 (7)
0.0039 (7)
−0.0009 (8)
0.0002 (8)
−0.0033 (10)
−0.0022 (9)
−0.0005 (9)
−0.0006 (9)
0.0013 (9)
0.0006 (9)
0.0026 (9)
−0.0005 (9)
0.0009 (9)
0.0006 (10)
0.0045 (10)
0.0004 (13)
−0.0014 (9)
0.0002 (12)
0.020 (2)
−0.01140 (15)
0.0007 (7)
O2
0.0020 (8)
0.0039 (8)
O3
0.0115 (9)
0.0013 (8)
−0.0020 (7)
−0.0005 (8)
0.0016 (10)
0.0003 (9)
N1
0.0157 (11)
0.0134 (12)
0.0123 (12)
0.0128 (12)
0.0165 (12)
0.0137 (12)
0.0135 (12)
0.0147 (13)
0.0135 (12)
0.0117 (12)
0.0188 (13)
0.0152 (13)
0.0193 (15)
0.0176 (13)
0.0134 (13)
0.0214 (17)
0.0070 (11)
0.0155 (12)
0.0170 (13)
0.0157 (13)
0.0180 (14)
0.0163 (13)
−0.0012 (9)
−0.0016 (10)
−0.0008 (10)
0.0000 (10)
−0.0018 (10)
0.0020 (10)
−0.0004 (10)
−0.0018 (10)
−0.0022 (10)
−0.0001 (9)
−0.0041 (11)
0.0009 (11)
−0.0038 (14)
−0.0017 (10)
0.0011 (12)
0.014 (2)
C2
C3
C4
0.0009 (9)
C5
0.0013 (10)
0.0004 (9)
C6
C7
−0.0006 (9)
−0.0012 (9)
−0.0002 (9)
0.0000 (9)
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
−0.0036 (11)
−0.0026 (10)
0.0046 (11)
0.0011 (10)
−0.0038 (11)
−0.0008 (15)
−0.0003 (9)
0.0018 (10)
0.0003 (11)
−0.0013 (12)
−0.0039 (11)
−0.0024 (10)
0.0108 (11)
0.0377 (16)
0.117 (4)
0.0198 (12)
0.0209 (13)
0.0197 (13)
0.0180 (13)
0.0300 (15)
0.0265 (14)
0.0016 (10)
0.0025 (11)
0.0018 (11)
0.0010 (11)
0.0016 (11)
0.0021 (11)
0.0031 (9)
0.0014 (10)
−0.0007 (11)
0.0094 (11)
0.0127 (11)
0.0025 (10)
Geometric parameters (Å, º)
Br1—C20
O1—C5
1.901 (3)
C9—C10
1.357 (3)
1.239 (3)
1.211 (3)
1.354 (3)
C11—H11A
C11—H11B
C11—H11C
0.9800
0.9800
0.9800
O2—C14
O3—C14
Acta Cryst. (2014). C70, 790-795
sup-3

supporting information
O3—C15
N1—H1
N1—C2
N1—C9
C2—C3
C2—C13
C3—C4
C3—C14
C4—H4
C4—C10
C4—C17
C5—C6
C5—C10
C6—H6A
C6—H6B
C6—C7
C7—C8
C7—C11
C7—C12
C8—H8A
C8—H8B
C8—C9
1.454 (3)
0.89 (3)
1.391 (3)
1.362 (3)
1.351 (3)
1.505 (3)
1.528 (3)
1.471 (3)
1.0000
C12—H12A
C12—H12B
C12—H12C
C13—H13A
C13—H13B
C13—H13C
C15—H15A
C15—H15B
C15—C16
C16—H16A
C16—H16B
C16—H16C
C17—C18
C17—C22
C18—H18
C18—C19
C19—H19
C19—C20
C20—C21
C21—H21
C21—C22
C22—H22
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9900
0.9900
1.485 (4)
0.9800
1.520 (3)
1.526 (3)
1.515 (3)
1.441 (3)
0.9900
0.9800
0.9800
1.390 (3)
1.397 (3)
0.9500
0.9900
1.530 (3)
1.533 (3)
1.532 (3)
1.533 (3)
0.9900
1.392 (4)
0.9500
1.385 (4)
1.384 (4)
0.9500
0.9900
1.390 (4)
0.9500
1.497 (3)
C14—O3—C15
C2—N1—H1
C9—N1—H1
C9—N1—C2
N1—C2—C13
C3—C2—N1
C3—C2—C13
C2—C3—C4
C2—C3—C14
C14—C3—C4
C3—C4—H4
C10—C4—C3
C10—C4—H4
C10—C4—C17
C17—C4—C3
C17—C4—H4
O1—C5—C6
O1—C5—C10
C10—C5—C6
C5—C6—H6A
C5—C6—H6B
C5—C6—C7
H6A—C6—H6B
C7—C6—H6A
C7—C6—H6B
115.35 (19)
117.3 (19)
120.2 (19)
122.3 (2)
113.0 (2)
120.5 (2)
126.5 (2)
121.0 (2)
120.0 (2)
118.9 (2)
108.1
H11A—C11—H11C
H11B—C11—H11C
C7—C12—H12A
C7—C12—H12B
C7—C12—H12C
H12A—C12—H12B
H12A—C12—H12C
H12B—C12—H12C
C2—C13—H13A
C2—C13—H13B
C2—C13—H13C
H13A—C13—H13B
H13A—C13—H13C
H13B—C13—H13C
O2—C14—O3
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
122.2 (2)
126.7 (2)
111.2 (2)
110.1
110.53 (18)
108.1
110.66 (19)
111.08 (19)
108.1
O2—C14—C3
120.2 (2)
121.0 (2)
118.74 (19)
108.4
O3—C14—C3
O3—C15—H15A
O3—C15—H15B
O3—C15—C16
110.1
107.9 (2)
108.4
110.1
108.4
H15A—C15—H15B
C16—C15—H15A
C16—C15—H15B
C15—C16—H16A
C15—C16—H16B
115.32 (19)
107.5
110.1
108.4
109.5
109.5
108.4
Acta Cryst. (2014). C70, 790-795
sup-4

supporting information
C6—C7—C8
108.26 (19)
110.12 (19)
109.4 (2)
110.3 (2)
109.7 (2)
109.03 (19)
108.9
C15—C16—H16C
H16A—C16—H16B
H16A—C16—H16C
H16B—C16—H16C
C18—C17—C4
109.5
C6—C7—C11
C6—C7—C12
C11—C7—C8
C11—C7—C12
C12—C7—C8
C7—C8—H8A
C7—C8—H8B
H8A—C8—H8B
C9—C8—C7
109.5
109.5
109.5
120.4 (2)
118.5 (2)
121.1 (2)
119.3
C18—C17—C22
C22—C17—C4
108.9
C17—C18—H18
C17—C18—C19
C19—C18—H18
C18—C19—H19
C20—C19—C18
C20—C19—H19
C19—C20—Br1
C21—C20—Br1
C21—C20—C19
C20—C21—H21
C20—C21—C22
C22—C21—H21
C17—C22—H22
C21—C22—C17
C21—C22—H22
107.8
121.3 (2)
119.3
113.18 (19)
108.9
C9—C8—H8A
C9—C8—H8B
N1—C9—C8
120.7
108.9
118.6 (2)
120.7
115.85 (19)
120.4 (2)
123.6 (2)
118.5 (2)
121.6 (2)
119.9 (2)
109.5
C10—C9—N1
C10—C9—C8
C5—C10—C4
C9—C10—C4
C9—C10—C5
C7—C11—H11A
C7—C11—H11B
C7—C11—H11C
H11A—C11—H11B
118.8 (2)
119.6 (2)
121.6 (2)
120.5
118.9 (2)
120.5
109.5
119.5
109.5
121.0 (2)
119.5
109.5
Br1—C20—C21—C22
O1—C5—C6—C7
O1—C5—C10—C4
O1—C5—C10—C9
N1—C2—C3—C4
N1—C2—C3—C14
N1—C9—C10—C4
N1—C9—C10—C5
C2—N1—C9—C8
C2—N1—C9—C10
C2—C3—C4—C10
C2—C3—C4—C17
C2—C3—C14—O2
C2—C3—C14—O3
C3—C4—C10—C5
C3—C4—C10—C9
C3—C4—C17—C18
C3—C4—C17—C22
C4—C3—C14—O2
C4—C3—C14—O3
C4—C17—C18—C19
C4—C17—C22—C21
C5—C6—C7—C8
C5—C6—C7—C11
C5—C6—C7—C12
−174.96 (19)
159.3 (2)
−7.0 (3)
C7—C8—C9—N1
C7—C8—C9—C10
C8—C9—C10—C4
C8—C9—C10—C5
C9—N1—C2—C3
C9—N1—C2—C13
−159.3 (2)
24.9 (3)
−176.9 (2)
3.2 (4)
173.0 (2)
−4.1 (4)
−10.4 (4)
168.4 (2)
178.3 (2)
7.5 (4)
C10—C4—C17—C18
C10—C4—C17—C22
C10—C5—C6—C7
C11—C7—C8—C9
C12—C7—C8—C9
C13—C2—C3—C4
C13—C2—C3—C14
C14—O3—C15—C16
C14—C3—C4—C10
C14—C3—C4—C17
C15—O3—C14—O2
C15—O3—C14—C3
C17—C4—C10—C5
C17—C4—C10—C9
C17—C18—C19—C20
C18—C17—C22—C21
C18—C19—C20—Br1
C18—C19—C20—C21
C19—C20—C21—C22
−67.8 (3)
112.2 (2)
−23.8 (3)
72.0 (2)
−172.4 (2)
−167.3 (2)
8.7 (4)
17.6 (3)
−167.4 (2)
177.2 (3)
−0.4 (4)
170.6 (3)
−164.8 (2)
72.0 (3)
−105.7 (3)
5.8 (4)
−174.8 (2)
160.6 (2)
−19.4 (3)
55.4 (3)
−1.3 (3)
179.3 (2)
−75.9 (3)
104.1 (2)
0.0 (4)
−124.6 (2)
−171.8 (2)
7.6 (3)
−177.6 (2)
177.8 (2)
48.7 (3)
−2.2 (4)
175.19 (19)
−2.7 (4)
2.9 (4)
−72.0 (3)
167.4 (2)
Acta Cryst. (2014). C70, 790-795
sup-5

supporting information
C6—C5—C10—C4
C6—C5—C10—C9
C6—C7—C8—C9
176.1 (2)
−3.9 (3)
−48.5 (3)
C20—C21—C22—C17
−0.4 (4)
2.4 (4)
C22—C17—C18—C19
Hydrogen-bond geometry (Å, º)
D—H···A
N1—H1···O1i
D—H
H···A
D···A
D—H···A
168 (3)
0.89 (3)
1.94 (3)
2.812 (2)
Symmetry code: (i) x, −y, z−1/2.
(II) Ethyl 4-(3-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate
Crystal data
C21H24BrNO3
Dx = 1.474 Mg m−3
Mr = 418.32
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9015 reflections
θ = 2.3–29.1°
Orthorhombic, Pbcn
a = 17.0813 (5) Å
b = 15.4877 (5) Å
c = 14.2544 (5) Å
V = 3771.0 (2) Å3
Z = 8
µ = 2.20 mm−1
T = 100 K
Prism, light yellow
0.40 × 0.21 × 0.19 mm
F(000) = 1728
Data collection
Bruker SMART BREEZE CCD area-detector
diffractometer
Radiation source: 2 kW sealed X-ray tube
Graphite monochromator
55070 measured reflections
5055 independent reflections
4278 reflections with I > 2σ(I)
Rint = 0.032
φ and ω scans
θmax = 29.1°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = −23→23
k = −21→21
l = −19→19
T
min = 0.839, Tmax = 1.000
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.032
wR(F2) = 0.084
S = 1.03
Hydrogen site location: mixed
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0428P)2 + 3.6244P]
where P = (Fo2 + 2Fc2)/3
5055 reflections
243 parameters
0 restraints
(Δ/σ)max = 0.002
Δρmax = 1.31 e Å−3
Δρmin = −0.38 e Å−3
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Br1
0.92434 (2)
0.52663 (2)
0.66172 (2)
0.01998 (7)
Acta Cryst. (2014). C70, 790-795
sup-6

supporting information
O1
0.61002 (8)
0.60547 (9)
0.66301 (8)
0.61112 (9)
0.61780 (9)
0.63546 (9)
0.65961 (9)
0.6397
0.46449 (8)
0.83120 (9)
0.77388 (8)
0.58166 (9)
0.66563 (11)
0.67997 (11)
0.60546 (10)
0.6174
0.36349 (9)
0.54611 (11)
0.41978 (10)
0.66708 (10)
0.63433 (12)
0.54285 (12)
0.47927 (11)
0.4146
0.0170 (3)
0.0273 (3)
0.0235 (3)
0.0132 (3)
0.0132 (3)
0.0132 (3)
0.0117 (3)
0.014*
O2
O3
N1
C2
C3
C4
H4
C10
C9
0.62185 (9)
0.60504 (9)
0.57528 (9)
0.5176
0.52300 (10)
0.51293 (10)
0.43036 (11)
0.4335
0.51443 (11)
0.60705 (11)
0.64894 (11)
0.6542
0.0105 (3)
0.0105 (3)
0.0126 (3)
0.015*
C8
H8A
H8B
C7
0.5968
0.4240
0.7130
0.015*
0.59747 (10)
0.57615 (10)
0.5981
0.35080 (10)
0.36838 (11)
0.3214
0.59090 (12)
0.48787 (12)
0.4489
0.0129 (3)
0.0143 (3)
0.017*
C6
H6A
H6B
C5
0.5185
0.3662
0.4816
0.017*
0.60455 (9)
0.68524 (11)
0.6988
0.45362 (11)
0.33164 (12)
0.3228
0.44924 (11)
0.59932 (14)
0.6654
0.0112 (3)
0.0208 (4)
0.031*
C11
H11A
H11B
H11C
C12
H12A
H12B
H12C
C13
H13A
H13B
H13C
C14
C15
H15A
H15B
C16
H16A
H16B
H16C
C17
C18
H18
C19
C20
H20
C21
H21
C22
H22
0.7152
0.3804
0.5743
0.031*
0.6978
0.2794
0.5636
0.031*
0.55061 (12)
0.4946
0.27318 (12)
0.2868
0.62687 (14)
0.6252
0.0217 (4)
0.033*
0.5663
0.2602
0.6915
0.033*
0.5610
0.2230
0.5869
0.033*
0.60140 (11)
0.5964
0.73340 (12)
0.7060
0.70714 (13)
0.7688
0.0193 (4)
0.029*
0.5525
0.7633
0.6916
0.029*
0.6446
0.7751
0.7085
0.029*
0.63211 (10)
0.66536 (13)
0.6813
0.76888 (11)
0.86167 (13)
0.9033
0.50625 (13)
0.38140 (16)
0.4305
0.0172 (3)
0.0281 (4)
0.034*
0.6131
0.8785
0.3577
0.034*
0.72312 (12)
0.7739
0.86129 (14)
0.8415
0.30382 (16)
0.3275
0.0285 (4)
0.043*
0.7285
0.9198
0.2785
0.043*
0.7052
0.8223
0.2541
0.043*
0.74878 (10)
0.78958 (9)
0.7620
0.59554 (10)
0.56824 (11)
0.5547
0.47466 (11)
0.55396 (11)
0.6099
0.0124 (3)
0.0130 (3)
0.016*
0.87044 (10)
0.91306 (10)
0.9685
0.56085 (11)
0.57960 (11)
0.5752
0.55114 (12)
0.47084 (13)
0.4702
0.0137 (3)
0.0161 (3)
0.019*
0.87189 (11)
0.8996
0.60498 (12)
0.6168
0.39144 (13)
0.3351
0.0199 (4)
0.024*
0.79094 (10)
0.7640
0.61342 (12)
0.6315
0.39305 (12)
0.3381
0.0177 (3)
0.021*
Acta Cryst. (2014). C70, 790-795
sup-7

supporting information
H1
0.6037 (14)
0.5739 (15)
0.7262 (18)
0.021 (6)*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Br1
O1
0.01611 (10)
0.0224 (6)
0.0349 (8)
0.0262 (7)
0.0179 (7)
0.0113 (7)
0.0111 (7)
0.0122 (7)
0.0108 (7)
0.0098 (7)
0.0140 (7)
0.0144 (7)
0.0167 (8)
0.0095 (7)
0.0193 (8)
0.0283 (9)
0.0218 (9)
0.0120 (7)
0.0332 (11)
0.0278 (10)
0.0149 (7)
0.0132 (7)
0.0155 (7)
0.0139 (8)
0.0213 (9)
0.0195 (8)
0.02866 (11)
0.0199 (6)
0.0137 (6)
0.0184 (6)
0.0137 (7)
0.0122 (7)
0.0124 (7)
0.0129 (7)
0.0119 (7)
0.0116 (7)
0.0132 (8)
0.0116 (7)
0.0127 (7)
0.0143 (7)
0.0209 (9)
0.0139 (8)
0.0165 (8)
0.0159 (8)
0.0183 (9)
0.0272 (10)
0.0104 (7)
0.0151 (8)
0.0119 (7)
0.0141 (8)
0.0221 (9)
0.0200 (8)
0.01518 (10)
0.0087 (5)
0.0332 (8)
0.0259 (7)
0.0079 (6)
0.0162 (8)
0.0161 (8)
0.0101 (7)
0.0088 (7)
0.0101 (7)
0.0105 (7)
0.0126 (8)
0.0135 (8)
0.0097 (7)
0.0223 (9)
0.0228 (9)
0.0196 (9)
0.0235 (9)
0.0327 (11)
0.0306 (11)
0.0120 (7)
0.0106 (7)
0.0137 (8)
0.0203 (9)
0.0164 (8)
0.0134 (8)
0.00677 (7)
0.0009 (5)
0.0049 (6)
0.0052 (5)
−0.0008 (5)
0.0000 (6)
−0.0007 (6)
−0.0011 (6)
0.0000 (5)
0.0006 (5)
0.0001 (6)
0.0008 (6)
−0.0009 (6)
0.0024 (6)
0.0069 (7)
−0.0023 (7)
0.0005 (7)
−0.0019 (6)
0.0053 (8)
−0.0017 (8)
−0.0011 (6)
−0.0014 (6)
0.0003 (6)
0.0006 (6)
0.0002 (7)
0.0012 (7)
−0.00292 (6)
−0.0005 (5)
0.0042 (6)
0.0088 (6)
0.0009 (5)
−0.0011 (6)
−0.0011 (6)
−0.0003 (6)
−0.0003 (5)
−0.0004 (5)
0.0022 (6)
0.0014 (6)
−0.0002 (6)
−0.0013 (6)
0.0020 (7)
0.0063 (8)
0.0027 (7)
−0.0006 (7)
0.0059 (9)
0.0012 (9)
0.0025 (6)
0.0023 (6)
−0.0016 (6)
0.0040 (6)
0.0084 (7)
0.0033 (6)
−0.00298 (7)
−0.0006 (5)
0.0020 (6)
0.0111 (5)
−0.0009 (5)
−0.0025 (6)
0.0009 (6)
0.0027 (6)
0.0012 (6)
0.0001 (6)
0.0021 (6)
0.0010 (6)
−0.0017 (6)
−0.0011 (6)
0.0047 (7)
0.0020 (7)
−0.0065 (7)
0.0047 (7)
0.0103 (8)
0.0088 (9)
−0.0008 (6)
−0.0019 (6)
−0.0033 (6)
−0.0014 (6)
0.0043 (7)
0.0051 (6)
O2
O3
N1
C2
C3
C4
C10
C9
C8
C7
C6
C5
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
Geometric parameters (Å, º)
Br1—C19
O1—C5
O2—C14
O3—C14
O3—C15
N1—C2
N1—C9
N1—H1
C2—C3
C2—C13
C3—C4
C3—C14
C4—H4
C4—C10
1.9009 (17)
C6—C5
1.510 (2)
1.237 (2)
1.209 (2)
1.343 (2)
1.466 (2)
1.386 (2)
1.370 (2)
0.86 (2)
C11—H11A
C11—H11B
C11—H11C
C12—H12A
C12—H12B
C12—H12C
C13—H13A
C13—H13B
C13—H13C
C15—H15A
C15—H15B
C15—C16
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9900
0.9900
1.482 (3)
0.9800
1.357 (2)
1.502 (2)
1.524 (2)
1.474 (2)
1.0000
1.516 (2)
C16—H16A
Acta Cryst. (2014). C70, 790-795
sup-8

supporting information
C4—C17
C10—C9
C10—C5
C9—C8
1.532 (2)
1.360 (2)
1.451 (2)
1.500 (2)
0.9900
C16—H16B
C16—H16C
C17—C18
C17—C22
C18—H18
C18—C19
C19—C20
C20—H20
C20—C21
C21—H21
C21—C22
C22—H22
0.9800
0.9800
1.394 (2)
1.396 (2)
0.9500
C8—H8A
C8—H8B
C8—C7
0.9900
1.386 (2)
1.387 (2)
0.9500
1.532 (2)
1.537 (2)
1.533 (2)
1.533 (2)
0.9900
C7—C6
C7—C11
C7—C12
C6—H6A
C6—H6B
1.389 (3)
0.9500
1.389 (3)
0.9500
0.9900
C14—O3—C15
C2—N1—H1
C9—N1—C2
C9—N1—H1
N1—C2—C13
C3—C2—N1
C3—C2—C13
C2—C3—C4
C2—C3—C14
C14—C3—C4
C3—C4—H4
C3—C4—C17
C10—C4—C3
C10—C4—H4
C10—C4—C17
C17—C4—H4
C9—C10—C4
C9—C10—C5
C5—C10—C4
N1—C9—C8
C10—C9—N1
C10—C9—C8
C9—C8—H8A
C9—C8—H8B
C9—C8—C7
H8A—C8—H8B
C7—C8—H8A
C7—C8—H8B
C8—C7—C6
C8—C7—C11
C8—C7—C12
C11—C7—C6
C12—C7—C6
C12—C7—C11
C7—C6—H6A
113.99 (15)
118.2 (16)
121.67 (14)
119.5 (16)
114.04 (15)
119.69 (15)
126.23 (16)
120.52 (15)
118.99 (16)
120.49 (15)
108.4
H11A—C11—H11C
H11B—C11—H11C
C7—C12—H12A
C7—C12—H12B
C7—C12—H12C
H12A—C12—H12B
H12A—C12—H12C
H12B—C12—H12C
C2—C13—H13A
C2—C13—H13B
C2—C13—H13C
H13A—C13—H13B
H13A—C13—H13C
H13B—C13—H13C
O2—C14—O3
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
111.75 (13)
109.02 (13)
108.4
109.5
109.5
109.5
110.65 (13)
108.4
122.23 (16)
126.45 (17)
111.32 (15)
110.3
O2—C14—C3
120.49 (14)
119.58 (14)
119.92 (14)
116.08 (14)
120.08 (15)
123.76 (15)
109.0
O3—C14—C3
O3—C15—H15A
O3—C15—H15B
O3—C15—C16
110.3
107.04 (16)
108.6
H15A—C15—H15B
C16—C15—H15A
C16—C15—H15B
C15—C16—H16A
C15—C16—H16B
C15—C16—H16C
H16A—C16—H16B
H16A—C16—H16C
H16B—C16—H16C
C18—C17—C4
110.3
110.3
109.0
109.5
112.76 (13)
107.8
109.5
109.5
109.0
109.5
109.0
109.5
108.35 (13)
110.82 (14)
108.72 (14)
109.92 (14)
109.56 (14)
109.43 (14)
108.5
109.5
119.53 (14)
118.56 (15)
121.91 (15)
120.0
C18—C17—C22
C22—C17—C4
C17—C18—H18
C19—C18—C17
C19—C18—H18
119.98 (15)
120.0
Acta Cryst. (2014). C70, 790-795
sup-9

supporting information
C7—C6—H6B
H6A—C6—H6B
C5—C6—C7
108.5
C18—C19—Br1
C18—C19—C20
C20—C19—Br1
C19—C20—H20
C19—C20—C21
C21—C20—H20
C20—C21—H21
C22—C21—C20
C22—C21—H21
C17—C22—H22
C21—C22—C17
C21—C22—H22
118.78 (13)
121.97 (16)
119.24 (13)
121.1
107.5
115.28 (14)
108.5
C5—C6—H6A
C5—C6—H6B
O1—C5—C10
O1—C5—C6
108.5
117.76 (16)
121.1
121.10 (15)
120.22 (15)
118.63 (14)
109.5
119.4
C10—C5—C6
C7—C11—H11A
C7—C11—H11B
C7—C11—H11C
H11A—C11—H11B
121.13 (16)
119.4
109.5
119.7
109.5
120.58 (17)
119.7
109.5
Br1—C19—C20—C21
N1—C2—C3—C4
N1—C2—C3—C14
N1—C9—C8—C7
C2—N1—C9—C10
C2—N1—C9—C8
C2—C3—C4—C10
C2—C3—C4—C17
C2—C3—C14—O2
C2—C3—C14—O3
C3—C4—C10—C9
C3—C4—C10—C5
C3—C4—C17—C18
C3—C4—C17—C22
C4—C3—C14—O2
C4—C3—C14—O3
C4—C10—C9—N1
C4—C10—C9—C8
C4—C10—C5—O1
C4—C10—C5—C6
C4—C17—C18—C19
C4—C17—C22—C21
C10—C4—C17—C18
C10—C4—C17—C22
C10—C9—C8—C7
C9—N1—C2—C3
C9—N1—C2—C13
C9—C10—C5—O1
−179.58 (13)
−8.9 (2)
C9—C10—C5—C6
C9—C8—C7—C6
C9—C8—C7—C11
C9—C8—C7—C12
C8—C7—C6—C5
C7—C6—C5—O1
C7—C6—C5—C10
C5—C10—C9—N1
C5—C10—C9—C8
C11—C7—C6—C5
C12—C7—C6—C5
C13—C2—C3—C4
C13—C2—C3—C14
−6.4 (2)
−49.12 (18)
71.56 (18)
−168.13 (14)
49.17 (18)
160.14 (15)
−22.5 (2)
171.99 (15)
−159.09 (14)
13.9 (2)
−162.93 (14)
28.5 (2)
−94.13 (18)
−10.1 (3)
−171.17 (14)
5.4 (2)
170.08 (15)
−28.9 (2)
−72.07 (18)
167.65 (14)
173.19 (16)
−5.9 (3)
152.04 (14)
68.23 (19)
−111.52 (18)
170.86 (17)
−9.0 (2)
C14—O3—C15—C16
C14—C3—C4—C10
C14—C3—C4—C17
C15—O3—C14—O2
C15—O3—C14—C3
C17—C4—C10—C9
C17—C4—C10—C5
C17—C18—C19—Br1
C17—C18—C19—C20
C18—C17—C22—C21
C18—C19—C20—C21
C19—C20—C21—C22
C20—C21—C22—C17
C22—C17—C18—C19
161.23 (17)
−152.46 (14)
84.92 (18)
3.3 (3)
9.8 (2)
−173.61 (14)
−10.0 (2)
−176.83 (15)
94.34 (18)
−84.68 (17)
178.21 (12)
−0.3 (3)
172.64 (14)
−178.60 (15)
179.09 (16)
−53.5 (2)
−0.7 (3)
126.79 (17)
24.2 (2)
−1.1 (3)
1.6 (3)
−14.3 (2)
−0.7 (3)
163.81 (15)
170.98 (16)
1.1 (2)
Hydrogen-bond geometry (Å, º)
D—H···A
N1—H1···O1i
D—H
0.86 (2)
H···A
D···A
D—H···A
166 (2)
2.05 (2)
2.8896 (19)
Symmetry code: (i) x, −y+1, z+1/2.
Acta Cryst. (2014). C70, 790-795
sup-10

supporting information
(III) Ethyl 4-(2-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate
Crystal data
C21H24BrNO3
Mr = 418.32
F(000) = 1728
Dx = 1.445 Mg m−3
Monoclinic, P21/c
a = 14.5012 (18) Å
b = 18.299 (2) Å
c = 15.1952 (19) Å
β = 107.5262 (15)°
V = 3844.9 (8) Å3
Z = 8
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9934 reflections
θ = 2.2–27.7°
µ = 2.16 mm−1
T = 100 K
Prism, translucent yellow
0.34 × 0.16 × 0.08 mm
Data collection
Bruker SMART BREEZE CCD area-detector
diffractometer
Radiation source: 2 kW sealed X-ray tube
φ and ω scans
8935 independent reflections
6859 reflections with I > 2σ(I)
Rint = 0.065
θ
max = 27.7°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = −18→18
k = −23→23
l = −19→19
T
min = 0.866, Tmax = 1.000
45465 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.036
wR(F2) = 0.081
S = 1.02
8935 reflections
485 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Hydrogen site location: mixed
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0324P)2 + 2.2792P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 1.46 e Å−3
Δρmin = −0.47 e Å−3
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Br1A
O1A
O2A
O3A
N1A
C2A
C3A
C4A
H4A
0.39565 (2)
0.28043 (11)
0.04711 (13)
0.20232 (12)
−0.01715 (15)
0.00080 (17)
0.08940 (16)
0.17328 (16)
0.2055
0.30789 (2)
0.45760 (9)
0.20468 (10)
0.23877 (9)
0.42917 (11)
0.35786 (13)
0.32797 (13)
0.37166 (13)
0.3416
0.25454 (2)
0.12019 (11)
0.24987 (15)
0.29061 (12)
0.17929 (14)
0.21030 (16)
0.22333 (16)
0.20857 (16)
0.1714
0.01430 (7)
0.0122 (4)
0.0262 (5)
0.0148 (4)
0.0110 (4)
0.0117 (5)
0.0100 (5)
0.0096 (5)
0.012*
Acta Cryst. (2014). C70, 790-795
sup-11

supporting information
C10A
C9A
0.13654 (16)
0.04751 (17)
0.01507 (17)
−0.0255
0.44210 (13)
0.46991 (13)
0.54547 (13)
0.5659
0.15653 (16)
0.15143 (16)
0.11637 (17)
0.1524
0.0094 (5)
0.0099 (5)
0.0113 (5)
0.014*
C8A
H8AA
H8AB
C7A
−0.0254
0.5422
0.0511
0.014*
0.10023 (17)
0.17181 (17)
0.1422
0.59772 (13)
0.55891 (13)
0.5549
0.12310 (17)
0.08212 (16)
0.0145
0.0114 (5)
0.0111 (5)
0.013*
C6A
H6AA
H6AB
C5A
0.2305
0.5895
0.0934
0.013*
0.20149 (17)
0.15088 (18)
0.1035
0.48342 (13)
0.61815 (14)
0.6387
0.12076 (16)
0.22402 (17)
0.2515
0.0104 (5)
0.0160 (5)
0.024*
C11A
H11A
H11B
H11C
C12A
H12A
H12B
H12C
C13A
H13A
H13B
H13C
C14A
C15A
H15A
H15B
C16A
H16A
H16B
H16C
C17A
C18A
C19A
H19A
C20A
H20A
C21A
H21A
C22A
H22A
Br1B
O1B
0.2014
0.6544
0.2267
0.024*
0.1801
0.5744
0.2584
0.024*
0.06180 (18)
0.0299
0.66689 (14)
0.6541
0.06839 (18)
0.0037
0.0168 (6)
0.025*
0.1156
0.7003
0.0720
0.025*
0.0152
0.6907
0.0942
0.025*
−0.08558 (18)
−0.1282
0.32166 (14)
0.3590
0.22696 (19)
0.2398
0.0171 (6)
0.026*
−0.0639
0.2885
0.2799
0.026*
−0.1209
0.2938
0.1720
0.026*
0.10710 (17)
0.23069 (18)
0.2953
0.25154 (14)
0.16497 (13)
0.1544
0.25480 (17)
0.32241 (18)
0.3160
0.0133 (5)
0.0155 (5)
0.019*
0.1841
0.1298
0.2833
0.019*
0.2338 (2)
0.1693
0.15485 (15)
0.1633
0.42185 (18)
0.4279
0.0205 (6)
0.031*
0.2796
0.1898
0.4607
0.031*
0.2547
0.1049
0.4415
0.031*
0.24881 (17)
0.34612 (17)
0.41183 (18)
0.4777
0.39335 (13)
0.37375 (14)
0.40080 (14)
0.3862
0.29969 (16)
0.32615 (16)
0.40664 (17)
0.4236
0.0099 (5)
0.0129 (5)
0.0155 (5)
0.019*
0.38027 (19)
0.4250
0.44895 (15)
0.4683
0.46146 (17)
0.5156
0.0181 (6)
0.022*
0.28354 (19)
0.2619
0.46919 (14)
0.5022
0.43783 (17)
0.4757
0.0167 (6)
0.020*
0.21920 (18)
0.1529
0.44091 (13)
0.4540
0.35874 (17)
0.3437
0.0142 (5)
0.017*
0.08223 (2)
0.21907 (11)
0.41353 (12)
0.26479 (11)
0.51999 (15)
0.48978 (17)
0.39436 (17)
0.31871 (16)
0.00989 (2)
−0.03473 (9)
0.16979 (9)
0.12336 (9)
−0.01424 (12)
0.04219 (13)
0.05815 (13)
0.01002 (13)
0.13780 (2)
0.35984 (12)
0.13408 (12)
0.11364 (11)
0.30637 (14)
0.24329 (16)
0.21022 (16)
0.23282 (16)
0.01685 (7)
0.0139 (4)
0.0158 (4)
0.0130 (4)
0.0116 (4)
0.0104 (5)
0.0094 (5)
0.0090 (5)
O2B
O3B
N1B
C2B
C3B
C4B
Acta Cryst. (2014). C70, 790-795
sup-12

supporting information
H4B
0.2658
0.0421
0.2405
0.011*
C10B
C9B
0.36467 (16)
0.46114 (17)
0.50953 (17)
0.5407
−0.02951 (13)
−0.04440 (13)
−0.09235 (13)
−0.0612
0.32331 (16)
0.35161 (16)
0.43263 (16)
0.4867
0.0090 (5)
0.0096 (5)
0.0114 (5)
0.014*
C8B
H8BA
H8BB
C7B
0.5607
−0.1214
0.4182
0.014*
0.43782 (17)
0.35073 (17)
0.3012
−0.14455 (13)
−0.09960 (13)
−0.1333
0.45732 (16)
0.46295 (16)
0.4724
0.0117 (5)
0.0109 (5)
0.013*
C6B
H6BA
H6BB
C5B
0.3715
−0.0673
0.5176
0.013*
0.30492 (17)
0.48777 (19)
0.5411
−0.05315 (13)
−0.17893 (15)
−0.2101
0.37865 (16)
0.55204 (18)
0.5476
0.0110 (5)
0.0182 (6)
0.027*
C12B
H12D
H12E
H12F
C11B
H11D
H11E
H11F
C13B
H13D
H13E
H13F
C14B
C15B
H15C
H15D
C16B
H16D
H16E
H16F
C17B
C18B
C19B
H19B
C20B
H20B
C21B
H21B
C22B
H22B
H1B
0.4409
−0.2084
0.5715
0.027*
0.5131
−0.1402
0.5974
0.027*
0.40569 (19)
0.3742
−0.20507 (14)
−0.1832
0.38480 (18)
0.3243
0.0165 (6)
0.025*
0.3601
−0.2376
0.4017
0.025*
0.4623
−0.2332
0.3820
0.025*
0.57203 (17)
0.5937
0.07931 (14)
0.1214
0.22026 (18)
0.2611
0.0155 (5)
0.023*
0.5504
0.0959
0.1559
0.023*
0.6257
0.0448
0.2287
0.023*
0.36205 (17)
0.22766 (18)
0.2565
0.12248 (13)
0.18339 (14)
0.1822
0.15021 (16)
0.05020 (18)
−0.0011
0.0112 (5)
0.0164 (6)
0.020*
0.2440
0.2307
0.0827
0.020*
0.11964 (19)
0.0924
0.17455 (16)
0.2141
0.0134 (2)
−0.0301
0.0240 (6)
0.036*
0.0918
0.1763
0.0647
0.036*
0.1043
0.1274
−0.0183
0.036*
0.27431 (17)
0.17577 (17)
0.13963 (19)
0.0721
−0.04582 (13)
−0.05192 (14)
−0.10322 (15)
−0.1060
0.15652 (16)
0.10999 (17)
0.04075 (18)
0.0103
0.0107 (5)
0.0128 (5)
0.0196 (6)
0.023*
0.2024 (2)
0.1784
−0.15016 (15)
−0.1847
0.01647 (19)
−0.0317
0.0233 (6)
0.028*
0.3010 (2)
0.3444
−0.14683 (15)
−0.1797
0.06268 (18)
0.0471
0.0200 (6)
0.024*
0.33544 (18)
0.4029
−0.09546 (13)
−0.0937
0.13130 (17)
0.1625
0.0136 (5)
0.016*
0.576 (2)
−0.0714 (19)
−0.0236 (14)
0.4467 (14)
0.3237 (18)
0.1738 (17)
0.011 (7)*
0.006 (7)*
H1A
Atomic displacement parameters (Å2)
U11
U22
0.01685 (13)
U33
U12
U13
U23
Br1A
0.01041 (12)
0.01641 (13)
0.00394 (10)
0.00521 (10)
0.00192 (10)
Acta Cryst. (2014). C70, 790-795
sup-13

supporting information
O1A
O2A
O3A
N1A
C2A
0.0075 (8)
0.0155 (9)
0.0138 (9)
−0.0009 (7)
−0.0007 (8)
0.0021 (7)
0.0033 (7)
0.0070 (9)
0.0019 (7)
0.0054 (8)
0.0031 (10)
0.0021 (9)
0.0024 (9)
0.0012 (9)
0.0013 (9)
0.0044 (10)
0.0041 (10)
0.0049 (10)
0.0004 (9)
0.0040 (11)
0.0069 (11)
0.0092 (11)
0.0063 (10)
0.0044 (11)
0.0052 (12)
0.0036 (9)
0.0062 (10)
0.0017 (10)
0.0028 (11)
0.0069 (11)
0.0038 (10)
0.00179 (9)
0.0046 (7)
0.0071 (8)
0.0014 (7)
0.0031 (8)
0.0049 (10)
0.0010 (9)
0.0018 (9)
0.0023 (9)
0.0040 (9)
0.0034 (10)
0.0036 (10)
0.0043 (10)
0.0022 (9)
0.0052 (11)
0.0057 (11)
0.0070 (10)
0.0041 (9)
0.0035 (11)
0.0016 (12)
0.0033 (10)
0.0041 (10)
−0.0005 (11)
−0.0011 (7)
0.0065 (9)
0.0129 (10)
0.0091 (8)
0.0128 (10)
0.0111 (9)
0.0512 (14)
0.0223 (10)
0.0156 (11)
0.0102 (12)
0.0113 (12)
0.0100 (11)
0.0080 (11)
0.0068 (11)
0.0134 (12)
0.0147 (13)
0.0118 (12)
0.0067 (11)
0.0193 (14)
0.0230 (14)
0.0261 (15)
0.0173 (13)
0.0257 (15)
0.0209 (15)
0.0094 (12)
0.0123 (12)
0.0133 (13)
0.0092 (12)
0.0111 (13)
0.0145 (13)
0.01687 (13)
0.0172 (9)
0.0042 (7)
0.0059 (10)
0.0118 (12)
0.0080 (11)
0.0079 (11)
0.0079 (11)
0.0096 (11)
0.0088 (12)
0.0093 (12)
0.0125 (12)
0.0083 (11)
0.0143 (13)
0.0154 (13)
0.0121 (13)
0.0087 (12)
0.0124 (12)
0.0233 (15)
0.0123 (12)
0.0135 (12)
0.0103 (12)
0.0200 (14)
0.0222 (14)
0.0152 (13)
0.00708 (12)
0.0066 (8)
0.0129 (11)
0.0130 (13)
0.0102 (12)
0.0107 (12)
0.0115 (12)
0.0125 (12)
0.0124 (13)
0.0105 (12)
0.0100 (12)
0.0148 (13)
0.0136 (13)
0.0129 (13)
0.0152 (14)
0.0153 (13)
0.0077 (12)
0.0165 (14)
0.0083 (12)
0.0143 (13)
0.0217 (14)
0.0240 (15)
0.0181 (14)
0.0125 (13)
0.02538 (15)
0.0185 (10)
0.0108 (9)
0.0031 (9)
0.0037 (9)
−0.0011 (10)
−0.0009 (9)
0.0023 (9)
0.0002 (10)
−0.0012 (9)
−0.0006 (10)
−0.0011 (9)
−0.0010 (9)
0.0008 (10)
0.0012 (10)
0.0004 (10)
−0.0027 (10)
−0.0018 (11)
0.0046 (11)
0.0059 (11)
−0.0013 (11)
0.0003 (11)
0.0017 (11)
0.0037 (9)
C3A
C4A
C10A
C9A
0.0007 (9)
0.0006 (10)
0.0021 (10)
−0.0007 (10)
−0.0008 (10)
−0.0008 (10)
0.0028 (11)
0.0012 (11)
0.0030 (10)
0.0011 (10)
0.0040 (10)
0.0048 (12)
−0.0016 (10)
−0.0007 (10)
−0.0039 (11)
−0.0067 (12)
−0.0026 (11)
−0.0009 (10)
0.00182 (10)
−0.0003 (7)
−0.0021 (7)
0.0021 (7)
C8A
C7A
C6A
C5A
C11A
C12A
C13A
C14A
C15A
C16A
C17A
C18A
C19A
C20A
C21A
C22A
Br1B
O1B
0.0023 (10)
0.0050 (11)
0.0015 (11)
−0.0020 (11)
0.0037 (10)
0.00505 (11)
0.0005 (8)
O2B
0.0155 (9)
0.0220 (10)
0.0145 (9)
0.0020 (7)
O3B
0.0105 (8)
0.0124 (9)
0.0051 (7)
N1B
0.0045 (10)
0.0103 (12)
0.0104 (12)
0.0072 (11)
0.0077 (11)
0.0116 (12)
0.0100 (12)
0.0124 (12)
0.0109 (12)
0.0102 (12)
0.0170 (13)
0.0175 (13)
0.0111 (12)
0.0109 (12)
0.0195 (14)
0.0187 (14)
0.0122 (12)
0.0104 (12)
0.0163 (14)
0.0172 (12)
0.0105 (12)
0.0095 (12)
0.0101 (12)
0.0101 (12)
0.0084 (12)
0.0125 (13)
0.0122 (13)
0.0125 (13)
0.0117 (13)
0.0199 (15)
0.0140 (14)
0.0193 (14)
0.0128 (13)
0.0107 (13)
0.0223 (15)
0.0105 (12)
0.0137 (13)
0.0196 (15)
0.0133 (11)
0.0115 (12)
0.0074 (11)
0.0092 (11)
0.0092 (11)
0.0095 (12)
0.0117 (12)
0.0106 (12)
0.0101 (12)
0.0104 (12)
0.0177 (14)
0.0183 (14)
0.0177 (13)
0.0105 (12)
0.0177 (13)
0.0276 (16)
0.0095 (12)
0.0145 (13)
0.0190 (14)
0.0020 (9)
0.0025 (9)
C2B
0.0000 (10)
−0.0011 (9)
0.0012 (9)
0.0003 (10)
−0.0026 (9)
0.0009 (9)
C3B
C4B
C10B
C9B
0.0006 (9)
−0.0001 (9)
−0.0016 (9)
0.0030 (10)
0.0027 (10)
−0.0009 (10)
−0.0062 (10)
0.0069 (11)
0.0022 (11)
0.0042 (11)
−0.0031 (10)
0.0055 (11)
0.0115 (12)
0.0031 (10)
0.0044 (10)
0.0015 (11)
−0.0002 (10)
0.0011 (10)
0.0005 (10)
−0.0016 (10)
−0.0034 (10)
−0.0014 (11)
0.0002 (11)
−0.0011 (11)
0.0011 (10)
0.0029 (11)
0.0073 (12)
−0.0029 (10)
0.0002 (10)
−0.0071 (11)
C8B
C7B
C6B
C5B
C12B
C11B
C13B
C14B
C15B
C16B
C17B
C18B
C19B
Acta Cryst. (2014). C70, 790-795
sup-14

supporting information
C20B
C21B
C22B
0.0330 (16)
0.0263 (15)
0.0133 (12)
0.0161 (14)
0.0146 (14)
0.0121 (13)
0.0178 (14)
0.0191 (14)
0.0137 (13)
−0.0082 (12)
0.0030 (12)
0.0017 (10)
0.0032 (12)
0.0069 (12)
0.0013 (10)
−0.0046 (11)
−0.0027 (11)
0.0026 (10)
Geometric parameters (Å, º)
Br1A—C18A
O1A—C5A
1.904 (2)
Br1B—C18B
1.909 (2)
1.241 (3)
1.208 (3)
1.343 (3)
1.451 (3)
1.385 (3)
1.361 (3)
0.83 (3)
1.355 (3)
1.504 (3)
1.528 (3)
1.475 (3)
1.0000
O1B—C5B
1.237 (3)
1.215 (3)
1.351 (3)
1.454 (3)
1.387 (3)
1.363 (3)
0.80 (3)
1.354 (3)
1.503 (3)
1.524 (3)
1.476 (3)
1.0000
O2A—C14A
O3A—C14A
O3A—C15A
N1A—C2A
O2B—C14B
O3B—C14B
O3B—C15B
N1B—C2B
N1A—C9A
N1B—C9B
N1A—H1A
N1B—H1B
C2A—C3A
C2B—C3B
C2A—C13A
C3A—C4A
C2B—C13B
C3B—C4B
C3A—C14A
C4A—H4A
C3B—C14B
C4B—H4B
C4A—C10A
C4A—C17A
C10A—C9A
C10A—C5A
C9A—C8A
1.522 (3)
1.537 (3)
1.368 (3)
1.436 (3)
1.505 (3)
0.9900
C4B—C10B
C4B—C17B
C10B—C9B
C10B—C5B
C9B—C8B
1.519 (3)
1.534 (3)
1.362 (3)
1.443 (3)
1.503 (3)
0.9900
C8A—H8AA
C8A—H8AB
C8A—C7A
C8B—H8BA
C8B—H8BB
C8B—C7B
0.9900
0.9900
1.541 (3)
1.536 (3)
1.534 (3)
1.525 (3)
0.9900
1.539 (3)
1.531 (3)
1.538 (3)
1.532 (3)
0.9900
C7A—C6A
C7B—C6B
C7A—C11A
C7A—C12A
C6A—H6AA
C6A—H6AB
C6A—C5A
C7B—C12B
C7B—C11B
C6B—H6BA
C6B—H6BB
C6B—C5B
0.9900
0.9900
1.512 (3)
0.9800
1.514 (3)
0.9800
C11A—H11A
C11A—H11B
C11A—H11C
C12A—H12A
C12A—H12B
C12A—H12C
C13A—H13A
C13A—H13B
C13A—H13C
C15A—H15A
C15A—H15B
C15A—C16A
C16A—H16A
C16A—H16B
C16A—H16C
C12B—H12D
C12B—H12E
C12B—H12F
C11B—H11D
C11B—H11E
C11B—H11F
C13B—H13D
C13B—H13E
C13B—H13F
C15B—H15C
C15B—H15D
C15B—C16B
C16B—H16D
C16B—H16E
C16B—H16F
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9900
0.9900
0.9900
0.9900
1.509 (4)
0.9800
1.505 (4)
0.9800
0.9800
0.9800
0.9800
0.9800
Acta Cryst. (2014). C70, 790-795
sup-15

supporting information
C17A—C18A
C17A—C22A
C18A—C19A
C19A—H19A
C19A—C20A
C20A—H20A
C20A—C21A
C21A—H21A
C21A—C22A
C22A—H22A
1.393 (3)
1.407 (3)
1.395 (3)
0.9500
C17B—C18B
C17B—C22B
C18B—C19B
C19B—H19B
C19B—C20B
C20B—H20B
C20B—C21B
C21B—H21B
C21B—C22B
C22B—H22B
1.395 (3)
1.401 (3)
1.390 (4)
0.9500
1.382 (4)
0.9500
1.381 (4)
0.9500
1.389 (4)
0.9500
1.391 (4)
0.9500
1.381 (3)
0.9500
1.381 (4)
0.9500
C14A—O3A—C15A
C2A—N1A—H1A
C9A—N1A—C2A
C9A—N1A—H1A
N1A—C2A—C13A
C3A—C2A—N1A
C3A—C2A—C13A
C2A—C3A—C4A
C2A—C3A—C14A
C14A—C3A—C4A
C3A—C4A—H4A
C3A—C4A—C17A
C10A—C4A—C3A
C10A—C4A—H4A
C10A—C4A—C17A
C17A—C4A—H4A
C9A—C10A—C4A
C9A—C10A—C5A
C5A—C10A—C4A
N1A—C9A—C10A
N1A—C9A—C8A
C10A—C9A—C8A
C9A—C8A—H8AA
C9A—C8A—H8AB
C9A—C8A—C7A
H8AA—C8A—H8AB
C7A—C8A—H8AA
C7A—C8A—H8AB
C6A—C7A—C8A
C11A—C7A—C8A
C11A—C7A—C6A
C12A—C7A—C8A
C12A—C7A—C6A
C12A—C7A—C11A
C7A—C6A—H6AA
C7A—C6A—H6AB
H6AA—C6A—H6AB
116.77 (19)
118.2 (17)
123.0 (2)
118.6 (17)
113.0 (2)
120.2 (2)
126.8 (2)
121.9 (2)
119.7 (2)
118.4 (2)
108.9
C14B—O3B—C15B
C2B—N1B—H1B
C9B—N1B—C2B
C9B—N1B—H1B
N1B—C2B—C13B
C3B—C2B—N1B
C3B—C2B—C13B
C2B—C3B—C4B
C2B—C3B—C14B
C14B—C3B—C4B
C3B—C4B—H4B
C3B—C4B—C17B
C10B—C4B—C3B
C10B—C4B—H4B
C10B—C4B—C17B
C17B—C4B—H4B
C9B—C10B—C4B
C9B—C10B—C5B
C5B—C10B—C4B
N1B—C9B—C8B
C10B—C9B—N1B
C10B—C9B—C8B
C9B—C8B—H8BA
C9B—C8B—H8BB
C9B—C8B—C7B
H8BA—C8B—H8BB
C7B—C8B—H8BA
C7B—C8B—H8BB
C6B—C7B—C8B
C6B—C7B—C12B
C6B—C7B—C11B
C12B—C7B—C8B
C11B—C7B—C8B
C11B—C7B—C12B
C7B—C6B—H6BA
C7B—C6B—H6BB
H6BA—C6B—H6BB
114.45 (19)
117.8 (19)
122.3 (2)
118.8 (19)
112.9 (2)
119.5 (2)
127.6 (2)
121.1 (2)
120.0 (2)
118.9 (2)
108.5
112.70 (19)
110.48 (19)
108.9
112.42 (19)
109.25 (19)
108.5
107.00 (19)
108.9
109.69 (19)
108.5
121.4 (2)
119.9 (2)
118.4 (2)
120.4 (2)
116.2 (2)
123.4 (2)
109.0
120.7 (2)
119.7 (2)
119.6 (2)
116.2 (2)
120.0 (2)
123.9 (2)
109.1
109.0
109.1
112.81 (19)
107.8
112.27 (19)
107.9
109.0
109.1
109.0
109.1
108.19 (19)
110.5 (2)
109.8 (2)
108.96 (19)
110.1 (2)
109.2 (2)
108.7
108.03 (19)
109.36 (19)
110.6 (2)
108.64 (19)
110.8 (2)
109.4 (2)
108.7
108.7
108.7
107.6
107.6
Acta Cryst. (2014). C70, 790-795
sup-16

supporting information
C5A—C6A—C7A
114.4 (2)
108.7
C5B—C6B—C7B
C5B—C6B—H6BA
C5B—C6B—H6BB
O1B—C5B—C10B
O1B—C5B—C6B
C10B—C5B—C6B
C7B—C12B—H12D
C7B—C12B—H12E
C7B—C12B—H12F
114.42 (19)
108.7
C5A—C6A—H6AA
C5A—C6A—H6AB
O1A—C5A—C10A
O1A—C5A—C6A
108.7
108.7
120.9 (2)
120.0 (2)
119.1 (2)
109.5
121.5 (2)
120.2 (2)
118.3 (2)
109.5
C10A—C5A—C6A
C7A—C11A—H11A
C7A—C11A—H11B
C7A—C11A—H11C
H11A—C11A—H11B
H11A—C11A—H11C
H11B—C11A—H11C
C7A—C12A—H12A
C7A—C12A—H12B
C7A—C12A—H12C
H12A—C12A—H12B
H12A—C12A—H12C
H12B—C12A—H12C
C2A—C13A—H13A
C2A—C13A—H13B
C2A—C13A—H13C
H13A—C13A—H13B
H13A—C13A—H13C
H13B—C13A—H13C
O2A—C14A—O3A
O2A—C14A—C3A
O3A—C14A—C3A
O3A—C15A—H15A
O3A—C15A—H15B
O3A—C15A—C16A
H15A—C15A—H15B
C16A—C15A—H15A
C16A—C15A—H15B
C15A—C16A—H16A
C15A—C16A—H16B
C15A—C16A—H16C
H16A—C16A—H16B
H16A—C16A—H16C
H16B—C16A—H16C
C18A—C17A—C4A
C18A—C17A—C22A
C22A—C17A—C4A
C17A—C18A—Br1A
C17A—C18A—C19A
C19A—C18A—Br1A
C18A—C19A—H19A
C20A—C19A—C18A
C20A—C19A—H19A
109.5
109.5
109.5
109.5
109.5
H12D—C12B—H12E
H12D—C12B—H12F
H12E—C12B—H12F
C7B—C11B—H11D
C7B—C11B—H11E
C7B—C11B—H11F
H11D—C11B—H11E
H11D—C11B—H11F
H11E—C11B—H11F
C2B—C13B—H13D
C2B—C13B—H13E
C2B—C13B—H13F
H13D—C13B—H13E
H13D—C13B—H13F
H13E—C13B—H13F
O2B—C14B—O3B
O2B—C14B—C3B
O3B—C14B—C3B
O3B—C15B—H15C
O3B—C15B—H15D
O3B—C15B—C16B
H15C—C15B—H15D
C16B—C15B—H15C
C16B—C15B—H15D
C15B—C16B—H16D
C15B—C16B—H16E
C15B—C16B—H16F
H16D—C16B—H16E
H16D—C16B—H16F
H16E—C16B—H16F
C18B—C17B—C4B
C18B—C17B—C22B
C22B—C17B—C4B
C17B—C18B—Br1B
C19B—C18B—Br1B
C19B—C18B—C17B
C18B—C19B—H19B
C20B—C19B—C18B
C20B—C19B—H19B
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
122.3 (2)
127.0 (2)
110.7 (2)
109.3
122.5 (2)
126.3 (2)
111.2 (2)
110.2
109.3
110.2
111.6 (2)
108.0
107.5 (2)
108.5
109.3
110.2
109.3
110.2
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
125.4 (2)
116.9 (2)
117.6 (2)
121.46 (18)
121.8 (2)
116.74 (18)
120.3
124.7 (2)
116.4 (2)
118.9 (2)
121.88 (19)
115.91 (19)
122.2 (2)
120.2
119.5 (2)
120.3
119.6 (2)
120.2
Acta Cryst. (2014). C70, 790-795
sup-17

supporting information
C19A—C20A—H20A
C19A—C20A—C21A
C21A—C20A—H20A
C20A—C21A—H21A
C22A—C21A—C20A
C22A—C21A—H21A
C17A—C22A—H22A
C21A—C22A—C17A
C21A—C22A—H22A
119.8
C19B—C20B—H20B
C19B—C20B—C21B
C21B—C20B—H20B
C20B—C21B—H21B
C22B—C21B—C20B
C22B—C21B—H21B
C17B—C22B—H22B
C21B—C22B—C17B
C21B—C22B—H22B
120.1
120.4 (2)
119.8
119.9 (2)
120.1
120.3
120.2
119.3 (2)
120.3
119.6 (2)
120.2
119.0
118.9
122.1 (2)
119.0
122.2 (2)
118.9
Br1A—C18A—C19A—C20A
N1A—C2A—C3A—C4A
N1A—C2A—C3A—C14A
N1A—C9A—C8A—C7A
C2A—N1A—C9A—C10A
C2A—N1A—C9A—C8A
C2A—C3A—C4A—C10A
C2A—C3A—C4A—C17A
C2A—C3A—C14A—O2A
C2A—C3A—C14A—O3A
C3A—C4A—C10A—C9A
C3A—C4A—C10A—C5A
C3A—C4A—C17A—C18A
C3A—C4A—C17A—C22A
C4A—C3A—C14A—O2A
C4A—C3A—C14A—O3A
C4A—C10A—C9A—N1A
C4A—C10A—C9A—C8A
C4A—C10A—C5A—O1A
C4A—C10A—C5A—C6A
C4A—C17A—C18A—Br1A
C4A—C17A—C18A—C19A
C4A—C17A—C22A—C21A
C10A—C4A—C17A—C18A
C10A—C4A—C17A—C22A
C10A—C9A—C8A—C7A
C9A—N1A—C2A—C3A
C9A—N1A—C2A—C13A
C9A—C10A—C5A—O1A
C9A—C10A—C5A—C6A
C9A—C8A—C7A—C6A
C9A—C8A—C7A—C11A
C9A—C8A—C7A—C12A
C8A—C7A—C6A—C5A
C7A—C6A—C5A—O1A
C7A—C6A—C5A—C10A
C5A—C10A—C9A—N1A
C5A—C10A—C9A—C8A
179.88 (19)
2.6 (4)
Br1B—C18B—C19B—C20B
N1B—C2B—C3B—C4B
N1B—C2B—C3B—C14B
N1B—C9B—C8B—C7B
C2B—N1B—C9B—C10B
C2B—N1B—C9B—C8B
C2B—C3B—C4B—C10B
C2B—C3B—C4B—C17B
C2B—C3B—C14B—O2B
C2B—C3B—C14B—O3B
C3B—C4B—C10B—C9B
C3B—C4B—C10B—C5B
C3B—C4B—C17B—C18B
C3B—C4B—C17B—C22B
C4B—C3B—C14B—O2B
C4B—C3B—C14B—O3B
C4B—C10B—C9B—N1B
C4B—C10B—C9B—C8B
C4B—C10B—C5B—O1B
C4B—C10B—C5B—C6B
C4B—C17B—C18B—Br1B
C4B—C17B—C18B—C19B
C4B—C17B—C22B—C21B
C10B—C4B—C17B—C18B
C10B—C4B—C17B—C22B
C10B—C9B—C8B—C7B
C9B—N1B—C2B—C3B
C9B—N1B—C2B—C13B
C9B—C10B—C5B—O1B
C9B—C10B—C5B—C6B
C9B—C8B—C7B—C6B
C9B—C8B—C7B—C12B
C9B—C8B—C7B—C11B
C8B—C7B—C6B—C5B
C7B—C6B—C5B—O1B
C7B—C6B—C5B—C10B
C5B—C10B—C9B—N1B
C5B—C10B—C9B—C8B
−179.9 (2)
−6.8 (3)
−178.9 (2)
157.0 (2)
−2.6 (4)
174.0 (2)
−159.6 (2)
12.6 (4)
177.8 (2)
−14.1 (3)
105.6 (3)
19.8 (4)
−166.5 (2)
25.5 (3)
−96.5 (3)
−9.1 (4)
−160.9 (2)
18.3 (3)
171.1 (2)
−27.2 (3)
154.4 (2)
−122.8 (2)
58.0 (3)
−168.2 (2)
120.5 (2)
−64.0 (3)
−161.7 (2)
17.7 (3)
171.8 (2)
−8.1 (3)
−11.2 (3)
168.4 (2)
10.3 (3)
10.1 (3)
−170.9 (2)
−8.5 (3)
−170.6 (2)
−6.1 (3)
173.4 (2)
−0.6 (3)
174.5 (2)
−173.7 (2)
−117.9 (2)
57.6 (3)
179.4 (2)
−179.4 (2)
115.4 (2)
−63.7 (3)
21.4 (3)
−22.6 (3)
7.0 (4)
−14.3 (4)
165.5 (2)
173.1 (2)
−5.0 (3)
−173.5 (2)
−176.1 (2)
3.0 (3)
48.6 (3)
−49.2 (3)
−167.8 (2)
72.0 (3)
−71.7 (3)
168.2 (2)
−51.3 (3)
−154.2 (2)
26.7 (3)
52.6 (3)
155.3 (2)
−26.5 (3)
−171.5 (2)
7.5 (4)
175.5 (2)
−4.9 (4)
Acta Cryst. (2014). C70, 790-795
sup-18

supporting information
C11A—C7A—C6A—C5A
C12A—C7A—C6A—C5A
C13A—C2A—C3A—C4A
C13A—C2A—C3A—C14A
C14A—O3A—C15A—C16A
C14A—C3A—C4A—C10A
C14A—C3A—C4A—C17A
C15A—O3A—C14A—O2A
C15A—O3A—C14A—C3A
C17A—C4A—C10A—C9A
C17A—C4A—C10A—C5A
C17A—C18A—C19A—C20A
C18A—C17A—C22A—C21A
C18A—C19A—C20A—C21A
C19A—C20A—C21A—C22A
C20A—C21A—C22A—C17A
C22A—C17A—C18A—Br1A
C22A—C17A—C18A—C19A
69.5 (3)
−170.2 (2)
−176.8 (2)
1.7 (4)
C12B—C7B—C6B—C5B
170.7 (2)
−68.8 (3)
173.5 (2)
−5.7 (4)
177.9 (2)
−155.3 (2)
82.7 (3)
2.9 (3)
C11B—C7B—C6B—C5B
C13B—C2B—C3B—C4B
C13B—C2B—C3B—C14B
C14B—O3B—C15B—C16B
C14B—C3B—C4B—C10B
C14B—C3B—C4B—C17B
C15B—O3B—C14B—O2B
C15B—O3B—C14B—C3B
C17B—C4B—C10B—C9B
C17B—C4B—C10B—C5B
C17B—C18B—C19B—C20B
C18B—C17B—C22B—C21B
C18B—C19B—C20B—C21B
C19B—C20B—C21B—C22B
C20B—C21B—C22B—C17B
C22B—C17B—C18B—Br1B
C22B—C17B—C18B—C19B
−88.5 (3)
167.4 (2)
−73.0 (3)
0.9 (3)
−178.5 (2)
−104.7 (2)
68.8 (3)
−0.7 (4)
2.2 (4)
−177.29 (19)
96.4 (3)
−82.0 (3)
0.1 (4)
1.4 (4)
1.3 (4)
1.3 (4)
−0.2 (4)
−1.6 (4)
178.40 (17)
−1.0 (3)
−1.3 (4)
−0.1 (4)
178.55 (17)
−1.4 (4)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1B—H1B···O1Ai
N1A—H1A···O1Bii
0.80 (3)
0.83 (3)
2.02 (3)
2.07 (3)
2.818 (3)
2.884 (3)
174 (3)
165 (2)
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2.
Acta Cryst. (2014). C70, 790-795
sup-19

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