Comparison of computationally cheap methods for providing insight into the crystal packing of highly bromomethylated azobenzenes

Article abstract of DOI:10.1107/S2053229618015309

For five bromomethylated azobenzenes, namely (E)-[4-(bromomethyl)phenyl][4-(dibromomethyl)phenyl]diazene, C₁₄H₁₁Br₃N₂, (E)-1,2-bis[4-(dibromomethyl)phenyl]diazene, C₁₄H₁₀Br₄N

Full text of DOI:10.1107/S2053229618015309

research papers
Comparison of computationally cheap methods for
providing insight into the crystal packing of highly
bromomethylated azobenzenes1
ISSN 2053-2296
Christophe M. L. Vande Velde,a* Matthias Zellerb and Vladimir A. Azovc*
aFaculty of Applied Engineering, Advanced Reactor Technology, University of Antwerp, Groenenborgerlaan 171,
Antwerpen 2020, Belgium, bDepartment of Chemistry, Purdue University, West Lafayette, IN 47907, USA, and
cDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein, Free State, 9300, South Africa.
*Correspondence e-mail: christophe.vandevelde@uantwerpen.be, azovv@ufs.ac.za
Received 2 August 2018
Accepted 29 October 2018
Edited by A. R. Kennedy, University of Strath-
clyde, Scotland
For five bromomethylated azobenzenes, namely (E)-[4-(bromomethyl)phenyl]-
[4-(dibromomethyl)phenyl]diazene, C14H11Br3N2, (E)-1,2-bis[4-(dibromomethyl)-
phenyl]diazene, C14H10Br4N2, (E)-[3-(bromomethyl)phenyl][3-(dibromomethyl)-
phenyl]diazene, C14H11Br3N2, (E)-[3-(dibromomethyl)phenyl][3-(tribromomethyl)-
phenyl]diazene, C14H10Br4N2, and (E)-1,2-bis[3-(dibromomethyl)phenyl]diazene,
C14H9Br5N2, the computationally cheap CLP PIXEL approach and CrystalExplorer
were used for calculating lattice energies and performing Hirshfeld surface analysis
via the enrichment ratios of atomic contacts. The procedures and caveats are
discussed in detail. The findings from these tools are contrasted with the results of
geometric analysis of the structures. We conclude that an energy-based discussion of
the crystal packing provides substantially more insight than one based purely on
geometry, as has so long been the custom in crystallography. In addition, we find a
surprising shortage of halogen–halogen interactions in these highly bromomethyl-
ated compounds.
1 This paper is dedicated to the memory of
Professor Philip Coppens, a true giant in
crystallography, and an inspiration.
Keywords: CLP calculations; Hirshfeld surface
analysis; enrichment ratio; crystal structure;
CrystalExplorer; azobenzene; crystal packing;
halogen bonding.
CCDC references: 1876016; 1876015;
1876014; 1876013; 1876012
Supporting information: this article has
supporting information at journals.iucr.org/c
1. Introduction
In this article, we look at five different azobenzene derivatives
(Merino, 2011), all bromomethylated to various degrees. We
will discuss the geometry of the crystals in terms of distances
and angles, but also in terms of CLP PIXEL (Gavezzotti, 2008,
2011) and CrystalExplorer (CE; McKinnon et al., 2004)
calculations, as well as Hirshfeld plots and the enrichment
ratios resulting from them, and compare between these
various instruments at the fingertips of today’s crystal-
lographers. We will compare the values for the lattice energies
that result from CE and CLP-PIXEL, and, for good measure,
include numbers from the UNI force field as implemented in
CLP and Mercury (Macrae et al., 2008). In terms of crystal
packing, one would expect to find plenty of halogen–halogen
interactions and halogen bonds (Metrangolo et al., 2008;
Desiraju & Parthasarathy, 1989) in these compounds, and their
significance to the structures will also be discussed.
Analysis of the X-ray structures of derivatives 3 and 4 (see
Fig. 1) gave evidence of a dynamic disorder due to a pedalling
motion (Harada & Ogawa, 2009) of the central N N double
bond. Using variable-temperature X-ray and van ’t Hoff plots
it was possible to determine the thermodynamic parameters
for the pedal motion (Vande Velde et al., 2015). Computa-
tional methods were employed to look into the differences in
the temperature-dependent behaviour of the dynamic dis-
order of these two compounds.
With these findings, we became motivated to perform an
X-ray study of the whole family of similar brominated azo-
# 2018 International Union of Crystallography
1692 https://doi.org/10.1107/S2053229618015309
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benzene derivatives to get insight into their packing modes
and stabilizing intermolecular interactions in the crystalline
state. Compounds 5, 6 and 7 (see Fig. 1) have been isolated as
the by-products of the bromination reactions. To make the
series of compounds more extensive, we prepared additional
derivatives of 2 by bromination of 7, which afforded
compounds 8 and 9 (Fig. 1). All new brominated azobenzenes
easily afforded X-ray-quality crystals that showed rather
different packing motifs. We used their crystal structures as
benchmarks for in-depth testing of various crystal structure
analysis tools.
reflux and the mixture was then hot-filtered. The filtrate was
washed with CCl4 (10 ml). The organic phase was washed with
warm water and dried (Na2SO4). The residue was recrys-
tallized from butanone and MeOH to afford 0.81 g of 3. The
butanone mother liquor was evaporated to dryness and then
chromatographed on silica [CH2Cl2/petroleum ether (PE), 1:1
v/v] to give an additional 60 mg of 3 (total yield: 0.87 g,
2.36 mmol, 49%), as well as traces of compounds 5 (yield:
38 mg, 0.085 mmol, 1.8%) and 6 (yield: 18 mg, 0.034 mmol,
0.7%). Compound 3 has been characterized and reported
before (Azov et al., 2014; Jousselme et al., 2003). Compound 5
was recrystallized by slow diffusion of hexane into a chloro-
form solution, affording orange crystals (m.p. 146–148 ꢀC).
1
RF = 0.41 (CH2Cl2/cyclohexane, 1:2 v/v). H NMR (CDCl3,
2. Experimental
200 MHz): ꢀ 4.56 (s, 2H), 6.71 (s, 1H), 7.52–758 (m, 2H), 7.69–
7.74 (m, 2H), 7.88–7.95 (m, 4H). 13C NMR (CDCl3, 50 MHz): ꢀ
32.6, 40.0, 123.1, 123.4, 127.5, 129.9, 141.0, 144.2, 152.1, 152.9.
MS (EI, 70 eV) m/z (I%): 444 (15) [M+], 365 (100), 286 (40),
169 (15), 168 (15). Compound 6 was recrystallized by slow
diffusion of hexane into a chloroform solution, affording long
(up to 10 mm) rod-shaped red–orange crystals (m.p. 151–
2.1. Synthesis and crystallization
The brominated azobenzene derivatives were prepared by
radical bromination of (E)-1,2-bis(4-methylphenyl)diazene, 1,
and (E)-1,2-bis(3-methylphenyl)diazene, 2, using N-bromo-
succinimide (NBS)/benzoyl peroxide (BPO) (Fig. 1) according
to a literature procedure (Jousselme et al., 2003). Our target
products were the symmetric dibrominated derivatives 3 and
4, which were later employed for the preparation of functional
TTF-AB macrocycles (Azov et al., 2014). Along with 3 and 4,
the polybrominated derivatives 5 and 6 could be separated
from the reaction of 1, whereas tribrominated derivative 7 was
separated from the bromination of 2. All compounds could be
easily crystallized, affording X-ray-quality crystals.
1
153 ꢀC). RF = 0.45 (CH2Cl2/cyclohexane, 1:2 v/v). H NMR
(CDCl3): ꢀ 6.71 (s, 2H), 7.70–7.76 (m, 4H), 7.89–7.96 (m, 4H).
13C NMR (CDCl3): ꢀ 39.3, 123.2, 127.5, 144.4, 152.8. MS (EI,
70 eV) m/z (I%): 522 (20) [M+], 443 (100), 364 (100), 285 (20),
168 (30).
2.1.2. (E)-1,2-Bis[3-(bromomethyl)phenyl]diazene (4) and
(E)-[3-(dibromomethyl)phenyl][3-(bromomethyl)phenyl]dia-
zene (7). To compound 2 (1.8 g, 8.57 mmol) in dry CCl4
(60 ml) were added NBS (4.27 g, 24 mmol, 2.8 equiv.) and
BPO (75 mg, 0.31 mmol). The reaction mixture was stirred for
6 h under reflux and the mixture was then hot-filtered. The
filtrate was washed with CCl4 (15 ml). The organic phase was
washed with warm water and dried (Na2SO4). The crude
2.1.1. (E)-1,2-Bis[4-(bromomethyl)phenyl]diazene (2), (E)-
[4-(dibromomethyl)phenyl][4-(bromomethyl)phenyl]diazene
(5) and (E)-1,2-bis[4-(dibromomethyl)phenyl]diazene (6). To
compound 1 (1.0 g, 4.8 mmol) in dry CCl4 (40 ml) were added
NBS (2.05 g, 11.5 mmol, 2.4 equiv.) and BPO (47 mg,
0.18 mmol). The reaction mixture was stirred for 2.5 h under
Figure 1
Synthesis of the polybromomethylated azobenzene derivatives 1–9.
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Table 1
Experimental details.
All determinations were carried out at 100 K on a Bruker SMART 1000 diffractometer. The absorption correction was multi-scan, using SADABS (Krause et al.,
2015) for 5–8 and TWINABS (Sheldrick, 2012) for 9. H-atom parameters were constrained.
5
6
7
Crystal data
Chemical formula
Mr
Crystal system, space group
C14H11Br3N2
446.98
Monoclinic, P21/c
8.538 (1), 5.283 (1), 32.801 (4)
C14H10Br4N2
525.88
Monoclinic, C2/c
20.379 (3), 8.6401 (10), 9.8451 (10)
C14H11Br3N2
446.98
Monoclinic, P21/c
9.1219 (12), 16.904 (2),
10.3633 (14)
90, 112.122 (2), 90
1480.4 (3)
˚
a, b, c (A)
ꢁ, ꢂ, ꢃ (ꢀ)
90, 99.692 (5), 90
1458.4 (4)
4
Mo Kꢁ
8.29
0.45 Â 0.35 Â 0.18
90, 114.797 (2), 90
1573.7 (3)
4
Mo Kꢁ
10.22
3
˚
V (A )
Z
Radiation type
4
Mo Kꢁ
8.16
0.52 Â 0.45 Â 0.15
ꢄ (mmÀ1
Crystal size (mm)
)
0.51 Â 0.48 Â 0.38
Data collection
Tmin, Tmax
0.316, 0.746
13694, 4445, 3947
0.406, 0.746
5663, 2322, 2049
0.349, 0.746
12573, 4362, 3587
No. of measured, independent and
observed [I > 2ꢅ(I)] reflections
Rint
0.040
0.732
0.028
0.730
0.038
0.729
À1
˚
(sin ꢆ/ꢇ)max (A
)
Refinement
R[F2 > 2ꢅ(F2)], wR(F2), S
No. of reflections
No. of parameters
0.039, 0.088, 1.15
4445
172
1.41, À1.06
0.024, 0.056, 1.02
2322
92
0.82, À0.60
0.041, 0.104, 1.03
4362
172
2.24, À1.56
À3
˚
Áꢈmax, Áꢈmin (e A
)
8
9
Crystal data
Chemical formula
Mr
C14H10Br4N2
525.88
C14H9Br5N2
604.78
Crystal system, space group
˚
Triclinic, P1
4.899 (2), 8.294 (2), 9.942 (3)
98.103 (4), 103.640 (3), 96.650 (3)
384.0 (2)
Triclinic, P1
7.0161 (11), 8.5634 (13), 14.897 (2)
103.257 (2), 102.974 (2), 91.703 (2)
845.8 (2)
a, b, c (A)
ꢁ, ꢂ, ꢃ (ꢀ)
3
˚
V (A )
Z
Radiation type
1
2
Mo Kꢁ
10.47
0.45 Â 0.25 Â 0.20
Mo Kꢁ
11.87
0.45 Â 0.43 Â 0.21
ꢄ (mmÀ1
Crystal size (mm)
)
Data collection
Tmin, Tmax
0.308, 0.746
5417, 2249, 1993
0.014, 0.052
15148, 8987, 6827
No. of measured, independent and observed
[I > 2ꢅ(I)] reflections
Rint
0.042
0.729
0.066
0.731
À1
˚
(sin ꢆ/ꢇ)max (A
)
Refinement
R[F2 > 2ꢅ(F2)], wR(F2), S
No. of reflections
0.033, 0.085, 1.05
2249
0.051, 0.137, 0.99
8987
No. of parameters
No. of restraints
92
0
213
58
1.81, À1.56
À3
˚
Áꢈmax, Áꢈmin (e A
)
1.08, À1.11
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS2013 (Sheldrick, 2008b), SHELXL2018 (Sheldrick, 2015), shelXle (Hu¨bschle et al., 2011) and
SHELXL2018 (Sheldrick, 2015).
mixture was separated by two consecutive chromatographies
on silica (CH2Cl2/PE, 1:1 v/v, then toluene/PE, 2:3 v/v), with
separations being complicated by the similar RF values of the
products. Recrystallization from MeCN afforded 0.66 g
(1.79 mmol, 21%) of analytically pure 4 that has been
reported previously (Azov et al., 2014; Jousselme et al., 2003).
Additionally, 1.05 g (2.35 mmol, 27%) of tribromide 7 was
obtained as an orange crystalline solid. X-ray-quality crystals
were grown by slow diffusion of hexane into a chloroform
solution (m.p. 120–121 ꢀC). RF = 0.45 (CH2Cl2/cyclohexane,
1:2 v/v). H NMR (CDCl3, 200 MHz): ꢀ 4.59 (s, 2H), 6.74 (s,
1H), 7.48–7.59 (m, 2H), 7.70–7.74 (m, 2H), 7.86–7.97 (m, 2H),
8.10–8.12 (m, 2H). 13C NMR (CDCl3, 50 MHz): ꢀ 32.7, 40.1,
120.5, 123.0, 123.5, 124.6, 129.1, 129.6 (Â), 131.8, 139.0, 143.0,
152.2, 152.6. MS (EI, 70 eV) m/z (I%): 444 (80) [M+], 365 (50),
275 (40), 247 (60), 197 (60), 169 (100).
1
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2.1.3. (E)-1,2-Bis[3-(dibromomethyl)phenyl]diazene (8)
and (E)-[3-(tribromomethyl)phenyl][3-(dibromomethyl)phen-
yl]diazene (9). To compound 7 (0.95 g, 2.13 mmol) in dry CCl4
(30 ml) were added NBS (0.76 g, 4.3 mmol, 2 equiv.) and BPO
(31 mg). The reaction mixture was stirred for 2 h under reflux
and the mixture was then hot-filtered. The filtrate was washed
with CCl4 (10 ml). The organic phase was washed with warm
water and dried (Na2SO4). The crude mixture was separated
by chromatography on silica (toluene/PE, 2:3 v/v) to afford
0.43 g (0.817 mmol, 38%) of 8 and 0.15 g (0.248 mmol, 12%) of
9, both orange crystalline solids. X-ray-quality crystals of
tetrabromide 8 were grown by slow diffusion of hexane into a
chloroform solution (m.p. 142–143 ꢀC). RF = 0.50 (CH2Cl2/
to these conditions, the occupancy ratio refined to
0.9601 (19):0.0399 (19).
All H atoms were modelled in riding mode. C—H distances
2
3
˚
were 0.95, 1.00 and 0.99 A for sp CH, sp CH and CH2 groups,
respectively. In all cases, Uiso(H) values were set at 1.2Ueq(C).
Displacement ellipsoid plots of all structures can also be
found in the supporting information as Figs. S11–S15.
2.3. Calculations
CLP PIXEL calculations (Gavezzotti, 2008, 2011) were
based on electron-density cubes calculated with GAUS-
SIAN09 (Frisch et al., 2016) from B3LYP/6-311(d,p) and MP2/
6-311(d,p) wavefunctions of the various molecules at the fixed
geometries from the crystals, with carbon–hydrogen distances
1
cyclohexane, 1:2 v/v). H NMR (CDCl3, 200 MHz): ꢀ 6.75 (s,
2H), 7.52–7.60 (m, 2H), 7.71–7.77 (m, 2H), 7.89–7.95 (m, 2H),
8.12–8.14 (m, 2H). 13C NMR (CDCl3, 50 MHz): ꢀ 40.0, 120.6,
124.7, 129.3, 129.6, 143.0, 152.1. MS (EI, 70 eV) m/z (I%):
522 (80) [M+], 443 (60), 275 (70), 247 (100), 168 (30). X-ray-
quality crystals of pentabromide 9 were grown by slow diffu-
sion of hexane into a chloroform solution (m.p. 130–132 ꢀC).
˚
renormalized to neutron values (1.083 A). CLP results for the
MP2 6-311G(d,p) densities are consistently about 3 kJ molÀ1
in energy above the results based on B3LYP 6-311G(d,p)
densities, and are reproduced in full in Table S1 in the
supporting information, with a summary in Table 2. Standard
CLP parameters were used, where a cluster was built up to a
1
RF = 0.57 (CH2Cl2/cyclohexane, 1:2 v/v). H NMR (CDCl3,
˚
distance of 40 A between molecular centres of mass.
200 MHz): ꢀ 6.75 (s, 1H), 7.53–7.62 (m, 2H), 7.73–7.77 (m, 1H),
7.90–7.96 (m, 2H), 8.14–8.18 (m, 2H), 8.58–8.60 (m, 1H). 13C
NMR (CDCl3, 50 MHz): ꢀ 34.8, 40.0, 120.6, 121.5, 124.0, 124.7,
129.0, 129.1, 129.4, 129.7, 143.1, 148.1, 151.6, 152.1. MS (EI,
70 eV) m/z (I%): 600 (40) [M+], 521 (100), 353 (20), 325 (30),
275 (40), 247 (70), 168 (20), 167 (20).
CE lattice energies were calculated with CrystalExplorer 17
(McKinnon et al., 2004; Turner et al., 2017). A B3LYP/6-
311G(d,p) wavefunction was calculated for a single molecule
with the TONTO quantum chemical program (Jayatilaka &
Grimwood, 2003), and intermolecular energies were then
calculated according to the CE algorithm. It should be noted
that the scale factors used for the various terms in the
expression for the lattice energy have been optimized for the
6-31G(d,p) basis set (which in its standard form does not
include Br) (Thomas et al., 2018), but we expect the differ-
ences with respect to 6-311G(d,p) to be minimal. Clusters
2.2. X-ray crystallography
Crystal data, data collection and structure refinement
details are summarized in Table 1. Structure 9 was found to be
nonmerohedrally twinned. The orientation matrices for the
two components were identified using the program CELL_
NOW (Sheldrick, 2008a), with the two components being
related by a 180ꢀ rotation around the real a axis. The two
components were integrated using SAINT (Bruker, 2010) and
corrected for absorption using TWINABS (Sheldrick, 2012).
The structure was solved using direct methods with only the
non-overlapping reflections of component 1. The structure
was refined using the HKLF 5 routine with all reflections of
both components (including the overlapping ones), resulting
in a fraction of 0.481 (1) for the second component.
˚
were formed with molecules within a distance of 10 A from
the Hirshfeld surface (McKinnon et al., 2004, 1998; Spackman
& McKinnon, 2002) of the central molecule, and all fragments
found within this distance were completed to full molecules.
Convergence of the calculated lattice energies was only
reached with clusters of this size (see Fig. 2). It should be
noted that the output of CE features the total interaction
energy of the cluster with the central entity, which, when the
cluster is centred around one molecule, needs to be halved to
arrive at a number per mole for the lattice energy.
Fingerprint di–de plots (Spackman & McKinnon, 2002)
were generated in CE from the calculated Hirshfeld surfaces,
and the percentage populations divided over the various
atomic species were recorded. These percentages were then
used in a spreadsheet for calculating enrichment ratios as
defined by Jelsch and co-authors (Jelsch et al., 2014).
If disorder was evident from the difference maps, various
models were tried for the best fit. Often the disorder popu-
lations were sufficiently low that the original model still
yielded the best fit. For structure 9, minor but clearly resolved
disorder was observed for the dibromomethyl group. The
major and minor moieties were restrained to have similar
geometries (SAME restraint of SHELXL, with an s.u. value of
3. Results and discussion
3.1. Structures
2
˚
0.02 A ). Atom C10 was included in the disorder modeling and
1,2 and 1,3 C—C distances involving the major and minor
components of C10 were restrained to be similar (SADI
ij
˚
restraint of SHELXL, with an s.u. value of 0.02 A). U
components of the anisotropic displacement parameters for
3.1.1. Compound 5. Compound 5 contains only three Br
atoms. It crystallizes in the space group P21/c, with one mol-
ecule in the asymmetric unit, and packs in a herringbone
pattern (Fig. 3).
˚
disordered atoms closer to each other than 2.0 A were
restrained to be similar (SIMU restraint of SHELXL). Subject
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Table 2
Lattice energies (kJ molÀ1) resulting from the various calculations for
compounds 5–9.
5
6
7
8
9
Mercury-UNI
À135.9
À157.7
À142.1
À123.3
À120.1
À145.4
À147.0
À136.2
À117.7
À114.1
À139.7
À165.4
À151.1
À130.2
À127.3
À151.8
À165.4
À138.9
À111.4
À107.2
À142.1
AA-CLP2015 (UNI) À133.3
CLP/PIXEL/B3LYP
CLP/PIXEL/MP2
CE-B3LYP
À116.7
À113.3
À146.7
Melting point (ꢀC)
146–148 151–153 120–121 142–143 130–132
if these contacts were to be distributed randomly. Numbers
higher than one mean that the contacts between atoms of two
particular elements are more likely to occur than on the basis
of random distribution, whereas numbers smaller than one
indicate that the structure tends to avoid these contacts by
preferring others.
Figure 2
Energy dependence on cluster size for CE energies for the five
brominated azobenzenes 5–9.
The enrichment ratio tables are asymmetric, because the
contact percentages for calculating the enrichment ratios can
be quite different inside and outside the Hirshfeld surface.
Enrichment is defined as a percentage of contacts relative to
the expected contact percentage on a random distribution of
all the atomic species over the Hirshfeld surface. This means
the contact percentages and the enrichment for a particular
pair of atom species are also dependent on the total amount of
surface that these particular atomic species occupy. As an
example, from the data summarized in Table 3, we see that
contacts between H on the inside of the surface and Br outside
occur less often than randomly expected (i.e. the sum of all H
in a single molecule of 5 tends to preferentially contact atoms
other than Br), whereas Br on the inside of the surface has a
slight tendency over the random distribution for contacting
hydrogen on the outside (i.e. hydrogen-containing patches in
the many surrounding molecules tend to cluster around the Br
atoms). The reason for this is that the total amount of surface
taken up by H atoms (46.7%) is larger than that taken up by
Br (36.3%). Hence, the same absolute contact surface between
Br and H will represent a larger percentage with respect to the
Contacts are listed in Table S2 in the supporting informa-
tion. There is an HÁ Á ÁBr contact within the columns from the
CHBr2 H atom to one of the Br atoms of the translated
molecule along the c axis (Fig. 3, E), and of the same H atom
to the Br atom of the CH2Br group in the next column (Fig. 3,
D). The same molecules are in close contact through a BrÁ Á ÁBr
interaction (Fig. 3, C). The Br atom in the CHBr2 group that is
not involved in these contacts instead interacts with one of the
H atoms in the CH2Br group in the next column (Fig. 3, A), as
well as with the Br atom in the same group (Fig. 3, B), and with
its own symmetry-equivalent through inversion symmetry in
the next layer (Fig. 3, F). Due to the tilt of the columns, ꢉ–ꢉ
interactions are strongly tilted or laterally displaced over a
large distance, but this allows C—HÁ Á Áꢉ interactions to occur
in a herringbone pattern.
From the Hirshfeld surfaces and the resulting fingerprint
plots (see Figs. S6–S10 in the supporting information) calcu-
lated in CE, we can then calculate enrichment ratios (Jelsch et
al., 2014), i.e. the actual contact percentage for every indivi-
dual kind of atom pairs compared to the expected percentage
Figure 3
The crystal packing of compound 5. Contacts shorter than the van der Waals radii of the central molecule (magenta) are indicated as cyan dotted lines.
The accompanying capitals refer to the contacts as specified in Table S2 of the supporting information.
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within the column (À33.3 kJ molÀ1). By far the largest
contribution is dispersion. Interactions with molecules at (Àx,
Table 3
Contact enrichment ratios in crystals of compound 5; colour coding from
red to green between 0 and the maximum value in the table.
1
2
1
2
y + , Àz + ) (i.e. perpendicularly oriented molecules in
neighbouring columns) give comparable numbers between
À29.4 and À32.2 kJ molÀ1. Here the relative size of the
dispersion contribution is smaller with respect to electrostatic
and polarization contributions, pointing to a slightly larger
contribution to the total of the BrÁ Á ÁBr and HÁ Á ÁBr contacts.
The total lattice energy according to CLP/PIXEL/MP2 is
À113.3 kJ molÀ1 and according to CE-B3LYP/6-311(d,p) is
À146.7 kJ molÀ1
.
3.1.2. Compound 6. Compound 6 crystallizes in the space
group C2/c, contains four Br atoms per molecule and seems to
be packed rather loosely, with only a few interactions apparent
from the geometry. It can be described as a structure
consisting of layers of tilted molecules that avoid both C—
HÁ Á Áꢉ and ꢉ–ꢉ contacts in this way (Fig. 4). There appear to
be HÁ Á ÁBr interactions (Fig. 4, B and C), a BrÁ Á ÁN interaction
(Fig. 4, A) and a BrÁ Á Áꢉ interaction (see Table S3 in the
supporting information).
total Br surface than it will to the total H surface, which can
lead to these apparent differences in the enrichment ratios.
This is analogous to the fingerprint plot itself not being mirror-
symmetric along its diagonal.
From the enrichment ratio diagram above, we find indeed
that there is no parallel packing (no enriched CÁ Á ÁC, CÁ Á ÁN or
NÁ Á ÁN contacts), but instead CÁ Á ÁH and NÁ Á ÁH contacts have a
high rate of occurrence, as well as BrÁ Á ÁBr contacts, pointing
to a herringbone packing pattern with halogen–halogen
interactions between bromines, and edge-to-face ring inter-
actions.
From an energy perspective (numbers in the text are given
for the CLP/MP2/6-311G(d,p) calculations, see Table S1 for a
full listing of both CE and CLP calculated energies, with a
summary in Table 2), the largest interactions exist between
molecules related through translation symmetry along b, i.e.
In order for the CLP program to work with half a molecule
in the asymmetric unit, the corresponding symmetry-equiva-
lent half needs to be inserted in the CIF file, and the space
group adapted to C2. CLP with PIXEL/MP2 calculates
the sublimation enthalpy to be À120.1 kJ molÀ1 (CE
À145.4 kJ molÀ1), with individual interactions between mol-
ecules not larger than À22.4 kJ molÀ1
.
The most important contributions to the lattice energy are
given in Table S1 in the supporting information. It is to be
noted that dispersion interactions are again by far the greatest
Figure 4
The crystal packing of compound 6. Contacts shorter than the van der Waals radii with the central molecule (magenta) are indicated as cyan dotted lines.
The accompanying capitals refer to the contacts as specified in Table S3 of the supporting information.
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Table 4
Contact enrichment ratios in crystals of compound 6; colour coding from
red to green between 0 and the maximum value in the table.
Table 5
Contact enrichment ratios in crystals of compound 7; colour coding from
red to green between 0 and the maximum value in the table.
contributing component in all the interactions between
neighbouring molecules.
molecular parallel pairs, forming layers, with end-to-face
contacts between the layers (Fig. 5).
The enrichment ratios given in Table 4 essentially corro-
borate the interactions described above, i.e. HÁ Á ÁBr and HÁ Á ÁN
interactions, BrÁ Á ÁC interactions and a clear lack of BrÁ Á ÁBr
halogen interactions. C atoms on the inside of the surface are
slightly more likely to be contacted by H atoms and Br atoms,
indicating a complete lack of face-to-face ꢉ–ꢉ interactions.
The small differences from 1 of the enrichment values in
Table 4 indicate low interaction selectivity for this structure –
the packing appears to be based more on molecular shape and
dispersion contributions than on specific interactions.
3.1.3. Compound 7. Compound 7 crystallizes in the space
group P21/c and contains three Br atoms per molecule. It
adopts an anti conformation around the double bond. The
packing can be described as stacks of lengthwise-displaced
From the geometry, one would judge that the network of
interactions appears a lot stronger than in compound 6,
sporting many NÁ Á ÁH (Fig. 5, B), BrÁ Á ÁN (Fig. 5, C), BrÁ Á ÁBr
(Fig. 5, E) and HÁ Á ÁBr (Fig. 5, A and D) interactions, as well as
a large number of ring–ring contacts. The PIXEL/MP2
calculations, however, give a sublimation enthalpy of only
À114.1 kJ molÀ1 (CE À139.7 kJ molÀ1). There is one mol-
ecular pair which has interactions that are clearly stronger
than the others – the molecules that form a full-length parallel
molecular pair in the packing (À31.2 kJ molÀ1), which also
includes the BrÁ Á ÁH interaction (Fig. 5, A). Other strong
contributors are the contacts with the molecule in the next
pair, that is still parallel to the first pair, but only overlaps with
one of its two phenyl rings (À23.7 kJ molÀ1). This is another
Figure 5
The crystal packing of compound 7. Contacts shorter than the van der Waals radii with the central molecule (magenta) are indicated as cyan dotted lines.
The accompanying capitals refer to the contacts as specified in Table S4 of the supporting information.
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Table 6
Contact enrichment ratios in crystals of compound 8; colour coding from
red to green between 0 and the maximum value in the table.
Table 7
Separate terms [correction factors for the 6-31(d,p) basis set already
included for CE-B3LYP for comparability between the methods] in the
total lattice energies according to CLP/PIXEL/MP2 and CE/B3LYP
(kJ molÀ1).
Ele = electrostatic, pol = polarization, disp = dispersion, rep = repulsion and
tot = total.
ele
pol
disp
rep
tot
CE-B3LYP
5
6
7
8
À90.9
À87.7
À80.0
À79.5
À82.8
À8.7
À6.0
À4.4
À7.6
À3.2
À169.5
À180.6
À165.5
À191.3
À186.5
122.4
128.9
110.2
126.6
130.4
À146.7
À145.4
À139.7
À151.8
À142.1
9
CLP/PIXEL/MP2
5
6
7
8
9
À92.3
À86.8
À79.7
À81.2
À84.2
À29.8
À28
À198.6
À209
207.4
200.5
180.4
198.6
217.4
À113.3
À120.1
À114.1
À127.3
À107.2
indication that the dispersion interactions are in this structure
again much more important than Br-related interactions. The
Type II (Desiraju & Parthasarathy, 1989) BrÁ Á ÁBr contact
À26.9
À28.3
À27
À187.8
À216.5
À213.5
ꢀ
˚
[3.5206 (7) A and 97.5 (1) , designated E in Fig. 5], which
would feature prominently in a geometry-based discussion, is
actually very low down the list of interaction strengths
(À5.1 kJ molÀ1). The stabilization for the molecule next to the
pair, which features an interaction between the N2 bridge
nitrogen and the dibromomethyl Br2 of the pair (Fig. 5, C), is
À12.9 kJ molÀ1. The interaction between atoms H7 and Br2
(D in Fig. 5) is reflected in a stabilization energy of just
which have ꢉ–ꢉ interactions combined with HÁ Á ÁBr contacts
(Fig. 6, A and B), and BrÁ Á ÁBr interactions between the stacks
(Fig. 6, C).
We expect the ꢉ-stacked molecules along the ac diagonal to
have the highest stabilization (À46.9 kJ molÀ1; interactions A
and B in Fig. 6), and the stabilization for the molecules next to
the stack to be much smaller. For this adjacent stack in the b
direction, there are no contacts shorter than the van der Waals
radii for the (x, y + 1, z) molecule, but the stabilization is still
À21.5 kJ molÀ1. For the next molecule down along ab (x À 1,
y À 1, z), a BrÁ Á ÁBr contact can be seen, but it is very long
À11.8 kJ molÀ1
.
The enrichment ratios (Table 5) clearly show the full-length
parallel contact, with high numbers for CÁ Á ÁC (ꢉ–ꢉ) and
NÁ Á ÁN contacts. Also HÁ Á ÁBr is increased, while again, Br
atoms surprisingly seem to avoid each other.
˚
3.1.4. Compound 8. Compound 8 contains four Br atoms
and crystallizes in the space group P1 with half a molecule in
the asymmetric unit, and consequently an anti conformation
around the double bond (Fig. 6). To give correct results in
CLP, the half-molecule needs to be inverted and added to the
CIF and the space group needs to be changed to P1. The
packing consists of stacks of lengthwise-displaced molecules
(4.04 A) and of the wrong geometry for a halogen bond.
Together with the H4Á Á ÁBr1 interaction, this yields
À13.5 kJ molÀ1. The next molecule down (Àx + 2, Ày + 1, Àz)
is not in the CLP list of stabilizing interactions, which means
its stabilization is smaller than À3.0 kJ molÀ1, and the inter-
acting Br atoms that show a close contact (Fig. 6, C) may
actually be forced into the repulsive region by other stronger
Figure 6
The crystal packing of compound 8. Contacts shorter than the van der Waals radii with the central molecule (magenta) are indicated as cyan dotted lines.
The accompanying capitals refer to the contacts as specified in Table S5 of the supporting information.
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Table 8
Contact enrichment ratios in crystals of compound 9; colour coding from
red to green between 0 and the maximum value in the table.
interactions. There is another contact between Br2 and Br2 at
(Àx, Ày + 1, Àz), which is barely longer than the van der
˚
Waals distance (3.705 A), and appears to have no stabilizing
contribution (> À3.0 kJ molÀ1) either. Between the layers
along the ab plane, interactions seem to be non-existent from a
geometrical viewpoint. CLP, however, calculates intermolecular
stabilization energies of À24.2, À8.2 and À3.4 kJ molÀ1. This is
comparable with the stabilization between the columns in the b
direction. Overall, the stabilization energy is À127.3 kJ molÀ1
(CE-B3LYP À151.8 kJ molÀ1), which is the strongest among
these five structures.
In this case also, the enrichment ratios (Table 6) indicate
that the molecules are parallel displaced along their long axis,
making C contact N and vice versa, as well as producing CÁ Á ÁC
contacts. As in compound 7, there is a larger propensity for H
atoms to contact Br.
3.1.5. Compound 9. Compound 9 is an approximately 50:50
merohedrally twinned crystal, in which additional disorder
occurs in the orientation of the dibromomethyl groups. The
space group is P1, and since the molecule does not have point
symmetry, the asymmetric unit is the whole molecule. The
molecule contains five Br atoms. Since the rotational disorder
of the dibromomethyl group is relatively minor (4.7%), only
the major component was retained for calculations and
analysis.
The packing can be described as sideways parallel-displaced
stacks of ribbons, with CHBr2 groups forming the interface
between the stacks (see Fig. 7). There are plenty of apparent
interactions, all of them involving Br (see Fig. 7, and Table S6
in the supporting information). Nevertheless, the over-
all lattice energy is only À107.2 kJ molÀ1 (CE-B3LYP
À142.12 kJ molÀ1). Both repulsion and dispersion sum up to
numbers slightly higher than for compound 5 (Table 7). The
strongest interactions according to the CLP-PIXEL calcula-
tion unsurprisingly are those between the molecules above
and below the ribbons. The molecules are displaced laterally
over approximately half the ring diagonal, and have otherwise
complete overlap. Stabilization is À42.5 and À36.0 kJ molÀ1
due to mainly the sum of the dispersion and the repulsion
contributions. There are no contacts shorter than the van der
Waals radii. The other interactions in Fig. 7 of Br1 with H and
N (A and B), and of Br2 with H and N (C, D and E) lead to
stabilizations of À30.5 and À22.0 kJ molÀ1, respectively. This
is similar to the stabilization between the central molecule and
the molecule at (Àx + 2, Ày + 1, Àz + 2) (À21.7 kJ molÀ1),
although the latter displays no contacts shorter than the van
der Waals radii by a large margin. The Type I BrÁ Á ÁBr inter-
actions shorter than the van der Waals radii that are present in
the structure (Fig. 7, H and I) barely show up in the interaction
energy list – both are at or under À3.0 kJ molÀ1 (CE inter-
action energy À5.3 and > À4.0 kJ molÀ1), but close contacts
do exist from ring hydrogens to Br of a neighbouring molecule
(Fig. 7, F and G), yielding a À14.9 kJ molÀ1 stabilization.
Figure 7
The crystal packing of compound 9. Contacts shorter than the van der Waals radii with the central molecule (magenta) are indicated as cyan dotted lines.
The accompanying capitals refer to the contacts as specified in Table S6 of the supporting information. Unconnected dots indicate the disorder in the
CHBr2 group.
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˚
a 10 A cluster, the largest number of different intermolecular
interaction pairs was 39 for compound 5. The same remark can
be made as for CLP – since the software is not written for
parallel processing, several calculations can be run at the same
time on several processor cores without interference.
3.2.2. Results. Table 2 and Fig. 8 list the lattice energies that
result from the various calculations. It is obvious that CLP-
PIXEL and AA-CLP faithfully reproduce each other’s order
of stability for the various compounds. For CE-B3LYP, the
trend is approximately the same, but especially for compound
5, a comparatively lower value for the lattice energy is found.
We have been unable to find a reason for this. Both CE and
CLP-PIXEL rely on calibration with regard to a set of (small
molecule) structures for which sublimation enthalpy data are
available and/or high level ab initio pairwise interaction
calculations or periodic calculations have been performed. For
CLP, this resulted in a number of empirical constants that are
taken into account in the expressions for the various terms.
For CE, the correction is made after the calculation of the
separate terms, by using pre-factors to calculate a total lattice
energy. These pre-factors have only been calibrated for the
combinations of HF/6-31G and B3LYP/6-31(d,p) methods and
basis sets. While we have used the 6-311(d,p) basis set instead,
it seems unlikely that the resulting error would only affect 5.
In addition, as can be seen from Table 2, the two compounds
with the lowest melting points (7 and 9) also correspond to the
lowest lattice stabilization energies, as calculated with CE.
This indicates that the comparative value for 5 calculated with
CE could be nearer to reality than the AA-CLP and CLP-
PIXEL results, as the latter would suggest that the melting
point of 5 should be even lower than that of 7 and 9, while it is
in fact comparable to 6 and 8. The assumption that the melting
point should reflect the lattice energy seems reasonable here,
especially given the similarity of the five compounds studied.
Comparing between the various terms in the expressions
used (see Table 7), the Coulombic term is quasi-identical
within 2% between CE and CLP. CLP gives appreciably larger
values for both dispersion and repulsion (by approximately
30–40%), and the values for the polarization term show very
large differences; in CLP, they are a factor 4–8 greater than in
CE and, in absolute value, they contribute ꢂ25% to the total
lattice energy. For CE, their total contribution is only between
2 and 6%.
Figure 8
Calculated lattice energies (kJ molÀ1
calculations made on the five brominated azobenzenes 5–9.
) according to the various
Again the enrichment ratios (Table 8) indicate full-length
parallel contacts (displaced sideways) with even higher values
for CÁ Á ÁC and NÁ Á ÁN due to the contact taking place on both
sides of the molecule, as well as a larger propensity for H
atoms to contact Br, and to an extent N has also an increased
probability of contacting Br.
3.2. Calculations
3.2.1. Methods. We will briefly discuss here our experiences
with the various software packages used during this work. A
summary of the results is available in Fig. 8 and Table 2.
Computationally very cheap, and with the absolutely
shortest learning curve, is the UNI force field calculation in
Mercury (Gavezzotti, 1994; Gavezzotti & Filippini, 1994;
Macrae et al., 2008), which takes seconds or less to learn and
perform. Unfortunately, the results are only suitable for
obtaining a very rough idea of the intermolecular interactions.
The UNI force field atom–atom formalism in CLP (i.e. AA–
CLP) is also very fast (on the order of seconds), but due to the
input file format it takes much longer to set up correctly. The
values that can be obtained, and especially the order of
stability for these five compounds, are quite comparable with
the more sophisticated PIXEL calculations.
CLP PIXEL requires a quantum chemical program that will
write an electron-density cube. The calculation of the wave
function takes some time, especially if a high level wave
function and basis set are chosen (MP2 is recommended, but
we found results to be quite similar using a B3LYP functional).
The PIXEL calculations themselves took about 14 h each on a
single core of an i5 5300U processor at 2.3 GHz, and if
multiple cores are available, multiple calculations can be run
in parallel without interference.
Overall, the total lattice energies calculated by CLP are
around 80% (between 75 and 85%) of those calculated by CE.
Calculating larger and larger clusters in CE will only
increase this difference further. The energy has probably not
˚
fully converged with the 10 A clusters used, but at least the
differences become small (<1 kJ molÀ1), as demonstrated in
Fig. 2. It can also be clearly inferred from Fig. 2 that it is
insufficient, when determining minimum cluster size, to be
satisfied with a small number of steps that show no appreciable
difference. This is due to the discrete process of taking extra
molecules into account. Taking compound 9 as an example, we
find that no noticeable energy difference occurs between 6 and
CrystalExplorer is a much more graphical implementation
of a similar idea. It comes bundled with its own quantum
chemistry program, TONTO, so no external programs are
needed for calculating wave functions. The final calculation
takes a bit longer – typically about 2 h per interaction pair in
the case of these molecules, again on a single core of an i5
5300U processor at 2.3 GHz, and as the cluster of molecules
grows, the number of interaction pairs also grows quickly. For
˚
˚
8.5 A, but from 8.5 to 10 A, there is another appreciable step
in the energies, which is larger than 1 kJ molÀ1 again.
ꢁ
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Bruker (2009). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2010). SAINT and CELL_NOW. Bruker AXS Inc.,
Madison, Wisconsin, USA.
Desiraju, G. R. & Parthasarathy, R. (1989). J. Am. Chem. Soc. 111,
8725–8726.
4. Conclusions
Halogen–halogen interactions as a substantial contributor to
the lattice energies of these kinds of structures seem quite
overrated, despite them very often being the current focal
point in the literature. Of the five structures investigated here,
only one displays what would be classified as a Type II halogen
bond, which, however, turns out to have no appreciable
energetic contribution to the lattice energy whatsoever.
Apart from the lack of halogen–halogen interactions, it
appears that rod-shaped brominated molecules have a bewil-
dering variety of options to pack, the diversity of which is
nicely illustrated by the differently looking color-coded
enrichment ratio tables. The constant factor in all of the
packing systems observed is that packing in these molecules is
mainly determined by molecular shape and dispersion inter-
actions (edge-to-face HÁ Á Áꢉ and face-to-face ꢉ–ꢉ), and not by
specific interactions involving the halogen atoms, which
mainly appear to be accommodated in the lattice as well as
possible.
Frisch, M. J., et al. (2016). GAUSSIAN09. Gaussian Inc., Wallingford,
CT, USA. http://www.gaussian.com.
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Hubschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst.
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Jayatilaka, D. & Grimwood, D. J. (2003). Proceedings of Computa-
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Jelsch, C., Ejsmont, K. & Huder, L. (2014). IUCrJ, 1, 119–128.
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Delaunay, J., Allain, M., Richomme, P. & Roncali, J. (2003). Chem.
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Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J.
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Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe,
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392.
Many new, visual and computationally cheap tools have
been made available in the last few years to the molecular
crystallographer. This article sums up and compares a number
of them. We can conclude that for these bromomethylated
azobenzenes, the AA-CLP approach is perfectly adequate for
calculating a ranking of the lattice energies when compared to
CLP-PIXEL, but do note that the melting points of the
compounds seem to suggest that the CE energies are closer to
reality, especially for compound 5.
Acknowledgements
We are grateful to Mr Christian Herbst (University of
Bremen) for his help with the preparation of the new azo-
benzene derivatives in the course of his semester project and
¨
to Dr Thomas Dulcks and Ms Dorit Kemken (University of
Bremen) for the mass spectrometric characterization.
Thomas, S. P., Spackman, P. R., Jayatilaka, D. & Spackman, M. A.
(2018). J. Chem. Theory Comput. 14, 1614–1623.
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J.,
Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017).
CrystalExplorer17. University of Western Australia.
Vande Velde, C. M. L., Zeller, M. & Azov, V. A. (2015).
CrystEngComm, 17, 5751–5756.
References
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Azov, V. A., Cordes, J., Schluter, D., Dulcks, T., Bockmann, M. &
Doltsinis, N. L. (2014). J. Org. Chem. 79, 11714–11721.
ꢁ
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Comparison of computationally cheap methods
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supporting information
supporting information
Acta Cryst. (2018). C74, 1692-1702 [https://doi.org/10.1107/S2053229618015309]
Comparison of computationally cheap methods for providing insight into the
crystal packing of highly bromomethylated azobenzenes
Christophe M. L. Vande Velde, Matthias Zeller and Vladimir A. Azov
Computing details
For all structures, data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT
(Bruker, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure:
SHELXL2018 (Sheldrick, 2015) and shelXle(Hübschle et al., 2011); software used to prepare material for publication:
SHELXL2018 (Sheldrick, 2015).
(E)-[4-(Bromomethyl)phenyl][4-(dibromomethyl)phenyl]diazene (5)
Crystal data
C14H11Br3N2
Dx = 2.036 Mg m−3
Mr = 446.98
Melting point: 146–148 C K
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 6003 reflections
θ = 2.5–31.0°
Monoclinic, P21/c
a = 8.538 (1) Å
b = 5.283 (1) Å
c = 32.801 (4) Å
β = 99.692 (5)°
V = 1458.4 (4) Å3
Z = 4
µ = 8.29 mm−1
T = 100 K
Plate, orange
0.45 × 0.35 × 0.18 mm
F(000) = 856
Data collection
Bruker SMART 1000
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
ω scans
13694 measured reflections
4445 independent reflections
3947 reflections with I > 2σ(I)
Rint = 0.040
θ
max = 31.4°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
h = −12→12
k = −7→7
T
min = 0.316, Tmax = 0.746
l = −47→46
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.039
wR(F2) = 0.088
S = 1.15
4445 reflections
172 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
Acta Cryst. (2018). C74, 1692-1702
sup-1

supporting information
w = 1/[σ2(Fo2) + (0.0221P)2 + 4.4145P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.003
Δρmax = 1.41 e Å−3
Δρmin = −1.06 e Å−3
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Br1
Br2
Br3
N1
N2
C1
C2
H2
C3
H3
C4
C5
H5
C6
H6
C7
H7
C11
C12
H12
C13
H13
C14
C15
H15
C16
H16
C17
H17A
H17B
0.61597 (4)
0.92730 (4)
0.67770 (4)
0.6931 (4)
0.8014 (4)
0.6963 (4)
0.7807 (4)
0.837587
0.7804 (4)
0.836770
0.6985 (4)
0.6105 (4)
0.552169
0.6084 (4)
0.547020
0.7088 (4)
0.648722
0.8005 (4)
0.7182 (4)
0.658565
0.7239 (4)
0.668797
0.8103 (4)
0.8945 (4)
0.955100
0.8909 (4)
0.949921
0.8106 (4)
0.768991
0.920742
1.05498 (6)
0.72243 (7)
1.00291 (6)
0.7036 (6)
0.8208 (6)
0.7378 (6)
0.9300 (7)
1.052512
0.9398 (6)
1.070822
0.7599 (6)
0.5728 (6)
0.452275
0.5639 (7)
0.438890
0.7544 (6)
0.603256
0.7837 (6)
0.5901 (7)
0.471034
0.5723 (6)
0.439258
0.7486 (6)
0.9373 (7)
1.055490
0.9551 (7)
1.083574
0.7318 (6)
0.564811
0.747939
0.95232 (2)
0.95898 (2)
0.54184 (2)
0.75752 (9)
0.74401 (8)
0.80072 (9)
0.82415 (10)
0.811275
0.86638 (10)
0.882433
0.88542 (9)
0.86189 (10)
0.874761
0.81934 (10)
0.803044
0.93152 (10)
0.938825
0.70107 (10)
0.67781 (10)
0.690584
0.63590 (10)
0.620078
0.01420 (8)
0.01715 (9)
0.01277 (8)
0.0146 (5)
0.0142 (5)
0.0123 (6)
0.0137 (6)
0.016*
0.0115 (6)
0.014*
0.0106 (6)
0.0126 (6)
0.015*
0.0137 (6)
0.016*
0.0109 (6)
0.013*
0.0120 (6)
0.0139 (6)
0.017*
0.0129 (6)
0.015*
0.61663 (10)
0.64037 (10)
0.627698
0.68238 (10)
0.698432
0.57118 (10)
0.560795
0.565756
0.0120 (6)
0.0140 (6)
0.017*
0.0140 (6)
0.017*
0.0139 (6)
0.017*
0.017*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Br1
Br2
0.01541 (16)
0.00833 (15)
0.01421 (16)
0.0289 (2)
0.01425 (15)
0.01414 (15)
0.00470 (12)
0.00497 (13)
0.00615 (11)
0.00154 (11)
−0.00083 (11)
0.00409 (12)
Acta Cryst. (2018). C74, 1692-1702
sup-2

supporting information
Br3
N1
N2
C1
C2
C3
C4
C5
C6
0.00854 (15)
0.0130 (13)
0.0145 (13)
0.0090 (14)
0.0130 (15)
0.0078 (14)
0.0076 (13)
0.0078 (14)
0.0104 (15)
0.0075 (13)
0.0083 (14)
0.0126 (15)
0.0100 (14)
0.0104 (14)
0.0104 (15)
0.0100 (15)
0.0147 (15)
0.01608 (16)
0.0186 (14)
0.0177 (14)
0.0173 (16)
0.0151 (15)
0.0121 (14)
0.0130 (14)
0.0143 (15)
0.0167 (16)
0.0116 (14)
0.0157 (15)
0.0154 (15)
0.0141 (15)
0.0134 (15)
0.0176 (16)
0.0181 (16)
0.0141 (15)
0.01370 (14)
0.0126 (12)
0.0111 (12)
0.0108 (13)
0.0136 (14)
0.0151 (14)
0.0119 (13)
0.0164 (14)
0.0142 (14)
0.0147 (14)
0.0121 (13)
0.0138 (14)
0.0144 (14)
0.0126 (13)
0.0148 (14)
0.0139 (14)
0.0135 (14)
−0.00059 (12)
−0.0007 (11)
−0.0002 (11)
0.0018 (12)
−0.0015 (12)
−0.0030 (11)
0.0028 (11)
−0.0031 (12)
−0.0023 (12)
0.0013 (11)
0.0019 (12)
−0.0005 (12)
−0.0011 (12)
0.0028 (12)
−0.0024 (12)
−0.0021 (12)
0.0023 (12)
0.00187 (11)
0.0031 (10)
0.0037 (10)
0.0022 (11)
0.0045 (12)
0.0037 (11)
0.0039 (11)
0.0038 (11)
0.0026 (11)
0.0047 (11)
0.0015 (11)
0.0027 (11)
0.0019 (11)
0.0031 (11)
0.0049 (11)
0.0023 (11)
0.0044 (12)
0.00244 (11)
0.0008 (10)
0.0001 (10)
0.0003 (11)
0.0018 (11)
−0.0005 (11)
0.0013 (11)
0.0008 (11)
−0.0008 (12)
−0.0010 (11)
0.0015 (11)
0.0019 (11)
−0.0006 (11)
−0.0003 (11)
0.0005 (12)
−0.0030 (12)
0.0003 (11)
C7
C11
C12
C13
C14
C15
C16
C17
Geometric parameters (Å, º)
Br1—C7
Br2—C7
Br3—C17
N1—N2
N1—C1
N2—C11
C1—C6
C1—C2
C2—C3
C2—H2
C3—C4
C3—H3
C4—C5
C4—C7
C5—C6
C5—H5
1.948 (3)
C6—H6
C7—H7
0.9500
1.0000
1.938 (3)
1.974 (3)
1.254 (4)
1.424 (4)
1.421 (4)
1.391 (5)
1.398 (5)
1.386 (4)
0.9500
1.389 (4)
0.9500
1.394 (5)
1.500 (4)
1.394 (4)
0.9500
C11—C12
C11—C16
C12—C13
C12—H12
C13—C14
C13—H13
C14—C15
C14—C17
C15—C16
C15—H15
C16—H16
C17—H17A
C17—H17B
1.393 (5)
1.397 (5)
1.387 (4)
0.9500
1.403 (5)
0.9500
1.389 (5)
1.494 (4)
1.387 (4)
0.9500
0.9500
0.9900
0.9900
N2—N1—C1
N1—N2—C11
C6—C1—C2
C6—C1—N1
C2—C1—N1
C3—C2—C1
C3—C2—H2
C1—C2—H2
C2—C3—C4
C2—C3—H3
C4—C3—H3
113.4 (3)
113.6 (3)
120.3 (3)
115.6 (3)
124.1 (3)
119.3 (3)
120.4
120.4
120.6 (3)
119.7
Br1—C7—H7
108.2
C12—C11—C16
C12—C11—N2
C16—C11—N2
C13—C12—C11
C13—C12—H12
C11—C12—H12
C12—C13—C14
C12—C13—H13
C14—C13—H13
C15—C14—C13
120.0 (3)
124.2 (3)
115.7 (3)
119.6 (3)
120.2
120.2
120.7 (3)
119.7
119.7
119.1 (3)
119.7
Acta Cryst. (2018). C74, 1692-1702
sup-3

supporting information
C3—C4—C5
C3—C4—C7
C5—C4—C7
C6—C5—C4
C6—C5—H5
C4—C5—H5
C1—C6—C5
C1—C6—H6
C5—C6—H6
C4—C7—Br2
C4—C7—Br1
Br2—C7—Br1
C4—C7—H7
Br2—C7—H7
120.1 (3)
121.2 (3)
118.6 (3)
119.6 (3)
120.2
120.2
120.0 (3)
120.0
C15—C14—C17
C13—C14—C17
C16—C15—C14
C16—C15—H15
C14—C15—H15
C15—C16—C11
C15—C16—H16
C11—C16—H16
C14—C17—Br3
C14—C17—H17A
Br3—C17—H17A
C14—C17—H17B
Br3—C17—H17B
H17A—C17—H17B
120.9 (3)
120.0 (3)
120.6 (3)
119.7
119.7
119.9 (3)
120.0
120.0
110.3 (2)
109.6
109.6
109.6
120.0
111.0 (2)
112.3 (2)
108.96 (15)
108.2
109.6
108.1
108.2
C1—N1—N2—C11
N2—N1—C1—C6
N2—N1—C1—C2
C6—C1—C2—C3
N1—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
C2—C3—C4—C7
C3—C4—C5—C6
C7—C4—C5—C6
C2—C1—C6—C5
N1—C1—C6—C5
C4—C5—C6—C1
C3—C4—C7—Br2
C5—C4—C7—Br2
C3—C4—C7—Br1
178.9 (3)
−163.6 (3)
16.2 (5)
2.3 (5)
−177.5 (3)
0.6 (5)
−2.5 (5)
174.6 (3)
1.6 (5)
−175.5 (3)
−3.2 (5)
176.7 (3)
1.2 (5)
C5—C4—C7—Br1
N1—N2—C11—C12
N1—N2—C11—C16
−117.6 (3)
−16.0 (5)
164.7 (3)
−1.4 (5)
179.4 (3)
−0.7 (5)
2.0 (5)
−177.9 (3)
−1.3 (5)
178.6 (3)
−0.8 (5)
2.1 (5)
−178.6 (3)
−73.7 (4)
106.1 (3)
C16—C11—C12—C13
N2—C11—C12—C13
C11—C12—C13—C14
C12—C13—C14—C15
C12—C13—C14—C17
C13—C14—C15—C16
C17—C14—C15—C16
C14—C15—C16—C11
C12—C11—C16—C15
N2—C11—C16—C15
C15—C14—C17—Br3
C13—C14—C17—Br3
−57.0 (4)
120.1 (3)
65.3 (4)
(E)-1,2-Bis[4-(dibromomethyl)phenyl]diazene (6)
Crystal data
C14H10Br4N2
Dx = 2.220 Mg m−3
Mr = 525.88
Melting point: 151-153 C K
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2626 reflections
θ = 2.4–30.9°
µ = 10.22 mm−1
T = 100 K
Block, red
0.51 × 0.48 × 0.38 mm
Monoclinic, C2/c
a = 20.379 (3) Å
b = 8.6401 (10) Å
c = 9.8451 (10) Å
β = 114.797 (2)°
V = 1573.7 (3) Å3
Z = 4
F(000) = 992
Data collection
Bruker SMART 1000
Graphite monochromator
diffractometer
ω scans
Radiation source: fine-focus sealed tube
Acta Cryst. (2018). C74, 1692-1702
sup-4

supporting information
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
Rint = 0.028
max = 31.2°, θmin = 2.2°
θ
T
min = 0.406, Tmax = 0.746
h = −24→29
k = −12→12
l = −14→13
5663 measured reflections
2322 independent reflections
2049 reflections with I > 2σ(I)
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.024
wR(F2) = 0.056
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0249P)2 + 1.3279P]
where P = (Fo2 + 2Fc2)/3
S = 1.02
2322 reflections
92 parameters
0 restraints
(Δ/σ)max = 0.002
Δρmax = 0.82 e Å−3
Δρmin = −0.60 e Å−3
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Extinction correction: SHELXL2018
(Sheldrick, 2015),
Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.00183 (16)
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Br1
Br2
N1
C1
C2
H2
C3
H3
C4
C5
H5
C6
H6
C7
H7
0.23156 (2)
0.36677 (2)
0.48068 (10)
0.44107 (11)
0.44206 (13)
0.470686
0.40098 (13)
0.401720
0.35791 (12)
0.35691 (12)
0.327697
0.44833 (3)
0.26407 (2)
0.9973 (2)
0.8564 (2)
0.7356 (2)
0.743489
0.6056 (2)
0.522915
0.5935 (2)
0.7138 (2)
0.706657
0.8452 (2)
0.927179
0.4548 (2)
0.461829
0.27413 (3)
0.50812 (3)
0.5356 (2)
0.5167 (2)
0.4222 (3)
0.367280
0.4103 (3)
0.347309
0.4902 (2)
0.5828 (3)
0.636582
0.5966 (3)
0.660821
0.4738 (3)
0.549495
0.01427 (7)
0.01505 (8)
0.0120 (4)
0.0096 (4)
0.0124 (4)
0.015*
0.0124 (4)
0.015*
0.0102 (4)
0.0116 (4)
0.014*
0.39902 (12)
0.398937
0.31141 (13)
0.290721
0.0119 (4)
0.014*
0.0118 (4)
0.014*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Br1
Br2
0.00683 (12)
0.01663 (14)
0.01807 (11)
0.00894 (10)
0.01567 (13)
0.01627 (13)
−0.00205 (7)
−0.00040 (7)
0.00252 (9)
0.00363 (10)
−0.00163 (8)
0.00142 (7)
Acta Cryst. (2018). C74, 1692-1702
sup-5

supporting information
N1
C1
C2
C3
C4
C5
C6
C7
0.0100 (10)
0.0058 (10)
0.0119 (11)
0.0133 (11)
0.0079 (10)
0.0103 (11)
0.0115 (11)
0.0111 (11)
0.0096 (7)
0.0094 (8)
0.0125 (9)
0.0110 (9)
0.0092 (8)
0.0122 (9)
0.0103 (8)
0.0104 (9)
0.0146 (10)
0.0104 (10)
0.0136 (11)
0.0138 (11)
0.0113 (10)
0.0129 (11)
0.0133 (11)
0.0144 (11)
−0.0021 (6)
−0.0015 (7)
−0.0025 (8)
−0.0019 (7)
−0.0019 (7)
−0.0010 (7)
−0.0006 (7)
−0.0023 (7)
0.0032 (8)
0.0004 (8)
0.0060 (9)
0.0065 (9)
0.0017 (8)
0.0055 (9)
0.0046 (9)
0.0057 (9)
0.0006 (6)
0.0003 (7)
−0.0026 (8)
−0.0031 (7)
0.0006 (7)
0.0007 (7)
−0.0009 (7)
−0.0021 (7)
Geometric parameters (Å, º)
Br1—C7
Br2—C7
N1—N1i
N1—C1
C1—C6
C1—C2
C2—C3
C2—H2
1.958 (2)
C3—C4
1.407 (3)
0.9500
1.388 (3)
1.494 (3)
1.395 (3)
0.9500
1.945 (2)
1.255 (4)
1.429 (3)
1.389 (3)
1.404 (3)
1.376 (3)
0.9500
C3—H3
C4—C5
C4—C7
C5—C6
C5—H5
C6—H6
C7—H7
0.9500
1.0000
N1i—N1—C1
C6—C1—C2
C6—C1—N1
C2—C1—N1
C3—C2—C1
C3—C2—H2
C1—C2—H2
C2—C3—C4
C2—C3—H3
C4—C3—H3
C5—C4—C3
C5—C4—C7
C3—C4—C7
114.3 (2)
C4—C5—C6
C4—C5—H5
C6—C5—H5
C1—C6—C5
C1—C6—H6
C5—C6—H6
C4—C7—Br2
C4—C7—Br1
Br2—C7—Br1
C4—C7—H7
Br2—C7—H7
Br1—C7—H7
119.7 (2)
120.2
120.2
120.2 (2)
119.9
119.9
111.44 (16)
110.73 (15)
109.11 (10)
108.5
108.5
108.5
120.49 (19)
115.77 (18)
123.7 (2)
119.1 (2)
120.5
120.5
120.8 (2)
119.6
119.6
119.76 (19)
119.2 (2)
120.99 (19)
N1i—N1—C1—C6
N1i—N1—C1—C2
C6—C1—C2—C3
N1—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
C2—C3—C4—C7
C3—C4—C5—C6
178.6 (2)
−2.6 (4)
−0.2 (3)
−179.0 (2)
0.6 (3)
−0.3 (3)
178.0 (2)
−0.4 (3)
C7—C4—C5—C6
C2—C1—C6—C5
N1—C1—C6—C5
C4—C5—C6—C1
C5—C4—C7—Br2
C3—C4—C7—Br2
C5—C4—C7—Br1
C3—C4—C7—Br1
−178.7 (2)
−0.4 (3)
178.4 (2)
0.8 (3)
−128.80 (19)
52.9 (3)
109.6 (2)
−68.7 (2)
Symmetry code: (i) −x+1, −y+2, −z+1.
Acta Cryst. (2018). C74, 1692-1702
sup-6

supporting information
(E)-[3-(Bromomethyl)phenyl][3-(dibromomethyl)phenyl]diazene (7)
Crystal data
C14H11Br3N2
Mr = 446.98
Dx = 2.006 Mg m−3
Melting point: 120-121 C K
Monoclinic, P21/c
a = 9.1219 (12) Å
b = 16.904 (2) Å
c = 10.3633 (14) Å
β = 112.122 (2)°
V = 1480.4 (3) Å3
Z = 4
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 3951 reflections
θ = 2.4–30.6°
µ = 8.16 mm−1
T = 100 K
Plate, orange
0.52 × 0.45 × 0.15 mm
F(000) = 856
Data collection
Bruker SMART 1000
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
ω scans
12573 measured reflections
4362 independent reflections
3587 reflections with I > 2σ(I)
Rint = 0.038
θ
max = 31.2°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
h = −12→9
k = −23→23
l = −15→14
T
min = 0.349, Tmax = 0.746
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.041
wR(F2) = 0.104
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.03
4362 reflections
172 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0501P)2 + 3.0958P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 2.24 e Å−3
Δρmin = −1.56 e Å−3
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Br1
Br2
Br3
N1
N2
C1
1.09235 (4)
0.94505 (5)
−0.00058 (5)
0.4960 (4)
0.5936 (3)
0.5604 (4)
0.7098 (4)
0.779123
0.54419 (2)
0.41237 (2)
0.24139 (2)
0.43930 (17)
0.39273 (16)
0.48745 (18)
0.47785 (19)
0.438302
0.34234 (3)
0.11026 (4)
0.40366 (4)
0.3487 (3)
0.4327 (3)
0.2701 (3)
0.2674 (3)
0.322746
0.01965 (10)
0.02092 (10)
0.02690 (11)
0.0157 (6)
0.0136 (5)
0.0134 (6)
0.0139 (6)
0.017*
C2
H2
Acta Cryst. (2018). C74, 1692-1702
sup-7

supporting information
C3
C4
H4
C5
H5
C6
H6
C7
0.7572 (4)
0.6551 (4)
0.688248
0.5056 (4)
0.437065
0.4570 (4)
0.353993
0.9147 (4)
0.917280
0.5242 (4)
0.3667 (4)
0.298856
0.3095 (4)
0.4110 (4)
0.371548
0.5673 (5)
0.635204
0.6254 (4)
0.732794
0.1423 (5)
0.108921
0.133999
0.52686 (19)
0.58540 (19)
0.618877
0.5950 (2)
0.635233
0.54534 (19)
0.550622
0.51828 (19)
0.556187
0.34393 (18)
0.34994 (19)
0.387776
0.3004 (2)
0.2447 (2)
0.210409
0.2392 (2)
0.201636
0.2887 (2)
0.285066
0.1825 (3)
0.1023 (3)
0.044799
0.1060 (3)
0.052167
0.1888 (3)
0.190390
0.1700 (3)
0.096781
0.5071 (3)
0.4934 (3)
0.431683
0.5702 (3)
0.6609 (3)
0.712955
0.6753 (3)
0.737713
0.5980 (3)
0.607032
0.5578 (4)
0.540690
0.646449
0.0138 (6)
0.0166 (6)
0.020*
0.0177 (7)
0.021*
0.0157 (6)
0.019*
0.0157 (6)
0.019*
0.0133 (6)
0.0144 (6)
0.017*
0.0153 (6)
0.0178 (7)
0.021*
0.0184 (7)
0.022*
0.0160 (6)
0.019*
H7
C11
C12
H12
C13
C14
H14
C15
H15
C16
H16
C17
H17A
H17B
0.3077 (2)
0.363708
0.291236
0.0226 (7)
0.027*
0.027*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Br1
Br2
Br3
N1
N2
C1
C2
C3
C4
C5
0.00936 (17)
0.0205 (2)
0.02557 (18)
0.01986 (16)
0.0289 (2)
0.02167 (16)
0.02431 (17)
0.0310 (2)
−0.00070 (13)
0.00050 (13)
−0.00430 (15)
−0.0008 (11)
0.0004 (10)
−0.0020 (12)
−0.0004 (12)
0.0000 (12)
−0.0015 (13)
0.0010 (13)
−0.0001 (12)
−0.0018 (13)
−0.0024 (12)
0.0012 (12)
0.00316 (13)
0.01055 (14)
−0.00094 (14)
0.0036 (11)
0.0034 (10)
0.0021 (11)
0.0006 (11)
0.0007 (11)
0.0025 (13)
0.0012 (12)
0.0020 (12)
0.0048 (12)
0.0029 (11)
0.0030 (12)
0.0044 (12)
0.0045 (13)
0.0001 (12)
0.0024 (12)
0.0108 (15)
−0.00445 (13)
−0.00337 (12)
0.00581 (15)
0.0013 (10)
0.0010 (10)
−0.0012 (11)
0.0002 (11)
−0.0013 (11)
0.0029 (11)
0.0032 (12)
−0.0003 (12)
−0.0012 (11)
−0.0015 (11)
0.0000 (11)
−0.0050 (11)
0.0003 (12)
0.0032 (12)
−0.0007 (12)
−0.0020 (14)
0.01277 (19)
0.0137 (15)
0.0107 (14)
0.0125 (16)
0.0109 (16)
0.0120 (16)
0.0169 (18)
0.0152 (17)
0.0105 (16)
0.0159 (17)
0.0131 (16)
0.0130 (16)
0.0128 (16)
0.0171 (18)
0.0173 (18)
0.0105 (16)
0.0166 (19)
0.0168 (12)
0.0148 (12)
0.0140 (13)
0.0150 (14)
0.0137 (13)
0.0144 (14)
0.0167 (14)
0.0165 (14)
0.0161 (14)
0.0131 (13)
0.0151 (14)
0.0176 (14)
0.0198 (15)
0.0161 (14)
0.0174 (14)
0.0266 (18)
0.0150 (12)
0.0141 (11)
0.0115 (12)
0.0125 (13)
0.0122 (12)
0.0154 (14)
0.0170 (14)
0.0172 (14)
0.0144 (13)
0.0122 (12)
0.0133 (13)
0.0148 (13)
0.0152 (14)
0.0163 (14)
0.0177 (14)
0.0269 (17)
C6
C7
C11
C12
C13
C14
C15
C16
C17
−0.0018 (12)
−0.0054 (14)
−0.0006 (13)
−0.0027 (13)
−0.0027 (15)
Acta Cryst. (2018). C74, 1692-1702
sup-8

supporting information
Geometric parameters (Å, º)
Br1—C7
Br2—C7
Br3—C17
N1—N2
N1—C1
N2—C11
C1—C2
C1—C6
C2—C3
C2—H2
C3—C4
C3—C7
C4—C5
C4—H4
C5—C6
C5—H5
1.957 (3)
1.948 (3)
1.985 (4)
1.260 (4)
1.425 (4)
1.430 (4)
1.383 (5)
1.400 (5)
1.390 (4)
0.9500
1.398 (4)
1.497 (5)
1.388 (5)
0.9500
1.387 (5)
0.9500
C6—H6
C7—H7
0.9500
1.0000
C11—C12
C11—C16
C12—C13
C12—H12
C13—C14
C13—C17
C14—C15
C14—H14
C15—C16
C15—H15
C16—H16
C17—H17A
C17—H17B
1.393 (5)
1.398 (5)
1.385 (5)
0.9500
1.404 (5)
1.487 (5)
1.380 (6)
0.9500
1.395 (5)
0.9500
0.9500
0.9900
0.9900
N2—N1—C1
N1—N2—C11
C2—C1—C6
C2—C1—N1
C6—C1—N1
C1—C2—C3
C1—C2—H2
C3—C2—H2
C2—C3—C4
C2—C3—C7
C4—C3—C7
C5—C4—C3
C5—C4—H4
C3—C4—H4
C6—C5—C4
C6—C5—H5
C4—C5—H5
C5—C6—C1
C5—C6—H6
C1—C6—H6
C3—C7—Br2
C3—C7—Br1
Br2—C7—Br1
C3—C7—H7
Br2—C7—H7
114.6 (3)
113.1 (3)
121.0 (3)
124.5 (3)
114.4 (3)
119.1 (3)
120.4
Br1—C7—H7
107.5
C12—C11—C16
C12—C11—N2
C16—C11—N2
C13—C12—C11
C13—C12—H12
C11—C12—H12
C12—C13—C14
C12—C13—C17
C14—C13—C17
C15—C14—C13
C15—C14—H14
C13—C14—H14
C14—C15—C16
C14—C15—H15
C16—C15—H15
C15—C16—C11
C15—C16—H16
C11—C16—H16
C13—C17—Br3
C13—C17—H17A
Br3—C17—H17A
C13—C17—H17B
Br3—C17—H17B
H17A—C17—H17B
120.8 (3)
123.5 (3)
115.7 (3)
119.6 (3)
120.2
120.2
120.4
119.6 (3)
119.7 (3)
120.6 (3)
120.8 (3)
119.6
119.6
119.9 (3)
120.1
120.1
119.4 (3)
120.3
120.3
111.4 (2)
109.4
120.1 (3)
122.3 (3)
117.6 (3)
120.5 (3)
119.7
119.7
119.5 (3)
120.2
120.2
119.7 (3)
120.2
120.2
111.9 (2)
113.0 (2)
109.14 (17)
107.5
109.4
109.4
109.4
108.0
107.5
C1—N1—N2—C11
N2—N1—C1—C2
N2—N1—C1—C6
−178.5 (3)
9.4 (5)
−173.0 (3)
C4—C3—C7—Br1
N1—N2—C11—C12
N1—N2—C11—C16
114.7 (3)
−3.0 (4)
177.5 (3)
Acta Cryst. (2018). C74, 1692-1702
sup-9

supporting information
C6—C1—C2—C3
N1—C1—C2—C3
C1—C2—C3—C4
C1—C2—C3—C7
C2—C3—C4—C5
C7—C3—C4—C5
C3—C4—C5—C6
C4—C5—C6—C1
C2—C1—C6—C5
N1—C1—C6—C5
C2—C3—C7—Br2
C4—C3—C7—Br2
C2—C3—C7—Br1
0.2 (5)
177.6 (3)
0.6 (5)
C16—C11—C12—C13
−0.3 (5)
−179.7 (3)
−0.1 (5)
178.8 (3)
0.5 (5)
−178.3 (3)
−0.7 (5)
0.3 (5)
N2—C11—C12—C13
C11—C12—C13—C14
C11—C12—C13—C17
C12—C13—C14—C15
C17—C13—C14—C15
C13—C14—C15—C16
C14—C15—C16—C11
C12—C11—C16—C15
N2—C11—C16—C15
C12—C13—C17—Br3
C14—C13—C17—Br3
−177.8 (3)
−0.3 (5)
178.2 (3)
−0.8 (5)
1.5 (5)
−1.2 (5)
−178.9 (3)
56.7 (4)
−121.7 (3)
−66.9 (4)
0.2 (5)
179.6 (3)
88.1 (3)
−93.0 (3)
(E)-1,2-Bis[3-(dibromomethyl)phenyl]diazene (8)
Crystal data
C14H10Br4N2
Mr = 525.88
F(000) = 248
Dx = 2.274 Mg m−3
Triclinic, P1
Melting point: 130-132 C K
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2578 reflections
θ = 2.5–31.2°
µ = 10.47 mm−1
T = 100 K
Block, red
0.45 × 0.25 × 0.20 mm
a = 4.899 (2) Å
b = 8.294 (2) Å
c = 9.942 (3) Å
α = 98.103 (4)°
β = 103.640 (3)°
γ = 96.650 (3)°
V = 384.0 (2) Å3
Z = 1
Data collection
Bruker SMART 1000
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
ω scans
5417 measured reflections
2249 independent reflections
1993 reflections with I > 2σ(I)
Rint = 0.042
θ
max = 31.2°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
h = −6→7
k = −11→11
l = −14→14
T
min = 0.308, Tmax = 0.746
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.033
wR(F2) = 0.085
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0356P)2 + 0.5445P]
where P = (Fo2 + 2Fc2)/3
S = 1.05
2249 reflections
92 parameters
0 restraints
(Δ/σ)max < 0.001
Δρmax = 1.08 e Å−3
Δρmin = −1.11 e Å−3
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Extinction correction: SHELXL2018
(Sheldrick, 2015),
Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.022 (2)
Acta Cryst. (2018). C74, 1692-1702
sup-10

supporting information
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Br1
Br2
N1
C1
C2
H2
C3
H3
C4
H4
C5
C6
H6
C7
H7
0.70209 (6)
0.20145 (6)
0.0313 (5)
0.4352 (5)
0.5243 (6)
0.638710
0.4455 (6)
0.505053
0.2802 (6)
0.225421
0.1935 (5)
0.2684 (6)
0.206496
0.5238 (6)
0.667019
0.44619 (3)
0.33924 (4)
−0.0658 (3)
0.1125 (3)
−0.0295 (4)
−0.023851
−0.1808 (4)
−0.277981
−0.1874 (3)
−0.289857
−0.0453 (3)
0.1049 (3)
0.201498
0.34815 (3)
0.06638 (3)
0.4728 (3)
0.2374 (3)
0.1812 (3)
0.116479
0.01868 (11)
0.01621 (11)
0.0132 (5)
0.0112 (5)
0.0120 (5)
0.014*
0.0139 (5)
0.017*
0.0134 (5)
0.016*
0.0112 (5)
0.0121 (5)
0.015*
0.0128 (5)
0.015*
0.2198 (3)
0.181129
0.3148 (3)
0.340843
0.3726 (3)
0.3332 (3)
0.371228
0.1914 (3)
0.136699
0.2695 (4)
0.248602
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Br1
Br2
N1
C1
C2
C3
C4
C5
C6
C7
0.02306 (17)
0.01474 (16)
0.0128 (10)
0.0096 (11)
0.0128 (11)
0.0187 (13)
0.0165 (12)
0.0099 (11)
0.0126 (11)
0.0114 (11)
0.00910 (16)
0.01765 (18)
0.0114 (11)
0.0097 (12)
0.0116 (13)
0.0075 (12)
0.0070 (12)
0.0106 (13)
0.0093 (12)
0.0102 (12)
0.01960 (17)
0.01783 (17)
0.0144 (11)
0.0123 (12)
0.0098 (11)
0.0140 (12)
0.0146 (12)
0.0117 (11)
0.0136 (12)
0.0150 (12)
−0.00228 (11)
0.00473 (11)
0.0008 (9)
0.0010 (9)
0.0021 (10)
0.0035 (10)
0.0006 (10)
0.0002 (9)
0.0019 (9)
0.0005 (9)
0.00056 (11)
0.00286 (10)
0.0016 (8)
−0.0007 (8)
0.0000 (9)
0.0019 (10)
0.0010 (9)
0.0005 (8)
0.0016 (9)
0.0007 (9)
0.00057 (11)
0.00875 (11)
0.0026 (9)
0.0021 (9)
0.0009 (10)
−0.0004 (10)
0.0011 (10)
0.0024 (9)
0.0024 (10)
0.0018 (10)
Geometric parameters (Å, º)
Br1—C7
Br2—C7
N1—N1i
N1—C5
C1—C2
C1—C6
C1—C7
1.938 (3)
C2—H2
C3—C4
C3—H3
C4—C5
C4—H4
C5—C6
C6—H6
0.9500
1.384 (4)
0.9500
1.393 (4)
0.9500
1.393 (4)
0.9500
1.965 (3)
1.253 (5)
1.429 (4)
1.393 (4)
1.397 (4)
1.491 (4)
Acta Cryst. (2018). C74, 1692-1702
sup-11

supporting information
C2—C3
1.402 (4)
C7—H7
1.0000
N1i—N1—C5
C2—C1—C6
C2—C1—C7
C6—C1—C7
C1—C2—C3
C1—C2—H2
C3—C2—H2
C4—C3—C2
C4—C3—H3
C2—C3—H3
C3—C4—C5
C3—C4—H4
C5—C4—H4
113.9 (3)
120.1 (3)
117.7 (2)
122.2 (2)
120.1 (3)
119.9
119.9
119.4 (3)
120.3
C4—C5—C6
C4—C5—N1
C6—C5—N1
C5—C6—C1
C5—C6—H6
C1—C6—H6
C1—C7—Br1
C1—C7—Br2
Br1—C7—Br2
C1—C7—H7
Br1—C7—H7
Br2—C7—H7
120.1 (3)
115.8 (2)
124.1 (3)
119.6 (3)
120.2
120.2
112.63 (19)
111.38 (18)
109.85 (14)
107.6
107.6
107.6
120.3
120.6 (3)
119.7
119.7
C6—C1—C2—C3
C7—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
C3—C4—C5—C6
C3—C4—C5—N1
N1i—N1—C5—C4
N1i—N1—C5—C6
0.4 (4)
C4—C5—C6—C1
N1—C5—C6—C1
C2—C1—C6—C5
C7—C1—C6—C5
C2—C1—C7—Br1
C6—C1—C7—Br1
C2—C1—C7—Br2
C6—C1—C7—Br2
−1.2 (4)
178.0 (2)
0.4 (4)
−179.7 (2)
−128.1 (2)
52.1 (3)
108.0 (2)
−71.9 (3)
−179.5 (2)
−0.4 (4)
−0.4 (4)
1.2 (4)
−178.1 (3)
176.8 (3)
−2.4 (4)
Symmetry code: (i) −x, −y, −z+1.
(E)-[3-(Dibromomethyl)phenyl][3-(tribromomethyl)phenyl]diazene (9)
Crystal data
C14H9Br5N2
Mr = 604.78
F(000) = 564
Dx = 2.375 Mg m−3
Triclinic, P1
Melting point: 142-143 C K
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 1139 reflections
θ = 2.5–31.1°
a = 7.0161 (11) Å
b = 8.5634 (13) Å
c = 14.897 (2) Å
α = 103.257 (2)°
β = 102.974 (2)°
γ = 91.703 (2)°
V = 845.8 (2) Å3
Z = 2
µ = 11.87 mm−1
T = 100 K
Block, orange
0.45 × 0.43 × 0.21 mm
Data collection
Bruker SMART 1000
diffractometer
Radiation source: sealed tube
ω scans
8987 independent reflections
6827 reflections with I > 2σ(I)
Rint = 0.066
θ
max = 31.3°, θmin = 1.5°
Absorption correction: multi-scan
(TWINABS; Sheldrick, 2012)
h = −10→9
k = −12→12
l = 0→21
T
min = 0.014, Tmax = 0.052
15148 measured reflections
Acta Cryst. (2018). C74, 1692-1702
sup-12

supporting information
Refinement
Refinement on F2
Secondary atom site location: difference Fourier
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.051
wR(F2) = 0.137
map
Hydrogen site location: inferred from
neighbouring sites
S = 0.99
8987 reflections
213 parameters
58 restraints
Primary atom site location: structure-invariant
direct methods
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0797P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 1.81 e Å−3
Δρmin = −1.56 e Å−3
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refined as a 2-component twin. The structure was solved using direct methods with only the non-
overlapping reflections of component 1. The structure was refined using the hklf 5 routine with all reflections of both
components (including the overlapping ones), resulting in a BASF value of 0.481 (1).
Minor but clearly resolved disorder was observed for the dibromomethyl group. The major and minor moieties were
restrained to have similar geometries (SAME restraint of SHELXL, e.s.d. 0.02 Angstrom). The carbon atom C10 was
included in the disorder modeling and 1,2 and 1,3 C—C distances involving the major and minor components of C10
were restrained to be similar (SADI restraint of SHELXL, e.s.d. 0.02 Angstrom). 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 refined to 0.9601 (19) to 0.0399 (19).
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Occ. (<1)
Br1
Br2
N1
N2
C1
C3
C4
H4
C5
H5
C6
H6
C7
H7
C8
H8
C9
H9
C11
C12
C14
0.90836 (8)
0.46223 (8)
0.7664 (6)
0.7756 (6)
0.7187 (7)
0.6536 (7)
0.6279 (8)
0.595699
0.7064 (7)
0.729007
0.6409 (8)
0.619070
0.8868 (8)
0.901178
0.9118 (8)
0.944967
0.6853 (8)
0.693124
0.8212 (7)
0.8889 (8)
0.8450 (7)
1.08792 (7)
1.07967 (7)
0.6292 (6)
0.4901 (6)
0.6301 (7)
0.9644 (6)
0.6584 (7)
0.667201
0.7811 (7)
0.874865
0.5070 (7)
0.413565
0.3130 (8)
0.208546
0.4452 (7)
0.431907
0.4911 (7)
0.387486
0.4838 (7)
0.5986 (7)
0.6200 (7)
0.36771 (5)
0.37101 (5)
0.5351 (3)
0.5496 (3)
0.4368 (4)
0.3090 (4)
0.2506 (4)
0.186613
0.4171 (4)
0.467909
0.2697 (4)
0.218693
0.7556 (4)
0.766690
0.8309 (4)
0.893937
0.3621 (4)
0.374978
0.6464 (4)
0.8152 (4)
0.7228 (4)
0.02429 (15)
0.02458 (15)
0.0191 (9)
0.0206 (9)
0.0181 (10)
0.0177 (10)
0.0203 (10)
0.024*
0.0179 (10)
0.021*
0.0238 (11)
0.029*
0.0258 (12)
0.031*
0.0251 (12)
0.030*
0.0212 (10)
0.025*
0.0191 (10)
0.0228 (11)
0.0205 (10)
Acta Cryst. (2018). C74, 1692-1702
sup-13

supporting information
H14
C15
H15
C16
Br3
C10
H10
Br4
0.831452
0.8403 (8)
0.821753
0.6612 (7)
0.58568 (11)
0.9060 (9)
0.878219
0.71615 (10)
1.16852 (11)
0.942 (6)
0.724552
0.3321 (7)
0.240510
0.7963 (7)
0.97768 (9)
0.7456 (8)
0.840293
0.72607 (10)
0.78735 (12)
0.735 (2)
0.711806
0.6629 (4)
0.610947
0.025*
0.0217 (11)
0.026*
0.3236 (4)
0.17782 (4)
0.8944 (4)
0.866313
0.97006 (5)
0.98005 (6)
0.9006 (16)
0.942383
0.0186 (10)
0.03647 (18)
0.0281 (13)
0.034*
0.0349 (2)
0.0371 (2)
0.034 (7)
0.041*
0.9601 (19)
0.9601 (19)
0.9601 (19)
0.9601 (19)
0.0399 (19)
0.0399 (19)
0.0399 (19)
0.0399 (19)
Br5
C10B
H10B
Br4B
Br5B
0.851659
0.910 (3)
1.209 (3)
0.724703
0.930 (2)
0.711 (3)
0.8670 (14)
0.9683 (15)
0.049 (5)
0.0371 (2)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Br1
Br2
N1
N2
C1
C3
C4
C5
C6
0.0214 (3)
0.0248 (3)
0.020 (2)
0.024 (2)
0.018 (2)
0.025 (2)
0.024 (2)
0.023 (2)
0.025 (3)
0.028 (3)
0.027 (3)
0.024 (2)
0.019 (2)
0.023 (3)
0.022 (2)
0.025 (2)
0.019 (2)
0.0642 (4)
0.035 (3)
0.0415 (4)
0.0384 (4)
0.040 (11)
0.063 (10)
0.0384 (4)
0.0195 (3)
0.0212 (3)
0.020 (2)
0.020 (2)
0.017 (3)
0.017 (3)
0.021 (3)
0.016 (3)
0.021 (3)
0.024 (3)
0.025 (3)
0.014 (3)
0.021 (3)
0.025 (3)
0.018 (3)
0.017 (3)
0.021 (3)
0.0289 (4)
0.030 (3)
0.0424 (4)
0.0395 (5)
0.035 (11)
0.045 (10)
0.0395 (5)
0.0315 (3)
0.0314 (3)
0.017 (2)
0.019 (2)
0.018 (2)
0.009 (2)
0.014 (2)
0.012 (2)
0.021 (3)
0.031 (3)
0.026 (3)
0.023 (3)
0.018 (3)
0.021 (3)
0.023 (3)
0.025 (3)
0.017 (3)
0.0136 (3)
0.017 (3)
0.0201 (3)
0.0274 (4)
0.022 (10)
0.027 (9)
0.0274 (4)
0.00001 (18)
0.0047 (2)
0.0109 (2)
0.0021 (16)
0.0053 (17)
0.0016 (18)
0.0024 (18)
0.0027 (19)
0.0036 (18)
0.002 (2)
0.009 (2)
0.005 (2)
0.004 (2)
0.0026 (19)
0.005 (2)
0.0070 (2)
0.0091 (2)
0.0049 (18)
0.0067 (19)
0.004 (2)
−0.0006 (19)
0.000 (2)
−0.0009 (19)
−0.001 (2)
0.015 (2)
0.012 (2)
0.003 (2)
0.007 (2)
0.007 (2)
0.008 (2)
0.006 (2)
0.006 (2)
0.0060 (2)
0.007 (3)
0.0066 (2)
0.0008 (16)
0.0013 (17)
−0.0003 (17)
0.0005 (18)
0.0005 (19)
0.0020 (18)
0.000 (2)
C7
C8
C9
0.005 (2)
0.004 (2)
−0.0007 (19)
0.0020 (18)
0.001 (2)
0.0022 (19)
0.0035 (19)
0.0016 (18)
0.0024 (3)
0.001 (2)
0.0067 (3)
−0.0099 (3)
−0.002 (10)
0.009 (8)
C11
C12
C14
C15
C16
Br3
C10
Br4
Br5
C10B
Br4B
Br5B
0.005 (2)
0.006 (2)
0.0063 (19)
0.0029 (3)
0.000 (2)
0.0107 (3)
−0.0045 (3)
−0.001 (10)
−0.004 (7)
−0.0045 (3)
0.0022 (3)
0.0095 (3)
0.007 (10)
0.000 (8)
−0.0099 (3)
0.0095 (3)
Geometric parameters (Å, º)
Br1—C3
Br2—C3
N1—N2
N1—C1
1.960 (5)
C7—H7
0.9500
1.394 (8)
0.9500
1.962 (5)
1.259 (7)
1.428 (7)
C8—C12
C8—H8
C9—H9
0.9500
Acta Cryst. (2018). C74, 1692-1702
sup-14

supporting information
N2—C11
C1—C5
C1—C9
C3—C16
C3—Br3
C4—C16
C4—C6
C4—H4
C5—C16
C5—H5
C6—C9
C6—H6
C7—C8
C7—C15
1.420 (7)
1.391 (8)
1.403 (8)
1.505 (8)
1.935 (5)
1.383 (7)
1.392 (8)
0.9500
1.394 (7)
0.9500
1.381 (8)
0.9500
C11—C15
C11—C14
C12—C14
C12—C10B
C12—C10
C14—H14
C15—H15
C10—Br4
1.381 (8)
1.407 (8)
1.398 (8)
1.484 (19)
1.495 (9)
0.9500
0.9500
1.954 (7)
1.960 (6)
1.0000
1.86 (2)
1.95 (3)
1.0000
C10—Br5
C10—H10
C10B—Br4B
C10B—Br5B
C10B—H10B
1.374 (9)
1.394 (8)
N2—N1—C1
N1—N2—C11
C5—C1—C9
C5—C1—N1
C9—C1—N1
C16—C3—Br3
C16—C3—Br1
Br3—C3—Br1
C16—C3—Br2
Br3—C3—Br2
Br1—C3—Br2
C16—C4—C6
C16—C4—H4
C6—C4—H4
C1—C5—C16
C1—C5—H5
C16—C5—H5
C9—C6—C4
C9—C6—H6
C4—C6—H6
C8—C7—C15
C8—C7—H7
C15—C7—H7
C7—C8—C12
C7—C8—H8
C12—C8—H8
C6—C9—C1
C6—C9—H9
C1—C9—H9
113.7 (5)
115.5 (5)
119.9 (5)
115.8 (5)
124.2 (5)
115.2 (4)
110.3 (3)
106.9 (3)
110.6 (3)
107.0 (2)
106.4 (2)
120.8 (5)
119.6
119.6
120.7 (5)
119.6
119.6
120.7 (5)
119.7
119.7
119.9 (6)
120.0
120.0
120.4 (6)
119.8
119.8
119.1 (5)
120.5
C15—C11—C14
C15—C11—N2
C14—C11—N2
C8—C12—C14
C8—C12—C10B
C14—C12—C10B
C8—C12—C10
C14—C12—C10
C12—C14—C11
C12—C14—H14
C11—C14—H14
C11—C15—C7
C11—C15—H15
C7—C15—H15
C4—C16—C5
C4—C16—C3
C5—C16—C3
C12—C10—Br4
C12—C10—Br5
Br4—C10—Br5
C12—C10—H10
Br4—C10—H10
Br5—C10—H10
C12—C10B—Br4B
C12—C10B—Br5B
Br4B—C10B—Br5B
C12—C10B—H10B
Br4B—C10B—H10B
Br5B—C10B—H10B
120.3 (5)
115.8 (5)
123.9 (5)
120.3 (6)
116.3 (10)
122.8 (11)
122.6 (6)
117.1 (6)
118.7 (5)
120.7
120.7
120.3 (6)
119.9
119.9
118.8 (5)
124.0 (5)
117.1 (5)
111.1 (4)
112.4 (4)
107.9 (3)
108.4
108.4
108.4
110.8 (14)
107.0 (18)
115 (2)
108.1
108.1
108.1
120.5
C1—N1—N2—C11
N2—N1—C1—C5
N2—N1—C1—C9
−179.5 (4)
179.9 (4)
−0.3 (7)
N2—C11—C15—C7
C8—C7—C15—C11
C6—C4—C16—C5
179.4 (5)
0.6 (8)
−0.6 (8)
Acta Cryst. (2018). C74, 1692-1702
sup-15

supporting information
C9—C1—C5—C16
N1—C1—C5—C16
C16—C4—C6—C9
C15—C7—C8—C12
C4—C6—C9—C1
0.0 (8)
179.8 (4)
0.7 (8)
0.7 (8)
−0.5 (8)
0.1 (8)
−179.7 (5)
−177.1 (5)
3.4 (7)
−1.6 (8)
−173 (2)
177.3 (5)
1.1 (8)
172 (2)
−177.9 (5)
0.3 (8)
C6—C4—C16—C3
C1—C5—C16—C4
C1—C5—C16—C3
Br3—C3—C16—C4
Br1—C3—C16—C4
Br2—C3—C16—C4
Br3—C3—C16—C5
Br1—C3—C16—C5
Br2—C3—C16—C5
C8—C12—C10—Br4
178.8 (5)
0.3 (8)
−179.2 (4)
1.6 (7)
−119.5 (5)
123.0 (5)
−179.0 (4)
59.9 (5)
−57.5 (5)
−58.4 (7)
120.5 (5)
62.7 (7)
−118.4 (5)
178.3 (15)
7 (3)
C5—C1—C9—C6
N1—C1—C9—C6
N1—N2—C11—C15
N1—N2—C11—C14
C7—C8—C12—C14
C7—C8—C12—C10B
C7—C8—C12—C10
C8—C12—C14—C11
C10B—C12—C14—C11
C10—C12—C14—C11
C15—C11—C14—C12
N2—C11—C14—C12
C14—C11—C15—C7
C14—C12—C10—Br4
C8—C12—C10—Br5
C14—C12—C10—Br5
C8—C12—C10B—Br4B
C14—C12—C10B—Br4B
C8—C12—C10B—Br5B
C14—C12—C10B—Br5B
53 (3)
−118.3 (12)
179.7 (5)
−1.1 (8)
Acta Cryst. (2018). C74, 1692-1702
sup-16