Synthesis, crystal structures, photoluminescence, electrochemistry and DFT study of aluminium(III) and gallium(III) complexes containing a novel tetradentate Schiff base ligand

Article abstract of DOI:10.1107/S2053229619008805

Single crystals of the aluminium and gallium complexes of 6,6′-{(1E,1′E)-[1,2-phenylenebis(azanylylidene)]bis(methanylylidene)}bis(2-methoxyphenol), namely diaqua(6,6′-{(1E,1′E)-[1,2-phenylenebis(azanylylidene)]bis(methanylylidene)}bis(2-methoxyphenolato)-κ⁴ O ¹,N,N′,O ^1′)aluminium(III) nitrate ethanol monosolvate, [Al(C22H18N2O4)(H2O)2]NO3·C2H5OH, 1, and diaqua(6,6′-{(1E,1′E)-[1,2-phenylenebis(azanylylidene)]bis(methanylylidene)}bis(2-methoxyphenolato)-κ⁴ O ¹,N,N′,O ^1′)gallium(III) nitrate ethanol monosolvate, [Ga(C22H18N2O4)(H2O)2]NO3·C2H5OH, 2, were obtained after successful synthesis in ethanol. Both complexes crystallized in the triclinic space group P , with two molecules in the asymmetric unit. In both structures, in one of the independent molecules the tetradentate ligand is almost planar while in the other independent molecule the ligand shows significant distortions from planarity, as illustrated by the largest distance from the plane constructed through the central metal atom and the O,N,N′,O′-coordinating atoms of the ligand in 1 of 1.155(3)? and a distance of 1.1707(3)? in 2. The possible reason for this is that there are various strong π-interactions in the structures. This was confirmed by density functional theory (DFT) calculations, as were the other crystallographic data. DFT was also used to predict the outcome of cyclic voltammetry experiments. Ligand oxidation is more stabilized in the gallium complex. Solid-state photoluminescence gave an 80nm red-shifted spectrum for the gallium complex, whereas the aluminium complex maintains the ligand curve with a smaller red shift of 40nm.

Full text of DOI:10.1107/S2053229619008805

research papers
Synthesis, crystal structures, photoluminescence,
electrochemistry and DFT study of aluminium(III)
and gallium(III) complexes containing a novel
tetradentate Schiff base ligand
ISSN 2053-2296
a
a
b
James Charles Truscott, Jeanet Conradie, Hendrik C. Swart, Mart-Marie
b
a
Duvenhage and Hendrik Gideon Visser *
Received 3 April 2019
Accepted 20 June 2019
a
b
Chemistry, University of the Free State, Bloemfontein, Free State, 9301, South Africa, and Physics, University of the Free
State, Bloemfontein, Free State, 9301, South Africa. *Correspondence e-mail: visserhg@ufs.ac.za
Edited by I. D. Williams, Hong Kong University
of Science and Technology, Hong Kong
0
0
Single crystals of the aluminium and gallium complexes of 6,6 -{(1E,1 E)-
1,2-phenylenebis(azanylylidene)]bis(methanylylidene)}bis(2-methoxyphenol),
Keywords: gallium; photoluminescence; alumi-
nium; DFT; computational chemistry; crystal
structure.
[
0
0
namely diaqua(6,6 -{(1E,1 E)-[1,2-phenylenebis(azanylylidene)]bis(methanylyl-
idene)}bis(2-methoxyphenolato)-ꢀ O ,N,N ,O )aluminium(III) nitrate ethanol
0
1
4
1
0
0
CCDC references: 1935699; 1935698
monosolvate, [Al(C H N O )(H O) ]NO ꢀC H OH, 1, and diaqua(6,6 -
22
18
2
4
2
2
3
2
5
0
{
(1E,1 E)-[1,2-phenylenebis(azanylylidene)]bis(methanylylidene)}bis(2-methoxy-
0
0
Supporting information: this article has
4
1
1
phenolato)-ꢀ O ,N,N ,O )gallium(III) nitrate ethanol monosolvate, [Ga(C H -
22
18
supporting information at journals.iucr.org/c
N O )(H O) ]NO ꢀC H OH, 2, were obtained after successful synthesis in
2
4
2
2
3
2
5
ethanol. Both complexes crystallized in the triclinic space group P1, with two
molecules in the asymmetric unit. In both structures, in one of the independent
molecules the tetradentate ligand is almost planar while in the other independent
molecule the ligand shows significant distortions from planarity, as illustrated by
the largest distance from the plane constructed through the central metal atom
0
0
˚
and the O,N,N ,O -coordinating atoms of the ligand in 1 of 1.155 (3) A and a
˚
distance of 1.1707 (3) A in 2. The possible reason for this is that there are various
strong ꢁ-interactions in the structures. This was confirmed by density functional
theory (DFT) calculations, as were the other crystallographic data. DFTwas also
used to predict the outcome of cyclic voltammetry experiments. Ligand oxidation
is more stabilized in the gallium complex. Solid-state photoluminescence gave an
80 nm red-shifted spectrum for the gallium complex, whereas the aluminium
complex maintains the ligand curve with a smaller red shift of 40 nm.
1
. Introduction
Aluminium is the most abundant metal on earth and has been
used widely in many industrial fields, including motor vehicles
and electronics. This of course has an impact on the envir-
onment and human health (Jeyanthi et al., 2013; Flaten, 2001;
Martyn et al., 1989; Goswami et al., 2013b; Gupta et al., 2015).
Complexes of aluminium and its third-row congener gallium
with Schiff base ligands (Schiff, 1864) are currently of much
interest for use as fluorescent probes and as organic light-
emitting diodes (OLEDs) (Sivaraman et al., 2012, 2014;
Goswami et al., 2013a; Han et al., 2012). Gallium-containing
OLEDs tend to exhibit higher electroluminescent yields than
equivalent metal centres, such as aluminium (Burrows et al.,
1994; Wang et al., 1999).
The photoluminescence properties of organometallic com-
plexes are influenced by many factors, including the effects of
trapped guest molecules, intermolecular interactions and, of
course, the types of substituents (electronic and steric prop-
erties) on the ligands attached to the metal atom (Artizzu et
#
2019 International Union of Crystallography
Acta Cryst. (2019). C75
https://doi.org/10.1107/S2053229619008805 1 of 8

research papers
al., 2011; Goldman & Wehry, 1970; Forster & Rokos, 1976;
Alexander et al., 2017).
(Sawyer & Roberts, 1974), mounted on a Luggin capillary
(Evans et al., 1983). All cited potentials are referenced against
+
the FcH/FcH couple, as suggested by the International Union
One of the many examples of Schiff bases which exhibit
excellent results as chemosensors for aluminium is a combi-
nation of salicylic acid and phenylenediamines forming
various tetradentate ligands. It is clear though, from this work,
that there is uncertainty as to the nature of the aluminium
complexes formed (Wang et al., 2013; Gupta et al., 2014; Dong
et al., 2010).
of Pure and Applied Chemistry (IUPAC) (Gritzner & Kuta,
1984).
Density functional theory (DFT) calculations were carried
out using the ADF (Amsterdam Density Functional) 2014
programme with the PW91 (Wang, 1991) GGA (Generalized
Gradient Approximation) functional. The all-electron Slater-
type TZP (triple-ꢂ polarized) basis set, with a fine mesh for
numerical integration and tight convergence criteria, was used
for minimum-energy searches. Numerical frequencies were
computed to ensure that all optimized geometries were true
minima on the energy surface.
2.2. Synthesis and crystallization
2.2.1. H PAMM. o-Vanillin (1.5235 g, 0.01 mol) was added
2
to 1,2-phenylenediamine (0.5435 g, 0.005 mol) and placed in a
ball mill at 25 Hz for 40 min. After completion, the product
obtained was bright red. The reaction mixture was left to dry
and needle-like crystals formed upon drying (yield 1.7005 g,
Our interest lies in the basic understanding of the synthesis
and structural properties that influence the luminescence of
these types of complexes. In this article, we present the
synthesis, characterization and photoluminescence properties
of the aluminium and gallium complexes of the novel Schiff
1
9
1
1
1
0.35%). H NMR (300 MHz, DMSO): ꢃ 13.00 (s, 1H), 8.92 (s,
H), 7.43 (d, J = 8.6 Hz, 2H), 7.24 (s, 1H), 7.12 (s, 1H), 6.91 (s,
13
H), 3.81 (s, 4H). C NMR (75 MHz, DMSO): ꢃ 164.83 (s),
51.08 (s), 148.35 (s), 142.57 (s), 128.29 (s), 124.25 (s), 120.28
ꢃ1
(
s), 119.80 (s), 119.03 (s), 115.89 (s), 56.13 (s). IR (cm ):
0
0
based ligand 6,6 -{(1E,1 E)-[1,2-phenylenebis(azanylylidene)]-
bis(methanylylidene)}bis(2-methoxyphenol) (H PAMM), nam-
ꢄ(C N) = 1567.9, ꢄ(C—O) = 1246.0 and ꢄ(C—N) = 1076.5.
2
ꢃ1
ꢃ1
UV–Vis: ꢅmax = 270 nm, " = 17320 M cm . Elemental
analysis (C, H and N) calculated (%): C 70.2, H 5.36, N 7.44;
found: C 70.34, H 5.20, N 7.49.
ely [Al(PAMM)(H O) ]NO ꢀC H OH, 1, and [Ga(PAMM)-
2
2
3
2
5
(
H O) ]NO ꢀC H OH, 2 (see Scheme 1).
2
2
3
2
5
2
.2.2. [Al(PAMM)(H O) ]NO ꢀC H OH, 1. A solution of
2
2
3
2
5
H PAMM (0.1564 g, 0.416 mmol) in chloroform (20 ml) was
2
2
. Experimental
added slowly to a solution of aluminium nitrate nonahydrate
(0.1558 g, 0.415 mmol) in methanol (10 ml), followed by a
solution of sodium acetate (0.0399 g, 0.486 mmol) in methanol
2.1. Materials and methods
Chemicals were of analytical grade, while all the solvents
ꢁ
were purified and dried prior to use. IR spectra were recorded
with a Hitachi 270-50 spectrophotometer, while the NMR
spectra were obtained at 298 K on a Bruker Avance DPX 300
NMR spectrometer (300.130 MHz) and a Bruker Avance II
(10 ml). The reaction was stirred under reflux at 70 C for 24 h.
A precipitate formed upon cooling and was filtered off (yield
1
0.1632 g, 89.30%). H NMR (600 MHz, DMSO): ꢃ 9.31 (s, 1H),
8.17 (dt, J = 7.2, 3.6 Hz, 1H), 7.58 (dd, J = 6.2, 3.3 Hz, 1H), 7.34
(d, J = 7.5 Hz, 1H), 7.24 (s, 1H), 6.84 (s, 1H), 3.93 (s, 3H). IR
600 NMR spectrometer (600.130 MHz). The chemical shifts
were reported relative to dimethyl sulfoxide (DMSO)
ꢃ1
(cm ): ꢄ(O—H) = 3319.9, ꢄ(C—O) = 1109.4 and ꢄ(C—N) =
1
0.00 ppm) for the H and C NMR spectra.
13
ꢃ1
ꢃ1
(
1134.8. UV–Vis: ꢅmax = 315 nm, " = 19836 M cm . Ele-
mental analysis (C, N and H) calculated (%): C 60.41, H 5.07,
N 6.40; found: C 60.64, H 4.98, N 6.74.
Photoluminescence excitation and emission data were
collected with a Cary Eclipse fluorescence spectrophotometer
equipped with a Xenon flash lamp. The absorption spectra
were collected on a PerkinElmer Lambda 950 UV–Vis spec-
trophotometer.
2.2.3. [Ga(PAMM)(H O) ]NO ꢀC H OH, 2. A solution of
2
2
3
2
5
H PAMM (0.1518 g, 0.404 mmol) in chloroform (20 ml) was
2
added slowly to a solution of gallium(III) nitrate hydrate
(0.1011 g, 0.393 mmol) in methanol (10 ml), followed by a
solution of sodium acetate (0.0400 g, 0.472 mmol) in methanol
Electrochemical studies by means of cyclic voltammetry
ꢃ4
ꢁ
ꢃ3
were performed at 25.0 C on 5 ꢂ 10 mol dm solutions of
ꢃ3
ꢁ
the complexes in CH CN/0.1 mol dm tetra-n-butylammo-
3
(10 ml). The reaction was stirred under reflux at 70 C for 24 h.
A precipitate formed upon cooling and was filtered off (yield
nium hexafluorophosphate, i.e. [(n-Bu )N][PF ], electrolyte
4
6
1
systems, under a blanket of purified argon, utilizing a BAS
00B/W electrochemical analyser. A three-electrode cell was
0.1657 g, 85.07%). H NMR (300 MHz, DMSO): ꢃ 9.29 (s, 1H),
7.95 (s, 1H), 7.24 (d, J = 7.4 Hz, 1H), 7.17 (d, J = 7.6 Hz, 1H),
1
ꢃ6
2
ꢃ1
used, with a glassy carbon (surface area 7.07 ꢂ 10 m )
6.79 (t, J = 7.6 Hz, 1H), 3.87 (s, 3H), 2.37 (s, 3H). IR (cm ):
ꢄ(O—H) = 3590.9, ꢄ(C—O) = 1239.9 and ꢄ(C—N) = 1077.2.
+
working electrode, a Pt auxiliary electrode and an Ag/Ag
(0.010 mol dm
ꢃ3
ꢃ1
ꢃ1
AgNO3 in CH CN) reference electrode
3
UV–Vis: ꢅmax = 320 nm, " = 34195 M cm . Elemental
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Ga and Al complexes of a novel tetradentate Schiff base
Acta Cryst. (2019). C75

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Table 1
Experimental details.
For both structures: triclinic, P1, Z = 4. Experiments were carried out at 100 K with Mo Kꢆ radiation using a Bruker APEXII CCD diffractometer. H atoms were
treated by a mixture of independent and constrained refinement.
1
2
Crystal data
Chemical formula
[Al(C22
545.47
H
18
N
2
O
4
)(H O)
2
2
]NO
3
ꢀC
2 6
H O
[Ga(C22
588.21
H
18
N
2
O
4
)(H
2
O) ]NO
2
3
2 6
ꢀC H O
M
r
˚
ꢁ
a, b, c (A)
ꢆ, ꢇ, ꢈ ( )
V (A )
ꢉ (mm
Crystal size (mm)
12.413 (5), 13.394 (5), 16.368 (5)
87.899 (5), 79.578 (5), 66.635 (5)
2455.1 (15)
0.15
0.30 ꢂ 0.27 ꢂ 0.13
12.399 (5), 13.580 (5), 16.419 (5)
86.818 (5), 78.871 (5), 66.124 (5)
2479.7 (16)
1.17
0.58 ꢂ 0.24 ꢂ 0.23
˚
3
ꢃ1
)
Data collection
No. of measured, independent and observed
64029, 11817, 7331
47407, 11972, 10426
[
I > 2ꢊ(I)] reflections
R
int
0.062
0.661
0.027
0.661
˚
ꢃ1
)
(sin ꢋ/ꢅ)max (A
Refinement
2
2
2
R[F > 2ꢊ(F )], wR(F ), S
No. of reflections
0.056, 0.163, 1.02
0.044, 0.114, 1.06
11817
718
19
0.80, ꢃ0.77
11886
682
20
1.84, ꢃ2.07
No. of parameters
No. of restraints
Áꢌmax, Áꢌmin (e A
˚
ꢃ3
)
Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2015) and SHELXTL (Bruker, 2010).
analysis (C, H and N) calculated (%): C 55.03, H 4.62, N 5.38;
found: C 55.14, H 4.54, N 5.51.
Interestingly, both structures have one of the two solvent
molecules disordered. Both 1 and 2 show 50/50 positional
disorder for the ethanol molecule, the only difference being
2.3. Single-crystal X-ray crystallography
Crystal data, data collection and structure refinement
details are summarized in Table 1. For 1 and 2, all H atoms
were positioned in geometrically idealized positions and
˚
constrained to ride on their parent atoms, with C—H = 0.93 A
2
and U (H) = 1.2U (C) for sp CH, and with C—H = 0.96 A
˚
iso
eq
and U (H) = 1.5U (C) for methyl groups. Disorder of the
iso
eq
ethanol solvent species was observed for both complexes and
during the refinement, distance and similarity restraints were
applied to the chemically equivalent bond lengths and angles.
3
. Results and discussion
3.1. Synthesis and crystal structures
H PAMM, [Al(PAMM)(H O) ]ꢀNO ꢀCH CH OH (1) and
2
2
2
3
3
2
[
Ga(PAMM)(H O) ]ꢀNO ꢀCH CH OH (2) were successfully
2
2
3
3
2
synthesized and characterized by IR, UV–Vis, elemental
1
analysis and H NMR spectroscopy. The free ligand was
prepared in the solid state with excellent yields, using a ball
mill.
The aluminium and gallium complexes are isomorphous
and crystallize in the triclinic space group P1 with two inde-
pendent molecules in the asymmetric unit. Each metal centre
has an octahedral coordination geometry (Fig. 1). The central
metal atoms are bound to the tetradentate ligands via two N
and two O atoms. Two water molecules are also attached to
the central metal atom in each case to complete the octahedral
environments. Two nitrate counter-ions and two solvent mol-
ecules (ethanol) complete the asymmetric units in each case.
Figure 1
Structural representations of (a) 1 and (b) 2. H atoms, solvent molecules
and counter-ions have been omitted for clarity
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Truscott et al.
Ga and Al complexes of a novel tetradentate Schiff base 3 of 8

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Table 2
Selected geometric parameters (A, ) for 1.
Table 3
Selected geometric parameters (A, ) for 2.
˚
ꢁ
˚
ꢁ
N01—Al1
N02—Al1
N03—Al2
N04—Al2
2.007 (2)
1.988 (2)
1.991 (2)
1.998 (2)
O1—Al1
O2—Al1
O7—Al2
O8—Al2
1.8197 (19)
1.8066 (19)
1.812 (2)
Ga01—O4
Ga01—O3
Ga01—N1
Ga01—N2
1.8829 (18)
1.8941 (18)
2.009 (2)
Ga02—O5A
Ga02—O4A
Ga02—N1A
Ga02—N2A
1.887 (2)
1.8878 (18)
2.005 (2)
2.019 (2)
1.809 (2)
2.022 (2)
O2—Al1—O1
O1—Al1—N02
O2—Al1—N01
N02—Al1—N01
93.64 (8)
92.09 (9)
93.08 (9)
81.16 (9)
O8—Al2—O7
O8—Al2—N03
O7—Al2—N04
N03—Al2—N04
92.64 (9)
93.18 (9)
92.57 (9)
81.73 (9)
O4—Ga01—O3
O3—Ga01—N1
O4—Ga01—N2
N1—Ga01—N2
91.95 (8)
92.60 (8)
93.84 (8)
81.59 (9)
O5A—Ga02—O4A
O4A—Ga02—N1A
O5A—Ga02—N2A
N1A—Ga02—N2A
91.11 (8)
93.96 (8)
92.88 (8)
82.20 (9)
Table 4
Selected intramolecular hydrogen (bonds (A, ) for 1 and 2.
that the molecule in 1 seems to flip around the O atom while
the disordered molecules are side-by-side in 2. The Ga—N,
Ga—O, Al—N and Al—O (Tables 2 and 3) bond lengths are
considered to fall within the normal range (Knapp et al., 2015;
Obrey et al., 2002). The deviations from perfect octahedral
geometry of the complex molecules in 1 and 2 are best illu-
strated by the N02—Al1—N01 and N1A—Ga02—N2A angles
˚
ꢁ
Complex 1
O5—H52ꢀ ꢀ ꢀO16
0.87 (2)
0.83 (3)
1.83 (3)
1.73 (3)
2.684 (3)
2.573 (4)
169 (3)
178 (7)
O11—H11Bꢀ ꢀ ꢀO1A
Complex 2
O2—H2Bꢀ ꢀ ꢀO7
0.85 (3)
0.85 (3)
2.47 (4)
1.91 (4)
3.116 (3)
2.727 (3)
134 (5)
161 (6)
ꢁ
of 81.16 (9) and 82.20 (9) , respectively.
O2—H2Bꢀ ꢀ ꢀO16
The tetradentate ligand reveals interesting characteristics in
terms of its deviation from planarity in both 1 and 2. When a
plane is constructed through the central metal atom and the
˚
interaction [distance 3.7031 (4) A] is observed between the
central arene rings (phenylenediamine building block) of the
molecules containing atoms Ga01 and Ga02, which also pack
in a head-to-head orientation (Yahsi, 2016).
0
0
N,N ,O,O -coordinating atoms of the ligand (Figs. 2a and 2b)
for both molecules in the asymmetric units of 1 and 2, a clear
deviation from near planarity is observed for one of the
˚
complexes in each case. In 1, atom C9A is 1.155 (3) A from the
plane through Al1/N01/N02/O1/O6, while atom C18 is only
˚
The more planar molecules in 1 mimic the ꢁ–ꢁ interaction
˚
of 2, with a centroid-to-centroid distance of 3.654 (3) A
0.257 (3) A from the plane through Al2/N03/N04/O7/O8. In 2,
the longest distance from the plane through Ga01/N1/N2/O3/
between the two methoxyphenyl rings, but in this case no
other interactions are observed.
˚
O4 is observed for atom C7 [1.1707 (3) A], while the furthest
atom (C6A) from the Ga02/N1A/N2A/O3A/O4A plane in the
˚
second molecule is only at a distance of 0.2925 (3) A. Intra-
C—Hꢀ ꢀ ꢀꢁ interactions (Table 6) in 1 and 2 are similar
(Figs. 3 and 4) and occur between neighbouring molecules,
from a methoxy substituent of one molecule towards an arene
ring of another (Al2 and Ga02).
molecular O—Hꢀ ꢀ ꢀO interactions are present in both 1 and 2
and are summarized in Table 4.
The more planar molecules in 2 (Ga02) pack above each
other in a head-to-head fashion so that ꢁ–ꢁ interactions with a
3.2. Photoluminescence
˚
centroid-to-centroid distance of 3.9722 (5) A can occur
between the methoxyphenyl rings (Table 5). Another ꢁ–ꢁ
The emission spectra of the free ligand and complexes 1 and
2 were obtained in the solid state at room temperature (Fig. 5).
Figure 2
(a) Deviation from planarity through the Al—N—N—O—O planes of the tetradentate ligand in 1. (b) Deviation from planarity through the Ga—N—
N—O—O planes of the tetradentate ligand in 2.
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Ga and Al complexes of a novel tetradentate Schiff base
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research papers
Table 5
Geometrical parameters (A, ) for ꢁ–ꢁ stacking for 1 and 2.
˚
ꢁ
a
b
c
Rc
d
e
f
g
B
h
À
Complex
Cgi
[Res]ꢀ ꢀ ꢀCgj
R1v
R2v
A
iii
1
2
Cg5
[2]ꢀ ꢀ ꢀCg6
3.654 (3)
ꢃ3.3184 (10)
ꢃ3.3995 (12)
7.61 (15)
24.73
21.49
i
Cg1
Cg3
[2]ꢀ ꢀ ꢀCg2
3.972 (5)
3.703 (4)
3.7819 (11)
3.4169 (13)
3.1648 (11)
3.3194 (18)
19.59 (18)
7.64 (13)
17.81
22.68
37.18
26.31
ii
[2]ꢀ ꢀ ꢀCg4
Symmetry codes (i) ꢃx, ꢃy + 1, ꢃz; (ii) x, y ꢃ 1, z ꢃ 1; (iii) ꢃx + 1, ꢃy, ꢃz + 1. Notes: (a) for 1, Cg5 and Cg6 are the centroids of the C8–C13 and C14–C19 rings, respectively. For 2,
Cg1, Cg2, Cg3 and Cg4 are the centroids of the C1–C3/C18–C20, C1A–C3A/C18A–C20A, C5A–C10A and C11A–C16A rings, respectively; (b) [Res] = Residue; (c) Residue–centroid
distance between ring i and ring j; (d) vertical distance from ring centroid i to ring j; (e) vertical distance from ring centroid j to ring i; (f) dihedral angle between the first ring mean plane
and the second ring mean plane of the partner molecule; (g) angle between the centroid of the first ring and the second ring; (h) angle between the centroid of the first ring and the normal
to the mean plane of the second ring of the partner molecule.
The ligand in the solid state was excited at 335 nm and emitted
three peaks at 470, 492 and 511 nm, showing that it is lumi-
nescent. These excitations may be attributed to ꢁ–ꢁ* transi-
tions (Miles et al., 1981).
The solid state of 2 emits green light at 545 nm upon exci-
tation at 355 nm. The emission is due to a ligand-centred
charge-transfer excited state, modulated by the presence of
the Ga atom. It is indicated from this observation that the
intraligand charge-transfer (ILCT) emitting state lies below
any ligand–metal charge transfer (LMCT) excited states (Paul
et al., 2015). The red shift in the luminescence maxima of 2 was
Table 6
Geometrical parameters (A, ) for X—Hꢀ ꢀ ꢀꢁ interactions.
Complex X—H(I) Res(I)!Cg(J) Hꢀ ꢀ ꢀCg X—Hꢀ ꢀ ꢀCg Yꢀ ꢀ ꢀCg
˚
ꢁ
ii
1
2
C021—H02A [1]!Cg2
2.86 (8) 170
2.80 (2) 162
3.817 (3)
3.729 (3)
i
C21—H21B
[1]!Cg11
Symmetry codes: (i) ꢃx + 1, ꢃy + 1, ꢃz; (ii) x, y, z ꢃ 1.
Figure 3
Figure 4
Illustration of (a) the ꢁ–ꢁ and C—Hꢀ ꢀ ꢀꢁ interactions, and (b) the
Illustration of (a) the ꢁ–ꢁ interactions and (b) the hydrogen-bond
interactions in 2.
hydrogen-bond interactions in 1.
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Ga and Al complexes of a novel tetradentate Schiff base 5 of 8

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Table 7
Selected experimental and DFT-calculated geometric parameters (A, ) for the indicated complexes.
˚
ꢁ
Complex
Bond
Bond length via XRD
Bond length via DFT
Angle
Bond angle via XRD
Bond angle via DFT
Complex 1
N01—Al1
N02—Al1
O1—Al1
2.007 (2)
1.988 (2)
1.8197 (19)
1.8066 (19)
1.887 (2)
1.8878 (18)
2.019 (2)
2.005 (2)
2.007
1.987
1.820
1.807
1.891
1.889
2.022
2.009
O2—Al1—O1
O2—Al1—N01
N02—Al1—N01
O1—Al1—N02
O4A—Ga02—O5A
O5A—Ga02—N2A
N2A—Ga02—N1A
N1A—Ga02—O4A
93.64 (8)
93.08 (9)
81.16 (9)
92.09 (9)
91.11 (8)
92.88 (8)
82.20 (9)
93.96 (8)
94.5
92.8
81.6
91.6
91.5
93.1
81.9
94.2
O2—Al1
Complex 2
O5A—Ga02
O4A—Ga02
N2A—Ga02
N1A—Ga02
Solvent molecules are incapable of forming ꢁ–ꢁ orbital
overlaps with the ligands and simply act as spacer molecules,
which reduces the intermolecular interactions involving the
arene groups.
When comparing the photoluminescence spectra of 1 and 2
with that of the ligand (Fig. 5), the gallium complex deviates
from the ligand curve, resulting in a new curve (80 nm red
shifted), whereas the aluminium complex maintains the ligand
curve with a slight red shift (40 nm).
3.3. Computational chemistry
Selected bond lengths and angles of the optimized struc-
tures of 1 and 2 are given in Table 7. The optimized metal–
ligand bond lengths compare well with the experimental
single-crystal X-ray structure values; all calculated metal–
˚
Figure 5
Comparison of the solid-state photoluminescence for H
oxygen and metal–nitrogen bonds are within 0.02 A of the
XRD data. The angles involving the metal atom are within
0
2
PAMM, 1 and 2.
ꢁ
.8 of the XRD data. Slightly larger DFT-calculated bond
10
compared to that of the ligand. In elements with stable d
lengths than experimental bond lengths are generally
observed for gas-phase DFT optimizations, and therefore
differences between the experimentally measured metal–
ligand bond lengths and the calculated bond lengths below a
configurations, the photoluminescence properties of the
complexes are only determined by the organic ligand (Liuzzo
et al., 2010). The difference in emission properties between the
ligand and the complex can therefore be attributed to the Ga
atom. The ligand conformational rigidity is increased by the
Ga atom and this is favourable for the formation of a more
planar and conjugated structure. The reduction in the energy
gap between the HOMO (highest occupied molecular orbital)
and LUMO (lowest unoccupied molecular orbital) of the
ligand (2.139 eV) on coordination of the metal ions (1.752 and
˚
threshold of 0.02 A are considered meaningless. Interestingly,
the optimized structures also show deviations from planarity
for the tetradentate ligands, with the largest distances of the C
atoms from the metal—N—N—O—O plane being 0.63 and
0.92 A for 1 and 2, respectively.
The Ga-d-based molecular orbitals of 2 are shown in Fig. 6.
It is interesting to note that the d-based orbitals point directly
˚
2
1.694 eV for 1 and 2, respectively) enhances the mobility of
along the bonds in the direction of the ligands; namely dz
the electron transition due to back-coupling ꢁ-bonding
between the metal and ligand, and this leads to a decrease in
the electronic transition energy of the ILCT (Ali, 1987).
(HOMO-72) and d
the orbitals pointing in between the bonds between Ga and
the ligands, which are the dꢁ (HOMO-70 and HOMO-69) and
2
2
(HOMO-71) have lower energies than
x ꢃy
Figure 6
The Kohn–Sham Ga-d-based molecular orbitals of 2, obtained from PW91/STO-TZP DFT calculation. The MO plots use a contour of 60 e nm . Colour
code of atoms: Ga green, C pink, O red, N orange and H sky blue.
ꢃ3
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Figure 7
The Kohn–Sham frontier orbitals of H
Colour code of atoms: Al yellow, Ga green, C pink, O red, N orange and H sky blue.
ꢃ3
2
PAMM and 1 and 2, obtained from PW91/STO-TZP DFT calculation. The MO plots use a contour of 60 e nm
.
dxy (HOMO-68) types of mainly d-based molecular orbitals.
Selected frontier molecular orbitals of H PAMM and 1 and
2
2
are compared in Fig. 7. They have similar features and are all
ligand based. The HOMOs are mainly on the arene rings of
the methoxyphenyl rings, while the LUMOs are spread over
the ligand backbone showing effective communication
through ꢁ-orbitals throughout the ligand.
The oxidation and reduction of a complex generally involve
the removal of an electron from the HOMO, or the addition of
an electron to the LUMO of the complex (Conradie, 2015).
Since the HOMO and LUMO of H PAMM and complexes 1
2
and 2 are ligand based, the first oxidation and first reduction of
these complexes will involve the ligand and is not expected to
be metal based. Due to the low-lying d orbitals of 2, Ga-metal-
based oxidation and reduction are not expected. The elec-
trochemical oxidation and reduction of H PAMM and com-
2
plexes 1 and 2 will be discussed in the next section.
Figure 8
Cyclic voltammograms of 0.0005 mol dm solutions of H
middle) and 1 (bottom) in acetonitrile, with supporting electrolyte
tetrabutylammonium hexafluorophosphate and a glassy carbon working
electrode, at a scan rate of 0.100 V s , with potential versus FcH/FcH .
Scans are initiated in the direction indicated by the arrows.
ꢃ3
3
.4. Cyclic voltammetry
2
PAMM (top), 2
(
The cyclic voltammograms (CVs) of H PAMM, 1 and 2, at a
2
ꢃ1
scan rate of 0.100 Vs , are given in Fig. 8. The ligand, 1 and 2
show several irreversible oxidation and reduction peaks
ꢃ1
+
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Acta Cryst. (2019). C75
Truscott et al.
Ga and Al complexes of a novel tetradentate Schiff base 7 of 8

research papers
(
0
Elgrishi et al., 2018). The first oxidation peak of the ligand at
+
.74 V versus FcH/FcH shifts to a higher more positive
Bruker (2010). APEX2, SAINT and SHELXTL. Bruker AXS Inc.,
Madison, Wisconsin, USA.
Burrows, P. E., Sapochak, L. S., McCarty, D. M., Forrest, S. R. &
Thompson, M. E. (1994). Appl. Phys. Lett. 64, 2718–2720.
Conradie, J. (2015). J. Phys. Conf. Ser. 633, 012045.
Dong, L., ChongWu Zeng, X., Mu, L., Xue, S., Tao, Z. & Zhang, J.
(2010). Sens. Actuators B Chem. 145, 433–437.
Elgrishi, N., Rountree, K. J., McCarthy, B. D., Rountree, E. S.,
Eisenhart, T. T. & Dempsey, J. L. (2018). J. Chem. Educ. 95, 197–
+
potential, i.e. 0.93 V versus FcH/FcH , when complexed to 2,
but to a lower less positive potential, i.e. 0.53 V versus FcH/
+
FcH , when complexed to 1. The first oxidation peaks of the
ligand and complexes 1 and 2 are assigned to ligand oxidation,
based on the character of their HOMOs. Ligand oxidation is
thus stabilized when complexed to Ga, and occur at a higher
more positive potential for 2 than for the free ligand. The first
206.
Evans, D. H., O’Connell, K. M., Petersen, R. A. & Kelly, M. J. (1983).
J. Chem. Educ. 60, 290–293.
+
reduction peak of the ligand at ꢃ2.04 V versus FcH/FcH
shifts to a higher less negative potential, i.e. ꢃ1.71 and
Flaten, T. P. (2001). Brain Res. Bull. 55, 187–196.
Forster, T. & Rokos, K. (1976). Chem. Phys. Lett. 1, 279–280.
Goldman, M. & Wehry, E. L. (1970). Anal. Chem. 42, 1178–1185.
Goswami, S., Manna, A., Paul, S., Aich, K., Das, A. K. & Chakraborty,
S. (2013a). Dalton Trans. 42, 8078–8085.
Goswami, S., Paul, S. & Manna, A. (2013b). RSC Adv. 3, 10639–
10643.
Gritzner, G. & Kuta, J. (1984). Pure Appl. Chem. 56, 461–466.
Gupta, V. K., Shoora, S. K., Kumawat, L. K. & Jain, A. K. (2015).
Sens. Actuators B Chem. 209, 15–24.
+
ꢃ1.79 V versus FcH/FcH , when complexed to 1 and 2,
respectively. The first reduction peaks of the ligand and the
complexes are assigned to ligand reduction, based on the
character of their LUMOs. Upon reduction, a radical anion is
formed with the ꢁ-electron density spread over the aromatic
backbone of the ligand. This ligand reduction is easier at a less
negative potential when complexed to Ga or Al.
Gupta, V. K., Singh, A. K. & Kumawat, L. K. (2014). Sens. Actuators
B Chem. 195, 98–108.
Han, T., Feng, X., Tong, B., Shi, J., Chen, L., Zhi, J. & Dong, Y. (2012).
Chem. Commun. 48, 416–418.
Jeyanthi, D., Iniya, M., Krishnaveni, K. & Chellappa, D. (2013). RSC
Adv. 3, 20984–20989.
Knapp, C. E., Marchand, P., Dyer, C., Parkin, I. P. & Carmalt, C. J.
(2015). New J. Chem. 39, 6585–6592.
4
. Conclusions
This study reports some coordination-chemistry aspects of
0
0
the novel Schiff base ligand 6,6 -{(1E,1 E)-[1,2-phenylene-
bis(azanylylidene)]bis(methanylylidene)}bis(2-methoxyphenol)
(H PAMM) complexed to aluminium (1) and gallium (2). The
2
Liuzzo, V., Oberhauser, W. & Pucci, A. (2010). Inorg. Chem.
Commun. 13, 686–688.
Martyn, C. N., Osmond, C., Edwardson, J. A., Barker, D. J. P., Harris,
E. C. & Lacey, R. F. (1989). Lancet, 333, 59–62.
Miles, D. W., Redington, P. K., Miles, D. L. & Eyring, H. (1981). Proc.
Natl Acad. Sci. USA, 78, 7521–7525.
crystal structures and packing of both 1 and 2 are very similar,
even to the point of having one of the complex molecules in
the asymmetric unit being almost planar, whereas the other
deviates substantially from planarity. Planarity is attributed to
strong ꢁ–ꢁ interactions. DFT calculations indicate that the
ideal geometry would not be planar, but rather twisted.
Obrey, S. J., Bott, S. G. & Barron, A. R. (2002). Inorg. Chem. 41, 571–
5
76.
Paul, M. K., Dilipkumar Singh, Y., Bedamani Singh, N. & Sarkar, U.
2015). J. Mol. Struct. 1081, 316–328.
Acknowledgements
(
Sawyer, D. T. & Roberts, J. L. (1974). Experimental Electrochemistry
for Chemists, p. 54. London: John Wiley & Sons.
Schiff, H. (1864). Ann. Chem. Pharm. 131, 118–119.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.
This work has received support from the South African
National Research Foundation and the Central Research
Fund of the University of the Free State, Bloemfontein, South
Africa. The High-Performance Computing facility of the UFS
is acknowledged for computer time.
Sivaraman, G., Anand, T. & Chellappa, D. (2012). Analyst, 137, 5881–
5884.
Sivaraman, G., Anand, T. & Chellappa, D. (2014). ChemPlusChem,
pp. 1761–1766.
References
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Artizzu, F., Mercuri, M. L., Serpe, A. & Deplano, P. (2011). Coord.
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755.
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of 8 Truscott et al.
Ga and Al complexes of a novel tetradentate Schiff base
Acta Cryst. (2019). C75

supporting information
supporting information
Acta Cryst. (2019). C75 [https://doi.org/10.1107/S2053229619008805]
Synthesis, crystal structures, photoluminescence, electrochemistry and DFT
study of aluminium(III) and gallium(III) complexes containing a novel
tetradentate Schiff base ligand
James Charles Truscott, Jeanet Conradie, Hendrik C. Swart, Mart-Marie Duvenhage and
Hendrik Gideon Visser
Computing details
For both structures, data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction:
SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL (Bruker, 2010); software used to prepare
material for publication: SHELXL2013 (Sheldrick, 2015).
Diaqua(6,6′-{(1E,1′E)-[1,2-phenylenebis(azanylylidene)]bis(methanylylidene)}bis(2-methoxyphenolato)-
4
1
1′
κ O ,N,N′,O )aluminium(III) nitrate ethanol monosolvate (shelx)
Crystal data
[
18 2 4 2 2 3
Al(C22H N O )(H O) ]NO ·C
2 6
H O
Z = 4
M
r
= 545.47
F(000) = 1144
D = 1.476 Mg m
x
−3
Triclinic, P1
a = 12.413 (5) Å
b = 13.394 (5) Å
c = 16.368 (5) Å
α = 87.899 (5)°
β = 79.578 (5)°
γ = 66.635 (5)°
V = 2455.1 (15) Å
Mo Kα radiation, λ = 0.71069 Å
Cell parameters from 9867 reflections
θ = 1.0–1.0°
µ = 0.15 mm
T = 100 K
−1
Cuboid, yellow
0.30 × 0.27 × 0.13 mm
3
Data collection
Bruker APEXII CCD
diffractometer
R
int = 0.062
θ
max = 28.0°, θmin = 1.7°
φ and ω scans
h = −16→12
k = −17→17
l = −21→21
6
4029 measured reflections
1817 independent reflections
331 reflections with I > 2σ(I)
1
7
Refinement
2
Refinement on F
718 parameters
Least-squares matrix: full
19 restraints
2
2
R[F > 2σ(F )] = 0.056
Hydrogen site location: mixed
H atoms treated by a mixture of independent
and constrained refinement
2
wR(F ) = 0.163
S = 1.02
11817 reflections
Acta Cryst. (2019). C75
sup-1

supporting information
2
2
2
−3
w = 1/[σ (F
where P = (F
Δ/σ)max < 0.001
o
) + (0.0684P) + 2.3877P]
Δρmax = 0.80 e Å
2
2
−3
o
+ 2F
c
)/3
Δρmin = −0.76 e Å
(
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.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
Occ. (<1)
C1
0.5080 (2)
0.9140 (2)
0.0336 (4)
0.1042
0.0057
0.8417 (3)
0.8370
0.3196 (2)
0.1954 (2)
0.2269 (4)
0.1691
0.1971
0.1404 (2)
0.1180
0.35492 (16)
0.08411 (17)
0.5388 (3)
0.5528
0.4979
0.07802 (19)
0.0262
0.0242 (6)
0.0224 (6)
0.0752 (14)
0.090*
0.090*
0.0297 (6)
0.036*
C5A
C1T
H1T1
H1T2
C4A
H4A
C2
0.5570 (3)
0.5862
0.3951 (2)
0.4250
0.32735 (18)
0.3640
0.0309 (7)
0.037*
H2
C2T
H2TA
H2TB
H2TC
C3
−0.0622 (4)
−0.0398
−0.0709
−0.1366
0.5619 (3)
0.5935
0.2631 (4)
0.3009
0.2005
0.3107
0.4253 (2)
0.4763
0.6162 (3)
0.6544
0.6420
0.6013
0.24553 (19)
0.2276
0.0695 (12)
0.104*
0.104*
0.104*
0.0345 (7)
0.041*
H3
C3A
H3A
C4
0.7767 (3)
0.7283
0.5199 (3)
0.5256
0.1189 (2)
0.0818
0.3800 (2)
0.3993
0.1491 (2)
0.1451
0.18989 (18)
0.1346
0.0351 (7)
0.042*
0.0343 (7)
0.041*
H4
C2A
H2A
C1A
H1A
C5
0.7835 (3)
0.7404
0.8534 (3)
0.8564
0.4696 (3)
0.4420
0.1526 (2)
0.1369
0.2090 (2)
0.2322
0.3064 (2)
0.2758
0.2262 (2)
0.2738
0.23351 (18)
0.2856
0.21672 (18)
0.1794
0.0349 (7)
0.042*
0.0282 (6)
0.034*
0.0319 (7)
0.038*
H5
C20A
C6
C7
0.9197 (2)
0.4603 (2)
0.3410 (3)
0.3340
0.2309 (2)
0.2781 (2)
0.1778 (2)
0.2031
0.16182 (17)
0.29950 (17)
0.29453 (17)
0.2413
0.0226 (6)
0.0255 (6)
0.0265 (6)
0.032*
H7
C19A
H19A
C18A
C8
C17A
H17A
C9
1.0190 (2)
0.9933
1.0854 (2)
0.2809 (2)
1.1076 (3)
1.0837
0.3174 (2)
0.2917
0.3842 (2)
0.1087 (2)
0.4048 (2)
0.3719
0.22613 (16)
0.2762
0.22816 (16)
0.32543 (17)
0.30642 (18)
0.3531
0.0228 (6)
0.027*
0.0223 (6)
0.0243 (6)
0.0320 (7)
0.038*
0.2189 (3)
0.0800 (2)
0.27187 (18)
0.0280 (6)
Acta Cryst. (2019). C75
sup-2

supporting information
H9
0.2180
0.1070
0.2187
0.034*
C16A
H16A
C10
H10
C11
1.1634 (3)
1.1795
0.1608 (3)
0.1201
0.1625 (3)
0.1226
1.1970 (3)
1.2340
1.1755 (2)
0.2228 (2)
1.1224 (2)
0.2825 (2)
0.4968 (2)
1.1073 (2)
1.1604 (2)
0.5028 (2)
1.1856 (3)
1.2233
0.4719 (3)
0.4831
0.31399 (19)
0.3654
0.29680 (19)
0.2611
0.37686 (18)
0.3941
0.24454 (18)
0.2503
0.16792 (16)
0.42984 (17)
0.15751 (15)
0.40557 (16)
0.60431 (16)
−0.13148 (16)
−0.20851 (16)
0.68710 (16)
−0.27980 (18)
−0.3294
0.0375 (7)
0.045*
0.0319 (7)
0.038*
0.0304 (6)
0.036*
0.0312 (7)
0.037*
0.0232 (6)
0.0264 (6)
0.0189 (5)
0.0226 (6)
0.0224 (6)
0.0206 (5)
0.0230 (6)
0.0227 (6)
0.0341 (7)
0.041*
0.0138 (2)
−0.0039
−0.0279 (2)
−0.0730
0.5246 (2)
0.5716
0.5069 (2)
−0.0021 (2)
0.4335 (2)
0.0675 (2)
0.1922 (2)
0.2922 (2)
0.3190 (2)
0.1578 (2)
0.2562 (2)
0.2734
H11
C15A
H15A
C14A
C12
C13A
C13
C14
C12A
C11A
C15
C10A
H10A
C16
0.5523 (3)
0.5559
0.1992 (2)
0.1753
0.73854 (17)
0.7924
0.0276 (6)
0.033*
H16
C9A
H9A
C17
1.1544 (3)
1.1738
0.5973 (3)
0.6306
0.1664 (3)
0.1227
0.2776 (2)
0.3057
−0.2774 (2)
−0.3251
0.70969 (18)
0.7446
0.0429 (8)
0.051*
0.0307 (6)
0.037*
H17
C8A
H8A
C18
1.0957 (3)
1.0715
0.5923 (3)
0.6225
0.1423 (2)
0.0848
0.3129 (2)
0.3648
−0.20543 (19)
−0.2053
0.63031 (17)
0.6118
0.0370 (7)
0.044*
0.0279 (6)
0.034*
H18
C7A
C19
C6A
H6A
C20
1.0715 (2)
0.5422 (2)
1.0075 (2)
0.9814
0.5427 (2)
0.5748
0.2045 (2)
0.2716 (2)
0.1765 (2)
0.1212
0.3105 (2)
0.3623
−0.13123 (17)
0.57628 (16)
−0.05780 (17)
−0.0630
0.49339 (17)
0.4796
0.0254 (6)
0.0229 (6)
0.0236 (6)
0.028*
0.0242 (6)
0.029*
H20
C021
H02A
H02B
H02C
C21
H21A
H21B
H21C
C22
H22A
H22B
H22C
C022
1.2292 (3)
1.3074
1.2332
1.1764
0.1731 (3)
0.0886
0.1892
0.2023
0.4375 (3)
0.5126
0.3993
0.4467 (2)
0.3945
0.5154
−0.28041 (17)
−0.3033
−0.2708
−0.3188
0.5381 (2)
0.5411
0.5923
0.5004
0.79402 (17)
0.8127
0.8015
0.0296 (6)
0.044*
0.044*
0.044*
0.0380 (7)
0.057*
0.057*
0.057*
0.0331 (7)
0.050*
0.050*
0.4554
−0.1105 (3)
−0.0724
−0.1341
−0.1726
0.0573 (3)
0.0259
0.0069
0.1235
0.6319 (2)
0.3874
1.2547 (3)
0.8257
0.10115 (19)
0.050*
0.0314 (7)
Acta Cryst. (2019). C75
sup-3

supporting information
H02D
H02E
H02F
N01
N02
N03
N04
N07
N08
O1
1.2020
1.2669
1.3299
0.6898
0.6611
0.5966
0.1403
0.0475
0.1192
0.047*
0.047*
0.047*
0.99260 (19)
0.98374 (19)
0.5016 (2)
0.4048 (2)
1.2872 (2)
0.7856 (2)
1.09202 (16)
0.0628 (2)
0.0025
0.29061 (16)
0.22294 (16)
0.27866 (17)
0.20796 (17)
−0.06382 (18)
0.43557 (19)
0.35187 (13)
0.3039 (3)
0.3565
0.15943 (13)
0.01499 (13)
0.43608 (13)
0.33505 (14)
0.07667 (15)
0.45715 (14)
−0.06456 (11)
0.5058 (2)
0.4995
0.0201 (5)
0.0201 (5)
0.0225 (5)
0.0242 (5)
0.0290 (5)
0.0286 (5)
0.0204 (4)
0.0765 (9)
0.115*
O1A
H1AA
O2
1.10899 (16)
1.20306 (17)
1.18555 (16)
1.20062 (17)
0.89451 (16)
0.33834 (17)
0.44928 (17)
0.45715 (17)
0.23163 (18)
0.2739 (2)
0.57291 (18)
0.6790 (2)
0.8200 (2)
0.8595 (2)
1.18516 (17)
1.2986 (2)
1.05248 (7)
0.41964 (7)
1.4110 (4)
1.4261
1.3324
1.4689
1.4043 (5)
1.4649
1.4190 (11)
1.3585
1.4964
1.4144 (5)
1.4471
1.4270 (10)
1.5061
1.3700
0.41676 (14)
0.55492 (14)
0.40955 (14)
0.20279 (15)
0.44340 (14)
0.08916 (14)
0.14838 (14)
0.08044 (15)
−0.03909 (15)
0.30139 (17)
0.05570 (15)
0.49714 (18)
0.34409 (16)
0.4692 (2)
0.01059 (15)
−0.15766 (16)
0.32514 (6)
0.17640 (6)
0.3722 (3)
0.4338
0.3968
0.3330
0.2113 (3)
0.1696
0.3067 (5)
0.3460
0.2868
0.2145 (3)
0.1796
0.3121 (6)
0.2989
0.3598
0.08147 (10)
0.09594 (11)
−0.20349 (11)
0.04417 (13)
0.05168 (11)
0.46022 (11)
0.55821 (11)
0.70789 (11)
0.50890 (12)
0.48967 (13)
0.40929 (12)
0.47098 (16)
0.42420 (13)
0.47657 (15)
0.07687 (13)
0.09207 (15)
0.04415 (5)
0.45372 (5)
−0.0676 (2)
−0.0534
−0.0806
−0.1149
−0.0212 (3)
−0.0512
−0.0030 (6)
0.0440
0.0127
0.0158 (3)
−0.0283
0.0117 (6)
0.0219
0.0568
0.0203 (4)
0.0249 (4)
0.0238 (4)
0.0256 (4)
0.0199 (4)
0.0245 (4)
0.0248 (4)
0.0259 (4)
0.0295 (4)
0.0324 (5)
0.0251 (4)
0.0496 (6)
0.0372 (5)
0.0478 (6)
0.0325 (5)
0.0413 (6)
0.01802 (17)
0.02215 (19)
0.0651 (12)
0.098*
0.098*
0.098*
0.0478 (6)
0.072*
0.0478 (6)
0.057*
0.057*
0.0496 (6)
0.074*
0.0496 (6)
0.059*
0.059*
O3
O4
O5
O6
O7
O8
O9
O10
O11
O12
O13
O14
O15
O16
O18
Al1
Al2
C4R
H4R1
H4R2
H4R3
O4T
H4T
C4T
H4T1
H4T2
O4U
H4U
C4U
H4U1
H4U2
O17
H52
H51
H61
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1.37647 (19)
1.203 (3)
1.269 (2)
−0.04004 (17)
0.1372 (18)
0.200 (4)
0.06044 (16)
0.049 (2)
0.021 (3)
0.0444 (6)
0.048 (10)*
0.097 (18)*
0.056 (12)*
0.879 (3)
0.461 (3)
0.0022 (14)
Acta Cryst. (2019). C75
sup-4

supporting information
H62
0.891 (3)
0.205 (2)
0.269 (4)
0.563 (3)
0.620 (3)
0.500 (2)
0.301 (3)
0.364 (2)
0.003 (2)
0.028 (3)
0.077 (2)
0.494 (2)
0.496 (3)
0.389 (2)
0.443 (2)
0.049 (11)*
0.061 (13)*
0.071 (14)*
0.045 (10)*
0.081 (15)*
H11B
H11A
H12B
H12A
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
C1
0.0277 (14)
0.0218 (13)
0.057 (3)
0.0304 (16)
0.0418 (18)
0.065 (3)
0.0180 (13)
0.0152 (12)
0.085 (3)
0.0283 (15)
0.0234 (14)
0.061 (3)
0.0214 (14)
0.0275 (14)
0.057 (3)
0.0336 (16)
0.0290 (15)
0.075 (3)
−0.0039 (11)
−0.0058 (10)
0.001 (3)
−0.0148 (13)
−0.0134 (13)
−0.020 (2)
−0.0039 (11)
−0.0028 (11)
−0.009 (2)
−0.0068 (12)
−0.0101 (13)
−0.006 (2)
0.0037 (10)
0.0080 (10)
−0.007 (3)
0.0061 (12)
0.0061 (12)
0.003 (2)
C5A
C1T
C4A
C2
C2T
C3
0.0456 (19)
0.0359 (17)
0.0455 (19)
0.0341 (17)
0.0313 (16)
0.0401 (17)
0.0211 (13)
0.0301 (15)
0.0319 (15)
0.0203 (13)
0.0242 (14)
0.0256 (14)
0.0365 (17)
0.0314 (16)
0.0474 (19)
0.0317 (16)
0.0281 (15)
0.0342 (16)
0.0200 (13)
0.0283 (15)
0.0162 (12)
0.0228 (14)
0.0231 (14)
0.0189 (13)
0.0236 (14)
0.0252 (14)
0.0394 (18)
0.0302 (15)
0.063 (2)
0.0253 (15)
0.0332 (16)
0.0335 (16)
0.0338 (16)
0.0252 (14)
0.0335 (16)
0.0165 (12)
0.0207 (13)
0.0221 (13)
0.0210 (13)
0.0213 (13)
0.0208 (13)
0.0397 (17)
0.0261 (14)
0.0491 (19)
0.0328 (16)
0.0285 (15)
0.0380 (17)
0.0227 (13)
0.0221 (13)
0.0159 (12)
0.0187 (13)
0.0173 (12)
0.0167 (12)
0.0193 (13)
0.0177 (12)
0.0361 (17)
0.0302 (15)
0.0401 (18)
0.0340 (16)
0.0291 (16)
0.0280 (14)
0.0187 (13)
0.0347 (17)
0.0422 (18)
0.0252 (15)
0.0363 (17)
0.0271 (15)
0.0250 (15)
0.0266 (14)
0.0232 (14)
0.0203 (14)
0.0200 (13)
0.0185 (13)
0.0224 (14)
0.0225 (15)
0.0238 (14)
0.0236 (15)
0.0325 (16)
0.0339 (16)
0.0287 (16)
0.0239 (14)
0.0235 (14)
0.0200 (13)
0.0220 (14)
0.0203 (13)
0.0206 (13)
0.0232 (14)
0.0196 (13)
0.0220 (15)
0.0192 (14)
0.0267 (16)
0.0249 (15)
0.0327 (17)
0.0250 (15)
0.0252 (14)
−0.0170 (14)
−0.0223 (14)
−0.0163 (14)
−0.0180 (14)
−0.0125 (12)
−0.0161 (14)
−0.0048 (10)
−0.0075 (11)
−0.0049 (12)
−0.0019 (11)
−0.0056 (11)
−0.0046 (11)
−0.0173 (14)
−0.0067 (12)
−0.0240 (16)
−0.0114 (13)
−0.0114 (12)
−0.0192 (14)
−0.0053 (11)
−0.0055 (12)
−0.0011 (10)
−0.0033 (11)
−0.0017 (11)
−0.0014 (10)
−0.0059 (11)
−0.0035 (11)
−0.0144 (14)
−0.0085 (12)
−0.0267 (17)
−0.0166 (13)
−0.0210 (15)
−0.0136 (12)
−0.0080 (11)
−0.0075 (14)
−0.0028 (14)
−0.0107 (13)
0.0033 (13)
−0.0011 (12)
−0.0110 (13)
−0.0030 (11)
−0.0056 (11)
−0.0068 (11)
−0.0023 (10)
−0.0059 (10)
−0.0050 (11)
−0.0087 (12)
−0.0094 (12)
−0.0143 (14)
−0.0125 (13)
−0.0040 (12)
−0.0121 (13)
−0.0043 (11)
−0.0030 (11)
−0.0047 (10)
−0.0050 (11)
−0.0026 (10)
−0.0034 (10)
−0.0040 (11)
−0.0021 (11)
0.0055 (13)
−0.0047 (11)
0.0068 (15)
−0.0075 (12)
0.0010 (14)
−0.0027 (12)
−0.0021 (11)
0.0119 (13)
0.0085 (14)
0.0143 (13)
0.0104 (13)
0.0086 (12)
0.0091 (12)
0.0084 (11)
0.0063 (11)
0.0060 (11)
0.0086 (10)
0.0055 (10)
0.0014 (11)
0.0107 (13)
0.0026 (11)
0.0062 (14)
0.0018 (13)
0.0022 (12)
0.0024 (13)
0.0035 (11)
0.0023 (11)
0.0026 (10)
0.0008 (10)
−0.0024 (10)
0.0018 (10)
0.0036 (11)
0.0000 (10)
−0.0032 (12)
−0.0008 (11)
−0.0143 (14)
−0.0011 (12)
−0.0082 (13)
0.0006 (12)
0.0012 (11)
C3A
C4
C2A
C1A
C5
C20A
C6
C7
C19A
C18A
C8
C17A
C9
C16A
C10
C11
C15A
C14A
C12
C13A
C13
C14
C12A
C11A
C15
C10A
C16
C9A
C17
C8A
C18
C7A
0.0367 (17)
0.051 (2)
0.0316 (16)
0.0295 (15)
Acta Cryst. (2019). C75
sup-5

supporting information
C19
C6A
C20
C021
C21
C22
C022
N01
N02
N03
N04
N07
N08
O1
O1A
O2
O3
O4
O5
O6
O7
O8
O9
O10
O11
O12
O13
O14
O15
O16
O18
Al1
Al2
C4R
O4T
C4T
O4U
C4U
O17
0.0227 (14)
0.0268 (14)
0.0231 (14)
0.0285 (15)
0.0372 (18)
0.0419 (18)
0.0359 (17)
0.0203 (11)
0.0206 (11)
0.0255 (12)
0.0294 (13)
0.0304 (13)
0.0384 (15)
0.0237 (9)
0.0380 (16)
0.0246 (10)
0.0308 (11)
0.0267 (10)
0.0206 (10)
0.0209 (9)
0.0310 (10)
0.0340 (11)
0.0349 (11)
0.0362 (11)
0.0342 (13)
0.0319 (11)
0.0346 (11)
0.0487 (14)
0.0620 (14)
0.0244 (11)
0.0480 (14)
0.0185 (4)
0.0274 (4)
0.052 (2)
0.0188 (13)
0.0149 (12)
0.0186 (13)
0.0305 (15)
0.0424 (18)
0.0403 (17)
0.0281 (15)
0.0157 (10)
0.0158 (10)
0.0188 (11)
0.0185 (11)
0.0187 (12)
0.0236 (12)
0.0173 (9)
0.099 (3)
0.0196 (9)
0.0233 (9)
0.0231 (9)
0.0169 (9)
0.0172 (9)
0.0226 (9)
0.0217 (9)
0.0256 (10)
0.0295 (10)
0.0217 (11)
0.0190 (10)
0.0331 (10)
0.0199 (10)
0.0528 (13)
0.0204 (10)
0.0181 (10)
0.0146 (4)
0.0183 (4)
0.065 (3)
0.0224 (14)
0.0271 (15)
0.0260 (14)
0.0244 (15)
0.0384 (18)
0.0208 (14)
0.0387 (17)
0.0215 (11)
0.0219 (11)
0.0177 (11)
0.0226 (12)
0.0391 (14)
0.0237 (12)
0.0188 (9)
0.084 (2)
0.0167 (9)
0.0254 (10)
0.0206 (10)
0.0363 (11)
0.0189 (10)
0.0201 (10)
0.0194 (9)
0.0179 (9)
0.0247 (10)
0.0334 (12)
0.0229 (10)
0.0604 (15)
0.0402 (13)
0.0459 (13)
0.0500 (13)
0.0614 (15)
0.0191 (4)
0.0188 (4)
0.045 (2)
−0.0042 (11)
−0.0066 (11)
−0.0041 (11)
−0.0102 (12)
−0.0217 (15)
−0.0205 (15)
−0.0190 (13)
−0.0047 (9)
−0.0055 (9)
−0.0036 (9)
−0.0069 (10)
−0.0074 (10)
−0.0130 (11)
−0.0069 (7)
−0.0208 (16)
−0.0086 (8)
−0.0155 (8)
−0.0103 (8)
−0.0057 (8)
−0.0052 (7)
−0.0097 (8)
−0.0107 (8)
−0.0131 (9)
−0.0154 (9)
−0.0043 (10)
−0.0078 (8)
0.0043 (9)
−0.0016 (11)
−0.0041 (11)
−0.0022 (11)
0.0033 (11)
−0.0055 (14)
−0.0063 (13)
−0.0145 (13)
−0.0038 (9)
−0.0037 (9)
−0.0033 (9)
−0.0065 (10)
−0.0150 (11)
−0.0049 (10)
−0.0034 (7)
−0.0100 (15)
−0.0054 (7)
−0.0068 (8)
−0.0013 (8)
−0.0033 (8)
−0.0030 (7)
−0.0082 (8)
−0.0078 (8)
−0.0043 (8)
−0.0061 (8)
−0.0028 (9)
−0.0066 (9)
0.0002 (10)
−0.0085 (10)
−0.0113 (11)
−0.0126 (9)
−0.0224 (11)
−0.0031 (3)
−0.0051 (3)
0.0040 (18)
−0.0113 (11)
−0.0113 (11)
0.0002 (10)
0.0002 (10)
−0.0118 (11)
−0.0005 (10)
0.0029 (11)
0.0009 (11)
0.0082 (12)
0.0159 (15)
0.0084 (13)
0.0076 (13)
0.0078 (9)
0.0055 (9)
0.0038 (9)
0.0045 (9)
0.0034 (10)
0.0067 (10)
0.0028 (7)
0.024 (2)
0.0059 (7)
0.0058 (8)
0.0059 (7)
0.0077 (8)
0.0040 (8)
0.0055 (7)
0.0024 (7)
0.0037 (8)
0.0084 (8)
0.0033 (9)
0.0017 (8)
0.0015 (10)
−0.0024 (9)
0.0024 (10)
0.0052 (9)
0.0103 (10)
0.0054 (3)
0.0040 (3)
−0.0008 (19)
0.0024 (10)
0.0024 (10)
0.0015 (10)
0.0015 (10)
0.0024 (11)
−0.0102 (9)
−0.0404 (11)
−0.0040 (8)
−0.0122 (10)
−0.0051 (3)
−0.0069 (3)
0.006 (2)
−0.0404 (11)
−0.0404 (11)
0.0043 (9)
0.0620 (14)
0.0620 (14)
0.0346 (11)
0.0346 (11)
0.0264 (12)
0.0528 (13)
0.0528 (13)
0.0331 (10)
0.0331 (10)
0.0281 (11)
0.0459 (13)
0.0459 (13)
0.0604 (15)
0.0604 (15)
0.0793 (18)
0.0043 (9)
−0.0105 (9)
Geometric parameters (Å, º)
C1—C2
1.396 (4)
C16—H16
0.9300
C1—C6
1.405 (4)
1.419 (3)
1.385 (4)
1.398 (4)
1.426 (3)
C9A—C8A
C9A—H9A
C17—C18
C17—H17
C8A—C7A
1.367 (4)
0.9300
1.370 (4)
0.9300
C1—N03
C5A—C4A
C5A—C20A
C5A—N02
1.415 (4)
Acta Cryst. (2019). C75
sup-6

supporting information
C1T—O1A
C1T—C2T
C1T—H1T1
C1T—H1T2
C4A—C3A
C4A—H4A
C2—C3
1.293 (6)
1.517 (6)
0.9700
0.9700
1.381 (4)
0.9300
1.382 (4)
0.9300
0.9600
0.9600
0.9600
1.390 (4)
0.9300
1.384 (5)
0.9300
1.383 (4)
0.9300
1.379 (4)
0.9300
1.399 (4)
0.9300
1.390 (4)
0.9300
1.420 (3)
1.423 (3)
1.301 (4)
1.430 (4)
0.9300
1.296 (3)
1.442 (4)
0.9300
1.406 (4)
1.417 (4)
1.405 (4)
1.418 (4)
1.354 (4)
0.9300
1.360 (4)
0.9300
1.403 (4)
0.9300
1.406 (4)
0.9300
1.376 (4)
0.9300
1.376 (4)
0.9300
1.376 (3)
C8A—H8A
C18—C19
C18—H18
C7A—C6A
C19—C20
C6A—N02
C6A—H6A
C20—N03
C20—H20
C021—O4
C021—H02A
C021—H02B
C021—H02C
C21—O10
C21—H21A
C21—H21B
C21—H21C
C22—O9
C22—H22A
C22—H22B
C22—H22C
C022—O3
C022—H02D
C022—H02E
C022—H02F
N01—Al1
N02—Al1
N03—Al2
N04—Al2
N07—O18
N07—O17
N07—O16
N08—O13
N08—O14
N08—O15
O1—Al1
0.9300
1.409 (4)
0.9300
1.441 (4)
1.435 (4)
1.294 (3)
0.9300
1.303 (4)
0.9300
1.431 (3)
0.9600
0.9600
0.9600
1.436 (3)
0.9600
0.9600
0.9600
1.431 (3)
0.9600
0.9600
0.9600
1.425 (3)
0.9600
0.9600
0.9600
2.007 (2)
1.988 (2)
1.991 (2)
1.998 (2)
1.229 (3)
1.252 (3)
1.263 (3)
1.233 (3)
1.235 (3)
1.261 (3)
1.8197 (19)
0.8200
1.8066 (19)
1.918 (2)
0.870 (18)
0.845 (19)
1.958 (2)
0.871 (18)
0.860 (18)
1.812 (2)
1.809 (2)
1.925 (2)
0.852 (19)
C2—H2
C2T—H2TA
C2T—H2TB
C2T—H2TC
C3—C4
C3—H3
C3A—C2A
C3A—H3A
C4—C5
C4—H4
C2A—C1A
C2A—H2A
C1A—C20A
C1A—H1A
C5—C6
C5—H5
C20A—N01
C6—N04
C7—N04
C7—C8
C7—H7
C19A—N01
C19A—C18A
C19A—H19A
C18A—C13A
C18A—C17A
C8—C13
C8—C9
C17A—C16A
C17A—H17A
C9—C10
O1A—H1AA
O2—Al1
O5—Al1
O5—H52
O5—H51
O6—Al1
O6—H61
O6—H62
O7—Al2
C9—H9
C16A—C15A
C16A—H16A
C10—C11
C10—H10
C11—C12
C11—H11
C15A—C14A
C15A—H15A
C14A—O3
O8—Al2
O11—Al2
O11—H11B
Acta Cryst. (2019). C75
sup-7

supporting information
C14A—C13A
C12—O10
C12—C13
C13A—O2
C13—O7
1.413 (4)
1.376 (3)
1.411 (4)
1.324 (3)
1.330 (3)
1.316 (3)
1.415 (4)
1.421 (4)
1.321 (3)
1.410 (4)
1.417 (4)
1.375 (3)
1.378 (4)
1.372 (3)
1.372 (4)
1.400 (4)
0.9300
O11—H11A
O12—Al2
0.826 (19)
1.977 (2)
0.852 (18)
0.848 (19)
1.340 (7)
1.504 (9)
0.9600
0.9600
0.9600
1.410 (4)
0.8200
0.9700
0.9700
1.376 (9)
1.2082
0.9700
0.9700
O12—H12B
O12—H12A
C4R—C4T
C4R—C4U
C4R—H4R1
C4R—H4R2
C4R—H4R3
O4T—C4T
O4T—H4T
C4T—H4T1
C4T—H4T2
O4U—C4U
O4U—H4U
C4U—H4U1
C4U—H4U2
C14—O8
C14—C19
C14—C15
C12A—O1
C12A—C7A
C12A—C11A
C11A—O4
C11A—C10A
C15—O9
C15—C16
C10A—C9A
C10A—H10A
C16—C17
1.404 (4)
C2—C1—C6
C2—C1—N03
C6—C1—N03
119.3 (2)
125.6 (3)
115.1 (2)
120.2 (2)
124.6 (3)
115.1 (2)
113.9 (4)
108.8
108.8
108.8
108.8
107.7
119.9 (3)
120.0
120.0
119.9 (3)
120.0
120.0
109.5
109.5
109.5
109.5
C18—C19—C14
C18—C19—C20
C14—C19—C20
N02—C6A—C7A
N02—C6A—H6A
C7A—C6A—H6A
N03—C20—C19
N03—C20—H20
C19—C20—H20
O4—C021—H02A
O4—C021—H02B
H02A—C021—H02B
O4—C021—H02C
H02A—C021—H02C
H02B—C021—H02C
O10—C21—H21A
O10—C21—H21B
H21A—C21—H21B
O10—C21—H21C
H21A—C21—H21C
H21B—C21—H21C
O9—C22—H22A
O9—C22—H22B
H22A—C22—H22B
O9—C22—H22C
H22A—C22—H22C
H22B—C22—H22C
O3—C022—H02D
O3—C022—H02E
119.5 (2)
117.7 (2)
122.8 (2)
124.5 (2)
117.8
117.8
124.8 (3)
117.6
117.6
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
C4A—C5A—C20A
C4A—C5A—N02
C20A—C5A—N02
O1A—C1T—C2T
O1A—C1T—H1T1
C2T—C1T—H1T1
O1A—C1T—H1T2
C2T—C1T—H1T2
H1T1—C1T—H1T2
C3A—C4A—C5A
C3A—C4A—H4A
C5A—C4A—H4A
C3—C2—C1
C3—C2—H2
C1—C2—H2
C1T—C2T—H2TA
C1T—C2T—H2TB
H2TA—C2T—H2TB
C1T—C2T—H2TC
H2TA—C2T—H2TC
H2TB—C2T—H2TC
C2—C3—C4
C2—C3—H3
C4—C3—H3
C4A—C3A—C2A
C4A—C3A—H3A
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
120.6 (3)
119.7
119.7
120.0 (3)
120.0
109.5
Acta Cryst. (2019). C75
sup-8

supporting information
C2A—C3A—H3A
C5—C4—C3
C5—C4—H4
120.0
120.0 (3)
120.0
120.0
121.0 (3)
119.5
119.5
119.3 (3)
120.3
120.3
120.0 (3)
120.0
H02D—C022—H02E
O3—C022—H02F
H02D—C022—H02F
H02E—C022—H02F
C19A—N01—C20A
C19A—N01—Al1
C20A—N01—Al1
C6A—N02—C5A
C6A—N02—Al1
C5A—N02—Al1
C20—N03—C1
C20—N03—Al2
C1—N03—Al2
109.5
109.5
109.5
109.5
C3—C4—H4
C1A—C2A—C3A
C1A—C2A—H2A
C3A—C2A—H2A
C2A—C1A—C20A
C2A—C1A—H1A
C20A—C1A—H1A
C4—C5—C6
C4—C5—H5
C6—C5—H5
C5A—C20A—C1A
C5A—C20A—N01
C1A—C20A—N01
C5—C6—C1
122.2 (2)
124.05 (18)
113.73 (17)
121.5 (2)
124.28 (18)
113.89 (17)
121.2 (2)
124.53 (19)
114.18 (18)
121.2 (2)
124.68 (19)
113.82 (18)
120.7 (2)
120.7 (2)
118.6 (2)
121.5 (3)
118.1 (3)
120.4 (3)
128.82 (16)
109.5
129.86 (16)
117.7 (2)
116.4 (2)
121 (2)
126 (3)
109 (4)
110 (3)
111 (2)
108 (3)
120.0
119.5 (3)
114.8 (2)
125.7 (3)
120.0 (3)
125.0 (3)
115.0 (2)
125.1 (2)
117.4
C7—N04—C6
C7—N04—Al2
C6—N04—Al2
O18—N07—O17
O18—N07—O16
O17—N07—O16
O13—N08—O14
O13—N08—O15
O14—N08—O15
C12A—O1—Al1
C1T—O1A—H1AA
C13A—O2—Al1
C14A—O3—C022
C11A—O4—C021
Al1—O5—H52
Al1—O5—H51
H52—O5—H51
Al1—O6—H61
Al1—O6—H62
H61—O6—H62
C13—O7—Al2
C5—C6—N04
C1—C6—N04
N04—C7—C8
N04—C7—H7
C8—C7—H7
117.4
124.6 (2)
117.7
N01—C19A—C18A
N01—C19A—H19A
C18A—C19A—H19A
C13A—C18A—C17A
C13A—C18A—C19A
C17A—C18A—C19A
C13—C8—C9
C13—C8—C7
C9—C8—C7
C16A—C17A—C18A
C16A—C17A—H17A
C18A—C17A—H17A
C10—C9—C8
C10—C9—H9
C8—C9—H9
C17A—C16A—C15A
C17A—C16A—H16A
C15A—C16A—H16A
C9—C10—C11
117.7
119.5 (3)
123.0 (2)
117.4 (2)
119.2 (3)
122.7 (3)
118.0 (2)
120.8 (3)
119.6
119.6
121.2 (3)
119.4
119.4
120.3 (3)
119.9
119.9
119.7 (3)
120.2
120.2
120.3 (3)
119.8
119.8
120.2 (3)
119.9
130.62 (17)
130.45 (17)
117.1 (2)
117.0 (2)
124 (3)
125 (3)
111 (4)
112 (2)
116 (3)
C14—O8—Al2
C15—O9—C22
C12—O10—C21
Al2—O11—H11B
Al2—O11—H11A
H11B—O11—H11A
Al2—O12—H12B
Al2—O12—H12A
H12B—O12—H12A
O2—Al1—O1
O2—Al1—O5
O1—Al1—O5
O2—Al1—O6
O1—Al1—O6
C9—C10—H10
C11—C10—H10
C12—C11—C10
C12—C11—H11
C10—C11—H11
C14A—C15A—C16A
C14A—C15A—H15A
106 (4)
93.64 (8)
91.91 (9)
93.74 (9)
90.49 (9)
90.72 (8)
Acta Cryst. (2019). C75
sup-9

supporting information
C16A—C15A—H15A
O3—C14A—C15A
O3—C14A—C13A
C15A—C14A—C13A
C11—C12—O10
C11—C12—C13
O10—C12—C13
O2—C13A—C18A
O2—C13A—C14A
C18A—C13A—C14A
O7—C13—C8
O7—C13—C12
C8—C13—C12
O8—C14—C19
O8—C14—C15
C19—C14—C15
O1—C12A—C7A
O1—C12A—C11A
C7A—C12A—C11A
O4—C11A—C10A
O4—C11A—C12A
C10A—C11A—C12A
O9—C15—C16
119.9
O5—Al1—O6
O2—Al1—N02
O1—Al1—N02
O5—Al1—N02
O6—Al1—N02
O2—Al1—N01
O1—Al1—N01
O5—Al1—N01
O6—Al1—N01
N02—Al1—N01
O8—Al2—O7
O8—Al2—O11
O7—Al2—O11
O8—Al2—O12
O7—Al2—O12
O11—Al2—O12
O8—Al2—N03
O7—Al2—N03
174.80 (9)
174.22 (9)
92.09 (9)
88.49 (10)
88.67 (9)
93.08 (9)
172.56 (10)
89.23 (9)
86.03 (8)
81.16 (9)
92.64 (9)
93.25 (9)
90.98 (10)
90.12 (9)
92.38 (9)
175.12 (10)
93.18 (9)
173.99 (9)
87.18 (10)
89.12 (10)
173.64 (10)
92.57 (9)
90.32 (10)
86.01 (9)
81.73 (9)
109.5
109.5
109.5
109.5
109.5
109.5
109.5
112.5 (6)
109.1
109.1
109.1
109.1
107.8
104.5
117.6 (7)
107.9
107.9
107.9
107.9
125.2 (3)
114.0 (2)
120.7 (2)
125.3 (3)
120.9 (3)
113.8 (2)
124.0 (2)
117.5 (2)
118.4 (2)
123.8 (2)
117.5 (2)
118.6 (2)
123.9 (2)
118.0 (2)
118.2 (2)
123.9 (2)
118.2 (2)
117.9 (2)
125.1 (2)
113.7 (2)
121.2 (3)
125.2 (2)
113.5 (2)
121.2 (3)
119.8 (3)
120.1
120.1
119.9 (3)
120.0
120.0
120.6 (3)
119.7
119.7
120.3 (3)
119.8
119.8
120.2 (3)
119.9
O11—Al2—N03
O12—Al2—N03
O8—Al2—N04
O7—Al2—N04
O11—Al2—N04
O12—Al2—N04
N03—Al2—N04
C4T—C4R—H4R1
C4T—C4R—H4R2
H4R1—C4R—H4R2
C4T—C4R—H4R3
H4R1—C4R—H4R3
H4R2—C4R—H4R3
C4T—O4T—H4T
C4R—C4T—O4T
C4R—C4T—H4T1
O4T—C4T—H4T1
C4R—C4T—H4T2
O4T—C4T—H4T2
H4T1—C4T—H4T2
C4U—O4U—H4U
O4U—C4U—C4R
O4U—C4U—H4U1
C4R—C4U—H4U1
O4U—C4U—H4U2
C4R—C4U—H4U2
H4U1—C4U—H4U2
O9—C15—C14
C16—C15—C14
C11A—C10A—C9A
C11A—C10A—H10A
C9A—C10A—H10A
C15—C16—C17
C15—C16—H16
C17—C16—H16
C8A—C9A—C10A
C8A—C9A—H9A
C10A—C9A—H9A
C18—C17—C16
C18—C17—H17
C16—C17—H17
C9A—C8A—C7A
C9A—C8A—H8A
C7A—C8A—H8A
C17—C18—C19
C17—C18—H18
C19—C18—H18
C12A—C7A—C8A
C12A—C7A—C6A
C8A—C7A—C6A
119.9
120.9 (3)
119.6
119.6
120.0 (2)
122.3 (2)
117.7 (3)
107.2
C20A—C5A—C4A—C3A
−1.1 (4)
O1—C12A—C7A—C6A
4.1 (4)
Acta Cryst. (2019). C75
sup-10

supporting information
N02—C5A—C4A—C3A
C6—C1—C2—C3
N03—C1—C2—C3
C1—C2—C3—C4
C5A—C4A—C3A—C2A
C2—C3—C4—C5
C4A—C3A—C2A—C1A
C3A—C2A—C1A—C20A
C3—C4—C5—C6
C4A—C5A—C20A—C1A
N02—C5A—C20A—C1A
C4A—C5A—C20A—N01
N02—C5A—C20A—N01
C2A—C1A—C20A—C5A
C2A—C1A—C20A—N01
C4—C5—C6—C1
−179.3 (3)
−2.3 (4)
177.5 (3)
−0.9 (5)
0.2 (4)
1.8 (5)
0.9 (5)
−1.0 (4)
0.4 (5)
1.0 (4)
C11A—C12A—C7A—C6A
−174.5 (2)
0.5 (5)
178.9 (3)
−0.3 (4)
−178.5 (3)
−179.4 (2)
0.6 (4)
−1.3 (4)
178.7 (2)
−4.8 (4)
176.9 (3)
178.8 (3)
0.6 (4)
−175.4 (2)
6.1 (3)
−171.3 (2)
10.6 (4)
7.3 (3)
−170.8 (2)
176.4 (2)
−10.2 (4)
−16.8 (4)
164.9 (2)
169.2 (2)
−9.1 (3)
C9A—C8A—C7A—C12A
C9A—C8A—C7A—C6A
C17—C18—C19—C14
C17—C18—C19—C20
O8—C14—C19—C18
C15—C14—C19—C18
O8—C14—C19—C20
C15—C14—C19—C20
C12A—C7A—C6A—N02
C8A—C7A—C6A—N02
C18—C19—C20—N03
C14—C19—C20—N03
C18A—C19A—N01—C20A
C18A—C19A—N01—Al1
C5A—C20A—N01—C19A
C1A—C20A—N01—C19A
C5A—C20A—N01—Al1
C1A—C20A—N01—Al1
C7A—C6A—N02—C5A
C7A—C6A—N02—Al1
C4A—C5A—N02—C6A
C20A—C5A—N02—C6A
C4A—C5A—N02—Al1
C20A—C5A—N02—Al1
C19—C20—N03—C1
C19—C20—N03—Al2
C2—C1—N03—C20
179.3 (2)
−177.2 (2)
1.1 (3)
0.0 (4)
178.1 (2)
−3.6 (4)
176.5 (3)
4.5 (4)
−175.3 (2)
−175.6 (2)
4.6 (3)
4.1 (4)
−179.3 (3)
1.6 (4)
C4—C5—C6—N04
C2—C1—C6—C5
N03—C1—C6—C5
C2—C1—C6—N04
N03—C1—C6—N04
N01—C19A—C18A—C13A
N01—C19A—C18A—C17A
N04—C7—C8—C13
N04—C7—C8—C9
−177.5 (3)
0.4 (4)
−176.2 (3)
0.3 (4)
C13A—C18A—C17A—C16A
C19A—C18A—C17A—C16A
C13—C8—C9—C10
−178.6 (2)
4.2 (4)
0.2 (4)
C7—C8—C9—C10
C18A—C17A—C16A—C15A
C8—C9—C10—C11
179.4 (3)
1.8 (5)
C6—C1—N03—C20
C2—C1—N03—Al2
C6—C1—N03—Al2
C8—C7—N04—C6
C8—C7—N04—Al2
C5—C6—N04—C7
C1—C6—N04—C7
C5—C6—N04—Al2
180.0 (2)
177.7 (2)
−2.6 (3)
−179.3 (2)
−6.4 (4)
−11.0 (4)
169.1 (2)
175.4 (2)
−4.5 (3)
13.5 (4)
−167.85 (18)
−4.5 (3)
176.65 (17)
−2.1 (4)
178.7 (2)
7.1 (4)
−174.5 (2)
2.8 (4)
−0.4 (4)
−0.1 (4)
−1.2 (5)
179.2 (3)
−1.8 (4)
−179.2 (3)
0.9 (4)
177.9 (2)
−5.7 (4)
−3.3 (4)
173.2 (2)
2.1 (3)
−177.1 (2)
−176.9 (2)
3.9 (4)
179.7 (2)
0.7 (4)
C9—C10—C11—C12
C17A—C16A—C15A—C14A
C16A—C15A—C14A—O3
C16A—C15A—C14A—C13A
C10—C11—C12—O10
C10—C11—C12—C13
C17A—C18A—C13A—O2
C19A—C18A—C13A—O2
C17A—C18A—C13A—C14A
C19A—C18A—C13A—C14A
O3—C14A—C13A—O2
C15A—C14A—C13A—O2
O3—C14A—C13A—C18A
C15A—C14A—C13A—C18A
C9—C8—C13—O7
C1—C6—N04—Al2
C7A—C12A—O1—Al1
C11A—C12A—O1—Al1
C18A—C13A—O2—Al1
C14A—C13A—O2—Al1
C15A—C14A—O3—C022
C13A—C14A—O3—C022
C10A—C11A—O4—C021
C12A—C11A—O4—C021
C8—C13—O7—Al2
C7—C8—C13—O7
C9—C8—C13—C12
C12—C13—O7—Al2
C19—C14—O8—Al2
−177.91 (18)
−3.6 (4)
0.5 (4)
Acta Cryst. (2019). C75
sup-11

supporting information
C7—C8—C13—C12
−178.6 (2)
179.6 (2)
−0.3 (3)
−1.1 (4)
179.0 (2)
−2.5 (3)
176.2 (2)
176.0 (2)
−5.3 (4)
0.3 (3)
−179.7 (2)
179.3 (2)
−0.6 (4)
−179.2 (3)
2.4 (5)
179.3 (2)
0.4 (4)
2.1 (5)
−0.1 (4)
−3.5 (5)
0.1 (4)
−177.5 (3)
3.8 (4)
C15—C14—O8—Al2
176.38 (17)
C11—C12—C13—O7
O10—C12—C13—O7
C11—C12—C13—C8
O10—C12—C13—C8
O1—C12A—C11A—O4
C7A—C12A—C11A—O4
O1—C12A—C11A—C10A
C7A—C12A—C11A—C10A
O8—C14—C15—O9
C19—C14—C15—O9
O8—C14—C15—C16
C19—C14—C15—C16
O4—C11A—C10A—C9A
C12A—C11A—C10A—C9A
O9—C15—C16—C17
C14—C15—C16—C17
C11A—C10A—C9A—C8A
C15—C16—C17—C18
C10A—C9A—C8A—C7A
C16—C17—C18—C19
O1—C12A—C7A—C8A
C11A—C12A—C7A—C8A
C16—C15—O9—C22
C14—C15—O9—C22
C11—C12—O10—C21
C13—C12—O10—C21
C13A—O2—Al1—O1
C13A—O2—Al1—O5
C13A—O2—Al1—O6
C13A—O2—Al1—N01
C12A—O1—Al1—O2
C12A—O1—Al1—O5
C12A—O1—Al1—O6
C12A—O1—Al1—N02
C14—O8—Al2—O7
C14—O8—Al2—O11
C14—O8—Al2—O12
C14—O8—Al2—N03
C13—O7—Al2—O8
C13—O7—Al2—O11
C13—O7—Al2—O12
C13—O7—Al2—N04
C4U—C4R—C4T—O4T
C4T—C4R—C4U—O4U
13.3 (4)
−167.7 (2)
0.1 (4)
180.0 (2)
−172.4 (2)
−78.5 (2)
96.9 (2)
10.8 (2)
159.5 (2)
67.4 (2)
−109.9 (2)
−21.2 (2)
−172.2 (2)
−81.1 (2)
95.4 (2)
6.3 (2)
178.1 (2)
84.8 (2)
−91.7 (2)
−5.6 (2)
−171 (6)
7 (4)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O5—H52···O16
O11—H11B···O1A
0.87 (2)
0.85 (3)
1.83 (3)
1.73 (3)
2.684 (3)
2.573 (4)
169 (3)
178 (7)
Diaqua(6,6′-{(1E,1′E)-[1,2-phenylenebis(azanylylidene)]bis(methanylylidene)}bis(2-methoxyphenolato)-
4
1
1′
κ O ,N,N′,O )gallium(III) nitrate ethanol monosolvate (16rjt1_0m)
Crystal data
[
18 2 4 2 2 3
Ga(C22H N O )(H O) ]NO ·C
2 6
H O
Z = 4
M
r
= 588.21
F(000) = 1216
D = 1.576 Mg m
x
−3
Triclinic, P1
a = 12.399 (5) Å
b = 13.580 (5) Å
c = 16.419 (5) Å
α = 86.818 (5)°
β = 78.871 (5)°
γ = 66.124 (5)°
V = 2479.7 (16) Å
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 11972 reflections
θ = 1.0–1.0°
µ = 1.17 mm
T = 100 K
−1
Cuboid, yellow
0.57 × 0.24 × 0.23 mm
3
Data collection
Bruker APEXII CCD
diffractometer
φ and ω scans
47407 measured reflections
11972 independent reflections
10426 reflections with I > 2σ(I)
Acta Cryst. (2019). C75
sup-12

supporting information
R
int = 0.027
k = −16→17
l = −21→20
θ
max = 28.0°, θmin = 1.6°
h = −16→16
Refinement
2
Refinement on F
Hydrogen site location: mixed
Least-squares matrix: full
H atoms treated by a mixture of independent
and constrained refinement
2
2
R[F > 2σ(F )] = 0.044
2
2
2
2
wR(F ) = 0.114
w = 1/[σ (F
o
) + (0.0422P) + 5.8146P]
2
2
S = 1.06
where P = (F
o
+ 2F )/3
c
1
1886 reflections
(Δ/σ)max = 0.002
Δρmax = 1.84 e Å
Δρmin = −2.07 e Å
−
3
682 parameters
0 restraints
−
3
2
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.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
Occ. (<1)
Ga01
Ga02
O6
N2A
C7A
H7A
O4
C15A
H15A
C12A
O3
0.45155 (2)
0.08156 (2)
0.29643 (18)
0.0987 (2)
−0.0959 (3)
−0.1286
0.39050 (16)
0.2812 (2)
0.2812
0.2796 (2)
0.40813 (16)
0.31225 (16)
0.4966 (2)
0.5227
0.17569 (2)
0.32174 (2)
−0.05042 (15)
0.28745 (17)
0.2234 (2)
0.1951
0.08262 (14)
0.4138 (2)
0.3858
0.4998 (2)
0.14689 (14)
0.09519 (14)
0.3212 (2)
0.3755
0.95269 (2)
0.54724 (2)
0.90092 (12)
0.66651 (13)
0.29245 (18)
0.2584
0.91687 (10)
0.72964 (17)
0.7826
0.57193 (16)
1.06566 (10)
1.20518 (11)
1.05411 (17)
1.0593
0.01661 (6)
0.01661 (6)
0.0244 (4)
0.0206 (4)
0.0292 (5)
0.035*
0.0185 (3)
0.0247 (5)
0.030*
0.0224 (5)
0.0187 (3)
0.0213 (4)
0.0225 (5)
0.027*
O5
C4
H4
C21
H21A
H21B
H21C
C18
O25
O6A
O1
C17
H17
O16
C22
H22A
0.2664 (3)
0.2509
0.1932
0.0603 (2)
−0.0015
0.1174
1.28266 (17)
1.2734
1.3084
0.0263 (6)
0.039*
0.039*
0.3243
0.0417
1.3184
0.039*
0.5848 (2)
0.2711 (2)
0.04001 (17)
0.61681 (16)
0.4886 (2)
0.5152
0.32134 (19)
0.2458 (3)
0.2277
0.26915 (19)
0.53867 (18)
0.42112 (15)
0.04865 (14)
0.1814 (2)
0.2061
0.49178 (16)
−0.1268 (2)
−0.1531
0.83385 (16)
0.49337 (14)
0.28984 (11)
0.94634 (11)
0.77038 (15)
0.7198
0.92363 (15)
0.8949 (2)
0.9490
0.0199 (5)
0.0349 (3)
0.0231 (4)
0.0188 (3)
0.0210 (5)
0.025*
0.0351 (5)
0.0314 (6)
0.047*
Acta Cryst. (2019). C75
sup-13

supporting information
H22B
H22C
O2A
C2A
H2AC
O5A
C15
H15
O4A
O10
C22A
H22D
H22E
H22F
C11A
O2
0.3023
0.1735
−0.1858
−0.0927
0.8588
0.8728
0.047*
0.047*
−0.08101 (17)
−0.0556 (3)
−0.0852
0.16622 (17)
0.4045 (3)
0.4309
0.04988 (17)
0.3168 (2)
0.3271 (3)
0.3154
0.44875 (14)
0.1040 (2)
0.0755
0.41135 (14)
0.0944 (2)
0.1262
0.35558 (14)
0.84316 (16)
0.6109 (3)
0.6327
0.59385 (11)
0.67441 (18)
0.6381
0.53847 (11)
0.69046 (17)
0.6437
0.43888 (11)
0.42534 (14)
0.4661 (2)
0.4107
0.0209 (4)
0.0274 (6)
0.033*
0.0216 (4)
0.0293 (6)
0.035*
0.0208 (4)
0.0324 (4)
0.0349 (3)
0.052*
0.4115
0.2921
0.5756
0.6732
0.4666
0.5026
0.052*
0.052*
0.2196 (2)
0.29328 (17)
0.3445 (2)
−0.0052 (2)
0.1678 (2)
0.4232 (2)
−0.0401 (2)
0.2210 (2)
0.1295 (2)
−0.0894 (2)
−0.1178
0.52160 (19)
0.3483 (3)
0.3352
0.3817 (2)
0.00006 (19)
0.2764 (2)
0.0575 (3)
0.0885
0.42986 (19)
0.30294 (15)
0.9705 (2)
0.1777 (2)
0.99308 (18)
0.1152 (2)
0.2303 (2)
0.3868 (2)
0.54519 (18)
0.1882 (2)
0.1358
0.27638 (16)
0.0283 (3)
0.0168
0.06723 (19)
0.21935 (16)
0.93433 (18)
0.4449 (2)
0.4997
0.59469 (16)
0.95132 (13)
0.48120 (15)
0.64648 (16)
0.46706 (17)
0.76905 (15)
0.42517 (15)
0.67492 (16)
0.93591 (18)
0.37179 (17)
0.3910
0.98134 (13)
0.68225 (18)
0.6304
0.84022 (15)
0.56512 (13)
0.45785 (13)
0.20350 (16)
0.1953
0.0198 (5)
0.0265 (4)
0.0409 (5)
0.0217 (5)
0.0440 (6)
0.0210 (5)
0.0196 (5)
0.0214 (5)
0.0443 (6)
0.0245 (5)
0.029*
0.0180 (4)
0.0339 (7)
0.041*
0.0181 (5)
0.0197 (4)
0.0235 (5)
0.0287 (6)
0.043*
O11
C3A
O12
C16
C5A
C16A
O7
C6A
H6A
N1
C14
H14
C11
N1A
N3
C21A
H21D
H21E
H21F
N4
−0.0178
0.1135
0.4699
0.3810
0.1849
0.1723
0.043*
0.043*
0.2209 (2)
0.2115 (2)
−0.0400 (2)
−0.0711
0.51356 (18)
0.0034 (2)
0.6505 (3)
0.6480
0.0431 (2)
0.3280 (2)
0.3104 (3)
0.2732
0.56655 (18)
0.65943 (17)
0.1895 (2)
0.1376
0.20938 (16)
0.30990 (19)
0.2923 (2)
0.2693
0.2177 (2)
−0.0041 (2)
−0.0219 (2)
−0.0676
0.92205 (16)
0.90632 (17)
0.50775 (16)
0.5212
0.83601 (13)
0.39546 (15)
0.76180 (18)
0.7101
0.70141 (16)
0.82891 (16)
0.75171 (18)
0.7457
0.0278 (5)
0.0430 (6)
0.0217 (5)
0.026*
0.0177 (4)
0.0181 (5)
0.0270 (6)
0.032*
0.0219 (5)
0.0210 (5)
0.0292 (6)
0.035*
O9
C4A
H4A
N2
C10A
C19
H19
C18A
C12
C13
H13
C8
0.3146 (3)
0.2457 (2)
1.27768 (17)
0.0310 (6)
Acta Cryst. (2019). C75
sup-14

supporting information
H8
0.2764
0.2298
1.3280
0.037*
C10
C5
C9
0.3942 (2)
0.4317 (2)
0.3389 (2)
−0.0531 (2)
−0.0579
0.0328 (3)
0.0609
−0.0613 (3)
−0.0936
−0.0041 (2)
0.1613 (2)
0.1683
0.3384 (2)
0.3781
0.3390 (3)
0.3786
−0.0192 (3)
−0.0259
0.5900 (2)
0.6618 (3)
0.6666
0.20751 (19)
0.2934 (2)
0.1830 (2)
0.3023 (2)
0.3263
0.1886 (2)
0.2175
0.0734 (2)
0.0234
0.3440 (2)
0.3171 (2)
0.2914
0.5236 (2)
0.5687
0.4803 (2)
0.4969
0.1167 (2)
0.0973
1.12989 (15)
1.12719 (16)
1.20792 (16)
0.26230 (16)
0.2084
0.78431 (17)
0.8215
0.75655 (19)
0.7750
0.31235 (15)
0.70624 (16)
0.7595
0.62578 (18)
0.6093
0.70562 (18)
0.7419
0.81145 (18)
0.8668
0.0181 (5)
0.0230 (5)
0.0206 (5)
0.0246 (5)
0.030*
0.0280 (6)
0.034*
0.0317 (6)
0.038*
0.0196 (5)
0.0222 (5)
0.027*
0.0264 (6)
0.032*
0.0280 (6)
0.034*
0.0315 (6)
0.038*
C8A
H8A
C19A
H19A
C1A
H1AA
C9A
C17A
H17A
C13A
H13A
C14A
H14A
C20A
H20A
C3
0.30404 (19)
0.3594 (2)
0.3810
0.91141 (16)
0.91662 (19)
0.9681
0.0203 (5)
0.0285 (6)
0.034*
C2
H2
C20
H20
0.7193 (3)
0.7615
0.3496 (2)
0.3666
0.7677 (2)
0.7197
0.0325 (6)
0.039*
C1
H1
0.7257 (3)
0.7736
0.3818 (3)
0.4188
0.8447 (2)
0.8480
0.0341 (7)
0.041*
C6
H6
0.4077 (3)
0.4333
0.3553 (2)
0.4111
1.2003 (2)
1.1988
0.0354 (7)
0.042*
C7
H7
0.3474 (3)
0.3278
0.3337 (3)
0.3776
1.2728 (2)
1.3195
0.0417 (8)
0.050*
C6B
H6BA
H6BB
H6BC
C5B
H5BA
H5BB
C2B
H2BA
H2BB
H2BC
O13
H13B
C4B
H4BA
H4BB
C3B
H3BA
0.5687 (4)
0.5848
0.5405
0.6410
0.4736 (3)
0.5019
0.4014
0.0900 (6)
0.1568
0.1002
0.0170
0.0912 (4)
0.1064
0.0849 (8)
0.0103
0.1508
0.0713 (5)
0.1363
0.2399 (3)
0.3000
0.2110
0.1853
0.2769 (3)
0.3074
0.3332
0.1407 (6)
0.1376
0.0689
0.1746
0.2902 (3)
0.2909
0.1940 (6)
0.2076
0.1529
0.1925 (5)
0.1454
0.3791 (3)
0.3556
0.3396
0.3925
0.4573 (2)
0.4964
0.4436
0.0735 (4)
0.0966
0.0607
0.1130
0.0223 (4)
0.0686
0.0085 (5)
−0.0097
−0.0351
−0.0128 (4)
−0.0542
0.0535 (9)
0.080*
0.080*
0.080*
0.0349 (3)
0.042*
0.042*
0.0292 (5)
0.044*
0.044*
0.044*
0.0324 (4)
0.049*
0.0349 (3)
0.042*
0.042*
0.0217 (5)
0.026*
0.492 (6)
0.492 (6)
0.492 (6)
0.492 (6)
0.492 (6)
0.492 (6)
0.492 (6)
0.492 (6)
0.492 (6)
0.508 (6)
0.508 (6)
Acta Cryst. (2019). C75
sup-15

supporting information
H3BB
C1B
H1BA
H1BB
H1BC
O15
H15B
O14
H14B
H1A
H1B
H2A
H2B
H2AA
H2AB
O0AA
H0AA
H0AB
−0.0019
0.0688 (9)
0.0606
0.0020
0.1421
0.0815 (5)
0.0410
0.4471 (2)
0.5091
0.614 (5)
0.626 (5)
0.223 (3)
0.289 (5)
−0.070 (5)
−0.122 (5)
0.23809 (18)
0.2378
0.2048
0.1200 (7)
0.0566
0.1597
0.0994
0.2894 (4)
0.3283
0.1992 (3)
0.1478
−0.004 (3)
0.033 (4)
0.304 (4)
0.367 (2)
0.498 (3)
0.468 (4)
0.19361 (15)
0.1355
−0.0326
0.0651 (6)
0.0495
0.1077
0.0857
−0.0210 (4)
0.0197
0.4926 (2)
0.4985
0.922 (3)
0.9960 (16)
0.971 (4)
0.952 (4)
0.613 (3)
0.556 (3)
0.50397 (13)
0.5278
0.026*
0.0535 (9)
0.080*
0.080*
0.080*
0.0409 (5)
0.061*
0.0653 (9)
0.098*
0.098*
0.098*
0.098*
0.098*
0.098*
0.098*
0.0288 (4)
0.043*
0.043*
0.508 (6)
0.508 (6)
0.508 (6)
0.508 (6)
0.508 (6)
0.508 (6)
0.508 (6)
0.2974
0.2011
0.5188
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
Ga01
Ga02
O6
N2A
C7A
O4
C15A
C12A
O3
0.02039 (10)
0.02039 (10)
0.0307 (10)
0.0242 (11)
0.0301 (13)
0.0250 (9)
0.0257 (13)
0.0210 (12)
0.0258 (9)
0.0249 (9)
0.0256 (13)
0.0255 (13)
0.0194 (11)
0.0359 (8)
0.0306 (10)
0.0202 (8)
0.0214 (12)
0.0285 (11)
0.0360 (16)
0.0253 (9)
0.0365 (15)
0.0266 (9)
0.0347 (15)
0.0291 (10)
0.0352 (10)
0.0359 (8)
0.01428 (10)
0.01428 (10)
0.0245 (9)
0.0177 (10)
0.0338 (14)
0.0179 (8)
0.0247 (13)
0.0186 (12)
0.0160 (8)
0.0218 (9)
0.0138 (11)
0.0271 (13)
0.0144 (11)
0.0359 (8)
0.0239 (9)
0.0159 (8)
0.0198 (12)
0.0205 (10)
0.0267 (14)
0.0169 (8)
0.0216 (13)
0.0206 (9)
0.0346 (15)
0.0182 (8)
0.0208 (9)
0.0359 (8)
0.01347 (10)
0.01347 (10)
0.0236 (9)
0.0166 (10)
0.0239 (12)
0.0142 (8)
0.0198 (12)
0.0214 (12)
0.0140 (8)
0.0151 (8)
0.0274 (13)
0.0198 (12)
0.0225 (12)
0.0299 (8)
0.0153 (8)
0.0170 (8)
0.0155 (11)
0.0529 (14)
0.0392 (17)
0.0174 (9)
0.0245 (13)
0.0166 (8)
0.0170 (12)
0.0145 (8)
0.0377 (11)
0.0299 (8)
−0.00593 (7)
−0.00250 (7)
−0.00250 (7)
−0.0055 (8)
−0.0040 (8)
−0.0061 (10)
−0.0046 (7)
−0.0060 (10)
−0.0002 (9)
−0.0004 (7)
0.0012 (7)
−0.0044 (10)
0.0033 (10)
−0.0012 (9)
−0.0031 (6)
−0.0042 (7)
−0.0022 (7)
−0.0013 (9)
−0.0160 (10)
−0.0135 (13)
−0.0034 (7)
−0.0072 (11)
−0.0058 (7)
−0.0079 (11)
−0.0048 (7)
−0.0035 (8)
−0.0031 (6)
0.00317 (7)
0.00317 (7)
0.0036 (7)
0.0040 (8)
−0.0046 (10)
0.0041 (6)
0.0026 (10)
0.0007 (9)
0.0015 (6)
0.0035 (7)
0.0012 (9)
0.0065 (10)
0.0068 (9)
0.0044 (6)
0.0029 (7)
0.0030 (6)
0.0065 (9)
0.0012 (9)
0.0051 (12)
0.0006 (7)
0.0051 (10)
0.0038 (7)
0.0058 (11)
0.0012 (6)
−0.0055 (8)
0.0044 (6)
−0.00593 (7)
−0.0170 (8)
−0.0055 (8)
−0.0119 (11)
−0.0104 (7)
−0.0056 (11)
−0.0032 (10)
−0.0096 (7)
−0.0098 (7)
−0.0075 (10)
−0.0080 (11)
−0.0052 (9)
−0.0133 (7)
−0.0117 (8)
−0.0049 (7)
−0.0036 (10)
−0.0028 (8)
−0.0183 (12)
−0.0055 (7)
−0.0122 (11)
−0.0081 (7)
−0.0117 (12)
−0.0087 (7)
−0.0085 (8)
−0.0133 (7)
O5
C4
C21
C18
O25
O6A
O1
C17
O16
C22
O2A
C2A
O5A
C15
O4A
O10
C22A
Acta Cryst. (2019). C75
sup-16

supporting information
C11A
O2
0.0184 (11)
0.0202 (9)
0.0165 (11)
0.0159 (8)
0.0439 (12)
0.0161 (11)
0.0271 (11)
0.0196 (12)
0.0174 (11)
0.0187 (11)
0.0285 (11)
0.0249 (13)
0.0142 (9)
0.0439 (17)
0.0162 (11)
0.0153 (9)
0.0196 (10)
0.0369 (15)
0.0172 (10)
0.0171 (10)
0.0203 (10)
0.0151 (9)
0.0154 (11)
0.0251 (13)
0.0177 (11)
0.0202 (12)
0.0345 (15)
0.0331 (15)
0.0142 (10)
0.0174 (11)
0.0192 (11)
0.0281 (13)
0.0293 (14)
0.0262 (14)
0.0187 (11)
0.0208 (12)
0.0244 (13)
0.0306 (14)
0.0305 (15)
0.0150 (11)
0.0283 (14)
0.0313 (15)
0.0346 (16)
0.0254 (14)
0.0389 (18)
0.047 (2)
0.0191 (12)
0.0388 (11)
0.0392 (12)
0.0186 (12)
0.0552 (15)
0.0163 (11)
0.0184 (12)
0.0203 (12)
0.0762 (18)
0.0239 (13)
0.0199 (10)
0.0203 (13)
0.0166 (11)
0.0168 (10)
0.0160 (10)
0.0167 (12)
0.0353 (13)
0.0662 (17)
0.0191 (11)
0.0172 (10)
0.0160 (11)
0.0239 (13)
0.0196 (12)
0.0207 (12)
0.0272 (14)
0.0179 (13)
0.0157 (11)
0.0207 (12)
0.0177 (12)
0.0158 (12)
0.0195 (13)
0.0288 (15)
0.0160 (11)
0.0161 (11)
0.0291 (14)
0.0272 (14)
0.0202 (13)
0.0234 (12)
0.0313 (15)
0.0333 (16)
0.0412 (17)
0.0317 (16)
0.0242 (15)
0.064 (2)
−0.0025 (9)
−0.0048 (7)
−0.0288 (11)
−0.0043 (10)
0.0013 (9)
−0.0010 (9)
−0.0026 (8)
−0.0124 (10)
−0.0018 (9)
−0.0029 (11)
−0.0048 (9)
−0.0002 (9)
−0.0040 (9)
−0.0111 (11)
−0.0012 (10)
−0.0031 (8)
−0.0131 (12)
−0.0047 (9)
−0.0012 (8)
−0.0036 (9)
−0.0041 (11)
−0.0136 (10)
−0.0217 (12)
−0.0017 (9)
−0.0011 (8)
−0.0006 (9)
0.0025 (11)
−0.0032 (10)
−0.0050 (9)
−0.0098 (11)
0.0054 (11)
−0.0008 (9)
−0.0009 (10)
−0.0008 (9)
−0.0033 (10)
−0.0072 (11)
−0.0071 (12)
−0.0008 (9)
−0.0037 (9)
−0.0018 (10)
−0.0071 (11)
−0.0075 (12)
−0.0023 (9)
−0.0048 (11)
0.0042 (12)
−0.0016 (13)
0.0024 (13)
0.0069 (14)
−0.0032 (17)
−0.0031 (6)
−0.0061 (10)
−0.0035 (8)
−0.0031 (6)
−0.0001 (9)
0.0068 (8)
−0.0003 (9)
0.0038 (9)
−0.0004 (10)
0.0037 (9)
−0.0011 (9)
0.0025 (9)
−0.0031 (11)
−0.0018 (10)
0.0042 (8)
0.0019 (12)
0.0020 (9)
O11
C3A
O12
C16
C5A
C16A
O7
C6A
N1
C14
C11
N1A
N3
C21A
N4
O9
C4A
N2
C10A
C19
C18A
C12
C13
C8
C10
C5
C9
C8A
C19A
C1A
C9A
C17A
C13A
C14A
C20A
C3
C2
C20
C1
C6
C7
0.0513 (13)
0.0250 (13)
0.0339 (12)
0.0222 (12)
0.0174 (11)
0.0211 (12)
0.0298 (12)
0.0239 (13)
0.0192 (10)
0.0410 (17)
0.0176 (11)
0.0219 (10)
0.0350 (13)
0.0353 (15)
0.0312 (12)
0.0496 (14)
0.0210 (11)
0.0176 (10)
0.0168 (11)
0.0273 (14)
0.0245 (12)
0.0202 (12)
0.0301 (14)
0.0369 (16)
0.0187 (11)
0.0277 (13)
0.0199 (12)
0.0271 (13)
0.0354 (15)
0.0424 (17)
0.0196 (11)
0.0252 (13)
0.0230 (13)
0.0257 (14)
0.0431 (17)
0.0202 (12)
0.0300 (14)
0.0313 (15)
0.0322 (15)
0.0493 (19)
0.060 (2)
−0.0032 (10)
−0.0024 (9)
−0.0039 (10)
−0.0123 (9)
−0.0100 (11)
−0.0068 (8)
−0.0174 (14)
−0.0025 (9)
−0.0036 (8)
−0.0122 (9)
−0.0184 (13)
−0.0069 (9)
−0.0134 (10)
−0.0044 (9)
−0.0049 (8)
−0.0010 (9)
−0.0098 (11)
−0.0054 (10)
−0.0057 (10)
−0.0150 (12)
−0.0128 (13)
−0.0019 (9)
−0.0071 (10)
−0.0040 (9)
−0.0085 (11)
−0.0131 (12)
−0.0172 (13)
−0.0042 (9)
−0.0054 (10)
−0.0082 (11)
−0.0099 (11)
−0.0151 (13)
−0.0062 (9)
−0.0169 (12)
−0.0165 (12)
−0.0225 (13)
−0.0184 (14)
−0.0228 (16)
−0.0221 (16)
−0.0133 (7)
−0.0119 (11)
−0.0085 (8)
−0.0133 (7)
0.0019 (8)
0.0042 (8)
0.0060 (11)
0.0012 (9)
0.0076 (10)
−0.0001 (9)
0.0054 (7)
−0.0023 (9)
0.0062 (10)
0.0049 (9)
0.0023 (9)
−0.0012 (11)
−0.0049 (11)
0.0007 (8)
−0.0017 (9)
0.0001 (9)
−0.0004 (10)
0.0062 (10)
0.0120 (11)
−0.0005 (9)
0.0046 (9)
0.0012 (11)
0.0003 (11)
0.0121 (11)
0.0056 (9)
0.0043 (11)
0.0093 (12)
0.0076 (13)
−0.0095 (12)
−0.0146 (13)
−0.0032 (17)
0.0044 (6)
−0.0046 (10)
−0.0055 (8)
0.0044 (6)
C6B
C5B
C2B
O13
C4B
0.050 (2)
0.0359 (8)
0.0301 (13)
0.0352 (10)
0.0359 (8)
0.0359 (8)
0.0338 (14)
0.0208 (9)
0.0359 (8)
0.0299 (8)
0.0239 (12)
0.0377 (11)
0.0299 (8)
Acta Cryst. (2019). C75
sup-17

supporting information
C3B
C1B
O15
O14
O0AA
0.0210 (11)
0.050 (2)
0.0513 (13)
0.0270 (13)
0.0275 (10)
0.0203 (10)
0.047 (2)
0.0439 (12)
0.092 (2)
0.0191 (11)
0.064 (2)
0.0392 (12)
0.0654 (19)
0.0322 (11)
−0.0044 (9)
−0.0221 (16)
−0.0288 (11)
−0.0124 (14)
−0.0039 (8)
−0.0017 (9)
−0.0032 (17)
−0.0124 (10)
−0.0095 (13)
−0.0013 (8)
−0.0001 (9)
−0.0032 (17)
−0.0003 (9)
0.0062 (17)
0.0030 (8)
0.0191 (9)
Geometric parameters (Å, º)
Ga01—O4
Ga01—O3
Ga01—N1
Ga01—N2
Ga01—O2
Ga01—O1
Ga02—O5A
Ga02—O4A
Ga02—N1A
Ga02—N2A
Ga02—O0AA
Ga02—O2A
O6—C12
1.8829 (18)
C5A—C6A
1.419 (4)
1.8941 (18)
2.009 (2)
2.022 (2)
2.0262 (19)
2.0644 (19)
1.887 (2)
1.8878 (18)
2.005 (2)
2.019 (2)
2.042 (2)
2.0881 (19)
1.373 (3)
1.428 (3)
1.291 (4)
1.420 (3)
1.368 (4)
1.405 (4)
0.9300
1.319 (3)
1.363 (4)
1.419 (4)
0.9300
1.373 (3)
1.375 (4)
1.421 (4)
1.315 (3)
1.365 (3)
1.427 (3)
1.296 (3)
1.433 (4)
0.9300
C5A—C4A
C16A—C17A
O7—N4
C6A—H6A
N1—C3
1.436 (3)
1.441 (4)
1.257 (3)
0.9300
1.419 (3)
1.397 (4)
0.9300
1.417 (4)
1.298 (3)
0.9600
C14—C13
C14—H14
C11—C12
N1A—C4A
C21A—H21D
C21A—H21E
C21A—H21F
N4—O9
C4A—H4A
C10A—C9A
C19—C20
C19—H19
C18A—C19A
C12—C13
C13—H13
C8—C9
0.9600
0.9600
O6—C22
1.236 (3)
0.9300
1.425 (3)
1.386 (4)
0.9300
1.393 (4)
1.376 (4)
0.9300
1.377 (4)
1.403 (5)
0.9300
1.415 (4)
1.422 (3)
1.417 (4)
1.374 (4)
0.9300
1.386 (4)
0.9300
1.385 (4)
0.9300
N2A—C17A
N2A—C18A
C7A—C6A
C7A—C8A
C7A—H7A
O4—C11
C15A—C14A
C15A—C16A
C15A—H15A
C12A—O25
C12A—C13A
C12A—C11A
O3—C10
C8—C7
C8—H8
C10—C5
C10—C9
C5—C6
O5—C9
O5—C21
C4—N1
C4—C5
C8A—C9A
C8A—H8A
C19A—C20A
C19A—H19A
C1A—C20A
C1A—H1AA
C17A—H17A
C13A—C14A
C13A—H13A
C14A—H14A
C20A—H20A
C3—C2
C4—H4
C21—H21A
C21—H21B
C21—H21C
C18—C19
C18—C3
C18—N2
O25—C22A
O6A—C9A
0.9600
0.9600
0.9600
1.398 (3)
1.405 (4)
1.417 (3)
1.424 (4)
1.369 (3)
0.9300
1.407 (4)
0.9300
0.9300
0.9300
1.393 (4)
1.382 (4)
C2—C1
Acta Cryst. (2019). C75
sup-18

supporting information
O6A—C21A
O1—H1A
O1—H1B
C17—N2
C17—C16
1.431 (3)
0.854 (19)
0.850 (19)
1.293 (3)
1.437 (4)
0.9300
1.253 (3)
0.9600
0.9600
C2—H2
C20—C1
C20—H20
C1—H1
C6—C7
C6—H6
C7—H7
0.9300
1.388 (5)
0.9300
0.9300
1.364 (5)
0.9300
0.9300
1.517 (5)
0.9600
0.9600
0.9600
1.302 (5)
0.9700
0.9700
1.252 (10)
0.9600
0.9600
0.9600
1.373 (8)
0.8200
0.9700
0.9700
1.369 (7)
1.575 (11)
0.9700
0.9700
0.9600
0.9600
0.9600
0.8200
0.8200
0.8624
0.8623
C17—H17
O16—N4
C22—H22A
C22—H22B
C22—H22C
O2A—H2AA
O2A—H2AB
C2A—C1A
C2A—C3A
C2A—H2AC
O5A—C11A
C15—C14
C6B—C5B
C6B—H6BA
C6B—H6BB
C6B—H6BC
C5B—O14
C5B—H5BA
C5B—H5BB
C2B—C4B
C2B—H2BA
C2B—H2BB
C2B—H2BC
O13—C4B
O13—H13B
C4B—H4BA
C4B—H4BB
C3B—O15
C3B—C1B
C3B—H3BA
C3B—H3BB
C1B—H1BA
C1B—H1BB
C1B—H1BC
O15—H15B
O14—H14B
O0AA—H0AA
O0AA—H0AB
0.9600
0.832 (19)
0.838 (19)
1.386 (4)
1.395 (4)
0.9300
1.323 (3)
1.365 (4)
1.417 (4)
0.9300
1.313 (3)
1.240 (3)
0.9600
0.9600
0.9600
1.412 (3)
0.855 (19)
0.854 (19)
1.259 (3)
1.412 (4)
1.422 (3)
1.240 (3)
1.417 (3)
1.418 (4)
C15—C16
C15—H15
O4A—C10A
O10—N3
C22A—H22D
C22A—H22E
C22A—H22F
C11A—C16A
O2—H2A
O2—H2B
O11—N3
C3A—C18A
C3A—N1A
O12—N3
C16—C11
C5A—C10A
O4—Ga01—O3
O4—Ga01—N1
O3—Ga01—N1
O4—Ga01—N2
O3—Ga01—N2
N1—Ga01—N2
O4—Ga01—O2
O3—Ga01—O2
N1—Ga01—O2
N2—Ga01—O2
O4—Ga01—O1
O3—Ga01—O1
N1—Ga01—O1
N2—Ga01—O1
91.95 (8)
175.43 (8)
92.60 (8)
93.84 (8)
173.36 (8)
81.59 (9)
90.60 (9)
93.72 (8)
89.56 (9)
89.48 (8)
89.74 (8)
90.02 (7)
89.80 (8)
86.76 (8)
O6A—C21A—H21E
109.5
109.5
109.5
109.5
H21D—C21A—H21E
O6A—C21A—H21F
H21D—C21A—H21F
H21E—C21A—H21F
O9—N4—O16
109.5
120.9 (3)
120.4 (2)
118.7 (2)
125.2 (2)
117.4
O9—N4—O7
O16—N4—O7
N1A—C4A—C5A
N1A—C4A—H4A
C5A—C4A—H4A
C17—N2—C18
C17—N2—Ga01
C18—N2—Ga01
117.4
123.5 (2)
123.54 (18)
112.92 (16)
Acta Cryst. (2019). C75
sup-19

supporting information
O2—Ga01—O1
176.23 (8)
91.11 (8)
174.56 (8)
93.96 (8)
92.88 (8)
174.46 (9)
82.20 (9)
89.90 (9)
91.77 (8)
87.98 (9)
92.08 (9)
92.01 (8)
89.17 (8)
90.03 (9)
86.84 (8)
177.85 (8)
117.4 (2)
122.1 (2)
124.87 (18)
112.76 (17)
120.2 (3)
119.9
O4A—C10A—C5A
O4A—C10A—C9A
C5A—C10A—C9A
C20—C19—C18
C20—C19—H19
C18—C19—H19
C19A—C18A—C3A
C19A—C18A—N2A
C3A—C18A—N2A
O6—C12—C13
O6—C12—C11
C13—C12—C11
C12—C13—C14
C12—C13—H13
C14—C13—H13
C9—C8—C7
C9—C8—H8
C7—C8—H8
O3—C10—C5
O3—C10—C9
C5—C10—C9
C10—C5—C6
C10—C5—C4
C6—C5—C4
125.0 (2)
117.0 (2)
118.0 (2)
119.7 (3)
120.1
O5A—Ga02—O4A
O5A—Ga02—N1A
O4A—Ga02—N1A
O5A—Ga02—N2A
O4A—Ga02—N2A
N1A—Ga02—N2A
O5A—Ga02—O0AA
O4A—Ga02—O0AA
N1A—Ga02—O0AA
N2A—Ga02—O0AA
O5A—Ga02—O2A
O4A—Ga02—O2A
N1A—Ga02—O2A
N2A—Ga02—O2A
O0AA—Ga02—O2A
C12—O6—C22
C17A—N2A—C18A
C17A—N2A—Ga02
C18A—N2A—Ga02
C6A—C7A—C8A
C6A—C7A—H7A
C8A—C7A—H7A
C11—O4—Ga01
C14A—C15A—C16A
C14A—C15A—H15A
C16A—C15A—H15A
O25—C12A—C13A
O25—C12A—C11A
C13A—C12A—C11A
C10—O3—Ga01
C9—O5—C21
N1—C4—C5
N1—C4—H4
C5—C4—H4
120.1
119.5 (2)
124.5 (3)
115.9 (2)
125.4 (2)
113.6 (2)
121.0 (2)
120.4 (3)
119.8
119.8
120.0 (3)
120.0
120.0
125.0 (2)
116.9 (2)
118.0 (2)
119.7 (2)
123.7 (2)
116.5 (2)
125.3 (2)
113.8 (2)
121.0 (2)
120.0 (2)
120.0
120.0
120.0 (3)
120.0
120.0
120.6 (3)
119.7
119.9
127.10 (16)
120.9 (3)
119.5
O5—C9—C8
O5—C9—C10
C8—C9—C10
119.5
125.7 (3)
113.2 (2)
121.2 (2)
126.03 (15)
116.6 (2)
124.8 (2)
117.6
117.6
109.5
109.5
109.5
109.5
109.5
109.5
119.4 (2)
125.0 (2)
115.6 (2)
116.8 (2)
117.0 (2)
107 (4)
C9A—C8A—C7A
C9A—C8A—H8A
C7A—C8A—H8A
C20A—C19A—C18A
C20A—C19A—H19A
C18A—C19A—H19A
C20A—C1A—C2A
C20A—C1A—H1AA
C2A—C1A—H1AA
O6A—C9A—C8A
O6A—C9A—C10A
C8A—C9A—C10A
N2A—C17A—C16A
N2A—C17A—H17A
C16A—C17A—H17A
C12A—C13A—C14A
C12A—C13A—H13A
C14A—C13A—H13A
C15A—C14A—C13A
C15A—C14A—H14A
C13A—C14A—H14A
O5—C21—H21A
O5—C21—H21B
H21A—C21—H21B
O5—C21—H21C
H21A—C21—H21C
H21B—C21—H21C
C19—C18—C3
C19—C18—N2
C3—C18—N2
C12A—O25—C22A
C9A—O6A—C21A
Ga01—O1—H1A
Ga01—O1—H1B
119.7
125.2 (2)
113.4 (2)
121.4 (2)
125.4 (2)
117.3
117.3
120.5 (3)
119.8
119.8
119.7 (3)
120.1
107 (4)
120.1
Acta Cryst. (2019). C75
sup-20

supporting information
H1A—O1—H1B
N2—C17—C16
N2—C17—H17
C16—C17—H17
110 (3)
125.5 (2)
117.3
117.3
109.5
109.5
109.5
109.5
109.5
C1A—C20A—C19A
C1A—C20A—H20A
C19A—C20A—H20A
C2—C3—C18
C2—C3—N1
C18—C3—N1
C1—C2—C3
C1—C2—H2
C3—C2—H2
C19—C20—C1
C19—C20—H20
C1—C20—H20
C2—C1—C20
C2—C1—H1
C20—C1—H1
C7—C6—C5
C7—C6—H6
C5—C6—H6
C6—C7—C8
120.4 (3)
119.8
119.8
120.3 (2)
123.9 (2)
115.8 (2)
119.5 (3)
120.3
120.3
120.4 (3)
119.8
119.8
120.7 (3)
119.6
119.6
120.4 (3)
119.8
119.8
120.6 (3)
119.7
O6—C22—H22A
O6—C22—H22B
H22A—C22—H22B
O6—C22—H22C
H22A—C22—H22C
H22B—C22—H22C
Ga02—O2A—H2AA
Ga02—O2A—H2AB
H2AA—O2A—H2AB
C1A—C2A—C3A
C1A—C2A—H2AC
C3A—C2A—H2AC
C11A—O5A—Ga02
C14—C15—C16
109.5
111 (4)
109 (4)
113 (3)
119.7 (3)
120.2
120.2
127.81 (16)
121.1 (3)
119.4
C14—C15—H15
C16—C15—H15
119.4
C6—C7—H7
C10A—O4A—Ga02
O25—C22A—H22D
O25—C22A—H22E
H22D—C22A—H22E
O25—C22A—H22F
H22D—C22A—H22F
H22E—C22A—H22F
O5A—C11A—C16A
O5A—C11A—C12A
C16A—C11A—C12A
Ga01—O2—H2A
Ga01—O2—H2B
127.15 (16)
109.5
109.5
109.5
109.5
C8—C7—H7
119.7
109.5
109.5
109.5
109.5
109.5
109.5
112.8 (3)
109.0
109.0
109.0
109.0
107.8
109.5
109.5
109.5
109.5
109.5
109.5
109.5
110.5 (6)
109.5
109.5
109.5
109.5
108.1
C5B—C6B—H6BA
C5B—C6B—H6BB
H6BA—C6B—H6BB
C5B—C6B—H6BC
H6BA—C6B—H6BC
H6BB—C6B—H6BC
O14—C5B—C6B
O14—C5B—H5BA
C6B—C5B—H5BA
O14—C5B—H5BB
C6B—C5B—H5BB
H5BA—C5B—H5BB
C4B—C2B—H2BA
C4B—C2B—H2BB
H2BA—C2B—H2BB
C4B—C2B—H2BC
H2BA—C2B—H2BC
H2BB—C2B—H2BC
C4B—O13—H13B
C2B—C4B—O13
C2B—C4B—H4BA
O13—C4B—H4BA
C2B—C4B—H4BB
O13—C4B—H4BB
H4BA—C4B—H4BB
O15—C3B—C1B
O15—C3B—H3BA
109.5
109.5
125.6 (2)
116.7 (2)
117.8 (2)
126 (3)
121 (3)
108 (3)
119.7 (2)
124.9 (3)
115.4 (2)
119.2 (3)
116.7 (2)
124.0 (2)
119.3 (2)
124.1 (2)
116.6 (2)
119.9 (2)
123.2 (2)
116.9 (2)
121.1 (3)
119.5
H2A—O2—H2B
C2A—C3A—C18A
C2A—C3A—N1A
C18A—C3A—N1A
C15—C16—C11
C15—C16—C17
C11—C16—C17
C10A—C5A—C6A
C10A—C5A—C4A
C6A—C5A—C4A
C11A—C16A—C15A
C11A—C16A—C17A
C15A—C16A—C17A
C7A—C6A—C5A
C7A—C6A—H6A
C5A—C6A—H6A
130.8 (6)
104.6
119.5
Acta Cryst. (2019). C75
sup-21

supporting information
C4—N1—C3
122.7 (2)
123.77 (18)
113.12 (17)
120.0 (3)
120.0
C1B—C3B—H3BA
O15—C3B—H3BB
C1B—C3B—H3BB
H3BA—C3B—H3BB
C3B—C1B—H1BA
C3B—C1B—H1BB
H1BA—C1B—H1BB
C3B—C1B—H1BC
H1BA—C1B—H1BC
H1BB—C1B—H1BC
C3B—O15—H15B
C5B—O14—H14B
104.6
104.6
104.6
105.7
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
C4—N1—Ga01
C3—N1—Ga01
C15—C14—C13
C15—C14—H14
C13—C14—H14
O4—C11—C12
O4—C11—C16
C12—C11—C16
C4A—N1A—C3A
C4A—N1A—Ga02
C3A—N1A—Ga02
O12—N3—O10
O12—N3—O11
O10—N3—O11
O6A—C21A—H21D
120.0
116.8 (2)
125.0 (2)
118.1 (2)
122.4 (2)
124.02 (18)
113.50 (17)
120.8 (3)
118.1 (2)
121.0 (3)
109.5
Ga02—O0AA—H0AA
Ga02—O0AA—H0AB
H0AA—O0AA—H0AB
110.3
110.0
103.7
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
i
O1—H1B···O4
O1—H1A···O3
0.85 (2)
0.85 (2)
0.84 (2)
0.83 (2)
0.85 (2)
0.86 (2)
0.86 (2)
2.11 (4)
2.06 (3)
2.17 (4)
2.20 (4)
1.90 (2)
1.77 (2)
1.83 (3)
2.800 (2)
2.816 (3)
2.872 (3)
2.844 (3)
2.727 (3)
2.620 (5)
2.656 (6)
138 (4)
147 (5)
141 (5)
134 (5)
161 (5)
170 (6)
162 (6)
i
ii
O2A—H2AB···O5A
O2A—H2AA···O4A
O2—H2B···O16
O2—H2A···O13
ii
iii
iii
O2—H2A···O15
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x, −y+1, −z+1; (iii) x, y, z+1.
Acta Cryst. (2019). C75
sup-22