Phenoxide and alkoxide complexes of Mg, Al and Zn, and their use for the ring-opening polymerization of ?-caprolactone with initiators of different natures

Article abstract of DOI:10.1107/S2053229618005090

A new packing polymorph of bis(2,6-di-tert-butyl-4-methylphenolato-κO)bis(tetrahydrofuran-κO)magnesium, [Mg(C₁₅H₂₃O)₂(C₄H₈O)₂] or Mg(BHT)₂(THF)₂, (BHT is the 2,6-di-tert-butyl-4-methylphenoxide anion and THF is tetrahydrofuran), (1), has the same space group (P2₁) as the previously reported modification [Nifant'ev et al. (2017d). Dalton Trans.46, 12132–12146], but contains three crystallographically independent molecules instead of one. The structure of (1) exhibits rotational disorder of the tert-butyl groups and positional disorder of a THF ligand. The complex of bis(2,6-di-tert-butyl-4-methylphenolato-κO)bis(μ₂-ethyl glycolato-κ²O,O′:κO)dimethyldialuminium, [Al₂(CH₃)₂(C₄H₇O₃)₂(C₁₅H₂₃O)₂] or [(BHT)AlMe(OCH₂COOEt)]₂, (2), is a dimer located on an inversion centre and has an Al₂O₂ rhomboid core. The 2-ethoxy-2-oxoethanolate ligand (OCH₂COOEt) displays a μ₂-κ²O,O′:κO semi-bridging coordination mode, forming a five-membered heteronuclear Al–O–C–C–O ring. The same ligand exhibits positional disorder of the terminal methyl group. The redetermined structure of the heptanuclear complex octakis(μ₃-benzyloxo-κO:κO:κO)hexaethylheptazinc, [Zn₇(C₂H₅)₆(C₇H₇O)₈] or [Zn₇(OCH₂Ph)₈Et₆], (3), possesses a bicubic Zn₇O₈ core located at an inversion centre and demonstrates positional disorder of one crystallographically independent phenyl group. Cambridge Structural Database surveys are given for complexes structurally analogous to (2) and (3). Complexes (2) and (3), as well as derivatives of (1), are of interest as catalysts for the ring-opening polymerization of ?-caprolactone, and polymerization results are reported.

Full text of DOI:10.1107/S2053229618005090

research papers
Phenoxide and alkoxide complexes of Mg, Al and
Zn, and their use for the ring-opening polymerization
of "-caprolactone with initiators of different natures
ISSN 2053-2296
Mikhail E. Minyaev,a* Ilya E. Nifant’ev,a,b Andrey V. Shlyakhtin,a,b Pavel V.
Ivchenkoa,b and Konstantin A. Lyssenkoc
Received 14 February 2018
Accepted 29 March 2018
aA.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky prospect, Moscow
119991, Russian Federation, bChemistry Department, M.V. Lomonosov Moscow State University, 1 Leninskie Gory Str.,
Building 3, Moscow 119991, Russian Federation, and cA.N. Nesmeyanov Institute of Organoelement Compounds,
Russian Academy of Sciences, 28 Vavilova Str., Moscow 119991, Russian Federation. *Correspondence e-mail:
mminyaev@mail.ru
Edited by V. Langer, Chalmers University of
Technology, Sweden
Keywords: magnesium; aluminium; zinc;
butylated hydroxytoluene; coordination
compounds; packing polymorphism; ring-
opening polymerization; "-caprolactone; crystal
structure; NMR.
A new packing polymorph of bis(2,6-di-tert-butyl-4-methylphenolato-ꢀO)bis-
(tetrahydrofuran-ꢀO)magnesium, [Mg(C15H23O)2(C4H8O)2] or Mg(BHT)2(THF)2,
(BHT is the 2,6-di-tert-butyl-4-methylphenoxide anion and THF is tetrahydro-
furan), (1), has the same space group (P21) as the previously reported
modification [Nifant’ev et al. (2017d). Dalton Trans. 46, 12132–12146], but
contains three crystallographically independent molecules instead of one. The
structure of (1) exhibits rotational disorder of the tert-butyl groups and
positional disorder of a THF ligand. The complex of bis(2,6-di-tert-butyl-4-
methylphenolato-ꢀO)bis(ꢁ2-ethyl glycolato-ꢀ2O,O0:ꢀO)dimethyldialuminium,
[Al2(CH3)2(C4H7O3)2(C15H23O)2] or [(BHT)AlMe(OCH2COOEt)]2, (2), is a
dimer located on an inversion centre and has an Al2O2 rhomboid core. The
2-ethoxy-2-oxoethanolate ligand (OCH2COOEt) displays a ꢁ2-ꢀ2O,O0:ꢀO semi-
bridging coordination mode, forming a five-membered heteronuclear Al–O–C–
C–O ring. The same ligand exhibits positional disorder of the terminal methyl
group. The redetermined structure of the heptanuclear complex octakis(ꢁ3-
benzyloxo-ꢀO:ꢀO:ꢀO)hexaethylheptazinc, [Zn7(C2H5)6(C7H7O)8] or [Zn7-
(OCH2Ph)8Et6], (3), possesses a bicubic Zn7O8 core located at an inversion
centre and demonstrates positional disorder of one crystallographically
independent phenyl group. Cambridge Structural Database surveys are given
for complexes structurally analogous to (2) and (3). Complexes (2) and (3), as
well as derivatives of (1), are of interest as catalysts for the ring-opening
polymerization of "-caprolactone, and polymerization results are reported.
CCDC references: 1833490; 1833489;
1833488
Supporting information: this article has
supporting information at journals.iucr.org/c
1. Introduction
Aryloxide complexes of nontoxic metals are among prospec-
tive catalysts in the ring-opening polymerization (ROP) of
cyclic esters (Dubois et al., 2009; Devaine-Pressing et al., 2015;
Klitzke et al., 2014; Li, Chen et al., 2012; Sarazin & Carpentier,
2015; Sun et al., 2014; Wheaton et al., 2009; Zhang et al., 2014)
for obtaining various polymers and polymeric materials,
including biodegradable ones. Therefore, the number of
aryloxide complexes of main group and transition metals has
increased dramatically in recent years. ortho-Disubstituted
bulky phenols, including 2,6-di-tert-butyl-4-methylphenol
(butylated hydroxytoluene or BHT-H), have been used
successfully to synthesize highly active catalysts for the ROP
of rac-lactide, "-caprolactone and !-pentadecalactone (see
Chen et al., 2012; Fang et al., 2012; Ivchenko et al., 2017;
Nifant’ev et al., 2016, 2017a,b,d; Wilson et al., 2014, 2015, and
references therein) or cyclic phosphoesters (Nifant’ev et al.,
2017c, 2018). We report herein the synthesis and structures of
# 2018 International Union of Crystallography
548 https://doi.org/10.1107/S2053229618005090
Acta Cryst. (2018). C74, 548–557

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Mg, Al and Zn complexes (Scheme 1) and present results on
the ROP of "-caprolactone ("-CL) associated with these
complexes.
OCH2COOEt, O(CH2)3CON(CH3)2 and O-C6H4-4-tBu; see
Nifant’ev et al., 2016, 2017d]. While using any of these
complexes as a catalyst, polymerization of "-caprolactone
("-CL) leads to the formation of poly-"-caprolactone (PCL)
with a terminal OR group. However, analogous reactions
involving either Mg(BHT)2(THF)2 or Mg(BHT)(n-Bu)-
(THF)2 and other alcohols, including secondary, tertiary or
sterically crowded ones, usually provides insoluble or poorly
THF-soluble suspensions in equilibrium with soluble species
and not precipitating from solution after days or weeks.
Obtained by centrifugation, the precipitates contained less of
the BHT ligand than expected. It should be noted that isolated
samples of complexes ‘Mgx(BHT)y(OR)2x–y(THF)z’ (OR =
t
t
iPrO, BuO or BuCH2O) underwent slow metathesis in
toluene, providing, upon crystallization from toluene/hexane
1
mixtures, Mg(BHT)2(THF)2 (based on H NMR data), for
which the unit-cell dimensions were analogous to those found
previously for Mg(BHT)2(THF)2 (Nifant’ev et al., 2017d).
Nevertheless, polymerization of "-CL with Mg(BHT)2(THF)2
t
activated by 1 molar equivalent of alcohol (iPrOH, BuOH,
tBuCH2OH and cholesterol) in THF leads to PCL containing a
corresponding OR terminal group [see Fig. 1 (bottom) and the
1H NMR spectra in Figs. S2–S5 in the supporting information].
The latter allowed us to think that we were dealing with
polynuclear alkoxide complexes containing terminal BHT
groups as a result of aggregation (Nifant’ev et al., 2017d).
Indeed, the tetranuclear complex [Mg4(BHT)2(OCH2CH2-
NH2)6], which was obtained from the reactions of
Mg(BHT)2(THF)2 with HOCH2CH2NH2 in 4:6 and even 1:1
molar ratios (Minyaev et al., 2017), can be regarded as such an
example.
Mg(BHT)2(THF)2 itself (THF is tetrahydrofuran) is cata-
lytically inactive but displays high catalytic activity in the
polymerization of cyclic esters when activated by alcohols (e.g.
Chen et al., 2012), whereas the [Mg(BHT)(OR)(THF)n]2
complexes (n = 0 or 1) do not require an initiator for the ROP
process to occur (Nifant’ev et al., 2016, 2017d). The reaction of
either Mg(BHT)2(THF)2 or Mg(BHT)(n-Bu)(THF)2 with 1
molar equivalent of a primary alcohol allowed us to prepare
dimeric complexes possessing definite compositions and
established crystal structures [Fig. 1, top; OR = OEt, OCH2Ph,
However, some Mg–BHT complexes bearing secondary
alkoxide anions and being soluble in THF can presumably be
synthesized. A cyclohexyl-protected furanose form of glucose
was used to produce its soluble Mg–BHT derivative (Fig. 2,
1
middle; the structure of the intermediate is based on its H
NMR spectrum). Due to its high solubility in THF or toluene,
we were not able to obtain pure crystalline samples of the
complex. An attempt to crystallize it from a toluene/hexane
mixture resulted in a slow metathesis reaction providing
crystals of another polymorphic modification of Mg(BHT)2-
Figure 1
The synthesis of various Mg–BHT complexes containing alkoxide anions and the catalytic polymerization of "-caprolactone.
ꢀ
Acta Cryst. (2018). C74, 548–557
Minyaev et al.
Ring-opening polymerization of "-caprolactone 549

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Figure 2
The synthesis of an Mg–BHT derivative of a cyclohexyl-protected furanose and polymerization of "-caprolactone.
(THF)2, (1) (based on 1H NMR and X-ray studies), for which
the unit-cell dimensions differed from those reported
previously for Mg(BHT)2(THF)2 (Nifant’ev et al., 2017d).
Another proof for the BHT–Mg–(protected glucose) forma-
tion is polymerization of "-CL by the complex, leading to
PCL with a corresponding terminal group (Fig. 2, right; see
absence of the BHT ligand. It should be noted that complex
(3) was obtained previously from ZnEt2 and benzyl alcohol (in
a 1:1 ratio) in THF (Fig. 3, bottom right) and has been studied
crystallographically by Li, Nie et al. (2012).
1
2. Experimental
Fig. S6 in the supporting information for the H NMR spec-
trum).
All synthetic manipulations were performed under a purified
argon atmosphere using Schlenk glassware, dry-box techni-
ques and absolute solvents. "-Caprolactone was distilled from
CaH2 under reduced pressure in argon. Tetrahydrofuran was
predried over NaOH and distilled from potassium/benzo-
phenone ketyl. Hexane was distilled from Na/K alloy in the
presence of 18-crown-6 and benzophenone ketyl. Toluene was
distilled from sodium/benzophenone ketyl. Toluene-d8 and
We were able to crystallize two other complexes that might
exhibit ROP catalytic activity, which were then studied in the
polymerization of "-CL. The reaction of (BHT)2AlMe with
ethyl glycolate (ethyl 2-hydroxyacetate) in toluene upon loss
of BHT-H leads to the formation of the binuclear complex
[(BHT)AlMe(OCH2COOEt)]2, (2), which was crystallized
from a toluene/hexane mixture (Fig. 3, top). An analogous
reaction of [(BHT)Zn(ꢁ2-Et)]2 with benzyl alcohol produced
the heptanuclear complex [Zn7(OCH2Ph)8Et6], (3) (Fig. 3,
bottom left). We undertook an X-ray diffraction study of (3) in
order to confirm its structure, since the 1H NMR spectrum of
its toluene-d8 solution sample prepared from a single crystal
suggested the existence of two forms in solution and the
1
benzene-d6 were distilled from Na/K alloy. H NMR spectra
were recorded with Bruker AVANCE 400 and Bruker AM-
300 spectrometers in toluene-d8, benzene-d6 (for the com-
plexes) and in CDCl3 (for the polymers). C/H elemental
analysis was performed with a PerkinElmer 2400 Series II
elemental analyzer. Gel-permeation chromatography (GPC)
Figure 3
Syntheses of [(BHT)AlMe(OCH2COOEt)]2, (2) (top), and of [Zn7(OCH2Ph)8Et6], (3) (bottom).
ꢀ
550 Minyaev et al.
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Acta Cryst. (2018). C74, 548–557

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Table 1
Experimental details.
All experiments were carried out at 120 K with Mo Kꢃ radiation using a Bruker SMART APEXII diffractometer. Absorption was corrected for by multi-scan
methods (SADABS; Bruker, 2008). H-atom parameters were constrained.
(1)
(2)
(3)
Crystal data
Chemical formula
Mr
Crystal system, space group
[Mg(C15H23O)2(C4H8O)2]
607.18
Monoclinic, P21
[Al2(CH3)2(C4H7O3)2(C15H23O)2]
728.88
Monoclinic, C2/c
27.7603 (18), 9.0454 (6),
18.4921 (13)
[Zn7(C2H5)6(C7H7O)8]
1488.95
Orthorhombic, Pbca
13.9163 (5), 20.4248 (7),
23.0316 (8)
˚
a, b, c (A)
16.847 (3), 15.6786 (18), 21.787 (2)
ꢃ, ꢄ, ꢅ (ꢃ)
90, 106.954 (4), 90
5504.9 (12)
90, 118.401 (2), 90
4084.5 (5)
90, 90, 90
6546.4 (4)
3
˚
V (A )
Z
6
0.08
4
0.12
4
2.57
ꢁ (mmꢁ1
Crystal size (mm)
)
0.48 ꢂ 0.40 ꢂ 0.37
0.45 ꢂ 0.33 ꢂ 0.23
0.41 ꢂ 0.35 ꢂ 0.29
Data collection
Tmin, Tmax
0.951, 0.975
69149, 29225, 20602
0.952, 0.979
17279, 5888, 4280
0.438, 0.542
75283, 9558, 8071
No. of measured, independent and
observed [I > 2ꢆ(I)] reflections
Rint
0.036
0.682
0.044
0.703
0.034
0.703
ꢁ1
˚
(sin ꢇ/ꢈ)max (A
)
Refinement
R[F2 > 2ꢆ(F2)], wR(F2), S
No. of reflections
0.047, 0.122, 0.98
29225
0.043, 0.109, 1.01
5888
0.024, 0.055, 1.02
9558
No. of parameters
No. of restraints
Áꢉmax, Áꢉmin (e A
Absolute structure
Absolute structure parameter
1238
17
241
2
395
0
ꢁ3
˚
)
0.27, ꢁ0.21
0.38, ꢁ0.26
0.39, ꢁ0.33
Refined as an inversion twin
0.07 (15)
–
–
–
–
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXT (Sheldrick, 2015a), SHELXL2017 (Sheldrick, 2015b) and SHELXTL (Sheldrick, 2008).
2.1.2. Synthesis of (BHT)2AlMe. A solution of AlMe3
(740 mg, 10 mmol, 97% purity) in hexane (4 ml) was added
dropwise to a stirred solution of 2,6-di-tert-butyl-4-methyl-
phenol (4.408 g, 20 mmol) in hexane (7 ml). The reaction
mixture was stirred for 10 min until the product started to
precipitate. The reaction mixture was heated under reflux for
40 min and then cooled to room temperature. After 3 h, the
mother liquor was decanted. The crystalline precipitate was
recrystallized from boiling hexane (5 ml) and dried under
vacuum. The yield of colourless crystals was 3.992 g
measurements were recorded on an Agilent PL-GPC 220
chromatograph equipped with a PLgel Olexis column (eluent:
THF, 1 ml minꢁ1, 313 K), using universal calibration with
polystyrene (PS) standard. Mg(BHT)2(THF)2 was prepared as
described previously (Nifant’ev et al., 2017d).
2.1. Synthesis and crystallization
2.1.1. Crystallization of Mg(BHT)2(THF)2, (1). A solution of
(3a0R,50S,60S,6a0R)-50-(1,4-dioxaspiro[4.5]decan-2-yl)tetrahydro-
spiro[cyclohexane-1,20-furo[2,3-d][1,3]dioxol]-60-ol (C18H28O6;
340 mg, 0.4 mmol) in THF (2 ml) was added dropwise to a
solution of Mg(BHT)2(THF)2 (243 mg, 0.4 mmol) in THF
(2 ml). The reaction mixture was stirred for 30 min. The
solvent was almost completely evaporated from the solution
under reduced pressure. The residue was then washed with
hexane (3 ꢂ 1.5 ml) and dried under vacuum, providing an
amorphous powder. The 1H NMR spectrum showed the
presence of coordinated glucose and BHT (in a 1:1 ratio), and
the absence of free BHT-H. The solid was dissolved in toluene
(1.5 ml) and hexane (9 ml) was layered on top. Crystals of (1)
formed after two weeks. Some of these were taken for X-ray
diffraction analysis. The remaining crystals were washed with
hexane (3 ꢂ 1 ml) and dried under vacuum. The yield was
1
(8.30 mmol, 83%). H NMR (C6D6, 302 K, 300 MHz): ꢂ 7.14
(4H, s, Hmeta), 2.32 (6H, s, CH3, BHT), 1.59 (36H, s, tBu, BHT),
0.24 (3H, s, Al–CH3).
2.1.3. Synthesis of [(BHT)AlMe(OCH2COOEt)]2, (2). A
solution of ethyl 2-hydroxyacetate (HOCH2COOEt; 104 mg,
1.0 mmol) in toluene (1 ml) was added dropwise to a stirred
solution of (BHT)2AlMe (481 mg, 1.0 mmol) in toluene (3 ml)
containing 4 drops of THF. The resulting solution was stirred
for 3 min. Hexane (16 ml) was layered on top of the solution.
Colourless crystals formed after 10 d. Some crystals were
taken for X-ray studies. The mother liquor was decanted. The
remaining crystals were washed with hexane (2 ꢂ 2 ml) and
dried under vacuum. The yield of (2) was 288 mg (0.40 mmol,
79%). Analysis found (calculated for C40H66Al2O8) (%): C
65.54 (65.91), H 9.52 (9.13). m/z: 728.44 (100.0%), 729.44
(43.6%), 730.45 (9.6%), 731.45 (2.1%), 730.44 (1.6%). 1H
NMR (C6D5CD3, 300 K, 400 MHz): ꢂ ꢁ0.20 (3H, s, Al–CH3),
0.57 (3H, t, CH2–CH3, 3JHH = 7.07 Hz), 1.62 [18H, s, C(CH3)3],
1
140 mg. H NMR (C6D5CD3, 299 K, 300 MHz): ꢂ 1.27–1.37
(4H, m, O–CH2–CH2, THF), 1.60 [18H, s, Ar–C(CH3)3], 2.41
(3H, s, Ar–CH3), 3.66–3.76 (4H, m, O–CH2, THF), 7.21 (2H, s,
Hmeta).
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Ring-opening polymerization of "-caprolactone 551

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2.33 (3H, s, Cipso–CH3), 3.37–3.47 (1H, m, CH2–CH3), 3.52–
3.62 (1H, m, CH2–CH3), 4.23–4.35 (2H, m, O–CH2–CO), 7.19
(2H, s, Hmeta). See Fig. S1 in the supporting information for the
1H NMR spectrum.
obtained using catalyst (3) is given in Fig. S7 of the supporting
information.
2.2. Refinement
2.1.4. Synthesis of [(BHT)ZnEt]2. A solution of ZnEt2 in
hexane (20 ml, 1.0 M, 20 mmol) was added dropwise to a
stirred solution of 2,6-di-tert-butyl-4-methylphenol (4.407 g,
20 mmol) in toluene (6 ml). The reaction mixture was stirred
for 30 min. The next day the mother liquor was decanted from
the precipitated crystals, which were then washed with hexane
(2 ꢂ 10 ml) and dried under dynamic vacuum. The yield of
Crystal data, data collection and structure refinement
details are summarized in Table 1. The H atoms were posi-
˚
tioned geometrically (C—H = 0.95 A for aromatic, 0.98 A for
˚
˚
methyl and 0.99 A for methylene H atoms) and refined as
riding atoms, with relative isotropic displacement parameters
Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C)
otherwise. A rotating group model was applied for methyl
groups.
1
colourless crystals was 5.589 g (8.89 mmol, 89%). H NMR
(C6D6, 293 K, 400 MHz): ꢂ 7.20 (2H, s, Hmeta), 2.27 (3H, s, CH3,
Reflections 101 and 100 in (1) were affected by the beam
stop and were therefore omitted from the refinement.
Reflections 606 and 508 in (1) were also omitted from the
refinement since their (Iobs ꢁ Icalcd)/ꢆ(W) values were over 10.
Complex (1) was refined as an inversion twin with a domain
ratio of 0.93 (15):0.07 (15), where the rather high s.u. value
might be explained by low anomalous scattering, as well as by
pseudosymmetry. Two of the three independent molecules in
(1) exhibit rotational disorder of the tert-butyl groups, with
ratios of 0.741 (3):0.259 (3) and 0.900 (3):0.100 (3) for the
C28A–C30A/C28B–C30B and C23C–C25C/C23D–C25D
atoms, respectively (Figs. 4a and 4b). The third molecule
contains a conformationally disordered THF molecule [atoms
C32E/C32F; the disorder ratio is 0.809 (6):0.191 (6); Fig. 4c].
The terminal methyl group in the OCH2COOCH2CH3 ligand
in (2) is almost equally disordered over two positions, with a
ratio of 0.507 (11):0.493 (11) for the C19A/C19B atoms (Fig. 5).
One of four non-equivalent phenyl groups is disordered over
two positions; the ratio is 0.622 (6):0.378 (6) for atoms C30A–
C34A/C30B–C34B (Fig. 6a). All the disorder was refined in a
regular manner, including the same anisotropic displacement
parameters for similar atoms. All six C—CH3 bond lengths in
each of the two disordered tert-butyl groups and the four
CH2—CH2 bond lengths in the disordered THF fragment in
(1), together with two CH2—CH3 bond lengths in (2), were
BHT), 1.63 (18H, s, tBu, BHT), 1.13 (3H, t, –CH2CH3, 3JHH
3
8.08 Hz), 0.60 (3H, q, –CH2CH3, JHH = 8.08 Hz).
=
2.1.5. Synthesis of [Zn7(OCH2Ph)8Et6], (3). A solution of
benzyl alcohol (110 mg, 1.02 mmol) in toluene (2 ml) was
added to crystals of [(BHT)ZnEt]2 (325 mg, 0.52 mmol). The
mixture was stirred for 2 min to give a colourless solution.
After 30 min, hexane (8 ml) was layered on top of the solu-
tion. Colourless crystals of [Zn7(OCH2Ph)8Et6], (3), formed
over a period of 10 d (yield: 183 mg, 0.12 mmol, 84%). Half
of the crystals were taken for X-ray studies. The other half
were washed with hexane (2 ꢂ 0.5 ml) and dried under
1
vacuum. H NMR (C6D5CD3, 300 K, 400 MHz): ꢂ ꢁ0.07 to
+0.26 (6H, m, Zn–CH2–CH3), 0.95–1.03 (9H, m, Zn–CH2–
CH3), 4.67–5.24 (8H, m, Zn–CH2–Ph), 7.07–7.55 (20H, m, Zn–
CH2–C6H5).
2.1.6. Polymerization of "-caprolactone. In a typical poly-
merization experiment, 1 ml of a 0.1 M solution of ROH in
THF (0.1 mmol) was added dropwise to a solution of Mg-
(BHT)2(THF)2 (61 mg, 0.1 mmol) in THF (1 ml). The reaction
mixture was stirred for 20 min. A solution of "-CL (1.141 g,
10.0 mmol) in THF (up to 3 ml of the solution) was added at
i
once to the resulting stirred suspension (for ROH = PrOH,
tBuOH and tBuCH2OH). The "-CL/ROH/Mg molar ratio was
100:1:1. After a certain amount of time (see reaction time in
Table 5), a sample of the reaction mixture was dissolved in
CDCl3 containing a small amount of acetic acid to neutralize
the catalyst. The "-CL conversion into PCL was calculated
from a recordered 1H NMR spectrum, based on integral
intensities of the CH2OC O proton resonance signals being
4.14 ppm for "-CL and 3.98 ppm for PCL. The vial was then
taken out of the dry-box. The resulting viscous solution was
poured into a large excess of methanol (up to 100 ml)
containing a few drops (a fivefold excess with respect to Mg)
of acetic acid. The resulting precipitate was filtered off and
reprecipitated from a THF/methanol mixture (ca 1:10 v/v),
filtered off and dried under dynamic vacuum until a constant
mass was noted. For cholesterol and cyclohexyl-protected
furanose, the "-CL/ROH/Mg molar ratios were 60:1:1 and
˚
restrained to be equal within 0.002 A for each group of
distances using free variables.
3. Results and discussion
3.1. Mg(BHT)2(THF)2, (1)
The asymmetric unit of (1) contains three independent
Mg(BHT)2(THF)2 molecules (Fig. 4), which exhibit disorder
either of the tert-butyl groups (Figs. 4a and 4b) or a coordi-
nated THF molecule (Fig. 4c). The Mg atom adopts a distorted
tetrahedral environment. The O—Mg—O angles lie in the
following ranges for all three molecules: 89.26 (7)–89.59 (7)ꢃ
for OTHF–Mg–OTHF, 97.82 (7)–125.24 (8)ꢃ for OTHF–Mg–OBHT
and 122.30 (8)–125.31 (8)ꢃ for OBHT–Mg–OBHT, which is in
1
75:1:1, respectively. The H NMR spectra of PCL with term-
inal RO groups can be found in the supporting information
(Figs. S2–S6).
agreement with steric hindrance of the ligands. The Mg—
˚
O
BHT bond lengths are shorter by 0.18–0.21 A than the Mg—
Complexes (2) and (3) were generated in situ. "-CL poly-
merization experiments with (2) and (3) were performed
1
under similar conditions. The H NMR spectrum of PCL
OTHF bond lengths (Table 2), presumably due to the presence
of a negative charge at the phenoxide BHTꢁ anion regardless
of its bulkiness.
ꢀ
552 Minyaev et al.
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Acta Cryst. (2018). C74, 548–557

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Table 2
Selected bond lengths (A) for (1).
˚
Mg1—O1A
Mg1—O2A
Mg1—O3A
Mg1—O4A
Mg2—O1C
Mg2—O2C
1.8575 (17)
1.8653 (16)
2.0438 (18)
2.0595 (18)
1.8557 (17)
1.8639 (17)
Mg2—O3C
Mg2—O4C
Mg3—O2E
Mg3—O1E
Mg3—O4E
Mg3—O3E
2.0502 (18)
2.0699 (18)
1.8554 (17)
1.8660 (17)
2.0444 (18)
2.0653 (18)
The crystal structure of another packing polymorph modi-
fication of Mg(BHT)2(THF)2 has been established previously
by our group (Nifant’ev et al., 2017d). It belongs to the same
space group (P21), but contains one crystallographically
independent molecule and has quite different unit-cell
dimensions. The Mg—O bond lengths and O—Mg—O angles
are nearly identical in both polymorphs of Mg(BHT)2(THF)2.
Very similar Mg—O bond lengths and O—Mg—O angles have
also been found in Mg(BHT)2(DMSO)2 (DMSO is dimethyl
sulfoxide; Nifant’ev et al., 2017d).
The crystal structures of Mg–BHT derivatives are currently
being studied, mainly due to their application in the ROP of
cyclic esters, but until recently they were poorly explored. A
short survey of the Cambridge Structural Database (CSD,
Version 5.38, with updates to May 2017; Groom et al., 2016) for
crystal structures of Mg–OAr complexes, including Mg–BHT
compounds, has been presented recently (Minyaev et al.,
2017), which, however, does not cover the latest dimeric Mg–
BHT structures published by Nifant’ev et al. (2017d).
3.2. [(BHT)AlMe(OCH2COOEt)]2, (2)
The molecule of [(BHT)AlMe(OCH2COOEt)]2, (2), is
located on an inversion centre, forming a dimeric structure
(Fig. 5) and having an Al2O2 rhomboid core (Fig. 3, top,
coloured atoms). The terminal BHT ligand is ꢀO-coordinated
to the Al atom, whereas the OCH2COOEt ligand displays a
ꢁ2-ꢀ2O,O0:ꢀO semi-bridging coordination mode, forming a
five-membered heteronuclear Al–O–C–C–O ring. The
shortest Al—O bond is Al1—O1(BHT) involving the steri-
cally more crowded BHT ligand (Table 3). Atoms Al1, O1, O2
and C20 lie in one plane, with the greatest deviation of
˚
0.0037 (6) A being for atom Al1. The Al coordination number
(CNAl) is 5. The closest polyhedron for the Al environment is
a trigonal bipyramid, with atoms O2i and O3 in axial, and
atoms O1, O2 and C20 in equatorial positions (see the selected
bond lengths and angles in Table 3) [symmetry code: (i) ꢁx + 1,
ꢁy + 1, ꢁz + 1]. The fragment containing 14 atoms (Al1, Al1i,
O2, O2i, O3, O3i, C16, C16i, C17, C17i, O4, O4i, C18 and C18i)
Table 3
Selected geometric parameters (A, ) for (2).
ꢃ
˚
Al1—O1
Al1—O2
Al1—O2i
1.7390 (10)
1.8665 (10)
1.9080 (10)
Al1—C20
Al1—O3
1.9562 (14)
2.1219 (10)
Figure 4
Al1—O2—Al1i
O2—Al1—O2i
O2—Al1—O3
107.13 (5)
72.87 (5)
77.98 (4)
O2i—Al1—O3
O1—Al1—C20
150.25 (4)
119.07 (6)
The structures of the three crystallographically independent molecules of
Mg(BHT)2(THF)2, (1). Displacement ellipsoids were set at the 50%
probability level and H atoms have been omitted. The minor components
of disorder are shown with open solid lines.
Symmetry code: (i) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1.
ꢀ
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Ring-opening polymerization of "-caprolactone 553

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Figure 5
The crystal structure of [(BHT)AlMe(OCH2COOEt)]2, (2). Displace-
ment ellipsoids were set at the 50% probability level and H atoms have
been omitted. The second components of the C19A/C19B disorder are
shown with open solid lines. [Symmetry code: (i) ꢁx + 1, ꢁy + 1, ꢁz + 1.]
is nearly planar, with the greatest deviations from the plane
i
being of 0.0828 (7) A for atoms Al1/Al1 , 0.0764 (8) A for O3/
˚
˚
i
i
˚
O3 and 0.0378 (10) A for O4/O4 . The terminal CH3 group of
the OCH2COOEt ligand is nearly equally disordered over two
positions [see x2.2 (Refinement) and Fig. 5].
Some negligible nonvalence interactions are present in the
crystal structure, including a rather long C18—Hꢄ ꢄ ꢄO3iii
interaction [the C18ꢄ ꢄ ꢄO3iii distance is 3.5142 (18) A; sym-
˚
3
2
metry code: (iii) ꢁx + 1, y, ꢁz + ].
According to the CSD, there are numerous structures of Al
derivatives possessing the Al2O2 rhomboid core. However, the
number of closely related Al compounds containing (RO)Al-
(Alkyl/Aryl)(OAryl) fragments with CNAl = 5 is limited to seven
structures. These are the five dinuclear complexes [AlMe(O-2,6-
R2C6H3)(ꢁ2-OCH2THF-ꢀ2O,O0:ꢀO)]2 [where OCH2THF is
tetrahydrofuran-2-ylmethoxide; R = Me (CSD refcode FIL-
LOC) or tBu (FILMAP); Boyle et al., 2005), [AlEt(THF)(ꢁ2-
mbpcp-ꢀ2O,O0:ꢀO]2 [mbpcp is 2,20-methylenebis(4-chloro-
phenoxide); HIBKAF; Zevaco et al., 2007], [AlR(THF)(ꢁ2-
OC6H4OC6H4O-ꢀ3O,O0,O00:ꢀO)] [OC6H4OC6H4O is the 2,20-
oxobis(phenoxide) dianion; R = tBu (PAKLEU) and Ph
(PAKLIY); Ziemkowska et al., 2011], [AlMe(THF)(ꢁ2-BINOL-
ꢀ2O,O0:ꢀO)]2 [BINOL is the binaphthoxide dianion; PERKAY
(Arai et al., 1998) and PERKAY01 (Graves et al., 2007)], and the
two tetranuclear complexes [R02(AlR00)4(ꢁ2-OAryl)2] [where R0 =
OPh, R00 = Et and OAryl = OPh (IWEBIW; Karpiniec et al.,
2011); R0 = Me, R00 = Me and OAryl = O-3,5-(CF3)2C6H3
Figure 6
(a) The asymmetric unit and (b) the molecule in the crystal structure of
[Zn7(OCH2Ph)8Et6], (3). Displacement ellipsoids were set at the 50%
probability level and
H atoms have been omitted. The second
components of the phenyl-ring disorder (atoms C30–C34) are shown
with open solid lines (left). For the entire molecule (right), all but the
Cipso atoms of the phenyl groups have been omitted. Cipso atoms are
labelled as ‘Ph’ and the disorder is not shown. [Symmetry code: (ii) ꢁx + 1,
ꢁy + 1, ꢁz + 1.]
(WODXET; Martinez et al., 2008)]. None of these compounds
contains a glycolate O–CR2–COO–R fragment.
On the other hand, there are five mononuclear Al structures
bearing the ꢁO–CR2–COO–R anionic ligand, viz. [Al(L-ꢀ4O,O0,-
N,N0)(OCHMeCOOMe-ꢀ2O,O0)]ꢄtoluene (NIFPAU; Nomura et
al., 2007), [Al(L-ꢀ4O,O0,N,N0)(OCHMeCOOMe-ꢀO)] (ODA-
ꢀ
554 Minyaev et al.
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Acta Cryst. (2018). C74, 548–557

research papers
Table 4
Selected geometric parameters (A, ) for (3).
3.3. [Zn7(OCH2Ph)8Et6], (3)
ꢃ
˚
The structure of [Zn7(OCH2Ph)8Et6] is located on an
inversion centre. The asymmetric unit is shown in Fig. 6(a).
The phenylmethanolate ligand displays a ꢁ3-ꢀO:ꢀO:ꢀO coor-
dination mode. The site occupancy for atom Zn1 is 50%. The
heptanuclear complex (Fig. 6b) has a distorted bicubic Zn7O8
core (Fig. 3, bottom, coloured atoms; see also selected Zn—O
bond lengths and O—Zn—O angles in Table 4), in which the
central Zn1 atom has CNZn = 6, whereas CNZn = 4 for the
other Zn atoms. All Znꢄ ꢄ ꢄZn distances are in the range from
Zn1—O1
Zn1—O2
Zn1—O3
Zn2—O1
Zn2—O2
Zn2—O4
Zn3—O2
Zn3—O3
2.1148 (9)
2.1062 (10)
2.1332 (9)
2.0596 (10)
2.0922 (10)
2.1203 (10)
2.0631 (10)
2.0524 (10)
Zn3—O4
Zn4—O1
Zn4—O3
Zn4—O4
Zn2—C1
Zn3—C3
Zn4—C5
2.0553 (10)
2.1228 (10)
2.0858 (10)
2.0511 (10)
1.9637 (15)
1.9655 (16)
1.9695 (15)
O2—Zn1—O1
O2—Zn1—O1i
O1—Zn1—O3
O1—Zn1—O3i
O2—Zn1—O3
O2—Zn1—O3i
O1—Zn2—O2
O1—Zn2—O4
81.39 (4)
98.61 (4)
81.72 (4)
98.28 (4)
82.72 (4)
97.28 (4)
83.04 (4)
82.80 (4)
O2—Zn2—O4
O3—Zn3—O2
O4—Zn3—O2
O3—Zn3—O4
O3—Zn4—O1
O4—Zn4—O1
O4—Zn4—O3
82.36 (4)
85.79 (4)
84.67 (4)
83.54 (4)
82.65 (4)
82.94 (4)
82.82 (4)
˚
3.0771 (2) (for Zn3ꢄ ꢄ ꢄZn4) to 3.1443 (2) A (for Zn1ꢄ ꢄ ꢄZn2).
The crystal structure of the complex [Zn7(OCH2Ph)8Et6] has
been established previously (CSD refcode BANRUF; Li, Nie
et al., 2012). However, sufficiently good single-crystal quality
has allowed us to obtain a better crystallographic model
presented herein.
Symmetry code: (i) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1.
The cubic Zn4O4 core is rather robust and common – there
are 61 crystal structures upon exclusion of duplicates in the
CSD. The bicubic Zn7O8 core seems to be common as well.
Eleven structures have been found, including [Zn7(C2H5)6(ꢁ2-
OCH2Ph)8]. Other similar complexes possessing the [Zn7(ꢁ3-
FUW; Tang et al., 2006) and [Al(L-ꢀ4O,O0,N,N0)(OCMe2-
COOMe-ꢀ2O,O0)] (QADCUW; Kan et al., 2016), where
ligands L are dianionic salen-like tetradentate ligands, and
[Al(L0-ꢀ3O,O0,N)(OCHMeCOOiPr-ꢀ2O,O0)] [L0 is a bis-
(phenoxide) derivative of pyridine; ZOVYAM; Klitzke et al.,
2014) and [Al{O-2-(Me2NCH2)-4-Me-6-(CPh3)C6H2-ꢀ2O,N}-
(OCHMeCOOCHMeCOOiPr-ꢀ2O,O0)(THF)]+[B(C6F5)4]ꢁꢄ-
0.5(cyclopentane) (YIBWUC; Dagorne et al., 2007). The ꢁO–
CR2-COO–Alkyl ligand exhibits the ꢀO coordination mode in
one case and the ꢁ2-ꢀ2O,O0:ꢀO coordination mode in four of
OR)8R06] structural motif are EMEYA/ZNOMEZ (R = Me
0
´
and OR = OMe; Lewinski et al., 2003; Ziegler & Weiss, 1970),
KOHSEG (R = Me and OR0 = OCH2CH2OMe; Polarz et al.,
2005), ICEVUI [R = Et and OR0 = OCH2–C3H5 (C3H5 is
cyclopropyl); Boyle et al., 2004], MIGXIJ (R = CH2I and OR0 =
OMe; Charette et al., 2002), MOZNET (R = Et and OR0 =
OMe; Ishimori et al., 1976), YIGHAY/YIGHAY01 (R = Et
and OR0 = OEt; Jana et al., 2007; Redshaw et al., 2010)
and YOKXUS ({Zn7Me6(ꢁ3-OMe)6[ꢁ3-OZnMe(tBuN CH–
CH NtBu-ꢀ2N,N0)]2}ꢄtoluene; Lewinski et al., 2008).
the five complexes. The structure of [(BHT)AlMe(OCH2
-
COOEt)]2, (2), remains the sole example of a dimeric complex
possessing the Al2O2 rhomboid core and incorporating both
aryloxy and glycolate ligands.
The structure of (2) seems to be structurally analogous to
the Mg complex [(BHT)Mg(THF)(ꢁ-OCH2COOEt)]2 (Nif-
ant’ev et al., 2017d), where the CH3 ligand is replaced with the
THF molecule. However, the Mg2O4C4 core of the latter is not
flat, unlike that in (2). Both complexes demonstrate good
(Mg) or moderate (Al, see below) catalytic activity in the ROP
of "-CL without activation by alcohol.
Three remaining structures for metal–organic framework
(MOF) applications have more complex structures:
[Zn7(H2L)3(OMe)2]ꢄH2O (FORTOX) and [Cd2{Zn7L(HL)2-
(OH)2}(Py)2(H2O)]ꢄDMF (FORTIR) (Liu et al., 2014), and
[Zn7L03(OH)2]ꢄ6DMFꢄ2H2O (HAKZUR; Fang et al., 2016),
where L and L0 are ꢁ5-coordinated hexaanionic (L) or
tetraanionic (L0) salen-like hexadentate ligands. A sole
example of a similar Mg7O8 bicubic core was found in the
Table 5
Catalytic experimental data for "-caprolactone polymerization using Mg(BHT)2(THF)2 as precatalyst (BHT is the 2,6-di-tert-butyl-4-methylphenoxide
anion and THF is tetrahydrofuran) and different initiators ROH (["-CL] = 2 M, 293 K).
Mn is the number average molecular mass and Conv. is a monomer-to-polymer conversion value.
a
b
c
c
Run
Catalyst
ROH activator
"-CL/ROH
Reaction time (min)
Conv. (%)
>99
11
89
>99
>99
>98
35
98
33
Mn,theo.
Mn, NMR
Mn,GPC
ÐM
1
2
3
4
5
6
7
8
9
(1)
(1)
(1)
(1)
(1)
(1)
(2)
(2)
(3)
iPrOH
100
100
100
100
60
20
20
360
20
20
20
20
60
11470
1330
10230
11300
7240
8820
4100
11290
3870
12940
n.d.
13120
n.d.
1.30
n.d.
1.76
1.24
1.37
2.14
3.45
2.82
3.22
tBuOH
tBuOH
14110
12170
7050
9130
n.d.
23800
11200
6940
7740
8200
16400
6400
tBuCH2OH
Cholesterol
Cyclohexyl-protected furanose
75
No
No
No
100
100
100
n.d.
7530
60
Notes: (a) theoretically calculated Mn,theo = M"-CL ꢂ ["-CL]0/[I]0 ꢂ conversion + MROH, where M"-CL is the molecular mass of "-CL, MROH is the molecular mass of the initiator and
["-CL]0/[I]0 is the monomer-to-initiator initial concentration ratio; (b) determined from 1H NMR spectra by analysis of the signal integration of the RO and PCL fragments, see the
supporting information; (c) determined by GPC versus polystyrene standards and corrected by a factor of 0.56 (Save et al., 2002), where ÐM is a polydispersity index determined as ÐM
Mw/Mn, where Mw is weight average molecular mass.
=
ꢀ
Acta Cryst. (2018). C74, 548–557
Minyaev et al.
Ring-opening polymerization of "-caprolactone 555

research papers
heptanuclear complex [Mg7(ꢁ3-O)8(L00-ꢀ2O,N)6] (QUFBAW;
Ghosh et al., 2015) [L00 = O-2,4-tBu2C6H2-6-(–CH N-C6H4-4-
OMe)].
analysis of the catalysts) and partially supported by the TIPS
RAS State Plan (analysis of the obtained polymers).
Funding information
3.4. Results of the ROP of "-CL
Funding for this research was provided by: Russian Science
Foundation (grant No. 16-13-10344); TIPS RAS State Plan.
In ROP experiments catalyzed by (1) activated by primary
and secondary ROH initiators (Figs. 1 and 2), we observed
nearly quantitative "-CL conversions after 20 min into PCL
polymers with a narrow molecular weight distribution (Table 5,
runs 1 and 4–6). The OR/"-CL unit ratios in polymers deter-
mined by end-group analysis of the 1H NMR spectra are close
to the starting monomer/initiator ratios. These facts confirm
the living character of the ROP initiated by different BHT–
Mg–OR complexes with sterically unhindered initiators. In the
References
Arai, T., Sasai, H., Yamaguchi, K. & Shibasaki, M. (1998). J. Am.
Chem. Soc. 120, 441–442.
Boyle, T. J., Alam, T. M., Bunge, S. D., Segall, J. M., Avilucea, G. R.,
Tissot, R. G. & Rodriguez, M. A. (2005). Organometallics, 24, 731–
737.
Boyle, T. J., Bunge, S. D., Andrews, N. L., Matzen, L. E., Sieg, K.,
Rodriguez, M. A. & Headley, T. J. (2004). Chem. Mater. 16, 3279–
3288.
t
case of BuOH activation, we observed low catalyst activity
(Table 5, run 2) and the final formation of a high molecular
mass polymer with a higher polydispersity index (ÐM) (Table 5,
run 3). Presumably, the relatively low activity at the initial
stage of polymerization (compare runs 2 and 3) is addressed
by the difference between the initiation and propagation rates
that leads to a broadening of the molecular weight distribution
of PCL and to a deviation between the theoretical and
experimental Mn values. The same effect was observed earlier
for the ROP of lactide initiated by unreactive phenolate and
hydroxyamide BHT–Mg complexes (Nifant’ev et al., 2017d).
Catalysts (2) and (3) demonstrated moderate activity, with the
formation of poly("-CL) having relatively broad molecular
weight distributions (Table 5, runs 7–9); theoretical molecular
weights do not correlate with Mn determined by GPC.
Bruker (2008). SMART and SAINT. Bruker AXS Inc., Madison,
Wisconsin, USA.
Charette, A., Beauchemin, A., Francoeur, S., Belanger-Gariepy, F. &
Enright, G. D. (2002). Chem. Commun. pp. 466–467.
Chen, H.-Y., Mialon, L., Abboud, K. A. & Miller, S. A. (2012).
Organometallics, 31, 5252–5261.
Dagorne, S., Le Bideau, F., Welter, R., Bellemin-Laponnaz, S. &
Maisse-Franc¸ois, A. (2007). Chem. Eur. J. 13, 3202–3217.
Devaine-Pressing, K., Lehr, J. H., Pratt, M. E., Dawe, L. N., Sarjeant,
A. A. & Kozak, C. M. (2015). Dalton Trans. 44, 12365–12375.
Dubois, P., Coulembier, O. & Raquez, J.-M. (2009). Handbook of
ring-opening polymerization, pp. 1–408. Weinheim: Wiley-VCH.
Fang, Y., Gong, W., Liu, L., Liu, Y. & Cui, Y. (2016). Inorg. Chem. 55,
10102–10105.
Fang, H.-J., Lai, P.-S., Chen, J.-Y., Hsu, S. C. N., Peng, W.-D., Ou, S.-W.,
Lai, Y.-C., Chen, Y.-J., Chung, H., Chen, Y., Huang, T.-C., Wu, B.-S.
& Chen, H.-Y. (2012). J. Polym. Sci. Part A Polym. Chem. 50, 2697–
2704.
Ghosh, S., Chakraborty, D. & Ramkumar, V. (2015). J. Polym. Sci.
Part A Polym. Chem. 53, 1474–1491.
Graves, C. R., Zhou, H., Stern, C. L. & Nguyen, S. T. (2007). J. Org.
Chem. 72, 9121–9133.
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta
Cryst. B72, 171–179.
Ishimori, M., Hagiwara, T., Tsuruta, T., Kai, Y., Yasuoka, N. & Kasai,
N. (1976). Bull. Chem. Soc. Jpn, 49, 1165–1166.
Ivchenko, P. V., Shlyakhtin, A. V. & Nifant’ev, I. E. (2017). Mendeleev
Commun. 27, 278–280.
4. Concluding remarks
The structure of a new packing polymorph of Mg(BHT)2-
(THF)2 has been determined. Formed in situ, its BHT–Mg
derivatives from reactions with various ROH alcohols [iPrOH,
tBuOH, tBuCH2OH, cholesterol and a bis(cyclohexyl)-
protected furanose form of glucose] have demonstrated
catalytic activity in the ROP of "-CL, providing poly-"-
caprolactone with corresponding OR terminal groups and a
narrow molecular weight distribution. This proves the idea of
the formation of the Mgx(BHT)y(OR)2x–y complexes in THF,
which are yet to be studied. The structure of the new dimeric
complex [(BHT)AlMe(OCH2COOEt)]2 contains a rather
common Al2O2 rhomboid core and a five-membered Al–O–
C–C–O heterocycle due to the ꢁ2-ꢀ2O,O0:ꢀO semi-bridging
coordination mode of the ethyl glycolate ligand. The structure
of [Zn7(C2H5)6(ꢁ3-OCH2Ph)8], possessing a bicubic Zn7O8
core, has been redetermined, which resulted in a better crys-
tallographic model than that published previously. The Al and
Zn complexes formed in situ have moderate activity in "-
caprolactone polymerization.
¨
Jana, S., Berger, R. J. F., Frohlich, R., Pape, T. & Mitzel, N. W. (2007).
Inorg. Chem. 46, 4293–4297.
Kan, C., Ge, J. & Ma, H. (2016). Dalton Trans. 45, 6682–6695.
Karpiniec, S. S., McGuinness, D. S., Gardiner, M. G., Yates, B. F. &
Patel, J. (2011). Organometallics, 30, 1569–1576.
Klitzke, J. S., Roisnel, T., Kirillov, E., Casagrande, O. de L. Jr &
Carpentier, J.-F. (2014). Organometallics, 33, 5693–5707.
´
Lewinski, J., Marciniak, W., Lipkowski, J. & Justyniak, I. (2003). J.
Am. Chem. Soc. 125, 12698–12699.
Lewinski, J., Suwala, K., Kubisiak, M., Ochal, Z., Justyniak, I. &
Lipkowski, J. (2008). Angew. Chem. Int. Ed. 47, 7888–7891.
Li, C.-Y., Chen, P.-S., Hsu, S.-J., Lin, C.-H., Huang, H.-Y. & Ko, B.-T.
(2012). J. Organomet. Chem. 716, 175–181.
Li, Q., Nie, K., Xu, B., Yao, Y., Zhang, Y. & Shen, Q. (2012).
Polyhedron, 31, 58–63.
Liu, Y., Xi, X., Ye, C., Gong, T., Yang, Z. & Cui, Y. (2014). Angew.
Chem. Int. Ed. 53, 13821–13826.
Martinez, G., Pedrosa, S., Tabernero, V., Mosquera, M. E. G. &
Cuenca, T. (2008). Organometallics, 27, 2300–2305.
Minyaev, M. E., Churakov, A. V. & Nifant’ev, I. E. (2017). Acta Cryst.
C73, 854–861.
Acknowledgements
This work was supported by the Russian Science Foundation
(design and synthesis of the catalysts and polymers, X-ray
ꢀ
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research papers
Nifant’ev, I. E., Ivchenko, P. V., Shlyakhtin, A. V. & Ivanyuk, A. V.
(2017a). Polym. Sci. Ser. B, 59, 147–156.
Save, M., Schappacher, M. & Soum, A. (2002). Macromol. Chem.
Phys. 203, 889–899.
Nifant’ev, I. E., Minyaev, M. E., Shlyakhtin, A. V., Ivchenko, P. V. &
Churakov, A. V. (2017b). Mendeleev Commun. 27, 341–343.
Nifant’ev, I. E., Shlyakhtin, A. V., Bagrov, V. V., Komarov, P. D.,
Kosarev, M. A., Tavtorkin, A. N., Minyaev, M. E., Roznyatovsky, V.
A. & Ivchenko, P. V. (2017c). Polym. Chem. 8, 6806–6816.
Nifant’ev, I. E., Shlyakhtin, A. V., Bagrov, V. V., Komarov, P. D.,
Kosarev, M. A., Tavtorkin, A. N., Minyaev, M. E., Roznyatovsky,
V. A. & Ivchenko, P. V. (2018). Mendeleev Commun. 28, 155–157.
Nifant’ev, I. E., Shlyakhtin, A. V., Bagrov, V. V., Minyaev, M. E.,
Churakov, A. V., Karchevsky, S. G., Birin, K. P. & Ivchenko, P. V.
(2017d). Dalton Trans. 46, 12132–12146.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sheldrick, G. M. (2015a). Acta Cryst. C71, 3–8.
Sheldrick, G. M. (2015b). Acta Cryst. A71, 3–8.
Sun, Y., Wang, L., Yu, D., Tang, N. & Wu, J. (2014). J. Mol. Catal. A
Chem. 393, 175–181.
Tang, Z., Pang, X., Sun, J., Du, H., Chen, X., Wang, X. & Jing, X.
(2006). J. Polym. Sci. Part A Polym. Chem. 44, 4932–4936.
Wheaton, C. A., Hayes, P. G. & Ireland, B. J. (2009). Dalton Trans. pp.
4832–4846.
Wilson, J. A., Hopkins, S. A., Wright, P. M. & Dove, A. P. (2014).
Polym. Chem. 5, 2691–2694.
Nifant’ev, I. E., Shlyakhtin, A. V., Tavtorkin, A. N., Ivchenko, P. V.,
Borisov, R. S. & Churakov, A. V. (2016). Catal. Commun. 87, 106–
111.
Nomura, N., Ishii, R., Yamamoto, Y. & Kondo, T. (2007). Chem. Eur.
J. 13, 4433–4451.
Wilson, J. A., Hopkins, S. A., Wright, P. M. & Dove, A. P. (2015).
Macromolecules, 48, 950–958.
Zevaco, T. A., Sypien, J. K., Janssen, A., Walter, O. & Dinjus, E.
(2007). J. Organomet. Chem. 692, 1963–1973.
Zhang, J., Xiong, J., Sun, Y., Tang, N.
Macromolecules, 47, 7789–7796.
& Wu, J. (2014).
¨
Polarz, S., Neues, F., van den Berg, M. W. E., Grunert, W. & Khodeir,
L. (2005). J. Am. Chem. Soc. 127, 12028–12034.
Ziegler, M. L. & Weiss, J. (1970). Angew. Chem. Int. Ed. 9, 905–
906.
Ziemkowska, W., Zuk, P., Cyranski, M. K. & Kunicki, A. (2011). J.
Mol. Struct. 1006, 606–610.
Redshaw, C., Jana, S., Shang, C., Elsegood, M. R. J., Lu, X. & Guo,
Z. X. (2010). Chem. Commun. 46, 9055–9057.
Sarazin, Y. & Carpentier, J.-F. (2015). Chem. Rev. 115, 3564–3614.
ꢀ
Acta Cryst. (2018). C74, 548–557
Minyaev et al.
Ring-opening polymerization of "-caprolactone 557

supporting information
supporting information
Acta Cryst. (2018). C74, 548-557 [https://doi.org/10.1107/S2053229618005090]
Phenoxide and alkoxide complexes of Mg, Al and Zn, and their use for the ring-
opening polymerization of ∊-caprolactone with initiators of different natures
Mikhail E. Minyaev, Ilya E. Nifant'ev, Andrey V. Shlyakhtin, Pavel V. Ivchenko and Konstantin A.
Lyssenko
Computing details
For all structures, data collection: APEX2 (Bruker, 2008). Cell refinement: APEX2 (Bruker, 2008) for Mg; SAINT
(Bruker, 2008) for Al, Zn. Data reduction: APEX2 (Bruker, 2008) for Mg; SAINT (Bruker, 2008) for Al, Zn. For all
structures, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure:
SHELXL2017 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for
publication: SHELXTL (Sheldrick, 2008).
Bis(2,6-di-tert-butyl-4-methylphenolato-κO)bis(tetrahydrofuran-κO)magnesium (Mg)
Crystal data
[Mg(C15H23O)2(C4H8O)2]
Mr = 607.18
F(000) = 2004
Dx = 1.099 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 999 reflections
θ = 3–25°
Monoclinic, P21
a = 16.847 (3) Å
b = 15.6786 (18) Å
c = 21.787 (2) Å
β = 106.954 (4)°
V = 5504.9 (12) Å3
Z = 6
µ = 0.08 mm−1
T = 120 K
Block, colourless
0.48 × 0.40 × 0.37 mm
Data collection
Bruker SMART APEXII
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
ω scans
69149 measured reflections
29225 independent reflections
20602 reflections with I > 2σ(I)
Rint = 0.036
θ
max = 29.0°, θmin = 1.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = −22→22
k = −21→21
l = −29→29
T
min = 0.951, Tmax = 0.975
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.047
wR(F2) = 0.122
S = 0.98
29225 reflections
1238 parameters
17 restraints
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0599P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Acta Cryst. (2018). C74, 548-557
sup-1

supporting information
Δρmax = 0.27 e Å−3
Δρmin = −0.20 e Å−3
Absolute structure: Refined as an inversion twin
Absolute structure parameter: 0.07 (15)
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. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Refined as a 2-component inversion twin.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Occ. (<1)
Mg1
O1A
C1A
C2A
C3A
H3A
C4A
C5A
H5A
C6A
C7A
0.17592 (5)
0.20462 (10)
0.22385 (13)
0.19674 (14)
0.21622 (14)
0.196822
0.26265 (14)
0.29009 (14)
0.322360
0.27261 (14)
0.14616 (17)
0.06190 (17)
0.032959
0.27788 (5)
0.21640 (10)
0.16511 (15)
0.07843 (15)
0.02827 (15)
−0.028928
0.05811 (15)
0.14227 (15)
0.163535
0.19696 (14)
0.03859 (16)
0.0843 (2)
0.081997
0.09003 (4)
0.16622 (7)
0.21712 (10)
0.21239 (11)
0.26792 (11)
0.264581
0.32782 (11)
0.33133 (11)
0.371735
0.27851 (11)
0.14826 (11)
0.12368 (13)
0.156681
0.01458 (16)
0.0186 (3)
0.0147 (4)
0.0174 (5)
0.0178 (5)
0.021*
0.0175 (5)
0.0185 (5)
0.022*
0.0160 (5)
0.0264 (6)
0.0368 (7)
0.055*
C8A
H8A
H8B
0.028188
0.055973
0.084668
0.055*
H8C
0.070930
0.143925
0.114053
0.055*
C9A
H9A
H9B
0.1283 (2)
0.094656
0.180842
0.098154
0.19456 (19)
0.209079
0.159990
0.245345
0.28155 (16)
0.263464
0.252041
−0.05665 (18)
−0.063019
−0.087349
−0.080170
0.04316 (16)
0.102612
0.020668
0.009095
0.00094 (16)
−0.057335
0.021825
0.15546 (13)
0.185034
0.172454
0.113461
0.09819 (12)
0.092667
0.057111
0.112964
0.38607 (11)
0.372745
0.415765
0.0417 (8)
0.063*
0.063*
0.063*
0.0322 (7)
0.048*
0.048*
0.048*
0.0233 (5)
0.035*
0.035*
H9C
C10A
H10A
H10B
H10C
C11A
H11A
H11B
H11C
C12A
C13A
H13A
H13B
H13C
0.341403
0.001234
0.407510
0.035*
0.30524 (14)
0.35577 (17)
0.377356
0.402133
0.319862
0.28902 (15)
0.30896 (17)
0.367312
0.268783
0.303435
0.28699 (11)
0.35697 (12)
0.359530
0.370790
0.384956
0.0190 (5)
0.0295 (6)
0.044*
0.044*
0.044*
Acta Cryst. (2018). C74, 548-557
sup-2

supporting information
C14A
H14A
H14B
H14C
C15A
H15A
H15B
H15C
O2A
0.23293 (16)
0.198484
0.255079
0.199221
0.36377 (15)
0.333225
0.35324 (16)
0.343431
0.411434
0.345716
0.30458 (16)
0.296225
0.27005 (12)
0.225895
0.273987
0.299494
0.24538 (12)
0.200064
0.0246 (6)
0.037*
0.037*
0.037*
0.0249 (6)
0.037*
0.410231
0.385083
0.264332
0.363076
0.257730
0.251878
0.037*
0.037*
0.17724 (10)
0.18788 (14)
0.11733 (14)
0.12829 (15)
0.081180
0.20528 (15)
0.27348 (15)
0.326520
0.26779 (14)
0.03165 (14)
−0.00309 (15)
0.034914
−0.008860
−0.057501
−0.03380 (15)
−0.015008
−0.086738
−0.041135
0.03941 (17)
0.080095
−0.014601
0.057683
0.21425 (17)
0.266248
0.214861
0.167419
0.35116 (13)
0.3468 (2)
0.316927
0.403184
0.317621
0.23572 (10)
0.17449 (14)
0.14383 (14)
0.07743 (15)
0.056485
0.04013 (15)
0.07282 (14)
0.048810
0.13970 (14)
0.18638 (15)
0.17668 (17)
0.203499
0.115981
0.204378
0.14667 (18)
0.151933
0.176639
0.086257
0.28087 (17)
0.308929
0.308890
0.284951
−0.03141 (17)
−0.062106
−0.007424
−0.070893
0.17313 (13)
0.2298 (2)
0.282518
0.01027 (7)
−0.02957 (10)
−0.07949 (10)
−0.11847 (11)
−0.150529
−0.11268 (11)
−0.06606 (11)
−0.062083
−0.02450 (10)
−0.09245 (11)
−0.03510 (11)
0.002813
−0.026565
−0.044903
−0.15050 (11)
−0.188877
−0.157467
−0.141965
−0.10896 (12)
−0.073141
−0.116612
−0.147641
−0.15714 (12)
−0.137934
−0.198533
−0.163647
0.02010 (10)
0.07634 (15)
0.059762
0.0178 (3)
0.0142 (4)
0.0161 (5)
0.0186 (5)
0.022*
0.0207 (5)
0.0186 (5)
0.022*
0.0160 (5)
0.0187 (5)
0.0254 (6)
0.038*
0.038*
0.038*
0.0272 (6)
0.041*
0.041*
0.041*
0.0282 (6)
0.042*
0.042*
0.042*
0.0273 (6)
0.041*
0.041*
0.041*
0.0170 (5)
0.0265 (7)
0.040*
0.040*
0.040*
0.0284 (8)
0.043*
0.043*
0.043*
0.0341 (9)
0.051*
0.051*
C16A
C17A
C18A
H18A
C19A
C20A
H20A
C21A
C22A
C23A
H23A
H23B
H23C
C24A
H24A
H24B
H24C
C25A
H25A
H25B
H25C
C26A
H26A
H26B
H26C
C27A
C28A
H28A
H28B
H28C
C29A
H29A
H29B
H29C
C30A
H30A
H30B
H30C
C28B
0.741 (3)
0.741 (3)
0.741 (3)
0.741 (3)
0.741 (3)
0.741 (3)
0.741 (3)
0.741 (3)
0.741 (3)
0.741 (3)
0.741 (3)
0.741 (3)
0.259 (3)
0.243815
0.199438
0.0971 (2)
0.064573
0.060124
0.118092
0.2227 (2)
0.185364
0.242822
0.271734
0.102642
0.102586
0.05057 (17)
0.017009
0.072372
0.4064 (2)
0.421046
0.376229
0.457078
0.3935 (2)
0.400583
0.447886
0.359037
0.3593 (6)
0.081717
−0.02217 (17)
−0.056247
0.004032
−0.041369
0.0920 (2)
0.051*
0.0265 (7)
0.1647 (7)
Acta Cryst. (2018). C74, 548-557
sup-3

supporting information
H28D
H28E
H28F
C29B
H29D
H29E
H29F
C30B
H30D
H30E
H30F
O3A
C31A
H31A
H31B
C32A
H32A
H32B
C33A
H33A
H33B
C34A
H34A
H34B
O4A
C35A
H35A
H35B
C36A
H36A
H36B
C37A
H37A
H37B
C38A
H38A
H38B
Mg2
0.413099
0.355170
0.314665
0.4315 (4)
0.436230
0.430288
0.479305
0.3625 (7)
0.362193
0.415471
0.187343
0.104464
0.196938
0.1327 (6)
0.143696
0.071050
0.157661
0.2680 (3)
0.274944
0.288303
0.117225
0.102665
0.101854
0.0137 (5)
−0.029349
0.020722
0.040*
0.040*
0.040*
0.0284 (8)
0.043*
0.043*
0.043*
0.0341 (9)
0.051*
0.051*
0.259 (3)
0.259 (3)
0.259 (3)
0.259 (3)
0.259 (3)
0.259 (3)
0.259 (3)
0.259 (3)
0.259 (3)
0.259 (3)
0.259 (3)
0.045780
0.0065 (5)
−0.038218
0.035032
0.316975
0.301170
0.014199
0.051*
0.21528 (10)
0.22131 (17)
0.272203
0.172627
0.22412 (17)
0.281599
0.188751
0.19046 (17)
0.129032
0.211663
0.22418 (18)
0.191799
0.39920 (10)
0.47038 (15)
0.465192
0.471146
0.55161 (15)
0.573289
0.596714
0.52283 (16)
0.523285
0.559228
0.43306 (16)
0.398803
0.08075 (8)
0.12539 (12)
0.162049
0.142119
0.08740 (12)
0.096614
0.097496
0.01743 (12)
0.002905
−0.011447
0.02059 (12)
−0.016430
0.021086
0.09549 (8)
0.04862 (13)
0.005186
0.059623
0.05082 (14)
0.009674
0.059604
0.10549 (14)
0.131510
0.088860
0.14453 (13)
0.173569
0.0204 (4)
0.0254 (6)
0.030*
0.030*
0.0252 (6)
0.030*
0.030*
0.0276 (6)
0.033*
0.033*
0.0278 (6)
0.033*
0.283127
0.433435
0.033*
0.06468 (10)
0.00794 (16)
0.013287
0.32664 (11)
0.38130 (18)
0.370900
0.442112
0.3588 (2)
0.333430
0.410156
0.2943 (2)
0.305157
0.235172
0.3098 (2)
0.359261
0.0223 (4)
0.0294 (6)
0.035*
0.035*
0.0354 (7)
0.042*
0.042*
0.0395 (7)
0.047*
0.047*
0.0309 (6)
0.037*
0.020174
−0.07942 (16)
−0.112361
−0.108563
−0.06624 (17)
−0.104540
−0.074344
0.02379 (16)
0.028414
0.047659
0.258875
0.170227
0.037*
0.48928 (5)
0.46410 (10)
0.44362 (14)
0.39177 (14)
0.37384 (15)
0.339640
0.40371 (15)
0.45252 (15)
0.472451
0.78096 (5)
0.71592 (10)
0.66282 (15)
0.69130 (14)
0.63517 (15)
0.654603
0.55210 (15)
0.52463 (15)
0.467613
0.24224 (3)
0.16788 (7)
0.11796 (11)
0.05679 (11)
0.00495 (11)
−0.035416
0.00962 (11)
0.06924 (11)
0.073329
0.01475 (17)
0.0176 (3)
0.0163 (5)
0.0159 (5)
0.0203 (5)
0.024*
0.0208 (5)
0.0217 (5)
0.026*
O1C
C1C
C2C
C3C
H3G
C4C
C5C
H5G
C6C
C7C
0.47381 (15)
0.35692 (15)
0.57710 (15)
0.78313 (15)
0.12375 (11)
0.04690 (11)
0.0194 (5)
0.0196 (5)
Acta Cryst. (2018). C74, 548-557
sup-4

supporting information
C8C
H8G
0.42852 (17)
0.405763
0.84818 (16)
0.906143
0.06002 (13)
0.055018
0.0283 (6)
0.042*
H8H
0.460480
0.839128
0.029519
0.042*
H8I
0.464843
0.840627
0.103876
0.042*
C9C
H9H
0.30162 (15)
0.279878
0.79980 (16)
0.858120
0.09097 (12)
0.084301
0.0238 (5)
0.036*
H9I
0.334519
0.792613
0.135860
0.036*
H9J
0.255344
0.759251
0.080735
0.036*
C10C
H10G
H10H
H10I
C11C
H11G
H11H
H11I
C12C
C13C
H13G
H13H
H13I
C14C
H14G
H14H
H14I
C15C
H15G
H15H
H15I
O2C
C16C
C17C
C18C
H18G
C19C
C20C
H20G
C21C
C22C
C23C
H23G
H23H
H23I
C24C
H24G
H24H
H24I
C25C
0.30240 (17)
0.280329
0.256343
0.335803
0.38602 (16)
0.327366
0.398563
0.420697
0.53072 (17)
0.5520 (2)
0.500642
0.586901
0.581861
0.61309 (16)
0.638984
0.650543
0.602021
0.48823 (18)
0.437704
0.473783
0.526164
0.47794 (9)
0.47035 (14)
0.39140 (14)
0.38813 (15)
0.335976
0.45755 (16)
0.53330 (16)
0.581132
0.54191 (14)
0.30943 (13)
0.23198 (16)
0.231738
0.232852
0.182027
0.29958 (18)
0.299002
0.247358
0.79911 (18)
0.857319
0.758303
0.791893
0.49366 (16)
0.498243
0.434634
0.510308
0.54106 (17)
0.44641 (19)
0.412949
0.425656
0.440423
0.5913 (2)
0.588816
0.566075
0.650873
0.54488 (16)
0.510105
0.604116
0.522854
0.73893 (10)
0.67951 (14)
0.64271 (14)
0.57683 (15)
0.551144
0.54732 (16)
0.58659 (16)
0.567793
0.65251 (15)
0.67441 (13)
0.63238 (19)
0.641635
0.571025
0.657717
0.77083 (16)
0.782245
0.790418
−0.02220 (12)
−0.025738
−0.032978
−0.051894
−0.04824 (11)
−0.072873
−0.033868
−0.075371
0.18729 (12)
0.18130 (14)
0.168149
0.222826
0.149106
0.20685 (12)
0.172034
0.245734
0.215211
0.24100 (12)
0.228893
0.247338
0.280932
0.31926 (7)
0.36146 (10)
0.35805 (10)
0.40066 (11)
0.397360
0.44750 (12)
0.45229 (11)
0.484673
0.41145 (10)
0.31074 (10)
0.32136 (14)
0.365790
0.0314 (6)
0.047*
0.047*
0.047*
0.0251 (6)
0.038*
0.038*
0.038*
0.0275 (6)
0.0479 (9)
0.072*
0.072*
0.072*
0.0346 (7)
0.052*
0.052*
0.052*
0.0305 (6)
0.046*
0.046*
0.046*
0.0168 (3)
0.0150 (5)
0.0164 (5)
0.0218 (5)
0.026*
0.0250 (6)
0.0236 (5)
0.028*
0.0181 (5)
0.0181 (5)
0.0266 (7)
0.040*
0.040*
0.040*
0.0292 (7)
0.044*
0.044*
0.900 (3)
0.900 (3)
0.900 (3)
0.900 (3)
0.900 (3)
0.900 (3)
0.900 (3)
0.900 (3)
0.900 (3)
0.313007
0.292056
0.31950 (15)
0.363597
0.289490
0.346098
0.30562 (17)
0.801241
0.6559 (2)
0.311012
0.24079 (11)
0.044*
0.0272 (7)
Acta Cryst. (2018). C74, 548-557
sup-5

supporting information
H25G
H25H
H25I
C23D
H23J
H23K
H23L
C24D
H24J
H24K
H24L
C25D
H25J
H25K
H25L
C26C
H26G
H26H
H26I
C27C
C28C
H28G
H28H
H28I
0.253017
0.309492
0.351911
0.2645 (14)
0.249378
0.301363
0.214284
0.3147 (16)
0.258750
0.348517
0.340108
0.2602 (14)
0.217462
0.233742
0.297900
0.45155 (19)
0.398358
0.455331
0.677040
0.594198
0.684462
0.7197 (15)
0.777570
0.722441
0.687793
0.7228 (15)
0.730359
0.690161
0.778799
0.5948 (10)
0.610907
0.569474
0.553119
0.47610 (19)
0.446515
0.500201
0.435616
0.69677 (16)
0.6616 (2)
0.693278
0.601060
0.212290
0.234846
0.230571
0.3537 (10)
0.337591
0.397716
0.353078
0.2507 (8)
0.221260
0.229254
0.263247
0.2804 (11)
0.240919
0.310630
0.270281
0.49314 (13)
0.476433
0.535398
0.497039
0.42256 (11)
0.48195 (12)
0.488076
0.475412
0.520029
0.041*
0.041*
0.041*
0.0266 (7)
0.040*
0.040*
0.040*
0.0292 (7)
0.044*
0.044*
0.044*
0.0272 (7)
0.041*
0.041*
0.041*
0.0368 (7)
0.055*
0.055*
0.900 (3)
0.900 (3)
0.900 (3)
0.100 (3)
0.100 (3)
0.100 (3)
0.100 (3)
0.100 (3)
0.100 (3)
0.100 (3)
0.100 (3)
0.100 (3)
0.100 (3)
0.100 (3)
0.100 (3)
0.497071
0.055*
0.62675 (15)
0.69326 (16)
0.745144
0.702785
0.674039
0.0199 (5)
0.0328 (7)
0.049*
0.049*
0.049*
0.668167
C29C
H29G
H29H
H29I
C30C
H30G
H30H
H30I
0.61635 (16)
0.669418
0.598521
0.574485
0.66154 (15)
0.714853
0.622403
0.669553
0.44741 (10)
0.44378 (17)
0.394523
0.494142
0.43824 (16)
0.380208
0.472967
0.47121 (16)
0.532628
0.449521
0.43757 (17)
0.469546
0.79185 (17)
0.821258
0.798132
0.816834
0.68227 (18)
0.711801
0.704716
0.621051
0.90238 (10)
0.97125 (15)
0.964495
0.970927
1.05433 (16)
1.074749
1.099401
1.02920 (16)
1.029831
1.067349
0.93968 (16)
0.907159
0.940656
0.83053 (11)
0.8176 (2)
0.868559
0.43533 (13)
0.441395
0.474075
0.398669
0.36560 (11)
0.373547
0.326371
0.360544
0.24898 (8)
0.20274 (12)
0.164923
0.188081
0.23796 (13)
0.227461
0.0302 (6)
0.045*
0.045*
0.045*
0.0259 (6)
0.039*
0.039*
0.039*
0.0208 (4)
0.0259 (6)
0.031*
0.031*
0.0284 (6)
0.034*
0.034*
0.0286 (6)
0.034*
0.034*
0.0259 (6)
0.031*
O3C
C31C
H31G
H31H
C32C
H32G
H32H
C33C
H33G
H33H
C34C
H34G
H34H
O4C
0.227007
0.30870 (13)
0.323604
0.336267
0.30778 (12)
0.345937
0.378439
0.306751
0.031*
0.60087 (10)
0.63864 (16)
0.631805
0.23673 (8)
0.18536 (13)
0.157454
0.0224 (4)
0.0319 (7)
0.038*
C35C
H35G
Acta Cryst. (2018). C74, 548-557
sup-6

supporting information
H35H
C36C
H36G
H36H
C37C
H37G
H37H
C38C
H38G
H38H
Mg3
O1E
C1E
C2E
C3E
H3M
C4E
C5E
H5M
C6E
C7E
0.614449
0.72996 (18)
0.739823
0.766309
0.74501 (17)
0.775005
0.777874
0.65845 (16)
0.654455
0.767490
0.8026 (2)
0.742552
0.817193
0.8625 (2)
0.914323
0.833832
0.88518 (18)
0.874530
0.158840
0.22180 (15)
0.235911
0.194897
0.27908 (14)
0.272350
0.318864
0.28313 (13)
0.326919
0.038*
0.0446 (8)
0.053*
0.053*
0.0372 (7)
0.045*
0.045*
0.0290 (6)
0.035*
0.646008
0.946030
0.272419
0.035*
0.84127 (5)
0.84189 (10)
0.85372 (14)
0.93401 (14)
0.94041 (15)
0.993735
0.87273 (16)
0.79523 (15)
0.748367
0.78389 (14)
1.01802 (14)
1.06339 (18)
1.116508
0.26654 (5)
0.22858 (10)
0.17093 (14)
0.13763 (14)
0.07375 (15)
0.050991
0.04224 (16)
0.07789 (15)
0.057998
0.14151 (14)
0.16896 (15)
0.21803 (19)
0.239275
0.42775 (3)
0.34672 (7)
0.30520 (10)
0.30924 (10)
0.26562 (11)
0.268852
0.21804 (11)
0.21307 (11)
0.180258
0.25435 (10)
0.35449 (11)
0.31366 (14)
0.341317
0.01572 (19)
0.0174 (3)
0.0144 (4)
0.0161 (5)
0.0196 (5)
0.023*
0.0223 (5)
0.0206 (5)
0.025*
0.0167 (5)
0.0177 (5)
0.0345 (7)
0.052*
C8E
H8M
H8N
1.029152
0.266223
0.292562
0.052*
H8O
1.073427
0.179861
0.281087
0.052*
C9E
H9M
H9N
1.01425 (16)
1.070720
0.986078
0.22701 (19)
0.241981
0.197097
0.41014 (13)
0.435626
0.437336
0.0314 (6)
0.047*
0.047*
H9O
0.983550
0.279081
0.393051
0.047*
C10E
H10M
H10N
H10O
C11E
H11M
H11N
H11O
C12E
C13E
H13M
H13N
H13O
C14E
H14M
H14N
H14O
C15E
H15M
1.07265 (16)
1.123870
1.086349
1.042555
0.88206 (17)
0.933153
0.884715
0.834343
0.69729 (14)
0.63240 (15)
0.579020
0.626031
0.650972
0.66347 (15)
0.701295
0.658921
0.608590
0.70275 (17)
0.742848
0.09300 (17)
0.114087
0.059101
0.38563 (13)
0.416091
0.352319
0.408357
0.17243 (12)
0.191831
0.132056
0.163927
0.24325 (11)
0.18378 (11)
0.178066
0.189906
0.145647
0.30041 (11)
0.339175
0.306631
0.291953
0.23043 (13)
0.267271
0.0299 (6)
0.045*
0.045*
0.045*
0.0301 (6)
0.045*
0.045*
0.045*
0.0195 (5)
0.0280 (6)
0.042*
0.042*
0.042*
0.0262 (6)
0.039*
0.039*
0.039*
0.0323 (6)
0.048*
0.057378
−0.02746 (18)
−0.059543
−0.001827
−0.066087
0.18177 (15)
0.14472 (18)
0.173350
0.083457
0.153859
0.16605 (18)
0.191144
0.104535
0.192403
0.27782 (17)
0.304564
Acta Cryst. (2018). C74, 548-557
sup-7

supporting information
H15N
H15O
O2E
0.648102
0.720762
0.304032
0.286014
0.223909
0.191933
0.048*
0.048*
0.87487 (10)
0.89840 (14)
0.94776 (14)
0.96889 (14)
1.002005
0.94358 (14)
0.89729 (14)
0.879765
0.87520 (14)
0.97575 (15)
0.89988 (17)
0.868339
0.864511
0.918411
1.03031 (16)
1.049302
0.997910
1.078435
1.02830 (18)
0.995160
1.045773
1.077395
0.96306 (16)
0.950470
0.929362
0.20255 (10)
0.14983 (14)
0.18083 (14)
0.12492 (15)
0.145701
0.04003 (15)
0.01044 (15)
−0.047409
0.06160 (15)
0.27471 (15)
0.33385 (16)
0.321102
0.324800
0.393368
0.29726 (16)
0.356433
0.290598
0.259080
0.29358 (17)
0.282597
0.353446
0.256692
−0.01719 (16)
−0.076443
−0.000176
−0.012133
0.02167 (16)
−0.07489 (17)
−0.085375
−0.102739
−0.098090
0.03319 (16)
0.094098
0.50252 (7)
0.55264 (10)
0.61378 (11)
0.66584 (11)
0.706138
0.66137 (11)
0.60160 (11)
0.597842
0.54666 (11)
0.62351 (11)
0.61012 (13)
0.640350
0.566137
0.615320
0.58007 (12)
0.587889
0.534999
0.589671
0.69287 (12)
0.722269
0.696339
0.704097
0.71948 (11)
0.705770
0.747263
0.0193 (4)
0.0156 (5)
0.0164 (5)
0.0180 (5)
0.022*
0.0180 (5)
0.0178 (5)
0.021*
0.0174 (5)
0.0195 (5)
0.0284 (6)
0.043*
0.043*
0.043*
0.0252 (5)
0.038*
0.038*
0.038*
0.0309 (6)
0.046*
0.046*
0.046*
0.0250 (6)
0.037*
0.037*
C16E
C17E
C18E
H18M
C19E
C20E
H20M
C21E
C22E
C23E
H23M
H23N
H23O
C24E
H24M
H24N
H24O
C25E
H25M
H25N
H25O
C26E
H26M
H26N
H26O
C27E
C28E
H28M
H28N
H28O
C29E
H29M
H29N
H29O
C30E
H30M
H30N
H30O
O3E
1.022022
0.743179
0.037*
0.82595 (15)
0.81384 (19)
0.782310
0.868140
0.783366
0.87288 (17)
0.881830
0.840185
0.926583
0.73893 (16)
0.710516
0.706663
0.744343
0.72870 (10)
0.69061 (17)
0.698848
0.713461
0.726779
0.681833
0.60041 (19)
0.48212 (11)
0.48802 (12)
0.518624
0.503210
0.445985
0.43195 (11)
0.426343
0.390972
0.446509
0.45858 (13)
0.491673
0.419136
0.449982
0.43645 (8)
0.48615 (14)
0.518373
0.508047
0.528618
0.487236
0.44951 (19)
0.0227 (5)
0.0344 (7)
0.052*
0.052*
0.052*
0.0254 (6)
0.038*
0.038*
0.038*
0.0353 (7)
0.053*
0.053*
0.053*
0.0267 (4)
0.0447 (8)
0.054*
0.054*
0.054*
0.054*
0.0518 (13)
0.008758
0.004061
0.0624 (2)
0.055972
0.033964
0.123149
0.30804 (12)
0.2868 (2)
0.333025
0.233028
0.305021
C31E
H31M
H31N
H31P
H31Q
C32E
0.809 (6)
0.809 (6)
0.191 (6)
0.191 (6)
0.809 (6)
0.224472
0.2772 (3)
Acta Cryst. (2018). C74, 548-557
sup-8

supporting information
H32M
H32N
C32F
H32P
H32Q
C33E
H33M
H33N
H33P
H33Q
C34E
H34M
H34N
O4E
C35E
H35M
H35N
C36E
H36M
H36N
C37E
H37M
H37N
C38E
H38M
H38N
0.564641
0.589055
0.6086 (7)
0.614213
0.566099
0.58647 (19)
0.549235
0.561549
0.562664
0.547602
0.67171 (16)
0.673140
0.686864
0.87436 (11)
0.88202 (18)
0.848767
0.940658
0.84882 (17)
0.787393
0.869488
0.88378 (17)
0.941683
0.286217
0.219956
0.3330 (12)
0.388267
0.298102
0.3462 (3)
0.325667
0.397554
0.294108
0.394513
0.36607 (19)
0.356814
0.477814
0.429683
0.4705 (3)
0.493401
0.482031
0.39872 (17)
0.357354
0.412111
0.374721
0.384336
0.39269 (14)
0.348077
0.404695
0.41964 (8)
0.35987 (13)
0.322356
0.359561
0.35929 (13)
0.345485
0.062*
0.062*
0.0518 (13)
0.062*
0.062*
0.0567 (10)
0.068*
0.068*
0.068*
0.068*
0.0344 (7)
0.041*
0.041*
0.0211 (4)
0.0282 (6)
0.034*
0.034*
0.0307 (6)
0.037*
0.037*
0.0290 (6)
0.035*
0.809 (6)
0.809 (6)
0.191 (6)
0.191 (6)
0.191 (6)
0.809 (6)
0.809 (6)
0.191 (6)
0.191 (6)
0.426089
0.39055 (10)
0.42680 (16)
0.393951
0.427443
0.51645 (17)
0.517206
0.554238
0.54225 (16)
0.562697
0.330910
0.42958 (13)
0.438888
0.441030
0.46561 (12)
0.502720
0.481454
0.849637
0.87957 (17)
0.929753
0.587506
0.035*
0.0262 (6)
0.031*
0.45984 (16)
0.453406
0.459822
0.830143
0.031*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Mg1
O1A
C1A
C2A
C3A
C4A
C5A
C6A
C7A
C8A
C9A
C10A
C11A
C12A
C13A
C14A
C15A
O2A
0.0163 (4)
0.0231 (9)
0.0142 (11)
0.0192 (12)
0.0205 (12)
0.0193 (12)
0.0185 (12)
0.0151 (11)
0.0386 (15)
0.0300 (15)
0.072 (2)
0.0144 (4)
0.0186 (8)
0.0172 (11)
0.0179 (11)
0.0155 (11)
0.0168 (11)
0.0206 (12)
0.0167 (11)
0.0224 (13)
0.0477 (18)
0.0289 (15)
0.0168 (12)
0.0219 (12)
0.0177 (11)
0.0247 (14)
0.0187 (12)
0.0237 (13)
0.0154 (8)
0.0133 (4)
0.0145 (8)
0.0142 (11)
0.0156 (12)
0.0186 (12)
0.0178 (12)
0.0161 (12)
0.0174 (11)
0.0155 (12)
0.0248 (15)
0.0199 (14)
0.0202 (13)
0.0159 (12)
0.0185 (12)
0.0201 (13)
0.0251 (14)
0.0281 (14)
0.0148 (8)
−0.0007 (3)
0.0047 (3)
0.0060 (7)
0.0062 (8)
0.0057 (9)
0.0075 (9)
0.0078 (9)
0.0044 (9)
0.0064 (9)
0.0034 (11)
−0.0043 (12)
0.0069 (14)
0.0175 (13)
0.0048 (10)
0.0051 (9)
0.0001 (11)
0.0113 (11)
0.0096 (11)
0.0059 (7)
−0.0021 (3)
0.0003 (7)
0.0001 (9)
−0.0012 (9)
−0.0003 (9)
0.0021 (9)
−0.0027 (9)
−0.0030 (9)
−0.0018 (10)
0.0025 (13)
−0.0047 (12)
−0.0054 (10)
0.0027 (10)
−0.0043 (10)
−0.0071 (11)
−0.0041 (10)
−0.0037 (11)
−0.0023 (6)
−0.0029 (7)
−0.0007 (9)
−0.0044 (10)
−0.0015 (10)
0.0017 (9)
−0.0011 (10)
−0.0027 (9)
−0.0160 (12)
−0.0187 (14)
−0.0302 (16)
−0.0100 (13)
0.0004 (11)
−0.0044 (10)
−0.0099 (12)
0.0005 (11)
−0.0102 (11)
0.0032 (7)
0.063 (2)
0.0309 (14)
0.0204 (12)
0.0382 (16)
0.0320 (14)
0.0240 (13)
0.0236 (8)
Acta Cryst. (2018). C74, 548-557
sup-9

supporting information
C16A
C17A
C18A
C19A
C20A
C21A
C22A
C23A
C24A
C25A
C26A
C27A
C28A
C29A
C30A
C28B
C29B
C30B
O3A
C31A
C32A
C33A
C34A
O4A
C35A
C36A
C37A
C38A
Mg2
0.0210 (11)
0.0210 (12)
0.0220 (12)
0.0257 (13)
0.0220 (12)
0.0203 (12)
0.0194 (12)
0.0223 (13)
0.0213 (13)
0.0315 (14)
0.0333 (15)
0.0157 (11)
0.0154 (15)
0.0207 (17)
0.038 (2)
0.0118 (10)
0.0141 (11)
0.0171 (11)
0.0191 (12)
0.0159 (11)
0.0146 (10)
0.0209 (12)
0.0343 (14)
0.0404 (16)
0.0246 (13)
0.0218 (13)
0.0193 (11)
0.0333 (18)
0.0288 (18)
0.035 (2)
0.0104 (10)
0.0133 (11)
0.0161 (12)
0.0175 (12)
0.0192 (12)
0.0130 (11)
0.0150 (11)
0.0201 (13)
0.0172 (12)
0.0267 (14)
0.0276 (14)
0.0170 (11)
0.0287 (18)
0.031 (2)
0.0004 (9)
0.0005 (9)
0.0055 (9)
0.0053 (9)
0.0047 (9)
0.0068 (10)
0.0082 (10)
0.0047 (9)
0.0039 (9)
0.0070 (10)
0.0018 (10)
0.0056 (11)
0.0102 (11)
0.0063 (9)
0.0034 (13)
−0.0002 (14)
0.0141 (15)
0.0034 (13)
−0.0002 (14)
0.0141 (15)
0.0092 (7)
0.0074 (11)
0.0086 (11)
0.0058 (11)
0.0167 (12)
0.0067 (7)
0.0059 (11)
0.0062 (12)
0.0158 (13)
0.0152 (12)
0.0046 (3)
0.0059 (7)
0.0081 (9)
0.0066 (9)
0.0038 (10)
0.0079 (10)
0.0088 (10)
0.0052 (10)
0.0058 (10)
0.0109 (12)
0.0087 (10)
0.0005 (12)
0.0070 (11)
0.0044 (11)
0.0035 (15)
−0.0008 (11)
0.0109 (12)
0.0054 (6)
0.0080 (9)
0.0060 (9)
0.0006 (8)
0.0018 (9)
−0.0012 (10)
0.0021 (10)
0.0028 (10)
−0.0004 (9)
0.0037 (10)
−0.0018 (11)
0.0031 (12)
0.0101 (12)
0.0015 (12)
0.0011 (10)
−0.0028 (15)
0.0071 (14)
−0.0128 (18)
−0.0028 (15)
0.0071 (14)
−0.0128 (18)
−0.0016 (7)
−0.0029 (11)
0.0001 (11)
−0.0028 (12)
−0.0046 (12)
0.0027 (8)
0.0068 (12)
0.0061 (13)
0.0014 (14)
0.0024 (13)
0.0004 (3)
0.0033 (7)
0.0024 (9)
0.0037 (9)
0.0036 (10)
0.0018 (10)
0.0093 (11)
0.0068 (10)
0.0062 (10)
−0.0022 (11)
0.0095 (10)
0.0118 (12)
0.0035 (11)
0.0166 (12)
0.0370 (17)
0.0196 (14)
0.0074 (13)
−0.0024 (7)
−0.0003 (9)
−0.0017 (9)
−0.0021 (9)
−0.0044 (10)
−0.0009 (9)
0.0002 (9)
−0.0002 (9)
−0.0060 (11)
−0.0044 (11)
0.0064 (11)
−0.0107 (11)
0.0007 (9)
−0.0138 (15)
−0.0033 (14)
0.0017 (16)
−0.0138 (15)
−0.0033 (14)
0.0017 (16)
−0.0019 (7)
−0.0055 (10)
−0.0002 (10)
0.0051 (11)
−0.0014 (11)
−0.0026 (7)
−0.0007 (12)
−0.0097 (14)
−0.0006 (16)
−0.0066 (12)
0.0020 (3)
−0.0006 (6)
0.0004 (9)
0.0042 (9)
0.0001 (10)
−0.0022 (10)
0.0008 (10)
0.0016 (9)
0.0035 (10)
0.0070 (11)
0.0036 (11)
0.0052 (11)
−0.0025 (10)
0.0008 (10)
0.0028 (12)
−0.0010 (12)
0.0048 (10)
0.0022 (6)
0.032 (2)
0.0287 (18)
0.031 (2)
0.0154 (15)
0.0207 (17)
0.038 (2)
0.0333 (18)
0.0288 (18)
0.035 (2)
0.032 (2)
0.0289 (9)
0.0355 (15)
0.0302 (14)
0.0329 (14)
0.0431 (16)
0.0182 (9)
0.0244 (14)
0.0213 (14)
0.0225 (14)
0.0269 (14)
0.0160 (4)
0.0218 (8)
0.0171 (11)
0.0163 (11)
0.0208 (12)
0.0244 (13)
0.0278 (13)
0.0235 (13)
0.0220 (12)
0.0334 (15)
0.0212 (12)
0.0378 (16)
0.0330 (14)
0.0412 (16)
0.079 (2)
0.0150 (8)
0.0159 (12)
0.0160 (12)
0.0229 (13)
0.0208 (13)
0.0284 (9)
0.0282 (14)
0.0423 (17)
0.054 (2)
0.0444 (17)
0.0149 (4)
0.0174 (8)
0.0169 (11)
0.0164 (11)
0.0235 (12)
0.0217 (12)
0.0185 (12)
0.0204 (12)
0.0171 (11)
0.0217 (13)
0.0219 (12)
0.0277 (14)
0.0251 (13)
0.0239 (13)
0.0334 (16)
0.0495 (18)
0.0199 (13)
0.0163 (8)
0.0140 (11)
0.0174 (11)
0.0187 (9)
0.0240 (13)
0.0295 (14)
0.0254 (14)
0.0239 (14)
0.0210 (9)
0.0339 (15)
0.0407 (17)
0.0453 (18)
0.0262 (14)
0.0136 (4)
0.0141 (8)
0.0170 (11)
0.0162 (11)
0.0155 (12)
0.0172 (12)
0.0200 (12)
0.0141 (12)
0.0195 (12)
0.0307 (15)
0.0291 (14)
0.0232 (14)
0.0171 (12)
0.0150 (12)
0.0237 (15)
0.0204 (14)
0.0189 (13)
0.0142 (8)
0.0135 (11)
0.0133 (11)
O1C
C1C
C2C
C3C
C4C
C5C
C6C
C7C
C8C
C9C
C10C
C11C
C12C
C13C
C14C
C15C
O2C
0.0288 (15)
0.0528 (18)
0.0201 (8)
0.0197 (11)
0.0194 (12)
C16C
C17C
−0.0012 (9)
−0.0015 (9)
Acta Cryst. (2018). C74, 548-557
sup-10

supporting information
C18C
C19C
C20C
C21C
C22C
C23C
C24C
C25C
C23D
C24D
C25D
C26C
C27C
C28C
C29C
C30C
O3C
C31C
C32C
C33C
C34C
O4C
C35C
C36C
C37C
C38C
Mg3
0.0244 (13)
0.0321 (14)
0.0285 (14)
0.0218 (12)
0.0151 (11)
0.0206 (14)
0.0221 (15)
0.0186 (14)
0.0206 (14)
0.0221 (15)
0.0186 (14)
0.0446 (17)
0.0187 (12)
0.0246 (14)
0.0256 (14)
0.0209 (13)
0.0271 (9)
0.0333 (14)
0.0267 (14)
0.0273 (14)
0.0305 (14)
0.0183 (9)
0.0274 (15)
0.0245 (15)
0.0223 (14)
0.0239 (13)
0.0174 (4)
0.0203 (12)
0.0231 (13)
0.0251 (13)
0.0210 (12)
0.0211 (12)
0.0304 (15)
0.0202 (15)
0.0451 (19)
0.0304 (15)
0.0202 (15)
0.0451 (19)
0.0333 (16)
0.0242 (13)
0.0518 (19)
0.0309 (15)
0.0372 (15)
0.0149 (8)
0.0165 (12)
0.0154 (12)
0.0226 (13)
0.0205 (13)
0.0273 (10)
0.0454 (17)
0.062 (2)
0.0232 (13)
0.0206 (13)
0.0165 (12)
0.0119 (11)
0.0194 (12)
0.0314 (16)
0.0472 (19)
0.0170 (14)
0.0314 (16)
0.0472 (19)
0.0170 (14)
0.0351 (16)
0.0160 (12)
0.0180 (13)
0.0321 (15)
0.0201 (13)
0.0220 (9)
0.0267 (14)
0.0430 (17)
0.0350 (16)
0.0299 (14)
0.0224 (9)
0.0281 (15)
0.051 (2)
0.0425 (18)
0.0327 (15)
0.0138 (4)
0.0146 (8)
0.0125 (11)
0.0135 (11)
0.0206 (12)
0.0174 (12)
0.0145 (12)
0.0142 (11)
0.0191 (12)
0.0385 (17)
0.0345 (16)
0.0311 (15)
0.0285 (14)
0.0150 (12)
0.0195 (13)
0.0217 (13)
0.0338 (15)
0.0155 (8)
−0.0039 (10)
0.0009 (11)
0.0026 (11)
−0.0014 (10)
−0.0024 (10)
−0.0042 (12)
0.0024 (12)
−0.0049 (13)
−0.0042 (12)
0.0024 (12)
−0.0049 (13)
0.0011 (14)
−0.0009 (10)
−0.0016 (13)
−0.0092 (12)
0.0038 (11)
0.0026 (7)
0.0040 (11)
0.0006 (11)
−0.0017 (11)
0.0028 (11)
−0.0031 (7)
−0.0042 (13)
−0.0040 (15)
−0.0097 (13)
−0.0061 (12)
0.0008 (3)
0.0032 (7)
−0.0001 (9)
0.0014 (9)
0.0051 (10)
0.0016 (11)
−0.0019 (10)
0.0013 (9)
0.0006 (10)
−0.0094 (13)
−0.0036 (12)
0.0036 (12)
0.0009 (12)
0.0044 (10)
0.0024 (12)
−0.0027 (12)
0.0098 (12)
−0.0005 (7)
−0.0007 (9)
−0.0027 (9)
−0.0019 (10)
−0.0003 (10)
0.0108 (10)
0.0092 (11)
0.0054 (10)
0.0054 (9)
0.0070 (9)
0.0118 (12)
0.0130 (13)
0.0037 (11)
0.0118 (12)
0.0130 (13)
0.0037 (11)
0.0158 (13)
0.0038 (9)
−0.0002 (11)
0.0053 (11)
0.0066 (10)
0.0095 (7)
0.0069 (11)
0.0102 (12)
0.0077 (12)
0.0139 (12)
0.0070 (7)
0.0162 (12)
0.0172 (14)
0.0051 (12)
0.0039 (11)
0.0048 (3)
0.0064 (6)
0.0064 (9)
0.0059 (9)
0.0105 (10)
0.0090 (10)
0.0045 (10)
0.0044 (9)
0.0083 (9)
0.0184 (13)
0.0071 (11)
0.0041 (11)
0.0118 (12)
0.0004 (9)
−0.0009 (10)
0.0065 (10)
0.0018 (12)
0.0049 (7)
0.0064 (9)
0.0077 (9)
0.0050 (9)
0.0073 (9)
0.0024 (10)
0.0068 (10)
0.0047 (10)
−0.0019 (9)
0.0000 (10)
0.0024 (13)
0.0010 (13)
−0.0015 (13)
0.0024 (13)
0.0010 (13)
−0.0015 (13)
0.0197 (13)
−0.0010 (10)
0.0039 (13)
−0.0103 (12)
0.0046 (11)
0.0035 (7)
0.0058 (11)
0.0039 (11)
−0.0075 (12)
−0.0018 (11)
0.0015 (7)
0.0057 (13)
−0.0055 (17)
0.0081 (14)
−0.0024 (12)
−0.0022 (3)
−0.0023 (6)
0.0015 (9)
0.0013 (9)
0.0000 (9)
−0.0055 (10)
−0.0030 (9)
0.0026 (9)
0.0005 (10)
0.0030 (13)
−0.0153 (13)
0.0021 (12)
−0.0129 (12)
−0.0007 (9)
−0.0020 (11)
−0.0059 (11)
0.0063 (12)
0.0022 (7)
0.0440 (18)
0.0276 (14)
0.0162 (5)
O1E
C1E
C2E
C3E
C4E
C5E
C6E
C7E
0.0210 (8)
0.0173 (8)
0.0203 (11)
0.0207 (12)
0.0232 (12)
0.0308 (13)
0.0267 (13)
0.0202 (12)
0.0162 (11)
0.0380 (16)
0.0204 (13)
0.0247 (14)
0.0351 (15)
0.0187 (12)
0.0216 (13)
0.0198 (12)
0.0327 (15)
0.0230 (9)
0.0115 (10)
0.0146 (11)
0.0175 (11)
0.0200 (12)
0.0196 (12)
0.0151 (11)
0.0200 (11)
0.0314 (15)
0.0389 (16)
0.0313 (15)
0.0284 (14)
0.0219 (12)
0.0385 (16)
0.0375 (15)
0.0254 (14)
0.0190 (9)
C8E
C9E
C10E
C11E
C12E
C13E
C14E
C15E
O2E
C16E
C17E
C18E
C19E
0.0151 (11)
0.0173 (11)
0.0195 (12)
0.0212 (12)
0.0192 (12)
0.0169 (11)
0.0199 (12)
0.0184 (12)
0.0139 (11)
0.0167 (11)
0.0147 (11)
0.0156 (11)
−0.0008 (9)
−0.0024 (9)
−0.0027 (9)
0.0018 (9)
Acta Cryst. (2018). C74, 548-557
sup-11

supporting information
C20E
C21E
C22E
C23E
C24E
C25E
C26E
C27E
C28E
C29E
C30E
O3E
C31E
C32E
C32F
C33E
C34E
O4E
0.0191 (12)
0.0166 (11)
0.0246 (13)
0.0401 (16)
0.0289 (14)
0.0431 (16)
0.0355 (15)
0.0253 (13)
0.0508 (18)
0.0407 (15)
0.0258 (14)
0.0194 (9)
0.0333 (16)
0.0252 (19)
0.0252 (19)
0.0245 (17)
0.0223 (14)
0.0290 (9)
0.0166 (11)
0.0218 (12)
0.0170 (12)
0.0205 (13)
0.0210 (12)
0.0251 (14)
0.0200 (13)
0.0251 (13)
0.0303 (15)
0.0201 (12)
0.0515 (19)
0.0345 (11)
0.068 (2)
0.058 (3)
0.058 (3)
0.078 (3)
0.0372 (16)
0.0155 (8)
0.0232 (13)
0.0267 (14)
0.0166 (12)
0.0198 (13)
0.0195 (12)
0.0152 (11)
0.0170 (12)
0.0270 (14)
0.0275 (14)
0.0218 (13)
0.0182 (12)
0.0169 (12)
0.0195 (14)
0.0173 (12)
0.0234 (14)
0.0272 (10)
0.0414 (18)
0.079 (3)
−0.0045 (9)
−0.0051 (10)
−0.0056 (10)
0.0022 (12)
−0.0098 (11)
−0.0150 (13)
−0.0023 (11)
−0.0113 (11)
−0.0225 (14)
−0.0096 (12)
−0.0107 (14)
0.0056 (8)
0.0104 (16)
−0.005 (2)
−0.005 (2)
0.0106 (17)
0.0106 (13)
−0.0007 (7)
−0.0052 (12)
−0.0018 (12)
0.0014 (11)
−0.0004 (11)
0.0084 (9)
0.0068 (9)
0.0066 (10)
0.0135 (12)
0.0113 (11)
0.0051 (12)
0.0058 (11)
0.0050 (10)
0.0063 (12)
0.0115 (11)
−0.0010 (11)
0.0083 (7)
0.0241 (14)
0.027 (2)
−0.0024 (9)
−0.0030 (9)
−0.0027 (9)
−0.0046 (11)
−0.0028 (11)
−0.0068 (11)
0.0022 (10)
−0.0034 (10)
−0.0038 (11)
−0.0064 (10)
−0.0015 (13)
−0.0022 (8)
0.0014 (17)
−0.010 (2)
0.079 (3)
0.067 (3)
0.027 (2)
−0.010 (2)
0.002 (2)
0.0119 (16)
0.0039 (12)
0.0084 (7)
0.0131 (12)
0.0045 (12)
0.0123 (12)
0.0066 (11)
0.0402 (17)
0.0197 (9)
0.0259 (14)
0.0343 (16)
0.0387 (16)
0.0245 (13)
−0.0012 (14)
−0.0026 (7)
0.0005 (11)
0.0076 (12)
−0.0016 (11)
−0.0063 (10)
C35E
C36E
C37E
C38E
0.0379 (16)
0.0282 (14)
0.0328 (15)
0.0330 (14)
Geometric parameters (Å, º)
Mg1—O1A
Mg1—O2A
Mg1—O3A
Mg1—O4A
O1A—C1A
C1A—C2A
C1A—C6A
C2A—C3A
C2A—C7A
C3A—C4A
C3A—H3A
C4A—C5A
C4A—C11A
C5A—C6A
C5A—H5A
C6A—C12A
C7A—C8A
C7A—C9A
C7A—C10A
C8A—H8A
C8A—H8B
C8A—H8C
C9A—H9A
1.8575 (17)
C22C—C25D
C22C—C23C
C22C—C24C
C23C—H23G
C23C—H23H
C23C—H23I
C24C—H24G
C24C—H24H
C24C—H24I
C25C—H25G
C25C—H25H
C25C—H25I
C23D—H23J
C23D—H23K
C23D—H23L
C24D—H24J
C24D—H24K
C24D—H24L
C25D—H25J
C25D—H25K
C25D—H25L
C26C—H26G
C26C—H26H
1.538 (4)
1.8653 (16)
2.0438 (18)
2.0595 (18)
1.331 (3)
1.428 (3)
1.440 (3)
1.399 (3)
1.541 (3)
1.392 (3)
0.9500
1.393 (3)
1.510 (3)
1.396 (3)
0.9500
1.536 (3)
1.540 (4)
1.540 (4)
1.542 (4)
0.9800
1.538 (3)
1.539 (3)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
Acta Cryst. (2018). C74, 548-557
sup-12

supporting information
C9A—H9B
C9A—H9C
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.540 (3)
1.541 (3)
1.546 (3)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
C26C—H26I
C27C—C29C
C27C—C30C
C27C—C28C
C28C—H28G
C28C—H28H
C28C—H28I
C29C—H29G
C29C—H29H
C29C—H29I
C30C—H30G
C30C—H30H
C30C—H30I
O3C—C34C
O3C—C31C
C31C—C32C
C31C—H31G
C31C—H31H
C32C—C33C
C32C—H32G
C32C—H32H
C33C—C34C
C33C—H33G
C33C—H33H
C34C—H34G
C34C—H34H
O4C—C35C
O4C—C38C
C35C—C36C
C35C—H35G
C35C—H35H
C36C—C37C
C36C—H36G
C36C—H36H
C37C—C38C
C37C—H37G
C37C—H37H
C38C—H38G
C38C—H38H
Mg3—O2E
0.9800
1.536 (4)
1.536 (3)
1.545 (3)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.461 (3)
1.466 (3)
1.528 (3)
0.9900
0.9900
1.530 (4)
0.9900
0.9900
1.512 (4)
0.9900
0.9900
0.9900
0.9900
1.454 (3)
1.458 (3)
1.530 (4)
0.9900
0.9900
1.522 (4)
0.9900
0.9900
1.528 (4)
0.9900
0.9900
0.9900
C10A—H10A
C10A—H10B
C10A—H10C
C11A—H11A
C11A—H11B
C11A—H11C
C12A—C14A
C12A—C15A
C12A—C13A
C13A—H13A
C13A—H13B
C13A—H13C
C14A—H14A
C14A—H14B
C14A—H14C
C15A—H15A
C15A—H15B
C15A—H15C
O2A—C16A
C16A—C21A
C16A—C17A
C17A—C18A
C17A—C22A
C18A—C19A
C18A—H18A
C19A—C20A
C19A—C26A
C20A—C21A
C20A—H20A
C21A—C27A
C22A—C23A
C22A—C25A
C22A—C24A
C23A—H23A
C23A—H23B
C23A—H23C
C24A—H24A
C24A—H24B
C24A—H24C
C25A—H25A
C25A—H25B
C25A—H25C
C26A—H26A
C26A—H26B
C26A—H26C
C27A—C30A
0.9800
0.9800
1.341 (3)
1.427 (3)
1.440 (3)
1.389 (3)
1.540 (3)
1.395 (3)
0.9500
1.391 (3)
1.518 (3)
1.407 (3)
0.9500
1.548 (3)
1.534 (3)
1.539 (3)
1.546 (3)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9900
1.8554 (17)
1.8660 (17)
2.0444 (18)
2.0653 (18)
1.334 (3)
1.429 (3)
1.437 (3)
1.406 (3)
1.550 (3)
Mg3—O1E
Mg3—O4E
Mg3—O3E
O1E—C1E
C1E—C2E
C1E—C6E
C2E—C3E
C2E—C7E
0.9800
0.9800
0.9800
1.531 (3)
Acta Cryst. (2018). C74, 548-557
sup-13

supporting information
C27A—C28A
C27A—C29B
C27A—C28B
C27A—C29A
C27A—C30B
C28A—H28A
C28A—H28B
C28A—H28C
C29A—H29A
C29A—H29B
C29A—H29C
C30A—H30A
C30A—H30B
C30A—H30C
C28B—H28D
C28B—H28E
C28B—H28F
C29B—H29D
C29B—H29E
C29B—H29F
C30B—H30D
C30B—H30E
C30B—H30F
O3A—C34A
O3A—C31A
C31A—C32A
C31A—H31A
C31A—H31B
C32A—C33A
C32A—H32A
C32A—H32B
C33A—C34A
C33A—H33A
C33A—H33B
C34A—H34A
C34A—H34B
O4A—C38A
O4A—C35A
C35A—C36A
C35A—H35A
C35A—H35B
C36A—C37A
C36A—H36A
C36A—H36B
C37A—C38A
C37A—H37A
C37A—H37B
C38A—H38A
1.533 (3)
1.537 (4)
1.537 (4)
1.539 (3)
1.539 (4)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
C3E—C4E
C3E—H3M
C4E—C5E
C4E—C11E
C5E—C6E
C5E—H5M
C6E—C12E
C7E—C9E
C7E—C10E
C7E—C8E
C8E—H8M
C8E—H8N
C8E—H8O
C9E—H9M
C9E—H9N
1.389 (3)
0.9500
1.395 (3)
1.516 (3)
1.393 (3)
0.9500
1.543 (3)
1.532 (3)
1.537 (3)
1.537 (3)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.533 (3)
1.539 (3)
1.544 (3)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
C9E—H9O
C10E—H10M
C10E—H10N
C10E—H10O
C11E—H11M
C11E—H11N
C11E—H11O
C12E—C14E
C12E—C15E
C12E—C13E
C13E—H13M
C13E—H13N
C13E—H13O
C14E—H14M
C14E—H14N
C14E—H14O
C15E—H15M
C15E—H15N
C15E—H15O
O2E—C16E
C16E—C21E
C16E—C17E
C17E—C18E
C17E—C22E
C18E—C19E
C18E—H18M
C19E—C20E
C19E—C26E
C20E—C21E
C20E—H20M
C21E—C27E
C22E—C23E
C22E—C24E
0.9800
0.9800
0.9800
0.9800
0.9800
1.462 (3)
1.464 (3)
1.527 (3)
0.9900
0.9900
1.531 (4)
0.9900
0.9900
1.512 (4)
0.9900
0.9900
0.9900
1.334 (3)
1.433 (3)
1.434 (3)
1.395 (3)
1.541 (3)
1.392 (3)
0.9500
1.388 (3)
1.508 (3)
1.398 (3)
0.9500
0.9900
1.454 (3)
1.457 (3)
1.528 (4)
0.9900
0.9900
1.529 (4)
0.9900
0.9900
1.527 (4)
0.9900
0.9900
0.9900
1.542 (3)
1.537 (4)
1.541 (3)
Acta Cryst. (2018). C74, 548-557
sup-14

supporting information
C38A—H38B
Mg2—O1C
Mg2—O2C
Mg2—O3C
Mg2—O4C
O1C—C1C
C1C—C6C
C1C—C2C
C2C—C3C
C2C—C7C
C3C—C4C
C3C—H3G
C4C—C5C
C4C—C11C
C5C—C6C
C5C—H5G
C6C—C12C
C7C—C10C
C7C—C8C
0.9900
C22E—C25E
C23E—H23M
C23E—H23N
C23E—H23O
C24E—H24M
C24E—H24N
C24E—H24O
C25E—H25M
C25E—H25N
C25E—H25O
C26E—H26M
C26E—H26N
C26E—H26O
C27E—C29E
C27E—C28E
C27E—C30E
C28E—H28M
C28E—H28N
C28E—H28O
C29E—H29M
C29E—H29N
C29E—H29O
C30E—H30M
C30E—H30N
C30E—H30O
O3E—C31E
1.541 (3)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.535 (3)
1.538 (3)
1.543 (4)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.449 (3)
1.458 (3)
1.504 (4)
1.509 (4)
0.9900
0.9900
0.9900
0.9900
1.517 (4)
0.9900
0.9900
1.513 (5)
0.9900
0.9900
1.512 (4)
0.9900
0.9900
0.9900
0.9900
0.9900
0.9900
1.461 (3)
1.463 (3)
1.8557 (17)
1.8639 (17)
2.0502 (18)
2.0699 (18)
1.333 (3)
1.430 (3)
1.435 (3)
1.394 (3)
1.546 (3)
1.389 (3)
0.9500
1.388 (3)
1.516 (3)
1.403 (3)
0.9500
1.543 (3)
1.538 (3)
1.541 (3)
1.543 (3)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.541 (4)
1.541 (4)
1.544 (4)
0.9800
0.9800
0.9800
C7C—C9C
C8C—H8G
C8C—H8H
C8C—H8I
C9C—H9H
C9C—H9I
C9C—H9J
C10C—H10G
C10C—H10H
C10C—H10I
C11C—H11G
C11C—H11H
C11C—H11I
C12C—C15C
C12C—C13C
C12C—C14C
C13C—H13G
C13C—H13H
C13C—H13I
C14C—H14G
C14C—H14H
C14C—H14I
C15C—H15G
C15C—H15H
C15C—H15I
O2C—C16C
C16C—C17C
C16C—C21C
C17C—C18C
O3E—C34E
C31E—C32E
C31E—C32F
C31E—H31M
C31E—H31N
C31E—H31P
C31E—H31Q
C32E—C33E
C32E—H32M
C32E—H32N
C32F—C33E
C32F—H32P
C32F—H32Q
C33E—C34E
C33E—H33M
C33E—H33N
C33E—H33P
C33E—H33Q
C34E—H34M
C34E—H34N
O4E—C35E
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.341 (3)
1.432 (3)
1.433 (3)
1.401 (3)
O4E—C38E
Acta Cryst. (2018). C74, 548-557
sup-15

supporting information
C17C—C22C
C18C—C19C
C18C—H18G
C19C—C20C
C19C—C26C
C20C—C21C
C20C—H20G
C21C—C27C
C22C—C25C
C22C—C23D
C22C—C24D
1.545 (3)
1.388 (3)
0.9500
1.393 (4)
1.518 (3)
1.399 (3)
0.9500
1.543 (3)
1.534 (2)
1.537 (4)
1.537 (4)
C35E—C36E
C35E—H35M
C35E—H35N
C36E—C37E
C36E—H36M
C36E—H36N
C37E—C38E
C37E—H37M
C37E—H37N
C38E—H38M
C38E—H38N
1.512 (4)
0.9900
0.9900
1.526 (4)
0.9900
0.9900
1.524 (4)
0.9900
0.9900
0.9900
0.9900
O1A—Mg1—O2A
O1A—Mg1—O3A
O2A—Mg1—O3A
O1A—Mg1—O4A
O2A—Mg1—O4A
O3A—Mg1—O4A
C1A—O1A—Mg1
O1A—C1A—C2A
O1A—C1A—C6A
C2A—C1A—C6A
C3A—C2A—C1A
C3A—C2A—C7A
C1A—C2A—C7A
C4A—C3A—C2A
C4A—C3A—H3A
C2A—C3A—H3A
C3A—C4A—C5A
C3A—C4A—C11A
C5A—C4A—C11A
C4A—C5A—C6A
C4A—C5A—H5A
C6A—C5A—H5A
C5A—C6A—C1A
C5A—C6A—C12A
C1A—C6A—C12A
C8A—C7A—C9A
C8A—C7A—C2A
C9A—C7A—C2A
C8A—C7A—C10A
C9A—C7A—C10A
C2A—C7A—C10A
C7A—C8A—H8A
C7A—C8A—H8B
H8A—C8A—H8B
C7A—C8A—H8C
H8A—C8A—H8C
125.31 (8)
124.33 (8)
98.36 (7)
98.34 (7)
116.34 (8)
89.26 (7)
174.09 (15)
121.33 (19)
119.9 (2)
118.8 (2)
118.9 (2)
119.0 (2)
122.1 (2)
123.2 (2)
118.4
H23G—C23C—H23H
C22C—C23C—H23I
H23G—C23C—H23I
H23H—C23C—H23I
C22C—C24C—H24G
C22C—C24C—H24H
H24G—C24C—H24H
C22C—C24C—H24I
H24G—C24C—H24I
H24H—C24C—H24I
C22C—C25C—H25G
C22C—C25C—H25H
H25G—C25C—H25H
C22C—C25C—H25I
H25G—C25C—H25I
H25H—C25C—H25I
C22C—C23D—H23J
C22C—C23D—H23K
H23J—C23D—H23K
C22C—C23D—H23L
H23J—C23D—H23L
H23K—C23D—H23L
C22C—C24D—H24J
C22C—C24D—H24K
H24J—C24D—H24K
C22C—C24D—H24L
H24J—C24D—H24L
H24K—C24D—H24L
C22C—C25D—H25J
C22C—C25D—H25K
H25J—C25D—H25K
C22C—C25D—H25L
H25J—C25D—H25L
H25K—C25D—H25L
C19C—C26C—H26G
C19C—C26C—H26H
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
118.4
117.2 (2)
120.8 (2)
122.1 (2)
123.3 (2)
118.3
118.3
118.6 (2)
119.7 (2)
121.7 (2)
107.4 (2)
109.7 (2)
111.9 (2)
110.9 (2)
106.0 (2)
110.9 (2)
109.5
109.5
109.5
109.5
109.5
Acta Cryst. (2018). C74, 548-557
sup-16

supporting information
H8B—C8A—H8C
109.5
H26G—C26C—H26H
109.5
C7A—C9A—H9A
C7A—C9A—H9B
H9A—C9A—H9B
C7A—C9A—H9C
H9A—C9A—H9C
H9B—C9A—H9C
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
C19C—C26C—H26I
H26G—C26C—H26I
H26H—C26C—H26I
C29C—C27C—C30C
C29C—C27C—C21C
C30C—C27C—C21C
C29C—C27C—C28C
C30C—C27C—C28C
C21C—C27C—C28C
C27C—C28C—H28G
C27C—C28C—H28H
H28G—C28C—H28H
C27C—C28C—H28I
H28G—C28C—H28I
H28H—C28C—H28I
C27C—C29C—H29G
C27C—C29C—H29H
H29G—C29C—H29H
C27C—C29C—H29I
H29G—C29C—H29I
H29H—C29C—H29I
C27C—C30C—H30G
C27C—C30C—H30H
H30G—C30C—H30H
C27C—C30C—H30I
H30G—C30C—H30I
H30H—C30C—H30I
C34C—O3C—C31C
C34C—O3C—Mg2
109.5
109.5
109.5
112.4 (2)
108.4 (2)
111.15 (19)
106.7 (2)
105.6 (2)
112.5 (2)
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
C7A—C10A—H10A
C7A—C10A—H10B
H10A—C10A—H10B
C7A—C10A—H10C
H10A—C10A—H10C
H10B—C10A—H10C
C4A—C11A—H11A
C4A—C11A—H11B
H11A—C11A—H11B
C4A—C11A—H11C
H11A—C11A—H11C
H11B—C11A—H11C
C6A—C12A—C14A
C6A—C12A—C15A
C14A—C12A—C15A
C6A—C12A—C13A
C14A—C12A—C13A
C15A—C12A—C13A
C12A—C13A—H13A
C12A—C13A—H13B
H13A—C13A—H13B
C12A—C13A—H13C
H13A—C13A—H13C
H13B—C13A—H13C
C12A—C14A—H14A
C12A—C14A—H14B
H14A—C14A—H14B
C12A—C14A—H14C
H14A—C14A—H14C
H14B—C14A—H14C
C12A—C15A—H15A
C12A—C15A—H15B
H15A—C15A—H15B
C12A—C15A—H15C
H15A—C15A—H15C
H15B—C15A—H15C
C16A—O2A—Mg1
O2A—C16A—C21A
O2A—C16A—C17A
C21A—C16A—C17A
C18A—C17A—C16A
109.5
109.5
110.80 (19)
110.23 (19)
110.6 (2)
112.5 (2)
105.9 (2)
106.6 (2)
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
108.36 (18)
124.33 (14)
125.52 (14)
106.21 (19)
110.5
110.5
110.5
110.5
108.7
103.2 (2)
111.1
111.1
111.1
111.1
109.1
101.6 (2)
111.4
111.4
111.4
C31C—O3C—Mg2
O3C—C31C—C32C
O3C—C31C—H31G
C32C—C31C—H31G
O3C—C31C—H31H
C32C—C31C—H31H
H31G—C31C—H31H
C31C—C32C—C33C
C31C—C32C—H32G
C33C—C32C—H32G
C31C—C32C—H32H
C33C—C32C—H32H
H32G—C32C—H32H
C34C—C33C—C32C
C34C—C33C—H33G
C32C—C33C—H33G
C34C—C33C—H33H
C32C—C33C—H33H
109.5
109.5
109.5
109.5
109.5
153.76 (14)
121.66 (19)
119.43 (19)
118.91 (19)
119.0 (2)
111.4
Acta Cryst. (2018). C74, 548-557
sup-17

supporting information
C18A—C17A—C22A
C16A—C17A—C22A
C17A—C18A—C19A
C17A—C18A—H18A
C19A—C18A—H18A
C20A—C19A—C18A
C20A—C19A—C26A
C18A—C19A—C26A
C19A—C20A—C21A
C19A—C20A—H20A
C21A—C20A—H20A
C20A—C21A—C16A
C20A—C21A—C27A
C16A—C21A—C27A
C23A—C22A—C25A
C23A—C22A—C17A
C25A—C22A—C17A
C23A—C22A—C24A
C25A—C22A—C24A
C17A—C22A—C24A
C22A—C23A—H23A
C22A—C23A—H23B
H23A—C23A—H23B
C22A—C23A—H23C
H23A—C23A—H23C
H23B—C23A—H23C
C22A—C24A—H24A
C22A—C24A—H24B
H24A—C24A—H24B
C22A—C24A—H24C
H24A—C24A—H24C
H24B—C24A—H24C
C22A—C25A—H25A
C22A—C25A—H25B
H25A—C25A—H25B
C22A—C25A—H25C
H25A—C25A—H25C
H25B—C25A—H25C
C19A—C26A—H26A
C19A—C26A—H26B
H26A—C26A—H26B
C19A—C26A—H26C
H26A—C26A—H26C
H26B—C26A—H26C
C30A—C27A—C28A
C29B—C27A—C28B
C30A—C27A—C29A
C28A—C27A—C29A
119.8 (2)
121.14 (19)
123.0 (2)
118.5
H33G—C33C—H33H
109.3
104.2 (2)
110.9
110.9
110.9
O3C—C34C—C33C
O3C—C34C—H34G
C33C—C34C—H34G
O3C—C34C—H34H
C33C—C34C—H34H
H34G—C34C—H34H
C35C—O4C—C38C
C35C—O4C—Mg2
C38C—O4C—Mg2
O4C—C35C—C36C
O4C—C35C—H35G
C36C—C35C—H35G
O4C—C35C—H35H
C36C—C35C—H35H
H35G—C35C—H35H
C37C—C36C—C35C
C37C—C36C—H36G
C35C—C36C—H36G
C37C—C36C—H36H
C35C—C36C—H36H
H36G—C36C—H36H
C36C—C37C—C38C
C36C—C37C—H37G
C38C—C37C—H37G
C36C—C37C—H37H
C38C—C37C—H37H
H37G—C37C—H37H
O4C—C38C—C37C
O4C—C38C—H38G
C37C—C38C—H38G
O4C—C38C—H38H
C37C—C38C—H38H
H38G—C38C—H38H
O2E—Mg3—O1E
118.5
117.4 (2)
121.6 (2)
121.0 (2)
123.2 (2)
118.4
110.9
108.9
105.29 (19)
126.95 (15)
127.77 (15)
102.8 (2)
111.2
111.2
111.2
111.2
109.1
103.5 (2)
111.1
111.1
111.1
111.1
109.0
104.9 (2)
110.8
110.8
110.8
110.8
108.8
106.0 (2)
110.5
110.5
110.5
110.5
108.7
125.01 (8)
124.69 (8)
98.32 (8)
98.22 (8)
116.48 (8)
89.38 (8)
154.25 (15)
122.12 (19)
119.3 (2)
118.5 (2)
118.5 (2)
114.8 (2)
126.58 (19)
123.3 (2)
118.4
118.4 (2)
115.9 (2)
125.61 (19)
111.4 (2)
111.57 (19)
108.7 (2)
106.0 (2)
106.6 (2)
112.48 (19)
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
O2E—Mg3—O4E
O1E—Mg3—O4E
O2E—Mg3—O3E
O1E—Mg3—O3E
O4E—Mg3—O3E
C1E—O1E—Mg3
O1E—C1E—C2E
O1E—C1E—C6E
C2E—C1E—C6E
C3E—C2E—C1E
C3E—C2E—C7E
C1E—C2E—C7E
109.0 (2)
103.7 (5)
108.9 (2)
105.6 (2)
C4E—C3E—C2E
Acta Cryst. (2018). C74, 548-557
sup-18

supporting information
C29B—C27A—C30B
C28B—C27A—C30B
C30A—C27A—C21A
C28A—C27A—C21A
C29B—C27A—C21A
C28B—C27A—C21A
C29A—C27A—C21A
C30B—C27A—C21A
C27A—C28A—H28A
C27A—C28A—H28B
H28A—C28A—H28B
C27A—C28A—H28C
H28A—C28A—H28C
H28B—C28A—H28C
C27A—C29A—H29A
C27A—C29A—H29B
H29A—C29A—H29B
C27A—C29A—H29C
H29A—C29A—H29C
H29B—C29A—H29C
C27A—C30A—H30A
C27A—C30A—H30B
H30A—C30A—H30B
C27A—C30A—H30C
H30A—C30A—H30C
H30B—C30A—H30C
C27A—C28B—H28D
C27A—C28B—H28E
H28D—C28B—H28E
C27A—C28B—H28F
H28D—C28B—H28F
H28E—C28B—H28F
C27A—C29B—H29D
C27A—C29B—H29E
H29D—C29B—H29E
C27A—C29B—H29F
H29D—C29B—H29F
H29E—C29B—H29F
C27A—C30B—H30D
C27A—C30B—H30E
H30D—C30B—H30E
C27A—C30B—H30F
H30D—C30B—H30F
H30E—C30B—H30F
C34A—O3A—C31A
C34A—O3A—Mg1
102.7 (6)
107.4 (6)
106.9 (2)
116.9 (2)
117.8 (4)
113.9 (4)
109.4 (2)
110.3 (5)
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
C4E—C3E—H3M
C2E—C3E—H3M
C3E—C4E—C5E
C3E—C4E—C11E
C5E—C4E—C11E
C6E—C5E—C4E
C6E—C5E—H5M
C4E—C5E—H5M
C5E—C6E—C1E
C5E—C6E—C12E
C1E—C6E—C12E
C9E—C7E—C10E
C9E—C7E—C8E
C10E—C7E—C8E
C9E—C7E—C2E
C10E—C7E—C2E
C8E—C7E—C2E
C7E—C8E—H8M
C7E—C8E—H8N
H8M—C8E—H8N
C7E—C8E—H8O
H8M—C8E—H8O
H8N—C8E—H8O
C7E—C9E—H9M
C7E—C9E—H9N
H9M—C9E—H9N
C7E—C9E—H9O
H9M—C9E—H9O
H9N—C9E—H9O
C7E—C10E—H10M
C7E—C10E—H10N
H10M—C10E—H10N
C7E—C10E—H10O
H10M—C10E—H10O
H10N—C10E—H10O
C4E—C11E—H11M
C4E—C11E—H11N
H11M—C11E—H11N
C4E—C11E—H11O
H11M—C11E—H11O
H11N—C11E—H11O
C14E—C12E—C15E
C14E—C12E—C6E
C15E—C12E—C6E
C14E—C12E—C13E
C15E—C12E—C13E
C6E—C12E—C13E
C12E—C13E—H13M
118.3
118.3
117.5 (2)
121.7 (2)
120.8 (2)
122.6 (2)
118.7
118.7
119.5 (2)
119.6 (2)
120.92 (19)
105.6 (2)
107.6 (2)
108.0 (2)
116.79 (19)
110.7 (2)
107.84 (19)
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
108.27 (17)
123.21 (14)
127.25 (14)
106.42 (19)
111.1 (2)
111.43 (19)
109.0 (2)
106.3 (2)
106.3 (2)
112.55 (19)
109.5
C31A—O3A—Mg1
O3A—C31A—C32A
Acta Cryst. (2018). C74, 548-557
sup-19

supporting information
O3A—C31A—H31A
C32A—C31A—H31A
O3A—C31A—H31B
C32A—C31A—H31B
H31A—C31A—H31B
C31A—C32A—C33A
C31A—C32A—H32A
C33A—C32A—H32A
C31A—C32A—H32B
C33A—C32A—H32B
H32A—C32A—H32B
C34A—C33A—C32A
C34A—C33A—H33A
C32A—C33A—H33A
C34A—C33A—H33B
C32A—C33A—H33B
H33A—C33A—H33B
O3A—C34A—C33A
O3A—C34A—H34A
C33A—C34A—H34A
O3A—C34A—H34B
C33A—C34A—H34B
H34A—C34A—H34B
C38A—O4A—C35A
C38A—O4A—Mg1
110.4
110.4
110.4
110.4
108.6
103.5 (2)
111.1
111.1
111.1
111.1
109.0
101.8 (2)
111.4
111.4
111.4
111.4
109.3
104.1 (2)
110.9
110.9
110.9
110.9
109.0
105.51 (19)
127.50 (15)
126.88 (15)
106.5 (2)
110.4
110.4
110.4
110.4
108.6
104.8 (2)
110.8
110.8
110.8
110.8
C12E—C13E—H13N
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
H13M—C13E—H13N
C12E—C13E—H13O
H13M—C13E—H13O
H13N—C13E—H13O
C12E—C14E—H14M
C12E—C14E—H14N
H14M—C14E—H14N
C12E—C14E—H14O
H14M—C14E—H14O
H14N—C14E—H14O
C12E—C15E—H15M
C12E—C15E—H15N
H15M—C15E—H15N
C12E—C15E—H15O
H15M—C15E—H15O
H15N—C15E—H15O
C16E—O2E—Mg3
O2E—C16E—C21E
O2E—C16E—C17E
C21E—C16E—C17E
C18E—C17E—C16E
C18E—C17E—C22E
C16E—C17E—C22E
C19E—C18E—C17E
C19E—C18E—H18M
C17E—C18E—H18M
C20E—C19E—C18E
C20E—C19E—C26E
C18E—C19E—C26E
C19E—C20E—C21E
C19E—C20E—H20M
C21E—C20E—H20M
C20E—C21E—C16E
C20E—C21E—C27E
C16E—C21E—C27E
C23E—C22E—C24E
C23E—C22E—C25E
C24E—C22E—C25E
C23E—C22E—C17E
C24E—C22E—C17E
C25E—C22E—C17E
C22E—C23E—H23M
C22E—C23E—H23N
H23M—C23E—H23N
C22E—C23E—H23O
H23M—C23E—H23O
H23N—C23E—H23O
109.5
174.41 (15)
121.0 (2)
120.2 (2)
118.7 (2)
118.9 (2)
119.5 (2)
121.5 (2)
122.9 (2)
118.5
C35A—O4A—Mg1
O4A—C35A—C36A
O4A—C35A—H35A
C36A—C35A—H35A
O4A—C35A—H35B
C36A—C35A—H35B
H35A—C35A—H35B
C35A—C36A—C37A
C35A—C36A—H36A
C37A—C36A—H36A
C35A—C36A—H36B
C37A—C36A—H36B
H36A—C36A—H36B
C38A—C37A—C36A
C38A—C37A—H37A
C36A—C37A—H37A
C38A—C37A—H37B
C36A—C37A—H37B
H37A—C37A—H37B
O4A—C38A—C37A
O4A—C38A—H38A
C37A—C38A—H38A
O4A—C38A—H38B
118.5
117.5 (2)
120.9 (2)
121.5 (2)
123.2 (2)
118.4
118.4
118.6 (2)
119.1 (2)
122.3 (2)
110.9 (2)
106.2 (2)
106.5 (2)
110.24 (19)
110.36 (19)
112.6 (2)
109.5
108.9
102.9 (2)
111.2
111.2
111.2
111.2
109.1
103.1 (2)
111.2
111.2
109.5
109.5
109.5
109.5
111.2
109.5
Acta Cryst. (2018). C74, 548-557
sup-20