Structural insights into methyl- or methoxy-substituted 1-(α-aminobenzyl)-2-naphthol structures: The role of c—h???π interactions

Article abstract of DOI:10.1107/S2053229619001050

Aminobenzylnaphthols are a class of compounds containing a large aromatic molecular surface which makes them suitable candidates to study the role of C—H???π interactions. We have investigated the effect of methyl or methoxy substituents on the assembling

Full text of DOI:10.1107/S2053229619001050

research papers
Structural insights into methyl- or methoxy-
substituted 1-(a-aminobenzyl)-2-naphthol
structures: the role of C—Hꢀ ꢀ ꢀp interactions
ISSN 2053-2296
Maria Annunziata M. Capozzi,a Giancarlo Terraneob and Cosimo Cardellicchioc*
a
Dipartimento di Chimica, Universita di Bari, via Orabona 4, Bari 70125, Italy, bDepartment of Chemistry, Materials and
´
Chemical Engineering ‘Giulio Natta’, via Mancinelli 7, Milan 20131, Italy, and cCNR–ICCOM, Dipartimento di Chimica,
Received 21 November 2018
Accepted 21 January 2019
´
Universita di Bari, via Orabona 4, Bari 70125, Italy. *Correspondence e-mail: cardellicchio@ba.iccom.cnr.it
Edited by D. S. Yufit, University of Durham,
England
Aminobenzylnaphthols are a class of compounds containing a large aromatic
molecular surface which makes them suitable candidates to study the role of
C—Hꢀ ꢀ ꢀꢀ interactions. We have investigated the effect of methyl or methoxy
substituents on the assembling of aromatic units by preparing and determining the
crystal structures of (S,S)-1-{(4-methylphenyl)[(1-phenylethyl)amino]methyl}-
naphthalen-2-ol, C26H25NO, and (S,S)-1-{(4-methoxyphenyl)[(1-phenylethyl)-
amino]methyl}naphthalen-2-ol, C26H25NO2. The methyl group influenced the
overall crystal packing even if the H atoms of the methyl group did not
participate directly either in hydrogen bonding or C—Hꢀ ꢀ ꢀꢀ interactions. The
introduction of the methoxy moiety caused the formation of new hydrogen
bonds, in which the O atom of the methoxy group was directly involved.
Moreover, the methoxy group promoted the formation of an interesting
C—Hꢀ ꢀ ꢀꢀ interaction which altered the orientation of an aromatic unit.
Keywords: C—Hꢀ ꢀ ꢀꢀ interactions; amino-
benzylnaphthol; crystal structure; packing; small
molecule; Hirshfeld; CrystalExplorer.
CCDC references: 1892228; 1892227
Supporting information: this article has
supporting information at journals.iucr.org/c
1. Introduction
Crystal engineering is currently an important branch of
chemistry and full comprehension of the intermolecular
interactions building up the crystal packing of molecular
entities is fundamental for assembling new molecular solid
materials and tuning their properties (Desiraju, 2013; Moulton
& Zaworotko, 2001). Several supramolecular tools have been
used over the years to achieve new solid systems ranging from
¨
hydrogen bonding (Desiraju, 2011; Aakeroy & Seddon, 1993)
and dipolar interactions (Lee et al., 2004) to halogen bonding
(Cavallo et al., 2016). Alongside these noncovalent contacts,
C—Hꢀ ꢀ ꢀꢀ interactions have consolidated their role as impor-
tant supramolecular tools for the assembly of molecules
containing aromatic residues (Nishio et al., 2009; Nishio, 2011).
These interactions generally occur between a C—H group of
an aliphatic/aromatic moiety or XH (where X is a heteroatom)
group and the ꢀ-cloud of an aromatic ring (or some deloca-
lized ꢀ-system; Mohan et al., 2010). Despite being weak, C—
Hꢀ ꢀ ꢀꢀ interactions are ubiquitous in nature and hence they
have attracted the attention of a broad scientific community
(Laughrey et al., 2008; Plevin et al., 2010). Nowadays, it is well
established that C—Hꢀ ꢀ ꢀꢀ interactions play a key role in
influencing the assembling phenomena of both small and large
molecules in solution and the solid state, ranging from protein
structures or molecular aggregations of biomolecules to the
crystal packing of simple systems such as benzene or naph-
thalene (Karthikeyan et al., 2013; Morita et al., 2006; Nishio et
al., 1995). Recently, C—Hꢀ ꢀ ꢀꢀ interactions have also proved
their ability to control supramolecular elements in stereo-
# 2019 International Union of Crystallography
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https://doi.org/10.1107/S2053229619001050 189

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Table 1
Experimental details.
4
5
Crystal data
Chemical formula
Mr
C26H25NO
367.47
C26H25NO2
383.47
Crystal system, space group
Temperature (K)
Orthorhombic, P212121
296
9.6571 (2), 13.0874 (3), 16.4113 (4)
2074.16 (8)
Orthorhombic, P212121
100
11.740 (3), 11.933 (3), 14.662 (4)
2054.0 (9)
˚
a, b, c (A)
3
˚
V (A )
Z
Radiation type
4
4
Mo Kꢁ
0.07
0.4 ꢃ 0.36 ꢃ 0.12
Mo Kꢁ
0.08
0.08 ꢃ 0.06 ꢃ 0.06
ꢂ (mmꢂ1
Crystal size (mm)
)
Data collection
Diffractometer
Absorption correction
Tmin, Tmax
Bruker APEXII CCD
Multi-scan (SADABS; Bruker, 2001)
0.709, 0.746
Bruker APEXII CCD
Multi-scan (SADABS; Bruker, 2001)
0.687, 0.746
No. of measured, independent and observed
[I > 2ꢃ(I)] reflections
Rint
25559, 6385, 5093
14384, 6032, 4110
0.044
0.717
0.052
0.706
ꢂ1
˚
(sin ꢄ/ꢅ)max (A
)
Refinement
R[F2 > 2ꢃ(F2)], wR(F2), S
No. of reflections
No. of parameters
0.043, 0.115, 1.02
6385
260
0.052, 0.104, 1.01
6032
269
H-atom treatment
H atoms treated by a mixture of independent
and constrained refinement
0.17, ꢂ0.16
H atoms treated by a mixture of independent
and constrained refinement
0.20, ꢂ0.20
ꢂ3
˚
Áꢆmax, Áꢆmin (e A
Absolute structure
)
Flack x determined using 1885 quotients
[(I+) ꢂ (Iꢂ)]/[(I+) + (Iꢂ)] (Parsons et al., 2013)
0.6 (6)
Flack x determined using 1348 quotients
[(I+) ꢂ (Iꢂ)]/[(I+) + (Iꢂ)] (Parsons et al., 2013)
0.4 (10)
Absolute structure parameter
Computer programs: APEX2 (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL2016 (Sheldrick, 2015), ORTEP-3 (Farrugia,2012) and Mercury (Macrae et
al., 2008).
selective organic reactions (Naso et al., 2009; Krenske &
Houk, 2013; Capozzi et al., 2013) and in catalyst design (Neel
et al., 2017). As proof of their fundamental role in directing the
crystal packing of small molecules, in 1999, Umezawa et al.
showed that more than 40% of organic crystals in the
Cambridge Structural Database (CSD; Groom et al., 2016)
contain C—Hꢀ ꢀ ꢀꢀ contacts.
Aminobenzylnaphthols are a class of compounds containing
three different aromatic units which can be easily obtained by
a straightforward synthetic route named the Betti reaction
´
¨ ¨
(Cardellicchio et al., 2010; Szatmari & Fulop, 2013). The Betti
reaction is a multicomponent condensation reaction between
2-naphthols, arylaldehydes and amines, which yields amino-
benzylnaphthol structures (Fig. 1). From a crystal engineering
point of view, the presence of large aromatic molecular
surfaces and the ability to modify the three ꢀ-systems by an
easy synthetic methodology make aminobenzylnaphthols
suitable candidates to study the role of C—Hꢀ ꢀ ꢀꢀ interactions
in the formation of their crystal structures and, more generally,
to increase the knowledge of these weak, but fundamental,
interactions.
Recently, some of us (Capozzi, Capitelli et al., 2014;
Cardellicchio et al., 2012) applied the Betti reaction using
chiral (R)- or (S)-arylethylamines (Fig. 1) to obtain a library of
chiral aminobenzylnaphthol compounds. One of the most
interesting features of this reaction is the chiral induction of
the stereogenic centre of the starting amine on the formation
of a new stereocentre of the aminobenzylnaphthol. For
example, starting from an (S)-arylethylamine, the simple
addition of ethanol to the crude reaction mixture caused the
Figure 1
Synthetic scheme for the Betti reaction between 2-naphthol, (S)-aryl-
ethylamine and arylaldehydes and labelling of the aryl groups in the
aminobenzylnaphthol scaffold. PhA denotes the arylaldehyde, while PhB
denotes the arylamino base.
ꢁ
190 Capozzi et al.
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Acta Cryst. (2019). C75, 189–195

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preferential crystallization of the corresponding (S,S)-amino-
benzylnaphthols only (Cardellicchio et al., 2012). In these
(S,S)-aminobenzylnaphthols, beyond the expected intra-
molecular hydrogen bonding between the hydroxy group and
the secondary amine N atom, the presence of three aryl groups
in the molecule promotes the formation of an extended
network of C—Hꢀ ꢀ ꢀꢀ interactions. This pattern of C—Hꢀ ꢀ ꢀꢀ
contacts is a unique supramolecular feature of these mol-
ecules, as witnessed by an analysis of previously reported
aminobenzylnaphthols, in which there is one among the
shortest distances ever observed between an H atom and an
2. Experimental
2.1. Synthesis and crystallization
Aminobenzylnaphthols 4 and 5 were synthesized according
to a reported simple and straightforward procedure (Cardel-
licchio et al., 2012; Capozzi, Capitelli et al., 2014). Addition of
ethanol to the crude reaction mixture, with subsequent
digestion of the slurry with ultrasound, caused the precipita-
tion of (S,S)-5 (35% yield). Further product was obtained by
chromatographic separation of the crude reaction mixture.
Analytical data for 4: 40% yield; m.p. 136–138 ꢄC (ethanol;
literature 132–134 ꢄC). [ꢁ]D20 = +200.6 (c = 1, CHCl3); literature
[ꢁ]D20 = ꢂ191.9 (c = 3.1, CHCl3) for (R,R)-4 (Cimarelli et al.,
2001).
˚
aryl plane (2.49 A; Ran & Wong, 2006). Among the structures
analyzed in the previous work, aminobenzylnaphthols 1–3,
obtained employing 4-fluoro-, 4-chloro- and 4-bromo-
benzaldehyde as the aldehyde in the Betti condensation, were
of particular interest (Fig. 1; R = F, Cl, Br; R0 = H). These
molecules were found to be isostructural, with the halogen
atom not being involved in any peculiar binding interactions,
while the C—Hꢀ ꢀ ꢀꢀ interactions dominated the crystal
packing. As a continuation of our work (Capozzi & Cardel-
licchio, 2017; Capozzi, Capitelli et al., 2014; Capozzi, Cardel-
licchio et al., 2014) on the synthesis and application of
aminobenzylnaphthols, we decided to extend this class of
molecules and investigate the effect of nonhalogen substi-
tuents on the phenyl groups, with a particular focus on methyl
or methoxy groups. The methyl substituent was chosen
because it is known to have almost the same molecular volume
as a Cl atom. On the other hand, the methoxy group was
selected because the presence of a further O atom may favour
the formation of new weak hydrogen bonds and enhance the
formation of C—Hꢀ ꢀ ꢀꢀ interactions due to its electron-rich
character. In the present work, we reacted 2-naphthol, (S)-1-
phenylethylamine and 4-tolualdehyde or 4-anisaldehyde to
yield the corresponding aminobenzylnaphthols (S,S)-1-[(4-
methylphenyl)[(1-phenylethyl)amino]methyl]naphthalen-2-ol,
4, and (S,S)-1-[(4-methoxyphenyl)[(1-phenylethyl)amino]-
methyl]naphthalen-2-ol, 5 (Fig. 1; R = Me and OMe; R0 = H).
These aminobenzylnaphthols are characterized by the
presence of three aryl groups, i.e. the naphthyl and two phenyl
groups. The first phenyl group was transferred to the final
product by the original aldehyde, while the second was pro-
vided by the chiral base. For a better description of these
compounds (see Fig. 1), the first phenyl group will be indicated
as PhA (A is aldehyde) and the second as PhB (B is base).
Within this description, aminobenzylnaphthols 1–5 have their
crucial substituent at the para position of the PhA group. On
the other hand, the aminobenzylnaphthol in which the meth-
oxy group is present on the PhB group has been reported
previously (Cardellicchio et al., 2012). We found two similar
structures in the CSD (Version of 2018; Groom et al., 2016).
The first is an aminobenzylnaphthol bearing two methyl
groups on the PhA unit in the ortho and para positions (CSD
refcode OWOTIF; Pelit & Turgut, 2016). The second is an
aminobenzylnaphthol substituted with a methoxy group in the
ortho position of the PhA group (CSD refcode MOJKOM; Xu
et al., 2005). However, as will be shown later, the ortho
substitution causes a different packing pattern.
Analytical data for 5: m.p. 118–120 ꢄC (ethanol; literature
109–112 ꢄC). [ꢁ]D20 = + 206.7 (c = 0.9, CHCl3); literature [ꢁ]D20
ꢂ190.4 (c = 1.9, CHCl3) for (R,R)-5 (Cimarelli et al., 2001).
=
2.2. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. The H atoms have been
identified using a mixed method, namely same H atoms were
inferred from neighbouring sites and some were located from
difference Fourier maps.
3. Results and discussion
Compounds 4 and 5 crystallize in the orthorhombic space
group P212121. The molecular representation and the atomic
labelling scheme are shown in Fig. 2, and the crystallographic
data are reported in Table 1. The main common structural
feature of aminobenzylnaphthols 4 and 5 is a strong intra-
molecular O—Hꢀ ꢀ ꢀN hydrogen bond occurring between the
hydroxy group and the N atom. In the analyzed structures, the
geometrical parameters describing these interactions are as
follows: O1ꢀ ꢀ ꢀN1 = 2.564 (2) A in 4 and 2.568 (3) A in 5, and
O1—H1ꢀ ꢀ ꢀN1 = 148ꢄ in 4 and 147ꢄ in 5. These values are
similar to those observed in the halogenated aminobenzyl-
naphthols 1–3 (Cardellicchio et al., 2012) and highlight how
the intramolecular hydrogen bond is preserved in all the
structures regardless of the functionalization attached on the
aromatic units.
˚
˚
Interestingly, two additional intermolecular hydrogen
bonds are also present in 4; in these contacts, the hydroxy O1
atom of an adjacent molecule functions as a ditopic electron-
density donor site towards the H atom on the amino group
(H2) and the aromatic H26 atom of the PhB unit, creating a
hydrogen-bonded supramolecular chain of aminobenzyl-
naphthol 4 which propagates along the crystallographic a axis.
The geometrical parameters are as follows: N1ꢀ ꢀ ꢀO1i =
i
i
ꢄ
˚
˚
3.168 (2) A and N1—H2ꢀ ꢀ ꢀO1 = 169.3 (19) , and H26ꢀ ꢀ ꢀO1 =
i
ꢄ
2.714 (2) A and C26—H26ꢀ ꢀ ꢀO1 = 151 [see Fig. 3; symmetry
code: (i) x + 12, ꢂy + 12, ꢂz + 1]. These intermolecular hydrogen
bonds are not present in 5 or in halogenated aminobenzyl-
naphthols 1–3.
The most interesting structural feature in aminobenzyl-
naphthols 4 and 5 is the presence, as expected, of a series of
ꢁ
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Figure 2
A molecular representation with atom labels and displacement ellipsoids drawn at the 50% probability level of aminobenzylnaphthols (a) 4 and (b) 5.
Colour code: C grey, O red, N light blue and H white.
short C—Hꢀ ꢀ ꢀꢀ interactions. As has been mentioned already,
the Cl atom and the methyl groups have nearly the same
volume; thus, if we make the hypothesis that the crystal
packing is mainly driven by steric requirements, we could
expect that compounds 4 and 2 (CSD refcode PARXOX;
Cardellicchio et al., 2012) would show strong similarities in
their packing motifs. However, the methyl group has three
electrophilic H atoms, which may be involved in contacts with
the extended ꢀ-cloud of the three aromatic moieties. If this is
the case, we may expect some differences in the crystal
packing between compound 4 and chlorinated derivative 2.
An initial confirmation that the forces which drive the
formation of the two crystal packings are different is provided
by a comparison between the fingerprint analysis (Fig. 4) of
the Hirshfeld surfaces (Spackman & Jayatilaka, 2009;
Spackman & McKinnon, 2002), performed by the Crystal-
Explorer (Version 17) program package. This method
summarizes the information about intermolecular contacts
into a characteristic plot that behaves as the ‘fingerprint’ of
that crystal, different from a fingerprint of another crystal. As
shown in Fig. 4, the fingerprint plots of molecules 4 and 2 are
clearly different and thus the noncovalent contacts driving the
assembly of these two systems should be different. If the weak
interactions building up the crystal are different, they may
affect the geometry of each molecule differently. The result is
that the shapes of molecules 2 and 4 are dissimilar (Fig. 4).
In chlorinated system 2, besides the intramolecular hydro-
gen bonds occurring between the hydroxy and amino groups,
and between the meta-H atom of the PhA unit and the hy-
droxy O atom, additional intramolecular C—Hꢀ ꢀ ꢀꢀ inter-
actions stabilize the conformation of the molecule.
Specifically, the ortho-H atom (H14) of the PhA group points
Figure 3
Ball-and-stick representation of the hydrogen-bonded supramolecular chain in aminobenzylnaphthol 4. The hydrogen bonds are shown as light-blue
dotted lines. H atoms not involved in hydrogen bonds have been omitted for clarity. The colour code and labels are as in Fig. 2.
ꢁ
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Figure 6
(a) An overlay of the two methoxy-substituted aminobenzylnaphthols 5
and 6, and CrystalExplorer fingerprint plots of aminobenzylnaphthols (b)
6 and (c) 5.
Figure 4
˚
aryl plane (distance of 0.10 A) suggest that this interaction is
(a) An overlay of the crystal structures of compounds 2 and 4, and
CrystalExplorer fingerprint plots of aminobenzylnaphthols (b) 4 and (c)
2. The colour code is as in Fig. 2, with Cl atoms in green. H atoms have
been omitted for clarity.
stronger than the other C—Hꢀ ꢀ ꢀꢀ interactions. A confirmation
is obtained from the plot of the electrostatic potential on the
Hirshfeld surface (Spackman et al., 2008). This plot, calculated
with CrystalExplorer, provides evidence of electrostatic
complementarity between the interacting molecules. In
particular, the electrophilic H atom involved in this interaction
with the electron-rich phenyl plane is shown as a light-blue
area (Fig. 5). At the same time, the meta-H atom (H23) of the
same PhB group points towards the plane of the naphthyl
moiety (the distance from H23 to the naphthyl plane is
towards the naphthyl group (the distance between H14 and
˚
the naphthyl plane is 2.65 A) and the H atom in the 5-position
(H7) of the naphthyl group interacts with the ꢀ-cloud of the
PhB plane (the distance between H7 and the PhB plane is
˚
2.775 A; Fig. 5a).
In the case of methylated compound 4, the aromatic PhB
unit experiences a different network of C—Hꢀ ꢀ ꢀꢀ interactions
(Fig. 5). The ortho-H atom (H22) of this group points towards
the aromatic plane of the PhA moiety (the distance from H22
˚
2.780 A). One H atom (H18C) of the methyl group of the PhA
moiety is also involved in a short contact with the plane of the
˚
naphthyl moiety, but its distance from the plane (2.926 A) is
˚
to the naphthyl plane is 2.634 A). The short distance from this
H atom to the plane and the close proximity of the centroid of
the aromatic system to the projection of this atom onto the
typical of a very weak interaction (Fig. 5).
Aminobenzylnaphthol 5 has a methoxy group at the para
position of the PhA group and its crystal structure will be
Figure 5
˚
The C—Hꢀ ꢀ ꢀꢀ interaction networks in (a) 2 and (b) 4. The distances (A) are highlighted in green. (c) Map of the electrostatic potential on the Hirshfeld
surface of 4.
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Figure 7
The hydrogen-bonding networks in (a) 6 and (b) 5. Hydrogen bonds are highlighted in light blue.
compared with aminobenzylnaphthol
6
(CSD refcode
x ꢂ 1, y, z] and with the meta-H atom of the anisyl group of
ii
˚
PARYOY; Cardellicchio et al., 2012), which possesses a
methoxy group at the para position of the PhB unit. Although
the structures of 5 and 6 overlap almost perfectly, the
‘fingerprint’ analysis of CrystalExplorer (Fig. 6) suggests that
there are some differences in the crystal packings, specifically
with respect to the hydrogen-bonding network.
another molecule [O1ꢀ ꢀ ꢀH24 = 2.642 A; symmetry code: (ii)
1
3
x ꢂ , ꢂy + , ꢂz + 1]. Another weak hydrogen bond was
2
2
observed between the O atom of the methoxy group with the
H atom in the 6-position of the naphthyl group [O2ꢀ ꢀ ꢀH6iii =
1
2
3
˚
2.633 A; symmetry code: (iii) ꢂx + 1, y + , ꢂz + 2].
The occurrence of an extended network of weak hydrogen
contacts does not reduce the impact of the C—Hꢀ ꢀ ꢀꢀ inter-
actions in the stabilization of the assembly of the system in 5,
as shown in Fig. 8. Specifically, the ortho hydrogen (H15) of
the PhB group points towards the plane of the naphthyl group
of an adjacent molecule (the distance from H15 to the naph-
Compound 6 has two independent molecules in the asym-
metric unit which are connected through reciprocal hydrogen
bonds between two hydroxy O atoms and two H atoms placed
in the 3-position of the naphthyl group (Oꢀ ꢀ ꢀH = 2.511 and
˚
2.700 A). Moreover, in 6, the methoxy O atom is also involved
˚
˚
in further weak hydrogen bonds (average Oꢀ ꢀ ꢀH = 2.59 A;
thyl plane is 2.646 A). Confirmation was provided by the
Fig. 7). On the other hand, in 5, the displacement of the
methoxy group in the para position of PhA modifies the
bonding pattern around the O atom. In fact, the hydroxy O
atom in 5 is involved in two weak hydrogen bonds (Fig. 7), i.e.
with one H atom of the methyl group belonging to the
mapping of the electrostatic potential on the Hirshfeld surface
(Fig. 8). The blue area corresponds to the electrophilic H
atoms involved in this interaction with the an electron-rich
naphthyl plane. The same naphthyl moiety functions as elec-
tron-density donor site for two other C—Hꢀ ꢀ ꢀꢀ contacts, i.e.
one H atom (H13A) of the methyl group points towards the
i
˚
methoxy moiety [O1ꢀ ꢀ ꢀH26C = 2.539 A; symmetry code: (i)
Figure 8
˚
(a) The C—Hꢀ ꢀ ꢀꢀ interaction network in 5. The corresponding distances (A) are highlighted in green. (b) Electrostatic potential on the Hirshfeld surface
of 5.
ꢁ
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˚
plane is 2.835 A), while the H atom of the amino group is in
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˚
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We have shown that, in contrast to the halogen series, the
selective introduction of methyl or methoxy substituents to
the phenyl ring of aminobenzylnaphthols affected deeply their
crystal structures. In the case of the methyl group, formally
isovolumetric with the Cl atom, a different packing and mol-
ecular assembly was found, notwithstanding that the H atoms
of the methyl group do not participate directly either in
hydrogen bonding or C—Hꢀ ꢀ ꢀꢀ interactions. On the other
hand, the introduction of a methoxy group caused the
formation of new hydrogen bonds, in which the methoxy O
atom is directly involved. Moreover, different from the
previous case of the introduction of the methoxy group into
the other phenyl moiety of the molecule, a new interesting C—
Hꢀ ꢀ ꢀꢀ interaction was observed, even if not directly connected
to the introduced substituents.
Neel, A. J., Hilton, M. J., Sigman, M. S. & Toste, F. D. (2017). Nature,
543, 637–646.
Acknowledgements
Nishio, M. (2011). Phys. Chem. Chem. Phys. 13, 13873–13900.
Nishio, M., Umezawa, Y., Hirota, M. & Takeuchi, Y. (1995).
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`
Italian Ministero dell’Istruzione, dell’Universita e della
Ricerca (MIUR) is gratefully acknowledged for support.
Nishio, M., Umezawa, Y., Honda, K., Tsuboyama, S. & Suezawa, H.
(2009). CrystEngComm, 11, 1757–1788.
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–
259.
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ꢁ
Acta Cryst. (2019). C75, 189–195
Capozzi et al.
The role of C—Hꢀ interactions 195

supporting information
supporting information
Acta Cryst. (2019). C75, 189-195 [https://doi.org/10.1107/S2053229619001050]
Structural insights into methyl- or methoxy-substituted 1-(α-aminobenzyl)-2-
naphthol structures: the role of C—H···π interactions
Maria Annunziata M. Capozzi, Giancarlo Terraneo and Cosimo Cardellicchio
Computing details
For both structures, data collection: APEX2 (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction:
SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: ORTEP-3 (Farrugia,2012) and Mercury (Macrae et al.,
2008); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015).
(S,S)-1-{(4-Methylphenyl)[(1-phenylethyl)amino]methyl}naphthalen-2-ol (4)
Crystal data
C26H25NO
Dx = 1.177 Mg m−3
Mr = 367.47
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 8050 reflections
θ = 2.5–29.1°
Orthorhombic, P212121
a = 9.6571 (2) Å
b = 13.0874 (3) Å
c = 16.4113 (4) Å
V = 2074.16 (8) Å3
Z = 4
µ = 0.07 mm−1
T = 296 K
Irregular block, colourless
0.4 × 0.36 × 0.12 mm
F(000) = 784
Data collection
Bruker APEXII CCD
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
φ and ω scans
25559 measured reflections
6385 independent reflections
5093 reflections with I > 2σ(I)
Rint = 0.044
θ
max = 30.6°, θmin = 3.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = −13→13
k = −17→18
l = −20→23
T
min = 0.709, Tmax = 0.746
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.043
wR(F2) = 0.115
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0636P)2 + 0.0702P]
where P = (Fo2 + 2Fc2)/3
S = 1.02
6385 reflections
260 parameters
(Δ/σ)max < 0.001
Δρmax = 0.17 e Å−3
Δρmin = −0.16 e Å−3
0 restraints
Hydrogen site location: mixed
Absolute structure: Flack x determined using
1885 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et
al., 2013)
Absolute structure parameter: 0.6 (6)
Acta Cryst. (2019). C75, 189-195
sup-1

supporting information
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
C11
H11
C19
H19
C10
C5
0.76319 (17)
0.815665
0.77755 (19)
0.696122
0.57671 (18)
0.4353 (2)
0.6765 (2)
0.769699
0.43689 (12)
0.494052
0.37333 (13)
0.415889
0.57166 (13)
0.59950 (15)
0.64958 (14)
0.634327
0.48474 (9)
0.507855
0.62733 (10)
0.638191
0.45560 (9)
0.44372 (11)
0.44489 (12)
0.452324
0.0325 (3)
0.039*
0.0373 (3)
0.045*
0.0348 (3)
0.0434 (4)
0.0449 (4)
0.054*
C9
H9
C2
H2
C3
H3
0.50493 (18)
0.851 (2)
0.36515 (19)
0.295238
0.39871 (13)
0.3152 (16)
0.42810 (16)
0.380264
0.48665 (10)
0.5297 (12)
0.47607 (13)
0.484040
0.0371 (4)
0.038 (5)*
0.0472 (4)
0.057*
C21
C1
C12
C26
H26
C4
0.90423 (17)
0.61122 (16)
0.82430 (18)
1.0341 (2)
1.044452
0.43092 (13)
0.46893 (13)
0.41055 (14)
0.42097 (17)
0.382118
0.65697 (9)
0.47721 (9)
0.40225 (10)
0.62176 (12)
0.574699
0.0337 (3)
0.0319 (3)
0.0375 (4)
0.0483 (5)
0.058*
0.3319 (2)
0.239350
0.52411 (17)
0.541309
0.45466 (13)
0.446912
0.0511 (5)
0.061*
H4
C22
H22
C24
H24
C17
H17
C6
0.89314 (19)
0.806937
1.1355 (2)
1.212509
0.7791 (2)
0.710229
0.4018 (2)
0.309510
0.49056 (16)
0.499174
0.52631 (18)
0.557936
0.32630 (17)
0.284640
0.70028 (18)
0.717513
0.72639 (11)
0.750702
0.72494 (13)
0.747808
0.35845 (11)
0.380006
0.42078 (15)
0.412192
0.0467 (4)
0.056*
0.0522 (5)
0.063*
0.0490 (5)
0.059*
0.0602 (6)
0.072*
H6
C8
H8
0.6390 (3)
0.706961
0.74720 (16)
0.797000
0.42379 (15)
0.418014
0.0589 (5)
0.071*
C25
H25
C14
H14
C23
H23
C13
H13
C7
1.1489 (2)
1.235360
0.9797 (2)
1.046760
1.0072 (2)
0.997417
0.9266 (2)
0.960163
0.46830 (19)
0.460595
0.4485 (3)
0.490989
0.5373 (2)
0.576593
0.47088 (19)
0.527102
0.65590 (14)
0.631760
0.29086 (14)
0.268405
0.76006 (12)
0.806916
0.36760 (13)
0.396063
0.0558 (5)
0.067*
0.0656 (7)
0.079*
0.0552 (5)
0.066*
0.0526 (5)
0.063*
0.5010 (3)
0.476832
0.77289 (19)
0.838987
0.41091 (17)
0.395707
0.0679 (7)
0.082*
H7
Acta Cryst. (2019). C75, 189-195
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supporting information
C20
0.7614 (3)
0.840690
0.679349
0.754025
0.9353 (2)
0.8353 (3)
0.805379
0.9915 (3)
1.024472
1.066485
0.919501
0.52696 (15)
0.609285
0.77733 (16)
0.27401 (18)
0.231248
0.238973
0.67573 (14)
0.666678
0.658115
0.0663 (7)
0.099*
0.099*
H20A
H20B
H20C
C15
C16
H16
0.289540
0.732733
0.099*
0.3653 (2)
0.3035 (2)
0.245476
0.3419 (4)
0.272672
0.387592
0.350370
0.29898 (10)
0.290086
0.34748 (10)
0.24776 (12)
0.28301 (13)
0.255416
0.16420 (15)
0.162806
0.152084
0.124463
0.50527 (9)
0.515243
0.53991 (8)
0.0646 (7)
0.0622 (6)
0.075*
0.0999 (12)
0.150*
0.150*
0.150*
0.0480 (3)
0.072*
0.0349 (3)
C18
H18A
H18B
H18C
O1
H1
N1
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
C11
C19
C10
C5
C9
C2
C3
C21
C1
C12
C26
C4
C22
C24
C17
C6
0.0320 (7)
0.0373 (8)
0.0378 (8)
0.0404 (9)
0.0451 (9)
0.0358 (8)
0.0335 (9)
0.0353 (8)
0.0308 (7)
0.0307 (7)
0.0430 (10)
0.0325 (8)
0.0380 (9)
0.0410 (10)
0.0535 (11)
0.0540 (12)
0.0660 (14)
0.0344 (10)
0.0368 (10)
0.0502 (11)
0.0325 (9)
0.0761 (16)
0.0880 (17)
0.0435 (11)
0.0682 (14)
0.0747 (19)
0.0443 (7)
0.0390 (7)
0.0323 (7)
0.0417 (8)
0.0372 (8)
0.0488 (10)
0.0398 (9)
0.0383 (9)
0.0533 (11)
0.0374 (8)
0.0344 (7)
0.0470 (9)
0.0570 (12)
0.0641 (12)
0.0644 (12)
0.0652 (13)
0.0575 (11)
0.0610 (13)
0.0403 (10)
0.0708 (14)
0.106 (2)
0.0763 (15)
0.0707 (13)
0.0493 (12)
0.0647 (13)
0.111 (2)
0.0807 (16)
0.182 (4)
0.0363 (6)
0.0329 (6)
0.0330 (7)
−0.0024 (6)
−0.0011 (7)
0.0034 (7)
0.0103 (8)
0.0018 (8)
−0.0044 (7)
−0.0065 (8)
0.0040 (6)
−0.0004 (6)
0.0054 (7)
0.0029 (8)
0.0086 (8)
0.0018 (8)
−0.0037 (9)
0.0003 (9)
0.0220 (10)
0.0005 (10)
0.0021 (9)
0.0056 (12)
−0.0037 (10)
−0.0031 (9)
0.0210 (11)
−0.0284 (13)
0.0237 (13)
0.0130 (13)
0.024 (2)
−0.0028 (6)
0.0010 (6)
0.0010 (6)
0.0014 (7)
0.0056 (8)
0.0011 (6)
0.0040 (7)
−0.0009 (6)
−0.0006 (5)
−0.0017 (6)
0.0060 (8)
0.0010 (8)
0.0062 (7)
−0.0070 (8)
0.0035 (8)
0.0032 (10)
0.0115 (11)
0.0072 (8)
0.0112 (9)
0.0015 (8)
0.0043 (8)
0.0126 (13)
−0.0052 (11)
0.0046 (8)
−0.0006 (9)
0.0143 (12)
−0.0034 (6)
−0.0031 (5)
0.0023 (6)
0.0017 (6)
0.0005 (6)
0.0005 (7)
0.0061 (8)
−0.0044 (6)
−0.0083 (8)
0.0017 (6)
−0.0015 (6)
0.0060 (7)
−0.0162 (9)
−0.0051 (10)
−0.0104 (8)
−0.0099 (9)
0.0001 (8)
0.0108 (11)
0.0126 (10)
−0.0172 (11)
0.0142 (13)
−0.0193 (9)
0.0050 (10)
0.0198 (11)
0.0191 (10)
0.0084 (12)
−0.0076 (10)
0.0014 (18)
−0.0007 (6)
0.0012 (5)
0.0327 (7)
0.0295 (7)
0.0410 (9)
0.0498 (10)
0.0372 (8)
0.0548 (11)
0.0285 (7)
0.0304 (7)
0.0348 (8)
0.0447 (9)
0.0567 (11)
0.0377 (8)
0.0503 (10)
0.0358 (9)
0.0655 (13)
0.0705 (14)
0.0623 (13)
0.0541 (12)
0.0391 (9)
0.0548 (11)
0.0784 (15)
0.0460 (11)
0.0396 (10)
0.0376 (10)
0.0432 (12)
0.0632 (8)
0.0328 (7)
C8
C25
C14
C23
C13
C7
C20
C15
C16
C18
O1
−0.0087 (5)
0.0030 (6)
N1
Acta Cryst. (2019). C75, 189-195
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supporting information
Geometric parameters (Å, º)
C11—N1
C11—C12
C11—C1
C11—H11
C19—N1
C19—C21
C19—C20
C19—H19
C10—C9
C10—C5
C10—C1
C5—C6
C5—C4
C9—C8
C9—H9
C2—O1
C2—C1
C2—C3
C3—C4
C3—H3
1.486 (2)
1.516 (2)
1.531 (2)
0.9800
1.474 (2)
1.517 (2)
1.531 (3)
0.9800
1.414 (3)
1.426 (2)
1.430 (2)
1.409 (3)
1.416 (3)
1.372 (3)
0.9300
1.357 (2)
1.386 (2)
1.414 (3)
1.344 (3)
0.9300
C22—H22
C24—C25
C24—C23
C24—H24
C17—C16
C17—H17
C6—C7
C6—H6
C8—C7
C8—H8
C25—H25
C14—C15
C14—C13
C14—H14
C23—H23
C13—H13
C7—H7
C20—H20A
C20—H20B
C20—H20C
C15—C16
C15—C18
C16—H16
C18—H18A
C18—H18B
C18—H18C
O1—H1
0.9300
1.370 (3)
1.374 (3)
0.9300
1.384 (3)
0.9300
1.359 (4)
0.9300
1.391 (4)
0.9300
0.9300
1.367 (4)
1.391 (3)
0.9300
0.9300
0.9300
0.9300
0.9600
0.9600
0.9600
1.386 (4)
1.507 (3)
0.9300
0.9600
0.9600
C21—C22
C21—C26
C12—C13
C12—C17
C26—C25
C26—H26
C4—H4
1.385 (2)
1.387 (2)
1.387 (3)
1.387 (3)
1.387 (3)
0.9300
0.9600
0.8200
0.9300
C22—C23
1.376 (3)
N1—H2
0.84 (2)
N1—C11—C12
N1—C11—C1
C12—C11—C1
N1—C11—H11
C12—C11—H11
C1—C11—H11
N1—C19—C21
N1—C19—C20
C21—C19—C20
N1—C19—H19
C21—C19—H19
C20—C19—H19
C9—C10—C5
C9—C10—C1
C5—C10—C1
C6—C5—C4
109.22 (13)
110.67 (13)
111.29 (12)
108.5
108.5
108.5
115.29 (14)
108.06 (15)
109.73 (15)
107.8
107.8
107.8
116.81 (16)
123.38 (15)
119.81 (15)
121.59 (19)
119.71 (19)
C23—C24—H24
C16—C17—C12
C16—C17—H17
C12—C17—H17
C7—C6—C5
C7—C6—H6
C5—C6—H6
C9—C8—C7
C9—C8—H8
120.3
120.8 (2)
119.6
119.6
121.6 (2)
119.2
119.2
121.1 (2)
119.5
119.5
120.42 (18)
119.8
119.8
121.4 (2)
119.3
119.3
120.47 (18)
C7—C8—H8
C24—C25—C26
C24—C25—H25
C26—C25—H25
C15—C14—C13
C15—C14—H14
C13—C14—H14
C24—C23—C22
C6—C5—C10
Acta Cryst. (2019). C75, 189-195
sup-4

supporting information
C4—C5—C10
C8—C9—C10
C8—C9—H9
C10—C9—H9
O1—C2—C1
O1—C2—C3
C1—C2—C3
C4—C3—C2
C4—C3—H3
118.70 (17)
121.52 (19)
119.2
C24—C23—H23
C22—C23—H23
C12—C13—C14
C12—C13—H13
C14—C13—H13
C6—C7—C8
119.8
119.8
120.9 (2)
119.5
119.5
119.2 (2)
120.4
120.4
119.2
123.13 (16)
116.03 (16)
120.84 (17)
120.99 (18)
119.5
C6—C7—H7
C8—C7—H7
C19—C20—H20A
C19—C20—H20B
H20A—C20—H20B
C19—C20—H20C
H20A—C20—H20C
H20B—C20—H20C
C14—C15—C16
C14—C15—C18
C16—C15—C18
C17—C16—C15
C17—C16—H16
C15—C16—H16
C15—C18—H18A
C15—C18—H18B
H18A—C18—H18B
C15—C18—H18C
H18A—C18—H18C
H18B—C18—H18C
C2—O1—H1
109.5
C2—C3—H3
119.5
109.5
109.5
109.5
109.5
C22—C21—C26
C22—C21—C19
C26—C21—C19
C2—C1—C10
C2—C1—C11
C10—C1—C11
C13—C12—C17
C13—C12—C11
C17—C12—C11
C21—C26—C25
C21—C26—H26
C25—C26—H26
C3—C4—C5
117.74 (16)
118.77 (15)
123.31 (15)
118.59 (15)
121.27 (15)
120.06 (14)
117.66 (18)
120.93 (17)
121.40 (16)
120.80 (17)
119.6
119.6
121.06 (18)
119.5
119.5
121.26 (17)
119.4
109.5
117.9 (2)
121.3 (3)
120.8 (3)
121.4 (2)
119.3
119.3
109.5
109.5
109.5
109.5
109.5
109.5
109.5
114.37 (13)
107.9 (14)
110.6 (14)
C3—C4—H4
C5—C4—H4
C23—C22—C21
C23—C22—H22
C21—C22—H22
C25—C24—C23
C25—C24—H24
119.4
119.32 (19)
120.3
C19—N1—C11
C19—N1—H2
C11—N1—H2
C9—C10—C5—C6
C1—C10—C5—C6
C9—C10—C5—C4
C1—C10—C5—C4
C5—C10—C9—C8
C1—C10—C9—C8
O1—C2—C3—C4
C1—C2—C3—C4
N1—C19—C21—C22
C20—C19—C21—C22
N1—C19—C21—C26
C20—C19—C21—C26
O1—C2—C1—C10
C3—C2—C1—C10
O1—C2—C1—C11
C3—C2—C1—C11
C9—C10—C1—C2
1.3 (3)
C19—C21—C26—C25
C2—C3—C4—C5
C6—C5—C4—C3
−174.10 (19)
−1.4 (3)
179.6 (2)
0.2 (3)
−0.9 (3)
174.29 (19)
0.4 (3)
179.65 (18)
179.5 (2)
−1.2 (3)
−1.0 (3)
−0.1 (4)
−0.4 (4)
0.0 (4)
−178.70 (18)
−179.34 (17)
0.7 (2)
C10—C5—C4—C3
−0.2 (3)
C26—C21—C22—C23
C19—C21—C22—C23
C13—C12—C17—C16
C11—C12—C17—C16
C4—C5—C6—C7
179.72 (19)
−177.60 (18)
1.6 (3)
156.02 (16)
−81.7 (2)
−29.1 (2)
93.1 (2)
178.49 (15)
−0.7 (2)
2.0 (2)
C10—C5—C6—C7
C10—C9—C8—C7
C23—C24—C25—C26
C21—C26—C25—C24
C25—C24—C23—C22
C21—C22—C23—C24
C17—C12—C13—C14
C11—C12—C13—C14
0.5 (4)
1.3 (3)
−178.04 (19)
−177.21 (16)
179.60 (16)
Acta Cryst. (2019). C75, 189-195
sup-5

supporting information
C5—C10—C1—C2
C9—C10—C1—C11
C5—C10—C1—C11
N1—C11—C1—C2
C12—C11—C1—C2
N1—C11—C1—C10
C12—C11—C1—C10
N1—C11—C12—C13
C1—C11—C12—C13
N1—C11—C12—C17
C1—C11—C12—C17
C22—C21—C26—C25
−0.4 (2)
−3.8 (2)
C15—C14—C13—C12
C5—C6—C7—C8
C9—C8—C7—C6
−1.4 (4)
0.0 (4)
1.1 (4)
−0.1 (4)
179.2 (2)
−1.9 (3)
1.7 (3)
−177.6 (2)
−68.79 (19)
168.07 (16)
155.82 (14)
−81.33 (17)
176.11 (14)
−28.1 (2)
93.51 (17)
155.40 (14)
−82.96 (18)
−124.92 (17)
112.60 (18)
55.8 (2)
C13—C14—C15—C16
C13—C14—C15—C18
C12—C17—C16—C15
C14—C15—C16—C17
C18—C15—C16—C17
C21—C19—N1—C11
C20—C19—N1—C11
C12—C11—N1—C19
C1—C11—N1—C19
−66.7 (2)
0.8 (3)
(S,S)-1-{(4-Methoxyphenyl)[(1-phenylethyl)amino]methyl}naphthalen-2-ol (5)
Crystal data
C26H25NO2
Dx = 1.240 Mg m−3
Mr = 383.47
Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121
a = 11.740 (3) Å
b = 11.933 (3) Å
c = 14.662 (4) Å
V = 2054.0 (9) Å3
Z = 4
Cell parameters from 2502 reflections
θ = 3.4–26.2°
µ = 0.08 mm−1
T = 100 K
Block, colourless
0.08 × 0.06 × 0.06 mm
F(000) = 816
Data collection
Bruker APEXII CCD
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
φ and ω scans
14384 measured reflections
6032 independent reflections
4110 reflections with I > 2σ(I)
Rint = 0.052
θ
max = 30.1°, θmin = 3.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = −16→16
k = −16→14
l = −20→15
T
min = 0.687, Tmax = 0.746
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.052
wR(F2) = 0.104
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0395P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00
6032 reflections
269 parameters
(Δ/σ)max < 0.001
Δρmax = 0.20 e Å−3
Δρmin = −0.20 e Å−3
0 restraints
Hydrogen site location: mixed
Absolute structure: Flack x determined using
1348 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et
al., 2013)
Absolute structure parameter: 0.4 (10)
Acta Cryst. (2019). C75, 189-195
sup-6

supporting information
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
C1
C2
H2
C3
H3
C4
H4
C5
H5
C6
H6
C7
H7
C8
H8
C9
C10
C11
H11
C12
H12
C13
H13A
H13B
H13C
C14
C15
H15
C16
H16
C17
H17
C18
H18
C19
H19
C20
C21
H21
0.1062 (2)
0.0389 (2)
−0.017558
0.0559 (2)
0.011362
0.1409 (2)
0.253 (3)
0.52051 (19)
0.5187 (2)
0.572363
0.4398 (2)
0.440334
0.3562 (2)
0.521 (2)
0.2770 (2)
0.278093
0.1990 (2)
0.147784
0.1963 (2)
0.142427
0.2718 (2)
0.268220
0.3555 (2)
0.4392 (2)
0.4371 (2)
0.358719
0.4324 (2)
0.414290
0.5079 (2)
0.533485
0.571153
0.466613
0.3230 (2)
0.3237 (2)
0.391081
0.2259 (2)
0.227766
0.1247 (2)
0.058721
0.1226 (2)
0.054920
0.2211 (2)
0.218874
0.4846 (2)
0.4265 (2)
0.357829
0.57247 (17)
0.65293 (19)
0.661193
0.71758 (19)
0.770022
0.70665 (18)
0.354 (2)
0.77580 (18)
0.828972
0.76612 (19)
0.812549
0.6860 (2)
0.679225
0.61723 (18)
0.564547
0.62498 (17)
0.55647 (16)
0.47002 (16)
0.450891
0.34783 (17)
0.392351
0.27549 (19)
0.234720
0.304344
0.241762
0.31054 (18)
0.23891 (18)
0.210486
0.2093 (2)
0.161607
0.25117 (18)
0.231693
0.32152 (19)
0.349238
0.0207 (5)
0.0253 (6)
0.030*
0.0263 (6)
0.032*
0.0207 (5)
0.034 (8)*
0.0268 (6)
0.032*
0.0300 (6)
0.036*
0.0281 (6)
0.034*
0.0218 (5)
0.026*
0.0177 (5)
0.0172 (5)
0.0174 (5)
0.021*
0.0212 (5)
0.025*
0.1634 (2)
0.120181
0.2470 (3)
0.261290
0.3111 (2)
0.367709
0.2922 (2)
0.336122
0.2064 (2)
0.18835 (19)
0.25973 (19)
0.267183
0.1123 (2)
0.052793
0.0598 (2)
0.118297
0.024464
0.003697
0.1589 (2)
0.2367 (2)
0.254658
0.2879 (2)
0.340004
0.2610 (2)
0.295386
0.1834 (2)
0.164826
0.1329 (2)
0.080846
0.37925 (19)
0.4719 (2)
0.460227
0.0281 (6)
0.042*
0.042*
0.042*
0.0211 (5)
0.0269 (6)
0.032*
0.0315 (6)
0.038*
0.0292 (6)
0.035*
0.0268 (6)
0.032*
0.0242 (6)
0.029*
0.0182 (5)
0.0226 (5)
0.027*
0.35117 (18)
0.398952
0.48108 (16)
0.44731 (17)
0.418728
Acta Cryst. (2019). C75, 189-195
sup-7

supporting information
C22
H22
C23
C24
H24
C25
H25
C26
H26A
H26B
H26C
N1
0.5826 (2)
0.644083
0.5992 (2)
0.5072 (2)
0.518854
0.3977 (2)
0.336197
0.8031 (2)
0.800623
0.804260
0.870522
0.20138 (18)
0.08566 (15)
0.117998
0.4683 (2)
0.428133
0.5700 (2)
0.6312 (2)
0.700722
0.5882 (2)
0.629017
0.5560 (3)
0.542804
0.485582
0.597747
0.49887 (18)
0.60723 (14)
0.595921
0.45508 (18)
0.432046
0.49737 (17)
0.52992 (18)
0.556944
0.52203 (18)
0.544302
0.4845 (2)
0.419976
0.516180
0.499350
0.39540 (15)
0.51500 (14)
0.466289
0.0255 (6)
0.031*
0.0246 (6)
0.0253 (6)
0.030*
0.0222 (5)
0.027*
0.0392 (8)
0.059*
0.059*
0.059*
0.0206 (4)
0.0290 (5)
0.044*
O1
H1
O2
0.70444 (15)
0.61855 (16)
0.51157 (13)
0.0332 (5)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
C1
C2
C3
C4
C5
C6
C7
C8
0.0176 (11)
0.0165 (12)
0.0207 (12)
0.0176 (12)
0.0319 (14)
0.0364 (16)
0.0278 (14)
0.0201 (12)
0.0160 (11)
0.0135 (10)
0.0160 (11)
0.0164 (11)
0.0193 (12)
0.0171 (11)
0.0279 (14)
0.0304 (15)
0.0297 (14)
0.0266 (14)
0.0186 (12)
0.0151 (10)
0.0212 (12)
0.0181 (12)
0.0180 (11)
0.0261 (13)
0.0191 (11)
0.0153 (12)
0.0169 (10)
0.0256 (10)
0.0180 (8)
0.0183 (13)
0.0280 (14)
0.0328 (15)
0.0251 (14)
0.0291 (15)
0.0294 (15)
0.0253 (15)
0.0237 (13)
0.0189 (12)
0.0191 (12)
0.0186 (11)
0.0284 (14)
0.0376 (16)
0.0298 (14)
0.0321 (15)
0.0388 (16)
0.0323 (15)
0.0277 (15)
0.0345 (15)
0.0238 (13)
0.0275 (14)
0.0369 (16)
0.0386 (15)
0.0268 (14)
0.0248 (14)
0.070 (2)
0.0261 (13)
−0.0022 (10)
0.0015 (11)
−0.0065 (11)
−0.0071 (10)
−0.0118 (12)
−0.0057 (12)
0.0022 (11)
−0.0015 (11)
−0.0047 (10)
−0.0026 (9)
−0.0008 (9)
−0.0040 (10)
−0.0042 (11)
−0.0062 (10)
−0.0100 (12)
−0.0054 (13)
−0.0022 (12)
−0.0067 (11)
−0.0082 (11)
−0.0017 (10)
−0.0011 (11)
0.0033 (11)
−0.0067 (11)
−0.0063 (11)
0.0002 (10)
−0.0068 (13)
−0.0041 (9)
0.0061 (8)
−0.0031 (10)
0.0020 (11)
0.0060 (11)
0.0011 (10)
0.0017 (11)
−0.0049 (13)
−0.0043 (12)
0.0013 (10)
−0.0037 (10)
−0.0010 (9)
−0.0034 (10)
−0.0036 (10)
−0.0065 (11)
−0.0058 (10)
0.0014 (11)
0.0041 (12)
−0.0062 (12)
−0.0076 (11)
−0.0017 (10)
−0.0028 (10)
−0.0010 (10)
0.0006 (11)
−0.0036 (10)
−0.0025 (11)
0.0005 (11)
−0.0017 (12)
−0.0045 (9)
0.0012 (9)
−0.0002 (10)
−0.0093 (12)
−0.0076 (13)
−0.0020 (10)
0.0021 (12)
0.0094 (11)
0.0071 (12)
0.0016 (11)
−0.0011 (10)
−0.0002 (10)
0.0020 (9)
0.0055 (11)
0.0092 (13)
0.0024 (10)
0.0054 (11)
−0.0020 (13)
−0.0043 (12)
0.0037 (12)
0.0046 (11)
0.0049 (10)
0.0003 (11)
0.0050 (11)
0.0080 (11)
0.0030 (11)
0.0029 (11)
0.0093 (16)
0.0066 (9)
0.0316 (15)
0.0253 (14)
0.0195 (13)
0.0195 (14)
0.0241 (14)
0.0311 (15)
0.0215 (13)
0.0182 (12)
0.0191 (12)
0.0177 (12)
0.0188 (12)
0.0272 (15)
0.0165 (12)
0.0208 (14)
0.0253 (15)
0.0256 (15)
0.0260 (15)
0.0196 (13)
0.0158 (12)
0.0192 (13)
0.0216 (13)
0.0173 (13)
0.0229 (14)
0.0228 (13)
0.0326 (17)
0.0206 (11)
0.0378 (12)
0.0291 (11)
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
N1
0.0245 (11)
0.0236 (10)
0.0525 (12)
O1
O2
0.0051 (8)
0.0045 (9)
−0.0119 (8)
−0.0030 (8)
Acta Cryst. (2019). C75, 189-195
sup-8

supporting information
Geometric parameters (Å, º)
C1—O1
C1—C10
C1—C2
C2—C3
C2—H2
C3—C4
C3—H3
C4—C5
C4—C9
C5—C6
C5—H5
C6—C7
C6—H6
C7—C8
C7—H7
C8—C9
C8—H8
C9—C10
C10—C11
C11—N1
C11—C20
C11—H11
C12—N1
C12—C14
C12—C13
C12—H12
C13—H13A
C13—H13B
C13—H13C
1.356 (3)
1.388 (3)
1.420 (4)
1.350 (4)
0.9300
1.421 (4)
0.9300
1.411 (4)
1.423 (3)
1.360 (4)
0.9300
1.395 (4)
0.9300
1.370 (3)
0.9300
1.423 (3)
0.9300
1.432 (3)
1.520 (3)
1.487 (3)
1.522 (3)
0.9800
1.486 (3)
1.518 (4)
1.521 (3)
0.9800
C14—C19
C14—C15
C15—C16
C15—H15
C16—C17
C16—H16
C17—C18
C17—H17
C18—C19
C18—H18
C19—H19
C20—C21
C20—C25
C21—C22
C21—H21
C22—C23
C22—H22
C23—O2
C23—C24
C24—C25
C24—H24
C25—H25
C26—O2
C26—H26A
C26—H26B
C26—H26C
N1—H4
1.388 (4)
1.392 (4)
1.382 (4)
0.9300
1.390 (4)
0.9300
1.376 (4)
0.9300
1.387 (4)
0.9300
0.9300
1.382 (3)
1.391 (3)
1.397 (3)
0.9300
1.377 (4)
0.9300
1.380 (3)
1.388 (4)
1.389 (3)
0.9300
0.9300
1.434 (3)
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
0.90 (3)
0.8200
O1—H1
O1—C1—C10
O1—C1—C2
C10—C1—C2
C3—C2—C1
C3—C2—H2
C1—C2—H2
C2—C3—C4
C2—C3—H3
C4—C3—H3
C5—C4—C3
C5—C4—C9
C3—C4—C9
C6—C5—C4
C6—C5—H5
C4—C5—H5
C5—C6—C7
123.5 (2)
115.4 (2)
121.1 (2)
120.8 (2)
119.6
119.6
121.0 (2)
119.5
C19—C14—C15
C19—C14—C12
C15—C14—C12
C16—C15—C14
C16—C15—H15
C14—C15—H15
C15—C16—C17
C15—C16—H16
C17—C16—H16
C18—C17—C16
C18—C17—H17
C16—C17—H17
C17—C18—C19
C17—C18—H18
C19—C18—H18
C18—C19—C14
118.3 (2)
121.3 (2)
120.2 (2)
121.1 (2)
119.4
119.4
119.8 (3)
120.1
120.1
119.8 (3)
120.1
120.1
120.2 (2)
119.9
119.5
121.4 (2)
120.0 (2)
118.6 (2)
121.2 (3)
119.4
119.4
119.5 (2)
119.9
120.9 (2)
Acta Cryst. (2019). C75, 189-195
sup-9

supporting information
C5—C6—H6
C7—C6—H6
C8—C7—C6
C8—C7—H7
C6—C7—H7
C7—C8—C9
C7—C8—H8
C9—C8—H8
120.2
120.2
121.1 (3)
119.4
119.4
121.2 (2)
119.4
119.4
117.0 (2)
120.4 (2)
122.5 (2)
118.1 (2)
122.4 (2)
119.5 (2)
110.58 (19)
108.55 (19)
114.41 (19)
107.7
107.7
107.7
112.0 (2)
107.22 (19)
113.8 (2)
107.9
C18—C19—H19
C14—C19—H19
C21—C20—C25
C21—C20—C11
C25—C20—C11
C20—C21—C22
C20—C21—H21
C22—C21—H21
C23—C22—C21
C23—C22—H22
C21—C22—H22
C22—C23—O2
C22—C23—C24
O2—C23—C24
C23—C24—C25
C23—C24—H24
C25—C24—H24
C24—C25—C20
C24—C25—H25
C20—C25—H25
O2—C26—H26A
O2—C26—H26B
H26A—C26—H26B
O2—C26—H26C
H26A—C26—H26C
H26B—C26—H26C
C12—N1—C11
C12—N1—H4
119.5
119.5
118.6 (2)
120.0 (2)
121.4 (2)
121.6 (2)
119.2
119.2
118.9 (2)
120.5
C4—C9—C8
C4—C9—C10
C8—C9—C10
C1—C10—C9
C1—C10—C11
C9—C10—C11
N1—C11—C10
N1—C11—C20
C10—C11—C20
N1—C11—H11
C10—C11—H11
C20—C11—H11
N1—C12—C14
N1—C12—C13
C14—C12—C13
N1—C12—H12
C14—C12—H12
C13—C12—H12
C12—C13—H13A
C12—C13—H13B
H13A—C13—H13B
C12—C13—H13C
H13A—C13—H13C
H13B—C13—H13C
120.5
124.4 (2)
120.5 (2)
115.1 (2)
119.9 (3)
120.1
120.1
120.5 (2)
119.7
119.7
109.5
109.5
109.5
109.5
109.5
109.5
113.89 (19)
108.4 (19)
109.7 (19)
109.5
107.9
107.9
109.5
109.5
109.5
109.5
109.5
109.5
C11—N1—H4
C1—O1—H1
C23—O2—C26
117.6 (2)
O1—C1—C2—C3
C10—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
C2—C3—C4—C9
C3—C4—C5—C6
C9—C4—C5—C6
C4—C5—C6—C7
C5—C6—C7—C8
C6—C7—C8—C9
C5—C4—C9—C8
C3—C4—C9—C8
C5—C4—C9—C10
C3—C4—C9—C10
C7—C8—C9—C4
−176.4 (2)
2.4 (4)
N1—C12—C14—C15
C13—C12—C14—C15
C19—C14—C15—C16
C12—C14—C15—C16
C14—C15—C16—C17
C15—C16—C17—C18
C16—C17—C18—C19
C17—C18—C19—C14
C15—C14—C19—C18
C12—C14—C19—C18
N1—C11—C20—C21
C10—C11—C20—C21
N1—C11—C20—C25
C10—C11—C20—C25
C25—C20—C21—C22
−68.0 (3)
53.8 (3)
−0.6 (4)
174.2 (2)
0.3 (4)
0.3 (4)
−0.6 (4)
0.3 (4)
−0.5 (4)
176.7 (2)
−1.4 (3)
−178.1 (2)
−0.1 (4)
−0.7 (4)
0.7 (4)
0.0 (4)
0.7 (3)
178.8 (2)
−176.7 (2)
1.4 (3)
0.3 (4)
−174.5 (2)
−103.3 (2)
132.7 (2)
74.4 (3)
−49.6 (3)
1.3 (4)
−0.7 (3)
Acta Cryst. (2019). C75, 189-195
sup-10

supporting information
C7—C8—C9—C10
O1—C1—C10—C9
C2—C1—C10—C9
O1—C1—C10—C11
C2—C1—C10—C11
C4—C9—C10—C1
C8—C9—C10—C1
C4—C9—C10—C11
C8—C9—C10—C11
C1—C10—C11—N1
C9—C10—C11—N1
C1—C10—C11—C20
C9—C10—C11—C20
N1—C12—C14—C19
C13—C12—C14—C19
176.7 (2)
176.4 (2)
−2.2 (3)
−2.9 (4)
178.4 (2)
0.4 (3)
−176.9 (2)
179.7 (2)
2.4 (3)
−22.4 (3)
158.3 (2)
100.5 (3)
−78.8 (3)
106.6 (3)
−131.6 (2)
C11—C20—C21—C22
179.1 (2)
−0.1 (4)
178.0 (2)
−1.5 (4)
1.7 (4)
−177.8 (2)
−0.5 (4)
−1.0 (4)
−178.8 (2)
−55.6 (3)
178.9 (2)
−81.2 (2)
152.5 (2)
−3.3 (4)
176.2 (2)
C20—C21—C22—C23
C21—C22—C23—O2
C21—C22—C23—C24
C22—C23—C24—C25
O2—C23—C24—C25
C23—C24—C25—C20
C21—C20—C25—C24
C11—C20—C25—C24
C14—C12—N1—C11
C13—C12—N1—C11
C10—C11—N1—C12
C20—C11—N1—C12
C22—C23—O2—C26
C24—C23—O2—C26
Acta Cryst. (2019). C75, 189-195
sup-11