Two (E)-2-({[4-(dialkyl-amino)-phenyl]imino}-meth-yl)-4-nitro-phenols

Article abstract of DOI:10.1107/S0108270112025589

The slow evaporation of analytical NMR samples resulted in the formation of crystals of (E)-2-({[4-(dimethyl-amino)-phenyl]-imino}-methyl)-4-nitro-phenol, C₁₅H₁₅N₃O₃, (I), and (E)-2-({[4-(diethyl-amino)-phenyl]-

Full text of DOI:10.1107/S0108270112025589

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
was too low for it to be utilized for that method (Drozdzak &
Nishioka, 2010). Previously, the electronic properties of (I)
were investigated (Avramovici et al., 1973, 1974) and it was
also studied for the preparation of organometallic GaIII
complexes (Chesnut et al., 1998). To the best of our know-
ledge, (II) has not been discussed previously in the literature.
ISSN 0108-2701
Two (E)-2-({[4-(dialkylamino)phenyl]-
imino}methyl)-4-nitrophenols
Arto Valkonen,a* Erkki Kolehmainen,a Aleksandra
b
b
b
´
´
Grzegorska, Borys Osmiałowski, Ryszard Gawinecki
and Kari Rissanena
aDepartment of Chemistry, University of Jyvaskyla, PO Box 35, FIN-40014 Jyvaskyla,
Finland, and bDepartment of Chemistry, University of Technology and Life Sciences,
¨
¨
¨
¨
The crystal structure of (I) is ordered (Fig. 1), but in (II) a
small static disorder exists in one ethyl group (Fig. 2), with the
occupancy of the major component being 0.789 (6). The
molecules of both compounds are rather planar. However, the
dihedral angle between the two aromatic rings in (I) is
13.44 (19)ꢁ, significantly larger than that in (II) [2.57 (8)ꢁ].
Furthermore, the dimethylamino group shows torsion angles
of ꢂ13.8 (6) (C16—N15—C12—C13) and 5.2 (6)ꢁ (C18—
N15—C12—C11) with respect to the parent benzene ring in
(I). The corresponding angles in (II) are ꢂ2.1 (3) [major
component; for the minor C16B—N15—C12—C13 compo-
nent the angle is 37.1 (4)ꢁ] and ꢂ14.6 (3)ꢁ, respectively.
Overall, the structure of (II) is more planar than that of (I)
and the only significant deviation from the plane is found for
the diethylamino group.
Seminaryjna 3, PL-85-326 Bydgoszcz, Poland
Correspondence e-mail: arto.m.valkonen@jyu.fi
Received 15 March 2012
Accepted 5 June 2012
Online 1 July 2012
The slow evaporation of analytical NMR samples resulted
in the formation of crystals of (E)-2-({[4-(dimethylamino)-
phenyl]imino}methyl)-4-nitrophenol, C15H15N3O3, (I), and
(E)-2-({[4-(diethylamino)phenyl]imino}methyl)-4-nitro-
phenol, C17H19N3O3, (II). Despite the small structural
difference between these two N-salicylideneaniline deriva-
tives, they show different space groups and diverse molecular
packing. The molecules of both compounds are close to being
planar due to an intramolecular O—Hꢀ ꢀ ꢀN hydrogen bond.
The 4-alkylamino-substituted benzene ring is inclined at an
angle of 13.44 (19)ꢁ in (I) and 2.57 (8)ꢁ in (II) with respect to
the 4-nitro-substituted phenol ring. Only very weak inter-
molecular ꢀ–ꢀ stacking and C—Hꢀ ꢀ ꢀO interactions were
found in these structures.
The presence of an intramolecular hydrogen bond in (I) was
predicted according to previous studies on salicylideneanilines
Comment
(E)-2-({[4-(Dimethylamino)phenyl]imino}methyl)-4-nitrophe-
nol, (I), and (E)-2-({[4-(diethylamino)phenyl]imino}methyl)-
4-nitrophenol, (II), are products from the condensation reac-
tion of N,N-dimethyl-p-phenylenediamine or N,N-diethyl-p-
phenylenediamine, respectively, with 2-hydroxy-5-nitrobenz-
aldehyde. These two compounds have the potential to occur in
two tautomeric forms, and they were prepared in order to
check whether increased acidity of OH (due to the presence of
an NO2 group in the para position) and increased basicity of
the –N CH– N atom would result in the enamine form of
these compounds. This study shows that they occur in the solid
state in the imine form (Figs. 1 and 2). However, in solution
there is a fast H-atom exchange, observed from the chemical
shifts of atoms C1, C6, C7 and N4, between the imine (with
–OH) and enaminone (with –NH) forms. As previously
observed with similar compounds (Gawinecki et al., 2007), the
enaminone form predominates in chloroform solution.
Recently, (I) was studied to obtain novel Grubbs-type
bidentate Schiff base ruthenium catalysts, but its pKa value
Figure 1
A view of the asymmetric unit of (I), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level.
Figure 2
Aview of the asymmetric unit of (II), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level. Dashed
bonds indicate the minor disorder component.
Acta Cryst. (2012). C68, o279–o282
doi:10.1107/S0108270112025589
# 2012 International Union of Crystallography o279

organic compounds
Figure 4
A packing diagram for (II), viewed along the a axis, showing two adjacent
chains along the b axis and the C—Hꢀ ꢀ ꢀO interactions (dashed lines).
and the phenylenediamine (C9–C14) rings at (ꢂx + 1, y,
3
˚
ꢂz + 2) [3.759 (2) A] and (ꢂx + 1, ꢂy + 1, ꢂz + 1)
˚
[3.878 (2) A] (Fig. 3). These ꢀ–ꢀ interactions and two C—
Figure 3
Hꢀ ꢀ ꢀO interactions connect the molecules into antiparallel
stacks. The other three C—Hꢀ ꢀ ꢀO contacts connect the stacks
to neighbouring ones.
A packing diagram for (I), viewed along the b axis, showing the stacked
molecules and the C—Hꢀ ꢀ ꢀO interactions (dashed lines) between methyl
and nitro groups.
There is only one C—Hꢀ ꢀ ꢀO contact between the methyl
groups and the nitro group in (II) (Table 2). Arylic atoms C5
and C14 donate C—Hꢀ ꢀ ꢀO contacts, which are accepted by
nitro and hydroxy groups, respectively. In (II), there are ꢀ–ꢀ
stacking interactions between the phenol (C1–C6) ring and
the phenylenediamine (C9–C14) ring at (ꢂx + 2, ꢂy, ꢂz + 1)
and proved by spectroscopic methods in solution about
40 years ago (Avramovici et al., 1973). Due to the conjugated
system and the intramolecular hydrogen bond with an S(6)
graph-set motif (Bernstein et al., 1995) in the solid state, the
benzylideneamine group becomes closely planar, as demon-
strated by the torsion angles of 179.7 (4) (C5—C6—C7—N8)
and 0.9 (6)ꢁ (C1—C6—C7—N8) between the imine bond and
the phenolic ring in (I). In (II), these torsion angles are similar,
with values of ꢂ178.28 (15) and 0.9 (2)ꢁ, respectively.
˚
[centroid–centroid distance = 3.5826 (10) A], and between two
˚
phenol (C1–C6) rings [3.6267 (9) A; symmetry code for the
second ring (ꢂx + 2, ꢂy, ꢂz + 2)]. Due to the different
intermolecular interactions, the packing in (II) is different, as
can be seen in Fig. 4. Furthermore, the only C—Hꢀ ꢀ ꢀO contact
between a methyl (C17) and a nitro group is not sufficiently
strong to hold the C16—C17 ethyl group completely in one
conformation. The minor component does not show a similar
close contact.
The hydroxy H atom in both compounds was found from an
˚
electron-density map within bonding distance (ꢃ1 A) of the O
atom, before being refined at its geometrically idealized
position. Although this shows signs of the structures occurring
in the imine form, reliable determination of H-atom positions
is difficult. More evidence of the predominant imine form can
be seen from the bond distances. The O1—C1 distance in both
˚
˚
compounds [1.338 (5) A in (I) and 1.334 (2) A in (II)] is close
to normal values reported for single C—O bonds in phenols
and salicylideneamines (e.g. Ozeryanskii et al., 2006). Also, the
Experimental
A solution of N,N-dimethyl-p-phenylenediamine (0.68 g, 5 mmol)
and 2-hydroxy-5-nitrobenzaldehyde (0.83 g, 5 mmol) in ethanol
(20 ml) was refluxed for 15 min. The solid which precipitated from
the cooled reaction mixture was filtered off and recrystallized twice
from ethanol to give crystals of (I). Compound (II) was obtained in a
similar manner using N,N-diethyl-1,4-phenylenediamine (0.82 g, 5 mmol)
as the starting material.
˚
N8—C7 bond is short in both compounds [1.294 (5) A in (I)
˚
and 1.289 (2) A in (II)], strongly indicating the existence of a
conjugated C N bond, while the long C6—C7 bond
˚
˚
[1.446 (5) A in (I) and 1.457 (2) A in (II)] implies a single
bond. Based on these facts, the presence of an intramolecular
O—Hꢀ ꢀ ꢀN bond (Tables 1 and 2) and the pure E isomer in
both compounds are justified. These features are similar to
what has been observed in related 4-dimethylamino-N-
salicylideneanilines (Filipenko et al., 1983; Aldoshin et al.,
Analysis for compound (I): yield 91%; red crystals, m.p. 488–
491 K. Elemental analysis calculated for C15H15N3O3: C 63.15, H 5.30,
1
N 14.73%; found: C 63.01, H 5.49, N 14.59%. H NMR (CDCl3): ꢁ
15.19 (br s, 1H, OH/NH), 8.65 (s, 1H, H7), 8.31 (s, 1H, H5), 8.19 (d, J =
9.0 Hz, 1H, H3), 7.32 (d, J = 9.0 Hz, 2H, H10 and H14), 7.02 (d, J =
9.2 Hz, 1H, H2), 6.75 (d, J = 9.0 Hz, 2H, H11 and H13), 3.03 (s, 6H,
2 ꢄ CH3); 13C NMR (CDCl3): ꢁ 167.4 (C1), 154.5 (C7), 150.6 (C12),
139.6 (C9), 134.4 (C4), 127.5 (C5), 127.4 (C3), 122.4 (C10 and C14),
118.5 (C6), 118.2 (C2), 112.6 (C11 and C13), 40.4 (C16 and C18);
15N NMR (CDCl3/ext. CH3NO2): ꢁ ꢂ13.1 (N4), ꢂ93.8 (N8), ꢂ331.3
(N15).
¨
1984; Wozniak et al., 1995; Pizzala et al., 2000; Gul et al., 2007).
Whereas these structures, including the present ones, show
phenol–imine forms, the related 4,5-bis(dimethylamino)-1-[(2-
hydroxy-5-nitrobenzylidene)amino]naphthalene is reported
to have the enaminone form (Ozeryanskii et al., 2006).
The molecule of (I) has intermolecular C—Hꢀ ꢀ ꢀO contacts
between the methyl groups and the nitro group (Fig. 3), and
between atom C2 and the nitro group (Table 1). There are also
two different weak ꢀ–ꢀ stacking interactions, with rather long
centroid–centroid distances between the phenol (C1–C6) ring
Analysis for compound (II): yield 89%; red crystals, m.p. 441–
443 K. Elemental analysis calculated for C17H19N3O3: C 65.16, H 6.11,
1
N 13.41%; found: C 65.11, H 6.17, N 13.37%. H NMR (CDCl3): ꢁ
15.30 (br s, 1H, OH/NH), 8.63 (s, 1H, H7), 8.30 (s, 1H, H5), 8.18 (d, J =
Acta Cryst. (2012). C68, o279–o282
ꢅ
o280 Valkonen et al. C15H15N3O3 and C17H19N3O3

organic compounds
Table 1
Hydrogen-bond geometry (A, ) for (I).
Table 2
Hydrogen-bond geometry (A, ) for (II).
ꢁ
ꢁ
˚
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
O1—H1ꢀ ꢀ ꢀN8
0.84
0.98
0.98
0.98
0.95
1.84
2.62
2.69
2.60
2.64
2.583 (4)
3.495 (5)
3.062 (5)
3.411 (5)
3.352 (5)
147
148
103
140
132
O1—H1ꢀ ꢀ ꢀN8
0.84
0.95
0.98
0.95
1.81
2.64
2.60
2.56
2.557 (2)
3.421 (2)
3.195 (3)
3.328 (2)
148
139
119
138
C16—H16Aꢀ ꢀ ꢀO4Ai
C16—H16Aꢀ ꢀ ꢀO4Aii
C16—H16Cꢀ ꢀ ꢀO4Biii
C2—H2ꢀ ꢀ ꢀO4Biv
C14—H14ꢀ ꢀ ꢀO1i
C17—H17Bꢀ ꢀ ꢀO4Aii
C5—H5ꢀ ꢀ ꢀO4Biii
1
3
Symmetry codes: (i) ꢂx þ 1; ꢂy; ꢂz þ 1; (ii) ꢂx þ 2; y þ ; ꢂz þ ; (iii) ꢂx þ 3; ꢂy,
2
2
3
2
1
2
3
2
1
2
ꢂz þ 2.
Symmetry codes: (i) ꢂx þ 1; y; ꢂz þ ; (ii) x ꢂ ; ꢂy þ ; z ꢂ ; (iii) ꢂx þ 1; ꢂy þ 1,
ꢂz þ 1; (iv) x; y þ 1; z.
Refinement
9.0 Hz, 1H, H3), 7.30 (d, J = 9.0 Hz, 2H, H10 and H14), 7.01 (d, J =
9.2 Hz, 1H, H2), 6.70 (d, J = 9.0 Hz, 2H, H11 and H13), 3.41 (q, J =
7.1 Hz, 4H, 2 ꢄ CH2), 1.21 (t, J = 7.1 Hz, 6H, 2 ꢄ CH3); 13C NMR
(CDCl3): ꢁ 167.5 (C1), 153.7 (C7), 148.1 (C12), 139.5 (C9), 133.3 (C4),
127.5 (C5), 127.2 (C3), 122.7 (C10 and C14), 118.6 (C6), 118.2 (C2), 111.9
(C11 and C13), 44.58 (C16 and C18), 12.56 (C17 and C19); 15N NMR
(CDCl3/ext. CH3NO2): ꢁ ꢂ13.4 (N4), ꢂ95.3 (N8), ꢂ302.3 (N15).
Single crystals of both compounds suitable for X-ray diffraction
were obtained by very slow evaporation of analytical samples from
NMR tubes, where CDCl3 was used as solvent.
R[F2 > 2ꢅ(F2)] = 0.056
wR(F2) = 0.123
S = 1.04
3790 reflections
228 parameters
8 restraints
H-atom parameteꢂrs3 constrained
˚
Áꢆmax = 0.38 e A
ꢂ3
˚
Áꢆmin = ꢂ0.25 e A
All H atoms were located from electron-density maps, but they
were calculated at their idealized positions and allowed to ride on
their parent atoms, with C—H = 0.95 (aromatic), 0.98 (methyl) or
˚
˚
0.99 A (methylene) and O—H = 0.84 A, and with Uiso(H) = 1.2Ueq(C)
for aromatic or methylene groups or 1.5Ueq(C,O) for methyl or
hydroxy groups. The treatment of disorder in (II) required the use of
similarity restraints to equalize the bonding distances N15—C16 and
N15—C16B, and also the C16—C17 and C16B—C17B distances
Compound (I)
Crystal data
˚
(s.u. = 0.02 A). Similarity restraints were also applied for the minor
component to make the anisotropic displacement parameters of
3
˚
C15H15N3O3
Mr = 285.30
Monoclinic, C2=c
a = 31.688 (2) A
b = 6.7674 (5) A
V = 2702.4 (3) A
Z = 8
2
C16B and C17B more similar (s.u. = 0.02 A ).
Mo Kꢃ radiation
ꢄ = 0.10 mmꢂ1
T = 123 K
0.15 ꢄ 0.13 ꢄ 0.03 mm
˚
˚
˚
˚
For both compounds, data collection: COLLECT (Bruker, 2008);
cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data
reduction: DENZO-SMN; program(s) used to solve structure:
SIR2004 (Burla et al., 2005); program(s) used to refine structure:
SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3
(Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to
prepare material for publication: SHELXL97.
c = 13.146 (1) A
ꢂ = 106.545 (6)ꢁ
Data collection
Bruker Kappa APEXII CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.985, Tmax = 0.997
4611 measured reflections
2467 independent reflections
1242 reflections with I > 2ꢅ(I)
Rint = 0.108
The Academy of Finland is gratefully acknowledged for
funding to KR (project Nos. 130629, 122350 and 140718).
Refinement
R[F2 > 2ꢅ(F2)] = 0.082
wR(F2) = 0.167
S = 1.02
193 parameters
H-atom parameteꢂrs3 constrained
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: LG3082). Services for accessing these data are
described at the back of the journal.
˚
Áꢆmax = 0.27 e A
ꢂ3
˚
2467 reflections
Áꢆmin = ꢂ0.25 e A
References
Compound (II)
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381–388.
Crystal data
3
˚
V = 1525.31 (5) A
Z = 4
Mo Kꢃ radiation
ꢄ = 0.10 mmꢂ1
T = 123 K
C17H19N3O3
Mr = 313.35
Monoclinic, P21=c
˚
a = 6.5848 (1) A
˚
b = 22.2544 (4) A
˚
c = 10.8735 (2) A
0.20 ꢄ 0.16 ꢄ 0.06 mm
ꢂ = 106.811 (1)ꢁ
Data collection
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&
Bruker Kappa APEXII CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.981, Tmax = 0.994
6646 measured reflections
3790 independent reflections
2653 reflections with I > 2ꢅ(I)
Rint = 0.030
Filipenko, O. S., Ponomarev, V. I., Bolotin, B. M. & Atovmyan, L. O. (1983).
Kristallografiya, 28, 889–895.
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Valkonen et al. C15H15N3O3 and C17H19N3O3 o281

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Dobrowolska, W., Sobczyk, L. & Grech, E. (2006). Eur. J. Org. Chem. pp.
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Acta Cryst. (2012). C68, o279–o282

supplementary materials
supplementary materials
Acta Cryst. (2012). C68, o279–o282 [doi:10.1107/S0108270112025589]
Two (E)-2-({[4-(dialkylamino)phenyl]imino}methyl)-4-nitrophenols
Arto Valkonen, Erkki Kolehmainen, Aleksandra Grzegórska, Borys Ośmiałowski, Ryszard
Gawinecki and Kari Rissanen
(I) (E)-2-({[4-(dimethylamino)phenyl]imino}methyl)-4-nitrophenol
Crystal data
C15H15N3O3
Mr = 285.30
F(000) = 1200
Dx = 1.402 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 3324 reflections
θ = 0.4–28.3°
Monoclinic, C2/c
Hall symbol: -C 2yc
a = 31.688 (2) Å
b = 6.7674 (5) Å
c = 13.146 (1) Å
β = 106.545 (6)°
V = 2702.4 (3) Å3
Z = 8
µ = 0.10 mm−1
T = 123 K
Plate, red
0.15 × 0.13 × 0.03 mm
Data collection
Bruker Kappa APEXII CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
Detector resolution: 9 pixels mm-1
φ and ω scans
4611 measured reflections
2467 independent reflections
1242 reflections with I > 2σ(I)
Rint = 0.108
θmax = 25.4°, θmin = 3.1°
h = −38→37
k = −7→8
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
l = −15→15
T
min = 0.985, Tmax = 0.997
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.082
wR(F2) = 0.167
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.01
2467 reflections
193 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0415P)2 + 5.4351P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.27 e Å−3
Δρmin = −0.25 e Å−3
Acta Cryst. (2012). C68, o279–o282
sup-1

supplementary materials
Special details
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles;
correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
O1
0.52621 (9)
0.5043
1.0161 (4)
0.9460
0.6531 (3)
0.6235
0.0392 (9)
0.059*
H1
O4A
O4B
N4
0.71055 (9)
0.67200 (9)
0.67536 (11)
0.48098 (11)
0.31176 (10)
0.56150 (13)
0.60210 (14)
0.6039
0.6370 (5)
0.3711 (4)
0.5524 (5)
0.6959 (5)
0.3775 (5)
0.9003 (6)
0.9886 (6)
1.1284
0.8492 (2)
0.7984 (2)
0.8074 (3)
0.5994 (3)
0.4226 (3)
0.6902 (3)
0.7378 (4)
0.7440
0.0353 (8)
0.0297 (7)
0.0271 (9)
0.0226 (8)
0.0288 (9)
0.0258 (10)
0.0324 (12)
0.039*
N8
N15
C1
C2
H2
C3
0.63947 (13)
0.6671
0.8768 (6)
0.9379
0.7759 (3)
0.8075
0.0282 (11)
0.034*
H3
C4
0.63598 (12)
0.59640 (12)
0.5953
0.6738 (6)
0.5812 (6)
0.4411
0.7670 (3)
0.7212 (3)
0.7166
0.0203 (10)
0.0203 (10)
0.024*
C5
H5
C6
0.55827 (13)
0.51652 (12)
0.5152
0.6899 (6)
0.5931 (6)
0.4530
0.6818 (3)
0.6357 (3)
0.6319
0.0207 (10)
0.0227 (10)
0.027*
C7
H7
C9
0.43969 (13)
0.43060 (12)
0.4535
0.6029 (6)
0.4040 (6)
0.3171
0.5577 (3)
0.5674 (3)
0.6036
0.0221 (10)
0.0218 (10)
0.026*
C10
H10
C11
H11
C12
C13
H13
C14
H14
C16
H16A
H16B
H16C
C18
H18A
H18B
H18C
0.38834 (13)
0.3828
0.3317 (6)
0.1954
0.5246 (3)
0.5326
0.0237 (10)
0.028*
0.35325 (13)
0.36290 (13)
0.3401
0.4541 (6)
0.6552 (6)
0.7438
0.4695 (3)
0.4624 (3)
0.4276
0.0231 (10)
0.0250 (10)
0.030*
0.40491 (13)
0.4104
0.7256 (6)
0.8624
0.5054 (3)
0.4992
0.0244 (10)
0.029*
0.27433 (12)
0.2703
0.5130 (7)
0.5892
0.3847 (4)
0.4447
0.0320 (12)
0.048*
0.2476
0.4368
0.3522
0.048*
0.2801
0.6034
0.3321
0.048*
0.30268 (15)
0.3230
0.1728 (6)
0.0898
0.4367 (4)
0.4114
0.0378 (12)
0.057*
0.2723
0.1425
0.3962
0.057*
0.3066
0.1464
0.5121
0.057*
Acta Cryst. (2012). C68, o279–o282
sup-2

supplementary materials
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
O1
0.0297 (18)
0.0213 (16)
0.0276 (16)
0.027 (2)
0.0207 (19)
0.0203 (19)
0.028 (2)
0.034 (3)
0.028 (2)
0.027 (2)
0.022 (2)
0.021 (2)
0.023 (2)
0.021 (2)
0.022 (2)
0.022 (2)
0.027 (2)
0.023 (2)
0.030 (3)
0.016 (2)
0.033 (3)
0.0243 (18)
0.040 (2)
0.0250 (18)
0.026 (2)
0.030 (2)
0.029 (2)
0.023 (3)
0.017 (3)
0.023 (2)
0.020 (3)
0.022 (2)
0.025 (2)
0.020 (2)
0.026 (2)
0.021 (2)
0.025 (3)
0.028 (3)
0.023 (2)
0.018 (2)
0.047 (3)
0.036 (3)
0.057 (2)
0.040 (2)
0.0339 (19)
0.029 (2)
0.018 (2)
0.034 (2)
0.026 (3)
0.043 (3)
0.030 (3)
0.017 (2)
0.020 (2)
0.017 (2)
0.027 (3)
0.020 (2)
0.021 (3)
0.027 (3)
0.016 (2)
0.029 (3)
0.025 (3)
0.032 (3)
0.041 (3)
0.0043 (14)
−0.0061 (15)
0.0002 (14)
−0.0033 (17)
0.0004 (16)
0.0024 (17)
0.005 (2)
0.0009 (17)
0.0006 (14)
0.0045 (14)
0.0082 (17)
0.0071 (16)
0.0030 (16)
0.006 (2)
0.0084 (16)
−0.0023 (17)
0.0003 (15)
−0.0010 (18)
−0.0013 (17)
0.0029 (18)
0.006 (2)
O4A
O4B
N4
N8
N15
C1
C2
−0.003 (2)
−0.007 (2)
−0.0035 (18)
0.0014 (18)
0.0020 (19)
−0.0018 (18)
−0.0007 (19)
0.0028 (18)
0.0057 (19)
0.003 (2)
0.006 (2)
0.001 (2)
C3
0.003 (2)
−0.003 (2)
−0.0048 (19)
−0.0009 (19)
0.004 (2)
C4
0.0105 (19)
0.0109 (19)
0.0062 (18)
0.010 (2)
C5
C6
C7
−0.0031 (19)
−0.001 (2)
0.0034 (19)
0.004 (2)
C9
0.0067 (19)
0.005 (2)
C10
C11
C12
C13
C14
C16
C18
0.0113 (19)
0.009 (2)
0.0037 (19)
0.000 (2)
0.0067 (19)
0.0023 (19)
0.007 (2)
0.0083 (19)
0.008 (2)
0.0028 (19)
0.001 (2)
0.005 (2)
−0.004 (2)
0.005 (2)
0.000 (2)
Geometric parameters (Å, º)
O1—C1
O1—H1
O4A—N4
O4B—N4
N4—C4
N8—C7
N8—C9
N15—C12
N15—C18
N15—C16
C1—C2
C1—C6
C2—C3
C2—H2
C3—C4
C3—H3
C4—C5
C5—C6
C5—H5
1.338 (5)
C6—C7
1.446 (5)
0.8400
C7—H7
0.9500
1.235 (4)
1.234 (4)
1.462 (5)
1.294 (5)
1.414 (5)
1.384 (5)
1.438 (5)
1.470 (5)
1.395 (6)
1.430 (6)
1.374 (6)
0.9500
C9—C10
1.390 (5)
1.395 (5)
1.386 (5)
0.9500
C9—C14
C10—C11
C10—H10
C11—C12
C11—H11
C12—C13
C13—C14
C13—H13
C14—H14
C16—H16A
C16—H16B
C16—H16C
C18—H18A
C18—H18B
C18—H18C
1.410 (6)
0.9500
1.404 (6)
1.374 (6)
0.9500
0.9500
0.9800
0.9800
1.380 (6)
0.9500
0.9800
0.9800
1.378 (5)
1.383 (5)
0.9500
0.9800
0.9800
C1—O1—H1
109.5
C10—C9—N8
C14—C9—N8
C11—C10—C9
126.1 (4)
116.1 (4)
120.4 (4)
O4B—N4—O4A
O4B—N4—C4
123.1 (4)
118.9 (3)
Acta Cryst. (2012). C68, o279–o282
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supplementary materials
O4A—N4—C4
C7—N8—C9
C12—N15—C18
C12—N15—C16
C18—N15—C16
O1—C1—C2
O1—C1—C6
C2—C1—C6
C3—C2—C1
C3—C2—H2
C1—C2—H2
C2—C3—C4
C2—C3—H3
C4—C3—H3
C5—C4—C3
C5—C4—N4
C3—C4—N4
C4—C5—C6
C4—C5—H5
C6—C5—H5
C5—C6—C1
C5—C6—C7
C1—C6—C7
N8—C7—C6
N8—C7—H7
C6—C7—H7
C10—C9—C14
118.0 (3)
121.1 (4)
120.2 (4)
119.3 (4)
118.2 (3)
118.7 (4)
121.4 (4)
119.9 (4)
121.1 (4)
119.4
C11—C10—H10
C9—C10—H10
C10—C11—C12
C10—C11—H11
C12—C11—H11
N15—C12—C13
N15—C12—C11
C13—C12—C11
C14—C13—C12
C14—C13—H13
C12—C13—H13
C13—C14—C9
C13—C14—H14
C9—C14—H14
N15—C16—H16A
N15—C16—H16B
119.8
119.8
122.0 (4)
119.0
119.0
122.1 (4)
121.2 (4)
116.7 (4)
120.8 (4)
119.6
119.4
119.6
118.5 (4)
120.7
122.2 (4)
118.9
120.7
118.9
122.0 (4)
118.7 (4)
119.3 (4)
120.7 (4)
119.6
109.5
109.5
H16A—C16—H16B
N15—C16—H16C
H16A—C16—H16C
H16B—C16—H16C
N15—C18—H18A
N15—C18—H18B
H18A—C18—H18B
N15—C18—H18C
H18A—C18—H18C
H18B—C18—H18C
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
119.6
117.7 (4)
120.9 (4)
121.4 (4)
120.5 (4)
119.7
119.7
117.8 (4)
O1—C1—C2—C3
C6—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
C2—C3—C4—N4
O4B—N4—C4—C5
O4A—N4—C4—C5
O4B—N4—C4—C3
O4A—N4—C4—C3
C3—C4—C5—C6
N4—C4—C5—C6
C4—C5—C6—C1
C4—C5—C6—C7
O1—C1—C6—C5
C2—C1—C6—C5
O1—C1—C6—C7
C2—C1—C6—C7
C9—N8—C7—C6
−179.1 (4)
0.9 (7)
C5—C6—C7—N8
179.7 (4)
0.9 (6)
C1—C6—C7—N8
−0.7 (7)
0.2 (6)
C7—N8—C9—C10
12.4 (6)
−169.9 (4)
1.0 (6)
C7—N8—C9—C14
−179.8 (4)
0.5 (6)
C14—C9—C10—C11
N8—C9—C10—C11
C9—C10—C11—C12
C18—N15—C12—C13
C16—N15—C12—C13
C18—N15—C12—C11
C16—N15—C12—C11
C10—C11—C12—N15
C10—C11—C12—C13
N15—C12—C13—C14
C11—C12—C13—C14
C12—C13—C14—C9
C10—C9—C14—C13
N8—C9—C14—C13
178.6 (4)
0.4 (6)
−179.3 (4)
−179.5 (4)
0.7 (6)
−176.6 (4)
−13.8 (6)
5.2 (6)
0.0 (6)
−179.9 (3)
0.1 (6)
168.0 (4)
176.7 (4)
−1.7 (6)
−176.8 (4)
1.5 (6)
−178.7 (4)
179.4 (4)
−0.6 (6)
−1.8 (6)
178.3 (4)
−177.6 (4)
−0.1 (6)
−1.1 (6)
−179.0 (4)
Acta Cryst. (2012). C68, o279–o282
sup-4

supplementary materials
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O1—H1···N8
0.84
0.98
0.98
0.98
0.95
1.84
2.62
2.69
2.60
2.64
2.583 (4)
3.495 (5)
3.062 (5)
3.411 (5)
3.352 (5)
147
148
103
140
132
C16—H16A···O4Ai
C16—H16A···O4Aii
C16—H16C···O4Biii
C2—H2···O4Biv
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) x−1/2, −y+3/2, z−1/2; (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z.
(II) (E)-2-({[4-(diethylamino)phenyl]imino}methyl)-4-nitrophenol
Crystal data
C17H19N3O3
Mr = 313.35
F(000) = 664
Dx = 1.365 Mg m−3
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 6.5848 (1) Å
b = 22.2544 (4) Å
c = 10.8735 (2) Å
β = 106.811 (1)°
V = 1525.31 (5) Å3
Z = 4
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 3812 reflections
θ = 0.4–28.3°
µ = 0.10 mm−1
T = 123 K
Plate, red
0.20 × 0.16 × 0.06 mm
Data collection
Bruker Kappa APEXII CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
Detector resolution: 9 pixels mm-1
φ and ω scans
6646 measured reflections
3790 independent reflections
2653 reflections with I > 2σ(I)
Rint = 0.030
θmax = 28.3°, θmin = 2.7°
h = −8→8
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = −29→25
l = −14→14
T
min = 0.981, Tmax = 0.994
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.056
wR(F2) = 0.123
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.04
3790 reflections
228 parameters
8 restraints
Primary atom site location: structure-invariant
direct methods
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0343P)2 + 0.8927P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.38 e Å−3
Δρmin = −0.25 e Å−3
Special details
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles;
correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.
Acta Cryst. (2012). C68, o279–o282
sup-5

supplementary materials
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 > 2σ(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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Occ. (<1)
O1
0.62487 (19)
0.6717
−0.00420 (6)
0.0187
0.65774 (11)
0.6108
0.0292 (3)
0.044*
H1
O4A
O4B
N4
1.2373 (2)
1.4676 (2)
1.2831 (2)
0.8984 (2)
0.9700 (2)
0.7858 (3)
0.7423 (3)
0.6000
−0.11842 (6)
−0.07660 (6)
−0.08873 (7)
0.05530 (6)
0.21352 (7)
−0.02429 (8)
−0.06292 (8)
−0.0745
1.14921 (12)
1.06910 (13)
1.06541 (14)
0.58184 (13)
0.19249 (16)
0.75424 (15)
0.84506 (16)
0.8365
0.0369 (3)
0.0371 (3)
0.0272 (3)
0.0219 (3)
0.0344 (4)
0.0224 (4)
0.0253 (4)
0.030*
N8
N15
C1
C2
H2
C3
0.9037 (3)
0.8736
−0.08426 (8)
−0.1102
0.94667 (16)
1.0086
0.0246 (4)
0.029*
H3
C4
1.1114 (3)
1.1597 (3)
1.3029
−0.06732 (7)
−0.02930 (7)
−0.0184
0.95727 (15)
0.86918 (16)
0.8788
0.0221 (4)
0.0219 (4)
0.026*
C5
H5
C6
0.9984 (3)
1.0492 (3)
1.1925
−0.00712 (7)
0.03371 (7)
0.0443
0.76660 (15)
0.67494 (16)
0.6838
0.0210 (4)
0.0223 (4)
0.027*
C7
H7
C9
0.9309 (3)
1.1272 (3)
1.2536
0.09557 (7)
0.11697 (8)
0.1042
0.48881 (15)
0.48217 (16)
0.5441
0.0206 (3)
0.0223 (4)
0.027*
C10
H10
C11
H11
C12
C13
H13
C14
H14
C16
H16A
H16B
C17
H17A
H17B
H17C
C16B
H16C
H16D
C17B
H17D
H17E
H17F
1.1391 (3)
1.2742
0.15641 (7)
0.1705
0.38660 (16)
0.3846
0.0230 (4)
0.028*
0.9561 (3)
0.7602 (3)
0.6329
0.17650 (8)
0.15488 (8)
0.1676
0.29146 (17)
0.30041 (17)
0.2393
0.0245 (4)
0.0260 (4)
0.031*
0.7495 (3)
0.6148
0.11537 (8)
0.1014
0.39666 (16)
0.3998
0.0240 (4)
0.029*
0.7773 (4)
0.6813
0.23028 (11)
0.1952
0.0887 (3)
0.0666
0.0257 (7)
0.031*
0.789 (6)
0.789 (6)
0.789 (6)
0.789 (6)
0.789 (6)
0.789 (6)
0.789 (6)
0.211 (6)
0.211 (6)
0.211 (6)
0.211 (6)
0.211 (6)
0.211 (6)
0.211 (6)
0.8178
0.2419
0.0111
0.031*
0.6615 (5)
0.5351
0.28215 (12)
0.2923
0.1294 (2)
0.0591
0.0313 (7)
0.047*
0.7557
0.3171
0.1500
0.047*
0.6191
0.2705
0.2053
0.047*
0.7851 (15)
0.7019
0.2594 (4)
0.2614
0.1507 (9)
0.2133
0.029 (3)
0.034*
0.8367
0.3001
0.1382
0.034*
0.658 (2)
0.5326
0.2316 (5)
0.2562
0.0247 (11)
−0.0137
0.051 (3)
0.076*
0.6143
0.1909
0.0404
0.076*
0.7465
0.2296
−0.0341
0.076*
Acta Cryst. (2012). C68, o279–o282
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supplementary materials
C18
1.1665 (3)
1.1560
0.24487 (8)
0.2607
0.19747 (19)
0.1107
0.0305 (4)
0.037*
H18A
H18B
C19
1.2844
0.2155
0.2198
0.037*
1.2213 (4)
1.3548
0.29653 (10)
0.3150
0.2927 (2)
0.2897
0.0458 (6)
0.069*
H19A
H19B
H19C
1.2368
0.2813
0.3795
0.069*
1.1077
0.3266
0.2704
0.069*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
O1
0.0257 (7)
0.0429 (8)
0.0272 (7)
0.0342 (9)
0.0271 (8)
0.0257 (8)
0.0251 (9)
0.0268 (9)
0.0333 (10)
0.0282 (9)
0.0225 (8)
0.0266 (9)
0.0241 (9)
0.0252 (9)
0.0215 (8)
0.0220 (8)
0.0270 (9)
0.0211 (9)
0.0219 (8)
0.0341 (16)
0.0333 (16)
0.031 (6)
0.0352 (7)
0.0383 (8)
0.0400 (8)
0.0231 (8)
0.0187 (7)
0.0366 (9)
0.0228 (8)
0.0270 (9)
0.0211 (8)
0.0196 (8)
0.0201 (8)
0.0188 (8)
0.0198 (8)
0.0188 (8)
0.0225 (8)
0.0225 (8)
0.0196 (8)
0.0251 (9)
0.0243 (9)
0.0242 (13)
0.0263 (13)
0.021 (5)
0.0249 (7)
0.0310 (7)
0.0424 (8)
0.0251 (8)
0.0207 (7)
0.0404 (9)
0.0192 (8)
0.0238 (9)
0.0221 (9)
0.0181 (8)
0.0244 (8)
0.0193 (8)
0.0242 (8)
0.0191 (8)
0.0213 (8)
0.0256 (9)
0.0280 (9)
0.0299 (9)
0.0264 (9)
0.0203 (14)
0.0343 (14)
0.038 (5)
−0.0052 (6)
0.0046 (5)
0.0132 (6)
0.0072 (6)
0.0098 (7)
0.0083 (6)
0.0087 (7)
0.0065 (7)
0.0099 (7)
0.0125 (7)
0.0059 (7)
0.0091 (7)
0.0092 (7)
0.0088 (7)
0.0084 (7)
0.0036 (7)
0.0089 (7)
0.0098 (7)
0.0045 (7)
0.0079 (7)
0.0100 (12)
0.0099 (11)
0.016 (4)
0.0048 (5)
0.0119 (6)
0.0113 (6)
0.0021 (6)
−0.0021 (6)
0.0178 (7)
−0.0044 (6)
−0.0038 (7)
−0.0012 (7)
−0.0018 (6)
−0.0023 (7)
−0.0032 (6)
−0.0016 (7)
−0.0019 (6)
−0.0003 (7)
−0.0002 (7)
0.0028 (7)
0.0057 (7)
−0.0010 (7)
0.0004 (11)
0.0045 (10)
−0.003 (4)
0.011 (5)
O4A
O4B
N4
0.0053 (6)
0.0031 (6)
0.0033 (7)
−0.0018 (6)
−0.0002 (7)
−0.0020 (7)
−0.0067 (7)
−0.0025 (7)
0.0020 (7)
−0.0012 (7)
−0.0010 (7)
−0.0009 (7)
−0.0011 (7)
0.0020 (7)
−0.0020 (7)
0.0005 (7)
0.0015 (7)
−0.0020 (7)
−0.0001 (11)
0.0031 (12)
0.008 (4)
N8
N15
C1
C2
C3
C4
C5
C6
C7
C9
C10
C11
C12
C13
C14
C16
C17
C16B
C17B
C18
C19
0.049 (7)
0.045 (6)
0.042 (7)
−0.002 (5)
−0.0006 (8)
−0.0057 (10)
−0.012 (6)
0.0139 (8)
0.0217 (11)
0.0297 (10)
0.0578 (15)
0.0283 (9)
0.0337 (11)
0.0362 (10)
0.0497 (13)
0.0077 (8)
−0.0002 (10)
Geometric parameters (Å, º)
O1—C1
1.334 (2)
C10—H10
0.9500
O1—H1
0.8400
C11—C12
C11—H11
C12—C13
C13—C14
C13—H13
C14—H14
C16—C17
C16—H16A
C16—H16B
C17—H17A
1.414 (2)
0.9500
O4A—N4
O4B—N4
N4—C4
1.2316 (19)
1.233 (2)
1.456 (2)
1.289 (2)
1.413 (2)
1.379 (2)
1.457 (2)
1.481 (3)
1.553 (9)
1.406 (2)
1.384 (2)
0.9500
N8—C7
N8—C9
0.9500
N15—C12
N15—C18
N15—C16
N15—C16B
1.518 (4)
0.9900
0.9900
0.9800
Acta Cryst. (2012). C68, o279–o282
sup-7

supplementary materials
C1—C2
C1—C6
C2—C3
C2—H2
C3—C4
C3—H3
C4—C5
C5—C6
C5—H5
C6—C7
C7—H7
C9—C14
C9—C10
C10—C11
1.400 (2)
1.420 (2)
1.377 (2)
0.9500
C17—H17B
C17—H17C
C16B—C17B
C16B—H16C
C16B—H16D
C17B—H17D
C17B—H17E
C17B—H17F
C18—C19
0.9800
0.9800
1.515 (13)
0.9900
0.9900
0.9800
0.9800
0.9800
1.519 (3)
0.9900
0.9900
0.9800
0.9800
0.9800
1.391 (2)
0.9500
1.382 (2)
1.389 (2)
0.9500
1.457 (2)
0.9500
C18—H18A
C18—H18B
C19—H19A
C19—H19B
C19—H19C
1.390 (2)
1.399 (2)
1.380 (2)
C1—O1—H1
O4A—N4—O4B
O4A—N4—C4
O4B—N4—C4
C7—N8—C9
C12—N15—C18
C12—N15—C16
C18—N15—C16
C12—N15—C16B
C18—N15—C16B
O1—C1—C2
O1—C1—C6
C2—C1—C6
C3—C2—C1
C3—C2—H2
C1—C2—H2
C2—C3—C4
C2—C3—H3
C4—C3—H3
C5—C4—C3
C5—C4—N4
C3—C4—N4
C4—C5—C6
C4—C5—H5
C6—C5—H5
C5—C6—C1
C5—C6—C7
C1—C6—C7
N8—C7—C6
N8—C7—H7
C6—C7—H7
C14—C9—C10
C14—C9—N8
C10—C9—N8
109.5
C14—C13—C12
C14—C13—H13
C12—C13—H13
C13—C14—C9
121.18 (16)
119.4
122.88 (15)
118.29 (15)
118.83 (14)
123.82 (15)
121.03 (15)
120.63 (16)
117.62 (16)
113.4 (4)
108.0 (4)
118.84 (15)
121.43 (15)
119.73 (15)
120.65 (16)
119.7
119.4
121.70 (16)
119.2
C13—C14—H14
C9—C14—H14
119.2
N15—C16—C17
N15—C16—H16A
C17—C16—H16A
N15—C16—H16B
C17—C16—H16B
111.1 (2)
109.4
109.4
109.4
109.4
H16A—C16—H16B
C16—C17—H17A
C16—C17—H17B
H17A—C17—H17B
C16—C17—H17C
H17A—C17—H17C
H17B—C17—H17C
C17B—C16B—N15
C17B—C16B—H16C
N15—C16B—H16C
C17B—C16B—H16D
N15—C16B—H16D
H16C—C16B—H16D
C16B—C17B—H17D
C16B—C17B—H17E
H17D—C17B—H17E
C16B—C17B—H17F
H17D—C17B—H17F
H17E—C17B—H17F
N15—C18—C19
108.0
109.5
109.5
109.5
109.5
109.5
109.5
100.1 (8)
111.8
119.7
119.03 (16)
120.5
120.5
121.75 (16)
118.65 (15)
119.59 (15)
119.89 (16)
120.1
111.8
111.8
111.8
109.5
109.5
109.5
109.5
109.5
109.5
109.5
114.89 (16)
108.5
108.5
108.5
120.1
118.95 (15)
119.82 (15)
121.22 (15)
119.51 (15)
120.2
120.2
117.97 (15)
116.11 (15)
125.91 (15)
N15—C18—H18A
C19—C18—H18A
N15—C18—H18B
Acta Cryst. (2012). C68, o279–o282
sup-8

supplementary materials
C11—C10—C9
C11—C10—H10
C9—C10—H10
C10—C11—C12
C10—C11—H11
C12—C11—H11
N15—C12—C13
N15—C12—C11
C13—C12—C11
120.65 (16)
119.7
C19—C18—H18B
108.5
H18A—C18—H18B
C18—C19—H19A
C18—C19—H19B
H19A—C19—H19B
C18—C19—H19C
H19A—C19—H19C
H19B—C19—H19C
107.5
109.5
109.5
109.5
109.5
109.5
109.5
119.7
122.02 (16)
119.0
119.0
121.84 (16)
121.65 (16)
116.47 (15)
O1—C1—C2—C3
C6—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
C2—C3—C4—N4
O4A—N4—C4—C5
O4B—N4—C4—C5
O4A—N4—C4—C3
O4B—N4—C4—C3
C3—C4—C5—C6
N4—C4—C5—C6
C4—C5—C6—C1
C4—C5—C6—C7
O1—C1—C6—C5
C2—C1—C6—C5
O1—C1—C6—C7
C2—C1—C6—C7
C9—N8—C7—C6
C5—C6—C7—N8
C1—C6—C7—N8
C7—N8—C9—C14
C7—N8—C9—C10
C14—C9—C10—C11
−179.48 (15)
0.3 (3)
N8—C9—C10—C11
−179.88 (15)
−0.5 (3)
C9—C10—C11—C12
C18—N15—C12—C13
C16—N15—C12—C13
C16B—N15—C12—C13
C18—N15—C12—C11
C16—N15—C12—C11
C16B—N15—C12—C11
C10—C11—C12—N15
C10—C11—C12—C13
N15—C12—C13—C14
C11—C12—C13—C14
C12—C13—C14—C9
C10—C9—C14—C13
N8—C9—C14—C13
−0.6 (3)
167.89 (17)
−2.1 (3)
0.5 (3)
178.95 (15)
173.99 (15)
−6.2 (2)
37.1 (4)
−14.6 (3)
175.41 (18)
−145.4 (4)
−176.66 (16)
1.0 (2)
−4.5 (2)
175.30 (15)
−0.1 (2)
−178.58 (14)
−0.2 (2)
176.75 (17)
−0.9 (3)
179.04 (15)
179.86 (15)
0.1 (2)
0.3 (3)
0.2 (2)
179.99 (15)
82.2 (2)
0.6 (2)
C12—N15—C16—C17
C18—N15—C16—C17
C12—N15—C16B—C17B
C18—N15—C16B—C17B
C12—N15—C18—C19
C16—N15—C18—C19
C16B—N15—C18—C19
−179.09 (15)
179.41 (14)
−178.28 (15)
0.9 (2)
−88.1 (2)
−106.0 (6)
117.0 (6)
−72.0 (2)
98.3 (2)
−178.65 (15)
1.1 (3)
61.1 (4)
−0.1 (2)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O1—H1···N8
0.84
0.95
0.98
0.95
1.81
2.64
2.60
2.56
2.557 (2)
3.421 (2)
3.195 (3)
3.328 (2)
148
139
119
138
C14—H14···O1i
C17—H17B···O4Aii
C5—H5···O4Biii
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+3, −y, −z+2.
Acta Cryst. (2012). C68, o279–o282
sup-9