research communications
6-Methyl-2-oxo-N-(quinolin-6-yl)-2H-chromene-3-carboxamide: and Hirshfeld surface analysis
aFP–ENAS–Faculdade de Ciências de Saúde, Escola Superior de Saúde da UFP, Universidade Fernando Pessoa, Rua Carlos da Maia, 296, P-4200-150 Porto, Portugal, bREQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal, cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and dCIQUP/Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, 4169-007 Porto, Portugal
*Correspondence e-mail: jnlow111@gmail.com
The title coumarin derivative, C20H14N2O3, displays intramolecular N—H⋯O and weak C—H⋯O hydrogen bonds, which probably contribute to the approximate planarity of the molecule [dihedral angle between the coumarin and quinoline ring systems = 6.08 (6)°]. The supramolecular structures feature C—H⋯O hydrogen bonds and π–π interactions, as confirmed by Hirshfeld surface analyses.
Keywords: crystal structure; coumarin; carboxamide; Hirshfeld surface analysis.
CCDC reference: 1491340
1. Chemical context
Coumarin and its derivatives are widely recognized by their unique biological properties (Matos et al., 2014; Vazquez-Rodriguez et al., 2013; Chimenti et al., 2010). Our work in this area has shown that coumarin is a valid scaffold for the development of new drugs for aging related diseases, specifically within the class of monoamino oxidase B inhibitors (Matos et al., 2009). On the other hand, quinoline is a nitrogen heterocycle also often used in drug-discovery programs due to its remarkable biological properties, some of them related to neurodegenerative diseases (Sridharan et al., 2011), for instance, as γ-secretase and acetylcholinesterase inhibitors (Camps et al., 2009). As part of our ongoing studies in this area (Gomes et al., 2016), we describe the synthesis and of the title coumarin–quinoline hybrid, 6-methyl-2-oxo-N-(quinolin-6-yl)-2H-chromene-3-carboxamide, (1) (see Scheme).
2. Structural commentary
Fig. 1 shows an ellipsoid plot of the molecular structure of (1). An inspection of the bond lengths shows that there is a slight asymmetry of the electronic distribution around the coumarin ring: the C3—C4 [1.3609 (15) Å] and C3—C2 [1.4600 (18) Å)] bond lengths are shorter and longer, respectively, than those expected for a Car—Car bond, suggesting that the electronic density is rather located near the C3—C4 bond at the pyrone ring, as occurs in other coumarin-3-carboxamide derivatives (Gomes et al., 2016). Also, the C3—C31 bond length [1.5075 (18) Å] is similar to the mean value displayed by other coumarin-3-carboxamide derivatives previously characterized (Gomes et al., 2016) and is of the same order as a Csp3—Csp3 bond.
The C—N rotamer of the amide group governs the conformation of the molecule: the −anti orientation where the N atom is −cis positioned with respect to the oxo O atom of the coumarin system allows the establishment of an intramolecular N32—H32⋯O2 hydrogen bond between the amino group of the carboxamide and the oxo group of the coumarin system, and of a weak intramolecular C317—H317⋯O31 hydrogen bond that connects the quinoline ring with the O atom of the carboxamide group (Table 1). Both these interactions form S(6) rings and connect the spacer carboxamide group with the heteroaromatic rings, probably constraining the rotation/bending of those rings with respect to the plane formed by the amide atoms. In fact, the molecule is roughly planar, as may be evaluated by the set of values for the dihedral angles which are less than 7° (Table 2).
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3. Supramolecular features
In the crystal of (1), molecules are linked by a weak C314—H314⋯O31i hydrogen bond to form a C(8) chain, which runs parallel to the a axis (Fig. 2 and Table 1). There are several π–π contacts that will be described below.
4. Hirshfeld surface analyses
The Hirshfeld surfaces and two-dimensional fingerprint (FP) plots (Rohl et al., 2008) were generated using Crystal Explorer (Wolff et al., 2012). Compound (1) has three O atoms and an N atom that can potentially act as acceptors for hydrogen bonds, but one of the lone pairs of the oxo O atoms of the coumarin nucleus and of the amide moiety are involved in the establishment of intramolecular hydrogen bonds, as discussed above. As such, they contribute to the electronic density of the pro-molecule in the calculation of the Hirshfeld surface, leaving only the remaining pairs available for participation in the supramolecular structure formation. The surface mapped over dnorm displays several red spots that correspond to areas of close contacts between the surface and the neighbouring environment, and the FP plot is presented in Fig. 3.
The contributions from various contacts, listed in Table 3, were selected by partial analysis of the FP plot. Taking out the H⋯H contacts on the surface that are inherent to organic molecules, the most significant contacts can be divided in three groups: (i) H⋯O/O⋯H together with H⋯N/N⋯H that correspond to weak C—H⋯O/N intermolecular interactions (24.5%); (ii) C⋯C and N⋯C/C⋯N contacts that are related with π–π stacking (17.9%): (iii) H⋯C/C⋯H contacts (14.3%).
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The H⋯N/O contacts appear as three highlighted red spots on the top and bottom edges of the surface which form pairs of spots of comlementary size, indicating the contact points of the labelled atoms participating in the C–H⋯N/O interactions (Fig. 3). The strongest spots correspond to oxo atom O31 of the carboxamide acceptor and donor atom H314, which forms the C314—H314⋯O31i hydrogen bond (Table 1), and the other spots correspond to very weak hydrogen-bond contacts, one involving pyrone atom O1 and a H atom of the methyl group (C61—H61B⋯O1ii; Table 1), and the other appearing perpendicular to the quinoline N atom indicating a very weak C8—H8⋯N311ii contact (Table 1). In spite of the weakness of these contacts, their relative strength is reflected in the FP plots where the pair of sharp spikes pointing to south-west is highlighted in light blue.
In this structure, C/N⋯C contacts prevail over the C—H⋯C ones. In fact, the packing in (1) is built up by several π–π interactions (Table 4). The red spots in the frontal zone of the surface correspond to these close contacts. Furthermore, the FP plot also reveals an intense cluster at de/di at 1.8 Å characteristic of C⋯C contacts. Also, when the surface is mapped with shape index, several complementary triangular red hollows and blue bumps appear that are characteristic of the six-ring stacking (Fig. 4). The molecules stack in a column in a head-to-tail fashion along the b axis (Fig. 5). The molecules in these stacks lie across centres of symmetry at (, 1, ), a centrosymetrically related contact between the pyran and pyridine rings, and across the centre at (, , ), which involves three short centrosymmetrically related contacts: (i) between the pyran and pyridine rings, (ii) between the pyran ring and the quinoline phenyl ring and (iii) between the coumarin phenyl ring and the pyridine ring.
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5. Database survey
As reported by Gomes et al. (2016), a search made in the Cambridge Structural Database (CSD, Version 35.7; Groom et al., 2016) revealed the existence of 35 deposited compounds (42 molecules) containing the coumarin carboxamide unit, all of which contained the same intramolecular hydrogen bonds. The present compound also contains these bonds, as described above.
6. Synthesis and crystallization
6-Methylcoumarin-3-carboxylic acid (Murata et al.., 2005) (1 mmol) was dissolved in dichloromethane and 3-[3-(dimethylamino)propyl]-1-ethylcarbodiimide (1.10 mmol) and 4-dimethylaminopyridine (1.10 mmol) were added. The mixture was kept under a of argon at 273 K for 5 min. 6-Aminoquinoline (1 mmol) was then added in small portions. The reaction mixture was stirred for 4 h at room temperature. The obtained precipitate was filtered off and recrystallized from methanol to give colourless needles of (1). Overall yield: 53%; m.p. 545–546 K.
7. Refinement
H atoms were treated as riding atoms, with aromatic C—H = 0.95 Å, with Uiso(H) = 1.2Ueq(C), and methyl C—H = 0.98 Å, with Uiso(H) = 1.5Ueq(C). The amino H atoms were freely refined. Crystal data, data collection and structure details are summarized in Table 5.
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Supporting information
CCDC reference: 1491340
https://doi.org/10.1107/S2056989016011026/hb7596sup1.cif
contains datablocks 1, general. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016011026/hb7596Isup2.hkl
Data collection: GDA https://www.opengda.org/OpenGDA.html; cell
XIA2 0.4.0.370-g47f3bc3, (Winter, 2010; data reduction: XIA2 0.4.0.370-g47f3bc3 (Winter, 2010; program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: ShelXle (Hübschle et al., 2011) SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2014/17 (Sheldrick, 2015b) PLATON (Spek, 2009).C20H14N2O3 | F(000) = 688 |
Mr = 330.33 | Dx = 1.451 Mg m−3 |
Monoclinic, P21/n | Synchrotron' radiation, λ = 0.68891 Å |
a = 7.799 (3) Å | Cell parameters from 3773 reflections |
b = 7.014 (3) Å | θ = 2.6–33.9° |
c = 27.640 (18) Å | µ = 0.09 mm−1 |
β = 90.18 (6)° | T = 100 K |
V = 1512.0 (13) Å3 | Needle, colourless |
Z = 4 | 0.18 × 0.01 × 0.004 mm |
Three-circle diffractometer | 4587 independent reflections |
Radiation source: synchrotron, DLS beamline I19, undulator | 3717 reflections with I > 2σ(I) |
Si 111, double crystal monochromator | Rint = 0.060 |
Detector resolution: 5.81 pixels mm-1 | θmax = 29.5°, θmin = 2.9° |
profile data from ω–scans | h = −11→11 |
Absorption correction: empirical (using intensity measurements) aimless ccp4 (Evans, 2006) | k = −10→10 |
l = −39→39 | |
18408 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.156 | w = 1/[σ2(Fo2) + (0.0954P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max = 0.001 |
4587 reflections | Δρmax = 0.54 e Å−3 |
231 parameters | Δρmin = −0.25 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.61633 (10) | 0.57511 (12) | 0.33247 (3) | 0.02193 (19) | |
O2 | 0.42390 (10) | 0.67655 (12) | 0.38475 (3) | 0.0244 (2) | |
O31 | 0.79011 (10) | 0.65810 (12) | 0.49728 (3) | 0.0240 (2) | |
N32 | 0.50968 (12) | 0.71842 (13) | 0.47835 (3) | 0.0186 (2) | |
N311 | 0.21868 (12) | 0.98576 (13) | 0.65151 (3) | 0.0204 (2) | |
C2 | 0.57274 (14) | 0.62613 (16) | 0.37867 (4) | 0.0196 (2) | |
C3 | 0.70619 (13) | 0.61438 (15) | 0.41571 (4) | 0.0177 (2) | |
C4 | 0.86585 (13) | 0.55411 (15) | 0.40316 (4) | 0.0180 (2) | |
H4 | 0.9519 | 0.5451 | 0.4275 | 0.022* | |
C5 | 1.07250 (14) | 0.44450 (15) | 0.33910 (4) | 0.0200 (2) | |
H5 | 1.1628 | 0.4362 | 0.3622 | 0.024* | |
C4A | 0.90818 (14) | 0.50369 (15) | 0.35425 (4) | 0.0182 (2) | |
C6 | 1.10480 (15) | 0.39806 (16) | 0.29103 (4) | 0.0222 (2) | |
C7 | 0.97020 (15) | 0.41362 (17) | 0.25763 (4) | 0.0238 (2) | |
H7 | 0.9904 | 0.3821 | 0.2247 | 0.029* | |
C8 | 0.80789 (15) | 0.47398 (17) | 0.27134 (4) | 0.0230 (2) | |
H8 | 0.7184 | 0.4858 | 0.2482 | 0.028* | |
C8A | 0.77937 (14) | 0.51669 (16) | 0.31972 (4) | 0.0195 (2) | |
C31 | 0.67345 (13) | 0.66578 (15) | 0.46783 (4) | 0.0185 (2) | |
C34A | 0.18814 (13) | 0.89163 (15) | 0.56639 (4) | 0.0176 (2) | |
C38A | 0.28705 (13) | 0.91692 (15) | 0.60890 (4) | 0.0178 (2) | |
C61 | 1.27981 (16) | 0.3329 (2) | 0.27477 (5) | 0.0312 (3) | |
H61A | 1.3103 | 0.2147 | 0.2916 | 0.047* | |
H61B | 1.3647 | 0.4316 | 0.2824 | 0.047* | |
H61C | 1.2781 | 0.3101 | 0.2398 | 0.047* | |
C312 | 0.05500 (14) | 1.03063 (16) | 0.65149 (4) | 0.0219 (2) | |
H312 | 0.0075 | 1.0795 | 0.6806 | 0.026* | |
C313 | −0.05445 (14) | 1.01098 (16) | 0.61122 (4) | 0.0219 (2) | |
H313 | −0.1717 | 1.0466 | 0.6133 | 0.026* | |
C314 | 0.01123 (13) | 0.93934 (16) | 0.56876 (4) | 0.0199 (2) | |
H314 | −0.0609 | 0.9220 | 0.5413 | 0.024* | |
C315 | 0.26757 (13) | 0.82186 (15) | 0.52375 (4) | 0.0183 (2) | |
H315 | 0.2006 | 0.8037 | 0.4954 | 0.022* | |
C316 | 0.44016 (14) | 0.78004 (15) | 0.52286 (4) | 0.0178 (2) | |
C317 | 0.53856 (14) | 0.80040 (16) | 0.56555 (4) | 0.0197 (2) | |
H317 | 0.6569 | 0.7683 | 0.5655 | 0.024* | |
C318 | 0.46224 (14) | 0.86712 (16) | 0.60735 (4) | 0.0198 (2) | |
H318 | 0.5297 | 0.8798 | 0.6358 | 0.024* | |
H32 | 0.440 (2) | 0.709 (3) | 0.4521 (6) | 0.042 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0188 (4) | 0.0271 (4) | 0.0199 (4) | −0.0001 (3) | 0.0003 (3) | −0.0025 (3) |
O2 | 0.0186 (4) | 0.0295 (5) | 0.0250 (4) | 0.0018 (3) | −0.0007 (3) | −0.0027 (3) |
O31 | 0.0209 (4) | 0.0295 (5) | 0.0216 (4) | 0.0024 (3) | −0.0005 (3) | −0.0043 (3) |
N32 | 0.0184 (4) | 0.0194 (5) | 0.0180 (4) | 0.0012 (3) | 0.0018 (3) | −0.0009 (3) |
N311 | 0.0226 (4) | 0.0201 (5) | 0.0186 (5) | −0.0011 (3) | 0.0019 (3) | −0.0011 (3) |
C2 | 0.0200 (5) | 0.0186 (5) | 0.0203 (5) | −0.0020 (4) | 0.0014 (4) | −0.0007 (4) |
C3 | 0.0185 (5) | 0.0164 (5) | 0.0183 (5) | −0.0012 (4) | 0.0012 (4) | −0.0004 (4) |
C4 | 0.0192 (5) | 0.0155 (5) | 0.0193 (5) | −0.0012 (4) | 0.0008 (4) | 0.0000 (4) |
C5 | 0.0208 (5) | 0.0178 (5) | 0.0214 (5) | −0.0001 (4) | 0.0019 (4) | −0.0001 (4) |
C4A | 0.0199 (5) | 0.0154 (5) | 0.0194 (5) | −0.0022 (4) | 0.0021 (4) | −0.0006 (4) |
C6 | 0.0242 (5) | 0.0197 (5) | 0.0227 (5) | −0.0012 (4) | 0.0046 (4) | −0.0018 (4) |
C7 | 0.0273 (5) | 0.0240 (6) | 0.0202 (5) | −0.0030 (4) | 0.0042 (4) | −0.0024 (4) |
C8 | 0.0248 (5) | 0.0258 (6) | 0.0185 (5) | −0.0030 (4) | −0.0011 (4) | −0.0013 (4) |
C8A | 0.0188 (5) | 0.0193 (5) | 0.0202 (5) | −0.0024 (4) | 0.0021 (4) | −0.0007 (4) |
C31 | 0.0194 (5) | 0.0151 (5) | 0.0212 (5) | −0.0009 (4) | 0.0025 (4) | −0.0005 (4) |
C34A | 0.0178 (5) | 0.0144 (5) | 0.0205 (5) | −0.0002 (3) | 0.0016 (4) | 0.0011 (4) |
C38A | 0.0194 (5) | 0.0158 (5) | 0.0181 (5) | −0.0013 (4) | 0.0016 (4) | 0.0003 (4) |
C61 | 0.0253 (6) | 0.0408 (8) | 0.0274 (6) | 0.0069 (5) | 0.0052 (5) | −0.0060 (5) |
C312 | 0.0238 (5) | 0.0204 (5) | 0.0214 (5) | −0.0012 (4) | 0.0057 (4) | −0.0012 (4) |
C313 | 0.0188 (5) | 0.0216 (5) | 0.0251 (6) | 0.0002 (4) | 0.0032 (4) | 0.0006 (4) |
C314 | 0.0180 (5) | 0.0202 (5) | 0.0215 (5) | −0.0006 (4) | −0.0001 (4) | 0.0015 (4) |
C315 | 0.0195 (5) | 0.0167 (5) | 0.0188 (5) | 0.0004 (4) | −0.0001 (4) | 0.0003 (4) |
C316 | 0.0201 (5) | 0.0148 (5) | 0.0185 (5) | −0.0001 (4) | 0.0029 (4) | 0.0006 (4) |
C317 | 0.0183 (5) | 0.0203 (5) | 0.0206 (5) | 0.0010 (4) | 0.0016 (4) | 0.0002 (4) |
C318 | 0.0204 (5) | 0.0207 (5) | 0.0185 (5) | −0.0005 (4) | −0.0011 (4) | −0.0002 (4) |
O1—C2 | 1.3701 (16) | C7—H7 | 0.9500 |
O1—C8A | 1.3827 (14) | C8—C8A | 1.3887 (18) |
O2—C2 | 1.2255 (14) | C8—H8 | 0.9500 |
O31—C31 | 1.2201 (16) | C34A—C38A | 1.4149 (18) |
N32—C31 | 1.3618 (14) | C34A—C315 | 1.4200 (17) |
N32—C316 | 1.4136 (16) | C34A—C314 | 1.4214 (15) |
N32—H32 | 0.907 (18) | C38A—C318 | 1.4111 (16) |
N311—C312 | 1.3147 (15) | C61—H61A | 0.9800 |
N311—C38A | 1.3814 (16) | C61—H61B | 0.9800 |
C2—C3 | 1.4600 (18) | C61—H61C | 0.9800 |
C3—C4 | 1.3609 (15) | C312—C313 | 1.4075 (19) |
C3—C31 | 1.5075 (18) | C312—H312 | 0.9500 |
C4—C4A | 1.4368 (17) | C313—C314 | 1.3769 (17) |
C4—H4 | 0.9500 | C313—H313 | 0.9500 |
C5—C6 | 1.3918 (18) | C314—H314 | 0.9500 |
C5—C4A | 1.4119 (16) | C315—C316 | 1.3779 (15) |
C5—H5 | 0.9500 | C315—H315 | 0.9500 |
C4A—C8A | 1.3866 (18) | C316—C317 | 1.4128 (18) |
C6—C7 | 1.4000 (19) | C317—C318 | 1.3830 (17) |
C6—C61 | 1.5092 (17) | C317—H317 | 0.9500 |
C7—C8 | 1.3886 (17) | C318—H318 | 0.9500 |
C2—O1—C8A | 123.10 (10) | N32—C31—C3 | 115.51 (11) |
C31—N32—C316 | 129.15 (11) | C38A—C34A—C315 | 119.63 (10) |
C31—N32—H32 | 111.5 (11) | C38A—C34A—C314 | 117.32 (10) |
C316—N32—H32 | 119.3 (11) | C315—C34A—C314 | 123.05 (11) |
C312—N311—C38A | 117.43 (11) | N311—C38A—C318 | 119.26 (11) |
O2—C2—O1 | 116.17 (11) | N311—C38A—C34A | 122.75 (10) |
O2—C2—C3 | 126.42 (11) | C318—C38A—C34A | 117.98 (10) |
O1—C2—C3 | 117.42 (10) | C6—C61—H61A | 109.5 |
C4—C3—C2 | 119.32 (11) | C6—C61—H61B | 109.5 |
C4—C3—C31 | 118.40 (11) | H61A—C61—H61B | 109.5 |
C2—C3—C31 | 122.28 (10) | C6—C61—H61C | 109.5 |
C3—C4—C4A | 121.96 (11) | H61A—C61—H61C | 109.5 |
C3—C4—H4 | 119.0 | H61B—C61—H61C | 109.5 |
C4A—C4—H4 | 119.0 | N311—C312—C313 | 124.28 (11) |
C6—C5—C4A | 121.27 (12) | N311—C312—H312 | 117.9 |
C6—C5—H5 | 119.4 | C313—C312—H312 | 117.9 |
C4A—C5—H5 | 119.4 | C314—C313—C312 | 118.92 (10) |
C8A—C4A—C5 | 118.13 (11) | C314—C313—H313 | 120.5 |
C8A—C4A—C4 | 117.61 (11) | C312—C313—H313 | 120.5 |
C5—C4A—C4 | 124.25 (11) | C313—C314—C34A | 119.27 (11) |
C5—C6—C7 | 118.28 (11) | C313—C314—H314 | 120.4 |
C5—C6—C61 | 121.45 (12) | C34A—C314—H314 | 120.4 |
C7—C6—C61 | 120.28 (11) | C316—C315—C34A | 121.13 (11) |
C8—C7—C6 | 121.73 (11) | C316—C315—H315 | 119.4 |
C8—C7—H7 | 119.1 | C34A—C315—H315 | 119.4 |
C6—C7—H7 | 119.1 | C315—C316—C317 | 119.45 (11) |
C7—C8—C8A | 118.52 (12) | C315—C316—N32 | 117.26 (11) |
C7—C8—H8 | 120.7 | C317—C316—N32 | 123.29 (10) |
C8A—C8—H8 | 120.7 | C318—C317—C316 | 119.86 (10) |
O1—C8A—C4A | 120.59 (10) | C318—C317—H317 | 120.1 |
O1—C8A—C8 | 117.36 (11) | C316—C317—H317 | 120.1 |
C4A—C8A—C8 | 122.06 (11) | C317—C318—C38A | 121.90 (11) |
O31—C31—N32 | 124.57 (11) | C317—C318—H318 | 119.0 |
O31—C31—C3 | 119.91 (10) | C38A—C318—H318 | 119.0 |
C8A—O1—C2—O2 | 179.41 (9) | C4—C3—C31—O31 | 2.12 (16) |
C8A—O1—C2—C3 | −0.94 (15) | C2—C3—C31—O31 | −178.23 (10) |
O2—C2—C3—C4 | 179.54 (11) | C4—C3—C31—N32 | −177.74 (9) |
O1—C2—C3—C4 | −0.06 (15) | C2—C3—C31—N32 | 1.91 (15) |
O2—C2—C3—C31 | −0.09 (18) | C312—N311—C38A—C318 | 179.98 (10) |
O1—C2—C3—C31 | −179.70 (9) | C312—N311—C38A—C34A | −0.77 (16) |
C2—C3—C4—C4A | 0.81 (16) | C315—C34A—C38A—N311 | 179.40 (10) |
C31—C3—C4—C4A | −179.54 (9) | C314—C34A—C38A—N311 | −0.32 (16) |
C6—C5—C4A—C8A | −0.76 (16) | C315—C34A—C38A—C318 | −1.34 (15) |
C6—C5—C4A—C4 | −179.86 (10) | C314—C34A—C38A—C318 | 178.94 (10) |
C3—C4—C4A—C8A | −0.58 (16) | C38A—N311—C312—C313 | 0.74 (17) |
C3—C4—C4A—C5 | 178.52 (10) | N311—C312—C313—C314 | 0.39 (18) |
C4A—C5—C6—C7 | 0.76 (17) | C312—C313—C314—C34A | −1.51 (16) |
C4A—C5—C6—C61 | −179.40 (11) | C38A—C34A—C314—C313 | 1.45 (15) |
C5—C6—C7—C8 | 0.15 (18) | C315—C34A—C314—C313 | −178.25 (10) |
C61—C6—C7—C8 | −179.69 (11) | C38A—C34A—C315—C316 | −0.68 (16) |
C6—C7—C8—C8A | −1.03 (18) | C314—C34A—C315—C316 | 179.02 (10) |
C2—O1—C8A—C4A | 1.19 (16) | C34A—C315—C316—C317 | 2.29 (16) |
C2—O1—C8A—C8 | −178.25 (10) | C34A—C315—C316—N32 | −177.58 (9) |
C5—C4A—C8A—O1 | −179.57 (9) | C31—N32—C316—C315 | −178.87 (10) |
C4—C4A—C8A—O1 | −0.41 (15) | C31—N32—C316—C317 | 1.27 (18) |
C5—C4A—C8A—C8 | −0.15 (17) | C315—C316—C317—C318 | −1.86 (16) |
C4—C4A—C8A—C8 | 179.00 (10) | N32—C316—C317—C318 | 178.01 (10) |
C7—C8—C8A—O1 | −179.54 (10) | C316—C317—C318—C38A | −0.20 (17) |
C7—C8—C8A—C4A | 1.03 (18) | N311—C38A—C318—C317 | −178.93 (10) |
C316—N32—C31—O31 | 2.43 (19) | C34A—C38A—C318—C317 | 1.78 (16) |
C316—N32—C31—C3 | −177.72 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C314—H314···O31i | 0.95 | 2.50 | 3.278 (2) | 139 |
C8—H8···N311ii | 0.95 | 2.68 | 3.394 (3) | 133 |
C317—H317···O31 | 0.95 | 2.29 | 2.903 (2) | 122 |
N32—H32···O2 | 0.907 (18) | 1.879 (18) | 2.686 (2) | 147.3 (15) |
Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+3/2, z−1/2. |
Compound | θ1 (°) | θ2 (°) | θ3 (°) |
(1) | 6.08 (6) | 5.0 (12) | 1.73 (11) |
Notes: θ1 is the dihedral angle between the mean planes of the coumarin ring and quinoline ring; θ2 is the dihedral angle between the mean plane of the coumarin ring and the plane defined by atoms O31/C31/N32; θ3 is the dihedral angle between the mean plane of the quinoline ring and the plane defined by atoms O31/C31/N32. |
Compound | CgI | CgJ(aru) | Cg–Cg (Å) | CgI_Perp (Å) | CgJ_Perp (Å) | Slippage (Å) |
1 | Cg1 | Cg2(-x+1, -y, -z-1) | 3.548 (2) | 3.1477 (4) | 3.3051 (4) | 1.290 |
1 | Cg1 | Cg2(-x+1, -y+1, -z-1) | 3.911 (3) | -3.3848 (4) | -3.3352 (4) | 2.043 |
1 | Cg1 | Cg4(-x+1, -y+1, -z-1) | 3.525 (2) | -3.3851 (4) | -3.2952 (4) | 1.252 |
1 | Cg2 | Cg1(-x+1, -y, -z-1) | 3.548 (2) | 3.3050 (4) | 3.1476 (4) | 1.637 |
1 | Cg2 | Cg1(-x+1, -y+1, -z-1) | 3.911 (3) | -3.3352 (4) | -3.3849 (4) | 1.960 |
1 | Cg2 | Cg3(-x+1, -y+1, -z-1) | 3.797 (3) | -3.3389 (4) | -3.5276 (5) | 1.406 |
1 | Cg3 | Cg2(-x+1, -y+1, -z-1) | 3.798 (3) | -3.5277 (5) | -3.3388 (4) | 1.809 |
1 | Cg4 | Cg1(-x+1, -y+1, -z-1) | 3.525 (2) | -3.2951 (4) | -3.3852 (4) | 0.983 |
Notes: CgI(J) = Plane number I(J); Cg–Cg = distance between ring centroids; CgI_Perp = perpendicular distance of CgI on ring J; CgJ_Perp = perpendicular distance of CgJ on ring I; Slippage = distance between CgI and perpendicular projection of CgJ on ring I. Plane 1 is the plane of the coumarin pyran ring with Cg1 as centroid; Plane 2 is the plane of the quinoline pyridine ring with Cg2 as centroid; Plane 3 is the plane of the coumarin phenyl ring with Cg3 as centroid; Plane 4 is the plane of the quinoline phenyl ring with Cg4 as centroid. Some planes are repeated since they are inclined to each other and as a result give slightly different slippages |
Contact | H···H | H···O/O···H | H···N/N···H | C···C | N···C/C···N | H···C/C···H |
(%) | 40.6 | 21.2 | 3.3 | 13.2 | 4.7 | 14.3 |
Compound | θ1 (°) | θ2 (°) | θ3 (°) |
(1) | 6.08 (6) | 5.0 (12) | 1.73 (11) |
Notes: θ1 is the dihedral angle between the mean planes of the coumarin ring and quinoline ring; θ2 is the dihedral angle between the mean plane of the coumarin ring and the plane defined by atoms O31/C31/N32; θ3 is the dihedral angle between the mean plane of the quinoline ring and the plane defined by atoms O31/C31/N32. |
Compound | CgI | CgJ(aru) | Cg–Cg (Å) | CgI_Perp (Å) | CgJ_Perp (Å) | Slippage (Å) |
1 | Cg1 | Cg2(-x+1, -y, -z-1) | 3.548 (2) | 3.1477 (4) | 3.3051 (4) | 1.290 |
1 | Cg1 | Cg2(-x+1, -y+1, -z-1) | 3.911 (3) | -3.3848 (4) | -3.3352 (4) | 2.043 |
1 | Cg1 | Cg4(-x+1, -y+1, -z-1) | 3.525 (2) | -3.3851 (4) | -3.2952 (4) | 1.252 |
1 | Cg2 | Cg1(-x+1, -y, -z-1) | 3.548 (2) | 3.3050 (4) | 3.1476 (4) | 1.637 |
1 | Cg2 | Cg1(-x+1, -y+1, -z-1) | 3.911 (3) | -3.3352 (4) | -3.3849 (4) | 1.960 |
1 | Cg2 | Cg3(-x+1, -y+1, -z-1) | 3.797 (3) | -3.3389 (4) | -3.5276 (5) | 1.406 |
1 | Cg3 | Cg2(-x+1, -y+1, -z-1) | 3.798 (3) | -3.5277 (5) | -3.3388 (4) | 1.809 |
1 | Cg4 | Cg1(-x+1, -y+1, -z-1) | 3.525 (2) | -3.2951 (4) | -3.3852 (4) | 0.983 |
Notes: CgI(J) = Plane number I(J); Cg–Cg = distance between ring centroids; CgI_Perp = perpendicular distance of CgI on ring J; CgJ_Perp = perpendicular distance of CgJ on ring I; Slippage = distance between CgI and perpendicular projection of CgJ on ring I. Plane 1 is the plane of the coumarin pyran ring with Cg1 as centroid; Plane 2 is the plane of the quinoline pyridine ring with Cg2 as centroid; Plane 3 is the plane of the coumarin phenyl ring with Cg3 as centroid; Plane 4 is the plane of the quinoline phenyl ring with Cg4 as centroid. Some planes are repeated since they are inclined to each other and as a result give slightly different slippages |
Contact | H···H | H···O/O···H | H···N/N···H | C···C | N···C/C···N | H···C/C···H |
(%) | 40.6 | 21.2 | 3.3 | 13.2 | 4.7 | 14.3 |
Acknowledgements
The authors thank the staff at the National Crystallographic Service, University of Southampton, for the data collection, help and advice (Coles & Gale, 2012), and the Foundation for Science and Technology (FCT) and FEDER/COMPETE2020 (UID/QUι00081/2015 and POCI-01–0145-FEDER-006980). AF (SFRH/BD/80831/2011) and MJM (SFRH/BPD/95345/2013) were supported by grants from FCT, POPH and QREN.
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