Download citation
Download citation
link to html
The mol­ecules in (E)-N-(3,4,5-tri­meth­oxy­benzyl­idene)naph­thalen-1-amine, C20H19NO3, (I), and its reduction product N-(3,4,5-tri­meth­oxy­benzyl)naphthalen-1-amine, C20H21NO3, (II), are both conformationally chiral, but (I) crystallizes in a centrosymmetric space group, while (II) crystallizes with just one conformational enantio­mer in each crystal. A combination of two C-H...O hydrogen bonds links the mol­ecules of (I) into sheets containing a single type of R66(44) ring, and these sheets are linked into a continuous three-dimensional array by a single [pi]-[pi] stacking inter­action. The mol­ecules of (II) are linked into complex sheets by a combination of N-H...O, C-H...O and C-H...[pi](arene) hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229613034839/sf3215sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229613034839/sf3215Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229613034839/sf3215IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229613034839/sf3215Isup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229613034839/sf3215IIsup5.cml
Supplementary material

CCDC references: 979036; 979037

Introduction top

We report here the molecular and supra­molecular structures of (E)-N-(3,4,5-tri­meth­oxy­benzyl­idene)naphthalen-1-amine, (I) (Fig. 1), and its reduction product N-(3,4,5-tri­meth­oxy­benzyl)­naphthalen-1-amine, (II) (Fig. 2). Compound (I) was prepared using a thermal condensation reaction between 1-naphthyl­amine and 3,4,5-tri­meth­oxy­benzaldehyde, and (II) was prepared from (I) by reduction with sodium borohydride.

Experimental top

Synthesis and crystallization top

For the synthesis of (I), a mixture of 1-naphthyl­amine (2.1 mmol) and 3,4,5-tri­meth­oxy­benzaldehyde (2.1 mmol) was heated in an oil bath at 423 K for 8 min until complete disappearance of the starting materials, as monitored by thin-layer chromatography (TLC). The mixture was cooled to ambient temperature and the resulting brown solid was triturated with ethanol to afford the title compound, (I), as brown crystals (yield 86%, m.p. 402 K). Spectroscopic analysis: FT–IR (KBr, ν, cm-1): 3015, 2991, 2953, 2932, 2831, 1618 (C N), 1578 (CC), 1502, 1331, 1227 (C—O), 1130 (C—O), 772.

For the synthesis of (II), a twofold molar excess of sodium borohydride was added in portions over a period of 15 min to a solution of (I) (0.400 g) in ethanol (12 ml). After complete disappearance of the starting compound, (I), as monitored by TLC, the solvent was removed under reduced pressure, an excess of water was added and the product was exhaustively extracted with ethyl acetate. The combined organic extracts were dried using anhydrous sodium sulfate; the drying agent was then removed by filtration and the solvent removed under reduced pressure to afford (II) as pale-yellow crystals (yield 98%, m.p. 412 K). Spectroscopic analysis: FT–IR (KBr, ν, cm-1): 3413 (N—H), 3004, 2933, 2836, 1586 (CC), 1532, 1504, 1237 (C—O), 1114 (C—O), 1005, 778.

Crystals of (I) and (II) suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in air, of the corresponding solutions in methanol.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps, and they were then treated as riding. C-bound H atoms were permitted to ride in geometrically idealized positions, with C—H = 0.95 (aromatic and alkenyl), 0.98 (CH3) or 0.99 Å (CH2), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and k = 1.2 for all other C-bound H atoms. The H atom bonded to atom N1 in (II) was permitted to ride at the position located in a difference map, with Uiso(H) = 1.2Ueq(N), giving an N—H distance of 0.97 Å. Several low-angle reflections, (101) in (I) and (101) and (002) in (II), which had been wholly or partially attenuated by the beam-stop, were omitted from the data sets. In the absence of significant resonant scattering, the Flack x parameter (Flack, 1983) for (II) was indeterminate (Flack & Bernardinelli, 2000); accordingly, the Friedel-equivalent reflections for (II) were merged prior to the final refinements. It was not possible, therefore, to determine the absolute configuration of the molecule in the crystal of (II) selected for data collection. The reference molecule for (II) was selected to have the same sign for the torsion angle C13—C14—O14—C24 as that in the reference molecule for (I).

Results and discussion top

Despite their similar molecular constitutions, (I) and (II) crystallize in very different space groups, the centrosymmetric monoclinic space group P21/n in the case of (I) and the Sohnke orthorhombic space group P212121 in the case of (II). Both compounds crystallize with Z = 4 in unit cells of very similar volume, although it is perhaps surprising that the unit-cell volume for (I) is marginally greater than that for (II), presumably reflecting the stronger inter­molecular hydrogen-bonding in (II) (see below). Consistent with this, the density of (I) (1.296 Mg m-3) is slightly greater than that of (II) (1.283 Mg m-3).

In neither compound are the ring systems exactly coplanar with the central C—NCC linking unit, as indicated by the leading torsion angles (Tables 2 and 3). However, the torsion angles defining the orientation of the tri­meth­oxy­phenyl ring in (I) and of the naphthalene system in (II) with respect to the central spacer unit are both close to zero, but in (I) there is no geometric evidence for any electronic delocalization across the spacer unit. The dihedral angle between the tris­ubstituted aryl ring and the naphthalene system in (I) is 55.4 (2)°, whereas in (II) this angle is 88.2 (2)°. In both compounds, atom C24 of the 4-meth­oxy substituent is considerably displaced from the plane of the adjacent aryl ring, by 1.224 (3) Å in (I) and 1.018 (3) Å in (II). A conformation having atom C24 nearly coplanar with the adjacent aryl ring is precluded by the steric congestion between atom C24 and atoms O13 or O15 which would thereby result. Similar conformations have been observed in other 3,4,5-tri­meth­oxy­phenyl derivatives (Trilleras et al., 2005; Peralta et al., 2007; Cuervo et al., 2009). For compound (II), the torsion angles (Table 3) indicate considerable deviation from planarity for the methyl C atoms, C23 and C25 of the 3-meth­oxy and 5-meth­oxy substituents, which are displaced from the plane of the adjacent ring by 0.252 (3) and 0.468 (3) Å, respectively, as opposed to displacements of only 0.043 (3) and 0.128 (3) Å, respectively, in (I). However, in both compounds the two C—C—O angles at atom C14 have fairly similar values, whereas the corresponding pairs of values at atoms C13 and C15 differ by ca 10° (Tables 2 and 3), as typically found (Seip & Seip, 1973; Ferguson et al., 1996) for meth­oxy­aryl systems in which the meth­oxy C atom is effectively coplanar with the adjacent aryl ring. The N1—C17 distances are clearly consistent with the different oxidation levels in (I) and (II), and it is inter­esting to note the relative values of the bond angles at atoms N1 and C17, but no simple rationalization for this is possible.

The molecules of (I) and (II) exhibit no inter­nal symmetry and hence they are both conformationally chiral. For (I), the centrosymmetric space group accommodates equal numbers of the two conformational enanti­omers. However, for (II), in the absence of any twinning, for which no evidence was found, each crystal contains only a single conformational enanti­omer. It was not possible to establish the absolute configuration of the molecules in the crystal of (II) selected for data collection, but this lack has no chemical significance. Compound (I) thus crystallizes as a conformational racemate, while (II) crystallizes as a conformational conglomerate.

The molecules of (I) are linked into a three-dimensional array in the form of π-stacked hydrogen-bonded sheets. The sheets are built using two C—H···O hydrogen bonds (Table 4) and their formation is readily analysed in terms of two one-dimensional substructures (Ferguson et al., 1998a,b; Gregson et al., 2000). Molecules related by the 21 screw axis along (1/4, y, 1/4) are linked by the shorter hydrogen bond to form a C(7) chain (Bernstein et al., 1995) running parallel to the [010] direction (Fig. 3). In addition, molecules related by translation are linked by the longer of the two hydrogen bonds to form a C(11) chain running parallel to the [110] direction (Fig. 4). The combination of chains along [010] and [110] generates a sheet lying parallel to (001) and built from a single type of R66(44) ring (Fig. 5).

Two sheets of this type, related to one another by inversion, pass through each unit cell, in the domains 0 < z < 1/2 and 1/2 < z < 1.0, respectively, and all of the sheets are linked into a three-dimensional structure by the action of a single aromatic ππ stacking inter­action. The C5–C10 rings in the molecules at (x, y, z) and (2 - x, 1 - y, 1 - z), which lie in different hydrogen-bonded sheets, are strictly parallel, with an inter­planar spacing of 3.480 (2) Å; the ring-centroid separation is 3.798 (2) Å, corresponding to a near-ideal ring-centroid offset of 1.521 (2) Å (Fig. 6). Propagation of this inter­action by the space-group symmetry operators is sufficient to link all of the hydrogen-bonded sheets.

There are four independent hydrogen bonds in the crystal structure of (II) (Table 5), including an N—H···O hydrogen bond, which is necessarily absent from the structure of (I). However, despite the large number of hydrogen bonds in (II), the supra­molecular assembly is only two-dimensional. The overall sheet structure is of considerable complexity but, as in (I), its formation can be analysed in terms of simple substructures. The N—H···O hydrogen bond links molecules related by the 21 screw axis along (1/2, y, 1/4) into a C(7) chain running parallel to the [010] direction, and this chain formation is enhanced by a rather long, but nearly linear, C—H···O hydrogen bond which forms a C(5) motif, so that these two inter­actions together generate a C(5)C(7)[R22(10)] chain of rings (Fig. 7).

This chain of rings actually lies within a sheet generated by the two C—H···π(arene) hydrogen bonds. The inter­action having atom C4 as the donor links molecules related by translation into a chain running parallel to the [100] direction, while that involving atom C7 as the donor links molecules related by the 21 screw axis along (0, y, 1/4) into a chain running parallel to the [010] direction. In combination, these two chains generate a sheet lying parallel to (001) (Fig. 8). Two sheets pass through each unit cell, in the domains 0 < z < 1/2 and 1/2 < z < 1.0, and containing screw axes at z = 1/4 and z = 3/4, respectively. The only possible direction-specific inter­action between molecules in adjacent sheets is a C—H···π(arene) contact (Table 5), which not only involves a C—H bond of low acidity but is characterized by a rather long H···A distance, so that this contact is unlikely to be structurally significant.

Related literature top

For related literature, see: Bernstein et al. (1995); Cuervo et al. (2009); Ferguson et al. (1996, 1998a, 1998b); Flack (1983); Flack & Bernardinelli (2000); Gregson et al. (2000); Peralta et al. (2007); Seip & Seip (1973); Trilleras et al. (2005).

Computing details top

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 3. Part of the crystal structure of (I), showing the formation of a hydrogen-bonded C(7) chain parallel to [010]. Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash symbol (#) are at the symmetry positions (1/2 - x, 1/2 + y, 1/2 - z) and (1/2 - x, -1/2 + y, 1/2 - z), respectively.

Fig. 4. Part of the crystal structure of (I), showing the formation of a hydrogen-bonded C(11) chain parallel to [110]. Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash symbol (#) are at the symmetry positions (1 + x, 1 + y, z) and (-1 + x, -1 + y, z), respectively.

Fig. 5. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet of R66(44) rings parallel to (001). Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Fig. 6. Part of the crystal structure of (I), showing the formation of the ππ stacking interaction which links adjacent hydrogen-bonded sheets. For the sake of clarity, all H atoms have been omitted. The atom marked with an asterisk (*) is at the symmetry position (2 - x, 1 - y, 1 - z).

Fig. 7. Part of the crystal structure of (II) showing the formation of a hydrogen-bonded C(5)C(7)[R22(10)] chain of rings parallel to [010]. Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash symbol (#) are at the symmetry positions (1 - x, 1/2 + y, 1/2 - z) and (1 - x, -1/2 + y, 1/2 - z), respectively.

Fig. 8. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded sheet parallel to (001). Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
(I) (E)-N-(3,4,5-trimethoxybenzylidene)naphthalen-1-amine top
Crystal data top
C20H19NO3F(000) = 680
Mr = 321.36Dx = 1.283 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3821 reflections
a = 8.9697 (11) Åθ = 2.8–27.5°
b = 9.3300 (9) ŵ = 0.09 mm1
c = 19.9254 (12) ÅT = 120 K
β = 93.846 (8)°Block, brown
V = 1663.8 (3) Å30.29 × 0.28 × 0.20 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3820 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode2117 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.070
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.0°
φ and ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1212
Tmin = 0.958, Tmax = 0.983l = 2525
23021 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.170H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0849P)2 + 0.2545P]
where P = (Fo2 + 2Fc2)/3
3820 reflections(Δ/σ)max = 0.001
220 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C20H19NO3V = 1663.8 (3) Å3
Mr = 321.36Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.9697 (11) ŵ = 0.09 mm1
b = 9.3300 (9) ÅT = 120 K
c = 19.9254 (12) Å0.29 × 0.28 × 0.20 mm
β = 93.846 (8)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3820 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2117 reflections with I > 2σ(I)
Tmin = 0.958, Tmax = 0.983Rint = 0.070
23021 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0600 restraints
wR(F2) = 0.170H-atom parameters constrained
S = 1.02Δρmax = 0.29 e Å3
3820 reflectionsΔρmin = 0.28 e Å3
220 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.7281 (2)0.3879 (2)0.36376 (11)0.0296 (5)
C20.8085 (3)0.3861 (3)0.30740 (11)0.0351 (6)
H20.78220.32100.27190.042*
C30.9295 (3)0.4804 (3)0.30213 (12)0.0410 (6)
H30.98460.47790.26300.049*
C40.9690 (3)0.5751 (3)0.35213 (13)0.0407 (6)
H41.04960.63940.34710.049*
C50.9314 (3)0.6740 (3)0.46483 (13)0.0406 (6)
H51.01250.73820.46080.049*
C60.8559 (3)0.6750 (3)0.52169 (13)0.0423 (6)
H60.88520.73910.55720.051*
C70.7341 (3)0.5814 (3)0.52824 (12)0.0384 (6)
H70.68120.58370.56800.046*
C80.6916 (2)0.4873 (2)0.47775 (11)0.0318 (6)
H80.60960.42460.48270.038*
C90.7695 (2)0.4829 (2)0.41803 (11)0.0288 (5)
C100.8910 (2)0.5786 (2)0.41162 (12)0.0327 (6)
N10.6048 (2)0.2945 (2)0.37165 (9)0.0302 (5)
C170.5076 (2)0.2825 (2)0.32196 (10)0.0286 (5)
H170.52110.33580.28220.034*
C110.3764 (2)0.1899 (2)0.32425 (10)0.0281 (5)
C120.3613 (2)0.0951 (2)0.37753 (10)0.0286 (5)
H120.43850.08720.41240.034*
C130.2336 (2)0.0129 (2)0.37929 (10)0.0276 (5)
C140.1200 (2)0.0237 (2)0.32800 (10)0.0273 (5)
C150.1357 (2)0.1180 (2)0.27449 (10)0.0284 (5)
C160.2646 (2)0.2006 (2)0.27254 (10)0.0280 (5)
H160.27620.26420.23600.034*
O130.20582 (17)0.08364 (17)0.42864 (7)0.0352 (4)
C230.3156 (3)0.0947 (3)0.48375 (11)0.0377 (6)
H23A0.41110.12500.46710.057*
H23B0.28310.16540.51610.057*
H23C0.32810.00120.50590.057*
O140.00403 (17)0.06360 (17)0.32899 (7)0.0331 (4)
C240.1241 (3)0.0034 (3)0.36338 (14)0.0489 (7)
H24A0.08850.02130.40950.073*
H24B0.20530.07340.36440.073*
H24C0.16070.08320.33980.073*
O150.01854 (16)0.12059 (17)0.22703 (7)0.0355 (4)
C250.0380 (3)0.1994 (3)0.16682 (11)0.0423 (7)
H25A0.04870.30160.17760.064*
H25B0.04930.18530.13520.064*
H25C0.12780.16550.14640.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0279 (12)0.0276 (13)0.0333 (13)0.0027 (10)0.0012 (10)0.0049 (10)
C20.0367 (14)0.0343 (14)0.0349 (13)0.0023 (11)0.0059 (11)0.0018 (10)
C30.0388 (15)0.0436 (16)0.0423 (15)0.0041 (12)0.0147 (11)0.0043 (12)
C40.0340 (14)0.0348 (14)0.0540 (16)0.0046 (11)0.0082 (12)0.0055 (12)
C50.0330 (14)0.0324 (14)0.0565 (17)0.0066 (11)0.0037 (12)0.0011 (12)
C60.0365 (14)0.0354 (15)0.0543 (17)0.0040 (12)0.0015 (12)0.0138 (12)
C70.0327 (14)0.0397 (15)0.0434 (15)0.0005 (12)0.0056 (11)0.0067 (11)
C80.0260 (12)0.0300 (14)0.0393 (14)0.0006 (10)0.0023 (10)0.0016 (10)
C90.0236 (12)0.0271 (13)0.0356 (13)0.0006 (10)0.0011 (10)0.0046 (10)
C100.0274 (13)0.0279 (13)0.0428 (14)0.0027 (10)0.0019 (10)0.0023 (11)
N10.0309 (10)0.0294 (11)0.0306 (10)0.0049 (9)0.0039 (8)0.0005 (8)
C170.0341 (13)0.0264 (13)0.0258 (12)0.0003 (10)0.0062 (10)0.0003 (9)
C110.0307 (13)0.0269 (12)0.0272 (12)0.0019 (10)0.0057 (9)0.0050 (9)
C120.0297 (12)0.0292 (13)0.0267 (12)0.0020 (10)0.0004 (9)0.0018 (9)
C130.0328 (13)0.0252 (12)0.0250 (12)0.0018 (10)0.0037 (10)0.0009 (9)
C140.0304 (13)0.0250 (12)0.0268 (12)0.0033 (10)0.0039 (9)0.0036 (9)
C150.0316 (13)0.0287 (13)0.0248 (12)0.0011 (10)0.0016 (9)0.0050 (9)
C160.0341 (13)0.0250 (12)0.0254 (12)0.0026 (10)0.0058 (9)0.0002 (9)
O130.0359 (9)0.0391 (10)0.0300 (9)0.0100 (8)0.0018 (7)0.0084 (7)
C230.0414 (14)0.0425 (16)0.0285 (13)0.0058 (12)0.0029 (10)0.0091 (11)
O140.0320 (9)0.0347 (10)0.0327 (9)0.0064 (7)0.0029 (7)0.0014 (7)
C240.0373 (15)0.0496 (18)0.0614 (18)0.0045 (13)0.0163 (13)0.0060 (13)
O150.0356 (9)0.0386 (10)0.0313 (9)0.0059 (8)0.0049 (7)0.0038 (7)
C250.0469 (16)0.0467 (16)0.0318 (14)0.0095 (13)0.0089 (11)0.0077 (11)
Geometric parameters (Å, º) top
C1—C21.374 (3)C11—C121.395 (3)
C1—N11.425 (3)C12—C131.381 (3)
C1—C91.428 (3)C12—H120.9500
C2—C31.407 (3)C13—O131.368 (2)
C2—H20.9500C13—C141.398 (3)
C3—C41.361 (3)C14—O141.380 (2)
C3—H30.9500C14—C151.396 (3)
C4—C101.417 (3)C15—O151.366 (2)
C4—H40.9500C15—C161.392 (3)
C5—C61.358 (3)C16—H160.9500
C5—C101.412 (3)O13—C231.429 (2)
C5—H50.9500C23—H23A0.9800
C6—C71.412 (3)C23—H23B0.9800
C6—H60.9500C23—H23C0.9800
C7—C81.370 (3)O14—C241.429 (3)
C7—H70.9500C24—H24A0.9800
C8—C91.420 (3)C24—H24B0.9800
C8—H80.9500C24—H24C0.9800
C9—C101.421 (3)O15—C251.428 (3)
N1—C171.280 (2)C25—H25A0.9800
C17—C111.463 (3)C25—H25B0.9800
C17—H170.9500C25—H25C0.9800
C11—C161.393 (3)
C2—C1—N1122.4 (2)C13—C12—C11119.62 (19)
C2—C1—C9120.2 (2)C13—C12—H12120.2
N1—C1—C9117.40 (19)C11—C12—H12120.2
C1—C2—C3120.2 (2)O13—C13—C12125.09 (19)
C1—C2—H2119.9O13—C13—C14114.47 (19)
C3—C2—H2119.9C12—C13—C14120.4 (2)
C4—C3—C2121.0 (2)O14—C14—C13119.71 (19)
C4—C3—H3119.5O14—C14—C15120.35 (18)
C2—C3—H3119.5C15—C14—C13119.9 (2)
C3—C4—C10120.6 (2)O15—C15—C14115.33 (19)
C3—C4—H4119.7O15—C15—C16124.92 (19)
C10—C4—H4119.7C16—C15—C14119.76 (19)
C6—C5—C10120.9 (2)C15—C16—C11119.9 (2)
C6—C5—H5119.6C15—C16—H16120.1
C10—C5—H5119.6C11—C16—H16120.1
C5—C6—C7120.3 (2)C13—O13—C23116.76 (17)
C5—C6—H6119.8O13—C23—H23A109.5
C7—C6—H6119.8O13—C23—H23B109.5
C8—C7—C6120.5 (2)H23A—C23—H23B109.5
C8—C7—H7119.7O13—C23—H23C109.5
C6—C7—H7119.7H23A—C23—H23C109.5
C7—C8—C9120.3 (2)H23B—C23—H23C109.5
C7—C8—H8119.8C14—O14—C24114.13 (17)
C9—C8—H8119.8O14—C24—H24A109.5
C8—C9—C10118.7 (2)O14—C24—H24B109.5
C8—C9—C1122.3 (2)H24A—C24—H24B109.5
C10—C9—C1118.9 (2)O14—C24—H24C109.5
C5—C10—C4121.8 (2)H24A—C24—H24C109.5
C5—C10—C9119.2 (2)H24B—C24—H24C109.5
C4—C10—C9119.0 (2)C15—O15—C25117.36 (17)
C1—N1—C17117.48 (18)O15—C25—H25A109.5
N1—C17—C11122.34 (19)O15—C25—H25B109.5
N1—C17—H17118.8H25A—C25—H25B109.5
C11—C17—H17118.8O15—C25—H25C109.5
C16—C11—C12120.4 (2)H25A—C25—H25C109.5
C16—C11—C17118.38 (19)H25B—C25—H25C109.5
C12—C11—C17121.17 (19)
N1—C1—C2—C3179.9 (2)N1—C17—C11—C16169.9 (2)
C9—C1—C2—C31.6 (3)N1—C17—C11—C128.7 (3)
C1—C2—C3—C40.3 (4)C16—C11—C12—C130.8 (3)
C2—C3—C4—C101.5 (4)C17—C11—C12—C13177.7 (2)
C10—C5—C6—C70.7 (4)C11—C12—C13—O13179.9 (2)
C5—C6—C7—C80.7 (4)C11—C12—C13—C140.2 (3)
C6—C7—C8—C90.1 (4)O13—C13—C14—O142.5 (3)
C7—C8—C9—C100.5 (3)C12—C13—C14—O14177.21 (19)
C7—C8—C9—C1179.2 (2)O13—C13—C14—C15179.58 (19)
C2—C1—C9—C8179.0 (2)C12—C13—C14—C150.2 (3)
N1—C1—C9—C80.7 (3)O14—C14—C15—O153.0 (3)
C2—C1—C9—C102.3 (3)C13—C14—C15—O15180.00 (19)
N1—C1—C9—C10179.38 (19)O14—C14—C15—C16176.99 (19)
C6—C5—C10—C4179.5 (2)C13—C14—C15—C160.0 (3)
C6—C5—C10—C90.0 (4)O15—C15—C16—C11179.4 (2)
C3—C4—C10—C5178.8 (2)C14—C15—C16—C110.6 (3)
C3—C4—C10—C90.8 (4)C12—C11—C16—C151.0 (3)
C8—C9—C10—C50.6 (3)C17—C11—C16—C15177.53 (19)
C1—C9—C10—C5179.3 (2)C12—C13—O13—C232.8 (3)
C8—C9—C10—C4179.9 (2)C14—C13—O13—C23177.49 (19)
C1—C9—C10—C41.1 (3)C15—C14—O14—C2492.2 (2)
C2—C1—N1—C1746.8 (3)C13—C14—O14—C2490.8 (2)
C9—C1—N1—C17134.9 (2)C16—C15—O15—C258.6 (3)
C1—N1—C17—C11179.99 (19)C14—C15—O15—C25171.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O13i0.952.523.454 (3)169
C17—H17···O14ii0.952.403.331 (2)166
Symmetry codes: (i) x+1, y+1, z; (ii) x+1/2, y+1/2, z+1/2.
(II) N-(3,4,5-trimethoxybenzyl)naphthalen-1-amine top
Crystal data top
C20H21NO3F(000) = 688
Mr = 323.38Dx = 1.296 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2170 reflections
a = 9.4460 (17) Åθ = 2.7–27.5°
b = 11.0868 (18) ŵ = 0.09 mm1
c = 15.8195 (16) ÅT = 120 K
V = 1656.7 (4) Å3Block, pale yellow
Z = 40.41 × 0.39 × 0.32 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2168 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1799 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.078
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.8°
φ and ω scansh = 1212
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1214
Tmin = 0.955, Tmax = 0.973l = 2016
16040 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.046P)2 + 0.4465P]
where P = (Fo2 + 2Fc2)/3
2168 reflections(Δ/σ)max = 0.001
220 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C20H21NO3V = 1656.7 (4) Å3
Mr = 323.38Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 9.4460 (17) ŵ = 0.09 mm1
b = 11.0868 (18) ÅT = 120 K
c = 15.8195 (16) Å0.41 × 0.39 × 0.32 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2168 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1799 reflections with I > 2σ(I)
Tmin = 0.955, Tmax = 0.973Rint = 0.078
16040 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.105H-atom parameters constrained
S = 1.09Δρmax = 0.21 e Å3
2168 reflectionsΔρmin = 0.18 e Å3
220 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.1583 (2)0.6593 (2)0.39872 (15)0.0225 (5)
C20.1231 (3)0.5526 (2)0.43806 (15)0.0253 (5)
H20.19450.50750.46620.030*
C30.0173 (3)0.5090 (2)0.43722 (16)0.0279 (6)
H30.03850.43490.46460.033*
C40.1232 (3)0.5712 (2)0.39793 (16)0.0280 (5)
H40.21710.54050.39810.034*
C50.1997 (3)0.7497 (2)0.31591 (17)0.0316 (6)
H50.29380.71950.31450.038*
C60.1700 (3)0.8580 (2)0.27839 (17)0.0317 (6)
H60.24300.90170.25070.038*
C70.0316 (3)0.9049 (2)0.28072 (17)0.0311 (6)
H70.01160.98080.25550.037*
C80.0740 (3)0.8412 (2)0.31924 (16)0.0282 (6)
H80.16700.87370.32020.034*
C90.0484 (3)0.7277 (2)0.35786 (15)0.0238 (5)
C100.0924 (3)0.6816 (2)0.35684 (16)0.0252 (5)
N10.2942 (2)0.70652 (18)0.40028 (13)0.0251 (4)
H10.32760.75760.35470.030*
C170.4065 (3)0.6527 (2)0.44923 (16)0.0256 (5)
H17A0.37030.63770.50700.031*
H17B0.48430.71220.45400.031*
C110.4685 (2)0.5354 (2)0.41586 (15)0.0239 (5)
C120.4780 (3)0.5146 (2)0.32929 (15)0.0245 (5)
H120.44190.57210.29030.029*
C130.5407 (3)0.4088 (2)0.30039 (14)0.0222 (5)
C140.5933 (3)0.3236 (2)0.35702 (16)0.0240 (5)
C150.5822 (3)0.3443 (2)0.44355 (16)0.0258 (5)
C160.5209 (3)0.4509 (2)0.47294 (16)0.0259 (5)
H160.51500.46590.53200.031*
O130.55711 (19)0.37999 (15)0.21667 (11)0.0282 (4)
C230.5280 (3)0.4733 (2)0.15638 (16)0.0334 (6)
H23A0.42630.49080.15620.050*
H23B0.55730.44650.10000.050*
H23C0.58050.54630.17180.050*
O140.65142 (19)0.21920 (15)0.32366 (11)0.0299 (4)
C240.7927 (3)0.1905 (3)0.35080 (17)0.0333 (6)
H24A0.84640.26520.35910.050*
H24B0.83930.14100.30770.050*
H24C0.78860.14560.40410.050*
O150.6316 (2)0.25456 (17)0.49517 (12)0.0350 (5)
C250.6763 (3)0.2872 (3)0.57782 (16)0.0371 (7)
H25A0.73810.35800.57460.056*
H25B0.72830.21990.60330.056*
H25C0.59340.30620.61260.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0230 (11)0.0241 (11)0.0205 (11)0.0009 (10)0.0042 (10)0.0034 (10)
C20.0277 (12)0.0264 (12)0.0219 (12)0.0015 (10)0.0010 (10)0.0001 (10)
C30.0328 (13)0.0270 (12)0.0239 (12)0.0045 (11)0.0065 (11)0.0023 (11)
C40.0235 (12)0.0310 (13)0.0294 (13)0.0044 (11)0.0035 (11)0.0063 (11)
C50.0258 (12)0.0383 (14)0.0307 (13)0.0022 (12)0.0006 (11)0.0070 (12)
C60.0305 (14)0.0364 (14)0.0283 (13)0.0104 (12)0.0020 (11)0.0035 (12)
C70.0381 (15)0.0269 (13)0.0282 (13)0.0065 (12)0.0060 (12)0.0018 (11)
C80.0285 (13)0.0276 (12)0.0286 (13)0.0028 (11)0.0048 (11)0.0013 (11)
C90.0242 (12)0.0254 (12)0.0217 (11)0.0031 (10)0.0031 (10)0.0030 (10)
C100.0240 (12)0.0289 (12)0.0228 (12)0.0013 (10)0.0024 (10)0.0069 (11)
N10.0225 (9)0.0227 (10)0.0301 (11)0.0014 (9)0.0011 (9)0.0022 (9)
C170.0242 (12)0.0264 (12)0.0263 (12)0.0002 (10)0.0010 (10)0.0045 (10)
C110.0188 (11)0.0244 (12)0.0286 (13)0.0032 (10)0.0004 (10)0.0025 (10)
C120.0230 (11)0.0260 (12)0.0245 (12)0.0003 (10)0.0013 (10)0.0034 (10)
C130.0214 (12)0.0257 (12)0.0195 (11)0.0022 (10)0.0021 (10)0.0008 (9)
C140.0232 (11)0.0197 (11)0.0292 (12)0.0024 (10)0.0015 (10)0.0002 (10)
C150.0236 (12)0.0268 (12)0.0271 (13)0.0033 (10)0.0026 (10)0.0058 (11)
C160.0253 (12)0.0279 (13)0.0245 (12)0.0060 (11)0.0006 (10)0.0014 (10)
O130.0355 (10)0.0274 (9)0.0219 (9)0.0075 (8)0.0003 (7)0.0005 (7)
C230.0422 (15)0.0347 (14)0.0232 (12)0.0090 (13)0.0020 (12)0.0018 (11)
O140.0334 (10)0.0236 (9)0.0328 (9)0.0044 (8)0.0072 (8)0.0024 (8)
C240.0308 (13)0.0341 (14)0.0350 (14)0.0086 (12)0.0009 (12)0.0037 (12)
O150.0490 (12)0.0285 (8)0.0275 (9)0.0009 (9)0.0056 (9)0.0048 (7)
C250.0439 (16)0.0391 (14)0.0285 (14)0.0004 (14)0.0068 (12)0.0074 (12)
Geometric parameters (Å, º) top
C1—C21.378 (3)C11—C121.392 (3)
C1—N11.386 (3)C11—C161.392 (3)
C1—C91.440 (3)C12—C131.392 (3)
C2—C31.411 (4)C12—H120.9500
C2—H20.9500C13—O131.371 (3)
C3—C41.364 (4)C13—C141.393 (3)
C3—H30.9500C14—O141.385 (3)
C4—C101.417 (4)C14—C151.392 (4)
C4—H40.9500C15—O151.369 (3)
C5—C61.369 (4)C15—C161.396 (4)
C5—C101.420 (4)C16—H160.9500
C5—H50.9500O13—C231.434 (3)
C6—C71.408 (4)C23—H23A0.9800
C6—H60.9500C23—H23B0.9800
C7—C81.365 (4)C23—H23C0.9800
C7—H70.9500O14—C241.437 (3)
C8—C91.419 (3)C24—H24A0.9800
C8—H80.9500C24—H24B0.9800
C9—C101.425 (3)C24—H24C0.9800
N1—C171.443 (3)O15—C251.421 (3)
N1—H10.9698C25—H25A0.9800
C17—C111.520 (3)C25—H25B0.9800
C17—H17A0.9900C25—H25C0.9800
C17—H17B0.9900
C2—C1—N1122.7 (2)C12—C11—C16120.3 (2)
C2—C1—C9118.7 (2)C12—C11—C17120.6 (2)
N1—C1—C9118.5 (2)C16—C11—C17119.1 (2)
C1—C2—C3121.1 (2)C13—C12—C11119.4 (2)
C1—C2—H2119.4C13—C12—H12120.3
C3—C2—H2119.4C11—C12—H12120.3
C4—C3—C2121.4 (2)O13—C13—C12124.2 (2)
C4—C3—H3119.3O13—C13—C14115.0 (2)
C2—C3—H3119.3C12—C13—C14120.8 (2)
C3—C4—C10119.7 (2)O14—C14—C13117.6 (2)
C3—C4—H4120.1O14—C14—C15122.8 (2)
C10—C4—H4120.1C15—C14—C13119.6 (2)
C6—C5—C10121.1 (2)O15—C15—C14116.2 (2)
C6—C5—H5119.4O15—C15—C16123.9 (2)
C10—C5—H5119.4C14—C15—C16119.9 (2)
C5—C6—C7120.2 (2)C11—C16—C15120.1 (2)
C5—C6—H6119.9C11—C16—H16120.0
C7—C6—H6119.9C15—C16—H16120.0
C8—C7—C6119.9 (2)C13—O13—C23116.94 (19)
C8—C7—H7120.0O13—C23—H23A109.5
C6—C7—H7120.0O13—C23—H23B109.5
C7—C8—C9121.7 (2)H23A—C23—H23B109.5
C7—C8—H8119.1O13—C23—H23C109.5
C9—C8—H8119.1H23A—C23—H23C109.5
C8—C9—C10118.2 (2)H23B—C23—H23C109.5
C8—C9—C1122.5 (2)C14—O14—C24116.0 (2)
C10—C9—C1119.3 (2)O14—C24—H24A109.5
C4—C10—C5121.5 (2)O14—C24—H24B109.5
C4—C10—C9119.8 (2)H24A—C24—H24B109.5
C5—C10—C9118.8 (2)O14—C24—H24C109.5
C1—N1—C17122.3 (2)H24A—C24—H24C109.5
C1—N1—H1120.6H24B—C24—H24C109.5
C17—N1—H1113.7C15—O15—C25117.7 (2)
N1—C17—C11116.8 (2)O15—C25—H25A109.5
N1—C17—H17A108.1O15—C25—H25B109.5
C11—C17—H17A108.1H25A—C25—H25B109.5
N1—C17—H17B108.1O15—C25—H25C109.5
C11—C17—H17B108.1H25A—C25—H25C109.5
H17A—C17—H17B107.3H25B—C25—H25C109.5
N1—C1—C2—C3178.1 (2)N1—C17—C11—C1233.4 (3)
C9—C1—C2—C31.3 (4)N1—C17—C11—C16149.0 (2)
C1—C2—C3—C40.4 (4)C16—C11—C12—C130.2 (4)
C2—C3—C4—C100.1 (4)C17—C11—C12—C13177.3 (2)
C10—C5—C6—C70.8 (4)C11—C12—C13—O13179.1 (2)
C5—C6—C7—C81.1 (4)C11—C12—C13—C140.3 (4)
C6—C7—C8—C90.2 (4)O13—C13—C14—O142.0 (3)
C7—C8—C9—C101.0 (4)C12—C13—C14—O14178.6 (2)
C7—C8—C9—C1180.0 (2)O13—C13—C14—C15179.9 (2)
C2—C1—C9—C8177.0 (2)C12—C13—C14—C150.5 (4)
N1—C1—C9—C80.1 (3)O14—C14—C15—O150.3 (4)
C2—C1—C9—C102.0 (3)C13—C14—C15—O15177.7 (2)
N1—C1—C9—C10179.0 (2)O14—C14—C15—C16179.2 (2)
C3—C4—C10—C5179.4 (2)C13—C14—C15—C161.2 (4)
C3—C4—C10—C90.9 (3)C12—C11—C16—C150.5 (4)
C6—C5—C10—C4178.1 (2)C17—C11—C16—C15178.1 (2)
C6—C5—C10—C90.4 (4)O15—C15—C16—C11177.5 (2)
C8—C9—C10—C4177.3 (2)C14—C15—C16—C111.3 (4)
C1—C9—C10—C41.8 (3)C12—C13—O13—C2310.2 (3)
C8—C9—C10—C51.3 (3)C14—C13—O13—C23169.2 (2)
C1—C9—C10—C5179.6 (2)C15—C14—O14—C2455.7 (3)
C2—C1—N1—C175.3 (4)C13—C14—O14—C24126.2 (2)
C9—C1—N1—C17171.5 (2)C14—C15—O15—C25154.8 (2)
C1—N1—C17—C1173.6 (3)C16—C15—O15—C2526.3 (4)
Hydrogen-bond geometry (Å, º) top
Cg1 represents the centroid of the ring C11–C16 and Cg2 represents the centroid of the ring C1–C4/C10/C9.
D—H···AD—HH···AD···AD—H···A
N1—H1···O13i0.972.073.016 (3)163
C12—H12···O14i0.952.593.535 (3)176
C4—H4···Cg1ii0.952.693.632 (3)173
C7—H7···Cg2iii0.952.863.677 (3)145
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x1, y, z; (iii) x, y+1/2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC20H19NO3C20H21NO3
Mr321.36323.38
Crystal system, space groupMonoclinic, P21/nOrthorhombic, P212121
Temperature (K)120120
a, b, c (Å)8.9697 (11), 9.3300 (9), 19.9254 (12)9.4460 (17), 11.0868 (18), 15.8195 (16)
α, β, γ (°)90, 93.846 (8), 9090, 90, 90
V3)1663.8 (3)1656.7 (4)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.090.09
Crystal size (mm)0.29 × 0.28 × 0.200.41 × 0.39 × 0.32
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.958, 0.9830.955, 0.973
No. of measured, independent and
observed [I > 2σ(I)] reflections
23021, 3820, 2117 16040, 2168, 1799
Rint0.0700.078
(sin θ/λ)max1)0.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.060, 0.170, 1.02 0.042, 0.105, 1.09
No. of reflections38202168
No. of parameters220220
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.280.21, 0.18

Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) for (I) top
N1—C171.280 (2)
C1—N1—C17117.48 (18)O14—C14—C13119.71 (19)
N1—C17—C11122.34 (19)O14—C14—C15120.35 (18)
O13—C13—C12125.09 (19)O15—C15—C14115.33 (19)
O13—C13—C14114.47 (19)O15—C15—C16124.92 (19)
C2—C1—N1—C1746.8 (3)C12—C13—O13—C232.8 (3)
C1—N1—C17—C11179.99 (19)C13—C14—O14—C2490.8 (2)
N1—C17—C11—C128.7 (3)C16—C15—O15—C258.6 (3)
Selected geometric parameters (Å, º) for (II) top
N1—C171.443 (3)
C1—N1—C17122.3 (2)O14—C14—C13117.6 (2)
N1—C17—C11116.8 (2)O14—C14—C15122.8 (2)
O13—C13—C12124.2 (2)O15—C15—C14116.2 (2)
O13—C13—C14115.0 (2)O15—C15—C16123.9 (2)
C2—C1—N1—C175.3 (4)C12—C13—O13—C2310.2 (3)
C1—N1—C17—C1173.6 (3)C13—C14—O14—C24126.2 (2)
N1—C17—C11—C1233.4 (3)C16—C15—O15—C2526.3 (4)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O13i0.952.523.454 (3)169
C17—H17···O14ii0.952.403.331 (2)166
Symmetry codes: (i) x+1, y+1, z; (ii) x+1/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
Cg1 represents the centroid of the ring C11–C16 and Cg2 represents the centroid of the ring C1–C4/C10/C9.
D—H···AD—HH···AD···AD—H···A
N1—H1···O13i0.972.073.016 (3)163
C12—H12···O14i0.952.593.535 (3)176
C4—H4···Cg1ii0.952.693.632 (3)173
C7—H7···Cg2iii0.952.863.677 (3)145
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x1, y, z; (iii) x, y+1/2, z+1/2.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds