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Syntheses and X-ray structural investigations have been carried out for the two title compounds, viz. C17H17N3O2, (I), and C22H20N2O2, (II). The molecular skeleton of (I) is slightly non-planar; the dihedral angles between the conjugated linkage and the p-(di­methyl­amino)­phenyl ring, and between the linkage and the p-nitro­phenyl ring are 13.0 (2) and 13.8 (2)°, respectively. The dihedral angle between the slightly pyramidal di­methyl­amine substituent and the aromatic ring is 23.3 (1)°. The molecular skeleton of (II) is not planar; the dihedral angles between the conjugated linkage and the naphthalene ring, and between the linkage and the substituted phenyl ring are 36.1 (2) and 2.7 (3)°, respectively. The di­methyl­amine substituent in (II) has a pyramidal geometry; the dihedral angle between this substituent and the naphthalene ring is 71.7 (1)°. The dihedral angle between the nitro group and the plane of the substituted phenyl ring is 9.0 (3)°. There is a weak intermolecular C—H...O hydrogen bond in the crystal structure of (II), which links the mol­ecules into centrosymmetric dimers. Molecular mechanics calculations of molecular conformations have shown that the crystal environment influences the conformation more in (I) than in (II).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103020985/fr1427sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103020985/fr1427Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103020985/fr1427IIsup3.hkl
Contains datablock II

CCDC references: 226127; 226128

Comment top

The present investigation is a continuation of a project that includes the syntheses and structural studies of polar conjugated organic molecules (Antipin et al., 1997, 1998; Nesterov et al., 2000). These compounds have applications in non-linear optical, electrooptical, photorefractive, and optical limiting materials (Zyss et al., 1994; Kuzyk & Dirk, 1998).

Synthesis and X-ray structural investigations have been carried out for the title compounds, (I) and (II) (Figs. 1 and 2). Most of the geometric parameters in molecules (I) and (II) are very similar to the standard values (Allen et al., 1987) and very close to literature data for similar polyene derivatives (Childs et al., 1989; Ercan et al., 1996; Nesterov et al., 2000). The title compounds have a trans,trans geometry about conjugated linkages. The molecular skeleton of (I) is slightly non-planar; the dihedral angles between the conjugated linkage and the p-dimethylaminophenyl ring, and between the linkage and the p-nitrophenyl ring, are 13.0 (2) and 13.8 (2)°, respectively. Moreover, the dihedral angle between the slightly pyramidal dimethylamine substituent [the sum of the bond angles around the N atom is 353.5 (1)°] and the phenyl ring is 23.3 (1)°. The length of the C4—N2 bond is 1.388 (2) Å; although this bond is slightly longer than the average conjugated C—N single bond (1.370 Å), it is significantly shorter than the average non-conjugated C—N single bond (1.430 Å) found in the Cambridge Structural Database (CSD; Allen, 2002). As a result of the strong conjugation between donor and acceptor parts of the molecule in (I), substituted phenyl rings in this molecule have a noticeable quinoid structure, which is most? pronounced in the dimethylaniline phenyl ring (Table 1). The nitro group is essentially coplanar with the aromatic ring; the dihedral angle between planes of these fragments is 1.0 (2)°.

The molecular skeleton of (II) is not planar; the dihedral angles between the conjugated linkage and the naphthalene ring, and between the linkage and the substituted phenyl ring, are 36.1 (2) and 2.7 (3)°, respectively. The dimethylamine substituent in this molecule is more pyramidal [the sum of the bond angles around the N atom is 337.6 (2)°] than that in (I). Furthermore, the dihedral angle between this substituent and the naphthalene ring is 71.7 (1)°, and the C4—N1 bond is much longer than the corresponding C4—N2 bond in (I); its length [1.428 (2) Å] agrees with the standard bond length of the non-conjugated C—N single bond (Allen et al., 1987). These torsion angles and bond lengths indicate that there is considerably less effective? donor–acceptor interaction in (II) compared with (I). The elongation of the C4—N1 bond (Table 2) from the average value for conjugated C—N single bonds [1.370 Å; CSD; Allen, 2002) and the increase of the dihedral angle between such fragments of molecules can be explained by the steric interactions between the dimethylamine group and the H atom of the naphthalene ring. Similar values of bond lengths and dihedral angles have been found for substituted N,N-dimethylanilines and 1,8-naphthalenedicarboximide derivatives (Borbulevych et al., 2002; Kovalevsky et al., 2000). It can be concluded that compounds with aromatic systems such as naphthalene or anthracene do not have as strong a conjugation as similar compounds with benzene rings because of stronger steric interactions between bridging and aromatic parts of the molecules. The deviation of the nitro group from the plane of the substituted phenyl ring in (II) is more significant than the deviaiton in (I); the dihedral angle between these fragments is 9.0 (3)°. There is a weak intermolecular C9—H9A···O1 hydrogen bond in (II) between the H atom of a benzene ring and an O of the nitro group (Table 3), thus linking the molecules into centrosymmetric dimers. Similar hydrogen bonds have been reported previously (Zhang et al., 1998; Desiraju & Steiner, 1999; Huang et al., 2002). Molecules of both (I) and (II) form stacks, in which molecules are located in parallel planes that are not exactly aligned.

In order to investigate the influence of the crystal packing on the geometry of molecules in the crystals, a theoretical search for possible conformations by the molecular mechanics method (MM3; Allinger et al., 1989; Lii & Allinger, 1989) has been completed. It was confirmed that molecules of both (I) and (II) have to be non-planar in order to avoid steric interactions between neighboring H atoms of aromatic substituents and the conjugated bridge. The planarity of the molecules of (I) and (II) would lead to shortened intramolecular H···H distances (<2 Å), viz. H2A···H7A and H8A···H11A in (I), and H2A···H12A, H13A···H16A and H9A···H11A in (II). A search for the optimal geometry of molecules of (I) and (II) was performed using the stochastic search option in the MM3 program package. The results are summarized in Table 4. The comformation of the molecule of (II) corresponds to the second energy minimum found by MM3. The preferred conformation in this case is only slightly lower than the second one, which corresponds to the X-ray structure. However, in (I), the conformation that corresponds to the X-ray structure is higher in energy above the global minimum than in the case of (II) (Table 4). This result shows that the crystal environment influences the conformation in (I) more than in (II).

Experimental top

Compound (I) was synthesized according to literature data (Nesterov et al., 2000) and recrystallized from acetonitrile [m.p. 503 K]. Compound (II) [m.p. 411 K] was synthesized from the Wittig reaction of 1-(dimethylamino)-4-formyl-naphthalene and (4-nitrocinnamyl)(triphenyl)phosphonium chloride using sodium methoxide in methanol as a base. Crystals of (I) and (II) suitable for X-ray diffraction were grown by slow isothermal evaporation from ethanol solution.

Refinement top

All H atoms were positioned geometrically and treated as riding, with C—H distances of 0.95–0.98 Å. Uiso values for H atoms were assigned as 1.2Ueq(C) (1.5Ueq for methyl H atoms).

Computing details top

For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1994); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atom-numbering scheme. Non-H atoms are shown with displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. A view of (II), showing the atom-numbering scheme. Non-H atoms are shown with displacement ellipsoids at the 50% probability level.
(I) top
Crystal data top
C17H17N3O2F(000) = 624
Mr = 295.34Dx = 1.337 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 320 reflections
a = 6.1191 (18) Åθ = 4–24°
b = 7.168 (2) ŵ = 0.09 mm1
c = 33.449 (10) ÅT = 110 K
β = 91.408 (9)°Plate, dark red
V = 1466.7 (7) Å30.50 × 0.40 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1809 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.027
Graphite monochromatorθmax = 25.7°, θmin = 2.4°
ϕ and ω scansh = 76
7168 measured reflectionsk = 88
2740 independent reflectionsl = 4032
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)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.08P)2]
where P = (Fo2 + 2Fc2)/3
2740 reflections(Δ/σ)max < 0.001
201 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C17H17N3O2V = 1466.7 (7) Å3
Mr = 295.34Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.1191 (18) ŵ = 0.09 mm1
b = 7.168 (2) ÅT = 110 K
c = 33.449 (10) Å0.50 × 0.40 × 0.10 mm
β = 91.408 (9)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1809 reflections with I > 2σ(I)
7168 measured reflectionsRint = 0.027
2740 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0590 restraints
wR(F2) = 0.145H-atom parameters constrained
S = 1.02Δρmax = 0.49 e Å3
2740 reflectionsΔρmin = 0.20 e Å3
201 parameters
Special details top

Experimental. The compound was characterized by 1H and 13C NMR and GC—MS spectrometry. 1H NMR (CDCl3, 300 MHz) δ 8.38 (d, 1H, J = 8.83 Hz), 8.24 (d, 2H, J = 8.83 Hz), 7.64 (d, 2H, J = 8.82 Hz), 7.27 (d, 2H, J = 9.19 Hz), 7.25 (overlapping m, 1H), 7.08 (d, 1H, J = 15.81 Hz), 6.74 (d, 2H, J = 9.19 Hz), 3.01 (s, 6H) p.p.m.. 13C NMR (CDCl3, 75 MHz) δ 154.9, 150.1, 147.5, 142.5, 139.6, 137.8, 133.4, 127.5, 124.2, 122.7, 112.6, 40.5 p.p.m.. GC—MS: calculated for C17H17N3O2 295.34, found 295.34.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.9852 (2)0.6619 (2)0.03712 (4)0.0452 (4)
O21.2663 (2)0.8130 (2)0.06083 (4)0.0497 (5)
N10.2472 (2)0.7139 (2)0.28042 (4)0.0287 (4)
N20.0505 (2)0.7440 (2)0.43912 (4)0.0284 (4)
N31.0874 (3)0.7372 (2)0.06480 (5)0.0310 (4)
C10.1806 (3)0.7337 (2)0.32052 (5)0.0249 (4)
C20.3038 (3)0.8147 (3)0.35208 (6)0.0281 (5)
H2A0.44120.86980.34670.034*
C30.2288 (3)0.8155 (3)0.39082 (5)0.0266 (4)
H3A0.31680.87010.41150.032*
C40.0250 (3)0.7372 (2)0.40036 (5)0.0244 (4)
C50.0990 (3)0.6572 (3)0.36844 (5)0.0267 (4)
H5A0.23680.60220.37360.032*
C60.0220 (3)0.6580 (3)0.32987 (5)0.0264 (4)
H6A0.11010.60520.30900.032*
C70.4461 (3)0.7428 (3)0.27092 (6)0.0284 (5)
H7A0.54730.78580.29090.034*
C80.5208 (3)0.7121 (3)0.23098 (6)0.0288 (5)
H8A0.41990.66700.21120.035*
C90.7277 (3)0.7450 (3)0.22069 (5)0.0273 (4)
H9A0.82690.78010.24170.033*
C100.8170 (3)0.7326 (2)0.18055 (5)0.0242 (4)
C110.7044 (3)0.6488 (3)0.14781 (5)0.0260 (4)
H11A0.56740.59030.15180.031*
C120.7912 (3)0.6508 (3)0.10997 (5)0.0273 (5)
H12A0.71500.59490.08800.033*
C130.9922 (3)0.7365 (2)0.10488 (5)0.0240 (4)
C141.1098 (3)0.8190 (3)0.13617 (6)0.0280 (5)
H14A1.24690.87680.13180.034*
C151.0213 (3)0.8145 (3)0.17396 (5)0.0261 (4)
H15A1.10080.86810.19580.031*
C160.1044 (3)0.7830 (3)0.47203 (6)0.0364 (5)
H16A0.16580.90810.46870.055*
H16B0.22250.69060.47200.055*
H16C0.02880.77640.49750.055*
C170.2394 (3)0.6308 (3)0.44919 (6)0.0387 (5)
H17A0.36240.66150.43100.058*
H17B0.27990.65660.47680.058*
H17C0.20290.49840.44650.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0499 (9)0.0543 (11)0.0315 (8)0.0004 (7)0.0024 (7)0.0046 (7)
O20.0490 (9)0.0574 (11)0.0435 (10)0.0181 (8)0.0162 (7)0.0042 (8)
N10.0310 (9)0.0261 (9)0.0290 (9)0.0008 (6)0.0037 (7)0.0007 (7)
N20.0310 (9)0.0275 (10)0.0268 (9)0.0017 (7)0.0040 (7)0.0015 (7)
N30.0362 (9)0.0262 (10)0.0309 (10)0.0046 (7)0.0050 (7)0.0004 (7)
C10.0260 (10)0.0200 (10)0.0286 (10)0.0041 (7)0.0022 (8)0.0007 (8)
C20.0280 (10)0.0226 (10)0.0339 (11)0.0010 (8)0.0034 (8)0.0006 (8)
C30.0297 (10)0.0203 (10)0.0298 (11)0.0009 (8)0.0010 (8)0.0019 (8)
C40.0275 (10)0.0172 (10)0.0285 (11)0.0051 (7)0.0028 (8)0.0007 (8)
C50.0254 (9)0.0213 (10)0.0334 (11)0.0002 (7)0.0019 (8)0.0021 (8)
C60.0267 (10)0.0199 (10)0.0326 (11)0.0004 (7)0.0016 (8)0.0007 (8)
C70.0298 (10)0.0259 (11)0.0293 (11)0.0003 (8)0.0002 (8)0.0020 (8)
C80.0301 (10)0.0285 (11)0.0278 (11)0.0008 (8)0.0003 (8)0.0034 (8)
C90.0305 (10)0.0223 (10)0.0290 (11)0.0013 (7)0.0005 (8)0.0003 (8)
C100.0253 (9)0.0185 (10)0.0290 (10)0.0042 (7)0.0016 (8)0.0026 (8)
C110.0249 (9)0.0217 (10)0.0315 (11)0.0007 (7)0.0034 (8)0.0023 (8)
C120.0298 (10)0.0214 (10)0.0307 (11)0.0018 (8)0.0011 (8)0.0015 (8)
C130.0285 (10)0.0199 (10)0.0237 (10)0.0053 (7)0.0041 (8)0.0026 (8)
C140.0285 (10)0.0205 (10)0.0352 (11)0.0008 (8)0.0031 (8)0.0003 (8)
C150.0281 (10)0.0214 (10)0.0289 (10)0.0002 (8)0.0007 (8)0.0022 (8)
C160.0428 (12)0.0389 (13)0.0277 (11)0.0071 (9)0.0045 (9)0.0028 (9)
C170.0393 (12)0.0436 (14)0.0336 (12)0.0079 (10)0.0076 (9)0.0031 (10)
Geometric parameters (Å, º) top
O1—N31.230 (2)C8—C91.341 (2)
O2—N31.232 (2)C8—H8A0.9500
N1—C71.283 (2)C9—C101.464 (3)
N1—C11.418 (2)C9—H9A0.9500
N2—C41.388 (2)C10—C151.404 (2)
N2—C171.458 (2)C10—C111.413 (2)
N2—C161.462 (2)C11—C121.385 (3)
N3—C131.474 (2)C11—H11A0.9500
C1—C61.396 (2)C12—C131.389 (3)
C1—C21.407 (3)C12—H12A0.9500
C2—C31.385 (3)C13—C141.387 (3)
C2—H2A0.9500C14—C151.388 (3)
C3—C41.411 (3)C14—H14A0.9500
C3—H3A0.9500C15—H15A0.9500
C4—C51.416 (3)C16—H16A0.9800
C5—C61.384 (3)C16—H16B0.9800
C5—H5A0.9500C16—H16C0.9800
C6—H6A0.9500C17—H17A0.9800
C7—C81.439 (3)C17—H17B0.9800
C7—H7A0.9500C17—H17C0.9800
C7—N1—C1120.96 (16)C8—C9—H9A116.6
C4—N2—C17118.71 (15)C10—C9—H9A116.6
C4—N2—C16119.04 (16)C15—C10—C11118.36 (16)
C17—N2—C16115.83 (15)C15—C10—C9118.18 (16)
O1—N3—O2123.32 (16)C11—C10—C9123.41 (16)
O1—N3—C13118.56 (16)C12—C11—C10120.89 (17)
O2—N3—C13118.12 (16)C12—C11—H11A119.6
C6—C1—C2117.03 (17)C10—C11—H11A119.6
C6—C1—N1116.76 (16)C11—C12—C13118.51 (17)
C2—C1—N1126.15 (16)C11—C12—H12A120.7
C3—C2—C1121.32 (17)C13—C12—H12A120.7
C3—C2—H2A119.3C14—C13—C12122.69 (17)
C1—C2—H2A119.3C14—C13—N3118.38 (16)
C2—C3—C4121.66 (17)C12—C13—N3118.93 (16)
C2—C3—H3A119.2C13—C14—C15118.08 (17)
C4—C3—H3A119.2C13—C14—H14A121.0
N2—C4—C3120.91 (17)C15—C14—H14A121.0
N2—C4—C5122.26 (16)C14—C15—C10121.45 (17)
C3—C4—C5116.80 (16)C14—C15—H15A119.3
C6—C5—C4120.81 (17)C10—C15—H15A119.3
C6—C5—H5A119.6N2—C16—H16A109.5
C4—C5—H5A119.6N2—C16—H16B109.5
C5—C6—C1122.37 (17)H16A—C16—H16B109.5
C5—C6—H6A118.8N2—C16—H16C109.5
C1—C6—H6A118.8H16A—C16—H16C109.5
N1—C7—C8122.00 (18)H16B—C16—H16C109.5
N1—C7—H7A119.0N2—C17—H17A109.5
C8—C7—H7A119.0N2—C17—H17B109.5
C9—C8—C7122.30 (18)H17A—C17—H17B109.5
C9—C8—H8A118.8N2—C17—H17C109.5
C7—C8—H8A118.8H17A—C17—H17C109.5
C8—C9—C10126.89 (18)H17B—C17—H17C109.5
C7—N1—C1—C6165.24 (17)C7—C8—C9—C10174.95 (18)
C7—N1—C1—C211.6 (3)C8—C9—C10—C15164.89 (18)
C6—C1—C2—C31.3 (3)C8—C9—C10—C1112.6 (3)
N1—C1—C2—C3175.53 (17)C15—C10—C11—C121.3 (3)
C1—C2—C3—C40.7 (3)C9—C10—C11—C12176.14 (17)
C17—N2—C4—C3168.17 (17)C10—C11—C12—C130.3 (3)
C16—N2—C4—C317.4 (3)C11—C12—C13—C140.4 (3)
C17—N2—C4—C513.6 (3)C11—C12—C13—N3179.21 (16)
C16—N2—C4—C5164.29 (17)O1—N3—C13—C14178.96 (16)
C2—C3—C4—N2178.14 (17)O2—N3—C13—C140.8 (2)
C2—C3—C4—C50.2 (3)O1—N3—C13—C120.1 (2)
N2—C4—C5—C6177.92 (16)O2—N3—C13—C12179.67 (17)
C3—C4—C5—C60.4 (3)C12—C13—C14—C150.1 (3)
C4—C5—C6—C11.1 (3)N3—C13—C14—C15178.73 (16)
C2—C1—C6—C51.5 (3)C13—C14—C15—C101.2 (3)
N1—C1—C6—C5175.61 (16)C11—C10—C15—C141.8 (3)
C1—N1—C7—C8175.97 (17)C9—C10—C15—C14175.76 (16)
N1—C7—C8—C9178.88 (18)
(II) top
Crystal data top
C22H20N2O2Z = 2
Mr = 344.40F(000) = 364
Triclinic, P1Dx = 1.306 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.7383 (10) ÅCell parameters from 320 reflections
b = 10.3948 (16) Åθ = 4–24°
c = 12.8735 (19) ŵ = 0.08 mm1
α = 79.933 (8)°T = 110 K
β = 81.754 (8)°Prism, red
γ = 84.103 (8)°0.45 × 0.35 × 0.25 mm
V = 875.9 (2) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
2589 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.024
Graphite monochromatorθmax = 27.0°, θmin = 2.0°
ϕ and ω scansh = 88
6053 measured reflectionsk = 1312
3800 independent reflectionsl = 1612
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)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.187H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.1177P)2]
where P = (Fo2 + 2Fc2)/3
3800 reflections(Δ/σ)max < 0.001
237 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C22H20N2O2γ = 84.103 (8)°
Mr = 344.40V = 875.9 (2) Å3
Triclinic, P1Z = 2
a = 6.7383 (10) ÅMo Kα radiation
b = 10.3948 (16) ŵ = 0.08 mm1
c = 12.8735 (19) ÅT = 110 K
α = 79.933 (8)°0.45 × 0.35 × 0.25 mm
β = 81.754 (8)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2589 reflections with I > 2σ(I)
6053 measured reflectionsRint = 0.024
3800 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0690 restraints
wR(F2) = 0.187H-atom parameters constrained
S = 1.03Δρmax = 0.53 e Å3
3800 reflectionsΔρmin = 0.27 e Å3
237 parameters
Special details top

Experimental. The compound was characterized by 1H NMR (CDCl3, 250 MHz) δ 8.27 (m, 1H), 8.21 (d, 2H, J = 7.5 Hz), 8.18 (m, 1H), 7.69 (d, 1H, J = 8.0 Hz), 7.57 (d, 2H, J = 7.5 Hz), 7.55 (overlapping m, 3H), 7.26 (dd, 1H, J = 15.5, 10.8 Hz), 7.08 (d, 1H, J = 8.0 Hz), 6.99 (dd, 1H, J = 15.0, 10.8 Hz), 6.72 (d, 1H, J = 15.5 Hz), 2.93 (s, 6H) p.p.m.; and high resolution FAB mass spectrometry [calculated for C22H20N2O2 344.1525, found 344.1527].

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H distances of 0.95 Å for aromatic H atoms and 0.98 Å for CH3 groups.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O11.0384 (2)0.67282 (14)0.04024 (12)0.0411 (4)
O21.0984 (2)0.85891 (14)0.01712 (11)0.0364 (4)
N10.7908 (2)0.16723 (15)0.49113 (12)0.0261 (4)
N20.9982 (2)0.75348 (16)0.01141 (12)0.0288 (4)
C10.2790 (3)0.33263 (17)0.34026 (15)0.0252 (4)
C20.3249 (3)0.37768 (18)0.42734 (15)0.0269 (4)
H2A0.23800.44490.45510.032*
C30.4965 (3)0.32774 (18)0.47693 (15)0.0268 (4)
H3A0.52270.36130.53720.032*
C40.6256 (3)0.23116 (18)0.43893 (14)0.0242 (4)
C50.5962 (3)0.18934 (17)0.34257 (14)0.0236 (4)
C60.7396 (3)0.10256 (18)0.29210 (15)0.0270 (4)
H6A0.85780.06990.32360.032*
C70.7109 (3)0.06526 (19)0.19927 (15)0.0311 (5)
H7A0.80880.00720.16670.037*
C80.5366 (3)0.11261 (19)0.15176 (15)0.0299 (4)
H8A0.51600.08540.08770.036*
C90.3967 (3)0.19763 (18)0.19750 (15)0.0284 (4)
H9A0.28040.22950.16410.034*
C100.4215 (3)0.23920 (17)0.29347 (14)0.0241 (4)
C110.0900 (3)0.37378 (18)0.29624 (15)0.0272 (4)
H11A0.03670.31040.26540.033*
C120.0174 (3)0.48997 (18)0.29400 (14)0.0277 (4)
H12A0.02740.55570.32590.033*
C130.1990 (3)0.51763 (18)0.24444 (14)0.0268 (4)
H13A0.24760.44670.22070.032*
C140.3058 (3)0.63355 (18)0.22864 (14)0.0270 (4)
H14A0.26200.70350.25590.032*
C150.4843 (3)0.66225 (17)0.17299 (14)0.0239 (4)
C160.5573 (3)0.56818 (18)0.12539 (14)0.0259 (4)
H16A0.49020.48280.12930.031*
C170.7258 (3)0.59793 (18)0.07281 (14)0.0257 (4)
H17A0.77430.53400.04040.031*
C180.8219 (3)0.72228 (17)0.06835 (14)0.0243 (4)
C190.7555 (3)0.81793 (18)0.11390 (14)0.0272 (4)
H19A0.82420.90280.10990.033*
C200.5856 (3)0.78694 (18)0.16573 (14)0.0267 (4)
H20A0.53730.85200.19690.032*
C210.8687 (3)0.24241 (19)0.55964 (15)0.0315 (5)
H21A0.89620.32960.52010.047*
H21B0.99340.19700.58300.047*
H21C0.76910.25120.62190.047*
C220.7447 (3)0.03589 (18)0.54869 (16)0.0311 (5)
H22A0.69200.01260.50120.047*
H22B0.64390.04470.61050.047*
H22C0.86760.01170.57260.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0477 (9)0.0390 (9)0.0419 (9)0.0001 (7)0.0222 (7)0.0101 (7)
O20.0354 (8)0.0324 (8)0.0408 (9)0.0058 (6)0.0111 (6)0.0041 (6)
N10.0253 (8)0.0265 (8)0.0261 (8)0.0041 (6)0.0072 (6)0.0008 (6)
N20.0303 (9)0.0296 (9)0.0256 (9)0.0009 (7)0.0069 (6)0.0001 (7)
C10.0252 (9)0.0200 (9)0.0283 (10)0.0039 (7)0.0044 (7)0.0036 (7)
C20.0282 (10)0.0227 (10)0.0291 (10)0.0017 (7)0.0039 (7)0.0023 (7)
C30.0298 (10)0.0263 (10)0.0250 (10)0.0046 (8)0.0057 (7)0.0032 (7)
C40.0226 (9)0.0248 (9)0.0248 (9)0.0057 (7)0.0061 (7)0.0021 (7)
C50.0267 (9)0.0210 (9)0.0221 (9)0.0069 (7)0.0034 (7)0.0023 (7)
C60.0259 (9)0.0271 (10)0.0274 (10)0.0029 (7)0.0052 (7)0.0007 (7)
C70.0330 (10)0.0291 (10)0.0299 (11)0.0019 (8)0.0001 (8)0.0051 (8)
C80.0375 (11)0.0325 (11)0.0201 (9)0.0090 (8)0.0041 (8)0.0018 (8)
C90.0320 (10)0.0268 (10)0.0259 (10)0.0055 (8)0.0083 (8)0.0022 (7)
C100.0257 (9)0.0218 (9)0.0240 (9)0.0062 (7)0.0048 (7)0.0026 (7)
C110.0265 (9)0.0264 (10)0.0282 (10)0.0044 (7)0.0072 (7)0.0008 (7)
C120.0278 (10)0.0283 (10)0.0258 (10)0.0037 (8)0.0035 (7)0.0001 (7)
C130.0265 (9)0.0282 (10)0.0247 (10)0.0055 (7)0.0033 (7)0.0000 (7)
C140.0288 (10)0.0278 (10)0.0238 (10)0.0034 (8)0.0052 (7)0.0006 (7)
C150.0250 (9)0.0248 (9)0.0196 (9)0.0031 (7)0.0014 (7)0.0023 (7)
C160.0271 (9)0.0230 (9)0.0257 (10)0.0008 (7)0.0025 (7)0.0002 (7)
C170.0292 (10)0.0251 (10)0.0225 (9)0.0036 (7)0.0029 (7)0.0027 (7)
C180.0237 (9)0.0265 (10)0.0213 (9)0.0010 (7)0.0050 (7)0.0009 (7)
C190.0298 (10)0.0231 (9)0.0267 (10)0.0023 (7)0.0031 (7)0.0011 (7)
C200.0297 (10)0.0264 (10)0.0248 (10)0.0040 (8)0.0053 (7)0.0039 (7)
C210.0289 (10)0.0377 (11)0.0288 (10)0.0042 (8)0.0073 (8)0.0039 (8)
C220.0305 (10)0.0283 (10)0.0328 (11)0.0029 (8)0.0075 (8)0.0027 (8)
Geometric parameters (Å, º) top
O1—N21.230 (2)C11—C121.341 (3)
O2—N21.235 (2)C11—H11A0.9500
N1—C41.428 (2)C12—C131.440 (2)
N1—C211.457 (2)C12—H12A0.9500
N1—C221.475 (2)C13—C141.338 (3)
N2—C181.463 (2)C13—H13A0.9500
C1—C21.373 (3)C14—C151.465 (2)
C1—C101.441 (3)C14—H14A0.9500
C1—C111.461 (2)C15—C201.396 (3)
C2—C31.409 (2)C15—C161.403 (3)
C2—H2A0.9500C16—C171.385 (2)
C3—C41.369 (3)C16—H16A0.9500
C3—H3A0.9500C17—C181.381 (2)
C4—C51.430 (3)C17—H17A0.9500
C5—C61.419 (3)C18—C191.380 (3)
C5—C101.424 (2)C19—C201.388 (2)
C6—C71.364 (3)C19—H19A0.9500
C6—H6A0.9500C20—H20A0.9500
C7—C81.407 (3)C21—H21A0.9800
C7—H7A0.9500C21—H21B0.9800
C8—C91.366 (3)C21—H21C0.9800
C8—H8A0.9500C22—H22A0.9800
C9—C101.415 (3)C22—H22B0.9800
C9—H9A0.9500C22—H22C0.9800
C4—N1—C21115.40 (15)C11—C12—C13121.65 (18)
C4—N1—C22111.35 (14)C11—C12—H12A119.2
C21—N1—C22110.93 (14)C13—C12—H12A119.2
O1—N2—O2123.32 (15)C14—C13—C12126.32 (18)
O1—N2—C18117.90 (16)C14—C13—H13A116.8
O2—N2—C18118.78 (16)C12—C13—H13A116.8
C2—C1—C10118.02 (16)C13—C14—C15125.83 (18)
C2—C1—C11122.21 (17)C13—C14—H14A117.1
C10—C1—C11119.74 (17)C15—C14—H14A117.1
C1—C2—C3122.33 (18)C20—C15—C16118.26 (16)
C1—C2—H2A118.8C20—C15—C14119.67 (17)
C3—C2—H2A118.8C16—C15—C14122.07 (17)
C4—C3—C2120.53 (17)C17—C16—C15120.96 (17)
C4—C3—H3A119.7C17—C16—H16A119.5
C2—C3—H3A119.7C15—C16—H16A119.5
C3—C4—N1123.45 (17)C18—C17—C16118.74 (17)
C3—C4—C5119.59 (16)C18—C17—H17A120.6
N1—C4—C5116.96 (16)C16—C17—H17A120.6
C6—C5—C10118.70 (17)C17—C18—C19122.33 (16)
C6—C5—C4121.94 (16)C17—C18—N2118.40 (17)
C10—C5—C4119.32 (17)C19—C18—N2119.26 (16)
C7—C6—C5121.23 (17)C18—C19—C20118.29 (17)
C7—C6—H6A119.4C18—C19—H19A120.9
C5—C6—H6A119.4C20—C19—H19A120.9
C6—C7—C8120.09 (18)C19—C20—C15121.43 (17)
C6—C7—H7A120.0C19—C20—H20A119.3
C8—C7—H7A120.0C15—C20—H20A119.3
C9—C8—C7120.20 (18)N1—C21—H21A109.5
C9—C8—H8A119.9N1—C21—H21B109.5
C7—C8—H8A119.9H21A—C21—H21B109.5
C8—C9—C10121.43 (17)N1—C21—H21C109.5
C8—C9—H9A119.3H21A—C21—H21C109.5
C10—C9—H9A119.3H21B—C21—H21C109.5
C9—C10—C5118.33 (17)N1—C22—H22A109.5
C9—C10—C1121.91 (16)N1—C22—H22B109.5
C5—C10—C1119.73 (17)H22A—C22—H22B109.5
C12—C11—C1128.03 (18)N1—C22—H22C109.5
C12—C11—H11A116.0H22A—C22—H22C109.5
C1—C11—H11A116.0H22B—C22—H22C109.5
C10—C1—C2—C35.4 (3)C11—C1—C10—C98.1 (2)
C11—C1—C2—C3172.99 (16)C2—C1—C10—C54.6 (2)
C1—C2—C3—C40.2 (3)C11—C1—C10—C5173.84 (15)
C2—C3—C4—N1173.65 (15)C2—C1—C11—C1232.6 (3)
C2—C3—C4—C55.8 (3)C10—C1—C11—C12149.04 (19)
C21—N1—C4—C325.0 (2)C1—C11—C12—C13177.99 (17)
C22—N1—C4—C3102.6 (2)C11—C12—C13—C14172.96 (18)
C21—N1—C4—C5155.59 (16)C12—C13—C14—C15176.48 (17)
C22—N1—C4—C576.8 (2)C13—C14—C15—C20177.65 (18)
C3—C4—C5—C6171.52 (16)C13—C14—C15—C162.8 (3)
N1—C4—C5—C69.0 (2)C20—C15—C16—C170.2 (3)
C3—C4—C5—C106.4 (2)C14—C15—C16—C17179.69 (16)
N1—C4—C5—C10173.10 (14)C15—C16—C17—C180.3 (3)
C10—C5—C6—C71.0 (3)C16—C17—C18—C190.4 (3)
C4—C5—C6—C7178.92 (17)C16—C17—C18—N2179.18 (15)
C5—C6—C7—C80.1 (3)O1—N2—C18—C178.3 (2)
C6—C7—C8—C91.0 (3)O2—N2—C18—C17171.90 (16)
C7—C8—C9—C100.7 (3)O1—N2—C18—C19170.53 (16)
C8—C9—C10—C50.5 (3)O2—N2—C18—C199.2 (2)
C8—C9—C10—C1177.58 (16)C17—C18—C19—C200.1 (3)
C6—C5—C10—C91.3 (2)N2—C18—C19—C20178.74 (15)
C4—C5—C10—C9179.26 (15)C18—C19—C20—C150.6 (3)
C6—C5—C10—C1176.81 (15)C16—C15—C20—C190.6 (3)
C4—C5—C10—C11.1 (2)C14—C15—C20—C19179.86 (16)
C2—C1—C10—C9173.42 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9A···O1i0.952.463.395 (3)166
Symmetry code: (i) x1, y+1, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC17H17N3O2C22H20N2O2
Mr295.34344.40
Crystal system, space groupMonoclinic, P21/nTriclinic, P1
Temperature (K)110110
a, b, c (Å)6.1191 (18), 7.168 (2), 33.449 (10)6.7383 (10), 10.3948 (16), 12.8735 (19)
α, β, γ (°)90, 91.408 (9), 9079.933 (8), 81.754 (8), 84.103 (8)
V3)1466.7 (7)875.9 (2)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.090.08
Crystal size (mm)0.50 × 0.40 × 0.100.45 × 0.35 × 0.25
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7168, 2740, 1809 6053, 3800, 2589
Rint0.0270.024
(sin θ/λ)max1)0.6100.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.145, 1.02 0.069, 0.187, 1.03
No. of reflections27403800
No. of parameters201237
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.49, 0.200.53, 0.27

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1994), SHELXTL.

Selected geometric parameters (Å, º) for (I) top
N1—C71.283 (2)C3—C41.411 (3)
N1—C11.418 (2)C4—C51.416 (3)
N2—C41.388 (2)C5—C61.384 (3)
C1—C61.396 (2)C7—C81.439 (3)
C1—C21.407 (3)C8—C91.341 (2)
C2—C31.385 (3)C9—C101.464 (3)
C7—N1—C1120.96 (16)N1—C7—C8122.00 (18)
C4—N2—C17118.71 (15)C9—C8—C7122.30 (18)
C4—N2—C16119.04 (16)C8—C9—C10126.89 (18)
C17—N2—C16115.83 (15)
C7—N1—C1—C211.6 (3)N1—C7—C8—C9178.88 (18)
C17—N2—C4—C3168.17 (17)C7—C8—C9—C10174.95 (18)
C16—N2—C4—C317.4 (3)C8—C9—C10—C1112.6 (3)
C1—N1—C7—C8175.97 (17)
Selected geometric parameters (Å, º) for (II) top
N1—C41.428 (2)C12—C131.440 (2)
C1—C111.461 (2)C13—C141.338 (3)
C11—C121.341 (3)C14—C151.465 (2)
C4—N1—C21115.40 (15)C11—C12—C13121.65 (18)
C4—N1—C22111.35 (14)C14—C13—C12126.32 (18)
C21—N1—C22110.93 (14)C13—C14—C15125.83 (18)
C12—C11—C1128.03 (18)
C21—N1—C4—C325.0 (2)C11—C12—C13—C14172.96 (18)
C22—N1—C4—C3102.6 (2)C12—C13—C14—C15176.48 (17)
C2—C1—C11—C1232.6 (3)C13—C14—C15—C162.8 (3)
C1—C11—C12—C13177.99 (17)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C9—H9A···O1i0.952.463.395 (3)166
Symmetry code: (i) x1, y+1, z.
Selected geometric parameters in investigated molecules top
Molecule I
Torsion angle, °
C2—C1—N1—C7C8—C9—C10—C11Energy, kcal/mol
X-ray data11.6-12.6
MM3 best conformation29.1-14.718.06
MM3 conformation (X-ray like)12.3-13.819.24
Data range from MM31.43–29.1-14.7–10.118.06–19.32
Molecule II
C2—C1—C11—C12C13—C14—C15—C16Energy, kcal/mol
X-ray data32.6-2.8
MM3 best conformation-35.4-10.324.05
MM3 conformation (X-ray like)34.5-2.124.36
Data range from MM3-38.4–34.5-12.5–7.224.05–24.70
 

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