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The syntheses, X-ray structural investigations and calculations of the conformational preferences of the carbonyl substituent with respect to the pyran ring have been carried out for the two title compounds, viz. C15H14N2O2, (II), and C20H16N2O2·C2H3N, (III), respectively. In both mol­ecules, the heterocyclic ring adopts a flattened boat conformation. In (II), the carbonyl group and a double bond of the heterocyclic ring are syn, but in (III) they are anti. The carbonyl group forms a short contact with a methyl group H atom in (II). The dihedral angles between the pseudo-axial phenyl substituent and the flat part of the pyran ring are 92.7 (1) and 93.2 (1)° in (II) and (III), respectively. In the crystal structure of (II), inter­molecular N-H...N and N-H...O hydrogen bonds link the mol­ecules into a sheet along the (103) plane, while in (III), they link the mol­ecules into ribbons along the a axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010604844X/sq3047sup1.cif
Contains datablocks II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010604844X/sq3047IIsup2.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010604844X/sq3047IIIsup3.hkl
Contains datablock III

CCDC references: 632942; 632943

Comment top

The present investigation of the title compound, (II) and (III), is a continuation of our work that includes the syntheses and structural studies of heterocyclic compounds, such as 4H-pyran derivatives (Nesterov & Viltchinskaia, 2001; Nesterov et al., 2004, 2005), that can be obtained starting from different unsaturated nitriles (Nesterov et al., 2001a,b). Some 4H-pyran derivatives are potential bioactive compounds, such as calcium antagonists (Suarez et al., 2002) and potent apoptosis inducers (Kemnitzer et al., 2004; Zhang et al., 2005).

X-ray analysis shows that the molecules of (II) and (III) have slightly different structures (Figs. 1 and 2). In both molecules, the pyran ring adopts a flattened boat conformation: atoms O1 and C4 are displaced out of the C2/C3/C5/C6 plane [planar to within 0.026 (1) and 0.021 (1) Å in compounds (II) and (III), respectively] by 0.060 (1) and 0.023 (1) Å, respectively, in (II), and −0.110 (1) and −0.174 (1) Å, respectively, in (III). The bending of the heterocycle along the lines O1···C4, C2···C6 and C3···C5 is 4.1 (1), 5.1 (1) and 1.9 (1)°, respectively, in (II), compared with 13.2 (1), 9.3 (1) and 11.6 (1)°, respectively, in (III). The dihedral angles between the pseudo-axial phenyl substituent and the flat part of the pyran ring are 92.7 (1)° in (II) and 93.2 (1)° in (III).

The CO group has interesting orientational preferences relative to the C5C6 double bond. In compound (II), the groups are syn (`cisoid') [torsion angle C6—C5—C8—O2 = 38.0 (2)°], while in (III) they are anti (`transoid') [torsion angle C6—C5—C8—O2 = −141.4 (2)°]. In the first case, a short intramolecular contact (O2···H7A = 2.31 Å) is present. In the latter case, there is a short steric intramolecular contact [C7···C20 = 3.298 (2) Å] which is shorter than the sum of the van der Waals radii of two C atoms (Rowland & Taylor, 1996). Probably, the C···C contact plays a role in the orientation of the bulky phenyl substituent in the molecule of (III) relative to the heterocycle [torsion angle C5—C8—C9—C20 = 29.9 (2)°].

Similar to related compounds (Nesterov et al., 2004), in both (II) and (III) there is conjugation between the donor NH2 and the acceptor CN groups via the C2C3 double bond. In addition, the H atoms of the NH2 group participate in intermolecular N—H···N and N—H···O hydrogen bonds. In (II), these interactions link the molecules into a sheet along the (103) plane (Fig. 3), while in (III) they link the molecules into ribbons along the a axis (Fig. 4). In (III), the acetonitrile molecules do not participate in hydrogen bonds and do not form any short intermolecular contacts. Most of the geometric parameters in the molecules are very similar to the standard values (Allen et al., 1987) and previous results on related compounds (Nesterov et al., 2004, 2005).

Using computational methods (GAUSSIAN03; Frisch et al., 2003), we explored the conformational preferences of the carbonyl substituent with respect to the pyran ring in compounds (II) and (III). For the molecule of (II), a restricted Hartree–Fock calculation on the conformer in the crystal [basis set 6–311++G(d,p)] gave a conformation that was not significantly different from that found in the crystal itself. Next, an AM1 calculation was carried out to minimize the conformer in the crystal. Continuing at the AM1 level, the O2—C8—C5—C4 angle was rotated in 10° increments and the conformations encountered were minimized until the starting conformer was encountered again. A map of the total energy versus scan step number showed only one distinct minimum conformer, similar to that found in the crystal. Two maxima were encountered, with the carbonyl group either ca 90° out of the plane of the pyran ring (about 2.2 kcal mol−1 above the energy of the minimum; 1 kcal mol−1 = 4.184 kJ mol−1) or nearly anti with respect to the double bond of the pyran ring (about 4.1 kcal mol−1 above the energy of the minimum). The maxima show severe methyl–phenyl and methyl–methyl steric interactions, respectively.

In contrast with compound (II), the calculations on (III) indicated somewhat different intrinsic preferred conformations than those displayed in the crystal. For the molecule of (III), a restricted Hartree–Fock calculation on the conformer in the crystal [basis set 6–311++G(d,p)] gave a conformation with the carbonyl group and the double bond still anti, but with a somewhat different dihedral angle (−141° versus −119°). Continuing at the AM1 level, the O2—C8—C5—C4 angle was rotated in 10° increments and the conformations encountered were minimized until the starting conformer was encountered again. A map of the total energy versus scan step number showed two distinct minima and two distinct maxima. In the found global minimum, the carbonyl group and double bond are approaching a syn relationship, with an associated dihedral angle of 54°. The second minimum had this dihedral angle at about −119° (this was the starting conformer from the crystal), with an associated energy 0.08 kcal mol−1 above the global minimum. The first maximum is 3.26 kcal mol−1 higher in energy than the global minimum and it displays a severe steric interaction between the two phenyl rings; the dihedral angle between the carbonyl group and double bond is −38°. The second maximum is 4.04 kcal mol−1 higher in energy than the global minimum and it displays a severe steric interaction between the phenyl of the ketone moiety and the methyl group; the dihedral angle between the double bond and carbonyl group is about 176°. The calculations indicate that the preferred conformations of (II) and (III) result from an interplay of the steric interactions between the bulky groups in these molecules with the normal intrinsic preferences of enone-type moieties.

Experimental top

Compounds (II) and (III) were obtained by the reaction of benzylydenemalononitrile, (I), with acetylacetone and 1-benzoylacetone, respectively, according to a literature procedure (Nesterov & Viltchinskaia, 2001; Nesterov et al., 2004). The precipitates were isolated and recrystallized from ethanol [m.p. 421 K, yield 78% for (II)] or acetonitrile [m.p. 458 K, yield 87% for (III)]. Crystals of both compounds were grown by slow isothermic evaporation of ethanol and acetonitrile solutions, respectively. Both compounds were characterized by 1H and 13C NMR spectroscopy; details are available in the archived CIF.

Refinement top

For both compounds, all H atoms were placed in geometrically calculated positions and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H, C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for CH3, C—H = 0.98 Å and Uiso(H) = 1.2Ueq(C) for CH, and N—H = 0.86 Å and Uiso(H) = 1.2Ueq(N) for the NH2 groups.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of compound (II), showing the atom numbering used. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A view of compound (III), showing the atom numbering used. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3] Fig. 3. A projection of the crystal packing of (II) along the b axis. Dashed lines denote intermolecular N—H···N and N—H···O hydrogen bonds.
[Figure 4] Fig. 4. A projection of the crystal packing of (III) along the b axis. Dashed lines denote intermolecular N—H···N and N—H···O hydrogen bonds.
(II) 5-Acetyl-2-amino-6-methyl-4-phenyl-4H-pyran-3-carbonitrile top
Crystal data top
C15H14N2O2F(000) = 536
Mr = 254.28Dx = 1.281 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.001 (2) ÅCell parameters from 118 reflections
b = 13.910 (3) Åθ = 4–25°
c = 15.862 (3) ŵ = 0.09 mm1
β = 94.989 (5)°T = 295 K
V = 1319.1 (6) Å3Prism, colourless
Z = 40.30 × 0.25 × 0.20 mm
Data collection top
Bruker SMART APEX II CCD area-detector
diffractometer
3465 independent reflections
Radiation source: fine-focus sealed tube2448 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ϕ and ω scansθmax = 28.9°, θmin = 2.0°
Absorption correction: multi-scan
SADABS (Sheldrick, 2003)
h = 88
Tmin = 0.975, Tmax = 0.983k = 1818
13889 measured reflectionsl = 2121
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.061P)2 + 0.26P]
where P = (Fo2 + 2Fc2)/3
3465 reflections(Δ/σ)max < 0.001
174 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
C15H14N2O2V = 1319.1 (6) Å3
Mr = 254.28Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.001 (2) ŵ = 0.09 mm1
b = 13.910 (3) ÅT = 295 K
c = 15.862 (3) Å0.30 × 0.25 × 0.20 mm
β = 94.989 (5)°
Data collection top
Bruker SMART APEX II CCD area-detector
diffractometer
3465 independent reflections
Absorption correction: multi-scan
SADABS (Sheldrick, 2003)
2448 reflections with I > 2σ(I)
Tmin = 0.975, Tmax = 0.983Rint = 0.031
13889 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.128H-atom parameters constrained
S = 1.01Δρmax = 0.25 e Å3
3465 reflectionsΔρmin = 0.17 e Å3
174 parameters
Special details top

Experimental. Spectroscopic data for (II): 1H NMR (DMSO-d6, 300 MHz, δ, p.p.m): 7.33 (dd, 2H, J = 7.0 and 7.7 Hz), 7.24 (t, 1H, J = 2.2 and 2.2 Hz), 7.17 (d, 2H, J = 7.0 Hz), 6.86 (br s, 2H, NH2), 4.46 (s, 1H), 2.2 (s, 3H), 2.06 (s, 3H); 13C NMR (DMSO-d6, 75 MHz, δ, p.p.m): 198.3, 158.2, 154.7, 144.5, 128.7, 127.1, 126.9, 119.7, 115.0, 57.8, 38.7, 29.8, 18.4.

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
O10.62843 (17)0.48936 (7)0.69760 (6)0.0421 (3)
O20.87903 (19)0.74172 (8)0.82485 (7)0.0512 (3)
N10.4141 (2)0.42467 (9)0.59208 (9)0.0488 (3)
H1A0.30080.42190.55500.059*
H1B0.51020.37870.59590.059*
N20.0609 (2)0.59169 (11)0.55420 (10)0.0584 (4)
C10.1057 (2)0.58387 (10)0.59392 (9)0.0407 (3)
C20.4407 (2)0.50030 (9)0.64359 (9)0.0356 (3)
C30.3084 (2)0.57877 (9)0.64693 (8)0.0352 (3)
C40.3678 (2)0.66531 (9)0.70255 (8)0.0340 (3)
H4A0.25370.67170.74280.041*
C50.5918 (2)0.64825 (9)0.75277 (8)0.0338 (3)
C60.7020 (2)0.56475 (9)0.74956 (8)0.0345 (3)
C70.9089 (3)0.53198 (11)0.79983 (9)0.0426 (3)
H7A0.95440.57960.84170.064*
H7B1.02570.52290.76290.064*
H7C0.88000.47240.82740.064*
C80.6799 (3)0.72562 (10)0.81181 (9)0.0396 (3)
C90.5159 (3)0.78362 (16)0.85566 (13)0.0673 (5)
H9A0.59450.82410.89730.101*
H9B0.41790.74140.88290.101*
H9C0.42960.82280.81500.101*
C100.3586 (2)0.75513 (9)0.64727 (9)0.0357 (3)
C110.5140 (3)0.76929 (10)0.58859 (9)0.0422 (3)
H11A0.63650.72840.58780.051*
C120.4866 (3)0.84455 (12)0.53113 (10)0.0524 (4)
H12A0.59040.85360.49160.063*
C130.3073 (3)0.90576 (12)0.53221 (11)0.0569 (5)
H13A0.28890.95550.49300.068*
C140.1559 (3)0.89352 (13)0.59100 (13)0.0611 (5)
H14A0.03590.93560.59230.073*
C150.1811 (3)0.81822 (12)0.64881 (11)0.0494 (4)
H15A0.07780.81030.68870.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0413 (6)0.0310 (5)0.0506 (6)0.0028 (4)0.0147 (4)0.0015 (4)
O20.0480 (7)0.0476 (6)0.0558 (7)0.0081 (5)0.0077 (5)0.0085 (5)
N10.0494 (8)0.0337 (6)0.0591 (8)0.0043 (5)0.0193 (6)0.0069 (6)
N20.0480 (8)0.0602 (9)0.0628 (9)0.0128 (7)0.0193 (7)0.0154 (7)
C10.0404 (8)0.0363 (7)0.0440 (8)0.0035 (6)0.0044 (6)0.0047 (6)
C20.0351 (7)0.0316 (6)0.0388 (7)0.0037 (5)0.0053 (5)0.0037 (5)
C30.0321 (7)0.0341 (7)0.0381 (7)0.0017 (5)0.0052 (5)0.0017 (5)
C40.0332 (7)0.0328 (6)0.0355 (7)0.0011 (5)0.0004 (5)0.0008 (5)
C50.0358 (7)0.0351 (7)0.0298 (6)0.0026 (5)0.0007 (5)0.0010 (5)
C60.0359 (7)0.0344 (6)0.0321 (6)0.0039 (5)0.0034 (5)0.0029 (5)
C70.0424 (8)0.0418 (7)0.0415 (8)0.0018 (6)0.0084 (6)0.0039 (6)
C80.0465 (9)0.0374 (7)0.0338 (7)0.0013 (6)0.0031 (6)0.0003 (5)
C90.0642 (12)0.0732 (12)0.0638 (11)0.0065 (10)0.0014 (9)0.0305 (10)
C100.0349 (7)0.0319 (6)0.0386 (7)0.0004 (5)0.0060 (5)0.0004 (5)
C110.0472 (9)0.0370 (7)0.0421 (8)0.0012 (6)0.0020 (6)0.0001 (6)
C120.0662 (11)0.0477 (9)0.0429 (8)0.0080 (8)0.0021 (7)0.0064 (7)
C130.0674 (11)0.0427 (8)0.0567 (10)0.0046 (8)0.0169 (9)0.0146 (7)
C140.0502 (10)0.0446 (9)0.0856 (13)0.0109 (8)0.0115 (9)0.0119 (9)
C150.0400 (8)0.0446 (8)0.0633 (10)0.0055 (7)0.0020 (7)0.0069 (7)
Geometric parameters (Å, º) top
O1—C21.3634 (16)C7—H7B0.9600
O1—C61.3823 (16)C7—H7C0.9600
O2—C81.2158 (18)C8—C91.491 (2)
N1—C21.3331 (18)C9—H9A0.9600
N1—H1A0.8600C9—H9B0.9600
N1—H1B0.8600C9—H9C0.9600
N2—C11.1394 (19)C10—C151.382 (2)
C1—C31.4192 (19)C10—C111.388 (2)
C2—C31.3533 (19)C11—C121.388 (2)
C3—C41.5164 (18)C11—H11A0.9300
C4—C51.5205 (18)C12—C131.373 (3)
C4—C101.5246 (18)C12—H12A0.9300
C4—H4A0.9800C13—C141.368 (3)
C5—C61.3398 (19)C13—H13A0.9300
C5—C81.4927 (19)C14—C151.392 (2)
C6—C71.4873 (19)C14—H14A0.9300
C7—H7A0.9600C15—H15A0.9300
C2—O1—C6119.58 (10)H7B—C7—H7C109.5
C2—N1—H1A120.0O2—C8—C9119.99 (14)
C2—N1—H1B120.0O2—C8—C5121.91 (13)
H1A—N1—H1B120.0C9—C8—C5118.09 (14)
N2—C1—C3176.30 (16)C8—C9—H9A109.5
N1—C2—C3128.41 (13)C8—C9—H9B109.5
N1—C2—O1110.20 (12)H9A—C9—H9B109.5
C3—C2—O1121.39 (12)C8—C9—H9C109.5
C2—C3—C1119.50 (12)H9A—C9—H9C109.5
C2—C3—C4123.65 (12)H9B—C9—H9C109.5
C1—C3—C4116.81 (11)C15—C10—C11119.06 (14)
C3—C4—C5109.47 (11)C15—C10—C4119.96 (14)
C3—C4—C10108.72 (11)C11—C10—C4120.62 (12)
C5—C4—C10114.53 (11)C10—C11—C12119.94 (15)
C3—C4—H4A108.0C10—C11—H11A120.0
C5—C4—H4A108.0C12—C11—H11A120.0
C10—C4—H4A108.0C13—C12—C11120.51 (17)
C6—C5—C8119.99 (12)C13—C12—H12A119.7
C6—C5—C4122.16 (12)C11—C12—H12A119.7
C8—C5—C4117.70 (12)C14—C13—C12119.92 (15)
C5—C6—O1123.17 (12)C14—C13—H13A120.0
C5—C6—C7129.57 (12)C12—C13—H13A120.0
O1—C6—C7107.20 (11)C13—C14—C15120.17 (16)
C6—C7—H7A109.5C13—C14—H14A119.9
C6—C7—H7B109.5C15—C14—H14A119.9
H7A—C7—H7B109.5C10—C15—C14120.38 (17)
C6—C7—H7C109.5C10—C15—H15A119.8
H7A—C7—H7C109.5C14—C15—H15A119.8
C6—O1—C2—N1172.23 (12)C2—O1—C6—C53.2 (2)
C6—O1—C2—C38.4 (2)C2—O1—C6—C7179.41 (12)
N1—C2—C3—C14.0 (2)C6—C5—C8—O238.0 (2)
O1—C2—C3—C1175.23 (13)C4—C5—C8—O2146.39 (14)
N1—C2—C3—C4173.65 (14)C6—C5—C8—C9141.71 (16)
O1—C2—C3—C47.1 (2)C4—C5—C8—C933.9 (2)
C2—C3—C4—C50.75 (19)C3—C4—C10—C15104.94 (15)
C1—C3—C4—C5178.45 (12)C5—C4—C10—C15132.28 (14)
C2—C3—C4—C10125.02 (14)C3—C4—C10—C1168.15 (16)
C1—C3—C4—C1052.67 (16)C5—C4—C10—C1154.63 (17)
C3—C4—C5—C64.38 (18)C15—C10—C11—C121.7 (2)
C10—C4—C5—C6126.75 (14)C4—C10—C11—C12171.49 (13)
C3—C4—C5—C8179.87 (12)C10—C11—C12—C130.5 (2)
C10—C4—C5—C857.75 (16)C11—C12—C13—C140.9 (3)
C8—C5—C6—O1178.81 (12)C12—C13—C14—C151.1 (3)
C4—C5—C6—O13.4 (2)C11—C10—C15—C141.5 (2)
C8—C5—C6—C72.0 (2)C4—C10—C15—C14171.71 (15)
C4—C5—C6—C7173.40 (14)C13—C14—C15—C100.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.862.163.012 (2)170
N1—H1B···O2ii0.862.353.077 (2)143
Symmetry codes: (i) x, y+1, z+1; (ii) x+3/2, y1/2, z+3/2.
(III) 2-amino-5-benzoyl-6-methyl-4-phenyl-4H-pyran-3-carbonitrile acetonitrile solvate top
Crystal data top
C20H16N2O2·C2H3NZ = 2
Mr = 357.40F(000) = 376
Triclinic, P1Dx = 1.214 Mg m3
a = 8.273 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.313 (2) ÅCell parameters from 122 reflections
c = 13.881 (3) Åθ = 4–26°
α = 73.376 (7)°µ = 0.08 mm1
β = 82.308 (6)°T = 295 K
γ = 72.856 (7)°Prism, colourless
V = 977.8 (4) Å30.35 × 0.26 × 0.18 mm
Data collection top
Bruker SMART APEX II CCD area-detector
diffractometer
4059 independent reflections
Radiation source: fine-focus sealed tube2935 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
ϕ and ω scansθmax = 26.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1010
Tmin = 0.973, Tmax = 0.986k = 1111
8803 measured reflectionsl = 1717
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.069P)2 + 0.13P]
where P = (Fo2 + 2Fc2)/3
4059 reflections(Δ/σ)max < 0.001
246 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C20H16N2O2·C2H3Nγ = 72.856 (7)°
Mr = 357.40V = 977.8 (4) Å3
Triclinic, P1Z = 2
a = 8.273 (2) ÅMo Kα radiation
b = 9.313 (2) ŵ = 0.08 mm1
c = 13.881 (3) ÅT = 295 K
α = 73.376 (7)°0.35 × 0.26 × 0.18 mm
β = 82.308 (6)°
Data collection top
Bruker SMART APEX II CCD area-detector
diffractometer
4059 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2935 reflections with I > 2σ(I)
Tmin = 0.973, Tmax = 0.986Rint = 0.015
8803 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.133H-atom parameters constrained
S = 1.02Δρmax = 0.16 e Å3
4059 reflectionsΔρmin = 0.16 e Å3
246 parameters
Special details top

Experimental. Spectroscopic data for (III): 1H NMR (300 MHz, DMSO-d6, δ, p.p.m.): 7.58 (m, 3H), 7.44 (dd, 2H, J = 7.7 and 8.1 Hz), 7.25 (dd, 2H, J = 7.0 and 7.4 Hz), 7.15 (t, 1H, J = 2.2 and 2.2 Hz), 7.11 (d, 2H, J = 8.1 Hz), 6.95 (br s, 2H, NH2), 4.44 (s, 1H), 1.74 (s, 3H); 13C NMR (75 MHz, DMSO-d6, δ, p.p.m.): 195.3, 159.0, 149.5, 143.3, 137.6, 133.2, 128.8, 128.5, 128.4, 127.5, 127.0, 119.9, 114.0, 56.3, 40.7, 18.1.

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
O10.77768 (12)0.53571 (11)0.86219 (8)0.0522 (3)
O20.21121 (13)0.53689 (13)0.90116 (9)0.0629 (3)
N10.99301 (15)0.33017 (15)0.91442 (11)0.0607 (4)
H1A1.04160.23250.93600.073*
H1B1.05070.39690.90380.073*
N20.80537 (18)0.00362 (16)0.98724 (13)0.0742 (5)
C10.77121 (18)0.12800 (17)0.95269 (12)0.0513 (4)
C20.82827 (17)0.37810 (16)0.89744 (11)0.0467 (3)
C30.71878 (17)0.29035 (16)0.90994 (11)0.0457 (3)
C40.54018 (17)0.35898 (15)0.87556 (11)0.0430 (3)
H4A0.46410.32000.93070.052*
C50.49270 (17)0.53427 (15)0.85529 (10)0.0425 (3)
C60.60696 (17)0.61191 (16)0.85096 (11)0.0446 (3)
C70.5836 (2)0.78071 (17)0.83816 (13)0.0566 (4)
H7A0.46500.83170.84460.085*
H7B0.62880.82520.77270.085*
H7C0.64190.79420.88890.085*
C80.30751 (18)0.60763 (16)0.84744 (11)0.0461 (3)
C90.23473 (18)0.75439 (17)0.77085 (12)0.0501 (4)
C100.51551 (18)0.31014 (15)0.78432 (11)0.0462 (3)
C110.5914 (2)0.3624 (2)0.69131 (13)0.0686 (5)
H11A0.65950.42890.68370.082*
C120.5667 (3)0.3165 (3)0.60905 (16)0.0909 (7)
H12A0.61930.35100.54670.109*
C130.4642 (3)0.2197 (3)0.6197 (2)0.0947 (7)
H13A0.44600.19020.56440.114*
C140.3898 (3)0.1674 (2)0.7113 (2)0.0865 (7)
H14A0.32130.10130.71850.104*
C150.4148 (2)0.21142 (18)0.79316 (15)0.0619 (4)
H15A0.36330.17440.85540.074*
C160.0722 (2)0.8431 (2)0.79089 (15)0.0668 (5)
H16A0.01720.81550.85360.080*
C170.0070 (3)0.9708 (2)0.71874 (18)0.0823 (6)
H17A0.11441.03090.73310.099*
C180.0721 (3)1.0099 (2)0.62535 (17)0.0804 (6)
H18A0.01681.09490.57610.097*
C190.2328 (3)0.9238 (2)0.60418 (14)0.0709 (5)
H19A0.28580.95100.54080.085*
C200.3154 (2)0.79687 (19)0.67721 (12)0.0573 (4)
H20A0.42480.74020.66350.069*
N30.7793 (4)0.7106 (4)0.59208 (19)0.1369 (9)
C210.9075 (4)0.6273 (3)0.61432 (17)0.0904 (7)
C221.0649 (4)0.5261 (4)0.6454 (2)0.1309 (10)
H22A1.07380.42530.63690.157*
H22B1.07480.51760.71510.157*
H22C1.15380.56620.60550.157*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0402 (5)0.0417 (5)0.0719 (7)0.0168 (4)0.0087 (5)0.0023 (5)
O20.0440 (6)0.0584 (6)0.0865 (8)0.0210 (5)0.0041 (5)0.0153 (6)
N10.0407 (7)0.0482 (7)0.0884 (10)0.0151 (6)0.0104 (6)0.0040 (7)
N20.0567 (9)0.0461 (8)0.1071 (12)0.0129 (6)0.0133 (8)0.0027 (8)
C10.0405 (8)0.0469 (9)0.0636 (9)0.0139 (6)0.0072 (7)0.0057 (7)
C20.0415 (7)0.0430 (7)0.0523 (8)0.0125 (6)0.0045 (6)0.0053 (6)
C30.0417 (7)0.0403 (7)0.0533 (8)0.0127 (6)0.0059 (6)0.0065 (6)
C40.0390 (7)0.0391 (7)0.0498 (8)0.0152 (6)0.0023 (6)0.0053 (6)
C50.0421 (7)0.0393 (7)0.0466 (8)0.0131 (6)0.0028 (6)0.0094 (6)
C60.0404 (7)0.0413 (7)0.0508 (8)0.0121 (6)0.0054 (6)0.0073 (6)
C70.0564 (9)0.0443 (8)0.0731 (10)0.0186 (7)0.0099 (8)0.0132 (7)
C80.0423 (7)0.0460 (8)0.0561 (8)0.0151 (6)0.0020 (6)0.0197 (6)
C90.0437 (8)0.0488 (8)0.0610 (9)0.0100 (6)0.0108 (7)0.0181 (7)
C100.0433 (7)0.0349 (7)0.0588 (9)0.0069 (6)0.0108 (6)0.0097 (6)
C110.0805 (12)0.0677 (11)0.0620 (11)0.0278 (9)0.0016 (9)0.0181 (9)
C120.1113 (18)0.0924 (15)0.0606 (12)0.0118 (14)0.0040 (11)0.0234 (11)
C130.1143 (18)0.0772 (14)0.1012 (18)0.0009 (13)0.0467 (15)0.0437 (13)
C140.0927 (15)0.0644 (12)0.1171 (19)0.0185 (11)0.0407 (14)0.0336 (12)
C150.0596 (10)0.0460 (8)0.0848 (12)0.0167 (7)0.0173 (9)0.0160 (8)
C160.0498 (9)0.0653 (10)0.0781 (12)0.0056 (8)0.0048 (8)0.0174 (9)
C170.0583 (11)0.0709 (12)0.1028 (16)0.0043 (9)0.0201 (11)0.0148 (11)
C180.0806 (14)0.0656 (11)0.0881 (14)0.0083 (10)0.0361 (12)0.0067 (10)
C190.0834 (13)0.0691 (11)0.0614 (10)0.0226 (10)0.0158 (9)0.0110 (9)
C200.0561 (9)0.0564 (9)0.0619 (10)0.0139 (7)0.0071 (8)0.0187 (8)
N30.123 (2)0.162 (2)0.1048 (17)0.0401 (19)0.0209 (16)0.0058 (16)
C210.0921 (17)0.1099 (18)0.0715 (13)0.0485 (15)0.0108 (12)0.0022 (12)
C220.098 (2)0.167 (3)0.122 (2)0.029 (2)0.0130 (17)0.034 (2)
Geometric parameters (Å, º) top
O1—C21.3604 (17)C11—C121.387 (3)
O1—C61.3883 (17)C11—H11A0.9300
O2—C81.2224 (17)C12—C131.376 (3)
N1—C21.3340 (18)C12—H12A0.9300
N1—H1A0.8600C13—C141.358 (3)
N1—H1B0.8600C13—H13A0.9300
N2—C11.1437 (19)C14—C151.372 (3)
C1—C31.412 (2)C14—H14A0.9300
C2—C31.3534 (19)C15—H15A0.9300
C3—C41.5090 (19)C16—C171.372 (3)
C4—C51.5124 (18)C16—H16A0.9300
C4—C101.519 (2)C17—C181.373 (3)
C4—H4A0.9800C17—H17A0.9300
C5—C61.3353 (19)C18—C191.378 (3)
C5—C81.487 (2)C18—H18A0.9300
C6—C71.4867 (19)C19—C201.384 (2)
C7—H7A0.9600C19—H19A0.9300
C7—H7B0.9600C20—H20A0.9300
C7—H7C0.9600N3—C211.135 (3)
C8—C91.488 (2)C21—C221.401 (4)
C9—C201.386 (2)C22—H22A0.9600
C9—C161.394 (2)C22—H22B0.9600
C10—C111.379 (2)C22—H22C0.9600
C10—C151.384 (2)
C2—O1—C6120.09 (10)C10—C11—C12120.39 (19)
C2—N1—H1A120.0C10—C11—H11A119.8
C2—N1—H1B120.0C12—C11—H11A119.8
H1A—N1—H1B120.0C13—C12—C11120.0 (2)
N2—C1—C3176.54 (16)C13—C12—H12A120.0
N1—C2—C3128.03 (13)C11—C12—H12A120.0
N1—C2—O1110.56 (12)C14—C13—C12119.9 (2)
C3—C2—O1121.41 (12)C14—C13—H13A120.1
C2—C3—C1120.47 (13)C12—C13—H13A120.1
C2—C3—C4122.11 (12)C13—C14—C15120.5 (2)
C1—C3—C4117.38 (12)C13—C14—H14A119.8
C3—C4—C5109.97 (11)C15—C14—H14A119.8
C3—C4—C10112.28 (11)C14—C15—C10120.88 (19)
C5—C4—C10111.25 (11)C14—C15—H15A119.6
C3—C4—H4A107.7C10—C15—H15A119.6
C5—C4—H4A107.7C17—C16—C9120.41 (18)
C10—C4—H4A107.7C17—C16—H16A119.8
C6—C5—C8124.33 (12)C9—C16—H16A119.8
C6—C5—C4122.28 (12)C16—C17—C18120.00 (18)
C8—C5—C4113.29 (11)C16—C17—H17A120.0
C5—C6—O1121.50 (12)C18—C17—H17A120.0
C5—C6—C7130.02 (13)C17—C18—C19120.41 (18)
O1—C6—C7108.44 (11)C17—C18—H18A119.8
C6—C7—H7A109.5C19—C18—H18A119.8
C6—C7—H7B109.5C18—C19—C20120.01 (19)
H7A—C7—H7B109.5C18—C19—H19A120.0
C6—C7—H7C109.5C20—C19—H19A120.0
H7A—C7—H7C109.5C19—C20—C9119.92 (16)
H7B—C7—H7C109.5C19—C20—H20A120.0
O2—C8—C5117.93 (13)C9—C20—H20A120.0
O2—C8—C9118.64 (13)N3—C21—C22177.7 (3)
C5—C8—C9123.14 (13)C21—C22—H22A109.5
C20—C9—C16119.21 (15)C21—C22—H22B109.5
C20—C9—C8122.25 (13)H22A—C22—H22B109.5
C16—C9—C8118.21 (15)C21—C22—H22C109.5
C11—C10—C15118.41 (15)H22A—C22—H22C109.5
C11—C10—C4121.45 (13)H22B—C22—H22C109.5
C15—C10—C4120.14 (14)
C6—O1—C2—N1172.26 (12)O2—C8—C9—C20143.90 (15)
C6—O1—C2—C38.7 (2)C5—C8—C9—C2029.9 (2)
N1—C2—C3—C15.2 (2)O2—C8—C9—C1629.5 (2)
O1—C2—C3—C1175.92 (13)C5—C8—C9—C16156.76 (14)
N1—C2—C3—C4172.29 (15)C3—C4—C10—C1168.85 (17)
O1—C2—C3—C46.6 (2)C5—C4—C10—C1154.88 (18)
C2—C3—C4—C515.77 (19)C3—C4—C10—C15111.34 (15)
C1—C3—C4—C5166.69 (12)C5—C4—C10—C15124.92 (14)
C2—C3—C4—C10108.67 (16)C15—C10—C11—C120.1 (3)
C1—C3—C4—C1068.87 (16)C4—C10—C11—C12179.87 (16)
C3—C4—C5—C611.57 (19)C10—C11—C12—C130.8 (3)
C10—C4—C5—C6113.47 (15)C11—C12—C13—C141.1 (3)
C3—C4—C5—C8164.83 (12)C12—C13—C14—C150.5 (3)
C10—C4—C5—C870.13 (15)C13—C14—C15—C100.2 (3)
C8—C5—C6—O1177.80 (12)C11—C10—C15—C140.5 (2)
C4—C5—C6—O11.8 (2)C4—C10—C15—C14179.33 (15)
C8—C5—C6—C70.1 (3)C20—C9—C16—C170.1 (3)
C4—C5—C6—C7175.93 (14)C8—C9—C16—C17173.49 (16)
C2—O1—C6—C513.0 (2)C9—C16—C17—C181.5 (3)
C2—O1—C6—C7165.16 (13)C16—C17—C18—C191.6 (3)
C6—C5—C8—O2141.37 (15)C17—C18—C19—C200.1 (3)
C4—C5—C8—O234.94 (18)C18—C19—C20—C91.5 (3)
C6—C5—C8—C944.8 (2)C16—C9—C20—C191.6 (2)
C4—C5—C8—C9138.88 (13)C8—C9—C20—C19171.75 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.862.183.023 (2)167
N1—H1B···O2ii0.862.112.959 (2)170
Symmetry codes: (i) x+2, y, z+2; (ii) x+1, y, z.

Experimental details

(II)(III)
Crystal data
Chemical formulaC15H14N2O2C20H16N2O2·C2H3N
Mr254.28357.40
Crystal system, space groupMonoclinic, P21/nTriclinic, P1
Temperature (K)295295
a, b, c (Å)6.001 (2), 13.910 (3), 15.862 (3)8.273 (2), 9.313 (2), 13.881 (3)
α, β, γ (°)90, 94.989 (5), 9073.376 (7), 82.308 (6), 72.856 (7)
V3)1319.1 (6)977.8 (4)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.090.08
Crystal size (mm)0.30 × 0.25 × 0.200.35 × 0.26 × 0.18
Data collection
DiffractometerBruker SMART APEX II CCD area-detector
diffractometer
Bruker SMART APEX II CCD area-detector
diffractometer
Absorption correctionMulti-scan
SADABS (Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.975, 0.9830.973, 0.986
No. of measured, independent and
observed [I > 2σ(I)] reflections
13889, 3465, 2448 8803, 4059, 2935
Rint0.0310.015
(sin θ/λ)max1)0.6810.629
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.128, 1.01 0.044, 0.133, 1.02
No. of reflections34654059
No. of parameters174246
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.170.16, 0.16

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXTL (Sheldrick, 2001), SHELXTL.

Selected geometric parameters (Å, º) for (II) top
O1—C21.3634 (16)C2—C31.3533 (19)
O1—C61.3823 (16)C4—C101.5246 (18)
O2—C81.2158 (18)C5—C61.3398 (19)
N1—C21.3331 (18)C5—C81.4927 (19)
N2—C11.1394 (19)
C2—O1—C6119.58 (10)
C6—C5—C8—O238.0 (2)C3—C4—C10—C1168.15 (16)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.862.163.012 (2)170
N1—H1B···O2ii0.862.353.077 (2)143
Symmetry codes: (i) x, y+1, z+1; (ii) x+3/2, y1/2, z+3/2.
Selected geometric parameters (Å, º) for (III) top
O1—C21.3604 (17)C2—C31.3534 (19)
O1—C61.3883 (17)C4—C101.519 (2)
O2—C81.2224 (17)C5—C61.3353 (19)
N1—C21.3340 (18)C5—C81.487 (2)
N2—C11.1437 (19)
C2—O1—C6120.09 (10)
C6—C5—C8—O2141.37 (15)C3—C4—C10—C1168.85 (17)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.862.183.023 (2)167
N1—H1B···O2ii0.862.112.959 (2)170
Symmetry codes: (i) x+2, y, z+2; (ii) x+1, y, z.
 

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