Download citation
Download citation
link to html
The structures of the title compounds, C15H13N3O4, (I), and C16H15N3O5 [IUPAC name: ethyl 6-amino-5-cyano-2-methyl-4-(3-nitro­phenyl)-4H-pyrano-3-carboxyl­ate], (II), are very similar, with the heterocyclic rings adopting boat conformations. The pseudo-axial m-nitro­phenyl substituents are rotated by 84.0 (1) and 98.7 (1)° in (I) and (II), respectively, with respect to the four coplanar atoms of the boat. The dihedral angles between the phenyl rings and nitro groups are 12.1 (2) and 8.4 (2)° in (I) and (II), respectively. The two compounds have similar patterns of intermolecular N—H...O and N—H...N hydrogen bonding, which link mol­ecules into infinite tapes along b.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101002682/bm1442sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101002682/bm1442Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101002682/bm1442IIsup3.hkl
Contains datablock II

CCDC references: 164669; 164670

Comment top

The synthesis of hydrogenated compounds has been extensively studied, due to their biological properties. For example, derivatives of 1,4-dihydropyridine exhibit high biological activities as calcium channel blockers (Bossert et al., 1981) and as calcium agonists or antagonists (Triggle et al., 1980; Kokubun & Reuter, 1984; Bossert & Vater, 1989; Wang et al., 1989; Alajarin et al., 1995). 4H-Pyran derivatives have structures similar to those of 1,4-dihydropyridine and elicit the interest of organic chemists as well as of crystallographers. Many different methods have been proposed for the synthesis of 4H-pyran derivatives, for example by Junek & Aigner (1970) and Rappoport & Ladkani (1974). Structural studies of some derivatives of 4H-pyrans by X-ray analysis have been published (Florencio & Garcia-Blanco, 1987; Bellanato et al., 1987, 1988; Lokai et al., 1990; Marco et al., 1993). The present study represents a continuation of our investigations of the structures of 4H-pyran derivatives (Sharanina et al., 1986; Klokol et al., 1987; Shestopalov et al., 1991; Samet et al., 1996; Kislyi et al., 1999a,b). The crystal structures of 5-acetyl-2-amino-6-methyl-4-(3-nitrophenyl)-4H-pyran-3-carbonitrile, (I), and ethyl 6-amino-5-cyano-2-methyl-4-(3-nitrophenyl)-4H-pyrano-3-carboxylate, (II), are presented herein. \sch

The pyran rings in both molecules have boat conformations, with atoms O1 and C4 out of the C2/C3/C5/C6 plane by -0.179 (1) and -0.341 (1) Å, respectively, in (I), and by 0.151 (2) and 0.306 (2) Å, respectively, in (II). The C2/C3/C5/C6 plane is planar to within 0.005 (1) Å for (I) and 0.026 (1) Å for (II). The bending of the ring along O1···C4, C2···C6 and C3···C5 equals 24.0 (1), 15.1 (1) and 22.8 (2)°, respectively, in (I), and 21.2 (1), 12.7 (1) and 20.3 (2)°, respectively, in (II). The heterocycles in (I) and (II), in pyrans with comparable structures, and in derivatives of 1,4-dihydropyridine, for example, nifedipine (Triggle et al., 1980), nimodipine (Wang et al., 1989) and furnidipine (Alajarin et al., 1995), have similar conformations.

The dihedral angle between the pseudo-axial aryl substituent and the C2/C3/C5/C6 plane of the boat of the heterocycle is 84.0 (1)° in (I) and 98.7 (1)° in (II), minimizing possible intramolecular sterical contacts in both molecules. Similar orientations of sterically demanding substituents were found in all previously determined derivatives of 4H-pyrans (Sharanina et al., 1986; Klokol et al., 1987; Shestopalov et al., 1991; Samet et al., 1996; Kislyi et al., 1999a,b; Florencio & Garcia-Blanco, 1987; Bellanato et al., 1988; Lokai et al., 1990; Marco et al., 1993). The value of the angle is close to 90° in practically all known 4H-pyran derivatives containing sterically demanding substituents in the 4-position of the heterocycle.

The nitro groups are slightly rotated from the plane of the phenyl ring of the aryl substituent, by 12.1 (2)° in (I) and 8.4 (2)° in (II). As shown in Figs. 1 and 2, the substituents at C5 of the heterocycle have trans orientations with respect to the C5C6 double bond. The C6—C5—C8—O2 torsion angle is -179.3 (2)° in (I) and -157.2 (2)° in (II). It is interesting to note that the acetyl substituent has a cis geometry in the 1,4-dihydropyridine derivative described by Nesterov et al. (1985), and ester groups have cis geometry in substituted 4H-pyrans and form intramolecular hydrogen bonds with amino groups (Sharanina et al., 1986; Klokol et al., 1987; Shestopalov et al., 1991).

The bond lengths in the planar fragment N1—C2C3—C16/C17N2 in both structures are different from typical literature values (Allen et al., 1987). This bond length distribution was observed in all derivatives of 4H-pyrans that we investigated and has also been noted in the literature (Samet et al., 1996; Bellanato et al., 1987; Lokai et al., 1990; Marco et al., 1993). This regularity can be explained by the conjugation of bonds in the fragment. However, in the C6 C5—C8O2 fragment, located on the opposite side of the pyran ring in both compounds, the bond lengths agree with standard values (Allen et al., 1987) and this confirms the absence of conjugation in this fragment of both molecules. The mutual orientation of substituents of the pyran ring in both molecules gives rise to an intramolecular O2···H4A non-bonded interaction. The length of this interaction is 2.38 Å in (I) and 2.43 Å in (II), less than the sum of the relevant van der Waals radii (Rowlend & Taylor, 1996). The rest of the geometrical parameters in (I) and (II) have standard values (Allen et al., 1987).

The structures of (I) and (II) both exhibit intermolecular N1—H1B···O2(x, y - 1, z) and N1—H1A···N2(2 - x, 1 - y, 1 - z) hydrogen bonds, which connect molecules into infinite tapes along the b axis.

Related literature top

For related literature, see: Alajarin et al. (1995); Allen et al. (1987); Bellanato et al. (1987, 1988); Bossert & Vater (1989); Bossert et al. (1981); Florencio & Garcia-Blanco (1987); Junek, Aigner & ? (1970); Kislyi et al. (1999a, 1999b); Klokol et al. (1987); Kokubun & Reuter (1984); Marco et al. (1993); Nesterov et al. (1985); Rappoport & Ladkani (1974); Rowlend & Taylor (1996); Samet et al. (1996); Sharanina et al. (1986); Shestopalov et al. (1991); Triggle et al. (1980); Wang et al. (1989).

Experimental top

Compounds (I) and (II) were prepared by the reaction of m-nitrophenyl aldehyde (0.01 mol) with acetylacetone (0.01 mol) and ethyl acetoacetate (0.01 mol), respectively, in the presence of a catalytic amount of morpholine in ethanol (20 ml) under reflux (Sharanina et al., 1986). The precipitates were isolated and recrystallized from ethanol [m.p. 492 K for (I) and 457 K for (II); yield 90% for (I) and 86% for (II)]. Colourless crystals of (I) and (II) suitable for X-ray analysis were obtained by isothermal evaporation from ethanolic solutions.

Refinement top

AUTHOR - please check these details: H atoms were located from difference Fourier syntheses and idealized for refinement with N—H 0.86 Å, and C—H 0.93, 0.96 and 0.98 Å for aryl, methyl and methine H atoms, respectively, and with Uiso(H) = xUeq(N/C), where x = 1.5 for methyl H atoms and 1.2 for all others.

Structure description top

The synthesis of hydrogenated compounds has been extensively studied, due to their biological properties. For example, derivatives of 1,4-dihydropyridine exhibit high biological activities as calcium channel blockers (Bossert et al., 1981) and as calcium agonists or antagonists (Triggle et al., 1980; Kokubun & Reuter, 1984; Bossert & Vater, 1989; Wang et al., 1989; Alajarin et al., 1995). 4H-Pyran derivatives have structures similar to those of 1,4-dihydropyridine and elicit the interest of organic chemists as well as of crystallographers. Many different methods have been proposed for the synthesis of 4H-pyran derivatives, for example by Junek & Aigner (1970) and Rappoport & Ladkani (1974). Structural studies of some derivatives of 4H-pyrans by X-ray analysis have been published (Florencio & Garcia-Blanco, 1987; Bellanato et al., 1987, 1988; Lokai et al., 1990; Marco et al., 1993). The present study represents a continuation of our investigations of the structures of 4H-pyran derivatives (Sharanina et al., 1986; Klokol et al., 1987; Shestopalov et al., 1991; Samet et al., 1996; Kislyi et al., 1999a,b). The crystal structures of 5-acetyl-2-amino-6-methyl-4-(3-nitrophenyl)-4H-pyran-3-carbonitrile, (I), and ethyl 6-amino-5-cyano-2-methyl-4-(3-nitrophenyl)-4H-pyrano-3-carboxylate, (II), are presented herein. \sch

The pyran rings in both molecules have boat conformations, with atoms O1 and C4 out of the C2/C3/C5/C6 plane by -0.179 (1) and -0.341 (1) Å, respectively, in (I), and by 0.151 (2) and 0.306 (2) Å, respectively, in (II). The C2/C3/C5/C6 plane is planar to within 0.005 (1) Å for (I) and 0.026 (1) Å for (II). The bending of the ring along O1···C4, C2···C6 and C3···C5 equals 24.0 (1), 15.1 (1) and 22.8 (2)°, respectively, in (I), and 21.2 (1), 12.7 (1) and 20.3 (2)°, respectively, in (II). The heterocycles in (I) and (II), in pyrans with comparable structures, and in derivatives of 1,4-dihydropyridine, for example, nifedipine (Triggle et al., 1980), nimodipine (Wang et al., 1989) and furnidipine (Alajarin et al., 1995), have similar conformations.

The dihedral angle between the pseudo-axial aryl substituent and the C2/C3/C5/C6 plane of the boat of the heterocycle is 84.0 (1)° in (I) and 98.7 (1)° in (II), minimizing possible intramolecular sterical contacts in both molecules. Similar orientations of sterically demanding substituents were found in all previously determined derivatives of 4H-pyrans (Sharanina et al., 1986; Klokol et al., 1987; Shestopalov et al., 1991; Samet et al., 1996; Kislyi et al., 1999a,b; Florencio & Garcia-Blanco, 1987; Bellanato et al., 1988; Lokai et al., 1990; Marco et al., 1993). The value of the angle is close to 90° in practically all known 4H-pyran derivatives containing sterically demanding substituents in the 4-position of the heterocycle.

The nitro groups are slightly rotated from the plane of the phenyl ring of the aryl substituent, by 12.1 (2)° in (I) and 8.4 (2)° in (II). As shown in Figs. 1 and 2, the substituents at C5 of the heterocycle have trans orientations with respect to the C5C6 double bond. The C6—C5—C8—O2 torsion angle is -179.3 (2)° in (I) and -157.2 (2)° in (II). It is interesting to note that the acetyl substituent has a cis geometry in the 1,4-dihydropyridine derivative described by Nesterov et al. (1985), and ester groups have cis geometry in substituted 4H-pyrans and form intramolecular hydrogen bonds with amino groups (Sharanina et al., 1986; Klokol et al., 1987; Shestopalov et al., 1991).

The bond lengths in the planar fragment N1—C2C3—C16/C17N2 in both structures are different from typical literature values (Allen et al., 1987). This bond length distribution was observed in all derivatives of 4H-pyrans that we investigated and has also been noted in the literature (Samet et al., 1996; Bellanato et al., 1987; Lokai et al., 1990; Marco et al., 1993). This regularity can be explained by the conjugation of bonds in the fragment. However, in the C6 C5—C8O2 fragment, located on the opposite side of the pyran ring in both compounds, the bond lengths agree with standard values (Allen et al., 1987) and this confirms the absence of conjugation in this fragment of both molecules. The mutual orientation of substituents of the pyran ring in both molecules gives rise to an intramolecular O2···H4A non-bonded interaction. The length of this interaction is 2.38 Å in (I) and 2.43 Å in (II), less than the sum of the relevant van der Waals radii (Rowlend & Taylor, 1996). The rest of the geometrical parameters in (I) and (II) have standard values (Allen et al., 1987).

The structures of (I) and (II) both exhibit intermolecular N1—H1B···O2(x, y - 1, z) and N1—H1A···N2(2 - x, 1 - y, 1 - z) hydrogen bonds, which connect molecules into infinite tapes along the b axis.

For related literature, see: Alajarin et al. (1995); Allen et al. (1987); Bellanato et al. (1987, 1988); Bossert & Vater (1989); Bossert et al. (1981); Florencio & Garcia-Blanco (1987); Junek, Aigner & ? (1970); Kislyi et al. (1999a, 1999b); Klokol et al. (1987); Kokubun & Reuter (1984); Marco et al. (1993); Nesterov et al. (1985); Rappoport & Ladkani (1974); Rowlend & Taylor (1996); Samet et al. (1996); Sharanina et al. (1986); Shestopalov et al. (1991); Triggle et al. (1980); Wang et al. (1989).

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989) for (I); P3 (Siemens, 1989) for (II). Cell refinement: CAD-4 Software for (I); P3 for (II). For both compounds, data reduction: SHELXTL-Plus (Sheldrick, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular view of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The molecular view of (II) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
(I) 5-acetyl-2-amino-6-methyl-4-(3-nitrophenyl)-4H-pyran-3-carbonitrile top
Crystal data top
C15H13N3O4F(000) = 312
Mr = 299.28Dx = 1.411 Mg m3
Triclinic, P1Melting point: 492 K
a = 8.1470 (16) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.4120 (17) ÅCell parameters from 24 reflections
c = 11.149 (2) Åθ = 11–12°
α = 98.46 (3)°µ = 0.11 mm1
β = 108.69 (3)°T = 298 K
γ = 96.93 (3)°Parallelepiped prism, colourless
V = 704.3 (2) Å30.50 × 0.40 × 0.25 mm
Z = 2
Data collection top
Enraf-Nonius CAD4
diffractometer
Rint = 0.017
Radiation source: fine-focus sealed tubeθmax = 27.0°, θmin = 2.0°
Graphite monochromatorh = 010
θ/2θ scank = 1010
3277 measured reflectionsl = 1413
3019 independent reflections3 standard reflections every 97 reflections
1896 reflections with I > 2σ(I) intensity decay: 3%
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)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.1084P)2 + 0.037P]
where P = (Fo2 + 2Fc2)/3
3019 reflections(Δ/σ)max = 0.003
201 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C15H13N3O4γ = 96.93 (3)°
Mr = 299.28V = 704.3 (2) Å3
Triclinic, P1Z = 2
a = 8.1470 (16) ÅMo Kα radiation
b = 8.4120 (17) ŵ = 0.11 mm1
c = 11.149 (2) ÅT = 298 K
α = 98.46 (3)°0.50 × 0.40 × 0.25 mm
β = 108.69 (3)°
Data collection top
Enraf-Nonius CAD4
diffractometer
Rint = 0.017
3277 measured reflections3 standard reflections every 97 reflections
3019 independent reflections intensity decay: 3%
1896 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.169H-atom parameters constrained
S = 1.02Δρmax = 0.22 e Å3
3019 reflectionsΔρmin = 0.20 e Å3
201 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.40336 (19)0.49394 (16)0.30002 (15)0.0341 (4)
O20.4262 (2)1.05888 (19)0.3402 (2)0.0539 (5)
O30.7438 (3)1.2880 (3)0.1398 (3)0.0749 (7)
O40.8359 (4)1.1941 (3)0.0112 (3)0.0914 (9)
N10.6282 (3)0.3812 (2)0.4021 (2)0.0413 (5)
H1A0.73650.38140.44570.050*
H1B0.55200.29240.37950.050*
N21.0069 (3)0.7102 (3)0.5306 (2)0.0523 (6)
N30.7720 (3)1.1754 (3)0.0712 (2)0.0506 (6)
C20.5783 (3)0.5187 (2)0.3696 (2)0.0286 (5)
C30.6797 (3)0.6685 (2)0.39678 (19)0.0279 (4)
C40.6050 (3)0.8074 (2)0.34073 (19)0.0254 (4)
H4A0.65700.90780.40630.030*
C50.4070 (3)0.7779 (2)0.31246 (19)0.0270 (4)
C60.3164 (3)0.6254 (2)0.2869 (2)0.0292 (5)
C70.1242 (3)0.5591 (3)0.2389 (3)0.0446 (6)
H7A0.06220.62660.18430.067*
H7B0.08390.55810.31080.067*
H7C0.10230.44980.19040.067*
C80.3291 (3)0.9282 (2)0.3171 (2)0.0316 (5)
C90.1404 (3)0.9291 (3)0.2999 (3)0.0476 (6)
H9A0.12091.03980.31060.071*
H9B0.11040.87740.36320.071*
H9C0.06810.87080.21490.071*
C100.6480 (3)0.8320 (2)0.2202 (2)0.0278 (5)
C110.6887 (3)0.9885 (3)0.1993 (2)0.0313 (5)
H11A0.68981.07930.25840.038*
C120.7275 (3)1.0080 (3)0.0906 (2)0.0381 (5)
C130.7290 (3)0.8787 (3)0.0005 (2)0.0477 (6)
H13A0.75610.89550.07320.057*
C140.6886 (4)0.7225 (3)0.0207 (3)0.0523 (7)
H14A0.68750.63230.03900.063*
C150.6500 (3)0.6998 (3)0.1292 (2)0.0391 (6)
H15A0.62480.59420.14210.047*
C160.8596 (3)0.6910 (2)0.4715 (2)0.0334 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0332 (8)0.0151 (7)0.0487 (9)0.0005 (6)0.0109 (7)0.0001 (6)
O20.0517 (11)0.0174 (8)0.0979 (15)0.0066 (7)0.0345 (10)0.0078 (8)
O30.0943 (18)0.0408 (12)0.1029 (19)0.0090 (11)0.0474 (15)0.0275 (12)
O40.132 (2)0.0741 (17)0.0867 (18)0.0079 (16)0.0658 (17)0.0323 (14)
N10.0417 (11)0.0178 (9)0.0615 (14)0.0043 (7)0.0141 (10)0.0081 (8)
N20.0354 (12)0.0430 (12)0.0676 (15)0.0082 (9)0.0048 (10)0.0061 (10)
N30.0511 (13)0.0476 (13)0.0542 (13)0.0016 (10)0.0167 (11)0.0247 (11)
C20.0334 (11)0.0174 (9)0.0356 (11)0.0050 (8)0.0134 (9)0.0032 (8)
C30.0298 (11)0.0199 (9)0.0322 (11)0.0034 (8)0.0095 (8)0.0038 (8)
C40.0271 (10)0.0145 (8)0.0320 (10)0.0010 (7)0.0092 (8)0.0013 (7)
C50.0279 (10)0.0205 (9)0.0316 (10)0.0022 (8)0.0105 (8)0.0032 (7)
C60.0312 (11)0.0204 (9)0.0346 (11)0.0050 (8)0.0114 (9)0.0008 (8)
C70.0344 (12)0.0276 (11)0.0653 (17)0.0026 (9)0.0150 (11)0.0010 (11)
C80.0386 (12)0.0214 (10)0.0373 (12)0.0064 (8)0.0161 (9)0.0061 (8)
C90.0448 (14)0.0363 (13)0.0639 (17)0.0147 (11)0.0216 (12)0.0037 (12)
C100.0254 (10)0.0219 (10)0.0324 (11)0.0015 (8)0.0077 (8)0.0013 (8)
C110.0283 (10)0.0273 (10)0.0382 (12)0.0023 (8)0.0124 (9)0.0060 (9)
C120.0296 (11)0.0413 (13)0.0416 (13)0.0019 (9)0.0091 (10)0.0133 (10)
C130.0502 (15)0.0598 (17)0.0342 (13)0.0029 (12)0.0184 (11)0.0090 (11)
C140.0619 (17)0.0465 (15)0.0429 (14)0.0011 (12)0.0214 (12)0.0093 (11)
C150.0461 (13)0.0267 (11)0.0414 (13)0.0009 (9)0.0168 (11)0.0007 (9)
C160.0386 (13)0.0193 (10)0.0415 (12)0.0064 (8)0.0134 (10)0.0034 (8)
Geometric parameters (Å, º) top
O1—C21.359 (3)C6—C71.488 (3)
O1—C61.384 (3)C7—H7A0.9600
O2—C81.215 (3)C7—H7B0.9600
O3—N31.219 (3)C7—H7C0.9600
O4—N31.212 (3)C8—C91.489 (3)
N1—C21.333 (3)C9—H9A0.9600
N1—H1A0.8600C9—H9B0.9600
N1—H1B0.8600C9—H9C0.9600
N2—C161.147 (3)C10—C111.390 (3)
N3—C121.476 (3)C10—C151.396 (3)
C2—C31.356 (3)C11—C121.373 (3)
C3—C161.408 (3)C11—H11A0.9300
C3—C41.506 (3)C12—C131.379 (4)
C4—C51.523 (3)C13—C141.389 (4)
C4—C101.529 (3)C13—H13A0.9300
C4—H4A0.9800C14—C151.377 (4)
C5—C61.342 (3)C14—H14A0.9300
C5—C81.483 (3)C15—H15A0.9300
C2—O1—C6120.10 (16)H7B—C7—H7C109.5
C2—N1—H1A120.0O2—C8—C5118.1 (2)
C2—N1—H1B120.0O2—C8—C9118.0 (2)
H1A—N1—H1B120.0C5—C8—C9123.93 (19)
O4—N3—O3123.4 (2)C8—C9—H9A109.5
O4—N3—C12118.5 (3)C8—C9—H9B109.5
O3—N3—C12118.1 (2)H9A—C9—H9B109.5
N1—C2—C3127.8 (2)C8—C9—H9C109.5
N1—C2—O1111.45 (17)H9A—C9—H9C109.5
C3—C2—O1120.70 (18)H9B—C9—H9C109.5
C2—C3—C16119.32 (19)C11—C10—C15118.0 (2)
C2—C3—C4120.76 (18)C11—C10—C4120.38 (18)
C16—C3—C4119.79 (17)C15—C10—C4121.60 (18)
C3—C4—C5108.92 (15)C12—C11—C10119.5 (2)
C3—C4—C10112.81 (17)C12—C11—H11A120.3
C5—C4—C10111.17 (17)C10—C11—H11A120.3
C3—C4—H4A107.9C11—C12—C13123.2 (2)
C5—C4—H4A107.9C11—C12—N3118.5 (2)
C10—C4—H4A107.9C13—C12—N3118.3 (2)
C6—C5—C8124.87 (19)C12—C13—C14117.2 (2)
C6—C5—C4120.45 (18)C12—C13—H13A121.4
C8—C5—C4114.67 (16)C14—C13—H13A121.4
C5—C6—O1120.62 (19)C15—C14—C13120.7 (2)
C5—C6—C7132.0 (2)C15—C14—H14A119.7
O1—C6—C7107.31 (17)C13—C14—H14A119.7
C6—C7—H7A109.5C14—C15—C10121.4 (2)
C6—C7—H7B109.5C14—C15—H15A119.3
H7A—C7—H7B109.5C10—C15—H15A119.3
C6—C7—H7C109.5N2—C16—C3178.8 (3)
H7A—C7—H7C109.5
C6—O1—C2—N1162.48 (19)C4—C5—C8—O21.2 (3)
C6—O1—C2—C318.1 (3)C6—C5—C8—C93.0 (4)
N1—C2—C3—C162.1 (4)C4—C5—C8—C9176.4 (2)
O1—C2—C3—C16178.58 (19)C3—C4—C10—C11141.52 (19)
N1—C2—C3—C4173.7 (2)C5—C4—C10—C1195.8 (2)
O1—C2—C3—C45.6 (3)C3—C4—C10—C1537.6 (3)
C2—C3—C4—C526.3 (3)C5—C4—C10—C1585.1 (2)
C16—C3—C4—C5157.87 (19)C15—C10—C11—C120.7 (3)
C2—C3—C4—C1097.7 (2)C4—C10—C11—C12179.80 (19)
C16—C3—C4—C1078.2 (2)C10—C11—C12—C130.3 (3)
C3—C4—C5—C627.1 (3)C10—C11—C12—N3179.4 (2)
C10—C4—C5—C697.8 (2)O4—N3—C12—C11167.1 (3)
C3—C4—C5—C8152.41 (17)O3—N3—C12—C1112.2 (4)
C10—C4—C5—C882.7 (2)O4—N3—C12—C1312.1 (4)
C8—C5—C6—O1172.16 (19)O3—N3—C12—C13168.6 (3)
C4—C5—C6—O17.3 (3)C11—C12—C13—C140.2 (4)
C8—C5—C6—C710.4 (4)N3—C12—C13—C14179.3 (2)
C4—C5—C6—C7170.1 (2)C12—C13—C14—C150.4 (4)
C2—O1—C6—C517.2 (3)C13—C14—C15—C100.8 (4)
C2—O1—C6—C7164.83 (19)C11—C10—C15—C140.9 (4)
C6—C5—C8—O2179.3 (2)C4—C10—C15—C14179.9 (2)
(II) ethyl 6-amino-5-cyano-2-methyl-4-(3-nitrophenyl)-4H-pyrano-3-carboxylate top
Crystal data top
C16H15N3O5F(000) = 344
Mr = 329.31Dx = 1.375 Mg m3
Triclinic, P1Melting point: 457 K
a = 8.455 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.475 (1) ÅCell parameters from 24 reflections
c = 12.073 (2) Åθ = 11–12°
α = 83.05 (2)°µ = 0.10 mm1
β = 71.33 (2)°T = 298 K
γ = 76.35 (2)°Rhombohedral prism, colourless
V = 795.46 (19) Å30.50 × 0.40 × 0.30 mm
Z = 2
Data collection top
Siemens P3/PC
diffractometer
Rint = 0.027
Radiation source: fine-focus sealed tubeθmax = 29.1°, θmin = 2.6°
Graphite monochromatorh = 011
θ/2θ scank = 1111
4216 measured reflectionsl = 1516
3942 independent reflections2 standard reflections every 98 reflections
2553 reflections with I > 2σ(I) intensity decay: 5%
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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0686P)2 + 0.1782P]
where P = (Fo2 + 2Fc2)/3
3942 reflections(Δ/σ)max = 0.003
219 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C16H15N3O5γ = 76.35 (2)°
Mr = 329.31V = 795.46 (19) Å3
Triclinic, P1Z = 2
a = 8.455 (1) ÅMo Kα radiation
b = 8.475 (1) ŵ = 0.10 mm1
c = 12.073 (2) ÅT = 298 K
α = 83.05 (2)°0.50 × 0.40 × 0.30 mm
β = 71.33 (2)°
Data collection top
Siemens P3/PC
diffractometer
Rint = 0.027
4216 measured reflections2 standard reflections every 98 reflections
3942 independent reflections intensity decay: 5%
2553 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.154H-atom parameters constrained
S = 1.03Δρmax = 0.22 e Å3
3942 reflectionsΔρmin = 0.20 e Å3
219 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.42683 (16)0.72685 (15)0.66604 (12)0.0474 (3)
O20.4589 (2)1.27563 (17)0.63437 (16)0.0653 (4)
O30.20256 (19)1.22029 (17)0.72605 (14)0.0617 (4)
O40.7001 (4)1.3820 (4)0.8855 (3)0.1289 (10)
O50.7751 (5)1.2557 (4)1.0301 (2)0.1713 (15)
N10.6440 (2)0.52577 (19)0.59401 (16)0.0534 (4)
H1A0.74980.48200.56320.064*
H1B0.56740.46840.60920.064*
N21.0204 (2)0.7037 (2)0.49837 (19)0.0650 (5)
N30.7329 (4)1.2585 (4)0.9430 (2)0.1010 (9)
C20.5988 (2)0.6821 (2)0.61807 (15)0.0405 (4)
C30.7002 (2)0.7906 (2)0.60051 (15)0.0391 (4)
C40.6320 (2)0.9550 (2)0.65293 (15)0.0370 (4)
H4A0.68621.03460.59680.044*
C50.4407 (2)1.0016 (2)0.67051 (15)0.0374 (4)
C60.3494 (2)0.8905 (2)0.67722 (15)0.0404 (4)
C70.1637 (3)0.9081 (3)0.6947 (2)0.0571 (5)
H7A0.11751.01610.66960.086*
H7B0.10620.88910.77620.086*
H7C0.14760.83050.64970.086*
C80.3702 (2)1.1780 (2)0.67468 (16)0.0436 (4)
C90.1247 (3)1.3945 (3)0.7246 (2)0.0677 (7)
H9A0.00981.40960.71970.081*
H9B0.19061.44930.65630.081*
C100.1194 (4)1.4657 (3)0.8315 (2)0.0858 (9)
H10A0.05661.57620.83400.129*
H10B0.23361.46320.83110.129*
H10C0.06441.40410.89900.129*
C110.6699 (2)0.9597 (2)0.76780 (15)0.0398 (4)
C120.6902 (3)1.1026 (3)0.80095 (17)0.0493 (5)
H12A0.68411.19640.75250.059*
C130.7194 (3)1.1041 (3)0.90676 (19)0.0625 (6)
C140.7329 (3)0.9690 (4)0.9805 (2)0.0727 (7)
H14A0.75480.97311.05070.087*
C150.7131 (3)0.8278 (4)0.9478 (2)0.0717 (7)
H15A0.72100.73430.99650.086*
C160.6812 (3)0.8224 (3)0.84249 (18)0.0554 (5)
H16A0.66730.72550.82180.066*
C170.8771 (2)0.7416 (2)0.54422 (17)0.0442 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0398 (7)0.0349 (7)0.0630 (8)0.0114 (5)0.0052 (6)0.0068 (6)
O20.0635 (10)0.0371 (7)0.1021 (13)0.0161 (7)0.0327 (9)0.0027 (8)
O30.0559 (9)0.0413 (8)0.0753 (10)0.0017 (6)0.0083 (7)0.0104 (7)
O40.198 (3)0.0984 (18)0.123 (2)0.0604 (19)0.064 (2)0.0315 (16)
O50.276 (4)0.214 (3)0.0992 (18)0.140 (3)0.092 (2)0.0184 (19)
N10.0470 (9)0.0359 (8)0.0727 (11)0.0103 (7)0.0079 (8)0.0105 (8)
N20.0422 (10)0.0601 (11)0.0876 (14)0.0053 (8)0.0093 (9)0.0233 (10)
N30.128 (2)0.133 (3)0.0690 (16)0.069 (2)0.0285 (15)0.0298 (16)
C20.0426 (10)0.0358 (9)0.0411 (9)0.0082 (7)0.0089 (8)0.0048 (7)
C30.0380 (9)0.0360 (9)0.0419 (9)0.0070 (7)0.0088 (7)0.0073 (7)
C40.0401 (9)0.0342 (8)0.0377 (9)0.0110 (7)0.0102 (7)0.0034 (7)
C50.0411 (9)0.0336 (9)0.0376 (9)0.0062 (7)0.0124 (7)0.0037 (7)
C60.0406 (10)0.0361 (9)0.0425 (9)0.0076 (7)0.0092 (8)0.0042 (7)
C70.0418 (11)0.0498 (11)0.0813 (15)0.0105 (9)0.0181 (10)0.0088 (10)
C80.0506 (11)0.0357 (9)0.0487 (10)0.0069 (8)0.0217 (9)0.0033 (8)
C90.0737 (15)0.0496 (12)0.0681 (14)0.0093 (11)0.0203 (12)0.0059 (11)
C100.117 (2)0.0602 (15)0.0746 (17)0.0012 (15)0.0317 (16)0.0152 (13)
C110.0328 (9)0.0465 (10)0.0387 (9)0.0064 (7)0.0084 (7)0.0067 (8)
C120.0489 (11)0.0583 (12)0.0453 (10)0.0187 (9)0.0131 (8)0.0087 (9)
C130.0591 (13)0.0883 (17)0.0499 (12)0.0277 (12)0.0164 (10)0.0171 (12)
C140.0592 (14)0.119 (2)0.0437 (12)0.0168 (14)0.0204 (10)0.0095 (14)
C150.0726 (16)0.0856 (18)0.0501 (13)0.0029 (13)0.0241 (12)0.0108 (12)
C160.0590 (13)0.0558 (12)0.0486 (11)0.0054 (10)0.0184 (10)0.0006 (9)
C170.0439 (11)0.0376 (9)0.0533 (11)0.0083 (8)0.0149 (9)0.0105 (8)
Geometric parameters (Å, º) top
O1—C21.359 (2)C6—C71.489 (3)
O1—C61.389 (2)C7—H7A0.9600
O2—C81.203 (2)C7—H7B0.9600
O3—C81.331 (2)C7—H7C0.9600
O3—C91.468 (3)C9—C101.473 (4)
O4—N31.209 (3)C9—H9A0.9700
O5—N31.211 (3)C9—H9B0.9700
N1—C21.330 (2)C10—H10A0.9600
N1—H1A0.8600C10—H10B0.9600
N1—H1B0.8600C10—H10C0.9600
N2—C171.143 (2)C11—C121.384 (3)
N3—C131.469 (4)C11—C161.388 (3)
C2—C31.355 (2)C12—C131.379 (3)
C3—C171.413 (3)C12—H12A0.9300
C3—C41.508 (2)C13—C141.369 (4)
C4—C51.522 (2)C14—C151.367 (4)
C4—C111.527 (2)C14—H14A0.9300
C4—H4A0.9800C15—C161.389 (3)
C5—C61.333 (2)C15—H15A0.9300
C5—C81.473 (2)C16—H16A0.9300
C2—O1—C6119.90 (14)O2—C8—C5121.83 (18)
C8—O3—C9117.04 (18)O3—C8—C5115.19 (16)
C2—N1—H1A120.0O3—C9—C10110.2 (2)
C2—N1—H1B120.0O3—C9—H9A109.6
H1A—N1—H1B120.0C10—C9—H9A109.6
O4—N3—O5123.2 (3)O3—C9—H9B109.6
O4—N3—C13118.9 (2)C10—C9—H9B109.6
O5—N3—C13117.9 (3)H9A—C9—H9B108.1
N1—C2—C3128.39 (17)C9—C10—H10A109.5
N1—C2—O1110.66 (15)C9—C10—H10B109.5
C3—C2—O1120.95 (15)H10A—C10—H10B109.5
C2—C3—C17119.14 (16)C9—C10—H10C109.5
C2—C3—C4121.16 (16)H10A—C10—H10C109.5
C17—C3—C4119.26 (15)H10B—C10—H10C109.5
C3—C4—C5108.60 (14)C12—C11—C16118.43 (18)
C3—C4—C11112.88 (14)C12—C11—C4120.56 (17)
C5—C4—C11110.71 (14)C16—C11—C4121.00 (17)
C3—C4—H4A108.2C13—C12—C11119.2 (2)
C5—C4—H4A108.2C13—C12—H12A120.4
C11—C4—H4A108.2C11—C12—H12A120.4
C6—C5—C8124.14 (17)C14—C13—C12122.9 (2)
C6—C5—C4121.73 (15)C14—C13—N3118.6 (2)
C8—C5—C4114.09 (15)C12—C13—N3118.4 (3)
C5—C6—O1120.82 (16)C15—C14—C13117.9 (2)
C5—C6—C7130.77 (17)C15—C14—H14A121.0
O1—C6—C7108.40 (15)C13—C14—H14A121.0
C6—C7—H7A109.5C14—C15—C16120.7 (2)
C6—C7—H7B109.5C14—C15—H15A119.7
H7A—C7—H7B109.5C16—C15—H15A119.7
C6—C7—H7C109.5C11—C16—C15120.9 (2)
H7A—C7—H7C109.5C11—C16—H16A119.6
H7B—C7—H7C109.5C15—C16—H16A119.6
O2—C8—O3122.97 (17)N2—C17—C3179.2 (2)
C6—O1—C2—N1167.79 (16)C4—C5—C8—O220.6 (3)
C6—O1—C2—C312.2 (3)C6—C5—C8—O322.9 (3)
N1—C2—C3—C173.7 (3)C4—C5—C8—O3159.31 (15)
O1—C2—C3—C17176.35 (17)C8—O3—C9—C1092.6 (3)
N1—C2—C3—C4168.61 (18)C3—C4—C11—C12150.52 (17)
O1—C2—C3—C411.4 (3)C5—C4—C11—C1287.5 (2)
C2—C3—C4—C526.4 (2)C3—C4—C11—C1630.8 (2)
C17—C3—C4—C5161.32 (16)C5—C4—C11—C1691.1 (2)
C2—C3—C4—C1196.7 (2)C16—C11—C12—C130.5 (3)
C17—C3—C4—C1175.5 (2)C4—C11—C12—C13178.17 (17)
C3—C4—C5—C621.4 (2)C11—C12—C13—C141.3 (3)
C11—C4—C5—C6103.05 (19)C11—C12—C13—N3177.3 (2)
C3—C4—C5—C8156.43 (15)O4—N3—C13—C14170.9 (3)
C11—C4—C5—C879.12 (18)O5—N3—C13—C148.5 (4)
C8—C5—C6—O1176.34 (16)O4—N3—C13—C127.7 (4)
C4—C5—C6—O11.3 (3)O5—N3—C13—C12172.9 (3)
C8—C5—C6—C72.9 (3)C12—C13—C14—C151.2 (4)
C4—C5—C6—C7179.53 (19)N3—C13—C14—C15177.3 (2)
C2—O1—C6—C517.4 (3)C13—C14—C15—C160.3 (4)
C2—O1—C6—C7161.94 (17)C12—C11—C16—C150.3 (3)
C9—O3—C8—O24.4 (3)C4—C11—C16—C15179.01 (19)
C9—O3—C8—C5175.67 (17)C14—C15—C16—C110.4 (4)
C6—C5—C8—O2157.15 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O2i0.862.002.830 (2)161
N1—H1A···N2ii0.862.172.995 (2)160
Symmetry codes: (i) x, y1, z; (ii) x+2, y+1, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC15H13N3O4C16H15N3O5
Mr299.28329.31
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)298298
a, b, c (Å)8.1470 (16), 8.4120 (17), 11.149 (2)8.455 (1), 8.475 (1), 12.073 (2)
α, β, γ (°)98.46 (3), 108.69 (3), 96.93 (3)83.05 (2), 71.33 (2), 76.35 (2)
V3)704.3 (2)795.46 (19)
Z22
Radiation typeMo KαMo Kα
µ (mm1)0.110.10
Crystal size (mm)0.50 × 0.40 × 0.250.50 × 0.40 × 0.30
Data collection
DiffractometerEnraf-Nonius CAD4Siemens P3/PC
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3277, 3019, 1896 4216, 3942, 2553
Rint0.0170.027
(sin θ/λ)max1)0.6380.683
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.169, 1.02 0.058, 0.154, 1.03
No. of reflections30193942
No. of parameters201219
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.200.22, 0.20

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), P3 (Siemens, 1989), CAD-4 Software, P3, SHELXTL-Plus (Sheldrick, 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus, SHELXL97.

Selected geometric parameters (Å, º) for (I) top
O2—C81.215 (3)C3—C161.408 (3)
N1—C21.333 (3)C5—C61.342 (3)
N2—C161.147 (3)C5—C81.483 (3)
C2—C31.356 (3)
N1—C2—C3127.8 (2)C6—C5—C4120.45 (18)
N1—C2—O1111.45 (17)C8—C5—C4114.67 (16)
C3—C2—O1120.70 (18)C5—C6—O1120.62 (19)
C2—C3—C16119.32 (19)C5—C6—C7132.0 (2)
C2—C3—C4120.76 (18)O1—C6—C7107.31 (17)
C16—C3—C4119.79 (17)N2—C16—C3178.8 (3)
C6—C5—C8124.87 (19)
O1—C2—C3—C45.6 (3)C4—C5—C6—O17.3 (3)
C2—C3—C4—C1097.7 (2)C6—C5—C8—O2179.3 (2)
Selected geometric parameters (Å, º) for (II) top
O2—C81.203 (2)C3—C171.413 (3)
N1—C21.330 (2)C5—C61.333 (2)
N2—C171.143 (2)C5—C81.473 (2)
C2—C31.355 (2)
N1—C2—C3128.39 (17)C6—C5—C4121.73 (15)
N1—C2—O1110.66 (15)C8—C5—C4114.09 (15)
C3—C2—O1120.95 (15)C5—C6—O1120.82 (16)
C2—C3—C17119.14 (16)C5—C6—C7130.77 (17)
C2—C3—C4121.16 (16)O1—C6—C7108.40 (15)
C17—C3—C4119.26 (15)N2—C17—C3179.2 (2)
C6—C5—C8124.14 (17)
O1—C2—C3—C411.4 (3)C6—C5—C8—O2157.15 (19)
C2—C3—C4—C1196.7 (2)C8—O3—C9—C1092.6 (3)
C4—C5—C6—O11.3 (3)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O2i0.862.002.830 (2)161
N1—H1A···N2ii0.862.172.995 (2)160
Symmetry codes: (i) x, y1, z; (ii) x+2, y+1, z+1.
 

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