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The title compound, C19H18N2O4, adopts an almost flattened conformation. The di­hydro­pyrazole ring is almost coplanar with the seven-membered ring, the benzene ring, and the COO group. The plane defined by the α-di­carbonyl group intersects the seven-membered ring at an angle of 46.7 (1)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801004445/cv6009sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801004445/cv6009Isup2.hkl
Contains datablock I

CCDC reference: 162818

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.054
  • wR factor = 0.158
  • Data-to-parameter ratio = 18.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_369 Alert C Long C(sp2)-C(sp2) Bond C(1) - C(2) = 1.53 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Hinopurpurins (2-aryl-2,3-dihydro-3,3-dimethyl-5,6-cycloheptapyrazoledione) are known to be stable dyes (Mori et al., 1989). The title compound, 4-ethoxycarbonylphenylhinopurpurin, (I), showed a remarkably large negative halochromism; 484 nm in ethyl acetate, 517, 566, and 600 (sh) nm in trifluoroacetic acid, and 455 nm in concentrated sulfuric acid. However, the crystal structures of hinopurpurins have not ever been elucidated. We now report the structure of (I) to elucidate the properties as a dye.

The C—C and CC bond lengths of the seven-membered ring show apparent bond alternation. The C1O1 [1.220 (4) Å] and C2O2 [1.225 (4) Å] bond lengths are similar to that (1.259 Å) of tropone (Barrow et al., 1973). The N1—N2 [1.332 (3) Å] and N1C5 [1.328 (3) Å] bond lengths are close to those [1.343 Å for N—N and 1.322 Å for NC] of pyrazole (la Cour & Rasmussen, 1973).

The deviations of each atom from the least-squares plane of the seven-membered ring are -0.134 (4) Å for C1, 0.097 (4) Å for C2, 0.025 (4) Å for C3, -0.041 (4) Å for C4, -0.014 (4) Å for C5, 0.064 (4) Å for C6, and 0.032 (4) Å for C7. The diketone structure (A) (least-squares plane defined by C1, C2, O1 and O2) intersects the seven-membered ring (B) (defined by atoms C1–C7) at an angle of 15.5 (1)°. The dihydropyrazole ring (C) (defined by atoms N1, N2, C4, C5 and C8) is almost coplanar with the seven-membered ring (B), the benzene ring (D), the carboxy group (E) (defined by atoms C17, O3 and O4). The dihedral angles between planes B and C, between C and D, and between C and E are 4.1 (1), 5.3 (1) and 4.3 (4)°, respectively.

Experimental top

To a pyridine solution (2 ml) of 4-isopropyltropolone (164 mg, 1.0 mmol) was added drop by drop an aqueous solution of a diazotized 4-ethoxycarbonylaniline (248 mg, 1.5 mmol) at 273 to 278 K with stirring for 2 h. After the solution was diluted with water (10 ml), the precipitate was filtrered and dried. An ethanol solution of the precipitate was refluxed for 4 h and cooled to yield the title compound (I) (142 mg, 42%) by filtration (Mori et al., 1989). The single crystals of (I) were obtained by recrystallization from chloroform.

Refinement top

All H atoms were located at ideal positions and restrained with Uiso held fixed to 1.2Ueq of the parent atoms.

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal_GX (Hall & du Boulay, 1995); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids.
Ethyl 4-(2,3,5,6-tetrahydro-3,3-dimethyl-5,6-dioxo-1,2-cycloheptapyrazol-2-yl)- benzoate top
Crystal data top
C19H18N2O4Dx = 1.305 Mg m3
Mr = 338.35Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 16 reflections
a = 19.028 (3) Åθ = 9.2–17.9°
b = 19.166 (3) ŵ = 0.09 mm1
c = 9.4466 (5) ÅT = 296 K
V = 3445.1 (7) Å3Prism, red
Z = 80.33 × 0.27 × 0.13 mm
F(000) = 1424
Data collection top
Enraf-Nonius CAD-4
diffractometer
1280 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.000
Graphite monochromatorθmax = 28.0°, θmin = 2.6°
ω–2θ scansh = 025
Absorption correction: ψ scan
(North et al., 1968)
k = 250
Tmin = 0.969, Tmax = 0.998l = 012
4149 measured reflections3 standard reflections every 120 min
4149 independent reflections intensity decay: 0.5%
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)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158H-atom parameters constrained
S = 0.89 w = 1/[σ2(Fo2) + (0.0539P)2]
where P = (Fo2 + 2Fc2)/3
4149 reflections(Δ/σ)max = 0.001
226 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C19H18N2O4V = 3445.1 (7) Å3
Mr = 338.35Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 19.028 (3) ŵ = 0.09 mm1
b = 19.166 (3) ÅT = 296 K
c = 9.4466 (5) Å0.33 × 0.27 × 0.13 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
1280 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.000
Tmin = 0.969, Tmax = 0.9983 standard reflections every 120 min
4149 measured reflections intensity decay: 0.5%
4149 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.158H-atom parameters constrained
S = 0.89Δρmax = 0.20 e Å3
4149 reflectionsΔρmin = 0.24 e Å3
226 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.88831 (14)0.14229 (13)0.0112 (3)0.0469 (7)
N20.86161 (13)0.08041 (12)0.0463 (3)0.0435 (7)
O10.75989 (15)0.38435 (12)0.2298 (3)0.0966 (10)
O20.72097 (12)0.28665 (12)0.4086 (3)0.0699 (8)
O31.01239 (14)0.15229 (13)0.3384 (3)0.0802 (9)
O40.94270 (12)0.21630 (13)0.1981 (3)0.0688 (8)
C10.7870 (2)0.32710 (17)0.2157 (4)0.0602 (11)
C20.75567 (18)0.26834 (17)0.3058 (4)0.0526 (9)
C30.76344 (17)0.19528 (16)0.2746 (4)0.0517 (9)
H30.73500.16570.32750.062*
C40.80545 (16)0.16337 (15)0.1810 (3)0.0411 (8)
C50.85689 (16)0.19151 (15)0.0873 (3)0.0426 (8)
C60.87661 (17)0.26265 (15)0.0660 (4)0.0534 (9)
H60.91440.27020.00560.064*
C70.8474 (2)0.31988 (16)0.1223 (4)0.0598 (10)
H70.86910.36160.09770.072*
C80.80673 (16)0.08491 (14)0.1579 (3)0.0417 (8)
C90.73500 (16)0.05919 (15)0.1045 (4)0.0533 (9)
H9A0.73670.00960.09040.080*
H9B0.72400.08180.01660.080*
H9C0.69950.07010.17330.080*
C100.83016 (18)0.04850 (15)0.2944 (3)0.0556 (10)
H10A0.83110.00100.27950.083*
H10B0.79770.05930.36910.083*
H10C0.87630.06440.32000.083*
C110.88638 (16)0.02091 (15)0.0251 (3)0.0401 (8)
C120.86496 (17)0.04586 (15)0.0119 (3)0.0470 (9)
H120.83230.05200.08410.056*
C130.89192 (17)0.10316 (16)0.0580 (3)0.0472 (8)
H130.87760.14760.03120.057*
C140.93974 (16)0.09575 (17)0.1668 (4)0.0483 (8)
C150.95942 (17)0.02876 (18)0.2044 (4)0.0576 (10)
H150.99120.02270.27810.069*
C160.93345 (16)0.02937 (17)0.1359 (4)0.0532 (9)
H160.94740.07380.16380.064*
C170.96954 (19)0.1561 (2)0.2448 (4)0.0588 (10)
C180.9630 (2)0.27980 (19)0.2713 (4)0.0785 (13)
H18A1.01370.28140.28200.094*
H18B0.94200.28080.36480.094*
C190.93878 (19)0.34069 (18)0.1878 (4)0.0796 (13)
H19A0.95200.38290.23550.119*
H19B0.88860.33900.17820.119*
H19C0.96010.33960.09570.119*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0529 (18)0.0388 (15)0.0489 (17)0.0065 (14)0.0043 (15)0.0014 (14)
N20.0482 (16)0.0353 (15)0.0472 (18)0.0002 (13)0.0113 (14)0.0002 (14)
O10.109 (2)0.0492 (16)0.131 (3)0.0277 (15)0.001 (2)0.0067 (17)
O20.0709 (17)0.0655 (16)0.0734 (18)0.0176 (13)0.0015 (15)0.0229 (15)
O30.0790 (19)0.0847 (19)0.077 (2)0.0077 (15)0.0273 (17)0.0220 (16)
O40.0736 (17)0.0551 (16)0.0776 (19)0.0036 (13)0.0131 (15)0.0263 (15)
C10.072 (3)0.038 (2)0.070 (3)0.0117 (19)0.020 (2)0.005 (2)
C20.050 (2)0.051 (2)0.057 (2)0.0113 (16)0.014 (2)0.015 (2)
C30.051 (2)0.047 (2)0.058 (2)0.0047 (17)0.006 (2)0.0025 (18)
C40.0421 (18)0.0397 (18)0.042 (2)0.0014 (16)0.0009 (17)0.0016 (17)
C50.042 (2)0.0393 (19)0.046 (2)0.0035 (16)0.0019 (18)0.0035 (17)
C60.061 (2)0.043 (2)0.057 (2)0.0079 (17)0.0037 (19)0.0033 (18)
C70.074 (3)0.040 (2)0.066 (3)0.007 (2)0.012 (2)0.0039 (19)
C80.0471 (19)0.0381 (18)0.040 (2)0.0010 (16)0.0089 (17)0.0014 (16)
C90.050 (2)0.0447 (19)0.065 (2)0.0102 (16)0.0072 (19)0.0059 (18)
C100.073 (2)0.049 (2)0.046 (2)0.0006 (18)0.0039 (19)0.0044 (18)
C110.041 (2)0.0419 (19)0.037 (2)0.0050 (16)0.0009 (16)0.0014 (16)
C120.050 (2)0.047 (2)0.044 (2)0.0015 (17)0.0059 (17)0.0010 (17)
C130.054 (2)0.0411 (19)0.046 (2)0.0034 (16)0.0055 (19)0.0017 (17)
C140.046 (2)0.052 (2)0.047 (2)0.0071 (17)0.0009 (19)0.0089 (19)
C150.052 (2)0.066 (2)0.055 (2)0.0014 (18)0.014 (2)0.008 (2)
C160.056 (2)0.049 (2)0.054 (2)0.0008 (18)0.013 (2)0.0028 (18)
C170.050 (2)0.066 (3)0.061 (3)0.003 (2)0.003 (2)0.020 (2)
C180.086 (3)0.064 (3)0.085 (3)0.012 (2)0.003 (3)0.043 (3)
C190.070 (3)0.058 (2)0.110 (4)0.009 (2)0.009 (3)0.026 (3)
Geometric parameters (Å, º) top
N1—C51.328 (3)C9—H9B0.9600
N1—N21.332 (3)C9—H9C0.9600
N2—C81.486 (4)C10—H10A0.9600
N2—C111.406 (3)C10—H10B0.9600
O1—C11.220 (4)C10—H10C0.9600
O2—C21.225 (4)C11—C161.387 (4)
O3—C171.205 (4)C11—C121.388 (4)
O4—C171.337 (4)C12—C131.380 (4)
O4—C181.452 (3)C12—H120.9300
C1—C21.533 (5)C13—C141.380 (4)
C1—C71.455 (5)C13—H130.9300
C2—C31.439 (4)C14—C151.384 (4)
C3—C41.340 (4)C14—C171.484 (5)
C3—H30.9300C15—C161.380 (4)
C4—C51.426 (4)C15—H150.9300
C4—C81.520 (4)C16—H160.9300
C5—C61.428 (4)C18—C191.482 (5)
C6—C71.339 (4)C18—H18A0.9700
C6—H60.9300C18—H18B0.9700
C7—H70.9300C19—H19A0.9600
C8—C91.536 (4)C19—H19B0.9600
C8—C101.533 (4)C19—H19C0.9600
C9—H9A0.9600
C5—N1—N2109.0 (2)C8—C10—H10B109.5
N1—N2—C11118.4 (2)H10A—C10—H10B109.5
N1—N2—C8113.1 (2)C8—C10—H10C109.5
C11—N2—C8128.5 (2)H10A—C10—H10C109.5
C17—O4—C18117.7 (3)H10B—C10—H10C109.5
O1—C1—C7119.1 (4)C16—C11—C12119.2 (3)
O1—C1—C2115.8 (4)C16—C11—N2118.9 (3)
C7—C1—C2125.1 (3)C12—C11—N2121.9 (3)
O2—C2—C3119.8 (3)C13—C12—C11120.3 (3)
O2—C2—C1116.1 (3)C13—C12—H12119.9
C3—C2—C1124.2 (3)C11—C12—H12119.9
C4—C3—C2129.9 (3)C12—C13—C14121.3 (3)
C4—C3—H3115.1C12—C13—H13119.3
C2—C3—H3115.1C14—C13—H13119.3
C3—C4—C5130.3 (3)C13—C14—C15117.7 (3)
C3—C4—C8123.8 (3)C13—C14—C17122.8 (3)
C5—C4—C8105.9 (3)C15—C14—C17119.5 (3)
N1—C5—C4112.1 (3)C16—C15—C14122.2 (3)
N1—C5—C6118.9 (3)C16—C15—H15118.9
C4—C5—C6129.0 (3)C14—C15—H15118.9
C7—C6—C5128.1 (3)C15—C16—C11119.4 (3)
C7—C6—H6116.0C15—C16—H16120.3
C5—C6—H6116.0C11—C16—H16120.3
C6—C7—C1130.2 (3)O3—C17—O4123.6 (3)
C6—C7—H7114.9O3—C17—C14125.1 (4)
C1—C7—H7114.9O4—C17—C14111.3 (3)
N2—C8—C499.8 (2)O4—C18—C19108.9 (3)
N2—C8—C10111.5 (2)O4—C18—H18A109.9
C4—C8—C10109.5 (3)C19—C18—H18A109.9
N2—C8—C9111.9 (3)O4—C18—H18B109.9
C4—C8—C9110.5 (2)C19—C18—H18B109.9
C10—C8—C9112.8 (3)H18A—C18—H18B108.3
C8—C9—H9A109.5C18—C19—H19A109.5
C8—C9—H9B109.5C18—C19—H19B109.5
H9A—C9—H9B109.5H19A—C19—H19B109.5
C8—C9—H9C109.5C18—C19—H19C109.5
H9A—C9—H9C109.5H19A—C19—H19C109.5
H9B—C9—H9C109.5H19B—C19—H19C109.5
C8—C10—H10A109.5
C5—N1—N2—C11178.3 (3)C3—C4—C8—N2179.7 (3)
C5—N1—N2—C80.6 (3)C5—C4—C8—N20.7 (3)
O1—C1—C2—O219.3 (5)C3—C4—C8—C1062.6 (4)
C7—C1—C2—O2157.8 (3)C5—C4—C8—C10116.4 (3)
O1—C1—C2—C3159.3 (3)C3—C4—C8—C962.3 (4)
C7—C1—C2—C323.6 (5)C5—C4—C8—C9118.7 (3)
O2—C2—C3—C4170.4 (3)C8—N2—C11—C16173.8 (3)
C1—C2—C3—C411.1 (6)N1—N2—C11—C12175.4 (3)
C2—C3—C4—C52.5 (6)N1—N2—C11—C164.8 (4)
C2—C3—C4—C8178.7 (3)C8—N2—C11—C126.0 (5)
N2—N1—C5—C40.0 (4)C16—C11—C12—C132.0 (5)
N2—N1—C5—C6179.2 (3)N2—C11—C12—C13178.2 (3)
C3—C4—C5—N1179.4 (3)C11—C12—C13—C140.9 (5)
C8—C4—C5—N10.4 (3)C12—C13—C14—C150.5 (5)
C3—C4—C5—C61.4 (6)C12—C13—C14—C17179.7 (3)
C8—C4—C5—C6179.6 (3)C13—C14—C15—C160.7 (5)
N1—C5—C6—C7173.7 (3)C17—C14—C15—C16179.9 (3)
C4—C5—C6—C75.4 (6)C14—C15—C16—C110.4 (5)
C5—C6—C7—C12.2 (6)C12—C11—C16—C151.7 (5)
O1—C1—C7—C6164.0 (4)N2—C11—C16—C15178.4 (3)
C2—C1—C7—C619.0 (6)C18—O4—C17—O34.3 (5)
N1—N2—C8—C40.8 (3)C18—O4—C17—C14175.6 (3)
C11—N2—C8—C4177.9 (3)C13—C14—C17—O3178.4 (3)
N1—N2—C8—C9117.7 (3)C15—C14—C17—O32.4 (5)
N1—N2—C8—C10114.9 (3)C13—C14—C17—O41.6 (5)
C11—N2—C8—C1066.4 (4)C15—C14—C17—O4177.6 (3)
C11—N2—C8—C961.0 (4)C17—O4—C18—C19169.5 (3)

Experimental details

Crystal data
Chemical formulaC19H18N2O4
Mr338.35
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)296
a, b, c (Å)19.028 (3), 19.166 (3), 9.4466 (5)
V3)3445.1 (7)
Z8
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.33 × 0.27 × 0.13
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.969, 0.998
No. of measured, independent and
observed [I > 2σ(I)] reflections
4149, 4149, 1280
Rint0.000
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.158, 0.89
No. of reflections4149
No. of parameters226
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.24

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, MolEN (Fair, 1990), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), Xtal_GX (Hall & du Boulay, 1995), SHELXL97.

Selected geometric parameters (Å, º) top
N1—C51.328 (3)C2—C31.439 (4)
N1—N21.332 (3)C3—C41.340 (4)
N2—C81.486 (4)C4—C51.426 (4)
N2—C111.406 (3)C4—C81.520 (4)
O1—C11.220 (4)C5—C61.428 (4)
O2—C21.225 (4)C6—C71.339 (4)
C1—C21.533 (5)C8—C91.536 (4)
C1—C71.455 (5)C8—C101.533 (4)
O1—C1—C2—O219.3 (5)C18—O4—C17—C14175.6 (3)
N1—N2—C8—C9117.7 (3)C13—C14—C17—O3178.4 (3)
N1—N2—C8—C10114.9 (3)C13—C14—C17—O41.6 (5)
N1—N2—C11—C12175.4 (3)C17—O4—C18—C19169.5 (3)
N1—N2—C11—C164.8 (4)
 

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