organic compounds
Ethyl 1-phenyl-1,4-dihydroindeno[1,2-c]pyrazole-3-carboxylate
aCornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia, bDepartment of Chemistry, College of Science and Humanities, Shaqra University, Duwadimi, Saudi Arabia, cApplied Organic Chemistry Department, National Research Centre, Dokki, Giza, Egypt, dNational Center for Petrochemicals Technology, King Abdulaziz City for Science and Technology, PO Box 6086, Riyadh 11442, Saudi Arabia, and eSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
*Correspondence e-mail: gelhiti@ksu.edu.sa
The non-H atoms of the title molecule, C19H16N2O2, are almost coplanar (r.m.s. deviation = 0.019 Å), apart from the phenyl group, which is disordered with two components of almost equal occupancy: the dihedral angle between them is 78.9 (3)°. In the crystal, weak C—H⋯N hydrogen bonds link the molecules into [001] chains and aromatic π–π stacking interactions [shortest centroid–centroid separation = 3.747 (2) Å] form columns parallel to the c-axis direction.
Keywords: crystal structure; indenopyrazole.
CCDC reference: 1813277
Structure description
Pyrazole-3-carboylates can be synthesized using various efficient procedures (e.g. Khidre et al., 2016; Radwan et al., 2014). As part of our studies in this area, we now describe the synthesis and structure of the title compound.
The title molecule is almost planar (r.m.s. deviation = 0.017 Å) apart from the phenyl ring (Fig. 1), which is disordered with two components of almost equal occupancy [50.5 (4)% and 49.5 (4)%]. The components of the disordered phenyl rings are twisted by 54.6 (2) and 46.9 (2)° away from the least-squares plane of the rest of the molecule and the angle between the disorder components is 78.9 (3)°.
In the crystal, weak C—H⋯N hydrogen bonds (Table 1) link the molecules into [001] chains and aromatic π–π stacking interactions [shortest centroid–centroid separation = 3.747 (2) Å] generate columns parallel to the c-axis direction (Fig. 2).
Synthesis and crystallization
Ethyl 2-oxo-2-(1-oxo-2,3-dihydro-1H-inden-2-yl)acetate and phenyl hydrazine hydrochloride were refluxed in ethanol solution for 4 h. The mixture was left to cool and the solid obtained was filtered, washed (ethanol) and dried. Recrystallization from dimethylformamide solution provided pale-yellow crystals.
Refinement
Crystal data, data collection and structure . The phenyl ring was modelled with two disorder components with occupancies of 49.5 (4) and 50.5 (4)%.
details are summarized in Table 2Structural data
CCDC reference: 1813277
https://doi.org/10.1107/S2414314617018405/hb4196sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617018405/hb4196Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617018405/hb4196Isup3.cml
Data collection: CrysAlis PRO (Agilent, 2014); cell
CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).C19H16N2O2 | Dx = 1.265 Mg m−3 |
Mr = 304.34 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 1394 reflections |
a = 32.387 (3) Å | θ = 4.1–25.3° |
b = 9.8559 (15) Å | µ = 0.08 mm−1 |
c = 5.0043 (8) Å | T = 296 K |
V = 1597.4 (4) Å3 | Block, pale yellow |
Z = 4 | 0.38 × 0.13 × 0.05 mm |
F(000) = 640 |
Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer | 2661 reflections with I > 2σ(I) |
ω scans | Rint = 0.054 |
Absorption correction: gaussian (CrysAlisPro; Agilent, 2014) | θmax = 29.6°, θmin = 2.2° |
Tmin = 0.991, Tmax = 0.998 | h = −44→39 |
10362 measured reflections | k = −11→12 |
3460 independent reflections | l = −5→6 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.149 | w = 1/[σ2(Fo2) + (0.0805P)2 + 0.1345P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
3460 reflections | Δρmax = 0.18 e Å−3 |
240 parameters | Δρmin = −0.17 e Å−3 |
37 restraints |
Experimental. Version 1.171.37.35g (release 09-12-2014 CrysAlis171 .NET) (compiled Dec 9 2014,15:38:47) Numerical absorption correction based on gaussian integration over a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. All hydrogen atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and using a riding model with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl groups were allowed to rotate, but not to tip, to best fit the electron density. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.38927 (8) | 0.1784 (3) | 0.9703 (6) | 0.0522 (6) | |
C2 | 0.41595 (7) | 0.0900 (3) | 1.0968 (7) | 0.0532 (6) | |
C3 | 0.45872 (8) | 0.1067 (3) | 0.9863 (7) | 0.0593 (7) | |
H3A | 0.4683 | 0.0241 | 0.9010 | 0.071* | |
H3B | 0.4782 | 0.1330 | 1.1245 | 0.071* | |
C4 | 0.45247 (9) | 0.2195 (3) | 0.7847 (7) | 0.0580 (7) | |
C5 | 0.41075 (8) | 0.2621 (3) | 0.7730 (7) | 0.0552 (6) | |
C6 | 0.48178 (10) | 0.2807 (4) | 0.6220 (8) | 0.0705 (8) | |
H6 | 0.5093 | 0.2542 | 0.6295 | 0.085* | |
C7 | 0.46916 (13) | 0.3826 (4) | 0.4476 (8) | 0.0779 (10) | |
H7 | 0.4885 | 0.4246 | 0.3378 | 0.093* | |
C8 | 0.42798 (12) | 0.4225 (4) | 0.4353 (8) | 0.0748 (9) | |
H8 | 0.4202 | 0.4904 | 0.3164 | 0.090* | |
C9 | 0.39854 (10) | 0.3633 (3) | 0.5956 (7) | 0.0648 (8) | |
H9 | 0.3711 | 0.3903 | 0.5857 | 0.078* | |
C10 | 0.39149 (8) | 0.0192 (3) | 1.2805 (7) | 0.0537 (6) | |
C11 | 0.40527 (8) | −0.0897 (3) | 1.4630 (7) | 0.0588 (7) | |
C12 | 0.38793 (12) | −0.2480 (4) | 1.7995 (8) | 0.0749 (9) | |
H12A | 0.4093 | −0.2157 | 1.9192 | 0.090* | |
H12B | 0.3987 | −0.3246 | 1.6995 | 0.090* | |
C13 | 0.35063 (14) | −0.2894 (5) | 1.9549 (11) | 0.0985 (13) | |
H13A | 0.3399 | −0.2123 | 2.0491 | 0.148* | |
H13B | 0.3581 | −0.3588 | 2.0807 | 0.148* | |
H13C | 0.3300 | −0.3237 | 1.8349 | 0.148* | |
C14 | 0.31175 (11) | 0.2208 (5) | 1.0428 (9) | 0.050 (3) | 0.505 (4) |
C15 | 0.28917 (13) | 0.2838 (5) | 1.2438 (7) | 0.0645 (16) | 0.505 (4) |
H15 | 0.2983 | 0.2801 | 1.4197 | 0.077* | 0.505 (4) |
C16 | 0.25288 (12) | 0.3522 (5) | 1.1818 (8) | 0.075 (2) | 0.505 (4) |
H16 | 0.2378 | 0.3943 | 1.3163 | 0.090* | 0.505 (4) |
C17 | 0.23917 (12) | 0.3576 (6) | 0.9188 (9) | 0.074 (4) | 0.505 (4) |
H17 | 0.2149 | 0.4033 | 0.8774 | 0.089* | 0.505 (4) |
C18 | 0.26174 (13) | 0.2946 (6) | 0.7178 (7) | 0.083 (2) | 0.505 (4) |
H18 | 0.2526 | 0.2982 | 0.5419 | 0.099* | 0.505 (4) |
C19 | 0.29804 (13) | 0.2262 (5) | 0.7798 (8) | 0.0689 (18) | 0.505 (4) |
H19 | 0.3131 | 0.1840 | 0.6453 | 0.083* | 0.505 (4) |
C14A | 0.31445 (9) | 0.2308 (4) | 1.0024 (12) | 0.045 (2) | 0.495 (4) |
C15A | 0.31241 (10) | 0.3716 (3) | 0.9934 (12) | 0.0573 (14) | 0.495 (4) |
H15A | 0.3363 | 0.4229 | 1.0129 | 0.069* | 0.495 (4) |
C16A | 0.27464 (13) | 0.4357 (3) | 0.9553 (12) | 0.0685 (17) | 0.495 (4) |
H16A | 0.2733 | 0.5299 | 0.9493 | 0.082* | 0.495 (4) |
C17A | 0.23890 (10) | 0.3590 (4) | 0.9262 (12) | 0.072 (4) | 0.495 (4) |
H17A | 0.2136 | 0.4019 | 0.9007 | 0.086* | 0.495 (4) |
C18A | 0.24094 (9) | 0.2182 (4) | 0.9351 (11) | 0.0652 (17) | 0.495 (4) |
H18A | 0.2170 | 0.1669 | 0.9156 | 0.078* | 0.495 (4) |
C19A | 0.27872 (12) | 0.1541 (3) | 0.9732 (11) | 0.0565 (14) | 0.495 (4) |
H19A | 0.2801 | 0.0599 | 0.9792 | 0.068* | 0.495 (4) |
N1 | 0.35113 (6) | 0.1593 (2) | 1.0792 (6) | 0.0543 (6) | |
N2 | 0.35193 (6) | 0.0611 (2) | 1.2712 (6) | 0.0575 (6) | |
O1 | 0.44040 (7) | −0.1290 (3) | 1.4686 (7) | 0.0823 (8) | |
O2 | 0.37529 (6) | −0.1400 (2) | 1.6176 (5) | 0.0663 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0458 (13) | 0.0540 (14) | 0.0569 (15) | 0.0039 (10) | −0.0074 (12) | −0.0135 (12) |
C2 | 0.0431 (12) | 0.0557 (14) | 0.0607 (15) | 0.0047 (10) | −0.0058 (12) | −0.0127 (13) |
C3 | 0.0469 (13) | 0.0653 (16) | 0.0658 (17) | 0.0072 (11) | −0.0032 (13) | −0.0138 (15) |
C4 | 0.0532 (14) | 0.0636 (17) | 0.0571 (15) | 0.0008 (11) | −0.0005 (13) | −0.0135 (14) |
C5 | 0.0540 (14) | 0.0554 (14) | 0.0561 (15) | 0.0024 (11) | −0.0036 (13) | −0.0156 (13) |
C6 | 0.0594 (16) | 0.080 (2) | 0.072 (2) | −0.0042 (15) | 0.0023 (15) | −0.0102 (18) |
C7 | 0.087 (2) | 0.075 (2) | 0.072 (2) | −0.0097 (17) | 0.0097 (19) | −0.0071 (17) |
C8 | 0.093 (2) | 0.0641 (19) | 0.068 (2) | −0.0001 (16) | −0.0030 (18) | 0.0000 (16) |
C9 | 0.0684 (18) | 0.0589 (16) | 0.0669 (18) | 0.0061 (13) | −0.0076 (16) | −0.0089 (15) |
C10 | 0.0448 (12) | 0.0489 (13) | 0.0674 (16) | 0.0024 (10) | −0.0085 (12) | −0.0085 (13) |
C11 | 0.0498 (14) | 0.0550 (15) | 0.0717 (19) | 0.0048 (11) | −0.0071 (14) | −0.0122 (14) |
C12 | 0.086 (2) | 0.0666 (19) | 0.072 (2) | 0.0158 (16) | −0.0073 (19) | −0.0028 (17) |
C13 | 0.099 (3) | 0.100 (3) | 0.096 (3) | −0.005 (2) | −0.002 (3) | 0.018 (3) |
C14 | 0.039 (4) | 0.055 (5) | 0.056 (5) | 0.003 (3) | 0.005 (3) | 0.001 (4) |
C15 | 0.058 (3) | 0.084 (4) | 0.051 (3) | 0.015 (3) | 0.002 (3) | −0.001 (3) |
C16 | 0.064 (4) | 0.099 (5) | 0.062 (4) | 0.030 (3) | 0.007 (3) | −0.001 (3) |
C17 | 0.054 (7) | 0.098 (7) | 0.069 (7) | 0.023 (7) | −0.002 (7) | 0.000 (7) |
C18 | 0.062 (4) | 0.130 (7) | 0.057 (4) | 0.025 (4) | −0.010 (3) | 0.009 (4) |
C19 | 0.053 (3) | 0.091 (5) | 0.063 (4) | 0.012 (3) | 0.000 (3) | −0.019 (4) |
C14A | 0.040 (4) | 0.052 (5) | 0.043 (3) | 0.004 (3) | −0.005 (3) | −0.001 (3) |
C15A | 0.052 (3) | 0.050 (3) | 0.070 (4) | 0.003 (2) | 0.001 (3) | −0.007 (3) |
C16A | 0.063 (3) | 0.062 (3) | 0.081 (4) | 0.014 (3) | −0.002 (3) | −0.005 (3) |
C17A | 0.050 (6) | 0.098 (7) | 0.067 (7) | 0.026 (6) | −0.004 (6) | 0.008 (7) |
C18A | 0.041 (3) | 0.093 (5) | 0.062 (4) | 0.000 (3) | −0.006 (2) | 0.000 (3) |
C19A | 0.049 (3) | 0.061 (3) | 0.060 (3) | 0.000 (2) | −0.005 (3) | −0.001 (3) |
N1 | 0.0425 (10) | 0.0509 (12) | 0.0696 (15) | 0.0043 (8) | −0.0064 (10) | −0.0064 (11) |
N2 | 0.0440 (11) | 0.0502 (12) | 0.0782 (16) | 0.0002 (8) | −0.0075 (12) | −0.0025 (12) |
O1 | 0.0547 (12) | 0.0882 (16) | 0.104 (2) | 0.0218 (10) | −0.0061 (13) | 0.0110 (15) |
O2 | 0.0587 (11) | 0.0633 (12) | 0.0768 (14) | 0.0092 (9) | −0.0048 (11) | 0.0027 (11) |
C1—N1 | 1.363 (4) | C13—H13B | 0.9600 |
C1—C2 | 1.380 (4) | C13—H13C | 0.9600 |
C1—C5 | 1.463 (5) | C14—C15 | 1.3900 |
C2—C10 | 1.400 (5) | C14—C19 | 1.3900 |
C2—C3 | 1.501 (4) | C14—N1 | 1.424 (3) |
C3—C4 | 1.515 (5) | C15—C16 | 1.3900 |
C3—H3A | 0.9700 | C15—H15 | 0.9300 |
C3—H3B | 0.9700 | C16—C17 | 1.3900 |
C4—C6 | 1.388 (5) | C16—H16 | 0.9300 |
C4—C5 | 1.416 (4) | C17—C18 | 1.3900 |
C5—C9 | 1.393 (5) | C17—H17 | 0.9300 |
C6—C7 | 1.392 (6) | C18—C19 | 1.3900 |
C6—H6 | 0.9300 | C18—H18 | 0.9300 |
C7—C8 | 1.392 (5) | C19—H19 | 0.9300 |
C7—H7 | 0.9300 | C14A—C15A | 1.3900 |
C8—C9 | 1.376 (5) | C14A—C19A | 1.3900 |
C8—H8 | 0.9300 | C14A—N1 | 1.434 (4) |
C9—H9 | 0.9300 | C15A—C16A | 1.3900 |
C10—N2 | 1.347 (3) | C15A—H15A | 0.9300 |
C10—C11 | 1.478 (4) | C16A—C17A | 1.3900 |
C11—O1 | 1.202 (3) | C16A—H16A | 0.9300 |
C11—O2 | 1.337 (4) | C17A—C18A | 1.3900 |
C12—O2 | 1.459 (4) | C17A—H17A | 0.9300 |
C12—C13 | 1.494 (6) | C18A—C19A | 1.3900 |
C12—H12A | 0.9700 | C18A—H18A | 0.9300 |
C12—H12B | 0.9700 | C19A—H19A | 0.9300 |
C13—H13A | 0.9600 | N1—N2 | 1.364 (4) |
N1—C1—C2 | 107.3 (3) | H13A—C13—H13C | 109.5 |
N1—C1—C5 | 141.1 (2) | H13B—C13—H13C | 109.5 |
C2—C1—C5 | 111.6 (2) | C15—C14—C19 | 120.0 |
C1—C2—C10 | 105.2 (2) | C15—C14—N1 | 124.7 (3) |
C1—C2—C3 | 109.8 (3) | C19—C14—N1 | 115.1 (3) |
C10—C2—C3 | 145.0 (3) | C16—C15—C14 | 120.0 |
C2—C3—C4 | 101.7 (2) | C16—C15—H15 | 120.0 |
C2—C3—H3A | 111.4 | C14—C15—H15 | 120.0 |
C4—C3—H3A | 111.4 | C15—C16—C17 | 120.0 |
C2—C3—H3B | 111.4 | C15—C16—H16 | 120.0 |
C4—C3—H3B | 111.4 | C17—C16—H16 | 120.0 |
H3A—C3—H3B | 109.3 | C16—C17—C18 | 120.0 |
C6—C4—C5 | 120.0 (3) | C16—C17—H17 | 120.0 |
C6—C4—C3 | 128.2 (3) | C18—C17—H17 | 120.0 |
C5—C4—C3 | 111.9 (3) | C19—C18—C17 | 120.0 |
C9—C5—C4 | 120.6 (3) | C19—C18—H18 | 120.0 |
C9—C5—C1 | 134.4 (3) | C17—C18—H18 | 120.0 |
C4—C5—C1 | 105.0 (3) | C18—C19—C14 | 120.0 |
C4—C6—C7 | 118.7 (3) | C18—C19—H19 | 120.0 |
C4—C6—H6 | 120.6 | C14—C19—H19 | 120.0 |
C7—C6—H6 | 120.6 | C15A—C14A—C19A | 120.0 |
C8—C7—C6 | 120.8 (3) | C15A—C14A—N1 | 122.6 (2) |
C8—C7—H7 | 119.6 | C19A—C14A—N1 | 116.8 (3) |
C6—C7—H7 | 119.6 | C14A—C15A—C16A | 120.0 |
C9—C8—C7 | 121.2 (3) | C14A—C15A—H15A | 120.0 |
C9—C8—H8 | 119.4 | C16A—C15A—H15A | 120.0 |
C7—C8—H8 | 119.4 | C17A—C16A—C15A | 120.0 |
C8—C9—C5 | 118.6 (3) | C17A—C16A—H16A | 120.0 |
C8—C9—H9 | 120.7 | C15A—C16A—H16A | 120.0 |
C5—C9—H9 | 120.7 | C16A—C17A—C18A | 120.0 |
N2—C10—C2 | 111.3 (3) | C16A—C17A—H17A | 120.0 |
N2—C10—C11 | 122.1 (3) | C18A—C17A—H17A | 120.0 |
C2—C10—C11 | 126.7 (2) | C19A—C18A—C17A | 120.0 |
O1—C11—O2 | 123.6 (3) | C19A—C18A—H18A | 120.0 |
O1—C11—C10 | 122.3 (3) | C17A—C18A—H18A | 120.0 |
O2—C11—C10 | 114.1 (2) | C18A—C19A—C14A | 120.0 |
O2—C12—C13 | 107.3 (3) | C18A—C19A—H19A | 120.0 |
O2—C12—H12A | 110.3 | C14A—C19A—H19A | 120.0 |
C13—C12—H12A | 110.3 | C1—N1—N2 | 111.2 (2) |
O2—C12—H12B | 110.3 | C1—N1—C14 | 134.6 (3) |
C13—C12—H12B | 110.3 | N2—N1—C14 | 114.1 (3) |
H12A—C12—H12B | 108.5 | C1—N1—C14A | 125.2 (3) |
C12—C13—H13A | 109.5 | N2—N1—C14A | 123.6 (3) |
C12—C13—H13B | 109.5 | C10—N2—N1 | 105.1 (2) |
H13A—C13—H13B | 109.5 | C11—O2—C12 | 115.3 (2) |
C12—C13—H13C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···N2i | 0.93 | 2.56 | 3.489 (5) | 178 |
Symmetry code: (i) x, y, z−1. |
Footnotes
‡Additional corresponding author, e-mail: kariukib@cardiff.ac.uk.
Funding information
The project was supported by King Saud University, Deanship of Scientific Research, Research Chairs.
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