organic compounds
Ethyl 4,6-dimethyl-3-oxo-2-phenyl-3,7-dihydro-2H-pyrazolo[3,4-b]pyridine-5-carboxylate monohydrate
aLaboratoire de Chimie Organique et Analytique, University Sultan Moulay Slimane, Faculty of Science and Technology, BP 523, Beni-Mellal, Morocco, bUniv. Lille, CNRS, Centrale Lille, Ecole Nationale-Supérieure de Chimie de Lille (ENSCL), Univ. Artois, UMR 8181 – UCCS – Unité de Catalyse et Chimie du Solide, F-59000 Lille, France, and cLaboratoire de Spectro-Chimie Appliqué et Environnement, University Sultan Moulay Slimane, Faculty of Science and Technology, BP 523, Beni-Mellal, Morocco
*Correspondence e-mail: s.akhramez@gmail.com
In the title compound, C17H17N3O3·H2O, the dihedral angle between the 4,6-dimethyl-pyrazolo[3,4-b]pyridine-3-one unit [maximum deviation = 0.048 (2) Å] and the phenyl ring is 5.1 (1)°. The structure is characterized by disorder of the carboxylate O atoms, which are split into two parts with a major component of 0.898 (4). In the crystal, the organic molecules and lattice water molecules are linked via O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds. The molecules are also linked by C—H⋯π and weak offset π–π stacking interactions, forming sheets parallel to (001).
Keywords: crystal structure; pyrazolo[3,4-b]pyridine derivatives; biological activity; hydrogen bonding.
CCDC reference: 1509474
Structure description
The number of substituted pyrazolo[3,4-b]pyridines has increased in organic and pharmaceutical chemistry. These heterocyclic systems are found in a number of molecules possessing biological and pharmacological activities such as antimicrobial (Raviraj et al., 2013), anti-inflammatory (Fong & Heymsfield, 2009) and antiviral (Bernardino et al., 2007). Besides their pharmacological properties, pyrazolo[3,4-b]pyridines also exhibit corrosion inhibition properties (Gupta et al., 2015). As part of our research on the preparation of new pyrazolo[3,4-b]pyridine-3-ones (Fadel et al., 2011), the title compound was isolated and its was determined by X-ray diffraction.
The molecular structure is shown in Fig. 1. The dihedral angle between the 4,6-dimethyl-pyrazolo[3,4-b]pyridine-3-one unit [maximum deviation = 0.048 (2) Å] and the phenyl ring is 5.1 (1)°. In the crystal, the components are linked through O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds (Table 1, Fig. 2). The cohesion of the is enhanced by three π–π stacking interactions between the rings, Fig. 3, with centroid–centroid distances in the range 3.671 (2) to 3.784 (2) Å, forming molecular layers along the c-axis direction. These sheets are linked together by C17—H17A⋯π interactions (Table 1, Fig. 2).
Synthesis and crystallization
A solution of 3-amino-1-phenyl-1H-pyrazol-5(4H)-one (875 mg, 5 mmol) and ethyl acetoacetate (3,19 ml, 25 mmol) was refluxed in a sand bath (180–185° C) for 6 h. The reaction mixture was left overnight at room temperature. The grey crystals formed were collected by filtration and washed with diethyl ether. The dried orange crystals were obtained with 42% yield and melting point around 534 K.
1H NMR (300 MHz, CDCl3, δ p.p.m.): 1.39 (3H, H17), 2.28 (3H, H14), 2.77 (3H, H13), 4.40 (2H, H16), 7.21 (1H, H10), 7.40 (2H, H9 and H11), 7.85 (2H, H8 and H12);
13C NMR (75 MHz, CDCl3, δ p.p.m.): 14.56 (CH3), 22.16 (C13, C14), 61.73 (C16), 108.99 (C2, C4), 122.30 (C10), 125.72 (C9, C11), 129.12 (C9, C11), 137.40 (C7), 150.92 (C3), 153.73 (C6), 157.34 (C5), 159.16 (C15), 167.30 (C1).
Refinement
Crystal data, data collection and structure . The reflection (33) affected by the beam-stop was removed during The O atoms of the carboxylate group are disordered over two sets of sites, with a refined occupancy ratio of 0.898 (4):0.102 (4).
details are summarized in Table 2Structural data
CCDC reference: 1509474
https://doi.org/10.1107/S2414314616016199/xu4017sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016199/xu4017Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314616016199/xu4017Isup3.cml
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg et al., 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).C17H17N3O3·H2O | F(000) = 696 |
Mr = 329.35 | Dx = 1.336 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.5321 (15) Å | Cell parameters from 2879 reflections |
b = 18.794 (3) Å | θ = 2.1–25.0° |
c = 9.0491 (12) Å | µ = 0.10 mm−1 |
β = 113.903 (5)° | T = 293 K |
V = 1637.6 (4) Å3 | Block, orange |
Z = 4 | 0.32 × 0.24 × 0.15 mm |
Bruker DUO APEXII CCD diffractometer | 1709 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.056 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | θmax = 25.0°, θmin = 2.1° |
Tmin = 0.696, Tmax = 0.746 | h = −12→11 |
15373 measured reflections | k = −22→22 |
2879 independent reflections | l = −10→10 |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.166 | w = 1/[σ2(Fo2) + (0.0837P)2 + 0.5493P] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max < 0.001 |
2879 reflections | Δρmax = 0.26 e Å−3 |
235 parameters | Δρmin = −0.24 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.2341 (2) | −0.04229 (12) | 0.5100 (2) | 0.0593 (6) | |
O2 | −0.1524 (3) | 0.14716 (15) | 0.0298 (4) | 0.0671 (8) | 0.898 (4) |
O3 | −0.0117 (3) | 0.21966 (17) | −0.0281 (4) | 0.1033 (12) | 0.898 (4) |
O2A | −0.1029 (19) | 0.1830 (15) | 0.092 (3) | 0.0671 (8) | 0.102 (4) |
O3A | −0.121 (2) | 0.1625 (14) | −0.133 (2) | 0.1033 (12) | 0.102 (4) |
N1 | 0.3718 (2) | −0.06247 (12) | 0.3654 (3) | 0.0446 (6) | |
N2 | 0.3789 (2) | −0.04097 (13) | 0.2189 (3) | 0.0453 (6) | |
C1 | 0.2639 (3) | −0.03131 (16) | 0.3926 (3) | 0.0451 (7) | |
C2 | 0.1975 (3) | 0.01464 (15) | 0.2528 (3) | 0.0419 (7) | |
C3 | 0.0919 (3) | 0.06363 (15) | 0.2102 (3) | 0.0455 (7) | |
C4 | 0.0624 (3) | 0.10151 (16) | 0.0640 (3) | 0.0476 (7) | |
C5 | 0.1344 (3) | 0.08678 (16) | −0.0323 (3) | 0.0481 (7) | |
C6 | 0.2745 (3) | 0.00291 (14) | 0.1589 (3) | 0.0408 (7) | |
C7 | 0.4740 (3) | −0.11041 (15) | 0.4645 (3) | 0.0443 (7) | |
C15 | −0.0376 (4) | 0.1618 (2) | 0.0152 (4) | 0.0646 (9) | |
N3 | 0.2371 (2) | 0.03840 (12) | 0.0153 (3) | 0.0458 (6) | |
H3N | 0.2801 | 0.0295 | −0.0456 | 0.055* | |
C8 | 0.5713 (3) | −0.13804 (16) | 0.4129 (4) | 0.0508 (8) | |
H8 | 0.5677 | −0.1259 | 0.3117 | 0.061* | |
C9 | 0.6732 (3) | −0.18347 (16) | 0.5113 (4) | 0.0556 (8) | |
H9 | 0.7381 | −0.2015 | 0.4758 | 0.067* | |
C10 | 0.6803 (3) | −0.20245 (17) | 0.6610 (4) | 0.0616 (9) | |
H10 | 0.7498 | −0.2328 | 0.7271 | 0.074* | |
C11 | 0.5833 (4) | −0.17590 (17) | 0.7113 (4) | 0.0634 (9) | |
H11 | 0.5869 | −0.1889 | 0.8121 | 0.076* | |
C12 | 0.4808 (3) | −0.13044 (16) | 0.6156 (4) | 0.0562 (8) | |
H12 | 0.4158 | −0.1130 | 0.6518 | 0.067* | |
C13 | 0.0193 (3) | 0.07762 (19) | 0.3210 (4) | 0.0654 (10) | |
H13A | 0.0138 | 0.1280 | 0.3351 | 0.098* | |
H13B | 0.0706 | 0.0558 | 0.4241 | 0.098* | |
H13C | −0.0727 | 0.0580 | 0.2744 | 0.098* | |
C14 | 0.1036 (4) | 0.12011 (18) | −0.1943 (4) | 0.0657 (9) | |
H14A | 0.1171 | 0.1706 | −0.1817 | 0.099* | |
H14B | 0.0092 | 0.1103 | −0.2659 | 0.099* | |
H14C | 0.1650 | 0.1007 | −0.2386 | 0.099* | |
C16 | −0.2515 (4) | 0.2055 (2) | 0.0019 (6) | 0.0954 (14) | |
H16A | −0.2026 | 0.2497 | 0.0444 | 0.115* | |
H16B | −0.3065 | 0.2115 | −0.1130 | 0.115* | |
C17 | −0.3398 (5) | 0.1878 (2) | 0.0831 (6) | 0.1029 (15) | |
H17A | −0.4087 | 0.2242 | 0.0629 | 0.154* | |
H17B | −0.2849 | 0.1842 | 0.1972 | 0.154* | |
H17C | −0.3847 | 0.1431 | 0.0432 | 0.154* | |
O4 | 0.3690 (3) | 0.00542 (15) | 0.8210 (3) | 0.0673 (7) | |
H1W | 0.443 (5) | 0.023 (3) | 0.819 (6) | 0.131 (19)* | |
H2W | 0.317 (4) | −0.010 (2) | 0.720 (6) | 0.114 (16)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0515 (13) | 0.0909 (16) | 0.0426 (11) | 0.0058 (12) | 0.0263 (10) | 0.0118 (11) |
O2 | 0.0455 (16) | 0.0638 (18) | 0.092 (2) | 0.0074 (14) | 0.0281 (15) | 0.0040 (15) |
O3 | 0.088 (2) | 0.078 (2) | 0.167 (3) | 0.0230 (17) | 0.076 (2) | 0.048 (2) |
O2A | 0.0455 (16) | 0.0638 (18) | 0.092 (2) | 0.0074 (14) | 0.0281 (15) | 0.0040 (15) |
O3A | 0.088 (2) | 0.078 (2) | 0.167 (3) | 0.0230 (17) | 0.076 (2) | 0.048 (2) |
N1 | 0.0414 (14) | 0.0569 (15) | 0.0391 (13) | 0.0032 (12) | 0.0202 (11) | 0.0044 (11) |
N2 | 0.0426 (14) | 0.0588 (15) | 0.0386 (13) | 0.0019 (13) | 0.0208 (12) | 0.0017 (11) |
C1 | 0.0382 (16) | 0.0599 (18) | 0.0377 (15) | −0.0039 (14) | 0.0160 (14) | −0.0036 (14) |
C2 | 0.0345 (16) | 0.0557 (17) | 0.0366 (14) | −0.0047 (14) | 0.0155 (13) | −0.0040 (13) |
C3 | 0.0386 (17) | 0.0561 (17) | 0.0436 (16) | −0.0014 (14) | 0.0183 (14) | −0.0029 (14) |
C4 | 0.0374 (17) | 0.0568 (18) | 0.0478 (17) | −0.0009 (15) | 0.0164 (14) | −0.0026 (14) |
C5 | 0.0372 (17) | 0.0579 (18) | 0.0460 (16) | −0.0027 (15) | 0.0136 (14) | 0.0017 (14) |
C6 | 0.0392 (16) | 0.0506 (17) | 0.0333 (14) | −0.0037 (14) | 0.0154 (13) | −0.0025 (13) |
C7 | 0.0437 (17) | 0.0467 (16) | 0.0410 (16) | −0.0011 (14) | 0.0156 (14) | −0.0019 (13) |
C15 | 0.052 (2) | 0.078 (3) | 0.064 (2) | 0.011 (2) | 0.0243 (18) | 0.0137 (19) |
N3 | 0.0430 (14) | 0.0613 (15) | 0.0387 (13) | 0.0014 (13) | 0.0221 (11) | 0.0008 (12) |
C8 | 0.0470 (18) | 0.0544 (18) | 0.0496 (18) | −0.0001 (15) | 0.0183 (15) | −0.0016 (15) |
C9 | 0.0482 (19) | 0.0523 (18) | 0.065 (2) | 0.0031 (16) | 0.0216 (17) | −0.0080 (16) |
C10 | 0.062 (2) | 0.0532 (19) | 0.062 (2) | 0.0086 (17) | 0.0168 (18) | 0.0018 (16) |
C11 | 0.079 (2) | 0.057 (2) | 0.0509 (19) | 0.0140 (19) | 0.0230 (18) | 0.0108 (16) |
C12 | 0.067 (2) | 0.0563 (19) | 0.0494 (17) | 0.0076 (17) | 0.0274 (17) | 0.0025 (15) |
C13 | 0.054 (2) | 0.092 (3) | 0.0580 (19) | 0.0108 (18) | 0.0308 (17) | 0.0053 (18) |
C14 | 0.066 (2) | 0.077 (2) | 0.056 (2) | 0.0057 (18) | 0.0266 (18) | 0.0152 (17) |
C16 | 0.070 (3) | 0.102 (3) | 0.125 (3) | 0.042 (2) | 0.051 (3) | 0.037 (3) |
C17 | 0.107 (3) | 0.113 (3) | 0.112 (3) | 0.046 (3) | 0.068 (3) | 0.021 (3) |
O4 | 0.0592 (16) | 0.102 (2) | 0.0534 (15) | −0.0104 (14) | 0.0353 (13) | −0.0105 (13) |
O1—C1 | 1.241 (3) | C8—C9 | 1.378 (4) |
O2—C15 | 1.299 (4) | C8—H8 | 0.9300 |
O2—C16 | 1.464 (4) | C9—C10 | 1.373 (4) |
O3—C15 | 1.223 (4) | C9—H9 | 0.9300 |
O2A—C15 | 1.23 (2) | C10—C11 | 1.370 (4) |
O2A—C16 | 1.504 (16) | C10—H10 | 0.9300 |
O3A—C15 | 1.272 (18) | C11—C12 | 1.374 (4) |
N1—C1 | 1.386 (4) | C11—H11 | 0.9300 |
N1—C7 | 1.412 (4) | C12—H12 | 0.9300 |
N1—N2 | 1.417 (3) | C13—H13A | 0.9600 |
N2—C6 | 1.303 (3) | C13—H13B | 0.9600 |
C1—C2 | 1.455 (4) | C13—H13C | 0.9600 |
C2—C3 | 1.373 (4) | C14—H14A | 0.9600 |
C2—C6 | 1.411 (4) | C14—H14B | 0.9600 |
C3—C4 | 1.421 (4) | C14—H14C | 0.9600 |
C3—C13 | 1.511 (4) | C16—C17 | 1.439 (5) |
C4—C5 | 1.396 (4) | C16—H16A | 0.9700 |
C4—C15 | 1.487 (4) | C16—H16B | 0.9700 |
C5—N3 | 1.343 (4) | C17—H17A | 0.9600 |
C5—C14 | 1.503 (4) | C17—H17B | 0.9600 |
C6—N3 | 1.368 (3) | C17—H17C | 0.9600 |
C7—C8 | 1.387 (4) | O4—H1W | 0.86 (5) |
C7—C12 | 1.392 (4) | O4—H2W | 0.90 (5) |
N3—H3N | 0.8600 | ||
C15—O2—C16 | 116.8 (3) | C10—C9—C8 | 121.0 (3) |
C15—O2A—C16 | 118.7 (19) | C10—C9—H9 | 119.5 |
C1—N1—C7 | 128.7 (2) | C8—C9—H9 | 119.5 |
C1—N1—N2 | 113.8 (2) | C11—C10—C9 | 118.9 (3) |
C7—N1—N2 | 117.4 (2) | C11—C10—H10 | 120.6 |
C6—N2—N1 | 102.4 (2) | C9—C10—H10 | 120.6 |
O1—C1—N1 | 126.3 (3) | C10—C11—C12 | 121.2 (3) |
O1—C1—C2 | 130.1 (3) | C10—C11—H11 | 119.4 |
N1—C1—C2 | 103.7 (2) | C12—C11—H11 | 119.4 |
C3—C2—C6 | 122.2 (2) | C11—C12—C7 | 120.1 (3) |
C3—C2—C1 | 133.8 (2) | C11—C12—H12 | 119.9 |
C6—C2—C1 | 103.9 (2) | C7—C12—H12 | 119.9 |
C2—C3—C4 | 116.4 (2) | C3—C13—H13A | 109.5 |
C2—C3—C13 | 120.0 (3) | C3—C13—H13B | 109.5 |
C4—C3—C13 | 123.5 (3) | H13A—C13—H13B | 109.5 |
C5—C4—C3 | 120.9 (3) | C3—C13—H13C | 109.5 |
C5—C4—C15 | 117.7 (3) | H13A—C13—H13C | 109.5 |
C3—C4—C15 | 121.3 (3) | H13B—C13—H13C | 109.5 |
N3—C5—C4 | 120.3 (2) | C5—C14—H14A | 109.5 |
N3—C5—C14 | 115.0 (3) | C5—C14—H14B | 109.5 |
C4—C5—C14 | 124.7 (3) | H14A—C14—H14B | 109.5 |
N2—C6—N3 | 125.0 (2) | C5—C14—H14C | 109.5 |
N2—C6—C2 | 116.2 (2) | H14A—C14—H14C | 109.5 |
N3—C6—C2 | 118.7 (3) | H14B—C14—H14C | 109.5 |
C8—C7—C12 | 118.6 (3) | C17—C16—O2 | 107.5 (3) |
C8—C7—N1 | 120.2 (2) | C17—C16—O2A | 113.7 (11) |
C12—C7—N1 | 121.3 (3) | C17—C16—H16A | 110.2 |
O2A—C15—O3A | 107.0 (15) | O2—C16—H16A | 110.2 |
O3—C15—O2 | 124.0 (3) | C17—C16—H16B | 110.2 |
O3—C15—C4 | 123.4 (3) | O2—C16—H16B | 110.2 |
O2A—C15—C4 | 124.8 (11) | H16A—C16—H16B | 108.5 |
O3A—C15—C4 | 115.0 (13) | C16—C17—H17A | 109.5 |
O2—C15—C4 | 112.6 (3) | C16—C17—H17B | 109.5 |
C5—N3—C6 | 121.3 (2) | H17A—C17—H17B | 109.5 |
C5—N3—H3N | 119.3 | C16—C17—H17C | 109.5 |
C6—N3—H3N | 119.3 | H17A—C17—H17C | 109.5 |
C9—C8—C7 | 120.2 (3) | H17B—C17—H17C | 109.5 |
C9—C8—H8 | 119.9 | H1W—O4—H2W | 107 (4) |
C7—C8—H8 | 119.9 |
Cg3 is the centroid of the C7–C12 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N···O4i | 0.86 | 1.86 | 2.718 (3) | 177 |
O4—H1W···N2ii | 0.86 (5) | 2.07 (5) | 2.899 (3) | 164 (5) |
O4—H2W···O1 | 0.90 (5) | 1.84 (5) | 2.739 (3) | 172 (4) |
C17—H17A···Cg3iii | 0.96 | 2.79 | 3.717 (4) | 163 |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y, −z+1; (iii) −x, y+1/2, −z+1/2. |
Acknowledgements
X-Ray diffractometers are funded by Région NPDC, FEDER, CNRS and MESR.
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