organic compounds
9-(Thiophen-2-yl)-8,9-dihydro-3H-pyrazolo[4,3-f]quinolin-7(6H)-one ethanol monosolvate
aLianyungang Teacher's College, Lianyungang 222006, People's Republic of China
*Correspondence e-mail: jiarunhong@126.com
In the title compound, C14H11N3OS·C2H5OH, the dihedral angle between the pyridine N—Cfused—Cfused—C(thiophene) plane and the plane of the thiophene ring is 81.9 (3)°, indicating that they are close to perpendicular. The dihedral angle between this pyridine plane and the benzene ring is 1.3 (3)°. The thiophene ring is disordered over two coplanar orientations with an occupancy ratio of 0.692 (7):0.308 (7), while the ethanol solvent molecule is also disordered over two sets of site in a 0.66 (4):0.34 (4) ratio. In the crystal, chains are formed along the b axis by N—H⋯O and O—H⋯N interactions with adjacent chains being connected through C—H⋯N and C—H⋯S interactions.
Related literature
For background to the biological activity of quinolinone derivatives, see: Larsen et al. (1996); Chackal et al. (2002); Kalluraya & Sreenivasa (1998); Xu et al. (2000). For the synthesis of quinolinones, see: Suarez et al. (1999).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1998); cell SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812033533/zq2174sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812033533/zq2174Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812033533/zq2174Isup3.cml
The title compound was prepared by the reaction of thiophene-2-carbaldehyde (1 mmol), 2,2-dimethyl-1,3-dioxane-4,6-dione (1 mmol), and indazol-5-amine (1 mmol) in ethylene glycol (1.0 ml). Single crystals were obtained by slow evaporation of a 95% aqueous ethanol solution (yield 70%; m.p. 553–554 K).
IR (cm-1): 3194, 3013, 2967, 1681, 1502, 1390, 1241, 1162, 1049, 937, 843, 704. 1H NMR (DMSO-d6): 13.03 (s, 1H, NH), 10.21 (s, 1H, NH), 7.42 (d, J = 8.8 Hz, 1H, ArH), 7.31–7.30 (m, 1H, ArH), 7.02 (d, J = 8.8 Hz, 1H, ArH), 6.92–6.87 (m, 2H, ArH), 4.98 (d, J = 4.4 Hz, 1H, CH), 3.12–3.06 (m, 1H, CH2), 2.77–2.72 (m, 1H, CH2).
All H atoms were positioned geometrically and treated as riding, with N—H = 0.86 Å and Uiso(H) = 1.2Ueq(N), with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for methylene H atoms, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms, and with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O).
Data collection: SMART (Bruker, 1998); cell
SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of title compound, showing 30% probability displacement ellipsoids. | |
Fig. 2. A packing diagram of title compound viewed along the a axis. |
C14H11N3OS·C2H6O | F(000) = 664 |
Mr = 315.39 | Dx = 1.352 Mg m−3 |
Monoclinic, P21/c | Melting point = 553–554 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3831 (10) Å | Cell parameters from 1612 reflections |
b = 19.138 (2) Å | θ = 2.4–25.1° |
c = 8.7490 (9) Å | µ = 0.22 mm−1 |
β = 99.412 (1)° | T = 298 K |
V = 1549.9 (3) Å3 | Block, colourless |
Z = 4 | 0.38 × 0.19 × 0.12 mm |
Bruker SMART CCD area-detector diffractometer | 2707 independent reflections |
Radiation source: fine-focus sealed tube | 1526 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
phi and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→8 |
Tmin = 0.921, Tmax = 0.974 | k = −19→22 |
7663 measured reflections | l = −10→10 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | w = 1/[σ2(Fo2) + (0.0595P)2 + 0.7752P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
2707 reflections | Δρmax = 0.28 e Å−3 |
248 parameters | Δρmin = −0.26 e Å−3 |
0 restraints |
C14H11N3OS·C2H6O | V = 1549.9 (3) Å3 |
Mr = 315.39 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.3831 (10) Å | µ = 0.22 mm−1 |
b = 19.138 (2) Å | T = 298 K |
c = 8.7490 (9) Å | 0.38 × 0.19 × 0.12 mm |
β = 99.412 (1)° |
Bruker SMART CCD area-detector diffractometer | 2707 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1526 reflections with I > 2σ(I) |
Tmin = 0.921, Tmax = 0.974 | Rint = 0.041 |
7663 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 248 parameters |
wR(F2) = 0.154 | 0 restraints |
S = 1.02 | Δρmax = 0.28 e Å−3 |
2707 reflections | Δρmin = −0.26 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 0.4885 (3) | 0.37278 (15) | 0.4386 (3) | 0.0564 (8) | |
H1 | 0.4232 | 0.4008 | 0.4606 | 0.068* | |
N2 | 0.6055 (4) | 0.39328 (15) | 0.3787 (3) | 0.0602 (8) | |
N3 | 0.5568 (3) | 0.08861 (13) | 0.4727 (3) | 0.0482 (7) | |
H3 | 0.5116 | 0.0647 | 0.5330 | 0.058* | |
O1 | 0.6492 (3) | −0.01035 (12) | 0.3895 (3) | 0.0661 (8) | |
O2 | 0.7049 (18) | 0.5320 (7) | 0.454 (2) | 0.074 (3) | 0.66 (4) |
H2 | 0.6727 | 0.4921 | 0.4459 | 0.111* | 0.66 (4) |
S1 | 0.9693 (10) | 0.2364 (5) | 0.5804 (11) | 0.0641 (12) | 0.692 (7) |
O2' | 0.660 (4) | 0.5360 (13) | 0.388 (4) | 0.074 (6) | 0.34 (4) |
H2' | 0.6242 | 0.4973 | 0.3696 | 0.111* | 0.34 (4) |
C12' | 0.969 (8) | 0.219 (3) | 0.588 (9) | 0.064 (17) | 0.308 (7) |
H12' | 0.9461 | 0.2658 | 0.5743 | 0.077* | 0.308 (7) |
C1 | 0.6784 (4) | 0.33555 (18) | 0.3592 (4) | 0.0523 (9) | |
H1A | 0.7642 | 0.3344 | 0.3190 | 0.063* | |
C2 | 0.6089 (3) | 0.27598 (15) | 0.4074 (3) | 0.0414 (8) | |
C3 | 0.4862 (3) | 0.30217 (17) | 0.4600 (4) | 0.0454 (8) | |
C4 | 0.3889 (4) | 0.25971 (18) | 0.5179 (4) | 0.0519 (9) | |
H4 | 0.3085 | 0.2782 | 0.5529 | 0.062* | |
C5 | 0.4155 (3) | 0.18913 (17) | 0.5218 (4) | 0.0478 (9) | |
H5 | 0.3522 | 0.1592 | 0.5609 | 0.057* | |
C6 | 0.5368 (3) | 0.16138 (16) | 0.4678 (4) | 0.0400 (8) | |
C7 | 0.6358 (3) | 0.20320 (16) | 0.4120 (3) | 0.0396 (8) | |
C8 | 0.7669 (3) | 0.17000 (16) | 0.3616 (4) | 0.0437 (8) | |
H8 | 0.7972 | 0.1994 | 0.2809 | 0.052* | |
C9 | 0.7228 (4) | 0.09839 (17) | 0.2912 (4) | 0.0509 (9) | |
H9A | 0.6628 | 0.1052 | 0.1910 | 0.061* | |
H9B | 0.8090 | 0.0736 | 0.2744 | 0.061* | |
C10 | 0.6422 (4) | 0.05399 (18) | 0.3891 (4) | 0.0487 (9) | |
C11 | 0.8917 (3) | 0.16488 (19) | 0.4956 (4) | 0.0466 (8) | |
C12 | 0.963 (4) | 0.106 (2) | 0.569 (4) | 0.076 (10) | 0.692 (7) |
H12 | 0.9395 | 0.0605 | 0.5401 | 0.091* | 0.692 (7) |
S1' | 0.962 (3) | 0.0921 (16) | 0.570 (3) | 0.076 (3) | 0.308 (7) |
C13 | 1.0754 (5) | 0.1238 (3) | 0.6916 (6) | 0.0920 (15) | |
H13 | 1.1337 | 0.0921 | 0.7536 | 0.110* | |
C14 | 1.0840 (4) | 0.1937 (3) | 0.7042 (5) | 0.0813 (14) | |
H14 | 1.1510 | 0.2159 | 0.7785 | 0.098* | |
C15 | 0.749 (2) | 0.5536 (8) | 0.306 (3) | 0.114 (5) | 0.66 (4) |
H15A | 0.7454 | 0.5140 | 0.2359 | 0.137* | 0.66 (4) |
H15B | 0.6848 | 0.5897 | 0.2562 | 0.137* | 0.66 (4) |
C16 | 0.896 (2) | 0.5801 (13) | 0.344 (3) | 0.142 (6) | 0.66 (4) |
H16A | 0.9040 | 0.6091 | 0.4347 | 0.213* | 0.66 (4) |
H16B | 0.9190 | 0.6072 | 0.2589 | 0.213* | 0.66 (4) |
H16C | 0.9621 | 0.5417 | 0.3639 | 0.213* | 0.66 (4) |
C15' | 0.813 (5) | 0.5334 (19) | 0.378 (5) | 0.114 (10) | 0.34 (4) |
H15C | 0.8377 | 0.4902 | 0.3306 | 0.137* | 0.34 (4) |
H15D | 0.8723 | 0.5385 | 0.4788 | 0.137* | 0.34 (4) |
C16' | 0.827 (5) | 0.595 (3) | 0.276 (5) | 0.142 (12) | 0.34 (4) |
H16D | 0.7802 | 0.5855 | 0.1720 | 0.214* | 0.34 (4) |
H16E | 0.9277 | 0.6047 | 0.2752 | 0.214* | 0.34 (4) |
H16F | 0.7831 | 0.6354 | 0.3145 | 0.214* | 0.34 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0542 (19) | 0.0485 (18) | 0.065 (2) | 0.0099 (15) | 0.0051 (16) | 0.0007 (15) |
N2 | 0.072 (2) | 0.0467 (18) | 0.062 (2) | 0.0014 (16) | 0.0107 (17) | 0.0047 (14) |
N3 | 0.0484 (16) | 0.0392 (16) | 0.0604 (18) | −0.0001 (13) | 0.0187 (14) | 0.0006 (13) |
O1 | 0.0662 (17) | 0.0407 (15) | 0.097 (2) | −0.0024 (12) | 0.0311 (15) | −0.0068 (13) |
O2 | 0.087 (7) | 0.059 (3) | 0.085 (8) | −0.006 (4) | 0.041 (6) | 0.000 (5) |
S1 | 0.0519 (16) | 0.067 (3) | 0.0727 (19) | −0.0077 (14) | 0.0084 (13) | −0.0134 (15) |
O2' | 0.087 (14) | 0.059 (7) | 0.085 (15) | −0.006 (8) | 0.041 (11) | 0.000 (9) |
C12' | 0.052 (16) | 0.07 (4) | 0.073 (18) | −0.008 (19) | 0.008 (12) | −0.01 (2) |
C1 | 0.059 (2) | 0.045 (2) | 0.053 (2) | 0.0024 (18) | 0.0121 (17) | 0.0042 (17) |
C2 | 0.0448 (19) | 0.0381 (19) | 0.0393 (18) | −0.0010 (15) | 0.0010 (15) | 0.0022 (14) |
C3 | 0.043 (2) | 0.043 (2) | 0.048 (2) | 0.0020 (16) | −0.0002 (16) | 0.0005 (16) |
C4 | 0.0376 (19) | 0.056 (2) | 0.061 (2) | 0.0068 (17) | 0.0045 (17) | −0.0076 (18) |
C5 | 0.0383 (19) | 0.050 (2) | 0.056 (2) | −0.0058 (15) | 0.0100 (16) | −0.0019 (16) |
C6 | 0.0370 (17) | 0.0382 (18) | 0.0446 (19) | 0.0009 (15) | 0.0057 (15) | 0.0011 (15) |
C7 | 0.0387 (18) | 0.0425 (19) | 0.0369 (18) | 0.0004 (15) | 0.0043 (14) | 0.0013 (14) |
C8 | 0.0468 (19) | 0.0450 (19) | 0.0421 (19) | 0.0006 (16) | 0.0159 (15) | 0.0040 (15) |
C9 | 0.051 (2) | 0.056 (2) | 0.047 (2) | 0.0009 (17) | 0.0125 (17) | −0.0040 (16) |
C10 | 0.045 (2) | 0.047 (2) | 0.053 (2) | −0.0033 (17) | 0.0078 (17) | −0.0086 (17) |
C11 | 0.0355 (17) | 0.061 (2) | 0.047 (2) | 0.0016 (18) | 0.0153 (15) | 0.0003 (18) |
C12 | 0.075 (10) | 0.061 (19) | 0.087 (11) | 0.008 (9) | −0.002 (7) | 0.001 (9) |
S1' | 0.075 (5) | 0.061 (7) | 0.087 (6) | 0.008 (3) | −0.002 (4) | 0.001 (3) |
C13 | 0.063 (3) | 0.125 (5) | 0.084 (4) | 0.026 (3) | 0.001 (3) | 0.018 (3) |
C14 | 0.048 (3) | 0.127 (4) | 0.069 (3) | −0.014 (3) | 0.008 (2) | −0.022 (3) |
C15 | 0.108 (11) | 0.121 (9) | 0.110 (12) | −0.022 (8) | 0.009 (10) | 0.038 (8) |
C16 | 0.101 (13) | 0.188 (16) | 0.144 (15) | −0.013 (11) | 0.041 (10) | 0.031 (11) |
C15' | 0.11 (2) | 0.121 (18) | 0.111 (19) | −0.021 (17) | 0.009 (18) | 0.038 (17) |
C16' | 0.10 (3) | 0.19 (3) | 0.14 (3) | −0.01 (2) | 0.04 (2) | 0.03 (2) |
N1—N2 | 1.350 (4) | C7—C8 | 1.512 (4) |
N1—C3 | 1.365 (4) | C8—C11 | 1.519 (4) |
N1—H1 | 0.8600 | C8—C9 | 1.531 (4) |
N2—C1 | 1.325 (4) | C8—H8 | 0.9800 |
N3—C10 | 1.345 (4) | C9—C10 | 1.496 (5) |
N3—C6 | 1.405 (4) | C9—H9A | 0.9700 |
N3—H3 | 0.8600 | C9—H9B | 0.9700 |
O1—C10 | 1.233 (4) | C11—C12 | 1.41 (4) |
O2—C15 | 1.48 (3) | C11—S1' | 1.63 (3) |
O2—H2 | 0.8200 | C12—C13 | 1.41 (4) |
S1—C14 | 1.618 (12) | C12—H12 | 0.9300 |
S1—C11 | 1.667 (10) | S1'—C13 | 1.50 (3) |
O2'—C15' | 1.45 (6) | C13—C14 | 1.343 (6) |
O2'—H2' | 0.8200 | C13—H13 | 0.9300 |
C12'—C11 | 1.43 (6) | C14—H14 | 0.9300 |
C12'—C14 | 1.44 (7) | C15—C16 | 1.46 (4) |
C12'—H12' | 0.9300 | C15—H15A | 0.9700 |
C1—C2 | 1.412 (4) | C15—H15B | 0.9700 |
C1—H1A | 0.9300 | C16—H16A | 0.9600 |
C2—C3 | 1.400 (5) | C16—H16B | 0.9600 |
C2—C7 | 1.415 (4) | C16—H16C | 0.9600 |
C3—C4 | 1.379 (5) | C15'—C16' | 1.51 (8) |
C4—C5 | 1.373 (4) | C15'—H15C | 0.9700 |
C4—H4 | 0.9300 | C15'—H15D | 0.9700 |
C5—C6 | 1.406 (4) | C16'—H16D | 0.9600 |
C5—H5 | 0.9300 | C16'—H16E | 0.9600 |
C6—C7 | 1.375 (4) | C16'—H16F | 0.9600 |
N2—N1—C3 | 111.9 (3) | H9A—C9—H9B | 107.6 |
N2—N1—H1 | 124.1 | O1—C10—N3 | 121.8 (3) |
C3—N1—H1 | 124.1 | O1—C10—C9 | 122.5 (3) |
C1—N2—N1 | 106.1 (3) | N3—C10—C9 | 115.7 (3) |
C10—N3—C6 | 124.1 (3) | C12—C11—C12' | 99 (3) |
C10—N3—H3 | 118.0 | C12—C11—C8 | 130.9 (17) |
C6—N3—H3 | 118.0 | C12'—C11—C8 | 130 (3) |
C15—O2—H2 | 109.5 | C12'—C11—S1' | 105 (3) |
C14—S1—C11 | 94.4 (5) | C8—C11—S1' | 125.1 (10) |
C15'—O2'—H2' | 109.5 | C12—C11—S1 | 108.0 (18) |
C11—C12'—C14 | 114 (4) | C8—C11—S1 | 121.1 (4) |
C11—C12'—H12' | 122.8 | S1'—C11—S1 | 113.8 (10) |
C14—C12'—H12' | 122.8 | C11—C12—C13 | 113 (3) |
N2—C1—C2 | 111.2 (3) | C11—C12—H12 | 123.3 |
N2—C1—H1A | 124.4 | C13—C12—H12 | 123.3 |
C2—C1—H1A | 124.4 | C13—S1'—C11 | 97.5 (17) |
C3—C2—C1 | 104.7 (3) | C14—C13—C12 | 109.0 (16) |
C3—C2—C7 | 119.7 (3) | C14—C13—S1' | 119.1 (12) |
C1—C2—C7 | 135.6 (3) | C14—C13—H13 | 125.5 |
N1—C3—C4 | 131.3 (3) | C12—C13—H13 | 125.5 |
N1—C3—C2 | 106.1 (3) | S1'—C13—H13 | 115.4 |
C4—C3—C2 | 122.6 (3) | C13—C14—C12' | 104 (2) |
C5—C4—C3 | 117.4 (3) | C13—C14—S1 | 115.1 (5) |
C5—C4—H4 | 121.3 | C13—C14—H14 | 122.4 |
C3—C4—H4 | 121.3 | C12'—C14—H14 | 133.3 |
C4—C5—C6 | 121.1 (3) | S1—C14—H14 | 122.4 |
C4—C5—H5 | 119.4 | C16—C15—O2 | 106 (3) |
C6—C5—H5 | 119.4 | C16—C15—H15A | 110.4 |
C7—C6—N3 | 119.6 (3) | O2—C15—H15A | 110.4 |
C7—C6—C5 | 122.1 (3) | C16—C15—H15B | 110.4 |
N3—C6—C5 | 118.4 (3) | O2—C15—H15B | 110.4 |
C6—C7—C2 | 117.1 (3) | H15A—C15—H15B | 108.6 |
C6—C7—C8 | 119.2 (3) | O2'—C15'—C16' | 101 (6) |
C2—C7—C8 | 123.7 (3) | O2'—C15'—H15C | 111.5 |
C7—C8—C11 | 111.3 (3) | C16'—C15'—H15C | 111.5 |
C7—C8—C9 | 108.3 (3) | O2'—C15'—H15D | 111.5 |
C11—C8—C9 | 112.1 (3) | C16'—C15'—H15D | 111.5 |
C7—C8—H8 | 108.4 | H15C—C15'—H15D | 109.3 |
C11—C8—H8 | 108.4 | C15'—C16'—H16D | 109.5 |
C9—C8—H8 | 108.4 | C15'—C16'—H16E | 109.5 |
C10—C9—C8 | 114.0 (3) | H16D—C16'—H16E | 109.5 |
C10—C9—H9A | 108.8 | C15'—C16'—H16F | 109.5 |
C8—C9—H9A | 108.8 | H16D—C16'—H16F | 109.5 |
C10—C9—H9B | 108.8 | H16E—C16'—H16F | 109.5 |
C8—C9—H9B | 108.8 | ||
C3—N1—N2—C1 | 0.9 (4) | C14—C12'—C11—C8 | −179 (2) |
N1—N2—C1—C2 | −0.2 (4) | C14—C12'—C11—S1' | 4 (5) |
N2—C1—C2—C3 | −0.4 (4) | C14—C12'—C11—S1 | −163 (25) |
N2—C1—C2—C7 | 179.4 (3) | C7—C8—C11—C12 | 116 (2) |
N2—N1—C3—C4 | 179.6 (3) | C9—C8—C11—C12 | −5 (2) |
N2—N1—C3—C2 | −1.2 (3) | C7—C8—C11—C12' | −61 (4) |
C1—C2—C3—N1 | 0.9 (3) | C9—C8—C11—C12' | 177 (4) |
C7—C2—C3—N1 | −178.9 (3) | C7—C8—C11—S1' | 115.6 (12) |
C1—C2—C3—C4 | −179.8 (3) | C9—C8—C11—S1' | −5.9 (12) |
C7—C2—C3—C4 | 0.3 (5) | C7—C8—C11—S1 | −64.4 (5) |
N1—C3—C4—C5 | 178.6 (3) | C9—C8—C11—S1 | 174.2 (5) |
C2—C3—C4—C5 | −0.5 (5) | C14—S1—C11—C12 | −1.0 (18) |
C3—C4—C5—C6 | −0.4 (5) | C14—S1—C11—C12' | 14 (20) |
C10—N3—C6—C7 | −19.3 (4) | C14—S1—C11—C8 | 179.7 (3) |
C10—N3—C6—C5 | 161.2 (3) | C14—S1—C11—S1' | −0.3 (12) |
C4—C5—C6—C7 | 1.5 (5) | C12'—C11—C12—C13 | −1 (4) |
C4—C5—C6—N3 | −179.0 (3) | C8—C11—C12—C13 | −179.7 (11) |
N3—C6—C7—C2 | 179.0 (3) | S1'—C11—C12—C13 | −173 (28) |
C5—C6—C7—C2 | −1.5 (4) | S1—C11—C12—C13 | 1 (3) |
N3—C6—C7—C8 | −1.9 (4) | C12—C11—S1'—C13 | 7 (24) |
C5—C6—C7—C8 | 177.6 (3) | C12'—C11—S1'—C13 | −3 (3) |
C3—C2—C7—C6 | 0.6 (4) | C8—C11—S1'—C13 | 179.8 (6) |
C1—C2—C7—C6 | −179.2 (3) | S1—C11—S1'—C13 | −0.2 (17) |
C3—C2—C7—C8 | −178.5 (3) | C11—C12—C13—C14 | −1 (3) |
C1—C2—C7—C8 | 1.7 (5) | C11—C12—C13—S1' | 175 (17) |
C6—C7—C8—C11 | −89.4 (3) | C11—S1'—C13—C14 | 0.8 (17) |
C2—C7—C8—C11 | 89.7 (3) | C11—S1'—C13—C12 | −4 (14) |
C6—C7—C8—C9 | 34.2 (4) | C12—C13—C14—C12' | 2 (4) |
C2—C7—C8—C9 | −146.7 (3) | S1'—C13—C14—C12' | 1 (3) |
C7—C8—C9—C10 | −49.2 (4) | C12—C13—C14—S1 | −0.3 (18) |
C11—C8—C9—C10 | 74.0 (4) | S1'—C13—C14—S1 | −1.1 (14) |
C6—N3—C10—O1 | −175.2 (3) | C11—C12'—C14—C13 | −3 (5) |
C6—N3—C10—C9 | 2.4 (4) | C11—C12'—C14—S1 | 165 (21) |
C8—C9—C10—O1 | −149.4 (3) | C11—S1—C14—C13 | 0.8 (7) |
C8—C9—C10—N3 | 33.0 (4) | C11—S1—C14—C12' | −12 (17) |
C14—C12'—C11—C12 | 3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.86 | 1.99 | 2.838 (16) | 170 |
N3—H3···O1ii | 0.86 | 2.04 | 2.863 (4) | 160 |
O2—H2···N2 | 0.82 | 2.05 | 2.855 (14) | 167 |
C8—H8···S1iii | 0.98 | 2.86 | 3.802 (6) | 162 |
C9—H9A···N1iii | 0.97 | 2.56 | 3.529 (7) | 175 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H11N3OS·C2H6O |
Mr | 315.39 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 9.3831 (10), 19.138 (2), 8.7490 (9) |
β (°) | 99.412 (1) |
V (Å3) | 1549.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.22 |
Crystal size (mm) | 0.38 × 0.19 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.921, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7663, 2707, 1526 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.154, 1.02 |
No. of reflections | 2707 |
No. of parameters | 248 |
Δρmax, Δρmin (e Å−3) | 0.28, −0.26 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.86 | 1.99 | 2.838 (16) | 170 |
N3—H3···O1ii | 0.86 | 2.04 | 2.863 (4) | 160 |
O2—H2···N2 | 0.82 | 2.05 | 2.855 (14) | 167 |
C8—H8···S1iii | 0.98 | 2.86 | 3.802 (6) | 162.2 |
C9—H9A···N1iii | 0.97 | 2.56 | 3.529 (7) | 175.1 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) x, −y+1/2, z−1/2. |
Acknowledgements
The authors thank the National Science Foundation of China (No. 20672090) for financial support.
References
Bruker (1998). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chackal, S., Houssin, R. & Henichart, J.-P. (2002). J. Org. Chem. 67, 3502–3505. Web of Science CrossRef PubMed CAS Google Scholar
Kalluraya, B. & Sreenivasa, S. (1998). Il Farmaco 53, 399–404. Web of Science CrossRef CAS PubMed Google Scholar
Larsen, R. D., Corley, E. G., King, A. O., Carrol, J. D., Davis, P., Verhoeven, T. R., Reider, P. J., Labelle, M., Gauthier, J. Y., Xiang, Y. B. & Zamboni, R. J. (1996). J. Org. Chem. 61, 3398–3405. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Suarez, M., Ochoa, E., Verdecia, Y., Pita, B., Moran, L., Martin, N., Quinteiro, M., Seoane, C., Soto, J. L., Novoa, H., Blaton, N. & Peters, O. M. (1999). Tetrahedron, 55, 875–884. Google Scholar
Xu, M. X., Wang, X. L., Mo, S. W., Li, R. X. & Cai, S. H. (2000). Chin. J. Med. Chem. 1, 12–15. Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The quinoline ring system is an important structural unit widely existing in alkaloids, therapeutics and synthetic analogues with interesting biological activities (Larsen et al., 1996). A large variety of quinoline derivatives have been used as antimalarial, anti-inflammatory, antiasthmatic, antibacterial, antihypertensive and tyrokinase PDGF-RTK inhibiting agents (Kalluraya & Sreenivasa, 1998). Various quinolinone derivatives are known to display interesting biological properties, for example, quinolinones represent the structural basis of many biologically active compounds, such as those with cardiovascular, anti-osteoporosis, anti-tumor (Chackal et al., 2002), antiinflammatory, and anti-virus (Xu et al., 2000) activities and so on.
Due to their diverse ranges of biological properties, the synthesis of these important molecules has attracted widespread attention. Some researchers have reported the synthesis of quinolinones (Suarez et al., 1999). To the best of our knowledge, however, the pyrazolo[4,3-f]quinolin-7-one derivatives have not been investigated. Because of the biological activities they exhibit, these compounds have distinguished themselves as heterocycles of profound chemical and biological significance.
In this paper we report the crystal structure of the title compound, C14H11N3OS.C2H6O, which was synthesized by the reaction of thiophene-2-carbaldehyde, 2,2-dimethyl-1,3-dioxane-4,6-dione, and indazol-5-amine in ethylene glycol without catalyst under microwave irradiation.
In the crystal structure of the title compound, the pyridine ring exhibits an envelope-like structure. The dihedral angle between the pyridine C6/C7/C8/N3 plane and the C11/C12/C13/C14/S1 thiophene ring is 81.9 (3)°, indicating that they are close to perpendicular. The dihedral angle between the pyridine C6/C7/C8/N3 plane and the C2—C7 benzene ring is 1.3 (3)°. The thiophene ring is disordered over two coplanar orientations with an occupancy ratio of 0.692 (7):0.308 (7) while the ethanol solvent molecule is also disordered over two sets of positions with a ratio of 0.66 (4):0.34 (4). Chains are formed along the b axis by N-H···O and O-H···N interactions and adjacent chains are connected through C-H···N and C-H···S interactions.