organic compounds
Benzyl 5-phenylpyrazolo[5,1-a]isoquinoline-1-carboxylate
aState Key Laboratory of Heavy Oil Processing, College of Science, China University of Petroleum (East China), Qingdao Shandong 266555, People's Republic of China, and bState Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum (East China), Qingdao Shandong 266555, People's Republic of China
*Correspondence e-mail: lyk@upc.edu.cn
In the title compound, C25H18N2O2, the pyrazolo[5,1-a]isoquinoline ring system is approximately planar [maximum deviation = 0.027 (2) Å] and is oriented at dihedral angles of 57.22 (6) and 71.36 (7)° with respect to the two phenyl rings. The phenyl rings are twisted to each other by a dihedral angle of 66.33 (8)°. A weak intramolecular C—H⋯O hydrogen bond occurs. In the crystal, weak C—H⋯π interactions are present.
Related literature
For the biological activity of fused isoquinoline compounds, see: Aubry et al. (2004); Marco et al. (2005); Reddy et al. (1999). For related structures, see: Chen & Wu (2010); Ye et al. (2010); Yu et al. (2011a,b). For selected examples of multi-component reactions, see: Dömling & Ugi (2000); Nair et al. (2003); Ramon & Yus (2005).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: PROCESS-AUTO (Rigaku, 1998); cell PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536811050586/xu5395sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811050586/xu5395Isup2.hkl
The reaction was performed in test tube under nitrogen atmosphere. 2-(phenylethynyl)benzaldehyde (0.2 mmol) was added to a solution of sulfonohydrazide (0.2 mmol) in DCE (0.5 ml). The mixture was stirred at room temperature for 30 min. Then AgOTf (7.7 mg, 0.01 mmol) was added and the reaction mixture was heated to 70 oC for 1 h. Subsequently, benzyl acrylate (0.4 mmol) and DMAc (2 ml) were added in the mixture. After completion of reaction as indicated by TLC, the reaction was quenched with aqueous NH4Cl (10 ml, 1.0 M), extracted with EtOAc (10 ml), dried by anhydrous Na2SO4. Evaporation of the solvent followed by purification on silica gel provided the crystals suitable for X-ray analysis.
H atoms were positioned geometrically with C—H = 0.95–0.99 Å, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).
In the last decade, diversity-oriented synthesis has been widely used to efficiently generate diverse small molecules. Among the strategies employed in diversity-oriented chemical synthesis, multi-component reactions are very attractive processes that push the limits of synthetic efficiency by using more than two reactants to create novel products with an optimal number of new bonds and functionalities (Dömling & Ugi, 2000; Nair et al., 2003; Ramon & Yus, 2005). Among the family of isoquinolines, the fused isoquinolines have attracted much attention owing to their biological activities including potent inhibitor of human topoisomerase I and
against HIV-1 integrase in vitro (Aubry et al., 2004; Marco et al., 2005; Reddy et al., 1999). We report herein on the single-crystal X-ray diffraction study of the title compound, synthesized from 2-(phenylethynyl)benzaldehyde, sulfonohydrazide and benzyl acrylate in DCE/DMAc.The molecular structure of the title compound is shown in Fig. 1, the bond lengths and angles are normal and correspond to those observed in related structures (Chen & Wu, 2010; Ye et al., 2010; Yu et al., 2011a; Yu et al., 2011b). It is compound of three aromatic rings namely, a pyrazolo[5,1-a]isoquinoline ring [A = (N1, N2, C7—C17)], two benzene ring [B = (C1—C6)] and [C = (C20—C25], with the dihedral angles of 57.22 (6)°, 71.36 (6)° and 66.33 (8)° between the mean planes A/B, A/C and B/C, respectively; and the carboxyl group is twisted at an angle of 8.78 (9)° relative to the A skeleton. Atoms C16 in A ring and C20 in the benzene ring are joined by the ester group (C18/O1/O2/C19) giving the torsion angles C18—O2—C19—C20 and C19—O2—C18—C16 are -96.2 (2)° and -179.81 (17)°, respectively. Atom N1 has a trigonal configuration, the sum of three bond angles around it being 360°. The mean planes of the adjacent A moieties are parallel [at an angle 0.00 (5)°] or inclined at an angle of 37.69 (4)° in the crystal lattice.
In the π interactions (Fig. 2 and Table 1), forming a three-dimensional supramolecular framework (Fig. 3), where Cg1 and Cg2 are the centroids of C11, C16, C17, N1, N2 and C20–C25 rings, respectively.
molecules are connected via C—H···For the biological activity of fused isoquinoline compounds, see: Aubry et al. (2004); Marco et al. (2005); Reddy et al. (1999). For related structures, see: Chen & Wu (2010); Ye et al. (2010); Yu et al. (2011a,b). For selected examples of multi-component reactions, see: Dömling & Ugi (2000); Nair et al. (2003); Ramon & Yus (2005).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell
PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C25H18N2O2 | F(000) = 792 |
Mr = 378.41 | Dx = 1.296 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3378 reflections |
a = 9.161 (3) Å | θ = 2.1–25.0° |
b = 18.397 (6) Å | µ = 0.08 mm−1 |
c = 11.621 (4) Å | T = 173 K |
β = 98.132 (6)° | Block, colorless |
V = 1938.9 (12) Å3 | 0.22 × 0.15 × 0.11 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 1852 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.098 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
Detector resolution: 10 pixels mm-1 | h = −9→10 |
ω scans | k = −20→21 |
9583 measured reflections | l = −13→13 |
3378 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.87 | (Δ/σ)max < 0.001 |
3378 reflections | Δρmax = 0.18 e Å−3 |
263 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0076 (11) |
C25H18N2O2 | V = 1938.9 (12) Å3 |
Mr = 378.41 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.161 (3) Å | µ = 0.08 mm−1 |
b = 18.397 (6) Å | T = 173 K |
c = 11.621 (4) Å | 0.22 × 0.15 × 0.11 mm |
β = 98.132 (6)° |
Rigaku R-AXIS RAPID diffractometer | 1852 reflections with I > 2σ(I) |
9583 measured reflections | Rint = 0.098 |
3378 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 0.87 | Δρmax = 0.18 e Å−3 |
3378 reflections | Δρmin = −0.24 e Å−3 |
263 parameters |
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 | ||
N1 | 0.4210 (2) | 0.36318 (10) | 0.06266 (15) | 0.0314 (5) | |
N2 | 0.2711 (2) | 0.36122 (10) | 0.01947 (16) | 0.0355 (5) | |
O1 | 0.41215 (19) | 0.59556 (8) | 0.15872 (15) | 0.0450 (5) | |
O2 | 0.17077 (19) | 0.56806 (8) | 0.10441 (14) | 0.0401 (5) | |
C1 | 0.3320 (3) | 0.16526 (14) | −0.1618 (2) | 0.0455 (7) | |
H1A | 0.2871 | 0.1641 | −0.2407 | 0.055* | |
C2 | 0.3482 (3) | 0.10140 (14) | −0.0978 (2) | 0.0486 (7) | |
H2B | 0.3152 | 0.0567 | −0.1332 | 0.058* | |
C3 | 0.4124 (3) | 0.10268 (13) | 0.0176 (2) | 0.0476 (7) | |
H3A | 0.4236 | 0.0589 | 0.0612 | 0.057* | |
C4 | 0.4604 (3) | 0.16836 (12) | 0.0697 (2) | 0.0405 (7) | |
H4A | 0.5029 | 0.1693 | 0.1491 | 0.049* | |
C5 | 0.4462 (3) | 0.23300 (12) | 0.0054 (2) | 0.0339 (6) | |
C6 | 0.3809 (3) | 0.23078 (13) | −0.1113 (2) | 0.0414 (7) | |
H6A | 0.3701 | 0.2743 | −0.1557 | 0.050* | |
C7 | 0.5104 (3) | 0.30141 (12) | 0.06079 (19) | 0.0335 (6) | |
C8 | 0.6539 (3) | 0.30793 (12) | 0.1091 (2) | 0.0387 (6) | |
H8A | 0.7168 | 0.2669 | 0.1095 | 0.046* | |
C9 | 0.7137 (3) | 0.37483 (13) | 0.1595 (2) | 0.0359 (6) | |
C10 | 0.6211 (3) | 0.43691 (12) | 0.16259 (19) | 0.0320 (6) | |
C11 | 0.4672 (3) | 0.43004 (12) | 0.11022 (19) | 0.0298 (6) | |
C12 | 0.8650 (3) | 0.38081 (14) | 0.2056 (2) | 0.0468 (7) | |
H12A | 0.9282 | 0.3402 | 0.2021 | 0.056* | |
C13 | 0.9217 (3) | 0.44468 (14) | 0.2553 (2) | 0.0496 (7) | |
H13A | 1.0236 | 0.4480 | 0.2851 | 0.059* | |
C14 | 0.8296 (3) | 0.50468 (14) | 0.2621 (2) | 0.0463 (7) | |
H14A | 0.8684 | 0.5480 | 0.2992 | 0.056* | |
C15 | 0.6817 (3) | 0.50136 (12) | 0.2150 (2) | 0.0384 (7) | |
H15A | 0.6208 | 0.5429 | 0.2180 | 0.046* | |
C16 | 0.3387 (3) | 0.47398 (12) | 0.09507 (19) | 0.0308 (6) | |
C17 | 0.2256 (3) | 0.42822 (12) | 0.0405 (2) | 0.0363 (6) | |
H17A | 0.1263 | 0.4437 | 0.0207 | 0.044* | |
C18 | 0.3186 (3) | 0.55095 (13) | 0.1236 (2) | 0.0352 (6) | |
C19 | 0.1330 (3) | 0.64296 (12) | 0.1286 (2) | 0.0403 (7) | |
H19A | 0.0503 | 0.6591 | 0.0700 | 0.048* | |
H19B | 0.2187 | 0.6747 | 0.1218 | 0.048* | |
C20 | 0.0897 (3) | 0.65106 (12) | 0.2487 (2) | 0.0366 (6) | |
C21 | −0.0315 (3) | 0.69401 (12) | 0.2649 (2) | 0.0462 (7) | |
H21A | −0.0878 | 0.7166 | 0.1998 | 0.055* | |
C22 | −0.0709 (3) | 0.70417 (14) | 0.3754 (3) | 0.0585 (9) | |
H22A | −0.1525 | 0.7343 | 0.3851 | 0.070* | |
C23 | 0.0080 (4) | 0.67062 (15) | 0.4707 (3) | 0.0622 (9) | |
H23A | −0.0197 | 0.6773 | 0.5457 | 0.075* | |
C24 | 0.1283 (3) | 0.62686 (15) | 0.4565 (2) | 0.0548 (8) | |
H24A | 0.1831 | 0.6037 | 0.5219 | 0.066* | |
C25 | 0.1679 (3) | 0.61719 (13) | 0.3465 (2) | 0.0434 (7) | |
H25A | 0.2496 | 0.5870 | 0.3374 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0286 (13) | 0.0336 (11) | 0.0314 (12) | −0.0006 (10) | 0.0014 (9) | −0.0017 (9) |
N2 | 0.0279 (13) | 0.0405 (12) | 0.0365 (12) | 0.0008 (11) | −0.0010 (9) | 0.0006 (9) |
O1 | 0.0367 (12) | 0.0391 (10) | 0.0573 (12) | −0.0019 (9) | 0.0002 (9) | −0.0078 (8) |
O2 | 0.0341 (11) | 0.0390 (10) | 0.0454 (11) | 0.0070 (9) | −0.0014 (8) | −0.0059 (8) |
C1 | 0.0453 (19) | 0.0571 (17) | 0.0327 (16) | 0.0032 (15) | 0.0011 (13) | −0.0113 (13) |
C2 | 0.0451 (19) | 0.0430 (16) | 0.056 (2) | −0.0034 (14) | 0.0031 (15) | −0.0117 (14) |
C3 | 0.050 (2) | 0.0409 (16) | 0.0511 (19) | 0.0027 (14) | 0.0032 (15) | 0.0019 (13) |
C4 | 0.0387 (17) | 0.0444 (15) | 0.0364 (15) | 0.0014 (14) | −0.0012 (12) | −0.0027 (12) |
C5 | 0.0309 (16) | 0.0379 (14) | 0.0327 (15) | 0.0050 (12) | 0.0039 (11) | −0.0019 (11) |
C6 | 0.0427 (18) | 0.0430 (15) | 0.0372 (16) | 0.0037 (13) | 0.0016 (12) | −0.0028 (12) |
C7 | 0.0348 (17) | 0.0340 (14) | 0.0313 (15) | 0.0058 (13) | 0.0030 (12) | −0.0011 (11) |
C8 | 0.0380 (17) | 0.0358 (14) | 0.0408 (16) | 0.0084 (14) | 0.0005 (12) | 0.0008 (11) |
C9 | 0.0320 (16) | 0.0419 (15) | 0.0326 (15) | 0.0000 (13) | 0.0004 (12) | 0.0023 (11) |
C10 | 0.0298 (16) | 0.0376 (14) | 0.0282 (14) | −0.0023 (13) | 0.0031 (11) | 0.0054 (11) |
C11 | 0.0310 (16) | 0.0323 (13) | 0.0259 (13) | −0.0017 (12) | 0.0033 (11) | 0.0011 (10) |
C12 | 0.0360 (18) | 0.0512 (17) | 0.0509 (18) | 0.0050 (15) | −0.0018 (13) | 0.0007 (13) |
C13 | 0.0307 (17) | 0.0597 (18) | 0.0552 (19) | −0.0032 (16) | −0.0046 (13) | −0.0001 (15) |
C14 | 0.0427 (19) | 0.0461 (16) | 0.0466 (17) | −0.0047 (15) | −0.0061 (14) | −0.0030 (12) |
C15 | 0.0354 (17) | 0.0373 (15) | 0.0407 (16) | −0.0003 (13) | −0.0004 (12) | 0.0004 (12) |
C16 | 0.0308 (16) | 0.0344 (14) | 0.0267 (14) | −0.0002 (13) | 0.0021 (11) | −0.0014 (11) |
C17 | 0.0344 (17) | 0.0389 (15) | 0.0348 (15) | 0.0046 (13) | 0.0023 (12) | −0.0019 (11) |
C18 | 0.0343 (17) | 0.0422 (16) | 0.0284 (14) | 0.0039 (14) | 0.0026 (12) | 0.0027 (11) |
C19 | 0.0403 (17) | 0.0348 (14) | 0.0427 (16) | 0.0098 (13) | −0.0045 (12) | −0.0019 (11) |
C20 | 0.0291 (16) | 0.0317 (14) | 0.0479 (17) | −0.0012 (13) | 0.0018 (12) | −0.0028 (12) |
C21 | 0.0360 (18) | 0.0400 (15) | 0.063 (2) | 0.0044 (14) | 0.0078 (14) | 0.0011 (13) |
C22 | 0.052 (2) | 0.0469 (17) | 0.082 (3) | 0.0066 (16) | 0.0289 (18) | −0.0035 (16) |
C23 | 0.070 (2) | 0.0604 (19) | 0.063 (2) | −0.0046 (19) | 0.0314 (19) | −0.0062 (17) |
C24 | 0.055 (2) | 0.0675 (19) | 0.0416 (18) | −0.0006 (17) | 0.0048 (15) | 0.0052 (14) |
C25 | 0.0349 (17) | 0.0518 (16) | 0.0436 (17) | −0.0002 (14) | 0.0065 (13) | −0.0037 (13) |
N1—C11 | 1.390 (3) | C11—C16 | 1.418 (3) |
N1—N2 | 1.394 (3) | C12—C13 | 1.379 (3) |
N1—C7 | 1.403 (3) | C12—H12A | 0.9500 |
N2—C17 | 1.335 (3) | C13—C14 | 1.398 (3) |
O1—C18 | 1.215 (3) | C13—H13A | 0.9500 |
O2—C18 | 1.377 (3) | C14—C15 | 1.389 (3) |
O2—C19 | 1.458 (2) | C14—H14A | 0.9500 |
C1—C2 | 1.387 (3) | C15—H15A | 0.9500 |
C1—C6 | 1.387 (3) | C16—C17 | 1.414 (3) |
C1—H1A | 0.9500 | C16—C18 | 1.472 (3) |
C2—C3 | 1.387 (4) | C17—H17A | 0.9500 |
C2—H2B | 0.9500 | C19—C20 | 1.511 (3) |
C3—C4 | 1.394 (3) | C19—H19A | 0.9900 |
C3—H3A | 0.9500 | C19—H19B | 0.9900 |
C4—C5 | 1.400 (3) | C20—C21 | 1.397 (3) |
C4—H4A | 0.9500 | C20—C25 | 1.401 (3) |
C5—C6 | 1.403 (3) | C21—C22 | 1.395 (4) |
C5—C7 | 1.496 (3) | C21—H21A | 0.9500 |
C6—H6A | 0.9500 | C22—C23 | 1.379 (4) |
C7—C8 | 1.360 (3) | C22—H22A | 0.9500 |
C8—C9 | 1.438 (3) | C23—C24 | 1.394 (4) |
C8—H8A | 0.9500 | C23—H23A | 0.9500 |
C9—C12 | 1.417 (3) | C24—C25 | 1.389 (3) |
C9—C10 | 1.427 (3) | C24—H24A | 0.9500 |
C10—C15 | 1.410 (3) | C25—H25A | 0.9500 |
C10—C11 | 1.460 (3) | ||
C11—N1—N2 | 113.26 (18) | C12—C13—H13A | 119.9 |
C11—N1—C7 | 125.3 (2) | C14—C13—H13A | 119.9 |
N2—N1—C7 | 121.39 (18) | C15—C14—C13 | 120.4 (2) |
C17—N2—N1 | 103.16 (19) | C15—C14—H14A | 119.8 |
C18—O2—C19 | 116.05 (19) | C13—C14—H14A | 119.8 |
C2—C1—C6 | 120.3 (2) | C14—C15—C10 | 120.7 (2) |
C2—C1—H1A | 119.8 | C14—C15—H15A | 119.7 |
C6—C1—H1A | 119.8 | C10—C15—H15A | 119.7 |
C3—C2—C1 | 120.2 (2) | C17—C16—C11 | 105.01 (19) |
C3—C2—H2B | 119.9 | C17—C16—C18 | 124.5 (2) |
C1—C2—H2B | 119.9 | C11—C16—C18 | 130.4 (2) |
C2—C3—C4 | 119.9 (2) | N2—C17—C16 | 113.8 (2) |
C2—C3—H3A | 120.0 | N2—C17—H17A | 123.1 |
C4—C3—H3A | 120.0 | C16—C17—H17A | 123.1 |
C3—C4—C5 | 120.3 (2) | O1—C18—O2 | 122.1 (2) |
C3—C4—H4A | 119.8 | O1—C18—C16 | 128.4 (2) |
C5—C4—H4A | 119.8 | O2—C18—C16 | 109.6 (2) |
C4—C5—C6 | 119.0 (2) | O2—C19—C20 | 111.82 (18) |
C4—C5—C7 | 119.0 (2) | O2—C19—H19A | 109.3 |
C6—C5—C7 | 121.9 (2) | C20—C19—H19A | 109.3 |
C1—C6—C5 | 120.2 (2) | O2—C19—H19B | 109.3 |
C1—C6—H6A | 119.9 | C20—C19—H19B | 109.3 |
C5—C6—H6A | 119.9 | H19A—C19—H19B | 107.9 |
C8—C7—N1 | 117.0 (2) | C21—C20—C25 | 117.8 (2) |
C8—C7—C5 | 123.4 (2) | C21—C20—C19 | 119.9 (2) |
N1—C7—C5 | 119.6 (2) | C25—C20—C19 | 122.3 (2) |
C7—C8—C9 | 122.3 (2) | C22—C21—C20 | 121.0 (3) |
C7—C8—H8A | 118.9 | C22—C21—H21A | 119.5 |
C9—C8—H8A | 118.9 | C20—C21—H21A | 119.5 |
C12—C9—C10 | 118.8 (2) | C23—C22—C21 | 120.3 (3) |
C12—C9—C8 | 121.1 (2) | C23—C22—H22A | 119.9 |
C10—C9—C8 | 120.1 (2) | C21—C22—H22A | 119.9 |
C15—C10—C9 | 119.0 (2) | C22—C23—C24 | 119.9 (3) |
C15—C10—C11 | 123.4 (2) | C22—C23—H23A | 120.1 |
C9—C10—C11 | 117.6 (2) | C24—C23—H23A | 120.1 |
N1—C11—C16 | 104.8 (2) | C25—C24—C23 | 119.7 (3) |
N1—C11—C10 | 117.6 (2) | C25—C24—H24A | 120.1 |
C16—C11—C10 | 137.6 (2) | C23—C24—H24A | 120.1 |
C13—C12—C9 | 121.0 (2) | C24—C25—C20 | 121.4 (3) |
C13—C12—H12A | 119.5 | C24—C25—H25A | 119.3 |
C9—C12—H12A | 119.5 | C20—C25—H25A | 119.3 |
C12—C13—C14 | 120.1 (2) | ||
C11—N1—N2—C17 | 0.4 (2) | C9—C10—C11—C16 | 178.3 (2) |
C7—N1—N2—C17 | 177.82 (19) | C10—C9—C12—C13 | 1.7 (4) |
C6—C1—C2—C3 | 0.5 (4) | C8—C9—C12—C13 | −179.1 (2) |
C1—C2—C3—C4 | 0.2 (4) | C9—C12—C13—C14 | 0.7 (4) |
C2—C3—C4—C5 | −1.0 (4) | C12—C13—C14—C15 | −2.5 (4) |
C3—C4—C5—C6 | 1.0 (4) | C13—C14—C15—C10 | 1.9 (4) |
C3—C4—C5—C7 | −174.8 (2) | C9—C10—C15—C14 | 0.5 (3) |
C2—C1—C6—C5 | −0.5 (4) | C11—C10—C15—C14 | −179.2 (2) |
C4—C5—C6—C1 | −0.3 (4) | N1—C11—C16—C17 | 0.8 (2) |
C7—C5—C6—C1 | 175.4 (2) | C10—C11—C16—C17 | −176.7 (2) |
C11—N1—C7—C8 | −0.3 (3) | N1—C11—C16—C18 | −177.4 (2) |
N2—N1—C7—C8 | −177.46 (19) | C10—C11—C16—C18 | 5.1 (4) |
C11—N1—C7—C5 | −179.4 (2) | N1—N2—C17—C16 | 0.2 (2) |
N2—N1—C7—C5 | 3.4 (3) | C11—C16—C17—N2 | −0.7 (3) |
C4—C5—C7—C8 | 54.6 (3) | C18—C16—C17—N2 | 177.6 (2) |
C6—C5—C7—C8 | −121.1 (3) | C19—O2—C18—O1 | 0.0 (3) |
C4—C5—C7—N1 | −126.4 (2) | C19—O2—C18—C16 | −179.81 (17) |
C6—C5—C7—N1 | 58.0 (3) | C17—C16—C18—O1 | −171.4 (2) |
N1—C7—C8—C9 | −0.4 (3) | C11—C16—C18—O1 | 6.5 (4) |
C5—C7—C8—C9 | 178.6 (2) | C17—C16—C18—O2 | 8.4 (3) |
C7—C8—C9—C12 | −177.7 (2) | C11—C16—C18—O2 | −173.7 (2) |
C7—C8—C9—C10 | 1.5 (4) | C18—O2—C19—C20 | −96.2 (2) |
C12—C9—C10—C15 | −2.2 (3) | O2—C19—C20—C21 | −137.2 (2) |
C8—C9—C10—C15 | 178.5 (2) | O2—C19—C20—C25 | 43.3 (3) |
C12—C9—C10—C11 | 177.5 (2) | C25—C20—C21—C22 | 1.5 (3) |
C8—C9—C10—C11 | −1.7 (3) | C19—C20—C21—C22 | −178.0 (2) |
N2—N1—C11—C16 | −0.8 (2) | C20—C21—C22—C23 | −1.2 (4) |
C7—N1—C11—C16 | −178.12 (19) | C21—C22—C23—C24 | 0.5 (4) |
N2—N1—C11—C10 | 177.36 (18) | C22—C23—C24—C25 | −0.1 (4) |
C7—N1—C11—C10 | 0.0 (3) | C23—C24—C25—C20 | 0.5 (4) |
C15—C10—C11—N1 | −179.3 (2) | C21—C20—C25—C24 | −1.2 (3) |
C9—C10—C11—N1 | 1.0 (3) | C19—C20—C25—C24 | 178.4 (2) |
C15—C10—C11—C16 | −1.9 (4) |
Cg1 and Cg2 are the centroids of the N1/N2C11/C16/C17 and C20–C25 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15A···O1 | 0.95 | 2.17 | 3.012 (3) | 148 |
C1—H1A···Cg1i | 0.95 | 2.76 | 3.484 (3) | 134 |
C14—H14A···Cg2ii | 0.95 | 2.68 | 3.594 (3) | 161 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C25H18N2O2 |
Mr | 378.41 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 9.161 (3), 18.397 (6), 11.621 (4) |
β (°) | 98.132 (6) |
V (Å3) | 1938.9 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.22 × 0.15 × 0.11 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9583, 3378, 1852 |
Rint | 0.098 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.116, 0.87 |
No. of reflections | 3378 |
No. of parameters | 263 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.24 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).
Cg1 and Cg2 are the centroids of the N1/N2C11/C16/C17 and C20–C25 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15A···O1 | 0.95 | 2.17 | 3.012 (3) | 148 |
C1—H1A···Cg1i | 0.95 | 2.76 | 3.484 (3) | 134 |
C14—H14A···Cg2ii | 0.95 | 2.68 | 3.594 (3) | 161 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x+1, y, z. |
Acknowledgements
This work was supported by the Natural Science Foundation of Shandong Province, China (ZR2011BQ004) and the Fundamental Research Funds for the Central Universities in China (09CX04045A).
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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.
In the last decade, diversity-oriented synthesis has been widely used to efficiently generate diverse small molecules. Among the strategies employed in diversity-oriented chemical synthesis, multi-component reactions are very attractive processes that push the limits of synthetic efficiency by using more than two reactants to create novel products with an optimal number of new bonds and functionalities (Dömling & Ugi, 2000; Nair et al., 2003; Ramon & Yus, 2005). Among the family of isoquinolines, the fused isoquinolines have attracted much attention owing to their biological activities including potent inhibitor of human topoisomerase I and selective inhibition against HIV-1 integrase in vitro (Aubry et al., 2004; Marco et al., 2005; Reddy et al., 1999). We report herein on the single-crystal X-ray diffraction study of the title compound, synthesized from 2-(phenylethynyl)benzaldehyde, sulfonohydrazide and benzyl acrylate in DCE/DMAc.
The molecular structure of the title compound is shown in Fig. 1, the bond lengths and angles are normal and correspond to those observed in related structures (Chen & Wu, 2010; Ye et al., 2010; Yu et al., 2011a; Yu et al., 2011b). It is compound of three aromatic rings namely, a pyrazolo[5,1-a]isoquinoline ring [A = (N1, N2, C7—C17)], two benzene ring [B = (C1—C6)] and [C = (C20—C25], with the dihedral angles of 57.22 (6)°, 71.36 (6)° and 66.33 (8)° between the mean planes A/B, A/C and B/C, respectively; and the carboxyl group is twisted at an angle of 8.78 (9)° relative to the A skeleton. Atoms C16 in A ring and C20 in the benzene ring are joined by the ester group (C18/O1/O2/C19) giving the torsion angles C18—O2—C19—C20 and C19—O2—C18—C16 are -96.2 (2)° and -179.81 (17)°, respectively. Atom N1 has a trigonal configuration, the sum of three bond angles around it being 360°. The mean planes of the adjacent A moieties are parallel [at an angle 0.00 (5)°] or inclined at an angle of 37.69 (4)° in the crystal lattice.
In the crystal structure, molecules are connected via C—H···π interactions (Fig. 2 and Table 1), forming a three-dimensional supramolecular framework (Fig. 3), where Cg1 and Cg2 are the centroids of C11, C16, C17, N1, N2 and C20–C25 rings, respectively.