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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1056–o1057.
Published online 2010 April 10. doi:  10.1107/S160053681001278X
PMCID: PMC2979146

5-(4-Chloro­phen­yl)-3-(2,4-dimethyl­thiazol-5-yl)-1,2,4-triazolo[3,4-a]isoquinoline

Abstract

In the title mol­ecule, C21H15ClN4S, the triazoloisoquinoline ring system is approximately planar, with an r.m.s. deviation of 0.054 (2) Å and a maximum deviation of 0.098 (2) Å from the mean plane for the triazole ring C atom that is bonded to the thia­zole ring. The thia­zole and benzene rings are twisted by 66.36 (7) and 56.32 (7)°, respectively, with respect to the mean plane of the triazoloisoquinoline ring system. In the crystal structure, mol­ecules are linked by inter­molecular C—H(...)N inter­actions along the a axis. The mol­ecular conformation is stabilized by a weak intra­molecular π–π inter­action involving the thia­zole and benzene rings, with a centroid–centroid distance of 3.6546 (11) Å. In addition, two other intermolecular π–π stacking inter­actions are observed, between the triazole and benzene rings and between the dihydro­pyridine and benzene rings [centroid–centroid distances = 3.6489 (11) and 3.5967 (10) Å, respectively].

Related literature

For the synthesis and anti­helmintic activity of triazolo compounds similar to the title compound, see: Nadkarni et al. (2001 [triangle]). For related structures, see: Hui et al. (1999 [triangle]); Khan et al. (2010 [triangle]); Zou et al. (2004 [triangle]).

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Object name is e-66-o1056-scheme1.jpg

Experimental

Crystal data

  • C21H15ClN4S
  • M r = 390.89
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1056-efi1.jpg
  • a = 7.8286 (5) Å
  • b = 8.1754 (6) Å
  • c = 15.1264 (9) Å
  • α = 93.514 (5)°
  • β = 94.805 (5)°
  • γ = 105.963 (6)°
  • V = 923.92 (11) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.33 mm−1
  • T = 290 K
  • 0.40 × 0.25 × 0.24 mm

Data collection

  • Oxford Xcalibur diffractometer with an Eos (Nova) CCD detector
  • Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009 [triangle]) T min = 0.851, T max = 0.924
  • 19579 measured reflections
  • 3439 independent reflections
  • 2518 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.111
  • S = 1.09
  • 3439 reflections
  • 246 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2009 [triangle]); cell refinement: CrysAlis PRO CCD; data reduction: CrysAlis PRO RED (Oxford Diffraction, 2009 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681001278X/fj2293sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681001278X/fj2293Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the FIST program for data collection on the single-crystal diffractometer at SSCU, IISc, Bangalore. We also thank Professor T. N. Guru Row, IISc, Bangalore, for his help with the data collection. FNK thanks the DST for Fast Track Proposal funding.

supplementary crystallographic information

Comment

Drugs including alprazolam (tranquilizer), estazolam (hypnotic, sedative, tranquilizer), rilmazafon (hypnotic, anxiolytic, used in the case of neurotic insomnia), benatradin (diuretic), trapidil (hypotensive), trazodon (antidepressant, anxiolytic), etoperidone (antidepressant), nefazodone (antidepressant, 5-HT2 A-antagonist), anastazole (antineoplastic, non-steroidal aromatase inhibitor), letrozole (antineoplastic, aromatase inhibitor), ribavirin (antiviral), fluconazole, itraconazole, terconazole (antifungal) possess 1,2,4-Triazole as the structural element. Besides, it follows from the literature data that 1,2,4-triazoles and their fused systems show antibacterial, antifungal and antiflammatory properties. As part of our search for new isoquinoline analogues, we focused on synthesis of titled compounds and the crystal structure is reported.

In the title molecule (I), Fig. 1, the triazoloisoquinoline ring system (N1–N3/C1–C9/C16) is nearly planar, with an r.m.s. deviation of 0.054 (2) Å and a maximum deviation of 0.098 (2) Å from the mean plane for the triazole ring C16 atom which is bonded to the thiazole ring (S1/N4/C17/C18/C20). The thiazole (S1/N4/C17/C18/C20) and benzene (C10—C15) rings are twisted by 66.36 (7) and 56.32 (7)°, respectively, with respect to the mean plane of the triazoloisoquinoline ring system. The thiazole ring forms a dihedral angle of 23.34 (9)° with benzene ring.

In the crystal structure of (I), molecules are linked by intermolecular C—H···N interactions along the [100] direction (Table 1, Fig. 2). Furthermore, π-π interactions [Cg1···Cg5(x, y, z) = 3.6546 (11) Å and Cg2···Cg4(2-x, 2-y, 1-z) = 3.6489 (11) Å. Where Cg1, Cg2, Cg4 and Cg5 are the centroids of the S1/N4/C17/C18/C20, N1–N3/C1/C16, C2–C7 and C10–C15 rings, respectively] are observed.

Experimental

2-(3-(4-Chlorophenylisoquinolin-1-yl)hydrazine (1 mmol) was condensed with 2,4-dimethylthiazole-5-carbaldehyde (1.1 mmol) under refluxing conditions in isopropanol (10 ml) solvent to give the corresponding hydrazone in high yield. After removal of the solvent the compound was then oxidatively cyclized in nitrobenzene (10 ml) at 473 K. The product was recrystallized from dichlomethane to give block-shaped crystals.

Refinement

All H atoms were placed in calculated positions with C–H = 0.93 and 0.96 Å and were included in the refinement in the riding model approximation, with Uiso(H) = 1.2 or 1.5Ueq(C).

Figures

Fig. 1.
The title molecule with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
Fig. 2.
View of the packing diagram and the hydrogen bonding of (I) down the [100] direction. H atoms not involved in the motif shown have been omitted for clarity.

Crystal data

C21H15ClN4SZ = 2
Mr = 390.89F(000) = 404
Triclinic, P1Dx = 1.405 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.8286 (5) ÅCell parameters from 954 reflections
b = 8.1754 (6) Åθ = 2.0–20.4°
c = 15.1264 (9) ŵ = 0.33 mm1
α = 93.514 (5)°T = 290 K
β = 94.805 (5)°Block, pale yellow
γ = 105.963 (6)°0.40 × 0.25 × 0.24 mm
V = 923.92 (11) Å3

Data collection

Oxford Xcalibur Eos (Nova) CCD detector diffractometer3439 independent reflections
Radiation source: Enhance (Mo) X-ray Source2518 reflections with I > 2σ(I)
graphiteRint = 0.035
ω scansθmax = 25.5°, θmin = 3.0°
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009)h = −9→9
Tmin = 0.851, Tmax = 0.924k = −9→9
19579 measured reflectionsl = −18→18

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0635P)2] where P = (Fo2 + 2Fc2)/3
3439 reflections(Δ/σ)max < 0.001
246 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = −0.20 e Å3

Special details

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. 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)

xyzUiso*/Ueq
S10.55766 (7)0.44377 (7)0.27355 (3)0.05951 (19)
Cl10.90834 (9)0.16939 (8)0.06573 (5)0.0843 (2)
N10.84486 (17)0.86756 (18)0.31082 (9)0.0404 (3)
N20.69901 (19)1.0456 (2)0.36035 (10)0.0527 (4)
N30.57837 (19)0.9079 (2)0.31201 (11)0.0552 (4)
N40.4093 (2)0.4452 (2)0.11718 (11)0.0566 (4)
C10.8562 (2)1.0182 (2)0.36077 (11)0.0422 (4)
C21.0238 (2)1.1181 (2)0.40777 (11)0.0424 (4)
C31.0384 (3)1.2657 (2)0.46264 (12)0.0518 (5)
H30.93901.30530.46840.062*
C41.2006 (3)1.3523 (2)0.50822 (13)0.0567 (5)
H41.21031.45030.54520.068*
C51.3493 (3)1.2952 (3)0.49973 (13)0.0572 (5)
H51.45811.35450.53130.069*
C61.3375 (2)1.1514 (3)0.44506 (13)0.0542 (5)
H61.43881.11500.43900.065*
C71.1733 (2)1.0589 (2)0.39819 (11)0.0444 (4)
C81.1543 (2)0.9065 (2)0.34138 (12)0.0466 (4)
H81.25580.87100.33410.056*
C90.9971 (2)0.8117 (2)0.29783 (11)0.0423 (4)
C100.9794 (2)0.6564 (2)0.23864 (11)0.0428 (4)
C111.0353 (2)0.5235 (3)0.27137 (13)0.0519 (5)
H111.08700.53470.32990.062*
C121.0157 (3)0.3744 (3)0.21852 (14)0.0573 (5)
H121.05320.28530.24120.069*
C130.9398 (3)0.3592 (3)0.13168 (13)0.0541 (5)
C140.8902 (2)0.4919 (3)0.09643 (12)0.0527 (5)
H140.84330.48200.03710.063*
C150.9105 (2)0.6405 (2)0.14989 (12)0.0475 (4)
H150.87760.73110.12620.057*
C160.6634 (2)0.8009 (2)0.28300 (11)0.0453 (4)
C170.5732 (2)0.6376 (2)0.23238 (12)0.0471 (4)
C180.4858 (2)0.6136 (2)0.14858 (12)0.0498 (5)
C190.4738 (3)0.7494 (3)0.09026 (15)0.0764 (7)
H19A0.35630.76450.08840.115*
H19B0.49690.71760.03120.115*
H19C0.56050.85440.11320.115*
C200.4383 (2)0.3425 (3)0.17513 (14)0.0558 (5)
C210.3769 (4)0.1526 (3)0.16023 (18)0.0799 (7)
H21A0.25050.11370.16410.120*
H21B0.43820.10430.20480.120*
H21C0.40230.11730.10230.120*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0593 (3)0.0633 (4)0.0552 (3)0.0153 (3)0.0034 (2)0.0122 (2)
Cl10.0961 (5)0.0658 (4)0.0907 (5)0.0316 (3)−0.0026 (3)−0.0189 (3)
N10.0364 (8)0.0490 (9)0.0405 (8)0.0185 (7)0.0070 (6)0.0052 (6)
N20.0451 (9)0.0614 (10)0.0577 (10)0.0276 (8)0.0029 (7)−0.0021 (8)
N30.0402 (9)0.0680 (11)0.0614 (10)0.0249 (8)0.0008 (7)−0.0027 (8)
N40.0550 (10)0.0589 (11)0.0559 (10)0.0203 (9)−0.0029 (8)−0.0027 (8)
C10.0411 (10)0.0502 (10)0.0406 (9)0.0200 (8)0.0084 (7)0.0062 (8)
C20.0439 (10)0.0467 (10)0.0384 (9)0.0135 (8)0.0085 (7)0.0095 (8)
C30.0581 (12)0.0523 (11)0.0503 (11)0.0232 (10)0.0079 (9)0.0074 (9)
C40.0691 (13)0.0485 (11)0.0486 (11)0.0115 (10)0.0044 (9)0.0009 (9)
C50.0509 (12)0.0561 (13)0.0566 (12)0.0024 (10)0.0006 (9)0.0088 (10)
C60.0384 (10)0.0640 (13)0.0588 (12)0.0106 (9)0.0084 (8)0.0072 (10)
C70.0399 (10)0.0520 (11)0.0435 (10)0.0135 (8)0.0111 (7)0.0098 (8)
C80.0342 (9)0.0601 (12)0.0501 (10)0.0192 (9)0.0110 (8)0.0049 (9)
C90.0364 (9)0.0548 (11)0.0422 (9)0.0209 (8)0.0116 (7)0.0083 (8)
C100.0362 (9)0.0540 (11)0.0435 (10)0.0190 (8)0.0112 (7)0.0054 (8)
C110.0526 (11)0.0644 (13)0.0468 (11)0.0290 (10)0.0064 (8)0.0078 (9)
C120.0618 (12)0.0573 (12)0.0628 (13)0.0308 (11)0.0119 (10)0.0114 (10)
C130.0511 (11)0.0549 (12)0.0586 (12)0.0183 (10)0.0109 (9)−0.0014 (9)
C140.0518 (11)0.0665 (13)0.0436 (10)0.0232 (10)0.0066 (8)0.0011 (9)
C150.0457 (10)0.0586 (12)0.0454 (10)0.0242 (9)0.0099 (8)0.0085 (9)
C160.0344 (9)0.0608 (12)0.0442 (10)0.0189 (9)0.0041 (7)0.0053 (9)
C170.0354 (9)0.0592 (12)0.0495 (11)0.0181 (9)0.0048 (8)0.0037 (9)
C180.0460 (10)0.0538 (11)0.0521 (11)0.0215 (9)−0.0021 (8)−0.0002 (9)
C190.0994 (17)0.0625 (14)0.0660 (14)0.0318 (13)−0.0244 (12)0.0001 (11)
C200.0501 (11)0.0564 (12)0.0623 (13)0.0169 (10)0.0088 (9)0.0039 (10)
C210.0942 (18)0.0585 (14)0.0864 (17)0.0212 (13)0.0081 (13)0.0040 (12)

Geometric parameters (Å, °)

S1—C171.7150 (19)C8—C91.351 (2)
S1—C201.722 (2)C8—H80.9300
Cl1—C131.7387 (19)C9—C101.475 (2)
N1—C11.382 (2)C10—C111.382 (2)
N1—C161.392 (2)C10—C151.389 (2)
N1—C91.413 (2)C11—C121.381 (3)
N2—C11.310 (2)C11—H110.9300
N2—N31.376 (2)C12—C131.379 (3)
N3—C161.313 (2)C12—H120.9300
N4—C201.299 (3)C13—C141.371 (3)
N4—C181.378 (2)C14—C151.381 (2)
C1—C21.441 (2)C14—H140.9300
C2—C31.394 (2)C15—H150.9300
C2—C71.399 (2)C16—C171.460 (2)
C3—C41.374 (3)C17—C181.365 (3)
C3—H30.9300C18—C191.477 (3)
C4—C51.380 (3)C19—H19A0.9600
C4—H40.9300C19—H19B0.9600
C5—C61.372 (2)C19—H19C0.9600
C5—H50.9300C20—C211.490 (3)
C6—C71.405 (3)C21—H21A0.9600
C6—H60.9300C21—H21B0.9600
C7—C81.435 (2)C21—H21C0.9600
C17—S1—C2089.71 (9)C12—C11—H11119.5
C1—N1—C16104.18 (13)C10—C11—H11119.5
C1—N1—C9122.02 (14)C13—C12—C11119.11 (18)
C16—N1—C9133.80 (15)C13—C12—H12120.4
C1—N2—N3106.96 (14)C11—C12—H12120.4
C16—N3—N2109.14 (14)C14—C13—C12121.03 (18)
C20—N4—C18111.44 (17)C14—C13—Cl1119.56 (16)
N2—C1—N1110.74 (15)C12—C13—Cl1119.41 (16)
N2—C1—C2128.52 (16)C13—C14—C15119.30 (18)
N1—C1—C2120.68 (14)C13—C14—H14120.3
C3—C2—C7120.43 (17)C15—C14—H14120.3
C3—C2—C1122.28 (16)C14—C15—C10120.84 (18)
C7—C2—C1117.26 (16)C14—C15—H15119.6
C4—C3—C2119.62 (18)C10—C15—H15119.6
C4—C3—H3120.2N3—C16—N1108.91 (16)
C2—C3—H3120.2N3—C16—C17123.14 (15)
C3—C4—C5120.64 (19)N1—C16—C17127.92 (15)
C3—C4—H4119.7C18—C17—C16126.79 (17)
C5—C4—H4119.7C18—C17—S1109.80 (14)
C6—C5—C4120.41 (19)C16—C17—S1123.38 (14)
C6—C5—H5119.8C17—C18—N4114.72 (17)
C4—C5—H5119.8C17—C18—C19125.94 (18)
C5—C6—C7120.40 (18)N4—C18—C19119.29 (17)
C5—C6—H6119.8C18—C19—H19A109.5
C7—C6—H6119.8C18—C19—H19B109.5
C2—C7—C6118.48 (17)H19A—C19—H19B109.5
C2—C7—C8119.24 (16)C18—C19—H19C109.5
C6—C7—C8122.28 (16)H19A—C19—H19C109.5
C9—C8—C7123.62 (16)H19B—C19—H19C109.5
C9—C8—H8118.2N4—C20—C21124.4 (2)
C7—C8—H8118.2N4—C20—S1114.31 (16)
C8—C9—N1116.99 (16)C21—C20—S1121.26 (17)
C8—C9—C10123.21 (15)C20—C21—H21A109.5
N1—C9—C10119.80 (14)C20—C21—H21B109.5
C11—C10—C15118.60 (17)H21A—C21—H21B109.5
C11—C10—C9119.53 (16)C20—C21—H21C109.5
C15—C10—C9121.87 (16)H21A—C21—H21C109.5
C12—C11—C10121.00 (18)H21B—C21—H21C109.5
C1—N2—N3—C16−0.8 (2)N1—C9—C10—C1557.7 (2)
N3—N2—C1—N12.2 (2)C15—C10—C11—C12−3.1 (3)
N3—N2—C1—C2−174.89 (17)C9—C10—C11—C12178.05 (16)
C16—N1—C1—N2−2.68 (19)C10—C11—C12—C130.3 (3)
C9—N1—C1—N2177.60 (14)C11—C12—C13—C142.5 (3)
C16—N1—C1—C2174.71 (15)C11—C12—C13—Cl1−178.02 (15)
C9—N1—C1—C2−5.0 (2)C12—C13—C14—C15−2.5 (3)
N2—C1—C2—C30.4 (3)Cl1—C13—C14—C15178.05 (13)
N1—C1—C2—C3−176.44 (16)C13—C14—C15—C10−0.4 (3)
N2—C1—C2—C7178.86 (17)C11—C10—C15—C143.1 (3)
N1—C1—C2—C72.0 (2)C9—C10—C15—C14−178.05 (15)
C7—C2—C3—C4−0.7 (3)N2—N3—C16—N1−0.8 (2)
C1—C2—C3—C4177.71 (16)N2—N3—C16—C17177.39 (16)
C2—C3—C4—C50.4 (3)C1—N1—C16—N32.09 (18)
C3—C4—C5—C60.4 (3)C9—N1—C16—N3−178.24 (17)
C4—C5—C6—C7−1.1 (3)C1—N1—C16—C17−176.03 (17)
C3—C2—C7—C60.1 (3)C9—N1—C16—C173.6 (3)
C1—C2—C7—C6−178.40 (15)N3—C16—C17—C1866.9 (3)
C3—C2—C7—C8179.91 (16)N1—C16—C17—C18−115.2 (2)
C1—C2—C7—C81.4 (2)N3—C16—C17—S1−111.10 (18)
C5—C6—C7—C20.8 (3)N1—C16—C17—S166.8 (2)
C5—C6—C7—C8−179.03 (17)C20—S1—C17—C181.01 (14)
C2—C7—C8—C9−2.1 (3)C20—S1—C17—C16179.31 (15)
C6—C7—C8—C9177.69 (17)C16—C17—C18—N4−178.77 (15)
C7—C8—C9—N1−0.7 (3)S1—C17—C18—N4−0.5 (2)
C7—C8—C9—C10179.18 (16)C16—C17—C18—C193.7 (3)
C1—N1—C9—C84.3 (2)S1—C17—C18—C19−178.11 (17)
C16—N1—C9—C8−175.35 (17)C20—N4—C18—C17−0.5 (2)
C1—N1—C9—C10−175.59 (15)C20—N4—C18—C19177.28 (18)
C16—N1—C9—C104.8 (3)C18—N4—C20—C21−178.43 (18)
C8—C9—C10—C1156.7 (2)C18—N4—C20—S11.3 (2)
N1—C9—C10—C11−123.46 (18)C17—S1—C20—N4−1.35 (15)
C8—C9—C10—C15−122.2 (2)C17—S1—C20—C21178.36 (17)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6···N2i0.932.623.495 (2)158
C8—H8···N3i0.932.513.383 (2)156

Symmetry codes: (i) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2293).

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