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The title compound, C17H12ClN5S, has been synthesized as a potent anti­cancer agent. The dihedral angle between the thia­zole and triazole rings is 85.9 (2)°. There are inter­molecular N—H...N and C—H...Cl inter­actions in the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040146/ob6593sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040146/ob6593Isup2.hkl
Contains datablock I

CCDC reference: 296619

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.039
  • wR factor = 0.104
  • Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.03 PLAT322_ALERT_2_C Check Hybridisation of S1 in Main Residue . ? PLAT480_ALERT_4_C Long H...A H-Bond Reported H13 .. CL1 .. 2.87 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The aminothiazole ring system has found application in drug development for the treatment of allergies, hypertension, inflammation, schizophrenia, and bacterial and HIV infections (Arcadi et al., 1999). For example, aminothiazole BMS-387032 {N-[5-({[5-(1,1-dimethylethyl)-2-oxazolyl]methyl}thio)-2-thizolyl]-4- piperidinecarboxamide} has been selected to enter clinical development as an antitumour agent (Misra et al., 2004). In the search for novel aminothiazole compounds with potent antitumour activities and as a continuation of our studies of thiazole molecules (Shao et al., 2005), we have designed and synthesized such 2-aminothiazole compounds incorporating the 1H-1,2,4-triazole unit. In this paper, we report the crystal structure of the title compound, (I).

Fig. 1 shows the molecular structure of (I), which contains four planar subunits, namely the thiazole ring (P1), the substituted C5–C10 benzene ring (P2), the C12–C17 phenyl ring (P3) and the triazole ring (P4). The dihedral angles between P1 and P2, P3 and P4 are 6.1 (4), 14.0 (3) and 85.9 (2)°, respectively. The C11—N5 and C3—N3 bond lengths in (I) [1.354 (2) and 1.415 (2) Å] are longer than the corresponding distances in 2-amino-4-(2,5-dichlorophenyl)-5-(1H-1,2,4-triazol-1-yl)-1,3-thiazole [1.339 (3) and 1.402 (3) Å; Shao et al., 2004].

In (I), the molecules are associated via N—H···N and C—H···Cl interactions (Table 2 and Fig. 2).

Experimental top

α-Bromo-α-(1H-1,2,4-triazol-1-yl)-4-chloroacetophenone (2.66 g, 10 mmol) and dry sodium thiocyanate (0.97 g, 12 mmol) were stirred in ethanol (25 ml) for 3 h at 323 K. A solution of aniline (0.93 g, 10 mmol) in ethanol (5 ml) was added in one portion and the reaction mixture was stirred for 8 h. The ethanol was distilled off, and ethyl acetate and water were added (Volumes?). The aqueous phase was extracted twice with ethyl acetate, and the combined organic phases were dried with MgSO4, and the solvent was removed in vacuo. The residue was then purified via column chromatography on silica gel (Eluent?) to afford (I) in a yield of 15% (m.p. 483 K). Analysis: C 57.56, H 3.52, N 20.03%; calculated for [Formula missing]: C 57.71, H 3.42, N 19.79%. Spectroscopic analysis: 1H NMR (DMSO, δ, p.p.m.): 10.629 (s, 1H, N—H), 8.858 (s, 1H, Tr—H), 8.369 (s, 1H, Tr—H), 7.717, 7.691 (d, 2H, p-Cl—Ph—H, J = 7.8 Hz), 7.462, 7.436 (d, 2H, p-Cl—Ph—H, J = 7.8 Hz), 7.411–7.023 (m, 5H, Ph—H).

Refinement top

The amino H atom was located in a difference Fourier map and refined isotropically, with the distance restraint N—H = 0.83 (3) Å. Other H atoms were placed in calculated positions, with C—H = 0.93 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular configuration and atom-numbering scheme for (I). Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A packing diagram for (I), viewed down the a axis. Dashed lines indicate hydrogen bonds.
4-(4-Chlorophenyl)-N-phenyl-5-(1H-1,2,4-triazol-1-yl)thiazol-2-amine top
Crystal data top
C17H12ClN5SF(000) = 728
Mr = 353.83Dx = 1.469 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ynCell parameters from 3277 reflections
a = 9.5139 (18) Åθ = 2.2–26.4°
b = 13.681 (3) ŵ = 0.38 mm1
c = 12.439 (3) ÅT = 294 K
β = 98.828 (3)°Parallelepiped, colourless
V = 1599.9 (5) Å30.24 × 0.22 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
3279 independent reflections
Radiation source: fine-focus sealed tube2449 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ϕ and ω scansθmax = 26.4°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 911
Tmin = 0.903, Tmax = 0.928k = 1117
8842 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0499P)2 + 0.5099P]
where P = (Fo2 + 2Fc2)/3
3279 reflections(Δ/σ)max < 0.001
221 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
C17H12ClN5SV = 1599.9 (5) Å3
Mr = 353.83Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.5139 (18) ŵ = 0.38 mm1
b = 13.681 (3) ÅT = 294 K
c = 12.439 (3) Å0.24 × 0.22 × 0.20 mm
β = 98.828 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3279 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2449 reflections with I > 2σ(I)
Tmin = 0.903, Tmax = 0.928Rint = 0.031
8842 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.23 e Å3
3279 reflectionsΔρmin = 0.33 e Å3
221 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.62799 (5)0.29951 (4)0.77969 (5)0.04107 (16)
Cl10.37789 (8)0.87301 (4)0.94633 (6)0.0688 (2)
N10.94670 (18)0.55483 (14)0.74501 (17)0.0498 (5)
N20.86744 (17)0.48455 (14)0.88833 (15)0.0474 (5)
N30.77183 (15)0.47228 (12)0.79540 (13)0.0340 (4)
N40.41660 (16)0.39374 (11)0.83975 (13)0.0341 (4)
N50.38380 (17)0.22234 (13)0.82124 (15)0.0400 (4)
H50.427 (3)0.1713 (19)0.809 (2)0.054 (7)*
C10.9687 (2)0.53416 (17)0.8525 (2)0.0497 (6)
H11.05050.55380.89820.060*
C20.8222 (2)0.51438 (17)0.71211 (18)0.0455 (5)
H20.77560.51500.64070.055*
C30.64023 (19)0.42529 (14)0.79944 (16)0.0340 (4)
C40.52166 (18)0.46324 (14)0.83231 (15)0.0314 (4)
C50.49206 (18)0.56457 (14)0.86172 (15)0.0321 (4)
C60.5810 (2)0.64335 (15)0.8485 (2)0.0469 (5)
H60.66560.63230.82150.056*
C70.5462 (2)0.73707 (16)0.8746 (2)0.0500 (6)
H70.60650.78880.86500.060*
C80.4216 (2)0.75392 (15)0.91490 (17)0.0414 (5)
C90.3323 (2)0.67798 (16)0.93032 (18)0.0433 (5)
H90.24840.68970.95800.052*
C100.3683 (2)0.58415 (15)0.90442 (17)0.0382 (5)
H100.30830.53270.91580.046*
C110.45743 (18)0.30659 (14)0.81708 (16)0.0341 (4)
C120.25823 (18)0.20682 (14)0.86579 (16)0.0336 (4)
C130.2227 (2)0.11027 (15)0.88219 (18)0.0418 (5)
H130.28020.06020.86300.050*
C140.1027 (2)0.08796 (17)0.9267 (2)0.0524 (6)
H140.08000.02300.93790.063*
C150.0162 (2)0.16115 (18)0.9548 (2)0.0563 (6)
H150.06460.14610.98520.068*
C160.0503 (2)0.25682 (18)0.9374 (2)0.0567 (6)
H160.00830.30640.95600.068*
C170.1707 (2)0.28099 (15)0.8926 (2)0.0474 (6)
H170.19220.34600.88070.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0321 (3)0.0355 (3)0.0606 (4)0.0025 (2)0.0230 (2)0.0066 (2)
Cl10.0836 (5)0.0350 (3)0.0948 (5)0.0131 (3)0.0356 (4)0.0012 (3)
N10.0381 (10)0.0477 (11)0.0685 (13)0.0086 (8)0.0236 (9)0.0072 (9)
N20.0342 (9)0.0550 (12)0.0529 (11)0.0074 (8)0.0064 (8)0.0106 (9)
N30.0261 (8)0.0353 (9)0.0431 (9)0.0013 (7)0.0131 (7)0.0029 (7)
N40.0259 (8)0.0307 (8)0.0474 (10)0.0025 (6)0.0115 (7)0.0021 (7)
N50.0300 (9)0.0293 (9)0.0648 (12)0.0029 (7)0.0202 (8)0.0093 (8)
C10.0289 (10)0.0508 (13)0.0696 (16)0.0066 (9)0.0081 (10)0.0065 (12)
C20.0412 (11)0.0535 (13)0.0451 (12)0.0067 (10)0.0169 (9)0.0073 (10)
C30.0294 (10)0.0315 (10)0.0438 (11)0.0033 (8)0.0139 (8)0.0010 (8)
C40.0258 (9)0.0336 (10)0.0359 (10)0.0028 (8)0.0082 (8)0.0024 (8)
C50.0276 (9)0.0333 (10)0.0359 (10)0.0009 (8)0.0063 (8)0.0029 (8)
C60.0391 (11)0.0376 (11)0.0699 (15)0.0035 (9)0.0278 (11)0.0001 (11)
C70.0495 (13)0.0314 (11)0.0742 (16)0.0051 (10)0.0256 (11)0.0006 (11)
C80.0484 (12)0.0315 (10)0.0460 (12)0.0065 (9)0.0121 (10)0.0003 (9)
C90.0354 (11)0.0448 (12)0.0523 (13)0.0055 (9)0.0153 (9)0.0001 (10)
C100.0312 (10)0.0363 (11)0.0486 (12)0.0039 (8)0.0113 (9)0.0010 (9)
C110.0261 (9)0.0356 (11)0.0423 (11)0.0028 (8)0.0112 (8)0.0037 (9)
C120.0272 (9)0.0337 (10)0.0411 (11)0.0021 (8)0.0093 (8)0.0040 (8)
C130.0400 (11)0.0327 (11)0.0550 (13)0.0015 (9)0.0144 (10)0.0012 (9)
C140.0536 (13)0.0399 (12)0.0689 (16)0.0076 (10)0.0258 (12)0.0090 (11)
C150.0469 (13)0.0556 (15)0.0745 (17)0.0091 (11)0.0351 (12)0.0005 (12)
C160.0426 (12)0.0475 (13)0.0882 (18)0.0004 (10)0.0356 (12)0.0097 (13)
C170.0378 (11)0.0319 (11)0.0774 (16)0.0034 (9)0.0242 (11)0.0049 (10)
Geometric parameters (Å, º) top
S1—C31.740 (2)C6—C71.376 (3)
S1—C111.7579 (18)C6—H60.9300
Cl1—C81.741 (2)C7—C81.376 (3)
N1—C21.314 (3)C7—H70.9300
N1—C11.351 (3)C8—C91.374 (3)
N2—C11.311 (3)C9—C101.380 (3)
N2—N31.367 (2)C9—H90.9300
N3—C21.337 (2)C10—H100.9300
N3—C31.415 (2)C12—C171.385 (3)
N4—C111.298 (2)C12—C131.386 (3)
N4—C41.393 (2)C13—C141.378 (3)
N5—C111.354 (2)C13—H130.9300
N5—C121.408 (2)C14—C151.375 (3)
N5—H50.83 (3)C14—H140.9300
C1—H10.9300C15—C161.374 (3)
C2—H20.9300C15—H150.9300
C3—C41.360 (3)C16—C171.388 (3)
C4—C51.472 (3)C16—H160.9300
C5—C101.390 (3)C17—H170.9300
C5—C61.396 (3)
C3—S1—C1187.29 (9)C9—C8—C7120.66 (19)
C2—N1—C1102.45 (17)C9—C8—Cl1120.17 (16)
C1—N2—N3101.80 (17)C7—C8—Cl1119.18 (16)
C2—N3—N2109.34 (16)C8—C9—C10119.35 (18)
C2—N3—C3130.37 (18)C8—C9—H9120.3
N2—N3—C3120.21 (15)C10—C9—H9120.3
C11—N4—C4111.76 (15)C9—C10—C5121.59 (19)
C11—N5—C12128.22 (17)C9—C10—H10119.2
C11—N5—H5115.7 (17)C5—C10—H10119.2
C12—N5—H5114.5 (17)N4—C11—N5126.85 (17)
N2—C1—N1115.7 (2)N4—C11—S1115.28 (14)
N2—C1—H1122.1N5—C11—S1117.86 (14)
N1—C1—H1122.1C17—C12—C13119.55 (17)
N1—C2—N3110.7 (2)C17—C12—N5124.18 (18)
N1—C2—H2124.7C13—C12—N5116.27 (17)
N3—C2—H2124.7C14—C13—C12120.42 (19)
C4—C3—N3128.04 (18)C14—C13—H13119.8
C4—C3—S1112.29 (13)C12—C13—H13119.8
N3—C3—S1119.00 (13)C15—C14—C13120.4 (2)
C3—C4—N4113.33 (17)C15—C14—H14119.8
C3—C4—C5129.29 (17)C13—C14—H14119.8
N4—C4—C5117.37 (15)C16—C15—C14119.2 (2)
C10—C5—C6117.45 (18)C16—C15—H15120.4
C10—C5—C4118.81 (16)C14—C15—H15120.4
C6—C5—C4123.73 (17)C15—C16—C17121.3 (2)
C7—C6—C5121.27 (19)C15—C16—H16119.3
C7—C6—H6119.4C17—C16—H16119.3
C5—C6—H6119.4C12—C17—C16119.0 (2)
C8—C7—C6119.7 (2)C12—C17—H17120.5
C8—C7—H7120.2C16—C17—H17120.5
C6—C7—H7120.2
C1—N2—N3—C20.2 (2)C5—C6—C7—C80.2 (4)
C1—N2—N3—C3176.79 (18)C6—C7—C8—C90.6 (4)
N3—N2—C1—N10.0 (3)C6—C7—C8—Cl1179.37 (19)
C2—N1—C1—N20.3 (3)C7—C8—C9—C100.3 (3)
C1—N1—C2—N30.4 (2)Cl1—C8—C9—C10179.66 (16)
N2—N3—C2—N10.4 (2)C8—C9—C10—C50.8 (3)
C3—N3—C2—N1176.20 (19)C6—C5—C10—C91.6 (3)
C2—N3—C3—C497.8 (3)C4—C5—C10—C9177.90 (19)
N2—N3—C3—C478.5 (3)C4—N4—C11—N5176.91 (19)
C2—N3—C3—S192.3 (2)C4—N4—C11—S11.9 (2)
N2—N3—C3—S191.4 (2)C12—N5—C11—N410.5 (4)
C11—S1—C3—C40.52 (16)C12—N5—C11—S1168.27 (17)
C11—S1—C3—N3171.89 (16)C3—S1—C11—N40.80 (16)
N3—C3—C4—N4172.05 (18)C3—S1—C11—N5178.09 (17)
S1—C3—C4—N41.7 (2)C11—N5—C12—C1714.8 (3)
N3—C3—C4—C56.9 (3)C11—N5—C12—C13165.6 (2)
S1—C3—C4—C5177.28 (16)C17—C12—C13—C141.2 (3)
C11—N4—C4—C32.3 (2)N5—C12—C13—C14179.2 (2)
C11—N4—C4—C5176.81 (17)C12—C13—C14—C150.4 (4)
C3—C4—C5—C10173.1 (2)C13—C14—C15—C160.3 (4)
N4—C4—C5—C105.8 (3)C14—C15—C16—C170.3 (4)
C3—C4—C5—C67.4 (3)C13—C12—C17—C161.3 (3)
N4—C4—C5—C6173.69 (19)N5—C12—C17—C16179.2 (2)
C10—C5—C6—C71.3 (3)C15—C16—C17—C120.5 (4)
C4—C5—C6—C7178.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5···N1i0.83 (3)2.17 (3)2.990 (2)170 (2)
C13—H13···Cl1ii0.932.873.605 (2)137
Symmetry codes: (i) x+3/2, y1/2, z+3/2; (ii) x, y1, z.

Experimental details

Crystal data
Chemical formulaC17H12ClN5S
Mr353.83
Crystal system, space groupMonoclinic, P21/n
Temperature (K)294
a, b, c (Å)9.5139 (18), 13.681 (3), 12.439 (3)
β (°) 98.828 (3)
V3)1599.9 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.24 × 0.22 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.903, 0.928
No. of measured, independent and
observed [I > 2σ(I)] reflections
8842, 3279, 2449
Rint0.031
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.104, 1.02
No. of reflections3279
No. of parameters221
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.23, 0.33

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.

Selected geometric parameters (Å, º) top
S1—C31.740 (2)N3—C31.415 (2)
S1—C111.7579 (18)N4—C111.298 (2)
N1—C21.314 (3)N4—C41.393 (2)
N1—C11.351 (3)N5—C111.354 (2)
N2—N31.367 (2)N5—C121.408 (2)
N3—C21.337 (2)
C3—S1—C1187.29 (9)C11—N5—C12128.22 (17)
C2—N1—C1102.45 (17)N2—C1—N1115.7 (2)
C1—N2—N3101.80 (17)N1—C2—N3110.7 (2)
C2—N3—N2109.34 (16)C4—C3—S1112.29 (13)
C2—N3—C3130.37 (18)C3—C4—N4113.33 (17)
C11—N4—C4111.76 (15)
N2—N3—C3—C478.5 (3)C12—N5—C11—N410.5 (4)
C3—C4—C5—C10173.1 (2)C11—N5—C12—C1714.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5···N1i0.83 (3)2.17 (3)2.990 (2)170 (2)
C13—H13···Cl1ii0.932.873.605 (2)137
Symmetry codes: (i) x+3/2, y1/2, z+3/2; (ii) x, y1, z.
 

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